N-Benzyl­pyridin-2-amine

Abstract

In the title compound, C₁₂H₁₂N₂, the dihedral angle between the benzene and pyridine rings is 67.63 (8)°. Mol­ecules are linked into centrosymmetric dimers by a simple inter­molecular N—H⋯N hydrogen bond with graph-set motif R ₂ ²(8).

Related literature

For the application of Schiff base compounds in coordination chemistry, see: Garnovskii et al. (1993 ▶); Gong & Xu (2008 ▶). For the synthesis, see: Xu et al. (2009 ▶). For graph-set notation of hydrogen bonds, see: Bernstein et al. (1995 ▶). For another report on the structure of N-benzyl­pyridin-2-amine, see: Wang et al. (2010 ▶).

Experimental

Crystal data

• C₁₂H₁₂N₂

• M _r = 184.24

• Triclinic,

• a = 5.9233 (10) Å

• b = 8.0984 (15) Å

• c = 10.602 (2) Å

• α = 94.916 (15)°

• β = 91.36 (1)°

• γ = 94.451 (15)°

• V = 504.95 (16) ų

• Z = 2

• Mo Kα radiation

• μ = 0.07 mm⁻¹

• T = 295 K

• 0.25 × 0.20 × 0.18 mm

Data collection

• Rigaku SCXmini diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.980, T _max = 0.997

• 4612 measured reflections

• 1955 independent reflections

• 1039 reflections with I > 2σ(I)

• R _int = 0.062

Refinement

• R[F ² > 2σ(F ²)] = 0.076

• wR(F ²) = 0.183

• S = 1.06

• 1955 reflections

• 127 parameters

• H-atom parameters constrained

• Δρ_max = 0.14 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL/PC.

Supplementary Material

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2i	0.86	2.26	3.070 (3)	158

Symmetry code: (i) .

supplementary crystallographic information

Comment

Schiff base compounds have attracted great attention due to their application in coordination chemistry (Garnovskii et al., 1993; Gong & Xu, 2008), and also offer a simple method of synthesis novel amine compounds. The title compound is synthesized from the Schiff base (E)-N-benzylidenepyridin-2-amine, and the crystal structure is reported here.

In the molecule of the title compound (Fig. 1) bond lengths and angles have normal values. The dihedral angle between the benzene ring and pyridine ring is 67.63 (8)°. In the solid state the molecules are linked into centrosymmetric dimers by a simple N—H···N interaction with set graph-motif R₂²(8) (Bernstein et al., 1995), (Fig. 2; Table 1).

Experimental

The (E)-N-benzylidenepyridin-2-amine was prepared from benzaldehyde and pyridin-2-amine according to the reported method (Xu et al., 2009). To a mixture of (E)-N-benzylidenepyridin-2-amine (20 mmol), NaBH₄ (100 mmol) in 1,4-dioxane (50 ml), acetic acid (100 mmol) in 1,4-dioxane was added dropwise at 0°C. Then the mixture was heated at 120°C for 2 h then cooled and the solvent removed under vacuum. The residue was poured into water (20 ml) and extracted with chloroform three times (50 ml). The extract was dried (CaCl₂) and the solvent removed under vacuum to give the crude title compound. Pale yellow crystals suitable for X-ray analysis were obtained by slow evaporation of a 95% ethanol/water solution.

Refinement

All H atoms were detected in a difference map, but were placed in calculated positions and refined using a riding motion approxmation, with C—H = 0.93–0.97 Å, with U_iso(H) = 1.2U_eq(C); N—H = 0.86 Å, with U_iso(H) = 1.2U_eq(N).

Figures

Fig. 1.

The molecular structure of the title compound, showing the atomic numbering scheme. The displacement ellipsoids are drawn at the 30% probability level.

Fig. 2.

The diagram of the dimer linked by the intermolecular hydrogen bonds. The H atoms not involved in hydrogen bonds have been omitted for charity. Symmetry code: (a) -x + 1, -y, -z.

Crystal data

C12H12N2	Z = 2
Mr = 184.24	F(000) = 196
Triclinic, P1	Dx = 1.212 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.9233 (10) Å	Cell parameters from 904 reflections
b = 8.0984 (15) Å	θ = 2.5–27.4°
c = 10.602 (2) Å	µ = 0.07 mm−1
α = 94.916 (15)°	T = 295 K
β = 91.36 (1)°	Block, pale yellow
γ = 94.451 (15)°	0.25 × 0.20 × 0.18 mm
V = 504.95 (16) Å3

Data collection

Rigaku SCXmini diffractometer	1955 independent reflections
Radiation source: fine-focus sealed tube	1039 reflections with I > 2σ(I)
graphite	Rint = 0.062
Detector resolution: 13.6612 pixels mm-1	θmax = 26.0°, θmin = 3.1°
CCD profile fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.980, Tmax = 0.997	l = −13→13
4612 measured reflections

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.183	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0676P)2] where P = (Fo2 + 2Fc2)/3
1955 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.14 e Å−3
0 restraints	Δρmin = −0.15 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	0.4259 (5)	0.1591 (3)	0.1743 (3)	0.0497 (7)
C2	0.3612 (5)	0.2317 (4)	0.2902 (3)	0.0606 (9)
H2	0.2384	0.2966	0.2946	0.073*
C3	0.4814 (6)	0.2060 (4)	0.3978 (3)	0.0729 (10)
H3	0.4399	0.2533	0.4760	0.087*
C4	0.6631 (6)	0.1104 (4)	0.3901 (3)	0.0688 (9)
H4	0.7494	0.0940	0.4617	0.083*
C5	0.7120 (5)	0.0399 (4)	0.2725 (3)	0.0616 (9)
H5	0.8323	−0.0274	0.2667	0.074*
C6	0.1290 (5)	0.2807 (4)	0.0538 (3)	0.0609 (9)
H6A	0.1624	0.3874	0.1022	0.073*
H6B	−0.0012	0.2245	0.0903	0.073*
C7	0.0728 (5)	0.3080 (3)	−0.0806 (3)	0.0487 (7)
C8	0.2253 (5)	0.3955 (4)	−0.1514 (3)	0.0616 (8)
H8	0.3653	0.4367	−0.1155	0.074*
C9	0.1723 (6)	0.4224 (4)	−0.2746 (3)	0.0702 (10)
H9	0.2763	0.4823	−0.3210	0.084*
C10	−0.0325 (6)	0.3617 (4)	−0.3297 (3)	0.0712 (10)
H10	−0.0670	0.3785	−0.4135	0.085*
C11	−0.1851 (6)	0.2764 (4)	−0.2600 (3)	0.0686 (10)
H11	−0.3257	0.2362	−0.2958	0.082*
C12	−0.1314 (5)	0.2501 (4)	−0.1371 (3)	0.0587 (8)
H12	−0.2367	0.1911	−0.0910	0.070*
N1	0.3211 (4)	0.1824 (3)	0.0631 (2)	0.0584 (7)
H1A	0.3715	0.1364	−0.0055	0.070*
N2	0.5982 (4)	0.0617 (3)	0.1662 (2)	0.0553 (7)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0601 (19)	0.0431 (16)	0.0460 (18)	0.0067 (15)	0.0030 (14)	0.0010 (13)
C2	0.075 (2)	0.0526 (19)	0.055 (2)	0.0143 (17)	0.0093 (16)	0.0009 (14)
C3	0.100 (3)	0.071 (2)	0.047 (2)	0.012 (2)	0.0090 (18)	−0.0041 (15)
C4	0.082 (2)	0.068 (2)	0.055 (2)	0.007 (2)	−0.0131 (17)	0.0029 (16)
C5	0.067 (2)	0.060 (2)	0.058 (2)	0.0129 (17)	−0.0012 (16)	0.0041 (15)
C6	0.063 (2)	0.060 (2)	0.061 (2)	0.0195 (17)	0.0017 (15)	0.0045 (15)
C7	0.0485 (18)	0.0403 (16)	0.0586 (19)	0.0120 (14)	0.0035 (14)	0.0031 (13)
C8	0.0514 (19)	0.059 (2)	0.073 (2)	0.0014 (16)	0.0016 (16)	0.0005 (16)
C9	0.077 (3)	0.063 (2)	0.071 (2)	−0.0001 (19)	0.0092 (19)	0.0130 (17)
C10	0.085 (3)	0.069 (2)	0.061 (2)	0.011 (2)	−0.0070 (19)	0.0054 (17)
C11	0.061 (2)	0.071 (2)	0.072 (2)	0.0066 (19)	−0.0091 (18)	−0.0034 (18)
C12	0.054 (2)	0.0490 (18)	0.071 (2)	−0.0012 (15)	0.0063 (16)	0.0000 (15)
N1	0.0655 (17)	0.0619 (17)	0.0499 (16)	0.0249 (14)	0.0036 (12)	−0.0015 (11)
N2	0.0594 (16)	0.0534 (15)	0.0547 (16)	0.0156 (13)	0.0023 (12)	0.0045 (11)

Geometric parameters (Å, °)

C1—N2	1.338 (3)	C6—H6B	0.9700
C1—N1	1.354 (3)	C7—C12	1.368 (4)
C1—C2	1.391 (4)	C7—C8	1.381 (4)
C2—C3	1.369 (4)	C8—C9	1.376 (4)
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.374 (4)	C9—C10	1.370 (4)
C3—H3	0.9300	C9—H9	0.9300
C4—C5	1.373 (4)	C10—C11	1.365 (4)
C4—H4	0.9300	C10—H10	0.9300
C5—N2	1.331 (3)	C11—C12	1.372 (4)
C5—H5	0.9300	C11—H11	0.9300
C6—N1	1.444 (3)	C12—H12	0.9300
C6—C7	1.495 (4)	N1—H1A	0.8600
C6—H6A	0.9700
N2—C1—N1	115.7 (2)	C12—C7—C6	121.6 (3)
N2—C1—C2	121.5 (3)	C8—C7—C6	120.7 (3)
N1—C1—C2	122.7 (3)	C9—C8—C7	120.7 (3)
C3—C2—C1	118.9 (3)	C9—C8—H8	119.7
C3—C2—H2	120.5	C7—C8—H8	119.7
C1—C2—H2	120.5	C10—C9—C8	120.6 (3)
C2—C3—C4	120.0 (3)	C10—C9—H9	119.7
C2—C3—H3	120.0	C8—C9—H9	119.7
C4—C3—H3	120.0	C11—C10—C9	119.1 (3)
C5—C4—C3	117.3 (3)	C11—C10—H10	120.4
C5—C4—H4	121.3	C9—C10—H10	120.4
C3—C4—H4	121.3	C10—C11—C12	120.0 (3)
N2—C5—C4	124.2 (3)	C10—C11—H11	120.0
N2—C5—H5	117.9	C12—C11—H11	120.0
C4—C5—H5	117.9	C7—C12—C11	121.9 (3)
N1—C6—C7	111.6 (2)	C7—C12—H12	119.1
N1—C6—H6A	109.3	C11—C12—H12	119.1
C7—C6—H6A	109.3	C1—N1—C6	123.4 (2)
N1—C6—H6B	109.3	C1—N1—H1A	118.3
C7—C6—H6B	109.3	C6—N1—H1A	118.3
H6A—C6—H6B	108.0	C5—N2—C1	118.0 (3)
C12—C7—C8	117.7 (3)
N2—C1—C2—C3	1.8 (4)	C9—C10—C11—C12	−1.0 (5)
N1—C1—C2—C3	−177.8 (3)	C8—C7—C12—C11	0.2 (4)
C1—C2—C3—C4	0.3 (5)	C6—C7—C12—C11	179.2 (3)
C2—C3—C4—C5	−1.9 (5)	C10—C11—C12—C7	0.4 (5)
C3—C4—C5—N2	1.6 (5)	N2—C1—N1—C6	178.6 (2)
N1—C6—C7—C12	117.9 (3)	C2—C1—N1—C6	−1.7 (5)
N1—C6—C7—C8	−63.1 (4)	C7—C6—N1—C1	170.6 (3)
C12—C7—C8—C9	−0.2 (4)	C4—C5—N2—C1	0.3 (5)
C6—C7—C8—C9	−179.2 (3)	N1—C1—N2—C5	177.6 (3)
C7—C8—C9—C10	−0.5 (5)	C2—C1—N2—C5	−2.0 (4)
C8—C9—C10—C11	1.1 (5)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2i	0.86	2.26	3.070 (3)	158

Symmetry codes: (i) −x+1, −y, −z.