Crystal structure and DFT study of (E)-2-chloro-4-{[2-(2,4-di­nitro­phen­yl)hydrazin-1-yl­idene]meth­yl}phenol aceto­nitrile hemisolvate

Dege, N.; Faizi, M.S.H.; Doğan, O.E.; Ağar, E.; Golenya, I.A.

doi:10.1107/S205698901900642X

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ISSN: 2056-9890

Volume 75| Part 6| June 2019| Pages 770-773

https://doi.org/10.1107/S205698901900642X

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Crystal structure and DFT study of (E)-2-chloro-4-{[2-(2,4-dinitrophenyl)hydrazin-1-ylidene]methyl}phenol acetonitrile hemisolvate

Necmi Dege,^a Md. Serajul Haque Faizi,^b ^* Onur Erman Doğan,^a Erbil Ağar ^c and Irina A. Golenya ^d ^*

^aOndokuz Mayis University, Faculty of Arts and Sciences, Department of Physics, 55139, Kurupelit, Samsun, Turkey, ^bDepartment of Chemistry, Langat Singh College, B. R. A. Bihar University, Muzaffarpur, Bihar 842001, India, ^cOndokuz Mayis University, Faculty of Arts and Sciences, Department of Chemistry, 55139, Kurupelit, Samsun, Turkey, and ^dNational Taras Shevchenko University, Department of Chemistry, Volodymyrska str., 64, 01601 Kyiv, Ukraine
^*Correspondence e-mail: faizichemiitg@gmail.com, igolenya@ua.fm

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 5 May 2019; accepted 6 May 2019; online 10 May 2019)

The title Schiff base compound, C₁₃H₉ClN₄O₅·0.5CH₃CN, crystallizes as an acetonitrile hemisolvate; the solvent molecule being located on a twofold rotation axis. The molecule is nearly planar, with a dihedral angle between the two benzene rings of 3.7 (2)°. The configuration about the C=N bond is E, and there is an intramolecular N—H⋯O_nitro hydrogen bond present forming an S(6) ring motif. In the crystal, molecules are linked by O—H⋯O and N—H⋯O hydrogen bonds, forming layers lying parallel to (10 $[\overline{1}]$ ). The layers are linked by C—H⋯Cl hydrogen bonds, forming a supramolecular framework. Within the framework there are offset π–π stacking interactions [intercentroid distance = 3.833 (2) Å] present involving inversion-related molecules. The DFT study shows that the HOMO and LUMO are localized in the plane extending from the phenol ring to the 2,4-dinitrobenzene ring, and the HOMO–LUMO gap is found to be 0.13061 a.u.

Keywords: crystal structure; hydrazine; 2,4-dinitrophenyl; Schiff base; hydrogen bonding; supramolecular framework; DFT.

CCDC reference: 1912273

1. Chemical context

Over the past 25 years, extensive research has surrounded the synthesis and use of Schiff base compounds in organic and inorganic chemistry, as they have important medicinal and pharmaceutical applications. These compounds show biological activities including antibacterial, antifungal, anticancer and herbicidal activities (Desai et al., 2001 ; Singh & Dash, 1988 ; Karia & Parsania, 1999 ). Schiff bases are also becoming increasingly important in the dye and plastics industries as well as for liquid-crystal technology and the mechanistic investigation of drugs used in pharmacology, biochemistry and physiology (Sheikhshoaie & Sharif, 2006 ). 2,4-Dinitrophenylhydrazine is frequently used as a reagent for the characterization of aldehydes and ketones (Furniss et al., 1999 ). Its derivatives are widely used as dyes (Guillaumont & Nakamura, 2000 ). They are also found to have versatile coordinating abilities towards different metal ions (Raj & Kurup, 2007 ). The present work is a part of an ongoing structural study of Schiff bases and their utilization in the synthesis of quinoxaline derivatives (Faizi et al., 2016a ), fluorescence sensors (Faizi et al., 2016b ) and coordination compounds (Faizi & Prisyazhnaya, 2015 ). We report herein on the synthesis, crystal structure and DFT computational calculations of the title new Schiff base compound. The results of calculations by density functional theory (DFT) carried out at the B3LYP/6–311 G(d,p) level are compared with the experimentally determined molecular structure in the solid state.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The configuration about the C7=N1 bond is E, and there is intramolecular N—H⋯O_nitro hydrogen bond that generates an S(6) ring motif (Fig. 1 and Table 1). The N1—N2 bond length is 1.380 (3) Å and the N1=C7 bond length is 1.275 (4) Å. These bond lengths are comparable with those of some closely related compounds (Fun et al., 2013 ; Faizi et al., 2017 ; Ghosh et al., 2016 ). The C8—C9 and C8—C13 bonds [1.411 (5) and 1.414 (4) Å, respectively], which are adjacent to the imino N2 atom, are significantly longer than the average distance of 1.375 (3) Å for the other C—C bonds in the same benzene ring. This same pattern of bond lengths has been observed previously in some 2,4-dinitrophenylhydrazone derivatives (Ohba, 1996 ; Borwick et al., 1997 ). The title molecule is almost planar with the dihedral angle between the benzene rings being 3.70 (17)°. The nitro groups of the 2,4-dinitrophenyl unit are twisted slightly with respect to the C8–C13 benzene ring to which they are attached: nitro group N2/O4/O5 is inclined to the benzene ring by 2.1 (4)°, while nitro group N3/O2/O3 is inclined to it by 6.5 (5)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O5	0.86	2.01	2.619 (4)	127
O1—H1⋯O2ⁱ	0.82	2.37	3.114 (4)	152
O1—H1⋯O3ⁱ	0.82	2.25	2.998 (4)	152
N2—H2⋯O5ⁱⁱ	0.86	2.58	3.362 (4)	152
C9—H9⋯Cl1ⁱⁱⁱ	0.93	2.72	3.485 (4)	140
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) -x+1, -y+2, -z+1.

Figure 1
The molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 40% probability level. The intramolecular N—H⋯O hydrogen bond (see Table 1

), forming an S(6) ring motif, is shown as a dashed line.

3. Supramolecular features

In the crystal, molecules are linked by O—H⋯O and N—H⋯O hydrogen bonds (Table 1), forming layers lying parallel to (10 $[\overline{1}]$ ), as shown in Fig. 2. The layers are linked by C—H⋯Cl hydrogen bonds, forming a supramolecular framework (Fig. 3 and Table 1). Within the framework, inversion-related molecules are linked by offset π–π stacking interactions (Fig. 3); Cg1⋯Cg2ⁱ = 3.833 (2) Å, where Cg1 and Cg2 are the centroids of rings C1–C6 and C8–C13, respectively, α = 3.70 (17)°, β = 27.9°, γ = 24.5°, interplanar distances are 3.489 (2) and 3.388 (2) Å, offset = 1.791 Å; symmetry code: (i) −x + 1, −y + 1, −z + 1. There are no other significant intermolecular contacts present in the crystal.

Figure 2
A view along the a axis of the crystal packing of the title compound. Hydrogen bonds (see Table 1

) are shown as dashed lines. For clarity, the acetonitrile solvent molecules have been omitted and only hydrogen atoms H1 and H2 have been included.

Figure 3
A view normal to plane (110) of the crystal packing of the title compound. Hydrogen bonds (see Table 1

) are shown as dashed lines, and, for clarity, only hydrogen atoms H1, H2 and H9 have been included.

4. DFT study

The DFT quantum-chemical calculations were performed at the B3LYP/6-311 G(d,p) level (Becke, 1993 ) as implemented in GAUSSIAN09 (Frisch et al., 2009 ). The DFT structure optimization of the title compound was performed starting from the X-ray geometry, with experimental values of bond lengths and bond angles matching with theoretical values. The 6-311 G(d,p) basis set is well suited in its approach to the experimental data. The DFT study shows that the HOMO and LUMO are localized in the plane extending from the whole phenol ring to the 2,4-dinitrobenzene ring. The electron distribution of the HOMO-1, HOMO, LUMO and the LUMO+1 energy levels are shown in Fig. 4. The HOMO molecular orbital exhibits both σ and π character, whereas HOMO-1 is dominated by π-orbital density. The LUMO is mainly composed of π-density while LUMO+1 has both σ and π electronic density. The HOMO–LUMO gap was found to be 0.13061 a.u. and the frontier molecular orbital energies, E_HOMO and E_LUMO are −0.24019 and −0.10958 a.u., respectively.

Figure 4
Electron distribution of the HOMO-1, HOMO, LUMO and the LUMO+1 energy levels for the title compound.

5. Database survey

A search of the Cambridge Structural Database (CSD, version 5.40, update February 2019; Groom et al., 2016 ) for the 1-benzylidene-2-(2,4-dinitrophenyl)hydrazine skeleton gave 71 hits (see supporting information). 18 of these structures involve a halide substituent and 23 involve a hydroxyl substituent. Only one compound involves both a halide and an hydroxyl substituent and closely resembles the title compound, viz. 4-chloro-2-{[(2,4-dinitrophenyl)hydrazono]methyl}phenol (CSD refcode HUTHOV; Ghosh et al., 2016). Here the benzene rings are inclined to each other by 3.40 (9)°, compared to 3.70 (17)° in the title compound, and again there is an intramolecular N—H⋯O_nitro hydrogen bond present forming an S(6) ring motif. In fact, in all 71 structures (see supporting information) there is an intramolecular N—H⋯O_nitro hydrogen bond present forming an S(6) ring motif, and in the majority of the compounds the two benzene rings are almost coplanar with the dihedral angle varying between ca 0 to 8°, with a few exceptions.

6. Synthesis and crystallization

The title compound was prepared by refluxing a mixture of 4-chloro-3-hydroxybenzaldehyde (39.1 mg, 0.25 mmol) in ethanol (15 ml) and 2,4-dinitrophenylhydrazine (49.5 mg, 0.25 mmol) in ethanol (15 ml). The reaction mixture was stirred for 5 h under reflux. Orange plate-like crystals of the title compound were obtained by slow evaporation of a solution in ethanol (yield 68%, m.p. 542–544K).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The OH and NH hydrogen atoms and the C-bound H atoms were included in calculated positions and allowed to ride on the parent atoms: O—H = 0.82 Å, N—H = 0.86 Å, C—H = 0.93–0.96 Å with U_iso(H) = 1.5U_eq(O-hydroxyl, C-methyl) and 1.2U_eq(N,C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₉ClN₄O₅·0.5C₂H₃N
M_r	357.22
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	12.0614 (11), 9.6960 (6), 26.688 (2)
β (°)	99.619 (7)
V (Å³)	3077.2 (4)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.29
Crystal size (mm)	0.49 × 0.28 × 0.04

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002 )
T_min, T_max	0.908, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	8928, 3027, 1416
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.137, 0.93
No. of reflections	3027
No. of parameters	224
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.26
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2002), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), Mercury (Macrae et al., 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1912273

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S205698901900642X/su5496sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901900642X/su5496Isup2.hkl

CSD search S1. DOI: https://doi.org/10.1107/S205698901900642X/su5496sup3.pdf

Supporting information file. DOI: https://doi.org/10.1107/S205698901900642X/su5496Isup4.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

(E)-2-Chloro-4-{[2-(2,4-dinitrophenyl)hydrazin-1-ylidene]methyl}phenol acetonitrile hemisolvate top

Crystal data top

C₁₃H₉ClN₄O₅·0.5C₂H₃N	F(000) = 1464
M_r = 357.22	D_x = 1.542 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.0614 (11) Å	Cell parameters from 8879 reflections
b = 9.6960 (6) Å	θ = 1.6–27.9°
c = 26.688 (2) Å	µ = 0.28 mm⁻¹
β = 99.619 (7)°	T = 296 K
V = 3077.2 (4) Å³	Plate, orange
Z = 8	0.49 × 0.28 × 0.04 mm

Data collection top

Stoe IPDS 2 diffractometer	3027 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1416 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.056
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.0°, θ_min = 1.6°
rotation method scans	h = −14→14
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −11→11
T_min = 0.908, T_max = 0.989	l = −32→32
8928 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: mixed
wR(F²) = 0.137	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0568P)²] where P = (F_o² + 2F_c²)/3
3027 reflections	(Δ/σ)_max < 0.001
224 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.52434 (10)	1.07475 (11)	0.57323 (4)	0.0964 (4)
O1	0.6912 (2)	1.0735 (3)	0.66391 (9)	0.0832 (8)
H1	0.733227	1.065785	0.691276	0.125*
N1	0.6314 (2)	0.5959 (3)	0.49923 (11)	0.0606 (7)
N2	0.6383 (2)	0.4785 (3)	0.47069 (11)	0.0633 (8)
H2	0.684398	0.413575	0.481954	0.076*
O4	0.6517 (2)	0.1472 (3)	0.37327 (11)	0.0926 (9)
N4	0.6512 (3)	0.2398 (3)	0.40402 (13)	0.0736 (9)
O5	0.7122 (3)	0.2383 (3)	0.44573 (11)	0.0972 (9)
O2	0.2825 (3)	0.5344 (4)	0.27290 (12)	0.1162 (12)
N3	0.3566 (3)	0.4469 (5)	0.28233 (14)	0.0906 (11)
C4	0.6977 (3)	0.7239 (3)	0.57388 (12)	0.0547 (8)
O3	0.3675 (3)	0.3539 (4)	0.25304 (12)	0.1189 (12)
C8	0.5723 (3)	0.4668 (3)	0.42510 (13)	0.0572 (9)
C7	0.6998 (3)	0.6042 (3)	0.54105 (14)	0.0620 (9)
H7	0.751146	0.533624	0.550646	0.074*
C1	0.6946 (3)	0.9554 (3)	0.63640 (13)	0.0622 (9)
C3	0.6217 (3)	0.8310 (3)	0.55996 (12)	0.0600 (9)
H3	0.571249	0.825918	0.529585	0.072*
C2	0.6210 (3)	0.9437 (3)	0.59087 (13)	0.0618 (9)
C13	0.5754 (3)	0.3556 (3)	0.39104 (13)	0.0582 (9)
C9	0.4926 (3)	0.5706 (4)	0.40833 (14)	0.0666 (9)
H9	0.486539	0.645038	0.429653	0.080*
C5	0.7703 (3)	0.7353 (4)	0.61968 (13)	0.0653 (10)
H5	0.820955	0.664350	0.629757	0.078*
C12	0.5062 (3)	0.3507 (4)	0.34458 (13)	0.0664 (10)
H12	0.510551	0.276937	0.322720	0.080*
C11	0.4313 (3)	0.4545 (4)	0.33077 (13)	0.0683 (10)
C6	0.7698 (3)	0.8491 (4)	0.65093 (13)	0.0658 (10)
H6	0.819628	0.854208	0.681488	0.079*
C10	0.4249 (3)	0.5663 (4)	0.36269 (15)	0.0724 (10)
H10	0.374492	0.637587	0.352688	0.087*
C14	0.500000	0.8470 (10)	0.250000	0.108 (2)
N5	0.500000	0.7307 (8)	0.250000	0.129 (2)
C15	0.500000	0.9945 (8)	0.250000	0.133 (3)
H15A	0.477479	1.027514	0.280695	0.200*	0.5
H15B	0.448298	1.027514	0.221207	0.200*	0.5
H15C	0.574223	1.027514	0.248098	0.200*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1112 (8)	0.0726 (7)	0.0951 (8)	0.0330 (6)	−0.0125 (6)	−0.0092 (6)
O1	0.096 (2)	0.0762 (17)	0.0716 (18)	0.0121 (15)	−0.0028 (15)	−0.0197 (14)
N1	0.0692 (19)	0.0535 (17)	0.0591 (18)	0.0024 (14)	0.0106 (17)	−0.0066 (14)
N2	0.074 (2)	0.0512 (17)	0.0631 (19)	0.0102 (14)	0.0082 (17)	−0.0038 (14)
O4	0.116 (2)	0.0702 (17)	0.0891 (19)	0.0191 (16)	0.0082 (18)	−0.0220 (16)
N4	0.089 (2)	0.063 (2)	0.068 (2)	0.0086 (18)	0.009 (2)	−0.0067 (18)
O5	0.123 (2)	0.0750 (19)	0.0822 (19)	0.0406 (17)	−0.0170 (18)	−0.0116 (15)
O2	0.086 (2)	0.166 (3)	0.089 (2)	0.016 (2)	−0.0102 (19)	0.023 (2)
N3	0.067 (2)	0.142 (4)	0.063 (2)	−0.009 (3)	0.010 (2)	0.012 (2)
C4	0.058 (2)	0.0523 (19)	0.054 (2)	−0.0033 (17)	0.0103 (18)	0.0007 (17)
O3	0.102 (2)	0.181 (4)	0.068 (2)	0.004 (2)	−0.0016 (18)	−0.029 (2)
C8	0.065 (2)	0.052 (2)	0.054 (2)	−0.0015 (17)	0.0092 (19)	0.0003 (17)
C7	0.067 (2)	0.057 (2)	0.063 (2)	0.0063 (17)	0.013 (2)	−0.0013 (18)
C1	0.067 (2)	0.061 (2)	0.059 (2)	0.0006 (19)	0.0101 (19)	−0.0087 (18)
C3	0.065 (2)	0.058 (2)	0.054 (2)	0.0043 (18)	0.0010 (18)	0.0017 (17)
C2	0.068 (2)	0.055 (2)	0.061 (2)	0.0074 (18)	0.006 (2)	0.0002 (18)
C13	0.060 (2)	0.056 (2)	0.059 (2)	0.0045 (17)	0.0111 (19)	0.0004 (17)
C9	0.070 (2)	0.060 (2)	0.071 (3)	0.009 (2)	0.015 (2)	0.0028 (19)
C5	0.060 (2)	0.071 (2)	0.064 (2)	0.0143 (19)	0.009 (2)	0.003 (2)
C12	0.075 (3)	0.071 (2)	0.055 (2)	−0.005 (2)	0.016 (2)	−0.0022 (19)
C11	0.065 (2)	0.089 (3)	0.051 (2)	−0.007 (2)	0.010 (2)	0.007 (2)
C6	0.064 (2)	0.076 (2)	0.053 (2)	0.003 (2)	−0.0012 (18)	−0.0052 (19)
C10	0.071 (3)	0.075 (2)	0.072 (3)	0.010 (2)	0.013 (2)	0.011 (2)
C14	0.090 (5)	0.123 (7)	0.110 (6)	0.000	0.012 (4)	0.000
N5	0.121 (5)	0.120 (5)	0.137 (5)	0.000	−0.001 (4)	0.000
C15	0.103 (6)	0.103 (6)	0.196 (9)	0.000	0.029 (6)	0.000

Geometric parameters (Å, º) top

Cl1—C2	1.736 (3)	C3—C2	1.370 (4)
O1—C1	1.364 (4)	C3—H3	0.9300
O1—H1	0.8200	C13—C12	1.375 (5)
N1—C7	1.275 (4)	C9—C10	1.349 (5)
N1—N2	1.380 (3)	C9—H9	0.9300
N2—C8	1.343 (4)	C5—C6	1.384 (4)
N2—H2	0.8600	C5—H5	0.9300
O4—N4	1.217 (3)	C12—C11	1.362 (5)
N4—O5	1.228 (4)	C12—H12	0.9300
N4—C13	1.452 (4)	C11—C10	1.388 (5)
O2—N3	1.228 (5)	C6—H6	0.9300
N3—O3	1.215 (4)	C10—H10	0.9300
N3—C11	1.449 (5)	C14—N5	1.128 (9)
C4—C5	1.384 (4)	C14—C15	1.430 (10)
C4—C3	1.394 (4)	C15—H15A	0.9600
C4—C7	1.457 (4)	C15—H15B	0.9600
C8—C9	1.411 (5)	C15—H15C	0.9600
C8—C13	1.414 (4)	C15—H15Aⁱ	0.9600
C7—H7	0.9300	C15—H15Bⁱ	0.9600
C1—C2	1.384 (5)	C15—H15Cⁱ	0.9600
C1—C6	1.385 (5)

C1—O1—H1	109.5	C4—C5—H5	119.0
C7—N1—N2	116.5 (3)	C6—C5—H5	119.0
C8—N2—N1	119.2 (3)	C11—C12—C13	119.6 (3)
C8—N2—H2	120.4	C11—C12—H12	120.2
N1—N2—H2	120.4	C13—C12—H12	120.2
O4—N4—O5	122.1 (3)	C12—C11—C10	120.9 (4)
O4—N4—C13	118.9 (3)	C12—C11—N3	119.3 (4)
O5—N4—C13	118.9 (3)	C10—C11—N3	119.8 (4)
O3—N3—O2	122.3 (4)	C5—C6—C1	119.5 (3)
O3—N3—C11	119.6 (4)	C5—C6—H6	120.2
O2—N3—C11	118.1 (4)	C1—C6—H6	120.2
C5—C4—C3	117.8 (3)	C9—C10—C11	119.4 (4)
C5—C4—C7	121.5 (3)	C9—C10—H10	120.3
C3—C4—C7	120.6 (3)	C11—C10—H10	120.3
N2—C8—C9	119.8 (3)	N5—C14—C15	180.0
N2—C8—C13	124.8 (3)	C14—C15—H15A	109.5
C9—C8—C13	115.4 (3)	C14—C15—H15B	109.5
N1—C7—C4	120.2 (3)	H15A—C15—H15B	109.5
N1—C7—H7	119.9	C14—C15—H15C	109.5
C4—C7—H7	119.9	H15A—C15—H15C	109.5
O1—C1—C2	117.9 (3)	H15B—C15—H15C	109.5
O1—C1—C6	123.4 (3)	C14—C15—H15Aⁱ	109.471 (2)
C2—C1—C6	118.6 (3)	H15A—C15—H15Aⁱ	141.1
C2—C3—C4	120.2 (3)	H15B—C15—H15Aⁱ	56.3
C2—C3—H3	119.9	H15C—C15—H15Aⁱ	56.2
C4—C3—H3	119.9	C14—C15—H15Bⁱ	109.470 (3)
C3—C2—C1	121.8 (3)	H15A—C15—H15Bⁱ	56.3
C3—C2—Cl1	119.5 (3)	H15B—C15—H15Bⁱ	141.1
C1—C2—Cl1	118.8 (3)	H15C—C15—H15Bⁱ	56.3
C12—C13—C8	121.9 (3)	H15Aⁱ—C15—H15Bⁱ	109.5
C12—C13—N4	116.8 (3)	C14—C15—H15Cⁱ	109.470 (5)
C8—C13—N4	121.3 (3)	H15A—C15—H15Cⁱ	56.3
C10—C9—C8	122.8 (4)	H15B—C15—H15Cⁱ	56.2
C10—C9—H9	118.6	H15C—C15—H15Cⁱ	141.1
C8—C9—H9	118.6	H15Aⁱ—C15—H15Cⁱ	109.5
C4—C5—C6	122.0 (3)	H15Bⁱ—C15—H15Cⁱ	109.5

C7—N1—N2—C8	−176.8 (3)	O4—N4—C13—C8	−179.3 (3)
N1—N2—C8—C9	−3.5 (4)	O5—N4—C13—C8	1.0 (5)
N1—N2—C8—C13	176.4 (3)	N2—C8—C9—C10	178.9 (3)
N2—N1—C7—C4	−179.4 (3)	C13—C8—C9—C10	−1.0 (5)
C5—C4—C7—N1	179.5 (3)	C3—C4—C5—C6	−0.8 (5)
C3—C4—C7—N1	−0.4 (5)	C7—C4—C5—C6	179.4 (3)
C5—C4—C3—C2	0.7 (5)	C8—C13—C12—C11	−0.7 (5)
C7—C4—C3—C2	−179.4 (3)	N4—C13—C12—C11	178.3 (3)
C4—C3—C2—C1	0.0 (5)	C13—C12—C11—C10	0.9 (5)
C4—C3—C2—Cl1	−179.1 (2)	C13—C12—C11—N3	−178.4 (3)
O1—C1—C2—C3	177.5 (3)	O3—N3—C11—C12	−5.6 (5)
C6—C1—C2—C3	−0.6 (5)	O2—N3—C11—C12	172.9 (3)
O1—C1—C2—Cl1	−3.4 (4)	O3—N3—C11—C10	175.1 (4)
C6—C1—C2—Cl1	178.5 (3)	O2—N3—C11—C10	−6.4 (5)
N2—C8—C13—C12	−179.2 (3)	C4—C5—C6—C1	0.1 (5)
C9—C8—C13—C12	0.7 (5)	O1—C1—C6—C5	−177.5 (3)
N2—C8—C13—N4	1.8 (5)	C2—C1—C6—C5	0.6 (5)
C9—C8—C13—N4	−178.3 (3)	C8—C9—C10—C11	1.3 (5)
O4—N4—C13—C12	1.7 (5)	C12—C11—C10—C9	−1.2 (5)
O5—N4—C13—C12	−178.0 (3)	N3—C11—C10—C9	178.1 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5	0.86	2.01	2.619 (4)	127
O1—H1···O2ⁱⁱ	0.82	2.37	3.114 (4)	152
O1—H1···O3ⁱⁱ	0.82	2.25	2.998 (4)	152
N2—H2···O5ⁱⁱⁱ	0.86	2.58	3.362 (4)	152
C9—H9···Cl1^iv	0.93	2.72	3.485 (4)	140

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

Funding information

Funding for this research was provided by: Ondokuz Mayıs University (project number PYO.FEN.1906.19.001) .

References

Becke, A. D. (1993). J. Chem. Phys. 98, 5648–5652. CrossRef CAS Web of Science Google Scholar
Borwick, S. J., Howard, J. A. K., Lehmann, C. W. & O'Hagan, D. (1997). Acta Cryst. C53, 124–126. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Desai, S. B., Desai, P. B. & Desai, K. R. (2001). Heterocycl. Commun. 7, 83–90. CrossRef CAS Google Scholar
Faizi, M. S. H., Ali, A. & Potaskalov, V. A. (2016a). Acta Cryst. E72, 1366–1369. Web of Science CSD CrossRef IUCr Journals Google Scholar
Faizi, M. S. H., Dege, N., Haque, A., Kalibabchuk, V. A. & Cemberci, M. (2017). Acta Cryst. E73, 96–98. Web of Science CSD CrossRef IUCr Journals Google Scholar
Faizi, M. S. H., Gupta, S., Mohan, V. K., Jain, K. V. & Sen, P. (2016b). Sens. Actuators B Chem. 222, 15–20. Web of Science CrossRef CAS Google Scholar
Faizi, M. S. H. & Prisyazhnaya, E. V. (2015). Acta Cryst. E71, m175–m176. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., et al. (2009). GAUSSIAN09. Gaussian Inc., Wallingford, CT, USA. Google Scholar
Fun, H.-K., Chantrapromma, S., Nilwanna, B., Kobkeatthawin, T. & Boonnak, N. (2013). Acta Cryst. E69, o1203–o1204. CSD CrossRef CAS IUCr Journals Google Scholar
Furniss, B. S., Hannaford, A. J., Smith, P. W. G. & Tatchell, A. R. (1999). Vogel's Textbook of Practical Organic Chemistry, 5th ed. London: Longmans. Google Scholar
Ghosh, P., Kumar, N., Mukhopadhyay, S. K. & Banerjee, P. (2016). Sens. Actuators B Chem. 224, 899–906. Web of Science CSD CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Guillaumont, D. & Nakamura, S. (2000). Dyes Pigments, 46, 85–92. Web of Science CrossRef CAS Google Scholar
Karia, F. D. & Parsania, P. H. (1999). Asian J. Chem. 11, 991–995. CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ohba, S. (1996). Acta Cryst. C52, 2118–2119. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Raj, B. N. B. & Kurup, M. R. P. (2007). Spectrochim. Acta Part A, 66, 898–903. Google Scholar
Sheikhshoaie, I. & Sharif, M. A. (2006). Acta Cryst. E62, o3563–o3565. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Singh, W. M. & Dash, B. C. (1988). Pesticides, 22, 33–37. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2002). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar

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