4-Azido-2-chloro-6-methyl­quinoline

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.057

• wR(F ²) = 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 .

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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.

Experimental

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%].

Refinement

The H atoms were placed in calculated positions and allowed to ride on their carrier atoms with C—H = 0.93–0.96 Å and with U_iso = 1.2U_eq(C) for CH and U_iso = 1.5U_eq(C) for CH₃ groups.

Figures

Fig. 1.

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

Crystal data

C10H7ClN4	Z = 2
Mr = 218.65	F(000) = 224
Triclinic, P1	Dx = 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

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

Refinement

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(Fo2) + (0.1143P)2 + 0.0878P] where P = (Fo2 + 2Fc2)/3
1743 reflections	(Δ/σ)max < 0.001
137 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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)