(2-Chloro­benzo[h]quinolin-3-yl)methanol

Khan, F.N.; Mohana Roopan, S.; Hathwar, V.R.; Rajesh, R.; Khawar Rauf, M.

doi:10.1107/S1600536810010767

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o953

doi:10.1107/S1600536810010767

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(2-Chlorobenzo[h]quinolin-3-yl)methanol

F. Nawaz Khan,^a S. Mohana Roopan,^a Venkatesha R. Hathwar,^b R. Rajesh ^c and M. Khawar Rauf ^d ^*

^aChemistry Division, School of Advanced Sciences, VIT University, Vellore 632 014, Tamil Nadu, India, ^bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, Karnataka, India, ^cDepartment of Chemistry, Bharathiar University, Coimbatore, Tamil Nadu, India, and ^dDepartment of Chemistry, Quaid-i-Azam University Islamabad, 45320 Pakistan
^*Correspondence e-mail: khawar_rauf@hotmail.com

(Received 21 March 2010; accepted 22 March 2010; online 27 March 2010)

In the title molecule, C₁₄H₁₀ClNO, all non-H atoms are coplanar (r.m.s deviation = 0.0266 Å). In the crystal, symmetry-related molecules are hydrogen bonded via intermolecular O—H⋯O interactions, forming chains along the b axis.

Related literature

The title compound was obtained by the reduction of an aldehyde using Montmorillonite K-10 as catalyst. For background to the use of Montmorillonite clays as catalysts, see: Roopan et al. (2009b ). For related structures, see: Khan et al. (2010a ,b ); Roopan et al. (2009a ).

Experimental

Crystal data

C₁₄H₁₀ClNO
M_r = 243.68
Monoclinic, P 2₁ /c
a = 16.6953 (4) Å
b = 4.61459 (11) Å
c = 14.5588 (3) Å
β = 95.123 (2)°
V = 1117.16 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 295 K
0.35 × 0.30 × 0.28 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.896, T_max = 0.915
11643 measured reflections
2200 independent reflections
1717 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.093
S = 1.08
2200 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.19 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—H1⋯O1ⁱ	0.82	1.90	2.7154 (12)	175
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810010767/pv2269sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810010767/pv2269Isup2.hkl

checkCIF report

Comment top

Montmorillonite clays have been found to effectively catalyze a broad range of chemical reactions (Roopan et al., 2009b). In continuation of our green chemical approach on the structural chemistry of disubstituted quinolines (Khan et al., 2010a,b; Roopan et al., 2009a), we have demonstarted the reduction of an aldehyde using Montmorillonite K-10 as a catalyst, to obtain the title alcohol. In this article, the crystal structure of the title molecule is presented.

In the title molecule (Fig. 1) all non-hydrogen atoms are coplanar (r.m.s deviation = 0.0266 Å); the C—C—C—O torsion angles are -0.9 (2) and -179.73 (13)°. The crystal structure is composed of discrete molecules with bond lengths and angles quite typical for compounds of this class and agree well with the corresponding bond lengths and angles reported for some related compounds (Khan et al., 2010a & 2010b; Roopan et al., 2009). In the crystal, symmetry related molecules are hydrogen bonded via intermolecular O—H···O type interactions forming one dimensional chains along the b-axis. In addition, an intramolecular interaction, C3—H3···O1 further consolidated the crystal structure.

Related literature top

For background to the use of Montmorillonite clays as catalysts, see: Roopan et al. (2009b). For related crystal structures, see: Khan et al. (2010a,b); Roopan et al. (2009a).

Experimental top

2-Chlorbenzo[h]quinoline-3-carbaldehyde (241 mg, 1 mmol), sodium borohydride (38 mg, 1 mmol) and a catalytic amount of montmorillonite K-10 (100 mg) 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: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. Molecular structure of (I) showing atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

(2-Chlorobenzo[h]quinolin-3-yl)methanol top

Crystal data top

C₁₄H₁₀ClNO	F(000) = 504
M_r = 243.68	D_x = 1.449 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 11643 reflections
a = 16.6953 (4) Å	θ = 2.5–26.0°
b = 4.61459 (11) Å	µ = 0.32 mm⁻¹
c = 14.5588 (3) Å	T = 295 K
β = 95.123 (2)°	Block, colourless
V = 1117.16 (5) Å³	0.35 × 0.30 × 0.28 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer	2200 independent reflections
Radiation source: fine-focus sealed tube	1717 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −20→20
T_min = 0.896, T_max = 0.915	k = −5→5
11643 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0447P)² + 0.1644P] where P = (F_o² + 2F_c²)/3
2200 reflections	(Δ/σ)_max = 0.001
155 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₄H₁₀ClNO	V = 1117.16 (5) Å³
M_r = 243.68	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.6953 (4) Å	µ = 0.32 mm⁻¹
b = 4.61459 (11) Å	T = 295 K
c = 14.5588 (3) Å	0.35 × 0.30 × 0.28 mm
β = 95.123 (2)°

Data collection top

Oxford Diffraction Xcalibur diffractometer	2200 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1717 reflections with I > 2σ(I)
T_min = 0.896, T_max = 0.915	R_int = 0.028
11643 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.08	Δρ_max = 0.19 e Å⁻³
2200 reflections	Δρ_min = −0.22 e Å⁻³
155 parameters

Special details top

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 > 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
Cl1	0.38036 (3)	0.30225 (12)	0.55246 (3)	0.05783 (19)
N1	0.28031 (8)	0.6236 (3)	0.45110 (8)	0.0350 (3)
O1	0.47139 (8)	0.0886 (3)	0.28368 (8)	0.0497 (3)
H1	0.4911	0.2355	0.2633	0.074*
C2	0.37487 (9)	0.3556 (3)	0.36689 (10)	0.0315 (3)
C1	0.33981 (9)	0.4434 (3)	0.44662 (10)	0.0331 (4)
C7	0.18191 (9)	0.9418 (4)	0.37325 (11)	0.0366 (4)
C9	0.27796 (9)	0.6741 (3)	0.28570 (10)	0.0333 (4)
C3	0.34176 (9)	0.4759 (3)	0.28642 (10)	0.0339 (4)
H3	0.3619	0.4254	0.2311	0.041*
C4	0.24384 (10)	0.8084 (4)	0.20323 (11)	0.0426 (4)
H4	0.2637	0.7635	0.1472	0.051*
C8	0.24801 (9)	0.7420 (3)	0.37074 (10)	0.0309 (3)
C6	0.14987 (10)	1.0709 (4)	0.28978 (12)	0.0417 (4)
C13	0.14771 (10)	1.0095 (4)	0.45516 (12)	0.0478 (4)
H13	0.1685	0.9266	0.5105	0.057*
C5	0.18321 (11)	0.9994 (4)	0.20550 (12)	0.0477 (5)
H5	0.1625	1.0872	0.1510	0.057*
C14	0.44481 (9)	0.1482 (4)	0.37137 (11)	0.0395 (4)
H14A	0.4891	0.2296	0.4108	0.047*
H14B	0.4291	−0.0321	0.3990	0.047*
C10	0.08499 (11)	1.2661 (4)	0.29225 (15)	0.0551 (5)
H10	0.0639	1.3552	0.2381	0.066*
C11	0.05304 (11)	1.3253 (5)	0.37239 (16)	0.0638 (6)
H11	0.0100	1.4531	0.3726	0.077*
C12	0.08390 (12)	1.1971 (5)	0.45434 (15)	0.0609 (6)
H12	0.0612	1.2386	0.5089	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0679 (3)	0.0734 (4)	0.0331 (2)	0.0227 (3)	0.0093 (2)	0.0130 (2)
N1	0.0384 (7)	0.0381 (8)	0.0294 (7)	0.0009 (6)	0.0085 (5)	−0.0015 (6)
O1	0.0613 (8)	0.0343 (7)	0.0590 (8)	0.0033 (6)	0.0365 (6)	−0.0016 (6)
C2	0.0339 (8)	0.0279 (8)	0.0340 (8)	−0.0049 (7)	0.0095 (6)	−0.0023 (6)
C1	0.0390 (8)	0.0338 (9)	0.0274 (8)	−0.0005 (7)	0.0076 (6)	0.0018 (7)
C7	0.0335 (8)	0.0339 (9)	0.0424 (9)	−0.0040 (7)	0.0040 (7)	−0.0054 (7)
C9	0.0355 (8)	0.0351 (9)	0.0297 (8)	−0.0068 (7)	0.0049 (6)	−0.0011 (7)
C3	0.0388 (8)	0.0368 (9)	0.0277 (8)	−0.0058 (7)	0.0122 (6)	−0.0062 (7)
C4	0.0469 (10)	0.0511 (11)	0.0299 (8)	−0.0052 (9)	0.0047 (7)	−0.0014 (8)
C8	0.0316 (8)	0.0321 (8)	0.0293 (7)	−0.0040 (6)	0.0051 (6)	−0.0030 (6)
C6	0.0380 (9)	0.0358 (9)	0.0500 (10)	−0.0046 (7)	−0.0034 (7)	−0.0026 (8)
C13	0.0440 (10)	0.0516 (11)	0.0484 (10)	0.0057 (9)	0.0075 (8)	−0.0106 (8)
C5	0.0511 (10)	0.0491 (11)	0.0410 (9)	−0.0024 (9)	−0.0062 (8)	0.0071 (8)
C14	0.0422 (9)	0.0354 (10)	0.0429 (9)	0.0008 (7)	0.0145 (7)	0.0001 (7)
C10	0.0465 (11)	0.0458 (11)	0.0697 (13)	0.0043 (9)	−0.0130 (9)	−0.0032 (10)
C11	0.0427 (11)	0.0594 (13)	0.0874 (16)	0.0163 (10)	−0.0053 (10)	−0.0185 (12)
C12	0.0467 (11)	0.0668 (14)	0.0698 (13)	0.0104 (10)	0.0094 (9)	−0.0210 (11)

Geometric parameters (Å, º) top

Cl1—C1	1.7525 (15)	C4—C5	1.345 (2)
N1—C1	1.3014 (19)	C4—H4	0.9300
N1—C8	1.3585 (19)	C6—C10	1.412 (2)
O1—C14	1.4155 (19)	C6—C5	1.430 (2)
O1—H1	0.8200	C13—C12	1.372 (2)
C2—C3	1.368 (2)	C13—H13	0.9300
C2—C1	1.405 (2)	C5—H5	0.9300
C2—C14	1.507 (2)	C14—H14A	0.9700
C7—C13	1.402 (2)	C14—H14B	0.9700
C7—C6	1.415 (2)	C10—C11	1.353 (3)
C7—C8	1.441 (2)	C10—H10	0.9300
C9—C3	1.403 (2)	C11—C12	1.389 (3)
C9—C8	1.411 (2)	C11—H11	0.9300
C9—C4	1.424 (2)	C12—H12	0.9300
C3—H3	0.9300

C1—N1—C8	117.39 (13)	C10—C6—C5	121.83 (17)
C14—O1—H1	109.5	C7—C6—C5	119.57 (16)
C3—C2—C1	115.09 (14)	C12—C13—C7	120.52 (18)
C3—C2—C14	123.18 (14)	C12—C13—H13	119.7
C1—C2—C14	121.71 (14)	C7—C13—H13	119.7
N1—C1—C2	126.98 (14)	C4—C5—C6	121.58 (16)
N1—C1—Cl1	115.47 (11)	C4—C5—H5	119.2
C2—C1—Cl1	117.54 (12)	C6—C5—H5	119.2
C13—C7—C6	119.02 (16)	O1—C14—C2	112.85 (13)
C13—C7—C8	122.33 (15)	O1—C14—H14A	109.0
C6—C7—C8	118.64 (15)	C2—C14—H14A	109.0
C3—C9—C8	117.80 (13)	O1—C14—H14B	109.0
C3—C9—C4	122.41 (14)	C2—C14—H14B	109.0
C8—C9—C4	119.78 (15)	H14A—C14—H14B	107.8
C2—C3—C9	121.29 (14)	C11—C10—C6	120.88 (18)
C2—C3—H3	119.4	C11—C10—H10	119.6
C9—C3—H3	119.4	C6—C10—H10	119.6
C5—C4—C9	120.65 (16)	C10—C11—C12	120.66 (18)
C5—C4—H4	119.7	C10—C11—H11	119.7
C9—C4—H4	119.7	C12—C11—H11	119.7
N1—C8—C9	121.44 (14)	C13—C12—C11	120.30 (19)
N1—C8—C7	118.79 (13)	C13—C12—H12	119.8
C9—C8—C7	119.77 (13)	C11—C12—H12	119.8
C10—C6—C7	118.61 (17)

C8—N1—C1—C2	−0.2 (2)	C6—C7—C8—N1	178.27 (14)
C8—N1—C1—Cl1	178.89 (11)	C13—C7—C8—C9	177.63 (15)
C3—C2—C1—N1	0.1 (2)	C6—C7—C8—C9	−1.5 (2)
C14—C2—C1—N1	178.96 (15)	C13—C7—C6—C10	0.7 (2)
C3—C2—C1—Cl1	−178.97 (11)	C8—C7—C6—C10	179.84 (15)
C14—C2—C1—Cl1	−0.1 (2)	C13—C7—C6—C5	−178.81 (16)
C1—C2—C3—C9	0.6 (2)	C8—C7—C6—C5	0.4 (2)
C14—C2—C3—C9	−178.32 (14)	C6—C7—C13—C12	0.3 (3)
C8—C9—C3—C2	−1.0 (2)	C8—C7—C13—C12	−178.85 (16)
C4—C9—C3—C2	178.28 (15)	C9—C4—C5—C6	−1.2 (3)
C3—C9—C4—C5	−179.35 (15)	C10—C6—C5—C4	−178.47 (16)
C8—C9—C4—C5	0.0 (2)	C7—C6—C5—C4	1.0 (3)
C1—N1—C8—C9	−0.4 (2)	C3—C2—C14—O1	−0.9 (2)
C1—N1—C8—C7	179.86 (14)	C1—C2—C14—O1	−179.73 (13)
C3—C9—C8—N1	0.9 (2)	C7—C6—C10—C11	−1.1 (3)
C4—C9—C8—N1	−178.40 (14)	C5—C6—C10—C11	178.35 (18)
C3—C9—C8—C7	−179.28 (13)	C6—C10—C11—C12	0.6 (3)
C4—C9—C8—C7	1.4 (2)	C7—C13—C12—C11	−0.8 (3)
C13—C7—C8—N1	−2.6 (2)	C10—C11—C12—C13	0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.82	1.90	2.7154 (12)	175
C3—H3···O1	0.93	2.47	2.809 (2)	102

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀ClNO
M_r	243.68
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	16.6953 (4), 4.61459 (11), 14.5588 (3)
β (°)	95.123 (2)
V (Å³)	1117.16 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.35 × 0.30 × 0.28

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.896, 0.915
No. of measured, independent and observed [I > 2σ(I)] reflections	11643, 2200, 1717
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.093, 1.08
No. of reflections	2200
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.22

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.82	1.90	2.7154 (12)	175
C3—H3···O1	0.93	2.47	2.809 (2)	102

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Acknowledgements

We thank the Department of Science and Technology, India, for use of the CCD facility set up under the FIST–DST program at SSCU, IISc. We thank Professor T. N. Guru Row, IISc, Bangalore, for his help with the data collection. FNK thanks the DST for Fast Track Proposal funding.

References

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