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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): o2213.
Published online 2008 October 31. doi:  10.1107/S1600536808034673
PMCID: PMC2959552

(Cyano­meth­yl)triphenyl­phospho­nium chloride

Abstract

In the mol­ecule of the title compound, C20H17NP+·Cl, the coordination around the P atom is slightly distorted tetra­hedral. In the crystal structure, inter­molecular C—H(...)N and C—H(...)Cl hydrogen bonds link the mol­ecules. There is a π–π contact between the phenyl rings [centroid–centroid distance = 3.702 (3) Å].

Related literature

For related structures, see: Czerwinski (2004 [triangle]); Czerwinski & Ponnuswamy (1988 [triangle]); de Dubourg et al. (1986 [triangle]); Fischer & Wiebelhaus (1997 [triangle]); Shafiq et al. (2008 [triangle]); Skapski & Stephens (1974 [triangle]); Tahir et al. (2008 [triangle]).

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Object name is e-64-o2213-scheme1.jpg

Experimental

Crystal data

  • C20H17NP+·Cl
  • M r = 337.77
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2213-efi1.jpg
  • a = 11.8269 (5) Å
  • b = 11.8130 (4) Å
  • c = 12.8918 (5) Å
  • β = 92.213 (2)°
  • V = 1799.79 (12) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.30 mm−1
  • T = 296 (2) K
  • 0.26 × 0.20 × 0.16 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.928, T max = 0.950
  • 19927 measured reflections
  • 4465 independent reflections
  • 3145 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.111
  • S = 1.03
  • 4465 reflections
  • 208 parameters
  • H-atom parameters constrained
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808034673/hk2558sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808034673/hk2558Isup2.hkl

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

Acknowledgments

MS greatfully acknowledges the Higher Education Com­mis­sion, Islamabad, Pakistan, for providing his Scholarship under the Indigenous PhD Program (PIN 042–120567-PS2–276).

supplementary crystallographic information

Comment

Triphenyl phosphonium compounds are key reagents in the Wittig reactions, used to convert aldehydes and ketones into alkenes. The Wittig reaction has seen use in applications ranging from the synthesis of simple alkenes to the construction of complex biologically active molecules for the pharmaceutical industry.The title compound is synthesized for the derivatization of our already published structures (Shafiq et al., 2008; Tahir et al., 2008) using this particular reaction. Various structures have been published having the similar geometry around P atom (Skapski & Stephens, 1974; de Dubourg et al., 1986; Czerwinski & Ponnuswamy, 1988; Fischer & Wiebelhaus, 1997; Czerwinski, 2004).

In the molecule of the title compound (Fig 1), the geometry around P atom is slightly distorted tetrahedral (Table 1). Rings A (C1-C6), B (C7-C12) and C (C13-C18) are of course planar. The dihedral angles between them are A/B = 86.10 (11)°, A/C = 89.78 (10)° and B/C = 76.23 (12)°.

In the crystal structure, intramolecular C-H···Cl and intermolecular C-H···N and C-H···Cl hydrogen bonds (Table 2) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. The π—π contact between the phenyl rings, Cg3···Cg3i [symmetry code: (i) 2 - x, -y, 1 - z, where Cg3 is the centroid of the ring C (C13-C18)] may further stabilize the structure, with centroid-centroid distance of 3.702 (3) Å. There also exist a C—H···π contact (Table 2) between the phenyl rings.

Experimental

Triphenylphosphine (10 g, 0.038 mol) was dissolved in benzene (20 ml) under stirring at room temperature. To this solution, chloroacetonitrile (4 g, 0.0514 mole) was added dropwise. After complete addition, clear solution formed was left in the darkness for 2-3 d. Colorless crystals formed were separated for X-ray diffraction studies.

Refinement

H-atoms were positioned geometrically, with C-H = 0.93 and 0.97 Å for aromatic and methylene H, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids drawn at the 50% probability level.
Fig. 2.
A partial packing diagram. Hydrogen bonds are shown as dashed lines.

Crystal data

C20H17NP+·ClF(000) = 704
Mr = 337.77Dx = 1.247 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4467 reflections
a = 11.8269 (5) Åθ = 2.3–28.3°
b = 11.8130 (4) ŵ = 0.30 mm1
c = 12.8918 (5) ÅT = 296 K
β = 92.213 (2)°Prismatic, colorless
V = 1799.79 (12) Å30.26 × 0.20 × 0.16 mm
Z = 4

Data collection

Bruker KappaAPEXII CCD diffractometer4465 independent reflections
Radiation source: fine-focus sealed tube3145 reflections with I > 2σ(I)
graphiteRint = 0.034
Detector resolution: 7.40 pixels mm-1θmax = 28.3°, θmin = 2.3°
ω scansh = −15→15
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −10→15
Tmin = 0.928, Tmax = 0.950l = −17→14
19927 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0464P)2 + 0.4839P] where P = (Fo2 + 2Fc2)/3
4465 reflections(Δ/σ)max < 0.001
208 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = −0.31 e Å3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
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
Cl10.64049 (5)0.13296 (4)0.08789 (5)0.0652 (2)
P10.81585 (4)0.28430 (4)0.41401 (3)0.0347 (1)
N10.7328 (2)0.38278 (18)0.67432 (16)0.0773 (8)
C10.66854 (15)0.30928 (15)0.38497 (13)0.0396 (5)
C20.59647 (17)0.22052 (19)0.35858 (15)0.0539 (7)
C30.48330 (19)0.2418 (3)0.33767 (18)0.0708 (9)
C40.4421 (2)0.3502 (3)0.34392 (19)0.0758 (9)
C50.51305 (19)0.4389 (2)0.36860 (17)0.0674 (8)
C60.62701 (17)0.41952 (18)0.38895 (15)0.0530 (7)
C70.89873 (15)0.31735 (14)0.30527 (13)0.0392 (5)
C81.00699 (17)0.36037 (18)0.31824 (15)0.0537 (7)
C91.06821 (19)0.3851 (2)0.23237 (18)0.0710 (9)
C101.0223 (2)0.3654 (3)0.13446 (19)0.0809 (10)
C110.9166 (2)0.3196 (3)0.12143 (17)0.0825 (12)
C120.85329 (18)0.2966 (2)0.20620 (15)0.0620 (8)
C130.83557 (14)0.14007 (14)0.45185 (14)0.0386 (5)
C140.86489 (19)0.05919 (17)0.37959 (17)0.0576 (7)
C150.8752 (2)−0.05313 (17)0.40849 (19)0.0640 (8)
C160.85644 (18)−0.08481 (17)0.50791 (19)0.0611 (8)
C170.8289 (2)−0.00608 (19)0.58004 (18)0.0663 (8)
C180.81820 (19)0.10688 (17)0.55274 (16)0.0552 (7)
C190.86206 (15)0.37784 (14)0.51789 (13)0.0404 (5)
C200.78895 (19)0.37952 (16)0.60511 (16)0.0501 (7)
H20.624260.147040.355000.0647*
H30.434710.182640.319270.0849*
H40.365300.363620.331290.0908*
H50.484440.512060.371640.0809*
H60.675490.479490.405130.0636*
H81.038340.372590.384560.0644*
H91.140700.415040.240660.0853*
H101.063470.383490.076680.0970*
H110.887400.303820.054980.0990*
H120.780550.267420.197210.0744*
H140.877640.080590.311610.0690*
H150.89494−0.107150.359940.0767*
H160.86246−0.160630.526740.0733*
H170.81722−0.028390.647980.0795*
H180.799370.160270.602200.0662*
H19A0.867390.454050.490480.0485*
H19B0.937300.355220.542330.0485*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0647 (3)0.0431 (3)0.0854 (4)−0.0019 (2)−0.0289 (3)−0.0085 (2)
P10.0349 (2)0.0353 (2)0.0335 (2)0.0008 (2)−0.0029 (2)−0.0028 (2)
N10.0872 (15)0.0903 (16)0.0549 (12)0.0070 (12)0.0102 (11)−0.0203 (11)
C10.0354 (9)0.0521 (10)0.0312 (9)0.0023 (8)−0.0011 (7)−0.0010 (7)
C20.0478 (11)0.0621 (12)0.0512 (12)−0.0067 (10)−0.0057 (9)−0.0032 (10)
C30.0468 (13)0.0974 (19)0.0669 (15)−0.0187 (12)−0.0128 (11)0.0019 (13)
C40.0408 (12)0.122 (2)0.0638 (15)0.0114 (14)−0.0064 (10)0.0088 (15)
C50.0521 (13)0.0833 (16)0.0662 (14)0.0248 (12)−0.0052 (11)−0.0011 (12)
C60.0466 (11)0.0597 (12)0.0522 (12)0.0102 (9)−0.0052 (9)−0.0023 (10)
C70.0379 (9)0.0427 (9)0.0367 (9)0.0010 (7)−0.0009 (7)−0.0030 (7)
C80.0439 (11)0.0720 (14)0.0451 (11)−0.0083 (10)0.0007 (9)−0.0115 (10)
C90.0478 (12)0.103 (2)0.0630 (15)−0.0196 (12)0.0138 (11)−0.0119 (13)
C100.0630 (16)0.129 (2)0.0521 (14)−0.0080 (15)0.0210 (12)0.0016 (14)
C110.0623 (16)0.148 (3)0.0372 (12)−0.0081 (16)0.0014 (10)−0.0048 (14)
C120.0448 (11)0.1007 (18)0.0402 (11)−0.0116 (11)−0.0036 (9)−0.0066 (11)
C130.0354 (9)0.0345 (8)0.0458 (10)0.0013 (7)−0.0001 (7)−0.0017 (7)
C140.0790 (15)0.0447 (11)0.0492 (12)0.0012 (10)0.0054 (10)−0.0090 (9)
C150.0814 (16)0.0399 (10)0.0704 (15)0.0028 (10)0.0010 (12)−0.0138 (10)
C160.0608 (13)0.0360 (10)0.0862 (17)0.0014 (9)−0.0024 (12)0.0041 (10)
C170.0838 (16)0.0533 (12)0.0625 (14)0.0078 (12)0.0131 (12)0.0171 (11)
C180.0703 (14)0.0457 (10)0.0505 (12)0.0111 (10)0.0143 (10)0.0026 (9)
C190.0452 (10)0.0372 (9)0.0382 (9)0.0018 (7)−0.0078 (8)−0.0047 (7)
C200.0595 (12)0.0485 (11)0.0418 (11)0.0057 (9)−0.0060 (10)−0.0116 (8)

Geometric parameters (Å, °)

P1—C11.7923 (18)C16—C171.364 (3)
P1—C71.7845 (18)C17—C181.385 (3)
P1—C131.7851 (17)C19—C201.445 (3)
P1—C191.8046 (17)C2—H20.9300
N1—C201.133 (3)C3—H30.9300
C1—C21.385 (3)C4—H40.9300
C1—C61.394 (3)C5—H50.9300
C2—C31.378 (3)C6—H60.9300
C3—C41.374 (5)C8—H80.9300
C4—C51.372 (4)C9—H90.9300
C5—C61.382 (3)C10—H100.9300
C7—C81.382 (3)C11—H110.9300
C7—C121.388 (3)C12—H120.9300
C8—C91.377 (3)C14—H140.9300
C9—C101.375 (3)C15—H150.9300
C10—C111.367 (4)C16—H160.9300
C11—C121.376 (3)C17—H170.9300
C13—C141.388 (3)C18—H180.9300
C13—C181.381 (3)C19—H19A0.9700
C14—C151.382 (3)C19—H19B0.9700
C15—C161.362 (3)
Cl1···C19i3.3076 (17)C14···H23.0300
Cl1···C16ii3.556 (2)C15···H12i3.0900
Cl1···C19iii3.3830 (19)C18···H10viii3.0400
Cl1···C123.479 (2)C19···H182.9000
Cl1···H16ii2.8500C19···H82.7500
Cl1···H19Ai2.3400C19···H62.8600
Cl1···H8iii2.8400C20···H63.0900
Cl1···H19Biii2.4600C20···H182.5900
Cl1···H122.6600H2···C143.0300
Cl1···H6i2.8300H2···C132.7500
N1···H182.9100H5···N1v2.8900
N1···H17iv2.6100H6···Cl1ii2.8300
N1···H5v2.8900H6···H19A2.5000
C6···C203.353 (3)H6···C192.8600
C12···C143.586 (3)H6···C203.0900
C12···Cl13.479 (2)H8···H19B2.4100
C12···C15ii3.512 (3)H8···C192.7500
C14···C123.586 (3)H8···Cl1vii2.8400
C14···C16vi3.562 (3)H10···C18ix3.0400
C15···C17vi3.566 (3)H12···Cl12.6600
C15···C12i3.512 (3)H12···C15ii3.0900
C16···Cl1i3.556 (2)H12···C12.8500
C16···C14vi3.562 (3)H14···C122.9000
C17···C15vi3.566 (3)H14···C72.8100
C18···C203.312 (3)H16···Cl1i2.8500
C19···Cl1vii3.3830 (19)H17···N1x2.6100
C19···Cl1ii3.3076 (17)H18···N12.9100
C20···C63.353 (3)H18···C202.5900
C20···C183.312 (3)H18···C192.9000
C1···H122.8500H19A···Cl1ii2.3400
C7···H142.8100H19A···H62.5000
C8···H19A3.0300H19A···C83.0300
C8···H19B3.0400H19B···C83.0400
C12···H142.9000H19B···H82.4100
C13···H22.7500H19B···Cl1vii2.4600
C1—P1—C7111.03 (8)C2—C3—H3120.00
C1—P1—C13109.26 (8)C4—C3—H3120.00
C1—P1—C19108.56 (8)C3—C4—H4120.00
C7—P1—C13110.71 (8)C5—C4—H4120.00
C7—P1—C19106.81 (8)C4—C5—H5120.00
C13—P1—C19110.43 (8)C6—C5—H5120.00
P1—C1—C2120.70 (14)C1—C6—H6120.00
P1—C1—C6119.17 (14)C5—C6—H6120.00
C2—C1—C6120.13 (17)C7—C8—H8120.00
C1—C2—C3119.6 (2)C9—C8—H8120.00
C2—C3—C4120.2 (3)C8—C9—H9120.00
C3—C4—C5120.7 (2)C10—C9—H9120.00
C4—C5—C6120.0 (2)C9—C10—H10120.00
C1—C6—C5119.36 (19)C11—C10—H10120.00
P1—C7—C8121.33 (14)C10—C11—H11120.00
P1—C7—C12118.64 (14)C12—C11—H11120.00
C8—C7—C12120.02 (17)C7—C12—H12120.00
C7—C8—C9119.62 (18)C11—C12—H12120.00
C8—C9—C10120.1 (2)C13—C14—H14120.00
C9—C10—C11120.5 (2)C15—C14—H14120.00
C10—C11—C12120.3 (2)C14—C15—H15120.00
C7—C12—C11119.5 (2)C16—C15—H15120.00
P1—C13—C14120.47 (14)C15—C16—H16120.00
P1—C13—C18120.37 (14)C17—C16—H16120.00
C14—C13—C18119.13 (17)C16—C17—H17120.00
C13—C14—C15120.1 (2)C18—C17—H17120.00
C14—C15—C16120.1 (2)C13—C18—H18120.00
C15—C16—C17120.4 (2)C17—C18—H18120.00
C16—C17—C18120.4 (2)P1—C19—H19A109.00
C13—C18—C17119.83 (19)P1—C19—H19B109.00
P1—C19—C20114.38 (13)C20—C19—H19A109.00
N1—C20—C19178.6 (2)C20—C19—H19B109.00
C1—C2—H2120.00H19A—C19—H19B108.00
C3—C2—H2120.00
C7—P1—C1—C2100.11 (16)P1—C1—C6—C5−178.74 (15)
C7—P1—C1—C6−79.73 (16)C2—C1—C6—C51.4 (3)
C13—P1—C1—C2−22.28 (17)C1—C2—C3—C4−0.6 (3)
C13—P1—C1—C6157.89 (14)C2—C3—C4—C51.5 (4)
C19—P1—C1—C2−142.77 (15)C3—C4—C5—C6−0.9 (4)
C19—P1—C1—C637.40 (17)C4—C5—C6—C1−0.5 (3)
C1—P1—C7—C8146.77 (15)P1—C7—C8—C9−179.84 (17)
C1—P1—C7—C12−34.67 (18)C12—C7—C8—C91.6 (3)
C13—P1—C7—C8−91.68 (17)P1—C7—C12—C11−178.8 (2)
C13—P1—C7—C1286.88 (17)C8—C7—C12—C11−0.3 (3)
C19—P1—C7—C828.58 (18)C7—C8—C9—C10−1.0 (4)
C19—P1—C7—C12−152.86 (16)C8—C9—C10—C11−1.0 (4)
C1—P1—C13—C1495.07 (17)C9—C10—C11—C122.4 (5)
C1—P1—C13—C18−82.80 (17)C10—C11—C12—C7−1.8 (4)
C7—P1—C13—C14−27.51 (18)P1—C13—C14—C15−177.19 (17)
C7—P1—C13—C18154.62 (15)C18—C13—C14—C150.7 (3)
C19—P1—C13—C14−145.59 (16)P1—C13—C18—C17177.16 (17)
C19—P1—C13—C1836.54 (18)C14—C13—C18—C17−0.7 (3)
C1—P1—C19—C2048.05 (15)C13—C14—C15—C160.1 (3)
C7—P1—C19—C20167.85 (13)C14—C15—C16—C17−0.9 (3)
C13—P1—C19—C20−71.71 (15)C15—C16—C17—C180.9 (3)
P1—C1—C2—C3179.31 (16)C16—C17—C18—C130.0 (3)
C6—C1—C2—C3−0.9 (3)

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+3/2, y+1/2, −z+3/2; (v) −x+1, −y+1, −z+1; (vi) −x+2, −y, −z+1; (vii) x+1/2, −y+1/2, z+1/2; (viii) x−1/2, −y+1/2, z+1/2; (ix) x+1/2, −y+1/2, z−1/2; (x) −x+3/2, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C12—H12···Cl10.932.663.479 (2)147
C17—H17···N1x0.932.613.530 (3)171
C19—H19A···Cl1ii0.972.343.3076 (17)173
C19—H19B···Cl1vii0.972.463.3830 (19)160
C15—H15···Cg1i0.933.063.890 (3)150

Symmetry codes: (x) −x+3/2, y−1/2, −z+3/2; (ii) −x+3/2, y+1/2, −z+1/2; (vii) x+1/2, −y+1/2, z+1/2; (i) −x+3/2, y−1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2558).

References

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