Ni(II), Co(Li), Sb(Ili), Bi(III) & with Iodine Monochloride & Trichloride

Indian Journal of Chemistry Vol. 14A, January 1976, pp. 48-50

Adducts of Thiotrithiazyl Chloride with the Chlorides of Cu(lI), Ni(II), Co(lI), Sb(IlI), Bi(III) & with Iodine Monochloride & Trichloride

R. C. PAUL, RAJ P. SHARMA & RAJENDAR D. VERMA Department of Chemistry, Panja.b University, Chancligarh 160014

Received 25 June 1975; accepted 19 August 1975

Thiotrithiazyl chloride forms 1 : 1 adducts with CuCI., NiCI••CoCI•• SbCI3•BiCI3•ICI and ICI3. It also forms 2: 1 (li~and-SbCI3) adduct with SbCI3. The adducts are ionic in nature. The nature of the cations and the anions have been established by physical methods. The anions MCI;. where M = Cu. Ni, Co have been shown to be dimers with tetrahedral environment around metal atoms.

VARIETY of physical and chemical methods++ Phosphorus(V) chloride (BDH, AR) was used as have been used to study the structure of suc~. Iodine (~) and iodine (III) chlorides were A thiotrithiazyl compounds, S4NaX, where X purified by fractional crystallization and sublimation is anionic group. Only recently X-ray diffraction" respectively. Solvents were distilled and made and NMR studies? of S4N3NOa have established anhydrous before use. that the cation, S4N~, has seven membered planar Preparation of the adducts - Cobalt, nickel and ring structui e (I), copper chlorides and thiotrithiazyl chloride were _N, take~ in thionyl chloride in the required stoichio- metric quantities and the contents stirred. Re- S ,"" S r : : I actions occurred in suspension. The compounds N: ! N formed were filtered, washed with thionyl chloride v ; / / followed by dry carbon tetrachloride and dried in S-s vacuo. In the case of other chlorides, dichloro- 1 methane was used as the reaction medium. Re- actions occurred in suspension in this medium also. The equal SoN bond distances indicates that there Thiotrithiazyl chloride does not form adducts is a delocalization of -e-electrons except in the S-S bond. The S4N~ cation is stable towards strong w~th rei, chlorine and metals were of electron rich inorganic aromatics". Thiotrithiazyl chloride undergoes metathetical estimated by the standard methods, while nitrogen reactions in non-aqueous solutions'? and forms was determined microanalytically. The analytical results are given in Table 1. adducts with Lewis acids10,l1. It forms ionic halosulphates and haloselenates on treatment with Physical measurements - Infrared spectra of the halosulphonic acids or sulphur trioxide-f and selenium compounds were recorded in nujol on a Perkin trioxide-" respectively. It also reacts with excess Elmer 337 spectrophotometer using sodium chloride or silver chloride plates. Far infrared of the com- of protonic acids, HAI4, [A = S03CF3' N(S02F)2' pounds were recorded on DM4 Grubb-Parsons N(S02CFa)S02Cl, N(S02CFa)S02F, or MeS03J to (courtesy lIT, Delhi). give the corresponding compounds. The preparation and characterization by various The reflectance spectra of the compounds were chemical and physical methods of the adducts of recorded on SP 700A, UV and visible spectrophoto- thiotrithiazyl chloride with chlorides of Co(II) , meter (courtesy lIT, Delhi). Nujol and solution Ni(II), Cu(II) , P(III) and (V), As(III), Sb(III), spectra of the compounds were recorded on a Beck- Bi(III) and iodine (I) and (III) are reported in mann DB spectrophotometer. Magnetic susceptibilities were determined at room this paper. temperature using Gouy's balance. Conductivity Materials and Methods measurements were carried out using Toshniwal Thiotrithiazyl chloride was prepared as described CLOljOl conductivity bridge. All the manipula- earlier-I. Anhydrous Ni(II) and Co(II) chlorides tions were carried out in a dry box as far as possible. were prepared by treating their anhydrous acetates Results and Discussion with acetyl chloride. Cu(II) and Bi(III) chlorides were made anhydrous by refluxing their chlorides . The presence of the cation, S4N~,in these adducts as with thiony I chloride. Phosphorus (III), As(III) in the pure chloride, was indicated by the spot test-", and Sb(III) chlorides were purified by distillation. and the IR spectra-? (Table 2). The bands in the

48 PAUL et a.. AD DUCTS OF THIOTRITHIAZYL CHLOIUDE

TABLE 1 - NATURE AND ANALYTICAL DATA OF THE COMPOUNDS OF THIOTRITHIAZYL CHLORIDE WITH METAL AND NON-METAL CHLORIDES

Metal/non -metal Adduct Colour m.p. Found (%)* Calc. (%) chloride (0C) ------S CI N S CI N

CuCl2 S4NaCuCla Mustard 178-80 37·72 31·28 12·0 37-64 31·32 12·35 (d) NiCl2 S4NaNiCIa Yellowish 150 38·07 31·83 12·2 38·15 31·74 12·52 CoCl2 S.NaCoCI3 Green 204 37·78 31·65 38·16 31·75 12·53 ssci, S4N3SbCl4 Light yellow 175-78 29·75 31-50 9·00 29·49 32·71 9·69 (d) (S.Na)2SbCls Bright yellow 200-202 39-65 27-80 12·70 40·03 27·75 13·13 (d) BiCla S.N3BiCl• Lig ht yellow 173-78 24·65 27·30 8·12 24·56 27·25 8·06 (d) rCI S.N3ICI2 Yellow 162-64 34·72 19·15 11·35 34·80 19·28 11·42 (d) ICla S.N3ICl. do 130 (d) 29·20 32·24 9·46 29·18 32·32 9·58 *Satisfactory metal analyses were also obtained.

aT1(P)+-_aT1(F) transitions. This indicates a tetra- TABLE 2 - INFRARED SPECTRA (CM-I) OF THE ADDUCTS OF hedral environment around Ni(II) in its adduct. THIOTRITHIAZYL CHLORIDE WITH METAL AND NON-METAL The electronic spectrum of solid thiotrithiazyl CHLORIDES chloride in the range 320-800 nm exhibits an absorption band at 376 nm, which is attributed to S4N! Adduct Cation Anion cation's. The electronic spectrum of solid S4NaCoC13 shows two distinct bands at 375 and 705 nm. The "S.N3CuCI3 1176,1028,1000,720,672,463, 250 313 former is attributed to S4N; cation, while the latter "S.N3NiCI3 1160, 1000, 72~ 68~ 450, 323 290 may be assigned to tetrahedral Co(II) .c The spectrum S.N3CoCl3 1160, 1020, 998, 720, 680, 466, 305 of the compound in nitromethane solution has 448 bands at 386 and 679 nm. The band at 386 nrnis 'S.N3SbCl. 1180, 1030, 720, 680, 565, 525, 310, 280, 245 475 due to S4Nt, while the band at 679 nm (E = 306) c(S.Na)2SbCIs 1183,1030,725,678,563,476 435, 298, 283 is evidently due to 4T1(P)+-_4A2 transition, indi- 'S.N3BiCl. 1182,1024,720,670,323 279,286 cating a tetrahedral geometry around Co(II). cS.N3ICI2 1175,1018,722,674,464,320 272 The electronic spectra of S4N31C12 and S4Na1C14 S.N.ICI. 1177,1135,1028,721,671,470, 245 323 also show characteristic absorption bands due to S4N! cation. Magnetic measurements- The complexes S4N3MCla, where M = Cu, Ni or Co, are paramagnetic and far IR region at 250, 290 and 305 crrr'! in S4NaCuCla, have magnetic moments of 1'78, 3·43 and 4·3 S4NaNiCla, and S4NaCoC13respectively are ascribed BM respectively at room temperature. The mag- to the M-Cl bonds-". In the complexes, S4NaSbC14 netic moment value of 3·43 BM for S4N3NiCla and (S4N3)2SbC15,the characteristic bands due to is quite close to the range 3·6-4·0 BM for the

SbC14 and SbC125 anions are comparable with the tetrahedral Ni(II) complexes with aTl ground term. values reported for those anionsw->. The far in- The square planar complexes of Ni(II) are dia- frared absorption bands in the case of BiCl; anion magnetic, while octahedral complexes have a are at 279 and 286 crrr ", which are quite comparable magnetic moment of the order of 2·83 BM with the values reported for BiCl;i in (Et4N)4BiCl4 S4N3CoClahas a magnetic moment of 4·3 BM at room (ref. 19a). S4N3ICI2 and S4N3ICI4 show bands at temperature which is within the range (4·2-4·8 BM) 272 and 245 cm-l respectively indicating the presence for d7 Co(II) in a tetrahedral or pseudotetrahedral of anions ICI4: and 1C14 (ref. 20, 21). (Csv) symmetry with 4A2 as the ground state term-", Regular tetrahedral Ni(II) complexes are blue. The magnetic moments of Cu(II) complexes are The occasional appearance of a green or red colour generally in the range 1·75-2·2 BM, regardless of in a tetrahedral Ni(II) complex is attributed to stereochemistry. The magnetic moment of 1·78 charge transfer absorption tailing from UV into observed for S4N3CuCla though does not establish visible region22. The rather odd colour of the unambiguously the stereochemistry of the complex, nickel chloride and the other adducts may be due yet it does not contradict the proposed tetrahedral to the yellow colour of the cation, S4N~. Both structure. Cs2CuC14• which has a tetrahedral distri- tetrahedral and octahedral Ni(II) complexes exhibit bution of ligands about Cu(II) , has a magnetic three bands in their electronic spectra, two of which moment of 2·0 BM. in the tetrahedral Ni(II) complexes occur at 600- Electrical conductivity - Iodine monochloride '750 nm and 1250-1450 nm. The electronic spectra undergoes autoionizationw as of S4NaNiCla exhibits two bands at 1370 and :800 nm corresponding to aA2(F)+-_aTl(F) and

49 INDIAN J. CHEM., VOL. 14A, JANUARY 1976

Thiotrithiazyl chloride dissolves in ICI to a small 4. FRIEDMAN, P., Inorg. Chem., 8 (1969), 692. extent and the solution shows an increase in con- 5. ADAMS,D. B., BANISTER,A. J., CLARK,D. T. & KILCAST, D., Int. J. sulfur Chem, A, 1 (1971), 143. ductance indicating the formation of ion pairs. 6. CORDES, A. \~T., KRUH, R. F. & GORDON, E. K., Inorg. Since S4N3Cl is a chloride ion donor, evidently it Chem; 4 (1965), 681. increases the concentration of the anion in this 7. LOGAN, N. & JOLLY, W. L., Inorg. Chem., 4 (1965), solvent system. This indicates the formation of 1508. 8. JOLLY, W. L., Advances Chern. Ser., Sulphur research the S4NaIC12' trends, (No. 110) (1972), lOt. All these compounds are insoluble in common 9. BANISTER, A. J., Nature, Lond (Phys. Sci.), 237 (1972), organic solvents. The insolubility of these com- 92. to. BECKE-GOEHRING, M. & LATSCHA, H. P., Z. Nature, 17& plexes in any suitable solvent makes the determi- (1962), 125. nation of molecular weights rather difficult. The It. BANISTER, A. J. & DAINTY, P. J., J. chem. Soc. (Dalton), existence of CoO; or NiCl; with larger cations or (1972), 2658. cationic ligands has been reported24,2s. In the 12. PAUL, R. C., ARORA, C. L. & MALHOTRA,K. C., Chemy case of Co(II) and Cu(II) the existence of dimeric tea., (1968), 1810. 13. PAUL, R. C., SHARMA,R. D. & MALHOTRA,K. C., Indian species, M2Clij- have also been establishedw=". J. cu-«, 12 (1974), 320. Thus, on the basis of the available evidence, struc- 14. ROESKY, H. W. & DIETL, M., Z. Naturf., 26 (1971), ture II may be proposed for S4N3MCl3' where 977. 15. PAUL, R. C., SHARMA,R. P. & VERMA, R. D., Indian j, M = Cu, Co or Ni and has a tetrahedral or pseudo- Chem., 12 (1974), 761. tetrahedral environment. 16. PAUL, R. C., SHARMA,R. P. & VERMA, R. D., Indian j. Chem, (in press). Cl"'M/Cl)M/Clj20 2 17. BANISTER, A. J. & PADLEY, J. S., J. chem, Soc., A, (1967), 1437. [ 18. NAKAMOTO,K., Infrared spectra of inorganic coordination Cl/ 'Cl "'Cl . compounds (Wiley In terscience, New York), 110. 19. (a) AHLIJAH, G. Y. & GOLDSTEIN,M., J. Chem, Soc., (A) (II) (1970), 327; (b) SZYMANSKI, H. A., YOLIN, R. & MARABOLE,L., J. chem, Phys., 47 (1967), 1877. The X-ray diffraction of (S4N3)2SbCls shows the 20. MAKI, A. G. & FORNERIS, R., Spectrochim, Acta, 23A existence of SbCI~- single anion'". It is, therefore, (1967), 2309. probable that in other complexes, the anions exist 21. STAMMREICH,H. & FORNERIS, R., Spectrochim. Acta, 16- (1960), 363. as single entity, which may be due to the stabilizing 22. COTTON, F. A. & WILKINSON, G., Advanced inorganic effect of larger S4Nt cation. chemistry (Interscience, New York), 883. 23. CORNOG,J. & KARGES, R. A.,j. Am. chem, Soc., 54 (1932} Acknowledgement 1882. 24. KOLODINI, R. A., MORRIS, J. N. & TAYLOR, R. C., J. One of us (R.P.S.) is thankful to the UGC, New chem, Soc. (Dalton), (1973), 328. Delhi, for financial assistance. 25. BRYNESTAD,J. & PEDRO SMITH, G., J. Am. chem, Soc., 92 (1970), 3198. References 26. WILLETTE, R. D., Chem. Commun., (1973), 607. 27. HARRISON, W. L., PODDOCK, N. L., TROTTER, J. & 1. GLEMSER, 0., Chem . Ber., 94 (1961), 1443. WINGFIELD, Chern, Commun., (1972), 23. 2. JOHNSON, D. A., BLYHOLDER, G. D. & CORDES, A. W., 28. CHOW, C., WILLETTE, R. D. & GERSTEIN,J. chem, Phys., Inorg. Chem., 4 (1965), 1790. 61 (1975), 27t. 3. SISLER, H. H. & PARKASH, H., Inorg. Chem., 7 (1968), 29. KRUSS, K. & ZIEGLER, lVI., Z. anorg . allgem. Chem., 388 2200. (1972), 158.