N-[(2-Chloro-3-quinol­yl)meth­yl]-4-fluoro­aniline

Jerry P Jasinski; Albert E Pek; C S Chidan Kumar; H S Yathirajan; Suresh Kumar

doi:10.1107/S1600536810036056

. 2010 Sep 11;66(Pt 10):o2548–o2549. doi: 10.1107/S1600536810036056

N-[(2-Chloro-3-quinolyl)methyl]-4-fluoroaniline

Jerry P Jasinski ^a,^*, Albert E Pek ^a, C S Chidan Kumar ^b, H S Yathirajan ^b, Suresh Kumar ^c

PMCID: PMC2983417 PMID: 21587537

Abstract

In the title compound, C₁₆H₁₂ClFN₂, the dihedral angle between the quinoline ring system and the flourophenyl ring is 86.70 (4)°. In the crystal, molecules are linked into chains along the a axis by N—H⋯N hydrogen bonds. In addition, C—H⋯π interactions involving the two benzene rings are observed.

Related literature

For general background, properties and the biological activity of quinolines, see: Campbell et al. (1988 ▶); Dutta et al. (2002 ▶); Markees et al. (1970 ▶); Meth-Cohn et al. (1981 ▶); Michael et al. (1997 ▶); Morimoto et al. (1991 ▶); Padwa et al. (1999 ▶); Rajendran & Karavembu (2002 ▶); Robert & Meunier et al. (1998 ▶). For the synthesis of quinolines, see: Kouznetsov et al. (2005 ▶). For related structures, see: Butcher et al. 2007 ▶); Lynch et al. (2001 ▶); Subashini et al. (2009 ▶); Yathirajan et al. (2007 ▶); Wu et al. (2009 ▶); Khan et al. (2010 ▶). For bond-length data, see: Allen et al. (1987 ▶) .

Experimental

Crystal data

C₁₆H₁₂ClFN₂
M _r = 286.73
Triclinic,
a = 7.3661 (8) Å
b = 8.8967 (9) Å
c = 11.5129 (12) Å
α = 68.704 (1)°
β = 74.468 (1)°
γ = 75.445 (1)°
V = 667.25 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100 K
0.55 × 0.50 × 0.25 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.858, T _max = 0.932
8162 measured reflections
3930 independent reflections
3633 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.094
S = 1.03
3930 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036056/ci5158sup1.cif

e-66-o2548-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036056/ci5158Isup2.hkl

e-66-o2548-Isup2.hkl^{(192.6KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C1–C6 and C11–C16 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H18⋯N1ⁱ	0.86	2.30	3.1353 (12)	165
C4—H4⋯Cg2ⁱⁱ	0.93	2.91	3.7494 (13)	151
C10—H10A⋯Cg1ⁱⁱⁱ	0.97	2.62	3.5365 (12)	157
C10—H10B⋯Cg2^iv	0.97	2.98	3.8083 (11)	145

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

JPJ thanks Dr Matthias Zeller and the YSU Department of Chemistry for their assistance with the data collection. The diffractometer was funded by NSF grant 0087210, by the Ohio Board of Regents grant CAP-491, and by YSU. CSC thanks the University of Mysore for research facilities and HSY thanks the University of Mysore for sabbatical leave.

supplementary crystallographic information

Comment

Quinoline derivatives represent a major class of heterocycles, and a number of preparations using them have been known since the late 1800s. Quinolines are found in natural products (Morimoto et al., 1991; Michael et al., 1997), numerous commercial products, including fragrances, dyes (Padwa et al., 1999) and biologically active compounds (Markees et al., 1970; Campbell et al., 1988). Quinoline alkaloids such as quinine, chloroquin, mefloquine and amodiaquine are used as efficient drugs for the treatment of malaria (Robert & Meunier, 1998). Several quinoline derivatives have been evaluated in vitro against a number of parasites of HTLV-1 transformed cells. 2-Chloro substituted quinolines are vital synthetic intermediates in the construction of a large number of linearly fused tri- and tetra- cyclic quinolines studied for the DNA intercalating properties (Meth-Cohn et al., 1981; Rajendran & Karavembu, 2002; Dutta et al., 2002). A review on recent progress in the synthesis of quinolines (Kouznetsov et al. 2005) has been described. The crystal structure studies of 8-chloro-2-methylquinoline (Wu et al., 2009), 2-chloro-4-methylquinoline (Lynch et al., 2001), 4-chloro-8-(trifluoromethyl)quinoline (Yathirajan et al., 2007), 1-(quinolin-2-yl)ethanone (Butcher et al., 2007) and 2-chloro-7-methylquinoline-3-carbaldehyde (Subashini et al., 2009) have been reported. In view of the importance of quinolines, the paper reports the synthesis and crystal structure of the title compound.

In the title molecule (Fig. 1), the 2-chloroquinoline ring system and 4-fluoroaniline ring are bonded to a methane carbon, C10. The dihedral angle between the mean planes of the planar chloroquinoline ring system (dihedral angle between rings = 0.92 (5)°) and the flourophenyl ring is 86.70 (4)°. Bond distances (Allen et al., 1987) and angles are in normal ranges.

The molecules are linked into chains along the a axis by N—H···N hydrogen bonds (Fig. 2). In addition, C—H···π interactions involving the two benzene rings (Table 1) influence crystal packing in the unit cell.

Experimental

In a mixture of 3-(chloromethyl)-2-chloroquinoline (0.003 mol) and substituted phenyl amine (0.003 mol) in 20 ml of absolute ethanol, 1 ml of triethylamine (TEA) was added and refluxed for 12–15 hrs (Fig. 3). After completion of the reaction, content of the flask was reduced to half and left overnight. The crystalline mass obtained was filtered off, washed with water, dried and re-crystallized from ethanol to give N-[(2-chloroquinolin-3-yl)methyl]-4-fluoroaniline. X-ray quality crystals were obtained by slow evaporation of a methanol solution (m.p. 413–415 K).