Crystal structure and Hirshfeld surface analysis of methyl 4-[(E)-2-(5-bromo-2-meth­oxy­benzyl­idene)hydrazin­yl]-3-nitro­benzoate

Malek, T.J.; Gandhi, S.A.; Barot, V.; Patel, M.; Patel, U.H.

doi:10.1107/S2056989018011325

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ISSN: 2056-9890

Volume 74| Part 9| September 2018| Pages 1239-1243

https://doi.org/10.1107/S2056989018011325

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Crystal structure and Hirshfeld surface analysis of methyl 4-[(E)-2-(5-bromo-2-methoxybenzylidene)hydrazinyl]-3-nitrobenzoate

Tanvirbanu J. Malek,^a Sahaj A. Gandhi,^b ^* Vijay Barot,^c Mukesh Patel ^c and Urmila H. Patel ^d

^aLDRP–Institute of Technology & Research, Kadi Sarva Vishwavidhayalay, Gandhinagar, India, ^bBhavan's Shri I. L. Pandya Arts –Science and Smt. J. M. Shah Commerce College, Dakor, Gujarat, India, ^cP.G. Center in Chemistry, Smt. S. M. Panchal Science College, Talod, India, and ^dDepartment of Physics, Sardar Patel University, Vallabh Vidyanagar, India
^*Correspondence e-mail: sahajg7@gmail.com

Edited by D. Chopra, Indian Institute of Science Education and Research Bhopal, India (Received 9 July 2018; accepted 8 August 2018; online 14 August 2018)

The title compound, C₁₆H₁₄BrN₃O₅, is a novel halogen (Br) substituted hydrazine derivative. The hydrazine derivatives were the group of compounds with the general structure, R₁R₂C=NNH₂ (Uppal et al., 2011 ), with the central RC=NNH₂ moiety bridging two different groups on both sides. An all-trans configuration of the backbone (RC=NNH₂) results in an extended molecular conformation. The dihedral angle between the 5-bromo-2-methoxyphenyl ring and the nitrophenyl ring is 4.4 (3)°. Intramolecular N—H⋯O interactions form S(6) graph-set motifs, while C—H⋯O and C—H⋯N interactions form S(5) graph-set motifs. Symmetry-related molecules are linked by C—H⋯O intermolecular interactions forming an R₂¹(10) graph-set motif. There are nearly face-to-face directional specific π–π stacking interactions between the centroids of the nitrophenyl ring and the benzene ring of the 5-bromo-2-methoxy group [centroid–centroid distance = 3.6121 (5) Å and slippage = 1.115 Å], which also contributes to the molecular packing. The Hirshfeld surface analysis was performed in order to visualize, explore and quantify the intermolecular interactions in the crystal lattice of the title compound.

Keywords: crystal structure; hydrazine derivative; graph set motif; hydrogen bond; Hirshfeld surface analysis.

CCDC reference: 1860856

1. Chemical context

Hydrazine and its derivatives have attracted much attention due to their synthetic potential for organic and inorganic chemical reactions and diverse useful properties (Levrand et al., 2007 ; Li et al., 2011 ). Hydrazine-based coupling methods are used in medical biotechnology to couple drugs to targeted antibodies, e.g. antibodies against a certain type of cancer cell (Wu et al., 2005 ). Hydrazine possesses diverse biological and pharmacological properties, such as antimicrobial, anti-inflammatory, analgesic, antifungal, antitubercular, antiviral, anticancer, antiplatelet, antimalarial, anticonvulsant, cardio-protective, antihelmintic, antiprotozoal (Rollas & Küçükgüzel, 2007 ), antitrypanosomal and antischistosomiasis (Narang et al., 2012 ). These compounds contain a C=N bond, which is conjugated with a lone pair of electrons of the functional N atom (Corey & Enders, 1976 ). The N atom of the hydrazine is nucleophilic and the C atom has both an electrophilic and a nucleophilic nature (Corey & Enders, 1976). The α-hydrogen of hydrazine is more potent than that of acidic ketones (Belskaya et al., 2010 ). The combination of hydrazine with other functional groups results in new compounds with unique physical and chemical characteristics (Xavier et al., 2012 ). Owing to their biological and pharmacological properties, hydrazine derivatives play an important role for the synthesis of heterocyclic compounds (Banerjee et al., 2009 ).

2. Structural commentary

Fig. 1 displays the title molecule with the atom-labelling scheme. Intramolecular N2—H2A⋯O4 interactions form S(6) graph-set motifs and C3—H3⋯O1 and C6—H6⋯N3 interactions form S(5) graph-set motifs. The central bridging moiety R₂C=NNHR₁ adopts an all-trans conformation about the C10—C9, C9—N3, N3—N2 and N2—C5 bonds, with torsion angles of 176.0 (6), −178.1 (5), −177.0 (6) and 173.6 (6)°, leading to an extended molecular conformation, thereby causing the terminal bromomethoxyphenyl ring and nitrophenylring to occupy almost the same plane; the dihedral angle between the rings is 4.4 (3)°.

Figure 1
The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features and Hirshfeld surface analysis

A significant number of weak C—H⋯O, C—H⋯N and N—H⋯O intramolecular interactions and C—H⋯O intermolecular interactions (Table 1), along with direction-specific nearly face-to-face π–π stacking interactions, are responsible for the stability of the molecular packing. Intermolecular C—H⋯O hydrogen-bond interactions forming R₂¹(10) ring (Fig. 2). There are nearly face-to-face direction-specific π–π stacking interactions between the centroids of the nitrophenyl ring (x, y, z) and the benzene ring of the 5-bromo-2-methoxy group (x − 1, y, z) [centroid–centroid distance = 3.6121 (5) Å and slippage = 1.115 Å], which also contributes to the molecular packing. The Br atom does not take part in any interactions. The nearest Br⋯C7(−x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ) distance in the molecular structure is 3.6112 (7) Å.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O4	0.83	2.03	2.635 (3)	129
C3—H3⋯O1	0.93	2.39	2.712 (4)	100
C6—H6⋯N3	0.93	2.40	2.731 (4)	101
C6—H6⋯O4ⁱ	0.93	2.59	3.444 (5)	152
C15—H15⋯O4ⁱ	0.93	2.46	3.358 (4)	161
Symmetry code: (i) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A view of part of the crystal structure of the title compound, showing the formation of C—H⋯O hydrogen bonds (dashed bonds).

Hirshfeld surface analysis serves as a powerful tool for gaining additional insight into intermolecular interactions of molecular crystals. The Hirshfeld surfaces are mapped with 2D fingerprint plots presented using CrystalExplorer3.1 and it provides a summary of the intermolecular contacts in the crystal (McKinnon et al., 2004 ; Spackman & Jayatilaka, 2009 ). The 2D fingerprint plots (Fig. 3) show that the intermolecular H⋯H and O⋯H interactions dominate and complement the Hirshfeld surfaces. The fingerprint plots can also be decomposed to highlight particular atom-pair close contacts (Luo et al., 2013 ) and enables separation of contributions from different interaction types. Two sharp spikes pointing towards the upper left of the plot are typical C—H⋯O hydrogen bonds. This portion corresponds to H⋯O interactions comprising 25.1% of the total Hirshfed surfaces. Two sharp spikes pointing towards the lower left of the plot are typical Br⋯H hydrogen bonds. This portion corresponds to Br⋯H interactions comprising 11.7% of the total Hirshfeld surfaces. The broad region bearing short and narrow spikes at the middle of plot is reflected as H⋯H interaction comprising 27.2% of the total Hirshfeld surfaces. Apart from these, the presence of Br⋯C, Br⋯N, Br⋯O, C⋯O, H⋯N, N⋯O and O⋯O interactions were observed (Pi chart; Fig. 4g), which are summarized in Table 2 (Li et al., 2013 ; Luo & Sun, 2014 ; Seth et al., 2011 ).

Table 2
Summary of the various contacts and their contributions to the Hirshfeld surface

Contacts	Percentage contribution
Br⋯C/C⋯Br	1.6
Br⋯H/H⋯Br	11.7
Br⋯N/N⋯Br	0.7
Br⋯O/O⋯Br	2.8
C⋯C	8.1
C⋯H/H⋯C	12.5
C⋯O/O⋯C	2.7
H⋯H	27.2
H⋯N/N⋯H	5.5
H⋯O/O⋯H	25.1
N⋯O/O⋯N	1.1
O⋯O	1.0

Figure 3
The full two-dimensional fingerprint plots, and those delineated into (a) all interactions (b) Br⋯H, (c) C⋯C, (d) C⋯H/H⋯C, (e) H⋯H and (f) H⋯O/O⋯H contacts showing the percentages of contacts contributed to the total Hirshfeld surface area. (g) Pi chart.

4. Database survey

While searching for 2-phenylhydrazine in the Cambridge Structural Database (CSD, Version 53.7; Groom et al., 2016 ), four significant structures were found [CSD refcodes AYSOD (Tahir et al., 2011 ), DUSBID (Mufakkar et al. 2010 ), DUSNUB (Shad et al. 2010 ) and DUSNUB01 (Toledano-Magaña et al., 2015 )]. Also, the crystal structure of the unsubstituted phenyl hydrazine has been reported in the CSD [ZZZGWW02 (Vickery et al., 1985 ) and ZZZGWW03 (Günes, et al., 2003 )]. The two phenyl rings in AYSOD (two molecules in the asymmetric unit), DUSBID and DUSNUB (two molecules in the asymmetric unit) are inclined to each other by 2.44 (18) and 14.08 (19)° (in molecules A and B), 9.30 (6)°, and 13.01 (10) and 14.05 (10)° (in molecules A and B), respectively, compared to 4.4 (3)° in the title compound. The crystal packing of the two compounds is significantly different. In AYSOD, N—H groups do not form hydrogen bonds, in DUSBID, the molecules are linked by N—H⋯π interactions, and in DUSNUB, both molecules form inversion dimers linked by pairs of N—H⋯O hydrogen bonds, thereby generating R₂²(16) motif rings (Bernstein et al., 1995 ). In the title compound, intramolecular N—H⋯O and only intermolecular C—H⋯O hydrogen bonds are present; there are no C—H⋯π interactions. Very few similar hydrazine derivatives are reported in the literature (Cortés et al., 2013 ; Dey & Chopra, 2017 ). In those crystal structures, a halogen group (Cl and F, respectively) is present, while in this crystal structure, Br is present.

5. Synthesis and crystallization

The title compound was synthesized in one step by heating the hydrazine derivative 3-nitrobenzohydrazide (0.181 mg) with a slight excess of 5-bromo-2-methoxybenzaldehyde (0.215 mg) in an acetic acid solution (10 ml). The reaction mixture was refluxed for 8 h. The solid product formed during reflux was filtered off, washed and dried over anhydrous calcium chloride in a vacuum desiccator (yield 75%). The final product was soluble in acetone, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), methanol, ethanol and ethyl acetate, etc. Transparent orange-coloured needle-shaped diffraction-quality single crystals of the title compound were grown by slow evaporation using methanol as the solvent at room temperature.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The coordinates of the H atoms of the N2—H2 and C9—H9 groups were refined [N2—H2 = 0.83 (6) Å and C9—H9 = 0.90 (5) Å]. Other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å, and refined as riding with U_iso(H) = xU_eq(C), where x = 1.5 for methyl and x = 1.2 for all other H atoms.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₆H₁₄BrN₃O₅
M_r	408.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.3262 (11), 14.8369 (19), 14.0764 (13)
β (°)	106.558 (14)
V (Å³)	1666.8 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.50
Crystal size (mm)	0.09 × 0.08 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (North et al., 1968 )
T_min, T_max	0.666, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4830, 3187, 1726
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.096, 0.202, 1.09
No. of reflections	3187
No. of parameters	235
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.69
Computer programs: APEX2 and SAINT (Bruker, 2008 ), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1860856

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018011325/dx2007sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018011325/dx2007Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018011325/dx2007Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Methyl 4-[(E)-2-(5-bromo-2-methoxybenzylidene)hydrazinyl]-3-nitrobenzoate top

Crystal data top

C₁₆H₁₄BrN₃O₅	F(000) = 824
M_r = 408.21	D_x = 1.627 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.3262 (11) Å	Cell parameters from 1261 reflections
b = 14.8369 (19) Å	θ = 3.3–23.2°
c = 14.0764 (13) Å	µ = 2.50 mm⁻¹
β = 106.558 (14)°	T = 293 K
V = 1666.8 (4) Å³	Plate, yellow
Z = 4	0.09 × 0.08 × 0.06 mm

Data collection top

Bruker APEXII CCD diffractometer	1726 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.065
φ and ω scans	θ_max = 29.0°, θ_min = 3.6°
Absorption correction: multi-scan (North et al., 1968)	h = −10→11
T_min = 0.666, T_max = 1.000	k = −19→10
4830 measured reflections	l = −9→18
3187 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.096	w = 1/[σ²(F_o²) + (0.0381P)² + 5.1653P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.202	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 0.66 e Å⁻³
3187 reflections	Δρ_min = −0.69 e Å⁻³
235 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0076 (10)

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.

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

	x	y	z	U_iso*/U_eq
C1	0.3935 (9)	0.2162 (5)	0.6270 (5)	0.038 (2)
H1	0.415174	0.223200	0.695123	0.046*
C2	0.2457 (9)	0.1749 (5)	0.5739 (5)	0.0348 (19)
C3	0.2169 (9)	0.1645 (5)	0.4728 (5)	0.0339 (18)
H3	0.118584	0.137270	0.435409	0.041*
C4	0.3340 (9)	0.1944 (5)	0.4272 (5)	0.0328 (18)
C5	0.4810 (9)	0.2391 (5)	0.4784 (5)	0.0308 (17)
C6	0.5083 (9)	0.2468 (6)	0.5818 (5)	0.040 (2)
H6	0.606744	0.273342	0.620051	0.049*
C7	0.1197 (10)	0.1486 (6)	0.6245 (6)	0.0386 (19)
C8	−0.1484 (10)	0.0834 (7)	0.6023 (6)	0.061 (3)
H8A	−0.236862	0.055874	0.551367	0.091*
H8B	−0.107222	0.041302	0.655468	0.091*
H8C	−0.190635	0.135968	0.626904	0.091*
C9	0.8528 (10)	0.3310 (6)	0.4527 (5)	0.040 (2)
C10	1.0108 (9)	0.3711 (6)	0.5111 (5)	0.0373 (19)
C11	1.1267 (10)	0.4052 (5)	0.4648 (6)	0.040 (2)
C12	1.2709 (10)	0.4470 (6)	0.5203 (6)	0.046 (2)
H12	1.345065	0.471252	0.488742	0.055*
C13	1.3069 (10)	0.4532 (6)	0.6226 (6)	0.052 (2)
H13	1.404718	0.480982	0.659877	0.063*
C14	1.1940 (10)	0.4174 (6)	0.6681 (5)	0.043 (2)
C15	1.0485 (9)	0.3762 (5)	0.6140 (5)	0.0357 (18)
H15	0.975310	0.351682	0.646202	0.043*
C16	1.1856 (12)	0.4401 (7)	0.3120 (6)	0.069 (3)
H16A	1.141419	0.428322	0.242387	0.104*
H16B	1.185656	0.503869	0.323555	0.104*
H16C	1.298062	0.417511	0.335016	0.104*
N1	0.2911 (8)	0.1797 (5)	0.3208 (4)	0.0370 (16)
N2	0.5978 (8)	0.2714 (5)	0.4364 (5)	0.0424 (18)
N3	0.7457 (8)	0.3049 (5)	0.4962 (4)	0.0393 (16)
O1	−0.0146 (7)	0.1088 (4)	0.5621 (4)	0.0494 (16)
O2	0.1325 (7)	0.1613 (4)	0.7107 (4)	0.0548 (17)
O3	0.1809 (8)	0.1260 (5)	0.2817 (4)	0.0612 (18)
O4	0.3693 (6)	0.2228 (4)	0.2728 (3)	0.0544 (17)
O5	1.0838 (7)	0.3963 (4)	0.3644 (4)	0.0545 (17)
BR1	1.24638 (13)	0.41918 (8)	0.80847 (6)	0.0681 (5)
H2A	0.576 (7)	0.270 (4)	0.375 (4)	0.014 (16)*
H9	0.825 (7)	0.329 (4)	0.386 (4)	0.012 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.037 (4)	0.050 (6)	0.025 (3)	0.001 (4)	0.004 (4)	0.002 (4)
C2	0.035 (4)	0.046 (5)	0.025 (3)	0.004 (4)	0.011 (3)	0.004 (3)
C3	0.033 (4)	0.040 (5)	0.028 (3)	0.005 (4)	0.007 (3)	0.004 (3)
C4	0.038 (4)	0.040 (5)	0.020 (3)	0.002 (4)	0.008 (3)	−0.003 (3)
C5	0.025 (4)	0.039 (5)	0.028 (3)	0.001 (4)	0.006 (3)	−0.003 (3)
C6	0.033 (4)	0.056 (6)	0.030 (3)	−0.003 (4)	0.006 (4)	−0.005 (4)
C7	0.038 (4)	0.041 (6)	0.039 (4)	0.008 (4)	0.016 (4)	0.004 (4)
C8	0.038 (5)	0.091 (8)	0.059 (5)	−0.003 (5)	0.022 (4)	0.007 (5)
C9	0.037 (5)	0.051 (6)	0.027 (4)	0.002 (4)	0.004 (4)	−0.001 (4)
C10	0.032 (4)	0.044 (5)	0.035 (4)	0.007 (4)	0.008 (4)	0.003 (4)
C11	0.035 (4)	0.040 (6)	0.042 (4)	0.006 (4)	0.010 (4)	0.004 (4)
C12	0.039 (5)	0.042 (6)	0.056 (5)	−0.008 (4)	0.012 (4)	−0.001 (4)
C13	0.039 (5)	0.055 (6)	0.060 (5)	0.000 (4)	0.011 (5)	0.003 (5)
C14	0.044 (5)	0.042 (6)	0.037 (4)	0.003 (4)	0.002 (4)	−0.001 (4)
C15	0.031 (4)	0.037 (5)	0.038 (4)	−0.006 (4)	0.007 (4)	−0.003 (4)
C16	0.073 (6)	0.095 (9)	0.052 (5)	−0.006 (6)	0.037 (5)	0.010 (5)
N1	0.034 (4)	0.053 (5)	0.025 (3)	0.001 (3)	0.011 (3)	0.003 (3)
N2	0.038 (4)	0.064 (5)	0.025 (3)	−0.002 (4)	0.008 (3)	−0.004 (3)
N3	0.033 (4)	0.053 (5)	0.030 (3)	−0.009 (3)	0.004 (3)	−0.003 (3)
O1	0.044 (3)	0.070 (5)	0.040 (3)	−0.005 (3)	0.021 (3)	0.000 (3)
O2	0.060 (4)	0.079 (5)	0.031 (3)	0.002 (3)	0.023 (3)	0.000 (3)
O3	0.065 (4)	0.081 (5)	0.032 (3)	−0.035 (4)	0.004 (3)	−0.012 (3)
O4	0.046 (3)	0.090 (5)	0.028 (3)	−0.012 (3)	0.013 (3)	−0.001 (3)
O5	0.054 (4)	0.075 (5)	0.038 (3)	−0.008 (3)	0.020 (3)	0.005 (3)
BR1	0.0721 (8)	0.0855 (9)	0.0375 (5)	−0.0200 (6)	0.0007 (5)	−0.0053 (5)

Geometric parameters (Å, º) top

C1—C6	1.369 (10)	C9—H9	0.90 (5)
C1—C2	1.386 (10)	C10—C15	1.394 (9)
C1—H1	0.9300	C10—C11	1.404 (10)
C2—C3	1.383 (9)	C11—O5	1.362 (9)
C2—C7	1.479 (10)	C11—C12	1.379 (11)
C3—C4	1.385 (9)	C12—C13	1.388 (11)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.399 (10)	C13—C14	1.385 (11)
C4—N1	1.454 (8)	C13—H13	0.9300
C5—N2	1.361 (9)	C14—C15	1.377 (10)
C5—C6	1.411 (9)	C14—BR1	1.899 (7)
C6—H6	0.9300	C15—H15	0.9300
C7—O2	1.201 (8)	C16—O5	1.428 (9)
C7—O1	1.346 (9)	C16—H16A	0.9600
C8—O1	1.437 (9)	C16—H16B	0.9600
C8—H8A	0.9600	C16—H16C	0.9600
C8—H8B	0.9600	N1—O3	1.221 (8)
C8—H8C	0.9600	N1—O4	1.240 (7)
C9—N3	1.277 (9)	N2—N3	1.371 (8)
C9—C10	1.464 (11)	N2—H2A	0.83 (6)

C6—C1—C2	121.8 (6)	C11—C10—C9	120.8 (7)
C6—C1—H1	119.1	O5—C11—C12	124.1 (7)
C2—C1—H1	119.1	O5—C11—C10	115.8 (7)
C3—C2—C1	118.1 (7)	C12—C11—C10	120.1 (7)
C3—C2—C7	121.8 (7)	C11—C12—C13	120.9 (8)
C1—C2—C7	120.0 (6)	C11—C12—H12	119.5
C2—C3—C4	120.2 (7)	C13—C12—H12	119.5
C2—C3—H3	119.9	C14—C13—C12	118.6 (8)
C4—C3—H3	119.9	C14—C13—H13	120.7
C3—C4—C5	122.8 (6)	C12—C13—H13	120.7
C3—C4—N1	115.5 (7)	C15—C14—C13	121.5 (7)
C5—C4—N1	121.7 (6)	C15—C14—BR1	119.1 (6)
N2—C5—C4	124.8 (6)	C13—C14—BR1	119.4 (6)
N2—C5—C6	119.6 (7)	C14—C15—C10	120.0 (7)
C4—C5—C6	115.5 (6)	C14—C15—H15	120.0
C1—C6—C5	121.6 (7)	C10—C15—H15	120.0
C1—C6—H6	119.2	O5—C16—H16A	109.5
C5—C6—H6	119.2	O5—C16—H16B	109.5
O2—C7—O1	123.1 (7)	H16A—C16—H16B	109.5
O2—C7—C2	125.0 (8)	O5—C16—H16C	109.5
O1—C7—C2	111.9 (6)	H16A—C16—H16C	109.5
O1—C8—H8A	109.5	H16B—C16—H16C	109.5
O1—C8—H8B	109.5	O3—N1—O4	122.3 (6)
H8A—C8—H8B	109.5	O3—N1—C4	119.6 (6)
O1—C8—H8C	109.5	O4—N1—C4	118.0 (6)
H8A—C8—H8C	109.5	C5—N2—N3	119.2 (6)
H8B—C8—H8C	109.5	C5—N2—H2A	118 (4)
N3—C9—C10	119.5 (7)	N3—N2—H2A	122 (4)
N3—C9—H9	119 (4)	C9—N3—N2	116.3 (6)
C10—C9—H9	121 (4)	C7—O1—C8	116.8 (6)
C15—C10—C11	118.9 (7)	C11—O5—C16	118.2 (7)
C15—C10—C9	120.3 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4	0.83	2.03	2.635 (3)	129
C3—H3···O1	0.93	2.39	2.712 (4)	100
C6—H6···N3	0.93	2.40	2.731 (4)	101
C6—H6···O4ⁱ	0.93	2.59	3.444 (5)	152
C15—H15···O4ⁱ	0.93	2.46	3.358 (4)	161

Symmetry code: (i) x−1/2, −y−1/2, z−1/2.

Summary of various contacts and their contributions to the Hirshfeld surface top

Contacts	Percentage contribution
Br···C/ C···Br	1.6
Br···H/ H···Br	11.7
Br···N/ N···Br	0.7
Br···O/ O···Br	2.8
C···C	8.1
C···H/ H···C	12.5
C···O/ O···C	2.7
H···H	27.2
H···N/ N···H	5.5
H···O/ O···H	25.1
N···O/ O···N	1.1
O···O	1.0

Acknowledgements

Authors are thankful to the DST–FIST, New Delhi, for providing the Kappa APEXII single-crystal X-ray diffractometer facility at Department of Physics, Sardar Patel University, Vallabh vidyanagar, Gujarat, India. One of the authors (TJM) is thankful to LDRP–Institute of Technology & Research, Gandhinagar, for giving necessary permission.

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