Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033351/kp2118sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033351/kp2118Isup2.hkl |
CCDC reference: 657742
The title compound, 1-(benzofuran-2-yl)-2-chloroethanone, was synthesized from 1-benzofuran-2-ylethanone by chlorination with thionyl chloride in the carbon tetrachloride solution. Crystals suitable for the diffraction experiment were obtained by slow evaporation from the ethanol solution. Structure was solved with the direct methods and refined using SHELX98 package (Sheldrick, 1997).
Hydrogen atoms were put in the calculated positions and constrained during refinement (C—H 0.98 Å, aromatic C—H 0.93 Å, U fixed at 0.080 Å2).
Aryl-2-chloroethanone and alkyl-2-chloroethanons are precursors of appropriate beta-amino-alfa-aryl (or alkyl) ethanols (Zaidlewicz et al., 2005; Tanis et al., 2006). These compounds containing the amino function exhibit the pharmacological activity. Many beta-amine arylethanol derivatives such as albuterol, isoproterenol, sotalol and terbutaline are well known beta-blockers or agonists and used in treatment of asthma, glaucoma, and cardiovascular disease (Gareth, 2001). All of them are nonselective beta-adrenoreceptor blocking agents comparable to propranolol (Weerawarna et al., 1991; Fothergill et al., 1977). Aromatic beta-aminoalcohols are also widely used as substrates in studies of the oxidation in liver by cytochrome P450 enzymes (Narimatsu et al., 2003). Furthermore, many compounds mentioned above show an anti-arrythmic properties. Developing methods of their enantioselective synthesis is of particular importance.
We have found that crystal structure of the title compound is not known yet, although it is a well known substrate for the synthesis of benzofuran derivatives revealing different biological activity. Therefore, the aim of the study was to determine its molecular and crystal structures.
The molecule is planar with the dihedral angle of 1.9 (2) o between the best planes of benzofuran ring system and C2—C8—O2—C9 group containing carbonyl moiety. The chloromethylene moiety is almost co-planar with the ring system: the C2—C8—C9—Cl1 torsion angle is -175.8 (2) o, with the r.m.s. deviation of Cl1 from that plane of 0.079 (4) Å. The carbonyl O2 is in syn position relative to benzofuran O1, the O1—C2—C8—O2 torsion angle is 1.6 (4) o. The chlorine atom is positioned in syn orientation relative to carbonyl O2, with the O2—C8—C9—Cl1 torsion angle 4.7 (4) o. The valence geometry of the investigated compound is similar to that found for unsubstitituted compounds at position 3. In the reported structure the O1—C2 distance is 1.385 (3) Å and it is similar to 1.385 Å found in 2-acetylbenzo(b)furan (Thiruvalluvar et al., 2003). However, the substituted compounds: [2-acetyl-3-(benzoylamino)-1-benzofuran (Ocak Ískeleli et al., 2005), 2-acetyl-3-aminobenzofuran (Bachechi et al., 1988), and 1-(3-amino-1-benzofuran-2-yl)-2-mesitylethanone (Arıcı et al., 2004) reveal somewhat longer bond distances of 1.403–1.411 Å.
The packing analysis revealed that each molecule forms a pair of intermolecular C—H···O contact of 3.238 (3) Å along the b axis involving its C9—H methylene group and carbonyl oxygen, the C9···O2 (0.5 - x, 1/2 + y, z). The packing interactions are completed by stacking of the ring systems of the molecules related by a centre of inversion (1 - x, 1 - y, -z). Interaction π···π between adjacent molecules is characterized by distance between centroids of the furane moieties of 3.785 (3) Å. In these dimers anti-parallel orientation of molecules occurs.
For related literature, see: Arıcı et al. (2004); Bachechi et al. (1988); Fothergill et al. (1977); Gareth (2001); Ocak Ískeleli et al. (2005); Narimatsu et al. (2003); Tanis et al. (2006); Thiruvalluvar et al. (2003); Weerawarna et al. (1991); Zaidlewicz et al. (2005).
Data collection: CrysAlis CCD (Oxford Diffraction, 2000); cell refinement: CrysAlis RED or CCD? (Oxford Diffraction, 2000); data reduction: CrysAlis RED (Oxford Diffraction, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: CIFTAB in SHELXL97.
Fig. 1. A view of (I) with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
C10H7ClO2 | F(000) = 800 |
Mr = 194.61 | Dx = 1.485 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P2ac2ab | Cell parameters from 2172 reflections |
a = 9.550 (2) Å | θ = 3.1–31.4° |
b = 10.303 (2) Å | µ = 0.40 mm−1 |
c = 17.695 (4) Å | T = 293 K |
V = 1741.1 (6) Å3 | Plate, colorless |
Z = 8 | 0.34 × 0.14 × 0.08 mm |
Oxford Diffraction Sapphire CCD diffractometer | 2726 independent reflections |
Radiation source: fine-focus sealed tube | 1768 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
θ/2θ scans | θmax = 31.4°, θmin = 3.1° |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2000) | h = −13→13 |
Tmin = 0.876, Tmax = 0.968 | k = −14→13 |
16159 measured reflections | l = −25→23 |
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)] = 0.086 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.24 | w = 1/[σ2(Fo2) + (0.0534P)2] where P = (Fo2 + 2Fc2)/3 |
2726 reflections | (Δ/σ)max = 0.003 |
118 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C10H7ClO2 | V = 1741.1 (6) Å3 |
Mr = 194.61 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.550 (2) Å | µ = 0.40 mm−1 |
b = 10.303 (2) Å | T = 293 K |
c = 17.695 (4) Å | 0.34 × 0.14 × 0.08 mm |
Oxford Diffraction Sapphire CCD diffractometer | 2726 independent reflections |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2000) | 1768 reflections with I > 2σ(I) |
Tmin = 0.876, Tmax = 0.968 | Rint = 0.074 |
16159 measured reflections |
R[F2 > 2σ(F2)] = 0.086 | 0 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.24 | Δρmax = 0.28 e Å−3 |
2726 reflections | Δρmin = −0.26 e Å−3 |
118 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C2 | 0.3196 (3) | 0.4735 (2) | −0.04559 (15) | 0.0381 (6) | |
O1 | 0.3670 (2) | 0.35910 (16) | −0.07774 (10) | 0.0438 (5) | |
C3 | 0.3858 (3) | 0.5771 (2) | −0.07517 (15) | 0.0397 (6) | |
H2A | 0.3715 | 0.6636 | −0.0623 | 0.048* | |
C3A | 0.4825 (3) | 0.5288 (3) | −0.13015 (15) | 0.0394 (6) | |
C4 | 0.5801 (3) | 0.5831 (3) | −0.17913 (16) | 0.0512 (8) | |
H4A | 0.5930 | 0.6726 | −0.1811 | 0.061* | |
C5 | 0.6573 (3) | 0.5017 (3) | −0.22456 (17) | 0.0556 (8) | |
H5A | 0.7237 | 0.5364 | −0.2573 | 0.067* | |
C6 | 0.6373 (3) | 0.3680 (3) | −0.22217 (17) | 0.0552 (8) | |
H6A | 0.6900 | 0.3153 | −0.2540 | 0.066* | |
C7 | 0.5418 (3) | 0.3114 (3) | −0.17416 (16) | 0.0499 (7) | |
H7A | 0.5291 | 0.2220 | −0.1722 | 0.060* | |
C7A | 0.4662 (3) | 0.3948 (3) | −0.12934 (14) | 0.0395 (6) | |
O2 | 0.1674 (2) | 0.35466 (18) | 0.03153 (11) | 0.0526 (6) | |
C8 | 0.2114 (3) | 0.4601 (2) | 0.01174 (15) | 0.0393 (6) | |
C9 | 0.1580 (3) | 0.5860 (3) | 0.04366 (17) | 0.0456 (7) | |
H9A | 0.1140 | 0.6356 | 0.0036 | 0.055* | |
H9B | 0.2365 | 0.6362 | 0.0626 | 0.055* | |
Cl1 | 0.03617 (8) | 0.56222 (7) | 0.11742 (4) | 0.0546 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C2 | 0.0427 (15) | 0.0291 (13) | 0.0425 (15) | 0.0002 (11) | −0.0063 (12) | −0.0020 (12) |
O1 | 0.0514 (12) | 0.0303 (10) | 0.0497 (12) | 0.0004 (8) | 0.0019 (9) | −0.0016 (9) |
C3 | 0.0428 (16) | 0.0306 (13) | 0.0456 (16) | 0.0018 (11) | −0.0027 (13) | −0.0018 (12) |
C3A | 0.0404 (16) | 0.0355 (14) | 0.0422 (16) | 0.0013 (11) | −0.0085 (12) | 0.0007 (12) |
C4 | 0.056 (2) | 0.0460 (17) | 0.0511 (18) | −0.0035 (14) | 0.0006 (15) | 0.0045 (14) |
C5 | 0.052 (2) | 0.068 (2) | 0.0468 (18) | 0.0014 (15) | 0.0039 (15) | 0.0052 (16) |
C6 | 0.061 (2) | 0.064 (2) | 0.0412 (17) | 0.0169 (16) | −0.0033 (16) | −0.0043 (16) |
C7 | 0.0599 (19) | 0.0405 (16) | 0.0494 (17) | 0.0079 (14) | −0.0064 (15) | −0.0051 (14) |
C7A | 0.0426 (16) | 0.0373 (14) | 0.0387 (15) | 0.0014 (12) | −0.0059 (13) | −0.0007 (11) |
O2 | 0.0625 (14) | 0.0335 (10) | 0.0619 (14) | −0.0017 (9) | 0.0071 (10) | 0.0069 (10) |
C8 | 0.0419 (16) | 0.0326 (14) | 0.0432 (15) | 0.0005 (12) | −0.0102 (12) | 0.0014 (12) |
C9 | 0.0459 (17) | 0.0372 (15) | 0.0538 (18) | −0.0026 (12) | 0.0055 (13) | −0.0012 (13) |
Cl1 | 0.0539 (5) | 0.0548 (5) | 0.0549 (5) | 0.0004 (3) | 0.0070 (4) | −0.0025 (4) |
C2—C3 | 1.346 (4) | C5—H5A | 0.9300 |
C2—O1 | 1.385 (3) | C6—C7 | 1.376 (4) |
C2—C8 | 1.454 (4) | C6—H6A | 0.9300 |
O1—C7A | 1.366 (3) | C7—C7A | 1.374 (4) |
C3—C3A | 1.431 (4) | C7—H7A | 0.9300 |
C3—H2A | 0.9300 | O2—C8 | 1.216 (3) |
C3A—C7A | 1.389 (4) | C8—C9 | 1.504 (4) |
C3A—C4 | 1.391 (4) | C9—Cl1 | 1.766 (3) |
C4—C5 | 1.376 (4) | C9—H9A | 0.9700 |
C4—H4A | 0.9300 | C9—H9B | 0.9700 |
C5—C6 | 1.391 (5) | ||
C3—C2—O1 | 111.2 (2) | C7—C6—H6A | 119.0 |
C3—C2—C8 | 132.9 (2) | C5—C6—H6A | 119.0 |
O1—C2—C8 | 115.9 (2) | C7A—C7—C6 | 116.1 (3) |
C7A—O1—C2 | 105.79 (19) | C7A—C7—H7A | 122.0 |
C2—C3—C3A | 107.0 (2) | C6—C7—H7A | 122.0 |
C2—C3—H2A | 126.5 | O1—C7A—C7 | 125.6 (3) |
C3A—C3—H2A | 126.5 | O1—C7A—C3A | 110.6 (2) |
C7A—C3A—C4 | 118.8 (3) | C7—C7A—C3A | 123.8 (3) |
C7A—C3A—C3 | 105.4 (2) | O2—C8—C2 | 122.1 (2) |
C4—C3A—C3 | 135.7 (3) | O2—C8—C9 | 123.0 (3) |
C5—C4—C3A | 118.5 (3) | C2—C8—C9 | 114.9 (2) |
C5—C4—H4A | 120.7 | C8—C9—Cl1 | 112.41 (19) |
C3A—C4—H4A | 120.7 | C8—C9—H9A | 109.1 |
C4—C5—C6 | 120.8 (3) | Cl1—C9—H9A | 109.1 |
C4—C5—H5A | 119.6 | C8—C9—H9B | 109.1 |
C6—C5—H5A | 119.6 | Cl1—C9—H9B | 109.1 |
C7—C6—C5 | 122.0 (3) | H9A—C9—H9B | 107.9 |
C3—C2—O1—C7A | −0.2 (3) | C6—C7—C7A—O1 | −179.7 (2) |
C8—C2—O1—C7A | 179.8 (2) | C6—C7—C7A—C3A | −0.5 (4) |
O1—C2—C3—C3A | 0.1 (3) | C4—C3A—C7A—O1 | 179.6 (2) |
C8—C2—C3—C3A | −179.9 (3) | C3—C3A—C7A—O1 | −0.2 (3) |
C2—C3—C3A—C7A | 0.0 (3) | C4—C3A—C7A—C7 | 0.3 (4) |
C2—C3—C3A—C4 | −179.7 (3) | C3—C3A—C7A—C7 | −179.5 (3) |
C7A—C3A—C4—C5 | −0.4 (4) | C3—C2—C8—O2 | −178.4 (3) |
C3—C3A—C4—C5 | 179.3 (3) | O1—C2—C8—O2 | 1.6 (4) |
C3A—C4—C5—C6 | 0.7 (4) | C3—C2—C8—C9 | 2.1 (4) |
C4—C5—C6—C7 | −0.8 (5) | O1—C2—C8—C9 | −177.8 (2) |
C5—C6—C7—C7A | 0.7 (4) | O2—C8—C9—Cl1 | 4.7 (4) |
C2—O1—C7A—C7 | 179.5 (3) | C2—C8—C9—Cl1 | −175.83 (19) |
C2—O1—C7A—C3A | 0.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···O2i | 0.97 | 2.49 | 3.238 (3) | 134 |
Symmetry code: (i) −x+1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C10H7ClO2 |
Mr | 194.61 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 9.550 (2), 10.303 (2), 17.695 (4) |
V (Å3) | 1741.1 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.40 |
Crystal size (mm) | 0.34 × 0.14 × 0.08 |
Data collection | |
Diffractometer | Oxford Diffraction Sapphire CCD |
Absorption correction | Numerical (CrysAlis RED; Oxford Diffraction, 2000) |
Tmin, Tmax | 0.876, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16159, 2726, 1768 |
Rint | 0.074 |
(sin θ/λ)max (Å−1) | 0.732 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.086, 0.165, 1.24 |
No. of reflections | 2726 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.26 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2000), CrysAlis RED or CCD? (Oxford Diffraction, 2000), CrysAlis RED (Oxford Diffraction, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), CIFTAB in SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···O2i | 0.97 | 2.49 | 3.238 (3) | 133.6 |
Symmetry code: (i) −x+1/2, y+1/2, z. |
Aryl-2-chloroethanone and alkyl-2-chloroethanons are precursors of appropriate beta-amino-alfa-aryl (or alkyl) ethanols (Zaidlewicz et al., 2005; Tanis et al., 2006). These compounds containing the amino function exhibit the pharmacological activity. Many beta-amine arylethanol derivatives such as albuterol, isoproterenol, sotalol and terbutaline are well known beta-blockers or agonists and used in treatment of asthma, glaucoma, and cardiovascular disease (Gareth, 2001). All of them are nonselective beta-adrenoreceptor blocking agents comparable to propranolol (Weerawarna et al., 1991; Fothergill et al., 1977). Aromatic beta-aminoalcohols are also widely used as substrates in studies of the oxidation in liver by cytochrome P450 enzymes (Narimatsu et al., 2003). Furthermore, many compounds mentioned above show an anti-arrythmic properties. Developing methods of their enantioselective synthesis is of particular importance.
We have found that crystal structure of the title compound is not known yet, although it is a well known substrate for the synthesis of benzofuran derivatives revealing different biological activity. Therefore, the aim of the study was to determine its molecular and crystal structures.
The molecule is planar with the dihedral angle of 1.9 (2) o between the best planes of benzofuran ring system and C2—C8—O2—C9 group containing carbonyl moiety. The chloromethylene moiety is almost co-planar with the ring system: the C2—C8—C9—Cl1 torsion angle is -175.8 (2) o, with the r.m.s. deviation of Cl1 from that plane of 0.079 (4) Å. The carbonyl O2 is in syn position relative to benzofuran O1, the O1—C2—C8—O2 torsion angle is 1.6 (4) o. The chlorine atom is positioned in syn orientation relative to carbonyl O2, with the O2—C8—C9—Cl1 torsion angle 4.7 (4) o. The valence geometry of the investigated compound is similar to that found for unsubstitituted compounds at position 3. In the reported structure the O1—C2 distance is 1.385 (3) Å and it is similar to 1.385 Å found in 2-acetylbenzo(b)furan (Thiruvalluvar et al., 2003). However, the substituted compounds: [2-acetyl-3-(benzoylamino)-1-benzofuran (Ocak Ískeleli et al., 2005), 2-acetyl-3-aminobenzofuran (Bachechi et al., 1988), and 1-(3-amino-1-benzofuran-2-yl)-2-mesitylethanone (Arıcı et al., 2004) reveal somewhat longer bond distances of 1.403–1.411 Å.
The packing analysis revealed that each molecule forms a pair of intermolecular C—H···O contact of 3.238 (3) Å along the b axis involving its C9—H methylene group and carbonyl oxygen, the C9···O2 (0.5 - x, 1/2 + y, z). The packing interactions are completed by stacking of the ring systems of the molecules related by a centre of inversion (1 - x, 1 - y, -z). Interaction π···π between adjacent molecules is characterized by distance between centroids of the furane moieties of 3.785 (3) Å. In these dimers anti-parallel orientation of molecules occurs.