Dependence of the Distortion of the Square Pyramids in N, N-Dimethylethylenediammonium Pentachloroantimonate(III) on the Geometry of Hydrogen Bonds

Abstract N ,N-Dimethylethylenediammonium pentachloroantimonate(III) crystallizes in the monoclinic system, in space group P2 1 /c (a = 12.460(2), b = 10.252(2), c = 10.330(2) Å, β = 97.75(3)°, V = 1307.5(4) Å 3 , Z = 4, d c = 1.997, d m = 1.99(2) g/cm 3 ). The crystal structure of [(CH 3 ) 2 NH(CH 2 ) 2 NH 3 ][SbCl 5 ] consists of isolated [SbCl 5 ] 2- anions and [(CH 3 ) 2 NH(CH 2 ) 2 NH 3 ] 2+ cations. The [SbCl 5 ] 2- anion has a distorted square pyramidal geometry, presenting one short axial and four long equatorial Sb-Cl bonds. The square pyramids are characteristically stacked one close to the other, parallel to the c axis. The voids between the anionic sublattice are filled by [(CH 3 ) 2 NH(CH 2 ) 2 NH 3 ]2+ cations. The five non-equivalent Sb-Cl bond distances within the [SbCl 5 ] 2- square pyramid are significantly different. The equatorial Sb-Cl bonds are in the range 2.427(2)-2.968(2) Å, whereas the axial one is 2.384(1) Å long. The study reveals that N-H...C1 hydrogen bonds are responsible for the deformation of equatorial Sb-Cl bonds from the mean value of 2.654(7) Å. Analysis of intermolecular interactions between the [SbCl 5 ] 2- pyramids in the structure, reflected in changes of Sb-Cl bond lengths from the values characteristic of non-interacting pyramids, leads to the conclusion that the van der Waals radius of Sb is significantly smaller than that estimated by Pauling.