3-[(3,4-Dichloro­phen­yl)amino­carbon­yl]propionic acid

Shah, F.A.; Tahir, M.N.; Ali, S.; Ahmed, S.; Danish, M.

doi:10.1107/S1600536809015025

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1130

doi:10.1107/S1600536809015025

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3-[(3,4-Dichlorophenyl)aminocarbonyl]propionic acid

Farooq Ali Shah,^a M. Nawaz Tahir,^b ^* Saqib Ali,^a Sajjad Ahmed ^a and Muhammad Danish ^c

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan, and ^cDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 22 April 2009; accepted 22 April 2009; online 25 April 2009)

In the title compound, C₁₀H₉Cl₂NO₃, inversion dimers occur due to pairs of intermolecular O—H⋯O hydrogen bonds from the carboxyl groups forming R₂²(8) loops. The dimers are linked into C(4) chains along the a axis by intermolecular N—H⋯O links. A short intramolecular C—H⋯O contact occurs in the molecule.

Related literature

For a related structure, see: Shah et al. (2008 ). For background, see: Pellerito & Nagy (2002 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₀H₉Cl₂NO₃
M_r = 262.08
Monoclinic, P 2₁ /n
a = 4.8441 (4) Å
b = 10.3388 (10) Å
c = 22.457 (2) Å
β = 90.613 (3)°
V = 1124.62 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 296 K
0.25 × 0.12 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.925, T_max = 0.949
11915 measured reflections
2912 independent reflections
2028 reflections with I > 3σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.182
S = 1.05
2912 reflections
172 parameters
Only H-atom coordinates refined
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O3ⁱ	0.81 (3)	2.10 (3)	2.887 (3)	165 (3)
O1—H1O⋯O2ⁱⁱ	0.80 (4)	1.87 (4)	2.665 (3)	170 (4)
C6—H6⋯O3	0.88 (4)	2.58 (4)	2.960 (4)	107 (3)
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+3, -z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809015025/hb2958sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015025/hb2958Isup2.hkl

checkCIF report

Comment top

In order to get a better insight in how the metallic species behave inside the biological systems, it is necessary to study their coordination behavior with biomolecules i.e. ligands having hetero-donor oxygen and nitrogen atoms (Pellerito & Nagy, 2002). Therefore, the title compound (I) has been prepared for the study of complexation with different metals.

The title compound is the structural isomer of 3-(3,5-dichloroanilinocarbonyl) propionic acid (Shah et al., 2008). Due to the change of chloro substitution, the packing of the title compound has been changed. In this structure there does not exist any kind of π-interaction. The dimeric nature and the linkage of the dimers in title compound is in agreement with the reported structural isomer. In (I) the C==O bond distances for carboxylate and carbonyl group have values of (C10==O2: 1.236 (3) Å) and (C7==O3: 1.214 (3) Å), and in comparison to 1.219 (3) and 1.225 (2) Å, respectively. The C—N bond distances are compareable within experimental errors. In both compounds similar intermolecular H-bonding (Table 2, Fig. 2) has been observed. The dihedral angle between the aromatic ring (C1—C6) and (C8—C10/O1/O2) have a value of 20.45 (20)°, whereas with (C1/N1/C7/O3) its value is 39.02 (16)°. The value of dihedral angle between (C8—C10/O1/O2) and (C1/N1/C7/O3) is 18.69 (18)°. There exist an intramolecular H-bond of C—H···O type and completes a six-membered heterocyclic ring adjacent to the benzene ring. There does not exist any kind of π-interactions.

Related literature top

For a related structure, see: Shah et al. (2008). For background, see: Pellerito & Nagy (2002). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

3,4-dichloroanilline (16.2 g, 0.1 mol) and succinic anhydride (10 g, 0.1 mole) were mixed in glacial acetic acid and stirred overnight. The solution was filtered and precipitated material was washed with distilled water. The acid formed was recrystallized from acetone to yield colourless blocks of (I). (Yield: 80%).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown by small spheres of arbitrary radius. The dashed lines represent the intramolecular H-bonds.
	Fig. 2. The partial unit cell packing of (I) showing the dimeric nature and the linkage of dimers along the a axis.

3-[(3,4-Dichlorophenyl)aminocarbonyl]propionic acid top

Crystal data top

C₁₀H₉Cl₂NO₃	F(000) = 536
M_r = 262.08	D_x = 1.548 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2912 reflections
a = 4.8441 (4) Å	θ = 2.7–28.9°
b = 10.3388 (10) Å	µ = 0.57 mm⁻¹
c = 22.457 (2) Å	T = 296 K
β = 90.613 (3)°	Block, colourless
V = 1124.62 (17) Å³	0.25 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2912 independent reflections
Radiation source: fine-focus sealed tube	2028 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 7.5 pixels mm^-1	θ_max = 28.9°, θ_min = 2.7°
ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −13→13
T_min = 0.925, T_max = 0.949	l = −30→30
11915 measured reflections

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.182	Only H-atom coordinates refined
S = 1.05	w = 1/[σ²(F_o²) + (0.0667P)² + 1.6338P] where P = (F_o² + 2F_c²)/3
2912 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.89 e Å⁻³
0 restraints	Δρ_min = −0.84 e Å⁻³

Crystal data top

C₁₀H₉Cl₂NO₃	V = 1124.62 (17) Å³
M_r = 262.08	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.8441 (4) Å	µ = 0.57 mm⁻¹
b = 10.3388 (10) Å	T = 296 K
c = 22.457 (2) Å	0.25 × 0.12 × 0.10 mm
β = 90.613 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2912 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2028 reflections with I > 3σ(I)
T_min = 0.925, T_max = 0.949	R_int = 0.028
11915 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.182	Only H-atom coordinates refined
S = 1.05	Δρ_max = 0.89 e Å⁻³
2912 reflections	Δρ_min = −0.84 e Å⁻³
172 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.2707 (3)	0.56808 (11)	0.26822 (5)	0.0954 (5)
Cl2	0.6942 (3)	0.37607 (10)	0.20648 (6)	0.0945 (5)
O1	0.7844 (5)	1.3991 (2)	−0.01026 (13)	0.0584 (9)
O2	0.4038 (4)	1.3685 (2)	0.04204 (12)	0.0551 (8)
O3	0.9245 (4)	0.9675 (2)	0.08819 (12)	0.0546 (8)
N1	0.4948 (5)	0.9009 (2)	0.11088 (11)	0.0372 (7)
C1	0.5572 (5)	0.7772 (3)	0.13420 (12)	0.0341 (8)
C2	0.4079 (7)	0.7353 (3)	0.18269 (14)	0.0427 (9)
C3	0.4538 (8)	0.6133 (3)	0.20585 (14)	0.0500 (10)
C4	0.6432 (8)	0.5320 (3)	0.18016 (16)	0.0543 (11)
C5	0.7934 (8)	0.5742 (3)	0.13222 (18)	0.0568 (11)
C6	0.7517 (7)	0.6968 (3)	0.10907 (15)	0.0448 (9)
C7	0.6785 (5)	0.9883 (3)	0.09118 (12)	0.0345 (8)
C8	0.5505 (6)	1.1164 (3)	0.07282 (17)	0.0438 (9)
C9	0.7506 (6)	1.2040 (3)	0.04237 (17)	0.0437 (9)
C10	0.6312 (5)	1.3316 (3)	0.02430 (13)	0.0384 (8)
H1N	0.334 (7)	0.922 (3)	0.1111 (15)	0.0447*
H1O	0.722 (9)	1.470 (4)	−0.0157 (19)	0.0701*
H2	0.278 (7)	0.793 (4)	0.2003 (15)	0.0513*
H5	0.939 (8)	0.518 (4)	0.1166 (17)	0.0680*
H6	0.846 (7)	0.722 (4)	0.0777 (16)	0.0537*
H8A	0.489 (8)	1.153 (4)	0.1063 (16)	0.0527*
H8B	0.377 (8)	1.101 (3)	0.0478 (15)	0.0527*
H9A	0.899 (7)	1.225 (4)	0.0680 (16)	0.0523*
H9B	0.840 (7)	1.164 (4)	0.0077 (16)	0.0523*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1600 (13)	0.0566 (6)	0.0704 (7)	−0.0127 (7)	0.0418 (7)	0.0207 (5)
Cl2	0.1284 (11)	0.0363 (5)	0.1187 (10)	0.0107 (6)	−0.0093 (8)	0.0277 (5)
O1	0.0476 (13)	0.0356 (12)	0.0924 (19)	0.0084 (10)	0.0234 (12)	0.0257 (12)
O2	0.0400 (11)	0.0410 (12)	0.0846 (17)	0.0114 (9)	0.0176 (11)	0.0226 (11)
O3	0.0251 (10)	0.0418 (12)	0.0969 (18)	0.0059 (8)	0.0058 (10)	0.0219 (12)
N1	0.0260 (10)	0.0317 (12)	0.0541 (14)	0.0044 (9)	0.0040 (10)	0.0114 (10)
C1	0.0337 (13)	0.0263 (12)	0.0423 (14)	−0.0008 (10)	−0.0030 (10)	0.0043 (10)
C2	0.0540 (17)	0.0294 (13)	0.0449 (16)	−0.0031 (12)	0.0066 (13)	0.0006 (12)
C3	0.073 (2)	0.0331 (15)	0.0440 (16)	−0.0104 (14)	0.0021 (15)	0.0056 (12)
C4	0.072 (2)	0.0276 (14)	0.063 (2)	0.0001 (14)	−0.0119 (17)	0.0098 (14)
C5	0.059 (2)	0.0345 (16)	0.077 (2)	0.0123 (15)	0.0027 (18)	0.0006 (16)
C6	0.0445 (16)	0.0358 (15)	0.0542 (18)	0.0066 (12)	0.0086 (13)	0.0038 (13)
C7	0.0279 (12)	0.0302 (13)	0.0455 (14)	0.0028 (10)	0.0029 (10)	0.0078 (11)
C8	0.0307 (14)	0.0320 (14)	0.069 (2)	0.0075 (11)	0.0112 (13)	0.0165 (14)
C9	0.0319 (14)	0.0315 (14)	0.068 (2)	0.0042 (11)	0.0091 (13)	0.0137 (13)
C10	0.0305 (13)	0.0305 (13)	0.0543 (16)	0.0010 (10)	0.0021 (11)	0.0090 (12)

Geometric parameters (Å, º) top

Cl1—C3	1.730 (4)	C4—C5	1.377 (5)
Cl2—C4	1.734 (3)	C5—C6	1.384 (5)
O1—C10	1.286 (4)	C7—C8	1.518 (4)
O2—C10	1.236 (3)	C8—C9	1.497 (5)
O3—C7	1.214 (3)	C9—C10	1.495 (4)
O1—H1O	0.80 (4)	C2—H2	0.96 (4)
N1—C1	1.414 (4)	C5—H5	0.98 (4)
N1—C7	1.346 (4)	C6—H6	0.88 (4)
N1—H1N	0.81 (3)	C8—H8A	0.90 (4)
C1—C6	1.382 (4)	C8—H8B	1.02 (4)
C1—C2	1.383 (4)	C9—H9A	0.94 (4)
C2—C3	1.382 (4)	C9—H9B	0.99 (4)
C3—C4	1.376 (5)

C10—O1—H1O	112 (3)	C8—C9—C10	114.0 (2)
C1—N1—C7	126.1 (2)	O1—C10—O2	123.3 (3)
C7—N1—H1N	117 (2)	O1—C10—C9	114.8 (2)
C1—N1—H1N	116 (2)	O2—C10—C9	121.9 (3)
N1—C1—C6	122.5 (3)	C1—C2—H2	119 (2)
N1—C1—C2	117.6 (3)	C3—C2—H2	121 (2)
C2—C1—C6	119.9 (3)	C4—C5—H5	119 (2)
C1—C2—C3	119.9 (3)	C6—C5—H5	121 (2)
Cl1—C3—C2	118.0 (3)	C1—C6—H6	121 (3)
C2—C3—C4	120.4 (3)	C5—C6—H6	120 (3)
Cl1—C3—C4	121.6 (3)	C7—C8—H8A	106 (3)
C3—C4—C5	119.7 (3)	C7—C8—H8B	110.2 (18)
Cl2—C4—C5	119.1 (3)	C9—C8—H8A	111 (3)
Cl2—C4—C3	121.2 (3)	C9—C8—H8B	112.2 (19)
C4—C5—C6	120.5 (3)	H8A—C8—H8B	104 (3)
C1—C6—C5	119.7 (3)	C8—C9—H9A	111 (2)
O3—C7—N1	123.5 (3)	C8—C9—H9B	114 (2)
O3—C7—C8	122.6 (3)	C10—C9—H9A	105 (2)
N1—C7—C8	113.9 (2)	C10—C9—H9B	109 (2)
C7—C8—C9	112.8 (2)	H9A—C9—H9B	104 (3)

C7—N1—C1—C2	140.0 (3)	Cl1—C3—C4—C5	−177.0 (3)
C7—N1—C1—C6	−42.4 (4)	C2—C3—C4—Cl2	−177.3 (3)
C1—N1—C7—O3	4.2 (5)	C2—C3—C4—C5	2.0 (5)
C1—N1—C7—C8	−175.8 (3)	Cl2—C4—C5—C6	178.1 (3)
N1—C1—C2—C3	177.7 (3)	C3—C4—C5—C6	−1.2 (6)
C6—C1—C2—C3	0.0 (5)	C4—C5—C6—C1	−0.2 (5)
N1—C1—C6—C5	−176.8 (3)	O3—C7—C8—C9	9.0 (5)
C2—C1—C6—C5	0.8 (5)	N1—C7—C8—C9	−171.0 (3)
C1—C2—C3—Cl1	177.6 (2)	C7—C8—C9—C10	−179.4 (3)
C1—C2—C3—C4	−1.4 (5)	C8—C9—C10—O1	−169.1 (3)
Cl1—C3—C4—Cl2	3.7 (5)	C8—C9—C10—O2	11.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3ⁱ	0.81 (3)	2.10 (3)	2.887 (3)	165 (3)
O1—H1O···O2ⁱⁱ	0.80 (4)	1.87 (4)	2.665 (3)	170 (4)
C6—H6···O3	0.88 (4)	2.58 (4)	2.960 (4)	107 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₉Cl₂NO₃
M_r	262.08
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	4.8441 (4), 10.3388 (10), 22.457 (2)
β (°)	90.613 (3)
V (Å³)	1124.62 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.57
Crystal size (mm)	0.25 × 0.12 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.925, 0.949
No. of measured, independent and observed [I > 3σ(I)] reflections	11915, 2912, 2028
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.679

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.182, 1.05
No. of reflections	2912
No. of parameters	172
H-atom treatment	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	0.89, −0.84

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3ⁱ	0.81 (3)	2.10 (3)	2.887 (3)	165 (3)
O1—H1O···O2ⁱⁱ	0.80 (4)	1.87 (4)	2.665 (3)	170 (4)
C6—H6···O3	0.88 (4)	2.58 (4)	2.960 (4)	107 (3)

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

Acknowledgements

The authors acknowledge the the Higher Education Commission, Islamabad, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore. S. Ali is also grateful to the PSF for financial support under project No. PSF/R&D/C–QU/Chem(270).

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