Crystal structure of a 1:1 cocrystal of nicotinamide with 2-chloro-5-nitro­benzoic acid

Bairagi, K.M.; Pal, P.; Bhandary, S.; Venugopala, K.N.; Chopra, D.; Nayak, S.K.

doi:10.1107/S2056989019013859

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ISSN: 2056-9890

Volume 75| Part 11| November 2019| Pages 1712-1718

https://doi.org/10.1107/S2056989019013859

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Crystal structure of a 1:1 cocrystal of nicotinamide with 2-chloro-5-nitrobenzoic acid

Keshab M. Bairagi,^a Priyanka Pal,^a Subhrajyoti Bhandary,^b Katharigatta N. Venugopala,^c,^d ^* Deepak Chopra ^b and Susanta K. Nayak ^a ^*

^aDepartment of Chemistry, Visvesvaraya National Institute of Technology, Nagpur 440 010, Maharashtra, India, ^bDepartment of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhauri, Bhopal 462 066, Madhya Pradesh, India, ^cDepartment of Pharmaceutical Sciences, College of Clinical Pharmacy, King Faisal University, Al-Ahsa 31982, Kingdom of Saudi Arabia, and ^dDepartment of Biotechnology and Food Technology, Durban University of Technology, Durban 4001, South Africa
^*Correspondence e-mail: kvenugopala@kfu.edu.sa, sknayak@chm.vnit.ac.in

Edited by E. V. Boldyreva, Russian Academy of Sciences, Russia (Received 20 August 2019; accepted 10 October 2019; online 22 October 2019)

In the title 1:1 cocrystal, C₇H₄ClNO₄·C₆H₆N₂O, nicotinamide (NIC) and 2-chloro-5-nitrobenzoic acid (CNBA) cocrystallize with one molecule each of NIC and CNBA in the asymmetric unit. In this structure, CNBA and NIC form hydrogen bonds through O—H⋯N, N—H⋯O and C—H⋯O interactions along with N—H⋯O dimer hydrogen bonds of NIC. Further additional weak π–π interactions stabilize the molecular assembly of this cocrystal.

Keywords: crystal structure; cocrystal; Hirshfeld surface; 2-chloro-5-nitrobenzoic acid; nicotinamide.

CCDC references: 1958621; 1958621

1. Chemical context

Nicotinamide (NIC) derivatives are used in various applications, for example, in the prevention of type 1 diabetes (Elliott et al., 1993 ) and nicotinamide cofactors are also used in preparative enzymatic synthesis (Chenault & Whitesides, 1987 ). The nicotinamide formulation has also been used for treatment in palliative radiotherapy (Horsman et al., 1993 ). The pharmacological result for the active pharmaceutical ingredient (API) will increase if it becomes cocrystallized with a coformer or other active component (Schultheiss & Newman, 2009 ; Lemmerer et al., 2010 ). Chlorobenzoic acid derivatives are widely used in the pharmaceutical industry. 2-Chloro-4-nitrobenzoic acid is used for immunodeficiency diseases as an antiviral and anticancer agent (Lemmerer et al., 2010). In the title compound, NIC is cocrystallized with the CNBA coformer as it acts as an excellent candidate for cocrystallization because of the hydrogen-bond acceptor and donor parts (Dragovic et al., 1995 ).

2. Structural commentary

The title compound CNBA–NIC (1:1) crystallizes in the monoclinic space group P2₁/c with four molecules of NIC and CNBA in the unit cell. The dihedral angle between the amide plane with the mean plane of the phenyl part in NIC is 23.87 (1)°, and the dihedral angles of the carboxyl and nitro groups with the chlorophenyl ring in CNBA are 24.92 (1) and 3.56 (1)°, respectively. In the asymmetric unit, an (CNBA)O–H⋯N interaction plays a prime role in the molecular recognition of this cocrystal (Fig. 1).

Figure 1
The asymmetric unit of the title compound, showing 50% probability ellipsoids, the atom labelling and hydrogen bonding with dotted lines.

3. Supramolecular features

In the crystal structure of the title cocrystal, a strong (CNBA)O—H⋯N(NIC) hydrogen bond and additional (NIC)N—H⋯O(CNBA) and (NIC)C—H⋯O(CNBA) hydrogen bonds are observed (Fig. 2 and Table 1). In this cocrystal, the NIC molecule forms a dimer with itself having an R₂²(8) graph-set motif (Etter et al., 1990 ). These dimers are further connected via C—H⋯O hydrogen bonding and form a tetrameric ring with two molecules each of NIC and CNBA with R₂²(10) graph-set motifs (Etter et al., 1990) (Fig. 2). Furthermore, weak π–π interactions are observed for both NIC [3.68 (7) Å] and CNBA [3.73 (7) Å] which stabilize the molecular assembly along the bc plane (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.90 (2)	2.005 (19)	2.9004 (15)	171.4 (14)
N1—H1B⋯O3	0.873 (19)	2.116 (19)	2.9715 (14)	166.6 (16)
O2—H2⋯N2	1.07 (2)	1.49 (2)	2.5543 (13)	172 (2)
C3—H3⋯O4	0.986 (15)	2.516 (15)	3.4505 (16)	158.2 (12)
C4—H4⋯O5	0.979 (14)	2.442 (15)	3.3256 (17)	149.9 (12)
C5—H5⋯O5	0.956 (15)	2.450 (16)	3.0878 (17)	124.0 (11)
C6—H6⋯O3	0.959 (15)	2.608 (15)	3.452 (1)	147.0 (11)
C10—H10⋯O4	0.955 (15)	2.599 (16)	3.5010 (18)	157.6 (15)

Figure 2
Hydrogen bonds in the title compound showing the dimer formation through N—H⋯O interactions and tetramer formation through C—H⋯O interactions.

Figure 3
Weak π–π interactions stabilize the molecular assembly of both molecules in the crystal.

4. Hirshfeld surface analysis

To understand the role of intermolecular interactions, we have utilized the Hirshfeld surface analysis visualizing tool (Spackman & Jayatilaka, 2009 ). The Hirshfeld surfaces and two-dimensional fingerprint plots developed using CrystalExplorer (Version 3.1; Wolff et al., 2012 ) are shown in Fig. 4. The red spot on the surface represents a strong interaction through O—H⋯N and N—H⋯O hydrogen bonding, whereas the blue color represents a lack of interaction. The d_norm map of the title compound NIC·CNBA and its pure components is shown in Fig. 4, where individual molecular interactions were estimated. The fingerprint plot shows that O⋯H/H⋯O and H⋯H contribute the major part of the interaction in all compounds (Fig. 4). The O⋯H/H⋯O contact contributes 40% to the cocrystal NIC molecule (Fig. 5) and 20.5% to the pure NIC molecule (NICOAM01; Miwa et al., 1999 ) (Fig. 6), and H⋯H contributes 22% to the cocrystal NIC molecule and 41% to the pure NIC molecule. Similarly, O⋯H/H⋯O contacts contribute 33% to the cocrystal CNBA molecule (Fig. 7) and 36.6% to the pure CNBA molecule (CLNBZA; Ferguson & Sim, 1962 ) (Fig. 8), and H⋯H contributes 15.2% to the cocrystal CNBA molecule and 17.7% to the pure NIC molecule.

Figure 4
Hirshfeld surfaces developed on (i) d_norm mapped over the pure NIC molecule, (ii) d_norm mapped over the NIC molecule in title compound, (iii) d_norm mapped over the pure CNBA molecule and (iv) d_norm mapped over the CNBA molecule in title compound.

Figure 5
Two-dimensional fingerprint plots and relative contributions of various interactions to the Hirshfeld surface of the NIC cocrystal molecule.

Figure 6
Two-dimensional fingerprint plots and relative contributions of various interactions to the Hirshfeld surface of the pure NIC molecule.

Figure 7
Two-dimensional fingerprint plots and relative contributions of various interactions to the Hirshfeld surface of the CNBA cocrystal molecule.

Figure 8
Two-dimensional fingerprint plots and relative contributions of various interactions to the Hirshfeld surface of the pure CNBA molecule

5. Database survey

A search for the title cocrystal in the Cambridge Structural Database (CSD, Version 5.40, update of February 2019; Groom et al., 2016 ) found no hits. However, searches for NIC and CNBA gave 237 and 9 hits, respectively. A search for the NIC molecule showed that the N atom on the phenyl ring forms strong O—H⋯N hydrogen bonds with a carboxyl H atom in the most of the cocrystals [ABULIU (Lou & Hu, 2011 ), BICQAH (Aitipamula et al., 2013 ), BICQEL (Aitipamula et al., 2013), BOBQUG (Zhang et al., 2013 ), CUYXUQ (Lemmerer & Bernstein, 2010 ), DINRUP (Lemmerer et al., 2013 ), DINSEA (Lemmerer et al., 2013), EDAPOQ (Orola & Veidis, 2009 ) etc]. For the CNBA search, two structures were found similar to the title compound where strong hydrogen bonding is formed by the carboxyl H atom with a pyridine N atom [AJIWIA (Gotoh & Ishida, 2009 ) and OCAZAT (Ishida et al., 2001 )]. AJIWIA also shows halogen bonds through C—O⋯Cl bonding and forms a dimer through C—H⋯O hydrogen bonding.

6. Synthesis and crystallization

All the chemicals used for the synthesis were purchased from Alfa Aesar and used without further purification. A stock solution was prepared from an equimolar mixture of 2-chloro-5 nitrobenzoic acid (82.44 mg, 0.409 mmol) and nicotinamide (50 mg, 0.409 mmol) in a minimum amount of ethanol and made up to a volume of 10 ml. Ten different combinations of the mixture were prepared using ethanol–hexane as the solvent mixture over the ratio range 1:1 to 1:10. The mixture was kept in a 5 ml beaker and covered with parafilm, with four to five small holes in it. These solutions were allowed to evaporate slowly at room temperature (27 °C) over several days to obtain single crystals. After a few days, colourless crystals were obtained from ethanol–hexane solutions with concentration ratios of 1:10, 1:2 and 1:4. The melting point of the obtained crystal was 159.7 °C.

7. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 2. All H atoms were found in a difference Fourier maps and were refind freely.

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₄ClNO₄·C₆H₆N₂O
M_r	323.69
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	7.4897 (1), 26.3607 (5), 7.0623 (1)
β (°)	96.356 (1)
V (Å³)	1385.77 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.31
Crystal size (mm)	0.28 × 0.22 × 0.15

Data collection
Diffractometer	Bruker Kappa APEXII DUO
Absorption correction	Multi-scan (SADABS; Bruker, 2001 )
T_min, T_max	0.874, 0.908
No. of measured, independent and observed [I > 2σ(I)] reflections	29950, 4123, 3316
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.708

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.094, 1.08
No. of reflections	4123
No. of parameters	239
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.26
Computer programs: APEX2 (Bruker, 2012 ), SAINT (Bruker, 2012), SHELXS18 (Sheldrick, 2015 ), SHELXL2018 (Sheldrick, 2015), Mercury (Macrae et al., 2008 ), OLEX2 (Dolomanov et al., 2009 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC references: 1958621; 1958621

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989019013859/eb2025sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019013859/eb2025Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS18 (Sheldrick, 2015); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and PLATON (Spek, 2009).

2-Chloro-5-nitrobenzoic acid–nicotinamide (1/1) top

Crystal data top

C₇H₄ClNO₄·C₆H₆N₂O	D_x = 1.551 Mg m⁻³
M_r = 323.69	Melting point: 159.7 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.4897 (1) Å	Cell parameters from 4123 reflections
b = 26.3607 (5) Å	θ = 1.5–30.2°
c = 7.0623 (1) Å	µ = 0.31 mm⁻¹
β = 96.356 (1)°	T = 123 K
V = 1385.77 (4) Å³	Block, colorless
Z = 4	0.28 × 0.22 × 0.15 mm
F(000) = 664

Data collection top

Bruker Kappa APEXII DUO diffractometer	4123 independent reflections
Radiation source: fine-focus sealed tube	3316 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scans	θ_max = 30.2°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
T_min = 0.874, T_max = 0.908	k = −37→37
29950 measured reflections	l = −9→9

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	All H-atom parameters refined
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0394P)² + 0.4303P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
4123 reflections	Δρ_max = 0.30 e Å⁻³
239 parameters	Δρ_min = −0.26 e Å⁻³

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. Single-crystal X-ray diffraction data were collected on a Bruker KAPPA APEX II DUO diffractometer using graphite-monochromated Mo-Kα radiation (λ = 0.71073Å)(Bruker, 2012). The data collection was performed at 153 (2) K. The temperature was monitored by an Oxford Cryostream cooling system (Oxford Cryostat). the program SAINT (Bruker, 2012) were used for cell refinement and data reduction. The data were scaled and absorption correction performed using SADABS(Bruker, 2001). The structure was solved by direct methods using SHELXS-18(Sheldrick, 2015) and refined by full-matrix least-squares methods based on F2 using SHELXL-2018/3(Sheldrick, 2015). The computing , Mercury(Macrae et al., 2008) and PLATON (Spek, 2009) were used for molecular graphics and molecular interactions. All non-hydrogen atoms were refined anisotropically.

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

	x	y	z	U_iso*/U_eq
Cl1	−0.18141 (5)	0.18331 (2)	0.33099 (6)	0.04137 (12)
O2	0.39368 (12)	0.16413 (3)	0.29015 (14)	0.0267 (2)
O1	0.87918 (13)	0.45197 (3)	1.35865 (13)	0.0268 (2)
O5	0.29333 (16)	0.39338 (4)	0.38136 (16)	0.0381 (3)
O3	0.16833 (14)	0.13103 (3)	0.43221 (14)	0.0308 (2)
O4	0.50015 (15)	0.34087 (4)	0.32242 (18)	0.0417 (3)
N1	0.87836 (15)	0.53606 (4)	1.29452 (16)	0.0226 (2)
N2	0.57395 (14)	0.41744 (4)	0.85619 (15)	0.0208 (2)
N3	0.34615 (16)	0.35059 (4)	0.35149 (16)	0.0262 (2)
C6	0.75383 (15)	0.50921 (4)	0.89924 (17)	0.0189 (2)
C1	0.83945 (15)	0.48801 (4)	1.24921 (17)	0.0193 (2)
C2	0.74506 (15)	0.47734 (4)	1.05512 (16)	0.0172 (2)
C12	0.21719 (17)	0.30889 (4)	0.35036 (17)	0.0209 (2)
C4	0.59051 (17)	0.44720 (5)	0.70484 (18)	0.0221 (2)
C13	0.28144 (16)	0.25993 (4)	0.35032 (17)	0.0193 (2)
C5	0.67736 (17)	0.49327 (5)	0.72106 (18)	0.0217 (2)
C9	−0.02066 (17)	0.23039 (5)	0.34499 (19)	0.0243 (3)
C3	0.65244 (16)	0.43172 (4)	1.02733 (17)	0.0201 (2)
C8	0.16239 (16)	0.21927 (4)	0.35036 (16)	0.0191 (2)
C10	−0.08225 (18)	0.28024 (5)	0.3432 (2)	0.0291 (3)
C7	0.24078 (17)	0.16659 (4)	0.36051 (17)	0.0205 (2)
C11	0.03681 (19)	0.32024 (5)	0.34746 (19)	0.0261 (3)
H3	0.639 (2)	0.4084 (6)	1.134 (2)	0.022 (4)*
H6	0.813 (2)	0.5415 (6)	0.909 (2)	0.022 (4)*
H13	0.404 (2)	0.2537 (6)	0.352 (2)	0.028 (4)*
H4	0.540 (2)	0.4339 (6)	0.581 (2)	0.025 (4)*
H5	0.691 (2)	0.5138 (6)	0.612 (2)	0.026 (4)*
H1A	0.947 (2)	0.5426 (6)	1.405 (3)	0.035 (4)*
H1B	0.850 (2)	0.5613 (7)	1.216 (3)	0.038 (5)*
H11	−0.006 (2)	0.3550 (7)	0.346 (3)	0.040 (5)*
H10	−0.208 (3)	0.2870 (7)	0.338 (3)	0.042 (5)*
H2	0.462 (3)	0.1292 (9)	0.326 (3)	0.074 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02685 (18)	0.0403 (2)	0.0562 (3)	−0.01523 (14)	0.00135 (15)	0.00272 (16)
O2	0.0251 (5)	0.0190 (4)	0.0362 (5)	0.0037 (3)	0.0040 (4)	0.0050 (4)
O1	0.0362 (5)	0.0207 (4)	0.0216 (5)	−0.0011 (4)	−0.0050 (4)	0.0024 (3)
O5	0.0529 (7)	0.0147 (4)	0.0430 (6)	−0.0008 (4)	−0.0109 (5)	−0.0029 (4)
O3	0.0424 (6)	0.0172 (4)	0.0346 (5)	−0.0037 (4)	0.0115 (4)	0.0017 (4)
O4	0.0345 (6)	0.0268 (5)	0.0654 (8)	−0.0094 (4)	0.0126 (5)	0.0039 (5)
N1	0.0265 (5)	0.0186 (5)	0.0213 (5)	0.0006 (4)	−0.0040 (4)	−0.0017 (4)
N2	0.0211 (5)	0.0163 (5)	0.0243 (5)	−0.0016 (4)	−0.0008 (4)	−0.0014 (4)
N3	0.0357 (6)	0.0165 (5)	0.0253 (6)	−0.0031 (4)	−0.0022 (4)	0.0021 (4)
C6	0.0196 (5)	0.0151 (5)	0.0220 (6)	−0.0004 (4)	0.0022 (4)	−0.0009 (4)
C1	0.0187 (5)	0.0192 (6)	0.0200 (6)	0.0007 (4)	0.0023 (4)	−0.0015 (4)
C2	0.0167 (5)	0.0164 (5)	0.0184 (5)	0.0018 (4)	0.0015 (4)	−0.0014 (4)
C12	0.0275 (6)	0.0164 (5)	0.0184 (6)	−0.0018 (4)	0.0006 (4)	0.0000 (4)
C4	0.0247 (6)	0.0197 (6)	0.0207 (6)	0.0010 (5)	−0.0022 (5)	−0.0025 (4)
C13	0.0209 (5)	0.0183 (5)	0.0186 (6)	−0.0003 (4)	0.0011 (4)	0.0004 (4)
C5	0.0268 (6)	0.0184 (6)	0.0194 (6)	0.0004 (4)	0.0006 (5)	0.0017 (4)
C9	0.0216 (6)	0.0256 (6)	0.0257 (6)	−0.0044 (5)	0.0025 (5)	0.0000 (5)
C3	0.0216 (5)	0.0173 (5)	0.0212 (6)	−0.0002 (4)	0.0015 (4)	0.0001 (4)
C8	0.0216 (5)	0.0177 (5)	0.0177 (6)	−0.0017 (4)	0.0012 (4)	−0.0002 (4)
C10	0.0217 (6)	0.0320 (7)	0.0335 (7)	0.0045 (5)	0.0027 (5)	0.0004 (5)
C7	0.0266 (6)	0.0167 (5)	0.0174 (6)	−0.0019 (4)	−0.0011 (4)	−0.0008 (4)
C11	0.0305 (7)	0.0218 (6)	0.0255 (7)	0.0061 (5)	0.0010 (5)	−0.0004 (5)

Geometric parameters (Å, º) top

Cl1—C9	1.7244 (13)	C1—C2	1.4977 (16)
O2—C7	1.2994 (15)	C2—C3	1.3913 (16)
O2—H2	1.07 (2)	C12—C13	1.3774 (16)
O1—C1	1.2399 (14)	C12—C11	1.3816 (18)
O5—N3	1.2215 (15)	C4—C5	1.3766 (17)
O3—C7	1.2208 (14)	C4—H4	0.977 (16)
O4—N3	1.2209 (16)	C13—C8	1.3941 (16)
N1—C1	1.3307 (16)	C13—H13	0.932 (16)
N1—H1A	0.901 (19)	C5—H5	0.957 (16)
N1—H1B	0.876 (18)	C9—C10	1.3921 (19)
N2—C3	1.3383 (16)	C9—C8	1.3984 (17)
N2—C4	1.3426 (16)	C3—H3	0.984 (15)
N3—C12	1.4626 (16)	C8—C7	1.5064 (16)
C6—C5	1.3887 (17)	C10—C11	1.379 (2)
C6—C2	1.3922 (16)	C10—H10	0.955 (18)
C6—H6	0.959 (15)	C11—H11	0.971 (18)

C7—O2—H2	111.9 (13)	C12—C13—H13	120.6 (9)
C1—N1—H1A	118.6 (11)	C8—C13—H13	119.6 (9)
C1—N1—H1B	122.7 (12)	C4—C5—C6	119.08 (11)
H1A—N1—H1B	118.4 (16)	C4—C5—H5	121.5 (9)
C3—N2—C4	118.98 (10)	C6—C5—H5	119.4 (9)
O4—N3—O5	123.56 (12)	C10—C9—C8	121.40 (11)
O4—N3—C12	118.49 (11)	C10—C9—Cl1	116.76 (10)
O5—N3—C12	117.95 (12)	C8—C9—Cl1	121.80 (10)
C5—C6—C2	118.89 (11)	N2—C3—C2	122.20 (11)
C5—C6—H6	118.5 (9)	N2—C3—H3	116.1 (9)
C2—C6—H6	122.6 (9)	C2—C3—H3	121.7 (9)
O1—C1—N1	123.25 (11)	C13—C8—C9	117.65 (11)
O1—C1—C2	118.88 (10)	C13—C8—C7	117.57 (10)
N1—C1—C2	117.87 (11)	C9—C8—C7	124.77 (11)
C3—C2—C6	118.46 (11)	C11—C10—C9	120.57 (12)
C3—C2—C1	117.96 (10)	C11—C10—H10	119.3 (11)
C6—C2—C1	123.47 (10)	C9—C10—H10	120.1 (11)
C13—C12—C11	122.95 (11)	O3—C7—O2	124.84 (11)
C13—C12—N3	118.27 (11)	O3—C7—C8	122.60 (11)
C11—C12—N3	118.78 (11)	O2—C7—C8	112.54 (10)
N2—C4—C5	122.26 (11)	C10—C11—C12	117.62 (12)
N2—C4—H4	116.2 (9)	C10—C11—H11	120.6 (11)
C5—C4—H4	121.6 (9)	C12—C11—H11	121.8 (11)
C12—C13—C8	119.79 (11)

C5—C6—C2—C3	−2.96 (17)	C1—C2—C3—N2	−175.60 (10)
C5—C6—C2—C1	173.20 (11)	C12—C13—C8—C9	1.77 (17)
O1—C1—C2—C3	21.57 (16)	C12—C13—C8—C7	−176.93 (11)
N1—C1—C2—C3	−159.19 (11)	C10—C9—C8—C13	−1.15 (19)
O1—C1—C2—C6	−154.61 (12)	Cl1—C9—C8—C13	176.29 (9)
N1—C1—C2—C6	24.63 (17)	C10—C9—C8—C7	177.44 (12)
O4—N3—C12—C13	11.29 (17)	Cl1—C9—C8—C7	−5.12 (18)
O5—N3—C12—C13	−168.81 (12)	C8—C9—C10—C11	−0.3 (2)
O4—N3—C12—C11	−168.07 (12)	Cl1—C9—C10—C11	−177.83 (11)
O5—N3—C12—C11	11.83 (17)	C13—C8—C7—O3	151.23 (12)
C3—N2—C4—C5	−3.55 (18)	C9—C8—C7—O3	−27.36 (19)
C11—C12—C13—C8	−1.03 (19)	C13—C8—C7—O2	−26.97 (15)
N3—C12—C13—C8	179.64 (11)	C9—C8—C7—O2	154.44 (12)
N2—C4—C5—C6	1.33 (19)	C9—C10—C11—C12	1.0 (2)
C2—C6—C5—C4	1.97 (17)	C13—C12—C11—C10	−0.4 (2)
C4—N2—C3—C2	2.47 (17)	N3—C12—C11—C10	178.92 (12)
C6—C2—C3—N2	0.78 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.90 (2)	2.005 (19)	2.9004 (15)	171.4 (14)
N1—H1B···O3	0.873 (19)	2.116 (19)	2.9715 (14)	166.6 (16)
O2—H2···N2	1.07 (2)	1.49 (2)	2.5543 (13)	172 (2)
C3—H3···O4	0.986 (15)	2.516 (15)	3.4505 (16)	158.2 (12)
C4—H4···O5	0.979 (14)	2.442 (15)	3.3256 (17)	149.9 (12)
C5—H5···O5	0.956 (15)	2.450 (16)	3.0878 (17)	124.0 (11)
C6—H6···O3	0.959 (15)	2.608 (15)	3.452 (1)	147.0 (11)
C10—H10···O4	0.955 (15)	2.599 (16)	3.5010 (18)	157.6 (15)

Acknowledgements

The authors are thankful to IISER, Bhopal, for the single-crystal X-ray data collection.

Funding information

Funding for this research was provided by: National Research Foundation and Durban University of Technology, South Africa (grant Nos. 96807 and 98884), and SERB, DST India (grant No. ECR/2016/001820) for research support and instrument facilities.

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