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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1827.
Published online 2009 July 11. doi:  10.1107/S160053680902649X
PMCID: PMC2977089

N-(4-Chloro­phen­yl)succinamic acid

Abstract

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 [triangle],b [triangle],c [triangle]). For the modes of inter­linking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976 [triangle]). 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 [triangle]).

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Object name is e-65-o1827-scheme1.jpg

Experimental

Crystal data

  • C10H10ClNO3
  • M r = 227.64
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1827-efi1.jpg
  • a = 15.908 (1) Å
  • b = 4.8778 (4) Å
  • c = 14.286 (1) Å
  • β = 109.787 (6)°
  • V = 1043.09 (13) Å3
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.121
  • S = 1.04
  • 1837 reflections
  • 143 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.26 e Å−3

Data collection: CAD-4-PC (Enraf–Nonius, 1996 [triangle]); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902649X/bv2121sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902649X/bv2121Isup2.hkl

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

Acknowledgments

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions of his research fellowship.

supplementary crystallographic information

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).

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.

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 Ueq of the parent atom).

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.

Crystal data

C10H10ClNO3F(000) = 472
Mr = 227.64Dx = 1.450 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 15.908 (1) Åθ = 6.6–18.1°
b = 4.8778 (4) ŵ = 3.16 mm1
c = 14.286 (1) ÅT = 299 K
β = 109.787 (6)°Prism, colourless
V = 1043.09 (13) Å30.55 × 0.43 × 0.15 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer1643 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.026
graphiteθmax = 67.0°, θmin = 3.0°
ω/2θ scansh = −18→18
Absorption correction: ψ scan (North et al., 1968)k = 0→5
Tmin = 0.265, Tmax = 0.623l = −17→8
3006 measured reflections3 standard reflections every 120 min
1837 independent reflections intensity decay: 1.0%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.121w = 1/[σ2(Fo2) + (0.0621P)2 + 0.4605P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.004
1837 reflectionsΔρmax = 0.30 e Å3
143 parametersΔρmin = −0.26 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction 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 (Å2)

xyzUiso*/Ueq
C10.71205 (12)0.4065 (4)0.91702 (13)0.0401 (4)
C20.72512 (14)0.5563 (4)0.84114 (15)0.0508 (5)
H20.76750.69580.85600.061*
C30.67546 (16)0.4998 (5)0.74299 (15)0.0572 (6)
H30.68340.60280.69190.069*
C40.61449 (13)0.2907 (5)0.72194 (14)0.0498 (5)
C50.60089 (14)0.1398 (5)0.79657 (15)0.0524 (5)
H50.5591−0.00130.78130.063*
C60.64971 (14)0.1987 (4)0.89477 (15)0.0478 (5)
H60.64040.09810.94570.057*
C70.79738 (13)0.3002 (4)1.09135 (13)0.0410 (4)
C80.83960 (13)0.4299 (4)1.19225 (13)0.0439 (5)
H8A0.86610.60371.18440.053*
H8B0.79360.46691.22100.053*
C90.91033 (14)0.2509 (4)1.26240 (14)0.0453 (5)
H9A0.88480.07201.26550.054*
H9B0.95840.22611.23580.054*
C100.94834 (12)0.3632 (4)1.36527 (14)0.0422 (4)
N10.76140 (12)0.4779 (3)1.01677 (11)0.0448 (4)
H1N0.7718 (15)0.641 (4)1.0297 (17)0.054*
O10.79464 (12)0.0511 (3)1.08006 (11)0.0594 (5)
O21.01272 (13)0.2126 (4)1.42350 (12)0.0704 (6)
H2O1.032 (2)0.281 (6)1.481 (2)0.084*
O30.92375 (12)0.5735 (4)1.39202 (10)0.0695 (5)
Cl10.55277 (5)0.21449 (18)0.59903 (4)0.0831 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0446 (9)0.0350 (10)0.0343 (9)0.0029 (8)0.0052 (7)−0.0037 (7)
C20.0572 (12)0.0453 (12)0.0449 (11)−0.0117 (10)0.0109 (9)−0.0018 (9)
C30.0683 (13)0.0631 (14)0.0383 (10)−0.0065 (11)0.0158 (9)0.0009 (10)
C40.0457 (10)0.0640 (14)0.0353 (10)0.0035 (10)0.0081 (8)−0.0096 (9)
C50.0463 (10)0.0561 (13)0.0480 (11)−0.0113 (10)0.0071 (9)−0.0092 (10)
C60.0508 (11)0.0496 (12)0.0382 (10)−0.0095 (9)0.0089 (8)−0.0018 (8)
C70.0493 (10)0.0305 (10)0.0361 (9)−0.0018 (8)0.0053 (8)−0.0045 (7)
C80.0554 (11)0.0318 (10)0.0348 (9)0.0005 (8)0.0024 (8)−0.0044 (7)
C90.0522 (11)0.0385 (10)0.0370 (10)0.0028 (8)0.0045 (8)−0.0046 (8)
C100.0461 (10)0.0382 (10)0.0367 (9)0.0020 (8)0.0068 (8)0.0002 (8)
N10.0583 (10)0.0279 (8)0.0369 (8)−0.0039 (7)0.0011 (7)−0.0042 (6)
O10.0879 (11)0.0271 (8)0.0449 (8)−0.0005 (7)−0.0014 (7)−0.0053 (6)
O20.0840 (12)0.0641 (11)0.0407 (8)0.0300 (9)−0.0082 (8)−0.0093 (7)
O30.0830 (11)0.0628 (11)0.0412 (8)0.0300 (9)−0.0070 (7)−0.0147 (7)
Cl10.0851 (5)0.1153 (7)0.0360 (3)−0.0133 (4)0.0037 (3)−0.0179 (3)

Geometric parameters (Å, °)

C1—C61.378 (3)C7—N11.342 (2)
C1—C21.380 (3)C7—C81.508 (2)
C1—N11.418 (2)C8—C91.506 (3)
C2—C31.384 (3)C8—H8A0.9700
C2—H20.9300C8—H8B0.9700
C3—C41.369 (3)C9—C101.491 (3)
C3—H30.9300C9—H9A0.9700
C4—C51.372 (3)C9—H9B0.9700
C4—Cl11.7373 (19)C10—O31.205 (2)
C5—C61.384 (3)C10—O21.305 (2)
C5—H50.9300N1—H1N0.819 (17)
C6—H60.9300O2—H2O0.85 (3)
C7—O11.225 (2)
C6—C1—C2119.75 (18)N1—C7—C8114.84 (15)
C6—C1—N1121.52 (18)C9—C8—C7112.54 (16)
C2—C1—N1118.68 (18)C9—C8—H8A109.1
C1—C2—C3120.3 (2)C7—C8—H8A109.1
C1—C2—H2119.9C9—C8—H8B109.1
C3—C2—H2119.9C7—C8—H8B109.1
C4—C3—C2119.3 (2)H8A—C8—H8B107.8
C4—C3—H3120.3C10—C9—C8113.89 (16)
C2—C3—H3120.3C10—C9—H9A108.8
C3—C4—C5121.03 (19)C8—C9—H9A108.8
C3—C4—Cl1119.83 (17)C10—C9—H9B108.8
C5—C4—Cl1119.14 (17)C8—C9—H9B108.8
C4—C5—C6119.6 (2)H9A—C9—H9B107.7
C4—C5—H5120.2O3—C10—O2123.09 (18)
C6—C5—H5120.2O3—C10—C9123.94 (17)
C1—C6—C5119.98 (19)O2—C10—C9112.96 (17)
C1—C6—H6120.0C7—N1—C1125.55 (16)
C5—C6—H6120.0C7—N1—H1N116.6 (17)
O1—C7—N1123.35 (17)C1—N1—H1N117.8 (17)
O1—C7—C8121.79 (17)C10—O2—H2O110 (2)
C6—C1—C2—C30.4 (3)O1—C7—C8—C926.2 (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—C51.1 (4)C8—C9—C10—O32.1 (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—C13.3 (3)
Cl1—C4—C5—C6180.00 (17)C8—C7—N1—C1−174.84 (18)
C2—C1—C6—C50.4 (3)C6—C1—N1—C742.0 (3)
N1—C1—C6—C5178.14 (19)C2—C1—N1—C7−140.3 (2)
C4—C5—C6—C1−0.5 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.82 (2)2.12 (2)2.931 (2)173 (2)
O2—H2O···O3ii0.85 (3)1.85 (3)2.693 (2)179 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BV2121).

References

  • Enraf–Nonius (1996). CAD-4-PC Enraf–Nonius, Delft, The Netherlands.
  • Gowda, B. T., Foro, S., Saraswathi, B. S., Terao, H. & Fuess, H. (2009a). Acta Cryst. E65, o388. [PMC free article] [PubMed]
  • Gowda, B. T., Foro, S., Saraswathi, B. S., Terao, H. & Fuess, H. (2009b). Acta Cryst. E65, o399. [PMC free article] [PubMed]
  • Gowda, B. T., Foro, S., Saraswathi, B. S., Terao, H. & Fuess, H. (2009c). Acta Cryst. E65, o873. [PMC free article] [PubMed]
  • Jagannathan, N. R., Rajan, S. S. & Subramanian, E. (1994). J. Chem. Crystallogr.24, 75–78.
  • Leiserowitz, L. (1976). Acta Cryst. B32, 775–802.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Stoe & Cie (1987). REDU4 Stoe & Cie GmbH, Darmstadt, Germany.

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