Structure of tri(para-tolyl)bismuth dicarboxylates p-Tol3Bi[OC(O)CH2Cl]2 and p-Tol3Bi[OC(O)C6H3F2-2,5]2 ∙ TolH

Abstract

By reacting tri(para-tolyl)bismuth with chloroacetic and 2,5-difluorobenzoic acids in ether in the presence of tert-butyl hydroperoxide, tri(para-tolyl)bismuth dicarboxylates were synthesized. After recrystallization from toluene, they were isolated as p-Tol3Bi[OC(O)CH2Cl]2 (1) and solvate p-Tol3Bi[OC(O)C6H3F2-2,5]2 ∙ TolH (2), the structure of which was proven by X-ray diffraction analysis (XRD). Crystallographic characteristics of 1 [C25H25O4Сl2Bi, M = 669,33; triclinic syngony, space group P-1; cell parameters: a = 10,370(6) Å, b = 11,731(4) Å, c = 12,746(6) Å;  = 106,77(2), β = 103,90(2),  = 108,764(18), V = 1307,5(10) Å3, Z = 2; calc = 1,700 g/cm3;  = 6,973 mm–1; F(000) = 648,0; region collection at 2q: 6,34–71,62; –17 ≤ h ≤ 17, –19 ≤ k ≤ 19, –20 ≤ l ≤ 20; total reflections 83762; independent reflections 12095 (Rint = 0,0546); GOOF = 1,035; R-factor = 0,0353], 2 [C42H35BiF4O4, M = 888,68; triclinic syngony, space group P–1; cell parameters: a = 9,403(4) Å, b = 11,009(6) Å, c = 18,757(8) Å;  = 78,80(2), β = 88,918(17),  = 66,61(2), V = 1744,5(15) Å3, Z = 2; calc = 1,692 g/cm3;  = 5,118 mm–1; F(000) = 876,0; collection area by 2q: 6,22–54,362; –12 ≤ h ≤ 12, –14 ≤ k ≤ 14, –24 ≤ l ≤ 24; total reflections 40062; independent reflections 7698 (Rint = 0,0337); GOOF = 1,054; [R-factor = 0,0268]. From the X-ray diffraction data it follows that the bismuth atoms in 1 and 2 have a distorted trigonal-bipyramidal coordination with the oxygen atoms of the carboxyl groups in the axial positions (OBiO 170,91(6) and 170,49(15), respectively; BiO 2,2875(19) Å, 2,292(2) Å for 1 and 2,262(3) Å, 2,317(3) Å for 2) and equatorial tolyl ligands (BiC 2,188(3)2,210(2) Å for 1 and 2,198(4)2,219(4) Å for 2). The presence of a coordination bond between the central metal atom and the carbonyl oxygen atom [Bi∙∙∙O=C 2,991(3) Å, 2,997(3) Å in 1 and 2,879(3) Å, 2,922(3) Å in 2] allows us to speak about an increase in the coordination number of the bismuth atom to 7. In structures 1 and 2, the maximum equatorial angle on the side of the Bi∙∙∙O=C contact (139,21(9) and 142,18(15)) is significantly larger than the other two equatorial angles. Complete tables of atomic coordinates, bond lengths and bond angles for compounds 1 and 2 have been deposited with the Cambridge Crystallographic Data Centre (CCDC 1913595 and 2051942; depos-it@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).