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A dissertation submitted to the
in partial fulfillment of the requirements
for the award of the degree of
MASTER OF SCIENCE
M. Mohan Raj
DEPARTMENT OF CHEMISTRY
TIRUCHIRAPPALLI- 620 024
Department of Chemistry, Bharathidasan University,
Tiruchirappalli - 620 024, India
Dr. K. Panchanatheswaran, M.Sc., Ph.D(Hawaii) May , 2004
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.
Table of Contents Acknowledgement I Abstract II List of Tables III List of Figures IV Introduction 1 Scope of the Work 12 .
Synthetic Chemistry 14 Results and Discussion 16 Conclusion 42 References 43 . Instrumentation 13 2).Experimental Aspects 1).
S. K. Department of Chemistry. unstinted support. My sincere thanks are due to all the faculty members. M. Dr. I thank and acknowledge . Professor and Head. useful discussions and constant encouragement throughout the course of this study. Jose Kavitha spent her valuable time in solving the crystal structure of the one of the products. Professor. Panchanatheswaran.ACKNOWLEDGEMENT It is with great pleasure that I thank my guide Dr. for his valuable guidance. is gratefully thanked for having provided the necessary facilities. research scholars and the non-teaching staff for their encouragement. Ms. Palaniandavar.
R. M. I am very happy to thank my seniors Ms. S. Krishnamoorthy for their support and help. Thanjavur and Mr. T. SASTRA. Government Arts College. S. Sarangarajan. Mr. Chandrasekar. With profound gratitude Mr.her services. Mothi Mohamed. E. and Mr. Lecturer. Baby Mariyatra. Ariyalur are thanked for their support. . Lecturer. B.
I thank God Almighty for His merciful blessings (M. for boosting my spirits. and to my friends. 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. Suguna. MOHAN RAJ) . Ms. classmates and juniors for providing me support and comfort. Above all.I offer my special thanks to my colleague. P.
ABSTRACT The reaction of Methylene Blue with silver nitrate has yielded a violet solid. . Recrystallization of the product in water gave the diffraction quality crystals. 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. Analogous reaction with mercury(II) chloride gave violet brown solid. whose structure was found to contain Methylene Blue cation and nitrate anion along with two water molecules. The colourless solids were not characterized completely. C-H…O and pi-pi interactions have been found in the product. Single crystal X-ray investigations were used to determine the crystal and molecular structure of the product. Several intermolecular attractions involving N-H…O. soluble in water. The compound crystallized in the space group P-1. Attempts to crystallize the product were not successful. The leuco base of Methylene Blue was obtained by its reaction with silver nitrate and mercury(II) chloride. methanol and ethanol.
Bond Angles in Methylene Blue Derivatives 25 5. Bond Lengths in Methylene Blue Derivatives 24 4. 27 . UV Spectral data for Methylene Blue and its ‘Product’ with Silver Nitrate.°2×103 ) for Methylene Blue Nitrate. 23 3.List of Tables _________________________________________________ Title Page No.7-Bis (dimethylamino)phenothiazin-5-ium nitrate dihydrate. _________________________________________________ 1. Atomic coordinates (× 104) and equivalent isotropic displacement parameters (. Crystal data and structure refinement for 3. 26 6. Examples of Antipsychotic Phenothazine Drugs 9 2.
33 . Hydrogen coordinates ( X 104 ) and isotrpic displacement parameters (. 31 10.°2×103) for Methylene Blue Nitrate.°2×103) for Methylene Blue Nitrate. 32 11. Bond lengths [A°] and angles [°] for Methylene Blue Nitrate.7. 30 9. Anisotropic displacement parameters (. 28 8. Hydrogen bonds for Methylene Blue Nitrate. Analytical data for the products obtained by the reactions of Methylene Blue with AgNO3 and HgCl2.
List of Figures Title Page No. 35 . Packing diagram of the molecules showing the interlinking of the stacked aromatic moieties by N-H…O and C-H…O hydrogen bonds. IR spectrum of Methylene Blue 19 5. 6 3. UV-Visible spectrum of Methylene Blue Nitrate. IR spectrum of the Methylene Blue Nitrate. Structures of Methylene Blue derivatives. 22 8. 21 7. Molecular structure of Methylenes Blue Nitrate with 50% probability displacement ellipsoids 34 9. Structures of Phenothiazine drugs. Atom numbering scheme in Methylene Blue derivatives 7 4. 20 6. 4 2. UV-Visible spectrum of Methylene Blue. 1.
nitrate and the water molecules. 37 .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.
38 13. IR spectrum of the product between Leucomethylene Blue and Mercury(II) Chloride 41 .12. 40 15. Packing diagram showing the supramolecular network of the molecules with the one-dimensional chains linking the adjacent stacked aromatic moieties. 39 14. the chains being interlinked via C-H…O hydrogen bonds. IR spectrum of the product between Methylene Blue and Mercury(II) Chloride. IR spectrum of the product between Leucomethylene Blue and Silver Nitrate.
CHAPTER I .
. Paul Ehrlich who later discussed the antisyphilis drug.... Methylene Blue is not only a good colouring agent for living cells but also an excellent redox indicator in aqueous solution as indicated below. Robert Koch discovered the tubercle bacillus with the help of Methylene Blue.. 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. Salvarsan.HClmethylene blue(blue) leucomethylene blue(colorless) H The redox system of Methylene Blue – Leucomethylene Blue ..... one of the greatest advances in medical science.. SNN23N(CH)32(CH) NS)N(CH32)(CH23N+ ..INTRODUCTION Methylene Blue: Historiography1 Methylene Blue was first synthesized by the German chemist Heinrich in 1876...reductionoxidationClH2+.....
3.Preparation of Methylene Blue2: Methylene Blue. sulfuric acid and sodium dichromate at .phenylenediamine in situ with sodium thiosulfate .N-dimethyl-p.7-bis-(dimethlamino)phenothiazonium chloride is by the far the most important phenothiazine dyestuff and is prepared by the oxidation of N.
.................... __ __ O2) NSN(CH3)(CH23NHNNMe22 .... NaSOO___ _ .................... ___ _ O+ HSO3Methylene blue(Indamine Thiosulfonic acid) Leuco methylene blue .... SOCu4NS2MeN2MeN2MeN2MeN2MeN ....... 222233NMe222NMeMeNNMe2NMe2NMe2NMe2NMe2NHNHNMe22SOSH3SOSH+.... which is finally treated with copper(II) sulfate and further quantity of dichromate at 60-70°C to give Methylene Blue.0°C under carefully controlled conditions... Further dimethylamine is then added together with more dichromate to form the green indamine thiosulfonic acid.....
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 .
7-diaminophenothiazine with substituents on the amino groups.recrystallisation from dilute hydrochloric acid and brine.7-di-aminophenothiazonium chloride. known as Lauth’s violet. . Phenothiazine Dyes2: Phenothiazine dyes are mostly salts of the oxidized form of 3.7-dibromophenothiazonium bromide prepared from phenothiazine with amines. An alternative and versatile laboratory synthesis of 3. The first phenothiazine dye to be made was 3.7-diaminosubstituted phenothiazine dyes is based upon the reaction of 3.
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 .
It is readily re-oxidised to Methylene Blue on exposure to air and can be N-acylated. The suspension of capsules is applied to the underside of a sheet of paper. in a nonpolar high boiling solvent and the solution is encapsulated in gelatin walled microcapsules. or in a variety of waterimmiscible solvents. (m. along with other “color formers”. Thus N-benzoyl-leuco-Methylene Blue is obtained by benzoylation of leuco-Methlyene Blue with benzoyl chloride in pyridine.Leuco-Methylene Blue2: A pale yellow water insoluble solid. In these systems it is dissolved. Benzoyl-leuco-Methylene Blue is used in carbonless. pressuresensitive copying papers. by reduction of Methylene Blue in aqueous solution with sodium dithionite. . for example Crystal Violet Lactone. generally an activated mineral such as silica or attapulgite clay. in aqueous alkaline medium. Application of pressure. sheet of paper the upper surface of which is coated with an “acidic” material. by either writing or typing. underlying. to this paper causes the impression to a second. 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.p 185°C) may be obtained from the indaminethiosulfonic acid precursor by boiling an aqueous solution with dilute acid or more conveniently.
The following are examples. Methylene Blue Derivatives . Methylene Blue thiocyanate4: + C3HCH3CH3CH3NNSNNCS_ Methylene Blue urate hydrate5: SNNN3CH3CH3CHH3C+ HNNNHNHOOO2OH Fig. 2.Methylene Blue forms several derivatives containing different anions whose structures were determined by X-ray Crystallography.
........................................................ OOO ......................... Methylene Blue Derivatives O.............. .............................. C1CCCCCCCCCCCCCCSC2345687911121314NN10N3132717237 Fig........................................................................ 3...........................................................................................................................9bis(dimethylamino)phenazathionium) acetone solvate6: + C3HCH3CH3CH3NNSNC3HO+2NCCNNCCNCuSSSS3CH Fig........... Atom numbering Scheme in Methylene Blue Derivatives .................. ...................................................................................................................................................................................... .............................................................................Bis(malenonitrilethiolato)-copper(II)bis(3.................... 2................................... ...............................................................
They produce strong sedation without inducing sleep and cause a state of indifference. 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. Phenothiazine Derivatives Many phenothiazine derivatives have been synthesized and several of them are useful in the treatment of psychotic states. Some fairly consistent patterns of relation between structure and antipsychotic activity among individual classes of compounds has been .Phenothiazine Drugs7 Antipsychotic Agents: Drug substances. Chlorpromazine is one of the derivatives. which was effective in the treatment of various psychotic disorders and also efficacious against nausea and vomiting.
. In addition.noted. A basic tertiary amino moiety provides maximum antipsychotic potency 7. water solubility. Stereochemical and conformational considerations are important for determination of psychotropic activity. A third carbon unbranched side chain gives the most active compound in tranquilizing area i. amino group separated by third carbon atoms is optimal for antipsychotic activity. lipidwater partitioning acid-base properties and surface activity have been established to play a significant role in exhibiting potent antispychotic properties.e.
Generic and Proprietary Name Chemical Name Side Chain R R1 Chloropromazine (Thorazine.II . Largatil) 2-Chloro-10 (3-dimethylamnio)propylphenothazine.
-(CH2) 3-(NH3) 2 Cl Promazine (sparine) 10-(3-dimethylamino)propyl-phenothiazine.III -(CH2) 3-N (NH3)2 H Triflupromazine (vesprin) .
IV -(CH2) 3-N(NH3)2 CF3 Promethazine (Phenergan) 10-(2-Dimethylaminopropyl) phenothiazine.10-(3-dimetylamino)propyl)-2-(trifluoromethylphenothiazine. V N(CH2)CHCH3(CH3)2 .
H Trifluoperazine (Stelazine) 10(3-(4-methyl-)piperazinyl)) Propyl-2trifluoromethylphenothiazine. VI NNCH33()CH2 CF3 .
Prolixin) 10-(3-(4-(2-hydroxyethyl) piperazinyl) propyl)-2-trifluoromethyl phenothiazine. VIII .Prochloroperazine (Compazine) 2-chloro-10 (3-(4-methyl-1piperazinyl))-propyl phenothiazine. VII NNCH33()CH2 Cl Fluphenazine (Permititil.
IX N3()CH2CH3 OSCH Table 1: Examples of Antipsychotic Phenothiazine Drugs7 .CH2)(3NNH2CC2HHO CF3 Mosoridazine (Serentil) 10-2-(1-methylsulfinyl) Phenothiazine.
It was shown that extracts of urine from human patients dosed with 10 mg sample of MB contained MB but also a leuco. The metabolism and excretion of MB in living organisms was the subject of a number of investigations the earliest dating back to 1885.dye forms. Early investigations showed that MB was eliminated form the body in unchanged from as well as in some leuco.The reaction between Chondroitin 4-Sulfate with Methylene Blue has been studied9. _______________________ Structure of Chondroitin 4-Sulfate n)( HOHHOOOOSO3HCCHOH2HCOOHOOOOHO+NaCNHO . to distinguish between cancerous and normal tissue and it has potential as a prophylactic treatment for Alzheimer’s disease. A detailed investigation was carried out in 1972 which confirmed these studies. It can be used to treat urinary tract infections.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.dye form. The results show that via an electrostatic interaction Methylene Blue aggregates on Chondroitin 4-Sulfate as concluded by CD spectra .
This method is based on the quantitative colour bleaching of the dye.max of the dye at 660 nm12. Methylene Blue is used as a redox indicator in the estimation of titanium(III) chloride. . Methylene Blue by arsine catalysed by Ag or Au nano particles in micellar medium.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. 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 arsine has been generated in situ from sodium arsenate by sodium borohydride reduction. Methylene Blue can be reduced to the leuco-base form by reduction with ascorbic acid also13. Methylene Blue can be oxidised by ammonium persulfate in presence of Au(III). The absorbance measurement was carried out at the . in place of starch in iodometric titrations. resulting in the destruction of neighboring biomolecules and cell death. its insoluble perchlorate and dichromate can serve as the basis of gravimetric determinations2.
CHAPTER II .
Scope of the Work .
the reactions of Methylene Blue with AgNO3 and HgCl2 have been attempted. with both Ag+ & Hg2+ is studied. although it has many sites for coordination. 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+. The leuco base of Methylene Blue can also be prepared by the reaction with reducing agents. This can also react with metal salts. In order to ascertain the interaction of Ag+ & Hg2+. It will be interesting to know about its reactions towards its metal salts. The structural unit of Methylene Blue viz. phenothiazine is present in many psychiatric drugs. sulfur based extractants are proposed for the above purpose. a sulfur containing heterocyclic compound.Scope of the work Methylene Blue is a cationic dye and important for its analytical and biological applications. perhaps in different fashion. No metal complexes of Methylene Blue is known at present. The interaction of Methylene Blue. The above ions closely resemble Pd2+ and are chosen for model studies. .
CHAPTER III .
Experimental Aspects .
Bharathidasan University.Experimental Aspects 1. England with Brucker Nonius KappaCCD area detector. Tiruchirappalli. X-ray intensisty data were collected using the EPSRC National Crystallographic Services Southampton. The structure solution and refinement were carried out using the following programs. Tiruchirappalli. Instrumentation The IR spectrum was taken as KBr pellets using Perkin Elmer FTIR spectrophotometer at the Department of Chemistry. The UV-Visible spectra were recorded using carry 300-model Varian UV-Visible spectrophotometer at the Department of Chemistry. . Bharathidasan University. SHELXS97 and SHELXL97. Molecular diagrams were obtained with ORTEP3 package using 50 % probability thermal ellipsoids for the non hydrogen atoms and PLATON97 package.
(ii) Reaction of Mercury(II) Chloride with Methylene Blue Mercury(II) chloride (0. 1436. 1356. 1398. 2 mmol) and Methylene Blue (0. 1486. 1336. 1 mmol) was dissolved in methanol and Methylene Blue (0.339 g. 1443. 948. The mixture was stirred for few minutes. Diffraction quality violet crystals were obtained upon complete evaporation of water. m. 1176. 252.2. 663. Synthetic Chemistry (i) Reaction of Silver Nitrate with Methylene Blue Silver nitrate (0. 1 mmol) in water was added to it. 851. 1035. 886. The mixture was stirred for half an hour. 1599. IR (cm-1): 3463. 884.373 g.p >280°C. The brown solid was filtered off. 1 mmol) were mixed in 40 ml of water. 814. 1177. 961. 1056. 612. .p >280°C. 1219. m. 1491.145 g. 821. 1082.2 g. 1599. 1147. IR (cm-1): 3418. 1384. 1138. Yield: 73%. 1241.
1 mmol) in water. This indicated the formation of Leucomethylene Blue. The mixture was treated with Methylene Blue (0. The blue coloured solution became colourless.186 g. .2 g) was added to 50 ml of water in a roundbottomed flask followed by 0. which was found to be unstable to air.09 g of glucose. The mixture was heated in steps of 10°C up to 50°C.(iii) Preparation of Leucomethylene Blue Sodium hydroxide (0.
The mixture was stirred for some time and filtered. m. The filtrate was evaporated to give rose red solid. 879. The mixture was stirred for some time and filtered.0844 g.135 g. 1089. 1154. . 1454. 879. 1071. 1382. Reaction of Mercury(II) Chloride with Leucomethylene Blue Mercury(II) chloride(0. p >280°C.p >280°C. 1642.(iv). (v) Reaction of Silver Nitrate with Leucomethylene Blue Silver nitrate (0. 1382. 1 mmol) was dissolved in water and to that aqueous solution of Leucomethylene Blue (which was prepared by procedure (iii)) was added. IR (cm-1): 1634. m. IR (cm-1): 3439. 1 mmol) was dissolved in methanol and to that aqueous solution of Leucomethylene Blue (which was prepared by procedure (iii)) was added. 2920. 1024. The filtrate was evaporated to give rose red solid.
CHAPTER IV .
Results and Discussion .
(CH3)2NNSN(CH3)2+N(CH3)2SN(CH3)2N+ . 8). The Methylene Blue cation can be represented by structures I and II. 2). 6 & 7)(Table. 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. shows the presence of nitrate ion.Results and Discussion Reaction of Silver Nitrate with Methylene Blue: The product is insoluble in chloroform whereas Methylene Blue is partially soluble in chloroform. 4 & 5). The peak at 961 cm-1 which is absent in Methylene Blue. The X-ray crystal structure shows that the product (1) Methylene Blue nitrate consists of Methylene Blue cation. The Ortep diagram of the product is shown in (Fig. In order to assign the structure of the solid X-ray Crystallographic investigation was undertaken. The spectrum has peaks due to Methylene Blue and the nitrate ion. nitrate anion and two water molecules. The IR spectrum of the product shows features very different from that of Methylene Blue (Fig.
The two C-S bonds are equal in length. supporting that structure II is more appropriate .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 (1.373(4) A°) compared with the other carbon-carbon bonds.359(4) A°) and C4-C12 (1.
The nitrate ion and the water molecules form one-dimensional chain in a direction (Fig.2H2O(MB(NO32O). 10).5H2O) the degree of hydration of the nitrate salt (MBNO3. The relevant crystallographic data are given in Tables 5 to 10. From the IR spectral data it can be inferred that coordination might have occurred through sulfur. These intermolecular interactions contribute to the supramolecular structure of the product (Fig. The analytical data (Table 11) also suggest the formula. This is supported by the . 11). The bond lengths and angles are comparable to those of other Methylene Blue derivatives (Table 3 & 4). Reaction of Mercury(II) Chloride with Methylene Blue In the IR spectrum of Methylene Blue (Fig. C16H18N4SO3. 13). This interaction occurs pairwise (Fig.2Hfor the cation.740(18) Aº as well as interlinking of the aromatic moieties by hydrogen bonds. nitrate and water molecules (Fig.). 12). The adjacent stacked pair is stabilized by hydrogen bonding interaction involving N(10) of the aromatic ring. This is linked to the aromatic ring via C-H…O and NH…O interactions.cs which occurs at 1250 cm-1 is shifted to 1241 cm-1 in the product (2) (Fig. The formulation of (MB)2HgCl4 is also possible for the product.2H2O) is lower. 4) the . 9). This is indicative of a reaction. 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. In contrast to the chloride salt (MBCl.
.analytical data (Table 11).
the . Reaction of Mercury(II) Chloride with Lecuomethylene Blue: In the IR spectrum for the Methylene Blue (fig.C=C is shifted from 1599 cm-1 to 1642 cm-1. attempts to prepare crystals of products of the reactions of Lecuomethylene Blue with mercury(II) chloride and silver nitrate were not successful. 15). 4) the .C=C is shifted from 1599 cm-1 to 1634 cm-1 in the product (4) (Fig. might have occurred through the N atom. which is significantly shifted to 1454 cm-1. in the product (3) (Fig. However.Reaction of Silver Nitrate with Lecuomethylene Blue: In the IR spectrum of Methylene Blue (Fig. if any. This shows that the reaction has occurred and the coordination might have occurred through the N atom. although several attempts were made. Similarly. 4) the . 14).CN stretching frequency occurs at 1446 cm-1. the .CN stretching frequency occurs at 1446 cm-1. Similarly. The correct structures can be assigned using X-ray crystallographic investigations. which is shifted to 1454 cm1 in the product. . This shows that the reaction has occurred between the two reagents and the coordination.
Fig. 1446. 1395. 536. 854.4013060801001204000400100020003000%TWavenumber[cm-1] IR cm-1 : 3397. 884. 1180. 4. 1220. 1064. 1036. 1339. 666. 1143. 808. 947. 1489. IR spectrum of Methylene Blue . 1250. 1599. 1354.
1599. 1443. 252. IR spectrum of Methylene Blue Nitrate . 1147.0cm-1%T IR (cm-1): 3418.7354045505560657074. 1356. 5.03000200015001000450. Fig. 1176. 961. 1486.028. 1384. 612. 884. 814.4000. 1082.
UV-Visible spectrum of Methylene Blue . 6.Fig.
Fig. . UV-Visible spectrum of Methylene Blue Nitrate. 7.
Table 2: UV Spectral data for Methylene Blue and its ‘product’
with Silver Nitrate
Diluted 400 times
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
324 N(10)-C(14) 1.353 1.438 C(13)-C(14) 1.418 1.329 1.336 1.337 1.N(10)-C(11) 1.439 1.343 C(11)-C(12) 1.401 1.443 .42 1.
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