N-(3-Chloro-2-methyl­phen­yl)succinamic acid

Gowda, B.T.; Foro, S.; Chaithanya, U.

doi:10.1107/S1600536812022763

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1869

doi:10.1107/S1600536812022763

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N-(3-Chloro-2-methylphenyl)succinamic acid

B. Thimme Gowda,^a ^* Sabine Foro ^b and U. Chaithanya ^a

^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 16 May 2012; accepted 18 May 2012; online 23 May 2012)

In the title compound, C₁₁H₁₂ClNO₃, the dihedral angle between the benzene ring and the amide group is 44.9 (2)°. In the crystal, molecules form inversion dimers via pairs of O—H⋯O hydrogen bonds. These dimers are further linked into sheets parallel to (013) via N—H⋯O hydrogen bonds.

Related literature

For our studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Gowda et al. (2000 ); Chaithanya et al. (2012 ), of N-chloroarylamides, see: Gowda & Rao (1989 ); Jyothi & Gowda (2004 ) and N-bromoarylsulfonamides, see: Gowda & Mahadevappa (1983 ), Usha & Gowda (2006 ).

Experimental

Crystal data

C₁₁H₁₂ClNO₃
M_r = 241.67
Triclinic, $[P \overline 1]$
a = 4.7672 (9) Å
b = 6.297 (1) Å
c = 19.135 (3) Å
α = 87.24 (1)°
β = 83.95 (1)°
γ = 88.28 (2)°
V = 570.37 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 K
0.40 × 0.20 × 0.02 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 = 0.881, T_max = 0.994
3270 measured reflections
2072 independent reflections
1578 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.127
S = 1.20
2072 reflections
152 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O2ⁱ	0.83 (2)	1.84 (2)	2.666 (3)	176 (5)
N1—H1N⋯O1ⁱⁱ	0.83 (2)	2.10 (2)	2.905 (3)	163 (3)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y, z.

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: 10.1107/S1600536812022763/bt5924sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022763/bt5924Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812022763/bt5924Isup3.cml

checkCIF report

Comment top

As part of our studies on the substituent effects on the structures and other aspects of N-(aryl)-amides (Gowda et al., 2000; Chaithanya et al., 2012); N-chloroarylsulfonamides (Gowda & Rao, 1989; Jyothi & Gowda, 2004) and N-bromoaryl- sulfonamides (Gowda & Mahadevappa, 1983; Usha & Gowda, 2006), in the present work, the crystal structure of N-(3-Chloro-2-methylphenyl)succinamic acid has been determined (Fig. 1). The conformation of the N—H bond in the amide segment is syn to the ortho–methyl and meta–Cl in the benzene ring, in contrast to the anti conformation observed between the N—H bond and the meta–Cl in N-(3-chloro-4-methylphenyl)- succinamic acid (I) (Chaithanya et al., 2012).

Further, the conformations of the amide oxygen and the carboxyl oxygen of the acid segments are anti to each other and both are anti to the H atoms on the adjacent –CH₂ groups.

The C═O and O—H bonds of the acid groups are in syn position to each other, similar to that observed in (I).

The dihedral angle between the phenyl ring and the amide group is 44.9 (2)°, compared to the values of 40.6 (2)° and 44.9 (3)° in the two independent molecules of (I).

In the crystal, the molecules form centrosymmetric dimers via O-H···O hydrogen bonds. These dimers are further linked into sheets parallel to (0 1 3) via intermolecular N–H···O hydrogen bonds. (Table 1, Fig.2).

Related literature top

For our studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Gowda et al. (2000); Chaithanya et al. (2012), of N-chloroarylamides, see: Gowda & Rao (1989); Jyothi & Gowda (2004) and N-bromoarylsulfonamides, see: Gowda & Mahadevappa (1983), Usha & Gowda (2006).

Experimental top

The solution of succinic anhydride (0.01 mole) in toluene (25 ml) was treated dropwise with the solution of 3-chloro-2-methylaniline (0.01 mole) also in toluene (20 ml) 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 3-chloro-2-methyl-aniline. The resultant (the title compound) 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 ethanol. The purity of the compound was checked and characterized by its infrared spectrum.

Plate like colorless single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation of the solvent at room temperature.

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 atom labelling scheme. The displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

N-(3-Chloro-2-methylphenyl)succinamic acid top

Crystal data top

C₁₁H₁₂ClNO₃	Z = 2
M_r = 241.67	F(000) = 252
Triclinic, P1	D_x = 1.407 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.7672 (9) Å	Cell parameters from 1394 reflections
b = 6.297 (1) Å	θ = 3.2–27.9°
c = 19.135 (3) Å	µ = 0.33 mm⁻¹
α = 87.24 (1)°	T = 293 K
β = 83.95 (1)°	Plate, colourless
γ = 88.28 (2)°	0.40 × 0.20 × 0.02 mm
V = 570.37 (17) Å³

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2072 independent reflections
Radiation source: fine-focus sealed tube	1578 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
Rotation method data acquisition using ω and phi scans	θ_max = 25.4°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −5→5
T_min = 0.881, T_max = 0.994	k = −7→7
3270 measured reflections	l = −22→22

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ²(F_o²) + (0.0209P)² + 0.6764P] where P = (F_o² + 2F_c²)/3
2072 reflections	(Δ/σ)_max = 0.004
152 parameters	Δρ_max = 0.29 e Å⁻³
2 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₁H₁₂ClNO₃	γ = 88.28 (2)°
M_r = 241.67	V = 570.37 (17) Å³
Triclinic, P1	Z = 2
a = 4.7672 (9) Å	Mo Kα radiation
b = 6.297 (1) Å	µ = 0.33 mm⁻¹
c = 19.135 (3) Å	T = 293 K
α = 87.24 (1)°	0.40 × 0.20 × 0.02 mm
β = 83.95 (1)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2072 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1578 reflections with I > 2σ(I)
T_min = 0.881, T_max = 0.994	R_int = 0.013
3270 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	2 restraints
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	Δρ_max = 0.29 e Å⁻³
2072 reflections	Δρ_min = −0.24 e Å⁻³
152 parameters

Special details top

Experimental. Absorption correction: 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

	x	y	z	U_iso*/U_eq
Cl1	0.7008 (3)	1.2310 (2)	0.02839 (6)	0.0864 (4)
O1	0.0716 (4)	0.7206 (4)	0.30679 (13)	0.0603 (7)
O2	0.5808 (6)	0.1513 (5)	0.42666 (16)	0.0873 (11)
O3	0.2228 (7)	0.1937 (5)	0.50625 (15)	0.0877 (11)
H3O	0.286 (10)	0.084 (5)	0.525 (2)	0.105*
N1	0.5099 (5)	0.8278 (4)	0.26805 (14)	0.0415 (7)
H1N	0.682 (4)	0.810 (5)	0.2711 (17)	0.050*
C1	0.4362 (6)	0.9970 (5)	0.22052 (16)	0.0393 (7)
C2	0.5859 (6)	1.0149 (5)	0.15377 (16)	0.0406 (8)
C3	0.5154 (7)	1.1899 (6)	0.11106 (18)	0.0514 (9)
C4	0.3030 (8)	1.3342 (6)	0.1311 (2)	0.0613 (10)
H4	0.2607	1.4479	0.1009	0.074*
C5	0.1540 (8)	1.3084 (6)	0.1963 (2)	0.0607 (10)
H5	0.0081	1.4037	0.2101	0.073*
C6	0.2212 (7)	1.1408 (5)	0.24147 (18)	0.0492 (9)
H6	0.1222	1.1245	0.2859	0.059*
C7	0.3272 (6)	0.7039 (5)	0.30781 (16)	0.0396 (7)
C8	0.4613 (6)	0.5332 (5)	0.35262 (17)	0.0442 (8)
H8A	0.5407	0.4215	0.3228	0.053*
H8B	0.6147	0.5938	0.3739	0.053*
C9	0.2546 (7)	0.4374 (5)	0.40990 (17)	0.0468 (8)
H9A	0.1956	0.5453	0.4433	0.056*
H9B	0.0886	0.3960	0.3891	0.056*
C10	0.3694 (6)	0.2483 (5)	0.44866 (17)	0.0437 (8)
C11	0.8049 (7)	0.8513 (6)	0.12881 (19)	0.0561 (10)
H11A	0.9893	0.9016	0.1341	0.067*
H11B	0.7911	0.8271	0.0801	0.067*
H11C	0.7743	0.7208	0.1562	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0936 (8)	0.0975 (9)	0.0604 (6)	0.0060 (7)	0.0040 (6)	0.0424 (6)
O1	0.0262 (11)	0.0745 (17)	0.0765 (17)	0.0014 (11)	−0.0078 (11)	0.0376 (14)
O2	0.0694 (18)	0.087 (2)	0.090 (2)	0.0396 (16)	0.0279 (16)	0.0509 (17)
O3	0.095 (2)	0.081 (2)	0.0711 (19)	0.0421 (17)	0.0320 (16)	0.0445 (16)
N1	0.0246 (12)	0.0503 (16)	0.0477 (15)	0.0015 (12)	−0.0063 (12)	0.0195 (13)
C1	0.0326 (16)	0.0368 (17)	0.0493 (19)	−0.0006 (13)	−0.0128 (14)	0.0105 (14)
C2	0.0360 (16)	0.0434 (18)	0.0427 (18)	−0.0029 (14)	−0.0102 (14)	0.0102 (14)
C3	0.051 (2)	0.052 (2)	0.050 (2)	−0.0023 (17)	−0.0102 (16)	0.0185 (17)
C4	0.066 (2)	0.048 (2)	0.069 (3)	0.0076 (19)	−0.019 (2)	0.0244 (19)
C5	0.065 (2)	0.042 (2)	0.075 (3)	0.0200 (18)	−0.014 (2)	0.0042 (19)
C6	0.0474 (19)	0.0468 (19)	0.052 (2)	0.0069 (16)	−0.0061 (16)	0.0051 (16)
C7	0.0284 (16)	0.0479 (19)	0.0415 (17)	0.0030 (13)	−0.0059 (13)	0.0110 (14)
C8	0.0305 (16)	0.0520 (19)	0.0481 (19)	0.0028 (14)	−0.0067 (14)	0.0200 (16)
C9	0.0398 (17)	0.050 (2)	0.0474 (19)	0.0075 (15)	0.0019 (15)	0.0169 (16)
C10	0.0350 (17)	0.0481 (19)	0.0450 (18)	0.0026 (14)	0.0019 (14)	0.0148 (15)
C11	0.050 (2)	0.063 (2)	0.052 (2)	0.0112 (18)	0.0030 (17)	0.0125 (18)

Geometric parameters (Å, º) top

Cl1—C3	1.741 (4)	C4—H4	0.9300
O1—C7	1.222 (3)	C5—C6	1.383 (5)
O2—C10	1.210 (4)	C5—H5	0.9300
O3—C10	1.279 (4)	C6—H6	0.9300
O3—H3O	0.831 (19)	C7—C8	1.512 (4)
N1—C7	1.338 (4)	C8—C9	1.510 (4)
N1—C1	1.427 (4)	C8—H8A	0.9700
N1—H1N	0.834 (18)	C8—H8B	0.9700
C1—C6	1.387 (4)	C9—C10	1.493 (4)
C1—C2	1.397 (4)	C9—H9A	0.9700
C2—C3	1.394 (4)	C9—H9B	0.9700
C2—C11	1.503 (4)	C11—H11A	0.9600
C3—C4	1.376 (5)	C11—H11B	0.9600
C4—C5	1.374 (5)	C11—H11C	0.9600

C10—O3—H3O	112 (3)	O1—C7—C8	121.8 (3)
C7—N1—C1	125.5 (2)	N1—C7—C8	114.8 (2)
C7—N1—H1N	119 (2)	C9—C8—C7	112.7 (2)
C1—N1—H1N	115 (2)	C9—C8—H8A	109.0
C6—C1—C2	121.4 (3)	C7—C8—H8A	109.0
C6—C1—N1	119.7 (3)	C9—C8—H8B	109.0
C2—C1—N1	118.8 (3)	C7—C8—H8B	109.0
C3—C2—C1	116.3 (3)	H8A—C8—H8B	107.8
C3—C2—C11	121.9 (3)	C10—C9—C8	114.1 (3)
C1—C2—C11	121.7 (3)	C10—C9—H9A	108.7
C4—C3—C2	122.9 (3)	C8—C9—H9A	108.7
C4—C3—Cl1	117.6 (3)	C10—C9—H9B	108.7
C2—C3—Cl1	119.5 (3)	C8—C9—H9B	108.7
C5—C4—C3	119.3 (3)	H9A—C9—H9B	107.6
C5—C4—H4	120.3	O2—C10—O3	122.5 (3)
C3—C4—H4	120.3	O2—C10—C9	122.8 (3)
C4—C5—C6	120.0 (3)	O3—C10—C9	114.7 (3)
C4—C5—H5	120.0	C2—C11—H11A	109.5
C6—C5—H5	120.0	C2—C11—H11B	109.5
C5—C6—C1	120.0 (3)	H11A—C11—H11B	109.5
C5—C6—H6	120.0	C2—C11—H11C	109.5
C1—C6—H6	120.0	H11A—C11—H11C	109.5
O1—C7—N1	123.3 (3)	H11B—C11—H11C	109.5

C7—N1—C1—C6	45.2 (5)	C3—C4—C5—C6	1.0 (6)
C7—N1—C1—C2	−135.5 (3)	C4—C5—C6—C1	−0.9 (6)
C6—C1—C2—C3	2.8 (5)	C2—C1—C6—C5	−1.1 (5)
N1—C1—C2—C3	−176.5 (3)	N1—C1—C6—C5	178.2 (3)
C6—C1—C2—C11	−175.6 (3)	C1—N1—C7—O1	1.3 (6)
N1—C1—C2—C11	5.1 (5)	C1—N1—C7—C8	178.8 (3)
C1—C2—C3—C4	−2.7 (5)	O1—C7—C8—C9	−17.7 (5)
C11—C2—C3—C4	175.7 (4)	N1—C7—C8—C9	164.6 (3)
C1—C2—C3—Cl1	177.4 (2)	C7—C8—C9—C10	171.9 (3)
C11—C2—C3—Cl1	−4.2 (5)	C8—C9—C10—O2	−16.0 (5)
C2—C3—C4—C5	0.8 (6)	C8—C9—C10—O3	165.6 (3)
Cl1—C3—C4—C5	−179.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O2ⁱ	0.83 (2)	1.84 (2)	2.666 (3)	176 (5)
N1—H1N···O1ⁱⁱ	0.83 (2)	2.10 (2)	2.905 (3)	163 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂ClNO₃
M_r	241.67
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	4.7672 (9), 6.297 (1), 19.135 (3)
α, β, γ (°)	87.24 (1), 83.95 (1), 88.28 (2)
V (Å³)	570.37 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.40 × 0.20 × 0.02

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	0.881, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	3270, 2072, 1578
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.127, 1.20
No. of reflections	2072
No. of parameters	152
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24

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
O3—H3O···O2ⁱ	0.831 (19)	1.84 (2)	2.666 (3)	176 (5)
N1—H1N···O1ⁱⁱ	0.834 (18)	2.10 (2)	2.905 (3)	163 (3)

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

Acknowledgements

BTG thanks the University Grants Commission, Government of India, New Delhi, for a special grant under theUGC–BSR one-time grant to faculty.

References

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