Di-μ-thio­semicarbazide-κ4 S:S-bis­[chlori­dobis(triphenyl­phosphane-κP)silver(I)]

Yupa Wattanakanjana; Chaveng Pakawatchai; Ruthairat Nimthong

doi:10.1107/S1600536812051562

. 2013 Jan 9;69(Pt 2):m83–m84. doi: 10.1107/S1600536812051562

Di-μ-thiosemicarbazide-κ⁴ S:S-bis[chloridobis(triphenylphosphane-κP)silver(I)]

Yupa Wattanakanjana ^a,^*, Chaveng Pakawatchai ^b, Ruthairat Nimthong ^b

PMCID: PMC3569183 PMID: 23424427

Abstract

The dinuclear title complex, [Ag₂Cl₂(CH₅N₃S)₂(C₁₈H₁₅P)₂], lies across an inversion center. The Ag^I ion exhibits a slightly distorted tetrahedral coordination geometry formed by a P atom from a triphenylphosphane ligand, two metal-bridging S atoms from thiosemicabazide ligands and one chloride ion. The S atoms bridge two symmetry-related Ag^I ions, forming a strictly planar Ag₂S₂ core with an Ag⋯Ag separation of 2.7802 (7) Å. There is an intramolecular N—H⋯Cl hydrogen bond. In the crystal, N—H⋯Cl and N—H⋯S hydrogen bonds link complex molecules, forming layers parallel to (001). These layers are connected through π–π stacking interactions [centroid–centroid distance = 3.665 (2) Å], leading to the formation of a three-dimensional network.

Related literature

For metal(I) complexes of phosphine ligands as precursors for the preparation of mixed-ligand complexes, see: Ferrari et al. (2007 ▶); Pakawatchai et al. (2012 ▶). For potential applications of thiosemicarbazide derivatives and their metal complexes, see: Pandeya et al. (1999 ▶); Wujec et al. (2009 ▶); Mohareb & Mohamed (2012 ▶); He et al. (2012 ▶). For examples of related discrete complexes, see: Wattanakanjana et al. (2012 ▶); Lobana et al. (2008 ▶).

Experimental

Crystal data

[Ag₂Cl₂(CH₅N₃S)₂(C₁₈H₁₅P)₂]
M _r = 993.46
Triclinic,
a = 8.7845 (4) Å
b = 9.4656 (4) Å
c = 13.7529 (6) Å
α = 109.276 (1)°
β = 98.306 (1)°
γ = 99.739 (1)°
V = 1038.94 (8) Å³
Z = 1
Mo Kα radiation
μ = 1.28 mm⁻¹
T = 293 K
0.38 × 0.30 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.638, T _max = 0.880
14302 measured reflections
5026 independent reflections
4627 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 0.069
S = 1.06
5026 reflections
251 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.55 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: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(28KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812051562/lh5573sup1.cif

e-69-00m83-sup1.cif^{(28KB, cif)}

Click here for additional data file.^{(246.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051562/lh5573Isup2.hkl

e-69-00m83-Isup2.hkl^{(246.1KB, 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
N3—H3B⋯Cl1ⁱ	0.87 (2)	2.67 (2)	3.535 (2)	171 (2)
N2—H2⋯S1ⁱⁱ	0.83 (2)	2.66 (2)	3.4320 (15)	155 (2)
N1—H1B⋯Cl1ⁱⁱⁱ	0.85 (2)	2.63 (2)	3.4088 (16)	154 (2)
N1—H1A⋯Cl1	0.89 (2)	2.45 (2)	3.3239 (16)	170 (2)

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

Acknowledgments

We gratefully acknowledge financial support from the Center for Innovation in Chemistry (PERCH–CIC), the Commission on Higher Education, Ministry of Education, the Department of Chemistry and the Graduate School, Prince of Songkla University.

supplementary crystallographic information

Comment

Metal(I) complexes of phosphine ligands have been extensively studied as precursors for preparing mixed-ligand complexes (Ferrari et al., 2007; Pakawatchai et al., 2012) having different geometries such as mononuclear and dinuclear. Thiosemicabazide and thiosemicarbazide derivatives, as well as their metal complexes, have recently attracted considerable attention because of their relevance in biological systems such as antitumor, antimicrobial, antibacterial and antifungal activities (Pandeya et al., 1999; Wujec et al., 2009; Mohareb et al., 2012; He et al., 2012). Herein, the crystal structure of a dinuclear silver(I) chloride complex containing triphenylphosphane and thiosemicarbazide is described.

The molecular structure of the title dinuclear compound is shown in Fig. 1. The molecule lies acroos a crystallographic inversion center which is at the center of the Ag₂S₂ core with a Ag···Ag separation of 2.7802 (7) Å. The bond angles around Ag^I ion are approximately in the range of 111.851 (15)–123.445 (15)°. Geometrical distortion from ideal angles (109.47°) can be explained by the need to accommodate the bulky triphenylphosphane groups. The P1—Ag1 bond length of 2.4225 (4) Å is slightly longer than that found in for example [Ag₂(C₆H₇N₂S)₂(C₁₈H₁₅P)₂], which is 2.4088 (6) Å (Wattanakanjana et al., 2012). The bridging Ag—S bond length (Ag1—S1 = 2.5202 (4) Å) is shorter than those observed in related silver(I) complexes containing S-bridged donor ligand, due to 2.5832 (8)–2.7208 (11) Å for [Ag₂Cl₂(l-S-pySH)₂(PPh₃)₂] and 2.6306 (4)–2.6950 (7) Å for [Ag₂Br₂(l-S-pySH)₂(PPh₃)₂] (Lobana et al., 2008). There is intramolecular N—H···Cl hydrogen bond with the geometry N1···Cl1 = 3.3239 (16) Å. In the crystal, an N1—H1B···Cl1 hydrogen bond connects molecules forming one dimensional chain alongs [010]. Each chain is linked through N2—H2···S1 and N3—H3B···Cl1 hydrogen bonds forming a layer parallel to (001) (Fig. 2). In addition, the layers are stacked via π···π stacking interactions [centroid–centroid distance = 3.665 (2) Å, centroid = C31—C36 ring] froming the three dimensional network (Fig. 3).

Experimental

Triphenylphosphane (0.37 g, 1.41 mmol) was dissolved in 30 cm³ of acetonitrile at 335 K. AgCl (0.10 g, 0.70 mmol) was added and the mixture was stirred for 2.5 h. Thiosemicabazide (0.06 g, 0.66 mmol) was added and the new reaction mixture was heated under reflux for 5 h. The resulting clear solution was filtered off and left to evaporate at room temperature. The crystalline solid, which was deposited upon standing for few days, was filtered off and dried under reduced pressure.