The charge distribution has been determined by multipole refinements against single-crystal X-ray diffraction data. In the refinements a comparison was made between the densities based on H-atom parameters from X-ray and neutron data, respectively. X-ray study: (Mo K ) = 0.71073 Å, F(000) = 408; at 30 K: R(F) = 0.015 for 6686 reflections; at 295 K: R(F) = 0.022 for 4630 reflections. The nickel ion is octahedrally surrounded by four water molecules and two chloride ions, forming a locally neutral Ni(H2O)4Cl2 complex. Two of the water molecules are coordinated to nickel approximately in one of the tetrahedral (`lone-pair') directions; the other two are trigonally coordinated. At 30 K one H atom in one of the trigonally coordinated water molecules is disordered, with equal occupation of two different positions. Owing to the polarizing influence of the nickel ion there are two peaks in the lone-pair plane of the water molecules when these are tetrahedrally coordinated; for those trigonally coordinated there is just one peak. The individual (`partial') charge densities, calculated from the deformation functions of only nickel or the separate water molecules, have also been calculated to study the effects of superposition of the individual densities. In the individual density of nickel an excess is observed in the diagonal directions and a deficiency in the ligand directions. However, owing to the influence of the whole crystalline environment, the maxima around nickel are not found in the planes defined by nickel and the six ligands.