N-(3-Chloro-4-methyl­phen­yl)maleamic acid

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

doi:10.1107/S1600536812007842

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o889

doi:10.1107/S1600536812007842

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N-(3-Chloro-4-methylphenyl)maleamic 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 21 February 2012; accepted 21 February 2012; online 29 February 2012)

In the title compound, C₁₁H₁₀ClNO₃, the dihedral angle between the benzene ring and the amide group is 6.6 (10)° and an intramolecular O—H⋯O hydrogen bond occurs. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, generating C(7) zigzag chains.

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 , 2003 , 2007 ); Chaithanya et al. (2012 ). For N-chloroarylamides, see: Jyothi & Gowda (2004 ). For N-bromoarylsulfonamides, see: Usha & Gowda (2006 ).

Experimental

Crystal data

C₁₁H₁₀ClNO₃
M_r = 239.65
Monoclinic, P 2₁ /c
a = 9.005 (1) Å
b = 13.491 (2) Å
c = 8.757 (1) Å
β = 97.91 (1)°
V = 1053.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 293 K
0.48 × 0.40 × 0.34 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.849, T_max = 0.890
4069 measured reflections
2147 independent reflections
1798 reflections with I > 2σ(I)
R_int = 0.011

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.105
S = 1.04
2147 reflections
152 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 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
N1—H1N⋯O2ⁱ	0.87 (2)	2.11 (2)	2.9546 (19)	164 (2)
O3—H3O⋯O1	0.87 (2)	1.62 (2)	2.4885 (17)	173 (2)
Symmetry code: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); 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/S1600536812007842/kp2391sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007842/kp2391Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812007842/kp2391Isup3.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, 2003, 2007; Chaithanya et al., 2012), N-chloroarylsulfonamides (Jyothi & Gowda, 2004) and N-bromoarylsulfonamides (Usha & Gowda, 2006), in the present work, the crystal structure of N-(3-chloro-4-methylphenyl)maleamic acid has been determined (Fig. 1). The conformations of the N—H and the C=O bonds in the amide segment are anti to each other. The conformation of the N—H bond is also anti to the meta–chloro atom. Further, the conformation of the amide C═O is anti to the H atom on the adjacent –CH group, while the carboxyl C═O of the acid segment is syn to the adjacent –CH group. Furthermore, the C═O and O—H bond of the acid group are in relatively rare anti position to each other, due to the donation of hydrogen bond to the amide by the carboxyl group, in contrast to the more general syn conformation observed in N-(3-chloro-4-methylphenyl)-succinamic acid (I) (Chaithanya et al., 2012).

The dihedral angle between the phenyl ring and the amide group in the title compound is 6.55 (99)°, compared to the values of 40.58 (22)° and 44.93 (27)° in the two derivatives of (I).

In the structure, the pairs of O—H···O and N—H···O intermolecular hydrogen bonds pack the molecules into chains (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, 2003, 2007); Chaithanya et al. (2012). For N-chloroarylamides, see: Jyothi & Gowda (2004). For N-bromoarylsulfonamides, see: Usha & Gowda (2006).

Experimental top

Maleic anhydride (0.025 mol) in toluene (25 mL) was treated dropwise with 3-chloro-4-methylaniline (0.025 mol) also in toluene (20 mL) with constant stirring. The resulting mixture was stirred for about 30 min and set aside for an additional 30 min at room temperature for the completion of reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted 3-chloro-4-methylaniline. The resultant solid N-(3-chloro-4-methylphenyl)-maleamic acid was filtered under suction and washed thoroughly with water to remove the unreacted maleic anhydride and maleic acid. It was recrystallised to constant melting point from ethanol. The purity of the compound was checked and characterized by its infrared spectra.

Prism like pale yellow single crystals of the title compound used in X-ray diffraction studies were grown in an ethanol solution by slow evaporation of the solvent (0.5 g in about 30 mL of ethanol) 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 with displacement ellipsoids drawn at the 50% probability level. Intramolecular hydrogen bond in shown.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

N-(3-Chloro-4-methylphenyl)maleamic acid top

Crystal data top

C₁₁H₁₀ClNO₃	F(000) = 496
M_r = 239.65	D_x = 1.511 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1538 reflections
a = 9.005 (1) Å	θ = 2.8–27.9°
b = 13.491 (2) Å	µ = 0.35 mm⁻¹
c = 8.757 (1) Å	T = 293 K
β = 97.91 (1)°	Prism, yellow
V = 1053.7 (2) Å³	0.48 × 0.40 × 0.34 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2147 independent reflections
Radiation source: fine-focus sealed tube	1798 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.011
Rotation method data acquisition using ω and phi scans	θ_max = 26.4°, θ_min = 2.8°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −11→8
T_min = 0.849, T_max = 0.890	k = −16→14
4069 measured reflections	l = −7→10

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0582P)² + 0.2934P] where P = (F_o² + 2F_c²)/3
2147 reflections	(Δ/σ)_max < 0.001
152 parameters	Δρ_max = 0.33 e Å⁻³
2 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₁H₁₀ClNO₃	V = 1053.7 (2) Å³
M_r = 239.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.005 (1) Å	µ = 0.35 mm⁻¹
b = 13.491 (2) Å	T = 293 K
c = 8.757 (1) Å	0.48 × 0.40 × 0.34 mm
β = 97.91 (1)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2147 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1798 reflections with I > 2σ(I)
T_min = 0.849, T_max = 0.890	R_int = 0.011
4069 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	2 restraints
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.33 e Å⁻³
2147 reflections	Δρ_min = −0.27 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	0.66874 (17)	0.04762 (11)	0.39541 (18)	0.0309 (3)
C2	0.59803 (18)	0.12392 (11)	0.30833 (19)	0.0359 (4)
H2	0.6327	0.1887	0.3217	0.043*
C3	0.47494 (18)	0.10217 (11)	0.20120 (19)	0.0355 (4)
C4	0.41627 (17)	0.00764 (12)	0.17621 (18)	0.0332 (4)
C5	0.49161 (19)	−0.06669 (12)	0.2641 (2)	0.0398 (4)
H5	0.4571	−0.1315	0.2503	0.048*
C6	0.61566 (18)	−0.04879 (12)	0.3714 (2)	0.0381 (4)
H6	0.6637	−0.1009	0.4275	0.046*
C7	0.85614 (17)	0.14437 (12)	0.56761 (18)	0.0324 (3)
C8	0.98127 (18)	0.13165 (12)	0.69471 (19)	0.0351 (4)
H8	1.0081	0.0665	0.7197	0.042*
C9	1.06040 (18)	0.20092 (13)	0.77789 (19)	0.0378 (4)
H9	1.1357	0.1758	0.8509	0.045*
C10	1.05105 (18)	0.31142 (12)	0.77605 (19)	0.0366 (4)
C11	0.27987 (18)	−0.01421 (14)	0.0625 (2)	0.0434 (4)
H11A	0.2960	0.0081	−0.0380	0.052*
H11B	0.1949	0.0196	0.0930	0.052*
H11C	0.2614	−0.0843	0.0598	0.052*
N1	0.79351 (15)	0.06004 (10)	0.51139 (16)	0.0338 (3)
H1N	0.827 (2)	0.0067 (12)	0.560 (2)	0.041*
O1	0.81351 (14)	0.22693 (9)	0.51661 (15)	0.0483 (3)
O2	1.13005 (15)	0.35781 (10)	0.87433 (15)	0.0507 (4)
O3	0.95988 (16)	0.35732 (9)	0.67213 (17)	0.0537 (4)
H3O	0.911 (2)	0.3136 (16)	0.611 (2)	0.064*
Cl1	0.38990 (6)	0.19890 (3)	0.09113 (6)	0.0620 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0306 (7)	0.0240 (7)	0.0350 (8)	−0.0015 (6)	−0.0065 (6)	−0.0020 (6)
C2	0.0396 (8)	0.0203 (7)	0.0427 (9)	−0.0025 (6)	−0.0119 (7)	−0.0008 (6)
C3	0.0381 (8)	0.0234 (7)	0.0407 (9)	0.0018 (6)	−0.0099 (7)	−0.0006 (7)
C4	0.0324 (8)	0.0264 (8)	0.0375 (8)	−0.0021 (6)	−0.0064 (6)	−0.0040 (6)
C5	0.0425 (9)	0.0218 (8)	0.0503 (10)	−0.0058 (6)	−0.0112 (7)	−0.0008 (7)
C6	0.0421 (9)	0.0219 (8)	0.0453 (9)	−0.0008 (6)	−0.0118 (7)	0.0024 (7)
C7	0.0323 (7)	0.0259 (7)	0.0359 (8)	−0.0011 (6)	−0.0064 (6)	−0.0018 (6)
C8	0.0372 (8)	0.0264 (8)	0.0378 (9)	0.0012 (6)	−0.0083 (7)	0.0009 (6)
C9	0.0374 (8)	0.0341 (9)	0.0368 (8)	0.0010 (7)	−0.0125 (7)	0.0008 (7)
C10	0.0370 (8)	0.0322 (8)	0.0376 (8)	−0.0037 (7)	−0.0051 (7)	−0.0042 (7)
C11	0.0395 (9)	0.0356 (9)	0.0497 (10)	−0.0037 (7)	−0.0135 (8)	−0.0050 (8)
N1	0.0354 (7)	0.0229 (6)	0.0385 (7)	−0.0005 (5)	−0.0115 (6)	0.0022 (5)
O1	0.0517 (7)	0.0246 (6)	0.0584 (8)	−0.0014 (5)	−0.0286 (6)	0.0011 (5)
O2	0.0559 (8)	0.0382 (7)	0.0511 (8)	−0.0093 (6)	−0.0174 (6)	−0.0103 (6)
O3	0.0593 (8)	0.0273 (6)	0.0638 (9)	−0.0037 (6)	−0.0298 (6)	−0.0009 (6)
Cl1	0.0708 (4)	0.0261 (2)	0.0743 (4)	0.00032 (19)	−0.0426 (3)	0.0058 (2)

Geometric parameters (Å, º) top

C1—C2	1.383 (2)	C7—N1	1.334 (2)
C1—C6	1.392 (2)	C7—C8	1.481 (2)
C1—N1	1.4170 (19)	C8—C9	1.330 (2)
C2—C3	1.382 (2)	C8—H8	0.9300
C2—H2	0.9300	C9—C10	1.493 (2)
C3—C4	1.386 (2)	C9—H9	0.9300
C3—Cl1	1.7364 (16)	C10—O2	1.212 (2)
C4—C5	1.384 (2)	C10—O3	1.296 (2)
C4—C11	1.500 (2)	C11—H11A	0.9600
C5—C6	1.378 (2)	C11—H11B	0.9600
C5—H5	0.9300	C11—H11C	0.9600
C6—H6	0.9300	N1—H1N	0.869 (15)
C7—O1	1.2410 (19)	O3—H3O	0.871 (16)

C2—C1—C6	119.32 (14)	N1—C7—C8	114.71 (13)
C2—C1—N1	124.51 (13)	C9—C8—C7	128.69 (15)
C6—C1—N1	116.16 (13)	C9—C8—H8	115.7
C3—C2—C1	118.80 (14)	C7—C8—H8	115.7
C3—C2—H2	120.6	C8—C9—C10	132.10 (15)
C1—C2—H2	120.6	C8—C9—H9	113.9
C2—C3—C4	123.73 (14)	C10—C9—H9	113.9
C2—C3—Cl1	117.95 (12)	O2—C10—O3	120.32 (16)
C4—C3—Cl1	118.31 (12)	O2—C10—C9	118.75 (16)
C5—C4—C3	115.58 (14)	O3—C10—C9	120.92 (14)
C5—C4—C11	121.39 (14)	C4—C11—H11A	109.5
C3—C4—C11	123.03 (14)	C4—C11—H11B	109.5
C6—C5—C4	122.79 (15)	H11A—C11—H11B	109.5
C6—C5—H5	118.6	C4—C11—H11C	109.5
C4—C5—H5	118.6	H11A—C11—H11C	109.5
C5—C6—C1	119.74 (15)	H11B—C11—H11C	109.5
C5—C6—H6	120.1	C7—N1—C1	128.23 (13)
C1—C6—H6	120.1	C7—N1—H1N	115.1 (13)
O1—C7—N1	122.59 (14)	C1—N1—H1N	116.2 (13)
O1—C7—C8	122.70 (14)	C10—O3—H3O	108.9 (16)

C6—C1—C2—C3	0.9 (3)	C2—C1—C6—C5	−1.5 (3)
N1—C1—C2—C3	−178.44 (16)	N1—C1—C6—C5	177.89 (15)
C1—C2—C3—C4	0.6 (3)	O1—C7—C8—C9	3.8 (3)
C1—C2—C3—Cl1	−178.99 (13)	N1—C7—C8—C9	−176.65 (18)
C2—C3—C4—C5	−1.5 (3)	C7—C8—C9—C10	1.3 (3)
Cl1—C3—C4—C5	178.12 (13)	C8—C9—C10—O2	173.92 (19)
C2—C3—C4—C11	178.21 (16)	C8—C9—C10—O3	−5.7 (3)
Cl1—C3—C4—C11	−2.2 (2)	O1—C7—N1—C1	−3.5 (3)
C3—C4—C5—C6	0.9 (3)	C8—C7—N1—C1	177.01 (15)
C11—C4—C5—C6	−178.86 (17)	C2—C1—N1—C7	6.7 (3)
C4—C5—C6—C1	0.6 (3)	C6—C1—N1—C7	−172.69 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.87 (2)	2.11 (2)	2.9546 (19)	164 (2)
O3—H3O···O1	0.87 (2)	1.62 (2)	2.4885 (17)	173 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀ClNO₃
M_r	239.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.005 (1), 13.491 (2), 8.757 (1)
β (°)	97.91 (1)
V (Å³)	1053.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.48 × 0.40 × 0.34

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	0.849, 0.890
No. of measured, independent and observed [I > 2σ(I)] reflections	4069, 2147, 1798
R_int	0.011
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.105, 1.04
No. of reflections	2147
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)	0.33, −0.27

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	0.869 (15)	2.111 (15)	2.9546 (19)	163.8 (18)
O3—H3O···O1	0.871 (16)	1.621 (17)	2.4885 (17)	173 (2)

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

Acknowledgements

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

References

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