(+)-(2R,3S)-3-Bromo-2-chloro-N,N-diiso­propyl-3-phenyl­propan­amide and (+)-(2R,3S)-3-bromo-2-chloro-N-(4-nitro­phenyl)-3-phenyl­propan­amide

The stereochemistries at positions 2 and 3 of the title compounds, C₁₅H₂₁BrClNO, (I), and C₁₅H₁₂BrClN₂O₃, (II), have been confirmed by X-ray structural analysis. The halogen atoms adopt an antiperiplanar arrangement in each case.

S1. Comment

The title compounds, (I) and (II), were investigated as part of a study of the stereoselective bromination of halohydrocinnamates, and the structural determinations were undertaken to determine the absolute configurations at the 2 and 3 positions in the molecules.

Compound (II) crystallizes with two unique molecules in the asymmetric unit of the orthorhombic unit cell. Small differences in bond lengths and angles between the discrete molecular units can be ascribed to crystal-packing effects. The stereochemistries at the 2 and 3 positions of both compounds were found to be R and S, respectively. The correct choice of absolute structure was confirmed by the values of the Flack parameters [0.052 (16) for (I) and 0.027 (6) for (II); Flack, 1983]. The halogen atoms were found to be antiperiplanar in both cases, with torsion angles Cl1—C2—C3—Br = −175.4 (3)° for (I), and Cl11—C12—C13—Br11 = 177.20 (16)° and Cl21—C22—C23—Br21 = 177.40 (14)° for the two unique molecules of (II).

The unit cell of (I) contains well separated molecules with the shortest intermolecular contact, not involving H atoms, being 3.301 (1) Å for C2···O1(-y + 1, x, z + 1/4). In contrast, the structure of (II) is stabilized by a combination of hydrogen-bond and columnar interactions. Pairs of unique molecules form via N—H···O intermolecular hydrogen bonds parallel to the c axis [H21A···O222(3/2 − x, −y, −1/2 + z) 2.41, N21···O222 3.245 Å and N21—H21A···O222 158°; see Table 3]. Columnar interactions involve the nitrophenyl and phenyl rings of both unique molecules, with mean interplanar separations C14···C19/C24···C29 3.398, C110···C115/C24···C29 3.425, C210···215/C14···C19 3.458 and C110···C115/C210···C215 3.566 Å (Spek, 1995).

S2. Experimental

A mixture of (S)-2-chloro-N,N-diisopropyl-3-phenylpropanamide (500 mg, 1.86 mmol) and N-bromosuccinimide (331 mg, 1.86 mmol) in CCl₄ (25 ml) was heated at reflux under nitrogen. The reaction was initiated by irradiation with a 160 W mercury lamp. After 2 h, the mixture was cooled, washed with water, dried (MgSO₄) and the solvent removed under reduced pressure. Colourless crystals of (I) were obtained from CH₂Cl₂ (Wong et al., 2000), [α]_D = +106.6°. Compound (II) was prepared by stirring a mixture of (2R,3S)-3-bromo-2-chloro-3-phenylpropanoic acid chloride (6.82 g, 24.2 mmol) and p-nitroaniline (3.34 g, 24.2 mmol) in CH₂Cl₂ (50 ml) under an anhydrous atmosphere for 2 d. The solution was washed with 1 M HCl (6 times) and dried (MgSO₄). The solvent was removed under reduced pressure and the product purified by column chromatography, eluting with CH₂Cl₂. The resulting solid (II) was recrytallized from hexane/CH₂Cl₂ (Wong et al., 2000), [α]_D = +22.7°.

Computing details

For both compounds, data collection: SMART (Siemens, 1994); cell refinement: SMART; data reduction: SHELXTL/PC (Sheldrick, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

(I) (+)-(2R,3S)-3-Bromo-2-chloro-N,N-diisopropyl-3-phenylpropanamide

Crystal data

C15H21BrClNO	Dx = 1.369 Mg m^−3
Mr = 346.69	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41	Cell parameters from 21617 reflections
Hall symbol: P 41	θ = 2.3–26.4°
a = 8.8863 (19) Å	µ = 2.60 mm^−1
c = 21.299 (6) Å	T = 168 K
V = 1681.9 (7) Å^3	Plate, colourless
Z = 4	0.76 × 0.34 × 0.10 mm
F(000) = 712

Data collection

CCD area-detector diffractometer	2921 independent reflections
Radiation source: fine-focus sealed tube	2304 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.102
ϕ and ω scans	θmax = 26.4°, θmin = 2.3°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1997)	h = −11→11
Tmin = 0.332, Tmax = 0.771	k = −11→11
21617 measured reflections	l = −14→26

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.133	w = 1/[σ^2(Fo^2) + (0.0849P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
2921 reflections	Δρmax = 0.64 e Å^−3
176 parameters	Δρmin = −0.71 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1168 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.052 (16)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. andis not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C9	0.2529 (7)	0.3014 (8)	0.2412 (3)	0.0378 (15)
H9	0.3204	0.3563	0.2672	0.045*
C8	0.1234 (7)	0.2365 (6)	0.2677 (4)	0.0370 (15)
H8	0.1034	0.2460	0.3113	0.044*
C7	0.0249 (7)	0.1580 (7)	0.2287 (4)	0.0428 (17)
H7	−0.0631	0.1138	0.2460	0.051*
C6	0.0527 (7)	0.1433 (7)	0.1658 (4)	0.0452 (17)
H6	−0.0150	0.0889	0.1397	0.054*
C5	0.1819 (8)	0.2094 (8)	0.1403 (3)	0.0453 (18)
H5	0.2007	0.2016	0.0965	0.054*
C4	0.2831 (6)	0.2863 (6)	0.1783 (3)	0.0340 (14)
C3	0.4227 (7)	0.3485 (7)	0.1487 (4)	0.0394 (15)
H3	0.4101	0.3467	0.1020	0.047*
Br1	0.60110 (8)	0.22026 (8)	0.17171 (4)	0.0526 (3)
C2	0.4730 (6)	0.5055 (6)	0.1684 (3)	0.0311 (13)
H2	0.5049	0.5061	0.2134	0.037*
Cl1	0.30793 (16)	0.63876 (15)	0.15554 (7)	0.0349 (3)
C1	0.6018 (6)	0.5636 (6)	0.1256 (3)	0.0248 (12)
O1	0.5841 (4)	0.5456 (4)	0.0697 (2)	0.0322 (9)
N1	0.7241 (5)	0.6319 (5)	0.1517 (2)	0.0279 (11)
C10	0.7523 (7)	0.6510 (6)	0.2187 (3)	0.0325 (14)
H10	0.6579	0.6223	0.2412	0.039*
C12	0.7864 (7)	0.8144 (7)	0.2356 (4)	0.0414 (16)
H12A	0.8869	0.8412	0.2204	0.062*
H12B	0.7825	0.8267	0.2813	0.062*
H12C	0.7114	0.8803	0.2160	0.062*
C13	0.8445 (7)	0.6878 (7)	0.1073 (3)	0.0335 (14)
H13	0.9268	0.7274	0.1347	0.040*
C14	0.9157 (8)	0.5626 (9)	0.0689 (4)	0.0503 (19)
H14A	0.9240	0.4718	0.0948	0.075*
H14B	1.0162	0.5939	0.0552	0.075*
H14C	0.8530	0.5414	0.0322	0.075*
C15	0.7901 (8)	0.8216 (8)	0.0695 (4)	0.0460 (17)
H15A	0.7153	0.7881	0.0387	0.069*
H15B	0.8754	0.8677	0.0476	0.069*
H15C	0.7443	0.8955	0.0978	0.069*
C11	0.8758 (9)	0.5444 (7)	0.2410 (4)	0.0481 (18)
H52A	0.8433	0.4401	0.2348	0.072*
H52B	0.8954	0.5618	0.2857	0.072*
H52C	0.9679	0.5630	0.2170	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C9	0.032 (3)	0.043 (4)	0.038 (4)	−0.014 (3)	−0.006 (3)	0.005 (3)
C8	0.038 (3)	0.027 (3)	0.045 (4)	−0.007 (3)	0.001 (3)	0.009 (3)
C7	0.032 (3)	0.027 (3)	0.070 (5)	−0.012 (3)	0.005 (3)	0.006 (3)
C6	0.037 (3)	0.041 (3)	0.057 (5)	−0.016 (3)	−0.007 (4)	−0.005 (3)
C5	0.046 (4)	0.050 (4)	0.040 (4)	−0.020 (3)	0.002 (3)	−0.007 (3)
C4	0.031 (3)	0.035 (3)	0.036 (4)	−0.009 (2)	−0.006 (3)	0.001 (3)
C3	0.048 (4)	0.029 (3)	0.042 (4)	0.000 (3)	−0.001 (3)	0.000 (3)
Br1	0.0406 (4)	0.0424 (4)	0.0750 (6)	0.0072 (3)	0.0061 (4)	0.0081 (4)
C2	0.026 (3)	0.034 (3)	0.034 (4)	−0.008 (2)	−0.002 (3)	−0.002 (3)
Cl1	0.0395 (8)	0.0310 (7)	0.0343 (8)	−0.0067 (6)	0.0059 (7)	0.0054 (6)
C1	0.027 (3)	0.027 (3)	0.020 (3)	−0.001 (2)	0.000 (2)	0.005 (2)
O1	0.027 (2)	0.036 (2)	0.033 (3)	−0.0089 (17)	−0.0031 (18)	0.0037 (19)
N1	0.026 (2)	0.025 (2)	0.033 (3)	−0.0025 (19)	0.004 (2)	0.006 (2)
C10	0.036 (3)	0.030 (3)	0.031 (4)	−0.013 (3)	−0.005 (3)	0.001 (3)
C12	0.034 (3)	0.035 (3)	0.055 (5)	−0.008 (3)	−0.002 (3)	−0.011 (3)
C13	0.024 (3)	0.037 (3)	0.040 (4)	−0.009 (3)	0.001 (3)	−0.001 (3)
C14	0.031 (3)	0.062 (5)	0.057 (5)	−0.009 (3)	0.018 (3)	−0.002 (4)
C15	0.050 (4)	0.037 (4)	0.052 (5)	−0.015 (3)	0.005 (3)	0.012 (3)
C11	0.056 (4)	0.035 (4)	0.054 (5)	−0.002 (3)	−0.018 (4)	0.002 (3)

Geometric parameters (Å, º)

C9—C4	1.373 (10)	C2—Cl1	1.905 (6)
C9—C8	1.405 (9)	C1—O1	1.213 (7)
C8—C7	1.395 (10)	C1—N1	1.363 (7)
C7—C6	1.367 (11)	N1—C10	1.458 (8)
C6—C5	1.399 (9)	N1—C13	1.513 (7)
C5—C4	1.389 (9)	C10—C11	1.525 (10)
C4—C3	1.498 (9)	C10—C12	1.526 (8)
C3—C2	1.525 (8)	C13—C15	1.514 (9)
C3—Br1	2.013 (7)	C13—C14	1.518 (9)
C2—C1	1.551 (8)
C4—C9—C8	120.8 (6)	C1—C2—Cl1	106.1 (4)
C7—C8—C9	118.7 (7)	O1—C1—N1	124.2 (5)
C6—C7—C8	121.2 (6)	O1—C1—C2	115.9 (5)
C7—C6—C5	119.2 (6)	N1—C1—C2	119.8 (5)
C4—C5—C6	120.8 (7)	C1—N1—C10	126.0 (5)
C9—C4—C5	119.3 (6)	C1—N1—C13	117.1 (5)
C9—C4—C3	122.5 (5)	C10—N1—C13	116.9 (5)
C5—C4—C3	118.2 (6)	N1—C10—C11	110.9 (6)
C4—C3—C2	117.7 (5)	N1—C10—C12	112.1 (6)
C4—C3—Br1	109.9 (4)	C11—C10—C12	112.0 (5)
C2—C3—Br1	102.7 (4)	N1—C13—C15	111.3 (5)
C3—C2—C1	111.1 (5)	N1—C13—C14	113.0 (5)
C3—C2—Cl1	107.7 (4)	C15—C13—C14	115.0 (6)
C4—C9—C8—C7	−0.8 (10)	C3—C2—C1—O1	45.6 (7)
C9—C8—C7—C6	0.1 (10)	Cl1—C2—C1—O1	−71.1 (6)
C8—C7—C6—C5	−0.4 (10)	C3—C2—C1—N1	−135.2 (5)
C7—C6—C5—C4	1.4 (11)	Cl1—C2—C1—N1	108.1 (5)
C8—C9—C4—C5	1.8 (10)	O1—C1—N1—C10	−177.6 (6)
C8—C9—C4—C3	−177.6 (6)	C2—C1—N1—C10	3.3 (8)
C6—C5—C4—C9	−2.1 (10)	O1—C1—N1—C13	−0.1 (8)
C6—C5—C4—C3	177.3 (6)	C2—C1—N1—C13	−179.2 (5)
C9—C4—C3—C2	−42.5 (9)	C1—N1—C10—C11	106.5 (6)
C5—C4—C3—C2	138.1 (6)	C13—N1—C10—C11	−71.0 (6)
C9—C4—C3—Br1	74.5 (7)	C1—N1—C10—C12	−127.5 (6)
C5—C4—C3—Br1	−104.9 (6)	C13—N1—C10—C12	54.9 (7)
C4—C3—C2—C1	−170.3 (5)	C1—N1—C13—C15	69.7 (7)
Br1—C3—C2—C1	68.9 (5)	C10—N1—C13—C15	−112.5 (6)
C4—C3—C2—Cl1	−54.6 (7)	C1—N1—C13—C14	−61.5 (7)
Br1—C3—C2—Cl1	−175.4 (3)	C10—N1—C13—C14	116.2 (6)

(II) (+)-(2R,3S)-3-Bromo-2-chloro-N-(4-nitrophenyl)-3-phenylpropanamide

Crystal data

C15H12BrClN2O3	Dx = 1.609 Mg m^−3
Mr = 383.63	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 40975 reflections
a = 13.900 (4) Å	θ = 2.0–26.5°
b = 14.648 (5) Å	µ = 2.78 mm^−1
c = 15.553 (5) Å	T = 170 K
V = 3166.8 (17) Å^3	Block, pale yellow
Z = 8	0.64 × 0.30 × 0.20 mm
F(000) = 1536

Data collection

CCD area-detector diffractometer	6487 independent reflections
Radiation source: fine-focus sealed tube	5023 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
ϕ and ω scans	θmax = 26.5°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1997)	h = −17→17
Tmin = 0.371, Tmax = 0.574	k = −18→16
40975 measured reflections	l = −19→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0309P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max < 0.001
6487 reflections	Δρmax = 0.36 e Å^−3
397 parameters	Δρmin = −0.65 e Å^−3
0 restraints	Absolute structure: Flack (1983), 2852 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.027 (6)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based

on F, with F set to zero for negative F². The threshold expression of

F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C19	0.0566 (2)	0.3773 (2)	0.1383 (2)	0.0335 (8)
H19	0.0607	0.3835	0.0776	0.040*
C18	0.0403 (2)	0.4536 (3)	0.1884 (2)	0.0391 (9)
H18	0.0345	0.5120	0.1623	0.047*
C17	0.0326 (3)	0.4444 (3)	0.2773 (2)	0.0398 (9)
H17	0.0216	0.4967	0.3120	0.048*
C16	0.0407 (2)	0.3597 (3)	0.3148 (2)	0.0427 (10)
H16	0.0346	0.3535	0.3753	0.051*
C15	0.0579 (2)	0.2834 (3)	0.2643 (2)	0.0338 (8)
H15	0.0636	0.2251	0.2905	0.041*
C14	0.0669 (2)	0.2916 (2)	0.17542 (19)	0.0279 (8)
C13	0.0896 (2)	0.2086 (2)	0.1228 (2)	0.0298 (8)
H13	0.0888	0.1540	0.1614	0.036*
Br11	0.22035 (2)	0.22079 (3)	0.07224 (3)	0.04693 (11)
C12	0.0237 (2)	0.1907 (2)	0.04730 (19)	0.0288 (7)
H12	0.0252	0.2437	0.0068	0.035*
Cl11	−0.09659 (6)	0.17288 (6)	0.08585 (6)	0.0444 (2)
C11	0.0487 (2)	0.1030 (2)	−0.0004 (2)	0.0290 (7)
O11	0.07335 (18)	0.03402 (16)	0.03619 (15)	0.0415 (6)
N11	0.03642 (18)	0.11036 (16)	−0.08716 (16)	0.0285 (6)
H11A	0.0233	0.1656	−0.1062	0.034*
C110	0.0418 (2)	0.0419 (2)	−0.1502 (2)	0.0247 (7)
C111	0.0417 (2)	0.0707 (2)	−0.2358 (2)	0.0277 (8)
H111	0.0421	0.1341	−0.2488	0.033*
C112	0.0409 (2)	0.0078 (2)	−0.3012 (2)	0.0291 (8)
H112	0.0399	0.0269	−0.3596	0.035*
C113	0.0417 (2)	−0.0832 (2)	−0.2806 (2)	0.0269 (7)
N12	0.0385 (2)	−0.1500 (2)	−0.3492 (2)	0.0381 (7)
O121	0.0379 (2)	−0.23186 (19)	−0.32907 (17)	0.0658 (9)
O122	0.03745 (19)	−0.12469 (17)	−0.42397 (16)	0.0501 (7)
C114	0.0428 (2)	−0.1136 (2)	−0.1959 (2)	0.0303 (8)
H114	0.0431	−0.1771	−0.1834	0.036*
C115	0.0435 (2)	−0.0508 (2)	−0.1306 (2)	0.0269 (7)
H115	0.0450	−0.0704	−0.0724	0.032*
C29	0.6858 (2)	0.8692 (3)	0.1582 (2)	0.0340 (8)
H29	0.6796	0.8046	0.1560	0.041*
C28	0.7066 (3)	0.9117 (3)	0.2352 (2)	0.0452 (10)
H28	0.7154	0.8758	0.2855	0.054*
C27	0.7146 (3)	1.0045 (3)	0.2401 (3)	0.0510 (11)
H27	0.7275	1.0329	0.2938	0.061*
C26	0.7040 (3)	1.0563 (3)	0.1677 (3)	0.0494 (11)
H26	0.7110	1.1207	0.1713	0.059*
C25	0.6829 (2)	1.0156 (2)	0.0880 (3)	0.0391 (9)
H25	0.6748	1.0519	0.0379	0.047*
C24	0.6741 (2)	0.9207 (2)	0.0841 (2)	0.0303 (8)
C23	0.6516 (2)	0.8769 (2)	−0.0006 (2)	0.0274 (7)
H23	0.6499	0.9254	−0.0458	0.033*
Br21	0.52362 (2)	0.81695 (3)	0.00453 (2)	0.04684 (11)
C22	0.7214 (2)	0.8029 (2)	−0.02867 (18)	0.0263 (7)
H22	0.7233	0.7530	0.0152	0.032*
Cl21	0.83885 (6)	0.85410 (7)	−0.03951 (6)	0.0427 (2)
C21	0.6982 (2)	0.7631 (2)	−0.1174 (2)	0.0276 (8)
O21	0.67049 (17)	0.81173 (15)	−0.17529 (14)	0.0378 (6)
N21	0.71489 (18)	0.67149 (16)	−0.12412 (15)	0.0260 (6)
H21A	0.7302	0.6432	−0.0761	0.031*
C210	0.7106 (2)	0.6170 (2)	−0.19812 (19)	0.0239 (7)
C211	0.7207 (2)	0.5229 (2)	−0.1865 (2)	0.0257 (7)
H211	0.7281	0.4985	−0.1303	0.031*
C212	0.7199 (2)	0.4657 (2)	−0.2568 (2)	0.0296 (8)
H212	0.7268	0.4017	−0.2494	0.036*
C213	0.7090 (2)	0.5024 (2)	−0.3385 (2)	0.0281 (7)
N22	0.7106 (2)	0.4408 (2)	−0.4122 (2)	0.0425 (8)
O222	0.7211 (2)	0.3589 (2)	−0.39816 (18)	0.0645 (8)
O221	0.7015 (2)	0.47252 (19)	−0.48425 (17)	0.0646 (8)
C214	0.6984 (2)	0.5950 (2)	−0.3511 (2)	0.0318 (8)
H214	0.6908	0.6187	−0.4075	0.038*
C215	0.6989 (2)	0.6532 (2)	−0.2809 (2)	0.0303 (8)
H215	0.6913	0.7172	−0.2887	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C19	0.039 (2)	0.037 (2)	0.0251 (19)	0.0005 (15)	0.0059 (15)	−0.0011 (17)
C18	0.036 (2)	0.035 (2)	0.047 (2)	−0.0007 (16)	0.0001 (18)	−0.0063 (17)
C17	0.033 (2)	0.046 (2)	0.040 (2)	−0.0019 (18)	0.0013 (17)	−0.0223 (19)
C16	0.038 (2)	0.067 (3)	0.0230 (19)	−0.001 (2)	−0.0008 (16)	−0.0140 (19)
C15	0.0373 (19)	0.043 (2)	0.0216 (18)	0.0022 (17)	0.0003 (14)	0.0029 (17)
C14	0.0286 (16)	0.034 (2)	0.0207 (17)	−0.0014 (14)	0.0011 (13)	−0.0068 (15)
C13	0.0276 (16)	0.037 (2)	0.0246 (18)	−0.0002 (15)	0.0029 (13)	0.0010 (15)
Br11	0.03405 (18)	0.0556 (2)	0.0512 (2)	−0.00105 (18)	0.00936 (18)	−0.0180 (2)
C12	0.0332 (16)	0.0316 (19)	0.0215 (17)	0.0063 (15)	0.0003 (14)	−0.0001 (14)
Cl11	0.0307 (4)	0.0540 (6)	0.0485 (6)	−0.0010 (4)	0.0026 (4)	−0.0198 (5)
C11	0.0311 (16)	0.0309 (19)	0.0250 (18)	0.0035 (13)	−0.0017 (16)	−0.0001 (17)
O11	0.0655 (17)	0.0336 (15)	0.0253 (13)	0.0126 (12)	−0.0102 (12)	0.0007 (11)
N11	0.0452 (16)	0.0181 (14)	0.0221 (16)	0.0024 (12)	−0.0003 (13)	0.0023 (12)
C110	0.0239 (17)	0.0281 (19)	0.0220 (18)	0.0004 (14)	−0.0020 (14)	−0.0046 (14)
C111	0.0315 (19)	0.0264 (18)	0.0251 (19)	0.0029 (15)	−0.0018 (14)	0.0021 (14)
C112	0.0313 (18)	0.033 (2)	0.0228 (18)	0.0039 (15)	−0.0027 (15)	−0.0008 (15)
C113	0.0251 (17)	0.029 (2)	0.0263 (19)	−0.0017 (15)	−0.0003 (14)	−0.0038 (15)
N12	0.0411 (18)	0.0360 (19)	0.037 (2)	−0.0061 (14)	0.0024 (15)	−0.0106 (15)
O121	0.117 (3)	0.0322 (17)	0.0476 (18)	−0.0214 (18)	−0.0021 (17)	−0.0127 (13)
O122	0.0764 (18)	0.0485 (16)	0.0255 (15)	0.0024 (14)	−0.0029 (14)	−0.0118 (13)
C114	0.0348 (19)	0.0226 (18)	0.033 (2)	−0.0039 (15)	−0.0012 (15)	0.0038 (15)
C115	0.0305 (18)	0.0263 (19)	0.0239 (18)	−0.0008 (14)	−0.0033 (14)	0.0020 (14)
C29	0.0327 (18)	0.039 (2)	0.030 (2)	0.0016 (15)	−0.0033 (15)	−0.0031 (17)
C28	0.039 (2)	0.065 (3)	0.032 (2)	0.007 (2)	0.0002 (17)	−0.0109 (19)
C27	0.033 (2)	0.070 (3)	0.050 (3)	0.002 (2)	−0.001 (2)	−0.028 (2)
C26	0.040 (2)	0.041 (2)	0.067 (3)	−0.0070 (18)	0.007 (2)	−0.027 (2)
C25	0.0356 (18)	0.031 (2)	0.051 (3)	−0.0023 (15)	0.0084 (17)	−0.0113 (18)
C24	0.0248 (16)	0.034 (2)	0.032 (2)	0.0007 (14)	0.0026 (15)	−0.0091 (17)
C23	0.0271 (15)	0.0267 (17)	0.0284 (18)	−0.0026 (12)	−0.0021 (15)	−0.0016 (16)
Br21	0.03060 (17)	0.0615 (2)	0.0485 (2)	−0.01033 (17)	0.00140 (18)	−0.0226 (2)
C22	0.0349 (16)	0.0221 (17)	0.0220 (17)	0.0025 (15)	−0.0039 (14)	0.0006 (13)
Cl21	0.0279 (4)	0.0629 (6)	0.0372 (5)	−0.0019 (4)	0.0014 (4)	−0.0105 (4)
C21	0.0340 (18)	0.024 (2)	0.0248 (19)	0.0018 (14)	0.0057 (14)	0.0019 (14)
O21	0.0619 (15)	0.0274 (13)	0.0239 (13)	0.0072 (12)	−0.0080 (11)	0.0017 (11)
N21	0.0407 (15)	0.0225 (15)	0.0147 (14)	0.0037 (13)	−0.0003 (12)	0.0035 (11)
C210	0.0259 (16)	0.0248 (18)	0.0211 (18)	0.0011 (14)	0.0041 (14)	0.0011 (13)
C211	0.0276 (16)	0.0267 (19)	0.0228 (18)	−0.0017 (15)	0.0012 (15)	0.0025 (13)
C212	0.0248 (16)	0.0260 (18)	0.038 (2)	−0.0003 (15)	0.0045 (16)	−0.0024 (15)
C213	0.0278 (17)	0.0317 (19)	0.0249 (19)	−0.0016 (15)	0.0046 (15)	−0.0115 (15)
N22	0.0380 (17)	0.053 (2)	0.037 (2)	−0.0090 (15)	0.0104 (15)	−0.0136 (16)
O222	0.087 (2)	0.0435 (18)	0.063 (2)	0.0130 (17)	−0.0067 (17)	−0.0252 (14)
O221	0.098 (2)	0.0695 (19)	0.0259 (17)	−0.0237 (17)	0.0190 (16)	−0.0141 (14)
C214	0.0358 (19)	0.038 (2)	0.0214 (19)	−0.0014 (15)	0.0032 (14)	0.0017 (15)
C215	0.047 (2)	0.0236 (18)	0.0204 (18)	0.0030 (15)	0.0036 (15)	0.0001 (14)

Geometric parameters (Å, º)

C19—C18	1.381 (5)	C29—C28	1.379 (5)
C19—C14	1.389 (5)	C29—C24	1.388 (5)
C18—C17	1.393 (5)	C28—C27	1.367 (6)
C17—C16	1.376 (5)	C27—C26	1.366 (6)
C16—C15	1.387 (5)	C26—C25	1.407 (5)
C15—C14	1.393 (4)	C25—C24	1.396 (4)
C14—C13	1.498 (4)	C24—C23	1.498 (4)
C13—C12	1.513 (4)	C23—C22	1.519 (4)
C13—Br11	1.988 (3)	C23—Br21	1.986 (3)
C12—C11	1.524 (4)	C22—C21	1.532 (4)
C12—Cl11	1.796 (3)	C22—Cl21	1.805 (3)
C11—O11	1.210 (4)	C21—O21	1.211 (4)
C11—N11	1.364 (4)	C21—N21	1.366 (4)
N11—C110	1.405 (4)	N21—C210	1.402 (4)
C110—C115	1.392 (4)	C210—C211	1.397 (4)
C110—C111	1.396 (4)	C210—C215	1.402 (4)
C111—C112	1.373 (4)	C211—C212	1.378 (4)
C112—C113	1.371 (5)	C212—C213	1.389 (4)
C113—C114	1.391 (4)	C213—C214	1.378 (5)
C113—N12	1.448 (4)	C213—N22	1.458 (4)
N12—O122	1.220 (4)	N22—O221	1.220 (4)
N12—O121	1.240 (4)	N22—O222	1.228 (4)
C114—C115	1.370 (4)	C214—C215	1.386 (4)
C18—C19—C14	120.9 (3)	C28—C29—C24	120.0 (4)
C19—C18—C17	119.7 (4)	C27—C28—C29	121.0 (4)
C16—C17—C18	120.1 (3)	C26—C27—C28	119.8 (4)
C17—C16—C15	120.0 (3)	C27—C26—C25	120.9 (4)
C16—C15—C14	120.6 (3)	C24—C25—C26	118.5 (4)
C19—C14—C15	118.7 (3)	C29—C24—C25	119.7 (3)
C19—C14—C13	121.8 (3)	C29—C24—C23	121.4 (3)
C15—C14—C13	119.4 (3)	C25—C24—C23	118.8 (3)
C14—C13—C12	115.9 (3)	C24—C23—C22	115.2 (3)
C14—C13—Br11	109.6 (2)	C24—C23—Br21	109.9 (2)
C12—C13—Br11	105.1 (2)	C22—C23—Br21	105.51 (19)
C13—C12—C11	112.8 (3)	C23—C22—C21	113.3 (3)
C13—C12—Cl11	109.3 (2)	C23—C22—Cl21	107.9 (2)
C11—C12—Cl11	104.6 (2)	C21—C22—Cl21	105.3 (2)
O11—C11—N11	124.6 (3)	O21—C21—N21	125.1 (3)
O11—C11—C12	122.6 (3)	O21—C21—C22	120.9 (3)
N11—C11—C12	112.7 (3)	N21—C21—C22	114.0 (3)
C11—N11—C110	128.9 (3)	C21—N21—C210	127.9 (3)
C115—C110—C111	120.3 (3)	C211—C210—N21	116.8 (3)
C115—C110—N11	122.9 (3)	C211—C210—C215	120.3 (3)
C111—C110—N11	116.7 (3)	N21—C210—C215	122.9 (3)
C112—C111—C110	120.2 (3)	C212—C211—C210	119.7 (3)
C113—C112—C111	118.6 (3)	C211—C212—C213	119.5 (3)
C112—C113—C114	122.2 (3)	C214—C213—C212	121.5 (3)
C112—C113—N12	119.0 (3)	C214—C213—N22	120.0 (3)
C114—C113—N12	118.8 (3)	C212—C213—N22	118.6 (3)
O122—N12—O121	122.3 (3)	O221—N22—O222	123.2 (3)
O122—N12—C113	119.8 (3)	O221—N22—C213	119.0 (3)
O121—N12—C113	117.9 (3)	O222—N22—C213	117.8 (3)
C115—C114—C113	119.2 (3)	C213—C214—C215	119.6 (3)
C114—C115—C110	119.5 (3)	C214—C215—C210	119.4 (3)
C14—C19—C18—C17	−1.1 (5)	C24—C29—C28—C27	0.8 (5)
C19—C18—C17—C16	−0.2 (5)	C29—C28—C27—C26	−1.3 (6)
C18—C17—C16—C15	0.8 (5)	C28—C27—C26—C25	1.3 (6)
C17—C16—C15—C14	−0.1 (5)	C27—C26—C25—C24	−0.7 (5)
C18—C19—C14—C15	1.8 (5)	C28—C29—C24—C25	−0.3 (5)
C18—C19—C14—C13	−176.8 (3)	C28—C29—C24—C23	179.9 (3)
C16—C15—C14—C19	−1.2 (5)	C26—C25—C24—C29	0.2 (5)
C16—C15—C14—C13	177.4 (3)	C26—C25—C24—C23	−180.0 (3)
C19—C14—C13—C12	−53.0 (4)	C29—C24—C23—C22	−54.6 (4)
C15—C14—C13—C12	128.4 (3)	C25—C24—C23—C22	125.6 (3)
C19—C14—C13—Br11	65.8 (3)	C29—C24—C23—Br21	64.4 (3)
C15—C14—C13—Br11	−112.8 (3)	C25—C24—C23—Br21	−115.4 (3)
C14—C13—C12—C11	−177.4 (3)	C24—C23—C22—C21	−177.4 (3)
Br11—C13—C12—C11	61.4 (3)	Br21—C23—C22—C21	61.2 (3)
C14—C13—C12—Cl11	−61.6 (3)	C24—C23—C22—Cl21	−61.2 (3)
Br11—C13—C12—Cl11	177.20 (16)	Br21—C23—C22—Cl21	177.40 (14)
C13—C12—C11—O11	39.2 (4)	C23—C22—C21—O21	39.0 (4)
Cl11—C12—C11—O11	−79.3 (3)	Cl21—C22—C21—O21	−78.8 (3)
C13—C12—C11—N11	−143.2 (3)	C23—C22—C21—N21	−143.1 (3)
Cl11—C12—C11—N11	98.2 (3)	Cl21—C22—C21—N21	99.2 (3)
O11—C11—N11—C110	5.2 (5)	O21—C21—N21—C210	5.0 (5)
C12—C11—N11—C110	−172.3 (3)	C22—C21—N21—C210	−172.9 (3)
C11—N11—C110—C115	12.6 (5)	C21—N21—C210—C211	−173.3 (3)
C11—N11—C110—C111	−169.9 (3)	C21—N21—C210—C215	8.1 (5)
C115—C110—C111—C112	1.5 (5)	N21—C210—C211—C212	−178.1 (3)
N11—C110—C111—C112	−176.1 (3)	C215—C210—C211—C212	0.5 (5)
C110—C111—C112—C113	−0.9 (5)	C210—C211—C212—C213	0.0 (5)
C111—C112—C113—C114	0.3 (5)	C211—C212—C213—C214	−0.4 (5)
C111—C112—C113—N12	178.4 (3)	C211—C212—C213—N22	178.6 (3)
C112—C113—N12—O122	1.8 (5)	C214—C213—N22—O221	−0.7 (5)
C114—C113—N12—O122	180.0 (3)	C212—C213—N22—O221	−179.7 (3)
C112—C113—N12—O121	−179.0 (3)	C214—C213—N22—O222	179.3 (3)
C114—C113—N12—O121	−0.8 (5)	C212—C213—N22—O222	0.4 (5)
C112—C113—C114—C115	−0.2 (5)	C212—C213—C214—C215	0.2 (5)
N12—C113—C114—C115	−178.4 (3)	N22—C213—C214—C215	−178.7 (3)
C113—C114—C115—C110	0.8 (5)	C213—C214—C215—C210	0.3 (5)
C111—C110—C115—C114	−1.4 (5)	C211—C210—C215—C214	−0.6 (5)
N11—C110—C115—C114	176.0 (3)	N21—C210—C215—C214	177.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···O121^i	0.88	2.00	2.847 (4)	162

Symmetry code: (i) −x, y+1/2, −z−1/2.