(S)-3-[(R)-2,4-Dimethyl­pent-4-eno­yl]-4-isopropyl-5,5-diphenyl-1,3-oxazolidin-2-one

The title compound, C₂₅H₂₉NO₃, was prepared in the course of the generation of depsipeptide libraries resembling the Jasplakinolide family of natural products. The dihedral angle between the phenyl ring planes is 74.1 (3)° The oxazolidinone ring adopts a slightly distorted ⁴E conformation with an axial projection of the isopropyl substituent, which is easily rationalized by pseudo-allylic strain exerted by the exocyclic imide carbonyl. The two carbonyl groups adopt a noncolinear S-shaped conformation.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.032
• wR factor = 0.086
• Data-to-parameter ratio = 8.5

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT026_ALERT_3_A Ratio Observed / Unique Reflections too Low ....         28 Perc.

Author Response: The quality of the crystal was not very good and the data collection was performed at room temperature.

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N      -   C6      ..       5.29 su
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C13

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           25.03
           From the CIF: _reflns_number_total               2223
           Count of symmetry unique reflns         2230
           Completeness (_total/calc)             99.69%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C7     = .          R

   1 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

The title compound, (I), was synthesized in the course of the generation of depsipeptide libraries resembling the Jasplakinolide family of natural products (Hu et al., 2007). The relative configuration of (I) is in accordance with the model for diastereoselective alkylation of acylated chiral oxazolidinones derived from amino acids (Evans & Takacs, 1980) and their modified diphenyl analogs (Hintermann & Seebach, 1998). The stereogenic centres were assigned based on the known chirality of the starting material (C3 S and C7 R).

Related literature

For related literature, see: Evans & Takacs (1980); Hintermann & Seebach (1998); Hu et al. (2007).

S2. Experimental

To a solution of (S)-4-isopropyl-5,5-diphenyl-3-propionyloxazolidin-2-one (1.6 g, 4.8 mmol, 1.0 eq) in 20 ml dry THF was added dropwise via syringe a freshly prepared solution of lithium diisoproylamide (6.2 mmol, 1.3 eq) in 12 ml dry THF at 195 K. The solution was stirred at 195 K for 30 min and then a solution of 1.4 g (6.2 mmol dry ZnBr₂ in 12 ml dry THF was added via syringe at 195 K. After stirring for 30 min at 195 K 5.1 ml (50 mmol, 10 eq) 3-bromo-2-methylprop-1-ene were added in one portion via syringe. The mixture was allowed to warm to 258 K and stirred at 258 K for 20 h, treated with 20 ml saturated aqueous NH₄Cl solution and diluted with 50 ml Et₂O. The organic layer was separated and washed with 5% aqueous HCl solution (2 × 20 ml), 5% aqueous NaOH solution (2 × 20 ml) and brine (1 × 15 ml). The solution was dried with MgSO₄, filtered and concentrated to give 1.9 g of a light yellow solid. Recrystallization with Et₂O/pentane afforded 1.4 g (75%) of (I) as colourless blocks.

[α]²⁷³_D -190.5 (c 1.0, CHCl₃); mp 392.5–393.0 K; R_f = 0.43 (cyclohexane/ethyl acetate 19:1); ¹H NMR (500.1 MHz, CDCl₃) δ = 7.46 (d, J = 8.2 Hz, 2H), 7.40 (d, J = 7.7 Hz, 2H), 7.34 (dd, J = 16.4, 8.1 Hz, 4H), 7.30–7.25 (m, 2H, p-phenyl), 5.38 (d, J = 3.0 Hz, 1H, NCH) 4.77 (s, 1H, =CHH), 4.74 (s, 1H, =CHH), 3.96–3.87 (m, 1H, O=C—CH), 2.57 (dd, J = 14.0, 7.2 Hz, 1H, CHH), 2.02 (dd, J = 14.0, 7.5 Hz, 1H, CHH), 1.99–1.92 (m, 1H, CH₃—CH-CH₃), 1.76 (s, 3H, =C—CH₃), 0.86 (d, J = 7.0 Hz, 3H, O=C—C—CH₃), 0.80 (d, J = 6.8 Hz, 3H, CH₃-CH—CH₃), 0.76 (d, J = 6.7 Hz, 3H, CH₃—CH—CH₃); ¹³C NMR (125.8 MHz, CDCl₃) δ = 176.6 (C=O), 152.9 (C=O), 143.0 (quart. arom. C), 142.4 (quart. arom. C), 138.2 (C=CH₂), 128.8 (2x, arom. CH), 128.5 (arom. CH), 128.4 (2x, arom. CH), 127.9 (arom. CH), 125.9 (2x, arom. CH), 125.6 (2x, arom. CH), 112.2 (C=CH₂), 64.5 (CH), 41.7 (CH2), 35.4 (CH), 29.8 (CH), 22.2 (CH₃), 21.7 (CH₃), 16.3 (CH₃), 16.3(CH₃); HRMS (FAB): m/z calculated for C₂₅H₃₀NO₃; [M+H]⁺: 392.2220; found: 392.2244.

S3. Refinement

Anomalous dispersion was negligible and Friedel pairs were merged before refinement.

The H atoms were placed in calculated positions, with C—H = 0.93–0.98 Å and were refined as riding, with U_iso(H)= 1.5U_eq(C) for methyl and 1.2U_eq(C) for all other H atoms; the methyl groups were allowed to rotate but not to tip to best fit the electron density.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).

Figures

Fig. 1. : The molecular structure of (I). Displacement ellipsoids for the non-hydrogen atoms are shown at the 20% probability level.

(S)-3-[(R)-2,4-Dimethylpent-4-enoyl]-4-isopropyl-5,5-diphenyl- 1,3-oxazolidin-2-one

Crystal data

C25H29NO3	F(000) = 840
Mr = 391.49	Dx = 1.186 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 15624 reflections
a = 8.7567 (11) Å	θ = 3.1–25.0°
b = 10.0467 (17) Å	µ = 0.08 mm^−1
c = 24.921 (5) Å	T = 291 K
V = 2192.4 (6) Å^3	Block, colourless
Z = 4	0.25 × 0.25 × 0.23 mm

Data collection

Nonius KappaCCD area-detector diffractometer	628 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.064
Graphite monochromator	θmax = 25.0°, θmin = 3.1°
Detector resolution: 19 vertical, 18 horizontal pixels mm^-1	h = −10→10
338 frames via ω–rotation (Δω = 1%) and two times 20 s per frame (three sets at different κ–angles) scans	k = −11→11
15624 measured reflections	l = −29→29
2223 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H-atom parameters constrained
S = 1.01	[1.0 exp(7.90(sinθ/λ)^2)]/[σ^2(Fo^2)]
2223 reflections	(Δ/σ)max < 0.001
262 parameters	Δρmax = 0.10 e Å^−3
0 restraints	Δρmin = −0.13 e Å^−3

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.

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.

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

	x	y	z	Uiso*/Ueq
O1	0.2130 (4)	0.6030 (4)	0.84026 (17)	0.0393 (11)
O2	0.3031 (5)	0.4620 (4)	0.77804 (16)	0.0449 (12)
O3	0.6121 (5)	0.3935 (4)	0.90646 (18)	0.0455 (13)
N	0.4382 (5)	0.5084 (5)	0.85736 (18)	0.0387 (14)
C1	0.6965 (6)	0.7027 (6)	0.8894 (2)	0.055 (2)
H1A	0.7582	0.7774	0.8790	0.083*
H1B	0.7215	0.6274	0.8674	0.083*
H1C	0.7155	0.6816	0.9263	0.083*
C2	0.5262 (7)	0.7379 (6)	0.8820 (2)	0.0410 (17)
H2A	0.5021	0.8103	0.9069	0.049*
C3	0.4273 (6)	0.6170 (6)	0.8977 (2)	0.0384 (17)
H3A	0.4581	0.5839	0.9330	0.046*
C4	0.2510 (6)	0.6376 (6)	0.8961 (3)	0.0402 (18)
C5	0.3168 (8)	0.5165 (6)	0.8208 (3)	0.0427 (18)
C6	0.5360 (8)	0.3987 (7)	0.8662 (3)	0.0458 (19)
C7	0.5342 (7)	0.2882 (6)	0.8239 (2)	0.0381 (17)
H7A	0.5001	0.3252	0.7896	0.046*
C8	0.6941 (7)	0.2323 (6)	0.8174 (2)	0.0461 (19)
H8A	0.6878	0.1522	0.7957	0.055*
H8B	0.7316	0.2065	0.8525	0.055*
C9	0.8104 (8)	0.3254 (7)	0.7918 (3)	0.049 (2)
C10	0.7793 (8)	0.4454 (7)	0.7734 (2)	0.054 (2)
H10A	0.6803	0.4785	0.7756	0.065*
H10B	0.8563	0.4969	0.7583	0.065*
C11	0.4984 (7)	0.7896 (6)	0.8246 (2)	0.052 (2)
H11A	0.5617	0.8660	0.8182	0.078*
H11B	0.3930	0.8142	0.8207	0.078*
H11C	0.5230	0.7211	0.7992	0.078*
C12	0.4201 (6)	0.1795 (6)	0.8422 (2)	0.057 (2)
H12A	0.4171	0.1096	0.8160	0.086*
H12B	0.3203	0.2178	0.8459	0.086*
H12C	0.4524	0.1437	0.8761	0.086*
C13	0.9699 (7)	0.2650 (6)	0.7874 (2)	0.062 (2)
H13A	1.0378	0.3283	0.7711	0.093*
H13B	0.9657	0.1862	0.7657	0.093*
H13C	1.0067	0.2426	0.8225	0.093*
C21	0.1919 (7)	0.7761 (7)	0.9059 (3)	0.0411 (17)
C22	0.2239 (7)	0.8402 (7)	0.9540 (3)	0.048 (2)
H22A	0.2860	0.7991	0.9794	0.057*
C23	0.1631 (7)	0.9663 (7)	0.9646 (3)	0.055 (2)
H23A	0.1856	1.0092	0.9967	0.066*
C24	0.0692 (8)	1.0271 (7)	0.9271 (3)	0.058 (2)
H24A	0.0279	1.1106	0.9340	0.070*
C25	0.0375 (8)	0.9627 (7)	0.8796 (3)	0.059 (2)
H25A	−0.0237	1.0041	0.8540	0.071*
C26	0.0958 (7)	0.8368 (7)	0.8694 (3)	0.049 (2)
H26A	0.0701	0.7930	0.8378	0.059*
C27	0.1700 (7)	0.5358 (6)	0.9326 (3)	0.0373 (17)
C28	0.0354 (7)	0.4759 (6)	0.9156 (2)	0.0416 (17)
H28A	−0.0045	0.4956	0.8819	0.050*
C29	−0.0390 (7)	0.3871 (7)	0.9487 (3)	0.0485 (19)
H29A	−0.1289	0.3475	0.9369	0.058*
C30	0.0162 (7)	0.3552 (6)	0.9990 (3)	0.052 (2)
H30A	−0.0341	0.2942	1.0208	0.062*
C31	0.1508 (8)	0.4179 (7)	1.0162 (3)	0.056 (2)
H31A	0.1902	0.3990	1.0500	0.067*
C32	0.2255 (7)	0.5080 (7)	0.9831 (3)	0.049 (2)
H32A	0.3137	0.5499	0.9952	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.039 (3)	0.041 (3)	0.038 (3)	0.006 (3)	0.001 (2)	−0.005 (2)
O2	0.048 (3)	0.056 (3)	0.031 (3)	0.004 (3)	0.000 (3)	−0.005 (3)
O3	0.054 (3)	0.039 (3)	0.043 (3)	0.005 (3)	−0.010 (3)	−0.005 (3)
N	0.038 (3)	0.039 (4)	0.039 (4)	0.010 (3)	−0.005 (3)	−0.004 (3)
C1	0.050 (4)	0.056 (5)	0.059 (5)	−0.011 (4)	0.003 (4)	−0.006 (4)
C2	0.047 (4)	0.036 (4)	0.040 (5)	0.004 (4)	0.004 (4)	−0.002 (4)
C3	0.042 (4)	0.041 (4)	0.032 (4)	−0.004 (4)	−0.004 (3)	−0.009 (4)
C4	0.039 (4)	0.042 (5)	0.040 (5)	0.001 (4)	−0.007 (4)	−0.002 (4)
C5	0.050 (5)	0.035 (5)	0.043 (5)	−0.008 (4)	−0.006 (5)	0.010 (4)
C6	0.043 (5)	0.047 (5)	0.047 (5)	−0.012 (5)	0.018 (4)	−0.007 (5)
C7	0.040 (4)	0.039 (4)	0.036 (5)	0.011 (4)	0.001 (4)	0.001 (4)
C8	0.059 (5)	0.041 (4)	0.038 (4)	0.002 (4)	−0.007 (4)	−0.007 (4)
C9	0.051 (5)	0.050 (5)	0.045 (5)	−0.005 (5)	0.000 (4)	−0.011 (4)
C10	0.065 (5)	0.051 (5)	0.047 (5)	0.001 (4)	0.010 (4)	−0.002 (4)
C11	0.058 (5)	0.042 (5)	0.057 (5)	−0.001 (4)	0.005 (4)	0.003 (4)
C12	0.056 (5)	0.052 (5)	0.063 (5)	−0.014 (4)	−0.007 (4)	−0.007 (4)
C13	0.046 (5)	0.075 (6)	0.066 (6)	0.002 (5)	−0.004 (4)	0.005 (5)
C21	0.041 (4)	0.046 (5)	0.037 (5)	0.001 (4)	0.015 (4)	0.006 (4)
C22	0.054 (5)	0.047 (5)	0.042 (5)	0.004 (4)	0.002 (4)	−0.002 (4)
C23	0.061 (6)	0.046 (5)	0.058 (5)	−0.006 (5)	0.015 (4)	−0.011 (5)
C24	0.064 (5)	0.043 (5)	0.067 (6)	0.010 (5)	0.024 (5)	−0.005 (5)
C25	0.066 (5)	0.045 (5)	0.067 (6)	0.007 (5)	0.008 (5)	0.013 (5)
C26	0.056 (5)	0.041 (5)	0.051 (5)	0.011 (4)	0.006 (4)	−0.012 (4)
C27	0.039 (4)	0.033 (4)	0.039 (5)	0.011 (4)	0.005 (4)	0.001 (4)
C28	0.044 (4)	0.037 (4)	0.043 (4)	0.010 (4)	−0.006 (4)	0.001 (4)
C29	0.047 (4)	0.042 (5)	0.056 (5)	−0.005 (4)	−0.011 (4)	−0.008 (4)
C30	0.048 (5)	0.047 (5)	0.061 (6)	0.005 (4)	0.010 (4)	0.005 (4)
C31	0.062 (6)	0.063 (6)	0.041 (5)	−0.010 (5)	−0.011 (4)	0.008 (4)
C32	0.049 (5)	0.055 (5)	0.044 (5)	−0.014 (4)	0.001 (4)	−0.003 (4)

Geometric parameters (Å, º)

O1—C5	1.348 (7)	C11—H11B	0.9600
O1—C4	1.471 (7)	C11—H11C	0.9600
O2—C5	1.203 (7)	C12—H12A	0.9600
O3—C6	1.205 (7)	C12—H12B	0.9600
N—C5	1.404 (7)	C12—H12C	0.9600
N—C6	1.413 (7)	C13—H13A	0.9600
N—C3	1.486 (6)	C13—H13B	0.9600
C1—C2	1.543 (7)	C13—H13C	0.9600
C1—H1A	0.9600	C21—C26	1.382 (8)
C1—H1B	0.9600	C21—C22	1.390 (8)
C1—H1C	0.9600	C22—C23	1.399 (8)
C2—C11	1.541 (7)	C22—H22A	0.9300
C2—C3	1.542 (7)	C23—C24	1.387 (8)
C2—H2A	0.9800	C23—H23A	0.9300
C3—C4	1.558 (7)	C24—C25	1.377 (7)
C3—H3A	0.9800	C24—H24A	0.9300
C4—C21	1.505 (8)	C25—C26	1.388 (7)
C4—C27	1.541 (8)	C25—H25A	0.9300
C6—C7	1.531 (8)	C26—H26A	0.9300
C7—C8	1.517 (7)	C27—C32	1.379 (7)
C7—C12	1.549 (7)	C27—C28	1.390 (7)
C7—H7A	0.9800	C28—C29	1.380 (7)
C8—C9	1.523 (8)	C28—H28A	0.9300
C8—H8A	0.9700	C29—C30	1.381 (8)
C8—H8B	0.9700	C29—H29A	0.9300
C9—C10	1.318 (7)	C30—C31	1.403 (7)
C9—C13	1.527 (7)	C30—H30A	0.9300
C10—H10A	0.9300	C31—C32	1.387 (8)
C10—H10B	0.9300	C31—H31A	0.9300
C11—H11A	0.9600	C32—H32A	0.9300
C5—O1—C4	109.9 (5)	C2—C11—H11B	109.5
C5—N—C6	127.3 (6)	H11A—C11—H11B	109.5
C5—N—C3	110.4 (5)	C2—C11—H11C	109.5
C6—N—C3	120.4 (5)	H11A—C11—H11C	109.5
C2—C1—H1A	109.5	H11B—C11—H11C	109.5
C2—C1—H1B	109.5	C7—C12—H12A	109.5
H1A—C1—H1B	109.5	C7—C12—H12B	109.5
C2—C1—H1C	109.5	H12A—C12—H12B	109.5
H1A—C1—H1C	109.5	C7—C12—H12C	109.5
H1B—C1—H1C	109.5	H12A—C12—H12C	109.5
C11—C2—C1	110.0 (5)	H12B—C12—H12C	109.5
C11—C2—C3	114.3 (5)	C9—C13—H13A	109.5
C1—C2—C3	109.4 (5)	C9—C13—H13B	109.5
C11—C2—H2A	107.6	H13A—C13—H13B	109.5
C1—C2—H2A	107.6	C9—C13—H13C	109.5
C3—C2—H2A	107.6	H13A—C13—H13C	109.5
N—C3—C2	111.7 (5)	H13B—C13—H13C	109.5
N—C3—C4	98.3 (5)	C26—C21—C22	119.1 (6)
C2—C3—C4	116.5 (5)	C26—C21—C4	120.7 (6)
N—C3—H3A	109.9	C22—C21—C4	120.0 (7)
C2—C3—H3A	109.9	C21—C22—C23	120.4 (7)
C4—C3—H3A	109.9	C21—C22—H22A	119.8
O1—C4—C21	107.2 (5)	C23—C22—H22A	119.8
O1—C4—C27	107.3 (5)	C24—C23—C22	119.8 (7)
C21—C4—C27	111.0 (5)	C24—C23—H23A	120.1
O1—C4—C3	102.5 (5)	C22—C23—H23A	120.1
C21—C4—C3	117.3 (5)	C25—C24—C23	119.5 (7)
C27—C4—C3	110.6 (5)	C25—C24—H24A	120.3
O2—C5—O1	123.1 (7)	C23—C24—H24A	120.3
O2—C5—N	128.6 (7)	C24—C25—C26	120.7 (7)
O1—C5—N	108.3 (6)	C24—C25—H25A	119.6
O3—C6—N	119.9 (6)	C26—C25—H25A	119.6
O3—C6—C7	123.2 (7)	C21—C26—C25	120.4 (7)
N—C6—C7	116.9 (6)	C21—C26—H26A	119.8
C8—C7—C6	109.5 (5)	C25—C26—H26A	119.8
C8—C7—C12	111.4 (5)	C32—C27—C28	119.3 (6)
C6—C7—C12	108.4 (5)	C32—C27—C4	120.8 (6)
C8—C7—H7A	109.2	C28—C27—C4	119.8 (6)
C6—C7—H7A	109.2	C29—C28—C27	119.9 (6)
C12—C7—H7A	109.2	C29—C28—H28A	120.1
C7—C8—C9	115.8 (5)	C27—C28—H28A	120.1
C7—C8—H8A	108.3	C28—C29—C30	121.9 (6)
C9—C8—H8A	108.3	C28—C29—H29A	119.0
C7—C8—H8B	108.3	C30—C29—H29A	119.0
C9—C8—H8B	108.3	C29—C30—C31	117.8 (7)
H8A—C8—H8B	107.4	C29—C30—H30A	121.1
C10—C9—C8	124.7 (7)	C31—C30—H30A	121.1
C10—C9—C13	121.8 (7)	C32—C31—C30	120.5 (6)
C8—C9—C13	113.5 (6)	C32—C31—H31A	119.7
C9—C10—H10A	120.0	C30—C31—H31A	119.7
C9—C10—H10B	120.0	C27—C32—C31	120.6 (6)
H10A—C10—H10B	120.0	C27—C32—H32A	119.7
C2—C11—H11A	109.5	C31—C32—H32A	119.7
C5—N—C3—C2	−95.7 (5)	C12—C7—C8—C9	171.5 (5)
C6—N—C3—C2	99.1 (6)	C7—C8—C9—C10	−3.3 (9)
C5—N—C3—C4	27.2 (6)	C7—C8—C9—C13	178.8 (5)
C6—N—C3—C4	−138.1 (5)	O1—C4—C21—C26	11.1 (7)
C11—C2—C3—N	51.9 (7)	C27—C4—C21—C26	−105.8 (7)
C1—C2—C3—N	−71.9 (6)	C3—C4—C21—C26	125.6 (6)
C11—C2—C3—C4	−59.9 (7)	O1—C4—C21—C22	−174.0 (5)
C1—C2—C3—C4	176.3 (5)	C27—C4—C21—C22	69.1 (7)
C5—O1—C4—C21	151.1 (5)	C3—C4—C21—C22	−59.5 (8)
C5—O1—C4—C27	−89.6 (5)	C26—C21—C22—C23	−1.9 (9)
C5—O1—C4—C3	27.0 (6)	C4—C21—C22—C23	−176.8 (6)
N—C3—C4—O1	−30.9 (6)	C21—C22—C23—C24	0.6 (9)
C2—C3—C4—O1	88.4 (6)	C22—C23—C24—C25	−0.4 (10)
N—C3—C4—C21	−148.0 (6)	C23—C24—C25—C26	1.4 (10)
C2—C3—C4—C21	−28.6 (8)	C22—C21—C26—C25	2.8 (9)
N—C3—C4—C27	83.2 (6)	C4—C21—C26—C25	177.8 (6)
C2—C3—C4—C27	−157.4 (5)	C24—C25—C26—C21	−2.6 (10)
C4—O1—C5—O2	172.0 (6)	O1—C4—C27—C32	154.9 (5)
C4—O1—C5—N	−10.2 (6)	C21—C4—C27—C32	−88.3 (7)
C6—N—C5—O2	−30.7 (10)	C3—C4—C27—C32	43.8 (8)
C3—N—C5—O2	165.3 (6)	O1—C4—C27—C28	−28.2 (7)
C6—N—C5—O1	151.7 (5)	C21—C4—C27—C28	88.6 (7)
C3—N—C5—O1	−12.3 (6)	C3—C4—C27—C28	−139.3 (5)
C5—N—C6—O3	−163.2 (6)	C32—C27—C28—C29	−1.6 (9)
C3—N—C6—O3	−0.6 (9)	C4—C27—C28—C29	−178.5 (6)
C5—N—C6—C7	14.5 (9)	C27—C28—C29—C30	0.1 (10)
C3—N—C6—C7	177.1 (5)	C28—C29—C30—C31	1.0 (10)
O3—C6—C7—C8	−38.4 (9)	C29—C30—C31—C32	−0.5 (10)
N—C6—C7—C8	144.0 (5)	C28—C27—C32—C31	2.0 (9)
O3—C6—C7—C12	83.4 (7)	C4—C27—C32—C31	178.9 (6)
N—C6—C7—C12	−94.3 (6)	C30—C31—C32—C27	−1.0 (10)
C6—C7—C8—C9	−68.6 (7)