2,4-Di­chloro-N-(2,5-dioxopyrrolidin-1-yl)benzamide

Stondus, J.; Anthal, S.; Karanth, S.; Narayana, B.; Sarojini, B.K.; Kant, R.

doi:10.1107/S2414314618017406

organic compounds

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ISSN: 2414-3146

Volume 3| Part 12| December 2018| x181740

https://doi.org/10.1107/S2414314618017406

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2,4-Dichloro-N-(2,5-dioxopyrrolidin-1-yl)benzamide

Jigmat Stondus,^a Sumati Anthal,^a S. Karanth,^b B. Narayana,^b B. K. Sarojini ^c and Rajni Kant ^a ^*

^aX-ray Crystallography Laboratory, Department of Physics, University of Jammu, Jammu 180 006, India, ^bDepartment of Chemistry, Mangalore University, Mangalagangothri 574 199, India, and ^cDepartment of Industrial Chemistry, Mangalore University, Mangalagangothri 574 199, India
^*Correspondence e-mail: rkant.ju@gmail.com

Edited by A. J. Lough, University of Toronto, Canada (Received 27 November 2018; accepted 8 December 2018; online 14 December 2018)

In the title compound, C₁₁H₈Cl₂N₂O₃, the plane of the pyrrolidine ring (r.m.s. deviation = 0.065 Å) makes a dihedral angle of 52.9 (2)° with the plane of the benzene ring. The least-squares plane of the central amide fragment makes dihedral angles of 49.3 (7) and 77.9 (7)° with those of the benzene and pyrrolidine rings, respectively. In the crystal, molecules are linked via N—H⋯O hydrogen bonds, forming chains along the b-axis direction. π–π interactions link these chains into a two-dimensional network parallel to (100).

Keywords: pyrrolidine ring; benzene ring; dihedral angle; hydrogen bonding; crystal structure.

CCDC reference: 1871635

Structure description

Imides are compounds that contain a nitrogen atom linked to two carbonyl groups. The title compound belongs to the class of imides that contain two acyl groups bound to nitrogen. These compounds, being structurally related to derivatives of ammonia, can pass through biological membranes because of their neutral and hydrophobic nature (Prado et al., 2004 ). Compounds containing this moiety have been reported to be potent antibacterial and antifungal agents (Nayakh et al., 2016 ). Furthermore, the N-substituted imides in dechlorinated Rebeccamycin have proved to be highly efficient as topoisomerase I inhibitors (Anizon et al., 1997 ) and hydroxylated thalidomides are found to be potent TNF-α inhibitors (Nakamura et al., 2006 ). The nitrogen atom plays a significant role in attributing pharmacological functions to these molecules such as analgesic, anti-inflammatory and anti-viral properties (Abdel-Aziz, 2007 ). Various synthetic routes are available for the synthesis of biologically potent imides (Barchin et al., 2002 ), including the acid-mediated condensation of an amine with an anhydride (Jayatunga et al., 2015 ). The reactivity and structures of substituted phthalimides (Su et al., 2015 ) have also been reported.

The molecular structure of the title compound is illustrated in Fig. 1. The molecule is composed of a benzene ring, a pyrrolidine ring and an amide fragment. The bond distances are in normal ranges and are comparable with the values reported for related structures (e.g. Saeed et al., 2010 ; Su et al., 2015). The pyrrolidine ring (r.m.s. deviation = 0.065 Å) makes a dihedral angle of 52.9 (2)° with the benzene ring. The central amide fragment makes dihedral angle of 49.3 (7)° and 77.9 (7)° with benzene and pyrrolidine rings, respectively.

Figure 1
The molecular structure of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.

In the crystal, N—H⋯O hydrogen bonds link the molecules along the b-axis direction, forming chains (Table 1, Fig. 2). The crystal structure also features π–π interactions (Fig. 3): Cg1⋯Cg2ⁱ = 3.9338 (3) Å, interplanar spacing = 3.587 Å and centroid shift = 1.57 Å and Cg2⋯Cg2ⁱⁱ = 3.9334 (3) Å, interplanar spacing = 3.533 Å and centroid shift = 1.73 Å [symmetry codes: (i) −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (ii) −x, −y + 1, −z + 1; Cg1 and Cg2 are the centroids of pyrrolidine and benzene rings, respectively]. The π–π interactions link the hydrogen-bonded chains into a two-dimensional network parallel to (100).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.15	3.006 (3)	171
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Part of the crystal structure showing N—H⋯O hydrogen bonds as dashed lines.

Figure 3
Part of the crystal structure showing the π–π stacking interactions.

Synthesis and crystallization

The title compound was obtained by refluxing a mixture of 2,4-dichlorobenzohydrazide (0.41 g, 2 mmol) and succinic anhydride (0.20 g, 2 mmol) for 5 h in 10 ml acetic acid. After the completion of the reaction, the reaction mixture was cooled and quenched into ice-cold water with stirring. The solid obtained was filtered, washed and dried. Single crystals were obtained by slow evaporation of a methanol solution (yield = 83%, m.p. = 435–437 K).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₈Cl₂N₂O₃
M_r	287.09
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.8233 (5), 7.4705 (5), 20.1932 (12)
β (°)	94.866 (6)
V (Å³)	1175.92 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.55
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.843, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4484, 2306, 1790
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.102, 1.03
No. of reflections	2306
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.25
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1871635

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2414314618017406/lh4042sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618017406/lh4042Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618017406/lh4042Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

2,4-Dichloro-N-(2,5-dioxopyrrolidin-1-yl)benzamide top

Crystal data top

C₁₁H₈Cl₂N₂O₃	F(000) = 584
M_r = 287.09	D_x = 1.622 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.8233 (5) Å	Cell parameters from 1764 reflections
b = 7.4705 (5) Å	θ = 3.8–28.5°
c = 20.1932 (12) Å	µ = 0.55 mm⁻¹
β = 94.866 (6)°	T = 293 K
V = 1175.92 (13) Å³	Block, white
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	2306 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1790 reflections with I > 2σ(I)
Detector resolution: 16.1049 pixels mm^-1	R_int = 0.022
ω scans	θ_max = 26.0°, θ_min = 3.8°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	h = −5→9
T_min = 0.843, T_max = 1.000	k = −9→5
4484 measured reflections	l = −23→24

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.039	w = 1/[σ²(F_o²) + (0.0446P)² + 0.4192P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.102	(Δ/σ)_max = 0.001
S = 1.03	Δρ_max = 0.27 e Å⁻³
2306 reflections	Δρ_min = −0.25 e Å⁻³
164 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.033 (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. All the H-atoms were geometrically fixed and allowed to ride on their corresponding non-H atoms with Uiso(H)= 1.2Ueq(C/N).

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

	x	y	z	U_iso*/U_eq
Cl1	0.33079 (8)	0.67402 (9)	0.44687 (3)	0.0499 (2)
Cl2	−0.26441 (8)	0.82692 (10)	0.54467 (3)	0.0497 (2)
O3	−0.4599 (2)	0.4080 (3)	0.70363 (9)	0.0631 (6)
O2	−0.0342 (2)	0.6697 (2)	0.83595 (8)	0.0445 (4)
O1	−0.1790 (2)	0.8061 (2)	0.69526 (8)	0.0481 (5)
N2	−0.2154 (2)	0.5067 (2)	0.76313 (8)	0.0322 (4)
N1	−0.1163 (2)	0.5140 (2)	0.70973 (9)	0.0349 (5)
H1	−0.061713	0.421471	0.697493	0.042*
C8	−0.1680 (3)	0.5927 (3)	0.82315 (10)	0.0322 (5)
C9	−0.3159 (3)	0.5717 (3)	0.86544 (11)	0.0397 (6)
H9A	−0.354223	0.687723	0.879901	0.048*
H9B	−0.282461	0.499738	0.904372	0.048*
C10	−0.4579 (3)	0.4793 (4)	0.82189 (11)	0.0424 (6)
H10A	−0.484555	0.363709	0.840305	0.051*
H10B	−0.561064	0.551838	0.818213	0.051*
C11	−0.3888 (3)	0.4575 (3)	0.75525 (11)	0.0378 (5)
C7	−0.1084 (3)	0.6725 (3)	0.67729 (10)	0.0305 (5)
C1	0.0002 (3)	0.6678 (3)	0.61942 (10)	0.0283 (5)
C6	−0.0586 (3)	0.7415 (3)	0.55805 (10)	0.0302 (5)
C5	0.0427 (3)	0.7430 (3)	0.50520 (11)	0.0327 (5)
H5	0.001763	0.791103	0.464426	0.039*
C4	0.2062 (3)	0.6717 (3)	0.51414 (11)	0.0324 (5)
C3	0.2692 (3)	0.5985 (3)	0.57392 (12)	0.0364 (5)
H3	0.379787	0.552033	0.579194	0.044*
C2	0.1649 (3)	0.5952 (3)	0.62609 (11)	0.0341 (5)
H2	0.205534	0.543537	0.666277	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0441 (4)	0.0653 (5)	0.0439 (4)	0.0074 (3)	0.0241 (3)	0.0035 (3)
Cl2	0.0327 (3)	0.0773 (5)	0.0398 (4)	0.0180 (3)	0.0069 (2)	0.0149 (3)
O3	0.0549 (12)	0.0935 (16)	0.0397 (11)	−0.0197 (11)	−0.0030 (9)	−0.0141 (11)
O2	0.0408 (10)	0.0535 (10)	0.0383 (10)	−0.0099 (8)	−0.0018 (7)	−0.0023 (8)
O1	0.0596 (11)	0.0449 (10)	0.0427 (10)	0.0190 (9)	0.0213 (8)	0.0043 (8)
N2	0.0348 (10)	0.0410 (11)	0.0218 (9)	−0.0029 (8)	0.0073 (7)	−0.0005 (8)
N1	0.0423 (11)	0.0375 (10)	0.0268 (10)	0.0055 (8)	0.0136 (8)	0.0013 (9)
C8	0.0378 (13)	0.0337 (12)	0.0248 (11)	0.0013 (10)	0.0010 (9)	0.0029 (10)
C9	0.0451 (14)	0.0493 (14)	0.0257 (11)	0.0001 (11)	0.0090 (10)	−0.0004 (11)
C10	0.0370 (13)	0.0537 (15)	0.0376 (13)	−0.0044 (11)	0.0096 (10)	0.0023 (12)
C11	0.0379 (13)	0.0428 (13)	0.0324 (13)	−0.0047 (11)	0.0011 (10)	0.0005 (11)
C7	0.0294 (11)	0.0391 (12)	0.0230 (11)	0.0035 (9)	0.0021 (8)	0.0013 (10)
C1	0.0277 (11)	0.0322 (11)	0.0256 (11)	0.0015 (9)	0.0059 (8)	−0.0007 (9)
C6	0.0254 (11)	0.0357 (11)	0.0297 (11)	0.0023 (9)	0.0035 (9)	0.0029 (10)
C5	0.0341 (12)	0.0405 (12)	0.0240 (11)	0.0006 (10)	0.0053 (9)	0.0028 (10)
C4	0.0316 (11)	0.0359 (12)	0.0311 (12)	−0.0020 (10)	0.0115 (9)	−0.0028 (10)
C3	0.0266 (11)	0.0416 (13)	0.0415 (13)	0.0071 (10)	0.0066 (10)	−0.0016 (11)
C2	0.0323 (12)	0.0397 (13)	0.0301 (12)	0.0061 (10)	0.0010 (9)	0.0031 (10)

Geometric parameters (Å, º) top

Cl1—C4	1.738 (2)	C10—C11	1.501 (3)
Cl2—C6	1.732 (2)	C10—H10A	0.9700
O3—C11	1.198 (3)	C10—H10B	0.9700
O2—C8	1.203 (3)	C7—C1	1.502 (3)
O1—C7	1.212 (3)	C1—C2	1.394 (3)
N2—N1	1.381 (2)	C1—C6	1.398 (3)
N2—C8	1.394 (3)	C6—C5	1.382 (3)
N2—C11	1.402 (3)	C5—C4	1.383 (3)
N1—C7	1.357 (3)	C5—H5	0.9300
N1—H1	0.8600	C4—C3	1.378 (3)
C8—C9	1.503 (3)	C3—C2	1.386 (3)
C9—C10	1.522 (3)	C3—H3	0.9300
C9—H9A	0.9700	C2—H2	0.9300
C9—H9B	0.9700

N1—N2—C8	122.35 (18)	N2—C11—C10	106.75 (18)
N1—N2—C11	121.57 (17)	O1—C7—N1	122.24 (19)
C8—N2—C11	113.77 (17)	O1—C7—C1	123.7 (2)
C7—N1—N2	117.59 (17)	N1—C7—C1	114.07 (18)
C7—N1—H1	121.2	C2—C1—C6	118.07 (19)
N2—N1—H1	121.2	C2—C1—C7	120.84 (19)
O2—C8—N2	124.7 (2)	C6—C1—C7	121.05 (18)
O2—C8—C9	128.7 (2)	C5—C6—C1	121.40 (19)
N2—C8—C9	106.57 (19)	C5—C6—Cl2	117.57 (16)
C8—C9—C10	106.14 (18)	C1—C6—Cl2	120.99 (16)
C8—C9—H9A	110.5	C6—C5—C4	118.7 (2)
C10—C9—H9A	110.5	C6—C5—H5	120.6
C8—C9—H9B	110.5	C4—C5—H5	120.6
C10—C9—H9B	110.5	C3—C4—C5	121.7 (2)
H9A—C9—H9B	108.7	C3—C4—Cl1	120.41 (17)
C11—C10—C9	105.48 (18)	C5—C4—Cl1	117.90 (17)
C11—C10—H10A	110.6	C4—C3—C2	118.9 (2)
C9—C10—H10A	110.6	C4—C3—H3	120.6
C11—C10—H10B	110.6	C2—C3—H3	120.6
C9—C10—H10B	110.6	C3—C2—C1	121.2 (2)
H10A—C10—H10B	108.8	C3—C2—H2	119.4
O3—C11—N2	123.6 (2)	C1—C2—H2	119.4
O3—C11—C10	129.7 (2)

C8—N2—N1—C7	−70.5 (3)	O1—C7—C1—C2	128.9 (2)
C11—N2—N1—C7	91.2 (2)	N1—C7—C1—C2	−48.9 (3)
N1—N2—C8—O2	−5.2 (3)	O1—C7—C1—C6	−48.9 (3)
C11—N2—C8—O2	−168.2 (2)	N1—C7—C1—C6	133.3 (2)
N1—N2—C8—C9	173.64 (19)	C2—C1—C6—C5	0.0 (3)
C11—N2—C8—C9	10.7 (2)	C7—C1—C6—C5	177.8 (2)
O2—C8—C9—C10	174.2 (2)	C2—C1—C6—Cl2	177.57 (17)
N2—C8—C9—C10	−4.6 (2)	C7—C1—C6—Cl2	−4.6 (3)
C8—C9—C10—C11	−2.3 (3)	C1—C6—C5—C4	−0.8 (3)
N1—N2—C11—O3	4.9 (4)	Cl2—C6—C5—C4	−178.47 (17)
C8—N2—C11—O3	168.0 (2)	C6—C5—C4—C3	0.5 (3)
N1—N2—C11—C10	−175.33 (19)	C6—C5—C4—Cl1	179.68 (17)
C8—N2—C11—C10	−12.2 (3)	C5—C4—C3—C2	0.6 (3)
C9—C10—C11—O3	−171.9 (3)	Cl1—C4—C3—C2	−178.55 (17)
C9—C10—C11—N2	8.3 (3)	C4—C3—C2—C1	−1.4 (3)
N2—N1—C7—O1	2.9 (3)	C6—C1—C2—C3	1.2 (3)
N2—N1—C7—C1	−179.25 (18)	C7—C1—C2—C3	−176.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.15	3.006 (3)	171

Symmetry code: (i) −x, y−1/2, −z+3/2.

Acknowledgements

RK acknowledges the Department of Science & Technology for a single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. BN thanks the UGC for financial assistance through a BSR one-time grant for the purchase of chemicals. SK thanks the Department of Science and Technology for financial support through an INSPIRE Fellowship.

Funding information

Funding for this research was provided by: Department of Science and Technology, Government of India (grant No. EMR/204/000467 to Rajni Kant).

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