Hl. Chen et al., SYNTHESIS AND CRYSTAL-STRUCTURE OF ORGANOCOBALT(III) COMPLEXES WITH SECONDARY ALKYLS OR BULKY SCHIFF-BASE EQUATORIAL LIGANDS, Inorganic chemistry, 35(6), 1996, pp. 1502-1508
Alkylcobalt(III) Schiff base B-12 model complexes with secondary alkyl
s or a bulky diamine in the equatorial position were synthesized and c
haracterized. Structures have been first determined by X-ray diffracti
on analysis for i-C4H9Co(salen)(gamma-pic) (I), n-C3H7Co(salen)(gamma-
pic) (II) and C2H5Co(SB) (III), where salen = N,N'-ethylenebis-(salicy
lideneamine) dianion; SB = ,2-tetramethyl-N,N'-ethylenebis(salicyliden
eamine) dianion, gamma-pic = gamma-picoline. Crystal data for I(CoC26N
3O2H30): space group P2(1)/c with a = 6.661(5) Angstrom, b = 18.612(2)
Angstrom, c = 19.533(3) Angstrom, beta = 98.93(1)degrees, V = 2392.10
Angstrom(3), D-calcd = 1.320 g . cm(-3), Z = 4, and R = 0.048 for 446
9 measured reflections. Crystal data for II (CoC25N3O2H28): space grou
p P2(1)/c, a = 9.609(6) Angstrom, b = 19.169(8) Angstrom, c = 12.995(9
) Angstrom, beta = 106.9(7)degrees, V = 2290.4 Angstrom(3), D-calcd =
1.332 g . cm(-1), Z = 4, and R = 0.048 for 4358 measured reflections.
Crystal data for III (CoC22N2O2H27): space group P2(1)/c, a = 8.318(3)
Angstrom, b = 21.579(2) Angstrom, c = 11.572(2) Angstrom, beta = 93.3
5(1)degrees, V = 2073.7 Angstrom(3), D-calcd = 1.314 g . cm(-1), Z = 4
, and R = 0.060 for 3954 measured reflections. The crystal structure d
ata reveal that complexes I and II display six-coordinate octahedral g
eometry; their Co-C, Co-N bond lengths, as well as the Co-C-C angles,
are very close to those in 5'-deoxyadenosylcobalamin. Complex III is o
ne of the very few compounds having five-coordinate square pyramidal g
eometry and observed instability of the Co-C bond.