4-Chloro-6,7-dimeth­oxy­quinoline

Wu, M.

doi:10.1107/S1600536811042589

organic compounds

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Volume 67| Part 11| November 2011| Page o3012

doi:10.1107/S1600536811042589

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4-Chloro-6,7-dimethoxyquinoline

Min Wu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: wuminnj@163.com

(Received 16 September 2011; accepted 14 October 2011; online 22 October 2011)

The title molecule, C₁₁H₁₀ClNO₂, is almost planar with the C atoms of the methoxy groups deviating by −0.082 (2) and 0.020 (2) Å from the least-squares plane defined by the atoms of the quinoline ring system (r.m.s. deviation = 0.002 Å). An intramolecular C—H⋯Cl interaction generates an S(5) ring motif.

Related literature

For related structures, see: Davies & Bond (2001 ); Yathirajan et al. (2007 ). For biological properties of quinoline derivatives, see: Franck et al. (2004 ); Moret et al. (2006 ); Furuta et al. (2006 ); Ilovich et al. (2008 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₁H₁₀ClNO₂
M_r = 223.65
Monoclinic, P 2₁ /c
a = 12.5530 (17) Å
b = 4.6499 (7) Å
c = 18.274 (3) Å
β = 105.786 (2)°
V = 1026.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 296 K
0.3 × 0.2 × 0.2 mm

Data collection

Rigaku SCXmini diffractometer
6840 measured reflections
1808 independent reflections
1542 reflections with I > 2σ(I)
R_int = 0.034
3 standard reflections every 150 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.115
S = 1.08
1808 reflections
139 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯Cl1	0.93	2.70	3.0827 (17)	105

Data collection: CrystalClear (Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811042589/lr2029sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042589/lr2029Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536811042589/lr2029Isup3.cml

checkCIF report

Comment top

Quinoline derivatives have been interesting to researchers for many years because a large number of natural products contain these heterocycles and also because their varied biological activities ( Franck et al. 2004; Moret et al. 2006; Furuta et al. 2006 & Ilovich et al. 2008).

Prompted by the properties of quinoline derivatives, the title compound, C₁₁H₁₀ClNO₂, has been synthesized. Bond lengths and angles are in the usual range (Davies & Bond 2001 & Yathirajan et al. 2007) and the whole molecule is almost planar with the carbon atoms of the methoxyl groups deviating 0.08 (C10) and 0.02Å (C11) from the least-square plane defined by the atoms of the quinoline ring. There are intramolecular C8 — H8 ···Cl1 interactions (Table 1) generating S(5) ring motifs (Bernstein et al. 1995) . Figure 1 shows the molecular structure of the title compound and Figure 2 is a partial paking view of the crystal structure down the b axis.

Related literature top

For related structures, see: Davies & Bond (2001); Yathirajan et al. (2007). For biological properties of quinoline derivatives, see: Franck et al. (2004); Moret et al. (2006); Furuta et al. (2006); Ilovich et al. (2008). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of 6,7- dimethoxynaphthalen-1-ol (20.4 g, 100 mmol) and POCl₃ (60 ml, 640 mmol) was heated under reflux for 6 h. The excess of phosporus oxychoride was distilled out under reduced pressure. 200 g crush ice was added to the residue followed by 50% aqueous NaOH until the pH was adjusted to 8. The resulting solid was collected by filtration and washed with water to give the crude product. Purification of the crude product by a column chromatography (petroleum ether: EtOAc = 8:1 v.v) afforded the title compound (15.6 g, 70%) as pink crystals.The purity of the product, 4- chloro- 6, 7- dimethoxy- quinoline, was determined using a reversed- phase C-18 analytical HPLC column (99% purity). Crystals of the title compound suitable for X– ray diffraction were obtained by slow evaporation of methanol solution at room temperature. m. p. 403- 404 K; ¹H NMR (DMSO– d₆): δ8.57 (d, J = 5.1 Hz, 1H), 7.40 (d, J = 4.8 Hz, 1H), 7.37 (s, 1H), 7.32 (s, 1H), 4.04 (s, 3H), 4.03 (s. 3H). MS (ESI, m/z): 224 (M+1).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Partial packing view of the title compound, viewed down the b axis.

4-Chloro-6,7-dimethoxyquinoline top

Crystal data top

C₁₁H₁₀ClNO₂	F(000) = 464
M_r = 223.65	D_x = 1.447 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.5530 (17) Å	Cell parameters from 30 reflections
b = 4.6499 (7) Å	θ = 3–25°
c = 18.274 (3) Å	µ = 0.35 mm⁻¹
β = 105.786 (2)°	T = 296 K
V = 1026.4 (3) Å³	Block, pink
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection top

Rigaku SCXmini diffractometer	R_int = 0.034
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 1.7°
Graphite monochromator	h = −14→14
ω scans	k = −5→5
6840 measured reflections	l = −21→21
1808 independent reflections	3 standard reflections every 150 reflections
1542 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0662P)² + 0.1562P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1808 reflections	Δρ_max = 0.29 e Å⁻³
139 parameters	Δρ_min = −0.22 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.029 (4)

Crystal data top

C₁₁H₁₀ClNO₂	V = 1026.4 (3) Å³
M_r = 223.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.5530 (17) Å	µ = 0.35 mm⁻¹
b = 4.6499 (7) Å	T = 296 K
c = 18.274 (3) Å	0.3 × 0.2 × 0.2 mm
β = 105.786 (2)°

Data collection top

Rigaku SCXmini diffractometer	R_int = 0.034
6840 measured reflections	3 standard reflections every 150 reflections
1808 independent reflections	intensity decay: none
1542 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.037	1 restraint
wR(F²) = 0.115	H-atom parameters constrained
S = 1.08	Δρ_max = 0.29 e Å⁻³
1808 reflections	Δρ_min = −0.22 e Å⁻³
139 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.18445 (16)	0.9064 (4)	0.34245 (10)	0.0508 (5)
C2	0.23248 (18)	0.7745 (5)	0.40978 (11)	0.0608 (5)
H2	0.2071	0.8077	0.4523	0.073*
C3	0.32020 (19)	0.5895 (5)	0.41333 (12)	0.0668 (6)
H3	0.3522	0.4999	0.4596	0.080*
C4	0.31375 (16)	0.6656 (4)	0.28823 (10)	0.0486 (5)
C5	0.35750 (15)	0.6077 (4)	0.22615 (11)	0.0503 (5)
H5	0.4173	0.4832	0.2326	0.060*
C6	0.31298 (14)	0.7325 (4)	0.15691 (10)	0.0469 (4)
C7	0.22217 (14)	0.9277 (4)	0.14727 (9)	0.0443 (4)
C8	0.17947 (14)	0.9890 (4)	0.20641 (9)	0.0441 (4)
H8	0.1208	1.1173	0.1997	0.053*
C9	0.22416 (14)	0.8581 (3)	0.27829 (9)	0.0437 (4)
C10	0.43422 (17)	0.4878 (5)	0.09810 (13)	0.0659 (6)
H10A	0.4997	0.5563	0.1344	0.099*
H10B	0.4482	0.4703	0.0492	0.099*
H10C	0.4142	0.3033	0.1139	0.099*
C11	0.09705 (17)	1.2379 (5)	0.06201 (12)	0.0580 (5)
H11A	0.0339	1.1499	0.0729	0.087*
H11B	0.0780	1.2972	0.0097	0.087*
H11C	0.1195	1.4025	0.0942	0.087*
Cl1	0.07193 (4)	1.13418 (12)	0.33477 (3)	0.0656 (3)
N1	0.36194 (14)	0.5307 (4)	0.35576 (9)	0.0623 (5)
O1	0.34547 (11)	0.6869 (3)	0.09331 (7)	0.0585 (4)
O2	0.18526 (11)	1.0371 (3)	0.07552 (7)	0.0561 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0588 (11)	0.0528 (10)	0.0423 (10)	−0.0142 (9)	0.0164 (8)	−0.0043 (8)
C2	0.0742 (13)	0.0699 (12)	0.0404 (11)	−0.0112 (10)	0.0193 (10)	0.0013 (9)
C3	0.0824 (14)	0.0736 (13)	0.0398 (11)	−0.0076 (11)	0.0088 (10)	0.0115 (10)
C4	0.0543 (10)	0.0463 (10)	0.0428 (10)	−0.0079 (8)	0.0094 (8)	0.0014 (8)
C5	0.0505 (10)	0.0487 (10)	0.0506 (11)	0.0030 (8)	0.0120 (8)	0.0001 (8)
C6	0.0498 (10)	0.0491 (9)	0.0438 (10)	−0.0047 (8)	0.0162 (8)	−0.0054 (8)
C7	0.0504 (10)	0.0460 (9)	0.0363 (9)	−0.0045 (7)	0.0114 (7)	−0.0014 (7)
C8	0.0467 (9)	0.0452 (9)	0.0405 (9)	−0.0029 (7)	0.0121 (7)	−0.0012 (7)
C9	0.0487 (9)	0.0445 (9)	0.0381 (9)	−0.0113 (7)	0.0123 (7)	−0.0036 (7)
C10	0.0635 (12)	0.0696 (13)	0.0717 (14)	0.0061 (11)	0.0303 (10)	−0.0091 (11)
C11	0.0643 (12)	0.0611 (11)	0.0474 (11)	0.0071 (10)	0.0134 (9)	0.0054 (9)
Cl1	0.0735 (4)	0.0778 (4)	0.0532 (4)	0.0040 (3)	0.0302 (3)	−0.0051 (2)
N1	0.0685 (11)	0.0630 (10)	0.0506 (10)	−0.0002 (8)	0.0083 (8)	0.0112 (8)
O1	0.0633 (8)	0.0695 (9)	0.0478 (8)	0.0123 (7)	0.0239 (6)	−0.0024 (6)
O2	0.0675 (8)	0.0654 (8)	0.0380 (7)	0.0129 (7)	0.0188 (6)	0.0068 (6)

Geometric parameters (Å, º) top

C1—C2	1.360 (3)	C6—C7	1.430 (3)
C1—C9	1.411 (3)	C7—C8	1.361 (2)
C1—Cl1	1.740 (2)	C7—O2	1.365 (2)
C2—C3	1.385 (3)	C8—C9	1.418 (2)
C2—H2	0.9300	C8—H8	0.9300
C3—N1	1.325 (3)	C10—O1	1.433 (2)
C3—H3	0.9300	C10—H10A	0.9600
C4—N1	1.370 (2)	C10—H10B	0.9600
C4—C9	1.410 (3)	C10—H10C	0.9600
C4—C5	1.414 (3)	C11—O2	1.418 (2)
C5—C6	1.366 (3)	C11—H11A	0.9600
C5—H5	0.9300	C11—H11B	0.9600
C6—O1	1.349 (2)	C11—H11C	0.9600

C2—C1—C9	120.67 (19)	C7—C8—C9	120.25 (17)
C2—C1—Cl1	119.85 (16)	C7—C8—H8	119.9
C9—C1—Cl1	119.48 (14)	C9—C8—H8	119.9
C1—C2—C3	118.27 (19)	C4—C9—C1	116.33 (16)
C1—C2—H2	120.9	C4—C9—C8	119.53 (16)
C3—C2—H2	120.9	C1—C9—C8	124.14 (17)
N1—C3—C2	124.90 (18)	O1—C10—H10A	109.5
N1—C3—H3	117.6	O1—C10—H10B	109.5
C2—C3—H3	117.6	H10A—C10—H10B	109.5
N1—C4—C9	123.24 (18)	O1—C10—H10C	109.5
N1—C4—C5	117.57 (17)	H10A—C10—H10C	109.5
C9—C4—C5	119.19 (16)	H10B—C10—H10C	109.5
C6—C5—C4	120.80 (17)	O2—C11—H11A	109.5
C6—C5—H5	119.6	O2—C11—H11B	109.5
C4—C5—H5	119.6	H11A—C11—H11B	109.5
O1—C6—C5	126.01 (17)	O2—C11—H11C	109.5
O1—C6—C7	114.29 (15)	H11A—C11—H11C	109.5
C5—C6—C7	119.69 (17)	H11B—C11—H11C	109.5
C8—C7—O2	125.52 (16)	C3—N1—C4	116.59 (18)
C8—C7—C6	120.54 (15)	C6—O1—C10	117.47 (15)
O2—C7—C6	113.94 (15)	C7—O2—C11	117.24 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Cl1	0.93	2.70	3.0827 (17)	105

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀ClNO₂
M_r	223.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.5530 (17), 4.6499 (7), 18.274 (3)
β (°)	105.786 (2)
V (Å³)	1026.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6840, 1808, 1542
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.115, 1.08
No. of reflections	1808
No. of parameters	139
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.22

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Cl1	0.93	2.70	3.0827 (17)	105

Acknowledgements

We gratefully acknowledge financial support by the Natural Science Foundation of Jiangsu Province (BK2009293) and the Educational Commission of Jiangsu Province (JHB 2011–2).

References

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