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The mol­ecular structures of eth­yl 5-amino-3-(4,6-dimethyl­pyrimidin-2-ylamino)-1-meth­yl-1H-pyrazole-4-carboxyl­ate, C13H18N6O2, (I), and eth­yl 5-amino-3-(4,6-dimethyl­pyrimidin-2-ylamino)-1-(2-nitro­phenyl­sulfon­yl)-1H-pyrazole-4-carboxyl­­ate, C18H19N7O6S, (II), have been determined. There are two intra­molecular N—H...O bonds and one inter­molecular N—H...O hydrogen bond in (I). The rings formed by the N—H...O hydrogen bonds are almost planar. In (II), three intra­molecular N—H...O hydrogen bonds exist.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105007821/av1221sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105007821/av1221Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105007821/av1221IIsup3.hkl
Contains datablock II

CCDC references: 273042; 273043

Comment top

Many pyrazoles and pyrimidines show fungicidal or herbicidal activities (Malhotra et al., 1997; Takao et al., 1994; Ohvchi & Okada, 1998; Kleschick et al., 1992). Some of these kinds of compounds, such as flumetsulam, metosulam and pyrazosulfuron, have been commercialized as agrochemicals. The pyrazole and pyrimidine derivatives have also been investigated extensively in pharmacological applications (Kees et al., 1996; Lesyk et al., 1998). In order to discover further biologically active pyrazole and pyrimidine compounds, a series of novel pyrimidinylaminopyrazole derivatives were designed and synthesized. Some of them showed high fungicidal or herbicidal activity. It has been reported that the position of the acid H atom on a pyrazole ring is not stationary. For example, for 3{5}-substituted pyrazoles, the position of the acid H atom could be correlated with the Hammett σm parameter of the 3{5}-substituent. Substituents with positive σm values prefer the 3-positon, while those with negative σm adopt the 5-position (Lopez et al., 1993; Malcolm et al., 1996). It is possible that the substitution reaction occurs at the two endocyclic N atoms simultaneously, and thus a pair of isomers could be obtained. For instance, when the 4-position substitutents are cyano and ethoxycarbonyl groups, respectively, the ratios of isomer (III) to isomer (IV) are 100:83 and 100:1.13 (Ren et al., 2004). When ethyl 3-(4,6-dimethylpyrimidin-2-ylamino)-5-amino-1H-pyrazole- 4-carboxylate was reacted with methyl iodide and 2-nitrobenzenesulfonyl chloride, only one primary product was obtained in each case, which was found by X-ray determination to be (I) and (II), respectively (Figs. 1 and 2). According to Fig. 2, the nitro group in the ortho-position is twisted by 48.07 (13)° from the plane of the phenyl ring. This tilting of the nitro group avoids unfavourable steric contacts with atom O1 (Jeyakanthan et al., 1999). Similarly, the interplanar angle between the phenyl ring F' and the pyrazole ring A' is 77.08 (9)°. The molecular structure of (II) is stabilized by three N—H···O-type intramolecular hydrogen bonds (Table 4). Rings A', B', C' and D' are not coplanar; the dihedral angles between the the planes of rings B', C' and D' and the palne of the pyrazole ring A' are 2.4 (5), 1.7 (6) and 4.4 (5)°, respectively. The molecular structure of (I) is stabilized by two intramolecular N—H···O hydrogen bonds and one intermolecular N—H···O hydrogen bond (Table 2). The hydrogen bonds of the molecular structure of (I) are longer than the corresponding bonds of (II), but rings A, B and C are almost coplanar. For (I) and (II), the dihedral angles between the pyrimidine ring and the pyrazole ring are 7.9 (2) and 14.1 (1)°, respectively.

Experimental top

Ethyl 3-(4,6-dimethylpyrimidin-2-ylamino)-5-amino-1H-pyrazole-4-carboxylate (0.69 g, 2.5 mmol) and anhydrous kalium carbonate (0.41 g, 3 mmol) were mixed in acetone (30 ml) and kept in ice-cold conditions. A solution of 2-nitrobenzene-1-sulfonyl chloride (0.66 g, 3 mmol) in acetone (5 ml) was added dropwise with stirring for 10 min. The mixture was stirred at room temperature overnight, and then the solvent was evaporated to dryness in a vacuum. The residue was washed with water. The resulting pale-yellow precipitate was filtered off and recrystallized from ethanol, and well shaped crystals of (II) were obtained. Compound (I) was synthesized using the same procedure, except that dimethyl sulfate was used as a starting material, and the product was purified by silica column chromatography (eluant ethyl acetate/petroleum ether 1:5) and recrystallized from ethanol. Crystals of (I) and (II) suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared.

Refinement top

H atoms attached to C atoms were included in calculated positions and treated as riding atoms using SHELXL97 default parameters [C—H = 0.93, 0.96 or 0.97 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C). For (I), the H atoms of atoms N3 and N6 were located from difference Fourier maps and refined isotropically, with the N—H distance restrained to 0.86 (1) Å. For (II), the H atoms of atoms N3 and N4 were located from difference Fourier maps and refined isotropically with the N—H distance restrained to 0.87 (1).

Computing details top

For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at 50% probability level.
[Figure 2] Fig. 2. A view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at 50% probability level.
[Figure 3] Fig. 3. A packing diagram of (I), showing the intermolecular hydrogen bonds as dashed lines. [Symmetry code: (A) 2 − x, 1/2 + y, 1/2 − z.]
(I) Ethyl 5-amino-3-(4,6-dimethylpyrimidin-2-ylamino)-1-methyl-1H- pyrazole-4-carboxylate top
Crystal data top
C13H18N6O2Dx = 1.261 Mg m3
Mr = 290.33Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 825 reflections
a = 7.5466 (15) Åθ = 2.4–25.5°
b = 9.042 (2) ŵ = 0.09 mm1
c = 22.412 (8) ÅT = 293 K
V = 1529.3 (7) Å3Prism, yellow
Z = 40.38 × 0.30 × 0.20 mm
F(000) = 616
Data collection top
Bruker Smart 1000 CCD area detector
diffractometer
1629 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.048
Graphite monochromatorθmax = 26.5°, θmin = 2.4°
ϕ and ω scansh = 59
7861 measured reflectionsk = 1111
1836 independent reflectionsl = 2822
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)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101 w = 1/[σ2(Fo2) + (0.0529P)2 + 0.2041P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max = 0.001
1836 reflectionsΔρmax = 0.17 e Å3
204 parametersΔρmin = 0.13 e Å3
3 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.014 (2)
Crystal data top
C13H18N6O2V = 1529.3 (7) Å3
Mr = 290.33Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.5466 (15) ŵ = 0.09 mm1
b = 9.042 (2) ÅT = 293 K
c = 22.412 (8) Å0.38 × 0.30 × 0.20 mm
Data collection top
Bruker Smart 1000 CCD area detector
diffractometer
1629 reflections with I > 2σ(I)
7861 measured reflectionsRint = 0.048
1836 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0383 restraints
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.17 e Å3
1836 reflectionsΔρmin = 0.13 e Å3
204 parameters
Special details top

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
N11.1476 (3)0.0360 (2)0.14949 (8)0.0443 (5)
N20.9392 (3)0.0621 (2)0.07917 (9)0.0510 (5)
N30.8989 (3)0.1682 (2)0.11810 (8)0.0444 (5)
H30.801 (2)0.168 (3)0.0981 (10)0.053*
N41.0657 (2)0.3276 (2)0.18130 (8)0.0416 (4)
N51.0323 (3)0.4665 (2)0.20579 (8)0.0418 (4)
N60.8102 (3)0.6522 (3)0.20842 (10)0.0528 (6)
H6A0.840 (4)0.678 (3)0.2439 (6)0.063*
H6B0.7034 (19)0.672 (3)0.1975 (11)0.063*
O10.5761 (2)0.30987 (19)0.09362 (7)0.0466 (4)
O20.5227 (2)0.5323 (2)0.13480 (9)0.0638 (5)
C11.2426 (3)0.0891 (3)0.14458 (11)0.0483 (6)
C21.1893 (4)0.2033 (3)0.10863 (11)0.0557 (7)
H21.25570.28970.10590.067*
C31.0336 (4)0.1864 (3)0.07637 (11)0.0558 (7)
C41.0024 (3)0.0425 (3)0.11612 (9)0.0391 (5)
C50.9224 (3)0.2980 (2)0.14997 (9)0.0361 (5)
C60.7943 (3)0.4123 (3)0.15343 (9)0.0386 (5)
C70.8723 (3)0.5186 (3)0.19083 (9)0.0396 (5)
C80.6205 (3)0.4271 (3)0.12755 (10)0.0415 (5)
C90.4022 (3)0.3112 (3)0.06501 (12)0.0554 (7)
H9A0.38980.39770.03980.066*
H9B0.30900.31270.09480.066*
C100.3915 (4)0.1735 (3)0.02862 (11)0.0615 (7)
H10A0.47660.17820.00320.092*
H10B0.27460.16430.01220.092*
H10C0.41640.08950.05340.092*
C111.4110 (4)0.0949 (4)0.17995 (16)0.0745 (9)
H11A1.45330.00380.18680.112*
H11B1.49860.14980.15820.112*
H11C1.38910.14250.21750.112*
C120.9660 (6)0.3055 (4)0.03575 (16)0.0945 (12)
H12A0.83990.31410.04010.142*
H12B1.02080.39790.04600.142*
H12C0.99410.28090.00480.142*
C131.1718 (3)0.5367 (3)0.23903 (11)0.0508 (6)
H13A1.14450.63960.24420.076*
H13B1.28150.52700.21770.076*
H13C1.18250.49040.27740.076*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0425 (10)0.0417 (10)0.0485 (9)0.0101 (9)0.0048 (8)0.0047 (9)
N20.0598 (12)0.0428 (11)0.0503 (10)0.0072 (10)0.0097 (10)0.0087 (9)
N30.0455 (10)0.0396 (10)0.0481 (10)0.0110 (9)0.0131 (9)0.0077 (9)
N40.0399 (9)0.0376 (10)0.0473 (10)0.0077 (9)0.0062 (8)0.0038 (9)
N50.0407 (10)0.0383 (10)0.0465 (9)0.0058 (9)0.0066 (8)0.0046 (9)
N60.0534 (12)0.0457 (12)0.0593 (12)0.0161 (10)0.0136 (10)0.0129 (11)
O10.0377 (8)0.0501 (10)0.0522 (9)0.0099 (8)0.0099 (7)0.0109 (8)
O20.0513 (10)0.0586 (11)0.0815 (12)0.0239 (10)0.0181 (9)0.0221 (10)
C10.0482 (13)0.0443 (13)0.0524 (13)0.0129 (12)0.0007 (11)0.0010 (11)
C20.0676 (16)0.0391 (13)0.0602 (14)0.0181 (13)0.0014 (13)0.0042 (12)
C30.0743 (17)0.0391 (13)0.0539 (13)0.0060 (13)0.0018 (14)0.0076 (11)
C40.0439 (11)0.0345 (10)0.0388 (10)0.0045 (10)0.0000 (9)0.0006 (9)
C50.0386 (10)0.0345 (11)0.0352 (9)0.0055 (9)0.0013 (8)0.0009 (8)
C60.0411 (11)0.0377 (11)0.0371 (10)0.0056 (10)0.0031 (9)0.0020 (9)
C70.0413 (11)0.0384 (12)0.0391 (10)0.0070 (10)0.0022 (10)0.0001 (9)
C80.0392 (11)0.0425 (12)0.0428 (11)0.0083 (10)0.0037 (10)0.0035 (10)
C90.0371 (12)0.0680 (17)0.0611 (14)0.0053 (13)0.0127 (11)0.0087 (14)
C100.0573 (15)0.0725 (19)0.0546 (14)0.0059 (15)0.0089 (12)0.0082 (14)
C110.0651 (18)0.0646 (18)0.094 (2)0.0301 (16)0.0218 (17)0.0122 (18)
C120.123 (3)0.0550 (19)0.105 (2)0.015 (2)0.035 (2)0.0359 (18)
C130.0418 (12)0.0513 (14)0.0594 (13)0.0018 (12)0.0070 (11)0.0098 (13)
Geometric parameters (Å, º) top
N1—C41.328 (3)C2—H20.9300
N1—C11.343 (3)C3—C121.500 (4)
N2—C31.332 (3)C5—C61.417 (3)
N2—C41.344 (3)C6—C71.404 (3)
N3—C41.379 (3)C6—C81.440 (3)
N3—C51.386 (3)C9—C101.490 (4)
N3—H30.865 (10)C9—H9A0.9700
N4—C51.317 (3)C9—H9B0.9700
N4—N51.394 (3)C10—H10A0.9600
N5—C71.339 (3)C10—H10B0.9600
N5—C131.437 (3)C10—H10C0.9600
N6—C71.355 (3)C11—H11A0.9600
N6—H6A0.860 (10)C11—H11B0.9600
N6—H6B0.860 (10)C11—H11C0.9600
O1—C81.347 (3)C12—H12A0.9600
O1—C91.461 (3)C12—H12B0.9600
O2—C81.215 (3)C12—H12C0.9600
C1—C21.370 (4)C13—H13A0.9600
C1—C111.499 (4)C13—H13B0.9600
C2—C31.389 (4)C13—H13C0.9600
C4—N1—C1115.6 (2)O2—C8—O1122.7 (2)
C3—N2—C4115.7 (2)O2—C8—C6124.9 (2)
C4—N3—C5129.94 (18)O1—C8—C6112.38 (19)
C4—N3—H3117.6 (19)O1—C9—C10106.4 (2)
C5—N3—H3112.4 (18)O1—C9—H9A110.4
C5—N4—N5104.14 (17)C10—C9—H9A110.4
C7—N5—N4112.42 (18)O1—C9—H9B110.4
C7—N5—C13129.4 (2)C10—C9—H9B110.4
N4—N5—C13118.03 (19)H9A—C9—H9B108.6
C7—N6—H6A115 (2)C9—C10—H10A109.5
C7—N6—H6B115 (2)C9—C10—H10B109.5
H6A—N6—H6B117 (3)H10A—C10—H10B109.5
C8—O1—C9117.70 (18)C9—C10—H10C109.5
N1—C1—C2121.8 (2)H10A—C10—H10C109.5
N1—C1—C11116.0 (2)H10B—C10—H10C109.5
C2—C1—C11122.2 (2)C1—C11—H11A109.5
C1—C2—C3118.1 (2)C1—C11—H11B109.5
C1—C2—H2120.9H11A—C11—H11B109.5
C3—C2—H2120.9C1—C11—H11C109.5
N2—C3—C2121.4 (2)H11A—C11—H11C109.5
N2—C3—C12116.9 (3)H11B—C11—H11C109.5
C2—C3—C12121.7 (3)C3—C12—H12A109.5
N1—C4—N2127.4 (2)C3—C12—H12B109.5
N1—C4—N3119.1 (2)H12A—C12—H12B109.5
N2—C4—N3113.49 (19)C3—C12—H12C109.5
N4—C5—N3123.49 (19)H12A—C12—H12C109.5
N4—C5—C6112.53 (19)H12B—C12—H12C109.5
N3—C5—C6123.96 (19)N5—C13—H13A109.5
C7—C6—C5104.20 (19)N5—C13—H13B109.5
C7—C6—C8124.0 (2)H13A—C13—H13B109.5
C5—C6—C8131.8 (2)N5—C13—H13C109.5
N5—C7—N6123.6 (2)H13A—C13—H13C109.5
N5—C7—C6106.69 (19)H13B—C13—H13C109.5
N6—C7—C6129.7 (2)
C5—N4—N5—C71.2 (2)N4—C5—C6—C70.1 (3)
C5—N4—N5—C13174.9 (2)N3—C5—C6—C7178.8 (2)
C4—N1—C1—C21.7 (3)N4—C5—C6—C8179.3 (2)
C4—N1—C1—C11177.4 (2)N3—C5—C6—C80.3 (4)
N1—C1—C2—C30.6 (4)N4—N5—C7—N6179.0 (2)
C11—C1—C2—C3178.4 (3)C13—N5—C7—N63.5 (4)
C4—N2—C3—C21.7 (4)N4—N5—C7—C61.3 (2)
C4—N2—C3—C12179.7 (3)C13—N5—C7—C6174.2 (2)
C1—C2—C3—N21.2 (4)C5—C6—C7—N50.9 (2)
C1—C2—C3—C12179.7 (3)C8—C6—C7—N5179.9 (2)
C1—N1—C4—N21.2 (3)C5—C6—C7—N6178.4 (2)
C1—N1—C4—N3179.2 (2)C8—C6—C7—N62.4 (4)
C3—N2—C4—N10.5 (4)C9—O1—C8—O20.3 (3)
C3—N2—C4—N3179.1 (2)C9—O1—C8—C6179.7 (2)
C5—N3—C4—N11.3 (4)C7—C6—C8—O20.3 (4)
C5—N3—C4—N2179.1 (2)C5—C6—C8—O2179.3 (2)
N5—N4—C5—N3179.54 (19)C7—C6—C8—O1179.7 (2)
N5—N4—C5—C60.6 (2)C5—C6—C8—O10.8 (3)
C4—N3—C5—N46.7 (4)C8—O1—C9—C10177.5 (2)
C4—N3—C5—C6172.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O10.87 (1)2.13 (2)2.806 (2)135 (2)
N6—H6A···N4i0.86 (1)2.27 (2)3.082 (3)158 (3)
N6—H6B···O20.86 (1)2.33 (2)2.933 (3)128 (3)
Symmetry code: (i) x+2, y+1/2, z+1/2.
(II) 5-amino-3-(4,6-dimethylpyrimidin-2-ylamino)-1-(2-nitrophenylsulfonyl)-1H- pyrazole-4-carboxylate top
Crystal data top
C18H19N7O6SF(000) = 960
Mr = 461.46Dx = 1.471 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 10.536 (2) ÅCell parameters from 965 reflections
b = 13.715 (3) Åθ = 2.9–25.0°
c = 14.443 (3) ŵ = 0.21 mm1
β = 93.570 (8)°T = 293 K
V = 2083.1 (7) Å3Prism, yellow
Z = 40.30 × 0.25 × 0.20 mm
Data collection top
Bruker Smart 1000 CCD area detector
diffractometer
4118 independent reflections
Radiation source: fine-focus sealed tube2700 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ϕ and ω scansθmax = 26.3°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 713
Tmin = 0.920, Tmax = 0.960k = 1715
9353 measured reflectionsl = 1717
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)] = 0.050H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.134 w = 1/[σ2(Fo2) + (0.064P)2 + 0.3838P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
4118 reflectionsΔρmax = 0.28 e Å3
299 parametersΔρmin = 0.28 e Å3
3 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0039 (7)
Crystal data top
C18H19N7O6SV = 2083.1 (7) Å3
Mr = 461.46Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.536 (2) ŵ = 0.21 mm1
b = 13.715 (3) ÅT = 293 K
c = 14.443 (3) Å0.30 × 0.25 × 0.20 mm
β = 93.570 (8)°
Data collection top
Bruker Smart 1000 CCD area detector
diffractometer
4118 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2700 reflections with I > 2σ(I)
Tmin = 0.920, Tmax = 0.960Rint = 0.033
9353 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0503 restraints
wR(F2) = 0.134H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.28 e Å3
4118 reflectionsΔρmin = 0.28 e Å3
299 parameters
Special details top

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
S10.57284 (6)0.12638 (5)0.22549 (5)0.0438 (2)
N10.69234 (18)0.05903 (14)0.26817 (14)0.0425 (5)
N20.78835 (19)0.10974 (14)0.32040 (14)0.0430 (5)
N30.6384 (2)0.10196 (16)0.21611 (17)0.0499 (6)
H3A0.575 (2)0.0796 (19)0.1806 (17)0.060*
H3B0.664 (3)0.1613 (10)0.215 (2)0.060*
N40.98180 (19)0.05405 (15)0.39663 (16)0.0474 (6)
H4A1.025 (2)0.0004 (12)0.4048 (19)0.057*
N50.9867 (2)0.22207 (15)0.40477 (14)0.0445 (5)
N61.16411 (19)0.12307 (16)0.45559 (15)0.0497 (6)
N70.6725 (3)0.11561 (18)0.02380 (18)0.0617 (7)
O10.49884 (15)0.06442 (13)0.16489 (13)0.0533 (5)
O20.51682 (18)0.17169 (15)0.30025 (14)0.0630 (6)
O31.00872 (17)0.14395 (13)0.36592 (14)0.0579 (5)
O40.84198 (16)0.22107 (12)0.29616 (12)0.0469 (5)
O50.7269 (3)0.04895 (16)0.06355 (17)0.0845 (8)
O60.6219 (3)0.11078 (19)0.05265 (18)0.1118 (11)
C10.7172 (2)0.03886 (17)0.26109 (16)0.0366 (6)
C20.8317 (2)0.05307 (17)0.31064 (16)0.0369 (6)
C30.8694 (2)0.04090 (17)0.34392 (16)0.0374 (6)
C41.0454 (2)0.13825 (18)0.41982 (17)0.0408 (6)
C51.0572 (3)0.30159 (19)0.42412 (18)0.0499 (7)
C61.1811 (3)0.2942 (2)0.45954 (19)0.0575 (8)
H61.22960.34980.47240.069*
C71.2319 (3)0.2031 (2)0.47556 (19)0.0544 (7)
C80.9927 (3)0.3963 (2)0.4053 (3)0.0748 (10)
H8A0.94280.39270.34750.112*
H8B1.05530.44690.40190.112*
H8C0.93820.41070.45440.112*
C91.3653 (3)0.1879 (3)0.5150 (3)0.0807 (11)
H9A1.36830.13160.55440.121*
H9B1.39250.24420.55040.121*
H9C1.42050.17830.46540.121*
C100.9035 (2)0.14145 (17)0.32715 (17)0.0401 (6)
C110.9102 (3)0.31255 (17)0.31087 (19)0.0485 (7)
H11A0.94410.31750.37470.058*
H11B0.98010.31660.27040.058*
C120.8169 (3)0.3917 (2)0.2893 (2)0.0674 (9)
H12A0.75320.39110.33400.101*
H12B0.85990.45340.29150.101*
H12C0.77730.38180.22830.101*
C130.6420 (2)0.21922 (17)0.16187 (18)0.0403 (6)
C140.6728 (2)0.20987 (18)0.07062 (19)0.0437 (6)
C150.7072 (3)0.2879 (2)0.0193 (2)0.0562 (8)
H150.72670.27980.04220.067*
C160.7128 (3)0.3781 (2)0.0594 (3)0.0672 (9)
H160.73600.43190.02510.081*
C170.6846 (3)0.3895 (2)0.1487 (3)0.0685 (9)
H170.68970.45110.17550.082*
C180.6484 (3)0.3110 (2)0.2007 (2)0.0556 (8)
H180.62830.32000.26190.067*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0326 (3)0.0495 (4)0.0487 (4)0.0019 (3)0.0029 (3)0.0044 (3)
N10.0396 (11)0.0392 (11)0.0468 (13)0.0028 (9)0.0129 (10)0.0011 (10)
N20.0420 (12)0.0386 (11)0.0466 (13)0.0062 (9)0.0117 (10)0.0036 (10)
N30.0478 (13)0.0405 (12)0.0594 (15)0.0054 (11)0.0131 (11)0.0063 (12)
N40.0412 (12)0.0415 (12)0.0568 (14)0.0058 (10)0.0177 (11)0.0041 (11)
N50.0466 (12)0.0467 (13)0.0397 (13)0.0099 (10)0.0006 (10)0.0022 (10)
N60.0386 (12)0.0656 (15)0.0439 (13)0.0117 (11)0.0044 (10)0.0008 (11)
N70.0812 (18)0.0550 (16)0.0496 (16)0.0070 (13)0.0089 (14)0.0024 (13)
O10.0359 (9)0.0564 (11)0.0654 (13)0.0043 (8)0.0147 (9)0.0069 (10)
O20.0536 (12)0.0782 (14)0.0584 (13)0.0090 (10)0.0146 (10)0.0128 (11)
O30.0434 (11)0.0542 (11)0.0741 (14)0.0031 (9)0.0126 (10)0.0024 (10)
O40.0511 (11)0.0380 (9)0.0502 (11)0.0036 (8)0.0078 (9)0.0019 (8)
O50.116 (2)0.0569 (13)0.0825 (17)0.0343 (13)0.0214 (15)0.0006 (13)
O60.187 (3)0.0845 (18)0.0593 (16)0.0117 (18)0.0240 (18)0.0163 (14)
C10.0363 (12)0.0388 (13)0.0347 (14)0.0065 (11)0.0023 (10)0.0011 (11)
C20.0357 (12)0.0393 (13)0.0355 (13)0.0039 (10)0.0000 (10)0.0004 (11)
C30.0374 (13)0.0399 (13)0.0346 (13)0.0066 (11)0.0012 (10)0.0043 (11)
C40.0398 (13)0.0480 (15)0.0340 (14)0.0096 (12)0.0032 (11)0.0004 (12)
C50.0623 (18)0.0510 (16)0.0374 (15)0.0165 (14)0.0112 (13)0.0056 (13)
C60.0574 (18)0.069 (2)0.0470 (17)0.0342 (16)0.0098 (14)0.0132 (15)
C70.0439 (15)0.080 (2)0.0395 (16)0.0207 (15)0.0032 (12)0.0086 (15)
C80.090 (2)0.0479 (18)0.087 (3)0.0164 (16)0.014 (2)0.0126 (17)
C90.0417 (17)0.124 (3)0.075 (2)0.0263 (19)0.0085 (15)0.008 (2)
C100.0426 (14)0.0418 (14)0.0359 (14)0.0037 (11)0.0027 (11)0.0020 (11)
C110.0579 (17)0.0429 (14)0.0444 (15)0.0092 (12)0.0018 (13)0.0005 (13)
C120.080 (2)0.0433 (16)0.078 (2)0.0008 (15)0.0019 (18)0.0000 (15)
C130.0321 (12)0.0410 (13)0.0462 (16)0.0060 (10)0.0093 (11)0.0011 (12)
C140.0380 (13)0.0438 (15)0.0482 (17)0.0038 (11)0.0053 (12)0.0016 (12)
C150.0470 (16)0.0587 (18)0.0622 (19)0.0011 (13)0.0021 (14)0.0121 (15)
C160.0528 (18)0.0546 (19)0.093 (3)0.0110 (14)0.0093 (17)0.0148 (19)
C170.063 (2)0.0428 (17)0.097 (3)0.0074 (14)0.0130 (19)0.0106 (18)
C180.0525 (17)0.0508 (17)0.0620 (19)0.0052 (13)0.0091 (14)0.0147 (15)
Geometric parameters (Å, º) top
S1—O21.407 (2)C5—C81.484 (4)
S1—O11.4182 (17)C6—C71.373 (4)
S1—N11.650 (2)C6—H60.9300
S1—C131.755 (3)C7—C91.498 (4)
N1—C11.373 (3)C8—H8A0.9600
N1—N21.408 (2)C8—H8B0.9600
N2—C31.304 (3)C8—H8C0.9600
N3—C11.339 (3)C9—H9A0.9600
N3—H3A0.874 (10)C9—H9B0.9600
N3—H3B0.860 (10)C9—H9C0.9600
N4—C41.366 (3)C11—C121.484 (4)
N4—C31.380 (3)C11—H11A0.9700
N4—H4A0.869 (10)C11—H11B0.9700
N5—C41.317 (3)C12—H12A0.9600
N5—C51.339 (3)C12—H12B0.9600
N6—C71.331 (3)C12—H12C0.9600
N6—C41.340 (3)C13—C181.378 (3)
N7—O61.198 (3)C13—C141.383 (4)
N7—O51.205 (3)C14—C151.364 (4)
N7—C141.459 (3)C15—C161.366 (4)
O3—C101.211 (3)C15—H150.9300
O4—C101.333 (3)C16—C171.350 (5)
O4—C111.455 (3)C16—H160.9300
C1—C21.378 (3)C17—C181.381 (4)
C2—C31.423 (3)C17—H170.9300
C2—C101.441 (3)C18—H180.9300
C5—C61.376 (4)
O2—S1—O1119.83 (12)C5—C8—H8B109.5
O2—S1—N1107.90 (12)H8A—C8—H8B109.5
O1—S1—N1105.81 (10)C5—C8—H8C109.5
O2—S1—C13106.81 (13)H8A—C8—H8C109.5
O1—S1—C13110.00 (12)H8B—C8—H8C109.5
N1—S1—C13105.64 (11)C7—C9—H9A109.5
C1—N1—N2112.89 (18)C7—C9—H9B109.5
C1—N1—S1131.64 (16)H9A—C9—H9B109.5
N2—N1—S1115.46 (15)C7—C9—H9C109.5
C3—N2—N1102.64 (18)H9A—C9—H9C109.5
C1—N3—H3A119.2 (19)H9B—C9—H9C109.5
C1—N3—H3B115.7 (19)O3—C10—O4123.0 (2)
H3A—N3—H3B124 (3)O3—C10—C2123.8 (2)
C4—N4—C3129.6 (2)O4—C10—C2113.2 (2)
C4—N4—H4A116.0 (18)O4—C11—C12106.6 (2)
C3—N4—H4A112.9 (18)O4—C11—H11A110.4
C4—N5—C5115.3 (2)C12—C11—H11A110.4
C7—N6—C4115.5 (2)O4—C11—H11B110.4
O6—N7—O5124.6 (3)C12—C11—H11B110.4
O6—N7—C14117.7 (3)H11A—C11—H11B108.6
O5—N7—C14117.7 (2)C11—C12—H12A109.5
C10—O4—C11115.60 (19)C11—C12—H12B109.5
N3—C1—N1123.5 (2)H12A—C12—H12B109.5
N3—C1—C2131.1 (2)C11—C12—H12C109.5
N1—C1—C2105.34 (19)H12A—C12—H12C109.5
C1—C2—C3105.3 (2)H12B—C12—H12C109.5
C1—C2—C10129.7 (2)C18—C13—C14117.7 (2)
C3—C2—C10125.0 (2)C18—C13—S1117.4 (2)
N2—C3—N4125.1 (2)C14—C13—S1124.16 (19)
N2—C3—C2113.8 (2)C15—C14—C13122.1 (3)
N4—C3—C2121.1 (2)C15—C14—N7115.9 (3)
N5—C4—N6128.1 (2)C13—C14—N7122.0 (2)
N5—C4—N4118.6 (2)C14—C15—C16119.1 (3)
N6—C4—N4113.3 (2)C14—C15—H15120.5
N5—C5—C6121.2 (3)C16—C15—H15120.5
N5—C5—C8115.7 (3)C17—C16—C15120.2 (3)
C6—C5—C8123.1 (3)C17—C16—H16119.9
C7—C6—C5118.7 (3)C15—C16—H16119.9
C7—C6—H6120.6C16—C17—C18121.0 (3)
C5—C6—H6120.6C16—C17—H17119.5
N6—C7—C6121.0 (2)C18—C17—H17119.5
N6—C7—C9116.5 (3)C13—C18—C17119.9 (3)
C6—C7—C9122.5 (3)C13—C18—H18120.0
C5—C8—H8A109.5C17—C18—H18120.0
O2—S1—N1—C1121.9 (2)C8—C5—C6—C7179.2 (3)
O1—S1—N1—C17.5 (3)C4—N6—C7—C60.2 (4)
C13—S1—N1—C1124.1 (2)C4—N6—C7—C9179.6 (2)
O2—S1—N1—N259.2 (2)C5—C6—C7—N61.4 (4)
O1—S1—N1—N2171.39 (17)C5—C6—C7—C9179.3 (3)
C13—S1—N1—N254.7 (2)C11—O4—C10—O30.7 (4)
C1—N1—N2—C30.1 (3)C11—O4—C10—C2179.9 (2)
S1—N1—N2—C3179.19 (17)C1—C2—C10—O3173.9 (3)
N2—N1—C1—N3178.8 (2)C3—C2—C10—O35.5 (4)
S1—N1—C1—N32.3 (4)C1—C2—C10—O46.7 (4)
N2—N1—C1—C20.6 (3)C3—C2—C10—O4173.9 (2)
S1—N1—C1—C2179.5 (2)C10—O4—C11—C12168.9 (2)
N3—C1—C2—C3178.8 (3)O2—S1—C13—C189.9 (2)
N1—C1—C2—C30.8 (3)O1—S1—C13—C18141.41 (19)
N3—C1—C2—C101.7 (5)N1—S1—C13—C18104.8 (2)
N1—C1—C2—C10179.7 (2)O2—S1—C13—C14160.0 (2)
N1—N2—C3—N4180.0 (2)O1—S1—C13—C1428.5 (2)
N1—N2—C3—C20.4 (3)N1—S1—C13—C1485.3 (2)
C4—N4—C3—N214.2 (4)C18—C13—C14—C150.7 (4)
C4—N4—C3—C2166.3 (2)S1—C13—C14—C15169.2 (2)
C1—C2—C3—N20.8 (3)C18—C13—C14—N7178.3 (2)
C10—C2—C3—N2179.7 (2)S1—C13—C14—N711.8 (3)
C1—C2—C3—N4179.6 (2)O6—N7—C14—C1547.1 (4)
C10—C2—C3—N40.1 (4)O5—N7—C14—C15130.5 (3)
C5—N5—C4—N63.2 (4)O6—N7—C14—C13133.9 (3)
C5—N5—C4—N4176.3 (2)O5—N7—C14—C1348.6 (4)
C7—N6—C4—N52.3 (4)C13—C14—C15—C160.7 (4)
C7—N6—C4—N4177.2 (2)N7—C14—C15—C16178.4 (2)
C3—N4—C4—N512.5 (4)C14—C15—C16—C170.1 (4)
C3—N4—C4—N6167.0 (3)C15—C16—C17—C180.8 (5)
C4—N5—C5—C61.7 (4)C14—C13—C18—C170.1 (4)
C4—N5—C5—C8178.7 (3)S1—C13—C18—C17170.7 (2)
N5—C5—C6—C70.4 (4)C16—C17—C18—C130.8 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O10.87 (1)2.14 (2)2.789 (3)131 (2)
N3—H3B···O40.86 (1)2.30 (2)2.881 (3)125 (2)
N4—H4A···O30.87 (1)2.06 (2)2.769 (3)138 (2)

Experimental details

(I)(II)
Crystal data
Chemical formulaC13H18N6O2C18H19N7O6S
Mr290.33461.46
Crystal system, space groupOrthorhombic, P212121Monoclinic, P21/c
Temperature (K)293293
a, b, c (Å)7.5466 (15), 9.042 (2), 22.412 (8)10.536 (2), 13.715 (3), 14.443 (3)
α, β, γ (°)90, 90, 9090, 93.570 (8), 90
V3)1529.3 (7)2083.1 (7)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.090.21
Crystal size (mm)0.38 × 0.30 × 0.200.30 × 0.25 × 0.20
Data collection
DiffractometerBruker Smart 1000 CCD area detector
diffractometer
Bruker Smart 1000 CCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.920, 0.960
No. of measured, independent and
observed [I > 2σ(I)] reflections
7861, 1836, 1629 9353, 4118, 2700
Rint0.0480.033
(sin θ/λ)max1)0.6280.623
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.101, 1.09 0.050, 0.134, 1.04
No. of reflections18364118
No. of parameters204299
No. of restraints33
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.17, 0.130.28, 0.28

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.

Selected geometric parameters (Å, º) for (I) top
N3—C51.386 (3)C5—C61.417 (3)
N6—C71.355 (3)C6—C71.404 (3)
O1—C81.347 (3)C6—C81.440 (3)
O2—C81.215 (3)
N3—C5—C6123.96 (19)O2—C8—C6124.9 (2)
N6—C7—C6129.7 (2)O1—C8—C6112.38 (19)
O2—C8—O1122.7 (2)
N3—C5—C6—C80.3 (4)C7—C6—C8—O20.3 (4)
C8—C6—C7—N62.4 (4)C5—C6—C8—O10.8 (3)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O10.865 (10)2.13 (2)2.806 (2)135 (2)
N6—H6A···N4i0.860 (10)2.266 (15)3.082 (3)158 (3)
N6—H6B···O20.860 (10)2.33 (2)2.933 (3)128 (3)
Symmetry code: (i) x+2, y+1/2, z+1/2.
Selected geometric parameters (Å, º) for (II) top
S1—O11.4182 (17)O3—C101.211 (3)
S1—N11.650 (2)O4—C101.333 (3)
N1—C11.373 (3)C1—C21.378 (3)
N3—C11.339 (3)C2—C101.441 (3)
N4—C31.380 (3)
O1—S1—N1105.81 (10)N4—C3—C2121.1 (2)
N3—C1—N1123.5 (2)O3—C10—C2123.8 (2)
N3—C1—C2131.1 (2)O4—C10—C2113.2 (2)
O1—S1—N1—C17.5 (3)C1—C2—C10—O46.7 (4)
S1—N1—C1—N32.3 (4)C3—C2—C10—O4173.9 (2)
N3—C1—C2—C101.7 (5)O5—N7—C14—C1348.6 (4)
C10—C2—C3—N40.1 (4)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O10.874 (10)2.14 (2)2.789 (3)131 (2)
N3—H3B···O40.860 (10)2.30 (2)2.881 (3)125 (2)
N4—H4A···O30.869 (10)2.063 (19)2.769 (3)138 (2)
 

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