Crystal structure, Hirshfeld surface analysis and inter­action energy and DFT studies of 1-methyl-3-(prop-2-yn-1-yl)-2,3-di­hydro-1H-1,3-benzo­diazol-2-one

Saber, A.; Srhir, M.; Hökelek, T.; Mague, J.T.; Hamou Ahabchane, N.; Sebbar, N.K.; Essassi, E.M.

doi:10.1107/S2056989019015779

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Volume 75| Part 12| December 2019| Pages 1940-1946

https://doi.org/10.1107/S2056989019015779

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Crystal structure, Hirshfeld surface analysis and interaction energy and DFT studies of 1-methyl-3-(prop-2-yn-1-yl)-2,3-dihydro-1H-1,3-benzodiazol-2-one

Asmaa Saber,^a Mohamed Srhir,^a ^* Tuncer Hökelek,^b Joel T. Mague,^c Noureddine Hamou Ahabchane,^a Nada Kheira Sebbar ^d,^a and El Mokhtar Essassi ^a

^aLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, ^bDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, and ^dLaboratoire de Chimie Appliquée et Environnement, Equipe de Chimie Bioorganique Appliquée, Faculté des Sciences, Université Ibn Zohr, Agadir, Morocco
^*Correspondence e-mail: mohamedsrhir2018@gmail.com

Edited by A. J. Lough, University of Toronto, Canada (Received 12 November 2019; accepted 21 November 2019; online 29 November 2019)

In the title molecule, C₁₁H₁₀N₂O, the dihydrobenzimidazol-2-one moiety is essentially planar, with the prop-2-yn-1-yl substituent rotated well out of this plane. In the crystal, C—H_Mthy⋯π(ring) interactions and C—H_Prop⋯O_Dhyr (Mthy = methyl, Prop = prop-2-yn-1-yl and Dhyr = dihydro) hydrogen bonds form corrugated layers parallel to (10 $[\overline{1}]$ ), which are associated through additional C—H_Bnz⋯O_Dhyr (Bnz = benzene) hydrogen bonds and head-to-tail, slipped, π-stacking [centroid-to-centroid distance = 3.7712 (7) Å] interactions between dihydrobenzimidazol-2-one moieties. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (44.1%), H⋯C/C⋯H (33.5%) and O⋯H/H⋯O (13.4%) interactions. Hydrogen-bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry calculations indicate that in the crystal, C—H⋯O hydrogen-bond energies are 46.8 and 32.5 (for C—H_Prop⋯O_Dhyr) and 20.2 (for C—H_Bnz⋯O_Dhyr) kJ mol⁻¹. Density functional theory (DFT) optimized structures at the B3LYP/6–311 G(d,p) level are compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.

Keywords: crystal structure; benzimidazol-2-one; hydrogen bond; C—H⋯π(ring) interaction; π-stacking; Hirshfeld surface.

CCDC reference: 1967468

1. Chemical context

Benzimidazole is an aromatic heterocyclic organic compound that plays an important role in medicinal chemistry and pharmacology. The most prominent benzimidazole moiety present in nature is N-ribosyl-dimethylbenzimidazole and it serves as the axial ligand for cobalt in vitamin B12 (Walia et al., 2011 ). Benzimidazole derivatives possess many biological activities such as anti-microbial, anti-fungal, anti-histaminic, anti-inflammatory, anti-viral, anti-oxidant, anti-cancer and anti-ulcerative (Farukh & Mubashira, 2009 ; Ayhan-Kılcıgil et al., 2007 ; Soderlind et al., 1999 ; Luo et al., 2011 ; Navarrete-Vázquez et al., 2011 ). They are considered to be an important moiety for the development of molecules of pharmaceutical interest (Mondieig et al., 2013 ; Lakhrissi et al., 2008 ). As a continuation of our research on the development of N-substituted benzimidazole derivatives and the evaluation of their potential pharmacological activities (Saber et al., 2018a ,b , 2020 ; Ouzidan et al., 2011 ), we have studied the alkylation reaction of iodomethane with 1-(prop-2-ynyl)-1H-benzoimidazol-2(3H)-one in the presence of tetra-n-butylammonium bromide as catalyst and potassium carbonate as base, to give the title compound, I in good yield. We report herein on its synthesis, the molecular and crystal structures along with the Hirshfeld surface analysis and the intermolecular interaction energies and the density functional theory (DFT) computational calculations carried out at the B3LYP/6–311 G(d,p) level for comparison with the experimentally determined molecular structure in the solid state.

2. Structural commentary

In the title compound, the dihydrobenzimidazol-2-one moiety is planar to within 0.0160 (8) Å (r.m.s. deviation = 0.0082) with atom C7 deviating the most from the mean plane and a prop-2-yn-1-yl substituent rotated well out of this plane as shown by the C1—N2—C9—C10 torsion angle of 62.16 (13)° (Fig. 1).

Figure 1
The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal, inversion dimers are formed by pairs of C—H_Mthy⋯Cg1ⁱ interactions [Mthy = methyl; symmetry code: (i) − x, 1 − y, 1 − z; Cg1 is the centroid of the benzene (A; C1–C6), ring]; which are connected along the b-axis direction by C—H_Bnz⋯O_Dhyr hydrogen bonds (Bnz = benzene and Dhyr = dihydro) and along the a-axis direction at ca 90° to this and parallel to (10 $[\overline{1}]$ ) by inversion-related C—H_Prop⋯O_Dhyr hydrogen bonds (Table 1). The resulting corrugated layers are parallel to (10 $[\overline{1}]$ ) and are connected in pairs by slipped, head-to-tail π-stacking interactions between the dihydrobenzimidazol-2-one moieties, [Cg2⋯Cg1ⁱⁱ = 3.7712 (7) Å, dihedral angle = 0.96 (6)°; symmetry code: (ii) 1 – x, 1 – y, 1 – z; Cg1 and Cg2 are the centroids of rings A and B (N1/N2/C1/C6/C7) and C—H_Prop⋯O_Dhyr (Prop = prop-2-yn-1-yl) hydrogen bonds (Table 1, Figs. 2 and 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1^ix	1.005 (15)	2.566 (15)	3.4885 (15)	152.6 (11)
C8—H8C⋯Cg1^v	1.004 (16)	2.626 (15)	3.5413 (13)	151.1 (12)
C9—H9B⋯O1^vi	0.978 (15)	2.347 (15)	3.3198 (14)	172.9 (12)
C11—H11⋯O1^vii	1.010 (15)	2.181 (15)	3.1569 (15)	162.1 (12)
Symmetry codes: (v) -x, -y+1, -z+1; (vi) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ix) x, y-1, z.

Figure 2
A partial packing diagram viewed along the a-axis direction with C—H⋯O hydrogen bonds, C—H⋯π(ring) and π-stacking interactions shown, respectively, by black, green and orange dashed lines.

Figure 3
A partial packing diagram viewed along the b-axis direction with intermolecular interactions depicted as in Fig. 2

4. Hirshfeld surface analysis

In order to visualize the intermolecular interactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis (Hirshfeld, 1977 ; Spackman & Jayatilaka, 2009 ) was carried out using Crystal Explorer 17.5 (Turner et al., 2017 ). In the HS plotted over d_norm (Fig. 4), the white surface indicates contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distant contact) than the van der Waals radii, respectively (Venkatesan et al., 2016 ). The bright-red spots appearing near O1 and the hydrogen atom H11 indicate their roles as the donors and/or acceptors, respectively; they also appear as blue and red regions corresponding to positive and negative potentials on the HS mapped over electrostatic potential (Spackman et al., 2008 ; Jayatilaka et al., 2005 ) as shown in Fig. 5. The blue regions indicate positive electrostatic potential (hydrogen-bond donors), while the red regions indicate negative electrostatic potential (hydrogen-bond acceptors). The shape-index of the HS is a tool to visualize π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π interactions. Fig. 6 clearly suggests that there are π– π interactions in (I).

Figure 4
View of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm in the range −0.3997 to 1.3219 a.u.

Figure 5
View of the three-dimensional Hirshfeld surface of the title compound plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u. using the STO-3 G basis set at the Hartree–Fock level of theory. Hydrogen-bond donors and acceptors are shown as blue and red regions around the atoms corresponding to positive and negative potentials, respectively.

Figure 6
Hirshfeld surface of the title compound plotted over shape-index.

The overall two-dimensional fingerprint plot, Fig. 7a, and those delineated into H⋯H, H⋯C/C⋯H, H⋯O/O ⋯ H, C⋯C, H⋯N/N⋯H and N⋯C/C⋯N contacts (McKinnon et al., 2007 ) are illustrated in Fig. 7b–g, respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction is H⋯H contributing 44.1% to the overall crystal packing, which is reflected in Fig. 7b as widely scattered points of high density due to the large hydrogen content of the molecule with the tip at d_e = d_i = 1.22 Å. The presence of C—H⋯π interactions gives rise to pairs of characteristic wings in the fingerprint plot delineated into H⋯C/C⋯H contacts, Fig. 7c., contributing 33.5% to the HS (Table 2); these are viewed as pairs of spikes with the tips at d_e + d_i = 2.56 Å. The pair of wings in Fig. 7d has a symmetrical distribution of points with the edges at d_e + d_i = 2.09 Å arising from the H⋯O/O⋯H contacts (13.4% contribution). The C⋯C contacts, Fig. 7e, have an arrow-shaped distribution of points with the tip at d_e = d_i = 1.75 Å. The H⋯N/N⋯N contacts, contributing 2.9% to the overall crystal packing, are depicted in Fig. 7f as widely scattered points. Finally, the N⋯C/C⋯N interactions, contributing 2.4% to the overall crystal packing, are shown in Fig. 7g as tiny characteristic wings with the tips at d_e + d_i = 3.45 Å.

Table 2
Selected interatomic distances (Å)

O1⋯H9A	2.491 (14)	C11⋯O1^vii	3.1569 (15)
O1⋯H3ⁱ	2.566 (15)	C2⋯H8A^iv	2.82 (2)
O1⋯H8B	2.516 (19)	C3⋯H8C^v	2.859 (15)
O1⋯H9Bⁱⁱ	2.346 (14)	C3⋯H8A^iv	2.92 (2)
O1⋯H11ⁱⁱⁱ	2.181 (15)	C4⋯H8C^v	2.810 (15)
C2⋯C10	3.3889 (16)	C5⋯H8C^v	2.935 (15)
C3⋯C8^iv	3.5335 (17)	C8⋯H5	2.983 (14)
C4⋯C8^v	3.4947 (17)	C9⋯H2	2.975 (14)
C4⋯C7^iv	3.5437 (16)	C10⋯H4^viii	2.976 (15)
C5⋯C8^v	3.5884 (17)	C11⋯H5^iv	2.865 (15)
C6⋯C6^iv	3.5349 (14)	C11⋯H4^viii	2.705 (15)
C9⋯O1^vi	3.3198 (14)
Symmetry codes: (i) x, y+1, z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) -x, -y+1, -z+1; (vi) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (viii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 7
The full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯O/O⋯H, (e) C⋯C, (f) H⋯N/N⋯H and (g) N⋯C/C⋯N interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.

The Hirshfeld surface representations with the function d_norm plotted onto the surface are shown for the H⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions in Fig. 8a–c, respectively.

Figure 8
The Hirshfeld surface representations with the function d_norm plotted onto the surface for (a) H⋯H, (b) H⋯C/C⋯H and (c) H⋯O/O⋯H interactions.

The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H and H⋯ O/O⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ).

5. Interaction energy calculations

The intermolecular interaction energies were calculated using the CE–B3LYP/6–31G(d,p) energy model available in CrystalExplorer17.5 (Turner et al., 2017), where a cluster of molecules is generated by applying crystallographic symmetry operations with respect to a selected central molecule within the default radius of 3.8 Å (Turner et al., 2014 ). The total intermolecular energy (E_tot) is the sum of electrostatic (E_ele), polarization (E_pol), dispersion (E_dis) and exchange-repulsion (E_rep) energies (Turner et al., 2015 ) with scale factors of 1.057, 0.740, 0.871 and 0.618, respectively (Mackenzie et al., 2017 ). Hydrogen-bonding interaction energies (in kJ mol⁻¹) were calculated to be −17.4 (E_ele), −3.5 (E_pol), −62.6 (E_dis), 46.5 (E_rep) and −46.8 (E_tot) for C11—H11⋯O1, −12.4 (E_ele), −1.9 (E_pol), −41.6 (E_dis), 29.6 (E_rep) and −32.5 (E_tot) for C9—H9B⋯O1 and −13.7 (E_ele), −3.7 (E_pol), −15.5 (E_dis), 17.0 (E_rep) and −20.2 (E_tot) for C3—H3⋯O1.

6. DFT calculations

The optimized structure of the title compound in the gas phase was generated theoretically via density functional theory (DFT) using the standard B3LYP functional and 6–311 G(d,p) basis-set calculations (Becke, 1993 ) as implemented in GAUSSIAN 09 (Frisch et al., 2009 ). The theoretical and experimental results are in good agreement (Table 3). 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. The DFT calculations provide some important information on the reactivity and site selectivity of the molecular framework. E_HOMO and E_LUMO clarify the inevitable charge-exchange collaboration inside the studied material and are given in Table 4 along with the electronegativity (χ), hardness (η), potential (μ), electrophilicity (ω) and softness (σ). The significance of η and σ is for the evaluation of both the reactivity and stability. The electron transition from the HOMO to the LUMO energy level is shown in Fig. 9. The HOMO and LUMO are localized in the plane extending from the whole 1-methyl-3-(prop-2-yn-1-yl)-2,3-dihydro-1H-1,3-benzodiazol-2-one ring. The energy band gap [ΔE = E_LUMO − E_HOMO] of the molecule is about 5.4115 eV, and the frontier molecular orbital energies, E_HOMO and E_LUMO are −5.8885 and −0.4770 eV, respectively.

Table 3
Comparison of the selected (X-ray and DFT) geometric data (Å, °)

Bonds/angles	X-ray	B3LYP/6–311 G(d,p)
O1—C7	1.2281 (13)	1.24660
N1—C7	1.3735 (14)	1.39764
N1—C6	1.3874 (15)	1.40100
N1—C8	1.4526 (14)	1.45375
N2—C7	1.3807 (14)	1.40268
N2—C1	1.3910 (13)	1.40222
N2—C9	1.4545 (14)	1.46036
C7—N1—C6	110.19 (9)	110.10303
C7—N1—C8	124.14 (10)	122.94288
C6—N1—C8	125.66 (10)	126.95366
C7—N2—C1	110.16 (9)	110.18664
C7—N2—C9	123.55 (9)	122.02491
C1—N2—C9	126.00 (9)	126.78733
C2—C1—N2	131.64 (10)	132.00719

Table 4
Calculated energies for the title compound

Molecular Energy (a.u.) (eV)
Total Energy TE (eV)	−16594.1662
E_HOMO (eV)	−5.8885
E_LUMO (eV)	−0.4770
Energy gap, ΔE (eV)	5.4115
Dipole moment, μ (Debye)	2.8313
Ionization potential, I (eV)	5.8885
Electron affinity, A	2.6040
Electro negativity, χ	0.31828
Hardness, η	2.7058
Electrophilicity index, ω	1.8719
Softness, σ	0.3696
Fraction of electron transferred, ΔN	0.7054

Figure 9
The energy band gap of the title compound.

7. Database survey

The syntheses of several N-substituted benzimidazol-2-one analogues have been reported (Saber et al., 2018a,b; 2020; Belaziz et al., 2012 ; Bouayad et al., 2015 ; Belaziz et al., 2013 ). In a search of the Cambridge Crystallographic Database (CSD; Version 5.40, update of September 2019; Groom et al., 2016 ) using benzimidazol-2-one with an exocyclic carbon atom bound to each nitrogen generated 94 hits. In these, the bicyclic ring system is either planar, has a slight twist end-to-end, or, in the cases where the exocyclic substituents form a ring, has a very shallow bowl shape.

The closest examples to the title compound, I, are II (HISFUN; Saber et al., 2018b), III (URAQAG; Ouzidan et al., 2011a ) and IV (AGAXOX; Kandri Rodi et al., 2013 ). In the title compound, the C—N bonds to the exocyclic groups are 1.4526 (14) and 1.4545 (19) Å while in II–IV the corresponding distances range from 1.445 (3) to 1.4632 (11) Å, and so are quite comparable. The exocyclic groups in I are in an anti-arrangement with the prop-2-yn-1-yl group rotated by 62.16 (13)° out of the plane of the bicyclic moiety (as measured by the C1—N2—C9—C10 torsion angle). In the other three, these substituents are also anti and in II the corresponding torsion angle is 73.46 (18)° while in III they are 82.58 (15) and 74.31 (14)°. In IV the torsion angles are 106.0 (3) and 113.4 (3)° indicating a rotation in the opposite direction from the first three.

8. Synthesis and crystallization

To a mixture of 1-(prop-2-ynyl)-1H-benzimidazol-2(3H)-one (3.61 mmol), iodomethane (6.73 mmol) and potassium carbonate (6.24 mmol) in DMF (15 ml) was added a catalytic amount of tetra-n-butylammonium bromide (0.37 mmol). The mixture was stirred for 24 h. The solid material was removed by filtration and the solvent evaporated under vacuum. The solid product was purified by recrystallization from ethanol to afford colorless crystals (yield: in 82%).

9. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. Hydrogen atoms were located in a difference Fourier map and refined freely.

Table 5
Experimental details

Crystal data
Chemical formula	C₁₁H₁₀N₂O
M_r	186.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	7.1507 (3), 8.8177 (4), 15.4602 (7)
β (°)	97.914 (2)
V (Å³)	965.52 (7)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.68
Crystal size (mm)	0.32 × 0.31 × 0.12

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.83, 0.92
No. of measured, independent and observed [I > 2σ(I)] reflections	6896, 1812, 1679
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.086, 1.06
No. of reflections	1812
No. of parameters	168
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1967468

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989019015779/lh5936sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019015779/lh5936Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019015779/lh5936Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2056989019015779/lh5936Isup4.cml

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: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

1-Methyl-3-(prop-2-yn-1-yl)-2,3-dihydro-1H-1,3-benzodiazol-2-one top

Crystal data top

C₁₁H₁₀N₂O	F(000) = 392
M_r = 186.21	D_x = 1.281 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
a = 7.1507 (3) Å	Cell parameters from 5848 reflections
b = 8.8177 (4) Å	θ = 5.8–70.1°
c = 15.4602 (7) Å	µ = 0.68 mm⁻¹
β = 97.914 (2)°	T = 150 K
V = 965.52 (7) Å³	Plate, colourless
Z = 4	0.32 × 0.31 × 0.12 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	1812 independent reflections
Radiation source: INCOATEC IµS micro-focus source	1679 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.030
Detector resolution: 10.4167 pixels mm^-1	θ_max = 70.1°, θ_min = 5.8°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −10→9
T_min = 0.83, T_max = 0.92	l = −18→18
6896 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	All H-atom parameters refined
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.0402P)² + 0.2239P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1812 reflections	Δρ_max = 0.18 e Å⁻³
168 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: dual	Extinction coefficient: 0.0100 (12)

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
O1	0.31019 (11)	0.82725 (9)	0.64517 (6)	0.0345 (2)
N1	0.24854 (12)	0.64929 (11)	0.53316 (6)	0.0280 (2)
N2	0.36075 (12)	0.56773 (10)	0.66470 (6)	0.0250 (2)
C1	0.33940 (14)	0.44082 (11)	0.61080 (7)	0.0235 (2)
C2	0.37638 (15)	0.28918 (12)	0.62754 (8)	0.0289 (3)
H2	0.426 (2)	0.2543 (16)	0.6872 (10)	0.039 (4)*
C3	0.34025 (16)	0.18941 (14)	0.55731 (8)	0.0353 (3)
H3	0.364 (2)	0.0783 (17)	0.5684 (10)	0.043 (4)*
C4	0.27117 (17)	0.24106 (15)	0.47421 (8)	0.0378 (3)
H4	0.246 (2)	0.1678 (17)	0.4255 (10)	0.046 (4)*
C5	0.23359 (16)	0.39392 (15)	0.45751 (7)	0.0339 (3)
H5	0.190 (2)	0.4305 (16)	0.3992 (10)	0.042 (4)*
C6	0.26803 (14)	0.49324 (12)	0.52720 (7)	0.0255 (3)
C7	0.30715 (14)	0.69684 (12)	0.61712 (7)	0.0260 (2)
C8	0.17860 (17)	0.75002 (16)	0.46162 (8)	0.0381 (3)
H8A	0.255 (3)	0.747 (2)	0.4146 (13)	0.076 (6)*
H8B	0.176 (3)	0.854 (2)	0.4867 (13)	0.072 (5)*
H8C	0.044 (2)	0.7264 (17)	0.4370 (10)	0.047 (4)*
C9	0.44506 (16)	0.56993 (13)	0.75585 (7)	0.0283 (3)
H9A	0.4344 (19)	0.6753 (16)	0.7764 (9)	0.033 (3)*
H9B	0.376 (2)	0.5012 (16)	0.7898 (9)	0.038 (3)*
C10	0.64427 (15)	0.52362 (12)	0.76752 (7)	0.0281 (3)
C11	0.80385 (17)	0.48197 (14)	0.77883 (8)	0.0342 (3)
H11	0.938 (2)	0.4443 (17)	0.7926 (10)	0.050 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0298 (4)	0.0254 (4)	0.0471 (5)	0.0006 (3)	0.0015 (3)	−0.0012 (3)
N1	0.0239 (4)	0.0309 (5)	0.0277 (5)	−0.0020 (3)	−0.0012 (4)	0.0074 (4)
N2	0.0254 (5)	0.0249 (5)	0.0236 (4)	0.0005 (3)	−0.0007 (3)	−0.0007 (3)
C1	0.0196 (5)	0.0264 (5)	0.0244 (5)	−0.0023 (4)	0.0028 (4)	−0.0014 (4)
C2	0.0249 (5)	0.0281 (6)	0.0337 (6)	−0.0008 (4)	0.0041 (4)	0.0011 (4)
C3	0.0298 (6)	0.0300 (6)	0.0469 (7)	−0.0021 (4)	0.0088 (5)	−0.0072 (5)
C4	0.0339 (6)	0.0427 (7)	0.0384 (6)	−0.0083 (5)	0.0107 (5)	−0.0158 (5)
C5	0.0286 (6)	0.0486 (7)	0.0248 (6)	−0.0089 (5)	0.0048 (4)	−0.0032 (5)
C6	0.0207 (5)	0.0307 (6)	0.0254 (5)	−0.0046 (4)	0.0037 (4)	0.0014 (4)
C7	0.0189 (5)	0.0261 (5)	0.0328 (6)	−0.0007 (4)	0.0025 (4)	0.0025 (4)
C8	0.0294 (6)	0.0450 (7)	0.0380 (7)	−0.0013 (5)	−0.0019 (5)	0.0189 (6)
C9	0.0296 (6)	0.0332 (6)	0.0218 (5)	0.0004 (4)	0.0019 (4)	−0.0014 (4)
C10	0.0333 (6)	0.0293 (5)	0.0206 (5)	−0.0018 (4)	−0.0004 (4)	0.0014 (4)
C11	0.0330 (6)	0.0381 (6)	0.0298 (6)	0.0022 (5)	−0.0016 (4)	0.0030 (5)

Geometric parameters (Å, º) top

O1—C7	1.2281 (13)	C4—C5	1.3915 (19)
N1—C7	1.3735 (14)	C4—H4	0.989 (16)
N1—C6	1.3874 (15)	C5—C6	1.3839 (16)
N1—C8	1.4526 (14)	C5—H5	0.967 (15)
N2—C7	1.3807 (14)	C8—H8A	0.97 (2)
N2—C1	1.3910 (13)	C8—H8B	0.99 (2)
N2—C9	1.4545 (14)	C8—H8C	1.004 (16)
C1—C2	1.3805 (15)	C9—C10	1.4689 (16)
C1—C6	1.4011 (14)	C9—H9A	0.988 (14)
C2—C3	1.3937 (17)	C9—H9B	0.978 (15)
C2—H2	0.991 (15)	C10—C11	1.1885 (17)
C3—C4	1.3883 (19)	C11—H11	1.009 (16)
C3—H3	1.005 (15)

O1···H9A	2.491 (14)	C11···O1^vii	3.1569 (15)
O1···H3ⁱ	2.566 (15)	C2···H8A^iv	2.82 (2)
O1···H8B	2.516 (19)	C3···H8C^v	2.859 (15)
O1···H9Bⁱⁱ	2.346 (14)	C3···H8A^iv	2.92 (2)
O1···H11ⁱⁱⁱ	2.181 (15)	C4···H8C^v	2.810 (15)
C2···C10	3.3889 (16)	C5···H8C^v	2.935 (15)
C3···C8^iv	3.5335 (17)	C8···H5	2.983 (14)
C4···C8^v	3.4947 (17)	C9···H2	2.975 (14)
C4···C7^iv	3.5437 (16)	C10···H4^viii	2.976 (15)
C5···C8^v	3.5884 (17)	C11···H5^iv	2.865 (15)
C6···C6^iv	3.5349 (14)	C11···H4^viii	2.705 (15)
C9···O1^vi	3.3198 (14)

C7—N1—C6	110.19 (9)	C5—C6—N1	132.12 (10)
C7—N1—C8	124.14 (10)	C5—C6—C1	120.83 (11)
C6—N1—C8	125.66 (10)	N1—C6—C1	107.04 (9)
C7—N2—C1	110.16 (9)	O1—C7—N1	127.43 (10)
C7—N2—C9	123.55 (9)	O1—C7—N2	126.43 (10)
C1—N2—C9	126.00 (9)	N1—C7—N2	106.14 (9)
C2—C1—N2	131.64 (10)	N1—C8—H8A	112.7 (12)
C2—C1—C6	121.90 (10)	N1—C8—H8B	106.7 (11)
N2—C1—C6	106.45 (9)	H8A—C8—H8B	111.1 (16)
C1—C2—C3	117.07 (11)	N1—C8—H8C	111.9 (9)
C1—C2—H2	120.7 (8)	H8A—C8—H8C	108.5 (15)
C3—C2—H2	122.3 (8)	H8B—C8—H8C	105.7 (13)
C4—C3—C2	121.20 (11)	N2—C9—C10	112.38 (9)
C4—C3—H3	120.5 (9)	N2—C9—H9A	106.5 (8)
C2—C3—H3	118.3 (9)	C10—C9—H9A	109.8 (8)
C3—C4—C5	121.63 (11)	N2—C9—H9B	109.9 (8)
C3—C4—H4	119.6 (9)	C10—C9—H9B	108.2 (8)
C5—C4—H4	118.8 (9)	H9A—C9—H9B	110.1 (11)
C6—C5—C4	117.35 (11)	C11—C10—C9	177.63 (12)
C6—C5—H5	120.9 (8)	C10—C11—H11	176.1 (9)
C4—C5—H5	121.7 (8)

C7—N2—C1—C2	178.91 (11)	C2—C1—C6—C5	−0.69 (15)
C9—N2—C1—C2	4.89 (17)	N2—C1—C6—C5	178.96 (9)
C7—N2—C1—C6	−0.69 (11)	C2—C1—C6—N1	−179.67 (9)
C9—N2—C1—C6	−174.72 (9)	N2—C1—C6—N1	−0.02 (11)
N2—C1—C2—C3	−179.33 (10)	C6—N1—C7—O1	179.51 (10)
C6—C1—C2—C3	0.23 (15)	C8—N1—C7—O1	0.13 (17)
C1—C2—C3—C4	0.37 (16)	C6—N1—C7—N2	−1.13 (11)
C2—C3—C4—C5	−0.54 (18)	C8—N1—C7—N2	179.49 (9)
C3—C4—C5—C6	0.08 (17)	C1—N2—C7—O1	−179.51 (10)
C4—C5—C6—N1	179.20 (11)	C9—N2—C7—O1	−5.31 (16)
C4—C5—C6—C1	0.52 (15)	C1—N2—C7—N1	1.12 (11)
C7—N1—C6—C5	−178.10 (11)	C9—N2—C7—N1	175.32 (9)
C8—N1—C6—C5	1.27 (18)	C7—N2—C9—C10	−111.11 (11)
C7—N1—C6—C1	0.72 (11)	C1—N2—C9—C10	62.16 (13)
C8—N1—C6—C1	−179.91 (9)

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1^ix	1.005 (15)	2.566 (15)	3.4885 (15)	152.6 (11)
C8—H8C···Cg1^v	1.004 (16)	2.626 (15)	3.5413 (13)	151.1 (12)
C9—H9B···O1^vi	0.978 (15)	2.347 (15)	3.3198 (14)	172.9 (12)
C11—H11···O1^vii	1.010 (15)	2.181 (15)	3.1569 (15)	162.1 (12)

Symmetry codes: (v) −x, −y+1, −z+1; (vi) −x+1/2, y−1/2, −z+3/2; (vii) −x+3/2, y−1/2, −z+3/2; (ix) x, y−1, z.

Comparison of the selected (X-ray and DFT) geometric data (Å, °) top

Bonds/angles	X-ray	B3LYP/6-311 G(d,p)
O1—C7	1.2281 (13)	1.24660
N1—C7	1.3735 (14)	1.39764
N1—C6	1.3874 (15)	1.40100
N1—C8	1.4526 (14)	1.45375
N2—C7	1.3807 (14)	1.40268
N2—C1	1.3910 (13)	1.40222
N2—C9	1.4545 (14)	1.46036
C7—N1—C6	110.19 (9)	110.10303
C7—N1—C8	124.14 (10)	122.94288
C6—N1—C8	125.66 (10)	126.95366
C7—N2—C1	110.16 (9)	110.18664
C7—N2—C9	123.55 (9)	122.02491
C1—N2—C9	126.00 (9)	126.78733
C2—C1—N2	131.64 (10)	132.00719

Calculated energies for the title compound top

Molecular Energy (a.u.) (eV)
Total Energy TE (eV)	-16594.1662
E_HOMO (eV)	-5.8885
E_LUMO (eV)	-0.4770
Energy gap, ΔE (eV)	5.4115
Dipole moment, µ (Debye)	2.8313
Ionization potential, I (eV)	5.8885
Electron affinity, A	2.6040
Electro negativity, χ	0.31828
Hardness, η	2.7058
Electrophilicity index, ω	1.8719
Softness, σ	0.3696
Fraction of electron transferred, ΔN	0.7054

Funding information

The support of NSF–MRI grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged. TH is grateful to Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004).

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