(Z)-3-[(3,5-Di­chloro­anilino)methyl­idene]-5-(4-methyl­phen­yl)furan-2(3H)-one

Grinev, V.S.; Osipov, A.K.; Yegorova, A.Y.

doi:10.1107/S2414314618012245

organic compounds

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ISSN: 2414-3146

Volume 3| Part 8| August 2018| x181224

https://doi.org/10.1107/S2414314618012245

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(Z)-3-[(3,5-Dichloroanilino)methylidene]-5-(4-methylphenyl)furan-2(3H)-one

Vyacheslav S. Grinev,^a,^b ^* Alexander K. Osipov ^a and Alevtina Yu. Yegorova ^a

^aInstitute of Chemistry, N.G. Chernyshevsky National Research Saratov State University, Ulitsa Astrakhanskaya, 83, Saratov 410012, Russian Federation, and ^bInstitute of Biochemistry and Physiology of Plants and Microorganisms, Russian Academy of Sciences, 13 Prospekt Entuziastov, Saratov 410049, Russian Federation
^*Correspondence e-mail: grinev@ibppm.ru

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 24 August 2018; accepted 28 August 2018; online 31 August 2018)

The crystal structure of the title compound, C₁₈H₁₃Cl₂NO₂, at 120 K has triclinic (P $[\overline{1}]$ ) symmetry. The molecule demonstrates non-planarity in the solid state and a Z configuration for the exocyclic C=C bond. The Z form is stabilized by the presence of an intramolecular N—H⋯O hydrogen bond with an O⋯H interatomic distance of 2.18 (2) Å.

Keywords: crystal structure; push–pull enamine; arylaminomethylene derivative; furan-2(3H)-one.

CCDC reference: 1863632

Structure description

Enamine derivatives of furan-2(3H)-ones have a push–pull character and may be of interest for the creation of molecular switches (Osipov et al., 2017 ). The title molecule is non-planar (Fig. 1) with the p-tolyl substituent rotated about the mean plane of the furanone ring by approximately −10° [C18—C17—C6—O1 torsion angle = −9.68 (19)°]. The C4=C7 bond adopts the Z configuration. The benzene ring of the 3,5-dichlorophenyl substituent is also out of the plane of the molecule [the dihedral angle between the mean planes of the furanone and 3,5-dichlorophenyl rings is 14.74 (7)°], which is a consequence of the repulsion of hydrogen atoms H16 of the aromatic substituent and H7 of enamine fragment (the interatomic distance is 2.12 Å, which is less than the sum of van der Waals radii of 2.38 Å). An additional stabilization factor of the molecule in the Z-configuration is the intramolecular hydrogen bond with an O3⋯H8 interatomic distance of 2.18 (2) Å (Table 1, Fig. 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N8—H8⋯O3	0.89 (2)	2.18 (2)	2.8553 (16)	132.2 (19)

Figure 1
The molecular structure of the title compound with the atom labelling and displacement ellipsoids drawn at the 50% probability level.

Molecules in the crystal are oriented in a head-to-tail fashion (Fig. 2). The interplanar distances between identically oriented molecules are more than 7 Å. The shortest intercentroid distance in the crystal is between the furanone and 3,5-dichlorophenyl rings [Cg1⋯Cg2ⁱ = 3.5817 (9) Å; symmetry code: (i) −x + 1, −y + 1, −z + 1; Cg1 and Cg2 are the centroids of the furanone and 3,5-dichlorophenyl rings, respectively].

Figure 2
The crystal packing of the title compound, viewed down the a axis.

Synthesis and crystallization

The synthesis of title compound was performed according to the method described by Osipov et al. (2017). Briefly, about 7 ml of benzene, 1.78 g (12.02 mmol) of triethyl orthoformate, 0.40 g (1.67 mmol) of 5-(p-tolyl)furan-2(3H)-one and 0.27 g (1.67 mmol) of 3,5-dichloroaniline were placed into a round-bottom flask equipped with a Liebig reflux condenser, and the reaction mixture was refluxed for 2 h. The precipitate of 3-[(3,5-dichloroanilino)methylidene]-5-(4-methylphenyl)furan-2(3H)-one was filtered off, washed with benzene and then with chloroform, dried, and recrystallized from DMF. Yield 0.45 g (78%), yellow crystals. A suitable single-crystal for X-ray analysis was obtained by slow cooling of a saturated solution of the title compound in benzene.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₈H₁₃Cl₂NO₂
M_r	346.19
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	120
a, b, c (Å)	7.4005 (8), 10.4272 (11), 10.5704 (11)
α, β, γ (°)	86.076 (2), 72.382 (2), 81.325 (2)
V (Å³)	768.30 (14)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.43
Crystal size (mm)	0.6 × 0.1 × 0.1

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.670, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	14989, 3956, 3576
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.102, 1.05
No. of reflections	3956
No. of parameters	213
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.26
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXT2014 (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1863632

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012245/vm4038sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012245/vm4038Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618012245/vm4038Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

(Z)-3-[(3,5-Dichloroanilino)methylidene]-5-(4-methylphenyl)furan-2(3H)-one top

Crystal data top

C₁₈H₁₃Cl₂NO₂	Z = 2
M_r = 346.19	F(000) = 356
Triclinic, P1	D_x = 1.496 Mg m⁻³
a = 7.4005 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4272 (11) Å	Cell parameters from 9480 reflections
c = 10.5704 (11) Å	θ = 2.8–33.6°
α = 86.076 (2)°	µ = 0.43 mm⁻¹
β = 72.382 (2)°	T = 120 K
γ = 81.325 (2)°	Needle, metallic orangish yellow
V = 768.30 (14) Å³	0.6 × 0.1 × 0.1 mm

Data collection top

Bruker APEXII CCD diffractometer	3576 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.019
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θ_max = 28.7°, θ_min = 2.0°
T_min = 0.670, T_max = 0.747	h = −9→9
14989 measured reflections	k = −14→14
3956 independent reflections	l = −14→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0584P)² + 0.3381P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3956 reflections	Δρ_max = 0.65 e Å⁻³
213 parameters	Δρ_min = −0.25 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 structure was solved by the internal phasing method and refined by the least-squares method in the anisotropic full-matrix approximation in accordance with F²_hkl. The hydrogen atom of NH group in the compound was localized from a difference electron density map and refined in the isotropic approximation.

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

	x	y	z	U_iso*/U_eq
Cl12	0.73598 (6)	0.17894 (4)	0.95054 (4)	0.03192 (11)
Cl15	0.28370 (5)	0.00476 (4)	0.70818 (4)	0.03283 (11)
O1	0.85703 (14)	0.63696 (9)	0.18548 (9)	0.0221 (2)
O3	0.87688 (16)	0.58521 (10)	0.39293 (10)	0.0284 (2)
N8	0.71111 (18)	0.35501 (11)	0.49406 (12)	0.0236 (2)
H8	0.782 (3)	0.412 (2)	0.506 (2)	0.041 (5)*
C2	0.8260 (2)	0.56018 (12)	0.29926 (13)	0.0218 (3)
C4	0.72893 (19)	0.45467 (13)	0.28098 (13)	0.0220 (3)
C5	0.70627 (19)	0.47396 (13)	0.15031 (13)	0.0220 (3)
H5	0.648261	0.420524	0.109156	0.026*
C6	0.78279 (18)	0.58216 (12)	0.09699 (13)	0.0192 (2)
C7	0.6746 (2)	0.36063 (13)	0.37583 (13)	0.0232 (3)
H7	0.608028	0.296280	0.357858	0.028*
C9	0.64593 (19)	0.26777 (12)	0.59953 (13)	0.0213 (3)
C10	0.7183 (2)	0.26434 (13)	0.70751 (13)	0.0232 (3)
H10	0.810977	0.318045	0.708104	0.028*
C11	0.65202 (19)	0.18079 (13)	0.81396 (13)	0.0215 (3)
C13	0.51978 (18)	0.09828 (12)	0.81629 (12)	0.0213 (3)
H13	0.477960	0.040465	0.889271	0.026*
C14	0.45206 (19)	0.10446 (13)	0.70717 (13)	0.0217 (3)
C16	0.51059 (19)	0.18805 (13)	0.59919 (13)	0.0222 (3)
H16	0.459533	0.190915	0.526541	0.027*
C17	0.80132 (18)	0.65033 (12)	−0.02995 (12)	0.0190 (2)
C18	0.86162 (18)	0.77317 (12)	−0.05282 (13)	0.0198 (2)
H18	0.891237	0.813026	0.015255	0.024*
C19	0.87821 (18)	0.83680 (12)	−0.17475 (13)	0.0206 (2)
H19	0.918467	0.920294	−0.188607	0.025*
C20	0.83712 (19)	0.78098 (13)	−0.27751 (13)	0.0213 (3)
C21	0.7763 (2)	0.65877 (13)	−0.25387 (14)	0.0237 (3)
H21	0.746755	0.619139	−0.322100	0.028*
C22	0.75842 (19)	0.59414 (13)	−0.13209 (13)	0.0222 (3)
H22	0.716687	0.511095	−0.118071	0.027*
C23	0.8603 (2)	0.85101 (14)	−0.41077 (14)	0.0274 (3)
H23A	0.748654	0.916703	−0.405238	0.041*
H23B	0.870926	0.788438	−0.478604	0.041*
H23C	0.976178	0.893178	−0.434616	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl12	0.0422 (2)	0.0348 (2)	0.02564 (18)	−0.01046 (15)	−0.01803 (15)	0.00003 (14)
Cl15	0.0342 (2)	0.0421 (2)	0.02820 (19)	−0.01988 (16)	−0.01268 (15)	0.00627 (14)
O1	0.0303 (5)	0.0196 (4)	0.0175 (4)	−0.0055 (4)	−0.0081 (4)	0.0014 (3)
O3	0.0406 (6)	0.0261 (5)	0.0205 (5)	−0.0074 (4)	−0.0107 (4)	0.0007 (4)
N8	0.0277 (6)	0.0219 (5)	0.0211 (5)	−0.0065 (4)	−0.0061 (5)	0.0020 (4)
C2	0.0254 (6)	0.0195 (6)	0.0180 (6)	−0.0012 (5)	−0.0041 (5)	0.0004 (4)
C4	0.0220 (6)	0.0205 (6)	0.0217 (6)	−0.0014 (5)	−0.0047 (5)	0.0008 (5)
C5	0.0217 (6)	0.0214 (6)	0.0232 (6)	−0.0039 (5)	−0.0070 (5)	0.0019 (5)
C6	0.0188 (6)	0.0189 (6)	0.0195 (6)	−0.0010 (4)	−0.0057 (5)	−0.0013 (4)
C7	0.0242 (6)	0.0223 (6)	0.0224 (6)	−0.0037 (5)	−0.0061 (5)	0.0014 (5)
C9	0.0224 (6)	0.0191 (6)	0.0191 (6)	0.0004 (5)	−0.0029 (5)	0.0002 (4)
C10	0.0250 (6)	0.0212 (6)	0.0230 (6)	−0.0044 (5)	−0.0059 (5)	−0.0008 (5)
C11	0.0250 (6)	0.0217 (6)	0.0178 (6)	−0.0014 (5)	−0.0070 (5)	−0.0017 (5)
C13	0.0236 (6)	0.0220 (6)	0.0168 (6)	−0.0020 (5)	−0.0049 (5)	0.0014 (5)
C14	0.0202 (6)	0.0243 (6)	0.0204 (6)	−0.0042 (5)	−0.0053 (5)	0.0000 (5)
C16	0.0220 (6)	0.0264 (6)	0.0178 (6)	−0.0015 (5)	−0.0068 (5)	0.0012 (5)
C17	0.0174 (5)	0.0191 (6)	0.0191 (6)	−0.0003 (4)	−0.0043 (4)	−0.0001 (4)
C18	0.0201 (6)	0.0206 (6)	0.0194 (6)	−0.0023 (5)	−0.0067 (5)	−0.0012 (4)
C19	0.0207 (6)	0.0190 (6)	0.0219 (6)	−0.0024 (5)	−0.0062 (5)	0.0011 (5)
C20	0.0193 (6)	0.0235 (6)	0.0196 (6)	0.0023 (5)	−0.0061 (5)	0.0004 (5)
C21	0.0254 (6)	0.0248 (6)	0.0230 (6)	−0.0009 (5)	−0.0108 (5)	−0.0042 (5)
C22	0.0226 (6)	0.0201 (6)	0.0249 (6)	−0.0030 (5)	−0.0084 (5)	−0.0022 (5)
C23	0.0317 (7)	0.0290 (7)	0.0198 (6)	0.0020 (6)	−0.0083 (5)	0.0010 (5)

Geometric parameters (Å, º) top

Cl12—C11	1.7338 (14)	C11—C13	1.3911 (19)
Cl15—C14	1.7362 (14)	C13—H13	0.9500
O1—C2	1.3771 (15)	C13—C14	1.3841 (18)
O1—C6	1.4079 (15)	C14—C16	1.3887 (18)
O3—C2	1.2171 (17)	C16—H16	0.9500
N8—H8	0.89 (2)	C17—C18	1.4010 (17)
N8—C7	1.3521 (18)	C17—C22	1.4000 (18)
N8—C9	1.4040 (17)	C18—H18	0.9500
C2—C4	1.4543 (19)	C18—C19	1.3886 (17)
C4—C5	1.4381 (18)	C19—H19	0.9500
C4—C7	1.3671 (18)	C19—C20	1.3968 (18)
C5—H5	0.9500	C20—C21	1.3964 (19)
C5—C6	1.3504 (18)	C20—C23	1.5158 (18)
C6—C17	1.4533 (17)	C21—H21	0.9500
C7—H7	0.9500	C21—C22	1.3907 (19)
C9—C10	1.3965 (19)	C22—H22	0.9500
C9—C16	1.3956 (19)	C23—H23A	0.9800
C10—H10	0.9500	C23—H23B	0.9800
C10—C11	1.3880 (18)	C23—H23C	0.9800

C2—O1—C6	107.58 (10)	C13—C14—Cl15	117.97 (10)
C7—N8—H8	116.8 (14)	C13—C14—C16	122.82 (12)
C7—N8—C9	125.78 (12)	C16—C14—Cl15	119.19 (10)
C9—N8—H8	117.4 (14)	C9—C16—H16	120.7
O1—C2—C4	107.75 (11)	C14—C16—C9	118.67 (12)
O3—C2—O1	121.51 (12)	C14—C16—H16	120.7
O3—C2—C4	130.74 (12)	C18—C17—C6	121.04 (12)
C5—C4—C2	106.19 (11)	C22—C17—C6	120.34 (12)
C7—C4—C2	123.25 (12)	C22—C17—C18	118.62 (12)
C7—C4—C5	130.56 (13)	C17—C18—H18	119.9
C4—C5—H5	126.4	C19—C18—C17	120.17 (12)
C6—C5—C4	107.27 (12)	C19—C18—H18	119.9
C6—C5—H5	126.4	C18—C19—H19	119.2
O1—C6—C17	115.91 (11)	C18—C19—C20	121.57 (12)
C5—C6—O1	111.20 (11)	C20—C19—H19	119.2
C5—C6—C17	132.89 (12)	C19—C20—C23	120.65 (12)
N8—C7—C4	123.02 (13)	C21—C20—C19	117.97 (12)
N8—C7—H7	118.5	C21—C20—C23	121.37 (12)
C4—C7—H7	118.5	C20—C21—H21	119.5
C10—C9—N8	117.85 (12)	C22—C21—C20	121.07 (12)
C16—C9—N8	121.80 (12)	C22—C21—H21	119.5
C16—C9—C10	120.34 (12)	C17—C22—H22	119.7
C9—C10—H10	120.7	C21—C22—C17	120.60 (12)
C11—C10—C9	118.57 (13)	C21—C22—H22	119.7
C11—C10—H10	120.7	C20—C23—H23A	109.5
C10—C11—Cl12	118.97 (11)	C20—C23—H23B	109.5
C10—C11—C13	122.77 (12)	C20—C23—H23C	109.5
C13—C11—Cl12	118.25 (10)	H23A—C23—H23B	109.5
C11—C13—H13	121.6	H23A—C23—H23C	109.5
C14—C13—C11	116.80 (12)	H23B—C23—H23C	109.5
C14—C13—H13	121.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···O3	0.89 (2)	2.18 (2)	2.8553 (16)	132.2 (19)

Funding information

The work was supported by the RFBR (research project No. 16–03-00530).

References

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