4-[(1-Adamant­yl)carbamo­yl]pyridinium chloride

Yingchun Wang

doi:10.1107/S1600536810052499

. 2010 Dec 24;67(Pt 1):o210. doi: 10.1107/S1600536810052499

4-[(1-Adamantyl)carbamoyl]pyridinium chloride

Yingchun Wang ^a,^*

PMCID: PMC3050416 PMID: 21522711

Abstract

In the title compound, C₁₆H₂₁N₂O⁺·Cl⁻, the amide group makes a dihedral angle of 25.9 (1)° with respect to the pyridine ring. In the crystal, intermolecular N—H⋯Cl bonds and weak C—H⋯Cl and C—H⋯O contacts link the cations and the anions into layers parallel to the ac plane. The layers are packed along [010] by hydrophobic interactions between adamantane units.

Related literature

For biomedical properties of adamantane-1-amine derivatives, see: Lees (2005 ▶); Nayyar et al. (2007 ▶). For ferroelectric properties of pyridinium salts, see: Ye et al. (2010 ▶); Zhang et al. (2010 ▶).

Experimental

Crystal data

C₁₆H₂₁N₂O⁺·Cl⁻
M _r = 292.80
Monoclinic,
a = 7.117 (4) Å
b = 23.093 (13) Å
c = 11.241 (5) Å
β = 127.56 (2)°
V = 1464.5 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.950, T _max = 0.950
14193 measured reflections
3377 independent reflections
2910 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.139
S = 1.11
3377 reflections
202 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL/PC.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810052499/si2302sup1.cif

e-67-0o210-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810052499/si2302Isup2.hkl

e-67-0o210-Isup2.hkl^{(165.7KB, 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—H1A⋯Cl1ⁱ	0.90	2.16	3.017 (2)	160
N2—H2A⋯Cl1ⁱⁱ	0.90	2.50	3.293 (2)	147
C2—H2B⋯Cl1ⁱⁱⁱ	0.96	2.79	3.535 (3)	136
C3—H3A⋯Cl1^iv	0.96	2.78	3.536 (3)	136
C4—H4A⋯O1ⁱⁱ	0.96	2.35	3.203 (3)	147

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

Acknowledgments

The author is grateful to the starter fund of Southeast University for financial support to buy the X-ray diffractometer.

supplementary crystallographic information

Comment

The study of amantadine and its derivatives has attracted much attention owing to their multifunction and technological applications in many areas, such as biomedicine (Lees 2005; Nayyar et al.2007). Amantadine can crystallize in different space groups owing to its randomness. As one part of our systematic research on dielectric, ferroelectric, and phase-transition materials (Ye et al. 2010; Zhang et al. 2010), we synthesize the title compound and investigated its dielectric property. In the range of 110 K to its melting point (428–432 K), the dielectric constant increases smoothly as a function of temperature. It means that this compound might not undergo a distinct structural phase transition in the measured temperature range.

The asymmetric unit of the title compound contains one protonated N- (1-adamantyl)isonicotinamide basic ion and one negative chlorine ion (Fig. 1). The torsion angles of C2—C1—C6—O1 and C2—C1—C6—N2 are 24.5 (3) ånd -157.5 (2) °, C5—C1—C6—O1 and C5—C1—C6—N2 are -151.3 (2) ° and 26.7 (3) °. Intermolecular N—H···Cl bonds and weak C—H···Cl and C—H···O contacts link cationic molecules parallel to (1 0 1) (Table 1). The layers are packed by hydrophobic interactions between adamantane units along the b-axis (Fig 2).

Experimental

Isonicotinic acid 5 g was added in thionyl chloride (50 ml), and the mixture reacted at 353 K for 5 h. Then the solvate was removed under reduced pressure, the isonicotinoyl chloride was obtained. The l-aminodiamantane hydrochloride (10 mmol) and triethylamine 2.02 g (20 mmol) dissolved in chloroform (40 ml) at 273 K, then the isonicotinoyl chloride 1.51 g (10 mmol) was added. Then the reactant mixture was stired for 7 h at room temperature and some flaxen solid appeared. After filtering the mixture, the solid was dissolved in water and was neutralized with sodium carbonate, The mixed solution was extracted by dichloromethane. The N-(1-adamantyl)isonicotinamide was obtained when the dichloromethane was evaporated under reduced pressure.

The N(1-adamantyl)isonicotinamide 2.56 g (10 mmol) was dissolved in methanol and the chlorhydric acid 1 ml (12 mmol/ml) was added. The crystals suitable for structure determination were grown by slow evaporation of the filter solution at room temperature.