Research Article Synthesis, Crystal Structure, and...

Hindawi Publishing CorporationJournal of ChemistryVolume 2013 Article ID 871395 7 pageshttpdxdoiorg1011552013871395

Research ArticleSynthesis Crystal Structure and Comparative Study of a NewOrganic Material 34-Diaminobenzophenone Semihydrate

Tarek Ben Rhaiem Habib Boughzala and Ahmed Driss

Laboratoire de Materiaux et Cristallochimie Faculte des Sciences de Tunis Universite de Tunis El Manar 2092 Tunis Tunisia

Correspondence should be addressed to Habib Boughzala habibboughzalaipeinrnutn

Received 22 May 2013 Accepted 15 July 2013

Academic Editor Liviu Mitu

Copyright copy 2013 Tarek Ben Rhaiem et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

The new organic 34-diaminobenzophenone semihydrate (34ABPH) is grown by slow evaporation method The compoundcrystallizes in the monoclinic space group C2 The unit cell dimensions are 119886 = 28703 (8) A 119887 = 4722 (2) A 119888 = 87076 (10)A and 120573= 9940 (2)∘ with 119885 = 2 The crystal structure analysis reveals that the C

13

H12

N2

O molecules chains are organized intoa double ribbon in the (bc) plane The structural components interact by NndashHsdot sdot sdotO and OndashHsdot sdot sdotO hydrogen bonds building upa two-dimensional network The presence of functional groups in the molecular structure is confirmed by the Fourier transforminfrared (FT-IR) spectroscopy Thermogravimetric analysis (TGA) confirms the presence of the water molecule

1 Introduction

During the crystallization process it is common that one ormore solvent molecules are involved in the structure leadingto pseudopolymorphic forms Sometimes a single moleculecan give up to 15 forms between polymorphic and pseu-dopolymorphic These different forms are generated by thecrystallization conditions (solvent temperature ) Thiscrystallization phenomenon is very important in the pharma-ceutical industry because it directly affects the bioavailabilityof drugs In ourworkwe have synthesized and analyzed a newpseudopolymorphic in the diaminobenzophenones familyTo go deeper in molecular polymorphism many papers canbe found in the literature [1 2]

The diamine compounds are important in biologicalactive natural products [3ndash5] and in medicinal chemistry[6 7] They are also used as auxiliaries and chiral ligandsin asymmetric catalysis [8] In this work a new member ofthis family 2C

13H12N2OsdotH2O is presented Water is a highly

versatile component at the interface of organic molecule Infact it can act both as a hydrogen bond donor and acceptorCompared to other solvent molecules it imposes few stericconstraints It is able to establish hydrogen bond networksoccupying less space than the hydrophilic side chains of aprotein Therefore we performed a brief comparative study

between our compound and a similar anhydrous to show therole of the water molecule in the crystal cohesion

2 Experimental

21 Synthesis of (34ABPH) The crystals of the compoundwere prepared by slow evaporation at room temperature bymixing 34-diaminobenzophenone C

13H12N2O (047mmol)

with a solution of manganese dibromide MnBr2(023mmol)

in a mixture of ethanol and water (3 1 vv) Few weeks lateryellow crystals were obtained

22 Investigation Techniques The title compound was stud-ied by various physicochemical methods X-ray diffractionDSC TGA and IR spectroscopy

23 X-Ray Diffraction A single crystal was selected using apolarizing microscope in order to perform X-ray diffrac-tion analysis Reflections intensities data were collected onan Enraf-Nonius CAD4 diffractometer [9] using graphitemonochromated MoK120572 radiation 120582 = 071073 A

24 Computing Details Program used to solve the structureis SHELXS97 [10] program used to refine the structure isSHELXL97 [10] structures projections were drawn with the

2 Journal of Chemistry

Table 1 Crystal data of 2C13H12N2OsdotH2O

Empirical formula 2C13H12N2OsdotH2OFormula weight (gsdotmolminus1) 44251Crystal system MonoclinicSpace group C2119886 28703 (8) A119887 4722 (2) A119888 87076 (10) A120573 9940 (2)∘

119885 2Volume 11643 (6) A3

120588cal 1262 gsdotcmminus3

F(000) 468120583MoK120572 0084mmminus1

Crystal size 024 times 016 times 012mmMeasured reflections 1748Independent reflections 1687119877int 00129Refined parameters 202119877[1198652

gt 2120590(1198652

)] 0050wR(1198652) 0132Goodness of fit 116

DIAMOND program version 30 [11] Crystal data and exper-imental parameters used for the intensity data collection aresummarized in Table 1

25 Physical Measurements The Fourier transform infrared(FT-IR) technique was carried out to confirm the presenceof functional groups and to find their vibrational modesThe sample was mixed thoroughly with dried KBr Thespectrum was recorded in the range of 400 to 4000 cmminus1using a Bruker Vector 22 FT-IR spectrometer The TG curvewas recorded on a balance UGINE EYRAUD type B 60DSC from SETARAM instrumentations can provide furtherinformation about phase changes and reactions occurring atelevated temperatures

3 Results and Discussion

31 Crystal Structure In accordance with the single crystalX-ray study the title compound crystallizes as amonohydrate(Figure 1) The molecule is twisted with a dihedral angle of541 (2)∘ between the 34-diaminophenyl and phenyl ringsBond lengths and angles in the phenyl cycle are withinthe normal ranges and comparable with those found inhomologous diaminobenzophenone [12] Due to the 2-foldaxis passing through the H

2O position in the [010] direction

the asymmetric part of the unit cell consists of a C13H12N2O

molecule and a half watermoleculeThenitrogen atoms of theamine groups are in a trigonal pyramidal configuration (sumof valence angles is 3541∘ for N1 and 328∘ for N2) and deviatefromphenyl plane respectively byndash0076 (4) A and 00041 (2)A Conjugation between the nitrogen unshared electron pairand the 120587 system of the phenyl fragment leads to a shortening

Table 2 Hydrogen bond geometry (A ∘)

DndashHsdot sdot sdotA DndashH Hsdot sdot sdotA Dsdot sdot sdotA DndashHsdot sdot sdotAN1ndashH1Bsdot sdot sdotO1i 096 (4) 210 (4) 2956 (4) 148 (3)O2ndashH11sdot sdot sdotO1 091 (4) 203 (4) 2884 (3) 153 (5)N1ndashH1Asdot sdot sdotN2 088 (3) 243 (3) 2772 (5) 104 (1)N1ndashH1Asdot sdot sdotN2ii 088 (3) 225 (3) 3100 (5) 163 (3)N2ndashH2Asdot sdot sdotO2iii 091 (4) 228 (4) 3162 (3) 163 (4)Symmetry codes (i) 119909 119910 119911 minus 1 (ii) minus119909 119910 minus119911 minus 1 (iii) 119909 119910 + 1 119911

of the N1ndashC11 bond (1384 (3) A) and N2ndashC12 bond (1402 (4)A) relatively to the standard length of a purely single NndashCsp2bond (143ndash145 A) [13 14] On the other hand the C1ndashC2bond (1480 (4) A) is longer than its neighbour C1ndashC8 (1476(4) A) This is probably due to the electron delocalisation atthe C8 side of the molecule (Figure 1)

The crystal structure analysis reveals that the C13H12N2O

molecules chains are organized into a double ribbon inthe (119887 119888) plane These planes are connected in pairsby intermolecular hydrogen bonds O2ndashH11sdot sdot sdotO1 and N1ndashH1Asdot sdot sdotN2ii (symmetry code (ii) minusx y minusz ndash 1) (see Figure 2and Table 2)

Each water molecule is surrounded by four organicmolecules C

13H12N2O and linked to the carboxyl group

and the amine radical (Figure 3) The sequence of theorganic entities C

13H12N2O and the water molecules is pro-

vided by hydrogen bonds NndashHsdot sdot sdotO and OndashHsdot sdot sdotO A two-dimensional network ensures the cohesion and the structurestability

Before making any structural comparison it is necessaryto standardize the networks of the two structures Simplymake a change in the mark of the second orthorhombicstructure C

13H12N2O (441015840-diaminobenzophenone [12])

Compared to the anhydrous form (441015840-diaminobenz-ophenone [12]) the title compound structure exhibits sev-eral common properties (cell parameters range absence ofcentrosymmetry and structural arrangement) On the otherhand the addition of two water molecules per unit cellincreases the volume cell of about 80 A3 40 A3 would bethe volume occupied by a single water molecule in this typeof structural arrangement Furthermore the water moleculeseems to be lowering the crystal symmetry and enhancing thecrystal cohesion by increasing the hydrogen bonds density

The alignment of the water molecules along (a) and(c) axes induces their expansion compared to those of theanhydrous structure a 24306 (2) to 28703 (8) A (18)and b 81110 (7) to 87076 (10) A (7) The title compoundb parameter narrowing is probably due to the moleculescloseness in the network further to the presence of thehydrogen bonds around the water molecule (Table 3)

To learn more about the water role in the structureand as published earlier [15] the anhydrous 34-diamino-benzophenone exhibits powerful properties in the analysisof oligonucleotides by matrix-assisted laser desorptionioni-zation time-of-flight mass spectrometry It will be interestingto know if the semihydrated form (the title compound) willhave comparable behavior or not Similar work is planned

Journal of Chemistry 3

ab

c

C1i

C10i

O2

O1

C13

C7

C6 C5

C4

C3C2C1

C8

C9

C10

C11

C12

N1

N2

C2i

C9i

C8i

C3i

C4i

C5i

C6i

C7i

O1i

C11i

C12i

C13i

N1i

N2i

Figure 1 The molecular structure of the title compound showing the atom numbering scheme Displacement ellipsoids are drawn at the50 probability level and H atoms are shown as small spheres of arbitrary radii Symmetry code (i) minusx y minusz

O1

O2

N1N2

H1BH1A

H2A

H11O1

O2

N1N2

H1AAA

H2AAAAA

H111111111111111

a

c

Figure 2 The crystal packing of the title compound viewed along the b-axis showing the NndashHsdot sdot sdotNO and OndashHsdot sdot sdotO interaction (dottedlines)

32 IR Spectroscopy The infrared (IR) spectroscopy is oneof the major physical methods for investigating molecularstructure Figure 4 shows the recorded IR spectrum of thetitle compound

Based on the previous literature results and the theoreticalsimulation of IR spectrum the large band centred around3600 cmminus1 is attributed to the stretching modes of OndashHradicalsThe bands located at 3380 cmminus1 and 3190 cmminus1might


N2

O1

O2

O1ii

O2ii

O2iii

O1iv

N2ii

N2i

N2iv

O1i

a

b

c

Figure 3 The role of water in the packing stabilization H atoms not involved in hydrogen bonding (dashed lines) have been omitted forclarity Displacement ellipsoids are drawn at 50 probability level Symmetry codes (i) minusx y minusz (ii) x y minus 1 z (iii) x y + 1 z (iv) minusx y minus 1minusz

Table 3 The crystallographic parameters of C13H12N2O and2C13H12N2OsdotH2O

Compound C13H12N2O C13H12N2O 2C13H12N2OsdotH2OSpace group P 212121 P 212121 C 2Crystalsystem

Orthorhombic Orthorhombic Monoclinic

119886 (A) 54982 (5) 24306 (2) 28703 (8)119887 (A) 81110 (7) 54982 (5) 4722 (2)119888 (A) 24306 (2) 81110 (7) 87076 (10)120572 (∘) 90 90 90120573 (∘) 90 90 9940 (2)120574 (∘) 90 90 90119881(A3) 108395 (16) 108395 (16) 11643 (6)119885 4 4 2

be assigned to the asymmetric and symmetric stretchingmodes of NndashH in the amine group and the out-of-planebending mode of this group is probably responsible for the

10080604020

03500 2500 1500 500

Wavenumber (cmminus1)

Tran

smitt

ance

()

Figure 4 Experimental IR spectrum of compound2C13

H12

N2

OsdotH2

O

band at 1447 cmminus1 The bands centred at 3000 cmminus1 could beattributed to the stretching vibration of the =CndashH bonds inthe aromatic group The typical stretching band of carboxylgroup (gtC=O) is shown at 1728 cmminus1 However the rangeof bands between 1550 and 1700 cmminus1 is attributed to thestretching vibration of the aromatic group (C=C) Finally thebands between 500 and 1150 cmminus1 are probably the result ofthe bending vibration of the (=CndashH) and (NH

2) groups


Tran

smitt

ance

()

20004000

80

40

00


Figure 5 Calculated IR spectrum of compound 2C13

H12

N2

OsdotH2

O

Table 4 Calculated and experimental IR bands

Calculatedfrequencies(cmminus1)

Experimentalfrequencies(cmminus1)

Attribution

39913862 3600 Stretching (OndashH)

35203392

33803190 Stretching (NndashH)

3058 3000 Stretching (CndashH)1945 1728 Stretching (C=O)1790 1550ndash1700 Stretching (C=C)1748 1512 Bending (OndashH)1688 1447 Bending (NndashH)1242ndash1628 1200ndash1330 Stretching (C=C) (CndashN)500ndash1150 500ndash1150 Bending (CndashH) (NndashH)

33 Theoretical IR Spectroscopy The semiempirical parame-terized model number 3 (PM3) treatment used by ldquoCACherdquo[16] program allows the IR vibrational frequencies calcula-tions On the other hand the observed bands assignmentbecomes easier by comparing the observed frequencies andthose calculated Figure 5 shows the IR calculated spectrumafter an optimisation of the molecular configuration Thismodel is very close to the obtained one by the structuralinvestigations The main observed vibrational bands areidentified in the calculated one (see Table 4)

34 Morphology of (34ABPH) The crystal morphology isa key element in many industrial processes and has anenormous impact at the processing and postprocessingstages of pharmaceuticals agrochemicals petrochemicalsand cementsThemorphology of crystalline solids influencestheir physical properties Crystal morphology can alter thedissolution rate of chemicals and bioavailability of drugs andmechanical properties such as filtration grinding dustingand handling and packaging and storage of crystallineproducts

TheBravais-Friedel-Donnay-Harker (BFDH) laws [17 18]are strictly based on the symmetry of the crystal lattice togenerate an ordered list of possible growing faces The viewof the observed and calculated crystal morphologies reveals a

Figure 6 Predicted morphology of 2C13

H12

N2

OsdotH2

O Growthshape from BFDH rules

Figure 7 Images of the growthmorphologies of 2C13

H12

N2

OsdotH2

O

similarity between the two shapes (see Figures 6 and 7) Thisexamination is used to assign the crystal growth axe as the(001) and to identify the crystallographic axis and the physicalones

35 Thermal and Calorimetric Analysis Calorimetric andthermal studies were carried out to investigate the thermalbehaviour of the studied phase Both techniques were used


and

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

50 100 150 200 250 300 350Temperature (∘C)

Exo

Hea

tflow

(mV

)

andExo

Figure 8 DSC curve of 2C13

H12

N2

OsdotH2

O

0 5000 10000 15000 20000 25000 30000 35000 40000 45000 50000t (s)

Temperature

TGA curve

m (mg)

3703603503403303203103002902802702602502402302202102001901801701601501401301201101009080706050403020100

TemperatuTemperatu

TGA curveTGA

m (mg)( )( g) T (∘C)4140393837363534333231302928272625242322212019181716151413121110

98765432

Figure 9 TG curve of 2C13

H12

N2

OsdotH2

O

under controlled atmosphere and led to complimentarilyresults

351 Differential Scanning Calorimetry The DSC curveobtained in the temperature range of [50∘C 350∘C] and undernitrogen atmosphere reveals two endothermic phenomena(Figure 8) The first one happening at 80∘C is due to thecompound dehydrationThe second one at 140∘C is probablydue to the departure of ammonia and carbon dioxide asshown by the TGA investigations

352 Thermogravimetric Analysis The thermogravimetriccurve analysis of the title compound (Figure 9) was obtainedwith heating rate of 50∘Csdothminus1 under argon atmosphere in

temperature range (25∘Cminus300∘C) It shows two mass lossesThe first [413 plusmn 015] happening at 80∘C was attributedto the departure of the water molecule (theoretical value409) The second mass loss [3105 plusmn 027] beginningaround 140∘C can be explained by the departure of fourammonia and two carbon monoxide molecules result of theproduct decomposition (theoretical value 2802)

4 Conclusion

We have synthesized in the present work a new organic com-pound 2C

13H12N2OsdotH2O A single crystal X-ray diffraction

was carried out in order to solve the structure and to performstructural analysis This compound has been characterizedby IR vibrational spectroscopy The semiempirical PM3


treatment allows the IR vibrational frequencies calculationsThe observed crystal morphology was compared to the simu-lated one obtained by the Bravais-Friedel Donnay-Harkermodel Calorimetric and thermal studies were carried out toinvestigate the thermal behaviour of the studied phase Pho-toluminescence tests are planned to value this compound

References

[1] I M R Landre F T Martins J A Ellena M H Dos Santosand A C Doriguetto ldquoPseudopolymorphism in hy-droxy-benzo-phenones the dihydrate of 221015840441015840-tetra-hydroxy-benzophenonerdquo Acta Crystallographica C vol 68 no 4 ppo156ndasho159 2012

[2] I M R Landre T E Souza R S Correa F T Martins and AC Doriguetto ldquoA monohydrate pseudopolymorph of 34-dihy-droxybenzophenone and the role of water in the crystal assem-bly of benzophenonesrdquo Acta Crystallographica C vol 66 no 9pp o463ndasho465 2010

[3] A Pasini and F Zunino ldquoNew cisplatin analoguesmdashon the wayto better antitumor agentsrdquo Angewandte Chemie InternationalEdition vol 26 no 7 pp 615ndash624 1987

[4] M Otsuka T Masuda A Haupt et al ldquoMan-designedbleomycin with altered sequence specificity in DNA cleavagerdquoJournal of the AmericanChemical Society vol 112 no 2 pp 838ndash845 1990

[5] D Zaouali Zgolli H Boughzala and A Driss ldquo4-Sulfamoyla-nilinium chloriderdquo Acta Crystallographica E vol 66 no 6 po1488 2010

[6] E T Michalson and J Szmuszkovicz ldquoMedicinal agents inco-rporating the 12-diamine functionalityrdquo Progress in DrugResearch vol 33 pp 135ndash149 1989

[7] J Reedijk ldquoImproved understanding in platinum antitumourchemistryrdquo Journal of the Chemical Society Chemical Commu-nications no 7 pp 801ndash806 1996

[8] H-U Blaser ldquoThe chiral pool as a source of enantioselectivecatalysts and auxiliariesrdquo Chemical Reviews vol 92 no 5 pp935ndash952 1992

[9] Enraf-Nonius CAD-4 EXPRESS Enraf-Nonius Delft TheNetherlands 1994

[10] G M Sheldrick ldquoA short history of SHELXrdquo Acta Crystallo-graphica A vol 64 no 1 pp 112ndash122 2007

[11] K Brandenburg DIAMOND Crystal Impact GbR BonnGermany 2006

[12] Y-H Wen Y-H He Y-L Feng and S W Ng ldquoAn orthorhom-bic modification of 441015840-diaminobenzophenonerdquo Acta Crystal-lographica E vol 62 no 5 pp o1787ndasho1788 2006

[13] E M Burke-Laing and M Laing ldquoStructures of nitrogen-containing aromatic compounds III Benzalazine redetermi-nation and refinementrdquoActa Crystallographica B vol 32 no 12pp 3216ndash3224 1976

[14] F H Allen O Kennard D G Watson L Brammer A GOrpen and R Taylor ldquoTables of bond lengths determined byx-ray and neutron diffraction Part 1 Bond lengths in organiccompoundsrdquo Journal of the Chemical Society Perkin Transac-tions 2 no 12 pp S1ndashS19 1987

[15] Y Fu S Xu C PanM Ye H Zou and B Guo ldquoAmatrix of 34-diaminobenzophenone for the analysis of oligonucleotides bymatrix-assisted laser desorptionionization time-of-flight massspectrometryrdquoNucleic Acids Research vol 34 no 13 article e942006

[16] Cache worksystem Pro Version 75085 Fujitsu Limited 2000ndash2006 Oxford Molecular

[17] A Bravais Etudes Crystallographiques Academie des SciencesParis France 2010

[18] J D H Donnay and D Harker ldquoA new law of crystal morphol-ogy extending the Law of Bravaisrdquo American Mineralogist vol22 p 463 1937

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Table 1 Crystal data of 2C13H12N2OsdotH2O

Empirical formula 2C13H12N2OsdotH2OFormula weight (gsdotmolminus1) 44251Crystal system MonoclinicSpace group C2119886 28703 (8) A119887 4722 (2) A119888 87076 (10) A120573 9940 (2)∘

119885 2Volume 11643 (6) A3

120588cal 1262 gsdotcmminus3

F(000) 468120583MoK120572 0084mmminus1

Crystal size 024 times 016 times 012mmMeasured reflections 1748Independent reflections 1687119877int 00129Refined parameters 202119877[1198652

gt 2120590(1198652

)] 0050wR(1198652) 0132Goodness of fit 116

DIAMOND program version 30 [11] Crystal data and exper-imental parameters used for the intensity data collection aresummarized in Table 1

25 Physical Measurements The Fourier transform infrared(FT-IR) technique was carried out to confirm the presenceof functional groups and to find their vibrational modesThe sample was mixed thoroughly with dried KBr Thespectrum was recorded in the range of 400 to 4000 cmminus1using a Bruker Vector 22 FT-IR spectrometer The TG curvewas recorded on a balance UGINE EYRAUD type B 60DSC from SETARAM instrumentations can provide furtherinformation about phase changes and reactions occurring atelevated temperatures

3 Results and Discussion

31 Crystal Structure In accordance with the single crystalX-ray study the title compound crystallizes as amonohydrate(Figure 1) The molecule is twisted with a dihedral angle of541 (2)∘ between the 34-diaminophenyl and phenyl ringsBond lengths and angles in the phenyl cycle are withinthe normal ranges and comparable with those found inhomologous diaminobenzophenone [12] Due to the 2-foldaxis passing through the H

2O position in the [010] direction

the asymmetric part of the unit cell consists of a C13H12N2O

molecule and a half watermoleculeThenitrogen atoms of theamine groups are in a trigonal pyramidal configuration (sumof valence angles is 3541∘ for N1 and 328∘ for N2) and deviatefromphenyl plane respectively byndash0076 (4) A and 00041 (2)A Conjugation between the nitrogen unshared electron pairand the 120587 system of the phenyl fragment leads to a shortening

Table 2 Hydrogen bond geometry (A ∘)

DndashHsdot sdot sdotA DndashH Hsdot sdot sdotA Dsdot sdot sdotA DndashHsdot sdot sdotAN1ndashH1Bsdot sdot sdotO1i 096 (4) 210 (4) 2956 (4) 148 (3)O2ndashH11sdot sdot sdotO1 091 (4) 203 (4) 2884 (3) 153 (5)N1ndashH1Asdot sdot sdotN2 088 (3) 243 (3) 2772 (5) 104 (1)N1ndashH1Asdot sdot sdotN2ii 088 (3) 225 (3) 3100 (5) 163 (3)N2ndashH2Asdot sdot sdotO2iii 091 (4) 228 (4) 3162 (3) 163 (4)Symmetry codes (i) 119909 119910 119911 minus 1 (ii) minus119909 119910 minus119911 minus 1 (iii) 119909 119910 + 1 119911

of the N1ndashC11 bond (1384 (3) A) and N2ndashC12 bond (1402 (4)A) relatively to the standard length of a purely single NndashCsp2bond (143ndash145 A) [13 14] On the other hand the C1ndashC2bond (1480 (4) A) is longer than its neighbour C1ndashC8 (1476(4) A) This is probably due to the electron delocalisation atthe C8 side of the molecule (Figure 1)

The crystal structure analysis reveals that the C13H12N2O

molecules chains are organized into a double ribbon inthe (119887 119888) plane These planes are connected in pairsby intermolecular hydrogen bonds O2ndashH11sdot sdot sdotO1 and N1ndashH1Asdot sdot sdotN2ii (symmetry code (ii) minusx y minusz ndash 1) (see Figure 2and Table 2)

Each water molecule is surrounded by four organicmolecules C

13H12N2O and linked to the carboxyl group

and the amine radical (Figure 3) The sequence of theorganic entities C

13H12N2O and the water molecules is pro-

vided by hydrogen bonds NndashHsdot sdot sdotO and OndashHsdot sdot sdotO A two-dimensional network ensures the cohesion and the structurestability

Before making any structural comparison it is necessaryto standardize the networks of the two structures Simplymake a change in the mark of the second orthorhombicstructure C

13H12N2O (441015840-diaminobenzophenone [12])

Compared to the anhydrous form (441015840-diaminobenz-ophenone [12]) the title compound structure exhibits sev-eral common properties (cell parameters range absence ofcentrosymmetry and structural arrangement) On the otherhand the addition of two water molecules per unit cellincreases the volume cell of about 80 A3 40 A3 would bethe volume occupied by a single water molecule in this typeof structural arrangement Furthermore the water moleculeseems to be lowering the crystal symmetry and enhancing thecrystal cohesion by increasing the hydrogen bonds density

The alignment of the water molecules along (a) and(c) axes induces their expansion compared to those of theanhydrous structure a 24306 (2) to 28703 (8) A (18)and b 81110 (7) to 87076 (10) A (7) The title compoundb parameter narrowing is probably due to the moleculescloseness in the network further to the presence of thehydrogen bonds around the water molecule (Table 3)

To learn more about the water role in the structureand as published earlier [15] the anhydrous 34-diamino-benzophenone exhibits powerful properties in the analysisof oligonucleotides by matrix-assisted laser desorptionioni-zation time-of-flight mass spectrometry It will be interestingto know if the semihydrated form (the title compound) willhave comparable behavior or not Similar work is planned


ab

c

C1i

C10i

O2

O1

C13

C7

C6 C5

C4

C3C2C1

C8

C9

C10

C11

C12

N1

N2

C2i

C9i

C8i

C3i

C4i

C5i

C6i

C7i

O1i

C11i

C12i

C13i

N1i

N2i


O1

O2

N1N2

H1BH1A

H2A

H11O1

O2

N1N2

H1AAA

H2AAAAA

H111111111111111

a

c





N2

O1

O2

O1ii

O2ii

O2iii

O1iv

N2ii

N2i

N2iv

O1i

a

b

c





119886 (A) 54982 (5) 24306 (2) 28703 (8)119887 (A) 81110 (7) 54982 (5) 4722 (2)119888 (A) 24306 (2) 81110 (7) 87076 (10)120572 (∘) 90 90 90120573 (∘) 90 90 9940 (2)120574 (∘) 90 90 90119881(A3) 108395 (16) 108395 (16) 11643 (6)119885 4 4 2


10080604020

03500 2500 1500 500


Tran

smitt

ance

()


H12

N2

OsdotH2

O


2) groups


Tran

smitt

ance

()

20004000

80

40

00



H12

N2

OsdotH2

O




Attribution


35203392







H12

N2

OsdotH2



H12

N2

OsdotH2

O




and

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

50 100 150 200 250 300 350Temperature (∘C)

Exo

Hea

tflow

(mV

)

andExo


H12

N2

OsdotH2

O

0 5000 10000 15000 20000 25000 30000 35000 40000 45000 50000t (s)

Temperature

TGA curve

m (mg)

3703603503403303203103002902802702602502402302202102001901801701601501401301201101009080706050403020100

TemperatuTemperatu

TGA curveTGA

m (mg)( )( g) T (∘C)4140393837363534333231302928272625242322212019181716151413121110

98765432


H12

N2

OsdotH2

O





4 Conclusion






References




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


ab

c

C1i

C10i

O2

O1

C13

C7

C6 C5

C4

C3C2C1

C8

C9

C10

C11

C12

N1

N2

C2i

C9i

C8i

C3i

C4i

C5i

C6i

C7i

O1i

C11i

C12i

C13i

N1i

N2i


O1

O2

N1N2

H1BH1A

H2A

H11O1

O2

N1N2

H1AAA

H2AAAAA

H111111111111111

a

c





N2

O1

O2

O1ii

O2ii

O2iii

O1iv

N2ii

N2i

N2iv

O1i

a

b

c





119886 (A) 54982 (5) 24306 (2) 28703 (8)119887 (A) 81110 (7) 54982 (5) 4722 (2)119888 (A) 24306 (2) 81110 (7) 87076 (10)120572 (∘) 90 90 90120573 (∘) 90 90 9940 (2)120574 (∘) 90 90 90119881(A3) 108395 (16) 108395 (16) 11643 (6)119885 4 4 2


10080604020

03500 2500 1500 500


Tran

smitt

ance

()


H12

N2

OsdotH2

O


2) groups


Tran

smitt

ance

()

20004000

80

40

00



H12

N2

OsdotH2

O




Attribution


35203392







H12

N2

OsdotH2



H12

N2

OsdotH2

O




and

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

50 100 150 200 250 300 350Temperature (∘C)

Exo

Hea

tflow

(mV

)

andExo


H12

N2

OsdotH2

O

0 5000 10000 15000 20000 25000 30000 35000 40000 45000 50000t (s)

Temperature

TGA curve

m (mg)

3703603503403303203103002902802702602502402302202102001901801701601501401301201101009080706050403020100

TemperatuTemperatu

TGA curveTGA

m (mg)( )( g) T (∘C)4140393837363534333231302928272625242322212019181716151413121110

98765432


H12

N2

OsdotH2

O





4 Conclusion






References




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N2

O1

O2

O1ii

O2ii

O2iii

O1iv

N2ii

N2i

N2iv

O1i

a

b

c





119886 (A) 54982 (5) 24306 (2) 28703 (8)119887 (A) 81110 (7) 54982 (5) 4722 (2)119888 (A) 24306 (2) 81110 (7) 87076 (10)120572 (∘) 90 90 90120573 (∘) 90 90 9940 (2)120574 (∘) 90 90 90119881(A3) 108395 (16) 108395 (16) 11643 (6)119885 4 4 2


10080604020

03500 2500 1500 500


Tran

smitt

ance

()


H12

N2

OsdotH2

O


2) groups


Tran

smitt

ance

()

20004000

80

40

00



H12

N2

OsdotH2

O




Attribution


35203392







H12

N2

OsdotH2



H12

N2

OsdotH2

O




and

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

50 100 150 200 250 300 350Temperature (∘C)

Exo

Hea

tflow

(mV

)

andExo


H12

N2

OsdotH2

O

0 5000 10000 15000 20000 25000 30000 35000 40000 45000 50000t (s)

Temperature

TGA curve

m (mg)

3703603503403303203103002902802702602502402302202102001901801701601501401301201101009080706050403020100

TemperatuTemperatu

TGA curveTGA

m (mg)( )( g) T (∘C)4140393837363534333231302928272625242322212019181716151413121110

98765432


H12

N2

OsdotH2

O





4 Conclusion






References




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Tran

smitt

ance

()

20004000

80

40

00



H12

N2

OsdotH2

O




Attribution


35203392







H12

N2

OsdotH2



H12

N2

OsdotH2

O




and

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

50 100 150 200 250 300 350Temperature (∘C)

Exo

Hea

tflow

(mV

)

andExo


H12

N2

OsdotH2

O

0 5000 10000 15000 20000 25000 30000 35000 40000 45000 50000t (s)

Temperature

TGA curve

m (mg)

3703603503403303203103002902802702602502402302202102001901801701601501401301201101009080706050403020100

TemperatuTemperatu

TGA curveTGA

m (mg)( )( g) T (∘C)4140393837363534333231302928272625242322212019181716151413121110

98765432


H12

N2

OsdotH2

O





4 Conclusion






References




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


and

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

50 100 150 200 250 300 350Temperature (∘C)

Exo

Hea

tflow

(mV

)

andExo


H12

N2

OsdotH2

O

0 5000 10000 15000 20000 25000 30000 35000 40000 45000 50000t (s)

Temperature

TGA curve

m (mg)

3703603503403303203103002902802702602502402302202102001901801701601501401301201101009080706050403020100

TemperatuTemperatu

TGA curveTGA

m (mg)( )( g) T (∘C)4140393837363534333231302928272625242322212019181716151413121110

98765432


H12

N2

OsdotH2

O





4 Conclusion






References




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



References




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Research Article Synthesis, Crystal Structure, and...

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