Charge Density in Orthorhombic NiSO₄.7H₂O at Room Temperature and 25 K

The charge-density distribution in the title compound nickel sulfate heptahydrate has been determined by multipole refinement against single-crystal X-ray intensity data. For the refinement at 25 K hydrogen positions and displacement parameters were fixed to values determined from neutron data. The charge density based on the deformation functions of all atoms in the structure is compared with the individual densities calculated from the deformation functions of only nickel or the separate water molecules. In this way the effects of simple superposition of the individual densities have been studied. The individual deformation density around nickel is in good qualitative agreement with that expected for an approximately octahedral Ni(H₂O)₆²⁺ complex in a weak ligand field. However, the maximum densities are not found precisely in the planes defined by nickel and the six water ligands, which illustrates that it is necessary to consider the crystal field due to the whole crystalline environment. The individual densities of the water molecules show clear polarization of the lone-pair densities according to the coordination of the water molecules: tetrahedral coordination leads to two resolved lone-pair peaks, whereas planar trigonal coordination leads to just one single peak. Crystal data: NiSO₄.7H₂O, M_r = 280.87, P2₁2₁2₁, Z = 4. At T = 25 K: a = 6.706 (3), b = 11.796 (6), c = 11.949 (6) Å, V = 945 (1) ų, D_x = 1.977 Mg m⁻³. At 295 K: a = 6.751 (4), b = 11.746 (7), c = 12.003 (8) Å, V = 952 (1) ų, D_x = 1.959 Mg m⁻³. X-ray study: F(000) = 584, λ(Mo Kα) = 0.71069 Å, μ = 2.255 mm⁻¹. At 25 K: R(F) = 0.014 for 10 185 reflections. At 295 K: R(F) = 0.015 for 5723 reflections. Neutron study at 25 K: λ = 1.215 Å, μ = 0.261 mm⁻¹, R(F) = 0.034 for 1381 reflections.

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