organic compounds
4,4′-Dimethoxybiphenyl-3,3′-dicarboxylic acid
aCentre for Materials Science and Nanotechnology, Department of Chemistry, University of Oslo, PO Box 1126, 0315 Oslo, Norway, binGAP National Centre of Research-based Innovation, Department of Chemistry, University of Oslo, PO Box 1126, 0315 Oslo, Norway, and cDepartment of Chemistry, University of Bergen, PO Box 7803, 5020 Bergen, Norway
*Correspondence e-mail: fredrik.lundvall@smn.uio.no
The title compound, C16H14O6, was recrystallized under solvothermal conditions. The molecules are located on inversion centres, with one complete molecule generated from the by inversion. There are intramolecular O—H⋯O hydrogen bonds involving the carboxylic acid group and the O atom of the adjacent methoxy group. In the crystal, molecules are linked via O—H⋯O hydrogen bonds, forming chains propagating along [100]. The chains are linked via C—H⋯O hydrogen bonds, forming sheets parallel to (001).
CCDC reference: 997556
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2004) and ChemBioDraw Ultra (CambridgeSoft, 2009); software used to prepare material for publication: publCIF (Westrip, 2010) and WinGX (Farrugia, 2012).
Supporting information
CCDC reference: 997556
10.1107/S1600536814008599/qm2105sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814008599/qm2105Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814008599/qm2105Isup3.cml
The title compound was synthesized by a slightly modified version of the method used by Wang et al. (2009).
In the synthesis of methyl 5-iodo-2-methoxybenzoate, the reaction time was increased from 30 to 60 minutes.
In the Ullmann-coupling of 2 equivalents of methyl 5-iodo-2-methoxybenzoate to form dimethyl 4,4'-dimethoxy-3,3'-dicarboxylate, the reaction temperature was increased to 225 °C and the reaction time was set to 8 h.
In the synthesis of the title compound, dimethyl 4,4'-dimethoxy-3,3'-dicarboxylate and potassium hydroxide was stirred in a mixture of water and THF under reflux for 18 h. The mixture was concentrated under reduced pressure, washed with diethyl ether and acidified with nitric acid. The product was separated from the mixture by filtration and washed with water. The 1H NMR spectrum of the title compound is in good agreement with what was reported by Wang et al. (2009).
The title compound (151 mg, 0.5 mmol) was subjected to solvothermal conditions (H2O, 100 °C for 2 days) in the precence of Ca(NO3)2˙4H2O (118 mg, 0.5 mmol) and NaOH (40 mg, 1.0 mmol). The procedure did not yield the desired MOF, the title compound was however recrystallized into single crystals suitable for X-ray diffraction.
The structure was refined by full-matrix least squares using SHELXL97 (Sheldrick, 2008) as implemented in the WinGX suite (Farrugia, 2012). H-atoms were positioned geometrically at distances of 0.82 (OH), 0.93 (CH) and 0.96 Å (CH3) and refined using a riding model with Uiso (H)=1.2 Ueq (CH) and Uiso (H)=1.5 Ueq (OH and CH3)
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2004) and ChemBioDraw Ultra (CambridgeSoft, 2009); software used to prepare material for publication: publCIF (Westrip, 2010) and WinGX (Farrugia, 2012).C16H14O6 | F(000) = 632 |
Mr = 302.27 | Dx = 1.445 Mg m−3 |
Orthorhombic, Ibam | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -I 2 2c | Cell parameters from 2142 reflections |
a = 13.138 (2) Å | θ = 2.6–28.2° |
b = 15.615 (3) Å | µ = 0.11 mm−1 |
c = 6.7726 (11) Å | T = 296 K |
V = 1389.4 (4) Å3 | Needle, yellow |
Z = 4 | 0.65 × 0.10 × 0.09 mm |
Bruker APEXII CCD diffractometer | 779 independent reflections |
Radiation source: fine-focus sealed tube | 689 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→15 |
Tmin = 0.931, Tmax = 0.990 | k = −19→19 |
5188 measured reflections | l = −8→8 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0765P)2 + 0.4964P] where P = (Fo2 + 2Fc2)/3 |
779 reflections | (Δ/σ)max < 0.001 |
67 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.13 e Å−3 |
C16H14O6 | V = 1389.4 (4) Å3 |
Mr = 302.27 | Z = 4 |
Orthorhombic, Ibam | Mo Kα radiation |
a = 13.138 (2) Å | µ = 0.11 mm−1 |
b = 15.615 (3) Å | T = 296 K |
c = 6.7726 (11) Å | 0.65 × 0.10 × 0.09 mm |
Bruker APEXII CCD diffractometer | 779 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 689 reflections with I > 2σ(I) |
Tmin = 0.931, Tmax = 0.990 | Rint = 0.018 |
5188 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.24 e Å−3 |
779 reflections | Δρmin = −0.13 e Å−3 |
67 parameters |
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 | Occ. (<1) | |
C1 | 0.44707 (14) | 0.48358 (10) | 0.0000 | 0.0371 (5) | |
C2 | 0.36404 (15) | 0.53875 (11) | 0.0000 | 0.0386 (5) | |
H2 | 0.3761 | 0.5974 | 0.0000 | 0.046* | |
C3 | 0.26411 (14) | 0.51030 (12) | 0.0000 | 0.0396 (5) | |
C4 | 0.24524 (16) | 0.42222 (12) | 0.0000 | 0.0428 (5) | |
C5 | 0.32608 (16) | 0.36538 (12) | 0.0000 | 0.0478 (6) | |
H5 | 0.3141 | 0.3067 | 0.0000 | 0.057* | |
C6 | 0.42446 (16) | 0.39603 (12) | 0.0000 | 0.0457 (6) | |
H6 | 0.4779 | 0.3570 | 0.0000 | 0.055* | |
C7 | 0.18295 (17) | 0.57787 (13) | 0.0000 | 0.0492 (6) | |
C8 | 0.1198 (2) | 0.30898 (14) | 0.0000 | 0.0694 (8) | |
H8A | 0.0471 | 0.3030 | 0.0000 | 0.104* | |
H8B | 0.1474 | 0.2821 | 0.1157 | 0.104* | 0.50 |
H8C | 0.1474 | 0.2821 | −0.1157 | 0.104* | 0.50 |
O1 | 0.08706 (12) | 0.55256 (10) | 0.0000 | 0.0868 (8) | |
H1 | 0.0839 | 0.5026 | −0.0370 | 0.130* | 0.50 |
O2 | 0.20123 (13) | 0.65265 (9) | 0.0000 | 0.0658 (6) | |
O3 | 0.14575 (12) | 0.39725 (9) | 0.0000 | 0.0629 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0400 (11) | 0.0292 (10) | 0.0422 (10) | −0.0009 (7) | 0.000 | 0.000 |
C2 | 0.0414 (11) | 0.0260 (8) | 0.0484 (11) | −0.0003 (7) | 0.000 | 0.000 |
C3 | 0.0390 (10) | 0.0284 (10) | 0.0515 (11) | 0.0009 (8) | 0.000 | 0.000 |
C4 | 0.0365 (11) | 0.0331 (10) | 0.0586 (12) | −0.0037 (7) | 0.000 | 0.000 |
C5 | 0.0461 (12) | 0.0253 (9) | 0.0718 (15) | −0.0020 (8) | 0.000 | 0.000 |
C6 | 0.0415 (11) | 0.0281 (10) | 0.0675 (14) | 0.0039 (8) | 0.000 | 0.000 |
C7 | 0.0403 (12) | 0.0308 (10) | 0.0765 (15) | 0.0016 (8) | 0.000 | 0.000 |
C8 | 0.0497 (13) | 0.0349 (11) | 0.124 (2) | −0.0119 (10) | 0.000 | 0.000 |
O1 | 0.0360 (9) | 0.0414 (9) | 0.183 (2) | 0.0040 (7) | 0.000 | 0.000 |
O2 | 0.0488 (9) | 0.0284 (8) | 0.1201 (16) | 0.0036 (6) | 0.000 | 0.000 |
O3 | 0.0399 (9) | 0.0307 (8) | 0.1181 (15) | −0.0046 (6) | 0.000 | 0.000 |
C1—C2 | 1.390 (3) | C5—H5 | 0.9300 |
C1—C6 | 1.399 (2) | C6—H6 | 0.9300 |
C1—C1i | 1.482 (4) | C7—O2 | 1.192 (2) |
C2—C3 | 1.386 (3) | C7—O1 | 1.320 (3) |
C2—H2 | 0.9300 | C8—O3 | 1.420 (2) |
C3—C4 | 1.398 (3) | C8—H8A | 0.9600 |
C3—C7 | 1.500 (3) | C8—H8B | 0.9600 |
C4—O3 | 1.364 (3) | C8—H8C | 0.9600 |
C4—C5 | 1.384 (3) | O1—H1 | 0.8200 |
C5—C6 | 1.378 (3) | ||
C2—C1—C6 | 116.04 (18) | C5—C6—C1 | 122.59 (18) |
C2—C1—C1i | 121.45 (19) | C5—C6—H6 | 118.7 |
C6—C1—C1i | 122.5 (2) | C1—C6—H6 | 118.7 |
C3—C2—C1 | 123.00 (17) | O2—C7—O1 | 119.04 (19) |
C3—C2—H2 | 118.5 | O2—C7—C3 | 123.1 (2) |
C1—C2—H2 | 118.5 | O1—C7—C3 | 117.88 (17) |
C2—C3—C4 | 118.92 (18) | O3—C8—H8A | 109.5 |
C2—C3—C7 | 116.61 (17) | O3—C8—H8B | 109.5 |
C4—C3—C7 | 124.48 (18) | H8A—C8—H8B | 109.5 |
O3—C4—C5 | 123.50 (18) | O3—C8—H8C | 109.5 |
O3—C4—C3 | 116.84 (18) | H8A—C8—H8C | 109.5 |
C5—C4—C3 | 119.67 (19) | H8B—C8—H8C | 109.5 |
C6—C5—C4 | 119.79 (17) | C7—O1—H1 | 109.5 |
C6—C5—H5 | 120.1 | C4—O3—C8 | 120.52 (17) |
C4—C5—H5 | 120.1 | ||
C6—C1—C2—C3 | 0.0 | C4—C5—C6—C1 | 0.0 |
C1i—C1—C2—C3 | 180.0 | C2—C1—C6—C5 | 0.0 |
C1—C2—C3—C4 | 0.0 | C1i—C1—C6—C5 | 180.0 |
C1—C2—C3—C7 | 180.0 | C2—C3—C7—O2 | 0.0 |
C2—C3—C4—O3 | 180.0 | C4—C3—C7—O2 | 180.0 |
C7—C3—C4—O3 | 0.0 | C2—C3—C7—O1 | 180.0 |
C2—C3—C4—C5 | 0.0 | C4—C3—C7—O1 | 0.0 |
C7—C3—C4—C5 | 180.0 | C5—C4—O3—C8 | 0.0 |
O3—C4—C5—C6 | 180.0 | C3—C4—O3—C8 | 180.0 |
C3—C4—C5—C6 | 0.0 |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3 | 0.82 | 1.85 | 2.545 (2) | 141 |
O1—H1···O1ii | 0.82 | 2.42 | 2.816 (3) | 111 |
C5—H5···O2iii | 0.93 | 2.41 | 3.341 (2) | 175 |
Symmetry codes: (ii) −x, −y+1, z; (iii) −x+1/2, y−1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3 | 0.82 | 1.85 | 2.545 (2) | 141.3 |
O1—H1···O1i | 0.82 | 2.42 | 2.816 (3) | 110.8 |
C5—H5···O2ii | 0.93 | 2.41 | 3.341 (2) | 175 |
Symmetry codes: (i) −x, −y+1, z; (ii) −x+1/2, y−1/2, −z. |
Acknowledgements
We acknowledge the support from the Norwegian Research Council (project 190980), inGAP and the Department of Chemistry, UiO.
References
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As a part of a larger project, the title compound was synthesized for use as an organic linker in MOFs (Metal-Organic Frameworks).
The title compound has previously been reported (Wang et al., 2009) as an intermediate in the synthesis of an arylamide. The crystal structure was however not reported in this publication.
The structure of the title compound C16H14O6, has an orthorhombic Ibam symmetry. The asymmetric unit of the compound contains one half of the molecule, with the complete molecule being generated by an inversion centre. The two benzene rings appear as planar relative to each other and the carboxylic acid groups are located in a trans fashion with regards to the bond between the benzene rings. Biphenyl compounds commonly feature a torsion angle between the benzene rings, and the relatively large thermal parameters of the atoms furthest away from the molecular axis could indicate that a small torsion angle is present. Thus, the apparent planar configuration of the benzene rings might be considered a crystallographical artifact. Intramolecular hydrogen bonding between H1 and O3 directs the orientation of the hydroxyl group. Intermolecular hydrogen bonds between the O1 oxygen atoms of neighbouring molecules arrange the molecules in one-dimensional zigzag chains. These chains are further packed to form two-dimensional layers stabilized by hydrogen bonds between the carbonyl oxygen (O2) and one aromatic hydrogen (H5). It is worth noting that the carboxylic acid dimer motif thus is absent in this structure. The molecules are ordered along the c axis in a staggered motif with an intermolecular distance equal to one half of the c axis. This distance might indicate some weak π–π stacking interaction between the two-dimensional layers.