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The title compound, 1,4-bis­(di­nitro­methyl)­penta­cyclo­[4.2.0.02,5.03,8.04,7]­octane, C10H8N4O8, crystallizes in the monoclinic space group P21/c. The asymmetric unit consists of two half-mol­ecules located about centers of inversion. There are no significant differences in chemically equivalent bond lengths and angles between the two half-mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001374/cv6001sup1.cif
Contains datablocks global, 1

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001374/cv6001Isup2.hkl
Contains datablock I

CCDC reference: 159749

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.050
  • wR factor = 0.139
  • Data-to-parameter ratio = 8.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Amber Alert Alert Level B:
THETM_01 Alert B The value of sine(theta_max)/wavelength is less than 0.575 Calculated sin(theta_max)/wavelength = 0.5515
Author response: The mean intensity of the x-ray reflections drops rapidly from about 132 for the low resolution data to about 25 for 1.4 to 1.7 A data to about 3 0.95 A data, therefore no data was collected beyond 0.91 A resolution. There was also significant decay during data collection (6.75%).

Yellow Alert Alert Level C:
REFNR_01 Alert C Ratio of reflections to parameters is < 10 for a centrosymmetric structure sine(theta)/lambda 0.5515 Proportion of unique data used 1.0000 Ratio reflections to parameters 8.9500 PLAT_320 Alert C Check Hybridisation of C1 in main residue ? PLAT_320 Alert C Check Hybridisation of C2 in main residue ? PLAT_320 Alert C Check Hybridisation of C6 in main residue ? PLAT_320 Alert C Check Hybridisation of C8 in main residue ? PLAT_320 Alert C Check Hybridisation of C1' in main residue ? PLAT_320 Alert C Check Hybridisation of C2' in main residue ? PLAT_320 Alert C Check Hybridisation of C6' in main residue ? PLAT_320 Alert C Check Hybridisation of C8' in main residue ?
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
9 Alert Level C = Please check

Comment top

Cubane and its derivatives are highly strained stable molecules. Substituted cubanes are of interest because, with the proper number and type of energetic substituents, they have proved to be very high-energy high-density materials (Zhang et al., 2000). The rigid framework of the cubane skeleton, in which multiple functional groups would possess unique arrangements, shows also potential applications for use in pharmaceutical and polymer chemistry (Butcher et al., 1995). Functionalization of the cubane skeleton has involved displacement directly at the cubyl C atoms either via carbanions (Eaton et al., 1987), radicals (Moriarty et al., 1989) or hypervalent iodine methods (Eaton & Cunkle, 1986). In this study, we report on the next logical step in this synthetic area, exocyclic carbanionic functionalization involving the cubylcarbinyl carbanion, as in the conversion of 1,4-bis(nitromethyl)cubane to 1,4-bis(dinitromethyl)cubane, (I).

Fig. 1 shows the structure and labeling scheme for the title compound. Selected metrical parameters for the title compound are given in Table 1. The average C—C bond length (within the cube) of 21 disubstituted cubanes in the Cambridge Structural Database is 1.564 Å (n = 93; Allen & Kennard, 1993). Butcher et al. (1995) reported lengthening of the C—C bond when a π-donating or accepting group is oriented orthogonal to a cube edge and shortening of the C—C bond when such a substituent is nearly eclipsed with (i.e. parallel to) the cube edge. Based on the larger number of entries now in the Cambridge Structural Database, the average C—C bond length when a π-donating or accepting group is oriented orthagonal to a cube edge is 1.582 Å (n = 7), and 1.549 Å (n = 7) when such a group is parallel to the cube edge. When the nitro group is moved one carbon away from the cube this effect is absent, as the C—C bond lengths in (I) are 1.563 (3) or 1.565 (3) Å.

Experimental top

The title compound, (I), was synthesized by nucleophilic displacement upon C(NO2)4 by the anion derived from 1,4-bis(nitromethyl)cubane, (Ia). The dianion of (Ia), generated at 273 K in methanol with 4.3 equivalents of KOH, was treated with 5.3 equivalents of tetranitromethane. The mixture was stirred for 10 min at 273 K, then was poured into chilled 1 M acetic acid. After work-up, chromatography and crystallization from CCl4, the title compound was obtained in 18% yield. Clear pale yellow crystals of the title compound were grown from 2-butanone/n-octane.

Computing details top

Data collection: Bruker XSCANS (Bruker, 1994); cell refinement: Bruker XSCANS (Bruker, 1994); data reduction: Bruker XPREP (Bruker, 1994); program(s) used to solve structure: SHELXS (Sheldrick, 1990); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. View of 1,4-bis(dinitromethyl)cubane showing the labeling of all non-H atoms. Displacement ellipsoids are at the 20% probability level. H atoms are drawn as small circles of arbitrary radii. Symmetry atoms required to complete the cubane structure are included but not labeled.
1,4-bis(dinitromethyl)cubane top
Crystal data top
C10H8N4O8F(000) = 640
Mr = 312.20Dx = 1.628 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54178 Å
a = 11.2481 (4) ÅCell parameters from 30 reflections
b = 7.1112 (3) Åθ = 5.6–31.4°
c = 16.1263 (7) ŵ = 1.27 mm1
β = 99.043 (5)°T = 294 K
V = 1273.87 (9) Å3Plate, pale yellow
Z = 40.60 × 0.46 × 0.06 mm
Data collection top
Siemens P4
diffractometer
1636 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.054
Graphite monochromatorθmax = 58.2°, θmin = 4.0°
2θ/ω scansh = 1212
Absorption correction: analytical
(XPREP; Siemens, 1994)
k = 77
Tmin = 0.539, Tmax = 0.927l = 017
3788 measured reflections3 standard reflections every 97 reflections
1790 independent reflections intensity decay: 6.8%
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)] = 0.050H-atom parameters constrained
wR(F2) = 0.139 w = 1/[σ2(Fo2) + (0.0782P)2 + 0.7744P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.008
1790 reflectionsΔρmax = 0.42 e Å3
200 parametersΔρmin = 0.26 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0091 (10)
Crystal data top
C10H8N4O8V = 1273.87 (9) Å3
Mr = 312.20Z = 4
Monoclinic, P21/cCu Kα radiation
a = 11.2481 (4) ŵ = 1.27 mm1
b = 7.1112 (3) ÅT = 294 K
c = 16.1263 (7) Å0.60 × 0.46 × 0.06 mm
β = 99.043 (5)°
Data collection top
Siemens P4
diffractometer
1636 reflections with I > 2σ(I)
Absorption correction: analytical
(XPREP; Siemens, 1994)
Rint = 0.054
Tmin = 0.539, Tmax = 0.927θmax = 58.2°
3788 measured reflections3 standard reflections every 97 reflections
1790 independent reflections intensity decay: 6.8%
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.139H-atom parameters constrained
S = 1.03Δρmax = 0.42 e Å3
1790 reflectionsΔρmin = 0.26 e Å3
200 parameters
Special details top

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.95847 (19)0.4103 (3)0.92759 (13)0.0345 (6)
C20.9926 (2)0.3137 (3)1.01527 (14)0.0409 (6)
H2A0.98710.17861.02610.049*
C60.8901 (2)0.5678 (4)0.96865 (14)0.0407 (6)
H6A0.81020.61640.94580.049*
C81.0763 (2)0.5302 (4)0.94488 (14)0.0398 (6)
H8A1.13160.55150.90460.048*
C90.9134 (2)0.3174 (3)0.84614 (14)0.0372 (6)
H9A0.88380.41320.80430.045*
N10.8127 (2)0.1822 (4)0.85533 (15)0.0557 (6)
N21.0093 (2)0.2019 (3)0.81482 (14)0.0501 (6)
O10.8132 (3)0.0323 (5)0.8249 (3)0.170 (2)
O20.7335 (2)0.2421 (4)0.88931 (14)0.0782 (7)
O31.0095 (3)0.2009 (5)0.73980 (15)0.1019 (10)
O41.0800 (2)0.1185 (4)0.86542 (15)0.0812 (8)
C1'1.47427 (19)0.0807 (3)0.92380 (13)0.0321 (6)
C2'1.37897 (19)0.0096 (3)0.97758 (13)0.0354 (6)
H2'A1.29150.01680.96100.042*
C6'1.5476 (2)0.1750 (3)1.00375 (13)0.0358 (6)
H6'A1.58170.30201.00600.043*
C8'1.5482 (2)0.1039 (3)0.94319 (13)0.0352 (6)
H8'A1.58280.17890.90190.042*
C9'1.44922 (19)0.1721 (3)0.83997 (13)0.0333 (6)
H9'A1.52320.17460.81500.040*
N1'1.40485 (18)0.3693 (3)0.84740 (12)0.0427 (6)
N2'1.35171 (18)0.0707 (3)0.78136 (12)0.0414 (5)
O1'1.3251 (2)0.3934 (3)0.88786 (17)0.0810 (8)
O2'1.4559 (2)0.4940 (3)0.81795 (17)0.0852 (8)
O3'1.2984 (2)0.1578 (3)0.72260 (12)0.0690 (7)
O4'1.3362 (2)0.0935 (3)0.79557 (12)0.0650 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0314 (11)0.0400 (13)0.0322 (12)0.0018 (10)0.0056 (9)0.0009 (10)
C20.0511 (14)0.0349 (13)0.0368 (13)0.0018 (11)0.0071 (11)0.0017 (10)
C60.0320 (12)0.0507 (14)0.0384 (13)0.0107 (10)0.0022 (10)0.0037 (11)
C80.0352 (12)0.0522 (15)0.0341 (13)0.0044 (11)0.0116 (10)0.0021 (11)
C90.0340 (12)0.0421 (13)0.0355 (12)0.0022 (10)0.0054 (10)0.0017 (10)
N10.0459 (13)0.0577 (15)0.0610 (15)0.0099 (11)0.0005 (11)0.0067 (12)
N20.0495 (13)0.0553 (14)0.0461 (13)0.0019 (11)0.0091 (10)0.0135 (11)
O10.108 (2)0.091 (2)0.328 (6)0.0539 (19)0.090 (3)0.103 (3)
O20.0598 (13)0.1038 (19)0.0784 (15)0.0229 (13)0.0338 (12)0.0069 (14)
O30.135 (2)0.121 (2)0.0549 (15)0.0443 (19)0.0323 (14)0.0192 (14)
O40.0670 (14)0.0977 (18)0.0747 (15)0.0370 (13)0.0023 (12)0.0149 (14)
C1'0.0308 (11)0.0389 (13)0.0274 (11)0.0015 (9)0.0073 (9)0.0024 (10)
C2'0.0277 (11)0.0498 (14)0.0290 (12)0.0015 (10)0.0057 (9)0.0018 (10)
C6'0.0403 (12)0.0373 (13)0.0304 (12)0.0049 (10)0.0078 (10)0.0030 (10)
C8'0.0409 (12)0.0389 (13)0.0279 (12)0.0028 (10)0.0116 (10)0.0039 (10)
C9'0.0321 (11)0.0406 (13)0.0285 (11)0.0001 (10)0.0083 (9)0.0023 (9)
N1'0.0472 (12)0.0418 (12)0.0409 (11)0.0003 (10)0.0127 (10)0.0043 (9)
N2'0.0442 (11)0.0497 (13)0.0290 (11)0.0014 (10)0.0019 (9)0.0007 (9)
O1'0.0850 (15)0.0600 (13)0.1128 (18)0.0194 (12)0.0615 (15)0.0052 (13)
O2'0.1037 (18)0.0485 (13)0.115 (2)0.0033 (13)0.0534 (16)0.0200 (13)
O3'0.0741 (14)0.0720 (14)0.0503 (12)0.0048 (11)0.0229 (10)0.0084 (10)
O4'0.0865 (15)0.0523 (13)0.0490 (11)0.0230 (11)0.0116 (10)0.0038 (9)
Geometric parameters (Å, º) top
C1—C91.487 (3)C1'—C9'1.487 (3)
C1—C61.563 (3)C1'—C8'1.560 (3)
C1—C81.563 (3)C1'—C2'1.565 (3)
C1—C21.565 (3)C1'—C6'1.567 (3)
C2—C8i1.550 (3)C2'—C6'ii1.555 (3)
C2—C6i1.552 (4)C2'—C8'ii1.557 (3)
C6—C8i1.551 (3)C6'—C2'ii1.555 (3)
C6—C2i1.552 (4)C6'—C8'ii1.562 (3)
C8—C6i1.551 (3)C8'—C2'ii1.557 (3)
C8—C2i1.550 (3)C8'—C6'ii1.562 (3)
C9—N21.504 (3)C9'—N1'1.499 (3)
C9—N11.510 (3)C9'—N2'1.514 (3)
N1—O11.174 (4)N1'—O2'1.195 (3)
N1—O21.196 (3)N1'—O1'1.201 (3)
N2—O41.203 (3)N2'—O4'1.207 (3)
N2—O31.210 (3)N2'—O3'1.209 (3)
C9—C1—C6124.78 (18)C9'—C1'—C8'124.70 (18)
C9—C1—C8124.19 (18)C9'—C1'—C2'126.64 (18)
C6—C1—C889.61 (17)C8'—C1'—C2'90.41 (17)
C9—C1—C2127.2 (2)C9'—C1'—C6'124.13 (19)
C6—C1—C289.95 (17)C8'—C1'—C6'90.00 (16)
C8—C1—C289.85 (16)C2'—C1'—C6'90.00 (15)
C8i—C2—C6i90.49 (18)C6'ii—C2'—C8'ii90.57 (16)
C8i—C2—C189.55 (17)C6'ii—C2'—C1'89.47 (16)
C6i—C2—C189.66 (17)C8'ii—C2'—C1'89.88 (15)
C8i—C6—C2i90.75 (17)C2'ii—C6'—C8'ii90.71 (17)
C8i—C6—C189.57 (17)C2'ii—C6'—C1'89.61 (17)
C2i—C6—C189.91 (17)C8'ii—C6'—C1'89.61 (16)
C6i—C8—C2i90.92 (17)C2'ii—C8'—C1'89.81 (16)
C6i—C8—C189.74 (17)C2'ii—C8'—C6'ii90.50 (15)
C2i—C8—C189.98 (17)C1'—C8'—C6'ii89.41 (16)
C1—C9—N2112.09 (18)C1'—C9'—N1'110.74 (18)
C1—C9—N1110.68 (19)C1'—C9'—N2'112.00 (19)
N2—C9—N1105.9 (2)N1'—C9'—N2'106.14 (18)
O1—N1—O2124.6 (3)O2'—N1'—O1'123.8 (2)
O1—N1—C9119.0 (3)O2'—N1'—C9'118.4 (2)
O2—N1—C9116.3 (2)O1'—N1'—C9'117.6 (2)
O4—N2—O3124.7 (3)O4'—N2'—O3'125.1 (2)
O4—N2—C9118.3 (2)O4'—N2'—C9'117.0 (2)
O3—N2—C9116.9 (2)O3'—N2'—C9'117.8 (2)
Symmetry codes: (i) x+2, y+1, z+2; (ii) x+3, y, z+2.

Experimental details

Crystal data
Chemical formulaC10H8N4O8
Mr312.20
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)11.2481 (4), 7.1112 (3), 16.1263 (7)
β (°) 99.043 (5)
V3)1273.87 (9)
Z4
Radiation typeCu Kα
µ (mm1)1.27
Crystal size (mm)0.60 × 0.46 × 0.06
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionAnalytical
(XPREP; Siemens, 1994)
Tmin, Tmax0.539, 0.927
No. of measured, independent and
observed [I > 2σ(I)] reflections
3788, 1790, 1636
Rint0.054
θmax (°)58.2
(sin θ/λ)max1)0.551
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.139, 1.03
No. of reflections1790
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.42, 0.26

Computer programs: Bruker XSCANS (Bruker, 1994), Bruker XPREP (Bruker, 1994), SHELXS (Sheldrick, 1990), SHELXTL (Sheldrick, 1997).

Selected bond lengths (Å) top
C1—C61.563 (3)C1'—C8'1.560 (3)
C1—C81.563 (3)C1'—C2'1.565 (3)
C1—C21.565 (3)C1'—C6'1.567 (3)
 

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