Lewis-base adducts of Group 1B metal(I) compounds. Part 17. Synthesis and crystal structures of adducts of copper(I) cyanide with nitrogen bases

Abstract

Compounds of the type [Cu(CN)L_n][L = diethylamine, (1), triethylamine, (2), 4-methylpyridine, (3), or 1,10-phenanthroline, (4)] have been synthesized by recrystallization of copper(I) cyanide from (or with) the parent base and their crystal structures have been determined by single-crystal X-ray diffraction methods; n= 1 except in the case of (3) where n= 1.5. Crystals of (1) are monoclinic, space group P2₁/n, with a= 15.108(7), b= 7.321(5), c= 13.699(6)Å, β= 103.00(4)°, and Z= 8; R was 0.044 for N_o= 871 independent ‘observed’ reflections. For (2), crystals are orthorhombic, space group Pnma, with a= 9.501(4), b= 8.921(4), c= 11.279(5)Å, and Z= 4; R= 0.039, N_o= 369. For (3), crystals are monoclinic, space group Cc, with a= 9.587(3), b= 16.326(4), c= 14.022(4)Å, β= 109.38(2)°, and Z= 4; R= 0.031, N_o= 1 070. For (4), crystals are trigonal, space group P3₁, with a= 9.175(5), c= 11.753(8)Å, and Z= 3; R= 0.041, N_o= 812. All complexes are one-dimensional polymers, that in (2) being disposed completely in a mirror plane except for the substituent alkyl groups. Copper atoms in (1) and (2) are trigonally planar co-ordinated by C,N(cyanide) and N(base), as is one of the two copper atoms in (3); the other copper atom in (3) is unusual, being four-co-ordinated pseudo-tetrahedrally by C,N(cyanide) and two N(base). A similar copper environment is found in (4).