1-(1-Amino-4-bromo-9,10-dioxo-9,10-dihydro­anthracen-2-ylcarbon­yl)-1,3-dicyclo­hexyl­urea

In the title compound, C₂₈H₃₀BrN₃O₄, the mol­ecules are linked by C—H...Br and N—H...O hydrogen bonds into one-dimensional chains, which are arranged into a three-dimensional network through a combination of C—H...O hydrogen bonds and two kinds of π–π inter­actions between the benzene rings of the anthraquinone units.

S1. Comment

Anthraquinone compounds, as very stable basis dyestuffs, have been the subject of much technical and scientific interest. It has been reported that anthraquinone dichroic dyes dissolved in liquid crystals can strongly enhance photoinduced reorientational efficiency (Janossy et al., 1990; Janossy & Lloyd, 1991; Yaegashi et al., 2005). Recently, we have investigated a series of anthraquinone derivatives as highly efficient dyes for photoindued reorientation. During the study, the crystal structure of the title N-substituted amidate, (I), was determined. Some chromophores with an acylureido substitutent have been reported to exhibit unexpected strong solvatochromism, which provides important contributions to the development of sensitive tools (Cornelia et al., 2005; Bosignore or Bonsignore et al., 1999). We now present the title molecule, whose structure exhibits some interesting features in that the N-acylureido group is attached to the anthraquinone group.

The molecular structure is presented in Fig. 1. In contrast to the nearly planar arrangement observed in pyridinium 1-amino-4-bromo-9,10-anthraquinone-2-sulphonate (Skar\,zyński et al., 1978) and 1-hydroxy-4-(4-methylphenylamino)-9,10-anthraquinone (Black et al., 1992), the anthraquinone unit of (I) loses its planarity as a result of the repulsion between atoms Br1 and O2. The two benzene rings A and C form a `V' intersecting at atoms C4 and C11 with a dihedral angle of 11.2 (2)°. This arrangement also forces the two carbonyl O atoms to move out from the two mean planes A and C, and atoms O1 and O2 deviate from the central ring plane B by 0.3189 (5) and 0.4973 (5) Å, respectively. In addition, the dihedral angles between plane B and planes A and C are 20.1 (2) and 9.2 (2)°, respectively.

In the N-acylureido unit, the two carbonyl groups twist substantially at the central atom N2, with a dihedral angle of 77.3 (1)° between the O3/C15/N2 and N2/C22/O4 planes, which increases the distance between atoms O3 and N3. Therefore, no intramolecular N3—H3···O3 hydrogen bond is formed as expected [ambiguous usage; could be taken to mean that the bond either was or was not expected]. Moreover, carbonyl atom O3 deviates from the anthraquinone plane by 0.6200 (6) Å, which weakens the conjugation between the carbonyl and anthraquinone groups.

Each of the cyclohexyl groups D and E in (I) adopts a common chair conformation, as is required for the minimum energy. Moreover, for each ring the bond distances are similar to those in 1,3-dicyclohexylurea (Govindasamy & Subramanian, 1997).

The molecules of (I) are stacked into a three-dimensional framework via a variety of weak but direction-specific intermolecular forces, and the formation of this framework is readily analysed by means of the substructure approach. N—H···O and C—H···Br hydrogen bonds link the molecules into polymer chains, which are linked into segments by the combined action of a C—H···O hydrogen bond and a π–π stacking interaction between rings A and A# from adjacent molecules (Table 2). These segments are further linked by a single π–π stacking interaction between rings C and C*.

Atoms N3 and C20 at (x, y, z) acts as hydrogen-bond donors to, respectively, atom O4 in the molecule at (−x + 1/2, y − 1/2, −z + 1/2) and atom Br1 in the molecule at (−x + 1/2, y − 1/2, −z + 1/2). In this manner, a one-dimensional polymer chain is generated along the b direction (Fig. 2).

Probably as a result of π–π stacking interaction bringing atoms C17 and O2 into close proximity, atom C17 in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom O2 in the molecule at (−x, y, −z + 1/2) to produce a centrosymmetric motif. Adjacent one-dimensional chains are strongly linked into segments by a combination of these hydrogen-bond pairs and π–π stacking interactions, with a centre-to-centre distance of 3.573 (6) Å between benzene rings A and A#.

These segments are strongly linked by π–π stacking interactions between two related rings C and C*, which are parallel to each other, with an interplanar spacing of 3.387 (6) Å and a ring-centroid separation of 3.641 (6) Å (Fig. 4). Propagation by the space group of this interaction is sufficient to link all of these segments into a three-dimensional framework (Fig. 5).

S2. Experimental

For the synthesis of (I), a solution of 1-amino-4-bromo-9,10-dioxoanthracene-2-carboxylic acid (1.0 g), 1,3-dicyclohexylcarbodiimide (0.7 g), 4-dimethylaminopyridine (0.03 g) and cyclohexanol (0.5 g) in dry dimethylformamide (DMF, 30 ml) was stirred at 373 K for 4 h. The hot solution was cooled to room temperature and poured into methanol (50 ml) with stirring. The resulting precipitate was collected by filtration, washed with methanol and dried in vacuum. The product was obtained as a yellow powder in 82% yield. The yellow crystal used for the X-ray analysis was grown by slow evaporation of a DMF solution at room temperature (m.p. 558–560 K). ¹H NMR (500 MHz, DMSO, δ, p.p.m.): 8.14–8.17 (m, 2H), 8.08–8.10 (d, 2H), 7.84–7.91 (m, 2H), 7.76 (s, 1H), 4.0–4.12 (m, 1H), 3.24–3.26 (m, 1H), 1.91 (d, J = 11.6 Hz, 2H), 1.78 (d, J = 13.2 Hz, 2H), 1.57–1.62 (m, 3H), 1.47–1.50 (m, 4H), 1.38–1.42 (m, 1H), 1.25–1.34 (m, 2H), 1.07–1.13 (m, 3H), 0.94–1.00 (m, 3H).

S3. Refinement

Amide H atoms were found in a difference map and refined with U_iso(H) values of 1.2U_eq(N); N—H bond lengths were restrained to 0.88 Å [if `restrained' should s.u. values be provided for N—H parameters; if `constrained' N—H = 0.86–0.89 Å]. All other H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined as riding, with U_iso(H) values of 1.2U_eq(C). In the absence of significant anomalous scattering effects, Friedel pairs were merged in the final refinement cycles. Should s.u. values be omitted from H···A and D—H···A in Table 2?

Data collection: Bruker SMART; cell refinement: Bruker SMART; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL and Mercury (Version 1.4; Bruno et al., 2002); software used to prepare material for publication: SHELXTL and local programs.

Computing details

Data collection: APEX-II (Bruker, 1997); cell refinement: APEX-II; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a one-dimensional chain along the b axis via N—H···O and C—H···Br hydrogen bonds (dashed lines). For the sake of clarity, H atoms not involved in the motif have been omitted. Atoms O4 and Br1 are both at the symmetry positions (−x + 1/2, y − 1/2, −z + 1/2).
	Fig. 3. Part of the crystal structure of (I), showing the π–π stacking interaction and pairs of C17—H17A···O2 hydrogen bonds (dashed lines). For clarity, H atoms not involved in the motif and the unit-cell box have been omitted. The has (#) symbol denotes the symmetry code (−x, y, −z + 1/2).
	Fig. 4. Part of the crystal structure of (I), showing the π–π stacking interaction that links these segments together. For clarity, all H atoms and the unit-cell box have been omitted. The asterisk (*) denotes the symmetry code ????
	Fig. 5. A stereoview of part of the crystal structure of (I), viewed down b axis, showing the formation of the three-dimensional framework by a combination of hydrogen bonds (dashed lines) and π–π stacking interactions. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

1-(1-Amino-4-bromo-9,10-dioxo-9,10-dihydroanthracene-2-carbonyl)- 1,3-dicyclohexylurea

Crystal data

C28H30BrN3O4	F(000) = 2288
Mr = 552.45	Dx = 1.447 Mg m^−3
Monoclinic, C2/c	Melting point = 558–560 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 20.725 (6) Å	Cell parameters from 2090 reflections
b = 9.727 (3) Å	θ = 2.3–19.1°
c = 25.306 (7) Å	µ = 1.66 mm^−1
β = 96.095 (4)°	T = 293 K
V = 5073 (2) Å^3	Lamellar?, red
Z = 8	0.26 × 0.14 × 0.08 mm

Data collection

Bruker APEX-II CCD area-detector diffractometer	4495 independent reflections
Radiation source: fine-focus sealed tube	2936 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ϕ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −24→13
Tmin = 0.757, Tmax = 0.880	k = −11→11
13483 measured reflections	l = −29→30

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0411P)^2 + 5.4394P] where P = (Fo^2 + 2Fc^2)/3
4495 reflections	(Δ/σ)max < 0.001
325 parameters	Δρmax = 0.42 e Å^−3
4 restraints	Δρmin = −0.40 e Å^−3

Special details

Experimental. CCD area detector (Sheldrick, 1997) was used to correct for the MoKalpha radiation through π and ω scans.

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
Br1	0.02259 (2)	0.87783 (4)	0.177974 (19)	0.07391 (18)
O1	0.01793 (13)	0.2110 (3)	0.14725 (11)	0.0711 (8)
O2	−0.07001 (15)	0.7114 (3)	0.11035 (13)	0.1000 (11)
O3	0.13060 (10)	0.4226 (2)	0.33055 (9)	0.0497 (6)
O4	0.24075 (12)	0.7628 (2)	0.26289 (9)	0.0522 (6)
N1	0.08687 (14)	0.2865 (3)	0.23465 (12)	0.0610 (9)
H1A	0.1046	0.2720	0.2676	0.073*
H1B	0.0661	0.2170	0.2178	0.073*
N2	0.20622 (12)	0.5665 (2)	0.30319 (9)	0.0362 (6)
N3	0.24832 (12)	0.5585 (2)	0.22228 (9)	0.0359 (6)
H3A	0.2416	0.4717	0.2250	0.043*
C1	0.08699 (15)	0.6603 (3)	0.23276 (13)	0.0432 (8)
H1	0.1068	0.7328	0.2522	0.052*
C2	0.04130 (15)	0.6893 (3)	0.18992 (13)	0.0458 (8)
C3	0.01350 (15)	0.5830 (4)	0.15881 (13)	0.0478 (8)
C4	−0.03753 (18)	0.6075 (4)	0.11316 (16)	0.0629 (11)
C5	−0.04808 (17)	0.4994 (5)	0.07270 (14)	0.0629 (11)
C6	−0.0817 (2)	0.5296 (6)	0.02335 (18)	0.0951 (17)
H6	−0.0992	0.6166	0.0166	0.114*
C7	−0.0886 (3)	0.4295 (8)	−0.0152 (2)	0.113 (2)
H7	−0.1092	0.4508	−0.0487	0.135*
C8	−0.0657 (3)	0.3004 (8)	−0.00534 (19)	0.108 (2)
H8	−0.0714	0.2339	−0.0318	0.129*
C9	−0.0341 (2)	0.2667 (5)	0.04404 (16)	0.0821 (14)
H9	−0.0191	0.1777	0.0511	0.099*
C10	−0.02509 (17)	0.3681 (5)	0.08284 (14)	0.0614 (11)
C11	0.00859 (16)	0.3321 (4)	0.13600 (14)	0.0530 (9)
C12	0.03225 (14)	0.4461 (3)	0.17134 (12)	0.0429 (8)
C13	0.07353 (14)	0.4158 (3)	0.21806 (13)	0.0418 (8)
C14	0.10359 (14)	0.5289 (3)	0.24724 (11)	0.0364 (7)
C15	0.14791 (15)	0.5005 (3)	0.29687 (12)	0.0383 (7)
C16	0.24618 (15)	0.5578 (3)	0.35528 (11)	0.0398 (7)
H16	0.2271	0.4855	0.3757	0.048*
C17	0.2438 (2)	0.6885 (4)	0.38667 (14)	0.0709 (12)
H17A	0.1990	0.7099	0.3914	0.085*
H17B	0.2609	0.7635	0.3671	0.085*
C18	0.2831 (2)	0.6753 (5)	0.44104 (15)	0.0827 (14)
H18A	0.2839	0.7633	0.4591	0.099*
H18B	0.2622	0.6093	0.4624	0.099*
C19	0.3505 (2)	0.6304 (5)	0.43637 (16)	0.0783 (13)
H19A	0.3733	0.7025	0.4195	0.094*
H19B	0.3727	0.6155	0.4716	0.094*
C20	0.3525 (2)	0.5031 (5)	0.40519 (15)	0.0837 (14)
H20A	0.3344	0.4284	0.4244	0.100*
H20B	0.3973	0.4804	0.4013	0.100*
C21	0.31452 (18)	0.5157 (5)	0.34978 (14)	0.0662 (11)
H21A	0.3350	0.5835	0.3290	0.079*
H21B	0.3147	0.4281	0.3314	0.079*
C22	0.23285 (14)	0.6394 (3)	0.26063 (12)	0.0344 (7)
C23	0.27625 (14)	0.6083 (3)	0.17532 (12)	0.0380 (7)
H23	0.2890	0.7044	0.1817	0.046*
C24	0.22695 (16)	0.6040 (4)	0.12656 (13)	0.0497 (9)
H24A	0.1906	0.6633	0.1321	0.060*
H24B	0.2106	0.5110	0.1213	0.060*
C25	0.25696 (18)	0.6506 (4)	0.07729 (14)	0.0620 (10)
H25A	0.2252	0.6423	0.0464	0.074*
H25B	0.2693	0.7466	0.0811	0.074*
C26	0.31610 (19)	0.5651 (4)	0.06891 (13)	0.0609 (10)
H26A	0.3032	0.4703	0.0622	0.073*
H26B	0.3353	0.5988	0.0381	0.073*
C27	0.36552 (17)	0.5722 (4)	0.11728 (13)	0.0570 (9)
H27A	0.3814	0.6658	0.1218	0.068*
H27B	0.4021	0.5137	0.1118	0.068*
C28	0.33687 (15)	0.5271 (3)	0.16726 (12)	0.0452 (8)
H28A	0.3263	0.4300	0.1647	0.054*
H28B	0.3688	0.5398	0.1978	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0649 (3)	0.0551 (3)	0.0993 (4)	0.0116 (2)	−0.0027 (2)	0.0262 (2)
O1	0.0713 (18)	0.0630 (18)	0.0749 (19)	−0.0044 (14)	−0.0109 (14)	−0.0127 (15)
O2	0.075 (2)	0.093 (2)	0.121 (3)	0.0170 (18)	−0.0382 (19)	0.029 (2)
O3	0.0462 (13)	0.0560 (14)	0.0464 (14)	−0.0095 (11)	0.0031 (11)	0.0160 (12)
O4	0.0808 (17)	0.0280 (12)	0.0500 (14)	−0.0066 (11)	0.0173 (12)	−0.0039 (10)
N1	0.064 (2)	0.0414 (16)	0.071 (2)	0.0026 (14)	−0.0230 (16)	0.0035 (15)
N2	0.0361 (14)	0.0381 (14)	0.0339 (14)	−0.0011 (11)	0.0019 (11)	0.0044 (11)
N3	0.0484 (16)	0.0255 (12)	0.0350 (15)	−0.0037 (11)	0.0089 (12)	0.0008 (11)
C1	0.0372 (18)	0.0437 (19)	0.049 (2)	0.0003 (15)	0.0062 (16)	0.0039 (15)
C2	0.0333 (17)	0.0496 (19)	0.055 (2)	0.0039 (15)	0.0076 (16)	0.0163 (17)
C3	0.0312 (18)	0.065 (2)	0.047 (2)	0.0032 (16)	0.0036 (15)	0.0164 (17)
C4	0.044 (2)	0.082 (3)	0.061 (3)	−0.004 (2)	−0.0051 (19)	0.026 (2)
C5	0.036 (2)	0.100 (3)	0.051 (2)	−0.020 (2)	−0.0025 (17)	0.021 (2)
C6	0.055 (3)	0.155 (5)	0.070 (3)	−0.036 (3)	−0.019 (2)	0.039 (3)
C7	0.079 (4)	0.203 (7)	0.051 (3)	−0.071 (4)	−0.018 (3)	0.030 (4)
C8	0.097 (4)	0.174 (6)	0.051 (3)	−0.081 (4)	0.004 (3)	−0.005 (4)
C9	0.068 (3)	0.123 (4)	0.056 (3)	−0.045 (3)	0.008 (2)	−0.011 (3)
C10	0.040 (2)	0.100 (3)	0.044 (2)	−0.026 (2)	0.0043 (17)	0.000 (2)
C11	0.0364 (19)	0.069 (3)	0.053 (2)	−0.0072 (18)	0.0018 (17)	−0.0017 (19)
C12	0.0331 (18)	0.055 (2)	0.0407 (19)	−0.0037 (15)	0.0023 (15)	0.0038 (16)
C13	0.0315 (17)	0.0472 (19)	0.047 (2)	0.0029 (14)	0.0048 (15)	0.0062 (15)
C14	0.0306 (16)	0.0408 (18)	0.0381 (18)	−0.0017 (14)	0.0054 (14)	0.0037 (14)
C15	0.0366 (18)	0.0361 (17)	0.0414 (19)	0.0057 (14)	0.0002 (15)	−0.0001 (15)
C16	0.0417 (18)	0.0464 (18)	0.0311 (17)	−0.0031 (15)	0.0023 (14)	0.0060 (14)
C17	0.086 (3)	0.077 (3)	0.047 (2)	0.024 (2)	−0.002 (2)	−0.014 (2)
C18	0.103 (4)	0.098 (3)	0.043 (2)	0.014 (3)	−0.009 (2)	−0.021 (2)
C19	0.073 (3)	0.110 (4)	0.048 (2)	−0.025 (3)	−0.011 (2)	−0.004 (2)
C20	0.063 (3)	0.128 (4)	0.055 (3)	0.031 (3)	−0.016 (2)	−0.001 (3)
C21	0.056 (2)	0.090 (3)	0.050 (2)	0.025 (2)	−0.0089 (18)	−0.012 (2)
C22	0.0342 (16)	0.0350 (18)	0.0326 (17)	−0.0008 (14)	−0.0032 (13)	0.0026 (14)
C23	0.0413 (18)	0.0341 (17)	0.0387 (18)	−0.0055 (14)	0.0055 (14)	−0.0010 (14)
C24	0.0418 (19)	0.061 (2)	0.045 (2)	0.0000 (17)	−0.0013 (16)	0.0044 (17)
C25	0.064 (2)	0.080 (3)	0.041 (2)	−0.005 (2)	−0.0012 (18)	0.0103 (19)
C26	0.075 (3)	0.069 (2)	0.042 (2)	−0.014 (2)	0.0185 (19)	−0.0063 (18)
C27	0.053 (2)	0.066 (2)	0.054 (2)	0.0004 (18)	0.0173 (19)	−0.0046 (19)
C28	0.0429 (19)	0.0493 (19)	0.043 (2)	−0.0039 (16)	0.0020 (16)	−0.0013 (16)

Geometric parameters (Å, º)

Br1—C2	1.892 (3)	C14—C15	1.501 (4)
O1—C11	1.223 (4)	C16—C21	1.495 (5)
O2—C4	1.212 (5)	C16—C17	1.503 (5)
O3—C15	1.222 (3)	C16—H16	0.9800
O4—C22	1.212 (3)	C17—C18	1.529 (5)
N1—C13	1.346 (4)	C17—H17A	0.9700
N1—H1A	0.8863	C17—H17B	0.9700
N1—H1B	0.8858	C18—C19	1.481 (6)
N2—C15	1.363 (4)	C18—H18A	0.9700
N2—C22	1.447 (4)	C18—H18B	0.9700
N2—C16	1.483 (4)	C19—C20	1.471 (6)
N3—C22	1.315 (4)	C19—H19A	0.9700
N3—C23	1.459 (4)	C19—H19B	0.9700
N3—H3A	0.8600	C20—C21	1.539 (5)
C1—C14	1.364 (4)	C20—H20A	0.9700
C1—C2	1.391 (4)	C20—H20B	0.9700
C1—H1	0.9300	C21—H21A	0.9700
C2—C3	1.387 (5)	C21—H21B	0.9700
C3—C12	1.414 (5)	C23—C28	1.516 (4)
C3—C4	1.500 (5)	C23—C24	1.517 (4)
C4—C5	1.468 (6)	C23—H23	0.9800
C5—C10	1.378 (5)	C24—C25	1.521 (5)
C5—C6	1.395 (5)	C24—H24A	0.9700
C6—C7	1.375 (8)	C24—H24B	0.9700
C6—H6	0.9300	C25—C26	1.515 (5)
C7—C8	1.356 (8)	C25—H25A	0.9700
C7—H7	0.9300	C25—H25B	0.9700
C8—C9	1.388 (7)	C26—C27	1.512 (5)
C8—H8	0.9300	C26—H26A	0.9700
C9—C10	1.390 (5)	C26—H26B	0.9700
C9—H9	0.9300	C27—C28	1.518 (4)
C10—C11	1.490 (5)	C27—H27A	0.9700
C11—C12	1.475 (5)	C27—H27B	0.9700
C12—C13	1.415 (4)	C28—H28A	0.9700
C13—C14	1.430 (4)	C28—H28B	0.9700
C13—N1—H1A	119.6	H17A—C17—H17B	108.0
C13—N1—H1B	119.4	C19—C18—C17	111.8 (4)
H1A—N1—H1B	117.5	C19—C18—H18A	109.3
C15—N2—C22	123.2 (2)	C17—C18—H18A	109.3
C15—N2—C16	118.8 (3)	C19—C18—H18B	109.3
C22—N2—C16	117.9 (2)	C17—C18—H18B	109.3
C22—N3—C23	123.5 (2)	H18A—C18—H18B	107.9
C22—N3—H3A	118.3	C20—C19—C18	111.8 (3)
C23—N3—H3A	118.3	C20—C19—H19A	109.3
C14—C1—C2	122.1 (3)	C18—C19—H19A	109.3
C14—C1—H1	119.0	C20—C19—H19B	109.3
C2—C1—H1	119.0	C18—C19—H19B	109.3
C3—C2—C1	119.9 (3)	H19A—C19—H19B	107.9
C3—C2—Br1	124.5 (2)	C19—C20—C21	112.4 (4)
C1—C2—Br1	115.6 (3)	C19—C20—H20A	109.1
C2—C3—C12	119.1 (3)	C21—C20—H20A	109.1
C2—C3—C4	122.3 (3)	C19—C20—H20B	109.1
C12—C3—C4	118.5 (3)	C21—C20—H20B	109.1
O2—C4—C5	121.0 (4)	H20A—C20—H20B	107.9
O2—C4—C3	121.3 (4)	C16—C21—C20	109.6 (3)
C5—C4—C3	117.6 (4)	C16—C21—H21A	109.8
C10—C5—C6	119.4 (4)	C20—C21—H21A	109.8
C10—C5—C4	120.7 (3)	C16—C21—H21B	109.8
C6—C5—C4	119.8 (4)	C20—C21—H21B	109.8
C7—C6—C5	119.4 (5)	H21A—C21—H21B	108.2
C7—C6—H6	120.3	O4—C22—N3	125.8 (3)
C5—C6—H6	120.3	O4—C22—N2	120.7 (3)
C8—C7—C6	121.1 (5)	N3—C22—N2	113.5 (2)
C8—C7—H7	119.5	N3—C23—C28	110.1 (2)
C6—C7—H7	119.5	N3—C23—C24	111.2 (2)
C7—C8—C9	120.5 (6)	C28—C23—C24	111.9 (3)
C7—C8—H8	119.8	N3—C23—H23	107.8
C9—C8—H8	119.8	C28—C23—H23	107.8
C8—C9—C10	118.9 (5)	C24—C23—H23	107.8
C8—C9—H9	120.5	C23—C24—C25	111.1 (3)
C10—C9—H9	120.5	C23—C24—H24A	109.4
C5—C10—C9	120.6 (4)	C25—C24—H24A	109.4
C5—C10—C11	120.4 (4)	C23—C24—H24B	109.4
C9—C10—C11	119.1 (4)	C25—C24—H24B	109.4
O1—C11—C12	123.3 (3)	H24A—C24—H24B	108.0
O1—C11—C10	118.9 (3)	C26—C25—C24	111.0 (3)
C12—C11—C10	117.7 (3)	C26—C25—H25A	109.4
C3—C12—C13	120.7 (3)	C24—C25—H25A	109.4
C3—C12—C11	120.4 (3)	C26—C25—H25B	109.4
C13—C12—C11	118.9 (3)	C24—C25—H25B	109.4
N1—C13—C12	122.8 (3)	H25A—C25—H25B	108.0
N1—C13—C14	119.6 (3)	C27—C26—C25	110.5 (3)
C12—C13—C14	117.6 (3)	C27—C26—H26A	109.5
C1—C14—C13	119.9 (3)	C25—C26—H26A	109.5
C1—C14—C15	120.8 (3)	C27—C26—H26B	109.5
C13—C14—C15	119.0 (3)	C25—C26—H26B	109.5
O3—C15—N2	122.2 (3)	H26A—C26—H26B	108.1
O3—C15—C14	119.9 (3)	C26—C27—C28	111.7 (3)
N2—C15—C14	117.9 (3)	C26—C27—H27A	109.3
N2—C16—C21	112.2 (3)	C28—C27—H27A	109.3
N2—C16—C17	112.0 (3)	C26—C27—H27B	109.3
C21—C16—C17	111.5 (3)	C28—C27—H27B	109.3
N2—C16—H16	106.9	H27A—C27—H27B	107.9
C21—C16—H16	106.9	C23—C28—C27	111.4 (3)
C17—C16—H16	106.9	C23—C28—H28A	109.4
C16—C17—C18	111.1 (3)	C27—C28—H28A	109.4
C16—C17—H17A	109.4	C23—C28—H28B	109.4
C18—C17—H17A	109.4	C27—C28—H28B	109.4
C16—C17—H17B	109.4	H28A—C28—H28B	108.0
C18—C17—H17B	109.4
C14—C1—C2—C3	−3.3 (5)	C2—C1—C14—C15	−173.7 (3)
C14—C1—C2—Br1	177.7 (2)	N1—C13—C14—C1	−175.6 (3)
C1—C2—C3—C12	0.0 (5)	C12—C13—C14—C1	6.6 (4)
Br1—C2—C3—C12	179.0 (2)	N1—C13—C14—C15	−1.9 (4)
C1—C2—C3—C4	178.0 (3)	C12—C13—C14—C15	−179.7 (3)
Br1—C2—C3—C4	−3.0 (5)	C22—N2—C15—O3	168.7 (3)
C2—C3—C4—O2	−21.6 (6)	C16—N2—C15—O3	−8.0 (4)
C12—C3—C4—O2	156.4 (4)	C22—N2—C15—C14	−12.9 (4)
C2—C3—C4—C5	160.1 (3)	C16—N2—C15—C14	170.3 (3)
C12—C3—C4—C5	−21.9 (5)	C1—C14—C15—O3	125.1 (3)
O2—C4—C5—C10	−161.7 (4)	C13—C14—C15—O3	−48.5 (4)
C3—C4—C5—C10	16.6 (5)	C1—C14—C15—N2	−53.2 (4)
O2—C4—C5—C6	18.4 (6)	C13—C14—C15—N2	133.1 (3)
C3—C4—C5—C6	−163.3 (3)	C15—N2—C16—C21	129.4 (3)
C10—C5—C6—C7	−3.1 (6)	C22—N2—C16—C21	−47.5 (4)
C4—C5—C6—C7	176.8 (4)	C15—N2—C16—C17	−104.4 (3)
C5—C6—C7—C8	2.9 (8)	C22—N2—C16—C17	78.7 (4)
C6—C7—C8—C9	−0.8 (8)	N2—C16—C17—C18	177.8 (3)
C7—C8—C9—C10	−1.1 (7)	C21—C16—C17—C18	−55.5 (5)
C6—C5—C10—C9	1.2 (6)	C16—C17—C18—C19	53.9 (5)
C4—C5—C10—C9	−178.7 (3)	C17—C18—C19—C20	−54.0 (5)
C6—C5—C10—C11	−177.6 (3)	C18—C19—C20—C21	55.3 (5)
C4—C5—C10—C11	2.5 (5)	N2—C16—C21—C20	−177.8 (3)
C8—C9—C10—C5	0.9 (6)	C17—C16—C21—C20	55.7 (4)
C8—C9—C10—C11	179.7 (4)	C19—C20—C21—C16	−55.9 (5)
C5—C10—C11—O1	166.8 (3)	C23—N3—C22—O4	−1.8 (5)
C9—C10—C11—O1	−12.0 (5)	C23—N3—C22—N2	−179.7 (2)
C5—C10—C11—C12	−16.5 (5)	C15—N2—C22—O4	115.2 (3)
C9—C10—C11—C12	164.7 (3)	C16—N2—C22—O4	−68.0 (4)
C2—C3—C12—C13	6.6 (5)	C15—N2—C22—N3	−66.7 (3)
C4—C3—C12—C13	−171.5 (3)	C16—N2—C22—N3	110.1 (3)
C2—C3—C12—C11	−173.9 (3)	C22—N3—C23—C28	128.9 (3)
C4—C3—C12—C11	8.1 (5)	C22—N3—C23—C24	−106.5 (3)
O1—C11—C12—C3	−172.7 (3)	N3—C23—C24—C25	−177.8 (3)
C10—C11—C12—C3	10.8 (5)	C28—C23—C24—C25	−54.2 (4)
O1—C11—C12—C13	6.9 (5)	C23—C24—C25—C26	56.1 (4)
C10—C11—C12—C13	−169.6 (3)	C24—C25—C26—C27	−57.1 (4)
C3—C12—C13—N1	172.4 (3)	C25—C26—C27—C28	56.4 (4)
C11—C12—C13—N1	−7.1 (5)	N3—C23—C28—C27	177.5 (2)
C3—C12—C13—C14	−9.8 (5)	C24—C23—C28—C27	53.3 (3)
C11—C12—C13—C14	170.7 (3)	C26—C27—C28—C23	−54.5 (4)
C2—C1—C14—C13	−0.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20B···Br1^i	0.97	2.91 (1)	3.711 (5)	140 (1)
C17—H17A···O2^ii	0.97	2.67 (1)	3.617 (5)	166 (1)
N3—H3A···O4^i	0.86	2.08 (1)	2.907 (5)	161 (1)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x, y, −z+1/2.