(Cyano­meth­yl)triphenyl­phospho­nium chloride

Muhammad Shafiq; M Nawaz Tahir; Islam Ullah Khan; Muhammad Nadeem Arshad; Zaib-un-Nisa

doi:10.1107/S1600536808034673

. 2008 Oct 31;64(Pt 11):o2213. doi: 10.1107/S1600536808034673

(Cyanomethyl)triphenylphosphonium chloride

Muhammad Shafiq ^a, M Nawaz Tahir ^b,^*, Islam Ullah Khan ^a, Muhammad Nadeem Arshad ^a, Zaib-un-Nisa ^a

PMCID: PMC2959552 PMID: 21581070

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 ▶); Czerwinski & Ponnuswamy (1988 ▶); de Dubourg et al. (1986 ▶); Fischer & Wiebelhaus (1997 ▶); Shafiq et al. (2008 ▶); Skapski & Stephens (1974 ▶); Tahir et al. (2008 ▶).

Experimental

Crystal data

C₂₀H₁₇NP⁺·Cl⁻
M _r = 337.77
Monoclinic,
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 ▶) 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
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.31 e Å⁻³

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

Supplementary Material

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

e-64-o2213-sup1.cif^{(21.9KB, cif)}

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

e-64-o2213-Isup2.hkl^{(214.4KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

P1—C1	1.7923 (18)
P1—C7	1.7845 (18)
P1—C13	1.7851 (17)
P1—C19	1.8046 (17)

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C1—P1—C7	111.03 (8)
C1—P1—C13	109.26 (8)
C1—P1—C19	108.56 (8)
C7—P1—C13	110.71 (8)
C7—P1—C19	106.81 (8)
C13—P1—C19	110.43 (8)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯Cl1	0.93	2.66	3.479 (2)	147
C17—H17⋯N1ⁱ	0.93	2.61	3.530 (3)	171
C19—H19A⋯Cl1ⁱⁱ	0.97	2.34	3.3076 (17)	173
C19—H19B⋯Cl1ⁱⁱⁱ	0.97	2.46	3.3830 (19)	160

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

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.