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In the title complex, [Ag(NO3)(C14H14N4S4)]n, the AgI atom lies on a twofold axis and shows a distorted tetrahedral coordination, comprised of two N-atom donors from two thia­diazole groups of separate ligands and two O-atom donors from one nitrate ligand. Each bis­(thio­ether) ligand also lies on a twofold axis and bridges two adjacent Ag atoms to form an infinite chain along the c axis, with an Ag...Ag separation of 11.462 (4) Å. Adjacent one-dimensional chains are further linked into double-chain motifs through weak Ag...S and [pi]-[pi] stacking interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104019183/ob1194sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104019183/ob1194Isup2.hkl
Contains datablock I

CCDC reference: 224559

Comment top

The rational design of coordination architectures is one of the most exciting fields in current coordination and supramolecular chemistry (Braga et al., 1998). Ligand design is an important aspect in adjusting the coordination framework, and the different numbers and relative orientations of coordination donors in the ligands may lead to the formation of unique frameworks with tailored properties and functions (Blake et al., 1999; Sun et al., 2001; Li et al., 2003; Xie et al., 2004). Di- and triaryl and heteroaryl thioether ligands have shown interesting coordination ability with metal ions (Hong, Zhao et al., 2000; Bu, Hou et al., 2002; Bu, Chen et al., 2002), and the range of heteroaryl groups studied has been enlarged in recent years from pyridine derivatives (Sharma et al., 1999; Constable et al., 2002; Xie & Bu, 2003; Bu et al., 2003) to other heterocyclic thioether ligands (Yang et al., 1997; Hong et al., 2000; Dong et al., 2003; Fan et al., 2003; Zou et al., 2004). In previous work, we have synthesized a bis(thioether) ligand, PBT, which contains two 2-(5-methyl-1,3,4-thiadiazolyl)thio groups separated by an o-xylenediyl spacer (Zheng & Liu, 2003). In this paper, we report the crystal structure of the title compound, (I), which is a new Ag complex with this ligand. \sch

In (I), atoms Ag1, N3 and O2 lie on a twofold axis (Fig. 1). The compound is a one-dimensional polymer and the geometry of the AgI cation is a distorted tetrahedron, comprised of two N donors from two thiadiazole rings of separate PBT ligands and two O donors from one nitrate, with Ag—N and Ag—O bond distances within the range expected for such coordination (Carlucci et al., 1998; Engelhardt et al., 1985; Gotsis & White, 1987).

As in uncoordinated PBT (Zheng & Liu, 2003), the two terminal 2-(5-methyl-1,3,4-thiadiazolyl)thio groups in (I) point in opposite directions to the phenyl plane, in order to reduce the steric repulsion between them. The dihedral angle between the two thiadiazole planes is 50.5 (2)°, and that between the terminal group and the central phenyl plane is 86.6 (3)°. Each PBT ligand bridges two adjacent Ag atoms through Ag—Nthiadiazole coordination to form an infinite chain along the c axis, with an Ag···Ag separation of 11.462 (4) Å (e.g. Ag1A···Ag1B in Fig. 2).

In the crystal packing of (I), adjacent one-dimensional chains are potentially linked into a double-chain motif (Fig. 2) through Ag···S weak interactions [3.54 (3) Å; Orpen et al., 1989; Suenaga et al., 1999; Zheng et al., 2003) and ππ stacking interactions [the interplanar distance between parallel neighbouring thiadiazole rings from two chains is 3.33 (3) Å, and the corresponding centroid-to-centroid distance is 3.72 (4) Å]. All Ag atoms are coplanar and all ligands contribute symmetrically to the plane of the Ag atoms. The two terminal thiadiazole groups of the PBT ligands lie above and below this plane.

Compared with other AgI complexes with bis(thiadiazolylthioether) ligands (Zheng et al., 2003), only one N atom of the thiadiazole ring coordinates to the Ag atom in (I). The reason may be that in PBT, two thiadiazole rings are bridged by a relatively rigid o-xylyl spacer and stretched to the same side of the benzene ring (cis conformation), and this therefore makes the methyl group on the thiadiazole stretch outside. The bulkiness of the methyl group probably hinders the coordination of the neighbouring N atom.

Experimental top

The ligand PBT was prepared in our previous work (Zheng & Liu, 2003) by the reaction of 5-methyl-2-sulfanyl-1,3,4-thiodiazole and 1,2-dibromomethylbenzene. A solution of AgNO3 (90 mg, 0.5 mmol) in methanol (10 ml) was carefully layered on a solution of PBT (183 mg, 0.5 mmol) in chloroform (10 ml), and the mixture was kept in darkness. Colourless crystals of (I) suitable for X-ray analysis were obtained after about two weeks (yield 55%). Elemental analysis, calculated: C 31.32, H 2.61, N 13.05%; found: C 31.17, H 2.68, N 12.83%. IR (KBr pellet, ν, cm−1): 2946 (m), 2868 (w), 1730 (w), 1631 (m), 1497 (m), 1468 (s), 1436 (versus), 1408 (versus), 1376 (versus), 1286 (versus), 1250 (versus), 1190 (s), 1158 (m), 1111 (versus), 1052 (s), 1030 (s), 982 (m), 817 (m), 786 (s), 713 (s), 611 (s).

Refinement top

H atoms were placed geometrically and refined using a riding model, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids. [Symmetry code: (i) x, y, z − 1.]
[Figure 2] Fig. 2. A view of the double-chain motif linked through Ag···S weak interactions in (I), with all H atoms omitted for clarity. Atoms labelled with the suffix A, B, C, D, E or F are at the symmetry positions (-x, y, 3/2 − z), (-x, y, 5/2 − z), (-x, y, 7/2 − z), (x, −y, z − 1/2), (x, −y, 1/2 + z) and (x, −y, 3/2 + z), respectively. Please provide symmetry codes for atoms labelled AA, AB, AC, AD, AE and AF.
catena-Poly[[(nitrato-κ2O,O')silver(I)]-µ-2,2'-[1,4- phenylenebis(methylenethio)]bis(5-methyl-1,3,4-thiadiazole)-κ2N3,N3'] top
Crystal data top
[Ag(NO3)(C14H14N4S4)]F(000) = 1072
Mr = 536.41Dx = 1.853 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 538 reflections
a = 10.670 (5) Åθ = 2.7–24.9°
b = 15.720 (7) ŵ = 1.51 mm1
c = 11.462 (5) ÅT = 293 K
β = 90.627 (7)°Block, colourless
V = 1922.4 (15) Å30.25 × 0.15 × 0.08 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1710 independent reflections
Radiation source: fine-focus sealed tube1389 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ϕ and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996; Blessing, 1995)
h = 1212
Tmin = 0.704, Tmax = 0.889k = 1810
3722 measured reflectionsl = 1213
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.025 w = 1/[σ2(Fo2) + (0.025P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.054(Δ/σ)max = 0.002
S = 1.02Δρmax = 0.37 e Å3
1710 reflectionsΔρmin = 0.41 e Å3
124 parameters
Crystal data top
[Ag(NO3)(C14H14N4S4)]V = 1922.4 (15) Å3
Mr = 536.41Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.670 (5) ŵ = 1.51 mm1
b = 15.720 (7) ÅT = 293 K
c = 11.462 (5) Å0.25 × 0.15 × 0.08 mm
β = 90.627 (7)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1710 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996; Blessing, 1995)
1389 reflections with I > 2σ(I)
Tmin = 0.704, Tmax = 0.889Rint = 0.022
3722 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.054H-atom parameters constrained
S = 1.02Δρmax = 0.37 e Å3
1710 reflectionsΔρmin = 0.41 e Å3
124 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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
xyzUiso*/Ueq
Ag10.00000.09190 (2)0.75000.04673 (13)
S10.22589 (7)0.02562 (4)1.09301 (6)0.04044 (19)
S20.07117 (7)0.18455 (4)1.03058 (6)0.03927 (19)
O10.09705 (19)0.23593 (14)0.72647 (18)0.0563 (6)
O20.00000.3541 (2)0.75000.1222 (17)
N10.1611 (2)0.03348 (13)0.89466 (17)0.0361 (5)
N20.10473 (19)0.04552 (13)0.90370 (16)0.0318 (5)
N30.00000.2766 (2)0.75000.0539 (10)
C10.2954 (3)0.1345 (2)0.9999 (3)0.0577 (9)
H1A0.28350.16850.93100.087*
H1B0.26380.16451.06630.087*
H1C0.38310.12331.01120.087*
C20.2268 (3)0.05257 (17)0.9860 (2)0.0369 (6)
C30.1294 (2)0.08380 (16)1.0023 (2)0.0288 (6)
C40.1202 (2)0.20187 (17)1.1815 (2)0.0354 (6)
H4A0.09500.15451.23010.043*
H4B0.21060.20801.18700.043*
C50.0564 (2)0.28233 (15)1.21941 (19)0.0281 (6)
C60.1089 (2)0.35968 (17)1.1893 (2)0.0370 (6)
H6A0.18320.36021.14760.044*
C70.0546 (3)0.43595 (17)1.2192 (2)0.0419 (7)
H7A0.09180.48701.19770.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0624 (2)0.0416 (2)0.03587 (19)0.0000.01746 (15)0.000
S10.0524 (5)0.0407 (4)0.0280 (4)0.0131 (3)0.0108 (3)0.0057 (3)
S20.0547 (5)0.0341 (4)0.0287 (4)0.0106 (3)0.0090 (3)0.0037 (3)
O10.0491 (13)0.0551 (14)0.0649 (14)0.0062 (11)0.0045 (11)0.0011 (12)
O20.178 (4)0.030 (2)0.159 (4)0.0000.061 (3)0.000
N10.0502 (14)0.0306 (13)0.0274 (12)0.0004 (11)0.0010 (10)0.0037 (10)
N20.0394 (13)0.0295 (12)0.0264 (12)0.0009 (10)0.0034 (9)0.0001 (10)
N30.078 (3)0.036 (2)0.048 (2)0.0000.008 (2)0.000
C10.079 (2)0.0465 (19)0.0470 (18)0.0244 (18)0.0081 (16)0.0085 (16)
C20.0491 (17)0.0328 (15)0.0288 (14)0.0031 (13)0.0031 (12)0.0024 (12)
C30.0297 (14)0.0322 (15)0.0245 (12)0.0016 (11)0.0001 (10)0.0003 (11)
C40.0423 (16)0.0370 (16)0.0269 (13)0.0064 (13)0.0053 (11)0.0063 (12)
C50.0334 (14)0.0286 (14)0.0221 (12)0.0024 (11)0.0047 (10)0.0011 (11)
C60.0365 (15)0.0411 (18)0.0336 (14)0.0060 (13)0.0046 (12)0.0014 (13)
C70.0555 (19)0.0281 (15)0.0420 (16)0.0110 (13)0.0074 (13)0.0059 (13)
Geometric parameters (Å, º) top
Ag1—N2i2.200 (2)C1—C21.489 (4)
Ag1—N22.200 (2)C1—H1A0.9600
Ag1—O12.506 (2)C1—H1B0.9600
Ag1—O1i2.506 (2)C1—H1C0.9600
S1—C31.719 (2)C4—C51.503 (3)
S1—C21.736 (3)C4—H4A0.9700
S2—C31.733 (3)C4—H4B0.9700
S2—C41.822 (2)C5—C61.384 (4)
O1—N31.249 (3)C5—C5ii1.400 (5)
O2—N31.217 (5)C6—C71.377 (4)
N1—C21.289 (3)C6—H6A0.9300
N1—N21.384 (3)C7—C7ii1.369 (6)
N2—C31.305 (3)C7—H7A0.9300
N3—O1i1.249 (3)
N2i—Ag1—N2141.29 (11)N1—C2—C1123.4 (2)
N2i—Ag1—O1114.85 (7)N1—C2—S1113.7 (2)
N2—Ag1—O1100.30 (7)C1—C2—S1122.9 (2)
N2i—Ag1—O1i100.30 (7)N2—C3—S1113.09 (19)
N2—Ag1—O1i114.85 (7)N2—C3—S2120.93 (18)
O1—Ag1—O1i50.71 (10)S1—C3—S2125.95 (14)
C3—S1—C287.57 (12)C5—C4—S2105.89 (16)
C3—S2—C4102.36 (11)C5—C4—H4A110.6
N3—O1—Ag195.46 (19)S2—C4—H4A110.6
C2—N1—N2112.4 (2)C5—C4—H4B110.6
C3—N2—N1113.3 (2)S2—C4—H4B110.6
C3—N2—Ag1129.54 (17)H4A—C4—H4B108.7
N1—N2—Ag1117.04 (14)C6—C5—C5ii118.51 (15)
O2—N3—O1i120.81 (18)C6—C5—C4118.8 (2)
O2—N3—O1120.81 (18)C5ii—C5—C4122.65 (14)
O1i—N3—O1118.4 (4)C7—C6—C5122.1 (2)
C2—C1—H1A109.5C7—C6—H6A119.0
C2—C1—H1B109.5C5—C6—H6A119.0
H1A—C1—H1B109.5C7ii—C7—C6119.43 (16)
C2—C1—H1C109.5C7ii—C7—H7A120.3
H1A—C1—H1C109.5C6—C7—H7A120.3
H1B—C1—H1C109.5
N2i—Ag1—O1—N382.86 (12)C3—S1—C2—C1178.7 (3)
N2—Ag1—O1—N3113.77 (11)N1—N2—C3—S10.4 (3)
O1i—Ag1—O1—N30.0Ag1—N2—C3—S1174.91 (11)
C2—N1—N2—C30.2 (3)N1—N2—C3—S2178.53 (16)
C2—N1—N2—Ag1175.74 (17)Ag1—N2—C3—S23.2 (3)
N2i—Ag1—N2—C3157.5 (2)C2—S1—C3—N20.4 (2)
O1—Ag1—N2—C347.1 (2)C2—S1—C3—S2178.37 (19)
O1i—Ag1—N2—C34.2 (2)C4—S2—C3—N2174.7 (2)
N2i—Ag1—N2—N127.32 (15)C4—S2—C3—S17.4 (2)
O1—Ag1—N2—N1128.14 (17)C3—S2—C4—C5171.42 (17)
O1i—Ag1—N2—N1179.44 (15)S2—C4—C5—C681.5 (2)
Ag1—O1—N3—O2180.0S2—C4—C5—C5ii96.2 (3)
Ag1—O1—N3—O1i0.0C5ii—C5—C6—C71.0 (4)
N2—N1—C2—C1178.9 (3)C4—C5—C6—C7178.8 (2)
N2—N1—C2—S10.1 (3)C5—C6—C7—C7ii0.1 (5)
C3—S1—C2—N10.3 (2)
Symmetry codes: (i) x, y, z+3/2; (ii) x, y, z+5/2.

Experimental details

Crystal data
Chemical formula[Ag(NO3)(C14H14N4S4)]
Mr536.41
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)10.670 (5), 15.720 (7), 11.462 (5)
β (°) 90.627 (7)
V3)1922.4 (15)
Z4
Radiation typeMo Kα
µ (mm1)1.51
Crystal size (mm)0.25 × 0.15 × 0.08
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996; Blessing, 1995)
Tmin, Tmax0.704, 0.889
No. of measured, independent and
observed [I > 2σ(I)] reflections
3722, 1710, 1389
Rint0.022
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.054, 1.02
No. of reflections1710
No. of parameters124
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.41

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.

Selected geometric parameters (Å, º) top
Ag1—N22.200 (2)Ag1—O12.506 (2)
N2i—Ag1—N2141.29 (11)N2—Ag1—O1i114.85 (7)
N2—Ag1—O1100.30 (7)O1—Ag1—O1i50.71 (10)
Symmetry code: (i) x, y, z+3/2.
 

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