Crystal and Molecular Structures of Dichloromethane-solvated Tris(morpholinocarbodithioato)-complexes of Chromium(III), Manganese(III), and Rhodium(III). Comparison of Co-ordination Spheres


The title complexes [(I)-(III)] are nearly isomorphous with the known cobalt(III) analogue (IV). The principal differences between (I)-(III) arise from the nature of the central metal atoms, packing and other effects being essentially the same. They may be considered as trigonally distorted octahedral, with an approximate three-fold rotation axis. The manganese complex (II) deviated most significantly from this model, with elongated bonds in the z and slightly elongated bonds along the x direction, which can only be attributed to Jahn-Teller effects. The MS6 co-ordination sphere is highly symmetrical in the chromium complex(I), as expected for the 4A ground-state, even more so than in (IV). The mean increase in metal-ligand bond distance from CoIII to RhIII, with identical d6 (1A1) configurations, is very close to 0.1 Å. The “bite” angle of the bidentate ligand appears to be determined largely by M-L distance. Crystal data: (I), space group P1, Z = 2, a = 13.255(9), b = 10.642(5), c = 11.395(1)Å, α = 115.16(4), β = 104.4(1), γ = 100.19(6)°, R = 4.3%, 2 218 reflections; (II), space group P1, a = 13.067(3), b = 10.824(6), c = 11.475(5)Å, α = 116.23(5), β = 104.06(3), γ = 100.19(4)°. R 4.0%, 2 062 reflections; (III), space group. P1 Z = 2, a = 13.343(4), b = 10.596(1), c = 11.191 (1)Å, α = 114.20(1), β = 103.18(2), γ = 101.29(2)°. R 4.3% 3 529 reflections.



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