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,ß=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,=91.98(1)°,\=107.86(1)°,=74.59(1)°,V=741.2(2) A³, andR=0.044.