THE PHENOMENON OF CONGLOMERATE CRYSTALLIZATION .29. THE CRYSTALLIZATION BEHAVIOR OF BIDENTATE CARBONATO AMINES OF CO(III) - THE CRYSTAL-STRUCTURES OF THE RACEMATES [CO(TN)2CO3]IH2O, [CO(TN)2CO3]CLO4, AND OF [CO(TN)2CO3]PF6

[Co(tn)2CO3]I.H2O, (I) ICoO44N,C7H22, crystallizes as a racemate, spac e group P2(1)/c, with lattice constants a = 8 .791(2), b = 10.0057(7), c = 16.542(3) angstrom and beta = 95.40(2)-degrees; V = 1448.77 angst rom3 and d(calc; M = 412.11, Z = 4) = 1.889 g CM-3. A total of 2871 da ta were collected over the range of 4-degrees less-than-or-equal-to 2t heta less-than-or-equal-to 50; of these, 2098 (independent and with I greater-than-or-equal-to 3sigma(I)) were used in the structural analys is. Data were corrected for absorption (mu = 33.0 cm-1) and the relati ve transmission coefficients ranged from 0.647 to 0.999. The final R(F ) and R(w)(F) residuals were, respectively, 0.030 and 0.043. [CO(tn)2C O3]ClO4, (II), CoCl07N4C7H20, crystallizes as a racemate, space group P2(1)/n, with lattice constants a = 9.535(2), b = 13.189(3), c = 12.30 1(2) angstrom and beta = 114.19(2)-degrees; V = 1410.98 angstrom3 and d(calc; M = 354.63, Z = 4) = 1.669 g cm-3. A total of 2897 data were c ollected over the range of 4-degrees less-than-or-equal-to 2theta less -than-or-equal-to 50-degrees; of these, 2105 (independent and with I g reater-than-or-equal-to 3sigma(I)) were used in the structural analysi s. Data were corrected for absorption (mu = 14.4 cm-1) and the relativ e transmission coefficients ranged from 0.706 to 0.999. The final R(F) and R(w)(F) residuals were, respectively, 0.084 and 0.112. [Co(tn)2CO 3]PF6, (III) CoPF6O3N4C7H20, crystallizes as a racemate, space group P 2(1)/c, with lattice constants a = 9.902(2), b = 13.477(2), c = 12.051 (3) angstrom and beta = 112.90(2)-degrees; V = 1481.43 angstrom3 and d (calc; M = 412.16, Z = 4) = 1.740 g dm-3. A total of 2879 data were co llected over the range of 4-degrees less-than-or-equal-to 2theta less- than-or-equal-to 50-degrees; of these, 2146 (independent and with I gr eater-than-or-equal-to 3sigma(i)) were used in the structural analysis . Data were corrected for absorption (mu = 13.4 cm-1) and the relative transmission coefficients ranged from 0.898 to 0.999. The final R(F) and R(w)(F) residual were, respectively, 0.060 and 0.080. As is obviou s from the space groups, all three compounds of the series crystallize as racemates. In all three structures, the six-membered rings of the cation have the chair conformation, the carbonato ligand is planar and , in (II), the perchlorate anions do not have the very large amplitude s of libration normally expected from such species, apparently as a re sult of motional stabilization through hydrogen bonding to the cation. The hexafluorophosphate anion of (III) shows some disorder between tw o sites (ca 75:25), which is particularly obvious at one of the fluori nes(F5). This fluorine is near a terminal -NH2 fragment, and the disor der may be due to attempts to, separately, hydrogen bond to both of th e -NH2 hydrogens, thus occupying two lattices sites. Packing similarit ies and differences within the members of the carbonato series and tho se of related carbonato and oxalato compounds are discussed.