Donor-Akzeptor-Komplexe von Halogenidionen mit 1.4-Diiodtetrafluorbenzol/Donor-Acceptor Complexes of Halide Ions with 1,4-Diiodotetrafluorobenzene

Abstract

(Ph4P)X as well as (Me4N)X (X = Cl, Br, I) react with 1,4-diiodotetrafluorobenzene in CH2C12 and CH3CN solutions, respectively, to give the donoracceptor complexes (Ph4PM (C6F4I2)Cl2]·4 CH2Cl2 (1), (Ph4P)2[(C6F4I2)Br2]·2 CH2Cl2 (2), (Me4N)[(C6F4I2)Cl] (3), (Me4N)[(C6F4I2)Br]·CH3CN (4), (Ph4P)2[(C6F4I2)3Br2]·4CH2Cl2 (5), (Ph4P)2[(C6F4I2)3I2] (6) and (Me4N)2[(C6F4I2)3I2] (7). All complexes have been characterized by single X-ray crystallographic structure determinations. 1: Space group P1̄, Z = 1, lattice dimensions at 203 K: a = 1090.2(1), b = 1206.2(1), c = 1242.8(1) pm, α = 91,84(1)°, β = 106.60(1)°, γ = 99.84(1)°. 2: Space group P1̄, Z = 1, lattice dimensions at 233 K: a = 1129.7(2), b = 1183.9(1), c = 1293.4(1) pm, α = 65.52(1)°, β = 65.74(1)°, γ = 89.02(1)°. 3: Space group P21/n, Z = 4, lattice dimensions at 243 K: a = 714.8(1), b = 2405.7(3), c = 930.8(1) pm, β = 96.38(1)°. 4: Space group P21/c, Z = 4, lattice dimensions at 203 K: a = 1400.8(1), b = 1669.9(2), c = 795.9(1) pm, β = 102.81(1)°. 5: Space group Pbca, Z = 4, lattice dimensions at 223 K: a = 2106.0(4), b = 1566.8(3), c = 2445.8(4) pm. 6 : Space group P1̄, Z = 1, lattice dimensions at 203 K: a = 1150.9(1), b = 1278.9(1), c = 1292.9(2) pm, α = 65.47(1)°, β = 82.07(1)°, γ = 83.62(1)°. 7: Space group Pbca, Z = 4, lattice dimensions at 223 K: a = 1210.5(5), b = 1429.0(6), c = 2470.3(12) pm. In all complexes the acceptor molecule C6F4I2 coordinates with the halide donor ions in linear arrangements C-I· · ·X- . In 1 and 2 the halide ions act as terminal donors to form the dianionic species [X· · ·I-C6F4-I· · ·X]2- (X = Cl, Br). Complexes 3 and 4 form polymeric anionic zigzag chains with μ-X- bridges and bond angles I· · ·Cl· · ·I of 77.2° and I· · ·Br· · ·I of 74.3°. Complexes 5 - 7 are characterized by three-dimensional anionic networks via /x3-X- bridging halide ions and μ-bridging 1,4-diiodotetrafluorobenzene molecules.