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

Tafeenko, V.A.; Aslanov, L.A.; Proskurnina, M.V.; Sosonyuk, S.E.; Khlevin, D.A.

doi:10.1107/S1600536809021898

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1580

doi:10.1107/S1600536809021898

Open

access

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

Viktor A. Tafeenko,^a Leonid A. Aslanov,^a ^* Marina V. Proskurnina,^a Sergei E. Sosonyuk ^a and Dmitrii A. Khlevin ^a

^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 ); Miller & Allemann (2007 ).

Experimental

Crystal data

3C₇H₉ClO₃·CHCl₃
M_r = 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 ) T_min = 0.530, T_max = 0.694
1832 measured reflections
987 independent reflections
966 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.51 e Å⁻³
Absolute structure: Flack (1983 ), 481 Friedel pairs
Flack parameter: −0.01 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: CAD-4 Software; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809021898/si2178sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809021898/si2178Isup2.hkl

checkCIF report

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.

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

	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.
	Fig. 2. The packing motif of the crystal structure. Symmetry codes: (i) -x + y+2/3, -x + 1/3, z + 1/3
	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·CHCl₃	D_x = 1.556 Mg m⁻³
M_r = 649.16	Melting point: decomposition K
Hexagonal, R3m	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: R 3 -2"	Cell parameters from 25 reflections
a = 18.687 (5) Å	θ = 32–45°
c = 6.8723 (16) Å	µ = 6.09 mm⁻¹
V = 2078.3 (9) Å³	T = 295 K
Z = 3	Prism, colourless
F(000) = 1002	0.1 × 0.07 × 0.06 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	966 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 71.9°, θ_min = 4.7°
Nonprofiled ω scans	h = −22→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→22
T_min = 0.530, T_max = 0.694	l = −8→8
1832 measured reflections	2 standard reflections every 120 min
987 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.054	w = 1/[σ²(F_o²) + (0.021P)² + 2.2041P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.168	(Δ/σ)_max = 0.001
S = 1.18	Δρ_max = 0.28 e Å⁻³
987 reflections	Δρ_min = −0.51 e Å⁻³
69 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0016 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 481 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.01 (2)

Crystal data top

3C₇H₉ClO₃·CHCl₃	Z = 3
M_r = 649.16	Cu Kα radiation
Hexagonal, R3m	µ = 6.09 mm⁻¹
a = 18.687 (5) Å	T = 295 K
c = 6.8723 (16) Å	0.1 × 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)	R_int = 0.036
T_min = 0.530, T_max = 0.694	2 standard reflections every 120 min
1832 measured reflections	intensity decay: none
987 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.168	Δρ_max = 0.28 e Å⁻³
S = 1.18	Δρ_min = −0.51 e Å⁻³
987 reflections	Absolute structure: Flack (1983), 481 Friedel pairs
69 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
Cl1	0.29956 (13)	0.14978 (7)	0.6438 (3)	0.0671 (7)
Cl2	0.61527 (5)	0.38473 (5)	0.7368 (3)	0.0619 (6)
O1	0.3605 (3)	0.0525 (2)	0.3740 (6)	0.0560 (10)
O2	0.5272 (3)	0.26359 (14)	0.3179 (9)	0.0583 (13)
C1	0.3610 (3)	0.18052 (16)	0.4256 (8)	0.0341 (12)
H1	0.3232	0.1616	0.3143	0.041*
C2	0.4122 (3)	0.1378 (2)	0.4156 (6)	0.0397 (10)
H2	0.4393	0.1436	0.5414	0.048*
C3	0.4782 (3)	0.1795 (3)	0.2586 (8)	0.0510 (12)
H3	0.5115	0.1527	0.2434	0.061*
C4	0.4419 (4)	0.1856 (3)	0.0684 (8)	0.0543 (12)
H4	0.4228	0.1467	−0.0311	0.065*
C5	0.6667	0.3333	0.654 (2)	0.048 (3)
H5	0.6667	0.3333	0.5111	0.058*
H11	0.361 (4)	0.024 (4)	0.453 (10)	0.063 (19)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0535 (11)	0.0777 (11)	0.0619 (10)	0.0268 (5)	0.0216 (8)	0.0108 (4)
Cl2	0.0497 (8)	0.0497 (8)	0.0932 (14)	0.0300 (8)	0.0052 (4)	−0.0052 (4)
O1	0.077 (3)	0.0298 (16)	0.058 (2)	0.0241 (18)	−0.0182 (19)	−0.0027 (15)
O2	0.026 (2)	0.054 (2)	0.085 (3)	0.0128 (11)	0.001 (2)	0.0003 (11)
C1	0.026 (3)	0.033 (2)	0.040 (3)	0.0132 (13)	−0.002 (2)	−0.0012 (11)
C2	0.039 (2)	0.0310 (19)	0.052 (2)	0.0196 (17)	−0.0126 (18)	−0.0054 (17)
C3	0.039 (2)	0.052 (3)	0.071 (3)	0.029 (2)	0.004 (2)	−0.003 (2)
C4	0.054 (3)	0.061 (3)	0.051 (2)	0.031 (2)	0.013 (2)	0.000 (2)
C5	0.033 (3)	0.033 (3)	0.078 (8)	0.0166 (16)	0.000	0.000

Geometric parameters (Å, º) top

Cl1—C1	1.799 (6)	C2—C3	1.526 (7)
Cl2—C5	1.759 (5)	C2—H2	0.9800
O1—C2	1.420 (5)	C3—C4	1.503 (8)
O1—H11	0.77 (7)	C3—H3	0.9800
O2—C3ⁱ	1.426 (6)	C4—C4ⁱ	1.320 (11)
O2—C3	1.426 (6)	C4—H4	0.9300
C1—C2	1.524 (5)	C5—Cl2ⁱⁱ	1.759 (5)
C1—C2ⁱ	1.524 (5)	C5—Cl2ⁱⁱⁱ	1.759 (5)
C1—H1	0.9800	C5—H5	0.9800

C2—O1—H11	114 (5)	O2—C3—C2	105.7 (4)
C3ⁱ—O2—C3	102.6 (5)	C4—C3—C2	111.9 (4)
C2—C1—C2ⁱ	113.8 (5)	O2—C3—H3	111.8
C2—C1—Cl1	109.8 (3)	C4—C3—H3	111.8
C2ⁱ—C1—Cl1	109.8 (3)	C2—C3—H3	111.8
C2—C1—H1	107.7	C4ⁱ—C4—C3	107.6 (3)
C2ⁱ—C1—H1	107.7	C4ⁱ—C4—H4	126.2
Cl1—C1—H1	107.7	C3—C4—H4	126.2
O1—C2—C1	110.1 (4)	Cl2ⁱⁱ—C5—Cl2ⁱⁱⁱ	110.0 (4)
O1—C2—C3	110.7 (4)	Cl2ⁱⁱ—C5—Cl2	110.0 (4)
C1—C2—C3	108.8 (4)	Cl2ⁱⁱⁱ—C5—Cl2	110.0 (4)
O1—C2—H2	109.1	Cl2ⁱⁱ—C5—H5	108.9
C1—C2—H2	109.1	Cl2ⁱⁱⁱ—C5—H5	108.9
C3—C2—H2	109.1	Cl2—C5—H5	108.9
O2—C3—C4	103.3 (4)

Symmetry codes: (i) x, x−y, z; (ii) −x+y+1, −x+1, z; (iii) −y+1, x−y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O1^iv	0.77 (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 formula	3C₇H₉ClO₃·CHCl₃
M_r	649.16
Crystal system, space group	Hexagonal, R3m
Temperature (K)	295
a, c (Å)	18.687 (5), 6.8723 (16)
V (Å³)	2078.3 (9)
Z	3
Radiation type	Cu Kα
µ (mm⁻¹)	6.09
Crystal size (mm)	0.1 × 0.07 × 0.06

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.530, 0.694
No. of measured, independent and observed [I > 2σ(I)] reflections	1832, 987, 966
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.168, 1.18
No. of reflections	987
No. of parameters	69
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.51
Absolute structure	Flack (1983), 481 Friedel pairs
Absolute structure parameter	−0.01 (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···A	D—H	H···A	D···A	D—H···A
O1—H11···O1ⁱ	0.77 (7)	1.98 (7)	2.723 (3)	162 (7)

Symmetry code: (i) −x+y+2/3, −x+1/3, z+1/3.

References

Brandenburg, K. (2000). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Miller, D. J. & Allemann, R. K. (2007). Mini-Rev. Med. Chem. 7, 107–113. CrossRef CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
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. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1580

doi:10.1107/S1600536809021898

Open

access