2-Amino-4-chloro­benzoic acid

Farag, A.M.; Teoh, S.G.; Osman, H.; Yeap, C.S.; Fun, H.-K.

doi:10.1107/S1600536810050166

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o37

https://doi.org/10.1107/S1600536810050166

Open

access

2-Amino-4-chlorobenzoic acid

Abeer Mohamed Farag,^a Siang Guan Teoh,^a Hasnah Osman,^a Chin Sing Yeap ^b ‡ and Hoong-Kun Fun ^b ^*§

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 23 November 2010; accepted 1 December 2010; online 4 December 2010)

The title compound, C₇H₆ClNO₂, is almost planar, with an r.m.s. deviation of 0.040 Å. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, molecules are linked into centrosymmetric dimers by pairs of O—H⋯O hydrogen bonds. These dimers are stacked along [010].

Related literature

For the pharmacological properties of quinazolinone derivatives, see: Prakash Naik et al. (2009 ); Bembenek et al. (2010 ); Miller et al. (2010 ); Sikorska et al. (1998 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₇H₆ClNO₂
M_r = 171.58
Monoclinic, C 2/c
a = 15.4667 (10) Å
b = 3.7648 (2) Å
c = 23.7598 (15) Å
β = 93.015 (3)°
V = 1381.59 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 100 K
0.53 × 0.17 × 0.05 mm

Data collection

Bruker APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.780, T_max = 0.975
34764 measured reflections
3645 independent reflections
3175 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.089
S = 1.07
3645 reflections
112 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯O1ⁱ	0.853 (16)	1.787 (16)	2.6354 (8)	173.0 (16)
N1—H1N1⋯O1	0.851 (15)	2.102 (14)	2.6918 (9)	126.0 (13)
Symmetry code: (i) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810050166/hb5757sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810050166/hb5757Isup2.hkl

checkCIF report

Comment top

Anthranilic acid is required as a starting compound to prepare quinoline derivatives. Quinazolinones are well known as biologically active compounds. Quinazolinones have been studied for their interesting pharmacological properties such as analgesic, antiinflammatory, antibacterial, anticonvulsant, antihypertensive, antimalarial, anticancer activities and as treatment of diabetic complications such as cataracts, nephropathy and neuropathy (Prakash Naik et al., 2009), as well as used as prolyl hydroxylase inhibitors (Bembenek et al., 2010) and antibacterial drugs (Miller et al., 2010). New complexes have been prepared from 2-amino-4-chlorobenzoic acid by Sikorska et al., (1998).

The title compound (Fig. 1) is almost planar with maximum deviation of 0.097 (1) Å at atom O1. An intramolecular N1—H1N1···O1 hydrogen bond generates S(6) ring motif (Bernstein et al., 1995). In the crystal, the molecules are linked into centrosymmetric dimers by O2—H1O2···O1 hydrogen bonds and these dimers are stacked down b axis (Fig. 2, Table 1).

Related literature top

For the pharmacological activity of quinazolinone derivatives, see: Prakash Naik et al. (2009); Bembenek et al. (2010); Miller et al. (2010); Sikorska et al. (1998). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

The attempt to prepare the Schiff base ligand by stirring 2-amino-4-chlorobenzoic acid (1 mol) and salicyldehyde (1 mol) together at 70 °C for 3 h in 10 ml of ethanol was unsuccessful. The resulting orange solution was filtered and orange needles were formed after a few days of slow evaporation of the solvent at room temperature. Unfortunately, the crystals were that of the starting material (2-amino-4-chlorobenzoic acid) with melting point 119 °C.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of title compound with 50% probability ellipsoids for non-H atoms.
	Fig. 2. The crystal packing of title compound viewed down b axis, showing the molecules are linked into dimers.

2-Amino-4-chlorobenzoic acid top

Crystal data top

C₇H₆ClNO₂	F(000) = 704
M_r = 171.58	D_x = 1.650 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9945 reflections
a = 15.4667 (10) Å	θ = 2.6–37.5°
b = 3.7648 (2) Å	µ = 0.49 mm⁻¹
c = 23.7598 (15) Å	T = 100 K
β = 93.015 (3)°	Needle, orange
V = 1381.59 (14) Å³	0.53 × 0.17 × 0.05 mm
Z = 8

Data collection top

Bruker APEXII DUO CCD diffractometer	3645 independent reflections
Radiation source: fine-focus sealed tube	3175 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
φ and ω scans	θ_max = 37.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −26→26
T_min = 0.780, T_max = 0.975	k = −6→6
34764 measured reflections	l = −38→40

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0479P)² + 0.5195P] where P = (F_o² + 2F_c²)/3
3645 reflections	(Δ/σ)_max = 0.001
112 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₇H₆ClNO₂	V = 1381.59 (14) Å³
M_r = 171.58	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 15.4667 (10) Å	µ = 0.49 mm⁻¹
b = 3.7648 (2) Å	T = 100 K
c = 23.7598 (15) Å	0.53 × 0.17 × 0.05 mm
β = 93.015 (3)°

Data collection top

Bruker APEXII DUO CCD diffractometer	3645 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3175 reflections with I > 2σ(I)
T_min = 0.780, T_max = 0.975	R_int = 0.035
34764 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.55 e Å⁻³
3645 reflections	Δρ_min = −0.21 e Å⁻³
112 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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) top

	x	y	z	U_iso*/U_eq
Cl1	0.400495 (11)	0.03406 (5)	0.207389 (8)	0.02000 (6)
O1	0.01970 (4)	0.31432 (19)	0.06195 (2)	0.02250 (12)
O2	0.11545 (4)	0.57721 (19)	0.00817 (2)	0.02167 (12)
N1	0.07764 (4)	0.0546 (2)	0.16254 (3)	0.02152 (13)
C1	0.15675 (4)	0.1453 (2)	0.14497 (3)	0.01451 (11)
C2	0.23039 (4)	0.0671 (2)	0.18024 (3)	0.01549 (12)
H2A	0.2241	−0.0407	0.2150	0.019*
C3	0.31151 (4)	0.1502 (2)	0.16319 (3)	0.01506 (11)
C4	0.32545 (4)	0.3164 (2)	0.11206 (3)	0.01691 (12)
H4A	0.3810	0.3700	0.1015	0.020*
C5	0.25346 (4)	0.3983 (2)	0.07761 (3)	0.01614 (12)
H5A	0.2610	0.5113	0.0434	0.019*
C6	0.16899 (4)	0.31592 (19)	0.09275 (3)	0.01417 (11)
C7	0.09544 (5)	0.4008 (2)	0.05369 (3)	0.01611 (12)
H1O2	0.0692 (10)	0.603 (5)	−0.0126 (7)	0.038 (4)*
H1N1	0.0309 (10)	0.083 (4)	0.1425 (6)	0.034 (4)*
H2N1	0.0757 (11)	−0.069 (5)	0.1911 (7)	0.042 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01555 (8)	0.02243 (10)	0.02140 (9)	0.00327 (6)	−0.00502 (6)	−0.00029 (6)
O1	0.0145 (2)	0.0335 (3)	0.0191 (2)	−0.0014 (2)	−0.00278 (17)	0.0055 (2)
O2	0.0174 (2)	0.0316 (3)	0.0157 (2)	−0.0006 (2)	−0.00240 (18)	0.0067 (2)
N1	0.0141 (2)	0.0308 (4)	0.0196 (3)	−0.0016 (2)	0.0007 (2)	0.0075 (3)
C1	0.0134 (2)	0.0150 (3)	0.0150 (2)	0.0001 (2)	−0.00005 (19)	0.0001 (2)
C2	0.0147 (3)	0.0169 (3)	0.0146 (2)	0.0013 (2)	−0.0012 (2)	0.0011 (2)
C3	0.0136 (2)	0.0155 (3)	0.0158 (2)	0.0016 (2)	−0.00237 (19)	−0.0019 (2)
C4	0.0134 (2)	0.0203 (3)	0.0169 (3)	−0.0005 (2)	−0.0001 (2)	−0.0009 (2)
C5	0.0152 (3)	0.0187 (3)	0.0144 (2)	−0.0007 (2)	0.0000 (2)	−0.0002 (2)
C6	0.0139 (2)	0.0154 (3)	0.0130 (2)	0.0005 (2)	−0.00089 (19)	−0.0004 (2)
C7	0.0159 (3)	0.0183 (3)	0.0140 (2)	0.0013 (2)	−0.00138 (19)	−0.0003 (2)

Geometric parameters (Å, º) top

Cl1—C3	1.7425 (7)	C2—C3	1.3746 (10)
O1—C7	1.2415 (9)	C2—H2A	0.9300
O2—C7	1.3197 (9)	C3—C4	1.3933 (10)
O2—H1O2	0.854 (16)	C4—C5	1.3816 (10)
N1—C1	1.3572 (9)	C4—H4A	0.9300
N1—H1N1	0.851 (16)	C5—C6	1.4078 (9)
N1—H2N1	0.826 (17)	C5—H5A	0.9300
C1—C2	1.4093 (10)	C6—C7	1.4651 (10)
C1—C6	1.4185 (9)

C7—O2—H1O2	107.8 (11)	C5—C4—C3	117.38 (6)
C1—N1—H1N1	123.2 (10)	C5—C4—H4A	121.3
C1—N1—H2N1	117.9 (12)	C3—C4—H4A	121.3
H1N1—N1—H2N1	117.7 (15)	C4—C5—C6	121.95 (7)
N1—C1—C2	118.55 (6)	C4—C5—H5A	119.0
N1—C1—C6	123.17 (6)	C6—C5—H5A	119.0
C2—C1—C6	118.28 (6)	C5—C6—C1	119.45 (6)
C3—C2—C1	119.92 (6)	C5—C6—C7	119.34 (6)
C3—C2—H2A	120.0	C1—C6—C7	121.20 (6)
C1—C2—H2A	120.0	O1—C7—O2	121.70 (7)
C2—C3—C4	123.01 (6)	O1—C7—C6	123.38 (7)
C2—C3—Cl1	118.00 (5)	O2—C7—C6	114.92 (6)
C4—C3—Cl1	118.99 (5)

N1—C1—C2—C3	178.90 (7)	N1—C1—C6—C5	−179.53 (8)
C6—C1—C2—C3	−1.19 (11)	C2—C1—C6—C5	0.57 (11)
C1—C2—C3—C4	0.96 (12)	N1—C1—C6—C7	−0.92 (12)
C1—C2—C3—Cl1	−177.87 (6)	C2—C1—C6—C7	179.18 (7)
C2—C3—C4—C5	−0.05 (12)	C5—C6—C7—O1	174.64 (7)
Cl1—C3—C4—C5	178.77 (6)	C1—C6—C7—O1	−3.97 (12)
C3—C4—C5—C6	−0.59 (12)	C5—C6—C7—O2	−5.06 (11)
C4—C5—C6—C1	0.33 (11)	C1—C6—C7—O2	176.34 (7)
C4—C5—C6—C7	−178.31 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O1ⁱ	0.853 (16)	1.787 (16)	2.6354 (8)	173.0 (16)
N1—H1N1···O1	0.851 (15)	2.102 (14)	2.6918 (9)	126.0 (13)

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₇H₆ClNO₂
M_r	171.58
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	15.4667 (10), 3.7648 (2), 23.7598 (15)
β (°)	93.015 (3)
V (Å³)	1381.59 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.53 × 0.17 × 0.05

Data collection
Diffractometer	Bruker APEXII DUO CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.780, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	34764, 3645, 3175
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.857

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.089, 1.07
No. of reflections	3645
No. of parameters	112
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.21

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O1ⁱ	0.853 (16)	1.787 (16)	2.6354 (8)	173.0 (16)
N1—H1N1···O1	0.851 (15)	2.102 (14)	2.6918 (9)	126.0 (13)

Symmetry code: (i) −x, −y+1, −z.

Footnotes

‡Thomson Reuters ResearcherID: A-5523-2009.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the RU research grant (815002). AMF thanks the Libyan Government for providing a scholarship. HKF and CSY thank USM for the Research University Grant No. 1001/PFIZIK/811160.

References

Bembenek, S. D., Hocutt, F. M., Leonard, B. E. Jr, Rabinowitz, M. H., Rosen, M. D., Tarantino, K. T. & Venkatesan, H. (2010). US Patent Appl. 20100204226. Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Miller, J. R., Venkataraman, T., Melnick, M. M., Lall, M., Donovan, C., Sarver, R. W., Lee, D.-Y., Ohren, J. & Emerson, D. (2010). Chem. Biol. Drug Des. 75, 444–454. Web of Science CrossRef CAS PubMed Google Scholar
Prakash Naik, H. R., Bhojya Naik, H. S., Ravikumar Naik, T. R., Raghavendra, M., Aravinda, T. & Lamani, D. S. (2009). Phosphorus Sulfur Silicon Relat. Elem. 184, 460–470. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sikorska, M., Mrozek, R. & Rzqczynska, Z. (1998). J. Therm. Anal. Calorim. 51, 467–475. CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar