Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104019183/ob1194sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104019183/ob1194Isup2.hkl |
CCDC reference: 224559
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).
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).
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.
[Ag(NO3)(C14H14N4S4)] | F(000) = 1072 |
Mr = 536.41 | Dx = 1.853 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 538 reflections |
a = 10.670 (5) Å | θ = 2.7–24.9° |
b = 15.720 (7) Å | µ = 1.51 mm−1 |
c = 11.462 (5) Å | T = 293 K |
β = 90.627 (7)° | Block, colourless |
V = 1922.4 (15) Å3 | 0.25 × 0.15 × 0.08 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 1710 independent reflections |
Radiation source: fine-focus sealed tube | 1389 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | h = −12→12 |
Tmin = 0.704, Tmax = 0.889 | k = −18→10 |
3722 measured reflections | l = −12→13 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-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 = 1.02 | Δρmax = 0.37 e Å−3 |
1710 reflections | Δρmin = −0.41 e Å−3 |
124 parameters |
[Ag(NO3)(C14H14N4S4)] | V = 1922.4 (15) Å3 |
Mr = 536.41 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.670 (5) Å | µ = 1.51 mm−1 |
b = 15.720 (7) Å | T = 293 K |
c = 11.462 (5) Å | 0.25 × 0.15 × 0.08 mm |
β = 90.627 (7)° |
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 = 0.889 | Rint = 0.022 |
3722 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.37 e Å−3 |
1710 reflections | Δρmin = −0.41 e Å−3 |
124 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ag1 | 0.0000 | 0.09190 (2) | 0.7500 | 0.04673 (13) | |
S1 | 0.22589 (7) | 0.02562 (4) | 1.09301 (6) | 0.04044 (19) | |
S2 | 0.07117 (7) | 0.18455 (4) | 1.03058 (6) | 0.03927 (19) | |
O1 | 0.09705 (19) | 0.23593 (14) | 0.72647 (18) | 0.0563 (6) | |
O2 | 0.0000 | 0.3541 (2) | 0.7500 | 0.1222 (17) | |
N1 | 0.1611 (2) | −0.03348 (13) | 0.89466 (17) | 0.0361 (5) | |
N2 | 0.10473 (19) | 0.04552 (13) | 0.90370 (16) | 0.0318 (5) | |
N3 | 0.0000 | 0.2766 (2) | 0.7500 | 0.0539 (10) | |
C1 | 0.2954 (3) | −0.1345 (2) | 0.9999 (3) | 0.0577 (9) | |
H1A | 0.2835 | −0.1685 | 0.9310 | 0.087* | |
H1B | 0.2638 | −0.1645 | 1.0663 | 0.087* | |
H1C | 0.3831 | −0.1233 | 1.0112 | 0.087* | |
C2 | 0.2268 (3) | −0.05257 (17) | 0.9860 (2) | 0.0369 (6) | |
C3 | 0.1294 (2) | 0.08380 (16) | 1.0023 (2) | 0.0288 (6) | |
C4 | 0.1202 (2) | 0.20187 (17) | 1.1815 (2) | 0.0354 (6) | |
H4A | 0.0950 | 0.1545 | 1.2301 | 0.043* | |
H4B | 0.2106 | 0.2080 | 1.1870 | 0.043* | |
C5 | 0.0564 (2) | 0.28233 (15) | 1.21941 (19) | 0.0281 (6) | |
C6 | 0.1089 (2) | 0.35968 (17) | 1.1893 (2) | 0.0370 (6) | |
H6A | 0.1832 | 0.3602 | 1.1476 | 0.044* | |
C7 | 0.0546 (3) | 0.43595 (17) | 1.2192 (2) | 0.0419 (7) | |
H7A | 0.0918 | 0.4870 | 1.1977 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0624 (2) | 0.0416 (2) | 0.03587 (19) | 0.000 | −0.01746 (15) | 0.000 |
S1 | 0.0524 (5) | 0.0407 (4) | 0.0280 (4) | 0.0131 (3) | −0.0108 (3) | −0.0057 (3) |
S2 | 0.0547 (5) | 0.0341 (4) | 0.0287 (4) | 0.0106 (3) | −0.0090 (3) | −0.0037 (3) |
O1 | 0.0491 (13) | 0.0551 (14) | 0.0649 (14) | −0.0062 (11) | 0.0045 (11) | 0.0011 (12) |
O2 | 0.178 (4) | 0.030 (2) | 0.159 (4) | 0.000 | 0.061 (3) | 0.000 |
N1 | 0.0502 (14) | 0.0306 (13) | 0.0274 (12) | −0.0004 (11) | −0.0010 (10) | −0.0037 (10) |
N2 | 0.0394 (13) | 0.0295 (12) | 0.0264 (12) | −0.0009 (10) | −0.0034 (9) | 0.0001 (10) |
N3 | 0.078 (3) | 0.036 (2) | 0.048 (2) | 0.000 | 0.008 (2) | 0.000 |
C1 | 0.079 (2) | 0.0465 (19) | 0.0470 (18) | 0.0244 (18) | −0.0081 (16) | −0.0085 (16) |
C2 | 0.0491 (17) | 0.0328 (15) | 0.0288 (14) | 0.0031 (13) | 0.0031 (12) | −0.0024 (12) |
C3 | 0.0297 (14) | 0.0322 (15) | 0.0245 (12) | −0.0016 (11) | 0.0001 (10) | −0.0003 (11) |
C4 | 0.0423 (16) | 0.0370 (16) | 0.0269 (13) | 0.0064 (13) | −0.0053 (11) | −0.0063 (12) |
C5 | 0.0334 (14) | 0.0286 (14) | 0.0221 (12) | 0.0024 (11) | −0.0047 (10) | −0.0011 (11) |
C6 | 0.0365 (15) | 0.0411 (18) | 0.0336 (14) | −0.0060 (13) | 0.0046 (12) | 0.0014 (13) |
C7 | 0.0555 (19) | 0.0281 (15) | 0.0420 (16) | −0.0110 (13) | −0.0074 (13) | 0.0059 (13) |
Ag1—N2i | 2.200 (2) | C1—C2 | 1.489 (4) |
Ag1—N2 | 2.200 (2) | C1—H1A | 0.9600 |
Ag1—O1 | 2.506 (2) | C1—H1B | 0.9600 |
Ag1—O1i | 2.506 (2) | C1—H1C | 0.9600 |
S1—C3 | 1.719 (2) | C4—C5 | 1.503 (3) |
S1—C2 | 1.736 (3) | C4—H4A | 0.9700 |
S2—C3 | 1.733 (3) | C4—H4B | 0.9700 |
S2—C4 | 1.822 (2) | C5—C6 | 1.384 (4) |
O1—N3 | 1.249 (3) | C5—C5ii | 1.400 (5) |
O2—N3 | 1.217 (5) | C6—C7 | 1.377 (4) |
N1—C2 | 1.289 (3) | C6—H6A | 0.9300 |
N1—N2 | 1.384 (3) | C7—C7ii | 1.369 (6) |
N2—C3 | 1.305 (3) | C7—H7A | 0.9300 |
N3—O1i | 1.249 (3) | ||
N2i—Ag1—N2 | 141.29 (11) | N1—C2—C1 | 123.4 (2) |
N2i—Ag1—O1 | 114.85 (7) | N1—C2—S1 | 113.7 (2) |
N2—Ag1—O1 | 100.30 (7) | C1—C2—S1 | 122.9 (2) |
N2i—Ag1—O1i | 100.30 (7) | N2—C3—S1 | 113.09 (19) |
N2—Ag1—O1i | 114.85 (7) | N2—C3—S2 | 120.93 (18) |
O1—Ag1—O1i | 50.71 (10) | S1—C3—S2 | 125.95 (14) |
C3—S1—C2 | 87.57 (12) | C5—C4—S2 | 105.89 (16) |
C3—S2—C4 | 102.36 (11) | C5—C4—H4A | 110.6 |
N3—O1—Ag1 | 95.46 (19) | S2—C4—H4A | 110.6 |
C2—N1—N2 | 112.4 (2) | C5—C4—H4B | 110.6 |
C3—N2—N1 | 113.3 (2) | S2—C4—H4B | 110.6 |
C3—N2—Ag1 | 129.54 (17) | H4A—C4—H4B | 108.7 |
N1—N2—Ag1 | 117.04 (14) | C6—C5—C5ii | 118.51 (15) |
O2—N3—O1i | 120.81 (18) | C6—C5—C4 | 118.8 (2) |
O2—N3—O1 | 120.81 (18) | C5ii—C5—C4 | 122.65 (14) |
O1i—N3—O1 | 118.4 (4) | C7—C6—C5 | 122.1 (2) |
C2—C1—H1A | 109.5 | C7—C6—H6A | 119.0 |
C2—C1—H1B | 109.5 | C5—C6—H6A | 119.0 |
H1A—C1—H1B | 109.5 | C7ii—C7—C6 | 119.43 (16) |
C2—C1—H1C | 109.5 | C7ii—C7—H7A | 120.3 |
H1A—C1—H1C | 109.5 | C6—C7—H7A | 120.3 |
H1B—C1—H1C | 109.5 | ||
N2i—Ag1—O1—N3 | 82.86 (12) | C3—S1—C2—C1 | −178.7 (3) |
N2—Ag1—O1—N3 | −113.77 (11) | N1—N2—C3—S1 | 0.4 (3) |
O1i—Ag1—O1—N3 | 0.0 | Ag1—N2—C3—S1 | −174.91 (11) |
C2—N1—N2—C3 | −0.2 (3) | N1—N2—C3—S2 | 178.53 (16) |
C2—N1—N2—Ag1 | 175.74 (17) | Ag1—N2—C3—S2 | 3.2 (3) |
N2i—Ag1—N2—C3 | −157.5 (2) | C2—S1—C3—N2 | −0.4 (2) |
O1—Ag1—N2—C3 | 47.1 (2) | C2—S1—C3—S2 | −178.37 (19) |
O1i—Ag1—N2—C3 | −4.2 (2) | C4—S2—C3—N2 | 174.7 (2) |
N2i—Ag1—N2—N1 | 27.32 (15) | C4—S2—C3—S1 | −7.4 (2) |
O1—Ag1—N2—N1 | −128.14 (17) | C3—S2—C4—C5 | −171.42 (17) |
O1i—Ag1—N2—N1 | −179.44 (15) | S2—C4—C5—C6 | −81.5 (2) |
Ag1—O1—N3—O2 | 180.0 | S2—C4—C5—C5ii | 96.2 (3) |
Ag1—O1—N3—O1i | 0.0 | C5ii—C5—C6—C7 | 1.0 (4) |
N2—N1—C2—C1 | 178.9 (3) | C4—C5—C6—C7 | 178.8 (2) |
N2—N1—C2—S1 | −0.1 (3) | C5—C6—C7—C7ii | 0.1 (5) |
C3—S1—C2—N1 | 0.3 (2) |
Symmetry codes: (i) −x, y, −z+3/2; (ii) −x, y, −z+5/2. |
Experimental details
Crystal data | |
Chemical formula | [Ag(NO3)(C14H14N4S4)] |
Mr | 536.41 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.670 (5), 15.720 (7), 11.462 (5) |
β (°) | 90.627 (7) |
V (Å3) | 1922.4 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.51 |
Crystal size (mm) | 0.25 × 0.15 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) |
Tmin, Tmax | 0.704, 0.889 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3722, 1710, 1389 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.054, 1.02 |
No. of reflections | 1710 |
No. of parameters | 124 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.41 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
Ag1—N2 | 2.200 (2) | Ag1—O1 | 2.506 (2) |
N2i—Ag1—N2 | 141.29 (11) | N2—Ag1—O1i | 114.85 (7) |
N2—Ag1—O1 | 100.30 (7) | O1—Ag1—O1i | 50.71 (10) |
Symmetry code: (i) −x, y, −z+3/2. |
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 π–π 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.