Banerjee, B K

Ghosh, S K

Sanyal, R M

English

IACS Institutional Repository

CRYSTALLOGRAPHIC DATA FOR NICKEL AND COBALT BIURET COMPLEXESS. K. GHOSH, R. M. SANYAL and B. K. BANERJEEPlanning and Development Division Fertilizer Corporation of I ndia Ltd., Sindhi, Bihar(Received Fehrwiry 19, 1965)ABSTRACT. The orystallographic properties of nickel biuret and cobalt biuret com- ploxoB have been studied }>y means of X-ray diffraction data. The powder diffraction data showed that both the complexes belong to the monoclinic system. The cell dimensions for nickel biuret is a 10.08 A, b -9.82 A, cr 4.31 A and p =  101°18', whiltj that of cobalt biuret is a=0.O6 A, b —ll.OoA, c.= 11.23 A, and /I '110°55'. The systematic extinctions observed are consistent with the spatjo group P2j/a with two molecules per unit cell for nickel biui*et and P2i/c with two molecules per unit coll for cobalt biuret.I N T R O D U C T I O NBiuret is an organic compound derived from the products of the thermal decomposition of urea or urea nitrate. Because of its poisonous effect on some plants its presence in urea used as fertilizer is undesirable.Schiff (1896) first reported the formation of chelate complexes of biuret with Cii and Ni salts. These complex formations subsequently serves a very useful method for the estimation of biuret in a very low concentration in urea. I t  has also boon found that biuret can bo estimated most satisfactorily by complex formation with Co-salts (Sanyal and Pal, 1964). The behaviour of chelat­ing molecules and chelate complexes could ultimately be understood if the structure of the moJecules are known in detail. Such question as the specificity (or the lack thereof) of a chelating molecule^ for inorganic ions, solubility, stability of the salts formed and many other physical properties could be easily answered only when the c^xact structures are known.In order to explain such factors a preliminary investigation on the crystal­lographic properties of these complex salts have been undertaken.E X P E R I M E N T A LThe nickel and cobalt biuret complex samples were prepared in accordance with the method followed by the previous workers in this laboratory (Sanyal and Pah 1964). The samples were recrystallized from aqueous solution.X-ray diffraction patterns of the above samples were obtained in Phillips X-ray diffractometer PW1060/51 with Geiger counter as detector. Filtered CuK^ radiation and cobalt radiation with iron filter was used. The interplanarno18distances of the lattices were calculated from the measurement on X-ray diffrac­tion patterns with maximum accuracy.The phase identification was done by the usual method of Hanawalt et al (1938)..cInterpretation of X-ray data :The X-ray data are given in Tables IIlan d  IV. The powder pattern was indexed by Ito ’s method (Ito, 1950; Azarof|and Buerger, 1958). The interplanar spacing and corresponding Q values {Q,,^ ■== ’ild% i)  are listed in Tables I I  and IV.Crystallographic Data for Nickel and Cobalt, etc. 171Nickel biuret :The first three lines in the Tables II  w ^e first selected as Qtoo> Qoio Then tho higher orders of these lines i.e. etc. wore computed. Aninspection of the observed Q’s failed to show the computed values for those higher orders of Q i.e., Qioo> Qsoo ®tc. So it was decided to seleid other possible values for the pinacoidal Q’f-. Accordingly, the first three lines wore selected as Qsoo and Qooi' 1-t can be seen that the observed ^ ’s are in quite agreement with the calculated Q values for other higher orders of reflection.TABLE ISelection of 0^20 and QqqiQhkl Computed Observed Error inQ200 .0359Q400 .1438 .1449 . +  .0011/4= + .0002Qeoo .3235 .3235Q020 .0412Q040 .1649 .1666 1 .0017/4 = + .0004Qogo .3711Qool .0541Q002 .2163 .2200 +  .0037/4 = + .0009Qo03 .4867Prom the table it can be seen, that Q200 == .0359-f .0002 =  .0361 == 2a**== .0412-f .0004 =  .0416 =  25**Qpoi =  .0541+.0009 =  .0550 =  c** 'The dimensions of the reciprocal cell then becomes, a* =  .0948 5* =  .1019 0* =  .2345a*. =  90“/?* =  78“41' y* =  90“Finally the other values were detorinined using the equajtion,=  A*a**+P5**+l*c**=2Alfco*6* cos y+2klb*c* cos a*+21Ac*o*oosy?* (1)172 ?. K. Qhoah, R. M. Sanyal andTABLE I Igreeinent of observed and eomputodB. K . Barierjee’s for nickel biuret co]PowderdiagramlinedK Q observed Q computed hJcL1. 5.275 .0359 .0361 2002. 4.925 .0412 .0416 0203. 4..300 .0541 .0550 0014. 3.910 .0654 .0654 Oil5. 3.690 .0734 .0734 2 o r6. 3.427 .0851 .0812 1117, 3.340 .0896 .0916 3108. 3.230 .0959 .0966 0219. 3.160 .1001 .1034 42110. 3.122 .1026 .1026 13011. 3.040 .1082 .1082 20112. 3,000 .1111 .1124 12113. 2.866 .1217 .1228 32014. 2.820 .1257 .1297 23015. 2.772 .1301 .1304 40216. 2.730 .1342 .1310 13217. 2.627 .1449 .1438 40018. 2.522 .1572 .1548 41019. 2.450 .1666 . .1649 04020. 2.400 .1736 .1748 33021. 2,327 .1847 .1830 I2T22. 2.242 • 1989 .1980 32123. 2.217 .2035 .2025 24024. 2.132 .2200 .2163 00225. 2.069 .2336 .2304 01226. 2.045 .2391 .2372 14127. 1.930 .2685 .2678 42128. 1.824 .3006 • 2936 21229. 1.758 .3235 •3235 60030. 1.681 .8539 • 3522 31231. 1.605 .3882 .3864 042CrystalhgrapUc Data for Nickel and Cobalt, eitc. 173The direct cell dimensions are as follows:a =  10 .68A a  =» 00°b =  9.821 /) 101°18'c =  4 .3 l l  90°Tho crystal therefore belongs to the nioioclinic system. The indexed powder pattern showed the following ftystemati<^ extinctions.I1 . OiO absent when k is odd. |2. AOO absent when h is odd.3. hffl absent when h is odd. tThe space group indicated by these data isThe observed density o f2.653 gm cm“  ^indicates 2 molecules per unit coll; calculated density =  2.64 gm cm~^. The molecules must be centro-synimetrical with nickel atom at symmetry centres.Cohalt biuret:In  this case first three lines in Table IV was selected as Q^ qq, 6002*I t  can be seen that the observed Q’s are in quite agreement with the calculated Q values for other higher orders of reflection.TABLE IIISelection of Q020 OooiQlikl Computed Observed Error in QueiQ l O O .0312Q200 .1248 .1245 -.0003/4=--.0000Q300 .2809 .2805 -.0004/9 = - .0 0 0 0Q020 .0329Qo40 .1317 .1322 + .0005/4=+.0001Qoeo .2064 .2980 +  .0016/9 = + .0001Q002 .0365Qo04 .1459 .1457 - .0 0 0 2 /4 = -.0 0 0 0Qo06 .3284 .3280 -.0 0 0 4 /9 = -.0 0 0 0> table it can be seen that,.0312+.0000 =  .0312Qozq = .0329+.0001 =  .0330©002 .0364+.0000 =  .03651 7 4  S. K. Qhosh, B. M. Sanyal and B. K. BanerjeeTABLE IVFinal agreement of observed and computed ’s for cobalt biuret complexPowderdiagramlinesdk Q observed Q calculated hkh1. 5.660 .0312 .0312 1002. 6.610 .0329 .0330 0203. 6.235 .0364 .0364 0024. 6.036 .0394 .0394 1105. 4.990 .0401 .0400 2026. 4.890 .0419 .0419 0217. 4.820 .0430 .0430 10^8. 4.780 .0437 .0444 132"9. 4.490 .0496 .0447 01210. 4.420 .0511 .0481 2 iT11. 4.160 .0577 .0606 11112. 3.995 .0627 .0642 12013. 3.645 .0753 .0728 22214. 8.310 .0913 .0913 10216. 3.260 .0941 .0903 01316. 3.120 .1027 .1000 11217. 3.060 .1068 .1050 13018. 3.020 .1096 .1103 03219. 2.834 .1245 .1248 20020. 2.785 .1289 .1262 13121. 2.750 .1322 .1320 04022. 2.680 .1392 .1403 04123. 2.620 .1467 .1459 00424. 2.246 .1984 .1986 23026. 2.214 .2040 .2096 20226. 2.114 .2238 .2252 10427. 1.888 .2806 .2808 30028. 1.810 .3062 .3013 03529. 1.796 .3100 .3122 22330. 1.772 .3185 .3138 32031. 1.745 .3284 .3284 006The dimensions of the reciprocal cell thus becomes,GrystalhgrapMc Data for Nickel and Cobalt, etc. 176a* =  .1766 a*=a 90®b* =  .0905 /?*=469°4'c* =  ,0964Finally the other values were detormmed usingThe direct cell dimensions are as follow^;a — 6.06A a =  190®h =  ll.OSA /? =  il0®55'c =  11.23A r=^90®In case of cobalt biuret complex the cr^ial belongs to the monoclinic systcMU, Tlie indexed powder pattern showed the following extinctions.1. oko absent when k is odd.2. ool absent when I is odd.3. hoi absent w'hen I is odd.The space group indicated by these data isThe observed density of 2.542 gmcm~® indicates two molecules per unit ceil; calculated density =  2.436 gm cm~®.A C K N O W L E D G M E N TThanks are due to Dr. K. R. Chakravorty, General Manager, Planning and Development Division, for his constant encouragement and kind permission to publish this paper,R E F E R E N C E S  Schiff, H., 1896, Ber 29. 296.Bull of Indian Standard Institution IS 1781-1961 BS. 12.Nowak, K, Jadwiga, W. and Nikiel S„ 1964, Chem. Abut. 60, 2292.Sanyal, R. M. and Pal P. K., 1964, Technology 1, 64.Hanawalt, J. D. et d , 1938, Ind. Eng. Chem., Anal. Ed. 10, 457-512.Azarofif, L. V. and Buergor M. J. 1958, The powder method in X-ray crystallography. Mo Qraw-Hill Book Co. Inc. 106-123.Ito, 1,1950, X-ray studies of Polymorphism, Maruzon Co. Ltd., Tokyo, 187-228.

Crystallographic Data for Nickel and Cobalt Biuret Complexes

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Crystallographic Data for Nickel and Cobalt Biuret Complexes

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