N-(3-Chloro­phen­yl)succinamic acid

Abstract

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,

• a = 10.0308 (8) Å

• b = 11.1810 (9) Å

• c = 19.036 (2) Å

• V = 2135.0 (3) ų

• 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 ▶) 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[F ² > 2σ(F ²)] = 0.058

• wR(F ²) = 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

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The H atoms of the OH and NH group were located in a difference map and refined with a distance restraint of O—H = 0.82 (2) %A and N—H = 0.86 (2) %A. The other H atoms were positioned with idealized geometry using a riding model with C—H = 0.93–0.97 Å. All H atoms were refined with isotropic displacement parameters set to 1.2 times of the U_eq of the parent atom.

Figures

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.

Crystal data

C10H10ClNO3	F(000) = 944
Mr = 227.64	Dx = 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

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	Rint = 0.045
Rotation method data acquisition using ω and φ scans.	θmax = 26.4°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −9→12
Tmin = 0.922, Tmax = 0.980	k = −12→13
8200 measured reflections	l = −22→23

Refinement

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(Fo2) + (0.0603P)2 + 1.1737P] where P = (Fo2 + 2Fc2)/3
2184 reflections	(Δ/σ)max = 0.012
142 parameters	Δρmax = 0.30 e Å−3
2 restraints	Δρmin = −0.39 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.