Bis[μ-2,5-bis­(pyridin-2-yl)-1,3,4-thia­diazole-κ4 N 2,N 3:N 4,N 5]bis­[(nitrato-κO)silver(I)] tetra­hydrate

Abdelhakim Laachir; Fouad Bentiss; Salaheddine Guesmi; Mohamed Saadi; Lahcen El Ammari

doi:10.1107/S1600536813014578

. 2013 May 31;69(Pt 6):m351–m352. doi: 10.1107/S1600536813014578

Bis[μ-2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole-κ⁴ N ²,N ³:N ⁴,N ⁵]bis[(nitrato-κO)silver(I)] tetrahydrate

Abdelhakim Laachir ^a, Fouad Bentiss ^a,^*, Salaheddine Guesmi ^a, Mohamed Saadi ^b, Lahcen El Ammari ^b

PMCID: PMC3684907 PMID: 23795009

Abstract

The self-assembly of an angular 2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole ligand (L) with silver nitrate (AgNO₃) produced a new dinuclear silver(I) coordination complex, [Ag₂(C₁₂H₈N₄S)₂(NO₃)₂]·4H₂O, which crystallizes with two Ag atoms bridged by two L ligands. The Ag atom is surrounded by four N atoms of L and by one O from the nitrate anion defining a distorted square pyramid. The atoms comprising the dication are nearly coplanar, with an r.m.s. deviation of 0.1997 Å. Molecules are linked by C—H⋯O and O—H⋯O hydrogen bonds through nitrate anions and water molecules, forming a two-dimensional porous network. The overall structure involves stacking of Ag complex layers along the b axis. The cohesion in the three-dimensional architecture is ensured by O⋯Ag interactions.

Related literature

For the synthesis of the ligand, see: Lebrini et al. (2005 ▶). For background to coordination polymers, see: Brammer (2004 ▶); Ghosh et al. (2004 ▶); Maspoch et al. (2004 ▶). For complexes with the same ligand but with other metals and counter-anions, see: Bentiss et al. (2012 ▶); Niu et al. (2009 ▶).

Experimental

Crystal data

[Ag₂(C₁₂H₈N₄S)₂(NO₃)₂]·4H₂O
M _r = 892.41
Triclinic,
a = 5.4251 (1) Å
b = 10.6894 (3) Å
c = 14.5865 (3) Å
α = 108.910 (1)°
β = 91.447 (1)°
γ = 102.440 (1)°
V = 777.30 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.47 mm⁻¹
T = 296 K
0.42 × 0.32 × 0.23 mm

Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T _min = 0.739, T _max = 0.867
29938 measured reflections
5388 independent reflections
3919 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.090
S = 1.01
5388 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.93 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) 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/S1600536813014578/tk5229sup1.cif

e-69-0m351-sup1.cif^{(26.4KB, cif)}

Click here for additional data file.^{(258.5KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813014578/tk5229Isup2.hkl

e-69-0m351-Isup2.hkl^{(258.5KB, 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
O4—H4B⋯O5	0.86	2.08	2.777 (4)	138
O4—H4A⋯O4ⁱ	0.86	2.51	2.980 (9)	115
C1—H1⋯O2ⁱⁱ	0.93	2.44	3.342 (3)	164
C12—H12⋯O2ⁱⁱⁱ	0.93	2.48	3.376 (4)	162
O5—H5A⋯O2^iv	0.86	2.05	2.874 (3)	162
O5—H5A⋯O1^iv	0.86	2.46	3.191 (3)	143
O5—H5B⋯O1^v	0.86	1.99	2.851 (3)	176

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

Acknowledgments

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

supplementary crystallographic information

Comment

The design and construction of novel coordination polymers are very important parts of crystal engineering not only for the purpose of generating functional materials (Maspoch et al., 2004) but also for their fascinating structures (Brammer, 2004). So far, the design and synthesis of new ligands with various coordinating modes, the exploration of synthetic methods to construct coordination polymers, and investigation on the effect of various factors upon architectures have greatly contributed to this field (Ghosh et al., 2004). The compound 2,5-bis(2-pyridyl)-1,3,4-thiadiazole was usually used as a bidentate ligand to form five-atom ring complexes and sometimes it coordinates two metal atoms by four nitrogen atoms as double-bidentate ligand. The structures of monomeric complexes of the neutral 2,5-bis(2-pyridyl)-1,3,4-thiadiazole derivative with Cu²⁺ (nitrate, perchlorate and trifluoromethanesulfonate) and Ag⁺ (SbF₆^-) have been previously reported (Bentiss et al., 2012; Niu et al., 2009). Recently, the study of the new di-nuclear silver(I) coordination complexes with 2,5-bis(2-pyridyl)-1,3,4-thiadiazole showed that the supramolecular structures of its silver complexes can change with the size of counter-anions of the same polyhedron (Niu et al., 2009). As a continuation of our work, in this contribution, we report here the synthesis and the single-crystal structure determination of the new dimeric complex formed by 2,5-bis(2-pyridyl)-1,3,4-thiadiazole (L) with silver nitrate as counter ions.

The asymmetric unit of the title compound, [2,5-bis(2-pyridyl)-1,3,4- thiadiazole]silver(I) nitrate, dihydrate is doubled by the application of a centre of inversion, resulting in a Ag₂-containing dimeric complex. The structure shows the silver cation in a distorted square pyramid site formed by four nitrogen atoms belonging to one organic ligand and an O atom of a nitrate anion (Fig. 1). Each ligand molecule is build up by two six-membered rings linked through a five-membered ring. The two silver atoms and ligands are nearly coplanar, with a r.m.s. deviation of 0.1997 Å. The molecules are linked together by C–H···O and O–H···O hydrogen bonds through nitrate and water molecules, forming a two-dimensional porous network. The overall structure involves stacking of Ag complex layers nearly along the b axis. The cohesion in the crystal is ensured by O3–Ag1 interaction (Fig. 2 and Table 2).

Experimental

2,5-Bis(2-pyridyl)-1,3,4-thiadiazole ligand (L) was synthesized as described previously by Lebrini et al. (2005). AgNO₃ (0.75 mmol, 0.13 g) in water (5 ml ) was added to L (0.21 mmol, 50 mg) dissolved in ethanol (13 ml). The resulting solution was stirred for 30 min. The solution was filtered and allowed to stand at ambient temperature. After seven days, yellow blocks crystallized. Crystals were washed with water and dried under vacuum (yield 34%). These crystals were used as isolated for single-crystal X-ray analysis. Anal. Calc. for C₂₄H₂₄Ag₂N₁₀O₁₀S₂. C, 37.60; H, 3.13; N, 18.28 S, 8.37; Found: C, 37.69; H, 3.17; N, 18.21; S, 8.34.