The unexpected syntheses of [Co(picam)(3)](3+) salts and the crystal structure of [Co(picam)(3)]I-3 center dot H2O (I)

Compounds of composition [Co(picam)(3)]I-3 . 2H(2)O(II) were unexpectedly obtained while attempting to synthesize [cis-Co(picam)(2)(NO2)(2)](+) derivatives, using procedures expected to succeed in producing the cis-dinitro cation. The structure of the title compound was determined, at which point we realized the nature of the product obtained. (I) crystallizes in the monoclinic system, P2(1)/c (No. 14), Z = 4, a = 14.521(7), b = 15.003(4), c = 11.347(4) Angstrom, beta = 95.01(4)degrees, V = 2462.60 Angstrom(3) and d = 2.107 g-cm(-3). F(000) = 1480, R(F) = 0.037 and Rw(F) = 0.044 for 3095 reflections. Data were corrected for absorption obtained from Psi-scans (mu = 44.397 cm(-1)) and the transmission coefficients ranged from 0.2615 to 0.3878. The cations exist in the lattice as enantiomeric pairs with chiroptical descriptors Delta(delta delta lambda)[fac-Co(picam)(3)](+) and Lambda(lambda lambda delta)[fac-Co(picam)(3)](+). The analogous perchlorate was obtained also and identified only by its elemental analysis.