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ISSN: 2056-9890
Volume 67| Part 5| May 2011| Page o1139

N,N′-Bis(2-chloro­phen­yl)succinamide

aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
*Correspondence e-mail: gowdabt@yahoo.com

(Received 17 March 2011; accepted 10 April 2011; online 16 April 2011)

There is one half-mol­ecule in the asymmetric unit of the title compound, C16H14Cl2N2O2, with a center of symmetry at the mid-point of the central C—C bond. The N—H and C=O bonds in the C—NH—C(O)—C fragment are anti to each other and the amide O atom is anti to the H atoms attached to the adjacent C atoms. However, the conformation of the N—H bond in the amide fragments is syn to the ortho-chloro groups in the adjacent benzene rings. The dihedral angle between the benzene ring and the NH—C(O)—CH2 fragment is 47.0 (2)°. In the crystal, a series of N—H⋯O inter­molecular hydrogen bonds link the mol­ecules into chains along the b axis.

Related literature

For our study of the effect of substituents on the structures of N-(ar­yl)-amides, see: Gowda et al. (2000[Gowda, B. T., Paulus, H. & Fuess, H. (2000). Z. Naturforsch. Teil A, 55, 791-800.]); Saraswathi et al. (2011a[Saraswathi, B. S., Foro, S. & Gowda, B. T. (2011a). Acta Cryst. E67, o607.],b[Saraswathi, B. S., Foro, S. & Gowda, B. T. (2011b). Acta Cryst. E67, o966.]) and on N-(ar­yl)-methane­sulfonamides, see: Gowda et al. (2007[Gowda, B. T., Foro, S. & Fuess, H. (2007). Acta Cryst. E63, o2597.]). For a similar structure, see Pierrot et al. (1984[Pierrot, M., Baldy, A., Maire, J. C., Mehrotra, R. C., Kapoor, T. S. & Bachlas, B. P. (1984). Acta Cryst. C40, 1931-1934.]).

[Scheme 1]

Experimental

Crystal data
  • C16H14Cl2N2O2

  • Mr = 337.19

  • Monoclinic, P 21 /n

  • a = 4.820 (2) Å

  • b = 11.445 (3) Å

  • c = 14.242 (4) Å

  • β = 98.10 (3)°

  • V = 777.8 (4) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.43 mm−1

  • T = 293 K

  • 0.44 × 0.08 × 0.04 mm

Data collection
  • Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector

  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.835, Tmax = 0.983

  • 2501 measured reflections

  • 1563 independent reflections

  • 900 reflections with I > 2σ(I)

  • Rint = 0.038

Refinement
  • R[F2 > 2σ(F2)] = 0.075

  • wR(F2) = 0.139

  • S = 1.16

  • 1563 reflections

  • 103 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.22 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1N⋯O1i 0.86 (2) 2.11 (2) 2.936 (4) 161 (3)
Symmetry code: (i) x+1, y, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]); cell refinement: CrysAlis RED (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Amide and sulfonamide moieties are important constituents of many biologically significant compounds. As a part of studying the substituent effects on structures of this class of compounds(Gowda et al., 2000, 2007; Saraswathi et al., 2011a,b), the structure of (I) has been determined (Fig.1). (I) sits on a center of symmetry passing through the mid-point of the central C—C bond to give a half molecule per asymmetric unit. This is similar to that obseved in bis(2-chlorophenylaminocarbonylmethyl)disulfide (II)(Pierrot et al., 1984), N,N-bis(2-methylphenyl)-succinamide (III)(Saraswathi et al., 2011a) and N,N-bis(3-chlorophenyl)- succinamide (III)(Saraswathi et al., 2011b).

The conformations of the N—H and C=O bonds in the C—NH—C(O)—C segments are anti to each other and the amide O atoms are anti to the H atoms attached to the adjacent C atoms. But the conformations of the N—H bonds in the amide fragments are syn to the ortho- chloro groups in the adjacent benzene rings, in contrast to the anti conformations observed with respect to the ortho-methyl groups in (III) and with respect to the meta-chloro groups in (IV).

The dihedral angle between the benzene ring and the NH—C(O)—CH2 segment in the two halves of the molecule is 47.0 (2)°, compared to the values of 62.1 (2)° in (III) and 32.8 (1)° in (Iv).

The torsion angles of N1–C7–C8–C8a and O1–C7–C8–C8a in (I) are 172.2 (5)° and -7.8 (4)°, in contrast to the values of 150.9 (3)° and -30.5 (4)° in (III) and -175.4 (2)° and 5.9 (4)° in (IV). The differences in the torsion angles may be due to the steric hindrances caused by the different substituents.

Similarly, the torsion angles of C2—C1—N1—C7 and C6—C1—N1—C7 are -47.6 (6)° and 133.7 (4)°, compared to the values of -64.0 (4)° and 117.6 (3)° in (III) and -35.0 (3)° and 147.5 (2)° in (IV).

The packing of molecules in the crystal linked by of N—H···O hydrogen bonds (Table 1) is shown in Fig. 2.

Related literature top

For our study of the effect of substituents on the structures of N-(aryl)-amides, see: Gowda et al. (2000); Saraswathi et al. (2011a,b) and on N-(aryl)-methanesulfonamides, see: Gowda et al. (2007). For a similar structure, see Pierrot et al. (1984).

Experimental top

Succinic anhydride (0.01 mol) in toluene (25 ml) was treated drop wise with 2-chloroaniline (0.01 mol) also in toluene (20 ml) with constant stirring. The resulting mixture was stirred for one hour and set aside for an additional hour at room temperature for completion of the reaction. The mixture was then treated with dilute hydrochloric acid to remove unreacted 2-chloroaniline. The resultant solid N-(2-chlorophenyl)-succinamic acid was filtered under suction and washed thoroughly with water to remove the unreacted succinic anhydride and succinic acid. The compound was recrystallized to constant melting point from ethanol. The purity of the compound was checked by elemental analysis and characterized by its infrared and NMR spectra.

The N-(2-chlorophenyl)succinamic acid obtained was then treated with phosphorous oxychloride and excess of 2-chloroaniline at room temperature with constant stirring. The resultant mixture was stirred for 4 h, kept aside for additional 6 h for completion of the reaction and poured slowly into crushed ice with constant stirring. It was kept aside for a day. The resultant solid, N,N-bis(2-chlorophenyl)- succinamide was filtered under suction, washed thoroughly with water, dilute sodium hydroxide solution and finally with water. It was recrystallized to constant melting point from a mixture of acetone and chloroform. The purity of the compound was checked by elemental analysis, and characterized by its infrared and NMR spectra.

Needle like colorless single crystals used in the X-ray diffraction studies were were grown in a mixture of acetone and chloroform at room temperature.

Refinement top

The H atom of the NH group was located in a difference map and later restrained to the distance N—H = 0.86 (2) Å. The other H atoms were positioned with idealized geometry using a riding model with the aromatic C—H = 0.93Å and the methylene C—H = 0.97 Å. All H atoms were refined with isotropic displacement parameters (set to 1.2 times of the Ueq of the parent atom).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I), showing the atom labelling scheme and displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Molecular packing of (I) with hydrogen bonding shown as dashed lines.
N,N'-Bis(2-chlorophenyl)succinamide top
Crystal data top
C16H14Cl2N2O2F(000) = 348
Mr = 337.19Dx = 1.440 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 475 reflections
a = 4.820 (2) Åθ = 2.9–27.8°
b = 11.445 (3) ŵ = 0.43 mm1
c = 14.242 (4) ÅT = 293 K
β = 98.10 (3)°Needle, colourless
V = 777.8 (4) Å30.44 × 0.08 × 0.04 mm
Z = 2
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
1563 independent reflections
Radiation source: fine-focus sealed tube900 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
Rotation method data acquisition using ω scansθmax = 26.4°, θmin = 2.9°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
h = 65
Tmin = 0.835, Tmax = 0.983k = 1014
2501 measured reflectionsl = 176
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.075Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 1.16 w = 1/[σ2(Fo2) + (0.0376P)2 + 0.5594P]
where P = (Fo2 + 2Fc2)/3
1563 reflections(Δ/σ)max = 0.002
103 parametersΔρmax = 0.25 e Å3
1 restraintΔρmin = 0.22 e Å3
Crystal data top
C16H14Cl2N2O2V = 777.8 (4) Å3
Mr = 337.19Z = 2
Monoclinic, P21/nMo Kα radiation
a = 4.820 (2) ŵ = 0.43 mm1
b = 11.445 (3) ÅT = 293 K
c = 14.242 (4) Å0.44 × 0.08 × 0.04 mm
β = 98.10 (3)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
1563 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
900 reflections with I > 2σ(I)
Tmin = 0.835, Tmax = 0.983Rint = 0.038
2501 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0751 restraint
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 1.16Δρmax = 0.25 e Å3
1563 reflectionsΔρmin = 0.22 e Å3
103 parameters
Special details top

Experimental. CrysAlis RED (Oxford Diffraction, 2009) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.0199 (7)0.1565 (3)0.8739 (3)0.0360 (10)
C20.0563 (7)0.1162 (3)0.7889 (3)0.0372 (10)
C30.0371 (9)0.0099 (4)0.7516 (3)0.0486 (11)
H30.01930.01640.69550.058*
C40.2122 (9)0.0569 (4)0.7966 (4)0.0584 (13)
H40.27600.12830.77100.070*
C50.2940 (10)0.0188 (4)0.8796 (4)0.0596 (13)
H50.41510.06390.90990.072*
C60.1964 (9)0.0869 (4)0.9185 (3)0.0490 (11)
H60.25040.11140.97550.059*
C70.0733 (8)0.3461 (4)0.9476 (3)0.0392 (10)
C80.0844 (9)0.4520 (4)0.9871 (4)0.0621 (14)
H8A0.21150.42871.04300.075*
H8B0.19770.47990.94060.075*
N10.0847 (6)0.2633 (3)0.9133 (2)0.0392 (9)
H1N0.251 (5)0.287 (3)0.909 (3)0.047*
O10.3255 (5)0.3362 (2)0.9469 (2)0.0506 (9)
Cl10.2688 (2)0.20113 (11)0.72809 (8)0.0586 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0217 (18)0.040 (2)0.045 (2)0.0046 (18)0.0007 (18)0.002 (2)
C20.028 (2)0.037 (2)0.046 (3)0.0015 (19)0.0026 (18)0.006 (2)
C30.041 (2)0.050 (3)0.052 (3)0.004 (2)0.002 (2)0.016 (2)
C40.046 (3)0.039 (3)0.088 (4)0.006 (2)0.002 (3)0.014 (3)
C50.052 (3)0.047 (3)0.081 (4)0.013 (2)0.012 (3)0.002 (3)
C60.043 (3)0.051 (3)0.054 (3)0.002 (2)0.012 (2)0.001 (2)
C70.025 (2)0.049 (3)0.043 (2)0.0019 (19)0.0035 (18)0.010 (2)
C80.030 (2)0.061 (3)0.096 (4)0.005 (2)0.013 (2)0.040 (3)
N10.0212 (17)0.035 (2)0.063 (2)0.0055 (16)0.0102 (17)0.0159 (17)
O10.0202 (14)0.0527 (19)0.079 (2)0.0032 (13)0.0082 (14)0.0217 (16)
Cl10.0566 (7)0.0597 (7)0.0648 (8)0.0032 (7)0.0266 (6)0.0035 (7)
Geometric parameters (Å, º) top
C1—C61.384 (5)C5—H50.9300
C1—C21.393 (5)C6—H60.9300
C1—N11.408 (5)C7—O11.220 (4)
C2—C31.377 (5)C7—N11.350 (5)
C2—Cl11.730 (4)C7—C81.498 (5)
C3—C41.364 (6)C8—C8i1.445 (8)
C3—H30.9300C8—H8A0.9700
C4—C51.369 (6)C8—H8B0.9700
C4—H40.9300N1—H1N0.857 (19)
C5—C61.384 (6)
C6—C1—C2117.6 (4)C5—C6—C1121.0 (4)
C6—C1—N1121.7 (4)C5—C6—H6119.5
C2—C1—N1120.7 (4)C1—C6—H6119.5
C3—C2—C1121.1 (4)O1—C7—N1123.0 (4)
C3—C2—Cl1119.2 (3)O1—C7—C8122.1 (4)
C1—C2—Cl1119.7 (3)N1—C7—C8115.0 (3)
C4—C3—C2120.3 (4)C8i—C8—C7115.9 (4)
C4—C3—H3119.9C8i—C8—H8A108.3
C2—C3—H3119.9C7—C8—H8A108.3
C3—C4—C5120.0 (4)C8i—C8—H8B108.3
C3—C4—H4120.0C7—C8—H8B108.3
C5—C4—H4120.0H8A—C8—H8B107.4
C4—C5—C6120.1 (4)C7—N1—C1124.4 (3)
C4—C5—H5120.0C7—N1—H1N113 (3)
C6—C5—H5120.0C1—N1—H1N122 (3)
C6—C1—C2—C31.1 (6)C2—C1—C6—C50.2 (6)
N1—C1—C2—C3177.7 (4)N1—C1—C6—C5178.9 (4)
C6—C1—C2—Cl1178.3 (3)O1—C7—C8—C8i7.8 (9)
N1—C1—C2—Cl13.0 (5)N1—C7—C8—C8i172.2 (5)
C1—C2—C3—C41.4 (6)O1—C7—N1—C10.6 (7)
Cl1—C2—C3—C4177.9 (3)C8—C7—N1—C1179.3 (4)
C2—C3—C4—C50.5 (7)C6—C1—N1—C747.6 (6)
C3—C4—C5—C60.8 (7)C2—C1—N1—C7133.7 (4)
C4—C5—C6—C11.2 (7)
Symmetry code: (i) x, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1ii0.86 (2)2.11 (2)2.936 (4)161 (3)
Symmetry code: (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC16H14Cl2N2O2
Mr337.19
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)4.820 (2), 11.445 (3), 14.242 (4)
β (°) 98.10 (3)
V3)777.8 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.43
Crystal size (mm)0.44 × 0.08 × 0.04
Data collection
DiffractometerOxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2009)
Tmin, Tmax0.835, 0.983
No. of measured, independent and
observed [I > 2σ(I)] reflections
2501, 1563, 900
Rint0.038
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.075, 0.139, 1.16
No. of reflections1563
No. of parameters103
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.25, 0.22

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.857 (19)2.11 (2)2.936 (4)161 (3)
Symmetry code: (i) x+1, y, z.
 

Acknowledgements

BSS thanks the University Grants Commission, Government of India, New Delhi, for the award of a research fellowship under its faculty improvement program.

References

First citationGowda, B. T., Foro, S. & Fuess, H. (2007). Acta Cryst. E63, o2597.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationGowda, B. T., Paulus, H. & Fuess, H. (2000). Z. Naturforsch. Teil A, 55, 791–800.  CAS Google Scholar
First citationOxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.  Google Scholar
First citationPierrot, M., Baldy, A., Maire, J. C., Mehrotra, R. C., Kapoor, T. S. & Bachlas, B. P. (1984). Acta Cryst. C40, 1931–1934.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationSaraswathi, B. S., Foro, S. & Gowda, B. T. (2011a). Acta Cryst. E67, o607.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSaraswathi, B. S., Foro, S. & Gowda, B. T. (2011b). Acta Cryst. E67, o966.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 5| May 2011| Page o1139
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