Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010352/cf6082sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010352/cf6082Isup2.hkl |
CCDC reference: 170788
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.002 Å
- R factor = 0.040
- wR factor = 0.097
- Data-to-parameter ratio = 11.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Crystals of the title compound were supplied by Dr Philip Pagoria, Energetic Materials Laboratory, Lawrence Livermore National Laboratory, Livermore, CA 94550, USA. Crystal and reflection data were obtained using standard procedures (Butcher et al., 1995).
Data collection: XSCANS (Bruker, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C4H4N6O5 | F(000) = 440 |
Mr = 216.13 | Dx = 1.919 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.7159 (8) Å | Cell parameters from 58 reflections |
b = 15.8498 (14) Å | θ = 2.8–18.3° |
c = 8.4139 (7) Å | µ = 0.18 mm−1 |
β = 101.041 (7)° | T = 294 K |
V = 748.16 (14) Å3 | Chunky prism, yellow |
Z = 4 | 0.4 × 0.3 × 0.25 mm |
Bruker P4 diffractometer | 1185 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 27.5°, θmin = 2.6° |
2θ/ω scans | h = 0→7 |
Absorption correction: integration (Wuensch & Prewitt, 1965) | k = −20→18 |
Tmin = 0.990, Tmax = 0.993 | l = −10→10 |
3771 measured reflections | 3 standard reflections every 97 reflections |
1716 independent reflections | intensity decay: 1.0% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.041P)2 + 0.0834P] where P = (Fo2 + 2Fc2)/3 |
1716 reflections | (Δ/σ)max < 0.001 |
152 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C4H4N6O5 | V = 748.16 (14) Å3 |
Mr = 216.13 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.7159 (8) Å | µ = 0.18 mm−1 |
b = 15.8498 (14) Å | T = 294 K |
c = 8.4139 (7) Å | 0.4 × 0.3 × 0.25 mm |
β = 101.041 (7)° |
Bruker P4 diffractometer | 1185 reflections with I > 2σ(I) |
Absorption correction: integration (Wuensch & Prewitt, 1965) | Rint = 0.015 |
Tmin = 0.990, Tmax = 0.993 | 3 standard reflections every 97 reflections |
3771 measured reflections | intensity decay: 1.0% |
1716 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.23 e Å−3 |
1716 reflections | Δρmin = −0.21 e Å−3 |
152 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 | ||
N1 | −0.1565 (3) | 0.90540 (9) | 0.47096 (18) | 0.0240 (4) | |
O1 | −0.3630 (2) | 0.93827 (9) | 0.40265 (17) | 0.0348 (4) | |
C2 | −0.0702 (3) | 0.92079 (11) | 0.6322 (2) | 0.0228 (4) | |
N2 | −0.2081 (3) | 0.96805 (11) | 0.7048 (2) | 0.0305 (4) | |
H2A | −0.344 (4) | 0.9849 (15) | 0.639 (3) | 0.050 (7)* | |
H2B | −0.159 (4) | 0.9802 (16) | 0.814 (3) | 0.060 (8)* | |
C3 | 0.1558 (3) | 0.88493 (11) | 0.6943 (2) | 0.0233 (4) | |
N3 | 0.2748 (3) | 0.89943 (10) | 0.86104 (19) | 0.0280 (4) | |
O3A | 0.1754 (3) | 0.94651 (10) | 0.94385 (17) | 0.0434 (4) | |
O3B | 0.4660 (3) | 0.86564 (10) | 0.91133 (17) | 0.0409 (4) | |
N4 | 0.2750 (3) | 0.83913 (9) | 0.60789 (18) | 0.0236 (4) | |
C5 | 0.1862 (3) | 0.82688 (11) | 0.4549 (2) | 0.0226 (4) | |
N5 | 0.3341 (3) | 0.77874 (10) | 0.36491 (18) | 0.0275 (4) | |
O5A | 0.2944 (3) | 0.78509 (11) | 0.21769 (16) | 0.0444 (4) | |
O5B | 0.4921 (3) | 0.73514 (10) | 0.43965 (17) | 0.0450 (4) | |
C6 | −0.0360 (3) | 0.85960 (11) | 0.3750 (2) | 0.0225 (4) | |
N6 | −0.1406 (3) | 0.85208 (11) | 0.2225 (2) | 0.0305 (4) | |
H6A | −0.069 (4) | 0.8211 (15) | 0.153 (3) | 0.044 (7)* | |
H6B | −0.286 (4) | 0.8754 (15) | 0.191 (3) | 0.046 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0202 (8) | 0.0256 (8) | 0.0256 (8) | 0.0026 (7) | 0.0024 (7) | 0.0005 (6) |
O1 | 0.0251 (7) | 0.0416 (9) | 0.0351 (8) | 0.0122 (6) | −0.0010 (6) | −0.0029 (6) |
C2 | 0.0257 (9) | 0.0213 (9) | 0.0219 (9) | −0.0041 (8) | 0.0059 (8) | 0.0000 (7) |
N2 | 0.0286 (9) | 0.0364 (10) | 0.0269 (9) | 0.0051 (8) | 0.0064 (8) | −0.0052 (7) |
C3 | 0.0251 (9) | 0.0247 (10) | 0.0201 (9) | −0.0012 (8) | 0.0045 (8) | 0.0008 (7) |
N3 | 0.0299 (9) | 0.0316 (9) | 0.0227 (8) | −0.0030 (7) | 0.0053 (7) | −0.0002 (7) |
O3A | 0.0543 (10) | 0.0470 (10) | 0.0282 (8) | 0.0096 (8) | 0.0059 (7) | −0.0114 (7) |
O3B | 0.0291 (8) | 0.0611 (11) | 0.0293 (8) | 0.0084 (8) | −0.0023 (6) | −0.0012 (7) |
N4 | 0.0241 (8) | 0.0240 (8) | 0.0226 (8) | 0.0009 (7) | 0.0045 (6) | 0.0022 (6) |
C5 | 0.0229 (9) | 0.0232 (9) | 0.0219 (9) | 0.0019 (8) | 0.0050 (7) | −0.0011 (7) |
N5 | 0.0244 (8) | 0.0335 (9) | 0.0247 (8) | 0.0037 (7) | 0.0051 (7) | −0.0001 (7) |
O5A | 0.0388 (9) | 0.0725 (12) | 0.0208 (7) | 0.0162 (8) | 0.0034 (6) | −0.0040 (7) |
O5B | 0.0467 (9) | 0.0582 (10) | 0.0314 (8) | 0.0310 (8) | 0.0104 (7) | 0.0081 (7) |
C6 | 0.0233 (9) | 0.0218 (9) | 0.0228 (9) | −0.0009 (8) | 0.0048 (7) | −0.0005 (7) |
N6 | 0.0267 (9) | 0.0379 (10) | 0.0249 (9) | 0.0055 (8) | 0.0000 (7) | −0.0047 (7) |
N1—O1 | 1.3172 (19) | N3—O3A | 1.231 (2) |
N1—C6 | 1.366 (2) | N4—C5 | 1.305 (2) |
N1—C2 | 1.374 (2) | C5—C6 | 1.417 (3) |
C2—N2 | 1.319 (2) | C5—N5 | 1.454 (2) |
C2—C3 | 1.417 (3) | N5—O5B | 1.213 (2) |
N2—H2A | 0.90 (2) | N5—O5A | 1.2199 (19) |
N2—H2B | 0.93 (3) | C6—N6 | 1.313 (2) |
C3—N4 | 1.307 (2) | N6—H6A | 0.91 (2) |
C3—N3 | 1.455 (2) | N6—H6B | 0.90 (2) |
N3—O3B | 1.218 (2) | ||
O1—N1—C6 | 117.61 (15) | O3A—N3—C3 | 117.41 (16) |
O1—N1—C2 | 118.88 (15) | C5—N4—C3 | 119.05 (16) |
C6—N1—C2 | 123.48 (15) | N4—C5—C6 | 123.90 (17) |
N2—C2—N1 | 115.16 (17) | N4—C5—N5 | 115.89 (15) |
N2—C2—C3 | 129.84 (17) | C6—C5—N5 | 120.18 (15) |
N1—C2—C3 | 114.99 (16) | O5B—N5—O5A | 123.27 (17) |
C2—N2—H2A | 113.7 (15) | O5B—N5—C5 | 118.57 (15) |
C2—N2—H2B | 118.8 (16) | O5A—N5—C5 | 118.15 (15) |
H2A—N2—H2B | 128 (2) | N6—C6—N1 | 116.05 (17) |
N4—C3—C2 | 123.59 (17) | N6—C6—C5 | 129.00 (18) |
N4—C3—N3 | 115.28 (16) | N1—C6—C5 | 114.96 (16) |
C2—C3—N3 | 121.11 (16) | C6—N6—H6A | 119.7 (14) |
O3B—N3—O3A | 123.39 (17) | C6—N6—H6B | 118.1 (15) |
O3B—N3—C3 | 119.20 (16) | H6A—N6—H6B | 122 (2) |
O1—N1—C2—N2 | 0.4 (2) | C3—N4—C5—C6 | −0.8 (3) |
C6—N1—C2—N2 | 178.30 (17) | C3—N4—C5—N5 | 177.14 (16) |
O1—N1—C2—C3 | −178.31 (15) | N4—C5—N5—O5B | 19.2 (3) |
C6—N1—C2—C3 | −0.4 (2) | C6—C5—N5—O5B | −162.75 (18) |
N2—C2—C3—N4 | −179.66 (19) | N4—C5—N5—O5A | −159.94 (17) |
N1—C2—C3—N4 | −1.2 (3) | C6—C5—N5—O5A | 18.1 (3) |
N2—C2—C3—N3 | −1.5 (3) | O1—N1—C6—N6 | −0.7 (2) |
N1—C2—C3—N3 | 176.96 (15) | C2—N1—C6—N6 | −178.62 (17) |
N4—C3—N3—O3B | −3.7 (3) | O1—N1—C6—C5 | 179.17 (15) |
C2—C3—N3—O3B | 177.99 (17) | C2—N1—C6—C5 | 1.2 (2) |
N4—C3—N3—O3A | 175.65 (17) | N4—C5—C6—N6 | 179.17 (18) |
C2—C3—N3—O3A | −2.6 (3) | N5—C5—C6—N6 | 1.3 (3) |
C2—C3—N4—C5 | 1.8 (3) | N4—C5—C6—N1 | −0.7 (3) |
N3—C3—N4—C5 | −176.47 (16) | N5—C5—C6—N1 | −178.52 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.90 (2) | 2.05 (2) | 2.861 (2) | 149 (2) |
N2—H2A···O1 | 0.90 (2) | 2.10 (2) | 2.571 (2) | 111.2 (18) |
N2—H2B···O3A | 0.93 (3) | 2.08 (3) | 2.697 (2) | 123 (2) |
N2—H2B···O3Aii | 0.93 (3) | 2.36 (3) | 3.224 (2) | 154 (2) |
N6—H6A···O5Biii | 0.91 (2) | 2.10 (2) | 2.974 (2) | 160 (2) |
N6—H6A···O5A | 0.91 (2) | 2.12 (2) | 2.711 (2) | 121.1 (18) |
N6—H6A···N4iii | 0.91 (2) | 2.69 (2) | 3.189 (2) | 114.9 (18) |
N6—H6B···O3Biv | 0.90 (2) | 2.51 (2) | 3.115 (2) | 125.0 (19) |
Symmetry codes: (i) −x−1, −y+2, −z+1; (ii) −x, −y+2, −z+2; (iii) x−1/2, −y+3/2, z−1/2; (iv) x−1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C4H4N6O5 |
Mr | 216.13 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 5.7159 (8), 15.8498 (14), 8.4139 (7) |
β (°) | 101.041 (7) |
V (Å3) | 748.16 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.4 × 0.3 × 0.25 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | Integration (Wuensch & Prewitt, 1965) |
Tmin, Tmax | 0.990, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3771, 1716, 1185 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.097, 1.01 |
No. of reflections | 1716 |
No. of parameters | 152 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.21 |
Computer programs: XSCANS (Bruker, 1994), XSCANS, SHELXTL (Sheldrick, 1997), SHELXS97 (Sheldrick, 1990), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.90 (2) | 2.05 (2) | 2.861 (2) | 149 (2) |
N2—H2A···O1 | 0.90 (2) | 2.10 (2) | 2.571 (2) | 111.2 (18) |
N2—H2B···O3A | 0.93 (3) | 2.08 (3) | 2.697 (2) | 123 (2) |
N2—H2B···O3Aii | 0.93 (3) | 2.36 (3) | 3.224 (2) | 154 (2) |
N6—H6A···O5Biii | 0.91 (2) | 2.10 (2) | 2.974 (2) | 160 (2) |
N6—H6A···O5A | 0.91 (2) | 2.12 (2) | 2.711 (2) | 121.1 (18) |
N6—H6A···N4iii | 0.91 (2) | 2.69 (2) | 3.189 (2) | 114.9 (18) |
N6—H6B···O3Biv | 0.90 (2) | 2.51 (2) | 3.115 (2) | 125.0 (19) |
Symmetry codes: (i) −x−1, −y+2, −z+1; (ii) −x, −y+2, −z+2; (iii) x−1/2, −y+3/2, z−1/2; (iv) x−1, y, z−1. |
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The title compound, 2,6-diamino-3,5-dinitro-1,4-pyrazine 1-oxide (ANPZO), (I), is a very stable and relatively insensitive energetic material with a very high density of 1.919 Mg m-3. Every H atom is involved in intramolecular hydrogen-bonding interactions to its neighboring oxygen atom as well as participating in intermolecular interactions with adjoining molecules. Thus, it is related to other similar compounds, such as 1,3,5-triamino-2,4,6-trinitrobenzene (TATB; Cady & Larson, 1965; Kolb & Rizzo, 1979) and 2,6-diamino-3,5,-dinitropyrazine (ANPZ; Gilardi & George, 1984), which have a similar extensive system of intra- and intermolecular hydrogen-bonding interactions resulting in a sheet-like packing system, high densities (1.937 and 1.812 Mg m-3, respectively), and relative insensitivity. These intermolecular hydrogen-bonding interactions result in ruffled parallel sheets in the [101] direction. One of the potentially useful features of ANPZO is its relative insensitivity. Sensitivity is often tested via the drop-height method, i.e. the height of the drop of a steel ball required to detonate the compound, with large values reflecting insensitivity. In such testing, the parent molecule, ANPZ (2,6-diamino-3,5-dinitro-1,4-pyrazine), has values which are so large they cannot be accurately measured, while ANPZO has a value of 117 cm (Pagoria, 2001). These values indicate that ANPZO is safer compared to other commonly used energetic compounds such as trinitrotoluene (80 cm) and HMX (32 cm). Fig. 1 shows the structure and labeling scheme for the title compound. Hydrogen-bonding metrical parameters are given in Table 1.