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Acta Cryst. (2009). E65, m281    [ doi:10.1107/S1600536809004802 ]

[mu]-Bis(diphenylarsino)methane-[kappa]2As:As'-bis[chloridogold(I)]

U. Monkowius, M. Zabel and H. Yersin

Abstract top

The title structure, [Au2Cl2(C25H22As2)], consists of discrete molecules disposed about a crystallographic twofold axis. The Au atom exhibits a nearly linear coordination by As and Cl atoms. Au...Au interactions [3.4285Å(4) Å] and a weak intermolecular C-H...Cl hydrogen bond are present.

Comment top

The title compound was prepared from dpam [dpam = bis(diphenylarsino)methane] and (tht)AuCl (tht = tetrahydrothiophene) in methylene chloride in nearly quantitative yields. It is isomorphous to the crystal structure of the phosphorus congener [dppm(AuCl)2], which was determined by Schmidbaur et al. (1977b) [a = 22.31 (1) Å, b = 7.215 (7) Å, c = 18.12 (1) Å and β = 120.43 (8)°]. The structure consists of discrete molecules of [dpam(AuCl)2] disposed about a crystallographic twofold axis, which passes through the C1 atom. The Au atom is in a standard linear coordination [As—Au—Cl 174.82 (4)°] with As—Au and Au—Cl bond lengths of 2.3426 (5) and 2.289 (2) Å, respectively. The Au—As···As—Au torsion angle is 66.78 (2)°, yielding a staggered conformation of both Ph2AsAuCl moieties and an intramolecular Au···Au distance of 3.4285 (4) Å, indicative of attractive aurophilic interactions. The shortest intermolecular Au···Au distance is 5.863 Å. In its crystal, the complexes are linked to infinite chains via weak C—H···Cl intermolecular hydrogen bonds with C···Cl distance of 3.658 (4) Å and a C1—H1a···Cl1ii angle of 163° (symmetry code: (ii) -x, y + 1, -z + 1/2).

For comparison, the geometrical data of the phosphorus compound are: Au—P 2.238 (5), Au—Cl 2.288 (7), Au···Au 3.351 (2) Å, P—Au—Cl 175 (2), Au—P···P—Au 67 (1)°. It should be noted, that a second polymorph of the phosphorus complex exists: Unlike the herein presented structure, there are no aurophilic bonds between the gold(I) atoms (Healy, 2003).

All attempts to prepare the 1:1 complex [(dpamAuCl)2] starting from the title compound analogous to the published synthesis of phosphorus complex [(dppmAuCl)2] (Schmidbaur et al., 1977a) failed.

Related literature top

For related structures, see: Healy (2003); Schmidbaur et al. (1977a,b). For the synthesis of related complexes, see: Monkowius et al. (2003a,b).

Experimental top

The title compound was prepared analogously to a previously published procedure (Monkowius et al., 2003a,b): dpam (0.22 g, 0.47 mmol) and (tht)AuCl (0.30 g, 0.94 mmol, tht = tetrahydrothiophene) were stirred in methylene chloride (20 ml) at room temperature for 2 h. The product was precipitated with n-pentane and isolated by filtration. Recrystallization from methylene chloride/diethyl ether yields colourless crystals suitable for X-ray crystallography. Yield: 0.40 g (0.43 mmol, 91%); 1H NMR (300 MHz, CDCl3): 7.55–7.60 (m, Ph—H, 8 H), 7.37–7.51 (m, Ph—H, 12 H), 3.48 p.p.m. (s, CH2, 2 H); 13C NMR (75.5 MHz, CDCl3): 134.63, 132.93, 130.44, 129.23, 25.08 p.p.m.; MS (ESI): m/z (%) = 1605.3 [L2Au3Cl2]+ (5), 1373.3 [L2Au3Cl]+ (47), 1141.3 [L2Au]+ (76), 901.1 [M—Cl]+ (25), 669.2 [LAu]+ (100); EA (C25H22As2Au2Cl2) calc.: C 32.04, H 2.37, found: C 32.01, H 2.37.

Refinement top

The H atoms were positioned with idealized geometry and were refined isotropic using a riding model with C—H = 0.95 and 0.99 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: IPDS Software (Stoe & Cie, 1998); cell refinement: IPDS Software (Stoe & Cie, 1998); data reduction: IPDS Software (Stoe & Cie, 1998); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. View of the title compound with the atom numbering scheme (symmetry code: (i) -x, y, -z + 1/2). Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
[Figure 2] Fig. 2. Crystal structure of the title compound depicting the intermolecular hydrogen bonds between H1A and Cl1ii (symmetry code: (ii) -x, y + 1, -z + 1/2). The H atoms not involved in hydrogen bonding have been omitted.
µ-Bis(diphenylarsino)methane-κ2As:As'-bis[chloridogold(I)] top
Crystal data top
[Au2Cl2(C25H22As2)]F(000) = 1720
Mr = 937.11Cell parameters were determined by indexing 8000 reflections with I/sigma limit 6.0.
Monoclinic, C2/cDx = 2.384 Mg m−3
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 22.7171 (18) ÅCell parameters from 8000 reflections
b = 7.3151 (6) Åθ = 2.1–26.9°
c = 18.2047 (15) ŵ = 13.96 mm−1
β = 120.342 (8)°T = 173 K
V = 2610.8 (4) Å3Prism, colourless
Z = 40.24 × 0.20 × 0.18 mm
Data collection top
Stoe IPDS
diffractometer		2790 independent reflections
Radiation source: fine-focus sealed tube2431 reflections with I > 2σ(I)
graphiteRint = 0.062
rotation scansθmax = 26.9°, θmin = 2.1°
Absorption correction: analytical
[from crystal shape; X-SHAPE and X-RED in IPDS Software (Stoe & Cie, 1998)]		h = −28→28
Tmin = 0.051, Tmax = 0.083k = −9→9
12353 measured reflectionsl = −22→22
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.055 w = 1/[σ2(Fo2) + (0.0315P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.001
2790 reflectionsΔρmax = 1.65 e Å−3
142 parametersΔρmin = −0.70 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001Fc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00085 (4)
Crystal data top
[Au2Cl2(C25H22As2)]V = 2610.8 (4) Å3
Mr = 937.11Z = 4
Monoclinic, C2/cMo Kα radiation
a = 22.7171 (18) ŵ = 13.96 mm−1
b = 7.3151 (6) ÅT = 173 K
c = 18.2047 (15) Å0.24 × 0.20 × 0.18 mm
β = 120.342 (8)°
Data collection top
Stoe IPDS
diffractometer		2790 independent reflections
Absorption correction: analytical
[from crystal shape; X-SHAPE and X-RED in IPDS Software (Stoe & Cie, 1998)]		2431 reflections with I > 2σ(I)
Tmin = 0.051, Tmax = 0.083Rint = 0.062
12353 measured reflectionsθmax = 26.9°
Refinement top
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.055Δρmax = 1.65 e Å−3
S = 0.96Δρmin = −0.70 e Å−3
2790 reflectionsAbsolute structure: ?
142 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. Data were collected applying an imaging plate system (Stoe) with the following measurement parameters:

Detector distance [mm] 65 Phi movement mode Oscillation Phi incr. [degrees] 1.2 Number of exposures 200 Irradiation / exposure [min] 2.00

For a detailed description of the method see: Sheldrick, G. M., Paulus, E., Vertesy, L. & Hahn, F. (1995). Acta Cryst. B51, 89–98.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su'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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Au10.00458 (1)0.59917 (2)0.15885 (1)0.0364 (1)
As1−0.05684 (2)0.86199 (5)0.15224 (2)0.0286 (1)
Cl10.07339 (7)0.35726 (17)0.17281 (11)0.0617 (5)
C10.000001.0152 (8)0.250000.0335 (16)
C2−0.08392 (19)1.0208 (6)0.0560 (3)0.0345 (11)
C3−0.0783 (2)0.9600 (7)−0.0115 (3)0.0430 (14)
C4−0.0981 (2)1.0716 (9)−0.0818 (3)0.0553 (18)
C5−0.1228 (2)1.2445 (8)−0.0834 (3)0.0583 (17)
C6−0.1289 (3)1.3050 (8)−0.0165 (4)0.074 (2)
C7−0.1091 (3)1.1941 (7)0.0543 (3)0.0640 (19)
C8−0.13949 (18)0.8231 (6)0.1565 (2)0.0330 (10)
C9−0.1733 (3)0.6586 (8)0.1285 (4)0.0591 (19)
C10−0.2351 (3)0.6299 (9)0.1269 (5)0.078 (2)
C11−0.2608 (2)0.7632 (10)0.1543 (4)0.0641 (18)
C12−0.2273 (3)0.9248 (9)0.1831 (4)0.064 (2)
C13−0.1665 (2)0.9580 (8)0.1839 (3)0.0515 (16)
H1A−0.029101.094500.262600.0400*
H3A−0.060700.84140−0.010000.0520*
H4A−0.094801.02880−0.128800.0660*
H5A−0.135601.32180−0.131000.0700*
H6A−0.146701.42340−0.018400.0890*
H7A−0.112801.237000.101100.0770*
H9A−0.154700.564500.110400.0720*
H10A−0.258800.517400.106600.0930*
H11A−0.302500.743600.153400.0760*
H12A−0.245601.016400.203000.0770*
H13A−0.143901.072300.203100.0620*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Au10.0406 (1)0.0289 (1)0.0443 (1)0.0048 (1)0.0248 (1)0.0023 (1)
As10.0285 (2)0.0273 (2)0.0273 (2)0.0012 (1)0.0121 (1)−0.0007 (2)
Cl10.0723 (8)0.0355 (6)0.1015 (11)0.0191 (6)0.0618 (8)0.0183 (7)
C10.026 (2)0.032 (3)0.034 (3)0.00000.009 (2)0.0000
C20.0340 (18)0.032 (2)0.0292 (19)−0.0015 (16)0.0098 (15)0.0020 (16)
C30.0330 (19)0.057 (3)0.037 (2)0.0046 (19)0.0163 (17)0.004 (2)
C40.041 (2)0.087 (4)0.041 (3)0.004 (2)0.023 (2)0.014 (3)
C50.054 (3)0.065 (3)0.044 (3)−0.007 (3)0.016 (2)0.017 (3)
C60.107 (5)0.036 (3)0.058 (3)0.010 (3)0.026 (3)0.011 (3)
C70.106 (4)0.038 (3)0.038 (3)0.010 (3)0.029 (3)0.001 (2)
C80.0248 (16)0.041 (2)0.0267 (18)−0.0002 (16)0.0082 (14)−0.0010 (17)
C90.051 (3)0.049 (3)0.084 (4)−0.013 (2)0.039 (3)−0.021 (3)
C100.058 (3)0.071 (4)0.108 (5)−0.028 (3)0.045 (4)−0.019 (4)
C110.035 (2)0.092 (4)0.065 (3)−0.008 (3)0.025 (2)0.001 (3)
C120.043 (3)0.087 (4)0.065 (4)0.006 (3)0.029 (2)−0.015 (3)
C130.040 (2)0.054 (3)0.057 (3)−0.006 (2)0.022 (2)−0.017 (2)
Geometric parameters (Å, °) top
Au1—As12.3426 (5)C11—C121.360 (10)
Au1—Cl12.2887 (16)C12—C131.395 (9)
As1—C11.941 (3)C1—H1A0.9900
As1—C21.926 (5)C1—H1Ai0.9900
As1—C81.939 (5)C3—H3A0.9500
C2—C31.372 (7)C4—H4A0.9500
C2—C71.385 (7)C5—H5A0.9500
C3—C41.388 (7)C6—H6A0.9500
C4—C51.378 (9)C7—H7A0.9500
C5—C61.367 (8)C9—H9A0.9500
C6—C71.391 (8)C10—H10A0.9500
C8—C91.379 (8)C11—H11A0.9500
C8—C131.381 (7)C12—H12A0.9500
C9—C101.405 (11)C13—H13A0.9500
C10—C111.355 (10)
Au1···C6ii3.773 (6)C1···H13Ai2.9600
Au1···C7ii3.756 (6)C1···H13A2.9600
Au1···C4iii3.910 (6)C1···H7A3.0900
Au1···C5iii3.759 (5)C3···H11Aviii3.0300
Au1···C8i3.601 (4)C4···H11Aviii3.0200
Au1···C9i3.857 (7)C13···H1A2.8800
Au1···Au1i3.4286 (4)C13···H4Aix2.9500
Au1···H7Aii3.5200H1A···C132.8800
Au1···H9A3.2700H1A···H13A2.2700
Au1···H3A3.1900H1A···Cl1x2.7000
Au1···H6Aii3.5600H3A···Au13.1900
Au1···H4Aiii3.6100H4A···Au1iii3.6100
Au1···H5Aiii3.3100H4A···Cl1v3.0400
Cl1···H1Aiv2.7000H4A···C13xi2.9500
Cl1···H13Aiv2.8900H5A···Au1iii3.3100
Cl1···H4Av3.0400H5A···Cl1iii3.0300
Cl1···H5Aiii3.0300H6A···Au1vii3.5600
Cl1···H11Avi3.1300H7A···Au1vii3.5200
C3···C3iii3.416 (8)H7A···C13.0900
C3···C4iii3.481 (7)H7A···H13A2.5900
C4···Au1iii3.910 (6)H9A···Au13.2700
C4···C3iii3.481 (7)H11A···Cl1xii3.1300
C5···Au1iii3.759 (5)H11A···C3viii3.0300
C6···Au1vii3.773 (6)H11A···C4viii3.0200
C7···Au1vii3.756 (6)H13A···C12.9600
C8···Au1i3.601 (4)H13A···H1A2.2700
C9···Au1i3.857 (7)H13A···H7A2.5900
C1···H7Ai3.0900H13A···Cl1x2.8900
As1—Au1—Cl1174.82 (4)As1—C1—H1Ai110.00
Au1—As1—C1108.88 (12)As1i—C1—H1A110.00
Au1—As1—C2116.75 (14)H1A—C1—H1Ai108.00
Au1—As1—C8116.18 (13)As1i—C1—H1Ai110.00
C1—As1—C2104.16 (19)C2—C3—H3A120.00
C1—As1—C8104.90 (11)C4—C3—H3A120.00
C2—As1—C8104.72 (19)C3—C4—H4A120.00
As1—C1—As1i109.5 (3)C5—C4—H4A120.00
As1—C2—C3119.2 (3)C4—C5—H5A120.00
As1—C2—C7120.7 (4)C6—C5—H5A120.00
C3—C2—C7120.1 (4)C5—C6—H6A120.00
C2—C3—C4120.1 (5)C7—C6—H6A120.00
C3—C4—C5119.9 (5)C2—C7—H7A120.00
C4—C5—C6120.1 (5)C6—C7—H7A120.00
C5—C6—C7120.4 (6)C8—C9—H9A120.00
C2—C7—C6119.4 (5)C10—C9—H9A120.00
As1—C8—C9118.9 (4)C9—C10—H10A120.00
As1—C8—C13121.7 (4)C11—C10—H10A120.00
C9—C8—C13119.4 (5)C10—C11—H11A120.00
C8—C9—C10120.1 (6)C12—C11—H11A120.00
C9—C10—C11119.8 (6)C11—C12—H12A119.00
C10—C11—C12120.4 (6)C13—C12—H12A120.00
C11—C12—C13120.9 (6)C8—C13—H13A120.00
C8—C13—C12119.3 (5)C12—C13—H13A120.00
As1—C1—H1A110.00
Au1—As1—C1—As1i−34.87 (4)C3—C2—C7—C60.4 (9)
C2—As1—C1—As1i−160.10 (16)C7—C2—C3—C4−0.3 (8)
C8—As1—C1—As1i90.12 (13)As1—C2—C7—C6−179.4 (5)
Au1—As1—C2—C312.2 (5)C2—C3—C4—C50.7 (8)
C1—As1—C2—C3132.3 (4)C3—C4—C5—C6−1.1 (8)
C8—As1—C2—C3−117.9 (4)C4—C5—C6—C71.2 (10)
Au1—As1—C2—C7−168.1 (4)C5—C6—C7—C2−0.8 (10)
C1—As1—C2—C7−48.1 (5)As1—C8—C9—C10−176.9 (5)
C8—As1—C2—C761.9 (5)C13—C8—C9—C100.8 (8)
C2—As1—C8—C9104.0 (4)As1—C8—C13—C12177.9 (4)
Au1—As1—C8—C9−26.4 (4)C9—C8—C13—C120.3 (7)
C1—As1—C8—C9−146.6 (4)C8—C9—C10—C11−1.1 (10)
C2—As1—C8—C13−73.6 (4)C9—C10—C11—C120.2 (11)
Au1—As1—C8—C13156.0 (3)C10—C11—C12—C131.0 (10)
C1—As1—C8—C1335.7 (4)C11—C12—C13—C8−1.2 (8)
As1—C2—C3—C4179.4 (4)
Symmetry codes: (i) −x, y, −z+1/2; (ii) x, y−1, z; (iii) −x, −y+2, −z; (iv) −x, y−1, −z+1/2; (v) −x, −y+1, −z; (vi) x+1/2, y−1/2, z; (vii) x, y+1, z; (viii) −x−1/2, −y+3/2, −z; (ix) x, −y+2, z+1/2; (x) −x, y+1, −z+1/2; (xi) x, −y+2, z−1/2; (xii) x−1/2, y+1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···Cl1x0.992.703.658 (4)163
Symmetry codes: (x) −x, y+1, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Au1—As12.3426 (5)As1—C21.926 (5)
Au1—Cl12.2887 (16)As1—C81.939 (5)
As1—C11.941 (3)
As1—Au1—Cl1174.82 (4)C2—As1—C8104.72 (19)
Au1—As1—C1108.88 (12)As1—C1—As1i109.5 (3)
Au1—As1—C2116.75 (14)As1—C2—C3119.2 (3)
Au1—As1—C8116.18 (13)As1—C2—C7120.7 (4)
C1—As1—C2104.16 (19)As1—C8—C9118.9 (4)
C1—As1—C8104.90 (11)As1—C8—C13121.7 (4)
Symmetry codes: (i) −x, y, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···Cl1ii0.992.703.658 (4)163
Symmetry codes: (ii) −x, y+1, −z+1/2.
Acknowledgements top

This work was supported by the Bundesministerium für Bildung und Forschung (BMBF).

references
References top

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.

Healy, P. C. (2003). Acta Cryst. E59, m1112–m1114.

Monkowius, U., Nogai, S. & Schmidbaur, H. (2003a). Organometallics, 22, 145–152.

Monkowius, U., Nogai, S. & Schmidbaur, H. (2003b). Z. Naturforsch. Teil B, 58, 751–758.

Schmidbaur, H., Wohlleben, A., Schubert, U., Frank, A. & Huttner, G. (1977a). Chem. Ber. 110, 2751–2757.

Schmidbaur, H., Wohlleben, A., Wagner, F., Orama, O. & Huttner, G. (1977b). Chem. Ber. 110, 1748–1754.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Stoe & Cie (1998). IPDS Software. Stoe & Cie GmbH, Darmstadt, Germany.