Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615021944/fp3020sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615021944/fp3020Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615021944/fp3020IIsup3.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615021944/fp3020sup4.pdf |
CCDC references: 1437501; 1437500
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).
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.
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.
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.
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.
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.
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?]
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—N═C—C═N—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, πC═N···πC═N, πphenyl···πC═N, 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···πC═N (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···πC═N 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 π–π 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.
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.
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).
C15H14N6O4 | F(000) = 712 |
Mr = 342.32 | Dx = 1.508 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9382 (16) Å | Cell parameters from 2932 reflections |
b = 7.3484 (15) Å | θ = 2.9–25.8° |
c = 25.847 (5) Å | µ = 0.11 mm−1 |
β = 90.05 (3)° | T = 150 K |
V = 1507.7 (5) Å3 | Polyhedron, red |
Z = 4 | 0.31 × 0.14 × 0.08 mm |
Bruker SMART CCD area-detector diffractometer | 2175 reflections with I > 2σ(I) |
CCD rotation images, thin slices scans | Rint = 0.039 |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | θmax = 27.9°, θmin = 1.6° |
Tmin = 0.95, Tmax = 0.99 | h = −10→10 |
12121 measured reflections | k = −9→9 |
3365 independent reflections | l = −33→33 |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.038 | H 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 reflections | Δρmax = 0.29 e Å−3 |
233 parameters | Δρmin = −0.18 e Å−3 |
C15H14N6O4 | V = 1507.7 (5) Å3 |
Mr = 342.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.9382 (16) Å | µ = 0.11 mm−1 |
b = 7.3484 (15) Å | T = 150 K |
c = 25.847 (5) Å | 0.31 × 0.14 × 0.08 mm |
β = 90.05 (3)° |
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 = 0.99 | Rint = 0.039 |
12121 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 2 restraints |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.87 | Δρmax = 0.29 e Å−3 |
3365 reflections | Δρmin = −0.18 e Å−3 |
233 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.30892 (12) | 0.20393 (13) | 0.26910 (4) | 0.0347 (3) | |
O2 | 0.49328 (15) | 0.41876 (16) | 0.26383 (4) | 0.0471 (3) | |
O3 | 1.11253 (13) | 1.39299 (13) | 0.47028 (4) | 0.0333 (3) | |
O4 | 1.22167 (13) | 1.66213 (14) | 0.46602 (4) | 0.0381 (3) | |
N1 | 0.60264 (15) | 0.57642 (16) | 0.34966 (4) | 0.0270 (3) | |
H1N | 0.5994 (18) | 0.5906 (19) | 0.3166 (3) | 0.032* | |
N2 | 0.68109 (14) | 0.70148 (15) | 0.38056 (4) | 0.0255 (3) | |
N3 | 0.86691 (14) | 1.12670 (15) | 0.36312 (4) | 0.0251 (3) | |
N4 | 0.95062 (15) | 1.25696 (15) | 0.39075 (4) | 0.0251 (3) | |
H4N | 0.9728 (17) | 1.2425 (19) | 0.4227 (4) | 0.030* | |
N5 | 0.41343 (15) | 0.30492 (16) | 0.28948 (4) | 0.0291 (3) | |
N6 | 1.14979 (15) | 1.53197 (16) | 0.44560 (4) | 0.0272 (3) | |
C1 | 0.53689 (16) | 0.42342 (18) | 0.37167 (5) | 0.0230 (3) | |
C2 | 0.44424 (17) | 0.29060 (18) | 0.34426 (5) | 0.0246 (3) | |
C3 | 0.37566 (17) | 0.13959 (19) | 0.36908 (6) | 0.0298 (3) | |
H3A | 0.3147 | 0.0547 | 0.3500 | 0.036* | |
C4 | 0.39677 (19) | 0.11451 (19) | 0.42111 (6) | 0.0331 (4) | |
H4A | 0.3513 | 0.0132 | 0.4375 | 0.040* | |
C5 | 0.48780 (18) | 0.24393 (19) | 0.44908 (6) | 0.0312 (4) | |
H5 | 0.5026 | 0.2282 | 0.4845 | 0.037* | |
C6 | 0.55555 (17) | 0.39336 (18) | 0.42543 (5) | 0.0275 (3) | |
H6 | 0.6153 | 0.4772 | 0.4452 | 0.033* | |
C7 | 0.73489 (17) | 0.84686 (18) | 0.35836 (5) | 0.0259 (3) | |
H7 | 0.7187 | 0.8640 | 0.3231 | 0.031* | |
C8 | 0.82108 (17) | 0.98371 (18) | 0.38888 (5) | 0.0243 (3) | |
C9 | 1.01205 (16) | 1.40734 (17) | 0.36605 (5) | 0.0214 (3) | |
C10 | 1.10995 (16) | 1.54146 (18) | 0.39096 (5) | 0.0228 (3) | |
C11 | 1.17754 (18) | 1.68724 (19) | 0.36358 (5) | 0.0295 (4) | |
H11 | 1.2431 | 1.7730 | 0.3807 | 0.035* | |
C12 | 1.1485 (2) | 1.7056 (2) | 0.31161 (6) | 0.0351 (4) | |
H12 | 1.1958 | 1.8016 | 0.2932 | 0.042* | |
C13 | 1.04659 (19) | 1.5778 (2) | 0.28672 (6) | 0.0316 (4) | |
H13 | 1.0241 | 1.5908 | 0.2516 | 0.038* | |
C14 | 0.97949 (17) | 1.43429 (18) | 0.31305 (5) | 0.0264 (3) | |
H14 | 0.9106 | 1.3523 | 0.2956 | 0.032* | |
C15 | 0.85593 (19) | 0.9528 (2) | 0.44505 (5) | 0.0317 (4) | |
H15A | 0.9751 | 0.9402 | 0.4503 | 0.048* | |
H15B | 0.8000 | 0.8438 | 0.4562 | 0.048* | |
H15C | 0.8151 | 1.0544 | 0.4647 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0361 (6) | 0.0309 (6) | 0.0372 (6) | −0.0059 (5) | −0.0092 (5) | −0.0081 (5) |
O2 | 0.0625 (8) | 0.0463 (7) | 0.0324 (6) | −0.0254 (6) | −0.0032 (6) | 0.0022 (5) |
O3 | 0.0467 (7) | 0.0246 (6) | 0.0285 (6) | −0.0060 (5) | −0.0045 (5) | 0.0039 (5) |
O4 | 0.0490 (7) | 0.0298 (6) | 0.0357 (6) | −0.0132 (5) | −0.0118 (5) | −0.0052 (5) |
N1 | 0.0309 (7) | 0.0229 (6) | 0.0271 (6) | −0.0067 (5) | −0.0037 (5) | −0.0018 (5) |
N2 | 0.0247 (6) | 0.0207 (6) | 0.0311 (7) | −0.0032 (5) | −0.0024 (5) | −0.0037 (5) |
N3 | 0.0264 (7) | 0.0204 (6) | 0.0285 (6) | −0.0040 (5) | −0.0029 (5) | −0.0032 (5) |
N4 | 0.0315 (7) | 0.0213 (6) | 0.0224 (6) | −0.0053 (5) | −0.0038 (5) | −0.0009 (5) |
N5 | 0.0316 (7) | 0.0245 (7) | 0.0313 (7) | −0.0028 (5) | −0.0036 (6) | −0.0047 (5) |
N6 | 0.0298 (7) | 0.0241 (7) | 0.0276 (7) | −0.0022 (5) | −0.0043 (5) | −0.0014 (5) |
C1 | 0.0204 (7) | 0.0190 (7) | 0.0295 (8) | 0.0008 (6) | 0.0008 (6) | −0.0020 (6) |
C2 | 0.0241 (8) | 0.0229 (8) | 0.0267 (8) | 0.0010 (6) | −0.0014 (6) | −0.0026 (6) |
C3 | 0.0299 (8) | 0.0230 (8) | 0.0366 (9) | −0.0055 (6) | −0.0044 (7) | −0.0044 (7) |
C4 | 0.0372 (9) | 0.0242 (8) | 0.0379 (9) | −0.0089 (7) | 0.0010 (7) | 0.0021 (7) |
C5 | 0.0334 (9) | 0.0321 (9) | 0.0281 (8) | −0.0036 (7) | −0.0010 (6) | 0.0011 (7) |
C6 | 0.0271 (8) | 0.0235 (8) | 0.0320 (8) | −0.0031 (6) | −0.0029 (6) | −0.0057 (6) |
C7 | 0.0271 (8) | 0.0235 (8) | 0.0270 (8) | −0.0009 (6) | −0.0027 (6) | −0.0005 (6) |
C8 | 0.0235 (8) | 0.0199 (7) | 0.0294 (8) | 0.0001 (6) | 0.0003 (6) | −0.0006 (6) |
C9 | 0.0208 (7) | 0.0174 (7) | 0.0260 (7) | 0.0015 (6) | 0.0014 (6) | −0.0016 (6) |
C10 | 0.0232 (7) | 0.0207 (7) | 0.0245 (7) | 0.0014 (6) | −0.0019 (6) | −0.0012 (6) |
C11 | 0.0329 (9) | 0.0219 (8) | 0.0337 (9) | −0.0066 (6) | −0.0048 (7) | −0.0008 (6) |
C12 | 0.0440 (10) | 0.0254 (8) | 0.0358 (9) | −0.0086 (7) | −0.0018 (7) | 0.0055 (7) |
C13 | 0.0407 (9) | 0.0292 (8) | 0.0250 (8) | −0.0015 (7) | −0.0039 (7) | 0.0021 (6) |
C14 | 0.0288 (8) | 0.0217 (7) | 0.0288 (8) | −0.0006 (6) | −0.0028 (6) | −0.0035 (6) |
C15 | 0.0408 (9) | 0.0252 (8) | 0.0291 (8) | −0.0069 (7) | −0.0059 (7) | 0.0001 (6) |
O1—N5 | 1.2312 (14) | C4—H4A | 0.9300 |
O2—N5 | 1.2416 (15) | C5—C6 | 1.3672 (19) |
O3—N6 | 1.2400 (14) | C5—H5 | 0.9300 |
O4—N6 | 1.2322 (14) | C6—H6 | 0.9300 |
N1—C1 | 1.3641 (17) | C7—C8 | 1.4495 (19) |
N1—N2 | 1.3673 (15) | C7—H7 | 0.9300 |
N1—H1N | 0.861 (8) | C8—C15 | 1.4950 (19) |
N2—C7 | 1.2859 (17) | C9—C14 | 1.4078 (18) |
N3—C8 | 1.2962 (16) | C9—C10 | 1.4103 (18) |
N3—N4 | 1.3664 (15) | C10—C11 | 1.3917 (19) |
N4—C9 | 1.3664 (17) | C11—C12 | 1.369 (2) |
N4—H4N | 0.852 (8) | C11—H11 | 0.9300 |
N5—C2 | 1.4407 (17) | C12—C13 | 1.396 (2) |
N6—C10 | 1.4488 (17) | C12—H12 | 0.9300 |
C1—C2 | 1.4122 (18) | C13—C14 | 1.3639 (19) |
C1—C6 | 1.4145 (19) | C13—H13 | 0.9300 |
C2—C3 | 1.3927 (19) | C14—H14 | 0.9300 |
C3—C4 | 1.368 (2) | C15—H15A | 0.9600 |
C3—H3A | 0.9300 | C15—H15B | 0.9600 |
C4—C5 | 1.3959 (19) | C15—H15C | 0.9600 |
C1—N1—N2 | 118.98 (11) | C1—C6—H6 | 119.2 |
C1—N1—H1N | 120.2 (10) | N2—C7—C8 | 119.36 (13) |
N2—N1—H1N | 120.7 (10) | N2—C7—H7 | 120.3 |
C7—N2—N1 | 116.67 (12) | C8—C7—H7 | 120.3 |
C8—N3—N4 | 115.84 (11) | N3—C8—C7 | 114.54 (12) |
C9—N4—N3 | 119.74 (11) | N3—C8—C15 | 124.77 (12) |
C9—N4—H4N | 118.7 (10) | C7—C8—C15 | 120.66 (12) |
N3—N4—H4N | 121.3 (10) | N4—C9—C14 | 120.20 (12) |
O1—N5—O2 | 121.46 (12) | N4—C9—C10 | 123.28 (12) |
O1—N5—C2 | 119.35 (12) | C14—C9—C10 | 116.52 (12) |
O2—N5—C2 | 119.19 (12) | C11—C10—C9 | 121.22 (12) |
O4—N6—O3 | 121.98 (11) | C11—C10—N6 | 116.67 (12) |
O4—N6—C10 | 118.74 (11) | C9—C10—N6 | 122.08 (12) |
O3—N6—C10 | 119.28 (11) | C12—C11—C10 | 120.66 (13) |
N1—C1—C2 | 124.03 (12) | C12—C11—H11 | 119.7 |
N1—C1—C6 | 119.91 (12) | C10—C11—H11 | 119.7 |
C2—C1—C6 | 116.03 (12) | C11—C12—C13 | 118.87 (14) |
C3—C2—C1 | 121.55 (13) | C11—C12—H12 | 120.6 |
C3—C2—N5 | 116.41 (12) | C13—C12—H12 | 120.6 |
C1—C2—N5 | 122.04 (12) | C14—C13—C12 | 121.10 (14) |
C4—C3—C2 | 120.84 (13) | C14—C13—H13 | 119.5 |
C4—C3—H3A | 119.6 | C12—C13—H13 | 119.5 |
C2—C3—H3A | 119.6 | C13—C14—C9 | 121.53 (13) |
C3—C4—C5 | 118.71 (14) | C13—C14—H14 | 119.2 |
C3—C4—H4A | 120.6 | C9—C14—H14 | 119.2 |
C5—C4—H4A | 120.6 | C8—C15—H15A | 109.5 |
C6—C5—C4 | 121.28 (14) | C8—C15—H15B | 109.5 |
C6—C5—H5 | 119.4 | H15A—C15—H15B | 109.5 |
C4—C5—H5 | 119.4 | C8—C15—H15C | 109.5 |
C5—C6—C1 | 121.58 (13) | H15A—C15—H15C | 109.5 |
C5—C6—H6 | 119.2 | H15B—C15—H15C | 109.5 |
C18H18N6O6·0.5C4H8O | F(000) = 1888 |
Mr = 450.43 | Dx = 1.457 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 27.312 (6) Å | Cell parameters from 1905 reflections |
b = 7.5929 (16) Å | θ = 2.2–25.1° |
c = 20.625 (4) Å | µ = 0.11 mm−1 |
β = 106.241 (7)° | T = 150 K |
V = 4106.4 (15) Å3 | Polyhedron, red |
Z = 8 | 0.41 × 0.19 × 0.07 mm |
Bruker SMART CCD area-detector diffractometer | 2876 reflections with I > 2σ(I) |
CCD rotation images, thin slices scans | Rint = 0.049 |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | θmax = 28.0°, θmin = 1.6° |
Tmin = 0.96, Tmax = 0.98 | h = −34→35 |
16722 measured reflections | k = −9→9 |
4588 independent reflections | l = −26→25 |
Refinement on F2 | 38 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.062 | H 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 reflections | Δρmax = 0.84 e Å−3 |
348 parameters | Δρmin = −0.77 e Å−3 |
C18H18N6O6·0.5C4H8O | V = 4106.4 (15) Å3 |
Mr = 450.43 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 27.312 (6) Å | µ = 0.11 mm−1 |
b = 7.5929 (16) Å | T = 150 K |
c = 20.625 (4) Å | 0.41 × 0.19 × 0.07 mm |
β = 106.241 (7)° |
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 = 0.98 | Rint = 0.049 |
16722 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 38 restraints |
wR(F2) = 0.168 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.34 | Δρmax = 0.84 e Å−3 |
4588 reflections | Δρmin = −0.77 e Å−3 |
348 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.17870 (8) | 1.3512 (3) | 0.76591 (9) | 0.0683 (6) | |
O2 | 0.22326 (6) | 1.2051 (2) | 0.71278 (8) | 0.0531 (5) | |
O3 | 0.50321 (6) | 0.5392 (2) | 0.42151 (8) | 0.0502 (5) | |
O4 | 0.46806 (6) | 0.4790 (2) | 0.31644 (8) | 0.0434 (4) | |
N1 | 0.19247 (7) | 1.1720 (2) | 0.58179 (9) | 0.0313 (4) | |
H1N | 0.2163 (7) | 1.157 (3) | 0.6180 (8) | 0.048 (8)* | |
N2 | 0.19374 (6) | 1.1111 (2) | 0.52012 (8) | 0.0299 (4) | |
N3 | 0.27870 (6) | 0.9045 (2) | 0.44555 (8) | 0.0281 (4) | |
N4 | 0.28346 (7) | 0.8452 (2) | 0.38623 (9) | 0.0315 (4) | |
H4N | 0.2596 (6) | 0.856 (3) | 0.3495 (7) | 0.042 (7)* | |
N5 | 0.18406 (8) | 1.2873 (3) | 0.71332 (10) | 0.0443 (5) | |
N6 | 0.46624 (7) | 0.5401 (2) | 0.37109 (9) | 0.0337 (4) | |
C1 | 0.14879 (8) | 1.2471 (3) | 0.58896 (10) | 0.0290 (5) | |
C2 | 0.14367 (8) | 1.3073 (3) | 0.65172 (11) | 0.0325 (5) | |
C3 | 0.09841 (9) | 1.3851 (3) | 0.65634 (12) | 0.0393 (6) | |
H3 | 0.0960 | 1.4251 | 0.6980 | 0.047* | |
C4 | 0.05777 (9) | 1.4031 (3) | 0.60067 (12) | 0.0400 (6) | |
H4 | 0.0278 | 1.4559 | 0.6039 | 0.048* | |
C5 | 0.06196 (9) | 1.3407 (3) | 0.53863 (12) | 0.0384 (6) | |
H5 | 0.0341 | 1.3500 | 0.5006 | 0.046* | |
C6 | 0.10589 (8) | 1.2667 (3) | 0.53269 (11) | 0.0334 (5) | |
H6 | 0.1076 | 1.2282 | 0.4906 | 0.040* | |
C7 | 0.23542 (7) | 1.0343 (3) | 0.51720 (10) | 0.0266 (5) | |
C8 | 0.23569 (7) | 0.9678 (3) | 0.45052 (10) | 0.0265 (5) | |
C9 | 0.32886 (7) | 0.7676 (3) | 0.38426 (10) | 0.0271 (5) | |
C10 | 0.33396 (8) | 0.7112 (3) | 0.32212 (10) | 0.0328 (5) | |
H10 | 0.3070 | 0.7248 | 0.2833 | 0.039* | |
C11 | 0.37878 (8) | 0.6354 (3) | 0.31816 (10) | 0.0314 (5) | |
H11 | 0.3821 | 0.5969 | 0.2768 | 0.038* | |
C12 | 0.41876 (7) | 0.6169 (3) | 0.37593 (10) | 0.0281 (5) | |
C13 | 0.41411 (8) | 0.6691 (3) | 0.43844 (10) | 0.0301 (5) | |
H13 | 0.4412 | 0.6540 | 0.4771 | 0.036* | |
C14 | 0.36930 (7) | 0.7432 (3) | 0.44275 (10) | 0.0283 (5) | |
H14 | 0.3658 | 0.7771 | 0.4845 | 0.034* | |
C15 | 0.28221 (8) | 1.0154 (3) | 0.57567 (11) | 0.0355 (5) | |
H15A | 0.3083 | 0.9562 | 0.5611 | 0.053* | |
H15B | 0.2742 | 0.9479 | 0.6107 | 0.053* | |
H15C | 0.2941 | 1.1299 | 0.5927 | 0.053* | |
O5 | 0.19003 (7) | 1.0375 (2) | 0.33805 (8) | 0.0559 (5) | |
C16 | 0.18927 (8) | 0.9788 (3) | 0.39144 (10) | 0.0306 (5) | |
O6A | 0.15276 (9) | 0.8689 (4) | 0.40072 (14) | 0.0303 (5) | 0.5 |
C17A | 0.10352 (15) | 0.8570 (5) | 0.3481 (2) | 0.0293 (9) | 0.5 |
H17A | 0.1094 | 0.8468 | 0.3040 | 0.035* | 0.5 |
H17B | 0.0837 | 0.9628 | 0.3485 | 0.035* | 0.5 |
C18A | 0.07520 (18) | 0.7016 (6) | 0.3610 (3) | 0.0428 (11) | 0.5 |
H18A | 0.0453 | 0.6848 | 0.3238 | 0.064* | 0.5 |
H18B | 0.0653 | 0.7197 | 0.4017 | 0.064* | 0.5 |
H18C | 0.0966 | 0.5992 | 0.3660 | 0.064* | 0.5 |
O6B | 0.14485 (8) | 0.9632 (4) | 0.40577 (14) | 0.0303 (5) | 0.5 |
C17B | 0.10085 (17) | 1.0003 (7) | 0.3487 (2) | 0.0442 (11) | 0.5 |
H17C | 0.0709 | 0.9451 | 0.3562 | 0.053* | 0.5 |
H17D | 0.1063 | 0.9496 | 0.3081 | 0.053* | 0.5 |
C18B | 0.09143 (19) | 1.1959 (7) | 0.3383 (2) | 0.0532 (13) | 0.5 |
H18D | 0.0625 | 1.2150 | 0.3000 | 0.080* | 0.5 |
H18E | 0.1210 | 1.2509 | 0.3307 | 0.080* | 0.5 |
H18F | 0.0848 | 1.2458 | 0.3778 | 0.080* | 0.5 |
O1C | 0.00132 (19) | 0.4558 (5) | 0.2852 (3) | 0.0898 (15) | 0.5 |
C1C | 0.0326 (2) | 0.6129 (7) | 0.3021 (3) | 0.0614 (16) | 0.5 |
H1CA | 0.0156 | 0.7005 | 0.3223 | 0.074* | 0.5 |
H1CB | 0.0387 | 0.6629 | 0.2618 | 0.074* | 0.5 |
C2C | 0.0826 (2) | 0.5585 (8) | 0.3516 (3) | 0.0698 (18) | 0.5 |
H2A | 0.0812 | 0.5706 | 0.3979 | 0.084* | 0.5 |
H2B | 0.1107 | 0.6278 | 0.3454 | 0.084* | 0.5 |
C3C | 0.0874 (2) | 0.3652 (7) | 0.3334 (3) | 0.081 (2) | 0.5 |
H3A | 0.1161 | 0.3487 | 0.3150 | 0.098* | 0.5 |
H3B | 0.0920 | 0.2905 | 0.3728 | 0.098* | 0.5 |
C4C | 0.0374 (2) | 0.3238 (8) | 0.2808 (4) | 0.079 (2) | 0.5 |
H4A | 0.0423 | 0.3235 | 0.2360 | 0.095* | 0.5 |
H4B | 0.0252 | 0.2086 | 0.2893 | 0.095* | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0732 (14) | 0.0949 (16) | 0.0344 (10) | −0.0037 (11) | 0.0112 (9) | −0.0194 (10) |
O2 | 0.0353 (10) | 0.0782 (14) | 0.0402 (10) | −0.0052 (9) | 0.0012 (8) | −0.0067 (9) |
O3 | 0.0265 (9) | 0.0807 (13) | 0.0382 (9) | 0.0123 (8) | 0.0004 (7) | −0.0041 (8) |
O4 | 0.0395 (9) | 0.0529 (11) | 0.0390 (9) | 0.0121 (8) | 0.0129 (7) | −0.0057 (8) |
N1 | 0.0278 (10) | 0.0377 (11) | 0.0271 (10) | 0.0005 (8) | 0.0058 (8) | −0.0013 (8) |
N2 | 0.0279 (10) | 0.0334 (10) | 0.0286 (10) | −0.0014 (8) | 0.0084 (8) | 0.0025 (8) |
N3 | 0.0238 (9) | 0.0302 (10) | 0.0301 (9) | −0.0016 (7) | 0.0071 (7) | 0.0010 (8) |
N4 | 0.0234 (10) | 0.0410 (11) | 0.0282 (10) | 0.0020 (8) | 0.0041 (8) | 0.0015 (8) |
N5 | 0.0461 (13) | 0.0533 (13) | 0.0324 (11) | −0.0147 (10) | 0.0090 (10) | −0.0068 (10) |
N6 | 0.0266 (10) | 0.0395 (11) | 0.0345 (10) | 0.0031 (8) | 0.0076 (8) | 0.0006 (9) |
C1 | 0.0283 (12) | 0.0266 (11) | 0.0328 (11) | −0.0053 (9) | 0.0097 (9) | 0.0001 (9) |
C2 | 0.0339 (12) | 0.0325 (12) | 0.0301 (11) | −0.0102 (10) | 0.0074 (9) | −0.0028 (9) |
C3 | 0.0485 (15) | 0.0376 (13) | 0.0380 (13) | −0.0081 (11) | 0.0224 (12) | −0.0055 (11) |
C4 | 0.0387 (14) | 0.0387 (14) | 0.0480 (15) | 0.0005 (10) | 0.0208 (12) | −0.0012 (11) |
C5 | 0.0311 (12) | 0.0393 (14) | 0.0431 (13) | 0.0027 (10) | 0.0073 (10) | 0.0022 (11) |
C6 | 0.0362 (13) | 0.0353 (12) | 0.0288 (11) | 0.0005 (10) | 0.0095 (10) | −0.0025 (9) |
C7 | 0.0246 (11) | 0.0250 (11) | 0.0291 (11) | −0.0016 (9) | 0.0060 (9) | 0.0053 (9) |
C8 | 0.0236 (11) | 0.0276 (11) | 0.0275 (11) | 0.0001 (9) | 0.0056 (8) | 0.0084 (9) |
C9 | 0.0215 (11) | 0.0275 (11) | 0.0322 (11) | −0.0014 (8) | 0.0076 (9) | 0.0011 (9) |
C10 | 0.0250 (11) | 0.0399 (13) | 0.0289 (11) | 0.0011 (9) | 0.0003 (9) | −0.0008 (10) |
C11 | 0.0295 (12) | 0.0364 (12) | 0.0276 (11) | 0.0007 (9) | 0.0068 (9) | −0.0034 (9) |
C12 | 0.0232 (11) | 0.0274 (11) | 0.0334 (11) | 0.0007 (8) | 0.0073 (9) | 0.0010 (9) |
C13 | 0.0252 (11) | 0.0345 (12) | 0.0282 (11) | 0.0003 (9) | 0.0034 (9) | 0.0005 (9) |
C14 | 0.0246 (11) | 0.0323 (12) | 0.0280 (11) | −0.0008 (9) | 0.0072 (9) | 0.0004 (9) |
C15 | 0.0308 (12) | 0.0387 (13) | 0.0333 (12) | 0.0023 (10) | 0.0031 (10) | −0.0028 (10) |
O5 | 0.0509 (11) | 0.0739 (13) | 0.0362 (10) | −0.0103 (9) | 0.0011 (8) | 0.0222 (9) |
C16 | 0.0243 (10) | 0.0413 (13) | 0.0260 (11) | 0.0068 (9) | 0.0067 (8) | 0.0020 (10) |
O6A | 0.0222 (8) | 0.0439 (12) | 0.0255 (8) | 0.0071 (8) | 0.0080 (6) | −0.0046 (10) |
C17A | 0.0264 (18) | 0.029 (2) | 0.029 (2) | 0.0051 (16) | 0.0016 (14) | −0.0033 (19) |
C18A | 0.034 (2) | 0.033 (3) | 0.054 (3) | −0.0018 (17) | 0.000 (2) | −0.002 (2) |
O6B | 0.0222 (8) | 0.0439 (12) | 0.0255 (8) | 0.0071 (8) | 0.0080 (6) | −0.0046 (10) |
C17B | 0.0274 (18) | 0.065 (3) | 0.035 (2) | 0.004 (2) | 0.0010 (16) | 0.001 (2) |
C18B | 0.047 (3) | 0.067 (3) | 0.037 (3) | 0.019 (2) | −0.003 (2) | 0.002 (2) |
O1C | 0.092 (3) | 0.068 (3) | 0.125 (4) | −0.010 (3) | 0.056 (4) | −0.020 (3) |
C1C | 0.056 (4) | 0.041 (3) | 0.085 (4) | −0.001 (3) | 0.016 (3) | −0.008 (3) |
C2C | 0.059 (4) | 0.078 (5) | 0.061 (4) | 0.000 (3) | −0.003 (3) | −0.008 (3) |
C3C | 0.081 (5) | 0.054 (4) | 0.085 (5) | 0.008 (3) | −0.016 (4) | 0.006 (3) |
C4C | 0.067 (4) | 0.067 (4) | 0.099 (5) | −0.002 (4) | 0.016 (4) | −0.024 (4) |
O1—N5 | 1.234 (2) | C13—H13 | 0.9300 |
O2—N5 | 1.242 (3) | C14—H14 | 0.9300 |
O3—N6 | 1.230 (2) | C15—H15A | 0.9600 |
O4—N6 | 1.233 (2) | C15—H15B | 0.9600 |
N1—N2 | 1.363 (2) | C15—H15C | 0.9600 |
N1—C1 | 1.367 (3) | O5—C16 | 1.193 (2) |
N1—H1N | 0.849 (10) | C16—O6B | 1.332 (3) |
N2—C7 | 1.295 (3) | C16—O6A | 1.354 (3) |
N3—C8 | 1.299 (3) | O6A—C17A | 1.476 (4) |
N3—N4 | 1.344 (2) | C17A—C18A | 1.475 (5) |
N4—C9 | 1.383 (3) | C17A—H17A | 0.9700 |
N4—H4N | 0.855 (10) | C17A—H17B | 0.9700 |
N5—C2 | 1.439 (3) | C18A—H18A | 0.9600 |
N6—C12 | 1.450 (3) | C18A—H18B | 0.9600 |
C1—C6 | 1.408 (3) | C18A—H18C | 0.9600 |
C1—C2 | 1.416 (3) | O6B—C17B | 1.455 (5) |
C2—C3 | 1.397 (3) | C17B—C18B | 1.512 (6) |
C3—C4 | 1.362 (3) | C17B—H17C | 0.9700 |
C3—H3 | 0.9300 | C17B—H17D | 0.9700 |
C4—C5 | 1.399 (3) | C18B—H18D | 0.9600 |
C4—H4 | 0.9300 | C18B—H18E | 0.9600 |
C5—C6 | 1.361 (3) | C18B—H18F | 0.9600 |
C5—H5 | 0.9300 | O1C—C4C | 1.426 (6) |
C6—H6 | 0.9300 | O1C—C1C | 1.452 (6) |
C7—C8 | 1.467 (3) | C1C—C2C | 1.515 (6) |
C7—C15 | 1.499 (3) | C1C—H1CA | 0.9700 |
C8—C16 | 1.495 (3) | C1C—H1CB | 0.9700 |
C9—C10 | 1.395 (3) | C2C—C3C | 1.529 (6) |
C9—C14 | 1.402 (3) | C2C—H2A | 0.9700 |
C10—C11 | 1.375 (3) | C2C—H2B | 0.9700 |
C10—H10 | 0.9300 | C3C—C4C | 1.521 (6) |
C11—C12 | 1.380 (3) | C3C—H3A | 0.9700 |
C11—H11 | 0.9300 | C3C—H3B | 0.9700 |
C12—C13 | 1.388 (3) | C4C—H4A | 0.9700 |
C13—C14 | 1.372 (3) | C4C—H4B | 0.9700 |
N2—N1—C1 | 119.55 (17) | C7—C15—H15C | 109.5 |
N2—N1—H1N | 124.1 (16) | H15A—C15—H15C | 109.5 |
C1—N1—H1N | 116.0 (16) | H15B—C15—H15C | 109.5 |
C7—N2—N1 | 116.64 (17) | O5—C16—O6B | 119.3 (2) |
C8—N3—N4 | 121.05 (17) | O5—C16—O6A | 124.3 (2) |
N3—N4—C9 | 119.03 (17) | O5—C16—C8 | 122.90 (19) |
N3—N4—H4N | 122.0 (15) | O6B—C16—C8 | 115.6 (2) |
C9—N4—H4N | 119.0 (15) | O6A—C16—C8 | 109.9 (2) |
O1—N5—O2 | 121.3 (2) | C16—O6A—C17A | 119.3 (3) |
O1—N5—C2 | 119.0 (2) | O6A—C17A—C18A | 109.4 (3) |
O2—N5—C2 | 119.67 (19) | O6A—C17A—H17A | 109.8 |
O3—N6—O4 | 122.50 (18) | C18A—C17A—H17A | 109.8 |
O3—N6—C12 | 118.84 (18) | O6A—C17A—H17B | 109.8 |
O4—N6—C12 | 118.66 (17) | C18A—C17A—H17B | 109.8 |
N1—C1—C6 | 120.36 (19) | H17A—C17A—H17B | 108.2 |
N1—C1—C2 | 123.07 (19) | C17A—C18A—H18A | 109.5 |
C6—C1—C2 | 116.56 (19) | C17A—C18A—H18B | 109.5 |
C3—C2—C1 | 121.0 (2) | H18A—C18A—H18B | 109.5 |
C3—C2—N5 | 117.3 (2) | C17A—C18A—H18C | 109.5 |
C1—C2—N5 | 121.7 (2) | H18A—C18A—H18C | 109.5 |
C4—C3—C2 | 120.8 (2) | H18B—C18A—H18C | 109.5 |
C4—C3—H3 | 119.6 | C16—O6B—C17B | 113.6 (3) |
C2—C3—H3 | 119.6 | O6B—C17B—C18B | 112.0 (4) |
C3—C4—C5 | 118.8 (2) | O6B—C17B—H17C | 109.2 |
C3—C4—H4 | 120.6 | C18B—C17B—H17C | 109.2 |
C5—C4—H4 | 120.6 | O6B—C17B—H17D | 109.2 |
C6—C5—C4 | 121.5 (2) | C18B—C17B—H17D | 109.2 |
C6—C5—H5 | 119.3 | H17C—C17B—H17D | 107.9 |
C4—C5—H5 | 119.3 | C17B—C18B—H18D | 109.5 |
C5—C6—C1 | 121.4 (2) | C17B—C18B—H18E | 109.5 |
C5—C6—H6 | 119.3 | H18D—C18B—H18E | 109.5 |
C1—C6—H6 | 119.3 | C17B—C18B—H18F | 109.5 |
N2—C7—C8 | 115.70 (18) | H18D—C18B—H18F | 109.5 |
N2—C7—C15 | 124.65 (19) | H18E—C18B—H18F | 109.5 |
C8—C7—C15 | 119.63 (18) | C4C—O1C—C1C | 102.8 (5) |
N3—C8—C7 | 116.30 (18) | O1C—C1C—C2C | 107.3 (4) |
N3—C8—C16 | 122.38 (18) | O1C—C1C—H1CA | 110.3 |
C7—C8—C16 | 121.28 (17) | C2C—C1C—H1CA | 110.3 |
N4—C9—C10 | 118.59 (18) | O1C—C1C—H1CB | 110.3 |
N4—C9—C14 | 121.89 (18) | C2C—C1C—H1CB | 110.3 |
C10—C9—C14 | 119.52 (19) | H1CA—C1C—H1CB | 108.5 |
C11—C10—C9 | 120.16 (19) | C1C—C2C—C3C | 102.7 (4) |
C11—C10—H10 | 119.9 | C1C—C2C—H2A | 111.2 |
C9—C10—H10 | 119.9 | C3C—C2C—H2A | 111.2 |
C10—C11—C12 | 119.60 (19) | C1C—C2C—H2B | 111.2 |
C10—C11—H11 | 120.2 | C3C—C2C—H2B | 111.2 |
C12—C11—H11 | 120.2 | H2A—C2C—H2B | 109.1 |
C11—C12—C13 | 121.13 (19) | C4C—C3C—C2C | 104.5 (4) |
C11—C12—N6 | 119.24 (18) | C4C—C3C—H3A | 110.9 |
C13—C12—N6 | 119.63 (18) | C2C—C3C—H3A | 110.9 |
C14—C13—C12 | 119.48 (19) | C4C—C3C—H3B | 110.9 |
C14—C13—H13 | 120.3 | C2C—C3C—H3B | 110.9 |
C12—C13—H13 | 120.3 | H3A—C3C—H3B | 108.9 |
C13—C14—C9 | 120.08 (19) | O1C—C4C—C3C | 108.0 (5) |
C13—C14—H14 | 120.0 | O1C—C4C—H4A | 110.1 |
C9—C14—H14 | 120.0 | C3C—C4C—H4A | 110.1 |
C7—C15—H15A | 109.5 | O1C—C4C—H4B | 110.1 |
C7—C15—H15B | 109.5 | C3C—C4C—H4B | 110.1 |
H15A—C15—H15B | 109.5 | H4A—C4C—H4B | 108.4 |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C15H14N6O4 | C18H18N6O6·0.5C4H8O |
Mr | 342.32 | 450.43 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, C2/c |
Temperature (K) | 150 | 150 |
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) |
V (Å3) | 1507.7 (5) | 4106.4 (15) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.11 |
Crystal size (mm) | 0.31 × 0.14 × 0.08 | 0.41 × 0.19 × 0.07 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS in SAINT-NT; Bruker, 2002) | Multi-scan (SADABS in SAINT-NT; Bruker, 2002) |
Tmin, Tmax | 0.95, 0.99 | 0.96, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12121, 3365, 2175 | 16722, 4588, 2876 |
Rint | 0.039 | 0.049 |
(sin θ/λ)max (Å−1) | 0.658 | 0.660 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.092, 0.87 | 0.062, 0.168, 1.34 |
No. of reflections | 3365 | 4588 |
No. of parameters | 233 | 348 |
No. of restraints | 2 | 38 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.18 | 0.84, −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).
(I) | (II) | |
C1—N1 | 1.3641 (17) | 1.367 (2) |
N1—N2 | 1.3673 (15) | 1.364 (2) |
N2—C7 | 1.2859 (17) | 1.291 (2) |
C7—C8 | 1.4495 (19) | 1.470 (2) |
C8—N3 | 1.2962 (16) | 1.299 (2) |
N3—N4 | 1.3664 (15) | 1.344 (2) |
N4—C9 | 1.3664 (17) | 1.383 (2) |
Code | D—H···A | D—H | H···A | D···A | D—H···A |
#1a | N1—H1N···O2 | 0.86 (1) | 2.04 (1) | 2.6484 (16) | 127 (1) |
#2a | N4—H4···O3 | 0.85 (1) | 1.99 (1) | 2.6215 (16) | 130 (1) |
#3a | N1—H1N···O1i | 0.86 (1) | 2.48 (1) | 3.2859 (16) | 157 (1) |
Symmetry code: (i) -x+1, y+1/2, -z+1/2. |
Code | D—H···A | D—H | H···A | D···A | D—H···A |
#1b | N1—H1N···O2 | 0.86 (2) | 1.95 (2) | 2.608 (2) | 132 (2) |
#2b | N4—H4N···O5 | 0.86 (2) | 2.31 (2) | 2.867 (2) | 123 (2) |
#3b | C10—H10···O2i | 0.93 | 2.40 | 3.287 (3) | 160 |
Symmetry code: (i) x, -y+2, z-1/2. |
Code | Group 1···Group 2 | ccd (Å) | da (°) | sa (°) | ipd (Å) |
#4a | Cg1···Cg4ii | 3.424 | 5.8 | 3.8 | 3.416 |
#5a | Cg2···Cg3iii | 3.437 | 5.2 | 5.3 | 3.422 |
#6a | Cg1···Cg2iv | 4.0345 (11) | 3.08 (7) | 32.90 (10) | 3.38 (4) |
#7a | O2···O1i | 2.7538 (16) | |||
#8a | O3···O3v | 2.8338 (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 C7═N2 bond and Cg4 that of the C8═N3 bond. |
Code | Group 1···Group 2 | ccd (Å) | sa (°) | da (°) | ipd (Å) |
#4b | Cg1···Cg2ii | 3.9766 (14) | 2.32 (10) | 30.95(5 | 3.409 (2) |
#5b | Cg1···Cg2iii | 3.7433 (14) | 2.32 (10) | 23.4 (8) | 3.43 (2) |
#6b | Cg3···Cg3iii | 3.524 | 0 | 9.85 (3) | 3.427 (2) |
#7b | Cg3···Cg4ii | 3.962 | 5.3 | 31.9 (3) | 3.36 (4) |
#8b | Cg3···Cg4iii | 3.831 | 5.3 | 26.1 (4) | 3.44 (2) |
#9b | Cg4···Cg4ii | 3.635 | 0 | 23.82 (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 C7═N2 bond and Cg4 that of the C8═N3 bond. |