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In the structure of the title complex, [(C6H5)4P][AuBr2], the [Ph4P]+ cations and the [AuBr2]- anions are located on crystallographic twofold axes with no unusual contacts. The Au-Br distance of the virtually linear anion is 2.3370 (19) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704216X/wm2140sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680704216X/wm2140Isup2.hkl
Contains datablock I

CCDC reference: 663552

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](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

Comment top

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)°).

Related literature top

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).

Experimental top

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%.

Refinement top

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.

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] 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.]
Tetraphenylphosphonium dibromidoaurate(I) top
Crystal data top
(C24H20P)[AuBr2]F(000) = 656
Mr = 696.14Dx = 2.015 Mg m3
Monoclinic, P2/nMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2yacCell parameters from 17 reflections
a = 10.372 (4) Åθ = 19.5–20.0°
b = 7.602 (3) ŵ = 9.97 mm1
c = 14.559 (9) ÅT = 295 K
β = 92.05 (5)°Block, colourless
V = 1147.2 (10) Å30.25 × 0.20 × 0.15 mm
Z = 2
Data collection top
Rigaku AFC-7R
diffractometer
1141 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anodeRint = 0.031
Graphite monochromatorθmax = 25.1°, θmin = 2.4°
ω/2θ scansh = 012
Absorption correction: ψ scan
(North et al., 1968)
k = 09
Tmin = 0.189, Tmax = 0.316l = 1717
2146 measured reflections3 standard reflections every 150 reflections
2029 independent reflections intensity decay: 2.7%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-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 reflectionsΔρmax = 0.53 e Å3
129 parametersΔρmin = 0.48 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001Fc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0051 (4)
Crystal data top
(C24H20P)[AuBr2]V = 1147.2 (10) Å3
Mr = 696.14Z = 2
Monoclinic, P2/nMo Kα radiation
a = 10.372 (4) ŵ = 9.97 mm1
b = 7.602 (3) ÅT = 295 K
c = 14.559 (9) Å0.25 × 0.20 × 0.15 mm
β = 92.05 (5)°
Data collection top
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 = 0.3163 standard reflections every 150 reflections
2146 measured reflections intensity decay: 2.7%
2029 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.089H-atom parameters constrained
S = 0.99Δρmax = 0.53 e Å3
2029 reflectionsΔρmin = 0.48 e Å3
129 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.250000.9998 (3)0.250000.0381 (7)
C10.2830 (5)0.8562 (6)0.3460 (4)0.0394 (19)
C20.3963 (5)0.8672 (7)0.3983 (4)0.0486 (19)
C30.4191 (6)0.7473 (10)0.4688 (5)0.063 (3)
C40.3294 (8)0.6203 (9)0.4871 (5)0.067 (3)
C50.2177 (7)0.6088 (9)0.4346 (5)0.062 (3)
C60.1932 (6)0.7254 (8)0.3640 (4)0.051 (2)
C70.1167 (5)1.1411 (6)0.2700 (4)0.0391 (19)
C80.0934 (6)1.2824 (8)0.2107 (4)0.056 (2)
C90.0045 (7)1.3976 (8)0.2281 (5)0.067 (3)
C100.0828 (7)1.3741 (9)0.3009 (6)0.076 (3)
C110.0622 (7)1.2337 (11)0.3585 (6)0.083 (3)
C120.0379 (6)1.1178 (8)0.3439 (5)0.061 (2)
Au10.750000.82371 (5)0.250000.0857 (2)
Br10.77409 (10)0.81831 (11)0.41295 (8)0.1106 (5)
H20.457300.956100.386100.0600*
H30.497200.752700.504900.0750*
H40.344700.540500.536600.0800*
H50.157400.519000.447000.0730*
H60.115600.716800.327900.0610*
H80.145401.298700.156900.0680*
H90.019001.496600.189500.0820*
H100.052201.020400.383500.0730*
H110.116501.214700.411300.0970*
H120.152601.455900.312000.0890*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0383 (10)0.0387 (11)0.0374 (13)0.00000.0020 (9)0.0000
C10.049 (3)0.031 (3)0.038 (4)0.006 (2)0.000 (3)0.000 (2)
C20.051 (3)0.046 (3)0.048 (4)0.002 (3)0.009 (3)0.001 (3)
C30.072 (5)0.067 (4)0.049 (5)0.011 (4)0.020 (4)0.014 (4)
C40.101 (6)0.053 (4)0.046 (4)0.023 (4)0.006 (4)0.009 (3)
C50.072 (5)0.054 (4)0.061 (5)0.002 (3)0.010 (4)0.013 (4)
C60.054 (4)0.051 (4)0.047 (4)0.004 (3)0.000 (3)0.007 (3)
C70.038 (3)0.034 (3)0.045 (4)0.000 (2)0.003 (3)0.002 (3)
C80.054 (4)0.058 (4)0.055 (4)0.005 (3)0.001 (3)0.008 (3)
C90.070 (5)0.048 (3)0.081 (6)0.011 (3)0.016 (4)0.001 (4)
C100.065 (5)0.059 (4)0.105 (7)0.014 (3)0.001 (5)0.023 (4)
C110.067 (5)0.069 (5)0.117 (7)0.013 (4)0.042 (5)0.010 (5)
C120.063 (4)0.048 (3)0.072 (5)0.002 (3)0.017 (4)0.008 (3)
Au10.0670 (3)0.0462 (2)0.1450 (6)0.00000.0207 (3)0.0000
Br10.1107 (7)0.0801 (6)0.1423 (10)0.0118 (5)0.0247 (6)0.0203 (6)
Geometric parameters (Å, º) top
Au1—Br12.3770 (19)C8—C91.371 (9)
Au1—Br1i2.3770 (19)C9—C101.370 (11)
P1—C11.797 (6)C10—C111.369 (11)
P1—C7ii1.783 (5)C11—C121.384 (10)
P1—C71.783 (5)C2—H20.9500
P1—C1ii1.797 (6)C3—H30.9500
C1—C61.394 (8)C4—H40.9500
C1—C21.380 (8)C5—H50.9500
C2—C31.387 (9)C6—H60.9500
C3—C41.374 (10)C8—H80.9700
C4—C51.368 (11)C9—H90.9500
C5—C61.374 (9)C10—H120.9700
C7—C81.394 (8)C11—H110.9800
C7—C121.386 (9)C12—H100.9500
Au1···C10iii3.892 (7)C12···Au1ii3.936 (7)
Au1···C11iv3.973 (9)C12···C63.398 (9)
Au1···C12iv3.936 (7)C1···H6ii2.9700
Au1···C10v3.892 (7)C1···H102.7700
Au1···C11ii3.973 (9)C4···H11x2.9800
Au1···C9v4.140 (7)C5···H11x2.8500
Au1···C12ii3.936 (7)C5···H8v3.0800
Au1···C9iii4.140 (7)C6···H102.7000
Au1···H9iii3.5800C7···H2ii2.7600
Au1···H12iii3.1000C7···H8ii2.9100
Au1···H9v3.5800C8···H2ii2.8900
Au1···H12v3.1000C9···H6xi3.0700
Br1···C12iv3.725 (7)H2···C8ii2.8900
Br1···C11iv3.685 (9)H2···C7ii2.7600
Br1···H11iv3.2200H4···Br1vi3.0900
Br1···H4vi3.0900H6···C1ii2.9700
Br1···H12iii3.2300H6···H102.5400
C2···C8ii3.536 (8)H6···C9xii3.0700
C6···C123.398 (9)H8···C7ii2.9100
C6···C6ii3.562 (9)H8···C5vii3.0800
C8···C8ii3.405 (9)H9···Au1viii3.5800
C8···C2ii3.536 (8)H9···Au1vii3.5800
C9···Au1vii4.140 (7)H10···C62.7000
C9···Au1viii4.140 (7)H10···C12.7700
C10···Au1viii3.892 (7)H10···H62.5400
C10···Au1vii3.892 (7)H11···C4x2.9800
C11···Au1ix3.973 (9)H11···C5x2.8500
C11···Br1ix3.685 (9)H11···Br1ix3.2200
C11···Au1ii3.973 (9)H12···Au1vii3.1000
C12···Au1ix3.936 (7)H12···Au1viii3.1000
C12···Br1ix3.725 (7)H12···Br1viii3.2300
Br1—Au1—Br1i178.02 (7)C7—C12—C11120.3 (6)
C1—P1—C7111.5 (3)C1—C2—H2120.00
C1—P1—C7ii111.5 (2)C3—C2—H2121.00
C1ii—P1—C7111.5 (2)C4—C3—H3120.00
C1—P1—C1ii105.2 (3)C2—C3—H3120.00
C1ii—P1—C7ii111.5 (3)C3—C4—H4120.00
C7—P1—C7ii105.9 (3)C5—C4—H4120.00
P1—C1—C2121.8 (4)C6—C5—H5120.00
P1—C1—C6118.0 (4)C4—C5—H5119.00
C2—C1—C6120.1 (5)C1—C6—H6120.00
C1—C2—C3119.2 (5)C5—C6—H6120.00
C2—C3—C4120.5 (6)C9—C8—H8120.00
C3—C4—C5120.2 (7)C7—C8—H8120.00
C4—C5—C6120.5 (6)C8—C9—H9120.00
C1—C6—C5119.6 (6)C10—C9—H9118.00
P1—C7—C12122.2 (4)C11—C10—H12120.00
C8—C7—C12119.0 (5)C9—C10—H12121.00
P1—C7—C8118.8 (4)C10—C11—H11121.00
C7—C8—C9119.4 (6)C12—C11—H11119.00
C8—C9—C10121.5 (6)C7—C12—H10119.00
C9—C10—C11119.5 (7)C11—C12—H10120.00
C10—C11—C12120.2 (7)
C7—P1—C1—C2114.7 (5)P1—C1—C6—C5177.4 (5)
C7—P1—C1—C668.6 (5)C2—C1—C6—C50.6 (9)
C1ii—P1—C1—C2124.4 (5)C1—C2—C3—C40.7 (10)
C1ii—P1—C1—C652.4 (5)C2—C3—C4—C51.3 (11)
C7ii—P1—C1—C23.4 (5)C3—C4—C5—C60.9 (11)
C7ii—P1—C1—C6173.3 (4)C4—C5—C6—C10.0 (10)
C1—P1—C7—C8168.0 (4)P1—C7—C8—C9176.5 (5)
C1—P1—C7—C1210.2 (6)C12—C7—C8—C91.7 (9)
C1ii—P1—C7—C874.8 (5)P1—C7—C12—C11178.0 (5)
C1ii—P1—C7—C12107.0 (5)C8—C7—C12—C110.2 (9)
C7ii—P1—C7—C846.6 (5)C7—C8—C9—C102.1 (10)
C7ii—P1—C7—C12131.6 (5)C8—C9—C10—C110.8 (11)
P1—C1—C2—C3176.9 (5)C9—C10—C11—C120.8 (12)
C6—C1—C2—C30.2 (9)C10—C11—C12—C71.1 (11)
Symmetry codes: (i) x+3/2, y, z+1/2; (ii) x+1/2, y, z+1/2; (iii) x+1, y1, z; (iv) x+1, y, z; (v) x+1/2, y1, z+1/2; (vi) x+1, y+1, z+1; (vii) x+1/2, y+1, z+1/2; (viii) x1, y+1, z; (ix) x1, y, z; (x) x, y+2, z+1; (xi) x, y+1, z; (xii) x, y1, z.

Experimental details

Crystal data
Chemical formula(C24H20P)[AuBr2]
Mr696.14
Crystal system, space groupMonoclinic, P2/n
Temperature (K)295
a, b, c (Å)10.372 (4), 7.602 (3), 14.559 (9)
β (°) 92.05 (5)
V3)1147.2 (10)
Z2
Radiation typeMo Kα
µ (mm1)9.97
Crystal size (mm)0.25 × 0.20 × 0.15
Data collection
DiffractometerRigaku AFC-7R
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.189, 0.316
No. of measured, independent and
observed [I > 2σ(I)] reflections
2146, 2029, 1141
Rint0.031
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.089, 0.99
No. of reflections2029
No. of parameters129
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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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