Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109017831/fa3184sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109017831/fa3184Isup2.hkl |
CCDC reference: 746043
To a suspension of methylthiophenyl boronic acid, CH3SC6H4-B(OH)2 (0.336 g, 0.2 mmol), in propan-2-ol (10 ml), solid CsCO3 (0.0386 g, 0.2 mmol) was added. After a few minutes of stirring, AuPPh3Cl (0.05 g, 0.1 mmol) was added and a condenser was attached to the reaction flask. The whitish suspension was refluxed at 333 K for 10 h, after which time the liquid looked clear. Clumps of white solid slowly formed. The propan-2-ol solution was then reduced to dryness under vacuum. The dry residue was rinsed with hexane and extracted with benzene (5 ml). Upon layering the benzene solution with hexane, shiny crystals of (I) grew within a week, with a yield of 90%. The sample used in data collection was mounted on a loop using Paratone oil. This compound was also characterized by 1H NMR spectroscopy (CDCl3, δ, p.p.m.): 7.70–7.45 [m, P(C6H5)3], 7.13–7.07 (m, C6H4), 2.5 (s, S—CH3).
The difference peak of 2.96 e Å-3 is 0.81 Å from the Au atom. Rigid-bond restraints on the displacement parameters of C23, C24 and C25 (DELU; three restraints) and isotropic behavior restraints at C24 (ISOR; six restraints) were applied during refinement. All H atoms were placed in calculated positions and refined using a riding model. Aromatic C—H = 0.95 Å, Uiso(H) = 1.2Ueq(C). The H atoms at methyl group C7 were located in a local difference Fourier calculation and refined as riding atoms with a variable torsion angle about the C7—S1 bond (AFIX 137), C—H = 0.98 Å, Uiso(H) = 1.5Ueq(C7). [Please rephrase this section using software-independent terminology]
Data collection: APEX2 (Bruker Nonius, 2008); cell refinement: APEX2 (Bruker Nonius, 2008); data reduction: APEX2 (Bruker Nonius, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Fig. 1. The structure of (I), showing the almost linear P—Au—C arrangement. | |
Fig. 2. Chain formation in (I), mediated by a weak C—H···π contact. [Symmetry code: (i) 1 + x, y, z]. |
[Au(C7H7S)(C18H15P)] | F(000) = 1128 |
Mr = 582.42 | Dx = 1.775 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P2ac2ab | Cell parameters from 9913 reflections |
a = 6.986 (4) Å | θ = 2.4–26.6° |
b = 15.553 (9) Å | µ = 6.93 mm−1 |
c = 20.060 (12) Å | T = 110 K |
V = 2180 (2) Å3 | Block, colourless |
Z = 4 | 0.17 × 0.10 × 0.10 mm |
Bruker APEXII diffractometer | 4680 independent reflections |
Radiation source: fine-focus sealed tube | 4396 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.135 |
ω scans | θmax = 27.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2006) | h = −8→8 |
Tmin = 0.391, Tmax = 0.544 | k = −19→19 |
24159 measured reflections | l = −25→25 |
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)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0425P)2 + 4.3846P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
4680 reflections | Δρmax = 2.96 e Å−3 |
254 parameters | Δρmin = −1.35 e Å−3 |
9 restraints | Absolute structure: (Flack, 1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.003 (11) |
[Au(C7H7S)(C18H15P)] | V = 2180 (2) Å3 |
Mr = 582.42 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.986 (4) Å | µ = 6.93 mm−1 |
b = 15.553 (9) Å | T = 110 K |
c = 20.060 (12) Å | 0.17 × 0.10 × 0.10 mm |
Bruker APEXII diffractometer | 4680 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2006) | 4396 reflections with I > 2σ(I) |
Tmin = 0.391, Tmax = 0.544 | Rint = 0.135 |
24159 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.099 | Δρmax = 2.96 e Å−3 |
S = 1.05 | Δρmin = −1.35 e Å−3 |
4680 reflections | Absolute structure: (Flack, 1983), with how many Friedel pairs? |
254 parameters | Absolute structure parameter: −0.003 (11) |
9 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
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 | 0.72064 (4) | 0.050031 (17) | 0.776484 (14) | 0.02846 (10) | |
S1 | 0.7156 (4) | 0.13156 (14) | 0.92545 (11) | 0.0393 (5) | |
P1 | 0.9351 (3) | 0.08800 (12) | 0.69512 (10) | 0.0238 (4) | |
C1 | 0.5167 (12) | 0.0226 (5) | 0.8463 (4) | 0.0298 (17) | |
C2 | 0.5125 (11) | 0.0643 (5) | 0.9094 (4) | 0.0285 (17) | |
C3 | 0.3661 (12) | 0.0552 (6) | 0.9541 (4) | 0.0339 (16) | |
H3 | 0.3683 | 0.0855 | 0.9952 | 0.041* | |
C4 | 0.2148 (14) | 0.0012 (6) | 0.9388 (4) | 0.043 (2) | |
H4 | 0.1140 | −0.0064 | 0.9700 | 0.051* | |
C5 | 0.2087 (13) | −0.0417 (5) | 0.8785 (5) | 0.0417 (19) | |
H5 | 0.1046 | −0.0785 | 0.8679 | 0.050* | |
C6 | 0.3612 (12) | −0.0297 (4) | 0.8327 (4) | 0.0281 (16) | |
H6 | 0.3563 | −0.0587 | 0.7911 | 0.034* | |
C7 | 0.6795 (16) | 0.1683 (6) | 1.0085 (5) | 0.051 (3) | |
H7A | 0.5686 | 0.2068 | 1.0098 | 0.076* | |
H7B | 0.7936 | 0.1993 | 1.0237 | 0.076* | |
H7C | 0.6565 | 0.1189 | 1.0378 | 0.076* | |
C8 | 0.8127 (11) | 0.1244 (4) | 0.6198 (3) | 0.0237 (15) | |
C9 | 0.6742 (12) | 0.1893 (5) | 0.6262 (4) | 0.0353 (19) | |
H9 | 0.6508 | 0.2144 | 0.6686 | 0.042* | |
C10 | 0.5727 (14) | 0.2167 (6) | 0.5718 (5) | 0.044 (2) | |
H10 | 0.4798 | 0.2609 | 0.5766 | 0.053* | |
C11 | 0.6047 (13) | 0.1804 (6) | 0.5101 (5) | 0.042 (2) | |
H11 | 0.5315 | 0.1984 | 0.4727 | 0.050* | |
C12 | 0.7447 (13) | 0.1173 (5) | 0.5028 (4) | 0.0367 (19) | |
H12 | 0.7700 | 0.0933 | 0.4602 | 0.044* | |
C13 | 0.8451 (12) | 0.0900 (5) | 0.5570 (4) | 0.0302 (17) | |
H13 | 0.9394 | 0.0466 | 0.5516 | 0.036* | |
C14 | 1.1012 (10) | 0.0050 (4) | 0.6669 (4) | 0.0238 (15) | |
C15 | 1.0400 (12) | −0.0816 (5) | 0.6720 (4) | 0.0307 (17) | |
H15 | 0.9199 | −0.0953 | 0.6915 | 0.037* | |
C16 | 1.1583 (14) | −0.1456 (5) | 0.6482 (4) | 0.038 (2) | |
H16 | 1.1188 | −0.2039 | 0.6514 | 0.045* | |
C17 | 1.3333 (13) | −0.1263 (5) | 0.6198 (4) | 0.037 (2) | |
H17 | 1.4125 | −0.1711 | 0.6031 | 0.044* | |
C18 | 1.3928 (12) | −0.0416 (5) | 0.6157 (4) | 0.0350 (18) | |
H18 | 1.5140 | −0.0283 | 0.5969 | 0.042* | |
C19 | 1.2761 (12) | 0.0239 (4) | 0.6392 (4) | 0.0282 (15) | |
H19 | 1.3172 | 0.0820 | 0.6360 | 0.034* | |
C20 | 1.0896 (10) | 0.1767 (4) | 0.7190 (4) | 0.0243 (14) | |
C21 | 1.1805 (12) | 0.1711 (5) | 0.7808 (4) | 0.0366 (18) | |
H21 | 1.1531 | 0.1244 | 0.8098 | 0.044* | |
C22 | 1.3102 (14) | 0.2335 (5) | 0.7999 (4) | 0.040 (2) | |
H22 | 1.3717 | 0.2296 | 0.8420 | 0.048* | |
C23 | 1.3508 (12) | 0.3013 (5) | 0.7580 (4) | 0.0312 (16) | |
H23 | 1.4423 | 0.3436 | 0.7703 | 0.037* | |
C24 | 1.2545 (13) | 0.3065 (5) | 0.6971 (4) | 0.0348 (16) | |
H24 | 1.2773 | 0.3542 | 0.6687 | 0.042* | |
C25 | 1.1305 (13) | 0.2454 (5) | 0.6780 (4) | 0.0331 (17) | |
H25 | 1.0701 | 0.2496 | 0.6357 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Au1 | 0.02780 (15) | 0.02841 (14) | 0.02918 (15) | 0.00254 (11) | 0.00644 (11) | 0.00542 (12) |
S1 | 0.0361 (11) | 0.0421 (11) | 0.0396 (11) | −0.0094 (10) | 0.0023 (10) | 0.0031 (8) |
P1 | 0.0243 (10) | 0.0219 (8) | 0.0253 (9) | −0.0019 (7) | 0.0016 (8) | −0.0007 (7) |
C1 | 0.033 (4) | 0.026 (4) | 0.030 (4) | 0.001 (3) | 0.000 (3) | 0.013 (3) |
C2 | 0.031 (4) | 0.023 (4) | 0.031 (4) | 0.009 (3) | 0.010 (3) | 0.011 (3) |
C3 | 0.035 (4) | 0.035 (4) | 0.031 (4) | 0.002 (4) | 0.004 (3) | 0.007 (4) |
C4 | 0.036 (5) | 0.054 (5) | 0.037 (5) | −0.004 (4) | 0.017 (4) | 0.008 (4) |
C5 | 0.029 (4) | 0.035 (4) | 0.061 (5) | −0.006 (4) | 0.008 (4) | 0.009 (4) |
C6 | 0.033 (4) | 0.023 (4) | 0.028 (4) | 0.001 (3) | −0.001 (3) | 0.004 (3) |
C7 | 0.053 (7) | 0.048 (5) | 0.052 (6) | −0.021 (5) | 0.003 (5) | 0.002 (4) |
C8 | 0.030 (4) | 0.016 (3) | 0.025 (3) | −0.010 (3) | 0.000 (3) | 0.003 (2) |
C9 | 0.035 (5) | 0.048 (5) | 0.023 (4) | 0.006 (4) | −0.002 (3) | 0.001 (3) |
C10 | 0.034 (5) | 0.056 (6) | 0.043 (5) | 0.010 (4) | 0.001 (4) | 0.010 (4) |
C11 | 0.035 (5) | 0.054 (6) | 0.036 (5) | −0.011 (4) | −0.010 (4) | 0.018 (4) |
C12 | 0.042 (6) | 0.040 (4) | 0.028 (4) | −0.007 (4) | 0.000 (4) | 0.003 (3) |
C13 | 0.034 (4) | 0.023 (3) | 0.033 (4) | 0.002 (3) | 0.004 (3) | 0.000 (3) |
C14 | 0.024 (4) | 0.023 (3) | 0.025 (4) | −0.001 (3) | 0.000 (3) | −0.004 (3) |
C15 | 0.037 (4) | 0.023 (3) | 0.032 (4) | −0.003 (3) | −0.004 (4) | 0.008 (3) |
C16 | 0.045 (5) | 0.023 (4) | 0.045 (5) | −0.001 (4) | −0.004 (4) | 0.005 (4) |
C17 | 0.042 (5) | 0.034 (4) | 0.035 (4) | 0.014 (4) | −0.008 (4) | −0.009 (3) |
C18 | 0.025 (4) | 0.037 (4) | 0.043 (4) | 0.004 (4) | 0.000 (3) | 0.002 (4) |
C19 | 0.024 (4) | 0.025 (3) | 0.036 (4) | −0.004 (3) | −0.008 (3) | 0.003 (3) |
C20 | 0.021 (3) | 0.020 (3) | 0.032 (4) | 0.002 (2) | 0.003 (3) | −0.006 (3) |
C21 | 0.042 (5) | 0.031 (4) | 0.037 (4) | 0.004 (3) | −0.011 (4) | 0.006 (3) |
C22 | 0.054 (6) | 0.029 (4) | 0.037 (4) | −0.001 (4) | −0.024 (4) | −0.001 (3) |
C23 | 0.030 (4) | 0.024 (3) | 0.039 (4) | −0.005 (3) | −0.001 (3) | −0.005 (3) |
C24 | 0.048 (4) | 0.022 (3) | 0.035 (3) | −0.006 (3) | −0.003 (3) | −0.007 (2) |
C25 | 0.041 (5) | 0.029 (4) | 0.030 (4) | −0.010 (3) | −0.005 (3) | 0.005 (3) |
Au1—C1 | 2.042 (8) | C11—H11 | 0.9500 |
Au1—P1 | 2.293 (2) | C12—C13 | 1.360 (11) |
S1—C7 | 1.779 (10) | C12—H12 | 0.9500 |
S1—C2 | 1.792 (8) | C13—H13 | 0.9500 |
P1—C20 | 1.816 (7) | C14—C19 | 1.374 (11) |
P1—C8 | 1.825 (7) | C14—C15 | 1.417 (10) |
P1—C14 | 1.826 (7) | C15—C16 | 1.379 (12) |
C1—C6 | 1.384 (11) | C15—H15 | 0.9500 |
C1—C2 | 1.423 (11) | C16—C17 | 1.382 (13) |
C2—C3 | 1.368 (10) | C16—H16 | 0.9500 |
C3—C4 | 1.385 (13) | C17—C18 | 1.384 (12) |
C3—H3 | 0.9500 | C17—H17 | 0.9500 |
C4—C5 | 1.382 (13) | C18—C19 | 1.387 (11) |
C4—H4 | 0.9500 | C18—H18 | 0.9500 |
C5—C6 | 1.418 (12) | C19—H19 | 0.9500 |
C5—H5 | 0.9500 | C20—C25 | 1.379 (10) |
C6—H6 | 0.9500 | C20—C21 | 1.395 (11) |
C7—H7A | 0.9800 | C21—C22 | 1.381 (12) |
C7—H7B | 0.9800 | C21—H21 | 0.9500 |
C7—H7C | 0.9800 | C22—C23 | 1.378 (11) |
C8—C13 | 1.388 (10) | C22—H22 | 0.9500 |
C8—C9 | 1.404 (11) | C23—C24 | 1.397 (12) |
C9—C10 | 1.368 (12) | C23—H23 | 0.9500 |
C9—H9 | 0.9500 | C24—C25 | 1.341 (11) |
C10—C11 | 1.378 (13) | C24—H24 | 0.9500 |
C10—H10 | 0.9500 | C25—H25 | 0.9500 |
C11—C12 | 1.394 (13) | ||
C1—Au1—P1 | 175.9 (2) | C12—C11—H11 | 120.1 |
C7—S1—C2 | 104.1 (4) | C13—C12—C11 | 119.8 (8) |
C20—P1—C8 | 105.2 (3) | C13—C12—H12 | 120.1 |
C20—P1—C14 | 104.0 (3) | C11—C12—H12 | 120.1 |
C8—P1—C14 | 105.1 (3) | C12—C13—C8 | 121.4 (7) |
C20—P1—Au1 | 113.3 (3) | C12—C13—H13 | 119.3 |
C8—P1—Au1 | 111.3 (3) | C8—C13—H13 | 119.3 |
C14—P1—Au1 | 117.0 (3) | C19—C14—C15 | 120.1 (7) |
C6—C1—C2 | 115.2 (7) | C19—C14—P1 | 122.6 (5) |
C6—C1—Au1 | 122.4 (6) | C15—C14—P1 | 117.3 (6) |
C2—C1—Au1 | 122.0 (6) | C16—C15—C14 | 118.7 (8) |
C3—C2—C1 | 123.5 (8) | C16—C15—H15 | 120.6 |
C3—C2—S1 | 122.3 (6) | C14—C15—H15 | 120.6 |
C1—C2—S1 | 114.2 (6) | C15—C16—C17 | 121.1 (8) |
C2—C3—C4 | 119.2 (8) | C15—C16—H16 | 119.5 |
C2—C3—H3 | 120.4 | C17—C16—H16 | 119.5 |
C4—C3—H3 | 120.4 | C16—C17—C18 | 119.8 (8) |
C5—C4—C3 | 120.7 (8) | C16—C17—H17 | 120.1 |
C5—C4—H4 | 119.6 | C18—C17—H17 | 120.1 |
C3—C4—H4 | 119.6 | C17—C18—C19 | 120.2 (8) |
C4—C5—C6 | 118.7 (8) | C17—C18—H18 | 119.9 |
C4—C5—H5 | 120.7 | C19—C18—H18 | 119.9 |
C6—C5—H5 | 120.7 | C14—C19—C18 | 120.2 (7) |
C1—C6—C5 | 122.7 (8) | C14—C19—H19 | 119.9 |
C1—C6—H6 | 118.7 | C18—C19—H19 | 119.9 |
C5—C6—H6 | 118.7 | C25—C20—C21 | 118.9 (7) |
S1—C7—H7A | 109.5 | C25—C20—P1 | 123.7 (6) |
S1—C7—H7B | 109.5 | C21—C20—P1 | 117.3 (5) |
H7A—C7—H7B | 109.5 | C22—C21—C20 | 120.1 (7) |
S1—C7—H7C | 109.5 | C22—C21—H21 | 120.0 |
H7A—C7—H7C | 109.5 | C20—C21—H21 | 120.0 |
H7B—C7—H7C | 109.5 | C23—C22—C21 | 120.3 (7) |
C13—C8—C9 | 118.1 (7) | C23—C22—H22 | 119.9 |
C13—C8—P1 | 123.8 (6) | C21—C22—H22 | 119.9 |
C9—C8—P1 | 118.1 (5) | C22—C23—C24 | 118.6 (7) |
C10—C9—C8 | 120.6 (8) | C22—C23—H23 | 120.7 |
C10—C9—H9 | 119.7 | C24—C23—H23 | 120.7 |
C8—C9—H9 | 119.7 | C25—C24—C23 | 121.3 (7) |
C9—C10—C11 | 120.2 (9) | C25—C24—H24 | 119.4 |
C9—C10—H10 | 119.9 | C23—C24—H24 | 119.4 |
C11—C10—H10 | 119.9 | C24—C25—C20 | 120.9 (8) |
C10—C11—C12 | 119.8 (8) | C24—C25—H25 | 119.6 |
C10—C11—H11 | 120.1 | C20—C25—H25 | 119.6 |
C6—C1—C2—C3 | −0.7 (11) | C8—P1—C14—C19 | 81.2 (7) |
Au1—C1—C2—C3 | 172.0 (6) | Au1—P1—C14—C19 | −154.8 (5) |
C6—C1—C2—S1 | −179.9 (5) | C20—P1—C14—C15 | 153.4 (6) |
Au1—C1—C2—S1 | −7.3 (8) | C8—P1—C14—C15 | −96.3 (7) |
C7—S1—C2—C3 | 4.6 (8) | Au1—P1—C14—C15 | 27.6 (7) |
C7—S1—C2—C1 | −176.1 (6) | C19—C14—C15—C16 | −0.6 (12) |
C1—C2—C3—C4 | 1.6 (12) | P1—C14—C15—C16 | 177.0 (6) |
S1—C2—C3—C4 | −179.2 (6) | C14—C15—C16—C17 | 0.0 (13) |
C2—C3—C4—C5 | −1.4 (13) | C15—C16—C17—C18 | 0.8 (13) |
C3—C4—C5—C6 | 0.3 (13) | C16—C17—C18—C19 | −1.0 (12) |
C2—C1—C6—C5 | −0.5 (11) | C15—C14—C19—C18 | 0.4 (11) |
Au1—C1—C6—C5 | −173.1 (6) | P1—C14—C19—C18 | −177.0 (6) |
C4—C5—C6—C1 | 0.7 (12) | C17—C18—C19—C14 | 0.4 (12) |
C20—P1—C8—C13 | 111.2 (7) | C8—P1—C20—C25 | −13.2 (7) |
C14—P1—C8—C13 | 1.8 (7) | C14—P1—C20—C25 | 97.0 (7) |
Au1—P1—C8—C13 | −125.8 (6) | Au1—P1—C20—C25 | −135.0 (6) |
C20—P1—C8—C9 | −70.5 (7) | C8—P1—C20—C21 | 171.0 (6) |
C14—P1—C8—C9 | −179.9 (6) | C14—P1—C20—C21 | −78.8 (6) |
Au1—P1—C8—C9 | 52.5 (6) | Au1—P1—C20—C21 | 49.3 (6) |
C13—C8—C9—C10 | 1.0 (12) | C25—C20—C21—C22 | −0.5 (12) |
P1—C8—C9—C10 | −177.4 (7) | P1—C20—C21—C22 | 175.4 (7) |
C8—C9—C10—C11 | 0.3 (14) | C20—C21—C22—C23 | −0.1 (14) |
C9—C10—C11—C12 | −1.8 (14) | C21—C22—C23—C24 | 1.6 (13) |
C10—C11—C12—C13 | 1.9 (13) | C22—C23—C24—C25 | −2.6 (13) |
C11—C12—C13—C8 | −0.6 (12) | C23—C24—C25—C20 | 2.0 (13) |
C9—C8—C13—C12 | −0.8 (11) | C21—C20—C25—C24 | −0.4 (12) |
P1—C8—C13—C12 | 177.5 (6) | P1—C20—C25—C24 | −176.1 (7) |
C20—P1—C14—C19 | −29.1 (7) |
Experimental details
Crystal data | |
Chemical formula | [Au(C7H7S)(C18H15P)] |
Mr | 582.42 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 110 |
a, b, c (Å) | 6.986 (4), 15.553 (9), 20.060 (12) |
V (Å3) | 2180 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 6.93 |
Crystal size (mm) | 0.17 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2006) |
Tmin, Tmax | 0.391, 0.544 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24159, 4680, 4396 |
Rint | 0.135 |
(sin θ/λ)max (Å−1) | 0.638 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.099, 1.05 |
No. of reflections | 4680 |
No. of parameters | 254 |
No. of restraints | 9 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.96, −1.35 |
Absolute structure | (Flack, 1983), with how many Friedel pairs? |
Absolute structure parameter | −0.003 (11) |
Computer programs: APEX2 (Bruker Nonius, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXTL (Sheldrick, 2008).
Compound | Space group | Au—P | Au—C | P—Au—C |
C38H32Au2P (Bennett et al., 2004) | P21/a | 2.295, 2.297 | 2.011, 2.062 | 176.8, 175.9 |
C30H24AuOP (Baukanova et al., 1994) | P1 | 2.288 | 2.040 | 179.5 |
C48H38Au2OP2 (Baukanova et al., 1994) | P21/c | 2.269, 2.280 | 2.052, 2.059 | 174.8, 174.7 |
C27H35AuP+.SbF6- (Herrero-Gomez et al., 2006) | P21/n | 2.2643 (10) | 2.299 (5), 2.423 (5)a | 157.2, 164.9 |
C30H42AuP (Partyka et al., 2006) | P1 | 2.291 | 2.051 | 174.5 |
C24H20AuP (Hong et al., 1994) | P1 | 2.296 (2), 2.295 | 2.045 (6), 2.054 | 175.5 (2), 177.6 |
C37H32Au2P2 (Hong et al., 1994) | C2/c | 2.300 (2) | 2.07 (2) | 175.8 (4) |
C50H42Au2P2.CH2Cl2 (Baukanova et al., 1997) | P21/c | 2.279 (8) | 2.05 (2) | 174.5 (5) |
C30H24AuP (Osawa et al., 2007) | P1 | 2.285 | 2.055 | 177.1 |
C53H77Au2NP2 (Kui et al., 2006) | C2/c | 2.302 (9), 2.302 (13) | 2.053 (9), 2.059 (13) | 175.82 (19), 177.93 (22) |
C18H32AuP (Sladek et al., 1995) | P21/n | 2.305 (1) | 2.055 (6) | 177.9 (2) |
C44H38Au2P2 (Sladek et al., 1995) | P1 | 2.284 (1) | 2.044 (4) | 174.8 (2) |
C39H34Au2P2.2C6H6 (Baukanova et al., 1997) | P21 | 2.296 (5), 2.296 (4) | 2.04 (2), 2.05 (2) | 179.0 (5), 168.6 (4) |
C13H20AuN3P+.C24H20B- (Forward et al., 1995) | P21/n | 2.274 (3) | 2.04 (1) | 176.5 (5) |
C12H17AuN3P (Forward et al., 1995) | P21/n | 2.289 (5) | 2.040 (2) | 170.1 (5) |
This work | P212121 | 2.293 (2) | 2.042 (8) | 175.9 (2) |
Note: (a) π side-on gold–phenyl ring bond. |
Gold carbanion connections are strong, as revealed by structural (Schmidbaur, 1995) and theoretical energy studies (Dargel et al., 1999). However, establishing such bonds usually demands reactive carbon precursors (organolithium or Grignard reagents) (Fernandez et al., 2004) with some reduction of gold to Au0. This inconvenience has prompted the search for more efficient procedures to generate Au—C bonds. Gray (2009), using boronic acids ArB(OH)2 as carbon-delivering substrates, has shown these reagents to give good yields of the desired aromatic carbanion products with LAuBr (where L is a bulky PR3, N-heterocyclic carbene) and an assisting base. In this report, we describe a transmetallation from boron to gold using Ph3PAuCl instead of LAuBr. The reaction proceeds with an excellent yield to give the title substituted triphenylphosphine gold(I) compound, [(Ph)3PAuI(2-C6H4SCH3], (I), under very controllable conditions.
Efficient protocols for generating Au—C bonded products are in demand, since the optical properties found for such compounds (Fackler, 2002; Gray, 2007) may be applied in opto-electronic devices (LEDs, organic LEDs or photovoltaic cells; Wong & Guo, 2008). Optical properties such as luminescence are enhanced by the heavy gold centre (spin-orbit coupling) attached to a variety of organic molecules such as pyrene (Heng et al., 2007), phenyls, heteroaromatic rings (Wong et al., 2007) and alkynyls (Yam et al., 2003), in mononuclear (King et al., 1992) and in polynuclear complexes (Hong et al., 1994; Rios et al., 2008).
Compound (I) is the first example of gold(I) attached to a thiomethyl aromatic carbanion. Even though the ortho thio unit on the ring could bond to Au to produce a four-membered chelate ring, the long Au1···S1 distance of 3.246 (3) Å shows that this does not happen. Connectivity of S to Au of a neighbouring molecule is apparently hindered by the phenyl rings of the phosphine, which obviate any aurophilic interactions [Au···Au = 6.986 (4) Å]. The propeller organization of the phenyl rings on the phosphine lowers the symmetry of the molecule (with no improper rotations), making it chiral.
From what is expected to be a racemic mixture of the product, only one of the two conformational enantiomers is present in the crystal structure (Fig. 1), so the crystalline product is in all likelihood a racemic conglomerate. The chiral space group P212121 is that which is most frequently observed for enantiopure crystals, according to Jacques et al. (1981).
Each mononuclear AuI centre has a linear ligand coordination with geometric parameters inside the remarkably narrow range found in this family of compounds. There are 17 examples in the Cambridge Structural Database (CSD, version 5.30; Allen, 2002) of gold(I) linearly bonded to a phosphine and to the C atom of an ortho-substituted phenyl group, including one with an Au—C π bond. Fifteen of these report three-dimensional coordinates (Table 1). Their Au—P and Au—C distances are similar to those of the title compound and they also show angular interactions involving phenyl rings (C—H···π interactions). Fourteen are non-chiral and in fact crystallize in centrosymmetric space groups. There is one chiral compound, the dimer [(µ2-2,2'-bis(phenylene)methane)-(µ2-1,2-bis(diphenylphosphino)ethane)-digold(I)], which crystallizes in the space group P21. In spite of the presence of four phenyl rings in (I), there are no π–π stacking interactions, but there are angular interactions between C-bound H atoms and phenyl rings of neighbouring molecules. There is one C—H···π contact of note, from C21—H21 to the centroid Cg1 of the C1–C6 ring of a neighbouring molecule, with H21···Cg1i = 2.83 Å, C21···Cg1i = 3.584 (9) Å and C21— H21···Cg1i = 137° [symmetry code: (i) 1 + x, y, z]. The molecules involved in these contacts form a chain parallel to the a axis (Fig. 2).