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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): m1700.
Published online 2009 November 28. doi:  10.1107/S1600536809050454
PMCID: PMC2972176

[(Z)-N-(4-Chloro­phen­yl)-O-methyl­thio­carbamato-κS](triphenyl­phosphine-κP)gold(I)

Abstract

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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-65-m1700-scheme1.jpg

Experimental

Crystal data

  • [Au(C8H7ClNOS)(C18H15P)]
  • M r = 659.89
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1700-efi1.jpg
  • a = 9.1781 (6) Å
  • b = 17.5679 (12) Å
  • c = 15.5384 (11) Å
  • β = 104.156 (2)°
  • V = 2429.3 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 6.34 mm−1
  • T = 223 K
  • 0.11 × 0.10 × 0.07 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.363, T max = 1.000
  • 17091 measured reflections
  • 5570 independent reflections
  • 4526 reflections with I > 2σ(I)
  • R int = 0.042

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.090
  • S = 1.06
  • 5570 reflections
  • 290 parameters
  • H-atom parameters constrained
  • Δρmax = 1.17 e Å−3
  • Δρmin = −0.62 e Å−3

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

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809050454/hy2256sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050454/hy2256Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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].

Experimental

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

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.

Figures

Fig. 1.
Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
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.]

Crystal data

[Au(C8H7ClNOS)(C18H15P)]F(000) = 1280
Mr = 659.89Dx = 1.804 Mg m3
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 mm1
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

Bruker SMART APEX CCD diffractometer5570 independent reflections
Radiation source: fine-focus sealed tube4526 reflections with I > 2σ(I)
graphiteRint = 0.042
[var phi] 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

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 = 1.06w = 1/[σ2(Fo2) + (0.0462P)2P] where P = (Fo2 + 2Fc2)/3
5570 reflections(Δ/σ)max = 0.001
290 parametersΔρmax = 1.17 e Å3
0 restraintsΔρmin = −0.62 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

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)

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, °)

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, °)

D—H···AD—HH···AD···AD—H···A
C3—H3···O1i0.942.523.365 (6)150

Symmetry codes: (i) −x, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2256).

References

  • Beurskens, P. T., Admiraal, G., Beurskens, G., Bosman, W. P., Garcia-Granda, S., Gould, R. O., Smits, J. M. M. & Smykalla, C. (1992). The DIRDIF Program System. Technical Report. Crystallography Laboratory, University of Nijmegen, The Netherlands.
  • Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
  • Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hall, V. J., Siasios, G. & Tiekink, E. R. T. (1993). Aust. J. Chem. 46, 561–570.
  • Ho, S. Y., Cheng, E. C.-C., Tiekink, E. R. T. & Yam, V. W.-W. (2006). Inorg. Chem. 45, 8165–8174. [PubMed]
  • Ho, S. Y. & Tiekink, E. R. T. (2007). CrystEngComm, 9, 368–378.
  • Kuan, F. S., Ho, S. Y., Tadbuppa, P. P. & Tiekink, E. R. T. (2008). CrystEngComm, 10, 548–564.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF. In preparation.

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