Copper(II) Halide Complexes of 2-Aminopyrimidines: Crystal Structures of [(2-aminopyrimidine) n CuCl2] (n=1,2) and (2-amino-5-bromopyrimidine)2CuBr2

Abstract

The reaction of CuX2(X=Cl, Br) with 2-aminopyrimidine in aqueous solution, or 2-amino-5-bromopyrimidine in aqueous acid yields compounds of the forms [LCuCl2] n (1), [L2CuCl2] (2) and [L'2CuBr2] (3) [L=2-aminopyrimidine; L'=2-amino-5-bromo-pyrimidine]. The three compounds all form layered structures in which each copper ion is coordinated to two 2-aminopyrimidine molecules and two halide ions. Common structural threads involve bridging ligation [either by monomeric (1) or hydrogen bonded ligand dimers (2 and 3)], N-H···X and N-H···N hydrogen bonding and π-π stacking interactions as well as semi-coordinate Cu···X bond formation (1 and 2) or Br···Br interactions (3). Compounds 1 and 2 crystallize as two-dimensional coordination polymers with asymmetrically bihalide bridged (CuX2) n chains cross-linked into sheets by the 2-aminopyrimidine molecules (1) or by hydrogen bonded L2 dimers (2). The halide bibridged chains expand their primary copper coordination spheres to give 4 + 2 coordination spheres in 1 and 2. In 3, the layer structure involves coordination of the hydrogen bonded L'2 dimers and C-Br···Br- interactions. Crystal data: (1): monoclinic, P21/m, a=3.929(1), b=12.373(2), c=7.050(1)å, β=91.206(4)°, V=342.7(1)Åsup3;, Z=2, D calc= 2.225Mg/m3, μ=3.878 mm-1, R=0.0269 for [|I|≥3σ(I)]. For (2): triclinic, P-1, a=4.095(4), b=7.309(5), c=10.123(6) å, α=86.28(6), β=78.44(6), γ=74.55(8)°, V=286.1(4) Å3, Z=1, D calc=1.884 Mg/m3, μ=2.360 mm-1, R=0.0506 for [|I|≥2σ(I)]. For (3): triclinic, P-1, a=6.074(4), b=7.673(3), c=8.887(3) å, α=108.43(3) β=100.86(5), γ=106.96(4)°, V=357.0(3) Å3, Z=1, D calc=2.657 Mg/m3, μ=12.714mm-1, R=0.0409 for [|I|≥2σ(I)].