Crystals of the title compounds are monoclinic, space group P21/a, with Z= 4 in a unit cell of dimensions: a= 19.727(6), b= 9.176(3), c= 21.481 (10)Å, β= 113.72(3)°. The structure has been elucidated from 4 448 non-zero diffracted intensities, measured on a four-circle diffractometer, by conventional heavy-atom methods, and refined to R 0.109. The anion consists of two slightly distorted square planar [PtCl2(CO)]– entities linked by an unbridged Pt–Pt bond such that the dihedral angle between the two planes is 60°. The carbonyl groups adopt a transoid configuration. The structure found is one of those predicted from spectroscopic observations. The Pt–Pt bond distance [2.584(2)Å] has a strong trans-influence on the Pt–Cl bond lengths.
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Modinos et al. (1975) studied this question.