Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001374/cv6001sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001374/cv6001Isup2.hkl |
CCDC reference: 159749
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.
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).
C10H8N4O8 | F(000) = 640 |
Mr = 312.20 | Dx = 1.628 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
a = 11.2481 (4) Å | Cell parameters from 30 reflections |
b = 7.1112 (3) Å | θ = 5.6–31.4° |
c = 16.1263 (7) Å | µ = 1.27 mm−1 |
β = 99.043 (5)° | T = 294 K |
V = 1273.87 (9) Å3 | Plate, pale yellow |
Z = 4 | 0.60 × 0.46 × 0.06 mm |
Siemens P4 diffractometer | 1636 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.054 |
Graphite monochromator | θmax = 58.2°, θmin = 4.0° |
2θ/ω scans | h = −12→12 |
Absorption correction: analytical (XPREP; Siemens, 1994) | k = −7→7 |
Tmin = 0.539, Tmax = 0.927 | l = 0→17 |
3788 measured reflections | 3 standard reflections every 97 reflections |
1790 independent reflections | intensity decay: 6.8% |
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)] = 0.050 | H-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 reflections | Δρmax = 0.42 e Å−3 |
200 parameters | Δρmin = −0.26 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0091 (10) |
C10H8N4O8 | V = 1273.87 (9) Å3 |
Mr = 312.20 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 11.2481 (4) Å | µ = 1.27 mm−1 |
b = 7.1112 (3) Å | T = 294 K |
c = 16.1263 (7) Å | 0.60 × 0.46 × 0.06 mm |
β = 99.043 (5)° |
Siemens P4 diffractometer | 1636 reflections with I > 2σ(I) |
Absorption correction: analytical (XPREP; Siemens, 1994) | Rint = 0.054 |
Tmin = 0.539, Tmax = 0.927 | θmax = 58.2° |
3788 measured reflections | 3 standard reflections every 97 reflections |
1790 independent reflections | intensity decay: 6.8% |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.42 e Å−3 |
1790 reflections | Δρmin = −0.26 e Å−3 |
200 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.95847 (19) | 0.4103 (3) | 0.92759 (13) | 0.0345 (6) | |
C2 | 0.9926 (2) | 0.3137 (3) | 1.01527 (14) | 0.0409 (6) | |
H2A | 0.9871 | 0.1786 | 1.0261 | 0.049* | |
C6 | 0.8901 (2) | 0.5678 (4) | 0.96865 (14) | 0.0407 (6) | |
H6A | 0.8102 | 0.6164 | 0.9458 | 0.049* | |
C8 | 1.0763 (2) | 0.5302 (4) | 0.94488 (14) | 0.0398 (6) | |
H8A | 1.1316 | 0.5515 | 0.9046 | 0.048* | |
C9 | 0.9134 (2) | 0.3174 (3) | 0.84614 (14) | 0.0372 (6) | |
H9A | 0.8838 | 0.4132 | 0.8043 | 0.045* | |
N1 | 0.8127 (2) | 0.1822 (4) | 0.85533 (15) | 0.0557 (6) | |
N2 | 1.0093 (2) | 0.2019 (3) | 0.81482 (14) | 0.0501 (6) | |
O1 | 0.8132 (3) | 0.0323 (5) | 0.8249 (3) | 0.170 (2) | |
O2 | 0.7335 (2) | 0.2421 (4) | 0.88931 (14) | 0.0782 (7) | |
O3 | 1.0095 (3) | 0.2009 (5) | 0.73980 (15) | 0.1019 (10) | |
O4 | 1.0800 (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'A | 1.2915 | 0.0168 | 0.9610 | 0.042* | |
C6' | 1.5476 (2) | 0.1750 (3) | 1.00375 (13) | 0.0358 (6) | |
H6'A | 1.5817 | 0.3020 | 1.0060 | 0.043* | |
C8' | 1.5482 (2) | −0.1039 (3) | 0.94319 (13) | 0.0352 (6) | |
H8'A | 1.5828 | −0.1789 | 0.9019 | 0.042* | |
C9' | 1.44922 (19) | 0.1721 (3) | 0.83997 (13) | 0.0333 (6) | |
H9'A | 1.5232 | 0.1746 | 0.8150 | 0.040* | |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0314 (11) | 0.0400 (13) | 0.0322 (12) | 0.0018 (10) | 0.0056 (9) | 0.0009 (10) |
C2 | 0.0511 (14) | 0.0349 (13) | 0.0368 (13) | 0.0018 (11) | 0.0071 (11) | 0.0017 (10) |
C6 | 0.0320 (12) | 0.0507 (14) | 0.0384 (13) | 0.0107 (10) | 0.0022 (10) | −0.0037 (11) |
C8 | 0.0352 (12) | 0.0522 (15) | 0.0341 (13) | −0.0044 (11) | 0.0116 (10) | −0.0021 (11) |
C9 | 0.0340 (12) | 0.0421 (13) | 0.0355 (12) | 0.0022 (10) | 0.0054 (10) | −0.0017 (10) |
N1 | 0.0459 (13) | 0.0577 (15) | 0.0610 (15) | −0.0099 (11) | 0.0005 (11) | −0.0067 (12) |
N2 | 0.0495 (13) | 0.0553 (14) | 0.0461 (13) | 0.0019 (11) | 0.0091 (10) | −0.0135 (11) |
O1 | 0.108 (2) | 0.091 (2) | 0.328 (6) | −0.0539 (19) | 0.090 (3) | −0.103 (3) |
O2 | 0.0598 (13) | 0.1038 (19) | 0.0784 (15) | −0.0229 (13) | 0.0338 (12) | −0.0069 (14) |
O3 | 0.135 (2) | 0.121 (2) | 0.0549 (15) | 0.0443 (19) | 0.0323 (14) | −0.0192 (14) |
O4 | 0.0670 (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) |
C1—C9 | 1.487 (3) | C1'—C9' | 1.487 (3) |
C1—C6 | 1.563 (3) | C1'—C8' | 1.560 (3) |
C1—C8 | 1.563 (3) | C1'—C2' | 1.565 (3) |
C1—C2 | 1.565 (3) | C1'—C6' | 1.567 (3) |
C2—C8i | 1.550 (3) | C2'—C6'ii | 1.555 (3) |
C2—C6i | 1.552 (4) | C2'—C8'ii | 1.557 (3) |
C6—C8i | 1.551 (3) | C6'—C2'ii | 1.555 (3) |
C6—C2i | 1.552 (4) | C6'—C8'ii | 1.562 (3) |
C8—C6i | 1.551 (3) | C8'—C2'ii | 1.557 (3) |
C8—C2i | 1.550 (3) | C8'—C6'ii | 1.562 (3) |
C9—N2 | 1.504 (3) | C9'—N1' | 1.499 (3) |
C9—N1 | 1.510 (3) | C9'—N2' | 1.514 (3) |
N1—O1 | 1.174 (4) | N1'—O2' | 1.195 (3) |
N1—O2 | 1.196 (3) | N1'—O1' | 1.201 (3) |
N2—O4 | 1.203 (3) | N2'—O4' | 1.207 (3) |
N2—O3 | 1.210 (3) | N2'—O3' | 1.209 (3) |
C9—C1—C6 | 124.78 (18) | C9'—C1'—C8' | 124.70 (18) |
C9—C1—C8 | 124.19 (18) | C9'—C1'—C2' | 126.64 (18) |
C6—C1—C8 | 89.61 (17) | C8'—C1'—C2' | 90.41 (17) |
C9—C1—C2 | 127.2 (2) | C9'—C1'—C6' | 124.13 (19) |
C6—C1—C2 | 89.95 (17) | C8'—C1'—C6' | 90.00 (16) |
C8—C1—C2 | 89.85 (16) | C2'—C1'—C6' | 90.00 (15) |
C8i—C2—C6i | 90.49 (18) | C6'ii—C2'—C8'ii | 90.57 (16) |
C8i—C2—C1 | 89.55 (17) | C6'ii—C2'—C1' | 89.47 (16) |
C6i—C2—C1 | 89.66 (17) | C8'ii—C2'—C1' | 89.88 (15) |
C8i—C6—C2i | 90.75 (17) | C2'ii—C6'—C8'ii | 90.71 (17) |
C8i—C6—C1 | 89.57 (17) | C2'ii—C6'—C1' | 89.61 (17) |
C2i—C6—C1 | 89.91 (17) | C8'ii—C6'—C1' | 89.61 (16) |
C6i—C8—C2i | 90.92 (17) | C2'ii—C8'—C1' | 89.81 (16) |
C6i—C8—C1 | 89.74 (17) | C2'ii—C8'—C6'ii | 90.50 (15) |
C2i—C8—C1 | 89.98 (17) | C1'—C8'—C6'ii | 89.41 (16) |
C1—C9—N2 | 112.09 (18) | C1'—C9'—N1' | 110.74 (18) |
C1—C9—N1 | 110.68 (19) | C1'—C9'—N2' | 112.00 (19) |
N2—C9—N1 | 105.9 (2) | N1'—C9'—N2' | 106.14 (18) |
O1—N1—O2 | 124.6 (3) | O2'—N1'—O1' | 123.8 (2) |
O1—N1—C9 | 119.0 (3) | O2'—N1'—C9' | 118.4 (2) |
O2—N1—C9 | 116.3 (2) | O1'—N1'—C9' | 117.6 (2) |
O4—N2—O3 | 124.7 (3) | O4'—N2'—O3' | 125.1 (2) |
O4—N2—C9 | 118.3 (2) | O4'—N2'—C9' | 117.0 (2) |
O3—N2—C9 | 116.9 (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 formula | C10H8N4O8 |
Mr | 312.20 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 11.2481 (4), 7.1112 (3), 16.1263 (7) |
β (°) | 99.043 (5) |
V (Å3) | 1273.87 (9) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 1.27 |
Crystal size (mm) | 0.60 × 0.46 × 0.06 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Analytical (XPREP; Siemens, 1994) |
Tmin, Tmax | 0.539, 0.927 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3788, 1790, 1636 |
Rint | 0.054 |
θmax (°) | 58.2 |
(sin θ/λ)max (Å−1) | 0.551 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.139, 1.03 |
No. of reflections | 1790 |
No. of parameters | 200 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.26 |
Computer programs: Bruker XSCANS (Bruker, 1994), Bruker XPREP (Bruker, 1994), SHELXS (Sheldrick, 1990), SHELXTL (Sheldrick, 1997).
C1—C6 | 1.563 (3) | C1'—C8' | 1.560 (3) |
C1—C8 | 1.563 (3) | C1'—C2' | 1.565 (3) |
C1—C2 | 1.565 (3) | C1'—C6' | 1.567 (3) |
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.