1-Allyl-2-amino­pyridin-1-ium bromide

Seethalakshmi, T.; Venkatesan, P.; Nallu, M.; Lynch, D.E.; Thamotharan, S.

doi:10.1107/S1600536813012452

organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page o884

doi:10.1107/S1600536813012452

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1-Allyl-2-aminopyridin-1-ium bromide

T. Seethalakshmi,^a P. Venkatesan,^b M. Nallu,^b Daniel E. Lynch ^c and S. Thamotharan ^d ^*

^aDepartment of Physics, Government Arts College (Autonomous), Karur 639 005, India, ^bSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, India, ^cFaculty of Health and Life Sciences, Coventry University, Coventry CV1 5FB, England, and ^dDepartment of Bioinformatics, School of Chemical and Biotechnology, SASTRA University, Thanjavur 613 401, India
^*Correspondence e-mail: thamu@scbt.sastra.edu

(Received 29 April 2013; accepted 7 May 2013; online 15 May 2013)

In the cation of the title salt, C₈H₁₁N₂⁺·Br⁻, the dihedral angle between the planes of the pyridinium ring and the allyl group is 79.4 (3)°. In the crystal, N—H⋯Br and weak C—H⋯Br hydrogen bonds link the cations and anions, forming chains of alternating R₂¹(7) and R₄²(8) rings, which run parallel to the c-axis direction. The crystal studied was an inversion twin with components in a 0.753 (12):0.247 (12) ratio.

Related literature

For related structures, see: Seethalakshmi et al. (2006a ,b ,c , 2007 , 2013 ). For the biolgical activity of alkyl-pyridinium salts, see: Sundararaman et al. (2013 ); Ilangovan et al. (2012 ). For hydrogen-bond graph-set motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₁₁N₂⁺·Br⁻
M_r = 215.10
Orthorhombic, P n a 2₁
a = 7.8205 (2) Å
b = 13.3560 (3) Å
c = 8.5621 (2) Å
V = 894.32 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.53 mm⁻¹
T = 120 K
0.30 × 0.14 × 0.03 mm

Data collection

Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.343, T_max = 0.876
14540 measured reflections
2033 independent reflections
1960 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.053
S = 1.06
2033 reflections
110 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.35 e Å⁻³
Absolute structure: Flack (1983 ), 945 Friedel pairs
Flack parameter: 0.247 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Br1ⁱ	0.84 (2)	2.61 (2)	3.412 (2)	160 (4)
N2—H2B⋯Br1ⁱⁱ	0.85 (2)	2.51 (2)	3.357 (2)	175 (3)
C6—H6A⋯Br1ⁱⁱⁱ	0.99	2.91	3.668 (3)	134
C6—H6B⋯Br1ⁱ	0.99	2.84	3.810 (3)	167
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813012452/lh5611sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813012452/lh5611Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813012452/lh5611Isup3.cml

checkCIF report

Comment top

As part of our studies on pyridinum salts (Seethalakshmi et al., 2006a,b,c, 2007, 2013), we report herein the crystal structure of the title compound, (I). The asymmetric unit of (I) is shown in Fig. 1. The dihedral angle between the planes of the pyridinium ring and allyl group (C6/C7/C8) is 79.4 (3)°. The corresponding bond lengths and angles of the cation in (I) are comparable with those of related structures reported earlier (Seethalakshmi et al., 2006a,b,c, 2007, 2013).

In the crystal (Fig. 2) the amino group acts as a donor for two different bromide anions (Table 1). These intermolecular N—H···Br hydrogen bonds link the cations via bromide anions into one-dimensional chains which run parallel to the c axis. In addition, weak intermolecular C—H···Br interactions are observed between C6 (via H6A and H6B) and two bromide anions. The N2—H2A···Br1ⁱ and C6—H6B···Br1ⁱ interactions combine to generate a R¹₂(7) ring (Bernstein et al., 1995) and two N—H···O hydrogen bonds and two C—H···Br interactions combine to form a R²₄(8) ring motif. These two ring motifs are arranged alternately and run parallel to the c axis (Fig. 3).

Related literature top

For related structures, see: Seethalakshmi et al. (2006a,b,c, 2007, 2013). For the biolgical activity of alkyl-pyridinium salts, see: Sundararaman et al. (2013); Ilangovan et al. (2012). For hydrogen-bond graph-set motifs, see: Bernstein et al. (1995).

Experimental top

A solution of 2-aminopyridine (1.175 g, 25 ml) and allyl bromide (1.51 g, 25 ml) in dry acetone (15 ml) was stirred for 44 h at room temperature (303 K). The solid that separated was filtered, washed with dry acetone and dried in vacuum to give the stable salt, which was recrystallized from an aqueous ethanol (80% v/v) solution (m.p. 419–421 K, yield 63%).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I), showing ellipsoids at the 50% probability level.
	Fig. 2. Part of the crystal structure of (I) viewed along the a axis. The hydrogen bonds are indicated as dashed lines.
	Fig. 3. Arrangement of alternate R¹₂(7) and R²₄(10) ring motifs in a one-dimensional chain.

1-Allyl-2-aminopyridin-1-ium bromide top

Crystal data top

C₈H₁₁N₂⁺·Br⁻	F(000) = 432
M_r = 215.10	D_x = 1.598 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 1211 reflections
a = 7.8205 (2) Å	θ = 2.9–27.5°
b = 13.3560 (3) Å	µ = 4.53 mm⁻¹
c = 8.5621 (2) Å	T = 120 K
V = 894.32 (4) Å³	Plate, colourless
Z = 4	0.30 × 0.14 × 0.03 mm

Data collection top

Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer	2033 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1960 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ϕ and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −17→17
T_min = 0.343, T_max = 0.876	l = −10→11
14540 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.023	w = 1/[σ²(F_o²) + (0.0198P)² + 0.704P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.053	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.43 e Å⁻³
2033 reflections	Δρ_min = −0.35 e Å⁻³
110 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.0051 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 945 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.247 (12)

Crystal data top

C₈H₁₁N₂⁺·Br⁻	V = 894.32 (4) Å³
M_r = 215.10	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 7.8205 (2) Å	µ = 4.53 mm⁻¹
b = 13.3560 (3) Å	T = 120 K
c = 8.5621 (2) Å	0.30 × 0.14 × 0.03 mm

Data collection top

Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer	2033 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1960 reflections with I > 2σ(I)
T_min = 0.343, T_max = 0.876	R_int = 0.058
14540 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.053	Δρ_max = 0.43 e Å⁻³
S = 1.06	Δρ_min = −0.35 e Å⁻³
2033 reflections	Absolute structure: Flack (1983), 945 Friedel pairs
110 parameters	Absolute structure parameter: 0.247 (12)
3 restraints

Special details top

Experimental. The minimum and maximum absorption values stated above are those calculated in SHELXL97 from the given crystal dimensions. The ratio of minimum to maximum apparent transmission was determined experimentally as 0.611792.

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
Br1	0.03564 (3)	0.120651 (14)	0.72785 (7)	0.01951 (9)
C1	0.2522 (4)	0.6591 (2)	0.6626 (3)	0.0171 (6)
C2	0.2481 (4)	0.75344 (18)	0.5884 (3)	0.0223 (5)
H2	0.2826	0.7598	0.4825	0.027*
C3	0.1942 (4)	0.8354 (2)	0.6696 (4)	0.0238 (6)
H3	0.1909	0.8989	0.6198	0.029*
C4	0.1434 (4)	0.8267 (2)	0.8268 (4)	0.0227 (6)
H4	0.1071	0.8837	0.8841	0.027*
C5	0.1474 (4)	0.7353 (2)	0.8941 (3)	0.0210 (5)
H5	0.1121	0.7285	0.9997	0.025*
C6	0.1943 (3)	0.55284 (19)	0.8940 (3)	0.0195 (5)
H6A	0.1970	0.5632	1.0085	0.023*
H6B	0.2962	0.5131	0.8647	0.023*
C7	0.0363 (3)	0.4961 (2)	0.8511 (3)	0.0221 (6)
H7	−0.0714	0.5267	0.8704	0.026*
C8	0.0379 (4)	0.4061 (2)	0.7883 (4)	0.0264 (6)
H8A	0.1437	0.3737	0.7678	0.032*
H8B	−0.0666	0.3736	0.7635	0.032*
N1	0.2010 (3)	0.65157 (19)	0.8142 (3)	0.0174 (5)
N2	0.3083 (3)	0.57779 (17)	0.5869 (2)	0.0208 (5)
H2A	0.339 (5)	0.524 (2)	0.630 (4)	0.049 (11)*
H2B	0.341 (5)	0.588 (3)	0.494 (3)	0.040 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02238 (13)	0.02017 (12)	0.01599 (12)	−0.00267 (8)	−0.00157 (17)	0.00066 (16)
C1	0.0158 (12)	0.0185 (14)	0.0168 (12)	−0.0021 (11)	−0.0001 (10)	−0.0016 (10)
C2	0.0245 (13)	0.0228 (14)	0.0196 (13)	−0.0015 (11)	0.0013 (11)	0.0045 (10)
C3	0.0259 (15)	0.0163 (13)	0.0293 (15)	0.0019 (12)	−0.0013 (11)	0.0036 (10)
C4	0.0223 (14)	0.0220 (14)	0.0238 (15)	0.0013 (11)	0.0000 (11)	−0.0053 (11)
C5	0.0225 (14)	0.0230 (14)	0.0176 (12)	0.0010 (11)	−0.0009 (11)	−0.0037 (10)
C6	0.0255 (13)	0.0198 (12)	0.0131 (11)	0.0014 (10)	0.0020 (10)	0.0024 (9)
C7	0.0196 (13)	0.0238 (14)	0.0228 (14)	−0.0012 (10)	0.0014 (10)	0.0097 (11)
C8	0.0240 (14)	0.0286 (14)	0.0265 (13)	−0.0040 (11)	−0.0018 (10)	0.0051 (12)
N1	0.0211 (12)	0.0169 (11)	0.0141 (11)	−0.0002 (10)	0.0004 (10)	−0.0004 (9)
N2	0.0265 (12)	0.0215 (12)	0.0144 (11)	0.0023 (9)	0.0006 (9)	0.0014 (9)

Geometric parameters (Å, º) top

C1—N2	1.339 (4)	C6—N1	1.486 (3)
C1—N1	1.361 (3)	C6—C7	1.496 (4)
C1—C2	1.412 (4)	C6—H6A	0.9900
C2—C3	1.364 (4)	C6—H6B	0.9900
C2—H2	0.9500	C7—C8	1.317 (4)
C3—C4	1.408 (4)	C7—H7	0.9500
C3—H3	0.9500	C8—H8A	0.9500
C4—C5	1.350 (4)	C8—H8B	0.9500
C4—H4	0.9500	N2—H2A	0.844 (18)
C5—N1	1.376 (4)	N2—H2B	0.849 (19)
C5—H5	0.9500

N2—C1—N1	119.9 (3)	C7—C6—H6A	109.3
N2—C1—C2	120.9 (3)	N1—C6—H6B	109.3
N1—C1—C2	119.2 (3)	C7—C6—H6B	109.3
C3—C2—C1	119.6 (3)	H6A—C6—H6B	108.0
C3—C2—H2	120.2	C8—C7—C6	123.7 (3)
C1—C2—H2	120.2	C8—C7—H7	118.2
C2—C3—C4	120.5 (3)	C6—C7—H7	118.2
C2—C3—H3	119.7	C7—C8—H8A	120.0
C4—C3—H3	119.7	C7—C8—H8B	120.0
C5—C4—C3	118.4 (3)	H8A—C8—H8B	120.0
C5—C4—H4	120.8	C1—N1—C5	120.2 (3)
C3—C4—H4	120.8	C1—N1—C6	120.9 (3)
C4—C5—N1	122.0 (3)	C5—N1—C6	118.8 (2)
C4—C5—H5	119.0	C1—N2—H2A	125 (3)
N1—C5—H5	119.0	C1—N2—H2B	115 (3)
N1—C6—C7	111.5 (2)	H2A—N2—H2B	118 (4)
N1—C6—H6A	109.3

N2—C1—C2—C3	−178.4 (3)	C2—C1—N1—C5	−0.5 (4)
N1—C1—C2—C3	0.4 (4)	N2—C1—N1—C6	−4.5 (4)
C1—C2—C3—C4	0.2 (4)	C2—C1—N1—C6	176.6 (3)
C2—C3—C4—C5	−0.8 (4)	C4—C5—N1—C1	0.0 (4)
C3—C4—C5—N1	0.7 (4)	C4—C5—N1—C6	−177.2 (3)
N1—C6—C7—C8	122.7 (3)	C7—C6—N1—C1	−79.8 (3)
N2—C1—N1—C5	178.3 (3)	C7—C6—N1—C5	97.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Br1ⁱ	0.84 (2)	2.61 (2)	3.412 (2)	160 (4)
N2—H2B···Br1ⁱⁱ	0.85 (2)	2.51 (2)	3.357 (2)	175 (3)
C6—H6A···Br1ⁱⁱⁱ	0.99	2.91	3.668 (3)	134
C6—H6B···Br1ⁱ	0.99	2.84	3.810 (3)	167

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

Experimental details

Crystal data
Chemical formula	C₈H₁₁N₂⁺·Br⁻
M_r	215.10
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	120
a, b, c (Å)	7.8205 (2), 13.3560 (3), 8.5621 (2)
V (Å³)	894.32 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.53
Crystal size (mm)	0.30 × 0.14 × 0.03

Data collection
Diffractometer	Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.343, 0.876
No. of measured, independent and observed [I > 2σ(I)] reflections	14540, 2033, 1960
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.053, 1.06
No. of reflections	2033
No. of parameters	110
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.35
Absolute structure	Flack (1983), 945 Friedel pairs
Absolute structure parameter	0.247 (12)

Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Br1ⁱ	0.844 (18)	2.61 (2)	3.412 (2)	160 (4)
N2—H2B···Br1ⁱⁱ	0.849 (19)	2.511 (19)	3.357 (2)	175 (3)
C6—H6A···Br1ⁱⁱⁱ	0.99	2.91	3.668 (3)	133.6
C6—H6B···Br1ⁱ	0.99	2.84	3.810 (3)	166.5

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

Acknowledgements

The authors thank the EPSRC National Crystallography Service (University of Southampton, UK) for the X-ray data collection and Professor P. Kaliannan for his help. ST thanks the management of SASTRA University for their encouragement.

References

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