Adamantane-1-ammonium benzoate

Wen-Ni Zheng; Bo Wang

doi:10.1107/S1600536809036903

. 2009 Oct 17;65(Pt 11):o2769. doi: 10.1107/S1600536809036903

Adamantane-1-ammonium benzoate

Wen-Ni Zheng ^a, Bo Wang ^a,^*

PMCID: PMC2971192 PMID: 21578363

Abstract

In the title molecular salt, C₁₀H₁₅NH₃ ⁺·C₇H₅O₂ ⁻, both carboxyl O atoms act as acceptors for strong N—H⋯O intermolecular hydrogen-bond interactions with the ammonium group in the cation, generating infinite chains along the b axis. A weak C—H⋯π interaction is also present.

Related literature

For related structures, see: Tukada & Mochizuki (2003 ▶); Zhao et al. (2003 ▶); He & Wen (2006 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₀H₁₈N⁺·C₇H₅O₂ ⁻
M _r = 273.36
Monoclinic,
a = 10.918 (2) Å
b = 6.5664 (13) Å
c = 21.197 (4) Å
β = 100.07 (3)°
V = 1496.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 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 = 0.774, T _max = 1.000
15027 measured reflections
3437 independent reflections
2453 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.147
S = 1.04
3437 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.26 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: PRPKAPPA (Ferguson, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536809036903/jj2008sup1.cif

e-65-o2769-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036903/jj2008Isup2.hkl

e-65-o2769-Isup2.hkl^{(168.6KB, 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—H1A⋯O1ⁱ	0.89	1.83	2.7134 (17)	176
N1—H1B⋯O2ⁱⁱ	0.89	1.90	2.7840 (18)	173
N1—H1C⋯O2	0.89	1.92	2.7915 (18)	166
C16—H16A⋯Cg1ⁱⁱⁱ	0.97	2.74	3.702 (2)	174

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 is the centroid of the C2–C7 ring.

Acknowledgments

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

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). Here we report the synthesis and crystal structure of the title compound,(I), C₁₀H₁₅NH₃⁺ . C₇H₅O₂^-, a salt obtained from the reaction of adamantane-1-ammonium hydrochloride and sodium benzoate (Fig. 1).

The adamantane-1-ammonium cation contains four 6-membered rings in a cage-like structure each in a slightly distorted boat conformation and with a protonated N atom at the 1-position. Puckering parameters (Cremer & Pople, 1975) Q, θ and φ are for rings 1–4 [(1) 0.630 (2) Å, 1.48 (18)°,272 (54)°; (2) 0.6247 (19)Å,178.36 (17)°, 251 (423)°; (3) 0.621 (4)Å,0.67 (18)°, 240 (54)°; (4)0.6207 (19)Å, 0.55 (18)°, 218 (39)°] where (1) = C7–C9/C13–C15, (2) = C7/C8/C10/C11/C16/C15, (3) = C8/C9/C13/C12/C11/C10 and (4) = C11–C16. C—C distances range from 1.518 (2)Å to 1.531 (3)Å and C—C—C angles range from 108.93 (13)° to 109.91 (13)°, while the exocyclic C—N bond length is 1.4924 (19)Å. These values are similar to that observed in adamantane-1-ammonium 2-nitrobenzoate (C—C = 1.5254 (18)Å to 1.532 (2)Å, C—C—C 109.06 (13)° to 109.84 (11)°, C—N = 1.4967 (18)Å (He & Wen, 2006). Both the negativly charged and neutral oxygen atoms in the benzoate anion are involved in strong N—H···O intermolecular hydrogen bond interactions with the ammonium cation group generating infinite one-dimensional chains along the b axis of the unit cell (Fig. 2, Table 1). In addition, weak π-ring C16–H16A···Cg1 interactions exist which contribute to crystal stability (Cg1 is the center of gravity of ring 1).

Experimental

A mixture of adamantane-1- ammonium hydrochloride (10 mmol), sodiumbenzoate (10 mmol) 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 20 h.