Templated synthesis of cuprous chloride networks:: Synthesis and characterization of [Hpy]Cu3Cl6 and {[H3NMe]6Cl}[M3NMe]2Cu9Cl16

Solvothermal reactions with a 1:1 ratio of cuprous chloride and alkylamonium salts as templating agents in acetonitrile or ethanol yield two new polyanionic chains. The trimeric chain [Cu3Cl6](3-), 1, templated by pyridinium cations, crystallizes in the monoclinic space group P2(1)/m with a = 9.1274(8) Angstrom, b = 13.2831(5) Angstrom, c = 10.0923(7) Angstrom, beta = 112.562(5)degrees, and Z = 2. [Cu9Cl16],(7-) 2, is templated by the complex cation {[H3NMe](6)Cl}(5+) and two independent [H3NMe](+) cations. The polyanionic chain of 2 is constructed from the condensation of tetrameric cuprous chloride building blocks and crystallizes in the triclinic space group P1 with a = 10.091(2) Angstrom, b = 10.173(2) Angstrom, c = 23.723(3) Angstrom, alpha = 80.12(1), beta = 80.99(1)degrees, gamma = 70.68(2)degrees, and Z = 2. The targeted stoichiometry of [A][CuCl2], with A = pyridinium or methylammonium as templates, results in the formation of condensed oligomeric building blocks that are analogous to those observed for a variety of open-framework group 13 chalcogenides. The relationship between the charge density of the templating species and of the inorganic building blocks is discussed with respect to general principles for the construction of open frameworks.