research communications
and Hirshfeld surface analysis of 2,5-dibromoterephthalic acid ethylene glycol monosolvate
aMaterials and Textile Technology, Faculty of Science and Technology, Thammasat University, Khlong Luang, Pathum Thani, 12121, Thailand, and bDivision of Chemistry, Faculty of Science and Technology, Thammasat University, Khlong Luang, Pathum Thani, 12121, Thailand
*Correspondence e-mail: kc@tu.ac.th
The title compound, C8H4Br2O4·C2H6O2, crystallizes with one-half of a 2,5-dibromoterephthalic acid (H2Br2tp) molecule and one-half of an ethylene glycol (EG) molecule in the the The whole molecules are generated by application of inversion symmetry. The H2Br2tp molecule is not planar, with the dibromobenzene ring system inclined by a dihedral angle of 18.62 (3)° to the carboxylic group. In the crystal, the H2Br2tp and EG molecules are linked into sheets propagating parallel to (01) through O—H⋯O hydrogen bonds, thereby forming R44 (12) and R44 (28) graph-set motifs. Br⋯O and weak π–π stacking interactions are also observed. Hirshfeld surface analysis was used to confirm the existence of these interactions.
Keywords: crystal structure; halogen bonds; hydrogen bonds; solvate.
CCDC reference: 1941436
1. Chemical context
Terephthalic acid and its derivatives are important ligands in the construction of coordination frameworks with high dimensionalities and interesting topologies (Li et al., 1999; Seidel et al., 2011). They have also been shown to be versatile building blocks in crystal engineering to drive the self-assembly of functional supramolecular networks through intermolecular interactions such as hydrogen bonds, halogen bonds, and aromatic π–π stacking interactions (Lemmerer, 2011; Karmakar et al., 2014; Meng et al., 2015).
In this study, we present the 8H4Br2O4·C2H6O2 or H2Br2tp·EG, which is a pseudopolymorph of the previously reported compound 2,5-dibromoterephthalic acid dihydrate (Song et al., 2008).
of 2,5-dibromoterephthalic acid ethylene glycol monosolvate, C2. Structural commentary
The structures of the molecular components in the title compound are shown in Fig. 1. The contains one-half of a H2Br2tp molecule and one-half of an EG molecule. Both molecules are generated by application of inversion symmetry. The H2Br2tp molecule is not planar. Its dibromobenzene ring system (r.m.s. deviation = 0.006 Å) makes a dihedral angle of 18.62 (3)° with the carboxylic group (r.m.s. deviation = 0.013 Å). As a result of symmetry restrictions, the EG molecule adopts an anti-conformation with an O3—C5—C5i—O3i torsion angle of 180° [symmetry code: (i) 2 − x, −y, 2 − z].
3. Supramolecular features
In the crystal, the H2Br2tp and EG molecules are linked by strong-to-medium O—H⋯O hydrogen bonds between carboxylic acid and alcohol OH functions (Table 1), enclosing R44 (12) and R44 (28) graph-set motifs and forming sheets parallel to the (01) plane; Fig. 2. Br⋯O halogen bonding [Br⋯O = 3.2536 (4) Å; C—Br⋯O = 157.7 (3)°] and weak π–π stacking interactions [centroid-to-centroid distance = 4.283 (5) Å] are also observed (Fig. 3). The combination of these intermolecular interactions results in the formation of a three-dimensional supramolecular network.
4. Hirshfeld surface analysis
Hirshfeld surfaces (McKinnon et al., 2007) and their associated two-dimensional fingerprint plots (Spackman & McKinnon, 2002) were used to quantify the various intermolecular interactions, and were generated using CrystalExplorer17 (Turner et al., 2017). The shorter and longer contacts are indicated as red and blue spots on the Hirshfeld surfaces, and contacts with distances equal to the sum of the van der Waals radii are represented as white spots. Hirshfeld surfaces of the title compound mapped over the normalized distance, dnorm, using a standard surface resolution with a fixed colour scale of −0.7877 (red) to 0.9385 a.u. (blue) and the two-dimensional fingerprint plots are illustrated in Fig. 4. The dominant interactions between H and O atoms, corresponding to the discussed O—H⋯O hydrogen bonds, can be clearly be seen as red spots on the Hirshfeld surface. The faint-red spot visible on the dnorm surface can be assigned to Br⋯O contacts. Analysis of the two-dimensional fingerprint plots reveals that the H⋯O/O⋯H (28.8%) contacts are the dominant contributors to the Hirshfeld surface. The contribution of the Br⋯H/H⋯Br contacts is 22.1%, whereas Br⋯Br contacts are negligible (0.9%). Other contacts viz. H⋯H (17.7%), H⋯C/C⋯H (7.7%), Br⋯C/C⋯Br (7.2%), Br⋯O/O⋯Br (5.8%), C⋯O/O⋯C (4.5%), C⋯C (3.3%) and O⋯O (2.2%) also make significant contributions to the Hirshfeld surface.
5. Database survey
A search of the Cambridge Structural Database (Version 5.40, latest update May 2019; Groom et al., 2016) for the H2Br2tp entity resulted in just two matches. In the structure of the pseudopolymorphic H2Br2tp dihydrate (CSD refcode POFROS; Song et al., 2008), the H2Br2tp molecules are connected through water molecules by O—H⋯O hydrogen bonds, forming a three-dimensional supramolecular network. In the structure of bis{N-[1-(pyridin-2-yl-κN)ethylidene]pyridine-4-carbohydrazonato-κ2N′,O}nickel(II)–2,5-dibromoterephthalic acid (OBOJEX; Nakanishi & Sato, 2017), the H2Br2tp molecules form hydrogen-bonded zigzag chains with the complex molecules. The packing is further consolidated by π–π stacking and Br⋯Br halogen bonding.
6. Synthesis and crystallization
H2Br2tp and EG were purchased from commercial sources and used as received. A solution of H2Br2tp (0.020 g) in 5 ml of EG was heated (333 K) to reflux for 15 min. The reaction solution was held for 2–3 h and colourless block-shaped crystals suitable for single-crystal X-ray were obtained.
7. Refinement
Crystal data, data collection and structure . The carbon-bound H atoms were placed in geometrically calculated positions and refined as riding with C—H = 0.93 Å for aromatic and C—H = 0.97 Å for methylene hydrogen atoms with Uiso(H) = 1.2Ueq(C). The H atoms bound to O atoms were located from difference-Fourier maps but were refined with distance restraints of O—H = 0.82 ± 0.02 Å and Uiso(H) = 1.5Ueq(O).
details are summarized in Table 2Supporting information
CCDC reference: 1941436
https://doi.org/10.1107/S2056989019010260/wm5512sup1.cif
contains datablock I. DOI:Supporting information file. DOI: https://doi.org/10.1107/S2056989019010260/wm5512Isup3.cdx
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019010260/wm5512Isup4.hkl
Data collection: APEX3 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); 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 (Dolomanov et al., 2009).C8H4Br2O4·C2H6O2 | Z = 1 |
Mr = 386.00 | F(000) = 188 |
Triclinic, P1 | Dx = 2.089 Mg m−3 |
a = 4.2823 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 6.2607 (9) Å | Cell parameters from 5153 reflections |
c = 11.5497 (17) Å | θ = 3.3–28.8° |
α = 96.701 (5)° | µ = 6.62 mm−1 |
β = 93.930 (5)° | T = 296 K |
γ = 90.575 (5)° | Block, light colourless |
V = 306.76 (8) Å3 | 0.20 × 0.20 × 0.16 mm |
Bruker D8 QUEST CMOS PHOTON II diffractometer | 1208 independent reflections |
Radiation source: sealed x-ray tube, Micro focus tube | 1076 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
Detector resolution: 7.39 pixels mm-1 | θmax = 26.0°, θmin = 3.3° |
ω and φ scans | h = −5→5 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −7→7 |
Tmin = 0.576, Tmax = 0.747 | l = −14→14 |
9075 measured reflections |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.023 | w = 1/[σ2(Fo2) + (0.0175P)2 + 0.2228P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.052 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.34 e Å−3 |
1208 reflections | Δρmin = −0.28 e Å−3 |
91 parameters | Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
2 restraints | Extinction coefficient: 0.034 (3) |
Primary atom site location: dual |
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 | ||
Br1 | 0.28840 (7) | 0.90781 (4) | 0.67985 (2) | 0.03714 (15) | |
O1 | 0.9576 (5) | 0.3651 (3) | 0.75182 (16) | 0.0399 (5) | |
H1 | 1.013 (9) | 0.352 (6) | 0.8205 (14) | 0.071 (12)* | |
O2 | 0.6124 (5) | 0.5932 (3) | 0.82669 (15) | 0.0430 (5) | |
O3 | 1.1223 (5) | 0.2556 (3) | 0.95346 (17) | 0.0415 (5) | |
H3 | 1.205 (8) | 0.320 (5) | 1.0136 (19) | 0.065 (12)* | |
C1 | 0.7228 (6) | 0.4945 (4) | 0.7436 (2) | 0.0263 (5) | |
C2 | 0.6046 (5) | 0.5048 (4) | 0.6187 (2) | 0.0231 (5) | |
C3 | 0.4170 (6) | 0.6668 (4) | 0.5809 (2) | 0.0244 (5) | |
C4 | 0.3155 (6) | 0.6610 (4) | 0.4647 (2) | 0.0261 (5) | |
H4 | 0.190106 | 0.770860 | 0.441344 | 0.031* | |
C5 | 0.9128 (7) | 0.0972 (4) | 0.9857 (2) | 0.0371 (6) | |
H5A | 0.756819 | 0.056821 | 0.921709 | 0.044* | |
H5B | 0.805174 | 0.156980 | 1.052949 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0530 (2) | 0.03148 (18) | 0.02537 (18) | 0.01196 (12) | 0.00214 (11) | −0.00380 (10) |
O1 | 0.0505 (12) | 0.0469 (12) | 0.0215 (10) | 0.0198 (9) | −0.0049 (9) | 0.0034 (9) |
O2 | 0.0507 (12) | 0.0585 (13) | 0.0175 (9) | 0.0199 (10) | −0.0031 (8) | −0.0034 (9) |
O3 | 0.0535 (13) | 0.0409 (11) | 0.0290 (11) | −0.0047 (10) | −0.0110 (10) | 0.0079 (9) |
C1 | 0.0292 (13) | 0.0285 (13) | 0.0206 (12) | −0.0021 (10) | −0.0026 (10) | 0.0029 (10) |
C2 | 0.0261 (12) | 0.0261 (12) | 0.0170 (11) | −0.0032 (10) | −0.0007 (9) | 0.0037 (9) |
C3 | 0.0299 (13) | 0.0239 (12) | 0.0189 (11) | 0.0015 (10) | 0.0031 (10) | −0.0006 (9) |
C4 | 0.0307 (13) | 0.0272 (12) | 0.0204 (12) | 0.0050 (10) | −0.0011 (10) | 0.0044 (10) |
C5 | 0.0386 (15) | 0.0414 (15) | 0.0310 (14) | 0.0065 (12) | −0.0030 (12) | 0.0062 (12) |
Br1—C3 | 1.894 (2) | C2—C3 | 1.392 (3) |
O1—H1 | 0.825 (10) | C2—C4i | 1.394 (3) |
O1—C1 | 1.303 (3) | C3—C4 | 1.377 (3) |
O2—C1 | 1.207 (3) | C4—H4 | 0.9300 |
O3—H3 | 0.817 (10) | C5—C5ii | 1.493 (5) |
O3—C5 | 1.428 (4) | C5—H5A | 0.9700 |
C1—C2 | 1.504 (3) | C5—H5B | 0.9700 |
C1—O1—H1 | 112 (3) | C4—C3—C2 | 120.5 (2) |
C5—O3—H3 | 108 (3) | C2i—C4—H4 | 119.1 |
O1—C1—C2 | 112.1 (2) | C3—C4—C2i | 121.9 (2) |
O2—C1—O1 | 123.7 (2) | C3—C4—H4 | 119.1 |
O2—C1—C2 | 124.1 (2) | O3—C5—C5ii | 110.6 (3) |
C3—C2—C1 | 124.6 (2) | O3—C5—H5A | 109.5 |
C3—C2—C4i | 117.6 (2) | O3—C5—H5B | 109.5 |
C4i—C2—C1 | 117.8 (2) | C5ii—C5—H5A | 109.5 |
C2—C3—Br1 | 124.11 (18) | C5ii—C5—H5B | 109.5 |
C4—C3—Br1 | 115.39 (18) | H5A—C5—H5B | 108.1 |
O3—C5—C5ii—O3ii | 180.000 (1) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3 | 0.83 (1) | 1.75 (1) | 2.559 (3) | 165 (4) |
O3—H3···O2iii | 0.82 (1) | 1.97 (1) | 2.767 (3) | 166 (4) |
Symmetry code: (iii) −x+2, −y+1, −z+2. |
Acknowledgements
The authors thank the Faculty of Science and Technology, Thammasat University, for funds to purchase the X-ray diffractometer.
Funding information
This work was supported by a National Research Councils of Thailand grant provided by the Thammasat University (No. 20/2561).
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