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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1786.
Published online 2008 August 20. doi:  10.1107/S1600536808026238
PMCID: PMC2960518

3,7-Dichloro­quinoline-8-carboxylic acid

Abstract

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 [triangle]); Pornprom et al. (2006 [triangle]); Sunohara & Matsumoto (2004 [triangle]); Tresch & Grossmann (2002 [triangle]). For related complexes, see: Li et al. (2008 [triangle]); Turel et al. (2004 [triangle]); Zhang et al. (2007 [triangle]).

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Object name is e-64-o1786-scheme1.jpg

Experimental

Crystal data

  • C10H5Cl2NO2
  • M r = 242.05
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1786-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.063
  • wR(F 2) = 0.140
  • S = 1.01
  • 1834 reflections
  • 139 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.43 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

Experimental

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

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).

Figures

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.

Crystal data

C10H5Cl2NO2Z = 2
Mr = 242.05F000 = 244
Triclinic, P1Dx = 1.700 Mg m3
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 mm1
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

Bruker SMART APEXII diffractometer1834 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

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 Å3
139 parametersΔρmin = −0.43 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2136).

References

  • 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. [PMC free article] [PubMed]
  • 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. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • 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.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography