Crystal structure and Hirshfeld surface analysis of 3-(4-methoxyphenyl)-1-methyl-4-phenyl-1H-pyrazolo[3,4-d]pyrimidine

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.


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 ISSN 2056-9890 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-H9Á Á ÁN2 hydrogen bonds between aromatic hydrogen atoms and one of the pyrimidine N atoms as well as C12-H12BÁ Á ÁO1 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 [110] (Table 1 and Fig. 2). Centrosymmetric dimers with an R 2 2 (8) graph-set motif are formed by pairwise C17-H17Á Á ÁO1 hydrogen bonds. The chains are linked into layers parallel to (001) by C19-H19CÁ Á ÁCg1 interactions, and pairs of layers are joined into thicker slabs by C19-H19BÁ Á ÁCg4 interactions (Table 1

Figure 3
Packing of the crystal viewed along [100] with intermolecular interactions depicted as in Fig. 2.

Figure 1
The title molecule with the labeling scheme and displacement ellipsoids drawn at the 50% probability level.

Figure 4
Packing of the crystal viewed along [010] with intermolecular interactions depicted as in Fig. 2.

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 d norm , d i , d e , 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. Fig. 7a 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. 7b) reveal that the HÁ Á ÁH contacts clearly give the most significant contribution to the Hirshfeld surface (48.2%). In addition, CÁ Á ÁH/HÁ Á ÁC, NÁ Á ÁH/HÁ Á ÁN, OÁ Á ÁH/HÁ Á ÁO and CÁ Á ÁN/NÁ Á ÁC contacts contribute 23.9%, 17.4%, 5.3% and 2.6%, respectively, to the Hirshfeld surface. In particular, the NÁ Á ÁH/HÁ Á ÁN and OÁ Á ÁH/HÁ Á ÁO contacts indicate the presence of intermolecular C-HÁ Á ÁN and C-HÁ Á ÁO interactions, respectively. Much weaker CÁ Á ÁC (2.2%) and CÁ Á ÁO/ OÁ Á ÁC (0.5%) contacts also occur.
A view of the molecular electrostatic potential, in the range À0.0500 to 0.0500 a.u. using the 6-31G(d,p) basis set (DFT method), for the title compound is shown in Fig. 8    Two-dimensional fingerprint plots for the title structure, with a d norm view and relative contribution of the atom pairs to the Hirshfeld surface.

Figure 8
A view of the molecular electrostatic potential of the title compound in the range À0.05 to 0.05 a.u. using the 6-31G(d,p) basis set (DFT method). and acceptors for C-HÁ Á ÁO and C-HÁ Á ÁN hydrogen bonds are shown as blue and red areas around the atoms related with positive (hydrogen-bond donors) and negative (hydrogenbond acceptors) electrostatic potentials, respectively.

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.

Funding information
The support of NSF-MRI grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.  program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

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 F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > 2sigma(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.