Crystal structure and Hirshfeld surface analysis of 7-eth-oxy-5-methyl-2-(pyridin-3-yl)-11,12-di-hydro-5,11-methano-[1,2,4]triazolo[1,5-c][1,3,5]benzoxadiazo-cine.

The title compound, C19H19N5O2, was prepared by the reaction of 3-amino-5-(pyridin-3-yl)-1,2,4-triazole with acetone and 2-hy-droxy-3-eth-oxy-benzaldehyde. It crystallizes from ethanol in a tetra-gonal space group, with one mol-ecule 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 mol-ecules into supra-molecular chains propagating along the c-axis direction. Hirshfeld surface analysis and two-dimensional fingerprint plots have been used to analyse the inter-molecular inter-actions present in the crystal.

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 α1a-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.

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.

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) .

Figure 2

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

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.

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 ▸).

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.

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
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[F 2 > 2σ(F 2)], wR(F 2), S	0.042, 0.088, 0.90
No. of reflections	3629
No. of parameters	236
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (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 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018002621/xu5917sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018002621/xu5917Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018002621/xu5917Isup3.cml

CCDC reference: 1820439

Additional supporting information: crystallographic information; 3D view; checkCIF report

C19H19N5O2	Dx = 1.326 Mg m−3
Mr = 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

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	Rint = 0.053
rotation method scans	θmax = 26.5°, θmin = 1.7°
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	h = −20→21
Tmin = 0.959, Tmax = 0.984	k = −21→21
8018 measured reflections	l = −14→13

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(Fo2) + (0.0372P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.088	(Δ/σ)max < 0.001
S = 0.90	Δρmax = 0.15 e Å−3
3629 reflections	Δρmin = −0.12 e Å−3
236 parameters	Absolute structure: Refined as an inversion twin.
0 restraints	Absolute structure parameter: −3 (2)

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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