Adamantan-1-aminium p-toluene­sulfonate

Yi Zhang; Bo Wang

doi:10.1107/S1600536811003436

. 2011 Feb 2;67(Pt 3):o543. doi: 10.1107/S1600536811003436

Adamantan-1-aminium p-toluenesulfonate

Yi Zhang ^a,^*, Bo Wang ^a

PMCID: PMC3052013 PMID: 21522311

Abstract

There are two unique cations and anions in the asymmetric unit of the title molecular salt, C₁₀H₁₅NH₃ ⁺·C₇H₇O₃S⁻. In the crystal, all three hydrogen-bond donors of the protonated amine group make hydrogen-bond interactions with sulfonate O-atom acceptors, linking the cations and anions into chains parallel to the a axis. C—H⋯π interactions are also present.

Related literature

For related structures, see: Tukada & Mochizuki (2003 ▶); Zhao et al. (2003 ▶); Smith et al. (2004 ▶); He & Wen (2006 ▶); Zheng & Wang (2009 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For ribbon hydrogen-bonding motifs, see: Hulme & Tocher (2006 ▶).

Experimental

Crystal data

C₁₀H₁₈N⁺·C₇H₇O₃S⁻
M _r = 323.44
Triclinic,
a = 6.464 (2) Å
b = 11.589 (4) Å
c = 22.562 (8) Å
α = 92.975 (4)°
β = 94.034 (5)°
γ = 96.408 (5)°
V = 1672.4 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.960, T _max = 0.960
18425 measured reflections
7664 independent reflections
5720 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.149
S = 1.06
7664 reflections
421 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.36 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 (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003436/jh2261sup1.cif

e-67-0o543-sup1.cif^{(30.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811003436/jh2261Isup2.hkl

e-67-0o543-Isup2.hkl^{(371.2KB, hkl)}

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

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

Cg9 and Cg10 are the centroids of the C22–C27 and C29–C34 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O4	0.89 (2)	2.02 (2)	2.908 (3)	177 (3)
N1—H1D⋯O5ⁱ	0.90 (2)	1.99 (2)	2.883 (3)	177 (3)
N1—H1E⋯O6ⁱⁱ	0.89 (2)	1.92 (2)	2.806 (3)	173 (3)
N2—H2C⋯O1	0.91 (2)	1.93 (2)	2.834 (3)	174 (3)
N2—H2B⋯O2ⁱⁱⁱ	0.89 (2)	1.92 (2)	2.806 (3)	170 (3)
N2—H2A⋯O3^iv	0.89 (2)	2.01 (2)	2.901 (3)	175 (3)
C4—H4A⋯Cg10^iv	0.98	3.18	3.878 (3)	130
C7—H7B⋯Cg9ⁱⁱⁱ	0.97	2.87	3.801 (3)	161
C19—H19B⋯Cg10^v	0.97	2.91	3.861 (3)	167

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

Acknowledgments

This work was supported by the Start-up Projects for Postdoctoral Research Funds (1112000064) and Major Postdoctoral Research Funds (3212000602) of Southeast University.

supplementary crystallographic information

Comment

Owing to its highly symmetrical and stable structure, adamantane and its derivatives have generated much interest in the past and continue to be actively studied as evidenced by the large number of compounds containing amantadine that have been synthesized (Tukada & Mochizuki, 2003; Zhao et al., 2003; He & Wen, 2006). Our group have reported the crystal structures of the compounds of C₁₀H₁₅NH₃⁺ .C₇H₅O₂^-. Here we report the synthesis and CrystalStructure of the title compound, (I), C₁₀H₁₅NH₃⁺.C₇H₇O₃S^-, a salt obtained from the reaction of adamantane-1-ammonium hydrochloride and toluene-4-sulfonic acid sodium salt.

In the molecule of the title compound, the bond lengths and angles are within their normal ranges. There are two pairs of adamantane-1-ammonium cation and toluene-4-sulfonic acid anion in one asymmetric unit(Fig. 1). The dihedral angle between the benzene ring A (C22–C27) and benzene ring B (C29–C34) is A/B = 20.83 °. The two molecules are both stabilized by N—H···O hydrogen bonding, among which, N1—H1C···O4 and N2—H2C···O1 are intramolecular hydrogen bonds. All three hydrogen donors of the protonated amine group give direct hydrogen-bonding associations, with three of the sulfonate O-atom acceptors from three independent toluene-4-sulfonic acid anions. The hydrogen bonds are summarized in Tab. 1. Fig. 2 shows a view down the c axis. The N—H···O hydrogen bonds between the discrete adamantane-1-ammoniumcations and toluene-4-sulfonic acid anions result in a noteworthy one-dimensional ribbon-like structure parallel to (1 0 0) (Fig. 2). This ribbon motif is the dominant hydrogen-bonding motif (Hulme et al., 2006). In addition, strong π-ring C7 –H7A···Cg9ⁱⁱⁱ, C4 –H4B···Cg10^iv, C19 –H19B··· Cg10^v interactions exist which contribute to crystal stability [Cg9 and Cg10 is the center of gravity of ring A and B, Symmetry code: (iii) -x + 1, -y + 1, -z + 1; (iv) x - 1, y, z; (v) x, y - 1, z.]

Experimental

A mixture of adamantane-1-ammonium hydrochloride (10 mmol, 1.94 g), toluene-4-sulfonic acidsodium salt (10 mmol, 1.88 g) and methanol (50 ml) was stirred in a beaker. There were many solid powders produced and the solution was filtered. Colorless single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of the solvents over a period of a week.

The dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (ε = C/(T–T₀)), suggesting that this compound is not ferroelectric or there may be no distinct phase transition occurring within the measured temperature range between 93 K and 362 K (m.p. 99 ^oC).