N-Benzyl­pyridin-2-amine

Wang, J.; Dai, C.; Nie, J.

doi:10.1107/S1600536810044478

organic compounds

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Volume 66| Part 12| December 2010| Page o3076

https://doi.org/10.1107/S1600536810044478

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N-Benzylpyridin-2-amine

Jun Wang,^a Chuntao Dai ^a ^* and Jianhua Nie ^a

^aZhongshan Polytechnic, Zhongshan, Guangdong 528404, People's Republic of China
^*Correspondence e-mail: wangjun7203@126.com

(Received 26 October 2010; accepted 31 October 2010; online 6 November 2010)

In the crystal of the title compound, C₁₂H₁₂N₂, intermolecular N—H⋯N hydrogen bonds form rings of graph-set motif R₂²(8) and C—H⋯π interactions further consolidate the dimers. Neighbouring dimers are further connected into a three-dimensional network by C—H⋯π interactions. The benzyl and pyridyl rings form a dihedral angle of 67.2 (1)°

Related literature

For general background to the topologies and potential applications of metal coordination polymers, see: Benelli & Gatteschi (2002 ). For related structures, see: Davies et al. (2001 ); Wan et al. (2004 ); Zhou & Richeson (1995 ). For bond-length data, see: Allen et al. (1987 ). For hydrogen-bonding graph-set motifs, see: Bernstein et al. (1995 ). For another report on the structure of N-benzylpyridin-2-amine, see: Wang & Zhao (2010 ).

Experimental

Crystal data

C₁₂H₁₂N₂
M_r = 184.24
Triclinic, $[P \overline 1]$
a = 5.9014 (16) Å
b = 8.025 (2) Å
c = 10.561 (3) Å
α = 95.471 (4)°
β = 91.244 (4)°
γ = 94.779 (3)°
V = 495.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 296 K
0.23 × 0.20 × 0.19 mm

Data collection

Bruker APEXII area-detector diffractometer
2551 measured reflections
1762 independent reflections
1387 reflections with I > 2σ(I)
R_int = 0.012

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.115
S = 1.07
1762 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C6 and N1/C8–C12 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1ⁱ	0.86	2.24	3.0518 (19)	157
C12—H12⋯Cg1ⁱ	0.93	2.72	3.536 (2)	147
C4—H4⋯Cg2ⁱⁱ	0.93	3.14	3.804 (2)	130
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810044478/rz2510sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810044478/rz2510Isup2.hkl

checkCIF report

Comment top

The design and construction of metal-organic frameworks (MOFs) is of great research interest due to their intriguing topologies and potential applications as functional materials (Benelli & Gatteschi, 2002). The 2-benzylaminopyridine ligand possessing two nitrogen donors to coordinate to metal ions, provides unique opportunities for the construction of various coordination networks. Recently, some complexes based on this ligand have been reported (Davies et al., 2001; Wan et al., 2004; Zhou & Richeson, 1995). When reacted with Ce(NO₃)₃ under hydrothermal condition, we isolated single crystals of the 2-benzylaminopyridine ligand, whose structure is reported herein.

The structure of the title compound is depicted in Fig. 1. The benzyl and the pyridyl rings are not coplanar and form a dihedral angle of 67.2 (1)°. The C—C and C—N bond lengths show normal values (Allen et al., 1987). Intermolecular N—H···N hydrogen bonds (graph set motif R²₂(8); Bernstein et al., 1995) involving a centrosymmetrically related pair of molecules gives rise to a dimer, which is also stabilized by C—H···π stacking interactions (Table 1). C—H···π stacking interactions between neighbouring dimers further extend the structure to form a three-dimensional supramolecular network (Fig. 2).

Related literature top

For general background to the topologies and potential applications of metal coordination polymers, see: Benelli & Gatteschi (2002). For related structures, see: Davies et al. (2001); Wan et al. (2004); Zhou & Richeson (1995). For bond-length data, see: Allen et al. (1987). For hydrogen-bonding graph-set motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of Ce(NO₃)₃.6H₂O (0.163 g, 0.5 mmol), 2-benzylaminopyridine (0.092 g, 0.5 mmol), and H₂O (10 mL) was sealed in a 15 mL Teflon-lined reactor, which was heated in an oven to 423 K for 24 h and then cooled to room temperature at a rate of 5 Kh^-1. Colourless crystals were obtained in a yield of 58% based on 2-benzylaminopyridine.

Structure description top

For general background to the topologies and potential applications of metal coordination polymers, see: Benelli & Gatteschi (2002). For related structures, see: Davies et al. (2001); Wan et al. (2004); Zhou & Richeson (1995). For bond-length data, see: Allen et al. (1987). For hydrogen-bonding graph-set motifs, see: Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. View of the three-dimensional structure of the title compound. Hydrogen bonds and C—H···π interactions are shown as dased lines.

N-Benzylpyridin-2-amine top

Crystal data top

C₁₂H₁₂N₂	Z = 2
M_r = 184.24	F(000) = 196
Triclinic, P1	D_x = 1.234 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.9014 (16) Å	Cell parameters from 3415 reflections
b = 8.025 (2) Å	θ = 1.2–28.0°
c = 10.561 (3) Å	µ = 0.07 mm⁻¹
α = 95.471 (4)°	T = 296 K
β = 91.244 (4)°	Block, colourless
γ = 94.779 (3)°	0.23 × 0.20 × 0.19 mm
V = 495.9 (2) Å³

Data collection top

Bruker APEXII area-detector diffractometer	1387 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.012
Graphite monochromator	θ_max = 25.3°, θ_min = 1.9°
φ and ω scans	h = −6→7
2551 measured reflections	k = −9→9
1762 independent reflections	l = −9→12

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0576P)² + 0.0854P] where P = (F_o² + 2F_c²)/3
1762 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₂H₁₂N₂	γ = 94.779 (3)°
M_r = 184.24	V = 495.9 (2) Å³
Triclinic, P1	Z = 2
a = 5.9014 (16) Å	Mo Kα radiation
b = 8.025 (2) Å	µ = 0.07 mm⁻¹
c = 10.561 (3) Å	T = 296 K
α = 95.471 (4)°	0.23 × 0.20 × 0.19 mm
β = 91.244 (4)°

Data collection top

Bruker APEXII area-detector diffractometer	1387 reflections with I > 2σ(I)
2551 measured reflections	R_int = 0.012
1762 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.07	Δρ_max = 0.23 e Å⁻³
1762 reflections	Δρ_min = −0.24 e Å⁻³
127 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	−0.1362 (3)	0.24905 (19)	0.36541 (15)	0.0350 (4)
H1	−0.2427	0.1909	0.4122	0.042*
C2	0.0725 (3)	0.30933 (18)	0.42172 (14)	0.0308 (4)
C3	0.2280 (3)	0.39773 (19)	0.34991 (15)	0.0357 (4)
H3	0.3689	0.4396	0.3860	0.043*
C4	0.1748 (3)	0.4236 (2)	0.22596 (16)	0.0397 (4)
H4	0.2798	0.4832	0.1793	0.048*
C5	−0.0331 (3)	0.3616 (2)	0.17061 (16)	0.0408 (4)
H5	−0.0680	0.3788	0.0868	0.049*
C6	−0.1889 (3)	0.2740 (2)	0.24050 (16)	0.0403 (4)
H6	−0.3292	0.2317	0.2038	0.048*
C7	0.1283 (3)	0.2820 (2)	0.55703 (15)	0.0359 (4)
H7A	0.1617	0.3897	0.6065	0.043*
H7B	−0.0022	0.2242	0.5932	0.043*
C8	0.4265 (3)	0.15939 (18)	0.67594 (14)	0.0301 (4)
C9	0.3600 (3)	0.23242 (19)	0.79450 (14)	0.0353 (4)
H9	0.2360	0.2968	0.7998	0.042*
C10	0.4814 (3)	0.2067 (2)	0.90146 (15)	0.0412 (4)
H10	0.4406	0.2545	0.9805	0.049*
C11	0.6648 (3)	0.1099 (2)	0.89304 (15)	0.0397 (4)
H11	0.7507	0.0930	0.9649	0.048*
C12	0.7150 (3)	0.03973 (19)	0.77449 (15)	0.0359 (4)
H12	0.8367	−0.0269	0.7683	0.043*
N1	0.6010 (2)	0.06064 (16)	0.66736 (12)	0.0334 (3)
N2	0.3221 (2)	0.18353 (16)	0.56430 (12)	0.0355 (3)
H2	0.3734	0.1384	0.4947	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0330 (9)	0.0302 (8)	0.0414 (9)	0.0009 (6)	0.0061 (7)	0.0020 (7)
C2	0.0328 (8)	0.0249 (7)	0.0354 (8)	0.0081 (6)	0.0040 (6)	0.0010 (6)
C3	0.0314 (9)	0.0348 (9)	0.0405 (9)	0.0005 (7)	0.0013 (7)	0.0026 (7)
C4	0.0443 (10)	0.0352 (9)	0.0403 (9)	0.0000 (7)	0.0100 (7)	0.0075 (7)
C5	0.0503 (11)	0.0386 (9)	0.0340 (9)	0.0075 (8)	−0.0017 (7)	0.0041 (7)
C6	0.0358 (9)	0.0403 (9)	0.0431 (10)	0.0021 (7)	−0.0041 (7)	−0.0020 (7)
C7	0.0355 (9)	0.0356 (8)	0.0378 (9)	0.0096 (7)	0.0050 (7)	0.0037 (7)
C8	0.0329 (9)	0.0249 (7)	0.0326 (8)	0.0010 (6)	0.0036 (6)	0.0033 (6)
C9	0.0410 (10)	0.0312 (8)	0.0343 (9)	0.0064 (7)	0.0064 (7)	0.0015 (6)
C10	0.0544 (11)	0.0388 (9)	0.0301 (9)	0.0045 (8)	0.0067 (7)	−0.0003 (7)
C11	0.0481 (10)	0.0382 (9)	0.0323 (9)	0.0022 (8)	−0.0039 (7)	0.0043 (7)
C12	0.0355 (9)	0.0336 (8)	0.0389 (9)	0.0032 (7)	−0.0014 (7)	0.0055 (7)
N1	0.0357 (8)	0.0328 (7)	0.0322 (7)	0.0068 (6)	0.0009 (6)	0.0022 (5)
N2	0.0416 (8)	0.0377 (7)	0.0286 (7)	0.0147 (6)	0.0023 (6)	0.0012 (6)

Geometric parameters (Å, º) top

C1—C2	1.385 (2)	C7—H7B	0.9700
C1—C6	1.386 (2)	C8—N1	1.3502 (19)
C1—H1	0.9300	C8—N2	1.3559 (19)
C2—C3	1.395 (2)	C8—C9	1.409 (2)
C2—C7	1.500 (2)	C9—C10	1.366 (2)
C3—C4	1.378 (2)	C9—H9	0.9300
C3—H3	0.9300	C10—C11	1.383 (2)
C4—C5	1.381 (2)	C10—H10	0.9300
C4—H4	0.9300	C11—C12	1.372 (2)
C5—C6	1.380 (2)	C11—H11	0.9300
C5—H5	0.9300	C12—N1	1.3353 (19)
C6—H6	0.9300	C12—H12	0.9300
C7—N2	1.448 (2)	N2—H2	0.8600
C7—H7A	0.9700

C2—C1—C6	121.05 (15)	C2—C7—H7B	109.5
C2—C1—H1	119.5	H7A—C7—H7B	108.0
C6—C1—H1	119.5	N1—C8—N2	115.92 (13)
C1—C2—C3	118.30 (14)	N1—C8—C9	121.27 (14)
C1—C2—C7	120.76 (14)	N2—C8—C9	122.81 (14)
C3—C2—C7	120.94 (14)	C10—C9—C8	118.62 (15)
C4—C3—C2	120.63 (15)	C10—C9—H9	120.7
C4—C3—H3	119.7	C8—C9—H9	120.7
C2—C3—H3	119.7	C9—C10—C11	120.44 (15)
C3—C4—C5	120.50 (16)	C9—C10—H10	119.8
C3—C4—H4	119.8	C11—C10—H10	119.8
C5—C4—H4	119.8	C12—C11—C10	117.34 (15)
C6—C5—C4	119.57 (15)	C12—C11—H11	121.3
C6—C5—H5	120.2	C10—C11—H11	121.3
C4—C5—H5	120.2	N1—C12—C11	124.42 (15)
C5—C6—C1	119.96 (15)	N1—C12—H12	117.8
C5—C6—H6	120.0	C11—C12—H12	117.8
C1—C6—H6	120.0	C12—N1—C8	117.85 (13)
N2—C7—C2	110.93 (13)	C8—N2—C7	122.91 (13)
N2—C7—H7A	109.5	C8—N2—H2	118.5
C2—C7—H7A	109.5	C7—N2—H2	118.5
N2—C7—H7B	109.5

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C6 and N1/C8–C12 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.86	2.24	3.0518 (19)	157
C12—H12···Cg1ⁱ	0.93	2.72	3.536 (2)	147
C4—H4···Cg2ⁱⁱ	0.93	3.14	3.804 (2)	130

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂
M_r	184.24
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.9014 (16), 8.025 (2), 10.561 (3)
α, β, γ (°)	95.471 (4), 91.244 (4), 94.779 (3)
V (Å³)	495.9 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.23 × 0.20 × 0.19

Data collection
Diffractometer	Bruker APEXII area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2551, 1762, 1387
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.115, 1.07
No. of reflections	1762
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.24

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C6 and N1/C8–C12 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.86	2.24	3.0518 (19)	156.5
C12—H12···Cg1ⁱ	0.93	2.72	3.536 (2)	147
C4—H4···Cg2ⁱⁱ	0.93	3.14	3.804 (2)	130

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

Acknowledgements

The authors acknowledge Zhongshan Polytechnic for supporting this work.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3076

https://doi.org/10.1107/S1600536810044478

Open

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