Crystal structure and Hirshfeld surface of 5-bromo­salicylic acid di­methyl­formamide mono­solvate

Akerele, O.; Lemmerer, A.

doi:10.1107/S2056989026008984

early career research

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Volume 82| Part 10| October 2026|

https://doi.org/10.1107/S2056989026008984

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Crystal structure and Hirshfeld surface of 5-bromosalicylic acid dimethylformamide monosolvate

Oluwatoyin Akerele ^a ^* and Andreas Lemmerer ^a

^aJan Boeyens Structural Chemistry Laboratory, Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Private Bag 3, PO Wits, 2050, Johannesburg, South Africa
^*Correspondence e-mail: [email protected]

Edited by T. Akitsu, Tokyo University of Science, Japan (Received 14 August 2026; accepted 29 August 2026; online 3 September 2026)

This article is part of the collection Early Career Scientists in Structural Science.

The structure of the title compound, C₇H₅BrO₃·C₃H₇NO, at 173 K has triclinic (P1) symmetry with Z = 4. The asymmetric unit comprises two molecules of 5-bromosalicylic acid and two molecules of N,N-dimethylformamide (DMF). The crystal structure is dominated by strong O—H⋯O hydrogen bonds between the carboxylic acid group of the 5-bromosalicylic acid molecules and the carbonyl oxygen atom of the DMF molecules, with the solvent acting as a hydrogen-bond acceptor. This interaction prevents the formation of the common carboxylic acid dimer observed in many benzoic acid derivatives. Additional C—H⋯O hydrogen bonds and Br⋯O non-covalent interactions between neighbouring molecules contribute to the cohesion of the structure. Aromatic π–π stacking interactions between adjacent benzene rings further consolidate the crystal structure and generate a three-dimensional supramolecular assembly. Hirshfeld surface analysis confirms that H⋯H, H⋯O/O⋯H and Br⋯H/H⋯Br contacts make the largest contributions to the crystal packing. The inclusion of DMF therefore plays a significant role in directing the intermolecular interactions and overall supramolecular packing of the crystal structure.

Keywords: crystal structure; 5-bromosalicylic acid; DMF solvate; Hirshfeld surfaces; non-covalent interactions.

CCDC reference: 2579645

1. Chemical context

5-Bromosalicylic acid (5-bromo-2-hydroxybenzoic acid) is a halogenated derivative of salicylic acid that is widely used as an intermediate in organic synthesis. Due to the presence of both carboxylic acid and phenolic functional groups, it serves as a versatile precursor in the preparation of pharmaceuticals, agrochemicals, and functional materials. The incorporation of N,N-dimethylformamide (DMF) into the crystal structure influences the molecular conformation and crystal packing through hydrogen-bonding and other non-covalent interactions, making such solvates of interest in crystal engineering and solid-state chemistry (Edkins et al., 2022 ).

2. Structural commentary

The asymmetric unit consists of two molecules each of 5-bromosalicylic acid of DMF (Fig. 1). The carboxylic acid groups form discrete O2—H2⋯O1 and O6—H6⋯O5 hydrogen bonds to the carbonyl oxygen atoms of the two DMF molecules (Table 1) with O⋯O distances of 2.5500 (15) and 2.5381 (15) Å, respectively. Intramolecular O4—H4⋯O3 and O8—H8A⋯O7 hydrogen bonds occur within the two acid molecules. The acid–DMF hydrogen bonds prevent the formation of the usual carboxylic acid dimer (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8A⋯O7	0.84	1.84	2.5786 (16)	146
O2—H2⋯O1	0.84	1.71	2.5500 (15)	175
O6—H6⋯O5	0.84	1.71	2.5381 (15)	169
O4—H4⋯O3	0.84	1.83	2.5708 (17)	146
C1—H1⋯O3	0.95	2.45	3.165 (2)	132
C2—H2B⋯O5ⁱ	0.98	2.47	3.261 (2)	137
C8—H8⋯O8ⁱⁱ	0.95	2.49	3.323 (2)	146
C11—H11⋯O7	0.95	2.55	3.2248 (19)	128
C18—H18⋯O4ⁱⁱⁱ	0.95	2.54	3.354 (2)	144
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 1
The molecular structure of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Extended molecules of the title compound linked by non-covalent interactions.

3. Supramolecular features

In the crystal, C—H⋯O interactions are observed (Table 1). Two nearly linear Br⋯O halogen bonds link neighbouring 5-bromosalicylic acid molecules: Br1⋯O3(x, y + 1, z) = 3.2413 (12) Å, C9—Br1⋯O3 = 176.27°, and Br2⋯O7(x, y − 1, z) = 3.2513 (12) Å, C19—Br2⋯O7 = 172.13°. Together with the C—H⋯O contacts listed in Table 1, these interactions contribute to the crystal packing (Figs. 2 and 3). π–π stacking interactions are also observed [distance between the centroid of the C5–C10 ring and its symmetry equivalent at −x, −y − 1, −z − 2 = 3.6466 (9) Å, perpendicular distance = 3.4691 (6) Å and slippage = 1.124 Å].

Figure 3
Crystal structure of the title compound viewed along the a axis.

Hirshfeld surface analysis performed with CrystalExplorer21 (Spackman et al., 2021 ) indicates that the major contributions to the crystal packing arise from H⋯H (39.9%), H⋯O/O⋯H (19.4%), Br⋯H/H⋯Br (18.3%), H⋯C/C⋯H (9.5%), C⋯O/O⋯C (4.7%), C⋯C (3.3%), and Br⋯O/O⋯Br (2.8%) contacts (see Figs. 4 and 5). The visualization of important regions of intermolecular interactions on the surface, generated at high standard resolution, correlates with the contact percentages.

Figure 4
Hirshfeld surfaces of the title compound.

Figure 5
Contact percentages from fingerprint plots of the title compound.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 2026.2.0; Groom et al., 2016 ) revealed two closely related structures containing 5-bromosalicylic acid. These are the co-crystal of 3,6,9-trimethyldecahydro-3,12-epoxy[1,2]dioxepino[4,3-isoquinolin-10(3H)-one with 5-bromo-2-hydroxybenzoic acid (CSD refcode ISIMEF; Roy et al., 2021 ) and pure 5-bromosalicylic acid (CSD refcode IYAWIO01; Montis & Hursthouse, 2012 ). In IYAWIO01, pairs of O—H⋯O hydrogen bonds generate an R₂²(8) carboxylic acid dimer motif. In contrast, the co-crystal structure (ISIMEF) contains a nitrogen-containing heterocyclic co-former that disrupts the acid dimer and forms a heteromolecular hydrogen-bonded assembly involving the carboxylic acid group. In the title DMF solvate, the carboxylic acid group forms a strong O—H⋯O hydrogen bond with the carbonyl oxygen atom of the DMF molecule, preventing acid–acid dimer formation and leading to a different supramolecular arrangement. The crystal packing is further consolidated by Br⋯O halogen-bonding interaction and additional weak contacts.

5. Synthesis and crystallization

5-Bromosalicylic acid (20 mg) was dissolved in DMF (0.5 mL) under stirring at room temperature until a clear solution was obtained. The solution was then left to stand under ambient conditions. After 6 days, colourless crystals of the title DMF solvate, suitable for single-crystal X-ray diffraction analysis, were obtained by slow crystallization from the solution.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms bonded to carbon atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for aromatic and formyl H atoms and 0.98 Å for methyl H atoms. Hydrogen atoms bonded to oxygen atoms were located in difference-Fourier maps and subsequently refined using a rotating-group model, with O—H = 0.84 Å. Methyl and hydroxyl groups were allowed to rotate about their parent bonds. The H-atom displacement parameters were fixed at 1.2U_eq(C) for aromatic and formyl H atoms and 1.5U_eq(C,O) for methyl and hydroxyl H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₅BrO₃·C₃H₇NO
M_r	290.12
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	173
a, b, c (Å)	8.5524 (3), 9.5175 (3), 14.9678 (5)
α, β, γ (°)	95.923 (1), 99.795 (2), 100.461 (1)
V (Å³)	1169.27 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.51
Crystal size (mm)	0.51 × 0.23 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.547, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	40930, 5813, 5097
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.062, 1.03
No. of reflections	5813
No. of parameters	297
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.46
Computer programs: APEX4 (Bruker, 2021 ), SAINT (Bruker, 2016 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2579645

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989026008984/jp2033sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989026008984/jp2033Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989026008984/jp2033sup3.txt

LST file. DOI: https://doi.org/10.1107/S2056989026008984/jp2033sup4.txt

Supporting information file. DOI: https://doi.org/10.1107/S2056989026008984/jp2033Isup5.cml

checkCIF report

Computing details top

5-Bromo-2-hydroxybenzoic acid dimethylformamide monosolvate top

Crystal data top

C₇H₅BrO₃·C₃H₇NO	Z = 4
M_r = 290.12	F(000) = 584
Triclinic, P1	D_x = 1.648 Mg m⁻³
a = 8.5524 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5175 (3) Å	Cell parameters from 9989 reflections
c = 14.9678 (5) Å	θ = 2.5–28.3°
α = 95.923 (1)°	µ = 3.51 mm⁻¹
β = 99.795 (2)°	T = 173 K
γ = 100.461 (1)°	Block, colourless
V = 1169.27 (7) Å³	0.51 × 0.23 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	5097 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.052
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 28.3°, θ_min = 2.2°
T_min = 0.547, T_max = 0.746	h = −11→11
40930 measured reflections	k = −12→12
5813 independent reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.062	w = 1/[σ²(F_o²) + (0.0278P)² + 0.2966P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
5813 reflections	Δρ_max = 0.33 e Å⁻³
297 parameters	Δρ_min = −0.46 e Å⁻³
0 restraints

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.

Refinement. Single-crystal X-ray diffraction data were obtained at 173 (2) K on a Bruker D8 Venture PHOTON III 28-pixel array area detector (208 \× 128 mm2) diffractometer with a Mo K\a (\l= 0.71073 \%A) I\mS DIAMOND source (50 kV, 1.4 mA). Data collection and reduction were carried out using APEX4 and SAINT (Bruker, 2021; Bruker, 2016). The multi-scan method implemented in SADABS-2016 was used for empirical absorption corrections and correction of other systematic errors. The crystal structure was solved using intrinsic phasing SHELXT (Sheldrick, 2015) and refined using SHELXL (Sheldrick, 2008) within the Olex2 graphical user interface. All atoms were refined anisotropically before the inclusion of hydrogen atoms.

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

	x	y	z	U_iso*/U_eq
Br1	0.24557 (2)	0.90992 (2)	0.99013 (2)	0.04169 (6)
Br2	0.11748 (2)	−0.40750 (2)	0.65880 (2)	0.04226 (6)
O1	0.45314 (14)	0.20472 (11)	0.75929 (8)	0.0368 (2)
O5	0.33570 (14)	0.29235 (12)	0.43497 (8)	0.0381 (2)
O7	0.13035 (15)	0.25750 (12)	0.59788 (8)	0.0390 (2)
O8	0.00799 (16)	0.19629 (12)	0.73855 (8)	0.0427 (3)
H8A	0.045021	0.249767	0.702559	0.064*
O2	0.36799 (14)	0.40506 (11)	0.85473 (8)	0.0367 (2)
H2	0.395224	0.335766	0.825995	0.055*
O6	0.23087 (14)	0.09168 (11)	0.52209 (7)	0.0361 (2)
H6	0.252385	0.158605	0.490892	0.054*
O3	0.30139 (15)	0.23840 (12)	0.94363 (8)	0.0427 (3)
O4	0.18671 (16)	0.30712 (13)	1.08632 (8)	0.0435 (3)
H4	0.210778	0.251409	1.045891	0.065*
N2	0.34281 (16)	0.51893 (14)	0.40096 (9)	0.0355 (3)
N1	0.51487 (16)	−0.01708 (14)	0.75441 (9)	0.0351 (3)
C15	0.10489 (16)	0.02410 (15)	0.64352 (9)	0.0275 (3)
C4	0.31245 (17)	0.36294 (15)	0.92582 (10)	0.0314 (3)
C9	0.22763 (18)	0.71811 (15)	1.01831 (10)	0.0316 (3)
C6	0.20164 (18)	0.44069 (16)	1.06202 (10)	0.0320 (3)
C20	0.12885 (16)	−0.11631 (15)	0.62580 (10)	0.0298 (3)
H20	0.176193	−0.143184	0.575298	0.036*
C19	0.08332 (18)	−0.21607 (15)	0.68211 (10)	0.0320 (3)
C5	0.26317 (17)	0.47561 (15)	0.98422 (10)	0.0288 (3)
C1	0.46234 (18)	0.09204 (16)	0.79304 (10)	0.0334 (3)
H1	0.429615	0.083668	0.850143	0.040*
C10	0.27628 (17)	0.61624 (15)	0.96262 (10)	0.0294 (3)
H10	0.318147	0.641357	0.910262	0.035*
C16	0.03502 (18)	0.06247 (16)	0.71833 (10)	0.0326 (3)
C7	0.15243 (19)	0.54558 (18)	1.11597 (10)	0.0365 (3)
H7	0.109281	0.521697	1.168167	0.044*
C11	0.29387 (18)	0.41018 (16)	0.44427 (10)	0.0335 (3)
H11	0.222198	0.422971	0.485064	0.040*
C14	0.15624 (17)	0.13472 (16)	0.58590 (10)	0.0304 (3)
C8	0.16558 (19)	0.68325 (17)	1.09458 (10)	0.0359 (3)
H8	0.132202	0.754584	1.132006	0.043*
C17	−0.0081 (2)	−0.04037 (18)	0.77453 (11)	0.0389 (3)
H17	−0.054262	−0.014639	0.825735	0.047*
C18	0.01557 (19)	−0.17821 (17)	0.75643 (11)	0.0376 (3)
H18	−0.014496	−0.247759	0.794876	0.045*
C3	0.5218 (2)	−0.14650 (17)	0.79741 (13)	0.0447 (4)
H3A	0.495315	−0.131993	0.858439	0.067*
H3B	0.631176	−0.166591	0.802887	0.067*
H3C	0.443578	−0.228194	0.759914	0.067*
C2	0.5640 (2)	−0.0115 (2)	0.66674 (13)	0.0501 (4)
H2A	0.512595	0.057446	0.634142	0.075*
H2B	0.530541	−0.107422	0.630384	0.075*
H2C	0.682051	0.019077	0.676347	0.075*
C13	0.4530 (2)	0.5069 (2)	0.33809 (12)	0.0473 (4)
H13A	0.504693	0.424583	0.348527	0.071*
H13B	0.536313	0.595507	0.348326	0.071*
H13C	0.392531	0.492385	0.274963	0.071*
C12	0.2898 (2)	0.65488 (19)	0.41511 (14)	0.0483 (4)
H12A	0.207765	0.645326	0.453748	0.072*
H12B	0.243159	0.680008	0.355874	0.072*
H12C	0.382665	0.730932	0.445248	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.05939 (11)	0.02360 (8)	0.04263 (9)	0.00900 (7)	0.01085 (7)	0.00440 (6)
Br2	0.04500 (10)	0.02475 (8)	0.06018 (11)	0.00816 (6)	0.01501 (7)	0.01047 (7)
O1	0.0456 (6)	0.0282 (5)	0.0401 (6)	0.0120 (4)	0.0120 (5)	0.0063 (4)
O5	0.0508 (6)	0.0318 (6)	0.0395 (6)	0.0148 (5)	0.0187 (5)	0.0121 (4)
O7	0.0547 (7)	0.0282 (5)	0.0427 (6)	0.0173 (5)	0.0189 (5)	0.0121 (4)
O8	0.0576 (7)	0.0332 (6)	0.0481 (7)	0.0199 (5)	0.0268 (6)	0.0090 (5)
O2	0.0504 (6)	0.0259 (5)	0.0393 (6)	0.0106 (5)	0.0187 (5)	0.0075 (4)
O6	0.0508 (6)	0.0301 (6)	0.0344 (5)	0.0143 (5)	0.0180 (5)	0.0105 (4)
O3	0.0594 (7)	0.0264 (6)	0.0497 (7)	0.0137 (5)	0.0215 (6)	0.0126 (5)
O4	0.0571 (7)	0.0355 (6)	0.0477 (7)	0.0146 (5)	0.0223 (6)	0.0217 (5)
N2	0.0399 (7)	0.0316 (7)	0.0380 (7)	0.0100 (5)	0.0099 (5)	0.0099 (5)
N1	0.0381 (7)	0.0295 (6)	0.0389 (7)	0.0101 (5)	0.0074 (5)	0.0044 (5)
C15	0.0270 (6)	0.0269 (7)	0.0297 (7)	0.0072 (5)	0.0055 (5)	0.0059 (5)
C4	0.0328 (7)	0.0271 (7)	0.0353 (7)	0.0058 (5)	0.0082 (6)	0.0070 (5)
C9	0.0353 (7)	0.0250 (7)	0.0337 (7)	0.0048 (5)	0.0052 (6)	0.0050 (5)
C6	0.0321 (7)	0.0317 (7)	0.0344 (7)	0.0063 (5)	0.0079 (6)	0.0125 (6)
C20	0.0293 (7)	0.0278 (7)	0.0327 (7)	0.0056 (5)	0.0070 (5)	0.0047 (5)
C19	0.0326 (7)	0.0243 (7)	0.0393 (8)	0.0056 (5)	0.0066 (6)	0.0062 (6)
C5	0.0297 (7)	0.0258 (7)	0.0315 (7)	0.0049 (5)	0.0061 (5)	0.0072 (5)
C1	0.0349 (7)	0.0287 (7)	0.0356 (7)	0.0063 (6)	0.0060 (6)	0.0022 (6)
C10	0.0324 (7)	0.0250 (7)	0.0306 (7)	0.0026 (5)	0.0071 (5)	0.0066 (5)
C16	0.0332 (7)	0.0312 (7)	0.0356 (7)	0.0098 (6)	0.0093 (6)	0.0052 (6)
C7	0.0380 (8)	0.0419 (9)	0.0322 (7)	0.0077 (6)	0.0114 (6)	0.0098 (6)
C11	0.0382 (8)	0.0336 (8)	0.0316 (7)	0.0102 (6)	0.0094 (6)	0.0079 (6)
C14	0.0333 (7)	0.0293 (7)	0.0298 (7)	0.0087 (5)	0.0055 (5)	0.0067 (5)
C8	0.0385 (8)	0.0362 (8)	0.0337 (7)	0.0090 (6)	0.0098 (6)	0.0018 (6)
C17	0.0444 (9)	0.0398 (9)	0.0381 (8)	0.0098 (7)	0.0199 (7)	0.0087 (6)
C18	0.0386 (8)	0.0349 (8)	0.0417 (8)	0.0048 (6)	0.0123 (6)	0.0136 (6)
C3	0.0529 (10)	0.0279 (8)	0.0538 (10)	0.0118 (7)	0.0070 (8)	0.0063 (7)
C2	0.0585 (11)	0.0511 (11)	0.0504 (10)	0.0257 (9)	0.0220 (9)	0.0067 (8)
C13	0.0580 (11)	0.0458 (10)	0.0461 (9)	0.0124 (8)	0.0231 (8)	0.0182 (8)
C12	0.0549 (10)	0.0313 (9)	0.0631 (11)	0.0153 (7)	0.0126 (9)	0.0127 (8)

Geometric parameters (Å, º) top

Br1—C9	1.9009 (14)	C6—C7	1.388 (2)
Br2—C19	1.9036 (14)	C20—H20	0.9500
O1—C1	1.2411 (18)	C20—C19	1.381 (2)
O5—C11	1.2391 (18)	C19—C18	1.384 (2)
O7—C14	1.2292 (18)	C5—C10	1.3985 (19)
O8—H8A	0.8400	C1—H1	0.9500
O8—C16	1.3485 (18)	C10—H10	0.9500
O2—H2	0.8400	C16—C17	1.395 (2)
O2—C4	1.3073 (18)	C7—H7	0.9500
O6—H6	0.8400	C7—C8	1.370 (2)
O6—C14	1.3074 (17)	C11—H11	0.9500
O3—C4	1.2321 (18)	C8—H8	0.9500
O4—H4	0.8400	C17—H17	0.9500
O4—C6	1.3480 (18)	C17—C18	1.370 (2)
N2—C11	1.3192 (19)	C18—H18	0.9500
N2—C13	1.451 (2)	C3—H3A	0.9800
N2—C12	1.454 (2)	C3—H3B	0.9800
N1—C1	1.3224 (19)	C3—H3C	0.9800
N1—C3	1.453 (2)	C2—H2A	0.9800
N1—C2	1.447 (2)	C2—H2B	0.9800
C15—C20	1.394 (2)	C2—H2C	0.9800
C15—C16	1.402 (2)	C13—H13A	0.9800
C15—C14	1.4811 (19)	C13—H13B	0.9800
C4—C5	1.479 (2)	C13—H13C	0.9800
C9—C10	1.380 (2)	C12—H12A	0.9800
C9—C8	1.384 (2)	C12—H12B	0.9800
C6—C5	1.4029 (19)	C12—H12C	0.9800

C16—O8—H8A	109.5	C8—C7—C6	120.56 (14)
C4—O2—H2	109.5	C8—C7—H7	119.7
C14—O6—H6	109.5	O5—C11—N2	123.98 (14)
C6—O4—H4	109.5	O5—C11—H11	118.0
C11—N2—C13	120.83 (13)	N2—C11—H11	118.0
C11—N2—C12	121.35 (14)	O7—C14—O6	123.02 (13)
C13—N2—C12	117.82 (14)	O7—C14—C15	122.06 (13)
C1—N1—C3	121.27 (14)	O6—C14—C15	114.92 (12)
C1—N1—C2	120.51 (14)	C9—C8—H8	120.1
C2—N1—C3	118.21 (14)	C7—C8—C9	119.82 (14)
C20—C15—C16	119.67 (13)	C7—C8—H8	120.1
C20—C15—C14	120.93 (13)	C16—C17—H17	119.7
C16—C15—C14	119.38 (13)	C18—C17—C16	120.50 (14)
O2—C4—C5	115.34 (12)	C18—C17—H17	119.7
O3—C4—O2	122.88 (14)	C19—C18—H18	120.0
O3—C4—C5	121.78 (13)	C17—C18—C19	119.96 (14)
C10—C9—Br1	119.67 (11)	C17—C18—H18	120.0
C10—C9—C8	121.19 (14)	N1—C3—H3A	109.5
C8—C9—Br1	119.14 (11)	N1—C3—H3B	109.5
O4—C6—C5	122.19 (14)	N1—C3—H3C	109.5
O4—C6—C7	118.17 (13)	H3A—C3—H3B	109.5
C7—C6—C5	119.64 (14)	H3A—C3—H3C	109.5
C15—C20—H20	120.2	H3B—C3—H3C	109.5
C19—C20—C15	119.56 (13)	N1—C2—H2A	109.5
C19—C20—H20	120.2	N1—C2—H2B	109.5
C20—C19—Br2	119.71 (11)	N1—C2—H2C	109.5
C20—C19—C18	120.90 (14)	H2A—C2—H2B	109.5
C18—C19—Br2	119.38 (11)	H2A—C2—H2C	109.5
C6—C5—C4	119.55 (13)	H2B—C2—H2C	109.5
C10—C5—C4	120.86 (13)	N2—C13—H13A	109.5
C10—C5—C6	119.59 (13)	N2—C13—H13B	109.5
O1—C1—N1	124.04 (15)	N2—C13—H13C	109.5
O1—C1—H1	118.0	H13A—C13—H13B	109.5
N1—C1—H1	118.0	H13A—C13—H13C	109.5
C9—C10—C5	119.18 (13)	H13B—C13—H13C	109.5
C9—C10—H10	120.4	N2—C12—H12A	109.5
C5—C10—H10	120.4	N2—C12—H12B	109.5
O8—C16—C15	122.35 (14)	N2—C12—H12C	109.5
O8—C16—C17	118.25 (13)	H12A—C12—H12B	109.5
C17—C16—C15	119.40 (14)	H12A—C12—H12C	109.5
C6—C7—H7	119.7	H12B—C12—H12C	109.5

Br1—C9—C10—C5	179.73 (11)	C20—C15—C14—O7	176.93 (14)
Br1—C9—C8—C7	−179.77 (12)	C20—C15—C14—O6	−3.2 (2)
Br2—C19—C18—C17	179.33 (13)	C20—C19—C18—C17	0.4 (2)
O8—C16—C17—C18	179.43 (15)	C5—C6—C7—C8	−0.9 (2)
O2—C4—C5—C6	179.84 (13)	C10—C9—C8—C7	0.3 (2)
O2—C4—C5—C10	0.2 (2)	C16—C15—C20—C19	0.1 (2)
O3—C4—C5—C6	−0.2 (2)	C16—C15—C14—O7	−4.7 (2)
O3—C4—C5—C10	−179.81 (14)	C16—C15—C14—O6	175.13 (13)
O4—C6—C5—C4	0.6 (2)	C16—C17—C18—C19	0.2 (3)
O4—C6—C5—C10	−179.80 (14)	C7—C6—C5—C4	−178.79 (14)
O4—C6—C7—C8	179.72 (14)	C7—C6—C5—C10	0.9 (2)
C15—C20—C19—Br2	−179.47 (11)	C14—C15—C20—C19	178.40 (13)
C15—C20—C19—C18	−0.6 (2)	C14—C15—C16—O8	2.0 (2)
C15—C16—C17—C18	−0.8 (2)	C14—C15—C16—C17	−177.75 (14)
C4—C5—C10—C9	179.40 (14)	C8—C9—C10—C5	−0.3 (2)
C6—C5—C10—C9	−0.2 (2)	C3—N1—C1—O1	−179.67 (15)
C6—C7—C8—C9	0.3 (2)	C2—N1—C1—O1	−1.0 (2)
C20—C15—C16—O8	−179.60 (14)	C13—N2—C11—O5	−0.4 (2)
C20—C15—C16—C17	0.6 (2)	C12—N2—C11—O5	−179.75 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O7	0.84	1.84	2.5786 (16)	146
O2—H2···O1	0.84	1.71	2.5500 (15)	175
O6—H6···O5	0.84	1.71	2.5381 (15)	169
O4—H4···O3	0.84	1.83	2.5708 (17)	146
C1—H1···O3	0.95	2.45	3.165 (2)	132
C2—H2B···O5ⁱ	0.98	2.47	3.261 (2)	137
C8—H8···O8ⁱⁱ	0.95	2.49	3.323 (2)	146
C11—H11···O7	0.95	2.55	3.2248 (19)	128
C18—H18···O4ⁱⁱⁱ	0.95	2.54	3.354 (2)	144

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+2; (iii) −x, −y, −z+2.

References

Bruker (2016). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2021). APEX4. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Edkins, K., Tweedy, J., Fung, S. & Edkins, R. M. (2022). CrystEngComm 24, 1368–1376. CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Montis, R. & Hursthouse, M. B. (2012). CrystEngComm 14, 5242–5254. CrossRef CAS Google Scholar
Roy, M., Li, K., Nisar, M., Wong, L. W.-Y., Sung, H. H.-Y., Haynes, R. K. & Williams, I. D. (2021). Acta Cryst. C77, 262–270. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. CrossRef CAS IUCr Journals Google Scholar

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