The Phenomenon of Conglomerate Crystallization. XVIII. Clavic Dissymmetry in Coordination Compounds. XVI. The Crystal Structure of Racemic {[Co(NH3)(4)(CO3)]NO3}(2)center dot H2O

The x-ray crystal structure of {[Co(NH3)(4)(CO3)]NI3}(2)center dot H2O has been determined as part of a study of the intra-and interionic interactions present in crystals of several transition-metal-amine complexes chosen to examine the occurrence and causes of conglomerate crystallization. {[Co(NH3)(4)(CO3)]NO3}(2)center dot H2O crystallizes in the monoclinic space group P2(1)/n with cell constants a = 7.4960(9)angstrom, b = 22.673(6), c = 10.513(1), and beta = 91.41(1)degrees; V = 1786.12 angstrom(3), and d(calc; Z = 4) = 1.915 g cm(-3). In all, 5333 data were collected over the range of 4 degrees <= 2 theta <= 60 degrees of these, 3395 [independent and with I >= 3 sigma(I)] were used in the structural analysis. Data were corrected for absorption (mu = 19.361 cm(-1)) and the relative transmission coefficients ranged from 0.9987 to 0.8013. The data were of a quality such that both ammonia and water hydrogens were found in difference Fourier maps. The final R(F) and R-w(F) residuals were, respectively, 0.0333 and 0.0332. A trans effect is observed for both cations of {[Co(NH3)(4)(CO3)]NO3}(2)center dot H2O. The equatorial nitrogens, trans to the carbonato oxygens, have shorter Co-N distances than the axial nitrogens, trans to one another. The carbonato ligands are not symmetrically bonded to their respective metal centers. The Co-O distances for cation 1 are 1.913(1) and 1.903(1) angstrom and those for cation 2 are 1.916(1) and 1.896(1) angstrom. The structure reveals the existence of an intricate array of hydrogen bonds, involving both the chelating and nonchelating oxygens of the carbonato ligands as hydrogen bond acceptors of the amine hydrogens. The amine hydrogens are also involved in significant hydrogen-bonding interactions with the nitrate oxygens and water of crystallization, although they are generally weaker than those of the carbonata oxygens.