Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002945/tk6055sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002945/tk6055Isup2.hkl |
CCDC reference: 182629
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (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
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.
H atoms were located at calculated positions with C—H distances set to 0.95 Å and were constrained in refinement.
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).
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. |
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) Å3 | Plate, colorless |
Z = 4 | 0.40 × 0.30 × 0.20 mm |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters not refined |
wR(F2) = 0.150 | w = 1/[σ2(Fo2) + (0.0553P)2 + 1.0428P] where P = (Fo2 + 2Fc2)/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+0.001XFC2Λ3/SIN(2Θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0033 (9) |
C18H14BrP | V = 1539.5 (10) Å3 |
Mr = 341.16 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.371 (5) Å | µ = 2.76 mm−1 |
b = 8.9735 (19) Å | T = 295 K |
c = 16.556 (6) Å | 0.40 × 0.30 × 0.20 mm |
β = 92.33 (4)° |
Rigaku AFC-7R diffractometer | 1823 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.033 |
Tmin = 0.383, Tmax = 0.576 | 3 standard reflections every 150 reflections |
4223 measured reflections | intensity decay: 0.8% |
3540 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.150 | H-atom parameters not refined |
S = 1.01 | Δρmax = 0.79 e Å−3 |
3540 reflections | Δρmin = −0.70 e Å−3 |
182 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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···H15vi | 2.9730 |
Br···H33i | 3.1343 | C35···H15vi | 3.0505 |
Br···H34i | 3.2377 | C36···H22iv | 2.9884 |
P···Br | 3.278 (2) | H13···C26iii | 2.9502 |
C16···C32 | 3.422 (6) | H13···H26iii | 2.4752 |
C16···C26 | 3.547 (7) | H15···C34vii | 2.9730 |
C26···C36 | 3.563 (6) | H15···C35vii | 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···C36iv | 2.9884 |
C11···H26 | 2.7300 | H23···C31iv | 2.8968 |
C13···H35ii | 3.0707 | H23···C32iv | 2.9468 |
C16···H26 | 2.8383 | H26···C11 | 2.7300 |
C21···H36 | 2.6522 | H26···C16 | 2.8383 |
C23···H32i | 2.9144 | H26···H13iii | 2.4752 |
C26···H36 | 2.9457 | H32···C34viii | 3.0281 |
C26···H13iii | 2.9502 | H32···C23ix | 2.9144 |
C31···H16 | 2.5895 | H33···Brix | 3.1343 |
C31···H23iv | 2.8968 | H34···Brix | 3.2377 |
C32···H16 | 2.9499 | H35···C13x | 3.0707 |
C32···H23iv | 2.9468 | H36···C21 | 2.6522 |
C34···H32v | 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. |
Experimental details
Crystal data | |
Chemical formula | C18H14BrP |
Mr | 341.16 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 10.371 (5), 8.9735 (19), 16.556 (6) |
β (°) | 92.33 (4) |
V (Å3) | 1539.5 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.76 |
Crystal size (mm) | 0.40 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.383, 0.576 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4223, 3540, 1823 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.150, 1.01 |
No. of reflections | 3540 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.79, −0.70 |
Computer programs: MSC/AFC7 Diffractometer Control Software (Molecular Structure Corporation, 1999), MSC/AFC7 Diffractometer Control Software, TEXSAN for Windows (Molecular Structure Corporation, 2001), TEXSAN for Windows and SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), TEXSAN and PLATON (Spek, 2001).
Br—C12 | 1.905 (5) | P—C21 | 1.833 (4) |
P—C11 | 1.844 (4) | P—C31 | 1.832 (4) |
C11—P—C21 | 101.51 (18) | Br—C12—C13 | 117.7 (3) |
C11—P—C31 | 101.32 (18) | P—C21—C22 | 117.2 (3) |
C21—P—C31 | 102.83 (16) | P—C21—C26 | 124.7 (3) |
P—C11—C12 | 119.8 (3) | P—C31—C32 | 116.4 (3) |
P—C11—C16 | 123.1 (3) | P—C31—C36 | 125.1 (3) |
Br—C12—C11 | 120.8 (3) |
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(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.