Structure of organic and organoelemental compounds. Part 7

Abstract

Ionic derivatives of phosphorus [Ph3P(CH2)3Br]Br (1), [Ph3P(CH2)4Br]Br (2), [Ph3PCH2OMe][I3] (3), and [Ph3PCH2C(O)CH3][I3] (4) were synthesized by the interaction of tetraorganylphosphonium halides with halogens in benzene; they were structurally characterized. In phosphonium cations of these derivatives, the phosphorus atoms have a distorted tetragonal coordination. At the equimolar ratio of the initial reagents, derivatives with mononuclear anions are formed. In the case of tetraorganylphosphonium iodides, ionic complexes with trinuclear anions are formed at an excess of iodine. According to the X-ray diffraction data: 1 C42H42Br4P2, M 928.22; triclinic syngony, symmetry group P-1; cell parameters: a = 10.19(3), b = 11.20(3), c = 17.54(5) Å;  = 74.32(11), β = 89.27(15),  = 88.21(16); V = 1928(9) Å3, Z = 2, calc = 1.599 g/cm3,  = 4.288 mm1, F(000) = 928.0, 2θ data acquisition range, deg: 6.2657.5, crystal size 0.6×0.25×0.16 mm; reflection index ranges –13 ≤ h ≤ 13, –14 ≤ k ≤ 14, –23 ≤ l ≤ 23; total reflections 70337; independent reflections 9609; Rint 0.0403; GOOF 1.052; R1 = 0.0877, wR2 = 0.2667; residual electron density 2.26/–3,.9 e/Å3; 2 C22H23PBr2, M 478.19; monoclinic syngony, symmetry group P21/c; cell parameters: a = 12.144(13), b = 10.411(9), c = 17.21(2) Å; β = 105.40(7); V = 2097(4) Å3, Z = 4, calc = 1.514 g/cm3,  = 3.943 mm1, F(000) = 960.0, 2θ data acquisition range, deg: 6.1650.32, crystal size 0.41×0.19×0.14 mm; reflection index ranges –14 ≤ h ≤ 14, –12 ≤ k ≤ 12, –18 ≤ l ≤ 20; total reflections 15973; independent reflections 3698; Rint 0.0910; GOOF 1.041; R1 = 0.0544, wR2 = 0.1490; residual electron density 1.54/–1.42 e/Å3; 3 C40H40I6O2P2, M 1376.06; monoclinic syngony, symmetry group P21/c; cell parameters: a = 17.5087(8), b = 8.0263(3), c = 17.6892(8) Å; β = 113.365(5); V = 2282.02(17) Å3, Z = 2, calc = 2.003 g/cm3,  = 4.185 mm1, F(000) = 1288,0, 2θ data acquisition range, deg: 6.4655, crystal size 0.4×0.16×0.05 mm; reflection index ranges –22 ≤ h ≤ 22, –10 ≤ k ≤ 10, –22 ≤ l ≤ 22; total reflections 13867; independent reflections 5243; Rint 0.0315; GOOF 1.041; R1 = 0.0240, wR2 = 0.0456; residual electron density 0.88/–0.53 e/Å3; 4 C21H20OPI3, M 700.04; monoclinic syngony, symmetry group P21/n; cell parameters: a = 10.313(16), b = 13.276(17), c = 17,23(3) Å; β = 93.96(8); V = 2354(6) Å3, Z = 4, calc = 1.976 g/cm3,  = 4.060 mm−1, F(000) = 1312.0, data collection range for 2θ, deg: 6.14−54.34, crystal size 0.28×0.28×0.07 mm; reflection index ranges –13 ≤ h ≤ 13, –16 ≤ k ≤ 16, –22 ≤ l ≤ 22; total reflections 43863; independent reflections 5197; Rint 0.1525; GOOF 1.074; R1 = 0.0567, wR2 = 0.1330; residual electron density 1.85/–1.79 e/Å3. The complete tables of atomic coordinates, bond lengths, and bond angles for the structures have been deposited with the Cambridge Crystallographic Data Centre [No. 2420741 (1), 2419560 (2), 2362565 (3), 2332655 (4); deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).