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The two title semicarbazones, namely 2,3-dihydro-1H-indole-2,3-dione 3-semicarbazone, C9H8N4O2, (I), and 1-methyl-2,3-dihydro-1H-indole-2,3-dione 3-semicarbazone, C10H10N4O2, (II), show the same configuration, viz. Z around the imine C=N bond and E around the C(O)-NH2 bond, stabilized by two intra­molecular hydrogen bonds. The presence of a methyl group on the isatin N atom determines the difference in the packing; in (I), the mol­ecules are linked into chains which lie in the crystallographic (102) plane and run perpendicular to the b axis, while in (II), the mol­ecules are arranged to form helices running parallel to a crystallographic screw axis in the a direction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105024959/hj1061sup1.cif
Contains datablocks I, II, global, publication_text

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105024959/hj1061Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105024959/hj1061IIsup3.hkl
Contains datablock II

CCDC references: 244066; 244068

Comment top

Isatin derivatives are molecules that possess biological properties (Pandeya et al., 1999, and references therein). During the past few years, we have devoted our research to isatin derivatives and their metal complexes in order to study their biological activity (Rodríguez-Argüelles et al., 1999, 2004; Casas et al., 2000). In this framework, we report here the synthesis and solid state characterization of two semicarbazones, viz. isatin- and 1-methylisatin-3-semicarbazone, (I) and (II), respectively.

The configuration of (I) (Fig. 1) is Z with respect to the C2—N3 bond (with the configuration stabilized by an N2—H3···O2 intramolecular hydrogen bond; Table 2), while it is E with respect to the C1—N2 bond (stabilized by an N1—H2···N3 intramolecular hydrogen bond; Table 2). The same configurations have been found in uncomplexed isatin-3-thiosemicarbazone (Casas et al., 2000) and in isatinthiosemicarbazone ethyl or p-tolyl monosubstituted on the amine N atom (Bain et al., 1997; Revenko et al., 1994). The bond distances and angles are listed in Table 1 and are comparable to those reported in the literature for similar compounds (Allen, 2002). In the five-membered ring, the C2—C9 bond [1.505 (3) Å] is shorter than the corresponding bond in free isatin [1.555 (3) Å; Palenik et al., 1990]. This difference confirms the hypothesis that the bond lengthening of unsubstituted isatin is due to repulsion between the lone pair of the O atom in the cis position. The six- and five-membered rings are nearly planar [the dihedral angle between the mean planes of the two rings is 1.20 (6)°], and the dihedral angle between the mean planes of the isatin and semicarbazide groups is 5.42 (5)°. These molecules could take the keto–imine tautomeric form in solution, but in the crystal only the keto form is observed, as confirmed by the C9O2 distance [1.230 (2) Å]. This form is stabilized by intermolecular hydrogen bondings (i) between amine atom N1 and atom O2 at (x − 1, −y + 1/2, z + 1/2) and (ii) between isatin atom N4 and atom O1 of the semicarbazide moiety at (x + 1, −y + 1/2, z − 1/2) (Table 2). This short hydrogen bond justifies the unusually long distance N4—H (1.04 Å). These two bonds link the molecules in chains lying in the crystallographic (102) plane and running perpendicular to the b axis (Fig. 2). Forces which can probably be interpreted as due to stacking interactions between the six-membered isatin rings of centrosymmetrical molecules (in the range 3.340–3.519 Å) hold the chains together to form a complex network in directions c and a.

Fig. 3 shows an ORTEPIII (Burnett & Johnson, 1996) view of (II). The molecular geometry is similar to that of the non-methylated compound (I). The configuration is Z around the C2—N3 bond, stabilized by an intramolecular N2—H3···O2 bond, and E with respect to the C1—N2 bond as a consequence of the intramolecular N1—H2···N3 bond (Table 3). Again, the C2—C9 bond [1.497 (3) Å] is shorter than that in free isatin. The dihedral angles between the mean planes of the two rings is 1.04 (9)°, and that between the mean planes of the isatin and semicarbazide groups is 1.61 (9)°. The whole molecule is therefore essentially planar. In the crystal packing (Fig. 4), which is different from (I), the presence of hydrogen bonds between atoms N1 and O1 of molecules related by a 21 axis (Table 3) gives rise to a helix running parallel to the crystallographic a axis. Weak interactions C—H···O between an aromatic isatin C atom, a methyl C atom and a carbonyl O atom are also present; details are in Table 3.

Experimental top

The title compounds were obtained from isatin or 1-methylisatin and neutral semicarbazide (1:1 molar ratio) in an ethanol–water solution, following a similar procedure to that previously reported by Tomchin et al. (1973). The solids obtained by cooling were filtered, washed with ethanol 98% and dried under a vacuum. For isatin 3-semicarbazone H2L1·H2O: yellow powder, solid, m.p. 564 K. Analysis found: C 48.8, H 4.4, N 25.0%; calculated for for C9H8N4O2·H2O: C 48.7, H 4.5, N 25.2%. The yield was 54%. The solid was dissolved in ethyl acetate and after several days at room temperature the solution afforded crystals of (I) that were extremely small but suitable for X-ray diffraction studies and that did not contain the water molecule observed for the powder. For 1-methylisatin 3-semicarbazone HL2: yellow solid, m.p. 522 K 249° C. Analysis found: C 54.9, H 4.7, N 25.0%; calculated for C10H10N4O2: C 55.0, H 4.6, N 25.7%. Yield 57%. After several days at room temperature the solution afforded crystals of (II) that were suitable for X-ray diffraction studies.

Refinement top

In (I), all H atoms were located in a difference map, except aromatic atoms H4 and H7, which were calculated with standard geometries. In (II) all H atoms were visible in difference maps and subsequently allowed for as riding atoms with C—H 0.93 to 0.96 Å and N—H 0.86 Å with Uiso(H) = 1.2Ueq(C,N), or 1.5Ueq(C) for the methyl groups. In the absence of significant anomalous scattering i (II), the Flack parameter (Flack, 1983) was indeterminate (Flack & Bernardinelli, 2000), and the Friedel-equivalent reflections were merged prior to the final refinements.

Computing details top

Data collection: local program (Belletti et al., 1988) for (I); SMART (Bruker, 1997) for (II). Cell refinement: local program (Belletti et al., 1988) for (I); SMART for (II). Data reduction: local program (Belletti et al., 1988) for (I); SAINT (Bruker, 1997) for (II). For both compounds, program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. An ORTEPIII (Burnett & Johnson, 1996) view of the molecule of (I), with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram for (I), with hydrogen bonds indicated by dashed lines.
[Figure 3] Fig. 3. An ORTEPIII (Burnett & Johnson, 1996) view of the molecule of (II), with displacement ellipsoids drawn at the 50% probability level.
[Figure 4] Fig. 4. A packing diagram for (II), with hydrogen bonds indicated by dashed lines.
(I) 1H-indole-2,3-dione 3-semicarbazone top
Crystal data top
C9H8N4O2F(000) = 424
Mr = 204.19Dx = 1.483 Mg m3
Monoclinic, P21/cMelting point: 291 K
Hall symbol: -P 2ybcCu Kα radiation, λ = 1.54178 Å
a = 5.554 (1) ÅCell parameters from 20 reflections
b = 18.754 (3) Åθ = 20–30°
c = 8.974 (2) ŵ = 0.93 mm1
β = 101.84 (3)°T = 298 K
V = 914.8 (3) Å3Prism, pale yellow
Z = 40.3 × 0.2 × 0.2 mm
Data collection top
Siemens AED
diffractometer
Rint = 0.032
Radiation source: fine-focus sealed tubeθmax = 62.5°, θmin = 2.2°
Graphite monochromatorh = 65
θ–2θ scansk = 021
1438 measured reflectionsl = 010
1354 independent reflections1 standard reflections every 100 reflections
907 reflections with I > 2σ(I) intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: full with fixed elements per cycleSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H-atom parameters not refined
S = 0.93 w = 1/[σ2(Fo2) + (0.0504P)2]
where P = (Fo2 + 2Fc2)/3
1354 reflections(Δ/σ)max = 0.013
136 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = 0.15 e Å3
Crystal data top
C9H8N4O2V = 914.8 (3) Å3
Mr = 204.19Z = 4
Monoclinic, P21/cCu Kα radiation
a = 5.554 (1) ŵ = 0.93 mm1
b = 18.754 (3) ÅT = 298 K
c = 8.974 (2) Å0.3 × 0.2 × 0.2 mm
β = 101.84 (3)°
Data collection top
Siemens AED
diffractometer
Rint = 0.032
1438 measured reflections1 standard reflections every 100 reflections
1354 independent reflections intensity decay: 1%
907 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.092H-atom parameters not refined
S = 0.93Δρmax = 0.17 e Å3
1354 reflectionsΔρmin = 0.15 e Å3
136 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
H10.31410.21260.60250.089*
H20.46340.14670.53590.050*
H30.78100.25020.34170.074*
H40.76420.01360.36980.050*
H50.95030.11730.29320.065*
H61.26060.10780.15520.065*
H71.38270.00680.08980.050*
H81.30340.15600.09240.092*
O10.5024 (3)0.30826 (7)0.48589 (18)0.0571 (5)
O21.0307 (3)0.24314 (7)0.21098 (17)0.0516 (4)
N10.4202 (4)0.19444 (9)0.5468 (2)0.0540 (5)
N20.6855 (3)0.21900 (8)0.3862 (2)0.0455 (5)
N30.7266 (3)0.14809 (8)0.37596 (19)0.0431 (5)
N41.1815 (3)0.13399 (8)0.1535 (2)0.0465 (5)
C10.5303 (4)0.24379 (11)0.4767 (2)0.0440 (5)
C20.8857 (4)0.12954 (10)0.2964 (2)0.0392 (5)
C30.9602 (4)0.05687 (10)0.2719 (2)0.0402 (5)
C40.8875 (5)0.00943 (11)0.3137 (3)0.0522 (6)
C51.0005 (5)0.06931 (11)0.2705 (3)0.0602 (7)
C61.1839 (5)0.06316 (11)0.1876 (3)0.0597 (7)
C71.2581 (4)0.00260 (12)0.1448 (3)0.0550 (6)
C81.1426 (4)0.06185 (10)0.1863 (2)0.0436 (5)
C91.0355 (4)0.17762 (10)0.2165 (2)0.0411 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0673 (11)0.0379 (9)0.0789 (12)0.0021 (7)0.0445 (9)0.0033 (8)
O20.0578 (10)0.0352 (8)0.0694 (11)0.0025 (7)0.0307 (8)0.0010 (7)
N10.0657 (13)0.0401 (10)0.0683 (13)0.0008 (9)0.0421 (11)0.0014 (9)
N20.0527 (11)0.0352 (9)0.0578 (12)0.0010 (8)0.0329 (10)0.0018 (8)
N30.0466 (11)0.0368 (10)0.0503 (11)0.0022 (8)0.0202 (9)0.0009 (8)
N40.0494 (11)0.0390 (10)0.0590 (12)0.0006 (8)0.0295 (10)0.0005 (9)
C10.0457 (12)0.0399 (13)0.0518 (14)0.0012 (10)0.0230 (11)0.0023 (10)
C20.0389 (12)0.0378 (11)0.0448 (12)0.0024 (9)0.0177 (10)0.0002 (10)
C30.0417 (12)0.0352 (10)0.0462 (12)0.0007 (10)0.0152 (10)0.0004 (10)
C40.0596 (15)0.0424 (13)0.0595 (15)0.0030 (11)0.0237 (12)0.0035 (11)
C50.0778 (19)0.0351 (12)0.0708 (17)0.0010 (11)0.0223 (15)0.0006 (11)
C60.0736 (17)0.0393 (13)0.0683 (17)0.0136 (12)0.0198 (15)0.0060 (12)
C70.0561 (15)0.0513 (14)0.0640 (16)0.0108 (11)0.0271 (13)0.0040 (12)
C80.0445 (13)0.0411 (12)0.0482 (13)0.0014 (10)0.0163 (11)0.0025 (10)
C90.0405 (12)0.0378 (12)0.0488 (13)0.0023 (9)0.0181 (11)0.0009 (10)
Geometric parameters (Å, º) top
O1—C11.224 (2)C2—C31.454 (3)
O2—C91.230 (2)C2—C91.505 (3)
N1—C11.336 (3)C3—C41.383 (3)
N1—H10.9135C3—C81.395 (3)
N1—H20.9378C4—C51.380 (3)
N2—N31.356 (2)C4—H40.933
N2—C11.380 (3)C5—C61.384 (4)
N2—H30.9327C5—H50.976
N3—C21.293 (3)C6—C71.380 (3)
N4—C91.355 (3)C6—H61.009
N4—C81.411 (2)C7—C81.372 (3)
N4—H81.0396C7—H70.932
C1—N1—H1114.10C5—C4—C3118.7 (2)
C1—N1—H2117.46C5—C4—H4120.7
H1—N1—H2128.4C3—C4—H4120.6
N3—N2—C1120.29 (16)C4—C5—C6120.7 (2)
N3—N2—H3117.89C4—C5—H5121.7
C1—N2—H3121.27C6—C5—H5117.5
C2—N3—N2116.44 (17)C7—C6—C5121.3 (2)
C9—N4—C8111.21 (17)C7—C6—H6119.6
C9—N4—H8119.41C5—C6—H6119.1
C8—N4—H8129.37C8—C7—C6117.7 (2)
O1—C1—N1125.19 (19)C8—C7—H7120.9
O1—C1—N2118.37 (18)C6—C7—H7121.3
N1—C1—N2116.44 (17)C7—C8—C3121.9 (2)
N3—C2—C3125.72 (19)C7—C8—N4128.3 (2)
N3—C2—C9127.54 (19)C3—C8—N4109.80 (18)
C3—C2—C9106.70 (17)O2—C9—N4126.61 (19)
C4—C3—C8119.7 (2)O2—C9—C2127.49 (19)
C4—C3—C2133.9 (2)N4—C9—C2105.89 (17)
C8—C3—C2106.38 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.912.183.087 (3)173
N1—H2···N30.942.252.659 (3)106
N2—H3···O20.932.002.755 (2)137
N4—H8···O1ii1.041.742.777 (2)178
C6—H6···O1iii1.012.553.520 (3)161
Symmetry codes: (i) x1, y+1/2, z+1/2; (ii) x+1, y+1/2, z1/2; (iii) x+2, y1/2, z+1/2.
(II) 1-methylindole-2,3-dione 3-semicarbazone top
Crystal data top
C10H10N4O2Dx = 1.434 Mg m3
Mr = 218.22Melting point: 249 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3118 reflections
a = 3.984 (2) Åθ = 2.1–25.0°
b = 20.930 (6) ŵ = 0.11 mm1
c = 12.122 (2) ÅT = 298 K
V = 1010.8 (6) Å3Prism, yellow
Z = 40.4 × 0.3 × 0.2 mm
F(000) = 456
Data collection top
Bruker SMART 1000
diffractometer
910 independent reflections
Radiation source: fine-focus sealed tube782 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
Detector resolution: 8.192 pixels mm-1θmax = 23.3°, θmin = 1.9°
ω scansh = 44
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
k = 2323
Tmin = 0.939, Tmax = 0.980l = 1313
9231 measured reflections
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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0557P)2]
where P = (Fo2 + 2Fc2)/3
910 reflections(Δ/σ)max < 0.001
146 parametersΔρmax = 0.10 e Å3
0 restraintsΔρmin = 0.12 e Å3
Crystal data top
C10H10N4O2V = 1010.8 (6) Å3
Mr = 218.22Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 3.984 (2) ŵ = 0.11 mm1
b = 20.930 (6) ÅT = 298 K
c = 12.122 (2) Å0.4 × 0.3 × 0.2 mm
Data collection top
Bruker SMART 1000
diffractometer
910 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
782 reflections with I > 2σ(I)
Tmin = 0.939, Tmax = 0.980Rint = 0.038
9231 measured reflectionsθmax = 23.3°
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.077H-atom parameters constrained
S = 1.02Δρmax = 0.10 e Å3
910 reflectionsΔρmin = 0.12 e Å3
146 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
O10.7991 (6)0.16810 (8)0.98208 (13)0.0716 (6)
O21.1174 (5)0.03955 (8)0.71768 (13)0.0646 (6)
N10.5444 (6)0.23666 (11)0.86358 (17)0.0652 (7)
H10.48480.26290.91460.078*
H20.49410.24450.79590.078*
N20.8028 (7)0.14554 (10)0.80117 (14)0.0589 (6)
H30.90910.11050.81330.071*
N30.7246 (6)0.16223 (9)0.69678 (14)0.0488 (5)
N41.0444 (5)0.03808 (9)0.52878 (15)0.0486 (5)
C10.7134 (7)0.18433 (11)0.8892 (2)0.0550 (7)
C20.8210 (6)0.12407 (10)0.61916 (18)0.0435 (6)
C30.7599 (6)0.13253 (10)0.50235 (17)0.0422 (6)
C40.6054 (7)0.17950 (11)0.44031 (19)0.0484 (6)
H40.51000.21500.47410.058*
C50.5958 (7)0.17263 (13)0.3271 (2)0.0569 (7)
H50.49430.20400.28420.068*
C60.7346 (7)0.11983 (12)0.2768 (2)0.0602 (7)
H60.72410.11630.20040.072*
C70.8886 (7)0.07211 (12)0.33672 (18)0.0545 (7)
H70.98120.03650.30230.065*
C80.8998 (6)0.07924 (10)0.44936 (18)0.0427 (6)
C91.0115 (7)0.06289 (11)0.63179 (19)0.0481 (6)
C101.2050 (8)0.02279 (10)0.5055 (2)0.0622 (8)
H10A1.35330.01810.44360.093*
H10B1.03690.05420.48870.093*
H10C1.33110.03630.56880.093*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.1081 (17)0.0666 (11)0.0401 (10)0.0106 (13)0.0094 (10)0.0006 (8)
O20.0830 (14)0.0571 (10)0.0537 (10)0.0084 (11)0.0110 (10)0.0082 (8)
N10.0911 (19)0.0614 (13)0.0432 (12)0.0067 (14)0.0079 (12)0.0058 (10)
N20.0807 (17)0.0510 (11)0.0450 (12)0.0046 (13)0.0035 (12)0.0043 (9)
N30.0595 (13)0.0498 (11)0.0370 (11)0.0035 (11)0.0023 (10)0.0037 (9)
N40.0529 (13)0.0404 (10)0.0526 (11)0.0022 (11)0.0012 (11)0.0051 (9)
C10.0713 (19)0.0505 (14)0.0432 (15)0.0132 (15)0.0050 (16)0.0035 (12)
C20.0478 (15)0.0404 (12)0.0423 (13)0.0051 (12)0.0022 (12)0.0019 (10)
C30.0410 (14)0.0405 (11)0.0451 (13)0.0053 (12)0.0000 (12)0.0019 (9)
C40.0453 (14)0.0458 (13)0.0540 (15)0.0004 (12)0.0003 (13)0.0006 (11)
C50.0554 (17)0.0622 (16)0.0530 (15)0.0035 (15)0.0089 (14)0.0101 (12)
C60.0649 (18)0.0719 (17)0.0437 (14)0.0091 (17)0.0025 (15)0.0022 (13)
C70.0583 (17)0.0559 (14)0.0492 (14)0.0049 (16)0.0046 (13)0.0108 (12)
C80.0404 (14)0.0412 (12)0.0465 (13)0.0049 (12)0.0020 (12)0.0015 (10)
C90.0501 (15)0.0440 (13)0.0500 (14)0.0050 (12)0.0015 (13)0.0030 (11)
C100.0656 (19)0.0429 (14)0.0781 (18)0.0068 (16)0.0051 (17)0.0040 (12)
Geometric parameters (Å, º) top
O1—C11.225 (3)C3—C41.382 (3)
O2—C91.225 (3)C3—C81.403 (3)
N1—C11.323 (3)C4—C51.381 (3)
N1—H10.86C4—H40.93
N1—H20.86C5—C61.378 (4)
N2—N31.349 (3)C5—H50.93
N2—C11.387 (3)C6—C71.379 (4)
N2—H30.86C6—H60.93
N3—C21.293 (3)C7—C81.374 (3)
N4—C91.359 (3)C7—H70.93
N4—C81.414 (3)C10—H10A0.96
N4—C101.453 (3)C10—H10B0.96
C2—C31.448 (3)C10—H10C0.96
C2—C91.496 (3)
C1—N1—H1120.0C6—C5—C4120.8 (2)
C1—N1—H2120.0C6—C5—H5119.6
H1—N1—H2120.0C4—C5—H5119.6
N3—N2—C1120.7 (2)C5—C6—C7121.8 (2)
N3—N2—H3119.7C5—C6—H6119.1
C1—N2—H3119.7C7—C6—H6119.1
C2—N3—N2117.0 (2)C8—C7—C6117.3 (2)
C9—N4—C8110.70 (18)C8—C7—H7121.3
C9—N4—C10123.8 (2)C6—C7—H7121.3
C8—N4—C10125.53 (19)C7—C8—C3121.9 (2)
O1—C1—N1126.0 (2)C7—C8—N4128.6 (2)
O1—C1—N2118.2 (2)C3—C8—N4109.54 (19)
N1—C1—N2115.8 (2)O2—C9—N4126.5 (2)
N3—C2—C3125.9 (2)O2—C9—C2127.1 (2)
N3—C2—C9127.2 (2)N4—C9—C2106.37 (19)
C3—C2—C9106.87 (19)N4—C10—H10A109.5
C4—C3—C8119.6 (2)N4—C10—H10B109.5
C4—C3—C2134.0 (2)H10A—C10—H10B109.5
C8—C3—C2106.49 (19)N4—C10—H10C109.5
C5—C4—C3118.6 (2)H10A—C10—H10C109.5
C5—C4—H4120.7H10B—C10—H10C109.5
C3—C4—H4120.7
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.052.903 (3)171
N1—H2···N30.862.292.652 (3)105
N2—H3···O20.862.062.742 (3)136
C7—H7···O2ii0.932.483.379 (4)163
C10—H10C···O20.962.552.905 (3)102
Symmetry codes: (i) x1/2, y+1/2, z+2; (ii) x+5/2, y, z1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC9H8N4O2C10H10N4O2
Mr204.19218.22
Crystal system, space groupMonoclinic, P21/cOrthorhombic, P212121
Temperature (K)298298
a, b, c (Å)5.554 (1), 18.754 (3), 8.974 (2)3.984 (2), 20.930 (6), 12.122 (2)
α, β, γ (°)90, 101.84 (3), 9090, 90, 90
V3)914.8 (3)1010.8 (6)
Z44
Radiation typeCu KαMo Kα
µ (mm1)0.930.11
Crystal size (mm)0.3 × 0.2 × 0.20.4 × 0.3 × 0.2
Data collection
DiffractometerSiemens AED
diffractometer
Bruker SMART 1000
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.939, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
1438, 1354, 907 9231, 910, 782
Rint0.0320.038
θmax (°)62.523.3
(sin θ/λ)max1)0.5750.556
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.092, 0.93 0.028, 0.077, 1.02
No. of reflections1354910
No. of parameters136146
H-atom treatmentH-atom parameters not refinedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.150.10, 0.12

Computer programs: local program (Belletti et al., 1988), SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2003), SHELXL97.

Selected bond lengths (Å) for (I) top
O1—C11.224 (2)C2—C31.454 (3)
O2—C91.230 (2)C2—C91.505 (3)
N1—C11.336 (3)C3—C41.383 (3)
N2—N31.356 (2)C3—C81.395 (3)
N2—C11.380 (3)C4—C51.380 (3)
N3—C21.293 (3)C5—C61.384 (4)
N4—C91.355 (3)C6—C71.380 (3)
N4—C81.411 (2)C7—C81.372 (3)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.912.183.087 (3)173
N1—H2···N30.942.252.659 (3)106
N2—H3···O20.932.002.755 (2)137
N4—H8···O1ii1.041.742.777 (2)178
Symmetry codes: (i) x1, y+1/2, z+1/2; (ii) x+1, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.052.903 (3)171
N1—H2···N30.862.292.652 (3)105
N2—H3···O20.862.062.742 (3)136
C7—H7···O2ii0.932.483.379 (4)163
C10—H10C···O20.962.552.905 (3)102
Symmetry codes: (i) x1/2, y+1/2, z+2; (ii) x+5/2, y, z1/2.
 

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