supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

hb5235 scheme

Acta Cryst. (2009). E65, m1646    [ doi:10.1107/S160053680904906X ]

[(Z)-N-(2-Chlorophenyl)-O-methylthiocarbamato-[kappa]S](triphenylphosphine-[kappa]P)gold(I)

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

Abstract top

In the title compound, [Au(C8H7ClNOS)(C18H15P)], the AuI atom has a near-linear geometry, defined by an S,P-donor set [S-Au-P = 175.09 (5)°]. The proximity of the methoxy O atom to Au may be responsible for the deviation from linearity [Au...O = 2.959 (4) Å].

Comment top

The motivation for systematic studies of phosphinegold(I) thiocarbamides, e.g. (R3P)PAu[SC(OR')NR''], relates to the delineation of crystal packing characteristics, e.g. the propensity to form aurophilic (Au···Au) interactions (Ho & Tiekink, 2007; Kuan et al., 2008), as well as the examination of their luminescence characteristics (Ho et al. 2006). The title compound, (C5H5)3PAu[SC(OMe)N(C6H4Cl-o)], (I), was synthesized during the course of these studies.

The thiocarbamato anion functions as a thiolate ligand in (I), Fig. 1, as seen in the magnitudes of the C1—S1 and C1═N1 bond distances of 1.762 (5) and 1.269 (6) Å, respectively; the conformation about C1═N1 is Z. The central SC(O)N chromophore has small but significant twists from planarity as seen in the S1–C1–N1–C2 and O1–C1–N1–C2 torsion angles of 10.0 (7) and -173.1 (4) °, respectively. The N-bound aryl ring is twisted out of this plane: the C1–N1–C2–C3 torsion angle is -126.3 (5) °. The thiocarbamato and phosphine ligands define an approximately linear S, P donor set, Table. The deviation of the S1—Au—P1 angle [175.09 (5) °] from the ideal linear geometry is ascribed to the close approach of the O1 atom [2.959 (4) Å] to Au.

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

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

Refinement top

The H atoms were geometrically placed (C—H = 0.94–0.97 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C). A rotating group model was used for the methyl group. The maximum and minimum residual electron density peaks of 1.17 and 0.54 e Å-3, respectively, are located 0.86 Å and 0.38 Å from the Au and H20 atoms, respectively.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SHELXTL (Bruker, 2000); 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, 2006); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing displacement ellipsoids at the 50% probability level.
[(Z)-N-(2-Chlorophenyl)-O-methylthiocarbamato- κS](triphenylphosphine-κP)gold(I) top
Crystal data top
[Au(C8H7ClNOS)(C18H15P)]F(000) = 1280
Mr = 659.89Dx = 1.819 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 3828 reflections
a = 8.9388 (5) Åθ = 2.4–24.2°
b = 26.2804 (15) ŵ = 6.39 mm−1
c = 10.3233 (6) ÅT = 223 K
β = 96.599 (1)°Block, colourless
V = 2409.0 (2) Å30.13 × 0.10 × 0.07 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		5537 independent reflections
Radiation source: fine-focus sealed tube4400 reflections with I > 2σ(I)
graphiteRint = 0.047
ω scansθmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −11→10
Tmin = 0.521, Tmax = 1k = −34→33
17015 measured reflectionsl = −13→12
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0379P)2]
where P = (Fo2 + 2Fc2)/3
5537 reflections(Δ/σ)max < 0.001
290 parametersΔρmax = 1.17 e Å−3
0 restraintsΔρmin = −0.54 e Å−3
Crystal data top
[Au(C8H7ClNOS)(C18H15P)]V = 2409.0 (2) Å3
Mr = 659.89Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.9388 (5) ŵ = 6.39 mm−1
b = 26.2804 (15) ÅT = 223 K
c = 10.3233 (6) Å0.13 × 0.10 × 0.07 mm
β = 96.599 (1)°
Data collection top
Bruker SMART CCD
diffractometer		5537 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		4400 reflections with I > 2σ(I)
Tmin = 0.521, Tmax = 1Rint = 0.047
17015 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.085Δρmax = 1.17 e Å−3
S = 1.04Δρmin = −0.54 e Å−3
5537 reflectionsAbsolute structure: ?
290 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Au0.24654 (2)0.102793 (8)0.096786 (18)0.02961 (8)
Cl10.89614 (16)0.17339 (6)−0.09989 (13)0.0446 (3)
S10.37239 (14)0.14902 (5)−0.04703 (12)0.0313 (3)
P10.13681 (14)0.06089 (5)0.25093 (12)0.0267 (3)
O10.5076 (4)0.16834 (14)0.1853 (3)0.0349 (9)
N10.6237 (5)0.20523 (16)0.0254 (4)0.0320 (10)
C10.5160 (5)0.17848 (19)0.0581 (5)0.0283 (11)
C20.6239 (6)0.22061 (19)−0.1058 (5)0.0299 (11)
C30.7475 (5)0.21050 (19)−0.1725 (5)0.0301 (11)
C40.7550 (6)0.2287 (2)−0.2976 (5)0.0390 (13)
H40.83950.2213−0.34070.047*
C50.6403 (7)0.2573 (2)−0.3584 (5)0.0405 (13)
H50.64500.2697−0.44320.049*
C60.5180 (6)0.2676 (2)−0.2937 (6)0.0428 (14)
H60.43790.2869−0.33560.051*
C70.5101 (6)0.2503 (2)−0.1685 (5)0.0384 (13)
H70.42650.2589−0.12530.046*
C80.6204 (7)0.1907 (3)0.2779 (5)0.0468 (15)
H8A0.71690.17480.27020.070*
H8B0.59360.18550.36530.070*
H8C0.62710.22680.26080.070*
C90.1331 (5)0.10132 (18)0.3935 (5)0.0273 (10)
C100.2482 (6)0.1366 (2)0.4224 (5)0.0366 (13)
H100.32250.14070.36580.044*
C110.2530 (6)0.1655 (2)0.5335 (6)0.0444 (14)
H110.33260.18850.55380.053*
C120.1430 (7)0.1611 (2)0.6157 (6)0.0441 (15)
H120.14790.18060.69230.053*
C130.0248 (7)0.1275 (2)0.5843 (6)0.0454 (15)
H13−0.05270.12530.63840.055*
C140.0199 (6)0.0975 (2)0.4747 (5)0.0379 (13)
H14−0.05990.07450.45470.045*
C150.2397 (5)0.00408 (19)0.3076 (5)0.0301 (11)
C160.2844 (6)−0.0052 (2)0.4394 (5)0.0386 (13)
H160.26400.01850.50310.046*
C170.3602 (7)−0.0506 (2)0.4751 (7)0.0510 (16)
H170.3904−0.05720.56370.061*
C180.3912 (7)−0.0857 (2)0.3836 (8)0.0551 (18)
H180.4414−0.11610.40950.066*
C190.3488 (7)−0.0762 (2)0.2546 (7)0.0526 (17)
H190.3709−0.10010.19170.063*
C200.2728 (6)−0.0314 (2)0.2154 (6)0.0422 (14)
H200.2440−0.02530.12630.051*
C21−0.0550 (5)0.03955 (19)0.2088 (4)0.0262 (10)
C22−0.1585 (6)0.0739 (2)0.1473 (5)0.0367 (13)
H22−0.12740.10650.12450.044*
C23−0.3071 (6)0.0596 (3)0.1200 (6)0.0470 (15)
H23−0.37780.08300.08070.056*
C24−0.3536 (6)0.0114 (3)0.1495 (6)0.0462 (15)
H24−0.45510.00200.12940.055*
C25−0.2516 (6)−0.0228 (2)0.2083 (6)0.0449 (14)
H25−0.2829−0.05580.22830.054*
C26−0.1020 (6)−0.0087 (2)0.2384 (5)0.0332 (12)
H26−0.0322−0.03210.27910.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Au0.02941 (12)0.03086 (12)0.02991 (12)−0.00652 (9)0.00915 (8)0.00018 (9)
Cl10.0407 (8)0.0589 (10)0.0340 (7)0.0071 (7)0.0033 (6)−0.0004 (7)
S10.0317 (7)0.0374 (8)0.0257 (6)−0.0082 (6)0.0074 (5)0.0005 (5)
P10.0265 (7)0.0255 (7)0.0290 (7)−0.0051 (5)0.0073 (5)−0.0014 (5)
O10.035 (2)0.045 (2)0.0252 (19)−0.0108 (17)0.0040 (15)0.0024 (16)
N10.030 (2)0.032 (3)0.035 (2)−0.0076 (19)0.0042 (19)−0.0003 (19)
C10.026 (2)0.032 (3)0.028 (3)−0.001 (2)0.006 (2)−0.004 (2)
C20.032 (3)0.029 (3)0.029 (3)−0.009 (2)0.004 (2)−0.001 (2)
C30.032 (3)0.027 (3)0.030 (3)−0.009 (2)0.001 (2)0.000 (2)
C40.038 (3)0.045 (3)0.036 (3)−0.008 (3)0.012 (2)−0.004 (3)
C50.054 (4)0.037 (3)0.031 (3)−0.006 (3)0.008 (3)0.008 (2)
C60.045 (3)0.034 (3)0.049 (4)−0.001 (3)0.003 (3)0.013 (3)
C70.036 (3)0.034 (3)0.046 (3)−0.003 (2)0.010 (3)0.008 (3)
C80.050 (4)0.060 (4)0.029 (3)−0.018 (3)−0.003 (3)0.001 (3)
C90.026 (3)0.025 (3)0.031 (3)0.002 (2)0.004 (2)0.002 (2)
C100.031 (3)0.036 (3)0.043 (3)−0.003 (2)0.003 (2)−0.005 (2)
C110.040 (3)0.039 (3)0.052 (4)−0.006 (3)−0.004 (3)−0.014 (3)
C120.060 (4)0.034 (3)0.036 (3)0.012 (3)−0.002 (3)−0.006 (3)
C130.062 (4)0.037 (3)0.040 (3)0.007 (3)0.020 (3)0.000 (3)
C140.042 (3)0.035 (3)0.039 (3)−0.007 (3)0.015 (3)−0.003 (2)
C150.020 (2)0.029 (3)0.041 (3)−0.006 (2)0.006 (2)−0.003 (2)
C160.033 (3)0.040 (3)0.042 (3)0.000 (2)−0.001 (2)−0.002 (3)
C170.040 (3)0.044 (4)0.065 (4)0.000 (3)−0.009 (3)0.013 (3)
C180.037 (4)0.035 (3)0.093 (6)0.011 (3)0.004 (3)0.009 (4)
C190.043 (4)0.041 (4)0.078 (5)0.004 (3)0.023 (3)−0.009 (3)
C200.037 (3)0.041 (3)0.050 (4)−0.001 (3)0.010 (3)−0.006 (3)
C210.022 (2)0.033 (3)0.024 (2)−0.003 (2)0.0043 (19)−0.004 (2)
C220.037 (3)0.033 (3)0.039 (3)0.000 (2)0.003 (2)0.005 (2)
C230.033 (3)0.058 (4)0.050 (4)0.009 (3)0.001 (3)0.004 (3)
C240.024 (3)0.071 (5)0.043 (3)−0.007 (3)0.001 (2)−0.009 (3)
C250.044 (3)0.043 (3)0.047 (4)−0.020 (3)0.001 (3)0.000 (3)
C260.028 (3)0.031 (3)0.039 (3)−0.005 (2)−0.004 (2)0.006 (2)
Geometric parameters (Å, °) top
Au—S12.3086 (12)C11—H110.9400
Au—P12.2508 (12)C12—C131.386 (8)
Cl1—C31.746 (5)C12—H120.9400
S1—C11.762 (5)C13—C141.376 (8)
P1—C211.809 (5)C13—H130.9400
P1—C151.815 (5)C14—H140.9400
P1—C91.819 (5)C15—C201.389 (7)
O1—C11.350 (6)C15—C161.395 (7)
O1—C81.433 (6)C16—C171.400 (8)
N1—C11.269 (6)C16—H160.9400
N1—C21.414 (6)C17—C181.371 (9)
C2—C71.383 (7)C17—H170.9400
C2—C31.393 (7)C18—C191.365 (9)
C3—C41.385 (7)C18—H180.9400
C4—C51.365 (8)C19—C201.396 (8)
C4—H40.9400C19—H190.9400
C5—C61.372 (8)C20—H200.9400
C5—H50.9400C21—C261.380 (7)
C6—C71.380 (7)C21—C221.393 (7)
C6—H60.9400C22—C231.378 (8)
C7—H70.9400C22—H220.9400
C8—H8A0.9700C23—C241.378 (9)
C8—H8B0.9700C23—H230.9400
C8—H8C0.9700C24—C251.372 (8)
C9—C141.390 (7)C24—H240.9400
C9—C101.391 (7)C25—C261.388 (7)
C10—C111.372 (7)C25—H250.9400
C10—H100.9400C26—H260.9400
C11—C121.376 (8)
P1—Au—S1175.09 (5)C11—C12—C13119.3 (5)
C1—S1—Au102.08 (17)C11—C12—H12120.4
C21—P1—C15104.7 (2)C13—C12—H12120.4
C21—P1—C9105.7 (2)C14—C13—C12120.5 (5)
C15—P1—C9106.0 (2)C14—C13—H13119.7
C21—P1—Au117.37 (16)C12—C13—H13119.7
C15—P1—Au112.61 (16)C13—C14—C9119.9 (5)
C9—P1—Au109.65 (16)C13—C14—H14120.1
C1—O1—C8117.1 (4)C9—C14—H14120.1
C1—N1—C2119.9 (4)C20—C15—C16119.4 (5)
N1—C1—O1119.8 (4)C20—C15—P1118.1 (4)
N1—C1—S1126.9 (4)C16—C15—P1122.5 (4)
O1—C1—S1113.2 (3)C15—C16—C17118.8 (5)
C7—C2—C3117.3 (5)C15—C16—H16120.6
C7—C2—N1121.8 (5)C17—C16—H16120.6
C3—C2—N1120.5 (5)C18—C17—C16121.4 (6)
C4—C3—C2121.4 (5)C18—C17—H17119.3
C4—C3—Cl1118.5 (4)C16—C17—H17119.3
C2—C3—Cl1120.1 (4)C19—C18—C17119.6 (6)
C5—C4—C3120.3 (5)C19—C18—H18120.2
C5—C4—H4119.9C17—C18—H18120.2
C3—C4—H4119.9C18—C19—C20120.6 (6)
C4—C5—C6119.0 (5)C18—C19—H19119.7
C4—C5—H5120.5C20—C19—H19119.7
C6—C5—H5120.5C15—C20—C19120.2 (6)
C5—C6—C7121.3 (5)C15—C20—H20119.9
C5—C6—H6119.3C19—C20—H20119.9
C7—C6—H6119.3C26—C21—C22119.6 (5)
C6—C7—C2120.7 (5)C26—C21—P1122.4 (4)
C6—C7—H7119.7C22—C21—P1118.1 (4)
C2—C7—H7119.7C23—C22—C21119.4 (5)
O1—C8—H8A109.5C23—C22—H22120.3
O1—C8—H8B109.5C21—C22—H22120.3
H8A—C8—H8B109.5C22—C23—C24120.9 (6)
O1—C8—H8C109.5C22—C23—H23119.5
H8A—C8—H8C109.5C24—C23—H23119.5
H8B—C8—H8C109.5C25—C24—C23119.9 (5)
C14—C9—C10119.4 (5)C25—C24—H24120.1
C14—C9—P1121.9 (4)C23—C24—H24120.1
C10—C9—P1118.7 (4)C24—C25—C26119.9 (5)
C11—C10—C9119.9 (5)C24—C25—H25120.1
C11—C10—H10120.1C26—C25—H25120.1
C9—C10—H10120.1C21—C26—C25120.4 (5)
C10—C11—C12120.9 (5)C21—C26—H26119.8
C10—C11—H11119.5C25—C26—H26119.8
C12—C11—H11119.5
C2—N1—C1—O1−173.1 (4)C10—C9—C14—C13−1.8 (8)
C2—N1—C1—S110.0 (7)P1—C9—C14—C13177.5 (4)
C8—O1—C1—N12.5 (7)C21—P1—C15—C2074.9 (4)
C8—O1—C1—S1179.8 (4)C9—P1—C15—C20−173.6 (4)
Au—S1—C1—N1174.2 (4)Au—P1—C15—C20−53.7 (4)
Au—S1—C1—O1−2.9 (4)C21—P1—C15—C16−104.3 (4)
C1—N1—C2—C760.3 (7)C9—P1—C15—C167.2 (5)
C1—N1—C2—C3−126.3 (5)Au—P1—C15—C16127.1 (4)
C7—C2—C3—C4−1.1 (7)C20—C15—C16—C17−0.7 (8)
N1—C2—C3—C4−174.9 (5)P1—C15—C16—C17178.4 (4)
C7—C2—C3—Cl1179.8 (4)C15—C16—C17—C180.1 (9)
N1—C2—C3—Cl16.1 (7)C16—C17—C18—C190.6 (10)
C2—C3—C4—C50.1 (8)C17—C18—C19—C20−0.7 (10)
Cl1—C3—C4—C5179.2 (4)C16—C15—C20—C190.6 (8)
C3—C4—C5—C60.0 (9)P1—C15—C20—C19−178.6 (4)
C4—C5—C6—C71.0 (9)C18—C19—C20—C150.1 (9)
C5—C6—C7—C2−2.0 (9)C15—P1—C21—C269.0 (5)
C3—C2—C7—C62.1 (8)C9—P1—C21—C26−102.7 (4)
N1—C2—C7—C6175.7 (5)Au—P1—C21—C26134.7 (4)
C21—P1—C9—C1422.3 (5)C15—P1—C21—C22−172.6 (4)
C15—P1—C9—C14−88.5 (5)C9—P1—C21—C2275.7 (4)
Au—P1—C9—C14149.7 (4)Au—P1—C21—C22−46.9 (4)
C21—P1—C9—C10−158.4 (4)C26—C21—C22—C231.7 (8)
C15—P1—C9—C1090.8 (4)P1—C21—C22—C23−176.7 (4)
Au—P1—C9—C10−31.0 (5)C21—C22—C23—C24−1.8 (9)
C14—C9—C10—C113.2 (8)C22—C23—C24—C250.8 (9)
P1—C9—C10—C11−176.1 (4)C23—C24—C25—C260.3 (9)
C9—C10—C11—C12−1.8 (9)C22—C21—C26—C25−0.6 (8)
C10—C11—C12—C13−0.9 (9)P1—C21—C26—C25177.7 (4)
C11—C12—C13—C142.3 (9)C24—C25—C26—C21−0.3 (8)
C12—C13—C14—C9−0.9 (9)
Table 1
Selected geometric parameters (Å) top
Au—S12.3086 (12)Au—P12.2508 (12)
Acknowledgements top

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

references
References top

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. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Bruker (2000). SMART, SAINT and SADABS. 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.

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.

Westrip, S. P. (2009). publCIF. In preparation.