Crystal structure of (1S,2S,2'R,3a'S,5R)-2'-[(5-bromo-1H-indol-3-yl)meth-yl]-2-isopropyl-5,5'-dimethyl-dihydro-2'H-spiro-[cyclo-hexane-1,6'-imidazo[1,5-b]isoxazol]-4'(5'H)-one.

In the title compound, C24H32BrN3O2, the six-membered cyclo-hexane ring adopts a chair conformation and the isoxasolidine ring adopts a twisted conformation. The mol-ecule has five chiral centres and the absolute configuration has been determined in this analysis. The mol-ecular structure is stabilized by weak intra-molecular C-H⋯O and C-H⋯N contacts. In the crystal, mol-ecules are linked by N-H⋯N and C-H⋯O hydrogen bonds, forming undulating sheets parallel to the bc plane.

Chemical context

1,3-Dipolar cyclo­additions of alkenes with nitro­nes produce substituted isoxazolidines. Nitrone cyclo­adducts offer a general route to natural and unnatural amino acids (Aouadi et al., 2006 ▸, 2007 ▸) through opening of the isoxazolidine ring, usually by reductive cleavage of the weak N—O bond. Consequently, isoxazolidines have been used as key inter­mediates for the synthesis of various natural products, anti­fungals (Kumar et al., 2003 ▸), anti-tuberculosis (Kumar et al., 2010 ▸) and anti­viral agents (Loh et al., 2010 ▸). We present herein the synthesis, the mol­ecular structure and the spectroscopic data of the title compound, C24H32BrN3O2, (I).

Structural commentary

In the title compound (I) (Fig. 1 ▸), the five-membered isoxazolidine ring has a twist conformation. The O1—N2 bond length in the isoxazolidine ring is 1.475 (6) Å which is close to the values in related compounds (Lee et al., 2010 ▸; Molander & Cavalcanti, 2013 ▸). The cyclo­hexane ring adopts a chair conformation. The dihedral angle between the mean planes of the isoxazolidine and imidazolidinone rings is 73.1 (3)° while the C8—C9—C10—O1 torsion angle is 74.7 (7)°. In the molecule there are some short C—H⋯O and C—H⋯N contacts present (Table 1 ▸). The absolute configuration of (I) has been confirmed as C10(R),C12(S),C14(S),C16(R),C19(S) for the five arbitrarily numbered chiral centres in the mol­ecule.

Figure 1

The mol­ecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 40% probability level.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—HN1⋯N2i	0.89	2.34	3.087 (8)	141
C3—H3⋯O2ii	0.93	2.42	3.292 (9)	156
C16—H16⋯O1	0.98	2.55	3.091 (8)	115
C20—H20⋯N3	0.98	2.54	3.032 (10)	111
C21—H21A⋯N2	0.96	2.60	3.236 (9)	124

Symmetry codes: (i) ; (ii) .

Supra­molecular features

In the crystal packing of (I), the mol­ecules are linked through an inter­molecular N1—HN1⋯N2i hydrogen bond (Table 1 ▸) and a weak N1—HN1⋯O1i inter­action [3.053 (8) Å], forming undulating sheets parallel to the bc plane (Fig. 2 ▸). Within the chains, the mol­ecules are stabilized by a weak inter­molecular C3—H3⋯O2ii hydrogen bond (Table 1 ▸). Also present in the crystal are 39.3 Å3 solvent-accessible voids.

Figure 2

A view of the title structure, showing the mol­ecules of the title compound arranged in zigzag parallel chains sustained by weak N—H⋯N and N—H⋯O hydrogen bonds.

Synthesis and crystallization

To a solution of 3-allyl-5-bromo-1H-indole (1.40 mmol, 330 mg) in toluene (10 mL) was added 5(R),6(S),9(R)-6-isopropyl-1,9-dimethyl-1,4-diazo­aspiro­[4,5]-decan-1-ene-3-one-1-oxide (II) (1.19 mmol, 285 mg) and the mixture was stirred and heated at reflux at 383 K for 24 h under argon. TLC indicated the complete conversion of (II). The solution obtained was concentrated and the residue was purified by flash chromatography (petroleum ether–ethyl acetate 7:3) to afford the cyclo­adduct (I) as a white solid (507 mg, 90% yield) (Fig. 3 ▸). Colorless plate-shaped crystals of (I) were obtained by slow evaporation of a diethyl ether solution.

Figure 3

Reaction scheme for the synthesis of compound (I).

Spectroscopic investigations

NMR spectra were recorded on a Bruker Avance II 300 MHz spectrometer operating at 300 MHz for 1H and 75.46 MHz for 13C and were referenced to tetra­methyl­silane (δ = 0 p.p.m.). High-resolution (HR–ESI–QToF) mass spectra were recorded using a Bruker Micro ToF-Q II XL spectrometer.

The1H NMR spectrum of (I) shows the presence of an NH proton at 8.32 p.p.m. and the13C NMR spectrum confirms the existence of the C3 and C5 stereogenic centres at 66.4 p.p.m. and 78.0 p.p.m., respectively. The spectroscopic measurements are consistent with the crystal structure of (I). High-resolution mass spectrometry in the positive-ion mode exhibits an [M+H]+ fragment of 474.1759 m/z which is very close to the calculated value of 474.1756 m/z.

R f = 0.33 (PE–EtOAc 7:3). NMR 1H (300 MHz, CDCl3) δ(p.p.m.): 0.62 (d, 3H, J = 6.6 Hz), 0.83 (d, 3H, J = 6.6 Hz), 0.85 (m, 1H), 0.86 (d, 3H, J = 6.3 Hz), 1.11 (t, 1H, J = 12.3 Hz), 1.21–1.43 (m, 2H), 1.57–1.67 (m, 1H), 1.70–1.83 (m, 3H), 1.90–2.02 (m, 1H), 2.26 (ddd, 1H, J = 8.7 Hz, 10.2 Hz and 12 Hz), 2.69 (s, 3H, NCH3), 2.67–2.72 (m, 1H), 2.93–2.97 (m, 2H), 3.88–3.97 (m, 1H), 4.01 (brd, 1H, J = 8.4 Hz), 7.02 (brd, 1H, J = 4.8 Hz), 7.21 (m, 2H), 7.74 (brd, 1H, J = 1.8 Hz), 8.32 (brs, 1H, NH). 13C NMR (CDCl3, 75.46 MHz) δ(p.p.m.): 18.3, 22.0, 22.2 (CH2), 24.1, 24.3, 26.0, 28.1, 29.6, 34.5 (CH2), 38.8 (CH2), 40.3 (CH2), 48.0, 66.4, 78.0, 90.0, 112.3, 112.4, 112.7, 121.6, 123.5, 124.7, 129.1, 134.6, 173.0 (C=O). [α] = + 43.7 (c = 1, CH2Cl2).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All hydrogen atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.98 Å (methine), 0.97 Å (methyl­ene), 0.96 Å (meth­yl) and 0.93 Å (aromatic), with U iso(H) = 1.2U eq(C)(methine, methyl­ene, aromatic) or 1.5U eqC(meth­yl). The H atom on the nitro­gen N1 of the indole ring was found in a difference-Fourier map but was subsequently refined with the coordinates and isotropic displacement parameter also riding with U iso = 1.2 U eq(N). The bond length N1—HN1 was restrained to ensure proper geometry using the DFIX instruction of SHELXL2014/7 (Sheldrick, 2015 ▸). The absolute structure Flack parameter [−0.013 (13) for 1005 quotients (Parsons et al., 2013 ▸)] confirmed the configuration of the mol­ecule as C10(R),C12(S),C14(S),C16(R),C19(S) for the five arbitrarily numbered chiral centres in the mol­ecule.

Table 2

Experimental details

Crystal data
Chemical formula	C24H32BrN3O2
M r	474.43
Crystal system, space group	Monoclinic, P21
Temperature (K)	293
a, b, c (Å)	10.2640 (5), 9.6480 (5), 12.0480 (5)
β (°)	96.204 (5)
V (Å3)	1186.09 (10)
Z	2
Radiation type	Mo Kα
μ (mm−1)	1.76
Crystal size (mm)	0.46 × 0.39 × 0.11
Data collection
Diffractometer	Oxford Diffraction Xcalibur Atlas Gemini Ultra CCD
Absorption correction	Multi-scan (SCALEPACK; Otwinowski et al., 1997 ▸)
T min, T max	0.455, 0.802
No. of measured, independent and observed [I > 2σ(I)] reflections	10653, 4337, 2924
R int	0.104
(sin θ/λ)max (Å−1)	0.617
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.053, 0.135, 0.97
No. of reflections	4337
No. of parameters	272
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.31, −0.51
Absolute structure	Flack x determined using 1005 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)
Absolute structure parameter	−0.013 (13)

Computer programs: CrysAlis PRO (Agilent, 2013 ▸), SIR2011 (Burla et al., 2012 ▸), SHELXL2014 (Sheldrick, 2015 ▸), ORTEPIII (Burnett & Johnson, 1996 ▸) and ORTEP-3 for Windows and WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016010872/zs2365sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016010872/zs2365Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989016010872/zs2365Isup3.cml

CCDC reference: 1490701

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

C24H32BrN3O2	F(000) = 496
Mr = 474.43	Dx = 1.328 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 10.2640 (5) Å	Cell parameters from 8154 reflections
b = 9.6480 (5) Å	θ = 1.0–27.9°
c = 12.0480 (5) Å	µ = 1.76 mm−1
β = 96.204 (5)°	T = 293 K
V = 1186.09 (10) Å3	Plate, colorless
Z = 2	0.46 × 0.39 × 0.11 mm

Oxford Diffraction Xcalibur Atlas Gemini Ultra CCD diffractometer	4337 independent reflections
Radiation source: Enhance (Mo) X-ray source)	2924 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.104
ω/2θ scans	θmax = 26.0°, θmin = 2.7°
Absorption correction: multi-scan (SCALEPACK; Otwinowski et al., 1997)	h = −12→12
Tmin = 0.455, Tmax = 0.802	k = −11→11
10653 measured reflections	l = −13→14

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.053	w = 1/[σ2(Fo2) + (0.0631P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.135	(Δ/σ)max < 0.001
S = 0.97	Δρmax = 0.31 e Å−3
4337 reflections	Δρmin = −0.51 e Å−3
272 parameters	Absolute structure: Flack x determined using 1005 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
2 restraints	Absolute structure parameter: −0.013 (13)

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
Br	0.17985 (7)	0.23216 (8)	0.27079 (6)	0.0716 (3)
O1	0.4307 (4)	0.4046 (5)	0.6482 (4)	0.0455 (11)
N3	0.3297 (6)	0.6276 (6)	0.8208 (5)	0.0559 (16)
O2	0.5063 (6)	0.6393 (6)	0.9554 (4)	0.0728 (16)
N2	0.3578 (5)	0.4065 (6)	0.7471 (4)	0.0419 (12)
N1	0.6516 (6)	0.6022 (6)	0.3324 (5)	0.0521 (15)
C14	0.2644 (7)	0.5267 (7)	0.7427 (5)	0.0447 (15)
C6	0.4147 (7)	0.3475 (8)	0.3841 (6)	0.0472 (16)
H6	0.4007	0.2871	0.4418	0.057*
C9	0.6468 (6)	0.4016 (8)	0.5952 (5)	0.0478 (16)
H9A	0.7375	0.4153	0.6248	0.057*
H9B	0.6317	0.3025	0.5885	0.057*
C1	0.3301 (7)	0.3486 (8)	0.2869 (6)	0.0523 (18)
C11	0.5918 (7)	0.4126 (9)	0.7977 (6)	0.0513 (18)
H11A	0.6196	0.3164	0.8013	0.062*
H11B	0.6594	0.4698	0.8372	0.062*
C10	0.5591 (6)	0.4605 (7)	0.6774 (5)	0.0426 (15)
H10	0.5572	0.5619	0.6734	0.051*
C8	0.6248 (6)	0.4659 (7)	0.4806 (5)	0.0439 (15)
C13	0.4388 (7)	0.5769 (8)	0.8831 (6)	0.0523 (18)
C19	0.1319 (7)	0.4750 (8)	0.7834 (5)	0.0485 (17)
H19	0.0774	0.5582	0.7854	0.058*
C5	0.5213 (6)	0.4378 (7)	0.3948 (5)	0.0428 (15)
C12	0.4609 (6)	0.4315 (8)	0.8439 (5)	0.0471 (16)
H12	0.4518	0.3648	0.9039	0.057*
C16	0.1585 (6)	0.4977 (7)	0.5389 (5)	0.0472 (16)
H16	0.2112	0.4153	0.5275	0.057*
C15	0.2358 (7)	0.5914 (7)	0.6262 (6)	0.0500 (17)
H15A	0.3184	0.6159	0.5992	0.060*
H15B	0.1867	0.6764	0.6328	0.060*
C7	0.6991 (6)	0.5668 (8)	0.4386 (6)	0.0503 (17)
H7	0.7730	0.6064	0.4776	0.060*
C4	0.5407 (7)	0.5268 (7)	0.3039 (6)	0.0459 (16)
C18	0.0585 (7)	0.3816 (8)	0.6964 (6)	0.0544 (18)
H18A	−0.0241	0.3541	0.7220	0.065*
H18B	0.1096	0.2983	0.6884	0.065*
C3	0.4561 (8)	0.5248 (8)	0.2046 (6)	0.056 (2)
H3	0.4705	0.5828	0.1455	0.068*
C17	0.0316 (6)	0.4521 (9)	0.5829 (6)	0.0574 (19)
H17A	−0.0146	0.3883	0.5302	0.069*
H17B	−0.0241	0.5322	0.5896	0.069*
C21	0.1702 (8)	0.2603 (9)	0.9120 (6)	0.071 (2)
H21A	0.2474	0.2388	0.8770	0.107*
H21B	0.1833	0.2340	0.9892	0.107*
H21C	0.0968	0.2105	0.8754	0.107*
C2	0.3522 (8)	0.4357 (8)	0.1965 (6)	0.061 (2)
H2	0.2954	0.4324	0.1309	0.073*
C20	0.1432 (7)	0.4168 (9)	0.9030 (6)	0.0554 (18)
H20	0.2168	0.4641	0.9457	0.066*
C23	0.1317 (8)	0.5741 (9)	0.4278 (6)	0.068 (2)
H23A	0.2133	0.6015	0.4022	0.102*
H23B	0.0854	0.5139	0.3736	0.102*
H23C	0.0796	0.6549	0.4376	0.102*
C22	0.0205 (10)	0.4502 (13)	0.9589 (8)	0.097 (3)
H22A	0.0032	0.5479	0.9535	0.145*
H22B	−0.0527	0.4001	0.9222	0.145*
H22C	0.0338	0.4236	1.0361	0.145*
C24	0.2777 (9)	0.7638 (8)	0.8427 (8)	0.081 (3)
H24A	0.2015	0.7815	0.7912	0.121*
H24B	0.2542	0.7668	0.9177	0.121*
H24C	0.3431	0.8329	0.8338	0.121*
HN1	0.6758	0.6699	0.2885	0.07 (2)*

	U11	U22	U33	U12	U13	U23
Br	0.0695 (5)	0.0753 (5)	0.0667 (5)	−0.0179 (5)	−0.0081 (3)	0.0009 (5)
O1	0.042 (3)	0.058 (3)	0.036 (3)	−0.003 (2)	0.0033 (19)	0.000 (2)
N3	0.066 (4)	0.049 (4)	0.052 (4)	−0.006 (3)	0.004 (3)	−0.008 (3)
O2	0.078 (4)	0.092 (4)	0.047 (3)	−0.029 (3)	−0.001 (3)	−0.015 (3)
N2	0.042 (3)	0.053 (3)	0.031 (3)	−0.002 (3)	0.002 (2)	0.001 (2)
N1	0.059 (4)	0.049 (4)	0.049 (4)	−0.007 (3)	0.012 (3)	0.004 (3)
C14	0.051 (4)	0.046 (4)	0.037 (4)	0.000 (3)	0.002 (3)	−0.003 (3)
C6	0.058 (4)	0.048 (4)	0.037 (4)	−0.004 (3)	0.009 (3)	0.005 (3)
C9	0.043 (4)	0.056 (4)	0.045 (4)	0.012 (3)	0.006 (3)	0.011 (3)
C1	0.067 (5)	0.047 (4)	0.042 (4)	−0.001 (4)	−0.001 (3)	−0.007 (3)
C11	0.045 (4)	0.070 (5)	0.037 (4)	0.003 (4)	−0.002 (3)	0.007 (4)
C10	0.040 (3)	0.049 (4)	0.038 (4)	−0.006 (3)	0.003 (3)	0.000 (3)
C8	0.042 (3)	0.049 (4)	0.041 (4)	0.000 (3)	0.009 (3)	−0.001 (3)
C13	0.058 (4)	0.062 (5)	0.038 (4)	−0.013 (4)	0.008 (3)	−0.001 (3)
C19	0.048 (4)	0.052 (4)	0.046 (4)	0.009 (3)	0.006 (3)	0.002 (3)
C5	0.048 (4)	0.043 (4)	0.038 (4)	0.004 (3)	0.008 (3)	−0.003 (3)
C12	0.046 (4)	0.060 (5)	0.034 (3)	−0.009 (3)	0.003 (3)	0.003 (3)
C16	0.051 (4)	0.044 (4)	0.045 (4)	0.006 (3)	−0.003 (3)	0.004 (3)
C15	0.058 (4)	0.037 (4)	0.054 (5)	0.008 (3)	0.003 (3)	0.008 (3)
C7	0.047 (4)	0.054 (4)	0.051 (4)	−0.005 (4)	0.009 (3)	−0.004 (3)
C4	0.057 (4)	0.038 (4)	0.043 (4)	0.001 (3)	0.011 (3)	−0.003 (3)
C18	0.044 (4)	0.067 (5)	0.050 (4)	−0.002 (3)	0.000 (3)	−0.003 (4)
C3	0.075 (5)	0.055 (5)	0.039 (4)	0.003 (4)	0.009 (4)	0.003 (3)
C17	0.048 (4)	0.069 (5)	0.052 (4)	0.003 (4)	−0.007 (3)	−0.001 (4)
C21	0.073 (5)	0.085 (7)	0.057 (5)	−0.006 (5)	0.015 (4)	0.015 (4)
C2	0.082 (5)	0.061 (5)	0.036 (4)	−0.007 (4)	−0.008 (3)	0.000 (4)
C20	0.051 (4)	0.072 (5)	0.045 (4)	0.002 (4)	0.012 (3)	−0.002 (4)
C23	0.090 (6)	0.065 (5)	0.045 (4)	0.011 (5)	−0.011 (4)	0.006 (4)
C22	0.087 (6)	0.139 (9)	0.071 (6)	0.021 (7)	0.037 (5)	0.009 (6)
C24	0.104 (6)	0.063 (7)	0.075 (6)	0.002 (5)	0.009 (5)	−0.021 (5)

Br—C1	1.901 (7)	C5—C4	1.423 (9)
O1—C10	1.432 (7)	C12—H12	0.9800
O1—N2	1.475 (6)	C16—C17	1.523 (10)
N3—C13	1.369 (10)	C16—C23	1.526 (10)
N3—C24	1.453 (10)	C16—C15	1.540 (10)
N3—C14	1.465 (9)	C16—H16	0.9800
O2—C13	1.212 (9)	C15—H15A	0.9700
N2—C14	1.502 (9)	C15—H15B	0.9700
N2—C12	1.507 (8)	C7—H7	0.9300
N1—C7	1.362 (9)	C4—C3	1.401 (11)
N1—C4	1.362 (9)	C18—C17	1.526 (10)
N1—HN1	0.8929	C18—H18A	0.9700
C14—C15	1.535 (9)	C18—H18B	0.9700
C14—C19	1.576 (10)	C3—C2	1.365 (11)
C6—C1	1.381 (10)	C3—H3	0.9300
C6—C5	1.394 (10)	C17—H17A	0.9700
C6—H6	0.9300	C17—H17B	0.9700
C9—C8	1.508 (9)	C21—C20	1.537 (12)
C9—C10	1.519 (9)	C21—H21A	0.9600
C9—H9A	0.9700	C21—H21B	0.9600
C9—H9B	0.9700	C21—H21C	0.9600
C1—C2	1.413 (11)	C2—H2	0.9300
C11—C12	1.519 (9)	C20—C22	1.525 (10)
C11—C10	1.524 (9)	C20—H20	0.9800
C11—H11A	0.9700	C23—H23A	0.9600
C11—H11B	0.9700	C23—H23B	0.9600
C10—H10	0.9800	C23—H23C	0.9600
C8—C7	1.368 (9)	C22—H22A	0.9600
C8—C5	1.426 (9)	C22—H22B	0.9600
C13—C12	1.506 (11)	C22—H22C	0.9600
C19—C18	1.519 (10)	C24—H24A	0.9600
C19—C20	1.540 (10)	C24—H24B	0.9600
C19—H19	0.9800	C24—H24C	0.9600
C10—O1—N2	109.3 (4)	C17—C16—H16	108.6
C13—N3—C24	121.2 (7)	C23—C16—H16	108.6
C13—N3—C14	113.9 (6)	C15—C16—H16	108.6
C24—N3—C14	124.5 (7)	C14—C15—C16	114.8 (5)
O1—N2—C14	111.0 (5)	C14—C15—H15A	108.6
O1—N2—C12	104.6 (4)	C16—C15—H15A	108.6
C14—N2—C12	107.2 (5)	C14—C15—H15B	108.6
C7—N1—C4	107.9 (6)	C16—C15—H15B	108.6
C7—N1—HN1	130.2	H15A—C15—H15B	107.5
C4—N1—HN1	121.3	N1—C7—C8	111.6 (6)
N3—C14—N2	104.1 (5)	N1—C7—H7	124.2
N3—C14—C15	110.2 (5)	C8—C7—H7	124.2
N2—C14—C15	113.9 (5)	N1—C4—C3	130.3 (7)
N3—C14—C19	111.1 (5)	N1—C4—C5	108.1 (6)
N2—C14—C19	108.3 (5)	C3—C4—C5	121.6 (7)
C15—C14—C19	109.1 (5)	C19—C18—C17	112.5 (6)
C1—C6—C5	119.2 (6)	C19—C18—H18A	109.1
C1—C6—H6	120.4	C17—C18—H18A	109.1
C5—C6—H6	120.4	C19—C18—H18B	109.1
C8—C9—C10	113.7 (5)	C17—C18—H18B	109.1
C8—C9—H9A	108.8	H18A—C18—H18B	107.8
C10—C9—H9A	108.8	C2—C3—C4	118.5 (7)
C8—C9—H9B	108.8	C2—C3—H3	120.7
C10—C9—H9B	108.8	C4—C3—H3	120.7
H9A—C9—H9B	107.7	C16—C17—C18	111.2 (5)
C6—C1—C2	121.4 (7)	C16—C17—H17A	109.4
C6—C1—Br	120.7 (6)	C18—C17—H17A	109.4
C2—C1—Br	117.9 (6)	C16—C17—H17B	109.4
C12—C11—C10	101.5 (5)	C18—C17—H17B	109.4
C12—C11—H11A	111.5	H17A—C17—H17B	108.0
C10—C11—H11A	111.5	C20—C21—H21A	109.5
C12—C11—H11B	111.5	C20—C21—H21B	109.5
C10—C11—H11B	111.5	H21A—C21—H21B	109.5
H11A—C11—H11B	109.3	C20—C21—H21C	109.5
O1—C10—C9	107.0 (5)	H21A—C21—H21C	109.5
O1—C10—C11	102.8 (5)	H21B—C21—H21C	109.5
C9—C10—C11	114.9 (5)	C3—C2—C1	120.5 (7)
O1—C10—H10	110.6	C3—C2—H2	119.7
C9—C10—H10	110.6	C1—C2—H2	119.7
C11—C10—H10	110.6	C22—C20—C21	109.1 (8)
C7—C8—C5	105.6 (6)	C22—C20—C19	110.7 (7)
C7—C8—C9	126.7 (6)	C21—C20—C19	114.7 (6)
C5—C8—C9	127.7 (6)	C22—C20—H20	107.3
O2—C13—N3	125.9 (8)	C21—C20—H20	107.3
O2—C13—C12	126.4 (7)	C19—C20—H20	107.3
N3—C13—C12	107.6 (6)	C16—C23—H23A	109.5
C18—C19—C20	114.3 (6)	C16—C23—H23B	109.5
C18—C19—C14	110.7 (6)	H23A—C23—H23B	109.5
C20—C19—C14	115.3 (6)	C16—C23—H23C	109.5
C18—C19—H19	105.2	H23A—C23—H23C	109.5
C20—C19—H19	105.2	H23B—C23—H23C	109.5
C14—C19—H19	105.2	C20—C22—H22A	109.5
C6—C5—C4	118.7 (6)	C20—C22—H22B	109.5
C6—C5—C8	134.6 (6)	H22A—C22—H22B	109.5
C4—C5—C8	106.7 (6)	C20—C22—H22C	109.5
C13—C12—N2	105.9 (6)	H22A—C22—H22C	109.5
C13—C12—C11	113.3 (6)	H22B—C22—H22C	109.5
N2—C12—C11	105.8 (5)	N3—C24—H24A	109.5
C13—C12—H12	110.5	N3—C24—H24B	109.5
N2—C12—H12	110.5	H24A—C24—H24B	109.5
C11—C12—H12	110.5	N3—C24—H24C	109.5
C17—C16—C23	111.4 (6)	H24A—C24—H24C	109.5
C17—C16—C15	109.2 (6)	H24B—C24—H24C	109.5
C23—C16—C15	110.3 (6)
C10—O1—N2—C12	−14.5 (6)	C8—C5—C6—C1	179.1 (7)
C10—O1—N2—C14	100.9 (5)	C4—C5—C8—C7	−0.1 (7)
N2—O1—C10—C9	155.8 (5)	C4—C5—C8—C9	178.3 (6)
N2—O1—C10—C11	34.4 (6)	C6—C5—C8—C7	179.7 (8)
C7—N1—C4—C3	−179.9 (8)	C6—C5—C8—C9	−1.9 (13)
C7—N1—C4—C5	−2.0 (8)	N1—C7—C8—C5	−1.2 (8)
C4—N1—C7—C8	2.0 (8)	N1—C7—C8—C9	−179.6 (6)
O1—N2—C12—C11	−11.6 (7)	C5—C8—C9—C10	−78.1 (9)
O1—N2—C12—C13	109.0 (5)	C7—C8—C9—C10	100.1 (8)
C14—N2—C12—C11	−129.6 (6)	C8—C9—C10—O1	74.7 (7)
C14—N2—C12—C13	−9.0 (6)	C8—C9—C10—C11	−171.8 (6)
O1—N2—C14—N3	−103.0 (5)	O1—C10—C11—C12	−39.7 (7)
O1—N2—C14—C15	17.2 (7)	C9—C10—C11—C12	−155.6 (6)
O1—N2—C14—C19	138.7 (5)	C10—C11—C12—N2	31.3 (7)
C12—N2—C14—N3	10.8 (6)	C10—C11—C12—C13	−84.4 (7)
C12—N2—C14—C15	130.9 (6)	N2—C12—C13—O2	−175.3 (7)
C12—N2—C14—C19	−107.6 (5)	N2—C12—C13—N3	3.5 (7)
C14—N3—C13—O2	−177.5 (7)	C11—C12—C13—O2	−59.8 (10)
C14—N3—C13—C12	3.6 (8)	C11—C12—C13—N3	119.1 (6)
C24—N3—C13—O2	−4.7 (12)	N2—C14—C15—C16	67.4 (8)
C24—N3—C13—C12	176.5 (6)	N3—C14—C15—C16	−176.0 (6)
C13—N3—C14—N2	−9.2 (7)	C19—C14—C15—C16	−53.7 (7)
C13—N3—C14—C15	−131.7 (6)	N2—C14—C19—C18	−71.8 (7)
C13—N3—C14—C19	107.2 (7)	N2—C14—C19—C20	59.8 (7)
C24—N3—C14—N2	178.3 (6)	N3—C14—C19—C18	174.4 (6)
C24—N3—C14—C15	55.8 (9)	N3—C14—C19—C20	−54.0 (8)
C24—N3—C14—C19	−65.3 (8)	C15—C14—C19—C18	52.6 (7)
Br—C1—C2—C3	177.9 (6)	C15—C14—C19—C20	−175.8 (6)
C6—C1—C2—C3	−2.2 (12)	C14—C15—C16—C17	55.4 (8)
Br—C1—C6—C5	−177.7 (5)	C14—C15—C16—C23	178.1 (6)
C2—C1—C6—C5	2.4 (11)	C15—C16—C17—C18	−55.5 (8)
C1—C2—C3—C4	0.6 (12)	C23—C16—C17—C18	−177.4 (6)
C2—C3—C4—N1	178.3 (7)	C16—C17—C18—C19	58.6 (8)
C2—C3—C4—C5	0.7 (11)	C17—C18—C19—C14	−56.6 (8)
N1—C4—C5—C6	−178.5 (6)	C17—C18—C19—C20	171.3 (6)
N1—C4—C5—C8	1.3 (8)	C14—C19—C20—C21	−89.9 (8)
C3—C4—C5—C6	−0.4 (10)	C14—C19—C20—C22	146.0 (7)
C3—C4—C5—C8	179.4 (7)	C18—C19—C20—C21	40.0 (9)
C4—C5—C6—C1	−1.1 (10)	C18—C19—C20—C22	−84.1 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N1—HN1···N2i	0.89	2.34	3.087 (8)	141
C3—H3···O2ii	0.93	2.42	3.292 (9)	156
C16—H16···O1	0.98	2.55	3.091 (8)	115
C20—H20···N3	0.98	2.54	3.032 (10)	111
C21—H21A···N2	0.96	2.60	3.236 (9)	124
N1—HN1···O1i	0.89	2.66	3.053 (8)	108
C20—H20···Cg3	0.98	2.41	2.866 (8)	104