Acta Cryst. (2007). E63, o2887 [ doi:10.1107/S1600536807020570 ]
In the title compound, C14H10O5, each carboxyl group is coplanar with the attached aromatic ring. The dihedral angle between these planes is 72.56 (5)°. The carboxyl groups are linked by a pair of centrosymmetric O-H
O hydrogen bonds, creating a zigzag chain along the [2
1] direction.
The compound was purchased from Sigma-Aldrich [CAS 2215–89-6] and recrystallized from ethanol without further purification.
Structure solution and refinement was performed using the SHELX-97 suite of programs. Hydrogen atoms were refined in calculated positions, using a riding model (C–H = 0.95 Å; O–H = 0.84 Å).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001; Atwood & Barbour, 2003); software used to prepare material for publication: publCIF (Westrip, 2007).
![[Figure 1]](./kp2104fig1thm.gif)
| Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radius. |
![[Figure 2]](./kp2104fig2thm.gif)
| Fig. 2. The crystal packing of (I) viewed along [010] showing zigzag chain. H-bonds are displayed as dashed lines. |
| C14H10O5 | Z = 2 |
| Mr = 258.22 | F(000) = 268 |
| Triclinic, P1 | Dx = 1.518 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 5.3654 (9) Å | Cell parameters from 2085 reflections |
| b = 6.4093 (11) Å | θ = 2.4–27.7° |
| c = 16.847 (3) Å | µ = 0.12 mm−1 |
| α = 86.848 (3)° | T = 100 K |
| β = 83.106 (3)° | Needle, colourless |
| γ = 79.309 (3)° | 0.33 × 0.24 × 0.10 mm |
| V = 564.86 (16) Å3 |
| Bruker APEX CCD area-detector diffractometer | 1901 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.053 |
| graphite | θmax = 28.3°, θmin = 2.4° |
| ω scans | h = −7→6 |
| 6444 measured reflections | k = −8→8 |
| 2582 independent reflections | l = −22→22 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.123 | H-atom parameters constrained |
| S = 1.10 | w = 1/[σ2(Fo2) + (0.0549P)2 + 0.0103P] where P = (Fo2 + 2Fc2)/3 |
| 2582 reflections | (Δ/σ)max = 0.009 |
| 172 parameters | Δρmax = 0.38 e Å−3 |
| 0 restraints | Δρmin = −0.35 e Å−3 |
| C14H10O5 | γ = 79.309 (3)° |
| Mr = 258.22 | V = 564.86 (16) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 5.3654 (9) Å | Mo Kα radiation |
| b = 6.4093 (11) Å | µ = 0.12 mm−1 |
| c = 16.847 (3) Å | T = 100 K |
| α = 86.848 (3)° | 0.33 × 0.24 × 0.10 mm |
| β = 83.106 (3)° |
| Bruker APEX CCD area-detector diffractometer | 1901 reflections with I > 2σ(I) |
| 6444 measured reflections | Rint = 0.053 |
| 2582 independent reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
| wR(F2) = 0.123 | Δρmax = 0.38 e Å−3 |
| S = 1.10 | Δρmin = −0.35 e Å−3 |
| 2582 reflections | Absolute structure: ? |
| 172 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.1763 (2) | 1.24541 (18) | 0.02374 (7) | 0.0251 (3) | |
| H1 | 0.0651 | 1.3129 | −0.0037 | 0.030* | |
| C1 | 0.2712 (3) | 1.3777 (3) | 0.06123 (10) | 0.0176 (4) | |
| O2 | 0.2019 (2) | 1.57409 (18) | 0.05702 (7) | 0.0242 (3) | |
| C2 | 0.4720 (3) | 1.2816 (3) | 0.11236 (10) | 0.0171 (4) | |
| O3 | 1.0046 (2) | 1.03887 (17) | 0.26827 (7) | 0.0196 (3) | |
| C3 | 0.5979 (3) | 1.4139 (3) | 0.14919 (10) | 0.0179 (4) | |
| H3 | 0.5621 | 1.5629 | 0.1385 | 0.022* | |
| O4 | 1.1999 (2) | 0.12156 (17) | 0.43485 (7) | 0.0206 (3) | |
| C4 | 0.7753 (3) | 1.3304 (3) | 0.20139 (10) | 0.0187 (4) | |
| H4 | 0.8604 | 1.4211 | 0.2268 | 0.022* | |
| O5 | 0.7865 (2) | 0.22879 (18) | 0.47782 (7) | 0.0219 (3) | |
| H5 | 0.8076 | 0.1086 | 0.5012 | 0.026* | |
| C5 | 0.8262 (3) | 1.1128 (3) | 0.21581 (10) | 0.0166 (4) | |
| C6 | 0.7121 (3) | 0.9777 (3) | 0.17638 (10) | 0.0199 (4) | |
| H6 | 0.7564 | 0.8282 | 0.1845 | 0.024* | |
| C7 | 0.5332 (3) | 1.0625 (3) | 0.12509 (10) | 0.0194 (4) | |
| H7 | 0.4522 | 0.9711 | 0.0986 | 0.023* | |
| C8 | 0.9921 (3) | 0.8447 (3) | 0.30857 (10) | 0.0167 (4) | |
| C9 | 1.2095 (3) | 0.6890 (3) | 0.30130 (10) | 0.0186 (4) | |
| H9 | 1.3571 | 0.7134 | 0.2676 | 0.022* | |
| C10 | 1.2098 (3) | 0.4977 (3) | 0.34358 (10) | 0.0185 (4) | |
| H10 | 1.3584 | 0.3903 | 0.3391 | 0.022* | |
| C11 | 0.9941 (3) | 0.4623 (2) | 0.39243 (9) | 0.0155 (4) | |
| C12 | 0.7761 (3) | 0.6215 (2) | 0.39935 (10) | 0.0174 (4) | |
| H12 | 0.6280 | 0.5976 | 0.4329 | 0.021* | |
| C13 | 0.7753 (3) | 0.8134 (3) | 0.35746 (10) | 0.0184 (4) | |
| H13 | 0.6280 | 0.9219 | 0.3622 | 0.022* | |
| C14 | 0.9955 (3) | 0.2569 (3) | 0.43785 (10) | 0.0153 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0253 (7) | 0.0267 (7) | 0.0242 (7) | 0.0004 (6) | −0.0133 (6) | −0.0030 (6) |
| C1 | 0.0180 (9) | 0.0188 (9) | 0.0151 (8) | −0.0022 (7) | −0.0004 (7) | −0.0008 (7) |
| O2 | 0.0258 (7) | 0.0194 (7) | 0.0262 (7) | 0.0009 (5) | −0.0077 (6) | 0.0036 (5) |
| C2 | 0.0160 (9) | 0.0213 (9) | 0.0131 (8) | −0.0024 (7) | −0.0003 (7) | 0.0000 (7) |
| O3 | 0.0204 (7) | 0.0165 (6) | 0.0236 (7) | −0.0055 (5) | −0.0086 (5) | 0.0050 (5) |
| C3 | 0.0207 (9) | 0.0132 (8) | 0.0185 (9) | −0.0003 (7) | −0.0013 (7) | 0.0003 (7) |
| O4 | 0.0185 (7) | 0.0183 (7) | 0.0236 (7) | 0.0011 (5) | −0.0034 (5) | −0.0004 (5) |
| C4 | 0.0209 (9) | 0.0189 (9) | 0.0171 (9) | −0.0057 (7) | −0.0024 (7) | −0.0007 (7) |
| O5 | 0.0215 (7) | 0.0182 (6) | 0.0249 (7) | −0.0045 (5) | 0.0007 (5) | 0.0047 (5) |
| C5 | 0.0138 (8) | 0.0203 (9) | 0.0149 (8) | −0.0018 (7) | −0.0016 (7) | 0.0016 (7) |
| C6 | 0.0212 (9) | 0.0166 (9) | 0.0215 (9) | −0.0018 (7) | −0.0044 (7) | 0.0002 (7) |
| C7 | 0.0211 (9) | 0.0180 (9) | 0.0202 (9) | −0.0047 (7) | −0.0042 (7) | −0.0009 (7) |
| C8 | 0.0215 (9) | 0.0136 (8) | 0.0164 (9) | −0.0049 (7) | −0.0058 (7) | −0.0003 (7) |
| C9 | 0.0146 (9) | 0.0226 (9) | 0.0190 (9) | −0.0047 (7) | −0.0015 (7) | 0.0002 (7) |
| C10 | 0.0165 (9) | 0.0165 (9) | 0.0216 (9) | −0.0005 (7) | −0.0022 (7) | −0.0015 (7) |
| C11 | 0.0182 (9) | 0.0157 (9) | 0.0137 (8) | −0.0036 (7) | −0.0053 (7) | −0.0008 (7) |
| C12 | 0.0147 (8) | 0.0204 (9) | 0.0174 (9) | −0.0035 (7) | −0.0022 (7) | −0.0023 (7) |
| C13 | 0.0175 (9) | 0.0167 (9) | 0.0203 (9) | 0.0006 (7) | −0.0046 (7) | −0.0024 (7) |
| C14 | 0.0168 (9) | 0.0147 (8) | 0.0160 (8) | −0.0038 (7) | −0.0049 (7) | −0.0033 (7) |
| O1—C1 | 1.2933 (19) | C5—C6 | 1.386 (2) |
| O1—H1 | 0.8400 | C6—C7 | 1.385 (2) |
| C1—O2 | 1.2455 (19) | C6—H6 | 0.9500 |
| C1—C2 | 1.484 (2) | C7—H7 | 0.9500 |
| C2—C7 | 1.392 (2) | C8—C13 | 1.382 (2) |
| C2—C3 | 1.390 (2) | C8—C9 | 1.385 (2) |
| O3—C5 | 1.3820 (19) | C9—C10 | 1.384 (2) |
| O3—C8 | 1.3930 (19) | C9—H9 | 0.9500 |
| C3—C4 | 1.388 (2) | C10—C11 | 1.384 (2) |
| C3—H3 | 0.9500 | C10—H10 | 0.9500 |
| O4—C14 | 1.2633 (19) | C11—C12 | 1.400 (2) |
| C4—C5 | 1.385 (2) | C11—C14 | 1.485 (2) |
| C4—H4 | 0.9500 | C12—C13 | 1.383 (2) |
| O5—C14 | 1.274 (2) | C12—H12 | 0.9500 |
| O5—H5 | 0.8400 | C13—H13 | 0.9500 |
| C1—O1—H1 | 109.5 | C2—C7—H7 | 120.0 |
| O2—C1—O1 | 124.03 (15) | C13—C8—C9 | 121.36 (16) |
| O2—C1—C2 | 120.17 (15) | C13—C8—O3 | 121.04 (15) |
| O1—C1—C2 | 115.80 (15) | C9—C8—O3 | 117.50 (15) |
| C7—C2—C3 | 119.63 (16) | C10—C9—C8 | 119.44 (16) |
| C7—C2—C1 | 121.30 (15) | C10—C9—H9 | 120.3 |
| C3—C2—C1 | 119.06 (15) | C8—C9—H9 | 120.3 |
| C5—O3—C8 | 117.97 (12) | C9—C10—C11 | 120.15 (15) |
| C4—C3—C2 | 120.62 (16) | C9—C10—H10 | 119.9 |
| C4—C3—H3 | 119.7 | C11—C10—H10 | 119.9 |
| C2—C3—H3 | 119.7 | C10—C11—C12 | 119.74 (15) |
| C5—C4—C3 | 118.89 (16) | C10—C11—C14 | 119.96 (15) |
| C5—C4—H4 | 120.6 | C12—C11—C14 | 120.29 (15) |
| C3—C4—H4 | 120.6 | C13—C12—C11 | 120.30 (16) |
| C14—O5—H5 | 109.5 | C13—C12—H12 | 119.9 |
| O3—C5—C4 | 116.30 (14) | C11—C12—H12 | 119.9 |
| O3—C5—C6 | 122.47 (15) | C8—C13—C12 | 119.01 (16) |
| C4—C5—C6 | 121.16 (16) | C8—C13—H13 | 120.5 |
| C7—C6—C5 | 119.48 (16) | C12—C13—H13 | 120.5 |
| C7—C6—H6 | 120.3 | O4—C14—O5 | 123.99 (15) |
| C5—C6—H6 | 120.3 | O4—C14—C11 | 119.03 (15) |
| C6—C7—C2 | 120.07 (16) | O5—C14—C11 | 116.98 (14) |
| C6—C7—H7 | 120.0 | ||
| O2—C1—C2—C7 | 172.85 (16) | C5—O3—C8—C13 | −59.0 (2) |
| O1—C1—C2—C7 | −6.4 (2) | C5—O3—C8—C9 | 124.55 (16) |
| O2—C1—C2—C3 | −6.1 (2) | C13—C8—C9—C10 | 0.2 (3) |
| O1—C1—C2—C3 | 174.68 (15) | O3—C8—C9—C10 | 176.70 (14) |
| C7—C2—C3—C4 | −3.0 (3) | C8—C9—C10—C11 | 0.3 (2) |
| C1—C2—C3—C4 | 175.93 (15) | C9—C10—C11—C12 | −0.5 (2) |
| C2—C3—C4—C5 | 0.4 (3) | C9—C10—C11—C14 | −179.86 (14) |
| C8—O3—C5—C4 | 155.32 (15) | C10—C11—C12—C13 | 0.2 (2) |
| C8—O3—C5—C6 | −27.7 (2) | C14—C11—C12—C13 | 179.56 (14) |
| C3—C4—C5—O3 | 179.98 (14) | C9—C8—C13—C12 | −0.5 (2) |
| C3—C4—C5—C6 | 3.0 (3) | O3—C8—C13—C12 | −176.87 (14) |
| O3—C5—C6—C7 | 179.47 (15) | C11—C12—C13—C8 | 0.3 (2) |
| C4—C5—C6—C7 | −3.7 (3) | C10—C11—C14—O4 | 4.2 (2) |
| C5—C6—C7—C2 | 1.1 (3) | C12—C11—C14—O4 | −175.22 (15) |
| C3—C2—C7—C6 | 2.3 (3) | C10—C11—C14—O5 | −175.75 (14) |
| C1—C2—C7—C6 | −176.65 (15) | C12—C11—C14—O5 | 4.9 (2) |
We thank Professor L. J. Barbour for helpful discussions. Financial support for this work was provided by the National Research Foundation of South Africa, as well as SASOL Industries. The data collection was undertaken on an instrument managed by the Central Analytical Facility at the University of Stellenbosch.
Atwood, J. L. & Barbour, L. J. (2003). Cryst. Growth Des. 3, 3–8.
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Bruker (2002). SMART. Version 5.628. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2003). SAINT. Version 6.45. Bruker AXS Inc., Madison, Wisconsin, USA.
Eddaoudi, M., Moler, D. B., Li, H., Chen, B., Reineke, T. M., O'Keeffe, M. & Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319–330.
Férey, G., Mellot-Draznieks, C. M., Serre, C., Millange, F., Dutour, J., Surblé, S. & Margiolaki, I. (2005). Science, 309, 2040–2042.
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Westrip, S. P. (2007). publCIF. Version 1.0_c. In preparation.
Considerable attention is focused on the synthesis of new ligands for the construction of metal organic frameworks (MOF's) since they add structural diversity to these materials. This study originates from our interest in U-shaped ligands of the rigid aromatics containing their coordinating groups at the terminal site. Two such ligands may coordinate two metal centers, closing the circle and thus forming a box-like aperture. Upon crystallization these boxed structures may form a porous material. Materials of this type are increasingly in demand for applications in gas storage since they are selective to the shapes and sizes of the molecules that can pass through the enclosed pore. This selectivity is dependent on their structural framework and the pore size formed therein (Férey et al., 2005). It has been found that multidentate linkers such as carboxylates allow the formation of more rigid frameworks than, for example, commonly used poly-topic N-bound organic linkers. This functionality is due to their ability to incorporate metal ions into M—O—C clusters (Eddaoudi et al., 2001). To this end the dicarboxylic acid had been selected as an organic linker.
One such linker that was selected is 4,4'-oxydibenzoic acid, (I), commercially available from Sigma-Aldrich. However, its crystal structure has not been reported.
In the crystal structure, the respective acid groups are co-planar with their aromatic rings (Fig. 1). The angle subtended at the central oxygen atom, O3, is 117.97 (12)°. This is higher than the average C—O—C angle of 115° owing to the steric interactions between H6 and H13.
The angle between the least squares planes defined by the 6 carbon atoms of each benzene ring is 72.56 (0.05) °.
This structure forms a one-dimensional zigzag chain that is linked via the H-bonds between the acid proton of one molecule and the carbonyl oxygen of another. The infinite chain of intermolecular H-bonded molecules packs along [2 - 3 1].