4-Bromo-N,N′-di­phenyl­benzimidamide N′-oxide

Saha, A.; Chartrand, D.; Cibian, M.; Maris, T.; Hanan, G.S.

doi:10.1107/S2414314624009684

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 10| October 2024| x240968

https://doi.org/10.1107/S2414314624009684

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4-Bromo-N,N′-diphenylbenzimidamide N′-oxide

Arindam Saha,^a Daniel Chartrand,^a Mihaela Cibian,^b Thierry Maris ^a ^* and Garry S. Hanan ^a

^aDépartement de Chimie, Université de Montréal, Complexe des sciences, 1375, Avenue Thérèse-Lavoie-Roux, Montréal, Québec H2V 0B3, Canada, and ^bDépartement de biochimie, chimie, physique et science forensique, Université du Québec à Trois-Rivières. 3351, boul. des Forges, CP 500, Trois-Rivières, Québec, G9A 5H7, Canada
^*Correspondence e-mail: thierry.maris@umontreal.ca

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 27 September 2024; accepted 1 October 2024; online 8 October 2024)

The title compound, C₁₉H₁₅BrN₂O, crystallizes with two similar molecules in the asymmetric unit. The extended structure features dimers linked by pairs of N—H⋯O and C—H⋯O hydrogen bonds. The HNCNO moiety of the title compound shows delocalization over the N—C—N part, as evidenced by the similar C—N bond distances.

Keywords: amidine N-oxides; ligand synthesis; crystal structure.

CCDC reference: 2388273

Structure description

The title compound C₁₉H₁₅BrN₂O (AMOX-Br) is a symmetrically N,N′-disubstituted arylamidine N′-oxide. Its crystal structure was determined as part of a research project involving the synthesis of AMOX ligands and their coordination complexes with transition-metal ions for assessing their photophysical and electrochemical properties (Patel et al., 1979 ; Verma et al., 1995 ; Cibian et al., 2018 ). The asymmetric unit contains two molecules (labelled with suffixes A and B) in the orthorhombic Pna2₁ space group. Each molecule contains an O—N—C—N bridge bearing a central C-aryl ring with 4-bromo substitution and two side N-phenyl rings (Fig. 1).

Figure 1
View of the asymmetric unit containing two independent molecules with displacement ellipsoids drawn at the 50% probability level.

The N—C—N moieties in both molecules display electronic delocalization since the bond lengths are shorter than classical C—N single bonds (1.45 Å) and longer than localized C=N double bonds (1.27 Å) (Filgueiras de Athayde-Filho et al., 2003 ). This observation is evident from the similar N—C bond distances [C1A—N1A = 1.321 (11) Å, C1A—N2A = 1.338 (12) Å and C1B—N1B = 1.325 (11) Å, C1B—N2B = 1.366 (11) Å] for the two molecules of the asymmetric unit. Furthermore, these values are comparable to those reported for the N—C—N bond lengths in 4-bromo-N-phenylbenzamidoxime (Cibian et al., 2009 ). The N—C—N—O moiety is slightly twisted with a torsion angle of 3.9 (11)° for N2B—C1B—N1B—O1B and −3.9 (12)° for O1A—N1A—C1A—N2A. Considering the central and side phenyl rings, if rings C3A–C8A, C9A–C14A and C15A–C20A from molecule A are labelled 1, 2 and 3, respectively (4, 5 and 6, respectively, for the rings of molecule B, Fig. 2), the angle between planes 1 and 3 is 68.9 (3)° while the angle between planes 1 and 2 is 57.1 (3)°, with the corresponding angles for molecule B being 69.6 (3) and 56.9 (3)°, respectively. The angles between the planes of the side N-phenyl rings (2/3 & 5/6 for molecules A and B, respectively) are 73.6 (3) and 72.6 (3)°, respectively.

Figure 2
View of planes 1, 2, 3, 4, 5, and 6 for the phenyl rings of the molecules in the asymmetric unit and hydrogen bonds (dotted lines).

Hydrogen bonds are reported in Table 1. The extended structure displays cyclic dimers linked by pairs of N—H⋯O and C—H⋯O hydrogen bonds. No notable intermolecular π–π stacking interactions are observed but there are several C—H⋯π contacts that complement the conventional hydrogen bonds (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2, Cg3, Cg5 and Cg6 are the centroids of the C9A–C14A, C15A–C20A, C9B–C14B and C15B–C20B rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2A⋯O1B	0.88	2.20	3.005 (11)	152
C10A—H10A⋯O1Bⁱ	0.95	2.32	3.249 (12)	167
C16A—H16A⋯O1B	0.95	2.41	3.191 (12)	139
N2B—H2B⋯O1A	0.88	2.19	2.999 (10)	152
C10B—H10B⋯O1Aⁱⁱ	0.95	2.28	3.214 (12)	167
C16B—H16B⋯O1A	0.95	2.40	3.188 (12)	140
C4A—H4A⋯Cg2ⁱⁱ	0.95	2.77	3.614 (10)	149
C4B—H4B⋯Cg6ⁱⁱ	0.95	2.64	3.534 (10)	157
C8A—H8A⋯Cg3ⁱ	0.95	2.71	3.591 (10)	154
C8B—H8B⋯Cg5ⁱ	0.95	2.85	3.688 (10)	148
Symmetry codes: (i) ; (ii) .

Figure 3
View of the packing of the title compound in the unit cell.

Synthesis and crystallization

The compound was synthesized with some modification to the procedure reported in the literature (Cibian et al., 2018): 4-bromo-N,N′-diphenylbenzimidamide, AM–Br (0.84 g, 2.4 mmol, 1.0 eq.) was dissolved in dichloromethane in the presence of NaHCO₃ (1.19 g, 14.2 mmol, 5.0 eq.) and stirred for 10 minutes. Then, m-chloro-peroxibenzoic acid, m-CPBA, 70% (0.76 g, 3.1 mmol, 1.1 eq.) was added in small aliquotes to the AM–Br solution. The reaction mixture turned brown instantly and darkened within a minute of stirring. The reaction mixture was stirred at room temperature for 2 h and filtered under vacuum. The filtrate was washed with 2 M NaOH solution (2 × 80 ml), distilled water (2 × 80 ml) and brine (3 × 50 ml). The collected dichloromethane layer was dried with anhydrous Na₂SO₄ and the solvent was removed under vacuum. The sticky brown solid obtained was sonicated in a minimum volume of ethyl acetate/hexanes. The precipitate thus formed was filtered and washed with ethyl acetate/hexanes to give a pale-yellow amorphous powder (yield 76%) of the title compound. Bright-yellow needles suitable for X-ray diffraction measurements were grown over a period of 5 d at room temperature by the hexane anti-solvent layering technique with a dichloromethane solution of the compound (1:1 v/v).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The crystal studied was refined as a two-component inversion twin.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₅BrN₂O
M_r	367.24
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	150
a, b, c (Å)	17.7036 (16), 5.8468 (6), 31.418 (3)
V (Å³)	3252.0 (5)
Z	8
Radiation type	Ga Kα, λ = 1.34139 Å
μ (mm⁻¹)	2.30
Crystal size (mm)	0.19 × 0.03 × 0.03

Data collection
Diffractometer	Bruker Venture Metaljet
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.079, 0.201
No. of measured, independent and observed [I > 2σ(I)] reflections	100504, 6071, 4793
R_int	0.090
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.158, 1.07
No. of reflections	6071
No. of parameters	416
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.13, −0.64
Absolute structure	Refined as an inversion twin.
Absolute structure parameter	0.23 (6)
Computer programs: APEX4 (Bruker, 2022 ), SAINT (Bruker, 2020 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ), FinalCIF (Kratzert, 2024 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2388273

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314624009684/hb4487sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624009684/hb4487Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314624009684/hb4487Isup3.cml

checkCIF report

Computing details top

4-Bromo-N,N'-diphenylbenzimidamide N'-oxide top

Crystal data top

C₁₉H₁₅BrN₂O	D_x = 1.500 Mg m⁻³
M_r = 367.24	Ga Kα radiation, λ = 1.34139 Å
Orthorhombic, Pna2₁	Cell parameters from 9781 reflections
a = 17.7036 (16) Å	θ = 4.5–54.4°
b = 5.8468 (6) Å	µ = 2.30 mm⁻¹
c = 31.418 (3) Å	T = 150 K
V = 3252.0 (5) Å³	Needle, clear light colourless
Z = 8	0.19 × 0.03 × 0.03 mm
F(000) = 1488

Data collection top

Bruker Venture Metaljet diffractometer	6071 independent reflections
Radiation source: Metal Jet, Gallium Liquid Metal Jet Source	4793 reflections with I > 2σ(I)
Helios MX Mirror Optics monochromator	R_int = 0.090
Detector resolution: 10.42 pixels mm^-1	θ_max = 54.9°, θ_min = 2.5°
ω and φ scans	h = −21→21
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −6→7
T_min = 0.079, T_max = 0.201	l = −38→37
100504 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.055	w = 1/[σ²(F_o²) + (0.0728P)² + 6.1028P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.158	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 1.13 e Å⁻³
6071 reflections	Δρ_min = −0.64 e Å⁻³
416 parameters	Absolute structure: Refined as an inversion twin.
1 restraint	Absolute structure parameter: 0.23 (6)
Primary atom site location: dual

Special details top

Experimental. X-ray crystallographic data for I were collected from a single crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Venture diffractometer equipped with a Photon III CMOS Detector, a Helios MX optics and a Kappa goniometer. The crystal-to-detector distance was 4.0 cm, and the data collection was carried out in 1024 x 1024 pixel mode.

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. Refined as a 2-component inversion twin.

Hydrogen atoms attached to nitrogen were first located from Fourier difference map then refined using the equivalent calculated positions. The C-bound H atoms were geometrically placed and refined as riding atoms.

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

	x	y	z	U_iso*/U_eq
Br1A	0.61038 (7)	0.6881 (3)	0.25148 (3)	0.0760 (4)
O1A	0.4180 (4)	0.7299 (11)	0.4878 (2)	0.0500 (18)
N1A	0.4538 (4)	0.7506 (11)	0.4507 (3)	0.0344 (17)
C1A	0.4319 (4)	0.6209 (13)	0.4185 (3)	0.0351 (18)
N2A	0.3778 (4)	0.4681 (13)	0.4271 (2)	0.0417 (17)
H2A	0.363970	0.461329	0.453973	0.050*
C3A	0.4695 (4)	0.6315 (15)	0.3761 (3)	0.0369 (18)
C4A	0.5143 (5)	0.4453 (15)	0.3630 (3)	0.0402 (19)
H4A	0.516330	0.310580	0.379883	0.048*
C5A	0.5558 (5)	0.4585 (18)	0.3253 (3)	0.047 (2)
H5A	0.586546	0.334943	0.315994	0.057*
C6A	0.5504 (6)	0.6599 (19)	0.3018 (3)	0.051 (2)
C7A	0.5056 (6)	0.8449 (17)	0.3136 (3)	0.047 (2)
H7A	0.503148	0.978161	0.296394	0.057*
C8A	0.4644 (5)	0.8303 (17)	0.3516 (3)	0.043 (2)
H8A	0.433335	0.953821	0.360476	0.051*
C9A	0.5134 (5)	0.9239 (15)	0.4500 (3)	0.0396 (19)
C10A	0.4990 (5)	1.1212 (15)	0.4729 (3)	0.0380 (19)
H10A	0.451900	1.142036	0.486832	0.046*
C11A	0.5530 (5)	1.2838 (15)	0.4752 (3)	0.040 (2)
H11A	0.543730	1.417141	0.491620	0.048*
C12A	0.6217 (5)	1.2623 (15)	0.4542 (4)	0.042 (2)
H12A	0.658205	1.381271	0.455257	0.051*
C13A	0.6354 (5)	1.0632 (17)	0.4319 (3)	0.048 (2)
H13A	0.682490	1.045000	0.417789	0.057*
C14A	0.5821 (5)	0.8882 (14)	0.4296 (3)	0.0409 (19)
H14A	0.592282	0.750290	0.414638	0.049*
C15A	0.3389 (5)	0.3147 (16)	0.3995 (3)	0.041 (2)
C16A	0.3139 (5)	0.1128 (15)	0.4159 (3)	0.044 (2)
H16A	0.323975	0.076505	0.444787	0.053*
C17A	0.2739 (5)	−0.0410 (16)	0.3908 (3)	0.047 (2)
H17A	0.256372	−0.180680	0.402644	0.056*
C18A	0.2594 (5)	0.0097 (19)	0.3481 (3)	0.052 (3)
H18A	0.233473	−0.096676	0.330491	0.062*
C19A	0.2838 (6)	0.2216 (18)	0.3316 (4)	0.051 (3)
H19A	0.272754	0.260575	0.302911	0.061*
C20A	0.3238 (5)	0.3733 (16)	0.3568 (3)	0.045 (2)
H20A	0.340832	0.514948	0.345548	0.055*
C1B	0.3236 (4)	0.3768 (15)	0.5820 (3)	0.0370 (18)
Br1B	0.14367 (7)	0.2681 (2)	0.74742 (3)	0.0701 (4)
N1B	0.3017 (4)	0.2490 (11)	0.5494 (3)	0.0336 (17)
O1B	0.3366 (4)	0.2703 (11)	0.5123 (2)	0.0478 (17)
N2B	0.3789 (4)	0.5326 (12)	0.5731 (2)	0.0417 (17)
H2B	0.393219	0.539951	0.546301	0.050*
C3B	0.2863 (5)	0.3580 (16)	0.6241 (3)	0.0387 (19)
C4B	0.2924 (5)	0.1630 (16)	0.6482 (3)	0.0391 (19)
H4B	0.325401	0.044035	0.639406	0.047*
C5B	0.2506 (5)	0.1381 (18)	0.6856 (3)	0.048 (2)
H5B	0.254569	0.001873	0.701917	0.058*
C6B	0.2046 (6)	0.3074 (19)	0.6984 (3)	0.048 (2)
C7B	0.1990 (5)	0.5162 (18)	0.6760 (3)	0.050 (2)
H7B	0.167883	0.637004	0.686058	0.060*
C8B	0.2411 (5)	0.5390 (16)	0.6382 (3)	0.041 (2)
H8B	0.238858	0.677153	0.622357	0.049*
C9B	0.2439 (5)	0.0776 (15)	0.5503 (3)	0.0393 (19)
C10B	0.2578 (5)	−0.1214 (15)	0.5272 (3)	0.040 (2)
H10B	0.304907	−0.142167	0.513284	0.049*
C11B	0.2031 (6)	−0.2875 (16)	0.5248 (3)	0.042 (2)
H11B	0.212594	−0.422652	0.508851	0.051*
C12B	0.1340 (5)	−0.2606 (14)	0.5453 (4)	0.041 (2)
H12B	0.096363	−0.376087	0.543340	0.049*
C13B	0.1207 (5)	−0.0633 (17)	0.5685 (3)	0.042 (2)
H13B	0.074096	−0.045649	0.583136	0.051*
C14B	0.1746 (5)	0.1094 (15)	0.5707 (3)	0.0401 (19)
H14B	0.164413	0.246787	0.585759	0.048*
C15B	0.4160 (5)	0.6836 (15)	0.6013 (3)	0.040 (2)
C16B	0.4421 (4)	0.8874 (15)	0.5840 (3)	0.041 (2)
H16B	0.433158	0.921877	0.554880	0.050*
C17B	0.4814 (5)	1.0404 (17)	0.6097 (3)	0.049 (2)
H17B	0.498950	1.180375	0.597936	0.059*
C18B	0.4953 (5)	0.9913 (18)	0.6523 (4)	0.054 (3)
H18B	0.521577	1.097190	0.669808	0.065*
C19B	0.4695 (6)	0.7814 (18)	0.6691 (5)	0.053 (3)
H19B	0.479286	0.744164	0.698056	0.063*
C20B	0.4308 (5)	0.6319 (17)	0.6440 (3)	0.046 (2)
H20B	0.413583	0.491091	0.655569	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1A	0.0716 (8)	0.1182 (10)	0.0382 (7)	−0.0140 (7)	0.0150 (7)	0.0000 (9)
O1A	0.060 (4)	0.053 (4)	0.038 (4)	−0.010 (3)	0.018 (3)	−0.007 (3)
N1A	0.040 (4)	0.032 (4)	0.031 (5)	−0.006 (3)	0.006 (4)	−0.006 (3)
C1A	0.039 (4)	0.026 (4)	0.040 (5)	−0.002 (3)	0.003 (3)	0.002 (3)
N2A	0.045 (4)	0.044 (4)	0.036 (4)	−0.005 (3)	0.004 (3)	−0.004 (3)
C3A	0.037 (4)	0.036 (4)	0.037 (5)	−0.002 (4)	0.002 (4)	0.000 (4)
C4A	0.042 (5)	0.040 (5)	0.038 (4)	0.000 (4)	−0.001 (4)	−0.004 (4)
C5A	0.048 (5)	0.055 (6)	0.039 (5)	−0.005 (4)	0.003 (4)	−0.004 (4)
C6A	0.046 (5)	0.069 (7)	0.037 (5)	−0.012 (5)	−0.003 (4)	−0.003 (5)
C7A	0.057 (6)	0.040 (5)	0.046 (6)	−0.007 (5)	−0.015 (5)	0.001 (4)
C8A	0.038 (4)	0.047 (5)	0.043 (6)	0.001 (4)	−0.001 (4)	0.001 (4)
C9A	0.038 (4)	0.041 (5)	0.039 (4)	−0.002 (4)	−0.007 (4)	0.005 (4)
C10A	0.039 (4)	0.045 (5)	0.031 (4)	0.004 (4)	−0.002 (3)	0.001 (4)
C11A	0.049 (5)	0.043 (5)	0.028 (5)	0.002 (4)	−0.007 (4)	0.002 (4)
C12A	0.047 (5)	0.036 (5)	0.045 (6)	−0.005 (4)	−0.008 (4)	0.001 (4)
C13A	0.042 (5)	0.051 (6)	0.050 (6)	−0.002 (4)	−0.003 (4)	0.002 (5)
C14A	0.043 (5)	0.032 (4)	0.048 (5)	0.001 (4)	−0.003 (4)	−0.002 (4)
C15A	0.034 (4)	0.050 (5)	0.039 (5)	−0.001 (4)	0.005 (4)	−0.005 (4)
C16A	0.046 (5)	0.039 (5)	0.048 (5)	−0.004 (4)	−0.001 (4)	−0.005 (4)
C17A	0.050 (5)	0.032 (5)	0.059 (6)	−0.003 (4)	0.003 (4)	−0.002 (4)
C18A	0.049 (5)	0.049 (6)	0.057 (6)	−0.008 (5)	−0.010 (4)	−0.012 (5)
C19A	0.052 (6)	0.063 (7)	0.037 (7)	−0.005 (5)	−0.008 (4)	−0.007 (5)
C20A	0.043 (5)	0.045 (5)	0.049 (5)	−0.002 (4)	−0.003 (4)	−0.001 (4)
C1B	0.036 (4)	0.041 (5)	0.034 (4)	0.002 (4)	0.003 (3)	0.000 (4)
Br1B	0.0672 (7)	0.1061 (9)	0.0369 (6)	−0.0024 (6)	0.0184 (6)	0.0002 (7)
N1B	0.041 (4)	0.032 (4)	0.028 (5)	−0.001 (3)	0.004 (3)	−0.004 (3)
O1B	0.053 (4)	0.051 (4)	0.040 (4)	−0.004 (3)	0.010 (3)	−0.002 (3)
N2B	0.046 (4)	0.038 (4)	0.041 (4)	−0.007 (3)	0.006 (3)	−0.001 (3)
C3B	0.033 (4)	0.045 (5)	0.037 (5)	0.001 (4)	−0.001 (3)	0.001 (4)
C4B	0.038 (4)	0.041 (5)	0.038 (5)	−0.003 (4)	0.001 (4)	0.001 (4)
C5B	0.046 (5)	0.061 (6)	0.036 (5)	−0.013 (5)	−0.010 (4)	0.008 (4)
C6B	0.057 (6)	0.063 (6)	0.024 (5)	−0.002 (5)	−0.001 (4)	−0.007 (4)
C7B	0.041 (5)	0.066 (6)	0.043 (5)	0.006 (4)	0.005 (4)	−0.021 (5)
C8B	0.043 (5)	0.039 (5)	0.040 (5)	0.002 (4)	0.004 (4)	−0.002 (4)
C9B	0.043 (5)	0.039 (5)	0.035 (4)	0.000 (4)	0.004 (4)	0.000 (4)
C10B	0.046 (5)	0.040 (5)	0.036 (4)	0.003 (4)	−0.004 (4)	−0.005 (4)
C11B	0.053 (6)	0.037 (5)	0.037 (6)	−0.004 (4)	−0.005 (4)	−0.004 (4)
C12B	0.043 (5)	0.040 (5)	0.040 (6)	−0.005 (4)	−0.005 (4)	−0.002 (4)
C13B	0.036 (4)	0.044 (6)	0.047 (5)	0.003 (4)	−0.003 (4)	−0.003 (4)
C14B	0.037 (4)	0.042 (5)	0.041 (4)	0.001 (4)	0.004 (4)	−0.003 (4)
C15B	0.037 (5)	0.041 (5)	0.042 (5)	−0.005 (4)	−0.003 (4)	0.000 (4)
C16B	0.036 (4)	0.044 (5)	0.044 (5)	0.003 (4)	0.006 (4)	−0.007 (4)
C17B	0.048 (5)	0.044 (5)	0.054 (6)	−0.002 (4)	0.009 (4)	0.001 (5)
C18B	0.042 (5)	0.051 (6)	0.070 (7)	−0.008 (4)	−0.004 (5)	−0.011 (5)
C19B	0.052 (6)	0.057 (7)	0.048 (7)	−0.004 (5)	−0.007 (5)	−0.005 (5)
C20B	0.039 (5)	0.052 (6)	0.046 (5)	−0.001 (4)	0.002 (4)	0.004 (4)

Geometric parameters (Å, º) top

Br1A—C6A	1.911 (10)	C1B—N1B	1.325 (11)
O1A—N1A	1.333 (11)	C1B—N2B	1.366 (11)
N1A—C1A	1.321 (11)	C1B—C3B	1.485 (12)
N1A—C9A	1.463 (11)	Br1B—C6B	1.894 (10)
C1A—N2A	1.338 (11)	N1B—O1B	1.326 (10)
C1A—C3A	1.491 (12)	N1B—C9B	1.433 (11)
N2A—H2A	0.8800	N2B—H2B	0.8800
N2A—C15A	1.423 (12)	N2B—C15B	1.415 (12)
C3A—C4A	1.408 (12)	C3B—C4B	1.373 (14)
C3A—C8A	1.398 (14)	C3B—C8B	1.398 (13)
C4A—H4A	0.9500	C4B—H4B	0.9500
C4A—C5A	1.397 (13)	C4B—C5B	1.396 (13)
C5A—H5A	0.9500	C5B—H5B	0.9500
C5A—C6A	1.393 (15)	C5B—C6B	1.343 (15)
C6A—C7A	1.392 (15)	C6B—C7B	1.413 (15)
C7A—H7A	0.9500	C7B—H7B	0.9500
C7A—C8A	1.400 (14)	C7B—C8B	1.407 (13)
C8A—H8A	0.9500	C8B—H8B	0.9500
C9A—C10A	1.383 (12)	C9B—C10B	1.393 (12)
C9A—C14A	1.391 (12)	C9B—C14B	1.396 (12)
C10A—H10A	0.9500	C10B—H10B	0.9500
C10A—C11A	1.350 (13)	C10B—C11B	1.374 (13)
C11A—H11A	0.9500	C11B—H11B	0.9500
C11A—C12A	1.387 (14)	C11B—C12B	1.392 (14)
C12A—H12A	0.9500	C12B—H12B	0.9500
C12A—C13A	1.381 (14)	C12B—C13B	1.385 (14)
C13A—H13A	0.9500	C13B—H13B	0.9500
C13A—C14A	1.394 (13)	C13B—C14B	1.391 (13)
C14A—H14A	0.9500	C14B—H14B	0.9500
C15A—C16A	1.361 (13)	C15B—C16B	1.389 (13)
C15A—C20A	1.410 (13)	C15B—C20B	1.398 (13)
C16A—H16A	0.9500	C16B—H16B	0.9500
C16A—C17A	1.391 (13)	C16B—C17B	1.391 (13)
C17A—H17A	0.9500	C17B—H17B	0.9500
C17A—C18A	1.397 (15)	C17B—C18B	1.393 (15)
C18A—H18A	0.9500	C18B—H18B	0.9500
C18A—C19A	1.412 (16)	C18B—C19B	1.411 (15)
C19A—H19A	0.9500	C19B—H19B	0.9500
C19A—C20A	1.384 (14)	C19B—C20B	1.364 (15)
C20A—H20A	0.9500	C20B—H20B	0.9500

O1A—N1A—C9A	114.7 (7)	N1B—C1B—N2B	115.3 (7)
C1A—N1A—O1A	118.6 (7)	N1B—C1B—C3B	121.2 (8)
C1A—N1A—C9A	126.7 (8)	N2B—C1B—C3B	123.4 (7)
N1A—C1A—N2A	116.1 (7)	C1B—N1B—O1B	119.3 (7)
N1A—C1A—C3A	121.9 (7)	C1B—N1B—C9B	126.0 (8)
N2A—C1A—C3A	121.8 (7)	O1B—N1B—C9B	114.6 (7)
C1A—N2A—H2A	114.9	C1B—N2B—H2B	115.8
C1A—N2A—C15A	130.1 (8)	C1B—N2B—C15B	128.4 (7)
C15A—N2A—H2A	114.9	C15B—N2B—H2B	115.8
C4A—C3A—C1A	118.7 (8)	C4B—C3B—C1B	121.2 (8)
C8A—C3A—C1A	119.9 (8)	C4B—C3B—C8B	119.9 (9)
C8A—C3A—C4A	121.2 (9)	C8B—C3B—C1B	118.8 (8)
C3A—C4A—H4A	120.0	C3B—C4B—H4B	119.7
C5A—C4A—C3A	120.1 (9)	C3B—C4B—C5B	120.6 (9)
C5A—C4A—H4A	120.0	C5B—C4B—H4B	119.7
C4A—C5A—H5A	121.3	C4B—C5B—H5B	120.1
C6A—C5A—C4A	117.4 (9)	C6B—C5B—C4B	119.8 (9)
C6A—C5A—H5A	121.3	C6B—C5B—H5B	120.1
C5A—C6A—Br1A	118.2 (8)	C5B—C6B—Br1B	119.9 (8)
C5A—C6A—C7A	123.7 (10)	C5B—C6B—C7B	122.0 (9)
C7A—C6A—Br1A	118.1 (8)	C7B—C6B—Br1B	118.0 (7)
C6A—C7A—H7A	120.7	C6B—C7B—H7B	121.2
C6A—C7A—C8A	118.5 (9)	C8B—C7B—C6B	117.7 (9)
C8A—C7A—H7A	120.7	C8B—C7B—H7B	121.2
C3A—C8A—C7A	119.1 (9)	C3B—C8B—C7B	119.9 (9)
C3A—C8A—H8A	120.4	C3B—C8B—H8B	120.1
C7A—C8A—H8A	120.4	C7B—C8B—H8B	120.1
C10A—C9A—N1A	116.0 (7)	C10B—C9B—N1B	116.6 (7)
C10A—C9A—C14A	121.7 (8)	C10B—C9B—C14B	120.3 (8)
C14A—C9A—N1A	122.2 (8)	C14B—C9B—N1B	122.9 (8)
C9A—C10A—H10A	120.5	C9B—C10B—H10B	120.1
C11A—C10A—C9A	119.0 (8)	C11B—C10B—C9B	119.7 (8)
C11A—C10A—H10A	120.5	C11B—C10B—H10B	120.1
C10A—C11A—H11A	118.9	C10B—C11B—H11B	119.5
C10A—C11A—C12A	122.1 (9)	C10B—C11B—C12B	120.9 (9)
C12A—C11A—H11A	118.9	C12B—C11B—H11B	119.5
C11A—C12A—H12A	120.9	C11B—C12B—H12B	120.4
C13A—C12A—C11A	118.1 (9)	C13B—C12B—C11B	119.1 (8)
C13A—C12A—H12A	120.9	C13B—C12B—H12B	120.4
C12A—C13A—H13A	119.1	C12B—C13B—H13B	119.5
C12A—C13A—C14A	121.8 (9)	C12B—C13B—C14B	120.9 (9)
C14A—C13A—H13A	119.1	C14B—C13B—H13B	119.5
C9A—C14A—C13A	117.2 (8)	C9B—C14B—H14B	120.5
C9A—C14A—H14A	121.4	C13B—C14B—C9B	118.9 (8)
C13A—C14A—H14A	121.4	C13B—C14B—H14B	120.5
C16A—C15A—N2A	118.3 (9)	C16B—C15B—N2B	116.3 (8)
C16A—C15A—C20A	120.5 (9)	C16B—C15B—C20B	120.0 (9)
C20A—C15A—N2A	121.2 (8)	C20B—C15B—N2B	123.6 (8)
C15A—C16A—H16A	119.6	C15B—C16B—H16B	120.3
C15A—C16A—C17A	120.9 (9)	C15B—C16B—C17B	119.4 (9)
C17A—C16A—H16A	119.6	C17B—C16B—H16B	120.3
C16A—C17A—H17A	120.0	C16B—C17B—H17B	119.5
C16A—C17A—C18A	120.1 (9)	C16B—C17B—C18B	120.9 (9)
C18A—C17A—H17A	120.0	C18B—C17B—H17B	119.5
C17A—C18A—H18A	120.6	C17B—C18B—H18B	120.6
C17A—C18A—C19A	118.8 (9)	C17B—C18B—C19B	118.9 (10)
C19A—C18A—H18A	120.6	C19B—C18B—H18B	120.6
C18A—C19A—H19A	119.7	C18B—C19B—H19B	119.9
C20A—C19A—C18A	120.6 (11)	C20B—C19B—C18B	120.2 (12)
C20A—C19A—H19A	119.7	C20B—C19B—H19B	119.9
C15A—C20A—H20A	120.4	C15B—C20B—H20B	119.7
C19A—C20A—C15A	119.1 (10)	C19B—C20B—C15B	120.7 (10)
C19A—C20A—H20A	120.4	C19B—C20B—H20B	119.7

Br1A—C6A—C7A—C8A	−176.9 (7)	C1B—N1B—C9B—C10B	−140.5 (9)
O1A—N1A—C1A—N2A	−3.9 (12)	C1B—N1B—C9B—C14B	43.6 (13)
O1A—N1A—C1A—C3A	−179.3 (8)	C1B—N2B—C15B—C16B	−151.1 (8)
O1A—N1A—C9A—C10A	−37.2 (11)	C1B—N2B—C15B—C20B	32.5 (14)
O1A—N1A—C9A—C14A	139.3 (8)	C1B—C3B—C4B—C5B	−173.1 (8)
N1A—C1A—N2A—C15A	175.7 (8)	C1B—C3B—C8B—C7B	173.5 (8)
N1A—C1A—C3A—C4A	109.5 (9)	Br1B—C6B—C7B—C8B	−176.4 (7)
N1A—C1A—C3A—C8A	−65.9 (11)	N1B—C1B—N2B—C15B	−176.6 (8)
N1A—C9A—C10A—C11A	177.1 (8)	N1B—C1B—C3B—C4B	66.9 (11)
N1A—C9A—C14A—C13A	−178.4 (8)	N1B—C1B—C3B—C8B	−109.9 (10)
C1A—N1A—C9A—C10A	141.1 (9)	N1B—C9B—C10B—C11B	−176.4 (8)
C1A—N1A—C9A—C14A	−42.3 (13)	N1B—C9B—C14B—C13B	177.5 (8)
C1A—N2A—C15A—C16A	149.9 (9)	O1B—N1B—C9B—C10B	37.1 (11)
C1A—N2A—C15A—C20A	−32.7 (14)	O1B—N1B—C9B—C14B	−138.8 (8)
C1A—C3A—C4A—C5A	−174.1 (8)	N2B—C1B—N1B—O1B	3.9 (11)
C1A—C3A—C8A—C7A	174.2 (8)	N2B—C1B—N1B—C9B	−178.6 (8)
N2A—C1A—C3A—C4A	−65.7 (11)	N2B—C1B—C3B—C4B	−117.0 (10)
N2A—C1A—C3A—C8A	119.0 (9)	N2B—C1B—C3B—C8B	66.2 (11)
N2A—C15A—C16A—C17A	178.3 (8)	N2B—C15B—C16B—C17B	−177.9 (8)
N2A—C15A—C20A—C19A	−178.0 (9)	N2B—C15B—C20B—C19B	177.4 (9)
C3A—C1A—N2A—C15A	−8.9 (14)	C3B—C1B—N1B—O1B	−179.8 (7)
C3A—C4A—C5A—C6A	−0.3 (13)	C3B—C1B—N1B—C9B	−2.3 (13)
C4A—C3A—C8A—C7A	−1.0 (13)	C3B—C1B—N2B—C15B	7.1 (14)
C4A—C5A—C6A—Br1A	177.0 (7)	C3B—C4B—C5B—C6B	−0.8 (14)
C4A—C5A—C6A—C7A	−0.8 (14)	C4B—C3B—C8B—C7B	−3.3 (13)
C5A—C6A—C7A—C8A	0.9 (14)	C4B—C5B—C6B—Br1B	176.7 (7)
C6A—C7A—C8A—C3A	0.0 (13)	C4B—C5B—C6B—C7B	−2.4 (14)
C8A—C3A—C4A—C5A	1.2 (13)	C5B—C6B—C7B—C8B	2.7 (14)
C9A—N1A—C1A—N2A	177.8 (8)	C6B—C7B—C8B—C3B	0.2 (13)
C9A—N1A—C1A—C3A	2.4 (13)	C8B—C3B—C4B—C5B	3.7 (13)
C9A—C10A—C11A—C12A	1.9 (14)	C9B—C10B—C11B—C12B	−0.4 (15)
C10A—C9A—C14A—C13A	−2.0 (13)	C10B—C9B—C14B—C13B	1.7 (13)
C10A—C11A—C12A—C13A	−2.6 (15)	C10B—C11B—C12B—C13B	−0.2 (16)
C11A—C12A—C13A—C14A	0.9 (15)	C11B—C12B—C13B—C14B	1.6 (15)
C12A—C13A—C14A—C9A	1.3 (14)	C12B—C13B—C14B—C9B	−2.4 (14)
C14A—C9A—C10A—C11A	0.5 (13)	C14B—C9B—C10B—C11B	−0.3 (13)
C15A—C16A—C17A—C18A	0.6 (14)	C15B—C16B—C17B—C18B	0.4 (13)
C16A—C15A—C20A—C19A	−0.6 (14)	C16B—C15B—C20B—C19B	1.1 (14)
C16A—C17A—C18A—C19A	−2.1 (14)	C16B—C17B—C18B—C19B	0.8 (14)
C17A—C18A—C19A—C20A	2.2 (15)	C17B—C18B—C19B—C20B	−1.0 (15)
C18A—C19A—C20A—C15A	−0.9 (15)	C18B—C19B—C20B—C15B	0.1 (15)
C20A—C15A—C16A—C17A	0.8 (14)	C20B—C15B—C16B—C17B	−1.3 (13)

Hydrogen-bond geometry (Å, º) top

Cg2, Cg3, Cg5 and Cg6 are the centroids of the C9A–C14A, C15A–C20A, C9B–C14B and C15B–C20B rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2A···O1B	0.88	2.20	3.005 (11)	152
C10A—H10A···O1Bⁱ	0.95	2.32	3.249 (12)	167
C16A—H16A···O1B	0.95	2.41	3.191 (12)	139
N2B—H2B···O1A	0.88	2.19	2.999 (10)	152
C10B—H10B···O1Aⁱⁱ	0.95	2.28	3.214 (12)	167
C16B—H16B···O1A	0.95	2.40	3.188 (12)	140
C4A—H4A···Cg2ⁱⁱ	0.95	2.77	3.614 (10)	149
C4B—H4B···Cg6ⁱⁱ	0.95	2.64	3.534 (10)	157
C8A—H8A···Cg3ⁱ	0.95	2.71	3.591 (10)	154
C8B—H8B···Cg5ⁱ	0.95	2.85	3.688 (10)	148

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

Acknowledgements

We gratefully acknowledge all the personnel from the XRD facilities of Université de Montréal. Professor Frank Schaper is acknowledged for the crystallographic course and training of AS.

Funding information

Funding for this research was provided by: Natural Sciences and Engineering Research Council of Canada (NSERC); Centre in Green Chemistry and Catalysis (CGCC); Quebec Centre for Advanced Materials (CQMF); Université de Montréal ESP excellence scholarship (scholarship to A. Saha).

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