organic compounds
1,1′-Biphenyl-2,2′,5,5′-tetracarboxylic acid
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
In the title compound, C16H10O8 or H4bptc, the dihedral angle between the planes of the phenyl rings is 51.90 (4)°. The 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 MnII was formed, but instead crystals of H4bptc were obtained.
The molecular structure is illustrated in Fig. 1. The title compound crystallizes in the monoclinic C2/c. The 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.
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, + 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).
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 .
details are summarized in Table 2Structural data
CCDC reference: 1496472
10.1107/S2414314616012748/zl4011sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616012748/zl4011Isup3.hkl
Supporting information file. DOI: 10.1107/S2414314616012748/zl4011Isup3.cml
Data collection: APEX2 (Bruker, 2000); cell
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).C16H10O8 | F(000) = 680 |
Mr = 330.24 | Dx = 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 |
Bruker APEXII CCD diffractometer | 979 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.023 |
φ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −20→20 |
Tmin = 0.679, Tmax = 0.746 | k = −9→6 |
3734 measured reflections | l = −12→12 |
1227 independent reflections |
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(Fo2) + (0.0493P)2 + 0.7133P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.099 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.18 e Å−3 |
1227 reflections | Δρmin = −0.18 e Å−3 |
113 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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. |
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···O1iv | 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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