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The prevalent polymorph of the energetic material 5-nitro-2,4-dihydro-1,2,4,-triazol-3-one, α-NTO, crystallizes as a four-component twin with triclinic symmetry (space group P\bar 1). All crystals under investigation were fourlings, i.e. they contained each of the four possible twin components. Complete data sets were collected for two crystals, one with a predominant amount of one individual component (55%) and one with approximately equal volumes of each component. In both cases the fourling components are related by the twofold axes inherent in the holohedral symmetry of a pseudo-orthorhombic superlattice with ao = at, bo = bt and co = at + bt + 2ct. The triclinic unit cell contains four crystallographically independent planar molecules in the asymmetric unit, each of which forms a hydrogen-bonded flat chain parallel to at. Pairs of chains are combined into planar ribbons by additional hydrogen bonds. Thus, two independent ribbons extend parallel to at, creating a dihedral angle of ∼ 70°. The origin of the twinning is derived from consideration of the crystal packing and the hydrogen-bonding scheme.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768105022792/sn5022sup1.cif
Contains datablocks alpha-NTO, global

fcf

Structure factor file (CIF format) https://doi.org/10.1107/S0108768105022792/sn5022sup2.fcf
Contains datablock proba

CCDC reference: 1243661

Computing details top

Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
5-nitro-2,4-dihydro-3H-1,2,4,-triazol-3-one top
Crystal data top
C2H2N4O3Z = 8
Mr = 130.08F(000) = 528
Triclinic, P1Dx = 1.916 Mg m3
a = 5.1233 (8) ÅMo Kα radiation, λ = 0.71069 Å
b = 10.3140 (16) ÅCell parameters from 3399 reflections
c = 17.998 (3) Åθ = 2.6–28.2°
α = 106.610 (2)°µ = 0.18 mm1
β = 97.810 (2)°T = 293 K
γ = 90.130 (2)°Parallelpiped, colorless
V = 902.1 (2) Å30.34 × 0.26 × 0.20 mm
Data collection top
Bruker platform with 1K CCD
diffractometer
8966 independent reflections
Radiation source: normal-focus sealed tube8202 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.000
ω–scansθmax = 28.7°, θmin = 2.1°
Absorption correction: multi-scan
SADABS;Sheldrick1996;Blessing,ActaC.1995,A51,33
h = 66
Tmin = 0.851, Tmax = 1.000k = 1313
8966 measured reflectionsl = 2423
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0554P)2 + 0.2255P]
where P = (Fo2 + 2Fc2)/3
8966 reflections(Δ/σ)max = 0.002
328 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
C2H2N4O3γ = 90.130 (2)°
Mr = 130.08V = 902.1 (2) Å3
Triclinic, P1Z = 8
a = 5.1233 (8) ÅMo Kα radiation
b = 10.3140 (16) ŵ = 0.18 mm1
c = 17.998 (3) ÅT = 293 K
α = 106.610 (2)°0.34 × 0.26 × 0.20 mm
β = 97.810 (2)°
Data collection top
Bruker platform with 1K CCD
diffractometer
8966 independent reflections
Absorption correction: multi-scan
SADABS;Sheldrick1996;Blessing,ActaC.1995,A51,33
8202 reflections with I > 2σ(I)
Tmin = 0.851, Tmax = 1.000Rint = 0.000
8966 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.115H-atom parameters constrained
S = 1.12Δρmax = 0.34 e Å3
8966 reflectionsΔρmin = 0.36 e Å3
328 parameters
Special details top

Experimental. identical or equivalent reflections were not merged

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. Using the twin laws above, the structural model was refined as a four-component twin using the procedure associated with the HKLF 5 format for merohedral twins. Fractional contributions k1, k2, k3, k4 of the twin components were refined constraining k1 = 1 - k2 - k3 - k4. An HKLF 5 format data file was created where each line contained h,k,l, Fo2, σ(Fo2), m where m is the twin component number. Thus, four lines of the data file correspond to each measured reflection: h, k, l, Fo2, σ(Fo2), −1 h, −k, −h-l, Fo2, σ(Fo2), −2 −h, k, −k-l, Fo2, σ(Fo2), −3 −h, −k, h+k+l, Fo2, σ(Fo2), 4 The volumes of the fourling domains refine to 55: 9: 20: 16.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N110.3084 (4)0.06728 (18)0.89274 (10)0.0254 (4)
N210.4387 (4)0.1449 (2)0.93397 (11)0.0264 (4)
H210.36210.19070.95860.037*
C310.7044 (5)0.1426 (3)0.93212 (13)0.0264 (5)
O310.8741 (3)0.20130 (18)0.96269 (9)0.0356 (4)
N410.7383 (4)0.0578 (2)0.88705 (10)0.0260 (4)
H410.88420.03460.87470.037*
C510.4949 (5)0.0188 (2)0.86632 (11)0.0236 (5)
N510.4449 (4)0.0715 (2)0.81750 (10)0.0272 (5)
O510.6354 (4)0.1093 (2)0.79429 (11)0.0372 (5)
O610.2172 (4)0.1003 (2)0.80308 (11)0.0409 (5)
N121.0939 (4)0.43300 (19)0.89177 (10)0.0272 (4)
N221.0000 (4)0.3554 (2)0.93374 (10)0.0285 (5)
H221.10040.31060.95880.037*
C320.7344 (5)0.3559 (2)0.93208 (13)0.0247 (5)
O320.5925 (4)0.29716 (17)0.96306 (9)0.0349 (4)
N420.6593 (4)0.4398 (2)0.88654 (10)0.0256 (4)
H420.50140.46220.87410.037*
C520.8799 (5)0.4801 (2)0.86520 (11)0.0228 (5)
N520.8821 (4)0.5705 (2)0.81713 (11)0.0266 (4)
O520.6643 (4)0.6049 (2)0.79464 (11)0.0383 (5)
O621.0904 (4)0.6061 (2)0.80328 (12)0.0443 (5)
N130.0965 (4)0.04197 (19)0.60938 (10)0.0262 (4)
N230.0007 (4)0.07541 (19)0.56712 (11)0.0263 (4)
H230.09930.14590.54150.037*
C330.2647 (5)0.0701 (2)0.56948 (13)0.0251 (5)
O330.4089 (4)0.15743 (16)0.53844 (9)0.0365 (4)
N430.3376 (4)0.0603 (2)0.61626 (11)0.0258 (4)
H430.49440.09680.62930.037*
C530.1129 (4)0.1182 (2)0.63718 (12)0.0211 (4)
N530.1048 (4)0.2559 (2)0.68601 (11)0.0266 (4)
O530.3155 (4)0.31856 (19)0.70961 (11)0.0388 (5)
O630.1129 (4)0.2971 (2)0.69924 (11)0.0422 (5)
N140.7013 (4)0.53429 (19)0.60426 (10)0.0274 (4)
N240.5640 (4)0.41422 (19)0.56377 (11)0.0259 (4)
H240.63790.34330.53890.037*
C340.3013 (5)0.4189 (2)0.56700 (13)0.0269 (5)
O340.1287 (4)0.33027 (16)0.53764 (9)0.0374 (4)
N440.2754 (4)0.5511 (2)0.61176 (11)0.0262 (4)
H440.13140.58790.62460.037*
C540.5181 (5)0.6103 (2)0.63109 (12)0.0248 (5)
N540.5689 (4)0.7486 (2)0.67853 (11)0.0271 (4)
O540.3796 (4)0.80735 (19)0.70440 (11)0.0392 (5)
O640.7956 (4)0.7932 (2)0.68975 (11)0.0423 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0224 (11)0.0280 (9)0.0272 (9)0.0030 (9)0.0016 (8)0.0113 (7)
N210.0257 (11)0.0273 (10)0.0315 (9)0.0035 (8)0.0042 (8)0.0169 (8)
C310.0257 (13)0.0275 (12)0.0282 (11)0.0016 (10)0.0032 (9)0.0115 (10)
O310.0268 (10)0.0470 (10)0.0422 (9)0.0105 (8)0.0023 (7)0.0286 (7)
N410.0203 (10)0.0313 (10)0.0302 (9)0.0023 (8)0.0013 (8)0.0163 (8)
C510.0238 (12)0.0222 (10)0.0251 (10)0.0014 (9)0.0007 (9)0.0085 (8)
N510.0334 (12)0.0247 (10)0.0244 (9)0.0037 (9)0.0019 (8)0.0094 (7)
O510.0393 (11)0.0392 (11)0.0410 (9)0.0009 (9)0.0078 (8)0.0229 (8)
O610.0323 (12)0.0486 (12)0.0479 (10)0.0149 (9)0.0014 (8)0.0256 (9)
N120.0242 (11)0.0303 (10)0.0282 (9)0.0033 (9)0.0033 (8)0.0103 (7)
N220.0287 (12)0.0298 (11)0.0318 (10)0.0034 (9)0.0026 (8)0.0173 (8)
C320.0211 (12)0.0242 (12)0.0298 (11)0.0024 (9)0.0004 (8)0.0112 (9)
O320.0280 (10)0.0425 (10)0.0432 (9)0.0002 (8)0.0041 (8)0.0270 (7)
N420.0223 (11)0.0282 (10)0.0309 (9)0.0026 (8)0.0029 (8)0.0160 (8)
C520.0203 (11)0.0248 (11)0.0239 (10)0.0021 (9)0.0009 (8)0.0088 (8)
N520.0280 (11)0.0269 (10)0.0266 (10)0.0005 (8)0.0048 (8)0.0100 (8)
O520.0382 (11)0.0437 (12)0.0390 (9)0.0058 (9)0.0018 (8)0.0250 (9)
O620.0413 (12)0.0430 (11)0.0581 (11)0.0001 (9)0.0166 (9)0.0256 (9)
N130.0210 (11)0.0246 (9)0.0323 (10)0.0035 (8)0.0046 (8)0.0069 (7)
N230.0261 (11)0.0170 (9)0.0325 (10)0.0018 (8)0.0014 (8)0.0034 (7)
C330.0308 (14)0.0173 (11)0.0261 (11)0.0033 (9)0.0044 (9)0.0044 (9)
O330.0342 (10)0.0237 (8)0.0447 (9)0.0066 (8)0.0063 (8)0.0015 (7)
N430.0160 (10)0.0210 (9)0.0367 (10)0.0024 (8)0.0021 (8)0.0033 (8)
C530.0169 (11)0.0190 (10)0.0274 (10)0.0044 (8)0.0034 (8)0.0067 (8)
N530.0283 (11)0.0205 (10)0.0304 (10)0.0052 (8)0.0042 (8)0.0059 (8)
O530.0334 (11)0.0272 (9)0.0503 (10)0.0039 (8)0.0012 (8)0.0049 (8)
O630.0355 (11)0.0350 (10)0.0512 (10)0.0125 (9)0.0132 (8)0.0013 (8)
N140.0259 (11)0.0227 (9)0.0336 (10)0.0023 (8)0.0046 (8)0.0079 (7)
N240.0256 (11)0.0172 (9)0.0318 (9)0.0027 (8)0.0063 (7)0.0012 (7)
C340.0315 (14)0.0221 (12)0.0248 (11)0.0033 (10)0.0061 (9)0.0023 (9)
O340.0319 (10)0.0236 (8)0.0485 (10)0.0058 (8)0.0046 (8)0.0018 (7)
N440.0200 (10)0.0206 (9)0.0352 (10)0.0036 (8)0.0068 (8)0.0021 (7)
C540.0267 (13)0.0218 (11)0.0248 (10)0.0015 (10)0.0054 (9)0.0042 (8)
N540.0310 (12)0.0185 (9)0.0309 (10)0.0006 (8)0.0013 (8)0.0072 (8)
O540.0375 (11)0.0264 (10)0.0493 (10)0.0061 (8)0.0122 (8)0.0012 (8)
O640.0322 (11)0.0337 (10)0.0574 (11)0.0140 (9)0.0002 (9)0.0106 (9)
Geometric parameters (Å, º) top
N11—C511.283 (3)N13—C531.283 (3)
N11—N211.358 (3)N13—N231.365 (3)
N21—C311.367 (3)N23—C331.355 (3)
N21—H210.8600N23—H230.8600
C31—O311.220 (3)C33—O331.223 (3)
C31—N411.377 (3)C33—N431.386 (3)
N41—H410.8600N43—C531.348 (3)
N41—C511.348 (3)N43—H430.8600
C51—N511.454 (3)C53—N531.444 (3)
N51—O511.217 (3)N53—O531.216 (3)
N51—O611.217 (3)N53—O631.224 (3)
N12—C521.288 (3)N14—C541.280 (3)
N12—N221.373 (3)N14—N241.378 (3)
N22—C321.357 (3)N24—C341.356 (3)
N22—H220.8600N24—H240.8600
C32—O321.228 (3)C34—O341.220 (3)
C32—N421.374 (3)C34—N441.389 (3)
N42—C521.343 (3)N44—C541.341 (3)
N42—H420.8600N44—H440.8600
C52—N521.443 (3)C54—N541.440 (3)
N52—O621.208 (3)N54—O641.217 (3)
N52—O521.223 (3)N54—O541.220 (3)
C51—N11—N21102.69 (18)C53—N13—N23102.64 (19)
N11—N21—C31112.8 (2)C33—N23—N13113.47 (19)
N11—N21—H21123.6C33—N23—H23123.3
C31—N21—H21123.6N13—N23—H23123.3
O31—C31—N21128.8 (2)O33—C33—N23129.4 (2)
O31—C31—N41127.4 (2)O33—C33—N43127.5 (2)
N21—C31—N41103.7 (2)N23—C33—N43103.10 (19)
C51—N41—C31105.5 (2)C53—N43—C33106.10 (19)
C51—N41—H41127.2C53—N43—H43127.0
C31—N41—H41127.2C33—N43—H43127.0
N11—C51—N41115.2 (2)N13—C53—N43114.70 (19)
N11—C51—N51121.9 (2)N13—C53—N53122.04 (19)
N41—C51—N51122.8 (2)N43—C53—N53123.3 (2)
O51—N51—O61126.5 (2)O53—N53—O63126.9 (2)
O51—N51—C51116.5 (2)O53—N53—C53116.43 (19)
O61—N51—C51117.0 (2)O63—N53—C53116.7 (2)
C52—N12—N22101.7 (2)C54—N14—N24102.31 (19)
C32—N22—N12113.9 (2)C34—N24—N14113.47 (19)
C32—N22—H22123.0C34—N24—H24123.3
N12—N22—H22123.0N14—N24—H24123.3
O32—C32—N22129.6 (2)O34—C34—N24129.2 (2)
O32—C32—N42127.7 (2)O34—C34—N44128.2 (2)
N22—C32—N42102.7 (2)N24—C34—N44102.6 (2)
C52—N42—C32106.9 (2)C54—N44—C34106.8 (2)
C52—N42—H42126.6C54—N44—H44126.6
C32—N42—H42126.6C34—N44—H44126.6
N12—C52—N42114.8 (2)N14—C54—N44114.8 (2)
N12—C52—N52121.7 (2)N14—C54—N54122.6 (2)
N42—C52—N52123.5 (2)N44—C54—N54122.6 (2)
O62—N52—O52126.1 (2)O64—N54—O54127.2 (2)
O62—N52—C52119.2 (2)O64—N54—C54116.8 (2)
O52—N52—C52114.6 (2)O54—N54—C54116.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H21···O32i0.862.012.769 (2)147
N21—H21···O31ii0.862.513.089 (3)125
N41—H41···N11iii0.862.202.912 (3)141
N22—H22···O31iv0.862.042.791 (3)146
N22—H22···O32iii0.862.523.100 (3)126
N42—H42···N12ii0.862.192.913 (3)142
N23—H23···O34v0.862.012.778 (2)147
N23—H23···O33ii0.862.513.073 (3)123
N43—H43···N13iii0.862.222.923 (3)139
N24—H24···O33vi0.862.012.776 (2)147
N24—H24···O34iii0.862.523.081 (3)124
N44—H44···N14ii0.862.232.928 (3)139
Symmetry codes: (i) x+1, y, z+2; (ii) x1, y, z; (iii) x+1, y, z; (iv) x+2, y, z+2; (v) x, y, z+1; (vi) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaC2H2N4O3
Mr130.08
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)5.1233 (8), 10.3140 (16), 17.998 (3)
α, β, γ (°)106.610 (2), 97.810 (2), 90.130 (2)
V3)902.1 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.18
Crystal size (mm)0.34 × 0.26 × 0.20
Data collection
DiffractometerBruker platform with 1K CCD
diffractometer
Absorption correctionMulti-scan
SADABS;Sheldrick1996;Blessing,ActaC.1995,A51,33
Tmin, Tmax0.851, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
8966, 8966, 8202
Rint0.000
(sin θ/λ)max1)0.676
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.115, 1.12
No. of reflections8966
No. of parameters328
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.34, 0.36

Computer programs: SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H21···O32i0.862.012.769 (2)146.5
N21—H21···O31ii0.862.513.089 (3)125.0
N41—H41···N11iii0.862.202.912 (3)140.6
N22—H22···O31iv0.862.042.791 (3)146.1
N22—H22···O32iii0.862.523.100 (3)125.8
N42—H42···N12ii0.862.192.913 (3)141.9
N23—H23···O34v0.862.012.778 (2)147.4
N23—H23···O33ii0.862.513.073 (3)123.4
N43—H43···N13iii0.862.222.923 (3)138.7
N24—H24···O33vi0.862.012.776 (2)147.4
N24—H24···O34iii0.862.523.081 (3)123.5
N44—H44···N14ii0.862.232.928 (3)138.8
Symmetry codes: (i) x+1, y, z+2; (ii) x1, y, z; (iii) x+1, y, z; (iv) x+2, y, z+2; (v) x, y, z+1; (vi) x+1, y, z+1.
 

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