3,7-Dichloro­quinoline-8-carboxylic acid

Guo, X.-H.

doi:10.1107/S1600536808026238

organic compounds

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Volume 64| Part 9| September 2008| Page o1786

doi:10.1107/S1600536808026238

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3,7-Dichloroquinoline-8-carboxylic acid

Xin-Hong Guo ^a ^*

^aHuaiyin Teachers College, 111 West Changjiang Road, Huaian 223300, Jiangsu, People's Republic of China
^*Correspondence e-mail: xinhong_guo@hotmail.com

(Received 11 August 2008; accepted 14 August 2008; online 20 August 2008)

The title compound (trade name: quinclorac), C₁₀H₅Cl₂NO₂, was crystallized from a dimethyl sulfoxide solution. Quinclorac molecules are packed mainly via π–π stacking interactions between neighbouring heterocycles (interplanar distance: 3.31 Å) and via O—H⋯N hydrogen bonding.

Related literature

For the use of 3,7-dichloroquinoline-8-carboxylic acid as a herbicide, see: Nuria et al. (1997 ); Pornprom et al. (2006 ); Sunohara & Matsumoto (2004 ); Tresch & Grossmann (2002 ). For related complexes, see: Li et al. (2008 ); Turel et al. (2004 ); Zhang et al. (2007 ).

Experimental

Crystal data

C₁₀H₅Cl₂NO₂
M_r = 242.05
Triclinic, $[P \overline 1]$
a = 7.5002 (12) Å
b = 8.4016 (14) Å
c = 8.732 (3) Å
α = 102.529 (6)°
β = 93.439 (6)°
γ = 116.479 (4)°
V = 472.98 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.66 mm⁻¹
T = 173 (2) K
0.26 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.84, T_max = 0.88
5948 measured reflections
1834 independent reflections
1102 reflections with I > 2σ(I)
R_int = 0.067

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.140
S = 1.01
1834 reflections
139 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1ⁱ	0.84 (5)	1.91 (5)	2.753 (4)	173 (4)
Symmetry code: (i) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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: SHELXL97 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808026238/zl2136sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808026238/zl2136Isup2.hkl

checkCIF report

Comment top

Quinclorac (3,7-dichloroquinoline-8-carboxylic acid) is one of the most effective herbicides (Nuria et al., 1997; Pornprom et al., 2006; Sunohara & Matsumoto, 2004; Tresch & Grossmann, 2002), and is widely used in agriculture. In addition, as a quinolinecarboxylate derivate, quinclorac could chelate metal ions, forming corresponding complexes (Li et al., 2008; Turel et al., 2004; Zhang et al., 2007). As an extension of these studies, we report herein on the structure of quinclorac.

A quinclorac molecule, which is the asymmetric unit of the structure, is shown in Fig. 1. All the bond distances and bond angles of quinclorac are normal and call for no further comment. Two types of intermolecular interations are easily found in the structure of quinclorac (Fig. 2). There exists a π-π interaction between adjacent quinin cycles with an inversion center located halfway between the aromatic rings, thus forming stacks along the a direction. Quinclorac molecules of adjacent chains are joined through H-bonding of O1—H1···N1ⁱ (symmetry code: (i) 1 - x, 2 - y, 1 - z) (Table 1) into a triclinic supramolecular architecture (Fig. 2).

Related literature top

For the use of 3,7-dichloroquinoline-8-carboxylic acid as a herbicide, see: Nuria et al. (1997); Pornprom et al. (2006); Sunohara & Matsumoto (2004); Tresch & Grossmann (2002). For related complexes, see: Li et al. (2008); Turel et al. (2004); Zhang et al. (2007).

Experimental top

Quinclorac was obtained from a commercial source and used directly without further purification. Quinclorac (0.5 mmol, 0.121 g) was dissolved in 10 mL DMSO. After ether vapor slowly diffused into the solution at room temperature for several days, colorless prismlike crystals suitable for crystallographic research were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The asymmetric unit of quinclorac with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Packing diagram of quinclorac showing the π-π stacks along the a direction. Intermolecular H-bonding is indicated via dashed lines.

3,7-Dichloroquinoline-8-carboxylic acid top

Crystal data top

C₁₀H₅Cl₂NO₂	Z = 2
M_r = 242.05	F(000) = 244
Triclinic, P1	D_x = 1.700 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5002 (12) Å	Cell parameters from 958 reflections
b = 8.4016 (14) Å	θ = 2.1–25.5°
c = 8.732 (3) Å	µ = 0.66 mm⁻¹
α = 102.529 (6)°	T = 173 K
β = 93.439 (6)°	Prismlike, colorless
γ = 116.479 (4)°	0.26 × 0.22 × 0.20 mm
V = 472.98 (17) Å³

Data collection top

Bruker SMART APEXII diffractometer	1834 independent reflections
Radiation source: fine-focus sealed tube	1102 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
ω scans	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −9→9
T_min = 0.84, T_max = 0.88	k = −8→10
5948 measured reflections	l = −10→10

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.062P)²] where P = (F_o² + 2F_c²)/3
1834 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₁₀H₅Cl₂NO₂	γ = 116.479 (4)°
M_r = 242.05	V = 472.98 (17) Å³
Triclinic, P1	Z = 2
a = 7.5002 (12) Å	Mo Kα radiation
b = 8.4016 (14) Å	µ = 0.66 mm⁻¹
c = 8.732 (3) Å	T = 173 K
α = 102.529 (6)°	0.26 × 0.22 × 0.20 mm
β = 93.439 (6)°

Data collection top

Bruker SMART APEXII diffractometer	1834 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	1102 reflections with I > 2σ(I)
T_min = 0.84, T_max = 0.88	R_int = 0.067
5948 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.30 e Å⁻³
1834 reflections	Δρ_min = −0.43 e Å⁻³
139 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.3476 (6)	0.5471 (6)	0.2465 (5)	0.0354 (10)
H1	0.3861	0.5957	0.1583	0.043*
C2	0.2932 (6)	0.3616 (6)	0.2276 (5)	0.0324 (9)
C3	0.2343 (6)	0.2876 (6)	0.3515 (5)	0.0337 (10)
H3	0.1963	0.1613	0.3413	0.040*
C4	0.1686 (6)	0.3342 (6)	0.6269 (5)	0.0369 (10)
H4	0.1286	0.2086	0.6220	0.044*
C5	0.1655 (7)	0.4475 (6)	0.7605 (5)	0.0363 (10)
H5	0.1215	0.4011	0.8489	0.044*
C6	0.2272 (6)	0.6342 (6)	0.7699 (5)	0.0308 (9)
C7	0.2918 (6)	0.7078 (5)	0.6455 (5)	0.0253 (8)
C8	0.2910 (5)	0.5882 (5)	0.5036 (5)	0.0261 (8)
C9	0.2304 (6)	0.4002 (5)	0.4943 (5)	0.0261 (8)
C10	0.3645 (6)	0.9105 (5)	0.6610 (4)	0.0293 (9)
Cl1	0.29545 (15)	0.22889 (15)	0.04666 (12)	0.0385 (3)
Cl2	0.23077 (17)	0.77619 (16)	0.94953 (12)	0.0422 (3)
N1	0.3496 (5)	0.6591 (4)	0.3774 (4)	0.0283 (7)
O1	0.5586 (4)	0.9997 (4)	0.6659 (3)	0.0302 (6)
H1A	0.597 (7)	1.106 (7)	0.652 (5)	0.036*
O2	0.2510 (5)	0.9766 (4)	0.6634 (5)	0.0519 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.038 (2)	0.041 (3)	0.032 (2)	0.021 (2)	0.0079 (18)	0.012 (2)
C2	0.027 (2)	0.032 (2)	0.039 (2)	0.0174 (19)	0.0036 (17)	0.0030 (19)
C3	0.033 (2)	0.021 (2)	0.049 (2)	0.016 (2)	0.0051 (19)	0.008 (2)
C4	0.037 (2)	0.025 (2)	0.053 (3)	0.014 (2)	0.006 (2)	0.022 (2)
C5	0.043 (2)	0.035 (3)	0.036 (2)	0.019 (2)	0.0106 (19)	0.017 (2)
C6	0.0262 (19)	0.035 (2)	0.033 (2)	0.0165 (18)	0.0041 (16)	0.0098 (19)
C7	0.028 (2)	0.020 (2)	0.032 (2)	0.0138 (17)	0.0062 (16)	0.0073 (17)
C8	0.0180 (18)	0.024 (2)	0.034 (2)	0.0095 (16)	0.0014 (15)	0.0050 (17)
C9	0.0258 (18)	0.020 (2)	0.036 (2)	0.0126 (16)	0.0030 (16)	0.0091 (17)
C10	0.034 (2)	0.025 (2)	0.0246 (19)	0.0119 (18)	0.0010 (15)	0.0038 (18)
Cl1	0.0372 (6)	0.0432 (7)	0.0423 (6)	0.0303 (5)	0.0101 (5)	−0.0006 (5)
Cl2	0.0548 (7)	0.0433 (7)	0.0343 (6)	0.0280 (6)	0.0144 (5)	0.0089 (5)
N1	0.0318 (18)	0.0235 (18)	0.0295 (17)	0.0130 (15)	0.0066 (13)	0.0069 (15)
O1	0.0319 (16)	0.0189 (15)	0.0364 (16)	0.0071 (13)	0.0056 (12)	0.0120 (13)
O2	0.048 (2)	0.0257 (17)	0.092 (3)	0.0240 (16)	0.0204 (18)	0.0171 (18)

Geometric parameters (Å, º) top

C1—N1	1.308 (5)	C5—H5	0.9500
C1—C2	1.391 (6)	C6—C7	1.373 (6)
C1—H1	0.9500	C6—Cl2	1.743 (4)
C2—C3	1.362 (6)	C7—C8	1.414 (5)
C2—Cl1	1.731 (4)	C7—C10	1.510 (5)
C3—C9	1.403 (6)	C8—N1	1.369 (5)
C3—H3	0.9500	C8—C9	1.417 (5)
C4—C5	1.345 (6)	C10—O2	1.206 (5)
C4—C9	1.405 (5)	C10—O1	1.299 (5)
C4—H4	0.9500	O1—H1A	0.84 (5)
C5—C6	1.405 (6)

N1—C1—C2	124.6 (4)	C7—C6—Cl2	119.9 (3)
N1—C1—H1	117.7	C5—C6—Cl2	118.0 (3)
C2—C1—H1	117.7	C6—C7—C8	117.8 (4)
C3—C2—C1	118.9 (4)	C6—C7—C10	121.0 (3)
C3—C2—Cl1	121.5 (3)	C8—C7—C10	121.2 (3)
C1—C2—Cl1	119.6 (3)	N1—C8—C7	118.2 (4)
C2—C3—C9	119.2 (4)	N1—C8—C9	121.6 (3)
C2—C3—H3	120.4	C7—C8—C9	120.2 (4)
C9—C3—H3	120.4	C3—C9—C4	122.9 (4)
C5—C4—C9	120.5 (4)	C3—C9—C8	118.0 (4)
C5—C4—H4	119.7	C4—C9—C8	119.1 (3)
C9—C4—H4	119.7	O2—C10—O1	125.4 (4)
C4—C5—C6	120.2 (4)	O2—C10—C7	122.5 (3)
C4—C5—H5	119.9	O1—C10—C7	112.1 (3)
C6—C5—H5	119.9	C1—N1—C8	117.7 (3)
C7—C6—C5	122.1 (4)	C10—O1—H1A	113 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1ⁱ	0.84 (5)	1.91 (5)	2.753 (4)	173 (4)

Symmetry code: (i) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₅Cl₂NO₂
M_r	242.05
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	7.5002 (12), 8.4016 (14), 8.732 (3)
α, β, γ (°)	102.529 (6), 93.439 (6), 116.479 (4)
V (Å³)	472.98 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.26 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.84, 0.88
No. of measured, independent and observed [I > 2σ(I)] reflections	5948, 1834, 1102
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.140, 1.01
No. of reflections	1834
No. of parameters	139
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.43

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1ⁱ	0.84 (5)	1.91 (5)	2.753 (4)	173 (4)

Symmetry code: (i) −x+1, −y+2, −z+1.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1786

doi:10.1107/S1600536808026238

Open

access