2,4-Di­chloro-6-[(2-hy­droxy-5-methyl­anilino)methyl­idene]cyclo­hexa-2,4-dienone

Pal, T.K.; Alam, M.A.; Hossain, M.D.; Paul, S.; Miyatake, R.; Sheikh, M.C.

doi:10.1107/S2414314619014019

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 10| October 2019| x191401

https://doi.org/10.1107/S2414314619014019

Open

access

2,4-Dichloro-6-[(2-hydroxy-5-methylanilino)methylidene]cyclohexa-2,4-dienone

Tarun Kumar Pal,^a Md Ashraful Alam,^a Md Dulal Hossain,^a Subrata Paul,^b Ryuta Miyatake ^c and Md Chanmiya Sheikh ^d,^e ^*

^aDepartment of Chemistry, Rajshahi University of Engineering & Technology, Rajshahi 6204, Bangladesh, ^bDepartment of Pharmacy, University of Rajshahi, Rajshahi 6205, Bangladesh, ^cCenter for Environmental Conservation and Research Safety, University of Toyama, 3190 Gofuku, Toyama 930-8555, Japan, ^dGraduate School of Environmental and Life Science, Okayama University, Okayama 700-8530, Japan, and ^eDepartment of Applied Chemistry, Faculty of Engineering, University of Toyama, 3190 Gofuku, Toyama 930-8555, Japan
^*Correspondence e-mail: chansheikh@yahoo.com

Edited by H. Ishida, Okayama University, Japan (Received 3 October 2019; accepted 15 October 2019; online 29 October 2019)

The title compound, C₁₄H₁₁Cl₂NO₂, has been prepared by the condensation of 3,5-dichlorosalicylaldehyde and 2-amino-4-methylphenol. The asymmetric unit consists of two independent molecules, both of which are almost planar; the dihedral angle between the two benzene rings is 10.61 (8)° for one molecule and 2.46 (8)° for the other. There is an intramolecular N—H⋯O hydrogen bond that generates S(6) ring motifs in each molecule. In the crystal, the two independent molecules are linked by O—H⋯O and C—H⋯Cl hydrogen bonds, forming a pseudo-inversion dimer. A π–π interaction, with a centroid–centroid distance of 3.6065 (12) Å, is also observed.

Keywords: crystal structure; Schiff base; hydrogen bonding.

CCDC references: 1860532; 1860532

Structure description

Halogen atoms in Schiff base ligands (Dong et al., 2015 ; Pal et al., 2018 ) and their metal complexes are interesting because of their possible bioactivities (Dong et al., 2015; Rani & Bheeter, 2016 ). In view of the biological activities of these compounds, which are related to structural aspects, and as part of our studies on 2,4-dibromo-6-[(2-hydroxy-5-methylanilino)methylidene]cyclohexa-2,4-dienone, we report herein the synthesis and crystal structure of 2,4-dichloro-6-[(2-hydroxy-5-methylanilino)methylidene]cyclohexa-2,4-dienone.

The C2—O1 and C16—O3 bond lengths reveal double-bond character, while the C7—N1 and C15—N2 bonds show single-bond character (Khalaji et al., 2015 ; Pal et al., 2018). There is an intramolecular N—H⋯O hydrogen bond (Table 1) that generates S(6) ring motifs in each molecule. In the crystal, the two independent molecules are linked through two O—H⋯O hydrogen bonds, creating a pseudo-inversion dimer, with an R₂²(18) ring motif, in which C—H⋯Cl interactions further link the molecules (Fig. 1 and Table 1). A π–π stacking interaction, with a centroid–centroid distance of 3.6065 (12) Å, is also observed between the C16–C21 and C22–C27 rings.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.84 (3)	1.87 (3)	2.693 (2)	168 (3)
O4—H4⋯O1	0.83 (3)	1.89 (3)	2.685 (2)	160 (3)
N1—H1⋯O1	0.80 (2)	1.96 (2)	2.617 (2)	139 (2)
N2—H3⋯O3	0.87 (2)	1.90 (2)	2.603 (2)	137 (2)
C10—H10⋯Cl3	0.95	2.88	3.660 (2)	140
C24—H24⋯Cl1	0.95	2.72	3.661 (2)	172

Figure 1
The asymmetric unit of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as spheres of arbitrary radii. Intermolecular C—H⋯Cl and O—H⋯O and intramolecular N—H⋯O hydrogen bonds are indicated by dashed lines.

Synthesis and crystallization

An ethanol solution of 3,5-dichlorosalicylaldehyde (100 mg, 0.52 mmol) was added dropwise to an ethanol solution of 2-amino-4-methylphenol (77 mg, 0.62 mmol) with continuous stirring at 333 K. A bright-orange coloured precipitate of the title compound formed immediately. The resulting mixture was stirred for a further 1 h at room temperature for completion of the reaction. On cooling, an orange solid product was isolated by filtration, washed with hot ethanol and dried in a vacuum (yield 125 mg, 77%). Orange needle-like single crystals were obtained from an N,N-dimethylformamide–acetonitrile (1:7 v/v) solution by slow evaporation of the solvent at room temperature over a period of 15 d (m.p. 457 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₁Cl₂NO₂
M_r	296.15
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	16.6119 (5), 6.83947 (16), 22.5749 (6)
β (°)	98.255 (7)
V (Å³)	2538.30 (12)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.51
Crystal size (mm)	0.37 × 0.15 × 0.07

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995 )
T_min, T_max	0.697, 0.965
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	24092, 5794, 4366
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.100, 1.03
No. of reflections	5794
No. of parameters	361
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.39
Computer programs: RAPID-AUTO (Rigaku, 2001 ), SIR92 (Altomare et al., 1993 ), SHELXL97 (Sheldrick, 2008 ) and CrystalStructure (Rigaku, 2018 ).

Structural data

CCDC references: 1860532; 1860532

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314619014019/is4037sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619014019/is4037Isup2.hkl

Cover Letter with list of change. DOI: https://doi.org/10.1107/S2414314619014019/is4037sup3.doc

checkCIF report

Computing details top

Cell refinement: RAPID-AUTO (Rigaku, 2001); data reduction: RAPID-AUTO (Rigaku, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2018); software used to prepare material for publication: CrystalStructure (Rigaku, 2018).

2,4-Dichloro-6-[(2-hydroxy-5-methylanilino)methylidene]cyclohexa-2,4-dienone top

Crystal data top

C₁₄H₁₁Cl₂NO₂	F(000) = 1216.00
M_r = 296.15	D_x = 1.550 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71075 Å
a = 16.6119 (5) Å	Cell parameters from 16379 reflections
b = 6.83947 (16) Å	θ = 1.8–27.5°
c = 22.5749 (6) Å	µ = 0.51 mm⁻¹
β = 98.255 (7)°	T = 173 K
V = 2538.30 (12) Å³	Needle, orange
Z = 8	0.37 × 0.14 × 0.07 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	4366 reflections with F² > 2.0σ(F²)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.049
ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −21→21
T_min = 0.697, T_max = 0.965	k = −8→8
24092 measured reflections	l = −27→29
5794 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0427P)² + 1.2427P] where P = (F_o² + 2F_c²)/3
5794 reflections	(Δ/σ)_max = 0.001
361 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³
Primary atom site location: structure-invariant direct methods

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 was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
Cl1	0.25495 (3)	0.09343 (10)	−0.08874 (3)	0.03921 (16)
Cl2	0.51221 (3)	0.11130 (8)	−0.20767 (2)	0.03353 (14)
Cl3	0.50788 (3)	0.19328 (9)	0.35698 (3)	0.03368 (14)
Cl4	0.26343 (4)	0.11237 (10)	0.48780 (2)	0.04106 (16)
O1	0.37601 (9)	0.2150 (2)	0.01624 (6)	0.0307 (4)
O2	0.45249 (9)	0.3530 (2)	0.16615 (7)	0.0319 (4)
O3	0.37348 (9)	0.2238 (2)	0.25471 (6)	0.0312 (4)
O4	0.28678 (9)	0.1500 (3)	0.10445 (7)	0.0335 (4)
N1	0.52248 (11)	0.3018 (3)	0.06875 (8)	0.0238 (4)
N2	0.22374 (11)	0.1714 (3)	0.20494 (8)	0.0240 (4)
C1	0.49095 (12)	0.2179 (3)	−0.03532 (9)	0.0224 (4)
C2	0.40586 (12)	0.1912 (3)	−0.03220 (9)	0.0230 (4)
C3	0.35810 (12)	0.1351 (3)	−0.08807 (9)	0.0252 (4)
C4	0.39050 (13)	0.1133 (3)	−0.14003 (9)	0.0264 (4)
H4A	0.356340	0.078181	−0.175870	0.032*
C5	0.47392 (13)	0.1425 (3)	−0.14064 (9)	0.0253 (4)
C6	0.52355 (13)	0.1907 (3)	−0.08924 (9)	0.0258 (4)
H6	0.580302	0.206062	−0.089665	0.031*
C7	0.54515 (12)	0.2706 (3)	0.01641 (9)	0.0246 (4)
H7	0.601196	0.284176	0.012926	0.029*
C8	0.57277 (12)	0.3531 (3)	0.12254 (9)	0.0226 (4)
C9	0.53468 (12)	0.3730 (3)	0.17345 (9)	0.0253 (4)
C10	0.58203 (13)	0.4161 (3)	0.22768 (9)	0.0297 (5)
H10	0.557122	0.429067	0.262812	0.036*
C11	0.66529 (13)	0.4401 (3)	0.23091 (10)	0.0299 (5)
H11	0.696733	0.468769	0.268450	0.036*
C12	0.70405 (12)	0.4233 (3)	0.18025 (10)	0.0269 (5)
C13	0.65650 (12)	0.3793 (3)	0.12615 (9)	0.0252 (4)
H13	0.681486	0.366869	0.091027	0.030*
C14	0.79483 (13)	0.4497 (4)	0.18360 (11)	0.0359 (5)
H14A	0.808814	0.463165	0.143078	0.043*
H14B	0.822829	0.335619	0.203108	0.043*
H14C	0.811765	0.567534	0.206801	0.043*
C15	0.20603 (12)	0.1554 (3)	0.25913 (9)	0.0236 (4)
H15	0.150757	0.136914	0.264204	0.028*
C16	0.34976 (12)	0.1928 (3)	0.30534 (9)	0.0234 (4)
C17	0.40453 (12)	0.1814 (3)	0.36060 (9)	0.0243 (4)
C18	0.37823 (12)	0.1580 (3)	0.41483 (9)	0.0256 (5)
H18	0.416378	0.153527	0.450438	0.031*
C19	0.29454 (13)	0.1406 (3)	0.41776 (9)	0.0266 (5)
C20	0.23901 (12)	0.1389 (3)	0.36714 (9)	0.0251 (4)
H20	0.182907	0.120713	0.369653	0.030*
C21	0.26538 (12)	0.1643 (3)	0.31084 (9)	0.0225 (4)
C22	0.16925 (12)	0.1673 (3)	0.15075 (9)	0.0231 (4)
C23	0.20467 (12)	0.1583 (3)	0.09815 (9)	0.0260 (5)
C24	0.15371 (14)	0.1588 (3)	0.04366 (10)	0.0304 (5)
H24	0.176341	0.152636	0.007370	0.037*
C25	0.07038 (13)	0.1681 (3)	0.04194 (10)	0.0300 (5)
H25	0.036697	0.168583	0.004192	0.036*
C26	0.03407 (12)	0.1770 (3)	0.09397 (10)	0.0270 (5)
C27	0.08532 (12)	0.1767 (3)	0.14838 (9)	0.0257 (4)
H27	0.062516	0.183028	0.184586	0.031*
C28	−0.05674 (13)	0.1887 (4)	0.09160 (11)	0.0360 (5)
H28A	−0.071234	0.159467	0.131228	0.043*
H28B	−0.082835	0.093679	0.062499	0.043*
H28C	−0.075315	0.320734	0.079520	0.043*
H1	0.4750 (14)	0.283 (3)	0.0701 (10)	0.025 (6)*
H2	0.4343 (18)	0.314 (4)	0.1968 (14)	0.060 (9)*
H3	0.2752 (15)	0.184 (4)	0.2018 (10)	0.033 (7)*
H4	0.3040 (18)	0.164 (4)	0.0721 (14)	0.060 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0229 (3)	0.0649 (4)	0.0302 (3)	−0.0034 (3)	0.0053 (2)	−0.0073 (3)
Cl2	0.0391 (3)	0.0394 (3)	0.0252 (3)	−0.0016 (3)	0.0151 (2)	−0.0022 (2)
Cl3	0.0186 (2)	0.0485 (3)	0.0346 (3)	0.0009 (2)	0.0061 (2)	0.0030 (3)
Cl4	0.0320 (3)	0.0703 (4)	0.0227 (3)	−0.0026 (3)	0.0102 (2)	−0.0022 (3)
O1	0.0237 (8)	0.0454 (9)	0.0240 (8)	0.0020 (7)	0.0074 (6)	−0.0025 (7)
O2	0.0231 (8)	0.0434 (10)	0.0303 (9)	−0.0021 (7)	0.0079 (7)	0.0034 (7)
O3	0.0226 (8)	0.0473 (10)	0.0252 (8)	−0.0007 (7)	0.0084 (6)	0.0008 (7)
O4	0.0200 (8)	0.0538 (11)	0.0279 (8)	−0.0023 (7)	0.0081 (6)	−0.0002 (8)
N1	0.0197 (9)	0.0249 (9)	0.0270 (9)	−0.0011 (7)	0.0038 (7)	0.0006 (7)
N2	0.0186 (9)	0.0301 (10)	0.0239 (9)	−0.0012 (7)	0.0051 (7)	−0.0019 (7)
C1	0.0249 (10)	0.0199 (10)	0.0230 (10)	0.0000 (8)	0.0048 (8)	0.0017 (8)
C2	0.0237 (10)	0.0221 (10)	0.0236 (10)	0.0027 (8)	0.0044 (8)	0.0021 (8)
C3	0.0207 (10)	0.0282 (11)	0.0269 (11)	0.0010 (8)	0.0045 (8)	0.0005 (9)
C4	0.0304 (11)	0.0266 (11)	0.0220 (10)	0.0012 (9)	0.0029 (8)	0.0026 (9)
C5	0.0323 (11)	0.0244 (11)	0.0212 (10)	0.0008 (9)	0.0110 (9)	0.0020 (8)
C6	0.0258 (11)	0.0262 (11)	0.0268 (11)	−0.0030 (9)	0.0082 (9)	0.0022 (9)
C7	0.0229 (10)	0.0254 (11)	0.0264 (11)	−0.0013 (8)	0.0066 (8)	0.0008 (9)
C8	0.0253 (10)	0.0191 (10)	0.0232 (10)	−0.0001 (8)	0.0026 (8)	−0.0007 (8)
C9	0.0245 (10)	0.0247 (11)	0.0278 (11)	0.0015 (9)	0.0077 (8)	0.0038 (9)
C10	0.0335 (12)	0.0347 (12)	0.0224 (10)	0.0022 (10)	0.0089 (9)	0.0007 (9)
C11	0.0313 (12)	0.0337 (13)	0.0236 (11)	0.0004 (9)	−0.0005 (9)	−0.0003 (9)
C12	0.0232 (10)	0.0258 (11)	0.0311 (11)	0.0017 (9)	0.0018 (9)	0.0017 (9)
C13	0.0262 (11)	0.0260 (11)	0.0243 (10)	0.0007 (9)	0.0069 (8)	0.0000 (9)
C14	0.0253 (11)	0.0458 (14)	0.0358 (13)	−0.0036 (10)	0.0009 (10)	−0.0039 (11)
C15	0.0202 (10)	0.0241 (11)	0.0270 (11)	−0.0005 (8)	0.0056 (8)	−0.0020 (8)
C16	0.0233 (10)	0.0242 (10)	0.0235 (10)	0.0009 (8)	0.0064 (8)	−0.0021 (8)
C17	0.0188 (10)	0.0280 (11)	0.0269 (11)	0.0004 (8)	0.0061 (8)	−0.0012 (9)
C18	0.0236 (10)	0.0298 (12)	0.0228 (10)	−0.0011 (9)	0.0017 (8)	−0.0023 (9)
C19	0.0279 (11)	0.0319 (12)	0.0218 (10)	−0.0010 (9)	0.0100 (8)	−0.0027 (9)
C20	0.0192 (10)	0.0294 (11)	0.0280 (11)	0.0011 (8)	0.0079 (8)	−0.0018 (9)
C21	0.0217 (10)	0.0223 (10)	0.0238 (10)	0.0006 (8)	0.0048 (8)	−0.0035 (8)
C22	0.0233 (10)	0.0235 (10)	0.0225 (10)	−0.0018 (8)	0.0030 (8)	−0.0025 (8)
C23	0.0201 (10)	0.0312 (12)	0.0272 (11)	−0.0021 (9)	0.0056 (8)	−0.0012 (9)
C24	0.0311 (12)	0.0385 (13)	0.0231 (11)	−0.0034 (10)	0.0087 (9)	−0.0027 (9)
C25	0.0280 (11)	0.0346 (12)	0.0262 (11)	−0.0004 (9)	−0.0009 (9)	−0.0031 (9)
C26	0.0227 (10)	0.0282 (11)	0.0297 (11)	0.0011 (9)	0.0030 (9)	−0.0056 (9)
C27	0.0240 (10)	0.0299 (11)	0.0240 (10)	0.0006 (9)	0.0068 (8)	−0.0035 (9)
C28	0.0223 (11)	0.0455 (14)	0.0394 (13)	0.0029 (10)	0.0020 (9)	−0.0063 (11)

Geometric parameters (Å, º) top

Cl1—C3	1.735 (2)	C11—C12	1.395 (3)
Cl2—C5	1.737 (2)	C11—H11	0.9500
Cl3—C17	1.732 (2)	C12—C13	1.389 (3)
Cl4—C19	1.743 (2)	C12—C14	1.510 (3)
O1—C2	1.274 (2)	C13—H13	0.9500
O2—C9	1.358 (2)	C14—H14A	0.9800
O2—H2	0.84 (3)	C14—H14B	0.9800
O3—C16	1.279 (2)	C14—H14C	0.9800
O4—C23	1.352 (2)	C15—C21	1.417 (3)
O4—H4	0.83 (3)	C15—H15	0.9500
N1—C7	1.308 (3)	C16—C17	1.437 (3)
N1—C8	1.416 (3)	C16—C21	1.438 (3)
N1—H1	0.80 (2)	C17—C18	1.367 (3)
N2—C15	1.303 (3)	C18—C19	1.406 (3)
N2—C22	1.414 (3)	C18—H18	0.9500
N2—H3	0.87 (2)	C19—C20	1.362 (3)
C1—C6	1.414 (3)	C20—C21	1.413 (3)
C1—C7	1.415 (3)	C20—H20	0.9500
C1—C2	1.437 (3)	C22—C27	1.389 (3)
C2—C3	1.442 (3)	C22—C23	1.400 (3)
C3—C4	1.367 (3)	C23—C24	1.390 (3)
C4—C5	1.402 (3)	C24—C25	1.381 (3)
C4—H4A	0.9500	C24—H24	0.9500
C5—C6	1.364 (3)	C25—C26	1.396 (3)
C6—H6	0.9500	C25—H25	0.9500
C7—H7	0.9500	C26—C27	1.390 (3)
C8—C13	1.393 (3)	C26—C28	1.504 (3)
C8—C9	1.396 (3)	C27—H27	0.9500
C9—C10	1.388 (3)	C28—H28A	0.9800
C10—C11	1.384 (3)	C28—H28B	0.9800
C10—H10	0.9500	C28—H28C	0.9800

C9—O2—H2	114 (2)	H14A—C14—H14B	109.5
C23—O4—H4	112 (2)	C12—C14—H14C	109.5
C7—N1—C8	127.17 (18)	H14A—C14—H14C	109.5
C7—N1—H1	114.9 (16)	H14B—C14—H14C	109.5
C8—N1—H1	117.8 (16)	N2—C15—C21	123.07 (19)
C15—N2—C22	127.43 (18)	N2—C15—H15	118.5
C15—N2—H3	116.1 (16)	C21—C15—H15	118.5
C22—N2—H3	116.4 (16)	O3—C16—C17	123.15 (18)
C6—C1—C7	117.84 (18)	O3—C16—C21	121.93 (18)
C6—C1—C2	121.77 (18)	C17—C16—C21	114.91 (18)
C7—C1—C2	120.38 (18)	C18—C17—C16	122.67 (18)
O1—C2—C1	122.18 (18)	C18—C17—Cl3	119.61 (16)
O1—C2—C3	123.47 (18)	C16—C17—Cl3	117.70 (15)
C1—C2—C3	114.35 (18)	C17—C18—C19	119.83 (19)
C4—C3—C2	122.99 (19)	C17—C18—H18	120.1
C4—C3—Cl1	118.98 (16)	C19—C18—H18	120.1
C2—C3—Cl1	118.03 (15)	C20—C19—C18	121.09 (19)
C3—C4—C5	120.29 (19)	C20—C19—Cl4	120.45 (16)
C3—C4—H4A	119.9	C18—C19—Cl4	118.42 (16)
C5—C4—H4A	119.9	C19—C20—C21	119.58 (19)
C6—C5—C4	120.24 (19)	C19—C20—H20	120.2
C6—C5—Cl2	121.25 (17)	C21—C20—H20	120.2
C4—C5—Cl2	118.50 (16)	C20—C21—C15	117.83 (18)
C5—C6—C1	120.32 (19)	C20—C21—C16	121.75 (18)
C5—C6—H6	119.8	C15—C21—C16	120.40 (18)
C1—C6—H6	119.8	C27—C22—C23	120.73 (19)
N1—C7—C1	123.73 (19)	C27—C22—N2	123.16 (18)
N1—C7—H7	118.1	C23—C22—N2	116.09 (18)
C1—C7—H7	118.1	O4—C23—C24	124.8 (2)
C13—C8—C9	120.40 (19)	O4—C23—C22	116.94 (19)
C13—C8—N1	122.91 (19)	C24—C23—C22	118.29 (19)
C9—C8—N1	116.68 (18)	C25—C24—C23	120.4 (2)
O2—C9—C10	124.10 (19)	C25—C24—H24	119.8
O2—C9—C8	117.18 (19)	C23—C24—H24	119.8
C10—C9—C8	118.70 (19)	C24—C25—C26	122.1 (2)
C11—C10—C9	120.5 (2)	C24—C25—H25	119.0
C11—C10—H10	119.8	C26—C25—H25	119.0
C9—C10—H10	119.8	C27—C26—C25	117.34 (19)
C10—C11—C12	121.5 (2)	C27—C26—C28	121.0 (2)
C10—C11—H11	119.3	C25—C26—C28	121.6 (2)
C12—C11—H11	119.3	C22—C27—C26	121.20 (19)
C13—C12—C11	117.86 (19)	C22—C27—H27	119.4
C13—C12—C14	120.5 (2)	C26—C27—H27	119.4
C11—C12—C14	121.61 (19)	C26—C28—H28A	109.5
C12—C13—C8	121.09 (19)	C26—C28—H28B	109.5
C12—C13—H13	119.5	H28A—C28—H28B	109.5
C8—C13—H13	119.5	C26—C28—H28C	109.5
C12—C14—H14A	109.5	H28A—C28—H28C	109.5
C12—C14—H14B	109.5	H28B—C28—H28C	109.5

C6—C1—C2—O1	179.81 (19)	C22—N2—C15—C21	−179.03 (19)
C7—C1—C2—O1	0.6 (3)	O3—C16—C17—C18	176.6 (2)
C6—C1—C2—C3	0.1 (3)	C21—C16—C17—C18	−4.1 (3)
C7—C1—C2—C3	−179.18 (19)	O3—C16—C17—Cl3	−4.7 (3)
O1—C2—C3—C4	178.8 (2)	C21—C16—C17—Cl3	174.60 (15)
C1—C2—C3—C4	−1.4 (3)	C16—C17—C18—C19	1.1 (3)
O1—C2—C3—Cl1	−1.3 (3)	Cl3—C17—C18—C19	−177.52 (16)
C1—C2—C3—Cl1	178.49 (15)	C17—C18—C19—C20	2.6 (3)
C2—C3—C4—C5	1.1 (3)	C17—C18—C19—Cl4	−179.65 (17)
Cl1—C3—C4—C5	−178.84 (16)	C18—C19—C20—C21	−3.0 (3)
C3—C4—C5—C6	0.8 (3)	Cl4—C19—C20—C21	179.27 (16)
C3—C4—C5—Cl2	179.56 (16)	C19—C20—C21—C15	178.05 (19)
C4—C5—C6—C1	−2.1 (3)	C19—C20—C21—C16	−0.2 (3)
Cl2—C5—C6—C1	179.16 (16)	N2—C15—C21—C20	−178.05 (19)
C7—C1—C6—C5	−179.09 (19)	N2—C15—C21—C16	0.2 (3)
C2—C1—C6—C5	1.7 (3)	O3—C16—C21—C20	−177.08 (19)
C8—N1—C7—C1	179.40 (19)	C17—C16—C21—C20	3.6 (3)
C6—C1—C7—N1	179.33 (19)	O3—C16—C21—C15	4.7 (3)
C2—C1—C7—N1	−1.4 (3)	C17—C16—C21—C15	−174.60 (19)
C7—N1—C8—C13	0.6 (3)	C15—N2—C22—C27	10.8 (3)
C7—N1—C8—C9	−178.1 (2)	C15—N2—C22—C23	−170.8 (2)
C13—C8—C9—O2	177.48 (18)	C27—C22—C23—O4	179.84 (19)
N1—C8—C9—O2	−3.8 (3)	N2—C22—C23—O4	1.4 (3)
C13—C8—C9—C10	−1.1 (3)	C27—C22—C23—C24	−0.1 (3)
N1—C8—C9—C10	177.64 (19)	N2—C22—C23—C24	−178.47 (19)
O2—C9—C10—C11	−177.9 (2)	O4—C23—C24—C25	−179.8 (2)
C8—C9—C10—C11	0.5 (3)	C22—C23—C24—C25	0.1 (3)
C9—C10—C11—C12	0.4 (3)	C23—C24—C25—C26	−0.1 (3)
C10—C11—C12—C13	−0.7 (3)	C24—C25—C26—C27	0.2 (3)
C10—C11—C12—C14	179.9 (2)	C24—C25—C26—C28	179.5 (2)
C11—C12—C13—C8	0.1 (3)	C23—C22—C27—C26	0.1 (3)
C14—C12—C13—C8	179.5 (2)	N2—C22—C27—C26	178.4 (2)
C9—C8—C13—C12	0.8 (3)	C25—C26—C27—C22	−0.2 (3)
N1—C8—C13—C12	−177.85 (19)	C28—C26—C27—C22	−179.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.84 (3)	1.87 (3)	2.693 (2)	168 (3)
O4—H4···O1	0.83 (3)	1.89 (3)	2.685 (2)	160 (3)
N1—H1···O1	0.80 (2)	1.96 (2)	2.617 (2)	139 (2)
N2—H3···O3	0.87 (2)	1.90 (2)	2.603 (2)	137 (2)
C10—H10···Cl3	0.95	2.88	3.660 (2)	140
C24—H24···Cl1	0.95	2.72	3.661 (2)	172

Acknowledgements

The authors are grateful to the Department of Chemistry, Rajshahi University of Engineering & Technology (RUET), for the provision of laboratory facilities, and the Center for Environmental Conservation and Research Safety, University of Toyama, Japan, for providing facilities for single-crystal X-ray analysis. TKP is highly obliged to the director, Research and extension RUET, for providing internal research project funding.

Funding information

Funding for this research was provided by: Rajshahi University of Engineering and Technology (award No. DRE/5/RUET/200).

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Dong, Y. L., Li, C., Meng, X. F., Zhou, X. & Ma, J. J. (2015). J. Struct. Chem. 56, 1426–1430. Web of Science CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Khalaji, A. D., Hafez Ghoran, S., Pojarová, M. & Dušek, M. (2015). J. Struct. Chem. 56, 1410–1414. Web of Science CrossRef CAS Google Scholar
Pal, T. K., Hossain, M. D., Sheikh, M. C., Miyatake, R. & Alam, M. A. (2018). IUCrData, 3, x180388. Google Scholar
Rani, K. J. & Bheeter, S. R. (2016). Asian J. Biochem. Pharm. Res. 3, 72–81. Google Scholar
Rigaku (2001). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2018). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.