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The compounds (2′E,2′E)-2,2′-(propane-1,2-diyl­idene)bis­[1-(2-nitro­phen­yl)hy­drazine], C15H14N6O4, (I), and (2Z,3Z)-ethyl 3-[2-(2-nitro­phen­yl)hydrazinyl­idene]-2-[2-(4-nitro­phen­yl)hydrazinyl­idene]butano­ate tetrahydrofuran hemi­solvate, C18H18N6O6·0.5C4H8O, (II), are puzzling outliers deviating from a general synthetic route aimed at the preparation of substituted pyrazoles. Possible reasons for this outcome, which is exceptional in an otherwise firmly established synthetic procedure, are analyzed. Compound (I) is unsolvated, while compound (II) crystallizes with a tetra­hydro­furan solvent mol­ecule lying on an inversion centre. The eth­oxy­carbonyl chain of (II), in turn, appears disordered into two equally populated (50%) moieties. In both structures, a plethora of different commonly occurring weak inter­molecular inter­actions [viz. π(phen­yl)...π(phenyl), π(C=N)...π(C=N), π(phen­yl)...π(C=N), N—H...O and C—H...O] appear responsible for the crystal stability. Much less common are the short O(nitro)...O(nitro) contacts which are observed in the structure of (I), an example of unusual `electron donor–acceptor' (EDA) inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615021944/fp3020sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615021944/fp3020Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615021944/fp3020IIsup3.hkl
Contains datablock II

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615021944/fp3020sup4.pdf
Supplementary material

CCDC references: 1437501; 1437500

Introduction top

In previous articles, we presented a general synthetic route for obtaining a large library of substituted pyrazoles (Bustos et al., 2009; Faúndez-Gutiérrez et al., 2014), and several of them have been characterized by X-ray diffraction methods (Bustos et al., 2006, 2007, 2015; Bustos, Pérez-Cerda et al., 2012; Alvarez Thon, Bustos, Diaz-Marín et al., 2013). These compounds can be synthesized (see Scheme 1) by reaction of β-diketohidrazones, (1), with substituted aryl­hydrazines in acid media and with ethanol as solvent. As a first step, we propose that the aryl­hydrazines condense with one carbonyl group yielding α,β-dihydrazoketo derivatives as the inter­mediate, (2). Then, protonation of the remaining carbonyl group triggers an addition reaction with displacement of one molecule of H2O, yielding the respective pyrazole family, (3).

Likewise, we found (see Scheme 2) that α-hydrazo-β-ketoesters, (4), derivatives of ethyl aceto­acetate, react with aryl­hydrazines in a similar manner to β-diketohydrazones, but with inter­mediate (5) formed as a first step. Then, after protonation of the eth­oxy group, the addition reaction with displacement of one ethanol molecule occurs to give the pyrazolone derivatives, (6), as a major product (Bustos, Escobar-Fuentealba et al., 2012; Alvarez-Thon, Bustos, Espinoza-Santibañez et al., 2013; Alvarez-Thon et al., 2014).

However, depending of the nature of the used precursors, we have found some exceptions. In fact, the addition–displacement reaction does not occur when the inter­mediates, i.e. (2) or (5) in Schemes 1 and 2, contain the groups R1 = 4-NO2 and R2 = 2-NO2 in (2), and R1 = R2 = 2-NO2 in (5). In this manner, compounds (2) and (5) are stabilized as major products. Moreover, an additional unexpected by-product, i.e. (9), was formed from (7), which is a derivative of (2) in Scheme 1, probably due to loss of one molecule of ethyl acetate in the manner shown in Scheme 3.

We think that this behaviour is probably due to substituent groups (R2 = 2-NO2) present in the (2-nitro­phenyl)­hydrazinyl­idene fragments of (2) and (5) causing a strong electron-withdrawing effect on the unshared electron pair located on the N atom, thus avoiding the expected cyclization reaction to give (3) and (6), respectively (see Schemes 1 and 2). However, in the case of inter­mediate (2), the presence of one 2-NO2 group in each of the aromatic rings results in an electron-withdrawing effect that is strong enough to allow removal of an ethyl acetate molecule and give a by-product; the motion of electrons is shown in Scheme 3. In this work, we present the crystalline and molecular structure of α,β-dihydrazoester (5), with R1 = 4-NO2 and R2 = 2-NO2, and the by-product α-dihydrazone (9), which for simplicity we have labeled as compounds (I) and (II), respectively.

Structural studies of compounds such as (I) and (II) are relevant because they contain heterodienic systems forming intra- or inter­molecular hydrogen bonds which, inter alia, could have important implications in the development of new optical, magnetic and electronic systems (Bertolasi et al., 1999; Sharma et al., 1992).

Experimental top

Physical measurements top

Melting points were registered using digital STUARD SMP10 equipment. Elemental analyses were obtained on a Fison EA 1108 analyser. The UV–Visible spectra were registered in quartz cells (inter­nal diameter 10 mm) in the range 100–250 nm on a PerkinElmer Lambda 35 spectrophotometer, using a concentrated solution (1.0 × 10 -3 mol l-1) of compounds in CHCl3 and diluting to around 1.0 × 10 -5 mol l-1. IR spectra in solid state were registered on a ATR Jasco PRO450-S assembled on a Jasco FT–IR-4200 equipment. The 1H NMR and 13C NMR spectra were obtained in CDCl3 solution using a glass tube (inter­nal diameter 5 mm) on a Bruker Avance 400 spectrophotometer with the deuterated resonance of the solvent as standard. Single-crystal X-ray diffraction data was gathered with a Bruker SMART CCD area-detector diffractometer.

Synthesis and crystallization top

Reagents (ethyl aceto­acetate, sodium nitrite, sodium acetate, sodium hydroxide, 2-nitro­aniline, 4-nitro­aniline, 2-nitro­phenyl­hydrazine and 4-nitro­phenyl­hydrazine), solvents (ethanol, tetra­hydro­furan and CDCl3) and glacial acetic acid and were procured from common commercial sources (Merck Chemical and Sigma–Aldrich) and used without further purification.

Preparation of the precursors top

Precursors (1) and (4) were obtained according to literature procedures (Yao, 1964; Bertolasi et al.., 1999; Bustos et al., 2009). β-Diketohydrazone (1) {R = 4-NO2; systematic name: 3-[2-(4-nitro­phenyl)­hydrazinyl­idene]pentane-2,4-dione} was synthesized by coupling of an equimolar qu­antity (0.05 mol) of the ethyl acetyl­acetonate with the 4-nitro­phenyl­diazo­nium salt. Moreover, α-hydrazo-β-ketoester (4) {R = 2-NO2; systematic name: (Z)-ethyl 2-[2-(2-nitro­phenyl)­hydrazinyl­idene]-3-oxo­butano­ate} was synthesized by reaction of an equimolar qu­antity (0.05 mol) of ethyl aceto­acetate with the 2-nitro­phenyl­diazo­nium salt. The products were recrystallized from ethanol and the structures checked by IR spectroscopy.

\ Preparation of (2E,2'E)-2,2'-(propane-1,2-diyl­idene)bis­[1-(2-nitro­phenyl)\ hydrazine], (I) top

To a 100 ml round-bottomed flask were added (2.793 g, 10 mmol) of recrystallized ethyl (Z)-2-[(4-nitro­phenyl)­hydrazinyl­idene]-3-oxo­butano­ate, (4) (2.793 g, 10 mmol), 2-nitro­phenyl­hydrazine (97%; 1.578 g, 10 mmol), glacial acetic acid (5 ml) and ethanol (30 ml). The mixture was stirred and heated gently under reflux near the boiling point. After 36 h the reaction mixture was cooled at 263 K for 2 h and the red solid was filtered by suction, washed with an abundant qu­antity of water (500 ml) and dried in a vacuum oven at 313 K for 12 h. Single crystals suitable for diffraction studies were obtained by recrystallization of the crude compound from tetra­hydro­furan (THF) (yield 75.4%; uncorrected m.p. 569–571 K). Analysis calculated (%) for the dried compound C18H18N6O6: C 52.29, H 4.62, N 19.26; found: C 52.47, H 4.81, N 18.90.

\ Preparation of (2Z,3E)-ethyl 3-[2-(2-nitro­phenyl)­hydrazinyl­idene]-2-[2-(4-nitro­phenyl)­hydrazinilyl­idene]\ butano­ate, (II) top

This compound was synthesized using the same procedure as for (I) using 3-[2-(4-nitro­phenyl)­hydrazinyl­idene]pentane-2,4-dione, (1) (2.492 g, 10 mmol), and the same qu­anti­ties of 2-nitro­phenyl­hydrazine (97%), acetic acid and ethanol. The filtrate contained mainly (8) and was suspended in ethanol (40 ml) and the insoluble fraction corresponding to (II) was separated by filtration and recrystallized from THF (30 ml). After slow evaporation of the solvent, red crystals were obtained. [yield 5.2%; uncorrected m.p. 510–511 K (decomposition)]. Analysis calculated (%) for C15H14N6O4: C 52.63, H 4.12, N 24.55; found: C 53.01, H 4.61, N 25.07. IR and NMR data are available in the Supporting information.

Refinement top

Crystal data, data collection and structure refinement details for both structures are summarized in Table 1. The tetra­hydro­furan solvent molecule in (II) sits on an inversion centre and accordingly has a 50% occupancy. The eth­oxy­carbony substituent, in turn, appears disordered into two equally populated 50% moieties, which were refinend with restrained distances and displacement factors.

All H atoms were originally found in difference maps, but treated differently in the refinements. In all cases, they were assigned isotropic displacement parameters associated with their hosts, in the form Uiso(H) equal to xUeq(host). H atoms on N atoms were refined with restrained N—H distances of 0.85 (1) Å and with x = 1.2. H atoms on C atoms were repositioned in their expected sites and allowed to ride, with aromatic C—H = 0.93 Å and x = 1.2, and methyl C—H = 0.96 Å and x = 1.5; the latter groups were also allowed to rotate around their C—C bond. [The THF H atoms are not included in the CIF formulae for (II); are they included in the Crystal data?]

Results and discussion top

Figs. 1 and 2 show molecular views of (I) and (II), with the atom and ring numbering, for convenience. Fig. 2 shows, in addition, a detailed view of the way the disordered fractions co-exist in (II) (see discussion below). As shown in Table 1, the compounds are quite different from a crystalline point of view (space group, z and cell dimensions etc.). From a molecular side, both molecules share the same Ph—N—NC—CN—N—Ph nucleus, and the metric similarities can be assessed in Table 2, where bond lengths along the chain are presented, and from where the clear single/double bond sequence is apparent (see Scheme 4). The molecular differences reside in the location of the substituents in the central C—C bridge [i.e. methyl and H in (I), and methyl and disordered COOEt in (II)], as well as in the location of the external nitro groups [2- and 2'-positions in (I), and 2- and 4'-positions in (II)]. A further detail setting the structures apart is the regularity presented by unsolvated structure (I) contrasting with the disorder shown by structure (II), both in the tetra­hydro­furan solvent molecule (split into two 50% halves around an inversion centre), as well as in the COOEt group, also split into two 50% populated moieties. This disorder appears in such a way that, due to steric hindrance, each 50% branch in the latter group is only compatible with one of the 50% disordered solvato moieties, as shown in Fig. 2. Both molecules show a marked planar character [apart from the split NO2Et group in (II)], e.g. the central chain plus lateral phenyl groups (atoms N1–N4 and C1–C15) depart from planarity with a mean deviation of 0.0656 Å in (I) and 0.0329 Å in (II), with the nitro groups being rotated by less than 15° from this plane [14.54 (7) and 4.67 (7)° in (I), and 5.19 (11) and 5.18 (10) Å in (II)]. Regarding noncovalent inter­actions, a common feature for both molecules is the presence of intra­molecular N—H···O hydrogen bonds for both N—H donors (Tables 3 and 4, entries #1a/b and #2a/b). The acceptors, however, are not the same due to the different positioning of the nitro groups [2- and 2'-positions in (I), and 2- and 4'-positions in (II)], the latter one in (II) being completely out of reach for an N—H···O contact and being replaced by the nondisordered eth­oxy­carbonyl O atom, for which the inter­action serves as a clampering `anchor' (Figs. 1 and 2). These intra­molecular inter­actions provide for the rather planar geometry observed in both molecules. Their role in defining the molecular conformation in this family of compounds has been a matter of some discussion in the past. In particular, an extremely close relative to (I), viz. that with a methyl group at atom C7 instead of the present hydrogen H7 [hereinafter denoted structure (I')], was reported by Willey & Drew (1985), where the question was raised as to the reasons for the preferred (linear) E,E conformation instead of a (closed) E,Z one which would allow for strong stabilizing N—H···N intra­molecular hydrogen bonds (Scheme 2). The question remained open andi we can add that this preference is also observed in (I) and (II), as well as in most of the similar molecules reported more recently in the Cambridge Structural Database (CSD; Version 5.36, updated to May 2015; Groom & Allen, 2014). The only exceptions we could find were CSD refcodes IWINAD (Al-Zaydi et al., 2003) and VIVBUX (Hatano et al., 1991), which are characterized by an inter­nal R(6) closed loop. Structures (I) and (II) display a plethora of different weak inter­molecular inter­actions (πphenyl···πpheny, πCN···πCN, πphenyl···πCN, N—H···O, C—H···O andO···O), which are organized in different ways (Tables 5 and 6). In the simplest case of structure (II), the building block of the crystal packing consists of a stacking of π-bonded molecules defining columns parallel to the unique b axis, the shortest of the three cell lengths, and defined by the πphenyl···πphenyl (entries #4b and #5b in Table 6) and πC N···πCN (entries #6b to #9b in Table 6). These [010] substructures are in turn weakly connected by one single C—H···O inter­action (Table 4, entry #3b) linking columns along [001]. Fig. 4 presents a packing view along [010], showing columns in projection (one of them highlighted). The broad (100) planar arrays thus formed inter­act with each other via the heavily disordered part of the structure (the eth­oxy­carbonyl side chain and the tetra­hydro­furan solvent molecule, shown with double broken lines at the centre of Fig. 4) through some weak hydrogen bonds, omitted from the figures and the tables. In order to clarify the rather confusing view of this disordered part in Fig. 4, an inset has been included which presents a slightly rotated view of a single column, showing clearly the way in which the disordered moieties are located.

The case in structure (I) is far more inter­esting as it involves a diversity of inter­actions competing in the structural linkage. Some similarities with structure (II) can be envisaged, viz. a columnar array running along the unique b axis (Fig. 3a) and defined by the mixed πphenyl···πCN inter­actions reported as entries #4a and #5a in Table 5 and shown in Fig. 3(a). These substructures, in turn, are part of a fully π-bonded two-dimensional structure parallel to (001) by way of their inter-linkage via πphenyl···πphenyl bonds (Table 5, entry #6a). These two-dimensional structures are formed by similarly oriented molecules in each plane, but with an alternating orientation in adjacent planes [(210) and (210), see Figs. 5a and 5b]. A further inter­esting feature of these planes is that they are laterally padded by nitro groups, with N5/O1/O2 on one side and N6/O3/O4) on the other. Since neighbouring planes are generated either by a 21 axis along b (parallel to the planes) or an inversion centre, adjacent faces contain symmetry related nitro groups of the same kind. Thus, there are two types of inter­faces, that around the 21 axis, relating N5 nitro groups and that around the inversion centre, relating N6 nitro groups. In both inter­faces, a rather infrequent type of inter­action builds up, expressed as the short O···O contacts presented in Table 5 (entries #7a and #8a). These are a special case of the so-called `electron donor–acceptor' (EDA) Inter­actions. The properties of EDA inter­actions are much less known than those of hydrogen or π-bonds, but for the present analysis it will suffice to mention that they rank in strength in the range of the latter ones (π-bonds). For the inter­ested reader, a brief but illuminating summary can be found in Bertolasi et al. (2011, and references therein). Fig. 6 presents a view where the planes are seen in projection, and from which the different `inter­faces', 21 and 1, can be envisaged. In the first one, the O···O inter­action is stronger (Table 5, entry #7a) reinforced by a weak conventional N—H···O hydrogen bond (Table 3, entry #3a), with what a broad `sandwich-like' structure is generated, shown between square brackets in Fig. 6, which are in turn weakly connected by the remaining O···O inter­action (Table 5, entry #8a). Even if basically weak, the O···O contacts in (I) are rather short and they lie in the lower 30 percentile when compared with similar cases in the CSD (see Fig. S1 in the Supporting information).

A final remark about how small structural differences may lead to large changes in crystal organizations. As already mentioned, structures (I) and (I') differ by a C—H group in (I) being replaced by a C—CH3 group in (I'). Even if the change could be considered minor, the position of the methyl group is such that it shields its vicinal N—H hydrogen from any other possible inter­action short of the intra­molecular one which is already present. The structural changes which this subtle difference introduces are impressive, viz. no ππ bonds, of any type, are present in (I'), with a minimum centroid–centroid distance of ca 5Å; in addition, inter­molecular N—H···O hydrogen bonds are inhibited, and finally, no short O···O contacts are observed. As a consequence, the crystal structure of (I'), extremely different from that of (I), is only sustained by a few weak C—H···O hydrogen bonds and van der Waals inter­actions.

Conclusion top

Since our report on the synthesis of a large library of pyrazoles by reaction of β-diketohydrazones with substituted aryl­hydrazines (Bustos et al., 2009) we have had only few cases of products departing from the expected outcome. We have presented herein a full characterization of two of them and given a possible explanation for such a behaviour (departing from an otherwise firmly established synthetic route) based on the perturbing electron-withdrawing effect of the nitro substituents.

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom and ring numbering. Single broken lines represent intramolecular hydrogen bonds. Displacement ellipsoids are drawn at the 40% probability level. For interaction codes, see Table 3.
[Figure 2] Fig. 2. The molecular structure of (II), showing the atom and ring numbering. Single broken lines represent intramolecular hydrogen bonds. Double broken lines represent the disordered moieties, with the main figure and inset presenting two alternative co-existing possibilities. Displacement ellipsoids are drawn at the 40% probability level. For interaction codes, see Table 4.
[Figure 3] Fig. 3. Packing views showing the stacking interactions defining columnar arrays in (a) (I) and (b) (II). Double broken lines represent πphenyl···πphenyl interactions and single broken lines represent πCN···πCN or πphenyl···πCN interactions. [Symmetry codes in part (a): (ii) x, y-1, z; (iii) x, y+1, z; in part (b): (ii) -x+1/2, -y+3.2, -z+1; (iii) -x+1/2, -y+5/2, -z+1.] For interaction codes, see Tables 5 and 6.
[Figure 4] Fig. 4. Packing view of (II), projected down the direction of the columns (one of which is highlighted), showing the way in which they interact through one single type of C—H···O hydrogen bond (drawn in single broken lines). The disordered fraction of the structure is indicated with double broken lines. Inset: a clarifying view of one single column, showing a feasible distribution (of otherwise colliding parts) of these disordered fractions. For interaction codes, see Table 6.
[Figure 5] Fig. 5. Two different views of the planar arrays in (I), taken at different heights of z. Note the different orientations of the molecules in each array. Double broken lines represent πphenyl···πphenyl interactions and single broken lines represent πCN···πCN interactions. For interaction codes, see Table 5.
[Figure 6] Fig. 6. A packing view of (I), at a 90° angle from the viw in Fig 5, showing the planes in projection and the two different interfaces, i.e. one around the screw axis and the other generated by inversion centres. Single broken lines represent N—H···O hydrogen bonds and double broken lines represent O···O interactions. For interaction codes, see Table 5.
(I) (2'E,2'E)-2,2'-(Propane-1,2-diylidene)bis[1-(2-nitrophenyl)hydrazine] top
Crystal data top
C15H14N6O4F(000) = 712
Mr = 342.32Dx = 1.508 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.9382 (16) ÅCell parameters from 2932 reflections
b = 7.3484 (15) Åθ = 2.9–25.8°
c = 25.847 (5) ŵ = 0.11 mm1
β = 90.05 (3)°T = 150 K
V = 1507.7 (5) Å3Polyhedron, red
Z = 40.31 × 0.14 × 0.08 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2175 reflections with I > 2σ(I)
CCD rotation images, thin slices scansRint = 0.039
Absorption correction: multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
θmax = 27.9°, θmin = 1.6°
Tmin = 0.95, Tmax = 0.99h = 1010
12121 measured reflectionsk = 99
3365 independent reflectionsl = 3333
Refinement top
Refinement on F22 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092 w = 1/[σ2(Fo2) + (0.0516P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.87(Δ/σ)max = 0.001
3365 reflectionsΔρmax = 0.29 e Å3
233 parametersΔρmin = 0.18 e Å3
Crystal data top
C15H14N6O4V = 1507.7 (5) Å3
Mr = 342.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.9382 (16) ŵ = 0.11 mm1
b = 7.3484 (15) ÅT = 150 K
c = 25.847 (5) Å0.31 × 0.14 × 0.08 mm
β = 90.05 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3365 independent reflections
Absorption correction: multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
2175 reflections with I > 2σ(I)
Tmin = 0.95, Tmax = 0.99Rint = 0.039
12121 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0382 restraints
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 0.87Δρmax = 0.29 e Å3
3365 reflectionsΔρmin = 0.18 e Å3
233 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.30892 (12)0.20393 (13)0.26910 (4)0.0347 (3)
O20.49328 (15)0.41876 (16)0.26383 (4)0.0471 (3)
O31.11253 (13)1.39299 (13)0.47028 (4)0.0333 (3)
O41.22167 (13)1.66213 (14)0.46602 (4)0.0381 (3)
N10.60264 (15)0.57642 (16)0.34966 (4)0.0270 (3)
H1N0.5994 (18)0.5906 (19)0.3166 (3)0.032*
N20.68109 (14)0.70148 (15)0.38056 (4)0.0255 (3)
N30.86691 (14)1.12670 (15)0.36312 (4)0.0251 (3)
N40.95062 (15)1.25696 (15)0.39075 (4)0.0251 (3)
H4N0.9728 (17)1.2425 (19)0.4227 (4)0.030*
N50.41343 (15)0.30492 (16)0.28948 (4)0.0291 (3)
N61.14979 (15)1.53197 (16)0.44560 (4)0.0272 (3)
C10.53689 (16)0.42342 (18)0.37167 (5)0.0230 (3)
C20.44424 (17)0.29060 (18)0.34426 (5)0.0246 (3)
C30.37566 (17)0.13959 (19)0.36908 (6)0.0298 (3)
H3A0.31470.05470.35000.036*
C40.39677 (19)0.11451 (19)0.42111 (6)0.0331 (4)
H4A0.35130.01320.43750.040*
C50.48780 (18)0.24393 (19)0.44908 (6)0.0312 (4)
H50.50260.22820.48450.037*
C60.55555 (17)0.39336 (18)0.42543 (5)0.0275 (3)
H60.61530.47720.44520.033*
C70.73489 (17)0.84686 (18)0.35836 (5)0.0259 (3)
H70.71870.86400.32310.031*
C80.82108 (17)0.98371 (18)0.38888 (5)0.0243 (3)
C91.01205 (16)1.40734 (17)0.36605 (5)0.0214 (3)
C101.10995 (16)1.54146 (18)0.39096 (5)0.0228 (3)
C111.17754 (18)1.68724 (19)0.36358 (5)0.0295 (4)
H111.24311.77300.38070.035*
C121.1485 (2)1.7056 (2)0.31161 (6)0.0351 (4)
H121.19581.80160.29320.042*
C131.04659 (19)1.5778 (2)0.28672 (6)0.0316 (4)
H131.02411.59080.25160.038*
C140.97949 (17)1.43429 (18)0.31305 (5)0.0264 (3)
H140.91061.35230.29560.032*
C150.85593 (19)0.9528 (2)0.44505 (5)0.0317 (4)
H15A0.97510.94020.45030.048*
H15B0.80000.84380.45620.048*
H15C0.81511.05440.46470.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0361 (6)0.0309 (6)0.0372 (6)0.0059 (5)0.0092 (5)0.0081 (5)
O20.0625 (8)0.0463 (7)0.0324 (6)0.0254 (6)0.0032 (6)0.0022 (5)
O30.0467 (7)0.0246 (6)0.0285 (6)0.0060 (5)0.0045 (5)0.0039 (5)
O40.0490 (7)0.0298 (6)0.0357 (6)0.0132 (5)0.0118 (5)0.0052 (5)
N10.0309 (7)0.0229 (6)0.0271 (6)0.0067 (5)0.0037 (5)0.0018 (5)
N20.0247 (6)0.0207 (6)0.0311 (7)0.0032 (5)0.0024 (5)0.0037 (5)
N30.0264 (7)0.0204 (6)0.0285 (6)0.0040 (5)0.0029 (5)0.0032 (5)
N40.0315 (7)0.0213 (6)0.0224 (6)0.0053 (5)0.0038 (5)0.0009 (5)
N50.0316 (7)0.0245 (7)0.0313 (7)0.0028 (5)0.0036 (6)0.0047 (5)
N60.0298 (7)0.0241 (7)0.0276 (7)0.0022 (5)0.0043 (5)0.0014 (5)
C10.0204 (7)0.0190 (7)0.0295 (8)0.0008 (6)0.0008 (6)0.0020 (6)
C20.0241 (8)0.0229 (8)0.0267 (8)0.0010 (6)0.0014 (6)0.0026 (6)
C30.0299 (8)0.0230 (8)0.0366 (9)0.0055 (6)0.0044 (7)0.0044 (7)
C40.0372 (9)0.0242 (8)0.0379 (9)0.0089 (7)0.0010 (7)0.0021 (7)
C50.0334 (9)0.0321 (9)0.0281 (8)0.0036 (7)0.0010 (6)0.0011 (7)
C60.0271 (8)0.0235 (8)0.0320 (8)0.0031 (6)0.0029 (6)0.0057 (6)
C70.0271 (8)0.0235 (8)0.0270 (8)0.0009 (6)0.0027 (6)0.0005 (6)
C80.0235 (8)0.0199 (7)0.0294 (8)0.0001 (6)0.0003 (6)0.0006 (6)
C90.0208 (7)0.0174 (7)0.0260 (7)0.0015 (6)0.0014 (6)0.0016 (6)
C100.0232 (7)0.0207 (7)0.0245 (7)0.0014 (6)0.0019 (6)0.0012 (6)
C110.0329 (9)0.0219 (8)0.0337 (9)0.0066 (6)0.0048 (7)0.0008 (6)
C120.0440 (10)0.0254 (8)0.0358 (9)0.0086 (7)0.0018 (7)0.0055 (7)
C130.0407 (9)0.0292 (8)0.0250 (8)0.0015 (7)0.0039 (7)0.0021 (6)
C140.0288 (8)0.0217 (7)0.0288 (8)0.0006 (6)0.0028 (6)0.0035 (6)
C150.0408 (9)0.0252 (8)0.0291 (8)0.0069 (7)0.0059 (7)0.0001 (6)
Geometric parameters (Å, º) top
O1—N51.2312 (14)C4—H4A0.9300
O2—N51.2416 (15)C5—C61.3672 (19)
O3—N61.2400 (14)C5—H50.9300
O4—N61.2322 (14)C6—H60.9300
N1—C11.3641 (17)C7—C81.4495 (19)
N1—N21.3673 (15)C7—H70.9300
N1—H1N0.861 (8)C8—C151.4950 (19)
N2—C71.2859 (17)C9—C141.4078 (18)
N3—C81.2962 (16)C9—C101.4103 (18)
N3—N41.3664 (15)C10—C111.3917 (19)
N4—C91.3664 (17)C11—C121.369 (2)
N4—H4N0.852 (8)C11—H110.9300
N5—C21.4407 (17)C12—C131.396 (2)
N6—C101.4488 (17)C12—H120.9300
C1—C21.4122 (18)C13—C141.3639 (19)
C1—C61.4145 (19)C13—H130.9300
C2—C31.3927 (19)C14—H140.9300
C3—C41.368 (2)C15—H15A0.9600
C3—H3A0.9300C15—H15B0.9600
C4—C51.3959 (19)C15—H15C0.9600
C1—N1—N2118.98 (11)C1—C6—H6119.2
C1—N1—H1N120.2 (10)N2—C7—C8119.36 (13)
N2—N1—H1N120.7 (10)N2—C7—H7120.3
C7—N2—N1116.67 (12)C8—C7—H7120.3
C8—N3—N4115.84 (11)N3—C8—C7114.54 (12)
C9—N4—N3119.74 (11)N3—C8—C15124.77 (12)
C9—N4—H4N118.7 (10)C7—C8—C15120.66 (12)
N3—N4—H4N121.3 (10)N4—C9—C14120.20 (12)
O1—N5—O2121.46 (12)N4—C9—C10123.28 (12)
O1—N5—C2119.35 (12)C14—C9—C10116.52 (12)
O2—N5—C2119.19 (12)C11—C10—C9121.22 (12)
O4—N6—O3121.98 (11)C11—C10—N6116.67 (12)
O4—N6—C10118.74 (11)C9—C10—N6122.08 (12)
O3—N6—C10119.28 (11)C12—C11—C10120.66 (13)
N1—C1—C2124.03 (12)C12—C11—H11119.7
N1—C1—C6119.91 (12)C10—C11—H11119.7
C2—C1—C6116.03 (12)C11—C12—C13118.87 (14)
C3—C2—C1121.55 (13)C11—C12—H12120.6
C3—C2—N5116.41 (12)C13—C12—H12120.6
C1—C2—N5122.04 (12)C14—C13—C12121.10 (14)
C4—C3—C2120.84 (13)C14—C13—H13119.5
C4—C3—H3A119.6C12—C13—H13119.5
C2—C3—H3A119.6C13—C14—C9121.53 (13)
C3—C4—C5118.71 (14)C13—C14—H14119.2
C3—C4—H4A120.6C9—C14—H14119.2
C5—C4—H4A120.6C8—C15—H15A109.5
C6—C5—C4121.28 (14)C8—C15—H15B109.5
C6—C5—H5119.4H15A—C15—H15B109.5
C4—C5—H5119.4C8—C15—H15C109.5
C5—C6—C1121.58 (13)H15A—C15—H15C109.5
C5—C6—H6119.2H15B—C15—H15C109.5
(II) (2Z,3Z)-Ethyl 3-[2-(2-nitrophenyl)hydrazinylidene]-2-[2-(4-nitrophenyl)hydrazinylidene]butanoate tetrahydrofuran hemisolvate top
Crystal data top
C18H18N6O6·0.5C4H8OF(000) = 1888
Mr = 450.43Dx = 1.457 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 27.312 (6) ÅCell parameters from 1905 reflections
b = 7.5929 (16) Åθ = 2.2–25.1°
c = 20.625 (4) ŵ = 0.11 mm1
β = 106.241 (7)°T = 150 K
V = 4106.4 (15) Å3Polyhedron, red
Z = 80.41 × 0.19 × 0.07 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2876 reflections with I > 2σ(I)
CCD rotation images, thin slices scansRint = 0.049
Absorption correction: multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
θmax = 28.0°, θmin = 1.6°
Tmin = 0.96, Tmax = 0.98h = 3435
16722 measured reflectionsk = 99
4588 independent reflectionsl = 2625
Refinement top
Refinement on F238 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.062H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.168 w = 1/[σ2(Fo2) + (0.0657P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.34(Δ/σ)max = 0.001
4588 reflectionsΔρmax = 0.84 e Å3
348 parametersΔρmin = 0.77 e Å3
Crystal data top
C18H18N6O6·0.5C4H8OV = 4106.4 (15) Å3
Mr = 450.43Z = 8
Monoclinic, C2/cMo Kα radiation
a = 27.312 (6) ŵ = 0.11 mm1
b = 7.5929 (16) ÅT = 150 K
c = 20.625 (4) Å0.41 × 0.19 × 0.07 mm
β = 106.241 (7)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
4588 independent reflections
Absorption correction: multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
2876 reflections with I > 2σ(I)
Tmin = 0.96, Tmax = 0.98Rint = 0.049
16722 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06238 restraints
wR(F2) = 0.168H atoms treated by a mixture of independent and constrained refinement
S = 1.34Δρmax = 0.84 e Å3
4588 reflectionsΔρmin = 0.77 e Å3
348 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.17870 (8)1.3512 (3)0.76591 (9)0.0683 (6)
O20.22326 (6)1.2051 (2)0.71278 (8)0.0531 (5)
O30.50321 (6)0.5392 (2)0.42151 (8)0.0502 (5)
O40.46806 (6)0.4790 (2)0.31644 (8)0.0434 (4)
N10.19247 (7)1.1720 (2)0.58179 (9)0.0313 (4)
H1N0.2163 (7)1.157 (3)0.6180 (8)0.048 (8)*
N20.19374 (6)1.1111 (2)0.52012 (8)0.0299 (4)
N30.27870 (6)0.9045 (2)0.44555 (8)0.0281 (4)
N40.28346 (7)0.8452 (2)0.38623 (9)0.0315 (4)
H4N0.2596 (6)0.856 (3)0.3495 (7)0.042 (7)*
N50.18406 (8)1.2873 (3)0.71332 (10)0.0443 (5)
N60.46624 (7)0.5401 (2)0.37109 (9)0.0337 (4)
C10.14879 (8)1.2471 (3)0.58896 (10)0.0290 (5)
C20.14367 (8)1.3073 (3)0.65172 (11)0.0325 (5)
C30.09841 (9)1.3851 (3)0.65634 (12)0.0393 (6)
H30.09601.42510.69800.047*
C40.05777 (9)1.4031 (3)0.60067 (12)0.0400 (6)
H40.02781.45590.60390.048*
C50.06196 (9)1.3407 (3)0.53863 (12)0.0384 (6)
H50.03411.35000.50060.046*
C60.10589 (8)1.2667 (3)0.53269 (11)0.0334 (5)
H60.10761.22820.49060.040*
C70.23542 (7)1.0343 (3)0.51720 (10)0.0266 (5)
C80.23569 (7)0.9678 (3)0.45052 (10)0.0265 (5)
C90.32886 (7)0.7676 (3)0.38426 (10)0.0271 (5)
C100.33396 (8)0.7112 (3)0.32212 (10)0.0328 (5)
H100.30700.72480.28330.039*
C110.37878 (8)0.6354 (3)0.31816 (10)0.0314 (5)
H110.38210.59690.27680.038*
C120.41876 (7)0.6169 (3)0.37593 (10)0.0281 (5)
C130.41411 (8)0.6691 (3)0.43844 (10)0.0301 (5)
H130.44120.65400.47710.036*
C140.36930 (7)0.7432 (3)0.44275 (10)0.0283 (5)
H140.36580.77710.48450.034*
C150.28221 (8)1.0154 (3)0.57567 (11)0.0355 (5)
H15A0.30830.95620.56110.053*
H15B0.27420.94790.61070.053*
H15C0.29411.12990.59270.053*
O50.19003 (7)1.0375 (2)0.33805 (8)0.0559 (5)
C160.18927 (8)0.9788 (3)0.39144 (10)0.0306 (5)
O6A0.15276 (9)0.8689 (4)0.40072 (14)0.0303 (5)0.5
C17A0.10352 (15)0.8570 (5)0.3481 (2)0.0293 (9)0.5
H17A0.10940.84680.30400.035*0.5
H17B0.08370.96280.34850.035*0.5
C18A0.07520 (18)0.7016 (6)0.3610 (3)0.0428 (11)0.5
H18A0.04530.68480.32380.064*0.5
H18B0.06530.71970.40170.064*0.5
H18C0.09660.59920.36600.064*0.5
O6B0.14485 (8)0.9632 (4)0.40577 (14)0.0303 (5)0.5
C17B0.10085 (17)1.0003 (7)0.3487 (2)0.0442 (11)0.5
H17C0.07090.94510.35620.053*0.5
H17D0.10630.94960.30810.053*0.5
C18B0.09143 (19)1.1959 (7)0.3383 (2)0.0532 (13)0.5
H18D0.06251.21500.30000.080*0.5
H18E0.12101.25090.33070.080*0.5
H18F0.08481.24580.37780.080*0.5
O1C0.00132 (19)0.4558 (5)0.2852 (3)0.0898 (15)0.5
C1C0.0326 (2)0.6129 (7)0.3021 (3)0.0614 (16)0.5
H1CA0.01560.70050.32230.074*0.5
H1CB0.03870.66290.26180.074*0.5
C2C0.0826 (2)0.5585 (8)0.3516 (3)0.0698 (18)0.5
H2A0.08120.57060.39790.084*0.5
H2B0.11070.62780.34540.084*0.5
C3C0.0874 (2)0.3652 (7)0.3334 (3)0.081 (2)0.5
H3A0.11610.34870.31500.098*0.5
H3B0.09200.29050.37280.098*0.5
C4C0.0374 (2)0.3238 (8)0.2808 (4)0.079 (2)0.5
H4A0.04230.32350.23600.095*0.5
H4B0.02520.20860.28930.095*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0732 (14)0.0949 (16)0.0344 (10)0.0037 (11)0.0112 (9)0.0194 (10)
O20.0353 (10)0.0782 (14)0.0402 (10)0.0052 (9)0.0012 (8)0.0067 (9)
O30.0265 (9)0.0807 (13)0.0382 (9)0.0123 (8)0.0004 (7)0.0041 (8)
O40.0395 (9)0.0529 (11)0.0390 (9)0.0121 (8)0.0129 (7)0.0057 (8)
N10.0278 (10)0.0377 (11)0.0271 (10)0.0005 (8)0.0058 (8)0.0013 (8)
N20.0279 (10)0.0334 (10)0.0286 (10)0.0014 (8)0.0084 (8)0.0025 (8)
N30.0238 (9)0.0302 (10)0.0301 (9)0.0016 (7)0.0071 (7)0.0010 (8)
N40.0234 (10)0.0410 (11)0.0282 (10)0.0020 (8)0.0041 (8)0.0015 (8)
N50.0461 (13)0.0533 (13)0.0324 (11)0.0147 (10)0.0090 (10)0.0068 (10)
N60.0266 (10)0.0395 (11)0.0345 (10)0.0031 (8)0.0076 (8)0.0006 (9)
C10.0283 (12)0.0266 (11)0.0328 (11)0.0053 (9)0.0097 (9)0.0001 (9)
C20.0339 (12)0.0325 (12)0.0301 (11)0.0102 (10)0.0074 (9)0.0028 (9)
C30.0485 (15)0.0376 (13)0.0380 (13)0.0081 (11)0.0224 (12)0.0055 (11)
C40.0387 (14)0.0387 (14)0.0480 (15)0.0005 (10)0.0208 (12)0.0012 (11)
C50.0311 (12)0.0393 (14)0.0431 (13)0.0027 (10)0.0073 (10)0.0022 (11)
C60.0362 (13)0.0353 (12)0.0288 (11)0.0005 (10)0.0095 (10)0.0025 (9)
C70.0246 (11)0.0250 (11)0.0291 (11)0.0016 (9)0.0060 (9)0.0053 (9)
C80.0236 (11)0.0276 (11)0.0275 (11)0.0001 (9)0.0056 (8)0.0084 (9)
C90.0215 (11)0.0275 (11)0.0322 (11)0.0014 (8)0.0076 (9)0.0011 (9)
C100.0250 (11)0.0399 (13)0.0289 (11)0.0011 (9)0.0003 (9)0.0008 (10)
C110.0295 (12)0.0364 (12)0.0276 (11)0.0007 (9)0.0068 (9)0.0034 (9)
C120.0232 (11)0.0274 (11)0.0334 (11)0.0007 (8)0.0073 (9)0.0010 (9)
C130.0252 (11)0.0345 (12)0.0282 (11)0.0003 (9)0.0034 (9)0.0005 (9)
C140.0246 (11)0.0323 (12)0.0280 (11)0.0008 (9)0.0072 (9)0.0004 (9)
C150.0308 (12)0.0387 (13)0.0333 (12)0.0023 (10)0.0031 (10)0.0028 (10)
O50.0509 (11)0.0739 (13)0.0362 (10)0.0103 (9)0.0011 (8)0.0222 (9)
C160.0243 (10)0.0413 (13)0.0260 (11)0.0068 (9)0.0067 (8)0.0020 (10)
O6A0.0222 (8)0.0439 (12)0.0255 (8)0.0071 (8)0.0080 (6)0.0046 (10)
C17A0.0264 (18)0.029 (2)0.029 (2)0.0051 (16)0.0016 (14)0.0033 (19)
C18A0.034 (2)0.033 (3)0.054 (3)0.0018 (17)0.000 (2)0.002 (2)
O6B0.0222 (8)0.0439 (12)0.0255 (8)0.0071 (8)0.0080 (6)0.0046 (10)
C17B0.0274 (18)0.065 (3)0.035 (2)0.004 (2)0.0010 (16)0.001 (2)
C18B0.047 (3)0.067 (3)0.037 (3)0.019 (2)0.003 (2)0.002 (2)
O1C0.092 (3)0.068 (3)0.125 (4)0.010 (3)0.056 (4)0.020 (3)
C1C0.056 (4)0.041 (3)0.085 (4)0.001 (3)0.016 (3)0.008 (3)
C2C0.059 (4)0.078 (5)0.061 (4)0.000 (3)0.003 (3)0.008 (3)
C3C0.081 (5)0.054 (4)0.085 (5)0.008 (3)0.016 (4)0.006 (3)
C4C0.067 (4)0.067 (4)0.099 (5)0.002 (4)0.016 (4)0.024 (4)
Geometric parameters (Å, º) top
O1—N51.234 (2)C13—H130.9300
O2—N51.242 (3)C14—H140.9300
O3—N61.230 (2)C15—H15A0.9600
O4—N61.233 (2)C15—H15B0.9600
N1—N21.363 (2)C15—H15C0.9600
N1—C11.367 (3)O5—C161.193 (2)
N1—H1N0.849 (10)C16—O6B1.332 (3)
N2—C71.295 (3)C16—O6A1.354 (3)
N3—C81.299 (3)O6A—C17A1.476 (4)
N3—N41.344 (2)C17A—C18A1.475 (5)
N4—C91.383 (3)C17A—H17A0.9700
N4—H4N0.855 (10)C17A—H17B0.9700
N5—C21.439 (3)C18A—H18A0.9600
N6—C121.450 (3)C18A—H18B0.9600
C1—C61.408 (3)C18A—H18C0.9600
C1—C21.416 (3)O6B—C17B1.455 (5)
C2—C31.397 (3)C17B—C18B1.512 (6)
C3—C41.362 (3)C17B—H17C0.9700
C3—H30.9300C17B—H17D0.9700
C4—C51.399 (3)C18B—H18D0.9600
C4—H40.9300C18B—H18E0.9600
C5—C61.361 (3)C18B—H18F0.9600
C5—H50.9300O1C—C4C1.426 (6)
C6—H60.9300O1C—C1C1.452 (6)
C7—C81.467 (3)C1C—C2C1.515 (6)
C7—C151.499 (3)C1C—H1CA0.9700
C8—C161.495 (3)C1C—H1CB0.9700
C9—C101.395 (3)C2C—C3C1.529 (6)
C9—C141.402 (3)C2C—H2A0.9700
C10—C111.375 (3)C2C—H2B0.9700
C10—H100.9300C3C—C4C1.521 (6)
C11—C121.380 (3)C3C—H3A0.9700
C11—H110.9300C3C—H3B0.9700
C12—C131.388 (3)C4C—H4A0.9700
C13—C141.372 (3)C4C—H4B0.9700
N2—N1—C1119.55 (17)C7—C15—H15C109.5
N2—N1—H1N124.1 (16)H15A—C15—H15C109.5
C1—N1—H1N116.0 (16)H15B—C15—H15C109.5
C7—N2—N1116.64 (17)O5—C16—O6B119.3 (2)
C8—N3—N4121.05 (17)O5—C16—O6A124.3 (2)
N3—N4—C9119.03 (17)O5—C16—C8122.90 (19)
N3—N4—H4N122.0 (15)O6B—C16—C8115.6 (2)
C9—N4—H4N119.0 (15)O6A—C16—C8109.9 (2)
O1—N5—O2121.3 (2)C16—O6A—C17A119.3 (3)
O1—N5—C2119.0 (2)O6A—C17A—C18A109.4 (3)
O2—N5—C2119.67 (19)O6A—C17A—H17A109.8
O3—N6—O4122.50 (18)C18A—C17A—H17A109.8
O3—N6—C12118.84 (18)O6A—C17A—H17B109.8
O4—N6—C12118.66 (17)C18A—C17A—H17B109.8
N1—C1—C6120.36 (19)H17A—C17A—H17B108.2
N1—C1—C2123.07 (19)C17A—C18A—H18A109.5
C6—C1—C2116.56 (19)C17A—C18A—H18B109.5
C3—C2—C1121.0 (2)H18A—C18A—H18B109.5
C3—C2—N5117.3 (2)C17A—C18A—H18C109.5
C1—C2—N5121.7 (2)H18A—C18A—H18C109.5
C4—C3—C2120.8 (2)H18B—C18A—H18C109.5
C4—C3—H3119.6C16—O6B—C17B113.6 (3)
C2—C3—H3119.6O6B—C17B—C18B112.0 (4)
C3—C4—C5118.8 (2)O6B—C17B—H17C109.2
C3—C4—H4120.6C18B—C17B—H17C109.2
C5—C4—H4120.6O6B—C17B—H17D109.2
C6—C5—C4121.5 (2)C18B—C17B—H17D109.2
C6—C5—H5119.3H17C—C17B—H17D107.9
C4—C5—H5119.3C17B—C18B—H18D109.5
C5—C6—C1121.4 (2)C17B—C18B—H18E109.5
C5—C6—H6119.3H18D—C18B—H18E109.5
C1—C6—H6119.3C17B—C18B—H18F109.5
N2—C7—C8115.70 (18)H18D—C18B—H18F109.5
N2—C7—C15124.65 (19)H18E—C18B—H18F109.5
C8—C7—C15119.63 (18)C4C—O1C—C1C102.8 (5)
N3—C8—C7116.30 (18)O1C—C1C—C2C107.3 (4)
N3—C8—C16122.38 (18)O1C—C1C—H1CA110.3
C7—C8—C16121.28 (17)C2C—C1C—H1CA110.3
N4—C9—C10118.59 (18)O1C—C1C—H1CB110.3
N4—C9—C14121.89 (18)C2C—C1C—H1CB110.3
C10—C9—C14119.52 (19)H1CA—C1C—H1CB108.5
C11—C10—C9120.16 (19)C1C—C2C—C3C102.7 (4)
C11—C10—H10119.9C1C—C2C—H2A111.2
C9—C10—H10119.9C3C—C2C—H2A111.2
C10—C11—C12119.60 (19)C1C—C2C—H2B111.2
C10—C11—H11120.2C3C—C2C—H2B111.2
C12—C11—H11120.2H2A—C2C—H2B109.1
C11—C12—C13121.13 (19)C4C—C3C—C2C104.5 (4)
C11—C12—N6119.24 (18)C4C—C3C—H3A110.9
C13—C12—N6119.63 (18)C2C—C3C—H3A110.9
C14—C13—C12119.48 (19)C4C—C3C—H3B110.9
C14—C13—H13120.3C2C—C3C—H3B110.9
C12—C13—H13120.3H3A—C3C—H3B108.9
C13—C14—C9120.08 (19)O1C—C4C—C3C108.0 (5)
C13—C14—H14120.0O1C—C4C—H4A110.1
C9—C14—H14120.0C3C—C4C—H4A110.1
C7—C15—H15A109.5O1C—C4C—H4B110.1
C7—C15—H15B109.5C3C—C4C—H4B110.1
H15A—C15—H15B109.5H4A—C4C—H4B108.4

Experimental details

(I)(II)
Crystal data
Chemical formulaC15H14N6O4C18H18N6O6·0.5C4H8O
Mr342.32450.43
Crystal system, space groupMonoclinic, P21/cMonoclinic, C2/c
Temperature (K)150150
a, b, c (Å)7.9382 (16), 7.3484 (15), 25.847 (5)27.312 (6), 7.5929 (16), 20.625 (4)
β (°) 90.05 (3) 106.241 (7)
V3)1507.7 (5)4106.4 (15)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.110.11
Crystal size (mm)0.31 × 0.14 × 0.080.41 × 0.19 × 0.07
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS in SAINT-NT; Bruker, 2002)
Multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
Tmin, Tmax0.95, 0.990.96, 0.98
No. of measured, independent and
observed [I > 2σ(I)] reflections
12121, 3365, 2175 16722, 4588, 2876
Rint0.0390.049
(sin θ/λ)max1)0.6580.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.092, 0.87 0.062, 0.168, 1.34
No. of reflections33654588
No. of parameters233348
No. of restraints238
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)0.29, 0.180.84, 0.77

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL2014 Sheldrick, 2015), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006).

Comparative bond lengths (Å) for the backbone chain in (I) and (II) top
(I)(II)
C1—N11.3641 (17)1.367 (2)
N1—N21.3673 (15)1.364 (2)
N2—C71.2859 (17)1.291 (2)
C7—C81.4495 (19)1.470 (2)
C8—N31.2962 (16)1.299 (2)
N3—N41.3664 (15)1.344 (2)
N4—C91.3664 (17)1.383 (2)
Hydrogen-bond geometry (Å, °) for (I) top
CodeD—H···AD—HH···AD···AD—H···A
#1aN1—H1N···O20.86 (1)2.04 (1)2.6484 (16)127 (1)
#2aN4—H4···O30.85 (1)1.99 (1)2.6215 (16)130 (1)
#3aN1—H1N···O1i0.86 (1)2.48 (1)3.2859 (16)157 (1)
Symmetry code: (i) -x+1, y+1/2, -z+1/2.
Hydrogen-bond geometry (Å, °) for (II) top
CodeD—H···AD—HH···AD···AD—H···A
#1bN1—H1N···O20.86 (2)1.95 (2)2.608 (2)132 (2)
#2bN4—H4N···O50.86 (2)2.31 (2)2.867 (2)123 (2)
#3bC10—H10···O2i0.932.403.287 (3)160
Symmetry code: (i) x, -y+2, z-1/2.
ππ, N—O···π and O···O contacts in (I) (Å, °) top
CodeGroup 1···Group 2ccd (Å)da (°)sa (°)ipd (Å)
#4aCg1···Cg4ii3.4245.83.83.416
#5aCg2···Cg3iii3.4375.25.33.422
#6aCg1···Cg2iv4.0345 (11)3.08 (7)32.90 (10)3.38 (4)
#7aO2···O1i2.7538 (16)
#8aO3···O3v2.8338 (15)
Symmetry codes: (i) -x+1, y+1/2, -z+1/2; (ii) x, -1+y, z; (iii) x, y+1, z; (iv) x-1, y-1, z; (v) -x+2, -y+3, -z+1.

Notes: ccd is the centre-to-centre distance, da is the (dihedral) angle between groups, sa is the slippage angle, ipd is the (mean) distance from one plane to the neighbouring centroid. For details, see Janiak (2000). Cg1 is the centroid of the C1–C6 ring, Cg2 that of the C9–C14 ring, Cg3 that of the C7N2 bond and Cg4 that of the C8N3 bond.
ππ contacts in (II) (Å, °) top
CodeGroup 1···Group 2ccd (Å)sa (°)da (°)ipd (Å)
#4bCg1···Cg2ii3.9766 (14)2.32 (10)30.95(53.409 (2)
#5bCg1···Cg2iii3.7433 (14)2.32 (10)23.4 (8)3.43 (2)
#6bCg3···Cg3iii3.52409.85 (3)3.427 (2)
#7bCg3···Cg4ii3.9625.331.9 (3)3.36 (4)
#8bCg3···Cg4iii3.8315.326.1 (4)3.44 (2)
#9bCg4···Cg4ii3.635023.82 (4)3.325 (2)
Symmetry codes: (ii) -x+1/2, -y+3/2, -z+1; (iii) -x+1/2, -y+5/2, -z+1.

Notes: ccd is the centre-to-centre distance, da is the (dihedral) angle between groups, sa is the slippage angle, ipd is the (mean) distance from one plane to the neighbouring centroid. For details, see Janiak (2000). Cg1 is the centroid of the C1–C6 ring, Cg2 that of the C9–C14 ring, Cg3 that of the C7N2 bond and Cg4 that of the C8N3 bond.
 

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