3,5,7-Tripropyl-1-aza­adamantane-4,6,10-triol

Pierre-Loïc Saaidi; Pierre-Etienne Chazal; Philippe Maurin; Erwann Jeanneau; Jens Hasserodt

doi:10.1107/S1600536808006284

. 2008 Apr 4;64(Pt 5):o803–o804. doi: 10.1107/S1600536808006284

3,5,7-Tripropyl-1-azaadamantane-4,6,10-triol

Pierre-Loïc Saaidi ^a, Pierre-Etienne Chazal ^a, Philippe Maurin ^a, Erwann Jeanneau ^b,^*, Jens Hasserodt ^a

PMCID: PMC2961298 PMID: 21202295

Abstract

The title compound, C₁₈H₃₃NO₃, was prepared according to a highly diastereoselective hydrogenation procedure from 3,5,7-triallyl-1-azaadamantane-4,6,10-trione. The crystal structure of the title compound contains two crystallographically independent molecules (Z′ = 2), which are linked by intermolecular hydrogen bonding into chains. In contrast to the azaadamantanones, the azaadamantanetriol core of the title compound does not show any particular C—C bond elongation.

Related literature

For related literature on the consequences of through-bond donor–acceptor interactions in β-aminoketones azaadamantones, see: Lampkins et al. (2008 ▶). For details on molecular receptors based on a polyfunctionalized rigid platform, see: Guarise et al. (2006 ▶); Haberhauer et al. (2005 ▶); Li et al. (2005 ▶). For information about molecules displaying multiple formula units per crystallographic asymmetric unit, see: Steiner (2000 ▶). For bond lengths in similar compounds, see: Lampkins et al. (2008 ▶); Allen et al. (1987 ▶). Details on the synthesis can be found in: Risch (1985 ▶); Li et al. (2005 ▶). For details of data collection and refinement procedures, see: Görbitz (1999 ▶); Guarise et al. (2006 ▶); Prince (1982 ▶); Watkin (1994 ▶).

Experimental

Crystal data

C₁₈H₃₃NO₃
M _r = 311.45
Monoclinic,
a = 13.1922 (2) Å
b = 22.6174 (5) Å
c = 13.1144 (3) Å
β = 114.4470 (10)°
V = 3562.17 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 150 K
0.43 × 0.35 × 0.14 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
16642 measured reflections
8498 independent reflections
5272 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.054
S = 1.06
5272 reflections
397 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: COLLECT (Nonius, 2001 ▶).; cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 1996 ▶); software used to prepare material for publication: CRYSTALS.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808006284/nc2092sup1.cif

e-64-0o803-sup1.cif^{(29.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006284/nc2092Isup2.hkl

e-64-0o803-Isup2.hkl^{(423.9KB, 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
C26—H261⋯O4ⁱ	0.97	2.38	3.261 (3)	151
C35—H351⋯O4ⁱ	0.97	2.54	3.344 (3)	140
C31—H312⋯O1ⁱⁱ	0.97	2.54	3.355 (3)	142
O3—H3⋯N2ⁱⁱⁱ	0.84	1.87	2.696 (3)	168
O2—H2⋯O3	0.82	2.08	2.788 (3)	143
O4—H4⋯O5	0.84	1.96	2.696 (3)	147
O5—H5⋯N1^iv	0.83	1.90	2.713 (3)	167
O1—H1⋯O3	0.79	2.07	2.777 (3)	149
O6—H6⋯O5	0.83	2.07	2.810 (3)	148

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

supplementary crystallographic information

Comment

Recently, an increasing number of molecular receptors based on a polyfunctionalized rigid platform have been reported (Guarise et al., 2006; Haberhauer et al., 2005 ; Li et al., 2005). Among them, adamantane and aza-adamantane scaffolds offer the guarantee of a well-defined environment as a result of axial or equatorial substituent orientation. The title compound shows a perfectly constraint face with three hydroxyl groups in axial positions that could potentially be used, after introduction of suitable ligands, as oriented binding sites for a wide range of applications.

The asymmetric unit of the title compound consists of two independent molecules(A and B) per unit-cell (Z'=2) (Steiner, 2000). This feature arises from the different orientation of one of the propyl group (C11-C12-C13 and C29-C30-C31). Contrary to the case of aza-adamantanone systems which show several C-C bond elongations (Lampkins et al., 2008), all angles and distances within the two molecules agree well with the expected values from the literature (Allen et al., 2006). Each independant molecule of the title compound displays two intra-molecular O-H···O hydrogen bonds and one O-H···N inter-molecular. The later leads to the formation of infinite one-dimensional chains along [2 0 1]. The chains are composed of alternated molecules A and B.

Experimental

The title compound was prepared according to a hydrogenation procedure adapted from Risch (1985). A 100-ml reactor vessel was charged with 80 mg of 3,5,7-triallyl-1-aza-adamantane-4,6,10-trione (0.267 mmol) (Li et al., 2005), 88 mg of platinum oxide (0.388 mmol) and 20 ml of a 1:1 THF/0.1 N HCl mixture. The reaction mixture was hydrogenated (10 bar H₂) for 50 h at room temperature. After filtration over Celite, the aqueous solution was concentrated under reduced pressure (200 mbar) basified with potassium carbonate and extracted with four 80-ml portions of ethyl acetate. The combined organic phases were then dried over Na₂SO₄ and concentrated in vacuo. Flash chromatography purification (petroleum ether/ethyl acetate 1:1 then neat ethyl acetate) afforded the title compound as a cristalline white powder (54 mg, 65%). X-ray quality single crystals were obtained by slow evaporation from a cyclohexane/ethyl acetate solution.