Ethyl 3,7-dichloro-quinoline-8-carboxyl-ate.

The title compound, C(12)H(9)Cl(2)NO(2), was prepared by the esterification of 3,7-dichloro-quinoline-8-carboxylic acid with triethyl phosphite. The crystal structure is stabilized by aromatic π-π stacking between the benzene and the pyridine rings of neighbouring mol-ecules [centroid-centroid distances = 3.716 (2) and 3.642 (2) Å]. In addition, weak inter-molecular 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 ▶); 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

Crystal data

C12H9Cl2NO2

M = 270.10

Tetragonal,

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 ▶) T min = 0.950, T max = 0.969

19332 measured reflections

2750 independent reflections

1625 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 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

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: SHELXS97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034995/lx2075sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808034995/lx2075Isup2.hkl

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

C12H9Cl2NO2	Dx = 1.504 Mg m−3
Mr = 270.10	Melting point: not measured K
Tetragonal, I41/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I_4ad	Cell parameters from 2208 reflections
a = 25.4806 (3) Å	θ = 1.6–26.0°
c = 7.3497 (2) Å	µ = 0.53 mm−1
V = 4771.87 (15) Å3	T = 296 K
Z = 16	Needle, colorless
F(000) = 2208	0.10 × 0.08 × 0.06 mm

Bruker SMART APEX2 diffractometer	2750 independent reflections
Radiation source: fine-focus sealed tube	1625 reflections with I > 2σ(I)
graphite	Rint = 0.045
Detector resolution: 10.0 pixels mm-1	θmax = 27.5°, θmin = 1.6°
φ and ω scans	h = −32→33
Absorption correction: multi-scan (SADABS; Bruker, 1999)	k = −33→32
Tmin = 0.950, Tmax = 0.969	l = −9→9
19332 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H-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 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	0.65771 (2)	0.53635 (3)	0.60570 (9)	0.0725 (2)
Cl2	0.34654 (3)	0.47136 (3)	0.89519 (10)	0.0809 (3)
O1	0.57642 (7)	0.63042 (6)	0.8389 (2)	0.0714 (5)
O2	0.55721 (6)	0.62556 (5)	0.5418 (2)	0.0560 (4)
N1	0.46789 (7)	0.56227 (7)	0.7898 (3)	0.0535 (5)
C1	0.55677 (8)	0.54727 (8)	0.7053 (3)	0.0479 (5)
C2	0.59627 (8)	0.51296 (8)	0.6642 (3)	0.0511 (5)
C3	0.58827 (9)	0.45826 (9)	0.6676 (3)	0.0582 (6)
H3	0.6157	0.4356	0.6390	0.070*
C4	0.54076 (9)	0.43888 (9)	0.7125 (3)	0.0594 (6)
H4	0.5358	0.4027	0.7144	0.071*
C5	0.44775 (9)	0.45445 (8)	0.8039 (3)	0.0574 (6)
H5	0.4405	0.4187	0.8107	0.069*
C6	0.40972 (9)	0.49023 (9)	0.8394 (3)	0.0555 (6)
C7	0.42156 (9)	0.54368 (9)	0.8316 (3)	0.0577 (6)
H7	0.3949	0.5675	0.8577	0.069*
C8	0.50652 (8)	0.52712 (8)	0.7514 (3)	0.0458 (5)
C9	0.49847 (8)	0.47219 (8)	0.7565 (3)	0.0492 (5)
C10	0.56464 (8)	0.60545 (8)	0.7069 (3)	0.0505 (5)
C11	0.56478 (9)	0.68194 (8)	0.5254 (3)	0.0609 (6)
H11A	0.5999	0.6915	0.5639	0.073*
H11B	0.5398	0.7004	0.6015	0.073*
C12	0.55684 (13)	0.69615 (10)	0.3318 (4)	0.0967 (10)
H12A	0.5809	0.6766	0.2574	0.145*
H12B	0.5630	0.7330	0.3160	0.145*
H12C	0.5215	0.6880	0.2967	0.145*

	U11	U22	U33	U12	U13	U23
Cl1	0.0602 (4)	0.0814 (5)	0.0760 (5)	0.0005 (3)	0.0113 (3)	−0.0024 (3)
Cl2	0.0661 (4)	0.1000 (5)	0.0765 (5)	−0.0247 (4)	−0.0006 (3)	0.0114 (4)
O1	0.0916 (13)	0.0584 (10)	0.0642 (12)	−0.0132 (9)	−0.0061 (9)	−0.0109 (8)
O2	0.0650 (10)	0.0406 (8)	0.0624 (11)	−0.0065 (7)	−0.0037 (8)	0.0032 (7)
N1	0.0524 (11)	0.0480 (10)	0.0601 (12)	0.0009 (9)	−0.0024 (9)	0.0023 (8)
C1	0.0560 (13)	0.0447 (12)	0.0430 (13)	−0.0014 (10)	−0.0049 (10)	0.0001 (9)
C2	0.0580 (13)	0.0529 (13)	0.0424 (12)	0.0009 (10)	−0.0021 (10)	−0.0015 (10)
C3	0.0704 (16)	0.0530 (14)	0.0511 (14)	0.0128 (11)	−0.0018 (11)	−0.0042 (10)
C4	0.0804 (17)	0.0423 (12)	0.0555 (15)	0.0022 (12)	−0.0030 (12)	−0.0035 (10)
C5	0.0778 (17)	0.0462 (12)	0.0483 (14)	−0.0158 (12)	−0.0057 (11)	0.0036 (10)
C6	0.0584 (14)	0.0637 (15)	0.0445 (13)	−0.0129 (11)	−0.0065 (10)	0.0043 (10)
C7	0.0557 (14)	0.0595 (14)	0.0578 (15)	0.0034 (11)	−0.0035 (11)	0.0037 (11)
C8	0.0567 (13)	0.0418 (12)	0.0389 (12)	0.0007 (10)	−0.0072 (9)	0.0002 (9)
C9	0.0667 (15)	0.0412 (12)	0.0397 (13)	−0.0033 (10)	−0.0077 (10)	0.0014 (9)
C10	0.0456 (12)	0.0497 (13)	0.0562 (15)	−0.0038 (10)	0.0016 (10)	−0.0020 (11)
C11	0.0583 (14)	0.0392 (12)	0.0851 (18)	−0.0080 (10)	0.0071 (12)	0.0011 (11)
C12	0.139 (3)	0.0547 (16)	0.097 (2)	−0.0178 (17)	−0.0243 (19)	0.0215 (15)

Cl1—C2	1.729 (2)	C4—H4	0.9300
Cl2—C6	1.730 (2)	C5—C6	1.356 (3)
O1—C10	1.198 (2)	C5—C9	1.413 (3)
O2—C10	1.331 (2)	C5—H5	0.9300
O2—C11	1.454 (2)	C6—C7	1.396 (3)
N1—C7	1.309 (3)	C7—H7	0.9300
N1—C8	1.360 (2)	C8—C9	1.415 (3)
C1—C2	1.367 (3)	C11—C12	1.482 (3)
C1—C8	1.420 (3)	C11—H11A	0.9700
C1—C10	1.496 (3)	C11—H11B	0.9700
C2—C3	1.409 (3)	C12—H12A	0.9600
C3—C4	1.348 (3)	C12—H12B	0.9600
C3—H3	0.9300	C12—H12C	0.9600
C4—C9	1.409 (3)
C10—O2—C11	115.91 (17)	C6—C7—H7	118.1
C7—N1—C8	117.60 (18)	N1—C8—C9	122.72 (19)
C2—C1—C8	119.03 (18)	N1—C8—C1	117.63 (17)
C2—C1—C10	122.47 (18)	C9—C8—C1	119.65 (19)
C8—C1—C10	118.49 (18)	C4—C9—C5	124.3 (2)
C1—C2—C3	121.5 (2)	C4—C9—C8	118.6 (2)
C1—C2—Cl1	120.06 (16)	C5—C9—C8	117.1 (2)
C3—C2—Cl1	118.45 (17)	O1—C10—O2	124.7 (2)
C4—C3—C2	119.8 (2)	O1—C10—C1	124.5 (2)
C4—C3—H3	120.1	O2—C10—C1	110.81 (18)
C2—C3—H3	120.1	O2—C11—C12	107.63 (19)
C3—C4—C9	121.5 (2)	O2—C11—H11A	110.2
C3—C4—H4	119.3	C12—C11—H11A	110.2
C9—C4—H4	119.3	O2—C11—H11B	110.2
C6—C5—C9	119.07 (19)	C12—C11—H11B	110.2
C6—C5—H5	120.5	H11A—C11—H11B	108.5
C9—C5—H5	120.5	C11—C12—H12A	109.5
C5—C6—C7	119.6 (2)	C11—C12—H12B	109.5
C5—C6—Cl2	121.59 (18)	H12A—C12—H12B	109.5
C7—C6—Cl2	118.82 (19)	C11—C12—H12C	109.5
N1—C7—C6	123.9 (2)	H12A—C12—H12C	109.5
N1—C7—H7	118.1	H12B—C12—H12C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···N1i	0.97	2.46	3.299 (3)	145

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯N1i	0.97	2.46	3.299 (3)	145

Symmetry code: (i) .