Tris(5-bromo-2-methoxyphenyl)bismuth dicarboxylates [(C6H3(Br-5)(MeO-2)]3Bi[OC(O)CHal3]2 (Hal = F,Cl): synthesis and structure

Tris(5-bromo-2-methoxyphenyl)bismuth dicarboxylates [(C₆H₃(Br-5)(MeO-2)]₃Bi[OC(O)CHal₃]₂, Hal = F (II) and Cl (III), have been synthesized by the reaction between tris(5-bromo-2-methoxyphenyl)bismuth (I) and trifluoroacetic acid and thrichloroacetic acid, respectively, in the presence of hydrogen peroxide in ether. According to X-ray diffraction data, a crystal of complex I contains two types of crystallographically independent molecules (a and b) both with a trigonal pyramid configuration. The bismuth atoms in complexes II and III have a distorted trigonal bipyramidal coordination with carboxylate substituents in axial positions. Axial OBiO angles are 166.3(3)° (II) and 171.6(2)° (III); equatorial CBiC angles are 118.0(3)°–123.1(3)° (II) and 113.6(3)°–127.4(3)° (III). Bi–C bond lengths are 2.189(7)–2.200(8) Å (II) and 2.190(8)–2.219(7) Å (III), and Bi–О distances are 2.280(6), 2.459(16) Å (II) and 2.264(5), 2.266(5) Å (III). Intramolecular contacts between the central atom and the oxygen atoms of carbonyl groups (Bi···O 3.028(9), 3.162(9) Å (II); 3.117(9), 3.202(9) Å (III)) are observed at maximum equatorial angles. The oxygen atoms of methoxy groups are coordinated to the bismuth atom. The Bi···O distances in complexes II and III (3.028(16), 3.157(16), 3.162(16) and 3.17(16), 3.143(16), 3.202(16) Å, respectively) are slightly longer than in complex I (3.007(9)–3.136(4) Å).