(1R,2R)-2-(Pyridin-4-yl­methyl­amino)­cyclo­hexa­naminium chloride

Lin Cheng; Li-Min Zhang; Jian-Quan Wang

doi:10.1107/S1600536811005526

. 2011 Feb 19;67(Pt 3):o676. doi: 10.1107/S1600536811005526

(1R,2R)-2-(Pyridin-4-ylmethylamino)cyclohexanaminium chloride

Lin Cheng ^a,^*, Li-Min Zhang ^a, Jian-Quan Wang ^a

PMCID: PMC3051964 PMID: 21522424

Abstract

In the crystal structure of the title compound, C₁₂H₂₀N₃ ⁺·Cl⁻, the protonated (1R,2R)-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine cations and chloride anions are linked via N—H⋯N and N—H⋯Cl hydrogen bonds into a three-dimensional network.

Related literature

For coordination polymers, see: He et al. (2010 ▶). For related structures, see: Gou et al. (2010 ▶).

Experimental

Crystal data

C₁₂H₂₀N₃ ⁺·Cl⁻
M _r = 241.76
Orthorhombic,
a = 5.5256 (10) Å
b = 13.928 (2) Å
c = 16.685 (3) Å
V = 1284.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 291 K
0.25 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1995 ▶) T _min = 0.934, T _max = 0.952
5296 measured reflections
2516 independent reflections
2259 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.102
S = 1.06
2516 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ▶), 1031 Friedel pairs
Flack parameter: −0.04 (8)

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT-Plus (Bruker, 2000 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005526/bt5470sup1.cif

e-67-0o676-sup1.cif^{(16.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005526/bt5470Isup2.hkl

e-67-0o676-Isup2.hkl^{(123.6KB, 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
N1—H1B⋯N3ⁱ	0.89	2.13	2.926 (2)	148
N1—H1C⋯Cl1	0.89	2.32	3.201 (2)	172
N1—H1D⋯Cl1ⁱⁱ	0.89	2.28	3.1583 (19)	170
N2—H2C⋯Cl1ⁱⁱⁱ	0.89	2.72	3.5538 (19)	157

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

Acknowledgments

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

supplementary crystallographic information

Comment

Recent years have witnessed an explosion of great interest in chiral coordination polymers because of their potential utility in enantiomerically selective catalysis and separations, second-order nonlinearoptical (NLO) applications and magnetism (He et al. 2010). We tried to synthesize such polymers by use of chiral (1R,2R)-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine ligand and zinc chloride. However, Zn(II) ions weren't ligated to the chiral ligands and the hydrochloride of the ligand has been obtained in the reaction conditions. Herein, we report the structure of this hydrochloride, 1.HCl [1 = (1R,2R)-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine].

The asymmetric unit of the title compound contains a protonated (1R,2R)-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine and a chloride ion. In the molecule, the distances of the C—N bonds of the pyridine ring are 1.331 (3) and 1.338 (3) Å, which are shorter than those of C—N bonds (1.452 (3), 1.478 (2) and 1.498 (2) Å) of cyclohexane-1,2-diamine. The protonated (1R,2R)-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine cations and chloride anions are linked to each other, via N—H···N (N1···N3a 2.926 (2) Å, symmetry code: a, -1/2 + x, -3/2 - y, -1 - z) and N—H···Cl (N1···Cl1 3.201 (2) Å, N1···Cl1b 3.158 (2) Å, symmetry code: b, -1 + x, y, z) hydrogen bonds between the N atoms of aminium and the N atoms of adjacent pyridine rings, as well as the N atoms of aminium and chloride anions into a one-dimensional hydrogen bonding chain along the a axis (Fig.2), which are further constructed into a three-dimensional supramolecular network by interchain N—H···Cl hydrogen-bonds (N2···Cl1c 3.554 (2) Å, symmetry code: c, 1 - x, -1/2 + y, -1/2 - z) between secondary amines and chloride anions.

Experimental

1R,2R)-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine (0.021 g, 0.1 mmol) dissolved in water (5 ml) was added to a methanol solution (10 ml) ZnCl₂ (0.019 g, 0.1 mmol). The mixture solution was stirred for 2 h at room temperature and then filtered. The filtrate was allowed to evaporate slowly at room temperature. After 2 weeks, colorless block crystals were obtained in 33.1% yield (0.008 g).