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The crystal structures of only a few iron(II) and silver(I) coordination compounds containing 2,6bis(pyrazol-1-yl)pyrazine (bppz) ligands have been reported. Most of the iron compounds display a thermochromic spin crossover (SCO) on cooling below room temperature [1]. While the SCO complexes, [Fe(bppz)2Α2(nCH3NO2 {A=BF4, Co(C2B9H11)2}, were structurally charaterized [2,3], solvates containing methanol have not yet been investigated. Solvent effects are however known to dramatically influence the SCO behaviour in the solid state. In the structure of the mononuclear complex [Co(bppz)2](ClO4)2cMeOH, each cobalt(II) ion is coordinated by two chelating bppz ligands. These tridentate ligands are approximately planar with an angle of 88.3° between the two planes. Due to the sterical demands imposed by the ligand, the CoN6 octahedron is distorted with N-Co-N angles ranging between 74.3 and 117.9° and Co-N distances between 2.0634 and 2.1687 Å. One of the perchlorate units shows a rotational disorder for three of the O atoms with the axis of rotation located on the fourth Cl-O bond. A view of the molecule arrangement in the unit cell shows that the [Co(bppz)2] 2+ cations and the methanol molecules are alternatively arranged in the bc plane leading to a chessboard-like pattern composed of the centers of gravity of the methanol molecules and the [Co(bppz)2] 2+ cations. These 2D layers are separated by the perchlorate counteranions. The first counteranion layer is essentially planar and lies in the bc plane at x ≈ 0 with the central Cl atom showing only a slight deviation from the ideal position (0, 0.25, 0.25) for a p2mm lattice. The second perchlorate layer shows a marked deviation from the ideal position at x = 0.5, resulting in the formation of a puckered mesh structure, which can be derived from the 2D plane group p2.

Structure feature of 3-d metal and aluminum trifluoroacetates and their acetates analogs