First‐row transition metal–pyridine (py)–sulfate [(py)xM](SO4) complexes (M = Ni,Cu and Zn): crystal field theory in action

The crystal structures of three first‐row transition metal–pyridine–sulfate complexes, namely catena‐polytetrakis(pyridine‐κN)nickel(II)]‐μ‐sulfato‐κ²O:O′], Ni(SO₄)(C₅H₅N)₄]_n, (1), di‐μ‐sulfato‐κ⁴O:O‐bistris(pyridine‐κN)copper(II)], Cu₂(SO₄)₂(C₅H₅N)₆], (2), and catena‐polytetrakis(pyridine‐κN)zinc(II)]‐μ‐sulfato‐κ²O:O′‐bis(pyridine‐κN)zinc(II)]‐μ‐sulfato‐κ²O:O′], Zn₂(SO₄)₂(C₅H₅N)₆]_n, (3), are reported. Ni compound (1) displays a polymeric crystal structure, with infinite chains of Ni^II atoms adopting an octahedral N₄O₂ coordination environment that involves four pyridine ligands and two bridging sulfate ligands. Cu compound (2) features a dimeric molecular structure, with the Cu^II atoms possessing square‐pyramidal N₃O₂ coordination environments that contain three pyridine ligands and two bridging sulfate ligands. Zn compound (3) exhibits a polymeric crystal structure of infinite chains, with two alternating zinc coordination environments, i.e. octahedral N₄O₂ coordination involving four pyridine ligands and two bridging sulfate ligands, and tetrahedral N₂O₂ coordination containing two pyridine ligands and two bridging sulfate ligands. The observed coordination environments are consistent with those predicted by crystal field theory.