The absolute configuration of the title tetracyclic bis-oxazine, C14H17N3O5S, has been determined. It is an unexpected product from the attempt to synthesize a new class of bis-oxazolines. The seven-membered lactam ring exhibits four axial (O and N) and one equatorial (S) substituents. The ortho-condensed and cis-configurated oxazine rings are positioned on opposite sides of the lactam ring.
Supporting information
CCDC reference: 298465
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.002 Å
- R factor = 0.022
- wR factor = 0.052
- Data-to-parameter ratio = 10.7
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.22 Ratio
Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for O8 - C8 .. 5.21 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for N9 - C8 .. 6.18 su
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 26.20
From the CIF: _reflns_number_total 2965
Count of symmetry unique reflns 1753
Completeness (_total/calc) 169.14%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1212
Fraction of Friedel pairs measured 0.691
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).
(1aS,1bS,4aR,4bR,7aS,10
R)-Methyl 1a,1 b,4a,4 b,7a,10,11-octahydro-8-oxo-bis(2-
methyl-1,3-oxazino)[6,5,4-cd][4,5,6-de]thiazolo[3,2-
a]azepine-3-carboxylate
top
Crystal data top
C14H17N3O5S | F(000) = 712 |
Mr = 339.37 | Dx = 1.52 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 13957 reflections |
a = 6.3486 (5) Å | θ = 1.5–26° |
b = 8.9324 (5) Å | µ = 0.25 mm−1 |
c = 26.1484 (19) Å | T = 193 K |
V = 1482.83 (18) Å3 | Prism, colorless |
Z = 4 | 0.39 × 0.18 × 0.12 mm |
Data collection top
Stoe IPDS-2 diffractometer | Rint = 0.029 |
ω scans | θmax = 26.2°, θmin = 1.6° |
14439 measured reflections | h = −7→7 |
2965 independent reflections | k = −10→11 |
2697 reflections with I > 2σ(I) | l = −32→32 |
Refinement top
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0325P)2 + 0.0185P] where P = (Fo2 + 2Fc2)/3 |
Least-squares matrix: full | (Δ/σ)max = 0.001 |
R[F2 > 2σ(F2)] = 0.022 | Δρmax = 0.15 e Å−3 |
wR(F2) = 0.052 | Δρmin = −0.15 e Å−3 |
S = 1.03 | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
2965 reflections | Extinction coefficient: 0.0075 (11) |
277 parameters | Absolute structure: Flack, (1983), 1219 Friedel Pairs |
0 restraints | Absolute structure parameter: 0.03 (6) |
All H-atom parameters refined | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1A | 0.4889 (2) | 0.43624 (15) | 0.13921 (5) | 0.0245 (3) | |
C1B | 0.4599 (2) | 0.54497 (16) | 0.18415 (5) | 0.0265 (3) | |
C3 | 0.7859 (2) | 0.54570 (15) | 0.23061 (5) | 0.0281 (3) | |
C4A | 0.7495 (2) | 0.72264 (14) | 0.16491 (5) | 0.0272 (3) | |
C4B | 0.5144 (2) | 0.70885 (15) | 0.17388 (5) | 0.0285 (3) | |
C6 | 0.4622 (2) | 0.76047 (17) | 0.08775 (5) | 0.0301 (3) | |
C7A | 0.8075 (2) | 0.66406 (15) | 0.11169 (5) | 0.0257 (3) | |
C8 | 0.8609 (2) | 0.49754 (15) | 0.11235 (5) | 0.0253 (3) | |
C10 | 0.7732 (2) | 0.24293 (17) | 0.13470 (5) | 0.0265 (3) | |
C11 | 0.6125 (2) | 0.17385 (16) | 0.17083 (6) | 0.0307 (3) | |
C12 | 0.9010 (3) | 0.46565 (19) | 0.27187 (6) | 0.0354 (3) | |
C13 | 0.3470 (3) | 0.8159 (2) | 0.04195 (7) | 0.0432 (4) | |
C14 | 0.7890 (2) | 0.15315 (16) | 0.08549 (6) | 0.0337 (3) | |
C15 | 0.7753 (4) | 0.1542 (3) | −0.00438 (8) | 0.0560 (5) | |
N4 | 0.8737 (2) | 0.64603 (12) | 0.20380 (4) | 0.0287 (3) | |
N5 | 0.38804 (19) | 0.77166 (13) | 0.13264 (4) | 0.0316 (3) | |
N9 | 0.71188 (17) | 0.39911 (12) | 0.12815 (4) | 0.0243 (2) | |
O2 | 0.58207 (14) | 0.49415 (10) | 0.22740 (3) | 0.0282 (2) | |
O7 | 0.64687 (16) | 0.69357 (11) | 0.07369 (4) | 0.0302 (2) | |
O8 | 1.03879 (15) | 0.45673 (12) | 0.10183 (4) | 0.0310 (2) | |
O10 | 0.8293 (3) | 0.02206 (13) | 0.08541 (5) | 0.0593 (4) | |
O11 | 0.75765 (17) | 0.23427 (12) | 0.04368 (4) | 0.0391 (3) | |
S1 | 0.36550 (5) | 0.25550 (4) | 0.151072 (14) | 0.03186 (10) | |
H1A | 0.420 (2) | 0.4800 (15) | 0.1091 (5) | 0.018 (3)* | |
H1B | 0.311 (3) | 0.5357 (17) | 0.1941 (6) | 0.026 (4)* | |
H4A | 0.791 (3) | 0.8279 (18) | 0.1659 (6) | 0.034 (4)* | |
H4B | 0.482 (2) | 0.7665 (17) | 0.2045 (6) | 0.024 (3)* | |
H7A | 0.930 (2) | 0.7123 (16) | 0.1003 (5) | 0.024 (4)* | |
H10 | 0.907 (2) | 0.2383 (17) | 0.1490 (6) | 0.026 (4)* | |
H11A | 0.603 (3) | 0.0631 (19) | 0.1669 (6) | 0.037 (4)* | |
H11B | 0.643 (2) | 0.1975 (16) | 0.2067 (6) | 0.024 (3)* | |
H12A | 0.918 (3) | 0.359 (3) | 0.2633 (8) | 0.057 (6)* | |
H12B | 0.816 (3) | 0.466 (2) | 0.3039 (8) | 0.059 (6)* | |
H12C | 1.035 (3) | 0.519 (2) | 0.2782 (7) | 0.053 (5)* | |
H13A | 0.320 (4) | 0.739 (3) | 0.0208 (9) | 0.076 (7)* | |
H13B | 0.421 (4) | 0.886 (3) | 0.0236 (9) | 0.073 (7)* | |
H13C | 0.219 (4) | 0.864 (2) | 0.0517 (8) | 0.062 (6)* | |
H15A | 0.664 (4) | 0.084 (3) | −0.0076 (8) | 0.071 (7)* | |
H15B | 0.913 (4) | 0.095 (3) | −0.0049 (9) | 0.076 (8)* | |
H15C | 0.775 (4) | 0.234 (3) | −0.0329 (9) | 0.075 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.0173 (6) | 0.0272 (7) | 0.0289 (7) | 0.0013 (5) | 0.0006 (5) | 0.0015 (5) |
C1B | 0.0244 (7) | 0.0314 (7) | 0.0237 (7) | 0.0047 (6) | 0.0002 (5) | 0.0018 (6) |
C3 | 0.0313 (7) | 0.0255 (7) | 0.0275 (7) | 0.0016 (6) | −0.0015 (6) | −0.0038 (6) |
C4A | 0.0325 (8) | 0.0215 (7) | 0.0277 (7) | 0.0004 (6) | −0.0033 (5) | −0.0001 (5) |
C4B | 0.0314 (7) | 0.0296 (8) | 0.0245 (7) | 0.0061 (6) | 0.0022 (6) | −0.0009 (6) |
C6 | 0.0293 (7) | 0.0279 (7) | 0.0331 (7) | 0.0008 (6) | −0.0021 (6) | 0.0048 (6) |
C7A | 0.0229 (7) | 0.0262 (7) | 0.0279 (7) | −0.0021 (5) | 0.0002 (6) | 0.0037 (5) |
C8 | 0.0235 (6) | 0.0290 (6) | 0.0233 (6) | −0.0004 (6) | −0.0016 (6) | −0.0016 (5) |
C10 | 0.0226 (6) | 0.0251 (6) | 0.0317 (7) | 0.0023 (6) | −0.0012 (5) | 0.0009 (6) |
C11 | 0.0300 (8) | 0.0286 (7) | 0.0334 (8) | 0.0004 (6) | 0.0021 (6) | 0.0041 (6) |
C12 | 0.0389 (9) | 0.0348 (8) | 0.0326 (8) | 0.0002 (7) | −0.0079 (7) | 0.0032 (6) |
C13 | 0.0390 (9) | 0.0525 (10) | 0.0381 (9) | 0.0036 (9) | −0.0059 (8) | 0.0132 (8) |
C14 | 0.0325 (7) | 0.0303 (8) | 0.0382 (8) | −0.0032 (6) | 0.0056 (6) | −0.0027 (6) |
C15 | 0.0708 (14) | 0.0625 (13) | 0.0345 (10) | −0.0158 (13) | 0.0030 (9) | −0.0169 (9) |
N4 | 0.0320 (6) | 0.0261 (6) | 0.0280 (6) | −0.0006 (5) | −0.0045 (5) | −0.0007 (4) |
N5 | 0.0313 (6) | 0.0315 (6) | 0.0320 (6) | 0.0049 (5) | 0.0004 (5) | 0.0053 (5) |
N9 | 0.0199 (5) | 0.0241 (5) | 0.0291 (6) | 0.0003 (4) | 0.0026 (5) | −0.0003 (5) |
O2 | 0.0295 (5) | 0.0304 (5) | 0.0248 (5) | 0.0013 (4) | −0.0004 (4) | 0.0041 (4) |
O7 | 0.0303 (5) | 0.0344 (5) | 0.0259 (5) | 0.0031 (4) | −0.0010 (4) | 0.0030 (4) |
O8 | 0.0215 (5) | 0.0334 (5) | 0.0383 (6) | 0.0016 (4) | 0.0046 (4) | −0.0009 (4) |
O10 | 0.0916 (11) | 0.0272 (6) | 0.0591 (8) | 0.0075 (6) | 0.0183 (8) | −0.0056 (5) |
O11 | 0.0475 (6) | 0.0406 (6) | 0.0291 (5) | −0.0023 (6) | −0.0022 (4) | −0.0062 (5) |
S1 | 0.02373 (15) | 0.02887 (16) | 0.04296 (19) | −0.00326 (16) | 0.00116 (15) | 0.00499 (15) |
Geometric parameters (Å, º) top
C1A—N9 | 1.4825 (17) | C8—O8 | 1.2182 (17) |
C1A—C1B | 1.5357 (19) | C8—N9 | 1.3560 (18) |
C1A—S1 | 1.8211 (14) | C10—N9 | 1.4585 (19) |
C1A—H1A | 0.982 (14) | C10—C14 | 1.519 (2) |
C1B—O2 | 1.4443 (16) | C10—C11 | 1.521 (2) |
C1B—C4B | 1.528 (2) | C10—H10 | 0.926 (15) |
C1B—H1B | 0.986 (16) | C11—S1 | 1.8050 (16) |
C3—N4 | 1.2672 (18) | C11—H11A | 0.996 (16) |
C3—O2 | 1.3759 (17) | C11—H11B | 0.981 (15) |
C3—C12 | 1.486 (2) | C12—H12A | 0.99 (2) |
C4A—N4 | 1.4575 (18) | C12—H12B | 1.00 (2) |
C4A—C4B | 1.516 (2) | C12—H12C | 0.99 (2) |
C4A—C7A | 1.5318 (19) | C13—H13A | 0.89 (3) |
C4A—H4A | 0.976 (16) | C13—H13B | 0.92 (3) |
C4B—N5 | 1.4563 (18) | C13—H13C | 0.95 (2) |
C4B—H4B | 0.973 (15) | C14—O10 | 1.1985 (19) |
C6—N5 | 1.2686 (18) | C14—O11 | 1.3265 (19) |
C6—O7 | 1.3665 (17) | C15—O11 | 1.450 (2) |
C6—C13 | 1.488 (2) | C15—H15A | 0.95 (3) |
C7A—O7 | 1.4480 (17) | C15—H15B | 1.02 (3) |
C7A—C8 | 1.5256 (19) | C15—H15C | 1.03 (2) |
C7A—H7A | 0.937 (15) | | |
| | | |
N9—C1A—C1B | 113.90 (11) | C14—C10—C11 | 110.85 (12) |
N9—C1A—S1 | 104.22 (9) | N9—C10—H10 | 109.5 (9) |
C1B—C1A—S1 | 112.26 (9) | C14—C10—H10 | 105.0 (9) |
N9—C1A—H1A | 111.1 (8) | C11—C10—H10 | 110.2 (9) |
C1B—C1A—H1A | 107.9 (8) | C10—C11—S1 | 103.95 (9) |
S1—C1A—H1A | 107.3 (8) | C10—C11—H11A | 112.2 (10) |
O2—C1B—C4B | 108.50 (11) | S1—C11—H11A | 108.7 (10) |
O2—C1B—C1A | 109.64 (11) | C10—C11—H11B | 111.9 (9) |
C4B—C1B—C1A | 116.38 (11) | S1—C11—H11B | 111.1 (9) |
O2—C1B—H1B | 106.4 (9) | H11A—C11—H11B | 108.9 (12) |
C4B—C1B—H1B | 110.1 (9) | C3—C12—H12A | 110.9 (12) |
C1A—C1B—H1B | 105.3 (9) | C3—C12—H12B | 110.1 (12) |
N4—C3—O2 | 128.07 (13) | H12A—C12—H12B | 104.6 (16) |
N4—C3—C12 | 121.69 (14) | C3—C12—H12C | 108.1 (11) |
O2—C3—C12 | 110.24 (12) | H12A—C12—H12C | 114.1 (16) |
N4—C4A—C4B | 112.75 (12) | H12B—C12—H12C | 109.0 (17) |
N4—C4A—C7A | 110.08 (11) | C6—C13—H13A | 109.6 (15) |
C4B—C4A—C7A | 110.47 (11) | C6—C13—H13B | 113.5 (15) |
N4—C4A—H4A | 106.8 (10) | H13A—C13—H13B | 107 (2) |
C4B—C4A—H4A | 109.7 (10) | C6—C13—H13C | 110.7 (13) |
C7A—C4A—H4A | 106.8 (10) | H13A—C13—H13C | 110 (2) |
N5—C4B—C4A | 113.36 (11) | H13B—C13—H13C | 105.3 (19) |
N5—C4B—C1B | 112.00 (12) | O10—C14—O11 | 124.35 (15) |
C4A—C4B—C1B | 109.13 (12) | O10—C14—C10 | 122.08 (15) |
N5—C4B—H4B | 106.9 (8) | O11—C14—C10 | 113.56 (12) |
C4A—C4B—H4B | 106.9 (8) | O11—C15—H15A | 110.3 (14) |
C1B—C4B—H4B | 108.3 (9) | O11—C15—H15B | 109.3 (13) |
N5—C6—O7 | 127.00 (12) | H15A—C15—H15B | 107 (2) |
N5—C6—C13 | 122.43 (14) | O11—C15—H15C | 106.5 (13) |
O7—C6—C13 | 110.51 (13) | H15A—C15—H15C | 113.2 (18) |
O7—C7A—C8 | 109.99 (11) | H15B—C15—H15C | 110.4 (19) |
O7—C7A—C4A | 113.07 (11) | C3—N4—C4A | 118.68 (13) |
C8—C7A—C4A | 112.09 (11) | C6—N5—C4B | 116.77 (12) |
O7—C7A—H7A | 106.4 (9) | C8—N9—C10 | 118.01 (11) |
C8—C7A—H7A | 105.5 (9) | C8—N9—C1A | 125.49 (11) |
C4A—C7A—H7A | 109.3 (9) | C10—N9—C1A | 116.50 (10) |
O8—C8—N9 | 121.44 (12) | C3—O2—C1B | 116.59 (10) |
O8—C8—C7A | 119.68 (13) | C6—O7—C7A | 119.95 (10) |
N9—C8—C7A | 118.72 (12) | C14—O11—C15 | 115.67 (14) |
N9—C10—C14 | 115.02 (11) | C11—S1—C1A | 91.91 (6) |
N9—C10—C11 | 106.36 (11) | | |
| | | |
N9—C1A—C1B—O2 | −48.87 (16) | O7—C6—N5—C4B | 1.1 (2) |
S1—C1A—C1B—O2 | 69.28 (12) | C13—C6—N5—C4B | 178.24 (15) |
N9—C1A—C1B—C4B | 74.71 (15) | C4A—C4B—N5—C6 | 33.86 (18) |
S1—C1A—C1B—C4B | −167.14 (10) | C1B—C4B—N5—C6 | −90.17 (15) |
N4—C4A—C4B—N5 | −174.12 (11) | O8—C8—N9—C10 | 2.99 (19) |
C7A—C4A—C4B—N5 | −50.49 (16) | C7A—C8—N9—C10 | −172.45 (12) |
N4—C4A—C4B—C1B | −48.54 (15) | O8—C8—N9—C1A | −176.62 (12) |
C7A—C4A—C4B—C1B | 75.09 (14) | C7A—C8—N9—C1A | 7.94 (19) |
O2—C1B—C4B—N5 | −176.49 (10) | C14—C10—N9—C8 | −78.45 (15) |
C1A—C1B—C4B—N5 | 59.34 (16) | C11—C10—N9—C8 | 158.43 (12) |
O2—C1B—C4B—C4A | 57.16 (14) | C14—C10—N9—C1A | 101.19 (14) |
C1A—C1B—C4B—C4A | −67.01 (15) | C11—C10—N9—C1A | −21.93 (15) |
N4—C4A—C7A—O7 | 159.77 (11) | C1B—C1A—N9—C8 | −63.79 (17) |
C4B—C4A—C7A—O7 | 34.60 (15) | S1—C1A—N9—C8 | 173.54 (10) |
N4—C4A—C7A—C8 | 34.75 (15) | C1B—C1A—N9—C10 | 116.60 (13) |
C4B—C4A—C7A—C8 | −90.42 (14) | S1—C1A—N9—C10 | −6.07 (13) |
O7—C7A—C8—O8 | 117.99 (13) | N4—C3—O2—C1B | 9.05 (19) |
C4A—C7A—C8—O8 | −115.31 (14) | C12—C3—O2—C1B | −170.96 (12) |
O7—C7A—C8—N9 | −66.49 (15) | C4B—C1B—O2—C3 | −38.40 (14) |
C4A—C7A—C8—N9 | 60.21 (16) | C1A—C1B—O2—C3 | 89.69 (13) |
N9—C10—C11—S1 | 39.35 (12) | N5—C6—O7—C7A | −17.6 (2) |
C14—C10—C11—S1 | −86.35 (12) | C13—C6—O7—C7A | 165.04 (13) |
N9—C10—C14—O10 | −176.84 (15) | C8—C7A—O7—C6 | 122.99 (13) |
C11—C10—C14—O10 | −56.1 (2) | C4A—C7A—O7—C6 | −3.16 (17) |
N9—C10—C14—O11 | 4.24 (18) | O10—C14—O11—C15 | −0.1 (2) |
C11—C10—C14—O11 | 124.93 (14) | C10—C14—O11—C15 | 178.80 (15) |
O2—C3—N4—C4A | 1.6 (2) | C10—C11—S1—C1A | −38.23 (10) |
C12—C3—N4—C4A | −178.38 (13) | N9—C1A—S1—C11 | 25.78 (9) |
C4B—C4A—N4—C3 | 19.64 (17) | C1B—C1A—S1—C11 | −97.95 (10) |
C7A—C4A—N4—C3 | −104.21 (14) | | |