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The crystal structures presented herein consist of two positively charged CoIII(DMC) acetyl­ide complexes that take on a pseudo-octa­hedral symmetry and can be synthesized under weak-base conditions., Reported in this contribution are the synthesis and crystal structures of new mono- and bis-phenyl­acetyl­ides based on CoIII(DMC) (DMC is 5,12-dimethyl-1,4,8,11-tetra­aza­cyclo­tetra­deca­ne). Chlorido­(5,12-dimethyl-1,4,8,11-tetra­aza­cyclo­tetra­deca­ne)(phenyl­ethyn­yl)cobalt(III) chloride–aceto­nitrile–methanol (1/1/1), [Co(C8H5)Cl(C12H28N4)]Cl·CH3CN·CH3OH, 1, and (5,12-dimethyl-1,4,8,11-tetra­aza­cyclo­tetra­deca­ne)bis­(phenyl­ethyn­yl)cobalt(III) tri­fluoro­methane­sulfonate–di­chloro­methane (2/1), [Co(C8H5)2(C12H28N4)]2(CF3SO3)2·CH2Cl2, 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-octa­hedral 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 CoIII 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 mol­ecules 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 mol­ecules in 1 are disordered, the major occupancy rates refined to 0.643 (16) and 0.357 (16). Compound 2 also contains two mol­ecules in the asymmetric unit, together with two tri­fluoro­methane­sulfonate anions [of which one is disordered; occupancy values of 0.503 (16) and 0.497 (16)] and a disordered di­chloro­methane [occupancy values of 0.545 (12) and 0.455 (12)].