Pyridine-3-carboxamidinium chloride

Fei Liu; Fang Zhang; Qifan Chen; Huidong Zhang

doi:10.1107/S1600536811002704

. 2011 Mar 5;67(Pt 4):o781. doi: 10.1107/S1600536811002704

Pyridine-3-carboxamidinium chloride

Fei Liu ^a,^*, Fang Zhang ^a, Qifan Chen ^b, Huidong Zhang ^b

PMCID: PMC3099956 PMID: 21754072

Abstract

The title compound, C₆H₈N₃ ⁺·Cl⁻, crystallizes with two formula units in the asymmetric unit. The cations are non-planar with the –C(NH₂)₂ groups twisted relative to the ring planes by 36.7 (3) and 37.8 (3)°. The cations are linked into chains through N—H⋯N hydrogen bonds. N—H⋯Cl hydrogen bonds link the chains into a three-dimensional network.

Related literature

For structures of pyridine-carboxamidinium chlorides, see: Fan et al. (2009 ▶); Chen et al. (2010 ▶).

Experimental

Crystal data

C₆H₈N₃ ⁺·Cl⁻
M _r = 157.60
Orthorhombic,
a = 10.9485 (7) Å
b = 33.1581 (14) Å
c = 4.1488 (5) Å
V = 1506.1 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 293 K
0.40 × 0.35 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.845, T _max = 0.930
14201 measured reflections
3213 independent reflections
2953 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.071
S = 1.00
3213 reflections
182 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ▶), 1246 Friedel pairs
Flack parameter: 0.0019 (5)

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811002704/gk2326sup1.cif

e-67-0o781-sup1.cif^{(18KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002704/gk2326Isup2.hkl

e-67-0o781-Isup2.hkl^{(154.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯N4	0.86	2.07	2.880 (2)	157
N5—H5B⋯Cl2	0.86	2.29	3.1403 (15)	170
N6—H6B⋯Cl1	0.86	2.36	3.1562 (16)	155
N2—H2A⋯N1ⁱ	0.86	2.22	2.990 (2)	149
N2—H2B⋯Cl2ⁱⁱ	0.86	2.31	3.1452 (13)	165
N3—H3A⋯Cl2ⁱⁱⁱ	0.86	2.27	3.1040 (16)	164
N5—H5A⋯Cl1^iv	0.86	2.46	3.2373 (16)	150
N6—H6A⋯Cl1^iv	0.86	2.41	3.2013 (16)	152

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

The authors gratefully acknowledge financial support from the Education Department of Liaoning Province (2009 A 265) and Liaoning University.

supplementary crystallographic information

Comment

During the last decade, much interest has been focused on the synthesis of pyridine carboximidamidate derivatives because of their very potent antibacterial activities, interesting biological properties and applications in coordination chemistry.

The title compound is an organic salt which crystallizes with two formula units in the asymmetric unit (Fig. 1). The molecules are nonplanar with the C(NH₂)₂ groups twisted out of the ring planes with the twist angles of 36.7 (3) ° and 37.8 (3) °. The bond lengths and angles in title compound are in the normal ranges comparable with those in the related structure (Fan et al., 2009).

In the crystal structure, pyridine-3-carboximidamidate cations are linked by N—H···N hydrogen bonds to form one-dimensional supramolecular molecular chain (Fig. 2). Cl1 ion bridges two pyridine carboximidamidate cations through N—H···Cl hydrogen bonding and Cl2 ion triple-bridges three cations through N—H···Cl hydrogen bonding. Thus, one-dimensional chains of cations are linked by N—H···Cl interactions into a three-dimensional network (Fig. 3).

Experimental

To a solution of sodium methoxide (5.15 mmol) in methnol (50 ml) was added 3-cyanopyridine (5.2 g, 4.99 mmol). The mixture was stirred at room temperature for 2 h. Then ammonium chloride (2.9 g, 5.42 mmol) was slowly added to the resulting solution and the mixture was stirred at room temperature for 48 h. The resulting suspension was filtered and the solvent was removed from the filtrate under reduced pressure. Purification by washing with diethylether gave 3-amidinopyridine chloride (5.74 g, 94%) as an off-white solid. Block-shaped crystals suitable for X-ray diffraction were obtained by recrystallization from from ethanol.