2-(2,4-Di­chloro­phen­oxy)-N′-[2-(2,4-di­chloro­phen­oxy)acet­yl]acetohydrazide

El-Hiti, G.A.; Abdel-Wahab, B.F.; Yousif, E.; Hegazy, A.S.; Kariuki, B.M.

doi:10.1107/S2414314621003187

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 6| Part 4| April 2021| x210318

https://doi.org/10.1107/S2414314621003187

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2-(2,4-Dichlorophenoxy)-N′-[2-(2,4-dichlorophenoxy)acetyl]acetohydrazide

Gamal A El-Hiti,^a ^* Bakr F. Abdel-Wahab,^b Emad Yousif,^c Amany S. Hegazy ^d and Benson M. Kariuki ^d

^aCornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia, ^bApplied Organic Chemistry Department, National Research Centre, Dokki, Giza 12622, Egypt, ^cDepartment of Chemistry, College of Science, Al-Nahrain University, Baghdad 64021, Iraq, and ^dSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
^*Correspondence e-mail: gelhiti@ksu.edu.sa

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 24 March 2021; accepted 25 March 2021; online 9 April 2021)

The complete molecule of the title compound, C₁₆H₁₂Cl₄N₂O₄, is generated by a crystallographic centre of symmetry. In the crystal, N—H⋯O hydrogen bonds link the molecules into [010] chains featuring R₂²(10) loops. The chains are cross-linked by short Cl⋯N contacts [3.224 (2) Å].

Keywords: crystal structure; acylhydrazine; biological activity.

CCDC reference: 2073258

Structure description

Diacylhydrazines have insecticidal activities (Wang et al., 2017 ) and can also be used to recover metal ions from solution (Chekanova et al., 2004 ; Radushev et al., 2007 ). In addition, they are precursors in the synthesis of biologically active heterocycles (Zarei 2017 ; Stabile et al., 2010 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound, C₁₆H₁₂Cl₄N₂O₄ (I). The asymmetric unit consists of half a molecule, which is completed by inversion symmetry centred in the middle of the central N—N bond (Fig. 1).

Figure 1
The molecular structure of (I) showing 50% displacement ellipsoids. Symmetry code: (i) 1 − x, 2 − y, 1 − z.

The twist angle between the 2,4-dichlorophenoxy ring system and the N′-acetylacetohydrazide group in (I) is 77.8 (1)°; the latter has a crystallographically imposed trans conformation, in a manner similar to 2-[5-methyl-2-(propan-2-yl)phenoxy]-N′-{2-[5-methyl-2-(propan-2-yl)phenoxy]acetyl}acetohydrazide (Fun et al., 2011 ). The C—N—N—C torsion angles in the structures of 2-(4-chlorophenoxy)-N′-[2-(4-chlorophenoxy)acetyl]acetohydrazide monohydrate (Chen & Tan, 2010 ) and N,N′-bis[2-(quinolin-8-yloxy)acetoyl]hydrazine dihydrate (Zheng et al., 2007 ) are 72.7 and 117.6°, respectively, compared to 180.0° in (I).

In the crystal, each molecule is involved in four N—H⋯O hydrogen-bonding contacts, donating two and accepting two bonds, leading to the formation of ribbons propagating parallel to [010] (Table 1, Fig. 2). The ribbons are linked by short Cl⋯N contacts perpendicular to the plane of the ribbons and roughly in the c-axis direction. The contact involves the para Cl atom of the 2,4-dichlorophenoxy group and the nitrogen atom of the N′-acetylacetohydrazide group, with a Cl2⋯N1 distance of 3.224 (2) Å (sum of van der Waals' radii = 3.30 Å).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	1.94	2.774 (3)	164
Symmetry code: (i) x, y+1, z.

Figure 2
The crystal structure viewed down [010] showing N—H⋯O hydrogen bonds (green dotted lines) and short Cl⋯N interactions (red dotted lines).

Synthesis and crystallization

A mixture of 2-(naphthalen-2-yloxy)acetohydrazide (0.47 g, 2.0 mmol) and ethyl 2-cyano-3-ethoxyacrylate (0.34 g, 2.0 mmol) in anhydrous ethanol (10 ml) was heated under reflux for 2 h. The solid obtained on cooling was collected by filtration, washed with ethanol, dried, and recrystallized from dimethylformamide solution to give colourless plates of (I) in 67% yield; m.p. 249–250°C (lit. m.p. 250°C; Abdel-Wahab et al., 2017 ).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₂Cl₄N₂O₄
M_r	438.08
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.7398 (4), 4.6540 (2), 20.1866 (9)
β (°)	100.842 (4)
V (Å³)	898.71 (7)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	6.22
Crystal size (mm)	0.16 × 0.10 × 0.01

Data collection
Diffractometer	Rigaku Oxford Diffraction SuperNova, Dual, Cu at home/near, Atlas
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.869, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5415, 1797, 1504
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.153, 1.03
No. of reflections	1797
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.42
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXS (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2020 ) and CHEMDRAW Ultra (Cambridge Soft, 2016 ).

Structural data

CCDC reference: 2073258

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314621003187/hb4380sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621003187/hb4380Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314621003187/hb4380Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), Mercury (Macrae et al., 2020); software used to prepare material for publication: CHEMDRAW Ultra (Cambridge Soft, 2016).

2-(2,4-Dichlorophenoxy)-N'-[2-(2,4-dichlorophenoxy)acetyl]acetohydrazide top

Crystal data top

C₁₆H₁₂Cl₄N₂O₄	F(000) = 444
M_r = 438.08	D_x = 1.619 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 9.7398 (4) Å	Cell parameters from 2218 reflections
b = 4.6540 (2) Å	θ = 4.6–73.9°
c = 20.1866 (9) Å	µ = 6.22 mm⁻¹
β = 100.842 (4)°	T = 293 K
V = 898.71 (7) Å³	Plate, colourless
Z = 2	0.16 × 0.10 × 0.01 mm

Data collection top

Rigaku Oxford Diffraction SuperNova, Dual, Cu at home/near, Atlas diffractometer	1504 reflections with I > 2σ(I)
ω scans	R_int = 0.040
Absorption correction: gaussian (CrysalisPro; Rigaku OD, 2015)	θ_max = 74.2°, θ_min = 4.5°
T_min = 0.869, T_max = 1.000	h = −11→8
5415 measured reflections	k = −5→5
1797 independent reflections	l = −24→24

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.153	w = 1/[σ²(F_o²) + (0.0898P)² + 0.4345P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
1797 reflections	Δρ_max = 0.51 e Å⁻³
118 parameters	Δρ_min = −0.42 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.

Refinement. The H atoms were positioned geometrically (N—H = 0.86, C—H = 0.93–0.96 Å) and refined using a riding model with U_iso(H) = 1.2U_eq(C,N).

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

	x	y	z	U_iso*/U_eq
C1	0.8216 (2)	0.7834 (5)	0.36947 (12)	0.0365 (5)
C2	0.8980 (3)	0.5906 (6)	0.33765 (14)	0.0412 (6)
C3	0.8527 (3)	0.5101 (7)	0.27100 (16)	0.0526 (7)
H3	0.903880	0.379893	0.250485	0.063*
C4	0.7314 (3)	0.6258 (8)	0.23597 (15)	0.0557 (7)
C5	0.6554 (3)	0.8206 (8)	0.26484 (16)	0.0571 (8)
H5	0.574178	0.899439	0.239873	0.069*
C6	0.7006 (3)	0.8997 (7)	0.33185 (15)	0.0479 (6)
H6	0.649162	1.032065	0.351606	0.057*
C7	0.7949 (3)	1.0250 (5)	0.47047 (14)	0.0381 (6)
H7A	0.771884	1.200592	0.444919	0.046*
H7B	0.850851	1.075711	0.513877	0.046*
C8	0.6610 (2)	0.8789 (5)	0.48107 (12)	0.0333 (5)
N1	0.5616 (2)	1.0565 (4)	0.49304 (10)	0.0322 (4)
H1	0.573575	1.239427	0.492170	0.039*
O1	0.87343 (17)	0.8420 (4)	0.43541 (9)	0.0396 (4)
O2	0.6471 (2)	0.6192 (4)	0.48048 (13)	0.0548 (6)
Cl1	1.05074 (8)	0.44859 (19)	0.38265 (4)	0.0618 (3)
Cl2	0.67176 (10)	0.5161 (3)	0.15306 (4)	0.0858 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0307 (11)	0.0369 (12)	0.0445 (12)	−0.0022 (9)	0.0135 (9)	0.0014 (10)
C2	0.0338 (12)	0.0442 (13)	0.0488 (14)	0.0016 (10)	0.0161 (10)	−0.0001 (11)
C3	0.0470 (16)	0.0622 (17)	0.0533 (17)	−0.0043 (13)	0.0219 (13)	−0.0117 (13)
C4	0.0448 (15)	0.077 (2)	0.0469 (14)	−0.0155 (14)	0.0116 (12)	−0.0015 (14)
C5	0.0383 (14)	0.074 (2)	0.0575 (17)	−0.0014 (14)	0.0044 (12)	0.0117 (15)
C6	0.0338 (13)	0.0547 (15)	0.0561 (16)	0.0079 (11)	0.0109 (11)	0.0034 (13)
C7	0.0318 (11)	0.0326 (11)	0.0535 (14)	−0.0028 (9)	0.0172 (10)	−0.0078 (10)
C8	0.0323 (11)	0.0279 (10)	0.0419 (12)	0.0012 (9)	0.0124 (9)	−0.0020 (9)
N1	0.0296 (9)	0.0240 (8)	0.0459 (11)	−0.0006 (7)	0.0142 (8)	−0.0006 (7)
O1	0.0296 (8)	0.0439 (9)	0.0474 (9)	0.0059 (7)	0.0125 (7)	−0.0047 (8)
O2	0.0464 (11)	0.0265 (9)	0.1008 (17)	0.0003 (7)	0.0374 (11)	−0.0041 (9)
Cl1	0.0481 (4)	0.0707 (5)	0.0672 (5)	0.0257 (3)	0.0128 (3)	−0.0051 (4)
Cl2	0.0647 (6)	0.1438 (10)	0.0484 (5)	−0.0318 (6)	0.0094 (4)	−0.0157 (5)

Geometric parameters (Å, º) top

C1—O1	1.359 (3)	C5—H5	0.9300
C1—C6	1.386 (4)	C6—H6	0.9300
C1—C2	1.397 (3)	C7—O1	1.419 (3)
C2—C3	1.386 (4)	C7—C8	1.521 (3)
C2—Cl1	1.723 (3)	C7—H7A	0.9700
C3—C4	1.368 (5)	C7—H7B	0.9700
C3—H3	0.9300	C8—O2	1.216 (3)
C4—C5	1.368 (5)	C8—N1	1.329 (3)
C4—Cl2	1.742 (3)	N1—N1ⁱ	1.386 (4)
C5—C6	1.391 (4)	N1—H1	0.8600

O1—C1—C6	125.4 (2)	C1—C6—H6	119.7
O1—C1—C2	116.6 (2)	C5—C6—H6	119.7
C6—C1—C2	118.0 (2)	O1—C7—C8	111.03 (19)
C3—C2—C1	121.4 (3)	O1—C7—H7A	109.4
C3—C2—Cl1	119.6 (2)	C8—C7—H7A	109.4
C1—C2—Cl1	119.1 (2)	O1—C7—H7B	109.4
C4—C3—C2	118.8 (3)	C8—C7—H7B	109.4
C4—C3—H3	120.6	H7A—C7—H7B	108.0
C2—C3—H3	120.6	O2—C8—N1	122.4 (2)
C3—C4—C5	121.6 (3)	O2—C8—C7	122.6 (2)
C3—C4—Cl2	118.8 (3)	N1—C8—C7	114.89 (19)
C5—C4—Cl2	119.6 (3)	C8—N1—N1ⁱ	119.3 (2)
C4—C5—C6	119.5 (3)	C8—N1—H1	120.4
C4—C5—H5	120.3	N1ⁱ—N1—H1	120.4
C6—C5—H5	120.3	C1—O1—C7	118.22 (19)
C1—C6—C5	120.7 (3)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱⁱ	0.86	1.94	2.774 (3)	164

Symmetry code: (ii) x, y+1, z.

Funding information

The authors are grateful to the Deanship of Scientific Research, King Saud University for funding through the Vice Deanship of Scientific Research Chairs.

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