Crystal structure, Hirshfeld surface analysis and HOMO–LUMO analysis of (E)-N′-(3-hy­droxy-4-meth­oxy­benzyl­idene)nicotinohydrazide monohydrate

Sivajeyanthi, P.; Edison, B.; Balasubramani, K.; Premkumar, G.; Swu, T.

doi:10.1107/S2056989019006492

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ISSN: 2056-9890

Volume 75| Part 6| June 2019| Pages 804-807

https://doi.org/10.1107/S2056989019006492

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Crystal structure, Hirshfeld surface analysis and HOMO–LUMO analysis of (E)-N′-(3-hydroxy-4-methoxybenzylidene)nicotinohydrazide monohydrate

Palaniyappan Sivajeyanthi,^a Bellarmin Edison,^a Kasthuri Balasubramani,^a ^* Ganesan Premkumar ^b and Toka Swu ^b

^aDepartment of Chemistry, Government Arts College (Autonomous), Thanthonimalai, Karur 639 005, Tamil Nadu, India, and ^bDepartment of Chemistry, Pondicherry University, R.V. Nagar, Kalapet, Puducherry 605 014, India
^*Correspondence e-mail: manavaibala@gmail.com

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 4 February 2019; accepted 7 May 2019; online 14 May 2019)

The molecule of the title Schiff base compound, C₁₄H₁₃N₃O₃·H₂O, displays a trans configuration with respect to the C=N bond. The dihedral angle between the benzene and pyridine rings is 29.63 (7)°. The crystal structure features intermolecular N—H⋯O, C—H⋯O, O—H⋯O and O—H⋯N hydrogen-bonding interactions, leading to the formation of a supramolecular framework. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯H (37.0%), O⋯H/H⋯O (23.7%)), C⋯H/H⋯C (17.6%) and N⋯H/H⋯N (11.9%) interactions. The title compound has also been characterized by frontier molecular orbital analysis.

Keywords: crystal structure; Schiff base; intermolecular interactions; Hirshfeld surface analysis.

CCDC reference: 1587259

1. Chemical context

Schiff bases are nitrogen-containing compounds that were first obtained by the condensation reaction of aromatic amines and aldehydes (Schiff, 1864 ). A wide range of these compounds, with the general formula RHC=NR₁ (R and R₁ can be alkyl, aryl, cycloalkyl or heterocyclic groups) have been synthesized. Schiff bases are of great importance in the field of coordination chemistry because they are able to form stable complexes with metal ions (Souza et al., 1985 ). The chemical and biological significance of Schiff bases can be attributed to the presence of a lone electron pair in the sp²-hybridized orbital of the nitrogen atom of the azomethine group (Singh et al., 1975 ). These compounds are used in the fields of organic synthesis, chemical catalysis, medicine and pharmacy, as well as other new technologies (Tanaka et al., 2010 ). Schiff bases are also used as probes for investigating the structure of DNA (Tiwari et al., 2011 ) and have gained special attention in pharmacophore research and in the development of several bioactive lead molecules (Muralisankar et al., 2016 ). Schiff bases showing photochromic and thermochromic properties have been used in information storage, electronic display systems, optical switching devices and ophthalmic glasses (Amimoto et al., 2005 ). As a further contribution to this field of research, we report herein the crystal structure of the title compound, (E)-N′-(3-hydroxy-4-methoxybenzylidene)nicotinohydrazide monohydrate.

2. Structural commentary

The asymmetric unit of the title compound (Fig. 1) consists of one independent Schiff base molecule displaying a trans configuration with respect to the C=N bond and a water molecule. All the bond lengths are within the normal ranges (Allen et al., 1987 ). The C7=N3 bond length of 1.274 (2) Å is consistent with a double-bond character. The C6—N2 and N2—N3 bond lengths of 1.343 (2) and 1.3866 (16) Å, respectively, are comparable to those observed in related compounds (Sivajeyanthi et al., 2017 ; Balasubramani et al., 2018 ). The O1/C6/N2/N3/C7 core is almost planar (r.m.s. deviation = 0.022 Å) and forms dihedral angles of 20.75 (7) and 8.93 (5)°, respectively, with the pyridine and benzene rings.

Figure 1
The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level..

3. Supramolecular features

In the crystal of the title compound (Fig. 2), the water molecule interacts with three neighbouring nicotinohydrazide molecules with the O4 water oxygen atom acting as a hydrogen acceptor through N2—H2N⋯O4 and C2—H2⋯O4 hydrogen bonds (Table 1), and both water H atoms acting as bifurcated donors to form rings of R₂¹(5) graph-set motif. The nicotinohydrazide molecules are further linked by O—H⋯N and C—H⋯O hydrogen bonds to form a three-dimensional network.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4WA⋯O2ⁱ	0.85	2.28	3.0483 (17)	150
O4—H4WA⋯O3ⁱ	0.85	2.49	3.2011 (16)	141
O4—H4WB⋯O1ⁱⁱ	0.85	2.08	2.8429 (19)	150
O4—H4WB⋯N3ⁱⁱ	0.85	2.50	3.1875 (18)	139
N2—H2N⋯O4	0.86	2.06	2.8889 (18)	162
O2—H10⋯N1ⁱⁱⁱ	0.82	1.96	2.7411 (17)	159
C2—H2⋯O4	0.93	2.25	3.129 (2)	156
C4—H4⋯O3^iv	0.93	2.45	3.347 (2)	163
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x+2, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Crystal packing of the title compound, viewed down the a axis. Hydrogen bonds are shown as dashed lines.

4. Hirshfeld surface analysis

The three-dimensional d_norm surface is a useful tool for analysing and visualizing the intermolecular interactions, as it shows negative or positive values depending on whether an intermolecular contact is shorter or longer, respectively, than the sum of the van der Waals radii (Spackman & Jayatilaka, 2009 ; McKinnon et al., 2007 ). The d_norm surface of the title compound is shown in Fig. 3. The red points, which represent closer contacts and negative d_norm values, correspond to the N—H⋯O, O—H⋯O, O—H⋯N and C—H⋯O interactions. Two-dimensional fingerprint plots from the Hirshfeld surface analysis (Fig. 4) provide information about the intermolecular contacts and their percentage distributions on the Hirshfeld surface. The percentage of H⋯H contacts as closest contacts on the Hirshfeld surfaces is a universally applicable measure of the crystal lattice energy and can be used as a reference for the importance of other types of contacts. In the title compound, the percentage contributions of the various intermolecular contacts to the total Hirshfeld surface are as follows: H⋯H (37.0%), C⋯H/H⋯C (17.6%), N⋯H/H⋯N (11.9%), C⋯N/N⋯C (3.7%), O⋯H/H⋯O (23.7%), C⋯C (4.5%), N⋯N (0.3%) and O⋯C/C⋯O (1.2%).

Figure 3
Hirshfeld surfaces of the title compound mapped over d_norm.

Figure 4
Two-dimensional fingerprint plots for the title compound and relative contributions of the atom pairs to the Hirshfeld surface.

5. Frontier molecular orbitals

The HOMO (highest occupied molecular orbital) acts as an electron donor and LUMO (lowest occupied molecular orbital) acts as an electron acceptor. If the HOMO–LUMO energy gap is small, then the molecule is highly polarizable and has high chemical reactivity. The energy levels for the title compound were computed by DFT-B3LYP/6-311G++(d,p) method (Sivajeyanthi et al., 2017). The energy levels, energy gaps, chemical hardness, chemical potential, electronegativity and electrophilicity index are given in Table 2. As shown in Fig. 5, the frontier molecular orbital LUMO is located over the whole of the molecule. The energy gap of the molecule clearly shows the charge-transfer interaction involving donor and acceptor groups. If the HOMO–LUMO energy gap is small, then the molecule is defined as soft, i.e. it is highly polarizable and has high chemical reactivity, whereas if the energy gap is large the molecule can be defined as hard. Therefore from Table 2 we conclude that the title molecule belongs to the really hard materials.

Table 2
Calculated frontier molecular orbital energies (eV)

FMO	Energy
E_HOMO	−5.7171
E_LUMO	−1.8174
E_HOMO−1	−6.5750
E_LUMO+1	−1.2770
(E_HOMO − E_LUMO) gap	3.8997
(E_HOMO−1 − E_LUMO+1) gap	5.2980
Chemical hardness	1.9498
Chemical potential	3.7672
Electronegativity	−3.7672
Electrophilicity index	3.6393

Figure 5
Molecular orbital energy levels of the title compound.

6. Database survey

A search of the Cambridge Structural Database (Version 5.40, update November 2018; Groom et al., 2016 ) for uncoordinated N′-(benzylidene)nicotinohydrazide derivatives O-substituted at the 3,4 positions of the benzene ring yielded three hits, namely N′-(1,3-benzodioxol-5-ylmethylene)nicotinohydrazide monohydrate (refcode BUDNIY; Bao et al., 2009 ), N′-(3,4-dimethoxybenzylidene)nicotinohydrazide monohydrate (XODZOH; Novina et al., 2014 ) and the isomer N′-(4-hydroxy-3-methoxybenzylidene)nicotinohydrazide monohydrate (SEZREV; Shi et al., 2007 ). The conformation of the last molecule differs from the title compound mainly in the relative orientation of the pyridine ring with respect to the carbonyl group, as indicated by the value of 158.03 (15)° for the O1—C6—C1—C2 torsion angle in the title compound and of 10.2 (3)° for the corresponding angle in SEZREV. Moreover, in SEZREV the water molecule acts as acceptor of three H atoms from the same nicotinohydrazide molecule and as donor in two O—H⋯O hydrogen bonds.

7. Synthesis and crystallization

The title compound was synthesized by the reaction of a 1:1 molar ratio mixture of a hot ethanolic solution (20 ml) of nicotinohydrazide (0.137 mg) and a hot ethanolic solution of 3-hydroxy-4-methoxy benzaldehyde (0.152 mg). After refluxing for 8 h, the solution was then cooled and kept at room temperature to precipitate. Colourless block-shaped crystals suitable for X-ray analysis were obtained by slow evaporation of a 10 ml dimethyl sulfoxide/water (1:1 v/v) solution.

8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were positioned geometrically (O—H = 0.82 Å, N–H = 0.86 Å, C—H = 0.93–0.96 Å) and refined as riding with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(O, C-methyl)

Table 3
Experimental details

Crystal data
Chemical formula	C₁₄H₁₃N₃O₃·H₂O
M_r	289.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	7.1153 (4), 11.0075 (6), 18.2771 (10)
β (°)	105.766 (5)
V (Å³)	1377.64 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.25 × 0.18

Data collection
Diffractometer	Agilent Xcalibur Eos
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012 )
T_min, T_max	0.969, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	8396, 2549, 2027
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.101, 1.04
No. of reflections	2549
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.13
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008 ), SHELXL2017 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2006 ).

Supporting information

CCDC reference: 1587259

Crystal structure: contains datablocks global, I, 1. DOI: https://doi.org/10.1107/S2056989019006492/rz5252sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019006492/rz5252Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019006492/rz5252Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2017 (Sheldrick, 2015).

(E)-N'-(3-Hydroxy-4-methoxybenzylidene)nicotinohydrazide monohydrate top

Crystal data top

C₁₄H₁₃N₃O₃·H₂O	F(000) = 608
M_r = 289.29	D_x = 1.395 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.1153 (4) Å	Cell parameters from 3729 reflections
b = 11.0075 (6) Å	θ = 3.9–29.2°
c = 18.2771 (10) Å	µ = 0.10 mm⁻¹
β = 105.766 (5)°	T = 295 K
V = 1377.64 (14) Å³	Block, colourless
Z = 4	0.30 × 0.25 × 0.18 mm

Data collection top

Agilent Xcalibur Eos diffractometer	2549 independent reflections
Radiation source: fine-focus sealed tube	2027 reflections with I > 2σ(I)
Detector resolution: 15.9821 pixels mm^-1	R_int = 0.027
ω scans	θ_max = 25.5°, θ_min = 3.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −8→8
T_min = 0.969, T_max = 0.981	k = −13→12
8396 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0462P)² + 0.2987P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2549 reflections	Δρ_max = 0.16 e Å⁻³
192 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints	Extinction correction: SHELXL2017 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.030 (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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O3	−0.03769 (14)	0.40424 (10)	0.06695 (6)	0.0455 (3)
O2	0.20750 (15)	0.23383 (10)	0.06507 (7)	0.0537 (3)
H10	0.287088	0.178188	0.073527	0.081*
O1	1.15498 (17)	0.21431 (11)	0.30304 (8)	0.0604 (4)
N3	0.85559 (17)	0.37007 (12)	0.26300 (7)	0.0418 (3)
N2	1.03456 (17)	0.40123 (12)	0.31206 (7)	0.0410 (3)
H2N	1.053128	0.472235	0.332397	0.049*
N1	1.61018 (19)	0.51282 (12)	0.42610 (8)	0.0452 (4)
C8	0.5291 (2)	0.43898 (15)	0.20366 (8)	0.0371 (4)
C9	0.4682 (2)	0.33704 (14)	0.15750 (8)	0.0384 (4)
H9	0.555924	0.274429	0.157443	0.046*
C10	0.2791 (2)	0.32888 (14)	0.11216 (8)	0.0372 (4)
C11	0.1465 (2)	0.42290 (14)	0.11294 (8)	0.0355 (4)
C12	0.2059 (2)	0.52410 (15)	0.15746 (9)	0.0409 (4)
H12	0.118419	0.586791	0.157676	0.049*
C13	0.3972 (2)	0.53171 (15)	0.20196 (9)	0.0423 (4)
H13	0.437730	0.600772	0.231319	0.051*
C14	−0.1795 (2)	0.49637 (17)	0.06553 (10)	0.0492 (4)
H14A	−0.192906	0.508196	0.115902	0.074*
H14B	−0.302791	0.472017	0.032256	0.074*
H14C	−0.138193	0.570937	0.047468	0.074*
C7	0.7260 (2)	0.45278 (15)	0.25379 (8)	0.0411 (4)
H7	0.758441	0.525352	0.280265	0.049*
C6	1.1785 (2)	0.31829 (14)	0.32729 (9)	0.0390 (4)
C2	1.4323 (2)	0.47808 (14)	0.38578 (8)	0.0387 (4)
H2	1.343594	0.537888	0.362746	0.046*
C1	1.3728 (2)	0.35815 (13)	0.37638 (8)	0.0354 (4)
C5	1.5059 (2)	0.27035 (15)	0.41019 (10)	0.0502 (4)
H5	1.472088	0.188603	0.404400	0.060*
C4	1.6891 (2)	0.30435 (17)	0.45260 (11)	0.0599 (5)
H4	1.780614	0.246398	0.476287	0.072*
C3	1.7334 (2)	0.42511 (17)	0.45907 (10)	0.0533 (5)
H3	1.857046	0.447633	0.488254	0.064*
O4	1.07802 (17)	0.65762 (11)	0.34578 (7)	0.0594 (4)
H4WA	1.034030	0.696974	0.377588	0.089*
H4WB	1.043530	0.692674	0.302788	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0286 (5)	0.0448 (7)	0.0558 (7)	0.0044 (5)	−0.0009 (5)	−0.0023 (5)
O2	0.0385 (6)	0.0378 (6)	0.0712 (8)	0.0062 (5)	−0.0085 (5)	−0.0115 (6)
O1	0.0513 (7)	0.0382 (7)	0.0744 (9)	−0.0022 (5)	−0.0127 (6)	−0.0079 (6)
N3	0.0309 (6)	0.0455 (8)	0.0416 (7)	−0.0061 (6)	−0.0029 (5)	0.0026 (6)
N2	0.0311 (6)	0.0390 (7)	0.0448 (7)	−0.0032 (6)	−0.0037 (5)	−0.0026 (6)
N1	0.0361 (7)	0.0419 (8)	0.0509 (8)	−0.0062 (6)	0.0006 (6)	0.0030 (6)
C8	0.0317 (7)	0.0424 (9)	0.0351 (8)	−0.0033 (7)	0.0054 (6)	0.0051 (7)
C9	0.0306 (7)	0.0373 (8)	0.0437 (8)	0.0036 (6)	0.0039 (6)	0.0062 (7)
C10	0.0343 (8)	0.0327 (8)	0.0408 (8)	−0.0019 (6)	0.0038 (6)	0.0024 (7)
C11	0.0281 (7)	0.0388 (9)	0.0369 (8)	−0.0003 (6)	0.0039 (6)	0.0052 (7)
C12	0.0369 (8)	0.0403 (9)	0.0435 (8)	0.0051 (7)	0.0073 (6)	−0.0004 (7)
C13	0.0399 (8)	0.0422 (9)	0.0412 (8)	−0.0020 (7)	0.0049 (7)	−0.0052 (7)
C14	0.0325 (8)	0.0598 (11)	0.0520 (10)	0.0118 (8)	0.0056 (7)	0.0013 (8)
C7	0.0348 (8)	0.0446 (9)	0.0397 (8)	−0.0055 (7)	0.0030 (6)	0.0012 (7)
C6	0.0370 (8)	0.0345 (9)	0.0398 (8)	−0.0047 (7)	0.0007 (6)	0.0025 (7)
C2	0.0320 (8)	0.0364 (8)	0.0432 (8)	−0.0003 (6)	0.0023 (6)	0.0041 (7)
C1	0.0321 (7)	0.0359 (8)	0.0345 (7)	−0.0008 (6)	0.0026 (6)	0.0024 (6)
C5	0.0457 (9)	0.0361 (9)	0.0580 (10)	−0.0003 (7)	−0.0041 (8)	0.0050 (8)
C4	0.0432 (10)	0.0477 (11)	0.0728 (13)	0.0060 (8)	−0.0114 (9)	0.0120 (9)
C3	0.0328 (8)	0.0540 (11)	0.0611 (11)	−0.0043 (8)	−0.0075 (7)	0.0063 (9)
O4	0.0627 (8)	0.0475 (7)	0.0583 (7)	0.0186 (6)	−0.0002 (6)	−0.0017 (6)

Geometric parameters (Å, º) top

O3—C11	1.3664 (17)	C12—C13	1.386 (2)
O3—C14	1.4257 (19)	C12—H12	0.9300
O2—C10	1.3627 (18)	C13—H13	0.9300
O2—H10	0.8198	C14—H14A	0.9600
O1—C6	1.2223 (19)	C14—H14B	0.9600
N3—C7	1.274 (2)	C14—H14C	0.9600
N3—N2	1.3866 (16)	C7—H7	0.9300
N2—C6	1.343 (2)	C6—C1	1.4950 (19)
N2—H2N	0.8602	C2—C1	1.383 (2)
N1—C3	1.333 (2)	C2—H2	0.9300
N1—C2	1.3355 (19)	C1—C5	1.376 (2)
C8—C13	1.381 (2)	C5—C4	1.376 (2)
C8—C9	1.400 (2)	C5—H5	0.9300
C8—C7	1.459 (2)	C4—C3	1.364 (3)
C9—C10	1.378 (2)	C4—H4	0.9300
C9—H9	0.9300	C3—H3	0.9300
C10—C11	1.404 (2)	O4—H4WA	0.8500
C11—C12	1.377 (2)	O4—H4WB	0.8495

C11—O3—C14	117.37 (12)	H14A—C14—H14B	109.5
C10—O2—H10	109.5	O3—C14—H14C	109.5
C7—N3—N2	114.41 (13)	H14A—C14—H14C	109.5
C6—N2—N3	118.71 (13)	H14B—C14—H14C	109.5
C6—N2—H2N	120.6	N3—C7—C8	123.07 (15)
N3—N2—H2N	120.7	N3—C7—H7	118.5
C3—N1—C2	116.76 (14)	C8—C7—H7	118.5
C13—C8—C9	118.80 (13)	O1—C6—N2	122.66 (13)
C13—C8—C7	117.90 (14)	O1—C6—C1	120.37 (14)
C9—C8—C7	123.31 (14)	N2—C6—C1	116.97 (13)
C10—C9—C8	120.43 (14)	N1—C2—C1	123.65 (14)
C10—C9—H9	119.8	N1—C2—H2	118.2
C8—C9—H9	119.8	C1—C2—H2	118.2
O2—C10—C9	124.50 (13)	C5—C1—C2	117.67 (13)
O2—C10—C11	115.81 (12)	C5—C1—C6	118.33 (14)
C9—C10—C11	119.69 (14)	C2—C1—C6	123.84 (13)
O3—C11—C12	125.07 (13)	C4—C5—C1	119.55 (15)
O3—C11—C10	114.71 (13)	C4—C5—H5	120.2
C12—C11—C10	120.22 (13)	C1—C5—H5	120.2
C11—C12—C13	119.40 (14)	C3—C4—C5	118.38 (15)
C11—C12—H12	120.3	C3—C4—H4	120.8
C13—C12—H12	120.3	C5—C4—H4	120.8
C8—C13—C12	121.44 (15)	N1—C3—C4	123.96 (15)
C8—C13—H13	119.3	N1—C3—H3	118.0
C12—C13—H13	119.3	C4—C3—H3	118.0
O3—C14—H14A	109.5	H4WA—O4—H4WB	109.5
O3—C14—H14B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4WA···O2ⁱ	0.85	2.28	3.0483 (17)	150
O4—H4WA···O3ⁱ	0.85	2.49	3.2011 (16)	141
O4—H4WB···O1ⁱⁱ	0.85	2.08	2.8429 (19)	150
O4—H4WB···N3ⁱⁱ	0.85	2.50	3.1875 (18)	139
N2—H2N···O4	0.86	2.06	2.8889 (18)	162
O2—H10···N1ⁱⁱⁱ	0.82	1.96	2.7411 (17)	159
C2—H2···O4	0.93	2.25	3.129 (2)	156
C4—H4···O3^iv	0.93	2.45	3.347 (2)	163

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

Calculated frontier molecular orbital energies (eV) top

FMO	Energy
E_HOMO	-5.7171
E_LUMO	-1.8174
E_HOMO-1	-6.5750
E_LUMO+1	-1.2770
(E_HOMO - E_LUMO) gap	3.8997
(E_HOMO-1 - E_LUMO+1) gap	5.2980
Chemical hardness	1.9498
Chemical potential	3.7672
Electronegativity	-3.7672
Electrophilicity index	3.6393

Funding information

KB and PS thank the Department of Science and Technology (DST–SERB), New Delhi, India, grant No. SB/FT/CS-058/2013, for financial support.

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