Crystal structure, DFT and Hirshfeld surface analysis of (E)-N′-[(1-chloro-3,4-di­hydro­naph­thal­en-2-yl)methyl­idene]benzohydrazide monohydrate

Arjun, H.A.; Anil Kumar, G.N.; Elancheran, R.; Kabilan, S.

doi:10.1107/S2056989019017183

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ISSN: 2056-9890

Volume 76| Part 2| February 2020| Pages 132-136

https://doi.org/10.1107/S2056989019017183

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Crystal structure, DFT and Hirshfeld surface analysis of (E)-N′-[(1-chloro-3,4-dihydronaphthalen-2-yl)methylidene]benzohydrazide monohydrate

H. A. Arjun,^a G. N. Anil Kumar,^b ^* R. Elancheran ^a and S. Kabilan ^a ^*

^aDrug Discovery Lab, Department of Chemistry, Annamalai University, Chidambaram 608002, Tamil Nadu, India, and ^bDepartment of Physics, Ramaiah Institute of Technology, Bengaluru 560054, India
^*Correspondence e-mail: anilgn@msrit.edu, profdrskabilanau@gmail.com

Edited by H. Ishida, Okayama University, Japan (Received 13 December 2019; accepted 23 December 2019; online 3 January 2020)

In the title compound, C₁₈H₁₅ClN₂O·H₂O, a benzohydrazide derivative, the dihedral angle between the mean plane of the dihydronaphthalene ring system and the phenyl ring is 17.1 (2)°. In the crystal, O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds link the benzohydrazide and water molecules, forming a layer parallel to the bc plane. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contributions to the crystal packing are from H⋯H (45.7%) and H⋯C/C⋯H (20.2%) contacts.

Keywords: crystal structure; benzohydrazide derivative; Hirshfeld surface analysis.

CCDC reference: 1973816

1. Chemical context

Benzohydrazides are versatile compounds in medicinal chemistry that are used for the development of new drugs (Veeramanikandan et al., 2015 ). Benzohydrazide derivatives are potent inhibitors of prostate cancer (Arjun et al., 2019 ) and show anti-inflammatory (Todeschini et al., 1998 ), anti-malarial (Melnyk et al., 2006 ), entamoeba histolyica (Inam et al., 2016 ) and anti-tuberculosis (Bedia et al., 2006 ) activities. Herein we describe the molecular and crystal structures of the title compound, which can act as a potential multidrug ligand for various biological activities. The molecular packing was further studied with Hirshfeld surface analysis and PIXEL methods (Sowmya et al., 2018 ).

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The benzohydrazide molecule adopts an E configuration with respect to the C8=N2 bond. The cyclohexene ring (C9–C12/C17/C18) adopts nearly a half-chair conformation, as indicated by the total puckering amplitude Q_T of 0.431 (3) Å and spherical polar angle θ = 115.6 (3)° with φ = 264.4 (4)°; atom C10 shows a maximum deviation of 0.282 (4) Å from the mean plane. The phenyl ring (C1–C6) and the mean plane of the dihydronaphthalene ring system (C9–C18) are inclined to each other by 17.1 (2)°. The central hydrazine fragment (C8/N2/N6/C7/O1) is almost planar, making dihedral angles of 11.0 (2) and 8.49 (18)°, respectively, with the phenyl ring and the mean plane of the dihydronaphthalene ring system.

Figure 1
The molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The O—H⋯O hydrogen bond is indicated by a dashed line.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, the water molecule forms five hydrogen bonds with three benzohydrazide molecules. The benzohydrazide molecules are stacked in a column along the b-axis direction through O—H⋯O hydrogen bonds (O2—H2A⋯O1ⁱ and O2—H2B⋯O1; symmetry code as in Table 1) between the H atoms of the water molecule and the carbonyl O atoms of two adjacent benzohydrazide molecules (Fig. 2). The water molecule also acts as a hydrogen-bond acceptor from other benzohydrazide molecules: N—H⋯O and C—H⋯O hydrogen bonds (N6—H6⋯O2ⁱⁱ, C1—H1⋯O2ⁱⁱ and C8—H8⋯O2ⁱⁱ; Table 1) link the molecules, forming a layer parallel to the bc plane.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1ⁱ	0.78 (5)	2.06 (5)	2.829 (4)	166 (5)
O2—H2B⋯O1	0.96 (6)	1.90 (6)	2.858 (4)	171 (5)
N6—H6⋯O2ⁱⁱ	0.93 (5)	1.98 (5)	2.869 (4)	159 (4)
C1—H1⋯O2ⁱⁱ	0.93	2.47	3.350 (5)	158
C8—H8⋯O2ⁱⁱ	0.93	2.48	3.261 (5)	142
Symmetry codes: (i) x, y+1, z; (ii) $[-x+1, -y, z-{\script{1\over 2}}]$ .

Figure 2
A packing diagram of the title compound, showing the O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds (dashed lines). H atoms not involved in these interactions have been omitted.

Hirshfeld surface analysis was performed using CrystalExplorer17.5 (Spackman & Jayatilaka, 2009 ) to quantify and visualize the various intermolecular contacts in the crystal. The Hirshfeld surface for the title compound mapped over d_norm is shown in Fig. 3, where the dark-red spot represents a close contact of the water molecule, corresponding to the O—H⋯O interactions. Two-dimensional fingerprint plots are shown in Fig. 4. The most important contributions to the crystal packing are from H⋯H/H⋯H (45.7%), C⋯H/H⋯C (20.2%), O⋯H/H⋯O (9.4%), Cl⋯H/H⋯Cl (11.3%), C⋯C(6.4%) and C⋯N/N⋯C(3.4%) interactions.

Figure 3
Hirshfeld surface mapped over d_norm (range −0.575 to 1.326 a.u.) for the title compound showing the O—H⋯O hydrogen bond.

Figure 4
Two-dimensional fingerprint plots for the title compound with the percentage contribution of the intermolecular contacts. The d_i and d_e values are the closest internal and external distances (Å) from given points on the Hirshfeld surface.

4. Interaction energies and theoretical calculations

The various intermolecular interaction energies of the title crystal were calculated using the PIXEL-CLP module (Gavezzotti, 2003 ). The lattice energy of the crystal structure is found to be −67.2 kJ mol⁻¹ with the energy partitioned into Coulombic, polarization, dispersion and repulsion energy components of −68.4, −30.7, −95.3 and 128.1 kJ mol⁻¹, respectively. The important molecular pairs (motifs A–F) and their interaction energies are shown in Fig. 5, and the partitioned intermolecular energies along with the above interactions are given in Table 2. The N—H⋯O interaction energy in motif F (−32.8 kJ mol⁻¹) is strongest followed by the O—H⋯O interactions in motifs A and E (−27.1 and −23.9 kJ mol⁻¹, respectively), and the C—H⋯O interaction in motif B (−16 kJ mol⁻¹).

Table 2
List of intermolecular interaction energies (kJ mol⁻¹) in the crystal of the title compound

Code	Symmetry	Centroid distance	E_col	E_pol	E_{energy-dispersive}	E_rep	E_total	Interaction
A	x, y + 1, z	4.812	−37.4	−14.2	−64.3	88.7	−27.1	O—H⋯O
B	-x + 1, −y + 1, z − $[{1\over 2}]$	7.513	−6.7	−4.3	−20.9	15.9	−16.0	C—H⋯O
C	-x + 1, −y + $[{1\over 2}]$ , z	9.210	−2.2	−4.2	−16.1	6.6	−15.9	Cl⋯H
D	-x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , z + $[{1\over 2}]$	11.475	−1.9	−0.9	−8.9	3.8	−7.9	H⋯H
E	x, y, z	5.924	−33.1	−11.6	−12.3	33.1	−23.9	O—H⋯O
F	x, y − 1, z	4.077	−38.5	−12.0	−13.0	30.7	−32.8	N—H⋯O

Figure 5
Important molecular pairs in the crystal of the title compound and their interaction energies.

Density functional theory (DFT) calculations using the B3LYP (Becke, 1993 ) method at the 6-31++G(d,p) level were performed using GAUSSIAN09 (Frisch et al., 2009 ). The DFT-optimized structure of the title compound is found to be in good agreement with the experimental geometry. Frontier molecular orbitals are plotted to specify the distribution of electronic densities (Fig. 6); the HOMO–LUMO gap of 3.6349 eV indicates that the nature of molecule is soft. The quantum-chemical parameters, such as hardness (η), softness (ζ), chemical potential (μ), electrophilicity (ω) and electronegativity (χ), were also calculated (Table 3), using the HOMO and LUMO energies. The electrophilicity index (ω) of 4.3148 eV, which measures the energy lowering due to the electron flow between the donor and acceptor, also supports the soft nature of the title compound. The lower chemical potential (μ) of −3.9602 eV signifies the lesser resistance towards the deformation or polarization of the electron cloud of the atoms or molecule under a small perturbation of chemical reaction.

Table 3
HUMO–LUMO energies and quantum-chemical parameters (eV) for the title compound

HOMO energy: E_H	−5.7777
LUMO energy: E_L	−2.1428
Energy gap: E_g = E_H − E_L	3.6349
Chemical hardness: η = \|E_H − E_L\|/2	1.8174
Softness: ζ = 1/2η	0.2751
Electrophilicity index: ω = μ²/2η	4.3148
Chemical Potential: μ = −(E_H + E_L/2)	−3.9602
Electronegativity: χ = -μ	3.9602

Figure 6
The frontier molecular orbitals, highest-occupied molecular orbital (HOMO) and the lowest-unoccupied molecular orbital (LUMO), calculated for the title compound.

5. Database Survey

A search of the Cambridge Structural Database (Version 5.39; Groom et al., 2016 ) gave 1579 hits for the benzohydrazides with different substituents and 260 hits for their hydrate compounds. The water molecules mediate strong hydrogen bonds in hydrate compounds such as (E)-3,4,5-trimethoxy-N-[(6-methoxy-4-oxo-4H-chromen-3-yl)methylidene]benzohydrazide monohydrate (Ishikawa & Watanabe, 2014a ), (E)-4-methoxy-N-[(6-methyl-4-oxo-4H-chromen-3-yl)methylidene]benzohydrazide monohydrate (Ishikawa & Watanabe, 2014b ), N-[(E)-(3-fluoropyridin-2-yl)methylidene]benzohydrazide monohydrate (Nair et al., 2012 ), (E)-4-methoxy-N-(2,3,4-trimethoxybenzylidene)benzohydrazide monohydrate (Veeramanikandan et al., 2016 ), 4-chloro-N-[(E)-2-chlorobenzylidene]benzohydrazide monohydrate (Mague et al., 2014 ), 4-chloro-N-[(Z)-4-(dimethylamino)benzylidene]benzohydrazide monohydrate (Fun et al., 2008 ), (E)-N-(4-butoxy-3-methoxybenzylidene)benzohydrazide (Zhen & Han, 2005 ) and (E)-4-hydroxy-N-(3-hydroxybenzylidene)benzohydrazide monohydrate (Harrison et al., 2014 ). The presence of O—H⋯N hydrogen bonds in addition to water-mediated O—H⋯O interactions is a common feature in many of the reported structures, but such an O—H⋯N interaction is not observed in the title compound.

6. Synthesis and crystallization

Phosphoryl chloride (POCl₃) (0.171mol) was slowly added to dry dimethyl formamide at 273 K, and then 3,4-dihydronaphthalen-1(2H)-one (0.174 mol) was added. The mixture was stirred at 353 K for 1.5 h. The reaction mixture was then poured into aqueous sodium acetate (3 mol l⁻¹) and the product was extracted with ethyl acetate. Evaporating the ethyl acetate gave an oil, which on cooling solidified to yield 1-chloro-3,4-dihydronaphthalene-2-carbaldehyde. The title compound was prepared by refluxing 1-chloro-3,4-dihydronaphthalene-2-carbaldehyde (0.01 mol) with benzohydrazide (0.01 mol) in ethanol (5 ml) and few drops of acetic acid for 8 h. The reaction mixture was then cooled to room temperature, excess ethanol was removed under vacuum and the residue was quenched with ice. The precipitate was filtered, dried and crystallized from ethanol. The completion of the reaction was monitored by thin layer chromatography. Single crystals suitable for X-ray diffraction study were grown from an N,N-dimethylformamide solution by slow evaporation. Yield: 86%; m.p.: 438–440 K, colourless solid. ¹H NMR (DMSO-d₆, 400 MHz, ppm): δ 12.10 (s, 1H, NH), 8.77 (s, 1H), 7.87 (d, J = 7.2, 2H), 7.64–7.25 (m, 7H), 2.808–2.764 (m, 4H). ¹³C NMR: δ 163.34, 143.77, 144.5, 136.97, 132.72, 132.63, 131.65, 130.73, 129.80, 129.49, 128.16, 128.00, 127.41, 124.94, 29.50, 26.54, 23.65, 21.51. Mass calculated for C₁₈H₁₅ClN₂O [M+H]⁺: 310.08; found: 310.9758.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. The N-bound H atom (H6) and water H atoms (H2A and H2B) were located in a difference-Fourier map and refined isotropically. All C-bound H atoms were placed in idealized positions (C—H = 0.93 or 0.97 Å) and treated as riding with U_iso(H) = 1.2U_eq(C).

Table 4
Experimental details

Crystal data
Chemical formula	C₁₈H₁₅ClN₂O·H₂O
M_r	328.78
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	301
a, b, c (Å)	26.2059 (18), 4.8119 (3), 12.8084 (9)
V (Å³)	1615.14 (19)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.25
Crystal size (mm)	0.28 × 0.22 × 0.21

Data collection
Diffractometer	Bruker APEXII microsource
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.890, 0.915
No. of measured, independent and observed [I > 2σ(I)] reflections	51179, 4917, 3162
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.151, 1.03
No. of reflections	4917
No. of parameters	220
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.30
Absolute structure	Flack x determined using 1242 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.04 (2)
Computer programs: APEX2 and SAINT (Bruker, 2012), SIR2011 (Burla et al., 2012 ), SHELXL2018 (Sheldrick, 2015 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1973816

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989019017183/is5528sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019017183/is5528Isup2.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: SIR2011 (Burla et al., 2012); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(E)-N'-[(1-Chloro-3,4-dihydronaphthalen-2-yl)methylidene]\ benzohydrazide monohydrate top

Crystal data top

C₁₈H₁₅ClN₂O·H₂O	F(000) = 688
M_r = 328.78	D_x = 1.352 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 689 reflections
a = 26.2059 (18) Å	θ = 2.2–30.1°
b = 4.8119 (3) Å	µ = 0.25 mm⁻¹
c = 12.8084 (9) Å	T = 301 K
V = 1615.14 (19) Å³	Block, white
Z = 4	0.28 × 0.22 × 0.21 mm

Data collection top

Bruker APEXII microsource diffractometer	4917 independent reflections
Radiation source: microfocus sealed X-ray tube	3162 reflections with I > 2σ(I)
Mirror optics monochromator	R_int = 0.069
Detector resolution: 7.9 pixels mm^-1	θ_max = 30.6°, θ_min = 2.2°
ω and φ scans	h = −37→36
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −6→6
T_min = 0.890, T_max = 0.915	l = −18→18
51179 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.151	w = 1/[σ²(F_o²) + (0.0735P)² + 0.2866P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
4917 reflections	Δρ_max = 0.18 e Å⁻³
220 parameters	Δρ_min = −0.30 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 1242 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.04 (2)

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
Cl01	0.64431 (5)	0.3485 (3)	0.24491 (8)	0.0815 (4)
O1	0.48097 (11)	−0.3470 (5)	0.58021 (18)	0.0577 (6)
O2	0.48890 (14)	0.1565 (7)	0.6974 (2)	0.0676 (8)
N6	0.50596 (11)	−0.2027 (6)	0.4205 (2)	0.0463 (6)
N2	0.54124 (11)	−0.0257 (5)	0.4646 (2)	0.0469 (6)
C1	0.44073 (17)	−0.6214 (7)	0.3284 (3)	0.0589 (9)
H1	0.464242	−0.537211	0.284202	0.071*
C2	0.40586 (19)	−0.8116 (8)	0.2890 (3)	0.0699 (11)
H2	0.405810	−0.852699	0.218085	0.084*
C3	0.37164 (16)	−0.9389 (9)	0.3536 (4)	0.0677 (11)
H3	0.348710	−1.067883	0.326756	0.081*
C4	0.37102 (15)	−0.8766 (9)	0.4583 (4)	0.0661 (10)
H4	0.347389	−0.961795	0.501996	0.079*
C5	0.40541 (13)	−0.6878 (8)	0.4987 (3)	0.0543 (8)
H5	0.405023	−0.648210	0.569795	0.065*
C6	0.44038 (12)	−0.5569 (6)	0.4347 (2)	0.0440 (7)
C7	0.47695 (12)	−0.3606 (6)	0.4845 (2)	0.0429 (6)
C8	0.57029 (13)	0.1000 (8)	0.3996 (3)	0.0514 (8)
H8	0.566552	0.073299	0.328142	0.062*
C9	0.60942 (13)	0.2864 (7)	0.4405 (3)	0.0500 (7)
C10	0.61014 (14)	0.3515 (8)	0.5571 (3)	0.0546 (8)
H10A	0.593193	0.203807	0.595282	0.066*
H10B	0.591853	0.523334	0.570138	0.066*
C11	0.66436 (15)	0.3790 (9)	0.5944 (3)	0.0603 (9)
H11A	0.664204	0.450456	0.665242	0.072*
H11B	0.679939	0.196212	0.595934	0.072*
C12	0.69626 (13)	0.5672 (8)	0.5273 (3)	0.0548 (8)
C13	0.73640 (15)	0.7232 (10)	0.5674 (4)	0.0703 (11)
H13	0.743717	0.714146	0.638323	0.084*
C14	0.76533 (16)	0.8898 (10)	0.5042 (5)	0.0796 (14)
H14	0.791894	0.993296	0.532615	0.096*
C15	0.75553 (16)	0.9049 (10)	0.4007 (5)	0.0771 (13)
H15	0.775202	1.020496	0.358664	0.093*
C16	0.71653 (16)	0.7501 (10)	0.3565 (4)	0.0692 (11)
H16	0.710430	0.759136	0.285089	0.083*
C17	0.68627 (13)	0.5795 (8)	0.4204 (3)	0.0549 (8)
C18	0.64461 (13)	0.4061 (8)	0.3791 (3)	0.0536 (8)
H2A	0.4899 (19)	0.281 (11)	0.658 (4)	0.068 (14)*
H2B	0.4887 (19)	−0.005 (13)	0.653 (4)	0.082 (15)*
H6	0.4993 (18)	−0.204 (10)	0.349 (4)	0.071 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl01	0.0854 (7)	0.1131 (10)	0.0460 (5)	−0.0167 (6)	0.0052 (5)	0.0096 (6)
O1	0.0824 (17)	0.0516 (13)	0.0391 (11)	−0.0173 (12)	−0.0005 (11)	0.0002 (10)
O2	0.107 (2)	0.0580 (17)	0.0377 (12)	−0.0104 (15)	−0.0058 (13)	0.0033 (13)
N6	0.0548 (15)	0.0444 (14)	0.0396 (13)	−0.0079 (12)	−0.0029 (12)	0.0010 (11)
N2	0.0532 (15)	0.0418 (13)	0.0456 (13)	−0.0061 (11)	−0.0046 (11)	0.0014 (11)
C1	0.082 (2)	0.0491 (19)	0.0460 (18)	−0.0105 (17)	−0.0023 (17)	−0.0016 (15)
C2	0.099 (3)	0.056 (2)	0.054 (2)	−0.009 (2)	−0.017 (2)	−0.0074 (18)
C3	0.063 (2)	0.052 (2)	0.088 (3)	−0.0062 (18)	−0.016 (2)	−0.009 (2)
C4	0.051 (2)	0.063 (2)	0.085 (3)	−0.0085 (17)	0.0055 (19)	−0.004 (2)
C5	0.0508 (18)	0.0550 (19)	0.057 (2)	−0.0037 (15)	0.0072 (15)	−0.0048 (16)
C6	0.0511 (17)	0.0363 (13)	0.0445 (15)	0.0031 (12)	−0.0035 (13)	−0.0007 (12)
C7	0.0513 (16)	0.0380 (14)	0.0393 (15)	0.0017 (12)	−0.0007 (12)	0.0007 (12)
C8	0.0556 (18)	0.0532 (18)	0.0454 (17)	−0.0059 (15)	0.0009 (14)	0.0022 (14)
C9	0.0533 (18)	0.0493 (17)	0.0475 (18)	0.0011 (14)	0.0012 (14)	0.0040 (14)
C10	0.0507 (17)	0.064 (2)	0.0495 (18)	−0.0105 (16)	0.0004 (14)	−0.0084 (15)
C11	0.063 (2)	0.064 (2)	0.054 (2)	0.0048 (18)	−0.0070 (17)	0.0023 (17)
C12	0.0467 (17)	0.0496 (17)	0.068 (2)	0.0052 (14)	−0.0017 (16)	−0.0001 (17)
C13	0.055 (2)	0.073 (3)	0.083 (3)	−0.0009 (19)	−0.008 (2)	−0.008 (2)
C14	0.050 (2)	0.072 (3)	0.117 (5)	−0.0076 (19)	−0.003 (2)	−0.001 (3)
C15	0.056 (2)	0.069 (3)	0.107 (4)	−0.009 (2)	0.010 (2)	0.015 (2)
C16	0.062 (2)	0.069 (2)	0.077 (3)	0.0004 (19)	0.009 (2)	0.016 (2)
C17	0.0453 (17)	0.0497 (18)	0.070 (2)	0.0026 (14)	−0.0001 (15)	0.0058 (17)
C18	0.0548 (18)	0.0603 (19)	0.0457 (17)	−0.0032 (15)	0.0027 (15)	0.0074 (16)

Geometric parameters (Å, º) top

Cl01—C18	1.741 (4)	C8—H8	0.9300
O1—C7	1.233 (4)	C9—C18	1.342 (5)
O2—H2A	0.79 (6)	C9—C10	1.527 (5)
O2—H2B	0.96 (6)	C10—C11	1.505 (5)
N6—C7	1.352 (4)	C10—H10A	0.9700
N6—N2	1.378 (4)	C10—H10B	0.9700
N6—H6	0.93 (5)	C11—C12	1.502 (6)
N2—C8	1.280 (4)	C11—H11A	0.9700
C1—C2	1.389 (6)	C11—H11B	0.9700
C1—C6	1.396 (5)	C12—C13	1.390 (6)
C1—H1	0.9300	C12—C17	1.396 (5)
C2—C3	1.365 (7)	C13—C14	1.368 (7)
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.374 (7)	C14—C15	1.352 (7)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.381 (5)	C15—C16	1.385 (7)
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.381 (5)	C16—C17	1.404 (6)
C5—H5	0.9300	C16—H16	0.9300
C6—C7	1.489 (4)	C17—C18	1.472 (5)
C8—C9	1.459 (5)

H2A—O2—H2B	104 (5)	C9—C10—H10A	109.7
C7—N6—N2	118.4 (3)	C11—C10—H10A	109.7
C7—N6—H6	119 (3)	C9—C10—H10B	109.7
N2—N6—H6	122 (3)	C11—C10—H10B	109.7
C8—N2—N6	115.1 (3)	H10A—C10—H10B	108.2
C2—C1—C6	119.8 (4)	C12—C11—C10	113.4 (3)
C2—C1—H1	120.1	C12—C11—H11A	108.9
C6—C1—H1	120.1	C10—C11—H11A	108.9
C3—C2—C1	120.5 (4)	C12—C11—H11B	108.9
C3—C2—H2	119.7	C10—C11—H11B	108.9
C1—C2—H2	119.7	H11A—C11—H11B	107.7
C4—C3—C2	120.1 (4)	C13—C12—C17	118.7 (4)
C4—C3—H3	120.0	C13—C12—C11	122.4 (4)
C2—C3—H3	120.0	C17—C12—C11	118.9 (3)
C3—C4—C5	120.1 (4)	C14—C13—C12	121.2 (5)
C3—C4—H4	119.9	C14—C13—H13	119.4
C5—C4—H4	119.9	C12—C13—H13	119.4
C6—C5—C4	120.7 (4)	C13—C14—C15	120.4 (4)
C6—C5—H5	119.7	C13—C14—H14	119.8
C4—C5—H5	119.7	C15—C14—H14	119.8
C5—C6—C1	118.8 (3)	C14—C15—C16	120.8 (4)
C5—C6—C7	117.5 (3)	C14—C15—H15	119.6
C1—C6—C7	123.6 (3)	C16—C15—H15	119.6
O1—C7—N6	121.7 (3)	C15—C16—C17	119.6 (4)
O1—C7—C6	121.0 (3)	C15—C16—H16	120.2
N6—C7—C6	117.3 (3)	C17—C16—H16	120.2
N2—C8—C9	118.4 (3)	C16—C17—C12	119.4 (4)
N2—C8—H8	120.8	C16—C17—C18	122.8 (4)
C9—C8—H8	120.8	C12—C17—C18	117.9 (3)
C18—C9—C8	122.4 (3)	C9—C18—C17	122.8 (3)
C18—C9—C10	118.5 (3)	C9—C18—Cl01	120.5 (3)
C8—C9—C10	119.1 (3)	C17—C18—Cl01	116.6 (3)
C9—C10—C11	109.9 (3)

C7—N6—N2—C8	174.4 (3)	C10—C11—C12—C13	149.3 (4)
C6—C1—C2—C3	−0.8 (6)	C10—C11—C12—C17	−32.7 (5)
C1—C2—C3—C4	0.9 (7)	C17—C12—C13—C14	1.0 (6)
C2—C3—C4—C5	−0.8 (6)	C11—C12—C13—C14	179.0 (4)
C3—C4—C5—C6	0.7 (6)	C12—C13—C14—C15	−0.4 (7)
C4—C5—C6—C1	−0.7 (5)	C13—C14—C15—C16	−0.7 (8)
C4—C5—C6—C7	−178.7 (3)	C14—C15—C16—C17	1.1 (7)
C2—C1—C6—C5	0.8 (5)	C15—C16—C17—C12	−0.5 (6)
C2—C1—C6—C7	178.6 (3)	C15—C16—C17—C18	−179.1 (4)
N2—N6—C7—O1	0.9 (5)	C13—C12—C17—C16	−0.6 (5)
N2—N6—C7—C6	−178.0 (3)	C11—C12—C17—C16	−178.7 (4)
C5—C6—C7—O1	10.7 (5)	C13—C12—C17—C18	178.2 (4)
C1—C6—C7—O1	−167.2 (3)	C11—C12—C17—C18	0.1 (5)
C5—C6—C7—N6	−170.5 (3)	C8—C9—C18—C17	−175.8 (3)
C1—C6—C7—N6	11.6 (5)	C10—C9—C18—C17	5.0 (5)
N6—N2—C8—C9	−178.7 (3)	C8—C9—C18—Cl01	1.3 (5)
N2—C8—C9—C18	173.5 (3)	C10—C9—C18—Cl01	−177.9 (3)
N2—C8—C9—C10	−7.3 (5)	C16—C17—C18—C9	−166.5 (4)
C18—C9—C10—C11	−36.7 (5)	C12—C17—C18—C9	14.8 (5)
C8—C9—C10—C11	144.1 (3)	C16—C17—C18—Cl01	16.3 (5)
C9—C10—C11—C12	49.2 (5)	C12—C17—C18—Cl01	−162.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱ	0.78 (5)	2.06 (5)	2.829 (4)	166 (5)
O2—H2B···O1	0.96 (6)	1.90 (6)	2.858 (4)	171 (5)
N6—H6···O2ⁱⁱ	0.93 (5)	1.98 (5)	2.869 (4)	159 (4)
C1—H1···O2ⁱⁱ	0.93	2.47	3.350 (5)	158
C8—H8···O2ⁱⁱ	0.93	2.48	3.261 (5)	142

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

List of intermolecular interaction energies (kJ mol^-1) in the crystal of the title compound top

Code	Symmetry	Centroid distance	E_col	E_pol	E_disp	E_rep	E_total	Interaction
A	x, y + 1, z	4.812	-37.4	-14.2	-64.3	88.7	-27.1	O—H···O
B	-x + 1, -y + 1, z - 1/2	7.513	-6.7	-4.3	-20.9	15.9	-16.0	C—H···O
C	-x + 1, -y + 1/2, z	9.210	-2.2	-4.2	-16.1	6.6	-15.9	Cl···H
D	-x + 1/2, y - 1/2, z + 1/2	11.475	-1.9	-0.9	-8.9	3.8	-7.9	H···H
E	x, y, z	5.924	-33.1	-11.6	-12.3	33.1	-23.9	O—H···O
F	x, y - 1, z	4.077	-38.5	-12.0	-13.0	30.7	-32.8	N—H···O

HUMO–LUMO energies and quantum-chemical parameters (eV) for the title compound top

HOMO energy: E_H	-5.7777
LUMO energy: E_L	-2.1428
Energy gap: E_g = E_H - E_L	3.6349
Chemical hardness: η = \|E_H - E_L\|/2	1.8174
Softness: ζ = 1/2η	0.2751
Electrophilicity index: ω = µ²/2η	4.3148
Chemical Potential: µ = -(E_H + E_L/2)	-3.9602
Electronegativity: χ = -µ	3.9602

Acknowledgements

HAA thanks the DBT for support as a Senior Research Fellow and RE thanks DST–PURSE phase II for support as a Research Associate.

Funding information

Funding for this research was provided by: Government of India, the Ministry of Science & Technology, Department of Biotechnology (DBT) (grant No. BT/PR16268/NER/95/183/2015).

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