endo-4-Phenyl-7-n-propyl-2-oxa-6-thia-3-aza­bi­cyclo­[3.2.0^1,4]­hept-3-ene 6,6-dioxide

Two independent mol­ecules of the title compound, C₁₃H₁₅NO₃S, containing the novel endo-thia­bi­cyclo­[3.2.0^1,4]­hept-3-ene ring, crystallize in a triclinic cell. Both fused rings in the bicyclic system are non-planar, with the five-membered C₃NO rings adopting envelope conformations.

Key indicators

• Single-crystal X-ray study
• T = 130 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.057
• wR factor = 0.121
• Data-to-parameter ratio = 10.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



THETM_01  Alert A The value of sine(theta_max)/wavelength is less than 0.550
          Calculated sin(theta_max)/wavelength =    0.5384

Author response: The actual value of 0.5384 is not significantly less than the expected value. It corresponds to a collection algorithm error for a triclinic cell giving a slightly incomplete (94%) but more than adequate data set. The data/parameter ratio is 10.

 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           22.50
         From the CIF: _reflns_number_total               3157
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         3355
         Completeness (_total/calc)             94.10%
          Alert C: < 95% complete

REFNR_01  Alert C Ratio of reflections to parameters is < 10 for a
          centrosymmetric structure
          sine(theta)/lambda                0.5384
          Proportion of unique data used    1.0000
          Ratio reflections to parameters   9.9905

PLAT_320  Alert C Check Hybridisation of  C(21)  in main residue          ?


 1 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

S1. Comment

The title compound, (I), was prepared as part of a study of the use of carnivore odours in mammal pest control. It is closely related to two previously reported structures: exo-7-aza-6-oxa-4-n-propyl-3-thiabicyclo[5.4.1^1,7.1^2,5]undecane 3,3-dioxide (Woolhouse et al., 1993) and the exo-stereoisomer exo-7-phenyl-3-n-propyl-5-oxa-2-thia-6-azabicyclo[3.2.0^1,4]hept-6-ene 2,2-dioxide (Gainsford & Woolhouse, 2002), being formed from a thiete sulfone (Gainsford & Woolhouse, 1994). The crystal structure of (I) consists of two nearly identical independent molecules (one of these is shown in Fig. 1) and their centrosymmetrically related molecules. Most intermolecular interactions are between each independent molecule and their centrosymmetrically related molecules, e.g. C113—H113···O122ⁱ, with C113···O122ⁱ = 3.303 (5) Å [symmetry code: (i) 1 − x, 1 − y, 1 − z], making two infinite chains along the b crystal axis. The Cj1—Cj4—Oj5—Nj6—Cj7 five-membered rings, where j = 1 or 2, have envelope conformations, with flap atoms Cj4 at distances of 0.222 (7) and 0.185 (8) Å from the four-atom plane for p = 1 and 2, respectively. The four-membered C₃S fused rings are not planar, with mean deviations from the mean plane of 0.0787 (3) and 0.0487 (3) Å for j = 1 and 2, respectively. The angles between the mean planes through the two rings are identical at 66.0 (3)°. This is unlike the exo-molecule where the fused four- and five-membered rings are planar (Gainsford & Woolhouse, 2002). The pendant planar phenyl rings Cj8–Cj13 are twisted by 5.2 (2) and 6.9 (3)° for j = 1 and 2, respectively, from their bound five-membered ring. The same comments about the oxygen Oj5 binding in fused-ring systems constructed by cycloaddition apply (see Gainsford & Woolhouse, 2002).

S2. Experimental

Compound (I) was prepared as described previously by Gainsford & Woolhouse (2002). Crystals were grown from an ethyl acetate–hexane mixture.

S3. Refinement

All H atoms were constrained to ride on their parent atom, with a U_iso value 1.2 times the U_eq value of the parent atom.

Computing details

Data collection: SHELXTL (Siemens, 1983); cell refinement: SHELXTL; data reduction: SHELXTL; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 in WinGX (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 1990).

Figures

Fig. 1. The molecular structure of one of the two independent molecules of (I). Displacement ellipsoids are drawn at the 50% probability level. H atoms have arbitrary radii.

(I)

Crystal data

C13H15NO3S	Z = 4
Mr = 265.32	F(000) = 560
Triclinic, P1	Dx = 1.374 Mg m^−3
a = 5.282 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.241 (3) Å	Cell parameters from 24 reflections
c = 22.588 (6) Å	θ = 5.8–14.6°
α = 79.65 (2)°	µ = 0.25 mm^−1
β = 89.67 (4)°	T = 130 K
γ = 76.58 (3)°	Needle, colourless
V = 1282.4 (11) Å^3	0.84 × 0.32 × 0.18 mm

Data collection

Siemens/Nicolet R3m four-circle diffractometer	Rint = 0.035
Radiation source: fine-focus sealed tube	θmax = 22.5°, θmin = 2.3°
Graphite monochromator	h = 0→5
ω scans	k = −11→11
3583 measured reflections	l = −24→24
3157 independent reflections	3 standard reflections every 97 reflections
2378 reflections with I > 2σ(I)	intensity decay: 0.0%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0097P)^2 + 3.7137P] where P = (Fo^2 + 2Fc^2)/3
S = 1.16	(Δ/σ)max < 0.001
3157 reflections	Δρmax = 0.31 e Å^−3
316 parameters	Δρmin = −0.29 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0068 (8)

Special details

Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections. A standard 1.0 mm diameter collimator was used.

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.

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 > σ(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. An extinction paramter was refined.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S12	0.2613 (2)	0.69088 (12)	0.46531 (6)	0.0227 (4)
S22	0.2616 (3)	0.33210 (12)	−0.02285 (6)	0.0252 (4)
O121	−0.0047 (7)	0.6840 (3)	0.46455 (16)	0.0309 (9)
O122	0.4493 (6)	0.6030 (3)	0.43921 (15)	0.0253 (9)
O15	0.3399 (6)	0.9248 (3)	0.53905 (15)	0.0256 (9)
O221	0.5282 (7)	0.3370 (3)	−0.01971 (16)	0.0346 (10)
O222	0.0758 (7)	0.4388 (3)	−0.05378 (15)	0.0276 (9)
O25	0.2259 (7)	0.0468 (3)	0.05684 (17)	0.0338 (10)
N16	0.1571 (8)	0.8792 (4)	0.57727 (18)	0.0237 (10)
N26	0.4029 (8)	0.0741 (4)	0.0958 (2)	0.0319 (11)
C11	0.3846 (9)	0.7102 (5)	0.5373 (2)	0.0198 (12)
H11	0.523 (9)	0.643 (4)	0.554 (2)	0.024*
C13	0.3144 (10)	0.8471 (5)	0.4437 (2)	0.0242 (13)
H13	0.140 (10)	0.894 (5)	0.443 (2)	0.029*
C14	0.4592 (10)	0.8300 (4)	0.5047 (2)	0.0198 (12)
H14	0.644 (9)	0.827 (4)	0.503 (2)	0.024*
C17	0.1781 (9)	0.7628 (4)	0.5775 (2)	0.0193 (12)
C18	0.0097 (4)	0.6945 (2)	0.61509 (9)	0.0214 (12)
C19	−0.1806 (6)	0.7560 (2)	0.64896 (11)	0.0262 (13)
H19	−0.2029	0.8427	0.6480	0.031*
C110	−0.3381 (5)	0.6907 (2)	0.68425 (11)	0.0298 (13)
H110	−0.4681	0.7328	0.7074	0.036*
C111	−0.3054 (5)	0.5639 (2)	0.68568 (10)	0.0307 (14)
H111	−0.4131	0.5193	0.7098	0.037*
C112	−0.1152 (6)	0.5024 (2)	0.65181 (12)	0.0261 (13)
H112	−0.0929	0.4157	0.6528	0.031*
C113	0.0424 (5)	0.56766 (18)	0.61652 (10)	0.0254 (13)
H113	0.1724	0.5256	0.5934	0.031*
C114	0.4570 (9)	0.8744 (4)	0.38663 (15)	0.0309 (13)
H14A	0.6102	0.8046	0.3860	0.037*
H14B	0.5217	0.9502	0.3870	0.037*
C115	0.2907 (12)	0.8934 (5)	0.3294 (2)	0.0397 (15)
H15A	0.1258	0.9555	0.3320	0.048*
H15B	0.2469	0.8141	0.3256	0.048*
C116	0.4327 (14)	0.9380 (6)	0.2741 (3)	0.057 (2)
H16A	0.4735	1.0173	0.2775	0.068*
H16B	0.3215	0.9494	0.2379	0.068*
H16C	0.5945	0.8760	0.2711	0.068*
C21	0.1452 (10)	0.2656 (5)	0.0489 (2)	0.0251 (13)
H21	0.004 (10)	0.322 (5)	0.056 (2)	0.030*
C23	0.2068 (11)	0.1887 (5)	−0.0421 (2)	0.0288 (14)
H23	0.385 (10)	0.142 (5)	−0.045 (2)	0.035*
C24	0.0845 (11)	0.1605 (5)	0.0199 (3)	0.0283 (13)
H24	−0.096 (10)	0.160 (4)	0.019 (2)	0.034*
C27	0.3611 (10)	0.1936 (5)	0.0931 (2)	0.0251 (13)
C28	0.5188 (4)	0.2460 (2)	0.13003 (9)	0.0257 (13)
C29	0.7282 (6)	0.1707 (2)	0.16611 (11)	0.0321 (14)
H29	0.7705	0.0833	0.1674	0.039*
C210	0.8756 (5)	0.2231 (3)	0.20023 (11)	0.0358 (15)
H210	1.0187	0.1717	0.2249	0.043*
C211	0.8136 (5)	0.3509 (3)	0.19827 (10)	0.0365 (15)
H211	0.9144	0.3868	0.2216	0.044*
C212	0.6042 (6)	0.4263 (2)	0.16220 (12)	0.0325 (14)
H212	0.5619	0.5136	0.1609	0.039*
C213	0.4568 (5)	0.3738 (2)	0.12808 (11)	0.0270 (13)
H213	0.3136	0.4253	0.1034	0.032*
C214	0.0410 (9)	0.2064 (4)	−0.09788 (15)	0.0332 (14)
H24A	−0.1185	0.2721	−0.0959	0.040*
H24B	−0.0130	0.1282	−0.0992	0.040*
C215	0.1773 (12)	0.2421 (5)	−0.1553 (3)	0.0440 (16)
H25A	0.2415	0.3172	−0.1530	0.053*
H25B	0.3299	0.1738	−0.1590	0.053*
C216	0.0012 (16)	0.2674 (8)	−0.2102 (3)	0.087 (3)
H26A	−0.0454	0.1904	−0.2155	0.105*
H26B	0.0909	0.2985	−0.2457	0.105*
H26C	−0.1572	0.3300	−0.2053	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S12	0.0243 (7)	0.0209 (8)	0.0233 (8)	−0.0014 (6)	0.0018 (6)	−0.0100 (6)
S22	0.0293 (8)	0.0181 (8)	0.0259 (8)	−0.0025 (6)	0.0086 (6)	−0.0018 (6)
O121	0.030 (2)	0.033 (2)	0.033 (2)	−0.0068 (17)	0.0018 (17)	−0.0153 (18)
O122	0.030 (2)	0.021 (2)	0.024 (2)	0.0011 (16)	0.0039 (16)	−0.0116 (16)
O15	0.036 (2)	0.021 (2)	0.022 (2)	−0.0087 (17)	0.0101 (17)	−0.0091 (16)
O221	0.033 (2)	0.033 (2)	0.039 (2)	−0.0113 (18)	0.0076 (18)	−0.0078 (19)
O222	0.036 (2)	0.018 (2)	0.025 (2)	0.0008 (17)	0.0047 (17)	−0.0027 (16)
O25	0.043 (2)	0.016 (2)	0.039 (2)	−0.0047 (18)	0.0018 (19)	−0.0004 (18)
N16	0.031 (3)	0.024 (3)	0.018 (2)	−0.008 (2)	0.008 (2)	−0.007 (2)
N26	0.033 (3)	0.026 (3)	0.033 (3)	−0.003 (2)	0.002 (2)	−0.001 (2)
C11	0.020 (3)	0.016 (3)	0.026 (3)	−0.003 (2)	0.000 (2)	−0.011 (2)
C13	0.025 (3)	0.022 (3)	0.026 (3)	−0.004 (2)	0.004 (2)	−0.006 (2)
C14	0.020 (3)	0.019 (3)	0.021 (3)	−0.001 (2)	0.005 (2)	−0.009 (2)
C17	0.024 (3)	0.013 (3)	0.019 (3)	−0.002 (2)	−0.001 (2)	−0.003 (2)
C18	0.022 (3)	0.024 (3)	0.017 (3)	−0.004 (2)	0.000 (2)	−0.002 (2)
C19	0.029 (3)	0.023 (3)	0.027 (3)	−0.002 (2)	0.006 (2)	−0.010 (2)
C110	0.032 (3)	0.033 (3)	0.025 (3)	−0.006 (3)	0.005 (3)	−0.008 (3)
C111	0.039 (3)	0.036 (4)	0.019 (3)	−0.017 (3)	0.003 (3)	0.001 (3)
C112	0.035 (3)	0.021 (3)	0.022 (3)	−0.008 (2)	0.000 (2)	0.000 (2)
C113	0.027 (3)	0.023 (3)	0.024 (3)	−0.001 (2)	0.001 (2)	−0.008 (2)
C114	0.041 (3)	0.023 (3)	0.027 (3)	−0.006 (3)	0.007 (3)	−0.006 (3)
C115	0.064 (4)	0.026 (3)	0.030 (4)	−0.010 (3)	−0.001 (3)	−0.008 (3)
C116	0.087 (5)	0.049 (4)	0.023 (4)	0.004 (4)	0.007 (3)	−0.004 (3)
C21	0.022 (3)	0.018 (3)	0.033 (3)	0.000 (2)	0.004 (3)	−0.005 (3)
C23	0.031 (3)	0.015 (3)	0.039 (4)	−0.003 (2)	0.008 (3)	−0.003 (3)
C24	0.026 (3)	0.019 (3)	0.038 (4)	−0.002 (2)	0.002 (3)	−0.004 (3)
C27	0.027 (3)	0.016 (3)	0.029 (3)	0.000 (2)	0.009 (2)	0.000 (2)
C28	0.022 (3)	0.028 (3)	0.025 (3)	−0.005 (2)	0.009 (2)	−0.003 (3)
C29	0.030 (3)	0.034 (3)	0.025 (3)	0.001 (3)	0.004 (3)	0.001 (3)
C210	0.023 (3)	0.052 (4)	0.026 (3)	−0.001 (3)	0.002 (3)	0.000 (3)
C211	0.041 (4)	0.048 (4)	0.023 (3)	−0.015 (3)	0.010 (3)	−0.007 (3)
C212	0.040 (3)	0.030 (3)	0.028 (3)	−0.012 (3)	0.010 (3)	−0.002 (3)
C213	0.032 (3)	0.027 (3)	0.020 (3)	−0.005 (3)	0.003 (2)	−0.001 (2)
C214	0.046 (4)	0.021 (3)	0.034 (4)	−0.008 (3)	0.005 (3)	−0.006 (3)
C215	0.069 (5)	0.026 (3)	0.035 (4)	−0.005 (3)	0.009 (3)	−0.007 (3)
C216	0.105 (7)	0.092 (6)	0.031 (4)	0.042 (5)	0.005 (4)	−0.008 (4)

Geometric parameters (Å, º)

S12—O121	1.425 (4)	C114—H14B	0.9900
S12—O122	1.434 (3)	C115—C116	1.522 (8)
S12—C11	1.822 (5)	C115—H15A	0.9900
S12—C13	1.822 (5)	C115—H15B	0.9900
S22—O221	1.425 (4)	C116—H16A	0.9800
S22—O222	1.432 (4)	C116—H16B	0.9800
S22—C21	1.825 (5)	C116—H16C	0.9800
S22—C23	1.828 (5)	C21—C27	1.499 (7)
O15—N16	1.414 (5)	C21—C24	1.544 (7)
O15—C14	1.454 (5)	C21—H21	0.89 (5)
O25—N26	1.409 (5)	C23—C214	1.495 (6)
O25—C24	1.439 (6)	C23—C24	1.550 (8)
N16—C17	1.287 (6)	C23—H23	0.97 (5)
N26—C27	1.300 (6)	C24—H24	0.96 (5)
C11—C17	1.499 (7)	C27—C28	1.466 (6)
C11—C14	1.548 (7)	C28—C29	1.3900
C11—H11	0.94 (5)	C28—C213	1.3900
C13—C114	1.509 (6)	C29—C210	1.3900
C13—C14	1.540 (7)	C29—H29	0.9500
C13—H13	0.95 (5)	C210—C211	1.3900
C14—H14	0.97 (5)	C210—H210	0.9500
C17—C18	1.475 (5)	C211—C212	1.3900
C18—C19	1.3900	C211—H211	0.9500
C18—C113	1.3900	C212—C213	1.3900
C19—C110	1.3900	C212—H212	0.9500
C19—H19	0.9500	C213—H213	0.9500
C110—C111	1.3900	C214—C215	1.516 (7)
C110—H110	0.9500	C214—H24A	0.9900
C111—C112	1.3900	C214—H24B	0.9900
C111—H111	0.9500	C215—C216	1.499 (9)
C112—C113	1.3900	C215—H25A	0.9900
C112—H112	0.9500	C215—H25B	0.9900
C113—H113	0.9500	C216—H26A	0.9800
C114—C115	1.521 (7)	C216—H26B	0.9800
C114—H14A	0.9900	C216—H26C	0.9800
O121—S12—O122	118.9 (2)	C116—C115—H15B	109.4
O121—S12—C11	114.5 (2)	H15A—C115—H15B	108.0
O122—S12—C11	110.9 (2)	C115—C116—H16A	109.5
O121—S12—C13	114.9 (2)	C115—C116—H16B	109.5
O122—S12—C13	110.9 (2)	H16A—C116—H16B	109.5
C11—S12—C13	80.5 (2)	C115—C116—H16C	109.5
O221—S22—O222	118.8 (2)	H16A—C116—H16C	109.5
O221—S22—C21	113.2 (2)	H16B—C116—H16C	109.5
O222—S22—C21	112.3 (2)	C27—C21—C24	101.0 (4)
O221—S22—C23	114.7 (2)	C27—C21—S22	113.2 (4)
O222—S22—C23	111.2 (2)	C24—C21—S22	89.7 (3)
C21—S22—C23	80.6 (2)	C27—C21—H21	126 (3)
N16—O15—C14	108.5 (3)	C24—C21—H21	114 (3)
N26—O25—C24	109.2 (4)	S22—C21—H21	106 (3)
C17—N16—O15	110.8 (4)	C214—C23—C24	118.5 (5)
C27—N26—O25	110.3 (4)	C214—C23—S22	114.9 (4)
C17—C11—C14	100.9 (4)	C24—C23—S22	89.4 (3)
C17—C11—S12	114.5 (4)	C214—C23—H23	114 (3)
C14—C11—S12	88.9 (3)	C24—C23—H23	115 (3)
C17—C11—H11	119 (3)	S22—C23—H23	101 (3)
C14—C11—H11	117 (3)	O25—C24—C21	105.2 (4)
S12—C11—H11	112 (3)	O25—C24—C23	112.7 (4)
C114—C13—C14	118.8 (4)	C21—C24—C23	99.5 (4)
C114—C13—S12	117.4 (4)	O25—C24—H24	109 (3)
C14—C13—S12	89.1 (3)	C21—C24—H24	114 (3)
C114—C13—H13	115 (3)	C23—C24—H24	116 (3)
C14—C13—H13	113 (3)	N26—C27—C28	120.9 (4)
S12—C13—H13	99 (3)	N26—C27—C21	112.8 (5)
O15—C14—C13	111.9 (4)	C28—C27—C21	126.3 (4)
O15—C14—C11	104.7 (4)	C29—C28—C213	120.0
C13—C14—C11	99.4 (4)	C29—C28—C27	121.3 (2)
O15—C14—H14	108 (3)	C213—C28—C27	118.7 (2)
C13—C14—H14	116 (3)	C210—C29—C28	120.0
C11—C14—H14	116 (3)	C210—C29—H29	120.0
N16—C17—C18	120.4 (4)	C28—C29—H29	120.0
N16—C17—C11	113.1 (4)	C29—C210—C211	120.0
C18—C17—C11	126.5 (4)	C29—C210—H210	120.0
C19—C18—C113	120.0	C211—C210—H210	120.0
C19—C18—C17	120.5 (2)	C212—C211—C210	120.0
C113—C18—C17	119.5 (2)	C212—C211—H211	120.0
C18—C19—C110	120.0	C210—C211—H211	120.0
C18—C19—H19	120.0	C211—C212—C213	120.0
C110—C19—H19	120.0	C211—C212—H212	120.0
C19—C110—C111	120.0	C213—C212—H212	120.0
C19—C110—H110	120.0	C212—C213—C28	120.0
C111—C110—H110	120.0	C212—C213—H213	120.0
C112—C111—C110	120.0	C28—C213—H213	120.0
C112—C111—H111	120.0	C23—C214—C215	113.4 (4)
C110—C111—H111	120.0	C23—C214—H24A	108.9
C111—C112—C113	120.0	C215—C214—H24A	108.9
C111—C112—H112	120.0	C23—C214—H24B	108.9
C113—C112—H112	120.0	C215—C214—H24B	108.9
C112—C113—C18	120.0	H24A—C214—H24B	107.7
C112—C113—H113	120.0	C216—C215—C214	112.2 (5)
C18—C113—H113	120.0	C216—C215—H25A	109.2
C13—C114—C115	113.8 (4)	C214—C215—H25A	109.2
C13—C114—H14A	108.8	C216—C215—H25B	109.2
C115—C114—H14A	108.8	C214—C215—H25B	109.2
C13—C114—H14B	108.8	H25A—C215—H25B	107.9
C115—C114—H14B	108.8	C215—C216—H26A	109.5
H14A—C114—H14B	107.7	C215—C216—H26B	109.5
C114—C115—C116	111.1 (5)	H26A—C216—H26B	109.5
C114—C115—H15A	109.4	C215—C216—H26C	109.5
C116—C115—H15A	109.4	H26A—C216—H26C	109.5
C114—C115—H15B	109.4	H26B—C216—H26C	109.5
C14—O15—N16—C17	9.8 (5)	C14—C13—C114—C115	−178.2 (4)
C23—S22—C21—C24	−6.3 (3)	S12—C13—C114—C115	76.5 (5)
C13—S12—C11—C17	91.5 (4)	C13—C114—C115—C116	172.1 (5)
C23—S22—C21—C27	95.6 (4)	O221—S22—C21—C27	−17.3 (5)
C24—O25—N26—C27	9.0 (5)	O222—S22—C21—C27	−155.3 (4)
O121—S12—C11—C17	−21.7 (4)	O221—S22—C21—C24	−119.1 (3)
O122—S12—C11—C17	−159.6 (3)	O222—S22—C21—C24	102.9 (3)
O121—S12—C11—C14	−123.2 (3)	O221—S22—C23—C214	−121.0 (4)
O122—S12—C11—C14	98.9 (3)	O222—S22—C23—C214	17.3 (5)
C13—S12—C11—C14	−10.0 (3)	C21—S22—C23—C214	127.7 (4)
O121—S12—C13—C114	−114.8 (4)	O221—S22—C23—C24	117.6 (3)
O122—S12—C13—C114	23.6 (5)	O222—S22—C23—C24	−104.1 (3)
C11—S12—C13—C114	132.4 (4)	C21—S22—C23—C24	6.2 (3)
O121—S12—C13—C14	122.8 (3)	N26—O25—C24—C21	−12.3 (5)
O122—S12—C13—C14	−98.8 (3)	N26—O25—C24—C23	95.1 (5)
C11—S12—C13—C14	10.1 (3)	C27—C21—C24—O25	10.7 (5)
N16—O15—C14—C13	92.5 (4)	S22—C21—C24—O25	124.2 (4)
N16—O15—C14—C11	−14.2 (5)	C27—C21—C24—C23	−106.2 (4)
C114—C13—C14—O15	116.9 (5)	S22—C21—C24—C23	7.4 (4)
S12—C13—C14—O15	−121.9 (4)	C214—C23—C24—O25	123.4 (5)
C114—C13—C14—C11	−133.0 (4)	S22—C23—C24—O25	−118.4 (4)
S12—C13—C14—C11	−11.9 (3)	C214—C23—C24—C21	−125.6 (5)
C17—C11—C14—O15	12.9 (5)	S22—C23—C24—C21	−7.4 (4)
S12—C11—C14—O15	127.6 (3)	O25—N26—C27—C28	179.4 (4)
C17—C11—C14—C13	−102.8 (4)	O25—N26—C27—C21	−1.4 (6)
S12—C11—C14—C13	11.9 (3)	C24—C21—C27—N26	−6.0 (6)
O15—N16—C17—C18	179.0 (3)	S22—C21—C27—N26	−100.4 (5)
O15—N16—C17—C11	−0.7 (6)	C24—C21—C27—C28	173.2 (4)
C14—C11—C17—N16	−7.9 (5)	S22—C21—C27—C28	78.8 (5)
S12—C11—C17—N16	−101.7 (4)	N26—C27—C28—C29	4.3 (5)
C14—C11—C17—C18	172.5 (4)	C21—C27—C28—C29	−174.8 (4)
S12—C11—C17—C18	78.7 (5)	N26—C27—C28—C213	−176.3 (4)
N16—C17—C18—C19	2.5 (5)	C21—C27—C28—C213	4.5 (6)
C11—C17—C18—C19	−177.9 (4)	C213—C28—C29—C210	0.0
N16—C17—C18—C113	−177.5 (3)	C27—C28—C29—C210	179.4 (3)
C11—C17—C18—C113	2.1 (6)	C28—C29—C210—C211	0.0
C113—C18—C19—C110	0.0	C29—C210—C211—C212	0.0
C17—C18—C19—C110	−180.0 (2)	C210—C211—C212—C213	0.0
C18—C19—C110—C111	0.0	C211—C212—C213—C28	0.0
C19—C110—C111—C112	0.0	C29—C28—C213—C212	0.0
C110—C111—C112—C113	0.0	C27—C28—C213—C212	−179.4 (2)
C111—C112—C113—C18	0.0	C24—C23—C214—C215	176.0 (4)
C19—C18—C113—C112	0.0	S22—C23—C214—C215	72.3 (5)
C17—C18—C113—C112	180.0 (2)	C23—C214—C215—C216	−176.2 (5)