(1aS,1bS,4aR,4bR,7aS,10R)-Methyl 1a,1b,4a,4b,7a,8,10,11-octa­hydro-8-oxo-bis­(2-methyl-1,3-oxazino)[6,5,4-cd][4,5,6-de]thia­zolo[3,2-a]azepine-10-carboxyl­ate

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.

Key indicators

• Single-crystal X-ray study
• T = 193 K
• Mean [sigma](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

---

Computing details

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,10R)-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

Crystal data

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) Å^3	Prism, colorless
Z = 4	0.39 × 0.18 × 0.12 mm

Data collection

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

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0325P)^2 + 0.0185P] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max = 0.001
R[F^2 > 2σ(F^2)] = 0.022	Δρmax = 0.15 e Å^−3
wR(F^2) = 0.052	Δρmin = −0.15 e Å^−3
S = 1.03	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)