Interaction of pentaphenylantimony and penta(para-tolyl)antimony with biphenyl-2,2'-dicarboxylic acid. Reaction of pentaphenylantimony with biphenyl-4,4'-dicarboxylic acid. Structure of reaction products.

Abstract

The interaction of pentaphenylantimony and penta(para-tolyl)antimony with biphenyl-2,2'-dicarboxylic acid (molar ratio 2:1) in toluene and benzene, led to synthesis of binuclear derivatives 4-Ph4SbOC(O)C6H4C6H4OC(O)SbPh4 (1) and Tol4SbOC(O)C6H4C6H4SbTol4 ∙ 2PhH (2), yielding 70 % and 73 %, respectively. The reaction of pentaphenylantimony with biphenyl-4,4’-dicarboxylic acid in benzene produced Ph4SbOC(O)C6H4C6H4SbPh4 ∙ 3PhH (3) (81%). Crystallographic characteristics of the complexes: (1) [C62H48O4Sb2, M = 1100.50; monoclinic syngony, space group Pn; cell parameters: a = 9.889(5) Å, b = 25.446(14) Å, c = 10.321(5) Å; β = 105.85(2)°, V = 2498(2) Å3, Z = 2; rcalc = 1.463 g/cm3; m = 1.130 mm–1; F(000) = 1108.0; collection area by 2q: 5.98-53.82°; total reflections 25282; independent reflections 9696 (Rint = 0.0706); GOOF = 1.190; R-factor 0.0522]; (2) [C82H76O4Sb2, M = 1368.93; monoclinic syngony, space group C2/c; cell parameters: a = 12.009(7) Å, b = 30.69(2) Å, c = 19.374(11) Å; β = 93.57(2)°, V = 7126(8) Å3, Z = 1; rcalc = 1.276 g/cm3; m = 0.806 mm–1; F(000) = 2808.0; collection area by 2q: 5.72-54.34°; total reflections 69807; independent reflections 7887 (Rint = 0.0708); GOOF = 1.048; R-factor 0.0422; (3) [C80H66O4Sb2, M = 1334.85; triclinic syngony, space group P-1; cell parameters: a = 10.676(8) Å, b = 13.404(8) Å, c = 13.917(9) Å; a = 116.53(2)°, β = 104.21(3)°, g = 97.60(2)°, V = 1658.7(19) Å3, Z = 2; rcalc = 1.336 g/cm3; m = 0.864 mm–1; F(000) = 680.0; collection area by 2q: 5.988-54.57°; total reflections 35142; independent reflections 7353 (Rint = 0.0683); GOOF = 1.065; R-factor 0.0419]. The antimony atoms in the complexes have a distorted trigonal-bipyramidal coordination with the oxygen atom of the carboxyl group in the axial position.