Crystal structures and thermogravimetric analyses of six CuCN network structures with protonated N-alkylethanolamines as guest cations

The structures of six triperiodic CuCN network structures with conjugate acids of four N -alkylethanolamines as guest cations are described, namely, poly[2-hydroxyethan-1-aminium [μ 3 -cyanido-di-μ 2 -cyanido-dicuprate(I)]], {(C 2 H 8 NO)[Cu 2 (CN) 3 ]} n , 1 , poly[bis(2-hydroxy- N -methylethan-1-aminium) [di-μ 3 -cyanido-tri-μ 2 -cyanido-tricuprate(I)] monohydrate], {(C 4 H 12 NO) 2 [Cu 3 (CN) 5 ]·H 2 O} n , 2 , poly[tetrakis[ N -(2-hydroxyethyl)ethan-1-aminium] [chloridotetra-μ 3 -cyanido-penta-μ 2 -cyanido-tricuprate(I)]], {(C 4 H 12 NO) 4 [Cu 6 (CN) 9 Cl]} n , 3 , poly[tetrakis[ N -(2-hydroxyethyl)ethan-1-aminium] [penta-μ 3 -cyanido-hepta-μ 2 -cyanido-octacuprate(I)]], {(C 4 H 12 NO) 4 [Cu 8 (CN) 12 ]} n , 4 , poly[2-hydroxy- N , N -diisopropylethan-1-aminium [μ 3 -cyanido-μ 2 -cyanido-dicuprate(I)] monohydrate], {(C 8 H 20 NO)[Cu 3 (CN) 4 ]·H 2 O} n , 5 , and poly[2-hydroxy- N , N -diisopropylethan-1-aminium [μ 3 -cyanido-di-μ 2 -cyanido-dicuprate(I)]], {(C 8 H 20 NO)[Cu 2 (CN) 3 ]} n , 6 . In five of the structures ( 1 – 5 ), the CuCN network includes Cu atoms occurring in pairs, linked by cuprophilic interactions. Analysis with the intent of exploring the `template effect' of the cations on the CuCN network structure indicated five separate CuCN topologies. The two different crystal structures involving cations from N -ethylethanolamine have the same basic topology, whereas the two crystal structures involving cations from N , N -diisopropylethanolamine have different topologies, contrary to what might be expected from a template effect. Thermogravimetric analysis of the compounds usually shows loss of HCN(g) and the free base by 200 °C, with a CuCN(s) residue, but decomposition of one of the structures is more complex.