Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100001566/qb0179sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100001566/qb0179Isup2.hkl |
CCDC reference: 143332
In the recrystallization of dihalogenobis(tribenzylphosphine)nickel(II) from dichloromethane–butanol (1:1) under an oxygen atmosphere (Pérez et al., 1998), colorless needles of the title compound were obtained.
H atoms were calculated geometrically and included in the refinement, but were restrained to ride on their parent atoms. The isotropic displacement parameters of the H atoms were fixed to 1.3 times Ueq of their parent atoms.
Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: PARST (Nardelli, 1983).
C21H21OP | Dx = 1.211 Mg m−3 |
Mr = 320.35 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 30 reflections |
a = 16.685 (2) Å | θ = 13.8–27.9° |
c = 5.468 (1) Å | µ = 0.16 mm−1 |
V = 1318.3 (3) Å3 | T = 293 K |
Z = 3 | Prism, colourless |
F(000) = 510 | 0.56 × 0.32 × 0.20 mm |
Stoe STADI-4 four-circle diffractometer | Rint = 0.035 |
ω scans | θmax = 24.9° |
Absorption correction: ψ scan (EMPIR; Stoe & Cie, 1992) | h = −19→19 |
Tmin = 0.913, Tmax = 0.969 | k = −19→19 |
5177 measured reflections | l = 0→6 |
578 independent reflections | 2 standard reflections every 60 min |
558 reflections with F2 > 2σ(F2) | intensity decay: 0.0% |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0568P)2 + 0.3906P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.032 | (Δ/σ)max = 0.001 |
wR(F2) = 0.088 | Δρmax = 0.11 e Å−3 |
S = 1.07 | Δρmin = −0.12 e Å−3 |
578 reflections | Absolute structure: Flack (1983) |
70 parameters | Absolute structure parameter: 0.1 (2) |
C21H21OP | Z = 3 |
Mr = 320.35 | Mo Kα radiation |
Trigonal, R3 | µ = 0.16 mm−1 |
a = 16.685 (2) Å | T = 293 K |
c = 5.468 (1) Å | 0.56 × 0.32 × 0.20 mm |
V = 1318.3 (3) Å3 |
Stoe STADI-4 four-circle diffractometer | 558 reflections with F2 > 2σ(F2) |
Absorption correction: ψ scan (EMPIR; Stoe & Cie, 1992) | Rint = 0.035 |
Tmin = 0.913, Tmax = 0.969 | 2 standard reflections every 60 min |
5177 measured reflections | intensity decay: 0.0% |
578 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.088 | Δρmax = 0.11 e Å−3 |
S = 1.07 | Δρmin = −0.12 e Å−3 |
578 reflections | Absolute structure: Flack (1983) |
70 parameters | Absolute structure parameter: 0.1 (2) |
Refinement. The structure was solved by direct methods and Fourier synthesis. Non-H atoms were refined anisotropically by full-matrix least-squares techniques. H atoms were calculated geometrically and included in the refinement, but were restrained to ride on their parent atoms. The isotropic displacement parameters of the H atoms were fixed to 1.3 times Ueq of their parent atoms. |
x | y | z | Uiso*/Ueq | ||
P1 | 1.00000 | 0.00000 | 0.06651 (14) | 0.0428 (3) | |
O1 | 1.00000 | 0.00000 | −0.2056 (7) | 0.0642 (9) | |
C3 | 1.01310 (19) | 0.10515 (19) | 0.2058 (6) | 0.0506 (8) | |
C4 | 0.9339 (2) | 0.1221 (2) | 0.1568 (5) | 0.0519 (9) | |
C5 | 0.8622 (3) | 0.0922 (2) | 0.3190 (10) | 0.0762 (13) | |
C6 | 0.7891 (3) | 0.1080 (4) | 0.2739 (16) | 0.114 (3) | |
C7 | 0.7875 (5) | 0.1520 (7) | 0.0731 (18) | 0.148 (3) | |
C8 | 0.8578 (7) | 0.1819 (7) | −0.0891 (11) | 0.155 (4) | |
C9 | 0.9323 (5) | 0.1680 (5) | −0.0499 (8) | 0.103 (2) | |
H3A | 1.01956 | 0.10175 | 0.38120 | 0.0657* | |
H3B | 1.06973 | 0.15761 | 0.14544 | 0.0657* | |
H5 | 0.86227 | 0.06121 | 0.46020 | 0.0992* | |
H6 | 0.74078 | 0.08742 | 0.38572 | 0.1484* | |
H7 | 0.73836 | 0.16213 | 0.04435 | 0.1925* | |
H8 | 0.85624 | 0.21242 | −0.22991 | 0.2022* | |
H9 | 0.98054 | 0.18960 | −0.16231 | 0.1348* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0441 (4) | 0.0441 (4) | 0.0402 (5) | 0.0221 (2) | 0.0000 | 0.0000 |
O1 | 0.0738 (14) | 0.0738 (14) | 0.045 (2) | 0.0369 (7) | 0.0000 | 0.0000 |
C3 | 0.0493 (14) | 0.0433 (14) | 0.0576 (16) | 0.0220 (11) | −0.0052 (13) | −0.0040 (12) |
C4 | 0.0550 (16) | 0.0497 (14) | 0.0550 (17) | 0.0291 (12) | −0.0057 (13) | −0.0100 (13) |
C5 | 0.066 (2) | 0.0575 (17) | 0.105 (3) | 0.0307 (16) | 0.020 (2) | −0.0084 (19) |
C6 | 0.054 (2) | 0.092 (3) | 0.191 (7) | 0.033 (2) | −0.001 (3) | −0.059 (4) |
C7 | 0.138 (5) | 0.204 (7) | 0.178 (6) | 0.143 (6) | −0.101 (5) | −0.130 (6) |
C8 | 0.253 (9) | 0.266 (9) | 0.085 (3) | 0.233 (9) | −0.043 (5) | −0.035 (5) |
C9 | 0.155 (4) | 0.159 (5) | 0.066 (2) | 0.131 (4) | 0.005 (3) | 0.011 (3) |
P1—O1 | 1.488 (4) | C5—H5 | 0.930 |
P1—C3 | 1.823 (3) | C6—C7 | 1.33 (1) |
C4—C3 | 1.508 (6) | C6—H6 | 0.930 |
C4—C5 | 1.367 (5) | C9—C8 | 1.39 (2) |
C4—C9 | 1.373 (7) | C9—H9 | 0.930 |
C3—H3A | 0.970 | C7—C8 | 1.35 (1) |
C3—H3B | 0.970 | C7—H7 | 0.930 |
C5—C6 | 1.392 (8) | C8—H8 | 0.930 |
O1—P1—C3 | 114.7 (1) | C5—C6—C7 | 120.8 (7) |
C3—C4—C5 | 120.4 (3) | C5—C6—H6 | 119.6 |
C3—C4—C9 | 120.9 (4) | C7—C6—H6 | 119.6 |
C5—C4—C9 | 118.7 (4) | C4—C9—C8 | 119.2 (6) |
P1—C3—C4 | 114.3 (2) | C4—C9—H9 | 120.4 |
P1—C3—H3A | 108.7 | C8—C9—H9 | 120.4 |
P1—C3—H3B | 108.7 | C6—C7—C8 | 119.6 (9) |
C4—C3—H3A | 108.7 | C6—C7—H7 | 120.2 |
C4—C3—H3B | 108.7 | C8—C7—H7 | 120.2 |
H3A—C3—H3B | 107.6 | C9—C8—C7 | 121 (1) |
C4—C5—C6 | 120.4 (4) | C9—C8—H8 | 119.3 |
C4—C5—H5 | 119.8 | C7—C8—H8 | 119.3 |
C6—C5—H5 | 119.8 | ||
O1—P1—C3—C4 | 65.0 (3) | C4—C5—C6—C7 | 0 (1) |
O1—P1—C3—H3A | −173.4 | C4—C5—C6—H6 | −179.9 |
O1—P1—C3—H3B | −56.6 | H5—C5—C6—C7 | −179.9 |
C5—C4—C3—P1 | 93.6 (4) | H5—C5—C6—H6 | 0.1 |
C5—C4—C3—H3A | −27.9 | C5—C6—C7—C8 | 0 (1) |
C5—C4—C3—H3B | −144.8 | C5—C6—C7—H7 | 179.9 |
C9—C4—C3—P1 | −86.7 (4) | H6—C6—C7—C8 | 179.9 |
C9—C4—C3—H3A | 151.7 | H6—C6—C7—H7 | −0.1 |
C9—C4—C3—H3B | 34.9 | C4—C9—C8—C7 | 1 (1) |
C3—C4—C5—C6 | 179.9 (4) | C4—C9—C8—H8 | −179.3 |
C3—C4—C5—H5 | −0.1 | H9—C9—C8—C7 | −179.3 |
C9—C4—C5—C6 | 0.3 (7) | H9—C9—C8—H8 | 0.7 |
C9—C4—C5—H5 | −179.8 | C6—C7—C8—C9 | 0 (1) |
C3—C4—C9—C8 | 179.7 (6) | C6—C7—C8—H8 | 179.7 |
C3—C4—C9—H9 | −0.3 | H7—C7—C8—C9 | 179.7 |
C5—C4—C9—C8 | −0.6 (9) | H7—C7—C8—H8 | −0.3 |
C5—C4—C9—H9 | 179.4 |
Experimental details
Crystal data | |
Chemical formula | C21H21OP |
Mr | 320.35 |
Crystal system, space group | Trigonal, R3 |
Temperature (K) | 293 |
a, c (Å) | 16.685 (2), 5.468 (1) |
V (Å3) | 1318.3 (3) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 0.16 |
Crystal size (mm) | 0.56 × 0.32 × 0.20 |
Data collection | |
Diffractometer | Stoe STADI-4 four-circle diffractometer |
Absorption correction | ψ scan (EMPIR; Stoe & Cie, 1992) |
Tmin, Tmax | 0.913, 0.969 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 5177, 578, 558 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.592 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.088, 1.07 |
No. of reflections | 578 |
No. of parameters | 70 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.11, −0.12 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.1 (2) |
Computer programs: DIF4 (Stoe & Cie, 1992), DIF4, REDU4 (Stoe & Cie, 1992), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), PARST (Nardelli, 1983).
P1—O1 | 1.488 (4) | C4—C3 | 1.508 (6) |
P1—C3 | 1.823 (3) | ||
O1—P1—C3 | 114.7 (1) | C3—C4—C9 | 120.9 (4) |
C3—C4—C5 | 120.4 (3) | P1—C3—C4 | 114.3 (2) |
O1—P1—C3—C4 | 65.0 (3) | C9—C4—C3—P1 | −86.7 (4) |
C5—C4—C3—P1 | 93.6 (4) |
The title compound, (I), is an organic phosphorus compound that belongs to a type of tertiary phosphine oxides. In the final stages of the synthesis of dihalogenobis(tribenzylphosphine)nickel(II) complexes (Pérez et al., 1998), (I) was isolated as colourless needles, possibly formed by an oxidation process due to atmospheric oxygen. The P—O distance agrees with the mean distance of 1.50 Å calculated by Bye et al. (1982), based on 62 Ph3PO fragments. The P—C and C—C distances are similar to those found in compounds with tribenzylphosphine groups (Kilbourn & Powell, 1970). The two torsion angles P1—C3—C4—Ci (i = 5 and 9) show that the three benzyl groups differ by aproximatelly 180°. The molecules are packed at normal van der Waals distances.