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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o68.
Published online 2007 December 6. doi:  10.1107/S1600536807062034
PMCID: PMC2915026

(2,5-Diphenyl­pent-4-yn-1-en-3-yl­idene)triphenyl­phospho­rane

Abstract

The title compound, C45H27P, was obtained as a product of the reaction of triphenyl­methyl­enephospho­rane with one molar equivalent of 1,4-diphenyl­butadiyne in toluene. The compound was very stable under ambient conditions, but rapidly decomposed in solution when exposed to the air. The P atom is tetra­coordinated in an approximately tetrahedral geometry. The length of the C C triple bond [1.206 (2) Å] is in the normal range.

Related literature

Related crystal structures of α,β-unsaturated-C,P ylides have been reported, see: Koollenz et al. (1996 [triangle]).

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Object name is e-64-00o68-scheme1.jpg

Experimental

Crystal data

  • C35H27P
  • M r = 478.54
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00o68-efi1.jpg
  • a = 11.439 (2) Å
  • b = 11.609 (2) Å
  • c = 11.913 (2) Å
  • α = 116.00 (3)°
  • β = 97.24 (3)°
  • γ = 108.47 (3)°
  • V = 1281.9 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.13 mm−1
  • T = 383 (2) K
  • 0.27 × 0.25 × 0.22 mm

Data collection

  • Bruker SMART diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004 [triangle]) T min = 0.966, T max = 0.972
  • 9166 measured reflections
  • 4661 independent reflections
  • 4077 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.133
  • S = 1.06
  • 4661 reflections
  • 433 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.57 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT and SHELXTL (Sheldrick, 2001 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807062034/lw2053sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062034/lw2053Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the NSFC (Nos. 20572062 and 20372042) and by the Doctoral Program of the MOE (Nos. 20050422010 and 20050422011).

supplementary crystallographic information

Comment

In the title molecule (Fig.1) the phosphorane atom is coordinated in a tetragonal pyramid by three C atoms of phenyl groups and one sp2-C atom. The length of the C—C triple bond is in the range of classic one, and the carbon atoms linked to the C—C triple bond lie in nearly a line.

Experimental

To the solution of triphenylmethylenephosphorane(1.41 g, 5.11 mmol) in 30 ml of toluene was added 1,4-diphenylbutadiyne(1.05 g, 5.20 mmol) at room temperature, a deep red solution formed rapidly. After stirring for at least 24 h the reaction solution was filtrated. The solid residue was dried and extracted with pentane and diethyl ether, respectively. Purple red crystals were obtained suitable for X-ray diffraction analysis. (yield:1.59 g, 65.1%, d.p.: 87 °C)

Refinement

All H atoms were positioned geometrically. All the H atoms are refined using a riding model with C—H = 0.92–1.02 Å and with Uiso(H) = 1.2 times Ueq(C).

Figures

Fig. 1.
The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.

Crystal data

C35H27PZ = 2
Mr = 478.54F000 = 504
Triclinic, P1Dx = 1.240 Mg m3
a = 11.439 (2) ÅMo Kα radiation λ = 0.71073 Å
b = 11.609 (2) ÅCell parameters from 5612 reflections
c = 11.913 (2) Åθ = 2.2–23.2º
α = 116.00 (3)ºµ = 0.13 mm1
β = 97.24 (3)ºT = 383 (2) K
γ = 108.47 (3)ºCubic, purple red
V = 1281.9 (4) Å30.27 × 0.25 × 0.22 mm

Data collection

Bruker SMART diffractometer4661 independent reflections
Radiation source: fine-focus sealed tube4077 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.043
T = 383(2) Kθmax = 26.0º
ω scansθmin = 2.0º
Absorption correction: multi-scan(SADABS; Sheldrick, 2004)h = −14→14
Tmin = 0.966, Tmax = 0.972k = −13→14
9166 measured reflectionsl = −14→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.133  w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.002
4661 reflectionsΔρmax = 0.57 e Å3
433 parametersΔρmin = −0.29 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
P10.68533 (3)0.36252 (4)0.11133 (3)0.01164 (15)
C10.56521 (14)0.24722 (17)−0.05062 (14)0.0144 (3)
C20.47129 (15)0.11909 (18)−0.07668 (15)0.0164 (3)
C30.38692 (16)0.02065 (19)−0.20295 (16)0.0187 (4)
C40.39421 (15)0.04989 (18)−0.30372 (15)0.0193 (4)
C50.48380 (16)0.1796 (2)−0.27692 (16)0.0206 (4)
C60.56947 (15)0.27875 (19)−0.15066 (15)0.0168 (3)
C70.76840 (14)0.52987 (17)0.12146 (14)0.0147 (3)
C80.74427 (15)0.64557 (19)0.19848 (16)0.0188 (4)
C90.80051 (17)0.7702 (2)0.19820 (18)0.0242 (4)
C100.88218 (17)0.7816 (2)0.12299 (18)0.0243 (4)
C110.90960 (16)0.6678 (2)0.04955 (16)0.0223 (4)
C120.85367 (15)0.54293 (18)0.04849 (15)0.0163 (3)
C130.80689 (14)0.29439 (18)0.11596 (14)0.0142 (3)
C140.92794 (15)0.38344 (19)0.21428 (15)0.0163 (3)
C151.01613 (16)0.3280 (2)0.22863 (16)0.0197 (4)
C160.98606 (16)0.1863 (2)0.14545 (17)0.0222 (4)
C170.86805 (17)0.0994 (2)0.04615 (17)0.0224 (4)
C180.77842 (16)0.15322 (18)0.03089 (16)0.0191 (4)
C190.61694 (14)0.36449 (17)0.23325 (14)0.0135 (3)
C200.68991 (14)0.36051 (16)0.33433 (14)0.0132 (3)
C210.75197 (14)0.35583 (17)0.42069 (14)0.0156 (3)
C220.80550 (14)0.30986 (17)0.49926 (14)0.0153 (3)
C230.90307 (15)0.26281 (19)0.47269 (16)0.0199 (4)
C240.94525 (16)0.2043 (2)0.53938 (17)0.0232 (4)
C250.89336 (17)0.1928 (2)0.63495 (16)0.0233 (4)
C260.80095 (17)0.24431 (19)0.66597 (16)0.0211 (4)
C270.75698 (15)0.30231 (18)0.59963 (15)0.0182 (3)
C280.48816 (14)0.36477 (17)0.22947 (14)0.0142 (3)
C290.42860 (16)0.4080 (2)0.16165 (16)0.0205 (4)
C300.41673 (14)0.30236 (17)0.30066 (14)0.0143 (3)
C310.34931 (15)0.36725 (18)0.37822 (15)0.0167 (3)
C320.27977 (15)0.30599 (19)0.44037 (16)0.0199 (4)
C330.27776 (17)0.1813 (2)0.42805 (17)0.0234 (4)
C340.34548 (17)0.1160 (2)0.35238 (18)0.0233 (4)
C350.41519 (15)0.17774 (18)0.29087 (15)0.0185 (3)
H210.3514 (19)0.457 (2)0.3947 (19)0.024 (5)*
H50.630 (2)0.366 (2)−0.1330 (17)0.017 (4)*
H10.4642 (19)0.099 (2)−0.0043 (18)0.021 (5)*
H140.844 (2)0.003 (3)−0.013 (2)0.042 (6)*
H20.328 (2)−0.064 (2)−0.2167 (19)0.025 (5)*
H60.691 (2)0.639 (2)0.2514 (19)0.023 (5)*
H230.229 (2)0.134 (2)0.4727 (19)0.027 (5)*
H110.9484 (19)0.480 (2)0.2726 (19)0.021 (5)*
H30.338 (2)−0.017 (2)−0.390 (2)0.023 (5)*
H100.871 (2)0.462 (3)−0.004 (2)0.030 (5)*
H160.9390 (19)0.268 (2)0.4059 (19)0.021 (5)*
H240.348 (2)0.034 (3)0.343 (2)0.032 (6)*
H190.768 (2)0.240 (2)0.735 (2)0.028 (5)*
H270.475 (2)0.451 (2)0.1141 (19)0.025 (5)*
H40.487 (2)0.202 (2)−0.345 (2)0.028 (5)*
H150.698 (2)0.092 (2)−0.0382 (19)0.021 (5)*
H180.921 (2)0.153 (2)0.682 (2)0.029 (5)*
H131.050 (2)0.147 (2)0.1566 (19)0.027 (5)*
H121.095 (2)0.388 (2)0.295 (2)0.025 (5)*
H220.234 (2)0.355 (2)0.496 (2)0.028 (5)*
H250.461 (2)0.133 (3)0.238 (2)0.034 (6)*
H70.787 (2)0.853 (3)0.255 (2)0.042 (6)*
H200.693 (2)0.338 (2)0.621 (2)0.031 (5)*
H171.009 (2)0.167 (2)0.513 (2)0.032 (6)*
H80.924 (2)0.870 (3)0.125 (2)0.032 (6)*
H90.966 (2)0.670 (3)0.001 (2)0.033 (6)*
H260.339 (2)0.390 (2)0.1535 (18)0.022 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0118 (2)0.0110 (3)0.0152 (2)0.00594 (17)0.00547 (16)0.00793 (17)
C10.0143 (7)0.0151 (9)0.0155 (7)0.0084 (6)0.0046 (6)0.0077 (6)
C20.0179 (7)0.0137 (9)0.0211 (8)0.0078 (6)0.0067 (6)0.0106 (6)
C30.0175 (7)0.0137 (9)0.0246 (8)0.0072 (7)0.0055 (6)0.0092 (7)
C40.0178 (8)0.0172 (9)0.0186 (8)0.0085 (7)0.0038 (6)0.0054 (7)
C50.0194 (8)0.0279 (11)0.0186 (8)0.0114 (7)0.0076 (6)0.0136 (7)
C60.0149 (7)0.0145 (9)0.0229 (8)0.0053 (7)0.0066 (6)0.0115 (7)
C70.0128 (7)0.0152 (9)0.0180 (7)0.0061 (6)0.0030 (6)0.0101 (6)
C80.0160 (7)0.0181 (10)0.0266 (8)0.0090 (7)0.0082 (7)0.0131 (7)
C90.0214 (8)0.0144 (10)0.0413 (10)0.0104 (7)0.0079 (7)0.0161 (8)
C100.0196 (8)0.0217 (11)0.0393 (10)0.0057 (7)0.0050 (7)0.0248 (8)
C110.0189 (8)0.0272 (11)0.0235 (8)0.0068 (7)0.0059 (7)0.0173 (7)
C120.0159 (7)0.0156 (9)0.0182 (7)0.0049 (6)0.0052 (6)0.0105 (6)
C130.0157 (7)0.0175 (9)0.0184 (7)0.0108 (7)0.0101 (6)0.0125 (6)
C140.0171 (7)0.0167 (9)0.0202 (7)0.0086 (7)0.0095 (6)0.0113 (7)
C150.0170 (8)0.0278 (10)0.0238 (8)0.0128 (7)0.0096 (7)0.0175 (7)
C160.0237 (8)0.0287 (11)0.0337 (9)0.0196 (8)0.0181 (7)0.0231 (8)
C170.0291 (9)0.0138 (10)0.0349 (9)0.0138 (7)0.0185 (7)0.0153 (7)
C180.0179 (8)0.0154 (9)0.0238 (8)0.0075 (7)0.0086 (7)0.0089 (7)
C190.0144 (7)0.0145 (9)0.0164 (7)0.0076 (6)0.0072 (6)0.0100 (6)
C200.0139 (7)0.0100 (8)0.0165 (7)0.0055 (6)0.0075 (6)0.0064 (6)
C210.0157 (7)0.0170 (9)0.0169 (7)0.0083 (6)0.0076 (6)0.0092 (6)
C220.0144 (7)0.0110 (8)0.0164 (7)0.0031 (6)0.0014 (6)0.0061 (6)
C230.0180 (8)0.0241 (10)0.0217 (8)0.0095 (7)0.0077 (6)0.0140 (7)
C240.0187 (8)0.0281 (11)0.0282 (9)0.0135 (8)0.0066 (7)0.0162 (7)
C250.0245 (8)0.0242 (11)0.0233 (8)0.0100 (8)0.0018 (7)0.0152 (7)
C260.0253 (8)0.0200 (10)0.0176 (8)0.0069 (7)0.0070 (6)0.0110 (7)
C270.0186 (7)0.0171 (9)0.0195 (7)0.0082 (7)0.0078 (6)0.0087 (6)
C280.0147 (7)0.0127 (8)0.0172 (7)0.0077 (6)0.0062 (6)0.0074 (6)
C290.0180 (8)0.0257 (10)0.0266 (8)0.0133 (7)0.0099 (6)0.0165 (7)
C300.0108 (7)0.0135 (8)0.0167 (7)0.0054 (6)0.0034 (6)0.0063 (6)
C310.0157 (7)0.0153 (9)0.0205 (7)0.0088 (7)0.0061 (6)0.0086 (6)
C320.0185 (8)0.0191 (9)0.0244 (8)0.0095 (7)0.0109 (7)0.0107 (7)
C330.0237 (8)0.0243 (10)0.0286 (9)0.0098 (7)0.0144 (7)0.0171 (7)
C340.0268 (9)0.0169 (10)0.0340 (9)0.0115 (8)0.0148 (7)0.0161 (8)
C350.0193 (8)0.0151 (9)0.0224 (8)0.0092 (7)0.0091 (6)0.0086 (6)

Geometric parameters (Å, °)

P1—C191.7294 (15)C17—C181.390 (2)
P1—C131.8104 (15)C17—H140.95 (3)
P1—C71.8132 (18)C18—H150.95 (2)
P1—C11.8178 (19)C19—C201.403 (2)
C1—C61.394 (2)C19—C281.4693 (19)
C1—C21.401 (2)C20—C211.206 (2)
C2—C31.389 (2)C21—C221.427 (2)
C2—H10.99 (2)C22—C231.403 (2)
C3—C41.388 (2)C22—C271.405 (2)
C3—H20.92 (2)C23—C241.382 (2)
C4—C51.392 (3)C23—H160.96 (2)
C4—H30.95 (2)C24—C251.385 (3)
C5—C61.394 (3)C24—H170.98 (2)
C5—H40.96 (2)C25—C261.384 (2)
C6—H50.94 (2)C25—H180.95 (2)
C7—C81.393 (2)C26—C271.383 (2)
C7—C121.402 (2)C26—H190.96 (2)
C8—C91.387 (3)C27—H200.96 (2)
C8—H60.94 (2)C28—C291.343 (2)
C9—C101.389 (3)C28—C301.500 (2)
C9—H70.98 (2)C29—H271.00 (2)
C10—C111.388 (3)C29—H260.96 (2)
C10—H80.97 (3)C30—C351.394 (2)
C11—C121.381 (3)C30—C311.398 (2)
C11—H90.92 (2)C31—C321.392 (2)
C12—H100.97 (2)C31—H210.96 (2)
C13—C181.393 (2)C32—C331.382 (3)
C13—C141.407 (2)C32—H220.99 (2)
C14—C151.388 (2)C33—C341.391 (2)
C14—H110.95 (2)C33—H231.02 (2)
C15—C161.390 (3)C34—C351.390 (2)
C15—H120.93 (2)C34—H240.92 (2)
C16—C171.388 (3)C35—H250.96 (2)
C16—H131.00 (2)
C19—P1—C13108.20 (7)C16—C17—C18120.08 (17)
C19—P1—C7117.53 (8)C16—C17—H14123.3 (15)
C13—P1—C7105.18 (7)C18—C17—H14116.6 (15)
C19—P1—C1111.39 (7)C17—C18—C13119.88 (16)
C13—P1—C1107.73 (7)C17—C18—H15118.6 (12)
C7—P1—C1106.29 (8)C13—C18—H15121.5 (12)
C6—C1—C2119.66 (15)C20—C19—C28121.62 (13)
C6—C1—P1121.88 (13)C20—C19—P1115.92 (10)
C2—C1—P1118.32 (12)C28—C19—P1122.42 (11)
C3—C2—C1120.33 (15)C21—C20—C19179.42 (18)
C3—C2—H1119.9 (12)C20—C21—C22164.32 (18)
C1—C2—H1119.8 (12)C23—C22—C27118.19 (15)
C4—C3—C2119.99 (17)C23—C22—C21120.51 (14)
C4—C3—H2122.2 (12)C27—C22—C21121.19 (14)
C2—C3—H2117.8 (12)C24—C23—C22120.55 (15)
C3—C4—C5119.77 (16)C24—C23—H16119.4 (12)
C3—C4—H3120.6 (13)C22—C23—H16120.1 (12)
C5—C4—H3119.6 (13)C23—C24—C25120.65 (15)
C4—C5—C6120.66 (16)C23—C24—H17117.8 (13)
C4—C5—H4120.6 (13)C25—C24—H17121.4 (13)
C6—C5—H4118.8 (13)C26—C25—C24119.34 (16)
C1—C6—C5119.49 (16)C26—C25—H18118.5 (12)
C1—C6—H5120.1 (11)C24—C25—H18122.1 (12)
C5—C6—H5120.4 (11)C27—C26—C25120.76 (15)
C8—C7—C12119.35 (16)C27—C26—H19120.4 (13)
C8—C7—P1120.06 (12)C25—C26—H19118.8 (13)
C12—C7—P1120.55 (13)C26—C27—C22120.41 (15)
C9—C8—C7119.84 (15)C26—C27—H20121.1 (13)
C9—C8—H6120.2 (13)C22—C27—H20118.5 (13)
C7—C8—H6119.9 (13)C29—C28—C19125.09 (15)
C8—C9—C10120.66 (16)C29—C28—C30118.87 (14)
C8—C9—H7119.9 (15)C19—C28—C30115.91 (13)
C10—C9—H7119.4 (15)C28—C29—H27120.4 (11)
C11—C10—C9119.51 (18)C28—C29—H26118.9 (12)
C11—C10—H8119.9 (13)H27—C29—H26120.5 (16)
C9—C10—H8120.5 (12)C35—C30—C31118.12 (15)
C12—C11—C10120.36 (16)C35—C30—C28120.97 (13)
C12—C11—H9116.2 (15)C31—C30—C28120.91 (15)
C10—C11—H9123.4 (15)C32—C31—C30120.45 (16)
C11—C12—C7120.22 (16)C32—C31—H21116.8 (12)
C11—C12—H10120.6 (14)C30—C31—H21122.6 (12)
C7—C12—H10119.1 (14)C33—C32—C31120.64 (15)
C18—C13—C14120.01 (15)C33—C32—H22120.8 (13)
C18—C13—P1120.91 (12)C31—C32—H22118.5 (13)
C14—C13—P1118.87 (12)C32—C33—C34119.68 (16)
C15—C14—C13119.37 (16)C32—C33—H23122.9 (12)
C15—C14—H11119.8 (12)C34—C33—H23117.5 (12)
C13—C14—H11120.7 (12)C35—C34—C33119.51 (18)
C14—C15—C16120.36 (16)C35—C34—H24118.0 (13)
C14—C15—H12117.8 (13)C33—C34—H24122.4 (14)
C16—C15—H12121.8 (13)C34—C35—C30121.56 (15)
C17—C16—C15120.25 (15)C34—C35—H25119.7 (14)
C17—C16—H13120.0 (12)C30—C35—H25118.7 (14)
C15—C16—H13119.8 (13)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LW2053).

References

  • Bruker (2001). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Koollenz, G., Penn, G., Theuer, R., Fabian, W. M. F., Abd El-Nabi, H. A., Xiong, Z., Peters, K., Peters, E.-M. & von Schnering, H. G. (1996). Tetrahedron, 52, 15, 5427–5440.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Sheldrick, G. M. (2001). SHELXTL Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2004). SADABS University of Göttingen, Germany.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography