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Acta Cryst. (2008). E64, o1786    [ doi:10.1107/S1600536808026238 ]

3,7-Dichloroquinoline-8-carboxylic acid

X.-H. Guo

Abstract top

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

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.

Refinement top

All the non-hydrogen atoms were located from the Fourier maps, and were refined anisotropically. The hydroxyl hydrogen, H1A, was found from the Fourier difference maps and refined isotropically with a fixed O—H bond length. All other H atoms were positioned geometrically. All isotropic vibration parameters of hydrogen atoms were related to the atoms which they are bonded to with Uiso(H) = 1.2 Ueq(C,O).

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
[Figure 1] Fig. 1. The asymmetric unit of quinclorac with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] 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
C10H5Cl2NO2Z = 2
Mr = 242.05F000 = 244
Triclinic, P1Dx = 1.700 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.5002 (12) ÅCell parameters from 958 reflections
b = 8.4016 (14) Åθ = 2.1–25.5º
c = 8.732 (3) ŵ = 0.66 mm−1
α = 102.529 (6)ºT = 173 (2) K
β = 93.439 (6)ºPrismlike, colorless
γ = 116.479 (4)º0.26 × 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 tube1102 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.067
T = 173(2) Kθmax = 26.0º
ω scansθmin = 2.4º
Absorption correction: multi-scan
(SADABS; Bruker, 1999)		h = −9→9
Tmin = 0.84, Tmax = 0.88k = −8→10
5948 measured reflectionsl = −10→10
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.063H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.140  w = 1/[σ2(Fo2) + (0.062P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
1834 reflectionsΔρmax = 0.30 e Å−3
139 parametersΔρmin = −0.43 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C10H5Cl2NO2γ = 116.479 (4)º
Mr = 242.05V = 472.98 (17) Å3
Triclinic, P1Z = 2
a = 7.5002 (12) ÅMo Kα
b = 8.4016 (14) ŵ = 0.66 mm−1
c = 8.732 (3) ÅT = 173 (2) K
α = 102.529 (6)º0.26 × 0.22 × 0.20 mm
β = 93.439 (6)º
Data collection top
Bruker SMART APEXII
diffractometer		1834 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)		1102 reflections with I > 2σ(I)
Tmin = 0.84, Tmax = 0.88Rint = 0.067
5948 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.063139 parameters
wR(F2) = 0.140H atoms treated by a mixture of
independent and constrained refinement
S = 1.01Δρmax = 0.30 e Å−3
1834 reflectionsΔρmin = −0.43 e Å−3
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
xyzUiso*/Ueq
C10.3476 (6)0.5471 (6)0.2465 (5)0.0354 (10)
H10.38610.59570.15830.043*
C20.2932 (6)0.3616 (6)0.2276 (5)0.0324 (9)
C30.2343 (6)0.2876 (6)0.3515 (5)0.0337 (10)
H30.19630.16130.34130.040*
C40.1686 (6)0.3342 (6)0.6269 (5)0.0369 (10)
H40.12860.20860.62200.044*
C50.1655 (7)0.4475 (6)0.7605 (5)0.0363 (10)
H50.12150.40110.84890.044*
C60.2272 (6)0.6342 (6)0.7699 (5)0.0308 (9)
C70.2918 (6)0.7078 (5)0.6455 (5)0.0253 (8)
C80.2910 (5)0.5882 (5)0.5036 (5)0.0261 (8)
C90.2304 (6)0.4002 (5)0.4943 (5)0.0261 (8)
C100.3645 (6)0.9105 (5)0.6610 (4)0.0293 (9)
Cl10.29545 (15)0.22889 (15)0.04666 (12)0.0385 (3)
Cl20.23077 (17)0.77619 (16)0.94953 (12)0.0422 (3)
N10.3496 (5)0.6591 (4)0.3774 (4)0.0283 (7)
O10.5586 (4)0.9997 (4)0.6659 (3)0.0302 (6)
H1A0.597 (7)1.106 (7)0.652 (5)0.036*
O20.2510 (5)0.9766 (4)0.6634 (5)0.0519 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.038 (2)0.041 (3)0.032 (2)0.021 (2)0.0079 (18)0.012 (2)
C20.027 (2)0.032 (2)0.039 (2)0.0174 (19)0.0036 (17)0.0030 (19)
C30.033 (2)0.021 (2)0.049 (2)0.016 (2)0.0051 (19)0.008 (2)
C40.037 (2)0.025 (2)0.053 (3)0.014 (2)0.006 (2)0.022 (2)
C50.043 (2)0.035 (3)0.036 (2)0.019 (2)0.0106 (19)0.017 (2)
C60.0262 (19)0.035 (2)0.033 (2)0.0165 (18)0.0041 (16)0.0098 (19)
C70.028 (2)0.020 (2)0.032 (2)0.0138 (17)0.0062 (16)0.0073 (17)
C80.0180 (18)0.024 (2)0.034 (2)0.0095 (16)0.0014 (15)0.0050 (17)
C90.0258 (18)0.020 (2)0.036 (2)0.0126 (16)0.0030 (16)0.0091 (17)
C100.034 (2)0.025 (2)0.0246 (19)0.0119 (18)0.0010 (15)0.0038 (18)
Cl10.0372 (6)0.0432 (7)0.0423 (6)0.0303 (5)0.0101 (5)−0.0006 (5)
Cl20.0548 (7)0.0433 (7)0.0343 (6)0.0280 (6)0.0144 (5)0.0089 (5)
N10.0318 (18)0.0235 (18)0.0295 (17)0.0130 (15)0.0066 (13)0.0069 (15)
O10.0319 (16)0.0189 (15)0.0364 (16)0.0071 (13)0.0056 (12)0.0120 (13)
O20.048 (2)0.0257 (17)0.092 (3)0.0240 (16)0.0204 (18)0.0171 (18)
Geometric parameters (Å, °) top
C1—N11.308 (5)C5—H50.9500
C1—C21.391 (6)C6—C71.373 (6)
C1—H10.9500C6—Cl21.743 (4)
C2—C31.362 (6)C7—C81.414 (5)
C2—Cl11.731 (4)C7—C101.510 (5)
C3—C91.403 (6)C8—N11.369 (5)
C3—H30.9500C8—C91.417 (5)
C4—C51.345 (6)C10—O21.206 (5)
C4—C91.405 (5)C10—O11.299 (5)
C4—H40.9500O1—H1A0.84 (5)
C5—C61.405 (6)
N1—C1—C2124.6 (4)C7—C6—Cl2119.9 (3)
N1—C1—H1117.7C5—C6—Cl2118.0 (3)
C2—C1—H1117.7C6—C7—C8117.8 (4)
C3—C2—C1118.9 (4)C6—C7—C10121.0 (3)
C3—C2—Cl1121.5 (3)C8—C7—C10121.2 (3)
C1—C2—Cl1119.6 (3)N1—C8—C7118.2 (4)
C2—C3—C9119.2 (4)N1—C8—C9121.6 (3)
C2—C3—H3120.4C7—C8—C9120.2 (4)
C9—C3—H3120.4C3—C9—C4122.9 (4)
C5—C4—C9120.5 (4)C3—C9—C8118.0 (4)
C5—C4—H4119.7C4—C9—C8119.1 (3)
C9—C4—H4119.7O2—C10—O1125.4 (4)
C4—C5—C6120.2 (4)O2—C10—C7122.5 (3)
C4—C5—H5119.9O1—C10—C7112.1 (3)
C6—C5—H5119.9C1—N1—C8117.7 (3)
C7—C6—C5122.1 (4)C10—O1—H1A113 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N1i0.84 (5)1.91 (5)2.753 (4)173 (4)
Symmetry codes: (i) −x+1, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N1i0.84 (5)1.91 (5)2.753 (4)173 (4)
Symmetry codes: (i) −x+1, −y+2, −z+1.
references
References top

Bruker (1999). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Li, Z., Wu, F., Gong, Y., Zhang, Y. & Bai, C. (2008). Acta Cryst. E64, m227.

Nuria, L. M., George, M. & Rafael, D. P. (1997). Pestic. Sci. 51, 171–175.

Pornprom, T., Mahatamuchoke, P. & Usui, K. (2006). Pest Manag. Sci. 62, 1109–1115.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Sunohara, Y. & Matsumoto, H. (2004). Plant Sci. 167, 597–606.

Tresch, S. & Grossmann, K. (2002). Pestic. Biochem. Physiol. 75, 73–78.

Turel, I., Milena, P., Amalija, G., Enzo, A., Barbara, S., Alberta, B. & Gianni, S. (2004). Inorg. Chim. Acta, 98, 239–401.

Zhang, Y.-H., Wu, F.-J., Li, X.-M., Zhu, M.-C. & Gong, Y. (2007). Acta Cryst. E63, m1557.