1,2,3,4,5,7 Hexa­nitro­cubane

organic papers

o978

Structure Reports

Online

ISSN 1600-5368

1,2,3,4,5,7-Hexanitrocubane

Richard Gilardi,a_{* Ray J.} Butcherb_{and Mao-Xi Zhang}c

a_{Laboratory for the Structure of Matter, Naval}

Research Laboratory, Washington DC 20375, USA,b_{Department of Chemistry, Howard} University, Washington DC 20059, USA, and c_{Department of Chemistry, University of}

Chicago, Chicago IL 60637, USA

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study

T= 295 K

Mean(C±C) = 0.002 AÊ Disorder in main residue

Rfactor = 0.046

wRfactor = 0.136

Data-to-parameter ratio = 10.5

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

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

The hexanitrocubane structure, C8H2N6O12, reported herein,

is one of the last in the series of nitrocubanes, ranging from mono- to octanitrocubane. In this molecule, the H atoms participate in short hydrogen-bonding contacts to the nitro O atoms in adjoining molecules [2.50 (1) AÊ], thus linking mol-ecules into a two-dimensional sheet in the bc plane. In addition, the O O contacts in hexanitrocubane are shorter than van der Waals contact distances. The shortest of these [2.766 (3) AÊ] involve the O atoms of one of the attached nitro groups. These contacts involve molecules in an extended two-dimensional sheet parallel to theabplane.

Comment

Nitrocubanes have long been sought after as powerful, shock-insensitive, high-density explosives (Eaton, 1992). In these compounds are combined the energy associated with the highly strained cubane skeleton (Eaton, 1992) with that associated with polynitrated compounds. One of the more interesting stories in organic synthesis in recent years has been the long (ca20 years) development of methods (Eatonet al., 2000) to make octanitrocubane (Zhanget al., 2000), the `holy grail' of the energetic materials community. Theoretical predictions (Alster et al., 1981) had indicated that this compound would have one of the highest densities observed in compounds containing only C, H, N and O. In this search, the structures of 1,4-dinitro (Eaton et al., 1984), 1,3,5-trinitro-(Eaton et al., 1993), 1,3,5,7-tetranitro- (Eaton et al., 1993), 1,2,3,5,7-pentanitro- (Lukin et al., 1997), 1,2,3,4,5,6,8-hepta-nitro- (Zhanget al., 2000), and 1,2,3,4,5,6,7,8-octanitrocubane (Zhanget al., 2000) have been reported. However, to date the structure of the simplest member of this series, nitrocubane, is only now being reported (Butcher & Gilardi, 2002).

The structure of 1,2,3,4,5,7-hexanitrocubane, (I), is reported herein; previously the structure of its acetonitrile solvate had been reported (Lukin et al., 1997). Pure hexanitrocubane crystallizes in the orthorhombic space groupPnmawith four

molecules in the unit cell and thus the molecule has crystal-lographically imposed mirror symmetry passing through atoms C3, N3, O3A, O3B, C5, N5, O5A, O5B, C6, H6, C8, and H8. Positions C4Aand C7A, generated by the mirror plane, correspond to positions C2 and C1 in the conventional cubane numbering scheme. In hexanitrocubane, the CÐC bond lengths average 1.565 (6) AÊ, which is somewhat longer than the average found in all cubane structures, but well within the normal range (Butcher et al., 1995). The nitro O atoms attached to N7 are disordered over two positions, with occu-pancies of 0.600 (4) and 0.400 (4), which is not unusual for such moieties. As the number of nitro substituents increase, H atoms attached to the cubane skeleton become increasingly acidic (Lukin et al., 1997), and thus participate in stronger hydrogen-bonding interactions than is commonly observed for hydrocarbon H atoms. In this instance, H6 participates in short hydrogen-bonding contacts to O7AB in two adjoining mol-ecules (2.501 AÊ), thus linking molmol-ecules into a two-dimen-sional sheet in theabplane, as shown in Fig. 2. In addition, just as is the case in pentanitrocubane (Lukin et al., 1997), heptanitrocubane (Zhang et al., 2000), and octanitrocubane (Zhang et al., 2000), several O O contacts in hexanitro-cubane are shorter than the van der Waals contact distance of 3.04 AÊ (Rowland & Taylor, 1996). The shortest of these, 2.766 AÊ, involve the O atoms of the nitro group attached to C4. In hexanitrocubane, the nitro groups attached to C4 (and C4A which is related to C4 by the crystallographic mirror plane) are the only nitro groups that areorthoto three other nitro groups. These contacts are between the molecules that lie in an extended two-dimensional sheet parallel to thebcplane, as shown in Fig. 3.

Density is of critical importance to the performance of an explosive. The overall packing in hexanitrocubane described above leads to a density of 1.931 Mg mÿ3_{at 294 K. While this}

is less than that observed for pentanitrocubane (1.959 Mg mÿ3_{; Lukin et al., 1997), heptanitrocubane}

(2.028 Mg mÿ3_{; Zhang et al., 2000), and octanitrocubane}

(1.979 Mg mÿ3_{; Zhanget al., 2000), this is still an impressive}

value for a compound containing only C, H, N, and O, and is

Acta Cryst.(2002). E58, o978±o980 Richard Gilardiet al. C₈H₂N₆O₁₂

o979

organic papers

Figure 1

Displacement ellipsoid plot (50% probability level) of the title molecule, showing the atomic labeling scheme.

Figure 2

The molecules of (I) linking into a two-dimensional sheet in theabplane through short hydrogen-bonding contacts to C7 in adjoining molecules.

Figure 3

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much higher than the value previously observed for its acetonitrile solvate (1.676 Mg mÿ3_{; Lukin et al., 1997). The}

metrical parameters found for this unsolvated structure of hexanitrocubane are very similar to those found for the acetonitrile solvate (Lukinet al., 1997).

Experimental

The preparation of hexanitrobenzene has been reported previously (Lukin et al., 1997). Solvent-free crystals were grown by slow evaporation from a mixed HNO3/H2SO4solution at 313 K.

Crystal data

C8H2N6O12

Mr= 374.16 Orthorhombic,Pnma a= 13.936 (2) AÊ

b= 10.8870 (19) AÊ

c= 8.4833 (14) AÊ

V= 1287.1 (4) AÊ3

Z= 4

Dx= 1.931 Mg mÿ3

MoKradiation Cell parameters from 4545

re¯ections

= 2.8±28.3

= 0.19 mmÿ1

T= 295 (2) K Plate, orange 0.740.290.11 mm

Data collection

BrukerP4/CCD diffractometer

!scans

Absorption correction: multi-scan (Bruker, 2001)

Tmin= 0.819,Tmax= 0.962

9511 measured re¯ections 1655 independent re¯ections

1202 re¯ections withI> 2(I)

Rint= 0.026

max= 28.3

h=ÿ18!18

k=ÿ14!14

l=ÿ11!9

Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.046}

wR(F2_{) = 0.136}

S= 1.03 1655 re¯ections 157 parameters

All H-atom parameters re®ned

w= 1/[2_(F

o2) + (0.0747P)2 + 0.3718P]

whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.35 e AÊÿ3

min=ÿ0.24 e AÊÿ3

All H atoms were initially located in a difference Fourier map and re®ned isotropically. The nitro O atoms attached to N7 are disordered over two positions, with occupancies of 0.600 (4) and 0.400 (4), as is commonly found for such moieties.

Data collection:SMART(Bruker, 2001); cell re®nement:SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to re®ne structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.

The authors acknowledge the ®nancial support from the Of®ce of Naval Research, Mechanics Division. RJB wishes to acknowledge the ASEE/Navy Summer Faculty Research Program for support during the summer of 2002.

References

Alster, J., Sandus, O., Genter, R., Slagg, N., Ritchie, J. P., Dewar, M. & J. S. (1981). Working Group Meeting on High-Energy Molecules, Hilton Head, SC, USA, 28±29 April.

Bruker (2001).SMART(Version 5.624) andSAINT(Version 6.04). Bruker AXS Inc., Madison, Wisconsin, USA.

Butcher, R. J., Bashir-Hashemi, A. & Gilardi, R. (1995).J. Chem. Crystallogr.

25, 661±670.

Butcher, R. J. & Gilardi, R. (2002). In preparation.

Eaton, P. E. (1992).Angew. Chem. Int. Ed. Engl.31, 1421±1436.

Eaton, P. E., Gilardi, R. & Zhang, M.-X. (2000).Adv. Mater.12, 1143±1148. Eaton, P. E., Ravi Shankar, B. K., Price, G. D., Pluth, J. J., Gilbert, E. E., Alster,

J. & Sandus, O. (1984).J. Org. Chem.49, 185±186.

Eaton, P. E., Yusheng Xiong, Y. & Gilardi, R. (1993).J. Am. Chem. Soc.115, 10195±10202.

Lukin, K. A., Li, J., Eaton, P. E., Kanomata, N., Hain, J., Punzalan, E. & Gilardi, R. (1997).J. Am. Chem. Soc.119, 9591±9602.

Rowland, R. S. & Taylor, R. (1996).J. Phys. Chem.100, 7384±7391. Sheldrick, G. M. (1997).SHELXTL.Version 5.10. Bruker AXS Inc., Madison

Wisconsin USA.

Zhang, M.-X., Eaton, P. E. & Gilardi, R. (2000).Angew. Chem. Int. Ed. Engl.

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Acta Cryst. (2002). E58, o978–o980

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Acta Cryst. (2002). E58, o978–o980 [doi:10.1107/S1600536802013739]

1,2,3,4,5,7-Hexanitrocubane

Richard Gilardi, Ray J. Butcher and Mao-Xi Zhang

S1. Comment

Nitrocubanes have long been sought after as powerful, shock-insensitive, high-density explosives (Eaton, 1992). In these

compounds are combined the energy associated with the highly strained cubane skeleton (Eaton, 1992) with that

associated with polynitrated compounds. One of the more interesting stories in organic synthesis in recent years has been

the long (ca 20 years) development of methods (Eaton at al., 2000) to make octanitrocubane (Zhang et al., 2000), the

`holy grail′ of the energetic materials community. Theoretical predictions (Alster et al., 1981) had indicated that this

compound would have one of the highest densities observed in compounds containing only C, H, N and O. In this search,

the structures of 1,4-dinitro (Eaton et al., 1984), 1,3,5-trinitro- (Eaton et al., 1993), 1,3,5,7-tetranitro- (Eaton et al., 1993),

1,2,3,5,7-pentanitro- (Lukin et al., 1997), 1,2,3,4,5,6,8-heptanitro- (Zhang et al., 2000), and

1,2,3,4,5,6,7,8-octanitro-cubane (Zhang et al., 2000) have been reported. However, to date the structure of the simplest member of this series,

nitrocubane, is only now being reported (Butcher & Gilardi, 2002).

The structure of 1,2,3,4,5,7-hexanitrocubane, (I), is reported herein; previously the structure of its acetonitrile solvate

was reported (Lukin et al., 1997). Pure hexanitrocubane crystallizes in the orthorhombic space group Pnma with four

molecules in the unit cell, thus the molecule has crystallographically imposed mirror symmetry, which passes through

atoms C3, N3, O3A, O3B, C5, N5, O5A, O5B, C6, H6, C8, and H8. Positions C4A and C7A, generated by the mirror

plane, correspond to positions C2 and C1 in the conventional cubane numbering scheme. In hexanitrocubane, the C—C

bond lengths average 1.565 (6) Å, which is somewhat longer than the average found in all cubane structures, but well

within the normal range (Butcher et al., 1995). The nitro O atomd attached to N7 are disordered over two positions, with

occupancies of 0.600 (4) and 0.400 (4), which is not unusual for such moieties. As the number of nitro substituents

increase, H atoms attached to the cubane skeleton become increasingly acidic (Lukin et al., 1997), and thus participate in

stronger hydrogen-bonding interactions than is commonly observed for hydrocarbon H atoms. In this instance, both H6

and H8 participate in short hydrogen-bonding contacts to O7AB in adjoining molecules (2.501 Å), thus linking molecules

into a two-dimensional sheet in the bc plane, as shown in Fig. 1. In addition, just as is the case in pentanitrocubane (Lukin

et al., 1997), heptanitrocubane (Zhang et al., 2000), and octanitrocubane (Zhang et al., 2000), several O···O contacts in hexanitrocubane are shorter than the van der Waals contact distance of 3.04 Å (Rowland & Taylor, 1996). The shortest of

these, 2.766 Å, involve the O atoms of the nitro group attached to C4. In hexanitrocubane, the nitro groups attached to C4

(and C4A which is related to C4 by the crystallographic mirror plane) are the only nitro groups that are ortho to three

other nitro groups. These contacts are between the molecules that lie in an extended two-dimensional sheet parallel to the

ab plane, as shown in Fig. 2.

Density is of critical importance to the performance of an explosive. The overall packing in hexanitrocubane described

above leads to a density of 1.931 Mg m−3 _{at 294 K. While this is less than that observed for pentanitrocubane (1.959 Mg}

m−3_{; Lukin et al., 1997), heptanitrocubane (2.028 Mg m}−3_{; Zhang et al., 2000), and octanitrocubane (1.979 Mg m}−3_;

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Acta Cryst. (2002). E58, o978–o980

than the value previously observed for its acetonitrile solvate (1.676 Mg m−3_{; Lukin et al., 1997). The metrical parameters}

found for this unsolvated structure of hexanitrocubane are very similar to those found for the acetonitrile solvate (Lukin

et al., 1997).

S2. Experimental

The preparation of hexanitrobenzene has been reported previously (Lukin et al., 1997). Solvent-free crytals were grown

by slow evaporation from a mixed HNO3/H2SO4 solution at 313 K.

S3. Refinement

All H atoms were initially located in a difference Fourier map and refined isotropically. The nitro O atoms attached to N7

are disordered over two positions, with occupancies of 0.600 (4) and 0.400 (4), as is commonly found for such moieties.

Figure 1

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Acta Cryst. (2002). E58, o978–o980 Figure 2

The molecules of (I) linking into a two-dimensional sheet in the bc plane through short hydrogen-bonding contacts to C7

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Acta Cryst. (2002). E58, o978–o980 Figure 3

Short O···O contacts from the C4 nitro group linking up molecules in an extended two-dimensional sheet parallel to the

ab plane.

(I)

Crystal data

C8H2N6O12 Mr = 374.16

Orthorhombic, Pnma

a = 13.936 (2) Å

b = 10.8870 (19) Å

c = 8.4833 (14) Å

V = 1287.1 (4) Å3 Z = 4

F(000) = 752

Dx = 1.931 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4545 reflections

θ = 2.8–28.3°

µ = 0.19 mm−1 T = 295 K Plate, orange

0.74 × 0.29 × 0.11 mm

Data collection

Bruker P4/CCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: multi-scan (Bruker, 2001)

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Acta Cryst. (2002). E58, o978–o980

9511 measured reflections 1655 independent reflections 1202 reflections with I > 2σ(I)

Rint = 0.026

θmax = 28.3°, θmin = 2.8°

h = −18→18

k = −14→14

l = −11→9

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.046} wR(F2_{) = 0.136} S = 1.03 1655 reflections 157 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

All H-atom parameters refined

w = 1/[σ2_(F

o2) + (0.0747P)2 + 0.3718P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.35 e Å−3

Δρmin = −0.24 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 Occ. (<1)

C3 0.33820 (19) 0.2500 1.0939 (3) 0.0356 (5)

N3 0.3347 (2) 0.2500 1.2689 (3) 0.0518 (7)

O3A 0.4094 (2) 0.2500 1.3397 (3) 0.0794 (8)

O3B 0.2542 (2) 0.2500 1.3251 (3) 0.0773 (8)

C4 0.29000 (12) 0.14906 (14) 0.98930 (18) 0.0323 (4)

N4 0.24031 (12) 0.03958 (13) 1.05379 (18) 0.0427 (4)

O4A 0.27462 (14) −0.00370 (15) 1.17313 (19) 0.0716 (5)

O4B 0.17065 (13) 0.00225 (15) 0.9865 (2) 0.0725 (5)

C5 0.24530 (16) 0.2500 0.8802 (3) 0.0315 (5)

N5 0.14369 (16) 0.2500 0.8305 (3) 0.0452 (6)

O5A 0.12710 (16) 0.2500 0.6895 (3) 0.0625 (6)

O5B 0.08567 (15) 0.2500 0.9385 (3) 0.0760 (8)

C6 0.33648 (18) 0.2500 0.7732 (3) 0.0325 (5)

H6 0.336 (2) 0.2500 0.658 (3) 0.045 (7)*

C7 0.38139 (12) 0.14914 (14) 0.88278 (18) 0.0329 (4)

N7 0.43102 (11) 0.03600 (15) 0.8312 (2) 0.0438 (4)

O7AA 0.4809 (6) 0.0462 (8) 0.7150 (7) 0.0646 (16) 0.60

O7AB 0.4202 (5) −0.0520 (6) 0.9158 (7) 0.0768 (17) 0.60

O7BA 0.5027 (10) 0.0394 (12) 0.7631 (17) 0.121 (5) 0.40

O7BB 0.3923 (6) −0.0640 (8) 0.8610 (9) 0.0605 (18) 0.40

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H8 0.4926 (19) 0.2500 1.021 (3) 0.042 (8)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C3 0.0498 (14) 0.0238 (11) 0.0332 (11) 0.000 −0.0025 (10) 0.000

N3 0.092 (2) 0.0281 (11) 0.0351 (11) 0.000 −0.0040 (14) 0.000

O3A 0.117 (2) 0.0733 (17) 0.0480 (11) 0.000 −0.0317 (14) 0.000

O3B 0.111 (2) 0.0656 (16) 0.0549 (13) 0.000 0.0323 (14) 0.000

C4 0.0395 (9) 0.0229 (8) 0.0345 (7) 0.0000 (6) 0.0022 (7) −0.0006 (6)

N4 0.0555 (10) 0.0282 (7) 0.0446 (8) −0.0059 (7) 0.0095 (7) −0.0016 (6)

O4A 0.1071 (14) 0.0452 (9) 0.0623 (9) −0.0093 (9) −0.0083 (9) 0.0233 (8)

O4B 0.0769 (12) 0.0621 (10) 0.0784 (11) −0.0336 (9) −0.0040 (9) 0.0073 (9)

C5 0.0329 (12) 0.0247 (11) 0.0369 (11) 0.000 −0.0004 (10) 0.000

N5 0.0376 (12) 0.0329 (11) 0.0650 (14) 0.000 −0.0057 (11) 0.000

O5A 0.0580 (13) 0.0601 (14) 0.0694 (14) 0.000 −0.0271 (11) 0.000

O5B 0.0426 (12) 0.0911 (19) 0.0943 (18) 0.000 0.0200 (13) 0.000

C6 0.0373 (13) 0.0277 (11) 0.0326 (10) 0.000 0.0003 (10) 0.000

C7 0.0333 (8) 0.0266 (8) 0.0388 (8) 0.0023 (6) −0.0005 (7) −0.0020 (6)

N7 0.0370 (9) 0.0352 (8) 0.0593 (10) 0.0051 (7) −0.0041 (7) −0.0106 (7)

O7AA 0.061 (4) 0.061 (3) 0.0717 (18) 0.012 (3) 0.029 (2) −0.0052 (17)

O7AB 0.110 (5) 0.038 (2) 0.083 (3) 0.030 (3) 0.005 (2) 0.011 (2)

O7BA 0.053 (5) 0.060 (6) 0.251 (15) −0.012 (4) 0.060 (8) −0.062 (8)

O7BB 0.069 (4) 0.030 (2) 0.082 (5) 0.003 (3) 0.021 (3) 0.001 (3)

C8 0.0380 (14) 0.0276 (11) 0.0433 (12) 0.000 −0.0080 (11) 0.000

Geometric parameters (Å, º)

C3—N3 1.486 (3) N5—O5A 1.218 (3)

C3—C8 1.550 (4) N5—O5B 1.222 (3)

C3—C4 1.564 (2) C6—C7i _{1.569 (2)}

C3—C4i _{1.564 (2) C6—C7 1.569 (2)}

N3—O3A 1.202 (4) C6—H6 0.98 (3)

N3—O3B 1.218 (4) C7—N7 1.479 (2)

C4—N4 1.483 (2) C7—C8 1.572 (2)

C4—C7 1.562 (2) N7—O7BA 1.155 (14)

C4—C5 1.566 (2) N7—O7AB 1.206 (7)

N4—O4B 1.197 (2) N7—O7AA 1.211 (7)

N4—O4A 1.215 (2) N7—O7BB 1.241 (9)

C5—N5 1.478 (3) C8—C7i _{1.572 (2)}

C5—C6 1.562 (3) C8—H8 0.92 (3)

C5—C4i _{1.566 (2)}

N3—C3—C8 126.8 (2) C5—C6—C7 88.85 (13)

N3—C3—C4 123.56 (14) C7i_{—C6—C7 88.82 (16)}

C8—C3—C4 91.57 (14) C5—C6—H6 125.3 (17)

N3—C3—C4i _{123.56 (14) C7}i_{—C6—H6 126.5 (9)}

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C4—C3—C4i _{89.27 (17) N7—C7—C4 123.51 (14)}

O3A—N3—O3B 127.0 (3) N7—C7—C6 126.46 (14)

O3A—N3—C3 118.1 (3) C4—C7—C6 91.03 (13)

O3B—N3—C3 114.9 (3) N7—C7—C8 123.57 (14)

N4—C4—C7 126.49 (13) C4—C7—C8 90.84 (14)

N4—C4—C3 123.77 (14) C6—C7—C8 91.25 (12)

C7—C4—C3 88.72 (14) O7BA—N7—O7AB 115.6 (8)

N4—C4—C5 126.60 (15) O7BA—N7—O7AA 25.0 (9)

C7—C4—C5 88.97 (13) O7AB—N7—O7AA 129.0 (5)

C3—C4—C5 90.75 (12) O7BA—N7—O7BB 120.4 (8)

O4B—N4—O4A 125.80 (17) O7AB—N7—O7BB 29.3 (4)

O4B—N4—C4 118.39 (16) O7AA—N7—O7BB 119.7 (6)

O4A—N4—C4 115.81 (16) O7BA—N7—C7 121.7 (7)

N5—C5—C6 127.9 (2) O7AB—N7—C7 115.3 (4)

N5—C5—C4i _{123.35 (13) O7AA—N7—C7 115.6 (4)}

C6—C5—C4i _{91.14 (13) O7BB—N7—C7 117.9 (5)}

N5—C5—C4 123.35 (13) C3—C8—C7 88.86 (15)

C6—C5—C4 91.14 (13) C3—C8—C7i _{88.86 (15)}

C4i_{—C5—C4 89.14 (16) C7—C8—C7}i _{88.63 (17)}

O5A—N5—O5B 127.6 (3) C3—C8—H8 127.9 (17)

O5A—N5—C5 117.5 (2) C7—C8—H8 125.2 (9)

O5B—N5—C5 114.9 (2) C7i_{—C8—H8 125.2 (9)}

C5—C6—C7i _{88.85 (13)}

C8—C3—N3—O3A 0.000 (1) C4—C5—C6—C7 −0.16 (11)

C4—C3—N3—O3A 122.53 (19) N4—C4—C7—N7 0.2 (3)

C4i_{—C3—N3—O3A −122.53 (19) C3—C4—C7—N7 132.63 (15)}

C8—C3—N3—O3B 180.0 C5—C4—C7—N7 −136.60 (15)

C4—C3—N3—O3B −57.47 (19) N4—C4—C7—C6 136.61 (16)

C4i_{—C3—N3—O3B 57.47 (19) C3—C4—C7—C6 −90.93 (12)}

N3—C3—C4—N4 −3.4 (3) C5—C4—C7—C6 −0.16 (11)

C8—C3—C4—N4 134.15 (16) N4—C4—C7—C8 −132.13 (16)

C4i_{—C3—C4—N4 −134.30 (13) C3—C4—C7—C8 0.33 (12)}

N3—C3—C4—C7 −137.9 (2) C5—C4—C7—C8 91.10 (12)

C8—C3—C4—C7 −0.33 (12) C5—C6—C7—N7 134.57 (16)

C4i_{—C3—C4—C7 91.22 (14) C7}i_{—C6—C7—N7 −136.56 (13)}

N3—C3—C4—C5 133.2 (2) C5—C6—C7—C4 0.16 (12)

C8—C3—C4—C5 −89.29 (14) C7i_{—C6—C7—C4 89.04 (13)}

C4i_{—C3—C4—C5 2.26 (17) C5—C6—C7—C8 −90.70 (14)}

C7—C4—N4—O4B −98.4 (2) C7i_{—C6—C7—C8 −1.83 (17)}

C3—C4—N4—O4B 144.17 (19) C4—C7—N7—O7BA −173.7 (8)

C5—C4—N4—O4B 23.1 (3) C6—C7—N7—O7BA 65.2 (9)

C7—C4—N4—O4A 82.3 (2) C8—C7—N7—O7BA −56.3 (9)

C3—C4—N4—O4A −35.2 (2) C4—C7—N7—O7AB −25.1 (4)

C5—C4—N4—O4A −156.29 (17) C6—C7—N7—O7AB −146.2 (3)

N4—C4—C5—N5 1.9 (3) C8—C7—N7—O7AB 92.3 (4)

C7—C4—C5—N5 138.61 (18) C4—C7—N7—O7AA 158.6 (4)

supporting information

sup-8

Acta Cryst. (2002). E58, o978–o980

N4—C4—C5—C6 −136.53 (16) C8—C7—N7—O7AA −84.0 (5)

C7—C4—C5—C6 0.16 (12) C4—C7—N7—O7BB 7.6 (4)

C3—C4—C5—C6 88.87 (14) C6—C7—N7—O7BB −113.5 (4)

N4—C4—C5—C4i _{132.34 (12) C8—C7—N7—O7BB 125.0 (4)}

C7—C4—C5—C4i _{−90.97 (13) N3—C3—C8—C7 135.67 (8)}

C3—C4—C5—C4i _{−2.26 (17) C4—C3—C8—C7 0.33 (12)}

C6—C5—N5—O5A 0.0 C4i_{—C3—C8—C7 −88.98 (12)}

C4i_{—C5—N5—O5A 122.84 (16) N3—C3—C8—C7}i _{−135.67 (8)}

C4—C5—N5—O5A −122.84 (16) C4—C3—C8—C7i _{88.98 (12)}

C6—C5—N5—O5B 180.0 C4i_{—C3—C8—C7}i _{−0.33 (12)}

C4i_{—C5—N5—O5B −57.16 (16) N7—C7—C8—C3 −132.58 (16)}

C4—C5—N5—O5B 57.16 (16) C4—C7—C8—C3 −0.33 (12)

N5—C5—C6—C7i _{135.58 (8) C6—C7—C8—C3 90.72 (14)}

C4i_{—C5—C6—C7}i _{0.16 (11) N7—C7—C8—C7}i _{138.53 (13)}

C4—C5—C6—C7i _{−89.00 (11) C4—C7—C8—C7}i _{−89.22 (14)}

N5—C5—C6—C7 −135.58 (8) C6—C7—C8—C7i _{1.83 (17)}

C4i_{—C5—C6—C7 89.00 (11)}