Syntheses and crystal structures of benzyl N'-[(E)-2-hydroxybenzylidene]hydrazinecarboxylate and benzyl N'-[(E)-5-bromo-2-hydroxybenzylidene]hydrazinecarboxylate.

Benzyl N'-[(E)-2-hydroxybenzylidene]hydrazinecarboxylate, C15H14N2O3 (I) and benzyl N'-[(E)-5-bromo-2-hydroxybenzylidene]hydrazinecarboxylate (II), C15H13BrN2O3, have been synthesized by the reaction of either 2-hy-droxy-benzaldehyde or 5-bromo-2-hy-droxy-benzaldehyde with benzyl carbazate, respectively. Both the compounds crystallize in the monoclinic crystal system with space groups Pn (Z' = 1, I) and P21/c (Z' = 2, II). Mol-ecular conformations in each structure are similar, and both structures feature strong intra-molecular O-H⋯N hydrogen bonds, which form S(6) ring motifs. There are also strong N-H⋯O and weak C-H⋯O hydrogen bonds in both structures, but their modes of packing within their respective crystals are markedly different. Some comparisons are made with the structures of a few related compounds. © Vinaya et al. 2022.

Chemical context

Hy­droxy­benzyl­idene hydrazines exhibit a wide spectrum of biological activities (Sersen et al., 2017 ▸). Benzaldehyde­hydrazone derivatives have received considerable attention for several decades as a result of their pharmacological activity (Parashar et al., 1988 ▸) and photochromic properties (Hadjoudis et al., 1987 ▸). Benzaldehyde­hydrazone derivatives are also important inter­mediates in the synthesis of 1,3,4-oxa­diazo­les, which are versatile compounds with many useful properties (Borg et al., 1999 ▸). Synthesis and biological activities of new hydrazide derivatives (Özdemir et al., 2009 ▸) and biological activities of hydrazone derivatives (Rollas & Küçükgüzel, 2007 ▸) have been reported. In view of the importance of benzyl­idene hydrazines and benzaldehyde­hydrazone derivatives in general, this paper reports the crystal structures of the title compounds, C15H14N2O3 (I), and C15H13BrN2O3 (II).

Structural commentary

The mol­ecular structures of benzyl N′-[(E)-2-hydroxyben­zylidene]hydrazinecarboxylate (I) (Fig. 1 ▸) and benzyl N′-[(E)-5-bromo-2-hydroxybenzylidene]hydrazinecarboxylate (II) (Fig. 2 ▸) each consist of a central N′-methyl­idene­meth­oxy­carboxyl core flanked by a benzyl group attached to the singly bonded oxygen and a 2-hy­droxy­phenyl (I) or 5-bromo-2-hy­droxy­phenyl (II) attached to the methyl­idene. There are no unusual bond lengths or angles in either structure. The mol­ecules have strong intra­molecular O—H⋯N hydrogen bonds (Tables 1 ▸ and 2 ▸), forming S(6) ring motifs (Etter et al., 1990 ▸). The asymmetric unit of I contains a single mol­ecule while that of II contains two (labelled A and B in Fig. 2 ▸). In each case, the [(hy­droxy­phen­yl)methyl­idene]carbohydrazide moieties are essentially planar [r.m.s. deviations 0.0429 Å (I), 0.0905 Å (II ), 0.0692 (II )]. These form dihedral angles of 79.92 (3)°, 79.74 (4)°, and 74.27 (4)° to the benzyl groups of I, II , and II , respectively. Indeed, the V-shaped conformations of II , and II are strikingly similar, with I only deviating to any appreciable degree at the benzyl group, as evidenced by an overlay of the three mol­ecules (Fig. 3 ▸). The conformation of I differs from II and II primarily by the torsion angles about bonds O2—C9 and C9—C10 (Table 3 ▸).

Figure 1

An ellipsoid plot (50% probability) of I, showing the intra­molecular hydrogen bond (O1—H1O⋯N1) as a dashed line.

Figure 2

An ellipsoid plot of the asymmetric unit of II, showing the intra­molecular hydrogen bonds (O1A—H1AO⋯N1A and O1B—H1BO⋯N1B) as dashed lines.

Table 1

Hydrogen-bond geometry (Å, °) for I

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N1	0.90 (3)	1.73 (3)	2.546 (2)	148 (2)
N2—H2N⋯O1i	0.87 (2)	1.97 (2)	2.8225 (19)	168 (2)
C7—H7⋯O3ii	0.95	2.43	3.271 (2)	147

Symmetry codes: (i) ; (ii) .

Table 2

Hydrogen-bond geometry (Å, °) for II

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1A—H1AO⋯N1A	0.82 (2)	1.81 (2)	2.565 (2)	151 (2)
N2A—H2AN⋯O1A i	0.87 (2)	2.04 (2)	2.902 (2)	171 (2)
C3A—H3A⋯O2A ii	0.95	2.50	3.392 (2)	156
C6A—H6A⋯O3A i	0.95	2.38	3.296 (2)	161
O1B—H1BO⋯N1B	0.80 (2)	1.84 (2)	2.558 (2)	148 (2)
N2B—H2BN⋯O1B iii	0.88 (2)	2.04 (2)	2.915 (2)	171 (2)
C3B—H3B⋯O2B iv	0.95	2.44	3.360 (2)	164
C6B—H6B⋯O3B iii	0.95	2.39	3.297 (2)	159

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Figure 3

A least-squares fit overlay of I, II , and II showing the similarity of their conformations. That of I (blue) differs primarily in the orientation of the benzyl group (right). Diagram generated using Mercury (Macrae et al., 2020 ▸).

Table 3

Selected torsion angles (°) for I, II and II

I
C8—O2—C9—C10	−78.01 (18)	O2—C9—C10—C11	−59.9 (2)
II
C8A—O2A—C9A—C10A	−98.12 (19)	O2A—C9A—C10A—C11A	−88.3 (2)
C8B—O2B—C9B—C10B	−98.0 (2)	O2B—C9B—C10B—C11B	−84.5 (2)

The above torsion angles qu­antify the most substantive differences between the conformations of I, II and II.

Supra­molecular features

In addition to the strong O—H⋯N intramol­ecular hydrogen bonds in I and II, the structures both feature strong N—H⋯O and weaker C—H⋯O intermol­ecular hydrogen bonds. These inter­actions are summarized in Tables 1 ▸ and 2 ▸. The packing modes are, however, quite different.

In I, the V-shaped (Fig. 3 ▸) mol­ecules stack into columns along [100] (Fig. 4 ▸). These columns inter­act with n-glide-related columns via the strong N2—H2N⋯O1i (symmetry codes as per Table 1 ▸) hydrogen bonds to give C(7) chains (Etter et al., 1990 ▸) and with different n-glide-related columns via the bifurcated C6—H6⋯O3ii and C7—H7⋯O3ii (Table 1 ▸) hydrogen bonds. In combination, these inter­actions produce layers that extend in the ac plane (Fig. 5 ▸), which in turn stack along [010].

Figure 4

V-shaped mol­ecules of I stack into columns parallel to the a-axis direction.

Figure 5

A partial packing plot of I showing hydrogen bonding as dashed lines. N—H⋯O and a pair of C—H⋯O (bifurcated) hydrogen bonds link n-glide-related mol­ecules into layers parallel to ac.

In II, the independent mol­ecules (A and B) make hydrogen bonds to 21-screw-related copies of themselves via strong (N2—H2N⋯O1) and weak (C3—H3⋯O2 and C6—H6⋯O3) hydrogen bonds (Table 2 ▸), forming (8) and (13) ring motifs (Etter et al., 1990 ▸), leading to adjacent pairs of ribbons that extend along [010] (Fig. 6 ▸). The 5-bromo-2-hy­droxy­phenyl and benzyl groups of II and II have notably different environments. For example, inversion-related (−x, −y, −z) pairs of II mol­ecules have close contacts of 3.3379 (9) Å between their Br1A atoms and the centroid of the inversion-related C10A–C15A ring. There is no corresponding close contact for the II mol­ecule (Fig. 7 ▸).

Figure 6

A partial packing plot of II showing N—H⋯O and C—H⋯O hydrogen-bonded ribbons along [010] of II (upper) and II (lower) mol­ecules.

Figure 7

In spite of their similar conformations, inversion-related pairs of II mol­ecules (upper) are different from inversion-related pairs of II mol­ecules (lower). For II there are close contacts between bromine and the inversion-related benzene ring, as shown by the dotted line. No such inter­action exists for II .

The differences in packing are also apparent in the atom–atom contact coverages, as qu­anti­fied by CrystalExplorer (Spackman et al., 2021 ▸) fingerprint diagrams (Figs. 8 ▸ and 9 ▸).

Figure 8

Fingerprint plots obtained from a Hirshfeld surface analysis for I using CrystalExplorer, separated into (a) H⋯H (47.4% coverage), (b) C⋯H/H⋯C (24.4%), (c) O⋯H/H⋯O (17.5%), (d) C⋯C (4.2%). All other contacts are negligible.

Figure 9

Fingerprint plots obtained from a Hirshfeld surface analysis for II using CrystalExplorer, separated into (a) H⋯H (33.8% coverage), (b) C⋯H/H⋯C (23.8%), (c) O⋯H/H⋯O (15.4%), (d) Br⋯H/H⋯Br (12.6%). All other contacts are negligible.

Database survey

A search of the Cambridge Structure Database (CSD, v5.43 with updates as of June 2022; Groom et al., 2016 ▸) for a search fragment consisting of the structure of I, but with the two aromatic rings replaced by ‘any group’ gave 340 hits. A fragment including the benzyl group attached to the equivalent of O2 in I/II gave 105 hits, while a fragment including a phenyl ring at C7 gave 37 hits. A fragment consisting of I but without the phenolic OH group gave just four hits: HIXQIQ (Dong & Wang, 2014 ▸), QAVFAY (Shen et al., 2022 ▸), GEZTUD (Chang et al., 2018 ▸) and PIVKUD (Zhang et al., 2019 ▸). In HIXQIQ, a 5-chloro-2-hy­droxy-2-(meth­oxy­carbon­yl)-2,3-di­hydro-1H-in­den-1-yl­idene) group is attached to the hydrazine. QAVFAY features a four-membered 1,2-diazete ring, with the phenyl group fluorinated at its 4-position. Structures GEZTUD and PIVKUD each feature pyrazole rings; the former having a 2,2,2-tri­fluoro­ethyl group attached to the pyrazole and a methyl at the 4-position of the phenyl ring, and the latter having a 3,4,5-tri­meth­oxy­phenyl attached to its pyrazole ring.

New Schiff bases derived from benzyl carbazate with alkyl and heteroaryl ketones and crystal structures of benzyl 2-cyclo­pentyl­idenehydrazine­carboxyl­ate (JENFAM, (E)-benzyl 2-[1-(pyridin-3-yl)ethyl­idene]hydrazine-1-carboxyl­ate (JENFEQ), (E)-benzyl2-[1-(pyridin-4-yl)ethyl­idene]hydrazine­carboxyl­ate (JENFIU) (Nithya et al., 2017 ▸) have also been reported. A selection of other structures similar to I and II deposited in the CSD are listed in Table 4 ▸.

Table 4

A sample of structures similar to I and II in the CSD

R and R′ represent groups attached at the equivalent of C4 and R′′ represents the group attached at the equivalent of O3.

CSD refcode	R	R′	R′′	Reference
HODLOC	2-hy­droxy­phen­yl	H	meth­yl	Sun & Cheng (2008 ▸)
QOFLAZ	2-hy­droxy­phen­yl	H	eth­yl	Gao (2008 ▸)
KODVUV	4-hy­droxy­phen­yl	H	meth­yl	Cheng (2008a ▸)
XOGVEV	phen­yl	meth­yl	meth­yl	Cheng (2008b ▸)
XOGXEX	4-hy­droxy­phen­yl	H	eth­yl	Cheng (2008c ▸)
XOGXIB	3-meth­oxy-4-hy­droxy­phen­yl	H	meth­yl	Cheng (2008d ▸)
AZOTAL	3-hy­droxy­phen­yl	H	meth­yl	Li et al. (2011 ▸)
AWUJAE	3-hy­droxy­phen­yl	H	eth­yl	Hu et al. (2011 ▸)
WEFRUX	4-di­ethyl­amino-2-hy­droxy­phen­yl	H	meth­yl	Lv et al. (2017 ▸)

Synthesis and crystallization

Preparation of I and II followed similar synthetic routes. Either 2-hy­droxy­benzaldehyde (1.2 g, 0.01 mol) (for I) or 5-bromo-2-hy­droxy­benzaldehyde (2.0 g, 0.01 mol) (for II) and benzyl carbazate (1.66 g, 0.01 mol) were dissolved in methanol (25 ml) and stirred for 3 h at room temperature. The resulting solids were filtered off and recrystallized from ethanol to give I and II with yields of 80% in both cases. The general reaction scheme is summarized in Fig. 10 ▸. Single crystals suitable for X-ray analysis for both I and II were obtained by slow evaporation of methano­lic solutions at room temperature (m.p.: 400–402 K for I and 468–470 K for II).

Figure 10

Reaction scheme for the synthesis of I and II.

Crystal handling, data collection, and refinement

Crystals of I and II were each secured on the tips of fine glass fibres held in copper mounting pins. The crystal of I was mounted from a shallow liquid-nitro­gen dewar using tongs first developed for protein cryocrystallography (Parkin & Hope, 1998 ▸), while the crystal of II was mounted directly into a cold-nitro­gen stream. Data for both samples (Cu Kα for I and Mo Kα for II) were collected with the crystals held at 90.0 (2) K. Determination of the absolute structure for I was inconclusive via traditional full-matrix refinement of Flack’s parameter [x = −0.08 (18); Flack & Bernardinelli, 1999 ▸], but Hooft’s Bayesian approach [y = 0.00 (8); Hooft et al. (2008 ▸), as calculated using PLATON (Spek, 2020 ▸)] and Parsons’ quotient method [z = 0.04 (10); Parsons et al., 2013 ▸] give credence to the assignment. Refinement progress was checked using PLATON (Spek, 2020 ▸) and by an R-tensor (Parkin, 2000 ▸). Crystal data, data collection, and refinement statistics are summarized in Table 5 ▸. Carbon-bound hydrogen atoms were included using riding models, with C—H distances constrained to 0.95 Å for Csp 2H and 0.99 Å for R 2CH2. N—H and O—H hydrogen-atom coord­inates were refined. U iso(H) parameters were set to values of either 1.2U eq (C—H, N—H) or 1.5U eq (O—H) of the attached atom.

Table 5

Experimental details

	I	II
Crystal data
Chemical formula	C15H14N2O3	C15H13BrN2O3
M r	270.28	349.18
Crystal system, space group	Monoclinic, P n	Monoclinic, P21/c
Temperature (K)	90	90
a, b, c (Å)	4.5017 (12), 14.047 (4), 10.567 (3)	27.904 (2), 11.1207 (6), 9.0648 (7)
β (°)	96.300 (15)	94.485 (2)
V (Å3)	664.2 (3)	2804.3 (3)
Z	2	8
Radiation type	Cu Kα	Mo Kα
μ (mm−1)	0.79	2.94
Crystal size (mm)	0.41 × 0.23 × 0.02	0.24 × 0.22 × 0.05
Data collection
Diffractometer	Bruker D8 Venture dual source	Bruker D8 Venture dual source
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ▸)	Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max	0.589, 0.958	0.598, 0.862
No. of measured, independent and observed [I > 2σ(I)] reflections	7271, 2511, 2425	36145, 6401, 5004
R int	0.028	0.047
(sin θ/λ)max (Å−1)	0.625	0.650
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.024, 0.063, 1.04	0.028, 0.064, 1.03
No. of reflections	2511	6401
No. of parameters	187	391
No. of restraints	2	0
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.13, −0.13	0.36, −0.39
Absolute structure	Flack x determined using 1054 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)	–
Absolute structure parameter	0.04 (10)	–

Computer programs: APEX3 (Bruker, 2016 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2019/2 (Sheldrick, 2015b ▸), XP in SHELXTL (Sheldrick, 2008 ▸), CIFFIX (Parkin, 2013 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989022009100/yk2176sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022009100/yk2176Isup4.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989022009100/yk2176IIsup5.hkl

CCDC references: 2206989, 2206988

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H14N2O3	F(000) = 284
Mr = 270.28	Dx = 1.351 Mg m−3
Monoclinic, Pn	Cu Kα radiation, λ = 1.54184 Å
a = 4.5017 (12) Å	Cell parameters from 6841 reflections
b = 14.047 (4) Å	θ = 3.1–74.4°
c = 10.567 (3) Å	µ = 0.79 mm−1
β = 96.300 (15)°	T = 90 K
V = 664.2 (3) Å3	Plate, colourless
Z = 2	0.41 × 0.23 × 0.02 mm

Bruker D8 Venture dual source diffractometer	2511 independent reflections
Radiation source: microsource	2425 reflections with I > 2σ(I)
Detector resolution: 7.41 pixels mm-1	Rint = 0.028
φ and ω scans	θmax = 74.6°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −5→5
Tmin = 0.589, Tmax = 0.958	k = −17→16
7271 measured reflections	l = −13→12

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.063	w = 1/[σ2(Fo2) + (0.0283P)2 + 0.0531P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2511 reflections	Δρmax = 0.13 e Å−3
187 parameters	Δρmin = −0.13 e Å−3
2 restraints	Absolute structure: Flack x determined using 1054 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (10)

Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was flash-cooled in liquid nitrogen and mounted into the cold gas stream of a liquid-nitrogen based cryostat using specially designed tongs (Parkin & Hope, 1998). Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals.

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. Refinement progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF.

	x	y	z	Uiso*/Ueq
O1	0.7525 (3)	0.44387 (9)	0.34649 (11)	0.0268 (3)
H1O	0.631 (6)	0.4786 (18)	0.391 (3)	0.040*
O2	−0.0407 (3)	0.67535 (9)	0.56997 (11)	0.0243 (3)
O3	0.2021 (3)	0.64243 (9)	0.39780 (11)	0.0248 (3)
N1	0.4688 (3)	0.49495 (10)	0.53076 (13)	0.0202 (3)
N2	0.2728 (3)	0.55477 (11)	0.58048 (13)	0.0214 (3)
H2N	0.242 (5)	0.5508 (15)	0.660 (2)	0.026*
C1	0.7887 (3)	0.36137 (13)	0.54751 (15)	0.0205 (3)
C2	0.8612 (4)	0.37060 (12)	0.42217 (16)	0.0221 (4)
C3	1.0493 (4)	0.30492 (14)	0.37311 (16)	0.0275 (4)
H3	1.101603	0.312160	0.288959	0.033*
C4	1.1602 (4)	0.22882 (14)	0.44739 (19)	0.0300 (4)
H4	1.284895	0.183155	0.413092	0.036*
C5	1.0907 (4)	0.21882 (14)	0.57132 (18)	0.0289 (4)
H5	1.168389	0.166681	0.621816	0.035*
C6	0.9082 (4)	0.28486 (13)	0.62116 (15)	0.0244 (4)
H6	0.863234	0.278254	0.706480	0.029*
C7	0.5866 (4)	0.42754 (12)	0.60123 (15)	0.0204 (3)
H7	0.542993	0.420844	0.686734	0.025*
C8	0.1509 (4)	0.62582 (12)	0.50506 (15)	0.0196 (3)
C9	−0.1607 (4)	0.76046 (13)	0.50546 (17)	0.0251 (4)
H9A	−0.343944	0.780464	0.542188	0.030*
H9B	−0.215620	0.746317	0.414103	0.030*
C10	0.0630 (4)	0.83981 (12)	0.51860 (17)	0.0231 (4)
C11	0.1698 (4)	0.87256 (14)	0.63955 (19)	0.0311 (4)
H11	0.100670	0.844554	0.712731	0.037*
C12	0.3763 (5)	0.94578 (15)	0.6533 (2)	0.0401 (5)
H12	0.448310	0.967698	0.736024	0.048*
C13	0.4787 (5)	0.98720 (14)	0.5483 (3)	0.0418 (6)
H13	0.619778	1.037661	0.558367	0.050*
C14	0.3742 (5)	0.95472 (15)	0.4275 (2)	0.0390 (5)
H14	0.444340	0.982844	0.354578	0.047*
C15	0.1674 (4)	0.88122 (13)	0.41314 (18)	0.0285 (4)
H15	0.096956	0.859121	0.330295	0.034*

	U11	U22	U33	U12	U13	U23
O1	0.0369 (8)	0.0313 (7)	0.0138 (5)	0.0058 (5)	0.0090 (5)	0.0020 (5)
O2	0.0269 (6)	0.0267 (6)	0.0202 (6)	0.0045 (5)	0.0066 (5)	0.0022 (5)
O3	0.0317 (6)	0.0292 (6)	0.0137 (5)	0.0005 (5)	0.0040 (4)	0.0007 (5)
N1	0.0235 (7)	0.0242 (7)	0.0132 (6)	0.0005 (5)	0.0041 (5)	−0.0019 (5)
N2	0.0259 (8)	0.0276 (8)	0.0117 (6)	0.0044 (6)	0.0064 (5)	−0.0001 (5)
C1	0.0217 (8)	0.0251 (8)	0.0148 (7)	−0.0008 (6)	0.0029 (6)	−0.0008 (6)
C2	0.0246 (8)	0.0262 (9)	0.0154 (7)	−0.0010 (7)	0.0025 (6)	−0.0011 (7)
C3	0.0322 (10)	0.0338 (10)	0.0172 (8)	0.0015 (7)	0.0062 (7)	−0.0041 (7)
C4	0.0304 (10)	0.0316 (10)	0.0285 (9)	0.0069 (8)	0.0053 (7)	−0.0079 (8)
C5	0.0313 (9)	0.0284 (9)	0.0265 (9)	0.0061 (7)	0.0009 (7)	0.0018 (7)
C6	0.0268 (8)	0.0290 (9)	0.0174 (8)	0.0020 (7)	0.0024 (7)	0.0011 (6)
C7	0.0233 (8)	0.0269 (8)	0.0114 (7)	−0.0004 (6)	0.0035 (6)	0.0001 (6)
C8	0.0212 (8)	0.0231 (8)	0.0144 (8)	−0.0021 (6)	0.0019 (6)	−0.0019 (6)
C9	0.0216 (8)	0.0278 (9)	0.0256 (8)	0.0037 (7)	0.0009 (7)	0.0018 (7)
C10	0.0194 (7)	0.0252 (9)	0.0243 (8)	0.0063 (6)	0.0009 (6)	−0.0018 (7)
C11	0.0254 (9)	0.0386 (11)	0.0290 (9)	0.0068 (8)	0.0010 (7)	−0.0067 (8)
C12	0.0287 (10)	0.0389 (11)	0.0503 (13)	0.0061 (8)	−0.0067 (9)	−0.0187 (9)
C13	0.0240 (9)	0.0252 (10)	0.0741 (16)	0.0034 (8)	−0.0039 (10)	−0.0034 (10)
C14	0.0279 (10)	0.0339 (11)	0.0552 (12)	0.0039 (8)	0.0042 (9)	0.0155 (10)
C15	0.0251 (9)	0.031 (1)	0.0290 (9)	0.0055 (7)	0.0012 (7)	0.0053 (7)

O1—C2	1.361 (2)	C5—H5	0.9500
O1—H1O	0.90 (3)	C6—H6	0.9500
O2—C8	1.352 (2)	C7—H7	0.9500
O2—C9	1.451 (2)	C9—C10	1.498 (2)
O3—C8	1.204 (2)	C9—H9A	0.9900
N1—C7	1.283 (2)	C9—H9B	0.9900
N1—N2	1.365 (2)	C10—C15	1.384 (3)
N2—C8	1.355 (2)	C10—C11	1.393 (3)
N2—H2N	0.87 (2)	C11—C12	1.383 (3)
C1—C6	1.399 (2)	C11—H11	0.9500
C1—C2	1.405 (2)	C12—C13	1.376 (4)
C1—C7	1.459 (2)	C12—H12	0.9500
C2—C3	1.390 (3)	C13—C14	1.388 (4)
C3—C4	1.386 (3)	C13—H13	0.9500
C3—H3	0.9500	C14—C15	1.387 (3)
C4—C5	1.387 (3)	C14—H14	0.9500
C4—H4	0.9500	C15—H15	0.9500
C5—C6	1.381 (3)
C2—O1—H1O	107.5 (17)	O3—C8—O2	125.21 (16)
C8—O2—C9	114.27 (13)	O3—C8—N2	126.12 (17)
C7—N1—N2	118.33 (14)	O2—C8—N2	108.67 (14)
C8—N2—N1	117.65 (14)	O2—C9—C10	110.94 (13)
C8—N2—H2N	121.3 (14)	O2—C9—H9A	109.5
N1—N2—H2N	120.8 (15)	C10—C9—H9A	109.5
C6—C1—C2	118.71 (16)	O2—C9—H9B	109.5
C6—C1—C7	119.42 (15)	C10—C9—H9B	109.5
C2—C1—C7	121.85 (15)	H9A—C9—H9B	108.0
O1—C2—C3	118.50 (16)	C15—C10—C11	119.09 (18)
O1—C2—C1	121.20 (16)	C15—C10—C9	121.48 (16)
C3—C2—C1	120.30 (16)	C11—C10—C9	119.43 (17)
C4—C3—C2	119.79 (17)	C12—C11—C10	120.1 (2)
C4—C3—H3	120.1	C12—C11—H11	119.9
C2—C3—H3	120.1	C10—C11—H11	119.9
C3—C4—C5	120.55 (17)	C13—C12—C11	120.7 (2)
C3—C4—H4	119.7	C13—C12—H12	119.7
C5—C4—H4	119.7	C11—C12—H12	119.7
C6—C5—C4	119.83 (17)	C12—C13—C14	119.5 (2)
C6—C5—H5	120.1	C12—C13—H13	120.2
C4—C5—H5	120.1	C14—C13—H13	120.2
C5—C6—C1	120.81 (16)	C15—C14—C13	120.0 (2)
C5—C6—H6	119.6	C15—C14—H14	120.0
C1—C6—H6	119.6	C13—C14—H14	120.0
N1—C7—C1	118.70 (14)	C10—C15—C14	120.53 (19)
N1—C7—H7	120.7	C10—C15—H15	119.7
C1—C7—H7	120.7	C14—C15—H15	119.7
C7—N1—N2—C8	179.79 (15)	C9—O2—C8—O3	−7.2 (2)
C6—C1—C2—O1	−179.68 (16)	C9—O2—C8—N2	173.15 (13)
C7—C1—C2—O1	2.1 (2)	N1—N2—C8—O3	−1.1 (3)
C6—C1—C2—C3	−0.3 (2)	N1—N2—C8—O2	178.58 (13)
C7—C1—C2—C3	−178.51 (16)	C8—O2—C9—C10	−78.01 (18)
O1—C2—C3—C4	−179.13 (17)	O2—C9—C10—C15	119.80 (18)
C1—C2—C3—C4	1.4 (3)	O2—C9—C10—C11	−59.9 (2)
C2—C3—C4—C5	−1.5 (3)	C15—C10—C11—C12	0.3 (3)
C3—C4—C5—C6	0.3 (3)	C9—C10—C11—C12	−179.98 (17)
C4—C5—C6—C1	0.9 (3)	C10—C11—C12—C13	0.1 (3)
C2—C1—C6—C5	−0.9 (3)	C11—C12—C13—C14	−0.3 (3)
C7—C1—C6—C5	177.40 (16)	C12—C13—C14—C15	0.2 (3)
N2—N1—C7—C1	178.01 (14)	C11—C10—C15—C14	−0.4 (3)
C6—C1—C7—N1	−177.06 (15)	C9—C10—C15—C14	179.89 (17)
C2—C1—C7—N1	1.2 (2)	C13—C14—C15—C10	0.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.90 (3)	1.73 (3)	2.546 (2)	148 (2)
N2—H2N···O1i	0.87 (2)	1.97 (2)	2.8225 (19)	168 (2)
C7—H7···O3ii	0.95	2.43	3.271 (2)	147

C15H13BrN2O3	F(000) = 1408
Mr = 349.18	Dx = 1.654 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.904 (2) Å	Cell parameters from 9936 reflections
b = 11.1207 (6) Å	θ = 2.3–27.5°
c = 9.0648 (7) Å	µ = 2.94 mm−1
β = 94.485 (2)°	T = 90 K
V = 2804.3 (3) Å3	Plate, colourless
Z = 8	0.24 × 0.22 × 0.05 mm

Bruker D8 Venture dual source diffractometer	6401 independent reflections
Radiation source: microsource	5004 reflections with I > 2σ(I)
Detector resolution: 7.41 pixels mm-1	Rint = 0.047
φ and ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −36→36
Tmin = 0.598, Tmax = 0.862	k = −13→14
36145 measured reflections	l = −11→11

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028	Hydrogen site location: mixed
wR(F2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.024P)2 + 0.4336P] where P = (Fo2 + 2Fc2)/3
6401 reflections	(Δ/σ)max = 0.001
391 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat (Parkin & Hope, 1998). Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals.

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. Refinement progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF.

	x	y	z	Uiso*/Ueq
Br1A	−0.15724 (2)	0.00040 (2)	−0.27291 (2)	0.01837 (6)
O1A	−0.03689 (5)	0.32791 (12)	0.13515 (17)	0.0155 (3)
H1AO	−0.0212 (8)	0.285 (2)	0.195 (3)	0.023*
O2A	0.07623 (4)	0.09899 (12)	0.57652 (16)	0.0147 (3)
O3A	0.05320 (5)	0.27304 (12)	0.45841 (16)	0.0164 (3)
N1A	0.00001 (5)	0.13879 (14)	0.25999 (19)	0.0131 (4)
N2A	0.03016 (6)	0.08825 (15)	0.3687 (2)	0.0144 (4)
H2AN	0.0326 (8)	0.011 (2)	0.378 (3)	0.022*
C1A	−0.05776 (6)	0.12521 (17)	0.0571 (2)	0.0123 (4)
C2A	−0.06384 (6)	0.25104 (17)	0.0464 (2)	0.0128 (4)
C3A	−0.09807 (7)	0.29968 (17)	−0.0559 (2)	0.0151 (4)
H3A	−0.102322	0.384378	−0.061072	0.018*
C4A	−0.12600 (7)	0.22594 (18)	−0.1503 (2)	0.0161 (4)
H4A	−0.149393	0.259472	−0.220254	0.019*
C5A	−0.11949 (6)	0.10144 (17)	−0.1417 (2)	0.0135 (4)
C6A	−0.08603 (7)	0.05145 (17)	−0.0399 (2)	0.0133 (4)
H6A	−0.082137	−0.033375	−0.035397	0.016*
C7A	−0.02400 (7)	0.07044 (17)	0.1679 (2)	0.0135 (4)
H7A	−0.019897	−0.014331	0.171790	0.016*
C8A	0.05341 (7)	0.16443 (17)	0.4676 (2)	0.0134 (4)
C9A	0.11033 (7)	0.16320 (18)	0.6787 (2)	0.0159 (4)
H9A1	0.108034	0.132746	0.780527	0.019*
H9A2	0.102462	0.250018	0.677625	0.019*
C10A	0.16046 (7)	0.14533 (18)	0.6338 (2)	0.0152 (4)
C11A	0.18757 (7)	0.04758 (18)	0.6867 (3)	0.0199 (5)
H11A	0.175224	−0.004677	0.757468	0.024*
C12A	0.23246 (7)	0.0256 (2)	0.6372 (3)	0.0244 (5)
H12A	0.250802	−0.041479	0.673897	0.029*
C13A	0.25050 (7)	0.1014 (2)	0.5344 (3)	0.0236 (5)
H13A	0.280911	0.084987	0.498459	0.028*
C14A	0.22449 (7)	0.2012 (2)	0.4832 (3)	0.0234 (5)
H14A	0.237391	0.254413	0.414556	0.028*
C15A	0.17947 (7)	0.22296 (18)	0.5330 (2)	0.0184 (5)
H15A	0.161541	0.291233	0.498007	0.022*
Br1B	0.33187 (2)	0.24274 (2)	−0.24668 (2)	0.01864 (6)
O1B	0.46666 (5)	0.56485 (12)	0.12357 (18)	0.0175 (3)
H1BO	0.4824 (8)	0.526 (2)	0.183 (3)	0.026*
O2B	0.58093 (5)	0.33767 (12)	0.56327 (17)	0.0200 (3)
O3B	0.55787 (5)	0.51149 (12)	0.44468 (17)	0.0213 (3)
N1B	0.50017 (6)	0.37664 (15)	0.2571 (2)	0.0163 (4)
N2B	0.53006 (6)	0.32678 (15)	0.3664 (2)	0.0177 (4)
H2BN	0.5316 (8)	0.248 (2)	0.381 (3)	0.027*
C1B	0.44047 (7)	0.36259 (17)	0.0590 (2)	0.0144 (4)
C2B	0.43755 (7)	0.48817 (17)	0.0413 (2)	0.0155 (4)
C3B	0.40395 (7)	0.53794 (18)	−0.0621 (2)	0.0187 (5)
H3B	0.402207	0.622759	−0.073766	0.022*
C4B	0.37308 (7)	0.46506 (18)	−0.1480 (2)	0.0186 (5)
H4B	0.349893	0.499454	−0.217909	0.022*
C5B	0.37609 (7)	0.34063 (18)	−0.1317 (2)	0.0157 (4)
C6B	0.40953 (7)	0.28942 (18)	−0.0301 (2)	0.0153 (4)
H6B	0.411493	0.204431	−0.020934	0.018*
C7B	0.47346 (7)	0.30758 (17)	0.1725 (2)	0.0159 (5)
H7B	0.475081	0.222686	0.183473	0.019*
C8B	0.55672 (7)	0.40391 (18)	0.4573 (2)	0.0164 (4)
C9B	0.61708 (7)	0.40024 (19)	0.6607 (3)	0.0199 (5)
H9B1	0.616291	0.369612	0.762983	0.024*
H9B2	0.609811	0.487367	0.661257	0.024*
C10B	0.66606 (7)	0.38057 (18)	0.6078 (2)	0.0177 (5)
C11B	0.69188 (7)	0.27764 (19)	0.6499 (3)	0.0243 (5)
H11B	0.678700	0.220613	0.713444	0.029*
C12B	0.73692 (8)	0.2581 (2)	0.5992 (3)	0.0314 (6)
H12B	0.754349	0.187171	0.627110	0.038*
C13B	0.75634 (8)	0.3413 (2)	0.5085 (3)	0.0339 (6)
H13B	0.787039	0.327312	0.473303	0.041*
C14B	0.73134 (8)	0.4452 (2)	0.4685 (3)	0.0302 (6)
H14B	0.745077	0.503149	0.407352	0.036*
C15B	0.68621 (7)	0.4646 (2)	0.5178 (2)	0.0216 (5)
H15B	0.668973	0.535692	0.489816	0.026*

	U11	U22	U33	U12	U13	U23
Br1A	0.02056 (10)	0.01578 (11)	0.01793 (13)	−0.00204 (8)	−0.00389 (8)	−0.00260 (9)
O1A	0.0167 (7)	0.0096 (7)	0.0194 (9)	−0.0001 (5)	−0.0033 (6)	0.0007 (6)
O2A	0.0156 (7)	0.0133 (7)	0.0146 (9)	−0.0002 (5)	−0.0031 (6)	−0.0003 (6)
O3A	0.0195 (7)	0.0107 (7)	0.0193 (9)	−0.0015 (5)	0.0025 (6)	−0.0002 (6)
N1A	0.0121 (8)	0.0127 (8)	0.0143 (11)	0.0018 (6)	0.0009 (7)	0.0020 (7)
N2A	0.0173 (8)	0.0093 (8)	0.0159 (11)	0.0011 (7)	−0.0025 (7)	0.0005 (7)
C1A	0.0124 (9)	0.0113 (9)	0.0134 (12)	0.0006 (7)	0.0033 (8)	0.0007 (8)
C2A	0.0120 (9)	0.0116 (9)	0.0153 (12)	−0.0028 (8)	0.0051 (8)	−0.0014 (8)
C3A	0.0155 (10)	0.0102 (9)	0.0196 (13)	0.0018 (8)	0.0019 (9)	0.0018 (8)
C4A	0.015 (1)	0.0161 (10)	0.0172 (13)	0.0025 (8)	0.0018 (8)	0.0035 (9)
C5A	0.0113 (9)	0.0159 (10)	0.0132 (12)	−0.0019 (8)	−0.0002 (8)	−0.0021 (8)
C6A	0.0158 (10)	0.0101 (9)	0.0145 (12)	−0.0009 (8)	0.0049 (8)	0.0007 (8)
C7A	0.0145 (9)	0.0100 (9)	0.0164 (13)	0.0005 (7)	0.0042 (8)	0.0005 (8)
C8A	0.0109 (9)	0.0134 (10)	0.0164 (12)	−0.0005 (7)	0.0045 (8)	−0.0003 (8)
C9A	0.0176 (10)	0.0171 (10)	0.0125 (12)	−0.0022 (8)	−0.0018 (9)	−0.0042 (8)
C10A	0.0155 (10)	0.0172 (10)	0.0124 (12)	−0.0013 (8)	−0.0029 (8)	−0.0060 (8)
C11A	0.0235 (11)	0.0167 (10)	0.0185 (13)	−0.0030 (9)	−0.0049 (9)	0.0007 (9)
C12A	0.0185 (11)	0.0253 (12)	0.0278 (15)	0.0061 (9)	−0.0083 (9)	−0.0055 (10)
C13A	0.0137 (10)	0.0311 (13)	0.0257 (15)	−0.0020 (9)	0.0000 (9)	−0.0118 (10)
C14A	0.0211 (11)	0.0254 (12)	0.0237 (14)	−0.0073 (9)	0.0026 (10)	−0.0037 (10)
C15A	0.0214 (10)	0.0154 (10)	0.0176 (13)	−0.0007 (8)	−0.0029 (9)	−0.0026 (9)
Br1B	0.0178 (1)	0.01828 (11)	0.01947 (13)	−0.00271 (8)	−0.00094 (8)	−0.00299 (9)
O1B	0.0174 (7)	0.0116 (7)	0.0227 (10)	−0.0013 (6)	−0.0037 (6)	−0.0002 (6)
O2B	0.0174 (7)	0.0154 (7)	0.0259 (10)	−0.0012 (6)	−0.0070 (6)	−0.0003 (6)
O3B	0.0230 (7)	0.0118 (7)	0.0284 (10)	−0.0024 (6)	−0.0017 (7)	−0.0006 (6)
N1B	0.0153 (9)	0.0139 (9)	0.0193 (12)	0.0015 (6)	−0.0009 (8)	0.0029 (7)
N2B	0.0183 (9)	0.0115 (8)	0.0221 (12)	0.0006 (7)	−0.0058 (8)	0.0015 (8)
C1B	0.0126 (9)	0.0146 (10)	0.0162 (12)	0.0002 (8)	0.0031 (8)	0.0001 (8)
C2B	0.0137 (9)	0.0133 (10)	0.0200 (13)	−0.0021 (8)	0.0034 (8)	−0.0029 (9)
C3B	0.0197 (10)	0.0124 (10)	0.0243 (14)	0.0013 (8)	0.0028 (9)	0.0013 (9)
C4B	0.0189 (10)	0.0177 (10)	0.0189 (13)	0.0015 (8)	−0.0004 (9)	0.0017 (9)
C5B	0.0125 (9)	0.0172 (10)	0.0176 (13)	−0.0023 (8)	0.0037 (8)	−0.0034 (9)
C6B	0.0167 (10)	0.0111 (10)	0.0186 (13)	−0.0006 (8)	0.0039 (9)	−0.0004 (8)
C7B	0.0152 (10)	0.0102 (9)	0.0222 (13)	0.0003 (8)	0.0009 (9)	0.0003 (8)
C8B	0.0132 (10)	0.0165 (10)	0.0197 (13)	0.0002 (8)	0.0024 (8)	0.0011 (9)
C9B	0.018 (1)	0.0211 (11)	0.0195 (13)	−0.0016 (8)	−0.0056 (9)	−0.0039 (9)
C10B	0.0174 (10)	0.0190 (11)	0.0160 (13)	−0.0011 (8)	−0.0033 (9)	−0.0051 (9)
C11B	0.0229 (11)	0.0182 (11)	0.0307 (15)	−0.0014 (9)	−0.0041 (10)	−0.002 (1)
C12B	0.0240 (12)	0.0267 (13)	0.0419 (17)	0.0059 (10)	−0.0069 (11)	−0.0121 (12)
C13B	0.0198 (12)	0.0505 (16)	0.0320 (17)	−0.0009 (11)	0.0052 (11)	−0.0142 (13)
C14B	0.0285 (12)	0.0410 (15)	0.0213 (15)	−0.0098 (11)	0.0042 (10)	−0.0048 (11)
C15B	0.0255 (11)	0.0225 (11)	0.0160 (13)	−0.0015 (9)	−0.0032 (9)	−0.0018 (9)

Br1A—C5A	1.8949 (19)	Br1B—C5B	1.896 (2)
O1A—C2A	1.360 (2)	O1B—C2B	1.360 (2)
O1A—H1AO	0.82 (2)	O1B—H1BO	0.80 (2)
O2A—C8A	1.346 (2)	O2B—C8B	1.349 (2)
O2A—C9A	1.461 (2)	O2B—C9B	1.464 (2)
O3A—C8A	1.211 (2)	O3B—C8B	1.203 (2)
N1A—C7A	1.279 (2)	N1B—C7B	1.282 (2)
N1A—N2A	1.365 (2)	N1B—N2B	1.362 (2)
N2A—C8A	1.361 (3)	N2B—C8B	1.369 (3)
N2A—H2AN	0.87 (2)	N2B—H2BN	0.88 (2)
C1A—C6A	1.399 (3)	C1B—C6B	1.397 (3)
C1A—C2A	1.412 (3)	C1B—C2B	1.407 (3)
C1A—C7A	1.456 (3)	C1B—C7B	1.460 (3)
C2A—C3A	1.388 (3)	C2B—C3B	1.388 (3)
C3A—C4A	1.381 (3)	C3B—C4B	1.378 (3)
C3A—H3A	0.9500	C3B—H3B	0.9500
C4A—C5A	1.398 (3)	C4B—C5B	1.394 (3)
C4A—H4A	0.9500	C4B—H4B	0.9500
C5A—C6A	1.378 (3)	C5B—C6B	1.381 (3)
C6A—H6A	0.9500	C6B—H6B	0.9500
C7A—H7A	0.9500	C7B—H7B	0.9500
C9A—C10A	1.500 (3)	C9B—C10B	1.499 (3)
C9A—H9A1	0.9900	C9B—H9B1	0.9900
C9A—H9A2	0.9900	C9B—H9B2	0.9900
C10A—C11A	1.388 (3)	C10B—C15B	1.388 (3)
C10A—C15A	1.392 (3)	C10B—C11B	1.390 (3)
C11A—C12A	1.385 (3)	C11B—C12B	1.389 (3)
C11A—H11A	0.9500	C11B—H11B	0.9500
C12A—C13A	1.380 (3)	C12B—C13B	1.377 (4)
C12A—H12A	0.9500	C12B—H12B	0.9500
C13A—C14A	1.386 (3)	C13B—C14B	1.384 (4)
C13A—H13A	0.9500	C13B—H13B	0.9500
C14A—C15A	1.389 (3)	C14B—C15B	1.385 (3)
C14A—H14A	0.9500	C14B—H14B	0.9500
C15A—H15A	0.9500	C15B—H15B	0.9500
C2A—O1A—H1AO	105.5 (16)	C2B—O1B—H1BO	107.9 (17)
C8A—O2A—C9A	116.62 (15)	C8B—O2B—C9B	116.93 (16)
C7A—N1A—N2A	119.20 (16)	C7B—N1B—N2B	119.03 (17)
C8A—N2A—N1A	117.02 (16)	N1B—N2B—C8B	117.14 (17)
C8A—N2A—H2AN	121.5 (15)	N1B—N2B—H2BN	122.0 (15)
N1A—N2A—H2AN	121.3 (15)	C8B—N2B—H2BN	120.8 (15)
C6A—C1A—C2A	118.64 (18)	C6B—C1B—C2B	118.97 (18)
C6A—C1A—C7A	119.38 (17)	C6B—C1B—C7B	119.38 (18)
C2A—C1A—C7A	121.97 (18)	C2B—C1B—C7B	121.59 (18)
O1A—C2A—C3A	118.04 (17)	O1B—C2B—C3B	117.61 (18)
O1A—C2A—C1A	121.65 (18)	O1B—C2B—C1B	122.20 (18)
C3A—C2A—C1A	120.30 (18)	C3B—C2B—C1B	120.18 (18)
C4A—C3A—C2A	120.53 (18)	C4B—C3B—C2B	120.41 (19)
C4A—C3A—H3A	119.7	C4B—C3B—H3B	119.8
C2A—C3A—H3A	119.7	C2B—C3B—H3B	119.8
C3A—C4A—C5A	119.28 (18)	C3B—C4B—C5B	119.61 (19)
C3A—C4A—H4A	120.4	C3B—C4B—H4B	120.2
C5A—C4A—H4A	120.4	C5B—C4B—H4B	120.2
C6A—C5A—C4A	121.02 (18)	C6B—C5B—C4B	120.81 (18)
C6A—C5A—Br1A	119.71 (14)	C6B—C5B—Br1B	120.43 (15)
C4A—C5A—Br1A	119.27 (15)	C4B—C5B—Br1B	118.72 (15)
C5A—C6A—C1A	120.22 (18)	C5B—C6B—C1B	120.00 (18)
C5A—C6A—H6A	119.9	C5B—C6B—H6B	120.0
C1A—C6A—H6A	119.9	C1B—C6B—H6B	120.0
N1A—C7A—C1A	118.65 (17)	N1B—C7B—C1B	118.39 (18)
N1A—C7A—H7A	120.7	N1B—C7B—H7B	120.8
C1A—C7A—H7A	120.7	C1B—C7B—H7B	120.8
O3A—C8A—O2A	126.12 (19)	O3B—C8B—O2B	126.55 (19)
O3A—C8A—N2A	125.18 (19)	O3B—C8B—N2B	125.7 (2)
O2A—C8A—N2A	108.70 (16)	O2B—C8B—N2B	107.76 (17)
O2A—C9A—C10A	109.76 (16)	O2B—C9B—C10B	109.90 (17)
O2A—C9A—H9A1	109.7	O2B—C9B—H9B1	109.7
C10A—C9A—H9A1	109.7	C10B—C9B—H9B1	109.7
O2A—C9A—H9A2	109.7	O2B—C9B—H9B2	109.7
C10A—C9A—H9A2	109.7	C10B—C9B—H9B2	109.7
H9A1—C9A—H9A2	108.2	H9B1—C9B—H9B2	108.2
C11A—C10A—C15A	119.15 (19)	C15B—C10B—C11B	119.4 (2)
C11A—C10A—C9A	120.30 (19)	C15B—C10B—C9B	120.74 (19)
C15A—C10A—C9A	120.48 (18)	C11B—C10B—C9B	119.9 (2)
C12A—C11A—C10A	120.6 (2)	C12B—C11B—C10B	120.1 (2)
C12A—C11A—H11A	119.7	C12B—C11B—H11B	119.9
C10A—C11A—H11A	119.7	C10B—C11B—H11B	119.9
C13A—C12A—C11A	119.9 (2)	C13B—C12B—C11B	120.0 (2)
C13A—C12A—H12A	120.1	C13B—C12B—H12B	120.0
C11A—C12A—H12A	120.1	C11B—C12B—H12B	120.0
C12A—C13A—C14A	120.4 (2)	C12B—C13B—C14B	120.3 (2)
C12A—C13A—H13A	119.8	C12B—C13B—H13B	119.9
C14A—C13A—H13A	119.8	C14B—C13B—H13B	119.9
C13A—C14A—C15A	119.6 (2)	C13B—C14B—C15B	119.8 (2)
C13A—C14A—H14A	120.2	C13B—C14B—H14B	120.1
C15A—C14A—H14A	120.2	C15B—C14B—H14B	120.1
C14A—C15A—C10A	120.4 (2)	C14B—C15B—C10B	120.4 (2)
C14A—C15A—H15A	119.8	C14B—C15B—H15B	119.8
C10A—C15A—H15A	119.8	C10B—C15B—H15B	119.8
C7A—N1A—N2A—C8A	−177.37 (18)	C7B—N1B—N2B—C8B	−177.79 (18)
C6A—C1A—C2A—O1A	−178.68 (17)	C6B—C1B—C2B—O1B	−179.66 (18)
C7A—C1A—C2A—O1A	3.0 (3)	C7B—C1B—C2B—O1B	3.1 (3)
C6A—C1A—C2A—C3A	1.6 (3)	C6B—C1B—C2B—C3B	0.8 (3)
C7A—C1A—C2A—C3A	−176.79 (18)	C7B—C1B—C2B—C3B	−176.38 (19)
O1A—C2A—C3A—C4A	179.10 (18)	O1B—C2B—C3B—C4B	−179.38 (19)
C1A—C2A—C3A—C4A	−1.2 (3)	C1B—C2B—C3B—C4B	0.2 (3)
C2A—C3A—C4A—C5A	0.0 (3)	C2B—C3B—C4B—C5B	−0.7 (3)
C3A—C4A—C5A—C6A	0.6 (3)	C3B—C4B—C5B—C6B	0.2 (3)
C3A—C4A—C5A—Br1A	−179.20 (15)	C3B—C4B—C5B—Br1B	178.02 (16)
C4A—C5A—C6A—C1A	−0.2 (3)	C4B—C5B—C6B—C1B	0.8 (3)
Br1A—C5A—C6A—C1A	179.65 (14)	Br1B—C5B—C6B—C1B	−176.99 (15)
C2A—C1A—C6A—C5A	−0.9 (3)	C2B—C1B—C6B—C5B	−1.3 (3)
C7A—C1A—C6A—C5A	177.49 (18)	C7B—C1B—C6B—C5B	175.98 (19)
N2A—N1A—C7A—C1A	177.06 (16)	N2B—N1B—C7B—C1B	178.03 (17)
C6A—C1A—C7A—N1A	−176.88 (18)	C6B—C1B—C7B—N1B	−177.23 (19)
C2A—C1A—C7A—N1A	1.5 (3)	C2B—C1B—C7B—N1B	0.0 (3)
C9A—O2A—C8A—O3A	−11.2 (3)	C9B—O2B—C8B—O3B	−8.9 (3)
C9A—O2A—C8A—N2A	169.09 (15)	C9B—O2B—C8B—N2B	171.53 (16)
N1A—N2A—C8A—O3A	−7.7 (3)	N1B—N2B—C8B—O3B	−4.0 (3)
N1A—N2A—C8A—O2A	171.98 (15)	N1B—N2B—C8B—O2B	175.60 (16)
C8A—O2A—C9A—C10A	−98.12 (19)	C8B—O2B—C9B—C10B	−98.0 (2)
O2A—C9A—C10A—C11A	−88.3 (2)	O2B—C9B—C10B—C15B	95.9 (2)
O2A—C9A—C10A—C15A	88.5 (2)	O2B—C9B—C10B—C11B	−84.5 (2)
C15A—C10A—C11A—C12A	−1.6 (3)	C15B—C10B—C11B—C12B	−1.5 (3)
C9A—C10A—C11A—C12A	175.19 (19)	C9B—C10B—C11B—C12B	178.9 (2)
C10A—C11A—C12A—C13A	0.0 (3)	C10B—C11B—C12B—C13B	0.8 (4)
C11A—C12A—C13A—C14A	1.7 (3)	C11B—C12B—C13B—C14B	0.6 (4)
C12A—C13A—C14A—C15A	−1.8 (3)	C12B—C13B—C14B—C15B	−1.1 (4)
C13A—C14A—C15A—C10A	0.1 (3)	C13B—C14B—C15B—C10B	0.4 (3)
C11A—C10A—C15A—C14A	1.6 (3)	C11B—C10B—C15B—C14B	1.0 (3)
C9A—C10A—C15A—C14A	−175.24 (19)	C9B—C10B—C15B—C14B	−179.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1AO···N1A	0.82 (2)	1.81 (2)	2.565 (2)	151 (2)
N2A—H2AN···O1Ai	0.87 (2)	2.04 (2)	2.902 (2)	171 (2)
C3A—H3A···O2Aii	0.95	2.50	3.392 (2)	156
C6A—H6A···O3Ai	0.95	2.38	3.296 (2)	161
O1B—H1BO···N1B	0.80 (2)	1.84 (2)	2.558 (2)	148 (2)
N2B—H2BN···O1Biii	0.88 (2)	2.04 (2)	2.915 (2)	171 (2)
C3B—H3B···O2Biv	0.95	2.44	3.360 (2)	164
C6B—H6B···O3Biii	0.95	2.39	3.297 (2)	159