Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704216X/wm2140sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704216X/wm2140Isup2.hkl |
CCDC reference: 663552
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.009 Å
- R factor = 0.030
- wR factor = 0.089
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.189 0.316 Tmin and Tmax expected: 0.105 0.224 RR = 1.277 Please check that your absorption correction is appropriate. PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.28 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.71 PLAT128_ALERT_4_C Non-standard setting of Space group P2/c .... P2/n PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.709 Tmax scaled 0.224 Tmin scaled 0.134 PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Au1 (3) 1.71
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
The title compound was synthesized by adapted literature procedures (Braunstein & Clark, 1973; Buckley et al., 1997). The Au—Br distance is similar to that of the [n-Bu4N]+ salt (Braunstein et al., 1986).
Liquid bromine (3.0 ml) was added dropwise to a suspension of powdered metallic gold (2.0 g, 10.20 mmol) in a solution of tetraphenylphosphonium bromide (94.71 g, 10.20 mmol) in absolute ethanol (50 ml). The mixture was then stirred vigorously at room temperature for 2 h. More bromine (1.0 ml) was added and the resultant deep red solution stirred overnight at room temperature. The solution was then heated slowly to boiling to remove any excess bromine. Cooling to room temperature and filtration yielded the gold(III) complex [PPh4][AuBr4] as a deep red solid (yield 8.01 g, 82%). [PPh4][AuBr4] (2.0 g, 2.34 mmol) was then dissolved in warm (~320 K) absolute ethanol, followed by addition of acetone (10 ml) in 1 ml increments until the solution turned colourless. Cooling the solution to room temperature resulted in precipitation of colourless crystals of the title complex suitable for X-ray diffraction studies. Yield 1.38 g, 85%. m.p. 511–515 K. Analysis found: C 41.2, H 2.8%; calculated for C24H20PAuBr2 C 41.4, H 2.9%.
H atoms were constrained as riding atoms, fixed to their parent C atoms at a C—H distance of 0.95 Å. Uiso(H) values were set to 1.2Ueq of the parent atom.
As part of our studies on the synthesis, structural and spectroscopic characterization of gold(I) complexes, we synthesized the title complex, (I), by adaption of literature procedures (Buckley et al., 1997; Braunstein & Clark, 1973).
The molecular structure of (I) is presented in Fig. 1. The [Ph4P]+ cations and the [AuBr2]- anions are located on crystallographic twofold axes with no unusual contacts. The Au—Br distance of 2.3370 (19) Å is in good agreement with that of 2.376 (3) Å observed for the analogous [n-Bu4N]+ salt (Braunstein et al., 1986). The Br—Au—Br angle is nearly linear (178.02 (7)°).
The title compound was synthesized by adapted literature procedures (Braunstein & Clark, 1973; Buckley et al., 1997). The Au—Br distance is similar to that of the [n-Bu4N]+ salt (Braunstein et al., 1986).
Data collection: MSC/AFC7 Diffractometer Control Software (Molecular Structure Corporation, 1999); cell refinement: MSC/AFC7 Diffractometer Control Software (Molecular Structure Corporation, 1999); data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to refine structure: TEXSAN (Molecular Structure Corporation, 2001) and SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: TEXSAN (Molecular Structure Corporation, 2001) and PLATON (Spek, 2003).
Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level [Symmetry operation i): -x + 3/2, y, -z + 1/2.] |
(C24H20P)[AuBr2] | F(000) = 656 |
Mr = 696.14 | Dx = 2.015 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2yac | Cell parameters from 17 reflections |
a = 10.372 (4) Å | θ = 19.5–20.0° |
b = 7.602 (3) Å | µ = 9.97 mm−1 |
c = 14.559 (9) Å | T = 295 K |
β = 92.05 (5)° | Block, colourless |
V = 1147.2 (10) Å3 | 0.25 × 0.20 × 0.15 mm |
Z = 2 |
Rigaku AFC-7R diffractometer | 1141 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.031 |
Graphite monochromator | θmax = 25.1°, θmin = 2.4° |
ω/2θ scans | h = 0→12 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→9 |
Tmin = 0.189, Tmax = 0.316 | l = −17→17 |
2146 measured reflections | 3 standard reflections every 150 reflections |
2029 independent reflections | intensity decay: 2.7% |
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)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.0398P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
2029 reflections | Δρmax = 0.53 e Å−3 |
129 parameters | Δρmin = −0.48 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001Fc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0051 (4) |
(C24H20P)[AuBr2] | V = 1147.2 (10) Å3 |
Mr = 696.14 | Z = 2 |
Monoclinic, P2/n | Mo Kα radiation |
a = 10.372 (4) Å | µ = 9.97 mm−1 |
b = 7.602 (3) Å | T = 295 K |
c = 14.559 (9) Å | 0.25 × 0.20 × 0.15 mm |
β = 92.05 (5)° |
Rigaku AFC-7R diffractometer | 1141 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.031 |
Tmin = 0.189, Tmax = 0.316 | 3 standard reflections every 150 reflections |
2146 measured reflections | intensity decay: 2.7% |
2029 independent reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.53 e Å−3 |
2029 reflections | Δρmin = −0.48 e Å−3 |
129 parameters |
Experimental. The scan width was (1.68 + 0.35tanθ)° with an ω scan speed of 32° per minute (up to 4 scans to achieve I/σ(I) > 15). 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 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 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 > σ(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 | ||
P1 | 0.25000 | 0.9998 (3) | 0.25000 | 0.0381 (7) | |
C1 | 0.2830 (5) | 0.8562 (6) | 0.3460 (4) | 0.0394 (19) | |
C2 | 0.3963 (5) | 0.8672 (7) | 0.3983 (4) | 0.0486 (19) | |
C3 | 0.4191 (6) | 0.7473 (10) | 0.4688 (5) | 0.063 (3) | |
C4 | 0.3294 (8) | 0.6203 (9) | 0.4871 (5) | 0.067 (3) | |
C5 | 0.2177 (7) | 0.6088 (9) | 0.4346 (5) | 0.062 (3) | |
C6 | 0.1932 (6) | 0.7254 (8) | 0.3640 (4) | 0.051 (2) | |
C7 | 0.1167 (5) | 1.1411 (6) | 0.2700 (4) | 0.0391 (19) | |
C8 | 0.0934 (6) | 1.2824 (8) | 0.2107 (4) | 0.056 (2) | |
C9 | −0.0045 (7) | 1.3976 (8) | 0.2281 (5) | 0.067 (3) | |
C10 | −0.0828 (7) | 1.3741 (9) | 0.3009 (6) | 0.076 (3) | |
C11 | −0.0622 (7) | 1.2337 (11) | 0.3585 (6) | 0.083 (3) | |
C12 | 0.0379 (6) | 1.1178 (8) | 0.3439 (5) | 0.061 (2) | |
Au1 | 0.75000 | 0.82371 (5) | 0.25000 | 0.0857 (2) | |
Br1 | 0.77409 (10) | 0.81831 (11) | 0.41295 (8) | 0.1106 (5) | |
H2 | 0.45730 | 0.95610 | 0.38610 | 0.0600* | |
H3 | 0.49720 | 0.75270 | 0.50490 | 0.0750* | |
H4 | 0.34470 | 0.54050 | 0.53660 | 0.0800* | |
H5 | 0.15740 | 0.51900 | 0.44700 | 0.0730* | |
H6 | 0.11560 | 0.71680 | 0.32790 | 0.0610* | |
H8 | 0.14540 | 1.29870 | 0.15690 | 0.0680* | |
H9 | −0.01900 | 1.49660 | 0.18950 | 0.0820* | |
H10 | 0.05220 | 1.02040 | 0.38350 | 0.0730* | |
H11 | −0.11650 | 1.21470 | 0.41130 | 0.0970* | |
H12 | −0.15260 | 1.45590 | 0.31200 | 0.0890* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0383 (10) | 0.0387 (11) | 0.0374 (13) | 0.0000 | 0.0020 (9) | 0.0000 |
C1 | 0.049 (3) | 0.031 (3) | 0.038 (4) | 0.006 (2) | 0.000 (3) | 0.000 (2) |
C2 | 0.051 (3) | 0.046 (3) | 0.048 (4) | 0.002 (3) | −0.009 (3) | −0.001 (3) |
C3 | 0.072 (5) | 0.067 (4) | 0.049 (5) | 0.011 (4) | −0.020 (4) | 0.014 (4) |
C4 | 0.101 (6) | 0.053 (4) | 0.046 (4) | 0.023 (4) | 0.006 (4) | 0.009 (3) |
C5 | 0.072 (5) | 0.054 (4) | 0.061 (5) | −0.002 (3) | 0.010 (4) | 0.013 (4) |
C6 | 0.054 (4) | 0.051 (4) | 0.047 (4) | −0.004 (3) | 0.000 (3) | 0.007 (3) |
C7 | 0.038 (3) | 0.034 (3) | 0.045 (4) | 0.000 (2) | −0.003 (3) | −0.002 (3) |
C8 | 0.054 (4) | 0.058 (4) | 0.055 (4) | 0.005 (3) | −0.001 (3) | 0.008 (3) |
C9 | 0.070 (5) | 0.048 (3) | 0.081 (6) | 0.011 (3) | −0.016 (4) | 0.001 (4) |
C10 | 0.065 (5) | 0.059 (4) | 0.105 (7) | 0.014 (3) | 0.001 (5) | −0.023 (4) |
C11 | 0.067 (5) | 0.069 (5) | 0.117 (7) | 0.013 (4) | 0.042 (5) | −0.010 (5) |
C12 | 0.063 (4) | 0.048 (3) | 0.072 (5) | 0.002 (3) | 0.017 (4) | 0.008 (3) |
Au1 | 0.0670 (3) | 0.0462 (2) | 0.1450 (6) | 0.0000 | 0.0207 (3) | 0.0000 |
Br1 | 0.1107 (7) | 0.0801 (6) | 0.1423 (10) | −0.0118 (5) | 0.0247 (6) | 0.0203 (6) |
Au1—Br1 | 2.3770 (19) | C8—C9 | 1.371 (9) |
Au1—Br1i | 2.3770 (19) | C9—C10 | 1.370 (11) |
P1—C1 | 1.797 (6) | C10—C11 | 1.369 (11) |
P1—C7ii | 1.783 (5) | C11—C12 | 1.384 (10) |
P1—C7 | 1.783 (5) | C2—H2 | 0.9500 |
P1—C1ii | 1.797 (6) | C3—H3 | 0.9500 |
C1—C6 | 1.394 (8) | C4—H4 | 0.9500 |
C1—C2 | 1.380 (8) | C5—H5 | 0.9500 |
C2—C3 | 1.387 (9) | C6—H6 | 0.9500 |
C3—C4 | 1.374 (10) | C8—H8 | 0.9700 |
C4—C5 | 1.368 (11) | C9—H9 | 0.9500 |
C5—C6 | 1.374 (9) | C10—H12 | 0.9700 |
C7—C8 | 1.394 (8) | C11—H11 | 0.9800 |
C7—C12 | 1.386 (9) | C12—H10 | 0.9500 |
Au1···C10iii | 3.892 (7) | C12···Au1ii | 3.936 (7) |
Au1···C11iv | 3.973 (9) | C12···C6 | 3.398 (9) |
Au1···C12iv | 3.936 (7) | C1···H6ii | 2.9700 |
Au1···C10v | 3.892 (7) | C1···H10 | 2.7700 |
Au1···C11ii | 3.973 (9) | C4···H11x | 2.9800 |
Au1···C9v | 4.140 (7) | C5···H11x | 2.8500 |
Au1···C12ii | 3.936 (7) | C5···H8v | 3.0800 |
Au1···C9iii | 4.140 (7) | C6···H10 | 2.7000 |
Au1···H9iii | 3.5800 | C7···H2ii | 2.7600 |
Au1···H12iii | 3.1000 | C7···H8ii | 2.9100 |
Au1···H9v | 3.5800 | C8···H2ii | 2.8900 |
Au1···H12v | 3.1000 | C9···H6xi | 3.0700 |
Br1···C12iv | 3.725 (7) | H2···C8ii | 2.8900 |
Br1···C11iv | 3.685 (9) | H2···C7ii | 2.7600 |
Br1···H11iv | 3.2200 | H4···Br1vi | 3.0900 |
Br1···H4vi | 3.0900 | H6···C1ii | 2.9700 |
Br1···H12iii | 3.2300 | H6···H10 | 2.5400 |
C2···C8ii | 3.536 (8) | H6···C9xii | 3.0700 |
C6···C12 | 3.398 (9) | H8···C7ii | 2.9100 |
C6···C6ii | 3.562 (9) | H8···C5vii | 3.0800 |
C8···C8ii | 3.405 (9) | H9···Au1viii | 3.5800 |
C8···C2ii | 3.536 (8) | H9···Au1vii | 3.5800 |
C9···Au1vii | 4.140 (7) | H10···C6 | 2.7000 |
C9···Au1viii | 4.140 (7) | H10···C1 | 2.7700 |
C10···Au1viii | 3.892 (7) | H10···H6 | 2.5400 |
C10···Au1vii | 3.892 (7) | H11···C4x | 2.9800 |
C11···Au1ix | 3.973 (9) | H11···C5x | 2.8500 |
C11···Br1ix | 3.685 (9) | H11···Br1ix | 3.2200 |
C11···Au1ii | 3.973 (9) | H12···Au1vii | 3.1000 |
C12···Au1ix | 3.936 (7) | H12···Au1viii | 3.1000 |
C12···Br1ix | 3.725 (7) | H12···Br1viii | 3.2300 |
Br1—Au1—Br1i | 178.02 (7) | C7—C12—C11 | 120.3 (6) |
C1—P1—C7 | 111.5 (3) | C1—C2—H2 | 120.00 |
C1—P1—C7ii | 111.5 (2) | C3—C2—H2 | 121.00 |
C1ii—P1—C7 | 111.5 (2) | C4—C3—H3 | 120.00 |
C1—P1—C1ii | 105.2 (3) | C2—C3—H3 | 120.00 |
C1ii—P1—C7ii | 111.5 (3) | C3—C4—H4 | 120.00 |
C7—P1—C7ii | 105.9 (3) | C5—C4—H4 | 120.00 |
P1—C1—C2 | 121.8 (4) | C6—C5—H5 | 120.00 |
P1—C1—C6 | 118.0 (4) | C4—C5—H5 | 119.00 |
C2—C1—C6 | 120.1 (5) | C1—C6—H6 | 120.00 |
C1—C2—C3 | 119.2 (5) | C5—C6—H6 | 120.00 |
C2—C3—C4 | 120.5 (6) | C9—C8—H8 | 120.00 |
C3—C4—C5 | 120.2 (7) | C7—C8—H8 | 120.00 |
C4—C5—C6 | 120.5 (6) | C8—C9—H9 | 120.00 |
C1—C6—C5 | 119.6 (6) | C10—C9—H9 | 118.00 |
P1—C7—C12 | 122.2 (4) | C11—C10—H12 | 120.00 |
C8—C7—C12 | 119.0 (5) | C9—C10—H12 | 121.00 |
P1—C7—C8 | 118.8 (4) | C10—C11—H11 | 121.00 |
C7—C8—C9 | 119.4 (6) | C12—C11—H11 | 119.00 |
C8—C9—C10 | 121.5 (6) | C7—C12—H10 | 119.00 |
C9—C10—C11 | 119.5 (7) | C11—C12—H10 | 120.00 |
C10—C11—C12 | 120.2 (7) | ||
C7—P1—C1—C2 | −114.7 (5) | P1—C1—C6—C5 | 177.4 (5) |
C7—P1—C1—C6 | 68.6 (5) | C2—C1—C6—C5 | 0.6 (9) |
C1ii—P1—C1—C2 | 124.4 (5) | C1—C2—C3—C4 | −0.7 (10) |
C1ii—P1—C1—C6 | −52.4 (5) | C2—C3—C4—C5 | 1.3 (11) |
C7ii—P1—C1—C2 | 3.4 (5) | C3—C4—C5—C6 | −0.9 (11) |
C7ii—P1—C1—C6 | −173.3 (4) | C4—C5—C6—C1 | 0.0 (10) |
C1—P1—C7—C8 | 168.0 (4) | P1—C7—C8—C9 | −176.5 (5) |
C1—P1—C7—C12 | −10.2 (6) | C12—C7—C8—C9 | 1.7 (9) |
C1ii—P1—C7—C8 | −74.8 (5) | P1—C7—C12—C11 | 178.0 (5) |
C1ii—P1—C7—C12 | 107.0 (5) | C8—C7—C12—C11 | −0.2 (9) |
C7ii—P1—C7—C8 | 46.6 (5) | C7—C8—C9—C10 | −2.1 (10) |
C7ii—P1—C7—C12 | −131.6 (5) | C8—C9—C10—C11 | 0.8 (11) |
P1—C1—C2—C3 | −176.9 (5) | C9—C10—C11—C12 | 0.8 (12) |
C6—C1—C2—C3 | −0.2 (9) | C10—C11—C12—C7 | −1.1 (11) |
Symmetry codes: (i) −x+3/2, y, −z+1/2; (ii) −x+1/2, y, −z+1/2; (iii) x+1, y−1, z; (iv) x+1, y, z; (v) −x+1/2, y−1, −z+1/2; (vi) −x+1, −y+1, −z+1; (vii) −x+1/2, y+1, −z+1/2; (viii) x−1, y+1, z; (ix) x−1, y, z; (x) −x, −y+2, −z+1; (xi) x, y+1, z; (xii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | (C24H20P)[AuBr2] |
Mr | 696.14 |
Crystal system, space group | Monoclinic, P2/n |
Temperature (K) | 295 |
a, b, c (Å) | 10.372 (4), 7.602 (3), 14.559 (9) |
β (°) | 92.05 (5) |
V (Å3) | 1147.2 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 9.97 |
Crystal size (mm) | 0.25 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Rigaku AFC-7R |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.189, 0.316 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2146, 2029, 1141 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.089, 0.99 |
No. of reflections | 2029 |
No. of parameters | 129 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.48 |
Computer programs: MSC/AFC7 Diffractometer Control Software (Molecular Structure Corporation, 1999), TEXSAN (Molecular Structure Corporation, 2001) and SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), TEXSAN (Molecular Structure Corporation, 2001) and PLATON (Spek, 2003).
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As part of our studies on the synthesis, structural and spectroscopic characterization of gold(I) complexes, we synthesized the title complex, (I), by adaption of literature procedures (Buckley et al., 1997; Braunstein & Clark, 1973).
The molecular structure of (I) is presented in Fig. 1. The [Ph4P]+ cations and the [AuBr2]- anions are located on crystallographic twofold axes with no unusual contacts. The Au—Br distance of 2.3370 (19) Å is in good agreement with that of 2.376 (3) Å observed for the analogous [n-Bu4N]+ salt (Braunstein et al., 1986). The Br—Au—Br angle is nearly linear (178.02 (7)°).