Tetra(para-tolyl)antimony carboxylates p-Tol4SbOC(O)Ar; Ar = C6H3(NO2)2-3;5; C6H4Br-3; C6H4I-4. Synthesis and structural features

Abstract

Tetra(para-tolyl)antimony carboxylates p-Tol4SbOC(O)Ar, Ar = C6H3(NO2)2-3.5 (1), C6H4Br-3 (2), C6H4I-4 (3) were synthesized from equimolar amounts of penta(para-tolyl)antimony and carboxylic acid in benzene at room temperature. According to X-ray diffraction analysis performed at 293 K on a D8 Quest Bruker automatic four-circle diffractometer (two-coordinate CCD detector, Мо Кα-radiation, λ = 0,71073 Å, graphite monochromator), antimony atoms in crystals of 1 [C35H31N2O6Sb, M 697,38; monoclinic syngony, symmetry group Р21/n; cell parameters: a = 10,248(7), b = 10,801(7), c = 29,10(2) Å;  = 90, β = 92,60(3),  = 90 degrees; V = 3218(2) Å3; crystal size 0,4×0,31×0,07 mm; reflection index intervals –13 ≤ h ≤ 13, –13 ≤ k ≤ 13, –37 ≤ l ≤ 37; total reflections 105827; independent reflections 7128; Rint 0,0415; GOOF 1,061; R1 = 0,0250, wR2 = 0,0564; residual electron density 0,41/0,61 e/Å3], 2 [C35H32O2BrSb, M 686,27; triclinic syngony, symmetry group P1 ̅; cell parameters: a = 10,114(7), b = 11,548(6), c = 13,889(9) Å;  = 99,16(3), β = 94,63(3),  = 107,97(3) degrees; V = 1508,7(17) Å3; crystal size 0,48×0,4×0,32 mm; reflection index intervals –17 ≤ h ≤ 17, –19 ≤ k ≤ 19, –23 ≤ l ≤ 23; total reflections 97427; independent reflections 15399; Rint 0,0506; GOOF 1,015; R1 = 0,0454, wR2 = 0,0936; residual electron density 0,89/1.55 e/Å3], 3 [C35H32O2SbI, M 733,26; triclinic syngony, symmetry group P1 ̅; cell parameters: a = 10,008(6), b = 11,472(7), c = 15,534(9) Å;  = 68,92(3), β = 85,72(3),  = 70,37(2) degrees; V = 1565,4(15) Å3; crystal size 0,43×0,28×0,09 mm; reflection index intervals –14 ≤ h ≤ 13, –16 ≤ k ≤ 16, –22 ≤ l ≤ 22; total reflections 85719; independent reflections 10417; Rint 0,0295; GOOF 1,036; R1 = 0,0366, wR2 = 0,0933; residual electron density 1,18/2,19 e/Å3], have distorted trigonal bipyramidal coordination with carbon and oxygen atoms in axial positions (axial angles are 174,83(6) for 1, 174,44(6)° for 2, 178,86(8)° for 3). The SbO distances are 2,3469(17) Å for 1, 2,2984(18) Å for 2 and 2,277(2) Å for 3. The SbC bond lengths vary in a narrow range of values (2,113(2)2,152(2) Å for 1, 2,104(2)2,171(2) Å for 2, 2,111(2)2,161(3) Å for 3). The structural organization in crystal 1 is due to weak intermolecular contacts C=O•••H (2,58 Å), NO•••H (2,58–2,63 Å). Crystal 2 contains intermolecular contacts Br•••Н (2,95 Å) and С=О•••Sb (3,080 Å). In crystal 3 the carbonyl oxygen atom is weakly coordinated with the metal atom (С=О•••Sb 3,470 Å). Complete tables of atomic coordinates, bond lengths, and bond angles for the structures were deposited at the Cambridge Crystallographic Data Center (no. 2213730 for 1, no. 2221986 for 2, no. 2222094 for 3; deposit@ccdc.cam.ac.uk; https://www. ccdc.cam.ac.uk).