Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805027881/hg6244sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805027881/hg6244Isup2.hkl |
CCDC reference: 287599
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C)= 0.003 Å
- R factor = 0.036
- wR factor = 0.096
- Data-to-parameter ratio = 17.3
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
To a mixture of spiro[2H-1,3-benzoxazine-2,1'-cyclohexan]-4(3H)-one (217 mg, 1 mmol), pyridine (95 mg, 1.2 mmol) and toluene (10 ml) was added 2-bromobutanoyl bromide (276 mg, 1.2 mmol) dropwise at 278–288 K. This mixture was stirred at the same temperature for 30 min and then at 298 K for 20 h. The reaction mixture was poured into water (10 ml). The organic layer was washed successively with saturated aqueous NaHCO3 (5 ml) and brine (5 ml), dried over anhydrous Na2SO4, and evaporated in vacuo. The residue was dissolved in 2-propanol (3 ml) at 323–325 K, gradually cooled to 283 K and stirred at the same temperature for 1 h. The resulting crystals were collected, washed with 2-propanol (3 ml) and dried at 313 K for 20 h to afford 300 g (82% yield) of (I). Colorless crystals were obtained from CH2Cl2/EtOH solution after it was left to stand for 4 d. M.p. 342–344 K. 1H NMR (500 MHz, CDCl3): δ 1.13 (t, J = 7.3 Hz), 1.29 (m, 1H), 1.53–2.41 (m, 10H), 4.98 (dd, 1H, J = 5.2 and 8.8 Hz), 7.01 (m, 1H), 7.11 (m, 1H), 7.55 (m, 1H), 7.93 (m, 1H). ESI–MS: m/z 366 ([M+1]+).
The methyl H atoms were constrained to an ideal geometry [C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C)] and were allowed to rotate freely about the C—C bonds. The other H atoms were placed in calculated positions, with Uiso(H) = 1.2Ueq(C) and C—H = 0.93–0.89 Å, and included in the final cycles of refinement in the riding-model approximation.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. The molecule of (I). Displacment ellipsoids are drawn at the 50% probability level for non-H atoms. | |
Fig. 2. A packing diagram, viewed approximately along the c axis. |
C17H20BrNO3 | F(000) = 1504 |
Mr = 366.25 | Dx = 1.502 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2yc | Cell parameters from 10907 reflections |
a = 10.9022 (7) Å | θ = 2.2–27.3° |
b = 17.636 (1) Å | µ = 2.55 mm−1 |
c = 16.8688 (8) Å | T = 295 K |
β = 92.795 (2)° | Block, colorless |
V = 3239.5 (3) Å3 | 0.35 × 0.3 × 0.2 mm |
Z = 8 |
Rigaku R-AXIS RAPID diffractometer | 2919 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.032 |
ω scans | θmax = 27°, θmin = 2.2° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −12→13 |
Tmin = 0.444, Tmax = 0.600 | k = −22→22 |
14339 measured reflections | l = −21→21 |
3481 independent reflections |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0515P)2 + 2.5231P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.036 | (Δ/σ)max < 0.001 |
wR(F2) = 0.096 | Δρmax = 0.42 e Å−3 |
S = 1.07 | Δρmin = −0.34 e Å−3 |
3481 reflections | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
201 parameters | Extinction coefficient: 0.0024 (3) |
0 restraints |
C17H20BrNO3 | V = 3239.5 (3) Å3 |
Mr = 366.25 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.9022 (7) Å | µ = 2.55 mm−1 |
b = 17.636 (1) Å | T = 295 K |
c = 16.8688 (8) Å | 0.35 × 0.3 × 0.2 mm |
β = 92.795 (2)° |
Rigaku R-AXIS RAPID diffractometer | 3481 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2919 reflections with I > 2σ(I) |
Tmin = 0.444, Tmax = 0.600 | Rint = 0.032 |
14339 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.42 e Å−3 |
3481 reflections | Δρmin = −0.34 e Å−3 |
201 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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 1.05354 (2) | 0.406841 (16) | 0.130812 (16) | 0.05562 (13) | |
O1 | 0.66552 (16) | 0.43308 (10) | 0.23033 (10) | 0.0483 (4) | |
O2 | 0.78140 (14) | 0.22409 (9) | 0.28519 (8) | 0.0382 (3) | |
O3 | 0.80639 (18) | 0.33062 (10) | 0.05914 (9) | 0.0507 (4) | |
N1 | 0.76922 (16) | 0.32507 (10) | 0.19416 (10) | 0.0342 (4) | |
C1 | 0.7222 (3) | 0.51648 (16) | 0.06483 (17) | 0.0566 (6) | |
H1A | 0.6692 | 0.4732 | 0.0579 | 0.085* | |
H1B | 0.7061 | 0.5516 | 0.0221 | 0.085* | |
H1C | 0.7071 | 0.5408 | 0.1143 | 0.085* | |
C2 | 0.8568 (2) | 0.49064 (14) | 0.06518 (15) | 0.0478 (6) | |
H2A | 0.8733 | 0.4664 | 0.0152 | 0.057* | |
H2B | 0.9111 | 0.5339 | 0.0723 | 0.057* | |
C3 | 0.8782 (2) | 0.43601 (13) | 0.13189 (14) | 0.0395 (5) | |
H3 | 0.8602 | 0.4597 | 0.1826 | 0.047* | |
C4 | 0.8130 (2) | 0.36052 (12) | 0.12250 (12) | 0.0372 (5) | |
C5 | 0.69373 (19) | 0.36834 (12) | 0.24585 (12) | 0.0363 (5) | |
C6 | 0.6526 (2) | 0.32994 (12) | 0.31973 (12) | 0.0360 (5) | |
C7 | 0.5709 (2) | 0.36567 (14) | 0.37405 (14) | 0.0441 (5) | |
H7 | 0.539 | 0.4133 | 0.3616 | 0.053* | |
C8 | 0.5386 (2) | 0.33066 (17) | 0.44458 (14) | 0.0519 (6) | |
H8 | 0.4863 | 0.3543 | 0.4788 | 0.062* | |
C9 | 0.5868 (3) | 0.26038 (18) | 0.46142 (14) | 0.0546 (7) | |
H9 | 0.5671 | 0.2358 | 0.5079 | 0.066* | |
C10 | 0.6671 (2) | 0.22446 (15) | 0.40845 (14) | 0.0483 (6) | |
H10 | 0.6993 | 0.177 | 0.4215 | 0.058* | |
C11 | 0.69903 (19) | 0.25917 (13) | 0.33668 (12) | 0.0364 (5) | |
C12 | 0.77030 (19) | 0.24070 (12) | 0.20183 (12) | 0.0328 (4) | |
C13 | 0.6542 (2) | 0.20568 (12) | 0.17195 (14) | 0.0382 (5) | |
H13A | 0.6397 | 0.2189 | 0.1165 | 0.046* | |
H13B | 0.5872 | 0.2264 | 0.2009 | 0.046* | |
C14 | 0.6539 (2) | 0.11970 (15) | 0.17999 (17) | 0.0521 (6) | |
H14A | 0.579 | 0.0992 | 0.155 | 0.063* | |
H14B | 0.6566 | 0.1058 | 0.2357 | 0.063* | |
C15 | 0.7681 (3) | 0.08554 (14) | 0.13956 (18) | 0.0572 (7) | |
H15A | 0.7705 | 0.0312 | 0.1481 | 0.069* | |
H15B | 0.7602 | 0.0946 | 0.0828 | 0.069* | |
C16 | 0.8831 (2) | 0.11942 (15) | 0.17170 (16) | 0.0491 (6) | |
H16A | 0.9515 | 0.0977 | 0.1448 | 0.059* | |
H16B | 0.8939 | 0.1071 | 0.2276 | 0.059* | |
C17 | 0.8844 (2) | 0.20540 (13) | 0.16174 (14) | 0.0411 (5) | |
H17A | 0.8816 | 0.2182 | 0.1058 | 0.049* | |
H17B | 0.9596 | 0.226 | 0.1862 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.04312 (17) | 0.0630 (2) | 0.0600 (2) | −0.00825 (11) | −0.00591 (12) | 0.00954 (12) |
O1 | 0.0569 (10) | 0.0356 (8) | 0.0527 (10) | 0.0031 (7) | 0.0071 (8) | 0.0038 (7) |
O2 | 0.0402 (8) | 0.0410 (8) | 0.0328 (7) | 0.0032 (6) | −0.0062 (6) | 0.0031 (6) |
O3 | 0.0744 (12) | 0.0448 (9) | 0.0322 (8) | −0.0114 (8) | −0.0040 (8) | −0.0020 (7) |
N1 | 0.0393 (9) | 0.0314 (9) | 0.0319 (8) | −0.0042 (7) | 0.0004 (7) | 0.0007 (7) |
C1 | 0.0631 (16) | 0.0456 (14) | 0.0602 (15) | 0.0056 (12) | −0.0072 (13) | 0.0119 (12) |
C2 | 0.0531 (14) | 0.0402 (13) | 0.0497 (13) | −0.0097 (11) | −0.0024 (11) | 0.0085 (10) |
C3 | 0.0407 (11) | 0.0393 (11) | 0.0384 (11) | −0.0083 (9) | 0.0012 (9) | 0.0018 (9) |
C4 | 0.0405 (11) | 0.0356 (11) | 0.0353 (11) | −0.0029 (9) | −0.0006 (9) | 0.0026 (9) |
C5 | 0.0369 (11) | 0.0347 (12) | 0.0370 (11) | −0.0055 (9) | −0.0008 (9) | −0.0023 (9) |
C6 | 0.0356 (10) | 0.0381 (11) | 0.0338 (10) | −0.0056 (8) | −0.0023 (9) | −0.0026 (8) |
C7 | 0.0432 (12) | 0.0463 (13) | 0.0427 (12) | −0.0033 (10) | 0.0007 (10) | −0.0049 (10) |
C8 | 0.0487 (14) | 0.0685 (17) | 0.0389 (12) | −0.0054 (12) | 0.0074 (11) | −0.0078 (12) |
C9 | 0.0584 (15) | 0.0738 (19) | 0.0317 (12) | −0.0087 (13) | 0.0022 (11) | 0.0063 (11) |
C10 | 0.0519 (14) | 0.0534 (14) | 0.0388 (12) | −0.0023 (11) | −0.0053 (11) | 0.0074 (10) |
C11 | 0.0353 (10) | 0.0412 (12) | 0.0321 (10) | −0.0052 (9) | −0.0047 (9) | −0.0010 (9) |
C12 | 0.0334 (10) | 0.0335 (11) | 0.0312 (10) | −0.0020 (8) | −0.0028 (8) | 0.0013 (8) |
C13 | 0.0341 (10) | 0.0356 (11) | 0.0440 (11) | −0.0011 (8) | −0.0063 (9) | −0.0032 (9) |
C14 | 0.0495 (14) | 0.0381 (12) | 0.0674 (16) | −0.0093 (11) | −0.0112 (12) | −0.0009 (11) |
C15 | 0.0698 (18) | 0.0359 (13) | 0.0643 (17) | 0.0048 (12) | −0.0131 (14) | −0.0058 (11) |
C16 | 0.0484 (13) | 0.0454 (13) | 0.0528 (14) | 0.0113 (11) | −0.0035 (11) | −0.0016 (11) |
C17 | 0.0356 (11) | 0.0430 (13) | 0.0446 (12) | 0.0003 (9) | 0.0006 (9) | −0.0031 (10) |
Br1—C3 | 1.981 (2) | C8—C9 | 1.371 (4) |
O1—C5 | 1.208 (3) | C8—H8 | 0.93 |
O2—C11 | 1.421 (3) | C9—C10 | 1.429 (4) |
O2—C12 | 1.436 (2) | C9—H9 | 0.93 |
O3—C4 | 1.191 (3) | C10—C11 | 1.415 (3) |
N1—C5 | 1.446 (3) | C10—H10 | 0.93 |
N1—C4 | 1.462 (3) | C12—C13 | 1.475 (3) |
N1—C12 | 1.494 (3) | C12—C17 | 1.573 (3) |
C1—C2 | 1.537 (4) | C13—C14 | 1.522 (3) |
C1—H1A | 0.96 | C13—H13A | 0.97 |
C1—H1B | 0.96 | C13—H13B | 0.97 |
C1—H1C | 0.96 | C14—C15 | 1.569 (4) |
C2—C3 | 1.491 (3) | C14—H14A | 0.97 |
C2—H2A | 0.97 | C14—H14B | 0.97 |
C2—H2B | 0.97 | C15—C16 | 1.468 (4) |
C3—C4 | 1.513 (3) | C15—H15A | 0.97 |
C3—H3 | 0.98 | C15—H15B | 0.97 |
C5—C6 | 1.506 (3) | C16—C17 | 1.526 (3) |
C6—C11 | 1.372 (3) | C16—H16A | 0.97 |
C6—C7 | 1.452 (3) | C16—H16B | 0.97 |
C7—C8 | 1.401 (3) | C17—H17A | 0.97 |
C7—H7 | 0.93 | C17—H17B | 0.97 |
C11—O2—C12 | 118.96 (16) | C11—C10—H10 | 119.1 |
C5—N1—C4 | 119.45 (17) | C9—C10—H10 | 119.1 |
C5—N1—C12 | 118.42 (16) | C6—C11—C10 | 117.9 (2) |
C4—N1—C12 | 119.75 (17) | C6—C11—O2 | 120.44 (18) |
C2—C1—H1A | 109.5 | C10—C11—O2 | 121.6 (2) |
C2—C1—H1B | 109.5 | O2—C12—C13 | 106.21 (17) |
H1A—C1—H1B | 109.5 | O2—C12—N1 | 106.74 (16) |
C2—C1—H1C | 109.5 | C13—C12—N1 | 112.62 (17) |
H1A—C1—H1C | 109.5 | O2—C12—C17 | 108.04 (16) |
H1B—C1—H1C | 109.5 | C13—C12—C17 | 111.77 (18) |
C3—C2—C1 | 108.0 (2) | N1—C12—C17 | 111.11 (17) |
C3—C2—H2A | 110.1 | C12—C13—C14 | 113.07 (19) |
C1—C2—H2A | 110.1 | C12—C13—H13A | 109 |
C3—C2—H2B | 110.1 | C14—C13—H13A | 109 |
C1—C2—H2B | 110.1 | C12—C13—H13B | 109 |
H2A—C2—H2B | 108.4 | C14—C13—H13B | 109 |
C2—C3—C4 | 115.74 (19) | H13A—C13—H13B | 107.8 |
C2—C3—Br1 | 106.02 (16) | C13—C14—C15 | 109.8 (2) |
C4—C3—Br1 | 102.64 (16) | C13—C14—H14A | 109.7 |
C2—C3—H3 | 110.7 | C15—C14—H14A | 109.7 |
C4—C3—H3 | 110.7 | C13—C14—H14B | 109.7 |
Br1—C3—H3 | 110.7 | C15—C14—H14B | 109.7 |
O3—C4—N1 | 123.0 (2) | H14A—C14—H14B | 108.2 |
O3—C4—C3 | 119.4 (2) | C16—C15—C14 | 111.4 (2) |
N1—C4—C3 | 117.40 (18) | C16—C15—H15A | 109.4 |
O1—C5—N1 | 120.98 (19) | C14—C15—H15A | 109.4 |
O1—C5—C6 | 121.4 (2) | C16—C15—H15B | 109.4 |
N1—C5—C6 | 117.59 (18) | C14—C15—H15B | 109.4 |
C11—C6—C7 | 119.7 (2) | H15A—C15—H15B | 108 |
C11—C6—C5 | 117.36 (19) | C15—C16—C17 | 112.1 (2) |
C7—C6—C5 | 122.9 (2) | C15—C16—H16A | 109.2 |
C8—C7—C6 | 122.1 (2) | C17—C16—H16A | 109.2 |
C8—C7—H7 | 118.9 | C15—C16—H16B | 109.2 |
C6—C7—H7 | 118.9 | C17—C16—H16B | 109.2 |
C9—C8—C7 | 117.7 (2) | H16A—C16—H16B | 107.9 |
C9—C8—H8 | 121.1 | C16—C17—C12 | 109.52 (19) |
C7—C8—H8 | 121.1 | C16—C17—H17A | 109.8 |
C8—C9—C10 | 120.8 (2) | C12—C17—H17A | 109.8 |
C8—C9—H9 | 119.6 | C16—C17—H17B | 109.8 |
C10—C9—H9 | 119.6 | C12—C17—H17B | 109.8 |
C11—C10—C9 | 121.8 (2) | H17A—C17—H17B | 108.2 |
Experimental details
Crystal data | |
Chemical formula | C17H20BrNO3 |
Mr | 366.25 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 295 |
a, b, c (Å) | 10.9022 (7), 17.636 (1), 16.8688 (8) |
β (°) | 92.795 (2) |
V (Å3) | 3239.5 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.55 |
Crystal size (mm) | 0.35 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.444, 0.600 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14339, 3481, 2919 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.096, 1.07 |
No. of reflections | 3481 |
No. of parameters | 201 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.34 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Br1—C3 | 1.981 (2) | N1—C5 | 1.446 (3) |
O1—C5 | 1.208 (3) | N1—C4 | 1.462 (3) |
O2—C11 | 1.421 (3) | N1—C12 | 1.494 (3) |
O3—C4 | 1.191 (3) | ||
C11—O2—C12 | 118.96 (16) | C4—C3—Br1 | 102.64 (16) |
C5—N1—C4 | 119.45 (17) | C12—C13—C14 | 113.07 (19) |
C5—N1—C12 | 118.42 (16) | C13—C14—C15 | 109.8 (2) |
C4—N1—C12 | 119.75 (17) | C15—C16—C17 | 112.1 (2) |
C2—C3—Br1 | 106.02 (16) | C16—C17—C12 | 109.52 (19) |
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As we previously reported, the title compound (I) can be used to synthesize trans β-lactam with high diastereoselectivity (Jian et al., 2005). The bulky, chair-like, six-membered ring (which one?) in the compound plays an important role in the efficient asymmetric induction, which leads to trans β-lactams exclusively.
Fig. 1 shows the structure of (I). The compound crystallizes in the monoclinic space group C2/c with eight symmetry-equivalent molecules per unit cell. Selected molecular parameters are listed in Table 1. The molecular dimensions may be considered normal (Table 1). There are no π–π stacking or other weak intermolecular interactions in (I), and the crystal packing (Fig. 2) is controlled by van der Waals forces.