N,N′-(Ethane-1,2-di­yl)bis­(2-chloro­benzamide)

Mohamooda Sumaya, U.; Reuben Jonathan, D.; Dravida Thendral, E.R.A.; Revathi, B.K.; Usha, G.

doi:10.1107/S2414314616011901

organic compounds

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ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161190

https://doi.org/10.1107/S2414314616011901

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N,N′-(Ethane-1,2-diyl)bis(2-chlorobenzamide)

U. Mohamooda Sumaya,^a D. Reuben Jonathan,^b E. R. A. Dravida Thendral,^c B. K. Revathi ^c and G. Usha ^c ^*

^aDepartment of Physics, Bharathi Women's College, Chennai-108, Tamilnadu, India, ^bDepartment of Chemistry, Madras Christian College, Chennai-59, Tamilnadu, India, and ^cPG and Research Department of Physics, Queen Mary's College, Chennai-4, Tamilnadu, India
^*Correspondence e-mail: guqmc@yahoo.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 24 June 2016; accepted 21 July 2016; online 26 July 2016)

The title compound, C₁₆H₁₄Cl₂N₂O₂, crystallized with one half-molecule in the asymmetric unit; the whole molecule is generated by inversion symmetry, the center of inversion being situated at the middle of the bridging –CH₂—CH₂– bond. The dihedral angle between the amide group and the benzene ring is 52.4 (2)°. In the crystal, molecules are linked by two pairs of N—H⋯O hydrogen bonds forming a ladder-like structure propagating along the a-axis direction and enclosing R₂²(14) ring motifs. The compound was refined as a two-component twin [BASF = 0.18 (1)].

Keywords: crystal structure; ethylenediamine; benzamide; N—H⋯O hydrogen bonds; inversion dimers.

CCDC reference: 1495108

Structure description

Ethylenediamine, having two amines, is bifunctional and readily forms heterocycles such as imidazolidines. It is also widely used as a precursor to form various polymers (Wang et al., 2013 ). It is an ingredient in the common bronchodilator drug aminophylline, where it serves to solubilize the active ingredient theophylline. It has also been used in dermatologic preparations (Hogan, 1990 ). Ethylenediamine is one of the most frequent contact sensitizers (Zuidema, 1985 ). It is used as a solvent, miscible with water, oxygenated and aromatic solvents (Ashford, 1994 ). Ethylenediamine dihydroiodide (EDDI) has been added to animal feeds as a source of iodide (Lyday, 2000 ). N-substituted benzamides are well known anticancer compounds (Olsson et al., 2002 ), they exhibit potent anti-emetic activity (Vega-Noverola et al., 1989 ) and inhibit the activity of nuclear factor-B and the nuclear factor of activated T cells while inducing activator protein 1 activity in T-lymphocytes (Lindgren et al., 2001 ). In view of this interest we have synthesized the title compound and describe herein its crystal structure.

The bond lengths and bond angles in the title compound, Fig. 1, are close to those observed for similar compounds, for example in N,N′-ethane-1,2-diylbis(4-methoxybenzamide) (Aparicio et al., 2014 ), 4,4′-(ethane-1,2-diyldicarbamoyl)dibenzoic acid (Guarda et al., 2012 ) and 1,2-bis[(2-aminobenzoyl)amino]ethane (Bertolasi et al., 2009 ). In the title compound, the dihedral angle between the amide group (O1/N1/C2/C3) and the benzene ring (C3–C8) is 52.4 (2)°. In the above mentioned compounds, this dihedral angle is ca 25.9, 27.5 and 30.6°, respectively.

Figure 1
The molecular structure of the title compound, with atom labelling [symmetry code: (a) −x + 1, −y, −z + 1]. Displacement ellipsoids are drawn at the 30% probability level.

In the crystal, molecules are linked by two pairs of N—H⋯O hydrogen bonds, forming a ladder-like structure propagating along the a-axis direction and enclosing R₂²(14) loops (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.90 (5)	1.99 (5)	2.801 (4)	149 (4)
Symmetry code: (i) x+1, y, z.

Figure 2
A partial view along the b axis of the crystal packing of the title compound. The dashed lines indicate the hydrogen bonds (see Table 1

). For clarity only the H atoms involved in interactions have been included.

Synthesis and crystallization

The title compound was synthesized following a published procedure (Revathi et al., 2015 ). In a 250 ml round-bottomed flask, 25ml of ethylmethylketone was added to ethylenediamine (0.01mol) and stirred at room temperature. After 10 min, triethylamine (0.04 mol) was added and the mixture was stirred for 15 min. 2-Chlorobenzoyl chloride (0.04 mol) was then added and the reaction mixture was stirred at room temperature for 2 h. The precipitate that formed was filtered off and the filtrate evaporated to give crude title product. It was recrystallized twice from ethylmethylketone to give yellow block-like crystals of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The compound was refined as a two-component twin [BASF = 0.18 (1)].

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₄Cl₂N₂O₂
M_r	337.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	4.9667 (6), 23.701 (3), 7.1113 (8)
β (°)	104.189 (4)
V (Å³)	811.59 (17)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.41
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.885, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	11558, 1429, 1429
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.156, 1.17
No. of reflections	11558
No. of parameters	105
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.32
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993 ), SHELXL2014 (Sheldrick, 2015 ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Structural data

CCDC reference: 1495108

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2414314616011901/su4058sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616011901/su4058Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616011901/su4058Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

N,N'-(Ethane-1,2-diyl)bis(2-chlorobenzamide) top

Crystal data top

C₁₆H₁₄Cl₂N₂O₂	F(000) = 348
M_r = 337.19	D_x = 1.380 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 4.9667 (6) Å	Cell parameters from 6198 reflections
b = 23.701 (3) Å	θ = 2.6–29.3°
c = 7.1113 (8) Å	µ = 0.41 mm⁻¹
β = 104.189 (4)°	T = 293 K
V = 811.59 (17) Å³	Block, yellow
Z = 2	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1429 independent reflections
Radiation source: fine-focus sealed tube	1429 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
ω and φ scan	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −5→5
T_min = 0.885, T_max = 0.922	k = −28→28
11558 measured reflections	l = −8→8

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.064	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.156	w = 1/[σ²(F_o²) + 1.3152P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max < 0.001
11558 reflections	Δρ_max = 0.40 e Å⁻³
105 parameters	Δρ_min = −0.32 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. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq
C1	0.5857 (8)	−0.00874 (16)	0.5990 (6)	0.0425 (11)
H1A	0.4843	−0.0367	0.6536	0.051*
H1B	0.7574	−0.0259	0.5855	0.051*
C2	0.4659 (8)	0.06093 (16)	0.8173 (6)	0.0365 (10)
C3	0.5714 (8)	0.10688 (16)	0.9594 (6)	0.0371 (10)
C4	0.8101 (9)	0.09869 (18)	1.1056 (7)	0.0508 (12)
H4	0.9088	0.0652	1.1089	0.061*
C5	0.9046 (11)	0.1387 (2)	1.2456 (7)	0.0681 (15)
H5	1.0635	0.1321	1.3439	0.082*
C6	0.7609 (13)	0.1887 (2)	1.2385 (9)	0.0773 (17)
H6	0.8235	0.2160	1.3331	0.093*
C7	0.5285 (12)	0.1986 (2)	1.0949 (9)	0.0700 (16)
H7	0.4339	0.2327	1.0904	0.084*
C8	0.4345 (9)	0.15789 (17)	0.9560 (7)	0.0475 (11)
N1	0.6494 (7)	0.03913 (15)	0.7298 (5)	0.0407 (9)
O1	0.2278 (6)	0.04316 (12)	0.7882 (5)	0.0564 (9)
Cl1	0.1434 (3)	0.17296 (5)	0.7711 (2)	0.0786 (6)
H1	0.822 (10)	0.0537 (18)	0.761 (7)	0.069 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.034 (2)	0.046 (2)	0.048 (3)	0.0037 (19)	0.0094 (19)	−0.013 (2)
C2	0.026 (2)	0.043 (2)	0.041 (3)	0.0015 (17)	0.0086 (19)	−0.0049 (19)
C3	0.033 (2)	0.039 (2)	0.044 (3)	−0.0043 (18)	0.018 (2)	−0.0056 (19)
C4	0.045 (3)	0.050 (3)	0.054 (3)	−0.001 (2)	0.006 (2)	−0.008 (2)
C5	0.067 (4)	0.071 (4)	0.056 (4)	−0.015 (3)	−0.004 (3)	−0.018 (3)
C6	0.088 (4)	0.059 (4)	0.081 (5)	−0.024 (3)	0.014 (4)	−0.037 (3)
C7	0.086 (4)	0.042 (3)	0.085 (5)	−0.002 (3)	0.028 (4)	−0.016 (3)
C8	0.052 (3)	0.041 (2)	0.050 (3)	0.000 (2)	0.015 (2)	−0.001 (2)
N1	0.0215 (18)	0.056 (2)	0.045 (2)	−0.0040 (16)	0.0076 (16)	−0.0165 (17)
O1	0.0235 (16)	0.0612 (19)	0.089 (3)	−0.0107 (14)	0.0222 (16)	−0.0276 (17)
Cl1	0.0734 (10)	0.0652 (9)	0.0913 (12)	0.0220 (7)	0.0088 (8)	0.0099 (8)

Geometric parameters (Å, º) top

C1—N1	1.452 (5)	C4—H4	0.9300
C1—C1ⁱ	1.513 (8)	C5—C6	1.379 (7)
C1—H1A	0.9700	C5—H5	0.9300
C1—H1B	0.9700	C6—C7	1.362 (8)
C2—O1	1.224 (4)	C6—H6	0.9300
C2—N1	1.328 (5)	C7—C8	1.378 (6)
C2—C3	1.490 (5)	C7—H7	0.9300
C3—C8	1.384 (5)	C8—Cl1	1.736 (5)
C3—C4	1.386 (6)	N1—H1	0.90 (5)
C4—C5	1.371 (6)

N1—C1—C1ⁱ	111.5 (4)	C4—C5—C6	119.1 (5)
N1—C1—H1A	109.3	C4—C5—H5	120.5
C1ⁱ—C1—H1A	109.3	C6—C5—H5	120.5
N1—C1—H1B	109.3	C7—C6—C5	120.8 (5)
C1ⁱ—C1—H1B	109.3	C7—C6—H6	119.6
H1A—C1—H1B	108.0	C5—C6—H6	119.6
O1—C2—N1	122.2 (4)	C6—C7—C8	119.5 (5)
O1—C2—C3	122.0 (3)	C6—C7—H7	120.3
N1—C2—C3	115.7 (3)	C8—C7—H7	120.3
C8—C3—C4	117.5 (4)	C7—C8—C3	121.4 (5)
C8—C3—C2	122.5 (4)	C7—C8—Cl1	118.1 (4)
C4—C3—C2	120.0 (4)	C3—C8—Cl1	120.5 (3)
C5—C4—C3	121.7 (4)	C2—N1—C1	122.5 (3)
C5—C4—H4	119.1	C2—N1—H1	117 (3)
C3—C4—H4	119.1	C1—N1—H1	120 (3)

O1—C2—C3—C8	−52.3 (6)	C6—C7—C8—C3	0.0 (8)
N1—C2—C3—C8	130.1 (4)	C6—C7—C8—Cl1	−178.1 (4)
O1—C2—C3—C4	125.5 (5)	C4—C3—C8—C7	−1.2 (6)
N1—C2—C3—C4	−52.1 (5)	C2—C3—C8—C7	176.7 (4)
C8—C3—C4—C5	1.8 (7)	C4—C3—C8—Cl1	176.9 (3)
C2—C3—C4—C5	−176.2 (4)	C2—C3—C8—Cl1	−5.2 (5)
C3—C4—C5—C6	−1.1 (7)	O1—C2—N1—C1	−2.5 (6)
C4—C5—C6—C7	−0.1 (8)	C3—C2—N1—C1	175.2 (4)
C5—C6—C7—C8	0.7 (8)	C1ⁱ—C1—N1—C2	78.1 (6)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱ	0.90 (5)	1.99 (5)	2.801 (4)	149 (4)

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

Acknowledgements

We are grateful to the Central Instrumentation Facility, Queen Mary's College, Chennai-4, for computing facilities and the SAIF, IIT, Madras, for use of the X-ray data-collection facility.

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