organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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3-exo-Chloro-8-oxabi­cyclo­[3.2.1]oct-6-ene-2,4-diol chloro­form 0.33-solvate

aChemistry Department, Moscow State University, 119991 Moscow, Russian Federation
*Correspondence e-mail: Aslanov@struct.chem.msu.ru

(Received 20 May 2009; accepted 9 June 2009; online 13 June 2009)

The title compound, 3C7H9ClO3·CHCl3, crystallizes with mol­ecules of 3-exo-chloro-8-oxabicyclo­[3.2.1]oct-6-ene-2,4-diol (A) and chloro­form in a 3:1 ratio, in the space group R3m. Mol­ecules of A straddle a crystallographic mirror plane, whereas the chloro­form mol­ecules (C and H atoms) lie additionally on the threefold axis. The mol­ecules of A are linked into right- and left-helical chains by means of O—H⋯O hydrogen bonds, thus forming columns running along the c axis. Six inter­penetrated columns form a channel in which the solvent mol­ecules (chloro­form) are located.

Related literature

Inositetriphosphates analogues are potential prospective anti­tumoral compounds, see: Piettre et al. (1997[Piettre, S. R., Andre, C., Chanal, M. C., Ducep, J. B., Lesur, B., Piriou, F., Raboisson, P., Rondeau, J. M., Schelcher, C., Zimmermann, P. & Ganzborn, A. J. (1997). J. Med. Chem. 40, 4208-4221.]); Miller & Allemann (2007[Miller, D. J. & Allemann, R. K. (2007). Mini-Rev. Med. Chem. 7, 107-113.]).

[Scheme 1]

Experimental

Crystal data
  • 3C7H9ClO3·CHCl3

  • Mr = 649.16

  • Hexagonal, R 3m

  • a = 18.687 (5) Å

  • c = 6.8723 (16) Å

  • V = 2078.3 (9) Å3

  • Z = 3

  • Cu Kα radiation

  • μ = 6.09 mm−1

  • T = 295 K

  • 0.1 × 0.07 × 0.06 mm

Data collection
  • Enraf–Nonius CAD-4 diffractometer

  • Absorption correction: ψ scan (North et al., 1968[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.530, Tmax = 0.694

  • 1832 measured reflections

  • 987 independent reflections

  • 966 reflections with I > 2σ(I)

  • Rint = 0.036

  • 2 standard reflections frequency: 120 min intensity decay: none

Refinement
  • R[F2 > 2σ(F2)] = 0.054

  • wR(F2) = 0.168

  • S = 1.18

  • 987 reflections

  • 69 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.28 e Å−3

  • Δρmin = −0.51 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 481 Friedel pairs

  • Flack parameter: −0.01 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H11⋯O1i 0.77 (7) 1.98 (7) 2.723 (3) 162 (7)
Symmetry code: (i) [-x+y+{\script{2\over 3}}, -x+{\script{1\over 3}}, z+{\script{1\over 3}}].

Data collection: CAD-4 Software (Enraf–Nonius, 1989[Enraf-Nonius (1989). CAD-4 Software. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2000[Brandenburg, K. (2000). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

It is known (Piettre et al., (1997); Miller & Allemann, (2007)) that the analogous of inositetriphosphates are potential prospective antitumoral compounds. As we assume that the polyhydroxycycloheptanes are able to act like inositemonophosphatase inhibitors, so the 3-exo-chloro-8-oxa-bicyclo[3.2.1]oct-6-en-2,4-diendo-diol was synthesized. The elemental analysis of the compound we obtained, were in good agreement with the title compound, but 1H NMR data did not allow us to clarify the relative oxy-groups arrangement in the molecule. To determine the structure of the compound, we carried out an X-ray crystallographic analysis. Molecule of (A) (Fig.1) straddle a crystallographic mirror plane m passing through atoms Cl1, C1, H1, endocyclic oxygen O2, the midpoint of the double bond C4/C4ii, whereas the chloroform molecules (carbon C5 and hydrogen H5 atoms) lie additionally on the threefold axis. The 6-membered cycle of the molecule adopts a chair conformation, with atoms O2 and C1 displaced out of plane defined by the atoms C2/C2ii/C3/C3ii (plane 1) by -0.848 (3) and 0.543 (2) Å. Atoms O1, C4, Cl1, H1 (attached to C1) displaced out of plane 1 by 0.797 (2), 1.329 (3), 0.1990 (1), 1.44 (2) Å, while atoms H2 and H3 (attached to C2 and C3) by -.90 (3), -0.37 (3) Å, respectively. The packing motif, as shown in Fig.2 can be described as follows: the molecules (A) are linked into the interpenetrated right- and left-helical chains by means of O1—H···O1* hydrogen bonds thus to form columns, running along the c axis. The six interpenetrated columns form channels, where solvent molecules (chloroform) are located.

Related literature top

Inositetriphosphates analogues are potential prospective antitumoral compounds, see: Piettre et al. (1997); Miller & Allemann (2007).

Experimental top

1M hexane solution of DIBAL-H (6 ml) was added (Fig. 3) dropwise during 20 min at 213 K to a solution of compound (1) 3-chloro-8-oxabicyclo[3.2.1]-6-en-2,4-dione (5.75 mmol, 1000 mg) in 40 ml of dry THF under argon atmosphere. Reaction quenched with methanol and the mixture stirred for 4–5 h, concentrated to 20–30 ml, filtered through silica gel (2 cm, 60/200 µ), evaporated to dryness to yield compound 2 as yellow oil which was used for preparing of compound (3) without further purification. 1M hexane solution of DIBAL-H (6 ml) was added dropwise during 20 min at 213 K to a solution of compound (2) (1.72 mmol, 300 mg) in 20 ml of dry THF under argon atmosphere. The reaction was quenched with methanol (15 ml) and the mixture was stirred for 4–5 h, concentrated to 10 ml, filtered through silica gel (2 cm, 60/200 µ), evaporated to dryness to yield compound (3) as a colorless solid (280 mg) which was flesh-chromatographed on silica gel (40/60 µ, CH2Cl2 Et2O: 2:1, gradient 1:5) to give diol (3) (150 mg), Crystals suitable for diffraction analysis were obtained by slow diffusion of petroleum ether vapour into a CHCl3 solution.

Refinement top

The positions of the H atoms were determined from Fourier difference maps; H atoms attached to carbons were then placed in calculated positions and allowed to ride on their parent atoms [C—H = 0.93–0.98 Å. Uiso(H) = xUeq(parent atom), where x = 1.2.] Hydrogen attached to oxygen was refined freely.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. Symmetry codes: (ii) x, x-y, z; (iii) -y + 1, x-y, z; (iv) 1 - x + y, -x + 1, z.
[Figure 2] Fig. 2. The packing motif of the crystal structure. Symmetry codes: (i) -x + y+2/3, -x + 1/3, z + 1/3
[Figure 3] Fig. 3. Reaction scheme.
3-exo-Chloro-8-oxabicyclo[3.2.1]oct-6-ene-2,4-diol chloroform 0.33-solvate top
Crystal data top
3C7H9ClO3·CHCl3Dx = 1.556 Mg m3
Mr = 649.16Melting point: decomposition K
Hexagonal, R3mCu Kα radiation, λ = 1.54184 Å
Hall symbol: R 3 -2"Cell parameters from 25 reflections
a = 18.687 (5) Åθ = 32–45°
c = 6.8723 (16) ŵ = 6.09 mm1
V = 2078.3 (9) Å3T = 295 K
Z = 3Prism, colourless
F(000) = 10020.1 × 0.07 × 0.06 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
966 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.036
Graphite monochromatorθmax = 71.9°, θmin = 4.7°
Nonprofiled ω scansh = 220
Absorption correction: ψ scan
(North et al., 1968)
k = 022
Tmin = 0.530, Tmax = 0.694l = 88
1832 measured reflections2 standard reflections every 120 min
987 independent reflections intensity decay: none
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.054 w = 1/[σ2(Fo2) + (0.021P)2 + 2.2041P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.168(Δ/σ)max = 0.001
S = 1.18Δρmax = 0.28 e Å3
987 reflectionsΔρmin = 0.51 e Å3
69 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0016 (4)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 481 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.01 (2)
Crystal data top
3C7H9ClO3·CHCl3Z = 3
Mr = 649.16Cu Kα radiation
Hexagonal, R3mµ = 6.09 mm1
a = 18.687 (5) ÅT = 295 K
c = 6.8723 (16) Å0.1 × 0.07 × 0.06 mm
V = 2078.3 (9) Å3
Data collection top
Enraf–Nonius CAD-4
diffractometer
966 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.036
Tmin = 0.530, Tmax = 0.6942 standard reflections every 120 min
1832 measured reflections intensity decay: none
987 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.168Δρmax = 0.28 e Å3
S = 1.18Δρmin = 0.51 e Å3
987 reflectionsAbsolute structure: Flack (1983), 481 Friedel pairs
69 parametersAbsolute structure parameter: 0.01 (2)
1 restraint
Special details top

Experimental. As the solvent molecules release from the crystal at ambient air, so the experiment was carried out from the crystal placed in a glass capillary.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cl10.29956 (13)0.14978 (7)0.6438 (3)0.0671 (7)
Cl20.61527 (5)0.38473 (5)0.7368 (3)0.0619 (6)
O10.3605 (3)0.0525 (2)0.3740 (6)0.0560 (10)
O20.5272 (3)0.26359 (14)0.3179 (9)0.0583 (13)
C10.3610 (3)0.18052 (16)0.4256 (8)0.0341 (12)
H10.32320.16160.31430.041*
C20.4122 (3)0.1378 (2)0.4156 (6)0.0397 (10)
H20.43930.14360.54140.048*
C30.4782 (3)0.1795 (3)0.2586 (8)0.0510 (12)
H30.51150.15270.24340.061*
C40.4419 (4)0.1856 (3)0.0684 (8)0.0543 (12)
H40.42280.14670.03110.065*
C50.66670.33330.654 (2)0.048 (3)
H50.66670.33330.51110.058*
H110.361 (4)0.024 (4)0.453 (10)0.063 (19)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0535 (11)0.0777 (11)0.0619 (10)0.0268 (5)0.0216 (8)0.0108 (4)
Cl20.0497 (8)0.0497 (8)0.0932 (14)0.0300 (8)0.0052 (4)0.0052 (4)
O10.077 (3)0.0298 (16)0.058 (2)0.0241 (18)0.0182 (19)0.0027 (15)
O20.026 (2)0.054 (2)0.085 (3)0.0128 (11)0.001 (2)0.0003 (11)
C10.026 (3)0.033 (2)0.040 (3)0.0132 (13)0.002 (2)0.0012 (11)
C20.039 (2)0.0310 (19)0.052 (2)0.0196 (17)0.0126 (18)0.0054 (17)
C30.039 (2)0.052 (3)0.071 (3)0.029 (2)0.004 (2)0.003 (2)
C40.054 (3)0.061 (3)0.051 (2)0.031 (2)0.013 (2)0.000 (2)
C50.033 (3)0.033 (3)0.078 (8)0.0166 (16)0.0000.000
Geometric parameters (Å, º) top
Cl1—C11.799 (6)C2—C31.526 (7)
Cl2—C51.759 (5)C2—H20.9800
O1—C21.420 (5)C3—C41.503 (8)
O1—H110.77 (7)C3—H30.9800
O2—C3i1.426 (6)C4—C4i1.320 (11)
O2—C31.426 (6)C4—H40.9300
C1—C21.524 (5)C5—Cl2ii1.759 (5)
C1—C2i1.524 (5)C5—Cl2iii1.759 (5)
C1—H10.9800C5—H50.9800
C2—O1—H11114 (5)O2—C3—C2105.7 (4)
C3i—O2—C3102.6 (5)C4—C3—C2111.9 (4)
C2—C1—C2i113.8 (5)O2—C3—H3111.8
C2—C1—Cl1109.8 (3)C4—C3—H3111.8
C2i—C1—Cl1109.8 (3)C2—C3—H3111.8
C2—C1—H1107.7C4i—C4—C3107.6 (3)
C2i—C1—H1107.7C4i—C4—H4126.2
Cl1—C1—H1107.7C3—C4—H4126.2
O1—C2—C1110.1 (4)Cl2ii—C5—Cl2iii110.0 (4)
O1—C2—C3110.7 (4)Cl2ii—C5—Cl2110.0 (4)
C1—C2—C3108.8 (4)Cl2iii—C5—Cl2110.0 (4)
O1—C2—H2109.1Cl2ii—C5—H5108.9
C1—C2—H2109.1Cl2iii—C5—H5108.9
C3—C2—H2109.1Cl2—C5—H5108.9
O2—C3—C4103.3 (4)
Symmetry codes: (i) x, xy, z; (ii) x+y+1, x+1, z; (iii) y+1, xy, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H11···O1iv0.77 (7)1.98 (7)2.723 (3)162 (7)
Symmetry code: (iv) x+y+2/3, x+1/3, z+1/3.

Experimental details

Crystal data
Chemical formula3C7H9ClO3·CHCl3
Mr649.16
Crystal system, space groupHexagonal, R3m
Temperature (K)295
a, c (Å)18.687 (5), 6.8723 (16)
V3)2078.3 (9)
Z3
Radiation typeCu Kα
µ (mm1)6.09
Crystal size (mm)0.1 × 0.07 × 0.06
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.530, 0.694
No. of measured, independent and
observed [I > 2σ(I)] reflections
1832, 987, 966
Rint0.036
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.168, 1.18
No. of reflections987
No. of parameters69
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.28, 0.51
Absolute structureFlack (1983), 481 Friedel pairs
Absolute structure parameter0.01 (2)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2000), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H11···O1i0.77 (7)1.98 (7)2.723 (3)162 (7)
Symmetry code: (i) x+y+2/3, x+1/3, z+1/3.
 

References

First citationBrandenburg, K. (2000). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationEnraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.  Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationHarms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.  Google Scholar
First citationMiller, D. J. & Allemann, R. K. (2007). Mini-Rev. Med. Chem. 7, 107–113.  CrossRef CAS Google Scholar
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science Google Scholar
First citationPiettre, S. R., Andre, C., Chanal, M. C., Ducep, J. B., Lesur, B., Piriou, F., Raboisson, P., Rondeau, J. M., Schelcher, C., Zimmermann, P. & Ganzborn, A. J. (1997). J. Med. Chem. 40, 4208–4221.  Web of Science CrossRef CAS PubMed Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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