Crystal structure and Hirshfeld surface analysis of 4-bromo-2-[3-methyl-5-(2,4,6-tri-methyl-benz-yl)oxazolidin-2-yl]phenol.

The title compound, C20H24BrNO2, is chiral at the carbon atoms on either side of the oxygen atom of the oxazolidine ring and crystallizes as a racemate. The 1,3-oxazolidine ring adopts an envelope conformation with the N atom in an endo position. The mean plane of the oxazolidine ring makes dihedral angles of 77.74 (10) and 45.50 (11)°, respectively, with the 4-bromo-phenol and 1,3,5-tri-methyl-benzene rings. In the crystal, adjacent mol-ecules are connected via C-H⋯O hydrogen bonds and C-H⋯π inter-actions into layers parallel to the (200) plane. The packing is strengthened by van der Waals inter-actions between parallel mol-ecular layers. A Hirshfeld surface analysis shows that H⋯H (58.2%), C⋯H/H⋯C (18.9%), and Br⋯H/H⋯Br (11.5%) inter-actions are the most abundant in the crystal packing. © Khalilov et al. 2022.

Chemical context

Functionalization of amine and carbonyl compounds represents a cornerstone of organic synthesis, material science and medicinal chemistry (Zubkov et al., 2018 ▸; Shikhaliyev et al., 2019 ▸; Viswanathan et al., 2019 ▸; Gurbanov et al., 2020 ▸). In particular, the reaction of 1,2-amino alcohols with oxo compounds is an effective tool in the construction of a broad class of organic compounds such as amides, esters, enamino­nes, ureas, carbamates, aziridines, oxazolidines, oxazolines, oxazolidinones, oxazines, pyrroles, pyridones, morpholines, acridinones etc (Juhász et al., 2011 ▸; Tamura et al., 2014 ▸; Sepideh et al., 2018 ▸; Khalilov, 2021 ▸).

In the context of our recent studies, herein we report the structural analysis of a 1,3-oxazolidine, synthesized on the base of racemic 1,2-amino alcohol. Theoretically, in the solid state, this 1,3-oxazolidine can exist as eight optical isomers due to two CH and one N-chiral center. However, NMR analysis of the obtained product indicated the formation of a pair of diastereoisomers in a 1:1 ratio (Khalilov, 2021 ▸) and single-crystal X-ray analysis of the racemic mixture confirmed the 2R,3S,5R- and 2S,3R,5S-configuration of these isomers (Fig. 1 ▸).

Figure 1

Synthesis of the racemic mixture of 2R,3S,5R- and 2S,3R,5S-oxazolidines.

Thus, in the framework of our ongoing structural studies (Naghiyev et al., 2020 ▸, 2021 ▸, 2022 ▸; Khalilov et al., 2022 ▸), we report the crystal structure and Hirshfeld surface analysis of the racemic title compound, 4-bromo-2-[3-methyl-5-(2,4,6-tri­methyl­benz­yl)oxazolidin-2-yl]phenol.

Structural commentary

In the title compound, (Fig. 2 ▸), the 1,3-oxazolidine ring (O1/N3/C2/C4/C5) adopts an envelope conformation with the N atom in an endo position [the puckering parameters (Cremer & Pople, 1975 ▸) are Q(2) = 0.413 (2) Å, φ(2) = 256.7 (3)°]. The mean plane of th oxazolidine ring makes dihedral angles of 77.74 (10) and 45.50 (11)°, respectively, with the 4-bromo­phenol (C6–C11) and the 1,3,5-tri­methyl­benzene (C14–C19) rings. The mol­ecular conformation is stabilized by intra­molecular O11—H11⋯N3 and C20—H20C⋯O1 hydrogen bonds (Table 1 ▸). There are two stereogenic centers in the racaemic title compound and the chirality about the C2 and C5 atoms is R in the chosen asymmetric unit. The geometric properties of the title compound are normal and consistent with those of related compounds listed in the Database survey section.

Figure 2

The mol­ecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 and Cg3 are the centroids of the 4-bromo­phenol (C6–C11) and 1,3,5-tri­methyl­benzene (C14–C19) rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11—H11⋯N3	0.81 (4)	1.89 (4)	2.644 (2)	155 (3)
C4—H4A⋯O1i	0.99	2.58	3.564 (2)	171
C20—H20B⋯O11ii	0.98	2.57	3.548 (3)	173
C20—H20C⋯O1	0.98	2.55	3.332 (3)	136
C2—H2⋯Cg2i	1.00	2.91	3.908 (2)	176
C4—H4B⋯Cg3i	0.99	2.88	3.622 (2)	132
C21—H21C⋯Cg3iii	0.98	2.93	3.723 (4)	138

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

Supra­molecular features and Hirshfeld surface analysis

In the crystal, adjacent mol­ecules are connected via C—H⋯O hydrogen bonds and C—H⋯π inter­actions into layers parallel to the (200) plane (Table 1 ▸; Figs. 3 ▸ and 4 ▸). The packing is strengthened by van der Waals inter­actions between parallel mol­ecular layers.

Figure 3

A general view of the C—H⋯O hydrogen bonding and C—H⋯π inter­actions of the title compound. Symmetry codes: (i) x, −y +  , z +  ; (ii) x, y + 1, z; (iii) x, −y −  , z −  ; (iv) x, −y +  , z −  .

Figure 4

Packing view of the title compound along the b axis with the inter­actions depicted as in Fig. 3 ▸.

A Hirshfeld surface analysis was performed and the associated two-dimensional fingerprint plots were obtained with CrystalExplorer17.5 (Turner et al., 2017 ▸). The overall two-dimensional fingerprint plot for the title compound is given in Fig. 5 ▸ a, and those delineated into H⋯H (58.2%), C⋯H/H⋯C (18.9%), and Br⋯H/H⋯Br (11.5%) contacts are shown in Fig. 5 ▸ b–d, while numerical details of the different contacts are given in Table 2 ▸. The O⋯H/H⋯O (8.3%), C⋯C (1.4%), Br⋯C/C⋯Br (1.0%), Br⋯O/O⋯Br (0.5%) and Br⋯Br (0.3%) contacts have little directional influence on the mol­ecular packing. A a result, in the crystal packing, C—H⋯π (ring) and van der Waals inter­actions are dominant.

Figure 5

The two-dimensional fingerprint plots of the title compound, showing (a) all inter­actions, and delineated into (b) H⋯H, (c) C⋯H/H⋯C and (d) Br⋯H/H⋯Br inter­actions. [d e and d i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (inter­nal) the surface, respectively.]

Table 2

Summary of short inter­atomic contacts (Å) in the title compound

Contact	Distance	Symmetry operation
Br1⋯H10	2.96	1 − x,  + y,  − z
Br1⋯C12	3.598	1 − x,  + y,  − z
C9⋯C8	3.409	1 − x, −y, 1 − z
H9⋯H7	2.45	x,  − y, −  + z
H11⋯H20B	2.35	x, −1 + y, z
C15⋯H21C	2.80	x,  − y,  + z
H22B⋯C18	3.07	−x, 1 − y, 1 − z
H21B⋯H22B	2.51	−x,  + y,  − z

Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ▸) for similar structures with a 1,3-oxazolidine ring showed that the five most closely related to the title compound are (S)-5-chloro-N-({2-oxo-3-[4-(3-oxomorpholin-4-yl)phen­yl]oxa­zolidin-5-yl}meth­yl)-thio­phene-2-carboxamide [(I): Shen et al., 2018 ▸], 2,2-di­chloro-1-(2-phenyl-1,3-oxazolidin-3-yl)ethan­one [(II): Ye et al., 2010 ▸], (4-benzyl-2-oxo-1,3-oxazolidin-5-yl)- methyl methane­sulfonate [(III): Cunico et al., 2010 ▸], 2-bromo-4-(3,4-dimethyl-5-phenyl-1,3-oxazolidin-2-yl)-6-meth­oxy­phenol [(IV): Hariono et al., 2012 ▸] and (R)-2-phen­oxy-1-(4-phenyl-2-sulfanyl­idene-1,3-oxazolidin-3-yl)ethanone [(V): Caracelli et al., 2011 ▸].

In the crystal of (I), classical N—H⋯O hydrogen bonds and weak C— H⋯O hydrogen bonds link the mol­ecules into a three-dimensional supra­molecular architecture. In (II), mol­ecules are linked by weak inter­molecular C—H⋯O hydrogen bonds, forming one-dimensional chains. In the crystal of (III), N—H⋯O hydrogen bonds, involving one of the sulfur-bound oxo groups as acceptor, lead to the formation of supra­molecular chains along the b-axis direction. These chains are reinforced by C—H⋯O contacts, with the carbonyl O atom accepting three such inter­actions. In (IV), adjacent mol­ecules are connected via O—H⋯O and C—H⋯O hydrogen bonds and C—H⋯π inter­actions into a zigzag chain along the b-axis direction. In (V), mol­ecules are linked into supra­molecular arrays two mol­ecules thick in the bc plane through C—H⋯O, C—H⋯S and C—H⋯π inter­actions.

Synthesis and crystallization

The title compound was synthesized using our recently reported procedure (Khalilov, 2021 ▸), and colorless needle-like crystals were obtained upon recrystallization from an ethanol/water solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All C-bound H atoms were placed at calculated positions and refined using a riding model, with C—H = 0.95 to 1.00 Å, and with U iso(H) = 1.2 or 1.5U eq(C). The hydroxyl H atom was found in a difference-Fourier map and was refined freely.

Table 3

Experimental details

Crystal data
Chemical formula	C20H24BrNO2
M r	390.30
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	100
a, b, c (Å)	21.1019 (3), 9.01359 (11), 10.03985 (11)
β (°)	96.1425 (11)
V (Å3)	1898.66 (4)
Z	4
Radiation type	Cu Kα
μ (mm−1)	3.03
Crystal size (mm)	0.32 × 0.04 × 0.03
Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 ▸)
T min, T max	0.424, 0.882
No. of measured, independent and observed [I > 2σ(I)] reflections	21431, 4096, 3783
R int	0.043
(sin θ/λ)max (Å−1)	0.638
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.033, 0.096, 1.07
No. of reflections	4096
No. of parameters	225
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.58, −0.60

Computer programs: CrysAlis PRO (Rigaku OD, 2021 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2018 (Sheldrick, 2015b ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2020 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022005928/tx2051sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022005928/tx2051Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989022005928/tx2051Isup3.cml

CCDC reference: 2176709

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

C20H24BrNO2	F(000) = 808
Mr = 390.30	Dx = 1.365 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 21.1019 (3) Å	Cell parameters from 13703 reflections
b = 9.01359 (11) Å	θ = 2.1–78.6°
c = 10.03985 (11) Å	µ = 3.03 mm−1
β = 96.1425 (11)°	T = 100 K
V = 1898.66 (4) Å3	Needle, colourless
Z = 4	0.32 × 0.04 × 0.03 mm

XtaLAB Synergy, Dualflex, HyPix diffractometer	3783 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	Rint = 0.043
φ and ω scans	θmax = 79.6°, θmin = 2.1°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021)	h = −25→26
Tmin = 0.424, Tmax = 0.882	k = −11→11
21431 measured reflections	l = −12→10
4096 independent reflections

Refinement on F2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033	Hydrogen site location: mixed
wR(F2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.055P)2 + 1.11P] where P = (Fo2 + 2Fc2)/3
4096 reflections	(Δ/σ)max = 0.001
225 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.60 e Å−3

Experimental. CrysAlisPro 1.171.41.117a (Rigaku OD, 2021) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

	x	y	z	Uiso*/Ueq
Br1	0.54220 (2)	0.31515 (2)	0.43375 (2)	0.02813 (9)
O1	0.27633 (7)	0.25150 (17)	0.58702 (14)	0.0298 (3)
C2	0.32957 (9)	0.1726 (2)	0.65118 (19)	0.0232 (4)
H2	0.3517	0.2334	0.7256	0.028*
N3	0.30119 (8)	0.03941 (18)	0.70533 (15)	0.0240 (3)
C4	0.24396 (10)	0.0998 (2)	0.7578 (2)	0.0286 (4)
H4A	0.2548	0.1518	0.8441	0.034*
H4B	0.2124	0.0210	0.7696	0.034*
C5	0.21970 (10)	0.2075 (2)	0.6467 (2)	0.0275 (4)
H5	0.1901	0.1541	0.5785	0.033*
C6	0.37483 (9)	0.1367 (2)	0.54907 (18)	0.0226 (4)
C7	0.42805 (9)	0.2251 (2)	0.53991 (18)	0.0235 (4)
H7	0.4364	0.3066	0.5991	0.028*
C8	0.46904 (9)	0.1942 (2)	0.44404 (19)	0.0229 (4)
C9	0.45780 (9)	0.0753 (2)	0.35676 (18)	0.0238 (4)
H9	0.4865	0.0541	0.2925	0.029*
C10	0.40439 (10)	−0.0118 (2)	0.36452 (18)	0.0255 (4)
H10	0.3961	−0.0925	0.3043	0.031*
C11	0.36252 (9)	0.0175 (2)	0.45995 (18)	0.0237 (4)
O11	0.31123 (7)	−0.07205 (17)	0.46493 (15)	0.0287 (3)
H11	0.2980 (17)	−0.053 (4)	0.536 (4)	0.050 (9)*
C12	0.34457 (10)	−0.0365 (2)	0.8069 (2)	0.0295 (4)
H12A	0.3823	−0.0707	0.7665	0.044*
H12B	0.3228	−0.1218	0.8418	0.044*
H12C	0.3577	0.0323	0.8803	0.044*
C13	0.18595 (10)	0.3429 (2)	0.6965 (2)	0.0293 (4)
H13A	0.1502	0.3093	0.7453	0.035*
H13B	0.2162	0.3982	0.7606	0.035*
C14	0.16029 (10)	0.4466 (2)	0.5851 (2)	0.0288 (4)
C15	0.19383 (11)	0.5761 (2)	0.5574 (2)	0.0301 (4)
C16	0.16792 (12)	0.6723 (3)	0.4563 (2)	0.0361 (5)
H16	0.1904	0.7603	0.4389	0.043*
C17	0.11055 (12)	0.6426 (3)	0.3812 (3)	0.0430 (6)
C18	0.07858 (11)	0.5135 (4)	0.4079 (3)	0.0452 (6)
H18	0.0393	0.4915	0.3564	0.054*
C19	0.10236 (10)	0.4145 (3)	0.5084 (2)	0.0365 (5)
C20	0.25709 (13)	0.6141 (3)	0.6335 (2)	0.0393 (5)
H20A	0.2512	0.6344	0.7273	0.059*
H20B	0.2748	0.7021	0.5938	0.059*
H20C	0.2865	0.5304	0.6291	0.059*
C21	0.08362 (15)	0.7492 (5)	0.2732 (3)	0.0650 (10)
H21A	0.0776	0.8468	0.3131	0.097*
H21B	0.0425	0.7119	0.2318	0.097*
H21C	0.1133	0.7581	0.2050	0.097*
C22	0.06445 (12)	0.2765 (4)	0.5315 (3)	0.0523 (7)
H22A	0.0859	0.1897	0.4985	0.079*
H22B	0.0217	0.2853	0.4835	0.079*
H22C	0.0611	0.2651	0.6276	0.079*

	U11	U22	U33	U12	U13	U23
Br1	0.02612 (13)	0.02966 (14)	0.02922 (14)	−0.00322 (7)	0.00584 (9)	0.00477 (7)
O1	0.0269 (7)	0.0344 (8)	0.0296 (7)	0.0054 (6)	0.0103 (6)	0.0108 (6)
C2	0.0242 (9)	0.0241 (9)	0.0216 (8)	−0.0010 (7)	0.0035 (7)	0.0011 (7)
N3	0.0258 (8)	0.0261 (8)	0.0201 (7)	−0.0015 (6)	0.0024 (6)	0.0029 (6)
C4	0.0291 (9)	0.0332 (10)	0.0245 (9)	−0.0019 (8)	0.0076 (7)	0.0037 (8)
C5	0.0270 (10)	0.0315 (10)	0.0249 (9)	−0.0003 (8)	0.0068 (7)	0.0021 (8)
C6	0.0254 (9)	0.0250 (9)	0.0173 (8)	0.0018 (7)	0.0018 (6)	0.0021 (7)
C7	0.0269 (9)	0.0231 (8)	0.0201 (8)	0.0005 (7)	0.0007 (7)	0.0015 (7)
C8	0.0223 (9)	0.0250 (9)	0.0212 (9)	−0.0002 (7)	0.0014 (7)	0.0040 (7)
C9	0.0257 (9)	0.0273 (9)	0.0183 (8)	0.0048 (7)	0.0018 (6)	0.0014 (7)
C10	0.0296 (9)	0.0266 (9)	0.0197 (8)	0.0039 (8)	0.0005 (7)	−0.0025 (7)
C11	0.0260 (9)	0.0238 (9)	0.0209 (8)	−0.0015 (7)	0.0002 (7)	0.0039 (7)
O11	0.0297 (7)	0.0317 (8)	0.0249 (7)	−0.0075 (6)	0.0040 (6)	−0.0043 (6)
C12	0.0347 (10)	0.0290 (10)	0.0239 (9)	0.0027 (8)	−0.0009 (8)	0.0043 (8)
C13	0.0312 (10)	0.0322 (10)	0.0260 (10)	0.0005 (8)	0.0093 (8)	0.0018 (8)
C14	0.0282 (9)	0.0335 (10)	0.0264 (9)	0.0076 (8)	0.0109 (7)	0.0004 (8)
C15	0.0369 (11)	0.0319 (10)	0.0231 (9)	0.0056 (8)	0.0102 (8)	−0.0007 (8)
C16	0.0421 (13)	0.0376 (12)	0.0314 (11)	0.0092 (9)	0.0167 (10)	0.0062 (9)
C17	0.0364 (12)	0.0587 (15)	0.0361 (12)	0.0159 (11)	0.0142 (10)	0.0169 (11)
C18	0.0252 (10)	0.0668 (17)	0.0435 (13)	0.0095 (11)	0.0032 (9)	0.0111 (12)
C19	0.0240 (9)	0.0471 (13)	0.0392 (11)	0.0059 (9)	0.0072 (8)	0.0041 (10)
C20	0.0515 (14)	0.0358 (12)	0.0306 (11)	−0.0086 (10)	0.0039 (10)	−0.0001 (9)
C21	0.0446 (15)	0.094 (3)	0.0574 (17)	0.0211 (17)	0.0119 (13)	0.0422 (19)
C22	0.0265 (11)	0.0609 (17)	0.0689 (18)	−0.0046 (12)	0.0016 (11)	0.0095 (15)

Br1—C8	1.9019 (19)	C12—H12B	0.9800
O1—C2	1.424 (2)	C12—H12C	0.9800
O1—C5	1.448 (2)	C13—C14	1.513 (3)
C2—N3	1.472 (2)	C13—H13A	0.9900
C2—C6	1.509 (3)	C13—H13B	0.9900
C2—H2	1.0000	C14—C19	1.404 (3)
N3—C12	1.465 (2)	C14—C15	1.407 (3)
N3—C4	1.472 (3)	C15—C16	1.401 (3)
C4—C5	1.525 (3)	C15—C20	1.505 (3)
C4—H4A	0.9900	C16—C17	1.382 (4)
C4—H4B	0.9900	C16—H16	0.9500
C5—C13	1.524 (3)	C17—C18	1.385 (4)
C5—H5	1.0000	C17—C21	1.513 (4)
C6—C7	1.388 (3)	C18—C19	1.399 (4)
C6—C11	1.404 (3)	C18—H18	0.9500
C7—C8	1.389 (3)	C19—C22	1.510 (4)
C7—H7	0.9500	C20—H20A	0.9800
C8—C9	1.388 (3)	C20—H20B	0.9800
C9—C10	1.383 (3)	C20—H20C	0.9800
C9—H9	0.9500	C21—H21A	0.9800
C10—C11	1.396 (3)	C21—H21B	0.9800
C10—H10	0.9500	C21—H21C	0.9800
C11—O11	1.356 (2)	C22—H22A	0.9800
O11—H11	0.81 (4)	C22—H22B	0.9800
C12—H12A	0.9800	C22—H22C	0.9800
C2—O1—C5	108.79 (14)	H12A—C12—H12C	109.5
O1—C2—N3	104.01 (15)	H12B—C12—H12C	109.5
O1—C2—C6	109.02 (15)	C14—C13—C5	113.25 (17)
N3—C2—C6	112.83 (16)	C14—C13—H13A	108.9
O1—C2—H2	110.3	C5—C13—H13A	108.9
N3—C2—H2	110.3	C14—C13—H13B	108.9
C6—C2—H2	110.3	C5—C13—H13B	108.9
C12—N3—C2	112.92 (16)	H13A—C13—H13B	107.7
C12—N3—C4	113.51 (15)	C19—C14—C15	119.3 (2)
C2—N3—C4	102.26 (15)	C19—C14—C13	120.0 (2)
N3—C4—C5	101.41 (15)	C15—C14—C13	120.7 (2)
N3—C4—H4A	111.5	C16—C15—C14	119.4 (2)
C5—C4—H4A	111.5	C16—C15—C20	118.9 (2)
N3—C4—H4B	111.5	C14—C15—C20	121.7 (2)
C5—C4—H4B	111.5	C17—C16—C15	121.8 (2)
H4A—C4—H4B	109.3	C17—C16—H16	119.1
O1—C5—C13	110.61 (17)	C15—C16—H16	119.1
O1—C5—C4	104.45 (16)	C16—C17—C18	118.2 (2)
C13—C5—C4	113.71 (17)	C16—C17—C21	120.5 (3)
O1—C5—H5	109.3	C18—C17—C21	121.3 (3)
C13—C5—H5	109.3	C17—C18—C19	122.1 (2)
C4—C5—H5	109.3	C17—C18—H18	119.0
C7—C6—C11	119.50 (17)	C19—C18—H18	119.0
C7—C6—C2	119.82 (17)	C18—C19—C14	119.2 (2)
C11—C6—C2	120.64 (17)	C18—C19—C22	118.8 (2)
C6—C7—C8	119.94 (18)	C14—C19—C22	122.0 (2)
C6—C7—H7	120.0	C15—C20—H20A	109.5
C8—C7—H7	120.0	C15—C20—H20B	109.5
C9—C8—C7	121.00 (18)	H20A—C20—H20B	109.5
C9—C8—Br1	119.54 (14)	C15—C20—H20C	109.5
C7—C8—Br1	119.46 (15)	H20A—C20—H20C	109.5
C10—C9—C8	119.20 (17)	H20B—C20—H20C	109.5
C10—C9—H9	120.4	C17—C21—H21A	109.5
C8—C9—H9	120.4	C17—C21—H21B	109.5
C9—C10—C11	120.70 (18)	H21A—C21—H21B	109.5
C9—C10—H10	119.7	C17—C21—H21C	109.5
C11—C10—H10	119.7	H21A—C21—H21C	109.5
O11—C11—C10	118.61 (18)	H21B—C21—H21C	109.5
O11—C11—C6	121.74 (17)	C19—C22—H22A	109.5
C10—C11—C6	119.65 (18)	C19—C22—H22B	109.5
C11—O11—H11	105 (2)	H22A—C22—H22B	109.5
N3—C12—H12A	109.5	C19—C22—H22C	109.5
N3—C12—H12B	109.5	H22A—C22—H22C	109.5
H12A—C12—H12B	109.5	H22B—C22—H22C	109.5
N3—C12—H12C	109.5
C5—O1—C2—N3	23.8 (2)	C7—C6—C11—O11	179.93 (17)
C5—O1—C2—C6	144.39 (16)	C2—C6—C11—O11	−2.2 (3)
O1—C2—N3—C12	−163.70 (15)	C7—C6—C11—C10	0.9 (3)
C6—C2—N3—C12	78.3 (2)	C2—C6—C11—C10	178.71 (17)
O1—C2—N3—C4	−41.36 (18)	O1—C5—C13—C14	64.6 (2)
C6—C2—N3—C4	−159.35 (16)	C4—C5—C13—C14	−178.21 (18)
C12—N3—C4—C5	163.78 (17)	C5—C13—C14—C19	80.4 (2)
C2—N3—C4—C5	41.84 (18)	C5—C13—C14—C15	−99.8 (2)
C2—O1—C5—C13	125.28 (18)	C19—C14—C15—C16	1.7 (3)
C2—O1—C5—C4	2.6 (2)	C13—C14—C15—C16	−178.05 (18)
N3—C4—C5—O1	−27.6 (2)	C19—C14—C15—C20	−178.2 (2)
N3—C4—C5—C13	−148.32 (17)	C13—C14—C15—C20	2.1 (3)
O1—C2—C6—C7	98.9 (2)	C14—C15—C16—C17	−1.0 (3)
N3—C2—C6—C7	−146.13 (17)	C20—C15—C16—C17	178.9 (2)
O1—C2—C6—C11	−79.0 (2)	C15—C16—C17—C18	−0.1 (4)
N3—C2—C6—C11	36.0 (2)	C15—C16—C17—C21	179.6 (2)
C11—C6—C7—C8	−0.7 (3)	C16—C17—C18—C19	0.5 (4)
C2—C6—C7—C8	−178.59 (17)	C21—C17—C18—C19	−179.2 (3)
C6—C7—C8—C9	−0.2 (3)	C17—C18—C19—C14	0.2 (4)
C6—C7—C8—Br1	−179.44 (14)	C17—C18—C19—C22	179.8 (3)
C7—C8—C9—C10	1.0 (3)	C15—C14—C19—C18	−1.3 (3)
Br1—C8—C9—C10	−179.76 (14)	C13—C14—C19—C18	178.4 (2)
C8—C9—C10—C11	−0.9 (3)	C15—C14—C19—C22	179.1 (2)
C9—C10—C11—O11	−179.15 (17)	C13—C14—C19—C22	−1.1 (3)
C9—C10—C11—C6	−0.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···N3	0.81 (4)	1.89 (4)	2.644 (2)	155 (3)
C4—H4A···O1i	0.99	2.58	3.564 (2)	171
C20—H20B···O11ii	0.98	2.57	3.548 (3)	173
C20—H20C···O1	0.98	2.55	3.332 (3)	136
C2—H2···Cg2i	1.00	2.91	3.908 (2)	176
C4—H4B···Cg3i	0.99	2.88	3.622 (2)	132
C21—H21C···Cg3iii	0.98	2.93	3.723 (4)	138