organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 64| Part 2| February 2008| Pages o459-o460

(1R,2R,3R,4R,5S)-2,3-Bis[(2S′)-2-acet­­oxy-2-phenyl­acet­­oxy]-4-azido-1-[(2,4-di­nitro­phen­yl)hydrazono­meth­yl]bi­cyclo­[3.1.0]hexa­ne

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

(Received 18 December 2007; accepted 8 January 2008; online 16 January 2008)

In the title compound, C38H29N7O12, the five-membered ring adopts an envelope conformation in which the `flap' is cis to the cyclo­propane group. This conformation is similar to those of other bicyclo­[3.1.0]hexane analogues for which crystal structures have been reported. The absolute configuration of the stereogenic centers on the cyclo­pentane ring, as determined by comparison with the known configurations of the stereogenic centers in the (2S)-2-acet­oxy-2-phenyl­acet­oxy groups, is 1(R), 2(R), 3(R), 4(R) and 5(S). An intramolecular N—H⋯O hydrogen bond is present.

Related literature

For the synthesis of mimetics of biologically important furan­oside rings, see: Callam & Lowary (2000[Callam, C. S. & Lowary, T. L. (2000). Org. Lett. 2, 167-169.]); Callam & Lowary (2001[Callam, C. S. & Lowary, T. L. (2001). J. Org. Chem. 66, 8961-8972.]); Callam et al. (2001[Callam, C. S., Gadikota, R. R. & Lowary, T. L. (2001). J. Org. Chem. 66, 4549-4558.]); Centrone & Lowary (2002[Centrone, C. A. & Lowary, T. L. (2002). J. Org. Chem. 67, 8862-8870.]). For examples of the crystal structures of bicyclo­[3.1.0]hexane systems, see: Gurskaya et al. (1990[Gurskaya, G. V., Bochkarev, A. V., Zdanov, A. S., Papchikhin, A. A., Purygin, P. P. & Krayevsky, A. (1990). FEBS Lett. 265, 63-66.], 1996[Gurskaya, G. V., Zavodnik, V. E. & Surzhikov, S. A. (1996). Mol. Biol. 30, 540-546.]); Gallucci et al. (2000[Gallucci, J. C., Gadikota, R. R. & Lowary, T. L. (2000). Acta Cryst. C56, e365.]); Garcia et al. (1992[Garcia, J. G., Voll, R. J., Fronczek, F. R. & Younathan, E. S. (1992). Acta Cryst. C48, 1692-1694.]); Guthrie et al. (1981[Guthrie, R. D., Jenkins, I. S., Yamasaki, R., Skelton, B. W. & White, A. H. (1981). J. Chem. Soc. Perkin Trans. 1, pp. 2328-2334.]); Màrton-Merész et al. (1983[Màrton-Merész, M., Kuszmann, J., Pelczer, I., Pàrkànyi, L., Koritsànszky, T. & Kàlmàn, A. (1983). Tetrahedron, 39, 275-285.]); Biswas et al. (1996[Biswas, G., Chandra, T., Garg, N., Bhakuni, D. S., Pramanik, A., Avasthi, K. & Maulik, P. R. (1996). Acta Cryst. C52, 2563-2566.]); Bai et al. (2004[Bai, Y., Lowary, T. L. & Ferguson, M. J. (2004). Acta Cryst. E60, o2201-o2203.]). For related literature, see: Li & Lowary (2008[Li, J. & Lowary, T. L. (2008). Submitted to Org. Lett..]).

[Scheme 1]

Experimental

Crystal data
  • C33H29N7O12

  • Mr = 715.63

  • Monoclinic, P 21

  • a = 6.8522 (11) Å

  • b = 17.747 (3) Å

  • c = 13.729 (2) Å

  • β = 99.006 (2)°

  • V = 1648.9 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.11 mm−1

  • T = 193 (2) K

  • 0.63 × 0.56 × 0.04 mm

Data collection
  • Bruker SMART 1000 CCD area-detector/PLATFORM diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2003[Bruker (2003). SADABS (Version 2.10) and SAINT (Version 7.06A). Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.756, Tmax = 0.996

  • 13919 measured reflections

  • 3905 independent reflections

  • 3150 reflections with I > 2σ(I)

  • Rint = 0.040

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.104

  • S = 1.04

  • 3905 reflections

  • 471 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.20 e Å−3

  • Δρmin = −0.23 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N11—H11N⋯O10 0.88 2.00 2.618 (3) 126

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART. Version 5.054. Bruker AXS Inc., Madison, Wisconsin, U.SA.]); cell refinement: SAINT (Bruker, 2003[Bruker (2003). SADABS (Version 2.10) and SAINT (Version 7.06A). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT (Bruker, 2003[Bruker (2003). SADABS (Version 2.10) and SAINT (Version 7.06A). Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

As part of an ongoing program on the synthesis of furanose ring mimetics (Callam & Lowary, 2000; Callam & Lowary, 2001; Callam et al., 2001; Centrone & Lowary, 2002), we have endeavored to prepare compounds of the general structure (I). The route we developed for the preparation of these materials (Li & Lowary, 2008) started from an achiral starting material and relied upon a late stage resolution by derivatization with O-acetyl-(S)-mandelic acid. In the course of synthesizing (I), aldehyde (II) was prepared and, to determine the absolute configuration of the sterogenic centers in the cyclopentane ring, it was reacted with 2,4-dinitrophenylhydrazine to afford hydrazone derivative (III), which is a crystalline solid.

[Insert Scheme 1 here]

The structure of (III) in the crystal is shown in Fig. 1. The five-membered ring adopts an envelope conformation in which C3 is displaced below the plane formed by C1, C2, C4 and C5 and is therefore oriented cis to the fused cyclopropane moiety. Thus, the conformation of this ring is similar to that in other bicyclo[3.1.0]hexane analogues (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 absolute configuration of the stereogenic centers in the molecule could be established by comparison with those present in the (S)—O-acetylmandeloxyl substituents attached at C2 and C3. Thus, the absolute configuration was established as 1(R), 2(R), 3(R), 4(R), 5(S).

[Insert Figure 1 here]

Related literature top

For the synthesis of mimetics of biologically important furanoside rings, see: Callam & Lowary (2000); Callam & Lowary (2001); Callam et al. (2001); Centrone & Lowary (2002). For examples of the crystal structures of bicyclo[3.1.0]hexane systems, see: 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). For related literature, see: Li & Lowary (2008).

Experimental top

Compound (II) (5.8 mg, 0.011 mmol) was dissolved in CH3OH (1 ml) and 1M 2,4-dinitrophenylhydrizine (1 ml) was added. The mixture was swirled for 1 min and then the solution was concentrated. The resulting residue was purified by chromatography (3:1 hexane-EtOAc) to give (III) (yield 4.2 mg, 53%) as a yellow solid. This material was recrystallized from CH3OH to give a crystalline material (m.p. = 331–333 K).

Refinement top

Hydrogen atoms were generated in idealized positions (according to the sp2 or sp3 geometries of their parent carbon or nitrogen atoms), and then refined using a riding model with fixed C—H (0.95–1.00 Å) and N—H (0.88 Å) and with Uiso(H) = 120% of the Ueq for the parent atoms.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The title compound with numbering scheme used. Hydrogen bonding interactions shown as dotted lines. Ellipsoids are drawn at the 50% probability level. Hydrogen atoms of aromatic-groups have been omitted.
[Figure 2] Fig. 2. Scheme showing compounds (I), (II) and (III).
(1R,2R,3R,4R,5S)-2,3-Bis[(2S')-2-acetoxy-2-phenylacetoxy]-4-azido-1-[(2,4- dinitrophenyl)hydrazonomethyl]bicyclo[3.1.0]hexane top
Crystal data top
C33H29N7O12F(000) = 744
Mr = 715.63Dx = 1.441 Mg m3
Monoclinic, P21Melting point: 333 K
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 6.8522 (11) ÅCell parameters from 4802 reflections
b = 17.747 (3) Åθ = 2.3–22.4°
c = 13.729 (2) ŵ = 0.11 mm1
β = 99.006 (2)°T = 193 K
V = 1648.9 (5) Å3Plate, yellow
Z = 20.63 × 0.56 × 0.04 mm
Data collection top
Bruker SMART 1000 CCD area-detector/PLATFORM
diffractometer
3905 independent reflections
Radiation source: fine-focus sealed tube3150 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
Detector resolution: 8.192 pixels mm-1θmax = 27.6°, θmin = 1.9°
ω scansh = 88
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
k = 2222
Tmin = 0.757, Tmax = 0.996l = 1717
13919 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0581P)2 + 0.2055P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
3905 reflectionsΔρmax = 0.20 e Å3
471 parametersΔρmin = 0.23 e Å3
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.1 (10)
Crystal data top
C33H29N7O12V = 1648.9 (5) Å3
Mr = 715.63Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.8522 (11) ŵ = 0.11 mm1
b = 17.747 (3) ÅT = 193 K
c = 13.729 (2) Å0.63 × 0.56 × 0.04 mm
β = 99.006 (2)°
Data collection top
Bruker SMART 1000 CCD area-detector/PLATFORM
diffractometer
3905 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
3150 reflections with I > 2σ(I)
Tmin = 0.757, Tmax = 0.996Rint = 0.040
13919 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.104Δρmax = 0.20 e Å3
S = 1.04Δρmin = 0.23 e Å3
3905 reflectionsAbsolute structure: Flack (1983)
471 parametersAbsolute structure parameter: 0.1 (10)
1 restraint
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 > 2σ(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
xyzUiso*/Ueq
O100.0216 (3)0.17710 (12)0.26418 (16)0.0430 (5)
O110.0112 (4)0.21885 (13)0.11642 (18)0.0552 (7)
O120.1584 (4)0.05771 (17)0.14093 (19)0.0633 (7)
O130.1090 (9)0.0610 (2)0.1281 (3)0.1188 (17)
O200.0140 (3)0.20972 (11)0.40781 (13)0.0325 (4)
O210.2602 (4)0.20436 (16)0.33755 (19)0.0563 (7)
O220.1282 (3)0.31877 (12)0.21350 (14)0.0395 (5)
O230.2147 (4)0.40018 (15)0.33712 (19)0.0561 (7)
O300.2856 (3)0.23219 (11)0.60946 (15)0.0370 (5)
O310.1682 (3)0.34574 (11)0.55501 (17)0.0423 (5)
O320.5724 (3)0.38917 (12)0.57755 (17)0.0437 (5)
O330.6065 (5)0.29640 (16)0.4718 (2)0.0641 (7)
N10.2676 (5)0.08960 (15)0.6739 (2)0.0462 (7)
N20.3933 (6)0.10936 (17)0.7397 (3)0.0646 (9)
N30.5225 (8)0.1213 (3)0.7995 (4)0.113 (2)
N100.0001 (4)0.03342 (13)0.35238 (18)0.0331 (5)
N110.0016 (4)0.03229 (13)0.29748 (18)0.0326 (5)
H11N0.01520.07640.32420.039*
N120.0236 (4)0.16687 (14)0.17555 (18)0.0351 (6)
N130.1177 (5)0.00261 (19)0.0941 (2)0.0532 (8)
C10.0749 (4)0.09361 (16)0.4950 (2)0.0330 (6)
C20.0664 (4)0.15750 (15)0.4847 (2)0.0310 (6)
H20.19550.13700.47110.037*
C30.0947 (4)0.19714 (16)0.5849 (2)0.0329 (6)
H30.01240.23510.58710.040*
C40.0799 (5)0.13409 (17)0.6595 (2)0.0399 (7)
H40.04400.15310.72290.048*
C50.0736 (5)0.08206 (17)0.6058 (2)0.0407 (7)
H50.07950.02930.63070.049*
C60.2535 (5)0.11335 (18)0.5436 (2)0.0434 (8)
H6A0.28330.16740.55140.052*
H6B0.37100.08030.52960.052*
C100.0820 (4)0.02899 (16)0.4284 (2)0.0337 (6)
H100.14780.01600.44230.040*
C110.0292 (4)0.02746 (16)0.2031 (2)0.0295 (6)
C120.0412 (4)0.09040 (15)0.1406 (2)0.0297 (6)
C130.0683 (4)0.08305 (17)0.0436 (2)0.0333 (6)
H130.07700.12620.00360.040*
C140.0826 (5)0.01172 (18)0.0063 (2)0.0376 (7)
C150.0666 (5)0.05230 (19)0.0633 (2)0.0404 (7)
H150.07300.10110.03540.048*
C160.0419 (5)0.04441 (17)0.1591 (2)0.0367 (7)
H160.03290.08830.19780.044*
C200.0997 (4)0.22849 (16)0.3412 (2)0.0326 (6)
C210.0100 (5)0.28412 (16)0.2676 (2)0.0343 (6)
H210.07280.32380.30420.041*
C220.2309 (5)0.37810 (18)0.2566 (2)0.0410 (7)
C230.3617 (6)0.4100 (2)0.1896 (3)0.0552 (9)
H23A0.40460.46060.21190.066*
H23B0.28880.41270.12230.066*
H23C0.47760.37750.19040.066*
C240.1682 (4)0.24595 (16)0.1939 (2)0.0340 (6)
C250.3494 (5)0.22742 (18)0.2210 (2)0.0410 (7)
H250.37300.23740.28610.049*
C260.4943 (5)0.1948 (2)0.1538 (3)0.0472 (8)
H260.61830.18300.17270.057*
C270.4619 (5)0.17881 (19)0.0590 (3)0.0445 (8)
H270.56260.15570.01330.053*
C280.2813 (5)0.19683 (18)0.0312 (2)0.0401 (7)
H280.25790.18630.03380.048*
C290.1357 (5)0.23022 (17)0.0986 (2)0.0361 (6)
H290.01210.24250.07950.043*
C300.2988 (5)0.30679 (16)0.5946 (2)0.0336 (6)
C310.5036 (5)0.33491 (17)0.6404 (2)0.0370 (6)
H310.59800.29160.65110.044*
C320.6236 (5)0.3619 (2)0.4925 (3)0.0455 (8)
C330.7038 (6)0.4211 (3)0.4342 (3)0.0609 (10)
H33A0.84780.41610.44160.073*
H33B0.66990.47080.45770.073*
H33C0.64690.41560.36450.073*
C340.4884 (4)0.37238 (17)0.7377 (2)0.0346 (6)
C350.4782 (4)0.45038 (18)0.7455 (2)0.0385 (7)
H350.48470.48130.68960.046*
C360.4582 (5)0.48276 (19)0.8356 (3)0.0438 (8)
H360.45170.53600.84090.053*
C370.4477 (5)0.4391 (2)0.9167 (3)0.0469 (8)
H370.43350.46200.97770.056*
C380.4579 (5)0.3617 (2)0.9095 (2)0.0471 (8)
H380.45100.33120.96570.056*
C390.4780 (5)0.3286 (2)0.8205 (2)0.0436 (7)
H390.48470.27530.81600.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O100.0628 (14)0.0296 (11)0.0390 (12)0.0005 (10)0.0153 (10)0.0019 (9)
O110.0884 (19)0.0289 (12)0.0530 (14)0.0069 (12)0.0262 (13)0.0121 (11)
O120.088 (2)0.0608 (17)0.0464 (14)0.0106 (15)0.0278 (14)0.0110 (13)
O130.241 (6)0.064 (2)0.067 (2)0.016 (3)0.072 (3)0.0218 (18)
O200.0412 (11)0.0278 (10)0.0303 (10)0.0004 (8)0.0112 (8)0.0030 (8)
O210.0488 (14)0.0656 (16)0.0589 (15)0.0116 (12)0.0221 (11)0.0270 (13)
O220.0535 (13)0.0313 (11)0.0355 (11)0.0096 (10)0.0122 (9)0.0032 (9)
O230.0676 (16)0.0490 (15)0.0513 (16)0.0142 (13)0.0082 (12)0.0091 (12)
O300.0493 (12)0.0194 (9)0.0408 (11)0.0041 (9)0.0023 (9)0.0014 (9)
O310.0510 (13)0.0247 (10)0.0493 (13)0.0023 (9)0.0019 (10)0.0030 (9)
O320.0540 (13)0.0324 (11)0.0459 (13)0.0088 (10)0.0114 (10)0.0019 (10)
O330.089 (2)0.0449 (15)0.0640 (16)0.0043 (14)0.0289 (14)0.0105 (13)
N10.0712 (19)0.0270 (13)0.0392 (15)0.0008 (13)0.0046 (14)0.0003 (12)
N20.092 (3)0.0345 (17)0.059 (2)0.0112 (17)0.0134 (19)0.0037 (15)
N30.132 (4)0.069 (3)0.111 (4)0.031 (3)0.063 (3)0.034 (3)
N100.0405 (13)0.0231 (12)0.0352 (13)0.0021 (10)0.0050 (11)0.0063 (10)
N110.0425 (14)0.0209 (11)0.0341 (13)0.0011 (10)0.0053 (10)0.0039 (10)
N120.0409 (14)0.0265 (12)0.0394 (14)0.0003 (10)0.0112 (11)0.0030 (11)
N130.066 (2)0.0556 (19)0.0403 (16)0.0009 (15)0.0160 (14)0.0046 (15)
C10.0434 (16)0.0249 (13)0.0321 (15)0.0051 (12)0.0108 (12)0.0023 (12)
C20.0443 (16)0.0216 (13)0.0278 (14)0.0002 (12)0.0077 (12)0.0019 (11)
C30.0413 (16)0.0223 (13)0.0362 (16)0.0034 (12)0.0091 (12)0.0012 (12)
C40.065 (2)0.0263 (15)0.0296 (15)0.0030 (13)0.0107 (14)0.0010 (12)
C50.066 (2)0.0237 (14)0.0350 (16)0.0091 (14)0.0176 (15)0.0009 (12)
C60.0493 (19)0.0332 (16)0.053 (2)0.0090 (14)0.0240 (15)0.0072 (15)
C100.0404 (16)0.0223 (13)0.0382 (16)0.0037 (11)0.0062 (13)0.0018 (12)
C110.0275 (13)0.0261 (13)0.0341 (15)0.0015 (11)0.0021 (11)0.0008 (11)
C120.0305 (14)0.0250 (13)0.0331 (15)0.0008 (11)0.0037 (11)0.0004 (12)
C130.0330 (15)0.0333 (15)0.0339 (15)0.0007 (12)0.0067 (12)0.0030 (13)
C140.0411 (16)0.0391 (17)0.0322 (15)0.0008 (13)0.0048 (12)0.0017 (13)
C150.0468 (18)0.0307 (15)0.0448 (18)0.0031 (13)0.0104 (14)0.0058 (13)
C160.0435 (17)0.0255 (14)0.0418 (17)0.0018 (12)0.0094 (13)0.0017 (13)
C200.0396 (16)0.0276 (14)0.0318 (14)0.0051 (12)0.0096 (12)0.0025 (12)
C210.0445 (17)0.0277 (14)0.0326 (15)0.0010 (12)0.0126 (12)0.0012 (12)
C220.0500 (19)0.0319 (16)0.0393 (18)0.0047 (13)0.0011 (14)0.0069 (14)
C230.062 (2)0.045 (2)0.058 (2)0.0187 (18)0.0048 (17)0.0085 (17)
C240.0421 (16)0.0267 (14)0.0338 (15)0.0046 (12)0.0079 (12)0.0058 (12)
C250.0489 (18)0.0338 (16)0.0430 (17)0.0012 (14)0.0161 (14)0.0014 (14)
C260.0440 (18)0.0454 (19)0.055 (2)0.0042 (15)0.0144 (15)0.0017 (16)
C270.0469 (18)0.0374 (18)0.0470 (19)0.0032 (14)0.0008 (15)0.0013 (14)
C280.0515 (18)0.0364 (16)0.0330 (16)0.0030 (14)0.0082 (13)0.0015 (13)
C290.0407 (16)0.0312 (15)0.0379 (16)0.0055 (13)0.0113 (13)0.0031 (13)
C300.0483 (17)0.0229 (13)0.0305 (14)0.0036 (12)0.0088 (13)0.0011 (11)
C310.0452 (17)0.0263 (14)0.0390 (16)0.0028 (13)0.0052 (13)0.0023 (12)
C320.0401 (17)0.049 (2)0.0479 (19)0.0014 (15)0.0085 (14)0.0049 (16)
C330.061 (2)0.069 (3)0.054 (2)0.022 (2)0.0111 (18)0.001 (2)
C340.0320 (15)0.0301 (15)0.0396 (16)0.0031 (12)0.0006 (12)0.0059 (13)
C350.0363 (16)0.0314 (15)0.0455 (17)0.0014 (12)0.0010 (13)0.0038 (14)
C360.0346 (16)0.0370 (17)0.058 (2)0.0014 (13)0.0010 (14)0.0144 (16)
C370.0379 (17)0.053 (2)0.049 (2)0.0022 (15)0.0040 (14)0.0137 (17)
C380.0462 (18)0.053 (2)0.0410 (18)0.0026 (16)0.0047 (14)0.0025 (16)
C390.0464 (18)0.0339 (15)0.0499 (19)0.0046 (14)0.0056 (15)0.0000 (15)
Geometric parameters (Å, º) top
O10—N121.232 (3)C13—C141.375 (4)
O11—N121.223 (3)C13—H130.9500
O12—N131.226 (4)C14—C151.393 (5)
O13—N131.220 (5)C15—C161.360 (4)
O20—C21.447 (3)C15—H150.9500
O20—C201.334 (3)C16—H160.9500
O21—C201.189 (4)C20—C211.524 (4)
O22—C211.431 (3)C21—C241.521 (4)
O22—C221.351 (4)C21—H211.0000
O23—C221.194 (4)C22—C231.493 (5)
O30—C31.440 (3)C23—H23A0.9800
O30—C301.345 (3)C23—H23B0.9800
O31—C301.192 (4)C23—H23C0.9800
O32—C321.360 (4)C24—C251.390 (4)
O32—C311.422 (4)C24—C291.389 (4)
O33—C321.198 (4)C25—C261.373 (5)
N1—N21.199 (4)C25—H250.9500
N1—C41.496 (4)C26—C271.383 (5)
N2—N31.130 (5)C26—H260.9500
N10—N111.390 (3)C27—C281.388 (5)
N10—C101.263 (4)C27—H270.9500
N11—C111.341 (4)C28—C291.384 (4)
N11—H11N0.8800C28—H280.9500
N12—C121.451 (4)C29—H290.9500
N13—C141.446 (4)C30—C311.529 (4)
C1—C21.512 (4)C31—C341.510 (4)
C1—C51.534 (4)C31—H311.0000
C1—C61.523 (4)C32—C331.478 (5)
C1—C101.462 (4)C33—H33A0.9800
C2—C31.530 (4)C33—H33B0.9800
C2—H21.0000C33—H33C0.9800
C3—C41.531 (4)C34—C351.391 (4)
C3—H31.0000C34—C391.388 (5)
C4—C51.503 (5)C35—C361.390 (5)
C4—H41.0000C35—H350.9500
C5—C61.492 (5)C36—C371.367 (5)
C5—H51.0000C36—H360.9500
C6—H6A0.9900C37—C381.380 (5)
C6—H6B0.9900C37—H370.9500
C10—H100.9500C38—C391.381 (5)
C11—C121.419 (4)C38—H380.9500
C11—C161.420 (4)C39—H390.9500
C12—C131.379 (4)
C2—O20—C20117.6 (2)O20—C20—O21125.6 (3)
C21—O22—C22116.7 (2)O20—C20—C21109.6 (2)
C3—O30—C30118.0 (2)O21—C20—C21124.7 (3)
C32—O32—C31115.8 (3)O22—C21—C20108.9 (2)
N2—N1—C4116.5 (3)O22—C21—C24107.8 (2)
N1—N2—N3172.6 (4)O22—C21—H21109.3
N11—N10—C10116.0 (2)C20—C21—C24112.3 (2)
N10—N11—C11119.0 (2)C20—C21—H21109.3
N10—N11—H11N120.5C24—C21—H21109.3
C11—N11—H11N120.5O22—C22—O23123.0 (3)
O10—N12—O11122.3 (3)O22—C22—C23110.3 (3)
O10—N12—C12118.6 (2)O23—C22—C23126.8 (3)
O11—N12—C12119.1 (2)C22—C23—H23A109.5
O12—N13—O13122.7 (3)C22—C23—H23B109.5
O12—N13—C14119.8 (3)C22—C23—H23C109.5
O13—N13—C14117.6 (3)H23A—C23—H23B109.5
C2—C1—C5106.8 (2)H23A—C23—H23C109.5
C2—C1—C6116.0 (2)H23B—C23—H23C109.5
C2—C1—C10119.3 (2)C21—C24—C25120.0 (3)
C5—C1—C658.4 (2)C21—C24—C29120.9 (3)
C5—C1—C10120.6 (3)C25—C24—C29119.1 (3)
C6—C1—C10120.2 (3)C24—C25—C26120.2 (3)
O20—C2—C1111.8 (2)C24—C25—H25119.9
O20—C2—C3110.0 (2)C26—C25—H25119.9
O20—C2—H2110.1C25—C26—C27120.8 (3)
C1—C2—C3104.7 (2)C25—C26—H26119.6
C1—C2—H2110.1C27—C26—H26119.6
C3—C2—H2110.1C26—C27—C28119.5 (3)
O30—C3—C2113.1 (2)C26—C27—H27120.2
O30—C3—C4108.2 (2)C28—C27—H27120.2
O30—C3—H3110.2C27—C28—C29119.7 (3)
C2—C3—C4104.7 (2)C27—C28—H28120.2
C2—C3—H3110.2C29—C28—H28120.2
C4—C3—H3110.2C24—C29—C28120.7 (3)
N1—C4—C3109.1 (3)C24—C29—H29119.7
N1—C4—C5105.2 (3)C28—C29—H29119.7
N1—C4—H4112.8O30—C30—O31125.2 (3)
C3—C4—C5103.6 (2)O30—C30—C31109.8 (3)
C3—C4—H4112.8O31—C30—C31125.0 (3)
C5—C4—H4112.8O32—C31—C30110.0 (2)
C1—C5—C4107.4 (2)O32—C31—C34108.3 (2)
C1—C5—C660.4 (2)O32—C31—H31109.9
C1—C5—H5118.0C30—C31—C34108.8 (2)
C4—C5—C6120.2 (3)C30—C31—H31109.9
C4—C5—H5118.0C34—C31—H31109.9
C6—C5—H5118.0O32—C32—O33121.4 (3)
C1—C6—C561.1 (2)O32—C32—C33112.3 (3)
C1—C6—H6A117.7O33—C32—C33126.3 (3)
C1—C6—H6B117.7C32—C33—H33A109.5
C5—C6—H6A117.7C32—C33—H33B109.5
C5—C6—H6B117.7C32—C33—H33C109.5
H6A—C6—H6B114.8H33A—C33—H33B109.5
N10—C10—C1119.5 (3)H33A—C33—H33C109.5
N10—C10—H10120.3H33B—C33—H33C109.5
C1—C10—H10120.3C35—C34—C39119.0 (3)
N11—C11—C12124.4 (2)C31—C34—C39119.8 (3)
N11—C11—C16119.7 (2)C31—C34—C35121.2 (3)
C12—C11—C16115.9 (2)C34—C35—C36119.5 (3)
N12—C12—C11121.4 (2)C34—C35—H35120.2
N12—C12—C13116.0 (2)C36—C35—H35120.2
C11—C12—C13122.6 (3)C35—C36—C37121.0 (3)
C12—C13—C14118.3 (3)C35—C36—H36119.5
C12—C13—H13120.8C37—C36—H36119.5
C14—C13—H13120.8C36—C37—C38119.8 (3)
N13—C14—C13119.4 (3)C36—C37—H37120.1
N13—C14—C15118.9 (3)C38—C37—H37120.1
C13—C14—C15121.7 (3)C37—C38—C39120.0 (3)
C14—C15—C16119.4 (3)C37—C38—H38120.0
C14—C15—H15120.3C39—C38—H38120.0
C16—C15—H15120.3C34—C39—C38120.7 (3)
C11—C16—C15121.9 (3)C34—C39—H39119.6
C11—C16—H16119.0C38—C39—H39119.6
C15—C16—H16119.0
C20—O20—C2—C1130.2 (3)C2—C3—C4—N176.0 (3)
C20—O20—C2—C3114.0 (3)C2—C3—C4—C535.7 (3)
C2—O20—C20—O212.3 (4)N1—C4—C5—C189.7 (3)
C2—O20—C20—C21179.5 (2)N1—C4—C5—C6155.1 (3)
C22—O22—C21—C24154.8 (2)C3—C4—C5—C124.9 (3)
C22—O22—C21—C2083.2 (3)C3—C4—C5—C640.5 (4)
C21—O22—C22—O232.3 (5)C4—C5—C6—C193.9 (3)
C21—O22—C22—C23177.5 (3)N11—C11—C12—N120.1 (4)
C30—O30—C3—C299.5 (3)N11—C11—C12—C13179.5 (3)
C30—O30—C3—C4145.1 (2)C16—C11—C12—N12177.9 (3)
C3—O30—C30—O316.5 (4)C16—C11—C12—C131.5 (4)
C3—O30—C30—C31170.8 (2)N11—C11—C16—C15178.9 (3)
C32—O32—C31—C34170.2 (3)C12—C11—C16—C150.8 (4)
C32—O32—C31—C3071.1 (3)N12—C12—C13—C14178.9 (3)
C31—O32—C32—O331.7 (5)C11—C12—C13—C140.5 (4)
C31—O32—C32—C33176.8 (3)C12—C13—C14—N13177.9 (3)
N2—N1—C4—C392.0 (4)C12—C13—C14—C151.2 (4)
N2—N1—C4—C5157.4 (3)N13—C14—C15—C16177.3 (3)
C10—N10—N11—C11159.9 (3)C13—C14—C15—C161.9 (5)
N11—N10—C10—C1174.7 (3)C14—C15—C16—C110.8 (5)
N10—N11—C11—C12177.6 (3)O20—C20—C21—O22164.8 (2)
N10—N11—C11—C164.5 (4)O20—C20—C21—C2475.8 (3)
O10—N12—C12—C118.6 (4)O21—C20—C21—O2216.9 (4)
O10—N12—C12—C13171.9 (3)O21—C20—C21—C24102.4 (4)
O11—N12—C12—C11171.4 (3)O22—C21—C24—C25160.9 (3)
O11—N12—C12—C138.1 (4)O22—C21—C24—C2918.1 (4)
O12—N13—C14—C138.9 (5)C20—C21—C24—C2579.1 (3)
O12—N13—C14—C15170.3 (3)C20—C21—C24—C29101.9 (3)
O13—N13—C14—C13172.5 (4)C21—C24—C25—C26178.3 (3)
O13—N13—C14—C158.3 (5)C29—C24—C25—C260.7 (5)
C5—C1—C2—O20136.4 (2)C24—C25—C26—C270.9 (5)
C5—C1—C2—C317.4 (3)C25—C26—C27—C280.7 (5)
C6—C1—C2—O2073.9 (3)C26—C27—C28—C290.3 (5)
C6—C1—C2—C345.1 (3)C27—C28—C29—C240.0 (4)
C10—C1—C2—O2082.4 (3)C25—C24—C29—C280.2 (4)
C10—C1—C2—C3158.5 (3)C21—C24—C29—C28178.7 (3)
C2—C1—C5—C44.8 (3)O30—C30—C31—O32140.2 (2)
C2—C1—C5—C6110.6 (3)O30—C30—C31—C34101.3 (3)
C6—C1—C5—C4115.4 (3)O31—C30—C31—O3242.4 (4)
C10—C1—C5—C4135.7 (3)O31—C30—C31—C3476.0 (4)
C10—C1—C5—C6108.9 (3)O32—C31—C34—C3519.9 (4)
C2—C1—C6—C594.4 (3)O32—C31—C34—C39162.3 (3)
C10—C1—C6—C5109.5 (3)C30—C31—C34—C3599.6 (3)
C2—C1—C10—N1013.5 (4)C30—C31—C34—C3978.2 (3)
C5—C1—C10—N10149.2 (3)C31—C34—C35—C36178.0 (3)
C6—C1—C10—N10141.9 (3)C39—C34—C35—C360.2 (4)
O20—C2—C3—O3089.3 (3)C31—C34—C39—C38178.0 (3)
O20—C2—C3—C4153.2 (2)C35—C34—C39—C380.1 (5)
C1—C2—C3—O30150.5 (2)C34—C35—C36—C370.3 (5)
C1—C2—C3—C432.9 (3)C35—C36—C37—C380.3 (5)
O30—C3—C4—N144.9 (3)C36—C37—C38—C390.2 (5)
O30—C3—C4—C5156.5 (2)C37—C38—C39—C340.1 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11N···O100.882.002.618 (3)126

Experimental details

Crystal data
Chemical formulaC33H29N7O12
Mr715.63
Crystal system, space groupMonoclinic, P21
Temperature (K)193
a, b, c (Å)6.8522 (11), 17.747 (3), 13.729 (2)
β (°) 99.006 (2)
V3)1648.9 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.63 × 0.56 × 0.04
Data collection
DiffractometerBruker SMART 1000 CCD area-detector/PLATFORM
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.757, 0.996
No. of measured, independent and
observed [I > 2σ(I)] reflections
13919, 3905, 3150
Rint0.040
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.104, 1.04
No. of reflections3905
No. of parameters471
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.23
Absolute structureFlack (1983)
Absolute structure parameter0.1 (10)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11N···O100.882.002.618 (3)126.1
 

Acknowledgements

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

References

First citationBai, Y., Lowary, T. L. & Ferguson, M. J. (2004). Acta Cryst. E60, o2201–o2203.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationBiswas, G., Chandra, T., Garg, N., Bhakuni, D. S., Pramanik, A., Avasthi, K. & Maulik, P. R. (1996). Acta Cryst. C52, 2563–2566.  CSD CrossRef CAS IUCr Journals Google Scholar
First citationBruker (2001). SMART. Version 5.054. Bruker AXS Inc., Madison, Wisconsin, U.SA.  Google Scholar
First citationBruker (2003). SADABS (Version 2.10) and SAINT (Version 7.06A). Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCallam, C. S., Gadikota, R. R. & Lowary, T. L. (2001). J. Org. Chem. 66, 4549–4558.  Web of Science CrossRef PubMed CAS Google Scholar
First citationCallam, C. S. & Lowary, T. L. (2000). Org. Lett. 2, 167–169.  Web of Science CrossRef PubMed CAS Google Scholar
First citationCallam, C. S. & Lowary, T. L. (2001). J. Org. Chem. 66, 8961–8972.  Web of Science CrossRef PubMed CAS Google Scholar
First citationCentrone, C. A. & Lowary, T. L. (2002). J. Org. Chem. 67, 8862–8870.  Web of Science CrossRef PubMed CAS Google Scholar
First citationGallucci, J. C., Gadikota, R. R. & Lowary, T. L. (2000). Acta Cryst. C56, e365.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationGarcia, J. G., Voll, R. J., Fronczek, F. R. & Younathan, E. S. (1992). Acta Cryst. C48, 1692–1694.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationGurskaya, G. V., Bochkarev, A. V., Zdanov, A. S., Papchikhin, A. A., Purygin, P. P. & Krayevsky, A. (1990). FEBS Lett. 265, 63–66.  CSD CrossRef PubMed CAS Web of Science Google Scholar
First citationGurskaya, G. V., Zavodnik, V. E. & Surzhikov, S. A. (1996). Mol. Biol. 30, 540–546.  Google Scholar
First citationGuthrie, R. D., Jenkins, I. S., Yamasaki, R., Skelton, B. W. & White, A. H. (1981). J. Chem. Soc. Perkin Trans. 1, pp. 2328–2334.  CSD CrossRef Web of Science Google Scholar
First citationLi, J. & Lowary, T. L. (2008). Submitted to Org. Lett.Google Scholar
First citationMàrton-Merész, M., Kuszmann, J., Pelczer, I., Pàrkànyi, L., Koritsànszky, T. & Kàlmàn, A. (1983). Tetrahedron, 39, 275–285.  CSD CrossRef CAS Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 64| Part 2| February 2008| Pages o459-o460
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