(3R,6S,7R,8R,9S,9aS)-Meth­yl 6,9-diacet­oxy-7,8-diazido­perhydro-5-oxothia­zolo[3,2-a]azepine-3-carboxyl­ate

The absolute configuration has been determined for the bicyclic title compound, C₁₄H₁₇N₇O₇S, an inter­mediate in the synthesis of fixed chiral bis­(1,2-amino­hydr­oxy) compounds. In the crystal structure, the chair conformation of the seven-membered lactam ring exhibits four axial heteroatom substituents. The fused five-membered thia­zolidine ring prevents inversion of the seven-membered iduronic acid ring derivative to the thermodynamically more favourable chair conformation with four equatorial substitutions.

Key indicators

• Single-crystal X-ray study
• T = 193 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.023
• wR factor = 0.057
• Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    N5     -   N6      ..       9.06 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for    N8     -   N9      ..       8.28 su

Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       3.05 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.57 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C15
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         12
            C7  -N5  -N6  -N7   -178.20  1.10   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         31
            C8  -N8  -N9  -N10    18.00  0.00   1.555   1.555   1.555   1.555

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           26.21
           From the CIF: _reflns_number_total               3765
           Count of symmetry unique reflns         2163
           Completeness (_total/calc)            174.06%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1602
           Fraction of Friedel pairs measured     0.741
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   6 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
   4 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
   4 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: X-AREA (Stoe & Cie, 2003; cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: WinGX (Farrugia, 1999).

(3R,6S,7R,8R,9S,9aS)-Methyl 6,9-diacetoxy-7,8-diazidoperhydro- 5-oxothiazolo[3,2-a]azepine-3-carboxylate

Crystal data

C14H17N7O7S	F(000) = 888
Mr = 427.41	Dx = 1.514 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 26411 reflections
a = 8.6418 (4) Å	θ = 2–26°
b = 11.8765 (6) Å	µ = 0.23 mm^−1
c = 18.2755 (12) Å	T = 193 K
V = 1875.69 (18) Å^3	Plate, colourless
Z = 4	0.6 × 0.3 × 0.2 mm

Data collection

STOE IPDS-II diffractometer	Rint = 0.031
ω scans	θmax = 26.2°, θmin = 2.1°
27463 measured reflections	h = −10→10
3765 independent reflections	k = −14→14
3473 reflections with I > 2σ(I)	l = −22→22

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0405P)^2] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max = 0.001
R[F^2 > 2σ(F^2)] = 0.023	Δρmax = 0.18 e Å^−3
wR(F^2) = 0.057	Δρmin = −0.15 e Å^−3
S = 1.03	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
3765 reflections	Extinction coefficient: 0.0035 (8)
298 parameters	Absolute structure: Flack (1983), 1222 Friedel pairs
0 restraints	Absolute structure parameter: −0.02 (5)
H atoms treated by a mixture of independent and constrained refinement

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
S1	0.93658 (4)	0.78105 (3)	0.932394 (19)	0.02993 (9)
O1	0.72097 (14)	1.02073 (9)	0.84038 (6)	0.0422 (3)
O2	0.77775 (13)	1.07408 (9)	0.95457 (6)	0.0387 (3)
C2	0.79249 (18)	0.84106 (13)	0.99221 (7)	0.0303 (3)
O3	0.41574 (12)	0.87437 (10)	0.85470 (7)	0.0445 (3)
C3	0.67490 (16)	0.89081 (11)	0.93976 (8)	0.0274 (3)
O4	0.65824 (11)	0.79216 (9)	0.72530 (5)	0.0343 (2)
N4	0.65314 (13)	0.80757 (9)	0.88205 (6)	0.0257 (2)
O5	0.52800 (18)	0.79360 (19)	0.62079 (7)	0.0835 (6)
C5	0.52719 (16)	0.81647 (12)	0.83818 (8)	0.0297 (3)
N5	0.40742 (14)	0.59176 (12)	0.82761 (7)	0.0356 (3)
O6	0.69789 (10)	0.58136 (8)	0.92982 (5)	0.0274 (2)
N6	0.27310 (15)	0.61778 (11)	0.81167 (7)	0.0363 (3)
C6	0.52657 (15)	0.75261 (12)	0.76574 (8)	0.0302 (3)
O7	0.88241 (16)	0.45006 (11)	0.94269 (9)	0.0635 (4)
C7	0.52604 (15)	0.62456 (12)	0.77305 (8)	0.0286 (3)
N7	0.14630 (16)	0.63567 (16)	0.80547 (9)	0.0527 (4)
N8	0.78018 (14)	0.56883 (11)	0.73145 (7)	0.0349 (3)
C8	0.67658 (16)	0.56820 (12)	0.79691 (8)	0.0286 (3)
N9	0.86548 (15)	0.48517 (13)	0.72995 (7)	0.0415 (3)
C9	0.76799 (15)	0.61597 (11)	0.86206 (7)	0.0251 (3)
C9A	0.79345 (14)	0.74260 (11)	0.86352 (7)	0.0246 (3)
C10	0.72686 (15)	1.00102 (12)	0.90444 (8)	0.0295 (3)
N10	0.9475 (2)	0.41203 (16)	0.72358 (9)	0.0617 (4)
C11	0.8232 (2)	1.18381 (13)	0.92716 (12)	0.0501 (4)
H11A	0.8943	1.1744	0.8858	0.075*
H11B	0.8748	1.2262	0.9662	0.075*
H11C	0.7311	1.225	0.911	0.075*
C12	0.6455 (2)	0.80834 (14)	0.65298 (8)	0.0389 (4)
C13	0.7961 (2)	0.84535 (16)	0.62221 (9)	0.0455 (4)
H13A	0.8478	0.7812	0.599	0.068*
H13B	0.8615	0.8749	0.6616	0.068*
H13C	0.7784	0.9044	0.5857	0.068*
C14	0.76862 (17)	0.49567 (12)	0.96557 (8)	0.0326 (3)
C15	0.6889 (2)	0.46680 (14)	1.03475 (9)	0.0422 (4)
H15A	0.744	0.405	1.059	0.063*
H15B	0.5825	0.4435	1.0241	0.063*
H15C	0.6876	0.5328	1.067	0.063*
H21	0.8441 (19)	0.8953 (14)	1.0223 (9)	0.033 (4)*
H22	0.7459 (18)	0.7858 (14)	1.0232 (9)	0.030 (4)*
H3	0.5795 (19)	0.9057 (14)	0.9626 (9)	0.031 (4)*
H6	0.4343 (18)	0.7751 (13)	0.7410 (8)	0.026 (4)*
H7	0.4978 (18)	0.5928 (15)	0.7221 (9)	0.036 (4)*
H81	0.6503 (18)	0.4896 (14)	0.8091 (8)	0.025 (4)*
H9	0.8721 (18)	0.5806 (13)	0.8601 (8)	0.029 (4)*
H9A	0.8322 (17)	0.7637 (12)	0.8156 (8)	0.021 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.02403 (16)	0.03384 (18)	0.03193 (16)	−0.00140 (14)	−0.00650 (14)	−0.00153 (14)
O1	0.0503 (7)	0.0405 (6)	0.0359 (6)	−0.0046 (5)	−0.0076 (5)	0.0092 (5)
O2	0.0464 (6)	0.0277 (5)	0.0419 (6)	−0.0049 (5)	−0.0049 (5)	−0.0047 (4)
C2	0.0331 (8)	0.0327 (8)	0.0250 (6)	−0.0040 (6)	−0.0030 (6)	0.0005 (6)
O3	0.0287 (6)	0.0514 (7)	0.0534 (7)	0.0124 (5)	−0.0087 (5)	−0.0144 (5)
C3	0.0264 (7)	0.0295 (7)	0.0264 (7)	−0.0006 (5)	0.0022 (6)	−0.0028 (5)
O4	0.0280 (5)	0.0451 (6)	0.0297 (5)	−0.0064 (4)	−0.0024 (4)	0.0082 (5)
N4	0.0231 (5)	0.0257 (6)	0.0282 (6)	0.0001 (4)	−0.0023 (4)	−0.0028 (4)
O5	0.0585 (8)	0.1550 (17)	0.0369 (7)	−0.0463 (10)	−0.0175 (6)	0.0212 (9)
C5	0.0236 (6)	0.0303 (7)	0.0352 (7)	0.0005 (5)	−0.0019 (5)	0.0000 (6)
N5	0.0229 (6)	0.0473 (8)	0.0365 (6)	−0.0038 (5)	0.0019 (5)	0.0012 (6)
O6	0.0258 (5)	0.0289 (5)	0.0276 (5)	0.0015 (4)	0.0029 (4)	0.0038 (4)
N6	0.0294 (7)	0.0430 (8)	0.0364 (7)	−0.0074 (5)	0.0044 (5)	−0.0056 (6)
C6	0.0201 (6)	0.0388 (8)	0.0318 (7)	−0.0010 (5)	−0.0042 (5)	0.0008 (6)
O7	0.0610 (8)	0.0524 (8)	0.0771 (9)	0.0306 (6)	0.0298 (7)	0.0284 (7)
C7	0.0220 (6)	0.0371 (8)	0.0267 (6)	−0.0062 (5)	0.0013 (5)	−0.0028 (6)
N7	0.0256 (7)	0.0708 (11)	0.0616 (9)	0.0009 (7)	0.0050 (7)	−0.0050 (8)
N8	0.0313 (6)	0.0421 (7)	0.0313 (6)	0.0027 (6)	0.0054 (5)	−0.0080 (5)
C8	0.0262 (7)	0.0293 (7)	0.0305 (7)	−0.0016 (6)	0.0033 (5)	−0.0041 (6)
N9	0.0350 (7)	0.0543 (9)	0.0353 (7)	0.0035 (7)	0.0020 (6)	−0.0142 (6)
C9	0.0208 (6)	0.0292 (7)	0.0252 (6)	0.0000 (5)	0.0032 (5)	−0.0008 (5)
C9A	0.0199 (6)	0.0287 (7)	0.0252 (6)	−0.0012 (5)	−0.0004 (5)	0.0011 (5)
C10	0.0241 (6)	0.0296 (7)	0.0347 (7)	0.0018 (6)	−0.0017 (6)	−0.0016 (6)
N10	0.0537 (9)	0.0721 (11)	0.0593 (9)	0.0247 (9)	0.0065 (8)	−0.0198 (8)
C11	0.0485 (10)	0.0265 (7)	0.0754 (12)	−0.0043 (7)	−0.0123 (9)	0.0046 (8)
C12	0.0421 (8)	0.0453 (9)	0.0292 (7)	−0.0085 (7)	−0.0059 (6)	0.0042 (6)
C13	0.0463 (10)	0.0534 (10)	0.0369 (8)	−0.0097 (8)	0.0040 (7)	0.0048 (7)
C14	0.0325 (8)	0.0240 (7)	0.0412 (8)	0.0005 (6)	0.0007 (6)	0.0044 (6)
C15	0.0478 (9)	0.0384 (9)	0.0406 (8)	0.0041 (7)	0.0048 (7)	0.0105 (7)

Geometric parameters (Å, º)

S1—C2	1.8038 (15)	C6—H6	0.954 (16)
S1—C9A	1.8228 (13)	O7—C14	1.1980 (19)
O1—C10	1.1950 (18)	C7—C8	1.527 (2)
O2—C10	1.3362 (18)	C7—H7	1.034 (17)
O2—C11	1.450 (2)	N8—N9	1.2375 (19)
C2—C3	1.517 (2)	N8—C8	1.4941 (18)
C2—H21	0.957 (18)	C8—C9	1.5374 (19)
C2—H22	0.955 (17)	C8—H81	0.986 (16)
O3—C5	1.2213 (17)	N9—N10	1.127 (2)
C3—N4	1.4577 (17)	C9—C9A	1.5202 (19)
C3—C10	1.527 (2)	C9—H9	0.994 (16)
C3—H3	0.941 (17)	C9A—H9A	0.971 (15)
O4—C12	1.3401 (18)	C11—H11A	0.98
O4—C6	1.4359 (17)	C11—H11B	0.98
N4—C5	1.3559 (18)	C11—H11C	0.98
N4—C9A	1.4766 (17)	C12—C13	1.484 (2)
O5—C12	1.187 (2)	C13—H13A	0.98
C5—C6	1.526 (2)	C13—H13B	0.98
N5—N6	1.2361 (18)	C13—H13C	0.98
N5—C7	1.4822 (18)	C14—C15	1.480 (2)
O6—C14	1.3550 (17)	C15—H15A	0.98
O6—C9	1.4386 (16)	C15—H15B	0.98
N6—N7	1.1219 (19)	C15—H15C	0.98
C6—C7	1.527 (2)
C2—S1—C9A	92.81 (6)	C9—C8—H81	107.0 (9)
C10—O2—C11	115.84 (13)	N10—N9—N8	174.66 (19)
C3—C2—S1	103.49 (9)	O6—C9—C9A	109.17 (10)
C3—C2—H21	114.4 (10)	O6—C9—C8	110.18 (11)
S1—C2—H21	107.0 (10)	C9A—C9—C8	116.94 (11)
C3—C2—H22	111.1 (10)	O6—C9—H9	107.0 (9)
S1—C2—H22	112.2 (10)	C9A—C9—H9	106.7 (9)
H21—C2—H22	108.5 (13)	C8—C9—H9	106.3 (9)
N4—C3—C2	106.24 (11)	N4—C9A—C9	113.72 (10)
N4—C3—C10	108.27 (11)	N4—C9A—S1	105.54 (9)
C2—C3—C10	113.83 (12)	C9—C9A—S1	110.99 (9)
N4—C3—H3	109.6 (10)	N4—C9A—H9A	110.8 (9)
C2—C3—H3	112.3 (10)	C9—C9A—H9A	106.8 (9)
C10—C3—H3	106.5 (10)	S1—C9A—H9A	108.9 (8)
C12—O4—C6	119.31 (11)	O1—C10—O2	123.95 (14)
C5—N4—C3	118.59 (11)	O1—C10—C3	124.71 (13)
C5—N4—C9A	124.36 (11)	O2—C10—C3	111.33 (12)
C3—N4—C9A	114.48 (10)	O2—C11—H11A	109.5
O3—C5—N4	122.06 (13)	O2—C11—H11B	109.5
O3—C5—C6	119.44 (13)	H11A—C11—H11B	109.5
N4—C5—C6	118.50 (12)	O2—C11—H11C	109.5
N6—N5—C7	115.16 (13)	H11A—C11—H11C	109.5
C14—O6—C9	116.08 (10)	H11B—C11—H11C	109.5
N7—N6—N5	171.25 (17)	O5—C12—O4	122.56 (15)
O4—C6—C5	106.33 (11)	O5—C12—C13	127.31 (15)
O4—C6—C7	111.92 (11)	O4—C12—C13	110.13 (13)
C5—C6—C7	114.79 (12)	C12—C13—H13A	109.5
O4—C6—H6	109.1 (9)	C12—C13—H13B	109.5
C5—C6—H6	106.0 (9)	H13A—C13—H13B	109.5
C7—C6—H6	108.5 (10)	C12—C13—H13C	109.5
N5—C7—C8	106.37 (11)	H13A—C13—H13C	109.5
N5—C7—C6	108.83 (12)	H13B—C13—H13C	109.5
C8—C7—C6	117.34 (12)	O7—C14—O6	122.79 (14)
N5—C7—H7	110.3 (9)	O7—C14—C15	125.12 (14)
C8—C7—H7	107.4 (9)	O6—C14—C15	112.09 (12)
C6—C7—H7	106.6 (10)	C14—C15—H15A	109.5
N9—N8—C8	111.76 (13)	C14—C15—H15B	109.5
N8—C8—C7	106.25 (11)	H15A—C15—H15B	109.5
N8—C8—C9	108.08 (11)	C14—C15—H15C	109.5
C7—C8—C9	119.82 (12)	H15A—C15—H15C	109.5
N8—C8—H81	108.8 (9)	H15B—C15—H15C	109.5
C7—C8—H81	106.5 (9)
C9A—S1—C2—C3	−34.03 (10)	C6—C7—C8—C9	46.58 (18)
S1—C2—C3—N4	43.01 (12)	C8—N8—N9—N10	18E1 (10)
S1—C2—C3—C10	−76.03 (13)	C14—O6—C9—C9A	−128.22 (12)
C2—C3—N4—C5	163.42 (12)	C14—O6—C9—C8	102.08 (13)
C10—C3—N4—C5	−73.95 (15)	N8—C8—C9—O6	−159.52 (11)
C2—C3—N4—C9A	−33.98 (15)	C7—C8—C9—O6	78.73 (15)
C10—C3—N4—C9A	88.66 (13)	N8—C8—C9—C9A	75.08 (14)
C3—N4—C5—O3	−16.7 (2)	C7—C8—C9—C9A	−46.68 (17)
C9A—N4—C5—O3	−177.43 (13)	C5—N4—C9A—C9	−68.54 (16)
C3—N4—C5—C6	162.77 (12)	C3—N4—C9A—C9	130.00 (12)
C9A—N4—C5—C6	2.01 (19)	C5—N4—C9A—S1	169.57 (11)
C7—N5—N6—N7	−178.2 (11)	C3—N4—C9A—S1	8.11 (13)
C12—O4—C6—C5	−140.65 (13)	O6—C9—C9A—N4	−52.54 (14)
C12—O4—C6—C7	93.27 (16)	C8—C9—C9A—N4	73.36 (15)
O3—C5—C6—O4	120.95 (14)	O6—C9—C9A—S1	66.28 (12)
N4—C5—C6—O4	−58.52 (15)	C8—C9—C9A—S1	−167.82 (9)
O3—C5—C6—C7	−114.73 (15)	C2—S1—C9A—N4	15.90 (9)
N4—C5—C6—C7	65.81 (16)	C2—S1—C9A—C9	−107.74 (10)
N6—N5—C7—C8	−170.85 (13)	C11—O2—C10—O1	1.8 (2)
N6—N5—C7—C6	61.86 (16)	C11—O2—C10—C3	−177.17 (12)
O4—C6—C7—N5	168.32 (10)	N4—C3—C10—O1	13.18 (19)
C5—C6—C7—N5	47.00 (15)	C2—C3—C10—O1	131.07 (15)
O4—C6—C7—C8	47.55 (16)	N4—C3—C10—O2	−167.88 (11)
C5—C6—C7—C8	−73.77 (15)	C2—C3—C10—O2	−49.99 (16)
N9—N8—C8—C7	−147.21 (13)	C6—O4—C12—O5	1.7 (3)
N9—N8—C8—C9	83.00 (15)	C6—O4—C12—C13	−178.08 (13)
N5—C7—C8—N8	161.89 (11)	C9—O6—C14—O7	−0.4 (2)
C6—C7—C8—N8	−76.07 (15)	C9—O6—C14—C15	179.55 (12)
N5—C7—C8—C9	−75.46 (15)