4-(Methyl­amino)pyridine

Ng, S.W.

doi:10.1107/S1600536810008986

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o823

doi:10.1107/S1600536810008986

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4-(Methylamino)pyridine

Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 9 March 2010; accepted 9 March 2010; online 13 March 2010)

The non-H atoms of the title compound, C₆H₈N₂, lie in a common plane (r.m.s. deviation = 0.034 Å). In the crystal, adjacent molecules are linked by intermolecular N—H⋯N hydrogen bonds into a zigzag chain running along the c axis.

Related literature

For the non-linear optical activity of co-crystals with substituted 4-nitrophenol, see; Huang et al. (1997 ). For the crystal structure of 4-aminopyridine, see: Anderson et al. (2005 ) and for that of 4-dimethylpyridine, see: Ohms & Guth (1984 ).

Experimental

Crystal data

C₆H₈N₂
M_r = 108.14
Orthorhombic, P n a 2₁
a = 6.5645 (18) Å
b = 7.1230 (19) Å
c = 12.489 (4) Å
V = 584.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.12 × 0.12 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer
5127 measured reflections
707 independent reflections
521 reflections with I > 2σ(I)
R_int = 0.093

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.102
S = 0.99
707 reflections
78 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.88 (1)	2.06 (1)	2.930 (3)	168 (3)
Symmetry code: (i) $[-x, -y, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810008986/bt5213sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008986/bt5213Isup2.hkl

checkCIF report

Comment top

The amino nitrogen atom in 4-aminopyridine, a drug used for treating multiple sclerosis, is pyramidal; the amino group engages in a N–H···N hydrogen bonding interaction with adjacent pyridyl rings to generate a chain. The amino group uses its other nitrogen atom to form an N–H···π interaction with other pyridyl rings (Anderson et al., 2005).

In the title monomethyl-substituted analogue (Scheme I, Fig. 1), all non-hydrogen atoms lie in a common plane. However, the amino nitrogen atom is slightly pyramidal, this being displaced out of the trigonal plane by 0.18 (2) Å (Σangles 353 °). On the other hand, the amino nitrogen atom in 4-dimethylaminopyridine has unambiguously planar configuration (Ohms & Guth, 1984). In the present structure, adjacent molecules are linked by an N–H···N hydrogen bond to generate a helical chain motif (Table 1).

The compound belongs to a non-centrosymmetric space group, a feature that may render it useful for second-harmonic generation, particularly as it co-crystal with 2-methoxy-4-nitrophenol shows NLO activity (Huang et al., 1997).

Related literature top

For the non-linear optical activity of co-crystals with substituted 4-nitrophenol, see; Huang et al. (1997). For the crystal structure of 4-aminopyridine, see: Anderson et al. (2005) and for that of 4-dimethylpyridine, see: Ohms & Guth (1984).

Experimental top

4-Methylaminopyridine, as purchased from the Aldrich Chemical Company, is a crystalline material.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of a portion of the hydrogen-bonded chain structure of 4-methylaminopyridine at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

4-(Methylamino)pyridine top

Crystal data top

C₆H₈N₂	F(000) = 232
M_r = 108.14	D_x = 1.230 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 379 reflections
a = 6.5645 (18) Å	θ = 3.3–21.5°
b = 7.1230 (19) Å	µ = 0.08 mm⁻¹
c = 12.489 (4) Å	T = 100 K
V = 584.0 (3) Å³	Plate, colorless
Z = 4	0.12 × 0.12 × 0.02 mm

Data collection top

Bruker SMART APEX diffractometer	521 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.093
Graphite monochromator	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −7→8
5127 measured reflections	k = −9→8
707 independent reflections	l = −16→16

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0518P)²] where P = (F_o² + 2F_c²)/3
707 reflections	(Δ/σ)_max = 0.001
78 parameters	Δρ_max = 0.18 e Å⁻³
2 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₆H₈N₂	V = 584.0 (3) Å³
M_r = 108.14	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 6.5645 (18) Å	µ = 0.08 mm⁻¹
b = 7.1230 (19) Å	T = 100 K
c = 12.489 (4) Å	0.12 × 0.12 × 0.02 mm

Data collection top

Bruker SMART APEX diffractometer	521 reflections with I > 2σ(I)
5127 measured reflections	R_int = 0.093
707 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	2 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.18 e Å⁻³
707 reflections	Δρ_min = −0.20 e Å⁻³
78 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.2579 (4)	0.0086 (3)	0.49959 (18)	0.0219 (6)
H1	0.177 (4)	0.027 (5)	0.4440 (19)	0.036 (11)*
N2	−0.0105 (4)	−0.0122 (3)	0.8044 (2)	0.0232 (6)
C1	0.1745 (4)	−0.0004 (4)	0.5993 (2)	0.0193 (6)
C2	−0.0127 (4)	0.0889 (4)	0.6198 (2)	0.0217 (7)
H2	−0.0813	0.1550	0.5645	0.026*
C3	−0.0957 (5)	0.0794 (4)	0.7215 (2)	0.0256 (7)
H3	−0.2215	0.1417	0.7336	0.031*
C4	0.1690 (4)	−0.0944 (4)	0.7840 (2)	0.0220 (7)
H4	0.2337	−0.1593	0.8411	0.026*
C5	0.2673 (4)	−0.0917 (4)	0.6858 (2)	0.0207 (7)
H5	0.3959	−0.1511	0.6773	0.025*
C6	0.4412 (4)	−0.0966 (5)	0.4736 (2)	0.0302 (8)
H6A	0.5534	−0.0546	0.5195	0.045*
H6B	0.4772	−0.0753	0.3984	0.045*
H6C	0.4168	−0.2307	0.4853	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0237 (13)	0.0242 (14)	0.0178 (12)	0.0021 (12)	−0.0023 (10)	0.0025 (12)
N2	0.0277 (14)	0.0232 (12)	0.0189 (11)	0.0006 (12)	0.0005 (11)	−0.0001 (13)
C1	0.0189 (15)	0.0192 (15)	0.0198 (14)	−0.0048 (13)	−0.0055 (12)	−0.0010 (12)
C2	0.0231 (17)	0.0218 (16)	0.0201 (13)	0.0003 (13)	−0.0031 (12)	0.0033 (13)
C3	0.0293 (18)	0.0210 (16)	0.0264 (16)	0.0046 (14)	0.0013 (14)	−0.0005 (14)
C4	0.0248 (16)	0.0223 (16)	0.0188 (14)	−0.0016 (13)	−0.0039 (12)	0.0009 (13)
C5	0.0196 (16)	0.0205 (16)	0.0219 (14)	0.0009 (13)	−0.0024 (12)	−0.0011 (14)
C6	0.0242 (16)	0.0408 (19)	0.0256 (16)	0.0051 (14)	0.0028 (14)	0.0005 (14)

Geometric parameters (Å, º) top

N1—C1	1.362 (4)	C2—H2	0.9500
N1—C6	1.454 (4)	C3—H3	0.9500
N1—H1	0.88 (1)	C4—C5	1.386 (4)
N2—C4	1.340 (4)	C4—H4	0.9500
N2—C3	1.345 (4)	C5—H5	0.9500
C1—C5	1.401 (4)	C6—H6A	0.9800
C1—C2	1.407 (4)	C6—H6B	0.9800
C2—C3	1.384 (4)	C6—H6C	0.9800

C1—N1—C6	120.8 (2)	N2—C4—C5	124.8 (3)
C1—N1—H1	119 (2)	N2—C4—H4	117.6
C6—N1—H1	113 (2)	C5—C4—H4	117.6
C4—N2—C3	115.6 (3)	C4—C5—C1	119.1 (3)
N1—C1—C5	123.5 (3)	C4—C5—H5	120.4
N1—C1—C2	119.8 (3)	C1—C5—H5	120.4
C5—C1—C2	116.7 (3)	N1—C6—H6A	109.5
C3—C2—C1	119.3 (3)	N1—C6—H6B	109.5
C3—C2—H2	120.4	H6A—C6—H6B	109.5
C1—C2—H2	120.4	N1—C6—H6C	109.5
N2—C3—C2	124.5 (3)	H6A—C6—H6C	109.5
N2—C3—H3	117.7	H6B—C6—H6C	109.5
C2—C3—H3	117.7

C6—N1—C1—C5	7.2 (4)	C1—C2—C3—N2	−0.6 (5)
C6—N1—C1—C2	−174.3 (3)	C3—N2—C4—C5	−0.5 (5)
N1—C1—C2—C3	−179.8 (3)	N2—C4—C5—C1	−1.2 (5)
C5—C1—C2—C3	−1.1 (4)	N1—C1—C5—C4	−179.4 (3)
C4—N2—C3—C2	1.5 (5)	C2—C1—C5—C4	2.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.88 (1)	2.06 (1)	2.930 (3)	168 (3)

Symmetry code: (i) −x, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₈N₂
M_r	108.14
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	100
a, b, c (Å)	6.5645 (18), 7.1230 (19), 12.489 (4)
V (Å³)	584.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.12 × 0.12 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5127, 707, 521
R_int	0.093
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.102, 0.99
No. of reflections	707
No. of parameters	78
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.20

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.88 (1)	2.06 (1)	2.930 (3)	168 (3)

Symmetry code: (i) −x, −y, z−1/2.

Acknowledgements

I thank the University of Malaya for supporting this study.

References

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