Abstract
X-ray analysis of the octahedral coordination compound (CH 2) 6N 4·Mo(CO) 5 has established that that axial and equatorial carbonyl groups have distinctly different dimensions, and the overall molecular geometry indicates significant steric repulsion between the organic ligand and the equatorial carbonyl groups. Moving away from the quaternary nitrogen atom, the three non-equivalent sets of CN bonds vary in the order long, short and normal, relative to the standard bond length in the unsubstituted (CH 2) 6N 4 cage system. A survey of the crystallograpic data for representative (CH 2) 6N 4 adducts utilizing only one nitrogen lone pair leads to the conclusion that cage distortion decreases in the order methylation > borine adduct formation ≅ N-oxide formation ≅ protonation > metal coordination. The crystals are orthorhombic, space group Pbca, with a = 12.800(2), b =13.377(2), c = 17.524(3) Å and Z = 8. The structure has been refined to R = 0.039 for 2491 observed MoKα data.
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