4-Azido-2-chloro-6-methyl­quinoline

Natarajan, S.; Rajesh, K.; Vijayakumar, V.; Suresh, J.; Lakshman, P.L.N.

doi:10.1107/S1600536809007041

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o671

doi:10.1107/S1600536809007041

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4-Azido-2-chloro-6-methylquinoline

S. Natarajan,^a K. Rajesh,^b V. Vijayakumar,^b J. Suresh ^c and P. L. Nilantha Lakshman ^d ^*

^aDepartment of Physics, Madurai Kamaraj University, Madurai 625 021, India, ^bOrganic Chemistry Division, School of Science and Humanities, VIT University, Vellore 632 014, India, ^cDepartment of Physics, The Madura College, Madurai 625 011, India, and ^dDepartment of Food Science and Technology, Faculty of Agriculture, University of Ruhuna, Mapalana, Kamburupitiya 81100, Sri Lanka
^*Correspondence e-mail: nilanthalakshman@yahoo.co.uk

(Received 24 February 2009; accepted 25 February 2009; online 6 March 2009)

In the title compound, C₁₀H₇ClN₄, the quinoline ring system is planar [maximum deviation 0.0035 (10) Å]. The crystal structure is stabilized by van der Waals and π–π stacking interactions [centroid–centroid distance 3.6456 (17) Å].

Related literature

For quinoline derivatives as anti-tuberculosis agents, see: Jain et al. (2005 ).

Experimental

Crystal data

C₁₀H₇ClN₄
M_r = 218.65
Triclinic, $[P \overline 1]$
a = 6.9517 (4) Å
b = 7.6078 (6) Å
c = 10.0191 (9) Å
α = 75.694 (7)°
β = 82.147 (8)°
γ = 76.532 (7)°
V = 497.57 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 293 K
0.19 × 0.17 × 0.14 mm

Data collection

Nonius MACH-3 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.935, T_max = 0.952
2209 measured reflections
1743 independent reflections
1206 reflections with I > 2σ(I)
R_int = 0.019
2 standard reflections frequency: 60 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.180
S = 1.08
1743 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 .

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007041/at2729sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007041/at2729Isup2.hkl

checkCIF report

Comment top

Quinoline derivatives are a class of important materials as anti-tuberculosis agents (Jain et al., 2005). In the title molecule (Fig. 1), all non-H atoms of the molecule, except atoms Cl1, C10, N2, N3 and N4 are coplanar within 0.0035 (10) Å. Due to 4-azida substitution within the pyridine ring: C2═ C3 bond is longer and the C3—C4 bond is shorter than standard values for C═C (1.334 Å) and Csp²—Csp² (1.455 Å) bond lengths respectively. The dihedral angle between the C3/N2-N4 and C2/C1/N1/C5 rings is 6.16 (11)°.

There is a weak π···π interaction observed between the centres of N1/C1—C5 rings related through the symmetry operator –x, 1-y, 1-z, with centroids separation of 3.6456 (17) Å.

Related literature top

For quinoline derivatives as anti-tuberculosis agents, see: Jain et al. (2005).

Experimental top

A mixture of 2,4-dichloroquinoline (2.12 g, 10 mmol) and sodium azide (0.650 g, 10 mmol) in DMF (20 ml) was refluxed for 2 h. The progress of the reaction was monitored by TLC. After conforming that the reaction got completed, the reaction mixture was cooled and poured on to the crushed ice with stirring. The solid settled was filtered to dryness and purified over a column of silica gel (60–120 mesh; 50 g) eluting with Petroleum Ether–ethyl acetate (4.5:1.5) to give 4-azido-2-chloro- 6-methylquinoline. The product was re-crystallized from 100% chloroform [mp: 429–430 K, yield: 20%].

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.

4-Azido-2-chloro-6-methylquinoline top

Crystal data top

C₁₀H₇ClN₄	Z = 2
M_r = 218.65	F(000) = 224
Triclinic, P1	D_x = 1.459 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9517 (4) Å	Cell parameters from 25 reflections
b = 7.6078 (6) Å	θ = 2–25°
c = 10.0191 (9) Å	µ = 0.35 mm⁻¹
α = 75.694 (7)°	T = 293 K
β = 82.147 (8)°	Block, colourless
γ = 76.532 (7)°	0.19 × 0.17 × 0.14 mm
V = 497.57 (7) Å³

Data collection top

Nonius MACH-3 diffractometer	1206 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 25.0°, θ_min = 2.1°
ω–2θ scans	h = −1→8
Absorption correction: ψ scan (North et al., 1968)	k = −8→9
T_min = 0.935, T_max = 0.952	l = −11→11
2209 measured reflections	2 standard reflections every 60 min
1743 independent reflections	intensity decay: none

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.180	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.1143P)² + 0.0878P] where P = (F_o² + 2F_c²)/3
1743 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₀H₇ClN₄	γ = 76.532 (7)°
M_r = 218.65	V = 497.57 (7) Å³
Triclinic, P1	Z = 2
a = 6.9517 (4) Å	Mo Kα radiation
b = 7.6078 (6) Å	µ = 0.35 mm⁻¹
c = 10.0191 (9) Å	T = 293 K
α = 75.694 (7)°	0.19 × 0.17 × 0.14 mm
β = 82.147 (8)°

Data collection top

Nonius MACH-3 diffractometer	1206 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.019
T_min = 0.935, T_max = 0.952	2 standard reflections every 60 min
2209 measured reflections	intensity decay: none
1743 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.180	H-atom parameters constrained
S = 1.08	Δρ_max = 0.36 e Å⁻³
1743 reflections	Δρ_min = −0.35 e Å⁻³
137 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	0.1775 (5)	0.7084 (4)	0.2969 (3)	0.0365 (8)
C2	0.2459 (4)	0.5180 (3)	0.3035 (3)	0.0334 (7)
H2	0.2656	0.4702	0.2246	0.040*
C3	0.2820 (4)	0.4060 (3)	0.4303 (3)	0.0294 (7)
C4	0.2518 (4)	0.4825 (4)	0.5495 (3)	0.0291 (7)
C5	0.1836 (4)	0.6769 (4)	0.5274 (3)	0.0328 (7)
C6	0.1508 (5)	0.7579 (4)	0.6436 (3)	0.0432 (8)
H6	0.1047	0.8853	0.6320	0.052*
C7	0.1857 (5)	0.6525 (4)	0.7709 (3)	0.0448 (9)
H7	0.1636	0.7094	0.8454	0.054*
C8	0.2548 (5)	0.4583 (5)	0.7950 (3)	0.0407 (8)
C9	0.2849 (4)	0.3774 (4)	0.6839 (3)	0.0354 (7)
H9	0.3283	0.2495	0.6978	0.043*
C10	0.2945 (6)	0.3461 (6)	0.9386 (3)	0.0581 (10)
H10A	0.1764	0.3662	0.9996	0.087*
H10B	0.3994	0.3836	0.9706	0.087*
H10C	0.3331	0.2169	0.9371	0.087*
Cl1	0.13068 (16)	0.85050 (11)	0.13412 (9)	0.0604 (4)
N1	0.1475 (4)	0.7888 (3)	0.4003 (3)	0.0395 (7)
N2	0.3501 (4)	0.2108 (3)	0.4540 (3)	0.0396 (7)
N3	0.3912 (4)	0.1499 (3)	0.3461 (3)	0.0418 (7)
N4	0.4337 (5)	0.0798 (4)	0.2571 (3)	0.0614 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0458 (19)	0.0243 (14)	0.0406 (16)	−0.0080 (13)	−0.0078 (14)	−0.0063 (12)
C2	0.0435 (19)	0.0236 (15)	0.0374 (16)	−0.0062 (13)	−0.0066 (14)	−0.0138 (12)
C3	0.0317 (16)	0.0202 (13)	0.0404 (16)	−0.0029 (12)	−0.0044 (13)	−0.0160 (12)
C4	0.0304 (16)	0.0214 (14)	0.0388 (16)	−0.0021 (11)	−0.0035 (12)	−0.0158 (12)
C5	0.0359 (18)	0.0227 (14)	0.0432 (16)	−0.0032 (12)	−0.0034 (13)	−0.0165 (12)
C6	0.055 (2)	0.0272 (16)	0.053 (2)	−0.0039 (14)	−0.0025 (16)	−0.0249 (14)
C7	0.056 (2)	0.0417 (18)	0.0452 (19)	−0.0095 (16)	0.0017 (16)	−0.0291 (15)
C8	0.044 (2)	0.0449 (18)	0.0385 (17)	−0.0112 (15)	−0.0041 (14)	−0.0171 (14)
C9	0.0400 (19)	0.0255 (14)	0.0426 (17)	−0.0018 (13)	−0.0064 (14)	−0.0139 (13)
C10	0.075 (3)	0.062 (2)	0.041 (2)	−0.013 (2)	−0.0078 (18)	−0.0161 (17)
Cl1	0.0950 (9)	0.0351 (5)	0.0482 (6)	−0.0092 (5)	−0.0201 (5)	−0.0002 (4)
N1	0.0535 (18)	0.0188 (12)	0.0460 (15)	−0.0010 (11)	−0.0058 (12)	−0.0121 (11)
N2	0.0572 (18)	0.0208 (12)	0.0413 (14)	0.0034 (12)	−0.0084 (12)	−0.0164 (11)
N3	0.0582 (19)	0.0204 (12)	0.0487 (16)	−0.0013 (12)	−0.0104 (13)	−0.0146 (12)
N4	0.105 (3)	0.0314 (14)	0.0503 (17)	0.0002 (16)	−0.0140 (17)	−0.0239 (13)

Geometric parameters (Å, º) top

C1—N1	1.298 (4)	C6—H6	0.9300
C1—C2	1.403 (4)	C7—C8	1.413 (4)
C1—Cl1	1.745 (3)	C7—H7	0.9300
C2—C3	1.362 (4)	C8—C9	1.371 (4)
C2—H2	0.9300	C8—C10	1.505 (5)
C3—N2	1.419 (3)	C9—H9	0.9300
C3—C4	1.424 (3)	C10—H10A	0.9600
C4—C9	1.404 (4)	C10—H10B	0.9600
C4—C5	1.415 (4)	C10—H10C	0.9600
C5—N1	1.364 (4)	N2—N3	1.251 (3)
C5—C6	1.416 (4)	N3—N4	1.121 (3)
C6—C7	1.348 (4)

N1—C1—C2	126.1 (3)	C6—C7—C8	122.2 (3)
N1—C1—Cl1	117.0 (2)	C6—C7—H7	118.9
C2—C1—Cl1	116.9 (2)	C8—C7—H7	118.9
C3—C2—C1	117.2 (2)	C9—C8—C7	117.8 (3)
C3—C2—H2	121.4	C9—C8—C10	121.7 (3)
C1—C2—H2	121.4	C7—C8—C10	120.5 (3)
C2—C3—N2	124.0 (2)	C8—C9—C4	121.8 (3)
C2—C3—C4	120.3 (2)	C8—C9—H9	119.1
N2—C3—C4	115.7 (2)	C4—C9—H9	119.1
C9—C4—C5	119.6 (2)	C8—C10—H10A	109.5
C9—C4—C3	124.1 (2)	C8—C10—H10B	109.5
C5—C4—C3	116.3 (3)	H10A—C10—H10B	109.5
N1—C5—C4	123.2 (2)	C8—C10—H10C	109.5
N1—C5—C6	118.8 (2)	H10A—C10—H10C	109.5
C4—C5—C6	117.9 (3)	H10B—C10—H10C	109.5
C7—C6—C5	120.7 (3)	C1—N1—C5	116.7 (2)
C7—C6—H6	119.6	N3—N2—C3	114.1 (2)
C5—C6—H6	119.6	N4—N3—N2	173.6 (3)

N1—C1—C2—C3	0.9 (5)	C5—C6—C7—C8	−0.4 (5)
Cl1—C1—C2—C3	−179.7 (2)	C6—C7—C8—C9	−0.5 (5)
C1—C2—C3—N2	179.5 (3)	C6—C7—C8—C10	179.2 (3)
C1—C2—C3—C4	−0.4 (4)	C7—C8—C9—C4	1.0 (5)
C2—C3—C4—C9	179.8 (3)	C10—C8—C9—C4	−178.6 (3)
N2—C3—C4—C9	−0.1 (4)	C5—C4—C9—C8	−0.7 (4)
C2—C3—C4—C5	0.0 (4)	C3—C4—C9—C8	179.5 (3)
N2—C3—C4—C5	−179.9 (3)	C2—C1—N1—C5	−0.9 (5)
C9—C4—C5—N1	−179.9 (3)	Cl1—C1—N1—C5	179.7 (2)
C3—C4—C5—N1	0.0 (4)	C4—C5—N1—C1	0.4 (5)
C9—C4—C5—C6	−0.1 (4)	C6—C5—N1—C1	−179.3 (3)
C3—C4—C5—C6	179.7 (3)	C2—C3—N2—N3	5.8 (4)
N1—C5—C6—C7	−179.6 (3)	C4—C3—N2—N3	−174.3 (3)
C4—C5—C6—C7	0.7 (5)	C3—N2—N3—N4	176 (3)

Experimental details

Crystal data
Chemical formula	C₁₀H₇ClN₄
M_r	218.65
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.9517 (4), 7.6078 (6), 10.0191 (9)
α, β, γ (°)	75.694 (7), 82.147 (8), 76.532 (7)
V (Å³)	497.57 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.19 × 0.17 × 0.14

Data collection
Diffractometer	Nonius MACH-3 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.935, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	2209, 1743, 1206
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.180, 1.08
No. of reflections	1743
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.35

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

SN thanks the DST for the FIST programme.

References

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