CRYSTAL AND MOLECULAR-STRUCTURE OF 2 ZN-CU COMPOUNDS - ZN(NH3)2CU(CN)3 AND [ZN(EN)3]6[CU5(CN)17]CENTER-DOT-NH2O (N=8.4) CONTAINING NOVEL [CU2(CN)7]5- ION

The result of crystal structure analysis of two Zn - Cu bimetallic com plexes are reported. Poly-[diammine-zinc(II)-tricyanocuprate(I)], C3H6 N5CuZn, [Zn(NH3)2Cu(CN)3]infinity, M(r) = 241.03, monoclinic, space gr oup P2(1)/n, a = 6.395 (2), b 6.827 (2), c = 17.296(5) beta = 98.55(2) degrees, V = 746.7(3) angstrom3, Z = 4, D(m) = 2.12, D(x) = 2.14 Mgm-3 , lambda(CuK(alpha)) = 1.54178 angstrom, mu = 6.72 mm-1, F(000) = 472, T = 293 K, R = 0.0487 for 856 observed reflections (F greater-than-or -equal-to 4sigma(F)). The polymeric structure is formed by [(NH3)2Zn(N C)Cu(CN)]2 rings linked together by bridging cyano groups bonded to th e Cu(I) atoms. The Zn(II) atom is tetrahedrally coordinated by two amm onia molecules and two N-oriented cyano groups. The Cu(I) atom is defo rmed tetrahedrally coordinated by one N-bonded and three C-bonded cyan o groups. One of the Cu-C=N angles exhibits the unusual low value of 1 56.2(6)degrees. is-[tris(ethylenediamine)-zinc(Il)-tricyanocuprate bis [heptacyanodicuprate)-n-hydrate (n = 8.4), C53H160.8Cu5N5308.4Zn6, [Zn (en)3]6[Cu2(CN)7]2 [Cu(CN)3] . nH2O (n = 8.4), M, = 2385.40 rhombohedr al, space group R32, a = 15.475(9) angstrom, alpha = 59.14(4)degrees, V = 2569(3) angstrom3, Z = 1, (hexagonal setting: a = 15.273 angstrom, c = 38.150 angstrom, V = 7707 angstrom3, Z = 3), lambda(MoK(alpha)) = 0.71069 angstrom, mu = 2.5 mm-1, F(000) = 1242, T = 293 K, wR = 0.077 2 for 1519 observed reflections. The structure is ionic and is formed by three crystallographically independent [Zn(en)3]2+ cations, one pla nar [Cu(CN)3]2- anion and two [(NC)3Cu(CN)Cu(CN)3]5- anions. Two cryst allographically independent water molecules are disordered.