Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013915/om6043sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013915/om6043Isup2.hkl |
CCDC reference: 172224
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.033
- wR factor = 0.092
- Data-to-parameter ratio = 10.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 32.48 From the CIF: _reflns_number_total 1568 Count of symmetry unique reflns 1568 Completeness (_total/calc) 100.00% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
Crystals of the title compound were supplied by Dr Michael Chaykovsky, Naval Surface Warfare Center - White Oak, Silver Spring, MD.
Crystal and reflection data were obtained using standard procedures (Butcher et al., 1995).
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C4H4N4O7 | Dx = 1.953 Mg m−3 |
Mr = 220.11 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 69 reflections |
a = 6.7249 (5) Å | θ = 7.9–43.5° |
b = 9.979 (2) Å | µ = 0.19 mm−1 |
c = 11.1574 (10) Å | T = 293 K |
V = 748.74 (19) Å3 | Octahedron, colorless |
Z = 4 | 0.36 × 0.28 × 0.24 mm |
F(000) = 448 |
Bruker P4 diffractometer | 1371 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 32.5°, θmin = 2.7° |
2θ/ω scans | h = 0→10 |
Absorption correction: integration (Wuensch & Prewitt, 1965) | k = 0→15 |
Tmin = 0.627, Tmax = 0.689 | l = 0→16 |
1568 measured reflections | 3 standard reflections every 97 reflections |
1568 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.033 | All H-atom parameters refined |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0565P)2 + 0.024P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.002 |
1568 reflections | Δρmax = 0.30 e Å−3 |
153 parameters | Δρmin = −0.21 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: 0.024 (6) |
C4H4N4O7 | V = 748.74 (19) Å3 |
Mr = 220.11 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.7249 (5) Å | µ = 0.19 mm−1 |
b = 9.979 (2) Å | T = 293 K |
c = 11.1574 (10) Å | 0.36 × 0.28 × 0.24 mm |
Bruker P4 diffractometer | 1371 reflections with I > 2σ(I) |
Absorption correction: integration (Wuensch & Prewitt, 1965) | Rint = 0.000 |
Tmin = 0.627, Tmax = 0.689 | 3 standard reflections every 97 reflections |
1568 measured reflections | intensity decay: none |
1568 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.092 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.30 e Å−3 |
1568 reflections | Δρmin = −0.21 e Å−3 |
153 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 | ||
O2 | 0.2215 (2) | 0.12580 (14) | 0.51995 (12) | 0.0343 (3) | |
O3 | −0.0907 (2) | 0.06886 (16) | 0.47342 (15) | 0.0437 (4) | |
O4 | 0.16679 (18) | −0.01969 (13) | 0.37260 (11) | 0.0299 (3) | |
O61 | 0.5899 (3) | 0.18155 (14) | 0.68059 (14) | 0.0442 (4) | |
O62 | 0.7293 (2) | −0.01084 (19) | 0.71922 (13) | 0.0443 (4) | |
O81 | 0.4497 (3) | −0.22123 (14) | 0.24039 (12) | 0.0399 (3) | |
O82 | 0.6257 (3) | −0.32115 (13) | 0.37769 (14) | 0.0394 (3) | |
N6 | 0.5056 (2) | 0.00221 (14) | 0.57590 (12) | 0.0270 (3) | |
N61 | 0.6181 (2) | 0.06247 (16) | 0.66343 (13) | 0.0317 (3) | |
N8 | 0.4611 (2) | −0.13675 (13) | 0.42254 (12) | 0.0268 (3) | |
N81 | 0.5176 (2) | −0.23172 (13) | 0.34053 (13) | 0.0280 (3) | |
C1A | 0.4159 (3) | 0.08496 (15) | 0.48455 (14) | 0.0245 (3) | |
H1A | 0.485 (3) | 0.163 (2) | 0.4662 (18) | 0.019 (5)* | |
C1B | 0.3792 (2) | −0.01207 (15) | 0.38072 (13) | 0.0227 (3) | |
H1B | 0.422 (4) | 0.011 (2) | 0.3045 (16) | 0.023 (5)* | |
C3 | 0.0826 (3) | 0.05866 (17) | 0.45753 (14) | 0.0282 (3) | |
C7 | 0.5678 (3) | −0.13027 (17) | 0.53632 (15) | 0.0281 (3) | |
H72 | 0.522 (4) | −0.198 (3) | 0.585 (2) | 0.041 (7)* | |
H71 | 0.708 (4) | −0.134 (2) | 0.520 (2) | 0.034 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0323 (6) | 0.0374 (6) | 0.0331 (6) | 0.0111 (5) | −0.0041 (5) | −0.0100 (5) |
O3 | 0.0268 (6) | 0.0571 (9) | 0.0472 (8) | 0.0081 (6) | 0.0066 (6) | 0.0045 (7) |
O4 | 0.0233 (5) | 0.0340 (6) | 0.0323 (6) | 0.0025 (5) | −0.0036 (5) | −0.0071 (5) |
O61 | 0.0534 (9) | 0.0407 (7) | 0.0386 (7) | −0.0087 (7) | −0.0045 (7) | −0.0108 (6) |
O62 | 0.0370 (7) | 0.0620 (9) | 0.0339 (6) | −0.0021 (7) | −0.0129 (6) | 0.0056 (6) |
O81 | 0.0546 (9) | 0.0371 (6) | 0.0281 (6) | 0.0054 (7) | −0.0035 (6) | −0.0057 (5) |
O82 | 0.0452 (8) | 0.0290 (6) | 0.0440 (7) | 0.0112 (6) | 0.0008 (7) | 0.0016 (5) |
N6 | 0.0268 (6) | 0.0286 (6) | 0.0257 (6) | 0.0013 (5) | −0.0057 (5) | −0.0005 (5) |
N61 | 0.0278 (7) | 0.0420 (8) | 0.0252 (6) | −0.0069 (6) | −0.0027 (6) | −0.0018 (6) |
N8 | 0.0318 (7) | 0.0255 (5) | 0.0231 (5) | 0.0060 (5) | −0.0022 (5) | −0.0007 (5) |
N81 | 0.0307 (7) | 0.0239 (6) | 0.0295 (6) | −0.0010 (5) | 0.0040 (6) | −0.0005 (5) |
C1A | 0.0255 (7) | 0.0225 (6) | 0.0255 (6) | −0.0007 (5) | −0.0015 (6) | −0.0003 (5) |
C1B | 0.0216 (6) | 0.0251 (6) | 0.0213 (5) | 0.0015 (5) | 0.0012 (5) | 0.0016 (5) |
C3 | 0.0258 (7) | 0.0311 (7) | 0.0277 (7) | 0.0038 (6) | 0.0024 (6) | 0.0026 (6) |
C7 | 0.0300 (7) | 0.0275 (6) | 0.0268 (7) | 0.0029 (6) | −0.0047 (6) | 0.0017 (6) |
O2—C3 | 1.344 (2) | N6—C1A | 1.444 (2) |
O2—C1A | 1.425 (2) | N6—C7 | 1.455 (2) |
O3—C3 | 1.183 (2) | N8—N81 | 1.3709 (19) |
O4—C3 | 1.3526 (19) | N8—C1B | 1.4385 (19) |
O4—C1B | 1.4333 (19) | N8—C7 | 1.460 (2) |
O61—N61 | 1.219 (2) | C1A—C1B | 1.530 (2) |
O62—N61 | 1.217 (2) | C1A—H1A | 0.93 (2) |
O81—N81 | 1.211 (2) | C1B—H1B | 0.926 (19) |
O82—N81 | 1.2237 (19) | C7—H72 | 0.91 (3) |
N6—N61 | 1.3741 (19) | C7—H71 | 0.96 (2) |
C3—O2—C1A | 110.56 (12) | O4—C1B—C1A | 104.02 (12) |
C3—O4—C1B | 110.00 (13) | N8—C1B—C1A | 103.88 (12) |
N61—N6—C1A | 118.79 (13) | O3—C3—O2 | 124.32 (18) |
N61—N6—C7 | 117.05 (14) | O3—C3—O4 | 124.53 (18) |
C1A—N6—C7 | 115.18 (12) | O2—C3—O4 | 111.13 (14) |
O62—N61—O61 | 126.97 (17) | N6—C7—N8 | 99.37 (12) |
O62—N61—N6 | 116.03 (15) | O2—C1A—H1A | 106.4 (12) |
O61—N61—N6 | 116.91 (16) | N6—C1A—H1A | 115.1 (13) |
N81—N8—C1B | 119.17 (12) | C1B—C1A—H1A | 116.3 (13) |
N81—N8—C7 | 118.35 (14) | O4—C1B—H1B | 105.3 (15) |
C1B—N8—C7 | 115.60 (13) | N8—C1B—H1B | 113.0 (13) |
O81—N81—O82 | 126.82 (15) | C1A—C1B—H1B | 119.3 (13) |
O81—N81—N8 | 116.85 (14) | N6—C7—H72 | 113.0 (17) |
O82—N81—N8 | 116.27 (14) | N8—C7—H72 | 108.3 (17) |
O2—C1A—N6 | 110.56 (13) | N6—C7—H71 | 111.8 (14) |
O2—C1A—C1B | 104.06 (12) | N8—C7—H71 | 108.5 (15) |
N6—C1A—C1B | 103.89 (12) | H72—C7—H71 | 115 (2) |
O4—C1B—N8 | 110.87 (13) | ||
C1A—N6—N61—O62 | −162.26 (15) | N81—N8—C1B—O4 | 91.65 (17) |
C7—N6—N61—O62 | −16.6 (2) | C7—N8—C1B—O4 | −117.82 (15) |
C1A—N6—N61—O61 | 20.9 (2) | N81—N8—C1B—C1A | −157.18 (14) |
C7—N6—N61—O61 | 166.60 (17) | C7—N8—C1B—C1A | −6.65 (18) |
C1B—N8—N81—O81 | −18.6 (2) | O2—C1A—C1B—O4 | −2.48 (15) |
C7—N8—N81—O81 | −168.35 (16) | N6—C1A—C1B—O4 | 113.30 (14) |
C1B—N8—N81—O82 | 163.99 (15) | O2—C1A—C1B—N8 | −118.58 (13) |
C7—N8—N81—O82 | 14.3 (2) | N6—C1A—C1B—N8 | −2.80 (16) |
C3—O2—C1A—N6 | −106.42 (15) | C1A—O2—C3—O3 | 176.24 (18) |
C3—O2—C1A—C1B | 4.58 (17) | C1A—O2—C3—O4 | −5.10 (18) |
N61—N6—C1A—O2 | −90.98 (17) | C1B—O4—C3—O3 | −178.03 (18) |
C7—N6—C1A—O2 | 122.74 (15) | C1B—O4—C3—O2 | 3.32 (18) |
N61—N6—C1A—C1B | 157.92 (14) | N61—N6—C7—N8 | −161.69 (14) |
C7—N6—C1A—C1B | 11.64 (18) | C1A—N6—C7—N8 | −14.80 (18) |
C3—O4—C1B—N8 | 110.75 (14) | N81—N8—C7—N6 | 163.57 (14) |
C3—O4—C1B—C1A | −0.34 (17) | C1B—N8—C7—N6 | 12.79 (18) |
Experimental details
Crystal data | |
Chemical formula | C4H4N4O7 |
Mr | 220.11 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 6.7249 (5), 9.979 (2), 11.1574 (10) |
V (Å3) | 748.74 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.36 × 0.28 × 0.24 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | Integration (Wuensch & Prewitt, 1965) |
Tmin, Tmax | 0.627, 0.689 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1568, 1568, 1371 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.756 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.092, 1.07 |
No. of reflections | 1568 |
No. of parameters | 153 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.30, −0.21 |
Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXTL (Sheldrick, 1997a), SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997b), SHELXTL.
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The title compound, 6,8-diaza-6,8-dinitro-2,4-dioxabicyclo[3.3.0]octan-3-one, C4H4N4O7 (I), contains only C, H, N, and O, and has a remarkably high density of 1.953 g cm-3. This value is one of the top 12 in the CHNO realm [based on the results of a search of version 5.2 (April 2001) of the Cambridge Structural Database (Allen et al., 1991) using CONQUEST (CCDC, 2001)]. The synthesis of new energetic CHNO compounds that have high densities is a prime goal in the field of energetic compounds. Such high densities are usually only observed in strained polycyclic ring compounds such as the nitrocubanes (Zhang et al., 2000; Lukin et al., 1997; Lukin et al., 1996) and hexanitrohexaazaisowurtzitane (Nielsen et al., 1998) or in a few planar molecules linked by inter- and intramolecular hydrogen bonding (Gilardi & Butcher, 2001) that can stack in parallel layers. In the present instance, the central core of the molecule contains no double bonds and consists of a cyclic carbonate ring fused to an imidazolidine ring. The molecule is not planar but is folded about the C1A—C1B ring juction (the angle between the carbonate and imidazolidine rings is 61.3°). It is thus related to another dense energetic cyclic carbonate, 4,5-bis(fluorodinitromethyl)-1,3-dioxolan-2-one (Ammon & Bhattacharjee, 1984). Metrical parameters for the cyclic carbonate ring are within the normal range observed for such compounds (Allen et al., 1991). However, the metrical parameters of the imidazolidine ring are affected by the nitration of nitrogen atoms. This nitration results in a lengthening of the two C—N distances [C1A—N6 1.443 (2) and C1B—N8 1.440 (2) versus 1.466 Å], an increase in the C—N—C angles (115.4 versus 108.7°) and a corresponding decrease in the N—C—N angle (99.4 versus 103.6°).