(S) O Succinimidyl N [2 (tert but­oxy­carbonyl­amino)­propyl]­carbamate

organic papers

o222

Structure Reports

Online

ISSN 1600-5368

(

S

)-

O

-Succinimidyl

N

-[2-(

tert

-butoxycarbonylamino)-propyl]carbamate

Valeria Menschise,a_Claude

Didierjean,a_{Vincent Semetey,}b

Gilles Guichard,b_Jean-Paul

Briandb_{and Andre Aubry}a_*

a_{Laboratoire de Cristallographie et ModeÂlisation} des MateÂriaux MineÂraux, et Biologiques (LCM3B), UPRESA n_{7036, Groupe} Biocristal-lographie, Universite Henri PoincareÂ, Nancy I, Faculte des Sciences, BP 239, 54506 Vandoeuvre leÁs Nancy CEDEX, France, and b_{Laboratoire de Chimie Immunologique, UPR} 9021 CNRS, Institut de Biologie MoleÂculaire et Cellulaire 15, rue Descartes, 67000 Strasbourg, France

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.004 AÊ

Rfactor = 0.037

wRfactor = 0.097 Data-to-parameter ratio = 8.7

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2001 International Union of Crystallography Printed in Great Britain ± all rights reserved

The molecule of activated carbamate, (S )-2,5-dioxopyrrolidin-1-yl N-[2-(tert-butoxycarbonylamino)propyl]carbamate, t Bu-OCONHCH(Me)CH2NHCOONC4H4O2or C13H21N3O6,

pre-pared fromN-Boc-3_{HAla-OH, assumes a folded}

conforma-tion with the NÐCÐCÐN torsion angle equal to 55.9 (3)_.

Both NÐH groups are involved in intermolecular hydrogen bonds, forming in®nite chains in the crystal.

Comment

Unnatural biopolymers with a urea backbone, such asN,N -linked oligoureas [N(CONHR)-(CH2)m-]n (Nowick, 1999),

N,N0_{-linked oligoureas [NH-CHR-CH}

2-NH-CO-]n(Burgesset

al., 1995, 1997; Kim et al., 1996; Boeijen & Liskamp, 1999; Guichard et al., 1999, 2000; Tamilarasu et al., 1999), ureido-peptoids [NR-CH2-CH2-NH-CO-]n (Kruijzer et al., 1997; Wilson & Nowick, 1998) and oligomeric cyclic ureas (Kimet al., 1996) have been described recently as peptide backbone mimetics or as templates for the creation of arti®cial-sheets. The urea fragment appears particularly promising for drug discovery because of its expected metabolic stability and interesting hydrogen-bonding properties. We have recently reported a simple and effective synthesis of O-succinimidyl 2-(tert-butoxycarbonylamino)-2-subsituted-ethylcarbamate derivatives starting from the corresponding N-protected -amino acids and their use as activated monomers in the synthesis of di- and trisubstituted ureas and N,N0_-linked

oligoureas (Guichard et al., 1999). These derivatives are stable compounds that react readily with amines to form substituted ureas. Furthermore, the mild conditions required for their preparation are compatible with most functionalized side chains of amino acids as well as with standard protecting groups used in solid-phase peptide synthesis (Guichard et al., 2000). Herein, we report the crystal structure of (S)-O-succinimidyl N-[2-(tert -butoxy-carbonylamino)propyl]carbamate, (I), which was prepared in three steps from Boc-(S)-3_HAla-OH.

Bond distances and angles of the succinimide ring are in good agreement with those recently published by Tenonet al.

(2000) and Guichardet al.(1999) forN-methylsuccinimide and

O-succinimidyl (2-nitrophenyl)carbamate, respectively. The

succinimide ring in (I) is nearly planar, as in the unsubstituted succinimide (Mason, 1961) and O-succinimidyl (2-nitro-phenyl)carbamate (Guichardet al., 1999) molecules. Indeed, the puckering parameters of the succinimide ring in the title compound areq= 0.010 AÊ and'2= 314.0 for the sequence

N3ÐC10ÐC11ÐC12ÐC13 (Cremer & Pople, 1975).

The molecule (Fig. 1 and Table 1) assumes a folded shape with thegaucheconformation about the central C6ÐC8 bond in the main chain, the N1ÐC6ÐC8ÐN2 torsion angle being equal to 55.9 (3)_{. The molecules of the title compound in the}

crystal are linked into in®nite chains via C O HÐN hydrogen bonds (Fig. 2 and Table 2). The chains are stretched along the [100] direction and form a parallel sheet-like arrangement. All interactions between the chains are purely van der Waals in nature.

Experimental

O-succinimidyl carbamate was prepared by homologation of Boc-L -Ala-OH, with subsequent conversion of Boc-(S)-3_{HAla-OH [we}

used the nomenclature proposed by Seebach & Matthews (1997) for

-amino acids] to the corresponding acyl azide and trapping of the intermediate isocyanate, resulting from Curtius rearrangement of the acyl azide, with N-hydroxysuccinimide. Details of the synthetic procedures are available in the CIF ®le.

Crystal data

C13H21N3O6 Mr= 315.33

Monoclinic,P2

a= 5.1260 (2) AÊ

b= 8.5650 (4) AÊ

c= 18.7540 (9) AÊ

= 91.996 (3)

V= 822.88 (6) AÊ3 Z= 2

Dx= 1.273 Mg mÿ3

MoKradiation Cell parameters from 5236

re¯ections

= 4.0±26.3

= 0.10 mmÿ1 T= 293 (2) K Prismatic, colorless 0.300.250.22 mm

Data collection

KappaCCD diffractometer

'and! scans

5236 measured re¯ections 1792 independent re¯ections 1436 re¯ections withI> 2(I)

Rint= 0.030

max= 26.3 h= 0!6

k= 0!10

l=ÿ23!23

Re®nement

Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.037} wR(F2_{) = 0.097} S= 1.03 1792 re¯ections 205 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2_(F

o2) + (0.0553P)2

+ 0.0391P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001 max= 0.11 e AÊÿ3 min=ÿ0.17 e AÊÿ3

Table 1

Selected geometric parameters (_).

O1ÐC5ÐN1ÐC6 ÿ177.9 (2) C5ÐN1ÐC6ÐC8 ÿ139.7 (2)

N1ÐC6ÐC8ÐN2 55.9 (3)

C6ÐC8ÐN2ÐC9 ÿ141.7 (2)

C8ÐN2ÐC9ÐO4 179.76 (19) N2ÐC9ÐO4ÐN3 ÿ177.1 (2) C9ÐO4ÐN3ÐC10 90.4 (3)

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

N1ÐH1 O2i _{1.010 (10) 2.037 (18) 2.938 (2) 147 (2)} N2ÐH2 O3ii _{1.016 (10) 2.038 (14) 3.022 (3) 162 (3)} Symmetry codes: (i) 1‡x;y;z; (ii)xÿ1;y;z.

The absolute stereochemistry of the title compound is based on the known con®guration of Boc-L-Ala-OH (purchased from Neosystem, Strasbourg, France) since the homologation using the Arndt±Eistert

Acta Cryst.(2001). E57, o222±o224 Valeria Menschiseet al. C₁₃H₂₁N₃O₆

o223

organic papers

Figure 1

The molecular structure of (I) with the atom-numbering scheme and 25% probability displacement ellipsoids. H atoms are shown only at the N atoms and at the chiral center.

Figure 2

organic papers

o224

reaction is known to proceed without epimerization at thecarbon. The positions of H atoms attached to N atoms were located from a difference map and the NÐH bond distance was restrained to 1.03 (1) AÊ (Taylor & Kennard, 1983). The H atoms connected to carbon were placed in the calculated positions and included in the re®nement in the riding model approximation (CÐH distances are in the range 0.96±0.98 AÊ). The isotropic H-atom displacement para-meters were restricted to be 30% higher than the equivalent isotropic displacement parameters of the parent atom.

Data collection: COLLECT (Nonius, 1998); cell re®nement:

COLLECT; data reduction: HKL (Otwinowski & Minor, 1997); program(s) used to solve structure:SIR92 (Altomare et al., 1994); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: maXus (Mackay et al., 1999) and WebLab ViewerPro3.5 (MSI, 1999).

We would like to thank the Service Commun de Diffraction X sur Monocristaux (Universite Henri PoincareÂ, Nancy I) for providing access to crystallographic experimental facilities.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994).J. Appl. Cryst.27, 435±436.

Boeijen, R. M. & Liskamp, J. (1999).Eur. J. Org. Chem.pp. 2127±2135. Burgess, K., Ibarzo, J., Linthicum, D. S., Russell, D. H., Shin, H., Shitangkoon,

A., Totani, R. & Zhang, A. J. (1997).J. Am. Chem. Soc.119, 1556±1564. Burgess, K., Linthicum, D. S. & Shin, H. (1995).Angew. Chem. Int. Ed. Engl.

34, 907±908.

Cremer, D. & Pople, J. A. (1975).J. Am. Chem. Soc.97, 1354±1358. Guichard, G., Semetey, V., Didierjean, C., Aubry, A., Briand, J. P. & Rodriguez,

M. (1999).J. Org. Chem.64, 8702±8705.

Guichard, G., Semetey, V., Rodriguez, M. & Briand, J. P. (2000)Tetrahedron Lett.41, 1553±1557.

Kim, J. M., Wilson, T. E., Norman, T. C. & Schultz, P. G. (1996).Tetrahedron Lett.37, 5309±5312.

Kruijzer, J. A. W., Lefeber, D. J. & Liskamp, R. M. J. (1997).Tetrahedron Lett. 38, 5335±5338.

Mackay, S., Edwards, C., Henderson, A., Gilmore, C., Stewart, N., Shankland, K. & Donald, A. (1999).maXus. University of Glasgow, Scotland. Mason, R. (1961).Acta Cryst.14, 720±724.

MSI (1999).WebLab ViewerPro3.5. Molecular Simulation Inc., San Diego, California, USA.

Nonius (1998).COLLECT. Nonius BV, Delft, The Netherlands. Nowick, J. S. (1999).Acc. Chem. Res.32, 287±296.

Otwinowski, Z. & Minor, W. (1997).Methods Enzymol.276, 307±326. Seebach, D. & Matthews, J. (1997).Chem. Commun.pp. 2015±2022. Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen. Germany. Tamilarasu, N., Huq, I. & Rana, T. M. (1999).J. Am. Chem. Soc.121, 1597±

1598.

Taylor, R. & Kennard, O. (1983).Acta Cryst.B39, 133±138.

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Acta Cryst. (2001). E57, o222–o224

supporting information

Acta Cryst. (2001). E57, o222–o224 [doi:10.1107/S1600536801002410]

(

S

)-

O

-Succinimidyl

N

-[2-(

tert

-butoxycarbonylamino)propyl]carbamate

Valeria Menschise, Claude Didierjean, Vincent Semetey, Gilles Guichard, Jean-Paul Briand and

Andr

é

Aubry

S1. Comment

Unnatural biopolymers with a urea backbone, such as N,N-linked oligoureas [N(CONHR)-(CH2)m–]n (Nowick, 1999),

N,N′-linked oligoureas [NH-CHR-CH2—NH—CO–]n (Burgess et al., 1995, 1997; Kim et al., 1996; Boeijen & Liskamp,

1999; Guichard et al. 1999, 2000; Tamilarasu et al., 1999), ureidopeptoids [NR—CH2—CH2—NH—CO–]n (Kruijtzer et

al., 1997; Wilson & Nowick, 1998) and oligomeric cyclic ureas (Kim et al., 1996) have been described recently as

peptide backbone mimetics or as template for the creation of artificial β-sheets. The urea fragment appears particularly

promising for drug discovery because of its expected metabolic stability and interesting hydrogen-bonding properties. We

have recently reported a simple and effective synthesis of O-succinimidyl 2-(tert

-butoxycarbonylamino)-2-subsituted-ethylcarbamate derivatives starting from the corresponding N-protected β-amino acids and their use as activated

monomers in the synthesis of di- and trisubstituted ureas and N,N′-linked oligoureas (Guichard et al., 1999). These

derivatives are stable compounds that react readily with amines to form substituted ureas. Furthermore, the mild

conditions required for their preparation are compatible with most functionalized side chains of amino acids as well as

with standard protecting groups used in solid-phase peptide synthesis (Guichard et al., 2000). Herein, we report the

crystal structure of (S)—O-succinimidyl N-[2-(tert-butoxycarbonylamino)propyl]carbamate, (I), which was prepared in

three steps from Boc-(S)-β3_HAla-OH.

Bond distances and angles of the succinimide ring are in good agreement with those recently published by Tenon et al.

(2000) and Guichard et al. (1999) for N-methylsuccinimide and O-succinimidyl (2-nitrophenyl)carbamate, respectively.

The succinimide ring in (I) is nearly planar, like in the unsubstituted succinimide (Mason, 1961) and O-succinimidyl

(2-nitrophenyl)carbamate (Guichard et al., 1999) molecules. Indeed, the puckering parameters of the succinimide ring in the

title compound are q = 0.010 Å and φ2 = 314.0° for the sequence N3—C10—C11—C12—C13 (Cremer & Pople, 1975).

The molecule (Fig. 1 and Table 1) assumes a folded shape with the gauche conformation about the central C6—C8 bond

in the main chain, the N1—C6—C8—N2 torsion angle being equal to 55.9 (3)°. The molecules of the title compound in

the crystal are linked into the infinite chains via C═O···H—N hydrogen bonds (Table 2). The chains are stretched along

the [100] direction and form parallel β sheet-like arrangement. All interactions between the chains are purely van der

Waals in nature.

S2. Experimental

O-succinimidyl carbamate was prepared by homologation of Boc-L-Ala-OH, with subsequent conversion of

Boc-(S)-β3_{HAla-OH [we used the nomenclature proposed by Seebach & Matthews (1997) for β-amino acids] to the corresponding}

acyl azide and trapping of the intermediate isocyanate, resulting from Curtius rearrangement of the acyl azide, with N

supporting information

sup-2

Acta Cryst. (2001). E57, o222–o224 S3. Refinement

The absolute stereochemistry of the title compound is based on the known configuration of Boc-L-Ala-OH (purchased

from Neosystem, Strasbourg, France) since the homologation using the Arndt-Eistert reaction is known to proceed

without epimerization at the α carbon. The positions of H atoms attached to N atoms were located from a difference map

and the N—H bond distance was restrained to 1.03 (1) Å (Taylor & Kennard, 1983). The H atoms connected to carbon

were placed in the calculated positions and included in the refinement in the riding model approximation (C—H distances

are in the range 0.96–0.98 Å). The isotropic H-atom displacement parameters were restricted to be 30% higher than the

equivalent isotropic displacement parameters of the parent atom.

Figure 1

The molecular structure of (I) with the atom-numbering scheme and 25% probability displacement ellipsoids. Only H

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Acta Cryst. (2001). E57, o222–o224 Figure 2

Packing of the molecules showing the infinite chains and the hydrogen-bonding network (in dashed lines).

(S)—O-Succinimidyl N-[2-(tert-butoxycarbonylamino)propyl]carbamate

Crystal data

C13H21N3O6 Mr = 315.33 Monoclinic, P21 a = 5.1260 (2) Å

b = 8.5650 (4) Å

c = 18.7540 (9) Å

β = 91.996 (3)°

V = 822.88 (6) Å3 Z = 2

F(000) = 336

Dx = 1.273 Mg m−3

Mo Kα radiation, λ = 0.71070 Å Cell parameters from 5236 reflections

θ = 4.0–26.3°

µ = 0.10 mm−1 T = 293 K

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Acta Cryst. (2001). E57, o222–o224 Data collection

KappaCCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

oscillation scans

5236 measured reflections 1792 independent reflections

1436 reflections with I > 2σ(I)

Rint = 0.030

θmax = 26.3°, θmin = 4.0°

h = 0→6

k = 0→10

l = −23→23

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.037} wR(F2_{) = 0.097} S = 1.03 1792 reflections 205 parameters 3 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.0553P)2 + 0.0391P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001 Δρmax = 0.11 e Å−3 Δρmin = −0.17 e Å−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

C1 −0.2288 (4) 0.3268 (3) 0.57925 (13) 0.0505 (6)

C2 −0.0629 (5) 0.4397 (4) 0.53911 (19) 0.0799 (10)

H2A 0.0275 0.3847 0.5028 0.104*

H2B 0.0617 0.4879 0.5716 0.104*

H2C −0.1723 0.5186 0.5173 0.104*

C3 −0.4126 (5) 0.2386 (4) 0.52903 (14) 0.0640 (7)

H3A −0.3143 0.1870 0.4933 0.083*

H3B −0.5334 0.3103 0.5065 0.083*

H3C −0.5071 0.1624 0.5554 0.083*

C4 −0.3705 (6) 0.4101 (4) 0.63710 (17) 0.0717 (8)

H4A −0.2470 0.4659 0.6671 0.093*

H4B −0.4612 0.3352 0.6652 0.093*

H4C −0.4937 0.4823 0.6159 0.093*

O1 −0.0307 (3) 0.2195 (2) 0.61109 (9) 0.0533 (5)

C5 −0.0988 (4) 0.1042 (3) 0.65552 (13) 0.0464 (6)

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Acta Cryst. (2001). E57, o222–o224

N1 0.1146 (3) 0.0388 (3) 0.68556 (11) 0.0497 (5)

H1 0.283 (3) 0.081 (4) 0.6670 (12) 0.065*

C6 0.1006 (4) −0.0925 (3) 0.73422 (12) 0.0487 (6)

H6 −0.0739 −0.0946 0.7539 0.063*

C7 0.1472 (7) −0.2466 (4) 0.69701 (19) 0.0802 (10)

H7A 0.0171 −0.2611 0.6596 0.104*

H7B 0.1369 −0.3303 0.7308 0.104*

H7C 0.3173 −0.2459 0.6771 0.104*

C8 0.3002 (4) −0.0704 (3) 0.79532 (12) 0.0484 (6)

H8A 0.2844 −0.1552 0.8292 0.063*

H8B 0.4745 −0.0741 0.7768 0.063*

N2 0.2643 (3) 0.0775 (3) 0.83175 (11) 0.0507 (5)

H2 0.081 (3) 0.121 (4) 0.8364 (13) 0.066*

C9 0.4632 (5) 0.1632 (3) 0.85544 (13) 0.0507 (6)

O3 0.6921 (3) 0.1383 (3) 0.85408 (11) 0.0694 (6)

O4 0.3633 (3) 0.2988 (2) 0.88774 (10) 0.0644 (5)

N3 0.5616 (4) 0.3975 (3) 0.91066 (11) 0.0584 (6)

C10 0.6574 (6) 0.5138 (4) 0.86724 (16) 0.0653 (8)

O5 0.5707 (6) 0.5414 (4) 0.80823 (12) 0.1015 (8)

C11 0.8740 (5) 0.5889 (4) 0.90923 (16) 0.0725 (8)

H11A 0.8381 0.6990 0.9161 0.094*

H11B 1.0368 0.5789 0.8848 0.094*

C12 0.8908 (5) 0.5049 (4) 0.98018 (15) 0.0709 (9)

H12A 1.0620 0.4583 0.9879 0.092*

H12B 0.8601 0.5769 1.0189 0.092*

C13 0.6842 (5) 0.3813 (4) 0.97655 (15) 0.0606 (7)

O6 0.6276 (4) 0.2834 (3) 1.01994 (12) 0.0886 (7)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C1 0.0311 (10) 0.0514 (14) 0.0686 (15) 0.0023 (10) −0.0046 (10) 0.0046 (13)

C2 0.0481 (14) 0.079 (2) 0.112 (2) 0.0056 (15) −0.0033 (14) 0.042 (2)

C3 0.0483 (13) 0.0763 (19) 0.0667 (17) 0.0101 (14) −0.0066 (11) −0.0067 (16)

C4 0.0622 (16) 0.0658 (18) 0.087 (2) 0.0080 (15) −0.0030 (14) −0.0172 (18)

O1 0.0290 (7) 0.0590 (11) 0.0718 (11) 0.0008 (7) 0.0004 (7) 0.0189 (10)

C5 0.0313 (12) 0.0510 (15) 0.0566 (13) −0.0035 (10) −0.0002 (9) 0.0027 (12)

O2 0.0287 (8) 0.0807 (14) 0.0947 (13) −0.0057 (9) 0.0038 (8) 0.0272 (12)

N1 0.0289 (8) 0.0587 (13) 0.0614 (12) −0.0017 (9) 0.0021 (8) 0.0118 (11)

C6 0.0411 (11) 0.0487 (14) 0.0564 (13) −0.0054 (11) 0.0004 (10) 0.0034 (13)

C7 0.103 (2) 0.0571 (19) 0.079 (2) −0.0039 (17) −0.0194 (17) −0.0078 (17)

C8 0.0413 (11) 0.0508 (15) 0.0531 (13) 0.0011 (11) 0.0014 (9) 0.0025 (12)

N2 0.0334 (10) 0.0598 (14) 0.0589 (12) 0.0016 (9) 0.0003 (8) −0.0079 (11)

C9 0.0413 (13) 0.0609 (17) 0.0498 (13) 0.0011 (12) 0.0015 (10) −0.0048 (12)

O3 0.0344 (9) 0.0810 (14) 0.0929 (14) 0.0008 (9) 0.0027 (8) −0.0244 (12)

O4 0.0463 (9) 0.0648 (13) 0.0819 (12) 0.0027 (9) −0.0021 (8) −0.0224 (11)

N3 0.0545 (12) 0.0590 (14) 0.0613 (13) −0.0045 (11) −0.0046 (10) −0.0099 (12)

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Acta Cryst. (2001). E57, o222–o224

O5 0.130 (2) 0.099 (2) 0.0745 (14) 0.0048 (16) −0.0167 (14) 0.0116 (15)

C11 0.0668 (17) 0.065 (2) 0.086 (2) −0.0044 (15) 0.0131 (14) −0.0089 (18)

C12 0.0575 (15) 0.091 (2) 0.0638 (17) −0.0073 (16) 0.0008 (12) −0.0215 (18)

C13 0.0527 (14) 0.072 (2) 0.0568 (15) 0.0036 (14) 0.0036 (12) −0.0066 (16)

O6 0.0862 (14) 0.108 (2) 0.0720 (14) −0.0075 (14) 0.0033 (11) 0.0133 (15)

Geometric parameters (Å, º)

C1—O1 1.479 (3) C7—H7B 0.9600

C1—C4 1.507 (4) C7—H7C 0.9600

C1—C2 1.507 (4) C8—N2 1.454 (3)

C1—C3 1.511 (3) C8—H8A 0.9700

C2—H2A 0.9600 C8—H8B 0.9700

C2—H2B 0.9600 N2—C9 1.321 (3)

C2—H2C 0.9600 N2—H2 1.016 (10)

C3—H3A 0.9600 C9—O3 1.194 (3)

C3—H3B 0.9600 C9—O4 1.415 (3)

C3—H3C 0.9600 O4—N3 1.379 (3)

C4—H4A 0.9600 N3—C13 1.374 (3)

C4—H4B 0.9600 N3—C10 1.387 (4)

C4—H4C 0.9600 C10—O5 1.202 (4)

O1—C5 1.346 (3) C10—C11 1.486 (4)

C5—O2 1.210 (3) C11—C12 1.513 (4)

C5—N1 1.336 (3) C11—H11A 0.9700

N1—C6 1.451 (3) C11—H11B 0.9700

N1—H1 1.010 (10) C12—C13 1.498 (4)

C6—C7 1.516 (4) C12—H12A 0.9700

C6—C8 1.521 (3) C12—H12B 0.9700

C6—H6 0.9800 C13—O6 1.210 (4)

C7—H7A 0.9600

O1—C1—C4 110.2 (2) H7A—C7—H7B 109.5

O1—C1—C2 102.08 (17) C6—C7—H7C 109.5

C4—C1—C2 110.5 (3) H7A—C7—H7C 109.5

O1—C1—C3 110.2 (2) H7B—C7—H7C 109.5

C4—C1—C3 112.3 (2) N2—C8—C6 111.7 (2)

C2—C1—C3 111.1 (2) N2—C8—H8A 109.3

C1—C2—H2A 109.5 C6—C8—H8A 109.3

C1—C2—H2B 109.5 N2—C8—H8B 109.3

H2A—C2—H2B 109.5 C6—C8—H8B 109.3

C1—C2—H2C 109.5 H8A—C8—H8B 107.9

H2A—C2—H2C 109.5 C9—N2—C8 122.2 (2)

H2B—C2—H2C 109.5 C9—N2—H2 118.2 (17)

C1—C3—H3A 109.5 C8—N2—H2 119.5 (17)

C1—C3—H3B 109.5 O3—C9—N2 129.9 (2)

H3A—C3—H3B 109.5 O3—C9—O4 121.8 (2)

C1—C3—H3C 109.5 N2—C9—O4 108.29 (19)

supporting information

sup-7

Acta Cryst. (2001). E57, o222–o224

H3B—C3—H3C 109.5 C13—N3—O4 121.8 (2)

C1—C4—H4A 109.5 C13—N3—C10 116.2 (2)

C1—C4—H4B 109.5 O4—N3—C10 121.9 (2)

H4A—C4—H4B 109.5 O5—C10—N3 123.7 (3)

C1—C4—H4C 109.5 O5—C10—C11 130.4 (3)

H4A—C4—H4C 109.5 N3—C10—C11 105.9 (2)

H4B—C4—H4C 109.5 C10—C11—C12 106.2 (3)

C5—O1—C1 121.10 (16) C10—C11—H11A 110.5

O2—C5—N1 124.8 (2) C12—C11—H11A 110.5

O2—C5—O1 125.1 (2) C10—C11—H11B 110.5

N1—C5—O1 110.03 (17) C12—C11—H11B 110.5

C5—N1—C6 122.14 (18) H11A—C11—H11B 108.7

C5—N1—H1 113.6 (17) C13—C12—C11 106.1 (2)

C6—N1—H1 123.9 (17) C13—C12—H12A 110.5

N1—C6—C7 111.9 (2) C11—C12—H12A 110.5

N1—C6—C8 109.31 (19) C13—C12—H12B 110.5

C7—C6—C8 110.0 (2) C11—C12—H12B 110.5

N1—C6—H6 108.5 H12A—C12—H12B 108.7

C7—C6—H6 108.5 O6—C13—N3 124.2 (3)

C8—C6—H6 108.5 O6—C13—C12 130.1 (3)

C6—C7—H7A 109.5 N3—C13—C12 105.7 (3)

C6—C7—H7B 109.5

O1—C5—N1—C6 −177.9 (2) O3—C9—O4—N3 4.7 (3)

C5—N1—C6—C8 −139.7 (2) C9—O4—N3—C13 −86.4 (3)

N1—C6—C8—N2 55.9 (3) C13—N3—C10—O5 179.8 (3)

C6—C8—N2—C9 −141.7 (2) O4—N3—C10—O5 2.8 (4)

C8—N2—C9—O4 179.76 (19) C13—N3—C10—C11 −0.6 (3)

N2—C9—O4—N3 −177.1 (2) O4—N3—C10—C11 −177.5 (2)

C9—O4—N3—C10 90.4 (3) O5—C10—C11—C12 179.4 (3)

C4—C1—O1—C5 58.6 (3) N3—C10—C11—C12 −0.2 (3)

C2—C1—O1—C5 176.0 (2) C10—C11—C12—C13 0.8 (3)

C3—C1—O1—C5 −65.8 (3) O4—N3—C13—O6 −1.5 (4)

C1—O1—C5—O2 9.5 (4) C10—N3—C13—O6 −178.4 (3)

C1—O1—C5—N1 −170.7 (2) O4—N3—C13—C12 178.0 (2)

O2—C5—N1—C6 1.9 (4) C10—N3—C13—C12 1.1 (3)

C5—N1—C6—C7 98.2 (3) C11—C12—C13—O6 178.3 (3)

C7—C6—C8—N2 179.2 (2) C11—C12—C13—N3 −1.1 (3)

C8—N2—C9—O3 −2.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1—H1···O2i _{1.01 (1) 2.04 (2) 2.938 (2) 147 (2)}

N2—H2···O3ii _{1.02 (1) 2.04 (1) 3.022 (3) 162 (3)}