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The mol­ecules of 5-amino-1-(4-methoxy­benzo­yl)-3-methyl­pyrazole, C12H13N3O2, (I), and 5-amino-3-methyl-1-(2-nitro­benzo­yl)pyrazole, C11H10N4O3, (II), both contain intra­molecular N—H...O hydrogen bonds. The mol­ecules of (I) are linked into a chain of rings by a combination of N—H...N and N—H...π(arene) hydrogen bonds, while those of (II) are linked into a three-dimensional framework structure by N—H...N and C—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107067522/hj3064sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107067522/hj3064Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107067522/hj3064IIsup3.hkl
Contains datablock II

CCDC references: 681559; 681560

Comment top

5-Aminopyrazoles containing two or more functionalized substituent groups are versatile intermediates for the synthesis of polyheterocyclic systems (Bauer & Mahajanshetti, 1967; Tominaga et al., 1995), which are themselves of interest because of their potential bioactivity. We describe here the structures of two new 5-amino-1-aroylpyrazoles, 5-amino-1-(4-methoxybenzoyl)-3-methylpyrazole, (I) (Fig. 1), and 5-amino-3-methyl-1-(2-nitrobenzoyl)pyrazole, (II) (Fig. 2), which were both initially prepared for synthetic purposes using reactions between 3-aminocrotononitrile and an appropriately-substituted aroylhydrazide in the presence of sodium acetate.

The molecules of compounds (I) and (II) both contain an intramolecular N—H···O hydrogen bond (Tables 1 and 2), generating in each case an S(6) motif (Bernstein et al., 1995). These interactions may have some influence in controlling the molecular conformations, where the carbonyl groups are nearly coplanar with the adjacent pyrazole rings, as shown by the key torsion angles (Table 1). On the other hand the phenyl rings are twisted out of this plane; while the methoxy C atom C141 in (I) is effectively coplanar with the phenyl ring, the nitro group in (II) makes a dihedral angle of 23.8 (2)° with the adjacent phenyl ring.

Two factors may contribute to the difference between the phenyl ring conformations in (I) and (II). First, there is a short intramolecular C—H···N contact in (I) which, although probably not appropriately described as a hydrogen bond, may nonetheless be a weakly attractive interaction. Secondly, detailed comparison of the bond distances in the phenyl rings of (I) and (II) (Table 3) shows that in (I) the C12—C13 and C15—C16 distances are slightly, but significantly, shorter than the remainder, indicative of a modest degree of quinonoid character; the C1—C11 bond is significantly shorter in (I) than in (II), while C1—O1 is possibly longer in (I); and the C14—O14 bond is slightly short for its type [mean value (Allen et al., 1987) 1.370 Å, lower quartile value 1.363 Å]. The resulting polarized form, (Ia), would enhance the barrier to rotation about the C1—C11 bond in compound (I). The remaining bond distances and inter-bond angles show no unusual features.

The molecules of compound (I) are linked by a combination of N—H···N and N—H···π(arene) hydrogen bonds into a chain of rings generated by translation along the [100] direction (Fig. 3): within this chain, the N—H···N interaction generates a C(5) motif. The only direction-specific interaction of possible structural significance between adjacent chains is a rather long C—H···O contact, between molecules in pairs of chains related by inversion.

By contrast, the molecules of (II) are linked by one N—H···N and three C—H···O hydrogen bonds all involving nitro O atoms as the acceptors. It is sufficient to consider the framework formation in terms of just two hydrogen bonds, the N—H···N interaction and the shortest of the C—H···O interactions. Each of these two hydrogen bonds, acting independently, forms a simple chain, while the combination of the two interactions generates a third chain motif.

Amino atom N5 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H5B, to the ring atom N2 in the molecule at (1/2 + x, 3/2 - y, z), so forming a C(5) chain running parallel to the [100] direction and consisting of molecules related by the a-glide plane at y = 0.75 (Fig. 4). In the second chain motif, atom C16 at (x, y, z) acts as hydrogen-bond donor to nitro atom O122 in the molecule at (1 - x, 1 - y, -1/2 + z), so forming a C(6) chain running parallel to the [001] direction and consisting of molecules related by the 21 screw axis along (1/2, 1/2, z) (Fig. 5). Finally, the combination of these two hydrogen bonds, acting alternately, generates a C22(15) chain running parallel to the [011] direction (Fig. 6). The combination of the chains along [100], [011] and [001] is sufficient to generate a continuous three-dimensional framework structure. This framework may be modestly reinforced by the two hydrogen bonds involving C13 and C15, which generate, respectively, a C(5) chain parallel to [100] and a C(7) chain parallel to [011].

Hence, in each of (I) and (II), an N—H···N hydrogen bond forms a C(5) chain parallel to [100]. However, the hydrogen-bonded structure of (II) is much more complex than that of (I) by virtue of the presence of the nitro group with its two quite polar hydrogen-bond acceptors. It is noteworthy that the carbonyl O atom plays no significant role in the intermolecular hydrogen bonding in either compound, and that the resulting deficiency of hydrogen-bond acceptors in (I) leads to the formation of an N—H···π(arene) interaction.

Related literature top

For related literature, see: Allen et al. (1987).

Experimental top

Mixtures containing equimolar quantities (2 mmol of each component) of 3-aminocrotononitrile, an aroylhydrazide, 4-methoxybenzlhydrazide for (I) and 2-nitrobenzhydrazide for (II), and sodium acetate trihydrate in ethanol (50 ml) were heated under reflux for 2 h. The reaction mixtures were allowed to cool to ambient temperature, and then they were poured into water (50 ml) with vigorous stirring; stirring was then continued for 20 min. The resulting solid products were collected by filtration and recrystallized from ethanol to provide crystals of (I) and (II) suitable for single-crystal X-ray diffraction. For (I), colourless crystals, m.p. 354–355 K, yield 90%; MS (30 eV) m/z (%) 231 (16, M+), 135 (100), 107 (13), 77 (20). For (II), yellow crystals, m.p. 490–491 K, yield 97%; MS (70 eV) m/z (%) 246 (34, M+), 151 (66), 121 (70), 76 (85), 51 (91), 41 (100).

Refinement top

Crystals of (I) are triclinic; the space group P1 was selected and confirmed by the structure analysis. For (II), the systematic absences permitted Pna21 or Pnam (= Pnma) as possible space groups: Pna21 was selected and confirmed by the structure analysis. All H atoms were located in difference maps. H atoms bonded to C atoms were then treated as riding atoms in geometrically idealized positions with distances C—H 0.95 Å (aromatic and pyrazole) or 0.98 Å (methyl) and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups and 1.2 for all other H atoms. The H atoms bonded to N atoms were permitted to ride at the positions deduced from the difference maps with Uiso(H) = 1.2Ueq(N), giving N—H distances in the range 0.94–0.97 Å. In the absence of significant resonant scattering, it was not possible to determine the correct orientation of the structure of (II) relative to the polar axis direction: accordingly, the Friedel-equivalent reflections were merged prior to the final cycles of refinement.

Computing details top

For both compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: Sir2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. A molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the formation of a chain of rings along [100] built from N—H···O, N—H···N and N—H···π(arene) hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 + x, y, z) and (-1 + x, y, z), respectively.
[Figure 4] Fig. 4. Part of the crystal structure of (II), showing the formation of a chain of rings along [100] containing N—H···O and N—H···N hydrogen bonds only. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 + x, 3/2 - y, z) and (-1/2 + x, 3/2 - y, z), respectively.
[Figure 5] Fig. 5. Part of the crystal structure of (II), showing the formation of a chain along [001] containing N—H···O and C—H···O hydrogen bonds only. For the sake of clarity, H atoms bonded to C atoms and not involved in the hydrogen bonding have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 - x, 1 - y, -1/2 + z) and (1 - x, 1 - y, 1/2 + z), respectively.
[Figure 6] Fig. 6. A stereoview of part of the crystal structure of (II), showing the formation of a chain along [011] containing N—H···O, N—H···N and C—H···O hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms and not involved in the hydrogen bonding have been omitted.
(I) 5-Amino-1-(4-methoxybenzoyl)-3-methylpyrazole top
Crystal data top
C12H13N3O2Z = 2
Mr = 231.25F(000) = 244
Triclinic, P1Dx = 1.345 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.1920 (15) ÅCell parameters from 2614 reflections
b = 9.192 (2) Åθ = 3.3–27.5°
c = 10.546 (2) ŵ = 0.10 mm1
α = 73.69 (2)°T = 120 K
β = 85.634 (17)°Block, colourless
γ = 82.83 (3)°0.50 × 0.35 × 0.27 mm
V = 571.1 (2) Å3
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2614 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1936 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.3°
ϕ & ω scansh = 88
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1111
Tmin = 0.958, Tmax = 0.975l = 1313
13948 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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0703P)2 + 0.2759P]
where P = (Fo2 + 2Fc2)/3
2614 reflections(Δ/σ)max < 0.001
156 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
C12H13N3O2γ = 82.83 (3)°
Mr = 231.25V = 571.1 (2) Å3
Triclinic, P1Z = 2
a = 6.1920 (15) ÅMo Kα radiation
b = 9.192 (2) ŵ = 0.10 mm1
c = 10.546 (2) ÅT = 120 K
α = 73.69 (2)°0.50 × 0.35 × 0.27 mm
β = 85.634 (17)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2614 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1936 reflections with I > 2σ(I)
Tmin = 0.958, Tmax = 0.975Rint = 0.031
13948 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.142H-atom parameters constrained
S = 1.08Δρmax = 0.26 e Å3
2614 reflectionsΔρmin = 0.33 e Å3
156 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.67655 (19)0.41134 (14)0.18740 (12)0.0279 (3)
O140.1286 (2)0.08983 (14)0.10792 (13)0.0313 (3)
N10.5772 (2)0.32071 (16)0.40425 (13)0.0216 (3)
N20.4089 (2)0.27730 (16)0.49827 (13)0.0230 (3)
N50.9386 (2)0.39991 (17)0.39145 (15)0.0266 (3)
C10.5515 (3)0.33904 (18)0.26987 (16)0.0222 (4)
C30.4870 (3)0.27986 (18)0.61073 (16)0.0229 (4)
C40.6997 (3)0.32419 (19)0.59450 (17)0.0238 (4)
C50.7549 (3)0.35168 (19)0.46240 (17)0.0224 (4)
C110.3717 (3)0.26982 (19)0.23174 (16)0.0227 (4)
C120.2977 (3)0.13189 (19)0.30579 (17)0.0252 (4)
C130.1331 (3)0.07495 (19)0.26012 (18)0.0279 (4)
C140.0375 (3)0.15420 (19)0.14054 (17)0.0238 (4)
C150.1137 (3)0.28931 (19)0.06448 (16)0.0241 (4)
C160.2804 (3)0.34537 (19)0.11027 (16)0.0228 (4)
C310.3521 (3)0.2367 (2)0.73602 (17)0.0292 (4)
C1410.2301 (3)0.1654 (2)0.01429 (18)0.0326 (4)
H40.78690.33310.66170.029*
H5A0.94340.40260.29920.032*
H5B1.07200.36220.43810.032*
H120.36090.07780.38730.030*
H130.08390.01900.31020.033*
H150.05200.34230.01780.029*
H160.33390.43700.05820.027*
H14A0.29120.26860.01300.049*
H14B0.34700.10810.02580.049*
H14C0.12160.17120.08770.049*
H31A0.20090.23500.71540.044*
H31B0.35770.31140.78590.044*
H31C0.40900.13540.78910.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0253 (6)0.0350 (7)0.0229 (6)0.0061 (5)0.0021 (5)0.0067 (5)
O140.0336 (7)0.0306 (7)0.0318 (7)0.0089 (5)0.0097 (5)0.0072 (5)
N10.0180 (7)0.0260 (7)0.0206 (7)0.0030 (5)0.0005 (5)0.0058 (5)
N20.0204 (7)0.0268 (7)0.0207 (7)0.0035 (6)0.0011 (5)0.0048 (6)
N50.0187 (7)0.0333 (8)0.0275 (8)0.0040 (6)0.0007 (6)0.0075 (6)
C10.0210 (8)0.0222 (8)0.0224 (8)0.0004 (6)0.0009 (6)0.0059 (6)
C30.0233 (8)0.0214 (8)0.0234 (8)0.0018 (6)0.0024 (7)0.0051 (6)
C40.0237 (8)0.0238 (8)0.0243 (8)0.0024 (7)0.0037 (7)0.0066 (7)
C50.0192 (8)0.0220 (8)0.0262 (8)0.0016 (6)0.0026 (6)0.0069 (6)
C110.0211 (8)0.0265 (8)0.0215 (8)0.0012 (6)0.0003 (6)0.0090 (7)
C120.0302 (9)0.0222 (8)0.0231 (8)0.0000 (7)0.0067 (7)0.0058 (7)
C130.0360 (10)0.0206 (8)0.0275 (9)0.0045 (7)0.0060 (7)0.0054 (7)
C140.0230 (8)0.0241 (8)0.0270 (9)0.0016 (7)0.0024 (7)0.0116 (7)
C150.0225 (8)0.0283 (9)0.0207 (8)0.0011 (7)0.0009 (6)0.0071 (7)
C160.0211 (8)0.0252 (8)0.0210 (8)0.0016 (6)0.0016 (6)0.0057 (6)
C310.0288 (9)0.0360 (10)0.0222 (9)0.0059 (7)0.0009 (7)0.0058 (7)
C1410.0324 (10)0.0360 (10)0.0319 (10)0.0024 (8)0.0124 (8)0.0111 (8)
Geometric parameters (Å, º) top
O1—C11.224 (2)N5—H5B0.9693
N2—C31.322 (2)C15—C161.383 (2)
N2—N11.3973 (19)C15—C141.392 (2)
C4—C51.368 (2)C15—H150.95
C4—C31.411 (2)C14—C131.401 (2)
C4—H40.95C31—C31.490 (2)
C12—C131.376 (2)C31—H31A0.98
C12—C111.401 (2)C31—H31B0.98
C12—H120.95C31—H31C0.98
N1—C51.395 (2)C11—C161.398 (2)
N1—C11.398 (2)C16—H160.95
C1—C111.481 (2)C13—H130.95
O14—C141.359 (2)C141—H14A0.98
O14—C1411.432 (2)C141—H14B0.98
N5—C51.364 (2)C141—H14C0.98
N5—H5A0.9639
C3—N2—N1104.15 (13)C15—C14—C13120.01 (15)
C5—C4—C3106.09 (15)C3—C31—H31A109.5
C5—C4—H4127.0C3—C31—H31B109.5
C3—C4—H4127.0H31A—C31—H31B109.5
C13—C12—C11119.83 (16)C3—C31—H31C109.5
C13—C12—H12120.1H31A—C31—H31C109.5
C11—C12—H12120.1H31B—C31—H31C109.5
C5—N1—N2111.02 (13)N2—C3—C4112.68 (15)
C5—N1—C1127.54 (14)N2—C3—C31119.75 (15)
N2—N1—C1121.28 (13)C4—C3—C31127.56 (15)
O1—C1—N1119.61 (15)C16—C11—C12119.09 (15)
O1—C1—C11121.90 (15)C16—C11—C1116.60 (15)
N1—C1—C11118.48 (14)C12—C11—C1124.22 (15)
C14—O14—C141117.57 (14)C15—C16—C11121.27 (16)
C5—N5—H5A115.5C15—C16—H16119.4
C5—N5—H5B114.3C11—C16—H16119.4
H5A—N5—H5B117.0C12—C13—C14120.62 (16)
C16—C15—C14119.11 (15)C12—C13—H13119.7
C16—C15—H15120.4C14—C13—H13119.7
C14—C15—H15120.4O14—C141—H14A109.5
N5—C5—C4131.29 (16)O14—C141—H14B109.5
N5—C5—N1122.67 (15)H14A—C141—H14B109.5
C4—C5—N1106.04 (14)O14—C141—H14C109.5
O14—C14—C15124.61 (15)H14A—C141—H14C109.5
O14—C14—C13115.37 (15)H14B—C141—H14C109.5
C3—N2—N1—C51.05 (17)N1—N2—C3—C40.37 (18)
C3—N2—N1—C1176.71 (14)N1—N2—C3—C31178.99 (14)
C5—N1—C1—O112.6 (3)C5—C4—C3—N20.4 (2)
N2—N1—C1—O1162.24 (14)C5—C4—C3—C31179.73 (16)
C5—N1—C1—C11167.48 (15)C13—C12—C11—C161.7 (2)
N2—N1—C1—C1117.6 (2)C13—C12—C11—C1178.26 (15)
C3—C4—C5—N5178.67 (17)O1—C1—C11—C1630.8 (2)
C3—C4—C5—N11.03 (18)N1—C1—C11—C16149.09 (15)
N2—N1—C5—N5178.40 (15)O1—C1—C11—C12145.82 (17)
C1—N1—C5—N53.1 (3)N1—C1—C11—C1234.3 (2)
N2—N1—C5—C41.33 (18)C14—C15—C16—C110.7 (2)
C1—N1—C5—C4176.65 (15)C12—C11—C16—C152.3 (2)
C141—O14—C14—C151.0 (2)C1—C11—C16—C15179.13 (14)
C141—O14—C14—C13179.22 (15)C11—C12—C13—C140.5 (3)
C16—C15—C14—O14178.27 (15)O14—C14—C13—C12177.68 (15)
C16—C15—C14—C131.6 (2)C15—C14—C13—C122.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5A···O10.962.082.763 (2)126
N5—H5A···Cgi0.962.713.365 (2)126
N5—H5B···N2i0.972.213.160 (2)167
C12—H12···N20.952.492.889 (2)105
C16—H16···O1ii0.952.583.317 (2)135
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z.
(II) 5-Amino-3-methyl-1-(2-nitrobenzoyl)pyrazole top
Crystal data top
C11H10N4O3F(000) = 512
Mr = 246.23Dx = 1.504 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 1309 reflections
a = 11.4212 (15) Åθ = 3.2–27.5°
b = 7.1787 (14) ŵ = 0.11 mm1
c = 13.2595 (10) ÅT = 120 K
V = 1087.1 (3) Å3Block, yellow
Z = 40.55 × 0.51 × 0.45 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer
1309 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1197 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.2°
ϕ & ω scansh = 1414
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 99
Tmin = 0.943, Tmax = 0.950l = 1617
23596 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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-atom parameters constrained
S = 1.16 w = 1/[σ2(Fo2) + (0.0449P)2 + 0.5442P]
where P = (Fo2 + 2Fc2)/3
1309 reflections(Δ/σ)max < 0.001
165 parametersΔρmax = 0.20 e Å3
1 restraintΔρmin = 0.21 e Å3
Crystal data top
C11H10N4O3V = 1087.1 (3) Å3
Mr = 246.23Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 11.4212 (15) ŵ = 0.11 mm1
b = 7.1787 (14) ÅT = 120 K
c = 13.2595 (10) Å0.55 × 0.51 × 0.45 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer
1309 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1197 reflections with I > 2σ(I)
Tmin = 0.943, Tmax = 0.950Rint = 0.044
23596 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0391 restraint
wR(F2) = 0.097H-atom parameters constrained
S = 1.16Δρmax = 0.20 e Å3
1309 reflectionsΔρmin = 0.21 e Å3
165 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.67677 (17)0.4541 (3)0.50590 (15)0.0258 (4)
O1210.53764 (16)0.2764 (3)0.70553 (16)0.0266 (4)
O1220.36585 (18)0.3140 (3)0.77307 (17)0.0299 (5)
N10.64417 (19)0.6216 (3)0.64926 (17)0.0193 (4)
N20.56231 (18)0.7122 (3)0.71101 (17)0.0203 (4)
N50.85228 (19)0.5661 (3)0.63892 (19)0.0246 (5)
N120.43602 (19)0.3340 (3)0.70350 (17)0.0218 (5)
C10.6075 (2)0.5218 (4)0.56546 (18)0.0191 (5)
C30.6277 (2)0.7868 (3)0.7831 (2)0.0205 (5)
C40.7478 (2)0.7483 (4)0.7716 (2)0.0209 (5)
C50.7576 (2)0.6442 (3)0.6856 (2)0.0202 (5)
C110.4777 (2)0.5132 (3)0.5484 (2)0.0187 (5)
C120.3959 (2)0.4307 (3)0.6120 (2)0.0202 (5)
C130.2772 (2)0.4291 (4)0.5914 (2)0.0248 (6)
C140.2381 (2)0.5128 (4)0.5034 (2)0.0286 (6)
C150.3172 (3)0.5943 (4)0.4377 (2)0.0272 (6)
C160.4369 (2)0.5941 (4)0.4596 (2)0.0229 (5)
C310.5710 (3)0.8975 (4)0.8653 (2)0.0276 (6)
H5A0.83930.52620.57250.030*
H5B0.92320.62850.65370.030*
H40.80950.78680.81490.025*
H130.22350.37190.63660.030*
H140.15690.51430.48820.034*
H150.28990.65080.37730.033*
H160.49060.64930.41370.027*
H31A0.49150.93200.84480.041*
H31B0.61681.01050.87800.041*
H31C0.56750.82240.92700.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0246 (10)0.0291 (10)0.0237 (10)0.0021 (8)0.0031 (9)0.0039 (8)
O1210.0229 (9)0.0267 (9)0.0303 (10)0.0023 (8)0.0002 (9)0.0057 (9)
O1220.0329 (10)0.0329 (11)0.0240 (9)0.0048 (9)0.0085 (9)0.0004 (9)
N10.0165 (9)0.0211 (10)0.0203 (10)0.0001 (8)0.0011 (8)0.0026 (9)
N20.0196 (9)0.0212 (10)0.0201 (10)0.0021 (8)0.0020 (9)0.0047 (9)
N50.0194 (10)0.0259 (11)0.0286 (12)0.0009 (9)0.0018 (9)0.0008 (10)
N120.0246 (10)0.0198 (10)0.0210 (10)0.0034 (8)0.0011 (9)0.0025 (10)
C10.0204 (12)0.0182 (11)0.0186 (12)0.0021 (10)0.0011 (10)0.0005 (10)
C30.0247 (12)0.0175 (11)0.0193 (11)0.0002 (10)0.0033 (11)0.0039 (10)
C40.0211 (11)0.0230 (12)0.0185 (12)0.0024 (10)0.0029 (10)0.0041 (11)
C50.0170 (11)0.0187 (11)0.0250 (12)0.0020 (9)0.0019 (10)0.0049 (10)
C110.0208 (12)0.0159 (11)0.0195 (11)0.0002 (10)0.0003 (9)0.0033 (10)
C120.0216 (12)0.0180 (11)0.0210 (12)0.0001 (10)0.0031 (10)0.0013 (9)
C130.0205 (12)0.0245 (13)0.0293 (14)0.0033 (10)0.0016 (11)0.0066 (12)
C140.0234 (13)0.0295 (15)0.0329 (15)0.0031 (11)0.0082 (13)0.0113 (12)
C150.0319 (15)0.0265 (13)0.0232 (13)0.0046 (12)0.0090 (12)0.0042 (11)
C160.0272 (12)0.0221 (13)0.0194 (12)0.0015 (10)0.0026 (11)0.0028 (11)
C310.0334 (15)0.0262 (13)0.0233 (14)0.0010 (11)0.0000 (11)0.0050 (12)
Geometric parameters (Å, º) top
O1—C11.219 (3)C4—H40.95
O121—N121.232 (3)C11—C121.392 (4)
O122—N121.231 (3)C11—C161.393 (4)
N1—C11.387 (3)C12—C131.383 (4)
N1—C51.392 (3)C13—C141.386 (4)
N1—N21.403 (3)C13—H130.95
N2—C31.326 (3)C14—C151.385 (4)
N5—C51.366 (3)C14—H140.95
N5—H5A0.9383C15—C161.397 (4)
N5—H5B0.9457C15—H150.95
N12—C121.471 (3)C16—H160.95
C1—C111.501 (4)C31—H31A0.98
C3—C41.408 (4)C31—H31B0.98
C3—C311.496 (4)C31—H31C0.98
C4—C51.369 (4)
C1—N1—C5128.2 (2)C12—C11—C1126.1 (2)
C1—N1—N2120.4 (2)C16—C11—C1116.2 (2)
C5—N1—N2111.4 (2)C13—C12—C11122.9 (2)
C3—N2—N1103.5 (2)C13—C12—N12117.7 (2)
C5—N5—H5A115.2C11—C12—N12119.4 (2)
C5—N5—H5B112.9C12—C13—C14118.5 (3)
H5A—N5—H5B118.3C12—C13—H13120.7
O122—N12—O121123.9 (2)C14—C13—H13120.7
O122—N12—C12118.1 (2)C15—C14—C13120.2 (3)
O121—N12—C12118.0 (2)C15—C14—H14119.9
O1—C1—N1122.0 (2)C13—C14—H14119.9
O1—C1—C11121.8 (2)C14—C15—C16120.4 (3)
N1—C1—C11116.1 (2)C14—C15—H15119.8
N2—C3—C4113.0 (2)C16—C15—H15119.8
N2—C3—C31119.7 (2)C11—C16—C15120.2 (3)
C4—C3—C31127.2 (3)C11—C16—H16119.9
C5—C4—C3106.1 (2)C15—C16—H16119.9
C5—C4—H4126.9C3—C31—H31A109.5
C3—C4—H4126.9C3—C31—H31B109.5
N5—C5—C4131.8 (2)H31A—C31—H31B109.5
N5—C5—N1122.1 (2)C3—C31—H31C109.5
C4—C5—N1106.0 (2)H31A—C31—H31C109.5
C12—C11—C16117.7 (2)H31B—C31—H31C109.5
C1—N1—N2—C3178.4 (2)O1—C1—C11—C1658.7 (3)
C5—N1—N2—C30.1 (3)N1—C1—C11—C16117.2 (3)
C5—N1—C1—O17.7 (4)C16—C11—C12—C131.2 (4)
N2—N1—C1—O1174.0 (2)C1—C11—C12—C13179.6 (2)
C5—N1—C1—C11176.4 (2)C16—C11—C12—N12176.4 (2)
N2—N1—C1—C111.9 (3)C1—C11—C12—N122.8 (4)
N1—N2—C3—C40.4 (3)O122—N12—C12—C1324.6 (3)
N1—N2—C3—C31180.0 (2)O121—N12—C12—C13154.7 (2)
N2—C3—C4—C50.7 (3)O122—N12—C12—C11157.6 (2)
C31—C3—C4—C5179.6 (2)O121—N12—C12—C1123.1 (3)
C3—C4—C5—N5179.0 (3)C11—C12—C13—C140.3 (4)
C3—C4—C5—N10.7 (3)N12—C12—C13—C14177.4 (2)
C1—N1—C5—N50.6 (4)C12—C13—C14—C150.6 (4)
N2—N1—C5—N5179.0 (2)C13—C14—C15—C160.4 (4)
C1—N1—C5—C4177.9 (2)C12—C11—C16—C151.3 (4)
N2—N1—C5—C40.6 (3)C1—C11—C16—C15179.4 (2)
O1—C1—C11—C12120.5 (3)C14—C15—C16—C110.6 (4)
N1—C1—C11—C1263.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5A···O10.942.122.788 (3)127
N5—H5B···N2i0.952.103.033 (3)169
C13—H13···O121ii0.952.543.457 (3)161
C15—H15···O122iii0.952.543.409 (4)152
C16—H16···O122iv0.952.503.410 (3)161
Symmetry codes: (i) x+1/2, y+3/2, z; (ii) x1/2, y+1/2, z; (iii) x+1/2, y+1/2, z1/2; (iv) x+1, y+1, z1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC12H13N3O2C11H10N4O3
Mr231.25246.23
Crystal system, space groupTriclinic, P1Orthorhombic, Pna21
Temperature (K)120120
a, b, c (Å)6.1920 (15), 9.192 (2), 10.546 (2)11.4212 (15), 7.1787 (14), 13.2595 (10)
α, β, γ (°)73.69 (2), 85.634 (17), 82.83 (3)90, 90, 90
V3)571.1 (2)1087.1 (3)
Z24
Radiation typeMo KαMo Kα
µ (mm1)0.100.11
Crystal size (mm)0.50 × 0.35 × 0.270.55 × 0.51 × 0.45
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Bruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.958, 0.9750.943, 0.950
No. of measured, independent and
observed [I > 2σ(I)] reflections
13948, 2614, 1936 23596, 1309, 1197
Rint0.0310.044
(sin θ/λ)max1)0.6500.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.142, 1.08 0.039, 0.097, 1.16
No. of reflections26141309
No. of parameters156165
No. of restraints01
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.26, 0.330.20, 0.21

Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), Sir2004 (Burla et al., 2005), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N5—H5A···O10.962.082.763 (2)126
N5—H5A···Cgi0.962.713.365 (2)126
N5—H5B···N2i0.972.213.160 (2)167
C12—H12···N20.952.492.889 (2)105
C16—H16···O1ii0.952.583.317 (2)135
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N5—H5A···O10.942.122.788 (3)127
N5—H5B···N2i0.952.103.033 (3)169
C13—H13···O121ii0.952.543.457 (3)161
C15—H15···O122iii0.952.543.409 (4)152
C16—H16···O122iv0.952.503.410 (3)161
Symmetry codes: (i) x+1/2, y+3/2, z; (ii) x1/2, y+1/2, z; (iii) x+1/2, y+1/2, z1/2; (iv) x+1, y+1, z1/2.
Selected distances (Å) and torsion angles (°) for compounds (I) and (II) top
Parameter(I)(II)
C1-O11.224 (2)1.219 (3)
C1-C111.481 (2)1.501 (4)
C11-C121.401 (2)1.392 (4)
C12-C131.376 (2)1.383 (4)
C13-C141.401 (2)1.386 (4)
C14-C151.392 (2)1.385 (4)
C15-C161.383 (2)1.397 (4)
C16-C111.398 (2)1.393 (4)
C14-O141.359 (2)
N2-N1-C1-O1162.24 (14)174.0 (2)
N2-N1-C1-C11-17.6 (2)-1.9 (3)
N1-C1-C11-C12-34.3 (2))-63.6 (3)
C13-C14-O14-C141-179.22 (15)
C11-C12-N12-O121-23.1 (3)
 

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