Bis[μ-2,5-bis­(pyridin-2-yl)-1,3,4-thia­diazole-κ4N2,N3:N4,N5]bis­[(nitrato-κO)silver(I)] tetra­hydrate

Laachir, A.; Bentiss, F.; Guesmi, S.; Saadi, M.; El Ammari, L.

doi:10.1107/S1600536813014578

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Pages m351-m352

doi:10.1107/S1600536813014578

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Bis[μ-2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole-κ⁴N²,N³:N⁴,N⁵]bis[(nitrato-κO)silver(I)] tetrahydrate

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

^aLaboratoire de Chimie de Coordination et d'Analytique (LCCA), Faculté des Sciences, Université Chouaib Doukkali, BP 20, M-24000 El Jadida, Morocco, and ^bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: f_bentiss@yahoo.fr

(Received 21 May 2013; accepted 27 May 2013; online 31 May 2013)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.034
wR(F²) = 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

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
Symmetry codes: (i) -x, -y, -z+1; (ii) x+1, y, z; (iii) -x, -y, -z; (iv) -x+1, -y+1, -z+1; (v) -x+2, -y+1, -z+1.

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813014578/tk5229sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 (Bruker, 2009); 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).

Figures top

	Fig. 1. Plot of the crystal structure showing the molecules linked to the silver cation, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Symmetry code: (i) -x + 1, -y, -z; (ii) -x, -y, -z + 1; (iii) -x + 1, -y + 1, -z + 1.
	Fig. 2. Partial plot of the unit cell showing crystal packing. Hydrogen bonds are depicted as dashed lines. Symmetry codes: (c) -x, -y, -z + 1; (e) -x + 1, -y + 1, -z + 1; (h) -x, -y, -z.

Bis[µ-2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole-κ⁴N²,N³:N⁴,N⁵]bis[(nitrato-κO)silver(I)] tetrahydrate top

Crystal data top

[Ag₂(C₁₂H₈N₄S)₂(NO₃)₂]·4H₂O	Z = 1
M_r = 892.41	F(000) = 444
Triclinic, P1	D_x = 1.906 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.4251 (1) Å	Cell parameters from 29938 reflections
b = 10.6894 (3) Å	θ = 2.9–32.0°
c = 14.5865 (3) Å	µ = 1.47 mm⁻¹
α = 108.910 (1)°	T = 296 K
β = 91.447 (1)°	Block, colourless
γ = 102.440 (1)°	0.42 × 0.32 × 0.23 mm
V = 777.30 (3) Å³

Data collection top

Bruker X8 APEX diffractometer	5388 independent reflections
Radiation source: fine-focus sealed tube	3919 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 32.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −8→8
T_min = 0.739, T_max = 0.867	k = −15→15
29938 measured reflections	l = −20→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0369P)² + 0.5008P] where P = (F_o² + 2F_c²)/3
5388 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 0.92 e Å⁻³
0 restraints	Δρ_min = −0.93 e Å⁻³

Crystal data top

[Ag₂(C₁₂H₈N₄S)₂(NO₃)₂]·4H₂O	γ = 102.440 (1)°
M_r = 892.41	V = 777.30 (3) Å³
Triclinic, P1	Z = 1
a = 5.4251 (1) Å	Mo Kα radiation
b = 10.6894 (3) Å	µ = 1.47 mm⁻¹
c = 14.5865 (3) Å	T = 296 K
α = 108.910 (1)°	0.42 × 0.32 × 0.23 mm
β = 91.447 (1)°

Data collection top

Bruker X8 APEX diffractometer	5388 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	3919 reflections with I > 2σ(I)
T_min = 0.739, T_max = 0.867	R_int = 0.029
29938 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.01	Δρ_max = 0.92 e Å⁻³
5388 reflections	Δρ_min = −0.93 e Å⁻³
217 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against all reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on all data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ag1	0.88258 (4)	0.17155 (2)	0.082506 (13)	0.05506 (8)
S1	0.27700 (10)	−0.00777 (6)	0.27138 (4)	0.03914 (12)
N1	0.9412 (3)	0.2260 (2)	0.25072 (14)	0.0399 (4)
N2	0.5007 (4)	0.0657 (2)	0.13988 (14)	0.0442 (4)
N3	0.2802 (4)	−0.0253 (2)	0.09364 (14)	0.0435 (4)
N4	−0.1644 (4)	−0.2195 (2)	0.02161 (14)	0.0415 (4)
C1	1.1468 (4)	0.3134 (3)	0.30566 (19)	0.0473 (5)
H1	1.2796	0.3477	0.2749	0.057*
C2	1.1710 (5)	0.3552 (3)	0.4058 (2)	0.0568 (7)
H2	1.3189	0.4151	0.4414	0.068*
C3	0.9763 (6)	0.3080 (3)	0.4524 (2)	0.0606 (7)
H3	0.9894	0.3350	0.5201	0.073*
C4	0.7590 (5)	0.2191 (3)	0.39710 (17)	0.0491 (6)
H4	0.6221	0.1863	0.4268	0.059*
C5	0.7497 (4)	0.1801 (2)	0.29698 (16)	0.0367 (4)
C6	0.5261 (4)	0.0856 (2)	0.23297 (15)	0.0358 (4)
C7	0.1435 (4)	−0.0725 (2)	0.15227 (15)	0.0349 (4)
C8	−0.1038 (4)	−0.1714 (2)	0.11867 (15)	0.0345 (4)
C9	−0.2607 (4)	−0.2091 (3)	0.18250 (17)	0.0428 (5)
H9	−0.2114	−0.1748	0.2492	0.051*
C10	−0.4937 (5)	−0.2991 (3)	0.1457 (2)	0.0476 (5)
H10	−0.6027	−0.3273	0.1871	0.057*
C11	−0.5609 (5)	−0.3460 (3)	0.0472 (2)	0.0477 (5)
H11	−0.7186	−0.4042	0.0210	0.057*
C12	−0.3919 (5)	−0.3058 (3)	−0.01236 (18)	0.0476 (5)
H12	−0.4374	−0.3400	−0.0793	0.057*
O1	1.0220 (4)	0.6251 (2)	0.29332 (16)	0.0703 (6)
O2	0.6832 (4)	0.4674 (3)	0.2406 (2)	0.0785 (7)
O3	0.9959 (4)	0.4677 (2)	0.15475 (16)	0.0695 (6)
N5	0.9004 (4)	0.5189 (2)	0.22918 (16)	0.0474 (5)
O4	0.2764 (8)	0.0495 (3)	0.5333 (3)	0.1395 (14)
H4A	0.1511	0.0832	0.5559	0.209*
H4B	0.4079	0.1163	0.5542	0.209*
O5	0.4863 (4)	0.3278 (2)	0.61006 (16)	0.0730 (6)
H5A	0.4020	0.3769	0.6497	0.109*
H5B	0.6329	0.3453	0.6415	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.05582 (12)	0.06872 (16)	0.03379 (10)	−0.00435 (9)	0.01077 (7)	0.01998 (9)
S1	0.0410 (3)	0.0453 (3)	0.0288 (2)	0.0034 (2)	0.00920 (19)	0.0134 (2)
N1	0.0394 (9)	0.0424 (11)	0.0376 (10)	0.0057 (8)	0.0089 (7)	0.0152 (8)
N2	0.0441 (10)	0.0516 (12)	0.0328 (9)	−0.0017 (8)	0.0057 (7)	0.0170 (9)
N3	0.0451 (10)	0.0500 (12)	0.0312 (9)	−0.0005 (8)	0.0055 (7)	0.0153 (8)
N4	0.0433 (9)	0.0430 (11)	0.0335 (9)	0.0051 (8)	0.0079 (7)	0.0096 (8)
C1	0.0407 (11)	0.0489 (14)	0.0491 (13)	0.0011 (10)	0.0063 (10)	0.0185 (11)
C2	0.0464 (13)	0.0549 (16)	0.0543 (15)	−0.0029 (11)	−0.0047 (11)	0.0091 (13)
C3	0.0604 (16)	0.073 (2)	0.0359 (13)	0.0036 (14)	−0.0014 (11)	0.0101 (13)
C4	0.0462 (12)	0.0605 (16)	0.0370 (12)	0.0039 (11)	0.0085 (9)	0.0168 (11)
C5	0.0377 (10)	0.0376 (11)	0.0352 (10)	0.0076 (8)	0.0075 (8)	0.0135 (9)
C6	0.0377 (10)	0.0381 (11)	0.0335 (10)	0.0077 (8)	0.0104 (8)	0.0151 (9)
C7	0.0390 (10)	0.0364 (11)	0.0296 (9)	0.0094 (8)	0.0078 (7)	0.0110 (8)
C8	0.0378 (9)	0.0330 (11)	0.0331 (10)	0.0098 (8)	0.0078 (8)	0.0105 (8)
C9	0.0442 (11)	0.0481 (14)	0.0375 (11)	0.0081 (10)	0.0116 (9)	0.0176 (10)
C10	0.0427 (11)	0.0496 (14)	0.0540 (14)	0.0082 (10)	0.0157 (10)	0.0232 (12)
C11	0.0405 (11)	0.0409 (13)	0.0555 (15)	0.0031 (9)	0.0061 (10)	0.0124 (11)
C12	0.0474 (12)	0.0468 (14)	0.0387 (12)	0.0017 (10)	0.0030 (9)	0.0076 (10)
O1	0.0593 (12)	0.0748 (15)	0.0585 (12)	0.0083 (10)	−0.0056 (10)	0.0037 (11)
O2	0.0413 (10)	0.0866 (16)	0.1001 (18)	0.0029 (10)	0.0200 (11)	0.0283 (14)
O3	0.0732 (13)	0.0715 (14)	0.0570 (12)	0.0109 (11)	0.0245 (10)	0.0152 (11)
N5	0.0367 (9)	0.0564 (13)	0.0502 (12)	0.0083 (9)	0.0025 (8)	0.0211 (10)
O4	0.169 (4)	0.077 (2)	0.154 (4)	−0.004 (2)	−0.004 (3)	0.037 (2)
O5	0.0582 (11)	0.0823 (16)	0.0599 (13)	0.0109 (11)	0.0061 (10)	0.0029 (11)

Geometric parameters (Å, º) top

Ag1—N4ⁱ	2.2785 (19)	C3—H3	0.9300
Ag1—N1	2.3273 (19)	C4—C5	1.379 (3)
Ag1—N2	2.4421 (19)	C4—H4	0.9300
Ag1—N3ⁱ	2.5519 (19)	C5—C6	1.472 (3)
Ag1—O3	2.911 (2)	C7—C8	1.476 (3)
S1—C6	1.719 (2)	C8—C9	1.374 (3)
S1—C7	1.721 (2)	C9—C10	1.386 (3)
N1—C1	1.334 (3)	C9—H9	0.9300
N1—C5	1.343 (3)	C10—C11	1.369 (4)
N2—C6	1.303 (3)	C10—H10	0.9300
N2—N3	1.365 (3)	C11—C12	1.376 (4)
N3—C7	1.299 (3)	C11—H11	0.9300
N3—Ag1ⁱ	2.5519 (19)	C12—H12	0.9300
N4—C12	1.342 (3)	O1—N5	1.247 (3)
N4—C8	1.345 (3)	O2—N5	1.229 (3)
N4—Ag1ⁱ	2.2785 (19)	O3—N5	1.230 (3)
C1—C2	1.376 (4)	O4—H4A	0.8601
C1—H1	0.9300	O4—H4B	0.8601
C2—C3	1.365 (4)	O5—H5A	0.8601
C2—H2	0.9300	O5—H5B	0.8600
C3—C4	1.384 (4)

N4ⁱ—Ag1—N1	129.5 (1)	C5—C4—H4	120.7
N4ⁱ—Ag1—N2	159.9 (1)	C3—C4—H4	120.7
N1—Ag1—N2	70.1 (1)	N1—C5—C4	122.9 (2)
N4ⁱ—Ag1—N3ⁱ	69.0 (1)	N1—C5—C6	115.1 (2)
N1—Ag1—N3ⁱ	157.2 (1)	C4—C5—C6	122.0 (2)
N2—Ag1—N3ⁱ	90.9 (1)	N2—C6—C5	121.8 (2)
N4ⁱ—Ag1—O3	79.4 (1)	N2—C6—S1	113.6 (2)
N1—Ag1—O3	76.6 (1)	C5—C6—S1	124.6 (2)
N2—Ag1—O3	113.6 (1)	N3—C7—C8	122.4 (2)
N3ⁱ—Ag1—O3	124.0 (1)	N3—C7—S1	113.7 (2)
C6—S1—C7	87.2 (1)	C8—C7—S1	123.9 (2)
C1—N1—C5	117.4 (2)	N4—C8—C9	123.0 (2)
C1—N1—Ag1	123.0 (2)	N4—C8—C7	114.9 (2)
C5—N1—Ag1	119.2 (2)	C9—C8—C7	122.1 (2)
C6—N2—N3	112.7 (2)	C8—C9—C10	118.7 (2)
C6—N2—Ag1	113.1 (2)	C8—C9—H9	120.6
N3—N2—Ag1	133.5 (2)	C10—C9—H9	120.6
C7—N3—N2	112.8 (2)	C11—C10—C9	118.9 (2)
C7—N3—Ag1ⁱ	109.7 (2)	C11—C10—H10	120.5
N2—N3—Ag1ⁱ	135.3 (2)	C9—C10—H10	120.5
C12—N4—C8	117.2 (2)	C10—C11—C12	119.1 (2)
C12—N4—Ag1ⁱ	120.8 (2)	C10—C11—H11	120.5
C8—N4—Ag1ⁱ	121.8 (2)	C12—C11—H11	120.5
N1—C1—C2	123.0 (2)	N4—C12—C11	123.0 (2)
N1—C1—H1	118.5	N4—C12—H12	118.5
C2—C1—H1	118.5	C11—C12—H12	118.5
C3—C2—C1	119.4 (2)	N5—O3—Ag1	115.4 (2)
C3—C2—H2	120.3	O2—N5—O3	120.5 (2)
C1—C2—H2	120.3	O2—N5—O1	119.2 (2)
C2—C3—C4	118.7 (3)	O3—N5—O1	120.3 (2)
C2—C3—H3	120.6	H4A—O4—H4B	104.9
C4—C3—H3	120.6	H5A—O5—H5B	104.9
C5—C4—C3	118.6 (2)

N4ⁱ—Ag1—N1—C1	11.5 (2)	Ag1—N2—C6—S1	−171.2 (1)
N2—Ag1—N1—C1	−173.9 (2)	N1—C5—C6—N2	−10.6 (3)
N3ⁱ—Ag1—N1—C1	150.9 (2)	C4—C5—C6—N2	168.9 (2)
O3—Ag1—N1—C1	−52.4 (2)	N1—C5—C6—S1	169.5 (2)
N4ⁱ—Ag1—N1—C5	−176.3 (2)	C4—C5—C6—S1	−11.0 (3)
N2—Ag1—N1—C5	−1.7 (2)	C7—S1—C6—N2	−0.1 (2)
N3ⁱ—Ag1—N1—C5	−36.8 (3)	C7—S1—C6—C5	179.8 (2)
O3—Ag1—N1—C5	119.8 (2)	N2—N3—C7—C8	179.5 (2)
N4ⁱ—Ag1—N2—C6	164.0 (2)	Ag1ⁱ—N3—C7—C8	−14.6 (3)
N1—Ag1—N2—C6	−3.8 (2)	N2—N3—C7—S1	0.0 (3)
N3ⁱ—Ag1—N2—C6	163.3 (2)	Ag1ⁱ—N3—C7—S1	165.9 (1)
O3—Ag1—N2—C6	−68.5 (2)	C6—S1—C7—N3	0.1 (2)
N4ⁱ—Ag1—N2—N3	−4.9 (4)	C6—S1—C7—C8	−179.5 (2)
N1—Ag1—N2—N3	−172.7 (2)	C12—N4—C8—C9	1.4 (3)
N3ⁱ—Ag1—N2—N3	−5.6 (3)	Ag1ⁱ—N4—C8—C9	−173.6 (2)
O3—Ag1—N2—N3	122.5 (2)	C12—N4—C8—C7	−177.5 (2)
C6—N2—N3—C7	0.0 (3)	Ag1ⁱ—N4—C8—C7	7.5 (3)
Ag1—N2—N3—C7	168.9 (2)	N3—C7—C8—N4	6.5 (3)
C6—N2—N3—Ag1ⁱ	−161.0 (2)	S1—C7—C8—N4	−174.0 (2)
Ag1—N2—N3—Ag1ⁱ	8.0 (4)	N3—C7—C8—C9	−172.4 (2)
C5—N1—C1—C2	1.4 (4)	S1—C7—C8—C9	7.1 (3)
Ag1—N1—C1—C2	173.8 (2)	N4—C8—C9—C10	−1.0 (4)
N1—C1—C2—C3	−1.2 (4)	C7—C8—C9—C10	177.9 (2)
C1—C2—C3—C4	−0.1 (5)	C8—C9—C10—C11	−0.9 (4)
C2—C3—C4—C5	1.0 (5)	C9—C10—C11—C12	2.1 (4)
C1—N1—C5—C4	−0.4 (3)	C8—N4—C12—C11	−0.1 (4)
Ag1—N1—C5—C4	−173.1 (2)	Ag1ⁱ—N4—C12—C11	175.0 (2)
C1—N1—C5—C6	179.1 (2)	C10—C11—C12—N4	−1.7 (4)
Ag1—N1—C5—C6	6.4 (3)	N4ⁱ—Ag1—O3—N5	−174.6 (2)
C3—C4—C5—N1	−0.8 (4)	N1—Ag1—O3—N5	−39.4 (2)
C3—C4—C5—C6	179.8 (2)	N2—Ag1—O3—N5	21.6 (2)
N3—N2—C6—C5	−179.8 (2)	N3ⁱ—Ag1—O3—N5	129.9 (2)
Ag1—N2—C6—C5	8.9 (3)	Ag1—O3—N5—O2	−39.5 (3)
N3—N2—C6—S1	0.1 (3)	Ag1—O3—N5—O1	141.5 (2)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

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···O4ⁱⁱ	0.86	2.51	2.980 (9)	115
C1—H1···O2ⁱⁱⁱ	0.93	2.44	3.342 (3)	164
C12—H12···O2^iv	0.93	2.48	3.376 (4)	162
O5—H5A···O2^v	0.86	2.05	2.874 (3)	162
O5—H5A···O1^v	0.86	2.46	3.191 (3)	143
O5—H5B···O1^vi	0.86	1.99	2.851 (3)	176

Symmetry codes: (ii) −x, −y, −z+1; (iii) x+1, y, z; (iv) −x, −y, −z; (v) −x+1, −y+1, −z+1; (vi) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Ag₂(C₁₂H₈N₄S)₂(NO₃)₂]·4H₂O
M_r	892.41
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.4251 (1), 10.6894 (3), 14.5865 (3)
α, β, γ (°)	108.910 (1), 91.447 (1), 102.440 (1)
V (Å³)	777.30 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.47
Crystal size (mm)	0.42 × 0.32 × 0.23

Data collection
Diffractometer	Bruker X8 APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008)
T_min, T_max	0.739, 0.867
No. of measured, independent and observed [I > 2σ(I)] reflections	29938, 5388, 3919
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.090, 1.01
No. of reflections	5388
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.92, −0.93

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, y, z; (iii) −x, −y, −z; (iv) −x+1, −y+1, −z+1; (v) −x+2, −y+1, −z+1.

Acknowledgements

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

References

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