Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680101203X/cf6089sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680101203X/cf6089Isup2.hkl |
CCDC reference: 172212
All commercially available reagents were used as supplied. 1H NMR spectra were obtained from CDCl3 solution using TMS as internal standard on a Bruker DRX 200 instrument. FT—IR spectra were measured by a Nicolet 1795X FT—IR spectrophotometer. Elemental analyses were performed on a Carlo-Erba 1106 elemental analyser. The compound [Ph2P(CH2)3N=CH]C6H5 was prepared by the reaction between Ph2P(CH2)3NH2 and benzaldehyde in the presence of molecular sieves in benzene according to previously described procedures (Blinn et al., 1990); m.p. 79–80° 1H NMR (CDCl3, 200 MHz): p.p.m. 8.26 (s, 1H, –N=CH), 7.71–7.73 (m, 15H, Ph), 3.70 (t, 2H, –CH2—N), 2.10 (t, 2H, –P—CH2), 1.88 (m, 2H, –CH2—CH2—CH2). IR (KBr) cm-1 1574, 1478 (C=C), 1697 (C=N) 1492 (C—P). Anal. Calcd: C, 79.74; H, 6.69; N, 4.23. Found: C, 79.57; H, 6.43; N, 4.18.
Data collection: CAD-4-PC Software (Enraf-Nonius, 1989); cell refinement: CAD-4-PC Software; data reduction: TEXSAN (Molecular Structure Corporation, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecule with labelling of the non-H atoms and 30% probability ellipsoids. | |
Fig. 2. A view of the packing. |
C22H22NP | Dx = 1.209 Mg m−3 |
Mr = 331.38 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 5.768 (2) Å | θ = 15.1–15.9° |
b = 17.702 (3) Å | µ = 0.15 mm−1 |
c = 17.823 (4) Å | T = 293 K |
V = 1819.8 (8) Å3 | Prismatic, colourless |
Z = 4 | 0.4 × 0.3 × 0.2 mm |
F(000) = 704 |
Enraf-Nonius CAD-4 diffractometer | 3014 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 25.0°, θmin = 1.6° |
ω/2θ scans | h = −6→6 |
Absorption correction: ψ scan (North et al., 1968) | k = −20→21 |
Tmin = 0.946, Tmax = 0.970 | l = −20→21 |
3202 measured reflections | 5 standard reflections every 300 reflections |
3202 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.06P)2 + 0.35P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
3202 reflections | Δρmax = 0.29 e Å−3 |
217 parameters | Δρmin = −0.10 e Å−3 |
0 restraints | Absolute structure: Flack (1983); 1327 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.09 (10) |
C22H22NP | V = 1819.8 (8) Å3 |
Mr = 331.38 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.768 (2) Å | µ = 0.15 mm−1 |
b = 17.702 (3) Å | T = 293 K |
c = 17.823 (4) Å | 0.4 × 0.3 × 0.2 mm |
Enraf-Nonius CAD-4 diffractometer | 3014 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.946, Tmax = 0.970 | 5 standard reflections every 300 reflections |
3202 measured reflections | intensity decay: none |
3202 independent reflections |
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.099 | Δρmax = 0.29 e Å−3 |
S = 1.05 | Δρmin = −0.10 e Å−3 |
3202 reflections | Absolute structure: Flack (1983); 1327 Friedel pairs |
217 parameters | Absolute structure parameter: −0.09 (10) |
0 restraints |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
P1 | 1.24508 (8) | 1.32205 (3) | 1.15104 (2) | 0.05096 (14) | |
N1 | 1.7355 (3) | 1.47800 (8) | 1.00822 (8) | 0.0599 (4) | |
C1 | 1.5757 (3) | 1.20181 (11) | 1.14927 (11) | 0.0548 (4) | |
H1B | 1.6708 | 1.2320 | 1.1196 | 0.080* | |
C2 | 1.6446 (4) | 1.12841 (11) | 1.16820 (13) | 0.0636 (5) | |
H2A | 1.7849 | 1.1097 | 1.1504 | 0.080* | |
C3 | 1.5090 (4) | 1.08447 (12) | 1.21209 (12) | 0.0681 (6) | |
H3A | 1.5567 | 1.0358 | 1.2243 | 0.080* | |
C4 | 1.2995 (5) | 1.11147 (12) | 1.23889 (12) | 0.0733 (7) | |
H4A | 1.2074 | 1.0817 | 1.2699 | 0.080* | |
C5 | 1.2299 (4) | 1.18282 (10) | 1.21900 (11) | 0.0599 (5) | |
H5A | 1.0871 | 1.2004 | 1.2357 | 0.080* | |
C6 | 1.3654 (3) | 1.22925 (10) | 1.17491 (10) | 0.0485 (4) | |
C7 | 1.2363 (3) | 1.36542 (9) | 1.24433 (9) | 0.0478 (4) | |
C8 | 1.0424 (3) | 1.40853 (11) | 1.26416 (11) | 0.0559 (4) | |
H8A | 0.9231 | 1.4151 | 1.2297 | 0.080* | |
C9 | 1.0257 (4) | 1.44138 (11) | 1.33414 (12) | 0.0625 (5) | |
H9A | 0.8958 | 1.4699 | 1.3466 | 0.080* | |
C10 | 1.2000 (4) | 1.43205 (11) | 1.38502 (11) | 0.0618 (5) | |
H10A | 1.1881 | 1.4540 | 1.4323 | 0.080* | |
C11 | 1.3925 (4) | 1.39049 (12) | 1.36691 (11) | 0.0615 (5) | |
H11A | 1.5121 | 1.3851 | 1.4015 | 0.080* | |
C12 | 1.4084 (3) | 1.35677 (10) | 1.29746 (10) | 0.0523 (4) | |
H12A | 1.5378 | 1.3276 | 1.2861 | 0.080* | |
C13 | 1.4922 (3) | 1.37201 (11) | 1.10900 (10) | 0.0535 (4) | |
H13A | 1.4800 | 1.4254 | 1.1207 | 0.080* | |
H13B | 1.6345 | 1.3534 | 1.1313 | 0.080* | |
C14 | 1.5060 (4) | 1.36233 (11) | 1.02373 (10) | 0.0585 (5) | |
H14A | 1.5035 | 1.3089 | 1.0117 | 0.080* | |
H14B | 1.3708 | 1.3854 | 1.0009 | 0.080* | |
C15 | 1.7235 (4) | 1.39761 (10) | 0.99062 (10) | 0.0608 (5) | |
H15A | 1.8592 | 1.3723 | 1.0106 | 0.080* | |
H15B | 1.7232 | 1.3909 | 0.9366 | 0.080* | |
C16 | 1.9109 (4) | 1.50074 (11) | 1.04326 (10) | 0.0576 (5) | |
H16A | 2.0226 | 1.4654 | 1.0567 | 0.080* | |
C17 | 1.9500 (4) | 1.57962 (12) | 1.06419 (10) | 0.0563 (4) | |
C18 | 1.7897 (4) | 1.63596 (12) | 1.04701 (10) | 0.0615 (5) | |
H18A | 1.6529 | 1.6238 | 1.0222 | 0.080* | |
C19 | 1.8353 (4) | 1.71011 (12) | 1.06708 (12) | 0.0685 (6) | |
H19A | 1.7289 | 1.7478 | 1.0554 | 0.080* | |
C20 | 2.0387 (4) | 1.72848 (13) | 1.10443 (13) | 0.0706 (6) | |
H20A | 2.0682 | 1.7783 | 1.1178 | 0.080* | |
C21 | 2.1958 (4) | 1.67328 (14) | 1.12158 (14) | 0.0760 (6) | |
H21A | 2.3315 | 1.6853 | 1.1471 | 0.080* | |
C22 | 2.1516 (4) | 1.59971 (14) | 1.10068 (13) | 0.0680 (5) | |
H22A | 2.2607 | 1.5626 | 1.1115 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0468 (2) | 0.0558 (3) | 0.0503 (2) | −0.0015 (8) | −0.0055 (2) | −0.0044 (8) |
N1 | 0.0671 (10) | 0.0593 (8) | 0.0534 (8) | 0.0076 (9) | 0.0020 (9) | 0.0063 (7) |
C1 | 0.0475 (9) | 0.0543 (9) | 0.0627 (9) | −0.0016 (8) | −0.0059 (9) | −0.0041 (8) |
C2 | 0.0569 (11) | 0.0586 (10) | 0.0754 (12) | 0.0104 (9) | −0.0015 (10) | −0.0075 (9) |
C3 | 0.0880 (16) | 0.0532 (10) | 0.0631 (11) | 0.0031 (11) | −0.0043 (12) | −0.0044 (9) |
C4 | 0.0816 (19) | 0.0595 (11) | 0.0590 (11) | −0.0158 (12) | 0.0159 (12) | −0.0075 (9) |
C5 | 0.0583 (10) | 0.0575 (10) | 0.0639 (10) | −0.0068 (10) | 0.0111 (9) | −0.0140 (8) |
C6 | 0.0475 (9) | 0.0493 (8) | 0.0485 (8) | −0.0014 (7) | −0.0061 (7) | −0.0093 (7) |
C7 | 0.0481 (9) | 0.0418 (7) | 0.0534 (8) | −0.0002 (8) | 0.0032 (9) | 0.0007 (6) |
C8 | 0.0453 (9) | 0.0598 (10) | 0.0627 (11) | 0.0045 (8) | 0.0004 (9) | −0.0022 (9) |
C9 | 0.0564 (11) | 0.0535 (10) | 0.0778 (13) | 0.0038 (9) | 0.0088 (10) | −0.0086 (9) |
C10 | 0.0783 (15) | 0.0522 (10) | 0.0548 (10) | −0.0079 (10) | 0.0108 (10) | −0.0085 (8) |
C11 | 0.0691 (12) | 0.0624 (11) | 0.0530 (10) | −0.0033 (10) | −0.0078 (9) | −0.0013 (9) |
C12 | 0.0470 (10) | 0.0556 (9) | 0.0544 (9) | 0.0075 (8) | −0.0012 (8) | 0.0006 (8) |
C13 | 0.0581 (11) | 0.0554 (10) | 0.0469 (9) | −0.0021 (9) | −0.0004 (8) | 0.0007 (7) |
C14 | 0.0687 (12) | 0.0598 (10) | 0.0471 (9) | 0.0066 (9) | −0.0037 (9) | 0.0009 (8) |
C15 | 0.0685 (12) | 0.0620 (10) | 0.0519 (9) | 0.0067 (10) | 0.0070 (10) | −0.0065 (8) |
C16 | 0.0585 (11) | 0.0633 (11) | 0.0509 (10) | 0.0095 (9) | 0.0024 (9) | 0.0064 (8) |
C17 | 0.0574 (11) | 0.0632 (10) | 0.0484 (9) | 0.0097 (9) | 0.0084 (8) | 0.0074 (8) |
C18 | 0.0626 (12) | 0.0712 (11) | 0.0508 (9) | 0.0092 (10) | −0.0004 (9) | 0.0031 (8) |
C19 | 0.0795 (14) | 0.0591 (11) | 0.0670 (12) | 0.0161 (10) | 0.0036 (11) | 0.0003 (10) |
C20 | 0.0810 (15) | 0.0650 (12) | 0.0658 (12) | 0.0023 (11) | 0.0172 (12) | −0.0024 (10) |
C21 | 0.0674 (13) | 0.0809 (14) | 0.0796 (14) | −0.0055 (12) | 0.0045 (11) | −0.0025 (12) |
C22 | 0.0589 (11) | 0.0729 (13) | 0.0721 (12) | 0.0056 (10) | −0.0021 (10) | 0.0007 (10) |
P1—C7 | 1.8321 (17) | C11—C12 | 1.377 (3) |
P1—C6 | 1.8334 (19) | C11—H11A | 0.930 |
P1—C13 | 1.837 (2) | C12—H12A | 0.930 |
N1—C16 | 1.256 (3) | C13—C14 | 1.532 (2) |
N1—C15 | 1.459 (2) | C13—H13A | 0.970 |
C1—C6 | 1.384 (3) | C13—H13B | 0.970 |
C1—C2 | 1.400 (3) | C14—C15 | 1.521 (3) |
C1—H1B | 0.930 | C14—H14A | 0.970 |
C2—C3 | 1.352 (3) | C14—H14B | 0.970 |
C2—H2A | 0.930 | C15—H15A | 0.970 |
C3—C4 | 1.385 (3) | C15—H15B | 0.970 |
C3—H3A | 0.930 | C16—C17 | 1.463 (3) |
C4—C5 | 1.372 (3) | C16—H16A | 0.930 |
C4—H4A | 0.930 | C17—C22 | 1.379 (3) |
C5—C6 | 1.380 (3) | C17—C18 | 1.394 (3) |
C5—H5A | 0.930 | C18—C19 | 1.386 (3) |
C7—C12 | 1.380 (3) | C18—H18A | 0.930 |
C7—C8 | 1.399 (3) | C19—C20 | 1.388 (4) |
C8—C9 | 1.379 (3) | C19—H19A | 0.930 |
C8—H8A | 0.930 | C20—C21 | 1.367 (3) |
C9—C10 | 1.364 (3) | C20—H20A | 0.930 |
C9—H9A | 0.930 | C21—C22 | 1.378 (3) |
C10—C11 | 1.370 (3) | C21—H21A | 0.930 |
C10—H10A | 0.930 | C22—H22A | 0.930 |
C7—P1—C6 | 100.10 (8) | C14—C13—P1 | 113.02 (14) |
C7—P1—C13 | 100.94 (9) | C14—C13—H13A | 109.0 |
C6—P1—C13 | 103.42 (9) | P1—C13—H13A | 109.0 |
C16—N1—C15 | 117.25 (18) | C14—C13—H13B | 109.0 |
C6—C1—C2 | 119.64 (19) | P1—C13—H13B | 109.0 |
C6—C1—H1B | 120.2 | H13A—C13—H13B | 107.8 |
C2—C1—H1B | 120.2 | C15—C14—C13 | 112.46 (17) |
C3—C2—C1 | 120.6 (2) | C15—C14—H14A | 109.1 |
C3—C2—H2A | 119.7 | C13—C14—H14A | 109.1 |
C1—C2—H2A | 119.7 | C15—C14—H14B | 109.1 |
C2—C3—C4 | 120.4 (2) | C13—C14—H14B | 109.1 |
C2—C3—H3A | 119.8 | H14A—C14—H14B | 107.8 |
C4—C3—H3A | 119.8 | N1—C15—C14 | 110.87 (17) |
C5—C4—C3 | 118.9 (2) | N1—C15—H15A | 109.5 |
C5—C4—H4A | 120.5 | C14—C15—H15A | 109.5 |
C3—C4—H4A | 120.5 | N1—C15—H15B | 109.5 |
C4—C5—C6 | 122.0 (2) | C14—C15—H15B | 109.5 |
C4—C5—H5A | 119.0 | H15A—C15—H15B | 108.1 |
C6—C5—H5A | 119.0 | N1—C16—C17 | 123.85 (19) |
C5—C6—C1 | 118.39 (18) | N1—C16—H16A | 118.1 |
C5—C6—P1 | 116.83 (15) | C17—C16—H16A | 118.1 |
C1—C6—P1 | 124.72 (15) | C22—C17—C18 | 118.6 (2) |
C12—C7—C8 | 117.52 (16) | C22—C17—C16 | 119.75 (19) |
C12—C7—P1 | 123.80 (14) | C18—C17—C16 | 121.7 (2) |
C8—C7—P1 | 118.67 (15) | C19—C18—C17 | 119.7 (2) |
C9—C8—C7 | 120.94 (19) | C19—C18—H18A | 120.2 |
C9—C8—H8A | 119.5 | C17—C18—H18A | 120.2 |
C7—C8—H8A | 119.5 | C20—C19—C18 | 120.4 (2) |
C10—C9—C8 | 119.90 (19) | C20—C19—H19A | 119.8 |
C10—C9—H9A | 120.0 | C18—C19—H19A | 119.8 |
C8—C9—H9A | 120.0 | C21—C20—C19 | 120.0 (2) |
C11—C10—C9 | 120.37 (18) | C21—C20—H20A | 120.0 |
C11—C10—H10A | 119.8 | C19—C20—H20A | 120.0 |
C9—C10—H10A | 119.8 | C20—C21—C22 | 119.5 (2) |
C10—C11—C12 | 119.9 (2) | C20—C21—H21A | 120.3 |
C10—C11—H11A | 120.0 | C22—C21—H21A | 120.3 |
C12—C11—H11A | 120.0 | C17—C22—C21 | 121.8 (2) |
C11—C12—C7 | 121.35 (19) | C17—C22—H22A | 119.1 |
C11—C12—H12A | 119.3 | C21—C22—H22A | 119.1 |
C7—C12—H12A | 119.3 |
Experimental details
Crystal data | |
Chemical formula | C22H22NP |
Mr | 331.38 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 5.768 (2), 17.702 (3), 17.823 (4) |
V (Å3) | 1819.8 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.946, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3202, 3202, 3014 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.099, 1.05 |
No. of reflections | 3202 |
No. of parameters | 217 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.10 |
Absolute structure | Flack (1983); 1327 Friedel pairs |
Absolute structure parameter | −0.09 (10) |
Computer programs: CAD-4-PC Software (Enraf-Nonius, 1989), CAD-4-PC Software, TEXSAN (Molecular Structure Corporation, 1989), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Phosphines are among the most common ancillary ligands for transition metal complexes with the result that there are many reported systems (Newkome, 1993a,b; Uriarte et al., 1980). Ligands possessing both softer donor phosphines and harder donor nitrogen or oxygen sites have been studied extensively because they not only stabilize homobimetallic or heterobimetallic complexes but also provide catalyst system with hemilabile ligands that readily dissociate to provide vacant coordination sites for incoming substrates (Elliott et al., 1999). Issleib first synthesized the [Ph2P(CH2)3N=CH]C6H5 compound and prepared the Ni (Issleib et al., 1978), Pd and Pt (Issleib & Kipke, 1980) complexes with the ligand. Blinn et al. (1990) reported a new method to synthesize the ligand, which was obtained by reacting Ph2P(CH2)3NH2, from the reduction of Ph2P(CH2)3CN, with benzaldehyde in the presence of molecular sieves. However, they did not report a single-crystal structure. In addition, Hussain et al. (1990) and Banbery et al. (1991) prepared the ligand 2-[Ph2P(CH2)3N=CH]C6H4OH and its Re(V) complex. As the distance for C16—N1 is 1.256 (3) Å, typical for a double bond, this is a novel kind of Schiff base. There is a zigzag chain with a diphenylphosphine and a benzene ring in the molecule.