Diphenyl(pyridin-2-yl)­phosphane selenide

Wade L Davis; Alfred Muller

doi:10.1107/S160053681204007X

. 2012 Oct 6;68(Pt 11):o3073. doi: 10.1107/S160053681204007X

Diphenyl(pyridin-2-yl)phosphane selenide

Wade L Davis ^a, Alfred Muller ^a,^*

PMCID: PMC3515180 PMID: 23284407

Abstract

In the title compound, C₁₇H₁₄NPSe, the P atom has a distorted tetrahedral environment resulting in an effective cone angle of 163°. In the crystal, C—H⋯Se/N/π interactions are observed.

Related literature

For background to phosphorus- and selenium-containing ligands, see: Muller et al. (2006 ▶, 2008 ▶). For the free phosphine of the title compound, see: Charland et al. (1989 ▶). For background on cone angles, see: Otto (2001 ▶); Tolman (1977 ▶). For details of the conformational fit of the two molecules using Mercury, see: Macrae et al. (2008 ▶); Weng et al. (2008a ▶,b ▶).

Experimental

Crystal data

C₁₇H₁₄NPSe
M _r = 342.22
Orthorhombic,
a = 8.8092 (4) Å
b = 9.4066 (4) Å
c = 18.2661 (7) Å
V = 1513.61 (11) Å³
Z = 4
Cu Kα radiation
μ = 4.25 mm⁻¹
T = 100 K
0.24 × 0.17 × 0.12 mm

Data collection

Bruker APEX DUO 4K-CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.429, T _max = 0.629
6004 measured reflections
2501 independent reflections
2461 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.021
wR(F ²) = 0.053
S = 0.87
2501 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack (1983 ▶), with 992 Friedel pairs
Flack parameter: 0.053 (19)

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT and XPREP (Bruker, 2008 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶) and WinGX (Farrugia, 1999 ▶).

Supplementary Material

Click here for additional data file.^{(18.1KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681204007X/kp2438sup1.cif

e-68-o3073-sup1.cif^{(18.1KB, cif)}

Click here for additional data file.^{(120.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681204007X/kp2438Isup2.hkl

e-68-o3073-Isup2.hkl^{(120.4KB, hkl)}

Click here for additional data file.^{(5.2KB, cml)}

Supplementary material file. DOI: 10.1107/S160053681204007X/kp2438Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯Se1	0.95	2.87	3.427 (3)	118
C8—H8⋯N1	0.95	2.57	3.111 (3)	116
C14—H14⋯Se1	0.95	2.96	3.472 (2)	115
C5—H5⋯Se1ⁱ	0.95	3.07	3.923 (3)	150
C16—H16⋯Se1ⁱⁱ	0.95	3.26	3.938 (3)	130
C11—H11⋯Cg1ⁱⁱⁱ	0.95	2.77	3.630 (3)	151

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

Acknowledgments

Financial assistance from the Research Fund of the University of Johannesburg is gratefully acknowledged.

supplementary crystallographic information

Comment

As part our systematic investigation on the steric and electronic properties of phosphorus containing ligands, we are also utilizing the ¹J(³¹P-⁷⁷Se) multi-nuclear NMR coupling in Se—P bond as a probe (see Muller et al., 2008). The advantage of this approach is that there is no steric crowding effect, albeit crystal packing effects, as normally found in transition metal complexes with bulky ligands, e.g. in trans-[Rh(CO)Cl{P(OC₆H₅)₃}₂] cone angles variation from 156° to 167° was observed for the two phosphite ligands (Muller et al., 2006). Herein we report here the single-crystal structure of SePPh₂py, where Ph = C₆H₅ and py = C₅H₄N as part of our investigation.

Molecules of the title compound (Fig. 1) adopts a distorted tetrahedral arrangement about the P atom with average C—P—C and Se—P—C angles of 105.47° and 113.20° respectively. Describing the steric demand of phosphane ligands has been the topic of many studies and a variety of models have been developed. The Tolman cone angle (Tolman, 1977) is still the most commonly used model. Applying this model to the geometry obtained for the title compound (and adjusting the Se—P bond distance to 2.28 Å) we calculated an effective cone angle from the geometry found in the crystal structure of 163° (Otto, 2001). The angle calculated is 9° larger than that of the free phosphine (Charland et al., 1989; effective cone angle calculated as 154°), and could be ascribed to C—H···Se/N/π intra- and interactions observed in the title compound (Table 1, Fig. 2), whereas the free phosphine shows C—H···N/π interactions only. The difference in the orientation of the substituents for these two structures can be illustrated by superimposing their coordinates (Fig. 3); root mean squared deviation calculated as 0.0468 Å for P and ipso C atoms only using Mercury (Macrae et al., 2008; Weng et al., 2008a,b).

Experimental

Diphenyl-2-pyridylphosphine and KSeCN were purchased from Sigma–Aldrich and used without purification. Eqimolar amounts of KSeCN (5.8 mg, 0.04 mmol) and the diphenylpyridylphosphine (10.5 mg, 0.04 mmol) were dissolved in the minimum amounts of methanol (10 ml). The KSeCN solution was added dropwise (5 min) to the phosphine solution with stirring at room temperature. The final solution was left to evaporate slowly until dry to give crystals suitable for a single-crystal X-ray study. Analytical data: ³¹P {H} NMR (CDCl₃, 161.99 MHz): δ = 31.47 (t, ¹J(³¹P-⁷⁷Se) = 734 Hz).