organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Ethyl 3,7-di­chloro­quinoline-8-carboxyl­ate

aJiangsu Key Laboratory for the Chemistry of Low-dimensional Materials, Department of Chemistry, Huaiyin Teachers College, Huaian 223300, Jiangsu Province, People's Republic of China
*Correspondence e-mail: annleet@126.com

(Received 8 October 2008; accepted 28 October 2008; online 31 October 2008)

The title compound, C12H9Cl2NO2, was prepared by the esterification of 3,7-dichloro­quinoline-8-carboxylic acid with triethyl phosphite. The crystal structure is stabilized by aromatic ππ stacking between the benzene and the pyridine rings of neighbouring mol­ecules [centroid–centroid distances = 3.716 (2) and 3.642 (2) Å]. In addition, weak inter­molecular C—H⋯N hydrogen bonds are present in the structure.

Related literature

For the use of 3,7-dichloro­quinoline-8-carboxylic acid as a herbicide, see: Nuria et al. (1997[Nuria, L. M., George, M. & Rafael, D. P. (1997). Pestic. Sci. 51, 171-175.]); Pornprom et al. (2006[Pornprom, T., Mahatamuchoke, P. & Usui, K. (2006). Pest Manag. Sci. 62, 1109-1115.]); Sunohara & Matsumoto (2004[Sunohara, Y. & Matsumoto, H. (2004). Plant Sci. 167, 597-606.]); Tresch & Grossmann (2002[Tresch, S. & Grossmann, K. (2002). Pestic. Biochem. Physiol. 75, 73-78.]). For the usual preparative route, see: Yang et al. (2002[Yang, L., Wang, P. & Zhou, D. R. (2002). J. Harbin Inst. Technol. 9, 401-404.]). For related complexes, see: An et al. (2008[An, L.-T., Zhou, J., Zhou, J.-F. & Xia, M. (2008). Acta Cryst. E64, m1170.]); Che et al. (2005[Che, G.-B., Liu, C.-B., Cui, Y.-C. & Li, C.-B. (2005). Acta Cryst. E61, m2207-m2208.]); Guo (2008[Guo, X.-H. (2008). Acta Cryst. E64, o1786.]); Li et al. (2008[Li, Z., Wu, F., Gong, Y., Zhang, Y. & Bai, C. (2008). Acta Cryst. E64, m227.]); Turel et al. (2004[Turel, I., Milena, P., Amalija, G., Enzo, A., Barbara, S., Alberta, B. & Gianni, S. (2004). Inorg. Chim. Acta, 98, 239-401.]); Zhang et al. (2007[Zhang, Y.-H., Wu, F.-J., Li, X.-M., Zhu, M.-C. & Gong, Y. (2007). Acta Cryst. E63, m1557.]). For 3,7-dichloro­quinoline-8-carboxylic acid derivatives, see: Liang et al. (2006[Liang, Y., He, H.-W., Wang, Y.-Z. & Chen, T. (2006). Acta Cryst. E62, o3652-o3654.]);

[Scheme 1]

Experimental

Crystal data
  • C12H9Cl2NO2

  • Mr = 270.10

  • Tetragonal, I 41 /a

  • a = 25.4806 (3) Å

  • c = 7.3497 (2) Å

  • V = 4771.87 (15) Å3

  • Z = 16

  • Mo Kα radiation

  • μ = 0.53 mm−1

  • T = 296 (2) K

  • 0.10 × 0.08 × 0.06 mm

Data collection
  • Bruker SMART APEX2 diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 1999[Bruker (1999). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.950, Tmax = 0.969

  • 19332 measured reflections

  • 2750 independent reflections

  • 1625 reflections with I > 2σ(I)

  • Rint = 0.045

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.117

  • S = 1.05

  • 2750 reflections

  • 155 parameters

  • H-atom parameters constrained

  • Δρmax = 0.20 e Å−3

  • Δρmin = −0.25 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C11—H11A⋯N1i 0.97 2.46 3.299 (3) 145
Symmetry code: (i) [-y+{\script{5\over 4}}, x+{\script{1\over 4}}, -z+{\script{5\over 4}}].

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]).

Supporting information


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). Usually, it was prepared via Skraup cyclization from 2-methyl-3- chloroaniline, followed by chlorination and oxidation (Yang et al., 2002). Furthermore, quinolinecarboxylates can chelate to metal atoms, forming the complexes, such as trans-Dimethanolbis(quinoline-8-carboxylato-κ2N,O)- cobalt(II) (Che et al.,2005),catena-Poly[nickel(II)-bis(µ-3,7-dichloroquinoline-8-χarboxylato-κ3N,O:O')] (Zhang et al., 2007), catena-Poly[cobalt(II)-bis (l-3,7-dichloroquinoline-8-carboxylato-κ3N,O:O')] (Li et al., 2008). More recently, we also have reported a Zinc-quinclorac complex (An et al., 2008) and quinclorac (Guo, 2008). But the derivatives of 3,7-dichloroquinoline-8-carboxylic acid have been less reported (Liang et al., 2006). Here we report the crystal structure of the title compound, ethyl 3,7-dichloroquinoline-8-carboxylate (I) (Fig. 1).

In the title compound (I), as shown in Fig. 1, the plane (O1—C10—O2—C11) is nearly vertical to the quinoline ring, in which the dihedral angel is 86.6 (1). The quinoline unit is essentially planar, with a mean deviation of 0.007 (2) Å from the least-squares plane defined by the ten constituent atoms. The molecular packing (Fig. 2) is stabilized by aromatic ππ stackings between the benzene and the pyridine rings of the adjacent molecules. The Cg1···Cg2ii and Cg1···Cg2iii distances are 3.716 (2) and 3.642 (2) Å (Fig. 2; Cg1 and Cg2 are the centroids of the C1/C2/C3/C4/C9/C8 benzene ring and the N1/C7/C6/C5/C9/C8 pyridine ring, respectively, symmetry code as in Fig. 2). The crystal structure is further stabilized by intermolecular C11—H11A···Ni hydrogen bonds (Fig. 2 and Table 1; symmetry code as in 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 the usual preparative route, see: Yang et al. (2002). For related complexes, see: An et al. (2008); Che et al. (2005); Guo (2008); Li et al. (2008); Turel et al. (2004); Zhang et al. (2007). For 3,7-dichloroquinoline-8-carboxylic acid derivatives, see: Liang et al. (2006);

Experimental top

Ethyl 3,7-dichloroquinoline-8-carboxylate was obtained from the reaction of 3,7-dichloroquinoline-8-carboxylic acid with triethyl phosphite in refluxing condition. After recrystallization from ethanol, then it was dissolved the mixture of acetone/petroleum ether (1:4, V/V). The suitable single-crystal for X-ray analysis was obtained by slow evaporation.

Refinement top

All H atoms were geometrically positioned and refined using a riding model, with C—H = 0.93 (aromatic), 0.97 (methylene) and 0.96 Å (methyl) H atoms, and with Uiso(H) = 1.2Ueq(C) (aromatic, methylene) and 1.5Ueq(C) (methyl) H atoms.

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: SHELXS97 (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 molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. ππ stackings and C—H···N interactions (dotted lines) in the title compound. Cg denotes ring centroid. [Symmetry code: (i) -y+5/4, x+1/4, -z+5/4; (ii) -x+1, -y+1, -z+2; (iii)-x+1, -y+1, -z+1.]
Ethyl 3,7-dichloroquinoline-8-carboxylate top
Crystal data top
C12H9Cl2NO2Dx = 1.504 Mg m3
Mr = 270.10Melting point: not measured K
Tetragonal, I41/aMo Kα radiation, λ = 0.71073 Å
Hall symbol: -I_4adCell parameters from 2208 reflections
a = 25.4806 (3) Åθ = 1.6–26.0°
c = 7.3497 (2) ŵ = 0.53 mm1
V = 4771.87 (15) Å3T = 296 K
Z = 16Needle, colorless
F(000) = 22080.10 × 0.08 × 0.06 mm
Data collection top
Bruker SMART APEX2
diffractometer
2750 independent reflections
Radiation source: fine-focus sealed tube1625 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
Detector resolution: 10.0 pixels mm-1θmax = 27.5°, θmin = 1.6°
ϕ and ω scansh = 3233
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
k = 3332
Tmin = 0.950, Tmax = 0.969l = 99
19332 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0469P)2 + 1.2301P]
where P = (Fo2 + 2Fc2)/3
2750 reflections(Δ/σ)max < 0.001
155 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C12H9Cl2NO2Z = 16
Mr = 270.10Mo Kα radiation
Tetragonal, I41/aµ = 0.53 mm1
a = 25.4806 (3) ÅT = 296 K
c = 7.3497 (2) Å0.10 × 0.08 × 0.06 mm
V = 4771.87 (15) Å3
Data collection top
Bruker SMART APEX2
diffractometer
2750 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
1625 reflections with I > 2σ(I)
Tmin = 0.950, Tmax = 0.969Rint = 0.045
19332 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.117H-atom parameters constrained
S = 1.06Δρmax = 0.20 e Å3
2750 reflectionsΔρmin = 0.25 e Å3
155 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
xyzUiso*/Ueq
Cl10.65771 (2)0.53635 (3)0.60570 (9)0.0725 (2)
Cl20.34654 (3)0.47136 (3)0.89519 (10)0.0809 (3)
O10.57642 (7)0.63042 (6)0.8389 (2)0.0714 (5)
O20.55721 (6)0.62556 (5)0.5418 (2)0.0560 (4)
N10.46789 (7)0.56227 (7)0.7898 (3)0.0535 (5)
C10.55677 (8)0.54727 (8)0.7053 (3)0.0479 (5)
C20.59627 (8)0.51296 (8)0.6642 (3)0.0511 (5)
C30.58827 (9)0.45826 (9)0.6676 (3)0.0582 (6)
H30.61570.43560.63900.070*
C40.54076 (9)0.43888 (9)0.7125 (3)0.0594 (6)
H40.53580.40270.71440.071*
C50.44775 (9)0.45445 (8)0.8039 (3)0.0574 (6)
H50.44050.41870.81070.069*
C60.40972 (9)0.49023 (9)0.8394 (3)0.0555 (6)
C70.42156 (9)0.54368 (9)0.8316 (3)0.0577 (6)
H70.39490.56750.85770.069*
C80.50652 (8)0.52712 (8)0.7514 (3)0.0458 (5)
C90.49847 (8)0.47219 (8)0.7565 (3)0.0492 (5)
C100.56464 (8)0.60545 (8)0.7069 (3)0.0505 (5)
C110.56478 (9)0.68194 (8)0.5254 (3)0.0609 (6)
H11A0.59990.69150.56390.073*
H11B0.53980.70040.60150.073*
C120.55684 (13)0.69615 (10)0.3318 (4)0.0967 (10)
H12A0.58090.67660.25740.145*
H12B0.56300.73300.31600.145*
H12C0.52150.68800.29670.145*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0602 (4)0.0814 (5)0.0760 (5)0.0005 (3)0.0113 (3)0.0024 (3)
Cl20.0661 (4)0.1000 (5)0.0765 (5)0.0247 (4)0.0006 (3)0.0114 (4)
O10.0916 (13)0.0584 (10)0.0642 (12)0.0132 (9)0.0061 (9)0.0109 (8)
O20.0650 (10)0.0406 (8)0.0624 (11)0.0065 (7)0.0037 (8)0.0032 (7)
N10.0524 (11)0.0480 (10)0.0601 (12)0.0009 (9)0.0024 (9)0.0023 (8)
C10.0560 (13)0.0447 (12)0.0430 (13)0.0014 (10)0.0049 (10)0.0001 (9)
C20.0580 (13)0.0529 (13)0.0424 (12)0.0009 (10)0.0021 (10)0.0015 (10)
C30.0704 (16)0.0530 (14)0.0511 (14)0.0128 (11)0.0018 (11)0.0042 (10)
C40.0804 (17)0.0423 (12)0.0555 (15)0.0022 (12)0.0030 (12)0.0035 (10)
C50.0778 (17)0.0462 (12)0.0483 (14)0.0158 (12)0.0057 (11)0.0036 (10)
C60.0584 (14)0.0637 (15)0.0445 (13)0.0129 (11)0.0065 (10)0.0043 (10)
C70.0557 (14)0.0595 (14)0.0578 (15)0.0034 (11)0.0035 (11)0.0037 (11)
C80.0567 (13)0.0418 (12)0.0389 (12)0.0007 (10)0.0072 (9)0.0002 (9)
C90.0667 (15)0.0412 (12)0.0397 (13)0.0033 (10)0.0077 (10)0.0014 (9)
C100.0456 (12)0.0497 (13)0.0562 (15)0.0038 (10)0.0016 (10)0.0020 (11)
C110.0583 (14)0.0392 (12)0.0851 (18)0.0080 (10)0.0071 (12)0.0011 (11)
C120.139 (3)0.0547 (16)0.097 (2)0.0178 (17)0.0243 (19)0.0215 (15)
Geometric parameters (Å, º) top
Cl1—C21.729 (2)C4—H40.9300
Cl2—C61.730 (2)C5—C61.356 (3)
O1—C101.198 (2)C5—C91.413 (3)
O2—C101.331 (2)C5—H50.9300
O2—C111.454 (2)C6—C71.396 (3)
N1—C71.309 (3)C7—H70.9300
N1—C81.360 (2)C8—C91.415 (3)
C1—C21.367 (3)C11—C121.482 (3)
C1—C81.420 (3)C11—H11A0.9700
C1—C101.496 (3)C11—H11B0.9700
C2—C31.409 (3)C12—H12A0.9600
C3—C41.348 (3)C12—H12B0.9600
C3—H30.9300C12—H12C0.9600
C4—C91.409 (3)
C10—O2—C11115.91 (17)C6—C7—H7118.1
C7—N1—C8117.60 (18)N1—C8—C9122.72 (19)
C2—C1—C8119.03 (18)N1—C8—C1117.63 (17)
C2—C1—C10122.47 (18)C9—C8—C1119.65 (19)
C8—C1—C10118.49 (18)C4—C9—C5124.3 (2)
C1—C2—C3121.5 (2)C4—C9—C8118.6 (2)
C1—C2—Cl1120.06 (16)C5—C9—C8117.1 (2)
C3—C2—Cl1118.45 (17)O1—C10—O2124.7 (2)
C4—C3—C2119.8 (2)O1—C10—C1124.5 (2)
C4—C3—H3120.1O2—C10—C1110.81 (18)
C2—C3—H3120.1O2—C11—C12107.63 (19)
C3—C4—C9121.5 (2)O2—C11—H11A110.2
C3—C4—H4119.3C12—C11—H11A110.2
C9—C4—H4119.3O2—C11—H11B110.2
C6—C5—C9119.07 (19)C12—C11—H11B110.2
C6—C5—H5120.5H11A—C11—H11B108.5
C9—C5—H5120.5C11—C12—H12A109.5
C5—C6—C7119.6 (2)C11—C12—H12B109.5
C5—C6—Cl2121.59 (18)H12A—C12—H12B109.5
C7—C6—Cl2118.82 (19)C11—C12—H12C109.5
N1—C7—C6123.9 (2)H12A—C12—H12C109.5
N1—C7—H7118.1H12B—C12—H12C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11A···N1i0.972.463.299 (3)145
Symmetry code: (i) y+5/4, x+1/4, z+5/4.

Experimental details

Crystal data
Chemical formulaC12H9Cl2NO2
Mr270.10
Crystal system, space groupTetragonal, I41/a
Temperature (K)296
a, c (Å)25.4806 (3), 7.3497 (2)
V3)4771.87 (15)
Z16
Radiation typeMo Kα
µ (mm1)0.53
Crystal size (mm)0.10 × 0.08 × 0.06
Data collection
DiffractometerBruker SMART APEX2
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.950, 0.969
No. of measured, independent and
observed [I > 2σ(I)] reflections
19332, 2750, 1625
Rint0.045
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.117, 1.06
No. of reflections2750
No. of parameters155
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.25

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···AD—HH···AD···AD—H···A
C11—H11A···N1i0.972.463.299 (3)144.9
Symmetry code: (i) y+5/4, x+1/4, z+5/4.
 

Acknowledgements

This work was supported financially by Jiangsu Key Laboratory for the Chemistry of Low-dimensional Materials.

References

First citationAn, L.-T., Zhou, J., Zhou, J.-F. & Xia, M. (2008). Acta Cryst. E64, m1170.  Web of Science CrossRef IUCr Journals Google Scholar
First citationBruker (1999). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChe, G.-B., Liu, C.-B., Cui, Y.-C. & Li, C.-B. (2005). Acta Cryst. E61, m2207–m2208.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationGuo, X.-H. (2008). Acta Cryst. E64, o1786.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationLi, Z., Wu, F., Gong, Y., Zhang, Y. & Bai, C. (2008). Acta Cryst. E64, m227.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationLiang, Y., He, H.-W., Wang, Y.-Z. & Chen, T. (2006). Acta Cryst. E62, o3652–o3654.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationNuria, L. M., George, M. & Rafael, D. P. (1997). Pestic. Sci. 51, 171–175.  CrossRef Google Scholar
First citationPornprom, T., Mahatamuchoke, P. & Usui, K. (2006). Pest Manag. Sci. 62, 1109–1115.  Web of Science CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSunohara, Y. & Matsumoto, H. (2004). Plant Sci. 167, 597–606.  Web of Science CrossRef CAS Google Scholar
First citationTresch, S. & Grossmann, K. (2002). Pestic. Biochem. Physiol. 75, 73–78.  Web of Science CrossRef Google Scholar
First citationTurel, I., Milena, P., Amalija, G., Enzo, A., Barbara, S., Alberta, B. & Gianni, S. (2004). Inorg. Chim. Acta, 98, 239–401.  Google Scholar
First citationYang, L., Wang, P. & Zhou, D. R. (2002). J. Harbin Inst. Technol. 9, 401–404.  CAS Google Scholar
First citationZhang, Y.-H., Wu, F.-J., Li, X.-M., Zhu, M.-C. & Gong, Y. (2007). Acta Cryst. E63, m1557.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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