(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

Li, J.; Lowary, T.L.; McDonald, R.

doi:10.1107/S1600536808000718

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

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

doi:10.1107/S1600536808000718

Open

access

(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

Jing Li,^a Todd L. Lowary ^a and Robert McDonald ^b ^*

^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 & 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 , 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

Crystal data

C₃₃H₂₉N₇O₁₂
M_r = 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 ) T_min = 0.756, T_max = 0.996
13919 measured reflections
3905 independent reflections
3150 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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

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.

Supporting information

Crystal structure: contains datablocks global, III. DOI: 10.1107/S1600536808000718/bq2060sup1.cif

Structure factors: contains datablock III. DOI: 10.1107/S1600536808000718/bq2060IIIsup2.hkl

checkCIF report

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).

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

	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.
	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

C₃₃H₂₉N₇O₁₂	F(000) = 744
M_r = 715.63	D_x = 1.441 Mg m⁻³
Monoclinic, P2₁	Melting point: 333 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 6.8522 (11) Å	Cell parameters from 4802 reflections
b = 17.747 (3) Å	θ = 2.3–22.4°
c = 13.729 (2) Å	µ = 0.11 mm⁻¹
β = 99.006 (2)°	T = 193 K
V = 1648.9 (5) Å³	Plate, yellow
Z = 2	0.63 × 0.56 × 0.04 mm

Data collection top

Bruker SMART 1000 CCD area-detector/PLATFORM diffractometer	3905 independent reflections
Radiation source: fine-focus sealed tube	3150 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 8.192 pixels mm^-1	θ_max = 27.6°, θ_min = 1.9°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2003)	k = −22→22
T_min = 0.757, T_max = 0.996	l = −17→17
13919 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.0581P)² + 0.2055P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3905 reflections	Δρ_max = 0.20 e Å⁻³
471 parameters	Δρ_min = −0.23 e Å⁻³
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.1 (10)

Crystal data top

C₃₃H₂₉N₇O₁₂	V = 1648.9 (5) Å³
M_r = 715.63	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.8522 (11) Å	µ = 0.11 mm⁻¹
b = 17.747 (3) Å	T = 193 K
c = 13.729 (2) Å	0.63 × 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)
T_min = 0.757, T_max = 0.996	R_int = 0.040
13919 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.104	Δρ_max = 0.20 e Å⁻³
S = 1.04	Δρ_min = −0.23 e Å⁻³
3905 reflections	Absolute structure: Flack (1983)
471 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
O10	0.0216 (3)	−0.17710 (12)	0.26418 (16)	0.0430 (5)
O11	0.0112 (4)	−0.21885 (13)	0.11642 (18)	0.0552 (7)
O12	0.1584 (4)	−0.05771 (17)	−0.14093 (19)	0.0633 (7)
O13	0.1090 (9)	0.0610 (2)	−0.1281 (3)	0.1188 (17)
O20	−0.0140 (3)	0.20972 (11)	0.40781 (13)	0.0325 (4)
O21	0.2602 (4)	0.20436 (16)	0.33755 (19)	0.0563 (7)
O22	0.1282 (3)	0.31877 (12)	0.21350 (14)	0.0395 (5)
O23	0.2147 (4)	0.40018 (15)	0.33712 (19)	0.0561 (7)
O30	0.2856 (3)	0.23219 (11)	0.60946 (15)	0.0370 (5)
O31	0.1682 (3)	0.34574 (11)	0.55501 (17)	0.0423 (5)
O32	0.5724 (3)	0.38917 (12)	0.57755 (17)	0.0437 (5)
O33	0.6065 (5)	0.29640 (16)	0.4718 (2)	0.0641 (7)
N1	0.2676 (5)	0.08960 (15)	0.6739 (2)	0.0462 (7)
N2	0.3933 (6)	0.10936 (17)	0.7397 (3)	0.0646 (9)
N3	0.5225 (8)	0.1213 (3)	0.7995 (4)	0.113 (2)
N10	−0.0001 (4)	0.03342 (13)	0.35238 (18)	0.0331 (5)
N11	0.0016 (4)	−0.03229 (13)	0.29748 (18)	0.0326 (5)
H11N	−0.0152	−0.0764	0.3242	0.039*
N12	0.0236 (4)	−0.16687 (14)	0.17555 (18)	0.0351 (6)
N13	0.1177 (5)	−0.00261 (19)	−0.0941 (2)	0.0532 (8)
C1	−0.0749 (4)	0.09361 (16)	0.4950 (2)	0.0330 (6)
C2	0.0664 (4)	0.15750 (15)	0.4847 (2)	0.0310 (6)
H2	0.1955	0.1370	0.4711	0.037*
C3	0.0947 (4)	0.19714 (16)	0.5849 (2)	0.0329 (6)
H3	−0.0124	0.2351	0.5871	0.040*
C4	0.0799 (5)	0.13409 (17)	0.6595 (2)	0.0399 (7)
H4	0.0440	0.1531	0.7229	0.048*
C5	−0.0736 (5)	0.08206 (17)	0.6058 (2)	0.0407 (7)
H5	−0.0795	0.0293	0.6307	0.049*
C6	−0.2535 (5)	0.11335 (18)	0.5436 (2)	0.0434 (8)
H6A	−0.2833	0.1674	0.5514	0.052*
H6B	−0.3710	0.0803	0.5296	0.052*
C10	−0.0820 (4)	0.02899 (16)	0.4284 (2)	0.0337 (6)
H10	−0.1478	−0.0160	0.4423	0.040*
C11	0.0292 (4)	−0.02746 (16)	0.2031 (2)	0.0295 (6)
C12	0.0412 (4)	−0.09040 (15)	0.1406 (2)	0.0297 (6)
C13	0.0683 (4)	−0.08305 (17)	0.0436 (2)	0.0333 (6)
H13	0.0770	−0.1262	0.0036	0.040*
C14	0.0826 (5)	−0.01172 (18)	0.0063 (2)	0.0376 (7)
C15	0.0666 (5)	0.05230 (19)	0.0633 (2)	0.0404 (7)
H15	0.0730	0.1011	0.0354	0.048*
C16	0.0419 (5)	0.04441 (17)	0.1591 (2)	0.0367 (7)
H16	0.0329	0.0883	0.1978	0.044*
C20	0.0997 (4)	0.22849 (16)	0.3412 (2)	0.0326 (6)
C21	−0.0100 (5)	0.28412 (16)	0.2676 (2)	0.0343 (6)
H21	−0.0728	0.3238	0.3042	0.041*
C22	0.2309 (5)	0.37810 (18)	0.2566 (2)	0.0410 (7)
C23	0.3617 (6)	0.4100 (2)	0.1896 (3)	0.0552 (9)
H23A	0.4046	0.4606	0.2119	0.066*
H23B	0.2888	0.4127	0.1223	0.066*
H23C	0.4776	0.3775	0.1904	0.066*
C24	−0.1682 (4)	0.24595 (16)	0.1939 (2)	0.0340 (6)
C25	−0.3494 (5)	0.22742 (18)	0.2210 (2)	0.0410 (7)
H25	−0.3730	0.2374	0.2861	0.049*
C26	−0.4943 (5)	0.1948 (2)	0.1538 (3)	0.0472 (8)
H26	−0.6183	0.1830	0.1727	0.057*
C27	−0.4619 (5)	0.17881 (19)	0.0590 (3)	0.0445 (8)
H27	−0.5626	0.1557	0.0133	0.053*
C28	−0.2813 (5)	0.19683 (18)	0.0312 (2)	0.0401 (7)
H28	−0.2579	0.1863	−0.0338	0.048*
C29	−0.1357 (5)	0.23022 (17)	0.0986 (2)	0.0361 (6)
H29	−0.0121	0.2425	0.0795	0.043*
C30	0.2988 (5)	0.30679 (16)	0.5946 (2)	0.0336 (6)
C31	0.5036 (5)	0.33491 (17)	0.6404 (2)	0.0370 (6)
H31	0.5980	0.2916	0.6511	0.044*
C32	0.6236 (5)	0.3619 (2)	0.4925 (3)	0.0455 (8)
C33	0.7038 (6)	0.4211 (3)	0.4342 (3)	0.0609 (10)
H33A	0.8478	0.4161	0.4416	0.073*
H33B	0.6699	0.4708	0.4577	0.073*
H33C	0.6469	0.4156	0.3645	0.073*
C34	0.4884 (4)	0.37238 (17)	0.7377 (2)	0.0346 (6)
C35	0.4782 (4)	0.45038 (18)	0.7455 (2)	0.0385 (7)
H35	0.4847	0.4813	0.6896	0.046*
C36	0.4582 (5)	0.48276 (19)	0.8356 (3)	0.0438 (8)
H36	0.4517	0.5360	0.8409	0.053*
C37	0.4477 (5)	0.4391 (2)	0.9167 (3)	0.0469 (8)
H37	0.4335	0.4620	0.9777	0.056*
C38	0.4579 (5)	0.3617 (2)	0.9095 (2)	0.0471 (8)
H38	0.4510	0.3312	0.9657	0.056*
C39	0.4780 (5)	0.3286 (2)	0.8205 (2)	0.0436 (7)
H39	0.4847	0.2753	0.8160	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O10	0.0628 (14)	0.0296 (11)	0.0390 (12)	−0.0005 (10)	0.0153 (10)	0.0019 (9)
O11	0.0884 (19)	0.0289 (12)	0.0530 (14)	−0.0069 (12)	0.0262 (13)	−0.0121 (11)
O12	0.088 (2)	0.0608 (17)	0.0464 (14)	−0.0106 (15)	0.0278 (14)	−0.0110 (13)
O13	0.241 (6)	0.064 (2)	0.067 (2)	0.016 (3)	0.072 (3)	0.0218 (18)
O20	0.0412 (11)	0.0278 (10)	0.0303 (10)	−0.0004 (8)	0.0112 (8)	0.0030 (8)
O21	0.0488 (14)	0.0656 (16)	0.0589 (15)	0.0116 (12)	0.0221 (11)	0.0270 (13)
O22	0.0535 (13)	0.0313 (11)	0.0355 (11)	−0.0096 (10)	0.0122 (9)	0.0032 (9)
O23	0.0676 (16)	0.0490 (15)	0.0513 (16)	−0.0142 (13)	0.0082 (12)	−0.0091 (12)
O30	0.0493 (12)	0.0194 (9)	0.0408 (11)	−0.0041 (9)	0.0023 (9)	−0.0014 (9)
O31	0.0510 (13)	0.0247 (10)	0.0493 (13)	−0.0023 (9)	0.0019 (10)	0.0030 (9)
O32	0.0540 (13)	0.0324 (11)	0.0459 (13)	−0.0088 (10)	0.0114 (10)	−0.0019 (10)
O33	0.089 (2)	0.0449 (15)	0.0640 (16)	0.0043 (14)	0.0289 (14)	−0.0105 (13)
N1	0.0712 (19)	0.0270 (13)	0.0392 (15)	0.0008 (13)	0.0046 (14)	0.0003 (12)
N2	0.092 (3)	0.0345 (17)	0.059 (2)	0.0112 (17)	−0.0134 (19)	−0.0037 (15)
N3	0.132 (4)	0.069 (3)	0.111 (4)	0.031 (3)	−0.063 (3)	−0.034 (3)
N10	0.0405 (13)	0.0231 (12)	0.0352 (13)	−0.0021 (10)	0.0050 (11)	−0.0063 (10)
N11	0.0425 (14)	0.0209 (11)	0.0341 (13)	−0.0011 (10)	0.0053 (10)	−0.0039 (10)
N12	0.0409 (14)	0.0265 (12)	0.0394 (14)	−0.0003 (10)	0.0112 (11)	−0.0030 (11)
N13	0.066 (2)	0.0556 (19)	0.0403 (16)	−0.0009 (15)	0.0160 (14)	0.0046 (15)
C1	0.0434 (16)	0.0249 (13)	0.0321 (15)	−0.0051 (12)	0.0108 (12)	−0.0023 (12)
C2	0.0443 (16)	0.0216 (13)	0.0278 (14)	0.0002 (12)	0.0077 (12)	0.0019 (11)
C3	0.0413 (16)	0.0223 (13)	0.0362 (16)	−0.0034 (12)	0.0091 (12)	−0.0012 (12)
C4	0.065 (2)	0.0263 (15)	0.0296 (15)	−0.0030 (13)	0.0107 (14)	−0.0010 (12)
C5	0.066 (2)	0.0237 (14)	0.0350 (16)	−0.0091 (14)	0.0176 (15)	0.0009 (12)
C6	0.0493 (19)	0.0332 (16)	0.053 (2)	−0.0090 (14)	0.0240 (15)	−0.0072 (15)
C10	0.0404 (16)	0.0223 (13)	0.0382 (16)	−0.0037 (11)	0.0062 (13)	−0.0018 (12)
C11	0.0275 (13)	0.0261 (13)	0.0341 (15)	0.0015 (11)	0.0021 (11)	−0.0008 (11)
C12	0.0305 (14)	0.0250 (13)	0.0331 (15)	−0.0008 (11)	0.0037 (11)	−0.0004 (12)
C13	0.0330 (15)	0.0333 (15)	0.0339 (15)	−0.0007 (12)	0.0067 (12)	−0.0030 (13)
C14	0.0411 (16)	0.0391 (17)	0.0322 (15)	0.0008 (13)	0.0048 (12)	0.0017 (13)
C15	0.0468 (18)	0.0307 (15)	0.0448 (18)	0.0031 (13)	0.0104 (14)	0.0058 (13)
C16	0.0435 (17)	0.0255 (14)	0.0418 (17)	0.0018 (12)	0.0094 (13)	−0.0017 (13)
C20	0.0396 (16)	0.0276 (14)	0.0318 (14)	−0.0051 (12)	0.0096 (12)	−0.0025 (12)
C21	0.0445 (17)	0.0277 (14)	0.0326 (15)	−0.0010 (12)	0.0126 (12)	0.0012 (12)
C22	0.0500 (19)	0.0319 (16)	0.0393 (18)	−0.0047 (13)	0.0011 (14)	0.0069 (14)
C23	0.062 (2)	0.045 (2)	0.058 (2)	−0.0187 (18)	0.0048 (17)	0.0085 (17)
C24	0.0421 (16)	0.0267 (14)	0.0338 (15)	0.0046 (12)	0.0079 (12)	0.0058 (12)
C25	0.0489 (18)	0.0338 (16)	0.0430 (17)	−0.0012 (14)	0.0161 (14)	−0.0014 (14)
C26	0.0440 (18)	0.0454 (19)	0.055 (2)	−0.0042 (15)	0.0144 (15)	0.0017 (16)
C27	0.0469 (18)	0.0374 (18)	0.0470 (19)	−0.0032 (14)	0.0008 (15)	0.0013 (14)
C28	0.0515 (18)	0.0364 (16)	0.0330 (16)	0.0030 (14)	0.0082 (13)	0.0015 (13)
C29	0.0407 (16)	0.0312 (15)	0.0379 (16)	0.0055 (13)	0.0113 (13)	0.0031 (13)
C30	0.0483 (17)	0.0229 (13)	0.0305 (14)	−0.0036 (12)	0.0088 (13)	−0.0011 (11)
C31	0.0452 (17)	0.0263 (14)	0.0390 (16)	−0.0028 (13)	0.0052 (13)	−0.0023 (12)
C32	0.0401 (17)	0.049 (2)	0.0479 (19)	0.0014 (15)	0.0085 (14)	−0.0049 (16)
C33	0.061 (2)	0.069 (3)	0.054 (2)	−0.022 (2)	0.0111 (18)	0.001 (2)
C34	0.0320 (15)	0.0301 (15)	0.0396 (16)	−0.0031 (12)	−0.0006 (12)	−0.0059 (13)
C35	0.0363 (16)	0.0314 (15)	0.0455 (17)	0.0014 (12)	−0.0010 (13)	−0.0038 (14)
C36	0.0346 (16)	0.0370 (17)	0.058 (2)	0.0014 (13)	0.0010 (14)	−0.0144 (16)
C37	0.0379 (17)	0.053 (2)	0.049 (2)	−0.0022 (15)	0.0040 (14)	−0.0137 (17)
C38	0.0462 (18)	0.053 (2)	0.0410 (18)	−0.0026 (16)	0.0047 (14)	0.0025 (16)
C39	0.0464 (18)	0.0339 (15)	0.0499 (19)	−0.0046 (14)	0.0056 (15)	0.0000 (15)

Geometric parameters (Å, º) top

O10—N12	1.232 (3)	C13—C14	1.375 (4)
O11—N12	1.223 (3)	C13—H13	0.9500
O12—N13	1.226 (4)	C14—C15	1.393 (5)
O13—N13	1.220 (5)	C15—C16	1.360 (4)
O20—C2	1.447 (3)	C15—H15	0.9500
O20—C20	1.334 (3)	C16—H16	0.9500
O21—C20	1.189 (4)	C20—C21	1.524 (4)
O22—C21	1.431 (3)	C21—C24	1.521 (4)
O22—C22	1.351 (4)	C21—H21	1.0000
O23—C22	1.194 (4)	C22—C23	1.493 (5)
O30—C3	1.440 (3)	C23—H23A	0.9800
O30—C30	1.345 (3)	C23—H23B	0.9800
O31—C30	1.192 (4)	C23—H23C	0.9800
O32—C32	1.360 (4)	C24—C25	1.390 (4)
O32—C31	1.422 (4)	C24—C29	1.389 (4)
O33—C32	1.198 (4)	C25—C26	1.373 (5)
N1—N2	1.199 (4)	C25—H25	0.9500
N1—C4	1.496 (4)	C26—C27	1.383 (5)
N2—N3	1.130 (5)	C26—H26	0.9500
N10—N11	1.390 (3)	C27—C28	1.388 (5)
N10—C10	1.263 (4)	C27—H27	0.9500
N11—C11	1.341 (4)	C28—C29	1.384 (4)
N11—H11N	0.8800	C28—H28	0.9500
N12—C12	1.451 (4)	C29—H29	0.9500
N13—C14	1.446 (4)	C30—C31	1.529 (4)
C1—C2	1.512 (4)	C31—C34	1.510 (4)
C1—C5	1.534 (4)	C31—H31	1.0000
C1—C6	1.523 (4)	C32—C33	1.478 (5)
C1—C10	1.462 (4)	C33—H33A	0.9800
C2—C3	1.530 (4)	C33—H33B	0.9800
C2—H2	1.0000	C33—H33C	0.9800
C3—C4	1.531 (4)	C34—C35	1.391 (4)
C3—H3	1.0000	C34—C39	1.388 (5)
C4—C5	1.503 (5)	C35—C36	1.390 (5)
C4—H4	1.0000	C35—H35	0.9500
C5—C6	1.492 (5)	C36—C37	1.367 (5)
C5—H5	1.0000	C36—H36	0.9500
C6—H6A	0.9900	C37—C38	1.380 (5)
C6—H6B	0.9900	C37—H37	0.9500
C10—H10	0.9500	C38—C39	1.381 (5)
C11—C12	1.419 (4)	C38—H38	0.9500
C11—C16	1.420 (4)	C39—H39	0.9500
C12—C13	1.379 (4)

C2—O20—C20	117.6 (2)	O20—C20—O21	125.6 (3)
C21—O22—C22	116.7 (2)	O20—C20—C21	109.6 (2)
C3—O30—C30	118.0 (2)	O21—C20—C21	124.7 (3)
C32—O32—C31	115.8 (3)	O22—C21—C20	108.9 (2)
N2—N1—C4	116.5 (3)	O22—C21—C24	107.8 (2)
N1—N2—N3	172.6 (4)	O22—C21—H21	109.3
N11—N10—C10	116.0 (2)	C20—C21—C24	112.3 (2)
N10—N11—C11	119.0 (2)	C20—C21—H21	109.3
N10—N11—H11N	120.5	C24—C21—H21	109.3
C11—N11—H11N	120.5	O22—C22—O23	123.0 (3)
O10—N12—O11	122.3 (3)	O22—C22—C23	110.3 (3)
O10—N12—C12	118.6 (2)	O23—C22—C23	126.8 (3)
O11—N12—C12	119.1 (2)	C22—C23—H23A	109.5
O12—N13—O13	122.7 (3)	C22—C23—H23B	109.5
O12—N13—C14	119.8 (3)	C22—C23—H23C	109.5
O13—N13—C14	117.6 (3)	H23A—C23—H23B	109.5
C2—C1—C5	106.8 (2)	H23A—C23—H23C	109.5
C2—C1—C6	116.0 (2)	H23B—C23—H23C	109.5
C2—C1—C10	119.3 (2)	C21—C24—C25	120.0 (3)
C5—C1—C6	58.4 (2)	C21—C24—C29	120.9 (3)
C5—C1—C10	120.6 (3)	C25—C24—C29	119.1 (3)
C6—C1—C10	120.2 (3)	C24—C25—C26	120.2 (3)
O20—C2—C1	111.8 (2)	C24—C25—H25	119.9
O20—C2—C3	110.0 (2)	C26—C25—H25	119.9
O20—C2—H2	110.1	C25—C26—C27	120.8 (3)
C1—C2—C3	104.7 (2)	C25—C26—H26	119.6
C1—C2—H2	110.1	C27—C26—H26	119.6
C3—C2—H2	110.1	C26—C27—C28	119.5 (3)
O30—C3—C2	113.1 (2)	C26—C27—H27	120.2
O30—C3—C4	108.2 (2)	C28—C27—H27	120.2
O30—C3—H3	110.2	C27—C28—C29	119.7 (3)
C2—C3—C4	104.7 (2)	C27—C28—H28	120.2
C2—C3—H3	110.2	C29—C28—H28	120.2
C4—C3—H3	110.2	C24—C29—C28	120.7 (3)
N1—C4—C3	109.1 (3)	C24—C29—H29	119.7
N1—C4—C5	105.2 (3)	C28—C29—H29	119.7
N1—C4—H4	112.8	O30—C30—O31	125.2 (3)
C3—C4—C5	103.6 (2)	O30—C30—C31	109.8 (3)
C3—C4—H4	112.8	O31—C30—C31	125.0 (3)
C5—C4—H4	112.8	O32—C31—C30	110.0 (2)
C1—C5—C4	107.4 (2)	O32—C31—C34	108.3 (2)
C1—C5—C6	60.4 (2)	O32—C31—H31	109.9
C1—C5—H5	118.0	C30—C31—C34	108.8 (2)
C4—C5—C6	120.2 (3)	C30—C31—H31	109.9
C4—C5—H5	118.0	C34—C31—H31	109.9
C6—C5—H5	118.0	O32—C32—O33	121.4 (3)
C1—C6—C5	61.1 (2)	O32—C32—C33	112.3 (3)
C1—C6—H6A	117.7	O33—C32—C33	126.3 (3)
C1—C6—H6B	117.7	C32—C33—H33A	109.5
C5—C6—H6A	117.7	C32—C33—H33B	109.5
C5—C6—H6B	117.7	C32—C33—H33C	109.5
H6A—C6—H6B	114.8	H33A—C33—H33B	109.5
N10—C10—C1	119.5 (3)	H33A—C33—H33C	109.5
N10—C10—H10	120.3	H33B—C33—H33C	109.5
C1—C10—H10	120.3	C35—C34—C39	119.0 (3)
N11—C11—C12	124.4 (2)	C31—C34—C39	119.8 (3)
N11—C11—C16	119.7 (2)	C31—C34—C35	121.2 (3)
C12—C11—C16	115.9 (2)	C34—C35—C36	119.5 (3)
N12—C12—C11	121.4 (2)	C34—C35—H35	120.2
N12—C12—C13	116.0 (2)	C36—C35—H35	120.2
C11—C12—C13	122.6 (3)	C35—C36—C37	121.0 (3)
C12—C13—C14	118.3 (3)	C35—C36—H36	119.5
C12—C13—H13	120.8	C37—C36—H36	119.5
C14—C13—H13	120.8	C36—C37—C38	119.8 (3)
N13—C14—C13	119.4 (3)	C36—C37—H37	120.1
N13—C14—C15	118.9 (3)	C38—C37—H37	120.1
C13—C14—C15	121.7 (3)	C37—C38—C39	120.0 (3)
C14—C15—C16	119.4 (3)	C37—C38—H38	120.0
C14—C15—H15	120.3	C39—C38—H38	120.0
C16—C15—H15	120.3	C34—C39—C38	120.7 (3)
C11—C16—C15	121.9 (3)	C34—C39—H39	119.6
C11—C16—H16	119.0	C38—C39—H39	119.6
C15—C16—H16	119.0

C20—O20—C2—C1	−130.2 (3)	C2—C3—C4—N1	76.0 (3)
C20—O20—C2—C3	114.0 (3)	C2—C3—C4—C5	−35.7 (3)
C2—O20—C20—O21	2.3 (4)	N1—C4—C5—C1	−89.7 (3)
C2—O20—C20—C21	−179.5 (2)	N1—C4—C5—C6	−155.1 (3)
C22—O22—C21—C24	154.8 (2)	C3—C4—C5—C1	24.9 (3)
C22—O22—C21—C20	−83.2 (3)	C3—C4—C5—C6	−40.5 (4)
C21—O22—C22—O23	2.3 (5)	C4—C5—C6—C1	93.9 (3)
C21—O22—C22—C23	−177.5 (3)	N11—C11—C12—N12	0.1 (4)
C30—O30—C3—C2	99.5 (3)	N11—C11—C12—C13	179.5 (3)
C30—O30—C3—C4	−145.1 (2)	C16—C11—C12—N12	−177.9 (3)
C3—O30—C30—O31	−6.5 (4)	C16—C11—C12—C13	1.5 (4)
C3—O30—C30—C31	170.8 (2)	N11—C11—C16—C15	−178.9 (3)
C32—O32—C31—C34	170.2 (3)	C12—C11—C16—C15	−0.8 (4)
C32—O32—C31—C30	−71.1 (3)	N12—C12—C13—C14	178.9 (3)
C31—O32—C32—O33	1.7 (5)	C11—C12—C13—C14	−0.5 (4)
C31—O32—C32—C33	−176.8 (3)	C12—C13—C14—N13	177.9 (3)
N2—N1—C4—C3	92.0 (4)	C12—C13—C14—C15	−1.2 (4)
N2—N1—C4—C5	−157.4 (3)	N13—C14—C15—C16	−177.3 (3)
C10—N10—N11—C11	159.9 (3)	C13—C14—C15—C16	1.9 (5)
N11—N10—C10—C1	174.7 (3)	C14—C15—C16—C11	−0.8 (5)
N10—N11—C11—C12	177.6 (3)	O20—C20—C21—O22	164.8 (2)
N10—N11—C11—C16	−4.5 (4)	O20—C20—C21—C24	−75.8 (3)
O10—N12—C12—C11	−8.6 (4)	O21—C20—C21—O22	−16.9 (4)
O10—N12—C12—C13	171.9 (3)	O21—C20—C21—C24	102.4 (4)
O11—N12—C12—C11	171.4 (3)	O22—C21—C24—C25	−160.9 (3)
O11—N12—C12—C13	−8.1 (4)	O22—C21—C24—C29	18.1 (4)
O12—N13—C14—C13	−8.9 (5)	C20—C21—C24—C25	79.1 (3)
O12—N13—C14—C15	170.3 (3)	C20—C21—C24—C29	−101.9 (3)
O13—N13—C14—C13	172.5 (4)	C21—C24—C25—C26	178.3 (3)
O13—N13—C14—C15	−8.3 (5)	C29—C24—C25—C26	−0.7 (5)
C5—C1—C2—O20	−136.4 (2)	C24—C25—C26—C27	0.9 (5)
C5—C1—C2—C3	−17.4 (3)	C25—C26—C27—C28	−0.7 (5)
C6—C1—C2—O20	−73.9 (3)	C26—C27—C28—C29	0.3 (5)
C6—C1—C2—C3	45.1 (3)	C27—C28—C29—C24	0.0 (4)
C10—C1—C2—O20	82.4 (3)	C25—C24—C29—C28	0.2 (4)
C10—C1—C2—C3	−158.5 (3)	C21—C24—C29—C28	−178.7 (3)
C2—C1—C5—C4	−4.8 (3)	O30—C30—C31—O32	140.2 (2)
C2—C1—C5—C6	110.6 (3)	O30—C30—C31—C34	−101.3 (3)
C6—C1—C5—C4	−115.4 (3)	O31—C30—C31—O32	−42.4 (4)
C10—C1—C5—C4	135.7 (3)	O31—C30—C31—C34	76.0 (4)
C10—C1—C5—C6	−108.9 (3)	O32—C31—C34—C35	19.9 (4)
C2—C1—C6—C5	−94.4 (3)	O32—C31—C34—C39	−162.3 (3)
C10—C1—C6—C5	109.5 (3)	C30—C31—C34—C35	−99.6 (3)
C2—C1—C10—N10	−13.5 (4)	C30—C31—C34—C39	78.2 (3)
C5—C1—C10—N10	−149.2 (3)	C31—C34—C35—C36	178.0 (3)
C6—C1—C10—N10	141.9 (3)	C39—C34—C35—C36	0.2 (4)
O20—C2—C3—O30	−89.3 (3)	C31—C34—C39—C38	−178.0 (3)
O20—C2—C3—C4	153.2 (2)	C35—C34—C39—C38	−0.1 (5)
C1—C2—C3—O30	150.5 (2)	C34—C35—C36—C37	−0.3 (5)
C1—C2—C3—C4	32.9 (3)	C35—C36—C37—C38	0.3 (5)
O30—C3—C4—N1	−44.9 (3)	C36—C37—C38—C39	−0.2 (5)
O30—C3—C4—C5	−156.5 (2)	C37—C38—C39—C34	0.1 (5)

Hydrogen-bond geometry (Å, º) top

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

Experimental details

Crystal data
Chemical formula	C₃₃H₂₉N₇O₁₂
M_r	715.63
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	193
a, b, c (Å)	6.8522 (11), 17.747 (3), 13.729 (2)
β (°)	99.006 (2)
V (Å³)	1648.9 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.63 × 0.56 × 0.04

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector/PLATFORM diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.757, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	13919, 3905, 3150
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.104, 1.04
No. of reflections	3905
No. of parameters	471
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.23
Absolute structure	Flack (1983)
Absolute structure parameter	−0.1 (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···A	D—H	H···A	D···A	D—H···A
N11—H11N···O10	0.88	2.00	2.618 (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

Bai, Y., Lowary, T. L. & Ferguson, M. J. (2004). Acta Cryst. E60, o2201–o2203. Web of Science CSD CrossRef IUCr Journals Google Scholar
Biswas, 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
Bruker (2001). SMART. Version 5.054. Bruker AXS Inc., Madison, Wisconsin, U.SA. Google Scholar
Bruker (2003). SADABS (Version 2.10) and SAINT (Version 7.06A). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Callam, C. S., Gadikota, R. R. & Lowary, T. L. (2001). J. Org. Chem. 66, 4549–4558. Web of Science CrossRef PubMed CAS Google Scholar
Callam, C. S. & Lowary, T. L. (2000). Org. Lett. 2, 167–169. Web of Science CrossRef PubMed CAS Google Scholar
Callam, C. S. & Lowary, T. L. (2001). J. Org. Chem. 66, 8961–8972. Web of Science CrossRef PubMed CAS Google Scholar
Centrone, C. A. & Lowary, T. L. (2002). J. Org. Chem. 67, 8862–8870. Web of Science CrossRef PubMed CAS Google Scholar
Gallucci, J. C., Gadikota, R. R. & Lowary, T. L. (2000). Acta Cryst. C56, e365. Web of Science CSD CrossRef IUCr Journals Google Scholar
Garcia, 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
Gurskaya, 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
Gurskaya, G. V., Zavodnik, V. E. & Surzhikov, S. A. (1996). Mol. Biol. 30, 540–546. Google Scholar
Guthrie, 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
Li, J. & Lowary, T. L. (2008). Submitted to Org. Lett.. Google Scholar
Màrton-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
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

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

doi:10.1107/S1600536808000718

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

(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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(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