1,1′-Biphenyl-2,2′,5,5′-tetra­carb­oxy­lic acid

Li, Y.-H.; Lu, L.-P.

doi:10.1107/S2414314616012748

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 8| August 2016| x161274

doi:10.1107/S2414314616012748

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1,1′-Biphenyl-2,2′,5,5′-tetracarboxylic acid

Yan-Hong Li ^a,^b and Li-Ping Lu ^a ^*

^aInstitute of Molecular Science, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China, and ^bFenyang College, Shanxi Medical University, Fenyang, Shanxi 032200, People's Republic of China
^*Correspondence e-mail: luliping@sxu.edu.cn

Edited by M. Zeller, Purdue University, USA (Received 30 July 2016; accepted 8 August 2016; online 12 August 2016)

In the title compound, C₁₆H₁₀O₈ or H₄bptc, the dihedral angle between the planes of the phenyl rings is 51.90 (4)°. The asymmetric unit contains one half-molecule; complete molecules are generated by a twofold rotation axis. In the crystal, O—H⋯O and C—H⋯O hydrogen-bonding generate a two-dimensional supramolecular network. In addition, weak π–π interactions are also observed.

Keywords: crystal structure; biphenyltetracarboxylic acid; H₄bptc; hydrogen-bonding; π–π interaction.

CCDC reference: 1496472

Structure description

Polycarboxylate ligands, as good candidates for the construction of coordination polymers (CPs), have attracted the interest of many researchers (Su et al., 2014 ; Tian et al., 2011 ). For example, the anion of 1,1′-biphenyl-2,2′,5,5′-tetracarboxylic acid (H₄bptc) can bridge multiple metal centres via a variety of bonding modes, providing an abundance of structural motifs (Sun et al., 2010 ; Jia et al., 2010 ). As part of a study to design and attempt the assembly of coordination polymers employing H₄bptc as an exo-multidentate ligand we reacted H₄bptc with MnCl₂ and half an equivalent of base under hydrothermal conditions. However, no complex of Mn^II was formed, but instead crystals of H₄bptc were obtained.

The molecular structure is illustrated in Fig. 1. The title compound crystallizes in the monoclinic space group C2/c. The asymmetric unit consists of half a molecule, complete molecules are generated by a twofold rotation axis. The phenyl ring has a maximum deviation of 0.0144 (12) Å for atom C5. The C7 and C8 atoms deviate from the mean plane of the ring to which they are attached by 0.1191 (7) and 0.0987 (8) Å, respectively. The carboxyl O atoms (O1, O2, O3 and O4) deviate by 0.6257 (9), −0.3566 (1), −0.0388 (1) and 0.3591 (2) Å, respectively, from the best plane of the phenyl ring. The dihedral angle between the planes of the phenyl rings is 51.90 (4)°, showing the molecule to have a twisted conformation. In the compounds 1,1′-biphenyl-2,2′,4,4′-tetracarboxylic acid (Bu et al., 2010 ), 1,1′-biphenyl-2,2′,3,3′-tetracarboxylic acid (Holý et al., 2004 ), and 1,1′-biphenyl-2,2′,6,6′-tetracarboxylic acid (Holý et al., 1999 ), which are similar to the title compound but substituted at the two 2-positions of the benzene rings, the rings are twisted by 71.63 (5), 88.68 (5) and 86.26 (6)°, respectively. In the isomers substituted at the 3-positions such as 1,1′-biphenyl-3,3′,4,4′-tetracarboxylic acid (Li et al., 2009 ) and 1,1′-biphenyl-3,3′,5,5′-tetracarboxylic acid (Coles et al., 2002 ), the dihedral angles of the biphenyl unit are 0 and 40.71 (8)°, respectively. This indicates that substitution at the 2-position impacts the planarity of the biphenyl unit. The steric hindering effect of a 2-substituent obviously plays a key factor in biphenyl planarity in the isomers of 1,1′-biphenyl-tetracarboxylic acids.

Figure 1
View of the title molecule with 30% probability displacement ellipsoids. [Symmetry code: (i) −x, y, $[{1\over 2}]$ − z.]

In the crystal, the molecules are connected through O—H⋯O and C—H⋯O hydrogen bonds (Table 1) as well as π–π interactions, leading to the formation of a supramolecular network. All O atoms participate in the hydrogen-bonded network. Individual molecules are linked by strong O—H⋯O double hydrogen bonds into carboxylic acid dimers [R₂²(8) hydrogen-bond motif, Fig. 2] which, if considered as tectons, suggest that the self-assembling properties of interactions result in a unilayered sheet with a supramolecular R₄⁴(40) rhombus motif. From a topological point of view, the two-dimensional structure is a (4,4) network when the fused biphenyls are considered as nodes (Fig. 2). The overall supramolecular assembly also includes C—H⋯O hydrogen bonds (carboxylic acids in the position 5,5′-substituent at the biphenyl) and other weak interactions (Table 1). A supramolecular chain with R₂²(16) rings is formed in the c-axis direction via the C6—H6⋯O3(x, −y, $[{1\over 2}]$ + z) hydrogen-bond (Fig. 3). π–πⁱⁱ [symmetry code (ii) −x, −y, −z; centroid-to-centroid distance = 3.711 (1) Å] interactions between the C1–C6 rings strengthen the chains proceeding in this direction. On the other side of the phenyl ring, there is a COOH⋯π(−x,1 − y, −z) stacking interaction (carboxylic acids in the 2,2′-position at the biphenyl) with a C⋯centroid distance of 3.871 (1) Å (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O3ⁱ	0.93	2.52	3.438 (2)	168
O2—H2⋯O3ⁱⁱ	0.99	1.67	2.6615 (17)	176
O4—H4A⋯O1ⁱⁱⁱ	0.96	1.70	2.6535 (16)	174
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Figure 2
The two-dimensional hydrogen-bonded network.

Figure 3
View down the c axis of the interpenetrating corrugated sheets that comprise the crystal structure. [Symmetry codes: (i) x, −y, $[{1\over 2}]$ + z; (ii) −x, −y, −z; (iii) −x, 1 − y, −z.]

Synthesis and crystallization

A mixture containing MnCl₂·4H₂O (0.2 mmol, 39.4 mg), H₄bptc (0.2 mmol, 66.0 mg), KOH (0.2 mmol, 11.2 mg) and H₂O (6 ml) was stirred for 30 min at room temperature. The reaction mixture was sealed in a Teflon-lined stainless steel vessel and then heated to 393 K for three days. The resulting solution was allowed to gradually cool to room temperature. Colorless block-shaped crystals were collected by filtration and washed with water.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₀O₈
M_r	330.24
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	17.5105 (15), 7.7068 (7), 10.6885 (13)
β (°)	107.553 (1)
V (Å³)	1375.3 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.13
Crystal size (mm)	0.22 × 0.19 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000 )
T_min, T_max	0.679, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	3734, 1227, 979
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.099, 1.04
No. of reflections	1227
No. of parameters	113
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.18
Computer programs: APEX2 and SAINT (Bruker, 2000), SHELXS97 and SHELXTL (Sheldrick, 2008 ) and SHELXL2014 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1496472

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616012748/zl4011sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616012748/zl4011Isup3.hkl

Supporting information file. DOI: 10.1107/S2414314616012748/zl4011Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

1,1'-Biphenyl-2,2',5,5'-tetracarboxylic acid top

Crystal data top

C₁₆H₁₀O₈	F(000) = 680
M_r = 330.24	D_x = 1.595 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.5105 (15) Å	Cell parameters from 4946 reflections
b = 7.7068 (7) Å	θ = 2.0–28.7°
c = 10.6885 (13) Å	µ = 0.13 mm⁻¹
β = 107.553 (1)°	T = 298 K
V = 1375.3 (2) Å³	Block, colorless
Z = 4	0.22 × 0.19 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	979 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
φ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −20→20
T_min = 0.679, T_max = 0.746	k = −9→6
3734 measured reflections	l = −12→12
1227 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.035	w = 1/[σ²(F_o²) + (0.0493P)² + 0.7133P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.099	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.18 e Å⁻³
1227 reflections	Δρ_min = −0.18 e Å⁻³
113 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.00860 (9)	0.2360 (2)	0.18570 (15)	0.0226 (4)
C2	−0.04525 (9)	0.2980 (2)	0.06844 (15)	0.0246 (4)
C3	−0.02754 (9)	0.2807 (2)	−0.04963 (16)	0.0291 (4)
H3	−0.0642	0.3189	−0.1271	0.035*
C4	0.04383 (10)	0.2077 (2)	−0.05290 (16)	0.0289 (4)
H4	0.0553	0.1973	−0.1320	0.035*
C5	0.09824 (9)	0.1500 (2)	0.06265 (16)	0.0264 (4)
C6	0.07976 (9)	0.1613 (2)	0.17983 (16)	0.0255 (4)
H6	0.1158	0.1180	0.2562	0.031*
C7	−0.12042 (9)	0.3912 (2)	0.06627 (16)	0.0279 (4)
C8	0.17699 (10)	0.0806 (2)	0.06039 (16)	0.0300 (4)
O1	−0.12872 (7)	0.46968 (17)	0.16061 (12)	0.0367 (4)
O2	−0.17566 (7)	0.3840 (2)	−0.04713 (12)	0.0498 (4)
H2	−0.2235 (13)	0.448 (3)	−0.0423 (7)	0.075*
O3	0.19187 (7)	0.04896 (19)	−0.04157 (12)	0.0443 (4)
O4	0.22832 (7)	0.0609 (2)	0.17623 (12)	0.0534 (5)
H4A	0.2783 (14)	0.021 (3)	0.1674 (3)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0187 (8)	0.0260 (8)	0.0230 (8)	−0.0030 (6)	0.0059 (6)	−0.0011 (6)
C2	0.0186 (8)	0.0289 (9)	0.0258 (8)	−0.0002 (7)	0.0058 (7)	−0.0010 (7)
C3	0.0226 (8)	0.0394 (10)	0.0236 (9)	0.0040 (7)	0.0043 (7)	0.0007 (7)
C4	0.0285 (8)	0.0373 (10)	0.0231 (8)	0.0018 (8)	0.0109 (7)	−0.0014 (7)
C5	0.0207 (8)	0.0316 (10)	0.0270 (9)	0.0005 (7)	0.0075 (7)	−0.0028 (7)
C6	0.0194 (8)	0.0304 (9)	0.0251 (9)	0.0021 (7)	0.0044 (6)	0.0017 (7)
C7	0.0212 (8)	0.0362 (10)	0.0254 (9)	0.0027 (7)	0.0057 (7)	0.0024 (7)
C8	0.0238 (9)	0.0386 (10)	0.0280 (9)	0.0041 (7)	0.0084 (8)	−0.0030 (8)
O1	0.0270 (6)	0.0499 (8)	0.0329 (7)	0.0103 (6)	0.0085 (6)	−0.0054 (6)
O2	0.0270 (7)	0.0843 (11)	0.0315 (8)	0.0225 (7)	−0.0014 (6)	−0.0091 (7)
O3	0.0282 (7)	0.0753 (10)	0.0306 (7)	0.0160 (7)	0.0106 (6)	−0.0064 (7)
O4	0.0265 (7)	0.1027 (13)	0.0284 (7)	0.0241 (7)	0.0044 (6)	−0.0048 (7)

Geometric parameters (Å, º) top

C1—C6	1.391 (2)	C5—C6	1.388 (2)
C1—C2	1.405 (2)	C5—C8	1.486 (2)
C1—C1ⁱ	1.493 (3)	C6—H6	0.9300
C2—C3	1.394 (2)	C7—O1	1.221 (2)
C2—C7	1.494 (2)	C7—O2	1.3040 (19)
C3—C4	1.381 (2)	C8—O3	1.219 (2)
C3—H3	0.9300	C8—O4	1.301 (2)
C4—C5	1.386 (2)	O2—H2	0.99 (3)
C4—H4	0.9300	O4—H4A	0.96 (3)

C6—C1—C2	118.01 (14)	C4—C5—C8	119.52 (15)
C6—C1—C1ⁱ	118.27 (16)	C6—C5—C8	120.50 (15)
C2—C1—C1ⁱ	123.60 (15)	C5—C6—C1	121.52 (15)
C3—C2—C1	120.16 (14)	C5—C6—H6	119.2
C3—C2—C7	117.87 (14)	C1—C6—H6	119.2
C1—C2—C7	121.91 (14)	O1—C7—O2	123.28 (15)
C4—C3—C2	120.80 (15)	O1—C7—C2	123.30 (15)
C4—C3—H3	119.6	O2—C7—C2	113.40 (14)
C2—C3—H3	119.6	O3—C8—O4	123.70 (15)
C3—C4—C5	119.49 (15)	O3—C8—C5	122.41 (16)
C3—C4—H4	120.3	O4—C8—C5	113.87 (14)
C5—C4—H4	120.3	C7—O2—H2	109.5
C4—C5—C6	119.96 (14)	C8—O4—H4A	109.5

C6—C1—C2—C3	1.3 (2)	C2—C1—C6—C5	0.9 (2)
C1ⁱ—C1—C2—C3	−174.80 (12)	C1ⁱ—C1—C6—C5	177.23 (13)
C6—C1—C2—C7	−175.63 (15)	C3—C2—C7—O1	−151.99 (17)
C1ⁱ—C1—C2—C7	8.3 (2)	C1—C2—C7—O1	25.0 (3)
C1—C2—C3—C4	−1.9 (3)	C3—C2—C7—O2	26.5 (2)
C7—C2—C3—C4	175.08 (16)	C1—C2—C7—O2	−156.53 (16)
C2—C3—C4—C5	0.4 (3)	C4—C5—C8—O3	−10.7 (3)
C3—C4—C5—C6	1.8 (3)	C6—C5—C8—O3	170.92 (17)
C3—C4—C5—C8	−176.53 (16)	C4—C5—C8—O4	167.89 (16)
C4—C5—C6—C1	−2.5 (2)	C6—C5—C8—O4	−10.5 (2)
C8—C5—C6—C1	175.82 (15)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O3ⁱⁱ	0.93	2.52	3.438 (2)	168
O2—H2···O3ⁱⁱⁱ	0.99	1.67	2.6615 (17)	176
O4—H4A···O1^iv	0.96	1.70	2.6535 (16)	174

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

Acknowledgements

We gratefully acknowledge financial support by the Natural Science Foundation of China (grant No. 21571118) and thank Dr Feng Su of Shanxi University for his help with the data collection.

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