Crystal structure of [1,1′:3′,1′′-ter­phenyl]-2′,3,3′′-tri­carb­oxy­lic acid

Daniel A Decato; Orion B Berryman

doi:10.1107/S2056989015015029

. 2015 Aug 22;71(Pt 9):o667–o668. doi: 10.1107/S2056989015015029

Crystal structure of [1,1′:3′,1′′-terphenyl]-2′,3,3′′-tricarboxylic acid

Daniel A Decato ^a, Orion B Berryman ^a,^*

PMCID: PMC4555404 PMID: 26396894

Abstract

The asymmetric unit of the title compound, C₂₁H₁₄O₆, comprises two symmetrically independent molecules that form a locally centrosymmetric hydrogen-bonded dimer, with the planes of the corresponding carboxylic acid groups rotated by 15.8 (1) and 17.5 (1)° relative to those of the adjacent benzene rings. The crystal as a whole, however, exhibits a noncentrosymmetric packing, described by the polar space group Pca2₁. The dimers form layers along the ab plane, being interconnected by hydrogen bonds involving the remaining carboxylic acid groups. The plane of the central carboxylic acid group forms dihedral angles of 62.5 (1) and 63.0 (1)° with those of the adjacent benzene rings and functions as a hydrogen-bond donor and acceptor. As a donor, it interconnects adjacent layers, while as an acceptor it stabilizes the packing within the layers. The ‘distal’ carboxylic acid groups are nearly coplanar with the planes of the adjacent benzene rings, forming dihedral angles of 1.8 (1) and 7.1 (1)°. These groups also form intra- and inter-layer hydrogen bonds, but with ‘reversed’ functionality, as compared with the central carboxylic acid groups.

Keywords: crystal structure, hydrogen bonding, meta-terphenyl

Related literature

For a detailed discussion on local centers of symmetry in the space group Pca2₁, see: Marsh et al. (1998 ▸). For the synthesis of the starting material 3,3′′-dimethyl-[1,1′:3′,1′′-terphenyl]-2′-carboxylic acid, see: Du et al. (1986 ▸). graphic file with name e-71-0o667-scheme1.jpg

Experimental

Crystal data

C₂₁H₁₄O₆
M _r = 362.32
Orthorhombic,
a = 23.1735 (9) Å
b = 7.2480 (2) Å
c = 20.3320 (8) Å
V = 3415.0 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.3 × 0.05 × 0.05 mm

Data collection

Bruker D8 VENTURE DUO diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ▸) T _min = 0.695, T _max = 0.745
46489 measured reflections
6467 independent reflections
5899 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.091
S = 1.05
6467 reflections
511 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2012 ▸); cell refinement: SAINT (Bruker, 2012 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015015029/ld2133sup1.cif

e-71-0o667-sup1.cif^{(1.4MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015015029/ld2133Isup2.hkl

e-71-0o667-Isup2.hkl^{(514.1KB, hkl)}

Click here for additional data file.^{(29B, cml)}

Supporting information file. DOI: 10.1107/S2056989015015029/ld2133Isup3.cml

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S2056989015015029/ld2133fig1.tif

The asymmetric unit of the title compound, with displacement elipsoids drawn at 50% probability level. Hydrogen atoms presented by spheres of an arbitrary radius. Intra-dimer hydrogen bonds are represented by dotted lines.

Click here for additional data file.^{(2.3MB, tif)}

b . DOI: 10.1107/S2056989015015029/ld2133fig2.tif

Packing view along b axis. Hydrogen bonds are represented by dotted lines.

CCDC reference: 1418223

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O2H2O3ⁱ	0.91(5)	1.79(5)	2.657(3)	159(4)
O4H4O1ⁱⁱ	0.90(6)	1.84(6)	2.689(3)	156(5)
O2H2O3ⁱⁱⁱ	0.87(6)	1.76(6)	2.628(3)	171(5)
O4H4O1^iv	0.84(5)	1.90(5)	2.717(3)	166(4)
O6H6O5	0.92(4)	1.69(4)	2.593(3)	168(4)
O6H6O5	1.01(3)	1.58(3)	2.581(3)	172(6)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

This work was supported by grants from the National Science Foundation (NSF)–MRI (CHE-1337908) and the National Institutes of Health (CoBRE NIGMS P20GM103546). The University of Montana and the Center for Biomolecular Structure and Dynamics are aknowledged for their support of the University of Montana X-ray diffraction core facility.

supplementary crystallographic information

S1. Experimental

S1.1. Synthesis and crystallization

3,3''-dimethyl-[1,1':3',1''-terphenyl]-2'-carboxylic acid (0.432 g, 1.4 mmol) synthesized according to Du et al. (1986). The starting material was dissolved in 15 ml pyridine and brought to reflux. KMnO₄ (0.50 g, 3.1 mmol) in 1 ml of water was added, and allowed to react for 2 hours. Subsequently, 3 more additions of KMnO₄ (0.25 g, 1.6 mmol) in 1.5 ml of water were added every 2 hours for a total of 4 additions. After six hours, 10 ml of water was added and the reaction was refluxed overnight. The reaction mixture was filtered while hot to remove solid MnO₂. The filtrate was then concentrated under reduced pressure, and treated by 12M HCl. The resulting white precipitate was then filtered and purified via silica gel column chromatograph (50/50 hexanes/ethyl acetate with 0.5% acetic acid) to give of the title compound. (0.366 g Yield 70%) ¹H NMR (DMSO, 400 MHz): δ 7.46 (d, 2H J = 8 Hz), 7.58 (t, 2H, J = 8 Hz), 7.61 (t, 1H, J = 7.2 Hz), 7.68 (d, 2H, J = 8Hz), 7.97 (d, 2H, J = 8 Hz), 8.01 (s, 2H), 13.01 (s, O-H). ¹³C NMR (DMSO, 100 MHz): δ 128.4, 128.7, 129.1, 129.2, 129.3, 130.8, 132.7, 133.9, 138.0, 140.39, 167.0, 169.7. Single crystals suitable for X-ray diffraction were obtained by vapor diffusion of hexane into an ethyl acetate solution of the title compound.

S1.2. Refinement

All H atoms were located in difference Fourier maps but finally their positions were determined geometrically, except for the carboxy H atoms that were refined with isotropic thermal parameters. The O6—H6 bond length in the carboxylic acid dimer was restrained at the distance from the corresponding residual electron density peak to the oxygen (0.996 (2)Å) . This was done due to unreasonable lengthening (> 1.4 Å) of the H—O bond during the refinement. All other H atoms were refined using a riding model with fixed isotropic displacement parameters [Uiso(H) = 1.2Ueq(C) for the C(H) groups]. Additional crystal data, data collection and structure refinement details are summarized in Table 1.

S2. Results and discussion