Ethyl 1-O-tert-butyl-dimethyl-silyl-2,3-O-isopropyl-idene-5-[(2'S)-tetra-hydro-pyran-2-yl-oxy]-d-glycero-α-d-manno-hepto-furonate.

The title compound {systematic name: (2S,3R)-ethyl 3-[(3aS,4R,6S,6aS)-6-tert-butyl-dimethyl-silyl-oxy-2,2-dimethyl-per-hydro-furo[3,4-d][1,3]dioxol-4-yl]-2-nitro-3-[(S)-tetra-hydro-2H-pyran-2-yl-oxy]propanoate}, C(23)H(41)NO(10)Si, is the product of the Henry reaction of 1-O-tert-butyl-dimethyl-silyl-2,3-O-isopropyl-idene-α-d-lyxo-penta-dialdo-1,4-furan-ose with ethyl nitro-acetate and the subsequent protection of its C-5 hydr-oxy group as tetra-hydro-pyranyl, in order to avoid the retro-Henry reaction. The tetra-hydro-pyranyl group adopts a chair conformation. The absolute configuration, assumed from the synthesis, was confirmed from the diffraction data.

Related literature

For the preparation of the aldehyde precursor of the title compound, see: Brewster et al. (1987 ▶). For the Henry reaction, see: Soengas et al. (2003a ▶). For the protection as tetra­hydro­pyran, see: Soengas et al. (2003b ▶). For other related literature, see: Gruner et al. (2002 ▶); Lillelund et al. (2002 ▶); Ogawa et al. (2005 ▶); Chakraborty et al. (2002 ▶).

Experimental

Crystal data

C23H41NO10Si

M = 519.66

Orthorhombic,

a = 15.593 (3) Å

b = 9.563 (4) Å

c = 19.690 (3) Å

V = 2935.9 (15) Å3

Z = 4

Cu Kα radiation

μ = 1.13 mm−1

T = 293 (2) K

0.48 × 0.40 × 0.32 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.614, T max = 0.714

6473 measured reflections

5898 independent reflections

3434 reflections with I > 2σ(I)

R int = 0.037

3 standard reflections every 167 reflections intensity decay: 4%

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.264

S = 1.11

5898 reflections

325 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.27 e Å−3

Absolute structure: Flack (1983 ▶), 2569 Friedel pairs

Flack parameter: 0.04 (8)

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808021193/cf2203sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021193/cf2203Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C23H41N1O10Si	Dx = 1.176 Mg m−3
Mr = 519.66	Cu Kα radiation λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 18 reflections
a = 15.593 (3) Å	θ = 17.6–42.2º
b = 9.563 (4) Å	µ = 1.13 mm−1
c = 19.690 (3) Å	T = 293 (2) K
V = 2935.9 (15) Å3	Prism, colourless
Z = 4	0.48 × 0.40 × 0.32 mm
F000 = 1120

Enraf–Nonius TurboCAD-4 diffractometer	Rint = 0.037
Radiation source: fine-focus sealed tube	θmax = 73.4º
Monochromator: graphite	θmin = 3.6º
T = 293(2) K	h = −19→0
Non–profiled ω/2θ scans	k = −11→0
Absorption correction: ψ scan(North et al., 1968)	l = −24→24
Tmin = 0.614, Tmax = 0.714	3 standard reflections
6473 measured reflections	every 167 reflections
5898 independent reflections	intensity decay: 4%
3434 reflections with I > 2σ(I)

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.066	w = 1/[σ2(Fo2) + (0.1249P)2 + 1.1254P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.264	(Δ/σ)max < 0.001
S = 1.11	Δρmax = 0.22 e Å−3
5898 reflections	Δρmin = −0.27 e Å−3
325 parameters	Extinction correction: none
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2569 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.04 (8)

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.

	x	y	z	Uiso*/Ueq
O1	0.3708 (2)	0.3276 (4)	0.43815 (17)	0.0688 (9)
C2	0.4611 (3)	0.3178 (7)	0.4327 (3)	0.0722 (14)
H2	0.4895	0.3750	0.4673	0.087*
C3	0.4804 (3)	0.1651 (6)	0.4427 (3)	0.0713 (13)
H3	0.5281	0.1338	0.4142	0.086*
C4	0.3965 (3)	0.0870 (6)	0.4260 (3)	0.0696 (13)
H4	0.4041	0.0158	0.3908	0.084*
C5	0.3381 (3)	0.2059 (6)	0.4035 (2)	0.0666 (13)
H5	0.3447	0.2194	0.3545	0.080*
O6	0.4953 (2)	0.1368 (5)	0.51299 (19)	0.0879 (11)
C7	0.4381 (4)	0.0343 (7)	0.5360 (3)	0.0780 (15)
O8	0.3698 (2)	0.0295 (5)	0.4890 (2)	0.0854 (12)
C9	0.4844 (7)	−0.1044 (9)	0.5337 (7)	0.181 (6)
H9A	0.4487	−0.1755	0.5534	0.271*
H9B	0.5369	−0.0976	0.5589	0.271*
H9C	0.4969	−0.1282	0.4874	0.271*
C10	0.4081 (6)	0.0680 (17)	0.6031 (4)	0.194 (7)
H10A	0.3768	0.1545	0.6017	0.290*
H10B	0.4562	0.0774	0.6331	0.290*
H10C	0.3712	−0.0052	0.6191	0.290*
O11	0.4874 (2)	0.3565 (4)	0.36718 (17)	0.0756 (9)
Si12	0.50307 (12)	0.51726 (18)	0.33863 (9)	0.0858 (5)
C13	0.4458 (7)	0.6418 (10)	0.3943 (6)	0.166 (5)
H13A	0.3886	0.6087	0.4023	0.249*
H13B	0.4435	0.7318	0.3727	0.249*
H13C	0.4757	0.6497	0.4368	0.249*
C14	0.4610 (7)	0.5262 (12)	0.2497 (5)	0.148 (4)
H14A	0.4664	0.4362	0.2286	0.222*
H14B	0.4933	0.5939	0.2244	0.222*
H14C	0.4017	0.5532	0.2506	0.222*
C15	0.6207 (5)	0.5470 (9)	0.3385 (4)	0.107 (2)
C16	0.6623 (6)	0.4457 (13)	0.2889 (5)	0.156 (4)
H16A	0.7196	0.4765	0.2789	0.233*
H16B	0.6294	0.4425	0.2478	0.233*
H16C	0.6644	0.3541	0.3088	0.233*
C17	0.6555 (5)	0.5320 (17)	0.4098 (4)	0.173 (6)
H17A	0.6508	0.4363	0.4240	0.259*
H17B	0.6231	0.5904	0.4400	0.259*
H17C	0.7146	0.5599	0.4105	0.259*
C18	0.6407 (8)	0.6965 (12)	0.3132 (5)	0.175 (5)
H18A	0.7015	0.7115	0.3139	0.263*
H18B	0.6132	0.7633	0.3424	0.263*
H18C	0.6196	0.7075	0.2677	0.263*
C19	0.2448 (3)	0.1860 (7)	0.4193 (2)	0.0733 (15)
H19	0.2402	0.1481	0.4654	0.088*
O20	0.2148 (2)	0.0833 (5)	0.37335 (18)	0.0860 (12)
C21	0.1697 (4)	−0.0350 (9)	0.4032 (3)	0.099 (2)
H21	0.2024	−0.0686	0.4424	0.118*
C22	0.1651 (6)	−0.1488 (9)	0.3517 (4)	0.117 (3)
H22A	0.1470	−0.2345	0.3738	0.141*
H22B	0.2219	−0.1644	0.3331	0.141*
C23	0.1036 (7)	−0.1158 (13)	0.2942 (4)	0.141 (4)
H23A	0.1261	−0.0396	0.2670	0.169*
H23B	0.0971	−0.1971	0.2652	0.169*
C24	0.0191 (6)	−0.0760 (14)	0.3231 (5)	0.153 (4)
H24A	−0.0055	−0.1549	0.3471	0.184*
H24B	−0.0197	−0.0496	0.2869	0.184*
C25	0.0308 (5)	0.0476 (13)	0.3724 (5)	0.143 (4)
H25A	0.0524	0.1280	0.3476	0.172*
H25B	−0.0242	0.0725	0.3919	0.172*
O26	0.0894 (3)	0.0124 (7)	0.4255 (2)	0.1160 (17)
C27	0.1881 (4)	0.3190 (8)	0.4150 (3)	0.0892 (19)
H27	0.1297	0.2906	0.4273	0.107*
N28	0.1840 (4)	0.3743 (8)	0.3432 (3)	0.110 (2)
O29	0.2476 (3)	0.3920 (8)	0.3110 (3)	0.135 (2)
O30	0.1129 (4)	0.4028 (11)	0.3218 (3)	0.194 (4)
C31	0.2115 (5)	0.4367 (11)	0.4606 (4)	0.104 (2)
O32	0.2205 (4)	0.5543 (8)	0.4431 (4)	0.143 (2)
O33	0.2157 (3)	0.3927 (6)	0.5243 (2)	0.1067 (15)
C34	0.2439 (11)	0.4994 (13)	0.5745 (5)	0.188 (6)
H34A	0.2957	0.5446	0.5582	0.225*
H34B	0.1998	0.5702	0.5792	0.225*
C35	0.2591 (10)	0.4413 (15)	0.6345 (7)	0.204 (6)
H35A	0.2092	0.3909	0.6492	0.307*
H35B	0.2724	0.5129	0.6670	0.307*
H35C	0.3067	0.3781	0.6308	0.307*

	U11	U22	U33	U12	U13	U23
O1	0.0590 (17)	0.083 (2)	0.0645 (19)	0.0041 (17)	0.0043 (15)	0.0023 (17)
C2	0.062 (3)	0.092 (4)	0.063 (3)	0.001 (3)	0.003 (2)	−0.002 (3)
C3	0.060 (3)	0.088 (4)	0.067 (3)	0.002 (3)	0.007 (2)	0.015 (3)
C4	0.067 (3)	0.082 (3)	0.059 (3)	0.001 (3)	−0.002 (2)	0.001 (3)
C5	0.054 (2)	0.093 (4)	0.053 (2)	0.000 (2)	0.0011 (19)	−0.004 (2)
O6	0.0667 (19)	0.122 (3)	0.075 (2)	−0.020 (2)	−0.0152 (18)	0.030 (2)
C7	0.072 (3)	0.092 (4)	0.070 (3)	−0.010 (3)	−0.014 (2)	0.017 (3)
O8	0.070 (2)	0.104 (3)	0.082 (2)	−0.018 (2)	−0.0152 (18)	0.032 (2)
C9	0.160 (9)	0.090 (6)	0.292 (15)	−0.005 (6)	−0.124 (10)	0.046 (7)
C10	0.115 (6)	0.37 (2)	0.091 (5)	−0.079 (10)	0.017 (5)	−0.051 (8)
O11	0.074 (2)	0.084 (2)	0.0693 (19)	−0.0028 (19)	0.0122 (17)	0.0124 (17)
Si12	0.0864 (10)	0.0890 (11)	0.0821 (9)	−0.0053 (10)	−0.0054 (8)	0.0167 (9)
C13	0.180 (10)	0.097 (6)	0.221 (12)	0.021 (6)	0.074 (9)	0.001 (7)
C14	0.161 (8)	0.161 (9)	0.123 (6)	−0.035 (7)	−0.053 (6)	0.056 (7)
C15	0.107 (5)	0.140 (6)	0.075 (4)	−0.040 (5)	0.012 (4)	0.020 (4)
C16	0.123 (7)	0.198 (11)	0.146 (8)	−0.020 (7)	0.051 (6)	−0.017 (8)
C17	0.105 (6)	0.316 (17)	0.097 (6)	−0.070 (8)	−0.027 (4)	0.043 (8)
C18	0.204 (11)	0.182 (10)	0.140 (8)	−0.114 (9)	−0.012 (7)	0.043 (7)
C19	0.055 (2)	0.118 (5)	0.046 (2)	−0.001 (3)	−0.0017 (19)	0.005 (3)
O20	0.078 (2)	0.127 (3)	0.0523 (18)	−0.021 (2)	−0.0011 (17)	0.010 (2)
C21	0.085 (4)	0.145 (6)	0.067 (3)	−0.019 (4)	−0.009 (3)	0.013 (4)
C22	0.135 (6)	0.116 (6)	0.101 (5)	−0.029 (5)	0.007 (5)	0.016 (5)
C23	0.144 (8)	0.188 (10)	0.090 (5)	−0.059 (7)	−0.017 (5)	−0.007 (5)
C24	0.112 (7)	0.228 (12)	0.119 (7)	−0.055 (7)	−0.033 (5)	0.017 (7)
C25	0.088 (5)	0.213 (11)	0.129 (7)	−0.014 (6)	−0.036 (5)	0.006 (7)
O26	0.089 (3)	0.181 (5)	0.078 (3)	−0.028 (3)	0.007 (2)	0.010 (3)
C27	0.063 (3)	0.141 (6)	0.064 (3)	0.015 (3)	0.006 (2)	0.015 (4)
N28	0.080 (3)	0.169 (6)	0.080 (3)	0.041 (4)	0.001 (3)	0.033 (4)
O29	0.096 (3)	0.208 (6)	0.101 (3)	0.043 (4)	0.023 (3)	0.067 (4)
O30	0.095 (4)	0.361 (12)	0.125 (5)	0.065 (5)	−0.021 (3)	0.084 (6)
C31	0.083 (4)	0.132 (7)	0.099 (5)	0.043 (5)	0.008 (4)	0.005 (5)
O32	0.157 (5)	0.122 (5)	0.152 (6)	0.039 (4)	−0.002 (4)	0.018 (4)
O33	0.103 (3)	0.138 (4)	0.079 (3)	0.026 (3)	0.010 (2)	−0.013 (3)
C34	0.318 (17)	0.149 (9)	0.096 (7)	0.064 (10)	−0.028 (9)	−0.043 (7)
C35	0.236 (14)	0.219 (15)	0.158 (11)	0.051 (12)	−0.025 (10)	−0.081 (11)

O1—C2	1.415 (6)	C17—H17A	0.960
O1—C5	1.442 (6)	C17—H17B	0.960
C2—O11	1.403 (6)	C17—H17C	0.960
C2—C3	1.504 (8)	C18—H18A	0.960
C2—H2	0.980	C18—H18B	0.960
C3—O6	1.428 (6)	C18—H18C	0.960
C3—C4	1.542 (7)	C19—O20	1.414 (7)
C3—H3	0.980	C19—C27	1.552 (9)
C4—O8	1.419 (6)	C19—H19	0.980
C4—C5	1.523 (8)	O20—C21	1.456 (8)
C4—H4	0.980	C21—O26	1.403 (9)
C5—C19	1.499 (7)	C21—C22	1.488 (11)
C5—H5	0.980	C21—H21	0.980
O6—C7	1.401 (7)	C22—C23	1.517 (11)
C7—O8	1.410 (6)	C22—H22A	0.970
C7—C10	1.438 (10)	C22—H22B	0.970
C7—C9	1.511 (11)	C23—C24	1.485 (14)
C9—H9A	0.960	C23—H23A	0.970
C9—H9B	0.960	C23—H23B	0.970
C9—H9C	0.960	C24—C25	1.539 (15)
C10—H10A	0.960	C24—H24A	0.970
C10—H10B	0.960	C24—H24B	0.970
C10—H10C	0.960	C25—O26	1.429 (9)
O11—Si12	1.655 (4)	C25—H25A	0.970
Si12—C13	1.849 (9)	C25—H25B	0.970
Si12—C15	1.856 (7)	C27—C31	1.486 (12)
Si12—C14	1.871 (8)	C27—N28	1.510 (8)
C13—H13A	0.960	C27—H27	0.980
C13—H13B	0.960	N28—O29	1.188 (7)
C13—H13C	0.960	N28—O30	1.217 (7)
C14—H14A	0.960	C31—O32	1.184 (10)
C14—H14B	0.960	C31—O33	1.323 (9)
C14—H14C	0.960	O33—C34	1.487 (12)
C15—C17	1.511 (10)	C34—C35	1.327 (15)
C15—C16	1.521 (13)	C34—H34A	0.970
C15—C18	1.545 (12)	C34—H34B	0.970
C16—H16A	0.960	C35—H35A	0.960
C16—H16B	0.960	C35—H35B	0.960
C16—H16C	0.960	C35—H35C	0.960
C2—O1—C5	105.2 (4)	C15—C17—H17A	109.5
O11—C2—O1	110.1 (4)	C15—C17—H17B	109.5
O11—C2—C3	108.6 (4)	H17A—C17—H17B	109.5
O1—C2—C3	104.7 (4)	C15—C17—H17C	109.5
O11—C2—H2	111.1	H17A—C17—H17C	109.5
O1—C2—H2	111.1	H17B—C17—H17C	109.5
C3—C2—H2	111.1	C15—C18—H18A	109.5
O6—C3—C2	110.1 (5)	C15—C18—H18B	109.5
O6—C3—C4	104.7 (4)	H18A—C18—H18B	109.5
C2—C3—C4	105.8 (4)	C15—C18—H18C	109.5
O6—C3—H3	111.9	H18A—C18—H18C	109.5
C2—C3—H3	111.9	H18B—C18—H18C	109.5
C4—C3—H3	111.9	O20—C19—C5	106.1 (4)
O8—C4—C5	111.6 (4)	O20—C19—C27	110.2 (4)
O8—C4—C3	104.5 (4)	C5—C19—C27	115.9 (5)
C5—C4—C3	102.0 (4)	O20—C19—H19	108.1
O8—C4—H4	112.7	C5—C19—H19	108.1
C5—C4—H4	112.7	C27—C19—H19	108.1
C3—C4—H4	112.7	C19—O20—C21	116.2 (4)
O1—C5—C19	110.4 (4)	O26—C21—O20	107.8 (7)
O1—C5—C4	104.7 (4)	O26—C21—C22	114.0 (6)
C19—C5—C4	115.1 (5)	O20—C21—C22	108.5 (5)
O1—C5—H5	108.8	O26—C21—H21	108.8
C19—C5—H5	108.8	O20—C21—H21	108.8
C4—C5—H5	108.8	C22—C21—H21	108.8
C7—O6—C3	109.9 (4)	C21—C22—C23	112.8 (8)
O6—C7—O8	107.0 (4)	C21—C22—H22A	109.0
O6—C7—C10	110.3 (7)	C23—C22—H22A	109.0
O8—C7—C10	111.3 (6)	C21—C22—H22B	109.0
O6—C7—C9	107.5 (6)	C23—C22—H22B	109.0
O8—C7—C9	108.2 (6)	H22A—C22—H22B	107.8
C10—C7—C9	112.3 (9)	C24—C23—C22	109.1 (7)
C7—O8—C4	109.8 (4)	C24—C23—H23A	109.9
C7—C9—H9A	109.5	C22—C23—H23A	109.9
C7—C9—H9B	109.5	C24—C23—H23B	109.9
H9A—C9—H9B	109.5	C22—C23—H23B	109.9
C7—C9—H9C	109.5	H23A—C23—H23B	108.3
H9A—C9—H9C	109.5	C23—C24—C25	109.5 (7)
H9B—C9—H9C	109.5	C23—C24—H24A	109.8
C7—C10—H10A	109.5	C25—C24—H24A	109.8
C7—C10—H10B	109.5	C23—C24—H24B	109.8
H10A—C10—H10B	109.5	C25—C24—H24B	109.8
C7—C10—H10C	109.5	H24A—C24—H24B	108.2
H10A—C10—H10C	109.5	O26—C25—C24	110.9 (9)
H10B—C10—H10C	109.5	O26—C25—H25A	109.5
C2—O11—Si12	126.9 (4)	C24—C25—H25A	109.5
O11—Si12—C13	109.0 (4)	O26—C25—H25B	109.5
O11—Si12—C15	106.8 (3)	C24—C25—H25B	109.5
C13—Si12—C15	112.3 (5)	H25A—C25—H25B	108.1
O11—Si12—C14	108.0 (4)	C21—O26—C25	114.6 (6)
C13—Si12—C14	110.9 (6)	C31—C27—N28	108.1 (7)
C15—Si12—C14	109.8 (4)	C31—C27—C19	116.6 (5)
Si12—C13—H13A	109.5	N28—C27—C19	111.2 (5)
Si12—C13—H13B	109.5	C31—C27—H27	106.8
H13A—C13—H13B	109.5	N28—C27—H27	106.8
Si12—C13—H13C	109.5	C19—C27—H27	106.8
H13A—C13—H13C	109.5	O29—N28—O30	122.9 (6)
H13B—C13—H13C	109.5	O29—N28—C27	120.9 (5)
Si12—C14—H14A	109.5	O30—N28—C27	116.2 (6)
Si12—C14—H14B	109.5	O32—C31—O33	124.9 (9)
H14A—C14—H14B	109.5	O32—C31—C27	124.9 (8)
Si12—C14—H14C	109.5	O33—C31—C27	110.1 (8)
H14A—C14—H14C	109.5	C31—O33—C34	115.2 (8)
H14B—C14—H14C	109.5	C35—C34—O33	111.0 (12)
C17—C15—C16	112.5 (9)	C35—C34—H34A	109.4
C17—C15—C18	108.3 (8)	O33—C34—H34A	109.4
C16—C15—C18	107.3 (8)	C35—C34—H34B	109.4
C17—C15—Si12	109.8 (5)	O33—C34—H34B	109.4
C16—C15—Si12	109.0 (6)	H34A—C34—H34B	108.0
C18—C15—Si12	109.9 (7)	C34—C35—H35A	109.5
C15—C16—H16A	109.5	C34—C35—H35B	109.5
C15—C16—H16B	109.5	H35A—C35—H35B	109.5
H16A—C16—H16B	109.5	C34—C35—H35C	109.5
C15—C16—H16C	109.5	H35A—C35—H35C	109.5
H16A—C16—H16C	109.5	H35B—C35—H35C	109.5
H16B—C16—H16C	109.5
C5—O1—C2—O11	76.7 (5)	C14—Si12—C15—C16	−53.3 (8)
C5—O1—C2—C3	−39.8 (5)	O11—Si12—C15—C18	−179.2 (6)
O11—C2—C3—O6	151.5 (4)	C13—Si12—C15—C18	−59.8 (7)
O1—C2—C3—O6	−90.9 (5)	C14—Si12—C15—C18	64.0 (8)
O11—C2—C3—C4	−95.9 (5)	O1—C5—C19—O20	168.6 (4)
O1—C2—C3—C4	21.7 (5)	C4—C5—C19—O20	−73.1 (5)
O6—C3—C4—O8	3.3 (6)	O1—C5—C19—C27	45.9 (6)
C2—C3—C4—O8	−113.0 (5)	C4—C5—C19—C27	164.2 (4)
O6—C3—C4—C5	119.7 (4)	C5—C19—O20—C21	127.8 (5)
C2—C3—C4—C5	3.3 (5)	C27—C19—O20—C21	−105.9 (6)
C2—O1—C5—C19	166.9 (4)	C19—O20—C21—O26	71.9 (6)
C2—O1—C5—C4	42.4 (5)	C19—O20—C21—C22	−164.1 (5)
O8—C4—C5—O1	84.2 (5)	O26—C21—C22—C23	48.8 (9)
C3—C4—C5—O1	−26.8 (5)	O20—C21—C22—C23	−71.3 (8)
O8—C4—C5—C19	−37.1 (6)	C21—C22—C23—C24	−52.3 (11)
C3—C4—C5—C19	−148.2 (4)	C22—C23—C24—C25	56.2 (11)
C2—C3—O6—C7	122.7 (5)	C23—C24—C25—O26	−58.1 (11)
C4—C3—O6—C7	9.4 (6)	O20—C21—O26—C25	69.9 (8)
C3—O6—C7—O8	−18.8 (6)	C22—C21—O26—C25	−50.6 (10)
C3—O6—C7—C10	−140.0 (7)	C24—C25—O26—C21	54.9 (10)
C3—O6—C7—C9	97.3 (6)	O20—C19—C27—C31	179.8 (5)
O6—C7—O8—C4	21.1 (7)	C5—C19—C27—C31	−59.7 (7)
C10—C7—O8—C4	141.7 (8)	O20—C19—C27—N28	−55.6 (6)
C9—C7—O8—C4	−94.4 (7)	C5—C19—C27—N28	64.9 (7)
C5—C4—O8—C7	−124.3 (5)	C31—C27—N28—O29	79.4 (9)
C3—C4—O8—C7	−14.8 (6)	C19—C27—N28—O29	−49.8 (10)
O1—C2—O11—Si12	82.7 (5)	C31—C27—N28—O30	−98.5 (9)
C3—C2—O11—Si12	−163.2 (4)	C19—C27—N28—O30	132.2 (8)
C2—O11—Si12—C13	−19.6 (6)	N28—C27—C31—O32	3.7 (10)
C2—O11—Si12—C15	101.9 (5)	C19—C27—C31—O32	129.9 (8)
C2—O11—Si12—C14	−140.2 (5)	N28—C27—C31—O33	179.9 (5)
O11—Si12—C15—C17	−60.2 (9)	C19—C27—C31—O33	−54.0 (7)
C13—Si12—C15—C17	59.2 (9)	O32—C31—O33—C34	−7.5 (12)
C14—Si12—C15—C17	−177.0 (9)	C27—C31—O33—C34	176.4 (8)
O11—Si12—C15—C16	63.5 (6)	C31—O33—C34—C35	−170.2 (11)
C13—Si12—C15—C16	−177.1 (7)