Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615006403/qs3046sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615006403/qs3046Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615006403/qs3046IIsup3.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615006403/qs3046Isup4.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615006403/qs3046IIsup5.cml |
CCDC references: 1056707; 1056706
\ Pyrazole derivatives show a broad range of biological applications in the agrochemical and pharmaceutical fields, and a number of them have been commercialized. For example, the insecticide chlorantraniliprole {systematic name: 3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-1-(3-chloro-2-\ pyridin-2-yl)-1H- pyrazole-5-carboxamide} acts as a potent and selective activator of ryanodine receptors in insects with high activity in a broad range of Lepidoptera (Lahm et al., 2007), and celecoxib {systematic name: 4-[5-(4-methylphenyl)-3-(trifluoromethyl)pyrazol-1-yl]benzenesulfonamide} acts as a potent COX-2 inhibitor used in the treatment of inflammation and acute pain (Penning et al., 1997).
Fluoride-mediated nucleophilic substitution of 5-chloropyrazoles containing an electron-withdrawing group at the 4-position has recently been utilized in the preparation of 5-alkylaminopyrazoles and 5-alkoxypyrazoles (Shavnya et al., 2005). In a similar fashion, we have now studied a synthetic route for the preparation of 5-alkylamino derivatives from 5-chloro-1H-pyrazole-4-carbaldehydes via nucleophilic aromatic substitution with cyclohexylamine, as straightforward molecular diversification from the resulting 5-alkylamino-1H-4-carbaldehydes should then give access to a variety of new pyrazole derivatives. Thus, the reaction of 5-chloro-3-methyl-1-(pyridin-2-yl)-1H-pyrazole-4-carbaldehyde with cyclohexylamine, using caesium carbonate in N,N-dimethylformamide under microwave irradiation, affords the required substitution product 5-cyclohexylamino-3-methyl-1-(pyridin-2-yl)-1H-pyrazole-4-carbaldehyde, (I), in high yield. However, no such substitution reaction was observed with 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde, despite the use of entirely similar reaction conditions. This difference can plausibly be ascribed to the stronger activating ability of the 1-(pyridin-2-yl) substituent, in contrast with the lower activating ability of a 1-phenyl substituent. However, the use of ethanol rather than N,N-dimethylformamide as solvent in the reaction between 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde and cyclohexylamine in the presence of caesium carbonate under microwave irradiation affords the unexpected product (Z)-4-[(cyclohexylamino)methylidene]-3-methyl-1-phenyl-1H-\ pyrazol-5(4H)-one, (II). The production of (II) is presumably due to an initial condensation reaction at the formyl group to form an intermediate imine, followed by a hydrolysis reaction at position 5 (see scheme). We report here the molecular structures and supramolecular assembly of (I) and (II). The aims of this study are thus the confirmation of the molecular constitutions of (I) and (II) and the exploration and comparison of the supramolecular assembly in the two compounds.
For the synthesis of (I) and (II), cyclohexylamine (0.9024 mmol) and caesium carbonate (0.1470 mmol) were added to a solution of either 5-chloro-3-methyl-1-(pyridin-2-yl)-1H-pyrazole-4-carbaldehyde (0.4512 mmol) in N,N-dimethylformamide (1 ml) for (I) or 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (0.4532 mmol) in ethanol (1 ml) for (II). The resulting reaction mixtures were stirred and heated at 433 K for 10 min [for (I)] or 30 min [for (II)] under microwave irradiation. The mixtures were filtered, and the filtrates were diluted with water (50 ml) and then extracted with dichloromethane (3 × 15 ml). The combined organic extracts were dried over anhydrous sodium sulfate and then the solvent was removed under reduced pressure. The resulting crude products were purified by silica-gel column chromatography using dichloromethane–ethyl acetate as eluent (30:1 v/v). Crystallization from N,N-dimethylformamide at ambient temperature and in the presence of air gave crystals of (I) and (II) suitable for single-crystal X-ray diffraction.
Compound (I): colourless crystals, yield 93%, m.p. 378 K; HR—MS (ESI), m/z found [M+H]+ 285.1723, [M+Na]+ 307.1538; calculated for [C16H20N4O+H]+ 285.1710, [C16H20N4O+Na]+ 307.1529. Compound (II): pale-yellow crystals, yield 65%, m. p. 377 K; HR—MS (ESI), m/z found [M+H]+ 284.2011; [M+Na]+ 306.1575, calculated for [C17H21N3O+H]+ 284.1757, [C17H21N3O+Na]+ 306.1577.
Crystal data, data collection and structure refinement details are summarized in Table 1. A number of crystals of (II) were examined but it did not prove possible to obtain a satisfactory data set at 120 K, possibly because of crystal damage during cooling. However, an entirely satisfactory data set was collected for (II) at ambient temperature and it became obvious at an early stage that in one of the two independent molecules of (II) the cyclohexylamine unit exhibited positional disorder over two sets of atomic sites having unequal occupancies. For the minor disorder component, the bonded distances and the one-angle non-bonded distances were restrained to be identical to the corresponding distances in the major component, subject to uncertainties of 0.005 and 0.01 Å, respectively. The anisotropic displacement parameters for those pairs of partial-occupancy atoms occupying approximately the same physical space were constrained to be identical. The partial occupancy H atoms were included in calculated positions, with C—H = 0.97 (CH2) or 0.98 Å (aliphatic C—H) and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N). Subject to these conditions, the site occupancies refined to values of 0.65 (3) and 0.35 (3). For (I) and for the ordered components of (II), all H atoms were located in difference maps. For these components, C-bound H atoms were then treated as riding in geometrically idealized positions, with C—H = 0.95 (alkenyl, aromatic and pyridyl), 0.98 (CH3), 0.99 (CH2) or 1.00 Å (aliphatic C—H) at 120 K, or 0.93 (alkenyl, aromatic and pyridyl), 0.96 (CH3), 0.97 (CH2) or 0.98 Å (aliphatic C—H) at 294 K, and with Uiso(H) = kUeq(C) where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, or 1.2 for all other C-bound H atoms. For the H atoms bonded to ordered N atoms, the atomic coordinates were refined with Uiso(H) = 1.2Ueq(N), giving the N—H distances shown in Table 3. For (I), one low-angle reflection, i.e. 310, which had been attenuated by the beam stop, was omitted from the refinements. A rather high value of K was found for the group of very weak reflections having Fc/Fc(max) in the range 0 < Fc/Fc(max) < 0.007. Examination of the .fcf file for (II) showed that around a dozen high-angle reflections, although very weak, had quite high ratios of Fo2/Fc2, leading to a Level B alert in checkCIF. This accounts for the high value of K in the analysis of variance for the reflection group having Fc/Fc(max) in the range 0 < Fc/Fc(max) < 0.004. As there appeared to be no experimental justification for the removal of these weak reflections from the data set, they were retained.
The molecular constitutions of (I) and (II) (Figs. 1 and 2) confirm the occurrence of two different reaction pathways based on, respectively, nucleophilic substitution to form (I), and initial imine formation by condensation followed by hydrolysis to form (II) (see scheme).
In (I), the non-H atoms, apart from those of the cyclohexyl substituent, are nearly coplanar. Thus, the dihedral angle between the planes of the pyridyl and pyrazole rings is only 2.47 (5)°, while that between the planes of the pyrazole ring and the carbaldehyde unit is 5.06 (6)°. The pyridyl ring is oriented such that its N atom can participate in the formation of an intramolecular N—H···N hydrogen bond (Fig. 1 and Table 3), forming an S(6) (Bernstein et al., 1995) motif. Within the pyrazole ring of (I), the short N2—C3 distance (Table 2) is consistent with the presence of an isolated double bond. On the other hand, the three C—C distances, C3—C4, C4—C5 and C4—C41, span a range of little more than 0.02 Å, despite the fact that C4—C5 is formally a double bond and the other two are formally single bonds. In addition, the geometry at the amino atom N5 is planar within the rather large experimental uncertainty (Table 2), and the C—O distance is long, even for a conjugated aldehyde [mean value (Allen et al., 1987) = 1.211 Å; upper quartile value = 1.216 Å]. These observations thus suggest that the polarized form (Ia) (see scheme) is a significant contributor to the overall electronic structure of (I).
Compound (II) crystallizes with Z' = 2, and it will be convenient to refer to the molecules containing atoms O15 and O25 (Fig. 2) as types 1 and 2, respectively. The type 1 molecules exhibit positional disorder of the cyclohexylamine fragment (Fig. 2a), with site occupancies for the two disorder conponents of 0.65 (3) and 0.35 (3), respectively. With a common position for the amine N atom in the two disorder components, the positional difference between the cyclohexyl rings depends only on small differences in the two torsion angles defining their positions relative to the remainder of the molecule: the relevant C—N—C—C angles differ by 7.6 (8)° between the two forms, but the N—C—C—C angles differ by less than 1.0°. Accordingly, a search for possible additional crystallographic symmetry was made but found none. Despite this, the conformations of and bond distances in the two independent molecules are very similar. The key geometric parameters in the two disorder components of the type 1 molecule are essentially identical, and hence the discussion of geometry will be confined to the major form. The dihedral angles between the planes of the phenyl and pyrazole rings are 32.97 (5) and 29.73 (5)° for the type 1 and 2 molecules, respectively, and the corresponding values for the dihedral angles between the pyrazole rings and the exocyclic C═C—N units are 5.51 (16)° for the major conformer of the type 1 molecule and 5.57 (11)° for the type 2 molecule, where the overall orientation of the cyclohexylamine unit in each type of molecule permits the participation of the N—H bond in the formation of an intramolecular N—H···O hydrogen bond (Fig. 2 and Table 5), forming S(6) motifs, as in (I). Also as in (I), the geometry at the amine N atoms is planar within experimental uncertainty (Table 4). The Cx6—Nx7 distances (x = 1 or 2) differ little from the Nx2—Cx3 distances, while the Cx5—Ox5 distance is long in both molecules. As for (I), these observations suggest that the polarized form (IIa) (see scheme) is a major contributor to the overall electronic structure of (II). Accordingly, any hydrogen bonds involving the amine and carbonyl units are charge-assisted hydrogen bonds (Gilli et al., 1994).
As noted above, the molecule of (I) contains an intramolecular N—H···N hydrogen bond and the N—H bond plays no role in the supramolecular assembly. Instead, a combination of two C—H···O hydrogen bonds (Table 3) links the molecules of (I) into sheets, the formation of which is readily analysed in terms of two very simple substructures (Ferguson et al., 1998a,b; Gregson et al., 2000). The C—H···O hydrogen bond involving atom C51 links pairs of inversion-related molecules into centrosymmetric dimers characterized by an R22(14) motif, where the reference dimer is centred at (1/4, 3/4, 1/2). The C—H···O hydrogen bond involving atom C16 links molecules related by the 21 screw axis along (1/4, y, 1/4) to form a simple C(9) chain running parallel to the [010] direction. The effect of such chains is to link the reference dimer centred at (1/4, 3/4, 1/2) directly to the four related dimers centred at (1/4, 1/4, 0), (1/4, 1/4, 1), (1/4, 5/4, 0) and (1/4, 5/4, 1), so forming a hydrogen-bonded sheet lying parallel to (100) (Fig. 3) in the domain 0 < x < 0.5. A second such sheet, related to the first by inversion, lies in the domain 0.5 < x < 1.0, but there are no direction-specific interactions between adjacent sheets. There are no C—H···π interactions in the structure of (I) and the only short inter-ring contacts involve the pyrazole ring which, as noted above, shows no significant aromatic character.
The supramolecular assembly of (II) is entirely different from that in (I), even though the potentially available hydrogen-bond donors and acceptors are similar for the two compounds. In (II), each of the two independent molecules contains an intramolecular N—H···O hydrogen bond (Table 5), forming an S(6) motif. Each molecular type forms a centrosymmetric dimer, built from planar three-centre N—H···O hydrogen bonds, containing a central R22(4) ring flanked by two inversion-related S(6) rings (Fig. 4). For the selected asymmetric unit, the dimers formed by the type 1 and 2 molecules (Fig. 2) are centred at (1/2, 1/2, 1/2) and (1/2, 1, 0) respectively, but there are no direction-specific interactions between the dimers.
In summary, we have demonstrated the different types of reaction product dependent upon the nature of the 1-aryl substituent, consistent with the occurrence of two different reaction pathways, and we have demonstrated the very different modes of supramolecular assembly in (I) and (II).
Data collection: COLLECT (Nonius, 1999) for (I); CrysAlis PRO (Agilent, 2012) for (II). Cell refinement: DIRAX/LSQ (Duisenberg et al., 2000) for (I); CrysAlis PRO (Agilent, 2012) for (II). Data reduction: EVALCCD (Duisenberg et al., 2003) for (I); CrysAlis PRO (Agilent, 2012) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).
C16H20N4O | F(000) = 1216 |
Mr = 284.36 | Dx = 1.286 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 21.369 (2) Å | Cell parameters from 3370 reflections |
b = 20.489 (3) Å | θ = 27.5–2.8° |
c = 6.7444 (10) Å | µ = 0.08 mm−1 |
β = 95.978 (10)° | T = 120 K |
V = 2936.8 (7) Å3 | Block, colourless |
Z = 8 | 0.32 × 0.24 × 0.21 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3367 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2149 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 4.0° |
ϕ and ω scans | h = −23→27 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −26→26 |
Tmin = 0.788, Tmax = 0.983 | l = −8→8 |
10192 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.0561P)2 + 0.4348P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
3367 reflections | Δρmax = 0.21 e Å−3 |
194 parameters | Δρmin = −0.30 e Å−3 |
C16H20N4O | V = 2936.8 (7) Å3 |
Mr = 284.36 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.369 (2) Å | µ = 0.08 mm−1 |
b = 20.489 (3) Å | T = 120 K |
c = 6.7444 (10) Å | 0.32 × 0.24 × 0.21 mm |
β = 95.978 (10)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3367 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2149 reflections with I > 2σ(I) |
Tmin = 0.788, Tmax = 0.983 | Rint = 0.051 |
10192 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.21 e Å−3 |
3367 reflections | Δρmin = −0.30 e Å−3 |
194 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 | ||
N1 | 0.14685 (6) | 0.56995 (6) | 0.1959 (2) | 0.0179 (3) | |
N2 | 0.09455 (6) | 0.61028 (7) | 0.1463 (2) | 0.0200 (3) | |
C3 | 0.11659 (8) | 0.66985 (8) | 0.1628 (2) | 0.0197 (4) | |
C4 | 0.18315 (7) | 0.67205 (8) | 0.2203 (2) | 0.0192 (4) | |
C5 | 0.20087 (7) | 0.60579 (8) | 0.2411 (2) | 0.0178 (4) | |
N11 | 0.18853 (6) | 0.46476 (7) | 0.2333 (2) | 0.0206 (3) | |
C12 | 0.13779 (7) | 0.50181 (8) | 0.1891 (2) | 0.0180 (4) | |
C13 | 0.07774 (8) | 0.47694 (9) | 0.1360 (2) | 0.0222 (4) | |
H13 | 0.0425 | 0.5051 | 0.1092 | 0.027* | |
C14 | 0.07108 (8) | 0.40990 (9) | 0.1235 (3) | 0.0254 (4) | |
H14 | 0.0310 | 0.3911 | 0.0845 | 0.031* | |
C15 | 0.12321 (8) | 0.37033 (9) | 0.1681 (3) | 0.0258 (4) | |
H15 | 0.1195 | 0.3242 | 0.1609 | 0.031* | |
C16 | 0.18056 (8) | 0.39942 (8) | 0.2233 (2) | 0.0231 (4) | |
H16 | 0.2162 | 0.3722 | 0.2558 | 0.028* | |
C31 | 0.07300 (8) | 0.72615 (9) | 0.1171 (3) | 0.0276 (4) | |
H31A | 0.0310 | 0.7098 | 0.0693 | 0.041* | |
H31B | 0.0888 | 0.7535 | 0.0140 | 0.041* | |
H31C | 0.0706 | 0.7521 | 0.2381 | 0.041* | |
C41 | 0.22074 (8) | 0.72994 (8) | 0.2375 (3) | 0.0229 (4) | |
H41 | 0.2650 | 0.7247 | 0.2646 | 0.027* | |
O41 | 0.20020 (6) | 0.78596 (6) | 0.21984 (19) | 0.0304 (3) | |
N5 | 0.25577 (6) | 0.57556 (7) | 0.2949 (2) | 0.0220 (3) | |
H5 | 0.2518 (8) | 0.5328 (10) | 0.297 (3) | 0.026* | |
C51 | 0.31307 (7) | 0.60696 (8) | 0.3867 (2) | 0.0194 (4) | |
H51 | 0.3011 | 0.6470 | 0.4584 | 0.023* | |
C52 | 0.35723 (8) | 0.62656 (9) | 0.2328 (3) | 0.0233 (4) | |
H52A | 0.3356 | 0.6576 | 0.1361 | 0.028* | |
H52B | 0.3689 | 0.5875 | 0.1587 | 0.028* | |
C53 | 0.41653 (8) | 0.65845 (9) | 0.3370 (3) | 0.0294 (4) | |
H53A | 0.4451 | 0.6704 | 0.2364 | 0.035* | |
H53B | 0.4049 | 0.6989 | 0.4044 | 0.035* | |
C54 | 0.45051 (8) | 0.61238 (10) | 0.4900 (3) | 0.0312 (5) | |
H54A | 0.4872 | 0.6351 | 0.5606 | 0.037* | |
H54B | 0.4663 | 0.5741 | 0.4206 | 0.037* | |
C55 | 0.40692 (8) | 0.58925 (9) | 0.6413 (3) | 0.0268 (4) | |
H55A | 0.3964 | 0.6266 | 0.7248 | 0.032* | |
H55B | 0.4290 | 0.5562 | 0.7299 | 0.032* | |
C56 | 0.34627 (8) | 0.55978 (9) | 0.5383 (3) | 0.0235 (4) | |
H56A | 0.3563 | 0.5189 | 0.4698 | 0.028* | |
H56B | 0.3177 | 0.5487 | 0.6398 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0167 (7) | 0.0186 (7) | 0.0183 (7) | 0.0004 (6) | 0.0005 (5) | −0.0007 (6) |
N2 | 0.0180 (7) | 0.0217 (8) | 0.0199 (8) | 0.0037 (6) | 0.0002 (5) | 0.0014 (6) |
C3 | 0.0222 (9) | 0.0204 (9) | 0.0164 (8) | 0.0008 (7) | 0.0021 (6) | −0.0005 (7) |
C4 | 0.0215 (8) | 0.0204 (8) | 0.0157 (8) | −0.0009 (7) | 0.0018 (6) | 0.0008 (7) |
C5 | 0.0184 (8) | 0.0209 (9) | 0.0145 (8) | −0.0014 (7) | 0.0033 (6) | −0.0007 (6) |
N11 | 0.0234 (8) | 0.0195 (7) | 0.0190 (8) | 0.0001 (6) | 0.0032 (5) | −0.0004 (6) |
C12 | 0.0235 (9) | 0.0190 (8) | 0.0118 (8) | −0.0020 (7) | 0.0027 (6) | −0.0015 (6) |
C13 | 0.0225 (9) | 0.0252 (10) | 0.0187 (9) | −0.0023 (7) | 0.0006 (6) | −0.0002 (7) |
C14 | 0.0295 (10) | 0.0270 (10) | 0.0200 (9) | −0.0093 (8) | 0.0038 (7) | −0.0026 (7) |
C15 | 0.0379 (11) | 0.0191 (9) | 0.0214 (10) | −0.0051 (8) | 0.0079 (7) | −0.0011 (7) |
C16 | 0.0305 (9) | 0.0199 (9) | 0.0195 (9) | 0.0014 (7) | 0.0060 (7) | 0.0004 (7) |
C31 | 0.0245 (9) | 0.0231 (9) | 0.0343 (11) | 0.0038 (8) | −0.0013 (7) | 0.0021 (8) |
C41 | 0.0229 (9) | 0.0217 (9) | 0.0238 (9) | −0.0010 (7) | 0.0014 (7) | −0.0002 (7) |
O41 | 0.0317 (7) | 0.0184 (7) | 0.0405 (8) | −0.0003 (6) | 0.0010 (6) | 0.0007 (5) |
N5 | 0.0176 (7) | 0.0180 (8) | 0.0296 (8) | −0.0013 (6) | −0.0014 (6) | −0.0031 (6) |
C51 | 0.0172 (8) | 0.0184 (8) | 0.0219 (9) | −0.0021 (7) | −0.0010 (6) | −0.0010 (7) |
C52 | 0.0204 (9) | 0.0272 (9) | 0.0220 (9) | 0.0004 (7) | 0.0012 (7) | 0.0034 (7) |
C53 | 0.0204 (9) | 0.0349 (11) | 0.0324 (11) | −0.0049 (8) | 0.0003 (7) | 0.0104 (8) |
C54 | 0.0189 (9) | 0.0372 (11) | 0.0360 (11) | −0.0025 (8) | −0.0044 (7) | 0.0085 (9) |
C55 | 0.0256 (9) | 0.0272 (10) | 0.0258 (10) | −0.0023 (8) | −0.0055 (7) | 0.0073 (8) |
C56 | 0.0228 (9) | 0.0229 (9) | 0.0245 (10) | −0.0024 (7) | 0.0012 (7) | 0.0031 (7) |
N1—N2 | 1.4020 (18) | C31—H31C | 0.9800 |
N2—C3 | 1.309 (2) | C41—H41 | 0.9500 |
C3—C4 | 1.435 (2) | N5—C51 | 1.462 (2) |
C4—C5 | 1.412 (2) | N5—H5 | 0.88 (2) |
C5—N1 | 1.375 (2) | C51—C56 | 1.527 (2) |
C4—C41 | 1.430 (2) | C51—C52 | 1.527 (2) |
C41—O41 | 1.230 (2) | C51—H51 | 1.0000 |
C5—N5 | 1.343 (2) | C52—C53 | 1.530 (2) |
N1—C12 | 1.410 (2) | C52—H52A | 0.9900 |
C3—C31 | 1.495 (2) | C52—H52B | 0.9900 |
N11—C12 | 1.332 (2) | C53—C54 | 1.525 (2) |
N11—C16 | 1.350 (2) | C53—H53A | 0.9900 |
C12—C13 | 1.393 (2) | C53—H53B | 0.9900 |
C13—C14 | 1.383 (2) | C54—C55 | 1.527 (3) |
C13—H13 | 0.9500 | C54—H54A | 0.9900 |
C14—C15 | 1.385 (3) | C54—H54B | 0.9900 |
C14—H14 | 0.9500 | C55—C56 | 1.530 (2) |
C15—C16 | 1.379 (2) | C55—H55A | 0.9900 |
C15—H15 | 0.9500 | C55—H55B | 0.9900 |
C16—H16 | 0.9500 | C56—H56A | 0.9900 |
C31—H31A | 0.9800 | C56—H56B | 0.9900 |
C31—H31B | 0.9800 | ||
C5—N1—N2 | 111.59 (13) | C5—N5—H5 | 112.4 (12) |
C5—N1—C12 | 130.18 (14) | C51—N5—H5 | 120.5 (12) |
N2—N1—C12 | 118.21 (13) | N5—C51—C56 | 108.37 (13) |
C3—N2—N1 | 104.98 (12) | N5—C51—C52 | 112.15 (14) |
N2—C3—C4 | 112.95 (14) | C56—C51—C52 | 110.15 (13) |
N2—C3—C31 | 119.42 (15) | N5—C51—H51 | 108.7 |
C4—C3—C31 | 127.61 (15) | C56—C51—H51 | 108.7 |
C5—C4—C41 | 130.27 (15) | C52—C51—H51 | 108.7 |
C5—C4—C3 | 104.15 (14) | C51—C52—C53 | 109.95 (14) |
C41—C4—C3 | 125.47 (15) | C51—C52—H52A | 109.7 |
N5—C5—N1 | 120.21 (15) | C53—C52—H52A | 109.7 |
N5—C5—C4 | 133.46 (15) | C51—C52—H52B | 109.7 |
N1—C5—C4 | 106.32 (13) | C53—C52—H52B | 109.7 |
C12—N11—C16 | 117.29 (14) | H52A—C52—H52B | 108.2 |
N11—C12—C13 | 123.79 (15) | C54—C53—C52 | 111.07 (15) |
N11—C12—N1 | 116.84 (14) | C54—C53—H53A | 109.4 |
C13—C12—N1 | 119.37 (15) | C52—C53—H53A | 109.4 |
C14—C13—C12 | 117.73 (16) | C54—C53—H53B | 109.4 |
C14—C13—H13 | 121.1 | C52—C53—H53B | 109.4 |
C12—C13—H13 | 121.1 | H53A—C53—H53B | 108.0 |
C13—C14—C15 | 119.53 (16) | C53—C54—C55 | 111.33 (15) |
C13—C14—H14 | 120.2 | C53—C54—H54A | 109.4 |
C15—C14—H14 | 120.2 | C55—C54—H54A | 109.4 |
C16—C15—C14 | 118.53 (16) | C53—C54—H54B | 109.4 |
C16—C15—H15 | 120.7 | C55—C54—H54B | 109.4 |
C14—C15—H15 | 120.7 | H54A—C54—H54B | 108.0 |
N11—C16—C15 | 123.10 (16) | C54—C55—C56 | 111.46 (15) |
N11—C16—H16 | 118.5 | C54—C55—H55A | 109.3 |
C15—C16—H16 | 118.5 | C56—C55—H55A | 109.3 |
C3—C31—H31A | 109.5 | C54—C55—H55B | 109.3 |
C3—C31—H31B | 109.5 | C56—C55—H55B | 109.3 |
H31A—C31—H31B | 109.5 | H55A—C55—H55B | 108.0 |
C3—C31—H31C | 109.5 | C51—C56—C55 | 111.52 (14) |
H31A—C31—H31C | 109.5 | C51—C56—H56A | 109.3 |
H31B—C31—H31C | 109.5 | C55—C56—H56A | 109.3 |
O41—C41—C4 | 125.03 (16) | C51—C56—H56B | 109.3 |
O41—C41—H41 | 117.5 | C55—C56—H56B | 109.3 |
C4—C41—H41 | 117.5 | H56A—C56—H56B | 108.0 |
C5—N5—C51 | 125.51 (14) | ||
C5—N1—N2—C3 | −0.44 (18) | N2—N1—C12—C13 | −0.7 (2) |
C12—N1—N2—C3 | −179.22 (14) | N11—C12—C13—C14 | −1.8 (3) |
N1—N2—C3—C4 | 0.70 (18) | N1—C12—C13—C14 | 177.57 (15) |
N1—N2—C3—C31 | 179.12 (15) | C12—C13—C14—C15 | 1.5 (2) |
N2—C3—C4—C5 | −0.71 (19) | C13—C14—C15—C16 | −0.3 (3) |
C31—C3—C4—C5 | −178.97 (17) | C12—N11—C16—C15 | 0.7 (2) |
N2—C3—C4—C41 | 175.79 (16) | C14—C15—C16—N11 | −0.9 (3) |
C31—C3—C4—C41 | −2.5 (3) | C5—C4—C41—O41 | −178.60 (17) |
N2—N1—C5—N5 | 179.16 (14) | C3—C4—C41—O41 | 5.9 (3) |
C12—N1—C5—N5 | −2.3 (3) | N1—C5—N5—C51 | −166.12 (15) |
N2—N1—C5—C4 | 0.01 (18) | C4—C5—N5—C51 | 12.7 (3) |
C12—N1—C5—C4 | 178.60 (15) | C5—N5—C51—C56 | 143.57 (16) |
C41—C4—C5—N5 | 5.1 (3) | C5—N5—C51—C52 | −94.62 (19) |
C3—C4—C5—N5 | −178.60 (18) | N5—C51—C52—C53 | −179.43 (14) |
C41—C4—C5—N1 | −175.88 (16) | C56—C51—C52—C53 | −58.63 (18) |
C3—C4—C5—N1 | 0.39 (17) | C51—C52—C53—C54 | 58.3 (2) |
C16—N11—C12—C13 | 0.7 (2) | C52—C53—C54—C55 | −55.7 (2) |
C16—N11—C12—N1 | −178.70 (14) | C53—C54—C55—C56 | 53.4 (2) |
C5—N1—C12—N11 | 0.2 (3) | N5—C51—C56—C55 | −179.97 (14) |
N2—N1—C12—N11 | 178.76 (13) | C52—C51—C56—C55 | 56.99 (19) |
C5—N1—C12—C13 | −179.17 (16) | C54—C55—C56—C51 | −54.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N11 | 0.88 (2) | 1.958 (19) | 2.696 (2) | 140.4 (16) |
C16—H16···O41i | 0.95 | 2.43 | 3.441 (2) | 168 |
C51—H51···O41ii | 1.00 | 2.57 | 3.477 (2) | 151 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, −y+3/2, −z+1. |
C17H21N3O | Z = 4 |
Mr = 283.37 | F(000) = 608 |
Triclinic, P1 | Dx = 1.217 Mg m−3 |
a = 7.3348 (3) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 7.3614 (10) Å | Cell parameters from 5553 reflections |
c = 29.2335 (6) Å | θ = 3.0–69.9° |
α = 91.243 (3)° | µ = 0.61 mm−1 |
β = 92.678 (10)° | T = 294 K |
γ = 101.004 (4)° | Needle, pale yellow |
V = 1547.0 (2) Å3 | 0.24 × 0.07 × 0.05 mm |
Agilent SuperNova Dual diffractometer with Cu at zero and Atlas detector | 5553 independent reflections |
Radiation source: fine-focus sealed tube | 4785 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 5.3072 pixels mm-1 | θmax = 68.1°, θmin = 3.0° |
ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −8→8 |
Tmin = 0.868, Tmax = 0.970 | l = −35→35 |
48525 measured reflections |
Refinement on F2 | 17 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.0671P)2 + 0.3343P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
5553 reflections | Δρmax = 0.17 e Å−3 |
403 parameters | Δρmin = −0.19 e Å−3 |
C17H21N3O | γ = 101.004 (4)° |
Mr = 283.37 | V = 1547.0 (2) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.3348 (3) Å | Cu Kα radiation |
b = 7.3614 (10) Å | µ = 0.61 mm−1 |
c = 29.2335 (6) Å | T = 294 K |
α = 91.243 (3)° | 0.24 × 0.07 × 0.05 mm |
β = 92.678 (10)° |
Agilent SuperNova Dual diffractometer with Cu at zero and Atlas detector | 5553 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 4785 reflections with I > 2σ(I) |
Tmin = 0.868, Tmax = 0.970 | Rint = 0.051 |
48525 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 17 restraints |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.17 e Å−3 |
5553 reflections | Δρmin = −0.19 e Å−3 |
403 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) | |
N11 | 0.85583 (18) | 0.7725 (2) | 0.41579 (4) | 0.0491 (3) | |
N12 | 1.04864 (18) | 0.8406 (2) | 0.42198 (5) | 0.0528 (3) | |
C13 | 1.0894 (2) | 0.8147 (2) | 0.46486 (5) | 0.0475 (4) | |
C14 | 0.9308 (2) | 0.7291 (2) | 0.48826 (5) | 0.0441 (3) | |
C15 | 0.7777 (2) | 0.7001 (2) | 0.45505 (5) | 0.0439 (3) | |
O15 | 0.61219 (16) | 0.62744 (18) | 0.45914 (4) | 0.0566 (3) | |
C111 | 0.7668 (2) | 0.7933 (2) | 0.37306 (5) | 0.0476 (4) | |
C112 | 0.5874 (3) | 0.8250 (2) | 0.37051 (6) | 0.0553 (4) | |
H112 | 0.5244 | 0.8336 | 0.3971 | 0.066* | |
C113 | 0.5018 (3) | 0.8439 (3) | 0.32822 (7) | 0.0658 (5) | |
H113 | 0.3800 | 0.8631 | 0.3265 | 0.079* | |
C114 | 0.5939 (3) | 0.8347 (3) | 0.28899 (7) | 0.0772 (6) | |
H114 | 0.5357 | 0.8480 | 0.2606 | 0.093* | |
C115 | 0.7725 (3) | 0.8056 (4) | 0.29187 (7) | 0.0833 (7) | |
H115 | 0.8358 | 0.8001 | 0.2652 | 0.100* | |
C116 | 0.8604 (3) | 0.7844 (3) | 0.33334 (6) | 0.0666 (5) | |
H116 | 0.9819 | 0.7642 | 0.3347 | 0.080* | |
C131 | 1.2824 (2) | 0.8751 (3) | 0.48463 (6) | 0.0626 (5) | |
H13A | 1.3536 | 0.9565 | 0.4640 | 0.094* | |
H13B | 1.3384 | 0.7688 | 0.4892 | 0.094* | |
H13C | 1.2798 | 0.9391 | 0.5135 | 0.094* | |
C16 | 0.9184 (2) | 0.6963 (2) | 0.53432 (5) | 0.0472 (4) | 0.68 (3) |
H16 | 1.0268 | 0.7293 | 0.5529 | 0.057* | 0.68 (3) |
N17 | 0.7672 (2) | 0.62286 (19) | 0.55411 (4) | 0.0509 (3) | 0.68 (3) |
H17 | 0.6708 | 0.5829 | 0.5362 | 0.061* | 0.68 (3) |
C171 | 0.7421 (8) | 0.6004 (8) | 0.60308 (8) | 0.0555 (5) | 0.68 (3) |
H171 | 0.6978 | 0.4684 | 0.6080 | 0.067* | 0.68 (3) |
C172 | 0.5909 (13) | 0.7031 (12) | 0.6172 (2) | 0.0629 (12) | 0.68 (3) |
H17A | 0.6293 | 0.8340 | 0.6117 | 0.075* | 0.68 (3) |
H17B | 0.4774 | 0.6571 | 0.5988 | 0.075* | 0.68 (3) |
C173 | 0.5536 (19) | 0.6774 (13) | 0.6677 (2) | 0.0788 (18) | 0.68 (3) |
H17C | 0.4640 | 0.7514 | 0.6765 | 0.095* | 0.68 (3) |
H17D | 0.5008 | 0.5486 | 0.6726 | 0.095* | 0.68 (3) |
C174 | 0.731 (2) | 0.7345 (14) | 0.69727 (18) | 0.089 (2) | 0.68 (3) |
H17E | 0.7056 | 0.7086 | 0.7290 | 0.106* | 0.68 (3) |
H17F | 0.7755 | 0.8668 | 0.6952 | 0.106* | 0.68 (3) |
C175 | 0.8801 (18) | 0.6324 (18) | 0.68246 (15) | 0.0908 (17) | 0.68 (3) |
H17G | 0.8403 | 0.5012 | 0.6873 | 0.109* | 0.68 (3) |
H17H | 0.9934 | 0.6757 | 0.7012 | 0.109* | 0.68 (3) |
C176 | 0.9202 (11) | 0.6618 (17) | 0.63217 (16) | 0.0668 (12) | 0.68 (3) |
H17I | 0.9696 | 0.7916 | 0.6275 | 0.080* | 0.68 (3) |
H17J | 1.0121 | 0.5907 | 0.6233 | 0.080* | 0.68 (3) |
C18 | 0.9184 (2) | 0.6963 (2) | 0.53432 (5) | 0.0472 (4) | 0.32 (3) |
H18X | 1.0268 | 0.7293 | 0.5529 | 0.057* | 0.32 (3) |
N18 | 0.7672 (2) | 0.62286 (19) | 0.55411 (4) | 0.0509 (3) | 0.32 (3) |
H18 | 0.6682 | 0.5847 | 0.5370 | 0.061* | 0.32 (3) |
C181 | 0.7549 (14) | 0.6010 (17) | 0.60380 (14) | 0.0555 (5) | 0.32 (3) |
H181 | 0.6953 | 0.4727 | 0.6089 | 0.067* | 0.32 (3) |
C182 | 0.632 (2) | 0.727 (3) | 0.6226 (3) | 0.0629 (12) | 0.32 (3) |
H18A | 0.5106 | 0.6990 | 0.6065 | 0.075* | 0.32 (3) |
H18B | 0.6866 | 0.8548 | 0.6174 | 0.075* | 0.32 (3) |
C183 | 0.609 (2) | 0.700 (3) | 0.6738 (4) | 0.0788 (18) | 0.32 (3) |
H18C | 0.5359 | 0.7863 | 0.6853 | 0.095* | 0.32 (3) |
H18D | 0.5428 | 0.5756 | 0.6787 | 0.095* | 0.32 (3) |
C184 | 0.796 (3) | 0.732 (3) | 0.6997 (3) | 0.089 (2) | 0.32 (3) |
H18E | 0.7791 | 0.7067 | 0.7317 | 0.106* | 0.32 (3) |
H18F | 0.8568 | 0.8608 | 0.6976 | 0.106* | 0.32 (3) |
C185 | 0.919 (3) | 0.608 (4) | 0.6803 (3) | 0.0908 (17) | 0.32 (3) |
H18G | 0.8635 | 0.4801 | 0.6850 | 0.109* | 0.32 (3) |
H18H | 1.0396 | 0.6348 | 0.6966 | 0.109* | 0.32 (3) |
C186 | 0.9435 (17) | 0.637 (4) | 0.6293 (3) | 0.0668 (12) | 0.32 (3) |
H18I | 1.0068 | 0.7631 | 0.6245 | 0.080* | 0.32 (3) |
H18J | 1.0189 | 0.5535 | 0.6176 | 0.080* | 0.32 (3) |
N21 | 0.2331 (2) | 0.63012 (18) | 0.08195 (4) | 0.0491 (3) | |
N22 | 0.1660 (2) | 0.43879 (18) | 0.07478 (5) | 0.0533 (4) | |
C23 | 0.1905 (2) | 0.4051 (2) | 0.03193 (5) | 0.0478 (4) | |
C24 | 0.2739 (2) | 0.5671 (2) | 0.00926 (5) | 0.0443 (4) | |
C25 | 0.3038 (2) | 0.7147 (2) | 0.04306 (5) | 0.0439 (3) | |
O25 | 0.37499 (18) | 0.88094 (15) | 0.03984 (4) | 0.0577 (3) | |
C211 | 0.2112 (2) | 0.7113 (2) | 0.12484 (5) | 0.0486 (4) | |
C212 | 0.1853 (2) | 0.8922 (3) | 0.12845 (6) | 0.0582 (4) | |
H212 | 0.1815 | 0.9619 | 0.1024 | 0.070* | |
C213 | 0.1650 (3) | 0.9689 (3) | 0.17104 (7) | 0.0723 (6) | |
H213 | 0.1501 | 1.0913 | 0.1736 | 0.087* | |
C214 | 0.1666 (3) | 0.8663 (4) | 0.20937 (7) | 0.0827 (7) | |
H214 | 0.1532 | 0.9186 | 0.2380 | 0.099* | |
C215 | 0.1878 (3) | 0.6869 (4) | 0.20548 (7) | 0.0838 (7) | |
H215 | 0.1863 | 0.6167 | 0.2316 | 0.101* | |
C216 | 0.2114 (3) | 0.6073 (3) | 0.16355 (6) | 0.0656 (5) | |
H216 | 0.2273 | 0.4851 | 0.1614 | 0.079* | |
C231 | 0.1310 (3) | 0.2152 (2) | 0.01157 (7) | 0.0656 (5) | |
H23A | 0.0553 | 0.1392 | 0.0324 | 0.098* | |
H23B | 0.2386 | 0.1635 | 0.0058 | 0.098* | |
H23C | 0.0605 | 0.2203 | −0.0167 | 0.098* | |
C26 | 0.3037 (2) | 0.5852 (2) | −0.03669 (5) | 0.0469 (4) | |
H26 | 0.2699 | 0.4793 | −0.0554 | 0.056* | |
N27 | 0.3757 (2) | 0.7387 (2) | −0.05621 (4) | 0.0502 (3) | |
H27 | 0.414 (3) | 0.844 (3) | −0.0393 (6) | 0.060* | |
C271 | 0.3937 (2) | 0.7644 (3) | −0.10545 (5) | 0.0537 (4) | |
H271 | 0.5249 | 0.8137 | −0.1103 | 0.064* | |
C272 | 0.2827 (3) | 0.9097 (3) | −0.12060 (6) | 0.0658 (5) | |
H27A | 0.3256 | 1.0234 | −0.1026 | 0.079* | |
H27B | 0.1522 | 0.8664 | −0.1153 | 0.079* | |
C273 | 0.3050 (3) | 0.9479 (4) | −0.17133 (7) | 0.0789 (6) | |
H27G | 0.2271 | 1.0345 | −0.1808 | 0.095* | |
H27H | 0.4332 | 1.0042 | −0.1760 | 0.095* | |
C274 | 0.2522 (4) | 0.7735 (4) | −0.20009 (7) | 0.0914 (8) | |
H27E | 0.2759 | 0.8008 | −0.2318 | 0.110* | |
H27F | 0.1202 | 0.7252 | −0.1983 | 0.110* | |
C275 | 0.3611 (4) | 0.6279 (4) | −0.18447 (7) | 0.0942 (8) | |
H27I | 0.4919 | 0.6708 | −0.1894 | 0.113* | |
H27J | 0.3187 | 0.5147 | −0.2027 | 0.113* | |
C276 | 0.3374 (3) | 0.5870 (3) | −0.13382 (6) | 0.0702 (5) | |
H27C | 0.2087 | 0.5324 | −0.1291 | 0.084* | |
H27D | 0.4141 | 0.4993 | −0.1244 | 0.084* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N11 | 0.0423 (7) | 0.0615 (9) | 0.0402 (7) | 0.0006 (6) | 0.0047 (5) | 0.0052 (6) |
N12 | 0.0425 (7) | 0.0630 (9) | 0.0500 (8) | 0.0014 (6) | 0.0076 (6) | 0.0013 (6) |
C13 | 0.0439 (8) | 0.0498 (9) | 0.0488 (9) | 0.0090 (7) | 0.0040 (7) | −0.0036 (7) |
C14 | 0.0459 (8) | 0.0453 (8) | 0.0417 (8) | 0.0096 (7) | 0.0038 (6) | 0.0000 (6) |
C15 | 0.0446 (9) | 0.0461 (9) | 0.0399 (8) | 0.0051 (7) | 0.0069 (6) | 0.0019 (6) |
O15 | 0.0468 (7) | 0.0705 (8) | 0.0477 (6) | −0.0021 (6) | 0.0059 (5) | 0.0088 (5) |
C111 | 0.0517 (9) | 0.0472 (9) | 0.0412 (8) | 0.0023 (7) | 0.0039 (7) | 0.0055 (6) |
C112 | 0.0587 (10) | 0.0542 (10) | 0.0541 (10) | 0.0117 (8) | 0.0063 (8) | 0.0066 (8) |
C113 | 0.0623 (11) | 0.0625 (12) | 0.0716 (12) | 0.0095 (9) | −0.0064 (9) | 0.0188 (9) |
C114 | 0.0804 (15) | 0.0885 (15) | 0.0545 (11) | −0.0039 (12) | −0.0094 (10) | 0.0260 (10) |
C115 | 0.0789 (15) | 0.121 (2) | 0.0436 (10) | 0.0003 (13) | 0.0123 (9) | 0.0162 (11) |
C116 | 0.0573 (11) | 0.0948 (15) | 0.0460 (9) | 0.0077 (10) | 0.0103 (8) | 0.0084 (9) |
C131 | 0.0454 (9) | 0.0774 (13) | 0.0632 (11) | 0.0084 (9) | 0.0008 (8) | −0.0050 (9) |
C16 | 0.0509 (9) | 0.0458 (9) | 0.0440 (8) | 0.0086 (7) | −0.0013 (7) | −0.0012 (7) |
N17 | 0.0557 (8) | 0.0540 (8) | 0.0395 (7) | 0.0023 (6) | 0.0009 (6) | −0.0004 (6) |
C171 | 0.0772 (14) | 0.0455 (9) | 0.0407 (8) | 0.0024 (9) | 0.0082 (8) | 0.0025 (7) |
C172 | 0.075 (3) | 0.057 (2) | 0.0525 (14) | 0.003 (2) | 0.0107 (16) | −0.0052 (13) |
C173 | 0.118 (5) | 0.053 (2) | 0.0627 (19) | 0.002 (3) | 0.033 (3) | −0.0058 (15) |
C174 | 0.147 (8) | 0.0747 (16) | 0.0416 (12) | 0.013 (4) | 0.013 (2) | −0.0036 (12) |
C175 | 0.135 (5) | 0.098 (4) | 0.0416 (11) | 0.030 (3) | −0.0025 (17) | 0.0046 (14) |
C176 | 0.086 (2) | 0.071 (3) | 0.0420 (11) | 0.0137 (16) | −0.0041 (11) | 0.0018 (12) |
C18 | 0.0509 (9) | 0.0458 (9) | 0.0440 (8) | 0.0086 (7) | −0.0013 (7) | −0.0012 (7) |
N18 | 0.0557 (8) | 0.0540 (8) | 0.0395 (7) | 0.0023 (6) | 0.0009 (6) | −0.0004 (6) |
C181 | 0.0772 (14) | 0.0455 (9) | 0.0407 (8) | 0.0024 (9) | 0.0082 (8) | 0.0025 (7) |
C182 | 0.075 (3) | 0.057 (2) | 0.0525 (14) | 0.003 (2) | 0.0107 (16) | −0.0052 (13) |
C183 | 0.118 (5) | 0.053 (2) | 0.0627 (19) | 0.002 (3) | 0.033 (3) | −0.0058 (15) |
C184 | 0.147 (8) | 0.0747 (16) | 0.0416 (12) | 0.013 (4) | 0.013 (2) | −0.0036 (12) |
C185 | 0.135 (5) | 0.098 (4) | 0.0416 (11) | 0.030 (3) | −0.0025 (17) | 0.0046 (14) |
C186 | 0.086 (2) | 0.071 (3) | 0.0420 (11) | 0.0137 (16) | −0.0041 (11) | 0.0018 (12) |
N21 | 0.0635 (9) | 0.0408 (7) | 0.0389 (7) | −0.0008 (6) | 0.0035 (6) | 0.0043 (5) |
N22 | 0.0665 (9) | 0.0405 (7) | 0.0483 (8) | −0.0013 (6) | −0.0011 (6) | 0.0087 (6) |
C23 | 0.0530 (9) | 0.0410 (8) | 0.0481 (9) | 0.0072 (7) | −0.0051 (7) | 0.0044 (6) |
C24 | 0.0480 (8) | 0.0438 (8) | 0.0410 (8) | 0.0087 (7) | −0.0011 (6) | 0.0037 (6) |
C25 | 0.0482 (8) | 0.0422 (9) | 0.0397 (8) | 0.0048 (7) | −0.0004 (6) | 0.0060 (6) |
O25 | 0.0746 (8) | 0.0428 (7) | 0.0504 (6) | −0.0031 (6) | 0.0062 (6) | 0.0055 (5) |
C211 | 0.0452 (8) | 0.0571 (10) | 0.0394 (8) | −0.0005 (7) | 0.0020 (6) | 0.0026 (7) |
C212 | 0.0557 (10) | 0.0607 (11) | 0.0570 (10) | 0.0076 (8) | 0.0055 (8) | −0.0017 (8) |
C213 | 0.0583 (11) | 0.0790 (14) | 0.0772 (14) | 0.0068 (10) | 0.0134 (10) | −0.0199 (11) |
C214 | 0.0684 (13) | 0.114 (2) | 0.0565 (12) | −0.0068 (13) | 0.0161 (10) | −0.0232 (12) |
C215 | 0.0926 (16) | 0.1088 (19) | 0.0406 (10) | −0.0056 (14) | 0.0061 (10) | 0.0077 (11) |
C216 | 0.0777 (13) | 0.0699 (12) | 0.0451 (9) | 0.0027 (10) | 0.0038 (8) | 0.0111 (8) |
C231 | 0.0838 (14) | 0.0426 (10) | 0.0668 (11) | 0.0062 (9) | −0.0079 (10) | 0.0005 (8) |
C26 | 0.0485 (9) | 0.0487 (9) | 0.0427 (8) | 0.0083 (7) | −0.0017 (6) | −0.0007 (7) |
N27 | 0.0567 (8) | 0.0510 (8) | 0.0391 (7) | 0.0017 (7) | −0.0005 (6) | 0.0018 (6) |
C271 | 0.0499 (9) | 0.0684 (11) | 0.0395 (8) | 0.0024 (8) | 0.0024 (7) | 0.0074 (7) |
C272 | 0.0671 (12) | 0.0767 (13) | 0.0528 (10) | 0.0109 (10) | 0.0016 (8) | 0.0160 (9) |
C273 | 0.0638 (12) | 0.1108 (18) | 0.0594 (12) | 0.0077 (12) | −0.0022 (9) | 0.0321 (12) |
C274 | 0.0844 (16) | 0.138 (2) | 0.0441 (10) | 0.0010 (15) | −0.0050 (10) | 0.0190 (12) |
C275 | 0.116 (2) | 0.116 (2) | 0.0457 (11) | 0.0115 (16) | 0.0094 (11) | −0.0067 (11) |
C276 | 0.0837 (14) | 0.0795 (14) | 0.0445 (9) | 0.0092 (11) | 0.0036 (9) | −0.0034 (9) |
N11—N12 | 1.4091 (18) | C184—C185 | 1.514 (6) |
N12—C13 | 1.302 (2) | C184—H18E | 0.9700 |
C13—C14 | 1.425 (2) | C184—H18F | 0.9700 |
C14—C15 | 1.431 (2) | C185—C186 | 1.525 (4) |
C15—N11 | 1.3788 (19) | C185—H18G | 0.9700 |
C14—C16 | 1.377 (2) | C185—H18H | 0.9700 |
C16—N17 | 1.305 (2) | C186—H18I | 0.9700 |
C15—O15 | 1.2419 (19) | C186—H18J | 0.9700 |
N11—C111 | 1.407 (2) | N21—N22 | 1.4080 (18) |
C13—C131 | 1.486 (2) | N22—C23 | 1.299 (2) |
C111—C112 | 1.379 (2) | C23—C24 | 1.424 (2) |
C111—C116 | 1.383 (2) | C24—C25 | 1.431 (2) |
C112—C113 | 1.382 (2) | C25—N21 | 1.3825 (19) |
C112—H112 | 0.9300 | C24—C26 | 1.376 (2) |
C113—C114 | 1.365 (3) | C26—N27 | 1.307 (2) |
C113—H113 | 0.9300 | C25—O25 | 1.2431 (19) |
C114—C115 | 1.366 (3) | N21—C211 | 1.407 (2) |
C114—H114 | 0.9300 | C23—C231 | 1.485 (2) |
C115—C116 | 1.372 (3) | C211—C216 | 1.380 (2) |
C115—H115 | 0.9300 | C211—C212 | 1.383 (2) |
C116—H116 | 0.9300 | C212—C213 | 1.382 (3) |
C131—H13A | 0.9600 | C212—H212 | 0.9300 |
C131—H13B | 0.9600 | C213—C214 | 1.366 (3) |
C131—H13C | 0.9600 | C213—H213 | 0.9300 |
C16—H16 | 0.9300 | C214—C215 | 1.362 (4) |
N17—C171 | 1.461 (2) | C214—H214 | 0.9300 |
N17—H17 | 0.8600 | C215—C216 | 1.380 (3) |
C171—C176 | 1.513 (3) | C215—H215 | 0.9300 |
C171—C172 | 1.524 (3) | C216—H216 | 0.9300 |
C171—H171 | 0.9800 | C231—H23A | 0.9600 |
C172—C173 | 1.523 (3) | C231—H23B | 0.9600 |
C172—H17A | 0.9700 | C231—H23C | 0.9600 |
C172—H17B | 0.9700 | C26—H26 | 0.9300 |
C173—C174 | 1.513 (5) | N27—C271 | 1.465 (2) |
C173—H17C | 0.9700 | N27—H27 | 0.90 (2) |
C173—H17D | 0.9700 | C271—C276 | 1.510 (3) |
C174—C175 | 1.514 (5) | C271—C272 | 1.524 (3) |
C174—H17E | 0.9700 | C271—H271 | 0.9800 |
C174—H17F | 0.9700 | C272—C273 | 1.526 (3) |
C175—C176 | 1.524 (3) | C272—H27A | 0.9700 |
C175—H17G | 0.9700 | C272—H27B | 0.9700 |
C175—H17H | 0.9700 | C273—C274 | 1.496 (4) |
C176—H17I | 0.9700 | C273—H27G | 0.9700 |
C176—H17J | 0.9700 | C273—H27H | 0.9700 |
C181—C186 | 1.514 (4) | C274—C275 | 1.520 (4) |
C181—C182 | 1.523 (5) | C274—H27E | 0.9700 |
C181—H181 | 0.9800 | C274—H27F | 0.9700 |
C182—C183 | 1.524 (5) | C275—C276 | 1.528 (3) |
C182—H18A | 0.9700 | C275—H27I | 0.9700 |
C182—H18B | 0.9700 | C275—H27J | 0.9700 |
C183—C184 | 1.513 (6) | C276—H27C | 0.9700 |
C183—H18C | 0.9700 | C276—H27D | 0.9700 |
C183—H18D | 0.9700 | ||
C15—N11—C111 | 128.49 (13) | C185—C184—H18E | 109.5 |
C15—N11—N12 | 112.79 (12) | C183—C184—H18F | 109.5 |
C111—N11—N12 | 118.64 (13) | C185—C184—H18F | 109.5 |
C13—N12—N11 | 105.14 (13) | H18E—C184—H18F | 108.1 |
N12—C13—C14 | 112.21 (14) | C184—C185—C186 | 111.6 (6) |
N12—C13—C131 | 120.74 (15) | C184—C185—H18G | 109.3 |
C14—C13—C131 | 127.03 (15) | C186—C185—H18G | 109.3 |
C16—C14—C13 | 128.12 (15) | C184—C185—H18H | 109.3 |
C16—C14—C15 | 125.41 (15) | C186—C185—H18H | 109.3 |
C13—C14—C15 | 106.17 (13) | H18G—C185—H18H | 108.0 |
O15—C15—N11 | 126.52 (14) | C181—C186—C185 | 109.6 (5) |
O15—C15—C14 | 129.81 (14) | C181—C186—H18I | 109.8 |
N11—C15—C14 | 103.66 (13) | C185—C186—H18I | 109.8 |
C112—C111—C116 | 119.61 (16) | C181—C186—H18J | 109.8 |
C112—C111—N11 | 120.43 (15) | C185—C186—H18J | 109.8 |
C116—C111—N11 | 119.95 (16) | H18I—C186—H18J | 108.2 |
C111—C112—C113 | 119.65 (17) | C25—N21—C211 | 128.78 (13) |
C111—C112—H112 | 120.2 | C25—N21—N22 | 112.62 (12) |
C113—C112—H112 | 120.2 | C211—N21—N22 | 118.48 (13) |
C114—C113—C112 | 120.76 (19) | C23—N22—N21 | 105.28 (12) |
C114—C113—H113 | 119.6 | N22—C23—C24 | 112.31 (14) |
C112—C113—H113 | 119.6 | N22—C23—C231 | 120.50 (15) |
C113—C114—C115 | 119.20 (18) | C24—C23—C231 | 127.18 (15) |
C113—C114—H114 | 120.4 | C26—C24—C23 | 127.73 (15) |
C115—C114—H114 | 120.4 | C26—C24—C25 | 125.83 (15) |
C114—C115—C116 | 121.3 (2) | C23—C24—C25 | 106.16 (13) |
C114—C115—H115 | 119.3 | O25—C25—N21 | 126.31 (14) |
C116—C115—H115 | 119.3 | O25—C25—C24 | 130.08 (14) |
C115—C116—C111 | 119.45 (19) | N21—C25—C24 | 103.61 (13) |
C115—C116—H116 | 120.3 | C216—C211—C212 | 119.83 (16) |
C111—C116—H116 | 120.3 | C216—C211—N21 | 119.36 (16) |
C13—C131—H13A | 109.5 | C212—C211—N21 | 120.79 (15) |
C13—C131—H13B | 109.5 | C213—C212—C211 | 119.60 (19) |
H13A—C131—H13B | 109.5 | C213—C212—H212 | 120.2 |
C13—C131—H13C | 109.5 | C211—C212—H212 | 120.2 |
H13A—C131—H13C | 109.5 | C214—C213—C212 | 120.5 (2) |
H13B—C131—H13C | 109.5 | C214—C213—H213 | 119.7 |
N17—C16—C14 | 125.39 (15) | C212—C213—H213 | 119.7 |
N17—C16—H16 | 117.3 | C215—C214—C213 | 119.63 (19) |
C14—C16—H16 | 117.3 | C215—C214—H214 | 120.2 |
C16—N17—C171 | 127.7 (3) | C213—C214—H214 | 120.2 |
C16—N17—H17 | 116.1 | C214—C215—C216 | 121.2 (2) |
C171—N17—H17 | 116.1 | C214—C215—H215 | 119.4 |
N17—C171—C176 | 113.1 (3) | C216—C215—H215 | 119.4 |
N17—C171—C172 | 108.8 (3) | C215—C216—C211 | 119.2 (2) |
C176—C171—C172 | 111.6 (3) | C215—C216—H216 | 120.4 |
N17—C171—H171 | 107.7 | C211—C216—H216 | 120.4 |
C176—C171—H171 | 107.7 | C23—C231—H23A | 109.5 |
C172—C171—H171 | 107.7 | C23—C231—H23B | 109.5 |
C173—C172—C171 | 111.0 (3) | H23A—C231—H23B | 109.5 |
C173—C172—H17A | 109.4 | C23—C231—H23C | 109.5 |
C171—C172—H17A | 109.4 | H23A—C231—H23C | 109.5 |
C173—C172—H17B | 109.4 | H23B—C231—H23C | 109.5 |
C171—C172—H17B | 109.4 | N27—C26—C24 | 125.53 (15) |
H17A—C172—H17B | 108.0 | N27—C26—H26 | 117.2 |
C174—C173—C172 | 110.8 (3) | C24—C26—H26 | 117.2 |
C174—C173—H17C | 109.5 | C26—N27—C271 | 126.32 (15) |
C172—C173—H17C | 109.5 | C26—N27—H27 | 120.4 (12) |
C174—C173—H17D | 109.5 | C271—N27—H27 | 113.2 (12) |
C172—C173—H17D | 109.5 | N27—C271—C276 | 113.45 (15) |
H17C—C173—H17D | 108.1 | N27—C271—C272 | 108.77 (14) |
C173—C174—C175 | 111.3 (3) | C276—C271—C272 | 111.56 (15) |
C173—C174—H17E | 109.4 | N27—C271—H271 | 107.6 |
C175—C174—H17E | 109.4 | C276—C271—H271 | 107.6 |
C173—C174—H17F | 109.4 | C272—C271—H271 | 107.6 |
C175—C174—H17F | 109.4 | C271—C272—C273 | 110.61 (17) |
H17E—C174—H17F | 108.0 | C271—C272—H27A | 109.5 |
C174—C175—C176 | 111.7 (3) | C273—C272—H27A | 109.5 |
C174—C175—H17G | 109.3 | C271—C272—H27B | 109.5 |
C176—C175—H17G | 109.3 | C273—C272—H27B | 109.5 |
C174—C175—H17H | 109.3 | H27A—C272—H27B | 108.1 |
C176—C175—H17H | 109.3 | C274—C273—C272 | 111.25 (18) |
H17G—C175—H17H | 108.0 | C274—C273—H27G | 109.4 |
C171—C176—C175 | 109.2 (3) | C272—C273—H27G | 109.4 |
C171—C176—H17I | 109.8 | C274—C273—H27H | 109.4 |
C175—C176—H17I | 109.8 | C272—C273—H27H | 109.4 |
C171—C176—H17J | 109.8 | H27G—C273—H27H | 108.0 |
C175—C176—H17J | 109.8 | C273—C274—C275 | 111.48 (19) |
H17I—C176—H17J | 108.3 | C273—C274—H27E | 109.3 |
C186—C181—C182 | 110.7 (6) | C275—C274—H27E | 109.3 |
C186—C181—H181 | 107.8 | C273—C274—H27F | 109.3 |
C182—C181—H181 | 107.8 | C275—C274—H27F | 109.3 |
C181—C182—C183 | 110.9 (5) | H27E—C274—H27F | 108.0 |
C181—C182—H18A | 109.5 | C274—C275—C276 | 111.7 (2) |
C183—C182—H18A | 109.5 | C274—C275—H27I | 109.3 |
C181—C182—H18B | 109.5 | C276—C275—H27I | 109.3 |
C183—C182—H18B | 109.5 | C274—C275—H27J | 109.3 |
H18A—C182—H18B | 108.0 | C276—C275—H27J | 109.3 |
C184—C183—C182 | 110.9 (6) | H27I—C275—H27J | 108.0 |
C184—C183—H18C | 109.5 | C271—C276—C275 | 109.54 (18) |
C182—C183—H18C | 109.5 | C271—C276—H27C | 109.8 |
C184—C183—H18D | 109.5 | C275—C276—H27C | 109.8 |
C182—C183—H18D | 109.5 | C271—C276—H27D | 109.8 |
H18C—C183—H18D | 108.1 | C275—C276—H27D | 109.8 |
C183—C184—C185 | 110.7 (6) | H27C—C276—H27D | 108.2 |
C183—C184—H18E | 109.5 | ||
C15—N11—N12—C13 | −1.39 (18) | C183—C184—C185—C186 | 56.7 (12) |
C111—N11—N12—C13 | 175.60 (14) | C182—C181—C186—C185 | 57.6 (11) |
N11—N12—C13—C14 | 0.61 (18) | C184—C185—C186—C181 | −57.6 (12) |
N11—N12—C13—C131 | −178.27 (15) | C25—N21—N22—C23 | −1.38 (18) |
N12—C13—C14—C16 | −173.60 (15) | C211—N21—N22—C23 | 174.97 (14) |
C131—C13—C14—C16 | 5.2 (3) | N21—N22—C23—C24 | 0.44 (18) |
N12—C13—C14—C15 | 0.30 (19) | N21—N22—C23—C231 | −178.57 (15) |
C131—C13—C14—C15 | 179.09 (16) | N22—C23—C24—C26 | −173.52 (15) |
C111—N11—C15—O15 | 5.0 (3) | C231—C23—C24—C26 | 5.4 (3) |
N12—N11—C15—O15 | −178.35 (15) | N22—C23—C24—C25 | 0.57 (19) |
C111—N11—C15—C14 | −175.09 (15) | C231—C23—C24—C25 | 179.50 (16) |
N12—N11—C15—C14 | 1.53 (17) | C211—N21—C25—O25 | 5.6 (3) |
C16—C14—C15—O15 | −7.1 (3) | N22—N21—C25—O25 | −178.55 (15) |
C13—C14—C15—O15 | 178.80 (16) | C211—N21—C25—C24 | −174.19 (15) |
C16—C14—C15—N11 | 173.03 (15) | N22—N21—C25—C24 | 1.69 (17) |
C13—C14—C15—N11 | −1.08 (16) | C26—C24—C25—O25 | −6.8 (3) |
C15—N11—C111—C112 | 31.2 (3) | C23—C24—C25—O25 | 178.93 (17) |
N12—N11—C111—C112 | −145.22 (16) | C26—C24—C25—N21 | 172.92 (15) |
C15—N11—C111—C116 | −149.63 (18) | C23—C24—C25—N21 | −1.32 (16) |
N12—N11—C111—C116 | 33.9 (2) | C25—N21—C211—C216 | −153.67 (17) |
C116—C111—C112—C113 | 1.3 (3) | N22—N21—C211—C216 | 30.7 (2) |
N11—C111—C112—C113 | −179.59 (16) | C25—N21—C211—C212 | 27.8 (3) |
C111—C112—C113—C114 | −1.1 (3) | N22—N21—C211—C212 | −147.86 (16) |
C112—C113—C114—C115 | 0.3 (3) | C216—C211—C212—C213 | 1.8 (3) |
C113—C114—C115—C116 | 0.4 (4) | N21—C211—C212—C213 | −179.70 (16) |
C114—C115—C116—C111 | −0.3 (4) | C211—C212—C213—C214 | −1.3 (3) |
C112—C111—C116—C115 | −0.6 (3) | C212—C213—C214—C215 | −0.2 (3) |
N11—C111—C116—C115 | −179.74 (19) | C213—C214—C215—C216 | 1.3 (4) |
C13—C14—C16—N17 | 177.47 (16) | C214—C215—C216—C211 | −0.8 (3) |
C15—C14—C16—N17 | 4.7 (3) | C212—C211—C216—C215 | −0.7 (3) |
C14—C16—N17—C171 | −173.9 (3) | N21—C211—C216—C215 | −179.27 (18) |
C16—N17—C171—C176 | −3.9 (6) | C23—C24—C26—N27 | 177.69 (16) |
C16—N17—C171—C172 | 120.7 (5) | C25—C24—C26—N27 | 4.7 (3) |
N17—C171—C172—C173 | 177.7 (4) | C24—C26—N27—C271 | −174.29 (15) |
C176—C171—C172—C173 | −56.8 (5) | C26—N27—C271—C276 | −5.9 (2) |
C171—C172—C173—C174 | 54.8 (5) | C26—N27—C271—C272 | 118.84 (19) |
C172—C173—C174—C175 | −54.9 (6) | N27—C271—C272—C273 | 177.30 (16) |
C173—C174—C175—C176 | 56.7 (6) | C276—C271—C272—C273 | −56.8 (2) |
N17—C171—C176—C175 | −179.8 (5) | C271—C272—C273—C274 | 55.4 (2) |
C172—C171—C176—C175 | 57.1 (5) | C272—C273—C274—C275 | −55.1 (3) |
C174—C175—C176—C171 | −57.0 (6) | C273—C274—C275—C276 | 55.9 (3) |
C186—C181—C182—C183 | −57.5 (11) | N27—C271—C276—C275 | −179.97 (17) |
C181—C182—C183—C184 | 56.0 (12) | C272—C271—C276—C275 | 56.8 (2) |
C182—C183—C184—C185 | −55.4 (12) | C274—C275—C276—C271 | −56.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N17—H17···O15 | 0.86 | 2.32 | 2.9539 (17) | 131 |
N17—H17···O15i | 0.86 | 2.35 | 3.0331 (19) | 136 |
N27—H27···O25 | 0.90 (2) | 2.361 (18) | 2.9760 (17) | 125.6 (16) |
N27—H27···O25ii | 0.90 (2) | 2.30 (2) | 3.0526 (19) | 140.6 (17) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C16H20N4O | C17H21N3O |
Mr | 284.36 | 283.37 |
Crystal system, space group | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 120 | 294 |
a, b, c (Å) | 21.369 (2), 20.489 (3), 6.7444 (10) | 7.3348 (3), 7.3614 (10), 29.2335 (6) |
α, β, γ (°) | 90, 95.978 (10), 90 | 91.243 (3), 92.678 (10), 101.004 (4) |
V (Å3) | 2936.8 (7) | 1547.0 (2) |
Z | 8 | 4 |
Radiation type | Mo Kα | Cu Kα |
µ (mm−1) | 0.08 | 0.61 |
Crystal size (mm) | 0.32 × 0.24 × 0.21 | 0.24 × 0.07 × 0.05 |
Data collection | ||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Agilent SuperNova Dual diffractometer with Cu at zero and Atlas detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.788, 0.983 | 0.868, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10192, 3367, 2149 | 48525, 5553, 4785 |
Rint | 0.051 | 0.051 |
(sin θ/λ)max (Å−1) | 0.650 | 0.602 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.115, 1.02 | 0.046, 0.139, 1.10 |
No. of reflections | 3367 | 5553 |
No. of parameters | 194 | 403 |
No. of restraints | 0 | 17 |
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) | 0.21, −0.30 | 0.17, −0.19 |
Computer programs: COLLECT (Nonius, 1999), CrysAlis PRO (Agilent, 2012), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).
N1—N2 | 1.4020 (18) | C4—C41 | 1.430 (2) |
N2—C3 | 1.309 (2) | C41—O41 | 1.230 (2) |
C3—C4 | 1.435 (2) | C5—N5 | 1.343 (2) |
C4—C5 | 1.412 (2) | N1—C12 | 1.410 (2) |
C5—N1 | 1.375 (2) | ||
C5—N5—C51 | 125.51 (14) | C51—N5—H5 | 120.5 (12) |
C5—N5—H5 | 112.4 (12) | ||
N2—N1—C12—N11 | 178.76 (13) | C4—C5—N5—C51 | 12.7 (3) |
C3—C4—C41—O41 | 5.9 (3) | C5—N5—C51—C52 | −94.62 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N11 | 0.88 (2) | 1.958 (19) | 2.696 (2) | 140.4 (16) |
C16—H16···O41i | 0.95 | 2.43 | 3.441 (2) | 168 |
C51—H51···O41ii | 1.00 | 2.57 | 3.477 (2) | 151 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, −y+3/2, −z+1. |
N11—N12 | 1.4091 (18) | N21—N22 | 1.4080 (18) |
N12—C13 | 1.302 (2) | N22—C23 | 1.299 (2) |
C13—C14 | 1.425 (2) | C23—C24 | 1.424 (2) |
C14—C15 | 1.431 (2) | C24—C25 | 1.431 (2) |
C15—N11 | 1.3788 (19) | C25—N21 | 1.3825 (19) |
C14—C16 | 1.377 (2) | C24—C26 | 1.376 (2) |
C16—N17 | 1.305 (2) | C26—N27 | 1.307 (2) |
C15—O15 | 1.2419 (19) | C25—O25 | 1.2431 (19) |
C16—N17—C171 | 127.7 (3) | C26—N27—C271 | 126.32 (15) |
C16—N17—H17 | 116.1 | C26—N27—H27 | 120.4 (12) |
C171—N17—H17 | 116.1 | C271—N27—H27 | 113.2 (12) |
N12—N11—C111—C112 | −145.22 (16) | N22—N21—C211—C212 | −147.86 (16) |
C14—C16—N17—C171 | −173.9 (3) | C24—C26—N27—C271 | −174.29 (15) |
C16—N17—C171—C172 | 120.7 (5) | C26—N27—C271—C272 | 118.84 (19) |
N17—C171—C172—C173 | 177.7 (4) | N27—C271—C272—C273 | 177.30 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N17—H17···O15 | 0.86 | 2.32 | 2.9539 (17) | 131 |
N17—H17···O15i | 0.86 | 2.35 | 3.0331 (19) | 136 |
N27—H27···O25 | 0.90 (2) | 2.361 (18) | 2.9760 (17) | 125.6 (16) |
N27—H27···O25ii | 0.90 (2) | 2.30 (2) | 3.0526 (19) | 140.6 (17) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z. |