Crystal structure of ethyl 2-chloro-5,8-di-meth-oxy-quinoline-3-carboxyl-ate.

In the title compound, C14H14ClNO4, the dihedral angle between the quinoline ring system (r.m.s. deviation = 0.0142 Å) and ester planes is 18.99 (3)°. The C-O-C-Cm (m = meth-yl) torsion angle is -172.08 (10)°, indicating a trans conformation. In the crystal, the mol-ecules are linked by C-H⋯O and C-H⋯N inter-actions, generating layers lying parallel to (101). Aromatic π-π stacking [centroid-centroid distances = 3.557 (2) and 3.703 (2)Å] links the layers into a three-dimensional network.

Related literature

For the synthesis and applications of quinoline derivatives, see: Wang et al. (2011 ▶); Benzerka et al. (2012 ▶); Valdez et al. (2009 ▶). For our previous work, see: Bouraiou et al. (2012 ▶); Hayour et al. (2014 ▶); Benzerka et al. (2012 ▶).

Experimental

Crystal data

C14H14ClNO4

M = 295.71

Triclinic,

a = 7.512 (4) Å

b = 9.759 (5) Å

c = 9.811 (5) Å

α = 76.071 (10)°

β = 72.021 (10)°

γ = 86.037 (10)°

V = 664.0 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.30 mm−1

T = 150 K

0.25 × 0.14 × 0.12 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T min = 0.690, T max = 0.747

10769 measured reflections

5204 independent reflections

4090 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.103

S = 1.04

5204 reflections

184 parameters

H-atom parameters constrained

Δρmax = 0.5 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814017309/hg5402sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017309/hg5402Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814017309/hg5402Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814017309/hg5402fig1.tif

(Farrugia, 2012) the structure of the title compound with the atomic labelling scheme. Displacement are drawn at the 50% probability level.

Click here for additional data file.

b . DOI: 10.1107/S1600536814017309/hg5402fig2.tif

(Brandenburg & Berndt, 2001) A diagram of the layered crystal packing of (I) viewed down the b axis and showing hydrogen bond [C—H⋯O in red and C—H⋯N in black] as dashed line.

CCDC reference: 1016211

Additional supporting information: crystallographic information; 3D view; checkCIF report

C14H14ClNO4	Z = 2
Mr = 295.71	F(000) = 308
Triclinic, P1	Dx = 1.479 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.512 (4) Å	Cell parameters from 4109 reflections
b = 9.759 (5) Å	θ = 2.7–34.1°
c = 9.811 (5) Å	µ = 0.30 mm−1
α = 76.071 (10)°	T = 150 K
β = 72.021 (10)°	Prism, colorless
γ = 86.037 (10)°	0.25 × 0.14 × 0.12 mm
V = 664.0 (6) Å3

Bruker APEXII diffractometer	4090 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
CCD rotation images, thin slices scans	θmax = 34.7°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −11→11
Tmin = 0.690, Tmax = 0.747	k = −15→15
10769 measured reflections	l = −15→15
5204 independent 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0528P)2 + 0.079P] where P = (Fo2 + 2Fc2)/3
5204 reflections	(Δ/σ)max = 0.001
184 parameters	Δρmax = 0.5 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
C1	1.27548 (18)	1.02335 (11)	0.38370 (13)	0.0317 (2)
H1B	1.3474	1.0184	0.4504	0.048*
H1A	1.1478	1.0451	0.4304	0.048*
H1C	1.3262	1.0958	0.2965	0.048*
C2	1.28321 (17)	0.88354 (11)	0.34275 (11)	0.0266 (2)
H2A	1.2118	0.8873	0.2747	0.032*
H2B	1.4116	0.8599	0.2961	0.032*
C3	1.21881 (13)	0.64349 (10)	0.46758 (10)	0.01689 (16)
C4	1.11813 (13)	0.54830 (9)	0.61114 (10)	0.01547 (15)
C5	1.14674 (13)	0.39997 (10)	0.64961 (10)	0.01641 (16)
C6	0.92888 (13)	0.37156 (9)	0.87752 (10)	0.01595 (16)
C7	0.83649 (14)	0.28087 (10)	1.01633 (10)	0.01932 (17)
C8	0.82466 (19)	0.05352 (12)	1.17645 (13)	0.0316 (2)
H8A	0.8799	−0.0381	1.176	0.047*
H8B	0.6908	0.0448	1.2073	0.047*
H8C	0.8618	0.0943	1.2434	0.047*
C9	0.70785 (14)	0.33822 (11)	1.12113 (10)	0.02025 (18)
H9	0.6474	0.2795	1.2116	0.024*
C10	0.66446 (13)	0.48421 (11)	1.09552 (10)	0.01941 (17)
H10	0.5761	0.5196	1.1683	0.023*
C11	0.75286 (13)	0.57316 (10)	0.96332 (10)	0.01729 (16)
C12	0.88663 (12)	0.51757 (9)	0.85187 (10)	0.01559 (16)
C13	0.98519 (13)	0.60393 (9)	0.71557 (10)	0.01569 (16)
H13	0.9603	0.7001	0.6955	0.019*
C14	0.61166 (16)	0.78024 (12)	1.03759 (11)	0.0250 (2)
H14A	0.4863	0.7439	1.0691	0.038*
H14B	0.6108	0.8806	0.9999	0.038*
H14C	0.661	0.7598	1.1196	0.038*
N1	1.05905 (11)	0.31542 (8)	0.77389 (9)	0.01767 (15)
O1	1.20348 (11)	0.77897 (8)	0.47853 (8)	0.02506 (16)
O2	0.88630 (12)	0.14209 (8)	1.03191 (8)	0.02716 (17)
O3	1.30129 (11)	0.60788 (8)	0.35513 (8)	0.02479 (16)
O4	0.72630 (11)	0.71537 (8)	0.92457 (8)	0.02404 (16)
Cl1	1.31414 (4)	0.31664 (3)	0.52818 (3)	0.02578 (7)

	U11	U22	U33	U12	U13	U23
C1	0.0359 (6)	0.0187 (5)	0.0298 (5)	−0.0004 (4)	0.0026 (5)	−0.0019 (4)
C2	0.0336 (6)	0.0190 (4)	0.0186 (4)	−0.0029 (4)	0.0014 (4)	0.0003 (3)
C3	0.0171 (4)	0.0168 (4)	0.0160 (4)	−0.0001 (3)	−0.0032 (3)	−0.0043 (3)
C4	0.0161 (4)	0.0154 (4)	0.0144 (4)	0.0003 (3)	−0.0030 (3)	−0.0044 (3)
C5	0.0173 (4)	0.0158 (4)	0.0164 (4)	0.0020 (3)	−0.0038 (3)	−0.0064 (3)
C6	0.0172 (4)	0.0150 (4)	0.0156 (4)	−0.0006 (3)	−0.0043 (3)	−0.0040 (3)
C7	0.0221 (4)	0.0163 (4)	0.0184 (4)	−0.0029 (3)	−0.0048 (3)	−0.0028 (3)
C8	0.0421 (7)	0.0189 (5)	0.0245 (5)	−0.0025 (4)	−0.0018 (5)	0.0024 (4)
C9	0.0207 (4)	0.0213 (4)	0.0160 (4)	−0.0050 (3)	−0.0021 (3)	−0.0024 (3)
C10	0.0176 (4)	0.0231 (4)	0.0160 (4)	−0.0005 (3)	−0.0017 (3)	−0.0060 (3)
C11	0.0174 (4)	0.0179 (4)	0.0157 (4)	0.0019 (3)	−0.0033 (3)	−0.0051 (3)
C12	0.0153 (4)	0.0163 (4)	0.0144 (4)	−0.0002 (3)	−0.0030 (3)	−0.0041 (3)
C13	0.0170 (4)	0.0140 (4)	0.0149 (4)	0.0006 (3)	−0.0030 (3)	−0.0036 (3)
C14	0.0278 (5)	0.0267 (5)	0.0207 (4)	0.0105 (4)	−0.0046 (4)	−0.0120 (4)
N1	0.0199 (4)	0.0154 (3)	0.0174 (3)	0.0006 (3)	−0.0046 (3)	−0.0047 (3)
O1	0.0331 (4)	0.0153 (3)	0.0183 (3)	−0.0012 (3)	0.0037 (3)	−0.0026 (2)
O2	0.0384 (4)	0.0146 (3)	0.0212 (3)	−0.0004 (3)	−0.0009 (3)	−0.0010 (3)
O3	0.0300 (4)	0.0243 (4)	0.0163 (3)	−0.0032 (3)	0.0012 (3)	−0.0075 (3)
O4	0.0294 (4)	0.0186 (3)	0.0183 (3)	0.0073 (3)	0.0005 (3)	−0.0054 (3)
Cl1	0.02904 (13)	0.02190 (12)	0.02243 (12)	0.00813 (9)	−0.00059 (9)	−0.00934 (9)

C1—C2	1.5050 (17)	C7—C9	1.3760 (14)
C1—H1B	0.96	C8—O2	1.4257 (14)
C1—H1A	0.96	C8—H8A	0.96
C1—H1C	0.96	C8—H8B	0.96
C2—O1	1.4534 (13)	C8—H8C	0.96
C2—H2A	0.97	C9—C10	1.4189 (15)
C2—H2B	0.97	C9—H9	0.93
C3—O3	1.2062 (12)	C10—C11	1.3722 (14)
C3—O1	1.3463 (13)	C10—H10	0.93
C3—C4	1.4928 (13)	C11—O4	1.3656 (13)
C4—C13	1.3796 (13)	C11—C12	1.4254 (13)
C4—C5	1.4241 (14)	C12—C13	1.4068 (13)
C5—N1	1.3025 (13)	C13—H13	0.93
C5—Cl1	1.7500 (10)	C14—O4	1.4301 (12)
C6—N1	1.3677 (12)	C14—H14A	0.96
C6—C12	1.4173 (14)	C14—H14B	0.96
C6—C7	1.4286 (14)	C14—H14C	0.96
C7—O2	1.3650 (14)
C2—C1—H1B	109.5	H8A—C8—H8B	109.5
C2—C1—H1A	109.5	O2—C8—H8C	109.5
H1B—C1—H1A	109.5	H8A—C8—H8C	109.5
C2—C1—H1C	109.5	H8B—C8—H8C	109.5
H1B—C1—H1C	109.5	C7—C9—C10	122.07 (9)
H1A—C1—H1C	109.5	C7—C9—H9	119
O1—C2—C1	106.85 (9)	C10—C9—H9	119
O1—C2—H2A	110.4	C11—C10—C9	120.01 (9)
C1—C2—H2A	110.4	C11—C10—H10	120
O1—C2—H2B	110.4	C9—C10—H10	120
C1—C2—H2B	110.4	O4—C11—C10	126.18 (8)
H2A—C2—H2B	108.6	O4—C11—C12	114.27 (8)
O3—C3—O1	123.25 (9)	C10—C11—C12	119.55 (9)
O3—C3—C4	126.28 (9)	C13—C12—C6	117.50 (8)
O1—C3—C4	110.46 (8)	C13—C12—C11	122.18 (9)
C13—C4—C5	116.02 (8)	C6—C12—C11	120.29 (8)
C13—C4—C3	119.42 (9)	C4—C13—C12	121.12 (9)
C5—C4—C3	124.56 (8)	C4—C13—H13	119.4
N1—C5—C4	125.27 (8)	C12—C13—H13	119.4
N1—C5—Cl1	114.12 (7)	O4—C14—H14A	109.5
C4—C5—Cl1	120.60 (7)	O4—C14—H14B	109.5
N1—C6—C12	121.71 (8)	H14A—C14—H14B	109.5
N1—C6—C7	118.96 (9)	O4—C14—H14C	109.5
C12—C6—C7	119.31 (8)	H14A—C14—H14C	109.5
O2—C7—C9	125.81 (9)	H14B—C14—H14C	109.5
O2—C7—C6	115.43 (9)	C5—N1—C6	118.38 (8)
C9—C7—C6	118.76 (9)	C3—O1—C2	115.86 (8)
O2—C8—H8A	109.5	C7—O2—C8	116.99 (8)
O2—C8—H8B	109.5	C11—O4—C14	116.88 (8)
O3—C3—C4—C13	−160.43 (10)	C7—C6—C12—C11	−0.20 (13)
O1—C3—C4—C13	18.58 (12)	O4—C11—C12—C13	1.56 (13)
O3—C3—C4—C5	18.55 (16)	C10—C11—C12—C13	−178.38 (9)
O1—C3—C4—C5	−162.43 (9)	O4—C11—C12—C6	179.62 (8)
C13—C4—C5—N1	−0.45 (14)	C10—C11—C12—C6	−0.32 (14)
C3—C4—C5—N1	−179.46 (9)	C5—C4—C13—C12	0.60 (13)
C13—C4—C5—Cl1	−178.93 (7)	C3—C4—C13—C12	179.67 (8)
C3—C4—C5—Cl1	2.06 (13)	C6—C12—C13—C4	−0.11 (13)
N1—C6—C7—O2	−1.04 (13)	C11—C12—C13—C4	178.00 (9)
C12—C6—C7—O2	−179.64 (8)	C4—C5—N1—C6	−0.23 (14)
N1—C6—C7—C9	178.96 (9)	Cl1—C5—N1—C6	178.33 (7)
C12—C6—C7—C9	0.36 (14)	C12—C6—N1—C5	0.77 (13)
O2—C7—C9—C10	179.98 (9)	C7—C6—N1—C5	−177.79 (9)
C6—C7—C9—C10	−0.02 (15)	O3—C3—O1—C2	3.72 (15)
C7—C9—C10—C11	−0.50 (15)	C4—C3—O1—C2	−175.33 (8)
C9—C10—C11—O4	−179.27 (9)	C1—C2—O1—C3	−172.08 (10)
C9—C10—C11—C12	0.66 (14)	C9—C7—O2—C8	−11.40 (15)
N1—C6—C12—C13	−0.60 (13)	C6—C7—O2—C8	168.60 (9)
C7—C6—C12—C13	177.95 (9)	C10—C11—O4—C14	7.48 (15)
N1—C6—C12—C11	−178.76 (9)	C12—C11—O4—C14	−172.46 (9)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O3i	0.93	2.56	3.482 (2)	173
C14—H14C···N1ii	0.96	2.61	3.476 (2)	150
C13—H13···O1	0.93	2.34	2.6713 (19)	101
C13—H13···O4	0.93	2.42	2.7366 (19)	100

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O3i	0.93	2.56	3.482 (2)	173
C14—H14C⋯N1ii	0.96	2.61	3.476 (2)	150

Symmetry codes: (i) ; (ii) .