Download citation
Download citation
link to html
Both ions of the title compound, [Au(C4H8S)2](C6H4NO4S2), display crystallographic twofold symmetry. The Au atom exhibits linear coordination, with Au—S = 2.2948 (14) Å and S—Au—S = 178.47 (9)°. The crystal packing consists of layers of anions connected by C—H...O hydrogen bonds; the cations occupy cavities in these layers and the ions are linked by Au...N contacts of 3.009 (7) Å. Further C—H...O interactions connect the layers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199013086/bm1354sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199013086/bm1354Isup2.hkl
Contains datablock I

CCDC reference: 140941

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The structure of the title compound in the crystal. Ellipsoids represent 50% probability levels. H-atom radii are arbitrary. The Au···N contact is represented by a broken bond [symmetry code: (i) 3/2 − x, 1/2 + y, 1/2 − z]
[Figure 2] Fig. 2. The layer structure of the title compound (H atoms have been omitted for clarity). C···O contacts (hydrogen bonds) are indicated by thin and Au···N contacts by thick dashed lines.
Bis(tetrahydrothiophene)gold(I) (ortho-benzodisulfonyl)amide top
Crystal data top
[Au(C4H8S)2](C6H4NO4S2)F(000) = 1144
Mr = 591.52Dx = 2.129 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 10.6943 (16) ÅCell parameters from 53 reflections
b = 11.7250 (18) Åθ = 2.8–11.4°
c = 16.374 (3) ŵ = 8.44 mm1
β = 115.992 (10)°T = 173 K
V = 1845.5 (5) Å3Prism, colourless
Z = 40.16 × 0.12 × 0.08 mm
Data collection top
Siemens P4
diffractometer
1307 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.039
Graphite monochromatorθmax = 25°, θmin = 3.2°
ω scansh = 1112
Absorption correction: ψ scan
(XEMP; Siemens, 1994a)
k = 013
Tmin = 0.382, Tmax = 0.509l = 1918
3205 measured reflections3 standard reflections every 247 reflections
1619 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: Patterson
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.044H-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 parametersΔρmax = 0.51 e Å3
8 restraintsΔρmin = 0.48 e Å3
Crystal data top
[Au(C4H8S)2](C6H4NO4S2)V = 1845.5 (5) Å3
Mr = 591.52Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.6943 (16) ŵ = 8.44 mm1
b = 11.7250 (18) ÅT = 173 K
c = 16.374 (3) Å0.16 × 0.12 × 0.08 mm
β = 115.992 (10)°
Data collection top
Siemens P4
diffractometer
1307 reflections with I > 2σ(I)
Absorption correction: ψ scan
(XEMP; Siemens, 1994a)
Rint = 0.039
Tmin = 0.382, Tmax = 0.5093 standard reflections every 247 reflections
3205 measured reflections intensity decay: none
1619 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0298 restraints
wR(F2) = 0.044H-atom parameters constrained
S = 0.84Δρmax = 0.51 e Å3
1619 reflectionsΔρmin = 0.48 e Å3
110 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Au0.50000.51255 (3)0.25000.03008 (11)
S10.46774 (14)0.50993 (14)0.10191 (8)0.0364 (3)
C110.3312 (7)0.6137 (5)0.0442 (5)0.044 (2)
H11A0.33960.67900.08450.053*
H11B0.33580.64240.01130.053*
C120.1968 (7)0.5499 (6)0.0202 (5)0.056 (2)
H12A0.17840.54330.07430.067*
H12B0.11810.59110.02790.067*
C130.2121 (8)0.4342 (6)0.0125 (5)0.068 (3)
H13A0.20160.43930.07560.082*
H13B0.13880.38280.01230.082*
C140.3542 (8)0.3869 (5)0.0491 (5)0.047 (2)
H14A0.39110.34140.01360.056*
H14B0.34850.33730.09630.056*
N0.50000.7692 (6)0.25000.061 (3)
S30.62123 (17)0.83867 (12)0.24342 (11)0.0328 (4)
O10.6284 (4)0.8186 (3)0.1589 (3)0.0530 (13)
O20.7506 (4)0.8223 (3)0.3231 (2)0.0369 (10)
C1010.5608 (5)0.9792 (4)0.2455 (3)0.0242 (12)
C1020.6218 (6)1.0797 (4)0.2393 (4)0.0248 (13)
H1020.70461.07940.23140.030*
C1030.5606 (6)1.1811 (5)0.2448 (5)0.0315 (15)
H1030.60221.25140.24140.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Au0.03038 (18)0.02679 (19)0.02541 (17)0.0000.00517 (13)0.000
S10.0418 (8)0.0326 (8)0.0296 (7)0.0023 (8)0.0108 (6)0.0022 (8)
C110.069 (5)0.027 (3)0.022 (4)0.008 (3)0.006 (4)0.008 (3)
C120.048 (4)0.065 (4)0.040 (4)0.015 (3)0.006 (4)0.011 (3)
C130.069 (6)0.053 (4)0.053 (5)0.019 (4)0.001 (4)0.006 (4)
C140.072 (5)0.027 (3)0.039 (5)0.010 (3)0.021 (4)0.004 (3)
N0.043 (6)0.019 (4)0.114 (8)0.0000.028 (5)0.000
S30.0353 (10)0.0259 (8)0.0311 (9)0.0094 (7)0.0090 (8)0.0029 (7)
O10.064 (3)0.056 (3)0.028 (2)0.027 (2)0.010 (2)0.005 (2)
O20.036 (2)0.040 (2)0.027 (2)0.0150 (19)0.0059 (19)0.0012 (18)
C1010.022 (3)0.021 (3)0.024 (3)0.002 (2)0.005 (2)0.003 (3)
C1020.019 (3)0.037 (3)0.024 (3)0.001 (3)0.015 (3)0.001 (3)
C1030.031 (4)0.024 (3)0.039 (4)0.006 (2)0.015 (3)0.001 (3)
Geometric parameters (Å, º) top
Au—S12.2948 (14)S3—O11.438 (4)
Au—N3.009 (7)S3—O21.440 (4)
S1—C111.815 (6)S3—C1011.775 (5)
S1—C141.839 (6)C101—C1021.372 (7)
C11—C121.512 (9)C101—C101i1.372 (9)
C12—C131.494 (9)C102—C1031.379 (7)
C13—C141.514 (9)C103—C103i1.380 (12)
N—S31.574 (4)
S1i—Au—S1178.47 (9)S3i—N—Au121.2 (2)
S1i—Au—N90.77 (4)O1—S3—O2114.5 (3)
S1—Au—N90.77 (4)O1—S3—N112.0 (2)
C11—S1—C1493.8 (3)O2—S3—N111.2 (2)
C11—S1—Au104.8 (2)O1—S3—C101110.1 (2)
C14—S1—Au105.6 (3)O2—S3—C101108.7 (2)
C12—C11—S1105.1 (4)N—S3—C10199.3 (3)
C13—C12—C11107.5 (7)C102—C101—C101i120.8 (3)
C12—C13—C14109.2 (6)C102—C101—S3127.4 (4)
C13—C14—S1106.8 (4)C101i—C101—S3111.85 (17)
S3—N—S3i117.7 (4)C101—C102—C103118.8 (5)
S3—N—Au121.2 (2)C102—C103—C103i120.4 (3)
S1i—Au—S1—C11134.2 (2)S3i—N—S3—O1116.7 (2)
N—Au—S1—C1145.8 (2)Au—N—S3—O163.3 (2)
S1i—Au—S1—C1435.8 (2)S3i—N—S3—O2113.7 (2)
N—Au—S1—C14144.2 (2)Au—N—S3—O266.3 (2)
C14—S1—C11—C1223.5 (5)S3i—N—S3—C1010.57 (15)
Au—S1—C11—C1283.8 (5)Au—N—S3—C101179.43 (15)
S1—C11—C12—C1341.5 (7)O1—S3—C101—C10260.6 (5)
C11—C12—C13—C1443.5 (8)O2—S3—C101—C10265.5 (5)
C12—C13—C14—S124.5 (8)N—S3—C101—C102178.2 (5)
C11—S1—C14—C130.1 (5)O1—S3—C101—C101i119.5 (5)
Au—S1—C14—C13106.6 (5)O2—S3—C101—C101i114.4 (5)
S1i—Au—N—S3112.35 (8)N—S3—C101—C101i1.9 (5)
S1—Au—N—S367.65 (8)C101i—C101—C102—C1031.7 (9)
S1i—Au—N—S3i67.65 (8)S3—C101—C102—C103178.2 (4)
S1—Au—N—S3i112.35 (8)C101—C102—C103—C103i0.8 (11)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C103—H103···O2ii0.952.403.165 (7)138
C11—H11B···O2iii0.992.493.416 (8)156
Symmetry codes: (ii) x+3/2, y+1/2, z+1/2; (iii) x1/2, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formula[Au(C4H8S)2](C6H4NO4S2)
Mr591.52
Crystal system, space groupMonoclinic, C2/c
Temperature (K)173
a, b, c (Å)10.6943 (16), 11.7250 (18), 16.374 (3)
β (°) 115.992 (10)
V3)1845.5 (5)
Z4
Radiation typeMo Kα
µ (mm1)8.44
Crystal size (mm)0.16 × 0.12 × 0.08
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionψ scan
(XEMP; Siemens, 1994a)
Tmin, Tmax0.382, 0.509
No. of measured, independent and
observed [I > 2σ(I)] reflections
3205, 1619, 1307
Rint0.039
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.044, 0.84
No. of reflections1619
No. of parameters110
No. of restraints8
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.51, 0.48

Computer programs: XSCANS (Fait, 1991), XSCANS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994b), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C103—H103···O2i0.952.403.165 (7)138
C11—H11B···O2ii0.992.493.416 (8)156
Symmetry codes: (i) x+3/2, y+1/2, z+1/2; (ii) x1/2, y+3/2, z1/2.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds