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The coordination capability of Cl and Br in halogenocadmate(II) complexes is estimated by a solution of the structure of 1,3-propanediammonium dibromodichlorocadmate(II). The compound crystallizes as a layered anion structure with Cl bridges and Br terminals at 293 K: Imma, a = 741.56(7), b = 1869.5(5), and c -771.55(8) pm, Z = 4. In order to explain the stronger tendency of halogenocadmate(II) complexes to form layered structures as compared to halogenozincate(II), ab-initio calculations were performed. The stability of MX 5  3- (M = Cd, Zn; X = Cl, Br) is compared. Isolated ZnX 5  3-  and CdBr 5  3-  ions are not stable. On the other hand a trigonal bipyramid CdCl 5  3-  ion is considered to be subtly stable in the crystal mainly due to Coulomb attractive interactions between the positively charged metal cation Cd 2+  in a CdCl 3-  fragment and two Cl -  ions.

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Isolated versus Condensed Anion Structure VII: X-ray Structure Analysis of 1,3-Propanediammonium Dibromodichlorocadmate(II), [H 3 N(CH 2 ) 3 NH 3 ]CdBr 2 Cl 2 , and Estimation of Stability of Five-coordinated Halide Anions, MX 5  3- (M = Cd, Zn; X = Cl, Br) by Means of Ab-initio MO Calculations