Crystal structure and Hirshfeld surface analysis of 2,5-di­bromo­terephthalic acid ethyl­ene glycol monosolvate

Khotchasanthong, K.; Jittirattanakun, S.; Jiajaroen, S.; Theppitak, C.; Chainok, K.

doi:10.1107/S2056989019010260

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ISSN: 2056-9890

Volume 75| Part 8| August 2019| Pages 1228-1231

https://doi.org/10.1107/S2056989019010260

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Crystal structure and Hirshfeld surface analysis of 2,5-dibromoterephthalic acid ethylene glycol monosolvate

Kenika Khotchasanthong,^a Siripak Jittirattanakun,^b Suwadee Jiajaroen,^b Chatphorn Theppitak ^b and Kittipong Chainok ^a ^*

^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

Edited by M. Weil, Vienna University of Technology, Austria (Received 8 July 2019; accepted 18 July 2019; online 23 July 2019)

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 asymmetric unit. 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 ( $[\overline{1}]$ 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 crystal structure of 2,5-dibromoterephthalic acid ethylene glycol monosolvate, C₈H₄Br₂O₄·C₂H₆O₂ or H₂Br₂tp·EG, which is a pseudopolymorph of the previously reported compound 2,5-dibromoterephthalic acid dihydrate (Song et al., 2008 ).

2. Structural commentary

The structures of the molecular components in the title compound are shown in Fig. 1. The asymmetric unit 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].

Figure 1
The structures of the molecular components in the title compound with displacement ellipsoids drawn at the 50% probability level. The O—H⋯O hydrogen bond is shown by a dashed line.

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 ( $[\overline{1}]$ 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.

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O2ⁱ	0.82 (1)	1.97 (1)	2.767 (3)	166 (4)
Symmetry code: (i) -x+2, -y+1, -z+2.

Figure 2
View of a supramolecular two-dimensional sheet parallel to the ( $[\overline{1}]$ 01) direction, enclosing R₄⁴ (12) and R₄⁴ (28) graph-set motifs, sustained by O—H⋯O hydrogen bonds (dashed lines).

Figure 3
View along [111] of a supramolecular sheet sustained by Br⋯O halogen bonding and π–π stacking interactions (dashed lines).

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, d_norm, 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 d_norm 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.

Figure 4
Two-dimensional fingerprint plots of the title compound, showing (a) all interactions, and delineated into (b) H⋯O/O⋯H, (c) H⋯Br/Br⋯H, (d) H⋯H, (e) H⋯C/C⋯H, (f) H⋯O/O⋯H, (g) Br⋯O/O⋯Br, and (h) C⋯C interactions [d_e and d_i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (internal) the surface, respectively].

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 diffraction analysis were obtained.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. 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 U_iso(H) = 1.2U_eq(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 U_iso(H) = 1.5U_eq(O).

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₄Br₂O₄·C₂H₆O₂
M_r	386.00
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	4.2823 (6), 6.2607 (9), 11.5497 (17)
α, β, γ (°)	96.701 (5), 93.930 (5), 90.575 (5)
V (Å³)	306.76 (8)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	6.62
Crystal size (mm)	0.20 × 0.20 × 0.16

Data collection
Diffractometer	Bruker D8 QUEST CMOS PHOTON II
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.576, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	9075, 1208, 1076
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.052, 1.05
No. of reflections	1208
No. of parameters	91
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.28
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1941436

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019010260/wm5512sup1.cif

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

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: 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).

(I) top

Crystal data top

C₈H₄Br₂O₄·C₂H₆O₂	Z = 1
M_r = 386.00	F(000) = 188
Triclinic, P1	D_x = 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

Data collection top

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	R_int = 0.052
Detector resolution: 7.39 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω and φ scans	h = −5→5
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −7→7
T_min = 0.576, T_max = 0.747	l = −14→14
9075 measured reflections

Refinement top

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(F_o²) + (0.0175P)² + 0.2228P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.052	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.34 e Å⁻³
1208 reflections	Δρ_min = −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

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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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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