Synthesis, decomposition studies and crystal structure of a three-dimensional CuCN network structure with protonated N-methylethanolamine as the guest cation

The crystal structure is reported of a three-dimensional anionic CuICN network with noncoordinated protonated N-methyl­ethano­lamine cations providing charge neutrality. Pairs of cuprophilic Cu atoms are bridged by μ3-cyanide groups which link these units into 43 spirals along the c axis, and these are linked together by other cyanide groups. On heating the com­pound to 280 °C, a CuCN residue is formed, while further heating leaves a residue of elemental copper, isolated as the oxide.
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.