3-[(3,5-Dichloro­anilino)carbon­yl]propionic acid

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

doi:10.1107/S1600536809010319

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o873

doi:10.1107/S1600536809010319

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3-[(3,5-Dichloroanilino)carbonyl]propionic acid

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

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany, and ^cFaculty of Integrated Arts and Sciences, Tokushima University, Minamijosanjima-cho, Tokushima 770-8502, Japan
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 14 February 2009; accepted 20 March 2009; online 25 March 2009)

In the crystal structure of the title compound, C₁₀H₉Cl₂NO₃, the conformations of the amide O atom and the carbonyl O atom of the acid segment are anti to the H atoms of the adjacent –CH₂ groups. The C=O and O—H bonds of the acid group are in relatively rare anti positions with respect to each other. This is an obvious consequence of the concerted effects of both the all-anti molecular conformation and the intermolecular hydrogen bond donated to the amide carbonyl group. In the crystal, molecules are packed into infinite chains through intermolecular N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For the effect of ring and side-chain substitutions on the structures of amide compounds, see: Gowda et al. (2009 ). For the packing of molecules involving dimeric hydrogen-bonded association of each carboxyl group with a centrosymmetrically related neighbor, see: Jagannathan et al. (1994 ). For the various modes of interlinking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976 ).

Experimental

Crystal data

C₁₀H₉Cl₂NO₃
M_r = 262.08
Monoclinic, P 2₁ /n
a = 7.350 (1) Å
b = 10.318 (2) Å
c = 15.031 (3) Å
β = 99.44 (2)°
V = 1124.5 (3) Å³
Z = 4
Cu Kα radiation
μ = 5.15 mm⁻¹
T = 299 K
0.48 × 0.30 × 0.28 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.142, T_max = 0.242
4204 measured reflections
2005 independent reflections
1794 reflections with I > 2σ(I)
R_int = 0.111
3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.170
S = 1.13
2005 reflections
151 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O3ⁱ	0.95 (4)	1.93 (4)	2.857 (3)	167 (3)
O2—H2O⋯O1ⁱⁱ	0.82 (2)	1.85 (2)	2.656 (3)	170 (4)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+2, -z+1.

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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809010319/cs2111sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809010319/cs2111Isup2.hkl

checkCIF report

Comment top

The amide moiety is an important constituent of many biologically significant compounds. As a part of studying the effect of ring and side chain substitutions on the structures of this class of compounds (Gowda et al., 2009), we have determined the crystal structure of N-(3,5-dichlorophenyl)-succinamic acid (N35DCPSA, systematic name: 3-[(3,5-dichloro)-aminocarbonyl]propionic acid). The conformations of N—H and C=O bonds in the amide segment of the structure are anti to each other and those of the amide O atom and the carbonyl O atom of the acid segment are also anti to the H atoms attached to the adjacent C atoms (Fig.1). Further, C=O and O—H bonds of the acid group are anti to each other, contrary to the more general syn conformation observed for C=O and O—H bonds of the acid group e.g. N-(2,6-dimethylphenyl)- succinamic acid (N26DMPSA, Gowda et al., 2009). The various 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). In the present study, the rare anti conformation of the C=O and O—H bonds of the acid group has been observed. The torsional angles of the groups, C2—C1—N1—C7, C6—C1—N1—C7, C1—N1—C7—C8, C1—N1—C7—O1, N1—C7—C8—C9, C7—C8—C9—C10, O1—C7—C8—C9, C8—C9—C10—O2 and C8—C9—C10—O3 in the side chain of N35DCPSA are -180.0 (3)°, -1.3 (4)°, -174.4 (3)°, 4.3 (5)°, 178.9 (2)°, -175.5 (2)°, 0.4 (2)°, 175.0 (3)° and -5.3 (5)°, respectively, compared to the corresponding values of 114.1 (2)°, -66.5 (2)°, -176.2 (1)°, 2.0 (3)°, -145.4 (2)°, -175.5 (1)°, 36.3 (2)°, -161.1 (2)° and 19.1 (3)°, respectively, for N26DMPSA. The N—H···O and O—H···O intermolecular hydrogen bonds pack the molecules into infinite chains in the structure (Table 1, Fig.2).

Related literature top

For the effect of ring and side-chain

substitutions on the structures of amide compounds, see: Gowda et al. (2009). For the packing of molecules involving dimeric hydrogen-bonded association of each carboxyl group with a centrosymmetrically related neighbor, see: Jagannathan et al. (1994). For the various modes of interlinking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976).

Experimental top

The solution of succinic anhydride (0.025 mol) in toluene (25 ml) was treated dropwise with the solution of 3,5-dichloroaniline (0.025 mol) also in toluene (20 ml) with constant stirring. The resulting mixture was stirred for about one hour and set aside for an additional hour at room temperature for the completion of reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted 3,5-dichloroaniline. The resultant solid N-(3,5-dichlorophenyl)-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 an ethanol solution by slow evaporation at room temperature.

Computing details top

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 top

	Fig. 1. Molecular structure of the title molecule with atom labeling. Displacement ellipsoids are at the 50% probability level, H atoms represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing detail in the title crystal with hydrogen bonds shown as dashed lines.

3-[(3,5-Dichloroanilino)carbonyl]propionic acid top

Crystal data top

C₁₀H₉Cl₂NO₃	F(000) = 536
M_r = 262.08	D_x = 1.548 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 7.350 (1) Å	θ = 7.4–20.6°
b = 10.318 (2) Å	µ = 5.15 mm⁻¹
c = 15.031 (3) Å	T = 299 K
β = 99.44 (2)°	Prism, colourless
V = 1124.5 (3) Å³	0.48 × 0.30 × 0.28 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1794 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.111
Graphite monochromator	θ_max = 67.1°, θ_min = 5.2°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
T_min = 0.142, T_max = 0.242	l = −17→17
4204 measured reflections	3 standard reflections every 120 min
2005 independent reflections	intensity decay: 1.0%

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) = 0.170	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0804P)² + 0.4071P] where P = (F_o² + 2F_c²)/3
2005 reflections	(Δ/σ)_max = 0.009
151 parameters	Δρ_max = 0.37 e Å⁻³
1 restraint	Δρ_min = −0.54 e Å⁻³

Crystal data top

C₁₀H₉Cl₂NO₃	V = 1124.5 (3) Å³
M_r = 262.08	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 7.350 (1) Å	µ = 5.15 mm⁻¹
b = 10.318 (2) Å	T = 299 K
c = 15.031 (3) Å	0.48 × 0.30 × 0.28 mm
β = 99.44 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1794 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.111
T_min = 0.142, T_max = 0.242	3 standard reflections every 120 min
4204 measured reflections	intensity decay: 1.0%
2005 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	1 restraint
wR(F²) = 0.170	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.37 e Å⁻³
2005 reflections	Δρ_min = −0.54 e Å⁻³
151 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.2687 (3)	0.5234 (3)	0.51327 (16)	0.0360 (6)
C2	0.1971 (3)	0.4036 (3)	0.48363 (18)	0.0390 (6)
H2	0.1668	0.3863	0.4223	0.047*
C3	0.1715 (4)	0.3108 (3)	0.54585 (19)	0.0415 (6)
C4	0.2153 (4)	0.3313 (3)	0.63743 (19)	0.0453 (7)
H4	0.1971	0.2676	0.6789	0.054*
C5	0.2872 (4)	0.4502 (4)	0.66443 (18)	0.0453 (7)
C6	0.3155 (4)	0.5480 (3)	0.60551 (17)	0.0435 (7)
H6	0.3642	0.6276	0.6266	0.052*
C7	0.3499 (3)	0.7371 (3)	0.45487 (16)	0.0374 (6)
C8	0.3313 (4)	0.8125 (3)	0.36730 (17)	0.0421 (7)
H8A	0.3996	0.7685	0.3263	0.051*
H8B	0.2025	0.8148	0.3395	0.051*
C9	0.4014 (4)	0.9480 (3)	0.38180 (17)	0.0447 (7)
H9A	0.5322	0.9451	0.4055	0.054*
H9B	0.3400	0.9891	0.4268	0.054*
C10	0.3724 (4)	1.0293 (3)	0.29825 (18)	0.0436 (7)
N1	0.2863 (3)	0.6158 (3)	0.44600 (15)	0.0403 (6)
H1N	0.242 (4)	0.584 (4)	0.387 (3)	0.048*
O1	0.4152 (3)	0.7867 (3)	0.52683 (13)	0.0543 (6)
O2	0.4186 (4)	1.1531 (3)	0.30787 (14)	0.0622 (7)
H2O	0.459 (5)	1.167 (5)	0.3609 (15)	0.075*
O3	0.3114 (4)	0.9893 (3)	0.22424 (13)	0.0620 (7)
Cl1	0.07961 (12)	0.16217 (8)	0.50728 (6)	0.0580 (3)
Cl2	0.34909 (13)	0.47994 (11)	0.77952 (5)	0.0696 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0448 (12)	0.0368 (17)	0.0252 (12)	0.0015 (11)	0.0026 (9)	0.0014 (11)
C2	0.0487 (13)	0.0390 (17)	0.0287 (12)	0.0004 (12)	0.0050 (10)	−0.0022 (11)
C3	0.0490 (13)	0.0379 (17)	0.0382 (14)	−0.0009 (12)	0.0089 (10)	−0.0034 (12)
C4	0.0589 (16)	0.044 (2)	0.0339 (14)	−0.0048 (13)	0.0098 (11)	0.0050 (12)
C5	0.0585 (15)	0.051 (2)	0.0265 (13)	−0.0048 (13)	0.0071 (10)	0.0019 (12)
C6	0.0590 (15)	0.0454 (19)	0.0254 (13)	−0.0089 (13)	0.0044 (10)	−0.0008 (12)
C7	0.0463 (12)	0.0401 (17)	0.0242 (11)	−0.0013 (12)	0.0007 (9)	0.0008 (11)
C8	0.0598 (15)	0.0408 (17)	0.0237 (12)	−0.0014 (13)	0.0007 (10)	0.0025 (11)
C9	0.0643 (15)	0.0440 (19)	0.0230 (12)	−0.0036 (14)	−0.0009 (10)	0.0038 (12)
C10	0.0611 (15)	0.0426 (18)	0.0252 (12)	−0.0021 (13)	0.0012 (10)	0.0043 (12)
N1	0.0602 (12)	0.0370 (15)	0.0220 (10)	−0.0033 (11)	0.0019 (8)	−0.0001 (9)
O1	0.0824 (13)	0.0483 (15)	0.0272 (10)	−0.0156 (11)	−0.0056 (9)	0.0019 (9)
O2	0.1047 (17)	0.0458 (15)	0.0289 (11)	−0.0123 (13)	−0.0107 (10)	0.0092 (10)
O3	0.1032 (17)	0.0545 (16)	0.0224 (10)	−0.0094 (13)	−0.0071 (10)	0.0031 (9)
Cl1	0.0808 (6)	0.0403 (6)	0.0533 (5)	−0.0134 (4)	0.0127 (4)	−0.0065 (3)
Cl2	0.1032 (7)	0.0795 (8)	0.0243 (4)	−0.0260 (5)	0.0056 (4)	0.0014 (3)

Geometric parameters (Å, º) top

C1—C2	1.388 (4)	C7—N1	1.335 (4)
C1—C6	1.396 (4)	C7—C8	1.516 (4)
C1—N1	1.411 (4)	C8—C9	1.494 (5)
C2—C3	1.372 (4)	C8—H8A	0.97
C2—H2	0.93	C8—H8B	0.97
C3—C4	1.378 (4)	C9—C10	1.496 (4)
C3—Cl1	1.737 (3)	C9—H9A	0.97
C4—C5	1.371 (5)	C9—H9B	0.97
C4—H4	0.93	C10—O3	1.202 (4)
C5—C6	1.381 (4)	C10—O2	1.323 (4)
C5—Cl2	1.742 (3)	N1—H1N	0.95 (4)
C6—H6	0.93	O2—H2O	0.82 (2)
C7—O1	1.221 (3)

C2—C1—C6	120.0 (3)	N1—C7—C8	114.5 (2)
C2—C1—N1	116.5 (2)	C9—C8—C7	112.0 (2)
C6—C1—N1	123.5 (3)	C9—C8—H8A	109
C3—C2—C1	119.3 (2)	C7—C8—H8A	109
C3—C2—H2	120.3	C9—C8—H8B	109
C1—C2—H2	120.3	C7—C8—H8B	109
C2—C3—C4	122.6 (3)	H8A—C8—H8B	108
C2—C3—Cl1	118.5 (2)	C8—C9—C10	113.8 (2)
C4—C3—Cl1	118.9 (2)	C8—C9—H9A	109
C5—C4—C3	116.7 (3)	C10—C9—H9A	109
C5—C4—H4	121.7	C8—C9—H9B	109
C3—C4—H4	121.7	C10—C9—H9B	109
C4—C5—C6	123.7 (3)	H9A—C9—H9B	108
C4—C5—Cl2	118.5 (2)	O3—C10—O2	118.8 (3)
C6—C5—Cl2	117.8 (3)	O3—C10—C9	124.4 (3)
C5—C6—C1	117.7 (3)	O2—C10—C9	116.8 (3)
C5—C6—H6	121.1	C7—N1—C1	129.3 (2)
C1—C6—H6	121.1	C7—N1—H1N	118 (2)
O1—C7—N1	124.2 (3)	C1—N1—H1N	112 (2)
O1—C7—C8	121.3 (3)	C10—O2—H2O	109 (3)

O1—C7—C8—C9	0.2 (4)	O1—C7—N1—C1	4.3 (5)
N1—C7—C8—C9	178.9 (2)	C8—C7—N1—C1	−174.4 (3)
C7—C8—C9—C10	−175.5 (2)	C2—C1—N1—C7	180.0 (3)
C8—C9—C10—O3	−5.3 (5)	C6—C1—N1—C7	1.3 (4)
C8—C9—C10—O2	175.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3ⁱ	0.95 (4)	1.93 (4)	2.857 (3)	167 (3)
O2—H2O···O1ⁱⁱ	0.82 (2)	1.85 (2)	2.656 (3)	170 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₉Cl₂NO₃
M_r	262.08
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	299
a, b, c (Å)	7.350 (1), 10.318 (2), 15.031 (3)
β (°)	99.44 (2)
V (Å³)	1124.5 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	5.15
Crystal size (mm)	0.48 × 0.30 × 0.28

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.142, 0.242
No. of measured, independent and observed [I > 2σ(I)] reflections	4204, 2005, 1794
R_int	0.111
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.170, 1.13
No. of reflections	2005
No. of parameters	151
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.54

Computer programs: CAD-4-PC (Enraf–Nonius, 1996), REDU4 (Stoe & Cie, 1987), 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···O3ⁱ	0.95 (4)	1.93 (4)	2.857 (3)	167 (3)
O2—H2O···O1ⁱⁱ	0.82 (2)	1.85 (2)	2.656 (3)	170 (4)

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

Acknowledgements

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

References

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