(1S,5R)-1-(3,4-Dichloro­phen­yl)-3-oxa­bicyclo­[3.1.0]hexan-2-one

Görbitz, C.H.; Hansen, T.; Vestli, K.

doi:10.1107/S1600536809007533

organic compounds

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Volume 65| Part 4| April 2009| Page o686

doi:10.1107/S1600536809007533

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(1S,5R)-1-(3,4-Dichlorophenyl)-3-oxabicyclo[3.1.0]hexan-2-one

Carl Henrik Görbitz,^a ^* Tore Hansen ^a and Kristian Vestli ^a

^aDepartment of Chemistry, University of Oslo, P.O.Box 1033 Blindern, N-0315 Oslo, Norway
^*Correspondence e-mail: c.h.gorbitz@kjemi.uio.no

(Received 30 January 2009; accepted 2 March 2009; online 6 March 2009)

The absolute structure has been determined by X-ray analysis for the title compound, C₁₁H₈Cl₂O₂. The five-membered ring of the molecule is best described as a flattened envelope conformation with the methylene C atom located 0.208 (2) Å below the plane formed by the other four atoms. A weak intermolecular C—H⋯O hydrogen bond is present in the crystal structure

Related literature

The title compound was prepared as an intermediate in the search for potential triple neurotransmittor reuptake inhibitors, see: Milewska et al. (1996 ); Lin & Charette (2005 ); Tsuji et al. (1999 ); Džolić et al. (2003 ).

Experimental

Crystal data

C₁₁H₈Cl₂O₂
M_r = 243.07
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.0597 (4) Å
b = 11.1343 (7) Å
c = 12.6756 (8) Å
V = 996.36 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.62 mm⁻¹
T = 102 K
0.58 × 0.36 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.680, T_max = 0.894
8562 measured reflections
2341 independent reflections
2278 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.063
S = 1.10
2341 reflections
160 parameters
Only H-atom coordinates refined
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 952 Friedel pairs
Flack parameter: 0.04 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H71⋯O2ⁱ	0.880 (18)	2.366 (18)	3.2443 (16)	175.6 (16)
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809007533/xu2480sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007533/xu2480Isup2.hkl

checkCIF report

Comment top

The title compound was prepared as an intermediate in the search for potential triple neurotransmittor reuptake inhibitors (Milewska et al., 1996; Lin & Charette, 2005; Tsuji et al., 1999; Džolić et al., 2003); details will be published elsewhere.

The molecular structure is shown in Fig. 1. The five-membered ring of the molecule is best described as a flat envelope conformation with C1 located 0.208 (2) Å below the plane constituted by C2, C4, C5 and O1, on the opposite side of C3. In the crystal structure the weak C—H···O hydrogen bonding presents between benzene ring and the carbonyl O atom of the neighboring molecule (Table 1).

Related literature top

The title compound was prepared as an intermediate in the search for potential triple neurotransmittor reuptake inhibitors, see: Milewska et al. (1996); Lin & Charette (2005); Tsuji et al. (1999); Džolić et al. (2003).

Experimental top

Block-shaped single crystals were obtained from an acetonitrile solution by slow evaporation at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are shown at the 50% probability level and H atoms are shown as spheres of arbitrary size.

(1S,5R)-1-(3,4-dichlorophenyl)-3-oxabicyclo[3.1.0]hexan-2-one top

Crystal data top

C₁₁H₈Cl₂O₂	D_x = 1.620 Mg m⁻³
M_r = 243.07	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 6286 reflections
a = 7.0597 (4) Å	θ = 2.4–27.9°
b = 11.1343 (7) Å	µ = 0.62 mm⁻¹
c = 12.6756 (8) Å	T = 102 K
V = 996.36 (11) Å³	Block, colourless
Z = 4	0.58 × 0.36 × 0.18 mm
F(000) = 496

Data collection top

Bruker APEXII CCD diffractometer	2341 independent reflections
Radiation source: fine-focus sealed tube	2278 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 8.3 pixels mm^-1	θ_max = 27.9°, θ_min = 2.4°
Sets of exposures each taken over 0.5° ω rotation scans	h = −9→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
T_min = 0.680, T_max = 0.894	l = −16→16
8562 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	Only H-atom coordinates refined
wR(F²) = 0.063	w = 1/[σ²(F_o²) + (0.0387P)² + 0.112P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
2341 reflections	Δρ_max = 0.43 e Å⁻³
160 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 952 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (5)

Crystal data top

C₁₁H₈Cl₂O₂	V = 996.36 (11) Å³
M_r = 243.07	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.0597 (4) Å	µ = 0.62 mm⁻¹
b = 11.1343 (7) Å	T = 102 K
c = 12.6756 (8) Å	0.58 × 0.36 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	2341 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2278 reflections with I > 2σ(I)
T_min = 0.680, T_max = 0.894	R_int = 0.018
8562 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	Only H-atom coordinates refined
wR(F²) = 0.063	Δρ_max = 0.43 e Å⁻³
S = 1.10	Δρ_min = −0.20 e Å⁻³
2341 reflections	Absolute structure: Flack (1983), 952 Friedel pairs
160 parameters	Absolute structure parameter: 0.04 (5)
0 restraints

Special details top

Experimental. Crystallized from acetonitrile solution

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. Data were collected by measuring three sets of exposures with the detector set at 2θ = 29°, crystal-to-detector distance 6.00 cm. Refinement of F² against ALL reflections.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.76710 (6)	1.02347 (3)	0.53880 (3)	0.02383 (10)
Cl2	0.76768 (6)	0.86335 (3)	0.33094 (3)	0.02003 (10)
O1	0.89020 (18)	0.30003 (10)	0.51020 (9)	0.0219 (2)
O2	0.7597 (2)	0.41878 (9)	0.38886 (8)	0.0258 (3)
C1	0.9599 (2)	0.30985 (14)	0.61831 (12)	0.0195 (3)
H11	1.095 (3)	0.3243 (17)	0.6145 (14)	0.023*
H12	0.928 (3)	0.2377 (17)	0.6515 (15)	0.023*
C2	0.8628 (2)	0.41790 (14)	0.66439 (13)	0.0162 (3)
H21	0.921 (2)	0.4618 (19)	0.7169 (15)	0.019*
C3	0.6531 (2)	0.41869 (15)	0.65659 (14)	0.0183 (3)
H31	0.586 (3)	0.469 (2)	0.6993 (15)	0.022*
H32	0.590 (3)	0.3471 (17)	0.6365 (14)	0.022*
C4	0.7718 (2)	0.48380 (12)	0.57217 (10)	0.0153 (3)
C5	0.8034 (2)	0.40360 (13)	0.47933 (12)	0.0191 (3)
C6	0.7654 (2)	0.61725 (12)	0.56086 (11)	0.0154 (3)
C7	0.7598 (2)	0.68907 (12)	0.65134 (10)	0.0174 (3)
H71	0.756 (3)	0.6558 (15)	0.7143 (14)	0.021*
C8	0.7586 (2)	0.81285 (12)	0.64365 (11)	0.0183 (3)
H81	0.746 (3)	0.8709 (14)	0.7047 (13)	0.022*
C9	0.7631 (2)	0.86805 (11)	0.54561 (11)	0.0167 (3)
C10	0.7664 (2)	0.79786 (12)	0.45517 (10)	0.0155 (3)
C11	0.7674 (2)	0.67269 (12)	0.46254 (11)	0.0156 (3)
H111	0.776 (3)	0.6262 (14)	0.4035 (14)	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0310 (2)	0.01352 (15)	0.02696 (19)	0.00112 (17)	−0.00448 (17)	0.00012 (12)
Cl2	0.02456 (18)	0.01897 (16)	0.01656 (16)	−0.00227 (16)	−0.00294 (15)	0.00519 (12)
O1	0.0341 (6)	0.0156 (5)	0.0160 (5)	−0.0008 (5)	0.0016 (5)	−0.0023 (4)
O2	0.0423 (7)	0.0211 (5)	0.0141 (5)	−0.0054 (6)	−0.0031 (6)	−0.0004 (4)
C1	0.0258 (8)	0.0161 (7)	0.0165 (7)	0.0021 (6)	0.0009 (6)	0.0023 (6)
C2	0.0203 (7)	0.0157 (7)	0.0126 (7)	0.0001 (6)	−0.0008 (6)	0.0010 (6)
C3	0.0216 (7)	0.0158 (7)	0.0175 (8)	−0.0008 (6)	0.0022 (6)	0.0030 (6)
C4	0.0186 (7)	0.0153 (6)	0.0120 (6)	−0.0015 (6)	−0.0015 (5)	0.0013 (5)
C5	0.0255 (8)	0.0142 (6)	0.0176 (7)	−0.0050 (6)	0.0003 (6)	−0.0004 (5)
C6	0.0142 (6)	0.0156 (6)	0.0165 (6)	−0.0012 (6)	−0.0012 (6)	0.0015 (5)
C7	0.0194 (7)	0.0192 (6)	0.0137 (6)	−0.0003 (7)	−0.0009 (6)	0.0018 (5)
C8	0.0179 (7)	0.0194 (6)	0.0176 (6)	0.0010 (7)	−0.0016 (6)	−0.0029 (5)
C9	0.0157 (6)	0.0129 (6)	0.0215 (7)	−0.0006 (6)	−0.0034 (6)	0.0003 (5)
C10	0.0140 (7)	0.0171 (6)	0.0153 (6)	−0.0010 (6)	−0.0019 (6)	0.0045 (5)
C11	0.0154 (7)	0.0168 (6)	0.0144 (6)	−0.0012 (6)	−0.0010 (6)	0.0003 (5)

Geometric parameters (Å, º) top

Cl1—C9	1.7329 (13)	C3—H32	0.949 (19)
Cl2—C10	1.7353 (13)	C4—C6	1.4934 (18)
O1—C5	1.3631 (19)	C4—C5	1.4940 (19)
O1—C1	1.4602 (19)	C6—C11	1.3909 (18)
O2—C5	1.1996 (18)	C6—C7	1.3988 (19)
C1—C2	1.503 (2)	C7—C8	1.3817 (19)
C1—H11	0.97 (2)	C7—H71	0.880 (17)
C1—H12	0.93 (2)	C8—C9	1.3868 (19)
C2—C3	1.484 (2)	C8—H81	1.012 (17)
C2—C4	1.522 (2)	C9—C10	1.3877 (19)
C2—H21	0.92 (2)	C10—C11	1.3968 (19)
C3—C4	1.541 (2)	C11—H111	0.912 (17)
C3—H31	0.91 (2)

C5—O1—C1	110.94 (12)	C5—C4—C3	110.31 (12)
O1—C1—C2	105.73 (13)	C2—C4—C3	57.96 (9)
O1—C1—H11	107.3 (11)	O2—C5—O1	120.62 (14)
C2—C1—H11	109.6 (12)	O2—C5—C4	129.07 (14)
O1—C1—H12	106.0 (12)	O1—C5—C4	110.28 (13)
C2—C1—H12	113.7 (11)	C11—C6—C7	118.77 (12)
H11—C1—H12	113.8 (16)	C11—C6—C4	121.82 (12)
C3—C2—C1	115.72 (15)	C7—C6—C4	119.40 (12)
C3—C2—C4	61.65 (11)	C8—C7—C6	120.84 (13)
C1—C2—C4	106.25 (13)	C8—C7—H71	118.9 (11)
C3—C2—H21	119.1 (11)	C6—C7—H71	120.3 (11)
C1—C2—H21	120.2 (12)	C7—C8—C9	120.34 (12)
C4—C2—H21	119.1 (13)	C7—C8—H81	125.7 (9)
C2—C3—C4	60.40 (11)	C9—C8—H81	113.8 (9)
C2—C3—H31	118.9 (12)	C8—C9—C10	119.42 (12)
C4—C3—H31	113.9 (13)	C8—C9—Cl1	119.18 (10)
C2—C3—H32	118.9 (11)	C10—C9—Cl1	121.40 (10)
C4—C3—H32	117.8 (11)	C9—C10—C11	120.45 (12)
H31—C3—H32	115.4 (18)	C9—C10—Cl2	120.87 (10)
C6—C4—C5	121.57 (12)	C11—C10—Cl2	118.68 (10)
C6—C4—C2	124.48 (12)	C6—C11—C10	120.18 (13)
C5—C4—C2	104.70 (11)	C6—C11—H111	118.9 (10)
C6—C4—C3	121.22 (12)	C10—C11—H111	120.8 (10)

C1—C2—C4—C5	5.85 (15)	C3—C4—C5—O1	−57.45 (16)
O1—C1—C2—C4	−12.38 (16)	C2—C4—C6—C11	148.81 (15)
C2—C4—C5—O1	3.36 (16)	C3—C4—C6—C11	−140.85 (15)
C5—C4—C6—C11	7.2 (2)	C5—C4—C6—C7	−171.84 (15)
C5—O1—C1—C2	15.19 (17)	C2—C4—C6—C7	−30.3 (2)
O1—C1—C2—C3	53.50 (19)	C3—C4—C6—C7	40.1 (2)
C1—C2—C3—C4	−95.34 (15)	C11—C6—C7—C8	−0.7 (3)
C3—C2—C4—C6	108.17 (17)	C4—C6—C7—C8	178.38 (15)
C1—C2—C4—C6	−140.96 (15)	C6—C7—C8—C9	−0.1 (3)
C3—C2—C4—C5	−105.02 (14)	C7—C8—C9—C10	0.8 (3)
C1—C2—C4—C5	5.85 (15)	C7—C8—C9—Cl1	−178.46 (14)
C1—C2—C4—C3	110.87 (16)	C8—C9—C10—C11	−0.7 (2)
C2—C3—C4—C6	−113.68 (15)	Cl1—C9—C10—C11	178.55 (12)
C2—C3—C4—C5	95.02 (14)	C8—C9—C10—Cl2	178.79 (13)
C1—O1—C5—O2	169.94 (16)	Cl1—C9—C10—Cl2	−1.94 (19)
C1—O1—C5—C4	−11.76 (17)	C7—C6—C11—C10	0.8 (2)
C6—C4—C5—O2	−30.5 (3)	C4—C6—C11—C10	−178.25 (14)
C2—C4—C5—O2	−178.54 (17)	C9—C10—C11—C6	−0.1 (2)
C3—C4—C5—O2	120.66 (19)	Cl2—C10—C11—C6	−179.64 (12)
C6—C4—C5—O1	151.37 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H71···O2ⁱ	0.880 (18)	2.366 (18)	3.2443 (16)	175.6 (16)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₈Cl₂O₂
M_r	243.07
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	102
a, b, c (Å)	7.0597 (4), 11.1343 (7), 12.6756 (8)
V (Å³)	996.36 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.62
Crystal size (mm)	0.58 × 0.36 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.680, 0.894
No. of measured, independent and observed [I > 2σ(I)] reflections	8562, 2341, 2278
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.063, 1.10
No. of reflections	2341
No. of parameters	160
H-atom treatment	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.20
Absolute structure	Flack (1983), 952 Friedel pairs
Absolute structure parameter	0.04 (5)

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H71···O2ⁱ	0.880 (18)	2.366 (18)	3.2443 (16)	175.6 (16)

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

References

Bruker (2007). APEX2 and SAINT-Plus. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Džolić, Z., Krištafor, V., Cetina, M., Nagl, A., Hergold-Brundić, A., Mrvoš-Sermek, D., Burgemeister, T., Grdiša, M., Slade, N., Pavelic, K., Balzarini, J., De Clercq, E. & Mintas, M. (2003). Nucleosides Nucleotides Nucleic Acids, 22, 373–389. Web of Science PubMed Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Lin, W. & Charette, A. B. (2005). Adv. Synth. Catal. 347, 1547–1552. Web of Science CSD CrossRef CAS Google Scholar
Milewska, M. J., Gdaniec, M. & Poloński, T. (1996). Tetrahedron Asymmetry, 7, 3169–3180. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tsuji, T., Onishi, T. & Sakata, K. (1999). Tetrahedron Asymmetry, 10, 3819–3825. Web of Science CSD CrossRef CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o686

doi:10.1107/S1600536809007533

Open

access