2-Chloro­benzo[h]quinoline-3-carbaldehyde

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

doi:10.1107/S1600536809040720

organic compounds

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Volume 65| Part 11| November 2009| Page o2711

https://doi.org/10.1107/S1600536809040720

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2-Chlorobenzo[h]quinoline-3-carbaldehyde

S. Mohana Roopan,^a F. Nawaz Khan,^a R. Subashini,^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 6 October 2009; accepted 6 October 2009; online 10 October 2009)

The benzo[h]quinolinyl fused-ring of the title compound, C₁₄H₈ClNO, is planar (r.m.s. deviation = 0.016 Å); the formyl group is slightly bent out of the plane [the C—C—C—O torsion angle is 10.7 (4)°].

Related literature

For a review of the synthesis of quinolines by the Vilsmeier–Haack reaction, see: Meth-Cohn (1993 ).

Experimental

Crystal data

C₁₄H₈ClNO
M_r = 241.66
Monoclinic, P 2₁ /c
a = 3.9833 (2) Å
b = 12.4722 (6) Å
c = 21.4561 (13) Å
β = 90.687 (6)°
V = 1065.87 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 290 K
0.20 × 0.15 × 0.15 mm

Data collection

Oxford Diffraction Excalibur diffractometer
Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlisPro. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.936, T_max = 0.951
12099 measured reflections
1872 independent reflections
935 reflections with I > 2˘I)
R_int = 0.093

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.087
S = 0.81
1872 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlisPro. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809040720/tk2551sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040720/tk2551Isup2.hkl

checkCIF report

Related literature top

For a review of the synthesis of quinolines by the Vilsmeier–Haack reaction, see: Meth-Cohn (1993).

Experimental top

A Vilsmeier-Haack adduct prepared from phosphorus oxytrichloride (6.5 ml, 70 mmol) and N,N-dimethylformamide (2.3 ml, 30 mmol) at 273 K was added to N-(1-naphthyl)acetamide (1.85 g, 10 mmol), and the mixture was heated at 353 K for 15 h. The mixture was then poured onto ice, and the white product was collected and dried. The compound was purified by recrystallization from a petroleum ether/ethyl acetate mixture.

Structure description top

For a review of the synthesis of quinolines by the Vilsmeier–Haack reaction, see: Meth-Cohn (1993).

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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₄H₈ClNO at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-Chlorobenzo[h]quinoline-3-carbaldehyde top

Crystal data top

C₁₄H₈ClNO	F(000) = 496
M_r = 241.66	D_x = 1.506 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1012 reflections
a = 3.9833 (2) Å	θ = 1.9–20.4°
b = 12.4722 (6) Å	µ = 0.34 mm⁻¹
c = 21.4561 (13) Å	T = 290 K
β = 90.687 (6)°	Block, colorless
V = 1065.87 (10) Å³	0.20 × 0.15 × 0.15 mm
Z = 4

Data collection top

Oxford Diffraction Excalibur diffractometer	1872 independent reflections
Radiation source: fine-focus sealed tube	935 reflections with I > 2˘I)
Graphite monochromator	R_int = 0.093
ω scans	θ_max = 25.0°, θ_min = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −4→4
T_min = 0.936, T_max = 0.951	k = −14→14
12099 measured reflections	l = −25→25

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) = 0.087	H-atom parameters constrained
S = 0.81	w = 1/[σ²(F_o²) + (0.0379P)²] where P = (F_o² + 2F_c²)/3
1872 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₄H₈ClNO	V = 1065.87 (10) Å³
M_r = 241.66	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.9833 (2) Å	µ = 0.34 mm⁻¹
b = 12.4722 (6) Å	T = 290 K
c = 21.4561 (13) Å	0.20 × 0.15 × 0.15 mm
β = 90.687 (6)°

Data collection top

Oxford Diffraction Excalibur diffractometer	1872 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	935 reflections with I > 2˘I)
T_min = 0.936, T_max = 0.951	R_int = 0.093
12099 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 0.81	Δρ_max = 0.14 e Å⁻³
1872 reflections	Δρ_min = −0.19 e Å⁻³
154 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
Cl1	0.74845 (19)	0.87817 (5)	0.54210 (3)	0.0598 (3)
O1	0.1454 (5)	0.63739 (16)	0.45218 (9)	0.0658 (6)
N1	0.7413 (5)	0.74695 (15)	0.63554 (10)	0.0385 (6)
C1	0.6418 (6)	0.75706 (19)	0.57774 (13)	0.0390 (7)
C2	0.4576 (6)	0.6809 (2)	0.54353 (12)	0.0380 (7)
C3	0.3790 (6)	0.58737 (19)	0.57384 (12)	0.0399 (7)
H3	0.2557	0.5348	0.5531	0.048*
C4	0.4818 (6)	0.57031 (19)	0.63539 (12)	0.0347 (7)
C5	0.4052 (6)	0.4751 (2)	0.66944 (13)	0.0414 (7)
H5	0.2857	0.4201	0.6501	0.050*
C6	0.5043 (6)	0.4643 (2)	0.72937 (13)	0.0431 (7)
H6	0.4504	0.4018	0.7506	0.052*
C7	0.6893 (6)	0.5458 (2)	0.76127 (12)	0.0360 (7)
C8	0.7886 (6)	0.5348 (2)	0.82389 (13)	0.0473 (8)
H8	0.7339	0.4725	0.8453	0.057*
C9	0.9636 (7)	0.6135 (2)	0.85384 (13)	0.0513 (8)
H9	1.0257	0.6051	0.8955	0.062*
C10	1.0497 (6)	0.7069 (2)	0.82201 (13)	0.0474 (7)
H10	1.1693	0.7606	0.8426	0.057*
C11	0.9598 (6)	0.7202 (2)	0.76084 (12)	0.0388 (7)
H11	1.0219	0.7822	0.7399	0.047*
C12	0.7750 (6)	0.64093 (19)	0.72954 (12)	0.0319 (6)
C13	0.6639 (6)	0.65335 (19)	0.66560 (12)	0.0335 (7)
C14	0.3425 (7)	0.6954 (2)	0.47811 (14)	0.0496 (8)
H14	0.4283	0.7530	0.4558	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0849 (6)	0.0483 (5)	0.0463 (5)	−0.0102 (4)	−0.0001 (4)	0.0101 (4)
O1	0.0809 (16)	0.0710 (15)	0.0450 (14)	−0.0128 (12)	−0.0151 (12)	−0.0047 (12)
N1	0.0463 (15)	0.0353 (14)	0.0341 (15)	−0.0004 (10)	0.0016 (11)	−0.0006 (11)
C1	0.0404 (17)	0.0381 (16)	0.0387 (18)	−0.0002 (13)	0.0065 (14)	−0.0006 (14)
C2	0.0378 (17)	0.0421 (17)	0.0342 (18)	0.0034 (14)	0.0058 (14)	−0.0006 (14)
C3	0.0380 (16)	0.0431 (18)	0.0386 (18)	−0.0005 (13)	−0.0012 (14)	−0.0101 (14)
C4	0.0341 (16)	0.0356 (16)	0.0344 (18)	0.0033 (13)	0.0031 (13)	−0.0056 (14)
C5	0.0420 (17)	0.0370 (17)	0.0452 (19)	−0.0014 (13)	−0.0003 (15)	−0.0032 (15)
C6	0.0406 (17)	0.0362 (16)	0.053 (2)	0.0025 (14)	0.0051 (15)	0.0069 (15)
C7	0.0339 (16)	0.0377 (16)	0.0367 (18)	0.0071 (13)	0.0059 (14)	0.0009 (14)
C8	0.0514 (19)	0.0481 (18)	0.043 (2)	0.0077 (15)	0.0037 (15)	0.0110 (15)
C9	0.059 (2)	0.064 (2)	0.0311 (17)	0.0077 (17)	−0.0036 (15)	0.0004 (17)
C10	0.0527 (19)	0.0489 (18)	0.040 (2)	0.0048 (15)	−0.0053 (15)	−0.0048 (16)
C11	0.0417 (17)	0.0360 (16)	0.0385 (18)	0.0054 (13)	−0.0002 (14)	−0.0013 (14)
C12	0.0281 (15)	0.0329 (16)	0.0349 (17)	0.0069 (12)	0.0017 (13)	−0.0020 (13)
C13	0.0314 (16)	0.0347 (16)	0.0347 (17)	0.0045 (12)	0.0057 (13)	−0.0003 (13)
C14	0.058 (2)	0.053 (2)	0.0383 (19)	0.0027 (16)	0.0012 (16)	0.0024 (16)

Geometric parameters (Å, º) top

Cl1—C1	1.748 (3)	C6—H6	0.9300
O1—C14	1.200 (3)	C7—C8	1.403 (3)
N1—C1	1.303 (3)	C7—C12	1.412 (3)
N1—C13	1.371 (3)	C8—C9	1.361 (3)
C1—C2	1.402 (3)	C8—H8	0.9300
C2—C3	1.374 (3)	C9—C10	1.395 (3)
C2—C14	1.483 (3)	C9—H9	0.9300
C3—C4	1.394 (3)	C10—C11	1.366 (3)
C3—H3	0.9300	C10—H10	0.9300
C4—C13	1.417 (3)	C11—C12	1.399 (3)
C4—C5	1.429 (3)	C11—H11	0.9300
C5—C6	1.347 (3)	C12—C13	1.445 (3)
C5—H5	0.9300	C14—H14	0.9300
C6—C7	1.426 (3)

C1—N1—C13	117.6 (2)	C9—C8—C7	121.2 (3)
N1—C1—C2	125.7 (2)	C9—C8—H8	119.4
N1—C1—Cl1	115.3 (2)	C7—C8—H8	119.4
C2—C1—Cl1	119.0 (2)	C8—C9—C10	119.9 (3)
C3—C2—C1	116.6 (2)	C8—C9—H9	120.0
C3—C2—C14	118.8 (3)	C10—C9—H9	120.0
C1—C2—C14	124.5 (3)	C11—C10—C9	120.5 (3)
C2—C3—C4	120.8 (2)	C11—C10—H10	119.7
C2—C3—H3	119.6	C9—C10—H10	119.7
C4—C3—H3	119.6	C10—C11—C12	120.4 (3)
C3—C4—C13	117.7 (2)	C10—C11—H11	119.8
C3—C4—C5	123.3 (3)	C12—C11—H11	119.8
C13—C4—C5	119.0 (2)	C11—C12—C7	119.4 (2)
C6—C5—C4	120.6 (3)	C11—C12—C13	122.2 (2)
C6—C5—H5	119.7	C7—C12—C13	118.4 (2)
C4—C5—H5	119.7	N1—C13—C4	121.6 (2)
C5—C6—C7	122.1 (3)	N1—C13—C12	118.0 (2)
C5—C6—H6	119.0	C4—C13—C12	120.4 (2)
C7—C6—H6	119.0	O1—C14—C2	124.0 (3)
C8—C7—C12	118.5 (2)	O1—C14—H14	118.0
C8—C7—C6	121.9 (3)	C2—C14—H14	118.0
C12—C7—C6	119.6 (2)

C13—N1—C1—C2	0.9 (4)	C9—C10—C11—C12	1.1 (4)
C13—N1—C1—Cl1	−179.99 (16)	C10—C11—C12—C7	−1.6 (4)
N1—C1—C2—C3	−0.6 (4)	C10—C11—C12—C13	177.6 (2)
Cl1—C1—C2—C3	−179.69 (17)	C8—C7—C12—C11	1.0 (3)
N1—C1—C2—C14	178.9 (2)	C6—C7—C12—C11	−179.3 (2)
Cl1—C1—C2—C14	−0.2 (3)	C8—C7—C12—C13	−178.2 (2)
C1—C2—C3—C4	−0.5 (3)	C6—C7—C12—C13	1.4 (3)
C14—C2—C3—C4	−180.0 (2)	C1—N1—C13—C4	−0.1 (3)
C2—C3—C4—C13	1.1 (3)	C1—N1—C13—C12	179.6 (2)
C2—C3—C4—C5	179.4 (2)	C3—C4—C13—N1	−0.8 (3)
C3—C4—C5—C6	−178.3 (2)	C5—C4—C13—N1	−179.2 (2)
C13—C4—C5—C6	0.0 (4)	C3—C4—C13—C12	179.5 (2)
C4—C5—C6—C7	−0.3 (4)	C5—C4—C13—C12	1.1 (3)
C5—C6—C7—C8	179.2 (2)	C11—C12—C13—N1	−0.7 (3)
C5—C6—C7—C12	−0.4 (4)	C7—C12—C13—N1	178.5 (2)
C12—C7—C8—C9	0.0 (4)	C11—C12—C13—C4	179.0 (2)
C6—C7—C8—C9	−179.6 (2)	C7—C12—C13—C4	−1.8 (3)
C7—C8—C9—C10	−0.6 (4)	C3—C2—C14—O1	10.7 (4)
C8—C9—C10—C11	0.0 (4)	C1—C2—C14—O1	−168.7 (3)

Experimental details

Crystal data
Chemical formula	C₁₄H₈ClNO
M_r	241.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	290
a, b, c (Å)	3.9833 (2), 12.4722 (6), 21.4561 (13)
β (°)	90.687 (6)
V (Å³)	1065.87 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.20 × 0.15 × 0.15

Data collection
Diffractometer	Oxford Diffraction Excalibur
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.936, 0.951
No. of measured, independent and observed [I > 2˘I)] reflections	12099, 1872, 935
R_int	0.093
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.087, 0.81
No. of reflections	1872
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.19

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

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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Meth-Cohn, O. (1993). Heterocycles, 35, 539–557. CrossRef CAS Google Scholar
Oxford Diffraction (2009). CrysAlisPro. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar