Crystal structure of 4-bromo-N-[(3,6-di-tert-butyl-9H-carbazol-1-yl)methyl­idene]aniline

Kubono, K.; Matsumoto, T.; Taneda, M.

doi:10.1107/S2056989019012374

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 10| October 2019| Pages 1429-1431

https://doi.org/10.1107/S2056989019012374

Open

access

Crystal structure of 4-bromo-N-[(3,6-di-tert-butyl-9H-carbazol-1-yl)methylidene]aniline

Koji Kubono,^a Taisuke Matsumoto ^b and Masatsugu Taneda ^c ^*

^aDivision of Natural Sciences, Osaka Kyoiku University, Kashiwara, Osaka 582-8582, Japan, ^bInstitute for Materials Chemistry and Engineering, Kyushu University, Kasuga, Fukuoka 816-8580, Japan, and ^cDepartment of Science Education, Faculty of Education, Osaka Kyoiku University, Kashiwara, Osaka 582-8582, Japan
^*Correspondence e-mail: tane@cc.osaka-kyoiku.ac.jp

Edited by H. Ishida, Okayama University, Japan (Received 27 August 2019; accepted 5 September 2019; online 10 September 2019)

In the title compound, C₂₇H₂₉BrN₂, the carbazole ring system is essentially planar, with an r.m.s. deviation of 0.0781 (16) Å. An intramolecular N—H⋯N hydrogen bond forms an S(6) ring motif. One of the tert-butyl substituents shows rotational disorder over two sites with occupancies of 0.592 (3) and 0.408 (3). In the crystal, two molecules are associated into an inversion dimer through a pair of C—H⋯π interactions. The dimers are further linked by another pair of C—H⋯π interactions, forming a ribbon along the c-axis direction. A C—H⋯π interaction involving the minor disordered component and the carbazole ring system links the ribbons, generating a network sheet parallel to (100).

Keywords: crystal structure; carbazole; Schiff base; intramolecular hydrogen bond; C—H⋯π interaction.

CCDC reference: 1951647

1. Chemical context

Carbazole derivatives have been widely applied in various fields such as pharmaceuticals (Obora, 2018 ), electroluminescent materials (Krucaite & Grigalevicius, 2019 ; Taneda, et al., 2015 ) and dyes (Zhao et al., 2019 ). As a result of the high acidity of the N—H bond, 9H-carbazoles have also attracted much attention as hydrogen donors in hydrogen-bonding systems (Rubio et al., 2015 ; Wiosna-Sałyga et al., 2006 ). Substitution of the 1 position of 9H-carbazole with a hydrogen acceptor can afford an intramolecular hydrogen-bonding system in the molecules. In this work, a Schiff base including carbazole, N-(3,6-di-tert-butyl-9H-calbazol-1-ylmethylidene)-4-bromoaniline, is newly synthesized. 3,6-Di-tert-butyl-9H-carbazole is useful in order to substitute the 1-position of the 9H-carbazole moiety because the substitution reaction would only occur at its 1- and 8-positions. Thus, the title compound has two tert-butyl groups on the carbazole moiety. The title compound is a suitable model to investigate an intramolecular hydrogen bond between the heteroaromatic N—H and the N atom of the imino group. We report herein on its molecular and crystal structures.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The molecule adopts an E configuration with respect to the C=N double bond. The carbazole ring is almost planar with a maximum deviation of 0.0781 (16) Å at atom C8. There is an intramolecular N—H⋯N hydrogen bond involving the amino group (N3—H3) in the carbazole ring and an imine N atom (N2), generating an S(6) ring motif (Table 1). The dihedral angle between the mean planes of the carbazole ring system and the benzene C25–C30 ring is 42.72 (7)°. The bond lengths and angles of the title compound are normal and agree with those values in other carbazole imine compounds (Gibson et al., 2003 ; Nolla-Saltiel et al., 2018 ). One of the tert-butyl substituents shows rotational disorder around the C13—C20 bond axis over two sites with occupancies of 0.592 (3) and 0.408 (3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2 and Cg3 are the centroids of the C25–C30, C4–C9 and N3/C4/C5/C11/C10 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯N2	0.76 (2)	2.39 (2)	2.862 (2)	121.3 (16)
C22A—H22C⋯Cg1ⁱ	0.96	2.92	3.878 (4)	177
C29—H29⋯Cg2ⁱⁱ	0.93	2.95	3.613 (2)	129
C21B—H21E⋯Cg1ⁱ	0.96	2.62	3.391 (5)	138
C22B—H22D⋯Cg3ⁱⁱⁱ	0.96	2.92	3.839 (5)	159
Symmetry codes: (i) -x, -y, -z+1; (ii) -x, -y, -z; (iii) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, with atom labelling. Only the major disordered component is shown. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by spheres of arbitrary radius. The intramolecular N—H⋯N hydrogen bond is shown as a dashed line.

3. Supramolecular features

In the crystal, two molecules are associated through a pair of C—H⋯π interactions (C22A—H22C⋯Cg1ⁱ in the major disorder component or C21B—H21E⋯Cg1ⁱ in the minor disorder component; Cg1 is the centroid of the C25–C30 ring; symmetry code as in Table 1), forming a centrosymmetric dimer. The dimers are linked by another pair of C—H⋯π interactions (C29—H29⋯Cg2ⁱⁱ; Cg2 is the centroid of the C4–C9 ring; symmetry code as in Table 1), forming a ribbon along the c-axis direction (Fig. 2). These ribbons are linked via a C—H⋯π interaction involving the minor disorder component (C22B—H22D⋯Cg3ⁱⁱⁱ; Cg3 is the centroid of the N3/C4/C5/C11/C10 ring; symmetry code as in Table 1) into a network sheet parallel to (100) (Fig. 3).

Figure 2
A packing diagram of the title compound, showing the ribbon structure. The N—H⋯N hydrogen bonds and the C—H⋯π interactions are shown as dashed lines. H atoms not involved in the interactions and the minor disorder component have been omitted for clarity.

Figure 3
A packing diagram of the title compound viewed along the a axis, showing a sheet structure. The minor disorder component is shown with bold dashed lines. The N—H⋯N hydrogen bonds and the C—H⋯π interactions are shown as dashed lines. H atoms not involved in the interactions and the major disorder component have been omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.40; February 2019; Groom et al., 2016 ) gave 56 and 5 hits, respectively, for the 3,6-di-tert-butyl-9H-carbazole and 9H-carbazol-1-ylmethylidene fragments. Of these structures, the compounds that resemble the title compound are (3,6-di-tert-butyl-9H-carbazole-1,8-diyl)bis[N-(naphthalen-1-yl)methanimine] (Nolla-Saltiel et al., 2018) and 1,8-bis[(2,4,6-trimethylphenyl)iminomethyl]-3,6-dimethyl-9H-carbazole (Gibson et al., 2003).

5. Synthesis and crystallization

3,6-Di-tert-butyl-9H-carbazole-1-carbaldehyde (154 mg, 0.50 mmol) and 4-bromoaniline (86 mg, 0.50 mmol) were treated in xylene (10 ml) at 423 K under inert gas overnight, followed by evaporation. The recrystallization of the residue from a solvent mixture of acetone and methanol (1:1, v:v) afforded single crystals of the title compound suitable for X-ray structure analysis (97 mg, 0.21 mmol; yield 42%). ¹H NMR (CDCl₃, 400 MHz) δ = 1.47 [s, 9H, C(CH₃)₃], 1.49 [s, 9H, C(CH₃)₃], 7.22 (td, 2H, J_ortho = 8.6 Hz, J_meta = 2.4 Hz, ArH), 7.47–7.58 (m, 4H, ArH), 7.67 (d, 1H, J_meta = 1.8 Hz, ArH), 8.13 (d, 1H, J_meta = 1.8 Hz, ArH), 8.26 (d, 1H, J_meta = 1.7 Hz, ArH), 8.72 (s, 1H, CH=N), 10.55 (b, 1H, NH). HR–MS (m/z): calculated for [C₂₇H₃₀BrN₂]⁺, m/z = 461.1587; found, 461.1627.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atom attached to atom N3 was located in a difference-Fourier map and freely refined. The C-bound H atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined using a riding model with U_iso(H) = 1.2U_eq(C). Orientational disorder of the tert-butyl substituent (C20–C23) around the C13—C20 bond axis is observed and the occupancies refined to 0.592 (3) and 0.408 (3).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₇H₂₉BrN₂
M_r	461.42
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	9.9949 (5), 23.546 (1), 10.2919 (6)
β (°)	108.334 (6)
V (Å³)	2299.2 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.80
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku AFC HyPix-6000
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 )
T_min, T_max	0.610, 0.696
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	19373, 5268, 4580
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.076, 1.03
No. of reflections	5268
No. of parameters	312
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.54
Computer programs: CrysAlis PRO (Rigaku OD, 2018), SIR92 (Altomare et al., 1993 ), SHELXL2014 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and CrystalStructure (Rigaku, 2016 ).

Supporting information

CCDC reference: 1951647

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989019012374/is5522sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019012374/is5522Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019012374/is5522Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: CrystalStructure (Rigaku, 2016).

4-Bromo-N-[(3,6-di-tert-butyl-9H-carbazol-1-yl)methylidene]aniline top

Crystal data top

C₂₇H₂₉BrN₂	F(000) = 960.00
M_r = 461.42	D_x = 1.333 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
a = 9.9949 (5) Å	Cell parameters from 8890 reflections
b = 23.546 (1) Å	θ = 2.3–30.3°
c = 10.2919 (6) Å	µ = 1.80 mm⁻¹
β = 108.334 (6)°	T = 123 K
V = 2299.2 (2) Å³	Prism, yellow
Z = 4	0.40 × 0.30 × 0.20 mm

Data collection top

Rigaku AFC HyPix-6000 diffractometer	5268 independent reflections
Radiation source: rotating anode X-ray generator, FR-E+	4580 reflections with F² > 2.0σ(F²)
Multi-layer mirror optics monochromator	R_int = 0.025
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.5°, θ_min = 2.3°
ω scans	h = −10→12
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	k = −26→30
T_min = 0.610, T_max = 0.696	l = −13→13
19373 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0306P)² + 1.3852P] where P = (F_o² + 2F_c²)/3
5268 reflections	(Δ/σ)_max < 0.001
312 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³
Primary atom site location: structure-invariant direct methods

Special details top

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.

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.32389 (2)	−0.22866 (2)	−0.02368 (2)	0.04191 (8)
N2	0.10884 (14)	−0.03518 (6)	0.24791 (14)	0.0214 (3)
N3	0.13607 (14)	0.05539 (6)	0.44000 (14)	0.0194 (3)
C4	−0.00730 (16)	0.05269 (6)	0.37843 (15)	0.0178 (3)
C5	−0.07237 (16)	0.09426 (6)	0.43609 (15)	0.0171 (3)
C6	−0.21856 (16)	0.10061 (7)	0.38848 (16)	0.0190 (3)
H6	−0.2609	0.1292	0.4243	0.023*
C7	−0.30146 (16)	0.06474 (7)	0.28826 (16)	0.0202 (3)
C8	−0.23344 (17)	0.02255 (7)	0.23600 (16)	0.0210 (3)
H8	−0.2887	−0.0021	0.1703	0.025*
C9	−0.08739 (16)	0.01562 (6)	0.27729 (16)	0.0187 (3)
C10	0.16594 (16)	0.09673 (6)	0.54128 (16)	0.0183 (3)
C11	0.03872 (15)	0.12215 (6)	0.54154 (15)	0.0169 (3)
C12	0.03888 (16)	0.16442 (6)	0.63623 (15)	0.0172 (3)
H12	−0.0456	0.1811	0.6359	0.021*
C13	0.16444 (16)	0.18174 (6)	0.73110 (15)	0.0183 (3)
C14	0.29004 (16)	0.15590 (7)	0.72658 (16)	0.0213 (3)
H14	0.3748	0.1675	0.7894	0.026*
C15	0.29330 (16)	0.11409 (7)	0.63310 (17)	0.0216 (3)
H15	0.3781	0.0982	0.6319	0.026*
C16	−0.46276 (17)	0.06969 (7)	0.23445 (18)	0.0249 (4)
C17	−0.5292 (2)	0.01470 (9)	0.2628 (2)	0.0423 (5)
H17A	−0.5002	0.0079	0.3597	0.051*
H17B	−0.4991	−0.0163	0.2182	0.051*
H17C	−0.6300	0.0179	0.2285	0.051*
C18	−0.5096 (2)	0.07977 (9)	0.07942 (19)	0.0351 (4)
H18A	−0.6106	0.0811	0.0447	0.042*
H18B	−0.4758	0.0494	0.0359	0.042*
H18C	−0.4716	0.1152	0.0606	0.042*
C19	−0.51743 (19)	0.11897 (9)	0.2992 (2)	0.0386 (5)
H19A	−0.4766	0.1538	0.2812	0.046*
H19B	−0.4920	0.1132	0.3963	0.046*
H19C	−0.6182	0.1210	0.2610	0.046*
C20	0.16630 (17)	0.22683 (7)	0.83868 (17)	0.0226 (3)
C21A	0.2398 (4)	0.20070 (14)	0.9822 (3)	0.0349 (8)	0.592 (3)
H21A	0.2411	0.2281	1.0517	0.042*	0.592 (3)
H21B	0.3347	0.1903	0.9893	0.042*	0.592 (3)
H21C	0.1890	0.1676	0.9943	0.042*	0.592 (3)
C22A	0.0240 (4)	0.24682 (17)	0.8322 (4)	0.0458 (11)	0.592 (3)
H22A	−0.0202	0.2644	0.7452	0.055*	0.592 (3)
H22B	0.0317	0.2739	0.9040	0.055*	0.592 (3)
H22C	−0.0318	0.2151	0.8434	0.055*	0.592 (3)
C23A	0.2585 (4)	0.27633 (13)	0.8214 (3)	0.0344 (8)	0.592 (3)
H23A	0.2170	0.2935	0.7333	0.041*	0.592 (3)
H23B	0.3509	0.2625	0.8284	0.041*	0.592 (3)
H23C	0.2655	0.3040	0.8917	0.041*	0.592 (3)
C21B	0.0816 (5)	0.2036 (2)	0.9295 (4)	0.0310 (11)	0.408 (3)
H21D	0.1277	0.1705	0.9775	0.037*	0.408 (3)
H21E	−0.0118	0.1937	0.8731	0.037*	0.408 (3)
H21F	0.0762	0.2321	0.9943	0.037*	0.408 (3)
C22B	0.0843 (5)	0.28167 (19)	0.7672 (5)	0.0324 (11)	0.408 (3)
H22D	0.0760	0.3078	0.8359	0.039*	0.408 (3)
H22E	−0.0080	0.2711	0.7094	0.039*	0.408 (3)
H22F	0.1351	0.2994	0.7130	0.039*	0.408 (3)
C23B	0.3089 (4)	0.2460 (2)	0.9280 (5)	0.0346 (12)	0.408 (3)
H23D	0.3601	0.2140	0.9772	0.041*	0.408 (3)
H23E	0.2979	0.2739	0.9917	0.041*	0.408 (3)
H23F	0.3599	0.2622	0.8721	0.041*	0.408 (3)
C24	−0.02473 (16)	−0.02866 (7)	0.21740 (16)	0.0197 (3)
H24	−0.0838	−0.0533	0.1544	0.024*
C25	0.15800 (17)	−0.07912 (7)	0.18052 (16)	0.0207 (3)
C26	0.26499 (17)	−0.11434 (7)	0.25860 (18)	0.0235 (3)
H26	0.3037	−0.1079	0.3521	0.028*
C27	0.31439 (17)	−0.15892 (7)	0.19842 (19)	0.0263 (4)
H27	0.3834	−0.1833	0.2514	0.032*
C28	0.25953 (18)	−0.16661 (7)	0.05853 (19)	0.0263 (4)
C29	0.15945 (19)	−0.13042 (8)	−0.02231 (19)	0.0288 (4)
H29	0.1269	−0.1351	−0.1168	0.035*
C30	0.10778 (18)	−0.08681 (7)	0.03954 (17)	0.0261 (4)
H30	0.0389	−0.0625	−0.0140	0.031*
H3	0.187 (2)	0.0341 (9)	0.426 (2)	0.027 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03992 (12)	0.03025 (11)	0.05975 (15)	0.00525 (8)	0.02168 (10)	−0.01567 (9)
N2	0.0257 (7)	0.0183 (6)	0.0222 (7)	−0.0004 (5)	0.0103 (6)	−0.0001 (5)
N3	0.0172 (6)	0.0193 (7)	0.0222 (7)	0.0024 (5)	0.0069 (5)	−0.0017 (5)
C4	0.0192 (7)	0.0168 (7)	0.0181 (7)	0.0000 (6)	0.0066 (6)	0.0036 (6)
C5	0.0208 (7)	0.0157 (7)	0.0154 (7)	−0.0007 (6)	0.0065 (6)	0.0015 (6)
C6	0.0196 (7)	0.0182 (7)	0.0194 (8)	0.0025 (6)	0.0065 (6)	0.0007 (6)
C7	0.0185 (8)	0.0211 (8)	0.0198 (8)	0.0005 (6)	0.0045 (6)	0.0009 (6)
C8	0.0229 (8)	0.0183 (7)	0.0202 (8)	−0.0021 (6)	0.0045 (6)	−0.0017 (6)
C9	0.0225 (8)	0.0161 (7)	0.0188 (7)	0.0000 (6)	0.0082 (6)	0.0016 (6)
C10	0.0214 (8)	0.0160 (7)	0.0186 (7)	0.0009 (6)	0.0078 (6)	0.0021 (6)
C11	0.0166 (7)	0.0165 (7)	0.0175 (7)	−0.0006 (6)	0.0053 (6)	0.0035 (6)
C12	0.0163 (7)	0.0166 (7)	0.0193 (7)	0.0007 (6)	0.0063 (6)	0.0020 (6)
C13	0.0200 (7)	0.0178 (7)	0.0178 (7)	−0.0018 (6)	0.0068 (6)	0.0018 (6)
C14	0.0164 (7)	0.0246 (8)	0.0207 (8)	−0.0023 (6)	0.0025 (6)	0.0006 (6)
C15	0.0159 (7)	0.0234 (8)	0.0258 (8)	0.0029 (6)	0.0067 (6)	0.0020 (7)
C16	0.0175 (8)	0.0246 (8)	0.0291 (9)	−0.0008 (6)	0.0023 (7)	−0.0044 (7)
C17	0.0228 (9)	0.0388 (11)	0.0652 (14)	−0.0008 (8)	0.0135 (9)	0.0078 (10)
C18	0.0256 (9)	0.0400 (11)	0.0324 (10)	0.0030 (8)	−0.0013 (8)	−0.0039 (8)
C19	0.0195 (8)	0.0479 (12)	0.0426 (11)	0.0070 (8)	0.0017 (8)	−0.0161 (9)
C20	0.0229 (8)	0.0219 (8)	0.0220 (8)	−0.0047 (6)	0.0058 (6)	−0.0037 (6)
C21A	0.049 (2)	0.0336 (17)	0.0241 (16)	−0.0039 (14)	0.0149 (14)	−0.0042 (13)
C22A	0.0303 (17)	0.047 (2)	0.054 (2)	0.0007 (15)	0.0055 (16)	−0.0364 (19)
C23A	0.0448 (19)	0.0241 (15)	0.0292 (17)	−0.0123 (13)	0.0045 (14)	−0.0049 (13)
C21B	0.039 (3)	0.035 (2)	0.021 (2)	−0.012 (2)	0.0112 (19)	−0.0070 (18)
C22B	0.045 (3)	0.026 (2)	0.026 (2)	0.0088 (19)	0.012 (2)	−0.0038 (18)
C23B	0.021 (2)	0.038 (3)	0.043 (3)	−0.0064 (18)	0.006 (2)	−0.016 (2)
C24	0.0243 (8)	0.0169 (7)	0.0179 (7)	−0.0011 (6)	0.0066 (6)	0.0000 (6)
C25	0.0229 (8)	0.0171 (7)	0.0248 (8)	−0.0020 (6)	0.0114 (7)	−0.0019 (6)
C26	0.0199 (8)	0.0268 (8)	0.0244 (8)	−0.0016 (6)	0.0080 (7)	−0.0007 (7)
C27	0.0202 (8)	0.0238 (8)	0.0368 (10)	0.0024 (6)	0.0117 (7)	0.0028 (7)
C28	0.0258 (8)	0.0194 (8)	0.0389 (10)	−0.0004 (6)	0.0175 (8)	−0.0067 (7)
C29	0.0342 (9)	0.0286 (9)	0.0244 (9)	0.0021 (7)	0.0104 (7)	−0.0050 (7)
C30	0.0306 (9)	0.0232 (8)	0.0244 (9)	0.0054 (7)	0.0084 (7)	0.0016 (7)

Geometric parameters (Å, º) top

Br1—C28	1.8992 (16)	C19—H19B	0.9600
N2—C24	1.281 (2)	C19—H19C	0.9600
N2—C25	1.417 (2)	C20—C22A	1.479 (4)
N3—C4	1.374 (2)	C20—C23B	1.502 (4)
N3—C10	1.388 (2)	C20—C23A	1.530 (3)
N3—H3	0.76 (2)	C20—C21B	1.545 (5)
C4—C9	1.401 (2)	C20—C21A	1.555 (4)
C4—C5	1.406 (2)	C20—C22B	1.581 (5)
C5—C6	1.395 (2)	C21A—H21A	0.9600
C5—C11	1.444 (2)	C21A—H21B	0.9600
C6—C7	1.388 (2)	C21A—H21C	0.9600
C6—H6	0.9300	C22A—H22A	0.9600
C7—C8	1.403 (2)	C22A—H22B	0.9600
C7—C16	1.535 (2)	C22A—H22C	0.9600
C8—C9	1.396 (2)	C23A—H23A	0.9600
C8—H8	0.9300	C23A—H23B	0.9600
C9—C24	1.450 (2)	C23A—H23C	0.9600
C10—C15	1.387 (2)	C21B—H21D	0.9600
C10—C11	1.406 (2)	C21B—H21E	0.9600
C11—C12	1.393 (2)	C21B—H21F	0.9600
C12—C13	1.387 (2)	C22B—H22D	0.9600
C12—H12	0.9300	C22B—H22E	0.9600
C13—C14	1.409 (2)	C22B—H22F	0.9600
C13—C20	1.530 (2)	C23B—H23D	0.9600
C14—C15	1.384 (2)	C23B—H23E	0.9600
C14—H14	0.9300	C23B—H23F	0.9600
C15—H15	0.9300	C24—H24	0.9300
C16—C19	1.523 (2)	C25—C30	1.390 (2)
C16—C17	1.525 (3)	C25—C26	1.392 (2)
C16—C18	1.533 (3)	C26—C27	1.386 (2)
C17—H17A	0.9600	C26—H26	0.9300
C17—H17B	0.9600	C27—C28	1.382 (3)
C17—H17C	0.9600	C27—H27	0.9300
C18—H18A	0.9600	C28—C29	1.377 (3)
C18—H18B	0.9600	C29—C30	1.390 (2)
C18—H18C	0.9600	C29—H29	0.9300
C19—H19A	0.9600	C30—H30	0.9300

C24—N2—C25	117.55 (14)	C13—C20—C23A	108.37 (17)
C4—N3—C10	108.99 (13)	C23B—C20—C21B	109.3 (3)
C4—N3—H3	123.0 (15)	C13—C20—C21B	107.9 (2)
C10—N3—H3	127.4 (15)	C22A—C20—C21A	109.2 (2)
N3—C4—C9	129.86 (14)	C13—C20—C21A	107.92 (17)
N3—C4—C5	109.09 (13)	C23A—C20—C21A	106.8 (2)
C9—C4—C5	121.03 (14)	C23B—C20—C22B	107.0 (3)
C6—C5—C4	119.92 (14)	C13—C20—C22B	110.1 (2)
C6—C5—C11	133.48 (14)	C21B—C20—C22B	105.5 (3)
C4—C5—C11	106.59 (13)	C20—C21A—H21A	109.5
C7—C6—C5	120.68 (14)	C20—C21A—H21B	109.5
C7—C6—H6	119.7	H21A—C21A—H21B	109.5
C5—C6—H6	119.7	C20—C21A—H21C	109.5
C6—C7—C8	117.89 (14)	H21A—C21A—H21C	109.5
C6—C7—C16	122.38 (14)	H21B—C21A—H21C	109.5
C8—C7—C16	119.73 (14)	C20—C22A—H22A	109.5
C9—C8—C7	123.55 (15)	C20—C22A—H22B	109.5
C9—C8—H8	118.2	H22A—C22A—H22B	109.5
C7—C8—H8	118.2	C20—C22A—H22C	109.5
C8—C9—C4	116.87 (14)	H22A—C22A—H22C	109.5
C8—C9—C24	120.32 (14)	H22B—C22A—H22C	109.5
C4—C9—C24	122.80 (14)	C20—C23A—H23A	109.5
C15—C10—N3	130.74 (14)	C20—C23A—H23B	109.5
C15—C10—C11	120.66 (14)	H23A—C23A—H23B	109.5
N3—C10—C11	108.59 (13)	C20—C23A—H23C	109.5
C12—C11—C10	120.24 (14)	H23A—C23A—H23C	109.5
C12—C11—C5	133.04 (14)	H23B—C23A—H23C	109.5
C10—C11—C5	106.69 (13)	C20—C21B—H21D	109.5
C13—C12—C11	120.29 (14)	C20—C21B—H21E	109.5
C13—C12—H12	119.9	H21D—C21B—H21E	109.5
C11—C12—H12	119.9	C20—C21B—H21F	109.5
C12—C13—C14	117.91 (14)	H21D—C21B—H21F	109.5
C12—C13—C20	121.06 (14)	H21E—C21B—H21F	109.5
C14—C13—C20	121.03 (14)	C20—C22B—H22D	109.5
C15—C14—C13	123.11 (14)	C20—C22B—H22E	109.5
C15—C14—H14	118.4	H22D—C22B—H22E	109.5
C13—C14—H14	118.4	C20—C22B—H22F	109.5
C14—C15—C10	117.77 (14)	H22D—C22B—H22F	109.5
C14—C15—H15	121.1	H22E—C22B—H22F	109.5
C10—C15—H15	121.1	C20—C23B—H23D	109.5
C19—C16—C17	109.00 (16)	C20—C23B—H23E	109.5
C19—C16—C18	107.66 (15)	H23D—C23B—H23E	109.5
C17—C16—C18	108.79 (15)	C20—C23B—H23F	109.5
C19—C16—C7	112.37 (14)	H23D—C23B—H23F	109.5
C17—C16—C7	109.72 (14)	H23E—C23B—H23F	109.5
C18—C16—C7	109.22 (14)	N2—C24—C9	122.55 (15)
C16—C17—H17A	109.5	N2—C24—H24	118.7
C16—C17—H17B	109.5	C9—C24—H24	118.7
H17A—C17—H17B	109.5	C30—C25—C26	119.00 (15)
C16—C17—H17C	109.5	C30—C25—N2	122.63 (15)
H17A—C17—H17C	109.5	C26—C25—N2	118.32 (14)
H17B—C17—H17C	109.5	C27—C26—C25	120.68 (16)
C16—C18—H18A	109.5	C27—C26—H26	119.7
C16—C18—H18B	109.5	C25—C26—H26	119.7
H18A—C18—H18B	109.5	C28—C27—C26	118.97 (16)
C16—C18—H18C	109.5	C28—C27—H27	120.5
H18A—C18—H18C	109.5	C26—C27—H27	120.5
H18B—C18—H18C	109.5	C29—C28—C27	121.56 (15)
C16—C19—H19A	109.5	C29—C28—Br1	119.37 (14)
C16—C19—H19B	109.5	C27—C28—Br1	119.07 (13)
H19A—C19—H19B	109.5	C28—C29—C30	118.97 (16)
C16—C19—H19C	109.5	C28—C29—H29	120.5
H19A—C19—H19C	109.5	C30—C29—H29	120.5
H19B—C19—H19C	109.5	C25—C30—C29	120.66 (16)
C22A—C20—C13	113.32 (17)	C25—C30—H30	119.7
C23B—C20—C13	116.4 (2)	C29—C30—H30	119.7
C22A—C20—C23A	111.0 (2)

C10—N3—C4—C9	−175.87 (15)	N3—C10—C15—C14	−178.10 (16)
C10—N3—C4—C5	2.32 (17)	C11—C10—C15—C14	1.7 (2)
N3—C4—C5—C6	178.89 (13)	C6—C7—C16—C19	2.2 (2)
C9—C4—C5—C6	−2.7 (2)	C8—C7—C16—C19	−178.06 (16)
N3—C4—C5—C11	−1.96 (16)	C6—C7—C16—C17	−119.19 (18)
C9—C4—C5—C11	176.41 (14)	C8—C7—C16—C17	60.5 (2)
C4—C5—C6—C7	2.6 (2)	C6—C7—C16—C18	121.64 (17)
C11—C5—C6—C7	−176.26 (16)	C8—C7—C16—C18	−58.7 (2)
C5—C6—C7—C8	−0.6 (2)	C12—C13—C20—C22A	2.2 (3)
C5—C6—C7—C16	179.10 (14)	C14—C13—C20—C22A	−176.9 (2)
C6—C7—C8—C9	−1.4 (2)	C12—C13—C20—C23B	−174.8 (3)
C16—C7—C8—C9	178.89 (15)	C14—C13—C20—C23B	6.2 (3)
C7—C8—C9—C4	1.3 (2)	C12—C13—C20—C23A	−121.4 (2)
C7—C8—C9—C24	−179.34 (15)	C14—C13—C20—C23A	59.5 (2)
N3—C4—C9—C8	178.81 (15)	C12—C13—C20—C21B	61.9 (3)
C5—C4—C9—C8	0.8 (2)	C14—C13—C20—C21B	−117.1 (2)
N3—C4—C9—C24	−0.6 (3)	C12—C13—C20—C21A	123.2 (2)
C5—C4—C9—C24	−178.55 (14)	C14—C13—C20—C21A	−55.9 (2)
C4—N3—C10—C15	178.11 (16)	C12—C13—C20—C22B	−52.8 (3)
C4—N3—C10—C11	−1.74 (17)	C14—C13—C20—C22B	128.1 (2)
C15—C10—C11—C12	−1.3 (2)	C25—N2—C24—C9	−178.58 (14)
N3—C10—C11—C12	178.55 (13)	C8—C9—C24—N2	177.08 (15)
C15—C10—C11—C5	−179.37 (14)	C4—C9—C24—N2	−3.6 (2)
N3—C10—C11—C5	0.50 (17)	C24—N2—C25—C30	48.4 (2)
C6—C5—C11—C12	2.2 (3)	C24—N2—C25—C26	−134.37 (16)
C4—C5—C11—C12	−176.82 (16)	C30—C25—C26—C27	−4.4 (2)
C6—C5—C11—C10	179.87 (16)	N2—C25—C26—C27	178.28 (14)
C4—C5—C11—C10	0.88 (16)	C25—C26—C27—C28	2.5 (2)
C10—C11—C12—C13	−0.1 (2)	C26—C27—C28—C29	1.3 (3)
C5—C11—C12—C13	177.38 (15)	C26—C27—C28—Br1	−178.58 (12)
C11—C12—C13—C14	0.9 (2)	C27—C28—C29—C30	−3.1 (3)
C11—C12—C13—C20	−178.14 (14)	Br1—C28—C29—C30	176.80 (13)
C12—C13—C14—C15	−0.5 (2)	C26—C25—C30—C29	2.5 (3)
C20—C13—C14—C15	178.59 (15)	N2—C25—C30—C29	179.78 (15)
C13—C14—C15—C10	−0.8 (2)	C28—C29—C30—C25	1.1 (3)

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg3 are the centroids of the C25–C30, C4–C9 and N3/C4/C5/C11/C10 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N2	0.76 (2)	2.39 (2)	2.862 (2)	121.3 (16)
C22A—H22C···Cg1ⁱ	0.96	2.92	3.878 (4)	177
C29—H29···Cg2ⁱⁱ	0.93	2.95	3.613 (2)	129
C21B—H21E···Cg1ⁱ	0.96	2.62	3.391 (5)	138
C22B—H22D···Cg3ⁱⁱⁱ	0.96	2.92	3.839 (5)	159

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

Funding information

Funding for this research was provided by: the Cooperative Research Program of Network Joint Reserarch Center for Materials and Devices (Institute for Materials Chemistry and Engineering, Kyushu University) (No. 20192018).

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Gibson, V. C., Spitzmesser, S. K., White, A. J. P. & Williams, D. J. (2003). Dalton Trans. pp. 2718. Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Krucaite, G. & Grigalevicius, S. (2019). Synth. Met. 247, 90–108. Web of Science CrossRef CAS Google Scholar
Nolla-Saltiel, R., Geer, A. M., Lewis, W., Blake, A. J. & Kays, D. L. (2018). Chem. Commun. 54, 1825–1828. CAS Google Scholar
Obora, Y. (2018). Tetrahedron Lett. 59, 167–172. Web of Science CrossRef CAS Google Scholar
Rigaku (2016). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku OD (2018). CrysAlis PRO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rubio, O. H., Fuentes de Arriba, L., Monleón, L. M., Sanz, F., Simón, L., Alcázar, V. & Morán, J. R. (2015). Tetrahedron, 71, 1297–1303. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Taneda, M., Shizu, K., Tanaka, H. & Adachi, C. (2015). Chem. Commun. 51, 5028–5031. Web of Science CrossRef CAS Google Scholar
Wiosna-Sałyga, G., Dobkowski, J., Mudadu, M. S., Sazanovich, I., Thummel, R. P. & Waluk, J. (2006). Chem. Phys. Lett. 423, 288–292. Google Scholar
Zhao, F., Chen, Z., Fan, C., Liu, G. & Pu, S. (2019). Dyes Pigments, 164, 390–397. Web of Science CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.