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The title complex, [Co(C21H16N4)2][Co(NCS)4]·CH3OH, consists of one [Co{C(py)4}2]2+ complex cation [C(py)4 = tetra­kis­(pyridin-2-yl)methane], one [Co(NCS)4]2− complex anion and a methanol solvent mol­ecule. In the cation, the CoII atom is coordinated by six N atoms of two C(py)4 ligands in a distorted octa­hedral geometry. In the anion, the CoII atom is coordinated by the N atoms of four NCS ligands in a distorted tetra­hedral geometry. The methanol mol­ecule is disordered and was modelled over three orientations (occupancies 0.8:0.1:0.1). There are two weak hydrogen-bond-like inter­actions between the methanol solvent mol­ecule and NCS ligands of the anion [O...S = 3.283 (3) and 3.170 (2) Å].

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A second polymorph of the title compound, C21H16N4, is reported. The original polymorph was solved by our group [Matsumoto et al. (2003). Tetra­hedron Lett. 44, 2861-2864] in the monoclinic space group C2/c and refined to R = 0.050. Now the crystal structure of a tetra­gonal polymorph (space group P-421c) has been solved and refined to R = 0.036. In the crystal, there are no strong inter­molecular inter­actions. Reflecting the high symmetry of the mol­ecular structure, the asymmetric unit is a quarter of the mol­ecule, and the mol­ecule exhibits S4 symmetry along the c axis in the crystal.
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