Sodium (1R,2S,5S)-2-hydr­oxy-6,6-dimethyl­bicyclo­[3.1.1]heptane-2-carboxyl­ate penta­hydrate

Shi-Ying Ma; Ze-Bao Zheng; Ji-Kun Li

doi:10.1107/S1600536807063775

. 2007 Dec 6;64(Pt 1):m92. doi: 10.1107/S1600536807063775

Sodium (1R,2S,5S)-2-hydroxy-6,6-dimethylbicyclo[3.1.1]heptane-2-carboxylate pentahydrate

Shi-Ying Ma ^a,^*, Ze-Bao Zheng ^a, Ji-Kun Li ^b

PMCID: PMC2914966 PMID: 21200659

Abstract

In the title compound, Na⁺·C₁₀H₁₅O₃ ⁻·5H₂O, the vertices of a distorted octahedron centred on the Na⁺ cation are defined by six O atoms of water molecules. The edge-sharing Na(H₂O)₆ octahedra form a chain extended along the b-axis direction with adjacent Na⁺ cations related by a twofold screw symmetry operation. The organic anion, which is not in close contact with the Na⁺cation, is hydrogen-bonded to an uncoordinated water molecule and to water molecules of the Na(H₂O)₆ octahedra.

Related literature

For a crystal structure with similar chains of edge-sharing Na(H₂O)₆ octahedra, see: Huang et al. (2005 ▶).

Experimental

Crystal data

Na⁺·C₁₀H₁₅O₃ ⁻·5H₂O
M _r = 296.29
Monoclinic,
a = 6.647 (3) Å
b = 6.976 (3) Å
c = 16.608 (7) Å
β = 93.037 (7)°
V = 769.0 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 295 K
0.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.981, T _max = 0.987
4017 measured reflections
1479 independent reflections
1284 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.107
S = 1.02
1479 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a ▶); molecular graphics: SHELXTL (Sheldrick, 1997b ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063775/gk2115sup1.cif

e-64-00m92-sup1.cif^{(20.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063775/gk2115Isup2.hkl

e-64-00m92-Isup2.hkl^{(72.9KB, 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
O8—H18⋯O3ⁱ	0.85	1.90	2.737 (3)	170
O8—H17⋯O2	0.85	1.90	2.741 (3)	173
O7—H16⋯O1ⁱⁱ	0.85	2.05	2.859 (4)	158
O7—H15⋯O4ⁱⁱⁱ	0.85	2.12	2.887 (4)	150
O6—H14⋯O8^iv	0.85	1.88	2.727 (3)	175
O6—H13⋯O2	0.85	1.96	2.776 (3)	161
O5—H12⋯O8ⁱⁱⁱ	0.85	1.98	2.805 (3)	164
O5—H11⋯O1^v	0.85	1.96	2.791 (3)	166
O4—H10⋯O2	0.85	2.06	2.879 (3)	161
O4—H9⋯O1^v	0.85	2.10	2.949 (4)	174
O3—H3⋯O7ⁱⁱⁱ	0.82	2.02	2.809 (3)	161

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

Acknowledgments

The authors thank Taishan University for financial support.

supplementary crystallographic information

Comment

Sodium nopinate is an intermediate in the synthesis of nopinic acid. Hydroxyalkylamino salts of nopinic acid are new compounds useful in pharmaceutical compositions for alleviating ulcer conditions. In the course of synthesis of nopinic acid the crystal of sodium nopinate pentahydrate (I) was obtained in its crystallographic data are reported here (Fig.1). In the title compound the vertices of a distorted octahedron centred on Na⁺ cation are defined by six O atoms of water molecules. The edge-sharing Na(H₂O)₆ octahedra form a chain extended along the b axis with the adjacent Na⁺cations related by twofold screw axis symmetry. Similar chains were observed in sodium pyridine-4-carboxylate tetrahydrate (Huang et al., 2005).

Experimental

Potassium permanganate (0.03 mol) and NaOH (0.015 mol) were dissolved in the mixture of water (21 ml) and t-butylalcohol (9 ml).While stirring vigorously, enantiomerically pure (-)-β-pinene (0.01 mol) was dropped. The reaction mixture was maintained during 1 to 2 h at temperature of 283–293 K. The reaction was completed when the potassium permanganate reacted completely. The mixture was heated to 353 K,then filtered and the precipitate was washed with hot water. The filtrate was concentrated under vacuum to a volume of 10 ml. After standing for one night in refrigerator the product, sodium nopinate, was filtered and washed with ice water. The crude sodium nopinate was recrystallized from water. Analysis calculated for C₁₀H₁₅O₃Na: C 58.25, H 7.28, Na11.17%; found: C 58.23, H 7.25, N 11.15%. Crystals of (I) suitable for single-crystal X-ray analysis were selected directly from the sample after recrystallization.