N,N′-Dimethyl-N,N′-bis­(pyridin-2-yl)methane­diamine

Lee, M.-S.; Yoon, M.; Yang, O.; Lee, D.-H.; Park, G.

doi:10.1107/S1600536811046320

organic compounds

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Volume 67| Part 12| December 2011| Page o3226

https://doi.org/10.1107/S1600536811046320

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N,N′-Dimethyl-N,N′-bis(pyridin-2-yl)methanediamine

Moon-Sun Lee,^a Minyoung Yoon,^b O-bong Yang,^c Dong-Heon Lee ^a ^* and Gyungse Park ^d ^*

^aDepartment of Chemistry, Chonbuk National University, Jeonju, Chonbuk 561-756, Republic of Korea, ^bNational Creative Research Initiative Center for Smart Supramolecules (CSS), Department of Chemistry and Division of Advanced Materials Science, Pohang University of Science and Technology (POSTECH), Pohang 790-784, Republic of Korea, ^cSchool of Semiconductor and Chemical Engineering & Solar Energy Research Center, Chonbuk National University, Jeonju, Chonbuk 561-756, Republic of Korea, and ^dThe Department of Chemistry, College of Science and Technology, Kunsan National University, 68 Miryong-Dong, Kusan, Jeollabuk-Do 573-701, Republic of Korea
^*Correspondence e-mail: , parkg@kunsan.ac.kr

(Received 22 October 2011; accepted 3 November 2011; online 9 November 2011)

The title compound, C₁₃H₁₆N₄, consists of two pyridine rings which are linked by an N,N′-dimethylmethaneamine chain. The pyridine rings adopt a twist conformation and the dihedral angle between them is 60.85 (5)°. The crystal packing is stabilized by weak C—H⋯π interactions.

Related literature

For the synthesis of the title compound, see: Kahn et al. (1945 ). For applications of heteroaromatic amines, see: Mehrkhodavandi & Schrock (2001 ); Hall et al. (1998 ); Lee (2003 ).

Experimental

Crystal data

C₁₃H₁₆N₄
M_r = 228.30
Monoclinic, P 2₁ /n
a = 11.6652 (7) Å
b = 8.3921 (5) Å
c = 12.8966 (7) Å
β = 106.634 (2)°
V = 1209.69 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.12 × 0.08 × 0.08 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.963, T_max = 0.986
27844 measured reflections
2516 independent reflections
2105 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.125
S = 0.96
2516 reflections
218 parameters
All H-atom parameters refined
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the N1/C1–C5 and N4/C9–C15 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cg2ⁱ	0.99 (2)	2.64 (2)	3.484 (1)	143 (1)
C6—H7⋯Cg2ⁱⁱ	1.00 (2)	2.75 (2)	3.545 (2)	137 (1)
C10—H13⋯Cg1ⁱⁱⁱ	0.95 (2)	2.90 (1)	3.637 (1)	135 (1)
Symmetry codes: (i) -x+1, -y, -z+2; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x, y-1, z.

Data collection: APEX2 (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: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811046320/bx2378sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046320/bx2378Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811046320/bx2378Isup3.cml

checkCIF report

Comment top

Heteroaromatic amines based metal complexes have been extensively studied due to their numerous potential applications as catalysts, drugs, biomimetic chemistry, and so on. (Mehrkhodavandi, et al., (2001) , Hall, et al.,(1998), Lee, (2003). We are interested in the use of chelates containing pyridylamine. We report here the crystal structure of the title compound, Fig. 1, which consists of two 2-pyridyl rings which are linked together by a N,N'-dimethylmethaneamine chain .The pyridine rings adopt a twist conformation and the dihedral angle between them is 60.85 (5)°. The crystal packing is stabilized by weak C—H···π interactions, Fig. 2, Table 1.

Related literature top

For the synthesis of the title compound, see: Kahn et al. (1945). For applications of heteroaromatic amines, see: Mehrkhodavandi & Schrock (2001); Hall et al. (1998); Lee (2003).

Experimental top

N,N'-dimethyl-N,N'-di(pyridin-2-yl)methanediamine was prepared by a reported method, Kahn, et al., (1945). A solution of 2-(methylamino)pyridine (5.00 g, 4.62 × 10 ^-2 mol) in water (50 ml) was added dropwise to 37% formaldehyde solution (1.83 ml, 2.31 × 10^-2mol) at 0°C. The reation mixture was stirred at room temperature for overnight and the white precipitate formed was filtered,washed with water and dried. It was dissolved in acetone, dried over MgSO₄ and concentrated. It was recrystallized in acetonitrile. Yield: 92% (4.88 g)

Structure description top

For the synthesis of the title compound, see: Kahn et al. (1945). For applications of heteroaromatic amines, see: Mehrkhodavandi & Schrock (2001); Hall et al. (1998); Lee (2003).

Computing details top

Data collection: APEX2 (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: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound showing the labelling of the atoms. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. Part of the crystal structure of (I) showing the formation of a C—H···π interactions.

N,N'-Dimethyl-N,N'-bis(pyridin-2-yl)methanediamine top

Crystal data top

C₁₃H₁₆N₄	F(000) = 488
M_r = 228.30	D_x = 1.254 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2yn	Cell parameters from 2516 reflections
a = 11.6652 (7) Å	θ = 2.1–26.5°
b = 8.3921 (5) Å	µ = 0.08 mm⁻¹
c = 12.8966 (7) Å	T = 100 K
β = 106.634 (2)°	Rod, colourless
V = 1209.69 (12) Å³	0.12 × 0.08 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	2105 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.050
Graphite monochromator	θ_max = 26.5°, θ_min = 2.1°
θ/2φ scans	h = −14→14
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −10→10
T_min = 0.963, T_max = 0.986	l = −16→14
27844 measured reflections	4 standard reflections every 30 min
2516 independent reflections	intensity decay: 0.0%

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	All H-atom parameters refined
S = 0.96	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
2516 reflections	(Δ/σ)_max < 0.001
218 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₃H₁₆N₄	V = 1209.69 (12) Å³
M_r = 228.30	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.6652 (7) Å	µ = 0.08 mm⁻¹
b = 8.3921 (5) Å	T = 100 K
c = 12.8966 (7) Å	0.12 × 0.08 × 0.08 mm
β = 106.634 (2)°

Data collection top

Bruker APEXII diffractometer	2105 reflections with I > 2σ(I)
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	R_int = 0.050
T_min = 0.963, T_max = 0.986	4 standard reflections every 30 min
27844 measured reflections	intensity decay: 0.0%
2516 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.125	All H-atom parameters refined
S = 0.96	Δρ_max = 0.23 e Å⁻³
2516 reflections	Δρ_min = −0.21 e Å⁻³
218 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
N1	0.43474 (8)	0.22148 (11)	0.82931 (7)	0.0194 (3)
N2	0.61745 (8)	0.11262 (11)	0.82658 (8)	0.0203 (3)
N3	0.59838 (8)	−0.15394 (11)	0.89105 (8)	0.0189 (3)
N4	0.79220 (8)	−0.22454 (12)	0.98754 (7)	0.0182 (3)
C1	0.34526 (10)	0.32394 (15)	0.78856 (9)	0.0211 (3)
C2	0.33876 (11)	0.42500 (14)	0.70242 (9)	0.0214 (3)
C3	0.43186 (10)	0.41792 (14)	0.65514 (9)	0.0200 (3)
C4	0.52555 (10)	0.31431 (14)	0.69472 (9)	0.0173 (3)
C5	0.52473 (10)	0.21664 (13)	0.78366 (9)	0.0160 (3)
C6	0.71691 (12)	0.09942 (17)	0.78056 (12)	0.0272 (3)
C7	0.62117 (10)	0.01339 (13)	0.91939 (9)	0.0173 (3)
C8	0.47475 (11)	−0.19594 (16)	0.83643 (11)	0.0240 (3)
C9	0.67862 (10)	−0.27049 (13)	0.94043 (8)	0.0163 (3)
C10	0.64315 (11)	−0.43154 (14)	0.93928 (9)	0.0205 (3)
C11	0.72811 (12)	−0.54307 (15)	0.98755 (9)	0.0248 (3)
C12	0.84533 (12)	−0.49686 (15)	1.03581 (9)	0.0255 (3)
C13	0.87199 (11)	−0.33721 (14)	1.03368 (9)	0.0221 (3)
H1	0.2816 (13)	0.3259 (16)	0.8256 (12)	0.031 (4)*
H2	0.2701 (12)	0.4955 (17)	0.6790 (10)	0.029 (4)*
H3	0.4313 (12)	0.4841 (17)	0.5946 (11)	0.028 (4)*
H4	0.5883 (13)	0.3065 (16)	0.6629 (11)	0.025 (3)*
H5	0.7601 (15)	0.201 (2)	0.7856 (14)	0.048 (5)*
H6	0.7696 (15)	0.022 (2)	0.8232 (13)	0.047 (4)*
H7	0.6898 (15)	0.059 (2)	0.7046 (14)	0.045 (4)*
H8	0.5576 (11)	0.0536 (14)	0.9520 (10)	0.018 (3)*
H9	0.6997 (13)	0.0194 (15)	0.9712 (11)	0.023 (3)*
H10	0.4350 (13)	−0.1019 (18)	0.8023 (12)	0.032 (4)*
H11	0.4723 (12)	−0.2806 (19)	0.7818 (13)	0.035 (4)*
H12	0.4316 (13)	−0.2327 (17)	0.8900 (12)	0.033 (4)*
H13	0.5616 (13)	−0.4628 (16)	0.9100 (11)	0.028 (4)*
H14	0.7042 (13)	−0.6532 (18)	0.9862 (12)	0.032 (4)*
H15	0.9091 (13)	−0.5706 (18)	1.0696 (11)	0.033 (4)*
H16	0.9557 (12)	−0.3009 (15)	1.0693 (11)	0.021 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0190 (5)	0.0203 (5)	0.0189 (5)	0.0021 (4)	0.0054 (4)	0.0009 (4)
N2	0.0208 (5)	0.0187 (5)	0.0239 (5)	0.0052 (4)	0.0102 (4)	0.0059 (4)
N3	0.0177 (5)	0.0145 (5)	0.0211 (5)	−0.0003 (4)	0.0003 (4)	0.0002 (4)
N4	0.0185 (5)	0.0185 (5)	0.0166 (5)	0.0017 (4)	0.0035 (4)	0.0008 (4)
C1	0.0178 (6)	0.0235 (6)	0.0218 (6)	0.0025 (5)	0.0051 (5)	−0.0018 (5)
C2	0.0200 (6)	0.0186 (6)	0.0218 (6)	0.0038 (5)	−0.0002 (5)	−0.0010 (5)
C3	0.0260 (6)	0.0146 (6)	0.0170 (6)	−0.0035 (5)	0.0021 (5)	0.0005 (4)
C4	0.0186 (6)	0.0159 (6)	0.0177 (6)	−0.0029 (4)	0.0055 (5)	−0.0019 (4)
C5	0.0178 (6)	0.0133 (6)	0.0162 (5)	−0.0015 (4)	0.0037 (4)	−0.0029 (4)
C6	0.0236 (7)	0.0254 (7)	0.0363 (8)	0.0077 (6)	0.0145 (6)	0.0075 (6)
C7	0.0197 (6)	0.0149 (6)	0.0159 (6)	0.0004 (5)	0.0030 (5)	0.0000 (4)
C8	0.0196 (6)	0.0204 (7)	0.0274 (7)	−0.0006 (5)	−0.0007 (5)	−0.0002 (5)
C9	0.0208 (6)	0.0172 (6)	0.0120 (5)	0.0008 (5)	0.0063 (4)	0.0005 (4)
C10	0.0254 (7)	0.0185 (6)	0.0178 (6)	−0.0024 (5)	0.0067 (5)	−0.0015 (4)
C11	0.0400 (8)	0.0151 (6)	0.0208 (6)	0.0022 (5)	0.0111 (6)	0.0001 (5)
C12	0.0342 (7)	0.0219 (6)	0.0202 (6)	0.0119 (5)	0.0072 (5)	0.0039 (5)
C13	0.0224 (6)	0.0258 (7)	0.0173 (6)	0.0063 (5)	0.0044 (5)	0.0011 (5)

Geometric parameters (Å, º) top

N1—C1	1.3382 (15)	C4—H4	0.938 (15)
N1—C5	1.3431 (15)	C6—H5	0.983 (17)
N2—C5	1.3769 (15)	C6—H6	0.951 (18)
N2—C7	1.4485 (14)	C6—H7	0.998 (17)
N2—C6	1.4508 (15)	C7—H8	1.010 (13)
N3—C9	1.3773 (15)	C7—H9	0.968 (14)
N3—C8	1.4556 (15)	C8—H10	0.957 (16)
N3—C7	1.4563 (15)	C8—H11	0.996 (16)
N4—C13	1.3406 (15)	C8—H12	1.012 (16)
N4—C9	1.3463 (15)	C9—C10	1.4123 (16)
C1—C2	1.3823 (17)	C10—C11	1.3756 (17)
C1—H1	0.992 (15)	C10—H13	0.954 (14)
C2—C3	1.3907 (17)	C11—C12	1.3858 (19)
C2—H2	0.972 (14)	C11—H14	0.964 (15)
C3—C4	1.3753 (17)	C12—C13	1.3775 (18)
C3—H3	0.957 (15)	C12—H15	0.969 (15)
C4—C5	1.4121 (16)	C13—H16	1.001 (14)

C1—N1—C5	117.83 (10)	H6—C6—H7	108.0 (13)
C5—N2—C7	122.07 (9)	N2—C7—N3	112.76 (9)
C5—N2—C6	120.81 (10)	N2—C7—H8	107.5 (7)
C7—N2—C6	117.12 (9)	N3—C7—H8	108.9 (7)
C9—N3—C8	119.99 (10)	N2—C7—H9	109.8 (8)
C9—N3—C7	121.18 (9)	N3—C7—H9	107.0 (8)
C8—N3—C7	116.06 (10)	H8—C7—H9	111.0 (10)
C13—N4—C9	117.83 (10)	N3—C8—H10	107.8 (9)
N1—C1—C2	124.54 (11)	N3—C8—H11	109.9 (8)
N1—C1—H1	115.4 (8)	H10—C8—H11	110.5 (12)
C2—C1—H1	120.0 (8)	N3—C8—H12	111.2 (8)
C1—C2—C3	117.13 (11)	H10—C8—H12	107.2 (12)
C1—C2—H2	118.3 (8)	H11—C8—H12	110.2 (13)
C3—C2—H2	124.6 (8)	N4—C9—N3	117.13 (10)
C4—C3—C2	120.11 (11)	N4—C9—C10	121.76 (10)
C4—C3—H3	119.2 (9)	N3—C9—C10	121.10 (10)
C2—C3—H3	120.7 (9)	C11—C10—C9	118.39 (11)
C3—C4—C5	118.62 (11)	C11—C10—H13	119.9 (9)
C3—C4—H4	121.2 (9)	C9—C10—H13	121.6 (8)
C5—C4—H4	120.1 (9)	C10—C11—C12	120.22 (12)
N1—C5—N2	117.75 (10)	C10—C11—H14	118.5 (9)
N1—C5—C4	121.76 (10)	C12—C11—H14	121.3 (9)
N2—C5—C4	120.49 (10)	C13—C12—C11	117.55 (11)
N2—C6—H5	111.2 (10)	C13—C12—H15	118.8 (9)
N2—C6—H6	106.0 (10)	C11—C12—H15	123.7 (9)
H5—C6—H6	108.4 (14)	N4—C13—C12	124.25 (12)
N2—C6—H7	111.2 (10)	N4—C13—H16	116.8 (7)
H5—C6—H7	111.7 (14)	C12—C13—H16	118.9 (7)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N1/C1–C5 and N4/C9–C15 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cg2ⁱ	0.99 (2)	2.64 (2)	3.484 (1)	143 (1)
C6—H7···Cg2ⁱⁱ	1.00 (2)	2.75 (2)	3.545 (2)	137 (1)
C10—H13···Cg1ⁱⁱⁱ	0.95 (2)	2.90 (1)	3.637 (1)	135 (1)

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₆N₄
M_r	228.30
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	11.6652 (7), 8.3921 (5), 12.8966 (7)
β (°)	106.634 (2)
V (Å³)	1209.69 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.12 × 0.08 × 0.08

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.963, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	27844, 2516, 2105
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.125, 0.96
No. of reflections	2516
No. of parameters	218
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.21

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N1/C1–C5 and N4/C9–C15 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cg2ⁱ	0.99 (2)	2.64 (2)	3.484 (1)	143 (1)
C6—H7···Cg2ⁱⁱ	1.00 (2)	2.75 (2)	3.545 (2)	137 (1)
C10—H13···Cg1ⁱⁱⁱ	0.95 (2)	2.90 (1)	3.637 (1)	135 (1)

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) x, y−1, z.

Acknowledgements

This work was supported by the "Human Resource Development (project name: Advanced track for Si-based solar cell materials and devices, project No. 201040100660)" of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korean Government Ministry of Knowledge Economy.

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact, Bonn, Germany. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hall, J., Haner, R., Aime, S., Botta, M., Faulkner, S., Parker, D. & de Sousa, S. S. (1998). New J. Chem. pp. 627–631. Web of Science CrossRef Google Scholar
Kahn, H. J., Petrow, V. A., Wien, R. & Harrison, J. (1945). J. Chem. Soc. pp. 858–861 CrossRef Google Scholar
Lee, D.-H. (2003). J. Kor. Chem. Soc. 47, 427–431. CAS Google Scholar
Mehrkhodavandi, P. & Schrock, R. R. (2001). J. Am. Chem. Soc. 123, 10746–10747. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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