N-(4-Chloro­phen­yl)succinamic acid

In the title compound, C₁₀H₁₀ClNO₃, the conformation of the amide O atom and the carbonyl O atom of the acid segment are anti to each other and further, they are anti to the H atoms of their adjacent –CH₂ groups. The C=O and O—H bonds of the acid group are in the syn position relative to each other. In the crystal, mol­ecules are packed 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 substitution on the solid-state geometry of anilides, see: Gowda et al. (2009a,b,c). For the modes of inter­linking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976). The packing of mol­ecules involving dimeric hydrogen-bonded association of each carboxyl group with a centrosymmetrically related neighbor has also been observed, see: Jagannathan et al. (1994).

Experimental

Crystal data

• C₁₀H₁₀ClNO₃

• M_r = 227.64

• Monoclinic, P 2₁ /c

• a = 15.908 (1) Å

• b = 4.8778 (4) Å

• c = 14.286 (1) Å

• β = 109.787 (6)°

• V = 1043.09 (13) ų

• Z = 4

• Cu Kα radiation

• μ = 3.16 mm⁻¹

• T = 299 K

• 0.55 × 0.43 × 0.15 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (North et al., 1968) T_min = 0.265, T_max = 0.623

• 3006 measured reflections

• 1837 independent reflections

• 1643 reflections with I > 2σ(I)

• R_int = 0.026

• 3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

• R[F² > 2σ(F²)] = 0.042

• wR(F²) = 0.121

• S = 1.04

• 1837 reflections

• 143 parameters

• 1 restraint

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

• Δρ_max = 0.30 e Å⁻³

• Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1^i	0.819 (17)	2.117 (17)	2.931 (2)	173 (2)
O2—H2O⋯O3^ii	0.85 (3)	1.85 (3)	2.693 (2)	179 (3)
Symmetry codes: (i) x, y+1, z; (ii) -x+2, -y+1, -z+3.

Data collection: CAD-4-PC (Enraf–Nonius, 1996); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987); 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

S1. Comment

As a part of studying the effect of ring and side chain substitutions on the solid state geometry of anilides (Gowda et al., 2009a,b,c), we report herein the crystal structure of N-(4-chlorophenyl)succinamic acid (I). The conformations of N—H and C=O bonds in the amide segment are anti to each other and the conformation of the amide oxygen and the carbonyl oxygen of the acid segment are also anti to each other and further, they are anti to the H atoms of their adjacent –CH₂ groups (Fig. 1), similar to that observed in N-(4-chlorophenyl)succinamate (Gowda et al., 2009a) and N-(2-chlorophenyl)succinamic acid (Gowda et al., 2009b). The C=O and O—H bonds of the acid group are in syn position to each other. 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 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

For ourstudy of the effect of ring and side-chain substitution on the solid-state geometry of anilides, see: Gowda et al. (2009a,b,c). For the modes of interlinking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976). The packing of molecules involving dimeric hydrogen-bonded association of each carboxyl group with a centrosymmetrically related neighbor has also been observed, see: Jagannathan et al. (1994).

S2. Experimental

The solution of succinic anhydride (2.5 g) in toluene (25 cc) was treated dropwise with the solution of 4-chloroaniline (2.5 g) also in toluene (20 cc) 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 4-chloroaniline. The resultant solid N-(4-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 single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.

S3. Refinement

The H atom of the OH group was located in a diffrerence map and its position refined [O—H = 0.85 (3) Å]. The N-bound H atom was located in difference map and refined with restrained geometry to 0.86 (2) Å. The other H atoms were positioned with idealized geometry using a riding model [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).

Computing details

Data collection: CAD-4-PC (Enraf–Nonius, 1996); cell refinement: CAD-4-PC (Enraf–Nonius, 1996); data reduction: REDU4 (Stoe & Cie, 1987); 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

	Fig. 1. Molecular structure of (I), 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 (I) with hydrogen bonding shown as dashed lines.

N-(4-Chlorophenyl)succinamic acid

Crystal data

C10H10ClNO3	F(000) = 472
Mr = 227.64	Dx = 1.450 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 15.908 (1) Å	θ = 6.6–18.1°
b = 4.8778 (4) Å	µ = 3.16 mm^−1
c = 14.286 (1) Å	T = 299 K
β = 109.787 (6)°	Prism, colourless
V = 1043.09 (13) Å^3	0.55 × 0.43 × 0.15 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	1643 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 67.0°, θmin = 3.0°
ω/2θ scans	h = −18→18
Absorption correction: ψ scan (North et al., 1968)	k = 0→5
Tmin = 0.265, Tmax = 0.623	l = −17→8
3006 measured reflections	3 standard reflections every 120 min
1837 independent reflections	intensity decay: 1.0%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0621P)^2 + 0.4605P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.004
1837 reflections	Δρmax = 0.30 e Å^−3
143 parameters	Δρmin = −0.26 e Å^−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0090 (10)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.71205 (12)	0.4065 (4)	0.91702 (13)	0.0401 (4)
C2	0.72512 (14)	0.5563 (4)	0.84114 (15)	0.0508 (5)
H2	0.7675	0.6958	0.8560	0.061*
C3	0.67546 (16)	0.4998 (5)	0.74299 (15)	0.0572 (6)
H3	0.6834	0.6028	0.6919	0.069*
C4	0.61449 (13)	0.2907 (5)	0.72194 (14)	0.0498 (5)
C5	0.60089 (14)	0.1398 (5)	0.79657 (15)	0.0524 (5)
H5	0.5591	−0.0013	0.7813	0.063*
C6	0.64971 (14)	0.1987 (4)	0.89477 (15)	0.0478 (5)
H6	0.6404	0.0981	0.9457	0.057*
C7	0.79738 (13)	0.3002 (4)	1.09135 (13)	0.0410 (4)
C8	0.83960 (13)	0.4299 (4)	1.19225 (13)	0.0439 (5)
H8A	0.8661	0.6037	1.1844	0.053*
H8B	0.7936	0.4669	1.2210	0.053*
C9	0.91033 (14)	0.2509 (4)	1.26240 (14)	0.0453 (5)
H9A	0.8848	0.0720	1.2655	0.054*
H9B	0.9584	0.2261	1.2358	0.054*
C10	0.94834 (12)	0.3632 (4)	1.36527 (14)	0.0422 (4)
N1	0.76140 (12)	0.4779 (3)	1.01677 (11)	0.0448 (4)
H1N	0.7718 (15)	0.641 (4)	1.0297 (17)	0.054*
O1	0.79464 (12)	0.0511 (3)	1.08006 (11)	0.0594 (5)
O2	1.01272 (13)	0.2126 (4)	1.42350 (12)	0.0704 (6)
H2O	1.032 (2)	0.281 (6)	1.481 (2)	0.084*
O3	0.92375 (12)	0.5735 (4)	1.39202 (10)	0.0695 (5)
Cl1	0.55277 (5)	0.21449 (18)	0.59903 (4)	0.0831 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0446 (9)	0.0350 (10)	0.0343 (9)	0.0029 (8)	0.0052 (7)	−0.0037 (7)
C2	0.0572 (12)	0.0453 (12)	0.0449 (11)	−0.0117 (10)	0.0109 (9)	−0.0018 (9)
C3	0.0683 (13)	0.0631 (14)	0.0383 (10)	−0.0065 (11)	0.0158 (9)	0.0009 (10)
C4	0.0457 (10)	0.0640 (14)	0.0353 (10)	0.0035 (10)	0.0081 (8)	−0.0096 (9)
C5	0.0463 (10)	0.0561 (13)	0.0480 (11)	−0.0113 (10)	0.0071 (9)	−0.0092 (10)
C6	0.0508 (11)	0.0496 (12)	0.0382 (10)	−0.0095 (9)	0.0089 (8)	−0.0018 (8)
C7	0.0493 (10)	0.0305 (10)	0.0361 (9)	−0.0018 (8)	0.0053 (8)	−0.0045 (7)
C8	0.0554 (11)	0.0318 (10)	0.0348 (9)	0.0005 (8)	0.0024 (8)	−0.0044 (7)
C9	0.0522 (11)	0.0385 (10)	0.0370 (10)	0.0028 (8)	0.0045 (8)	−0.0046 (8)
C10	0.0461 (10)	0.0382 (10)	0.0367 (9)	0.0020 (8)	0.0068 (8)	0.0002 (8)
N1	0.0583 (10)	0.0279 (8)	0.0369 (8)	−0.0039 (7)	0.0011 (7)	−0.0042 (6)
O1	0.0879 (11)	0.0271 (8)	0.0449 (8)	−0.0005 (7)	−0.0014 (7)	−0.0053 (6)
O2	0.0840 (12)	0.0641 (11)	0.0407 (8)	0.0300 (9)	−0.0082 (8)	−0.0093 (7)
O3	0.0830 (11)	0.0628 (11)	0.0412 (8)	0.0300 (9)	−0.0070 (7)	−0.0147 (7)
Cl1	0.0851 (5)	0.1153 (7)	0.0360 (3)	−0.0133 (4)	0.0037 (3)	−0.0179 (3)

Geometric parameters (Å, º)

C1—C6	1.378 (3)	C7—N1	1.342 (2)
C1—C2	1.380 (3)	C7—C8	1.508 (2)
C1—N1	1.418 (2)	C8—C9	1.506 (3)
C2—C3	1.384 (3)	C8—H8A	0.9700
C2—H2	0.9300	C8—H8B	0.9700
C3—C4	1.369 (3)	C9—C10	1.491 (3)
C3—H3	0.9300	C9—H9A	0.9700
C4—C5	1.372 (3)	C9—H9B	0.9700
C4—Cl1	1.7373 (19)	C10—O3	1.205 (2)
C5—C6	1.384 (3)	C10—O2	1.305 (2)
C5—H5	0.9300	N1—H1N	0.819 (17)
C6—H6	0.9300	O2—H2O	0.85 (3)
C7—O1	1.225 (2)
C6—C1—C2	119.75 (18)	N1—C7—C8	114.84 (15)
C6—C1—N1	121.52 (18)	C9—C8—C7	112.54 (16)
C2—C1—N1	118.68 (18)	C9—C8—H8A	109.1
C1—C2—C3	120.3 (2)	C7—C8—H8A	109.1
C1—C2—H2	119.9	C9—C8—H8B	109.1
C3—C2—H2	119.9	C7—C8—H8B	109.1
C4—C3—C2	119.3 (2)	H8A—C8—H8B	107.8
C4—C3—H3	120.3	C10—C9—C8	113.89 (16)
C2—C3—H3	120.3	C10—C9—H9A	108.8
C3—C4—C5	121.03 (19)	C8—C9—H9A	108.8
C3—C4—Cl1	119.83 (17)	C10—C9—H9B	108.8
C5—C4—Cl1	119.14 (17)	C8—C9—H9B	108.8
C4—C5—C6	119.6 (2)	H9A—C9—H9B	107.7
C4—C5—H5	120.2	O3—C10—O2	123.09 (18)
C6—C5—H5	120.2	O3—C10—C9	123.94 (17)
C1—C6—C5	119.98 (19)	O2—C10—C9	112.96 (17)
C1—C6—H6	120.0	C7—N1—C1	125.55 (16)
C5—C6—H6	120.0	C7—N1—H1N	116.6 (17)
O1—C7—N1	123.35 (17)	C1—N1—H1N	117.8 (17)
O1—C7—C8	121.79 (17)	C10—O2—H2O	110 (2)
C6—C1—C2—C3	0.4 (3)	O1—C7—C8—C9	26.2 (3)
N1—C1—C2—C3	−177.3 (2)	N1—C7—C8—C9	−155.58 (18)
C1—C2—C3—C4	−1.2 (4)	C7—C8—C9—C10	−175.40 (17)
C2—C3—C4—C5	1.1 (4)	C8—C9—C10—O3	2.1 (3)
C2—C3—C4—Cl1	−179.15 (18)	C8—C9—C10—O2	−176.62 (19)
C3—C4—C5—C6	−0.2 (3)	O1—C7—N1—C1	3.3 (3)
Cl1—C4—C5—C6	180.00 (17)	C8—C7—N1—C1	−174.84 (18)
C2—C1—C6—C5	0.4 (3)	C6—C1—N1—C7	42.0 (3)
N1—C1—C6—C5	178.14 (19)	C2—C1—N1—C7	−140.3 (2)
C4—C5—C6—C1	−0.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.82 (2)	2.12 (2)	2.931 (2)	173 (2)
O2—H2O···O3^ii	0.85 (3)	1.85 (3)	2.693 (2)	179 (3)

Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y+1, −z+3.