(N,N-Diethyl­di­thio­carbamato)[tris(p-methoxy­phenyl)­phosphine]­gold(I)

Sulfur- and phospho­rus-donor atoms define an approximately linear geometry about the Au atom in the title compound, [Au(S₂CNEt₂){(p-MeO-C₆H₄)₃P}]. The key geometric parameters are Au—S 2.3350 (8) Å, Au—P 2.2528 (7) Å and an S—Au—P angle of 169.80 (3)°. The deviation from linearity is ascribed to a close intramolecular Au...S contact of 3.0564 (8) Å.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.033
• wR factor = 0.078
• Data-to-parameter ratio = 25.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Intramolecuar Au···S or Au···O interactions are found in structures with the general formula R₃PAu(S₂COR') (R, R' = alkyl, aryl) and are thought to be dictated by global crystal-packing considerations (Siasios & Tiekink, 1993a,b). Analogous Au···S interactions are found in the related crystal structures of (C₆H₅)₃PAu(S₂CNEt₂), (II) (Wijnhoven et al., 1972), (c-C₆H₁₁)₃PAu(S₂CNEt₂), (III) (Ho & Tiekink, 2001b), and dinuclear (Et₂NCS₂)AuP(C₆H₅)₂CH₂CH₂(C₆H₅)₂PAu(S₂CNEt₂), (IV) (Faamau & Tiekink, 1994). In connection with the above, the structure of the title compound, (p-MeO-C₆H₄)₃PAu(S₂CNEt₂), (I), was determined.

A linear geometry defined by sulfur, derived from a monodentate dithiocarbamate ligand, and P atoms, from the phosphine, is found in (I) (Fig. 1 and Table 1). The Au—S and Au—P separations of 2.3350 (8) and 2.2528 (7) Å, respectively, lie within the range of Au—S and Au—P distances found in the mononuclear structures of (II) and (III) mentioned above. To a first approximation, the geometry is linear but a significant distortion away from the ideal angle of 180° is noted as the S—Au—P angle is 169.80 (3)°. This may be correlated with the close approach of the non-coordinating S2 atom to the Au centre so that Au···S is 3.0564 (8) Å. This separation lies between the comparable Au···S separations found in (II) and (III), for which the angles subtended at gold were found to be 175.7 (1) and 171.61 (4)°, respectively.

There are two C—H···π contacts less than 3.2 Å. These occur between the methylene C4—H and the centroid of the C6—C11 ring (distance 2.95 Å and angle at H of 125° with symmetry operation 1 + x, y, z) and C17—H with the centroid of the C20—C25 ring (3.12 Å, 152° and x, 1/2 - y, -1/2 + z).

S2. Experimental

To a dichloromethane solution (4 ml) of (p-MeO-C₆H₄)₃PAuCl (0.20 g, 0.34 mmol; Ho & Tiekink, 2001a) was added NaS₂CNEt₂ (Merck; 58 mg, 0.34 mmol). The colourless solution immediately turned yellow indicating the formation of the product and was stirred for 2 h. The yellow solution was filtered through Celite and concentrated to approximately 1 ml to yield the product. The product was recrystallized by the vapour diffusion of methanol into a chloroform solution of the compound to yield X-ray quality pale-yellow crystals (168 mg, 71%); m.p. 404 K. ¹H NMR (CDCl₃): δ 7.57–7.49 (m, 6H, Ph), 6.95–6.91 (m, 6H, Ph), 3.93 (q, 4H, J = 7.5 Hz), 3.82 (s, 9H, OCH₃), 1.33 p.p.m. (t, 6H, J = 7.5 Hz). ³¹P{¹H} (CDCl₃): δ 32.5 p.p.m. ESI-MS: m/z 1247 [(M⁺—NEt₂)]₂. IR (KBr) 1499 ν(C—N), 1105 and 995 ν(C—S) cm^-1.

S3. Refinement

The C-bound H atoms were placed in their geometrically calculated positions and included in the final refinement in the riding-model approximation with an overall displacement parameter, U_iso, with U_iso for phenyl H, 1.25U_iso for methylene H and 1.5U_iso for CH₃ H atoms. The residual electron-density peak is located in the vicinity of the Au atom.

Computing details

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, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHEXLTL.

Figures

Fig. 1. The molecular structure and crystallographic numbering scheme for (I). Displacement ellipsoids are shown at the 50% probability level.

(I)

Crystal data

[Au(C5H10NS2)(C21H21O3P)]	F(000) = 1376
Mr = 697.57	Dx = 1.727 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 21862 reflections
a = 10.4567 (4) Å	θ = 1.8–30.0°
b = 15.6672 (7) Å	µ = 5.73 mm^−1
c = 17.0037 (7) Å	T = 223 K
β = 105.576 (1)°	Block, pale-yellow
V = 2683.36 (19) Å^3	0.42 × 0.10 × 0.10 mm
Z = 4

Data collection

Bruker AXS SMART CCD diffractometer	7806 independent reflections
Radiation source: fine-focus sealed tube	6349 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω scans	θmax = 30.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS, Bruker, 2000)	h = −14→14
Tmin = 0.218, Tmax = 0.564	k = −22→10
21862 measured reflections	l = −23→23

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0366P)^2] where P = (Fo^2 + 2Fc^2)/3
7806 reflections	(Δ/σ)max = 0.001
308 parameters	Δρmax = 2.14 e Å^−3
0 restraints	Δρmin = −1.26 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Au	0.253610 (11)	0.108658 (8)	0.285428 (7)	0.03034 (5)
S1	0.46076 (8)	0.07925 (6)	0.26427 (6)	0.03776 (19)
S2	0.32699 (10)	−0.08061 (7)	0.29502 (7)	0.0497 (2)
P1	0.05945 (7)	0.16064 (6)	0.29844 (5)	0.02776 (17)
O1	−0.2328 (2)	−0.06842 (16)	0.46939 (14)	0.0382 (5)
O2	−0.3150 (3)	0.23938 (18)	−0.02588 (14)	0.0451 (6)
O3	0.1353 (2)	0.49484 (16)	0.47388 (15)	0.0412 (6)
N1	0.5472 (3)	−0.0759 (2)	0.24463 (18)	0.0397 (7)
C1	0.4516 (3)	−0.0328 (2)	0.26652 (19)	0.0335 (7)
C2	0.5483 (4)	−0.1701 (3)	0.2446 (3)	0.0504 (10)
H2A	0.5906	−0.1905	0.2032	0.051 (2)*
H2B	0.4567	−0.1912	0.2301	0.051 (2)*
C3	0.6219 (5)	−0.2052 (3)	0.3269 (3)	0.0606 (12)
H3A	0.6211	−0.2671	0.3248	0.062 (3)*
H3B	0.5790	−0.1861	0.3678	0.062 (3)*
H3C	0.7129	−0.1850	0.3411	0.062 (3)*
C4	0.6530 (3)	−0.0341 (3)	0.2165 (2)	0.0490 (10)
H4A	0.7315	−0.0711	0.2285	0.051 (2)*
H4B	0.6778	0.0195	0.2465	0.051 (2)*
C5	0.6097 (4)	−0.0155 (3)	0.1257 (3)	0.0608 (12)
H5A	0.6820	0.0114	0.1094	0.062 (3)*
H5B	0.5336	0.0225	0.1139	0.062 (3)*
H5C	0.5856	−0.0684	0.0958	0.062 (3)*
C6	−0.0265 (3)	0.0929 (2)	0.35418 (18)	0.0267 (6)
C7	−0.0019 (3)	0.0053 (2)	0.36057 (18)	0.0290 (6)
H7	0.0631	−0.0184	0.3382	0.0411 (17)*
C8	−0.0716 (3)	−0.0466 (2)	0.39905 (18)	0.0305 (7)
H8	−0.0539	−0.1055	0.4033	0.0411 (17)*
C9	−0.1686 (3)	−0.0123 (2)	0.43189 (18)	0.0288 (6)
C10	−0.1939 (3)	0.0743 (2)	0.42636 (19)	0.0300 (6)
H10	−0.2597	0.0976	0.4483	0.0411 (17)*
C11	−0.1219 (3)	0.1266 (2)	0.38838 (19)	0.0286 (6)
H11	−0.1378	0.1858	0.3858	0.0411 (17)*
C12	−0.3418 (4)	−0.0358 (3)	0.4969 (2)	0.0454 (9)
H12A	−0.3789	−0.0813	0.5226	0.062 (3)*
H12B	−0.4096	−0.0138	0.4507	0.062 (3)*
H12C	−0.3105	0.0097	0.5361	0.062 (3)*
C13	−0.0581 (3)	0.1809 (2)	0.20087 (18)	0.0290 (6)
C14	−0.1937 (3)	0.1886 (3)	0.1924 (2)	0.0430 (9)
H14	−0.2262	0.1800	0.2382	0.0411 (17)*
C15	−0.2816 (3)	0.2085 (3)	0.1184 (2)	0.0418 (9)
H15	−0.3725	0.2147	0.1145	0.0411 (17)*
C16	−0.2358 (3)	0.2194 (2)	0.0501 (2)	0.0337 (7)
C17	−0.1014 (3)	0.2104 (3)	0.0572 (2)	0.0431 (9)
H17	−0.0696	0.2178	0.0109	0.0411 (17)*
C18	−0.0143 (3)	0.1910 (2)	0.1305 (2)	0.0380 (8)
H18	0.0763	0.1843	0.1338	0.0411 (17)*
C19	−0.4478 (4)	0.2637 (3)	−0.0308 (2)	0.0543 (11)
H19A	−0.4938	0.2768	−0.0870	0.062 (3)*
H19B	−0.4475	0.3136	0.0030	0.062 (3)*
H19C	−0.4928	0.2171	−0.0116	0.062 (3)*
C20	0.0797 (3)	0.2620 (2)	0.35186 (18)	0.0273 (6)
C21	0.1594 (3)	0.2661 (2)	0.4318 (2)	0.0324 (7)
H21	0.2001	0.2160	0.4572	0.0411 (17)*
C22	0.1801 (3)	0.3425 (2)	0.4751 (2)	0.0342 (7)
H22	0.2344	0.3438	0.5290	0.0411 (17)*
C23	0.1207 (3)	0.4162 (2)	0.4384 (2)	0.0314 (7)
C24	0.0410 (4)	0.4133 (2)	0.3586 (2)	0.0410 (8)
H24	0.0006	0.4636	0.3334	0.0411 (17)*
C25	0.0205 (3)	0.3371 (2)	0.3158 (2)	0.0368 (8)
H25	−0.0339	0.3361	0.2619	0.0411 (17)*
C26	0.2102 (4)	0.5013 (3)	0.5563 (2)	0.0518 (10)
H26A	0.2130	0.5604	0.5737	0.062 (3)*
H26B	0.2998	0.4811	0.5617	0.062 (3)*
H26C	0.1691	0.4668	0.5902	0.062 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au	0.02452 (7)	0.03545 (8)	0.03282 (7)	0.00610 (5)	0.01078 (5)	0.00062 (5)
S1	0.0274 (4)	0.0366 (5)	0.0528 (5)	0.0053 (4)	0.0168 (4)	0.0001 (4)
S2	0.0387 (5)	0.0437 (5)	0.0709 (7)	−0.0003 (4)	0.0220 (5)	−0.0021 (5)
P1	0.0241 (3)	0.0298 (4)	0.0312 (4)	0.0044 (3)	0.0106 (3)	0.0016 (3)
O1	0.0408 (13)	0.0359 (14)	0.0397 (12)	−0.0054 (11)	0.0138 (10)	0.0065 (11)
O2	0.0451 (14)	0.0529 (17)	0.0336 (12)	0.0053 (13)	0.0039 (11)	0.0077 (12)
O3	0.0493 (14)	0.0327 (13)	0.0435 (13)	−0.0010 (12)	0.0158 (11)	−0.0069 (11)
N1	0.0327 (14)	0.0383 (17)	0.0468 (17)	0.0099 (14)	0.0087 (13)	−0.0099 (14)
C1	0.0281 (14)	0.0358 (19)	0.0358 (16)	0.0082 (14)	0.0071 (12)	−0.0046 (15)
C2	0.047 (2)	0.043 (2)	0.058 (2)	0.0076 (19)	0.0103 (18)	−0.020 (2)
C3	0.066 (3)	0.037 (2)	0.072 (3)	0.013 (2)	0.006 (2)	−0.012 (2)
C4	0.0287 (16)	0.067 (3)	0.054 (2)	0.0093 (18)	0.0155 (16)	−0.010 (2)
C5	0.051 (2)	0.079 (3)	0.058 (3)	0.006 (2)	0.024 (2)	−0.012 (2)
C6	0.0260 (13)	0.0284 (16)	0.0257 (14)	0.0012 (12)	0.0067 (11)	0.0019 (12)
C7	0.0251 (13)	0.0309 (17)	0.0290 (14)	0.0035 (13)	0.0037 (11)	−0.0050 (13)
C8	0.0316 (15)	0.0233 (15)	0.0325 (15)	0.0001 (13)	0.0015 (12)	−0.0012 (13)
C9	0.0283 (14)	0.0302 (17)	0.0252 (14)	−0.0039 (13)	0.0024 (11)	0.0015 (13)
C10	0.0302 (15)	0.0308 (17)	0.0308 (15)	0.0024 (14)	0.0115 (12)	−0.0025 (13)
C11	0.0317 (15)	0.0249 (16)	0.0302 (15)	0.0041 (13)	0.0101 (12)	0.0001 (13)
C12	0.045 (2)	0.053 (3)	0.0417 (19)	−0.0081 (19)	0.0189 (16)	0.0039 (18)
C13	0.0273 (14)	0.0304 (17)	0.0305 (14)	0.0036 (13)	0.0100 (12)	0.0005 (13)
C14	0.0317 (16)	0.067 (3)	0.0317 (16)	0.0077 (17)	0.0110 (13)	0.0033 (17)
C15	0.0292 (15)	0.057 (2)	0.0394 (18)	0.0064 (16)	0.0089 (14)	0.0048 (17)
C16	0.0363 (16)	0.0290 (17)	0.0337 (16)	0.0017 (14)	0.0057 (13)	0.0043 (14)
C17	0.0441 (19)	0.054 (2)	0.0375 (18)	0.0066 (18)	0.0213 (16)	0.0127 (17)
C18	0.0325 (16)	0.046 (2)	0.0390 (17)	0.0070 (15)	0.0163 (14)	0.0081 (16)
C19	0.045 (2)	0.066 (3)	0.044 (2)	0.007 (2)	−0.0038 (17)	0.004 (2)
C20	0.0221 (13)	0.0304 (16)	0.0324 (15)	0.0009 (12)	0.0127 (11)	0.0017 (13)
C21	0.0323 (15)	0.0288 (17)	0.0358 (16)	0.0049 (14)	0.0089 (13)	0.0051 (14)
C22	0.0310 (15)	0.039 (2)	0.0313 (16)	0.0010 (14)	0.0056 (13)	0.0007 (14)
C23	0.0291 (15)	0.0305 (17)	0.0382 (17)	−0.0015 (13)	0.0151 (13)	−0.0011 (14)
C24	0.047 (2)	0.0325 (18)	0.0407 (19)	0.0079 (16)	0.0078 (16)	0.0052 (16)
C25	0.0375 (17)	0.0359 (19)	0.0335 (16)	0.0035 (15)	0.0033 (14)	0.0026 (15)
C26	0.056 (2)	0.047 (2)	0.049 (2)	0.001 (2)	0.0097 (19)	−0.014 (2)

Geometric parameters (Å, º)

Au—P1	2.2528 (7)	C9—C10	1.380 (5)
Au—S1	2.3350 (8)	C10—C11	1.385 (4)
S1—C1	1.760 (4)	C10—H10	0.9400
S2—C1	1.683 (3)	C11—H11	0.9400
P1—C13	1.808 (3)	C12—H12A	0.9700
P1—C6	1.814 (3)	C12—H12B	0.9700
P1—C20	1.813 (3)	C12—H12C	0.9700
O1—C9	1.364 (4)	C13—C14	1.391 (4)
O1—C12	1.438 (4)	C13—C18	1.400 (4)
O2—C16	1.371 (4)	C14—C15	1.380 (5)
O2—C19	1.420 (4)	C14—H14	0.9400
O3—C23	1.362 (4)	C15—C16	1.380 (5)
O3—C26	1.414 (4)	C15—H15	0.9400
N1—C1	1.339 (4)	C16—C17	1.385 (4)
N1—C4	1.471 (5)	C17—C18	1.366 (5)
N1—C2	1.476 (5)	C17—H17	0.9400
C2—C3	1.508 (6)	C18—H18	0.9400
C2—H2A	0.9800	C19—H19A	0.9700
C2—H2B	0.9800	C19—H19B	0.9700
C3—H3A	0.9700	C19—H19C	0.9700
C3—H3B	0.9700	C20—C25	1.393 (5)
C3—H3C	0.9700	C20—C21	1.393 (4)
C4—C5	1.516 (6)	C21—C22	1.390 (5)
C4—H4A	0.9800	C21—H21	0.9400
C4—H4B	0.9800	C22—C23	1.379 (5)
C5—H5A	0.9700	C22—H22	0.9400
C5—H5B	0.9700	C23—C24	1.391 (5)
C5—H5C	0.9700	C24—C25	1.384 (5)
C6—C11	1.386 (4)	C24—H24	0.9400
C6—C7	1.396 (4)	C25—H25	0.9400
C7—C8	1.369 (4)	C26—H26A	0.9700
C7—H7	0.9400	C26—H26B	0.9700
C8—C9	1.390 (4)	C26—H26C	0.9700
C8—H8	0.9400
P1—Au—S1	169.80 (3)	C6—C11—H11	119.6
C1—S1—Au	97.80 (11)	C10—C11—H11	119.6
C13—P1—C6	105.77 (14)	O1—C12—H12A	109.5
C13—P1—C20	105.36 (15)	O1—C12—H12B	109.5
C6—P1—C20	104.94 (14)	H12A—C12—H12B	109.5
C13—P1—Au	112.46 (10)	O1—C12—H12C	109.5
C6—P1—Au	115.23 (11)	H12A—C12—H12C	109.5
C20—P1—Au	112.26 (9)	H12B—C12—H12C	109.5
C9—O1—C12	117.1 (3)	C14—C13—C18	117.4 (3)
C16—O2—C19	116.8 (3)	C14—C13—P1	122.2 (2)
C23—O3—C26	118.0 (3)	C18—C13—P1	120.4 (2)
C1—N1—C4	123.2 (3)	C15—C14—C13	121.7 (3)
C1—N1—C2	120.7 (3)	C15—C14—H14	119.2
C4—N1—C2	116.1 (3)	C13—C14—H14	119.2
N1—C1—S2	123.3 (3)	C14—C15—C16	119.9 (3)
N1—C1—S1	116.6 (3)	C14—C15—H15	120.1
S2—C1—S1	120.05 (18)	C16—C15—H15	120.1
N1—C2—C3	111.5 (3)	O2—C16—C17	116.6 (3)
N1—C2—H2A	109.3	O2—C16—C15	124.2 (3)
C3—C2—H2A	109.3	C17—C16—C15	119.2 (3)
N1—C2—H2B	109.3	C18—C17—C16	120.9 (3)
C3—C2—H2B	109.3	C18—C17—H17	119.5
H2A—C2—H2B	108.0	C16—C17—H17	119.5
C2—C3—H3A	109.5	C17—C18—C13	121.0 (3)
C2—C3—H3B	109.5	C17—C18—H18	119.5
H3A—C3—H3B	109.5	C13—C18—H18	119.5
C2—C3—H3C	109.5	O2—C19—H19A	109.5
H3A—C3—H3C	109.5	O2—C19—H19B	109.5
H3B—C3—H3C	109.5	H19A—C19—H19B	109.5
N1—C4—C5	111.8 (3)	O2—C19—H19C	109.5
N1—C4—H4A	109.3	H19A—C19—H19C	109.5
C5—C4—H4A	109.3	H19B—C19—H19C	109.5
N1—C4—H4B	109.3	C25—C20—C21	118.0 (3)
C5—C4—H4B	109.3	C25—C20—P1	122.8 (2)
H4A—C4—H4B	107.9	C21—C20—P1	119.2 (2)
C4—C5—H5A	109.5	C22—C21—C20	121.5 (3)
C4—C5—H5B	109.5	C22—C21—H21	119.2
H5A—C5—H5B	109.5	C20—C21—H21	119.2
C4—C5—H5C	109.5	C21—C22—C23	119.7 (3)
H5A—C5—H5C	109.5	C21—C22—H22	120.2
H5B—C5—H5C	109.5	C23—C22—H22	120.2
C11—C6—C7	118.7 (3)	O3—C23—C24	115.3 (3)
C11—C6—P1	120.6 (2)	O3—C23—C22	125.1 (3)
C7—C6—P1	120.6 (2)	C24—C23—C22	119.6 (3)
C8—C7—C6	120.7 (3)	C23—C24—C25	120.6 (3)
C8—C7—H7	119.7	C23—C24—H24	119.7
C6—C7—H7	119.7	C25—C24—H24	119.7
C7—C8—C9	120.1 (3)	C20—C25—C24	120.6 (3)
C7—C8—H8	119.9	C20—C25—H25	119.7
C9—C8—H8	119.9	C24—C25—H25	119.7
O1—C9—C10	123.8 (3)	O3—C26—H26A	109.5
O1—C9—C8	116.2 (3)	O3—C26—H26B	109.5
C10—C9—C8	120.0 (3)	H26A—C26—H26B	109.5
C9—C10—C11	119.7 (3)	O3—C26—H26C	109.5
C9—C10—H10	120.2	H26A—C26—H26C	109.5
C11—C10—H10	120.2	H26B—C26—H26C	109.5
C6—C11—C10	120.8 (3)