A Structural Variability of Copper(I) Chloride-Tetrahydrothiophene Adducts Crystallizing in Polymeric Forms and Exhibiting Polymorphism: The Role of the Solvent

The function of the solvent in the sell-assembling mode of [CuCl] with tetrahydrothiophene is reported. Copper(1) chloride has been used in the form of [CuCOCl]n, which is slightly soluble in the most common solvents, and to allow an homogeneous phase reaction. The reaction of [CuCOCk]nwith THT gave [(CuCl)2(THT)3]x. 1, in CH3OH, [(CuCl)(THT)]x, 2 in THF [(CuCl)(THT)]x3, in CH2Cl2, and [(CuCl)3(THT)2]x, 4, in DME. Compound 1 consists of polymeric chains of centrosymmetric Cu2Cl2dinuclear units bridged by THT molecules running parallel to the [101] axis. In the structure of 2 we found polymeric layers generated from the [(CuCl)(THT)] asymmetric unit by the center of symmetry and by the twofold axis. In compound 3 the structure consists of layers generated through the center of symmetry by the [(Cu2Cl2)(THT)2] asymmetric unit, while 4 consists of layers generated through the center of symmetry by the [(Cu3Cl3)(THT)2] asymmetric unit. Crystallographic details are as follows: 2 is monoclinic, space group P21/c, a = 9.657(3) A, b = 6.441(2) A, c = 11.459(3) A, β = 111.96(2)°, V = 661.0(4) A3, and R = 0.075; 3 is monoclinic, space group P21/n, a = 19.327(7) A, b = 6.703(2) A, c = 10.116(3) A, β = 103.04(3)°, V = 1276.7(7) A3and R = 0.043; 4 is triclinic, space group P1̄, a = 12.513(2) A, b = 6.698(1) A, c = 9.651(1) A, α = 91.98(1)°, β = 107.86(1)°, γ = 74.59(1)°, V = 741.2(2) A3, and R = 0.044.