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access(R)-7-Bromo-2,3,4,4a-tetrahydro-1H-xanthen-1-one
aState Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
*Correspondence e-mail: xiaaibao1983@163.com
The title compound, C13H11BrO2, contains a tricyclic ring system with one chiral center which exhibits an R configuration. The is devoid of any classical hydrogen bonding.
Related literature
For related structures, see: Shi et al. (2004![[Shi, G.-F., Lu, R.-H., Yang, Y.-S., Li, C.-L., Yang, A.-M. & Cai, L.-X. (2004). Acta Cryst. E60, o878-o880.]](../../../../../../logos/arrows/e_arr.gif "Shi, G.-F., Lu, R.-H., Yang, Y.-S., Li, C.-L., Yang, A.-M. & Cai, L.-X. (2004). Acta Cryst. E60, o878-o880.")
); Ndjakou Lenta et al. (2007). Domino or cascade reactions allow, in principle, the formation of multiple new bonds and stereocenters in a one-pot system, see: Enders et al. (2007); Yu & Wang (2002).
![[Scheme 1]](pv2187scheme1.gif)
Experimental
Crystal data
|
Data collection: PROCESS-AUTO (Rigaku, 2006); cell PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 2007); 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); software used to prepare material for publication: CrystalStructure and PLATON (Spek, 2009).
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536809030244/pv2187sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536809030244/pv2187Isup2.hkl
A 1,4-dioxane (1 ml) solution of alicylic aldehyde (1 mmol) and cyclohex-2-enone (3.5 mmol) in the presence of (S)-1-methyl-2-(pyrrolidin-2-ylmethylthio)-1H-imidazole (0.3 mmol) as amine catalyst and benzoic acid (0.3 mmol) as additive was stirred at room temperature for 72 hrs. After completion of the reaction, the mixture was washed with water and extracted with ethyl acetate. The solvent was removed under reduced pressure and the residue was purified by silica gel using petroleum ether-aether (2:1)) as an Single crystals of the title compound were obtained by slow evaporation of an acetone solution.
An of (I) was determined by the Flack (1983) method without merging Friedel Pairs (1145) of reflections. H atoms were placed in calculated positions with in riding mode with C—H distances 0.93, 0.97 and 0.98 Å, for aryl, methylene and methine H-atoms; Uiso(H) = 1.2Ueq of the carrier atoms.
Data collection: PROCESS-AUTO (Rigaku, 2006); cell PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 2007); 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); software used to prepare material for publication: CrystalStructure (Rigaku/MSC and Rigaku, 2007) and PLATON Spek (2009).
![[Figure 1]](./pv2187fig1thm.gif) | Fig. 1. The asymmetric unit of the structure of the title compound, with the atomic labeling scheme. Displacement ellipsoids are drawn at the 40% probability level. |
![[Figure 2]](./pv2187fig2thm.gif) | Fig. 2. Unit cell packing of the title compound. |
| C13H11BrO2 | F(000) = 280.00 |
| Mr = 279.13 | Dx = 1.657 Mg m−3 |
| Monoclinic, P21 | Mo Kα radiation, λ = 0.71075 Å |
| Hall symbol: P 2yb | Cell parameters from 4299 reflections |
| a = 7.5419 (4) Å | θ = 3.2–27.4° |
| b = 6.9039 (3) Å | µ = 3.67 mm−1 |
| c = 10.7634 (5) Å | T = 296 K |
| β = 93.7110 (12)° | Chunk, yellow |
| V = 559.26 (5) Å3 | 0.40 × 0.37 × 0.26 mm |
| Z = 2 |
| Rigaku R-AXIS RAPID diffractometer | 1772 reflections with F2 > 2σ(F2) |
| Detector resolution: 10.00 pixels mm-1 | Rint = 0.036 |
| ω scans | θmax = 27.4° |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −9→9 |
| Tmin = 0.252, Tmax = 0.386 | k = −8→8 |
| 5496 measured reflections | l = −12→13 |
| 2525 independent reflections |
| Refinement on F2 | (Δ/σ)max = 0.001 |
| R[F2 > 2σ(F2)] = 0.033 | Δρmax = 0.64 e Å−3 |
| wR(F2) = 0.102 | Δρmin = −0.88 e Å−3 |
| S = 1.00 | Extinction correction: SHELXL97 (Sheldrick, 2008) |
| 2525 reflections | Extinction coefficient: 0.035 (3) |
| 147 parameters | Absolute structure: Flack (1983), 1145 Friedel pairs |
| H-atom parameters constrained | Absolute structure parameter: 0.01 (2) |
| w = 1/[σ2(Fo2) + (0.02P)2 + P] where P = (Fo2 + 2Fc2)/3 |
| C13H11BrO2 | V = 559.26 (5) Å3 |
| Mr = 279.13 | Z = 2 |
| Monoclinic, P21 | Mo Kα radiation |
| a = 7.5419 (4) Å | µ = 3.67 mm−1 |
| b = 6.9039 (3) Å | T = 296 K |
| c = 10.7634 (5) Å | 0.40 × 0.37 × 0.26 mm |
| β = 93.7110 (12)° |
| Rigaku R-AXIS RAPID diffractometer | 2525 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1772 reflections with F2 > 2σ(F2) |
| Tmin = 0.252, Tmax = 0.386 | Rint = 0.036 |
| 5496 measured reflections |
| R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
| wR(F2) = 0.102 | Δρmax = 0.64 e Å−3 |
| S = 1.00 | Δρmin = −0.88 e Å−3 |
| 2525 reflections | Absolute structure: Flack (1983), 1145 Friedel pairs |
| 147 parameters | Absolute structure parameter: 0.01 (2) |
Experimental. The structure of the title compound was confirmed by NMR and HRMS methods: 1HNMR (500 MHz, CDCl3): 7.33–7.31(m, 3H), 6.77–6.75(d, J=9.5 Hz,1H),5.00–4.97(m, 1H),2.62–2.58 (m, 1H), 2.51–2.46(m, 1H),2.42–2.35(m, 1H),2.13–2.07(m, 1H),2.04–1.96 (m, 1H), 1.75–1.65(m, 1H) p.p.m.; 13CNMR (125 MHz, CDCl3): 197.1, 154.8, 134.4, 131.8, 131.4, 129.9, 123.9, 117.8, 114.0, 74.8, 38.8, 29.6, 17.9 p.p.m.. HRMS: (EI+) m/z calcd for (C13H11BrO2)+ 277.9942, found 277.9949. |
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
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 > 2σ(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 | ||
| Br1 | 0.96613 (6) | 0.67049 (12) | 0.66752 (4) | 0.0633 (2) | |
| O1 | 0.5964 (5) | 0.6274 (8) | −0.0423 (3) | 0.0656 (16) | |
| O2 | 0.2944 (3) | 0.6625 (11) | 0.3348 (2) | 0.0473 (7) | |
| C1 | 0.4600 (6) | 0.6384 (11) | 0.0116 (4) | 0.0505 (16) | |
| C2 | 0.2803 (7) | 0.6187 (12) | −0.0570 (4) | 0.063 (2) | |
| C3 | 0.1314 (6) | 0.7222 (8) | 0.0028 (4) | 0.0557 (18) | |
| C4 | 0.1286 (5) | 0.6734 (16) | 0.1395 (3) | 0.0519 (11) | |
| C5 | 0.2999 (6) | 0.7335 (7) | 0.2089 (4) | 0.0440 (13) | |
| C6 | 0.4495 (4) | 0.6742 (14) | 0.4075 (3) | 0.0401 (8) | |
| C7 | 0.4396 (5) | 0.6820 (14) | 0.5352 (3) | 0.0434 (10) | |
| C8 | 0.5937 (5) | 0.6827 (14) | 0.6123 (3) | 0.0454 (11) | |
| C9 | 0.7562 (5) | 0.6759 (14) | 0.5602 (3) | 0.0412 (9) | |
| C10 | 0.7694 (5) | 0.6637 (16) | 0.4334 (3) | 0.0425 (9) | |
| C11 | 0.6136 (4) | 0.6623 (14) | 0.3548 (3) | 0.0393 (8) | |
| C12 | 0.6132 (5) | 0.6402 (11) | 0.2208 (4) | 0.0447 (15) | |
| C13 | 0.4640 (4) | 0.6636 (15) | 0.1494 (3) | 0.0413 (9) | |
| H5 | 0.3034 | 0.8753 | 0.2117 | 0.053* | |
| H7 | 0.3294 | 0.6868 | 0.5692 | 0.052* | |
| H8 | 0.5879 | 0.6877 | 0.6983 | 0.054* | |
| H10 | 0.8801 | 0.6564 | 0.4004 | 0.051* | |
| H12 | 0.7181 | 0.6095 | 0.1844 | 0.054* | |
| H21 | 0.2509 | 0.4820 | −0.0622 | 0.075* | |
| H22 | 0.2883 | 0.6705 | −0.1402 | 0.075* | |
| H31 | 0.0191 | 0.6841 | −0.0391 | 0.067* | |
| H32 | 0.1475 | 0.8609 | −0.0060 | 0.067* | |
| H41 | 0.0304 | 0.7408 | 0.1742 | 0.062* | |
| H42 | 0.1129 | 0.5347 | 0.1486 | 0.062* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0439 (2) | 0.0990 (4) | 0.0455 (2) | −0.0020 (5) | −0.00874 (17) | −0.0000 (5) |
| O1 | 0.062 (2) | 0.095 (5) | 0.0402 (16) | 0.016 (2) | 0.0060 (15) | −0.009 (2) |
| O2 | 0.0289 (13) | 0.070 (2) | 0.0433 (14) | 0.006 (3) | 0.0015 (10) | 0.005 (3) |
| C1 | 0.053 (2) | 0.056 (4) | 0.042 (2) | 0.012 (3) | −0.0026 (19) | −0.005 (2) |
| C2 | 0.063 (3) | 0.079 (7) | 0.043 (2) | 0.004 (3) | −0.015 (2) | −0.003 (3) |
| C3 | 0.044 (2) | 0.073 (5) | 0.048 (2) | 0.003 (2) | −0.012 (2) | 0.009 (2) |
| C4 | 0.035 (2) | 0.065 (3) | 0.056 (2) | −0.011 (5) | −0.0060 (17) | 0.009 (5) |
| C5 | 0.038 (2) | 0.054 (3) | 0.039 (2) | −0.000 (2) | −0.0029 (18) | 0.004 (2) |
| C6 | 0.0311 (18) | 0.045 (2) | 0.0437 (19) | −0.001 (3) | 0.0006 (14) | 0.007 (4) |
| C7 | 0.037 (2) | 0.053 (2) | 0.041 (2) | 0.000 (3) | 0.0100 (15) | 0.006 (3) |
| C8 | 0.047 (2) | 0.053 (3) | 0.0361 (19) | −0.002 (3) | 0.0038 (16) | −0.005 (3) |
| C9 | 0.0362 (19) | 0.047 (2) | 0.0400 (19) | −0.003 (4) | −0.0060 (14) | 0.005 (4) |
| C10 | 0.0340 (19) | 0.056 (2) | 0.0378 (18) | 0.001 (4) | 0.0050 (14) | −0.000 (4) |
| C11 | 0.0359 (19) | 0.044 (2) | 0.0376 (18) | −0.002 (3) | 0.0014 (14) | −0.005 (4) |
| C12 | 0.034 (2) | 0.058 (4) | 0.042 (2) | 0.006 (2) | 0.0051 (15) | 0.005 (3) |
| C13 | 0.040 (2) | 0.045 (2) | 0.0385 (19) | 0.001 (4) | 0.0004 (15) | 0.001 (4) |
| Br1—C9 | 1.899 (3) | C10—C11 | 1.403 (5) |
| O1—C1 | 1.215 (6) | C11—C12 | 1.450 (5) |
| O2—C5 | 1.444 (5) | C12—C13 | 1.330 (5) |
| O2—C6 | 1.367 (4) | C2—H21 | 0.970 |
| C1—C2 | 1.507 (7) | C2—H22 | 0.970 |
| C1—C13 | 1.492 (6) | C3—H31 | 0.970 |
| C2—C3 | 1.510 (8) | C3—H32 | 0.970 |
| C3—C4 | 1.511 (6) | C4—H41 | 0.970 |
| C4—C5 | 1.508 (6) | C4—H42 | 0.970 |
| C5—C13 | 1.509 (6) | C5—H5 | 0.980 |
| C6—C7 | 1.382 (5) | C7—H7 | 0.930 |
| C6—C11 | 1.397 (5) | C8—H8 | 0.930 |
| C7—C8 | 1.384 (5) | C10—H10 | 0.930 |
| C8—C9 | 1.381 (5) | C12—H12 | 0.930 |
| C9—C10 | 1.377 (5) | ||
| C5—O2—C6 | 116.2 (3) | C1—C2—H21 | 108.1 |
| O1—C1—C2 | 121.5 (4) | C1—C2—H22 | 108.1 |
| O1—C1—C13 | 121.2 (4) | C3—C2—H21 | 108.1 |
| C2—C1—C13 | 117.2 (4) | C3—C2—H22 | 108.1 |
| C1—C2—C3 | 114.7 (4) | H21—C2—H22 | 109.5 |
| C2—C3—C4 | 111.5 (5) | C2—C3—H31 | 109.0 |
| C3—C4—C5 | 110.8 (4) | C2—C3—H32 | 109.0 |
| O2—C5—C4 | 107.2 (4) | C4—C3—H31 | 109.0 |
| O2—C5—C13 | 111.3 (4) | C4—C3—H32 | 109.0 |
| C4—C5—C13 | 113.7 (4) | H31—C3—H32 | 109.5 |
| O2—C6—C7 | 118.2 (3) | C3—C4—H41 | 109.1 |
| O2—C6—C11 | 120.8 (3) | C3—C4—H42 | 109.1 |
| C7—C6—C11 | 120.8 (3) | C5—C4—H41 | 109.1 |
| C6—C7—C8 | 120.0 (3) | C5—C4—H42 | 109.1 |
| C7—C8—C9 | 119.2 (3) | H41—C4—H42 | 109.5 |
| Br1—C9—C8 | 118.7 (2) | O2—C5—H5 | 108.1 |
| Br1—C9—C10 | 119.4 (2) | C4—C5—H5 | 108.1 |
| C8—C9—C10 | 121.8 (3) | C13—C5—H5 | 108.1 |
| C9—C10—C11 | 119.1 (3) | C6—C7—H7 | 120.0 |
| C6—C11—C10 | 119.0 (3) | C8—C7—H7 | 120.0 |
| C6—C11—C12 | 117.7 (3) | C7—C8—H8 | 120.4 |
| C10—C11—C12 | 123.3 (3) | C9—C8—H8 | 120.4 |
| C11—C12—C13 | 120.6 (4) | C9—C10—H10 | 120.4 |
| C1—C13—C5 | 119.6 (3) | C11—C10—H10 | 120.4 |
| C1—C13—C12 | 121.5 (4) | C11—C12—H12 | 119.7 |
| C5—C13—C12 | 118.7 (3) | C13—C12—H12 | 119.7 |
| C5—O2—C6—C7 | 155.2 (7) | O2—C6—C7—C8 | 176.3 (8) |
| C5—O2—C6—C11 | −30.1 (12) | O2—C6—C11—C10 | −176.4 (9) |
| C6—O2—C5—C4 | 169.6 (7) | O2—C6—C11—C12 | 1.0 (13) |
| C6—O2—C5—C13 | 44.7 (8) | C7—C6—C11—C10 | −1.8 (14) |
| O1—C1—C2—C3 | −153.0 (6) | C7—C6—C11—C12 | 175.6 (8) |
| O1—C1—C13—C5 | 162.5 (7) | C11—C6—C7—C8 | 1.6 (14) |
| O1—C1—C13—C12 | −12.2 (13) | C6—C7—C8—C9 | 0.1 (12) |
| C2—C1—C13—C5 | −20.1 (11) | C7—C8—C9—Br1 | −178.5 (7) |
| C2—C1—C13—C12 | 165.2 (8) | C7—C8—C9—C10 | −1.6 (15) |
| C13—C1—C2—C3 | 29.6 (9) | Br1—C9—C10—C11 | 178.2 (7) |
| C1—C2—C3—C4 | −50.2 (8) | C8—C9—C10—C11 | 1.4 (15) |
| C2—C3—C4—C5 | 60.7 (8) | C9—C10—C11—C6 | 0.3 (11) |
| C3—C4—C5—O2 | −173.7 (6) | C9—C10—C11—C12 | −176.9 (9) |
| C3—C4—C5—C13 | −50.2 (9) | C6—C11—C12—C13 | 11.1 (13) |
| O2—C5—C13—C1 | 151.9 (7) | C10—C11—C12—C13 | −171.7 (9) |
| O2—C5—C13—C12 | −33.3 (10) | C11—C12—C13—C1 | −179.0 (8) |
| C4—C5—C13—C1 | 30.7 (10) | C11—C12—C13—C5 | 6.3 (12) |
| C4—C5—C13—C12 | −154.5 (8) |
Experimental details
| Crystal data | |
| Chemical formula | C13H11BrO2 |
| Mr | 279.13 |
| Crystal system, space group | Monoclinic, P21 |
| Temperature (K) | 296 |
| a, b, c (Å) | 7.5419 (4), 6.9039 (3), 10.7634 (5) |
| β (°) | 93.7110 (12) |
| V (Å3) | 559.26 (5) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 3.67 |
| Crystal size (mm) | 0.40 × 0.37 × 0.26 |
| Data collection | |
| Diffractometer | Rigaku R-AXIS RAPID diffractometer |
| Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
| Tmin, Tmax | 0.252, 0.386 |
| No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 5496, 2525, 1772 |
| Rint | 0.036 |
| (sin θ/λ)max (Å−1) | 0.648 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.102, 1.00 |
| No. of reflections | 2525 |
| No. of parameters | 147 |
| No. of restraints | ? |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.64, −0.88 |
| Absolute structure | Flack (1983), 1145 Friedel pairs |
| Absolute structure parameter | 0.01 (2) |
Computer programs: PROCESS-AUTO (Rigaku, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), CrystalStructure (Rigaku/MSC and Rigaku, 2007) and PLATON Spek (2009).
Acknowledgements
We acknowledge the help of Professor Jian-Ming Gu of Zhejiang University.
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
There has been growing interest in the study of domino or cascade reaction as it allows in principle the formation of multiple new bonds and stereocenters in one-pot system (Enders et al., 2007; Yu & Wang, 2002). Consequently, the title compound, (I), was synthesized as one of a series of oxa-Michael-aldol products under investigation. In this paper, the absolute configuration and crystal structure of (I) has been presented.
The title compound is shown in Fig. 1. One of the three fused rings in (I), the cyclohexanone ring (C1/C/C3/C4/C5/C13) adopts a distorted chair conformation while the ring O2/C5/C6/C11/C12/C13 is in a distorted half chair conformation. The bromophenyl ring (C6—C11/Br) is essentially planar as expected. The crystal structure is devoid of any classical hydrogen bonding. The crystal structures of closely related compound to (I) have been reported (Shi et al., 2004; Ndjakou Lenta et al., 2007).
ADDSYM in PLATON (Spek, 2009) suggested a pseudo mirror plane in the structure and P21/m as the alternate space group requiring all the atoms of the title compound to be coplanar with the atom, C2–C5 Sp2 hybridized which contravenes the true structure of the title compound.