Crystal structures of 5,12-dimethyl-1,4,8,11-tetra-aza-cyclo-tetra-decane cobalt(III) mono-phenyl-acetyl-ide and bis-phenyl-acetyl-ide.

Reported in this contribution are the synthesis and crystal structures of new mono- and bis-phenyl-acetyl-ides based on Co(III)(DMC) (DMC is 5,12-dimethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne). Chlorido-(5,12-dimethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)(phenyl-ethyn-yl)cobalt(III) chloride-aceto-nitrile-methanol (1/1/1), [Co(C(8)H(5))Cl(C(12)H(28)N(4))]Cl·CH(3)CN·CH(3)OH, 1, and (5,12-dimethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)bis-(phenyl-ethyn-yl)cobalt(III) tri-fluoro-methane-sulfonate-di-chloro-methane (2/1), [Co(C(8)H(5))(2)(C(12)H(28)N(4))](2)(CF(3)SO(3))(2)·CH(2)Cl(2), 2, were prepared under weak-base conditions in satisfactory yields. Single-crystal X-ray diffraction studies revealed that both 1 and 2 adopt a pseudo-octa-hedral symmetry in which the Cl-Co-C angles of 1 and C-Co-C of 2 range from 177.7†(2) to 178.0†(2)° and from 177.67†(9) to 179.67†(9)°, respectively. In both structures, the Co(III) metal center is coordinated in the equatorial plane by four N atoms, in which the N-Co-N angles range from 85.6†(3) to 94.4†(3)°. The structure of 1 features two crystallographically independent mol-ecules in its triclinic cell (Z' = 2), which are related to each other by pseudo-monoclinic symmetry. The crystal investigated was twinned by a symmetry operator of the approximate double-volume C-centered cell (180° rotation around [201] of the actual triclinic cell), with a refined twin ratio of 0.798†(3) to 0.202†(3). Both methanol solvent mol-ecules in 1 are disordered, the major occupancy rates refined to 0.643†(16) and 0.357†(16). Compound 2 also contains two mol-ecules in the asymmetric unit, together with two tri-fluoro-methane-sulfonate anions [of which one is disordered; occupancy values of 0.503†(16) and 0.497†(16)] and a disordered di-chloro-methane [occupancy values of 0.545†(12) and 0.455†(12)].