4,4′-Dimeth­oxybi­phenyl-3,3′-di­car­box­ylic acid

Lundvall, F.; Wragg, D.S.; Dietzel, P.D.C.; Fjellvåg, H.

doi:10.1107/S1600536814008599

organic compounds

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ISSN: 2056-9890

Volume 70| Part 5| May 2014| Page o615

doi:10.1107/S1600536814008599

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4,4′-Dimethoxybiphenyl-3,3′-dicarboxylic acid

Fredrik Lundvall,^a ^* David Stephen Wragg,^a,^b Pascal D. C. Dietzel ^c and Helmer Fjellvåg ^a

^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).

CCDC reference: 997556

Related literature

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

Experimental

Crystal data

C₁₆H₁₄O₆
M_r = 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 ) T_min = 0.931, T_max = 0.990
5188 measured reflections
779 independent reflections
689 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.136
S = 1.12
779 reflections
67 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯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 ); cell refinement: 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

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814008599/qm2105sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814008599/qm2105Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814008599/qm2105Isup3.cml

checkCIF report

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 π–π 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)_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.

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

	Fig. 1. [One molecular unit of the title compound with atom labels and 50% probability displacement ellipsoids. Hydrogen atoms are omitted for clarity.]
	Fig. 2. [Packing diagram of the title compound viewed along the c axis. Hydrogen bonds are indicated by dashed lines.]
	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

C₁₆H₁₄O₆	F(000) = 632
M_r = 302.27	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	779 independent reflections
Radiation source: fine-focus sealed tube	689 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→15
T_min = 0.931, T_max = 0.990	k = −19→19
5188 measured reflections	l = −8→8

Refinement top

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(F_o²) + (0.0765P)² + 0.4964P] where P = (F_o² + 2F_c²)/3
779 reflections	(Δ/σ)_max < 0.001
67 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₆H₁₄O₆	V = 1389.4 (4) Å³
M_r = 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

Data collection top

Bruker APEXII CCD diffractometer	779 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	689 reflections with I > 2σ(I)
T_min = 0.931, T_max = 0.990	R_int = 0.018
5188 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.12	Δρ_max = 0.24 e Å⁻³
779 reflections	Δρ_min = −0.13 e Å⁻³
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

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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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