(1RS,2RS,3SR,5RS,7RS)-2,5-Dichloro-8-oxabicyclo­[5.1.0]octan-3-ol

Çetinkaya, Y.; Menzek, A.; Hökelek, T.

doi:10.1107/S1600536811013304

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1145

doi:10.1107/S1600536811013304

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(1RS,2RS,3SR,5RS,7RS)-2,5-Dichloro-8-oxabicyclo[5.1.0]octan-3-ol

Yasin Çetinkaya,^a Abdullah Menzek ^a and Tuncer Hökelek ^b ^*

^aDepartment of Chemistry, Atatürk University, 25240 Erzurum, Turkey, and ^bDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 25 March 2011; accepted 8 April 2011; online 16 April 2011)

In the title compound, C₇H₁₀Cl₂O₂, the seven-membered ring displays a chair conformation. In the crystal, the hydroxy H atom is equally disordered over two orientations, and links with an adjacent molecule via an O—H⋯O hydrogen bond in both cases. Weak intermolecular C—H⋯O hydrogen bonding is also a feature of the crystal structure.

Related literature

For background to syn-bis-epoxides, see: Balcı (1981 ); Akbulut et al. (1987 ); Menzek & Balcı (1993 ); Saraçoğlu et al. (1999 ). For background to unsaturated bicyclic endopexide, see: Menzek et al. (2005 ). For background to epoxide and bis-epoxide, see: Şengül et al. (2008 ).

Experimental

Crystal data

C₇H₁₀Cl₂O₂
M_r = 197.05
Orthorhombic, P b c n
a = 21.9202 (5) Å
b = 9.9343 (3) Å
c = 8.1005 (2) Å
V = 1763.98 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 294 K
0.32 × 0.20 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.845, T_max = 0.900
32813 measured reflections
1801 independent reflections
1267 reflections with I > 2σ(I)
R_int = 0.110

Refinement

R[F² > 2σ(F²)] = 0.088
wR(F²) = 0.190
S = 1.18
1801 reflections
115 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O2ⁱ	0.83 (11)	1.96 (11)	2.746 (7)	159 (12)
O2—H2B⋯O2ⁱⁱ	0.85	1.84	2.692 (8)	174
C2—H21⋯O1ⁱⁱⁱ	0.97	2.43	3.398 (7)	172
Symmetry codes: (i) -x+1, -y+2, -z; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811013304/xu5182sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811013304/xu5182Isup2.hkl

checkCIF report

Comment top

Unsaturated bicyclic endopexides are important compounds for versatile chemical transformations in organic chemistry. In these endoperoxides, diradicals formed by thermal cleavage of the weak O-O bonds react to give the syn-bis-epoxides (Balcı, 1981; Akbulut et al., 1987; Menzek & Balcı, 1993; Saraçoğlu et al., 1999).

Unsaturated bicyclic endopexide, (1), (Scheme 1) was synthesized by the literature method (Menzek et al., 2005). Reaction of endoperoxide, (1), by heating at 453 (5) K gave a mixture of products (Scheme 1). The title compound, (2), was isolated from these mixtures. The other products were not identified. According to the NMR data of dichloride, (2), it was not easy to establish the exact configuration of the molecule. Therefore, the exact structure of dichloride, (2), was determined by X-ray single crystal analysis.

To rationalize the formation of dichloride, (2), we propose the following reaction mechanism as favourable mechanism (Scheme 1). Bis-epoxide, (3), is produced via diradicals formed by thermal cleavage of the weak O-O bonds. HCl formed by elimination from reaction products such as (3) can attack bis-epoxide, (3), to give intermediate (4). Cl^- can attack intermediate (4) to give dichloride, (2), as a nucleophile. An epoxide or bis-epoxide ring (Şengül et al., 2008) may be opened by as a nucleophile.

In the title compound, the seven-membered ring A (C1-C7) is, of course, not planar. The planar moieties B (O1/C1/C7), C (C3-C5), D (C2/C3/C5/C6) and E (C1/C2/C6/C7) are oriented at dihedral angles of B/C = 68.75 (46)°, B/D = 13.84 (28)°, B/E = 74.48 (32)°, C/D = 54.91 (42)°, C/E = 6.00 (42)° and D/E = 60.65 (30)°.

In the crystal, intermolecular O—H···O and C—H···O hydrogen bonds link the molecules into a three-dimensional network (Table 1 and Fig. 2).

Related literature top

For background to syn-bis-epoxides, see: Balcı (1981); Akbulut et al. (1987); Menzek & Balcı (1993); Saraçoğlu et al. (1999). For unsaturated bicyclic endopexide, see: Menzek et al. (2005). For epoxide or bis-epoxide, see: Şengül et al. (2008).

Experimental top

For the preparation of the title compound, a mixture of endoproxide (0.5 g, 2.6 mmol) and benzene (5 ml) was placed into a test tube, sealed under vacuum and heated at 453 (5) K for 3 d. After cooling to room temperature, the solvent was evaporated. The residue was submitted to column chromatography (silica gel, 90 g) with AcOEt/hexane (1:6) as eluant. Dichloride (yield: 0.056 g, 9%, m. p. 366-368 K) and a mixture of unidentified products were obtained. Dichloride was crystallized from ethyl acetate/hexane (1:1) as colorless block crystals.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. A view of the crystal packing of the title compound. The O-H···O and C-H···O hydrogen bonds are shown as dashed lines.

(1RS,2RS,3SR,5RS,7RS)-2,5-Dichloro- 8-oxabicyclo[5.1.0]octan-3-ol top

Crystal data top

C₇H₁₀Cl₂O₂	F(000) = 816
M_r = 197.05	D_x = 1.484 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4978 reflections
a = 21.9202 (5) Å	θ = 2.3–26.4°
b = 9.9343 (3) Å	µ = 0.68 mm⁻¹
c = 8.1005 (2) Å	T = 294 K
V = 1763.98 (8) Å³	Block, colorless
Z = 8	0.32 × 0.20 × 0.15 mm

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	1801 independent reflections
Radiation source: fine-focus sealed tube	1267 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.110
ω scans	θ_max = 26.4°, θ_min = 2.3°
Absorption correction: multi-scan (Blessing, 1995)	h = −27→27
T_min = 0.845, T_max = 0.900	k = −12→12
32813 measured reflections	l = −9→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.088	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.190	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ²(F_o²) + (0.020P)² + 5.1831P] where P = (F_o² + 2F_c²)/3
1801 reflections	(Δ/σ)_max < 0.001
115 parameters	Δρ_max = 0.28 e Å⁻³
2 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₇H₁₀Cl₂O₂	V = 1763.98 (8) Å³
M_r = 197.05	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 21.9202 (5) Å	µ = 0.68 mm⁻¹
b = 9.9343 (3) Å	T = 294 K
c = 8.1005 (2) Å	0.32 × 0.20 × 0.15 mm

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	1801 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	1267 reflections with I > 2σ(I)
T_min = 0.845, T_max = 0.900	R_int = 0.110
32813 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.088	2 restraints
wR(F²) = 0.190	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	Δρ_max = 0.28 e Å⁻³
1801 reflections	Δρ_min = −0.34 e Å⁻³
115 parameters

Special details top

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 > 2sigma(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	Occ. (<1)
Cl1	0.59049 (9)	0.41547 (16)	0.1157 (2)	0.0883 (6)
Cl2	0.62620 (9)	1.07361 (16)	0.1076 (2)	0.0841 (6)
O1	0.7389 (2)	0.8227 (5)	0.1601 (7)	0.1017 (17)
O2	0.5199 (2)	0.8930 (5)	0.0928 (7)	0.0941 (16)
H2A	0.511 (7)	0.945 (11)	0.017 (12)	0.090*	0.50
H2B	0.5050	0.8950	0.1900	0.090*	0.50
C1	0.7119 (3)	0.7145 (7)	0.0682 (10)	0.084 (2)
H1	0.7361	0.6806	−0.0247	0.101*
C2	0.6766 (2)	0.6091 (6)	0.1650 (9)	0.0732 (18)
H21	0.7003	0.5271	0.1751	0.088*
H22	0.6672	0.6421	0.2748	0.088*
C3	0.6182 (3)	0.5825 (6)	0.0692 (8)	0.0604 (15)
H3	0.628 (3)	0.578 (7)	−0.042 (9)	0.10 (2)*
C4	0.5669 (2)	0.6810 (5)	0.1042 (8)	0.0610 (14)
H41	0.5303	0.6467	0.0516	0.073*
H42	0.5595	0.6806	0.2223	0.073*
C5	0.5748 (2)	0.8269 (6)	0.0507 (8)	0.0582 (14)
H5	0.580 (2)	0.832 (5)	−0.066 (7)	0.057 (16)*
C6	0.6294 (3)	0.8926 (5)	0.1265 (7)	0.0558 (13)
H6	0.636 (2)	0.873 (5)	0.231 (7)	0.066 (18)*
C7	0.6885 (2)	0.8499 (6)	0.0502 (8)	0.0703 (17)
H7	0.6993	0.8954	−0.0531	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1032 (13)	0.0592 (9)	0.1024 (14)	−0.0091 (8)	−0.0189 (11)	0.0044 (9)
Cl2	0.1150 (14)	0.0573 (9)	0.0799 (11)	−0.0025 (9)	0.0052 (10)	−0.0046 (8)
O1	0.067 (3)	0.095 (4)	0.143 (5)	−0.021 (3)	−0.030 (3)	0.028 (3)
O2	0.067 (3)	0.084 (3)	0.132 (5)	0.024 (2)	0.023 (3)	0.012 (3)
C1	0.049 (3)	0.097 (5)	0.107 (6)	0.011 (3)	0.009 (4)	0.011 (5)
C2	0.055 (3)	0.069 (4)	0.096 (5)	0.014 (3)	−0.016 (3)	0.010 (3)
C3	0.066 (4)	0.052 (3)	0.063 (4)	0.001 (3)	0.001 (3)	−0.005 (3)
C4	0.049 (3)	0.058 (3)	0.075 (4)	0.001 (2)	−0.009 (3)	−0.004 (3)
C5	0.050 (3)	0.064 (3)	0.061 (4)	0.008 (3)	−0.001 (3)	0.004 (3)
C6	0.066 (3)	0.049 (3)	0.052 (3)	0.001 (2)	−0.009 (3)	0.000 (3)
C7	0.052 (3)	0.075 (4)	0.084 (4)	−0.006 (3)	0.009 (3)	0.014 (3)

Geometric parameters (Å, º) top

Cl1—C3	1.806 (6)	C3—C2	1.520 (8)
Cl2—C6	1.806 (6)	C3—C4	1.518 (7)
O1—C1	1.434 (8)	C3—H3	0.93 (7)
O1—C7	1.443 (7)	C4—C5	1.522 (8)
O2—C5	1.413 (7)	C4—H41	0.9700
O2—H2B	0.853 (5)	C4—H42	0.9700
O2—H2A	0.82 (2)	C5—H5	0.95 (5)
C1—C7	1.447 (9)	C6—C5	1.497 (8)
C1—H1	0.9800	C6—C7	1.497 (8)
C2—C1	1.521 (8)	C6—H6	0.88 (6)
C2—H21	0.9700	C7—H7	0.9800
C2—H22	0.9700

C5—O2—H2B	124.0 (5)	C3—C4—H41	107.7
C5—O2—H2A	109 (10)	C3—C4—H42	107.7
H2B—O2—H2A	125 (10)	C5—C4—H41	107.7
C1—O1—C7	60.4 (4)	C5—C4—H42	107.7
O1—C1—C2	117.3 (6)	H42—C4—H41	107.1
O1—C1—C7	60.1 (4)	O2—C5—C4	106.1 (5)
O1—C1—H1	115.7	O2—C5—C6	112.3 (5)
C2—C1—H1	115.7	O2—C5—H5	109 (3)
C7—C1—C2	120.7 (5)	C4—C5—H5	110 (3)
C7—C1—H1	115.7	C6—C5—C4	112.9 (5)
C1—C2—H21	110.4	C6—C5—H5	107 (3)
C1—C2—H22	110.4	Cl2—C6—H6	108 (4)
C3—C2—C1	106.6 (5)	C5—C6—Cl2	111.6 (4)
C3—C2—H21	110.4	C5—C6—C7	113.6 (5)
C3—C2—H22	110.4	C5—C6—H6	116 (4)
H21—C2—H22	108.6	C7—C6—Cl2	106.3 (4)
Cl1—C3—H3	104 (4)	C7—C6—H6	101 (4)
C2—C3—Cl1	109.6 (4)	O1—C7—C1	59.5 (4)
C2—C3—H3	108 (4)	O1—C7—C6	117.4 (6)
C4—C3—Cl1	107.7 (4)	O1—C7—H7	115.4
C4—C3—C2	114.6 (5)	C1—C7—C6	122.0 (5)
C4—C3—H3	113 (4)	C1—C7—H7	115.4
C3—C4—C5	118.4 (5)	C6—C7—H7	115.4

C7—O1—C1—C2	−111.5 (6)	C3—C4—C5—O2	177.8 (5)
C1—O1—C7—C6	112.7 (6)	C3—C4—C5—C6	−58.7 (7)
O1—C1—C7—C6	−105.2 (7)	Cl2—C6—C5—O2	−44.3 (6)
C2—C1—C7—O1	105.9 (8)	Cl2—C6—C5—C4	−164.2 (4)
C2—C1—C7—C6	0.7 (10)	C7—C6—C5—O2	−164.5 (5)
C3—C2—C1—O1	135.8 (5)	C7—C6—C5—C4	75.6 (7)
C3—C2—C1—C7	66.0 (8)	Cl2—C6—C7—C1	168.9 (6)
Cl1—C3—C2—C1	154.6 (5)	Cl2—C6—C7—O1	99.4 (5)
C4—C3—C2—C1	−84.1 (7)	C5—C6—C7—O1	−137.5 (5)
Cl1—C3—C4—C5	−170.8 (4)	C5—C6—C7—C1	−68.0 (8)
C2—C3—C4—C5	66.8 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O2ⁱ	0.83 (11)	1.96 (11)	2.746 (7)	159 (12)
O2—H2B···O2ⁱⁱ	0.85	1.84	2.692 (8)	174
C2—H21···O1ⁱⁱⁱ	0.97	2.43	3.398 (7)	172

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, y, −z+1/2; (iii) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₇H₁₀Cl₂O₂
M_r	197.05
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	294
a, b, c (Å)	21.9202 (5), 9.9343 (3), 8.1005 (2)
V (Å³)	1763.98 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.68
Crystal size (mm)	0.32 × 0.20 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID-S diffractometer
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.845, 0.900
No. of measured, independent and observed [I > 2σ(I)] reflections	32813, 1801, 1267
R_int	0.110
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.088, 0.190, 1.18
No. of reflections	1801
No. of parameters	115
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.34

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O2ⁱ	0.83 (11)	1.96 (11)	2.746 (7)	159 (12)
O2—H2B···O2ⁱⁱ	0.85	1.84	2.692 (8)	174
C2—H21···O1ⁱⁱⁱ	0.97	2.43	3.398 (7)	172

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, y, −z+1/2; (iii) −x+3/2, y−1/2, z.

Acknowledgements

The authors are indebted to the Department of Chemistry, Atatürk University, Erzurum, Turkey, for the use of X-ray diffractometer purchased under grant No. 2003/219 of the University Research Fund.

References

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