2-(4-Chloro­benzamido)­acetic acid

Khan, I.U.; Khan, M.H.; Arshad, M.N.; Akkurt, M.

doi:10.1107/S1600536811009536

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o916

doi:10.1107/S1600536811009536

Open

access

2-(4-Chlorobenzamido)acetic acid

Islam Ullah Khan,^a ^* Muneeb Hayat Khan,^a Muhammad Nadeem Arshad ^a and Mehmet Akkurt ^b ^*

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan, and ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey
^*Correspondence e-mail: iukhan@gcu.edu.pk, akkurt@erciyes.edu.tr

(Received 11 March 2011; accepted 13 March 2011; online 19 March 2011)

In the crystal structure of the title molecule, C₉H₈ClNO₃, adjacent molecules are arranged into centrosymmetric dimers through pairs of intermolecular O—H⋯O interactions. Intermolecular N—H⋯O hydrogen bonds link the dimers into a layer parallel to the bc plane. In the layer, molecules are packed in a face-to-face π-stacked arrangment, showing π–π stacking interactions between the benzene rings with a centroid–centroid distance of 3.6884 (8) Å.

Related literature

For crystallographic studies of benzamide derivatives, see: Donnelly et al. (2008 ); Mugnoli et al. (1991 ); Stensland et al. (1995 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₈ClNO₃
M_r = 213.61
Monoclinic, P 2₁ /c
a = 10.5035 (2) Å
b = 13.2105 (4) Å
c = 7.1226 (2) Å
β = 102.203 (1)°
V = 965.98 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 296 K
0.36 × 0.21 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer
9027 measured reflections
2365 independent reflections
1627 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.098
S = 1.02
2365 reflections
133 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.83 (2)	2.06 (2)	2.8491 (19)	160 (2)
O3—H1O⋯O1ⁱⁱ	0.83 (1)	1.85 (2)	2.6613 (16)	165 (2)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1.

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 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811009536/is2688sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811009536/is2688Isup2.hkl

checkCIF report

Comment top

Benzamide is originally a derivative of benzoic acid. Some benzamide derivatives are in use as Analgesics (Ethenzamide, Salicylamide), Antiemetics/Prokinetics (Alizapride, Bromopride, Cinitapride, Cisapride, Clebopride) and Antipsychotics (Amisulpride, Nemonapride, Remoxipride, Sulpiride, Sultopride). Other benzamides are being prepared and there crystallographic studies are done (Donnelly et al., 2008; Stensland et al., 1995; Mugnoli et al., 1991). The given benzamide derivative was prepared using the simple route using water as solvent.

In the title compound (I), (Fig. 1), the bond lengths and bond angles are in agreement with those reported in the literature (Allen et al., 1987). The C1—C6—C7—O1, C1—C6—C7—N1, O1—C7—N1—C8, N1—C8—C9—O2 and N1—C8—C9—O3 torsion angles are 20.2 (2), -159.08 (14), -3.2 (2), 17.7 (2) and -163.65 (14)°, respectively.

In the crystal structure, the molecules adopt a face-to-face π-stacked packing arrangement showing π–π stacking interactions involving the benzene rings [Cg1···Cg1ⁱ = 3.6884 (8) Å; symmetry code: (i) x, 3/2 - y, -1/2 + z; Cg1 is a centroid of the benzene ring (C1–C6)].

Related literature top

For crystallographic studies of benzamide derivatives, see: Donnelly et al. (2008); Mugnoli et al. (1991); Stensland et al. (1995). For standard bond lengths, see: Allen et al. (1987).

Experimental top

The calculated amount of glycine (0.5 g, 6.494 mmol) was carefully weighed and transferred to R.B.F (50 ml) containing 10 ml of distilled water. The pH of the water was maintained at 8 with 10% Sod. Carbonate solution which results in the complete dissolution of glycine. Then 4-chlorobenzoyl chloride (0.83 ml, 6.494 mmol) was added and pH was maintained at 8. After 3.5 h the TLC showed the completion of reaction giving a single spot of the product. The reaction mixture was then acidified with 3 N HCl up to pH 3 which resulted in the insoluble precipitate formation. Precipitates were filtered, washed, dried and then crystallized in methanol.

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 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The title molecule with atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
	Fig. 2. View of the centrosymmetric dimers forming through a pair of O—H···O interactions which are connected to each other through intermolecular N—H···O interactions. Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.

2-(4-Chlorobenzamido)acetic acid top

Crystal data top

C₉H₈ClNO₃	F(000) = 440
M_r = 213.61	D_x = 1.469 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3071 reflections
a = 10.5035 (2) Å	θ = 2.5–26.5°
b = 13.2105 (4) Å	µ = 0.37 mm⁻¹
c = 7.1226 (2) Å	T = 296 K
β = 102.203 (1)°	Needle, colourless
V = 965.98 (4) Å³	0.36 × 0.21 × 0.13 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1627 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 28.3°, θ_min = 3.3°
ϕ and ω scans	h = −13→13
9027 measured reflections	k = −17→17
2365 independent reflections	l = −9→9

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0427P)² + 0.1658P] where P = (F_o² + 2F_c²)/3
2365 reflections	(Δ/σ)_max = 0.001
133 parameters	Δρ_max = 0.21 e Å⁻³
2 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₉H₈ClNO₃	V = 965.98 (4) Å³
M_r = 213.61	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.5035 (2) Å	µ = 0.37 mm⁻¹
b = 13.2105 (4) Å	T = 296 K
c = 7.1226 (2) Å	0.36 × 0.21 × 0.13 mm
β = 102.203 (1)°

Data collection top

Bruker APEXII CCD diffractometer	1627 reflections with I > 2σ(I)
9027 measured reflections	R_int = 0.028
2365 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	2 restraints
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.21 e Å⁻³
2365 reflections	Δρ_min = −0.25 e Å⁻³
133 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 on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	1.15861 (4)	0.81838 (4)	0.19567 (7)	0.0678 (2)
O1	0.65691 (11)	0.52525 (8)	0.26411 (16)	0.0518 (4)
O2	0.46720 (11)	0.64368 (9)	0.49155 (17)	0.0576 (4)
O3	0.31367 (11)	0.53263 (9)	0.37136 (17)	0.0519 (4)
N1	0.53959 (13)	0.65903 (11)	0.1375 (2)	0.0515 (5)
C1	0.88594 (15)	0.60968 (12)	0.1921 (2)	0.0457 (5)
C2	1.00353 (16)	0.65563 (13)	0.1908 (2)	0.0499 (6)
C3	1.00957 (15)	0.75964 (13)	0.1880 (2)	0.0453 (5)
C4	0.90087 (16)	0.81827 (12)	0.1838 (2)	0.0465 (5)
C5	0.78344 (15)	0.77170 (11)	0.1832 (2)	0.0423 (5)
C6	0.77497 (14)	0.66710 (11)	0.1887 (2)	0.0379 (4)
C7	0.65311 (14)	0.61215 (11)	0.2002 (2)	0.0407 (5)
C8	0.41924 (16)	0.61044 (15)	0.1527 (2)	0.0539 (6)
C9	0.40478 (14)	0.59869 (11)	0.3568 (2)	0.0411 (5)
H1	0.88100	0.53940	0.19530	0.0550*
H1N	0.538 (2)	0.7167 (13)	0.092 (3)	0.0810*
H1O	0.315 (2)	0.5241 (19)	0.487 (2)	0.1020*
H2	1.07760	0.61690	0.19170	0.0600*
H4	0.90650	0.88850	0.18130	0.0560*
H5	0.70930	0.81080	0.17910	0.0510*
H8A	0.41540	0.54410	0.09330	0.0650*
H8B	0.34680	0.65000	0.08250	0.0650*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0478 (3)	0.0785 (4)	0.0752 (3)	−0.0209 (2)	0.0086 (2)	−0.0017 (2)
O1	0.0541 (7)	0.0422 (7)	0.0616 (7)	0.0003 (5)	0.0180 (5)	0.0100 (5)
O2	0.0571 (8)	0.0578 (7)	0.0566 (7)	−0.0178 (6)	0.0089 (6)	−0.0106 (6)
O3	0.0439 (6)	0.0499 (7)	0.0600 (7)	−0.0122 (5)	0.0067 (5)	0.0017 (6)
N1	0.0389 (8)	0.0556 (9)	0.0604 (9)	0.0027 (6)	0.0113 (6)	0.0169 (7)
C1	0.0449 (9)	0.0391 (8)	0.0547 (9)	0.0039 (7)	0.0141 (7)	0.0045 (7)
C2	0.0392 (9)	0.0546 (10)	0.0566 (10)	0.0065 (7)	0.0119 (7)	0.0016 (7)
C3	0.0414 (9)	0.0532 (10)	0.0401 (8)	−0.0082 (7)	0.0060 (6)	−0.0003 (7)
C4	0.0524 (10)	0.0391 (8)	0.0461 (9)	−0.0040 (7)	0.0061 (7)	0.0011 (7)
C5	0.0431 (9)	0.0409 (8)	0.0425 (8)	0.0065 (6)	0.0081 (6)	0.0036 (6)
C6	0.0395 (8)	0.0407 (8)	0.0338 (7)	0.0019 (6)	0.0084 (6)	0.0048 (6)
C7	0.0435 (9)	0.0406 (9)	0.0394 (8)	0.0018 (6)	0.0117 (6)	0.0035 (6)
C8	0.0374 (9)	0.0698 (12)	0.0530 (10)	−0.0044 (8)	0.0065 (7)	−0.0001 (8)
C9	0.0300 (8)	0.0351 (8)	0.0568 (9)	0.0026 (6)	0.0062 (7)	−0.0004 (7)

Geometric parameters (Å, º) top

Cl1—C3	1.7377 (17)	C3—C4	1.375 (2)
O1—C7	1.2325 (18)	C4—C5	1.378 (2)
O2—C9	1.1993 (19)	C5—C6	1.386 (2)
O3—C9	1.3153 (19)	C6—C7	1.489 (2)
O3—H1O	0.829 (14)	C8—C9	1.501 (2)
N1—C8	1.442 (2)	C1—H1	0.9300
N1—C7	1.334 (2)	C2—H2	0.9300
N1—H1N	0.827 (18)	C4—H4	0.9300
C1—C2	1.378 (2)	C5—H5	0.9300
C1—C6	1.387 (2)	C8—H8A	0.9700
C2—C3	1.376 (2)	C8—H8B	0.9700

C9—O3—H1O	108.0 (16)	N1—C8—C9	112.86 (13)
C7—N1—C8	120.26 (14)	O2—C9—O3	123.33 (14)
C7—N1—H1N	120.1 (15)	O2—C9—C8	125.00 (14)
C8—N1—H1N	119.6 (15)	O3—C9—C8	111.66 (13)
C2—C1—C6	120.68 (15)	C2—C1—H1	120.00
C1—C2—C3	118.96 (15)	C6—C1—H1	120.00
C2—C3—C4	121.49 (15)	C1—C2—H2	120.00
Cl1—C3—C2	119.31 (13)	C3—C2—H2	121.00
Cl1—C3—C4	119.18 (13)	C3—C4—H4	120.00
C3—C4—C5	119.17 (15)	C5—C4—H4	120.00
C4—C5—C6	120.53 (14)	C4—C5—H5	120.00
C1—C6—C5	119.16 (14)	C6—C5—H5	120.00
C1—C6—C7	117.49 (13)	N1—C8—H8A	109.00
C5—C6—C7	123.29 (14)	N1—C8—H8B	109.00
N1—C7—C6	118.25 (13)	C9—C8—H8A	109.00
O1—C7—N1	120.86 (14)	C9—C8—H8B	109.00
O1—C7—C6	120.89 (13)	H8A—C8—H8B	108.00

C8—N1—C7—C6	−177.54 (13)	C3—C4—C5—C6	0.6 (2)
C7—N1—C8—C9	67.7 (2)	C4—C5—C6—C7	176.22 (13)
C8—N1—C7—O1	3.2 (2)	C4—C5—C6—C1	−0.9 (2)
C2—C1—C6—C7	−177.03 (13)	C1—C6—C7—O1	20.2 (2)
C2—C1—C6—C5	0.3 (2)	C1—C6—C7—N1	−159.08 (14)
C6—C1—C2—C3	0.6 (2)	C5—C6—C7—O1	−156.98 (14)
C1—C2—C3—Cl1	177.54 (11)	C5—C6—C7—N1	23.8 (2)
C1—C2—C3—C4	−0.9 (2)	N1—C8—C9—O2	16.7 (2)
Cl1—C3—C4—C5	−178.18 (11)	N1—C8—C9—O3	−163.65 (14)
C2—C3—C4—C5	0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.83 (2)	2.06 (2)	2.8491 (19)	160 (2)
O3—H1O···O1ⁱⁱ	0.83 (1)	1.85 (2)	2.6613 (16)	165 (2)

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

Experimental details

Crystal data
Chemical formula	C₉H₈ClNO₃
M_r	213.61
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.5035 (2), 13.2105 (4), 7.1226 (2)
β (°)	102.203 (1)
V (Å³)	965.98 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.36 × 0.21 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9027, 2365, 1627
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.098, 1.02
No. of reflections	2365
No. of parameters	133
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.25

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), 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···O2ⁱ	0.827 (18)	2.060 (18)	2.8491 (19)	160 (2)
O3—H1O···O1ⁱⁱ	0.829 (14)	1.853 (16)	2.6613 (16)	165 (2)

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

Acknowledgements

The authors are grateful to the Higher Education Commission (HEC), Pakistan, for providing funds for the single-crystal XRD facilities at GC University, Lahore.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Donnelly, K., Gallagher, J. F. & Lough, A. J. (2008). Acta Cryst. C64, o335–o340. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Mugnoli, A., Carnasciali, M. M., Sancassan, F., Novi, M. & Petrillo, G. (1991). Acta Cryst. C47, 1916–1919. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stensland, B., Csöregh, I. & Högberg, T. (1995). Acta Cryst. B51, 847–856. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar