2,6-Di­bromo-3,4,5-tri­meth­oxy­benzoic acid

Meurer, F.; Dimova, T.; Bodensteiner, M.; Kolev, I.

doi:10.1107/S2056989023007831

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 79| Part 10| October 2023| Pages 916-919

https://doi.org/10.1107/S2056989023007831

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2,6-Dibromo-3,4,5-trimethoxybenzoic acid

Florian Meurer,^a Tanya Dimova,^b Michael Bodensteiner ^a ^* and Iliyan Kolev ^b ^*

^aFaculty of Chemistry and Pharmacy, University of Regensburg, Universitaetsstr. 31, 93053 Regensburg, Germany, and ^bFaculty of Pharmacy, Department of Pharmaceutical Chemistry, Medical University "Prof. Dr. Paraskev Stoyanov" Varna, 84 "Tzar Osvoboditel" Blvd., 9000 Varna, Bulgaria
^*Correspondence e-mail: michael.bodensteiner@ur.de, ilian.kolev@mu-varna.bg

Edited by J. Reibenspies, Texas A & M University, USA (Received 18 July 2023; accepted 7 September 2023; online 14 September 2023)

The title compound, 2,6-dibromo-3,4,5-trimethoxybenzoic acid (DBrTMBA), C₁₀H₁₀Br₂O₅, was obtained by bromination and transhalogenation of 2-iodo-3,4,5-trimethoxybenzoic acid with KBrO₃. Like the previously reported 2,6-diiodo-3,4,5-trimethoxybenzoic acid (DITMBA), the structure of the title compound features a catemeric arrangement of DBrTMBA molecules along an endless chain of carboxylic H–carbonyl interactions. A short carbonyl–phenyl contact hints at a possible lone pair(O)–π-hole interaction further stabilizing the chain-like structure over a dimeric arrangement of the carboxylic acid.

Keywords: crystal structure; Hirshfeld atom refinement (HAR); NoSpherA2; substituted trimethoxybenzoic acid.

CCDC reference: 2281408

1. Chemical context

Organobromine compounds are valuable precursors in organic and pharmaceutical synthesis. Their participation in homo- and cross-coupling reactions is undisputed and even preferred over the other halogen-containing compounds. In practice, many brominating agents are used for their synthesis, though few of them appear to be safe both for the user-chemist and environment. Therefore, in the present work, we present a new environmentally friendly method for the synthesis of 2,6-dibromo-3,4,5-trimethoxybenzoic acid. Its structure is closely related to those of mono- and diiodo-3,4,5-trimethoxybenzoic acids ITMBA and DITMBA (Kolev et al., 2021 , 2023 ).

2. Structural commentary

DBrTMBA (Fig. 1) crystallizes in the monoclinic space group P2₁/n with one acid molecule in the asymmetric unit (Z = 4). The carboxylic acid (O1/C7/O2) group is almost perpendicular to the geometrical C₆ mean plane and at an angle of 86.7 (2)°. This derivation is exactly in the middle of the reported geometries of the catemeric DITMBA, which is closer to 90° and the reported dimeric DITMBA·toluene, which deviates more from 90° (Kolev et al., 2023).

Figure 1
Labelling scheme and structure of DBrTMBA. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

Different to the also related structures of mono- and diiodo-3,4,5-trimethoxybenzoic acids ITMBA and DITMBA·toluene (Kolev et al., 2021, 2023), the title compound exhibits no dimeric structure in the solid state (Fig. 2). Instead, a hydrogen-bonded chain along the crystallographic b-axis direction between neighbouring acids is observed. Molecules of DBrTMBA are arranged in a catemeric fashion along this chain of carboxylic hydrogen interaction. The structure is thus very similar to that of solvent-free DITMBA (Kolev et al., 2023). The O1—O2 distance of the DBrTMBA intermolecular hydrogen-bonding interaction is 2.617 (5) Å (Table 1, Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.98 (5)	1.68 (3)	2.617 (5)	160 (5)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
Packing of DBrTMBA along the crystallographic b-axis direction.

Figure 3
Syndiotactic arrangement of DBrTMBA in the crystallographic b-axis direction with O(H)—O and O–center of gravity C₆ and distances in Å. Atoms that are not part of the carboxylic group are shown in stick representation for clarity.

Another interesting structural feature in this syndiotactic arrangement can be described as a carbonyl O2 lone pair(lp)–π (C₆) contact with a distance from O2 to the center of geometry of the benzene ring of 3.030 (4) Å (Fig. 2). This contact presumably contributes to the deviation from the dimeric structure as observed in ITMBA and DITMBA· toluene (Kolev et al., 2021, 2023). In the latter, the toluene solvent molecule seems to shield the C₆ π system from this kind of interaction, giving rise to a preferred dimeric structure in this solvate.

To understand the crystal packing of DBrTMBA and the contribution of these closest interaction contacts, the software program CrystalExplorer was used for a Hirshfeld surface and interaction analysis (Spackman et al., 2021 ). Fig. 4b–d show the closest contacts of the hydroxylic acid group as donor/acceptor in hydrogen bonding, as well as the O(lp)–π (C₆) interaction in Fig. 4f. The hydrogen donor/acceptor properties of the carboxylic group are visualized in the mapping of the electrostatic potential at the Hirshfeld surface (Fig. 4e).

Figure 4
Chemical scheme (a) and three different orientations (b)–(d) of the d_norm Hirshfeld surface of DBrTMBA. The closest contacts and the eleoctrostatic potential [−0.077, 0.252, (e)] at the Hirshfeld surface as well as the curvature of the Hirshfeld surface (f) and overview of the nearest neighbors accompanying Table 2

(g) are depicted.

Table 2 shows the interaction energies of DBrTMBA with the closest neighbor molecules in the crystal packing (colors in Fig. 4g). As expected, the strongest intermolecular interaction is exhibited over the carboxylic hydrogen contacts as well as the O(lp)–π (C₆) interaction (purple-coloured neighbors).

Table 2
Interaction Energies (kJ mol⁻¹) for the symmetry-generated neighbors of a molecule of DBrTMBA

Values calculated with CrystalExplorer at the B3LYP/6–31G(d,p) level of theory. el: electrostatic, pol: polarization, disp: energy-dispersive, rep: repulsion.

Color code	Symmetry operation	E_el	E_pol	E_disp	E_rep	E_total
Red	−x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$	−1.1	−1.0	−14.0	6.1	−10.3
Orange	x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$	−5.6	−0.7	−10.7	8.3	−10.7
Light green	x, y, z	−6.3	−1.5	−25.8	16.2	−20.2
Green	−x, −y, −z	−3.1	−0.8	−17.3	12.9	−11.0
Cyan	x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$	−3.3	−0.3	−7.3	8.7	−4.7
Blue	−x, −y, −z	−9.0	−2.0	37.6	22.1	−30.1
Purple	−x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$	−63.4	−17.1	−28.1	80.0	−54.7
Pink	−x, −y, −z	−1.8	−0.4	−13.8	11.4	−7.1

The fingerprint plots (Fig. 5) show the various contributions of Br⋯H, O⋯H, H⋯H and C⋯H interactions to the Hirshfeld surface, indicating a high contribution of Br⋯H and O⋯H interactions.

Figure 5
Fingerprint plots of the Hirshfeld surface of DBrTMBA.

4. Database survey

Five crystal structures from other authors featuring 3,4,5-trimethoxybenzoic acid (TMBA) are known in the Cambridge Structural Database (CSD, WebCSD search July 2023; Groom et al., 2016 ). The structure of the parent compound, which crystallizes in space group Pc, has been reported twice (Qadeer et al., 2007 , Bolte, 2011 ). Three other structures contain TMBA co-crystallized with other organic molecules (Thomas et al., 2019 ; Chen et al., 2018 ; Zhang et al., 2021 ). All of them reveal co-planar arrangements of the benzene rings and hydrogen-bonding interactions. Furthermore, we recently reported on the previously discussed mono- and diiodo-3,4,5-trimethoxybenzoic acids ITMBA and DITMBA (Kolev et al., 2021, 2023).

5. Synthesis and crystallization

The title compound was synthesized according to the following experimental procedure: A solution of 2-iodo-3,4,5-trimethoxybenzoic acid (0.36 mmol) in 0.2 M NaOH (0.5 mL) was added dropwise to a magnetically stirred aqueous sulfuric acid solution (3.2 M, 0.6 mL) of KBrO₃ (0.72 mmol). The temperature of the reaction mixture was then raised gradually from 294 to 338 K. The resulting solution was stirred for an additional 4.0 h at 338 K and then allowed to cool slowly down (without stirring) to room temperature. The desired product, 2,6-dibromo-3,4,5-trimethoxybenzoic acid, crystallized as long, thin needles (m.p. 417–421 K; yield: 30%).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. An Hirshfeld Atom Refinement (HAR) using NoSpherA2 in Olex2 was performed to obtain non-spherical atomic form factors as well as anisotropic hydrogen atomic displacement parameters (Hirshfeld, 1977 , Kleemiss et al., 2021 ). Orca5 (Neese et al., 2020 ) was used for the single-point calculations for the HAR procedure at def2-TZVP/M062X level of theory. The H—X distances were fixed to neutron distances from Allen & Bruno (2010 ) and refined anisotropically with displacement parameter restraints. The choice to fix the H—X distances to neutron distances was made because, even after several attempts at data collection, the data from DBrTMBA did not allow for the refinement of unrestrained hydrogen distances, but did allow for the refinement of softly restrained hydrogen atom anisotropic displacement parameters at these fixed distances.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₀H₁₀Br₂O₅
M_r	370.00
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	11.4047 (9), 7.1107 (3), 16.8997 (13)
β (°)	107.009 (8)
V (Å³)	1310.54 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	6.19
Crystal size (mm)	0.08 × 0.06 × 0.03

Data collection
Diffractometer	SuperNova, Dualflex, AtlasS2
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2022 )
T_min, T_max	0.749, 0.855
No. of measured, independent and observed [I ≥ 2u(I)] reflections	18764, 3245, 2254
R_int	0.084
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.123, 1.06
No. of reflections	3245
No. of parameters	218
No. of restraints	63
H-atom treatment	Only H-atom displacement parameters refined
Δρ_max, Δρ_min (e Å⁻³)	1.25, −1.48
Computer programs: CrysAlis PRO (Rigaku OD, 2022), SHELXT2018/2 (Sheldrick, 2015 ), OLEX2.refine (Bourhis et al., 2015 ), NoSpherA2 (Kleemiss et al., 2021), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2281408

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023007831/jy2033sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023007831/jy2033Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989023007831/jy2033Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO 1.171.43.36a (Rigaku OD, 2022); cell refinement: CrysAlis PRO 1.171.43.36a (Rigaku OD, 2022); data reduction: CrysAlis PRO 1.171.43.36a (Rigaku OD, 2022); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015); program(s) used to refine structure: olex2.refine 1.5-alpha (Bourhis et al., 2015), NoSpherA2 (Kleemiss et al., 2021); molecular graphics: Olex2 1.5-alpha (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

2,6-Dibromo-3,4,5-trimethoxybenzoic acid top

Crystal data top

C₁₀H₁₀Br₂O₅	F(000) = 718.856
M_r = 370.00	D_x = 1.875 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.4047 (9) Å	Cell parameters from 1911 reflections
b = 7.1107 (3) Å	θ = 3.1–28.8°
c = 16.8997 (13) Å	µ = 6.19 mm⁻¹
β = 107.009 (8)°	T = 100 K
V = 1310.54 (16) Å³	Block, clear colourless
Z = 4	0.08 × 0.06 × 0.03 mm

Data collection top

SuperNova, Dualflex, AtlasS2 diffractometer	3245 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	2254 reflections with I ≥ 2u(I)
Mirror monochromator	R_int = 0.084
Detector resolution: 5.2548 pixels mm^-1	θ_max = 28.3°, θ_min = 3.1°
ω scans	h = −17→19
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2022)	k = −12→6
T_min = 0.749, T_max = 0.855	l = −28→28
18764 measured reflections

Refinement top

Refinement on F²	4 constraints
Least-squares matrix: full	Primary atom site location: dual
R[F² > 2σ(F²)] = 0.053	Only H-atom displacement parameters refined
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0395P)² + 3.4625P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.0002
3245 reflections	Δρ_max = 1.25 e Å⁻³
218 parameters	Δρ_min = −1.48 e Å⁻³
63 restraints

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

	x	y	z	U_iso*/U_eq
Br1	0.86638 (5)	0.67372 (7)	0.45104 (4)	0.03398 (18)
Br2	0.43161 (5)	0.68854 (7)	0.17096 (3)	0.03341 (18)
O1	0.6558 (4)	0.9831 (5)	0.3032 (2)	0.0315 (9)
H1	0.692 (6)	1.0810 (6)	0.277 (4)	0.04 (2)
O2	0.7570 (4)	0.7934 (5)	0.2410 (3)	0.0384 (11)
O3	0.7246 (5)	0.3480 (5)	0.5004 (3)	0.0468 (12)
O4	0.5037 (4)	0.1913 (5)	0.4131 (3)	0.0442 (12)
O5	0.3643 (4)	0.3576 (5)	0.2669 (3)	0.0484 (13)
C4	0.6357 (4)	0.6586 (6)	0.3198 (3)	0.0200 (10)
C5	0.7054 (5)	0.5773 (7)	0.3932 (3)	0.0278 (12)
C3	0.5234 (5)	0.5822 (7)	0.2773 (4)	0.0284 (12)
C6	0.6606 (6)	0.4204 (7)	0.4262 (3)	0.0312 (13)
C2	0.4771 (5)	0.4239 (7)	0.3079 (4)	0.0319 (13)
C7	0.6884 (5)	0.8184 (7)	0.2838 (3)	0.0261 (12)
C1	0.5451 (6)	0.3442 (7)	0.3827 (4)	0.0300 (13)
C8	0.7911 (7)	0.1815 (8)	0.4937 (4)	0.0472 (17)
H00a	0.852 (3)	0.2105 (16)	0.457 (2)	0.056 (11)
H00b	0.844 (3)	0.136 (3)	0.5545 (5)	0.057 (10)
H00c	0.7277 (7)	0.0722 (18)	0.465 (2)	0.048 (10)
C10	0.3618 (7)	0.1753 (8)	0.2314 (5)	0.0523 (19)
H00d	0.2696 (10)	0.142 (3)	0.195 (2)	0.066 (11)
H00e	0.421 (3)	0.173 (2)	0.192 (2)	0.061 (11)
H00f	0.393 (4)	0.0726 (11)	0.2799 (5)	0.060 (11)
C9	0.4330 (7)	0.2341 (9)	0.4679 (5)	0.056 (2)
H00g	0.359 (2)	0.326 (5)	0.4373 (10)	0.062 (10)
H00h	0.397 (3)	0.1060 (11)	0.485 (2)	0.052 (10)
H00i	0.4904 (11)	0.302 (5)	0.5224 (12)	0.072 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0308 (3)	0.0207 (3)	0.0382 (4)	0.0033 (2)	−0.0091 (2)	−0.0047 (2)
Br2	0.0382 (4)	0.0181 (3)	0.0312 (3)	0.0032 (2)	−0.0097 (2)	−0.0045 (2)
O1	0.043 (2)	0.0208 (19)	0.038 (2)	−0.0014 (17)	0.0242 (19)	0.0003 (16)
H1	0.08 (4)	0.03 (3)	0.04 (3)	−0.024 (13)	0.033 (17)	−0.006 (13)
O2	0.061 (3)	0.0176 (19)	0.056 (3)	0.0006 (18)	0.047 (2)	0.0001 (18)
O3	0.083 (4)	0.029 (2)	0.031 (2)	0.010 (2)	0.021 (2)	0.0072 (18)
O4	0.068 (3)	0.021 (2)	0.062 (3)	0.0039 (19)	0.048 (3)	0.0028 (19)
O5	0.027 (2)	0.026 (2)	0.089 (4)	−0.0041 (17)	0.013 (2)	−0.007 (2)
C4	0.023 (3)	0.015 (2)	0.025 (3)	−0.0035 (19)	0.012 (2)	−0.0007 (18)
C5	0.035 (3)	0.022 (3)	0.028 (3)	0.004 (2)	0.012 (2)	0.000 (2)
C3	0.026 (3)	0.019 (3)	0.040 (3)	−0.002 (2)	0.009 (2)	−0.002 (2)
C6	0.049 (4)	0.020 (3)	0.028 (3)	0.002 (2)	0.018 (3)	0.004 (2)
C2	0.026 (3)	0.024 (3)	0.050 (4)	−0.005 (2)	0.016 (3)	−0.001 (2)
C7	0.036 (3)	0.014 (2)	0.035 (3)	0.003 (2)	0.022 (2)	−0.001 (2)
C1	0.043 (3)	0.015 (2)	0.040 (3)	−0.001 (2)	0.026 (3)	0.003 (2)
C8	0.068 (5)	0.028 (3)	0.039 (4)	0.009 (3)	0.006 (3)	0.008 (3)
H00a	0.069 (13)	0.05 (3)	0.041 (11)	0.005 (8)	0.006 (6)	0.012 (7)
H00b	0.072 (15)	0.05 (2)	0.042 (7)	0.006 (8)	0.005 (5)	0.014 (5)
H00c	0.066 (17)	0.031 (15)	0.040 (12)	0.011 (8)	0.008 (6)	0.008 (6)
C10	0.050 (5)	0.028 (3)	0.077 (6)	−0.005 (3)	0.016 (4)	−0.009 (3)
H00d	0.054 (7)	0.06 (3)	0.082 (14)	−0.012 (5)	0.015 (5)	−0.003 (8)
H00e	0.053 (10)	0.05 (3)	0.078 (13)	−0.008 (7)	0.016 (6)	−0.010 (8)
H00f	0.063 (13)	0.036 (19)	0.079 (14)	−0.003 (7)	0.018 (6)	−0.007 (8)
C9	0.076 (6)	0.036 (4)	0.081 (6)	0.010 (3)	0.063 (5)	0.010 (4)
H00g	0.082 (12)	0.038 (11)	0.09 (2)	0.012 (5)	0.059 (8)	0.008 (6)
H00h	0.081 (17)	0.033 (9)	0.073 (19)	0.012 (6)	0.070 (8)	0.003 (6)
H00i	0.10 (2)	0.041 (12)	0.092 (12)	0.008 (6)	0.051 (8)	0.007 (6)

Geometric parameters (Å, º) top

Br1—C5	1.935 (6)	C5—C6	1.408 (7)
Br2—C3	1.948 (6)	C3—C2	1.405 (7)
O1—C7	1.299 (6)	C6—C1	1.415 (8)
O2—C7	1.224 (6)	C2—C1	1.395 (8)
O3—C6	1.354 (7)	C8—H00a	1.0770
O3—C8	1.429 (7)	C8—H00b	1.0770
O4—C1	1.346 (6)	C8—H00c	1.0770
O4—C9	1.427 (7)	C10—H00d	1.0770
O5—C2	1.355 (7)	C10—H00e	1.0770
O5—C10	1.425 (7)	C10—H00f	1.0770
C4—C5	1.388 (7)	C9—H00g	1.0770
C4—C3	1.383 (7)	C9—H00h	1.0770
C4—C7	1.496 (7)	C9—H00i	1.0770

C1—C2—C3	119.3 (5)	C8—O3—C6	113.4 (5)
C1—C2—O5	121.0 (5)	C9—O4—C1	113.8 (4)
C1—C6—C5	119.2 (5)	H00a—C8—O3	109.5
C1—C6—O3	120.2 (5)	H00b—C8—H00a	109.5
C10—O5—C2	115.5 (5)	H00b—C8—O3	109.5
C2—C1—C6	120.1 (5)	H00c—C8—H00b	109.5
C2—C1—O4	120.6 (6)	H00c—C8—H00a	109.5
C2—C3—C4	120.9 (5)	H00c—C8—O3	109.5
C2—C3—Br2	119.5 (4)	H00d—C10—O5	109.5
C3—C2—O5	119.6 (5)	H00e—C10—H00d	109.5
C3—C4—C5	120.1 (5)	H00e—C10—O5	109.5
C4—C7—O2	122.1 (4)	H00f—C10—H00e	109.5
C4—C7—O1	113.8 (4)	H00f—C10—H00d	109.5
C4—C3—Br2	119.5 (4)	H00f—C10—O5	109.5
C4—C5—Br1	121.0 (4)	H00g—C9—O4	109.5
C5—C6—O3	120.5 (6)	H00h—C9—H00g	109.5
C6—C1—O4	119.3 (5)	H00h—C9—O4	109.5
C6—C5—C4	120.3 (5)	H00i—C9—H00h	109.5
C6—C5—Br1	118.8 (4)	H00i—C9—H00g	109.5
C7—C4—C3	120.5 (5)	H00i—C9—O4	109.5
C7—C4—C5	119.1 (5)	O2—C7—O1	124.0 (5)
C7—O1—H1	109.5

Br1—C5—C4—C3	176.9 (4)	O3—C6—C5—C4	−175.7 (5)
Br1—C5—C4—C7	2.2 (5)	O3—C6—C1—O4	−4.6 (6)
Br1—C5—C6—O3	5.3 (5)	O3—C6—C1—C2	177.3 (5)
Br1—C5—C6—C1	−177.5 (4)	O4—C1—C6—C5	178.3 (5)
Br2—C3—C4—C5	−176.2 (4)	O4—C1—C2—O5	4.4 (6)
Br2—C3—C4—C7	−1.7 (5)	O4—C1—C2—C3	−179.2 (5)
Br2—C3—C2—O5	−5.8 (5)	O5—C2—C3—C4	176.9 (5)
Br2—C3—C2—C1	177.8 (4)	O5—C2—C1—C6	−177.5 (5)
O1—C7—C4—C5	−96.1 (5)	C4—C5—C6—C1	1.4 (6)
O1—C7—C4—C3	89.3 (5)	C4—C3—C2—C1	0.5 (6)
O2—C7—C4—C5	83.0 (6)	C5—C6—C1—C2	0.2 (6)
O2—C7—C4—C3	−91.5 (6)	C3—C2—C1—C6	−1.2 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.98 (5)	1.68 (3)	2.617 (5)	160 (5)

Symmetry code: (i) −x+3/2, y+1/2, −z+1/2.

Interaction Energies (kJ mol^-1) for the symmetry-generated neighbors of a molecule of DBrTMBA top

Values calculated with CrystalExplorer at the B3LYP/6-31G(d,p) level of theory. el: electrostatic, pol: polarization, disp: dispersion, rep: repulsion.

Color code	Symmetry operation	E_el	E_pol	E_disp	E_rep	E_total
Red	-x + 1/2, y + 1/2, -z + 1/2	-1.1	-1.0	-14.0	6.1	-10.3
Orange	x + 1/2, -y + 1/2, z + 1/2	-5.6	-0.7	-10.7	8.3	-10.7
Light green	x, y, z	-6.3	-1.5	-25.8	16.2	-20.2
Green	-x, -y, -z	-3.1	-0.8	-17.3	12.9	-11.0
Cyan	x + 1/2, -y + 1/2, z + 1/2	-3.3	-0.3	-7.3	8.7	-4.7
Blue	-x, -y, -z	-9.0	-2.0	37.6	22.1	-30.1
Purple	-x + 1/2, y + 1/2, -z + 1/2	-63.4	-17.1	-28.1	80.0	-54.7
Pink	-x, -y, -z	-1.8	-0.4	-13.8	11.4	-7.1

Funding information

Funding for this research was provided by the Institutional grant program of Medical University "Prof. Dr. Paraskev Stoyanov", Varna, "Nauka" (Project 20023).

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