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N-(2-Chloro-5-methyl­phen­yl)succinamic acid

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 1 December 2011; accepted 19 December 2011; online 23 December 2011)

In the title compound, C11H12ClNO3, the conformation of the N—H bond in the amide segment is syn with respect to the ortho-Cl atom. The amide and carboxyl C=O groups are syn to each other. Furthermore, the C=O and O—H bonds of the carboxyl group are in syn positions with respect to each other. The dihedral angle between the benzene ring and the amide group is 47.8 (2)°. In the crystal, mol­ecules are connected by pairs of O—H⋯O hydrogen bonds, forming inversion dimers. The dimers are further linked by N—H⋯O hydrogen bonds into double chains along the b-axis direction.

Related literature

For our previous studies on the effects of substituents on the structures and other aspects of N-(ar­yl)-amides, see: Gowda et al. (2001[Gowda, B. T., Paulus, H. & Fuess, H. (2001). Z. Naturforsch. Teil A, 56, 386-394.]); Saraswathi et al. (2011[Saraswathi, B. S., Foro, S. & Gowda, B. T. (2011). Acta Cryst. E67, o2093.]), on N-(ar­yl)-methane­sulfonamides, see: Jayalakshmi & Gowda (2004[Jayalakshmi, K. L. & Gowda, B. T. (2004). Z. Naturforsch. Teil A, 59, 491-500.]), on N-(ar­yl)-aryl­sulfonamides, see: Gowda et al. (2005[Gowda, B. T., Shetty, M. & Jayalakshmi, K. L. (2005). Z. Naturforsch. Teil A, 60, 106-112.]) and on N-chloro­aryl­amides, see: Gowda et al. (1996[Gowda, B. T., Dou, S. Q. & Weiss, A. (1996). Z. Naturforsch. Teil A, 51, 627-636.]). For modes of hydrogen bonding in the structures of carb­oxy­lic acids, see: Leiserowitz (1976[Leiserowitz, L. (1976). Acta Cryst. B32, 775-802.]). For the centrosymmetrical dimeric hydrogen-bonding association of carb­oxy­lic groups, see: Jagannathan et al. (1994[Jagannathan, N. R., Rajan, S. S. & Subramanian, E. (1994). J. Chem. Crystallogr. 24, 75-78.]).

[Scheme 1]

Experimental

Crystal data
  • C11H12ClNO3

  • Mr = 241.67

  • Monoclinic, C 2/c

  • a = 23.780 (5) Å

  • b = 4.7784 (7) Å

  • c = 23.892 (5) Å

  • β = 121.20 (1)°

  • V = 2322.2 (8) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.32 mm−1

  • T = 293 K

  • 0.42 × 0.10 × 0.08 mm

Data collection
  • Oxford Diffraction Xcalibur with Sapphire CCD detector diffractometer

  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]) Tmin = 0.877, Tmax = 0.975

  • 4399 measured reflections

  • 2322 independent reflections

  • 1680 reflections with I > 2σ(I)

  • Rint = 0.020

Refinement
  • R[F2 > 2σ(F2)] = 0.062

  • wR(F2) = 0.128

  • S = 1.19

  • 2322 reflections

  • 152 parameters

  • 2 restraints

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

  • Δρmax = 0.28 e Å−3

  • Δρmin = −0.25 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O3—H3O⋯O2i 0.83 (2) 1.83 (2) 2.652 (4) 172 (5)
N1—H1N⋯O1ii 0.86 (2) 2.08 (2) 2.910 (4) 163 (3)
Symmetry codes: (i) [-x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]; (ii) x, y+1, z.

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

The amide and sulfonamide moieties are important constituents of many biologically important compounds. As a part of our studies of the substituent effects on the structures and other aspects of N-(aryl)-amides (Gowda et al., 2001; Saraswathi et al., 2011), N-(aryl)-methanesulfonamides (Jayalakshmi & Gowda, 2004), N-(aryl)-arylsulfonamides (Gowda et al., 2005) and N-chloro-arylsulfonamides (Gowda et al., 1996), in the present work, the crystal structure of N-(2-chloro-5-methylphenyl)succinamic acid (I) has been determined (Fig. 1). The conformation of the N—H bond in the amide segment is syn to the ortho–chloro group and anti to the meta–methyl group in the benzene ring, similar to the syn conformation observed between the amide hydrogen and the ortho-Cl and anti conformation between the amide hydrogen and the meta-Cl in the benzene ring of N-(2,5-dichlorophenyl)- succinamic acid (II) (Saraswathi et al., 2011).

Further, the conformations of the amide oxygen and the carboxyl oxygen of the acid segment are syn to each other.

The CO and O—H bonds of the acid group are in syn position to each other, similar to that observed in (II).

The dihedral angle between the phenyl ring and the amide group is 47.8 (2)°.

The intermolecular O—H···O and N—H···O hydrogen bonds pack the molecules into infinite chains along the b-axis direction (Table 1, Fig.2).

The modes of interlinking carboxylic acids by hydrogen bonds is described elsewhere (Leiserowitz, 1976). The packing of molecules involving dimeric hydrogen-bonded association of each carboxyl group with a centrosymmetrically related neighbor has also been observed (Jagannathan et al., 1994).

Related literature top

For our previous studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Gowda et al. (2001); Saraswathi et al. (2011), on N-(aryl)-methanesulfonamides, see: Jayalakshmi & Gowda (2004), on N-(aryl)-arylsulfonamides, see: Gowda et al. (2005) and on N-chloroarylamides, see: Gowda et al. (1996). For modes of hydrogen bonding in the structures of carboxylic acids, see: Leiserowitz (1976). For the centrosymmetrical dimeric hydrogen-bonding association of carboxylic groups, see: Jagannathan et al. (1994).

Experimental top

The solution of succinic anhydride (0.01 mole) in toluene (25 ml) was treated with the solution of 2-chloro,5-methylaniline (0.01 mole) also in toluene (20 ml), added dropwise with permanent 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 diluted hydrochloric acid to remove the unreacted 2-chloro-5-methyl-aniline. The resultant title compound was filtered under suction and washed thoroughly with water to remove the unreacted succinic anhydride and succinic acid. The product 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 colorless single crystals used in X-ray diffraction studies were grown from ethanolic solution by slow evaporation at room temperature.

Refinement top

The H atoms of the NH and OH groups were located in a difference map and later restrained to the distances N—H = 0.86 (2) Å and O—H = 0.82 (2) Å, respectively. The other H atoms were positioned with idealized geometry and refined using a riding model with the aromatic C—H = 0.93 Å and 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 the title compound, showing the atom labelling scheme and with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Molecular packing of the title compound with hydrogen bonds shown as dashed lines.
N-(2-Chloro-5-methylphenyl)succinamic acid top
Crystal data top
C11H12ClNO3F(000) = 1008
Mr = 241.67Dx = 1.382 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1604 reflections
a = 23.780 (5) Åθ = 2.6–27.9°
b = 4.7784 (7) ŵ = 0.32 mm1
c = 23.892 (5) ÅT = 293 K
β = 121.20 (1)°Rod, colourless
V = 2322.2 (8) Å30.42 × 0.10 × 0.08 mm
Z = 8
Data collection top
Oxford Diffraction Xcalibur with Sapphire CCD detector
diffractometer
2322 independent reflections
Radiation source: fine-focus sealed tube1680 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
ω and ϕ scansθmax = 26.4°, θmin = 3.4°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
h = 2928
Tmin = 0.877, Tmax = 0.975k = 45
4399 measured reflectionsl = 2029
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)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H atoms treated by a mixture of independent and constrained refinement
S = 1.19 w = 1/[σ2(Fo2) + (0.0268P)2 + 6.3165P]
where P = (Fo2 + 2Fc2)/3
2322 reflections(Δ/σ)max = 0.044
152 parametersΔρmax = 0.28 e Å3
2 restraintsΔρmin = 0.25 e Å3
Crystal data top
C11H12ClNO3V = 2322.2 (8) Å3
Mr = 241.67Z = 8
Monoclinic, C2/cMo Kα radiation
a = 23.780 (5) ŵ = 0.32 mm1
b = 4.7784 (7) ÅT = 293 K
c = 23.892 (5) Å0.42 × 0.10 × 0.08 mm
β = 121.20 (1)°
Data collection top
Oxford Diffraction Xcalibur with Sapphire CCD detector
diffractometer
2322 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
1680 reflections with I > 2σ(I)
Tmin = 0.877, Tmax = 0.975Rint = 0.020
4399 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0622 restraints
wR(F2) = 0.128H atoms treated by a mixture of independent and constrained refinement
S = 1.19Δρmax = 0.28 e Å3
2322 reflectionsΔρmin = 0.25 e Å3
152 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
Cl10.14042 (4)1.47549 (19)0.23661 (4)0.0481 (3)
O10.02815 (14)0.7770 (5)0.14193 (17)0.0703 (9)
O20.18862 (14)0.9786 (7)0.03462 (14)0.0749 (9)
O30.21661 (15)0.6674 (7)0.08465 (14)0.0783 (10)
H3O0.2438 (19)0.623 (10)0.0462 (12)0.094*
N10.01311 (13)1.2030 (5)0.14261 (14)0.0363 (6)
H1N0.0095 (16)1.378 (4)0.1481 (16)0.044*
C10.06702 (14)1.1156 (6)0.13712 (15)0.0330 (7)
C20.12917 (15)1.2274 (7)0.17838 (15)0.0362 (7)
C30.18210 (16)1.1446 (8)0.17339 (18)0.0473 (9)
H30.22351.22050.20110.057*
C40.17314 (17)0.9488 (8)0.12704 (18)0.0487 (9)
H40.20900.89160.12430.058*
C50.11180 (17)0.8360 (7)0.08458 (17)0.0423 (8)
C60.05926 (15)0.9222 (7)0.09027 (16)0.0377 (8)
H60.01770.84840.06200.045*
C70.03027 (15)1.0299 (7)0.14512 (16)0.0377 (7)
C80.08153 (15)1.1768 (7)0.15378 (18)0.0418 (8)
H8A0.10361.31590.11960.050*
H8B0.05991.27370.19550.050*
C90.13225 (16)0.9767 (8)0.15140 (17)0.0452 (8)
H9A0.10960.81640.17880.054*
H9B0.15531.06970.16980.054*
C100.18136 (16)0.8754 (8)0.08466 (19)0.0450 (9)
C110.1020 (2)0.6300 (8)0.03259 (19)0.0605 (11)
H11A0.10740.44310.04940.073*
H11B0.13390.66460.02010.073*
H11C0.05860.65090.00490.073*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0457 (5)0.0473 (5)0.0465 (5)0.0107 (4)0.0206 (4)0.0069 (4)
O10.0751 (19)0.0230 (14)0.147 (3)0.0019 (13)0.081 (2)0.0023 (16)
O20.0717 (18)0.081 (2)0.0607 (17)0.0415 (17)0.0259 (15)0.0011 (17)
O30.072 (2)0.084 (2)0.0667 (19)0.0466 (18)0.0269 (16)0.0004 (18)
N10.0339 (13)0.0231 (13)0.0559 (17)0.0001 (12)0.0261 (13)0.0033 (13)
C10.0331 (16)0.0245 (16)0.0432 (18)0.0027 (13)0.0210 (14)0.0072 (14)
C20.0366 (16)0.0327 (18)0.0381 (17)0.0027 (14)0.0185 (14)0.0039 (15)
C30.0334 (17)0.053 (2)0.055 (2)0.0001 (16)0.0220 (16)0.0081 (19)
C40.0430 (19)0.052 (2)0.061 (2)0.0101 (18)0.0338 (18)0.012 (2)
C50.056 (2)0.0349 (19)0.0450 (19)0.0061 (16)0.0326 (17)0.0065 (16)
C60.0382 (17)0.0322 (18)0.0430 (18)0.0004 (14)0.0212 (14)0.0030 (15)
C70.0319 (16)0.0283 (18)0.0519 (19)0.0012 (14)0.0210 (14)0.0002 (16)
C80.0342 (16)0.0336 (19)0.059 (2)0.0058 (15)0.0254 (16)0.0103 (17)
C90.0421 (18)0.045 (2)0.060 (2)0.0081 (17)0.0346 (17)0.0092 (18)
C100.0332 (17)0.040 (2)0.065 (2)0.0062 (15)0.0281 (17)0.0000 (18)
C110.080 (3)0.052 (2)0.064 (3)0.011 (2)0.047 (2)0.004 (2)
Geometric parameters (Å, º) top
Cl1—C21.740 (3)C4—H40.9300
O1—C71.214 (4)C5—C61.387 (4)
O2—C101.220 (4)C5—C111.506 (5)
O3—C101.300 (4)C6—H60.9300
O3—H3O0.832 (19)C7—C81.511 (4)
N1—C71.347 (4)C8—C91.517 (4)
N1—C11.418 (4)C8—H8A0.9700
N1—H1N0.858 (18)C8—H8B0.9700
C1—C61.388 (4)C9—C101.487 (5)
C1—C21.390 (4)C9—H9A0.9700
C2—C31.382 (4)C9—H9B0.9700
C3—C41.379 (5)C11—H11A0.9600
C3—H30.9300C11—H11B0.9600
C4—C51.384 (5)C11—H11C0.9600
C10—O3—H3O109 (4)O1—C7—C8122.3 (3)
C7—N1—C1125.0 (3)N1—C7—C8114.3 (3)
C7—N1—H1N117 (2)C7—C8—C9112.6 (3)
C1—N1—H1N118 (2)C7—C8—H8A109.1
C6—C1—C2118.4 (3)C9—C8—H8A109.1
C6—C1—N1121.5 (3)C7—C8—H8B109.1
C2—C1—N1120.1 (3)C9—C8—H8B109.1
C3—C2—C1120.7 (3)H8A—C8—H8B107.8
C3—C2—Cl1119.6 (3)C10—C9—C8114.4 (3)
C1—C2—Cl1119.7 (2)C10—C9—H9A108.7
C4—C3—C2119.6 (3)C8—C9—H9A108.7
C4—C3—H3120.2C10—C9—H9B108.7
C2—C3—H3120.2C8—C9—H9B108.7
C3—C4—C5121.2 (3)H9A—C9—H9B107.6
C3—C4—H4119.4O2—C10—O3123.0 (4)
C5—C4—H4119.4O2—C10—C9123.6 (3)
C4—C5—C6118.3 (3)O3—C10—C9113.4 (3)
C4—C5—C11120.9 (3)C5—C11—H11A109.5
C6—C5—C11120.9 (3)C5—C11—H11B109.5
C5—C6—C1121.8 (3)H11A—C11—H11B109.5
C5—C6—H6119.1C5—C11—H11C109.5
C1—C6—H6119.1H11A—C11—H11C109.5
O1—C7—N1123.4 (3)H11B—C11—H11C109.5
C7—N1—C1—C649.1 (5)C4—C5—C6—C10.2 (5)
C7—N1—C1—C2132.0 (3)C11—C5—C6—C1178.8 (3)
C6—C1—C2—C30.9 (5)C2—C1—C6—C51.0 (5)
N1—C1—C2—C3179.8 (3)N1—C1—C6—C5179.9 (3)
C6—C1—C2—Cl1178.8 (2)C1—N1—C7—O11.1 (6)
N1—C1—C2—Cl10.2 (4)C1—N1—C7—C8177.6 (3)
C1—C2—C3—C40.1 (5)O1—C7—C8—C95.4 (5)
Cl1—C2—C3—C4179.7 (3)N1—C7—C8—C9175.8 (3)
C2—C3—C4—C51.0 (5)C7—C8—C9—C1075.1 (4)
C3—C4—C5—C60.8 (5)C8—C9—C10—O212.7 (5)
C3—C4—C5—C11177.8 (3)C8—C9—C10—O3168.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3O···O2i0.83 (2)1.83 (2)2.652 (4)172 (5)
N1—H1N···O1ii0.86 (2)2.08 (2)2.910 (4)163 (3)
Symmetry codes: (i) x1/2, y+3/2, z; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC11H12ClNO3
Mr241.67
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)23.780 (5), 4.7784 (7), 23.892 (5)
β (°) 121.20 (1)
V3)2322.2 (8)
Z8
Radiation typeMo Kα
µ (mm1)0.32
Crystal size (mm)0.42 × 0.10 × 0.08
Data collection
DiffractometerOxford Diffraction Xcalibur with Sapphire CCD detector
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2009)
Tmin, Tmax0.877, 0.975
No. of measured, independent and
observed [I > 2σ(I)] reflections
4399, 2322, 1680
Rint0.020
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.062, 0.128, 1.19
No. of reflections2322
No. of parameters152
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O3—H3O···O2i0.832 (19)1.83 (2)2.652 (4)172 (5)
N1—H1N···O1ii0.858 (18)2.08 (2)2.910 (4)163 (3)
Symmetry codes: (i) x1/2, y+3/2, z; (ii) x, y+1, z.
 

Acknowledgements

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

References

First citationGowda, B. T., Dou, S. Q. & Weiss, A. (1996). Z. Naturforsch. Teil A, 51, 627–636.  CAS
First citationGowda, B. T., Paulus, H. & Fuess, H. (2001). Z. Naturforsch. Teil A, 56, 386–394.  CAS
First citationGowda, B. T., Shetty, M. & Jayalakshmi, K. L. (2005). Z. Naturforsch. Teil A, 60, 106–112.  CAS
First citationJagannathan, N. R., Rajan, S. S. & Subramanian, E. (1994). J. Chem. Crystallogr. 24, 75–78.  CSD CrossRef CAS Web of Science
First citationJayalakshmi, K. L. & Gowda, B. T. (2004). Z. Naturforsch. Teil A, 59, 491–500.  CAS
First citationLeiserowitz, L. (1976). Acta Cryst. B32, 775–802.  CrossRef CAS IUCr Journals Web of Science
First citationOxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.
First citationSaraswathi, B. S., Foro, S. & Gowda, B. T. (2011). Acta Cryst. E67, o2093.  Web of Science CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals

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