supplementary materials
Poly[(![[mu]](/logos/entities/mu_rmgif.gif)
-benzene-1,2,4,5-tetracarboxylato)tetrasilver(I)]
In the centrosymmetric title compound, [Ag4(C10H2O8)]n, the benzene ring has irregular bond lengths but remains planar (r.m.s. deviation 0.0002 Å). The Ag-O bond lengths are in the range 2.153 (3)-2.615 (4) Å. The carboxylate groups are oriented at dihedral angles of 26.4 (5) and 74.9 (4)° to the benzene ring. The coordination behaviour of each carboxylate O atom is different: in one carboxylate, the O atoms are coordinated to a single and two Ag atoms; in the other carboxylate, the O atoms are coordinated to two and three Ag atoms. Non-classical intermolecular C-H
O hydrogen bonding is present in the crystal structure. The title compound forms a three-dimensional polymeric network due to the coordination of the Ag atoms.
To the aqueous solution of sodium 1,2,4,5–benzenetetracarboxylate, freshly
prepared solution of AgNO3 was added dropwise with constant stirring until
the color was changed. The product was filtered and the filtrate was kept in
darkness for the crystallization by slow evaporation. Needle like crystals
were obtained after 72 h.
The H–atom was found in difference map but positioned geometrically due to
the presence of heavy atoms, C—H = 0.93 Å with Uiso(H) = 1.2Ueq(C) and
constrained to ride on the parent atom.
The maximum electron density peak appears at the fractional coordinates 0.1821
0.4015 0.7121 and is at a distance of 0.75 Å from Ag1.
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1993); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1993); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Poly[(µ-benzene-1,2,4,5-tetracarboxylato)tetrasilver(I)]
top
Crystal data top
| [Ag4(C10H2O8)] | F(000) = 628 |
| Mr = 340.80 | Dx = 3.943 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
| a = 8.328 (1) Å | θ = 11.7–21.0° |
| b = 6.317 (1) Å | µ = 6.76 mm−1 |
| c = 10.945 (2) Å | T = 296 K |
| β = 94.36 (2)° | Needle, pale yellow |
| V = 574.13 (16) Å3 | 0.30 × 0.10 × 0.08 mm |
| Z = 4 | |
Data collection top
Enraf–Nonius CAD-4
diffractometer | Rint = 0.012 |
| ω/2θ scans | θmax = 28.2°, θmin = 3.7° |
Absorption correction: ψ scan
(MolEN; Fair, 1990) | h = 0→10 |
| Tmin = 0.448, Tmax = 0.578 | k = 0→8 |
| 1680 measured reflections | l = −14→14 |
| 1308 independent reflections | 3 standard reflections every 120 min |
| 1268 reflections with I > 2σ(I) | intensity decay: 0.1% |
Refinement top
| Refinement on F2 | Primary atom site location: Patterson |
| Least-squares matrix: Full | Secondary atom site location: Difmap |
| R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
| wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.0599P)2 + 3.6455P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max < 0.001 |
| 1308 reflections | Δρmax = 1.20 e Å−3 |
| 101 parameters | Δρmin = −0.79 e Å−3 |
| 0 restraints | |
Crystal data top
| [Ag4(C10H2O8)] | V = 574.13 (16) Å3 |
| Mr = 340.80 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.328 (1) Å | µ = 6.76 mm−1 |
| b = 6.317 (1) Å | T = 296 K |
| c = 10.945 (2) Å | 0.30 × 0.10 × 0.08 mm |
| β = 94.36 (2)° | |
Data collection top
Enraf–Nonius CAD-4
diffractometer | 1268 reflections with I > 2σ(I) |
Absorption correction: ψ scan
(MolEN; Fair, 1990) | Rint = 0.012 |
| Tmin = 0.448, Tmax = 0.578 | θmax = 28.2° |
| 1680 measured reflections | 3 standard reflections every 120 min |
| 1308 independent reflections | intensity decay: 0.1% |
Refinement top
| R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
| wR(F2) = 0.089 | Δρmax = 1.20 e Å−3 |
| S = 1.01 | Δρmin = −0.79 e Å−3 |
| 1308 reflections | Absolute structure: ? |
| 101 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Special details top
Experimental. The structure was solved by Patterson method using SHELX86. The whole
molecule was recognized. |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell s.u.'s are taken
into account individually in the estimation of s.u.'s in distances, angles
and torsion angles; correlations between s.u.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell s.u.s is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| Ag1 | 0.09967 (6) | 0.44769 (6) | 0.70351 (4) | 0.0316 (2) | |
| Ag2 | −0.15558 (4) | 0.16471 (6) | 0.44813 (3) | 0.0250 (2) | |
| O1 | 0.1054 (4) | 0.2412 (6) | 0.5218 (3) | 0.0238 (10) | |
| O2 | 0.1422 (4) | 0.3437 (6) | 0.3300 (3) | 0.0264 (10) | |
| O3 | 0.3520 (4) | 0.6473 (6) | 0.1913 (3) | 0.0246 (10) | |
| O4 | 0.2066 (5) | 0.8108 (6) | 0.3346 (3) | 0.0273 (11) | |
| C1 | 0.3498 (5) | 0.4182 (8) | 0.4710 (4) | 0.0169 (11) | |
| C2 | 0.4363 (6) | 0.3358 (7) | 0.5701 (4) | 0.0184 (12) | |
| C3 | 0.4135 (5) | 0.5821 (8) | 0.4012 (4) | 0.0167 (11) | |
| C4 | 0.1874 (5) | 0.3273 (7) | 0.4386 (4) | 0.0191 (12) | |
| C5 | 0.3167 (5) | 0.6850 (8) | 0.2996 (4) | 0.0186 (12) | |
| H2 | 0.39517 | 0.22806 | 0.61643 | 0.0221* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Ag1 | 0.0447 (3) | 0.0225 (3) | 0.0247 (3) | −0.0009 (2) | −0.0155 (2) | −0.0012 (1) |
| Ag2 | 0.0254 (3) | 0.0282 (3) | 0.0195 (3) | −0.0047 (1) | −0.0097 (2) | 0.0011 (1) |
| O1 | 0.0201 (16) | 0.0262 (18) | 0.0240 (17) | −0.0079 (13) | −0.0045 (13) | −0.0005 (14) |
| O2 | 0.0254 (18) | 0.0292 (19) | 0.0221 (17) | −0.0027 (14) | −0.0152 (14) | −0.0006 (14) |
| O3 | 0.0222 (17) | 0.035 (2) | 0.0156 (16) | 0.0058 (14) | −0.0048 (13) | 0.0024 (14) |
| O4 | 0.0291 (19) | 0.033 (2) | 0.0187 (16) | 0.0134 (16) | −0.0057 (14) | 0.0017 (14) |
| C1 | 0.0131 (18) | 0.020 (2) | 0.0164 (19) | −0.0001 (16) | −0.0070 (15) | 0.0001 (16) |
| C2 | 0.017 (2) | 0.020 (2) | 0.017 (2) | −0.0003 (16) | −0.0064 (16) | 0.0033 (16) |
| C3 | 0.0150 (19) | 0.021 (2) | 0.0130 (18) | 0.0022 (16) | −0.0058 (14) | 0.0001 (16) |
| C4 | 0.016 (2) | 0.016 (2) | 0.024 (2) | 0.0017 (16) | −0.0059 (17) | −0.0050 (16) |
| C5 | 0.015 (2) | 0.022 (2) | 0.018 (2) | −0.0005 (16) | −0.0046 (16) | 0.0013 (16) |
Geometric parameters (Å, °) top
| Ag1—O1 | 2.382 (3) | O2—C4 | 1.224 (5) |
| Ag1—Ag2i | 3.0140 (8) | O3—C5 | 1.265 (5) |
| Ag1—O2i | 2.412 (4) | O4—C5 | 1.293 (6) |
| Ag1—O2ii | 2.314 (4) | C1—C2 | 1.359 (6) |
| Ag1—O4iii | 2.233 (4) | C1—C3 | 1.414 (7) |
| Ag2—O1 | 2.311 (3) | C1—C4 | 1.487 (6) |
| Ag2—O3iv | 2.153 (3) | C2—C3vi | 1.368 (7) |
| Ag2—O1v | 2.615 (4) | C3—C5 | 1.474 (6) |
| Ag2—O4i | 2.452 (3) | C2—H2 | 0.9300 |
| O1—C4 | 1.298 (5) | | |
| | | |
| Ag1···C2 | 3.334 (5) | O1···O4i | 3.154 (5) |
| Ag1···C4i | 3.097 (4) | O2···C5 | 2.635 (6) |
| Ag1···Ag1vii | 3.7449 (9) | O2···O3 | 3.072 (5) |
| Ag1···Ag1viii | 3.7449 (9) | O2···O4 | 2.999 (5) |
| Ag1···Ag2viii | 4.0452 (9) | O2···Ag2xii | 3.666 (4) |
| Ag1···O1viii | 4.022 (4) | O2···Ag2i | 3.939 (4) |
| Ag1···O1i | 3.495 (4) | O3···O2 | 3.072 (5) |
| Ag1···O3i | 4.061 (3) | O3···Ag1i | 4.061 (3) |
| Ag1···O3iii | 3.320 (4) | O4···C4 | 3.268 (6) |
| Ag1···C5i | 3.565 (4) | O4···Ag2xiii | 4.026 (4) |
| Ag1···Ag2ii | 3.6134 (9) | O4···O2 | 2.999 (5) |
| Ag1···C5iii | 3.077 (5) | O4···Ag1i | 3.031 (4) |
| Ag2···O1i | 3.788 (4) | O4···O1i | 3.155 (5) |
| Ag2···O4ix | 4.026 (4) | O1···H2 | 2.5500 |
| Ag2···C2x | 3.898 (5) | O3···H2xi | 2.5400 |
| Ag2···Ag1vii | 4.0452 (9) | C2···Ag1 | 3.334 (5) |
| Ag2···C2i | 3.923 (5) | C2···Ag2xiv | 3.898 (5) |
| Ag2···C1i | 3.250 (5) | C2···Ag2v | 3.928 (5) |
| Ag2···C2v | 3.928 (5) | C2···Ag2i | 3.923 (5) |
| Ag2···Ag1xi | 3.6134 (9) | C4···O4 | 3.268 (6) |
| Ag2···C4i | 3.458 (4) | C5···O2 | 2.635 (6) |
| Ag1···H2 | 3.0400 | C5···Ag1i | 3.565 (4) |
| Ag2···H2v | 3.2300 | H2···Ag1 | 3.0400 |
| O1···O2 | 2.240 (5) | H2···O1 | 2.5500 |
| O1···Ag2i | 3.788 (4) | H2···Ag2v | 3.2300 |
| O1···Ag1vii | 4.022 (4) | H2···O3ii | 2.5400 |
| O1···Ag1i | 3.496 (4) | | |
| | | |
| Ag2i—Ag1—O1 | 88.36 (9) | Ag2—O1—Ag2v | 88.62 (12) |
| O1—Ag1—O2i | 103.99 (12) | Ag2v—O1—C4 | 114.3 (3) |
| O1—Ag1—O2ii | 92.98 (12) | Ag1i—O2—C4 | 112.7 (3) |
| O1—Ag1—O4iii | 151.46 (13) | Ag1xi—O2—C4 | 122.4 (3) |
| Ag2i—Ag1—O2i | 68.57 (9) | Ag1i—O2—Ag1xi | 104.81 (13) |
| Ag2i—Ag1—O2ii | 162.28 (9) | Ag2xii—O3—C5 | 115.9 (3) |
| Ag2i—Ag1—O4iii | 74.22 (9) | Ag2i—O4—C5 | 120.3 (3) |
| O2i—Ag1—O2ii | 127.86 (12) | Ag1xv—O4—C5 | 119.1 (3) |
| O2i—Ag1—O4iii | 90.69 (14) | Ag1xv—O4—Ag2i | 119.34 (17) |
| O2ii—Ag1—O4iii | 97.10 (13) | C2—C1—C3 | 120.9 (4) |
| O1—Ag2—O3iv | 154.36 (13) | C2—C1—C4 | 117.4 (4) |
| O1—Ag2—O1v | 91.37 (12) | C3—C1—C4 | 121.7 (4) |
| Ag1i—Ag2—O1 | 80.89 (9) | C1—C2—C3vi | 117.2 (4) |
| O1—Ag2—O4i | 82.89 (13) | C1—C3—C5 | 121.6 (4) |
| O1v—Ag2—O3iv | 98.33 (13) | C1—C3—C2vi | 121.8 (4) |
| Ag1i—Ag2—O3iv | 78.00 (10) | C2vi—C3—C5 | 116.4 (4) |
| O3iv—Ag2—O4i | 120.81 (13) | O1—C4—O2 | 125.3 (4) |
| Ag1i—Ag2—O1v | 146.75 (8) | O1—C4—C1 | 120.8 (4) |
| O1v—Ag2—O4i | 88.69 (12) | O2—C4—C1 | 114.0 (4) |
| Ag1i—Ag2—O4i | 121.88 (9) | O3—C5—O4 | 127.9 (4) |
| Ag1—O1—Ag2 | 109.14 (14) | O3—C5—C3 | 118.1 (4) |
| Ag1—O1—C4 | 113.7 (3) | O4—C5—C3 | 114.0 (4) |
| Ag1—O1—Ag2v | 116.43 (13) | C1—C2—H2 | 121.00 |
| Ag2—O1—C4 | 111.9 (3) | C3vi—C2—H2 | 121.00 |
| | | |
| Ag2i—Ag1—O1—Ag2 | −100.23 (13) | O1—Ag2—O1v—C4v | 113.6 (3) |
| Ag2i—Ag1—O1—C4 | 25.5 (3) | O1—Ag2—O4i—C5i | 125.7 (4) |
| Ag2i—Ag1—O1—Ag2v | 161.49 (13) | Ag1—O1—C4—O2 | −132.9 (4) |
| O2i—Ag1—O1—Ag2 | −32.80 (17) | Ag1—O1—C4—C1 | 46.7 (5) |
| O2i—Ag1—O1—C4 | 92.9 (3) | Ag2—O1—C4—O2 | −8.7 (6) |
| O2i—Ag1—O1—Ag2v | −131.09 (14) | Ag2—O1—C4—C1 | 170.9 (3) |
| O2ii—Ag1—O1—Ag2 | 97.46 (15) | Ag2v—O1—C4—O2 | 90.2 (5) |
| O2ii—Ag1—O1—C4 | −136.8 (3) | Ag2v—O1—C4—C1 | −90.3 (4) |
| O2ii—Ag1—O1—Ag2v | −0.82 (15) | Ag1i—O2—C4—O1 | 61.0 (5) |
| O4iii—Ag1—O1—Ag2 | −151.8 (2) | Ag1i—O2—C4—C1 | −118.5 (3) |
| O4iii—Ag1—O1—C4 | −26.0 (5) | Ag1xi—O2—C4—O1 | −65.4 (6) |
| O4iii—Ag1—O1—Ag2v | 110.0 (3) | Ag1xi—O2—C4—C1 | 115.1 (4) |
| O1—Ag1—Ag2i—O4 | −5.35 (14) | Ag2xii—O3—C5—O4 | −31.4 (7) |
| O1—Ag1—Ag2i—O1i | 70.34 (12) | Ag2xii—O3—C5—C3 | 151.0 (3) |
| O1—Ag1—Ag2i—O3iii | −124.33 (13) | Ag2i—O4—C5—O3 | 176.4 (4) |
| O2i—Ag1—Ag2i—O4 | −111.08 (15) | Ag2i—O4—C5—C3 | −5.9 (5) |
| O4iii—Ag1—Ag2i—O4 | 151.77 (16) | Ag1xv—O4—C5—O3 | −16.2 (7) |
| O1—Ag1—O2i—C4i | −21.4 (3) | Ag1xv—O4—C5—C3 | 161.5 (3) |
| O1—Ag1—O2ii—C4ii | 162.7 (3) | C3—C1—C2—C3vi | −0.1 (7) |
| O1—Ag1—O4iii—C5iii | 17.6 (5) | C4—C1—C2—C3vi | 179.2 (4) |
| O3iv—Ag2—O1—Ag1 | 129.8 (3) | C2—C1—C3—C5 | −175.0 (4) |
| O3iv—Ag2—O1—C4 | 3.1 (5) | C2—C1—C3—C2vi | 0.1 (7) |
| O3iv—Ag2—O1—Ag2v | −112.6 (3) | C4—C1—C3—C5 | 5.7 (7) |
| O1v—Ag2—O1—Ag1 | −117.55 (14) | C4—C1—C3—C2vi | −179.2 (4) |
| O1v—Ag2—O1—C4 | 115.8 (3) | C2—C1—C4—O1 | 27.0 (6) |
| O1v—Ag2—O1—Ag2v | 0.03 (10) | C2—C1—C4—O2 | −153.5 (4) |
| Ag1i—Ag2—O1—Ag1 | 94.95 (13) | C3—C1—C4—O1 | −153.8 (4) |
| Ag1i—Ag2—O1—C4 | −31.8 (3) | C3—C1—C4—O2 | 25.8 (6) |
| Ag1i—Ag2—O1—Ag2v | −147.47 (8) | C1—C2—C3vi—C1vi | 0.1 (7) |
| O4i—Ag2—O1—Ag1 | −29.04 (15) | C1—C2—C3vi—C5vi | −175.3 (4) |
| O4i—Ag2—O1—C4 | −155.7 (3) | C1—C3—C5—O3 | −109.0 (5) |
| O4i—Ag2—O1—Ag2v | 88.54 (12) | C1—C3—C5—O4 | 73.0 (6) |
| O1—Ag2—O3iv—C5iv | 8.6 (6) | C2vi—C3—C5—O3 | 75.6 (6) |
| O1—Ag2—O1v—Ag1v | −110.74 (15) | C2vi—C3—C5—O4 | −102.3 (5) |
| O1—Ag2—O1v—Ag2v | −0.03 (11) | | |
| Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x, −y+3/2, z+1/2; (iv) −x, y−1/2, −z+1/2; (v) −x, −y, −z+1; (vi) −x+1, −y+1, −z+1; (vii) −x, y−1/2, −z+3/2; (viii) −x, y+1/2, −z+3/2; (ix) x, y−1, z; (x) x−1, y, z; (xi) x, −y+1/2, z−1/2; (xii) −x, y+1/2, −z+1/2; (xiii) x, y+1, z; (xiv) x+1, y, z; (xv) x, −y+3/2, z−1/2. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···O3ii | 0.9300 | 2.5400 | 3.422 (6) | 158.00 |
| Symmetry codes: (ii) x, −y+1/2, z+1/2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···O3i | 0.9300 | 2.5400 | 3.422 (6) | 158.00 |
| Symmetry codes: (i) x, −y+1/2, z+1/2. |
Enraf–Nonius (1993). CAD–4 EXPRESS. Enraf–Nonius, Delft, The Netherlands.
Fair, C. K. (1990). MolEN. Enraf–Nonius, Delft, The Netherlands.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Jaber, F., Charbonnier, F. & Faure, R. (1997). J. Chem. Crystallogr. 27, 397–400.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Tahir, M. N., Ülkü, D. & Muvsumov, E. M. (1996). Acta Cryst. C52, 593–595.
Ülkü, D., Tahir, M. N. & Movsumov, E. M. (1996). Acta Cryst. C52, 2678–2680.
![[Figure 1]](./rk2131fig1thm.gif)
The crystal structures of poly[bis(p–nitrosalicylato–O:O')disilver(I)] (Tahir et al., 1996) and poly[bis(3,5–dinitrobenzoato–O1:O2) disilver(I)–O2:Ag;Ag':O2'] (Ülkü et al., 1996) have been reported. In continuation to the interest relating to the chemistry of silver coordination with carboxylates, the title compound (I), (Fig. 1) was synthesized.
Crystal structure of silver(I) with 1,2,4,5–benzenetetracarboxylic acid (II) (Jaber et al., 1997) has also been reported. The present complex (I) has been prepared by different method with same ligand as in (II). Due to the change in reaction mechanism, the coordination of O atoms of all carboxylates with Ag atoms has been affected very much. In this centrosymmetric complex, the C–O bond lengths of the carboxylato–groups vary in the range of 1.224 (3) to 1.298 (5) Å. In the benzene ring, the bond lengths of opposite sides are equal having values of 1.359 (6), 1.368 (7) and 1.414 (7) Å. The largest bond is in between the C atoms bearing carboxylate–groups. Although the bond lengths in benzene ring are irregular but it remains planar. In (I), the metallic bond is of 3.0140 (8) Å. The carboxylato–group (O1/C4/O2) makes a dihedral angle of 26.37 (51)° with the benzene ring, while the group (O3/C5/O4) is oriented at 74.90 (37)°. Non–classical intermolecular C2—H2···O3 hydrogen bond was found in the molecular structure. The crystal structure of title compound is stabilized through three dimensional polymeric network.