Bis(μ-4,6-dimethyl­pyrimidine-2-thiol­ato)-κ3 N,S:S;κ3 S:N,S-bis­[(triphenyl­phosphane-κP)silver(I)]

Yupa Wattanakanjana; Chaveng Pakawatchai; Sukanya Kowittheeraphong; Ruthairat Nimthong

doi:10.1107/S1600536812048210

. 2012 Nov 30;68(Pt 12):m1572–m1573. doi: 10.1107/S1600536812048210

Bis(μ-4,6-dimethylpyrimidine-2-thiolato)-κ³ N,S:S;κ³ S:N,S-bis[(triphenylphosphane-κP)silver(I)]

Yupa Wattanakanjana ^a,^*, Chaveng Pakawatchai ^a, Sukanya Kowittheeraphong ^a, Ruthairat Nimthong ^a

PMCID: PMC3588805 PMID: 23468770

Abstract

The dinuclear title complex, [Ag₂(C₆H₇N₂S)₂(C₁₈H₁₅P)₂], comprises two inversion-related [Ag(C₆H₇N₂S)(C₁₈H₁₅P)] units. The pyrimidinethiolate anion acts both as a bridging and a chelating ligand. The Ag^I ions are linked via two μ ₂-S donor atoms, which generate a strictly planar Ag₂S₂ core with an Ag⋯Ag separation of 2.9569 (4) Å. The Ag^I ion presents a distorted tetrahedral coordination geometry. In the crystal, weak C—H⋯N and C—H⋯S hydrogen bonds link the complex molecules into a two-dimensional network parallel to (010).

Related literature

For the structures of metal(I) coordination compounds and their potential applications, see: Aslanidis et al. (1997 ▶); McFarlane et al. (1998 ▶); Nawaz et al. (2011 ▶); Hameau et al. (2012 ▶); Nimthong et al. (2012 ▶); Pakawatchai et al. (2012 ▶). For relevant examples of discrete complexes, see: Cox et al. (2000 ▶); Lobana et al. (2008 ▶); Isab et al. (2010 ▶). graphic file with name e-68-m1572-scheme1.jpg

Experimental

Crystal data

[Ag₂(C₆H₇N₂S)₂(C₁₈H₁₅P)₂]
M _r = 1018.67
Monoclinic,
a = 11.7050 (5) Å
b = 15.3084 (7) Å
c = 12.5331 (6) Å
β = 97.483 (1)°
V = 2226.62 (18) Å³
Z = 2
Mo Kα radiation
μ = 1.08 mm⁻¹
T = 293 K
0.29 × 0.18 × 0.09 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.793, T _max = 0.909
26686 measured reflections
5568 independent reflections
4798 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.088
S = 1.04
5568 reflections
266 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(26.4KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812048210/bh2464sup1.cif

e-68-m1572-sup1.cif^{(26.4KB, cif)}

Click here for additional data file.^{(267.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812048210/bh2464Isup2.hkl

e-68-m1572-Isup2.hkl^{(267.1KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯S1ⁱ	0.93	2.94	3.801 (3)	154
C14—H14⋯N2ⁱⁱ	0.93	2.69	3.471 (4)	143
C35—H35⋯N2ⁱⁱⁱ	0.93	2.93	3.756 (4)	151

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

We are grateful to the Department of Chemistry, and the Graduate School, Prince of Songkla University, for financial support of this work.

supplementary crystallographic information

Comment

In recent years, a large number of structural reports on metal(I) complexes containing heterocyclic thiones as ligands or mixed-ligands with triphenylphosphane have been studied (Aslanidis et al., 1997; McFarlane et al., 1998; Pakawatchai et al., 2012; Nimthong et al., 2012) because of not only their potential applications due to their antimicrobial activities (Nawaz et al., 2011), but also strongly luminescent properties (Hameau et al., 2012).

The structure of the title dinuclear mixed-ligand complex displays the distorted tetrahedral coordination of each Ag^I center, which exhibits a planar Ag₂S₂ moiety in which each of the doubly S-bridged Ag^I centers is surrounded by the one P atom of phosphane ligand and one N atom of the dmpymtH ligands (Fig. 1). The Ag—Ag distance of 2.9569 (4) Å in the four-membered Ag₂S₂ ring is shorter than in [Ag₂X₂(l-S-pySH)₂(PPh₃)₂] (X = Cl and Br), 3.8425 (8) and 3.8211 (4) Å, respectively (Lobana et al., 2008) and also shorter than the sum of the covalent radii of two Ag^I centers (3.44 Å). Focusing on the comparison of bond distances and bond angles around the Ag^I ion, the Ag—S bond lengths [2.5492 (6)–2.7897 (6) Å] are in good agreement with values reported for other silver(I) complexes with heterocyclic thione ligands, such as 2.5548 (9) Å for [Ag(PPh₃)(pymtH)Br]₂ (Cox et al., 2000) and 2.537 (2) Å for [Ag(Ph₃P)(Diaz)₂]₂(NO₃)₂ (Nawaz et al., 2011). The Ag1—P1 bond length of 2.4088 (6) Å is similar to that found in [Ag(PPh₃)(thiourea)(NO₃)]₂.[Ag(PPh₃)(thiourea)]₂(NO₃)₂ [2.4029 (10)–2.4157 (10) Å] (Isab et al., 2010). The two S1–Ag1–P1 angles of 116.81 (2) and 123.56 (2)° are larger than the normal tetrahedral value of 109.5°. In the crystal, the intermolecular interactions C14(sp²)—H14···N2 [H14···N2 = 2.686 (4) Å, C14(sp²)···N2 = 3.471 (4) Å and C14(sp²)—H14···N2 = 142.52 (8)°] and C14(sp²)—H14···S1 [H14···S1 = 2.942 (3) Å, C14(sp²)···S1 = 3.801 (3) Å and C14(sp²)—H14···S1 = 154.18 (9)°] form chains (Fig. 2). Moreover, secondary interactions C35(sp²)—H35···N2 [H35···N2 = 2.928 (4) Å, C35(sp²)···N2 = 3.756 (4) Å and C35(sp²)—H35···N2 = 150.48 (7)°] are also observed, which form the two-dimensional layer network (Fig. 3).

Experimental

Triphenylphosphane (0.31 g, 1.18 mmol) was dissolved in 30 cm³ of ethanol at 335 K. Silver acetate (0.10 g, 0.60 mmol) was added and the mixture was stirred for 3 h. 4,6-Dimethylpyrimidine-2(1H)-thione (0.18 g, 0.46 mmol) was added and the new reaction mixture was refluxed for 2 h where upon the precipitate gradually disappeared. The resulting clear solution was filtered off and left to evaporate at room temperature. The crystalline solid, which was deposited upon standing for several days, was filtered off and dried under reduced pressure.