Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801017780/om6062sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801017780/om6062Isup2.hkl |
CCDC reference: 176036
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- Disorder in main residue
- R factor = 0.056
- wR factor = 0.147
- Data-to-parameter ratio = 12.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 29.05 From the CIF: _reflns_number_total 2971 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 3195 Completeness (_total/calc) 92.99% Alert C: < 95% complete PLAT_301 Alert C Main Residue Disorder ........................ 8.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
The nitrolysis of 3,7-Di-tert-butyl-1,5-dinitro-3,7-diazabicyclo[3.3.1]nonane (Authors? Reference no? Acta E, submitted) was carried out in 100% nitric acid to afford the title compound in 52% yield.
One of the nitro groups, on N1, is disordered over three sites with occupancies of 0.54, 0.24 and 0.22; the other three nitro groups are well ordered.
Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C7H10N6O8 | F(000) = 632 |
Mr = 306.21 | Dx = 1.704 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.5750 (8) Å | Cell parameters from 5710 reflections |
b = 7.9570 (4) Å | θ = 4.6–56.6° |
c = 11.0684 (6) Å | µ = 0.16 mm−1 |
β = 93.436 (1)° | T = 293 K |
V = 1193.42 (11) Å3 | Prism, colorless |
Z = 4 | 0.66 × 0.66 × 0.23 mm |
CCD area-detector diffractometer | 2971 independent reflections |
Radiation source: normal-focus sealed tube | 2466 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 0.73 pixels mm-1 | θmax = 29.1°, θmin = 3.0° |
phi and ω scans | h = −18→17 |
Absorption correction: multi-scan (Sheldrick, 2001) | k = −4→10 |
Tmin = 0.89, Tmax = 0.96 | l = −14→13 |
8750 measured reflections |
Refinement on F2 | Secondary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: calc |
R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.147 | w = 1/[σ2(Fo2) + (0.067P)2 + 0.5997P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.003 |
2971 reflections | Δρmax = 0.39 e Å−3 |
230 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.035 (4) |
C7H10N6O8 | V = 1193.42 (11) Å3 |
Mr = 306.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.5750 (8) Å | µ = 0.16 mm−1 |
b = 7.9570 (4) Å | T = 293 K |
c = 11.0684 (6) Å | 0.66 × 0.66 × 0.23 mm |
β = 93.436 (1)° |
CCD area-detector diffractometer | 2971 independent reflections |
Absorption correction: multi-scan (Sheldrick, 2001) | 2466 reflections with I > 2σ(I) |
Tmin = 0.89, Tmax = 0.96 | Rint = 0.031 |
8750 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.39 e Å−3 |
2971 reflections | Δρmin = −0.23 e Å−3 |
230 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 | Occ. (<1) | |
C1 | 0.33494 (12) | −0.0635 (2) | 0.83763 (16) | 0.0257 (4) | |
N1 | 0.43303 (12) | −0.1355 (2) | 0.80170 (18) | 0.0421 (5) | |
O1A | 0.4365 (5) | −0.198 (3) | 0.7016 (11) | 0.057 (3) | 0.54 (3) |
O1B | 0.5017 (6) | −0.123 (2) | 0.8737 (9) | 0.044 (2) | 0.54 (3) |
O1A1 | 0.4300 (11) | −0.267 (3) | 0.743 (2) | 0.057 (4) | 0.24 (2) |
O1B1 | 0.5100 (14) | −0.072 (3) | 0.844 (2) | 0.054 (4) | 0.24 (2) |
O1A2 | 0.4478 (17) | −0.125 (4) | 0.6898 (19) | 0.066 (5) | 0.22 (2) |
O1B2 | 0.4910 (17) | −0.189 (4) | 0.8863 (18) | 0.061 (5) | 0.22 (2) |
C2 | 0.35097 (13) | 0.1261 (2) | 0.8510 (2) | 0.0317 (4) | |
H2A | 0.4011 | 0.1493 | 0.9149 | 0.038* | |
H2B | 0.3722 | 0.1734 | 0.7761 | 0.038* | |
N3 | 0.25659 (11) | 0.19864 (17) | 0.88066 (15) | 0.0292 (4) | |
N3A | 0.26203 (14) | 0.3584 (2) | 0.92798 (19) | 0.0422 (5) | |
O3A | 0.34280 (14) | 0.4095 (2) | 0.9653 (2) | 0.0679 (6) | |
O3B | 0.18524 (14) | 0.4362 (2) | 0.9338 (2) | 0.0640 (6) | |
C4 | 0.16666 (14) | 0.1608 (2) | 0.80566 (19) | 0.0308 (4) | |
H4A | 0.1681 | 0.2186 | 0.7286 | 0.037* | |
H4B | 0.1092 | 0.1992 | 0.8459 | 0.037* | |
C5 | 0.16023 (12) | −0.0292 (2) | 0.78487 (16) | 0.0245 (4) | |
N5 | 0.07644 (12) | −0.0604 (2) | 0.68953 (15) | 0.0350 (4) | |
O5A | 0.01917 (15) | 0.0519 (3) | 0.6662 (2) | 0.0820 (8) | |
O5B | 0.07125 (12) | −0.1982 (2) | 0.64403 (16) | 0.0525 (5) | |
C6 | 0.13347 (14) | −0.1297 (2) | 0.89680 (17) | 0.0286 (4) | |
H6A | 0.0725 | −0.0872 | 0.9265 | 0.034* | |
H6B | 0.1240 | −0.2471 | 0.8756 | 0.034* | |
N7 | 0.21284 (12) | −0.11332 (19) | 0.99003 (14) | 0.0293 (4) | |
N7A | 0.20085 (13) | 0.0021 (2) | 1.08030 (15) | 0.0342 (4) | |
O7A | 0.27214 (13) | 0.0302 (2) | 1.15008 (15) | 0.0523 (5) | |
O7B | 0.11930 (12) | 0.0642 (2) | 1.08749 (16) | 0.0487 (4) | |
C8 | 0.31272 (14) | −0.1515 (2) | 0.95676 (18) | 0.0311 (4) | |
H8A | 0.3199 | −0.2721 | 0.9475 | 0.037* | |
H8B | 0.3597 | −0.1147 | 1.0207 | 0.037* | |
C9 | 0.25533 (13) | −0.0999 (2) | 0.73855 (17) | 0.0283 (4) | |
H9A | 0.2493 | −0.2198 | 0.7244 | 0.034* | |
H9B | 0.2707 | −0.0454 | 0.6635 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0207 (8) | 0.0248 (8) | 0.0317 (9) | 0.0025 (6) | 0.0013 (7) | −0.0052 (7) |
N1 | 0.0259 (8) | 0.0501 (11) | 0.0499 (11) | 0.0082 (8) | 0.0007 (8) | −0.0149 (9) |
O1A | 0.037 (3) | 0.079 (7) | 0.055 (5) | 0.015 (4) | 0.007 (3) | −0.031 (5) |
O1B | 0.024 (3) | 0.055 (6) | 0.051 (4) | 0.007 (4) | −0.005 (2) | 0.001 (4) |
O1A1 | 0.045 (4) | 0.050 (7) | 0.075 (8) | 0.009 (4) | 0.010 (5) | −0.028 (6) |
O1B1 | 0.030 (4) | 0.053 (8) | 0.078 (9) | 0.000 (5) | 0.001 (6) | −0.013 (6) |
O1A2 | 0.058 (7) | 0.080 (10) | 0.064 (6) | 0.020 (7) | 0.026 (5) | 0.004 (7) |
O1B2 | 0.043 (6) | 0.068 (9) | 0.074 (7) | 0.028 (7) | 0.005 (5) | 0.021 (7) |
C2 | 0.0244 (9) | 0.0254 (9) | 0.0454 (11) | −0.0036 (7) | 0.0022 (8) | −0.0003 (8) |
N3 | 0.0297 (8) | 0.0160 (7) | 0.0418 (9) | −0.0013 (6) | 0.0004 (7) | −0.0014 (6) |
N3A | 0.0492 (11) | 0.0204 (8) | 0.0563 (12) | −0.0017 (7) | −0.0013 (9) | −0.0063 (7) |
O3A | 0.0560 (11) | 0.0368 (9) | 0.1086 (17) | −0.0091 (8) | −0.0136 (11) | −0.0282 (10) |
O3B | 0.0574 (11) | 0.0333 (8) | 0.1005 (16) | 0.0143 (8) | −0.0010 (10) | −0.0207 (9) |
C4 | 0.0293 (9) | 0.0224 (8) | 0.0399 (10) | 0.0021 (7) | −0.0042 (8) | 0.0039 (7) |
C5 | 0.0228 (8) | 0.0242 (8) | 0.0261 (8) | −0.0003 (6) | −0.0010 (6) | −0.0027 (6) |
N5 | 0.0272 (8) | 0.0439 (10) | 0.0334 (9) | 0.0003 (7) | −0.0030 (7) | −0.0062 (7) |
O5A | 0.0585 (12) | 0.0721 (14) | 0.1088 (18) | 0.0288 (10) | −0.0498 (12) | −0.0272 (12) |
O5B | 0.0435 (9) | 0.0549 (10) | 0.0573 (10) | −0.0030 (8) | −0.0114 (7) | −0.0250 (8) |
C6 | 0.0292 (9) | 0.0243 (8) | 0.0327 (9) | −0.0078 (7) | 0.0043 (7) | −0.0016 (7) |
N7 | 0.0354 (8) | 0.0250 (7) | 0.0276 (8) | −0.0018 (6) | 0.0036 (6) | 0.0010 (6) |
N7A | 0.0437 (10) | 0.0291 (8) | 0.0300 (8) | −0.0013 (7) | 0.0027 (7) | −0.0022 (7) |
O7A | 0.0536 (10) | 0.0583 (10) | 0.0433 (9) | 0.0052 (8) | −0.0110 (7) | −0.0166 (8) |
O7B | 0.0435 (9) | 0.0521 (10) | 0.0511 (10) | 0.0068 (7) | 0.0062 (7) | −0.0174 (7) |
C8 | 0.0336 (10) | 0.0238 (8) | 0.0354 (10) | 0.0072 (7) | −0.0021 (8) | 0.0018 (7) |
C9 | 0.0260 (9) | 0.0317 (9) | 0.0273 (9) | 0.0014 (7) | 0.0018 (7) | −0.0066 (7) |
C1—C9 | 1.521 (2) | N3A—O3B | 1.217 (2) |
C1—N1 | 1.524 (2) | N3A—O3A | 1.218 (3) |
C1—C2 | 1.530 (2) | C4—C5 | 1.531 (2) |
C1—C8 | 1.539 (3) | C5—C9 | 1.525 (2) |
N1—O1B | 1.194 (7) | C5—N5 | 1.525 (2) |
N1—O1A | 1.217 (7) | C5—C6 | 1.536 (2) |
N1—O1B1 | 1.226 (19) | N5—O5A | 1.203 (2) |
N1—O1A1 | 1.236 (12) | N5—O5B | 1.207 (2) |
N1—O1B2 | 1.262 (18) | C6—N7 | 1.452 (2) |
N1—O1A2 | 1.27 (2) | N7—N7A | 1.374 (2) |
C2—N3 | 1.460 (2) | N7—C8 | 1.458 (2) |
N3—N3A | 1.375 (2) | N7A—O7B | 1.219 (2) |
N3—C4 | 1.466 (2) | N7A—O7A | 1.222 (2) |
C9—C1—N1 | 109.55 (14) | O3A—N3A—N3 | 117.67 (18) |
C9—C1—C2 | 110.37 (15) | N3—C4—C5 | 109.04 (14) |
N1—C1—C2 | 105.94 (15) | C9—C5—N5 | 108.58 (14) |
C9—C1—C8 | 111.35 (15) | C9—C5—C4 | 111.89 (15) |
N1—C1—C8 | 105.76 (15) | N5—C5—C4 | 107.37 (14) |
C2—C1—C8 | 113.58 (16) | C9—C5—C6 | 108.98 (15) |
O1B—N1—O1A | 124.7 (5) | N5—C5—C6 | 105.70 (14) |
O1B1—N1—O1A1 | 123.4 (11) | C4—C5—C6 | 114.00 (15) |
O1B2—N1—O1A2 | 128.2 (13) | O5A—N5—O5B | 124.40 (18) |
O1B—N1—C1 | 117.0 (4) | O5A—N5—C5 | 118.24 (17) |
O1A—N1—C1 | 118.2 (3) | O5B—N5—C5 | 117.35 (16) |
O1B1—N1—C1 | 119.0 (9) | N7—C6—C5 | 108.98 (14) |
O1A1—N1—C1 | 117.1 (7) | N7A—N7—C6 | 117.47 (15) |
O1B2—N1—C1 | 116.7 (9) | N7A—N7—C8 | 118.39 (15) |
O1A2—N1—C1 | 114.9 (9) | C6—N7—C8 | 117.60 (15) |
N3—C2—C1 | 106.85 (14) | O7B—N7A—O7A | 124.92 (17) |
N3A—N3—C2 | 115.03 (15) | O7B—N7A—N7 | 117.77 (16) |
N3A—N3—C4 | 115.44 (15) | O7A—N7A—N7 | 117.26 (17) |
C2—N3—C4 | 120.23 (16) | N7—C8—C1 | 110.76 (14) |
O3B—N3A—O3A | 124.65 (18) | C1—C9—C5 | 105.48 (14) |
O3B—N3A—N3 | 117.62 (18) |
Experimental details
Crystal data | |
Chemical formula | C7H10N6O8 |
Mr | 306.21 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.5750 (8), 7.9570 (4), 11.0684 (6) |
β (°) | 93.436 (1) |
V (Å3) | 1193.42 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.16 |
Crystal size (mm) | 0.66 × 0.66 × 0.23 |
Data collection | |
Diffractometer | CCD area-detector diffractometer |
Absorption correction | Multi-scan (Sheldrick, 2001) |
Tmin, Tmax | 0.89, 0.96 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8750, 2971, 2466 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.683 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.147, 1.10 |
No. of reflections | 2971 |
No. of parameters | 230 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.23 |
Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001), SHELXTL (Sheldrick, 1997), SHELXTL.
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A key thrust of much current research in energetic materials is the development of higher performance materials to defeat increasingly hardened targets. Important goals are new crystalline explosive fillers with energy density exceeding HMX (1,3,5,7-tetranitro-1,3,5,7- tetrazacyclooctane), as well as new nitramines capable of replacing ammonium perchlorate as the mainstay of many present missile propellants. The title compound, (I), is a variant similar to HMX in that it contains four nitro groups, but only two are nitramines (four in HMX) and the other two are C-nitro groupings that are considered less sensitive than nitramines. However the density is 10% less than HMX (Cady et al., 1963), which lowers its efficacy as an energetic material. Although there could be a vertical twofold axis passing through C9, and this is roughly so for the ring system (two chair-shaped azacyclohexane rings), there is no crystallographic symmetry, and corresponding nitro groups, especially those on N3 and N7, deviate from each other in their orientation (Fig. 2).