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 self-assembling mode of [CuCl] with tetrahydrothiophene is reported. Copper(l) 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 [CuCOCl] n with THT gave [(CuCl)2(THT)3] x ,1, in CH3OH, [(CuCl)(THT)2] x ,2 in THF [(CuCl)(THT)] x ,3, in CH2Cl2, and [(CuCl)3(THT)2] x ,4, in DME. Compound1 consists of polymeric chains of centrosymmetric Cu2Cl2 dinuclear units bridged by THIT molecules running parallel to the [101] axis. In the structure of2 we found polymeric layers generated from the [(CuCl)(THT)] asymmetric unit by the center of symmetry and by the twofold axis. In compound3 the structure consists of layers generated through the center of symmetry by the [(Cu2Cl2)(THT)2] asymmetric unit, while4 consists of layers generated through the center of symmetry by the [(Cu3Cl3)(THT)2] asymmetric unit. Crystallographic details are as [ollows:2 is monoclinic, space group P21/c.a=9.657(3) A,b=6.441(2) A,c=11.459(3) A,\=111.96(2)°,V=661.0(4) A3. andR=0.075;3 is monoclinic, space group P21/n,a=19.327(7) A,b=6.703(2) A,c=10.116(3) A,s=103.04(3)°,V=1276.7(7) A3 andR=0.043:4 is triclinic, space group Pl,a=12.513(2) A,b=6.698(1) A,c=9.651(1) A,α=91.98(1)°,\=107.86(1)°,γ=74.59(1)°,V=741.2(2) A3, andR=0.044.