Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199013086/bm1354sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199013086/bm1354Isup2.hkl |
CCDC reference: 140941
The title compound was obtained in low yield (14%) from the reaction between (tht)AuCl and the silver salt of the imide in acetonitrile. After filtering off insoluble material, the solution was allowed to stand in a refrigerator at 255 K. After several days, some small crystals had separated.
H atoms were placed at calculated positions and refined with a riding model. Light-atom Uij values were restrained (command DELU). The N atom displays an appreciable component of the displacement parameter perpendicular to the anion plane, which may indicate slight disorder; removal of the N atom from the twofold axis, however, led to unstable refinement.
Data collection: XSCANS (Fait, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994b); software used to prepare material for publication: SHELXL97.
[Au(C4H8S)2](C6H4NO4S2) | F(000) = 1144 |
Mr = 591.52 | Dx = 2.129 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.6943 (16) Å | Cell parameters from 53 reflections |
b = 11.7250 (18) Å | θ = 2.8–11.4° |
c = 16.374 (3) Å | µ = 8.44 mm−1 |
β = 115.992 (10)° | T = 173 K |
V = 1845.5 (5) Å3 | Prism, colourless |
Z = 4 | 0.16 × 0.12 × 0.08 mm |
Siemens P4 diffractometer | 1307 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.039 |
Graphite monochromator | θmax = 25°, θmin = 3.2° |
ω scans | h = −11→12 |
Absorption correction: ψ scan (XEMP; Siemens, 1994a) | k = 0→13 |
Tmin = 0.382, Tmax = 0.509 | l = −19→18 |
3205 measured reflections | 3 standard reflections every 247 reflections |
1619 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: Patterson |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.044 | H-atom parameters constrained |
S = 0.84 | w = 1/[σ2(Fo2) + (0.0108P)2] where P = (Fo2 + 2Fc2)/3 |
1619 reflections | (Δ/σ)max = 0.001 |
110 parameters | Δρmax = 0.51 e Å−3 |
8 restraints | Δρmin = −0.48 e Å−3 |
[Au(C4H8S)2](C6H4NO4S2) | V = 1845.5 (5) Å3 |
Mr = 591.52 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.6943 (16) Å | µ = 8.44 mm−1 |
b = 11.7250 (18) Å | T = 173 K |
c = 16.374 (3) Å | 0.16 × 0.12 × 0.08 mm |
β = 115.992 (10)° |
Siemens P4 diffractometer | 1307 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XEMP; Siemens, 1994a) | Rint = 0.039 |
Tmin = 0.382, Tmax = 0.509 | 3 standard reflections every 247 reflections |
3205 measured reflections | intensity decay: none |
1619 independent reflections |
R[F2 > 2σ(F2)] = 0.029 | 8 restraints |
wR(F2) = 0.044 | H-atom parameters constrained |
S = 0.84 | Δρmax = 0.51 e Å−3 |
1619 reflections | Δρmin = −0.48 e Å−3 |
110 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 | ||
Au | 0.5000 | 0.51255 (3) | 0.2500 | 0.03008 (11) | |
S1 | 0.46774 (14) | 0.50993 (14) | 0.10191 (8) | 0.0364 (3) | |
C11 | 0.3312 (7) | 0.6137 (5) | 0.0442 (5) | 0.044 (2) | |
H11A | 0.3396 | 0.6790 | 0.0845 | 0.053* | |
H11B | 0.3358 | 0.6424 | −0.0113 | 0.053* | |
C12 | 0.1968 (7) | 0.5499 (6) | 0.0202 (5) | 0.056 (2) | |
H12A | 0.1784 | 0.5433 | 0.0743 | 0.067* | |
H12B | 0.1181 | 0.5911 | −0.0279 | 0.067* | |
C13 | 0.2121 (8) | 0.4342 (6) | −0.0125 (5) | 0.068 (3) | |
H13A | 0.2016 | 0.4393 | −0.0756 | 0.082* | |
H13B | 0.1388 | 0.3828 | −0.0123 | 0.082* | |
C14 | 0.3542 (8) | 0.3869 (5) | 0.0491 (5) | 0.047 (2) | |
H14A | 0.3911 | 0.3414 | 0.0136 | 0.056* | |
H14B | 0.3485 | 0.3373 | 0.0963 | 0.056* | |
N | 0.5000 | 0.7692 (6) | 0.2500 | 0.061 (3) | |
S3 | 0.62123 (17) | 0.83867 (12) | 0.24342 (11) | 0.0328 (4) | |
O1 | 0.6284 (4) | 0.8186 (3) | 0.1589 (3) | 0.0530 (13) | |
O2 | 0.7506 (4) | 0.8223 (3) | 0.3231 (2) | 0.0369 (10) | |
C101 | 0.5608 (5) | 0.9792 (4) | 0.2455 (3) | 0.0242 (12) | |
C102 | 0.6218 (6) | 1.0797 (4) | 0.2393 (4) | 0.0248 (13) | |
H102 | 0.7046 | 1.0794 | 0.2314 | 0.030* | |
C103 | 0.5606 (6) | 1.1811 (5) | 0.2448 (5) | 0.0315 (15) | |
H103 | 0.6022 | 1.2514 | 0.2414 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Au | 0.03038 (18) | 0.02679 (19) | 0.02541 (17) | 0.000 | 0.00517 (13) | 0.000 |
S1 | 0.0418 (8) | 0.0326 (8) | 0.0296 (7) | 0.0023 (8) | 0.0108 (6) | 0.0022 (8) |
C11 | 0.069 (5) | 0.027 (3) | 0.022 (4) | 0.008 (3) | 0.006 (4) | 0.008 (3) |
C12 | 0.048 (4) | 0.065 (4) | 0.040 (4) | 0.015 (3) | 0.006 (4) | 0.011 (3) |
C13 | 0.069 (6) | 0.053 (4) | 0.053 (5) | −0.019 (4) | −0.001 (4) | −0.006 (4) |
C14 | 0.072 (5) | 0.027 (3) | 0.039 (5) | −0.010 (3) | 0.021 (4) | −0.004 (3) |
N | 0.043 (6) | 0.019 (4) | 0.114 (8) | 0.000 | 0.028 (5) | 0.000 |
S3 | 0.0353 (10) | 0.0259 (8) | 0.0311 (9) | 0.0094 (7) | 0.0090 (8) | −0.0029 (7) |
O1 | 0.064 (3) | 0.056 (3) | 0.028 (2) | 0.027 (2) | 0.010 (2) | −0.005 (2) |
O2 | 0.036 (2) | 0.040 (2) | 0.027 (2) | 0.0150 (19) | 0.0059 (19) | −0.0012 (18) |
C101 | 0.022 (3) | 0.021 (3) | 0.024 (3) | 0.002 (2) | 0.005 (2) | −0.003 (3) |
C102 | 0.019 (3) | 0.037 (3) | 0.024 (3) | −0.001 (3) | 0.015 (3) | 0.001 (3) |
C103 | 0.031 (4) | 0.024 (3) | 0.039 (4) | −0.006 (2) | 0.015 (3) | 0.001 (3) |
Au—S1 | 2.2948 (14) | S3—O1 | 1.438 (4) |
Au—N | 3.009 (7) | S3—O2 | 1.440 (4) |
S1—C11 | 1.815 (6) | S3—C101 | 1.775 (5) |
S1—C14 | 1.839 (6) | C101—C102 | 1.372 (7) |
C11—C12 | 1.512 (9) | C101—C101i | 1.372 (9) |
C12—C13 | 1.494 (9) | C102—C103 | 1.379 (7) |
C13—C14 | 1.514 (9) | C103—C103i | 1.380 (12) |
N—S3 | 1.574 (4) | ||
S1i—Au—S1 | 178.47 (9) | S3i—N—Au | 121.2 (2) |
S1i—Au—N | 90.77 (4) | O1—S3—O2 | 114.5 (3) |
S1—Au—N | 90.77 (4) | O1—S3—N | 112.0 (2) |
C11—S1—C14 | 93.8 (3) | O2—S3—N | 111.2 (2) |
C11—S1—Au | 104.8 (2) | O1—S3—C101 | 110.1 (2) |
C14—S1—Au | 105.6 (3) | O2—S3—C101 | 108.7 (2) |
C12—C11—S1 | 105.1 (4) | N—S3—C101 | 99.3 (3) |
C13—C12—C11 | 107.5 (7) | C102—C101—C101i | 120.8 (3) |
C12—C13—C14 | 109.2 (6) | C102—C101—S3 | 127.4 (4) |
C13—C14—S1 | 106.8 (4) | C101i—C101—S3 | 111.85 (17) |
S3—N—S3i | 117.7 (4) | C101—C102—C103 | 118.8 (5) |
S3—N—Au | 121.2 (2) | C102—C103—C103i | 120.4 (3) |
S1i—Au—S1—C11 | 134.2 (2) | S3i—N—S3—O1 | −116.7 (2) |
N—Au—S1—C11 | −45.8 (2) | Au—N—S3—O1 | 63.3 (2) |
S1i—Au—S1—C14 | 35.8 (2) | S3i—N—S3—O2 | 113.7 (2) |
N—Au—S1—C14 | −144.2 (2) | Au—N—S3—O2 | −66.3 (2) |
C14—S1—C11—C12 | 23.5 (5) | S3i—N—S3—C101 | −0.57 (15) |
Au—S1—C11—C12 | −83.8 (5) | Au—N—S3—C101 | 179.43 (15) |
S1—C11—C12—C13 | −41.5 (7) | O1—S3—C101—C102 | −60.6 (5) |
C11—C12—C13—C14 | 43.5 (8) | O2—S3—C101—C102 | 65.5 (5) |
C12—C13—C14—S1 | −24.5 (8) | N—S3—C101—C102 | −178.2 (5) |
C11—S1—C14—C13 | 0.1 (5) | O1—S3—C101—C101i | 119.5 (5) |
Au—S1—C14—C13 | 106.6 (5) | O2—S3—C101—C101i | −114.4 (5) |
S1i—Au—N—S3 | 112.35 (8) | N—S3—C101—C101i | 1.9 (5) |
S1—Au—N—S3 | −67.65 (8) | C101i—C101—C102—C103 | 1.7 (9) |
S1i—Au—N—S3i | −67.65 (8) | S3—C101—C102—C103 | −178.2 (4) |
S1—Au—N—S3i | 112.35 (8) | C101—C102—C103—C103i | −0.8 (11) |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C103—H103···O2ii | 0.95 | 2.40 | 3.165 (7) | 138 |
C11—H11B···O2iii | 0.99 | 2.49 | 3.416 (8) | 156 |
Symmetry codes: (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1/2, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Au(C4H8S)2](C6H4NO4S2) |
Mr | 591.52 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 10.6943 (16), 11.7250 (18), 16.374 (3) |
β (°) | 115.992 (10) |
V (Å3) | 1845.5 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 8.44 |
Crystal size (mm) | 0.16 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | ψ scan (XEMP; Siemens, 1994a) |
Tmin, Tmax | 0.382, 0.509 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3205, 1619, 1307 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.044, 0.84 |
No. of reflections | 1619 |
No. of parameters | 110 |
No. of restraints | 8 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.48 |
Computer programs: XSCANS (Fait, 1991), XSCANS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994b), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C103—H103···O2i | 0.95 | 2.40 | 3.165 (7) | 138 |
C11—H11B···O2ii | 0.99 | 2.49 | 3.416 (8) | 156 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x−1/2, −y+3/2, z−1/2. |
We are interested in amine complexes of gold (Ahrens et al., 1999). These are often obtained by displacement of tetrahydrothiophene (tht) from the complex (tht)AuCl. As an alternative tht–gold starting material, we wished to prepare the title compound, bis(tetrahydrothiophene-S)gold(I) benzene-1,2-disulfonimidate (see Experimental), (I), but initial attempts resulted in disappointing yields. The structure nevertheless presents some interesting features.
The title compound (Fig. 1) crystallizes with imposed twofold symmetry for the anion and cation (the N and Au atoms lie on special positions 0,y,1/4 and 1/2,y,1/4, respectively). The gold centre displays the usual linear coordination, with Au—S = 2.2948 (14) Å and S—Au—Si = 178.47 (9)° [symmetry code: (i) 3/2 − x, 1/2 + y, 1/2 − z]. In [(tht)2Au]+[AuI2]− (Ahrland et al., 1984), the Au—S bonds were somewhat longer at 2.306 (7) and 2.335 (6) Å, and there was more deviations from linearity, with S—Au—S = 172.4 (2)°; this may be caused by the association of anion and cation via Au···Au interactions to form chains.
The tht ring adopts an envelope conformation, with C12 lying 0.58 (1) Å out of the plane of the other four atoms (r.m.s. deviation < 0.001 Å). The ring system of the anion is planar (r.m.s. deviation of nine atoms = 0.020 Å). Bond lengths and angles in both ring systems are as expected.
The crystal packing is determined not by Au···Au contacts [the shortest Au···Au distance is 7.9348 (9) Å], but rather by an Au···N contact of 3.009 (7) Å and by two short non-classical C—H···O hydrogen bonds (Table 1). A search for two-coordinate gold(I) complexes in the Cambridge Structural Database (Allen & Kennard, 1993) revealed only one shorter Au···N contact, namely 2.997 Å in adeninato(triethylphosphine)gold(I) (Tiekink et al., 1989). The next shortest is 3.148 (19) Å in the related purine(dimethylphenylphosphine)gold(I) compex (Pajunen et al., 1995). There are no other contacts less than 3.4 Å.
The H103···O2 hydrogen bonds link the anions to form a layer structure (Fig. 2), the cavities of which are occupied by the cations. Perpendicular to the layers, H11B···O2 hydrogen bonds link alternate anions and cations to form chains (not shown in Fig. 2). Neighbouring layers are therefore staggered.