Crystal structure and Hirshfeld surface analysis of 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

Saber, A.; Sebbar, N.K.; Hökelek, T.; Hni, B.; Mague, J.T.; Essassi, E.M.

doi:10.1107/S2056989018015219

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 74| Part 12| December 2018| Pages 1746-1750

https://doi.org/10.1107/S2056989018015219

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Crystal structure and Hirshfeld surface analysis of 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

Asmaa Saber,^a ^* Nada Kheira Sebbar,^b Tuncer Hökelek,^c Brahim Hni,^a Joel T. Mague ^d and El Mokhtar Essassi ^a

^aLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, ^bLaboratoire de Chimie Bioorganique Appliquée, Faculté des Sciences, Université Ibn Zohr, Agadir, Morocco, ^cDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, and ^dDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: as.saber.pro@gmail.com

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 23 October 2018; accepted 28 October 2018; online 9 November 2018)

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.

Keywords: crystal structure; hydrogen bond; benzodiazolone; Hirshfeld surface.

CCDC reference: 1875883

1. 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.

2. 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)°.

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⋯O2^vi	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) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The title molecule with the labelling scheme and 50% probability ellipsoids. Intramolecular C—H⋯O hydrogen bonds are shown as dashed lines.

3. 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.

4. 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. 6a, 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. 6b–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. 6b 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. 6b is due to the short interatomic H⋯H contacts (Table 2). The fingerprint plot, Fig. 6c, 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. 6d, 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. 6e) 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.

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⋯H10Aⁱ	2.595 (14)	C9⋯H2	2.981 (13)
O1⋯H20Cⁱⁱ	2.917 (15)	C9⋯H15^ix	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⋯H9Aⁱⁱⁱ	3.051 (14)
O2⋯H15^v	2.781 (14)	C14⋯H9Aⁱⁱⁱ	2.989 (14)
N1⋯C3^iv	3.3814 (12)	C16⋯H21A	3.080 (14)
N2⋯C21^v	3.4318 (13)	C17⋯H21A	2.979 (14)
N3⋯H3ⁱⁱⁱ	2.938 (13)	C18⋯H16^v	2.858 (14)
N3⋯H16^v	2.920 (14)	C18⋯H5	3.093 (14)
C1⋯C21^v	3.5839 (13)	C18⋯H20C	2.852 (15)
C2⋯C11^vi	3.5159 (12)	C18⋯H3ⁱⁱⁱ	2.701 (13)
C2⋯C9	3.4314 (13)	C19⋯H16	2.977 (14)
C3⋯C18^vii	3.3908 (13)	C21⋯H16	2.874 (14)
C3⋯C11^vi	3.3994 (12)	H2⋯H11B^vii	2.428 (18)
C7⋯C21^v	3.5253 (13)	H5⋯H11A	2.583 (18)
C16⋯C21	3.3315 (14)	H9B⋯H10C	2.495 (19)
C16⋯C18^viii	3.4599 (13)	H9B⋯H10B^x	2.44 (2)
C1⋯H21A^v	2.941 (14)	H9B⋯H15^ix	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) -x, -y+1, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x, y-1, z; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) x, y+1, z; (viii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ix) -x+1, -y+1, -z+1; (x) -x, -y+2, -z+1; (xi) -x+1, -y, -z.

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.

The Hirshfeld surface representations for the function d_norm are shown for the H⋯H, H⋯C/C⋯H, H⋯O/O⋯H and H⋯N/N⋯H interactions in Fig. 7a–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 ).

5. 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.

6. 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.

7. 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[F² > 2σ(F²)], wR(F²), S	0.039, 0.113, 1.09
No. of reflections	4912
No. of parameters	324
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.18
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1875883

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018015219/xu5947sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018015219/xu5947Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018015219/xu5947Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2056989018015219/xu5947Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); 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).

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 top

Crystal data top

C₂₁H₂₀N₄O₂	F(000) = 760
M_r = 360.41	D_x = 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 top

Bruker SMART APEX CCD diffractometer	4912 independent reflections
Radiation source: fine-focus sealed tube	4269 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 8.3333 pixels mm^-1	θ_max = 29.7°, θ_min = 1.8°
φ and ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −11→11
T_min = 0.89, T_max = 0.98	l = −25→25
33699 measured reflections

Refinement top

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(F_o²) + (0.0731P)² + 0.248P] where P = (F_o² + 2F_c²)/3
4912 reflections	(Δ/σ)_max < 0.001
324 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Special details top

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) top

	x	y	z	U_iso*/U_eq
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) top

	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) top

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···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···H10Aⁱ	2.595 (14)	C9···H2	2.981 (13)
O1···H20Cⁱⁱ	2.917 (15)	C9···H15^ix	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···H9Aⁱⁱⁱ	3.051 (14)
O2···H15^v	2.781 (14)	C14···H9Aⁱⁱⁱ	2.989 (14)
N1···C3^iv	3.3814 (12)	C16···H21A	3.080 (14)
N2···C21^v	3.4318 (13)	C17···H21A	2.979 (14)
N3···H3ⁱⁱⁱ	2.938 (13)	C18···H16^v	2.858 (14)
N3···H16^v	2.920 (14)	C18···H5	3.093 (14)
C1···C21^v	3.5839 (13)	C18···H20C	2.852 (15)
C2···C11^vi	3.5159 (12)	C18···H3ⁱⁱⁱ	2.701 (13)
C2···C9	3.4314 (13)	C19···H16	2.977 (14)
C3···C18^vii	3.3908 (13)	C21···H16	2.874 (14)
C3···C11^vi	3.3994 (12)	H2···H11B^vii	2.428 (18)
C7···C21^v	3.5253 (13)	H5···H11A	2.583 (18)
C16···C21	3.3315 (14)	H9B···H10C	2.495 (19)
C16···C18^viii	3.4599 (13)	H9B···H10B^x	2.44 (2)
C1···H21A^v	2.941 (14)	H9B···H15^ix	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)

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) top

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···O2^vi	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 information

JTM thanks 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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