3,5-Di­bromo-4-carbamoyl­benzoic acid 2-propanol monosolvate

Noland, W.E.; Herzig, R.J.; Fox, R.J.; Tritch, K.J.

doi:10.1107/S2414314621003916

organic compounds

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ISSN: 2414-3146

Volume 6| Part 4| April 2021| x210391

https://doi.org/10.1107/S2414314621003916

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3,5-Dibromo-4-carbamoylbenzoic acid 2-propanol monosolvate

Wayland E. Noland,^a Ryan J. Herzig,^a Renee J. Fox ^a and Kenneth J. Tritch ^a ^*

^aDepartment of Chemistry, University of Minnesota, 207 Pleasant St SE, Minneapolis, MN 55455, USA
^*Correspondence e-mail: trit0026@umn.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 6 April 2021; accepted 12 April 2021; online 20 April 2021)

In the title solvated crystal, C₈H₅Br₂NO₃·C₃H₈O, the acid molecules form inversion dimers by pairwise N—H⋯O hydrogen bonds between carbamoyl groups and the carboxyl and carbamoyl groups link to form head-to-tail inversion dimers. The 2-propanol hydroxyl group interposes between adjacent head-tail pairs, resulting in C₃³(10) chains of hydrogen bonds propagating along [100]. The molecules of 2-propanol are disordered over two sets of sites in a 0.598 (8):0.402 (8) ratio. The best-fit planes of the carbamoyl group and benzene ring are inclined by 88.26 (11)°. This is a greater inclination than was previously reported with CH₃, Cl, F or H in place of the Br atoms, although those analogues did not have a para carboxyl group.

Keywords: crystal structure; hydrogen bond; dibromoarene; solvate; benzamide.

CCDC reference: 1525812

Structure description

Although the structure of 2-bromobenzamide is reported twice (Izumi & Okamoto, 1972 ; Gulyás et al., 2015 ) in the current version of the Cambridge Structural Database (version 5.42, Nov 2020; Groom et al., 2016 ), no 2,6-dibromo- or 4-carboxylbenzamides were found. The title compound (I) is an example of both classes, and was accidentally prepared in an attempt to selectively hydrolyze the ester group of a cyano ester (II) (Fig. 1). The target was cyano acid (III), for a study in our laboratory involving co-crystals of (III) with anthracene (Noland et al., 2017 ).

Figure 1
The synthesis of (I).

In the title crystal (Fig. 2), molecules of (I) form typical amide inversion dimers based on pairwise N1—H1A⋯O1 hydrogen bonds (Table 1; Fig. 3). The carboxyl groups do not homo-dimerize. Instead, they participate in amido-carboxy N1—H1B⋯O2 hydrogen bonding that forms head-to-tail inversion dimers about the center of the unit cell. The solvent molecule of 2-propanol interposes between H3A of the acid group and O1 of the amide group, forming an O3—H3A⋯O4—H4B⋯O1 hydrogen-bonded chain. Excluding amide dimerization, these hydrogen bonds collectively form C₃³(10) chains propagating along [100]. The 2-propanol molecule is disordered over two sets of sites in a 0.598 (8):0.402 (8) ratio. The Br atoms and benzene ring do not participate in any short interactions.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O4	0.84 (1)	1.74 (1)	2.580 (12)	174 (3)
O3—H3A⋯O4′	0.84 (1)	1.72 (2)	2.560 (19)	173 (3)
N1—H1A⋯O1ⁱ	0.88 (1)	2.06 (1)	2.929 (2)	171 (3)
N1—H1B⋯O2ⁱⁱ	0.88 (1)	2.08 (1)	2.931 (3)	164 (3)
O4—H4B⋯O1ⁱⁱⁱ	0.84 (1)	2.05 (3)	2.802 (11)	149 (5)
O4′—H4C⋯O1ⁱⁱⁱ	0.84 (1)	1.90 (5)	2.606 (18)	141 (7)
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 2
The molecular structure of (I), with atomic numbering and displacement ellipsoids at the 50% probability level. For clarity, only the major disorder component of 2-propanol is shown.

Figure 3
Hydrogen bonding in the crystal of (I), viewed along [010]. For clarity, the minor component and the lower-left molecule of 2-propanol are omitted from the unit cell. The dashed green lines represent amide dimerization. The dashed magenta lines represent the hydrogen bonds that form chains along [100]. The dashed orange line and its magenta counterpart (O2⋯N1) illustrate head-to-tail dimerization.

A dihedral angle of 88.26 (11)° is observed between the best-fit planes of the carbamoyl group (O1/N1/C1) and the benzene ring (C2–C7; Fig. 4). The corresponding angle is also shown for 2,4,6-trimethyl- (IV; Gdaniec et al., 2004 ), 2,6-dichloro- (V; Mukherjee et al., 2013 ), 2,6-difluoro- (VI; Rauf et al., 2006 ), and unsubstituted (VII; Blake et al., 1972 ) benzamides. Although none of these reported crystals contain a para-carboxyl group, crystal (I) fits the expected trend. The ortho Br atoms cause a carbamoyl inclination slightly larger than the inclination observed with ortho methyl groups, which is in turn larger than inclinations caused by ortho Cl, F, or H atoms.

Figure 4
Substituted benzamides, in their crystals, viewed along carbamoyl group ipso bonds. The listed dihedral angles (ω) are between the best-fit planes of the respective benzene rings and carbamoyl groups.

Synthesis and crystallization

3,5-Dibromo-4-carbamoylbenzoic acid (I): a portion of compound (II) (589 mg, Fig. 1) taken from our prior study (Noland et al., 2017) was placed in a round-bottomed flask with water (5 ml), 2-propanol (5 ml) and NaOH (186 mg). The resulting mixture was refluxed for 1 h, and then cooled to 290 K. Hydrochloric acid (6 M) was added dropwise until the pH of the mixture was less than 4. An off-white precipitate was collected by suction filtration, and then triturated with 2-propanol, giving a white powder (476 mg, 78%), m.p. 528–529 K. ¹H NMR (500 MHz, DMSO-d₆) δ 13.705 (s, 1H, H3A), 8.124 (s, 1H, H1A or H1B), 8.069 (s, 2H, H4A, H6A), 7.887 (s, 1H, H1B or H1A); ¹³C NMR (126 MHz, DMSO-d₆) δ 166.8 (1 C, C1 or C8), 164.5 (1 C, C8 or C1), 144.3 (1 C, C5), 133.4 (1 C, C2), 132.0 (2 C, C4, C6), 119.7 (2 C, C3, C7); IR (KBr, cm⁻¹) 3442, 3314, 3185, 3088, 2921, 2487, 1719, 1648, 1604, 1542, 1371, 1270, 901, 743; MS (ESI, m/z) [M − H]⁻ calculated for C₈H₅⁸¹Br⁷⁹BrNO₃ 321.8543, found 321.8549.

Crystallization: a portion of the white powder was dissolved in refluxing 2-propanol and the resulting mixture was incrementally cooled to 268 K over 6 h. Crystals were collected by decantation, and then washed with 2-propanol.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₅Br₂NO₃·C₃H₈O
M_r	383.04
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	173
a, b, c (Å)	7.2866 (5), 8.5212 (6), 12.1832 (8)
α, β, γ (°)	71.376 (1), 81.745 (1), 83.682 (1)
V (Å³)	707.76 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	5.73
Crystal size (mm)	0.40 × 0.38 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.486, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	8139, 3128, 2683
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.645

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.065, 1.04
No. of reflections	3128
No. of parameters	201
No. of restraints	151
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.90
Computer programs: APEX3 and SAINT (Bruker, 2018 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1525812

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314621003916/hb4381sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621003916/hb4381Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314621003916/hb4381Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

3,5-Dibromo-4-carbamoylbenzoic acid 2-propanol monosolvate top

Crystal data top

C₈H₅Br₂NO₃·C₃H₈O	F(000) = 376
M_r = 383.04	D_x = 1.797 Mg m⁻³
Triclinic, P1	Melting point: 528 K
a = 7.2866 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5212 (6) Å	Cell parameters from 2971 reflections
c = 12.1832 (8) Å	θ = 2.6–27.3°
α = 71.376 (1)°	µ = 5.73 mm⁻¹
β = 81.745 (1)°	T = 173 K
γ = 83.682 (1)°	Block, colourless
V = 707.76 (8) Å³	0.40 × 0.38 × 0.16 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	2683 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.021
φ and ω scans	θ_max = 27.3°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −9→9
T_min = 0.486, T_max = 0.746	k = −11→10
8139 measured reflections	l = −15→15
3128 independent reflections

Refinement top

Refinement on F²	151 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.065	w = 1/[σ²(F_o²) + (0.0296P)² + 0.5063P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3128 reflections	Δρ_max = 0.63 e Å⁻³
201 parameters	Δρ_min = −0.90 e Å⁻³

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.

Angle of C2/C3/C4/C5/C6/C7 vs. N1/C1/O1 below Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

6.9373 (0.0020) x - 1.2809 (0.0074) y + 2.6193 (0.0107) z = 5.8890 (0.0086)

* 0.0044 (0.0015) C2 * -0.0085 (0.0016) C3 * 0.0048 (0.0015) C4 * 0.0030 (0.0015) C5 * -0.0070 (0.0015) C6 * 0.0033 (0.0015) C7

Rms deviation of fitted atoms = 0.0055

1.3629 (0.0122) x + 7.5482 (0.0167) y + 8.7867 (0.0367) z = 9.5168 (0.0262)

Angle to previous plane (with approximate esd) = 88.256 ( 0.113 )

* 0.0000 (0.0000) N1 * 0.0000 (0.0000) C1 * 0.0000 (0.0000) O1

Rms deviation of fitted atoms = 0.0000

Refinement. A direct-methods solution was calculated, followed by full-matrix least squares / difference Fourier cycles. All H atoms were placed in calculated positions (C—H = 0.95–1.00 Å, N—H = 0.88 Å, O—H = 0.84 Å) and refined as riding atoms with U_iso(H) set to 1.2 or 1.5U_eq(C/N/O).

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.61784 (4)	0.53550 (3)	0.84990 (2)	0.04348 (9)
Br2	0.61751 (4)	0.03664 (3)	0.63196 (2)	0.04169 (9)
O1	0.6947 (2)	0.0875 (2)	0.90019 (14)	0.0332 (4)
O2	0.8164 (3)	0.6055 (2)	0.30554 (14)	0.0405 (4)
O3	0.8603 (3)	0.7832 (2)	0.39910 (15)	0.0416 (4)
H3A	0.891 (4)	0.846 (3)	0.3317 (11)	0.050*
N1	0.3942 (3)	0.1688 (3)	0.87692 (17)	0.0327 (4)
H1A	0.355 (4)	0.097 (3)	0.9439 (12)	0.039*
H1B	0.312 (3)	0.227 (3)	0.8307 (19)	0.039*
C1	0.5730 (3)	0.1757 (3)	0.84327 (18)	0.0252 (4)
C2	0.6307 (3)	0.3004 (3)	0.72637 (17)	0.0241 (4)
C3	0.6625 (3)	0.4624 (3)	0.71657 (19)	0.0265 (4)
C4	0.7250 (3)	0.5743 (3)	0.61079 (19)	0.0278 (5)
H4A	0.748438	0.683825	0.606128	0.033*
C5	0.7527 (3)	0.5239 (3)	0.51214 (18)	0.0264 (5)
C6	0.7196 (3)	0.3647 (3)	0.51800 (19)	0.0276 (5)
H6A	0.737311	0.331352	0.449673	0.033*
C7	0.6603 (3)	0.2545 (3)	0.62524 (19)	0.0256 (4)
C8	0.8134 (3)	0.6414 (3)	0.3944 (2)	0.0308 (5)
O4	0.9365 (13)	0.9719 (9)	0.1879 (11)	0.0313 (15)	0.598 (8)
H4B	1.0530 (14)	0.964 (8)	0.184 (5)	0.047*	0.598 (8)
C9	0.872 (3)	1.205 (2)	0.2603 (12)	0.060 (2)	0.598 (8)
H9A	0.820755	1.320374	0.241438	0.091*	0.598 (8)
H9B	1.000209	1.198652	0.278449	0.091*	0.598 (8)
H9C	0.796644	1.135893	0.327854	0.091*	0.598 (8)
C10	0.8716 (7)	1.1441 (5)	0.1583 (4)	0.0345 (13)	0.598 (8)
H10A	0.739971	1.152928	0.141246	0.041*	0.598 (8)
C11	0.9845 (12)	1.2460 (14)	0.0493 (7)	0.0429 (18)	0.598 (8)
H11A	0.979250	1.201108	−0.014763	0.064*	0.598 (8)
H11B	1.113936	1.241251	0.064208	0.064*	0.598 (8)
H11C	0.933135	1.361577	0.028151	0.064*	0.598 (8)
O4'	0.978 (2)	0.9791 (14)	0.1997 (18)	0.0313 (15)	0.402 (8)
H4C	1.049 (8)	0.954 (10)	0.146 (5)	0.047*	0.402 (8)
C9'	0.883 (5)	1.202 (4)	0.2791 (18)	0.060 (2)	0.402 (8)
H9D	0.887410	1.321374	0.265058	0.091*	0.402 (8)
H9E	0.938938	1.140568	0.350651	0.091*	0.402 (8)
H9F	0.753869	1.174455	0.287647	0.091*	0.402 (8)
C10'	0.9900 (11)	1.1550 (7)	0.1784 (5)	0.0304 (17)	0.402 (8)
H10B	1.123331	1.176385	0.174482	0.036*	0.402 (8)
C11'	0.9228 (19)	1.250 (2)	0.0639 (10)	0.0429 (18)	0.402 (8)
H11D	0.793361	1.227577	0.065230	0.064*	0.402 (8)
H11E	1.000083	1.215842	0.001592	0.064*	0.402 (8)
H11F	0.931011	1.369041	0.049729	0.064*	0.402 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0693 (2)	0.03621 (15)	0.02540 (13)	−0.00969 (12)	0.00169 (12)	−0.01126 (10)
Br2	0.05996 (18)	0.02835 (13)	0.03767 (15)	−0.01118 (11)	−0.00300 (12)	−0.00992 (11)
O1	0.0278 (8)	0.0364 (9)	0.0226 (8)	−0.0049 (7)	−0.0010 (6)	0.0086 (7)
O2	0.0473 (10)	0.0395 (10)	0.0201 (8)	0.0044 (8)	0.0024 (7)	0.0058 (7)
O3	0.0468 (10)	0.0323 (9)	0.0294 (9)	−0.0094 (8)	0.0080 (8)	0.0101 (7)
N1	0.0295 (10)	0.0359 (11)	0.0200 (10)	−0.0038 (8)	0.0008 (8)	0.0080 (8)
C1	0.0314 (11)	0.0240 (10)	0.0155 (10)	−0.0062 (9)	0.0000 (8)	0.0007 (8)
C2	0.0260 (10)	0.0237 (10)	0.0170 (10)	−0.0044 (8)	−0.0003 (8)	0.0016 (8)
C3	0.0309 (11)	0.0270 (11)	0.0186 (10)	−0.0023 (9)	−0.0007 (8)	−0.0039 (8)
C4	0.0284 (11)	0.0238 (10)	0.0259 (11)	−0.0044 (9)	−0.0024 (9)	0.0005 (9)
C5	0.0221 (10)	0.0276 (11)	0.0195 (10)	−0.0012 (8)	0.0004 (8)	0.0053 (8)
C6	0.0295 (11)	0.0299 (11)	0.0184 (10)	0.0003 (9)	−0.0010 (8)	−0.0022 (9)
C7	0.0281 (11)	0.0231 (10)	0.0218 (10)	−0.0033 (8)	−0.0011 (8)	−0.0019 (8)
C8	0.0222 (10)	0.0311 (12)	0.0246 (11)	0.0025 (9)	0.0016 (9)	0.0080 (9)
O4	0.026 (4)	0.0233 (10)	0.034 (3)	−0.0051 (17)	0.008 (3)	0.0027 (10)
C9	0.091 (4)	0.0453 (19)	0.042 (4)	−0.0020 (19)	0.009 (4)	−0.016 (3)
C10	0.036 (3)	0.027 (2)	0.035 (2)	0.0005 (17)	−0.0004 (19)	−0.0050 (17)
C11	0.059 (6)	0.0292 (15)	0.032 (2)	−0.001 (4)	0.000 (3)	0.0010 (18)
O4'	0.026 (4)	0.0233 (10)	0.034 (3)	−0.0051 (17)	0.008 (3)	0.0027 (10)
C9'	0.091 (4)	0.0453 (19)	0.042 (4)	−0.0020 (19)	0.009 (4)	−0.016 (3)
C10'	0.039 (4)	0.020 (3)	0.030 (3)	−0.007 (2)	−0.009 (2)	−0.001 (2)
C11'	0.059 (6)	0.0292 (15)	0.032 (2)	−0.001 (4)	0.000 (3)	0.0010 (18)

Geometric parameters (Å, º) top

Br1—C3	1.893 (2)	C9—C10	1.492 (10)
Br2—C7	1.890 (2)	C9—H9A	0.9800
O1—C1	1.236 (3)	C9—H9B	0.9800
O2—C8	1.213 (3)	C9—H9C	0.9800
O3—C8	1.311 (3)	C10—C11	1.517 (8)
O3—H3A	0.839 (3)	C10—H10A	1.0000
N1—C1	1.311 (3)	C11—H11A	0.9800
N1—H1A	0.880 (3)	C11—H11B	0.9800
N1—H1B	0.880 (3)	C11—H11C	0.9800
C1—C2	1.515 (3)	O4'—C10'	1.448 (11)
C2—C3	1.389 (3)	O4'—H4C	0.840 (3)
C2—C7	1.390 (3)	C9'—C10'	1.497 (13)
C3—C4	1.385 (3)	C9'—H9D	0.9800
C4—C5	1.382 (3)	C9'—H9E	0.9800
C4—H4A	0.9500	C9'—H9F	0.9800
C5—C6	1.381 (3)	C10'—C11'	1.492 (12)
C5—C8	1.501 (3)	C10'—H10B	1.0000
C6—C7	1.385 (3)	C11'—H11D	0.9800
C6—H6A	0.9500	C11'—H11E	0.9800
O4—C10	1.437 (8)	C11'—H11F	0.9800
O4—H4B	0.840 (3)

C8—O3—H3A	110 (2)	H9A—C9—H9C	109.5
C1—N1—H1A	119.3 (18)	H9B—C9—H9C	109.5
C1—N1—H1B	121.2 (18)	O4—C10—C9	109.7 (8)
H1A—N1—H1B	119 (2)	O4—C10—C11	110.9 (7)
O1—C1—N1	124.32 (19)	C9—C10—C11	112.8 (10)
O1—C1—C2	118.97 (19)	O4—C10—H10A	107.8
N1—C1—C2	116.71 (19)	C9—C10—H10A	107.8
C3—C2—C7	117.58 (19)	C11—C10—H10A	107.8
C3—C2—C1	121.60 (19)	C10—C11—H11A	109.5
C7—C2—C1	120.79 (19)	C10—C11—H11B	109.5
C4—C3—C2	121.8 (2)	H11A—C11—H11B	109.5
C4—C3—Br1	118.38 (17)	C10—C11—H11C	109.5
C2—C3—Br1	119.85 (16)	H11A—C11—H11C	109.5
C5—C4—C3	118.9 (2)	H11B—C11—H11C	109.5
C5—C4—H4A	120.5	C10'—O4'—H4C	106 (6)
C3—C4—H4A	120.5	C10'—C9'—H9D	109.5
C6—C5—C4	121.02 (19)	C10'—C9'—H9E	109.5
C6—C5—C8	117.7 (2)	H9D—C9'—H9E	109.5
C4—C5—C8	121.3 (2)	C10'—C9'—H9F	109.5
C5—C6—C7	118.9 (2)	H9D—C9'—H9F	109.5
C5—C6—H6A	120.6	H9E—C9'—H9F	109.5
C7—C6—H6A	120.6	O4'—C10'—C9'	108.5 (13)
C6—C7—C2	121.8 (2)	O4'—C10'—C11'	109.7 (10)
C6—C7—Br2	118.33 (17)	C9'—C10'—C11'	113.5 (14)
C2—C7—Br2	119.82 (15)	O4'—C10'—H10B	108.3
O2—C8—O3	124.9 (2)	C9'—C10'—H10B	108.3
O2—C8—C5	122.0 (2)	C11'—C10'—H10B	108.3
O3—C8—C5	113.2 (2)	C10'—C11'—H11D	109.5
C10—O4—H4B	109 (5)	C10'—C11'—H11E	109.5
C10—C9—H9A	109.5	H11D—C11'—H11E	109.5
C10—C9—H9B	109.5	C10'—C11'—H11F	109.5
H9A—C9—H9B	109.5	H11D—C11'—H11F	109.5
C10—C9—H9C	109.5	H11E—C11'—H11F	109.5

O1—C1—C2—C3	−91.0 (3)	C4—C5—C6—C7	−0.9 (3)
N1—C1—C2—C3	89.3 (3)	C8—C5—C6—C7	−178.9 (2)
O1—C1—C2—C7	86.7 (3)	C5—C6—C7—C2	0.9 (3)
N1—C1—C2—C7	−93.0 (3)	C5—C6—C7—Br2	−179.53 (16)
C7—C2—C3—C4	−1.3 (3)	C3—C2—C7—C6	0.1 (3)
C1—C2—C3—C4	176.4 (2)	C1—C2—C7—C6	−177.6 (2)
C7—C2—C3—Br1	178.09 (16)	C3—C2—C7—Br2	−179.40 (16)
C1—C2—C3—Br1	−4.2 (3)	C1—C2—C7—Br2	2.8 (3)
C2—C3—C4—C5	1.3 (3)	C6—C5—C8—O2	7.2 (3)
Br1—C3—C4—C5	−178.05 (16)	C4—C5—C8—O2	−170.8 (2)
C3—C4—C5—C6	−0.2 (3)	C6—C5—C8—O3	−173.2 (2)
C3—C4—C5—C8	177.7 (2)	C4—C5—C8—O3	8.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O4	0.84 (1)	1.74 (1)	2.580 (12)	174 (3)
O3—H3A···O4′	0.84 (1)	1.72 (2)	2.560 (19)	173 (3)
N1—H1A···O1ⁱ	0.88 (1)	2.06 (1)	2.929 (2)	171 (3)
N1—H1B···O2ⁱⁱ	0.88 (1)	2.08 (1)	2.931 (3)	164 (3)
O4—H4B···O1ⁱⁱⁱ	0.84 (1)	2.05 (3)	2.802 (11)	149 (5)
O4′—H4C···O1ⁱⁱⁱ	0.84 (1)	1.90 (5)	2.606 (18)	141 (7)

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

Acknowledgements

The authors thank Victor G. Young, Jr (X-Ray Crystallographic Laboratory, University of Minnesota) for assistance with the crystallographic determination, and the Wayland E. Noland Research Fellowship Fund at the University of Minnesota for generous financial support of this project.

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