Abstract
The synthesis and crystal structure of an unprecedented compound, zinc phospho-rus hepta-chloride or catena-poly[phospho-rus tetra-chloride [[di-chlor-ido-zinc]-μ-chlorido]], ZnPCl(7) or {[PCl(4)][ZnCl(3)]} (n) , are reported. The reaction of ZnCl(2) with PCl(5) in a 1:1 molar ratio at 623 K produced single crystals of ZnPCl(7), which crystallizes in the ortho-rhom-bic space group Ama2. The Zn and P atoms lie on crystallographic mirror planes, as do four of the Cl atoms. One Cl atom lies on a twofold axis and one occupies a general position. Its extended structure features isolated [PCl(4)](+) tetra-hedra and one-dimensional chains of corner-sharing ZnCl(2)Cl(2/2) tetra-hedra. Bond-valence sum calculations support the assignment of formal oxidation states. This discovery extends the compositional and structural landscape of mixed-metal halides.