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The crystal and molecular structures of 2-[1-(2-aminoethyl)-2-imidazolidinylidene]-2-nitroacetonitrile [C7H11N5O2; space group P21/n; Z = 4; a = 7.4889 (8), b = 17.273 (2), c = 7.4073 (8) Å, β = 111.937 (6)°], (I), and 2,6-diamino-5-hydroxy-3-nitro-4H-pyrazolo[1,5-a]­pyrimidin-7-one monohydrate [C6H6N6O4·H2O; space group P21/n; Z = 4; a = 17.576 (3), b = 10.900 (2), c = 4.6738 (6) Å, β = 92.867 (8)°], (II), have been determined from X-ray, synchrotron and neutron powder diffraction data using various methods. The structures were originally solved from Guinier ­photographs with a grid search procedure and the program MRIA using a priori information from NMR and mass spectra on the possible geometry of the molecules. Because the conformation of molecule (I) changed during the bond-restrained Rietveld refinement, solvent water was found in (II) and, moreover, as both Guinier patterns were corrupted by texture, high-­resolution texture-free synchrotron data were collected at the BM16 beamline, ESRF, to confirm the original results. Using the set of |F|2 values derived from the synchrotron patterns after full-pattern decom­position procedures, the structures of (I) and (II) were solved by direct methods via SHELXS96, SIRPOW.92 and POWSIM without any preliminary models of the molecules, and by Patterson search methods via DIRDIF96 and PATSEE with the use of rigid fragments from each of the molecules. The neutron patterns allowed (I) and (II) to be solved using the grid search procedure and correct initial models of the molecules including H atoms. The results obtained from powder patterns measured on different devices demonstrate the high level of reproducibility and reliability of various powder software and equipment, with a certain preference for synchrotron facilities.

Supporting information

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Portable Document Format (PDF) file
Supplementary material

cif

Crystallographic Information File (CIF)
Contains datablocks cher, I2, II2

rtv

Rietveld powder data file (CIF format)
Contains datablock I2

sft

Structure factor file (SHELXL table format)
Supplementary material

rtv

Rietveld powder data file (CIF format)
Contains datablock cher_fitch_synchro_1

rtv

Rietveld powder data file (CIF format)
Contains datablock I2

rtv

Rietveld powder data file (CIF format)
Contains datablock II2

sft

Structure factor file (SHELXL table format)
Supplementary material

rtv

Rietveld powder data file (CIF format)
Contains datablock cher_fitch_synchro_2

rtv

Rietveld powder data file (CIF format)
Supplementary material

CCDC references: 1207685; 1207686; 1207687; 1207688

Computing details top

For both compounds, cell refinement: LSPAID (Visser et al., 1986); data reduction: MRIA (Zlokazov et al., 1992); program(s) used to solve structure: DIRDIF92, MRIA, PATSEE, POWSIM, SIRPOW.92, SHELXS96; program(s) used to refine structure: MRIA; molecular graphics: PLUTON92 (Spek, 1992); software used to prepare material for publication: MRIA.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
(I2) [1-(2-aminoethyl)-1,2-dihydroimidazolidene-2]nitroacetonitrile top
Crystal data top
C7H11N5O2F(000) = 416
Mr = 197.21Dx = 1.474 Mg m3
Monoclinic, P21/nSynchrotron radiation, λ = 0.85617(3) Å
a = 7.4889 (8) ŵ = 0.11 mm1
b = 17.273 (2) ÅT = 295 K
c = 7.4073 (8) ÅParticle morphology: lump-like
β = 111.937 (6)°light yellow
V = 888.8 (2) Å3cylinder, 15 × 1 mm
Z = 4
Data collection top
ESRF powder
diffractometer
Data collection mode: transmission
Radiation source: BM16 bending magnet at ESRF, synchrotron radiationScan method: continuous
Si 111 double crystal monochromator2θmin = 4°, 2θmax = 44°, 2θstep = 0.004°
Specimen mounting: specimen was sealed in a 1 mm diameter borosilicate glass capillary
Refinement top
Refinement on Inet135 parameters
Least-squares matrix: full with fixed elements per cycle112 restraints
Rp = 0.05010 constraints
Rwp = 0.064H atoms treated by a mixture of independent and constrained refinement
Rexp = 0.050Weighting scheme based on measured s.u.'s
χ2 = 2.103(Δ/σ)max = 0.10
10001 data pointsBackground function: Chebyshev polynomial up to the 5th order
Profile function: split-type pseudo-VoigtPreferred orientation correction: March-Dollase (Dollase, 1986), direction of preferred orientation [010], March-Dollase texture parameter r=1.066(4).
Crystal data top
C7H11N5O2V = 888.8 (2) Å3
Mr = 197.21Z = 4
Monoclinic, P21/nSynchrotron radiation, λ = 0.85617(3) Å
a = 7.4889 (8) ŵ = 0.11 mm1
b = 17.273 (2) ÅT = 295 K
c = 7.4073 (8) Åcylinder, 15 × 1 mm
β = 111.937 (6)°
Data collection top
ESRF powder
diffractometer
Scan method: continuous
Specimen mounting: specimen was sealed in a 1 mm diameter borosilicate glass capillary2θmin = 4°, 2θmax = 44°, 2θstep = 0.004°
Data collection mode: transmission
Refinement top
Rp = 0.050135 parameters
Rwp = 0.064112 restraints
Rexp = 0.050H atoms treated by a mixture of independent and constrained refinement
χ2 = 2.103(Δ/σ)max = 0.10
10001 data points
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.2150 (8)0.6302 (3)0.3818 (9)0.065 (6)*
O20.4715 (7)0.5869 (3)0.3457 (9)0.070 (6)*
N10.4562 (8)0.4475 (3)0.185 (1)0.032 (4)*
N20.2009 (7)0.3757 (3)0.1460 (8)0.048 (5)*
N30.1403 (8)0.3163 (3)0.5002 (7)0.057 (5)*
N40.3019 (9)0.5788 (4)0.334 (1)0.043 (5)*
N50.1526 (8)0.5103 (3)0.253 (1)0.063 (5)*
C20.2798 (9)0.4461 (5)0.205 (1)0.050 (6)*
C30.5080 (9)0.3741 (4)0.126 (1)0.069 (7)*
C40.3237 (9)0.3276 (5)0.0779 (9)0.081 (7)*
C50.1975 (9)0.5107 (5)0.257 (1)0.032 (5)*
C60.0017 (9)0.5084 (6)0.255 (1)0.026 (4)*
C70.0181 (9)0.3423 (4)0.1388 (8)0.072 (7)*
C80.0489 (9)0.2865 (4)0.3077 (9)0.054 (6)*
H10.525 (6)0.495 (3)0.188 (6)0.12 (3)*
H30.612 (7)0.352 (3)0.235 (7)0.12 (3)*
H310.548 (8)0.378 (3)0.017 (6)0.12 (3)*
H40.265 (8)0.320 (3)0.063 (6)0.12 (3)*
H410.345 (8)0.279 (3)0.145 (6)0.12 (3)*
H70.042 (8)0.315 (3)0.018 (7)0.12 (3)*
H710.068 (7)0.384 (3)0.140 (7)0.12 (3)*
H80.079 (7)0.272 (3)0.301 (6)0.12 (3)*
H810.115 (6)0.242 (3)0.290 (7)0.12 (3)*
H90.141 (6)0.369 (3)0.535 (6)0.12 (3)*
H910.230 (7)0.283 (3)0.601 (6)0.12 (3)*
Geometric parameters (Å, º) top
O1—N41.23 (1)C2—C51.398 (9)
O2—N41.247 (9)C3—C41.520 (9)
N1—C21.38 (1)C3—H30.97 (4)
N1—C31.441 (9)C3—H310.96 (6)
N1—H10.97 (5)C4—H40.98 (4)
N2—C21.351 (7)C4—H410.96 (5)
N2—C41.462 (9)C5—C61.46 (1)
N2—C71.468 (8)C7—C81.527 (8)
N3—C81.427 (8)C7—H70.96 (5)
N3—H90.95 (5)C7—H710.97 (5)
N3—H910.98 (4)C8—H80.98 (6)
N4—C51.409 (8)C8—H810.94 (5)
N5—C61.15 (1)
C2—N1—C3113.2 (6)N2—C4—H4111 (3)
C2—N1—H1122 (3)C3—C4—H4109 (3)
C3—N1—H1124 (3)N2—C4—H41109 (3)
C2—N2—C4111.6 (5)C3—C4—H41113 (3)
C2—N2—C7130.9 (5)H4—C4—H41110 (4)
C4—N2—C7117.5 (5)C2—C5—N4122.8 (5)
C8—N3—H9125 (3)C2—C5—C6121.3 (6)
C8—N3—H91119 (2)N4—C5—C6115.6 (6)
H9—N3—H91115 (4)N5—C6—C5176.8 (8)
O1—N4—O2122.2 (7)N2—C7—C8111.4 (5)
O1—N4—C5116.4 (6)N2—C7—H7109 (3)
O2—N4—C5121.3 (7)C8—C7—H7109 (3)
N2—C2—N1107.5 (5)N2—C7—H71109 (3)
N2—C2—C5128.6 (5)C8—C7—H71111 (3)
N1—C2—C5123.6 (6)H7—C7—H71107 (4)
N1—C3—C4102.2 (5)N3—C8—C7117.4 (5)
N1—C3—H3108 (3)N3—C8—H8104 (3)
C4—C3—H3111 (3)C7—C8—H8106 (3)
N1—C3—H31113 (3)N3—C8—H81111 (3)
C4—C3—H31112 (4)C7—C8—H81109 (3)
H3—C3—H31109 (4)H8—C8—H81110 (4)
N2—C4—C3104.7 (5)
(II2) 3,7-diamino-4-nitro-6-hydroxy-8-oxopyrazolo[1,5-a]pyrimidine monohydrate top
Crystal data top
C6H6N6O4·H2OF(000) = 504
Mr = 244.18Dx = 1.814 Mg m3
Monoclinic, P21/nSynchrotron radiation, λ = 0.95044(2) Å
a = 17.576 (3) ŵ = 1.39 mm1
b = 10.900 (2) ÅT = 295 K
c = 4.6738 (6) ÅParticle morphology: feather-like
β = 92.867 (8)°yellow-orange
V = 894.3 (3) Å3cylinder, 15 × 1.5 mm
Z = 4
Data collection top
ESRF powder
diffractometer
Data collection mode: transmission
Radiation source: BM16 bending magnet at ESRF, synchrotron radiationScan method: continuous
Si 111 double crystal monochromator2θmin = 5°, 2θmax = 55°, 2θstep = 0.005°
Specimen mounting: specimen was sealed in a 1.5 mm diameter borosilicate glass capillary
Refinement top
Refinement on Inet126 parameters
Least-squares matrix: full with fixed elements per cycle99 restraints
Rp = 0.05717 constraints
Rwp = 0.068H atoms treated by a mixture of independent and constrained refinement
Rexp = 0.043Weighting scheme based on measured s.u.'s
χ2 = 3.062(Δ/σ)max = 0.10
10001 data pointsBackground function: Chebyshev polynomial up to the 5th order
Profile function: split-type pseudo-VoigtPreferred orientation correction: March-Dollase (Dollase, 1986), direction of preferred orientation [100], March-Dollase texture parameter r=1.053(3).
Crystal data top
C6H6N6O4·H2OV = 894.3 (3) Å3
Mr = 244.18Z = 4
Monoclinic, P21/nSynchrotron radiation, λ = 0.95044(2) Å
a = 17.576 (3) ŵ = 1.39 mm1
b = 10.900 (2) ÅT = 295 K
c = 4.6738 (6) Åcylinder, 15 × 1.5 mm
β = 92.867 (8)°
Data collection top
ESRF powder
diffractometer
Scan method: continuous
Specimen mounting: specimen was sealed in a 1.5 mm diameter borosilicate glass capillary2θmin = 5°, 2θmax = 55°, 2θstep = 0.005°
Data collection mode: transmission
Refinement top
Rp = 0.057126 parameters
Rwp = 0.06899 restraints
Rexp = 0.043H atoms treated by a mixture of independent and constrained refinement
χ2 = 3.062(Δ/σ)max = 0.10
10001 data points
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.3574 (2)0.2495 (3)0.3957 (8)0.013 (1)*
O20.4173 (2)0.5256 (3)0.3330 (8)0.019 (2)*
O30.6433 (2)0.2693 (3)0.3727 (8)0.022 (2)*
O40.6913 (2)0.1096 (3)0.1366 (8)0.025 (2)*
O50.2484 (3)0.6438 (3)0.237 (1)0.020 (2)*
N10.4909 (3)0.1227 (4)0.293 (1)0.010 (1)*
N20.4644 (3)0.2226 (4)0.1357 (8)0.010 (1)*
N30.6025 (3)0.0020 (4)0.2864 (9)0.010 (1)*
N40.6403 (3)0.1871 (4)0.1899 (9)0.020 (2)*
N50.4948 (3)0.3590 (4)0.236 (1)0.010 (1)*
N60.3226 (3)0.4734 (4)0.1177 (9)0.010 (1)*
C20.5585 (3)0.0934 (5)0.188 (1)0.010 (1)*
C30.5739 (3)0.1794 (5)0.040 (1)0.010 (1)*
C40.5141 (4)0.2633 (5)0.059 (1)0.010 (1)*
C60.4308 (4)0.4286 (4)0.178 (1)0.010 (1)*
C70.3843 (3)0.3970 (4)0.044 (1)0.010 (1)*
C80.3972 (3)0.2866 (4)0.202 (1)0.010 (1)*
H30.580 (3)0.070 (4)0.38 (1)0.16 (3)*
H310.645 (3)0.026 (4)0.16 (1)0.16 (3)*
H50.534 (3)0.388 (4)0.37 (1)0.16 (3)*
H60.307 (3)0.537 (4)0.02 (1)0.16 (3)*
H610.280 (3)0.425 (4)0.20 (1)0.16 (3)*
H70.401 (3)0.505 (4)0.53 (1)0.16 (3)*
H80.252 (3)0.710 (4)0.120 (9)0.16 (3)*
H90.254 (3)0.667 (4)0.42 (1)0.16 (3)*
Geometric parameters (Å, º) top
O1—C81.239 (6)N3—H311.02 (5)
O2—C61.297 (6)N4—C31.393 (7)
O2—H70.98 (5)N5—C41.364 (7)
O3—N41.241 (6)N5—C61.395 (8)
O4—N41.248 (6)N5—H51.00 (5)
O5—H80.91 (4)N6—C71.423 (7)
O5—H90.90 (5)N6—H60.98 (5)
N1—C21.346 (7)N6—H611.01 (5)
N1—N21.382 (6)C2—C31.455 (7)
N2—C41.367 (8)C3—C41.393 (8)
N2—C81.419 (7)C6—C71.396 (8)
N3—C21.329 (7)C7—C81.424 (6)
N3—H30.99 (5)
C6—O2—H7112 (3)N3—C2—N1124.1 (5)
H8—O5—H9110 (4)N3—C2—C3127.6 (5)
C2—N1—N2105.9 (4)N1—C2—C3108.3 (4)
C4—N2—N1113.6 (4)C4—C3—N4125.2 (5)
C4—N2—C8123.5 (5)C4—C3—C2107.6 (5)
N1—N2—C8122.2 (4)N4—C3—C2126.7 (5)
C2—N3—H3121 (3)N5—C4—N2120.3 (5)
C2—N3—H31117 (3)N5—C4—C3134.8 (5)
H3—N3—H31110 (4)N2—C4—C3104.5 (5)
O3—N4—O4124.9 (4)O2—C6—N5117.5 (4)
O3—N4—C3117.1 (4)O2—C6—C7121.3 (4)
O4—N4—C3118.1 (5)N5—C6—C7121.2 (5)
C4—N5—C6118.5 (5)C6—C7—N6121.1 (5)
C4—N5—H5117 (3)C6—C7—C8120.7 (4)
C6—N5—H5122 (3)N6—C7—C8118.2 (4)
C7—N6—H6117 (3)O1—C8—N2120.4 (5)
C7—N6—H61112 (3)O1—C8—C7125.0 (4)
H6—N6—H61116 (4)N2—C8—C7114.5 (4)

Experimental details

(I2)(II2)
Crystal data
Chemical formulaC7H11N5O2C6H6N6O4·H2O
Mr197.21244.18
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/n
Temperature (K)295295
a, b, c (Å)7.4889 (8), 17.273 (2), 7.4073 (8)17.576 (3), 10.900 (2), 4.6738 (6)
β (°) 111.937 (6) 92.867 (8)
V3)888.8 (2)894.3 (3)
Z44
Radiation typeSynchrotron, λ = 0.85617(3) ÅSynchrotron, λ = 0.95044(2) Å
µ (mm1)0.111.39
Specimen shape, size (mm)Cylinder, 15 × 1Cylinder, 15 × 1.5
Data collection
DiffractometerESRF powder
diffractometer
ESRF powder
diffractometer
Specimen mountingSpecimen was sealed in a 1 mm diameter borosilicate glass capillarySpecimen was sealed in a 1.5 mm diameter borosilicate glass capillary
Data collection modeTransmissionTransmission
Scan methodContinuousContinuous
2θ values (°)2θmin = 4 2θmax = 44 2θstep = 0.0042θmin = 5 2θmax = 55 2θstep = 0.005
Refinement
R factors and goodness of fitRp = 0.050, Rwp = 0.064, Rexp = 0.050, χ2 = 2.103Rp = 0.057, Rwp = 0.068, Rexp = 0.043, χ2 = 3.062
No. of data points1000110001
No. of parameters135126
No. of restraints11299
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
(Δ/σ)max0.100.10

Computer programs: LSPAID (Visser et al., 1986), MRIA (Zlokazov et al., 1992), DIRDIF92, MRIA, PATSEE, POWSIM, SIRPOW.92, SHELXS96, MRIA, PLUTON92 (Spek, 1992).

 
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