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)](3)Bi[OC(O)CHal(3)](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)A degrees (II) and 171.6(2)A degrees (III); equatorial CBiC angles are 118.0(3)A degrees-123.1(3)A degrees (II) and 113.6(3)A degrees-127.4(3)A degrees (III). Bi-C bond lengths are 2.189(7)-2.200(8) (II) and 2.190(8)-2.219(7) (III), and Bi-D distances are 2.280(6), 2.459(16) (II) and 2.264(5), 2.266(5) (III). Intramolecular contacts between the central atom and the oxygen atoms of carbonyl groups (Bi center dot center dot center dot O 3.028(9), 3.162(9) (II); 3.117(9), 3.202(9) (III)) are observed at maximum equatorial angles. The oxygen atoms of methoxy groups are coordinated to the bismuth atom. The Bi center dot center dot center dot 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) , respectively) are slightly longer than in complex I (3.007(9)-3.136(4) ).