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In the title complex, [Co(C22H18N2O4)(CN)(H2O)]·0.5CH3CN, the CoIII cation is N,N′,O,O′-chelated by a 6,6′-dimeth­oxy-2,2′-[1,2-phenyl­enebis(nitrilo­methanylyl­idene)]diphenolate dianion, and is further coordinated by a cyanide anion and a water mol­ecule in the axial sites, completing a distorted octa­hedral coordination geometry. In the crystal, pairs of bifurcated O—H...(O,O) hydrogen bonds link adjacent mol­ecules, forming centrosymmetric dimers. The acetonitrile solvent mol­ecule shows 0.5 occupancy.

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In the anion of the title salt, C6H16N+·C18H13O8-, one of the carboxyl groups is deprotonated. Its O atoms are involved in inter­molecular hydrogen bonding with the carboxyl group of an adjacent anion and the amino group of an adjacent cation. The two benzoyloxy rings are oriented with respect to each other at a dihedral angle of 79.46 (6)°.

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In the title mol­ecular salt, C14H13N2O2+·ClO4, the ring systems in the cation are almost coplanar [dihedral angle = 5.53 (13)°]. Intra­molecular N—H...O and O—H...O hydrogen bonds generate S(6) and S(5) rings, respectively. In the crystal, the two H atoms involved in the intra­molecular hydrogen bonds also participate in inter­molecular links to acceptor O atoms of the perchlorate anions. A simple inter­molecular N—H...O bond also occurs. Together, these form a double-chain structure along [101].
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