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The asymmetric unit of the title compound, [Mn2(C6H6O7)2(H2O)4]·C12H10N2·2H2O, contains half of the centrosymmetric Mn complex dimer, half of a 1,2-bis­(pyridin-4-yl)ethene mol­ecule, which lies across an inversion center, and one water mol­ecule. Two citrate ligands bridge two MnII ions, and each MnII atom is coordinated by four O atoms from the citrate ligands (one from hy­droxy and three from carboxyl­ate groups) and two water O atoms, forming a distorted octa­hedral environment. In the crystal, O—H...O and O—H...N hydrogen bonds link the centrosymmetric dimers and lattice water mol­ecules into a three-dimensional structure which is further stabilized by inter­molecular π–π inter­actions [centroid–centroid distance = 3.959 (2) Å]. Weak C—H...O hydrogen bonding interactions are also observed.

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The asymmetric unit of the title hydrated salt, C18H40N4P+·Cl·2H2O, consists of two ionic mol­ecules and four water mol­ecules. The mol­ecular geometry around the penta­coordinate P atom is trigonal–bipyramidal, with a H atom and an apical N atom in axial positions and three N atoms with isobutyl substituents in equatorial positions. The Cl ions and water mol­ecules are connected via O—H...Cl hydrogen bonds, forming chains along [100]. The ethyl­ene bridging groups are disordered with refined site-occupancy ratios of 0.578 (9):0.422 (9).
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