Krishnaswamy, M

Ratho, T

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ON THE STRUCTURE OF COMPLEX SILVER LUTIDINE PER CHLORATET. RATHO AND Mrs. M. KRISHNASWAMYEBOIONAI ENaiNEBRlSO ColiLEGJS,R o u b k e l a{lieceived September J4, 1966.)ABSTRACT. The Dobyo Soherrer pattern p f complex Silver Lutidlne per Chlorate has been obtained and analysed. Tlie data obtained indicates that the crystal belongs to the monoolinio system with the unit coll dimensions 10.96 A.U., 6—12.04 A.U., and 0= 6.933 A.tJ. and p=101* 26'. There are two molecules per unit cell and the space group P^, P^lm or Pm  can be eussigned to the crystal.I N T R O D U C T I O NThe study of complex salts containing ligands is of importance for the study of stretching force constants between the various groups of atoms in the mole­cules. Diamagnetic properties of such complexes are also of interest. Silver Lutidine per Chlorate [Ag(C7H9N)2 Cl O4], is available in microcrystaUine form, white in colour. As it is not possible to obtain single crystals suitable for complete structural analysis, the powder method has been used to establish certain crystallographic data.E X P E R I M E N T A LFiltered CuK* radiation was obtained from a Machlett A-2 X-ray Diffraction tube running a t 35KV and 15 m.A. and the specimen was contained in a very fine capillary of Lindmann glass of 0.01 mm. wall thickness and 0.6 mm. diameter. The Debye Scherrer pattern was obtained in a photographic film using a Rigaku Camera of 9 cm. diameter. The time of exposure was 4 hours. Interplanar dis­tances were calculated with great accuracy from measurements on the photographic film. Attempts were made to index the power lines with Cubic, Tetragonal and Hexagonal systems and the data did not fit with any one of these systems of higher symmetry. Lipson’s (Lipson, 1949) method was then tried which did not give a good number of constant differences indicating there by that the crystal belongs clearly to the two systems of lower symmetry namely the monoclinic or the tricli­nic. In such cases the De Wolffes’ (1957) method or the most general method due to Ito (1960) is applicable. Here we have tried the latter method.In  the Table are listed the experimental X-ray data. As all the six parameters were to be found out the Ito ’s method was used and the powder pattern was in­dexed , Azaroff and Buerger (1968). The d  values and the corresponding Q  values =» Qijcii are all given in the Table. Here is given by QiAi =® A*o**-l-fc®6**+l*6'''*-f 2ifc?6*c''‘ cos a*-4-2Afc*a* cos cos y*where a*, yff*, y* and o*, h* and c* are the reciprocal angles and axes respectively.38327328 T .  B a t h o  a n d  M r s .  M .  K r i s h n a s w a m yTABLENo.of IntoiiHity linos dAQ^~\ldhhlobservedQhklcomputed Indices1. 8 8.07J 0.0164 0.01667 n o2. 8 6.074 0.0271 0.0276 0203. 8 5.382 0.0345 0.03468 2004. W 3.966 0.0636 0.0634 1215. v\v 3.869 0.0608 0.0672 2016. w 3.747 0.07122 0.0708 1307. 8 3.580 0.07801 0.07803 3008. w 3.406 0.0863 0.08664 0029. w 3.241 0.0952 0.0048 22110. m 3.009 0.1105 0.1104 0400.1109 ' 32l11. w 2.756 0.13JG 0.1.3200.1321 30204112. vw 2.682 0.1390 0.1387 4000.1386 40l0.1389 31213. w 2.606 0.1470 0.1465 13214. w 2.539 0.1652 0.1559 24l16. m 2.458 0.1656 0.16620.1663 42l42016. w 2.406 0.1728 0.1725 06017. m 2.344 0.1820 0.1821 4010.1819 40218. vvw 2.240 0.1978 0.1973 30219. m 2.152 0.2160 0.21650.2167 14260020. m 2.114 0.2238 0.22370.2240 51030321, m 2.066 0.2342 0.2.346 22322. 8 2.007 0.2486 0.2484 0600.2490 4410.24900.2491 602440O n  ( h e  S t r u c t u r e  o f  C o m p l e x  S i l v e r  L u t i d i n C t  e tc .TABLE—(contd).mNo.oflines Intensity d A observedQhklcomputed Indices23. w 1.928 0.269H 0.26910.2689 2334020.2685 4032i. vvw 1.877 0.2838 0.2831 2600.28400.2843 33316125. m 1.823 0.3004: 0.2999 22326. ww 1.764 0.3211 0.3216 54Ti n i . w 1.7U 0.3404 0.3404 1140.3404 61228. ww 1.698 0.3467 0.34660.3468 00417029. w 1.646 0.3693 0.3698 35230. w 1.604 0.3887 0.3892 55031. vw 1.573 0.4042 0.40462 12432. vw 1.541 0.4214 0.4215 3710.4214 3340.4215 55233. vw 1.501 0.4437 0.4442 1720.4439 1440.44390.4433 64205334. w 1.444 0.4779 0.4774 18135. vw 1.410 0.5031 0.5026 66336. w 1.378 0.5262 0.52600.5261 18263237. vw 1.354 0.5448 0.64490.6461 31527338. w 1.323 0.5709 0.6714 4530.6716 40539. vvw 1.283 0.6073 0.60770.6069 36447240. ww 1.240 0.6504 0.6502 6700.6060 62?330 T. Batho and Mrs. M, KrishnaswamyAfter certain trials the second, third, and the eighth reflections were taken as Qoio> Qzm Qwi- possible to find out the reciprocal cell dimensionsasa* =  0.0731 A.U. b* =  0.0831 A.U. c* =  0.1472 A.U.Tn order to select the reciprocal cell angles a*, /ff*, y*(hko), (hoi) and (okl) reflections were carefully examined and it was foimd that (hko) and (okl) reflec- tions were present if a* and y* were taken to be 90°. The angle could then be calculated after studying some pairs of (hoi) and (hoi) reflections after the equationcos/?''* _  Qkol Qhol4Ma*c*~Thus /?* was found out to bo 78° 34'. The six parameters of the reciprocal cell having been thus found the direct cell dimensions are obtainee asa =  10.970 A.U. b =  12.04 A.U. c =  6.933 A.U.a  =  90°101° 26' y =  90°The Buerger test for the reduced cell dimensions has been applied and the dimensions are found to be the reduced ones.The above data establishes the crystal to be monoclinic. Finally all the powder lines were indexed using the general formula given above and the pattern so indexed showed the following conditions :hkl—no condition hoi—no condition hko—no condition oko—no condition ooi—even presentThe probable space groups therefore are P j or P j/^  or P«. The observed density is 1.644 gms/cc. and the number of molecules per unit cell comes to be 2. The calculated density is 1.563 gms/cc.On the Structure of Complex Silver iMidine, ek. 331A C K N O W L E D G M E N T SWe are thankful to the Union Education Ministry for awarding a scholarship to one of us (Mrs. M. Itrislinaswamy). We are also thankful to Dr. D. V. Raman Rao, Professor of Chemistry of this institute for supplying the chemically pure sample used in this work.R E F E R E N C E SAzaroff, L. V. and Buerger, M. J., 1968, Powier Method, 160.Ito, T,, 1960, X-ray sludies in Polymorphism, Jtfaruzen Tojtyo.Lipson, H., 1949, Acta, CrysL 2, 43.Wolffe, P. M. De., 1957, Acta. Oryst, 10, 690,

On the Structure of Complex Silver Lutidine Per Chlorate

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On the Structure of Complex Silver Lutidine Per Chlorate

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