Poly[(μ₄-1,2,3-benzo­thia­diazole-7-carboxyl­ato)silver(I)]

In the crystal structure of the title compound, [Ag(C₇H₃N₂O₂S)]_n, the Ag^I atom is coordinated by two N atoms and three O atoms of four organic ligands forming a distorted square pyramid. The carboxyl­ate group acts as a bidentate ligand on one Ag^I atom and as a bridging group for a symmetry-related Ag^I atom, forming a dimer. Futhermore, the two N atoms of two thia­diazole rings bridge a third symmetry-related Ag^I atom, forming a six-membered ring. These two frameworks, AgO₂Ag and AgN₄Ag, extend in three directions, forming a three-dimensionnal polymer. The whole polymer is organized around inversion centers.

Related literature

For a metal-organic complex with inter­esting properties, see: Yaghi et al. (2003). For related structures, see: Chen & Mak (2005); Ng & Othman (1997); Brammer et al. (2002).

Experimental

Crystal data

• [Ag(C₇H₃N₂O₂S)]

• M_r = 287.04

• Monoclinic, P 2₁ /c

• a = 5.8332 (12) Å

• b = 14.786 (3) Å

• c = 8.6377 (17) Å

• β = 93.63 (3)°

• V = 743.5 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 2.95 mm⁻¹

• T = 293 K

• 0.20 × 0.18 × 0.17 mm

Data collection

• Rigaku SCXmini diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995) T_min = 0.630, T_max = 1.000

• 6233 measured reflections

• 1291 independent reflections

• 1144 reflections with I > 2σ(I)

• R_int = 0.044

Refinement

• R[F² > 2σ(F²)] = 0.041

• wR(F²) = 0.075

• S = 1.16

• 1291 reflections

• 118 parameters

• H-atom parameters constrained

• Δρ_max = 1.26 e Å⁻³

• Δρ_min = −0.63 e Å⁻³

Data collection: SCXmini Benchtop Crystallography System Software (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

S1. Comment

Metal organic complexes have drawn much attentions owing to their various structures and their interesting properties (Yaghi et al., 2003). As a bridging ligand benzo[d][1,2,3]thiadiazole-7-carboxylate (L) with three types of heteroatoms has been less investigated. Here we reported the structure of the title complex.

In the title compound, Ag^I is coordinated by two N atoms and three oxygen atoms of four organic ligands forming a distorted square pyramid. The carboxylate group acts as a bidentate ligand on one silver atom and as a bridging group for a symmetry related silver forming a dimer. Futhermore the two nitrogen atoms of two thiadiazole rings bridge a third symmetry related Ag atom forming a six membered ring (Fig. 1). The Ag-O and Ag-N distances are in good agreement with the values observed in related Ag^I complexes (Chen et al., 2005; Ng & Othman, 1997; Brammer et al., 2002) . The thiadiazole groups bridge two Ag^I anions using two nitrogen atoms living the sulfur atoms uncoordinated. In the dimer formed by the carboxylate group, Ag···Ag distance is 3.1168 (12)Å.

The two frameworks AgO2Ag and AgN4Ag extend in the three direction to form a three dimensionnal polymer (Fig. 2) .The whole polymer is organised around inversion centers.

Related literature

For a metal-organic complex with interesting properties, see: Yaghi et al. (2003). For related structures, see: Chen et al. (2005); Ng & Othman (1997); Brammer et al. (2002).

S2. Experimental

A mixture of Ag(I)nitrate (1.5mmol), benzo[d][1,2,3]thiadiazole-7-carboxylate acid (0.75 mmol), in 10 ml water solvent was sealed in a Teflon-lined stainless-steel Parr bomb that was heated at 413 K for 48 h. Red crystals of the title complex were collected after the bomb was allowed to cool to room temperature.Yield 20% based on metal salte.

S3. Refinement

Hydrogen atoms were included in calculated positions and treated as riding on their parent C atoms with C—H = 0.93Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SCXmini Benchtop Crystallography System Software (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The coordinated mode of the metal ions. Ellipsoids are drawn at the 30% probability level. H atom have been omitted for clarity. [ Symmetry codes: i -x+1, y-1/2,-z+1/2; ii -x, -y+1,-z+1; iii -x+1,-y+1,-z+1; iv x-1,-y+3/2,z+1/2].
	Fig. 2. Packing view of the 3D structure viewed along the a axis. H atoms have been omitted for clarity.

Poly[(µ₄-1,2,3-benzothiadiazole-7-carboxylato)silver(I)]

Crystal data

[Ag(C7H3N2O2S)]	F(000) = 552
Mr = 287.04	Dx = 2.564 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6859 reflections
a = 5.8332 (12) Å	θ = 3.5–27.7°
b = 14.786 (3) Å	µ = 2.95 mm^−1
c = 8.6377 (17) Å	T = 293 K
β = 93.63 (3)°	Block, yellow
V = 743.5 (3) Å^3	0.2 × 0.18 × 0.17 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer	1291 independent reflections
Radiation source: fine-focus sealed tube	1144 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ω scans	θmax = 25.0°, θmin = 3.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −6→6
Tmin = 0.630, Tmax = 1	k = −17→17
6233 measured reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H-atom parameters constrained
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0199P)^2 + 2.3752P] where P = (Fo^2 + 2Fc^2)/3
1291 reflections	(Δ/σ)max = 0.001
118 parameters	Δρmax = 1.26 e Å^−3
0 restraints	Δρmin = −0.63 e Å^−3

Special details

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

	x	y	z	Uiso*/Ueq
Ag1	0.22834 (8)	0.54824 (3)	0.55500 (6)	0.04253 (19)
S1	0.8176 (2)	0.67965 (9)	0.27803 (16)	0.0309 (3)
O2	0.9762 (7)	0.8433 (3)	0.1625 (4)	0.0393 (10)
N1	0.4925 (7)	0.6364 (3)	0.4372 (5)	0.0285 (10)
O1	0.8634 (7)	0.9824 (3)	0.2134 (5)	0.0437 (11)
N2	0.6579 (8)	0.6012 (3)	0.3649 (5)	0.0305 (11)
C1	0.8499 (10)	0.8983 (4)	0.2247 (6)	0.0341 (13)
C5	0.3213 (9)	0.7828 (4)	0.4920 (6)	0.0303 (13)
H5A	0.2098	0.7576	0.5511	0.036*
C2	0.6652 (9)	0.8593 (4)	0.3167 (6)	0.0268 (12)
C7	0.6539 (8)	0.7651 (3)	0.3390 (6)	0.0237 (11)
C6	0.4826 (9)	0.7294 (3)	0.4252 (6)	0.0257 (12)
C3	0.5022 (9)	0.9111 (4)	0.3794 (6)	0.0315 (13)
H3A	0.5038	0.9732	0.3631	0.038*
C4	0.3315 (9)	0.8741 (4)	0.4679 (6)	0.0328 (13)
H4A	0.2246	0.9119	0.5104	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0450 (3)	0.0259 (3)	0.0598 (3)	−0.0019 (2)	0.0278 (2)	−0.0036 (2)
S1	0.0320 (8)	0.0274 (7)	0.0347 (8)	0.0004 (6)	0.0123 (6)	−0.0004 (6)
O2	0.039 (2)	0.041 (2)	0.040 (2)	0.0007 (19)	0.0199 (19)	0.0042 (19)
N1	0.028 (2)	0.023 (2)	0.034 (3)	−0.0008 (19)	0.005 (2)	−0.001 (2)
O1	0.057 (3)	0.033 (2)	0.043 (3)	−0.014 (2)	0.016 (2)	0.0093 (19)
N2	0.032 (3)	0.022 (2)	0.038 (3)	−0.001 (2)	0.006 (2)	0.002 (2)
C1	0.037 (3)	0.036 (3)	0.030 (3)	−0.012 (3)	0.004 (3)	0.003 (3)
C5	0.025 (3)	0.028 (3)	0.039 (3)	−0.005 (2)	0.011 (2)	−0.004 (2)
C2	0.029 (3)	0.029 (3)	0.022 (3)	−0.004 (2)	0.000 (2)	−0.001 (2)
C7	0.022 (3)	0.026 (3)	0.023 (3)	−0.002 (2)	0.001 (2)	−0.002 (2)
C6	0.027 (3)	0.027 (3)	0.023 (3)	−0.002 (2)	0.001 (2)	0.001 (2)
C3	0.041 (3)	0.021 (3)	0.033 (3)	0.000 (2)	0.006 (3)	0.000 (2)
C4	0.031 (3)	0.028 (3)	0.041 (3)	0.002 (2)	0.010 (3)	−0.005 (3)

Geometric parameters (Å, º)

Ag1—N1	2.304 (4)	C1—C2	1.494 (7)
Ag1—N2^i	2.396 (4)	C5—C4	1.367 (7)
Ag1—O2^ii	2.402 (4)	C5—C6	1.383 (7)
Ag1—O1^iii	2.540 (4)	C5—H5A	0.9300
Ag1—Ag1^iv	3.1168 (12)	C2—C3	1.360 (7)
S1—C7	1.688 (5)	C2—C7	1.408 (7)
S1—N2	1.693 (4)	C7—C6	1.388 (7)
O2—C1	1.242 (7)	C3—C4	1.404 (7)
N1—N2	1.292 (6)	C3—H3A	0.9300
N1—C6	1.379 (6)	C4—H4A	0.9300
O1—C1	1.251 (7)
N1—Ag1—N2^i	117.94 (15)	O2—C1—C2	116.4 (5)
N1—Ag1—O2^ii	103.64 (15)	O1—C1—C2	118.4 (5)
N2^i—Ag1—O2^ii	132.00 (14)	C4—C5—C6	117.6 (5)
N1—Ag1—O1^iii	85.52 (15)	C4—C5—H5A	121.2
N2^i—Ag1—O1^iii	87.08 (14)	C6—C5—H5A	121.2
O2^ii—Ag1—O1^iii	120.64 (14)	C3—C2—C7	117.5 (5)
N1—Ag1—Ag1^iv	135.00 (11)	C3—C2—C1	122.7 (5)
N2^i—Ag1—Ag1^iv	83.21 (11)	C7—C2—C1	119.7 (5)
O2^ii—Ag1—Ag1^iv	83.74 (10)	C6—C7—C2	119.4 (5)
O1^iii—Ag1—Ag1^iv	54.53 (10)	C6—C7—S1	108.9 (4)
C7—S1—N2	92.1 (2)	C2—C7—S1	131.7 (4)
C1—O2—Ag1^v	97.2 (3)	N1—C6—C5	124.4 (5)
N2—N1—C6	113.3 (4)	N1—C6—C7	113.1 (4)
N2—N1—Ag1	121.7 (3)	C5—C6—C7	122.6 (5)
C6—N1—Ag1	124.8 (3)	C2—C3—C4	122.4 (5)
C1—O1—Ag1^vi	116.2 (4)	C2—C3—H3A	118.8
N1—N2—S1	112.7 (3)	C4—C3—H3A	118.8
N1—N2—Ag1^i	115.7 (3)	C5—C4—C3	120.4 (5)
S1—N2—Ag1^i	127.6 (2)	C5—C4—H4A	119.8
O2—C1—O1	125.1 (5)	C3—C4—H4A	119.8

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, −y+3/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x, −y+1, −z+1; (v) x+1, −y+3/2, z−1/2; (vi) −x+1, y+1/2, −z+1/2.