Crystal Structures of a Series of Complexes Produced by Reaction of Copper(I) Cyanide with Diamines

A new synthetic procedure developed recently in our laboratories has made possible the synthesis of variety of
new complexes of CuCN with diamines. Synthesis was effected by adding the ligand to a solution of CuCN in
aqueous sodium thiosulfate. This procedure also provides an alternative pathway to a novel diamine complex
reported by us previously, (CuCN)3(HMTA)2 (1) (where HMTA = hexamethylenetetramine). The other diamine
ligands used were 1,4-diazabicyclo[2.2.2]octane (dabco), 1,4-dimethylpiperazine (dmpip), piperazine (pip), 1,4-butanediamine (butda), N,N,N‘,N‘-tetramethylethylenediamine (tetmen), and N-phenylpiperazine (phpip). Complex
2, Cu2(CN)3(dabco-H), crystallizes in the hexagonal space group P63 with unit cell dimensions a = 8.174(3) Å,
c = 8.083(4) Å, and Z = 2. Complex 3, (CuCN)2(dmpip), crystallizes in the monoclinic space group C2/m with
unit cell dimensions a = 8.812(3) Å, b = 9.631(2) Å, c = 7.266(3) Å, β = 113.40(3)°, and Z = 2. Complex 4,
(CuCN)2(pip), crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 9.439(3) Å, b =
10.561(2) Å, c = 8.870(3) Å, β = 98.32(3)°, and Z = 4. Complex 5, Cu2(CN)3(pip-H), crystallizes in the monoclinic
space group C2/c with unit cell dimensions a = 20.573(9) Å, b = 8.354(2) Å, c = 15.989(6) Å, β = 133.70(3)°,
and Z = 8. Complex 6, (CuCN)2(butda), crystallizes in the monoclinic space group P21/c with unit cell dimensions
a = 10.456(2) Å, b = 5.550(1) Å, c = 8.669(3) Å, β = 106.80(2)°, and Z = 2. Complex 7, (CuCN)2(tetmen),
crystallizes in the orthorhombic space group Cmc21 with unit cell dimensions a = 11.889(4) Å, b = 33.380(8)
Å, c = 9.012(3) Å, and Z = 12. Complex 8, (CuCN)(phpip), crystallizes in the monoclinic space group P21/c
with unit cell dimensions a = 17.8819(3) Å, b = 6.9190(1) Å, c = 8.6972(1) Å, β = 96.720(1)°, and Z = 4.