Research Article Synthesis, Crystal Structure, and DFT ...
6
Research Article Synthesis, Crystal Structure, and DFT Calculations of 1,3-Diisobutyl Thiourea Ataf A. Altaf, 1 Adnan Shahzad, 2 Zarif Gul, 2 Sher A. Khan, 2 Amin Badshah, 3 Muhammad N. Tahir, 4 Zafar I. Zafar, 5 and Ezzat Khan 2 1 Department of Chemistry, Government College University, Faisalabad 38000, Pakistan 2 Department of Chemistry, University of Malakand, Dir Lower, Khyber Pakhtunkhwa, Chakdara 18550, Pakistan 3 Department of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan 4 Department of Physics, University of Sargodha, Sargodha, Punjab 40100, Pakistan 5 Inorganic Chemistry Division, Institute of Chemical Sciences, Bahauddin Zakariya University, Multan 60800, Pakistan Correspondence should be addressed to Ataf A. Altaf; atafali [email protected] and Ezzat Khan; [email protected] Received 13 November 2014; Revised 5 February 2015; Accepted 12 February 2015 Academic Editor: Marc Visseaux Copyright © 2015 Ataf A. Altaf et al. is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. 1,3-Diisobutyl thiourea was synthesized and characterized by single crystal X-ray diffraction. It gives a monoclinic ( = = 90 and ̸ = 90) structure with the space group P21/c. e unit cell dimensions are a = 11.5131 (4) ˚ A, b = 9.2355 (3) ˚ A, c = 11.3093 (5) ˚ A, = 90 ∘ , = 99.569 ∘ (2), = 90 ∘ , V = 1185.78 (8) ˚ A 3 , and Z = 4. e crystal packing is stabilized by intermolecular (N–H⋅⋅⋅ S) hydrogen bonding in the molecules. e optimized geometry and Mullikan’s charges of the said molecule calculated with the help of DFT using B3LYP-6-311G model support the crystal structure. 1. Introduction iourea derivatives are well known sulphur containing com- pounds acting as ligands in the field of coordination chem- istry [1–3]. Such ligands are capable of affording complexes with metal ions; the resultant complexes have been reported to have imperative antimicrobial [4] and anticonvulsant [5] applications. iourea derivatives and their complexes have numerous catalytic applications in asymmetric organocatal- ysis [6–8], have been used as cocatalysts in Pauson-Khand reactions [1], Pd-catalyzed reactions [1, 9], Heck and Suzuki coupling reactions, and so forth [2, 9]. iourea derivatives got much more attention in the field of highly enantio- and diastereoselective catalysis [10] and have also been applied as cocatalysts in nanoparticles and a number of other types of reactions [11, 12]. e challenging task in the chemistry of thiourea is its syntheses and structural characterization. Several research groups are trying to make this versatile group of compounds easily accessible and have reported various methods [13–16]. In continuation to our previous work [17] the title com- pound was obtained unexpectedly. Surprisingly a compre- hensive research survey does not show solid state structural data of title compound 1. e structure of the compound was determined by X-ray diffraction and its DFT optimized geometry was determined using B3LYP-6311G model of theory [18]. eoretical data obtained for the compound compare well with the experimental data. 2. Experimental All chemicals, that is, carbon disulphide and isobutyl amine, are commercially available and were used without further purification. Solvents were distilled prior to use. 2.1. Synthesis of 1,3-Di(isobutyl)thiourea. Solution of carbon disulphide (498.0 mmole; 50 mL) was prepared in petroleum ether (100 mL) and was cooled to 0 ∘ C in an ice bath, following Hindawi Publishing Corporation Journal of Chemistry Volume 2015, Article ID 913435, 5 pages http://dx.doi.org/10.1155/2015/913435
Transcript of Research Article Synthesis, Crystal Structure, and DFT ...
Research ArticleSynthesis Crystal Structure and DFT Calculations of13-Diisobutyl Thiourea
Ataf A Altaf1 Adnan Shahzad2 Zarif Gul2 Sher A Khan2 Amin Badshah3
Muhammad N Tahir4 Zafar I Zafar5 and Ezzat Khan2
1Department of Chemistry Government College University Faisalabad 38000 Pakistan2Department of Chemistry University of Malakand Dir Lower Khyber Pakhtunkhwa Chakdara 18550 Pakistan3Department of Chemistry Quaid-i-Azam University Islamabad 45320 Pakistan4Department of Physics University of Sargodha Sargodha Punjab 40100 Pakistan5Inorganic Chemistry Division Institute of Chemical Sciences Bahauddin Zakariya University Multan 60800 Pakistan
Correspondence should be addressed to Ataf A Altaf atafali altafyahoocom and Ezzat Khan ekhanuomedupk
Received 13 November 2014 Revised 5 February 2015 Accepted 12 February 2015
Academic Editor Marc Visseaux
Copyright copy 2015 Ataf A Altaf et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited
13-Diisobutyl thiourea was synthesized and characterized by single crystal X-ray diffraction It gives a monoclinic (120572 = 120574 = 90 and120573 = 90) structure with the space group P21c The unit cell dimensions are a = 115131 (4) A b = 92355 (3) A c = 113093 (5) A 120572 =90∘ 120573 = 99569∘ (2) 120574 = 90∘ V = 118578 (8) A3 and Z = 4The crystal packing is stabilized by intermolecular (NndashHsdot sdot sdot S) hydrogenbonding in the molecules The optimized geometry and Mullikanrsquos charges of the said molecule calculated with the help of DFTusing B3LYP-6-311G model support the crystal structure
1 Introduction
Thiourea derivatives are well known sulphur containing com-pounds acting as ligands in the field of coordination chem-istry [1ndash3] Such ligands are capable of affording complexeswith metal ions the resultant complexes have been reportedto have imperative antimicrobial [4] and anticonvulsant [5]applications Thiourea derivatives and their complexes havenumerous catalytic applications in asymmetric organocatal-ysis [6ndash8] have been used as cocatalysts in Pauson-Khandreactions [1] Pd-catalyzed reactions [1 9] Heck and Suzukicoupling reactions and so forth [2 9] Thiourea derivativesgot much more attention in the field of highly enantio- anddiastereoselective catalysis [10] and have also been appliedas cocatalysts in nanoparticles and a number of other typesof reactions [11 12] The challenging task in the chemistryof thiourea is its syntheses and structural characterizationSeveral research groups are trying tomake this versatile groupof compounds easily accessible and have reported variousmethods [13ndash16]
In continuation to our previous work [17] the title com-pound was obtained unexpectedly Surprisingly a compre-hensive research survey does not show solid state structuraldata of title compound 1 The structure of the compoundwas determined by X-ray diffraction and its DFT optimizedgeometry was determined using B3LYP-6311G model oftheory [18] Theoretical data obtained for the compoundcompare well with the experimental data
2 Experimental
All chemicals that is carbon disulphide and isobutyl amineare commercially available and were used without furtherpurification Solvents were distilled prior to use
21 Synthesis of 13-Di(isobutyl)thiourea Solution of carbondisulphide (4980mmole 50mL) was prepared in petroleumether (100mL) andwas cooled to 0∘C in an ice bath following
Hindawi Publishing CorporationJournal of ChemistryVolume 2015 Article ID 913435 5 pageshttpdxdoiorg1011552015913435
2 Journal of Chemistry
NH
SNH
NH
SSH
NH2 + CS2
12
Scheme 1 Reaction between CS2
and isobutylamine to afford 13-diisobutyl thiourea
the literature procedure [16 17] An excess amount of isobuty-lamine (9960mmole 6142mL) was slowly and carefullyadded with constant stirring The stirring was continuedovernight The solvent and all other volatiles were removedunder reduced pressure and the oily compoundwas dissolvedin ethyl acetate After 2 days needle-like colorless crystalsappeared in the solution they were further allowed for fewdays to grow well The same reaction was repeated by mixingequimolar amounts ofCS
2and isobutylamine by adopting the
same procedure but instead of the expected dithiocarbamate2 product 1 was exclusively obtained (Scheme 1)
22 X-Ray Crystallography A crystal of suitable dimensionswas selected for X-ray structure analysis The diffractionintensity data were collected on a Bruker kappa APEXIICCD diffractometer using graphite-monochromator Mo-K120572radiation (120582 = 071073 A) at ambient temperature For datacollection 120596 scan and multiscan absorption correction wasapplied Final refinement on1198652 was carried out by full-matrixleast-squares techniques Structure solution and refinementswere accomplished with SHELXL-97 [19] and publCIF [20]
23 DFT Calculations The geometry of title compound(1) was obtained from X-ray crystallographic data Themolecular structure of (1) (C
9H20N2S) in ground state is
optimized by DFT method including correlation correctionusing B3LYP-6311G model of theory [18] Mullikanrsquos chargeswere calculated by using the same model of theory the dataso-obtained are given in Table 5 and optimized structure ofthe compound is given in Figure 2 All calculations wereperformed by using Gauss-viewmolecule visualizer programand GAUSSIAN-03 program [18 21 22]
3 Results and Discussion
The reaction of primary or secondary amines with carbondisulphide gives dithiocarbamates the reaction is straight-forward and usually proceeds without the formation of sideproducts We treated isobutylamine with carbon disulphidein petroleum ether and instead of dithiocarbamate derivative2 compound 1 was exclusively obtained as solid (Scheme 1)The reaction proceeded at ambient temperature withoutadding a catalyst and excellent yield was achieved The reac-tion probably proceeds through formation of isothiocyanateintermediate which reacts further with amine and rearrangesto thiourea [16]
Single Crystal Studies The molecular structure of compound1 is given in Figure 1 with numbering scheme It crystallizesin monoclinic crystal system (120572 = 120574 = 90 120573 = 90) with thespace group P21c the crystal packing in unit cell is stabilized
Table 1 Crystal data and structure refinement
Crystal parameter ValueEmpirical formula C9H20N2SFormula weight 18834Temperature 296KWavelength 071073 ACrystal system MonoclinicSpace group P21c
Unit cell dimensions
119886 115131(4) A119887 92355(3) A119888 113093(5) A120573 99569(2)
Volume 118578(8) A3
Mu 0232mmminus1
119885 density 4 1055 g cmminus3
119865 (0 0 0) 4160(ℎ 119896 119897) min (minus13 minus9 minus13)(ℎ 119896 119897) max (13 11 13)Correction method MultiscanTheta (max) 25250119877 (reflection) 00716 (1637)1199081198772
02021 (2145)Data completeness 1000Goodness of fit 1053
C9 C7
C8
C6 N2
C5
S1
N1
C4 C2
C3
C1
Figure 1 Crystal structure (ORTEP plot) of 13-diisobutyl thioureamolecule with labeling scheme
by intermolecularNndashHsdot sdot sdot S bondingwith an average distanceof 2819 A which is relatively stronger than the reported one287 A [23] and is closer to 2837 A [24]The data pertinent tocrystal structure determination are summarized in Table 1
The geometry around nitrogen atom is distorted andcannot be predicted on the basis of hybridization Thedistortion can easily be traced out by the involvement of lonepair of electrons on nitrogen in delocalization phenomenonwith the 120587 electrons of C=SmoietyTheC5ndashN1 bond distance(1328 A) and C5ndashN2 (1343 A) are shorter than average CndashN single bond distance (1499 A) and similarly that of C=Sbond distance (1698 A) is longer than the average distance(1599 A) reported in literature [25] These data supportpartial double bond characters between NndashC and flow of
Journal of Chemistry 3
Table 2 Hydrogen bonding data for the title compound
X H Y 119889(XndashH) (A) 119889(HndashY) (A) 119889(XndashY) (A) lt(XHY) (∘)N1 H1a S1 0861(4) 2683(8) 3479(2) 15433(3)N2 H2a S1 0860(4) 2819(3) 3573(3) 14737(5)
Table 3 Selected bond lengths (experimental and calculated)belong to compound 1
Bonded atoms Experimental CalculatedS1ndashC5 1698(3) 17375N1ndashC5 1328(4) 13665N1ndashC4 1452(4) 14664N2ndashC5 1343(4) 13624N2ndashC6 1455(4) 14683C1ndashC2 1419(7) 15385C2ndashC4 1378(6) 15444C2ndashC3 1542(6) 15379C6ndashC7 1488(6) 15420C7ndashC8 1490(7) 15409C7ndashC9 1536(6) 15417
CS N
H
Figure 2 The packing of thiourea (1) molecules showing theintermolecular H-bonding
electron density from sulfur resulting in an elongation in SndashCbond
The elongation of CndashS bondmay also be explained on thebasis of intermolecular hydrogen bonding (data reported inTable 2) The solid state crystal packing and intermolecularinteractions are shown in Figure 2 The molecules of thetitle compound are organized and held together with thehelp of intermolecular NndashHsdot sdot sdot S hydrogen bonding with anaverage distance 2819 A which falls in the expected rangereported for analogous compounds that is 287 A [23] 284 A[26] and 2837 A [24] The experimental and calculated data(for gaseous molecule) DFT (B3LYP6-311G) are given inTable 3The calculated and experimental data related to bond
Table 4 Selected bond angles and torsion angles for compound 1 acomparison between experimental and theoretical data
Atoms Experimental CalculatedBond angle
C1ndashC2ndashC3 1129(4) 111391C1ndashC2ndashC4 1258(5) 109523C4ndashC2ndashC3 1105(4) 111876C2ndashC4ndashN1 1177(4) 114192C4ndashN1ndashC5 1264(3) 125221N1ndashC5ndashS1 1203(3) 123101S1ndashC5ndashN2 1224(3) 122101N1ndashC5ndashN2 1172(3) 114798C5ndashN2ndashC6 1252(3) 129550N2ndashC6ndashC7 1144(3) 112036C6ndashC7ndashC8 1133(4) 112558C6ndashC7ndashC9 1090(4) 112701C9ndashC7ndashC8 1109(4) 111702
Torsion angleC4ndashN1ndashC5ndashS1 17191 17009S1ndashC5ndashN2ndashC6 022 091C5ndashN1ndashC4ndashC2 15089 14907C5ndashN2ndashC6ndashC7 8997 8570N1ndashC4ndashC2ndashC1 4349 4576N1ndashC4ndashC2ndashC3 17510 17375N2ndashC6ndashC7ndashC8 6057 6073N2ndashC6ndashC7ndashC9 17535 17526
angles around N atom are approximately 120∘ which supportthe planarity and sp2 hybridization around nitrogen owing todelocalization of electrons in the molecule
DFT-Studies and Vibrational Spectra Analysis Experimentaldata correspond to solid phase while theoretical calculationsbelong to gaseous phase [22] DFT calculations are usuallyperformed on a single molecule in the unit cell [27] DFTcalculations for compound 1 were carried out by using theGAUSSIAN-03 program [18 21 22] The geometry of themolecule was optimized by DFTB3LYP with the 6-311Gbasis set [18] The optimized geometry obtained throughDFT was compared with crystal structure which supportsthe crystal structure The crystallographic and optimizedgeometric bond lengths and bond angles of compound 1 aregiven in Tables 3 and 4 respectively
Mullikanrsquos charges distribution on atoms of compound(1) is given in Table 5 It can be noticed from the tablethat negative charge density of nitrogen and terminal carbonappears in the range ofminus0660 andminus0508 respectively whichis considerably larger than other atoms bearing negative
4 Journal of Chemistry
Table 5 Calculated Mullikanrsquos charges for B3LYP6-311G
Atoms B3LYP6-311GC1 minus0508H1A 0168H1B 0187H1C 0177C2 minus0190H2 0218C3 minus0512H3A 0166H3B 0161H3C 0181C4 minus0161H4A 0164H4B 0238N1 minus0660HI 0314C5 0279S1 minus0163N2 minus0664H2(N) 0309C6 minus0111H6A 0225H6B 0219C7 minus0291H7 0194C8 minus0486H8A 0186H8B 0157H8C 0188C9 minus0492H9A 0180H9B 0183H9C 0155
charges which shows that nitrogen is donor sites for tradi-tional and terminal carbons are donor sites for nontraditionalhydrogen bonding
The experimental and calculated (B3LYP6-311G) IRabsorption frequency along with their respective intensitiesare given in Figure 3 The experimental bands are probablyassigned comparatively with related molecules [28] Thepresence of intermolecular interactions is responsible forthe higher value of ](C=S) stretching at 1227 cmminus1 Theabsorption bands at 3346 and 3237 cmminus1 are representing](N1ndashH) and ](N
2ndashH) stretching for title compound (1)
their corresponding quantum chemical calculated ](NndashH)stretching appeared to be shifted to higher frequency Thebands at 2954ndash2868 cmminus1 are assigned to ](CndashH) stretchingsimilar to the calculated one Strong IR bands in range 1600ndash1500 cmminus1 represent ](NndashH) bending [29] In addition strongband at 1227 cmminus1 corresponds to ](C=S) stretching Lowervalue of ](C=S) up to 750 cmminus1 is also reported [29 30] but
500 1000 1500 2000 2500 3000 3500 4000
Wave number (cmminus1)
ExperimentalTheoretical
Figure 3 Comparative infrared spectra of the title compound in thegaseous state (theoretical calculated using B3LYP6-311G method)and in the solid state (experimental)
intermolecular C=Ssdot sdot sdotHndashX interaction strongly affects theC=S stretching [30]
4 Conclusions
Reaction of CS2and isobutylamine affords the corresponding
thiourea instead of dithiocarbamate derivative The com-pound could easily be purified with the help of crystal-lization The crystal structure studies show the existenceof intermolecular NndashHsdot sdot sdot S type H-bonding All structuralparameters were also calculated (DFT) and were comparedwith the experimental data Solid state and gaseous phase data(bonding and vibration energies) are in close agreement witheach other
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work was supported by Higher Education Commissionof Pakistan under NRPUProject no 20-1488RampD09-5432
References
[1] Y Tang Y Zhang M Dai et al ldquoA highly efficient synthesisof the FGH ring of micrandilactone A application of thioureasas ligands in the co-catalyzed Pauson-Khand reaction and Pd-catalyzed carbonylative annulationrdquo Organic Letters vol 7 no5 pp 885ndash888 2005
[2] W Chen R Li B Han et al ldquoThe design and synthesisof bis(thiourea) ligands and their application in Pd-catalyzedheck and suzuki reactions under aerobic conditionsrdquo EuropeanJournal of Organic Chemistry no 5 pp 1177ndash1184 2006
[3] J Liu B Liang D Shu Y Hu Z Yang and A Lei ldquoAlkoxycar-bonylation of aryl iodides catalyzed by Pd with a thiourea typeligand under balloon pressure of COrdquo Tetrahedron vol 64 no40 pp 9581ndash9584 2008
[4] H Arslan N Duran G Borekci C K Ozer and C AkbayldquoAntimicrobial activity of some thiourea derivatives and their
Journal of Chemistry 5
nickel and copper complexesrdquoMolecules vol 14 no 1 pp 519ndash527 2009
[5] A O Celen B Kaymakcıoglu S Gumru H Z Toklu and FAricioglu ldquoSynthesis and anticonvulsant activity of substitutedthiourea derivativesrdquoMarmara Pharmaceutical Journal vol 15no 2 pp 43ndash47 2011
[6] S J Connon ldquoAsymmetric catalysis with bifunctional cinchonaalkaloid-based urea and thiourea organocatalystsrdquo ChemicalCommunications no 22 pp 2499ndash2510 2008
[7] M Frings I Thome and C Bolm ldquoSynthesis of chiral sulfox-imine-based thioureas and their application in asymmetricorganocatalysisrdquo Beilstein Journal of Organic Chemistry vol 8pp 1443ndash1451 2012
[8] T E Shubina M Freund S Schenker T Clark and S BTsogoeva ldquoSynthesis and evaluation of new guanidine-thioureaorganocatalyst for the nitro-Michael reaction theoretical stud-ies on mechanism and enantioselectivityrdquo Beilstein Journal ofOrganic Chemistry vol 8 pp 1485ndash1498 2012
[9] D Mingji B Liang C Wang et al ldquoA novel thiourea ligandapplied in the Pd-catalyzedHeck Suzuki and Suzuki carbonyla-tive reactionsrdquo Advanced Synthesis and Catalysis vol 346 no13-15 pp 1669ndash1673 2004
[10] T Bui S Syed and C F Barbas III ldquoThiourea-catalyzedhighly enantio- and diastereoselective additions of oxindolesto nitroolefins application to the formal synthesis of (+)-physostigminerdquo Journal of the American Chemical Society vol131 no 25 pp 8758ndash8759 2009
[11] SHegde S S Joshi TMukherjee and S Kapoor ldquoPhotochemi-cal synthesis of gold nanoparticles inNN1015840-dimethylformamidevia thiourea-derivatized polyoxometalaterdquo Research on Chemi-cal Intermediates vol 40 no 3 pp 1125ndash1133 2014
[12] X Han J Kwiatkowski T Xue K-W Huang and Y LuldquoAsymmetric mannich reaction of fluorinated ketoesters witha tryptophan-derived bifunctional thiourea catalystrdquo Ange-wandte ChemiemdashInternational Edition vol 48 no 41 pp 7604ndash7607 2009
[13] E C Taylor and R V Ravindranathan ldquoReaction of anthranilo-nitrile and N-methylanthranilonitrile with phenyl isocyanateand phenyl isothiocyanaterdquo The Journal of Organic Chemistryvol 27 no 7 pp 2622ndash2627 1962
[14] P Pazdera E Novacek and D Ondracek ldquoA new knowledgeabout the synthesis of 1-phenyl-3-(2-cyanophenyl) thioureardquoChemical Papers vol 43 pp 465ndash470 1989
[15] W Fathalla M Cajan J Marek and P Pazdera ldquoOne-potquinazolin-4-yl-thiourea synthesis via N-(2-cyanophenyl)ben-zimidoyl isothiocyanaterdquo Molecules vol 6 no 7 pp 588ndash6022001
[16] N Azizi A Khajeh-Amiri H Ghafuri and M BolourtchianldquoToward a practical and waste-free synthesis of thioureas inwaterrdquoMolecular Diversity vol 15 no 1 pp 157ndash161 2011
[17] E Khan A Badshah and R Kempe ldquoSynthesis and molecularstructure of bis(4-methylpiperidinodithiocarbamato) nickel(II)rdquoJournal of the Chemical Society of Pakistan vol 32 no 3 pp349ndash352 2010
[18] A Moores L Ricard and P Le Floch ldquoA1-methyl-phosphin-inium compound synthesis X-ray crystal structure and DFTcalculationsrdquo Angewandte Chemie vol 42 no 40 pp 4940ndash4944 2003
[19] G M Sheldrick ldquoA short history of SHELXrdquo Acta Crystallo-graphica Section A Foundations of Crystallography vol 64 no1 pp 112ndash122 2007
[20] S P Westrip ldquoPublCIF software for editing validating and for-matting crystallographic information filesrdquo Journal of AppliedCrystallography vol 43 no 4 pp 920ndash925 2010
[21] R Dahiya and D Pathak ldquoSynthetic studies on novel benzimi-dazolopeptides with antimicrobial cytotoxic and anthelminticpotentialrdquo European Journal of Medicinal Chemistry vol 42 no6 pp 772ndash798 2007
[22] C Yuksektepe N Caliskan M Genc and S Servi ldquoSyn-thesis crystal structure HF and DFT calculations of 1-(2-chlorobenzyl)-N-(1-(2-chlorobenzyl)-45-dihydro-1H-imidazol-2-yl) -1H-benzimidazol-2-aminerdquo CrystallographyReports vol 55 no 7 pp 1188ndash1193 2010
[23] S A Zakaria S HMuharamM SM YusofWMKhairulMA Kadir and B M Yamin ldquoSpectroscopic and structural studyof a series of pivaloylthiourea derivativesrdquoMalaysian Journal ofAnalytical Sciences vol 15 no 1 pp 37ndash45 2011
[24] C-R Lee T-H Tang L Chen and Y Wang ldquoA com-bined experimental and theoretical electron density study ofintra- and intermolecular interactions in thiourea SS-dioxiderdquoChemistrymdashA European Journal vol 9 no 13 pp 3112ndash31212003
[25] F H Allen O Kennard D G Watson L Brammer A GOrpen and R Taylor ldquoTables of bond lengths determinedby x-ray and neutron diffraction Part 1 Bond lengths inorganic compoundsrdquo Journal of the Chemical Society PerkinTransactions vol 2 no 12 pp S1ndashS19 1987
[26] C Suksai C Pakawatchai and T Tuntulani ldquoSynthesis andcrystal structure analysis of thiourea-pendant pyridinesrdquo Jour-nal of Chemical Crystallography vol 39 no 5 pp 348ndash352 2009
[27] A M R Teixeira H S Santos M R J R Albuquerque etal ldquoVibrational spectroscopy of xanthoxyline crystals and DFTcalculationsrdquo Brazilian Journal of Physics vol 42 no 3-4 pp180ndash185 2012
[28] G Binzet G Kavak N Kulcu S Ozbey U Florke andH Arslan ldquoSynthesis and characterization of novel thioureaderivatives and their nickel and copper complexesrdquo Journal ofChemistry vol 2013 Article ID 536562 9 pages 2013
[29] P M Ushasree R Jayavel C Subramanian and P RamasamyldquoGrowth of zinc thiourea sulfate (ZTS) single crystals a poten-tial semiorganic NLO materialrdquo Journal of Crystal Growth vol197 no 1-2 pp 216ndash220 1999
[30] A Saeed M F Erben and M Bolte ldquoSynthesis structuraland vibrational properties of 1-(adamantane-1-carbonyl)-3-halophenyl thioureasrdquo Spectrochimica ActamdashPart A Molecularand Biomolecular Spectroscopy vol 102 pp 408ndash413 2013
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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CatalystsJournal of
2 Journal of Chemistry
NH
SNH
NH
SSH
NH2 + CS2
12
Scheme 1 Reaction between CS2
and isobutylamine to afford 13-diisobutyl thiourea
the literature procedure [16 17] An excess amount of isobuty-lamine (9960mmole 6142mL) was slowly and carefullyadded with constant stirring The stirring was continuedovernight The solvent and all other volatiles were removedunder reduced pressure and the oily compoundwas dissolvedin ethyl acetate After 2 days needle-like colorless crystalsappeared in the solution they were further allowed for fewdays to grow well The same reaction was repeated by mixingequimolar amounts ofCS
2and isobutylamine by adopting the
same procedure but instead of the expected dithiocarbamate2 product 1 was exclusively obtained (Scheme 1)
22 X-Ray Crystallography A crystal of suitable dimensionswas selected for X-ray structure analysis The diffractionintensity data were collected on a Bruker kappa APEXIICCD diffractometer using graphite-monochromator Mo-K120572radiation (120582 = 071073 A) at ambient temperature For datacollection 120596 scan and multiscan absorption correction wasapplied Final refinement on1198652 was carried out by full-matrixleast-squares techniques Structure solution and refinementswere accomplished with SHELXL-97 [19] and publCIF [20]
23 DFT Calculations The geometry of title compound(1) was obtained from X-ray crystallographic data Themolecular structure of (1) (C
9H20N2S) in ground state is
optimized by DFT method including correlation correctionusing B3LYP-6311G model of theory [18] Mullikanrsquos chargeswere calculated by using the same model of theory the dataso-obtained are given in Table 5 and optimized structure ofthe compound is given in Figure 2 All calculations wereperformed by using Gauss-viewmolecule visualizer programand GAUSSIAN-03 program [18 21 22]
3 Results and Discussion
The reaction of primary or secondary amines with carbondisulphide gives dithiocarbamates the reaction is straight-forward and usually proceeds without the formation of sideproducts We treated isobutylamine with carbon disulphidein petroleum ether and instead of dithiocarbamate derivative2 compound 1 was exclusively obtained as solid (Scheme 1)The reaction proceeded at ambient temperature withoutadding a catalyst and excellent yield was achieved The reac-tion probably proceeds through formation of isothiocyanateintermediate which reacts further with amine and rearrangesto thiourea [16]
Single Crystal Studies The molecular structure of compound1 is given in Figure 1 with numbering scheme It crystallizesin monoclinic crystal system (120572 = 120574 = 90 120573 = 90) with thespace group P21c the crystal packing in unit cell is stabilized
Table 1 Crystal data and structure refinement
Crystal parameter ValueEmpirical formula C9H20N2SFormula weight 18834Temperature 296KWavelength 071073 ACrystal system MonoclinicSpace group P21c
Unit cell dimensions
119886 115131(4) A119887 92355(3) A119888 113093(5) A120573 99569(2)
Volume 118578(8) A3
Mu 0232mmminus1
119885 density 4 1055 g cmminus3
119865 (0 0 0) 4160(ℎ 119896 119897) min (minus13 minus9 minus13)(ℎ 119896 119897) max (13 11 13)Correction method MultiscanTheta (max) 25250119877 (reflection) 00716 (1637)1199081198772
02021 (2145)Data completeness 1000Goodness of fit 1053
C9 C7
C8
C6 N2
C5
S1
N1
C4 C2
C3
C1
Figure 1 Crystal structure (ORTEP plot) of 13-diisobutyl thioureamolecule with labeling scheme
by intermolecularNndashHsdot sdot sdot S bondingwith an average distanceof 2819 A which is relatively stronger than the reported one287 A [23] and is closer to 2837 A [24]The data pertinent tocrystal structure determination are summarized in Table 1
The geometry around nitrogen atom is distorted andcannot be predicted on the basis of hybridization Thedistortion can easily be traced out by the involvement of lonepair of electrons on nitrogen in delocalization phenomenonwith the 120587 electrons of C=SmoietyTheC5ndashN1 bond distance(1328 A) and C5ndashN2 (1343 A) are shorter than average CndashN single bond distance (1499 A) and similarly that of C=Sbond distance (1698 A) is longer than the average distance(1599 A) reported in literature [25] These data supportpartial double bond characters between NndashC and flow of
Journal of Chemistry 3
Table 2 Hydrogen bonding data for the title compound
X H Y 119889(XndashH) (A) 119889(HndashY) (A) 119889(XndashY) (A) lt(XHY) (∘)N1 H1a S1 0861(4) 2683(8) 3479(2) 15433(3)N2 H2a S1 0860(4) 2819(3) 3573(3) 14737(5)
Table 3 Selected bond lengths (experimental and calculated)belong to compound 1
Bonded atoms Experimental CalculatedS1ndashC5 1698(3) 17375N1ndashC5 1328(4) 13665N1ndashC4 1452(4) 14664N2ndashC5 1343(4) 13624N2ndashC6 1455(4) 14683C1ndashC2 1419(7) 15385C2ndashC4 1378(6) 15444C2ndashC3 1542(6) 15379C6ndashC7 1488(6) 15420C7ndashC8 1490(7) 15409C7ndashC9 1536(6) 15417
CS N
H
Figure 2 The packing of thiourea (1) molecules showing theintermolecular H-bonding
electron density from sulfur resulting in an elongation in SndashCbond
The elongation of CndashS bondmay also be explained on thebasis of intermolecular hydrogen bonding (data reported inTable 2) The solid state crystal packing and intermolecularinteractions are shown in Figure 2 The molecules of thetitle compound are organized and held together with thehelp of intermolecular NndashHsdot sdot sdot S hydrogen bonding with anaverage distance 2819 A which falls in the expected rangereported for analogous compounds that is 287 A [23] 284 A[26] and 2837 A [24] The experimental and calculated data(for gaseous molecule) DFT (B3LYP6-311G) are given inTable 3The calculated and experimental data related to bond
Table 4 Selected bond angles and torsion angles for compound 1 acomparison between experimental and theoretical data
Atoms Experimental CalculatedBond angle
C1ndashC2ndashC3 1129(4) 111391C1ndashC2ndashC4 1258(5) 109523C4ndashC2ndashC3 1105(4) 111876C2ndashC4ndashN1 1177(4) 114192C4ndashN1ndashC5 1264(3) 125221N1ndashC5ndashS1 1203(3) 123101S1ndashC5ndashN2 1224(3) 122101N1ndashC5ndashN2 1172(3) 114798C5ndashN2ndashC6 1252(3) 129550N2ndashC6ndashC7 1144(3) 112036C6ndashC7ndashC8 1133(4) 112558C6ndashC7ndashC9 1090(4) 112701C9ndashC7ndashC8 1109(4) 111702
Torsion angleC4ndashN1ndashC5ndashS1 17191 17009S1ndashC5ndashN2ndashC6 022 091C5ndashN1ndashC4ndashC2 15089 14907C5ndashN2ndashC6ndashC7 8997 8570N1ndashC4ndashC2ndashC1 4349 4576N1ndashC4ndashC2ndashC3 17510 17375N2ndashC6ndashC7ndashC8 6057 6073N2ndashC6ndashC7ndashC9 17535 17526
angles around N atom are approximately 120∘ which supportthe planarity and sp2 hybridization around nitrogen owing todelocalization of electrons in the molecule
DFT-Studies and Vibrational Spectra Analysis Experimentaldata correspond to solid phase while theoretical calculationsbelong to gaseous phase [22] DFT calculations are usuallyperformed on a single molecule in the unit cell [27] DFTcalculations for compound 1 were carried out by using theGAUSSIAN-03 program [18 21 22] The geometry of themolecule was optimized by DFTB3LYP with the 6-311Gbasis set [18] The optimized geometry obtained throughDFT was compared with crystal structure which supportsthe crystal structure The crystallographic and optimizedgeometric bond lengths and bond angles of compound 1 aregiven in Tables 3 and 4 respectively
Mullikanrsquos charges distribution on atoms of compound(1) is given in Table 5 It can be noticed from the tablethat negative charge density of nitrogen and terminal carbonappears in the range ofminus0660 andminus0508 respectively whichis considerably larger than other atoms bearing negative
4 Journal of Chemistry
Table 5 Calculated Mullikanrsquos charges for B3LYP6-311G
Atoms B3LYP6-311GC1 minus0508H1A 0168H1B 0187H1C 0177C2 minus0190H2 0218C3 minus0512H3A 0166H3B 0161H3C 0181C4 minus0161H4A 0164H4B 0238N1 minus0660HI 0314C5 0279S1 minus0163N2 minus0664H2(N) 0309C6 minus0111H6A 0225H6B 0219C7 minus0291H7 0194C8 minus0486H8A 0186H8B 0157H8C 0188C9 minus0492H9A 0180H9B 0183H9C 0155
charges which shows that nitrogen is donor sites for tradi-tional and terminal carbons are donor sites for nontraditionalhydrogen bonding
The experimental and calculated (B3LYP6-311G) IRabsorption frequency along with their respective intensitiesare given in Figure 3 The experimental bands are probablyassigned comparatively with related molecules [28] Thepresence of intermolecular interactions is responsible forthe higher value of ](C=S) stretching at 1227 cmminus1 Theabsorption bands at 3346 and 3237 cmminus1 are representing](N1ndashH) and ](N
2ndashH) stretching for title compound (1)
their corresponding quantum chemical calculated ](NndashH)stretching appeared to be shifted to higher frequency Thebands at 2954ndash2868 cmminus1 are assigned to ](CndashH) stretchingsimilar to the calculated one Strong IR bands in range 1600ndash1500 cmminus1 represent ](NndashH) bending [29] In addition strongband at 1227 cmminus1 corresponds to ](C=S) stretching Lowervalue of ](C=S) up to 750 cmminus1 is also reported [29 30] but
500 1000 1500 2000 2500 3000 3500 4000
Wave number (cmminus1)
ExperimentalTheoretical
Figure 3 Comparative infrared spectra of the title compound in thegaseous state (theoretical calculated using B3LYP6-311G method)and in the solid state (experimental)
intermolecular C=Ssdot sdot sdotHndashX interaction strongly affects theC=S stretching [30]
4 Conclusions
Reaction of CS2and isobutylamine affords the corresponding
thiourea instead of dithiocarbamate derivative The com-pound could easily be purified with the help of crystal-lization The crystal structure studies show the existenceof intermolecular NndashHsdot sdot sdot S type H-bonding All structuralparameters were also calculated (DFT) and were comparedwith the experimental data Solid state and gaseous phase data(bonding and vibration energies) are in close agreement witheach other
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work was supported by Higher Education Commissionof Pakistan under NRPUProject no 20-1488RampD09-5432
References
[1] Y Tang Y Zhang M Dai et al ldquoA highly efficient synthesisof the FGH ring of micrandilactone A application of thioureasas ligands in the co-catalyzed Pauson-Khand reaction and Pd-catalyzed carbonylative annulationrdquo Organic Letters vol 7 no5 pp 885ndash888 2005
[2] W Chen R Li B Han et al ldquoThe design and synthesisof bis(thiourea) ligands and their application in Pd-catalyzedheck and suzuki reactions under aerobic conditionsrdquo EuropeanJournal of Organic Chemistry no 5 pp 1177ndash1184 2006
[3] J Liu B Liang D Shu Y Hu Z Yang and A Lei ldquoAlkoxycar-bonylation of aryl iodides catalyzed by Pd with a thiourea typeligand under balloon pressure of COrdquo Tetrahedron vol 64 no40 pp 9581ndash9584 2008
[4] H Arslan N Duran G Borekci C K Ozer and C AkbayldquoAntimicrobial activity of some thiourea derivatives and their
Journal of Chemistry 5
nickel and copper complexesrdquoMolecules vol 14 no 1 pp 519ndash527 2009
[5] A O Celen B Kaymakcıoglu S Gumru H Z Toklu and FAricioglu ldquoSynthesis and anticonvulsant activity of substitutedthiourea derivativesrdquoMarmara Pharmaceutical Journal vol 15no 2 pp 43ndash47 2011
[6] S J Connon ldquoAsymmetric catalysis with bifunctional cinchonaalkaloid-based urea and thiourea organocatalystsrdquo ChemicalCommunications no 22 pp 2499ndash2510 2008
[7] M Frings I Thome and C Bolm ldquoSynthesis of chiral sulfox-imine-based thioureas and their application in asymmetricorganocatalysisrdquo Beilstein Journal of Organic Chemistry vol 8pp 1443ndash1451 2012
[8] T E Shubina M Freund S Schenker T Clark and S BTsogoeva ldquoSynthesis and evaluation of new guanidine-thioureaorganocatalyst for the nitro-Michael reaction theoretical stud-ies on mechanism and enantioselectivityrdquo Beilstein Journal ofOrganic Chemistry vol 8 pp 1485ndash1498 2012
[9] D Mingji B Liang C Wang et al ldquoA novel thiourea ligandapplied in the Pd-catalyzedHeck Suzuki and Suzuki carbonyla-tive reactionsrdquo Advanced Synthesis and Catalysis vol 346 no13-15 pp 1669ndash1673 2004
[10] T Bui S Syed and C F Barbas III ldquoThiourea-catalyzedhighly enantio- and diastereoselective additions of oxindolesto nitroolefins application to the formal synthesis of (+)-physostigminerdquo Journal of the American Chemical Society vol131 no 25 pp 8758ndash8759 2009
[11] SHegde S S Joshi TMukherjee and S Kapoor ldquoPhotochemi-cal synthesis of gold nanoparticles inNN1015840-dimethylformamidevia thiourea-derivatized polyoxometalaterdquo Research on Chemi-cal Intermediates vol 40 no 3 pp 1125ndash1133 2014
[12] X Han J Kwiatkowski T Xue K-W Huang and Y LuldquoAsymmetric mannich reaction of fluorinated ketoesters witha tryptophan-derived bifunctional thiourea catalystrdquo Ange-wandte ChemiemdashInternational Edition vol 48 no 41 pp 7604ndash7607 2009
[13] E C Taylor and R V Ravindranathan ldquoReaction of anthranilo-nitrile and N-methylanthranilonitrile with phenyl isocyanateand phenyl isothiocyanaterdquo The Journal of Organic Chemistryvol 27 no 7 pp 2622ndash2627 1962
[14] P Pazdera E Novacek and D Ondracek ldquoA new knowledgeabout the synthesis of 1-phenyl-3-(2-cyanophenyl) thioureardquoChemical Papers vol 43 pp 465ndash470 1989
[15] W Fathalla M Cajan J Marek and P Pazdera ldquoOne-potquinazolin-4-yl-thiourea synthesis via N-(2-cyanophenyl)ben-zimidoyl isothiocyanaterdquo Molecules vol 6 no 7 pp 588ndash6022001
[16] N Azizi A Khajeh-Amiri H Ghafuri and M BolourtchianldquoToward a practical and waste-free synthesis of thioureas inwaterrdquoMolecular Diversity vol 15 no 1 pp 157ndash161 2011
[17] E Khan A Badshah and R Kempe ldquoSynthesis and molecularstructure of bis(4-methylpiperidinodithiocarbamato) nickel(II)rdquoJournal of the Chemical Society of Pakistan vol 32 no 3 pp349ndash352 2010
[18] A Moores L Ricard and P Le Floch ldquoA1-methyl-phosphin-inium compound synthesis X-ray crystal structure and DFTcalculationsrdquo Angewandte Chemie vol 42 no 40 pp 4940ndash4944 2003
[19] G M Sheldrick ldquoA short history of SHELXrdquo Acta Crystallo-graphica Section A Foundations of Crystallography vol 64 no1 pp 112ndash122 2007
[20] S P Westrip ldquoPublCIF software for editing validating and for-matting crystallographic information filesrdquo Journal of AppliedCrystallography vol 43 no 4 pp 920ndash925 2010
[21] R Dahiya and D Pathak ldquoSynthetic studies on novel benzimi-dazolopeptides with antimicrobial cytotoxic and anthelminticpotentialrdquo European Journal of Medicinal Chemistry vol 42 no6 pp 772ndash798 2007
[22] C Yuksektepe N Caliskan M Genc and S Servi ldquoSyn-thesis crystal structure HF and DFT calculations of 1-(2-chlorobenzyl)-N-(1-(2-chlorobenzyl)-45-dihydro-1H-imidazol-2-yl) -1H-benzimidazol-2-aminerdquo CrystallographyReports vol 55 no 7 pp 1188ndash1193 2010
[23] S A Zakaria S HMuharamM SM YusofWMKhairulMA Kadir and B M Yamin ldquoSpectroscopic and structural studyof a series of pivaloylthiourea derivativesrdquoMalaysian Journal ofAnalytical Sciences vol 15 no 1 pp 37ndash45 2011
[24] C-R Lee T-H Tang L Chen and Y Wang ldquoA com-bined experimental and theoretical electron density study ofintra- and intermolecular interactions in thiourea SS-dioxiderdquoChemistrymdashA European Journal vol 9 no 13 pp 3112ndash31212003
[25] F H Allen O Kennard D G Watson L Brammer A GOrpen and R Taylor ldquoTables of bond lengths determinedby x-ray and neutron diffraction Part 1 Bond lengths inorganic compoundsrdquo Journal of the Chemical Society PerkinTransactions vol 2 no 12 pp S1ndashS19 1987
[26] C Suksai C Pakawatchai and T Tuntulani ldquoSynthesis andcrystal structure analysis of thiourea-pendant pyridinesrdquo Jour-nal of Chemical Crystallography vol 39 no 5 pp 348ndash352 2009
[27] A M R Teixeira H S Santos M R J R Albuquerque etal ldquoVibrational spectroscopy of xanthoxyline crystals and DFTcalculationsrdquo Brazilian Journal of Physics vol 42 no 3-4 pp180ndash185 2012
[28] G Binzet G Kavak N Kulcu S Ozbey U Florke andH Arslan ldquoSynthesis and characterization of novel thioureaderivatives and their nickel and copper complexesrdquo Journal ofChemistry vol 2013 Article ID 536562 9 pages 2013
[29] P M Ushasree R Jayavel C Subramanian and P RamasamyldquoGrowth of zinc thiourea sulfate (ZTS) single crystals a poten-tial semiorganic NLO materialrdquo Journal of Crystal Growth vol197 no 1-2 pp 216ndash220 1999
[30] A Saeed M F Erben and M Bolte ldquoSynthesis structuraland vibrational properties of 1-(adamantane-1-carbonyl)-3-halophenyl thioureasrdquo Spectrochimica ActamdashPart A Molecularand Biomolecular Spectroscopy vol 102 pp 408ndash413 2013
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 3
Table 2 Hydrogen bonding data for the title compound
X H Y 119889(XndashH) (A) 119889(HndashY) (A) 119889(XndashY) (A) lt(XHY) (∘)N1 H1a S1 0861(4) 2683(8) 3479(2) 15433(3)N2 H2a S1 0860(4) 2819(3) 3573(3) 14737(5)
Table 3 Selected bond lengths (experimental and calculated)belong to compound 1
Bonded atoms Experimental CalculatedS1ndashC5 1698(3) 17375N1ndashC5 1328(4) 13665N1ndashC4 1452(4) 14664N2ndashC5 1343(4) 13624N2ndashC6 1455(4) 14683C1ndashC2 1419(7) 15385C2ndashC4 1378(6) 15444C2ndashC3 1542(6) 15379C6ndashC7 1488(6) 15420C7ndashC8 1490(7) 15409C7ndashC9 1536(6) 15417
CS N
H
Figure 2 The packing of thiourea (1) molecules showing theintermolecular H-bonding
electron density from sulfur resulting in an elongation in SndashCbond
The elongation of CndashS bondmay also be explained on thebasis of intermolecular hydrogen bonding (data reported inTable 2) The solid state crystal packing and intermolecularinteractions are shown in Figure 2 The molecules of thetitle compound are organized and held together with thehelp of intermolecular NndashHsdot sdot sdot S hydrogen bonding with anaverage distance 2819 A which falls in the expected rangereported for analogous compounds that is 287 A [23] 284 A[26] and 2837 A [24] The experimental and calculated data(for gaseous molecule) DFT (B3LYP6-311G) are given inTable 3The calculated and experimental data related to bond
Table 4 Selected bond angles and torsion angles for compound 1 acomparison between experimental and theoretical data
Atoms Experimental CalculatedBond angle
C1ndashC2ndashC3 1129(4) 111391C1ndashC2ndashC4 1258(5) 109523C4ndashC2ndashC3 1105(4) 111876C2ndashC4ndashN1 1177(4) 114192C4ndashN1ndashC5 1264(3) 125221N1ndashC5ndashS1 1203(3) 123101S1ndashC5ndashN2 1224(3) 122101N1ndashC5ndashN2 1172(3) 114798C5ndashN2ndashC6 1252(3) 129550N2ndashC6ndashC7 1144(3) 112036C6ndashC7ndashC8 1133(4) 112558C6ndashC7ndashC9 1090(4) 112701C9ndashC7ndashC8 1109(4) 111702
Torsion angleC4ndashN1ndashC5ndashS1 17191 17009S1ndashC5ndashN2ndashC6 022 091C5ndashN1ndashC4ndashC2 15089 14907C5ndashN2ndashC6ndashC7 8997 8570N1ndashC4ndashC2ndashC1 4349 4576N1ndashC4ndashC2ndashC3 17510 17375N2ndashC6ndashC7ndashC8 6057 6073N2ndashC6ndashC7ndashC9 17535 17526
angles around N atom are approximately 120∘ which supportthe planarity and sp2 hybridization around nitrogen owing todelocalization of electrons in the molecule
DFT-Studies and Vibrational Spectra Analysis Experimentaldata correspond to solid phase while theoretical calculationsbelong to gaseous phase [22] DFT calculations are usuallyperformed on a single molecule in the unit cell [27] DFTcalculations for compound 1 were carried out by using theGAUSSIAN-03 program [18 21 22] The geometry of themolecule was optimized by DFTB3LYP with the 6-311Gbasis set [18] The optimized geometry obtained throughDFT was compared with crystal structure which supportsthe crystal structure The crystallographic and optimizedgeometric bond lengths and bond angles of compound 1 aregiven in Tables 3 and 4 respectively
Mullikanrsquos charges distribution on atoms of compound(1) is given in Table 5 It can be noticed from the tablethat negative charge density of nitrogen and terminal carbonappears in the range ofminus0660 andminus0508 respectively whichis considerably larger than other atoms bearing negative
4 Journal of Chemistry
Table 5 Calculated Mullikanrsquos charges for B3LYP6-311G
Atoms B3LYP6-311GC1 minus0508H1A 0168H1B 0187H1C 0177C2 minus0190H2 0218C3 minus0512H3A 0166H3B 0161H3C 0181C4 minus0161H4A 0164H4B 0238N1 minus0660HI 0314C5 0279S1 minus0163N2 minus0664H2(N) 0309C6 minus0111H6A 0225H6B 0219C7 minus0291H7 0194C8 minus0486H8A 0186H8B 0157H8C 0188C9 minus0492H9A 0180H9B 0183H9C 0155
charges which shows that nitrogen is donor sites for tradi-tional and terminal carbons are donor sites for nontraditionalhydrogen bonding
The experimental and calculated (B3LYP6-311G) IRabsorption frequency along with their respective intensitiesare given in Figure 3 The experimental bands are probablyassigned comparatively with related molecules [28] Thepresence of intermolecular interactions is responsible forthe higher value of ](C=S) stretching at 1227 cmminus1 Theabsorption bands at 3346 and 3237 cmminus1 are representing](N1ndashH) and ](N
2ndashH) stretching for title compound (1)
their corresponding quantum chemical calculated ](NndashH)stretching appeared to be shifted to higher frequency Thebands at 2954ndash2868 cmminus1 are assigned to ](CndashH) stretchingsimilar to the calculated one Strong IR bands in range 1600ndash1500 cmminus1 represent ](NndashH) bending [29] In addition strongband at 1227 cmminus1 corresponds to ](C=S) stretching Lowervalue of ](C=S) up to 750 cmminus1 is also reported [29 30] but
500 1000 1500 2000 2500 3000 3500 4000
Wave number (cmminus1)
ExperimentalTheoretical
Figure 3 Comparative infrared spectra of the title compound in thegaseous state (theoretical calculated using B3LYP6-311G method)and in the solid state (experimental)
intermolecular C=Ssdot sdot sdotHndashX interaction strongly affects theC=S stretching [30]
4 Conclusions
Reaction of CS2and isobutylamine affords the corresponding
thiourea instead of dithiocarbamate derivative The com-pound could easily be purified with the help of crystal-lization The crystal structure studies show the existenceof intermolecular NndashHsdot sdot sdot S type H-bonding All structuralparameters were also calculated (DFT) and were comparedwith the experimental data Solid state and gaseous phase data(bonding and vibration energies) are in close agreement witheach other
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work was supported by Higher Education Commissionof Pakistan under NRPUProject no 20-1488RampD09-5432
References
[1] Y Tang Y Zhang M Dai et al ldquoA highly efficient synthesisof the FGH ring of micrandilactone A application of thioureasas ligands in the co-catalyzed Pauson-Khand reaction and Pd-catalyzed carbonylative annulationrdquo Organic Letters vol 7 no5 pp 885ndash888 2005
[2] W Chen R Li B Han et al ldquoThe design and synthesisof bis(thiourea) ligands and their application in Pd-catalyzedheck and suzuki reactions under aerobic conditionsrdquo EuropeanJournal of Organic Chemistry no 5 pp 1177ndash1184 2006
[3] J Liu B Liang D Shu Y Hu Z Yang and A Lei ldquoAlkoxycar-bonylation of aryl iodides catalyzed by Pd with a thiourea typeligand under balloon pressure of COrdquo Tetrahedron vol 64 no40 pp 9581ndash9584 2008
[4] H Arslan N Duran G Borekci C K Ozer and C AkbayldquoAntimicrobial activity of some thiourea derivatives and their
Journal of Chemistry 5
nickel and copper complexesrdquoMolecules vol 14 no 1 pp 519ndash527 2009
[5] A O Celen B Kaymakcıoglu S Gumru H Z Toklu and FAricioglu ldquoSynthesis and anticonvulsant activity of substitutedthiourea derivativesrdquoMarmara Pharmaceutical Journal vol 15no 2 pp 43ndash47 2011
[6] S J Connon ldquoAsymmetric catalysis with bifunctional cinchonaalkaloid-based urea and thiourea organocatalystsrdquo ChemicalCommunications no 22 pp 2499ndash2510 2008
[7] M Frings I Thome and C Bolm ldquoSynthesis of chiral sulfox-imine-based thioureas and their application in asymmetricorganocatalysisrdquo Beilstein Journal of Organic Chemistry vol 8pp 1443ndash1451 2012
[8] T E Shubina M Freund S Schenker T Clark and S BTsogoeva ldquoSynthesis and evaluation of new guanidine-thioureaorganocatalyst for the nitro-Michael reaction theoretical stud-ies on mechanism and enantioselectivityrdquo Beilstein Journal ofOrganic Chemistry vol 8 pp 1485ndash1498 2012
[9] D Mingji B Liang C Wang et al ldquoA novel thiourea ligandapplied in the Pd-catalyzedHeck Suzuki and Suzuki carbonyla-tive reactionsrdquo Advanced Synthesis and Catalysis vol 346 no13-15 pp 1669ndash1673 2004
[10] T Bui S Syed and C F Barbas III ldquoThiourea-catalyzedhighly enantio- and diastereoselective additions of oxindolesto nitroolefins application to the formal synthesis of (+)-physostigminerdquo Journal of the American Chemical Society vol131 no 25 pp 8758ndash8759 2009
[11] SHegde S S Joshi TMukherjee and S Kapoor ldquoPhotochemi-cal synthesis of gold nanoparticles inNN1015840-dimethylformamidevia thiourea-derivatized polyoxometalaterdquo Research on Chemi-cal Intermediates vol 40 no 3 pp 1125ndash1133 2014
[12] X Han J Kwiatkowski T Xue K-W Huang and Y LuldquoAsymmetric mannich reaction of fluorinated ketoesters witha tryptophan-derived bifunctional thiourea catalystrdquo Ange-wandte ChemiemdashInternational Edition vol 48 no 41 pp 7604ndash7607 2009
[13] E C Taylor and R V Ravindranathan ldquoReaction of anthranilo-nitrile and N-methylanthranilonitrile with phenyl isocyanateand phenyl isothiocyanaterdquo The Journal of Organic Chemistryvol 27 no 7 pp 2622ndash2627 1962
[14] P Pazdera E Novacek and D Ondracek ldquoA new knowledgeabout the synthesis of 1-phenyl-3-(2-cyanophenyl) thioureardquoChemical Papers vol 43 pp 465ndash470 1989
[15] W Fathalla M Cajan J Marek and P Pazdera ldquoOne-potquinazolin-4-yl-thiourea synthesis via N-(2-cyanophenyl)ben-zimidoyl isothiocyanaterdquo Molecules vol 6 no 7 pp 588ndash6022001
[16] N Azizi A Khajeh-Amiri H Ghafuri and M BolourtchianldquoToward a practical and waste-free synthesis of thioureas inwaterrdquoMolecular Diversity vol 15 no 1 pp 157ndash161 2011
[17] E Khan A Badshah and R Kempe ldquoSynthesis and molecularstructure of bis(4-methylpiperidinodithiocarbamato) nickel(II)rdquoJournal of the Chemical Society of Pakistan vol 32 no 3 pp349ndash352 2010
[18] A Moores L Ricard and P Le Floch ldquoA1-methyl-phosphin-inium compound synthesis X-ray crystal structure and DFTcalculationsrdquo Angewandte Chemie vol 42 no 40 pp 4940ndash4944 2003
[19] G M Sheldrick ldquoA short history of SHELXrdquo Acta Crystallo-graphica Section A Foundations of Crystallography vol 64 no1 pp 112ndash122 2007
[20] S P Westrip ldquoPublCIF software for editing validating and for-matting crystallographic information filesrdquo Journal of AppliedCrystallography vol 43 no 4 pp 920ndash925 2010
[21] R Dahiya and D Pathak ldquoSynthetic studies on novel benzimi-dazolopeptides with antimicrobial cytotoxic and anthelminticpotentialrdquo European Journal of Medicinal Chemistry vol 42 no6 pp 772ndash798 2007
[22] C Yuksektepe N Caliskan M Genc and S Servi ldquoSyn-thesis crystal structure HF and DFT calculations of 1-(2-chlorobenzyl)-N-(1-(2-chlorobenzyl)-45-dihydro-1H-imidazol-2-yl) -1H-benzimidazol-2-aminerdquo CrystallographyReports vol 55 no 7 pp 1188ndash1193 2010
[23] S A Zakaria S HMuharamM SM YusofWMKhairulMA Kadir and B M Yamin ldquoSpectroscopic and structural studyof a series of pivaloylthiourea derivativesrdquoMalaysian Journal ofAnalytical Sciences vol 15 no 1 pp 37ndash45 2011
[24] C-R Lee T-H Tang L Chen and Y Wang ldquoA com-bined experimental and theoretical electron density study ofintra- and intermolecular interactions in thiourea SS-dioxiderdquoChemistrymdashA European Journal vol 9 no 13 pp 3112ndash31212003
[25] F H Allen O Kennard D G Watson L Brammer A GOrpen and R Taylor ldquoTables of bond lengths determinedby x-ray and neutron diffraction Part 1 Bond lengths inorganic compoundsrdquo Journal of the Chemical Society PerkinTransactions vol 2 no 12 pp S1ndashS19 1987
[26] C Suksai C Pakawatchai and T Tuntulani ldquoSynthesis andcrystal structure analysis of thiourea-pendant pyridinesrdquo Jour-nal of Chemical Crystallography vol 39 no 5 pp 348ndash352 2009
[27] A M R Teixeira H S Santos M R J R Albuquerque etal ldquoVibrational spectroscopy of xanthoxyline crystals and DFTcalculationsrdquo Brazilian Journal of Physics vol 42 no 3-4 pp180ndash185 2012
[28] G Binzet G Kavak N Kulcu S Ozbey U Florke andH Arslan ldquoSynthesis and characterization of novel thioureaderivatives and their nickel and copper complexesrdquo Journal ofChemistry vol 2013 Article ID 536562 9 pages 2013
[29] P M Ushasree R Jayavel C Subramanian and P RamasamyldquoGrowth of zinc thiourea sulfate (ZTS) single crystals a poten-tial semiorganic NLO materialrdquo Journal of Crystal Growth vol197 no 1-2 pp 216ndash220 1999
[30] A Saeed M F Erben and M Bolte ldquoSynthesis structuraland vibrational properties of 1-(adamantane-1-carbonyl)-3-halophenyl thioureasrdquo Spectrochimica ActamdashPart A Molecularand Biomolecular Spectroscopy vol 102 pp 408ndash413 2013
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
4 Journal of Chemistry
Table 5 Calculated Mullikanrsquos charges for B3LYP6-311G
Atoms B3LYP6-311GC1 minus0508H1A 0168H1B 0187H1C 0177C2 minus0190H2 0218C3 minus0512H3A 0166H3B 0161H3C 0181C4 minus0161H4A 0164H4B 0238N1 minus0660HI 0314C5 0279S1 minus0163N2 minus0664H2(N) 0309C6 minus0111H6A 0225H6B 0219C7 minus0291H7 0194C8 minus0486H8A 0186H8B 0157H8C 0188C9 minus0492H9A 0180H9B 0183H9C 0155
charges which shows that nitrogen is donor sites for tradi-tional and terminal carbons are donor sites for nontraditionalhydrogen bonding
The experimental and calculated (B3LYP6-311G) IRabsorption frequency along with their respective intensitiesare given in Figure 3 The experimental bands are probablyassigned comparatively with related molecules [28] Thepresence of intermolecular interactions is responsible forthe higher value of ](C=S) stretching at 1227 cmminus1 Theabsorption bands at 3346 and 3237 cmminus1 are representing](N1ndashH) and ](N
2ndashH) stretching for title compound (1)
their corresponding quantum chemical calculated ](NndashH)stretching appeared to be shifted to higher frequency Thebands at 2954ndash2868 cmminus1 are assigned to ](CndashH) stretchingsimilar to the calculated one Strong IR bands in range 1600ndash1500 cmminus1 represent ](NndashH) bending [29] In addition strongband at 1227 cmminus1 corresponds to ](C=S) stretching Lowervalue of ](C=S) up to 750 cmminus1 is also reported [29 30] but
500 1000 1500 2000 2500 3000 3500 4000
Wave number (cmminus1)
ExperimentalTheoretical
Figure 3 Comparative infrared spectra of the title compound in thegaseous state (theoretical calculated using B3LYP6-311G method)and in the solid state (experimental)
intermolecular C=Ssdot sdot sdotHndashX interaction strongly affects theC=S stretching [30]
4 Conclusions
Reaction of CS2and isobutylamine affords the corresponding
thiourea instead of dithiocarbamate derivative The com-pound could easily be purified with the help of crystal-lization The crystal structure studies show the existenceof intermolecular NndashHsdot sdot sdot S type H-bonding All structuralparameters were also calculated (DFT) and were comparedwith the experimental data Solid state and gaseous phase data(bonding and vibration energies) are in close agreement witheach other
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work was supported by Higher Education Commissionof Pakistan under NRPUProject no 20-1488RampD09-5432
References
[1] Y Tang Y Zhang M Dai et al ldquoA highly efficient synthesisof the FGH ring of micrandilactone A application of thioureasas ligands in the co-catalyzed Pauson-Khand reaction and Pd-catalyzed carbonylative annulationrdquo Organic Letters vol 7 no5 pp 885ndash888 2005
[2] W Chen R Li B Han et al ldquoThe design and synthesisof bis(thiourea) ligands and their application in Pd-catalyzedheck and suzuki reactions under aerobic conditionsrdquo EuropeanJournal of Organic Chemistry no 5 pp 1177ndash1184 2006
[3] J Liu B Liang D Shu Y Hu Z Yang and A Lei ldquoAlkoxycar-bonylation of aryl iodides catalyzed by Pd with a thiourea typeligand under balloon pressure of COrdquo Tetrahedron vol 64 no40 pp 9581ndash9584 2008
[4] H Arslan N Duran G Borekci C K Ozer and C AkbayldquoAntimicrobial activity of some thiourea derivatives and their
Journal of Chemistry 5
nickel and copper complexesrdquoMolecules vol 14 no 1 pp 519ndash527 2009
[5] A O Celen B Kaymakcıoglu S Gumru H Z Toklu and FAricioglu ldquoSynthesis and anticonvulsant activity of substitutedthiourea derivativesrdquoMarmara Pharmaceutical Journal vol 15no 2 pp 43ndash47 2011
[6] S J Connon ldquoAsymmetric catalysis with bifunctional cinchonaalkaloid-based urea and thiourea organocatalystsrdquo ChemicalCommunications no 22 pp 2499ndash2510 2008
[7] M Frings I Thome and C Bolm ldquoSynthesis of chiral sulfox-imine-based thioureas and their application in asymmetricorganocatalysisrdquo Beilstein Journal of Organic Chemistry vol 8pp 1443ndash1451 2012
[8] T E Shubina M Freund S Schenker T Clark and S BTsogoeva ldquoSynthesis and evaluation of new guanidine-thioureaorganocatalyst for the nitro-Michael reaction theoretical stud-ies on mechanism and enantioselectivityrdquo Beilstein Journal ofOrganic Chemistry vol 8 pp 1485ndash1498 2012
[9] D Mingji B Liang C Wang et al ldquoA novel thiourea ligandapplied in the Pd-catalyzedHeck Suzuki and Suzuki carbonyla-tive reactionsrdquo Advanced Synthesis and Catalysis vol 346 no13-15 pp 1669ndash1673 2004
[10] T Bui S Syed and C F Barbas III ldquoThiourea-catalyzedhighly enantio- and diastereoselective additions of oxindolesto nitroolefins application to the formal synthesis of (+)-physostigminerdquo Journal of the American Chemical Society vol131 no 25 pp 8758ndash8759 2009
[11] SHegde S S Joshi TMukherjee and S Kapoor ldquoPhotochemi-cal synthesis of gold nanoparticles inNN1015840-dimethylformamidevia thiourea-derivatized polyoxometalaterdquo Research on Chemi-cal Intermediates vol 40 no 3 pp 1125ndash1133 2014
[12] X Han J Kwiatkowski T Xue K-W Huang and Y LuldquoAsymmetric mannich reaction of fluorinated ketoesters witha tryptophan-derived bifunctional thiourea catalystrdquo Ange-wandte ChemiemdashInternational Edition vol 48 no 41 pp 7604ndash7607 2009
[13] E C Taylor and R V Ravindranathan ldquoReaction of anthranilo-nitrile and N-methylanthranilonitrile with phenyl isocyanateand phenyl isothiocyanaterdquo The Journal of Organic Chemistryvol 27 no 7 pp 2622ndash2627 1962
[14] P Pazdera E Novacek and D Ondracek ldquoA new knowledgeabout the synthesis of 1-phenyl-3-(2-cyanophenyl) thioureardquoChemical Papers vol 43 pp 465ndash470 1989
[15] W Fathalla M Cajan J Marek and P Pazdera ldquoOne-potquinazolin-4-yl-thiourea synthesis via N-(2-cyanophenyl)ben-zimidoyl isothiocyanaterdquo Molecules vol 6 no 7 pp 588ndash6022001
[16] N Azizi A Khajeh-Amiri H Ghafuri and M BolourtchianldquoToward a practical and waste-free synthesis of thioureas inwaterrdquoMolecular Diversity vol 15 no 1 pp 157ndash161 2011
[17] E Khan A Badshah and R Kempe ldquoSynthesis and molecularstructure of bis(4-methylpiperidinodithiocarbamato) nickel(II)rdquoJournal of the Chemical Society of Pakistan vol 32 no 3 pp349ndash352 2010
[18] A Moores L Ricard and P Le Floch ldquoA1-methyl-phosphin-inium compound synthesis X-ray crystal structure and DFTcalculationsrdquo Angewandte Chemie vol 42 no 40 pp 4940ndash4944 2003
[19] G M Sheldrick ldquoA short history of SHELXrdquo Acta Crystallo-graphica Section A Foundations of Crystallography vol 64 no1 pp 112ndash122 2007
[20] S P Westrip ldquoPublCIF software for editing validating and for-matting crystallographic information filesrdquo Journal of AppliedCrystallography vol 43 no 4 pp 920ndash925 2010
[21] R Dahiya and D Pathak ldquoSynthetic studies on novel benzimi-dazolopeptides with antimicrobial cytotoxic and anthelminticpotentialrdquo European Journal of Medicinal Chemistry vol 42 no6 pp 772ndash798 2007
[22] C Yuksektepe N Caliskan M Genc and S Servi ldquoSyn-thesis crystal structure HF and DFT calculations of 1-(2-chlorobenzyl)-N-(1-(2-chlorobenzyl)-45-dihydro-1H-imidazol-2-yl) -1H-benzimidazol-2-aminerdquo CrystallographyReports vol 55 no 7 pp 1188ndash1193 2010
[23] S A Zakaria S HMuharamM SM YusofWMKhairulMA Kadir and B M Yamin ldquoSpectroscopic and structural studyof a series of pivaloylthiourea derivativesrdquoMalaysian Journal ofAnalytical Sciences vol 15 no 1 pp 37ndash45 2011
[24] C-R Lee T-H Tang L Chen and Y Wang ldquoA com-bined experimental and theoretical electron density study ofintra- and intermolecular interactions in thiourea SS-dioxiderdquoChemistrymdashA European Journal vol 9 no 13 pp 3112ndash31212003
[25] F H Allen O Kennard D G Watson L Brammer A GOrpen and R Taylor ldquoTables of bond lengths determinedby x-ray and neutron diffraction Part 1 Bond lengths inorganic compoundsrdquo Journal of the Chemical Society PerkinTransactions vol 2 no 12 pp S1ndashS19 1987
[26] C Suksai C Pakawatchai and T Tuntulani ldquoSynthesis andcrystal structure analysis of thiourea-pendant pyridinesrdquo Jour-nal of Chemical Crystallography vol 39 no 5 pp 348ndash352 2009
[27] A M R Teixeira H S Santos M R J R Albuquerque etal ldquoVibrational spectroscopy of xanthoxyline crystals and DFTcalculationsrdquo Brazilian Journal of Physics vol 42 no 3-4 pp180ndash185 2012
[28] G Binzet G Kavak N Kulcu S Ozbey U Florke andH Arslan ldquoSynthesis and characterization of novel thioureaderivatives and their nickel and copper complexesrdquo Journal ofChemistry vol 2013 Article ID 536562 9 pages 2013
[29] P M Ushasree R Jayavel C Subramanian and P RamasamyldquoGrowth of zinc thiourea sulfate (ZTS) single crystals a poten-tial semiorganic NLO materialrdquo Journal of Crystal Growth vol197 no 1-2 pp 216ndash220 1999
[30] A Saeed M F Erben and M Bolte ldquoSynthesis structuraland vibrational properties of 1-(adamantane-1-carbonyl)-3-halophenyl thioureasrdquo Spectrochimica ActamdashPart A Molecularand Biomolecular Spectroscopy vol 102 pp 408ndash413 2013
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 5
nickel and copper complexesrdquoMolecules vol 14 no 1 pp 519ndash527 2009
[5] A O Celen B Kaymakcıoglu S Gumru H Z Toklu and FAricioglu ldquoSynthesis and anticonvulsant activity of substitutedthiourea derivativesrdquoMarmara Pharmaceutical Journal vol 15no 2 pp 43ndash47 2011
[6] S J Connon ldquoAsymmetric catalysis with bifunctional cinchonaalkaloid-based urea and thiourea organocatalystsrdquo ChemicalCommunications no 22 pp 2499ndash2510 2008
[7] M Frings I Thome and C Bolm ldquoSynthesis of chiral sulfox-imine-based thioureas and their application in asymmetricorganocatalysisrdquo Beilstein Journal of Organic Chemistry vol 8pp 1443ndash1451 2012
[8] T E Shubina M Freund S Schenker T Clark and S BTsogoeva ldquoSynthesis and evaluation of new guanidine-thioureaorganocatalyst for the nitro-Michael reaction theoretical stud-ies on mechanism and enantioselectivityrdquo Beilstein Journal ofOrganic Chemistry vol 8 pp 1485ndash1498 2012
[9] D Mingji B Liang C Wang et al ldquoA novel thiourea ligandapplied in the Pd-catalyzedHeck Suzuki and Suzuki carbonyla-tive reactionsrdquo Advanced Synthesis and Catalysis vol 346 no13-15 pp 1669ndash1673 2004
[10] T Bui S Syed and C F Barbas III ldquoThiourea-catalyzedhighly enantio- and diastereoselective additions of oxindolesto nitroolefins application to the formal synthesis of (+)-physostigminerdquo Journal of the American Chemical Society vol131 no 25 pp 8758ndash8759 2009
[11] SHegde S S Joshi TMukherjee and S Kapoor ldquoPhotochemi-cal synthesis of gold nanoparticles inNN1015840-dimethylformamidevia thiourea-derivatized polyoxometalaterdquo Research on Chemi-cal Intermediates vol 40 no 3 pp 1125ndash1133 2014
[12] X Han J Kwiatkowski T Xue K-W Huang and Y LuldquoAsymmetric mannich reaction of fluorinated ketoesters witha tryptophan-derived bifunctional thiourea catalystrdquo Ange-wandte ChemiemdashInternational Edition vol 48 no 41 pp 7604ndash7607 2009
[13] E C Taylor and R V Ravindranathan ldquoReaction of anthranilo-nitrile and N-methylanthranilonitrile with phenyl isocyanateand phenyl isothiocyanaterdquo The Journal of Organic Chemistryvol 27 no 7 pp 2622ndash2627 1962
[14] P Pazdera E Novacek and D Ondracek ldquoA new knowledgeabout the synthesis of 1-phenyl-3-(2-cyanophenyl) thioureardquoChemical Papers vol 43 pp 465ndash470 1989
[15] W Fathalla M Cajan J Marek and P Pazdera ldquoOne-potquinazolin-4-yl-thiourea synthesis via N-(2-cyanophenyl)ben-zimidoyl isothiocyanaterdquo Molecules vol 6 no 7 pp 588ndash6022001
[16] N Azizi A Khajeh-Amiri H Ghafuri and M BolourtchianldquoToward a practical and waste-free synthesis of thioureas inwaterrdquoMolecular Diversity vol 15 no 1 pp 157ndash161 2011
[17] E Khan A Badshah and R Kempe ldquoSynthesis and molecularstructure of bis(4-methylpiperidinodithiocarbamato) nickel(II)rdquoJournal of the Chemical Society of Pakistan vol 32 no 3 pp349ndash352 2010
[18] A Moores L Ricard and P Le Floch ldquoA1-methyl-phosphin-inium compound synthesis X-ray crystal structure and DFTcalculationsrdquo Angewandte Chemie vol 42 no 40 pp 4940ndash4944 2003
[19] G M Sheldrick ldquoA short history of SHELXrdquo Acta Crystallo-graphica Section A Foundations of Crystallography vol 64 no1 pp 112ndash122 2007
[20] S P Westrip ldquoPublCIF software for editing validating and for-matting crystallographic information filesrdquo Journal of AppliedCrystallography vol 43 no 4 pp 920ndash925 2010
[21] R Dahiya and D Pathak ldquoSynthetic studies on novel benzimi-dazolopeptides with antimicrobial cytotoxic and anthelminticpotentialrdquo European Journal of Medicinal Chemistry vol 42 no6 pp 772ndash798 2007
[22] C Yuksektepe N Caliskan M Genc and S Servi ldquoSyn-thesis crystal structure HF and DFT calculations of 1-(2-chlorobenzyl)-N-(1-(2-chlorobenzyl)-45-dihydro-1H-imidazol-2-yl) -1H-benzimidazol-2-aminerdquo CrystallographyReports vol 55 no 7 pp 1188ndash1193 2010
[23] S A Zakaria S HMuharamM SM YusofWMKhairulMA Kadir and B M Yamin ldquoSpectroscopic and structural studyof a series of pivaloylthiourea derivativesrdquoMalaysian Journal ofAnalytical Sciences vol 15 no 1 pp 37ndash45 2011
[24] C-R Lee T-H Tang L Chen and Y Wang ldquoA com-bined experimental and theoretical electron density study ofintra- and intermolecular interactions in thiourea SS-dioxiderdquoChemistrymdashA European Journal vol 9 no 13 pp 3112ndash31212003
[25] F H Allen O Kennard D G Watson L Brammer A GOrpen and R Taylor ldquoTables of bond lengths determinedby x-ray and neutron diffraction Part 1 Bond lengths inorganic compoundsrdquo Journal of the Chemical Society PerkinTransactions vol 2 no 12 pp S1ndashS19 1987
[26] C Suksai C Pakawatchai and T Tuntulani ldquoSynthesis andcrystal structure analysis of thiourea-pendant pyridinesrdquo Jour-nal of Chemical Crystallography vol 39 no 5 pp 348ndash352 2009
[27] A M R Teixeira H S Santos M R J R Albuquerque etal ldquoVibrational spectroscopy of xanthoxyline crystals and DFTcalculationsrdquo Brazilian Journal of Physics vol 42 no 3-4 pp180ndash185 2012
[28] G Binzet G Kavak N Kulcu S Ozbey U Florke andH Arslan ldquoSynthesis and characterization of novel thioureaderivatives and their nickel and copper complexesrdquo Journal ofChemistry vol 2013 Article ID 536562 9 pages 2013
[29] P M Ushasree R Jayavel C Subramanian and P RamasamyldquoGrowth of zinc thiourea sulfate (ZTS) single crystals a poten-tial semiorganic NLO materialrdquo Journal of Crystal Growth vol197 no 1-2 pp 216ndash220 1999
[30] A Saeed M F Erben and M Bolte ldquoSynthesis structuraland vibrational properties of 1-(adamantane-1-carbonyl)-3-halophenyl thioureasrdquo Spectrochimica ActamdashPart A Molecularand Biomolecular Spectroscopy vol 102 pp 408ndash413 2013
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
