- 1. Chemical context
- 2. Structural commentary
- 3. Supramolecular features
- 4. Hirshfeld surface and crystal void analysis
- 5. Interaction energy and energy framework calculations
- 6. DFT and Molecular electrostatic potential (MEP) calculations
- 7. Database survey
- 8. Refinement
- 9. Synthesis and crystallization
- Supporting information
- References
- 1. Chemical context
- 2. Structural commentary
- 3. Supramolecular features
- 4. Hirshfeld surface and crystal void analysis
- 5. Interaction energy and energy framework calculations
- 6. DFT and Molecular electrostatic potential (MEP) calculations
- 7. Database survey
- 8. Refinement
- 9. Synthesis and crystallization
- Supporting information
- References
research communications
H-pyrazolo[3,4-d]pyrimidin-1-yl)acetic acid
determination, Hirshfeld surface, crystal void, intermolecular interaction energy analyses, as well as DFT and energy framework calculations of 2-(4-oxo-4,5-dihydro-1aLaboratory of Organic and Physical Chemistry, Applied Bioorganic Chemistry Team, Faculty of Sciences, Ibn Zohr University, Agadir, Morocco, bLaboratory of Organic Synthesis and Molecular Physico-Chemistry, Department of Chemistry, Faculty of Sciences, Semlalia, BP 2390, Marrakech 40001, Morocco, cLaboratory of Organic Chemistry and Physical Chemistry, Research Team: Molecular Modeling, Materials and Environment, Department of Chemistry, Faculty of Sciences of Agadir, University Ibn Zohr, BP 8106 Agadir, Morocco, dLaboratory of Spectroscopy, Molecular Modeling, Materials, Nanomaterials, Water and Environment, CERNE2D, Faculty of Sciences, Mohammed V University in Rabat, Av. Ibn Battouta, BP 1014, Rabat, Morocco, eDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, fDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, and gLaboratory of Heterocyclic Organic Chemistry, Medicines Science Research Center, Pharmacochemistry Competence Center, Mohammed V University in Rabat, Faculty of Sciences, Av. Ibn Battouta, BP 1014, Rabat, Morocco
*Correspondence e-mail: ezaddine1996@gmail.com
In the title molecule, C7H6N4O3, the bicyclic ring system is planar with the carboxymethyl group inclined by 81.05 (5)° to this plane. In the crystal, corrugated layers parallel to (010) are generated by N—H⋯O, O—H⋯N and C—H⋯O hydrogen-bonding interactions. The layers are associated through C—H⋯π(ring) interactions. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯O/O⋯H (34.8%), H⋯N/N⋯H (19.3%) and H⋯H (18.1%) interactions. The volume of the crystal voids and the percentage of free space were calculated to be 176.30 Å3 and 10.94%, showing that there is no large cavity in the crystal packing. Computational methods revealed O—H⋯N, N—H⋯O and C—H⋯O hydrogen-bonding energies of 76.3, 55.2, 32.8 and 19.1 kJ mol−1, respectively. Evaluations of the electrostatic, dispersion and total energy frameworks indicate that the stabilization is dominated via dispersion energy contributions. Moreover, the optimized molecular structure, using density functional theory (DFT) at the B3LYP/6–311G(d,p) level, was compared with the experimentally determined one. The HOMO–LUMO energy gap was determined and the molecular electrostatic potential (MEP) surface was calculated at the B3LYP/6–31G level to predict sites for electrophilic and nucleophilic attacks.
CCDC reference: 2203303
1. Chemical context
The chemistry of et al., 2020; Sebbar et al., 2016; El Ghayati et al., 2021; Dinakaran et al., 2012; Lahmidi et al., 2018; Hni et al., 2019). In this regard, pyrazolo[3,4-d]pyrimidines are an important family of and their derivatives possess various pharmacological properties (Bakavoli et al., 2010; Severina et al., 2016), including their applications as anti-microbial (Holla et al., 2006; Bakavoli et al., 2010), anti-tumor (Kandeel et al., 2012), anti-inflammatory (El-Tombary, 2013), anti-oxidant (El-Mekabaty, 2015), anti-cancer (Gupta et al., 2008; Maher et al., 2019) and anti-convulsant (Severina et al., 2016) agents. Pyrazolopyrimidines can also be used in the treatment of Alzheimers' disease (Zhang et al., 2018), and they have a powerful activity against herpes viruses (Gudmundsson et al., 2009) and human leukaemia (HL-60) (Song et al., 2011).
still receives increasing interest because of the therapeutic importance of most especially those with nitrogen-containing heterocycles, which are of great interest as potential bioactive molecules (TaiaAs a continuation of our research in this context, the title compound, (I), was synthesized by basic hydrolysis of the methyl ester of 2-(4-oxo-4, 5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-1-yl)acetate. We report herein its synthesis, molecular and crystal structures along with Hirshfeld surface analysis, crystal void and intermolecular interaction energies. Moreover, the optimized molecular structure carried out at the B3LYP/6–311 G(d,p) level is compared with the experimentally determined structure, and energy framework as well as molecular electrostatic potential (MEP) surface computations carried out at the B3LYP/6-31G level to predict the reactive sites for the electrophilic and nucleophilic attacks on (I) are presented.
2. Structural commentary
The pyrazolopyrimidine moiety is planar to within 0.0143 (10) Å (r.m.s deviation = 0.0082 Å) with the flap atom N1, which is part of the NH group, being the furthest from the mean plane. The plane of the carboxyl group is inclined to the above plane by 81.05 (5)°. There are no unusual bond lengths or interatomic angles in the molecule (Fig. 1).
3. Supramolecular features
In the crystal, inversion dimers are formed by N1—H1⋯O1 hydrogen bonds (Table 1) and are connected into sheets by complementary C5—H5⋯O1 hydrogen bonds (Table 1). Adjacent sheets are connected by O2—H2A⋯N2 and C6—C6A⋯O3 hydrogen bonds (Table 1) to form corrugated (010) layers with the component sheets alternately arranged parallel to (11) and (16) (Figs. 2 and 3). These corrugated layers are associated through C6—H6B⋯Cg1 interactions (Table 1 and Fig. 3).
4. Hirshfeld surface and crystal void analysis
In order to visualize the intermolecular interactions in the crystal of (I), a Hirshfeld surface (HS) analysis (Hirshfeld, 1977) was carried out by using Crystal Explorer (Spackman et al., 2021). In the HS plotted over dnorm (Fig. 4), the white surface indicates contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter or longer than the sum of the van der Waals radii, respectively (Venkatesan et al., 2016). The bright-red spots indicate sites of donor and/or acceptor interactions and they also appear as blue and red regions corresponding to positive (hydrogen bond donors) and negative (hydrogen bond acceptors) potentials on the HS mapped over electrostatic potential (Spackman et al., 2008; Jayatilaka et al., 2005), as shown in Fig. 5. The shape-index of the HS is a tool to visualize the presence of π–π stacking by the appearance of adjacent red and blue triangles. Fig. 5 clearly suggests that there are no significant π–π interactions in (I), as the above pattern is absent.
The overall two-dimensional fingerprint plot, Fig. 6a, and those delineated into H⋯O/O⋯H, H⋯N/N⋯H, H⋯H, H⋯C/C⋯H, C⋯O/O⋯C, N⋯O/O⋯N, C⋯N/N⋯C, C⋯C and O⋯O contacts (McKinnon et al., 2007), and their relative contributions to the Hirshfeld surface, are illustrated in Fig. 6b–j. The most important interaction is H⋯O/O⋯H, contributing 34.8% to the overall crystal packing, which is shown in Fig. 6b where the pair of spikes have tips at de + di = 1.81 Å. The pair of spikes in the fingerprint plot delineated into H⋯N/N⋯H contacts, Fig. 6c, with a 19.3% contribution to the HS has a symmetric distribution of points with the tips at de + di = 1.74 Å. The H⋯H contacts contribute with 18.1% to the HS and are shown in Fig. 6c as widely scattered points of high density due to the large hydrogen content of the molecule with the tip at de = di = 1.28 Å. The high contribution of these interactions suggest that van der Waals interactions play the major role in the crystal packing (Hathwar et al., 2015). The presence of C—H⋯π interactions is shown by the pair of wings in the fingerprint plot delineated into H⋯C/C⋯H contacts with the tips at de + di = 2.93 Å (Fig. 6e) with a 9.0% contribution to the HS. The C⋯O/O⋯C (Fig. 6f), N⋯O/O⋯N (Fig. 6g) and C⋯N/N⋯C (Fig. 6h) contacts contribute with 6.7%, 5.9% and 3.1%, respectively, to the HS and the distributions of points appear with the tips at de + di = 2.95 Å, de + di = 3.15 Å and de + di = 3.38 Å. The C⋯C contacts, Fig. 6i, with a 2.1% contribution to the HS, have a bullet-shaped distribution of points with the tip at de = di = 1.73 Å. Finally, the contribution of the O⋯O contacts (Fig. 6j) to the HS is 1.0% with a low density of points.
The Hirshfeld surface representations with the function dnorm plotted onto the surface are shown for the H⋯O/O⋯H, H⋯N/N⋯H, H⋯H and H⋯C/C⋯H interactions in Fig. 7a–d, respectively.
The strength of the crystal packing is important for determining the response to an applied mechanical force. If the crystal packing results in significant voids, then the molecules are not tightly packed and a small amount of applied external mechanical force may easily break the crystal. To check the mechanical stability of the crystal, a void analysis was performed by adding up the electron densities of the spherically symmetric atoms contained in the et al., 2011). The void surface is defined as an isosurface of the procrystal electron density and is calculated for the whole where the void surface meets the boundary of the and capping faces are generated to create an enclosed volume. The volume of the crystal voids (Fig. 8a and b) and the percentage of free space in the are calculated as 176.30 Å3 and 10.94%, respectively. Thus, the crystal packing appears compact and the mechanical stability should be substantial.
(Turner5. Interaction energy and energy framework calculations
The intermolecular interaction energies were calculated using a CE–B3LYP/6–31G(d,p) energy model available in Crystal Explorer (Spackman et al., 2021), where a cluster of molecules is generated by applying operations with respect to a selected central molecule within the radius of 3.8 Å (Turner et al., 2014). The total intermolecular energy (Etot) is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange–repulsion (Erep) energies (Turner et al., 2015) with scale factors of 1.057, 0.740, 0.871 and 0.618, respectively (Mackenzie et al., 2017). Hydrogen-bonding interaction energies (in kJ mol−1) were calculated to be −73.0 (Eele), −16.4 (Epol), −27.3 (Edis), 93.6 (Erep) and −55.2 (Etot) for N1—H1⋯O1 hydrogen-bonding interactions, −103.5 (Eele), −22.1 (Epol), −13.2 (Edis), 98.8 (Erep) and −76.3 (Etot) for O2—H2A⋯N2 hydrogen-bonding interactions, −12.2 (Eele), −2.9 (Epol), −34.4 (Edis), 19.9 (Erep) and −32.8 (Etot) for C5—H5⋯O1 hydrogen-bonding interactions, and −19.5 (Eele), −3.2 (Epol), −12.3 (Edis), 23.8 (Erep) and −19.0 (Etot) for C6—H6A⋯O3 hydrogen-bonding interactions.
Energy frameworks combine the calculation of intermolecular interaction energies with a graphical representation of their magnitude (Turner et al., 2015). Energies between molecular pairs are represented as cylinders joining the centroids of pairs of molecules with the cylinder radius proportional to the relative strength of the corresponding interaction energy. Energy frameworks were constructed for Eele (red cylinders), Edis (green cylinders) and Etot (blue cylinders) (Fig. 9a, b and c). The results indicate that the stabilization is dominated via dispersion energy contributions in (I).
6. DFT and Molecular electrostatic potential (MEP) calculations
Density functional theory (DFT) using the standard B3LYP functional (Becke, 1993) and Pople's basis set 6–31G(d,p) implemented in GAUSSIAN 09 (Frisch et al., 2009) was used to optimize the molecular structure of (I) in the gas phase. The minimum was confirmed by frequency calculations, and the resulting optimized parameters (bond lengths and angles) agreed satisfactorily with the experimental structural data (Table 2). As a result, energies and other physico-chemical properties obtained from the optimized structure could be safely used to describe those of (I). The corresponding HOMO and LUMO energies were then used to estimate some parameters of global chemical reactivity, such as (χ), hardness (η), (I), (ω) and softness (σ) (Table 3). In addition, the molecular electrostatic potential (MEP) map, and (μ) of (I) were similarly calculated.
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Minor differences between theory and experiment are likely due to optimized values being obtained in the isolated gas phase, neglecting interactions in the solid phase. Briefly, the average O2—C7 and N4—C5 bond lengths calculated at the DFT/B3LYP/6-31G(d,p) level are 1.3767 and 1.3412 Å, respectively, which is slightly higher than the experimental values of 1.3148 (17) and 1.3182 (19) Å, respectively. Moreover, the torsion angles N4—N3—C3—N2 = −179.92° and C3—N2—C2—N1 = −0.53° agree well with the experimental ones of −178.88 (12) and −0.6 (2)°.
The optimized frontier molecular orbitals (HOMO and LUMO) are shown in Fig. 10. These orbitals play an important role in intramolecular charge transfer (ICT). The topological characteristics of these levels are important for interpreting kinetic stability and therefore potential chemical reactivity. The calculated energy band gap [ΔE = ELUMO – EHOMO] of the molecule is 5.25 eV which indicates a hard molecule with low polarizability and low chemical and biological activities but high kinetic stability. The LUMO is mainly centered on the plane extending over the whole aromatic ring system of (I). The numerical reactivity descriptors, which are mainly based on HOMO–LUMO energies, are summarized in Table 3. The (I) is defined as the amount of energy required to remove an electron from a molecule. The high indicates also high stability and hence chemical inertness. (A) is defined as the energy released when an electron is added to a neutral molecule. Therefore a large value indicates the tendency of the molecule to retain its electrons. A negative (μ) reflects molecular stability while hardness (η) characterizes the resistance of the cloud of molecular electrons to deformation during small disturbances. The overall index (ω) of a molecule is a measure of its stabilization energy following the addition of an external electronic charge or its resistance to exchange electron(s) with the system (Parr et al., 1999). For (I), the of 6.66 eV indicates high stability.
The molecular electrostatic potential (MEP) of the surface was calculated on the optimized B3LYP/6-31G (d,p) level using Gaussview software (Frisch et al., 2009). The MEP surface (Fig. 11) gives information about the reactive sites. The total electron density on which the electrostatic potential surface has been mapped is shown in Fig. 12 where a visual representation of chemically active sites and the comparative reactivity of atoms is also shown. The red regions denote the most negative electrostatic potential, the blue regions represent most positive electrostatic potential, and green regions represent the region of zero potential. Fig. 12 confirms the existence of intermolecular N—H⋯O, O—H⋯N and—H⋯O hydrogen-bonding interactions.
7. Database survey
A search of the Cambridge Structural Database (CSD, updated March 2022; Groom et al., 2016) with the search fragment A (R = C—CH, C—C—OH; R′ = R" = variable; Fig. 13) yielded 11 hits. These included structures with R = t-Bu, R" = H, R′ = Ph (RULHEN; Liu et al., 2015), p-anis (QIBVIH; Tan et al., 2007); R" = H, R = i-Pr, R′ = cyclobutanecarboxamido (QIBVON; Tan et al., 2007), R = n-Bu, R′ = benzamido (QIBWAA; Tan et al., 2007), R = 3-phenylpropyl, R′ = CH3S (IFICUV; Avasthi et al., 2002), R = 2-chloroethyl, R′ = H (XAZRAT; Khazi et al., 2012); R = 1-β-D-ribofuranosyl, R′ = H, R" = OMe (FOVHIH; Anderson et al., 1986), R′ = NH2, R" = H (YOMJIW; Ren et al., 2019); R = 2-deoxy-β-D-erythro-pentofuranosyl, R′ = NH2, R" = Br (HIPPAX; Seela et al., 1999), R" = I (HIPPEB; Seela et al., 1999); R = 2-deoxy-2-fluoro-β-D-arabino-furanosyl, R′ = NH2, R" = Br (EJEJUY; He et al., 2003). Like in (I), the pyrazolopyrimidine unit is essentially planar in these molecules, but with the variety of substituents and the presence of different hydrogen-bonding interactions, the packings in the crystal are quite different.
8. Refinement
Crystal data, data collection and structure . Hydrogen atoms attached to carbon were placed in idealized positions while those attached to nitrogen and to oxygen were placed in locations derived from a difference-Fourier map and their parameters adjusted to give N—H = 0.91 and O—H = 0.87 Å. All H atoms were included as riding contributions with isotropic displacement parameters tied to those of the attached atoms.
details are summarized in Table 4
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9. Synthesis and crystallization
Ethyl 2-(4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-1-yl)acetate (5 mmol) was dissolved in 10 ml of ethanol to which 10 ml of NaOH (aqueous, 10%wt) were added. The reaction mixture was stirred magnetically at room temperature for 4 h. After evaporation of ethanol and washing the aqueous phase with ethyl acetate, the mixture was acidified with an aqueous solution of HCl (3 N). The formed precipitate was filtered off and rinsed with ether. The crude product was recrystallized from ethanol to obtain colourless crystals of (I) in 72% yield.
Supporting information
CCDC reference: 2203303
https://doi.org/10.1107/S2056989022008489/wm5656sup1.cif
contains datablocks I, global. DOI:Supporting information file. DOI: https://doi.org/10.1107/S2056989022008489/wm5656Isup3.cdx
Supporting information file. DOI: https://doi.org/10.1107/S2056989022008489/wm5656Isup4.cml
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022008489/wm5656Isup5.hkl
Data collection: APEX3 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).C7H6N4O3 | F(000) = 800 |
Mr = 194.16 | Dx = 1.601 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54178 Å |
a = 15.3747 (4) Å | Cell parameters from 5261 reflections |
b = 4.6699 (1) Å | θ = 3.9–74.4° |
c = 23.0423 (5) Å | µ = 1.11 mm−1 |
β = 103.122 (1)° | T = 296 K |
V = 1611.20 (6) Å3 | Block, colourless |
Z = 8 | 0.24 × 0.18 × 0.11 mm |
Bruker D8 VENTURE PHOTON 100 CMOS diffractometer | 1598 independent reflections |
Radiation source: INCOATEC IµS micro–focus source | 1503 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.026 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 74.4°, θmin = 3.9° |
ω scans | h = −16→18 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | k = −5→5 |
Tmin = 0.81, Tmax = 0.89 | l = −28→28 |
5850 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.063P)2 + 0.6265P] where P = (Fo2 + 2Fc2)/3 |
S = 1.16 | (Δ/σ)max < 0.001 |
1598 reflections | Δρmax = 0.25 e Å−3 |
128 parameters | Δρmin = −0.33 e Å−3 |
0 restraints | Extinction correction: SHELXL 2018/3 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: dual | Extinction coefficient: 0.0304 (14) |
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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) while those attached to nitrogen and to oxygen were placed in locations derived from a difference map and their parameters adjusted to give N—H = 0.91 and O—H = 0.87 Å. All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.39351 (7) | 0.6126 (2) | 0.49522 (5) | 0.0517 (4) | |
H1 | 0.491406 | 0.298878 | 0.457379 | 0.078* | |
O2 | 0.17845 (7) | 0.3011 (2) | 0.24916 (4) | 0.0474 (3) | |
H2A | 0.169736 | 0.370596 | 0.213269 | 0.071* | |
O3 | 0.07906 (7) | −0.0274 (3) | 0.20612 (5) | 0.0586 (4) | |
N1 | 0.43440 (7) | 0.2658 (3) | 0.43684 (5) | 0.0417 (3) | |
N2 | 0.33583 (7) | 0.0013 (3) | 0.36309 (5) | 0.0397 (3) | |
N3 | 0.18190 (7) | 0.1198 (3) | 0.35967 (5) | 0.0375 (3) | |
C1 | 0.37053 (9) | 0.4290 (3) | 0.45639 (6) | 0.0389 (4) | |
C2 | 0.41582 (9) | 0.0694 (3) | 0.39270 (6) | 0.0421 (4) | |
H2 | 0.463751 | −0.024383 | 0.382697 | 0.051* | |
C3 | 0.27031 (9) | 0.1489 (3) | 0.38153 (5) | 0.0353 (3) | |
C4 | 0.28199 (9) | 0.3561 (3) | 0.42577 (5) | 0.0376 (3) | |
N4 | 0.13470 (8) | 0.3040 (3) | 0.38734 (5) | 0.0435 (3) | |
C5 | 0.19481 (10) | 0.4438 (3) | 0.42717 (6) | 0.0438 (4) | |
H5 | 0.181431 | 0.582221 | 0.452827 | 0.053* | |
C6 | 0.13600 (9) | −0.0569 (3) | 0.31065 (6) | 0.0410 (4) | |
H6A | 0.076673 | −0.099206 | 0.316240 | 0.049* | |
H6B | 0.167753 | −0.237123 | 0.311870 | 0.049* | |
C7 | 0.12731 (8) | 0.0757 (3) | 0.24955 (6) | 0.0387 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0478 (6) | 0.0593 (7) | 0.0440 (6) | −0.0021 (5) | 0.0021 (4) | −0.0198 (5) |
O2 | 0.0562 (6) | 0.0484 (6) | 0.0337 (5) | −0.0094 (5) | 0.0024 (4) | 0.0066 (4) |
O3 | 0.0537 (7) | 0.0787 (8) | 0.0370 (6) | −0.0145 (6) | −0.0030 (5) | −0.0075 (5) |
N1 | 0.0377 (6) | 0.0487 (7) | 0.0362 (6) | −0.0022 (5) | 0.0031 (5) | −0.0063 (5) |
N2 | 0.0409 (6) | 0.0435 (6) | 0.0333 (6) | −0.0011 (5) | 0.0057 (5) | −0.0058 (5) |
N3 | 0.0373 (6) | 0.0434 (6) | 0.0300 (6) | −0.0026 (5) | 0.0040 (4) | −0.0002 (4) |
C1 | 0.0435 (7) | 0.0425 (7) | 0.0293 (6) | −0.0021 (6) | 0.0050 (5) | −0.0036 (5) |
C2 | 0.0418 (7) | 0.0470 (8) | 0.0366 (7) | 0.0006 (6) | 0.0069 (6) | −0.0051 (6) |
C3 | 0.0380 (7) | 0.0392 (7) | 0.0278 (6) | −0.0021 (5) | 0.0056 (5) | 0.0016 (5) |
C4 | 0.0405 (7) | 0.0425 (7) | 0.0290 (6) | −0.0013 (5) | 0.0062 (5) | −0.0019 (5) |
N4 | 0.0415 (6) | 0.0525 (7) | 0.0364 (6) | 0.0021 (5) | 0.0087 (5) | −0.0001 (5) |
C5 | 0.0452 (8) | 0.0510 (8) | 0.0348 (7) | 0.0026 (6) | 0.0081 (6) | −0.0050 (6) |
C6 | 0.0418 (7) | 0.0433 (8) | 0.0348 (7) | −0.0092 (6) | 0.0018 (5) | −0.0003 (5) |
C7 | 0.0354 (7) | 0.0446 (8) | 0.0336 (7) | 0.0004 (5) | 0.0024 (5) | −0.0018 (5) |
O1—C1 | 1.2315 (17) | N3—C6 | 1.4468 (17) |
O2—C7 | 1.3148 (17) | C1—C4 | 1.4251 (18) |
O2—H2A | 0.8701 | C2—H2 | 0.9300 |
O3—C7 | 1.2028 (17) | C3—C4 | 1.3872 (19) |
N1—C2 | 1.3512 (18) | C4—C5 | 1.4090 (19) |
N1—C1 | 1.3961 (18) | N4—C5 | 1.3182 (19) |
N1—H1 | 0.9098 | C5—H5 | 0.9300 |
N2—C2 | 1.3030 (18) | C6—C7 | 1.5160 (18) |
N2—C3 | 1.3655 (17) | C6—H6A | 0.9700 |
N3—C3 | 1.3449 (17) | C6—H6B | 0.9700 |
N3—N4 | 1.3723 (16) | ||
C7—O2—H2A | 110.0 | C3—C4—C5 | 104.74 (12) |
C2—N1—C1 | 124.73 (11) | C3—C4—C1 | 118.71 (12) |
C2—N1—H1 | 121.4 | C5—C4—C1 | 136.54 (13) |
C1—N1—H1 | 113.9 | C5—N4—N3 | 105.83 (11) |
C2—N2—C3 | 112.91 (12) | N4—C5—C4 | 111.12 (13) |
C3—N3—N4 | 111.03 (11) | N4—C5—H5 | 124.4 |
C3—N3—C6 | 128.49 (12) | C4—C5—H5 | 124.4 |
N4—N3—C6 | 120.31 (11) | N3—C6—C7 | 114.60 (11) |
O1—C1—N1 | 120.51 (13) | N3—C6—H6A | 108.6 |
O1—C1—C4 | 127.62 (13) | C7—C6—H6A | 108.6 |
N1—C1—C4 | 111.86 (11) | N3—C6—H6B | 108.6 |
N2—C2—N1 | 124.94 (13) | C7—C6—H6B | 108.6 |
N2—C2—H2 | 117.5 | H6A—C6—H6B | 107.6 |
N1—C2—H2 | 117.5 | O3—C7—O2 | 124.87 (13) |
N3—C3—N2 | 125.93 (12) | O3—C7—C6 | 121.10 (13) |
N3—C3—C4 | 107.27 (12) | O2—C7—C6 | 113.99 (11) |
N2—C3—C4 | 126.80 (12) | ||
C2—N1—C1—O1 | −176.82 (13) | O1—C1—C4—C3 | 177.49 (14) |
C2—N1—C1—C4 | 2.4 (2) | N1—C1—C4—C3 | −1.64 (18) |
C3—N2—C2—N1 | −0.6 (2) | O1—C1—C4—C5 | −1.6 (3) |
C1—N1—C2—N2 | −1.4 (2) | N1—C1—C4—C5 | 179.24 (15) |
N4—N3—C3—N2 | −178.88 (12) | C3—N3—N4—C5 | −0.97 (15) |
C6—N3—C3—N2 | −3.7 (2) | C6—N3—N4—C5 | −176.57 (12) |
N4—N3—C3—C4 | 0.92 (15) | N3—N4—C5—C4 | 0.64 (16) |
C6—N3—C3—C4 | 176.06 (12) | C3—C4—C5—N4 | −0.10 (16) |
C2—N2—C3—N3 | −179.00 (13) | C1—C4—C5—N4 | 179.09 (15) |
C2—N2—C3—C4 | 1.2 (2) | C3—N3—C6—C7 | −83.22 (17) |
N3—C3—C4—C5 | −0.49 (15) | N4—N3—C6—C7 | 91.53 (15) |
N2—C3—C4—C5 | 179.30 (13) | N3—C6—C7—O3 | −168.31 (14) |
N3—C3—C4—C1 | −179.86 (11) | N3—C6—C7—O2 | 13.70 (18) |
N2—C3—C4—C1 | −0.1 (2) |
Cg1 is the centroid of the C3/C4/C5/N4/N3 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.91 | 1.90 | 2.8094 (16) | 175 |
O2—H2A···N2ii | 0.87 | 1.85 | 2.7120 (14) | 173 |
C5—H5···O1iii | 0.93 | 2.33 | 3.2305 (18) | 164 |
C6—H6A···O3iv | 0.97 | 2.36 | 3.2436 (18) | 152 |
C6—H6B···Cg1v | 0.97 | 2.98 | 3.7387 (15) | 136 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1/2, −y+3/2, −z+1; (iv) −x, y, −z+1/2; (v) x, y−1, z. |
X-ray | B3LYP/6-311G(d,p) | |
O1═C1 | 1.2315 (17) | 1.2450 |
O2—C7 | 1.3148 (17) | 1.3767 |
O3═C7 | 1.2028 (17) | 1.2273 |
N1—C2 | 1.3512 (18) | 1.3749 |
N1—C1 | 1.3961 (18) | 1.4047 |
N1—H1 | 0.9098 | 1.0128 |
N2═C2 | 1.3030 (18) | 1.3131 |
N2—C3 | 1.3655 (17) | 1.3742 |
N3—C3 | 1.3449 (17) | 1.3605 |
N3—N4 | 1.3723 (16) | 1.3955 |
N3—C6 | 1.4468 (17) | 1.4417 |
C3═C4 | 1.3872 (19) | 1.4048 |
N4═C5 | 1.3182 (19) | 1.3412 |
C2—N1—C1 | 124.73 (11) | 125.36 |
C2—N1—H1 | 121.4 | 120.93 |
C1—N1—H1 | 113.9 | 114.80 |
C2═N2—C3 | 112.91 (12) | 113.46 |
C3—N3—N4 | 111.03 (11) | 111.21 |
C3—N3—C6 | 128.49 (12) | 128.12 |
N4—N3—C6 | 120.31 (11) | 120.45 |
O1═C1—N1 | 120.51 (13) | 120.02 |
O1═C1—C4 | 127.62 (13) | 128.40 |
N2═C2—N1 | 124.94 (13) | 124.12 |
O3═C7—O2 | 124.87 (13) | 123.65 |
C2—N1—C1═O1 | –176.82 (13) | –178.60 |
C3—N2—C2—N1 | –0.6 (2) | –0.53 |
C1—N1—C2=N2 | –1.4 (2) | –1.25 |
N4—N3—C3—N2 | –178.88 (12) | –179.92 |
Total energy, TE (eV) | –19449.75 |
EHOMO (eV) | –6.66 |
ELUMO (eV) | –1.41 |
Gap, ΔE (eV) | 5.25 |
Dipole moment, µ (Debye) | 4.49 |
Ionisation potential, I (eV) | 6.66 |
Electron affinity, A | 1.42 |
Electronegativity, χ | 4.04 |
Hardness, η | 2.62 |
Electrophilicity index, ω | 3.11 |
Softness, σ | 0.38 |
Fraction of electron transferred, ΔN | 0.56 |
Funding information
JTM acknowledges NSF–MRI grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory. TH is grateful to Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004).
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