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

Solvothermal reactions with a 1:1 ratio of cuprous chloride and alkylamoniu m salts as templating agents in acetonitrile or ethanol yield two new polya nionic 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 cat ion {[H3NMe](6)Cl}(5+) and two independent [H3NMe](+) cations. The polyanio nic chain of 2 is constructed from the condensation of tetrameric cuprous c hloride building blocks and crystallizes in the triclinic space group P1 wi th 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 methyla mmonium as templates, results in the formation of condensed oligomeric buil ding blocks that are analogous to those observed for a variety of open-fram ework group 13 chalcogenides. The relationship between the charge density o f the templating species and of the inorganic building blocks is discussed with respect to general principles for the construction of open frameworks.