N-Benzyl­pyridin-2-amine

Wang, G.G.; Zhao, H.

doi:10.1107/S1600536810044351

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3077

https://doi.org/10.1107/S1600536810044351

Open

access

N-Benzylpyridin-2-amine

Gai Gai Wang ^a and Hong Zhao ^a ^*

^aSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: zhaohong@seu.edu.cn

(Received 26 October 2010; accepted 29 October 2010; online 6 November 2010)

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 R₂²(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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.076
wR(F²) = 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

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) -x+1, -y, -z.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810044351/bx2323sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810044351/bx2323Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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). [Please check amended text]

Experimental top

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.

Structure description top

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). [Please check amended text]

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures top

	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.

N-Benzylpyridin-2-amine top

Crystal data top

C₁₂H₁₂N₂	Z = 2
M_r = 184.24	F(000) = 196
Triclinic, P1	D_x = 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 top

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

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.183	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0676P)²] where P = (F_o² + 2F_c²)/3
1955 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₂H₁₂N₂	γ = 94.451 (15)°
M_r = 184.24	V = 504.95 (16) Å³
Triclinic, P1	Z = 2
a = 5.9233 (10) Å	Mo Kα radiation
b = 8.0984 (15) Å	µ = 0.07 mm⁻¹
c = 10.602 (2) Å	T = 295 K
α = 94.916 (15)°	0.25 × 0.20 × 0.18 mm
β = 91.36 (1)°

Data collection top

Rigaku SCXmini diffractometer	1955 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1039 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.997	R_int = 0.062
4612 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	0 restraints
wR(F²) = 0.183	H-atom parameters constrained
S = 1.06	Δρ_max = 0.14 e Å⁻³
1955 reflections	Δρ_min = −0.16 e Å⁻³
127 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	0.4259 (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 (Å²) top

	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, º) top

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, º) top

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) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂
M_r	184.24
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	5.9233 (10), 8.0984 (15), 10.602 (2)
α, β, γ (°)	94.916 (15), 91.36 (1), 94.451 (15)
V (Å³)	504.95 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.25 × 0.20 × 0.18

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.980, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	4612, 1955, 1039
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.183, 1.06
No. of reflections	1955
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.16

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86	2.26	3.070 (3)	157.6

Symmetry code: (i) −x+1, −y, −z.

Acknowledgements

This work was supported financially by a Southeast University grant for Young Researchers (No. 4007041027).

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Garnovskii, A. D., Nivorozhkin, A. L. & Minkin, V. I. (1993). Coord. Chem. Rev. 126, 1–69. CrossRef CAS Web of Science Google Scholar
Gong, X.-X. & Xu, H.-J. (2008). Acta Cryst. E64, o1188. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, J., Dai, C. & Nie, J. (2010). Acta Cryst. E66, o3076. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xu, H.-J., Tan, Q.-Y., Cui, L.-J. & Qian, K. (2009). Acta Cryst. E65, o945. Web of Science CSD CrossRef IUCr Journals Google Scholar