Chlorido{4-ethyl-1-[1-(pyrazin-2-yl)ethyl­idene]thio­semicabazidato-κS}bis­(triphenyl­phosphane-κP)silver(I)

Ramaiyer Venkatraman; Kleopatra D Ruddock; Himangshu S Das; Md Alamgir Hossain; Frank R Fronczek

doi:10.1107/S1600536813003152

. 2013 Feb 6;69(Pt 3):m137–m138. doi: 10.1107/S1600536813003152

Chlorido{4-ethyl-1-[1-(pyrazin-2-yl)ethylidene]thiosemicabazidato-κS}bis(triphenylphosphane-κP)silver(I)

Ramaiyer Venkatraman ^a,^*, Kleopatra D Ruddock ^a, Himangshu S Das ^b, Md Alamgir Hossain ^a, Frank R Fronczek ^c

PMCID: PMC3588416 PMID: 23476487

Abstract

The title compound, [Ag(C₉H₁₃N₅S)Cl(C₁₈H₁₅P)₂], crystallizes with four independent molecules in the asymmetric unit, in each of which the Ag atom is in a distorted tetrahedral coordination, defined by the chloride ligand, the S atom of the neutral ligand and two P atoms derived from the triphenyl phosphine ligands. The thiosemicarbazone acts as a monodentate ligand through its thione S atom. An intramolecular N—H⋯Cl hydrogen bond occurs in two of the independent molecules. In the crystal, the molecules are assembled through N—H⋯Cl hydrogen bonds, forming chains along [101].

Related literature

For general background to thiosemicarbazones, see: Akinchan et al. (2002 ▶); Ali & Livingstone (1974 ▶); Bermejo et al. (2003 ▶); Blanz & French (1968 ▶); Campbell (1975 ▶); Casas et al. (2000 ▶); Grecu & Neamtu (1967 ▶); Hossain et al. (2002 ▶); Huheey et al. (1993 ▶); Lobana et al. (1998 ▶, 2008 ▶); Pellerito & Negy (2002 ▶); Raper (1985 ▶); Venkatraman et al. (2009 ▶); Zhou et al. (2008 ▶).

Experimental

Crystal data

[Ag(C₉H₁₃N₅S)Cl(C₁₈H₁₅P)₂]
M _r = 891.17
Monoclinic,
a = 12.0640 (5) Å
b = 31.810 (2) Å
c = 21.9207 (15) Å
β = 98.029 (5)°
V = 8329.7 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.71 mm⁻¹
T = 90 K
0.27 × 0.22 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer with Oxford Cryostream system
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.831, T _max = 0.870
138032 measured reflections
54942 independent reflections
44399 reflections with I > 2σ(I)
R _int = 0.055

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.103
S = 1.03
54942 reflections
2007 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.03 e Å⁻³
Δρ_min = −0.85 e Å⁻³
Absolute structure: Flack (1983 ▶), 25,519 Friedel pairs
Flack parameter: 0.382 (11)

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXH (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXH.

Supplementary Material

Click here for additional data file.^{(102.8KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813003152/rk2386sup1.cif

e-69-0m137-sup1.cif^{(102.8KB, cif)}

Click here for additional data file.^{(2.6MB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813003152/rk2386Isup2.hkl

e-69-0m137-Isup2.hkl^{(2.6MB, 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
N1—H1N⋯Cl1	0.88 (2)	2.54 (2)	3.381 (3)	163 (3)
N3—H3N⋯Cl3	0.87 (2)	2.68 (3)	3.406 (3)	142 (3)
N6—H6N⋯Cl2	0.88 (2)	2.53 (2)	3.370 (3)	162 (3)
N8—H8N⋯Cl4	0.86 (2)	2.68 (3)	3.411 (3)	143 (3)
N11—H11N⋯Cl3	0.88 (2)	2.52 (2)	3.363 (3)	161 (3)
N13—H13N⋯Cl2	0.88 (2)	2.65 (2)	3.423 (3)	147 (3)
N16—H16N⋯Cl4	0.86 (2)	2.50 (2)	3.338 (3)	164 (3)
N18—H18N⋯Cl1ⁱ	0.86 (2)	2.70 (3)	3.425 (3)	143 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The National Science Foundation is acknowledged for a CAREER award (CHE–1056927) to MAH. Purchase of the diffractometer was made possible by grant No. LEQSF (1999–2000)–ENH–TR–13, administered by the Louisiana Board of Regents.

supplementary crystallographic information

Comment

Thiosemicarbazones are versatile ligands for several metals due to the keto–enol tautomeric form exhibited by the molecules (Ali & Livingstone, 1974; Campbell, 1975; Pellerito & Negy, 2002; Raper, 1985; Casas et al., 2000; Blanz & French, 1968; Grecu & Neamtu, 1967; Lobana et al., 1998; Bermejo et al., 2003; Akinchan et al., 2002; Zhou et al. 2008; Huheey et al., 1993). Among the metals that complex with thiosemicarbazones, Ag(I), and Cu(I) are known to interact with thiosemicarbazones differently and the resulting compounds exhibit variable structural features depending on the conditions of their preparation. Recently, the influence of substituents at the C² carbon of thiosemicarbazones on bonding and nuclearity of silver complexes were investigated (Lobana et al., 2008). Among the ligands that ligate with Ag(I) with pyrazine thiosemicarbazone received less attention.

In continuation of our study on metal complexes with thiosemicarbazones, we report herein a silver complex (Scheme 1) formed by the reaction of 2–acetylpyrazine N(4)–ethyl–3–thiosemicarbazone with AgCl in presence of triphenylphosphine as a coligand. The compound crystallizes with four independent molecules in asymmetric unit (Fig. 1). The Ag—S bond distances vary from 2.6816 (8)Å to 2.7412 (9)Å with a mean value of 2.7067 (9)Å. The Ag—S bond distance is smaller than the sum of ionic radii of Ag and S ions (2.78Å). On the other hand, the distances of Ag—P are in the range of 2.4784 (8)Å to 2.4877 (8)Å with a mean value of 2.4835 (8)Å which are smaller than that observed for Ag—S bonds. The average bond distance of Ag—P is comparable to the mononuclear silver complex of thiosemicarbazone (2.4409 (7)Å and 2.4879 (7)Å) reported by Lobana et al. (2008). In the asymmetric unit the four Ag—Cl bonds distances are almost similar (2.5900 (8)Å to 2.5932 (8)Å) with a mean value of 2.5921 (8)Å which is shorter than the sum of the ionic radii of silver and chloride (2.75Å). The C—S bond distances in all four units is identical to 1.704 (3)Å which is much longer than the literature value (1.6796 (9)Å) for the free ligand reported by Venkatraman et al. (2009). As shown in the Fig. 2, the molecules are linked with intra– and inter–molecular N—H···Cl hydrogen bonding interactions (Hossain et al., 2002).

Experimental

To a freshly prepared AgCl (0.143 g, 1 mmol) suspended in acetonitrile (20 ml) and was mixed with an acetonitrile solution of 2–acetylpyrazine N(4)–ethyl–3–thiosemicarbazone (0.223 g, 1 mmol,) (Venkatraman et al., 2009) and the resulting mixture was stirred overnight. To the white solid formed in acetonitrile, solid triphenylphosphine (0.530 g, 2 mmol) was added in two equal aliquots to obtain a clear solution. The solution was filtered and left for crystallization at room temperature.