Crystal structure and Hirshfeld surface analysis of diethyl 5-(2-cyano­phen­oxy)isophthalate

Muslim, M.; Ali, A.; Kamaal, S.; Ahmad, M.; Afzal, M.; Plutenko, M.O.

doi:10.1107/S2056989020004508

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ISSN: 2056-9890

Volume 76| Part 6| June 2020| Pages 905-908

https://doi.org/10.1107/S2056989020004508

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Crystal structure and Hirshfeld surface analysis of diethyl 5-(2-cyanophenoxy)isophthalate

Mohd Muslim,^a Arif Ali,^a Saima Kamaal,^a Musheer Ahmad,^a ^* Mohd Afzal ^b and Maksym O. Plutenko ^c ^*

^aDepartment of Applied Chemistry, ZHCET, Aligarh Muslim University, Aligarh, 202002, (UP), India, ^bCatalytic Chemistry Research Chair, Department of Chemistry, College of Science, KSU, Riyadh 11451, Saudi Arabia, and ^cDepartment of Chemistry, National Taras Shevchenko University, Volodymyrska Street 64, 01601 Kyiv, Ukraine
^*Correspondence e-mail: amusheer4@gmail.com, plutenkom@yahoo.com

Edited by J. Ellena, Universidade de Sâo Paulo, Brazil (Received 23 March 2020; accepted 1 May 2020; online 22 May 2020)

The title compound, C₁₉H₁₇NO₅, obtained by ether bond formation between the reagents, crystallizes in the monoclinic space group P2₁/c. The compound is non-planar, subtending a dihedral angle of 82.38 (4)° between the plane of hydroxy isophthalate-based ester and that of the benzonitrile moiety. The molecule is bent at the ether linkage, with a C_aryl—O—C_aryl bond angle of 116.74 (11)°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds and other weak interactions forming a supramolecular framework. A Hirshfeld surface analysis was performed to generate two-dimensional fingerprint plots, which reveal the type of interactions occurring in the vicinity of the molecule.

Keywords: crystal structure; 5-hydroxy-isophthalic acid; hydrogen bonding; 2-fluorobenzonitrile.

CCDC reference: 1981835

1. Chemical context

5-Hydroxyisophthalic acid and its derivatives have been used in the synthesis of several organic ligands. This type of ligand has an isophthalate moiety, which has oxygen-rich carbon chains that are sufficiently reactive to incorporate functionality, followed by conjugation with biomolecular compounds (Calderon et al., 2010 ; Khandare et al., 2012 ). Carboxylate-containing ligands have been used for the synthesis of coordination polymers because of their flexible nature. The flexibility of the ligand and hardness of metal ions improve the stability of coordination polymers (Ahmad et al., 2012 ). Coordination polymers have been used in various types of applications as a result of their physical properties, which include ferromagnetic behaviour, antiferromagnetic ordering, spin canting and metamagnetism (Wang et al., 2005 ; Liu et al., 2010 ). Several types of framework have been obtained, such as metal complexes, clusters, and metal–organic frameworks by linking of the flexible organic linker and metal ion, leading to interesting magnetic properties (Cheon & Suh, 2009 ; Wang et al., 2009 ). Organic ligands containing ether linkages have been used to synthesize magnetic materials because these types of organic ligands exhibit a binding ability that can efficiently transmit magnetic coupling (Coronado et al., 2000 ; Masciocchi et al., 2009 ; Yu et al., 2010 ).

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The compound crystallizes in the monoclinic space group P2₁/c. The asymmetric unit contains one unit of 5-hydroxy-isophthalic acid diethyl ester and one unit of benzonitrile, connected by an ether bridge linkage. The molecule is non-planar, with a C12—O5—C14 bond angle of 116.74 (11)° at the ether group, and a C14—O5—C12—C13 torsion angle at the bridge of −97.37 (2)°. The C12—O5 bond length, 1.4025 (17) Å, is comparable to the C-O bond lengths obtained for similar ligands. The C3—O1 and C3—O2 bond lengths are 1.3377 (18) and 1.2061 (19) Å, respectively, and are in the expected ranges (Cambridge Structural Database; Groom et al., 2016 ).

Figure 1
The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% level.

3. Supramolecular features

In the crystal, the molecules are connected through C2—H2A⋯O4, C16—H16⋯O2 and C13—H13⋯O4 hydrogen bonds (Table 1, Fig. 2). They are linked by a series of C10—H10C⋯π and C3—O2⋯C16, C7—O4⋯C2 and C20—N1⋯C7 weak interactions, forming an extended supramolecular framework (Fig. 3). π–π interactions with Cg1⋯Cg2(1 − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z) = 3.9572 (9) Å where Cg1 andCg2 are the centroids of the C4–C6/C11–C13 and C14–C19 rings, respectively, and a C—H⋯N interaction are also observed.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C4–C6/C11–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯O4ⁱ	0.98 (2)	2.50 (2)	3.2071 (2)	128 (1)
C13—H13⋯O4ⁱⁱ	0.936 (16)	2.514 (16)	3.4179 (2)	163.5 (12)
C16—H16⋯O2ⁱⁱⁱ	0.997 (17)	2.516 (17)	3.1941 (2)	125.7 (13)
C18—H18⋯N1^iv	0.945 (17)	2.629 (17)	3.430 (2)	143.0 (13)
C10—H10C⋯Cg1^v	1.00 (2)	2.96 (2)	3.7893 (19)	140 (2)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x+2, -y+1, -z+2; (v) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
A view along the b axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

Figure 3
A view along the a axis of the crystal packing of the title compound. The C—H⋯π and other weak interactions are indicated by dashed lines.

4. Hirshfeld analysis

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon, et al., 2007 ) were performed with Crystal Explorer17 (Turner et al., 2017 ) to investigate the intermolecular interactions and surface morphology of the crystal structure. The Hirshfeld surface mapped over d_norm (Fig. 4) in the colour range −0.174 to 1.315 a.u. from red (shorter distance than the sum of van der Waals radii) and white to blue (longer distance than the sum of van der Waals radii). The bright red spot on the d_norm surface corresponds to a weak interaction e.g. hydrogen bonding, blue indicates close contacts and a white spot shows van der Waals interactions. In the crystal there are three major types of interaction (H⋯H = 41.2%, H⋯O = 20.5%, C⋯H = 16.3%) on the d_norm surface. The two-dimensional fingerprint plots are shown in Fig. 5. The interaction order of d_norm on the 2D fingerprint plot (H⋯H)>(H⋯O)>(C⋯H) represents the nature of the packing in the crystal structure. The contribution of these major interactions (H⋯H, O⋯H/H⋯O, and C⋯H/H⋯C), governs the overall packing of crystal structure.

Figure 4
The Hirshfeld surface of the crystal structure mapped over d_norm, in the colour range −0.174 to 1.315 a.u..

Figure 5
(a) A full 2D fingerprint plot of the title compound, and delineated into (b) H⋯H (41.2%) (c) H⋯O/O⋯H (20.5%) and (d) C⋯H/H⋯C (16.3%) contacts, which are the major interactions present in the crystal structure.

5. Database survey

A search of the Cambridge Structural Database (CSD version 5.39, update of May 2018; Groom et al., 2016) for 5-hydroxy-isophthalic acid derivatives gave 38 hits for structures that include atomic coordinates. In most of the derivatives, the phenolic group is replaced by an alkoxy, a substituted alkoxy or a substituted phenoxy moiety. Only in three of the 5-hydroxy-isophthalic acid derivatives is the carboxyl group modified: IDIYIE (Petek et al., 2006 ), NUHTAM (Feng et al., 2009 ), EVIBOB (Yang et al., 2011 ). In all these compounds, the hydroxyl groups of the carboxyl moieties have been replaced by methoxy groups and the phenolic group is replaced by a substituted alkoxy or a substituted phenoxy moiety.

6. Synthesis and crystallization

5-Hydroxyisophthalic acid diethyl ester (3.7 g, 14.9 mmol) was mixed with dried K₂CO₃ (3.3g, 22.3 mmol) in a 100 ml round-bottom flask under an inert atmosphere and then treated with dry DMF (20 ml) . The mixture was stirred for 30 minutes at 353 K followed by addition of 2-fluoro-benzonitrile (1.8 ml, 16.6 mmol) and the resulting mixture was stirred for 24 h in an oil-bath at 353 K. After this period, the solution was allowed to cool to room temperature and then poured into ice-cold water (100 ml) with vigorous stirring, to afford a white precipitate, which was collected by filtration, washed with water, and dried under vacuum. Yield: 4.6 g (90%). Melting point 325 K. The ligand was crystallized from a solution in ethanol, the resultant solution was filtered and kept for slow evaporation. After 2–3 weeks, block-shaped colourless crystal were obtained, which were suitable for single-crystal X-ray diffraction analysis.

7. Refinement

Crytal data, data collection and structure refinement details are summarized in Table 2. The H atoms were freely refined.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₇NO₅
M_r	339.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.3581 (5), 10.5306 (6), 17.0141 (10)
β (°)	91.967 (2)
V (Å³)	1675.69 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.39 × 0.27 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.611, 0.746
No. of measured, independent and observed [I ≥ 2σ(I)] reflections	25974, 4149, 3134
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	1.174

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.110, 1.10
No. of reflections	4149
No. of parameters	294
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.31
Computer programs: APEX2 and SAINT (Bruker, 2016), olex2.solve and olex2.refine (Bourhis et al., 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1981835

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989020004508/ex2031sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020004508/ex2031Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020004508/ex2031Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: olex2.refine (Bourhis et al., 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Diethyl 5-(2-cyanophenoxy)benzene-1,3-dicarboxylate top

Crystal data top

C₁₉H₁₇NO₅	F(000) = 712.4237
M_r = 339.35	D_x = 1.345 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.3581 (5) Å	Cell parameters from 7552 reflections
b = 10.5306 (6) Å	θ = 3.2–28.2°
c = 17.0141 (10) Å	µ = 0.10 mm⁻¹
β = 91.967 (2)°	T = 100 K
V = 1675.69 (16) Å³	Block, colourless
Z = 4	0.39 × 0.27 × 0.16 mm

Data collection top

Bruker APEXII CCD diffractometer	3134 reflections with I ≥ 2σ(I)
φ and ω scans	R_int = 0.062
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 56.6°, θ_min = 5.8°
T_min = 0.611, T_max = 0.746	h = −12→12
25974 measured reflections	k = −14→14
4149 independent reflections	l = −22→22

Refinement top

Refinement on F²	0 constraints
Least-squares matrix: full	Primary atom site location: iterative
R[F² > 2σ(F²)] = 0.044	All H-atom parameters refined
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.035P)² + 0.7212P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
4149 reflections	Δρ_max = 0.30 e Å⁻³
294 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints

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

	x	y	z	U_iso*/U_eq
O1	0.22713 (11)	0.50496 (10)	0.53544 (6)	0.0229 (2)
O2	0.42747 (13)	0.38970 (12)	0.55579 (7)	0.0360 (3)
O3	0.06230 (11)	0.78631 (10)	0.73574 (6)	0.0213 (2)
O4	0.20643 (11)	0.84802 (11)	0.83720 (7)	0.0266 (3)
O5	0.64745 (11)	0.57614 (10)	0.80523 (6)	0.0232 (2)
N1	1.00269 (15)	0.58018 (13)	0.86616 (8)	0.0285 (3)
C1	0.1112 (2)	0.31216 (17)	0.48736 (11)	0.0312 (4)
H1a	0.026 (2)	0.3334 (18)	0.5175 (11)	0.036 (5)*
H1b	0.174 (2)	0.255 (2)	0.5194 (12)	0.044 (6)*
H1c	0.079 (2)	0.265 (2)	0.4393 (12)	0.045 (6)*
C2	0.19053 (19)	0.42986 (16)	0.46556 (9)	0.0255 (3)
H2a	0.279 (2)	0.4097 (17)	0.4384 (11)	0.030 (5)*
H2b	0.130 (2)	0.4875 (19)	0.4334 (11)	0.036 (5)*
C3	0.34773 (16)	0.47318 (14)	0.57513 (9)	0.0216 (3)
C4	0.37168 (16)	0.55112 (13)	0.64759 (9)	0.0187 (3)
C5	0.26900 (15)	0.63480 (14)	0.67416 (9)	0.0180 (3)
H5	0.1801 (18)	0.6472 (16)	0.6445 (10)	0.020 (4)*
C6	0.29409 (15)	0.70006 (13)	0.74438 (9)	0.0184 (3)
C7	0.18526 (15)	0.78627 (14)	0.77797 (9)	0.0193 (3)
C9	−0.05528 (16)	0.85475 (16)	0.77059 (10)	0.0238 (3)
H9a	−0.0642 (18)	0.8230 (17)	0.8257 (11)	0.026 (4)*
H9b	−0.0293 (18)	0.9469 (17)	0.7713 (10)	0.024 (4)*
C10	−0.18649 (17)	0.82704 (18)	0.72010 (11)	0.0282 (4)
H10a	−0.1759 (19)	0.8645 (18)	0.6671 (12)	0.033 (5)*
H10b	−0.202 (2)	0.735 (2)	0.7152 (11)	0.035 (5)*
H10c	−0.271 (2)	0.865 (2)	0.7460 (12)	0.044 (6)*
C11	0.42139 (16)	0.68242 (14)	0.78809 (9)	0.0198 (3)
H11	0.4401 (17)	0.7255 (16)	0.8374 (10)	0.021 (4)*
C12	0.52017 (15)	0.59670 (14)	0.76114 (9)	0.0193 (3)
C13	0.49852 (16)	0.53133 (14)	0.69155 (9)	0.0199 (3)
H13	0.5670 (17)	0.4739 (16)	0.6743 (9)	0.017 (4)*
C14	0.64157 (15)	0.49105 (14)	0.86643 (9)	0.0189 (3)
C15	0.51899 (17)	0.42882 (14)	0.88849 (9)	0.0216 (3)
H15	0.429 (2)	0.4474 (18)	0.8609 (11)	0.034 (5)*
C16	0.52654 (18)	0.34329 (15)	0.95050 (9)	0.0243 (3)
H16	0.4388 (18)	0.2977 (16)	0.9645 (10)	0.025 (4)*
C17	0.65468 (18)	0.31972 (15)	0.99145 (9)	0.0254 (3)
H17	0.659 (2)	0.2606 (18)	1.0337 (11)	0.034 (5)*
C18	0.77621 (17)	0.38328 (15)	0.97039 (9)	0.0229 (3)
H18	0.8631 (18)	0.3700 (16)	0.9991 (10)	0.023 (4)*
C19	0.77115 (15)	0.46874 (14)	0.90750 (9)	0.0194 (3)
C20	0.89888 (16)	0.53164 (15)	0.88389 (9)	0.0218 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0265 (6)	0.0223 (5)	0.0195 (5)	0.0021 (4)	−0.0050 (4)	−0.0020 (4)
O2	0.0327 (7)	0.0383 (7)	0.0368 (7)	0.0128 (6)	−0.0025 (5)	−0.0149 (6)
O3	0.0165 (5)	0.0264 (6)	0.0208 (5)	0.0056 (4)	−0.0010 (4)	−0.0018 (4)
O4	0.0237 (6)	0.0285 (6)	0.0274 (6)	−0.0002 (5)	−0.0019 (5)	−0.0096 (5)
O5	0.0154 (5)	0.0285 (6)	0.0252 (6)	−0.0019 (4)	−0.0048 (4)	0.0098 (5)
N1	0.0227 (7)	0.0311 (7)	0.0313 (8)	−0.0018 (6)	−0.0054 (6)	−0.0021 (6)
C1	0.0372 (10)	0.0299 (9)	0.0265 (9)	−0.0063 (8)	0.0035 (8)	−0.0051 (7)
C2	0.0340 (9)	0.0252 (8)	0.0172 (7)	−0.0020 (7)	−0.0022 (7)	−0.0022 (6)
C3	0.0219 (8)	0.0212 (7)	0.0218 (8)	0.0022 (6)	0.0006 (6)	0.0015 (6)
C4	0.0186 (7)	0.0183 (7)	0.0191 (7)	−0.0001 (6)	0.0005 (6)	0.0027 (6)
C5	0.0156 (7)	0.0185 (7)	0.0199 (7)	−0.0004 (6)	−0.0015 (6)	0.0039 (6)
C6	0.0173 (7)	0.0179 (7)	0.0200 (7)	−0.0004 (5)	0.0002 (6)	0.0036 (6)
C7	0.0174 (7)	0.0194 (7)	0.0212 (7)	−0.0007 (6)	−0.0006 (6)	0.0008 (6)
C9	0.0203 (8)	0.0280 (8)	0.0232 (8)	0.0073 (6)	0.0019 (6)	−0.0025 (7)
C10	0.0185 (8)	0.0373 (10)	0.0288 (9)	0.0051 (7)	0.0011 (7)	−0.0033 (8)
C11	0.0196 (7)	0.0212 (7)	0.0185 (7)	−0.0034 (6)	−0.0012 (6)	0.0024 (6)
C12	0.0139 (7)	0.0218 (7)	0.0220 (8)	−0.0019 (6)	−0.0026 (6)	0.0070 (6)
C13	0.0180 (7)	0.0192 (7)	0.0226 (8)	0.0017 (6)	0.0034 (6)	0.0048 (6)
C14	0.0192 (7)	0.0170 (7)	0.0204 (7)	0.0020 (6)	−0.0029 (6)	0.0001 (6)
C15	0.0192 (7)	0.0229 (7)	0.0225 (8)	0.0002 (6)	−0.0024 (6)	0.0001 (6)
C16	0.0274 (8)	0.0217 (7)	0.0241 (8)	−0.0002 (6)	0.0025 (6)	0.0009 (6)
C17	0.0334 (9)	0.0241 (8)	0.0187 (8)	0.0049 (7)	−0.0005 (6)	0.0024 (6)
C18	0.0245 (8)	0.0252 (8)	0.0184 (7)	0.0060 (6)	−0.0058 (6)	−0.0033 (6)
C19	0.0185 (7)	0.0197 (7)	0.0199 (7)	0.0018 (6)	−0.0024 (6)	−0.0041 (6)
C20	0.0194 (8)	0.0232 (7)	0.0222 (8)	0.0032 (6)	−0.0072 (6)	−0.0029 (6)

Geometric parameters (Å, º) top

O1—C2	1.4588 (18)	C9—H9a	1.002 (18)
O1—C3	1.3377 (18)	C9—H9b	1.001 (17)
O2—C3	1.2061 (19)	C9—C10	1.503 (2)
O3—C7	1.3355 (17)	C10—H10a	0.992 (19)
O3—C9	1.4583 (17)	C10—H10b	0.99 (2)
O4—C7	1.2100 (18)	C10—H10c	1.00 (2)
O5—C12	1.4025 (17)	C11—H11	0.964 (17)
O5—C14	1.3763 (18)	C11—C12	1.382 (2)
N1—C20	1.147 (2)	C12—C13	1.379 (2)
C1—H1a	0.99 (2)	C13—H13	0.936 (17)
C1—H1b	0.99 (2)	C14—C15	1.384 (2)
C1—H1c	1.00 (2)	C14—C19	1.399 (2)
C1—C2	1.498 (2)	C15—H15	0.973 (19)
C2—H2a	0.988 (19)	C15—C16	1.387 (2)
C2—H2b	0.98 (2)	C16—H16	0.988 (17)
C3—C4	1.492 (2)	C16—C17	1.388 (2)
C4—C5	1.391 (2)	C17—H17	0.950 (19)
C4—C13	1.397 (2)	C17—C18	1.378 (2)
C5—H5	0.967 (17)	C18—H18	0.945 (17)
C5—C6	1.391 (2)	C18—C19	1.398 (2)
C6—C7	1.493 (2)	C19—C20	1.436 (2)
C6—C11	1.395 (2)

C3—O1—C2	116.50 (12)	C10—C9—H9b	112.9 (10)
C9—O3—C7	115.44 (11)	H10a—C10—C9	109.7 (11)
C14—O5—C12	116.74 (11)	H10b—C10—C9	110.6 (11)
H1b—C1—H1a	108.8 (16)	H10b—C10—H10a	109.5 (15)
H1c—C1—H1a	108.1 (16)	H10c—C10—C9	108.3 (12)
H1c—C1—H1b	107.9 (17)	H10c—C10—H10a	110.4 (16)
C2—C1—H1a	110.9 (11)	H10c—C10—H10b	108.3 (16)
C2—C1—H1b	110.5 (12)	H11—C11—C6	121.8 (10)
C2—C1—H1c	110.5 (12)	C12—C11—C6	118.62 (14)
C1—C2—O1	110.56 (13)	C12—C11—H11	119.5 (10)
H2a—C2—O1	108.7 (10)	C11—C12—O5	119.28 (13)
H2a—C2—C1	111.7 (11)	C13—C12—O5	118.64 (13)
H2b—C2—O1	103.5 (11)	C13—C12—C11	122.08 (13)
H2b—C2—C1	111.8 (11)	C12—C13—C4	118.85 (14)
H2b—C2—H2a	110.3 (16)	H13—C13—C4	120.5 (10)
O2—C3—O1	124.32 (14)	H13—C13—C12	120.7 (10)
C4—C3—O1	112.32 (12)	C15—C14—O5	124.64 (13)
C4—C3—O2	123.35 (14)	C19—C14—O5	115.53 (13)
C5—C4—C3	122.10 (13)	C19—C14—C15	119.83 (14)
C13—C4—C3	117.47 (13)	H15—C15—C14	119.3 (11)
C13—C4—C5	120.30 (14)	C16—C15—C14	119.51 (14)
H5—C5—C4	120.5 (10)	C16—C15—H15	121.2 (11)
C6—C5—C4	119.60 (13)	H16—C16—C15	118.6 (10)
C6—C5—H5	119.9 (10)	C17—C16—C15	121.22 (15)
C7—C6—C5	122.14 (13)	C17—C16—H16	120.2 (10)
C11—C6—C5	120.52 (14)	H17—C17—C16	120.5 (11)
C11—C6—C7	117.28 (13)	C18—C17—C16	119.28 (15)
O4—C7—O3	124.15 (13)	C18—C17—H17	120.3 (11)
C6—C7—O3	112.38 (12)	H18—C18—C17	119.8 (10)
C6—C7—O4	123.46 (13)	C19—C18—C17	120.36 (14)
H9a—C9—O3	107.7 (10)	C19—C18—H18	119.8 (10)
H9b—C9—O3	107.3 (10)	C18—C19—C14	119.78 (14)
H9b—C9—H9a	109.9 (14)	C20—C19—C14	119.90 (13)
C10—C9—O3	106.54 (13)	C20—C19—C18	120.31 (13)
C10—C9—H9a	112.2 (10)	C19—C20—N1	178.46 (16)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C4–C6/C11–C13 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O4ⁱ	0.98 (2)	2.50 (2)	3.2071 (2)	128 (1)
C13—H13···O4ⁱⁱ	0.936 (16)	2.514 (16)	3.4179 (2)	163.5 (12)
C16—H16···O2ⁱⁱⁱ	0.997 (17)	2.516 (17)	3.1941 (2)	125.7 (13)
C18—H18···N1^iv	0.945 (17)	2.629 (17)	3.430 (2)	143.0 (13)
C10—H10C···Cg1^v	1.00 (2)	2.96 (2)	3.7893 (19)	140 (2)

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

Acknowledgements

The Department of Applied Chemistry, Faculty of Engineering and Technology, Aligarh Muslim University, UP, India, and Deanship of Scientific Research, Research Chair, King Saud University, Riyadh, KSA, are gratefully acknowledged for providing laboratory facilities. TEQIP-III, ZHCET, Aligarh Muslim University, is thanked for extensive help to procure chemicals.

Funding information

Musheer Ahmad acknowledges a start-up grant from the UGC, India. Mohd Afzal acknowledges support from the Deanship of Scientific Research, King Saud University, Riyadh, Saudi Arabia. AA, SK and MM thank the UGC for Non-NET Fellowships.

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