Crystal structure and Hirshfeld surface analysis of [2-(1H-benzimidazol-2-yl-κN3)aniline-κN]di­chlorido­zinc(II) N,N-di­methyl­formamide monosolvate

Muslim, M.; Faizi, M.S.H.; Ali, A.; Afzal, M.; Ahmad, M.; Dege, N.; Mashrai, A.

doi:10.1107/S2056989021003649

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ISSN: 2056-9890

Volume 77| Part 5| May 2021| Pages 491-494

https://doi.org/10.1107/S2056989021003649

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Crystal structure and Hirshfeld surface analysis of [2-(1H-benzimidazol-2-yl-κN³)aniline-κN]dichloridozinc(II) N,N-dimethylformamide monosolvate

Mohd Muslim,^a Md. Serajul Haque Faizi,^b Arif Ali,^a Mohd Afzal,^c Musheer Ahmad,^a ^* Necmi Dege ^d and Ashraf Mashrai ^e ^*

^aDepartment of Applied Chemistry, ZHCET, Faculty of Engineering and Technology, Aligarh Muslim University, Aligarh, 202002, (UP), India, ^bPG Department of Chemistry, Langat Singh College, B.R.A. Bihar University, Muzaffarpur, Bihar 842001, India, ^cDepartment of Chemistry, College of Science, King Saud University, Riyadh-11451, Kingdom of, Saudi Arabia, ^dOndokuz Mayis University, Arts and Sciences Faculty, Department of Physics, Atakum 55139 Samsun, Turkey, and ^eDepartment of Pharmacy, University of Science and Technology, Ibb Branch, Yemen
^*Correspondence e-mail: amusheer4@gmail.com, ashraf.yemen7@gmail.com

Edited by J. Ellena, Universidade de Sâo Paulo, Brazil (Received 11 February 2021; accepted 5 April 2021; online 9 April 2021)

The title compound, [ZnCl₂(C₁₃H₁₁N₃)]·C₃H₇NO, crystallized in the monoclinic crystal system in space group P2₁/n. The asymmetric unit contains one neutral complex molecule, which consists of a zinc ion, a bidentate ligand, and two chlorido ligands with dimethylformamide monosolvate. The ligand has two moieties, a benzimidazole and an aniline group. The benzimidazole and aniline planes are not coplanar, subtending a dihedral angle of 18.24 (8)°. The Zn(II) ion shows distorted tetrahedral geometry, being coordinated by an imidazole N atom, the aniline N atom, and two chlorido ligands. The packing features N—H⋯O, N—H⋯Cl, C—H⋯Cl hydrogen bonding.

Keywords: crystal structure; benzimidazole; aniline; bidentate ligand; heterocyclic; zinc(II) complex.

CCDC reference: 2033195

1. Chemical context

Benzimidazoles as organic ligands have attracted interest with regard to the synthesis of metal–organic frameworks, not only because of their coordination abilities to metal ions, but also their significant potential applications in biological systems (Ahmad & Bharadwaj; 2013 ; Sharma et al., 2016 ; Gu et al., 2017 ). Benzimidazole compounds and their metal complexes have been found to show diverse biological activity (Podunavac-Kuzmanovic & Cvetkovic, 2010 ), including inhibition against enteroviruses (Xue et al., 2011 ) and potent antitumor activity (Galarce et al., 2008 ). The bidentate ligand 2-(1H-benzo[d]imidazol-2-yl) aniline (L) has been used to prepare a series of mononuclear transition-metal complexes with halide anions as the active leaving group in our catalytic research. In this work, a mononuclear zinc complex ZnLCl₂ is reported. Zinc complexes bearing various ancillary ligands have been applied in the catalysis of the copolymerization of cyclohexene oxide and CO₂ (Kember et al., 2009 ).

2. Structural commentary

The asymmetric unit of the title complex (Fig. 1) contains one neutral complex molecule, which consists of one central zinc ion, one bidentate ligand, and two chlorido ligands with dimethylformamide solvent. The two ligand moieties, benzimidazole and aniline, are not coplanar structure, subtending a dihedral angle of 18.24 (8)°. The C1—N1 and C7—N2 bond lengths are 1.449 (2) and 1.335 (2) Å, respectively. The complex is a four-coordinated system by one imidazole nitrogen atom N2, one aniline nitrogen atom N1, and two chlorido ligands. The distances from the zinc(II) ion to the coordinating atoms are all in the expected ranges. The bond angles around the zinc(II) atom are in the range 88.64 (7) to 118.57 (3)°, of which the smallest angle N1—Zn1—N2 is formed by the two nitrogen atoms from the bidentate ligand.

Figure 1
A view of the title complex with the atom labeling and displacement ellipsoids drawn at the 40% level.

3. Supramolecular features

In the crystal, molecules are linked by N—H⋯Cl hydrogen bonds (Table 1, Fig. 2), forming sheets propagating along the b-axis direction (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.89	2.11	2.923 (2)	152
N1—H1B⋯Cl2ⁱⁱ	0.89	2.48	3.3592 (17)	170
N3—H3⋯O1	0.86	1.99	2.807 (2)	157
C2—H2⋯Cl2ⁱⁱ	0.93	2.93	3.734 (2)	145
C14—H14⋯Cl1ⁱⁱⁱ	0.93	2.95	3.836 (3)	160
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A packing view approximately along [10 $[\overline1]$ ] of the title complex. Hydrogen atoms are omitted for clarity.

Figure 3
Supramolecular view along the b axis of the crystal structure of the title complex formed through C—H⋯π, hydrogen-bonding, and other weak interactions.

4. Hirshfeld Surface analysis

A Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) was undertaken and the associated two-dimensional fingerprint plots (McKinnon, et al., 2007 ) generated using Crystal Explorer (Turner et al., 2017 ) to investigate the intermolecular interactions and surface morphology of the crystal structure. The Hirshfeld surface mapped over d_norm in the color range (^_0.464 to 1.340 a.u.) from red (shorter than the sum of the van der Waals radii) and white to blue (longer distance than the sum of the van der Waals radii). The bright red spot on the d_norm surface (Fig. 4a) indicates the N—H⋯O hydrogen bonding. C—H⋯Cl contacts are evident as distinct circular depressions (red spots) and other visible spots on the d_norm surface (Fig. 4a) are due to H⋯H contacts. The surfaces of the title complex were also mapped over d_e (0.834 to 2.650 Å), shape-index (−1.0000 to 1.0000 Å), and curvedness (−4.0000 to 0.4000 Å) in the given ranges. The flat green region on the d_e surface represents similar contact distances (Fig. 4b). The pattern of red and blue regions in the shape-index surface is characteristic of ring carbon atoms of the molecule inside the surface. The shape of the blue outline on the curved surface shown in Fig. 4d is evidence of the flat region toward the bottom of both sides of the molecules.

Figure 4
The Hirshfeld surface of the title complex mapped over (a) d_norm, (b) d_e, (c) shape-index, and (d) curvedness. Red spots 1,2, and 3 in (a) and (b) correspond to N—H⋯O, N—H⋯Cl, and C—H⋯Cl hydrogen bonds.

Five types of major interactions in the crystal structure (H⋯Cl = 30%, C⋯H = 18.2%, O⋯H = 4.8%, N⋯H = 2.8%, N⋯C = 1.5%) are shown in the two-dimensional fingerprint plots (Fig. 5). The interaction order (H⋯Cl)> (C⋯H)> (O⋯H)> (N⋯H)> (N⋯C) of d_norm on the 2D fingerprint plot represents the nature of packing in the title crystal structure (Muslim et al., 2020 ). The pattern of intermolecular interactions (H⋯Cl/Cl⋯H, C⋯H/H⋯C, O⋯H/H⋯O, N⋯H/H⋯O, and N⋯C/C⋯N) governs the overall packing and quantifies the contribution of the non-covalent interaction (C—H⋯Cl) to the extended supramolecular network (Seth et al., 2011 ; Seth, 2013 ; Manna et al., 2012 ; Mitra et al., 2014 ).

Figure 5
(a) A full two-dimensional fingerprint plot of the title complex, and delineated into (b) H⋯Cl/Cl⋯H (30%), (c) C⋯H/H⋯C (18.2%), and (d) O⋯H/H⋯O (4.8%) contacts, which are the major interactions present in the crystal structure.

5. Database survey

A search of the Cambridge Structural Database (CSD, version 5.39; Groom et al., 2016 ) gave thirteen hits for the [2-(1H-benzimidazol-2-yl]aniline)zinc(II) moiety. Two compounds whose structures are very similar to that of the title compound are [2-(1H-benzimidazol-2-yl)aniline]dichloridozinc(II) (AWOLEE; Eltayeb et al., 2011a ) in which the dimethylformamide solvent is absent and dichloro-[2-(1-methyl-1H-benzimidazol-2-yl)aniline]zinc(II) (ILELIW; Zhou et al., 2016 ) in which the NH group is replaced by an N—CH₃ group. Zinc compounds with different ligands include (2-{[2-(1H-benzimidazol-2-yl-κN³)phenyl]iminomethyl-κN}-5-methylphenolato-κO)chloridozinc(II) (AYINEC; Eltayeb et al., 2011b ) in which the zinc atom is surrounded by two imine nitrogen, one phenolic oxygen and one chlorine atoms. Other complexes include bis{N-[2-(1-butyl-5-nitro-1H-benzimidazol-2-yl)phenyl]-4- methylbenzenesulfonamidato}zinc(II) with an unknown solvate (BUXDIJ; Burlov et al., 2016 ) and bis{4-methyl-N-[2-(5-nitro-1-propyl-1H-benzimidazole-2-yl)phenyl]benzenesulfonamidato}zinc(II) chloroform solvate (BUXDOP; Burlov et al., 2016), bis{μ-[2-(5-amino-1-propyl-1H-benzimidazole-2-yl)phenyl](4-methylbenzene-1-sulfonyl)amido}bis(pivalato)dizinc acetonitrile ethanol solvate dihydrate (EDOVUR; Nikolaevskii et al., 2014 ), bis(μ₂-3-{[2-(1H-benzimidazole-2-yl)phenyl]carbonoimidoyl}benzene-1,2-diolato)dizinc(II) ethanol solvate (GABVUD; Wang et al., 2016 ), (acetato-O,O′)-[2-({[2-(1H-benzimidazole-2-yl)phenyl]imino}methyl)-5-(diethylamino)phenolato]zinc(II) isopropanol solvate (IKOYUE; Liao et al., 2016 ).

6. Synthesis and crystallization

A mixture of 2-(2-aminophenylbenzimidazole) (0.05 g, 0.14 mmol) and ZnCl₂·4H₂O (0.125 g, 0.4 mmol) was dissolved in 5 ml of dimethylformamide (DMF) and then sealed in a Teflon-lined autoclave and heated under autogenous pressure to 453 K for 2 d and then allow to cool to room temperature at the rate of 1 K per minute. The resulting solution was filtered and kept for slow evaporation. After one week, block-shaped colorless crystals suitable for single-crystal X-ray diffraction data collection were obtained.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were positioned geometrically (N—H = 0.86–0.89, C—H = 0.93–0.96 Å) included with U_iso(H) = 1.2U_eq(N, C) or 1.5U_eq(C-methyl).

Table 2
Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₃H₁₁N₃)]·C₃H₇NO
M_r	418.61
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	10.9394 (9), 13.3041 (7), 13.1665 (11)
β (°)	106.140 (7)
V (Å³)	1840.7 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.64
Crystal size (mm)	0.60 × 0.50 × 0.39

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002 )
T_min, T_max	0.460, 0.567
No. of measured, independent and observed [I > 2σ(I)] reflections	19616, 5643, 3891
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.717

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.097, 1.04
No. of reflections	5643
No. of parameters	219
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.62
Computer programs: X-AREA (Stoe & Cie, 2002), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), and XP in SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 2033195

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021003649/ex2042sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021003649/ex2042Isup4.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: XP in SHELXTL (Sheldrick, 2008).

[2-(1H-Benzimidazol-2-yl-κN³)aniline-κN]dichloridozinc(II) N,N-dimethylformamide monosolvate top

Crystal data top

[ZnCl₂(C₁₃H₁₁N₃)]·C₃H₇NO	F(000) = 856
M_r = 418.61	D_x = 1.511 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.9394 (9) Å	Cell parameters from 22582 reflections
b = 13.3041 (7) Å	θ = 1.5–31.0°
c = 13.1665 (11) Å	µ = 1.64 mm⁻¹
β = 106.140 (7)°	T = 296 K
V = 1840.7 (2) Å³	Prism, yellow
Z = 4	0.60 × 0.50 × 0.39 mm

Data collection top

STOE IPDS 2 diffractometer	5643 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	3891 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.036
Detector resolution: 6.67 pixels mm^-1	θ_max = 30.7°, θ_min = 2.2°
rotation method scans	h = −15→15
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −17→18
T_min = 0.460, T_max = 0.567	l = −18→18
19616 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0502P)² + 0.0362P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
5643 reflections	Δρ_max = 0.34 e Å⁻³
219 parameters	Δρ_min = −0.62 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.

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

	x	y	z	U_iso*/U_eq
Zn1	0.40345 (2)	0.83177 (2)	0.52883 (2)	0.04912 (8)
Cl2	0.61440 (5)	0.84302 (4)	0.60104 (5)	0.06630 (16)
Cl1	0.27561 (6)	0.87107 (5)	0.62724 (5)	0.07198 (17)
O1	0.41861 (16)	0.45845 (14)	0.17389 (14)	0.0726 (5)
N1	0.35146 (16)	0.90600 (12)	0.38489 (13)	0.0502 (4)
H1A	0.267634	0.900599	0.357590	0.060*
H1B	0.369650	0.970981	0.395980	0.060*
N3	0.37815 (15)	0.58840 (12)	0.32936 (13)	0.0504 (4)
H3	0.388210	0.563774	0.271825	0.060*
N2	0.36342 (15)	0.70047 (12)	0.44985 (13)	0.0476 (3)
N4	0.5564 (2)	0.35468 (17)	0.12569 (17)	0.0691 (5)
C7	0.38739 (18)	0.68676 (14)	0.35677 (15)	0.0455 (4)
C1	0.41353 (18)	0.86859 (16)	0.30855 (15)	0.0480 (4)
C13	0.34988 (17)	0.53440 (15)	0.40928 (16)	0.0486 (4)
C8	0.33936 (18)	0.60573 (14)	0.48466 (16)	0.0479 (4)
C6	0.42738 (18)	0.76471 (15)	0.29345 (15)	0.0482 (4)
C12	0.3365 (2)	0.43147 (16)	0.42430 (19)	0.0590 (5)
H12	0.345224	0.384308	0.374641	0.071*
C2	0.4613 (2)	0.93761 (18)	0.25020 (18)	0.0582 (5)
H2	0.452680	1.005994	0.261168	0.070*
C9	0.3122 (2)	0.57631 (17)	0.57798 (18)	0.0588 (5)
H9	0.304769	0.623164	0.628334	0.071*
C10	0.2969 (2)	0.47426 (18)	0.5923 (2)	0.0652 (6)
H10	0.277820	0.452174	0.653141	0.078*
C11	0.3097 (2)	0.40357 (18)	0.5165 (2)	0.0658 (6)
H11	0.299785	0.335685	0.529071	0.079*
C5	0.4888 (2)	0.73555 (19)	0.21791 (18)	0.0610 (5)
H5	0.499020	0.667438	0.206631	0.073*
C14	0.5136 (2)	0.4429 (2)	0.1430 (2)	0.0673 (6)
H14	0.558734	0.498851	0.131104	0.081*
C3	0.5212 (2)	0.9066 (2)	0.1763 (2)	0.0674 (6)
H3A	0.552587	0.953741	0.137785	0.081*
C4	0.5345 (2)	0.8051 (2)	0.1598 (2)	0.0694 (6)
H4	0.574124	0.783670	0.109566	0.083*
C15	0.4900 (4)	0.2641 (2)	0.1419 (3)	0.0947 (9)
H15A	0.458046	0.272789	0.202229	0.142*
H15B	0.547714	0.208200	0.153689	0.142*
H15C	0.420336	0.251482	0.080351	0.142*
C16	0.6699 (3)	0.3452 (3)	0.0881 (3)	0.1086 (13)
H16A	0.700566	0.410905	0.077503	0.163*
H16B	0.648854	0.308946	0.022441	0.163*
H16C	0.734825	0.309531	0.139603	0.163*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.05561 (14)	0.04018 (13)	0.05557 (14)	−0.00002 (10)	0.02208 (10)	−0.00610 (10)
Cl2	0.0557 (3)	0.0485 (3)	0.0914 (4)	0.0007 (2)	0.0149 (3)	−0.0107 (3)
Cl1	0.0790 (4)	0.0697 (4)	0.0814 (4)	0.0010 (3)	0.0458 (3)	−0.0117 (3)
O1	0.0641 (9)	0.0727 (11)	0.0876 (11)	−0.0039 (8)	0.0320 (9)	−0.0269 (9)
N1	0.0536 (9)	0.0383 (8)	0.0625 (10)	0.0024 (7)	0.0226 (8)	−0.0004 (7)
N3	0.0548 (9)	0.0409 (9)	0.0557 (9)	−0.0016 (7)	0.0155 (7)	−0.0098 (7)
N2	0.0513 (8)	0.0383 (8)	0.0561 (9)	0.0002 (7)	0.0198 (7)	−0.0054 (7)
N4	0.0641 (11)	0.0695 (13)	0.0731 (12)	0.0084 (10)	0.0178 (10)	−0.0187 (10)
C7	0.0450 (9)	0.0381 (10)	0.0536 (10)	0.0006 (7)	0.0138 (8)	−0.0064 (8)
C1	0.0458 (9)	0.0458 (10)	0.0531 (10)	0.0001 (8)	0.0152 (8)	−0.0010 (8)
C13	0.0411 (9)	0.0405 (10)	0.0621 (11)	0.0009 (7)	0.0108 (8)	−0.0044 (8)
C8	0.0442 (9)	0.0393 (9)	0.0612 (11)	−0.0011 (7)	0.0162 (8)	−0.0023 (8)
C6	0.0462 (9)	0.0459 (10)	0.0533 (10)	−0.0012 (8)	0.0152 (8)	−0.0047 (8)
C12	0.0551 (11)	0.0406 (11)	0.0781 (14)	−0.0027 (9)	0.0131 (10)	−0.0075 (10)
C2	0.0593 (12)	0.0504 (12)	0.0690 (13)	−0.0024 (9)	0.0245 (10)	0.0031 (10)
C9	0.0626 (12)	0.0531 (12)	0.0657 (12)	0.0021 (10)	0.0259 (10)	0.0019 (10)
C10	0.0634 (13)	0.0587 (14)	0.0778 (15)	−0.0017 (11)	0.0269 (11)	0.0136 (11)
C11	0.0586 (12)	0.0436 (11)	0.0936 (17)	−0.0033 (10)	0.0185 (12)	0.0092 (11)
C5	0.0686 (13)	0.0557 (13)	0.0651 (12)	0.0001 (10)	0.0295 (11)	−0.0092 (10)
C14	0.0619 (13)	0.0669 (15)	0.0772 (14)	−0.0053 (11)	0.0262 (11)	−0.0206 (12)
C3	0.0711 (14)	0.0680 (15)	0.0716 (14)	−0.0072 (12)	0.0340 (12)	0.0047 (12)
C4	0.0759 (15)	0.0767 (16)	0.0670 (14)	−0.0022 (13)	0.0388 (12)	−0.0059 (12)
C15	0.122 (3)	0.0664 (18)	0.098 (2)	0.0083 (18)	0.0341 (19)	−0.0014 (16)
C16	0.0760 (19)	0.124 (3)	0.134 (3)	0.0120 (18)	0.0440 (19)	−0.051 (2)

Geometric parameters (Å, º) top

Zn1—N2	2.0177 (16)	C6—C5	1.401 (3)
Zn1—N1	2.0715 (17)	C12—C11	1.376 (3)
Zn1—Cl1	2.2171 (6)	C12—H12	0.9300
Zn1—Cl2	2.2432 (7)	C2—C3	1.379 (3)
O1—C14	1.234 (3)	C2—H2	0.9300
N1—C1	1.449 (2)	C9—C10	1.387 (3)
N1—H1A	0.8900	C9—H9	0.9300
N1—H1B	0.8900	C10—C11	1.406 (4)
N3—C7	1.354 (2)	C10—H10	0.9300
N3—C13	1.378 (3)	C11—H11	0.9300
N3—H3	0.8600	C5—C4	1.380 (3)
N2—C7	1.335 (2)	C5—H5	0.9300
N2—C8	1.391 (2)	C14—H14	0.9300
N4—C14	1.307 (3)	C3—C4	1.382 (4)
N4—C15	1.453 (4)	C3—H3A	0.9300
N4—C16	1.465 (3)	C4—H4	0.9300
C7—C6	1.471 (3)	C15—H15A	0.9600
C1—C2	1.389 (3)	C15—H15B	0.9600
C1—C6	1.410 (3)	C15—H15C	0.9600
C13—C12	1.397 (3)	C16—H16A	0.9600
C13—C8	1.401 (3)	C16—H16B	0.9600
C8—C9	1.398 (3)	C16—H16C	0.9600

N2—Zn1—N1	88.64 (7)	C13—C12—H12	121.8
N2—Zn1—Cl1	115.06 (5)	C3—C2—C1	121.2 (2)
N1—Zn1—Cl1	111.40 (5)	C3—C2—H2	119.4
N2—Zn1—Cl2	109.06 (5)	C1—C2—H2	119.4
N1—Zn1—Cl2	110.14 (5)	C10—C9—C8	117.2 (2)
Cl1—Zn1—Cl2	118.57 (3)	C10—C9—H9	121.4
C1—N1—Zn1	114.12 (12)	C8—C9—H9	121.4
C1—N1—H1A	108.7	C9—C10—C11	121.2 (2)
Zn1—N1—H1A	108.7	C9—C10—H10	119.4
C1—N1—H1B	108.7	C11—C10—H10	119.4
Zn1—N1—H1B	108.7	C12—C11—C10	122.2 (2)
H1A—N1—H1B	107.6	C12—C11—H11	118.9
C7—N3—C13	108.43 (16)	C10—C11—H11	118.9
C7—N3—H3	125.8	C4—C5—C6	121.8 (2)
C13—N3—H3	125.8	C4—C5—H5	119.1
C7—N2—C8	106.38 (16)	C6—C5—H5	119.1
C7—N2—Zn1	121.43 (13)	O1—C14—N4	125.6 (3)
C8—N2—Zn1	130.43 (13)	O1—C14—H14	117.2
C14—N4—C15	120.1 (2)	N4—C14—H14	117.2
C14—N4—C16	121.0 (3)	C2—C3—C4	119.7 (2)
C15—N4—C16	118.9 (3)	C2—C3—H3A	120.2
N2—C7—N3	110.96 (17)	C4—C3—H3A	120.2
N2—C7—C6	126.08 (17)	C5—C4—C3	119.8 (2)
N3—C7—C6	122.84 (17)	C5—C4—H4	120.1
C2—C1—C6	119.87 (18)	C3—C4—H4	120.1
C2—C1—N1	118.52 (18)	N4—C15—H15A	109.5
C6—C1—N1	121.60 (17)	N4—C15—H15B	109.5
N3—C13—C12	132.33 (19)	H15A—C15—H15B	109.5
N3—C13—C8	105.54 (17)	N4—C15—H15C	109.5
C12—C13—C8	122.1 (2)	H15A—C15—H15C	109.5
N2—C8—C9	130.48 (18)	H15B—C15—H15C	109.5
N2—C8—C13	108.66 (17)	N4—C16—H16A	109.5
C9—C8—C13	120.83 (19)	N4—C16—H16B	109.5
C5—C6—C1	117.58 (19)	H16A—C16—H16B	109.5
C5—C6—C7	118.94 (18)	N4—C16—H16C	109.5
C1—C6—C7	123.39 (17)	H16A—C16—H16C	109.5
C11—C12—C13	116.5 (2)	H16B—C16—H16C	109.5
C11—C12—H12	121.8

C8—N2—C7—N3	0.9 (2)	N1—C1—C6—C7	−3.5 (3)
Zn1—N2—C7—N3	167.25 (13)	N2—C7—C6—C5	158.9 (2)
C8—N2—C7—C6	−175.14 (18)	N3—C7—C6—C5	−16.7 (3)
Zn1—N2—C7—C6	−8.8 (3)	N2—C7—C6—C1	−17.5 (3)
C13—N3—C7—N2	−1.5 (2)	N3—C7—C6—C1	166.93 (18)
C13—N3—C7—C6	174.63 (18)	N3—C13—C12—C11	178.7 (2)
Zn1—N1—C1—C2	−135.94 (17)	C8—C13—C12—C11	1.3 (3)
Zn1—N1—C1—C6	43.4 (2)	C6—C1—C2—C3	0.7 (3)
C7—N3—C13—C12	−176.2 (2)	N1—C1—C2—C3	−179.9 (2)
C7—N3—C13—C8	1.5 (2)	N2—C8—C9—C10	−177.7 (2)
C7—N2—C8—C9	178.2 (2)	C13—C8—C9—C10	0.2 (3)
Zn1—N2—C8—C9	13.6 (3)	C8—C9—C10—C11	0.7 (3)
C7—N2—C8—C13	0.1 (2)	C13—C12—C11—C10	−0.3 (3)
Zn1—N2—C8—C13	−164.58 (13)	C9—C10—C11—C12	−0.7 (4)
N3—C13—C8—N2	−1.0 (2)	C1—C6—C5—C4	0.0 (3)
C12—C13—C8—N2	177.06 (18)	C7—C6—C5—C4	−176.6 (2)
N3—C13—C8—C9	−179.33 (19)	C15—N4—C14—O1	0.5 (4)
C12—C13—C8—C9	−1.3 (3)	C16—N4—C14—O1	179.4 (3)
C2—C1—C6—C5	−0.7 (3)	C1—C2—C3—C4	−0.1 (4)
N1—C1—C6—C5	−179.96 (19)	C6—C5—C4—C3	0.7 (4)
C2—C1—C6—C7	175.8 (2)	C2—C3—C4—C5	−0.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.89	2.11	2.923 (2)	152
N1—H1B···Cl2ⁱⁱ	0.89	2.48	3.3592 (17)	170
N3—H3···O1	0.86	1.99	2.807 (2)	157
C2—H2···Cl2ⁱⁱ	0.93	2.93	3.734 (2)	145
C14—H14···Cl1ⁱⁱⁱ	0.93	2.95	3.836 (3)	160

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1, −y+2, −z+1; (iii) x+1/2, −y+3/2, z−1/2.

Acknowledgements

The Department of Applied Chemistry, ZHCET, Faculty of Engineering and Technology, Aligarh Muslim University, UP, India, is gratefully acknowledged for providing laboratory facilities. Author contributions are as follows. Conceptualization, AM, MA and MM; methodology, MA, AM and MSHF; investigation, ND, AA and MA; writing (original draft), MM and MSHF; writing (review and editing of the manuscript), MdA, MM and AA; visualization, MM, AA and MSHF; funding acquisition, AM; resources, ND and MA; supervision, AM and MA.

Funding information

MA and MSHF acknowledge the startup grant received from UGC, India.

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