CRYSTAL-STRUCTURES OF 10-SB-5 HYPERVALENT ORGANOANTIMONY HALIDES BEARING A BIDENTATE LIGAND (MARTIN LIGAND)

X-Ray structural analyses of stable 10-Sb-5 halides, (o-C6H4C(CF3)(2)O )Sb(p-CH3C6H4)(2)X (3a: X=F, 3b: X=Cl, 3c: X=Br, 3d: X=I), showed mono meric distorted trigonal bipyramidal structures with an apical O-Sb-ha logen bond. The bond lengths of the apical Sb-O bond {2.059(2) Angstro m in 3a, 2.055(1) Angstrom in 3b, 2.053(5) Angstrom in 3c, 2.056(2) An gstrom in 3d} are almost the same (2.056+/-0.003 Angstrom) and are muc h shorter than the corresponding Sb-O bond (2.150(1) Angstrom) in (o-C 6H4C(CF3)(2)O)Sb(p-CH3C6H4)(3) (2). NMR (CDCl3) of 3a-d suggest that t he solution structures of these compounds are essentially the same as those in the solid state. Single-crystal data are as follows: (3a), tr iclinic, <P(1)over bar>, with a = 8.880(2) Angstrom, b = 10.928(2) Ang strom, c = 11.856(2) Angstrom, alpha = 97.56(1)degrees, beta = 93.60(2 )degrees, gamma = 98.23(2)degrees, V = 1124.9(4) Angstrom(3), Z = 2, D calc = 1.67 g cm(-3), 4212 observed reflections, and R = 0.036, Rw = 0 .039; (3b), triclinic, <P(1)over bar>, with a = 9.307(2) Angstrom, b = 10.561(2) Angstrom, c = 11.886(4) Angstrom, alpha = 98.77(2)degrees, beta = 92.02(3)degrees, gamma = 97.63(2)degrees, V = 1142.6(6) Angstro m(3), Z = 2, Dcalc = 1.69 g cm(-3), 4876 observed reflections, and R = 0.022, Rw = 0.027; (3c), triclinic, <P(1)over bar>, with a = 9.510(8) Angstrom, b = 10.43(1) Angstrom, c = 11.92(1) Angstrom, alpha = 99.71 (8)degrees, beta = 91.95(8)degrees, gamma = 98.08(8)degrees, V = 1152( 2) Angstrom(3), Z = 2, Dcalc = 1.80 g cm(-3), 4253 observed reflection s, and R = 0.075, Rw = 0.097; (3d), triclinic, <P(1)over bar>, with a = 9.374(1) Angstrom, b = 10.588(2) Angstrom, c = 12.596(2) Angstrom, a lpha = 98.22(1)degrees, beta = 99.32(1)degrees, gamma = 105.19(1)degre es, V = 1167.7(2) Angstrom(3), Z = 2, Dcalc = 1.91 g cm(-3), 4640 obse rved reflections, and R = 0.027, Rw = 0.023.