3-Amino-1-methyl­pyrazin-1-ium chloride

Foucher, D.; Wylie, S.; Acosta, J.; Lough, A.J.

doi:10.1107/S1600536809051265

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o61

doi:10.1107/S1600536809051265

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3-Amino-1-methylpyrazin-1-ium chloride

Daniel Foucher,^a Stephen Wylie,^a Joshua Acosta ^a and Alan J. Lough ^b ^*

^aDepartment of Chemistry and Biology, Ryerson University, Toronto, Ontario, Canada, M5B 2K3, and ^bDepartment of Chemistry, University of Toronto, Toronto, Ontario, Canada, M5S 3H6
^*Correspondence e-mail: alough@chem.utoronto.ca

(Received 24 November 2009; accepted 27 November 2009; online 4 December 2009)

In the cation of the title compound, C₅H₈N₃⁺·Cl⁻, the C—N(H₂) bond distance [1.348 (3) Å] is at the lower end of the range for aryl amines. In the crystal structure, cations and anions are linked via N—H⋯Cl hydrogen bonds, forming one-dimensional chains along [100].

Related literature

For the synthesis and characterization of the title compound, see: Foucher et al. (1993 ). Additional preparative details of similar compounds are given by Goto et al. (1968 ). For related structures, see Chao et al. (1976 ); Kazheva et al. (2006 ); Foucher et al. (1989 ); Lu & Xi (2008 ). For the crystal structure of 3-amino-1- methylpyrazin-1-ium iodide, see: Foucher et al. (2009 ). For comparative bond-distance data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₅H₈N₃⁺·Cl⁻
M_r = 145.59
Orthorhombic, P b c a
a = 11.3164 (3) Å
b = 9.5029 (5) Å
c = 12.3877 (5) Å
V = 1332.16 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 150 K
0.24 × 0.16 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing 1995 ) T_min = 0.819, T_max = 0.946
9107 measured reflections
1526 independent reflections
1144 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.111
S = 1.10
1526 reflections
91 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H1N⋯Cl1	0.91 (3)	2.40 (3)	3.297 (2)	168 (2)
N7—H2N⋯Cl1ⁱ	0.94 (3)	2.37 (3)	3.289 (2)	168 (3)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: COLLECT (Nonius BV, 2002 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809051265/tk2586sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051265/tk2586Isup2.hkl

checkCIF report

Comment top

The title chloride compound, (I), was recovered from the ion exchange (Dowex 1-X8 ion exchange resin saturated with Cl^- anions) of the iodide precursor of N-methyl-3-aminopyrazinium iodide (Foucher et al., 1993). The proximity of the amine group to one of the diazine N atoms makes it an ideal chelating ligand to metals and geometrically suggests the possibility for amine-imine tautomerism. We have investigated the possibility that a smaller counter ion might induce a preference for the imine tautomer in these salts.

The molecular structure of (I) is shown in Fig. 1. The cation is the amine tautomer and resembles closely in terms of bond angles and bond lengths, other N-methylated amino pyrazinium salts (Kazheva et al., 2006; Foucher et al., 1989). The C5—N4—C3 bond angle in (I) [121.02 (18) °] is significantly wider than in 2-aminopyrazine [116.6 (1)°] (Chao et al., 1976) but similar to the angle found in N-methyl-3-aminopyrazinium iodide (121.3 (5)°; Foucher et al., 2010). 2-Aminopyrazine and both N-methyl-3-aminopyrazium salts are characterized by short amine-ring bond distances [N7—C6 in (I) = 1.348 (3) Å, 1.341 (1)Å (Chao et al., 1976) and 1.338 (8)Å (Foucher et al., 2009)] compared to typical values for C(sp²)-NH₂ bond lengths, i.e. 1.36 Å (Allen et al., 1987)] although these distances are significantly longer than the C=N(H) bond [1.285 (4) Å] in N-(4-imino-3,5-dimethylcyclohexa-2,5-dienylidene)-2,6-dimethylaniline (Lu & Xi, 2008). These short bond lengths are suggestive of a considerable degree of double bond character, where the lone pair of the amine participates in the resonance of the ring π system. In the crystal structure, cations and anions are linked via intermolecular N—H···Cl hydrogen bonds to form one-dimensional chains along [100], Table 1 and Fig. 2.

Related literature top

For the synthesis and characterization of the title compound, see: Foucher et al. (1993). Additional preparative details of similar compounds are given by Goto et al. (1968). For related structures, see Chao et al. (1976); Kazheva et al. (2006); Foucher et al. (1989); Lu & Xi (2008). For the crystal structure of N-methyl-3-aminopyrazinium iodide, see: Foucher et al. (2010). For comparative bond-distance data, see: Allen et al. (1987).

Experimental top

General procedures for the synthesis of this type of compound are given by Goto et al. (1968) and Kazheva et al. (2006). The title compound was recovered from the ion exchange (Dowex 1-X8 ion exchange resin saturated with Cl^- anion) of a concentrated aqueous solution containing 0.30 g (1.266 mmol) of N-methyl-3-pyrazinium iodide (Foucher et al., 1993). The aqueous fractions containing the crude title compound were collected and brought to dryness. Crystals suitable for X-ray diffraction were isolated from the recrystallization of the crude product from boiling ethanol. Yield 0.11 g, 78%. Characterization by NMR agreed with previous literature (Foucher et al., 1993).

Computing details top

Data collection: COLLECT (Nonius BV, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I) with displacement ellipsoids drawn at the 30% probability level. The dashed line indicates a hydrogen bond.
	Fig. 2. Part of the crystal structure of (I) with hydrogen bonds shown as dashed lines.

3-Amino-1-methylpyrazin-1-ium chloride top

Crystal data top

C₅H₈N₃⁺·Cl⁻	F(000) = 608
M_r = 145.59	D_x = 1.452 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9107 reflections
a = 11.3164 (3) Å	θ = 3.3–27.5°
b = 9.5029 (5) Å	µ = 0.48 mm⁻¹
c = 12.3877 (5) Å	T = 150 K
V = 1332.16 (10) Å³	Needle, pale yellow
Z = 8	0.24 × 0.16 × 0.12 mm

Data collection top

Nonius KappaCCD diffractometer	1526 independent reflections
Radiation source: fine-focus sealed tube	1144 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ϕ scans and ω scans with κ offsets	h = −14→14
Absorption correction: multi-scan (SORTAV; Blessing 1995)	k = −11→12
T_min = 0.819, T_max = 0.946	l = −16→15
9107 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0514P)² + 0.7939P] where P = (F_o² + 2F_c²)/3
1526 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₅H₈N₃⁺·Cl⁻	V = 1332.16 (10) Å³
M_r = 145.59	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.3164 (3) Å	µ = 0.48 mm⁻¹
b = 9.5029 (5) Å	T = 150 K
c = 12.3877 (5) Å	0.24 × 0.16 × 0.12 mm

Data collection top

Nonius KappaCCD diffractometer	1526 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing 1995)	1144 reflections with I > 2σ(I)
T_min = 0.819, T_max = 0.946	R_int = 0.047
9107 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.46 e Å⁻³
1526 reflections	Δρ_min = −0.28 e Å⁻³
91 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
Cl1	0.52068 (5)	0.20079 (5)	0.55295 (4)	0.02322 (19)
N1	0.80709 (16)	0.15734 (19)	0.21473 (15)	0.0255 (4)
C2	0.7861 (2)	0.0803 (2)	0.12664 (17)	0.0257 (5)
H2A	0.8438	0.0795	0.0710	0.031*
C3	0.68473 (19)	0.0018 (2)	0.11251 (17)	0.0256 (5)
H3A	0.6730	−0.0519	0.0487	0.031*
N4	0.60290 (15)	0.00317 (17)	0.19137 (13)	0.0202 (4)
C5	0.61964 (18)	0.0768 (2)	0.28134 (16)	0.0207 (5)
H5A	0.5618	0.0767	0.3369	0.025*
C6	0.72478 (18)	0.1552 (2)	0.29291 (17)	0.0212 (5)
N7	0.74454 (18)	0.2293 (2)	0.38395 (16)	0.0301 (5)
C8	0.49086 (19)	−0.0728 (2)	0.17540 (19)	0.0256 (5)
H8A	0.4646	−0.1126	0.2443	0.038*
H8B	0.5026	−0.1488	0.1231	0.038*
H8C	0.4308	−0.0075	0.1482	0.038*
H1N	0.691 (2)	0.227 (3)	0.438 (2)	0.035 (7)*
H2N	0.821 (3)	0.263 (3)	0.397 (2)	0.058 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0224 (3)	0.0264 (3)	0.0209 (3)	−0.0013 (2)	0.0005 (2)	−0.00014 (19)
N1	0.0213 (9)	0.0295 (9)	0.0257 (10)	0.0032 (8)	0.0023 (8)	0.0047 (8)
C2	0.0255 (11)	0.0306 (11)	0.0210 (11)	0.0062 (9)	0.0037 (9)	0.0048 (9)
C3	0.0299 (12)	0.0267 (11)	0.0202 (11)	0.0069 (9)	0.0027 (9)	0.0000 (9)
N4	0.0211 (9)	0.0195 (8)	0.0199 (9)	0.0032 (7)	−0.0003 (7)	0.0014 (7)
C5	0.0206 (10)	0.0225 (10)	0.0191 (11)	0.0037 (8)	0.0011 (8)	0.0008 (8)
C6	0.0206 (11)	0.0218 (10)	0.0212 (11)	0.0029 (8)	−0.0004 (8)	0.0025 (8)
N7	0.0209 (10)	0.0421 (12)	0.0272 (11)	−0.0047 (9)	0.0017 (9)	−0.0085 (9)
C8	0.0241 (11)	0.0273 (11)	0.0254 (12)	−0.0029 (9)	−0.0020 (9)	−0.0047 (9)

Geometric parameters (Å, º) top

N1—C2	1.335 (3)	C5—C6	1.411 (3)
N1—C6	1.344 (3)	C5—H5A	0.9500
C2—C3	1.380 (3)	C6—N7	1.348 (3)
C2—H2A	0.9500	N7—H1N	0.91 (3)
C3—N4	1.346 (3)	N7—H2N	0.94 (3)
C3—H3A	0.9500	C8—H8A	0.9800
N4—C5	1.330 (3)	C8—H8B	0.9800
N4—C8	1.472 (3)	C8—H8C	0.9800

C2—N1—C6	117.23 (18)	N1—C6—N7	118.70 (19)
N1—C2—C3	123.2 (2)	N1—C6—C5	121.26 (19)
N1—C2—H2A	118.4	N7—C6—C5	120.03 (19)
C3—C2—H2A	118.4	C6—N7—H1N	119.8 (16)
N4—C3—C2	118.34 (19)	C6—N7—H2N	118.6 (19)
N4—C3—H3A	120.8	H1N—N7—H2N	120 (2)
C2—C3—H3A	120.8	N4—C8—H8A	109.5
C5—N4—C3	121.02 (18)	N4—C8—H8B	109.5
C5—N4—C8	119.57 (17)	H8A—C8—H8B	109.5
C3—N4—C8	119.35 (18)	N4—C8—H8C	109.5
N4—C5—C6	118.90 (19)	H8A—C8—H8C	109.5
N4—C5—H5A	120.6	H8B—C8—H8C	109.5
C6—C5—H5A	120.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H1N···Cl1	0.91 (3)	2.40 (3)	3.297 (2)	168 (2)
N7—H2N···Cl1ⁱ	0.94 (3)	2.37 (3)	3.289 (2)	168 (3)

Symmetry code: (i) x+1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₅H₈N₃⁺·Cl⁻
M_r	145.59
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	150
a, b, c (Å)	11.3164 (3), 9.5029 (5), 12.3877 (5)
V (Å³)	1332.16 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.48
Crystal size (mm)	0.24 × 0.16 × 0.12

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing 1995)
T_min, T_max	0.819, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	9107, 1526, 1144
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.111, 1.10
No. of reflections	1526
No. of parameters	91
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.28

Computer programs: COLLECT (Nonius BV, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H1N···Cl1	0.91 (3)	2.40 (3)	3.297 (2)	168 (2)
N7—H2N···Cl1ⁱ	0.94 (3)	2.37 (3)	3.289 (2)	168 (3)

Symmetry code: (i) x+1/2, −y+1/2, −z+1.

Acknowledgements

The authors acknowledge NSERC Canada, the University of Toronto and the Dean's Seed Fund Initiative (Ryerson University) for funding.

References

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