Biphenyl-3,3′,4,4′-tetra­carboxylic acid dihydrate

Li, F.; Wang, W.-W.; Ji, X.; Cao, C.-C.; Zhu, D.-Y.

doi:10.1107/S1600536808044012

organic compounds

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Volume 65| Part 2| February 2009| Page o244

doi:10.1107/S1600536808044012

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Biphenyl-3,3′,4,4′-tetracarboxylic acid dihydrate

Fei Li,^a ^* Wu-Wei Wang,^a Xing Ji,^a Chang-Chun Cao ^a and Dong-Ya Zhu ^a ^*

^aSchool of Pharmaceutical Science, Nanjing Medical University, Nanjing 210029, People's Republic of China
^*Correspondence e-mail: sevencpu@163.com,

(Received 4 November 2008; accepted 26 December 2008; online 8 January 2009)

The asymmetric unit of the title compound, C₁₆H₁₀O₈·2H₂O, contains one-half of the centrosymmetric organic molecule and one water molecule. The dihedral angles between the carboxylate groups and the adjacent phenyl ring are 71.31 (3) and 16.67 (3)°, while the carboxylate groups are oriented at a dihedral angle of 72.01 (3)°. In the crystal structure, intermolecular O—H⋯O and bifurcated O—H⋯(O,O) hydrogen bonds link the molecules to form a three-dimensional supramolecular network.

Related literature

For general background, see: Du et al. (2006 , 2007 ); Desiraju (2003 ); Yaghi et al. (2003 ); Li et al. (2008 ). For a related structure, see: Coles et al. (2002 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₀O₈·2H₂O
M_r = 366.27
Triclinic, $[P \overline 1]$
a = 5.5858 (16) Å
b = 6.6618 (19) Å
c = 11.086 (3) Å
α = 93.126 (5)°
β = 91.404 (4)°
γ = 109.110 (4)°
V = 388.81 (19) Å³
Z = 1
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 296 (2) K
0.28 × 0.24 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.943, T_max = 0.973
1992 measured reflections
1362 independent reflections
1222 reflections with I > 2σ(I)
R_int = 0.008

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.090
S = 1.08
1362 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.82	1.88	2.683 (3)	168
O4—H4⋯O5ⁱⁱ	0.82	1.79	2.599 (3)	169
O5—H5A⋯O3ⁱⁱⁱ	0.85	2.45	3.129 (3)	137
O5—H5A⋯O2^iv	0.85	2.22	2.892 (3)	136
O5—H5B⋯O2	0.85	1.95	2.801 (3)	175
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) x, y+1, z; (iii) x-1, y-1, z; (iv) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808044012/hk2568sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808044012/hk2568Isup2.hkl

checkCIF report

Comment top

Non-covalent intermolecular interactions, mainly hydrogen bonding and aromatic stacking, play the key role to perfectly project and regulate the detailed crystal packing of supramolecular materials (Du et al., 2006; Desiraju, 2003). Aromatic carboxylates have also been proved to be effective building blocks in constructing various architectures (Yaghi et al., 2003; Li et al., 2008; Du et al., 2007). However, the crystal structures of these polycarboxyl acids themselves are rarely reported (Coles et al., 2002). We synthesized the title compound under hydrothermal condition, and report herein its crystal structure.

The asymmetric unit of the title compound (Fig. 1) contains one-half of the centrosymmetric molecule and one water molecule. The bond lengths (Allen et al., 1987) and angles are within normal ranges. The intramolecular O—H···O hydrogen bonding (Table 1) of the carboxylate O2 atom to the water molecule may cause to a small difference in the C1═O2 [1.2031 (18) Å] and C8═O3 [1.2156 (17) Å] double bonds of the carboxylate groups. The dihedral angles between the planar carboxylate groups (O1/C1/O2) and (O3/C8/O4) and the adjacent phenyl ring A (C2–C7) are 71.31 (3)° and 16.67 (3)°, respectively, while the carboxylate groups are oriented at a dihedral angle of 72.01 (3)°.

In the crystal structure, intra- and intermolecular O—H···O hydrogen bonds (Table 1) link the molecules to form a 3-D supramolecular network. Firstly, the O1—H1···O3 hydrogen bonds between the carboxyl units connect them into a 1-D zigzag chain (Fig. 2). Then, water molecules play the acceptor and donor roles, respectively, to participate in the formation of O4—H4···O5 and O5—H5B···O2 hydrogen bonds, giving rise to a 2-D supramolecular layer (Fig. 3). Finally, water molecules further act as donors to interconnect the supramolecular layers into 3-D networks with O5—H5A···O3 and O5—H5A···O2 hydrogen bonds (Fig. 4).

Related literature top

For general background, see: Du et al. (2006, 2007); Desiraju (2003); Yaghi et al. (2003); Li et al. (2008). For a related structure, see: Coles et al. (2002). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was recrystallized from the mixture of H₂O (15 ml) and HNO₃ (0.5 ml) under the hydrothermal conditions on cooling from 393 K. Colorless block shaped crystals were obtained at room temperature.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title molecule with the atom-numbering scheme. Hydrogen bond is shown as dashed line.
	Fig. 2. The one dimensional hydrogen bonded chain showing hydrogen bonds between the carboxyl units. Other H atoms have been omitted for clarity.
	Fig. 3. The two dimensional hydrogen-bonding layered structure along [011] direction.
	Fig. 4. The three dimensional hydrogen-bonded supramolecular network. The adjacent layers are shown in green and rose colors, and interlayer hydrogen bonds are shown as red dashed lines.

Biphenyl-3,3',4,4'-tetracarboxylic acid diydrate top

Crystal data top

C₁₆H₁₀O₈·2H₂O	Z = 1
M_r = 366.27	F(000) = 190
Triclinic, P1	D_x = 1.564 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.5858 (16) Å	Cell parameters from 1245 reflections
b = 6.6618 (19) Å	θ = 3.2–27.8°
c = 11.086 (3) Å	µ = 0.13 mm⁻¹
α = 93.126 (5)°	T = 296 K
β = 91.404 (4)°	Block, colourless
γ = 109.110 (4)°	0.28 × 0.24 × 0.22 mm
V = 388.81 (19) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1362 independent reflections
Radiation source: fine-focus sealed tube	1222 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.008
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −6→6
T_min = 0.943, T_max = 0.973	k = −7→7
1992 measured reflections	l = −9→13

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0467P)² + 0.0831P] where P = (F_o² + 2F_c²)/3
1362 reflections	(Δ/σ)_max < 0.001
120 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₆H₁₀O₈·2H₂O	γ = 109.110 (4)°
M_r = 366.27	V = 388.81 (19) Å³
Triclinic, P1	Z = 1
a = 5.5858 (16) Å	Mo Kα radiation
b = 6.6618 (19) Å	µ = 0.13 mm⁻¹
c = 11.086 (3) Å	T = 296 K
α = 93.126 (5)°	0.28 × 0.24 × 0.22 mm
β = 91.404 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1362 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1222 reflections with I > 2σ(I)
T_min = 0.943, T_max = 0.973	R_int = 0.008
1992 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.08	Δρ_max = 0.16 e Å⁻³
1362 reflections	Δρ_min = −0.16 e Å⁻³
120 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
O1	1.2031 (2)	0.8456 (2)	0.40618 (9)	0.0535 (3)
H1	1.2130	0.8530	0.4803	0.080*
O2	0.7989 (2)	0.6702 (2)	0.43405 (9)	0.0528 (3)
O3	0.8059 (2)	1.09274 (19)	0.35300 (9)	0.0501 (3)
O4	0.5352 (2)	1.08299 (18)	0.20056 (9)	0.0473 (3)
H4	0.4952	1.1658	0.2468	0.071*
O5	0.3760 (2)	0.35552 (17)	0.32212 (8)	0.0433 (3)
H5A	0.2608	0.2949	0.3695	0.065*
H5B	0.4996	0.4558	0.3561	0.065*
C1	0.9670 (3)	0.7526 (2)	0.36863 (12)	0.0355 (3)
C2	0.9236 (2)	0.7450 (2)	0.23342 (11)	0.0327 (3)
C3	1.0093 (3)	0.6076 (2)	0.16299 (12)	0.0352 (3)
H3	1.1062	0.5354	0.1992	0.042*
C4	0.9533 (3)	0.5744 (2)	0.03778 (11)	0.0329 (3)
C5	0.8074 (3)	0.6846 (3)	−0.01240 (12)	0.0426 (4)
H5	0.7650	0.6639	−0.0949	0.051*
C6	0.7238 (3)	0.8241 (3)	0.05735 (12)	0.0423 (4)
H6	0.6272	0.8963	0.0210	0.051*
C7	0.7815 (3)	0.8586 (2)	0.18104 (11)	0.0341 (3)
C8	0.7072 (3)	1.0210 (2)	0.25400 (12)	0.0349 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0436 (6)	0.0853 (9)	0.0246 (5)	0.0135 (6)	−0.0053 (4)	−0.0055 (5)
O2	0.0502 (7)	0.0738 (8)	0.0232 (5)	0.0062 (6)	0.0020 (5)	−0.0023 (5)
O3	0.0567 (7)	0.0651 (7)	0.0316 (6)	0.0290 (6)	−0.0118 (5)	−0.0202 (5)
O4	0.0621 (7)	0.0599 (7)	0.0298 (5)	0.0363 (6)	−0.0068 (5)	−0.0100 (5)
O5	0.0480 (6)	0.0484 (6)	0.0323 (5)	0.0154 (5)	0.0033 (4)	−0.0044 (4)
C1	0.0423 (8)	0.0418 (8)	0.0231 (7)	0.0164 (6)	−0.0016 (6)	−0.0054 (6)
C2	0.0342 (7)	0.0396 (7)	0.0216 (6)	0.0095 (6)	−0.0006 (5)	−0.0030 (5)
C3	0.0408 (8)	0.0430 (8)	0.0240 (7)	0.0175 (6)	−0.0019 (5)	−0.0016 (5)
C4	0.0375 (7)	0.0372 (7)	0.0226 (6)	0.0114 (6)	−0.0003 (5)	−0.0032 (5)
C5	0.0589 (10)	0.0540 (9)	0.0202 (7)	0.0276 (8)	−0.0063 (6)	−0.0065 (6)
C6	0.0559 (9)	0.0521 (9)	0.0265 (7)	0.0297 (8)	−0.0055 (6)	−0.0043 (6)
C7	0.0373 (7)	0.0390 (7)	0.0244 (7)	0.0113 (6)	−0.0004 (5)	−0.0036 (6)
C8	0.0381 (7)	0.0403 (8)	0.0250 (7)	0.0120 (6)	0.0007 (6)	−0.0025 (6)

Geometric parameters (Å, º) top

O1—C1	1.3065 (18)	C2—C7	1.399 (2)
O1—H1	0.8200	C3—C4	1.4047 (19)
O2—C1	1.2031 (18)	C3—H3	0.9300
O3—C8	1.2156 (17)	C4—C5	1.388 (2)
O4—C8	1.3052 (17)	C4—C4ⁱ	1.492 (3)
O4—H4	0.8200	C5—C6	1.380 (2)
O5—H5A	0.8500	C5—H5	0.9300
O5—H5B	0.8502	C6—C7	1.3901 (19)
C1—C2	1.5080 (18)	C6—H6	0.9300
C2—C3	1.380 (2)	C7—C8	1.4874 (19)

C1—O1—H1	109.5	C3—C4—C4ⁱ	121.05 (15)
C8—O4—H4	109.5	C6—C5—C4	121.45 (13)
H5A—O5—H5B	114.3	C6—C5—H5	119.3
O2—C1—O1	123.81 (12)	C4—C5—H5	119.3
O2—C1—C2	122.09 (13)	C5—C6—C7	121.10 (14)
O1—C1—C2	114.00 (12)	C5—C6—H6	119.5
C3—C2—C7	120.53 (12)	C7—C6—H6	119.5
C3—C2—C1	117.84 (12)	C6—C7—C2	118.11 (13)
C7—C2—C1	121.39 (12)	C6—C7—C8	120.75 (13)
C2—C3—C4	121.34 (13)	C2—C7—C8	121.04 (12)
C2—C3—H3	119.3	O3—C8—O4	123.78 (13)
C4—C3—H3	119.3	O3—C8—C7	122.06 (13)
C5—C4—C3	117.43 (13)	O4—C8—C7	114.11 (11)
C5—C4—C4ⁱ	121.52 (14)

O2—C1—C2—C3	−104.45 (17)	C5—C6—C7—C2	−1.1 (2)
O1—C1—C2—C3	72.09 (17)	C5—C6—C7—C8	175.44 (14)
O2—C1—C2—C7	70.0 (2)	C3—C2—C7—C6	1.8 (2)
O1—C1—C2—C7	−113.51 (16)	C1—C2—C7—C6	−172.41 (13)
C7—C2—C3—C4	−1.2 (2)	C3—C2—C7—C8	−174.64 (12)
C1—C2—C3—C4	173.25 (13)	C1—C2—C7—C8	11.1 (2)
C2—C3—C4—C5	−0.3 (2)	C6—C7—C8—O3	−161.23 (14)
C2—C3—C4—C4ⁱ	−179.98 (15)	C2—C7—C8—O3	15.2 (2)
C3—C4—C5—C6	1.1 (2)	C6—C7—C8—O4	16.55 (19)
C4ⁱ—C4—C5—C6	−179.21 (16)	C2—C7—C8—O4	−167.06 (13)
C4—C5—C6—C7	−0.4 (3)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱⁱ	0.82	1.88	2.683 (3)	168
O4—H4···O5ⁱⁱⁱ	0.82	1.79	2.599 (3)	169
O5—H5A···O3^iv	0.85	2.45	3.129 (3)	137
O5—H5A···O2^v	0.85	2.22	2.892 (3)	136
O5—H5B···O2	0.85	1.95	2.801 (3)	175

Symmetry codes: (ii) −x+2, −y+2, −z+1; (iii) x, y+1, z; (iv) x−1, y−1, z; (v) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₀O₈·2H₂O
M_r	366.27
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.5858 (16), 6.6618 (19), 11.086 (3)
α, β, γ (°)	93.126 (5), 91.404 (4), 109.110 (4)
V (Å³)	388.81 (19)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.28 × 0.24 × 0.22

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.943, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	1992, 1362, 1222
R_int	0.008
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.090, 1.08
No. of reflections	1362
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.16

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.82	1.88	2.683 (3)	168
O4—H4···O5ⁱⁱ	0.82	1.79	2.599 (3)	169
O5—H5A···O3ⁱⁱⁱ	0.85	2.45	3.129 (3)	137
O5—H5A···O2^iv	0.85	2.22	2.892 (3)	136
O5—H5B···O2	0.85	1.95	2.801 (3)	175

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) x, y+1, z; (iii) x−1, y−1, z; (iv) −x+1, −y+1, −z+1.

Acknowledgements

We acknowledge Tianjin Normal University for their active cooperation in this work.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Coles, S. J., Holmes, R., Hursthouse, M. B. & Price, D. J. (2002). Acta Cryst. E58, o626–o628. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Desiraju, G. R. (2003). J. Mol. Struct. 656, 5–15. Web of Science CrossRef CAS Google Scholar
Du, M., Li, C.-P. & Zhao, X.-J. (2006). CrystEngComm, 8, 552–562. Web of Science CSD CrossRef CAS Google Scholar
Du, M., Li, C.-P., Zhao, X.-J. & Yu, Q. (2007). CrystEngComm, 9, 1011–1028. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Li, C.-P., Tian, Y.-L. & Guo, Y.-M. (2008). Inorg. Chem. Commun. 11, 1405–1408. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yaghi, O. M., O'Keeffe, M., Ockwig, N. W., Chae, H. K., Eddaoudi, M. & Kim, J. (2003). Nature (London), 423, 705–714. Web of Science CrossRef PubMed CAS Google Scholar