Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801009783/wn6023sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801009783/wn6023Isup2.hkl |
CCDC reference: 170772
1-Bromo-3-phenylpropane (15.3 ml, 0.10 mol) was added dropwise to a stirred suspension of magnesium (2.55 g, 0.11 mol) in dry THF (30 ml). Dry THF (20 ml) was added and the reaction mixture was heated at reflux for 30 min. The solution was allowed to cool, transferred to a separate flask with dry ether (30 ml), stirred and treated dropwise with chlorodiphenylphosphine (17 ml, 0.095 mol) in dry ether (50 ml) at 273 K. The mixture was heated at reflux for 30 min, cooled to 273 K and treated dropwise with degassed 10% aqueous NH4Cl (30 ml). The mixture was allowed to come to room temperature, the organic phase removed and the aqueous phase extracted with dry ether (3 × 40 ml). The combined organic phases were dried (Na2SO4) and the solvents were removed in vacuo. The residue was recrystallized from dry ethanol to afford (I) as a white solid (melting point 329–331 K (23.17 g, 76%). Full spectroscopic and analytical data for (I) are included in Bennett et al. (2001). Single crystals suitable for X-ray diffraction were obtained from a CH2Cl2–toluene solution.
H atoms were placed geometrically and refined using a riding model with an isotropic displacement parameter fixed at 1.2Ueq for the C atom to which they are attached.
Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; 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.
C21H21P | Dx = 1.214 Mg m−3 |
Mr = 304.35 | Melting point = 329–331 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.7499 (2) Å | Cell parameters from 6675 reflections |
b = 18.0970 (11) Å | θ = 1.0–27.5° |
c = 16.0028 (8) Å | µ = 0.16 mm−1 |
β = 91.421 (3)° | T = 180 K |
V = 1664.67 (14) Å3 | Block, orange |
Z = 4 | 0.21 × 0.18 × 0.14 mm |
F(000) = 648 |
Nonius Kappa CCD diffractometer | 3785 independent reflections |
Radiation source: fine-focus sealed tube | 2390 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
Thin–slice ω and ϕ scans | θmax = 27.5°, θmin = 3.5° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −7→7 |
Tmin = 0.868, Tmax = 0.978 | k = −23→23 |
13665 measured reflections | l = −20→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.083P)2] where P = (Fo2 + 2Fc2)/3 |
3785 reflections | (Δ/σ)max = 0.015 |
199 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
C21H21P | V = 1664.67 (14) Å3 |
Mr = 304.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.7499 (2) Å | µ = 0.16 mm−1 |
b = 18.0970 (11) Å | T = 180 K |
c = 16.0028 (8) Å | 0.21 × 0.18 × 0.14 mm |
β = 91.421 (3)° |
Nonius Kappa CCD diffractometer | 3785 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 2390 reflections with I > 2σ(I) |
Tmin = 0.868, Tmax = 0.978 | Rint = 0.068 |
13665 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.67 e Å−3 |
3785 reflections | Δρmin = −0.54 e Å−3 |
199 parameters |
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 | 0.38330 (9) | −0.02295 (3) | 0.37180 (3) | 0.0305 (2) | |
C1 | 0.6735 (3) | −0.05700 (12) | 0.40425 (13) | 0.0310 (5) | |
H1A | 0.7916 | −0.0352 | 0.3676 | 0.037* | |
H1B | 0.7090 | −0.0408 | 0.4622 | 0.037* | |
C2 | 0.6885 (4) | −0.14091 (12) | 0.39975 (14) | 0.0340 (5) | |
H2A | 0.6939 | −0.1560 | 0.3404 | 0.041* | |
H2B | 0.5460 | −0.1623 | 0.4234 | 0.041* | |
C3 | 0.9016 (4) | −0.17267 (13) | 0.44688 (14) | 0.0355 (5) | |
H3A | 1.0410 | −0.1439 | 0.4320 | 0.043* | |
H3B | 0.8799 | −0.1671 | 0.5077 | 0.043* | |
C4 | 0.9425 (3) | −0.25283 (13) | 0.42740 (12) | 0.0314 (5) | |
C5 | 0.7861 (4) | −0.30692 (14) | 0.45131 (14) | 0.0384 (6) | |
H5A | 0.6556 | −0.2934 | 0.4832 | 0.046* | |
C6 | 0.8170 (4) | −0.37989 (14) | 0.42952 (14) | 0.0414 (6) | |
H6A | 0.7060 | −0.4157 | 0.4457 | 0.050* | |
C7 | 1.0067 (4) | −0.40163 (14) | 0.38465 (14) | 0.0403 (6) | |
H7A | 1.0274 | −0.4521 | 0.3703 | 0.048* | |
C8 | 1.1669 (4) | −0.34889 (14) | 0.36074 (15) | 0.0421 (6) | |
H8A | 1.2988 | −0.3630 | 0.3300 | 0.051* | |
C9 | 1.1334 (4) | −0.27524 (14) | 0.38202 (14) | 0.0380 (6) | |
H9A | 1.2434 | −0.2394 | 0.3652 | 0.046* | |
C10 | 0.4288 (3) | 0.07611 (12) | 0.35783 (13) | 0.0302 (5) | |
C11 | 0.2577 (4) | 0.11569 (13) | 0.31408 (15) | 0.0399 (6) | |
H11A | 0.1253 | 0.0902 | 0.2921 | 0.048* | |
C12 | 0.2755 (4) | 0.19098 (14) | 0.30181 (15) | 0.0442 (6) | |
H12A | 0.1578 | 0.2164 | 0.2706 | 0.053* | |
C13 | 0.4639 (4) | 0.22938 (13) | 0.33472 (15) | 0.0437 (6) | |
H13A | 0.4767 | 0.2812 | 0.3264 | 0.052* | |
C14 | 0.6347 (4) | 0.19134 (14) | 0.38030 (16) | 0.0447 (6) | |
H14A | 0.7632 | 0.2176 | 0.4042 | 0.054* | |
C15 | 0.6194 (4) | 0.11613 (13) | 0.39110 (14) | 0.0380 (6) | |
H15A | 0.7391 | 0.0908 | 0.4214 | 0.046* | |
C16 | 0.3647 (3) | −0.05199 (12) | 0.26151 (13) | 0.0291 (5) | |
C17 | 0.1706 (4) | −0.09216 (13) | 0.23362 (14) | 0.0365 (6) | |
H17A | 0.0550 | −0.1058 | 0.2721 | 0.044* | |
C18 | 0.1444 (4) | −0.11257 (13) | 0.14980 (16) | 0.0445 (6) | |
H18A | 0.0114 | −0.1398 | 0.1314 | 0.053* | |
C19 | 0.3129 (4) | −0.09307 (13) | 0.09364 (15) | 0.0434 (6) | |
H19A | 0.2951 | −0.1064 | 0.0364 | 0.052* | |
C20 | 0.5074 (4) | −0.05412 (14) | 0.12099 (14) | 0.0410 (6) | |
H20A | 0.6248 | −0.0417 | 0.0827 | 0.049* | |
C21 | 0.5318 (4) | −0.03317 (13) | 0.20408 (14) | 0.0363 (6) | |
H21A | 0.6645 | −0.0056 | 0.2219 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0319 (3) | 0.0324 (4) | 0.0272 (3) | −0.0028 (2) | 0.0023 (2) | −0.0026 (2) |
C1 | 0.0374 (11) | 0.0291 (13) | 0.0264 (12) | −0.0026 (9) | 0.0016 (9) | −0.0016 (10) |
C2 | 0.0354 (11) | 0.0326 (14) | 0.0339 (13) | −0.0026 (9) | −0.0022 (9) | −0.0008 (10) |
C3 | 0.0366 (12) | 0.0341 (14) | 0.0353 (13) | −0.0024 (10) | −0.0057 (10) | 0.0000 (10) |
C4 | 0.0351 (11) | 0.0339 (14) | 0.0249 (12) | −0.0017 (10) | −0.0059 (9) | −0.0006 (10) |
C5 | 0.0404 (13) | 0.0403 (16) | 0.0346 (13) | −0.0004 (10) | 0.0057 (10) | 0.0012 (11) |
C6 | 0.0535 (14) | 0.0370 (15) | 0.0337 (13) | −0.0090 (12) | 0.0015 (11) | 0.0033 (11) |
C7 | 0.0526 (14) | 0.0333 (15) | 0.0345 (14) | 0.0066 (11) | −0.0082 (11) | −0.0005 (11) |
C8 | 0.0368 (13) | 0.0478 (17) | 0.0415 (14) | 0.0058 (11) | −0.0028 (10) | −0.0036 (12) |
C9 | 0.0314 (11) | 0.0404 (16) | 0.0420 (14) | −0.0055 (10) | −0.0031 (10) | 0.0007 (11) |
C10 | 0.0352 (11) | 0.0323 (13) | 0.0229 (11) | 0.0033 (9) | 0.0009 (9) | −0.0034 (9) |
C11 | 0.0402 (13) | 0.0395 (16) | 0.0397 (14) | −0.0018 (11) | −0.0063 (10) | −0.0048 (11) |
C12 | 0.0493 (14) | 0.0374 (16) | 0.0451 (15) | 0.0044 (11) | −0.0131 (11) | 0.0006 (12) |
C13 | 0.0566 (15) | 0.0296 (14) | 0.0446 (15) | −0.0011 (11) | −0.0031 (12) | −0.0012 (11) |
C14 | 0.0451 (14) | 0.0355 (15) | 0.0530 (16) | −0.0056 (11) | −0.0094 (11) | −0.0051 (12) |
C15 | 0.0375 (12) | 0.0344 (15) | 0.0416 (14) | −0.0018 (10) | −0.0075 (10) | −0.0021 (11) |
C16 | 0.0317 (11) | 0.0256 (12) | 0.0297 (12) | 0.0007 (9) | −0.0025 (9) | −0.0025 (9) |
C17 | 0.0338 (12) | 0.0372 (14) | 0.0384 (14) | 0.0020 (10) | −0.0010 (10) | −0.0055 (11) |
C18 | 0.0436 (13) | 0.0399 (16) | 0.0491 (16) | 0.0060 (11) | −0.0155 (12) | −0.0131 (12) |
C19 | 0.0607 (16) | 0.0399 (16) | 0.0291 (13) | 0.0148 (12) | −0.0094 (11) | −0.0100 (11) |
C20 | 0.0512 (14) | 0.0413 (15) | 0.0308 (13) | 0.0048 (11) | 0.0060 (10) | −0.0007 (11) |
C21 | 0.0400 (12) | 0.0358 (14) | 0.0332 (13) | −0.0023 (10) | 0.0005 (10) | −0.0023 (10) |
P1—C10 | 1.826 (2) | C10—C11 | 1.392 (3) |
P1—C1 | 1.841 (2) | C10—C15 | 1.407 (3) |
P1—C16 | 1.842 (2) | C11—C12 | 1.381 (3) |
C1—C2 | 1.523 (3) | C11—H11A | 0.9500 |
C1—H1A | 0.9900 | C12—C13 | 1.380 (3) |
C1—H1B | 0.9900 | C12—H12A | 0.9500 |
C2—C3 | 1.535 (3) | C13—C14 | 1.391 (3) |
C2—H2A | 0.9900 | C13—H13A | 0.9500 |
C2—H2B | 0.9900 | C14—C15 | 1.375 (3) |
C3—C4 | 1.504 (3) | C14—H14A | 0.9500 |
C3—H3A | 0.9900 | C15—H15A | 0.9500 |
C3—H3B | 0.9900 | C16—C21 | 1.388 (3) |
C4—C5 | 1.389 (3) | C16—C17 | 1.396 (3) |
C4—C9 | 1.391 (3) | C17—C18 | 1.396 (3) |
C5—C6 | 1.378 (3) | C17—H17A | 0.9500 |
C5—H5A | 0.9500 | C18—C19 | 1.383 (3) |
C6—C7 | 1.378 (3) | C18—H18A | 0.9500 |
C6—H6A | 0.9500 | C19—C20 | 1.384 (3) |
C7—C8 | 1.387 (3) | C19—H19A | 0.9500 |
C7—H7A | 0.9500 | C20—C21 | 1.386 (3) |
C8—C9 | 1.390 (3) | C20—H20A | 0.9500 |
C8—H8A | 0.9500 | C21—H21A | 0.9500 |
C9—H9A | 0.9500 | ||
C10—P1—C1 | 103.38 (9) | C4—C9—H9A | 119.2 |
C10—P1—C16 | 99.67 (10) | C11—C10—C15 | 117.4 (2) |
C1—P1—C16 | 101.85 (9) | C11—C10—P1 | 117.72 (16) |
C2—C1—P1 | 111.86 (14) | C15—C10—P1 | 124.87 (16) |
C2—C1—H1A | 109.2 | C12—C11—C10 | 121.7 (2) |
P1—C1—H1A | 109.2 | C12—C11—H11A | 119.1 |
C2—C1—H1B | 109.2 | C10—C11—H11A | 119.1 |
P1—C1—H1B | 109.2 | C13—C12—C11 | 120.2 (2) |
H1A—C1—H1B | 107.9 | C13—C12—H12A | 119.9 |
C1—C2—C3 | 113.31 (17) | C11—C12—H12A | 119.9 |
C1—C2—H2A | 108.9 | C12—C13—C14 | 119.2 (2) |
C3—C2—H2A | 108.9 | C12—C13—H13A | 120.4 |
C1—C2—H2B | 108.9 | C14—C13—H13A | 120.4 |
C3—C2—H2B | 108.9 | C15—C14—C13 | 120.6 (2) |
H2A—C2—H2B | 107.7 | C15—C14—H14A | 119.7 |
C4—C3—C2 | 112.74 (17) | C13—C14—H14A | 119.7 |
C4—C3—H3A | 109.0 | C14—C15—C10 | 120.9 (2) |
C2—C3—H3A | 109.0 | C14—C15—H15A | 119.5 |
C4—C3—H3B | 109.0 | C10—C15—H15A | 119.5 |
C2—C3—H3B | 109.0 | C21—C16—C17 | 118.5 (2) |
H3A—C3—H3B | 107.8 | C21—C16—P1 | 122.65 (16) |
C5—C4—C9 | 117.6 (2) | C17—C16—P1 | 118.80 (17) |
C5—C4—C3 | 121.1 (2) | C18—C17—C16 | 120.7 (2) |
C9—C4—C3 | 121.3 (2) | C18—C17—H17A | 119.6 |
C6—C5—C4 | 121.1 (2) | C16—C17—H17A | 119.6 |
C6—C5—H5A | 119.4 | C19—C18—C17 | 119.8 (2) |
C4—C5—H5A | 119.4 | C19—C18—H18A | 120.1 |
C7—C6—C5 | 120.9 (2) | C17—C18—H18A | 120.1 |
C7—C6—H6A | 119.5 | C18—C19—C20 | 119.9 (2) |
C5—C6—H6A | 119.5 | C18—C19—H19A | 120.1 |
C6—C7—C8 | 119.1 (2) | C20—C19—H19A | 120.1 |
C6—C7—H7A | 120.4 | C19—C20—C21 | 120.3 (2) |
C8—C7—H7A | 120.4 | C19—C20—H20A | 119.9 |
C7—C8—C9 | 119.7 (2) | C21—C20—H20A | 119.9 |
C7—C8—H8A | 120.2 | C20—C21—C16 | 120.8 (2) |
C9—C8—H8A | 120.2 | C20—C21—H21A | 119.6 |
C8—C9—C4 | 121.5 (2) | C16—C21—H21A | 119.6 |
C8—C9—H9A | 119.2 | ||
C10—P1—C1—C2 | −166.65 (14) | P1—C10—C11—C12 | 178.82 (19) |
C16—P1—C1—C2 | −63.57 (16) | C10—C11—C12—C13 | −1.4 (4) |
P1—C1—C2—C3 | −165.08 (16) | C11—C12—C13—C14 | −0.1 (4) |
C1—C2—C3—C4 | −167.95 (18) | C12—C13—C14—C15 | 1.4 (4) |
C2—C3—C4—C5 | −66.5 (3) | C13—C14—C15—C10 | −1.3 (4) |
C2—C3—C4—C9 | 111.0 (2) | C11—C10—C15—C14 | −0.2 (3) |
C9—C4—C5—C6 | −1.1 (3) | P1—C10—C15—C14 | −177.28 (19) |
C3—C4—C5—C6 | 176.44 (19) | C10—P1—C16—C21 | 51.5 (2) |
C4—C5—C6—C7 | 1.2 (3) | C1—P1—C16—C21 | −54.4 (2) |
C5—C6—C7—C8 | −0.5 (3) | C10—P1—C16—C17 | −125.95 (18) |
C6—C7—C8—C9 | −0.2 (3) | C1—P1—C16—C17 | 128.06 (18) |
C7—C8—C9—C4 | 0.3 (3) | C21—C16—C17—C18 | −0.4 (3) |
C5—C4—C9—C8 | 0.3 (3) | P1—C16—C17—C18 | 177.23 (17) |
C3—C4—C9—C8 | −177.22 (19) | C16—C17—C18—C19 | 0.2 (3) |
C1—P1—C10—C11 | 164.72 (17) | C17—C18—C19—C20 | 0.7 (3) |
C16—P1—C10—C11 | 59.97 (19) | C18—C19—C20—C21 | −1.4 (4) |
C1—P1—C10—C15 | −18.2 (2) | C19—C20—C21—C16 | 1.3 (4) |
C16—P1—C10—C15 | −122.92 (19) | C17—C16—C21—C20 | −0.4 (3) |
C15—C10—C11—C12 | 1.5 (3) | P1—C16—C21—C20 | −177.88 (17) |
Experimental details
Crystal data | |
Chemical formula | C21H21P |
Mr | 304.35 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 180 |
a, b, c (Å) | 5.7499 (2), 18.0970 (11), 16.0028 (8) |
β (°) | 91.421 (3) |
V (Å3) | 1664.67 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.16 |
Crystal size (mm) | 0.21 × 0.18 × 0.14 |
Data collection | |
Diffractometer | Nonius Kappa CCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.868, 0.978 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13665, 3785, 2390 |
Rint | 0.068 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.153, 0.99 |
No. of reflections | 3785 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.54 |
Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Diphenyl(3-phenylpropyl)phosphine, (I), is a potentially chelating ligand that has been prepared by several groups for the study of tethered arene–RhI and RuII complexes of the type [Rh{η1-Ph2P(CH2)3C6H5}{η1:η6-Ph2P(CH2)3C6H5}] (Singewald et al., 1994, 1996) and [RuCl2{η1:η6-Ph2P(CH2)3C6H5}] (Bennett et al., 2001; Ghebreyessus & Nelson, 2000; Smith & Wright, 1998). (I) may coordinate to the metal centre through both the phosphorus donor atom and the alkyl arene. The chelate effect may stabilize oxidation states of the metal that are otherwise unstable by inhibiting decomposition, thought to proceed through loss of the η6-arene (Bennett & Harper, 2001). We report here the crystal structure of the free phosphine (I), determined at 180 (1) K.
In the solid state, the molecular conformation of (I) is such that the 3-phenylpropyl chain is extended away from the P atom (Fig. 1). The lone pair on the P atom remains uncoordinated, and the major directional intermolecular interactions in (I) are between phenyl rings, which adopt both face-to-face and edge-to-face arrangements (Fig. 2). The molecules may be considered to be linked into chains running along the screw diads parallel to the b direction. Molecules adjacent within these chains associate via face-to-face and edge-to-face interactions between four phenyl rings, two of which are bound directly to the P atom and two of which belong to 3-phenylpropyl chains. This arrangement is reminiscent of the so-called `phenyl embrace' (Dance & Scudder, 1996). Edge-to-face interactions also exist between chains giving rise to centrosymmetric fourfold motifs (Fig. 2).