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The crystal structure of di­phenyl­(3-phenyl­propyl)­phosphine, C21H21P, has been determined at 180 (1) K. The mol­ecules may be considered to be linked into chains running along screw diads in space group P21/c, with mol­ecules adjacent in these chains associated via face-to-face and edge-to-face interactions between phenyl rings. Edge-to-face interactions also exist between chains giving rise to centrosymmetric fourfold motifs.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801009783/wn6023sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801009783/wn6023Isup2.hkl
Contains datablock I

CCDC reference: 170772

Key indicators

  • Single-crystal X-ray study
  • T = 180 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.052
  • wR factor = 0.153
  • Data-to-parameter ratio = 19.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.868 0.978 Tmin' and Tmax expected: 0.966 0.978 RR' = 0.898 Please check that your absorption correction is appropriate.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular unit of (I) showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993).
[Figure 2] Fig. 2. View along the a direction showing molecules linked into chains along screw diads by edge-to-face interactions between phenyl rings, denoted by dotted lines (CAMERON; Watkin et al., 1996).
Diphenyl(3-phenylpropyl)phosphine top
Crystal data top
C21H21PDx = 1.214 Mg m3
Mr = 304.35Melting point = 329–331 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 5.7499 (2) ÅCell parameters from 6675 reflections
b = 18.0970 (11) Åθ = 1.0–27.5°
c = 16.0028 (8) ŵ = 0.16 mm1
β = 91.421 (3)°T = 180 K
V = 1664.67 (14) Å3Block, orange
Z = 40.21 × 0.18 × 0.14 mm
F(000) = 648
Data collection top
Nonius Kappa CCD
diffractometer
3785 independent reflections
Radiation source: fine-focus sealed tube2390 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.068
Thin–slice ω and ϕ scansθmax = 27.5°, θmin = 3.5°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
h = 77
Tmin = 0.868, Tmax = 0.978k = 2323
13665 measured reflectionsl = 2020
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153H-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 parametersΔρmax = 0.67 e Å3
0 restraintsΔρmin = 0.54 e Å3
Crystal data top
C21H21PV = 1664.67 (14) Å3
Mr = 304.35Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.7499 (2) ŵ = 0.16 mm1
b = 18.0970 (11) ÅT = 180 K
c = 16.0028 (8) Å0.21 × 0.18 × 0.14 mm
β = 91.421 (3)°
Data collection top
Nonius Kappa CCD
diffractometer
3785 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
2390 reflections with I > 2σ(I)
Tmin = 0.868, Tmax = 0.978Rint = 0.068
13665 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.153H-atom parameters constrained
S = 0.99Δρmax = 0.67 e Å3
3785 reflectionsΔρmin = 0.54 e Å3
199 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.38330 (9)0.02295 (3)0.37180 (3)0.0305 (2)
C10.6735 (3)0.05700 (12)0.40425 (13)0.0310 (5)
H1A0.79160.03520.36760.037*
H1B0.70900.04080.46220.037*
C20.6885 (4)0.14091 (12)0.39975 (14)0.0340 (5)
H2A0.69390.15600.34040.041*
H2B0.54600.16230.42340.041*
C30.9016 (4)0.17267 (13)0.44688 (14)0.0355 (5)
H3A1.04100.14390.43200.043*
H3B0.87990.16710.50770.043*
C40.9425 (3)0.25283 (13)0.42740 (12)0.0314 (5)
C50.7861 (4)0.30692 (14)0.45131 (14)0.0384 (6)
H5A0.65560.29340.48320.046*
C60.8170 (4)0.37989 (14)0.42952 (14)0.0414 (6)
H6A0.70600.41570.44570.050*
C71.0067 (4)0.40163 (14)0.38465 (14)0.0403 (6)
H7A1.02740.45210.37030.048*
C81.1669 (4)0.34889 (14)0.36074 (15)0.0421 (6)
H8A1.29880.36300.33000.051*
C91.1334 (4)0.27524 (14)0.38202 (14)0.0380 (6)
H9A1.24340.23940.36520.046*
C100.4288 (3)0.07611 (12)0.35783 (13)0.0302 (5)
C110.2577 (4)0.11569 (13)0.31408 (15)0.0399 (6)
H11A0.12530.09020.29210.048*
C120.2755 (4)0.19098 (14)0.30181 (15)0.0442 (6)
H12A0.15780.21640.27060.053*
C130.4639 (4)0.22938 (13)0.33472 (15)0.0437 (6)
H13A0.47670.28120.32640.052*
C140.6347 (4)0.19134 (14)0.38030 (16)0.0447 (6)
H14A0.76320.21760.40420.054*
C150.6194 (4)0.11613 (13)0.39110 (14)0.0380 (6)
H15A0.73910.09080.42140.046*
C160.3647 (3)0.05199 (12)0.26151 (13)0.0291 (5)
C170.1706 (4)0.09216 (13)0.23362 (14)0.0365 (6)
H17A0.05500.10580.27210.044*
C180.1444 (4)0.11257 (13)0.14980 (16)0.0445 (6)
H18A0.01140.13980.13140.053*
C190.3129 (4)0.09307 (13)0.09364 (15)0.0434 (6)
H19A0.29510.10640.03640.052*
C200.5074 (4)0.05412 (14)0.12099 (14)0.0410 (6)
H20A0.62480.04170.08270.049*
C210.5318 (4)0.03317 (13)0.20408 (14)0.0363 (6)
H21A0.66450.00560.22190.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0319 (3)0.0324 (4)0.0272 (3)0.0028 (2)0.0023 (2)0.0026 (2)
C10.0374 (11)0.0291 (13)0.0264 (12)0.0026 (9)0.0016 (9)0.0016 (10)
C20.0354 (11)0.0326 (14)0.0339 (13)0.0026 (9)0.0022 (9)0.0008 (10)
C30.0366 (12)0.0341 (14)0.0353 (13)0.0024 (10)0.0057 (10)0.0000 (10)
C40.0351 (11)0.0339 (14)0.0249 (12)0.0017 (10)0.0059 (9)0.0006 (10)
C50.0404 (13)0.0403 (16)0.0346 (13)0.0004 (10)0.0057 (10)0.0012 (11)
C60.0535 (14)0.0370 (15)0.0337 (13)0.0090 (12)0.0015 (11)0.0033 (11)
C70.0526 (14)0.0333 (15)0.0345 (14)0.0066 (11)0.0082 (11)0.0005 (11)
C80.0368 (13)0.0478 (17)0.0415 (14)0.0058 (11)0.0028 (10)0.0036 (12)
C90.0314 (11)0.0404 (16)0.0420 (14)0.0055 (10)0.0031 (10)0.0007 (11)
C100.0352 (11)0.0323 (13)0.0229 (11)0.0033 (9)0.0009 (9)0.0034 (9)
C110.0402 (13)0.0395 (16)0.0397 (14)0.0018 (11)0.0063 (10)0.0048 (11)
C120.0493 (14)0.0374 (16)0.0451 (15)0.0044 (11)0.0131 (11)0.0006 (12)
C130.0566 (15)0.0296 (14)0.0446 (15)0.0011 (11)0.0031 (12)0.0012 (11)
C140.0451 (14)0.0355 (15)0.0530 (16)0.0056 (11)0.0094 (11)0.0051 (12)
C150.0375 (12)0.0344 (15)0.0416 (14)0.0018 (10)0.0075 (10)0.0021 (11)
C160.0317 (11)0.0256 (12)0.0297 (12)0.0007 (9)0.0025 (9)0.0025 (9)
C170.0338 (12)0.0372 (14)0.0384 (14)0.0020 (10)0.0010 (10)0.0055 (11)
C180.0436 (13)0.0399 (16)0.0491 (16)0.0060 (11)0.0155 (12)0.0131 (12)
C190.0607 (16)0.0399 (16)0.0291 (13)0.0148 (12)0.0094 (11)0.0100 (11)
C200.0512 (14)0.0413 (15)0.0308 (13)0.0048 (11)0.0060 (10)0.0007 (11)
C210.0400 (12)0.0358 (14)0.0332 (13)0.0023 (10)0.0005 (10)0.0023 (10)
Geometric parameters (Å, º) top
P1—C101.826 (2)C10—C111.392 (3)
P1—C11.841 (2)C10—C151.407 (3)
P1—C161.842 (2)C11—C121.381 (3)
C1—C21.523 (3)C11—H11A0.9500
C1—H1A0.9900C12—C131.380 (3)
C1—H1B0.9900C12—H12A0.9500
C2—C31.535 (3)C13—C141.391 (3)
C2—H2A0.9900C13—H13A0.9500
C2—H2B0.9900C14—C151.375 (3)
C3—C41.504 (3)C14—H14A0.9500
C3—H3A0.9900C15—H15A0.9500
C3—H3B0.9900C16—C211.388 (3)
C4—C51.389 (3)C16—C171.396 (3)
C4—C91.391 (3)C17—C181.396 (3)
C5—C61.378 (3)C17—H17A0.9500
C5—H5A0.9500C18—C191.383 (3)
C6—C71.378 (3)C18—H18A0.9500
C6—H6A0.9500C19—C201.384 (3)
C7—C81.387 (3)C19—H19A0.9500
C7—H7A0.9500C20—C211.386 (3)
C8—C91.390 (3)C20—H20A0.9500
C8—H8A0.9500C21—H21A0.9500
C9—H9A0.9500
C10—P1—C1103.38 (9)C4—C9—H9A119.2
C10—P1—C1699.67 (10)C11—C10—C15117.4 (2)
C1—P1—C16101.85 (9)C11—C10—P1117.72 (16)
C2—C1—P1111.86 (14)C15—C10—P1124.87 (16)
C2—C1—H1A109.2C12—C11—C10121.7 (2)
P1—C1—H1A109.2C12—C11—H11A119.1
C2—C1—H1B109.2C10—C11—H11A119.1
P1—C1—H1B109.2C13—C12—C11120.2 (2)
H1A—C1—H1B107.9C13—C12—H12A119.9
C1—C2—C3113.31 (17)C11—C12—H12A119.9
C1—C2—H2A108.9C12—C13—C14119.2 (2)
C3—C2—H2A108.9C12—C13—H13A120.4
C1—C2—H2B108.9C14—C13—H13A120.4
C3—C2—H2B108.9C15—C14—C13120.6 (2)
H2A—C2—H2B107.7C15—C14—H14A119.7
C4—C3—C2112.74 (17)C13—C14—H14A119.7
C4—C3—H3A109.0C14—C15—C10120.9 (2)
C2—C3—H3A109.0C14—C15—H15A119.5
C4—C3—H3B109.0C10—C15—H15A119.5
C2—C3—H3B109.0C21—C16—C17118.5 (2)
H3A—C3—H3B107.8C21—C16—P1122.65 (16)
C5—C4—C9117.6 (2)C17—C16—P1118.80 (17)
C5—C4—C3121.1 (2)C18—C17—C16120.7 (2)
C9—C4—C3121.3 (2)C18—C17—H17A119.6
C6—C5—C4121.1 (2)C16—C17—H17A119.6
C6—C5—H5A119.4C19—C18—C17119.8 (2)
C4—C5—H5A119.4C19—C18—H18A120.1
C7—C6—C5120.9 (2)C17—C18—H18A120.1
C7—C6—H6A119.5C18—C19—C20119.9 (2)
C5—C6—H6A119.5C18—C19—H19A120.1
C6—C7—C8119.1 (2)C20—C19—H19A120.1
C6—C7—H7A120.4C19—C20—C21120.3 (2)
C8—C7—H7A120.4C19—C20—H20A119.9
C7—C8—C9119.7 (2)C21—C20—H20A119.9
C7—C8—H8A120.2C20—C21—C16120.8 (2)
C9—C8—H8A120.2C20—C21—H21A119.6
C8—C9—C4121.5 (2)C16—C21—H21A119.6
C8—C9—H9A119.2
C10—P1—C1—C2166.65 (14)P1—C10—C11—C12178.82 (19)
C16—P1—C1—C263.57 (16)C10—C11—C12—C131.4 (4)
P1—C1—C2—C3165.08 (16)C11—C12—C13—C140.1 (4)
C1—C2—C3—C4167.95 (18)C12—C13—C14—C151.4 (4)
C2—C3—C4—C566.5 (3)C13—C14—C15—C101.3 (4)
C2—C3—C4—C9111.0 (2)C11—C10—C15—C140.2 (3)
C9—C4—C5—C61.1 (3)P1—C10—C15—C14177.28 (19)
C3—C4—C5—C6176.44 (19)C10—P1—C16—C2151.5 (2)
C4—C5—C6—C71.2 (3)C1—P1—C16—C2154.4 (2)
C5—C6—C7—C80.5 (3)C10—P1—C16—C17125.95 (18)
C6—C7—C8—C90.2 (3)C1—P1—C16—C17128.06 (18)
C7—C8—C9—C40.3 (3)C21—C16—C17—C180.4 (3)
C5—C4—C9—C80.3 (3)P1—C16—C17—C18177.23 (17)
C3—C4—C9—C8177.22 (19)C16—C17—C18—C190.2 (3)
C1—P1—C10—C11164.72 (17)C17—C18—C19—C200.7 (3)
C16—P1—C10—C1159.97 (19)C18—C19—C20—C211.4 (4)
C1—P1—C10—C1518.2 (2)C19—C20—C21—C161.3 (4)
C16—P1—C10—C15122.92 (19)C17—C16—C21—C200.4 (3)
C15—C10—C11—C121.5 (3)P1—C16—C21—C20177.88 (17)

Experimental details

Crystal data
Chemical formulaC21H21P
Mr304.35
Crystal system, space groupMonoclinic, P21/c
Temperature (K)180
a, b, c (Å)5.7499 (2), 18.0970 (11), 16.0028 (8)
β (°) 91.421 (3)
V3)1664.67 (14)
Z4
Radiation typeMo Kα
µ (mm1)0.16
Crystal size (mm)0.21 × 0.18 × 0.14
Data collection
DiffractometerNonius Kappa CCD
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.868, 0.978
No. of measured, independent and
observed [I > 2σ(I)] reflections
13665, 3785, 2390
Rint0.068
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.153, 0.99
No. of reflections3785
No. of parameters199
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

 

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