2-(Methoxy­meth­oxy)-1-(4-oxobicyclo­[3.1.0]hexan-1-yl)ethyl 4-nitro­benzoate

Li, J.; Lowary, T.L.; Ferguson, M.J.

doi:10.1107/S160053680706686X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o329

https://doi.org/10.1107/S160053680706686X

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2-(Methoxymethoxy)-1-(4-oxobicyclo[3.1.0]hexan-1-yl)ethyl 4-nitrobenzoate

Jing Li,^a Todd L. Lowary ^a and Michael J. Ferguson ^b ^*

^aAlberta Ingenuity Centre for Carbohydrate Science, Department of Chemistry, University of Alberta, Edmonton, AB, T6G 2G2, Canada, and ^bX-ray Crystallography Laboratory, Department of Chemistry, University of Alberta, Edmonton, AB, T6G 2G2, Canada
^*Correspondence e-mail: michael.ferguson@ualberta.ca

(Received 7 December 2007; accepted 13 December 2007; online 21 December 2007)

In the title compound, C₁₇H₁₉NO₇, the cyclopentane ring is in an envelope conformation in which the methylene group forming the flap is cis to the cyclopropane group. The relative configuration between the 4-nitrobenzoyloxy substituent on the side chain and the cyclopropane ring is trans and the methoxylmethyl group adopts the expected conformation in which the two O atoms are gauche to one another.

Related literature

For the synthesis of mimetics of biologically important furanoside rings, see: Callam & Lowary (2000 , 2001 ); Callam et al. (2001 ); Centrone & Lowary (2002 ). For examples of crystal structures of bicyclo[3.1.0]hexane systems, see; Gurskaya et al. (1990 , 1996 ); Gallucci et al. (2000 ); Garcia et al. (1992 ); Guthrie et al. (1981 ); Màrton-Merész et al. (1983 ); Biswas et al. (1996 ); Bai et al. (2004 ). For related literature, see: Hamon & Shirley (1988 ); Li & Lowary (2008 ); Wolfe (1972 ).

Experimental

Crystal data

C₁₇H₁₉NO₇
M_r = 349.33
Triclinic, $[P \overline 1]$
a = 8.3387 (5) Å
b = 10.1389 (6) Å
c = 10.4935 (6) Å
α = 98.5259 (8)°
β = 100.4967 (8)°
γ = 101.1562 (7)°
V = 840.22 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 193 (2) K
0.52 × 0.50 × 0.47 mm

Data collection

Bruker PLATFORM diffractometer SMART 1000 CCD area-detector
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.946, T_max = 0.951
7436 measured reflections
3825 independent reflections
3476 reflections with I > 2σ(I)
R_int = 0.009

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.120
S = 1.05
3825 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a ); molecular graphics: SHELXTL (Sheldrick, 1997b ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053680706686X/lh2582sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680706686X/lh2582Isup2.hkl

checkCIF report

Comment top

In the course of our studies on the synthesis of mimetics of biologically important furanoside rings (Callam & Lowary, 2000; Callam & Lowary, 2001; Callam et al., 2001; Centrone & Lowary, 2002), we targeted compounds of the general structure (I) for synthesis. A key step in the route to these compounds (Li & Lowary, 2008) was a base-promoted ring contraction of epoxyketone (II) [see Fig. 1] (Hamon & Shirley, 1988), which gave a 1:1 mixture of two steroisomeric products (III) and (IV), both as racemic mixtures. In these products, it was critical to determine the relative configuration of the carbon bearing the OH group and the cyclopropane ring and doing so by spectroscopic methods was not possible. Therefore, derivatives of both (III) and (IV) were prepared in hopes of obtaining a crystalline material. We were pleased to discover that esterification of (IV) with 4-nitrobenzoyl chloride gave a crystalline product (V) from which the relative configuration of these two groups could be established by X-ray crystallography.

The molecular structure of (V) is shown in Fig. 2. In common with other bicyclo[3.1.0]hexane systems for which crystal structures have been reported (examples: Gurskaya et al., 1990; Gurskaya et al., 1996; Gallucci et al., 2000; Garcia et al., 1992; Guthrie et al., 1981; Màrton-Merész et al., 1983; Biswas et al., 1996; Bai et al., 2004), the five-membered ring is puckered into an envelope in which C3 is above the plane formed by C1, C2, C4 and C5. This places C3 cis to the cyclopropane moiety that is fused to the cyclopentane ring. As can clearly be seen, the relative configuration of the stereogenic centre substituted with the 4-nitrobenzoyloxy group and the cyclopropane is trans. Thus, it is possible to establish the structure of (IV) and, by inference, (III). The methoxymethoxy group present in the side chain adopted the expected conformation (Wolfe, 1972) in which the two O atoms are gauche to each other.

Related literature top

For the synthesis of mimetics of biologically important furanoside rings, see: Callam & Lowary (2000, 2001); Callam et al. (2001); Centrone & Lowary (2002). For examples of crystal structures of bicyclo[3.1.0]hexane systems, see; Gurskaya et al. (1990, 1996); Gallucci et al. (2000); Garcia et al. (1992); Guthrie et al. (1981); Màrton-Merész et al. (1983); Biswas, et al. (1996); Bai et al. (2004).

For related literature, see: Hamon & Shirley (1988); Li & Lowary (2008); Wolfe (1972).

Experimental top

1-[2'-(methoxymethoxy)-1'-4-nitrobenzoyloxyethyl]bicyclo[3.1.0]hexan-4-one (V). To a stirred solution of (IV) (1.23 g, 6.15 mmol) in CH₂Cl₂-pyridine (10:1, 8.8 ml) was added 4-nitrobenzoyl chloride (1.36 g, 7.38 mmol) at 273 K. The mixture was then warmed to room temperature and stirred for 1 h. The reaction mixture was quenched by adding CH₃OH, and then diluted with CH₂Cl₂. The solution was washed with 1 M HCl and water. The organic layer was dried (Na₂SO₄), filtered, concentrated, and the residue was purified by chromatography (1:1 EtOAc-hexane) to provide the product (V) as a light yellow solid (yield 1.60 g, 76%). This material was recrystallized from CH₂Cl₂ to provide a crystalline solid (m.p. 380–382 K). R_f 0.36 (1:1 EtOAc-Hexane); ¹H NMR (500 MHz, CDCl₃, δ_H) 8.32–8.30 (m, 2 H, Ar), 8.23–8.21 (m, 2 H, Ar), 5.11 (dd, 1 H, J = 4.7, 7.0 Hz, H-7), 4.67–4.64 (m, 2 H, OCH₂O), 3.95–3.88 (m, 2 H, MOMOCH₂), 3.35 (s, 3 H, OCH₃), 2.40–2.32 (m, 1 H, H-3), 2.16–2.13 (m, 3 H, H-2, H-3), 2.00 (dd, 1 H, J = 3.6, 9.4 Hz, H-5), 1.47 (dd, 1 H, J = 5.2, 9.4 Hz, H-6), 1.28 (dd, 1 H, J = 3.6, 5.2 Hz, H-6); ¹³C NMR (125 MHz, CDCl₃, δ_C) 212.3 (C-4), 163.9 (C-11), 150.7 (Ar), 135.2 (Ar), 130.4 (Ar x 2), 123.6 (Ar x 2), 96.6 (C-9), 76.2 (C-7), 67.3 (C-8), 55.5 (C-10), 34.3 (C-1), 32.8 (C-5), 32.6 (C-3), 22.7 (C-2), 17.9 (C-6). HRMS (ESI) m/z calculated for C₁₇H₁₉NO₇ + Na: 372.1054, found: 372.1055.

Structure description top

For the synthesis of mimetics of biologically important furanoside rings, see: Callam & Lowary (2000, 2001); Callam et al. (2001); Centrone & Lowary (2002). For examples of crystal structures of bicyclo[3.1.0]hexane systems, see; Gurskaya et al. (1990, 1996); Gallucci et al. (2000); Garcia et al. (1992); Guthrie et al. (1981); Màrton-Merész et al. (1983); Biswas, et al. (1996); Bai et al. (2004).

For related literature, see: Hamon & Shirley (1988); Li & Lowary (2008); Wolfe (1972).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top

	Fig. 1. Schemes of title (IV) and related compounds.
	Fig. 2. Perspective view of (V), showing the atom labelling scheme. Non- hydrogen atoms are represented by ellipsoids at the 50% probability level. Hydrogen atoms are shown with arbitrarily small radii.

2-(Methoxymethoxy)-1-(4-oxobicyclo[3.1.0]hexan-1-yl)ethyl 4-nitrobenzoate top

Crystal data top

C₁₇H₁₉NO₇	Z = 2
M_r = 349.33	F(000) = 368
Triclinic, P1	D_x = 1.381 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3387 (5) Å	Cell parameters from 7818 reflections
b = 10.1389 (6) Å	θ = 2.6–27.5°
c = 10.4935 (6) Å	µ = 0.11 mm⁻¹
α = 98.5259 (8)°	T = 193 K
β = 100.4967 (8)°	Fragment, colourless
γ = 101.1562 (7)°	0.52 × 0.50 × 0.47 mm
V = 840.22 (9) Å³

Data collection top

Bruker PLATFORM diffractometer/SMART 1000 CCD area-detector	3825 independent reflections
Radiation source: fine-focus sealed tube	3476 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.009
Detector resolution: 8.192 pixels mm^-1	θ_max = 27.5°, θ_min = 2.0°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→13
T_min = 0.946, T_max = 0.951	l = −13→13
7436 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0703P)² + 0.1568P] where P = (F_o² + 2F_c²)/3
3825 reflections	(Δ/σ)_max = 0.013
227 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₇H₁₉NO₇	γ = 101.1562 (7)°
M_r = 349.33	V = 840.22 (9) Å³
Triclinic, P1	Z = 2
a = 8.3387 (5) Å	Mo Kα radiation
b = 10.1389 (6) Å	µ = 0.11 mm⁻¹
c = 10.4935 (6) Å	T = 193 K
α = 98.5259 (8)°	0.52 × 0.50 × 0.47 mm
β = 100.4967 (8)°

Data collection top

Bruker PLATFORM diffractometer/SMART 1000 CCD area-detector	3825 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	3476 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.951	R_int = 0.009
7436 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.05	Δρ_max = 0.31 e Å⁻³
3825 reflections	Δρ_min = −0.17 e Å⁻³
227 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.09546 (12)	0.07242 (11)	0.73892 (11)	0.0553 (3)
O2	0.27720 (9)	0.22849 (8)	0.35099 (8)	0.03307 (19)
O3	0.36653 (10)	0.48159 (9)	0.28812 (8)	0.0367 (2)
O4	0.19060 (11)	0.53166 (10)	0.10951 (9)	0.0469 (2)
O5	0.54644 (13)	0.22855 (12)	0.42875 (11)	0.0650 (3)
O6	0.43439 (13)	−0.32377 (10)	−0.08313 (10)	0.0534 (3)
O7	0.18678 (14)	−0.29604 (11)	−0.15763 (10)	0.0602 (3)
N	0.32018 (14)	−0.26560 (10)	−0.07714 (10)	0.0398 (2)
C1	0.16536 (13)	0.31828 (10)	0.53155 (10)	0.0302 (2)
C2	−0.01745 (14)	0.24464 (13)	0.47296 (12)	0.0384 (3)
H2A	−0.0267	0.1788	0.3908	0.046*
H2B	−0.0864	0.3112	0.4527	0.046*
C3	−0.07499 (15)	0.16936 (15)	0.57953 (14)	0.0458 (3)
H3A	−0.1392	0.2220	0.6298	0.055*
H3B	−0.1466	0.0775	0.5389	0.055*
C4	0.08438 (15)	0.15744 (12)	0.66935 (12)	0.0391 (3)
C5	0.22604 (14)	0.26104 (11)	0.65309 (11)	0.0344 (2)
H5	0.3421	0.2453	0.6717	0.041*
C6	0.19962 (16)	0.40686 (12)	0.66433 (11)	0.0379 (3)
H6A	0.1024	0.4264	0.6994	0.046*
H6B	0.3003	0.4831	0.6890	0.046*
C7	0.28480 (13)	0.35255 (10)	0.44415 (10)	0.0294 (2)
H7	0.4011	0.3873	0.4990	0.035*
C8	0.24071 (13)	0.45645 (11)	0.36257 (11)	0.0331 (2)
H8A	0.1291	0.4203	0.3028	0.040*
H8B	0.2384	0.5422	0.4206	0.040*
C9	0.34064 (15)	0.57459 (13)	0.20414 (12)	0.0414 (3)
H9A	0.3415	0.6636	0.2582	0.050*
H9B	0.4348	0.5892	0.1586	0.050*
C10	0.18474 (19)	0.41015 (17)	0.01905 (14)	0.0547 (4)
H10A	0.0777	0.3849	−0.0454	0.066*
H10B	0.1956	0.3356	0.0674	0.066*
H10C	0.2769	0.4264	−0.0270	0.066*
C11	0.41618 (14)	0.18250 (11)	0.35071 (11)	0.0332 (2)
C12	0.38783 (13)	0.06385 (10)	0.23884 (10)	0.0297 (2)
C13	0.52157 (14)	0.00427 (11)	0.22180 (11)	0.0328 (2)
H13	0.6274	0.0381	0.2811	0.039*
C14	0.50030 (14)	−0.10469 (11)	0.11803 (11)	0.0328 (2)
H14	0.5905	−0.1461	0.1051	0.039*
C15	0.34449 (14)	−0.15100 (10)	0.03447 (10)	0.0317 (2)
C16	0.20974 (15)	−0.09435 (12)	0.04924 (12)	0.0385 (3)
H16	0.1041	−0.1290	−0.0101	0.046*
C17	0.23241 (14)	0.01446 (12)	0.15285 (12)	0.0361 (2)
H17	0.1416	0.0553	0.1651	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0480 (5)	0.0566 (6)	0.0701 (7)	0.0130 (4)	0.0196 (5)	0.0295 (5)
O2	0.0283 (4)	0.0314 (4)	0.0349 (4)	0.0070 (3)	0.0051 (3)	−0.0062 (3)
O3	0.0310 (4)	0.0466 (5)	0.0339 (4)	0.0100 (3)	0.0069 (3)	0.0108 (3)
O4	0.0386 (5)	0.0592 (6)	0.0436 (5)	0.0144 (4)	0.0021 (4)	0.0154 (4)
O5	0.0436 (5)	0.0701 (7)	0.0627 (6)	0.0286 (5)	−0.0171 (5)	−0.0310 (5)
O6	0.0586 (6)	0.0459 (5)	0.0544 (6)	0.0203 (4)	0.0154 (5)	−0.0091 (4)
O7	0.0642 (7)	0.0551 (6)	0.0463 (5)	0.0174 (5)	−0.0092 (5)	−0.0168 (4)
N	0.0500 (6)	0.0325 (5)	0.0347 (5)	0.0094 (4)	0.0092 (4)	−0.0001 (4)
C1	0.0295 (5)	0.0306 (5)	0.0287 (5)	0.0084 (4)	0.0044 (4)	0.0006 (4)
C2	0.0277 (5)	0.0490 (6)	0.0357 (6)	0.0080 (5)	0.0045 (4)	0.0033 (5)
C3	0.0306 (6)	0.0577 (8)	0.0489 (7)	0.0069 (5)	0.0108 (5)	0.0110 (6)
C4	0.0372 (6)	0.0409 (6)	0.0414 (6)	0.0102 (5)	0.0132 (5)	0.0075 (5)
C5	0.0317 (5)	0.0365 (5)	0.0335 (5)	0.0081 (4)	0.0040 (4)	0.0052 (4)
C6	0.0446 (6)	0.0356 (6)	0.0311 (5)	0.0095 (5)	0.0081 (5)	−0.0018 (4)
C7	0.0277 (5)	0.0277 (5)	0.0292 (5)	0.0063 (4)	0.0042 (4)	−0.0033 (4)
C8	0.0310 (5)	0.0350 (5)	0.0332 (5)	0.0091 (4)	0.0075 (4)	0.0035 (4)
C9	0.0384 (6)	0.0440 (6)	0.0402 (6)	0.0055 (5)	0.0052 (5)	0.0126 (5)
C10	0.0476 (7)	0.0665 (9)	0.0422 (7)	0.0082 (6)	−0.0013 (6)	0.0063 (6)
C11	0.0316 (5)	0.0335 (5)	0.0326 (5)	0.0104 (4)	0.0040 (4)	0.0004 (4)
C12	0.0307 (5)	0.0282 (5)	0.0294 (5)	0.0071 (4)	0.0065 (4)	0.0028 (4)
C13	0.0304 (5)	0.0332 (5)	0.0332 (5)	0.0096 (4)	0.0033 (4)	0.0024 (4)
C14	0.0354 (5)	0.0314 (5)	0.0345 (5)	0.0128 (4)	0.0099 (4)	0.0057 (4)
C15	0.0400 (6)	0.0260 (5)	0.0285 (5)	0.0068 (4)	0.0089 (4)	0.0025 (4)
C16	0.0314 (5)	0.0375 (6)	0.0395 (6)	0.0054 (4)	0.0012 (4)	−0.0040 (5)
C17	0.0292 (5)	0.0366 (5)	0.0397 (6)	0.0095 (4)	0.0057 (4)	−0.0018 (4)

Geometric parameters (Å, º) top

O1—C4	1.2155 (16)	C5—H5	1.0000
O2—C11	1.3306 (13)	C6—H6A	0.9900
O2—C7	1.4573 (11)	C6—H6B	0.9900
O3—C9	1.4029 (14)	C7—C8	1.5100 (15)
O3—C8	1.4249 (13)	C7—H7	1.0000
O4—C9	1.3962 (14)	C8—H8A	0.9900
O4—C10	1.4262 (18)	C8—H8B	0.9900
O5—C11	1.1978 (14)	C9—H9A	0.9900
O6—N	1.2194 (14)	C9—H9B	0.9900
O7—N	1.2222 (14)	C10—H10A	0.9800
N—C15	1.4771 (13)	C10—H10B	0.9800
C1—C6	1.4880 (14)	C10—H10C	0.9800
C1—C7	1.4991 (15)	C11—C12	1.5005 (14)
C1—C5	1.5223 (15)	C12—C17	1.3905 (15)
C1—C2	1.5301 (15)	C12—C13	1.3936 (15)
C2—C3	1.5395 (18)	C13—C14	1.3909 (15)
C2—H2A	0.9900	C13—H13	0.9500
C2—H2B	0.9900	C14—C15	1.3799 (15)
C3—C4	1.5194 (17)	C14—H14	0.9500
C3—H3A	0.9900	C15—C16	1.3796 (16)
C3—H3B	0.9900	C16—C17	1.3870 (15)
C4—C5	1.4746 (16)	C16—H16	0.9500
C5—C6	1.5271 (16)	C17—H17	0.9500

C11—O2—C7	118.68 (8)	O2—C7—H7	109.6
C9—O3—C8	113.65 (9)	C1—C7—H7	109.6
C9—O4—C10	112.74 (10)	C8—C7—H7	109.6
O6—N—O7	124.19 (10)	O3—C8—C7	106.79 (8)
O6—N—C15	117.96 (10)	O3—C8—H8A	110.4
O7—N—C15	117.85 (10)	C7—C8—H8A	110.4
C6—C1—C7	117.45 (9)	O3—C8—H8B	110.4
C6—C1—C5	60.96 (7)	C7—C8—H8B	110.4
C7—C1—C5	118.28 (9)	H8A—C8—H8B	108.6
C6—C1—C2	116.10 (9)	O4—C9—O3	113.68 (10)
C7—C1—C2	120.97 (9)	O4—C9—H9A	108.8
C5—C1—C2	108.03 (9)	O3—C9—H9A	108.8
C1—C2—C3	105.52 (9)	O4—C9—H9B	108.8
C1—C2—H2A	110.6	O3—C9—H9B	108.8
C3—C2—H2A	110.6	H9A—C9—H9B	107.7
C1—C2—H2B	110.6	O4—C10—H10A	109.5
C3—C2—H2B	110.6	O4—C10—H10B	109.5
H2A—C2—H2B	108.8	H10A—C10—H10B	109.5
C4—C3—C2	105.68 (9)	O4—C10—H10C	109.5
C4—C3—H3A	110.6	H10A—C10—H10C	109.5
C2—C3—H3A	110.6	H10B—C10—H10C	109.5
C4—C3—H3B	110.6	O5—C11—O2	125.11 (10)
C2—C3—H3B	110.6	O5—C11—C12	124.22 (10)
H3A—C3—H3B	108.7	O2—C11—C12	110.68 (9)
O1—C4—C5	125.17 (11)	C17—C12—C13	120.31 (10)
O1—C4—C3	125.78 (11)	C17—C12—C11	121.15 (9)
C5—C4—C3	108.97 (10)	C13—C12—C11	118.53 (9)
C4—C5—C1	107.41 (9)	C14—C13—C12	120.05 (10)
C4—C5—C6	115.41 (10)	C14—C13—H13	120.0
C1—C5—C6	58.41 (7)	C12—C13—H13	120.0
C4—C5—H5	119.9	C15—C14—C13	118.12 (10)
C1—C5—H5	119.9	C15—C14—H14	120.9
C6—C5—H5	119.9	C13—C14—H14	120.9
C1—C6—C5	60.63 (7)	C16—C15—C14	123.09 (10)
C1—C6—H6A	117.7	C16—C15—N	118.07 (10)
C5—C6—H6A	117.7	C14—C15—N	118.84 (10)
C1—C6—H6B	117.7	C15—C16—C17	118.32 (10)
C5—C6—H6B	117.7	C15—C16—H16	120.8
H6A—C6—H6B	114.8	C17—C16—H16	120.8
O2—C7—C1	108.39 (8)	C16—C17—C12	120.11 (10)
O2—C7—C8	106.47 (8)	C16—C17—H17	119.9
C1—C7—C8	113.09 (8)	C12—C17—H17	119.9

C6—C1—C2—C3	−52.63 (13)	C9—O3—C8—C7	178.58 (9)
C7—C1—C2—C3	154.16 (10)	O2—C7—C8—O3	−62.70 (10)
C5—C1—C2—C3	13.23 (12)	C1—C7—C8—O3	178.37 (8)
C1—C2—C3—C4	−20.30 (13)	C10—O4—C9—O3	−63.98 (14)
C2—C3—C4—O1	−156.31 (13)	C8—O3—C9—O4	−60.59 (13)
C2—C3—C4—C5	20.54 (14)	C7—O2—C11—O5	6.45 (18)
O1—C4—C5—C1	164.54 (12)	C7—O2—C11—C12	−173.72 (8)
C3—C4—C5—C1	−12.34 (13)	O5—C11—C12—C17	179.13 (13)
O1—C4—C5—C6	−132.77 (13)	O2—C11—C12—C17	−0.71 (15)
C3—C4—C5—C6	50.36 (13)	O5—C11—C12—C13	−1.43 (19)
C6—C1—C5—C4	109.58 (11)	O2—C11—C12—C13	178.73 (9)
C7—C1—C5—C4	−142.96 (10)	C17—C12—C13—C14	0.32 (17)
C2—C1—C5—C4	−0.81 (12)	C11—C12—C13—C14	−179.12 (10)
C7—C1—C5—C6	107.46 (10)	C12—C13—C14—C15	−0.23 (16)
C2—C1—C5—C6	−110.39 (10)	C13—C14—C15—C16	−0.01 (17)
C7—C1—C6—C5	−108.79 (10)	C13—C14—C15—N	179.31 (10)
C2—C1—C6—C5	97.02 (11)	O6—N—C15—C16	−173.37 (11)
C4—C5—C6—C1	−95.56 (11)	O7—N—C15—C16	6.64 (16)
C11—O2—C7—C1	−120.22 (10)	O6—N—C15—C14	7.28 (16)
C11—O2—C7—C8	117.82 (10)	O7—N—C15—C14	−172.71 (11)
C6—C1—C7—O2	155.15 (9)	C14—C15—C16—C17	0.16 (18)
C5—C1—C7—O2	85.13 (11)	N—C15—C16—C17	−179.17 (10)
C2—C1—C7—O2	−51.99 (12)	C15—C16—C17—C12	−0.07 (18)
C6—C1—C7—C8	−87.05 (11)	C13—C12—C17—C16	−0.17 (18)
C5—C1—C7—C8	−157.06 (9)	C11—C12—C17—C16	179.26 (11)
C2—C1—C7—C8	65.82 (12)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₉NO₇
M_r	349.33
Crystal system, space group	Triclinic, P1
Temperature (K)	193
a, b, c (Å)	8.3387 (5), 10.1389 (6), 10.4935 (6)
α, β, γ (°)	98.5259 (8), 100.4967 (8), 101.1562 (7)
V (Å³)	840.22 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.52 × 0.50 × 0.47

Data collection
Diffractometer	Bruker PLATFORM diffractometer/SMART 1000 CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.946, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	7436, 3825, 3476
R_int	0.009
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.120, 1.05
No. of reflections	3825
No. of parameters	227
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.17

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Acknowledgements

This work was supported by the Natural Science and Engineering Research Council of Canada, the Alberta Ingenuity Centre for Carbohydrate Science and the University of Alberta.

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