Crystal structure of 2-[(E)-2-(4-bromo-phen-yl)diazen-1-yl]-4,5-bis-(4-meth-oxy-phen-yl)-1H-imidazole: the first example of a structurally characterized tri-aryl-azo-imid-azole.

The title compound, C23H19BrN4O2, is a product of an azo coupling reaction between 3,4-bis-(4-meth-oxy-phen-yl)imidazole and 4-bromo-phenyl-diazo-nium tetra-fluoro-borate. Its crystal structure was determined using data collected at 120 K. The mol-ecule adopts a trans configuration with respect to the N=N double bond. The imidazole and aryl rings attached to the azo linkage are coplanar within 12.73 (14)°, which indicates significant electron delocalization within the mol-ecule. In the crystal, the mol-ecules form centrosymmetric dimers via pairs of N-H⋯O hydrogen bonds. © Temesgen et al. 2021.

Chemical context

Azo­imidazoles are a class of dyes that have found widespread applications in industry, as well as in laboratory research (Eymann et al., 2016 ▸; Tskhovrebov et al., 2014 ▸; Liu et al., 2019 ▸). They are widely used for dyeing natural and synthetic fibers. In addition, they have found applications as photoswitches and hold promise for utilization in photopharmacology (Crespi et al., 2019 ▸). Azo-functionalized imidazoles have been studied intensively as ligands in coordination chemistry (Sarker, Chand et al., 2007 ▸; Sarker, Sardar et al., 2007 ▸; Schütt et al., 2016 ▸; Das et al., 1997 ▸; Misra et al., 1997 ▸). They are also attractive as chelating bidentate ligands. Azo­imidazole coordination compounds have been reported for numerous metals, some of them showing inter­esting photochromic properties (Sarker, Sardar et al., 2007 ▸; Sarker, Chand et al., 2007 ▸; Crespi et al., 2019 ▸). Numerous publications have been devoted to the development of organic crystalline materials that contain various imidazole-based architectures (Akhriff et al., 2006 ▸). Following our inter­est in azo dyes (Nenajdenko et al., 2020 ▸; Tskhovrebov, Vasileva et al., 2018 ▸), imidazole chemistry, imidazolylidenes and corresponding metal–carbene com­plexes (Tskhovrebov, Lingnau et al., 2019 ▸; Tskhovrebov, Goddard et al., 2018 ▸; Mikhaylov et al., 2018 ▸; Tskhovrebov et al., 2012 ▸), we report here the synthesis and crystal structure of (E)-2-[(4-bromo­phen­yl)diazen­yl]-4,5-bis­(4-meth­oxy­phen­yl)-1H-imidazole. Although azo­imidazoles form a widely studied class of azo compounds, tri­aryl­azo­imidazoles have never been structurally characterized. This work presents the first example of structurally characterized tri­aryl­azo­imidazole.

The PASS program (Filimonov et al., 2014 ▸) predicted the potential activity of the title compound as a thiol protease inhibitor and an aspulvinone di­methyl­allyl­transferase inhib­itor at 81% and 76% probability levels, respectively.

Structural commentary

The mol­ecular structure of the title compound is shown in Fig. 1 ▸. Overall, bond dimensions within the mol­ecule are similar to those reported for structurally relevant azo compounds (Tskhovrebov et al., 2014 ▸, 2015 ▸; Liu et al., 2019 ▸; Eymann et al., 2016 ▸; Nenajdenko et al., 2020 ▸). The mol­ecule adopts a trans configuration with respect to the azo double bond. The N=N bond distance of 1.274 (3) Å is slightly longer than that in azo­benzene. The imidazole and aryl rings attached to the azo group are coplanar within 12.73 (14)°, which indicates significant electron delocalization within the mol­ecule. The two other aromatic rings, C4–C9 and C11–C16, form dihedral angles with the plane of the imidazole ring of 60.64 (14) and 22.38 (13)°, respectively.

Figure 1

Mol­ecular structure of the title compound. Displacement ellipsoids are shown at the 50% probability level. The hydrogen atoms are presented as small spheres of arbitrary radius.

Supra­molecular features

In the crystal, the title mol­ecules form centrosymmetric dimers via pairs of N—H⋯O hydrogen bonds (Fig. 2 ▸, Table 1 ▸). A similar supra­molecular motif has previously been observed by our group (Repina et al., 2020 ▸; Tskhovrebov, Novikov et al., 2019 ▸). The crystal packing involves some π–π stacking inter­actions (Fig. 3 ▸) with a shortest inter­centroid separation of 3.792 (2) Å between two imidazole rings related by the symmetry operation 1 − x, 1 − y, 1 − z.

Figure 2

The hydrogen-bonded centrosymmetric dimer. Dashed lines indicate the N—H⋯O hydrogen bonds.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.80 (3)	2.17 (3)	2.963 (3)	169 (3)

Symmetry code: (i) -x, -y+1, -z+1.

Figure 3

Crystal packing projected along the-a axis direction.

Database survey

A search of the Cambridge Structural Database (CSD version 5.41, update of March 2020; Groom et al., 2016 ▸) revealed that this is the first example of a structurally characterized tri­aryl­azomidazole. At the same time, the CSD search revealed several examples of structurally similar azo­imidazoles, which contain a proton at the imidazolic N atom, viz. 2-[(4-bromo­phen­yl)diazen­yl]-1H-imidazole (Pramanik et al., 2010 ▸), 2-(1-naphthyl­diazen­yl)-1H-imidazole (Pramanik et al., 2010 ▸), 2-[4-(N,N-di­hydroxy­ethyl­amino)­phenyl­azo]-4,5-di­cyano­imidazole (Carella et al., 2004 ▸), phenyl­azo­imidazole (Fun et al., 1999 ▸), 4-(4,5-di­cyano-1H-imidazolyazo)-N,N-di­ethyl­aniline (Zhang et al., 2007 ▸), 2-(p-tolyl­azo)imidazole (Bhunia et al., 2006 ▸) and 3,3′-({4-[(4,5-di­cyano-1H-imidazol-2-yl)diazen­yl]phen­yl}im­ino) dipropionic acid (Centore et al., 2013 ▸).

Synthesis and crystallization

Tri­aryl­azo­imidazole was prepared according to the literature method (Fun et al., 1999 ▸) via azo coupling of p-bromo­phenyl­diazo­nium tetra­fluoro­borate with di(p-anis­yl)imidazole and isolated in 84% yield as a red solid. Crystals suitable for X-ray analysis were obtained by slow evaporation of a saturated MeOH solution.

Refinement

Crystal data, details of data collection, and results of structure refinement are summarized in Table 2 ▸. The X-ray diffraction study was performed using the equipment of the Center for Mol­ecular Studies of INEOS RAS. The hydrogen atom of the NH group was localized in the difference-Fourier map and refined with a fixed isotropic displacement parameter [U iso(H) = 1.2U eq(N)]. The other hydrogen atoms were placed in calculated positions with C—H = 0.95–0.98 Å and refined using a riding model with fixed isotropic displacement parameters [U iso(H) = 1.5U eq(C) for CH3 groups and U iso(H) = 1.2U eq(C) for other groups].

Table 2

Experimental details

Crystal data
Chemical formula	C23H19BrN4O2
M r	463.32
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	120
a, b, c (Å)	10.7812 (9), 12.7877 (11), 15.4575 (13)
β (°)	109.635 (2)
V (Å3)	2007.2 (3)
Z	4
Radiation type	Mo Kα
μ (mm−1)	2.08
Crystal size (mm)	0.33 × 0.21 × 0.08
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max	0.597, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	22147, 6069, 3449
R int	0.084
(sin θ/λ)max (Å−1)	0.714
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.052, 0.122, 1.00
No. of reflections	6069
No. of parameters	276
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.44, −0.62

Computer programs: APEX3 (Bruker, 2018 ▸), SAINT (Bruker, 2013 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸) and SHELXTL (Sheldrick, 2008 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021002024/yk2143sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989021002024/yk2143Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989021002024/yk2143Isup3.cml

CCDC reference: 2064019

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

C23H19BrN4O2	F(000) = 944
Mr = 463.32	Dx = 1.533 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.7812 (9) Å	Cell parameters from 2288 reflections
b = 12.7877 (11) Å	θ = 2.6–25.4°
c = 15.4575 (13) Å	µ = 2.08 mm−1
β = 109.635 (2)°	T = 120 K
V = 2007.2 (3) Å3	Plate, orange
Z = 4	0.33 × 0.21 × 0.08 mm

Bruker APEXII CCD diffractometer	3449 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.084
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θmax = 30.5°, θmin = 2.0°
Tmin = 0.597, Tmax = 0.746	h = −14→15
22147 measured reflections	k = −18→18
6069 independent reflections	l = −21→21

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)] = 0.052	Hydrogen site location: mixed
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0498P)2] where P = (Fo2 + 2Fc2)/3
6069 reflections	(Δ/σ)max < 0.001
276 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.61 e Å−3

Experimental. SADABS-2014/5 (Bruker, 2014/5) was used for absorption correction. wR2(int) was 0.0815 before and 0.0536 after correction. The Ratio of minimum to maximum transmission is 0.8000. The λ/2 correction factor is 0.00150.

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	0.27445 (4)	0.40711 (3)	−0.14822 (2)	0.04431 (14)
O1	−0.01642 (18)	0.55364 (14)	0.68807 (12)	0.0212 (4)
O2	0.84035 (18)	0.33604 (14)	0.90163 (12)	0.0249 (4)
N1	0.2914 (2)	0.39235 (17)	0.42224 (15)	0.0191 (5)
H1	0.222 (3)	0.410 (2)	0.387 (2)	0.023*
N2	0.5047 (2)	0.35277 (17)	0.47136 (14)	0.0194 (5)
N3	0.4041 (2)	0.36812 (17)	0.30966 (15)	0.0204 (5)
N4	0.2927 (2)	0.38470 (16)	0.24827 (15)	0.0215 (5)
C1	0.3985 (3)	0.36862 (19)	0.39831 (17)	0.0176 (5)
C2	0.4641 (3)	0.37005 (19)	0.54552 (17)	0.0162 (5)
C3	0.3314 (3)	0.39603 (19)	0.51634 (17)	0.0178 (5)
C4	0.2423 (3)	0.43346 (19)	0.56408 (17)	0.0163 (5)
C5	0.2757 (3)	0.5239 (2)	0.61663 (17)	0.0192 (6)
H5	0.3570	0.5577	0.6235	0.023*
C6	0.1921 (3)	0.56603 (19)	0.65933 (17)	0.0177 (6)
H6	0.2161	0.6281	0.6949	0.021*
C7	0.0742 (3)	0.51714 (19)	0.64976 (17)	0.0175 (5)
C8	0.0393 (3)	0.4255 (2)	0.59788 (18)	0.0203 (6)
H8	−0.0416	0.3915	0.5918	0.024*
C9	0.1230 (3)	0.38447 (19)	0.55551 (17)	0.0190 (6)
H9	0.0990	0.3223	0.5202	0.023*
C10	0.0165 (3)	0.6508 (2)	0.7369 (2)	0.0321 (7)
H10A	0.0296	0.7048	0.6958	0.048*
H10B	0.0978	0.6422	0.7895	0.048*
H10C	−0.0552	0.6717	0.7588	0.048*
C11	0.5584 (3)	0.36163 (19)	0.64007 (17)	0.0175 (5)
C12	0.5186 (3)	0.34390 (19)	0.71556 (18)	0.0195 (6)
H12	0.4273	0.3382	0.7065	0.023*
C13	0.6090 (3)	0.3342 (2)	0.80404 (18)	0.0201 (6)
H13	0.5800	0.3203	0.8545	0.024*
C14	0.7421 (3)	0.34526 (19)	0.81732 (17)	0.0199 (6)
C15	0.7843 (3)	0.3655 (2)	0.74336 (18)	0.0208 (6)
H15	0.8753	0.3754	0.7531	0.025*
C16	0.6935 (3)	0.3714 (2)	0.65562 (18)	0.0200 (6)
H16	0.7232	0.3822	0.6050	0.024*
C17	0.7997 (3)	0.3123 (2)	0.97884 (18)	0.0289 (7)
H17A	0.7433	0.2501	0.9652	0.043*
H17B	0.7506	0.3716	0.9911	0.043*
H17C	0.8775	0.2989	1.0329	0.043*
C18	0.2974 (3)	0.38963 (19)	0.15723 (18)	0.0198 (6)
C19	0.4131 (3)	0.3895 (2)	0.13582 (18)	0.0234 (6)
H19	0.4961	0.3872	0.1835	0.028*
C20	0.4069 (3)	0.3928 (2)	0.04512 (19)	0.0270 (7)
H20	0.4851	0.3907	0.0298	0.032*
C21	0.2842 (3)	0.3992 (2)	−0.02354 (18)	0.0272 (7)
C22	0.1682 (3)	0.4025 (2)	−0.0033 (2)	0.0294 (7)
H22	0.0853	0.4075	−0.0508	0.035*
C23	0.1765 (3)	0.3983 (2)	0.08831 (19)	0.0250 (6)
H23	0.0984	0.4014	0.1037	0.030*

	U11	U22	U33	U12	U13	U23
Br1	0.0599 (3)	0.0551 (2)	0.01949 (15)	0.01172 (18)	0.01531 (15)	0.00843 (14)
O1	0.0173 (10)	0.0258 (10)	0.0236 (10)	−0.0033 (8)	0.0110 (8)	−0.0072 (8)
O2	0.0192 (11)	0.0302 (11)	0.0220 (10)	−0.0016 (8)	0.0025 (8)	0.0041 (8)
N1	0.0171 (12)	0.0223 (12)	0.0187 (11)	0.0021 (10)	0.0073 (10)	0.0012 (9)
N2	0.0197 (13)	0.0231 (12)	0.0192 (11)	0.0024 (9)	0.0116 (10)	0.0030 (9)
N3	0.0207 (13)	0.0200 (11)	0.0223 (11)	0.0010 (9)	0.0098 (10)	0.0001 (9)
N4	0.0229 (13)	0.0228 (12)	0.0212 (11)	−0.0008 (9)	0.0105 (10)	−0.0023 (9)
C1	0.0159 (14)	0.0201 (13)	0.0200 (13)	0.0009 (10)	0.0103 (11)	−0.0004 (10)
C2	0.0165 (14)	0.0168 (12)	0.0180 (12)	−0.0010 (10)	0.0096 (11)	0.0015 (9)
C3	0.0200 (14)	0.0182 (13)	0.0170 (12)	0.0008 (11)	0.0089 (11)	0.0011 (10)
C4	0.0156 (14)	0.0189 (13)	0.0157 (12)	0.0033 (10)	0.0068 (11)	0.0025 (9)
C5	0.0158 (14)	0.0244 (14)	0.0180 (12)	−0.0027 (11)	0.0062 (11)	0.0012 (10)
C6	0.0177 (14)	0.0189 (13)	0.0167 (12)	−0.0004 (10)	0.0062 (11)	−0.0008 (9)
C7	0.0159 (14)	0.0224 (14)	0.0162 (12)	0.0029 (11)	0.0080 (11)	0.0024 (10)
C8	0.0159 (14)	0.0224 (14)	0.0235 (13)	−0.0059 (10)	0.0080 (11)	−0.0009 (10)
C9	0.0214 (15)	0.0171 (14)	0.0204 (13)	0.0001 (10)	0.0095 (12)	−0.0023 (10)
C10	0.0271 (18)	0.0387 (18)	0.0361 (18)	−0.0066 (14)	0.0181 (15)	−0.0197 (14)
C11	0.0213 (15)	0.0138 (12)	0.0204 (13)	0.0017 (10)	0.0108 (11)	0.0014 (10)
C12	0.0167 (14)	0.0206 (14)	0.0228 (13)	0.0000 (11)	0.0087 (11)	0.0022 (10)
C13	0.0216 (15)	0.0205 (14)	0.0200 (13)	0.0005 (11)	0.0094 (12)	0.0015 (10)
C14	0.0197 (15)	0.0154 (13)	0.0210 (13)	−0.0009 (10)	0.0021 (11)	0.0008 (10)
C15	0.0176 (15)	0.0185 (13)	0.0289 (14)	0.0020 (11)	0.0112 (12)	0.0030 (11)
C16	0.0179 (15)	0.0199 (13)	0.0251 (14)	0.0019 (11)	0.0112 (12)	0.0025 (10)
C17	0.0272 (17)	0.0354 (17)	0.0201 (14)	−0.0006 (13)	0.0027 (13)	0.0011 (12)
C18	0.0239 (16)	0.0168 (13)	0.0215 (13)	−0.0027 (11)	0.0113 (12)	0.0003 (10)
C19	0.0246 (16)	0.0261 (15)	0.0205 (13)	0.0041 (12)	0.0087 (12)	0.0030 (11)
C20	0.0264 (17)	0.0315 (16)	0.0271 (15)	0.0039 (13)	0.0141 (13)	0.0044 (12)
C21	0.0401 (19)	0.0242 (15)	0.0184 (13)	0.0012 (13)	0.0113 (13)	0.0024 (11)
C22	0.0322 (18)	0.0274 (16)	0.0235 (14)	−0.0054 (13)	0.0028 (13)	−0.0007 (12)
C23	0.0203 (15)	0.0297 (16)	0.0245 (14)	−0.0048 (12)	0.0069 (12)	−0.0008 (12)

Br1—C21	1.897 (3)	C10—H10A	0.9800
O1—C7	1.382 (3)	C10—H10B	0.9800
O1—C10	1.435 (3)	C10—H10C	0.9800
O2—C14	1.381 (3)	C11—C12	1.390 (4)
O2—C17	1.435 (3)	C11—C16	1.400 (4)
N1—C1	1.360 (3)	C12—C13	1.393 (4)
N1—C3	1.372 (3)	C12—H12	0.9500
N1—H1	0.80 (3)	C13—C14	1.387 (4)
N2—C1	1.326 (3)	C13—H13	0.9500
N2—C2	1.375 (3)	C14—C15	1.389 (4)
N3—N4	1.274 (3)	C15—C16	1.382 (4)
N3—C1	1.392 (3)	C15—H15	0.9500
N4—C18	1.427 (3)	C16—H16	0.9500
C2—C3	1.388 (4)	C17—H17A	0.9800
C2—C11	1.477 (4)	C17—H17B	0.9800
C3—C4	1.474 (4)	C17—H17C	0.9800
C4—C5	1.390 (3)	C18—C23	1.383 (4)
C4—C9	1.397 (4)	C18—C19	1.393 (4)
C5—C6	1.392 (4)	C19—C20	1.382 (4)
C5—H5	0.9500	C19—H19	0.9500
C6—C7	1.379 (4)	C20—C21	1.392 (4)
C6—H6	0.9500	C20—H20	0.9500
C7—C8	1.399 (3)	C21—C22	1.388 (5)
C8—C9	1.384 (4)	C22—C23	1.389 (4)
C8—H8	0.9500	C22—H22	0.9500
C9—H9	0.9500	C23—H23	0.9500
C7—O1—C10	115.6 (2)	C12—C11—C2	122.6 (2)
C14—O2—C17	116.8 (2)	C16—C11—C2	119.6 (2)
C1—N1—C3	107.6 (2)	C11—C12—C13	121.8 (3)
C1—N1—H1	125 (2)	C11—C12—H12	119.1
C3—N1—H1	127 (2)	C13—C12—H12	119.1
C1—N2—C2	105.0 (2)	C14—C13—C12	119.0 (2)
N4—N3—C1	113.0 (2)	C14—C13—H13	120.5
N3—N4—C18	113.9 (2)	C12—C13—H13	120.5
N2—C1—N1	111.8 (2)	O2—C14—C13	123.9 (2)
N2—C1—N3	121.8 (2)	O2—C14—C15	115.7 (2)
N1—C1—N3	126.2 (2)	C13—C14—C15	120.4 (2)
N2—C2—C3	110.5 (2)	C16—C15—C14	119.9 (3)
N2—C2—C11	120.5 (2)	C16—C15—H15	120.1
C3—C2—C11	129.1 (2)	C14—C15—H15	120.1
N1—C3—C2	105.0 (2)	C15—C16—C11	121.1 (2)
N1—C3—C4	121.1 (2)	C15—C16—H16	119.4
C2—C3—C4	133.5 (2)	C11—C16—H16	119.4
C5—C4—C9	118.6 (2)	O2—C17—H17A	109.5
C5—C4—C3	118.6 (2)	O2—C17—H17B	109.5
C9—C4—C3	122.8 (2)	H17A—C17—H17B	109.5
C4—C5—C6	121.2 (3)	O2—C17—H17C	109.5
C4—C5—H5	119.4	H17A—C17—H17C	109.5
C6—C5—H5	119.4	H17B—C17—H17C	109.5
C7—C6—C5	119.6 (2)	C23—C18—C19	120.3 (2)
C7—C6—H6	120.2	C23—C18—N4	115.2 (2)
C5—C6—H6	120.2	C19—C18—N4	124.4 (2)
C6—C7—O1	124.0 (2)	C20—C19—C18	119.9 (3)
C6—C7—C8	120.1 (2)	C20—C19—H19	120.0
O1—C7—C8	115.9 (2)	C18—C19—H19	120.0
C9—C8—C7	119.8 (2)	C19—C20—C21	119.0 (3)
C9—C8—H8	120.1	C19—C20—H20	120.5
C7—C8—H8	120.1	C21—C20—H20	120.5
C8—C9—C4	120.8 (2)	C22—C21—C20	121.8 (3)
C8—C9—H9	119.6	C22—C21—Br1	118.8 (2)
C4—C9—H9	119.6	C20—C21—Br1	119.4 (2)
O1—C10—H10A	109.5	C21—C22—C23	118.3 (3)
O1—C10—H10B	109.5	C21—C22—H22	120.8
H10A—C10—H10B	109.5	C23—C22—H22	120.8
O1—C10—H10C	109.5	C18—C23—C22	120.6 (3)
H10A—C10—H10C	109.5	C18—C23—H23	119.7
H10B—C10—H10C	109.5	C22—C23—H23	119.7
C12—C11—C16	117.8 (2)
C1—N3—N4—C18	177.1 (2)	C3—C4—C9—C8	−176.7 (2)
C2—N2—C1—N1	−1.7 (3)	N2—C2—C11—C12	−158.2 (2)
C2—N2—C1—N3	173.7 (2)	C3—C2—C11—C12	22.9 (4)
C3—N1—C1—N2	2.4 (3)	N2—C2—C11—C16	21.6 (3)
C3—N1—C1—N3	−172.7 (2)	C3—C2—C11—C16	−157.2 (3)
N4—N3—C1—N2	180.0 (2)	C16—C11—C12—C13	−1.1 (4)
N4—N3—C1—N1	−5.3 (4)	C2—C11—C12—C13	178.8 (2)
C1—N2—C2—C3	0.4 (3)	C11—C12—C13—C14	1.7 (4)
C1—N2—C2—C11	−178.7 (2)	C17—O2—C14—C13	0.8 (4)
C1—N1—C3—C2	−2.0 (3)	C17—O2—C14—C15	−178.4 (2)
C1—N1—C3—C4	171.9 (2)	C12—C13—C14—O2	−179.2 (2)
N2—C2—C3—N1	1.0 (3)	C12—C13—C14—C15	−0.1 (4)
C11—C2—C3—N1	180.0 (2)	O2—C14—C15—C16	177.1 (2)
N2—C2—C3—C4	−171.7 (3)	C13—C14—C15—C16	−2.1 (4)
C11—C2—C3—C4	7.2 (5)	C14—C15—C16—C11	2.7 (4)
N1—C3—C4—C5	−115.9 (3)	C12—C11—C16—C15	−1.2 (4)
C2—C3—C4—C5	55.9 (4)	C2—C11—C16—C15	179.0 (2)
N1—C3—C4—C9	61.2 (3)	N3—N4—C18—C23	174.5 (2)
C2—C3—C4—C9	−127.0 (3)	N3—N4—C18—C19	−7.5 (4)
C9—C4—C5—C6	−0.6 (4)	C23—C18—C19—C20	−3.2 (4)
C3—C4—C5—C6	176.6 (2)	N4—C18—C19—C20	178.9 (2)
C4—C5—C6—C7	0.2 (4)	C18—C19—C20—C21	1.8 (4)
C5—C6—C7—O1	−178.9 (2)	C19—C20—C21—C22	0.1 (4)
C5—C6—C7—C8	0.4 (4)	C19—C20—C21—Br1	178.5 (2)
C10—O1—C7—C6	2.6 (4)	C20—C21—C22—C23	−0.6 (4)
C10—O1—C7—C8	−176.7 (2)	Br1—C21—C22—C23	−179.0 (2)
C6—C7—C8—C9	−0.6 (4)	C19—C18—C23—C22	2.8 (4)
O1—C7—C8—C9	178.7 (2)	N4—C18—C23—C22	−179.2 (2)
C7—C8—C9—C4	0.1 (4)	C21—C22—C23—C18	−0.8 (4)
C5—C4—C9—C8	0.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.80 (3)	2.17 (3)	2.963 (3)	169 (3)