supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

bt2568 scheme

Acta Cryst. (2007). E63, m2881    [ doi:10.1107/S1600536807054025 ]

Bis[[mu]-2-(3-pyridyl)benzimidazole]bis[bis(3,5-dicarboxybenzoato)silver(I)]

C.-K. Xia, W. Wu, L. Qiu and J.-M. Xie

Abstract top

In the binuclear title complex, [Ag2(C9H5O6)2(C12H9N3)2], the two AgI atoms are in a trigonal planar environment formed by two N atoms from two 2-(3-pyridyl)benzimidazole ligands and one O atom from a 3,5-dicarboxybenzoate ligand, forming a centrosymmetric cyclic dimer. Intermolecular N-H...O and O-H...O hydrogen-bonding interactions aggregate the binuclear units into a three-dimensional framework.

Comment top

1,3,5-Benzenetricarboxylatic acid has been often be used to construct supramolecular structures (Dai et al., 2003, Prior et al., 2003; Plater et al., 2001). In those coordination complexes, the 1,3,5-benzenetricarboxylatic acid ligand demonstrated versatile coordination modes and the tendence of forming hydrogen bonds. The structures are controlled by the extent of the depronation of 1,3,5-benzenetricarboxylatic acid, the nature of the auxiliary ligands, and the metal centers.

In the title compound each two AgI atom is bonded by two nitrogen atoms from two two 2-(3-pyridyl)benzimidazole ligands, forming a binuclear macrocycle. The coordination sphere is completed by a 3,5-dicarboxybenzoate ligand. The intermolecular N—H···O hydrogen bonding interactions connect the binuclear units into a two-dimensional undulating sheet with the protonated carboxylic acid groups on the opposite sides (Fig. 2). The sheets are further connected by O—H···O hydrogen bonding interactions into a three-dimensional framework (Fig. 3). Although there are aromatic rings, no apparent π···π stacking interactions have been found.

Related literature top

For related literature, see: Dai et al. (2003); Prior et al. (2003); Plater et al. (2001); Alcalde et al. (1992).

Experimental top

The 2-(3-pyridyl)benzimidazole was synthesized according to the literature (Alcalde et al., 1992). A solution of AgNO3 (0.104 g, 0.61 mmol), 2-(3-pyridyl)benzimidazole (0.14 g, 0.61 mmol), 1,3,5-benzenetricarboxylatic acid (0.128 g, 0.61 mmol) and H2O (15 ml) was stirred under ambient condition, adjust with dilute NaOH to pH=7.3, then sealed in Teflon-lined stainless steel vessel, heated at 403 K for 4 days and cooled to room temperature. The resulting product was recovered by filtration, washed with distilled water and dried in air. (60% yield).

Refinement top

After checking their presence in the different map, H atoms bonded to C and N were fixed geometrically and allowed to ride on their attached atoms, with C—H=0.93 Å, N—H=0.86 Å, Uiso(H)=1.2Ueq(C,N). The two carboxylic acid H atoms were located from a difference map and refined with a restraint of 0.83 (1)Å for the O—H distance.

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of (I), with the atomic labels and 30% probability displacement ellipsoids for non-H atoms. [Symmetry code: (i) 1 − x, 1 − y, −z.]
[Figure 2] Fig. 2. A view of the two-dimensional sheet of (I). The phenyl ring and two protonated carboxylic acid groups of the 3,5-dicarboxybenzoate ligands are omitted for clearity.
[Figure 3] Fig. 3. Three-dimensional supramolecular architecture constructed by intermolecular N—H···O and O—H···O hydrogen bonding interactions.
Bis[µ-2-(3-pyridyl)benzimidazole]bis[bis(3,5-dicarboxybenzoato)silver(I)] top
Crystal data top
[Ag2(C9H5O6)2(C12H9N3)2]F000 = 1024
Mr = 1024.44Dx = 1.880 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -p 2ybcCell parameters from 4455 reflections
a = 14.573 (3) Åθ = 2.2–27.5º
b = 7.7160 (15) ŵ = 1.16 mm−1
c = 16.662 (4) ÅT = 293 (2) K
β = 105.038 (3)ºPrism, white
V = 1809.3 (7) Å30.30 × 0.20 × 0.10 mm
Z = 2
Data collection top
Rigaku Mercury CCD
diffractometer		4111 independent reflections
Radiation source: fine-focus sealed tube3895 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 293(2) Kθmax = 27.5º
ω scanθmin = 2.5º
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2002)		h = −18→17
Tmin = 0.756, Tmax = 0.881k = −9→9
13327 measured reflectionsl = −21→21
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.070  w = 1/[σ2(Fo2) + (0.0272P)2 + 1.8597P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
4111 reflectionsΔρmax = 0.57 e Å−3
289 parametersΔρmin = −0.80 e Å−3
2 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0084 (4)
Crystal data top
[Ag2(C9H5O6)2(C12H9N3)2]V = 1809.3 (7) Å3
Mr = 1024.44Z = 2
Monoclinic, P21/cMo Kα
a = 14.573 (3) ŵ = 1.16 mm−1
b = 7.7160 (15) ÅT = 293 (2) K
c = 16.662 (4) Å0.30 × 0.20 × 0.10 mm
β = 105.038 (3)º
Data collection top
Rigaku Mercury CCD
diffractometer		4111 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2002)		3895 reflections with I > 2σ(I)
Tmin = 0.756, Tmax = 0.881Rint = 0.021
13327 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0302 restraints
wR(F2) = 0.070H atoms treated by a mixture of
independent and constrained refinement
S = 1.09Δρmax = 0.57 e Å−3
4111 reflectionsΔρmin = −0.80 e Å−3
289 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ag10.382999 (13)0.29268 (3)0.037544 (12)0.03468 (9)
C10.74977 (16)0.5248 (3)0.11466 (15)0.0309 (5)
H1A0.78740.62190.11400.037*
C20.77957 (18)0.4034 (3)0.17668 (16)0.0368 (6)
H2A0.83730.41770.21610.044*
C30.72380 (17)0.2614 (3)0.18019 (14)0.0295 (5)
H3A0.74270.17990.22240.035*
C40.63816 (14)0.2416 (3)0.11918 (13)0.0217 (4)
C50.61437 (14)0.3674 (3)0.05766 (13)0.0243 (4)
H5A0.55830.35380.01610.029*
C60.57592 (14)0.0933 (3)0.12172 (12)0.0220 (4)
C70.45294 (15)−0.0690 (3)0.11505 (13)0.0236 (4)
C80.36146 (16)−0.1367 (3)0.10454 (15)0.0309 (5)
H8A0.3076−0.07190.08020.037*
C90.35464 (18)−0.3034 (3)0.13187 (16)0.0332 (5)
H9A0.2948−0.35230.12540.040*
C100.43580 (18)−0.4018 (3)0.16943 (14)0.0318 (5)
H10A0.4282−0.51420.18690.038*
C110.52649 (17)−0.3358 (3)0.18106 (14)0.0290 (5)
H11A0.5801−0.40030.20640.035*
C120.53314 (15)−0.1673 (3)0.15278 (13)0.0233 (4)
C130.20664 (14)0.2894 (3)0.16465 (13)0.0202 (4)
C140.10780 (14)0.2457 (3)0.11280 (12)0.0202 (4)
C150.08006 (15)0.2934 (3)0.02933 (13)0.0214 (4)
H15A0.12290.34860.00510.026*
C16−0.01229 (15)0.2581 (3)−0.01784 (12)0.0226 (4)
C17−0.04769 (16)0.3129 (3)−0.10631 (13)0.0263 (5)
C18−0.07455 (15)0.1672 (3)0.01709 (13)0.0239 (4)
H18A−0.13540.1415−0.01500.029*
C19−0.04660 (14)0.1142 (3)0.09960 (13)0.0216 (4)
C20−0.11372 (14)0.0066 (3)0.13342 (13)0.0238 (4)
C210.04383 (14)0.1585 (3)0.14761 (12)0.0207 (4)
H21A0.06160.12930.20370.025*
N10.66800 (12)0.5074 (2)0.05512 (11)0.0248 (4)
N20.48148 (12)0.0938 (2)0.09546 (11)0.0238 (4)
N30.60976 (12)−0.0606 (2)0.15547 (11)0.0249 (4)
H3B0.6686−0.08730.17510.030*
O10.21436 (10)0.3257 (2)0.24162 (9)0.0267 (3)
O20.27345 (12)0.2860 (3)0.13320 (11)0.0373 (4)
O30.01671 (12)0.3937 (3)−0.13642 (10)0.0334 (4)
H3C−0.012 (2)0.424 (5)−0.1850 (13)0.059 (10)*
O4−0.12813 (13)0.2879 (3)−0.14653 (11)0.0483 (5)
O5−0.19001 (11)−0.0415 (3)0.08971 (10)0.0354 (4)
O6−0.08317 (11)−0.0325 (2)0.21275 (9)0.0290 (4)
H6B−0.127 (2)−0.084 (5)0.228 (2)0.072 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.02870 (11)0.03189 (13)0.04170 (13)0.00498 (7)0.00598 (8)0.01359 (8)
C10.0279 (11)0.0267 (12)0.0363 (12)−0.0075 (9)0.0050 (9)0.0005 (10)
C20.0318 (12)0.0334 (14)0.0365 (13)−0.0084 (10)−0.0069 (10)0.0042 (11)
C30.0276 (11)0.0291 (12)0.0276 (11)−0.0021 (9)−0.0005 (9)0.0054 (9)
C40.0199 (9)0.0218 (10)0.0231 (10)−0.0003 (8)0.0048 (8)−0.0011 (8)
C50.0198 (9)0.0272 (11)0.0247 (10)0.0001 (8)0.0037 (8)0.0025 (9)
C60.0211 (9)0.0228 (11)0.0215 (9)0.0001 (8)0.0042 (7)0.0002 (8)
C70.0227 (10)0.0238 (11)0.0245 (10)−0.0006 (8)0.0064 (8)0.0007 (8)
C80.0210 (10)0.0330 (13)0.0383 (12)−0.0016 (9)0.0072 (9)0.0000 (10)
C90.0286 (11)0.0353 (14)0.0384 (13)−0.0099 (10)0.0133 (10)−0.0032 (10)
C100.0436 (13)0.0250 (12)0.0294 (11)−0.0070 (10)0.0142 (10)0.0012 (9)
C110.0334 (12)0.0240 (11)0.0277 (11)0.0015 (9)0.0049 (9)0.0034 (9)
C120.0218 (10)0.0232 (11)0.0237 (10)−0.0004 (8)0.0035 (8)−0.0009 (8)
C130.0178 (9)0.0196 (10)0.0231 (9)−0.0016 (8)0.0050 (7)0.0000 (8)
C140.0175 (9)0.0228 (10)0.0201 (9)−0.0001 (8)0.0045 (7)−0.0037 (8)
C150.0227 (10)0.0216 (11)0.0211 (9)−0.0001 (8)0.0078 (8)−0.0008 (8)
C160.0243 (10)0.0241 (11)0.0184 (9)0.0008 (8)0.0036 (8)−0.0015 (8)
C170.0283 (11)0.0287 (12)0.0206 (10)0.0036 (9)0.0039 (8)−0.0007 (9)
C180.0197 (9)0.0264 (11)0.0232 (10)−0.0002 (8)0.0014 (8)−0.0038 (8)
C190.0197 (9)0.0210 (10)0.0236 (10)−0.0026 (8)0.0051 (7)−0.0025 (8)
C200.0205 (9)0.0246 (11)0.0265 (10)0.0003 (8)0.0064 (8)−0.0029 (9)
C210.0208 (9)0.0221 (10)0.0184 (9)0.0005 (8)0.0037 (7)−0.0001 (8)
N10.0224 (9)0.0256 (10)0.0268 (9)0.0004 (7)0.0069 (7)0.0036 (7)
N20.0198 (8)0.0240 (10)0.0264 (9)0.0009 (7)0.0040 (7)0.0024 (7)
N30.0183 (8)0.0231 (9)0.0310 (9)0.0012 (7)0.0023 (7)0.0034 (8)
O10.0187 (7)0.0379 (9)0.0216 (7)−0.0007 (6)0.0017 (6)−0.0071 (6)
O20.0223 (8)0.0587 (13)0.0342 (9)−0.0062 (8)0.0135 (7)−0.0057 (8)
O30.0291 (8)0.0483 (11)0.0225 (8)0.0030 (8)0.0061 (6)0.0082 (7)
O40.0313 (9)0.0744 (15)0.0297 (9)−0.0118 (9)−0.0093 (7)0.0133 (9)
O50.0254 (8)0.0451 (11)0.0321 (8)−0.0132 (7)0.0010 (6)0.0028 (8)
O60.0237 (8)0.0391 (10)0.0239 (7)−0.0098 (7)0.0057 (6)0.0003 (7)
Geometric parameters (Å, °) top
Ag1—N22.1508 (18)C11—H11A0.9300
Ag1—N1i2.1729 (18)C12—N31.378 (3)
Ag1—O22.5320 (17)C13—O21.220 (3)
C1—N11.345 (3)C13—O11.289 (3)
C1—C21.379 (3)C13—C141.513 (3)
C1—H1A0.9300C14—C151.393 (3)
C2—C31.375 (3)C14—C211.392 (3)
C2—H2A0.9300C15—C161.398 (3)
C3—C41.399 (3)C15—H15A0.9300
C3—H3A0.9300C16—C181.389 (3)
C4—C51.389 (3)C16—C171.491 (3)
C4—C61.467 (3)C17—O41.205 (3)
C5—N11.340 (3)C17—O31.329 (3)
C5—H5A0.9300C18—C191.390 (3)
C6—N21.331 (3)C18—H18A0.9300
C6—N31.352 (3)C19—C211.395 (3)
C7—N21.389 (3)C19—C201.500 (3)
C7—C121.398 (3)C20—O51.218 (3)
C7—C81.400 (3)C20—O61.316 (3)
C8—C91.377 (4)C21—H21A0.9300
C8—H8A0.9300N3—O1ii2.828 (2)
C9—C101.408 (4)N3—H3B0.8600
C9—H9A0.9300O3—O6iii2.772 (2)
C10—C111.382 (3)O3—H3C0.841 (18)
C10—H10A0.9300O6—O1iv2.487 (2)
C11—C121.395 (3)O6—H6B0.841 (18)
N2—Ag1—N1i152.96 (7)O1—C13—C14116.17 (17)
N2—Ag1—O299.17 (7)C15—C14—C21119.42 (18)
N1i—Ag1—O2107.84 (7)C15—C14—C13119.86 (18)
N1—C1—C2122.1 (2)C21—C14—C13120.72 (18)
N1—C1—H1A119.0C14—C15—C16119.83 (19)
C2—C1—H1A119.0C14—C15—H15A120.1
C1—C2—C3119.9 (2)C16—C15—H15A120.1
C1—C2—H2A120.0C18—C16—C15120.08 (19)
C3—C2—H2A120.0C18—C16—C17117.48 (19)
C2—C3—C4118.8 (2)C15—C16—C17122.4 (2)
C2—C3—H3A120.6O4—C17—O3123.1 (2)
C4—C3—H3A120.6O4—C17—C16122.8 (2)
C5—C4—C3117.7 (2)O3—C17—C16114.16 (19)
C5—C4—C6121.90 (19)C19—C18—C16120.49 (19)
C3—C4—C6120.4 (2)C19—C18—H18A119.8
N1—C5—C4123.40 (19)C16—C18—H18A119.8
N1—C5—H5A118.3C18—C19—C21119.07 (19)
C4—C5—H5A118.3C18—C19—C20118.82 (18)
N2—C6—N3111.94 (19)C21—C19—C20122.08 (19)
N2—C6—C4125.60 (19)O5—C20—O6123.3 (2)
N3—C6—C4122.40 (18)O5—C20—C19121.8 (2)
N2—C7—C12109.27 (18)O6—C20—C19114.88 (18)
N2—C7—C8129.9 (2)C14—C21—C19120.96 (19)
C12—C7—C8120.8 (2)C14—C21—H21A119.5
C9—C8—C7117.1 (2)C19—C21—H21A119.5
C9—C8—H8A121.5C5—N1—C1118.03 (19)
C7—C8—H8A121.5C5—N1—Ag1i119.99 (14)
C8—C9—C10121.8 (2)C1—N1—Ag1i121.82 (15)
C8—C9—H9A119.1C6—N2—C7105.49 (18)
C10—C9—H9A119.1C6—N2—Ag1131.45 (15)
C11—C10—C9121.7 (2)C7—N2—Ag1123.03 (14)
C11—C10—H10A119.1C6—N3—C12107.83 (17)
C9—C10—H10A119.1C6—N3—O1ii134.45 (14)
C10—C11—C12116.3 (2)C12—N3—O1ii115.70 (14)
C10—C11—H11A121.8C6—N3—H3B126.1
C12—C11—H11A121.8C12—N3—H3B126.1
N3—C12—C11132.2 (2)C13—O2—Ag1166.85 (16)
N3—C12—C7105.44 (19)C17—O3—O6iii105.52 (13)
C11—C12—C7122.3 (2)C17—O3—H3C106 (2)
O2—C13—O1123.97 (19)C20—O6—O1iv108.75 (13)
O2—C13—C14119.85 (19)C20—O6—H6B109 (3)
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+1/2, z−1/2; (iv) −x, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O1ii0.862.012.828 (2)158
O3—H3C···O6iii0.841 (18)1.941 (19)2.772 (2)169 (4)
O6—H6B···O1iv0.841 (18)1.647 (19)2.487 (2)176 (4)
Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+1/2, z−1/2; (iv) −x, y−1/2, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Ag1—N22.1508 (18)C17—O31.329 (3)
Ag1—N1i2.1729 (18)C20—O51.218 (3)
Ag1—O22.5320 (17)C20—O61.316 (3)
C17—O41.205 (3)
N2—Ag1—N1i152.96 (7)N1i—Ag1—O2107.84 (7)
N2—Ag1—O299.17 (7)
Symmetry codes: (i) −x+1, −y+1, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O1ii0.862.012.828 (2)158
O3—H3C···O6iii0.841 (18)1.941 (19)2.772 (2)169 (4)
O6—H6B···O1iv0.841 (18)1.647 (19)2.487 (2)176 (4)
Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+1/2, z−1/2; (iv) −x, y−1/2, −z+1/2.
Acknowledgements top

We thank the Social Development Foundation of Jiangsu Province of China (BS2006038) and the Social Development Foundation of Zhenjiang, Jiangsu Province of China (SH2006057).

references
References top

Alcalde, E., Dinares, I., Perez-Garia, L. & Roca, T. (1992). Synthesis, pp. 295–398.

Dai, J. C., Hu, S. M., Wu, X. T., Fu, Z. Y., Du, W. X., Zhang, H. H. & Sun, R. Q. (2003). New J. Chem. 27, 914–918.

Plater, M. J., Foreman, M. S., Howie, R. A., Skakle, J. M. S., Coronado, E., Cómez-García, C. J., Gelbrich, T. & Hursthouse, M. B. (2001). Inorg. Chim. Acta, 319, 159–175.

Prior, T. J., Bradshaw, D., Teat, S. J. & Rosseinsky, M. J. (2003). Chem. Commun. pp. 500–501.

Rigaku (2002). CrystalClear. Version 1.35. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Siemens (1994). SHELXTL-Plus. Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.