N,N-Bis(2-pyridylmeth­yl)aniline

Kang, J.-T.; Wang, G.-H.; Xu, J.-W.; Yang, W.

doi:10.1107/S1600536810001881

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o475

https://doi.org/10.1107/S1600536810001881

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N,N-Bis(2-pyridylmethyl)aniline

Jun-Tao Kang,^a Guan-Hua Wang,^a Jing-Wei Xu ^a ^* and Wei Yang ^a ^*

^aThe State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China
^*Correspondence e-mail: jwxu@ciac.jl.cn, yangwei1988@ciac.jl.cn

(Received 30 December 2009; accepted 15 January 2010; online 30 January 2010)

In the title compound, C₁₈H₁₇N₃, the two pyridyl rings make a dihedral angle of 54.55 (13)°. The dihedral angles between the phenyl ring and the two pyridyl rings are 73.61 (13) and 81.40 (13)°. In the crystal, weak intermolecular C—H⋯π interactions are observed.

Related literature

For bis(pyridin-2-ylmethyl)amine derivatives, see: Komatsu et al. (2007 ); Royzen et al. (2006 ); Xiang & Tong (2006 ). For related structures, see: Nielsen et al. (2005 , 2007 ); Bjernemose et al. (2003 ); Hazell et al. (2000 ); Ugozzoli et al. (2002 ). For the synthesis, see: Foxon et al. (2007 ).

Experimental

Crystal data

C₁₈H₁₇N₃
M_r = 275.35
Monoclinic, P 2₁ /c
a = 11.4866 (19) Å
b = 16.811 (3) Å
c = 7.7930 (12) Å
β = 101.471 (3)°
V = 1474.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.26 × 0.17 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.981, T_max = 0.991
7541 measured reflections
2591 independent reflections
1251 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.117
S = 0.93
2591 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C8–C12/N2 and C1–C6 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯Cg2ⁱ	0.97	2.98 (4)	3.825 (3)	146
C15—H15⋯Cg1ⁱⁱ	0.93	2.96 (3)	3.619 (4)	129
C17—H17⋯Cg2ⁱⁱⁱ	0.93	2.65 (3)	3.530 (3)	159
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x, -y+1, -z+2; (iii) x, y, z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810001881/is2511sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810001881/is2511Isup2.hkl

checkCIF report

Comment top

Bis(pyridin-2-ylmethyl)amine derivatives are often used as zinc probes (Royzen et al., 2006; Komatsu et al., 2007; Xiang & Tong, 2006). The title compound, N,N-bis(pyridin-2-ylmethyl)aniline, has been also used as a ligand in metal complexes (Nielsen et al., 2005, 2007; Bjernemose et al., 2003; Hazell et al., 2000; Ugozzoli et al., 2002). Herein, we report the molecular and crystal structure of this compound. The molecule has three rings trending to different orientations, of which the dihedral angle between the two pyridyl rings is 54.55 (13)°, and the dihedral angles between the phenyl ring and the two pyridyl rings are 73.61 (13) and 81.40 (13)°. Intermolecular C—H···π interactions exist in the crystal, which connect molecules into a two-dimensional layer structure.

Related literature top

For bis(pyridin-2-ylmethyl)amine derivatives, see: Komatsu et al. (2007); Royzen et al. (2006); Xiang & Tong (2006). For related structures, see: Nielsen et al. (2005, 2007); Bjernemose et al. (2003); Hazell et al. (2000); Ugozzoli et al. (2002). For the synthesis, see: Foxon et al. (2007).

Experimental top

The title compound was synthesized according to previous reported literature (Foxon et al., 2007). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the title compound in acetone at room temperature.

Structure description top

For bis(pyridin-2-ylmethyl)amine derivatives, see: Komatsu et al. (2007); Royzen et al. (2006); Xiang & Tong (2006). For related structures, see: Nielsen et al. (2005, 2007); Bjernemose et al. (2003); Hazell et al. (2000); Ugozzoli et al. (2002). For the synthesis, see: Foxon et al. (2007).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.

N,N-Bis(2-pyridylmethyl)aniline top

Crystal data top

C₁₈H₁₇N₃	F(000) = 584
M_r = 275.35	D_x = 1.240 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 649 reflections
a = 11.4866 (19) Å	θ = 2.4–19.7°
b = 16.811 (3) Å	µ = 0.08 mm⁻¹
c = 7.7930 (12) Å	T = 293 K
β = 101.471 (3)°	Block, colorless
V = 1474.8 (4) Å³	0.26 × 0.17 × 0.12 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2591 independent reflections
Radiation source: sealed tube	1251 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
φ and ω scans	θ_max = 25.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→13
T_min = 0.981, T_max = 0.991	k = −19→19
7541 measured reflections	l = −9→8

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0459P)²] where P = (F_o² + 2F_c²)/3
2591 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₈H₁₇N₃	V = 1474.8 (4) Å³
M_r = 275.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.4866 (19) Å	µ = 0.08 mm⁻¹
b = 16.811 (3) Å	T = 293 K
c = 7.7930 (12) Å	0.26 × 0.17 × 0.12 mm
β = 101.471 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	2591 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1251 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.991	R_int = 0.057
7541 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 0.93	Δρ_max = 0.14 e Å⁻³
2591 reflections	Δρ_min = −0.14 e Å⁻³
190 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.27837 (18)	0.47311 (12)	0.8924 (2)	0.0521 (6)
N2	0.2502 (2)	0.66652 (12)	0.6656 (3)	0.0633 (6)
N3	0.0590 (2)	0.36999 (13)	1.1010 (3)	0.0649 (6)
C1	0.3652 (2)	0.42824 (15)	0.8353 (3)	0.0472 (6)
C2	0.3695 (2)	0.34558 (15)	0.8561 (3)	0.0559 (7)
H2	0.3130	0.3204	0.9074	0.067*
C3	0.4559 (3)	0.30090 (16)	0.8019 (3)	0.0664 (8)
H3	0.4570	0.2461	0.8183	0.080*
C4	0.5403 (3)	0.33561 (18)	0.7243 (4)	0.0667 (8)
H4	0.5982	0.3049	0.6877	0.080*
C5	0.5375 (2)	0.41657 (18)	0.7018 (3)	0.0630 (8)
H5	0.5941	0.4409	0.6491	0.076*
C6	0.4515 (2)	0.46266 (16)	0.7564 (3)	0.0553 (7)
H6	0.4515	0.5175	0.7401	0.066*
C7	0.2770 (2)	0.55875 (14)	0.8723 (3)	0.0569 (7)
H7A	0.3572	0.5784	0.9120	0.068*
H7B	0.2283	0.5811	0.9487	0.068*
C8	0.2311 (2)	0.58934 (15)	0.6879 (3)	0.0469 (6)
C9	0.1736 (2)	0.54150 (14)	0.5561 (3)	0.0567 (7)
H9	0.1621	0.4878	0.5765	0.068*
C10	0.1332 (2)	0.57366 (17)	0.3930 (3)	0.0648 (8)
H10	0.0940	0.5420	0.3017	0.078*
C11	0.1510 (3)	0.65247 (19)	0.3663 (4)	0.0703 (9)
H11	0.1245	0.6758	0.2573	0.084*
C12	0.2089 (3)	0.69592 (16)	0.5048 (4)	0.0730 (9)
H12	0.2207	0.7498	0.4866	0.088*
C13	0.1675 (2)	0.43629 (15)	0.9124 (3)	0.0588 (7)
H13A	0.1477	0.3955	0.8233	0.071*
H13B	0.1055	0.4763	0.8889	0.071*
C14	0.1647 (2)	0.39913 (13)	1.0875 (3)	0.0470 (7)
C15	0.0517 (3)	0.33528 (16)	1.2541 (5)	0.0745 (9)
H15	−0.0216	0.3153	1.2668	0.089*
C16	0.1452 (3)	0.32745 (16)	1.3924 (4)	0.0713 (9)
H16	0.1360	0.3019	1.4946	0.086*
C17	0.2526 (3)	0.35824 (15)	1.3761 (4)	0.0631 (8)
H17	0.3177	0.3548	1.4683	0.076*
C18	0.2633 (2)	0.39451 (14)	1.2210 (3)	0.0538 (7)
H18	0.3357	0.4155	1.2067	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0523 (15)	0.0480 (13)	0.0571 (14)	0.0000 (12)	0.0131 (11)	0.0074 (10)
N2	0.0811 (18)	0.0502 (15)	0.0608 (16)	−0.0035 (12)	0.0198 (13)	0.0024 (11)
N3	0.0521 (16)	0.0707 (16)	0.0754 (18)	−0.0112 (13)	0.0209 (13)	−0.0024 (13)
C1	0.0477 (18)	0.0510 (17)	0.0402 (15)	−0.0018 (14)	0.0025 (12)	0.0056 (12)
C2	0.065 (2)	0.0538 (18)	0.0510 (17)	−0.0028 (15)	0.0166 (14)	0.0048 (13)
C3	0.078 (2)	0.0572 (18)	0.0641 (19)	0.0088 (17)	0.0151 (17)	0.0007 (15)
C4	0.062 (2)	0.075 (2)	0.064 (2)	0.0084 (17)	0.0129 (15)	−0.0038 (15)
C5	0.0474 (19)	0.081 (2)	0.0606 (19)	−0.0089 (17)	0.0098 (14)	0.0056 (16)
C6	0.0490 (17)	0.0583 (17)	0.0554 (17)	−0.0073 (15)	0.0027 (14)	0.0089 (13)
C7	0.067 (2)	0.0516 (17)	0.0518 (17)	0.0031 (14)	0.0115 (14)	0.0003 (12)
C8	0.0492 (17)	0.0454 (16)	0.0465 (16)	0.0047 (13)	0.0104 (12)	0.0013 (13)
C9	0.0641 (19)	0.0460 (15)	0.0554 (18)	0.0047 (14)	0.0007 (14)	0.0014 (14)
C10	0.060 (2)	0.072 (2)	0.0574 (19)	0.0117 (16)	−0.0015 (15)	−0.0101 (15)
C11	0.082 (2)	0.079 (2)	0.053 (2)	0.0183 (18)	0.0200 (17)	0.0141 (17)
C12	0.099 (3)	0.0552 (18)	0.072 (2)	0.0088 (18)	0.0345 (19)	0.0170 (17)
C13	0.0511 (18)	0.0672 (18)	0.0574 (18)	0.0035 (15)	0.0087 (13)	0.0072 (14)
C14	0.0452 (17)	0.0453 (15)	0.0528 (17)	−0.0010 (13)	0.0156 (14)	−0.0046 (12)
C15	0.070 (2)	0.071 (2)	0.094 (3)	−0.0126 (18)	0.043 (2)	−0.0042 (18)
C16	0.091 (3)	0.0649 (19)	0.067 (2)	0.004 (2)	0.037 (2)	0.0013 (16)
C17	0.067 (2)	0.0711 (19)	0.0524 (19)	0.0023 (17)	0.0146 (15)	−0.0002 (14)
C18	0.0471 (18)	0.0613 (18)	0.0550 (18)	−0.0075 (14)	0.0146 (15)	0.0003 (14)

Geometric parameters (Å, º) top

N1—C1	1.393 (3)	C7—H7B	0.9700
N1—C7	1.448 (3)	C8—C9	1.367 (3)
N1—C13	1.452 (3)	C9—C10	1.374 (3)
N2—C8	1.333 (3)	C9—H9	0.9300
N2—C12	1.343 (3)	C10—C11	1.363 (3)
N3—C14	1.332 (3)	C10—H10	0.9300
N3—C15	1.346 (3)	C11—C12	1.362 (4)
C1—C6	1.392 (3)	C11—H11	0.9300
C1—C2	1.399 (3)	C12—H12	0.9300
C2—C3	1.376 (3)	C13—C14	1.507 (3)
C2—H2	0.9300	C13—H13A	0.9700
C3—C4	1.372 (4)	C13—H13B	0.9700
C3—H3	0.9300	C14—C18	1.379 (3)
C4—C5	1.372 (3)	C15—C16	1.368 (4)
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.388 (3)	C16—C17	1.367 (4)
C5—H5	0.9300	C16—H16	0.9300
C6—H6	0.9300	C17—C18	1.381 (3)
C7—C8	1.519 (3)	C17—H17	0.9300
C7—H7A	0.9700	C18—H18	0.9300

C1—N1—C7	119.8 (2)	C8—C9—H9	120.4
C1—N1—C13	120.2 (2)	C10—C9—H9	120.4
C7—N1—C13	116.4 (2)	C11—C10—C9	119.3 (2)
C8—N2—C12	116.3 (2)	C11—C10—H10	120.3
C14—N3—C15	116.6 (2)	C9—C10—H10	120.3
C6—C1—N1	122.3 (2)	C12—C11—C10	117.7 (3)
C6—C1—C2	116.9 (3)	C12—C11—H11	121.1
N1—C1—C2	120.8 (2)	C10—C11—H11	121.1
C3—C2—C1	121.2 (3)	N2—C12—C11	124.6 (3)
C3—C2—H2	119.4	N2—C12—H12	117.7
C1—C2—H2	119.4	C11—C12—H12	117.7
C4—C3—C2	121.3 (3)	N1—C13—C14	116.8 (2)
C4—C3—H3	119.4	N1—C13—H13A	108.1
C2—C3—H3	119.4	C14—C13—H13A	108.1
C3—C4—C5	118.5 (3)	N1—C13—H13B	108.1
C3—C4—H4	120.7	C14—C13—H13B	108.1
C5—C4—H4	120.7	H13A—C13—H13B	107.3
C4—C5—C6	121.0 (3)	N3—C14—C18	123.0 (2)
C4—C5—H5	119.5	N3—C14—C13	114.1 (2)
C6—C5—H5	119.5	C18—C14—C13	122.9 (2)
C5—C6—C1	121.1 (3)	N3—C15—C16	124.2 (3)
C5—C6—H6	119.5	N3—C15—H15	117.9
C1—C6—H6	119.5	C16—C15—H15	117.9
N1—C7—C8	115.68 (19)	C17—C16—C15	118.2 (3)
N1—C7—H7A	108.4	C17—C16—H16	120.9
C8—C7—H7A	108.4	C15—C16—H16	120.9
N1—C7—H7B	108.4	C16—C17—C18	119.2 (3)
C8—C7—H7B	108.4	C16—C17—H17	120.4
H7A—C7—H7B	107.4	C18—C17—H17	120.4
N2—C8—C9	122.8 (2)	C14—C18—C17	118.8 (3)
N2—C8—C7	114.7 (2)	C14—C18—H18	120.6
C9—C8—C7	122.5 (2)	C17—C18—H18	120.6
C8—C9—C10	119.2 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C8–C12/N2 and C1–C6 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Cg2ⁱ	0.97	2.98 (4)	3.825 (3)	146
C15—H15···Cg1ⁱⁱ	0.93	2.96 (3)	3.619 (4)	129
C17—H17···Cg2ⁱⁱⁱ	0.93	2.65 (3)	3.530 (3)	159

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₇N₃
M_r	275.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.4866 (19), 16.811 (3), 7.7930 (12)
β (°)	101.471 (3)
V (Å³)	1474.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.26 × 0.17 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.981, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	7541, 2591, 1251
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.117, 0.93
No. of reflections	2591
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.14

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C8–C12/N2 and C1–C6 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Cg2ⁱ	0.97	2.98 (4)	3.825 (3)	146
C15—H15···Cg1ⁱⁱ	0.93	2.96 (3)	3.619 (4)	129
C17—H17···Cg2ⁱⁱⁱ	0.93	2.65 (3)	3.530 (3)	159

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

Acknowledgements

This work is supported by the State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Changchun, China.

References

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Volume 66| Part 2| February 2010| Page o475

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