Crystal structure and Hirshfeld surface analysis of 7-eth­oxy-5-methyl-2-(pyridin-3-yl)-11,12-di­hydro-5,11-methano­[1,2,4]triazolo[1,5-c][1,3,5]benzoxadiazo­cine

Aydemir, E.; Kansiz, S.; Gumus, M.K.; Gorobets, N.Y.; Dege, N.

doi:10.1107/S2056989018002621

research communications

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ISSN: 2056-9890

Volume 74| Part 3| March 2018| Pages 367-370

https://doi.org/10.1107/S2056989018002621

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Crystal structure and Hirshfeld surface analysis of 7-ethoxy-5-methyl-2-(pyridin-3-yl)-11,12-dihydro-5,11-methano[1,2,4]triazolo[1,5-c][1,3,5]benzoxadiazocine

Ercan Aydemir,^a,^b Sevgi Kansiz,^c ^* Mustafa Kemal Gumus,^b Nikolay Yu. Gorobets ^d,^e and Necmi Dege ^c

^aT.R. Ministry of Forestry and Water Affairs, 11th Regional Directorate, 55030, Ilkadım, Samsun, Turkey, ^bArtvin Coruh University, Science-Technology Research and Application Center, Artvin 08000, Turkey, ^cOndokuz Mayıs University, Faculty of Arts and Sciences, Department of Physics, 55139, Kurupelit, Samsun, Turkey, ^dSSI "Institute for Single Crystals" of National Academy of Sciences of Ukraine, 60 Nauky Ave., Kharkiv 61072, Ukraine, and ^eV.N. Karazin Kharkiv National University, Svobody sq. 4, Kharkiv 61077, Ukraine
^*Correspondence e-mail: sevgi.koroglu@omu.edu.tr

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 30 January 2018; accepted 13 February 2018; online 20 February 2018)

The title compound, C₁₉H₁₉N₅O₂, was prepared by the reaction of 3-amino-5-(pyridin-3-yl)-1,2,4-triazole with acetone and 2-hydroxy-3-ethoxybenzaldehyde. It crystallizes from ethanol in a tetragonal space group, with one molecule in the asymmetric unit. The 1,2,4-triazole five-membered ring is planar (maximum deviation = 0.0028 Å). The pyridine and phenyl rings are also planar with maximum deviations of 0.0091 and 0.0094 Å, respectively. In the crystal, N—H⋯N hydrogen bonds link the molecules into supramolecular chains propagating along the c-axis direction. Hirshfeld surface analysis and two-dimensional fingerprint plots have been used to analyse the intermolecular interactions present in the crystal.

Keywords: crystal structure; Biginelli condensation; benzoxadiazocine; Hirshfeld surfaces.

CCDC reference: 1820439

1. Chemical context

The title compound represents a conformationally restricted analogue of so-called Biginelli compounds known to exhibit multiple pharmacological activities. It was selected for a single-crystal X-ray analysis in order to probe the chemical and spatial requirements of some kinds of activity. 4-Aryl-3,4-dihydropyrimidine-2(1H)-ones and -thiones, known as Biginelli compounds, display a wide spectrum of significant pharmacological activities (Kappe, 2000 ). For example, these pyrimidine derivatives were assayed as antihypertensive agents, selective α_1a-adrenergic receptor antagonists, neuropeptide Y antagonists and were used as a lead for the development of anticancer drugs (Kappe, 2000). The Biginelli products have also been found to be potent hepatitis B replication inhibitors (Deres et al., 2003 ).

Recently, the ability of oxygen-bridged azolopyrimidine derivatives to inhibit Eg5 activity has been examined (Svetlík et al., 2010 ). As each of the above activities originates from stereo-selective binding of the drug molecule to its specific receptor, it is of interest to design a conformationally restricted probe molecule in order to examine geometric requirements of the given receptor binding site.

Since we had previously synthesized such a rigid type of oxygen-bridged triazolo-pyrimidine derivative, (I) (Gümüş et al., 2017 ), we decided to examine the structure of this heterocyclic system by X-ray analysis. A novel Biginelli-like assembly of 3-amino-5-(pyridin-3-yl)-1,2,4-triazole with acetone and 2-hydroxy-3-ethoxybenzaldehyde has been developed to enable easy access to 7-ethoxy-5-methyl-2-(pyridin-3-yl)-11,12-dihydro-5,11-methano[1,2,4]triazolo[1,5-c][1,3,5]benzoxadiazocine compounds as representatives of a new class of heterocycles.

2. Structural commentary

The asymmetric unit of the title compound contains one independent molecule (Fig. 1). In the 1,2,4-triazole ring, the average C=N and C—N bond lengths are 1.324 and 1.355 Å, respectively, while the N—N bond is 1.389 (4) Å. These values consistent with literature values (Şen et al., 2017a ,b ; Atalay et al., 2004 ). The 1,2,4-triazole ring is planar with a maximum deviation of 0.0028 Å. The N1/C1–C5 and C12–C17 rings are also planar with maximum deviations of 0.0091 and 0.0094 Å, respectively. The dihedral angle between the N1/C1–C5 and C6/N2/N3/C7/N4 rings is 13.1 (2)°, while the latter ring is inclined to the N3/C10–C8/N5/C7 plane by 6.87 (15)°. The C12–C17 and N3/C10–C8/N5/C7 planes form dihedral angles of 7.8 (2) and 88.82 (12)°, respectively, with the C9/C10/O1/C12/C13 plane.

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

3. Supramolecular features

In the crystal, the N—H⋯N hydrogen bonds link the molecules, forming the supramolecular chains propagating along the c-axis direction (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯N1ⁱ	0.86	2.13	2.907 (4)	149
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A partial view of the crystal packing of the title compound. Dashed lines denote the intermolecular N—H⋯N hydrogen bonds.

4. Hirshfeld surface analysis

Crystal Explorer17.5 (Turner et al., 2017 ) was used to analyse the interactions in the crystal; fingerprint plots mapped over d_norm (Figs. 3 and 4) were generated. The molecular Hirshfeld surfaces were obtained using a standard (high) surface resolution with the three-dimentional d_norm surfaces mapped over a fixed colour scale of −0.484 (red) to 1.652 (blue). There are two red spots in the d_norm surface (Fig. 3), which are on the N-acceptor atoms involved in the interactions listed in Table 1. The red spots indicate the regions of donor–acceptor interactions (Kansiz et al., 2018 ; Şen et al., 2017a,b, 2018 ; Yaman et al., 2018 ).

Figure 3
The Hirshfeld surface of C₁₉H₁₉N₅O₂ mapped with d_norm.

Figure 4
d_norm mapped on Hirshfeld surfaces to visualize the intermolecular interactions of C₁₉H₁₉N₅O₂.

The intermolecular interactions of the title compound are shown in the 2D fingerprint plots shown in Fig. 5. The H⋯H interactions appear in the middle of the scattered points in the two-dimensional fingerprint plots with a contribution to the overall Hirshfeld surface of 52.6% (Fig. 6). The contribution from the N⋯H/H⋯N contacts, corresponding to the N—H⋯N interaction, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bond interaction (16.3%). The whole fingerprint region and all other interactions, which are a combination of d_e and d_i, are displayed in Fig. 6.

Figure 5
Fingerprint plot of the title compound.

Figure 6
Two-dimensional fingerprint plots with a d_norm view of the H⋯H/H⋯H (52.6%), C⋯H/H⋯C (18.9%), N⋯H/H⋯N (16.3%) and O⋯H/H⋯O (7.2%) contacts in the title compound.

5. Database survey

There are no direct precedents for the structure of (I) in the crystallographic literature (CSD Version 5.38; Groom et al., 2016 ). However, there are several precedents for the triazolobenzoxadiazocines, including the structures of 5-(2-hydroxyphenyl)-7-methyl-4,5,6,7-tetrahydro[1,2,4]triazolo[1,5-a]pyrimidin-7-ol (Gorobets et al., 2010 ), ethyl 7-chloromethyl-5-(2-chlorophenyl)-7-hydroxy-2-methylsulfanyl-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxylate (Huang, 2009 ) and methyl 5′-(2-hydroxyphenyl)-5′,6′-dihydro-4′H-spiro[chromene-2,7′-[1,2,4]triazolo[1,5-a]pyrimidine]-3-carboxylate (Kettmann & Světlík, 2011 ).

6. Synthesis and crystallization

The synthesis of the title compound (Fig. 7) was described by Gümüş et al. (2017). 3-Amino-5-(pyridin-3-yl)-1,2,4-triazole(1.0 mmol), 2-hydroxy-3-ethoxybenzaldehyde (1.0 mmol), acetone (0.22 mL, 3.0 mmol), and abs. EtOH (2.0 mL) were mixed in a microwave process vial, and then a 4 N solution of HCl in dioxane (0.07 mL, 0.3 mmol) was added. The mixture was irradiated at 423 K for 30 min. The reaction mixture was cooled by an air flow and stirred for 24 h at room temperature for complete precipitation of the product. The precipitate was filtered off, washed with EtOH (1.0 mL) and Et₂O (3 × 1.0 mL), and dried. Compound (I) was obtained in the form of a white solid. It was recrystallized from ethanol.

Figure 7
Synthesis of the title compound.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned geometrically [N—H = 0.86 Å, C—H = 0.93 (aromatic), 0.96 (methyl) and 0.97 (methylene) Å] and refined using a riding model, with U_iso(H) = 1.2U_eq(N, C) and 1.5U_eq(methyl C).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₉N₅O₂
M_r	349.39
Crystal system, space group	Tetragonal, I $[\overline{4}]$
Temperature (K)	293
a, c (Å)	17.1509 (8), 11.9033 (7)
V (Å³)	3501.4 (4)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.54 × 0.34 × 0.16

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002 )
T_min, T_max	0.959, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	8018, 3629, 2449
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.088, 0.90
No. of reflections	3629
No. of parameters	236
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.12
Absolute structure	Refined as an inversion twin.
Absolute structure parameter	−3 (2)
Computer programs: X-AREA and X-RED (Stoe & Cie, 2002), SHELXL2017 (Sheldrick, 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1820439

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018002621/xu5917sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018002621/xu5917Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018002621/xu5917Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: WinGX (Farrugia, 2012); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

7-Ethoxy-5-methyl-2-(pyridin-3-yl)-11,12-dihydro-5,11-methano-1,2,4]-triazolo[1,5-c][1,3,5]benzoxadiazocine top

Crystal data top

C₁₉H₁₉N₅O₂	D_x = 1.326 Mg m⁻³
M_r = 349.39	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 8727 reflections
a = 17.1509 (8) Å	θ = 1.7–27.6°
c = 11.9033 (7) Å	µ = 0.09 mm⁻¹
V = 3501.4 (4) Å³	T = 293 K
Z = 8	Prism, colorless
F(000) = 1472	0.54 × 0.34 × 0.16 mm

Data collection top

Stoe IPDS 2 diffractometer	3629 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2449 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.053
rotation method scans	θ_max = 26.5°, θ_min = 1.7°
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	h = −20→21
T_min = 0.959, T_max = 0.984	k = −21→21
8018 measured reflections	l = −14→13

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F_o²) + (0.0372P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.088	(Δ/σ)_max < 0.001
S = 0.90	Δρ_max = 0.15 e Å⁻³
3629 reflections	Δρ_min = −0.12 e Å⁻³
236 parameters	Absolute structure: Refined as an inversion twin.
0 restraints	Absolute structure parameter: −3 (2)

Special details top

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. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.0390 (2)	0.7259 (2)	0.4925 (3)	0.0581 (10)
H1	−0.014021	0.716332	0.501878	0.070*
C2	0.0662 (2)	0.7372 (2)	0.3863 (3)	0.0597 (10)
H2	0.032912	0.733641	0.324888	0.072*
C3	0.1444 (2)	0.7541 (2)	0.3716 (3)	0.0558 (9)
H3	0.164641	0.761427	0.299904	0.067*
C4	0.19186 (19)	0.76002 (19)	0.4641 (3)	0.0451 (8)
C5	0.1594 (2)	0.7450 (2)	0.5683 (3)	0.0524 (9)
H5	0.191757	0.746889	0.630959	0.063*
C6	0.27446 (19)	0.78337 (18)	0.4538 (3)	0.0433 (8)
C7	0.3820 (2)	0.81015 (19)	0.3807 (3)	0.0452 (8)
C8	0.5188 (2)	0.8326 (2)	0.3714 (3)	0.0530 (9)
H8	0.557656	0.853590	0.319160	0.064*
C9	0.5062 (2)	0.8898 (2)	0.4669 (4)	0.0575 (10)
H9A	0.555879	0.903724	0.500282	0.069*
H9B	0.481787	0.936913	0.438785	0.069*
C10	0.4545 (2)	0.85180 (19)	0.5536 (3)	0.0484 (8)
C11	0.4295 (2)	0.9041 (2)	0.6485 (4)	0.0620 (11)
H11A	0.401451	0.947929	0.618728	0.093*
H11B	0.396382	0.875548	0.698823	0.093*
H11C	0.474656	0.922184	0.688324	0.093*
C12	0.53691 (18)	0.74016 (18)	0.5322 (3)	0.0432 (8)
C13	0.54834 (18)	0.75667 (19)	0.4207 (3)	0.0460 (8)
C14	0.5883 (2)	0.7029 (2)	0.3536 (3)	0.0557 (10)
H14	0.596039	0.713003	0.277630	0.067*
C15	0.6162 (2)	0.6352 (2)	0.4004 (4)	0.0631 (11)
H15	0.642215	0.599352	0.355389	0.076*
C16	0.6062 (2)	0.6195 (2)	0.5133 (3)	0.0576 (10)
H16	0.625672	0.573495	0.543568	0.069*
C17	0.56737 (19)	0.6719 (2)	0.5813 (3)	0.0471 (8)
C18	0.5850 (3)	0.5943 (3)	0.7453 (4)	0.0716 (12)
H18A	0.641332	0.593704	0.738080	0.086*
H18B	0.564269	0.547848	0.709738	0.086*
C19	0.5622 (3)	0.5965 (3)	0.8665 (4)	0.1006 (17)
H19A	0.582492	0.551306	0.903941	0.151*
H19B	0.583133	0.642681	0.900739	0.151*
H19C	0.506407	0.597026	0.872521	0.151*
N1	0.08383 (17)	0.72774 (19)	0.5838 (3)	0.0572 (8)
N2	0.31602 (16)	0.80437 (15)	0.5418 (2)	0.0458 (7)
N3	0.38723 (15)	0.82148 (16)	0.4920 (2)	0.0442 (7)
N4	0.31108 (15)	0.78598 (17)	0.3519 (2)	0.0467 (7)
N5	0.44380 (16)	0.82375 (18)	0.3130 (2)	0.0542 (8)
H5A	0.439554	0.826988	0.241203	0.065*
O1	0.49588 (12)	0.78802 (13)	0.60565 (18)	0.0468 (6)
O2	0.55363 (14)	0.66252 (14)	0.6933 (2)	0.0567 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.045 (2)	0.071 (3)	0.058 (3)	−0.0032 (17)	−0.0068 (19)	−0.002 (2)
C2	0.055 (2)	0.077 (3)	0.048 (2)	−0.0014 (19)	−0.0144 (18)	−0.001 (2)
C3	0.055 (2)	0.070 (2)	0.042 (2)	0.0003 (18)	−0.0024 (18)	0.0043 (18)
C4	0.0452 (19)	0.051 (2)	0.0389 (19)	0.0027 (15)	−0.0019 (16)	−0.0025 (16)
C5	0.050 (2)	0.065 (2)	0.043 (2)	0.0048 (17)	−0.0047 (17)	−0.0016 (18)
C6	0.0474 (19)	0.0454 (19)	0.0370 (19)	0.0039 (14)	−0.0035 (16)	−0.0014 (16)
C7	0.052 (2)	0.046 (2)	0.037 (2)	0.0000 (16)	−0.0011 (17)	0.0026 (16)
C8	0.050 (2)	0.054 (2)	0.055 (2)	−0.0108 (17)	−0.0034 (18)	0.0068 (19)
C9	0.062 (2)	0.0416 (19)	0.069 (3)	−0.0079 (16)	−0.012 (2)	0.0020 (19)
C10	0.052 (2)	0.0433 (18)	0.050 (2)	0.0020 (15)	−0.0100 (17)	−0.0025 (17)
C11	0.070 (3)	0.051 (2)	0.064 (3)	0.0125 (18)	−0.020 (2)	−0.0181 (19)
C12	0.0350 (17)	0.0465 (19)	0.048 (2)	−0.0012 (14)	−0.0029 (15)	−0.0062 (17)
C13	0.0388 (19)	0.050 (2)	0.049 (2)	−0.0059 (15)	−0.0008 (16)	−0.0023 (17)
C14	0.048 (2)	0.066 (2)	0.054 (2)	−0.0040 (18)	0.0081 (18)	−0.0043 (19)
C15	0.056 (2)	0.065 (3)	0.068 (3)	0.0102 (19)	0.014 (2)	−0.013 (2)
C16	0.048 (2)	0.056 (2)	0.069 (3)	0.0077 (17)	0.0038 (19)	−0.001 (2)
C17	0.0395 (19)	0.048 (2)	0.053 (2)	0.0002 (15)	−0.0013 (16)	0.0001 (17)
C18	0.070 (3)	0.072 (3)	0.073 (3)	0.020 (2)	−0.002 (2)	0.020 (2)
C19	0.101 (4)	0.119 (4)	0.082 (3)	0.032 (3)	0.009 (3)	0.039 (3)
N1	0.0495 (18)	0.075 (2)	0.0473 (19)	−0.0042 (15)	−0.0009 (15)	0.0003 (16)
N2	0.0471 (17)	0.0498 (16)	0.0404 (17)	0.0034 (12)	−0.0027 (14)	−0.0044 (13)
N3	0.0414 (16)	0.0491 (16)	0.0422 (18)	−0.0011 (12)	−0.0038 (13)	−0.0030 (13)
N4	0.0436 (17)	0.0571 (18)	0.0393 (17)	0.0005 (14)	−0.0050 (13)	0.0033 (13)
N5	0.0486 (18)	0.073 (2)	0.0410 (16)	−0.0050 (15)	−0.0034 (14)	0.0104 (16)
O1	0.0494 (13)	0.0459 (13)	0.0451 (13)	0.0082 (10)	−0.0054 (11)	−0.0044 (11)
O2	0.0557 (15)	0.0585 (16)	0.0559 (16)	0.0140 (12)	−0.0017 (13)	0.0087 (13)

Geometric parameters (Å, º) top

C1—N1	1.331 (5)	C10—C11	1.504 (5)
C1—C2	1.362 (5)	C11—H11A	0.9600
C1—H1	0.9300	C11—H11B	0.9600
C2—C3	1.384 (5)	C11—H11C	0.9600
C2—H2	0.9300	C12—C13	1.372 (5)
C3—C4	1.373 (5)	C12—O1	1.390 (4)
C3—H3	0.9300	C12—C17	1.409 (5)
C4—C5	1.383 (5)	C13—C14	1.399 (5)
C4—C6	1.477 (4)	C14—C15	1.374 (5)
C5—N1	1.343 (4)	C14—H14	0.9300
C5—H5	0.9300	C15—C16	1.380 (6)
C6—N2	1.317 (4)	C15—H15	0.9300
C6—N4	1.367 (4)	C16—C17	1.380 (5)
C7—N4	1.330 (4)	C16—H16	0.9300
C7—N3	1.342 (4)	C17—O2	1.364 (4)
C7—N5	1.352 (4)	C18—O2	1.428 (4)
C8—N5	1.469 (4)	C18—C19	1.495 (6)
C8—C13	1.515 (5)	C18—H18A	0.9700
C8—C9	1.517 (5)	C18—H18B	0.9700
C8—H8	0.9800	C19—H19A	0.9600
C9—C10	1.509 (5)	C19—H19B	0.9600
C9—H9A	0.9700	C19—H19C	0.9600
C9—H9B	0.9700	N2—N3	1.389 (4)
C10—O1	1.443 (4)	N5—H5A	0.8600
C10—N3	1.463 (4)

N1—C1—C2	123.7 (3)	H11A—C11—H11C	109.5
N1—C1—H1	118.1	H11B—C11—H11C	109.5
C2—C1—H1	118.1	C13—C12—O1	124.0 (3)
C1—C2—C3	118.7 (4)	C13—C12—C17	121.3 (3)
C1—C2—H2	120.7	O1—C12—C17	114.7 (3)
C3—C2—H2	120.7	C12—C13—C14	119.1 (3)
C4—C3—C2	119.2 (3)	C12—C13—C8	120.3 (3)
C4—C3—H3	120.4	C14—C13—C8	120.6 (3)
C2—C3—H3	120.4	C15—C14—C13	119.7 (4)
C3—C4—C5	117.8 (3)	C15—C14—H14	120.1
C3—C4—C6	121.4 (3)	C13—C14—H14	120.1
C5—C4—C6	120.7 (3)	C14—C15—C16	121.1 (4)
N1—C5—C4	123.5 (3)	C14—C15—H15	119.5
N1—C5—H5	118.2	C16—C15—H15	119.5
C4—C5—H5	118.2	C17—C16—C15	120.3 (4)
N2—C6—N4	116.6 (3)	C17—C16—H16	119.9
N2—C6—C4	121.8 (3)	C15—C16—H16	119.9
N4—C6—C4	121.5 (3)	O2—C17—C16	125.5 (3)
N4—C7—N3	111.2 (3)	O2—C17—C12	116.0 (3)
N4—C7—N5	128.1 (3)	C16—C17—C12	118.5 (3)
N3—C7—N5	120.7 (3)	O2—C18—C19	107.4 (4)
N5—C8—C13	112.8 (3)	O2—C18—H18A	110.2
N5—C8—C9	107.2 (3)	C19—C18—H18A	110.2
C13—C8—C9	108.2 (3)	O2—C18—H18B	110.2
N5—C8—H8	109.5	C19—C18—H18B	110.2
C13—C8—H8	109.5	H18A—C18—H18B	108.5
C9—C8—H8	109.5	C18—C19—H19A	109.5
C10—C9—C8	108.5 (3)	C18—C19—H19B	109.5
C10—C9—H9A	110.0	H19A—C19—H19B	109.5
C8—C9—H9A	110.0	C18—C19—H19C	109.5
C10—C9—H9B	110.0	H19A—C19—H19C	109.5
C8—C9—H9B	110.0	H19B—C19—H19C	109.5
H9A—C9—H9B	108.4	C1—N1—C5	116.8 (3)
O1—C10—N3	109.5 (3)	C6—N2—N3	101.2 (3)
O1—C10—C11	105.7 (3)	C7—N3—N2	109.4 (3)
N3—C10—C11	111.3 (3)	C7—N3—C10	126.8 (3)
O1—C10—C9	109.4 (3)	N2—N3—C10	123.7 (3)
N3—C10—C9	105.9 (3)	C7—N4—C6	101.6 (3)
C11—C10—C9	115.1 (3)	C7—N5—C8	115.0 (3)
C10—C11—H11A	109.5	C7—N5—H5A	122.5
C10—C11—H11B	109.5	C8—N5—H5A	122.5
H11A—C11—H11B	109.5	C12—O1—C10	115.3 (2)
C10—C11—H11C	109.5	C17—O2—C18	117.1 (3)

N1—C1—C2—C3	−2.2 (6)	C2—C1—N1—C5	2.8 (6)
C1—C2—C3—C4	−0.9 (6)	C4—C5—N1—C1	−0.4 (5)
C2—C3—C4—C5	3.0 (5)	N4—C6—N2—N3	−0.8 (3)
C2—C3—C4—C6	−175.7 (3)	C4—C6—N2—N3	−179.3 (3)
C3—C4—C5—N1	−2.5 (5)	N4—C7—N3—N2	−0.2 (4)
C6—C4—C5—N1	176.2 (3)	N5—C7—N3—N2	179.3 (3)
C3—C4—C6—N2	166.1 (3)	N4—C7—N3—C10	−176.5 (3)
C5—C4—C6—N2	−12.5 (5)	N5—C7—N3—C10	3.0 (5)
C3—C4—C6—N4	−12.4 (5)	C6—N2—N3—C7	0.5 (3)
C5—C4—C6—N4	169.0 (3)	C6—N2—N3—C10	177.0 (3)
N5—C8—C9—C10	68.7 (3)	O1—C10—N3—C7	−101.2 (4)
C13—C8—C9—C10	−53.3 (4)	C11—C10—N3—C7	142.3 (4)
C8—C9—C10—O1	67.4 (3)	C9—C10—N3—C7	16.6 (4)
C8—C9—C10—N3	−50.5 (3)	O1—C10—N3—N2	83.0 (4)
C8—C9—C10—C11	−173.8 (3)	C11—C10—N3—N2	−33.5 (4)
O1—C12—C13—C14	−177.8 (3)	C9—C10—N3—N2	−159.2 (3)
C17—C12—C13—C14	2.6 (5)	N3—C7—N4—C6	−0.2 (4)
O1—C12—C13—C8	2.9 (5)	N5—C7—N4—C6	−179.7 (3)
C17—C12—C13—C8	−176.7 (3)	N2—C6—N4—C7	0.7 (4)
N5—C8—C13—C12	−98.3 (4)	C4—C6—N4—C7	179.2 (3)
C9—C8—C13—C12	20.1 (4)	N4—C7—N5—C8	−166.6 (3)
N5—C8—C13—C14	82.4 (4)	N3—C7—N5—C8	14.0 (5)
C9—C8—C13—C14	−159.2 (3)	C13—C8—N5—C7	70.4 (4)
C12—C13—C14—C15	−0.7 (5)	C9—C8—N5—C7	−48.7 (4)
C8—C13—C14—C15	178.6 (3)	C13—C12—O1—C10	9.4 (4)
C13—C14—C15—C16	−0.7 (6)	C17—C12—O1—C10	−171.0 (3)
C14—C15—C16—C17	0.3 (6)	N3—C10—O1—C12	71.7 (3)
C15—C16—C17—O2	179.6 (4)	C11—C10—O1—C12	−168.4 (3)
C15—C16—C17—C12	1.5 (5)	C9—C10—O1—C12	−43.9 (4)
C13—C12—C17—O2	178.7 (3)	C16—C17—O2—C18	2.8 (5)
O1—C12—C17—O2	−0.9 (4)	C12—C17—O2—C18	−179.0 (3)
C13—C12—C17—C16	−3.0 (5)	C19—C18—O2—C17	−179.6 (4)
O1—C12—C17—C16	177.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N1ⁱ	0.86	2.13	2.907 (4)	149

Symmetry code: (i) −x+1/2, −y+3/2, z−1/2.

Acknowledgements

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).

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