Distortion of Crystal Structures of Some CoIII Ammine Complexes. II. Distortion of Crystal Structures of [Co(NH3)5NO2]X 2 (X = Cl, Br) on Cooling

Abstract

For two solid complexes, [Co(NH3)5NO2]X 2 (X = Cl−, Br−), pentaamminenitrocobalt(III) dichloride/dibromide, the anisotropy of structural distortion on cooling the samples from 290 to 150 K was studied by variable-temperature single-crystal X-ray diffraction. The changes in lattice parameters were used to calculate the strain tensors and to scan linear strain in various crystallographic directions. The changes in different intra- and intermolecular distances in the structure were followed. Lattice strain on cooling was compared with lattice strain in the same structures under high hydrostatic pressure and with structural distortion in the course of homogeneous nitro–nitrito linkage isomerization. The effect of isomorphous substitution (Br− for Cl−) with respect to structural strain was discussed. Structural strain in the monoclinic chloride and bromide was compared also with the previously obtained data [Boldyreva, Kivikoski & Howard (1997). Acta Cryst. B53, 394–404] on strain in the orthorhombic structure of another compound of the same CoIII nitropentaammine series, [Co(NH3)5NO2]CI(NO3).