CRYSTAL-STRUCTURES OF TRANS-[COCL2((CH3)2PCH2CH2P(CH3)2)2]CLO4, TRANS(CL,CL)CIS(P,P)-[COCL2(NH2CH2CH2P(CH3)2)2]PF6.0.5CH3OH, AND TRANS-[COCL2(NH2CH2CH2NH2)2]NO3

The crystal structures of trans-[CoCl2(dmpe)2]ClO4 (dmpe= 1,2-bis(dimethylphosphino)ethane) (1), trans(Cl, Cl)cis(P, P)-[CoCl2(edmp)2]PF6.0.5CH3OH (edmp=(2-aminoethyl)dimethylphosphine) (2) and trans[CoCl2(en)2]NO3 (en=1,2-ethanediamine) (3) were determined by the single-crystal X-ray diffraction method. Crystal data and final R values are: for 1, orthorhombic, Ccca, a = 15.192(3), b = 16.221(4), c = 18.129(3) angstrom, V = 4468(1) angstrom-3, D(x) = 1.58, D(m) = 1.60 g cm-3, and Z = 8 and R = 0.041 for 2360 reflections; for 2, orthorhombic, C222(1), a = 15.295(4), b = 18.583(5), c = 14.680(4) angstrom, V = 4172(2) angstrom-3, D(x) = 1.59, D(m) = 1.63 g cm-3, and Z = 8, and R = 0.099 for 4626 reflections; for 3, monoclinic, P2(1)/n, a = 6.348(1), b = 9.304(1), c = 9.853(1) angstrom, beta = 101.79(1)-degree, V = 569.6(1) angstrom-3, D(x) = 1.82, D(m) = 1.85 g cm-3, and Z = 2, and R = 0.043 for 1024 reflections. The Co-P bond distances (av 2.196(3) angstrom) in 2 is shorter by 0.063 angstrom than that (av 2.259(1) angstrom) in 1, while the Co-N bond distance (av 2.039(7) angstrom) in 2 is longer by 0.079 angstrom than that (av 1.960(3) angstrom) in 3, indicating the trans influence of the phosphino group. The metal-ligand bond distances were compared with those of the corresponding trans-dichloro complexes of Fe(II), Fe(III), Cr(III), and Rh(III).