Methyl 3-[(3,5-dichloro­anilino)carbon­yl]propionate

Saraswathi, B.S.; Gowda, B.T.; Foro, S.; Fuess, H.

doi:10.1107/S1600536810001455

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o387

https://doi.org/10.1107/S1600536810001455

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Methyl 3-[(3,5-dichloroanilino)carbonyl]propionate

B. S. Saraswathi,^a B. Thimme Gowda,^a ^* Sabine Foro ^b and Hartmut Fuess ^b

^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 10 January 2010; accepted 12 January 2010; online 16 January 2010)

In the title compound, C₁₁H₁₁Cl₂NO₃, the amide O atom and the carbonyl O atom of the ester segment are anti to each other and anti to the H atoms of the adjacent –CH₂ groups. In the crystal structure, molecules are packed into centrosymmetric dimers through intermolecular N—H⋯O hydrogen bonds. The dimers are linked into a layer structure extending parallel to ( $[\overline{1}]$ 02) by C—H⋯O hydrogen bonds.

Related literature

For related structures, see: Gowda et al. (2009a ,b ,c ).

Experimental

Crystal data

C₁₁H₁₁Cl₂NO₃
M_r = 276.11
Monoclinic, C 2/c
a = 12.865 (2) Å
b = 14.753 (3) Å
c = 14.114 (2) Å
β = 109.59 (2)°
V = 2523.7 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 299 K
0.50 × 0.16 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.785, T_max = 0.941
4503 measured reflections
2259 independent reflections
1453 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.166
S = 1.09
2259 reflections
157 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.85 (2)	2.17 (2)	3.017 (4)	172 (4)
C4—H4⋯O1ⁱⁱ	0.93	2.45	3.379 (5)	174
Symmetry codes: (i) $[-x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810001455/ci5017sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810001455/ci5017Isup2.hkl

checkCIF report

Comment top

As a part of studying the effect of ring and side chain substitutions on the structures of biologically significant compounds (Gowda et al., 2009a,b,c), the crystal structure of N-(3,5-dichlorophenyl)methylsuccinamate [systematic name: 3-[(3,5-dichloro)-aminocarbonyl]propionate] has been determined.

The conformation of the amide O atom and the carbonyl O atom of the ester segment are anti to each other and both are anti to the H atoms of the adjacent -CH₂ groups (Fig. 1), similar to that observed in N-(3,5-dichlorophenyl)methylsuccinamic acid (Gowda et al., 2009c) and N-(3,5-dimethylphenyl)ethylsuccinamate (Gowda et al., 2009a).

In the crystal, molecules are packed into centrosymmetric dimers through intermolecular N—H···O hydrogen bonds (Table 1 and Fig.2).

Related literature top

For related structures, see: Gowda et al. (2009a,b,c).

Experimental top

A solution of succinic anhydride (0.02 mol) in toluene (25 ml) was treated dropwise with a solution of 3,5-dichloroaniline (0.02 mol) in toluene (20 ml) with constant stirring. The resulting mixture was stirred for 1 h and set aside for an additional 1 hour at room temperature for the completion of reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted 3,5-dichloroaniline. The resultant solid N-(3,5-dichlorophenyl)succinamic acid was filtered under suction and washed thoroughly with water to remove the unreacted succinic anhydride and succinic acid. It was recrystallized to constant melting point from methanol. Pure N-(3,5-dichlorophenyl)succinamic acid in methanol was refluxed with 2 ml of conc. sulfuric acid for 2 h and was subjected to slow evaporation. The resulting N-(3,5-dichlorophenyl)methylsuccinamate was recrystallized from methanol. The purity of the compound was checked and characterized by its IR and NMR spectra. Single crystals were grown in a methanol solution by slow evaporation at room temperature.

Structure description top

In the crystal, molecules are packed into centrosymmetric dimers through intermolecular N—H···O hydrogen bonds (Table 1 and Fig.2).

For related structures, see: Gowda et al. (2009a,b,c).

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

	Fig. 1. Molecular structure of the title compound, showing the atomic labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of the title compound, showing hydrogen-bonded (dashed lines) dimers.

Methyl 3-[(3,5-dichloroanilino)carbonyl]propionate top

Crystal data top

C₁₁H₁₁Cl₂NO₃	F(000) = 1136
M_r = 276.11	D_x = 1.453 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1000 reflections
a = 12.865 (2) Å	θ = 3.0–28.1°
b = 14.753 (3) Å	µ = 0.51 mm⁻¹
c = 14.114 (2) Å	T = 299 K
β = 109.59 (2)°	Needle, colourless
V = 2523.7 (7) Å³	0.50 × 0.16 × 0.12 mm
Z = 8

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2259 independent reflections
Radiation source: fine-focus sealed tube	1453 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Rotation method data acquisition using ω and φ scans.	θ_max = 25.4°, θ_min = 3.0°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −11→15
T_min = 0.785, T_max = 0.941	k = −17→10
4503 measured reflections	l = −17→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0595P)² + 4.6291P] where P = (F_o² + 2F_c²)/3
2259 reflections	(Δ/σ)_max = 0.002
157 parameters	Δρ_max = 0.37 e Å⁻³
1 restraint	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₁H₁₁Cl₂NO₃	V = 2523.7 (7) Å³
M_r = 276.11	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 12.865 (2) Å	µ = 0.51 mm⁻¹
b = 14.753 (3) Å	T = 299 K
c = 14.114 (2) Å	0.50 × 0.16 × 0.12 mm
β = 109.59 (2)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2259 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1453 reflections with I > 2σ(I)
T_min = 0.785, T_max = 0.941	R_int = 0.035
4503 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	1 restraint
wR(F²) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.37 e Å⁻³
2259 reflections	Δρ_min = −0.21 e Å⁻³
157 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.0757 (3)	0.6059 (3)	0.6618 (3)	0.0532 (9)
C2	0.0482 (3)	0.5146 (3)	0.6460 (3)	0.0591 (10)
H2	−0.0243	0.4975	0.6116	0.071*
C3	0.1280 (3)	0.4501 (3)	0.6814 (3)	0.0616 (11)
C4	0.2370 (3)	0.4721 (3)	0.7337 (3)	0.0627 (11)
H4	0.2906	0.4276	0.7580	0.075*
C5	0.2620 (3)	0.5621 (3)	0.7481 (3)	0.0583 (10)
C6	0.1848 (3)	0.6306 (3)	0.7149 (3)	0.0565 (10)
H6	0.2048	0.6911	0.7275	0.068*
C7	−0.0024 (3)	0.7610 (3)	0.6273 (3)	0.0560 (10)
C8	−0.1087 (3)	0.8104 (3)	0.5736 (3)	0.0603 (11)
H8A	−0.1369	0.7910	0.5040	0.072*
H8B	−0.1632	0.7953	0.6047	0.072*
C9	−0.0911 (3)	0.9108 (3)	0.5778 (3)	0.0624 (11)
H9A	−0.0324	0.9245	0.5512	0.075*
H9B	−0.0665	0.9298	0.6477	0.075*
C10	−0.1908 (3)	0.9652 (3)	0.5209 (3)	0.0551 (10)
C11	−0.2543 (4)	1.1146 (3)	0.4756 (4)	0.0849 (15)
H11A	−0.3094	1.1103	0.5074	0.102*
H11B	−0.2866	1.0998	0.4056	0.102*
H11C	−0.2258	1.1753	0.4824	0.102*
N1	−0.0090 (2)	0.6699 (2)	0.6230 (3)	0.0569 (9)
H1N	−0.072 (2)	0.645 (3)	0.595 (3)	0.068*
O1	0.0828 (2)	0.8016 (2)	0.6710 (3)	0.0875 (11)
O2	−0.2818 (2)	0.93505 (18)	0.4784 (2)	0.0668 (8)
O3	−0.1659 (2)	1.05231 (19)	0.5228 (2)	0.0754 (9)
Cl1	0.09280 (11)	0.33629 (8)	0.66222 (11)	0.0926 (5)
Cl2	0.39797 (8)	0.59326 (9)	0.81343 (10)	0.0845 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0445 (19)	0.062 (2)	0.051 (2)	0.0079 (18)	0.0133 (17)	0.0045 (19)
C2	0.057 (2)	0.059 (3)	0.058 (2)	−0.0010 (19)	0.0150 (18)	−0.001 (2)
C3	0.067 (2)	0.056 (3)	0.064 (3)	0.010 (2)	0.024 (2)	0.004 (2)
C4	0.061 (2)	0.067 (3)	0.061 (3)	0.019 (2)	0.021 (2)	0.008 (2)
C5	0.048 (2)	0.070 (3)	0.056 (2)	0.0104 (19)	0.0149 (18)	0.002 (2)
C6	0.048 (2)	0.061 (2)	0.056 (2)	0.0050 (19)	0.0113 (18)	0.0050 (19)
C7	0.044 (2)	0.053 (2)	0.061 (3)	−0.0037 (18)	0.0048 (17)	0.0035 (19)
C8	0.045 (2)	0.057 (2)	0.066 (3)	−0.0019 (18)	0.0017 (18)	0.004 (2)
C9	0.045 (2)	0.058 (3)	0.072 (3)	−0.0013 (18)	0.0032 (19)	0.005 (2)
C10	0.052 (2)	0.054 (2)	0.055 (2)	−0.0041 (18)	0.0130 (18)	−0.0002 (19)
C11	0.096 (4)	0.058 (3)	0.101 (4)	0.018 (3)	0.033 (3)	0.010 (3)
N1	0.0402 (16)	0.055 (2)	0.065 (2)	−0.0013 (15)	0.0040 (15)	0.0031 (16)
O1	0.0455 (16)	0.0632 (19)	0.125 (3)	−0.0082 (14)	−0.0102 (16)	0.0064 (18)
O2	0.0458 (15)	0.0670 (18)	0.075 (2)	−0.0014 (13)	0.0035 (13)	0.0041 (15)
O3	0.0653 (18)	0.0543 (18)	0.095 (2)	0.0024 (14)	0.0120 (16)	0.0036 (16)
Cl1	0.0935 (9)	0.0592 (7)	0.1195 (12)	0.0048 (6)	0.0283 (8)	−0.0022 (7)
Cl2	0.0464 (6)	0.0885 (9)	0.1033 (10)	0.0137 (5)	0.0047 (6)	−0.0017 (7)

Geometric parameters (Å, º) top

C1—C2	1.391 (5)	C7—C8	1.510 (5)
C1—C6	1.401 (5)	C8—C9	1.496 (5)
C1—N1	1.407 (5)	C8—H8A	0.97
C2—C3	1.366 (5)	C8—H8B	0.97
C2—H2	0.93	C9—C10	1.499 (5)
C3—C4	1.387 (6)	C9—H9A	0.97
C3—Cl1	1.736 (4)	C9—H9B	0.97
C4—C5	1.365 (6)	C10—O2	1.207 (4)
C4—H4	0.93	C10—O3	1.322 (4)
C5—C6	1.384 (5)	C11—O3	1.440 (5)
C5—Cl2	1.743 (4)	C11—H11A	0.96
C6—H6	0.93	C11—H11B	0.96
C7—O1	1.219 (4)	C11—H11C	0.96
C7—N1	1.347 (5)	N1—H1N	0.850 (19)

C2—C1—C6	119.5 (4)	C7—C8—H8A	109.4
C2—C1—N1	117.8 (3)	C9—C8—H8B	109.4
C6—C1—N1	122.7 (4)	C7—C8—H8B	109.4
C3—C2—C1	119.8 (4)	H8A—C8—H8B	108.0
C3—C2—H2	120.1	C8—C9—C10	114.7 (3)
C1—C2—H2	120.1	C8—C9—H9A	108.6
C2—C3—C4	122.2 (4)	C10—C9—H9A	108.6
C2—C3—Cl1	119.4 (3)	C8—C9—H9B	108.6
C4—C3—Cl1	118.3 (3)	C10—C9—H9B	108.6
C5—C4—C3	116.9 (4)	H9A—C9—H9B	107.6
C5—C4—H4	121.5	O2—C10—O3	123.8 (4)
C3—C4—H4	121.5	O2—C10—C9	125.6 (4)
C4—C5—C6	123.6 (4)	O3—C10—C9	110.6 (3)
C4—C5—Cl2	118.7 (3)	O3—C11—H11A	109.5
C6—C5—Cl2	117.7 (3)	O3—C11—H11B	109.5
C5—C6—C1	117.9 (4)	H11A—C11—H11B	109.5
C5—C6—H6	121.1	O3—C11—H11C	109.5
C1—C6—H6	121.1	H11A—C11—H11C	109.5
O1—C7—N1	123.0 (4)	H11B—C11—H11C	109.5
O1—C7—C8	121.8 (4)	C7—N1—C1	128.6 (3)
N1—C7—C8	115.2 (3)	C7—N1—H1N	119 (3)
C9—C8—C7	111.0 (3)	C1—N1—H1N	113 (3)
C9—C8—H8A	109.4	C10—O3—C11	117.5 (3)

C6—C1—C2—C3	−0.8 (6)	O1—C7—C8—C9	3.2 (6)
N1—C1—C2—C3	179.3 (4)	N1—C7—C8—C9	−176.8 (4)
C1—C2—C3—C4	0.4 (6)	C7—C8—C9—C10	176.4 (4)
C1—C2—C3—Cl1	179.5 (3)	C8—C9—C10—O2	4.0 (6)
C2—C3—C4—C5	−0.6 (6)	C8—C9—C10—O3	−175.6 (4)
Cl1—C3—C4—C5	−179.6 (3)	O1—C7—N1—C1	−2.7 (7)
C3—C4—C5—C6	1.1 (6)	C8—C7—N1—C1	177.3 (4)
C3—C4—C5—Cl2	−180.0 (3)	C2—C1—N1—C7	−178.9 (4)
C4—C5—C6—C1	−1.5 (6)	C6—C1—N1—C7	1.2 (6)
Cl2—C5—C6—C1	179.6 (3)	O2—C10—O3—C11	3.3 (6)
C2—C1—C6—C5	1.3 (6)	C9—C10—O3—C11	−177.0 (4)
N1—C1—C6—C5	−178.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.85 (2)	2.17 (2)	3.017 (4)	172 (4)
C4—H4···O1ⁱⁱ	0.93	2.45	3.379 (5)	174

Symmetry codes: (i) −x−1/2, −y+3/2, −z+1; (ii) −x+1/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁Cl₂NO₃
M_r	276.11
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	299
a, b, c (Å)	12.865 (2), 14.753 (3), 14.114 (2)
β (°)	109.59 (2)
V (Å³)	2523.7 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.50 × 0.16 × 0.12

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.785, 0.941
No. of measured, independent and observed [I > 2σ(I)] reflections	4503, 2259, 1453
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.166, 1.09
No. of reflections	2259
No. of parameters	157
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.21

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···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.85 (2)	2.17 (2)	3.017 (4)	172 (4)
C4—H4···O1ⁱⁱ	0.93	2.45	3.379 (5)	174

Symmetry codes: (i) −x−1/2, −y+3/2, −z+1; (ii) −x+1/2, y−1/2, −z+3/2.

Acknowledgements

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

References

Gowda, B. T., Foro, S., Saraswathi, B. S. & Fuess, H. (2009a). Acta Cryst. E65, o2039. Web of Science CSD CrossRef IUCr Journals Google Scholar
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