Quinolin-3-amine

Islor, A.M.; Chandrakantha, B.; Shetty, P.; Gerber, T.; Hosten, E.; Betz, R.

doi:10.1107/S1600536812042626

organic compounds

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Volume 68| Part 11| November 2012| Page o3155

doi:10.1107/S1600536812042626

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Quinolin-3-amine

Arun M. Islor,^a B. Chandrakantha,^b Prakash Shetty,^b Thomas Gerber,^c Eric Hosten ^c and Richard Betz ^c ^*

^aNational Institute of Technology-Karnataka, Department of Chemistry, Organic Chemistry Laboratory, Surathkal, Mangalore 575 025, India, ^bManipal Institute of Technology, Department of Chemistry, Manipal 576 104, India, and ^cNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth, 6031, South Africa
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 6 October 2012; accepted 11 October 2012; online 20 October 2012)

In the crystal structur of the achiral title compound, C₉H₈N₂, N—H⋯N hydrogen bonds connect the molecules into zigzag chains in [100]. Weak intermolecular N–H⋯π interactions further consolidate the crystal packing.

Related literature

For novel applications of quinolin-3-amine and its derivatives, see: Rohmer et al. (2010 ); Kaneshiro et al. (2011 ). For the crystal structure of a rhodium coordination compound featuring the title compound as a ligand, see: Garralda et al. (1999 ). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₈N₂
M_r = 144.17
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.6223 (3) Å
b = 7.6289 (3) Å
c = 12.6967 (4) Å
V = 738.31 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 200 K
0.55 × 0.52 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.950, T_max = 0.988
6898 measured reflections
1077 independent reflections
1015 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.091
S = 1.03
1077 reflections
108 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1/C5–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯N1ⁱ	0.90 (2)	2.22 (2)	3.0761 (17)	158.2 (18)
N2—H2A⋯Cgⁱⁱ	0.85 (2)	2.60 (2)	3.3101 (15)	142.3 (19)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812042626/cv5347sup1.cif

Supporting information file. DOI: 10.1107/S1600536812042626/cv5347Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536812042626/cv5347Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536812042626/cv5347Isup4.cml

checkCIF report

Comment top

3-Aminoquinoline and its derivatives have found applications in matrix-assisted laser desorption ionization (MALDI) mass-spectrometry of oligosaccharides (Rohmer et al., 2010) and glycans (Kaneshiro et al., 2011). Herewith we present the crystal structure of 3-aminoquinoline, (I).

In (I) (Fig. 1), the molecule bears an amino group in meta position to the intracyclic nitrogen atom. Intracyclic angles in the six-membered ring containing the nitrogen atom cover a range of 117.42 (12)–125.27 (11) ° with the smallest angle found on the carbon atom bearing the amino group and the biggest angle present on the hydrogen-bearing carbon atom in ortho position to the intracyclic nitrogen atom. The molecule is essentially planar (r.m.s. deviation of of all fitted non-hydrogen atoms = 0.0091 Å). The least-squares planes defined by the non-hydrogen atoms of the heterocycle on the one hand and the atoms of the amino group on the other hand intersect at an angle of 11.97(2.58) °.

In the crystal, N–H···N hydrogen bonds (Table 1) are observed between the amino group and the intracyclic nitrogen atom that connect the molecules to zigzag chains along the crystallographic a axis (Fig. 2). In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for these contacts is C¹₁(5) on the unary level. In addition, a N–H···π interaction (Table 1) involving the non-heterocyclic moiety of the quinoline core as acceptor contribute to the crystal packing stability.

Related literature top

For novel applications of 3-aminoquinoline and its derivatives, see: Rohmer et al. (2010); Kaneshiro et al. (2011). For the crystal structure of a rhodium coordination compound featuring the title compound as a ligand, see: Garralda et al. (1999). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995).

Experimental top

To a solution of 3-nitroquinoline (1 g, 0.0057 mol) in methanol (20 ml) 10% palladium on carbon (0.10 g) was added. The batch was hydrogenated at a pressure of 10 bar for 12 h. Subsequently, the reaction mixture was filtered and concentrated under reduced pressure to afford the title compound as a pale yellow solid. The solid was dissolved in absolute ethanol and allowed to stand and evaporate at room temperature overnight. The crystalline solid that developed was filtered and dried under high vacuum (yield: 0.8 g, 97.5%).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids (drawn at the 50% probability level).
	Fig. 2. A portion of the crystal packing viewed along [010]. Dashed lines indicate N–H···N hydrogen bonds. Symmetry codes: (i) x - 1/2, -y + 1/2, -z + 1; (ii) x + 1/2, -y + 1/2, -z + 1.

Quinolin-3-amine top

Crystal data top

C₉H₈N₂	D_x = 1.297 Mg m⁻³
M_r = 144.17	Melting point = 366–368 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5242 reflections
a = 7.6223 (3) Å	θ = 2.7–28.3°
b = 7.6289 (3) Å	µ = 0.08 mm⁻¹
c = 12.6967 (4) Å	T = 200 K
V = 738.31 (5) Å³	Block, colourless
Z = 4	0.55 × 0.52 × 0.15 mm
F(000) = 304

Data collection top

Bruker APEXII CCD diffractometer	1077 independent reflections
Radiation source: fine-focus sealed tube	1015 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ϕ and ω scans	θ_max = 28.3°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→10
T_min = 0.950, T_max = 0.988	k = −9→10
6898 measured reflections	l = −16→16

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0591P)² + 0.1011P] where P = (F_o² + 2F_c²)/3
1077 reflections	(Δ/σ)_max < 0.001
108 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₉H₈N₂	V = 738.31 (5) Å³
M_r = 144.17	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.6223 (3) Å	µ = 0.08 mm⁻¹
b = 7.6289 (3) Å	T = 200 K
c = 12.6967 (4) Å	0.55 × 0.52 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	1077 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1015 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.988	R_int = 0.013
6898 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.23 e Å⁻³
1077 reflections	Δρ_min = −0.20 e Å⁻³
108 parameters

Special details top

Refinement. Due to the absence of a strong anomalous scatterer, the Flack parameter is meaningless. Thus, Friedel opposites (737 pairs) have been merged and the item was removed from the CIF.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.25487 (15)	0.26319 (16)	0.38612 (8)	0.0280 (3)
N2	−0.18546 (17)	0.08305 (19)	0.39280 (11)	0.0359 (3)
H2A	−0.258 (3)	0.023 (3)	0.3568 (15)	0.056 (6)*
H2B	−0.198 (2)	0.098 (3)	0.4628 (17)	0.043 (5)*
C1	0.30327 (17)	0.23241 (17)	0.28353 (9)	0.0249 (3)
C2	0.09884 (17)	0.21121 (18)	0.41581 (9)	0.0277 (3)
H2	0.0663	0.2323	0.4869	0.033*
C3	−0.02593 (17)	0.12565 (16)	0.35016 (9)	0.0253 (3)
C4	0.02155 (18)	0.09412 (17)	0.24707 (10)	0.0265 (3)
H4	−0.0576	0.0376	0.2003	0.032*
C5	0.18933 (16)	0.14693 (17)	0.21189 (9)	0.0244 (3)
C6	0.24840 (19)	0.11883 (19)	0.10713 (10)	0.0299 (3)
H6	0.1743	0.0609	0.0580	0.036*
C7	0.4113 (2)	0.17449 (19)	0.07635 (10)	0.0344 (3)
H7	0.4488	0.1553	0.0059	0.041*
C8	0.52397 (19)	0.2599 (2)	0.14793 (11)	0.0353 (3)
H8	0.6366	0.2982	0.1256	0.042*
C9	0.47097 (17)	0.28794 (19)	0.25005 (11)	0.0313 (3)
H9	0.5474	0.3448	0.2982	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0323 (5)	0.0323 (6)	0.0193 (5)	−0.0026 (5)	−0.0030 (4)	−0.0003 (4)
N2	0.0318 (6)	0.0443 (7)	0.0316 (6)	−0.0081 (5)	0.0052 (5)	−0.0086 (6)
C1	0.0277 (6)	0.0263 (6)	0.0207 (5)	0.0017 (5)	−0.0018 (5)	0.0009 (5)
C2	0.0340 (6)	0.0299 (6)	0.0191 (5)	−0.0004 (5)	−0.0012 (5)	−0.0007 (5)
C3	0.0279 (6)	0.0238 (5)	0.0243 (6)	0.0009 (5)	−0.0004 (5)	−0.0006 (5)
C4	0.0306 (6)	0.0264 (6)	0.0226 (5)	−0.0013 (5)	−0.0021 (5)	−0.0045 (5)
C5	0.0303 (6)	0.0228 (6)	0.0202 (5)	0.0027 (5)	−0.0006 (5)	−0.0003 (5)
C6	0.0382 (7)	0.0298 (6)	0.0218 (6)	0.0032 (5)	0.0015 (5)	−0.0037 (5)
C7	0.0430 (7)	0.0348 (7)	0.0254 (5)	0.0059 (6)	0.0084 (6)	−0.0008 (5)
C8	0.0320 (6)	0.0389 (7)	0.0350 (7)	0.0010 (6)	0.0070 (6)	0.0052 (6)
C9	0.0294 (7)	0.0347 (7)	0.0298 (6)	−0.0008 (5)	−0.0009 (5)	0.0008 (6)

Geometric parameters (Å, º) top

N1—C2	1.3091 (17)	C4—C5	1.4133 (18)
N1—C1	1.3740 (16)	C4—H4	0.9500
N2—C3	1.3701 (17)	C5—C6	1.4205 (17)
N2—H2A	0.85 (2)	C6—C7	1.369 (2)
N2—H2B	0.90 (2)	C6—H6	0.9500
C1—C9	1.4122 (18)	C7—C8	1.410 (2)
C1—C5	1.4167 (17)	C7—H7	0.9500
C2—C3	1.4231 (17)	C8—C9	1.375 (2)
C2—H2	0.9500	C8—H8	0.9500
C3—C4	1.3792 (17)	C9—H9	0.9500

C2—N1—C1	117.72 (11)	C4—C5—C1	118.88 (11)
C3—N2—H2A	119.4 (14)	C4—C5—C6	122.66 (12)
C3—N2—H2B	116.8 (12)	C1—C5—C6	118.45 (12)
H2A—N2—H2B	122.1 (18)	C7—C6—C5	120.52 (13)
N1—C1—C9	118.50 (12)	C7—C6—H6	119.7
N1—C1—C5	121.52 (12)	C5—C6—H6	119.7
C9—C1—C5	119.98 (11)	C6—C7—C8	120.78 (12)
N1—C2—C3	125.27 (11)	C6—C7—H7	119.6
N1—C2—H2	117.4	C8—C7—H7	119.6
C3—C2—H2	117.4	C9—C8—C7	120.04 (13)
N2—C3—C4	124.50 (12)	C9—C8—H8	120.0
N2—C3—C2	118.07 (11)	C7—C8—H8	120.0
C4—C3—C2	117.42 (12)	C8—C9—C1	120.22 (13)
C3—C4—C5	119.19 (12)	C8—C9—H9	119.9
C3—C4—H4	120.4	C1—C9—H9	119.9
C5—C4—H4	120.4

C2—N1—C1—C9	179.86 (12)	C9—C1—C5—C4	−179.41 (11)
C2—N1—C1—C5	−0.20 (19)	N1—C1—C5—C6	−179.74 (12)
C1—N1—C2—C3	−0.3 (2)	C9—C1—C5—C6	0.20 (18)
N1—C2—C3—N2	−178.55 (13)	C4—C5—C6—C7	179.12 (12)
N1—C2—C3—C4	0.3 (2)	C1—C5—C6—C7	−0.5 (2)
N2—C3—C4—C5	178.95 (12)	C5—C6—C7—C8	0.3 (2)
C2—C3—C4—C5	0.15 (18)	C6—C7—C8—C9	0.1 (2)
C3—C4—C5—C1	−0.61 (18)	C7—C8—C9—C1	−0.4 (2)
C3—C4—C5—C6	179.80 (12)	N1—C1—C9—C8	−179.82 (13)
N1—C1—C5—C4	0.66 (18)	C5—C1—C9—C8	0.2 (2)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1/C5–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N1ⁱ	0.90 (2)	2.22 (2)	3.0761 (17)	158.2 (18)
N2—H2A···Cgⁱⁱ	0.85 (2)	2.60 (2)	3.3101 (15)	142.3 (19)

Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₈N₂
M_r	144.17
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	200
a, b, c (Å)	7.6223 (3), 7.6289 (3), 12.6967 (4)
V (Å³)	738.31 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.55 × 0.52 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.950, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	6898, 1077, 1015
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.091, 1.03
No. of reflections	1077
No. of parameters	108
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.20

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEPIII (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1/C5–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N1ⁱ	0.90 (2)	2.22 (2)	3.0761 (17)	158.2 (18)
N2—H2A···Cgⁱⁱ	0.85 (2)	2.60 (2)	3.3101 (15)	142.3 (19)

Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) −x, y−1/2, −z+1/2.

Acknowledgements

AMI is thankful to the Director of the National Institute of Technology for providing research facilities and also thanks the Board for Research in Nuclear Sciences, the Department of Atomic Energy and the Government of India for a Young Scientist award.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3155

doi:10.1107/S1600536812042626

Open

access