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Acta Cryst. (2009). E65, m1700    [ doi:10.1107/S1600536809050454 ]

[(Z)-N-(4-Chlorophenyl)-O-methylthiocarbamato-[kappa]S](triphenylphosphine-[kappa]P)gold(I)

P. P. Tadbuppa and E. R. T. Tiekink

Abstract top

The title compound, [Au(C8H7ClNOS)(C18H15P)], is characterized by a linear S,P-donor set with a small deviation from the ideal linearity [S-Au-P = 175.14 (5)°] due to the close approach of the O atom to the Au atom [Au...O = 2.882 (3) Å]. Loosely associated dimers are formed in the crystal structure through C-H...O interactions.

Comment top

As a part of systematic studies of phosphinegold(I) thiocarbamides (Ho et al. 2006; Ho & Tiekink, 2007; Kuan et al., 2008), the title compound, [(C5H5)3P]Au[SC(OMe)N(C6H4Cl-p)], was synthesized.

The thiocarbamide functions as a thiolate ligand as seen in the magnitudes of the C1—S1 and C1—N1 bond distances of 1.756 (5) and 1.271 (6) Å, respectively; the conformation about C1—N1 is Z. While the central SC(O)N chromophore is planar as seen in the S1—C1—N1—C2 and O1—C1—N1—C2 torsion angles of -0.8 (7) and -179.0 (4)°, respectively, the N-bound aryl ring is orthogonal to this plane as seen in the C1–N1–C2–C3 torsion angle of -76.6 (6)°. The thiocarbamide and phosphine ligands define an S, P donor set (Table 1 and Fig. 1). The deviation of the S1—Au—P1 angle [175.14 (5)°] from linearity is traced to the close approach of the O1 atom to the Au atom [2.882 (3) Å]. In the crystal structure, centrosymmetrically related molecules associate via C—H···O interactions (Table 2 and Fig. 2). The dimeric units formed are consolidated into the crystal structure by C—H···π interactions. The closest such contact occurs between C24—H24 and the ring centroid (Cg) of (C15—C20)i [C24···Cgi = 3.552 (6), H24···Cgi = 2.73 Å, C24—H24···Cgi = 146°, symmetry code: (i) -1+x, y, z].

Related literature top

For structural systematics and luminescence properties of phosphinegold(I) carbonimidothioates, see: Ho et al. (2006); Ho & Tiekink (2007); Kuan et al. (2008). For the synthesis, see: Hall et al. (1993).

Experimental top

The title compound was prepared following the standard literature procedure from the reaction of Ph3AuCl and MeOC(S)N(H)(C6H4Cl-p) in the presence of base (Hall et al., 1993).

Refinement top

H atoms were geometrically placed (C—H = 0.94 and 0.97 Å) and refined as riding, with Uiso(H) = 1.2(1.5 for methyl)Ueq(C). The maximum and minimum residual electron density peaks of 1.17 and 0.62 e Å-3, respectively, were located 0.88 and 1.39 Å from the Au atom.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: PATTY in DIRDIF92 (Beurskens et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Supramolecular dimer in the title compound, mediated by C—H···O contacts (orange dashed lines). [Colour codes: Au orange; Cl cyan; S yellow; P pink; O red; N blue; C grey; and H green.]
[(Z)-N-(4-Chlorophenyl)-O-methylthiocarbamato- κS](triphenylphosphine-κP)gold(I) top
Crystal data top
[Au(C8H7ClNOS)(C18H15P)]F(000) = 1280
Mr = 659.89Dx = 1.804 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 4456 reflections
a = 9.1781 (6) Åθ = 2.3–25.0°
b = 17.5679 (12) ŵ = 6.34 mm−1
c = 15.5384 (11) ÅT = 223 K
β = 104.156 (2)°Block, colourless
V = 2429.3 (3) Å30.11 × 0.10 × 0.07 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		5570 independent reflections
Radiation source: fine-focus sealed tube4526 reflections with I > 2σ(I)
graphiteRint = 0.042
φ and ω scansθmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −11→10
Tmin = 0.363, Tmax = 1.000k = −22→22
17091 measured reflectionsl = −20→14
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0462P)2P]
where P = (Fo2 + 2Fc2)/3
5570 reflections(Δ/σ)max = 0.001
290 parametersΔρmax = 1.17 e Å−3
0 restraintsΔρmin = −0.62 e Å−3
Crystal data top
[Au(C8H7ClNOS)(C18H15P)]V = 2429.3 (3) Å3
Mr = 659.89Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.1781 (6) ŵ = 6.34 mm−1
b = 17.5679 (12) ÅT = 223 K
c = 15.5384 (11) Å0.11 × 0.10 × 0.07 mm
β = 104.156 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer		5570 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		4526 reflections with I > 2σ(I)
Tmin = 0.363, Tmax = 1.000Rint = 0.042
17091 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.090Δρmax = 1.17 e Å−3
S = 1.06Δρmin = −0.62 e Å−3
5570 reflectionsAbsolute structure: ?
290 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Au0.14582 (2)0.203115 (10)0.426452 (12)0.02944 (8)
Cl10.2539 (2)−0.28046 (9)0.29800 (15)0.0761 (6)
S10.19317 (16)0.07649 (7)0.40658 (8)0.0372 (3)
P10.08624 (13)0.32352 (7)0.45280 (8)0.0265 (3)
O10.2450 (4)0.10253 (19)0.5758 (2)0.0342 (8)
N10.2656 (4)−0.0229 (2)0.5444 (3)0.0352 (9)
C10.2379 (5)0.0450 (3)0.5172 (3)0.0303 (10)
C20.2605 (5)−0.0827 (3)0.4832 (3)0.0350 (11)
C30.1251 (5)−0.1125 (3)0.4349 (3)0.0378 (12)
H30.0343−0.09110.44100.045*
C40.1222 (6)−0.1735 (3)0.3779 (4)0.0428 (13)
H40.0304−0.19310.34430.051*
C50.2552 (7)−0.2045 (3)0.3715 (5)0.0461 (14)
C60.3906 (7)−0.1768 (3)0.4203 (5)0.0507 (16)
H60.4809−0.19960.41530.061*
C70.3939 (6)−0.1165 (3)0.4754 (4)0.0434 (13)
H70.4866−0.09760.50840.052*
C80.2730 (7)0.0813 (4)0.6684 (3)0.0519 (15)
H8A0.19660.04560.67620.078*
H8B0.26990.12630.70400.078*
H8C0.37120.05760.68700.078*
C90.1409 (5)0.3443 (3)0.5711 (3)0.0295 (10)
C100.2879 (6)0.3272 (3)0.6162 (4)0.0466 (14)
H100.35390.30470.58590.056*
C110.3363 (7)0.3434 (4)0.7058 (4)0.0535 (16)
H110.43510.33160.73680.064*
C120.2396 (7)0.3768 (3)0.7492 (4)0.0471 (14)
H120.27300.38850.80990.057*
C130.0944 (6)0.3936 (3)0.7049 (4)0.0436 (13)
H130.02830.41590.73520.052*
C140.0462 (6)0.3773 (3)0.6154 (3)0.0326 (11)
H14−0.05280.38920.58480.039*
C150.1717 (5)0.3984 (2)0.4012 (3)0.0267 (9)
C160.1530 (5)0.3965 (3)0.3101 (3)0.0323 (10)
H160.09890.35630.27700.039*
C170.2129 (6)0.4530 (3)0.2673 (3)0.0358 (11)
H170.19900.45130.20530.043*
C180.2926 (6)0.5118 (3)0.3152 (4)0.0382 (12)
H180.33280.55060.28620.046*
C190.3131 (6)0.5133 (3)0.4061 (4)0.0382 (12)
H190.36840.55300.43930.046*
C200.2532 (5)0.4570 (3)0.4485 (3)0.0344 (11)
H200.26810.45860.51050.041*
C21−0.1136 (5)0.3406 (3)0.4161 (3)0.0259 (9)
C22−0.2118 (6)0.2803 (3)0.4140 (4)0.0425 (13)
H22−0.17350.23150.43090.051*
C23−0.3653 (6)0.2911 (3)0.3874 (5)0.0500 (15)
H23−0.43070.24990.38680.060*
C24−0.4224 (6)0.3617 (3)0.3618 (4)0.0421 (13)
H24−0.52680.36890.34280.051*
C25−0.3268 (6)0.4219 (3)0.3641 (3)0.0361 (11)
H25−0.36640.47050.34700.043*
C26−0.1724 (5)0.4122 (3)0.3913 (3)0.0312 (10)
H26−0.10790.45400.39300.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Au0.03688 (12)0.02458 (11)0.02522 (11)0.00819 (7)0.00444 (8)0.00001 (7)
Cl10.0969 (14)0.0355 (8)0.1131 (17)−0.0060 (8)0.0587 (13)−0.0165 (9)
S10.0577 (8)0.0266 (6)0.0267 (6)0.0125 (6)0.0092 (6)0.0013 (5)
P10.0296 (6)0.0242 (6)0.0250 (6)0.0058 (5)0.0050 (5)−0.0002 (5)
O10.0384 (18)0.0375 (19)0.0250 (18)0.0022 (15)0.0045 (14)0.0035 (15)
N10.032 (2)0.037 (2)0.037 (2)0.0053 (17)0.0106 (18)0.0114 (19)
C10.028 (2)0.036 (3)0.027 (3)0.0034 (19)0.007 (2)0.003 (2)
C20.035 (3)0.028 (2)0.043 (3)0.003 (2)0.013 (2)0.012 (2)
C30.033 (3)0.034 (3)0.051 (3)0.004 (2)0.018 (2)0.008 (2)
C40.038 (3)0.035 (3)0.058 (4)−0.003 (2)0.016 (3)0.003 (3)
C50.056 (4)0.026 (3)0.065 (4)0.001 (2)0.030 (3)0.006 (2)
C60.047 (3)0.032 (3)0.081 (5)0.014 (2)0.033 (3)0.011 (3)
C70.032 (3)0.040 (3)0.061 (4)0.006 (2)0.019 (3)0.015 (3)
C80.064 (4)0.066 (4)0.021 (3)0.003 (3)0.002 (3)0.001 (3)
C90.038 (3)0.024 (2)0.025 (2)0.0043 (19)0.004 (2)0.0020 (18)
C100.043 (3)0.056 (4)0.036 (3)0.021 (3)0.000 (2)−0.006 (3)
C110.053 (4)0.067 (4)0.033 (3)0.017 (3)−0.005 (3)−0.002 (3)
C120.067 (4)0.043 (3)0.025 (3)0.001 (3)−0.002 (3)−0.003 (2)
C130.056 (3)0.045 (3)0.033 (3)0.003 (3)0.015 (3)−0.005 (2)
C140.036 (3)0.034 (3)0.027 (3)0.001 (2)0.008 (2)−0.001 (2)
C150.027 (2)0.023 (2)0.031 (2)0.0050 (17)0.0086 (19)−0.0006 (19)
C160.036 (3)0.029 (2)0.030 (3)0.003 (2)0.004 (2)−0.001 (2)
C170.040 (3)0.039 (3)0.029 (3)0.006 (2)0.011 (2)0.003 (2)
C180.037 (3)0.030 (3)0.049 (3)0.001 (2)0.014 (2)0.004 (2)
C190.038 (3)0.033 (3)0.043 (3)−0.003 (2)0.011 (2)−0.003 (2)
C200.041 (3)0.032 (3)0.027 (3)0.005 (2)0.003 (2)−0.003 (2)
C210.027 (2)0.030 (2)0.019 (2)0.0047 (18)0.0020 (18)0.0013 (18)
C220.042 (3)0.029 (3)0.050 (3)0.001 (2)−0.003 (3)0.011 (2)
C230.037 (3)0.050 (4)0.061 (4)−0.008 (2)0.008 (3)0.011 (3)
C240.033 (3)0.055 (4)0.038 (3)0.006 (2)0.008 (2)0.000 (3)
C250.041 (3)0.032 (3)0.033 (3)0.012 (2)0.004 (2)−0.001 (2)
C260.033 (3)0.030 (2)0.029 (3)0.0040 (19)0.007 (2)−0.002 (2)
Geometric parameters (Å, °) top
Au—S12.3018 (12)C11—H110.9400
Au—P12.2473 (12)C12—C131.374 (8)
Cl1—C51.755 (6)C12—H120.9400
S1—C11.756 (5)C13—C141.381 (7)
P1—C211.808 (4)C13—H130.9400
P1—C151.815 (5)C14—H140.9400
P1—C91.820 (5)C15—C201.375 (6)
O1—C11.352 (6)C15—C161.384 (6)
O1—C81.447 (6)C16—C171.383 (7)
N1—C11.271 (6)C16—H160.9400
N1—C21.409 (7)C17—C181.375 (7)
C2—C31.387 (7)C17—H170.9400
C2—C71.393 (7)C18—C191.380 (7)
C3—C41.387 (8)C18—H180.9400
C3—H30.9400C19—C201.375 (7)
C4—C51.362 (8)C19—H190.9400
C4—H40.9400C20—H200.9400
C5—C61.377 (9)C21—C221.385 (7)
C6—C71.357 (8)C21—C261.386 (6)
C6—H60.9400C22—C231.381 (8)
C7—H70.9400C22—H220.9400
C8—H8A0.9700C23—C241.366 (7)
C8—H8B0.9700C23—H230.9400
C8—H8C0.9700C24—C251.369 (7)
C9—C141.363 (7)C24—H240.9400
C9—C101.393 (7)C25—C261.387 (7)
C10—C111.384 (8)C25—H250.9400
C10—H100.9400C26—H260.9400
C11—C121.370 (8)
P1—Au—S1175.14 (5)C11—C12—C13120.7 (5)
C1—S1—Au100.35 (17)C11—C12—H12119.6
C21—P1—C15104.8 (2)C13—C12—H12119.6
C21—P1—C9107.1 (2)C12—C13—C14119.5 (5)
C15—P1—C9105.0 (2)C12—C13—H13120.2
C21—P1—Au111.82 (15)C14—C13—H13120.2
C15—P1—Au116.79 (15)C9—C14—C13120.6 (5)
C9—P1—Au110.73 (15)C9—C14—H14119.7
C1—O1—C8116.4 (4)C13—C14—H14119.7
C1—N1—C2120.3 (4)C20—C15—C16118.7 (4)
N1—C1—O1120.3 (4)C20—C15—P1123.0 (4)
N1—C1—S1126.9 (4)C16—C15—P1118.4 (3)
O1—C1—S1112.7 (3)C17—C16—C15120.7 (5)
C3—C2—C7118.8 (5)C17—C16—H16119.6
C3—C2—N1121.6 (4)C15—C16—H16119.6
C7—C2—N1119.4 (5)C18—C17—C16120.0 (5)
C4—C3—C2120.8 (5)C18—C17—H17120.0
C4—C3—H3119.6C16—C17—H17120.0
C2—C3—H3119.6C17—C18—C19119.3 (5)
C5—C4—C3118.5 (5)C17—C18—H18120.3
C5—C4—H4120.7C19—C18—H18120.3
C3—C4—H4120.7C20—C19—C18120.4 (5)
C4—C5—C6121.6 (6)C20—C19—H19119.8
C4—C5—Cl1119.2 (5)C18—C19—H19119.8
C6—C5—Cl1119.2 (4)C15—C20—C19120.8 (5)
C7—C6—C5120.1 (5)C15—C20—H20119.6
C7—C6—H6120.0C19—C20—H20119.6
C5—C6—H6120.0C22—C21—C26118.7 (4)
C6—C7—C2120.2 (5)C22—C21—P1119.0 (4)
C6—C7—H7119.9C26—C21—P1122.3 (4)
C2—C7—H7119.9C23—C22—C21120.8 (5)
O1—C8—H8A109.5C23—C22—H22119.6
O1—C8—H8B109.5C21—C22—H22119.6
H8A—C8—H8B109.5C24—C23—C22120.1 (5)
O1—C8—H8C109.5C24—C23—H23119.9
H8A—C8—H8C109.5C22—C23—H23119.9
H8B—C8—H8C109.5C23—C24—C25119.7 (5)
C14—C9—C10119.8 (5)C23—C24—H24120.1
C14—C9—P1122.9 (4)C25—C24—H24120.1
C10—C9—P1117.3 (4)C24—C25—C26120.8 (5)
C11—C10—C9119.6 (5)C24—C25—H25119.6
C11—C10—H10120.2C26—C25—H25119.6
C9—C10—H10120.2C21—C26—C25119.7 (5)
C12—C11—C10119.7 (5)C21—C26—H26120.1
C12—C11—H11120.1C25—C26—H26120.1
C10—C11—H11120.1
C2—N1—C1—O1−179.0 (4)P1—C9—C14—C13−178.5 (4)
C2—N1—C1—S1−0.8 (7)C12—C13—C14—C90.6 (8)
C8—O1—C1—N1−4.9 (6)C21—P1—C15—C20110.4 (4)
C8—O1—C1—S1176.7 (4)C9—P1—C15—C20−2.2 (4)
Au—S1—C1—N1175.8 (4)Au—P1—C15—C20−125.2 (4)
Au—S1—C1—O1−6.0 (3)C21—P1—C15—C16−69.1 (4)
C1—N1—C2—C3−76.6 (6)C9—P1—C15—C16178.3 (4)
C1—N1—C2—C7108.0 (5)Au—P1—C15—C1655.2 (4)
C7—C2—C3—C4−1.8 (8)C20—C15—C16—C17−1.0 (7)
N1—C2—C3—C4−177.2 (5)P1—C15—C16—C17178.5 (4)
C2—C3—C4—C51.2 (8)C15—C16—C17—C180.3 (7)
C3—C4—C5—C60.1 (9)C16—C17—C18—C190.5 (8)
C3—C4—C5—Cl1−178.7 (4)C17—C18—C19—C20−0.6 (8)
C4—C5—C6—C7−0.9 (9)C16—C15—C20—C190.9 (7)
Cl1—C5—C6—C7178.0 (4)P1—C15—C20—C19−178.6 (4)
C5—C6—C7—C20.3 (9)C18—C19—C20—C15−0.1 (8)
C3—C2—C7—C61.0 (8)C15—P1—C21—C22155.3 (4)
N1—C2—C7—C6176.5 (5)C9—P1—C21—C22−93.6 (4)
C21—P1—C9—C14−8.7 (5)Au—P1—C21—C2227.9 (4)
C15—P1—C9—C14102.3 (4)C15—P1—C21—C26−25.9 (4)
Au—P1—C9—C14−130.9 (4)C9—P1—C21—C2685.3 (4)
C21—P1—C9—C10173.1 (4)Au—P1—C21—C26−153.3 (3)
C15—P1—C9—C10−75.9 (5)C26—C21—C22—C230.3 (8)
Au—P1—C9—C1051.0 (5)P1—C21—C22—C23179.2 (5)
C14—C9—C10—C110.4 (9)C21—C22—C23—C240.6 (10)
P1—C9—C10—C11178.6 (5)C22—C23—C24—C25−1.1 (10)
C9—C10—C11—C12−0.6 (10)C23—C24—C25—C260.5 (8)
C10—C11—C12—C130.8 (10)C22—C21—C26—C25−0.8 (7)
C11—C12—C13—C14−0.8 (9)P1—C21—C26—C25−179.7 (4)
C10—C9—C14—C13−0.4 (8)C24—C25—C26—C210.4 (7)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i0.942.523.365 (6)150
Symmetry codes: (i) −x, −y, −z+1.
Table 1
Selected geometric parameters (Å) top
Au—S12.3018 (12)Au—P12.2473 (12)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i0.942.523.365 (6)150
Symmetry codes: (i) −x, −y, −z+1.
Acknowledgements top

The National University of Singapore (grant No. R-143-000-213-112) is thanked for support.

references
References top

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