Methyl N-(4-chloro­phenyl)succinamate

In the structure of the title compound {systematic name: methyl 3-[(4-chloro­phen­yl)amino­carbon­yl]propionate}, C₁₁H₁₂ClNO₃, the conformations of the N—H and C=O bonds in the amide fragment are trans to each other and the conformations of the amide O atom and the carbonyl O atom of the ester fragment are also trans to the H atoms attached to the adjacent C atoms. Mol­ecules are linked into a centrosymmetric R₂²(14) dimer by simple N—H⋯O inter­actions. Furthermore, a short intra­molecular C—H⋯O contact may stabilize the conformation adopted by the mol­ecule in the crystal.

Related literature

For background, see: Gowda et al. (2007); Gowda, Foro & Fuess (2008); Gowda, Foro, Sowmya et al. (2008); Jones et al. (1990); Wan et al. (2006). For related literature, see: Bernstein et al. (1995).

Experimental

Crystal data

• C₁₁H₁₂ClNO₃

• M_r = 241.67

• Orthorhombic, P b c a

• a = 14.190 (1) Å

• b = 5.6370 (5) Å

• c = 28.139 (3) Å

• V = 2250.8 (4) ų

• Z = 8

• Mo Kα radiation

• μ = 0.33 mm⁻¹

• T = 299 (2) K

• 0.50 × 0.48 × 0.44 mm

Data collection

• Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector

• Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) T_min = 0.852, T_max = 0.868

• 10377 measured reflections

• 2272 independent reflections

• 1649 reflections with I > 2σ(I)

• R_int = 0.043

Refinement

• R[F² > 2σ(F²)] = 0.050

• wR(F²) = 0.154

• S = 1.19

• 2272 reflections

• 173 parameters

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

• Δρ_max = 0.28 e Å⁻³

• Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1	0.94 (3)	2.22 (3)	2.833 (4)	121 (3)
N1—H1N⋯O2^i	0.82 (3)	2.22 (3)	3.020 (3)	163 (3)
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); 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, 2003); software used to prepare material for publication: SHELXL97.

Supporting information

S1. Comment

Amides are of interest as conjugation between the nitrogen lone pair electrons and the carbonyl pi-bond results in distinct physical and chemical properties. The amide moiety is also an important constituent of many biologically significant compounds. Thus, the structural studies of amides are of interest (see Gowda et al., 2007 and references therein; Gowda, Foro & Fuess, 2008; Gowda, Foro, Sowmya et al., 2008; Jones et al., 1990; Wan et al., 2006 as representative examples). As a part of studying the effect of ring and side-chain substitutions on the solid state geometry of this class of compounds, we report herein the crystal structure of N-(4-chlorophenyl)methylsuccinamate (N4CPMSA). The conformations of N—H and C=O bonds in the amide fragment are trans to each other and the conformations of the amide oxygen and the carbonyl oxygen of the ester segment are also trans to the H-atoms attached to the adjacent carbons (Fig. 1). The succinamido group and the benzene ring lie in the same plane with the Rms deviation of fitted atoms equal to 0.0720 Å. The molecules are linked into centrosymmetric R~2~^2^(14) dimer by simple N-H···O interactions (Bernstein et al., 1995). Furthermore, a short intramolecular C-H···.O contact may stabilize the conformation adopted by the molecule in the solid state (Table 1) is shown in Fig.2.

Related literature

For background, see: Gowda et al. (2007); Gowda, Foro & Fuess (2008); Gowda, Foro, Sowmya et al. (2008); Jones et al. (1990); Wan et al. (2006). For related literature, see: Bernstein et al. (1995).

S2. Experimental

The solution of succinic anhydride (0.025 mole) in toluene (25 cc) was treated dropwise with the solution of 4-chloroaniline (0.025 mole) in toluene (20 cc) with constant stirring. The resulting mixture was stirred for about 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 the unreacted 4-chloroaniline. The resultant solid N-(4-chlorophenyl)-succinamic acid was filtered under suction and washed thoroughly with water to remove the unreacted succinic anhydride and succinic acid. The slow crystallization of N-(4-chlorophenyl)-succinamic acid in hot methanol resulted in N-(4-chlorophenyl)-methylsuccinamate. It was further recrystallized to constant melting point from methanol. The purity of the compound was checked by elemental analysis and characterized by recording its infrared and NMR spectra. The single crystals used in X-ray diffraction studies were grown in methanolic solution by slow evaporation at room temperature.

S3. Refinement

The H atoms of the methyl group were positioned with idealized geometry using a riding model with C—H = 0.96 Å. The other H atoms were located in difference map, and their positional parameters were refined freely [N—H = 0.82 (3) Å, C—H = 0.90 (3)–1.01 (3) Å]. All H atoms were refined with isotropic displacement parameters with U_iso(H) = 1.2 U_eq(C-aromatic,N) or 1.5 U_eq (C-methyl).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. Molecular structure of the title compound, showing the atom labeling scheme. The displacement ellipsoids are drawn at the 50% probability level. The H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. A fragment of the structure of (I) , viewed along the b axis , dashed lines. shown N-H···O and C-H···O interactions

Methyl 3-[(4-chlorophenyl)aminocarbonyl]propionate

Crystal data

C11H12ClNO3	F(000) = 1008
Mr = 241.67	Dx = 1.426 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3422 reflections
a = 14.190 (1) Å	θ = 2.6–28.0°
b = 5.6370 (5) Å	µ = 0.33 mm^−1
c = 28.139 (3) Å	T = 299 K
V = 2250.8 (4) Å^3	Prism, colourless
Z = 8	0.50 × 0.48 × 0.44 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector	2272 independent reflections
Radiation source: fine-focus sealed tube	1649 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Rotation method data acquisition using ω and ϕ scans	θmax = 26.4°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	h = −17→17
Tmin = 0.852, Tmax = 0.868	k = −7→7
10377 measured reflections	l = −33→35

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.154	w = 1/[σ^2(Fo^2) + (0.0501P)^2 + 2.2683P] where P = (Fo^2 + 2Fc^2)/3
S = 1.19	(Δ/σ)max < 0.001
2272 reflections	Δρmax = 0.28 e Å^−3
173 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0109 (13)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.63844 (7)	1.51417 (17)	0.23361 (3)	0.0671 (3)
O1	0.67752 (18)	1.1013 (4)	0.00684 (8)	0.0659 (7)
O2	0.56516 (16)	0.4234 (4)	−0.09121 (8)	0.0591 (6)
O3	0.66393 (16)	0.6160 (5)	−0.13895 (8)	0.0635 (7)
N1	0.58842 (17)	0.9188 (5)	0.06256 (8)	0.0436 (6)
H1N	0.554 (2)	0.804 (6)	0.0675 (12)	0.052*
C1	0.60124 (18)	1.0708 (5)	0.10151 (9)	0.0384 (6)
C2	0.5627 (2)	1.0015 (6)	0.14469 (11)	0.0485 (7)
H2	0.525 (2)	0.866 (6)	0.1470 (11)	0.058*
C3	0.5731 (2)	1.1346 (6)	0.18498 (11)	0.0526 (8)
H3	0.546 (2)	1.083 (6)	0.2168 (12)	0.063*
C4	0.6234 (2)	1.3447 (5)	0.18267 (10)	0.0444 (7)
C5	0.6611 (2)	1.4180 (5)	0.14030 (11)	0.0439 (7)
H5	0.693 (2)	1.555 (6)	0.1384 (11)	0.053*
C6	0.65037 (19)	1.2848 (5)	0.09955 (11)	0.0423 (6)
H6	0.677 (2)	1.336 (6)	0.0706 (11)	0.051*
C7	0.62722 (19)	0.9364 (5)	0.01857 (10)	0.0399 (6)
C8	0.6017 (2)	0.7370 (5)	−0.01474 (10)	0.0418 (7)
H8A	0.532 (2)	0.724 (5)	−0.0177 (10)	0.050*
H8B	0.621 (2)	0.584 (6)	−0.0004 (11)	0.050*
C9	0.6451 (2)	0.7706 (6)	−0.06280 (10)	0.0448 (7)
H9A	0.712 (2)	0.773 (6)	−0.0601 (11)	0.054*
H9B	0.628 (2)	0.926 (6)	−0.0768 (11)	0.054*
C10	0.61912 (19)	0.5841 (5)	−0.09780 (10)	0.0417 (6)
C11	0.6445 (3)	0.4460 (7)	−0.17585 (12)	0.0674 (10)
H11A	0.6541	0.2885	−0.1638	0.081*
H11B	0.6861	0.4731	−0.2022	0.081*
H11C	0.5804	0.4629	−0.1862	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0874 (7)	0.0637 (6)	0.0502 (5)	−0.0054 (5)	0.0006 (4)	−0.0139 (4)
O1	0.0876 (17)	0.0558 (13)	0.0542 (13)	−0.0273 (13)	0.0239 (12)	−0.0081 (11)
O2	0.0642 (14)	0.0613 (14)	0.0520 (13)	−0.0215 (12)	0.0051 (10)	−0.0043 (11)
O3	0.0656 (14)	0.0797 (16)	0.0453 (12)	−0.0206 (13)	0.0149 (10)	−0.0109 (12)
N1	0.0475 (13)	0.0430 (14)	0.0403 (13)	−0.0096 (11)	0.0041 (10)	0.0028 (11)
C1	0.0374 (13)	0.0383 (14)	0.0396 (14)	0.0019 (11)	−0.0017 (11)	0.0051 (11)
C2	0.0546 (17)	0.0442 (16)	0.0467 (16)	−0.0106 (14)	0.0081 (13)	0.0033 (14)
C3	0.0629 (19)	0.0551 (19)	0.0398 (15)	−0.0065 (15)	0.0114 (14)	0.0034 (14)
C4	0.0473 (15)	0.0424 (16)	0.0436 (15)	0.0063 (13)	−0.0007 (12)	−0.0023 (12)
C5	0.0423 (15)	0.0366 (15)	0.0527 (17)	−0.0003 (12)	0.0028 (13)	−0.0003 (13)
C6	0.0444 (14)	0.0382 (15)	0.0442 (15)	−0.0025 (12)	0.0031 (12)	0.0071 (12)
C7	0.0392 (14)	0.0404 (15)	0.0401 (14)	0.0030 (12)	0.0031 (11)	0.0032 (12)
C8	0.0409 (14)	0.0426 (16)	0.0419 (15)	−0.0018 (13)	−0.0015 (12)	0.0014 (12)
C9	0.0440 (15)	0.0489 (17)	0.0415 (15)	−0.0067 (13)	0.0010 (12)	−0.0011 (13)
C10	0.0386 (14)	0.0468 (16)	0.0396 (14)	0.0019 (13)	−0.0003 (11)	0.0000 (12)
C11	0.068 (2)	0.085 (3)	0.0490 (18)	−0.007 (2)	0.0084 (16)	−0.0178 (18)

Geometric parameters (Å, º)

Cl1—C4	1.736 (3)	C4—C5	1.371 (4)
O1—C7	1.217 (3)	C5—C6	1.379 (4)
O2—C10	1.200 (3)	C5—H5	0.90 (3)
O3—C10	1.333 (3)	C6—H6	0.94 (3)
O3—C11	1.440 (4)	C7—C8	1.507 (4)
N1—C7	1.358 (4)	C8—C9	1.498 (4)
N1—C1	1.403 (4)	C8—H8A	1.00 (3)
N1—H1N	0.82 (3)	C8—H8B	0.99 (3)
C1—C2	1.388 (4)	C9—C10	1.487 (4)
C1—C6	1.395 (4)	C9—H9A	0.95 (3)
C2—C3	1.367 (4)	C9—H9B	0.99 (3)
C2—H2	0.94 (3)	C11—H11A	0.9600
C3—C4	1.384 (4)	C11—H11B	0.9600
C3—H3	1.01 (3)	C11—H11C	0.9600
C10—O3—C11	116.4 (3)	O1—C7—C8	122.8 (3)
C7—N1—C1	127.9 (2)	N1—C7—C8	114.5 (2)
C7—N1—H1N	117 (2)	C9—C8—C7	111.6 (2)
C1—N1—H1N	115 (2)	C9—C8—H8A	110.0 (17)
C2—C1—C6	118.3 (3)	C7—C8—H8A	110.2 (17)
C2—C1—N1	117.4 (3)	C9—C8—H8B	111.4 (18)
C6—C1—N1	124.2 (2)	C7—C8—H8B	109.3 (18)
C3—C2—C1	121.9 (3)	H8A—C8—H8B	104 (2)
C3—C2—H2	117 (2)	C10—C9—C8	114.0 (2)
C1—C2—H2	121 (2)	C10—C9—H9A	108.0 (19)
C2—C3—C4	119.1 (3)	C8—C9—H9A	109.9 (19)
C2—C3—H3	122.3 (19)	C10—C9—H9B	107.4 (19)
C4—C3—H3	118.6 (19)	C8—C9—H9B	111.6 (19)
C5—C4—C3	120.0 (3)	H9A—C9—H9B	106 (3)
C5—C4—Cl1	120.3 (2)	O2—C10—O3	122.7 (3)
C3—C4—Cl1	119.7 (2)	O2—C10—C9	126.1 (3)
C4—C5—C6	121.0 (3)	O3—C10—C9	111.2 (2)
C4—C5—H5	121 (2)	O3—C11—H11A	109.5
C6—C5—H5	118 (2)	O3—C11—H11B	109.5
C5—C6—C1	119.6 (3)	H11A—C11—H11B	109.5
C5—C6—H6	120.5 (19)	O3—C11—H11C	109.5
C1—C6—H6	119.9 (19)	H11A—C11—H11C	109.5
O1—C7—N1	122.7 (3)	H11B—C11—H11C	109.5
C7—N1—C1—C2	−172.7 (3)	N1—C1—C6—C5	−178.2 (3)
C7—N1—C1—C6	6.9 (4)	C1—N1—C7—O1	−3.2 (5)
C6—C1—C2—C3	−1.1 (5)	C1—N1—C7—C8	177.7 (3)
N1—C1—C2—C3	178.6 (3)	O1—C7—C8—C9	−0.4 (4)
C1—C2—C3—C4	0.0 (5)	N1—C7—C8—C9	178.7 (3)
C2—C3—C4—C5	0.7 (5)	C7—C8—C9—C10	−177.6 (2)
C2—C3—C4—Cl1	−179.2 (3)	C11—O3—C10—O2	−0.1 (4)
C3—C4—C5—C6	−0.4 (4)	C11—O3—C10—C9	−180.0 (3)
Cl1—C4—C5—C6	179.6 (2)	C8—C9—C10—O2	3.6 (4)
C4—C5—C6—C1	−0.7 (4)	C8—C9—C10—O3	−176.5 (3)
C2—C1—C6—C5	1.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1	0.94 (3)	2.22 (3)	2.833 (4)	121 (3)
N1—H1N···O2^i	0.82 (3)	2.22 (3)	3.020 (3)	163 (3)

Symmetry code: (i) −x+1, −y+1, −z.