Ethyl 2-amino-6-(4-bromo-phen-yl)-4-(4-fluoro-phen-yl)cyclo-hexa-1,3-diene-1-carboxyl-ate.

In the title compound, C21H19BrFNO2, two independent mol-ecules crystallize in the asymmetric unit. The cyclo-hexa-1,3-diene ring is in a slightly distorted screw-boat conformation. The dihedral angles between the mean planes of the 4-bromo-phenyl and 4-fluoro-phenyl rings are 81.0 (3) and 76.4 (2)° in the two independent mol-ecules. In the crystal, N-H⋯O hydrogen bonds link the molecules into [100] chains.

Related literature

For cyclo­hexenones as precursors for functionalized derivatives, see: Samshuddin et al. (2013 ▶); For 4-bromo-4′-fluoro­chalcone derivatives, see: Fun et al. (2012a ▶,b ▶,c ▶). For related structures, see: Jasinski et al. (2012 ▶); Kant et al. (2012 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For standard bond lengths, see Allen et al. (1987 ▶).

Experimental

Crystal data

C21H19BrFNO2

M = 416.28

Monoclinic,

a = 9.4599 (2) Å

b = 23.3634 (5) Å

c = 17.2312 (4) Å

β = 96.001 (2)°

V = 3787.51 (15) Å3

Z = 8

Cu Kα radiation

μ = 3.16 mm−1

T = 173 K

0.32 × 0.28 × 0.22 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer

Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T min = 0.587, T max = 1.000

25170 measured reflections

7427 independent reflections

5973 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.148

S = 1.03

7427 reflections

487 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.13 e Å−3

Δρmin = −0.53 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813023325/hg5341sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813023325/hg5341Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813023325/hg5341Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H19BrFNO2	F(000) = 1696
Mr = 416.28	Dx = 1.460 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.5418 Å
a = 9.4599 (2) Å	Cell parameters from 7321 reflections
b = 23.3634 (5) Å	θ = 3.2–72.3°
c = 17.2312 (4) Å	µ = 3.16 mm−1
β = 96.001 (2)°	T = 173 K
V = 3787.51 (15) Å3	Irregular, yellow
Z = 8	0.32 × 0.28 × 0.22 mm

Agilent Xcalibur (Eos, Gemini) diffractometer	7427 independent reflections
Radiation source: Enhance (Cu) X-ray Source	5973 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 16.0416 pixels mm-1	θmax = 72.5°, θmin = 3.2°
ω scans	h = −11→10
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	k = −28→25
Tmin = 0.587, Tmax = 1.000	l = −21→20
25170 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.148	w = 1/[σ2(Fo2) + (0.0771P)2 + 2.9658P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
7427 reflections	Δρmax = 1.13 e Å−3
487 parameters	Δρmin = −0.53 e Å−3
0 restraints

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
Br1A	0.37157 (5)	0.43234 (2)	0.64815 (2)	0.05829 (15)
F1A	−0.1959 (2)	0.20568 (10)	0.24677 (16)	0.0692 (7)
O1A	0.7906 (2)	0.41473 (10)	0.33655 (13)	0.0414 (5)
O2A	0.7261 (2)	0.46881 (9)	0.23026 (12)	0.0364 (5)
N1A	0.4536 (3)	0.45651 (12)	0.16870 (16)	0.0377 (6)
H1AA	0.523 (4)	0.4738 (13)	0.1701 (18)	0.022 (8)*
H1AB	0.382 (4)	0.4657 (16)	0.147 (2)	0.039 (10)*
C1A	1.0010 (5)	0.4226 (2)	0.4216 (3)	0.0819 (16)
H1AC	1.0218	0.3825	0.4110	0.123*
H1AD	0.9448	0.4249	0.4662	0.123*
H1AE	1.0903	0.4436	0.4337	0.123*
C2A	0.9191 (4)	0.44839 (17)	0.3518 (2)	0.0478 (8)
H2AA	0.8955	0.4888	0.3620	0.057*
H2AB	0.9752	0.4471	0.3064	0.057*
C3A	0.6981 (3)	0.43038 (12)	0.27564 (17)	0.0317 (6)
C4A	0.5687 (3)	0.39797 (12)	0.27159 (16)	0.0315 (6)
C5A	0.4532 (3)	0.41309 (12)	0.22021 (16)	0.0315 (6)
C6A	0.3182 (3)	0.38225 (13)	0.22013 (17)	0.0342 (6)
H6A	0.2340	0.3988	0.1947	0.041*
C7A	0.3106 (3)	0.33092 (12)	0.25538 (16)	0.0325 (6)
C8A	0.4461 (3)	0.30516 (12)	0.29415 (17)	0.0345 (6)
H8AA	0.4924	0.2827	0.2552	0.041*
H8AB	0.4227	0.2786	0.3357	0.041*
C9A	0.5506 (3)	0.35068 (12)	0.32998 (16)	0.0320 (6)
H9A	0.6451	0.3316	0.3416	0.038*
C10A	0.5058 (3)	0.37256 (12)	0.40751 (16)	0.0303 (6)
C11A	0.5381 (4)	0.33980 (13)	0.47408 (18)	0.0385 (7)
H11A	0.5885	0.3049	0.4704	0.046*
C12A	0.4988 (4)	0.35662 (14)	0.54587 (18)	0.0436 (7)
H12A	0.5218	0.3337	0.5910	0.052*
C13A	0.4255 (3)	0.40728 (14)	0.55037 (18)	0.0388 (7)
C14A	0.3931 (4)	0.44123 (15)	0.4856 (2)	0.0418 (7)
H14A	0.3431	0.4762	0.4897	0.050*
C15A	0.4342 (3)	0.42383 (14)	0.41475 (18)	0.0391 (7)
H15A	0.4130	0.4474	0.3701	0.047*
C16A	0.1765 (3)	0.29819 (13)	0.25295 (17)	0.0348 (6)
C17A	0.0446 (4)	0.32440 (14)	0.2399 (2)	0.0452 (8)
H17A	0.0400	0.3646	0.2319	0.054*
C18A	−0.0808 (4)	0.29345 (16)	0.2383 (2)	0.0500 (8)
H18A	−0.1703	0.3122	0.2308	0.060*
C19A	−0.0729 (4)	0.23585 (16)	0.2475 (2)	0.0472 (8)
C20A	0.0542 (4)	0.20668 (15)	0.2570 (2)	0.0518 (9)
H20A	0.0565	0.1661	0.2612	0.062*
C21A	0.1786 (4)	0.23819 (14)	0.2602 (2)	0.0443 (7)
H21A	0.2674	0.2189	0.2674	0.053*
Br1B	0.32238 (5)	0.06632 (2)	0.13555 (2)	0.06171 (15)
F1B	−0.1976 (3)	0.29436 (12)	0.58030 (17)	0.0815 (8)
O1B	0.7450 (2)	0.08834 (9)	0.46357 (12)	0.0365 (5)
O2B	0.7067 (2)	0.02371 (9)	0.55597 (12)	0.0341 (4)
N1B	0.4602 (3)	0.03596 (11)	0.62187 (15)	0.0357 (5)
H1BA	0.394 (4)	0.0269 (14)	0.6509 (19)	0.030 (8)*
H1BB	0.532 (4)	0.0150 (15)	0.618 (2)	0.036 (9)*
C1B	0.9329 (4)	0.09062 (15)	0.3842 (2)	0.0476 (8)
H1BC	0.8671	0.0900	0.3364	0.071*
H1BD	1.0235	0.0733	0.3740	0.071*
H1BE	0.9490	0.1303	0.4014	0.071*
C2B	0.8696 (3)	0.05690 (13)	0.4476 (2)	0.0387 (7)
H2BA	0.8437	0.0177	0.4292	0.046*
H2BB	0.9381	0.0542	0.4950	0.046*
C3B	0.6680 (3)	0.06649 (12)	0.51815 (17)	0.0311 (6)
C4B	0.5413 (3)	0.09959 (12)	0.52506 (17)	0.0322 (6)
C5B	0.4440 (3)	0.08185 (12)	0.57450 (17)	0.0315 (6)
C6B	0.3117 (3)	0.11419 (12)	0.57836 (17)	0.0353 (6)
H6B	0.2381	0.0980	0.6048	0.042*
C7B	0.2919 (3)	0.16682 (12)	0.54492 (18)	0.0367 (6)
C8B	0.4108 (4)	0.19339 (14)	0.5065 (2)	0.0478 (8)
H8BA	0.4680	0.2174	0.5454	0.057*
H8BB	0.3694	0.2190	0.4643	0.057*
C9B	0.5104 (3)	0.15061 (12)	0.47171 (18)	0.0344 (6)
H9B	0.6029	0.1709	0.4692	0.041*
C10B	0.4599 (3)	0.13196 (12)	0.38868 (18)	0.0338 (6)
C11B	0.5379 (3)	0.14645 (15)	0.32743 (19)	0.0439 (8)
H11B	0.6200	0.1698	0.3375	0.053*
C12B	0.4985 (4)	0.12771 (17)	0.2523 (2)	0.0492 (8)
H12B	0.5529	0.1379	0.2110	0.059*
C13B	0.3789 (4)	0.09399 (14)	0.23795 (19)	0.0425 (7)
C14B	0.2974 (4)	0.07961 (14)	0.2971 (2)	0.0427 (7)
H14B	0.2139	0.0571	0.2864	0.051*
C15B	0.3393 (3)	0.09842 (13)	0.3717 (2)	0.0408 (7)
H15B	0.2843	0.0882	0.4126	0.049*
C16B	0.1623 (3)	0.20068 (13)	0.55263 (18)	0.0383 (7)
C17B	0.1648 (4)	0.26074 (15)	0.5510 (2)	0.0506 (9)
H17B	0.2508	0.2799	0.5432	0.061*
C18B	0.0451 (5)	0.29259 (17)	0.5605 (2)	0.0583 (10)
H18B	0.0479	0.3332	0.5602	0.070*
C19B	−0.0789 (4)	0.26373 (18)	0.5706 (2)	0.0545 (9)
C20B	−0.0863 (4)	0.20618 (17)	0.5734 (2)	0.0496 (8)
H20B	−0.1734	0.1877	0.5806	0.060*
C21B	0.0355 (3)	0.17440 (14)	0.56566 (19)	0.0412 (7)
H21B	0.0319	0.1339	0.5693	0.049*

	U11	U22	U33	U12	U13	U23
Br1A	0.0728 (3)	0.0676 (3)	0.0371 (2)	0.0088 (2)	0.01827 (18)	−0.00322 (16)
F1A	0.0491 (12)	0.0690 (15)	0.0906 (18)	−0.0199 (11)	0.0129 (12)	0.0164 (13)
O1A	0.0323 (11)	0.0490 (12)	0.0426 (12)	−0.0040 (9)	0.0018 (9)	0.0067 (10)
O2A	0.0354 (11)	0.0427 (11)	0.0327 (10)	−0.0033 (9)	0.0117 (8)	0.0009 (9)
N1A	0.0364 (15)	0.0392 (14)	0.0367 (14)	−0.0076 (13)	−0.0002 (12)	0.0096 (11)
C1A	0.062 (3)	0.101 (4)	0.076 (3)	−0.025 (3)	−0.023 (2)	0.025 (3)
C2A	0.0348 (17)	0.057 (2)	0.050 (2)	−0.0069 (15)	−0.0012 (14)	0.0017 (16)
C3A	0.0294 (14)	0.0369 (15)	0.0303 (14)	0.0033 (11)	0.0090 (11)	−0.0031 (11)
C4A	0.0355 (15)	0.0318 (14)	0.0280 (13)	−0.0030 (12)	0.0068 (11)	0.0012 (11)
C5A	0.0356 (15)	0.0307 (14)	0.0290 (14)	−0.0035 (11)	0.0076 (11)	0.0007 (11)
C6A	0.0345 (15)	0.0361 (15)	0.0316 (14)	−0.0031 (12)	0.0016 (11)	0.0028 (11)
C7A	0.0360 (15)	0.0329 (14)	0.0287 (14)	−0.0028 (12)	0.0044 (11)	0.0001 (11)
C8A	0.0404 (16)	0.0305 (14)	0.0320 (14)	−0.0013 (12)	0.0015 (12)	0.0031 (11)
C9A	0.0315 (14)	0.0330 (14)	0.0313 (14)	−0.0011 (11)	0.0027 (11)	0.0031 (11)
C10A	0.0251 (13)	0.0332 (14)	0.0325 (14)	−0.0048 (11)	0.0025 (11)	0.0024 (11)
C11A	0.0459 (17)	0.0357 (15)	0.0339 (15)	0.0017 (13)	0.0038 (13)	0.0040 (12)
C12A	0.056 (2)	0.0441 (17)	0.0304 (15)	0.0007 (15)	0.0056 (14)	0.0080 (13)
C13A	0.0393 (16)	0.0478 (17)	0.0303 (15)	−0.0025 (14)	0.0080 (12)	−0.0032 (13)
C14A	0.0397 (17)	0.0468 (18)	0.0393 (17)	0.0067 (14)	0.0061 (13)	−0.0005 (13)
C15A	0.0404 (17)	0.0451 (17)	0.0315 (15)	0.0060 (13)	0.0018 (12)	0.0059 (12)
C16A	0.0393 (16)	0.0341 (15)	0.0314 (14)	−0.0049 (12)	0.0050 (12)	0.0039 (11)
C17A	0.0445 (18)	0.0381 (16)	0.054 (2)	−0.0030 (14)	0.0088 (15)	0.0052 (14)
C18A	0.0397 (18)	0.056 (2)	0.056 (2)	0.0000 (15)	0.0092 (15)	0.0112 (17)
C19A	0.0426 (18)	0.053 (2)	0.0471 (19)	−0.0129 (15)	0.0082 (15)	0.0070 (15)
C20A	0.058 (2)	0.0392 (18)	0.059 (2)	−0.0102 (16)	0.0086 (17)	0.0055 (15)
C21A	0.0453 (18)	0.0407 (17)	0.0469 (18)	−0.0027 (14)	0.0053 (14)	0.0029 (14)
Br1B	0.0622 (3)	0.0741 (3)	0.0478 (2)	0.0055 (2)	0.00066 (19)	−0.00554 (18)
F1B	0.0622 (15)	0.0926 (19)	0.0917 (19)	0.0427 (14)	0.0173 (14)	0.0110 (15)
O1B	0.0350 (11)	0.0394 (11)	0.0377 (11)	0.0048 (9)	0.0154 (9)	0.0039 (9)
O2B	0.0336 (10)	0.0355 (10)	0.0332 (10)	0.0024 (8)	0.0039 (8)	0.0014 (8)
N1B	0.0362 (13)	0.0371 (13)	0.0358 (13)	0.0046 (11)	0.0140 (11)	0.0068 (10)
C1B	0.0456 (18)	0.0488 (19)	0.052 (2)	−0.0019 (15)	0.0248 (16)	−0.0068 (16)
C2B	0.0348 (15)	0.0390 (16)	0.0440 (17)	0.0022 (13)	0.0127 (13)	−0.0027 (13)
C3B	0.0321 (14)	0.0334 (14)	0.0283 (14)	−0.0037 (11)	0.0057 (11)	−0.0051 (11)
C4B	0.0351 (15)	0.0297 (14)	0.0332 (14)	0.0009 (12)	0.0106 (11)	−0.0002 (11)
C5B	0.0356 (15)	0.0300 (13)	0.0299 (14)	−0.0001 (11)	0.0081 (11)	−0.0007 (11)
C6B	0.0390 (16)	0.0334 (14)	0.0359 (15)	0.0025 (12)	0.0150 (12)	0.0038 (12)
C7B	0.0390 (16)	0.0303 (14)	0.0430 (16)	0.0029 (12)	0.0144 (13)	0.0004 (12)
C8B	0.058 (2)	0.0322 (16)	0.058 (2)	0.0094 (15)	0.0280 (17)	0.0110 (14)
C9B	0.0356 (15)	0.0287 (14)	0.0415 (16)	0.0016 (12)	0.0160 (12)	0.0051 (12)
C10B	0.0326 (14)	0.0303 (14)	0.0403 (16)	0.0085 (11)	0.0120 (12)	0.0120 (12)
C11B	0.0329 (15)	0.057 (2)	0.0435 (18)	−0.0055 (14)	0.0102 (13)	0.0132 (15)
C12B	0.0404 (18)	0.068 (2)	0.0408 (18)	−0.0018 (16)	0.0120 (14)	0.0133 (16)
C13B	0.0422 (17)	0.0464 (17)	0.0391 (17)	0.0081 (14)	0.0045 (13)	0.0049 (14)
C14B	0.0372 (16)	0.0399 (16)	0.0515 (19)	−0.0001 (13)	0.0075 (14)	0.0062 (14)
C15B	0.0378 (16)	0.0385 (16)	0.0482 (18)	0.0005 (13)	0.0148 (14)	0.0095 (13)
C16B	0.0437 (17)	0.0360 (15)	0.0367 (16)	0.0048 (13)	0.0112 (13)	0.0015 (12)
C17B	0.055 (2)	0.0398 (17)	0.059 (2)	0.0078 (16)	0.0197 (17)	0.0024 (15)
C18B	0.071 (3)	0.046 (2)	0.060 (2)	0.0206 (19)	0.015 (2)	0.0042 (17)
C19B	0.051 (2)	0.067 (2)	0.047 (2)	0.0254 (19)	0.0099 (16)	0.0043 (17)
C20B	0.0385 (17)	0.070 (2)	0.0410 (18)	0.0084 (16)	0.0059 (14)	0.0041 (16)
C21B	0.0407 (17)	0.0443 (17)	0.0391 (16)	0.0046 (14)	0.0073 (13)	0.0021 (13)

Br1A—C13A	1.903 (3)	Br1B—C13B	1.903 (3)
F1A—C19A	1.359 (4)	F1B—C19B	1.357 (4)
O1A—C2A	1.449 (4)	O1B—C2B	1.439 (4)
O1A—C3A	1.345 (4)	O1B—C3B	1.348 (3)
O2A—C3A	1.237 (4)	O2B—C3B	1.228 (4)
N1A—H1AA	0.77 (3)	N1B—H1BA	0.87 (3)
N1A—H1AB	0.77 (4)	N1B—H1BB	0.85 (4)
N1A—C5A	1.348 (4)	N1B—C5B	1.346 (4)
C1A—H1AC	0.9800	C1B—H1BC	0.9800
C1A—H1AD	0.9800	C1B—H1BD	0.9800
C1A—H1AE	0.9800	C1B—H1BE	0.9800
C1A—C2A	1.489 (6)	C1B—C2B	1.519 (4)
C2A—H2AA	0.9900	C2B—H2BA	0.9900
C2A—H2AB	0.9900	C2B—H2BB	0.9900
C3A—C4A	1.434 (4)	C3B—C4B	1.442 (4)
C4A—C5A	1.379 (4)	C4B—C5B	1.382 (4)
C4A—C9A	1.516 (4)	C4B—C9B	1.515 (4)
C5A—C6A	1.466 (4)	C5B—C6B	1.469 (4)
C6A—H6A	0.9500	C6B—H6B	0.9500
C6A—C7A	1.350 (4)	C6B—C7B	1.363 (4)
C7A—C8A	1.507 (4)	C7B—C8B	1.498 (4)
C7A—C16A	1.478 (4)	C7B—C16B	1.477 (4)
C8A—H8AA	0.9900	C8B—H8BA	0.9900
C8A—H8AB	0.9900	C8B—H8BB	0.9900
C8A—C9A	1.537 (4)	C8B—C9B	1.537 (4)
C9A—H9A	1.0000	C9B—H9B	1.0000
C9A—C10A	1.531 (4)	C9B—C10B	1.524 (4)
C10A—C11A	1.386 (4)	C10B—C11B	1.391 (4)
C10A—C15A	1.388 (4)	C10B—C15B	1.389 (4)
C11A—H11A	0.9500	C11B—H11B	0.9500
C11A—C12A	1.385 (4)	C11B—C12B	1.381 (5)
C12A—H12A	0.9500	C12B—H12B	0.9500
C12A—C13A	1.378 (5)	C12B—C13B	1.379 (5)
C13A—C14A	1.377 (5)	C13B—C14B	1.382 (5)
C14A—H14A	0.9500	C14B—H14B	0.9500
C14A—C15A	1.381 (5)	C14B—C15B	1.377 (5)
C15A—H15A	0.9500	C15B—H15B	0.9500
C16A—C17A	1.388 (5)	C16B—C17B	1.404 (5)
C16A—C21A	1.407 (4)	C16B—C21B	1.387 (5)
C17A—H17A	0.9500	C17B—H17B	0.9500
C17A—C18A	1.387 (5)	C17B—C18B	1.379 (5)
C18A—H18A	0.9500	C18B—H18B	0.9500
C18A—C19A	1.356 (5)	C18B—C19B	1.379 (6)
C19A—C20A	1.378 (5)	C19B—C20B	1.348 (6)
C20A—H20A	0.9500	C20B—H20B	0.9500
C20A—C21A	1.384 (5)	C20B—C21B	1.389 (5)
C21A—H21A	0.9500	C21B—H21B	0.9500
C3A—O1A—C2A	117.3 (2)	C3B—O1B—C2B	116.9 (2)
H1AA—N1A—H1AB	125 (4)	H1BA—N1B—H1BB	122 (3)
C5A—N1A—H1AA	116 (2)	C5B—N1B—H1BA	120 (2)
C5A—N1A—H1AB	118 (3)	C5B—N1B—H1BB	117 (2)
H1AC—C1A—H1AD	109.5	H1BC—C1B—H1BD	109.5
H1AC—C1A—H1AE	109.5	H1BC—C1B—H1BE	109.5
H1AD—C1A—H1AE	109.5	H1BD—C1B—H1BE	109.5
C2A—C1A—H1AC	109.5	C2B—C1B—H1BC	109.5
C2A—C1A—H1AD	109.5	C2B—C1B—H1BD	109.5
C2A—C1A—H1AE	109.5	C2B—C1B—H1BE	109.5
O1A—C2A—C1A	106.4 (3)	O1B—C2B—C1B	105.4 (3)
O1A—C2A—H2AA	110.4	O1B—C2B—H2BA	110.7
O1A—C2A—H2AB	110.4	O1B—C2B—H2BB	110.7
C1A—C2A—H2AA	110.4	C1B—C2B—H2BA	110.7
C1A—C2A—H2AB	110.4	C1B—C2B—H2BB	110.7
H2AA—C2A—H2AB	108.6	H2BA—C2B—H2BB	108.8
O1A—C3A—C4A	112.1 (2)	O1B—C3B—C4B	111.6 (2)
O2A—C3A—O1A	121.7 (3)	O2B—C3B—O1B	121.7 (3)
O2A—C3A—C4A	126.2 (3)	O2B—C3B—C4B	126.7 (3)
C3A—C4A—C9A	120.5 (3)	C3B—C4B—C9B	118.8 (2)
C5A—C4A—C3A	120.7 (3)	C5B—C4B—C3B	120.2 (3)
C5A—C4A—C9A	118.4 (3)	C5B—C4B—C9B	120.7 (3)
N1A—C5A—C4A	124.0 (3)	N1B—C5B—C4B	124.9 (3)
N1A—C5A—C6A	115.6 (3)	N1B—C5B—C6B	115.2 (3)
C4A—C5A—C6A	120.4 (3)	C4B—C5B—C6B	119.9 (3)
C5A—C6A—H6A	119.2	C5B—C6B—H6B	119.2
C7A—C6A—C5A	121.5 (3)	C7B—C6B—C5B	121.7 (3)
C7A—C6A—H6A	119.2	C7B—C6B—H6B	119.2
C6A—C7A—C8A	118.2 (3)	C6B—C7B—C8B	119.0 (3)
C6A—C7A—C16A	122.2 (3)	C6B—C7B—C16B	121.6 (3)
C16A—C7A—C8A	119.6 (3)	C16B—C7B—C8B	119.1 (3)
C7A—C8A—H8AA	109.1	C7B—C8B—H8BA	108.5
C7A—C8A—H8AB	109.1	C7B—C8B—H8BB	108.5
C7A—C8A—C9A	112.5 (2)	C7B—C8B—C9B	115.0 (3)
H8AA—C8A—H8AB	107.8	H8BA—C8B—H8BB	107.5
C9A—C8A—H8AA	109.1	C9B—C8B—H8BA	108.5
C9A—C8A—H8AB	109.1	C9B—C8B—H8BB	108.5
C4A—C9A—C8A	110.5 (2)	C4B—C9B—C8B	111.3 (2)
C4A—C9A—H9A	107.3	C4B—C9B—H9B	106.5
C4A—C9A—C10A	113.4 (2)	C4B—C9B—C10B	111.5 (2)
C8A—C9A—H9A	107.3	C8B—C9B—H9B	106.5
C10A—C9A—C8A	110.9 (2)	C10B—C9B—C8B	114.0 (3)
C10A—C9A—H9A	107.3	C10B—C9B—H9B	106.5
C11A—C10A—C9A	118.7 (3)	C11B—C10B—C9B	120.2 (3)
C11A—C10A—C15A	118.0 (3)	C15B—C10B—C9B	121.9 (3)
C15A—C10A—C9A	123.3 (3)	C15B—C10B—C11B	117.8 (3)
C10A—C11A—H11A	119.1	C10B—C11B—H11B	119.3
C12A—C11A—C10A	121.7 (3)	C12B—C11B—C10B	121.5 (3)
C12A—C11A—H11A	119.1	C12B—C11B—H11B	119.3
C11A—C12A—H12A	120.7	C11B—C12B—H12B	120.5
C13A—C12A—C11A	118.5 (3)	C13B—C12B—C11B	119.0 (3)
C13A—C12A—H12A	120.7	C13B—C12B—H12B	120.5
C12A—C13A—Br1A	119.8 (2)	C12B—C13B—Br1B	120.4 (3)
C14A—C13A—Br1A	118.8 (2)	C12B—C13B—C14B	121.2 (3)
C14A—C13A—C12A	121.3 (3)	C14B—C13B—Br1B	118.5 (3)
C13A—C14A—H14A	120.4	C13B—C14B—H14B	120.6
C13A—C14A—C15A	119.2 (3)	C15B—C14B—C13B	118.8 (3)
C15A—C14A—H14A	120.4	C15B—C14B—H14B	120.6
C10A—C15A—H15A	119.4	C10B—C15B—H15B	119.1
C14A—C15A—C10A	121.2 (3)	C14B—C15B—C10B	121.8 (3)
C14A—C15A—H15A	119.4	C14B—C15B—H15B	119.1
C17A—C16A—C7A	122.1 (3)	C17B—C16B—C7B	121.2 (3)
C17A—C16A—C21A	117.3 (3)	C21B—C16B—C7B	121.2 (3)
C21A—C16A—C7A	120.6 (3)	C21B—C16B—C17B	117.5 (3)
C16A—C17A—H17A	119.1	C16B—C17B—H17B	119.3
C18A—C17A—C16A	121.8 (3)	C18B—C17B—C16B	121.4 (4)
C18A—C17A—H17A	119.1	C18B—C17B—H17B	119.3
C17A—C18A—H18A	120.7	C17B—C18B—H18B	121.0
C19A—C18A—C17A	118.6 (3)	C17B—C18B—C19B	118.1 (4)
C19A—C18A—H18A	120.7	C19B—C18B—H18B	121.0
F1A—C19A—C20A	118.7 (3)	F1B—C19B—C18B	118.9 (4)
C18A—C19A—F1A	118.5 (3)	C20B—C19B—F1B	118.3 (4)
C18A—C19A—C20A	122.8 (3)	C20B—C19B—C18B	122.7 (3)
C19A—C20A—H20A	121.0	C19B—C20B—H20B	120.6
C19A—C20A—C21A	118.0 (3)	C19B—C20B—C21B	118.9 (3)
C21A—C20A—H20A	121.0	C21B—C20B—H20B	120.6
C16A—C21A—H21A	119.3	C16B—C21B—C20B	121.3 (3)
C20A—C21A—C16A	121.5 (3)	C16B—C21B—H21B	119.3
C20A—C21A—H21A	119.3	C20B—C21B—H21B	119.3
Br1A—C13A—C14A—C15A	178.8 (3)	Br1B—C13B—C14B—C15B	178.6 (2)
F1A—C19A—C20A—C21A	−177.9 (3)	F1B—C19B—C20B—C21B	−178.3 (3)
O1A—C3A—C4A—C5A	170.7 (3)	O1B—C3B—C4B—C5B	175.9 (3)
O1A—C3A—C4A—C9A	−2.3 (4)	O1B—C3B—C4B—C9B	1.7 (4)
O2A—C3A—C4A—C5A	−8.9 (5)	O2B—C3B—C4B—C5B	−4.6 (5)
O2A—C3A—C4A—C9A	178.1 (3)	O2B—C3B—C4B—C9B	−178.8 (3)
N1A—C5A—C6A—C7A	165.1 (3)	N1B—C5B—C6B—C7B	168.0 (3)
C2A—O1A—C3A—O2A	6.0 (4)	C2B—O1B—C3B—O2B	4.4 (4)
C2A—O1A—C3A—C4A	−173.7 (3)	C2B—O1B—C3B—C4B	−176.1 (2)
C3A—O1A—C2A—C1A	179.5 (3)	C3B—O1B—C2B—C1B	179.4 (3)
C3A—C4A—C5A—N1A	3.0 (5)	C3B—C4B—C5B—N1B	3.5 (5)
C3A—C4A—C5A—C6A	−175.7 (3)	C3B—C4B—C5B—C6B	−176.9 (3)
C3A—C4A—C9A—C8A	−152.6 (3)	C3B—C4B—C9B—C8B	−157.6 (3)
C3A—C4A—C9A—C10A	82.2 (3)	C3B—C4B—C9B—C10B	73.9 (3)
C4A—C5A—C6A—C7A	−16.0 (4)	C4B—C5B—C6B—C7B	−11.6 (5)
C4A—C9A—C10A—C11A	−155.2 (3)	C4B—C9B—C10B—C11B	−118.5 (3)
C4A—C9A—C10A—C15A	24.8 (4)	C4B—C9B—C10B—C15B	58.9 (4)
C5A—C4A—C9A—C8A	34.3 (4)	C5B—C4B—C9B—C8B	28.3 (4)
C5A—C4A—C9A—C10A	−90.9 (3)	C5B—C4B—C9B—C10B	−100.2 (3)
C5A—C6A—C7A—C8A	−1.0 (4)	C5B—C6B—C7B—C8B	−2.8 (5)
C5A—C6A—C7A—C16A	−177.4 (3)	C5B—C6B—C7B—C16B	−176.5 (3)
C6A—C7A—C8A—C9A	33.8 (4)	C6B—C7B—C8B—C9B	29.7 (5)
C6A—C7A—C16A—C17A	−23.2 (5)	C6B—C7B—C16B—C17B	151.0 (3)
C6A—C7A—C16A—C21A	153.7 (3)	C6B—C7B—C16B—C21B	−25.7 (5)
C7A—C8A—C9A—C4A	−48.8 (3)	C7B—C8B—C9B—C4B	−40.7 (4)
C7A—C8A—C9A—C10A	77.8 (3)	C7B—C8B—C9B—C10B	86.4 (4)
C7A—C16A—C17A—C18A	−179.5 (3)	C7B—C16B—C17B—C18B	−178.0 (3)
C7A—C16A—C21A—C20A	−179.1 (3)	C7B—C16B—C21B—C20B	179.6 (3)
C8A—C7A—C16A—C17A	160.5 (3)	C8B—C7B—C16B—C17B	−22.7 (5)
C8A—C7A—C16A—C21A	−22.6 (4)	C8B—C7B—C16B—C21B	160.6 (3)
C8A—C9A—C10A—C11A	79.9 (3)	C8B—C9B—C10B—C11B	114.5 (3)
C8A—C9A—C10A—C15A	−100.2 (3)	C8B—C9B—C10B—C15B	−68.1 (4)
C9A—C4A—C5A—N1A	176.1 (3)	C9B—C4B—C5B—N1B	177.6 (3)
C9A—C4A—C5A—C6A	−2.7 (4)	C9B—C4B—C5B—C6B	−2.9 (4)
C9A—C10A—C11A—C12A	−179.0 (3)	C9B—C10B—C11B—C12B	176.7 (3)
C9A—C10A—C15A—C14A	178.5 (3)	C9B—C10B—C15B—C14B	−177.2 (3)
C10A—C11A—C12A—C13A	0.1 (5)	C10B—C11B—C12B—C13B	0.1 (5)
C11A—C10A—C15A—C14A	−1.5 (5)	C11B—C10B—C15B—C14B	0.3 (5)
C11A—C12A—C13A—Br1A	−179.3 (3)	C11B—C12B—C13B—Br1B	−179.1 (3)
C11A—C12A—C13A—C14A	−0.9 (5)	C11B—C12B—C13B—C14B	1.0 (5)
C12A—C13A—C14A—C15A	0.5 (5)	C12B—C13B—C14B—C15B	−1.5 (5)
C13A—C14A—C15A—C10A	0.8 (5)	C13B—C14B—C15B—C10B	0.8 (5)
C15A—C10A—C11A—C12A	1.0 (5)	C15B—C10B—C11B—C12B	−0.8 (5)
C16A—C7A—C8A—C9A	−149.8 (3)	C16B—C7B—C8B—C9B	−156.5 (3)
C16A—C17A—C18A—C19A	−1.9 (6)	C16B—C17B—C18B—C19B	−0.9 (6)
C17A—C16A—C21A—C20A	−2.0 (5)	C17B—C16B—C21B—C20B	2.8 (5)
C17A—C18A—C19A—F1A	179.2 (3)	C17B—C18B—C19B—F1B	179.8 (4)
C17A—C18A—C19A—C20A	−1.2 (6)	C17B—C18B—C19B—C20B	1.7 (6)
C18A—C19A—C20A—C21A	2.6 (6)	C18B—C19B—C20B—C21B	−0.2 (6)
C19A—C20A—C21A—C16A	−0.9 (5)	C19B—C20B—C21B—C16B	−2.1 (5)
C21A—C16A—C17A—C18A	3.5 (5)	C21B—C16B—C17B—C18B	−1.2 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···O2A	0.77 (3)	2.09 (3)	2.698 (4)	136 (3)
N1A—H1AB···O2Bi	0.77 (4)	2.17 (4)	2.915 (4)	162 (4)
N1B—H1BA···O2Aii	0.87 (3)	2.20 (4)	3.044 (3)	163 (3)
N1B—H1BB···O2B	0.85 (4)	2.07 (4)	2.714 (3)	132 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1AA⋯O2A	0.77 (3)	2.09 (3)	2.698 (4)	136 (3)
N1A—H1AB⋯O2B i	0.77 (4)	2.17 (4)	2.915 (4)	162 (4)
N1B—H1BA⋯O2A ii	0.87 (3)	2.20 (4)	3.044 (3)	163 (3)
N1B—H1BB⋯O2B	0.85 (4)	2.07 (4)	2.714 (3)	132 (3)

Symmetry codes: (i) ; (ii) .