Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103005961/ob1105sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103005961/ob1105Isup2.hkl |
CCDC reference: 199209
To a solution of (n-Bu4N)[AuBr4] (0.76 g, 1 mmol) in tetrahydrofran (15 ml), a mixture of pentafluorobenzenethiol (0.8 g, 4 mmol) and triethylamine (0.4 g, 4 mmol) in the same solvent (20 ml) was added dropwise at room temperature with stirring. After 3 h, a white precipitate was filtered off and tetrahydrofran was removed under reduced pressure to give a red residue. Red crystals of (I) were obtained by recrystallization from a mixed tetrahydrofran/methanol solution. Analysis; calculated for C40H36NF20S4Au: C 38.87, H 2.94, N 1.13%; found: C 38.63, H 2.83, N 1.12%. Isolated yield 41%.
The two independent tetra-n-butylammonium cations show orientational disorder, and atoms N1, N2, C8, C10, C12 and C14 lie on mirror planes perpendicular to c. The occupancy factors of atoms C7, C9, C11 and C13 and all the H atoms of the cations are 50%. H atoms were placed in calculated positions (C—H= 0.95 Å) but not refined.
Data collection: PROCESS (Rigaku, 1996); cell refinement: PROCESS; data reduction: TEXSAN (Molecular Structure Corporation, 2000); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: TEXSAN.
(C16H36N)[Au(C6F5S)4] | Dx = 1.713 Mg m−3 |
Mr = 1235.91 | Mo Kα radiation, λ = 0.7107 Å |
Tetragonal, I4/m | Cell parameters from 25852 reflections |
Hall symbol: -I 4 | θ = 1.7–27.5° |
a = 14.7427 (4) Å | µ = 3.36 mm−1 |
c = 22.0412 (6) Å | T = 296 K |
V = 4790.6 (2) Å3 | Prism, red |
Z = 4 | 0.32 × 0.15 × 0.10 mm |
F(000) = 2424.00 |
Rigaku RAXIS-RAPID Imaging Plate diffractometer | 1975 reflections with F2 > 2σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.039 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (Higashi, 1995) | h = −19→19 |
Tmin = 0.499, Tmax = 0.714 | k = −19→19 |
22114 measured reflections | l = −28→28 |
2835 independent reflections |
Refinement on F | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo) + 0.00063|Fo|2] |
wR(F2) = 0.043 | (Δ/σ)max = 0.0003 |
S = 1.05 | Δρmax = 2.55 e Å−3 |
1975 reflections | Δρmin = −0.96 e Å−3 |
176 parameters |
(C16H36N)[Au(C6F5S)4] | Z = 4 |
Mr = 1235.91 | Mo Kα radiation |
Tetragonal, I4/m | µ = 3.36 mm−1 |
a = 14.7427 (4) Å | T = 296 K |
c = 22.0412 (6) Å | 0.32 × 0.15 × 0.10 mm |
V = 4790.6 (2) Å3 |
Rigaku RAXIS-RAPID Imaging Plate diffractometer | 2835 independent reflections |
Absorption correction: multi-scan (Higashi, 1995) | 1975 reflections with F2 > 2σ(F2) |
Tmin = 0.499, Tmax = 0.714 | Rint = 0.039 |
22114 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 176 parameters |
wR(F2) = 0.043 | H-atom parameters not refined |
S = 1.05 | Δρmax = 2.55 e Å−3 |
1975 reflections | Δρmin = −0.96 e Å−3 |
Refinement. Refinement using reflections with F2 > 2.0 σ(F2). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Au1 | 0.0000 | 0.0000 | 0.20905 (2) | 0.06283 (8) | |
S1 | 0.14309 (10) | 0.06818 (10) | 0.20316 (8) | 0.0895 (5) | |
F1 | 0.1525 (3) | 0.2469 (3) | 0.1407 (2) | 0.131 (2) | |
F2 | 0.1437 (4) | 0.4121 (3) | 0.1891 (3) | 0.175 (2) | |
F3 | 0.1164 (3) | 0.4319 (4) | 0.3104 (4) | 0.192 (3) | |
F4 | 0.1015 (4) | 0.2830 (5) | 0.3811 (3) | 0.193 (3) | |
F5 | 0.1119 (4) | 0.1178 (3) | 0.3323 (2) | 0.140 (2) | |
N1 | 0.0000 | 0.0000 | 0.5000 | 0.068 (2) | |
N2 | 0.0000 | 0.0000 | 1.0000 | 0.090 (2) | |
C1 | 0.1333 (3) | 0.1773 (4) | 0.2360 (3) | 0.071 (2) | |
C2 | 0.1403 (4) | 0.2541 (4) | 0.2017 (3) | 0.087 (2) | |
C3 | 0.1358 (5) | 0.3396 (5) | 0.2256 (6) | 0.114 (3) | |
C4 | 0.1219 (5) | 0.3494 (6) | 0.2853 (6) | 0.121 (3) | |
C5 | 0.1143 (5) | 0.2740 (8) | 0.3212 (5) | 0.121 (3) | |
C6 | 0.1204 (4) | 0.1901 (5) | 0.2959 (3) | 0.093 (2) | |
C7 | −0.0311 (9) | 0.0792 (9) | 0.4591 (6) | 0.098 (4) | 0.50 |
C8 | −0.0594 (9) | 0.1623 (8) | 0.5000 | 0.119 (4) | |
C9 | −0.097 (1) | 0.234 (1) | 0.4562 (9) | 0.148 (7) | 0.50 |
C10 | −0.120 (1) | 0.319 (1) | 0.5000 | 0.213 (9) | |
C11 | 0.0833 (10) | 0.019 (1) | 1.0410 (6) | 0.116 (5) | 0.50 |
C12 | 0.165 (1) | 0.044 (1) | 1.0000 | 0.149 (6) | |
C13 | 0.247 (2) | 0.058 (1) | 1.041 (1) | 0.166 (9) | 0.50 |
C14 | 0.327 (1) | 0.084 (1) | 1.0000 | 0.190 (8) | |
H1 | 0.0172 | 0.0966 | 0.4331 | 0.1173* | 0.50 |
H2 | −0.0815 | 0.0604 | 0.4354 | 0.1173* | 0.50 |
H3 | −0.1046 | 0.1447 | 0.5283 | 0.1432* | 0.50 |
H4 | −0.0082 | 0.1853 | 0.5212 | 0.1432* | 0.50 |
H5 | −0.0529 | 0.2506 | 0.4266 | 0.1776* | 0.50 |
H6 | −0.1502 | 0.2132 | 0.4364 | 0.1776* | 0.50 |
H7 | −0.0658 | 0.3383 | 0.5197 | 0.2555* | 0.50 |
H8 | −0.1437 | 0.3674 | 0.4766 | 0.2555* | 0.50 |
H9 | −0.1630 | 0.3009 | 0.5295 | 0.2555* | 0.50 |
H10 | 0.0701 | 0.0681 | 1.0676 | 0.1388* | 0.50 |
H11 | 0.0974 | −0.0334 | 1.0641 | 0.1388* | 0.50 |
H12 | 0.1767 | −0.0034 | 0.9721 | 0.1788* | 0.50 |
H13 | 0.1525 | 0.0986 | 0.9784 | 0.1788* | 0.50 |
H14 | 0.2351 | 0.1054 | 1.0696 | 0.1995* | 0.50 |
H15 | 0.2597 | 0.0036 | 1.0629 | 0.1995* | 0.50 |
H16 | 0.3801 | 0.0925 | 1.0240 | 0.2280* | 0.50 |
H17 | 0.3379 | 0.0360 | 0.9718 | 0.2280* | 0.50 |
H18 | 0.3136 | 0.1378 | 0.9787 | 0.2280* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Au1 | 0.0556 (2) | 0.0556 | 0.0773 (3) | 0.0000 | 0.0000 | 0.0000 |
S1 | 0.0605 (7) | 0.0669 (8) | 0.141 (1) | −0.0023 (6) | 0.0196 (9) | 0.0058 (9) |
F1 | 0.137 (4) | 0.120 (3) | 0.138 (4) | −0.011 (2) | 0.002 (3) | 0.042 (3) |
F2 | 0.156 (4) | 0.077 (3) | 0.292 (6) | −0.014 (3) | 0.008 (5) | 0.062 (4) |
F3 | 0.119 (4) | 0.116 (4) | 0.340 (8) | −0.020 (3) | 0.036 (5) | −0.110 (5) |
F4 | 0.188 (6) | 0.248 (7) | 0.143 (4) | −0.020 (5) | 0.029 (4) | −0.075 (5) |
F5 | 0.171 (5) | 0.142 (4) | 0.107 (3) | −0.008 (3) | 0.012 (3) | 0.036 (3) |
N1 | 0.082 (5) | 0.0822 | 0.038 (5) | 0.0000 | 0.0000 | 0.0000 |
N2 | 0.108 (7) | 0.1080 | 0.054 (7) | 0.0000 | 0.0000 | 0.0000 |
C1 | 0.051 (3) | 0.061 (3) | 0.101 (4) | −0.006 (2) | −0.001 (3) | 0.009 (3) |
C2 | 0.065 (3) | 0.080 (4) | 0.117 (5) | −0.011 (3) | 0.003 (3) | 0.013 (4) |
C3 | 0.072 (4) | 0.061 (4) | 0.208 (9) | −0.010 (3) | 0.010 (5) | 0.016 (5) |
C4 | 0.059 (4) | 0.095 (6) | 0.21 (1) | −0.014 (3) | 0.014 (5) | −0.038 (7) |
C5 | 0.072 (4) | 0.151 (8) | 0.139 (7) | −0.015 (5) | 0.006 (5) | −0.037 (7) |
C6 | 0.073 (4) | 0.100 (5) | 0.105 (5) | −0.010 (3) | −0.006 (4) | −0.002 (5) |
C7 | 0.113 (10) | 0.102 (9) | 0.078 (7) | 0.006 (8) | −0.012 (7) | 0.019 (7) |
C8 | 0.149 (10) | 0.104 (8) | 0.104 (7) | 0.025 (7) | 0.0000 | 0.0000 |
C9 | 0.18 (2) | 0.12 (1) | 0.15 (1) | 0.02 (1) | 0.02 (1) | 0.00 (1) |
C10 | 0.21 (2) | 0.13 (1) | 0.30 (2) | 0.05 (1) | 0.0000 | 0.0000 |
C11 | 0.12 (1) | 0.14 (1) | 0.080 (7) | 0.00 (1) | −0.007 (8) | 0.005 (9) |
C12 | 0.13 (1) | 0.21 (2) | 0.105 (8) | −0.03 (1) | 0.0000 | 0.0000 |
C13 | 0.17 (2) | 0.17 (2) | 0.16 (2) | −0.03 (1) | 0.07 (2) | 0.00 (1) |
C14 | 0.18 (2) | 0.19 (2) | 0.20 (2) | −0.05 (1) | 0.0000 | 0.0000 |
Au1—S1 | 2.340 (1) | C8—H4 | 0.950 |
S1—C1 | 1.770 (6) | C9—C10 | 1.61 (2) |
F1—C2 | 1.361 (8) | C9—H5 | 0.950 |
F2—C3 | 1.343 (9) | C9—H6 | 0.950 |
F3—C4 | 1.339 (9) | C10—H7 | 0.950 |
F4—C5 | 1.34 (1) | C10—H8 | 0.950 |
F5—C6 | 1.340 (8) | C10—H9 | 0.950 |
N1—C7 | 1.54 (1) | C11—C12 | 1.55 (2) |
N2—C11 | 1.55 (1) | C11—H10 | 0.950 |
C1—C2 | 1.366 (8) | C11—H11 | 0.950 |
C1—C6 | 1.348 (9) | C12—C13 | 1.53 (2) |
C2—C3 | 1.37 (1) | C12—H12 | 0.950 |
C3—C4 | 1.34 (1) | C12—H13 | 0.950 |
C4—C5 | 1.37 (1) | C13—C14 | 1.55 (2) |
C5—C6 | 1.36 (1) | C13—H14 | 0.950 |
C7—C8 | 1.58 (2) | C13—H15 | 0.950 |
C7—H1 | 0.950 | C14—H16 | 0.950 |
C7—H2 | 0.950 | C14—H17 | 0.950 |
C8—C9 | 1.54 (2) | C14—H18 | 0.950 |
C8—H3 | 0.950 | ||
S1···F3i | 3.558 (5) | F3···C3ii | 3.177 (10) |
F1···C5i | 3.552 (9) | F3···C4ii | 3.54 (1) |
F1···C9ii | 3.55 (2) | F4···C9 | 3.44 (2) |
F2···C4ii | 3.145 (9) | F4···C14iv | 3.44 (1) |
F2···F3iii | 3.151 (8) | F5···C7v | 3.11 (1) |
F2···F3ii | 3.212 (7) | F5···C9v | 3.29 (2) |
F2···C5ii | 3.227 (9) | F5···C7 | 3.55 (1) |
F2···F4ii | 3.370 (8) | C1···C3i | 3.516 (8) |
S1—Au1—S1vi | 173.64 (9) | C9—C8—H4 | 110.4 |
S1—Au1—S1vii | 89.824 (5) | H3—C8—H4 | 109.5 |
S1—Au1—S1v | 89.824 (5) | C8—C9—C10 | 103 (1) |
Au1—S1—C1 | 107.1 (2) | C8—C9—H5 | 110.9 |
C7—N1—C7vi | 108 (1) | C8—C9—H6 | 111.0 |
C7—N1—C7viii | 109.9 (5) | C10—C9—H5 | 111.0 |
C7—N1—C7ix | 109.9 (5) | C10—C9—H6 | 111.0 |
C11—N2—C11vi | 108 (1) | H5—C9—H6 | 109.5 |
C11—N2—C11x | 109.9 (5) | C9—C10—H7 | 109.5 |
C11—N2—C11xi | 109.9 (5) | C9—C10—H8 | 109.5 |
S1—C1—C2 | 121.4 (5) | C9—C10—H9 | 109.5 |
S1—C1—C6 | 122.7 (5) | H7—C10—H8 | 109.5 |
C2—C1—C6 | 115.9 (6) | H7—C10—H9 | 109.5 |
F1—C2—C1 | 119.5 (6) | H8—C10—H9 | 109.5 |
F1—C2—C3 | 117.4 (7) | N2—C11—C12 | 108.6 (9) |
C1—C2—C3 | 123.1 (8) | N2—C11—H10 | 109.7 |
F2—C3—C2 | 119 (1) | N2—C11—H11 | 109.7 |
F2—C3—C4 | 121.0 (9) | C12—C11—H10 | 109.7 |
C2—C3—C4 | 119.1 (8) | C12—C11—H11 | 109.7 |
F3—C4—C3 | 120 (1) | H10—C11—H11 | 109.5 |
F3—C4—C5 | 119 (1) | C11—C12—C13 | 107.2 (9) |
C3—C4—C5 | 119.5 (8) | C11—C12—H12 | 110.1 |
F4—C5—C4 | 120 (1) | C11—C12—H13 | 110.0 |
F4—C5—C6 | 120 (1) | C13—C12—H12 | 110.0 |
C4—C5—C6 | 119.7 (9) | C13—C12—H13 | 110.0 |
F5—C6—C1 | 119.2 (6) | H12—C12—H13 | 109.5 |
F5—C6—C5 | 118.2 (8) | C12—C13—C14 | 106 (1) |
C1—C6—C5 | 122.6 (8) | C12—C13—H14 | 110.2 |
N1—C7—C8 | 109.4 (8) | C12—C13—H15 | 110.2 |
N1—C7—H1 | 109.5 | C14—C13—H14 | 110.2 |
N1—C7—H2 | 109.5 | C14—C13—H15 | 110.2 |
C8—C7—H1 | 109.5 | H14—C13—H15 | 109.5 |
C8—C7—H2 | 109.5 | C13—C14—H16 | 109.5 |
H1—C7—H2 | 109.5 | C13—C14—H17 | 109.5 |
C7—C8—C9 | 105.8 (9) | C13—C14—H18 | 109.4 |
C7—C8—H3 | 110.4 | H16—C14—H17 | 109.5 |
C7—C8—H4 | 110.4 | H16—C14—H18 | 109.5 |
C9—C8—H3 | 110.4 | H17—C14—H18 | 109.5 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1/2; (ii) −y+1/2, x+1/2, −z+1/2; (iii) y−1/2, −x+1/2, −z+1/2; (iv) −x+1/2, −y+1/2, z−1/2; (v) y, −x, z; (vi) −x, −y, z; (vii) −y, x, z; (viii) y, −x, −z+1; (ix) −y, x, −z+1; (x) y, −x, −z+2; (xi) −y, x, −z+2. |
Experimental details
Crystal data | |
Chemical formula | (C16H36N)[Au(C6F5S)4] |
Mr | 1235.91 |
Crystal system, space group | Tetragonal, I4/m |
Temperature (K) | 296 |
a, c (Å) | 14.7427 (4), 22.0412 (6) |
V (Å3) | 4790.6 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.36 |
Crystal size (mm) | 0.32 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Rigaku RAXIS-RAPID Imaging Plate diffractometer |
Absorption correction | Multi-scan (Higashi, 1995) |
Tmin, Tmax | 0.499, 0.714 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 22114, 2835, 1975 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.043, 1.05 |
No. of reflections | 1975 |
No. of parameters | 176 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 2.55, −0.96 |
Computer programs: PROCESS (Rigaku, 1996), PROCESS, TEXSAN (Molecular Structure Corporation, 2000), SIR92 (Altomare et al., 1994), TEXSAN, ORTEP-3 (Farrugia, 1997).
Au1—S1 | 2.340 (1) | S1—C1 | 1.770 (6) |
S1—Au1—S1i | 173.64 (9) | Au1—S1—C1 | 107.1 (2) |
S1—Au1—S1ii | 89.824 (5) |
Symmetry codes: (i) −x, −y, z; (ii) −y, x, z. |
Syntheses and structural determinations of gold(III) complexes with monodentate thiolate ligands have been poorly investigated, because reductive elimination reactions of thiolate ligands usually occur to afford a linear two-coordinated gold(I)–thiolate complex and a corresponding disulfide (Beck et al., 1967; Muller et al., 1978). The only example of an isolated gold(III) complex with four monodentate thiolate ligands, [Au(Smetetraz)4]− (Smetetraz is 1-methyl-1,2,3,4-tetrazole-5-thiolate; Abram et al., 1998; Nöth et al., 1998; Lang et al., 1999) contains an electron-withdrawing tetrazole unit in the ligand system, as has been confirmed by X-ray diffraction methods. Highly fluorinated thiolate ligands, such as pentafluorobenzenethiolate, are another candidate, and two types of corresponding gold(III) complexes, [AuIII(SC6F5)4]− with tetraethylammonium, (Et4N)+, and tetraphenylarsonum, (Ph3As)+, salts have been isolated (Muller et al., 1978). However, determinations of their crystal structures have not been achieved. Recently, we successfully synthesized and crystallized the four-coordinated gold(III) complex with pentafluorobenzenethiolate by using the tetra-n-butylammonium cation, which is bulkier than tetraethylammonium, as part of our investigation of gold–thiolate complexes (Watase et al., 2000). Here, we report the crystal structure of the title compound, (I).
In the anion of (I), the gold centre coordinated by four thiolate ligands has a typical square-planar geometry, where the Au atom deviates 0.130 (1) Å from the S4 plane and the S1—Au1—S1ii angle is 89.824 (5)° (Fig. 1 and Table 1). The four thiolate ligands are crystallographically equivalent, since the Au atom is situated on a crystallographic fourfold axis. All thiolate units are aligned almost orthogonally to the S4-plane and oriented in the same sense, like a windmill. In addition, this anion has a structure like a four-legged table, since all the S—C bonds deviate from the S4-plane to the same side, as shown in Fig. 2. The Au1—S1 bond length of 2.340 (1) Å is slightly shorter than those of [Au(Smetetraz)4]− [2.352 (1)–2.358 (1) Å; Abram et al., 1998; Nöth et al., 1998; Lang et al., 1999] but corresponds to those of general gold(III) complexes with dithio-chelating ligands (2.30–2.35 Å; Nakamoto et al., 1993; Fackler et al., 1999). The S1—C1 bond length of 1.770 (6) Å is longer than those of [Au(Smetetraz)4]− [1.722 (4)–1.743 (6) Å] but is compatible with those of (n-Bu4N)2[Pt2(µ-SC6F5)2(SC6F5)4], which is an isoelectronic platinum(II) complex with the same thiolate ligand [1.752 (2)–1.785 (7) Å; Rivera et al., 2001]. The ligands still have a thiolate character, as revealed by the S—C bond lengths, which lie in the normal range for a single bond (1.82 Å) rather than a double bond (1.56 Å; Cea-Olivares et al., 1995). The Au1—S1—C1 angle of 107.1 (2)° is consistent with the values of those in [Au(Smetetraz)4]− [106.2 (1)–107.2 (2) °] and (n-Bu4N)2[Pt2(µ-SC6F5)2(SC6F5)4] [105.7 (2)–109.5 (2)°].
The packing of (I) is depicted in Fig. 3. The crystal has a layered structure, in which the [Au(SC6F5)4]− anion and the [n-Bu4N]+ cation alternately stack along the c axis. There are two independent cations, which show disordered structures, since the N atoms have crystallographically imposed 4/m symmetry. The anion layer, viewed from the c axis, is shown in Fig. 4. A l l ligands of the anions are aligned orthogonally to the AuS4 plane and are oriented in the same sense, like a counterclockwise windmill. In the side view of this anion layer (Fig. 3), however, there exist two types of conformational isomers (i.e. enantiomers) of the anion in the crystal, situated alternately for the top and the bottom inversion. Each of an anion's phenyl rings is exactly parallel to one of the phenyl rings of an adjacent anion (Fig. 4), as a result of the space-group-imposed symmetry. The least-squares distance between the planes of two neighboring two phenyl rings is about 3.5 Å, and a weak intermolecular π–π interaction can exist, despite the Coulomb repulsion between anions. The phenyl ring and two of the F atoms of a neighboring anion also shows close contacts [F2···C4i = 3.145 (9) Å and F3···C3i = 3.177 (10) Å; symmetry code: (i) −x, −y, −z], respectively. These are comparable to the sum of the van der Waals radii (3.17 Å) of the C (1.70 Å) and F (1.47 Å) atoms (Bondi, 1964). The distances of the C—F···π intermolecular interactions in (I) are slightly shorter than the analogous π–π stacking interaction (3.6 Å) and C—F···π interaction (3.24 Å) of the reported Ti(IV) complex with the same thiolate ligand, [Et2NH2]3[Ti(SC6F5)5][SC6F5]2 (Carmalt et al., 2000). As a result of these intermolecular interactions, the anions of (I) are linked together and form a two-dimensional sheet-like structure in the (001) plane. In addition, the tetra-n-butylammonium cation has the most flattened conformation. The alkyl chains spread in the same direction as the Au—S bonds of the anion and may contribute to stabilize the crystal structure (Fig. 3).