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ISSN: 2056-9890

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

(Received 5 March 2014; accepted 15 April 2014; online 30 April 2014)

The title compound, C16H14O6, was recrystallized under solvothermal conditions. The mol­ecules are located on inversion centres, with one complete mol­ecule generated from the asymmetric unit 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).

Related literature

For the synthesis, see Wang et al. (2009[Wang, L., Xiao, Z.-Y., Hou, J.-L., Wang, G.-T., Jiang, X.-K. & Li, Z.-T. (2009). Tetrahedron, 65, 10544-10551.]).

[Scheme 1]

Experimental

Crystal data
  • C16H14O6

  • Mr = 302.27

  • Orthorhombic, I b a m

  • a = 13.138 (2) Å

  • b = 15.615 (3) Å

  • c = 6.7726 (11) Å

  • V = 1389.4 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.11 mm−1

  • T = 296 K

  • 0.65 × 0.10 × 0.09 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.931, Tmax = 0.990

  • 5188 measured reflections

  • 779 independent reflections

  • 689 reflections with I > 2σ(I)

  • Rint = 0.018

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.136

  • S = 1.12

  • 779 reflections

  • 67 parameters

  • H-atom parameters constrained

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.13 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1⋯O3 0.82 1.85 2.545 (2) 141
O1—H1⋯O1i 0.82 2.42 2.816 (3) 111
C5—H5⋯O2ii 0.93 2.41 3.341 (2) 175
Symmetry codes: (i) -x, -y+1, z; (ii) [-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z].

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2004[Brandenburg, K. (2004). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and ChemBioDraw Ultra (CambridgeSoft, 2009[CambridgeSoft (2009). ChemBioDraw Ultra. CambridgeSoft Corporation, Cambridge, Massachusetts, USA.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]) and WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]).

Supporting information


Comment top

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 ππ stacking interaction between the two-dimensional layers.

Related literature top

For the synthesis, see Wang et al. (2009).

Experimental top

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)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.

Refinement top

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)

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. [One molecular unit of the title compound with atom labels and 50% probability displacement ellipsoids. Hydrogen atoms are omitted for clarity.]
[Figure 2] Fig. 2. [Packing diagram of the title compound viewed along the c axis. Hydrogen bonds are indicated by dashed lines.]
[Figure 3] Fig. 3. [Packing diagram of the title compound viewed close to the a axis.]
4,4'-Dimethoxybiphenyl-3,3'-dicarboxylic acid top
Crystal data top
C16H14O6F(000) = 632
Mr = 302.27Dx = 1.445 Mg m3
Orthorhombic, IbamMo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2 2cCell parameters from 2142 reflections
a = 13.138 (2) Åθ = 2.6–28.2°
b = 15.615 (3) ŵ = 0.11 mm1
c = 6.7726 (11) ÅT = 296 K
V = 1389.4 (4) Å3Needle, yellow
Z = 40.65 × 0.10 × 0.09 mm
Data collection top
Bruker APEXII CCD
diffractometer
779 independent reflections
Radiation source: fine-focus sealed tube689 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
ϕ and ω scansθmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1615
Tmin = 0.931, Tmax = 0.990k = 1919
5188 measured reflectionsl = 88
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H-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 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.13 e Å3
Crystal data top
C16H14O6V = 1389.4 (4) Å3
Mr = 302.27Z = 4
Orthorhombic, IbamMo Kα radiation
a = 13.138 (2) ŵ = 0.11 mm1
b = 15.615 (3) ÅT = 296 K
c = 6.7726 (11) Å0.65 × 0.10 × 0.09 mm
Data collection top
Bruker APEXII CCD
diffractometer
779 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
689 reflections with I > 2σ(I)
Tmin = 0.931, Tmax = 0.990Rint = 0.018
5188 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.136H-atom parameters constrained
S = 1.12Δρmax = 0.24 e Å3
779 reflectionsΔρmin = 0.13 e Å3
67 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*/UeqOcc. (<1)
C10.44707 (14)0.48358 (10)0.00000.0371 (5)
C20.36404 (15)0.53875 (11)0.00000.0386 (5)
H20.37610.59740.00000.046*
C30.26411 (14)0.51030 (12)0.00000.0396 (5)
C40.24524 (16)0.42222 (12)0.00000.0428 (5)
C50.32608 (16)0.36538 (12)0.00000.0478 (6)
H50.31410.30670.00000.057*
C60.42446 (16)0.39603 (12)0.00000.0457 (6)
H60.47790.35700.00000.055*
C70.18295 (17)0.57787 (13)0.00000.0492 (6)
C80.1198 (2)0.30898 (14)0.00000.0694 (8)
H8A0.04710.30300.00000.104*
H8B0.14740.28210.11570.104*0.50
H8C0.14740.28210.11570.104*0.50
O10.08706 (12)0.55256 (10)0.00000.0868 (8)
H10.08390.50260.03700.130*0.50
O20.20123 (13)0.65265 (9)0.00000.0658 (6)
O30.14575 (12)0.39725 (9)0.00000.0629 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0400 (11)0.0292 (10)0.0422 (10)0.0009 (7)0.0000.000
C20.0414 (11)0.0260 (8)0.0484 (11)0.0003 (7)0.0000.000
C30.0390 (10)0.0284 (10)0.0515 (11)0.0009 (8)0.0000.000
C40.0365 (11)0.0331 (10)0.0586 (12)0.0037 (7)0.0000.000
C50.0461 (12)0.0253 (9)0.0718 (15)0.0020 (8)0.0000.000
C60.0415 (11)0.0281 (10)0.0675 (14)0.0039 (8)0.0000.000
C70.0403 (12)0.0308 (10)0.0765 (15)0.0016 (8)0.0000.000
C80.0497 (13)0.0349 (11)0.124 (2)0.0119 (10)0.0000.000
O10.0360 (9)0.0414 (9)0.183 (2)0.0040 (7)0.0000.000
O20.0488 (9)0.0284 (8)0.1201 (16)0.0036 (6)0.0000.000
O30.0399 (9)0.0307 (8)0.1181 (15)0.0046 (6)0.0000.000
Geometric parameters (Å, º) top
C1—C21.390 (3)C5—H50.9300
C1—C61.399 (2)C6—H60.9300
C1—C1i1.482 (4)C7—O21.192 (2)
C2—C31.386 (3)C7—O11.320 (3)
C2—H20.9300C8—O31.420 (2)
C3—C41.398 (3)C8—H8A0.9600
C3—C71.500 (3)C8—H8B0.9600
C4—O31.364 (3)C8—H8C0.9600
C4—C51.384 (3)O1—H10.8200
C5—C61.378 (3)
C2—C1—C6116.04 (18)C5—C6—C1122.59 (18)
C2—C1—C1i121.45 (19)C5—C6—H6118.7
C6—C1—C1i122.5 (2)C1—C6—H6118.7
C3—C2—C1123.00 (17)O2—C7—O1119.04 (19)
C3—C2—H2118.5O2—C7—C3123.1 (2)
C1—C2—H2118.5O1—C7—C3117.88 (17)
C2—C3—C4118.92 (18)O3—C8—H8A109.5
C2—C3—C7116.61 (17)O3—C8—H8B109.5
C4—C3—C7124.48 (18)H8A—C8—H8B109.5
O3—C4—C5123.50 (18)O3—C8—H8C109.5
O3—C4—C3116.84 (18)H8A—C8—H8C109.5
C5—C4—C3119.67 (19)H8B—C8—H8C109.5
C6—C5—C4119.79 (17)C7—O1—H1109.5
C6—C5—H5120.1C4—O3—C8120.52 (17)
C4—C5—H5120.1
C6—C1—C2—C30.0C4—C5—C6—C10.0
C1i—C1—C2—C3180.0C2—C1—C6—C50.0
C1—C2—C3—C40.0C1i—C1—C6—C5180.0
C1—C2—C3—C7180.0C2—C3—C7—O20.0
C2—C3—C4—O3180.0C4—C3—C7—O2180.0
C7—C3—C4—O30.0C2—C3—C7—O1180.0
C2—C3—C4—C50.0C4—C3—C7—O10.0
C7—C3—C4—C5180.0C5—C4—O3—C80.0
O3—C4—C5—C6180.0C3—C4—O3—C8180.0
C3—C4—C5—C60.0
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O30.821.852.545 (2)141
O1—H1···O1ii0.822.422.816 (3)111
C5—H5···O2iii0.932.413.341 (2)175
Symmetry codes: (ii) x, y+1, z; (iii) x+1/2, y1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O30.821.852.545 (2)141.3
O1—H1···O1i0.822.422.816 (3)110.8
C5—H5···O2ii0.932.413.341 (2)175
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, y1/2, z.
 

Acknowledgements

We acknowledge the support from the Norwegian Research Council (project 190980), inGAP and the Department of Chemistry, UiO.

References

First citationAltomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.  CrossRef Web of Science IUCr Journals
First citationBrandenburg, K. (2004). DIAMOND. Crystal Impact GbR, Bonn, Germany.
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationCambridgeSoft (2009). ChemBioDraw Ultra. CambridgeSoft Corporation, Cambridge, Massachusetts, USA.
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWang, L., Xiao, Z.-Y., Hou, J.-L., Wang, G.-T., Jiang, X.-K. & Li, Z.-T. (2009). Tetrahedron, 65, 10544–10551.  Web of Science CrossRef CAS
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals

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ISSN: 2056-9890
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