Crystal Structures of Cobalt(III) Complexes Containing 1,1,1-Tris(dimethylphosphinomethyl)ethane (mmtp), [CoCl3(mmtp)] and [Co(CN)3(mmtp)]·2H2O

Abstract
The crystal structures of [CoCl3(mmtp)] (mmtp = 1,1,1-tris(dimethylphosphinomethyl)ethane) (complex 1) and [Co(CN)3(mmtp)]·2H2O (complex 2) were determined by the single-crystal X-ray diffraction method. Crystal data and final R values are; for complex 1, orthorhombic, P21nb (c, a, b setting of Pna21), a = 13.545(1), b = 13.875(1), c = 9.315(1) Å, V = 1750.7(3) Å3, Dx = 1.58, Dm = 1.57(3) g cm−3, and Z = 4, and R = 0.046 for 1999 reflections. For complex 2, orthorhombic, P21nb, a = 14.345(2), b = 15.330(2), c = 9.229(1) Å, V = 2029.4(4) Å3, Dx = 1.39, Dm = 1.35(2) g cm−3, and Z = 4, and R = 0.039 for 2715 reflections. The Co–P bond distances of av 2.203(2) Å for complex 1 and of av 2.228(1) Å for complex 2 are fairly shorter than those (av 2.331(9) Å) in [Co(mmtp)2][Co(CN)6]·2.25H2O, in which the Co–P bonds are mutually in the trans positions, indicating the strong trans influence of the phosphino group.

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