(2-Bromo­phenyl)­di­phenyl­phosphine

The crystal structure of (2-bromo­phenyl)­di­phenyl­phosphine, C₁₈H₁₄BrP, (I), has been determined at 295 (1) K. The structure of (I) is isomorphous with the analogous methyl compound (2-methyl­phenyl)­di­phenyl­phosphine.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.043
• wR factor = 0.150
• Data-to-parameter ratio = 19.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

---

S1. Comment

(2-Bromophenyl)diphenylphosphine, (I), has been shown to coordinate to metal centres as both a monodentate ligand through the P-donor atom, and as a chelating hemilabile ligand through both the phosphine and the aryl bromide donor groups (Burk et al., 1988). The solid-state structure of (I) is isomorphous with the structure reported for (2-methylphenyl)diphenylphosphine, (II) (Bowmaker et al., 1987).

The structure consists of discrete molecular species which adopt a propellor-shaped conformation with the phenyl rings twisted away from the normal to the base of the PC₃ pyramid by 36, 27 and 53° [cf. (II): 36, 26 and 47°]. The bromide is located cis to the phosphorus lone pair. The P—C bond lengths [mean value 1.836 (6) Å] are similar to those recorded for triphenylphosphine [mean value 1.831 (2) Å; Dunne & Orpen, 1991], while the mean value of the C—P—C bonds of 101.9 (8)° is marginally smaller than the value of 102.8 (5)° observed for triphenylphosphine. Introduction of the bromide substituent on ring 1 in (I) results in a small increase in the P—C11—C12 angle to 119.8 (3)° compared to 117.1 (3) and 116.4 (3)° for P—C21—C22 and P—C31—C32. The corresponding angles in triphenylphosphine are 116.6 (1), 116.8 (1) and 117.5 (1)°. The molecules are linked in the crystal lattice through edge-to-face C—H···π interactions between the phenyl groups (Scudder & Dance, 1998). In accord with previous studies demonstrating the poor hydrogen-bond acceptor properties of C—X bonds (Aullón et al., 1998), there is no evidence of significant C—H···Br intermolecular interactions in (I) with the shortest H···Br distances being greater than 3.1 Å.

S2. Experimental

The title compound was obtained as a white crystalline powder from the PdCl₂(CH₃CN)₄-catalysed reaction between ortho-bromoiodobenzene and diphenyl(trimethylsilyl)phosphine (Tunney et al., 1987); m.p. 386–388 K. Crystals of the compound suitable for X-ray diffraction studies were obtained during an attempt to recrystallize the 1:2 copper(I) bromide complex by diffusion of ether into a solution of the complex in dichloromethane.

S3. Refinement

H atoms were located at calculated positions with C—H distances set to 0.95 Å and were constrained in refinement.

Computing details

Data collection: MSC/AFC7 Diffractometer Control Software (Molecular Structure Corporation, 1999); cell refinement: MSC/AFC7 Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 2001); program(s) used to solve structure: TEXSAN for Windows; program(s) used to refine structure: TEXSAN for Windows and SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: TEXSAN and PLATON (Spek, 2001).

Figures

Fig. 1. ORTEP-3 (Farrugia, 1997) plot of the title compound showing the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.

(2-bromophenyl)diphenylphosphine

Crystal data

C18H14BrP	F(000) = 688
Mr = 341.16	Dx = 1.472 Mg m^−3
Monoclinic, P21/c	Melting point: 386-388 K K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.7107 Å
a = 10.371 (5) Å	Cell parameters from 25 reflections
b = 8.9735 (19) Å	θ = 13.2–16.0°
c = 16.556 (6) Å	µ = 2.76 mm^−1
β = 92.33 (4)°	T = 295 K
V = 1539.5 (10) Å^3	Plate, colorless
Z = 4	0.40 × 0.30 × 0.20 mm

Data collection

Rigaku AFC-7R diffractometer	1823 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode	Rint = 0.033
Graphite monochromator	θmax = 27.5°, θmin = 2.6°
ω–2θ scans	h = −13→13
Absorption correction: ψ scan (North et al., 1968)	k = −11→0
Tmin = 0.383, Tmax = 0.576	l = −12→21
4223 measured reflections	3 standard reflections every 150 reflections
3540 independent reflections	intensity decay: 0.8%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters not refined
wR(F^2) = 0.150	w = 1/[σ^2(Fo^2) + (0.0553P)^2 + 1.0428P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3540 reflections	Δρmax = 0.79 e Å^−3
182 parameters	Δρmin = −0.70 e Å^−3
0 restraints	Extinction correction: SHELXL97, FC^*=KFC[1+0.001XFC^2Λ^3/SIN(2Θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0033 (9)

Special details

Experimental. The scan width was (1.73 + 0.30tanθ)° with an ω scan speed of 16° per minute (up to 5 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'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 on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2σ(F²) is used only for calculating -R-factor-obs 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 (Ų)

	x	y	z	Uiso*/Ueq
Br	0.68179 (6)	−0.08819 (5)	0.49050 (3)	0.0769 (2)
P	0.66009 (9)	0.25187 (12)	0.41885 (6)	0.0491 (3)
C11	0.8009 (4)	0.1368 (5)	0.3950 (2)	0.0509 (12)
C12	0.8118 (4)	−0.0069 (5)	0.4254 (3)	0.0544 (12)
C13	0.9161 (5)	−0.0958 (5)	0.4097 (3)	0.0727 (17)
C14	1.0121 (5)	−0.0434 (7)	0.3630 (4)	0.080 (2)
C15	1.0041 (5)	0.0973 (7)	0.3307 (3)	0.079 (2)
C16	0.8989 (4)	0.1866 (5)	0.3466 (3)	0.0655 (16)
C21	0.7193 (4)	0.3479 (4)	0.5108 (2)	0.0469 (12)
C22	0.6280 (4)	0.3961 (5)	0.5637 (3)	0.0562 (14)
C23	0.6644 (5)	0.4740 (5)	0.6328 (3)	0.0651 (17)
C24	0.7918 (5)	0.5022 (5)	0.6514 (3)	0.0680 (17)
C25	0.8842 (4)	0.4544 (6)	0.5997 (3)	0.0703 (17)
C26	0.8488 (4)	0.3782 (5)	0.5301 (3)	0.0617 (17)
C31	0.6671 (4)	0.3976 (4)	0.3417 (2)	0.0464 (12)
C32	0.6297 (4)	0.3566 (5)	0.2633 (3)	0.0568 (16)
C33	0.6202 (4)	0.4616 (6)	0.2021 (3)	0.0638 (16)
C34	0.6462 (5)	0.6088 (5)	0.2184 (3)	0.0635 (17)
C35	0.6828 (4)	0.6509 (5)	0.2958 (3)	0.0599 (16)
C36	0.6946 (4)	0.5467 (5)	0.3569 (2)	0.0501 (12)
H13	0.92140	−0.19370	0.43140	0.0870*
H14	1.08450	−0.10460	0.35300	0.0960*
H15	1.07010	0.13330	0.29760	0.0950*
H16	0.89360	0.28370	0.32390	0.0790*
H22	0.53930	0.37530	0.55230	0.0670*
H23	0.60030	0.50840	0.66770	0.0780*
H24	0.81640	0.55440	0.69950	0.0820*
H25	0.97280	0.47410	0.61210	0.0850*
H26	0.91330	0.34590	0.49480	0.0740*
H32	0.61050	0.25520	0.25150	0.0680*
H33	0.59560	0.43160	0.14870	0.0760*
H34	0.63900	0.68090	0.17650	0.0760*
H35	0.70010	0.75280	0.30730	0.0720*
H36	0.72180	0.57720	0.40980	0.0600*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br	0.1046 (5)	0.0595 (3)	0.0674 (3)	0.0035 (3)	0.0138 (3)	0.0047 (2)
P	0.0439 (5)	0.0515 (6)	0.0519 (6)	0.0024 (5)	0.0025 (4)	0.0004 (5)
C11	0.049 (2)	0.052 (2)	0.051 (2)	0.0040 (19)	−0.0082 (19)	−0.0110 (19)
C12	0.054 (2)	0.055 (2)	0.053 (2)	0.006 (2)	−0.0118 (19)	−0.011 (2)
C13	0.080 (3)	0.060 (3)	0.077 (3)	0.020 (3)	−0.012 (3)	−0.013 (2)
C14	0.060 (3)	0.087 (4)	0.092 (4)	0.026 (3)	−0.006 (3)	−0.032 (3)
C15	0.049 (3)	0.101 (5)	0.088 (4)	0.003 (3)	0.011 (2)	−0.019 (3)
C16	0.048 (2)	0.066 (3)	0.083 (3)	0.002 (2)	0.009 (2)	−0.004 (2)
C21	0.048 (2)	0.046 (2)	0.047 (2)	0.0107 (18)	0.0055 (17)	0.0094 (18)
C22	0.052 (2)	0.065 (3)	0.052 (2)	0.005 (2)	0.0063 (19)	0.003 (2)
C23	0.072 (3)	0.065 (3)	0.059 (3)	0.010 (2)	0.012 (2)	−0.004 (2)
C24	0.084 (3)	0.065 (3)	0.054 (3)	0.012 (3)	−0.010 (2)	−0.011 (2)
C25	0.054 (3)	0.087 (3)	0.069 (3)	0.007 (3)	−0.009 (2)	−0.016 (3)
C26	0.050 (3)	0.078 (3)	0.057 (3)	0.013 (2)	0.0025 (19)	−0.011 (2)
C31	0.042 (2)	0.053 (2)	0.044 (2)	0.0036 (17)	0.0004 (16)	−0.0032 (18)
C32	0.060 (3)	0.055 (2)	0.055 (3)	−0.002 (2)	−0.001 (2)	−0.002 (2)
C33	0.067 (3)	0.079 (3)	0.045 (2)	−0.006 (2)	−0.001 (2)	−0.004 (2)
C34	0.065 (3)	0.072 (3)	0.054 (3)	0.005 (2)	0.007 (2)	0.011 (2)
C35	0.062 (3)	0.052 (2)	0.066 (3)	−0.001 (2)	0.005 (2)	0.000 (2)
C36	0.051 (2)	0.053 (2)	0.046 (2)	−0.0004 (19)	0.0000 (18)	−0.0020 (18)

Geometric parameters (Å, º)

Br—C12	1.905 (5)	C32—C33	1.384 (7)
P—C11	1.844 (4)	C33—C34	1.373 (7)
P—C21	1.833 (4)	C34—C35	1.375 (7)
P—C31	1.832 (4)	C35—C36	1.379 (6)
C11—C12	1.387 (6)	C13—H13	0.9499
C11—C16	1.393 (6)	C14—H14	0.9502
C12—C13	1.377 (7)	C15—H15	0.9506
C13—C14	1.368 (8)	C16—H16	0.9496
C14—C15	1.372 (9)	C22—H22	0.9500
C15—C16	1.387 (7)	C23—H23	0.9499
C21—C22	1.385 (6)	C24—H24	0.9498
C21—C26	1.395 (6)	C25—H25	0.9499
C22—C23	1.380 (7)	C26—H26	0.9512
C23—C24	1.368 (7)	C32—H32	0.9500
C24—C25	1.379 (7)	C33—H33	0.9491
C25—C26	1.377 (7)	C34—H34	0.9493
C31—C32	1.389 (6)	C35—H35	0.9496
C31—C36	1.389 (6)	C36—H36	0.9494
Br···P	3.278 (2)	C34···H15^vi	2.9730
Br···H33^i	3.1343	C35···H15^vi	3.0505
Br···H34^i	3.2377	C36···H22^iv	2.9884
P···Br	3.278 (2)	H13···C26^iii	2.9502
C16···C32	3.422 (6)	H13···H26^iii	2.4752
C16···C26	3.547 (7)	H15···C34^vii	2.9730
C26···C36	3.563 (6)	H15···C35^vii	3.0505
C26···C16	3.547 (7)	H16···C31	2.5895
C32···C16	3.422 (6)	H16···C32	2.9499
C36···C26	3.563 (6)	H22···C36^iv	2.9884
C11···H26	2.7300	H23···C31^iv	2.8968
C13···H35^ii	3.0707	H23···C32^iv	2.9468
C16···H26	2.8383	H26···C11	2.7300
C21···H36	2.6522	H26···C16	2.8383
C23···H32^i	2.9144	H26···H13^iii	2.4752
C26···H36	2.9457	H32···C34^viii	3.0281
C26···H13^iii	2.9502	H32···C23^ix	2.9144
C31···H16	2.5895	H33···Br^ix	3.1343
C31···H23^iv	2.8968	H34···Br^ix	3.2377
C32···H16	2.9499	H35···C13^x	3.0707
C32···H23^iv	2.9468	H36···C21	2.6522
C34···H32^v	3.0281	H36···C26	2.9457
C11—P—C21	101.51 (18)	C12—C13—H13	119.88
C11—P—C31	101.32 (18)	C14—C13—H13	119.95
C21—P—C31	102.83 (16)	C13—C14—H14	119.87
P—C11—C12	119.8 (3)	C15—C14—H14	119.97
P—C11—C16	123.1 (3)	C14—C15—H15	120.25
C12—C11—C16	117.1 (4)	C16—C15—H15	120.22
Br—C12—C11	120.8 (3)	C11—C16—H16	119.35
Br—C12—C13	117.7 (3)	C15—C16—H16	119.22
C11—C12—C13	121.5 (4)	C21—C22—H22	119.63
C12—C13—C14	120.2 (5)	C23—C22—H22	119.62
C13—C14—C15	120.2 (5)	C22—C23—H23	119.62
C14—C15—C16	119.5 (5)	C24—C23—H23	119.76
C11—C16—C15	121.4 (4)	C23—C24—H24	120.26
P—C21—C22	117.2 (3)	C25—C24—H24	120.27
P—C21—C26	124.7 (3)	C24—C25—H25	119.90
C22—C21—C26	118.1 (4)	C26—C25—H25	119.73
C21—C22—C23	120.8 (4)	C21—C26—H26	119.64
C22—C23—C24	120.6 (5)	C25—C26—H26	119.69
C23—C24—C25	119.5 (5)	C31—C32—H32	119.61
C24—C25—C26	120.4 (4)	C33—C32—H32	119.56
C21—C26—C25	120.7 (4)	C32—C33—H33	119.82
P—C31—C32	116.4 (3)	C34—C33—H33	119.95
P—C31—C36	125.1 (3)	C33—C34—H34	120.21
C32—C31—C36	118.2 (3)	C35—C34—H34	120.30
C31—C32—C33	120.8 (4)	C34—C35—H35	119.63
C32—C33—C34	120.2 (5)	C36—C35—H35	119.69
C33—C34—C35	119.5 (4)	C31—C36—H36	119.73
C34—C35—C36	120.7 (4)	C35—C36—H36	119.69
C31—C36—C35	120.6 (3)
C21—P—C11—C12	91.1 (4)	C12—C13—C14—C15	−0.9 (8)
C21—P—C11—C16	−89.3 (4)	C13—C14—C15—C16	0.8 (9)
C31—P—C11—C12	−163.1 (3)	C14—C15—C16—C11	0.2 (8)
C31—P—C11—C16	16.4 (4)	P—C21—C22—C23	−177.6 (3)
C11—P—C21—C22	−154.5 (3)	C26—C21—C22—C23	1.0 (6)
C11—P—C21—C26	26.9 (4)	P—C21—C26—C25	178.3 (4)
C31—P—C21—C22	100.9 (3)	C22—C21—C26—C25	−0.2 (6)
C31—P—C21—C26	−77.7 (4)	C21—C22—C23—C24	−1.5 (7)
C11—P—C31—C32	74.0 (4)	C22—C23—C24—C25	1.1 (7)
C11—P—C31—C36	−112.5 (4)	C23—C24—C25—C26	−0.3 (7)
C21—P—C31—C32	178.7 (3)	C24—C25—C26—C21	−0.1 (7)
C21—P—C31—C36	−7.8 (4)	P—C31—C32—C33	174.0 (3)
P—C11—C12—Br	0.8 (5)	C36—C31—C32—C33	0.0 (6)
P—C11—C12—C13	−179.3 (4)	P—C31—C36—C35	−172.4 (3)
C16—C11—C12—Br	−178.7 (3)	C32—C31—C36—C35	1.1 (6)
C16—C11—C12—C13	1.1 (7)	C31—C32—C33—C34	−0.8 (7)
P—C11—C16—C15	179.3 (4)	C32—C33—C34—C35	0.6 (7)
C12—C11—C16—C15	−1.2 (7)	C33—C34—C35—C36	0.5 (7)
Br—C12—C13—C14	179.7 (4)	C34—C35—C36—C31	−1.3 (7)
C11—C12—C13—C14	−0.2 (8)

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