(4,6-Di­methyl­pyrimidine-2-thiol­ato)(tri­phenyl­phosphine)­gold(I)

The title compound, [Au(4,6-Me₂pymS)(PPh₃)] or [Au(C₆H₇N₂S)(C₁₈H₁₅P)], exhibits a linear Au atom S—Au—P geometry, with Au—P = 2.247 (2) Å, Au—S = 2.289 (2) Å and P—Au—S = 178.19 (11)°. There is an intramolecular interaction between one N atom of the 4,6-Me₂pymS ligand and the Au atom, with an Au...N distance of 3.154 (8) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.015 Å
• R factor = 0.047
• wR factor = 0.100
• Data-to-parameter ratio = 18.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The preparation of the novel two triphenylphosphanegold(I) complexes of the anions derived from pyridine-2-thione (2-pySH) and 1H-pyrimidine-2-thione (2-pymSH) have been recently reported with their X-ray crystal structures determination (Cookson & Tiekink, 1993). In this paper, we report the preparation, structural characterization, and some observations about the title compound, (I).

The anionic 4,6-Me₂pymS ligand is coordinated via the S atom (Fig. 1 and Table 1). The Au—S bond length and S—Au—P angle in (I) are close to those found for the two complexes [Au(2-pyS)(PPh₃)] [2.297 (2) Å and 177.9 (1)°, respectively] and [Au(2-pymS)(PPh₃)] [2.310 (3) Å and 174.7 (1)°, respectively]. The Au atom shows nearly linear coordination with the S and P atoms, despite a fairly close intermolecular interaction with an N atom of the 4,6-Me₂pymS ligand. This interaction Au1···N42 of 3.154 (8) Å, is slightly less than the sum of the van der Waals radii (Pauling, 1960) of the Au and N atoms, 3.25 Å. Given the linearity of the S–Au–P angle, the 4,6-Me₂pymS ligand appears to be ligating essentially in the monodentate mode through its S atom. There is no metal–metal interaction in the solid state but a weak intermolecular C—H···N hydrogen bond is present (Desiraju & Steiner, 1999). three-centered hydrogen bond exists between atom N46 and the H atoms of two phenyl groups of different molecules (Table 2).

In CDCl₃ solution at room temperature, the ¹H NMR data shows inequivalent methyl groups for the anionic 4,6-Me₂pymS ligand. This suggests that the ligand is not permitted to rotate freely in solution, which is consistent with the persistence of the intramolecular interaction between the N atom of the ligand and the Au atom.

S2. Experimental

The compound 4,6-dimethylpyrimidine-2(1H)-thione (4,6-Me₂pymSH) was prepared according to the literature method (Nigam et al., 1983) and the title complex was synthesized by the following procedure: 0.28 g (2 mmol) of 4,6-Me₂pymSH was dissolved in 30 ml of THF (freshly distilled) in a Schlenk tube kept under N₂ atmosphere. To the solution, 0.84 ml (6 mmol) of triethylamine, NEt₃, was added and the resulting mixture was stirred for 30 min. To this solution, 0.99 g (2 mmol) of [AuClP(Ph₃)] dissolved in 10 ml of THF was added, over a period of 10 min, and the mixture was stirred for about 3 h. A white flocculent precipitate was filtered off and identified as triethylamine hydrochloride, [(HNEt₃)Cl]. Slow evaporation of the solvent led to the appearance of a white microcrystalline solid [yield 1.0 g (92%)]. Well developed crystals of (I) suitable for X-ray analysis were obtained by recrystallization from a 1:1 (v/v) mixture of dichloromethane and n-hexane (m.p. 470–472 K).

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: SET4 in CAD-4 Software; data reduction: HELENA (Spek, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. View of molecule (I) with the atomic labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

(4,6-Dimethylpyrimidine-2-thiolato)triphenylphosphanegold(I)

Crystal data

[Au(C6H7N2S)(C18H15P)]	Z = 2
Mr = 598.43	F(000) = 580
Triclinic, P1	Dx = 1.730 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8282 (17) Å	Cell parameters from 25 reflections
b = 11.144 (2) Å	θ = 7.3–15.2°
c = 12.318 (3) Å	µ = 6.58 mm^−1
α = 97.104 (19)°	T = 293 K
β = 105.586 (18)°	Block, colorless
γ = 95.05 (2)°	0.20 × 0.15 × 0.10 mm
V = 1148.9 (4) Å^3

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.089
Graphite monochromator	θmax = 27.0°, θmin = 3.1°
ω/2θ scans	h = −11→11
Absorption correction: ψ scan (ABSPSI routine in PLATON; Spek, 1995)	k = −14→14
Tmin = 0.318, Tmax = 0.518	l = −15→15
8437 measured reflections	3 standard reflections every 300 reflections
5002 independent reflections	intensity decay: 12.4%
2962 reflections with I > 2σ(I)

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0366P)^2] where P = (Fo^2 + 2Fc^2)/3
5002 reflections	(Δ/σ)max = 0.016
264 parameters	Δρmax = 0.88 e Å^−3
0 restraints	Δρmin = −1.43 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
Au1	0.12719 (5)	0.01807 (3)	0.33320 (4)	0.04768 (13)
P1	0.0603 (3)	0.19773 (18)	0.3973 (2)	0.0412 (6)
C11	0.1190 (9)	0.3162 (7)	0.3212 (8)	0.044 (2)
C12	0.0856 (12)	0.2900 (8)	0.2039 (9)	0.062 (3)
H12	0.0373	0.2129	0.1665	0.074*
C13	0.1231 (14)	0.3775 (11)	0.1421 (10)	0.082 (3)
H13	0.0965	0.3606	0.0629	0.099*
C14	0.2003 (14)	0.4897 (9)	0.1984 (11)	0.075 (3)
H14	0.2282	0.5485	0.1575	0.090*
C15	0.2355 (13)	0.5143 (8)	0.3128 (12)	0.074 (3)
H15	0.2890	0.5902	0.3499	0.089*
C16	0.1936 (11)	0.4285 (7)	0.3775 (9)	0.057 (3)
H16	0.2159	0.4473	0.4563	0.069*
C21	−0.1516 (9)	0.1998 (7)	0.3777 (7)	0.0393 (19)
C22	−0.2205 (11)	0.3069 (8)	0.3699 (8)	0.052 (2)
H22	−0.1584	0.3807	0.3762	0.062*
C23	−0.3832 (13)	0.3027 (12)	0.3526 (10)	0.075 (3)
H23	−0.4302	0.3741	0.3479	0.090*
C24	−0.4722 (13)	0.1965 (13)	0.3428 (10)	0.082 (3)
H24	−0.5811	0.1956	0.3299	0.099*
C25	−0.4085 (12)	0.0881 (11)	0.3512 (9)	0.074 (3)
H25	−0.4730	0.0155	0.3447	0.089*
C26	−0.2459 (11)	0.0900 (8)	0.3697 (8)	0.058 (3)
H26	−0.2001	0.0183	0.3767	0.070*
C31	0.1562 (10)	0.2533 (7)	0.5460 (8)	0.044 (2)
C32	0.3148 (12)	0.2374 (8)	0.5904 (10)	0.062 (3)
H32	0.3670	0.1953	0.5445	0.074*
C33	0.3925 (12)	0.2832 (10)	0.7004 (10)	0.069 (3)
H33	0.4991	0.2744	0.7287	0.083*
C34	0.3165 (14)	0.3422 (10)	0.7707 (10)	0.076 (3)
H34	0.3707	0.3725	0.8463	0.091*
C35	0.1593 (14)	0.3563 (10)	0.7282 (10)	0.079 (3)
H35	0.1059	0.3962	0.7746	0.095*
C36	0.0829 (12)	0.3107 (8)	0.6170 (9)	0.060 (3)
H36	−0.0238	0.3193	0.5888	0.072*
S1	0.2033 (4)	−0.1631 (2)	0.2715 (3)	0.0678 (8)
C41	0.2393 (9)	−0.1429 (7)	0.1417 (8)	0.047 (2)
N42	0.2222 (8)	−0.0352 (6)	0.1043 (7)	0.0515 (19)
C43	0.2557 (11)	−0.0261 (8)	0.0062 (9)	0.057 (2)
C44	0.3061 (13)	−0.1215 (9)	−0.0503 (8)	0.067 (3)
H44	0.3325	−0.1132	−0.1174	0.080*
C431	0.2333 (14)	0.0916 (10)	−0.0381 (10)	0.087 (4)
H43A	0.1266	0.0876	−0.0856	0.130*
H43B	0.3060	0.1064	−0.0820	0.130*
H43C	0.2529	0.1567	0.0247	0.130*
C45	0.3174 (13)	−0.2289 (9)	−0.0075 (9)	0.064 (3)
C451	0.3623 (17)	−0.3385 (10)	−0.0653 (10)	0.098 (4)
H45A	0.4524	−0.3158	−0.0915	0.148*
H45B	0.2751	−0.3756	−0.1292	0.148*
H45C	0.3888	−0.3954	−0.0128	0.148*
N46	0.2823 (9)	−0.2391 (6)	0.0898 (7)	0.054 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.0466 (2)	0.03640 (17)	0.0677 (3)	0.00784 (13)	0.02587 (17)	0.01328 (14)
P1	0.0348 (13)	0.0367 (11)	0.0559 (16)	0.0047 (9)	0.0171 (12)	0.0117 (10)
C11	0.032 (5)	0.037 (4)	0.070 (7)	0.011 (3)	0.019 (5)	0.018 (4)
C12	0.066 (7)	0.057 (6)	0.063 (7)	−0.002 (5)	0.019 (6)	0.016 (5)
C13	0.093 (9)	0.090 (8)	0.071 (8)	0.003 (7)	0.026 (7)	0.035 (7)
C14	0.091 (9)	0.062 (7)	0.097 (10)	0.021 (6)	0.054 (8)	0.042 (7)
C15	0.075 (8)	0.040 (5)	0.119 (11)	0.000 (5)	0.050 (8)	0.012 (6)
C16	0.067 (7)	0.037 (5)	0.075 (7)	0.004 (4)	0.033 (6)	0.009 (5)
C21	0.029 (4)	0.053 (5)	0.036 (5)	0.001 (4)	0.009 (4)	0.007 (4)
C22	0.046 (6)	0.053 (5)	0.058 (6)	0.007 (4)	0.017 (5)	0.011 (4)
C23	0.048 (7)	0.102 (9)	0.077 (9)	0.024 (6)	0.015 (6)	0.015 (7)
C24	0.039 (6)	0.129 (11)	0.075 (9)	0.007 (7)	0.012 (6)	0.016 (8)
C25	0.040 (6)	0.100 (8)	0.083 (9)	−0.008 (6)	0.017 (6)	0.027 (7)
C26	0.045 (6)	0.064 (6)	0.069 (7)	−0.009 (4)	0.022 (5)	0.020 (5)
C31	0.035 (5)	0.039 (4)	0.061 (6)	0.003 (4)	0.016 (5)	0.015 (4)
C32	0.051 (6)	0.061 (6)	0.073 (8)	0.017 (5)	0.011 (6)	0.020 (5)
C33	0.031 (6)	0.086 (7)	0.074 (8)	0.001 (5)	−0.012 (6)	0.012 (6)
C34	0.073 (8)	0.088 (8)	0.057 (8)	−0.007 (6)	0.010 (7)	0.000 (6)
C35	0.060 (8)	0.099 (8)	0.074 (9)	0.011 (6)	0.018 (7)	−0.001 (7)
C36	0.050 (6)	0.070 (6)	0.055 (7)	−0.001 (5)	0.014 (6)	−0.006 (5)
S1	0.097 (2)	0.0404 (12)	0.091 (2)	0.0262 (13)	0.0551 (18)	0.0249 (13)
C41	0.031 (5)	0.041 (5)	0.061 (6)	0.001 (4)	0.000 (4)	0.009 (4)
N42	0.041 (4)	0.046 (4)	0.063 (6)	0.000 (3)	0.008 (4)	0.008 (4)
C43	0.048 (6)	0.062 (6)	0.058 (7)	−0.001 (5)	0.006 (5)	0.017 (5)
C44	0.075 (8)	0.081 (7)	0.036 (6)	0.006 (6)	0.004 (5)	0.009 (5)
C431	0.091 (9)	0.093 (8)	0.088 (9)	0.019 (7)	0.029 (7)	0.045 (7)
C45	0.070 (7)	0.063 (6)	0.055 (7)	0.010 (5)	0.014 (6)	0.001 (5)
C451	0.134 (12)	0.096 (9)	0.057 (8)	0.024 (8)	0.019 (8)	−0.006 (6)
N46	0.048 (5)	0.054 (4)	0.055 (6)	0.004 (4)	0.010 (4)	−0.002 (4)

Geometric parameters (Å, º)

Au1—P1	2.247 (2)	C31—C36	1.352 (12)
Au1—S1	2.289 (2)	C31—C32	1.396 (12)
Au1—N42	3.154 (8)	C32—C33	1.355 (13)
P1—C31	1.802 (9)	C32—H32	0.9300
P1—C21	1.823 (8)	C33—C34	1.372 (15)
P1—C11	1.827 (8)	C33—H33	0.9300
C11—C16	1.370 (11)	C34—C35	1.375 (14)
C11—C12	1.382 (12)	C34—H34	0.9300
C12—C13	1.379 (13)	C35—C36	1.364 (13)
C12—H12	0.9300	C35—H35	0.9300
C13—C14	1.375 (15)	C36—H36	0.9300
C13—H13	0.9300	S1—C41	1.749 (10)
C14—C15	1.346 (14)	C41—N46	1.316 (10)
C14—H14	0.9300	C41—N42	1.344 (10)
C15—C16	1.404 (13)	N42—C43	1.332 (12)
C15—H15	0.9300	C43—C44	1.371 (13)
C16—H16	0.9300	C43—C431	1.492 (13)
C21—C22	1.388 (11)	C44—C45	1.367 (13)
C21—C26	1.396 (11)	C44—H44	0.9300
C22—C23	1.390 (13)	C431—H43A	0.9600
C22—H22	0.9300	C431—H43B	0.9600
C23—C24	1.335 (15)	C431—H43C	0.9600
C23—H23	0.9300	C45—N46	1.332 (12)
C24—C25	1.380 (15)	C45—C451	1.476 (14)
C24—H24	0.9300	C451—H45A	0.9600
C25—C26	1.390 (13)	C451—H45B	0.9600
C25—H25	0.9300	C451—H45C	0.9600
C26—H26	0.9300
P1—Au1—S1	178.19 (11)	C36—C31—P1	123.5 (7)
P1—Au1—N42	123.97 (14)	C32—C31—P1	118.4 (7)
S1—Au1—N42	56.27 (14)	C33—C32—C31	119.9 (10)
C31—P1—C21	106.3 (4)	C33—C32—H32	120.0
C31—P1—C11	105.1 (4)	C31—C32—H32	120.0
C21—P1—C11	105.5 (4)	C32—C33—C34	121.0 (10)
C31—P1—Au1	114.3 (3)	C32—C33—H33	119.5
C21—P1—Au1	114.6 (3)	C34—C33—H33	119.5
C11—P1—Au1	110.2 (3)	C33—C34—C35	119.4 (10)
C16—C11—C12	120.2 (8)	C33—C34—H34	120.3
C16—C11—P1	121.6 (8)	C35—C34—H34	120.3
C12—C11—P1	118.2 (6)	C36—C35—C34	119.0 (11)
C13—C12—C11	120.5 (9)	C36—C35—H35	120.5
C13—C12—H12	119.7	C34—C35—H35	120.5
C11—C12—H12	119.7	C31—C36—C35	122.6 (10)
C14—C13—C12	119.5 (11)	C31—C36—H36	118.7
C14—C13—H13	120.3	C35—C36—H36	118.7
C12—C13—H13	120.3	C41—S1—Au1	104.4 (3)
C15—C14—C13	120.0 (10)	N46—C41—N42	126.4 (9)
C15—C14—H14	120.0	N46—C41—S1	114.3 (6)
C13—C14—H14	120.0	N42—C41—S1	119.3 (7)
C14—C15—C16	121.7 (10)	C43—N42—C41	115.7 (8)
C14—C15—H15	119.1	C43—N42—Au1	164.3 (6)
C16—C15—H15	119.1	C41—N42—Au1	80.0 (5)
C11—C16—C15	118.1 (10)	N42—C43—C44	120.9 (9)
C11—C16—H16	121.0	N42—C43—C431	116.4 (9)
C15—C16—H16	121.0	C44—C43—C431	122.6 (10)
C22—C21—C26	119.7 (8)	C45—C44—C43	119.6 (10)
C22—C21—P1	121.8 (6)	C45—C44—H44	120.2
C26—C21—P1	118.5 (6)	C43—C44—H44	120.2
C21—C22—C23	119.4 (9)	C43—C431—H43A	109.5
C21—C22—H22	120.3	C43—C431—H43B	109.5
C23—C22—H22	120.3	H43A—C431—H43B	109.5
C24—C23—C22	120.2 (11)	C43—C431—H43C	109.5
C24—C23—H23	119.9	H43A—C431—H43C	109.5
C22—C23—H23	119.9	H43B—C431—H43C	109.5
C23—C24—C25	122.4 (11)	N46—C45—C44	119.7 (9)
C23—C24—H24	118.8	N46—C45—C451	116.7 (9)
C25—C24—H24	118.8	C44—C45—C451	123.6 (11)
C24—C25—C26	118.6 (10)	C45—C451—H45A	109.5
C24—C25—H25	120.7	C45—C451—H45B	109.5
C26—C25—H25	120.7	H45A—C451—H45B	109.5
C25—C26—C21	119.8 (9)	C45—C451—H45C	109.5
C25—C26—H26	120.1	H45A—C451—H45C	109.5
C21—C26—H26	120.1	H45B—C451—H45C	109.5
C36—C31—C32	118.1 (9)	C41—N46—C45	117.6 (8)
N42—Au1—P1—C31	−133.1 (3)	C21—P1—C31—C32	166.6 (6)
N42—Au1—P1—C21	103.8 (3)	C11—P1—C31—C32	−81.8 (7)
N42—Au1—P1—C11	−15.0 (4)	Au1—P1—C31—C32	39.1 (7)
C31—P1—C11—C16	−11.2 (8)	C36—C31—C32—C33	−2.6 (13)
C21—P1—C11—C16	100.9 (7)	P1—C31—C32—C33	176.9 (7)
Au1—P1—C11—C16	−134.8 (7)	C31—C32—C33—C34	2.0 (15)
C31—P1—C11—C12	169.1 (7)	C32—C33—C34—C35	−0.7 (17)
C21—P1—C11—C12	−78.8 (7)	C33—C34—C35—C36	0.1 (17)
Au1—P1—C11—C12	45.5 (7)	C32—C31—C36—C35	2.1 (14)
C16—C11—C12—C13	−1.6 (15)	P1—C31—C36—C35	−177.4 (8)
P1—C11—C12—C13	178.1 (8)	C34—C35—C36—C31	−0.9 (17)
C11—C12—C13—C14	2.7 (17)	N42—Au1—S1—C41	−0.6 (3)
C12—C13—C14—C15	−1.4 (18)	Au1—S1—C41—N46	−178.7 (6)
C13—C14—C15—C16	−0.8 (17)	Au1—S1—C41—N42	1.4 (7)
C12—C11—C16—C15	−0.6 (13)	N46—C41—N42—C43	−1.4 (13)
P1—C11—C16—C15	179.7 (7)	S1—C41—N42—C43	178.4 (7)
C14—C15—C16—C11	1.9 (15)	N46—C41—N42—Au1	179.2 (8)
C31—P1—C21—C22	78.1 (8)	S1—C41—N42—Au1	−1.0 (5)
C11—P1—C21—C22	−33.2 (8)	P1—Au1—N42—C43	1 (2)
Au1—P1—C21—C22	−154.6 (6)	S1—Au1—N42—C43	−177 (2)
C31—P1—C21—C26	−102.4 (7)	P1—Au1—N42—C41	178.7 (4)
C11—P1—C21—C26	146.4 (7)	S1—Au1—N42—C41	0.8 (4)
Au1—P1—C21—C26	24.9 (8)	C41—N42—C43—C44	−0.8 (13)
C26—C21—C22—C23	−0.8 (14)	Au1—N42—C43—C44	177.0 (16)
P1—C21—C22—C23	178.7 (8)	C41—N42—C43—C431	178.5 (8)
C21—C22—C23—C24	−0.5 (16)	Au1—N42—C43—C431	−4 (3)
C22—C23—C24—C25	1.2 (19)	N42—C43—C44—C45	2.1 (15)
C23—C24—C25—C26	−0.5 (18)	C431—C43—C44—C45	−177.1 (10)
C24—C25—C26—C21	−0.9 (16)	C43—C44—C45—N46	−1.3 (15)
C22—C21—C26—C25	1.5 (14)	C43—C44—C45—C451	176.7 (10)
P1—C21—C26—C25	−178.0 (8)	N42—C41—N46—C45	2.2 (13)
C21—P1—C31—C36	−13.9 (8)	S1—C41—N46—C45	−177.6 (7)
C11—P1—C31—C36	97.6 (8)	C44—C45—N46—C41	−0.7 (14)
Au1—P1—C31—C36	−141.4 (7)	C451—C45—N46—C41	−178.9 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···N46^i	0.93	2.65	3.547 (13)	162
C33—H33···N46^ii	0.93	2.63	3.426 (14)	144

Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y, −z+1.