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In the title compounds, C6H8N3O2+·NO3 and C5­H6­N3­O2+·­CH3SO3, respectively, the cations are almost planar; the twist of the nitr­amino group about the C—N and N—N bonds does not exceed 10°. The deviations from coplanarity are accounted for by intermolecular N—H...O interactions. The coplanarity of the NHNO2 group and the phenyl ring leads to the deformation of the nitr­amino group. The C—N—N angle and one C—C—N angle at the junction of the phenyl ring and the nitr­amino group are increased from 120° by ca 6°, whereas the other junction C—C—N angle is decreased by ca 5°. Within the nitro group, the O—N—O angle is increased by ca 5° and one O—N—N angle is decreased by ca 5°, whereas the other O—N—N angle remains almost unchanged. The cations are connected to the anions by relatively strong N—H...O hydrogen bonds [shortest H...O separations 1.77 (2)–1.81 (3) Å] and much weaker C—H...O hydrogen bonds [H...O separations 2.30 (2)–2.63 (3) Å].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101004784/gd1147sup1.cif
Contains datablocks global, III, V

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101004784/gd1147IIIsup2.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101004784/gd1147Vsup3.hkl
Contains datablock V

CCDC references: 166997; 166998

Comment top

The reaction of primary nitramines with nitrous acid provides the same products as diazotation of the corresponding parent amines. When N-methylnitramine is treated with sodium nitrite in acidic solution, methanol and N,N-dimethylnitramine are formed. The latter is formed as a result of methylation of the substrate with diazomethane, the intermediate formed in the first step of the reaction. Because of the relative stability of aromatic diazonium salts they are the principal products, often formed quantitatively, of reactions of N-arylnitramines with nitrous acid (Wright 1969). We have assumed that this rule is applicable to the N-pyridylnitramines as well. Nitration of 4-aminopyridine with mixed acids provides the corresponding nitrimine, (I), in good yield (Deady & Korytsky, 1983). Methylation of (I) gives the nitrimine, (II), as the only product; the isomeric secondary nitramine has been obtained via another route (Daszkiewicz et al., 1997). The protonation of (II) must provide a cation, (III), containing a primary nitramino group bound to the positively charged aromatic ring. Its reaction with nitrous acid should give 1-methyl-4-pyridone as the main product. To our surprise, compound (II) is resistant to the action of nitrous acid and its rapid disproportionation gives 1-methyl-4-nitraminopyridine nitrate, (III), as the only product. Compound (II) cannot be rearranged like a typical nitramine under the influence of concentrated sulfuric acid, so the stability of its protonated form in (III) is not surprising. On the other hand, the primary nitramine is susceptible to rearrangement and forms 4-amino-3-nitropyridine in strongly acidic media. In spite of this, we were able to prepare from (I) the salt 4-nitraminopyridinium methanesulfonate, (V), and determine its structure, which is presented here with the structure of (III). The result confirms Deady & Korytsky's supposition that the rearrangement of pyridylnitramines requires double protonation of a substrate. \sch

The molecular structures of (III) and (V) are shown in Figs. 1 and 2. Compound (V) crystallizes with two independent molecules, A and B, in the asymmetric unit. The pyridine ring in (III) and (V) is not affected by the methyl substituent on N1, the positive charge or the character of the N-nitro group (primary, secondary or nitrimine). The C2—C3 and C5—C6 bonds are shorter (mean 1.356 Å) than the remaining C—C bonds (mean 1.396 Å) (Fig. 1). Another common feature is a decreased valence angle centred on C4, and slightly increased angles centred on C2 and C6. It is an inductive effect of the N-nitro group that is responsible for this apparent deformation. The Ar—N bonds are of the same length in all the molecules; the differences of ca 0.01 Å are incompatible with the expected differences between the formally single [(IV) (Meiyappan et al., 1999), (III) and (V) (present work)] and double bonds [(I) and (II) (Anulewicz et al., 1993; Krygowski et al., 1996)].

An interesting geometric parameter of all aromatic nitramines is the torsion angle along the Ar—N bond. This angle may be considered a gauge of the mesomeric interaction between the nitramine π-electron system and the aromatic sextet. The nitrimines (I) and (II) are planar or nearly planar, indicating conjugation between the ring and the substituent. It can be expected that protonation of the amide atom N9 can disconnect the conjugation, but this is not what has been observed: the molecules of (III) and (V) are nearly planar. The twist of the nitramino group about the C—N and N—N bonds does not exceed 10°. The deviations from coplanarity are accounted for with non-valence interactions.

In typical secondary nitramines in the benzene (Bujak et al., 1998; Ejsmont et al., 1998) and pyridine series (Zaleski et al., 1999a,b), the nitramino group is also almost planar. It is twisted with respect to the phenyl ring by ca 60° about the C—N bond [(VI) (Zaleski et al., 1999a)]. The length of the C—N bond is ca 0.025 Å longer, whereas the length of the N—N bond is almost the same as the corresponding bonds in the primary nitrimines, (I) and (II), and nitramines, (III) and (V). The twist of the nitramino group relative to the phenyl ring is steric in origin. It is impossible to accommodate the H3CNNO2 group and the phenyl ring on the same plane. Even when the methyl group is substituted by an H atom, coplanarity of the NHNO2 group and a phenyl ring leads to the deformation of the bond angles within the NNO2 group from 120°. The C4—N7—N8 and C3—C4—N7 angles are increased by ca 6°, whereas the C5—C4—N7 angle is decreased by ca 5°. Within the nitro group, there is an increase of ca 5° in the O9—N8—O10 angle and a decrease of the O10—N8—N7 angle, whereas the O9—N8—N7 angle remains close to 120°.

It should be mentioned that in the nitrimines, (I) and (II), a slightly different deformation of the NNO2 group is observed. The C4—N7—N8 angle remains close to 120°, whereas the C3—C4—N7 angle is more enlarged (by ca 10–11°). In the NO2 group as well, it is the O9—N8—N7 angle that is increased by ca 4°, whereas the O9—N8—O10 angle remains close to 120°. The reason for the observed differences is not clear. One possible explanation is an interaction between the lone electron pair on N7 and the NO2 group. Its relatively large size may lead to the increase of the valence angle centred on N8, rather than N7 as in the nitrimines (I) and (II).

The 1-methyl-4-nitraminopyridinium cations in (III) are connected to the NO3- anions by relatively strong N—H···O hydrogen bonds [H···O 1.77 (2) Å], forming pairs (Fig. 3). These pairs are interconnected with each other by much weaker C—H···O hydrogen bonds, forming layers close to the [101] plane. In the salt, (V), each 4-nitraminopyridinium cation is connected to two CH3SO3 anions by N—H···O hydrogen bonds [N···O 2.665 (2)–2.771 (2) Å], forming chains (Fig. 4). These hydrogen bonds are assisted by much weaker C—H···O ones [C···O 3.072 (3)–3.369 (3) Å], interconnecting the molecules into a three-dimensional structure. It should be mentioned that the hydrogen bonds binding one of the two independent cations are stronger than those in the other molecule: the H···O separations for the cation of molecule B are ca 0.06–0.12 Å shorter that those for the cation of molecule A.

Experimental top

The title compounds were prepared from readily accessible N-(4-pyridyl)nitramine and its methylated derivative. 1,2-Dihydro-1-methyl-4-nitriminopyridine (3.06 g, 20 mmol) was dissolved in 20% sulfuric acid (10 ml). A saturated aqueous solution of sodium nitrite (2.80 g, 40 mmol) was slowly added dropwise at room temperature. The solution was stirred at 298–303 K until evolution of gases ceased, and then cooled. The crude product (3.95 g, 91%) was collected by filtration, washed with iced water and dried in vacuo (m.p. 431–437 K). Crystallization from methanol (45 ml) provided light-yellow prisms of (III) (2.18 g), suitable for X-ray diffraction studies. Pure (III) melted at 433–436 K with decomposition. From the mother liquor, another crop of the product was isolated; it was contaminated with some inorganic salts. Spectroscopic analysis: IR (KBr, cm-1): 3100–2350 (broad, intense band with several sub-maxima, hydrogen-bonded N—H group), 1385, 1336, 1316, 1296 and 1254 (N—O stretching vibrations in nitrate anion and NNO2 group); 1H NMR (DMSO-d6, δ, p.p.m.): 12.1 (s, N—H), 8.65 (d, 2H), 7.77 (d, 3J = 7.5 Hz, 2H, aromatic H), 4.15 (s, 3H, N-methyl group); 13C NMR (DMSO-d6, δ, p.p.m.): 153.1 (C4), 145.2 (C2, C6), 113.9 (C3, C5), 45.8 (N—CH3). N-(4-Pyridyl)nitramine (1.39 g, 0.01 mol) was dissolved in 70% aqueous methanesulfonic acid (5.0 ml) and left for 12 h at room temperature. 4-Nitraminopyridinium methanesulfonate was collected by filtration, washed with tetrahydrofuran and dried in vacuo. The product formed large, colourless prisms of (V) (m.p. 436–439 K) suitable for X-ray diffraction studies. From the liquor another crop of the salt was obtained after dilution with tetrahydrofuran and cooling (total yield 1.71 g, 73%). Spectroscopic analysis: IR (KBr, cm-1): 1451, 1338 (N—NO2 stretching vibrations), 761, 753 (N—NO2 deformations); 1H NMR (DMSO-d6, δ, p.p.m.): 10.6 (s, N—H), 8.69 (d, 2H), 7.82 (d 3J = 7.5 Hz, 2H, aromatic H), 2.49 (s, 3H, S-methyl group); 13C NMR (DMSO-d6, δ, p.p.m.): 152.8 (C4), 142.2 (C2, C6), 113.4 (C3, C5), 39.6 (S—CH3).

Refinement top

In compound (III), the H atom coordinates were refined, leading to C—H distances in the range 0.90 (3)–0.95 (2) Å and N—H distances of 0.94 (2) Å, and H—C—H angles in the range 97 (2)–115 (2)°. In compound (V), the H atoms were treated as riding, with C—H = 0.96 and N—H = 0.90 Å.

Computing details top

For both compounds, cell refinement: Kuma Diffraction Software (Kuma Diffraction, 1997); data reduction: Kuma Diffraction Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990b); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (III) showing the atom-numbering scheme and with 50% probability displacement ellipsoids. H atoms are drawn as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The structures of molecules A and B of (V) and the anion, showing the atom-numbering scheme and with 50% probability displacement ellipsoids. H atoms are drawn as small spheres of arbitrary radii.
[Figure 3] Fig. 3. The packing diagram for (III). Hydrogen bonds are shown as dashed lines.
[Figure 4] Fig. 4. The packing diagram for (V). Hydrogen bonds are shown as dashed lines.
(III) 1-Methyl-4-nitraminopyridinium nitrate top
Crystal data top
C6H8N3O2+·NO3F(000) = 448
Mr = 216.16Dx = 1.584 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.108 (1) ÅCell parameters from 35 reflections
b = 17.598 (4) Åθ = 12–14°
c = 7.246 (1) ŵ = 0.14 mm1
β = 90.33 (3)°T = 293 K
V = 906.4 (3) Å3Prism, light yellow
Z = 40.5 × 0.4 × 0.4 mm
Data collection top
Kuma KM4
diffractometer
Rint = 0.014
Radiation source: fine-focus sealed tubeθmax = 30.1°, θmin = 2.9°
Graphite monochromatorh = 1010
ω scansk = 024
2824 measured reflectionsl = 100
2640 independent reflections2 standard reflections every 50 reflections
1746 reflections with I > 2σ(I) intensity decay: 1.1%
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) = 0.141All H-atom parameters refined
S = 1.03
2640 reflections(Δ/σ)max < 0.001
168 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C6H8N3O2+·NO3V = 906.4 (3) Å3
Mr = 216.16Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.108 (1) ŵ = 0.14 mm1
b = 17.598 (4) ÅT = 293 K
c = 7.246 (1) Å0.5 × 0.4 × 0.4 mm
β = 90.33 (3)°
Data collection top
Kuma KM4
diffractometer
Rint = 0.014
2824 measured reflections2 standard reflections every 50 reflections
2640 independent reflections intensity decay: 1.1%
1746 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.141All H-atom parameters refined
S = 1.03Δρmax = 0.30 e Å3
2640 reflectionsΔρmin = 0.18 e Å3
168 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.41533 (19)0.58830 (7)0.25002 (19)0.0417 (3)
C20.3782 (2)0.66302 (8)0.2501 (2)0.0430 (4)
C30.5025 (2)0.71522 (8)0.1821 (2)0.0415 (3)
C40.6729 (2)0.68986 (8)0.1098 (2)0.0366 (3)
C50.7077 (2)0.61148 (9)0.1089 (2)0.0439 (4)
C60.5790 (2)0.56292 (8)0.1795 (2)0.0453 (4)
N70.81323 (19)0.73406 (7)0.0355 (2)0.0443 (3)
N80.82239 (19)0.81143 (7)0.0425 (2)0.0434 (3)
O100.95126 (19)0.84000 (7)0.0420 (2)0.0577 (4)
O90.7056 (2)0.84584 (7)0.1291 (2)0.0704 (5)
C110.2770 (3)0.53398 (11)0.3242 (4)0.0587 (5)
N121.18647 (18)0.62500 (7)0.1671 (2)0.0434 (3)
O131.3313 (2)0.61432 (7)0.2549 (2)0.0708 (5)
O141.1052 (2)0.57168 (8)0.0930 (3)0.0787 (5)
O151.12243 (18)0.69110 (7)0.1524 (2)0.0592 (4)
H60.597 (3)0.5096 (12)0.185 (3)0.053 (5)*
H20.264 (3)0.6786 (11)0.303 (3)0.048 (5)*
H50.817 (3)0.5920 (12)0.061 (3)0.050 (5)*
H30.476 (3)0.7653 (11)0.189 (3)0.049 (5)*
H11A0.186 (5)0.5225 (19)0.241 (5)0.116 (11)*
H11B0.236 (4)0.5499 (18)0.438 (4)0.101 (10)*
H11C0.335 (4)0.4870 (19)0.324 (4)0.101 (9)*
H70.918 (3)0.7143 (14)0.026 (3)0.075 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0441 (7)0.0308 (6)0.0504 (7)0.0002 (5)0.0050 (6)0.0020 (5)
C20.0401 (7)0.0335 (7)0.0557 (9)0.0037 (6)0.0090 (7)0.0033 (6)
C30.0405 (7)0.0287 (6)0.0554 (9)0.0045 (5)0.0058 (6)0.0027 (6)
C40.0357 (7)0.0328 (6)0.0414 (7)0.0018 (5)0.0005 (5)0.0031 (5)
C50.0395 (7)0.0354 (7)0.0568 (9)0.0080 (6)0.0046 (7)0.0069 (6)
C60.0491 (9)0.0292 (6)0.0576 (10)0.0062 (6)0.0028 (7)0.0043 (6)
N70.0414 (7)0.0335 (6)0.0582 (8)0.0021 (5)0.0121 (6)0.0029 (5)
N80.0416 (7)0.0351 (6)0.0537 (8)0.0005 (5)0.0029 (6)0.0003 (5)
O100.0548 (7)0.0471 (7)0.0714 (8)0.0068 (6)0.0152 (6)0.0083 (6)
O90.0620 (8)0.0356 (6)0.1141 (13)0.0024 (6)0.0335 (8)0.0149 (7)
C110.0632 (12)0.0376 (9)0.0754 (14)0.0089 (8)0.0174 (11)0.0025 (9)
N120.0365 (6)0.0347 (6)0.0591 (8)0.0014 (5)0.0070 (6)0.0003 (6)
O130.0555 (8)0.0398 (6)0.1174 (13)0.0049 (5)0.0418 (8)0.0006 (7)
O140.0670 (9)0.0476 (7)0.1219 (14)0.0046 (6)0.0428 (9)0.0229 (8)
O150.0518 (7)0.0361 (6)0.0901 (10)0.0057 (5)0.0224 (7)0.0043 (6)
Geometric parameters (Å, º) top
N1—C21.341 (2)C6—H60.95 (2)
N1—C61.350 (2)N7—N81.364 (2)
N1—C111.475 (2)N7—H70.94 (2)
C2—C31.369 (2)N8—O91.206 (2)
C2—H20.94 (2)N8—O101.214 (2)
C3—C41.396 (2)C11—H11A0.90 (3)
C3—H30.90 (2)C11—H11B0.92 (3)
C4—N71.377 (2)C11—H11C0.93 (3)
C4—C51.401 (2)N12—O141.227 (2)
C5—C61.354 (2)N12—O131.227 (2)
C5—H50.92 (2)N12—O151.254 (2)
C2—N1—C6119.7 (1)C5—C6—H6123 (1)
C2—N1—C11120.2 (1)N8—N7—C4125.7 (1)
C6—N1—C11120.1 (1)N8—N7—H7111 (1)
N1—C2—C3122.0 (1)C4—N7—H7124 (2)
N1—C2—H2117 (1)O9—N8—O10125.3 (1)
C3—C2—H2121 (1)O9—N8—N7119.2 (1)
C2—C3—C4119.0 (1)O10—N8—N7115.5 (1)
C2—C3—H3120 (1)N1—C11—H11A112 (2)
C4—C3—H3121 (1)N1—C11—H11B110 (2)
N7—C4—C3126.8 (1)H11A—C11—H11B116 (3)
N7—C4—C5115.2 (1)N1—C11—H11C106 (2)
C3—C4—C5118.0 (1)H11A—C11—H11C97 (2)
C6—C5—C4120.0 (1)H11B—C11—H11C115 (3)
C6—C5—H5119 (1)O14—N12—O13120.5 (1)
C4—C5—H5121 (1)O14—N12—O15120.0 (1)
N1—C6—C5121.3 (1)O13—N12—O15119.5 (1)
N1—C6—H6115 (1)
C6—N1—C2—C30.7 (3)C2—N1—C6—C50.2 (3)
C11—N1—C2—C3179.8 (2)C11—N1—C6—C5179.3 (2)
N1—C2—C3—C40.3 (3)C4—C5—C6—N10.7 (3)
C2—C3—C4—N7179.7 (2)C3—C4—N7—N89.8 (3)
C2—C3—C4—C50.6 (2)C5—C4—N7—N8171.0 (2)
N7—C4—C5—C6179.7 (2)C4—N7—N8—O94.5 (3)
C3—C4—C5—C61.0 (2)C4—N7—N8—O10175.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N7—H7···O150.94 (2)1.77 (2)2.700 (2)171 (2)
C3—H3···O13i0.90 (2)2.39 (2)3.270 (2)165 (2)
C2—H2···O15i0.94 (2)2.52 (2)3.226 (2)131 (2)
C2—H2···O10i0.94 (2)2.51 (2)3.396 (2)156 (2)
C5—H5···O140.92 (2)2.37 (2)3.265 (2)166 (2)
C6—H6···O13ii0.95 (2)2.30 (2)3.229 (2)168 (2)
C11—H11C···O9iii0.93 (3)2.52 (3)3.330 (2)146 (2)
Symmetry codes: (i) x1, y+3/2, z+1/2; (ii) x+2, y+1, z; (iii) x+1, y1/2, z+1/2.
(V) 4-Nitraminopyridinium methanesulphonate top
Crystal data top
C5H6N3O2+·CH3SO3F(000) = 976
Mr = 235.22Dx = 1.627 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 11.824 (2) ÅCell parameters from 27 reflections
b = 8.138 (2) Åθ = 10–14°
c = 20.125 (4) ŵ = 0.35 mm1
β = 97.36 (3)°T = 293 K
V = 1920.5 (7) Å3Prism, colourless
Z = 80.45 × 0.40 × 0.35 mm
Data collection top
Kuma KM4
diffractometer
Rint = 0.017
Radiation source: fine-focus sealed tubeθmax = 25.1°, θmin = 1.9°
Graphite monochromatorh = 1314
ω scansk = 90
3500 measured reflectionsl = 230
3402 independent reflections2 standard reflections every 50 reflections
3022 reflections with I > 2σ(I) intensity decay: 2.0%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.099
S = 1.08(Δ/σ)max = 0.001
3402 reflectionsΔρmax = 0.32 e Å3
272 parametersΔρmin = 0.36 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0140 (10)
Crystal data top
C5H6N3O2+·CH3SO3V = 1920.5 (7) Å3
Mr = 235.22Z = 8
Monoclinic, P21/nMo Kα radiation
a = 11.824 (2) ŵ = 0.35 mm1
b = 8.138 (2) ÅT = 293 K
c = 20.125 (4) Å0.45 × 0.40 × 0.35 mm
β = 97.36 (3)°
Data collection top
Kuma KM4
diffractometer
Rint = 0.017
3500 measured reflections2 standard reflections every 50 reflections
3402 independent reflections intensity decay: 2.0%
3022 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.08Δρmax = 0.32 e Å3
3402 reflectionsΔρmin = 0.36 e Å3
272 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S1A0.96655 (4)0.16340 (6)0.88431 (2)0.03100 (16)
O1A0.89121 (13)0.2008 (2)0.82329 (8)0.0456 (4)
O2A1.02645 (14)0.0106 (2)0.88084 (9)0.0493 (4)
O3A1.04239 (12)0.3017 (2)0.90336 (9)0.0469 (4)
C1A0.8786 (2)0.1461 (3)0.94767 (12)0.0481 (6)
H1AB0.82650.05630.93760.058*
H1AC0.92460.12640.98980.058*
H1AD0.83630.24620.95030.058*
S1B0.78304 (4)0.15907 (6)0.60078 (2)0.03083 (16)
O1B0.82024 (14)0.3109 (2)0.57272 (9)0.0544 (5)
O2B0.81240 (14)0.1544 (2)0.67325 (8)0.0494 (4)
O3B0.82175 (14)0.0152 (2)0.56889 (9)0.0548 (5)
C1B0.63379 (18)0.1612 (3)0.58461 (12)0.0425 (5)
H1BB0.61080.16420.53710.051*
H1BC0.60380.06400.60300.051*
H1BD0.60500.25660.60490.051*
N1A0.93370 (15)0.4883 (2)0.75694 (9)0.0380 (4)
H1AE0.91680.38300.76520.046*
C6A0.85229 (17)0.5873 (3)0.72760 (11)0.0364 (5)
H6AA0.77640.54590.71550.044*
C5A0.87597 (16)0.7470 (3)0.71478 (10)0.0339 (4)
H5AA0.81720.81810.69370.041*
C4A0.98599 (16)0.8073 (2)0.73226 (9)0.0284 (4)
C3A1.06987 (18)0.7009 (3)0.76228 (11)0.0384 (5)
H3AB1.14680.73830.77410.046*
C2A1.03998 (19)0.5433 (3)0.77403 (12)0.0430 (5)
H2AB1.09670.46950.79540.052*
N7A1.00054 (14)0.9713 (2)0.71823 (9)0.0339 (4)
H7AA0.93781.02830.70200.041*
N8A1.10057 (16)1.0538 (2)0.72647 (9)0.0406 (4)
O9A1.18902 (14)0.9780 (2)0.73772 (12)0.0655 (6)
O10A1.09294 (16)1.2027 (2)0.71938 (10)0.0577 (5)
N1B1.00488 (17)0.5026 (3)0.58539 (10)0.0466 (5)
H1BE0.95550.41890.58690.056*
C6B1.1168 (2)0.4755 (3)0.60025 (12)0.0464 (6)
H6BA1.14360.36700.61260.056*
C5B1.19288 (19)0.5990 (3)0.59804 (11)0.0384 (5)
H5BA1.27330.57860.60770.046*
C4B1.15278 (16)0.7576 (2)0.58145 (9)0.0288 (4)
C3B1.03578 (17)0.7822 (3)0.56593 (10)0.0366 (5)
H3BB1.00580.88910.55360.044*
C2B0.96588 (19)0.6515 (3)0.56859 (11)0.0440 (6)
H2BB0.88510.66730.55790.053*
N7B1.23622 (15)0.8752 (2)0.58183 (9)0.0353 (4)
H7BA1.30900.84040.58620.042*
N8B1.21785 (17)1.0401 (2)0.57608 (9)0.0403 (4)
O9B1.12074 (15)1.0926 (2)0.57340 (10)0.0551 (5)
O10B1.30284 (16)1.1236 (2)0.57564 (11)0.0619 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0245 (3)0.0323 (3)0.0355 (3)0.00104 (19)0.00121 (19)0.0028 (2)
O1A0.0370 (8)0.0547 (10)0.0421 (8)0.0062 (7)0.0066 (7)0.0128 (7)
O2A0.0459 (9)0.0395 (9)0.0632 (11)0.0092 (7)0.0099 (8)0.0018 (8)
O3A0.0300 (8)0.0443 (9)0.0649 (10)0.0080 (7)0.0003 (7)0.0052 (8)
C1A0.0453 (13)0.0536 (14)0.0477 (13)0.0010 (11)0.0150 (11)0.0026 (11)
S1B0.0255 (3)0.0341 (3)0.0327 (3)0.00245 (19)0.00313 (19)0.00479 (19)
O1B0.0411 (9)0.0534 (10)0.0681 (11)0.0122 (8)0.0045 (8)0.0200 (9)
O2B0.0462 (9)0.0675 (11)0.0333 (8)0.0159 (8)0.0003 (7)0.0051 (8)
O3B0.0493 (10)0.0572 (11)0.0579 (11)0.0190 (8)0.0066 (8)0.0097 (8)
C1B0.0282 (10)0.0483 (13)0.0504 (13)0.0000 (9)0.0032 (9)0.0029 (10)
N1A0.0386 (10)0.0296 (9)0.0471 (10)0.0004 (8)0.0103 (8)0.0064 (8)
C6A0.0285 (10)0.0390 (12)0.0427 (11)0.0021 (9)0.0081 (8)0.0025 (9)
C5A0.0264 (10)0.0371 (11)0.0380 (11)0.0041 (8)0.0038 (8)0.0039 (9)
C4A0.0309 (10)0.0300 (10)0.0248 (9)0.0027 (8)0.0058 (7)0.0009 (7)
C3A0.0304 (10)0.0375 (12)0.0451 (12)0.0007 (9)0.0034 (9)0.0049 (9)
C2A0.0386 (12)0.0403 (12)0.0483 (13)0.0082 (10)0.0005 (10)0.0104 (10)
N7A0.0299 (9)0.0297 (9)0.0415 (9)0.0005 (7)0.0020 (7)0.0029 (7)
N8A0.0387 (10)0.0360 (10)0.0478 (11)0.0066 (8)0.0079 (8)0.0017 (8)
O9A0.0318 (9)0.0533 (11)0.1107 (16)0.0043 (8)0.0062 (9)0.0103 (11)
O10A0.0635 (11)0.0316 (9)0.0801 (13)0.0104 (8)0.0173 (10)0.0011 (8)
N1B0.0504 (12)0.0461 (11)0.0457 (11)0.0200 (10)0.0154 (9)0.0052 (9)
C6B0.0572 (15)0.0306 (11)0.0521 (14)0.0043 (10)0.0103 (11)0.0024 (10)
C5B0.0378 (11)0.0330 (11)0.0448 (12)0.0032 (9)0.0063 (9)0.0035 (9)
C4B0.0310 (10)0.0293 (10)0.0264 (9)0.0006 (8)0.0050 (7)0.0002 (8)
C3B0.0303 (10)0.0395 (12)0.0400 (11)0.0048 (9)0.0044 (8)0.0009 (9)
C2B0.0309 (11)0.0589 (15)0.0434 (12)0.0069 (10)0.0093 (9)0.0067 (11)
N7B0.0303 (9)0.0287 (9)0.0463 (10)0.0023 (7)0.0028 (7)0.0055 (7)
N8B0.0490 (11)0.0304 (9)0.0406 (10)0.0002 (9)0.0026 (8)0.0019 (8)
O9B0.0538 (10)0.0346 (9)0.0762 (12)0.0132 (8)0.0057 (9)0.0031 (8)
O10B0.0598 (11)0.0400 (10)0.0838 (13)0.0183 (9)0.0009 (10)0.0074 (9)
Geometric parameters (Å, º) top
S1A—O2A1.437 (2)C3A—C2A1.359 (3)
S1A—O1A1.454 (2)C3A—H3AB0.9600
S1A—O3A1.459 (2)C2A—H2AB0.9601
S1A—C1A1.752 (2)N7A—N8A1.352 (2)
C1A—H1AB0.9600N7A—H7AA0.9000
C1A—H1AC0.9601N8A—O9A1.210 (3)
C1A—H1AD0.9600N8A—O10A1.222 (3)
S1B—O3B1.438 (2)N1B—C2B1.325 (3)
S1B—O1B1.450 (2)N1B—C6B1.337 (3)
S1B—O2B1.456 (2)N1B—H1BE0.9000
S1B—C1B1.753 (2)C6B—C5B1.354 (3)
C1B—H1BB0.9600C6B—H6BA0.9600
C1B—H1BC0.9600C5B—C4B1.400 (3)
C1B—H1BD0.9600C5B—H5BA0.9601
N1A—C6A1.334 (3)C4B—N7B1.374 (3)
N1A—C2A1.337 (3)C4B—C3B1.393 (3)
N1A—H1AE0.9000C3B—C2B1.352 (3)
C6A—C5A1.361 (3)C3B—H3BB0.9600
C6A—H6AA0.9600C2B—H2BB0.9600
C5A—C4A1.393 (3)N7B—N8B1.361 (2)
C5A—H5AA0.9600N7B—H7BA0.9000
C4A—N7A1.380 (3)N8B—O10B1.214 (2)
C4A—C3A1.394 (3)N8B—O9B1.220 (2)
O2A—S1A—O1A113.1 (1)C2A—C3A—C4A118.4 (2)
O2A—S1A—O3A112.9 (1)C2A—C3A—H3AB121.0
O1A—S1A—O3A110.5 (1)C4A—C3A—H3AB120.6
O2A—S1A—C1A108.0 (1)N1A—C2A—C3A121.9 (2)
O1A—S1A—C1A106.0 (1)N1A—C2A—H2AB119.1
O3A—S1A—C1A105.8 (1)C3A—C2A—H2AB119.1
S1A—C1A—H1AB109.4N8A—N7A—C4A125.9 (2)
S1A—C1A—H1AC109.5N8A—N7A—H7AA117.1
H1AB—C1A—H1AC109.5C4A—N7A—H7AA117.0
S1A—C1A—H1AD109.5O9A—N8A—O10A125.2 (2)
H1AB—C1A—H1AD109.5O9A—N8A—N7A119.4 (2)
H1AC—C1A—H1AD109.5O10A—N8A—N7A115.3 (2)
O3B—S1B—O1B113.0 (1)C2B—N1B—C6B120.7 (2)
O3B—S1B—O2B112.2 (1)C2B—N1B—H1BE119.6
O1B—S1B—O2B111.5 (1)C6B—N1B—H1BE119.7
O3B—S1B—C1B107.2 (1)N1B—C6B—C5B120.9 (2)
O1B—S1B—C1B105.5 (1)N1B—C6B—H6BA119.6
O2B—S1B—C1B106.9 (1)C5B—C6B—H6BA119.5
S1B—C1B—H1BB109.6C6B—C5B—C4B119.1 (2)
S1B—C1B—H1BC109.4C6B—C5B—H5BA120.7
H1BB—C1B—H1BC109.5C4B—C5B—H5BA120.3
S1B—C1B—H1BD109.4N7B—C4B—C3B126.4 (2)
H1BB—C1B—H1BD109.5N7B—C4B—C5B114.8 (2)
H1BC—C1B—H1BD109.5C3B—C4B—C5B118.8 (2)
C6A—N1A—C2A120.9 (2)C2B—C3B—C4B118.2 (2)
C6A—N1A—H1AE119.5C2B—C3B—H3BB121.1
C2A—N1A—H1AE119.6C4B—C3B—H3BB120.7
N1A—C6A—C5A120.4 (2)N1B—C2B—C3B122.3 (2)
N1A—C6A—H6AA119.8N1B—C2B—H2BB118.9
C5A—C6A—H6AA119.7C3B—C2B—H2BB118.8
C6A—C5A—C4A119.8 (2)N8B—N7B—C4B125.4 (2)
C6A—C5A—H5AA120.3N8B—N7B—H7BA117.3
C4A—C5A—H5AA119.9C4B—N7B—H7BA117.3
N7A—C4A—C5A115.2 (2)O10B—N8B—O9B125.3 (2)
N7A—C4A—C3A126.1 (2)O10B—N8B—N7B115.4 (2)
C5A—C4A—C3A118.7 (2)O9B—N8B—N7B119.2 (2)
C2A—N1A—C6A—C5A0.3 (3)C2B—N1B—C6B—C5B0.5 (3)
N1A—C6A—C5A—C4A0.2 (3)N1B—C6B—C5B—C4B1.5 (3)
C6A—C5A—C4A—N7A178.9 (2)C6B—C5B—C4B—N7B178.8 (2)
C6A—C5A—C4A—C3A0.5 (3)C6B—C5B—C4B—C3B1.7 (3)
N7A—C4A—C3A—C2A178.3 (2)N7B—C4B—C3B—C2B179.6 (2)
C5A—C4A—C3A—C2A0.9 (3)C5B—C4B—C3B—C2B1.0 (3)
C6A—N1A—C2A—C3A0.2 (3)C6B—N1B—C2B—C3B0.3 (3)
C4A—C3A—C2A—N1A0.8 (3)C4B—C3B—C2B—N1B0.1 (3)
C5A—C4A—N7A—N8A175.3 (2)C3B—C4B—N7B—N8B9.6 (3)
C3A—C4A—N7A—N8A5.4 (3)C5B—C4B—N7B—N8B170.9 (2)
C4A—N7A—N8A—O9A11.6 (3)C4B—N7B—N8B—O10B178.0 (2)
C4A—N7A—N8A—O10A170.9 (2)C4B—N7B—N8B—O9B3.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N7A—H7AA···O2Bi0.901.832.734 (2)176
N7B—H7BA···O3Aii0.901.772.665 (2)172
N1A—H1AE···O1A0.901.942.771 (2)154
N1B—H1BE···O1B0.901.822.668 (2)157
C3A—H3AB···O9A0.962.162.737 (3)117
C3B—H3BB···O9B0.962.152.716 (3)117
C5A—H5AA···O1Aiii0.962.623.176 (3)117
C6A—H6AA···O1Aiii0.962.393.072 (3)127
C3B—H3BB···O3Bi0.962.463.169 (3)131
C5B—H5BA···O2Aii0.962.413.369 (3)173
C6B—H6BA···O10Aiv0.962.663.306 (3)125
Symmetry codes: (i) x, y+1, z; (ii) x+5/2, y+1/2, z+3/2; (iii) x+3/2, y+1/2, z+3/2; (iv) x, y1, z.

Experimental details

(III)(V)
Crystal data
Chemical formulaC6H8N3O2+·NO3C5H6N3O2+·CH3SO3
Mr216.16235.22
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/n
Temperature (K)293293
a, b, c (Å)7.108 (1), 17.598 (4), 7.246 (1)11.824 (2), 8.138 (2), 20.125 (4)
β (°) 90.33 (3) 97.36 (3)
V3)906.4 (3)1920.5 (7)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.140.35
Crystal size (mm)0.5 × 0.4 × 0.40.45 × 0.40 × 0.35
Data collection
DiffractometerKuma KM4
diffractometer
Kuma KM4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2824, 2640, 1746 3500, 3402, 3022
Rint0.0140.017
(sin θ/λ)max1)0.7050.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.141, 1.03 0.033, 0.099, 1.08
No. of reflections26403402
No. of parameters168272
H-atom treatmentAll H-atom parameters refinedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.180.32, 0.36

Computer programs: Kuma Diffraction Software (Kuma Diffraction, 1997), Kuma Diffraction Software, SHELXS97 (Sheldrick, 1990a), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1990b), SHELXL97.

Selected geometric parameters (Å, º) for (III) top
C4—N71.377 (2)N8—O91.206 (2)
N7—N81.364 (2)N8—O101.214 (2)
C2—N1—C6119.7 (1)C6—C5—C4120.0 (1)
N1—C2—C3122.0 (1)N1—C6—C5121.3 (1)
C2—C3—C4119.0 (1)N8—N7—C4125.7 (1)
N7—C4—C3126.8 (1)O9—N8—O10125.3 (1)
N7—C4—C5115.2 (1)O9—N8—N7119.2 (1)
C3—C4—C5118.0 (1)O10—N8—N7115.5 (1)
C3—C4—N7—N89.8 (3)C4—N7—N8—O94.5 (3)
C5—C4—N7—N8171.0 (2)C4—N7—N8—O10175.3 (2)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N7—H7···O150.94 (2)1.77 (2)2.700 (2)171 (2)
C3—H3···O13i0.90 (2)2.39 (2)3.270 (2)165 (2)
C2—H2···O15i0.94 (2)2.52 (2)3.226 (2)131 (2)
C2—H2···O10i0.94 (2)2.51 (2)3.396 (2)156 (2)
C5—H5···O140.92 (2)2.37 (2)3.265 (2)166 (2)
C6—H6···O13ii0.95 (2)2.30 (2)3.229 (2)168 (2)
C11—H11C···O9iii0.93 (3)2.52 (3)3.330 (2)146 (2)
Symmetry codes: (i) x1, y+3/2, z+1/2; (ii) x+2, y+1, z; (iii) x+1, y1/2, z+1/2.
Selected geometric parameters (Å, º) for (V) top
C4A—N7A1.380 (3)C4B—N7B1.374 (3)
N7A—N8A1.352 (2)N7B—N8B1.361 (2)
N8A—O9A1.210 (3)N8B—O10B1.214 (2)
N8A—O10A1.222 (3)N8B—O9B1.220 (2)
C6A—N1A—C2A120.9 (2)C2B—N1B—C6B120.7 (2)
N1A—C6A—C5A120.4 (2)N1B—C6B—C5B120.9 (2)
C6A—C5A—C4A119.8 (2)C6B—C5B—C4B119.1 (2)
N7A—C4A—C5A115.2 (2)N7B—C4B—C3B126.4 (2)
N7A—C4A—C3A126.1 (2)N7B—C4B—C5B114.8 (2)
C5A—C4A—C3A118.7 (2)C3B—C4B—C5B118.8 (2)
C2A—C3A—C4A118.4 (2)C2B—C3B—C4B118.2 (2)
N1A—C2A—C3A121.9 (2)N1B—C2B—C3B122.3 (2)
N8A—N7A—C4A125.9 (2)N8B—N7B—C4B125.4 (2)
O9A—N8A—O10A125.2 (2)O10B—N8B—O9B125.3 (2)
O9A—N8A—N7A119.4 (2)O10B—N8B—N7B115.4 (2)
O10A—N8A—N7A115.3 (2)O9B—N8B—N7B119.2 (2)
C5A—C4A—N7A—N8A175.3 (2)C3B—C4B—N7B—N8B9.6 (3)
C3A—C4A—N7A—N8A5.4 (3)C5B—C4B—N7B—N8B170.9 (2)
C4A—N7A—N8A—O9A11.6 (3)C4B—N7B—N8B—O10B178.0 (2)
C4A—N7A—N8A—O10A170.9 (2)C4B—N7B—N8B—O9B3.6 (3)
Hydrogen-bond geometry (Å, º) for (V) top
D—H···AD—HH···AD···AD—H···A
N7A—H7AA···O2Bi0.901.832.734 (2)176
N7B—H7BA···O3Aii0.901.772.665 (2)172
N1A—H1AE···O1A0.901.942.771 (2)154
N1B—H1BE···O1B0.901.822.668 (2)157
C3A—H3AB···O9A0.962.162.737 (3)117
C3B—H3BB···O9B0.962.152.716 (3)117
C5A—H5AA···O1Aiii0.962.623.176 (3)117
C6A—H6AA···O1Aiii0.962.393.072 (3)127
C3B—H3BB···O3Bi0.962.463.169 (3)131
C5B—H5BA···O2Aii0.962.413.369 (3)173
C6B—H6BA···O10Aiv0.962.663.306 (3)125
Symmetry codes: (i) x, y+1, z; (ii) x+5/2, y+1/2, z+3/2; (iii) x+3/2, y+1/2, z+3/2; (iv) x, y1, z.
 

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