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In the title complex, [Ag2(C7H4NO4)2(C16H16S2)], each AgI atom is trigonally coordinated by one S atom of a 2,11-dithia­[3.3]paracyclo­phane (dtpcp) ligand, and by one N and one O atom of a 6-carboxy­pyridine-2-carboxylate ligand. Dtpcp acts as a bidentate ligand, bridging two inversion-related AgI atoms to give a dinuclear silver(I) compound. The dinuclear moieties are inter­connected via O-H...O hydrogen bonds to form a two-dimensional zigzag sheet. Two such sheets are inter­woven via [pi]-[pi] inter­actions between pyridine rings, affording an inter­woven bilayer network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105006372/ob1220sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105006372/ob1220Isup2.hkl
Contains datablock I

CCDC reference: 269018

Comment top

The design of inorganic–organic hybrid frameworks, in particular the construction of polymeric silver(I) coordination networks, has become a growing active research area due to the potential application of these polymers as functional materials with controllable properties and novel molecular structures (Khlobystov et al., 2001; Hu et al., 2003; Yaghi & Li, 1996; Zhao et al., 2001). Recent developments in supramolecular chemistry have made it possible to select building blocks to assemble structures with specific networks. Many investigations in this field have been focused on the construction of metal-organic complexes containing N– or S-atom donor ligands. Very recently, attention has been diverted to the complexes based on mixed ligands. We chose here 2,6-pyridinedicarboxylic acid (H2pdc) with an N-atom donor and 2,11-dithia[3.3]paracyclophane (dtpcp) with an S-atom donor as mixed ligands. Although metal complexes of H2pdc have been studied extensively because of its ability to form stable chelates (Ducommun, et al., 1989; Sengupta et al., 1983; Zhou & Kostic, 1988), the structural characterization of its silver(I) complexes is very rare (Wang et al., 2004). On the other hand, reports on polymeric silver(I) complexes of thia-bridged paracyclophane are also very sparse (Munakata et al., 1996; Liu et al., 2004a,b). We report here the crystal structure of the title compound, [Ag2(dtpcp)(Hpdc)2], (I).

Compound (I) is a dinuclear complex having a center of symmetry and consisting of two AgI ions, one dtpcp molecule and two Hpdc anions (Fig. 1). One of the two carboxyl groups in the H2pdc ligand is deprotonated and the Hpdc anion is chelated to one AgI center through the pyridine N atom and one O atom of the deprotonated carboxyl group. Each AgI ion is three-coordinate in an approximately trigonal configuration by one of the S atoms of the dtpcp ligand, and N and O atoms of the Hpdc anion. The S1—C7···C8—S1i—C7i···C8i [symmetry code: (i) 1/2 − x, 1/2 − y, 1 − z] ring moiety exhibits a chair conformation, as observed in other dtpcp–silver(I) complexes (Liu et al., 2004a,b). The dtpcp ligand acts as a µ2 bridge, linking two Ag atoms with Ag—S bond distance of 2.4129 (6) Å, which is shorter than the values of 2.4787 (5)–2.5471 (6) Å observed in other dtpcp–silver(I) complexes (Liu et al., 2004a,b). The Ag—N bond length [2.287 (2) Å] and Ag—O bond length [2.353 (1) Å] in (I) are also shorter than those observed in another H2pdc–silver(I) complex (Wang et al., 2004). The shorter bond lengths around the AgI center may be attributable to the fact that the coordination number of Ag in (I) is smaller than in other reported dtpcp– or H2pdc–silver(I) complexes, in which the AgI ions are four-coordinate in a distorted tetrahedral configuration.

Each dinuclear silver(I) complex is interconnected with four adjacent ones through O4—H12···O2(x − 1/2, 3/2 − y, z − 1/2) hydrogen bonds (Table 2), propagating as a zigzag sheet. Two zigzag sheets are interwoven in an offset mode to give a bilayer network (Fig. 2). The chair conformation of the dtpcp ligand leads to a step-like arrangement of the two Ag(Hpdc) moieties (Fig. 1), allowing the formation of the bilayer structure. Within the bilayer, two pyridine rings from different sheets are partially overlapped, with an average interplanar distance of 3.30 Å, indicating strong ππ interactions between them. The bilayers are packed on top of? one another (Fig. 3). No short contacts were found between the bilayers.

Experimental top

A mixed solution (4.5 ml) of mesitylene (3 ml) and dimethylformamide (1.5 ml), containing dtpcp (0.03 mmol, 8.2 mg) and H2pdc (0.06 mmol, 10.0 mg), was introduced into a glass tube and layered with a methanol solution (4.5 ml) containing AgCF3CO2 (0.06 mmol, 13.2 mg). The glass tube was sealed under argon. After standing at room temperature for 3 d, colorless block-shaped crystals of (I) were isolated (yield 68%). Analysis calculated for C30H24Ag2N2O8S2: C 43.92, H 2.95, N 3.41%; found: C 43.66, H 2.91, N 3.38%.

Refinement top

All H atoms were found in difference Fourier maps and were subsequently refined with a fixed Uiso(H) value of 0.03 Å2. The C—H bond lengths are 0.89 (3)–1.00 (3) Å.

Computing details top

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.

Figures top
[Figure 1] Fig. 1. The structure and atom numbering of (I), showing displacement ellipsoids at the 50% probability level. H atoms, except those of the carboxylic acid groups, have been omitted for clarity. [Symmetry code: (i) 1/2 − x, 1/2 − y, 1 − z.]
[Figure 2] Fig. 2. The interwoven bilayer network of (I). H atoms, except those of the carboxylic acid groups, have been omitted. Broken lines indicate O—H···O hydrogen bonds.
[Figure 3] Fig. 3. The crystal structure of (I), viewed along the b axis. H atoms, except those of the carboxylic acid groups, have been omitted.
(µ-2,11-Dithia[3.3]paracyclophane-κ2S:S')bis[(2-carboxylatopyridine- 6-carboxylic acid-κ2N,O)silver(I)] top
Crystal data top
[Ag2(C16H16S2)(C7H4O4N)2]F(000) = 1632.0
Mr = 820.38Dx = 1.884 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.7107 Å
Hall symbol: -c 2ycCell parameters from 4714 reflections
a = 17.025 (10) Åθ = 3.2–27.5°
b = 12.828 (7) ŵ = 1.55 mm1
c = 14.096 (8) ÅT = 150 K
β = 110.075 (6)°Block, colorless
V = 2892 (3) Å30.30 × 0.25 × 0.20 mm
Z = 4
Data collection top
Rigaku/MSC Mercury CCD
diffractometer
3038 reflections with I > 2σ(I)
Detector resolution: 14.62 pixels mm-1Rint = 0.022
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(Jacobson, 1998)
h = 1622
Tmin = 0.665, Tmax = 0.733k = 1616
11072 measured reflectionsl = 1818
3250 independent reflections
Refinement top
Refinement on F2Only H-atom coordinates refined
R[F2 > 2σ(F2)] = 0.026 w = 1/[σ2(Fo2) + (0.0289P)2 + 3.8032P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.060(Δ/σ)max = 0.002
S = 1.09Δρmax = 0.61 e Å3
3038 reflectionsΔρmin = 0.49 e Å3
235 parameters
Crystal data top
[Ag2(C16H16S2)(C7H4O4N)2]V = 2892 (3) Å3
Mr = 820.38Z = 4
Monoclinic, C2/cMo Kα radiation
a = 17.025 (10) ŵ = 1.55 mm1
b = 12.828 (7) ÅT = 150 K
c = 14.096 (8) Å0.30 × 0.25 × 0.20 mm
β = 110.075 (6)°
Data collection top
Rigaku/MSC Mercury CCD
diffractometer
3250 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)
3038 reflections with I > 2σ(I)
Tmin = 0.665, Tmax = 0.733Rint = 0.022
11072 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.026235 parameters
wR(F2) = 0.060Only H-atom coordinates refined
S = 1.09Δρmax = 0.61 e Å3
3038 reflectionsΔρmin = 0.49 e Å3
Special details top

Refinement. Refinement using reflections with F2 > −10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ag10.50228 (1)0.58511 (1)0.61899 (1)0.02816 (7)
S10.41061 (3)0.44452 (4)0.53498 (4)0.0196 (1)
O10.62197 (9)0.6226 (1)0.7595 (1)0.0257 (3)
O20.7080 (1)0.7532 (1)0.8338 (1)0.0322 (4)
O30.40063 (9)0.7006 (1)0.4475 (1)0.0281 (3)
O40.32971 (9)0.8480 (1)0.4463 (1)0.0269 (3)
N10.5164 (1)0.7624 (1)0.6302 (1)0.0155 (3)
C10.2388 (1)0.4202 (2)0.4585 (2)0.0203 (4)
C20.1967 (1)0.3798 (2)0.5191 (2)0.0215 (4)
C30.1440 (1)0.2949 (2)0.4875 (2)0.0201 (4)
C40.1327 (1)0.2477 (2)0.3949 (2)0.0193 (4)
C50.1704 (1)0.2923 (2)0.3310 (2)0.0226 (4)
C60.2226 (1)0.3776 (2)0.3624 (2)0.0221 (4)
C70.3055 (1)0.5013 (2)0.5014 (2)0.0251 (4)
C80.0816 (1)0.1491 (2)0.3643 (2)0.0241 (4)
C90.5829 (1)0.7981 (2)0.7060 (1)0.0168 (4)
C100.5993 (1)0.9040 (2)0.7225 (2)0.0210 (4)
C110.5431 (1)0.9748 (2)0.6611 (2)0.0242 (4)
C120.4732 (1)0.9384 (2)0.5845 (2)0.0203 (4)
C130.4633 (1)0.8316 (2)0.5697 (1)0.0160 (4)
C140.6419 (1)0.7163 (2)0.7718 (1)0.0195 (4)
C150.3937 (1)0.7860 (2)0.4813 (1)0.0186 (4)
H10.204 (2)0.410 (2)0.580 (2)0.0301*
H20.117 (2)0.267 (2)0.531 (2)0.0301*
H30.164 (2)0.263 (2)0.269 (2)0.0301*
H40.250 (2)0.407 (2)0.320 (2)0.0301*
H50.301 (2)0.530 (2)0.563 (2)0.0301*
H60.307 (2)0.552 (2)0.452 (2)0.0301*
H70.094 (2)0.118 (2)0.315 (2)0.0301*
H80.020 (2)0.164 (2)0.342 (2)0.0301*
H90.650 (2)0.926 (2)0.774 (2)0.0301*
H100.553 (2)1.047 (2)0.673 (2)0.0301*
H110.432 (2)0.983 (2)0.541 (2)0.0301*
H120.289 (2)0.814 (2)0.408 (2)0.0301*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0210 (1)0.01937 (9)0.0361 (1)0.00372 (6)0.00042 (7)0.00345 (6)
S10.0144 (2)0.0191 (2)0.0241 (2)0.0026 (2)0.0051 (2)0.0022 (2)
O10.0205 (8)0.0250 (8)0.0248 (8)0.0001 (6)0.0010 (6)0.0036 (6)
O20.0181 (8)0.0336 (9)0.0312 (8)0.0008 (6)0.0091 (6)0.0024 (7)
O30.0228 (8)0.0253 (8)0.0270 (8)0.0020 (6)0.0032 (6)0.0069 (6)
O40.0154 (7)0.0261 (8)0.0290 (8)0.0028 (6)0.0055 (6)0.0038 (6)
N10.0115 (8)0.0201 (8)0.0149 (7)0.0007 (6)0.0046 (6)0.0005 (6)
C10.0119 (9)0.0172 (9)0.029 (1)0.0035 (7)0.0038 (8)0.0015 (8)
C20.016 (1)0.0221 (10)0.025 (1)0.0033 (8)0.0065 (8)0.0037 (8)
C30.0148 (10)0.0227 (10)0.0234 (10)0.0031 (8)0.0073 (8)0.0000 (8)
C40.0135 (9)0.0202 (9)0.0203 (9)0.0012 (7)0.0008 (8)0.0016 (7)
C50.021 (1)0.026 (1)0.0161 (9)0.0002 (8)0.0009 (8)0.0021 (8)
C60.0160 (10)0.024 (1)0.025 (1)0.0010 (8)0.0049 (8)0.0068 (8)
C70.016 (1)0.019 (1)0.038 (1)0.0007 (8)0.0071 (9)0.0035 (9)
C80.024 (1)0.027 (1)0.0184 (10)0.0052 (9)0.0034 (8)0.0019 (8)
C90.0116 (9)0.0250 (10)0.0143 (8)0.0014 (8)0.0049 (7)0.0014 (7)
C100.017 (1)0.027 (1)0.0173 (9)0.0054 (8)0.0034 (8)0.0032 (8)
C110.027 (1)0.020 (1)0.025 (1)0.0053 (9)0.0076 (9)0.0033 (8)
C120.019 (1)0.0222 (10)0.0186 (9)0.0015 (8)0.0050 (8)0.0028 (8)
C130.0117 (9)0.0214 (9)0.0152 (9)0.0001 (7)0.0051 (7)0.0003 (7)
C140.0141 (9)0.027 (1)0.0164 (9)0.0000 (8)0.0042 (7)0.0002 (8)
C150.0157 (10)0.0223 (10)0.0159 (9)0.0015 (8)0.0031 (7)0.0015 (7)
Geometric parameters (Å, º) top
Ag1—S12.4129 (6)C9—C101.390 (3)
Ag1—O12.353 (1)C9—C141.526 (3)
Ag1—N12.287 (2)C10—C111.386 (3)
S1—C71.837 (2)C11—C121.385 (3)
S1—C8i1.829 (2)C12—C131.387 (3)
O1—C141.245 (3)C13—C151.512 (2)
O2—C141.257 (2)O4—H120.84 (3)
O3—C151.218 (3)C2—H10.91 (3)
O4—C151.301 (2)C3—H20.95 (3)
N1—C91.342 (2)C5—H30.92 (3)
N1—C131.343 (2)C6—H40.95 (3)
C1—C21.390 (4)C7—H50.97 (3)
C1—C61.397 (3)C7—H60.96 (3)
C1—C71.505 (3)C8—H70.89 (3)
C2—C31.383 (3)C8—H81.00 (3)
C3—C41.391 (3)C10—H90.96 (3)
C4—C51.396 (3)C11—H100.95 (3)
C4—C81.512 (3)C12—H110.95 (3)
C5—C61.383 (3)
Ag1···S1ii3.0437 (9)N1···C14iii3.475 (3)
Ag1···O1iii3.183 (2)C3···C9viii3.572 (3)
O1···C7iii3.528 (3)C8···C8ix3.458 (4)
O2···C15iv3.171 (3)C9···C9iii3.453 (5)
O2···O3iv3.172 (3)C9···C13iii3.537 (3)
O2···O4iii3.586 (3)C10···C12iii3.382 (4)
O4···C7v3.278 (3)C10···C11iii3.484 (4)
O4···C14vi3.399 (3)C10···C13iii3.567 (3)
O4···C2v3.576 (3)C11···C11iii3.312 (5)
N1···C9iii3.329 (3)C11···C12x3.555 (3)
N1···C3vii3.456 (3)C12···C12x3.240 (5)
S1—Ag1—O1142.50 (4)O1—C14—O2126.6 (2)
S1—Ag1—N1144.31 (4)O1—C14—C9119.2 (2)
O1—Ag1—N172.45 (5)O2—C14—C9114.2 (2)
Ag1—S1—C7103.83 (7)O3—C15—O4125.7 (2)
Ag1—S1—C8i104.33 (7)O3—C15—C13121.1 (2)
C7—S1—C8i105.4 (1)O4—C15—C13113.2 (2)
Ag1—O1—C14115.5 (1)C15—O4—H12109 (2)
Ag1—N1—C9115.7 (1)C1—C2—H1119 (2)
Ag1—N1—C13125.6 (1)C3—C2—H1120 (2)
C9—N1—C13118.7 (2)C2—C3—H2119 (1)
C2—C1—C6118.5 (2)C4—C3—H2119 (1)
C2—C1—C7119.2 (2)C4—C5—H3120 (1)
C6—C1—C7122.0 (2)C6—C5—H3119 (2)
C1—C2—C3120.7 (2)C1—C6—H4118 (1)
C2—C3—C4120.7 (2)C5—C6—H4120 (1)
C3—C4—C5118.8 (2)S1—C7—H5106 (1)
C3—C4—C8120.8 (2)S1—C7—H6101 (2)
C5—C4—C8120.4 (2)C1—C7—H5110 (1)
C4—C5—C6120.3 (2)C1—C7—H6112 (1)
C1—C6—C5120.7 (2)H5—C7—H6115 (2)
S1—C7—C1111.3 (2)S1i—C8—H7109 (1)
S1i—C8—C4116.5 (1)S1i—C8—H899 (1)
N1—C9—C10122.2 (2)C4—C8—H7109 (2)
N1—C9—C14116.7 (2)C4—C8—H8111 (1)
C10—C9—C14121.1 (2)H7—C8—H8110 (3)
C9—C10—C11118.6 (2)C9—C10—H9119 (1)
C10—C11—C12119.4 (2)C11—C10—H9121 (1)
C11—C12—C13118.5 (2)C10—C11—H10119 (1)
N1—C13—C12122.5 (2)C12—C11—H10121 (1)
N1—C13—C15115.8 (2)C11—C12—H11123 (1)
C12—C13—C15121.7 (2)C13—C12—H11118 (1)
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+1, y+1, z+1; (iii) x+1, y, z+3/2; (iv) x+1/2, y+3/2, z+1/2; (v) x+1/2, y+3/2, z+1; (vi) x1/2, y+3/2, z1/2; (vii) x+1/2, y+1/2, z; (viii) x1/2, y1/2, z; (ix) x, y, z+1/2; (x) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H12···O2vi0.84 (3)1.66 (3)2.497 (2)180 (3)
Symmetry code: (vi) x1/2, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formula[Ag2(C16H16S2)(C7H4O4N)2]
Mr820.38
Crystal system, space groupMonoclinic, C2/c
Temperature (K)150
a, b, c (Å)17.025 (10), 12.828 (7), 14.096 (8)
β (°) 110.075 (6)
V3)2892 (3)
Z4
Radiation typeMo Kα
µ (mm1)1.55
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerRigaku/MSC Mercury CCD
diffractometer
Absorption correctionMulti-scan
(Jacobson, 1998)
Tmin, Tmax0.665, 0.733
No. of measured, independent and
observed [I > 2σ(I)] reflections
11072, 3250, 3038
Rint0.022
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.060, 1.09
No. of reflections3038
No. of parameters235
No. of restraints?
H-atom treatmentOnly H-atom coordinates refined
Δρmax, Δρmin (e Å3)0.61, 0.49

Computer programs: CrystalClear (Rigaku, 2001), CrystalClear, TEXSAN (Molecular Structure Corporation, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), TEXSAN.

Selected geometric parameters (Å, º) top
Ag1—S12.4129 (6)O2—C141.257 (2)
Ag1—O12.353 (1)O3—C151.218 (3)
Ag1—N12.287 (2)O4—C151.301 (2)
O1—C141.245 (3)
S1—Ag1—O1142.50 (4)O1—Ag1—N172.45 (5)
S1—Ag1—N1144.31 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H12···O2i0.84 (3)1.66 (3)2.497 (2)180 (3)
Symmetry code: (i) x1/2, y+3/2, z1/2.
 

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