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Transcript of Methylene
THE REACTIVITY OF METHYLENE BLUE TOWARDS
SILVER NITRATE AND MERCURY(II) CHLORIDE
A dissertation submitted to the
BHARATHIDASAN UNIVERSITY,
in partial fulfillment of the requirements
for the award of the degree of
MASTER OF SCIENCE
IN CHEMISTRY
By
M. Mohan Raj
(Regd.No. 2002MS05)
DEPARTMENT OF CHEMISTRY
BHARATHIDASAN UNIVERSITY
TIRUCHIRAPPALLI- 620 024
May 2004
Department of Chemistry, Bharathidasan
University,
Tiruchirappalli - 620 024, India
___________________________________
Dr. K. Panchanatheswaran, M.Sc., Ph.D(Hawaii) May , 2004
Professor
CERTIFICATE
This is to certify that the dissertation entitled “The Reactivity of
Methylene Blue Towards Silver Nitrate and Mercury(II) Chloride”
submitted in partial fulfilment for the degree of Master of Science in
Chemistry to Bharathidasan University, under the semester system, is a
bonafide record of work done by Mr. M. Mohan Raj (Reg.No :
2002MS05) under my supervision and guidance and that the dissertation
has not previously formed the basis for the award of any degree, diploma,
associateship, fellowship or other similar titles.
(K. Panchanatheswaran)
Table of Contents
Acknowledgement I
Abstract II
List of Tables III
List of Figures IV
Introduction 1
Scope of the Work 12
Experimental Aspects
1). Instrumentation 13
2). Synthetic Chemistry 14
Results and Discussion 16
Conclusion 42
References 43
ACKNOWLEDGEMENT
It is with great pleasure that I thank my guide Dr. K.
Panchanatheswaran, Professor, for his valuable guidance, unstinted
support, useful discussions and constant encouragement throughout
the course of this study.
Dr. M. Palaniandavar, Professor and Head, Department of
Chemistry, is gratefully thanked for having provided the necessary
facilities.
My sincere thanks are due to all the faculty members,
research scholars and the non-teaching staff for their
encouragement.
Ms. S. Jose Kavitha spent her valuable time in solving the
crystal structure of the one of the products, I thank and acknowledge
her services.
With profound gratitude Mr. T. R. Sarangarajan, Lecturer,
SASTRA, Thanjavur and Mr. S. Chandrasekar, Lecturer,
Government Arts College, Ariyalur are thanked for their support. I am
very happy to thank my seniors Ms. M. Baby Mariyatra, Mr. E.
Mothi Mohamed, and Mr. B. S. Krishnamoorthy for their
support and help.
I offer my special thanks to my colleague, Ms. P. Suguna, for
boosting my spirits, and to my friends, classmates and juniors for
providing me support and comfort.
I am greatly indebted to my parents and sister for their love for
me without which the completion this work would not have been
possible. Above all, I thank God Almighty for His merciful blessings
(M. MOHAN RAJ)
ABSTRACT
The reaction of Methylene Blue with silver nitrate has yielded a
violet solid, soluble in water, methanol and ethanol. Recrystallization
of the product in water gave the diffraction quality crystals. Single
crystal X-ray investigations were used to determine the crystal and
molecular structure of the product. The compound crystallized in the
space group P-1, whose structure was found to contain Methylene
Blue cation and nitrate anion along with two water molecules. Several
intermolecular attractions involving N-H…O, C-H…O and pi-pi
interactions have been found in the product. Analogous reaction with
mercury(II) chloride gave violet brown solid. Attempts to crystallize
the product were not successful. The product was formulated to be
either a complex of Methylene Blue with mercury (II) chloride or one
with Methylene Blue cations and tetrachloromercurate anion. The
leuco base of Methylene Blue was obtained by its reaction with silver
nitrate and mercury(II) chloride. The colourless solids were not
characterized completely.
List of Tables
_________________________________________________
Title Page No.
_________________________________________________
1. Examples of Antipsychotic Phenothazine Drugs 9
2. UV Spectral data for Methylene Blue and its
‘Product’ with Silver Nitrate. 23
3. Bond Lengths in Methylene Blue Derivatives 24
4. Bond Angles in Methylene Blue Derivatives 25
5. Crystal data and structure refinement for 3,7-Bis
(dimethylamino)phenothiazin-5-ium nitrate dihydrate. 26
6. Atomic coordinates (× 104) and equivalent isotropic
displacement parameters (.°2×103 ) for Methylene
Blue Nitrate. 27
7. Bond lengths [A°] and angles [°] for Methylene Blue
Nitrate. 28
8. Anisotropic displacement parameters (.°2×103) for
Methylene Blue Nitrate. 30
9. Hydrogen coordinates ( X 104 ) and isotrpic displacement
parameters (.°2×103) for Methylene Blue Nitrate. 31
10. Hydrogen bonds for Methylene Blue Nitrate. 32
11. Analytical data for the products obtained by the
reactions of Methylene Blue with AgNO3 and HgCl2. 33
List of Figures
Title Page No.
1. Structures of Phenothiazine drugs. 4
2. Structures of Methylene Blue derivatives. 6
3. Atom numbering scheme in Methylene Blue derivatives 7
4. IR spectrum of Methylene Blue 19
5. IR spectrum of the Methylene Blue Nitrate. 20
6. UV-Visible spectrum of Methylene Blue. 21
7. UV-Visible spectrum of Methylene Blue Nitrate. 22
8. Molecular structure of Methylenes Blue Nitrate with 50%
probability displacement ellipsoids 34
9. Packing diagram of the molecules showing the interlinking
of the stacked aromatic moieties by N-H…O and
C-H…O hydrogen bonds. 35
10. Packing diagram showing the one-dimensional chain along a
axis formed by the nitrate ions and the water molecules 36
11. Packing diagram showing the one-dimensional chain
linking the aromatic moieties and the hydrogen bonding
interaction involving N(10) of the aromatic ring, nitrate
and the water molecules. 37
12. Packing diagram showing the supramolecular network
of the molecules with the one-dimensional chains linking
the adjacent stacked aromatic moieties, the chains being
interlinked via C-H…O hydrogen bonds. 38
13. IR spectrum of the product between Methylene Blue and
Mercury(II) Chloride. 39
14. IR spectrum of the product between Leucomethylene
Blue and Silver Nitrate. 40
15. IR spectrum of the product between Leucomethylene
Blue and Mercury(II) Chloride 41
CHAPTER I
Introduction
INTRODUCTION
Methylene Blue: Historiography1
Methylene Blue was first synthesized by the German chemist
Heinrich in 1876. Robert Koch discovered the tubercle bacillus with
the help of Methylene Blue. Paul Ehrlich who later discussed the anti-
syphilis drug, Salvarsan, noticed that the dye imparted colour only to
the carriers of illnesses and at the same time destroy them without
attacking the body’s own cells. The revolutionary idea led to the
development of chemotherapy, one of the greatest advances in
medical science. Methylene Blue is not only a good colouring agent
for living cells but also an excellent redox indicator in aqueous
solution as indicated below.
SNN23N(CH)32(CH)
NS)N(CH32)(CH23N+
............................reductionoxidationClH2+.HClmethylene blue(blue)
leucomethylene blue(colorless)
H
The redox system of Methylene Blue – Leucomethylene Blue
Preparation of Methylene Blue2:
Methylene Blue, 3,7-bis-(dimethlamino)phenothiazonium
chloride is by the far the most important phenothiazine dyestuff and is
prepared by the oxidation of N,N-dimethyl-p- phenylenediamine in
situ with sodium thiosulfate , sulfuric acid and sodium dichromate at
0°C under carefully controlled conditions. Further dimethylamine is
then added together with more dichromate to form the green indamine
thiosulfonic acid, which is finally treated with copper(II) sulfate and
further quantity of dichromate at 60-70°C to give Methylene Blue.
222233NMe222NMeMeNNMe2NMe2NMe2NMe2NMe2NHNHNMe22SOSH3SOSH+........
NaSOO___
_
................
__
__
O2)
NSN(CH3)(CH23NHNNMe22
....................
SOCu4NS2MeN2MeN2MeN2MeN2MeN
....................
___
_
O+
HSO3Methylene blue(Indamine Thiosulfonic acid)
Leuco methylene blue
The dyestuff may be isolated as the sparingly soluble zinc
chloride double salt after first screening off the insoluble chrome
residues. Medicinal quality Methylene Blue is obtained by a further
recrystallisation from dilute hydrochloric acid and brine. An
alternative and versatile laboratory synthesis of 3,7-diamino-
substituted phenothiazine dyes is based upon the reaction of
3,7-dibromophenothiazonium bromide prepared from phenothiazine
with amines.
Phenothiazine Dyes2:
Phenothiazine dyes are mostly salts of the oxidized form of
3,7-diaminophenothiazine with substituents on the amino groups. The
first phenothiazine dye to be made was 3,7-di-aminophenothiazonium
chloride, known as Lauth’s violet.
Methylene Blue3:
SNNN3CH3CH3CHH3C+
Cl H_
O2
New Methylene Blue NXX:
SNEtNH+
MeNHEtMeCl
Toluidine Blue:
MeSNNH22MeN2MeN2MeN2MeN2MeN+
Cl
Methylene Blue:
Cl+NMe2NMe2NMe2NMe2NMe2NHSNMeMe
Brilliant Alizarine Blue G:
OHOHSO3_
2MeN2MeN2MeN2MeN2MeN+
SN
Fig. 1. Structures of Phenothiazine Dyes2
Leuco-Methylene Blue2:
A pale yellow water insoluble solid. (m.p 185°C) may be
obtained from the indaminethiosulfonic acid precursor by boiling an
aqueous solution with dilute acid or more conveniently, by reduction
of Methylene Blue in aqueous solution with sodium dithionite. It is
readily re-oxidised to Methylene Blue on exposure to air and can be
N-acylated. Thus N-benzoyl-leuco-Methylene Blue is obtained by
benzoylation of leuco-Methlyene Blue with benzoyl chloride in
pyridine, in aqueous alkaline medium, or in a variety of water-
immiscible solvents.
Benzoyl-leuco-Methylene Blue is used in carbonless, pressure-
sensitive copying papers. In these systems it is dissolved, along with
other “color formers”, for example Crystal Violet Lactone, in a non-
polar high boiling solvent and the solution is encapsulated in gelatin
walled microcapsules. The suspension of capsules is applied to the
underside of a sheet of paper. Application of pressure, by either
writing or typing, to this paper causes the impression to a second,
underlying, sheet of paper the upper surface of which is coated with
an “acidic” material, generally an activated mineral such as silica or
attapulgite clay. A methylene Blue print is formed by hydrolysis of
the N-benzoyl group on the active surface and subsequent aerial
oxidation of the Leucomethylene Blue so produced.
Methylene Blue forms several derivatives containing different
anions whose structures were determined by X-ray Crystallography.
The following are examples.
Methylene Blue thiocyanate4:
+
C3HCH3CH3CH3NNSNNCS_
Methylene Blue urate hydrate5:
SNNN3CH3CH3CHH3C+
HNNNHNHOOO2OH
Fig. 2. Methylene Blue Derivatives
Bis(malenonitrilethiolato)-copper(II)bis(3,9-
bis(dimethylamino)phenazathionium) acetone solvate6:
+
C3HCH3CH3CH3NNSNC3HO+2NCCNNCCNCuSSSS3CH
Fig. 2. Methylene Blue Derivatives
O............................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................
OOO
..................................................................................................................................................................
..................
C1CCCCCCCCCCCCCCSC2345687911121314NN10N3132717237
Fig. 3. Atom numbering Scheme in Methylene Blue Derivatives
Phenothiazine Drugs7
Antipsychotic Agents:
Drug substances, which depress Central Nervous System and are
able to calm severely disturbed psychiatric patients without affecting
consciousness or causing any neurological effects are called antipsychotic
agents. They produce strong sedation without inducing sleep and cause a
state of indifference.
Phenothiazine Derivatives
Many phenothiazine derivatives have been synthesized and several
of them are useful in the treatment of psychotic states. Chlorpromazine is
one of the derivatives, which was effective in the treatment of various
psychotic disorders and also efficacious against nausea and vomiting.
Some fairly consistent patterns of relation between structure and
antipsychotic activity among individual classes of compounds has been
noted. Stereochemical and conformational considerations are important for
determination of psychotropic activity. In addition, water solubility, lipid-
water partitioning acid-base properties and surface activity have been
established to play a significant role in exhibiting potent antispychotic
properties.
A third carbon unbranched side chain gives the most active compound
in tranquilizing area i.e. amino group separated by third carbon atoms is
optimal for antipsychotic activity. A basic tertiary amino moiety provides
maximum antipsychotic potency 7.
Generic and
Proprietary
Name
Chemical
Name
Side Chain
R
R1
Chloropromazine
(Thorazine,
Largatil)
2-Chloro-10 (3-dimethyl-
amnio)-
propylphenothazine,II
-(CH2) 3-(NH3) 2
Cl
Promazine
(sparine)
10-(3-dimethylamino)-
propyl-phenothiazine,III
-(CH2) 3-N (NH3)2
H
Triflupromazine
(vesprin)
10-(3-dimetylamino)-
propyl)-2-(trifluoromethyl-
phenothiazine, IV
-(CH2) 3-N(NH3)2
CF3
Promethazine
(Phenergan)
10-(2-Dimethylaminopropyl)
phenothiazine, V
N(CH2)CHCH3(CH3)2
H
Trifluoperazine
(Stelazine)
10(3-(4-methyl-)piperazinyl))
Propyl-2-
trifluoromethylphenothiazine,
VI
NNCH33()CH2
CF3
Prochloroperazine
(Compazine)
2-chloro-10 (3-(4-methyl-1-
piperazinyl))-propyl
phenothiazine, VII
NNCH33()CH2
Cl
Fluphenazine
(Permititil,Prolixin)
10-(3-(4-(2-hydroxyethyl)
piperazinyl)
propyl)-2-trifluoromethyl
phenothiazine, VIII
CH2)(3NNH2CC2HHO
CF3
Mosoridazine
(Serentil)
10-2-(1-methylsulfinyl)
Phenothiazine,IX
N3()CH2CH3
OSCH
Table 1: Examples of Antipsychotic Phenothiazine
Drugs7
The Biological and Analytical Chemistry of
Methylene Blue
The dye methylene blue (MB) is widely used as a stain and has
a number of biological uses as discussed below8. It can be used to treat
urinary tract infections, to distinguish between cancerous and normal tissue
and it has potential as a prophylactic treatment for Alzheimer’s disease.
The metabolism and excretion of MB in living organisms was the subject
of a number of investigations the earliest dating back to 1885. Early
investigations showed that MB was eliminated form the body in unchanged
from as well as in some leuco- dye forms. A detailed investigation was
carried out in 1972 which confirmed these studies. It was shown that
extracts of urine from human patients dosed with 10 mg sample of MB
contained MB but also a leuco- dye form.The reaction between
Chondroitin 4-Sulfate with Methylene Blue has been studied9. The results
show that via an electrostatic interaction Methylene Blue aggregates on
Chondroitin 4-Sulfate as concluded by CD spectra .
_______________________
Structure of Chondroitin 4-Sulfate
n)(
HOHHOOOOSO3HCCHOH2HCOOHOOOOHO+NaCNHO
Methylene Blue has well established photochemical properties and
has been used in a variety of photochemical applications including
photodynamic therapy(PDT)10, based on the property of cetain
biocompatible sensitizers to generate reactive species when they absob
light, resulting in the destruction of neighboring biomolecules and cell
death.
Methylene Blue is used as a redox indicator in the estimation of
titanium(III) chloride, in place of starch in iodometric titrations; its
insoluble perchlorate and dichromate can serve as the basis of gravimetric
determinations2. Methylene Blue can be oxidised by ammonium persulfate
in presence of Au(III). This serves as the basis for the determination
Pd(II)11. Arsenic can be determined in parts-per-million (ppm) level by
absorbance measurement. This method is based on the quantitative colour
bleaching of the dye, Methylene Blue by arsine catalysed by Ag or Au
nano particles in micellar medium. This arsine has been generated in situ
from sodium arsenate by sodium borohydride reduction. The absorbance
measurement was carried out at the .max of the dye at 660 nm12. Methylene
Blue can be reduced to the leuco-base form by reduction with ascorbic acid
also13.
CHAPTER II
Scope of the Work
Scope of the work
Methylene Blue is a cationic dye and important for its analytical and
biological applications. It will be interesting to know about its reactions
towards its metal salts, No metal complexes of Methylene Blue is known at
present, although it has many sites for coordination. The structural unit of
Methylene Blue viz, phenothiazine is present in many psychiatric drugs.
The leuco base of Methylene Blue can also be prepared by the reaction
with reducing agents. This can also react with metal salts, perhaps in
different fashion.
Extraction of palladium from the nuclear waste of the power plants is
one of the current challenges in nuclear chemistry. Making use of the
known affinity of sulfur to Pd2+, sulfur based extractants are proposed for
the above purpose. The interaction of Methylene Blue, a sulfur containing
heterocyclic compound, with both Ag+ & Hg2+ is studied. The above ions
closely resemble Pd2+ and are chosen for model studies. In order to
ascertain the interaction of Ag+ & Hg2+, the reactions of Methylene Blue
with AgNO3 and HgCl2 have been attempted.
CHAPTER III
Experimental Aspects
Experimental Aspects
1. Instrumentation
The IR spectrum was taken as KBr pellets using Perkin Elmer FTIR
spectrophotometer at the Department of Chemistry, Bharathidasan
University, Tiruchirappalli. The UV-Visible spectra were recorded using
carry 300-model Varian UV-Visible spectrophotometer at the Department
of Chemistry, Bharathidasan University, Tiruchirappalli. X-ray intensisty
data were collected using the EPSRC National Crystallographic Services
Southampton, England with Brucker Nonius KappaCCD area detector.
The structure solution and refinement were carried out using the following
programs, SHELXS97 and SHELXL97. Molecular diagrams were obtained
with ORTEP3 package using 50 % probability thermal ellipsoids for the
non hydrogen atoms and PLATON97 package.
2. Synthetic Chemistry
(i) Reaction of Silver Nitrate with Methylene Blue
Silver nitrate (0.339 g, 2 mmol) and Methylene Blue (0.373 g, 1
mmol) were mixed in 40 ml of water. The mixture was stirred for half an
hour. Diffraction quality violet crystals were obtained upon complete
evaporation of water. m.p >280°C.
IR (cm-1): 3418, 1599, 1486, 1443, 1384, 1356, 252, 1176, 1147, 1082,
961, 884, 814, 612.
(ii) Reaction of Mercury(II) Chloride with Methylene Blue
Mercury(II) chloride (0.145 g, 1 mmol) was dissolved in methanol
and Methylene Blue (0.2 g, 1 mmol) in water was added to it. The mixture
was stirred for few minutes. The brown solid was filtered off. m.p >280°C.
Yield: 73%.
IR (cm-1): 3463, 1599, 1491, 1436, 1398, 1336, 1241, 1219, 1177, 1138,
1056, 1035, 948, 886, 851, 821, 663.
(iii) Preparation of Leucomethylene Blue
Sodium hydroxide (0.2 g) was added to 50 ml of water in a round-
bottomed flask followed by 0.09 g of glucose. The mixture was treated
with Methylene Blue (0.186 g, 1 mmol) in water. The mixture was heated
in steps of 10°C up to 50°C. The blue coloured solution became colourless.
This indicated the formation of Leucomethylene Blue, which was found to
be unstable to air.
(iv). Reaction of Mercury(II) Chloride with Leucomethylene Blue
Mercury(II) chloride(0.135 g, 1 mmol) was dissolved in methanol
and to that aqueous solution of Leucomethylene Blue (which was prepared
by procedure (iii)) was added. The mixture was stirred for some time and
filtered. The filtrate was evaporated to give rose red solid. m.p >280°C.
IR (cm-1): 1634, 1454, 1382, 1089, 879.
(v) Reaction of Silver Nitrate with Leucomethylene Blue
Silver nitrate (0.0844 g, 1 mmol) was dissolved in water and to
that aqueous solution of Leucomethylene Blue (which was prepared by
procedure (iii)) was added. The mixture was stirred for some time and
filtered. The filtrate was evaporated to give rose red solid. m. p >280°C.
IR (cm-1): 3439, 2920, 1642, 1382, 1154, 1071, 1024, 879.
CHAPTER IV
Results and Discussion
Results and Discussion
Reaction of Silver Nitrate with Methylene Blue:
The product is insoluble in chloroform whereas Methylene Blue is
partially soluble in chloroform. The IR spectrum of the product shows
features very different from that of Methylene Blue (Fig. 4 & 5).
The spectrum has peaks due to Methylene Blue and the nitrate ion. The
peak at 961 cm-1 which is absent in Methylene Blue, shows the presence of
nitrate ion. The UV spectra of Methylene Blue nitrate indicates Red shift
of absorption to 293 nm with respect to the absorption at 259 nm in
Methylene Blue itself (Fig. 6 & 7)(Table. 2). In order to assign the
structure of the solid X-ray Crystallographic investigation was undertaken.
The Ortep diagram of the product is shown in (Fig. 8). The X-ray crystal
structure shows that the product (1) Methylene Blue nitrate consists of
Methylene Blue cation, nitrate anion and two water molecules. The
Methylene Blue cation can be represented by structures I and II.
(CH3)2NNSN(CH3)2+N(CH3)2SN(CH3)2N+
I II
Structure II is predominant in the chloride and thiocyanate salts.
The cation of the product adopts structure II as evident from the
pronounced shortening of bonds C1-C2 (1.359(4) A°) and C4-C12
(1.373(4) A°) compared with the other carbon-carbon bonds. The two C-S
bonds are equal in length, supporting that structure II is more appropriate
).2Hfor the cation. The bond lengths and angles are comparable to those of
other Methylene Blue derivatives (Table 3 & 4). The relevant
crystallographic data are given in Tables 5 to 10. In contrast to the
chloride salt (MBCl.5H2O) the degree of hydration of the nitrate salt
(MBNO3.2H2O) is lower. The analytical data (Table 11) also
suggest the formula, C16H18N4SO3.2H2O(MB(NO32O).
The crystal structure is stabilized by pi-pi interaction between the
adjacent aromatic moieties stacked in antiparallel fashon along b axis at a
distance of 3.740(18) Aº as well as interlinking of the aromatic moieties by
hydrogen bonds. This interaction occurs pairwise (Fig. 9). The nitrate ion
and the water molecules form one-dimensional chain in a direction (Fig.
10). This is linked to the aromatic ring via C-H…O and NH…O
interactions. The adjacent stacked pair is stabilized by hydrogen bonding
interaction involving N(10) of the aromatic ring, nitrate and water
molecules (Fig. 11). These intermolecular interactions contribute to the
supramolecular structure of the product (Fig. 12).
Reaction of Mercury(II) Chloride with Methylene Blue
In the IR spectrum of Methylene Blue (Fig. 4) the .cs which occurs
at 1250 cm-1 is shifted to 1241 cm-1 in the product (2) (Fig. 13). This is
indicative of a reaction. From the IR spectral data it can be inferred that
coordination might have occurred through sulfur. The formulation of
(MB)2HgCl4 is also possible for the product. This is supported by the
analytical data (Table 11).
Reaction of Silver Nitrate with Lecuomethylene Blue:
In the IR spectrum of Methylene Blue (Fig. 4) the .CN stretching
frequency occurs at 1446 cm-1, which is significantly shifted to 1454 cm-1,
in the product (3) (Fig. 14). Similarly, the .C=C is shifted from 1599 cm-1 to
1642 cm-1. This shows that the reaction has occurred and the coordination
might have occurred through the N atom.
Reaction of Mercury(II) Chloride with Lecuomethylene Blue:
In the IR spectrum for the Methylene Blue (fig. 4) the .CN
stretching frequency occurs at 1446 cm-1, which is shifted to 1454 cm-
1 in the product. Similarly, the .C=C is shifted from 1599 cm-1 to 1634 cm-1
in the product (4) (Fig. 15). This shows that the reaction has occurred
between the two reagents and the coordination, if any, might have occurred
through the N atom.
The correct structures can be assigned using X-ray crystallographic
investigations. However, attempts to prepare crystals of products of the
reactions of Lecuomethylene Blue with mercury(II) chloride and silver
nitrate were not successful, although several attempts were made.
4013060801001204000400100020003000%TWavenumber[cm-1]
IR cm-1
: 3397, 1599, 1489, 1446, 1395, 1354, 1339, 1250,
1220, 1180, 1143, 1064, 1036, 947, 884, 854, 808, 666, 536,
Fig. 4. IR spectrum of Methylene Blue
4000.03000200015001000450.028.7354045505560657074.0cm-1%T
IR (cm-1): 3418, 1599, 1486, 1443, 1384, 1356, 252, 1176, 1147, 1082,
961, 884, 814, 612.
Fig. 5. IR spectrum of Methylene Blue Nitrate
Fig. 6. UV-Visible spectrum of Methylene Blue
Fig. 7. UV-Visible spectrum of Methylene Blue Nitrate.
Table 2: UV Spectral data for Methylene Blue and its ‘product’
with Silver Nitrate
UV/10mg/10ml
Diluted 400 times
Methylene Blue
.max (nm)
Methylene Blue
nitrate
.max (nm)
665
665
259
293
Table 3: Bond Lengths in Methylene Blue Derivatives4,5,6
Chloride Thiocyanate Acetone solvate
C(1)-C(2) 1.341 1.357 1.343
C(1)-C(11) 1.417 1.411 1.426
C(2)-C(3) 1.445 1.436 1.423
C(3)-N(3) 1.331 1.48 1.344
C(3)-C(4) 1.419 1.391 1.416
N(3)-C(32) 1.454 1.489 1.463
N(3)-C(31) 1.465 1.546 1.444
C(4)-C(12) 1.349 1.341 1.375
S(5)-C(13) 1.738 1.736 1.728
S(5)-C(12) 1.721 1.742 1.729
C(6)-C(13) 1.356 1.356 1.368
C(6)-C(7) 1.401 1.401 1.391
C(7)-N(7) 1.344 1.314 1.355
C(7)-C(8) 1.423 1.447 1.443
N(7)-C(71) 1.444 1.536 1.456
N(7)-C(72) 1.444 1.508 1.453
C(8)-C(9) 1.349 1.346 1.35
C(9)-C(14) 1.421 1.409 1.409
N(10)-C(11) 1.336 1.329 1.324
N(10)-C(14) 1.337 1.353 1.343
C(11)-C(12) 1.439 1.418 1.438
C(13)-C(14) 1.42 1.401 1.443