catena-Poly[silver(I)-bis­[μ-4-methyl-1H-1,2,4-triazole-3(4H)-thione-κ2 S:S]-silver(I)-di-μ-thio­cyanato-κ2 S:N;κ2 N:S]

Kultida Kodcharat; Chaveng Pakawatchai; Saowanit Saithong

doi:10.1107/S160053681300946X

. 2013 Apr 13;69(Pt 5):m265–m266. doi: 10.1107/S160053681300946X

catena-Poly[silver(I)-bis[μ-4-methyl-1H-1,2,4-triazole-3(4H)-thione-κ² S:S]-silver(I)-di-μ-thiocyanato-κ² S:N;κ² N:S]

Kultida Kodcharat ^a, Chaveng Pakawatchai ^a, Saowanit Saithong ^a,^*

PMCID: PMC3647807 PMID: 23723773

Abstract

In the title one-dimensional coordination polymer, [Ag₂(NCS)₂(C₃H₅N₃S)₂]_n, the Ag^I atom adopts a distorted tetrahedral AgNS₃ geometry. Adjacent Ag^I atoms in the [001] chain are alternately linked by pairs of bridging 4-methyl-1H-1,2,4-triazole-3(4H)-thione (Hmptrz) ligands (via their S atoms) and double thiocyanate bridges linking through both S and N atoms (μ-1,3-SCN). An intrachain N—H⋯N hydrogen bond occurs between the NH group of the triazole ring and the N atom of the thiocyanate bridging ligand. A (101) sheet structure arises from interchain S⋯N short contacts [3.239 (3) Å] involving the thiocyanate S atom and the triazole-ring N atom and possible very weak π–π stacking [centroid–centroid separation = 4.0762 (18) Å] between the triazole rings.

Related literature

For examples of complexes with multifunctional ligand donors, see: Zhang et al.(2009 ▶); Wang et al. (2011 ▶). For background to complexes containing derivatives of the 1,2,4-triazole ligand, see: Zhang et al. (1999 ▶); Jiang et al. (2011 ▶). For the thiocyanate bridging ligand, end-to-end mode, see: Vicente et al. (1997 ▶); Chen et al. (1999 ▶); Diaz et al. (1999 ▶); Goher et al. (2000 ▶); Song et al. (2000 ▶); Cai et al. (2007 ▶); Saithong et al. (2007 ▶). graphic file with name e-69-0m265-scheme1.jpg

Experimental

Crystal data

[Ag₂(NCS)₂(C₃H₅N₃S)₂]
M _r = 562.22
Triclinic,
a = 7.4842 (6) Å
b = 7.5420 (6) Å
c = 8.4262 (7) Å
α = 79.985 (2)°
β = 84.329 (2)°
γ = 64.508 (1)°
V = 422.62 (6) Å³
Z = 1
Mo Kα radiation
μ = 2.82 mm⁻¹
T = 293 K
0.31 × 0.12 × 0.05 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.682, T _max = 0.879
5887 measured reflections
2083 independent reflections
1904 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.070
S = 1.05
2083 reflections
104 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); 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 ▶), PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(17.2KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681300946X/hb7066sup1.cif

e-69-0m265-sup1.cif^{(17.2KB, cif)}

Click here for additional data file.^{(102.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681300946X/hb7066Isup2.hkl

e-69-0m265-Isup2.hkl^{(102.4KB, hkl)}

Click here for additional data file.^{(3.7KB, mol)}

Supplementary material file. DOI: 10.1107/S160053681300946X/hb7066Isup3.mol

Click here for additional data file.^{(3.7KB, mol)}

Supplementary material file. DOI: 10.1107/S160053681300946X/hb7066Isup4.mol

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

Table 1. Selected bond lengths (Å).

Ag1—N4ⁱ	2.354 (3)
Ag1—S2	2.4987 (8)
Ag1—S1	2.5554 (8)
Ag1—S1ⁱⁱ	2.6688 (8)

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

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N4ⁱ	0.86 (2)	2.10 (2)	2.954 (4)	171 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from the Center of Excellent for Innovation in Chemistry (PERCH-CIC), Office of the Higher Education Commission, Ministry of Education, and Graduate School, Prince of Songkla University, are gratefully acknowledge.

supplementary crystallographic information

Comment

One of the active areas of meterial research is the coordination compounds of the metal ions with the multifunctional ligands leading to the structural diversities and properties (Zhang et al., 2009; Wang et al., 2011). For this work, we report the mixed ligands Ag(I) complex containg multidonor atoms, 4-methyl-1,2,4-triazole-3-thiol (Hmptrz) and thiocyanate ligands. The Hmptrz is one of 1,2,4-triazole derivative ligands - based heterocyclic thioamide containing thiol group which has three potential donor atoms. Both Hmptrz and thiocyanate group are amphidentate ligands, which can bind to the metal center with either the N or S atom or both of them (Zhang et al., 1999; Jiang et al., 2011).

The title complex exhibits a one-dimensional chain polymeric structure and the asymmetric unit consists of one Ag(I) atom, one Hmptrz molecule and one SCN^- anion. The chemical structure of this complex is shown in Scheme I and the crystal structure is depicted in Figure 1.

The Ag atom features a distorted tetrahedral environment with the range of angles from 101.00 (2) to 124.52 (3)^o. Each Ag is bonded by two µ₂-S-bridging atoms of two Hmptrz molecules with the distances of 2.5554 (8) and 2.6688 (8) Å. The other two coordination sites are occupied by S and N atoms from the different µ₂-1,3-SCN bridges coordinated as a pair alternating bidentate end to end fashion similar to those complexes of the same thiocyanate bridges (Chen et al., 1999; Diaz et al., 1999; Goher et al., 2000; Song et al., 2000; Cai et al., 2007; Saithong et al. 2007). The Cu—S_thiocyanato and Cu—N_thiocyanato bond distances are 2.4987 (8) and 2.2354 (4) Å, respectively. The SCN bond angle is almost perfectly linear [178.6 (3)°] as compare with the same µ₂-1,3-SCN configuration mode of those complexes (Vicente et al.,1997; Song et al., 2000). The S2—C4 and C4—N4 distances [1.646 (3) and 1.150 (4) Å] refer to thiocyanate resonance form which indicate to a π-delocalized system along the metal-thiocyanate chain (Zhang et al., 1999).

An infintite one-dimensional structure of this complex is based on [Ag(µ_2-Hmptrz)(µ₂-1,3-SCN)] double-bridges, in which both Hmptrz and SCN^- ligands adopt the µ₂-end-on and µ₂-end-to-end bridging mode, respectively. As illustated in Figure 2, the Hmptrz and thiocyanato ligands interconnect the Ag(I) ions into an infinite chain generated by the unit c translation runing parallel to c axis, which consist of four-membered ring [—Ag—S—Ag—S—] and eight-membered ring [—Ag—S═C═N—Ag—S═C═N—]. In addition, The Ag···Ag separation with the distances of 3.3241 (5) Å in the four-membered ring is slighty shorter than the sum of the van der Waals radii of Ag atoms (3.44 Å), which indicates that there is the Ag···Ag interaction.

The weak intra-molecular hydrogen bonding interaction [N1—H1···N4ⁱ, (i) = -x + 1, -y, -z + 1] is found between N(1) of triazole ring and N(4) of thiocyanate bridging ligand at 2.954 (4) Å. The inter-short contact at 3.239 (3) Å arises from S2 donor of triazole ring with N2 acceptor from the thiocyanate bridge of the neighbouring adjacent chain which is smaller than the sum of S and N van der Waals radii (1.80 + 1.55 Å). In addition, the π···π stacking between the triazole rings of the neighbouring chain is observed with the centroid-centriod distance of 4.0762 (18) Å. Both of these interactions generate the supramolecular layer interactions related by ac-plane. A view of intra-molecular hydrogen bonding is depected in Figure 3 and The layered network interactions in crystal packing are shown in Figure 4.

Experimental

A mixture of AgNO₃ (0.15 g, 0.88 mmol), KSCN (0.09 g, 0.87 mmol) in EtOH 30 ml was heated and stirred to 75 °C for 1 h. After that, the Hmptrz ligand (0.1 g, 0.087 mmol was added to the mixture and further continuous stirring for 12 h. The colorless crystals of the complex were obtained after the colorless filtrate was kept to stand at room temperature for a day. The complex melts at 130–132°C.