N-(2-Chloro-4-methyl­phen­yl)succinamic acid

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

doi:10.1107/S1600536812005648

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o785

doi:10.1107/S1600536812005648

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N-(2-Chloro-4-methylphenyl)succinamic acid

U. Chaithanya,^a Sabine Foro ^b and B. Thimme Gowda ^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 3 February 2012; accepted 8 February 2012; online 17 February 2012)

In the title compound, C₁₁H₁₂ClNO₃, the N—C=O fragment is twisted from the plane of the attached benzene ring by 48.39 (12)°. The carboxylic acid group is involved in O—H⋯O hydrogen bonding, which links pairs of molecules into centrosymmetric dimers. N—H⋯O hydrogen bonds link these dimers, related by translation along the a axis, into ribbons.

Related literature

For the crystal structures of related compounds studied by our group, see: Gowda et al. (2012 ) and references therein.

Experimental

Crystal data

C₁₁H₁₂ClNO₃
M_r = 241.67
Triclinic, $[P \overline 1]$
a = 4.8097 (8) Å
b = 7.3909 (9) Å
c = 16.147 (2) Å
α = 85.15 (1)°
β = 85.86 (1)°
γ = 89.57 (1)°
V = 570.45 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 K
0.40 × 0.18 × 0.09 mm

Data collection

Oxford Xcalibur diffractometer with Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.881, T_max = 0.971
3625 measured reflections
2284 independent reflections
1883 reflections with I > 2σ(I)
R_int = 0.011

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.120
S = 1.11
2284 reflections
152 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.84 (2)	2.16 (2)	2.973 (3)	163 (3)
O3—H3O⋯O2ⁱⁱ	0.83 (2)	1.85 (2)	2.674 (3)	172 (4)
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+2, -z+2.

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 ); 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/S1600536812005648/cv5244sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812005648/cv5244Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812005648/cv5244Isup3.cml

checkCIF report

Comment top

Recently, we reported the crystal structure of N-(2-chloro-5-methylphenyl)succinamic acid (Gowda et al., 2012). We report here the crystal structure of very closely related N-(2-chloro-4-methylphenyl)succinamic acid, (I).

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in related compounds (Gowda et al., 2012, and references therein). The conformations of the amide oxygen and the carboxyl oxygen of the acid segment are anti to each other and both are anti to the H atoms on the adjacent –CH₂ group.. The C═O and O—H bonds of the acid group are in syn position to each other. The dihedral angle between the benzene ring and the amide group is 48.39 (12)°.

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

Related literature top

For the crystal structures of related compounds studied in our group, see: Gowda et al. (2012) and references therein.

Experimental top

The solution of succinic anhydride (0.01 mole) in toluene (25 ml) was treated dropwise with the solution of 2-chloro-4-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 2-chloro-4-methylaniline. The resultant 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 and NMR spectra. Rod like colourless single crystals used in X-ray diffraction studies were grown in ethanol solution by slow evaporation 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. The molecular structure of (I) showing the atom labelling scheme and 50% probability displacement ellipsoids.
	Fig. 2. A portion of the crystal packing with hydrogen bonds shown as dashed lines.

N-(2-Chloro-4-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 = 4.8097 (8) Å	Cell parameters from 2016 reflections
b = 7.3909 (9) Å	θ = 2.5–27.9°
c = 16.147 (2) Å	µ = 0.33 mm⁻¹
α = 85.15 (1)°	T = 293 K
β = 85.86 (1)°	Rod, colourless
γ = 89.57 (1)°	0.40 × 0.18 × 0.09 mm
V = 570.45 (14) Å³

Data collection top

Oxford Xcalibur diffractometer with Sapphire CCD detector	2284 independent reflections
Radiation source: fine-focus sealed tube	1883 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.011
Rotation method data acquisition using ω and ϕ scans	θ_max = 26.4°, θ_min = 2.5°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −5→5
T_min = 0.881, T_max = 0.971	k = −9→9
3625 measured reflections	l = −17→20

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0348P)² + 0.5262P] where P = (F_o² + 2F_c²)/3
2284 reflections	(Δ/σ)_max = 0.001
152 parameters	Δρ_max = 0.28 e Å⁻³
2 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₁H₁₂ClNO₃	γ = 89.57 (1)°
M_r = 241.67	V = 570.45 (14) Å³
Triclinic, P1	Z = 2
a = 4.8097 (8) Å	Mo Kα radiation
b = 7.3909 (9) Å	µ = 0.33 mm⁻¹
c = 16.147 (2) Å	T = 293 K
α = 85.15 (1)°	0.40 × 0.18 × 0.09 mm
β = 85.86 (1)°

Data collection top

Oxford Xcalibur diffractometer with Sapphire CCD detector	2284 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1883 reflections with I > 2σ(I)
T_min = 0.881, T_max = 0.971	R_int = 0.011
3625 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	2 restraints
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.28 e Å⁻³
2284 reflections	Δρ_min = −0.25 e Å⁻³
152 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

	x	y	z	U_iso*/U_eq
C1	0.7464 (5)	0.1423 (3)	0.72556 (16)	0.0372 (5)
C2	0.6617 (5)	0.1119 (3)	0.64792 (16)	0.0397 (6)
C3	0.7600 (6)	−0.0346 (3)	0.60606 (18)	0.0479 (6)
H3	0.6972	−0.0528	0.5543	0.057*
C4	0.9510 (6)	−0.1542 (4)	0.64083 (19)	0.0516 (7)
C5	1.0408 (6)	−0.1206 (4)	0.7175 (2)	0.0544 (7)
H5	1.1728	−0.1976	0.7412	0.065*
C6	0.9412 (5)	0.0232 (4)	0.76017 (18)	0.0465 (6)
H6	1.0040	0.0408	0.8120	0.056*
C7	0.7910 (5)	0.4059 (3)	0.80500 (15)	0.0386 (6)
C8	0.6293 (5)	0.5544 (4)	0.84608 (17)	0.0431 (6)
H8A	0.4480	0.5081	0.8679	0.052*
H8B	0.5999	0.6544	0.8047	0.052*
C9	0.7800 (5)	0.6234 (4)	0.91616 (17)	0.0449 (6)
H9A	0.7896	0.5262	0.9602	0.054*
H9B	0.9696	0.6544	0.8955	0.054*
C10	0.6475 (5)	0.7848 (4)	0.95222 (16)	0.0441 (6)
C11	1.0540 (8)	−0.3163 (4)	0.5961 (2)	0.0790 (11)
H11A	1.0422	−0.2903	0.5371	0.095*
H11B	0.9409	−0.4201	0.6151	0.095*
H11C	1.2442	−0.3414	0.6075	0.095*
N1	0.6355 (4)	0.2886 (3)	0.76914 (14)	0.0404 (5)
H1N	0.463 (4)	0.306 (4)	0.7706 (17)	0.049*
O1	1.0450 (3)	0.3984 (3)	0.80286 (14)	0.0594 (6)
O2	0.4442 (4)	0.8624 (3)	0.92593 (15)	0.0741 (7)
O3	0.7748 (6)	0.8378 (4)	1.01368 (17)	0.0888 (9)
H3O	0.696 (8)	0.924 (4)	1.035 (2)	0.107*
Cl1	0.42759 (15)	0.26087 (10)	0.60111 (5)	0.0573 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0262 (11)	0.0349 (12)	0.0506 (14)	0.0017 (9)	0.0016 (10)	−0.0079 (10)
C2	0.0289 (12)	0.0395 (13)	0.0520 (15)	0.0062 (10)	−0.0033 (10)	−0.0110 (11)
C3	0.0484 (15)	0.0411 (14)	0.0554 (16)	0.0046 (12)	0.0006 (12)	−0.0164 (12)
C4	0.0498 (16)	0.0356 (13)	0.0685 (19)	0.0076 (11)	0.0104 (14)	−0.0118 (12)
C5	0.0447 (15)	0.0441 (15)	0.073 (2)	0.0164 (12)	−0.0009 (14)	0.0012 (14)
C6	0.0374 (14)	0.0482 (15)	0.0540 (16)	0.0057 (11)	−0.0033 (11)	−0.0056 (12)
C7	0.0255 (12)	0.0447 (13)	0.0474 (14)	0.0032 (10)	−0.0044 (10)	−0.0137 (11)
C8	0.0266 (12)	0.0492 (14)	0.0570 (16)	0.0044 (10)	−0.0076 (11)	−0.0217 (12)
C9	0.0332 (13)	0.0532 (15)	0.0516 (15)	0.0059 (11)	−0.0090 (11)	−0.0192 (12)
C10	0.0353 (13)	0.0533 (15)	0.0463 (14)	−0.0003 (11)	−0.0036 (11)	−0.0192 (12)
C11	0.094 (3)	0.0468 (17)	0.095 (3)	0.0276 (17)	0.015 (2)	−0.0168 (17)
N1	0.0214 (9)	0.0463 (12)	0.0568 (13)	0.0056 (8)	−0.0042 (9)	−0.0223 (10)
O1	0.0219 (9)	0.0689 (13)	0.0934 (16)	0.0049 (8)	−0.0080 (9)	−0.0395 (12)
O2	0.0578 (13)	0.0868 (16)	0.0892 (16)	0.0282 (12)	−0.0307 (12)	−0.0551 (13)
O3	0.0870 (18)	0.0996 (19)	0.0954 (19)	0.0402 (14)	−0.0513 (15)	−0.0655 (16)
Cl1	0.0547 (4)	0.0582 (4)	0.0627 (5)	0.0234 (3)	−0.0177 (3)	−0.0183 (3)

Geometric parameters (Å, º) top

C1—C2	1.382 (3)	C7—C8	1.512 (3)
C1—C6	1.395 (3)	C8—C9	1.512 (3)
C1—N1	1.420 (3)	C8—H8A	0.9700
C2—C3	1.387 (3)	C8—H8B	0.9700
C2—Cl1	1.736 (2)	C9—C10	1.490 (3)
C3—C4	1.385 (4)	C9—H9A	0.9700
C3—H3	0.9300	C9—H9B	0.9700
C4—C5	1.383 (4)	C10—O2	1.215 (3)
C4—C11	1.513 (4)	C10—O3	1.292 (3)
C5—C6	1.379 (4)	C11—H11A	0.9600
C5—H5	0.9300	C11—H11B	0.9600
C6—H6	0.9300	C11—H11C	0.9600
C7—O1	1.221 (3)	N1—H1N	0.839 (17)
C7—N1	1.343 (3)	O3—H3O	0.827 (19)

C2—C1—C6	117.9 (2)	C9—C8—H8A	109.2
C2—C1—N1	121.0 (2)	C7—C8—H8B	109.2
C6—C1—N1	121.1 (2)	C9—C8—H8B	109.2
C1—C2—C3	121.6 (2)	H8A—C8—H8B	107.9
C1—C2—Cl1	119.42 (18)	C10—C9—C8	114.3 (2)
C3—C2—Cl1	118.9 (2)	C10—C9—H9A	108.7
C4—C3—C2	120.5 (3)	C8—C9—H9A	108.7
C4—C3—H3	119.8	C10—C9—H9B	108.7
C2—C3—H3	119.8	C8—C9—H9B	108.7
C5—C4—C3	117.7 (2)	H9A—C9—H9B	107.6
C5—C4—C11	121.7 (3)	O2—C10—O3	122.8 (2)
C3—C4—C11	120.6 (3)	O2—C10—C9	124.0 (2)
C6—C5—C4	122.2 (3)	O3—C10—C9	113.2 (2)
C6—C5—H5	118.9	C4—C11—H11A	109.5
C4—C5—H5	118.9	C4—C11—H11B	109.5
C5—C6—C1	120.0 (3)	H11A—C11—H11B	109.5
C5—C6—H6	120.0	C4—C11—H11C	109.5
C1—C6—H6	120.0	H11A—C11—H11C	109.5
O1—C7—N1	123.2 (2)	H11B—C11—H11C	109.5
O1—C7—C8	121.7 (2)	C7—N1—C1	124.10 (19)
N1—C7—C8	115.08 (19)	C7—N1—H1N	117.9 (19)
C7—C8—C9	111.9 (2)	C1—N1—H1N	117.9 (19)
C7—C8—H8A	109.2	C10—O3—H3O	113 (3)

C6—C1—C2—C3	1.7 (4)	C2—C1—C6—C5	−0.8 (4)
N1—C1—C2—C3	−177.4 (2)	N1—C1—C6—C5	178.4 (2)
C6—C1—C2—Cl1	−178.02 (19)	O1—C7—C8—C9	−28.9 (4)
N1—C1—C2—Cl1	2.8 (3)	N1—C7—C8—C9	153.3 (2)
C1—C2—C3—C4	−1.0 (4)	C7—C8—C9—C10	173.0 (2)
Cl1—C2—C3—C4	178.8 (2)	C8—C9—C10—O2	−3.6 (4)
C2—C3—C4—C5	−0.7 (4)	C8—C9—C10—O3	177.9 (3)
C2—C3—C4—C11	178.7 (3)	O1—C7—N1—C1	0.6 (4)
C3—C4—C5—C6	1.7 (4)	C8—C7—N1—C1	178.4 (2)
C11—C4—C5—C6	−177.8 (3)	C2—C1—N1—C7	−132.0 (3)
C4—C5—C6—C1	−1.0 (4)	C6—C1—N1—C7	48.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.84 (2)	2.16 (2)	2.973 (3)	163 (3)
O3—H3O···O2ⁱⁱ	0.83 (2)	1.85 (2)	2.674 (3)	172 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂ClNO₃
M_r	241.67
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	4.8097 (8), 7.3909 (9), 16.147 (2)
α, β, γ (°)	85.15 (1), 85.86 (1), 89.57 (1)
V (Å³)	570.45 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.40 × 0.18 × 0.09

Data collection
Diffractometer	Oxford Xcalibur diffractometer with Sapphire CCD detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.881, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	3625, 2284, 1883
R_int	0.011
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.120, 1.11
No. of reflections	2284
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)	0.28, −0.25

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···O1ⁱ	0.839 (17)	2.159 (18)	2.973 (3)	163 (3)
O3—H3O···O2ⁱⁱ	0.827 (19)	1.85 (2)	2.674 (3)	172 (4)

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

Acknowledgements

BTG thanks the University Grants Commission, Government of India, New Delhi, for a special grant under a UGC-BSR one-time Grant to Faculty.

References

Gowda, B. T., Foro, S. & Chaithanya, U. (2012). Acta Cryst. E68, o221. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar