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The crystal structures of 10-chloroaquacobalamin perchlorate hydrate (10-Cl-H(2)OCbl.ClO(4)) (Mo Kalpha, 0.710 73 Å, monoclinic system, P2(1), a = 11.922(4) Å, b = 26.592(10) Å, c = 13.511(5) Å, beta = 93.05(3) degrees, 10 535 independent reflections, R(1) = 0.0426), 10-chlorocyanocobalamin-acetone hydrate (10-Cl-CNCbl) (Mo Kalpha, 0.710 73 Å, orthorhombic system, P2(1)2(1)2(1), a = 16.24(3) Å, b = 21.85(5) Å, c = 26.75(8) Å, 7699 independent reflections, R(1) = 0.0698), and 10-chloromethylcobalamin-acetone hydrate (10-Cl-MeCbl) (Mo Kalpha, 0.71073 Å, orthorhombic system, P2(1)2(1)2(1), a = 16.041(14) Å, b = 22.13(2) Å, c = 26.75(4) Å, 6792 independent reflections, R(1) = 0.0554), in which the C10 meso H is substituted by Cl, are reported. An unusual feature of the structures is disorder in the C ring, consistent with a two-site occupancy in which the major conformation has the C46 methyl group in the usual position, "upwardly" axial, and the C47 methyl group equatorial, while in the minor conformation both are pseudoequatorial, above and below the corrin ring. (13)C NMR chemical shifts of C46, C47, C12, and C13 suggest that the C ring disorder may persist in solution as a ring flip. Since molecular dynamics simulations fail to reveal any population of the minor conformation, the effect is likely to be electronic rather than steric. The axial bond lengths in 10-Cl-MeCbl are very similar to those in MeCbl (d(Co)(-)(C) = 1.979(7) vs 1.99(2); to 5,6-dimethylbenzimidazole, d(Co)(-)(NB3) = 2.200(7) vs 2.19(2)), but the bonds to the four equatorial N donors, d(Co)(-)(N(eq)), are on average 0.05 Å shorter. In 10-Cl-CNCbl, d(Co)(-)(C) and d(Co)(-)(NB3) are longer (by 0.10(2) and 0.03(1) Å, respectively) than the bond lengths observed in CNCbl itself, while conversely, the C-N bond length is shorter by 0.06(2) Å, but there is little difference in d(Co)(-)(N(eq)). The Co-O bond length to coordinated water in 10-Cl-H(2)OCbl(+) is very similar to that found in H(2)OCbl(+) itself, but the d(Co)(-)(NB3) bond is longer (1.967 vs1.925(2) Å), while the average d(Co)(-)(N(eq)) is very similar. The coordinated water molecule in 10-Cl-H(2)OCbl(+) is hydrogen bonded to the c side chain carbonyl oxygen, as in H(2)OCbl(+). NMR observations indicate that the H bond between coordinated H(2)O and the c side chain amide persists in solution. The equilibrium constant, K(Co), for coordination of bzm to Co(III) is smaller in 10-Cl-MeCbl and 10-Cl-CNCbl than in their C10-unsubstituted analogs (181 vs 452; 4.57 x 10(3) vs 3.35 x 10(5)), but could not be determined for 10-Cl-H(2)OCbl because hydrolysis of the phosphodiester is competitive with the establishment of the base-off equilibrium. Substitution of H by Cl at C10 causes the bands in the electronic spectrum of 10-Cl-XCbl complexes to move to lower energy, which is consistent with an increase in electron density in the corrin pi-conjugated system. This increased electron density is not due to greater electron donation from the axial ligand as bonds between these and the metal are either lon...