2-Chloro-3-hydroxy­methyl-6-methoxy­quinoline

Khan, F.N.; Mohana Roopan, S.; Hathwar, V.R.; Ng, S.W.

doi:10.1107/S1600536809054051

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o201

doi:10.1107/S1600536809054051

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2-Chloro-3-hydroxymethyl-6-methoxyquinoline

F. Nawaz Khan,^a S. Mohana Roopan,^a Venkatesha R. Hathwar ^b and Seik Weng Ng ^c ^*

^aChemistry Division, School of Science and Humanities, VIT University, Vellore 632 014, Tamil Nadu, India, ^bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, Karnataka, India, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 12 December 2009; accepted 15 December 2009; online 19 December 2009)

All the non-H atoms of the title compound, C₁₁H₁₀ClNO₂, are roughly coplanar (r.m.s. deviation = 0.058 Å). In the crystal, adjacent molecules are linked by an O—H⋯N hydrogen bond, generating chains running along the a axis.

Related literature

Substituted quinoline-3-carbaldehydes are intermediates for annelation and functional group modification; for a review of the synthesis of quinolines by the Vilsmeier–Haack reaction, see: Meth-Cohn (1993 ).

Experimental

Crystal data

C₁₁H₁₀ClNO₂
M_r = 223.65
Monoclinic, P 2₁ /n
a = 6.9738 (3) Å
b = 21.4668 (9) Å
c = 7.3479 (4) Å
β = 108.220 (5)°
V = 1044.87 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.28 × 0.21 × 0.20 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.910, T_max = 0.935
11517 measured reflections
2348 independent reflections
1487 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.108
S = 0.97
2348 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.82	2.16	2.913 (2)	153
Symmetry code: (i) x+1, y, z.

Data collection: SMART (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: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809054051/bt5140sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809054051/bt5140Isup2.hkl

checkCIF report

Related literature top

Experimental top

2-Chloro-8-methoxyquinoline-3-carbaldehyde (220 mg, 1 mmol), sodium borohydride (38 mg, 1 mmol) and a catalytic amount of montmorillonite K-10 were placed in a beaker. The contents were irradiated at 500 W for 5 min. The product was dissolved in ethyl acetate and the residue removed by filtration. The filtrate was subjected to column chromatography on silica, and ethyl acetate/petroleum ether was used as the eluant. The solvent was evaporated and the residue recrystallized from chloroform to give colorless crystals.

Computing details top

Data collection: SMART (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: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₁₁H₁₀ClNO₂ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-Chloro-3-hydroxymethyl-6-methoxyquinoline top

Crystal data top

C₁₁H₁₀ClNO₂	F(000) = 464
M_r = 223.65	D_x = 1.422 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1941 reflections
a = 6.9738 (3) Å	θ = 3.1–25.5°
b = 21.4668 (9) Å	µ = 0.34 mm⁻¹
c = 7.3479 (4) Å	T = 293 K
β = 108.220 (5)°	Block, colorless
V = 1044.87 (8) Å³	0.28 × 0.21 × 0.20 mm
Z = 4

Data collection top

Bruker SMART area-detector diffractometer	2348 independent reflections
Radiation source: fine-focus sealed tube	1487 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
T_min = 0.910, T_max = 0.935	k = −26→27
11517 measured reflections	l = −9→9

Refinement top

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.058P)²] where P = (F_o² + 2F_c²)/3
2348 reflections	(Δ/σ)_max = 0.001
138 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₁H₁₀ClNO₂	V = 1044.87 (8) Å³
M_r = 223.65	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.9738 (3) Å	µ = 0.34 mm⁻¹
b = 21.4668 (9) Å	T = 293 K
c = 7.3479 (4) Å	0.28 × 0.21 × 0.20 mm
β = 108.220 (5)°

Data collection top

Bruker SMART area-detector diffractometer	2348 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1487 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.935	R_int = 0.035
11517 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 0.97	Δρ_max = 0.21 e Å⁻³
2348 reflections	Δρ_min = −0.25 e Å⁻³
138 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.33210 (8)	0.65210 (2)	0.10064 (7)	0.0648 (2)
O1	0.97027 (18)	0.59162 (7)	0.33602 (19)	0.0672 (4)
H1	1.0200	0.5790	0.2554	0.101*
O2	0.4314 (2)	0.29302 (7)	0.3876 (2)	0.0766 (5)
N1	0.2607 (2)	0.53770 (7)	0.16969 (18)	0.0446 (4)
C1	0.4061 (3)	0.57605 (8)	0.1763 (2)	0.0430 (4)
C2	0.6156 (2)	0.56246 (8)	0.2401 (2)	0.0408 (4)
C3	0.6650 (2)	0.50291 (8)	0.2994 (2)	0.0437 (4)
H3	0.8004	0.4916	0.3461	0.052*
C4	0.5149 (2)	0.45775 (8)	0.2917 (2)	0.0390 (4)
C5	0.5600 (3)	0.39542 (9)	0.3483 (2)	0.0494 (5)
H5	0.6935	0.3821	0.3926	0.059*
C6	0.4070 (3)	0.35449 (9)	0.3379 (2)	0.0526 (5)
C7	0.2053 (3)	0.37443 (9)	0.2741 (2)	0.0546 (5)
H7	0.1027	0.3463	0.2698	0.065*
C8	0.1583 (3)	0.43397 (9)	0.2189 (2)	0.0507 (5)
H8	0.0238	0.4463	0.1758	0.061*
C9	0.3120 (2)	0.47761 (8)	0.2261 (2)	0.0405 (4)
C10	0.7702 (3)	0.61178 (9)	0.2442 (3)	0.0528 (5)
H10A	0.7575	0.6240	0.1138	0.063*
H10B	0.7430	0.6482	0.3103	0.063*
C11	0.6296 (4)	0.26820 (11)	0.4324 (4)	0.0912 (8)
H11A	0.6799	0.2747	0.3263	0.137*
H11B	0.6264	0.2244	0.4573	0.137*
H11C	0.7163	0.2887	0.5439	0.137*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0574 (3)	0.0603 (3)	0.0736 (4)	0.0151 (2)	0.0158 (3)	0.0111 (3)
O1	0.0365 (8)	0.0931 (11)	0.0762 (9)	−0.0030 (7)	0.0235 (7)	−0.0079 (8)
O2	0.0887 (12)	0.0522 (9)	0.0807 (10)	0.0010 (8)	0.0147 (8)	0.0016 (7)
N1	0.0306 (8)	0.0591 (9)	0.0412 (8)	0.0057 (7)	0.0069 (6)	−0.0035 (7)
C1	0.0389 (10)	0.0539 (10)	0.0365 (9)	0.0122 (8)	0.0123 (8)	−0.0006 (8)
C2	0.0347 (9)	0.0573 (11)	0.0341 (8)	0.0033 (8)	0.0161 (7)	−0.0036 (8)
C3	0.0277 (9)	0.0628 (11)	0.0403 (9)	0.0106 (8)	0.0103 (7)	−0.0021 (8)
C4	0.0328 (9)	0.0524 (10)	0.0307 (8)	0.0059 (8)	0.0083 (7)	−0.0051 (7)
C5	0.0420 (11)	0.0593 (12)	0.0428 (10)	0.0127 (9)	0.0076 (8)	−0.0032 (9)
C6	0.0589 (13)	0.0534 (12)	0.0427 (10)	−0.0005 (9)	0.0119 (9)	−0.0073 (9)
C7	0.0504 (12)	0.0631 (13)	0.0476 (10)	−0.0115 (10)	0.0115 (9)	−0.0095 (9)
C8	0.0334 (10)	0.0698 (13)	0.0443 (10)	−0.0022 (9)	0.0056 (8)	−0.0093 (9)
C9	0.0334 (9)	0.0559 (11)	0.0304 (8)	0.0047 (8)	0.0070 (7)	−0.0069 (8)
C10	0.0433 (11)	0.0653 (12)	0.0547 (11)	0.0001 (9)	0.0223 (9)	0.0013 (10)
C11	0.113 (2)	0.0600 (14)	0.1016 (18)	0.0275 (14)	0.0342 (16)	0.0121 (13)

Geometric parameters (Å, º) top

Cl1—C1	1.7496 (18)	C4—C9	1.411 (2)
O1—C10	1.414 (2)	C5—C6	1.366 (2)
O1—H1	0.8200	C5—H5	0.9300
O2—C6	1.366 (2)	C6—C7	1.403 (3)
O2—C11	1.421 (3)	C7—C8	1.350 (3)
N1—C1	1.295 (2)	C7—H7	0.9300
N1—C9	1.368 (2)	C8—C9	1.412 (2)
C1—C2	1.418 (2)	C8—H8	0.9300
C2—C3	1.360 (2)	C10—H10A	0.9700
C2—C10	1.505 (2)	C10—H10B	0.9700
C3—C4	1.415 (2)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.407 (2)	C11—H11C	0.9600

C10—O1—H1	109.5	C8—C7—C6	120.86 (18)
C6—O2—C11	117.08 (18)	C8—C7—H7	119.6
C1—N1—C9	117.42 (14)	C6—C7—H7	119.6
N1—C1—C2	126.53 (16)	C7—C8—C9	120.44 (17)
N1—C1—Cl1	115.57 (13)	C7—C8—H8	119.8
C2—C1—Cl1	117.90 (14)	C9—C8—H8	119.8
C3—C2—C1	115.52 (16)	N1—C9—C4	121.87 (16)
C3—C2—C10	123.17 (16)	N1—C9—C8	119.38 (15)
C1—C2—C10	121.30 (16)	C4—C9—C8	118.75 (16)
C2—C3—C4	121.42 (16)	O1—C10—C2	112.82 (16)
C2—C3—H3	119.3	O1—C10—H10A	109.0
C4—C3—H3	119.3	C2—C10—H10A	109.0
C5—C4—C9	119.71 (16)	O1—C10—H10B	109.0
C5—C4—C3	123.07 (16)	C2—C10—H10B	109.0
C9—C4—C3	117.21 (15)	H10A—C10—H10B	107.8
C6—C5—C4	119.79 (17)	O2—C11—H11A	109.5
C6—C5—H5	120.1	O2—C11—H11B	109.5
C4—C5—H5	120.1	H11A—C11—H11B	109.5
O2—C6—C5	125.23 (18)	O2—C11—H11C	109.5
O2—C6—C7	114.34 (18)	H11A—C11—H11C	109.5
C5—C6—C7	120.43 (18)	H11B—C11—H11C	109.5

C9—N1—C1—C2	−1.4 (2)	C4—C5—C6—C7	−1.1 (3)
C9—N1—C1—Cl1	179.45 (10)	O2—C6—C7—C8	−179.55 (16)
N1—C1—C2—C3	0.1 (2)	C5—C6—C7—C8	1.1 (3)
Cl1—C1—C2—C3	179.24 (12)	C6—C7—C8—C9	−0.6 (3)
N1—C1—C2—C10	−178.78 (16)	C1—N1—C9—C4	0.9 (2)
Cl1—C1—C2—C10	0.4 (2)	C1—N1—C9—C8	−179.17 (15)
C1—C2—C3—C4	1.7 (2)	C5—C4—C9—N1	179.93 (14)
C10—C2—C3—C4	−179.43 (15)	C3—C4—C9—N1	0.8 (2)
C2—C3—C4—C5	178.76 (15)	C5—C4—C9—C8	0.0 (2)
C2—C3—C4—C9	−2.1 (2)	C3—C4—C9—C8	−179.16 (14)
C9—C4—C5—C6	0.5 (2)	C7—C8—C9—N1	−179.89 (15)
C3—C4—C5—C6	179.60 (16)	C7—C8—C9—C4	0.1 (2)
C11—O2—C6—C5	−7.7 (3)	C3—C2—C10—O1	−6.8 (2)
C11—O2—C6—C7	173.00 (17)	C1—C2—C10—O1	171.94 (14)
C4—C5—C6—O2	179.68 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	2.16	2.913 (2)	153

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀ClNO₂
M_r	223.65
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.9738 (3), 21.4668 (9), 7.3479 (4)
β (°)	108.220 (5)
V (Å³)	1044.87 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.28 × 0.21 × 0.20

Data collection
Diffractometer	Bruker SMART area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.910, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	11517, 2348, 1487
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.108, 0.97
No. of reflections	2348
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.25

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	2.16	2.913 (2)	153

Symmetry code: (i) x+1, y, z.

Acknowledgements

We thank the Department of Science and Technology, India, for use of the diffraction facility at IISc under the IRHPA–DST program. FNK thanks the DST for Fast Track Proposal funding. We thank VIT University and the University of Malaya for supporting this study.

References

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