supplementary materials
4'-Hydroxybiphenyl-4-carboxylic acid
The title compound, C13H10O3, has potential oxygen donor and acceptor sites. Intermolecular hydrogen bonding between neighboring carboxylate groups leads to the formation of hydrogen-bonded dimers [graph-set motif R22(8)]. A second hydrogen-bonding interaction between the hydroxy groups generates a chain and extends the structure into a lamellar layer. One of the benzene rings is disordered over two positions with an occupancy ratio of 0.57 (2):0.43 (2).
4-Hydroxyl-biphenyl-4'-carboxylic acid was dissolved in a hot ethanol-water
solution (1:1; v/v) with stirring. Colorless single crystals
suitable for X-ray diffraction were obtained at room temperature by slow
evaporation of the solvent over a period of several days.
In the initial refinement with disorder not taken into account one of phenyl
rings showed significantly elongated thermal ellipsoids indicating disorder,
the dihedral angle between two phenyl rings is 5.66 (2) /%A, and the adjacent
distances of C-H···C-H interactions in the biphenylene are 2.044 (1) and
2.077 (1) /%A, respectively, thus leading to a static repulsion between two
phenyl rings,and the phenyl ring was thus refined as being
disordered over two positions. The occupancy ratio
refined to 0.57 (2) to 0.43 (2). The adps of the disordered atoms were
restrained to be close to isotropic and
those of equivalent atoms were set to be identical. Carbon-bound, hydroxyl and
carboxylate group H atoms were placed at calculated positions and were treated
as riding on their parent C or O atoms with C—H = 0.93 Å, with
Uiso(H) = 1.2 Ueq(C); O—H = 0.82 Å
and with Uiso(H) = 1.5 Ueq(O).
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
4'-Hydroxybiphenyl-4-carboxylic acid
top
Crystal data top
| C13H10O3 | F000 = 448 |
| Mr = 214.21 | Dx = 1.428 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation
λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 1560 reflections |
| a = 8.6500 (7) Å | θ = 1.4–28.0º |
| b = 5.5077 (5) Å | µ = 0.10 mm−1 |
| c = 20.9655 (18) Å | T = 293 (2) K |
| β = 94.145 (3)º | Plate, colorless |
| V = 996.22 (15) Å3 | 0.21 × 0.20 × 0.16 mm |
| Z = 4 | |
Data collection top
Bruker APEXII area-detector
diffractometer | 854 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.063 |
| Monochromator: graphite | θmax = 25.2º |
| T = 293(2) K | θmin = 2.0º |
| φ and ω scans | h = −10→10 |
| Absorption correction: none | k = −5→6 |
| 6310 measured reflections | l = −24→25 |
| 1800 independent reflections | |
Refinement top
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.058 | H-atom parameters constrained |
| wR(F2) = 0.183 | w = 1/[σ2(Fo2) + (0.0772P)2]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max < 0.001 |
| 1800 reflections | Δρmax = 0.18 e Å−3 |
| 160 parameters | Δρmin = −0.19 e Å−3 |
| 24 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods | |
Crystal data top
| C13H10O3 | V = 996.22 (15) Å3 |
| Mr = 214.21 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 8.6500 (7) Å | µ = 0.10 mm−1 |
| b = 5.5077 (5) Å | T = 293 (2) K |
| c = 20.9655 (18) Å | 0.21 × 0.20 × 0.16 mm |
| β = 94.145 (3)º | |
Data collection top
Bruker APEXII area-detector
diffractometer | 1800 independent reflections |
| Absorption correction: none | 854 reflections with I > 2σ(I) |
| 6310 measured reflections | Rint = 0.063 |
Refinement top
| R[F2 > 2σ(F2)] = 0.058 | 24 restraints |
| wR(F2) = 0.183 | H-atom parameters constrained |
| S = 1.01 | Δρmax = 0.18 e Å−3 |
| 1800 reflections | Δρmin = −0.19 e Å−3 |
| 160 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| | x | y | z | Uiso*/Ueq | Occ. (<1) |
| C1 | 1.3074 (3) | 0.0387 (7) | 0.03781 (15) | 0.0499 (9) | |
| C8 | 0.7212 (3) | 0.1508 (6) | 0.15024 (14) | 0.0448 (8) | |
| C9 | 0.6208 (3) | 0.3440 (6) | 0.13452 (16) | 0.0578 (10) | |
| H9 | 0.6499 | 0.4597 | 0.1054 | 0.069* | |
| C10 | 0.4806 (3) | 0.3688 (7) | 0.16071 (17) | 0.0593 (10) | |
| H10 | 0.4167 | 0.4999 | 0.1493 | 0.071* | |
| C11 | 0.4352 (3) | 0.2019 (7) | 0.20337 (15) | 0.0525 (9) | |
| C12 | 0.5302 (4) | 0.0092 (7) | 0.22074 (16) | 0.0596 (10) | |
| H12 | 0.5001 | −0.1052 | 0.2500 | 0.072* | |
| C13 | 0.6703 (4) | −0.0119 (6) | 0.19414 (15) | 0.0545 (9) | |
| H13 | 0.7339 | −0.1424 | 0.2064 | 0.065* | |
| O1 | 1.3852 (2) | −0.1522 (5) | 0.05016 (11) | 0.0704 (8) | |
| O2 | 1.3483 (2) | 0.2037 (5) | 0.00069 (12) | 0.0696 (8) | |
| H2 | 1.4342 | 0.1717 | −0.0112 | 0.104* | |
| O3 | 0.2936 (3) | 0.2362 (5) | 0.22900 (12) | 0.0720 (8) | |
| H3A | 0.2672 | 0.1099 | 0.2458 | 0.108* | |
| C2 | 1.15866 (19) | 0.0702 (5) | 0.06838 (10) | 0.0480 (8) | 0.43 (2) |
| C3 | 1.0867 (8) | 0.2959 (6) | 0.0682 (6) | 0.052 (3) | 0.43 (2) |
| H3 | 1.1327 | 0.4288 | 0.0498 | 0.063* | 0.43 (2) |
| C4 | 0.9458 (8) | 0.3228 (6) | 0.0954 (6) | 0.045 (2) | 0.43 (2) |
| H4 | 0.8976 | 0.4738 | 0.0952 | 0.054* | 0.43 (2) |
| C5 | 0.8770 (2) | 0.1241 (4) | 0.12279 (11) | 0.0441 (8) | 0.43 (2) |
| C6 | 0.9490 (7) | −0.1015 (7) | 0.1230 (5) | 0.045 (3) | 0.43 (2) |
| H6 | 0.9029 | −0.2345 | 0.1413 | 0.054* | 0.43 (2) |
| C7 | 1.0898 (8) | −0.1285 (7) | 0.0958 (6) | 0.052 (3) | 0.43 (2) |
| H7 | 1.1380 | −0.2795 | 0.0959 | 0.062* | 0.43 (2) |
| C2' | 1.15879 (19) | 0.0709 (5) | 0.06822 (10) | 0.0480 (8) | 0.57 (2) |
| C3' | 1.0571 (7) | 0.2579 (15) | 0.0469 (5) | 0.052 (2) | 0.57 (2) |
| H3' | 1.0845 | 0.3647 | 0.0153 | 0.063* | 0.57 (2) |
| C4' | 0.9160 (7) | 0.2818 (15) | 0.0734 (5) | 0.049 (2) | 0.57 (2) |
| H4' | 0.8485 | 0.4045 | 0.0588 | 0.059* | 0.57 (2) |
| C5' | 0.8725 (2) | 0.1234 (5) | 0.12205 (11) | 0.0441 (8) | 0.57 (2) |
| C6' | 0.9755 (6) | −0.0581 (16) | 0.1431 (4) | 0.048 (2) | 0.57 (2) |
| H6' | 0.9505 | −0.1621 | 0.1758 | 0.057* | 0.57 (2) |
| C7' | 1.1161 (6) | −0.0845 (15) | 0.1155 (4) | 0.047 (2) | 0.57 (2) |
| H7' | 1.1827 | −0.2097 | 0.1291 | 0.056* | 0.57 (2) |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| C1 | 0.0396 (18) | 0.061 (2) | 0.051 (2) | 0.0010 (18) | 0.0134 (16) | 0.0005 (19) |
| C8 | 0.0388 (17) | 0.044 (2) | 0.0527 (18) | −0.0001 (16) | 0.0113 (15) | −0.0022 (17) |
| C9 | 0.0445 (19) | 0.058 (2) | 0.073 (2) | 0.0005 (18) | 0.0159 (17) | 0.011 (2) |
| C10 | 0.0418 (19) | 0.057 (2) | 0.081 (2) | 0.0079 (18) | 0.0170 (18) | 0.008 (2) |
| C11 | 0.0338 (17) | 0.062 (3) | 0.064 (2) | −0.0032 (17) | 0.0160 (15) | −0.0135 (19) |
| C12 | 0.049 (2) | 0.061 (3) | 0.071 (2) | 0.0015 (18) | 0.0214 (18) | 0.0075 (19) |
| C13 | 0.0448 (19) | 0.051 (2) | 0.069 (2) | 0.0088 (17) | 0.0183 (17) | 0.0053 (18) |
| O1 | 0.0529 (15) | 0.0705 (18) | 0.0910 (18) | 0.0171 (13) | 0.0281 (13) | 0.0188 (15) |
| O2 | 0.0460 (14) | 0.083 (2) | 0.0837 (18) | 0.0127 (13) | 0.0307 (13) | 0.0194 (15) |
| O3 | 0.0418 (13) | 0.090 (2) | 0.0882 (18) | 0.0033 (13) | 0.0308 (12) | −0.0057 (16) |
| C2 | 0.0334 (17) | 0.062 (2) | 0.050 (2) | −0.0008 (17) | 0.0144 (15) | 0.0031 (18) |
| C3 | 0.040 (5) | 0.065 (7) | 0.054 (5) | 0.002 (5) | 0.015 (4) | 0.006 (5) |
| C4 | 0.046 (5) | 0.047 (6) | 0.043 (5) | 0.005 (4) | 0.012 (4) | 0.000 (4) |
| C5 | 0.0367 (17) | 0.049 (2) | 0.0476 (19) | −0.0041 (16) | 0.0129 (14) | 0.0004 (17) |
| C6 | 0.045 (5) | 0.052 (5) | 0.039 (5) | −0.002 (4) | 0.002 (4) | −0.008 (4) |
| C7 | 0.041 (5) | 0.061 (7) | 0.052 (5) | 0.003 (4) | 0.001 (4) | −0.001 (5) |
| C2' | 0.0334 (17) | 0.062 (2) | 0.050 (2) | −0.0008 (17) | 0.0144 (15) | 0.0031 (18) |
| C3' | 0.044 (4) | 0.057 (5) | 0.058 (4) | 0.004 (3) | 0.014 (4) | 0.008 (4) |
| C4' | 0.042 (4) | 0.049 (4) | 0.057 (4) | 0.012 (3) | 0.014 (3) | 0.000 (4) |
| C5' | 0.0367 (17) | 0.049 (2) | 0.0476 (19) | −0.0041 (16) | 0.0129 (14) | 0.0004 (17) |
| C6' | 0.036 (4) | 0.068 (5) | 0.039 (4) | 0.007 (3) | 0.010 (3) | 0.009 (4) |
| C7' | 0.029 (3) | 0.063 (5) | 0.049 (4) | 0.011 (3) | 0.005 (3) | 0.007 (4) |
Geometric parameters (Å, °) top
| C1—O2 | 1.264 (4) | C3—C4 | 1.3900 |
| C1—O1 | 1.265 (4) | C3—H3 | 0.9300 |
| C1—C2 | 1.488 (4) | C4—C5 | 1.3900 |
| C8—C13 | 1.379 (4) | C4—H4 | 0.9300 |
| C8—C9 | 1.398 (4) | C5—C6 | 1.3900 |
| C8—C5 | 1.510 (3) | C6—C7 | 1.3900 |
| C9—C10 | 1.374 (4) | C6—H6 | 0.9300 |
| C9—H9 | 0.9300 | C7—H7 | 0.9300 |
| C10—C11 | 1.360 (5) | C2'—C7' | 1.3793 |
| C10—H10 | 0.9300 | C2'—C3' | 1.4061 |
| C11—C12 | 1.375 (4) | C3'—C4' | 1.3820 |
| C11—O3 | 1.386 (4) | C3'—H3' | 0.9300 |
| C12—C13 | 1.375 (4) | C4'—C5' | 1.4147 |
| C12—H12 | 0.9300 | C4'—H4' | 0.9300 |
| C13—H13 | 0.9300 | C5'—C6' | 1.3903 |
| O2—H2 | 0.8200 | C6'—C7' | 1.3923 |
| O3—H3A | 0.8200 | C6'—H6' | 0.9300 |
| C2—C3 | 1.3900 | C7'—H7' | 0.9300 |
| C2—C7 | 1.3900 | | |
| | | |
| O2—C1—O1 | 123.7 (3) | C3—C4—C5 | 120.0 |
| O2—C1—C2 | 118.1 (3) | C3—C4—H4 | 120.0 |
| O1—C1—C2 | 118.2 (3) | C5—C4—H4 | 120.0 |
| C13—C8—C9 | 115.4 (3) | C6—C5—C4 | 120.0 |
| C13—C8—C5 | 121.9 (3) | C6—C5—C8 | 119.8 (2) |
| C9—C8—C5 | 122.7 (3) | C4—C5—C8 | 120.1 (2) |
| C10—C9—C8 | 122.2 (3) | C5—C6—C7 | 120.0 |
| C10—C9—H9 | 118.9 | C5—C6—H6 | 120.0 |
| C8—C9—H9 | 118.9 | C7—C6—H6 | 120.0 |
| C11—C10—C9 | 120.1 (3) | C6—C7—C2 | 120.0 |
| C11—C10—H10 | 120.0 | C6—C7—H7 | 120.0 |
| C9—C10—H10 | 120.0 | C2—C7—H7 | 120.0 |
| C10—C11—C12 | 120.1 (3) | C7'—C2'—C3' | 119.2 |
| C10—C11—O3 | 117.9 (3) | C4'—C3'—C2' | 119.5 |
| C12—C11—O3 | 122.0 (3) | C4'—C3'—H3' | 120.2 |
| C11—C12—C13 | 119.0 (3) | C2'—C3'—H3' | 120.2 |
| C11—C12—H12 | 120.5 | C3'—C4'—C5' | 121.3 |
| C13—C12—H12 | 120.5 | C3'—C4'—H4' | 119.4 |
| C12—C13—C8 | 123.3 (3) | C5'—C4'—H4' | 119.4 |
| C12—C13—H13 | 118.4 | C6'—C5'—C4' | 118.4 |
| C8—C13—H13 | 118.4 | C5'—C6'—C7' | 120.1 |
| C3—C2—C7 | 120.0 | C5'—C6'—H6' | 120.0 |
| C3—C2—C1 | 120.3 (2) | C7'—C6'—H6' | 120.0 |
| C7—C2—C1 | 119.7 (2) | C2'—C7'—C6' | 121.5 |
| C4—C3—C2 | 120.0 | C2'—C7'—H7' | 119.3 |
| C4—C3—H3 | 120.0 | C6'—C7'—H7' | 119.3 |
| C2—C3—H3 | 120.0 | | |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1i | 0.82 | 1.82 | 2.624 (3) | 168 |
| O3—H3A···O3ii | 0.82 | 2.20 | 3.0041 (18) | 168 |
| Symmetry codes: (i) −x+3, −y, −z; (ii) −x+1/2, 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 |
| O2—H2···O1i | 0.82 | 1.82 | 2.624 (3) | 168 |
| O3—H3A···O3ii | 0.82 | 2.20 | 3.0041 (18) | 168 |
| Symmetry codes: (i) −x+3, −y, −z; (ii) −x+1/2, y−1/2, −z+1/2. |
The authors thank South China Normal University for supporting this study.
Bernstein, J., Davis, R. E., Shimoni, L. & $ Chang, N.-L. (1995). Angew. Chem. Int. Ed. 34, 1555–1573.
Bruker (2004). APEX2 and SMART. Bruker AXS Inc, Madison, Wisconsin, USA.
Datta, A. & $ Pati, S. K. (2006). Chem. Soc. Rev. pp. 1305–1323.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Zwier, T. S. (1996). Annu. Rev. Phys. Chem. 47, 205–241.
![[Figure 1]](./zl2111fig1thm.gif)
![[Figure 2]](./zl2111fig2thm.gif)
Hydrogen-bonding interactions between ligands are specific and directional. When present in metal complexes they usually do not rely on the properties of the metal ions, but they play an important role in the overall structures and functions of the complexes and the way in which they pack in the solid state (Zwier et al., 1996; Datta & Pati, 2006). In this context we report here the crystal structure of the title compound, (I).
The molecular structure of (I) is shown in Fig. 1. The C—O and C—C bond distances show no remarkable features. The title molecular structure acts as both a hydrogen bonding donor and acceptor, forming dimers with neighboring molecules through O—H···O hydrogen bonding with a R22(8) graph set motif (Bernstein et al., 1995). A second hydrogen bonding interaction by the hydroxyl groups forms a chain and extends the structure into a lamellar layer (Table 1, Fig. 2).