Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011722/wn6030sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011722/wn6030Isup2.hkl |
CCDC reference: 170918
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: SMART (Bruker, 1994); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C4H4N6O4·C2H6OS | Z = 2 |
Mr = 278.26 | F(000) = 288 |
Triclinic, P1 | Dx = 1.662 Mg m−3 |
a = 5.7817 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.1353 (8) Å | Cell parameters from 3759 reflections |
c = 12.0270 (11) Å | θ = 2.5–28.3° |
α = 99.253 (2)° | µ = 0.32 mm−1 |
β = 94.113 (2)° | T = 93 K |
γ = 92.482 (2)° | Prism, yellow |
V = 556.04 (9) Å3 | 0.65 × 0.22 × 0.07 mm |
CCD area detector diffractometer | 2638 independent reflections |
Radiation source: fine-focus sealed tube | 2505 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 28.3°, θmin = 1.7° |
Absorption correction: integration (Wuensch & Prewitt, 1965) | h = −6→7 |
Tmin = 0.919, Tmax = 0.969 | k = −10→10 |
4175 measured reflections | l = −15→16 |
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)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0434P)2 + 0.3143P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max = 0.006 |
2638 reflections | Δρmax = 0.44 e Å−3 |
204 parameters | Δρmin = −0.25 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: 0.005 (2) |
C4H4N6O4·C2H6OS | γ = 92.482 (2)° |
Mr = 278.26 | V = 556.04 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.7817 (5) Å | Mo Kα radiation |
b = 8.1353 (8) Å | µ = 0.32 mm−1 |
c = 12.0270 (11) Å | T = 93 K |
α = 99.253 (2)° | 0.65 × 0.22 × 0.07 mm |
β = 94.113 (2)° |
CCD area detector diffractometer | 2638 independent reflections |
Absorption correction: integration (Wuensch & Prewitt, 1965) | 2505 reflections with I > 2σ(I) |
Tmin = 0.919, Tmax = 0.969 | Rint = 0.031 |
4175 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.44 e Å−3 |
2638 reflections | Δρmin = −0.25 e Å−3 |
204 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 | ||
S1S | 1.17993 (6) | 0.66666 (4) | 1.34974 (3) | 0.01204 (11) | |
O1S | 1.03544 (19) | 0.62121 (14) | 1.23767 (9) | 0.0172 (2) | |
N1 | 0.7338 (2) | 0.64907 (15) | 0.94637 (10) | 0.0127 (2) | |
C2 | 0.5825 (2) | 0.61920 (17) | 0.85410 (12) | 0.0123 (3) | |
N2 | 0.3974 (2) | 0.51846 (17) | 0.85675 (11) | 0.0159 (3) | |
H2A | 0.299 (4) | 0.494 (2) | 0.8020 (18) | 0.016 (5)* | |
H2B | 0.379 (4) | 0.480 (3) | 0.9132 (19) | 0.017 (5)* | |
C3 | 0.6322 (2) | 0.69773 (17) | 0.75867 (12) | 0.0121 (3) | |
N3 | 0.4786 (2) | 0.67906 (15) | 0.65560 (10) | 0.0134 (2) | |
O3A | 0.29497 (19) | 0.59424 (15) | 0.65159 (10) | 0.0215 (3) | |
O3B | 0.53576 (19) | 0.74861 (15) | 0.57813 (9) | 0.0193 (2) | |
N4 | 0.8207 (2) | 0.79105 (15) | 0.75808 (10) | 0.0123 (2) | |
C5 | 0.9692 (2) | 0.81529 (17) | 0.84709 (12) | 0.0123 (3) | |
N5 | 1.1745 (2) | 0.91916 (15) | 0.83599 (11) | 0.0140 (2) | |
O5A | 1.32413 (18) | 0.94817 (14) | 0.91680 (10) | 0.0190 (2) | |
O5B | 1.1932 (2) | 0.97274 (15) | 0.74713 (10) | 0.0208 (2) | |
C6 | 0.9299 (2) | 0.74434 (17) | 0.94705 (12) | 0.0121 (3) | |
N6 | 1.0750 (2) | 0.76880 (17) | 1.03955 (11) | 0.0155 (3) | |
H6A | 1.207 (4) | 0.820 (3) | 1.0382 (17) | 0.020 (5)* | |
H6B | 1.048 (4) | 0.724 (3) | 1.094 (2) | 0.023 (5)* | |
C1S | 0.9899 (3) | 0.7636 (2) | 1.44803 (14) | 0.0205 (3) | |
H1SA | 0.877 (4) | 0.682 (3) | 1.458 (2) | 0.038 (6)* | |
H1SB | 0.920 (4) | 0.848 (3) | 1.4155 (19) | 0.026 (5)* | |
H1SC | 1.080 (4) | 0.803 (3) | 1.518 (2) | 0.031 (6)* | |
C2S | 1.3558 (3) | 0.8471 (2) | 1.33623 (15) | 0.0215 (3) | |
H2SA | 1.463 (5) | 0.817 (3) | 1.282 (2) | 0.041 (7)* | |
H2SB | 1.441 (4) | 0.884 (3) | 1.407 (2) | 0.029 (6)* | |
H2SC | 1.259 (4) | 0.932 (3) | 1.315 (2) | 0.037 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1S | 0.01286 (18) | 0.01223 (18) | 0.01090 (18) | −0.00085 (12) | −0.00046 (12) | 0.00252 (12) |
O1S | 0.0177 (5) | 0.0214 (5) | 0.0114 (5) | −0.0058 (4) | −0.0017 (4) | 0.0028 (4) |
N1 | 0.0145 (6) | 0.0133 (6) | 0.0104 (5) | −0.0007 (4) | 0.0000 (4) | 0.0029 (4) |
C2 | 0.0141 (6) | 0.0120 (6) | 0.0110 (6) | 0.0010 (5) | 0.0018 (5) | 0.0022 (5) |
N2 | 0.0159 (6) | 0.0205 (6) | 0.0116 (6) | −0.0052 (5) | −0.0023 (5) | 0.0064 (5) |
C3 | 0.0121 (6) | 0.0137 (6) | 0.0107 (6) | 0.0005 (5) | 0.0001 (5) | 0.0033 (5) |
N3 | 0.0139 (6) | 0.0153 (6) | 0.0113 (6) | −0.0009 (4) | 0.0003 (4) | 0.0036 (4) |
O3A | 0.0174 (5) | 0.0272 (6) | 0.0200 (5) | −0.0096 (4) | −0.0054 (4) | 0.0103 (5) |
O3B | 0.0188 (5) | 0.0276 (6) | 0.0127 (5) | −0.0031 (4) | −0.0007 (4) | 0.0091 (4) |
N4 | 0.0129 (5) | 0.0118 (5) | 0.0125 (6) | 0.0018 (4) | 0.0018 (4) | 0.0026 (4) |
C5 | 0.0117 (6) | 0.0120 (6) | 0.0135 (6) | −0.0009 (5) | 0.0016 (5) | 0.0030 (5) |
N5 | 0.0129 (5) | 0.0140 (6) | 0.0152 (6) | −0.0004 (4) | 0.0012 (4) | 0.0030 (5) |
O5A | 0.0148 (5) | 0.0222 (5) | 0.0190 (5) | −0.0040 (4) | −0.0048 (4) | 0.0047 (4) |
O5B | 0.0199 (5) | 0.0259 (6) | 0.0178 (5) | −0.0070 (4) | −0.0002 (4) | 0.0107 (4) |
C6 | 0.0131 (6) | 0.0120 (6) | 0.0112 (6) | 0.0016 (5) | 0.0017 (5) | 0.0018 (5) |
N6 | 0.0150 (6) | 0.0193 (6) | 0.0126 (6) | −0.0031 (5) | −0.0006 (5) | 0.0056 (5) |
C1S | 0.0188 (7) | 0.0257 (8) | 0.0158 (7) | 0.0037 (6) | 0.0021 (6) | −0.0011 (6) |
C2S | 0.0218 (8) | 0.0209 (8) | 0.0216 (8) | −0.0091 (6) | −0.0051 (6) | 0.0090 (6) |
S1S—O1S | 1.5174 (11) | N3—O3B | 1.2226 (16) |
S1S—C2S | 1.7852 (16) | N3—O3A | 1.2347 (16) |
S1S—C1S | 1.7855 (16) | N4—C5 | 1.3069 (19) |
N1—C6 | 1.3438 (18) | C5—C6 | 1.4426 (19) |
N1—C2 | 1.3458 (18) | C5—N5 | 1.4535 (17) |
C2—N2 | 1.3251 (18) | N5—O5B | 1.2273 (17) |
C2—C3 | 1.4405 (19) | N5—O5A | 1.2396 (16) |
C3—N4 | 1.3018 (18) | C6—N6 | 1.3274 (19) |
C3—N3 | 1.4555 (17) | ||
O1S—S1S—C2S | 105.12 (7) | O3A—N3—C3 | 117.79 (11) |
O1S—S1S—C1S | 106.08 (7) | C3—N4—C5 | 119.07 (12) |
C2S—S1S—C1S | 98.55 (9) | N4—C5—C6 | 122.24 (13) |
C6—N1—C2 | 120.51 (12) | N4—C5—N5 | 114.15 (12) |
N2—C2—N1 | 117.72 (13) | C6—C5—N5 | 123.61 (13) |
N2—C2—C3 | 124.14 (13) | O5B—N5—O5A | 122.99 (12) |
N1—C2—C3 | 118.14 (12) | O5B—N5—C5 | 118.81 (12) |
N4—C3—C2 | 122.12 (13) | O5A—N5—C5 | 118.19 (12) |
N4—C3—N3 | 114.65 (12) | N6—C6—N1 | 118.34 (13) |
C2—C3—N3 | 123.22 (12) | N6—C6—C5 | 123.80 (13) |
O3B—N3—O3A | 123.32 (12) | N1—C6—C5 | 117.87 (12) |
O3B—N3—C3 | 118.88 (12) | ||
C6—N1—C2—N2 | 177.11 (13) | C3—N4—C5—C6 | −1.1 (2) |
C6—N1—C2—C3 | −2.6 (2) | C3—N4—C5—N5 | 179.04 (12) |
N2—C2—C3—N4 | −177.40 (13) | N4—C5—N5—O5B | −0.68 (19) |
N1—C2—C3—N4 | 2.3 (2) | C6—C5—N5—O5B | 179.41 (13) |
N2—C2—C3—N3 | 2.2 (2) | N4—C5—N5—O5A | −179.98 (12) |
N1—C2—C3—N3 | −178.10 (12) | C6—C5—N5—O5A | 0.1 (2) |
N4—C3—N3—O3B | 0.54 (19) | C2—N1—C6—N6 | −179.27 (12) |
C2—C3—N3—O3B | −179.13 (13) | C2—N1—C6—C5 | 1.2 (2) |
N4—C3—N3—O3A | −178.82 (13) | N4—C5—C6—N6 | −178.79 (13) |
C2—C3—N3—O3A | 1.5 (2) | N5—C5—C6—N6 | 1.1 (2) |
C2—C3—N4—C5 | −0.4 (2) | N4—C5—C6—N1 | 0.7 (2) |
N3—C3—N4—C5 | 179.91 (12) | N5—C5—C6—N1 | −179.40 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3A | 0.83 (2) | 2.10 (2) | 2.6703 (18) | 125.6 (17) |
N2—H2A···O1Si | 0.83 (2) | 2.10 (2) | 2.7884 (17) | 139.9 (18) |
N2—H2B···N1i | 0.80 (2) | 2.25 (2) | 3.0407 (18) | 170 (2) |
N6—H6A···O5A | 0.86 (2) | 2.06 (2) | 2.6831 (18) | 128.8 (18) |
N6—H6B···O1S | 0.82 (2) | 2.05 (2) | 2.8541 (17) | 171 (2) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C4H4N6O4·C2H6OS |
Mr | 278.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 93 |
a, b, c (Å) | 5.7817 (5), 8.1353 (8), 12.0270 (11) |
α, β, γ (°) | 99.253 (2), 94.113 (2), 92.482 (2) |
V (Å3) | 556.04 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.32 |
Crystal size (mm) | 0.65 × 0.22 × 0.07 |
Data collection | |
Diffractometer | CCD area detector diffractometer |
Absorption correction | Integration (Wuensch & Prewitt, 1965) |
Tmin, Tmax | 0.919, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4175, 2638, 2505 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.091, 1.14 |
No. of reflections | 2638 |
No. of parameters | 204 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.44, −0.25 |
Computer programs: SMART (Bruker, 1994), SMART, SHELXTL (Bruker, 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3A | 0.83 (2) | 2.10 (2) | 2.6703 (18) | 125.6 (17) |
N2—H2A···O1Si | 0.83 (2) | 2.10 (2) | 2.7884 (17) | 139.9 (18) |
N2—H2B···N1i | 0.80 (2) | 2.25 (2) | 3.0407 (18) | 170 (2) |
N6—H6A···O5A | 0.86 (2) | 2.06 (2) | 2.6831 (18) | 128.8 (18) |
N6—H6B···O1S | 0.82 (2) | 2.05 (2) | 2.8541 (17) | 171 (2) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
The title compound, 2,6-diamino-3,5-dinitro-1,4-pyrazine dimethyl sulfoxide solvate, (I), is a dimethyl sulfoxide (DMSO) solvate of the insensitive energetic molecule 2,6-diamino-3,5-dinitro-1,4-pyrazine (ANPZ). ANPZ is a member of an important family of insensitive energetic compounds (TATB: Cady & Larson, 1965; Kolb & Rizzo, 1979; ANPZ: Gilardi & Butcher, 2001; ANPZO: Gilardi & Butcher, 2001), in which the molecules exhibit both multiple intramolecular and intermolecular hydrogen bonding interactions (TATB is 1,3,5-triamino-2,4,6-trinitrobenzene and ANPZO is 2,6-diamino-3,5-dinitropyrazine-1-oxide).
The intermolecular hydrogen-bonding interactions result in a planar sheet-like packing arrangement where the spacing between the layers resembles that of graphite. The significant feature of this family of energetic molecules is their 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, in common with TATB, the benchmark compound as regards insensitivity, ANPZ has values which are so large they cannot be accurately measured, while ANPZO has a value of 117 cm (Pagoria et al., 1998). Thus ANPZ is much safer than other commonly used energetic compounds such as trinitrotoluene (80 cm) and HMX (32 cm). The primary motivating factor in determining the structure of the ANPZ solvate was to obtain more accurate metrical parameters for ANPZ as its crystals are invariably twinned (Gilardi & Butcher, 2001). The packing motif for the DMSO solvate consists of two ANPZ molecules linked by strong complementary hydrogen bonds and DMSO solvate molecules, each linked by two bifurcated hydrogen bonds to the ANPZ dimer. This central motif is further linked into planar sheets by weaker interactions between the DMSO methyl H atoms and the O atoms from the nitro groups. This packing arrangement is looser than that of ANPZ, and results in a lower density (1.662 Mg m-3 versus 1.812 Mg m-3 for ANPZ). Fig. 1 shows the structure and labeling scheme for the title compound, while Fig. 2 shows the packing arrangement. Hydrogen-bonding metrical parameters are given in Table 1.