Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017732/tk6130sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017732/tk6130Isup2.hkl |
CCDC reference: 222814
[NBu4][AuBr2] (50 mg, 0.072 mmol) and diphenylphosphinomethane mono-oxide (dppmO, 33.4 mg, 0.083 mmol) were dissolved in acetonitrile (10 ml) to give a clear solution. Slow evaporation of the solvent yielded well formed colorless crystals of (I); m.p. 506–507 K. The crystals slowly lost solvent over a period of weeks. Analysis found: C 46.0, H 3.5 N 1.7%; calculated for C27H25AuBrNOP2: C 45.15, H 3.51, N 1.95%.νmax (KBr)/cm−1: 1179 (P═O str). δH (400 MHz, CDCl3, p.p.m.): 3.53 [2H, dd, CH2, 2JP(Au)CH = 12 Hz, 2JP(O)CH = 12 Hz], 7.36–7.47 (8H, m, m-C6H5), 7.42–7.55 (4H, m, p-C6H5), 7.66–7.75 (8H, m, o-C6H5). δC (100 MHz, CDCl3, p.p.m.): 31.4 [dd, CH2, 1JCP(O) = 59 Hz, 1JCP(Au) = 26 Hz], 129.4 [d, m-C6H5(PAu), 3JCP(Au) = 12 Hz], 129.4 [d, m-C6H5(PO), 3JCP(Au) = 12 Hz], 129.7 [dd, i-C6H5(PAu), 1JCP(Au) = 61 Hz, 3JCP(O) = 4 Hz], 131.2 [d, o-C6H5(PAu), 2JCP(Au) = 10 Hz], 131.9 [dd, i-C6H5(PO), 1JCP(O) = 105 Hz, 3JCP(Au) = 3 Hz], 132.3 [d, p-C6H5(PAu), 4JCP(Au) = 3 Hz], 132.9 [d, p-C6H5(PO), 4JCP(O) = 3 Hz], 133.7 [d, o-C6H5(PO), 2JCP(Au) = 15 Hz], δP (162 MHz, CDCl3, p.p.m.): 25.0 [1P, s, P(O)]; 20.0 [1P, s,P(Au)].
H atoms were constrained in the riding model approximation, fixed to their parent C atoms at a C—H distance of 0.95 Å, and Uiso(H) values were set to 1.2Ueq of the parent atom.
Data collection: MSC/AFC7 Diffractometer Control Software for Windows (Molecular Structure Corporation, 1999); cell refinement: MSC/AFC7 Diffractometer Control Software for Windows; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-2001); 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 for Windows and PLATON (Spek, 1980-2001).
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. |
[AuBr(C25H22OP2)]·CH3CN | F(000) = 1384 |
Mr = 718.29 | Dx = 1.811 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 11.657 (3) Å | θ = 12.5–17.4° |
b = 22.436 (17) Å | µ = 7.24 mm−1 |
c = 11.209 (4) Å | T = 295 K |
β = 115.98 (2)° | Prismatic, colorless |
V = 2635 (2) Å3 | 0.30 × 0.30 × 0.20 mm |
Z = 4 |
Rigaku AFC-7R diffractometer | 4561 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.027 |
Graphite monochromator | θmax = 27.5°, θmin = 2.7° |
ω scans | h = −13→15 |
Absorption correction: ψ scan (North, Phillips & Matthews, 1968) | k = 0→29 |
Tmin = 0.135, Tmax = 0.235 | l = −14→5 |
6598 measured reflections | 3 standard reflections every 150 reflections |
6045 independent reflections | intensity decay: 5.0% |
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 not refined |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0339P)2 + 2.0179P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
6045 reflections | Δρmax = 1.05 e Å−3 |
299 parameters | Δρmin = −1.07 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: 0.00103 (10) |
[AuBr(C25H22OP2)]·CH3CN | V = 2635 (2) Å3 |
Mr = 718.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.657 (3) Å | µ = 7.24 mm−1 |
b = 22.436 (17) Å | T = 295 K |
c = 11.209 (4) Å | 0.30 × 0.30 × 0.20 mm |
β = 115.98 (2)° |
Rigaku AFC-7R diffractometer | 4561 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North, Phillips & Matthews, 1968) | Rint = 0.027 |
Tmin = 0.135, Tmax = 0.235 | 3 standard reflections every 150 reflections |
6598 measured reflections | intensity decay: 5.0% |
6045 independent reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters not refined |
S = 1.02 | Δρmax = 1.05 e Å−3 |
6045 reflections | Δρmin = −1.07 e Å−3 |
299 parameters |
Experimental. The scan width was (1.10 + 0.30tanθ)° with an ω scan speed of 16° per minute (up to 4 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 of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) 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 | ||
Au1 | 0.51548 (2) | 0.15206 (1) | 0.36269 (2) | 0.0379 (1) | |
Br1 | 0.45026 (7) | 0.13005 (3) | 0.13186 (5) | 0.0628 (2) | |
P1 | 0.57349 (10) | 0.17046 (5) | 0.57799 (11) | 0.0278 (3) | |
P2 | 0.80322 (10) | 0.24324 (5) | 0.59582 (10) | 0.0255 (3) | |
O1 | 0.7611 (3) | 0.24140 (15) | 0.4497 (3) | 0.0369 (10) | |
C1 | 0.6725 (4) | 0.23675 (19) | 0.6413 (4) | 0.0260 (11) | |
C111 | 0.4400 (4) | 0.1847 (2) | 0.6170 (4) | 0.0304 (11) | |
C112 | 0.3166 (5) | 0.1779 (3) | 0.5204 (5) | 0.0482 (18) | |
C113 | 0.2152 (5) | 0.1850 (3) | 0.5522 (7) | 0.064 (2) | |
C114 | 0.2365 (5) | 0.1990 (3) | 0.6787 (6) | 0.054 (2) | |
C115 | 0.3591 (5) | 0.2072 (3) | 0.7753 (6) | 0.0520 (19) | |
C116 | 0.4601 (4) | 0.2002 (2) | 0.7445 (5) | 0.0436 (16) | |
C121 | 0.6556 (4) | 0.10800 (19) | 0.6854 (4) | 0.0288 (12) | |
C122 | 0.6357 (5) | 0.0516 (2) | 0.6289 (5) | 0.0438 (17) | |
C123 | 0.6863 (6) | 0.0022 (2) | 0.7077 (6) | 0.057 (2) | |
C124 | 0.7597 (6) | 0.0085 (3) | 0.8415 (6) | 0.059 (2) | |
C125 | 0.7827 (5) | 0.0641 (3) | 0.8966 (5) | 0.0548 (17) | |
C126 | 0.7316 (5) | 0.1145 (2) | 0.8200 (5) | 0.0387 (16) | |
C211 | 0.8857 (4) | 0.31148 (19) | 0.6707 (4) | 0.0299 (12) | |
C212 | 0.9970 (4) | 0.3232 (2) | 0.6555 (5) | 0.0405 (17) | |
C213 | 1.0645 (5) | 0.3748 (3) | 0.7077 (6) | 0.0489 (17) | |
C214 | 1.0242 (5) | 0.4150 (3) | 0.7737 (5) | 0.0549 (19) | |
C215 | 0.9150 (6) | 0.4041 (3) | 0.7871 (6) | 0.0544 (19) | |
C216 | 0.8458 (5) | 0.3522 (2) | 0.7367 (5) | 0.0443 (17) | |
C221 | 0.9130 (4) | 0.1838 (2) | 0.6805 (4) | 0.0309 (12) | |
C222 | 0.9135 (5) | 0.1336 (2) | 0.6098 (6) | 0.0458 (17) | |
C223 | 0.9950 (6) | 0.0868 (3) | 0.6725 (8) | 0.066 (2) | |
C224 | 1.0770 (6) | 0.0912 (3) | 0.8036 (7) | 0.069 (3) | |
C225 | 1.0785 (6) | 0.1409 (3) | 0.8750 (6) | 0.065 (2) | |
C226 | 0.9966 (5) | 0.1877 (3) | 0.8146 (5) | 0.0428 (16) | |
N1 | 0.2404 (10) | 0.0100 (5) | 0.5836 (9) | 0.131 (4) | |
C2 | 0.4154 (8) | 0.0355 (4) | 0.8112 (10) | 0.101 (4) | |
C3 | 0.3168 (9) | 0.0220 (4) | 0.6819 (10) | 0.083 (3) | |
H11 | 0.61940 | 0.27080 | 0.60830 | 0.0310* | |
H12 | 0.70740 | 0.23610 | 0.73550 | 0.0310* | |
H112 | 0.30110 | 0.16840 | 0.43210 | 0.0580* | |
H113 | 0.13030 | 0.18020 | 0.48550 | 0.0760* | |
H114 | 0.16650 | 0.20290 | 0.70010 | 0.0650* | |
H115 | 0.37380 | 0.21770 | 0.86290 | 0.0620* | |
H116 | 0.54460 | 0.20610 | 0.81120 | 0.0520* | |
H122 | 0.58710 | 0.04710 | 0.53580 | 0.0520* | |
H123 | 0.67020 | −0.03640 | 0.66910 | 0.0680* | |
H124 | 0.79430 | −0.02570 | 0.89560 | 0.0700* | |
H125 | 0.83480 | 0.06830 | 0.98920 | 0.0650* | |
H126 | 0.74840 | 0.15300 | 0.85950 | 0.0470* | |
H212 | 1.02550 | 0.29570 | 0.60970 | 0.0480* | |
H213 | 1.14000 | 0.38270 | 0.69780 | 0.0590* | |
H214 | 1.07200 | 0.45030 | 0.81000 | 0.0660* | |
H215 | 0.88630 | 0.43220 | 0.83120 | 0.0650* | |
H216 | 0.77080 | 0.34480 | 0.74770 | 0.0530* | |
H222 | 0.85800 | 0.13120 | 0.51770 | 0.0550* | |
H223 | 0.99360 | 0.05180 | 0.62440 | 0.0790* | |
H224 | 1.13410 | 0.05930 | 0.84600 | 0.0840* | |
H225 | 1.13600 | 0.14320 | 0.96650 | 0.0780* | |
H226 | 0.99740 | 0.22220 | 0.86400 | 0.0510* | |
H21 | 0.38350 | 0.03040 | 0.87540 | 0.1210* | |
H22 | 0.48570 | 0.00940 | 0.83110 | 0.1210* | |
H23 | 0.44250 | 0.07560 | 0.81320 | 0.1210* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Au1 | 0.0416 (1) | 0.0435 (1) | 0.0264 (1) | −0.0076 (1) | 0.0129 (1) | −0.0052 (1) |
Br1 | 0.0873 (4) | 0.0667 (4) | 0.0301 (3) | −0.0218 (3) | 0.0217 (3) | −0.0120 (3) |
P1 | 0.0266 (5) | 0.0317 (6) | 0.0241 (5) | −0.0024 (4) | 0.0102 (4) | −0.0028 (4) |
P2 | 0.0277 (5) | 0.0290 (6) | 0.0204 (5) | −0.0016 (4) | 0.0110 (4) | 0.0001 (4) |
O1 | 0.0457 (18) | 0.047 (2) | 0.0189 (14) | −0.0025 (15) | 0.0150 (13) | 0.0015 (14) |
C1 | 0.0263 (19) | 0.028 (2) | 0.0225 (19) | 0.0009 (16) | 0.0095 (16) | −0.0008 (17) |
C111 | 0.0278 (19) | 0.030 (2) | 0.033 (2) | −0.0042 (17) | 0.0130 (17) | −0.0003 (18) |
C112 | 0.033 (2) | 0.071 (4) | 0.037 (3) | −0.002 (2) | 0.012 (2) | −0.001 (3) |
C113 | 0.032 (3) | 0.087 (5) | 0.070 (4) | 0.001 (3) | 0.019 (3) | 0.002 (4) |
C114 | 0.044 (3) | 0.060 (4) | 0.071 (4) | 0.004 (3) | 0.037 (3) | 0.006 (3) |
C115 | 0.053 (3) | 0.060 (4) | 0.057 (3) | −0.005 (3) | 0.037 (3) | −0.013 (3) |
C116 | 0.037 (2) | 0.056 (3) | 0.040 (3) | −0.007 (2) | 0.019 (2) | −0.015 (2) |
C121 | 0.029 (2) | 0.027 (2) | 0.032 (2) | −0.0006 (17) | 0.0149 (17) | 0.0007 (18) |
C122 | 0.048 (3) | 0.034 (3) | 0.042 (3) | 0.000 (2) | 0.013 (2) | −0.008 (2) |
C123 | 0.067 (4) | 0.033 (3) | 0.063 (4) | 0.007 (3) | 0.021 (3) | −0.005 (3) |
C124 | 0.069 (4) | 0.041 (3) | 0.059 (4) | 0.016 (3) | 0.022 (3) | 0.010 (3) |
C125 | 0.062 (3) | 0.051 (3) | 0.041 (3) | 0.004 (3) | 0.013 (3) | 0.005 (3) |
C126 | 0.047 (3) | 0.033 (3) | 0.028 (2) | 0.000 (2) | 0.009 (2) | −0.0035 (19) |
C211 | 0.035 (2) | 0.029 (2) | 0.025 (2) | −0.0051 (18) | 0.0124 (17) | −0.0002 (17) |
C212 | 0.044 (3) | 0.043 (3) | 0.036 (3) | −0.007 (2) | 0.019 (2) | −0.003 (2) |
C213 | 0.045 (3) | 0.048 (3) | 0.054 (3) | −0.017 (2) | 0.022 (2) | −0.002 (3) |
C214 | 0.066 (4) | 0.046 (3) | 0.043 (3) | −0.025 (3) | 0.015 (3) | −0.008 (3) |
C215 | 0.079 (4) | 0.044 (3) | 0.047 (3) | −0.010 (3) | 0.034 (3) | −0.013 (3) |
C216 | 0.052 (3) | 0.043 (3) | 0.047 (3) | −0.010 (2) | 0.030 (2) | −0.008 (2) |
C221 | 0.029 (2) | 0.035 (2) | 0.032 (2) | −0.0008 (18) | 0.0164 (18) | 0.0022 (19) |
C222 | 0.049 (3) | 0.041 (3) | 0.050 (3) | 0.007 (2) | 0.024 (2) | −0.002 (2) |
C223 | 0.078 (4) | 0.040 (3) | 0.091 (5) | 0.019 (3) | 0.048 (4) | 0.009 (3) |
C224 | 0.068 (4) | 0.071 (5) | 0.082 (5) | 0.041 (4) | 0.045 (4) | 0.039 (4) |
C225 | 0.053 (3) | 0.093 (5) | 0.046 (3) | 0.027 (3) | 0.019 (3) | 0.028 (3) |
C226 | 0.045 (3) | 0.055 (3) | 0.030 (2) | 0.008 (2) | 0.018 (2) | 0.006 (2) |
N1 | 0.145 (8) | 0.152 (9) | 0.099 (6) | −0.007 (7) | 0.055 (6) | −0.015 (6) |
C2 | 0.092 (6) | 0.098 (7) | 0.115 (7) | 0.002 (5) | 0.048 (6) | −0.009 (6) |
C3 | 0.101 (6) | 0.072 (5) | 0.098 (6) | 0.003 (5) | 0.064 (5) | 0.000 (5) |
Au1—Br1 | 2.4069 (19) | C213—C214 | 1.373 (9) |
Au1—P1 | 2.241 (2) | C214—C215 | 1.368 (10) |
P1—C1 | 1.825 (5) | C114—H114 | 0.9500 |
P1—C111 | 1.820 (5) | C115—H115 | 0.9495 |
P1—C121 | 1.822 (5) | C215—C216 | 1.388 (8) |
P2—O1 | 1.490 (3) | C116—H116 | 0.9495 |
P2—C1 | 1.812 (5) | C221—C226 | 1.390 (7) |
P2—C211 | 1.807 (5) | C221—C222 | 1.379 (7) |
P2—C221 | 1.804 (5) | C222—C223 | 1.383 (9) |
N1—C3 | 1.105 (14) | C122—H122 | 0.9498 |
C1—H11 | 0.9503 | C223—C224 | 1.361 (11) |
C1—H12 | 0.9509 | C123—H123 | 0.9494 |
C111—C116 | 1.387 (7) | C224—C225 | 1.368 (10) |
C111—C112 | 1.379 (7) | C124—H124 | 0.9513 |
C112—C113 | 1.385 (9) | C225—C226 | 1.381 (9) |
C113—C114 | 1.365 (9) | C125—H125 | 0.9502 |
C114—C115 | 1.376 (9) | C126—H126 | 0.9511 |
C115—C116 | 1.373 (8) | C2—H21 | 0.9506 |
C121—C122 | 1.388 (6) | C2—H23 | 0.9505 |
C121—C126 | 1.383 (7) | C2—H22 | 0.9508 |
C122—C123 | 1.378 (7) | C212—H212 | 0.9508 |
C123—C124 | 1.370 (9) | C213—H213 | 0.9507 |
C124—C125 | 1.365 (9) | C214—H214 | 0.9511 |
C125—C126 | 1.387 (8) | C215—H215 | 0.9480 |
C2—C3 | 1.433 (14) | C216—H216 | 0.9495 |
C211—C216 | 1.378 (7) | C222—H222 | 0.9498 |
C211—C212 | 1.405 (7) | C223—H223 | 0.9486 |
C212—C213 | 1.378 (8) | C224—H224 | 0.9508 |
C112—H112 | 0.9492 | C225—H225 | 0.9495 |
C113—H113 | 0.9496 | C226—H226 | 0.9494 |
Au1···O1 | 3.274 (4) | C221···H212 | 3.0926 |
Au1···C123i | 4.063 (6) | C222···H114vi | 3.0862 |
Au1···C115ii | 3.562 (7) | C225···H114vi | 2.9313 |
Au1···C116ii | 3.523 (5) | C226···H114vi | 2.8130 |
Au1···H122 | 2.9305 | H11···Br1iv | 3.0597 |
Au1···H123i | 3.2969 | H11···H216 | 2.4283 |
Au1···H222 | 3.6197 | H11···C216 | 3.0073 |
Au1···H112 | 2.9475 | H12···C126 | 2.8611 |
Au1···H115ii | 3.3570 | H12···C116 | 3.0371 |
Au1···H116ii | 3.2784 | H12···H126 | 2.2482 |
Br1···H22i | 3.2011 | H12···C216 | 3.0609 |
Br1···H11ii | 3.0597 | H12···H116 | 2.4870 |
O1···Au1 | 3.274 (4) | H12···O1iv | 2.2571 |
O1···C1ii | 3.183 (6) | H12···H216 | 2.5346 |
O1···H222 | 2.6862 | H22···Br1i | 3.2011 |
O1···H12ii | 2.2571 | H23···C115 | 3.0792 |
O1···H116ii | 2.5950 | H23···C116 | 2.9306 |
O1···H126ii | 2.5547 | H112···Au1 | 2.9475 |
N1···H215iii | 2.7159 | H112···C213vii | 2.9657 |
C1···O1iv | 3.183 (6) | H113···C214vii | 3.0258 |
C1···H126 | 2.8982 | H114···C222viii | 3.0862 |
C1···H116 | 2.9682 | H114···C221viii | 2.8975 |
C1···H216 | 2.7230 | H114···H212viii | 2.5698 |
C3···H215iii | 3.0629 | H114···C225viii | 2.9313 |
C115···Au1iv | 3.562 (7) | H114···C226viii | 2.8130 |
C116···C126 | 3.476 (8) | H115···Au1iv | 3.3571 |
C116···Au1iv | 3.523 (5) | H116···H12 | 2.4870 |
C121···C222 | 3.510 (9) | H116···H126 | 2.4959 |
C121···C221 | 3.470 (7) | H116···Au1iv | 3.2784 |
C123···Au1i | 4.063 (6) | H116···C126 | 2.9659 |
C126···C226 | 3.522 (9) | H116···C1 | 2.9682 |
C126···C221 | 3.497 (8) | H116···O1iv | 2.5950 |
C126···C116 | 3.476 (8) | H122···Au1 | 2.9305 |
C212···C226 | 3.526 (8) | H123···Au1i | 3.2969 |
C115···H23 | 3.0792 | H124···H213ix | 2.5707 |
C116···H23 | 2.9306 | H125···C214iv | 3.0027 |
C116···H12 | 3.0371 | H125···C213iv | 3.0087 |
C221···C126 | 3.497 (8) | H126···C1 | 2.8982 |
C221···C121 | 3.470 (7) | H126···H12 | 2.2482 |
C222···C121 | 3.510 (9) | H126···H116 | 2.4959 |
C126···H116 | 2.9659 | H126···O1iv | 2.5547 |
C226···C212 | 3.526 (8) | H212···H114vi | 2.5698 |
C126···H12 | 2.8611 | H212···C221 | 3.0926 |
C226···C126 | 3.522 (9) | H213···H124x | 2.5707 |
C211···H226 | 2.8161 | H215···C3xi | 3.0629 |
C213···H112v | 2.9657 | H215···N1xi | 2.7159 |
C213···H125ii | 3.0087 | H216···H11 | 2.4283 |
C214···H125ii | 3.0027 | H216···H12 | 2.5346 |
C214···H113v | 3.0258 | H216···C1 | 2.7230 |
C215···H222iv | 3.0421 | H222···C215ii | 3.0421 |
C216···H12 | 3.0609 | H222···Au1 | 3.6197 |
C216···H11 | 3.0073 | H222···O1 | 2.6862 |
C221···H114vi | 2.8975 | H226···C211 | 2.8161 |
Br1—Au1—P1 | 178.53 (4) | C114—C115—H115 | 120.11 |
Au1—P1—C1 | 114.21 (15) | C116—C115—H115 | 120.14 |
Au1—P1—C111 | 113.87 (14) | C111—C116—H116 | 119.66 |
Au1—P1—C121 | 113.16 (14) | C211—C216—C215 | 120.1 (6) |
C1—P1—C111 | 103.0 (2) | C115—C116—H116 | 119.60 |
C1—P1—C121 | 108.1 (2) | P2—C221—C222 | 118.8 (4) |
C111—P1—C121 | 103.5 (2) | C222—C221—C226 | 119.7 (5) |
O1—P2—C1 | 113.2 (2) | P2—C221—C226 | 121.5 (4) |
O1—P2—C211 | 112.7 (2) | C221—C222—C223 | 120.2 (6) |
O1—P2—C221 | 112.0 (2) | C121—C122—H122 | 119.88 |
C1—P2—C211 | 106.2 (2) | C123—C122—H122 | 120.03 |
C1—P2—C221 | 106.4 (2) | C222—C223—C224 | 119.6 (6) |
C211—P2—C221 | 105.8 (2) | C124—C123—H123 | 119.80 |
P1—C1—P2 | 115.0 (2) | C122—C123—H123 | 119.85 |
P2—C1—H11 | 108.09 | C125—C124—H124 | 120.28 |
P1—C1—H11 | 108.10 | C223—C224—C225 | 120.9 (7) |
P1—C1—H12 | 108.02 | C123—C124—H124 | 120.11 |
P2—C1—H12 | 108.07 | C124—C125—H125 | 119.32 |
H11—C1—H12 | 109.48 | C126—C125—H125 | 119.42 |
P1—C111—C112 | 120.0 (4) | C224—C225—C226 | 120.3 (6) |
P1—C111—C116 | 121.0 (4) | C221—C226—C225 | 119.3 (6) |
C112—C111—C116 | 119.0 (5) | C125—C126—H126 | 120.49 |
C111—C112—C113 | 120.0 (5) | C121—C126—H126 | 120.44 |
C112—C113—C114 | 120.4 (6) | C3—C2—H22 | 109.52 |
C113—C114—C115 | 120.1 (6) | C3—C2—H23 | 109.57 |
C114—C115—C116 | 119.7 (6) | H21—C2—H23 | 109.41 |
C111—C116—C115 | 120.7 (5) | H22—C2—H23 | 109.51 |
P1—C121—C126 | 122.7 (3) | H21—C2—H22 | 109.33 |
P1—C121—C122 | 117.7 (3) | C3—C2—H21 | 109.50 |
C122—C121—C126 | 119.5 (4) | C211—C212—H212 | 120.23 |
C121—C122—C123 | 120.1 (5) | C213—C212—H212 | 120.33 |
C122—C123—C124 | 120.3 (5) | C212—C213—H213 | 119.52 |
C123—C124—C125 | 119.6 (6) | C214—C213—H213 | 119.54 |
C124—C125—C126 | 121.3 (5) | C213—C214—H214 | 120.18 |
C121—C126—C125 | 119.1 (4) | C215—C214—H214 | 120.06 |
N1—C3—C2 | 177.9 (11) | C216—C215—H215 | 119.69 |
P2—C211—C216 | 125.1 (4) | C214—C215—H215 | 119.76 |
C212—C211—C216 | 119.2 (4) | C211—C216—H216 | 120.01 |
P2—C211—C212 | 115.7 (3) | C215—C216—H216 | 119.86 |
C111—C112—H112 | 120.02 | C223—C222—H222 | 119.89 |
C113—C112—H112 | 120.00 | C221—C222—H222 | 119.92 |
C211—C212—C213 | 119.4 (5) | C222—C223—H223 | 120.17 |
C212—C213—C214 | 120.9 (6) | C224—C223—H223 | 120.19 |
C114—C113—H113 | 119.78 | C223—C224—H224 | 119.47 |
C112—C113—H113 | 119.79 | C225—C224—H224 | 119.63 |
C113—C114—H114 | 119.87 | C224—C225—H225 | 119.88 |
C213—C214—C215 | 119.8 (6) | C226—C225—H225 | 119.85 |
C115—C114—H114 | 120.00 | C221—C226—H226 | 120.33 |
C214—C215—C216 | 120.5 (6) | C225—C226—H226 | 120.40 |
Au1—P1—C1—P2 | −46.7 (3) | H112—C112—C113—H113 | 0.21 |
C111—P1—C1—P2 | −170.7 (2) | C111—C112—C113—H113 | −179.86 |
C121—P1—C1—P2 | 80.2 (3) | H112—C112—C113—C114 | −179.62 |
Au1—P1—C111—C112 | 6.2 (5) | H113—C113—C114—H114 | 1.59 |
Au1—P1—C111—C116 | −176.3 (3) | H113—C113—C114—C115 | −178.70 |
C1—P1—C111—C112 | 130.5 (4) | C212—C213—C214—C215 | −0.6 (9) |
C1—P1—C111—C116 | −52.0 (4) | C112—C113—C114—H114 | −178.58 |
C121—P1—C111—C112 | −117.0 (4) | H114—C114—C115—C116 | 178.55 |
C121—P1—C111—C116 | 60.5 (4) | C113—C114—C115—H115 | 178.78 |
Au1—P1—C121—C122 | −22.2 (5) | C213—C214—C215—C216 | 1.2 (9) |
Au1—P1—C121—C126 | 160.4 (4) | H114—C114—C115—H115 | −1.52 |
C1—P1—C121—C122 | −149.7 (4) | C114—C115—C116—H116 | 179.65 |
C1—P1—C121—C126 | 32.9 (5) | H115—C115—C116—C111 | 179.81 |
C111—P1—C121—C122 | 101.5 (4) | H115—C115—C116—H116 | −0.29 |
C111—P1—C121—C126 | −75.9 (5) | C214—C215—C216—C211 | −1.0 (8) |
O1—P2—C1—P1 | 56.1 (3) | C126—C121—C122—H122 | −176.85 |
C211—P2—C1—P1 | −179.7 (2) | P1—C121—C126—H126 | −4.83 |
C221—P2—C1—P1 | −67.3 (3) | P1—C121—C122—H122 | 5.71 |
O1—P2—C211—C212 | −59.8 (4) | P2—C221—C222—C223 | −178.8 (5) |
O1—P2—C211—C216 | 118.5 (4) | C226—C221—C222—C223 | 1.3 (9) |
C1—P2—C211—C212 | 175.7 (3) | P2—C221—C226—C225 | 179.8 (5) |
C1—P2—C211—C216 | −6.0 (4) | C222—C221—C226—C225 | −0.3 (9) |
C221—P2—C211—C212 | 62.9 (4) | C122—C121—C126—H126 | 177.86 |
C221—P2—C211—C216 | −118.9 (4) | C221—C222—C223—C224 | −1.7 (11) |
O1—P2—C221—C222 | −22.1 (5) | C121—C122—C123—H123 | 177.98 |
O1—P2—C221—C226 | 157.7 (4) | H122—C122—C123—C124 | 178.03 |
C1—P2—C221—C222 | 102.1 (5) | H122—C122—C123—H123 | −1.99 |
C1—P2—C221—C226 | −78.1 (5) | H123—C123—C124—C125 | 179.96 |
C211—P2—C221—C222 | −145.3 (4) | H123—C123—C124—H124 | −0.12 |
C211—P2—C221—C226 | 34.6 (5) | C222—C223—C224—C225 | 1.1 (12) |
P2—C211—C212—C213 | 178.9 (4) | C122—C123—C124—H124 | 179.86 |
P1—C111—C112—H112 | −4.22 | C223—C224—C225—C226 | −0.2 (11) |
C116—C111—C112—H112 | 178.24 | H124—C124—C125—H125 | 1.09 |
P1—C111—C116—H116 | 4.26 | C123—C124—C125—H125 | −178.98 |
C216—C211—C212—C213 | 0.5 (7) | H124—C124—C125—C126 | −178.98 |
P2—C211—C216—C215 | −178.1 (4) | C224—C225—C226—C221 | −0.2 (10) |
C212—C211—C216—C215 | 0.1 (7) | C124—C125—C126—H126 | −179.92 |
C112—C111—C116—H116 | −178.23 | H125—C125—C126—C121 | −179.82 |
C211—C212—C213—C214 | −0.3 (8) | H125—C125—C126—H126 | 0.02 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y−1/2, −z+3/2; (iv) x, −y+1/2, z+1/2; (v) x+1, −y+1/2, z+1/2; (vi) x+1, y, z; (vii) x−1, −y+1/2, z−1/2; (viii) x−1, y, z; (ix) −x+2, y−1/2, −z+3/2; (x) −x+2, y+1/2, −z+3/2; (xi) −x+1, y+1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H12···O1iv | 0.95 | 2.26 | 3.183 (6) | 164 |
C116—H116···O1iv | 0.95 | 2.60 | 3.500 (7) | 159 |
C126—H126···O1iv | 0.95 | 2.55 | 3.499 (6) | 172 |
Symmetry code: (iv) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [AuBr(C25H22OP2)]·CH3CN |
Mr | 718.29 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 11.657 (3), 22.436 (17), 11.209 (4) |
β (°) | 115.98 (2) |
V (Å3) | 2635 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.24 |
Crystal size (mm) | 0.30 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | ψ scan (North, Phillips & Matthews, 1968) |
Tmin, Tmax | 0.135, 0.235 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6598, 6045, 4561 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.079, 1.02 |
No. of reflections | 6045 |
No. of parameters | 299 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 1.05, −1.07 |
Computer programs: MSC/AFC7 Diffractometer Control Software for Windows (Molecular Structure Corporation, 1999), MSC/AFC7 Diffractometer Control Software for Windows, TEXSAN for Windows (Molecular Structure Corporation, 1997-2001), TEXSAN for Windows and SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), TEXSAN for Windows and PLATON (Spek, 1980-2001).
Au1—Br1 | 2.4069 (19) | P2—O1 | 1.490 (3) |
Au1—P1 | 2.241 (2) | P2—C1 | 1.812 (5) |
P1—C1 | 1.825 (5) | P2—C211 | 1.807 (5) |
P1—C111 | 1.820 (5) | P2—C221 | 1.804 (5) |
P1—C121 | 1.822 (5) | N1—C3 | 1.105 (14) |
Br1—Au1—P1 | 178.53 (4) | C211—P2—C221 | 105.8 (2) |
Au1—P1—C1 | 114.21 (15) | P1—C1—P2 | 115.0 (2) |
Au1—P1—C111 | 113.87 (14) | P1—C111—C112 | 120.0 (4) |
Au1—P1—C121 | 113.16 (14) | P1—C111—C116 | 121.0 (4) |
C1—P1—C111 | 103.0 (2) | P1—C121—C126 | 122.7 (3) |
C1—P1—C121 | 108.1 (2) | P1—C121—C122 | 117.7 (3) |
C111—P1—C121 | 103.5 (2) | N1—C3—C2 | 177.9 (11) |
O1—P2—C1 | 113.2 (2) | P2—C211—C216 | 125.1 (4) |
O1—P2—C211 | 112.7 (2) | P2—C211—C212 | 115.7 (3) |
O1—P2—C221 | 112.0 (2) | P2—C221—C222 | 118.8 (4) |
C1—P2—C211 | 106.2 (2) | P2—C221—C226 | 121.5 (4) |
C1—P2—C221 | 106.4 (2) |
Mixed bidentate phosphine–phosphine oxide ligands of general formula R2P–Y–P(O)R2, where Y is an organic spacer group, represent an important class of bidentate chelating ligands incorporating both soft (P) and hard (O) donor atoms (Grushin, 2001). Transition metal complexes of these ligands show a variety of structural forms (e.g. Coyle et al., 1998; Saravanabharathi et al., 2002; Faller & Parr, 2000) with evidence for both bidentate and monodentate coordination of the ligand to the metal atom.
We report here the structure of the acetonitrile solvate of the 1:1 complex of Ph2P(CH2)P(O)Ph2 with gold(I) bromide, [(dppmO)AuBr]·CH3CN, (I). The structure comprises discrete molecules of [(dppmO)AuBr] and acetonitrile separated by normal van der Waals distances (Fig. 1). The dppmO ligand coordinates to the gold through the P atom to yield a linear two-coordinate P—Au—Br geometry, with Au—P = 2.241 (2) Å, Au—Br = 2.4069 (19) Å and P—Au—Br = 178.53 (4)°. These parameters are similar to those recorded for other two-coordinate R3PAuBr complexes (Bott et al., 2000). The P═O bond length of 1.490 (3) Å is also in accord with values recorded for other phosphine oxides (See et al., 1998).
The P—Au—Br and P═O groups lie almost parallel with the torsion angle O—P···P—Au 8.3 (2)°. For comparison, in the structure of the benzene solvate of the dioxide, dppmO2 (Antipin et al., 1980), the P═O bonds are almost antiparallel, whereas in the structures of adducts of dppmO2 with sodium halides (Hewertson et al., 1970; Ding et al., 2000) coordination of the O atoms to the sodium cation results in parallel P═O bonds and an Na···O distance of 2.457 (1) Å. An intermediate situation is observed for the structure of the 2:1 gold chloride complex with dppm, [(AuCl)2(dppm)] (Schmidbaur et al., 1977), where the Au—P···P—Au torsion angle is 67 (1)°, with an Au···Au distance of 3.351 (2) Å, the latter suggestive of a significant aurophilic interaction. In the present complex, the intramolecular Au···O distance of 3.274 (4) Å is slightly longer than the Au···O distances for the [(tmpp)AuX] complexes [X = Cl, Br, I; tmpp = tris(2,4,6-trimethoxyphenyl)phosphine)] (Baker et al., 1995), which are in the range 2.92 (2)–3.15 (1) Å. This result, together with the absence of any significant distortion from linearity of the P–Au–Br bond, indicates the presence of only weak, if any, bonding interactions between the Au and O atoms and that the conformational structure of the complex is best ascribed as an outcome of crystal-packing considerations.