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Acta Cryst. (2008). E64, m92    [ doi:10.1107/S1600536807063775 ]

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

S.-Y. Ma, Z.-B. Zheng and J.-K. Li

Abstract top

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.

Comment top

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).

Related literature top

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

Experimental top

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.

Refinement top

In the absence of signifcant anomalous scattering effects, Friedel pairs were averaged. The chirality of atoms C2, C3 and C5 were assigned from the known hand of the starting material.The H-atoms were included in the riding-model approximation with C—H = 0.96–0.98 Å and O—H = 0.82 Å (O-hydroxy) and 0.85 Å (O-water), and with Uiso(H) = 1.2 or 1.5 Ueq(C) and Uiso(H) = 1.5 (O-hydroxy) or 1.2 (O-water) Ueq(O). Friedel pairs were merged for the refinement process.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996; data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are omitted and only asymmetric unit is labelled.
Sodium (1R,2S,5S)-2-hydroxy-6,6-dimethylbicyclo[3.1.1]heptane-2-carboxylate pentahydrate top
Crystal data top
Na+·C10H15O3–·5H2OF000 = 320
Mr = 296.29Dx = 1.280 Mg m−3
Monoclinic, P21Melting point: 350 K
Hall symbol: P 2ybMo Kα radiation
λ = 0.71073 Å
a = 6.647 (3) ÅCell parameters from 1420 reflections
b = 6.976 (3) Åθ = 3.1–22.4º
c = 16.608 (7) ŵ = 0.13 mm−1
β = 93.037 (7)ºT = 295 K
V = 769.0 (6) Å3Block, colourless
Z = 20.15 × 0.12 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		1479 independent reflections
Radiation source: fine-focus sealed tube1284 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.039
T = 295 Kθmax = 25.1º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −7→7
Tmin = 0.981, Tmax = 0.987k = −5→8
4017 measured reflectionsl = −16→19
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.107  w = 1/[σ2(Fo2) + (0.069P)2 + 0.001P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1479 reflectionsΔρmax = 0.21 e Å−3
173 parametersΔρmin = −0.23 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
Na+·C10H15O3–·5H2OV = 769.0 (6) Å3
Mr = 296.29Z = 2
Monoclinic, P21Mo Kα
a = 6.647 (3) ŵ = 0.13 mm−1
b = 6.976 (3) ÅT = 295 K
c = 16.608 (7) Å0.15 × 0.12 × 0.10 mm
β = 93.037 (7)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		1479 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1284 reflections with I > 2σ(I)
Tmin = 0.981, Tmax = 0.987Rint = 0.039
4017 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042Δρmax = 0.21 e Å−3
wR(F2) = 0.107Δρmin = −0.23 e Å−3
S = 1.03Absolute structure: ?
1479 reflectionsFlack parameter: ?
173 parametersRogers parameter: ?
H-atom parameters constrained
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Na1−0.00585 (18)0.5552 (2)1.00549 (8)0.0409 (3)
O10.6546 (3)0.2810 (4)0.82272 (12)0.0526 (6)
O20.3527 (3)0.4065 (3)0.83467 (12)0.0430 (6)
O30.3247 (3)−0.0018 (3)0.77372 (14)0.0440 (6)
H30.20700.00840.78550.066*
O4−0.0358 (3)0.5789 (4)0.85286 (14)0.0507 (6)
H9−0.12680.49680.84040.061*
H100.07230.53210.83600.061*
O5−0.2377 (3)0.3046 (4)0.98716 (11)0.0426 (5)
H11−0.29090.29320.93970.051*
H12−0.33230.28081.01820.051*
O60.2300 (3)0.3093 (4)0.98658 (11)0.0417 (5)
H130.29440.33090.94460.050*
H140.31950.28851.02400.050*
O70.0435 (3)0.4926 (3)1.15078 (13)0.0474 (6)
H150.08190.37831.16050.057*
H160.13820.56271.17070.057*
O80.4976 (3)0.7554 (3)0.88678 (12)0.0493 (6)
H170.45860.64830.86720.059*
H180.45410.84030.85360.059*
C10.4727 (4)0.2977 (5)0.80066 (15)0.0352 (6)
C20.3845 (5)0.1694 (4)0.73196 (18)0.0356 (7)
C30.2004 (4)0.2543 (5)0.68807 (17)0.0384 (7)
H3A0.08940.28490.72240.046*
C40.1419 (5)0.1285 (6)0.6148 (2)0.0527 (9)
H4A0.1791−0.00530.62120.063*
H4B0.00280.14230.59480.063*
C50.2921 (5)0.2488 (6)0.56934 (18)0.0541 (10)
H50.25270.27410.51260.065*
C60.4990 (6)0.1655 (7)0.58425 (18)0.0586 (11)
H6A0.59820.25920.56920.070*
H6B0.51240.05400.55010.070*
C70.5440 (5)0.1063 (5)0.67306 (18)0.0451 (8)
H7A0.5565−0.03210.67550.054*
H7B0.67300.16030.69130.054*
C80.2550 (5)0.4173 (5)0.62814 (18)0.0463 (8)
C90.4265 (6)0.5520 (6)0.6499 (2)0.0581 (9)
H9A0.38820.63710.69190.087*
H9B0.45810.62530.60330.087*
H9C0.54260.47940.66850.087*
C100.0681 (7)0.5319 (7)0.6031 (3)0.0742 (12)
H10A0.09840.61870.56050.111*
H10B0.02500.60350.64850.111*
H10C−0.03730.44620.58450.111*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Na10.0433 (6)0.0359 (7)0.0437 (6)0.0011 (5)0.0047 (4)−0.0013 (6)
O10.0472 (12)0.0610 (16)0.0483 (12)0.0079 (13)−0.0090 (9)−0.0138 (12)
O20.0484 (12)0.0462 (14)0.0348 (11)0.0040 (11)0.0068 (9)−0.0075 (10)
O30.0505 (13)0.0341 (13)0.0482 (13)0.0017 (10)0.0094 (10)0.0087 (10)
O40.0494 (12)0.0487 (15)0.0547 (13)0.0013 (12)0.0076 (10)−0.0040 (12)
O50.0366 (10)0.0505 (13)0.0409 (10)−0.0013 (12)0.0025 (8)0.0008 (12)
O60.0373 (10)0.0504 (13)0.0378 (10)0.0015 (11)0.0056 (8)0.0033 (12)
O70.0507 (13)0.0440 (15)0.0478 (13)−0.0012 (11)0.0050 (10)−0.0024 (11)
O80.0604 (13)0.0484 (16)0.0381 (11)−0.0009 (12)−0.0061 (9)−0.0015 (11)
C10.0416 (15)0.0360 (16)0.0282 (13)0.0043 (16)0.0039 (11)0.0026 (15)
C20.0421 (16)0.0299 (17)0.0352 (15)−0.0014 (13)0.0051 (12)0.0011 (13)
C30.0433 (15)0.038 (2)0.0336 (14)−0.0013 (14)0.0033 (11)0.0007 (14)
C40.059 (2)0.053 (2)0.0450 (19)−0.0102 (18)−0.0072 (15)−0.0052 (17)
C50.073 (2)0.062 (3)0.0261 (15)−0.011 (2)0.0004 (14)−0.0043 (17)
C60.070 (2)0.072 (3)0.0349 (17)−0.006 (2)0.0152 (16)−0.0166 (18)
C70.0505 (17)0.047 (2)0.0384 (17)0.0018 (16)0.0111 (14)−0.0071 (15)
C80.064 (2)0.041 (2)0.0325 (16)−0.0047 (18)−0.0039 (15)0.0069 (15)
C90.093 (2)0.044 (2)0.0376 (17)−0.016 (2)0.0028 (16)0.0096 (17)
C100.101 (3)0.062 (3)0.058 (2)0.018 (3)−0.014 (2)0.010 (2)
Geometric parameters (Å, °) top
Na1—O52.340 (3)C2—C71.544 (4)
Na1—O62.356 (3)C3—C41.534 (5)
Na1—O72.457 (3)C3—C81.566 (4)
Na1—O42.538 (3)C3—H3A0.9800
Na1—Na1i3.4939 (15)C4—C51.533 (5)
Na1—Na1ii3.4939 (15)C4—H4A0.9700
O1—C11.250 (3)C4—H4B0.9700
O2—C11.257 (4)C5—C61.502 (5)
O3—C21.447 (4)C5—C81.556 (5)
O3—H30.8200C5—H50.9800
O4—H90.8500C6—C71.545 (5)
O4—H100.8500C6—H6A0.9700
O5—Na1i2.375 (3)C6—H6B0.9700
O5—H110.8500C7—H7A0.9700
O5—H120.8499C7—H7B0.9700
O6—Na1i2.324 (3)C8—C91.507 (5)
O6—H130.8500C8—C101.517 (6)
O6—H140.8499C9—H9A0.9600
O7—H150.8500C9—H9B0.9600
O7—H160.8501C9—H9C0.9600
O8—H170.8499C10—H10A0.9600
O8—H180.8498C10—H10B0.9600
C1—C21.541 (4)C10—H10C0.9600
C2—C31.512 (4)
O6ii—Na1—O599.06 (9)O3—C2—C7106.5 (3)
O5—Na1—O682.94 (9)C3—C2—C7111.8 (3)
O6ii—Na1—O5ii82.86 (9)C1—C2—C7112.8 (3)
O6—Na1—O5ii94.79 (9)C2—C3—C4108.8 (3)
O6ii—Na1—O797.62 (9)C2—C3—C8112.5 (2)
O5—Na1—O792.74 (9)C4—C3—C888.2 (2)
O6—Na1—O786.92 (8)C2—C3—H3A114.8
O5ii—Na1—O791.40 (9)C4—C3—H3A114.8
O6ii—Na1—O489.44 (9)C8—C3—H3A114.8
O5—Na1—O484.40 (9)C5—C4—C386.2 (3)
O6—Na1—O486.10 (9)C5—C4—H4A114.3
O5ii—Na1—O491.19 (9)C3—C4—H4A114.3
O7—Na1—O4172.73 (11)C5—C4—H4B114.3
O6ii—Na1—Na1i141.31 (8)C3—C4—H4B114.3
O5—Na1—Na1i42.58 (6)H4A—C4—H4B111.4
O6—Na1—Na1i41.36 (6)C6—C5—C4108.8 (3)
O5ii—Na1—Na1i135.80 (8)C6—C5—C8111.3 (3)
O7—Na1—Na1i82.63 (8)C4—C5—C888.6 (3)
O4—Na1—Na1i90.79 (8)C6—C5—H5115.1
O6ii—Na1—Na1ii42.06 (6)C4—C5—H5115.1
O5—Na1—Na1ii139.07 (8)C8—C5—H5115.1
O6—Na1—Na1ii134.67 (9)C5—C6—C7113.0 (3)
O5ii—Na1—Na1ii41.80 (6)C5—C6—H6A109.0
O7—Na1—Na1ii103.09 (8)C7—C6—H6A109.0
O4—Na1—Na1ii83.32 (8)C5—C6—H6B109.0
Na1i—Na1—Na1ii173.37 (8)C7—C6—H6B109.0
C2—O3—H3109.5H6A—C6—H6B107.8
Na1—O4—H9102.5C2—C7—C6115.1 (3)
Na1—O4—H10106.3C2—C7—H7A108.5
H9—O4—H10105.3C6—C7—H7A108.5
Na1—O5—H11115.4C2—C7—H7B108.5
Na1i—O5—H11103.2C6—C7—H7B108.5
Na1—O5—H12124.7H7A—C7—H7B107.5
Na1i—O5—H12110.5C9—C8—C10109.6 (3)
H11—O5—H12105.0C9—C8—C5118.6 (3)
Na1i—O6—H13122.3C10—C8—C5112.4 (3)
Na1—O6—H13110.3C9—C8—C3119.9 (3)
Na1i—O6—H14104.7C10—C8—C3110.1 (3)
Na1—O6—H14118.1C5—C8—C384.3 (2)
H13—O6—H14105.5C8—C9—H9A109.5
Na1—O7—H15112.1C8—C9—H9B109.5
Na1—O7—H16109.8H9A—C9—H9B109.5
H15—O7—H16104.8C8—C9—H9C109.5
H17—O8—H18106.1H9A—C9—H9C109.5
O1—C1—O2123.5 (3)H9B—C9—H9C109.5
O1—C1—O2123.5 (3)C8—C10—H10A109.5
O1—C1—C2119.1 (3)C8—C10—H10B109.5
O2—C1—C2117.2 (2)H10A—C10—H10B109.5
O2—C1—C2117.2 (2)C8—C10—H10C109.5
O3—C2—C3108.6 (2)H10A—C10—H10C109.5
O3—C2—C1103.2 (2)H10B—C10—H10C109.5
C3—C2—C1113.3 (3)
O6ii—Na1—O5—Na1i−174.16 (10)C1—C2—C3—C876.8 (3)
O6—Na1—O5—Na1i10.56 (7)C7—C2—C3—C8−52.0 (4)
O7—Na1—O5—Na1i−76.00 (9)C2—C3—C4—C5−86.5 (3)
O4—Na1—O5—Na1i97.30 (9)C8—C3—C4—C526.7 (3)
Na1ii—Na1—O5—Na1i170.35 (13)C3—C4—C5—C685.2 (3)
O5—Na1—O6—Na1i−10.82 (7)C3—C4—C5—C8−26.9 (2)
O5ii—Na1—O6—Na1i173.48 (10)C4—C5—C6—C7−42.5 (4)
O7—Na1—O6—Na1i82.33 (9)C8—C5—C6—C753.6 (4)
O4—Na1—O6—Na1i−95.64 (9)O3—C2—C7—C6126.2 (3)
Na1ii—Na1—O6—Na1i−172.26 (12)C3—C2—C7—C67.8 (4)
O2—O2—C1—O10.0 (7)C1—C2—C7—C6−121.3 (3)
O2—O2—C1—C20.0 (6)C5—C6—C7—C2−8.5 (5)
O1—C1—C2—O387.1 (3)C6—C5—C8—C937.7 (4)
O2—C1—C2—O3−88.8 (3)C4—C5—C8—C9147.3 (3)
O2—C1—C2—O3−88.8 (3)C6—C5—C8—C10167.4 (3)
O1—C1—C2—C3−155.6 (3)C4—C5—C8—C10−83.0 (4)
O2—C1—C2—C328.4 (4)C6—C5—C8—C3−83.3 (3)
O2—C1—C2—C328.4 (4)C4—C5—C8—C326.3 (2)
O1—C1—C2—C7−27.4 (4)C2—C3—C8—C9−36.5 (4)
O2—C1—C2—C7156.7 (3)C4—C3—C8—C9−146.1 (3)
O2—C1—C2—C7156.7 (3)C2—C3—C8—C10−164.9 (3)
O3—C2—C3—C4−73.2 (3)C4—C3—C8—C1085.4 (3)
C1—C2—C3—C4172.8 (3)C2—C3—C8—C583.3 (3)
C7—C2—C3—C444.0 (3)C4—C3—C8—C5−26.3 (2)
O3—C2—C3—C8−169.2 (2)
Symmetry codes: (i) −x, y−1/2, −z+2; (ii) −x, y+1/2, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O8—H18···O3iii0.851.902.737 (3)170
O8—H17···O20.851.902.741 (3)173
O7—H16···O1iv0.852.052.859 (4)158
O7—H15···O4i0.852.122.887 (4)150
O6—H14···O8v0.851.882.727 (3)175
O6—H13···O20.851.962.776 (3)161
O5—H12···O8i0.851.982.805 (3)164
O5—H11···O1vi0.851.962.791 (3)166
O4—H10···O20.852.062.879 (3)161
O4—H9···O1vi0.852.102.949 (4)174
O3—H3···O7i0.822.022.809 (3)161
Symmetry codes: (iii) x, y+1, z; (iv) −x+1, y+1/2, −z+2; (i) −x, y−1/2, −z+2; (v) −x+1, y−1/2, −z+2; (vi) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O8—H18···O3i0.851.902.737 (3)170
O8—H17···O20.851.902.741 (3)173
O7—H16···O1ii0.852.052.859 (4)158
O7—H15···O4iii0.852.122.887 (4)150
O6—H14···O8iv0.851.882.727 (3)175
O6—H13···O20.851.962.776 (3)161
O5—H12···O8iii0.851.982.805 (3)164
O5—H11···O1v0.851.962.791 (3)166
O4—H10···O20.852.062.879 (3)161
O4—H9···O1v0.852.102.949 (4)174
O3—H3···O7iii0.822.022.809 (3)161
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y+1/2, −z+2; (iii) −x, y−1/2, −z+2; (iv) −x+1, y−1/2, −z+2; (v) x−1, y, z.
references
References top

Huang, W., Xie, X., Cui, K., Gou, S. & Li, Y. (2005). Inorg. Chim. Acta, 358, 875–884.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.