Crystal and molecular structure of two Zn–Cu compounds: Zn(NH3)2Cu(CN)3 and [Zn(en)3]6[Cu5(CN)17] · nH2O (n = 8.4) containing novel [Cu2(CN)7]5− ion
Abstract
The result of crystal structure analysis of two Zn–Cu bimetallic complexes are reported. Poly-[diammine-zinc(II)-tricyanocuprate(I)], C3H6N5CuZn, [Zn(NH3)2Cu(CN)3]∞, Mr = 241.03, monoclinic, space group P21/n, a = 6.395(2), b = 6.827(2), c = 17.296(5) Å, β = 98.55(2)°, V = 746.7(3) Å3, Z = 4, Dm = 2.12, Dx = 2.14M gm−3, λ(CuKα) = 1.54178 Å, μ = 6.72 mm−1, F(000) = 472, T = 293 K, R = 0.0487 for 856 observed reflections (F ≧ 4σ(F)). The polymeric structure is formed by [(NH3)2Zn(NC)Cu(CN)]2 rings linked together by bridging cyano groups bonded to the Cu(I) atoms. The Zn(II) atom is tetrahedrally coordinated by two ammonia molecules and two N-oriented cyano groups. The Cu(I) atom is deformed tetrahedrally coordinated by one N-bonded and three C-bonded cyano groups. One of the Cu–C≡N angles exhibits the unusual low value of 156.2(6)°.
Hexakis-[tris(ethylenediamine)-zinc(II)-tricyanocuprate bis[heptacyanodicuprate)-n-hydrate (n = 8.4), C53H160.8Cu5N53O8.4Zn6, [Zn(en)3]6[Cu2(CN)7]2 [Cu(CN)3] · nH2O (n = 8.4), Mr = 2385.40 rhombohedral, space group R32, a = 15.475(9) Å, α = 59.14(4)°, V = 2569(3) Å3, Z = 1, (hexagonal setting: a = 15.273 Å, c = 38.150 Å, V = 7707 Å3, Z = 3), λ(MoKα) = 0.71069 Å, μ = 2.5 mm−1, F(000) = 1242, T = 293 K, wR = 0.0772 for 1519 observed reflections. The structure is ionic and is formed by three crystallographically independent [Zn(en)3]2+ cations, one planar [Cu(CN)3]2- anion and two [(NC)3Cu(CN)Cu(CN)3]5- anions. Two crystallographically independent water molecules arc disordered.
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