Synthesis, Decomposition Studies and Crystal Structure of a Three-Dimensional CuCN Network Structure with Protonated N-methylethanolamine As the Guest Cation

The compound poly[2-hydroxy-N-methylethan-1-aminium [μ3-cyanido-κ3 C:C:N-di-μ-cyanido-κ4 C:N-dicuprate(I)]], {(C3H10NO)[Cu2(CN)3]} n or [meoenH]Cu2(CN)3, crystallizes in the tetragonal space group P43. The structure consists of a three-dimensional (3D) anionic CuICN network with noncoordinated protonated N-methylethanolamine cations providing charge neutrality. Pairs of cuprophilic Cu atoms are bridged by the C atoms of μ3-cyanide ligands, which link these units into a 43 spiral along the c axis. The spirals are linked together into a 3D anionic network by the two other cyanide groups. The cationic moieties are linked into their own 43 spiral via N—H...O and O—H...O hydrogen bonds, and the cations interact with the 3D network via an unusual pair of N—H...N hydrogen bonds to one of the μ2-cyanide groups. Thermogravimetric analysis indicates an initial loss of the base cation and one cyanide as HCN at temperatures in the range 130–250 °C to form CuCN. We show how loss of a specific cyanide group from the 3D CuCN structure could form the linear CuCN structure. Further heating leaves a residue of elemental copper, isolated as the oxide.