PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m92.
Published online 2007 December 6. doi:  10.1107/S1600536807063775
PMCID: PMC2914966

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

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 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-00m92-scheme1.jpg

Experimental

Crystal data

  • Na+·C10H15O3 ·5H2O
  • M r = 296.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00m92-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.24 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

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.

Refinement

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.

Figures

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.

Crystal data

Na+·C10H15O3·5H2OF000 = 320
Mr = 296.29Dx = 1.280 Mg m3
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 mm1
β = 93.037 (7)ºT = 295 K
V = 769.0 (6) Å3Block, colourless
Z = 20.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer1479 independent reflections
Radiation source: fine-focus sealed tube1284 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.039
T = 295 Kθmax = 25.1º
[var phi] 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

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 Å3
173 parametersΔρmin = −0.23 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2115).

References

  • 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.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography