In the title compound, the benzodiazolone moieties are planar to within 0.017 (1) and 0.026 (1) Å, and oriented at a dihedral angle of 57.35 (3)°. In the crystal, two sets of intermolecular C—H⋯O hydrogen bonds generate layers parallel to the bc plane.
Keywords: crystal structure, hydrogen bond, benzodiazolone, Hirshfeld surface
Abstract
In the title compound, C21H20N4O2, the intramolecular C—H⋯O hydrogen-bonded benzodiazolone moieties are planar to within 0.017 (1) and 0.026 (1) Å, and are oriented at a dihedral angle of 57.35 (3)°. In the crystal, two sets of intermolecular C—H⋯O hydrogen bonds generate layers parallel to the bc plane. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (51.8%), H⋯C/C⋯H (30.7%) and H⋯O/O⋯H (11.2%) interactions.
Chemical context
The benzimidazole unit is an important pharmacophore and a privileged structure in the functions of biological molecules. Benzimidazole derivatives have attracted considerable attention from researchers because their bioactive and pharmaceutical properties. Many members of this family are widely used as anticonvulsant, anti-fungal, analgesic, antimicrobial, anti-histaminic and hypnotic or anti-inflammatory agents (Ayhan-Kılcıgil et al., 2007 ▸; Soderlind et al., 1999 ▸; Luo et al., 2011 ▸; Walia et al., 2011 ▸; Navarrete-Vázquez et al., 2001 ▸). Benzimidazolone derivatives also find commercial use as dyes for acrylic fibres. The search for new heterocyclic systems including the benzimidazolone moiety with biological activities therefore is of much current importance (Mondieig et al., 2013 ▸; Lakhrissi et al., 2008 ▸; Ouzidan et al., 2011 ▸; Dardouri et al., 2011 ▸). In this context, we are interested in the synthesis of the title compound, 1-{[2-oxo-3-(prop-1-en-2-yl)2,3-dihydro-1H-1,3-benzodiazol-1-yl)methyl}-3-(prop-1-en-2-yl)-2,3-dihydro-1H-1,3-benzodiazol-2-one, by reaction of dichloromethane with 1-(prop-1-en-2-yl)-1H-benzimidazol-2(3H)-one under phase-transfer catalysis (PTC) conditions using tetra-n-butylammonium bromide (TBAB) as catalyst and potassium carbonate as base. We report herein its crystal and molecular structures along with the Hirshfeld surface analysis.
Structural commentary
In the title compound (Fig. 1 ▸), the intramolecular C—H⋯O hydrogen-bonded (Table 1 ▸) benzodiazolone moieties are planar with the largest deviations being 0.017 (1) Å for atom C7 in the N1-containing unit (r.m.s. deviation = 0.011 Å) and 0.026 (1) Å for atom C18 in the N3-containing unit (r.m.s. deviation = 0.019 Å). The dihedral angle between the mean planes of the benzodiazolone moieties is 57.35 (3)°.
Figure 1.
The title molecule with the labelling scheme and 50% probability ellipsoids. Intramolecular C—H⋯O hydrogen bonds are shown as dashed lines.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C5—H5⋯O2 | 0.951 (14) | 2.493 (14) | 3.3598 (11) | 151.4 (10) |
| C10—H10A⋯O1i | 0.986 (14) | 2.596 (14) | 3.3498 (12) | 133.3 (11) |
| C10—H10B⋯O2vi | 0.998 (14) | 2.488 (14) | 3.4780 (12) | 171.4 (11) |
| C13—H13⋯O1 | 0.961 (13) | 2.477 (13) | 3.3381 (11) | 149.1 (11) |
Symmetry codes: (i) 
; (vi) 
.
Supramolecular features
Hydrogen bonding and van der Waals contacts are the dominant interactions in the crystal packing. In the crystal, two sets of intermolecular C—H⋯O hydrogen bonds (Table 1 ▸) generate layers parallel to the bc plane. In these layers, one of the benzodiazole units in each molecule is approximately parallel to the bc plane while the other half of the molecule protrudes from the surface (Fig. 2 ▸).
Figure 2.
The packing viewed along the b-axis direction giving an elevation view of two adjacent layers. Intermolecular C—H⋯O hydrogen bonds are shown as dashed lines.
Hirshfeld surface analysis
In order to visualize the intermolecular interactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis (Hirshfeld, 1977 ▸; Spackman & Jayatilaka, 2009 ▸) was carried out by using CrystalExplorer17.5 (Turner et al., 2017 ▸). In the HS plotted over d norm (Fig. 3 ▸), 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 (in close contact) or longer (distinct contact) than the van der Waals radii (Venkatesan et al., 2016 ▸). The bright-red spots appearing near O1, O2 and hydrogen atoms H5, H10A and H10B indicate their roles as the respective donors and acceptors in the dominant C—H ⋯ O hydrogen bonds; they also appear as blue and red regions corresponding to positive and negative potentials on the HS mapped over electrostatic potential (Spackman et al., 2008 ▸; Jayatilaka et al., 2005 ▸) as shown in Fig. 4 ▸. The blue regions indicate positive electrostatic potential (hydrogen-bond donors), while the red regions indicate negative electrostatic potential (hydrogen-bond acceptors). The shape-index of the HS is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π interactions. Fig. 5 ▸ clearly indicates that no π–π interactions are present in the title structure.
Figure 3.
View of the three-dimensional Hirshfeld surface of the title compound plotted over d norm in the range −0.1476 to 1.2686 a.u.
Figure 4.
View of the three-dimensional Hirshfeld surface of the title compound plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u. using the STO-3 G basis set at the Hartree–Fock level of theory. Hydrogen-bond donors and acceptors are shown as blue and red regions, respectively, around the atoms corresponding to positive and negative potentials.
Figure 5.
Hirshfeld surface of the title compound plotted over shape-index.
The overall two-dimensional fingerprint plot, Fig. 6 ▸ a, and those delineated into H⋯H, H⋯C/C⋯H, H⋯O/O⋯H, H⋯N/N⋯H, C⋯C and N⋯C/C⋯N contacts (McKinnon et al., 2007 ▸) are illustrated in Fig. 6 ▸ b–g, respectively, together with their relative contributions to the Hirshfeld surface. The most important contribution to the overall crystal packing (51.8%) is from H⋯H interactions, which are shown in Fig. 6 ▸ b as widely scattered points of high density due to the large hydrogen content of the molecule. The spike with the tip at d e = d i = 1.08 Å in Fig. 6 ▸ b is due to the short interatomic H⋯H contacts (Table 2 ▸). The fingerprint plot, Fig. 6 ▸ c, delineated into H⋯C/C⋯H contacts, which make a 30.7% contribution to the HS, shows a pair of characteristic wings and a pair of spikes with the tips at d e + d i ∼2.65 Å. The H⋯O/O⋯H contacts in the structure with a 11.2% contribution to the HS have a symmetrical distribution of points, Fig. 6 ▸ d, with the tips at d e + d i = 2.40 Å arising from the short intra- and/or interatomic C—H ⋯ O hydrogen bonding (Table 1 ▸) as well as from the H⋯O/O⋯H contacts (Table 2 ▸). Finally, the H⋯N/N⋯H (Fig. 6 ▸ e) contacts in the structure with a 5.1% contribution to the HS also have a symmetrical distribution of points, with the pair of wings appearing at d e + d i = 2.80 Å.
Figure 6.
The full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯O/O⋯H, (e) H⋯N/N⋯H, (f) C⋯C and (g) N⋯C/C⋯N interactions. The d i and d e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.
Table 2. Selected interatomic distances (Å).
| O1⋯C10 | 3.2233 (12) | C3⋯H11A vi | 3.017 (12) |
| O1⋯C13 | 3.3381 (12) | C4⋯H20B vii | 3.013 (14) |
| O1⋯C10i | 3.3499 (12) | C5⋯H11A | 2.980 (12) |
| O2⋯C20 | 3.1500 (13) | C7⋯H13 | 3.084 (13) |
| O2⋯C5 | 3.3598 (12) | C7⋯H21B v | 2.962 (14) |
| O1⋯H11B | 2.510 (12) | C7⋯H10A | 2.891 (14) |
| O1⋯H13 | 2.477 (13) | C8⋯H2 | 2.956 (13) |
| O1⋯H10A i | 2.595 (14) | C9⋯H2 | 2.981 (13) |
| O1⋯H20C ii | 2.917 (15) | C9⋯H15ix | 2.898 (13) |
| O1⋯H10A | 2.667 (14) | C10⋯H9B x | 3.051 (14) |
| O2⋯H3iii | 2.772 (13) | C11⋯H2iii | 3.077 (13) |
| O2⋯H5 | 2.493 (14) | C11⋯H13 | 3.009 (13) |
| O2⋯H11A | 2.505 (12) | C11⋯H5 | 2.972 (13) |
| O2⋯H20C | 2.581 (15) | C13⋯H11B | 2.965 (12) |
| O2⋯H10B iv | 2.487 (14) | C13⋯H9A iii | 3.051 (14) |
| O2⋯H15v | 2.781 (14) | C14⋯H9A iii | 2.989 (14) |
| N1⋯C3iv | 3.3814 (12) | C16⋯H21A | 3.080 (14) |
| N2⋯C21v | 3.4318 (13) | C17⋯H21A | 2.979 (14) |
| N3⋯H3iii | 2.938 (13) | C18⋯H16v | 2.858 (14) |
| N3⋯H16v | 2.920 (14) | C18⋯H5 | 3.093 (14) |
| C1⋯C21v | 3.5839 (13) | C18⋯H20C | 2.852 (15) |
| C2⋯C11vi | 3.5159 (12) | C18⋯H3iii | 2.701 (13) |
| C2⋯C9 | 3.4314 (13) | C19⋯H16 | 2.977 (14) |
| C3⋯C18vii | 3.3908 (13) | C21⋯H16 | 2.874 (14) |
| C3⋯C11vi | 3.3994 (12) | H2⋯H11B vii | 2.428 (18) |
| C7⋯C21v | 3.5253 (13) | H5⋯H11A | 2.583 (18) |
| C16⋯C21 | 3.3315 (14) | H9B⋯H10C | 2.495 (19) |
| C16⋯C18viii | 3.4599 (13) | H9B⋯H10B x | 2.44 (2) |
| C1⋯H21A v | 2.941 (14) | H9B⋯H15ix | 2.578 (19) |
| C1⋯H9A | 3.064 (13) | H10C⋯H9B | 2.495 (19) |
| C1⋯H11A vi | 2.946 (12) | H20A⋯H21B | 2.45 (2) |
| C2⋯H11A vi | 2.786 (12) | H20A⋯H20A xi | 2.34 (2) |
Symmetry codes: (i) ; (ii) 
; (iii) 
; (iv) 
; (v) 
; (vi) ; (vii) 
; (viii) 
; (ix) 
; (x) 
; (xi) 
.
The Hirshfeld surface representations for the function dnorm are shown for the H⋯H, H⋯C/C⋯H, H⋯O/O⋯H and H⋯N/N⋯H interactions in Fig. 7 ▸ a–d, respectively.
Figure 7.
The Hirshfeld surface representations with the function d norm plotted onto the surface for (a) H⋯H, (b) H⋯C/C⋯H, (c) H⋯O/O⋯H and (d) H⋯N/N⋯H interactions.
The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ▸).
Database survey
A search of the Cambridge Structural Database (CSD, version 5.39, update of August 2018; Groom et al., 2016 ▸) for benzimidazolin-2-one derivatives in which both nitrogen atoms form exocyclic C—N bonds gave 61 hits. In these structures, the bicyclic ring system is either planar, has a slight twist end-to-end or, in the cases where the exocyclic substituents form a ring, has a very shallow bowl shape. The closest examples to the title compound are NOTQUI (Díez-Barra et al., 1997 ▸) and XEVJOX (Huang et al., 2001 ▸) with ZICNEE (Shi & Thummel, 1995 ▸) as a more distant relative (see Fig. 8 ▸). In XEVJOX, the N—C—N angle connecting the two bicyclic units [114.19 (12)°] is essentially the same as in the title compound [114.04 (7)°]. In both of these, the bicyclic units are in an anti arrangement and this is basically the same for ZICNEE. Interestingly, the three bicyclic units in NOTQUI are close to all being syn to one another.
Figure 8.
NOTQUI, XEVJOX and ZICNEE.
Synthesis and crystallization
To a solution of 1-(prop-1-en-2-yl)-1H-benzimidazol-2(3H)-one (2.87mmol) in dichloromethane (30 ml) as reagent and solvent were added potassium carbonate (5.71 mmol) and a catalytic amount of tetra-n-butylammonium bromide (0.37 mmol). The mixture was heated for 24 h. The solid material was removed by filtration and the solvent evaporated under vacuum. The solid product was purified by recrystallization from ethanol solution to afford colourless crystals in 67% yield.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. H atoms were located in a difference-Fourier map and were freely refined.
Table 3. Experimental details.
| Crystal data | |
| Chemical formula | C21H20N4O2 |
| M r | 360.41 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 100 |
| a, b, c (Å) | 11.5244 (5), 8.6312 (4), 17.9845 (8) |
| β (°) | 94.134 (1) |
| V (Å3) | 1784.25 (14) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.09 |
| Crystal size (mm) | 0.40 × 0.39 × 0.22 |
| Data collection | |
| Diffractometer | Bruker SMART APEX CCD |
| Absorption correction | Multi-scan (SADABS; Krause et al., 2015 ▸) |
| T min, T max | 0.89, 0.98 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 33699, 4912, 4269 |
| R int | 0.027 |
| (sin θ/λ)max (Å−1) | 0.696 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.039, 0.113, 1.09 |
| No. of reflections | 4912 |
| No. of parameters | 324 |
| H-atom treatment | All H-atom parameters refined |
| Δρmax, Δρmin (e Å−3) | 0.47, −0.18 |
Supplementary Material
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018015219/xu5947sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018015219/xu5947Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989018015219/xu5947Isup3.cdx
Supporting information file. DOI: 10.1107/S2056989018015219/xu5947Isup4.cml
CCDC reference: 1875883
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Crystal data
| C21H20N4O2 | F(000) = 760 |
| Mr = 360.41 | Dx = 1.342 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 11.5244 (5) Å | Cell parameters from 9896 reflections |
| b = 8.6312 (4) Å | θ = 2.3–29.6° |
| c = 17.9845 (8) Å | µ = 0.09 mm−1 |
| β = 94.134 (1)° | T = 100 K |
| V = 1784.25 (14) Å3 | Block, colourless |
| Z = 4 | 0.40 × 0.39 × 0.22 mm |
Data collection
| Bruker SMART APEX CCD diffractometer | 4912 independent reflections |
| Radiation source: fine-focus sealed tube | 4269 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.027 |
| Detector resolution: 8.3333 pixels mm-1 | θmax = 29.7°, θmin = 1.8° |
| φ and ω scans | h = −15→15 |
| Absorption correction: multi-scan (SADABS; Krause et al., 2015) | k = −11→11 |
| Tmin = 0.89, Tmax = 0.98 | l = −25→25 |
| 33699 measured reflections |
Refinement
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.113 | All H-atom parameters refined |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0731P)2 + 0.248P] where P = (Fo2 + 2Fc2)/3 |
| 4912 reflections | (Δ/σ)max < 0.001 |
| 324 parameters | Δρmax = 0.47 e Å−3 |
| 0 restraints | Δρmin = −0.18 e Å−3 |
Special details
| Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = –30.00 and 210.00°. The scan time was 15 sec/frame. |
| 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 | 0.14989 (6) | 0.48310 (8) | 0.43717 (4) | 0.01960 (15) | |
| O2 | 0.23203 (6) | 0.33229 (8) | 0.13640 (4) | 0.01728 (15) | |
| N1 | 0.15509 (6) | 0.53341 (9) | 0.30979 (4) | 0.01421 (16) | |
| N2 | 0.14171 (6) | 0.73261 (9) | 0.38646 (4) | 0.01478 (16) | |
| N3 | 0.26416 (6) | 0.31586 (9) | 0.26564 (4) | 0.01347 (16) | |
| N4 | 0.39789 (6) | 0.21797 (9) | 0.19636 (4) | 0.01465 (16) | |
| C1 | 0.14167 (7) | 0.79263 (10) | 0.31433 (5) | 0.01364 (17) | |
| C2 | 0.13453 (8) | 0.94353 (11) | 0.28808 (5) | 0.01628 (18) | |
| H2 | 0.1277 (11) | 1.0298 (15) | 0.3234 (7) | 0.020 (3)* | |
| C3 | 0.13427 (8) | 0.96453 (11) | 0.21101 (5) | 0.01748 (18) | |
| H3 | 0.1274 (10) | 1.0686 (15) | 0.1888 (7) | 0.021 (3)* | |
| C4 | 0.14246 (8) | 0.83917 (11) | 0.16280 (5) | 0.01769 (18) | |
| H4 | 0.1443 (11) | 0.8573 (15) | 0.1091 (7) | 0.021 (3)* | |
| C5 | 0.15041 (8) | 0.68681 (11) | 0.18947 (5) | 0.01611 (18) | |
| H5 | 0.1568 (11) | 0.5978 (16) | 0.1588 (7) | 0.024 (3)* | |
| C6 | 0.14948 (7) | 0.66652 (10) | 0.26575 (5) | 0.01342 (17) | |
| C7 | 0.14860 (7) | 0.57243 (10) | 0.38459 (5) | 0.01462 (17) | |
| C8 | 0.12521 (8) | 0.81967 (11) | 0.45309 (5) | 0.01582 (18) | |
| C9 | 0.20574 (8) | 0.92203 (12) | 0.47637 (5) | 0.02068 (19) | |
| H9A | 0.2757 (12) | 0.9366 (16) | 0.4506 (7) | 0.027 (3)* | |
| H9B | 0.1940 (12) | 0.9911 (16) | 0.5186 (7) | 0.027 (3)* | |
| C10 | 0.01276 (8) | 0.78748 (12) | 0.48653 (5) | 0.01963 (19) | |
| H10A | 0.0075 (12) | 0.6777 (17) | 0.5012 (8) | 0.029 (3)* | |
| H10B | −0.0541 (12) | 0.8114 (16) | 0.4499 (8) | 0.026 (3)* | |
| H10C | 0.0073 (11) | 0.8515 (16) | 0.5326 (8) | 0.027 (3)* | |
| C11 | 0.15234 (7) | 0.37476 (10) | 0.28445 (5) | 0.01449 (17) | |
| H11A | 0.0994 (10) | 0.3665 (14) | 0.2396 (7) | 0.016 (3)* | |
| H11B | 0.1243 (11) | 0.3110 (14) | 0.3247 (7) | 0.018 (3)* | |
| C12 | 0.35153 (7) | 0.25387 (10) | 0.31484 (5) | 0.01369 (17) | |
| C13 | 0.36158 (8) | 0.24451 (11) | 0.39187 (5) | 0.01675 (18) | |
| H13 | 0.3032 (11) | 0.2870 (16) | 0.4215 (7) | 0.022 (3)* | |
| C14 | 0.46041 (9) | 0.16942 (11) | 0.42436 (5) | 0.01995 (19) | |
| H14 | 0.4683 (12) | 0.1616 (16) | 0.4794 (8) | 0.027 (3)* | |
| C15 | 0.54473 (8) | 0.10818 (12) | 0.38065 (5) | 0.0208 (2) | |
| H15 | 0.6129 (12) | 0.0591 (17) | 0.4037 (7) | 0.031 (3)* | |
| C16 | 0.53439 (8) | 0.11942 (11) | 0.30305 (5) | 0.01861 (19) | |
| H16 | 0.5928 (11) | 0.0792 (17) | 0.2729 (8) | 0.028 (3)* | |
| C17 | 0.43617 (7) | 0.19291 (10) | 0.27099 (5) | 0.01441 (17) | |
| C18 | 0.29128 (7) | 0.29272 (10) | 0.19241 (5) | 0.01344 (17) | |
| C19 | 0.45369 (8) | 0.16277 (10) | 0.13270 (5) | 0.01655 (18) | |
| C20 | 0.38248 (9) | 0.05439 (13) | 0.08298 (6) | 0.0238 (2) | |
| H20A | 0.4249 (13) | 0.0262 (18) | 0.0389 (8) | 0.040 (4)* | |
| H20B | 0.3693 (12) | −0.0429 (18) | 0.1112 (8) | 0.034 (4)* | |
| H20C | 0.3068 (13) | 0.0959 (18) | 0.0661 (8) | 0.033 (3)* | |
| C21 | 0.56303 (9) | 0.20343 (13) | 0.12450 (6) | 0.0232 (2) | |
| H21A | 0.6039 (12) | 0.2754 (17) | 0.1589 (8) | 0.028 (3)* | |
| H21B | 0.6045 (12) | 0.1602 (16) | 0.0827 (8) | 0.030 (3)* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0239 (3) | 0.0166 (3) | 0.0187 (3) | 0.0040 (3) | 0.0045 (3) | 0.0038 (2) |
| O2 | 0.0170 (3) | 0.0173 (3) | 0.0171 (3) | 0.0021 (2) | −0.0019 (2) | 0.0004 (2) |
| N1 | 0.0163 (3) | 0.0111 (4) | 0.0153 (3) | 0.0012 (3) | 0.0022 (3) | −0.0005 (3) |
| N2 | 0.0180 (3) | 0.0121 (4) | 0.0143 (3) | 0.0011 (3) | 0.0021 (3) | −0.0008 (3) |
| N3 | 0.0124 (3) | 0.0133 (3) | 0.0146 (3) | 0.0022 (3) | 0.0004 (3) | −0.0010 (3) |
| N4 | 0.0134 (3) | 0.0157 (4) | 0.0149 (3) | 0.0026 (3) | 0.0016 (3) | −0.0004 (3) |
| C1 | 0.0114 (4) | 0.0139 (4) | 0.0156 (4) | −0.0004 (3) | 0.0006 (3) | −0.0006 (3) |
| C2 | 0.0157 (4) | 0.0132 (4) | 0.0198 (4) | −0.0015 (3) | 0.0004 (3) | −0.0014 (3) |
| C3 | 0.0171 (4) | 0.0145 (4) | 0.0206 (4) | −0.0030 (3) | −0.0002 (3) | 0.0024 (3) |
| C4 | 0.0173 (4) | 0.0187 (5) | 0.0169 (4) | −0.0025 (3) | 0.0001 (3) | 0.0022 (3) |
| C5 | 0.0158 (4) | 0.0163 (4) | 0.0162 (4) | −0.0006 (3) | 0.0008 (3) | −0.0016 (3) |
| C6 | 0.0111 (4) | 0.0116 (4) | 0.0175 (4) | 0.0000 (3) | 0.0007 (3) | −0.0003 (3) |
| C7 | 0.0129 (4) | 0.0142 (4) | 0.0169 (4) | 0.0016 (3) | 0.0024 (3) | −0.0005 (3) |
| C8 | 0.0178 (4) | 0.0159 (4) | 0.0138 (4) | 0.0052 (3) | 0.0008 (3) | −0.0013 (3) |
| C9 | 0.0204 (4) | 0.0202 (5) | 0.0213 (4) | 0.0016 (4) | 0.0007 (3) | −0.0049 (4) |
| C10 | 0.0173 (4) | 0.0237 (5) | 0.0181 (4) | 0.0029 (3) | 0.0031 (3) | −0.0017 (4) |
| C11 | 0.0114 (4) | 0.0116 (4) | 0.0206 (4) | 0.0004 (3) | 0.0018 (3) | −0.0020 (3) |
| C12 | 0.0134 (4) | 0.0107 (4) | 0.0168 (4) | 0.0002 (3) | −0.0003 (3) | 0.0000 (3) |
| C13 | 0.0190 (4) | 0.0146 (4) | 0.0167 (4) | 0.0006 (3) | 0.0011 (3) | −0.0017 (3) |
| C14 | 0.0237 (5) | 0.0180 (4) | 0.0175 (4) | 0.0007 (3) | −0.0030 (3) | 0.0004 (3) |
| C15 | 0.0192 (4) | 0.0198 (5) | 0.0226 (4) | 0.0039 (3) | −0.0039 (3) | 0.0015 (4) |
| C16 | 0.0153 (4) | 0.0186 (4) | 0.0218 (4) | 0.0035 (3) | 0.0010 (3) | 0.0002 (3) |
| C17 | 0.0142 (4) | 0.0129 (4) | 0.0160 (4) | −0.0002 (3) | 0.0003 (3) | −0.0003 (3) |
| C18 | 0.0133 (4) | 0.0108 (4) | 0.0162 (4) | −0.0008 (3) | 0.0012 (3) | −0.0011 (3) |
| C19 | 0.0181 (4) | 0.0157 (4) | 0.0163 (4) | 0.0027 (3) | 0.0044 (3) | 0.0008 (3) |
| C20 | 0.0235 (5) | 0.0256 (5) | 0.0231 (4) | −0.0021 (4) | 0.0070 (4) | −0.0083 (4) |
| C21 | 0.0180 (4) | 0.0292 (5) | 0.0230 (5) | 0.0011 (4) | 0.0053 (4) | 0.0011 (4) |
Geometric parameters (Å, º)
| O1—C7 | 1.2194 (11) | C8—C10 | 1.4936 (13) |
| O2—C18 | 1.2241 (11) | C9—H9A | 0.967 (13) |
| N1—C7 | 1.3938 (11) | C9—H9B | 0.982 (14) |
| N1—C6 | 1.3943 (11) | C10—H10A | 0.986 (14) |
| N1—C11 | 1.4428 (11) | C10—H10B | 0.998 (14) |
| N2—C7 | 1.3853 (12) | C10—H10C | 1.001 (14) |
| N2—C1 | 1.3969 (11) | C11—H11A | 0.978 (12) |
| N2—C8 | 1.4386 (11) | C11—H11B | 0.982 (12) |
| N3—C18 | 1.3899 (11) | C12—C13 | 1.3843 (12) |
| N3—C12 | 1.3980 (11) | C12—C17 | 1.4003 (12) |
| N3—C11 | 1.4478 (11) | C13—C14 | 1.4010 (13) |
| N4—C18 | 1.3850 (11) | C13—H13 | 0.961 (13) |
| N4—C17 | 1.3991 (11) | C14—C15 | 1.3970 (14) |
| N4—C19 | 1.4343 (11) | C14—H14 | 0.991 (14) |
| C1—C2 | 1.3858 (12) | C15—C16 | 1.3956 (13) |
| C1—C6 | 1.4026 (12) | C15—H15 | 0.960 (14) |
| C2—C3 | 1.3976 (13) | C16—C17 | 1.3863 (12) |
| C2—H2 | 0.986 (12) | C16—H16 | 0.959 (14) |
| C3—C4 | 1.3940 (13) | C19—C21 | 1.3265 (13) |
| C3—H3 | 0.984 (13) | C19—C20 | 1.4975 (14) |
| C4—C5 | 1.4005 (13) | C20—H20A | 0.992 (15) |
| C4—H4 | 0.980 (13) | C20—H20B | 0.998 (15) |
| C5—C6 | 1.3839 (12) | C20—H20C | 0.971 (15) |
| C5—H5 | 0.951 (14) | C21—H21A | 0.973 (14) |
| C8—C9 | 1.3271 (14) | C21—H21B | 0.993 (15) |
| O1···C10 | 3.2233 (12) | C3···H11Avi | 3.017 (12) |
| O1···C13 | 3.3381 (12) | C4···H20Bvii | 3.013 (14) |
| O1···C10i | 3.3499 (12) | C5···H11A | 2.980 (12) |
| O2···C20 | 3.1500 (13) | C7···H13 | 3.084 (13) |
| O2···C5 | 3.3598 (12) | C7···H21Bv | 2.962 (14) |
| O1···H11B | 2.510 (12) | C7···H10A | 2.891 (14) |
| O1···H13 | 2.477 (13) | C8···H2 | 2.956 (13) |
| O1···H10Ai | 2.595 (14) | C9···H2 | 2.981 (13) |
| O1···H20Cii | 2.917 (15) | C9···H15ix | 2.898 (13) |
| O1···H10A | 2.667 (14) | C10···H9Bx | 3.051 (14) |
| O2···H3iii | 2.772 (13) | C11···H2iii | 3.077 (13) |
| O2···H5 | 2.493 (14) | C11···H13 | 3.009 (13) |
| O2···H11A | 2.505 (12) | C11···H5 | 2.972 (13) |
| O2···H20C | 2.581 (15) | C13···H11B | 2.965 (12) |
| O2···H10Biv | 2.487 (14) | C13···H9Aiii | 3.051 (14) |
| O2···H15v | 2.781 (14) | C14···H9Aiii | 2.989 (14) |
| N1···C3iv | 3.3814 (12) | C16···H21A | 3.080 (14) |
| N2···C21v | 3.4318 (13) | C17···H21A | 2.979 (14) |
| N3···H3iii | 2.938 (13) | C18···H16v | 2.858 (14) |
| N3···H16v | 2.920 (14) | C18···H5 | 3.093 (14) |
| C1···C21v | 3.5839 (13) | C18···H20C | 2.852 (15) |
| C2···C11vi | 3.5159 (12) | C18···H3iii | 2.701 (13) |
| C2···C9 | 3.4314 (13) | C19···H16 | 2.977 (14) |
| C3···C18vii | 3.3908 (13) | C21···H16 | 2.874 (14) |
| C3···C11vi | 3.3994 (12) | H2···H11Bvii | 2.428 (18) |
| C7···C21v | 3.5253 (13) | H5···H11A | 2.583 (18) |
| C16···C21 | 3.3315 (14) | H9B···H10C | 2.495 (19) |
| C16···C18viii | 3.4599 (13) | H9B···H10Bx | 2.44 (2) |
| C1···H21Av | 2.941 (14) | H9B···H15ix | 2.578 (19) |
| C1···H9A | 3.064 (13) | H10C···H9B | 2.495 (19) |
| C1···H11Avi | 2.946 (12) | H20A···H21B | 2.45 (2) |
| C2···H11Avi | 2.786 (12) | H20A···H20Axi | 2.34 (2) |
| C7—N1—C6 | 110.21 (7) | C8—C10—H10C | 109.8 (8) |
| C7—N1—C11 | 122.19 (7) | H10A—C10—H10C | 107.5 (11) |
| C6—N1—C11 | 127.12 (7) | H10B—C10—H10C | 109.9 (11) |
| C7—N2—C1 | 110.10 (7) | N1—C11—N3 | 114.04 (7) |
| C7—N2—C8 | 123.56 (7) | N1—C11—H11A | 109.1 (7) |
| C1—N2—C8 | 126.06 (8) | N3—C11—H11A | 107.2 (7) |
| C18—N3—C12 | 110.11 (7) | N1—C11—H11B | 107.4 (7) |
| C18—N3—C11 | 122.45 (7) | N3—C11—H11B | 108.7 (7) |
| C12—N3—C11 | 126.81 (7) | H11A—C11—H11B | 110.4 (10) |
| C18—N4—C17 | 109.78 (7) | C13—C12—N3 | 131.31 (8) |
| C18—N4—C19 | 124.12 (7) | C13—C12—C17 | 122.02 (8) |
| C17—N4—C19 | 125.86 (7) | N3—C12—C17 | 106.66 (7) |
| C2—C1—N2 | 131.38 (8) | C12—C13—C14 | 116.83 (8) |
| C2—C1—C6 | 121.47 (8) | C12—C13—H13 | 121.4 (8) |
| N2—C1—C6 | 107.15 (8) | C14—C13—H13 | 121.7 (8) |
| C1—C2—C3 | 117.10 (8) | C15—C14—C13 | 121.19 (9) |
| C1—C2—H2 | 119.7 (7) | C15—C14—H14 | 121.3 (8) |
| C3—C2—H2 | 123.2 (7) | C13—C14—H14 | 117.5 (8) |
| C4—C3—C2 | 121.38 (8) | C16—C15—C14 | 121.58 (9) |
| C4—C3—H3 | 117.6 (7) | C16—C15—H15 | 118.0 (8) |
| C2—C3—H3 | 121.0 (7) | C14—C15—H15 | 120.4 (8) |
| C3—C4—C5 | 121.44 (8) | C17—C16—C15 | 117.13 (8) |
| C3—C4—H4 | 119.7 (8) | C17—C16—H16 | 121.1 (8) |
| C5—C4—H4 | 118.8 (8) | C15—C16—H16 | 121.8 (8) |
| C6—C5—C4 | 116.95 (8) | C16—C17—N4 | 131.39 (8) |
| C6—C5—H5 | 118.6 (8) | C16—C17—C12 | 121.25 (8) |
| C4—C5—H5 | 124.4 (8) | N4—C17—C12 | 107.33 (7) |
| C5—C6—N1 | 131.61 (8) | O2—C18—N4 | 127.76 (8) |
| C5—C6—C1 | 121.65 (8) | O2—C18—N3 | 126.13 (8) |
| N1—C6—C1 | 106.75 (7) | N4—C18—N3 | 106.11 (7) |
| O1—C7—N2 | 127.56 (8) | C21—C19—N4 | 119.01 (9) |
| O1—C7—N1 | 126.66 (8) | C21—C19—C20 | 125.66 (9) |
| N2—C7—N1 | 105.77 (7) | N4—C19—C20 | 115.23 (8) |
| C9—C8—N2 | 118.63 (8) | C19—C20—H20A | 110.5 (9) |
| C9—C8—C10 | 127.17 (8) | C19—C20—H20B | 108.6 (8) |
| N2—C8—C10 | 114.13 (8) | H20A—C20—H20B | 107.6 (12) |
| C8—C9—H9A | 121.6 (8) | C19—C20—H20C | 113.4 (9) |
| C8—C9—H9B | 121.1 (8) | H20A—C20—H20C | 108.9 (12) |
| H9A—C9—H9B | 117.2 (12) | H20B—C20—H20C | 107.6 (12) |
| C8—C10—H10A | 110.9 (8) | C19—C21—H21A | 121.2 (8) |
| C8—C10—H10B | 110.3 (8) | C19—C21—H21B | 119.9 (8) |
| H10A—C10—H10B | 108.4 (11) | H21A—C21—H21B | 118.9 (12) |
| C7—N2—C1—C2 | 178.97 (9) | C18—N3—C11—N1 | −106.27 (9) |
| C8—N2—C1—C2 | 4.89 (14) | C12—N3—C11—N1 | 83.78 (10) |
| C7—N2—C1—C6 | −0.36 (9) | C18—N3—C12—C13 | −177.76 (9) |
| C8—N2—C1—C6 | −174.44 (8) | C11—N3—C12—C13 | −6.78 (15) |
| N2—C1—C2—C3 | −178.63 (8) | C18—N3—C12—C17 | 1.01 (9) |
| C6—C1—C2—C3 | 0.62 (13) | C11—N3—C12—C17 | 171.99 (8) |
| C1—C2—C3—C4 | −0.86 (13) | N3—C12—C13—C14 | 178.01 (9) |
| C2—C3—C4—C5 | 0.49 (14) | C17—C12—C13—C14 | −0.60 (13) |
| C3—C4—C5—C6 | 0.15 (13) | C12—C13—C14—C15 | 0.41 (14) |
| C4—C5—C6—N1 | 179.51 (9) | C13—C14—C15—C16 | 0.17 (15) |
| C4—C5—C6—C1 | −0.39 (13) | C14—C15—C16—C17 | −0.55 (15) |
| C7—N1—C6—C5 | −178.70 (9) | C15—C16—C17—N4 | −177.31 (9) |
| C11—N1—C6—C5 | −6.53 (15) | C15—C16—C17—C12 | 0.36 (14) |
| C7—N1—C6—C1 | 1.21 (9) | C18—N4—C17—C16 | 177.76 (9) |
| C11—N1—C6—C1 | 173.38 (8) | C19—N4—C17—C16 | 3.22 (16) |
| C2—C1—C6—C5 | 0.00 (13) | C18—N4—C17—C12 | −0.16 (10) |
| N2—C1—C6—C5 | 179.41 (8) | C19—N4—C17—C12 | −174.69 (8) |
| C2—C1—C6—N1 | −179.92 (8) | C13—C12—C17—C16 | 0.22 (14) |
| N2—C1—C6—N1 | −0.51 (9) | N3—C12—C17—C16 | −178.69 (8) |
| C1—N2—C7—O1 | −179.53 (8) | C13—C12—C17—N4 | 178.40 (8) |
| C8—N2—C7—O1 | −5.27 (14) | N3—C12—C17—N4 | −0.51 (9) |
| C1—N2—C7—N1 | 1.08 (9) | C17—N4—C18—O2 | −179.70 (9) |
| C8—N2—C7—N1 | 175.34 (7) | C19—N4—C18—O2 | −5.05 (15) |
| C6—N1—C7—O1 | 179.19 (8) | C17—N4—C18—N3 | 0.76 (10) |
| C11—N1—C7—O1 | 6.57 (13) | C19—N4—C18—N3 | 175.42 (8) |
| C6—N1—C7—N2 | −1.42 (9) | C12—N3—C18—O2 | 179.36 (9) |
| C11—N1—C7—N2 | −174.04 (7) | C11—N3—C18—O2 | 7.92 (14) |
| C7—N2—C8—C9 | 120.14 (10) | C12—N3—C18—N4 | −1.10 (9) |
| C1—N2—C8—C9 | −66.54 (12) | C11—N3—C18—N4 | −172.54 (7) |
| C7—N2—C8—C10 | −62.69 (11) | C18—N4—C19—C21 | 127.96 (10) |
| C1—N2—C8—C10 | 110.64 (10) | C17—N4—C19—C21 | −58.25 (13) |
| C7—N1—C11—N3 | −105.28 (9) | C18—N4—C19—C20 | −55.46 (12) |
| C6—N1—C11—N3 | 83.41 (10) | C17—N4—C19—C20 | 118.33 (10) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x, y−1, z; (iv) −x, y−1/2, −z+1/2; (v) −x+1, y+1/2, −z+1/2; (vi) −x, y+1/2, −z+1/2; (vii) x, y+1, z; (viii) −x+1, y−1/2, −z+1/2; (ix) −x+1, −y+1, −z+1; (x) −x, −y+2, −z+1; (xi) −x+1, −y, −z.
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C5—H5···O2 | 0.951 (14) | 2.493 (14) | 3.3598 (11) | 151.4 (10) |
| C10—H10A···O1i | 0.986 (14) | 2.596 (14) | 3.3498 (12) | 133.3 (11) |
| C10—H10B···O2vi | 0.998 (14) | 2.488 (14) | 3.4780 (12) | 171.4 (11) |
| C13—H13···O1 | 0.961 (13) | 2.477 (13) | 3.3381 (11) | 149.1 (11) |
Symmetry codes: (i) −x, −y+1, −z+1; (vi) −x, y+1/2, −z+1/2.
Funding Statement
This work was funded by Tulane University grant . Hacettepe University Scientific Research Project Unit grant 013 D04 602 004 to T. Hökelek.
References
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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) I, global. DOI: 10.1107/S2056989018015219/xu5947sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018015219/xu5947Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989018015219/xu5947Isup3.cdx
Supporting information file. DOI: 10.1107/S2056989018015219/xu5947Isup4.cml
CCDC reference: 1875883
Additional supporting information: crystallographic information; 3D view; checkCIF report