2-Chloro-3-hydroxy­methyl-7,8-dimethyl­quinoline

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

doi:10.1107/S160053680905404X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o200

doi:10.1107/S160053680905404X

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2-Chloro-3-hydroxymethyl-7,8-dimethylquinoline

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 non-H atoms of the title compound, C₁₂H₁₂ClNO, are co-planar (r.m.s. deviation = 0.055 Å). The hydroxy H atom is disordered over two positions of equal occupancy. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, generating zigzag chains running along the b 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

C₁₂H₁₂ClNO
M_r = 221.68
Monoclinic, P 2₁ /c
a = 17.4492 (12) Å
b = 4.6271 (2) Å
c = 14.3773 (7) Å
β = 113.297 (7)°
V = 1066.17 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 K
0.38 × 0.15 × 0.06 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.885, T_max = 0.981
10456 measured reflections
1884 independent reflections
1488 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.094
S = 1.05
1884 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.16 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
O1—H1a⋯O1ⁱ	0.82	1.91	2.715 (3)	167
O1—H1b⋯O1ⁱⁱ	0.82	1.91	2.720 (3)	168
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+1, -z+1.

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/S160053680905404X/bt5139sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680905404X/bt5139Isup2.hkl

checkCIF report

Related literature top

Experimental top

2-Chloro-7,8-dimethylquinoline-3-carbaldehyde (220 mg, 1 mmol), sodium borohydride (38 mg, 1 mmol) and 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. Thermal ellipsoid plot (Barbour, 2001) of C₁₂H₁₂ClNO at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-Chloro-3-hydroxymethyl-7,8-dimethylquinoline top

Crystal data top

C₁₂H₁₂ClNO	F(000) = 464
M_r = 221.68	D_x = 1.381 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 963 reflections
a = 17.4492 (12) Å	θ = 3.1–25.0°
b = 4.6271 (2) Å	µ = 0.33 mm⁻¹
c = 14.3773 (7) Å	T = 293 K
β = 113.297 (7)°	Plate, colorless
V = 1066.17 (10) Å³	0.38 × 0.15 × 0.06 mm
Z = 4

Data collection top

Bruker SMART area-detector diffractometer	1884 independent reflections
Radiation source: fine-focus sealed tube	1488 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→20
T_min = 0.885, T_max = 0.981	k = −5→5
10456 measured reflections	l = −17→17

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0496P)² + 0.1434P] where P = (F_o² + 2F_c²)/3
1884 reflections	(Δ/σ)_max = 0.001
139 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₂H₁₂ClNO	V = 1066.17 (10) Å³
M_r = 221.68	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.4492 (12) Å	µ = 0.33 mm⁻¹
b = 4.6271 (2) Å	T = 293 K
c = 14.3773 (7) Å	0.38 × 0.15 × 0.06 mm
β = 113.297 (7)°

Data collection top

Bruker SMART area-detector diffractometer	1884 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1488 reflections with I > 2σ(I)
T_min = 0.885, T_max = 0.981	R_int = 0.033
10456 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.05	Δρ_max = 0.16 e Å⁻³
1884 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.37792 (3)	0.62190 (11)	0.12385 (3)	0.0547 (2)
O1	0.46228 (9)	0.7503 (3)	0.45560 (9)	0.0578 (4)
H1A	0.4892	0.8991	0.4763	0.087*	0.50
H1B	0.4914	0.6102	0.4824	0.087*	0.50
N1	0.27105 (9)	0.2833 (3)	0.15172 (10)	0.0365 (3)
C1	0.33144 (11)	0.4587 (4)	0.19891 (12)	0.0361 (4)
C2	0.36337 (11)	0.5327 (3)	0.30325 (12)	0.0365 (4)
C3	0.32309 (11)	0.4071 (3)	0.35710 (12)	0.0381 (4)
H3	0.3403	0.4493	0.4256	0.046*
C4	0.25620 (10)	0.2154 (4)	0.31127 (12)	0.0349 (4)
C5	0.21258 (12)	0.0807 (4)	0.36385 (13)	0.0427 (5)
H5	0.2273	0.1186	0.4323	0.051*
C6	0.14924 (12)	−0.1037 (4)	0.31451 (13)	0.0440 (5)
H6	0.1210	−0.1899	0.3502	0.053*
C7	0.12436 (11)	−0.1703 (4)	0.21072 (13)	0.0398 (4)
C8	0.16551 (11)	−0.0432 (4)	0.15657 (12)	0.0370 (4)
C9	0.23169 (10)	0.1536 (3)	0.20687 (12)	0.0333 (4)
C10	0.43655 (11)	0.7321 (4)	0.34903 (13)	0.0454 (5)
H10A	0.4825	0.6623	0.3334	0.054*
H10B	0.4215	0.9231	0.3196	0.054*
C11	0.05264 (12)	−0.3765 (4)	0.16298 (16)	0.0558 (5)
H11A	0.0510	−0.4393	0.0986	0.084*	0.50
H11B	0.0013	−0.2809	0.1535	0.084*	0.50
H11C	0.0599	−0.5409	0.2064	0.084*	0.50
H11D	0.0238	−0.4015	0.2071	0.084*	0.50
H11E	0.0735	−0.5598	0.1521	0.084*	0.50
H11F	0.0149	−0.2998	0.0993	0.084*	0.50
C12	0.14234 (13)	−0.1070 (4)	0.04636 (13)	0.0516 (5)
H12A	0.1910	−0.1694	0.0363	0.077*	0.50
H12B	0.1203	0.0644	0.0073	0.077*	0.50
H12C	0.1009	−0.2568	0.0250	0.077*	0.50
H12D	0.0838	−0.0718	0.0095	0.077*	0.50
H12E	0.1545	−0.3056	0.0384	0.077*	0.50
H12F	0.1739	0.0156	0.0207	0.077*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0522 (3)	0.0662 (4)	0.0492 (3)	−0.0064 (2)	0.0237 (2)	0.0071 (2)
O1	0.0632 (9)	0.0508 (8)	0.0438 (7)	−0.0109 (7)	0.0045 (6)	−0.0114 (6)
N1	0.0374 (9)	0.0395 (8)	0.0307 (7)	0.0031 (7)	0.0116 (6)	0.0004 (6)
C1	0.0360 (10)	0.0362 (10)	0.0357 (9)	0.0056 (8)	0.0138 (8)	0.0032 (7)
C2	0.0369 (10)	0.0313 (9)	0.0366 (9)	0.0060 (8)	0.0094 (8)	−0.0016 (7)
C3	0.0420 (11)	0.0384 (10)	0.0283 (8)	0.0051 (8)	0.0078 (7)	−0.0053 (7)
C4	0.0375 (10)	0.0344 (9)	0.0308 (8)	0.0068 (8)	0.0113 (7)	−0.0004 (7)
C5	0.0478 (11)	0.0506 (12)	0.0310 (9)	0.0050 (9)	0.0169 (8)	0.0009 (8)
C6	0.0431 (11)	0.0482 (11)	0.0438 (10)	0.0061 (9)	0.0203 (8)	0.0099 (8)
C7	0.0345 (10)	0.0368 (10)	0.0439 (10)	0.0062 (8)	0.0110 (8)	0.0054 (8)
C8	0.0370 (10)	0.0361 (10)	0.0320 (9)	0.0055 (8)	0.0075 (7)	0.0004 (7)
C9	0.0351 (10)	0.0335 (9)	0.0293 (8)	0.0060 (8)	0.0105 (7)	0.0007 (7)
C10	0.0448 (12)	0.0382 (10)	0.0463 (10)	−0.0017 (9)	0.0107 (8)	−0.0033 (8)
C11	0.0454 (12)	0.0536 (13)	0.0631 (13)	−0.0041 (10)	0.0157 (10)	0.0039 (10)
C12	0.0547 (13)	0.0576 (13)	0.0342 (9)	−0.0056 (10)	0.0087 (9)	−0.0064 (8)

Geometric parameters (Å, º) top

Cl1—C1	1.7563 (17)	C7—C11	1.506 (3)
O1—C10	1.418 (2)	C8—C9	1.423 (2)
O1—H1A	0.8200	C8—C12	1.501 (2)
O1—H1B	0.8200	C10—H10A	0.9700
N1—C1	1.290 (2)	C10—H10B	0.9700
N1—C9	1.375 (2)	C11—H11A	0.9600
C1—C2	1.420 (2)	C11—H11B	0.9600
C2—C3	1.364 (2)	C11—H11C	0.9600
C2—C10	1.500 (2)	C11—H11D	0.9600
C3—C4	1.405 (2)	C11—H11E	0.9600
C3—H3	0.9300	C11—H11F	0.9600
C4—C5	1.412 (2)	C12—H12A	0.9600
C4—C9	1.418 (2)	C12—H12B	0.9600
C5—C6	1.354 (3)	C12—H12C	0.9600
C5—H5	0.9300	C12—H12D	0.9600
C6—C7	1.413 (2)	C12—H12E	0.9600
C6—H6	0.9300	C12—H12F	0.9600
C7—C8	1.382 (2)

C10—O1—H1A	109.5	O1—C10—C2	111.18 (14)
C10—O1—H1B	109.5	O1—C10—H10A	109.4
C1—N1—C9	117.49 (14)	C2—C10—H10A	109.4
N1—C1—C2	127.22 (15)	O1—C10—H10B	109.4
N1—C1—Cl1	115.28 (12)	C2—C10—H10B	109.4
C2—C1—Cl1	117.51 (13)	H10A—C10—H10B	108.0
C3—C2—C1	114.95 (16)	C7—C11—H11A	109.5
C3—C2—C10	123.59 (15)	C7—C11—H11B	109.5
C1—C2—C10	121.46 (15)	H11A—C11—H11B	109.5
C2—C3—C4	121.44 (15)	C7—C11—H11C	109.5
C2—C3—H3	119.3	H11A—C11—H11C	109.5
C4—C3—H3	119.3	H11B—C11—H11C	109.5
C3—C4—C5	123.44 (15)	C7—C11—H11D	109.5
C3—C4—C9	118.06 (15)	C7—C11—H11E	109.5
C5—C4—C9	118.49 (16)	H11D—C11—H11E	109.5
C6—C5—C4	119.92 (16)	C7—C11—H11F	109.5
C6—C5—H5	120.0	H11D—C11—H11F	109.5
C4—C5—H5	120.0	H11E—C11—H11F	109.5
C5—C6—C7	122.47 (16)	C8—C12—H12A	109.5
C5—C6—H6	118.8	C8—C12—H12B	109.5
C7—C6—H6	118.8	H12A—C12—H12B	109.5
C8—C7—C6	119.41 (16)	C8—C12—H12C	109.5
C8—C7—C11	122.41 (16)	H12A—C12—H12C	109.5
C6—C7—C11	118.17 (16)	H12B—C12—H12C	109.5
C7—C8—C9	118.95 (15)	C8—C12—H12D	109.5
C7—C8—C12	121.87 (16)	C8—C12—H12E	109.5
C9—C8—C12	119.19 (15)	H12D—C12—H12E	109.5
N1—C9—C4	120.81 (15)	C8—C12—H12F	109.5
N1—C9—C8	118.43 (14)	H12D—C12—H12F	109.5
C4—C9—C8	120.75 (15)	H12E—C12—H12F	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1a···O1ⁱ	0.82	1.91	2.715 (3)	167
O1—H1b···O1ⁱⁱ	0.82	1.91	2.720 (3)	168

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂ClNO
M_r	221.68
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	17.4492 (12), 4.6271 (2), 14.3773 (7)
β (°)	113.297 (7)
V (Å³)	1066.17 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.38 × 0.15 × 0.06

Data collection
Diffractometer	Bruker SMART area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.885, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	10456, 1884, 1488
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.094, 1.05
No. of reflections	1884
No. of parameters	139
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.22

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—H1a···O1ⁱ	0.82	1.91	2.715 (3)	167
O1—H1b···O1ⁱⁱ	0.82	1.91	2.720 (3)	168

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1.

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 also thank VIT University and the University of Malaya for supporting this study.

References

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Meth-Cohn, O. (1993). Heterocycles, 35, 539–557. CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
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