In the crystal structure of the title compound, C—H⋯O and C—H⋯N hydrogen bonds as well as C—H⋯π(ring) interactions link individual molecules into a three-dimensional network.
Keywords: crystal structure, hydrogen bond, C—H⋯π(ring) interactions, pyrazolopyrimidine, Hirshfeld surface analysis
Abstract
In the title molecule, C19H16N4O, the planar pyrazolopyrimidine moiety is inclined to the attached phenyl rings by 35.42 (4) and 54.51 (6)°. In the crystal, adjacent molecules are linked into chains parallel to [110] and [1
0] by C—H⋯O and C—H⋯N hydrogen bonds. Additional C—H⋯π(ring) interactions lead to the formation of the final three-dimensional network structure. The Hirshfeld surface analysis of the title compound suggests that the most significant contributions to the crystal packing are from H⋯H (48.2%), C⋯H/H⋯C (23.9%) and N⋯H/H⋯N (17.4%) contacts.
Chemical context
Pyrazolo[3,4-d]pyrimidine derivatives represent an important class of compounds because of their potent biological activities and thus find applications as antiproliferative (Tallani et al., 2010 ▸), antibacterial (Rostamizadeh et al., 2013 ▸) or antitumor agents (Tintori et al., 2015 ▸). The present contribution is a continuation of the investigation of pyrazolo[3,4-d]pyrimidine derivatives recently published by us (El Hafi et al., 2017 ▸, 2018a
▸,b
▸). We report herein the synthesis, molecular and crystal structures of the title compound, 3-(4-methoxyphenyl)-1-methyl-4-phenyl-1H-pyrazolo[3,4-d]pyrimidine (Fig. 1 ▸), along with the results of a Hirshfeld surface analysis.
Figure 1.
The title molecule with the labeling scheme and displacement ellipsoids drawn at the 50% probability level.
Structural commentary
The heterocyclic ring system is planar (r.m.s. deviation of the fitted atoms = 0.0194 Å) with a maximum displacement of 0.0329 (10) Å from the mean plane for atom C1. The attached benzene rings (C6–C11 and C13–C18) are inclined to the above plane by 35.42 (4) and 54.51 (6)°, respectively.
Supramolecular features
In the crystal, a combination of C9—H9⋯N2 hydrogen bonds between aromatic hydrogen atoms and one of the pyrimidine N atoms as well as C12—H12B⋯O1 hydrogen bonds between a methyl H atom and the methoxy O atoms of adjacent molecules lead to the formation of chains extending alternately parallel to [110] and [10] (Table 1 ▸ and Fig. 2 ▸). Centrosymmetric dimers with an 
(8) graph-set motif are formed by pairwise C17—H17⋯O1 hydrogen bonds. The chains are linked into layers parallel to (001) by C19—H19C⋯Cg1 interactions, and pairs of layers are joined into thicker slabs by C19—H19B⋯Cg4 interactions (Table 1 ▸ and Figs. 2 ▸–4 ▸
▸).
Table 1. Hydrogen-bond geometry (Å, °).
Cg1 and Cg4 are the centroids of the C3/C4/C5/N4/N3 and C13–C18 rings, respectively.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C9—H9⋯N2i | 0.988 (18) | 2.579 (17) | 3.3995 (19) | 140.3 (14) |
| C12—H12B⋯O1ii | 0.98 (2) | 2.49 (2) | 3.2694 (19) | 136.4 (15) |
| C17—H17⋯O1iii | 0.983 (17) | 2.618 (9) | 3.4973 (17) | 149.3 (14) |
| C19—H19B⋯Cg4iv | 1.02 (2) | 2.74 (2) | 3.5928 (19) | 141.9 (14) |
| C19—H19C⋯Cg1v | 0.995 (19) | 2.947 (19) | 3.9072 (19) | 162.0 (15) |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
; (v) 
.
Figure 2.
Details of the intermolecular interactions in a view along [100]. C—H⋯O and C—H⋯N hydrogen bonds are shown, respectively, as black and light-purple dashed lines while the C—H⋯π(ring) interactions are shown as green dashed lines. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) x + 1, y − 1, z; (iii) x − 1, y + 1, z.]
Figure 3.
Packing of the crystal viewed along [100] with intermolecular interactions depicted as in Fig. 2 ▸.
Figure 4.
Packing of the crystal viewed along [010] with intermolecular interactions depicted as in Fig. 2 ▸.
Database survey
A search of the Cambridge Structural Database (CSD, version 5.40, update November 2018; Groom et al., 2016 ▸) for the 1-methyl-1H-pyrazolo[3,4-d]pyrimidine skeleton yielded seven hits. In all of these structures, the pyrazolo[3,4-d]pyrimidine rings are planar, as in the title compound. In FEWVIP (El Hafi et al., 2018a
▸), centrosymmetric dimers with an (8) graph set motif are formed by pairwise N—H⋯O hydrogen bonds; the dimers are connected into chains parallel to [001], similar to those in the title compound. Neighbouring molecules in FAXFEP (Sheldrick & Bell, 1987a
▸) and in FOGXAA, FOGXEE, FOGXII, JAGROY (Sheldrick & Bell, 1987b
▸) are linked by N—H⋯O hydrogen bonds, whereas in XAXRUM (El Fal et al., 2017 ▸), C—H⋯N hydrogen bonds are responsible for the formation of double chains running parallel to [100].
Hirshfeld surface analysis
CrystalExplorer17 (Turner et al., 2017 ▸) was used to perform the Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ▸) and obtain the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ▸). Fig. 5 ▸ shows dnorm, di, de, shape-index, curvedness and electrostatic potential mapped over the Hirshfeld surface for the title compound while Fig. 6 ▸ illustrates the Hirshfeld surface of the molecule in the crystal, with the evident hydrogen-bonding interactions indicated as intense red spots.
Figure 5.
The Hirshfeld surfaces of the title compound mapped over (a) d norm, (b) d i, (c) d e, (d) shape-index, (e) curvedness and (f) electrostatic potential.
Figure 6.
d norm mapped on Hirshfeld surfaces for visualizing the intermolecular interactions of the title compound.
Fig. 7 ▸ a shows the two-dimensional fingerprint of the sum of the contacts contributing to the Hirshfeld surface represented in normal mode. The fingerprint plots provide information about the percentage contributions of various interatomic contacts in the structure. The blue color refers to the frequency of occurrence of the (d i, d e) pair with the full fingerprint outlined in gray. Individual fingerprint plots (Fig. 7 ▸ b) reveal that the H⋯H contacts clearly give the most significant contribution to the Hirshfeld surface (48.2%). In addition, C⋯H/H⋯C, N⋯H/H⋯N, O⋯H/H⋯O and C⋯N/N⋯C contacts contribute 23.9%, 17.4%, 5.3% and 2.6%, respectively, to the Hirshfeld surface. In particular, the N⋯H/H⋯N and O⋯H/H⋯O contacts indicate the presence of intermolecular C—H⋯N and C—H⋯O interactions, respectively. Much weaker C⋯C (2.2%) and C⋯O/O⋯C (0.5%) contacts also occur.
Figure 7.
Two-dimensional fingerprint plots for the title structure, with a d norm view and relative contribution of the atom pairs to the Hirshfeld surface.
A view of the molecular electrostatic potential, in the range −0.0500 to 0.0500 a.u. using the 6-31G(d,p) basis set (DFT method), for the title compound is shown in Fig. 8 ▸. The donors and acceptors for C—H⋯O and C—H⋯N hydrogen bonds are shown as blue and red areas around the atoms related with positive (hydrogen-bond donors) and negative (hydrogen-bond acceptors) electrostatic potentials, respectively.
Figure 8.
A view of the molecular electrostatic potential of the title compound in the range −0.05 to 0.05 a.u. using the 6–31G(d,p) basis set (DFT method).
Synthesis and crystallization
Under an atmosphere of argon, a mixture of 1-methyl-4-phenyl-1H-pyrazolo[3,4-d]pyrimidine (0.1 g, 0.47 mmol), 4-iodoanisole (0.22 g, 0.95 mmol), Cs2CO3 (0.46g, 1.42 mmol), K3PO4 (0.25 g, 1.18 mmol), 1,10-phenanthroline (0.034 g, 0.19 mmol), and Pd(OAc)2 (0.021 g, 0.094 mmol) in DMA (3 ml) was heated to 438 K for 48 h. After completion of the reaction, the mixture was allowed to cool to room temperature and the solvent was removed under reduced pressure. Water (15 ml) was added, and the resulting aqueous phase was extracted with CH2Cl2 (3 × 15 ml). The combined organic layers were dried with MgSO4 and concentrated under vacuum. The residue was purified by column chromatography on silica gel (EtOAc/petroleum ether). The title compound was recrystallized from ethanol at room temperature, giving colorless crystals (yield: 71%; m.p. 412–414 K).
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All H atoms were located in a difference-Fourier map and were freely refined.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C19H16N4O |
| M r | 316.36 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 150 |
| a, b, c (Å) | 6.5227 (3), 7.8979 (4), 30.7774 (15) |
| β (°) | 95.389 (2) |
| V (Å3) | 1578.51 (13) |
| Z | 4 |
| Radiation type | Cu Kα |
| μ (mm−1) | 0.69 |
| Crystal size (mm) | 0.30 × 0.24 × 0.04 |
| Data collection | |
| Diffractometer | Bruker D8 VENTURE PHOTON 100 CMOS |
| Absorption correction | Multi-scan (SADABS; Krause et al., 2015 ▸) |
| T min, T max | 0.85, 0.98 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 11542, 3069, 2613 |
| R int | 0.035 |
| (sin θ/λ)max (Å−1) | 0.617 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.039, 0.091, 1.06 |
| No. of reflections | 3069 |
| No. of parameters | 282 |
| H-atom treatment | All H-atom parameters refined |
| Δρmax, Δρmin (e Å−3) | 0.19, −0.18 |
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019004894/wm5499sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019004894/wm5499Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989019004894/wm5499Isup3.cml
CCDC reference: 1909062
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Crystal data
| C19H16N4O | F(000) = 664 |
| Mr = 316.36 | Dx = 1.331 Mg m−3 |
| Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
| a = 6.5227 (3) Å | Cell parameters from 8514 reflections |
| b = 7.8979 (4) Å | θ = 2.9–72.2° |
| c = 30.7774 (15) Å | µ = 0.69 mm−1 |
| β = 95.389 (2)° | T = 150 K |
| V = 1578.51 (13) Å3 | Plate, colourless |
| Z = 4 | 0.30 × 0.24 × 0.04 mm |
Data collection
| Bruker D8 VENTURE PHOTON 100 CMOS diffractometer | 3069 independent reflections |
| Radiation source: INCOATEC IµS micro-focus source | 2613 reflections with I > 2σ(I) |
| Mirror monochromator | Rint = 0.035 |
| Detector resolution: 10.4167 pixels mm-1 | θmax = 72.2°, θmin = 5.8° |
| ω scans | h = −7→8 |
| Absorption correction: multi-scan (SADABS; Krause et al., 2015) | k = −9→8 |
| Tmin = 0.85, Tmax = 0.98 | l = −37→33 |
| 11542 measured reflections |
Refinement
| Refinement on F2 | Hydrogen site location: difference Fourier map |
| Least-squares matrix: full | All H-atom parameters refined |
| R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.0337P)2 + 0.5793P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.091 | (Δ/σ)max < 0.001 |
| S = 1.06 | Δρmax = 0.19 e Å−3 |
| 3069 reflections | Δρmin = −0.18 e Å−3 |
| 282 parameters | Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.0035 (3) |
Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
| Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.20599 (16) | 0.66433 (13) | 0.47647 (3) | 0.0355 (3) | |
| N1 | 0.21981 (18) | −0.14300 (15) | 0.29349 (4) | 0.0310 (3) | |
| N2 | 0.53402 (18) | −0.27278 (15) | 0.32443 (4) | 0.0314 (3) | |
| N3 | 0.70112 (17) | −0.11435 (15) | 0.38386 (4) | 0.0302 (3) | |
| N4 | 0.66731 (18) | 0.02986 (15) | 0.40680 (4) | 0.0306 (3) | |
| C1 | 0.2383 (2) | −0.01161 (17) | 0.32134 (4) | 0.0257 (3) | |
| C2 | 0.3656 (2) | −0.26430 (19) | 0.29691 (5) | 0.0338 (3) | |
| H2 | 0.343 (3) | −0.360 (2) | 0.2760 (6) | 0.038 (4)* | |
| C3 | 0.5468 (2) | −0.14182 (18) | 0.35243 (4) | 0.0271 (3) | |
| C4 | 0.4895 (2) | 0.09486 (18) | 0.38968 (4) | 0.0267 (3) | |
| C5 | 0.4044 (2) | −0.00839 (17) | 0.35407 (4) | 0.0249 (3) | |
| C6 | 0.0795 (2) | 0.12152 (17) | 0.31411 (4) | 0.0257 (3) | |
| C7 | 0.1276 (2) | 0.29264 (18) | 0.31985 (5) | 0.0305 (3) | |
| H7 | 0.270 (3) | 0.330 (2) | 0.3290 (5) | 0.034 (4)* | |
| C8 | −0.0249 (3) | 0.4138 (2) | 0.31144 (5) | 0.0366 (4) | |
| H8 | 0.017 (3) | 0.533 (2) | 0.3158 (6) | 0.042 (5)* | |
| C9 | −0.2243 (2) | 0.3662 (2) | 0.29735 (5) | 0.0379 (4) | |
| H9 | −0.331 (3) | 0.454 (2) | 0.2911 (6) | 0.044 (5)* | |
| C10 | −0.2719 (2) | 0.1971 (2) | 0.29048 (5) | 0.0347 (3) | |
| H10 | −0.408 (3) | 0.162 (2) | 0.2792 (6) | 0.051 (5)* | |
| C11 | −0.1211 (2) | 0.07493 (19) | 0.29875 (5) | 0.0287 (3) | |
| H11 | −0.153 (2) | −0.048 (2) | 0.2930 (5) | 0.033 (4)* | |
| C12 | 0.8835 (2) | −0.2161 (2) | 0.39446 (6) | 0.0370 (4) | |
| H12A | 1.000 (3) | −0.162 (3) | 0.3834 (7) | 0.062 (6)* | |
| H12B | 0.912 (3) | −0.232 (2) | 0.4259 (7) | 0.057 (6)* | |
| H12C | 0.855 (3) | −0.330 (3) | 0.3805 (6) | 0.054 (5)* | |
| C13 | 0.4119 (2) | 0.24828 (17) | 0.41004 (4) | 0.0267 (3) | |
| C14 | 0.5384 (2) | 0.38855 (18) | 0.41690 (5) | 0.0298 (3) | |
| H14 | 0.678 (3) | 0.386 (2) | 0.4064 (5) | 0.037 (4)* | |
| C15 | 0.4749 (2) | 0.53140 (18) | 0.43856 (5) | 0.0311 (3) | |
| H15 | 0.565 (2) | 0.6368 (18) | 0.4445 (5) | 0.021 (3)* | |
| C16 | 0.2816 (2) | 0.53215 (18) | 0.45402 (4) | 0.0291 (3) | |
| C17 | 0.1517 (2) | 0.39289 (19) | 0.44698 (5) | 0.0313 (3) | |
| H17 | 0.017 (3) | 0.394 (2) | 0.4587 (6) | 0.041 (5)* | |
| C18 | 0.2157 (2) | 0.25287 (19) | 0.42500 (5) | 0.0300 (3) | |
| H18 | 0.124 (2) | 0.157 (2) | 0.4201 (5) | 0.033 (4)* | |
| C19 | 0.3310 (3) | 0.8127 (2) | 0.48265 (6) | 0.0407 (4) | |
| H19A | 0.252 (3) | 0.891 (3) | 0.5003 (6) | 0.057 (6)* | |
| H19B | 0.471 (3) | 0.782 (2) | 0.4976 (7) | 0.054 (5)* | |
| H19C | 0.356 (3) | 0.862 (2) | 0.4538 (6) | 0.046 (5)* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0375 (6) | 0.0338 (6) | 0.0346 (6) | 0.0032 (4) | 0.0009 (4) | −0.0060 (4) |
| N1 | 0.0310 (6) | 0.0318 (7) | 0.0298 (6) | 0.0027 (5) | 0.0009 (5) | −0.0055 (5) |
| N2 | 0.0314 (6) | 0.0314 (6) | 0.0314 (7) | 0.0052 (5) | 0.0035 (5) | −0.0016 (5) |
| N3 | 0.0262 (6) | 0.0331 (7) | 0.0304 (6) | 0.0050 (5) | −0.0010 (5) | 0.0001 (5) |
| N4 | 0.0277 (6) | 0.0338 (7) | 0.0297 (6) | 0.0020 (5) | 0.0001 (5) | −0.0002 (5) |
| C1 | 0.0248 (6) | 0.0284 (7) | 0.0240 (7) | −0.0009 (5) | 0.0034 (5) | 0.0004 (5) |
| C2 | 0.0348 (8) | 0.0334 (8) | 0.0330 (8) | 0.0031 (6) | 0.0027 (6) | −0.0068 (6) |
| C3 | 0.0261 (7) | 0.0297 (7) | 0.0258 (7) | 0.0013 (5) | 0.0039 (5) | 0.0019 (6) |
| C4 | 0.0251 (6) | 0.0295 (7) | 0.0254 (7) | −0.0005 (5) | 0.0012 (5) | 0.0013 (5) |
| C5 | 0.0247 (6) | 0.0265 (7) | 0.0238 (7) | 0.0006 (5) | 0.0031 (5) | 0.0008 (5) |
| C6 | 0.0272 (7) | 0.0298 (7) | 0.0201 (6) | 0.0023 (5) | 0.0022 (5) | 0.0008 (5) |
| C7 | 0.0340 (8) | 0.0304 (7) | 0.0265 (7) | 0.0003 (6) | −0.0006 (6) | 0.0004 (6) |
| C8 | 0.0489 (9) | 0.0295 (8) | 0.0312 (8) | 0.0066 (7) | 0.0029 (7) | 0.0009 (6) |
| C9 | 0.0402 (8) | 0.0421 (9) | 0.0320 (8) | 0.0161 (7) | 0.0060 (6) | 0.0047 (7) |
| C10 | 0.0274 (7) | 0.0465 (9) | 0.0302 (8) | 0.0059 (6) | 0.0024 (6) | 0.0043 (7) |
| C11 | 0.0277 (7) | 0.0333 (8) | 0.0251 (7) | 0.0008 (6) | 0.0025 (5) | 0.0006 (6) |
| C12 | 0.0273 (8) | 0.0407 (9) | 0.0421 (10) | 0.0082 (6) | −0.0004 (7) | 0.0055 (7) |
| C13 | 0.0274 (7) | 0.0304 (7) | 0.0216 (7) | 0.0007 (5) | −0.0017 (5) | −0.0004 (5) |
| C14 | 0.0268 (7) | 0.0338 (8) | 0.0285 (7) | −0.0015 (6) | 0.0009 (6) | −0.0003 (6) |
| C15 | 0.0322 (7) | 0.0304 (8) | 0.0301 (8) | −0.0036 (6) | 0.0001 (6) | −0.0010 (6) |
| C16 | 0.0330 (7) | 0.0312 (7) | 0.0219 (7) | 0.0049 (6) | −0.0030 (5) | −0.0006 (5) |
| C17 | 0.0252 (7) | 0.0395 (8) | 0.0286 (7) | 0.0013 (6) | 0.0001 (6) | −0.0010 (6) |
| C18 | 0.0270 (7) | 0.0330 (8) | 0.0294 (7) | −0.0034 (6) | −0.0010 (6) | −0.0015 (6) |
| C19 | 0.0536 (10) | 0.0306 (8) | 0.0374 (9) | −0.0015 (7) | 0.0012 (8) | −0.0042 (7) |
Geometric parameters (Å, º)
| O1—C16 | 1.3690 (17) | C9—C10 | 1.383 (2) |
| O1—C19 | 1.430 (2) | C9—H9 | 0.988 (18) |
| N1—C1 | 1.3441 (18) | C10—C11 | 1.385 (2) |
| N1—C2 | 1.3471 (18) | C10—H10 | 0.96 (2) |
| N2—C2 | 1.3243 (19) | C11—H11 | 1.003 (16) |
| N2—C3 | 1.3438 (18) | C12—H12A | 0.96 (2) |
| N3—C3 | 1.3464 (18) | C12—H12B | 0.98 (2) |
| N3—N4 | 1.3687 (17) | C12—H12C | 1.01 (2) |
| N3—C12 | 1.4476 (18) | C13—C14 | 1.3854 (19) |
| N4—C4 | 1.3310 (17) | C13—C18 | 1.401 (2) |
| C1—C5 | 1.4087 (19) | C14—C15 | 1.393 (2) |
| C1—C6 | 1.4778 (18) | C14—H14 | 0.997 (17) |
| C2—H2 | 0.993 (17) | C15—C16 | 1.389 (2) |
| C3—C5 | 1.4089 (18) | C15—H15 | 1.025 (15) |
| C4—C5 | 1.4351 (19) | C16—C17 | 1.393 (2) |
| C4—C13 | 1.4753 (19) | C17—C18 | 1.381 (2) |
| C6—C7 | 1.395 (2) | C17—H17 | 0.983 (17) |
| C6—C11 | 1.3982 (19) | C18—H18 | 0.973 (17) |
| C7—C8 | 1.387 (2) | C19—H19A | 1.00 (2) |
| C7—H7 | 0.987 (17) | C19—H19B | 1.02 (2) |
| C8—C9 | 1.384 (2) | C19—H19C | 0.995 (19) |
| C8—H8 | 0.990 (18) | ||
| C16—O1—C19 | 117.64 (12) | C9—C10—H10 | 121.0 (11) |
| C1—N1—C2 | 118.61 (12) | C11—C10—H10 | 119.0 (11) |
| C2—N2—C3 | 111.67 (12) | C10—C11—C6 | 120.35 (14) |
| C3—N3—N4 | 111.03 (11) | C10—C11—H11 | 120.7 (9) |
| C3—N3—C12 | 127.98 (13) | C6—C11—H11 | 118.9 (9) |
| N4—N3—C12 | 120.99 (12) | N3—C12—H12A | 109.5 (12) |
| C4—N4—N3 | 107.06 (11) | N3—C12—H12B | 111.7 (12) |
| N1—C1—C5 | 119.14 (12) | H12A—C12—H12B | 108.8 (17) |
| N1—C1—C6 | 115.69 (12) | N3—C12—H12C | 106.5 (11) |
| C5—C1—C6 | 125.16 (12) | H12A—C12—H12C | 111.6 (16) |
| N2—C2—N1 | 128.53 (14) | H12B—C12—H12C | 108.8 (16) |
| N2—C2—H2 | 116.0 (10) | C14—C13—C18 | 118.58 (13) |
| N1—C2—H2 | 115.4 (10) | C14—C13—C4 | 119.90 (12) |
| N2—C3—N3 | 125.60 (12) | C18—C13—C4 | 121.42 (12) |
| N2—C3—C5 | 126.66 (13) | C13—C14—C15 | 121.41 (13) |
| N3—C3—C5 | 107.73 (12) | C13—C14—H14 | 119.1 (10) |
| N4—C4—C5 | 110.07 (12) | C15—C14—H14 | 119.5 (10) |
| N4—C4—C13 | 118.00 (12) | C16—C15—C14 | 119.18 (13) |
| C5—C4—C13 | 131.88 (12) | C16—C15—H15 | 117.3 (8) |
| C1—C5—C3 | 115.24 (12) | C14—C15—H15 | 123.6 (8) |
| C1—C5—C4 | 140.59 (13) | O1—C16—C15 | 123.91 (13) |
| C3—C5—C4 | 104.08 (12) | O1—C16—C17 | 115.98 (13) |
| C7—C6—C11 | 119.32 (13) | C15—C16—C17 | 120.11 (13) |
| C7—C6—C1 | 121.63 (12) | C18—C17—C16 | 120.07 (13) |
| C11—C6—C1 | 118.95 (13) | C18—C17—H17 | 120.7 (10) |
| C8—C7—C6 | 119.76 (14) | C16—C17—H17 | 119.2 (10) |
| C8—C7—H7 | 119.1 (10) | C17—C18—C13 | 120.62 (13) |
| C6—C7—H7 | 121.1 (9) | C17—C18—H18 | 119.4 (9) |
| C9—C8—C7 | 120.50 (15) | C13—C18—H18 | 120.0 (9) |
| C9—C8—H8 | 122.8 (10) | O1—C19—H19A | 105.4 (11) |
| C7—C8—H8 | 116.7 (10) | O1—C19—H19B | 110.0 (11) |
| C10—C9—C8 | 120.07 (14) | H19A—C19—H19B | 113.1 (16) |
| C10—C9—H9 | 120.4 (10) | O1—C19—H19C | 109.8 (11) |
| C8—C9—H9 | 119.5 (10) | H19A—C19—H19C | 112.3 (15) |
| C9—C10—C11 | 119.94 (14) | H19B—C19—H19C | 106.3 (15) |
| C3—N3—N4—C4 | −0.08 (15) | C5—C1—C6—C7 | 36.6 (2) |
| C12—N3—N4—C4 | −179.99 (13) | N1—C1—C6—C11 | 34.01 (18) |
| C2—N1—C1—C5 | −2.4 (2) | C5—C1—C6—C11 | −147.05 (14) |
| C2—N1—C1—C6 | 176.60 (13) | C11—C6—C7—C8 | 1.8 (2) |
| C3—N2—C2—N1 | 2.3 (2) | C1—C6—C7—C8 | 178.07 (13) |
| C1—N1—C2—N2 | −1.2 (2) | C6—C7—C8—C9 | −0.1 (2) |
| C2—N2—C3—N3 | −179.20 (14) | C7—C8—C9—C10 | −1.6 (2) |
| C2—N2—C3—C5 | 0.1 (2) | C8—C9—C10—C11 | 1.6 (2) |
| N4—N3—C3—N2 | −179.83 (13) | C9—C10—C11—C6 | 0.1 (2) |
| C12—N3—C3—N2 | 0.1 (2) | C7—C6—C11—C10 | −1.8 (2) |
| N4—N3—C3—C5 | 0.79 (16) | C1—C6—C11—C10 | −178.18 (13) |
| C12—N3—C3—C5 | −179.31 (14) | N4—C4—C13—C14 | 52.12 (18) |
| N3—N4—C4—C5 | −0.66 (15) | C5—C4—C13—C14 | −130.58 (16) |
| N3—N4—C4—C13 | 177.20 (11) | N4—C4—C13—C18 | −124.27 (15) |
| N1—C1—C5—C3 | 4.26 (19) | C5—C4—C13—C18 | 53.0 (2) |
| C6—C1—C5—C3 | −174.66 (12) | C18—C13—C14—C15 | 0.7 (2) |
| N1—C1—C5—C4 | −179.91 (16) | C4—C13—C14—C15 | −175.81 (13) |
| C6—C1—C5—C4 | 1.2 (3) | C13—C14—C15—C16 | 0.7 (2) |
| N2—C3—C5—C1 | −3.2 (2) | C19—O1—C16—C15 | 2.7 (2) |
| N3—C3—C5—C1 | 176.16 (12) | C19—O1—C16—C17 | −177.26 (13) |
| N2—C3—C5—C4 | 179.52 (13) | C14—C15—C16—O1 | 178.62 (13) |
| N3—C3—C5—C4 | −1.11 (15) | C14—C15—C16—C17 | −1.4 (2) |
| N4—C4—C5—C1 | −175.01 (16) | O1—C16—C17—C18 | −179.36 (13) |
| C13—C4—C5—C1 | 7.5 (3) | C15—C16—C17—C18 | 0.7 (2) |
| N4—C4—C5—C3 | 1.10 (15) | C16—C17—C18—C13 | 0.8 (2) |
| C13—C4—C5—C3 | −176.36 (14) | C14—C13—C18—C17 | −1.4 (2) |
| N1—C1—C6—C7 | −142.30 (14) | C4—C13—C18—C17 | 175.00 (13) |
Hydrogen-bond geometry (Å, º)
Cg1 and Cg4 are the centroids of the C3/C4/C5/N4/N3 and C13–C18 rings, respectively.
| D—H···A | D—H | H···A | D···A | D—H···A |
| C9—H9···N2i | 0.988 (18) | 2.579 (17) | 3.3995 (19) | 140.3 (14) |
| C12—H12B···O1ii | 0.98 (2) | 2.49 (2) | 3.2694 (19) | 136.4 (15) |
| C17—H17···O1iii | 0.983 (17) | 2.618 (9) | 3.4973 (17) | 149.3 (14) |
| C19—H19B···Cg4iv | 1.02 (2) | 2.74 (2) | 3.5928 (19) | 141.9 (14) |
| C19—H19C···Cg1v | 0.995 (19) | 2.947 (19) | 3.9072 (19) | 162.0 (15) |
Symmetry codes: (i) x−1, y+1, z; (ii) x+1, y−1, z; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) x, y+1, z.
Funding Statement
This work was funded by National Science Foundation grant 1228232. Tulane University grant .
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019004894/wm5499sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019004894/wm5499Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989019004894/wm5499Isup3.cml
CCDC reference: 1909062
Additional supporting information: crystallographic information; 3D view; checkCIF report