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N4H9Cu7S4:  A Hydrazinium-Based Salt with a Layered Cu7S4- Framework

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posted on 05.02.2007, 00:00 by David B. Mitzi
Crystals of a hydrazinium-based copper(I) sulfide salt, N4H9Cu7S4 (1), have been isolated by an ambient temperature solution-based process. In contrast to previously reported hydrazinium salts of main-group metal chalcogenides, which consist of isolated metal chalcogenide anions, and ACu7S4 (A = NH4+, Rb+, Tl+, K+), which contains a more three-dimensional Cu7S4- framework with partial Cu-site occupancy, the structure of 1 [P21, a = 6.8621(4) Å, b = 7.9851(4) Å, c = 10.0983(5) Å, β = 99.360(1)°, Z = 2] is composed of extended two-dimensional Cu7S4- slabs with full Cu-site occupancy. The Cu7S4- slabs are separated by a mixture of hydrazinium and hydrazine moieties. Thermal decomposition of 1 into copper(I) sulfide proceeds at a significantly lower temperature than that observed for analogous hydrazinium salts of previously considered metal chalcogenides, completing the transition at temperatures as low as 120 °C. Solutions of 1 may be used in the solution deposition of a range of Cu-containing chalcogenide films.