Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017319/qs3025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017319/qs3025Isup2.hkl |
CCDC reference: 958904
Current interest in metal–organic coordination polymers is expanding rapidly due to their intriguing architectures and potential applications (Žurowska et al., 2006; Eddaoudi et al., 2005; Ye et al., 2006). In an effort to establish strategies aimed at designing novel metal–organic frameworks, we have chosen ligands with carboxylate groups, such as naphthaleneacetate (Duan et al., 2007), 3-hydroxybenzoate (Liu & Ng, 2007), dichlorophenoxyacetate (Gu et al., 2006) and methyl benzoate (Song et al., 2007), to bind metal centres into novel metal–organic networks. In this work, we chose sulfanediyldiacetic acid (also known as 2,2-thiodiglycolic acid) as a ligand to prepare a coordination polymer since it has, surprisingly, not been used as a ligand previously (Alarcón-Payer et al., 2005; Wu et al., 2005). This organic carboxylate ligand, which has various coordination modes, can link metal centres through its carboxylate groups or/and the S atom to form different extended architectures, and so is regarded as a good candidate for constructing various metal–organic coordination polymers. We report here the crystal structure of the title three-dimensional coordination polymer, (I).
Experimental details are summarized in Table 1.
Sulfanediyldiacetic acid was commercially available and was used without further purification. The title complex was prepared by the addition of AgNO3 (3.40 g, 20 mmol) and methenamine (1.40 g, 10 mmol) to a hot aqueous solution of sulfanediyldiacetic acid (10 ml, 10 mmol); the pH was adjusted to 6 using 0.1 M potassium hydroxide. The solution was left to evaporate at room temperature. Blue [Colourless given in CIF table - please clarify] prismatic crystals of (I) were separated from the filtered solution after three weeks. Analysis, calculated for C4H4Ag2O4S: C 13.27, H 1.11%; found: C 13.29, H 1.10%.
H atoms [on C atoms?] were placed in calculated positions, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C), and were refined in the riding-model approximation. Water [Carboxylate?] H atoms were located in a difference Fourier map and refined with O—H = 0.85 Å and Uiso(H) = 1.5Ueq(O).
Each AgII cation of (I) (Fig. 1) displays a distorted tetrahedral geometry defined by three of the four carboxylate O atoms and one S atom from different sulfanediyldiacetate ligands. The Ag—O bond lengths (Table 2) vary from 2.223 (4) to 2.488 (4) Å.
Fig. 2 shows part of the two-dimensional network of (I). The two types of carboxylate O atom of the sulfanediyldiacetate ligand are distinguished by two coordination modes, one mode being monodentate, always via a carbonyl O atom, and the other bidentate. Thus, the AgI cations are linked by monodentate sulfanediyldiacetate ligands to form a one-dimensional chain displaying eight-membered chelate rings. The chains are assembled by bidentate sulfanediyldiacetate ligands into a two-dimensional infinite layer structure displaying four- and 16-membered chelate rings. The layers are further connected by S atoms, giving rise to a three-dimensional network (Fig. 3).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Ag2(C4H4O4S)] | F(000) = 680 |
Mr = 363.87 | Dx = 3.565 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3598 reflections |
a = 5.2113 (10) Å | θ = 2.0–25.0° |
b = 20.355 (4) Å | µ = 6.04 mm−1 |
c = 6.7616 (13) Å | T = 296 K |
β = 109.045 (2)° | Prism, colourless |
V = 678.0 (2) Å3 | 0.32 × 0.24 × 0.18 mm |
Z = 4 |
Bruker P4 diffractometer | 1187 independent reflections |
Radiation source: fine-focus sealed tube | 1136 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 10.000 pixels mm-1 | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −6→6 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2000) | k = −24→18 |
Tmin = 0.192, Tmax = 0.337 | l = −8→7 |
3598 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.120 | w = 1/[σ2(Fo2) + (0.0846P)2 + 1.5664P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
1187 reflections | Δρmax = 1.25 e Å−3 |
101 parameters | Δρmin = −1.61 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008) |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0126 (15) |
[Ag2(C4H4O4S)] | V = 678.0 (2) Å3 |
Mr = 363.87 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.2113 (10) Å | µ = 6.04 mm−1 |
b = 20.355 (4) Å | T = 296 K |
c = 6.7616 (13) Å | 0.32 × 0.24 × 0.18 mm |
β = 109.045 (2)° |
Bruker P4 diffractometer | 1187 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2000) | 1136 reflections with I > 2σ(I) |
Tmin = 0.192, Tmax = 0.337 | Rint = 0.033 |
3598 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.25 e Å−3 |
1187 reflections | Δρmin = −1.61 e Å−3 |
101 parameters |
x | y | z | Uiso*/Ueq | ||
Ag1 | 0.62899 (9) | 0.90487 (2) | 0.62428 (8) | 0.0290 (3) | |
Ag2 | 0.33036 (9) | 0.84612 (2) | 0.89651 (8) | 0.0312 (3) | |
S1 | 0.6706 (3) | 0.62535 (6) | 0.7634 (2) | 0.0202 (4) | |
O1 | 0.8938 (8) | 0.4435 (2) | 0.7245 (8) | 0.0327 (11) | |
O2 | 0.5327 (9) | 0.4932 (2) | 0.7633 (8) | 0.0353 (11) | |
O3 | 0.8654 (8) | 0.8112 (2) | 0.8005 (7) | 0.0271 (10) | |
O4 | 0.4941 (10) | 0.7543 (2) | 0.7806 (8) | 0.0344 (11) | |
C1 | 0.8924 (11) | 0.5601 (3) | 0.7306 (9) | 0.0228 (12) | |
C2 | 0.8985 (11) | 0.6949 (3) | 0.8066 (9) | 0.0214 (12) | |
C3 | 0.7627 (11) | 0.4934 (3) | 0.7392 (9) | 0.0214 (12) | |
C4 | 0.7400 (11) | 0.7585 (3) | 0.7942 (8) | 0.0191 (12) | |
H1A | 0.9225 | 0.5651 | 0.5973 | 0.027* | |
H1B | 1.0667 | 0.5628 | 0.8407 | 0.027* | |
H2A | 1.0362 | 0.6913 | 0.9432 | 0.026* | |
H2B | 0.9887 | 0.6953 | 0.7018 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0269 (4) | 0.0250 (4) | 0.0377 (4) | 0.00393 (17) | 0.0140 (3) | −0.00127 (18) |
Ag2 | 0.0222 (4) | 0.0245 (4) | 0.0444 (4) | 0.00268 (17) | 0.0075 (3) | −0.0009 (2) |
S1 | 0.0212 (8) | 0.0157 (8) | 0.0242 (8) | −0.0008 (5) | 0.0079 (6) | −0.0002 (5) |
O1 | 0.023 (2) | 0.019 (2) | 0.053 (3) | 0.0001 (17) | 0.007 (2) | −0.006 (2) |
O2 | 0.033 (2) | 0.022 (2) | 0.059 (3) | −0.0039 (19) | 0.028 (2) | 0.000 (2) |
O3 | 0.023 (2) | 0.013 (2) | 0.042 (2) | −0.0007 (16) | 0.0070 (17) | 0.0025 (18) |
O4 | 0.027 (2) | 0.027 (3) | 0.054 (3) | −0.0044 (19) | 0.020 (2) | −0.008 (2) |
C1 | 0.021 (3) | 0.022 (3) | 0.027 (3) | −0.001 (2) | 0.009 (2) | −0.002 (2) |
C2 | 0.024 (3) | 0.017 (3) | 0.023 (3) | −0.002 (2) | 0.008 (2) | 0.002 (2) |
C3 | 0.024 (3) | 0.017 (3) | 0.022 (3) | −0.001 (2) | 0.005 (2) | 0.002 (2) |
C4 | 0.024 (3) | 0.016 (3) | 0.018 (3) | 0.000 (2) | 0.008 (2) | −0.003 (2) |
Ag1—Ag2 | 3.0182 (8) | O3—Ag2viii | 2.403 (4) |
Ag1—S1i | 2.5936 (16) | C1—S1 | 1.821 (6) |
Ag1—O1ii | 2.488 (4) | C1—C3 | 1.527 (7) |
Ag1—O2iii | 2.223 (4) | C1—H1A | 0.9700 |
Ag1—O3 | 2.370 (4) | C1—H1B | 0.9700 |
Ag2—S1iv | 2.6007 (16) | C2—S1 | 1.810 (6) |
Ag2—O1iii | 2.311 (4) | C2—C4 | 1.524 (7) |
Ag2—O3v | 2.403 (4) | C2—H2A | 0.9700 |
Ag2—O4 | 2.296 (4) | C2—H2B | 0.9700 |
S1—Ag1iv | 2.5936 (16) | C3—O1 | 1.245 (7) |
S1—Ag2i | 2.6007 (16) | C3—O2 | 1.261 (7) |
O1—Ag2vi | 2.311 (4) | C4—O3 | 1.248 (7) |
O1—Ag1vii | 2.488 (4) | C4—O4 | 1.258 (7) |
O2—Ag1vi | 2.223 (4) | ||
Ag1iv—S1—Ag2i | 135.24 (6) | S1—C2—H2B | 109.7 |
Ag2vi—O1—Ag1vii | 101.32 (15) | O1—C3—O2 | 125.3 (6) |
Ag1—O3—Ag2viii | 102.15 (15) | O1—C3—C1 | 117.4 (5) |
S1i—Ag1—Ag2 | 134.27 (4) | O2—C3—C1 | 117.2 (5) |
S1iv—Ag2—Ag1 | 99.58 (4) | O3—C4—O4 | 124.8 (5) |
O1ii—Ag1—S1i | 94.73 (12) | O3—C4—C2 | 117.4 (5) |
O1ii—Ag1—Ag2 | 121.32 (11) | O4—C4—C2 | 117.8 (5) |
O1iii—Ag2—S1iv | 104.76 (12) | C1—S1—Ag1iv | 101.11 (19) |
O1iii—Ag2—O3v | 79.02 (15) | C1—S1—Ag2i | 108.0 (2) |
O1iii—Ag2—Ag1 | 75.29 (12) | C2—S1—Ag1iv | 106.6 (2) |
O2iii—Ag1—Ag2 | 77.50 (12) | C2—S1—Ag2i | 100.76 (19) |
O2iii—Ag1—S1i | 132.15 (14) | C2—S1—C1 | 100.5 (3) |
O2iii—Ag1—O1ii | 92.47 (16) | C3—O1—Ag1vii | 136.5 (4) |
O2iii—Ag1—O3 | 132.22 (18) | C3—O1—Ag2vi | 120.0 (4) |
O3—Ag1—Ag2 | 70.20 (11) | C3—O2—Ag1vi | 121.9 (4) |
O3—Ag1—S1i | 95.34 (12) | C3—C1—S1 | 109.8 (4) |
O3—Ag1—O1ii | 76.23 (14) | C3—C1—H1A | 109.7 |
O3v—Ag2—Ag1 | 128.89 (11) | C3—C1—H1B | 109.7 |
O3v—Ag2—S1iv | 129.60 (12) | C4—O3—Ag1 | 119.6 (4) |
O4—Ag2—Ag1 | 77.96 (12) | C4—O3—Ag2viii | 137.2 (4) |
O4—Ag2—S1iv | 107.07 (14) | C4—O4—Ag2 | 113.7 (4) |
O4—Ag2—O1iii | 141.15 (19) | C4—C2—S1 | 109.9 (4) |
O4—Ag2—O3v | 96.96 (16) | C4—C2—H2A | 109.7 |
S1—C1—H1A | 109.7 | C4—C2—H2B | 109.7 |
S1—C1—H1B | 109.7 | H1A—C1—H1B | 108.2 |
S1—C2—H2A | 109.7 | H2A—C2—H2B | 108.2 |
Ag1—Ag2—O4—C4 | 46.6 (4) | O2iii—Ag1—Ag2—O4 | 179.74 (19) |
Ag2—Ag1—O3—Ag2viii | −139.47 (17) | O2iii—Ag1—O3—Ag2viii | −89.1 (2) |
Ag2—Ag1—O3—C4 | 50.5 (4) | O2iii—Ag1—O3—C4 | 100.9 (4) |
S1i—Ag1—Ag2—S1iv | 147.25 (7) | O2—C3—O1—Ag2vi | 25.7 (8) |
S1i—Ag1—Ag2—O1iii | −109.88 (13) | O2—C3—O1—Ag1vii | −134.2 (5) |
S1i—Ag1—Ag2—O3v | −47.58 (14) | O3—Ag1—Ag2—O4 | −36.03 (17) |
S1i—Ag1—Ag2—O4 | 41.68 (15) | O3—Ag1—Ag2—S1iv | 69.54 (11) |
S1i—Ag1—O3—Ag2viii | 85.18 (14) | O3—Ag1—Ag2—O1iii | 172.41 (15) |
S1i—Ag1—O3—C4 | −84.8 (4) | O3—Ag1—Ag2—O3v | −125.3 (2) |
S1iv—Ag2—O4—C4 | −49.8 (5) | O3v—Ag2—O4—C4 | 175.0 (4) |
S1—C1—C3—O1 | −178.2 (5) | O3—C4—O4—Ag2 | −23.1 (8) |
S1—C1—C3—O2 | 0.9 (7) | O4—C4—O3—Ag1 | −30.9 (8) |
S1—C2—C4—O3 | −173.2 (4) | C1—C3—O1—Ag1vii | 44.8 (8) |
S1—C2—C4—O4 | 7.5 (7) | C1—C3—O1—Ag2vi | −155.3 (4) |
O1ii—Ag1—Ag2—S1iv | 10.54 (12) | C1—C3—O2—Ag1vi | −160.8 (4) |
O1ii—Ag1—Ag2—O1iii | 113.4 (2) | C2—C4—O3—Ag1 | 149.9 (4) |
O1ii—Ag1—Ag2—O3v | 175.71 (16) | O4—C4—O3—Ag2viii | 163.6 (4) |
O1ii—Ag1—Ag2—O4 | −95.03 (18) | C2—C4—O3—Ag2viii | −15.6 (8) |
O1ii—Ag1—O3—Ag2viii | −8.40 (16) | C2—C4—O4—Ag2 | 156.2 (4) |
O1ii—Ag1—O3—C4 | −178.4 (5) | C3—C1—S1—Ag1iv | 58.3 (4) |
O1iii—Ag2—O4—C4 | 93.9 (5) | C3—C1—S1—Ag2i | −87.3 (4) |
O1—C3—O2—Ag1vi | 18.2 (8) | C3—C1—S1—C2 | 167.7 (4) |
O2iii—Ag1—Ag2—S1iv | −74.69 (14) | C4—C2—S1—Ag1iv | −86.5 (4) |
O2iii—Ag1—Ag2—O1iii | 28.18 (18) | C4—C2—S1—Ag2i | 57.6 (4) |
O2iii—Ag1—Ag2—O3v | 90.48 (18) | C4—C2—S1—C1 | 168.4 (4) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+1, y+1/2, −z+3/2; (iv) x, −y+3/2, z+1/2; (v) x−1, y, z; (vi) −x+1, y−1/2, −z+3/2; (vii) −x+2, y−1/2, −z+3/2; (viii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Ag2(C4H4O4S)] |
Mr | 363.87 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 5.2113 (10), 20.355 (4), 6.7616 (13) |
β (°) | 109.045 (2) |
V (Å3) | 678.0 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 6.04 |
Crystal size (mm) | 0.32 × 0.24 × 0.18 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.192, 0.337 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3598, 1187, 1136 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.120, 1.09 |
No. of reflections | 1187 |
No. of parameters | 101 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.25, −1.61 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).