Poly[(μ-benzene-1,2,4,5-tetra­carboxyl­ato)tetra­silver(I)]

Abstract

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.

Related literature

For related structures, see: Jaber et al. (1997 ▶); Tahir et al. (1996 ▶); Ülkü et al. (1996 ▶).

Experimental

Crystal data

• [Ag₄(C₁₀H₂O₈)]

• M _r = 340.80

• Monoclinic,

• a = 8.328 (1) Å

• b = 6.317 (1) Å

• c = 10.945 (2) Å

• β = 94.36 (2)°

• V = 574.13 (16) ų

• Z = 4

• Mo Kα radiation

• μ = 6.76 mm⁻¹

• T = 296 K

• 0.30 × 0.10 × 0.08 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (MolEN; Fair, 1990 ▶) T _min = 0.448, T _max = 0.578

• 1680 measured reflections

• 1308 independent reflections

• 1268 reflections with I > 2σ(I)

• R _int = 0.012

• 3 standard reflections frequency: 120 min intensity decay: 0.1%

Refinement

• R[F ² > 2σ(F ²)] = 0.026

• wR(F ²) = 0.089

• S = 1.01

• 1308 reflections

• 101 parameters

• H-atom parameters constrained

• Δρ_max = 1.20 e Å⁻³

• Δρ_min = −0.79 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1993 ▶); cell refinement: CAD-4 EXPRESS; 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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O3i	0.93	2.5400	3.422 (6)	158

Symmetry code: (i) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

The H–atom was found in difference map but positioned geometrically due to the presence of heavy atoms, C—H = 0.93 Å with U_iso(H) = 1.2U_eq(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.

Figures

Fig. 1.

A view of part of polimeric structure of title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 50% probability level. H atom is presented as a small sphere of arbitrary radius. The symmetry codes in labeling are i = -x+1, -y+1, -z+1; ii = -x, -y+1, -z+1; iii = x, -y+1/2, z-1/2; iv = x, -y+3/2, z-1/2; v = -x, y+1/2, -z+1/2; vi = x, -y+1/2, z+1/2; vii = -x, y-1/2, -z+1/2; viii = x, -y+3/2, z+1/2.

Crystal data

[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

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

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

Special details

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 (Ų)

	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 (Ų)

	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, °)

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, °)

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.