Synthesis, crystal structure at 219 K and Hirshfeld surface analyses of 1,4,6-tri­methyl­quinoxaline-2,3(1H,4H)-dione monohydrate

Zouitini, A.; Faizi, M.S.H.; Ouzidan, Y.; Ouazzani Chahdi, F.; Marrot, J.; Prim, D.; Dege, N.; Mashrai, A.

doi:10.1107/S2056989020009573

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ISSN: 2056-9890

Volume 76| Part 8| August 2020| Pages 1296-1301

https://doi.org/10.1107/S2056989020009573

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Synthesis, crystal structure at 219 K and Hirshfeld surface analyses of 1,4,6-trimethylquinoxaline-2,3(1H,4H)-dione monohydrate

Ayman Zouitini,^a Md. Serajul Haque Faizi,^b Younes Ouzidan,^c Fouad Ouazzani Chahdi,^a Jérôme Marrot,^d Damien Prim,^d Necmi Dege ^e and Ashraf Mashrai ^f ^*

^aLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, BP 2202, Fez, Morocco, ^bDepartment of Chemistry, Langat Singh College, B.R.A. Bihar University, Muzaffarpur, Bihar-842001, India, ^cLaboratoire de Chimie Physique et Chimie Bio-organique, Faculté des Sciences et Techniques Mohammedia, Université Hassan II, Casablanca, BP 146, 28800, Mohammedia, Morocco, ^dInstitut Lavoisier de Versailles, UVSQ, CNRS, Université Paris-Saclay, 78035 Versailles, France, ^eDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, Samsun, 55200, Turkey, and ^fDepartment of Pharmacy, University of Science and Technology, Ibb Branch, Ibb, Yemen
^*Correspondence e-mail: ashraf.yemen7@gmail.com

Edited by A. V. Yatsenko, Moscow State University, Russia (Received 17 June 2020; accepted 13 July 2020; online 17 July 2020)

The asymmetric unit of the title compound, C₁₁H₁₂N₂O₂·H₂O, contains a molecule of 1,4,6-trimethyl-1,4-dihydroquinoxaline-2,3-dione and a solvent water molecule. Four atoms of the benzene ring are disordered over two sets of sites in a 0.706 (7):0.294 (7) ratio while the N-bound methyl groups are rotationally disordered with occupancy ratios of 0.78 (4):0.22 (4) and 0.76 (5):0.24 (5). In the crystal, molecules are linked by O—H⋯O and C—H⋯O hydrogen bonds into layers lying parallel to (10 $[\overline{1}]$ ). The Hirshfeld surface analysis indicates that the most important contributions to the packing arrangement are due to H⋯H (51.3%) and O⋯H/H⋯O (28.6%) interactions. The molecular structure calculated by density functional theory is compared with the experimentally determined molecular structure, and the HOMO–LUMO energy gap has been calculated.

Keywords: crystal structure; quinoxaline-2,3-dione; Hirshfeld surface analysis; disorder; hydrogen bonding.

CCDC reference: 1936663

1. Chemical context

Quinoxalines are well-known important nitrogen-containing heterocyclic compounds with fused benzene and pyrazine rings. Quinoxalines and their derivatives display various pharmacological and biological activities, such as anticancer (Carta et al., 2006 ), antidiabetic (Bahekar et al., 2007 ), antiviral (Fonseca et al., 2004 ), antibacterial (El-Sabbagh et al., 2009 ), anti-inflammatory (Wagle et al., 2008 ) and antiprotozoal (Hui et al., 2006 ). The present work is a part of an ongoing structural study of quinoxaline derivatives (Faizi & Parashchenko 2015 ; Faizi et al., 2015 , 2018 ).

As a continuation of our research devoted to the synthesis and applications of new heterocyclic compounds obtained by N-alkylation reactions (Tribak et al., 2017 ; Qachchachi et al., 2016 ; Belaziz et al., 2012 ), we report here the synthesis of 1,4,6-trimethylquinoxaline-2,3(1H,4H)-dione obtained by the action of iodomethane on 6-methylquinoxaline-2,3(1H,4H)-dione, and the crystal structure of its monohydrate derivative along with the Hirshfeld surface analysis. The experimentally determined molecular structure is compared with that calculated at the DFT/B3LYP/6-311 G(d,p) level.

2. Structural commentary

The title compound crystallizes in space group P2₁/n with one quinoxaline and one water molecule per asymmetric unit. The organic molecule is disordered over two sets of sites with an occupancy ratio of 0.706 (7):0.294 (7). The disorder involves not only the orientation of the methyl group attached to the benzene ring, but also the positions of four carbon atoms of this ring, which are split (Fig. 1). Only the predominant orientation of the 1,4,6-trimethylquinoxaline-2,3(1H,4H)-dione molecule is discussed below. Besides this, the methyl groups attached to N1 and N2 nitrogen atoms are also rotationally disordered with occupancy ratios of 0.78 (4):0.22 (4) and 0.76 (5):0.24 (5), respectively. The quinoxaline ring system is essentially planar, the largest deviation from the mean plane being 0.015 (3) Å for the N2 atom. The C=O and Csp²—N bond lengths are typical of such type of compounds and indicate strong conjugation in the amide fragments.

Figure 1
The asymmetric unit of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 40% probability level. O—H⋯O hydrogen bonds are indicated by dashed lines. The benzene fragment of the organic molecule, C2/C3/C4/C5/C7, is disordered over two sets of sites.

3. Supramolecular features

In the crystal, molecules are linked by O—H⋯O and C—H⋯O hydrogen bonds (Table 1) into double layers lying parallel to (10 $[\overline{1}]$ ). The smallest element of the hydrogen-bonding motif, where the R₄²(8) rings are formed, is shown in Fig. 2, whereas the whole packing diagram is presented in Fig. 3. The water molecule behaves both as a donor and an acceptor of hydrogen atoms in the hydrogen bonds. As seen in Fig. 3, in centrosymmetric pairs of organic molecules, the aromatic and heterocyclic rings overlap with each other with an intercentroid distance of 3.522 (4) Å, indicating that some π–π interactions occur.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O1	0.86	2.09	2.936 (4)	170
O3—H3C⋯O1ⁱ	0.86	2.38	3.062 (4)	137
O3—H3C⋯O2ⁱ	0.86	2.19	2.972 (5)	150
C5A—H5A⋯O3ⁱⁱ	0.94	2.40	3.298 (13)	160
C8—H8E⋯O2ⁱⁱⁱ	0.97	2.45	3.335 (4)	151
Symmetry codes: (i) -x+1, -y+3, -z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A view along the a axis of a hydrogen-bonded fragment. The O—H⋯O and C—H⋯O hydrogen bonds (shown as dashed lines) form an R₄²(8) ring motif.

Figure 3
Packing diagram of the title compound viewed along the a-axis direction. Only the major disorder component is shown.

4. Hirshfeld surface analysis

The intermolecular interactions were investigated quantitatively and visualized with Crystal Explorer 17.5 (Turner et al., 2017 ; Spackman et al., 2009 ). The d_norm, water interaction, curvedness and 2D finger print plots are depicted in Fig. 4a–c and 5a–h, respectively. The red spots on the Hirshfeld surface represent O—H⋯O contacts while the blue regions correspond to weak interactions such as C—H⋯O contacts. The H⋯H interactions (51.3%) are the major factor in the crystal packing with O⋯H/H⋯O interactions (28.6%) representing the next highest contribution. The percentage contributions of other weak interactions are: C⋯C (8.2%), C⋯H/H⋯C (5.8%), C⋯N/N⋯C (4.5%), N⋯H/H⋯N (1.1%) and O⋯C/C⋯O (0.5%).

Figure 4
Views of the three-dimensional Hirshfeld surface for the title compound plotted over (a, b) d_norm and (c) shape-index.

Figure 5
Two-dimensional fingerprint plots showing (a) all interactions and those delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) C⋯C, (e) C⋯H/H⋯C, (f) C⋯N/N⋯C,(g) N⋯H/H⋯N and (h) O⋯C/C⋯O.

5. DFT calculations

The structure of the title organic molecule was optimized in the gas-phase approximation at the level of density functional theory (DFT) using the B3LYP functional (Becke, 1993 ) and 6-311 G(d,p) basis set as implemented in GAUSSIAN 09 (Frisch et al., 2009 ). The theoretical and experimental bond lengths and angles are in good agreement (Table 2). The energetic and spatial characteristics of the highest occupied molecular orbital (HOMO), acting as an electron donor, and the lowest unoccupied molecular orbital (LUMO), acting as an electron acceptor, are very important parameters for quantum chemistry. When the energy gap is small, the molecule is highly polarizable and has high chemical reactivity (Fukui, 1982 ; Khan et al., 2015 ). The DFT calculations provide some important information on the reactivity and site selectivity of the molecular framework, E_HOMO and E_LUMO, electronegativity (χ), hardness (η), electrophilicity (ω), softness (σ) and fraction of electrons transferred (ΔN). These data are given in Table 3. The parameters η and σ are significant for evaluation of both the reactivity and stability. The electron transition from HOMO to LUMO is shown in Fig. 6. The HOMO and LUMO are localized in the plane of the whole 1,4,6-trimethylquinoxaline-2,3(1H,4H)-dione bicyclic ring system. The energy gap [ΔE = E_LUMO − E_HOMO] of the molecule is 4.6907 eV, the frontier molecular orbital energies E_HOMO and E_LUMO being −6.1139 eV and −1.4232 eV, respectively. The dipole moment of (I) is estimated to be 5.56 Debye.

Table 2
Comparison of observed (X-ray data) and calculated (DFT) geometric parameters (Å, °)

Parameter	X-ray	B3LYP/6–311G(d,p)
O1—C9	1.228 (4)	1.217
O2—C10	1.226 (4)	1.211
N1—C6	1.401 (4)	1.407
N1—C8	1.470 (4)	1.468
N1—C9	1.351 (4)	1.375
N2—C1	1.409 (4)	1.375
N2—C10	1.365 (5)	1.384
N2—C11	1.458 (5)	1.464
O1—C9—N1	123.5 (3)	123.9
O2—C10—N2	122.8 (3)	123.4
O1—C9—C10	118.3 (3)	118.3

Table 3
DFT-calculated molecular characteristics for the title compound

Total Energy, TE (eV)	−20757.4747
E_HOMO (eV)	−6.1139
E_LUMO (eV)	−1.4232
Gap, ΔE (eV)	4.6907
Dipole moment, μ (D)	5.56
Ionization potential, I (eV)	6.1139
Electron affinity, A (eV)	1.4232
Electronegativity, χ	3.929
Hardness, η	2.345
Electrophilicity index, ω	3.291
Softness, σ	0.213
Fraction of electron transferred, ΔN	0.655

Figure 6
Frontier molecular orbitals of the 1,4,6-trimethylquinoxaline-2,3(1H,4H)-dione molecule.

6. Database survey

A search of the Cambridge Structural Database (CSD, version 5.39; Groom et al., 2016 ) gave nine hits for the 1,4,6-trimethylquinoxaline-2,3(1H,4H)-dione moiety. Two of them are metal complexes, bis(μ₂-nitrato-O,O,O′)-bis[1,4-bis(N,N- diisopropyl-acetamido)quinoxaline-2,3-dione-O,O′]tetrakis(nitrato-O,O′)diaquadineodymium(III) monohydrate (WIKSOZ; Song et al., 2007 ) and catena-(μ₂-iodo)-bis(1,4-dimethylquinoxalin-2,3-dionato)potassium (FADQOS; Benali et al., 2008 ). Seven organic compounds similar to the title compound are reported in the literature. In 1,4-dihexyl-1,4-dihydroquinoxaline-2,3-dione (FECROX; El Bourakadi et al., 2017a ), the methyl groups attached to the N atoms are replaced by hexyl groups. In 1,4-diallylquinoxaline-2,3(1H,4H)-dione (GURGAB; Mustaphi et al., 2001 ), the allyl groups are bound to the N atoms. In 1-ethyl-4-phenylethyl-1,4-dihydroquinoxaline-2,3-dione (IXATOQ; Akkurt et al., 2004 ), one N atom is bound to an ethyl group, and the other to an ethylphenyl group. In 6-methyl-1,4-bis[(pyridin-2-yl)methyl]-1,4-dihydroquinoxaline-2,3-dione (KELMIA; Zouitini et al., 2017 ), methylpyridinyl groups are attached to both N atoms. In 1,4-dibenzyl-6-chloro-1,4-dihydroquinoxaline-2,3-dione (PAWFEB; El Janati et al., 2017a ), the N atoms are attached to the benzyl groups, and the methyl group on the benzene ring is substituted by chlorine. In 1,4-dioctyl-1,4-dihydroquinoxaline-2,3-dione (WAPWAO; El Bourakadi et al., 2017b ), octyl groups are attached to the N atoms. In 6-chloro-1,4-diethyl-1,4-dihydroquinoxaline-2,3-dione (XEFMON; El Janati et al., 2017b ), the ethyl groups are attached to the N atoms, and the methyl group on the benzene ring is substituted by chlorine, as in PAWFEB. None of these structures contains solvent molecules.

7. Synthesis and crystallization

To a solution of 6-methyl-1,4-dihydroquinoxaline-2,3-dione (0.3 g, 1.73 mmol) in DMF (15 ml) potassium carbonate (0.47 g, 3.61 mmol) and tetra-n-butylammonium (0.07g, 0.23 mmol) were added. After 10 min of stirring, 0.27 ml (4.32 mmol) of iodomethane were added, and the mixture was stirred at room temperature for 6 h. The inorganic salts were filtered off, DMF was evaporated under reduced pressure and the residue was dissolved in dichloromethane. The organic phase was dried over Na₂SO₄ and then concentrated. The crude product was purified by chromatography on a silica gel column [eluent: hexane/ethylacetate (2/1)].

8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. Water molecules were refined as rigid groups with U_iso(H) = 1.5U_eq(O). Other H atoms were positioned geometrically, with C—H = 0.94 and 0.97 Å for aromatic and aliphatic H atoms, respectively, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C) or U_iso(H) = 1.5U_eq(C-methyl). The disorder of the organic molecule was taken into account using free variables.

Table 4
Experimental details

Crystal data
Chemical formula	C₁₁H₁₂N₂O₂·H₂O
M_r	222.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	219
a, b, c (Å)	7.0695 (4), 10.8321 (5), 14.4349 (6)
β (°)	101.556 (3)
V (Å³)	1082.98 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.18 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
No. of measured, independent and observed [I > 2σ(I)] reflections	32798, 1935, 1563
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.147, 1.24
No. of reflections	1935
No. of parameters	201
No. of restraints	30
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.18
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ), Mercury (Macrae et al., 2020 ), WinGX (Farrugia, 2012 ), PLATON (Spek, 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1936663

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009573/yk2133sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009573/yk2133Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2020); software used to prepare material for publication: WinGX (Farrugia, 2012), PLATON (Spek, 2020) and publCIF (Westrip, 2010).

1,4,6-Trimethylquinoxaline-2,3(1H,4H)-dione monohydrate top

Crystal data top

C₁₁H₁₂N₂O₂·H₂O	F(000) = 472
M_r = 222.24	D_x = 1.363 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.0695 (4) Å	Cell parameters from 7373 reflections
b = 10.8321 (5) Å	θ = 2.4–24.7°
c = 14.4349 (6) Å	µ = 0.10 mm⁻¹
β = 101.556 (3)°	T = 219 K
V = 1082.98 (9) Å³	Parallelepiped, yellow
Z = 4	0.30 × 0.18 × 0.04 mm

Data collection top

Bruker APEXII CCD diffractometer	1563 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.062
φ and ω scans	θ_max = 25.2°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −8→8
	k = −12→12
32798 measured reflections	l = −17→17
1935 independent 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)] = 0.067	H-atom parameters constrained
wR(F²) = 0.147	w = 1/[σ²(F_o²) + (0.0097P)² + 1.8308P] where P = (F_o² + 2F_c²)/3
S = 1.24	(Δ/σ)_max < 0.001
1935 reflections	Δρ_max = 0.21 e Å⁻³
201 parameters	Δρ_min = −0.18 e Å⁻³
30 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0031 (9)

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	Occ. (<1)
O1	0.3712 (4)	1.3409 (2)	0.00205 (17)	0.0479 (7)
O2	0.3853 (4)	1.2710 (3)	0.18106 (17)	0.0581 (8)
C1	0.2612 (4)	0.9861 (3)	0.0618 (3)	0.0409 (8)
C2A	0.2177 (14)	0.8598 (10)	0.0725 (6)	0.034 (2)	0.706 (7)
H2A	0.219201	0.830335	0.133895	0.041*	0.706 (7)
C2B	0.228 (5)	0.879 (3)	0.1074 (16)	0.048 (7)	0.294 (7)
H2B	0.237848	0.867991	0.172811	0.057*	0.294 (7)
C3A	0.1723 (13)	0.7756 (12)	−0.0031 (7)	0.037 (2)	0.706 (7)
C3B	0.175 (4)	0.788 (3)	0.0367 (16)	0.037 (5)	0.294 (7)
H3B	0.152151	0.706837	0.055446	0.045*	0.294 (7)
C4A	0.1703 (14)	0.8174 (10)	−0.0933 (6)	0.038 (2)	0.706 (7)
H4A	0.142000	0.761812	−0.144148	0.045*	0.706 (7)
C4B	0.156 (3)	0.811 (2)	−0.0554 (16)	0.035 (6)	0.294 (7)
C5A	0.210 (2)	0.9418 (16)	−0.1111 (9)	0.039 (3)	0.706 (7)
H5A	0.207157	0.970180	−0.172834	0.047*	0.706 (7)
C5B	0.193 (5)	0.923 (4)	−0.087 (2)	0.032 (6)	0.294 (7)
H5B	0.176018	0.933494	−0.153049	0.038*	0.294 (7)
C6	0.2535 (4)	1.0233 (3)	−0.0314 (2)	0.0369 (8)
N1	0.2915 (4)	1.1465 (2)	−0.05089 (18)	0.0359 (7)
C9	0.3382 (4)	1.2324 (3)	0.0177 (2)	0.0354 (7)
C10	0.3472 (5)	1.1936 (3)	0.1182 (2)	0.0402 (8)
N2	0.3101 (4)	1.0729 (3)	0.1354 (2)	0.0440 (7)
C8	0.2761 (6)	1.1869 (4)	−0.1493 (2)	0.0540 (10)
H8A	0.223018	1.120497	−0.191729	0.081*	0.22 (4)
H8B	0.403194	1.208575	−0.159941	0.081*	0.22 (4)
H8C	0.191973	1.258317	−0.161254	0.081*	0.22 (4)
H8D	0.322439	1.271095	−0.150220	0.081*	0.78 (4)
H8E	0.142263	1.183017	−0.182009	0.081*	0.78 (4)
H8F	0.353484	1.133275	−0.180695	0.081*	0.78 (4)
C11	0.3169 (7)	1.0381 (4)	0.2335 (3)	0.0696 (13)
H11A	0.279949	0.952205	0.236449	0.104*	0.24 (5)
H11B	0.228285	1.089532	0.259797	0.104*	0.24 (5)
H11C	0.446948	1.049549	0.269709	0.104*	0.24 (5)
H11D	0.356839	1.108652	0.274187	0.104*	0.76 (5)
H11E	0.408503	0.971326	0.250839	0.104*	0.76 (5)
H11F	0.189839	1.011308	0.240928	0.104*	0.76 (5)
O3	0.3982 (6)	1.4989 (3)	−0.1600 (2)	0.0833 (11)
H3A	0.382975	1.460410	−0.109907	0.125*
H3C	0.477462	1.559146	−0.144450	0.125*
C7A	0.1315 (8)	0.6428 (5)	0.0165 (4)	0.0528 (17)	0.706 (7)
H7A2	0.035271	0.639039	0.055782	0.079*	0.706 (7)
H7A3	0.249382	0.603381	0.049019	0.079*	0.706 (7)
H7A1	0.083495	0.600399	−0.042761	0.079*	0.706 (7)
C7B	0.0926 (19)	0.7135 (13)	−0.1317 (10)	0.062 (5)	0.294 (7)
H7B1	0.025634	0.753011	−0.189272	0.093*	0.294 (7)
H7B2	0.006626	0.655227	−0.110056	0.093*	0.294 (7)
H7B3	0.205065	0.670198	−0.143967	0.093*	0.294 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0528 (15)	0.0419 (15)	0.0475 (14)	−0.0027 (12)	0.0067 (11)	0.0004 (12)
O2	0.0675 (18)	0.0632 (18)	0.0414 (14)	−0.0097 (14)	0.0057 (12)	−0.0075 (14)
C1	0.0219 (15)	0.0408 (19)	0.059 (2)	0.0014 (14)	0.0050 (14)	0.0022 (17)
C2A	0.026 (3)	0.038 (6)	0.038 (5)	0.003 (3)	0.007 (4)	0.000 (5)
C2B	0.051 (9)	0.040 (10)	0.051 (13)	−0.009 (7)	0.008 (11)	−0.016 (11)
C3A	0.029 (3)	0.039 (5)	0.043 (8)	−0.003 (3)	0.006 (5)	−0.005 (6)
C3B	0.040 (8)	0.034 (10)	0.036 (13)	0.003 (7)	0.003 (10)	−0.004 (11)
C4A	0.035 (3)	0.039 (4)	0.037 (5)	0.003 (2)	0.002 (4)	−0.005 (4)
C4B	0.033 (7)	0.042 (11)	0.029 (14)	−0.002 (7)	0.008 (10)	−0.013 (11)
C5A	0.038 (5)	0.038 (5)	0.039 (6)	−0.002 (4)	0.002 (4)	0.006 (4)
C5B	0.014 (7)	0.042 (14)	0.038 (13)	0.005 (7)	0.003 (8)	0.005 (10)
C6	0.0200 (15)	0.0367 (18)	0.050 (2)	0.0025 (13)	−0.0020 (13)	−0.0011 (15)
N1	0.0297 (14)	0.0393 (15)	0.0358 (15)	0.0005 (12)	−0.0002 (11)	−0.0006 (12)
C9	0.0259 (16)	0.0385 (19)	0.0407 (18)	0.0022 (14)	0.0037 (13)	−0.0001 (15)
C10	0.0318 (17)	0.052 (2)	0.0362 (18)	−0.0002 (15)	0.0048 (14)	−0.0006 (16)
N2	0.0360 (15)	0.0523 (18)	0.0448 (17)	0.0004 (14)	0.0108 (13)	0.0091 (14)
C8	0.063 (3)	0.057 (2)	0.037 (2)	0.002 (2)	−0.0016 (17)	0.0010 (17)
C11	0.081 (3)	0.078 (3)	0.054 (3)	0.002 (3)	0.023 (2)	0.017 (2)
O3	0.127 (3)	0.069 (2)	0.0480 (17)	−0.041 (2)	0.0053 (18)	0.0030 (16)
C7A	0.055 (3)	0.041 (3)	0.063 (4)	−0.001 (2)	0.013 (3)	0.002 (3)
C7B	0.048 (8)	0.063 (9)	0.077 (10)	−0.005 (7)	0.014 (7)	−0.045 (8)

Geometric parameters (Å, º) top

O1—C9	1.228 (4)	N1—C8	1.470 (4)
O2—C10	1.226 (4)	C9—C10	1.499 (5)
C1—C2B	1.38 (3)	C10—N2	1.365 (5)
C1—C6	1.394 (5)	N2—C11	1.458 (5)
C1—N2	1.409 (4)	C8—H8A	0.9700
C1—C2A	1.418 (12)	C8—H8B	0.9700
C2A—C3A	1.409 (11)	C8—H8C	0.9700
C2A—H2A	0.9400	C8—H8D	0.9700
C2B—C3B	1.41 (2)	C8—H8E	0.9700
C2B—H2B	0.9400	C8—H8F	0.9700
C3A—C4A	1.375 (11)	C11—H11A	0.9700
C3A—C7A	1.504 (14)	C11—H11B	0.9700
C3B—C4B	1.34 (3)	C11—H11C	0.9700
C3B—H3B	0.9400	C11—H11D	0.9700
C4A—C5A	1.41 (2)	C11—H11E	0.9700
C4A—H4A	0.9400	C11—H11F	0.9700
C4B—C5B	1.34 (4)	O3—H3A	0.8603
C4B—C7B	1.53 (2)	O3—H3C	0.8598
C5A—C6	1.434 (17)	C7A—H7A2	0.9700
C5A—H5A	0.9400	C7A—H7A3	0.9700
C5B—C6	1.37 (4)	C7A—H7A1	0.9700
C5B—H5B	0.9400	C7B—H7B1	0.9700
C6—N1	1.401 (4)	C7B—H7B2	0.9700
N1—C9	1.351 (4)	C7B—H7B3	0.9700

C2B—C1—C6	136.5 (10)	H8B—C8—H8C	109.5
C2B—C1—N2	104.1 (10)	N1—C8—H8D	109.5
C6—C1—N2	119.4 (3)	H8A—C8—H8D	141.1
C6—C1—C2A	114.6 (5)	H8B—C8—H8D	56.3
N2—C1—C2A	126.0 (5)	H8C—C8—H8D	56.3
C3A—C2A—C1	124.1 (8)	N1—C8—H8E	109.5
C3A—C2A—H2A	117.9	H8A—C8—H8E	56.3
C1—C2A—H2A	117.9	H8B—C8—H8E	141.1
C1—C2B—C3B	107 (2)	H8C—C8—H8E	56.3
C1—C2B—H2B	126.6	H8D—C8—H8E	109.5
C3B—C2B—H2B	126.6	N1—C8—H8F	109.5
C4A—C3A—C2A	118.5 (11)	H8A—C8—H8F	56.3
C4A—C3A—C7A	121.8 (10)	H8B—C8—H8F	56.3
C2A—C3A—C7A	119.7 (9)	H8C—C8—H8F	141.1
C4B—C3B—C2B	123 (3)	H8D—C8—H8F	109.5
C4B—C3B—H3B	118.5	H8E—C8—H8F	109.5
C2B—C3B—H3B	118.5	N2—C11—H11A	109.5
C3A—C4A—C5A	121.5 (11)	N2—C11—H11B	109.5
C3A—C4A—H4A	119.2	H11A—C11—H11B	109.5
C5A—C4A—H4A	119.2	N2—C11—H11C	109.5
C3B—C4B—C5B	122 (3)	H11A—C11—H11C	109.5
C3B—C4B—C7B	123 (2)	H11B—C11—H11C	109.5
C5B—C4B—C7B	115 (2)	N2—C11—H11D	109.5
C4A—C5A—C6	117.4 (9)	H11A—C11—H11D	141.1
C4A—C5A—H5A	121.3	H11B—C11—H11D	56.3
C6—C5A—H5A	121.3	H11C—C11—H11D	56.3
C4B—C5B—C6	125 (2)	N2—C11—H11E	109.5
C4B—C5B—H5B	117.5	H11A—C11—H11E	56.3
C6—C5B—H5B	117.5	H11B—C11—H11E	141.1
C5B—C6—C1	106.7 (11)	H11C—C11—H11E	56.3
C5B—C6—N1	133.4 (11)	H11D—C11—H11E	109.5
C1—C6—N1	119.8 (3)	N2—C11—H11F	109.5
C1—C6—C5A	123.8 (6)	H11A—C11—H11F	56.3
N1—C6—C5A	116.4 (6)	H11B—C11—H11F	56.3
C9—N1—C6	122.5 (3)	H11C—C11—H11F	141.1
C9—N1—C8	117.6 (3)	H11D—C11—H11F	109.5
C6—N1—C8	119.9 (3)	H11E—C11—H11F	109.5
O1—C9—N1	123.5 (3)	H3A—O3—H3C	109.5
O1—C9—C10	118.3 (3)	C3A—C7A—H7A2	109.5
N1—C9—C10	118.2 (3)	C3A—C7A—H7A3	109.5
O2—C10—N2	122.8 (3)	H7A2—C7A—H7A3	109.5
O2—C10—C9	119.0 (3)	C3A—C7A—H7A1	109.5
N2—C10—C9	118.2 (3)	H7A2—C7A—H7A1	109.5
C10—N2—C1	121.9 (3)	H7A3—C7A—H7A1	109.5
C10—N2—C11	117.0 (3)	C4B—C7B—H7B1	109.5
C1—N2—C11	121.0 (3)	C4B—C7B—H7B2	109.5
N1—C8—H8A	109.5	H7B1—C7B—H7B2	109.5
N1—C8—H8B	109.5	C4B—C7B—H7B3	109.5
H8A—C8—H8B	109.5	H7B1—C7B—H7B3	109.5
N1—C8—H8C	109.5	H7B2—C7B—H7B3	109.5
H8A—C8—H8C	109.5

C6—C1—C2A—C3A	0.8 (11)	C5B—C6—N1—C9	175.2 (19)
N2—C1—C2A—C3A	−179.0 (7)	C1—C6—N1—C9	0.7 (4)
C6—C1—C2B—C3B	1 (4)	C5A—C6—N1—C9	−178.8 (8)
N2—C1—C2B—C3B	179.2 (19)	C5B—C6—N1—C8	−3 (2)
C1—C2A—C3A—C4A	0.2 (15)	C1—C6—N1—C8	−177.6 (3)
C1—C2A—C3A—C7A	179.0 (7)	C5A—C6—N1—C8	2.8 (9)
C1—C2B—C3B—C4B	−3 (4)	C6—N1—C9—O1	−179.7 (3)
C2A—C3A—C4A—C5A	−0.9 (17)	C8—N1—C9—O1	−1.3 (5)
C7A—C3A—C4A—C5A	−179.7 (10)	C6—N1—C9—C10	−0.6 (4)
C2B—C3B—C4B—C5B	2 (5)	C8—N1—C9—C10	177.8 (3)
C2B—C3B—C4B—C7B	−178 (2)	O1—C9—C10—O2	0.6 (5)
C3A—C4A—C5A—C6	0.5 (19)	N1—C9—C10—O2	−178.5 (3)
C3B—C4B—C5B—C6	0 (5)	O1—C9—C10—N2	179.9 (3)
C7B—C4B—C5B—C6	−179 (2)	N1—C9—C10—N2	0.8 (4)
C4B—C5B—C6—C1	−2 (3)	O2—C10—N2—C1	178.2 (3)
C4B—C5B—C6—N1	−177.0 (19)	C9—C10—N2—C1	−1.0 (4)
C2B—C1—C6—C5B	1 (2)	O2—C10—N2—C11	0.1 (5)
N2—C1—C6—C5B	−176.8 (15)	C9—C10—N2—C11	−179.1 (3)
C2B—C1—C6—N1	177.2 (19)	C2B—C1—N2—C10	−177.6 (14)
N2—C1—C6—N1	−0.9 (4)	C6—C1—N2—C10	1.1 (4)
C2A—C1—C6—N1	179.2 (5)	C2A—C1—N2—C10	−179.0 (5)
N2—C1—C6—C5A	178.5 (9)	C2B—C1—N2—C11	0.4 (14)
C2A—C1—C6—C5A	−1.3 (10)	C6—C1—N2—C11	179.1 (3)
C4A—C5A—C6—C1	0.7 (17)	C2A—C1—N2—C11	−1.1 (7)
C4A—C5A—C6—N1	−179.8 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1	0.86	2.09	2.936 (4)	170
O3—H3C···O1ⁱ	0.86	2.38	3.062 (4)	137
O3—H3C···O2ⁱ	0.86	2.19	2.972 (5)	150
C5A—H5A···O3ⁱⁱ	0.94	2.40	3.298 (13)	160
C8—H8E···O2ⁱⁱⁱ	0.97	2.45	3.335 (4)	151

Symmetry codes: (i) −x+1, −y+3, −z; (ii) −x+1/2, y−1/2, −z−1/2; (iii) x−1/2, −y+5/2, z−1/2.

Comparison of observed (X-ray data) and calculated (DFT) geometric parameters (Å, °) top

Parameter	X-ray	B3LYP/6–311G(d,p)
O1—C9	1.228 (4)	1.217
O2—C10	1.226 (4)	1.211
N1—C6	1.401 (4)	1.407
N1—C8	1.470 (4)	1.468
N1—C9	1.351 (4)	1.375
N2—C1	1.409 (4)	1.375
N2—C10	1.365 (5)	1.384
N2—C11	1.458 (5)	1.464
O1—C9—N1	123.5 (3)	123.9
O2—C10—N2	122.8 (3)	123.4
O1—C9—C10	118.3 (3)	118.3

DFT-calculated molecular characteristics for the title compound top

Total Energy, TE (eV)	-20757.4747
E_HOMO (eV)	-6.1139
E_LUMO (eV)	-1.4232
Gap, ΔE (eV)	4.6907
Dipole moment, µ (D)	5.56
Ionization potential, I (eV)	6.1139
Electron affinity, A (eV)	1.4232
Electronegativity, χ	3.929
Hardness, η	2.345
Electrophilicity index, ω	3.291
Softness, σ	0.213
Fraction of electron transferred, ΔN	0.655

Acknowledgements

Langat Singh College, B·R. Bihar University India is thanked for access to laboratory facilities.

Funding information

Funding for this research was provided by: University Grants Commission, New Delhi. This study was supported financially by Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Morocco and the University of Science and Technology, Ibb Branch, Ibb, Yemen.

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