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The crystal structure of the title compound, {[AsCl3(C5H5N)]·H2O} n , is characterized by polymeric chains consisting of alternating arsenic and chlorine atoms running parallel to the a axis. O-H⋯Cl and N-H⋯O hydrogen bonds mediated by non-coordinating water mol-ecules assemble these chains into a three-dimensional framework. The As(III) atom, the atoms of the pyridinium ring and the water O atom have m site symmetry and the bridging Cl atom has site symmetry 2. This is the first reported organotrichloro-arsenate(III) in which arsenic adopts a ψ-octa-hedral fivefold coordination.

catena-Poly[[[dichlorido(pyridin-1-ium-3-yl)arsenic(III)]-μ-chlorido] monohydrate]