N-(3-Chloro­phen­yl)succinamic acid

Gowda, B.T.; Foro, S.; Saraswathi, B.S.; Fuess, H.

doi:10.1107/S1600536810008949

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o842

doi:10.1107/S1600536810008949

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N-(3-Chlorophenyl)succinamic acid

B. Thimme Gowda,^a ^* Sabine Foro,^b B. S. Saraswathi ^a and Hartmut Fuess ^b

^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 7 March 2010; accepted 9 March 2010; online 17 March 2010)

In the title compound, C₁₀H₁₀ClNO₃, the N—H and C=O bonds in the amide segment are trans to each other. In the crystal structure, the molecules are linked into infinite chains through intermolecular N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For our study of the effect of ring and side-chain substitutions on the structures of anilides and for related structures, see: Gowda et al. (2009a ,b ; 2010 ); Jagannathan et al. (1994 ).

Experimental

Crystal data

C₁₀H₁₀ClNO₃
M_r = 227.64
Orthorhombic, P b c a
a = 10.0308 (8) Å
b = 11.1810 (9) Å
c = 19.036 (2) Å
V = 2135.0 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 299 K
0.24 × 0.20 × 0.06 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 = 0.922, T_max = 0.980
8200 measured reflections
2184 independent reflections
1137 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.152
S = 1.02
2184 reflections
142 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O1ⁱ	0.82 (2)	1.92 (2)	2.693 (3)	158 (5)
N1—H1N⋯O2ⁱⁱ	0.85 (2)	2.02 (2)	2.872 (4)	173 (3)
Symmetry codes: (i) -x, -y, -z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

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/S1600536810008949/bt5210sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008949/bt5210Isup2.hkl

checkCIF report

Comment top

As a part of studying the effect of ring and side chain substitutions on the structures of anilides (Gowda et al., 2009a,b; 2010), the crystal structure of N-(3-chlorophenyl)succinamic acid (I) has been determined. The conformations of N—H and C=O bonds in the amide segment are anti to each other, similar to those observed in N-(2-chlorophenyl)succinamic acid (II)(Gowda et al., 2009b) and N-(4-chlorophenyl)succinamic acid (III) (Gowda et al., 2009a) and N-(3-methylphenyl)succinamic acid (IV)(Gowda et al., 2010). But the conformation of the amide oxygen and the carbonyl oxygen of the acid segment are syn to each other, similar to that observed in (IV), but contrary contrary to the anti conformation observed in (II) and (III). Further, the conformation of both the C=O bonds are anti to the H atoms of their adjacent –CH₂ groups (Fig. 1) and the C=O and O—H bonds of the acid group are in syn position to each other, similar to that observed in (II), (III) and (IV).

The conformation of the amide hydrogen is syn to the meta- Cl group in the benzene ring, similar to that of the ortho-Cl in (II), but contrary to the anti conformation observed between the amide hydrogen and the meta-methyl group in (IV).

The N—H···O and O—H···O intermolecular hydrogen bonds pack the mpolecules into infinite chains in the structure (Table 1, Fig.2).

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 study of the effect of ring and side-chain substitutions on the

structures of anilides and for related structures, see: Gowda et al. (2009a,b; 2010); Jagannathan et al. (1994).

Experimental top

The solution of succinic anhydride (0.01 mole) in toluene (25 ml) was treated dropwise with the solution of m-chloroaniline (0.01 mole) also in toluene (20 ml) with constant stirring. The resulting mixture was stirred for about one h 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 m-chloroaniline. The resultant solid N-(3-chlorophenyl)succinamic acid 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 by elemental analysis and characterized by its infrared and NMR spectra. The plate like colorless single crystals used in X-ray diffraction studies were grown in ethanolic 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. Molecular structure of the title compound, showing the atom labelling scheme. The displacement ellipsoids are drawn at the 50% probability level. The H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

N-(3-Chlorophenyl)succinamic acid top

Crystal data top

C₁₀H₁₀ClNO₃	F(000) = 944
M_r = 227.64	D_x = 1.416 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2016 reflections
a = 10.0308 (8) Å	θ = 2.7–27.7°
b = 11.1810 (9) Å	µ = 0.34 mm⁻¹
c = 19.036 (2) Å	T = 299 K
V = 2135.0 (3) Å³	Plate, colourless
Z = 8	0.24 × 0.20 × 0.06 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2184 independent reflections
Radiation source: fine-focus sealed tube	1137 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Rotation method data acquisition using ω and ϕ scans.	θ_max = 26.4°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −9→12
T_min = 0.922, T_max = 0.980	k = −12→13
8200 measured reflections	l = −22→23

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0603P)² + 1.1737P] where P = (F_o² + 2F_c²)/3
2184 reflections	(Δ/σ)_max = 0.012
142 parameters	Δρ_max = 0.30 e Å⁻³
2 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₁₀H₁₀ClNO₃	V = 2135.0 (3) Å³
M_r = 227.64	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.0308 (8) Å	µ = 0.34 mm⁻¹
b = 11.1810 (9) Å	T = 299 K
c = 19.036 (2) Å	0.24 × 0.20 × 0.06 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2184 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1137 reflections with I > 2σ(I)
T_min = 0.922, T_max = 0.980	R_int = 0.045
8200 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	2 restraints
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.30 e Å⁻³
2184 reflections	Δρ_min = −0.39 e Å⁻³
142 parameters

Special details top

Experimental. CrysAlis RED (Oxford Diffraction, 2009) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.25030 (11)	0.71276 (10)	0.20800 (6)	0.0858 (4)
O1	−0.0249 (2)	0.23883 (19)	0.02471 (13)	0.0655 (7)
O2	0.1845 (3)	0.0367 (2)	−0.03891 (14)	0.0673 (7)
O3	0.0091 (3)	−0.0318 (2)	−0.09646 (13)	0.0651 (7)
H3O	0.033 (5)	−0.097 (2)	−0.081 (2)	0.098*
N1	0.1200 (3)	0.3941 (2)	0.03276 (15)	0.0539 (8)
H1N	0.181 (3)	0.431 (3)	0.0101 (16)	0.065*
C1	0.0900 (3)	0.4445 (3)	0.09884 (18)	0.0484 (8)
C2	0.1706 (4)	0.5390 (3)	0.12010 (18)	0.0523 (9)
H2	0.2395	0.5654	0.0913	0.063*
C3	0.1482 (4)	0.5930 (3)	0.1835 (2)	0.0574 (10)
C4	0.0471 (5)	0.5568 (4)	0.2270 (2)	0.0714 (12)
H4	0.0329	0.5943	0.2700	0.086*
C5	−0.0325 (5)	0.4644 (4)	0.2058 (2)	0.0741 (12)
H5	−0.1015	0.4393	0.2349	0.089*
C6	−0.0129 (4)	0.4072 (3)	0.1420 (2)	0.0627 (10)
H6	−0.0682	0.3446	0.1284	0.075*
C7	0.0649 (3)	0.2997 (3)	−0.00050 (19)	0.0480 (8)
C8	0.1239 (3)	0.2756 (3)	−0.07174 (17)	0.0519 (9)
H8A	0.2183	0.2590	−0.0664	0.062*
H8B	0.1151	0.3468	−0.1004	0.062*
C9	0.0587 (4)	0.1716 (3)	−0.10939 (18)	0.0566 (9)
H9A	−0.0373	0.1824	−0.1086	0.068*
H9B	0.0870	0.1716	−0.1581	0.068*
C10	0.0920 (4)	0.0530 (3)	−0.07727 (17)	0.0444 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0739 (7)	0.0821 (8)	0.1014 (9)	0.0073 (6)	−0.0183 (7)	−0.0295 (6)
O1	0.0610 (15)	0.0445 (13)	0.091 (2)	−0.0112 (12)	0.0190 (14)	0.0046 (12)
O2	0.0650 (17)	0.0477 (14)	0.0894 (19)	0.0055 (13)	−0.0291 (16)	0.0059 (13)
O3	0.0739 (18)	0.0504 (14)	0.0712 (17)	−0.0174 (15)	−0.0159 (14)	0.0058 (13)
N1	0.0531 (18)	0.0452 (16)	0.063 (2)	−0.0146 (14)	0.0162 (15)	−0.0029 (14)
C1	0.049 (2)	0.0408 (18)	0.055 (2)	0.0040 (16)	0.0087 (18)	0.0059 (16)
C2	0.045 (2)	0.054 (2)	0.058 (2)	0.0041 (18)	0.0071 (17)	0.0025 (17)
C3	0.053 (2)	0.057 (2)	0.062 (2)	0.0130 (18)	−0.009 (2)	0.0002 (19)
C4	0.088 (3)	0.075 (3)	0.052 (3)	0.019 (3)	0.008 (2)	0.004 (2)
C5	0.083 (3)	0.074 (3)	0.066 (3)	0.007 (3)	0.032 (2)	0.018 (2)
C6	0.060 (2)	0.054 (2)	0.074 (3)	−0.0032 (19)	0.018 (2)	0.0106 (19)
C7	0.0447 (18)	0.0346 (16)	0.065 (2)	0.0046 (15)	0.0048 (19)	0.0118 (16)
C8	0.056 (2)	0.0356 (17)	0.064 (2)	0.0035 (16)	0.0013 (19)	0.0076 (16)
C9	0.065 (2)	0.0490 (19)	0.056 (2)	0.0029 (18)	−0.0134 (19)	0.0037 (17)
C10	0.047 (2)	0.0430 (19)	0.0430 (19)	0.0012 (16)	0.0024 (17)	−0.0039 (15)

Geometric parameters (Å, º) top

Cl1—C3	1.749 (4)	C4—C5	1.366 (6)
O1—C7	1.226 (4)	C4—H4	0.9300
O2—C10	1.195 (4)	C5—C6	1.388 (5)
O3—C10	1.313 (4)	C5—H5	0.9300
O3—H3O	0.820 (19)	C6—H6	0.9300
N1—C7	1.349 (4)	C7—C8	1.504 (5)
N1—C1	1.411 (4)	C8—C9	1.515 (4)
N1—H1N	0.853 (18)	C8—H8A	0.9700
C1—C6	1.384 (5)	C8—H8B	0.9700
C1—C2	1.391 (5)	C9—C10	1.498 (4)
C2—C3	1.369 (5)	C9—H9A	0.9700
C2—H2	0.9300	C9—H9B	0.9700
C3—C4	1.371 (5)

C10—O3—H3O	111 (3)	C1—C6—H6	120.4
C7—N1—C1	130.1 (3)	C5—C6—H6	120.4
C7—N1—H1N	116 (2)	O1—C7—N1	123.5 (3)
C1—N1—H1N	114 (2)	O1—C7—C8	122.8 (3)
C6—C1—C2	119.4 (3)	N1—C7—C8	113.7 (3)
C6—C1—N1	124.6 (3)	C7—C8—C9	113.2 (3)
C2—C1—N1	116.0 (3)	C7—C8—H8A	108.9
C3—C2—C1	119.8 (3)	C9—C8—H8A	108.9
C3—C2—H2	120.1	C7—C8—H8B	108.9
C1—C2—H2	120.1	C9—C8—H8B	108.9
C2—C3—C4	121.6 (4)	H8A—C8—H8B	107.7
C2—C3—Cl1	118.5 (3)	C10—C9—C8	112.9 (3)
C4—C3—Cl1	119.9 (3)	C10—C9—H9A	109.0
C5—C4—C3	118.5 (4)	C8—C9—H9A	109.0
C5—C4—H4	120.7	C10—C9—H9B	109.0
C3—C4—H4	120.7	C8—C9—H9B	109.0
C4—C5—C6	121.7 (4)	H9A—C9—H9B	107.8
C4—C5—H5	119.2	O2—C10—O3	123.5 (3)
C6—C5—H5	119.2	O2—C10—C9	123.9 (3)
C1—C6—C5	119.1 (4)	O3—C10—C9	112.6 (3)

C7—N1—C1—C6	−4.0 (6)	N1—C1—C6—C5	−179.8 (3)
C7—N1—C1—C2	176.7 (3)	C4—C5—C6—C1	0.2 (6)
C6—C1—C2—C3	0.6 (5)	C1—N1—C7—O1	−1.2 (5)
N1—C1—C2—C3	179.9 (3)	C1—N1—C7—C8	178.9 (3)
C1—C2—C3—C4	−0.4 (5)	O1—C7—C8—C9	1.7 (4)
C1—C2—C3—Cl1	−179.2 (3)	N1—C7—C8—C9	−178.4 (3)
C2—C3—C4—C5	0.0 (6)	C7—C8—C9—C10	−71.0 (4)
Cl1—C3—C4—C5	178.8 (3)	C8—C9—C10—O2	−18.4 (5)
C3—C4—C5—C6	0.1 (6)	C8—C9—C10—O3	162.3 (3)
C2—C1—C6—C5	−0.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1ⁱ	0.82 (2)	1.92 (2)	2.693 (3)	158 (5)
N1—H1N···O2ⁱⁱ	0.85 (2)	2.02 (2)	2.872 (4)	173 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀ClNO₃
M_r	227.64
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	299
a, b, c (Å)	10.0308 (8), 11.1810 (9), 19.036 (2)
V (Å³)	2135.0 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.24 × 0.20 × 0.06

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	0.922, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	8200, 2184, 1137
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.152, 1.02
No. of reflections	2184
No. of parameters	142
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)	0.30, −0.39

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···O1ⁱ	0.820 (19)	1.92 (2)	2.693 (3)	158 (5)
N1—H1N···O2ⁱⁱ	0.853 (18)	2.024 (19)	2.872 (4)	173 (3)

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

Acknowledgements

BSS thanks the University Grants Commission, Government of India, New Delhi, for the award of a research fellowship under its faculty improvement program.

References

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