Comparative structural studies of the first row early transition metal(III) chloride tetrahydrofuran solvates

Abstract

Two compounds of empirical formula MCl 3- (THF) 3, M = V and Cr, have been characterized by single crystal X-ray studies. The VCl 3(THF) 3 molecule, which has a mer octahedral stereochemistry, crystallizes in the monoclinic space group P2 1/ c with a= 8.847(2), b= 12.861(5), c= 15.134(3) Å, β = 91.94(2)°, V = 1721(1) Å 3 and Z = 4. The V-Ci(1) and V-CI(2) distances have a mean value of 2.330 [3] Å while V-CI(3) = 2.297(2) Å, The VO(1) and VO(2) distances have a mean value of 2.061[8] Å while V-O(3) = 2.102(3) Å cis ClVCl angles average 92.0[5]° and cis OVO angles average 86.2[2]° . The isostmctural complex, CrCl 3(THF) 3, has a crystal structure made up of discrete octahedral mer-CrCl 3(THF) 3 molecules with the following unit cell dimensions (space group P2 1/c): a = 8.715(1), b= 12.786(3), c = 15.122(3) Å, β = 92.15(1)°, V = 1684(1) Å 3 and Z = 4. The CrCl(1) and CrCl(2) distances have a mean value of 2.310131 Å while CrCl(3) = 2.283(2) Å. The CrO(1) and CrO(2) distances have a mean value of 2.0101171 Å while CrO(3) = 2.077(4) Å. cis ClCrCl angles average 90.9[4]° and cis OCrO angles average 86.1 [2]°. The structures of these two octahedral complexes and those previously reported for ScCl 3(THF) 3 and TiCl 3(THF) 3 are compared and certain general trends are discussed.