Crystal structure and Hirshfeld surface analysis of 3-[2-(3,5-di­methyl­phen­yl)hydrazinyl­idene]benzo­furan-2(3H)-one

In the crystal, mol­ecules are connected by C—H⋯π and π–π stacking inter­actions, forming a layer lying parallel to the (11 ) plane.

Abstract

In the title compound, C₁₆H₁₄N₂O₂, the 2,3-di­hydro-1-benzo­furan ring system is essentially planar and makes a dihedral angle of 3.69 (7)° with the di­methyl­phenyl ring. The mol­ecular conformation is stabilized by an intra­molecular N—H⋯O hydrogen bond with an S(6) ring motif. In the crystal, mol­ecules are connected by C—H⋯π and π–π stacking inter­actions, forming a layer lying parallel to the (11 ) plane. One methyl group is disordered over two orientations, with occupancies of 0.67 (4) and 0.33 (4). Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯H (51.2%), O⋯H/H⋯O (17.9%), C⋯H/H⋯C (15.2%) and C⋯C (8.1%) contacts.

Chemical context

Hydrazones have many applications in diverse areas, such as in optical data storage, as mol­ecular switches and anti­microbial agents, in non-linear optics, mol­ecular recognition, dye-sensitized solar cells, color-changing materials, catalysis, liquid crystals, etc., mainly because of the azo-to-hydrazo tautomerism/isomerism and the optical properties of –N=N– unit (Maharramov et al., 2018 ▸; Ma et al., 2020 ▸, 2021 ▸; Viswanathan et al., 2019 ▸). Not only E/Z isomerization, but also azo-hydrazone tautomerism is important in organic and the coordination chemistry of hydrazone dyes (Ma et al., 2017a ▸,b ▸; Mahmoudi et al., 2017 ▸, 2018 ▸). The design of hydrazone dyes with electron donor or acceptor substituents has led to multidentante ligands, the corresponding coordination compounds of which have been applied effectively as catalysts in oxidation and C—C coupling reactions (Mahmudov et al., 2013 ▸; Mizar et al., 2012 ▸). Moreover, the functional properties of hydrazones or their metal complexes can be regulated by attaching functional groups to the =N—NH— unit (Gurbanov et al., 2020a ▸,b ▸; Kopylovich et al., 2011 ▸; Mahmudov et al., 2020 ▸; Shixaliyev et al., 2014 ▸). Thus, we have attached C=O groups and furan and aryl rings to the =N—NH— moiety, leading to a new hydrazone compound, (Z)-3-[2-(3,5-di­methyl­phen­yl)hydrazinyl­idene]benzo­furan-2(3H)-one, which can form inter­molecular inter­actions.

Structural commentary

The mol­ecular conformation of the title compound is stabilized by an intra­molecular N—H⋯O hydrogen bond (N2—H2⋯O2; Table 1 ▸) with an S(6) ring motif (Fig. 1 ▸). The 2,3-di­hydro-1-benzo­furan ring system (O1/C1–C8) of the title compound is essentially planar [maximum deviations = −0.031 (2) Å for C3 and 0.026 (2) Å for C6] and makes a dihedral angle of 3.69 (7)° with the di­methyl­phenyl C9–C14 ring. In the mol­ecule, the aromatic C9–C14 ring and the C=N—NH– unit are almost coplanar with a dihedral angle of 4.8 (8)° between them.

Table 1. Hydrogen-bond geometry (Å, °).

Cg2 and Cg3 are the centroids of the C3–C8 and C9–C14 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.93 (2)	2.12 (2)	2.840 (2)	133.8 (16)
C15—H15A⋯Cg3i	0.96	2.90	3.591 (3)	130
C16—H16F⋯Cg2ii	0.96	2.92	3.715 (3)	141

Symmetry codes: (i) x, -y-{\script{1\over 2}}, z-{\script{3\over 2}}; (ii) -x+1, -y+1, -z+1.

Figure 1.

The mol­ecular structure of the title compound with displacement ellipsoids for the non-hydrogen atoms drawn at the 30% probability level.

Supra­molecular features

In the crystal, mol­ecules are connected by C—H⋯π inter­actions [C15—H15A⋯Cg3ⁱ and C16—H16F⋯Cg2ⁱⁱ; symmetry codes as given in Table 1 ▸; Fig. 2 ▸] and π–π stacking inter­actions [Cg1⋯Cg2^îii = 3.6227 (11) Å, slippage = 1.226 Å; Cg1⋯Cg3 ^îi = 3.7128 (10) Å, slippage = 1.339 Å; Symmetry codes: (ii) −x + 1, −y + 1, −z + 1; (iii) −x + 2, −y + 1, −z + 2], where Cg1 and Cg2 are the centroids of the oxolane O1/C1–C3/C8 and benzene C3–C8 rings, respectively, of the 2,3-di­hydro-1-benzo­furan ring system while Cg3 is the centroid of the di­methyl­phenyl C9–C14 ring (Fig. 3 ▸). These inter­actions link the mol­ecules into a layer structure lying parallel to the (11 ) plane (Fig. 4 ▸).

Figure 2.

A partial packing view of the title compound, showing the C—H⋯π inter­actions (dashed lines). Only H atoms involved in the inter­actions and N-bound H atoms are shown for clarity [Symmetry codes: (i) x, −y −  , z −  ; (ii) −x + 1, −y + 1, −z + 1.]

Figure 3.

A partial packing view of the title compound, showing the π–π stacking inter­actions (dashed lines). Only N-bound H atoms are shown for clarity [Symmetry codes: (ii) −x + 1, −y + 1, −z + 1; (iii) 2 − x, 1 − y, 2 − z.]

Figure 4.

A packing diagram of the title compound viewed along the a-axis, showing C—H⋯π inter­actions (dashed lines). Only H atoms involved in the inter­actions and N-bound H atoms are shown for clarity.

Hirshfeld surface analysis

Crystal Explorer17 (Turner et al., 2017 ▸) was used to perform a Hirshfeld surface analysis and generate the associated two-dimensional fingerprint plots, with a standard resolution of the three-dimensional d _norm surfaces plotted over a fixed color scale of −0.0001 (red) to 1.5993 (blue) a.u. (Fig. 5a ▸). All of the disordered H atoms of the C16 methyl group were taken into account together. The shape-index of the Hirshfeld surface 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 ▸ b clearly indicates that there are π–π inter­actions in the title compound.

Figure 5.

Hirshfeld surfaces of the title mol­ecule, (a) mapped with d _norm in the range −0.0001 to 1.5993 a.u. and (b) plotted over shape-index.

Two-dimensional fingerprint plots for the H⋯H, O⋯H/H⋯O, C⋯H/H⋯C and C⋯C contacts are presented in Fig. 6 ▸. H⋯H inter­actions, which are located in the middle region of the fingerprint plot, contribute the most to overall crystal packing, with 51.2% (Fig. 6b ▸). The O⋯H/H⋯O contacts contribute 17.9% (Fig. 6c ▸) to the Hirshfeld surface, while the C⋯H/H⋯C contacts contribute 15.2% (Fig. 6d ▸), resulting in a pair of distinctive wings. The C⋯C inter­actions account for 8.1% of the Hirshfeld surface. The percentage contributions to the Hirshfeld surface including other minor ones are summarized in Table 2 ▸.

Figure 6.

Fingerprint plots showing (a) all inter­molecular inter­actions and delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) C⋯H/H⋯C and (e) C⋯C contacts.

Table 2. Percentage contributions of inter­atomic contacts to the Hirshfeld surface of the title compound.

Contact	Percentage contribution
H⋯H	51.2
O⋯H/H⋯O	17.9
C⋯H/H⋯C	15.2
C⋯C	8.1
N⋯C/C⋯N	4.2
N⋯H/H⋯N	1.9
O⋯C/C⋯O	0.9
N⋯N	0.6
O⋯O	0.1

Database survey

A search of the Cambridge Crystallographic Database (CSD version 5.42, updated September 2021; Groom et al., 2016 ▸) for the 1-benzo­furan-2(3H)-one unit gave 220 hits. Of these, the compound most similar to the title compound is 7-meth­oxy-3-(2-phenyl­hydrazinyl­idene)-1-benzo­furan-2(3H)-one, I (CSD refcode IBADIC; Atioğlu et al., 2021 ▸). Four compounds reported by Oliveira et al. (2019 ▸) are closely related to the title compound, viz. 2-(4-nitro-1H-imidazol-1-yl)-N′-[1-(pyridin-2-yl)ethyl­idene]acetohydrazide, II (TODMEH), 2-(2-nitro-1H-imidazol-1-yl)-N′-[1-(pyridin-2-yl)ethyl­idene]acetohydrazide, III (TODMIL), 2-(4-nitro-1H-imidazol-1-yl)-N′-[phen­yl(pyridin-2-yl)methyl­idene]acetohydrazide, IV (TODMOR) and 2-(4-nitro-1H-imidazol-1-yl)-N′-[phen­yl(pyridin-2-yl)methyl­idene]acetohydrazide, V (TODMUX). Compound I crystallizes in the monoclinic space group C2/c with Z = 8. In the crystal of I, pairs of mol­ecules are linked into dimers by N—H⋯O hydrogen bonds, forming an (12) ring motif, with the dimers stacked along the a-axis direction. These dimers are connected through π–π stacking inter­actions between the centroids of the benzene and furan rings of their 2,3-di­hydro-1-benzo­furan ring systems. Furthermore, there exists a C—H⋯π inter­action that consolidates the crystal packing. Compounds II and IV crystallize in the monoclinic space group P2₁/c with Z = 4. Compound III crystallizes in the monoclinic space group I2/a with Z = 8 and V crystallizes in the triclinic space group P with Z = 2. Compound VI crystallizes in the monoclinic space group P2₁/c with Z = 4. The E conformation in II, III and V is stabilized by a strong inter­molecular N—H⋯O inter­action. These inter­actions lead to the formation of dimeric structural arrangements. In the crystal of IV, an inter­molecular N—H⋯N hydrogen bond results in a helical chain structure along the b-axis direction. Non-classical inter­molecular C—H⋯N and C—H⋯O inter­actions are also observed in the crystals of II, III, IV and V.

Synthesis and crystallization

(Z)-3-[2-(3,5-Di­methyl­phen­yl)hydrazinyl­idene]benzo­furan-2(3H)-one was synthesized according to the reported method (Shikhaliyev et al., 2018 ▸, 2019 ▸). A 20 mL screw-neck vial was charged with DMSO (10 mL), (E)-2-{[2-(3,5-di­methyl­phen­yl)hydrazinyl­idene]meth­yl}phenol (240 mg, 1 mmol), tetra­methyl­ethylenedi­amine (TMEDA) (295 mg, 2.5 mmol), CuCl (2 mg, 0.02 mmol) and CCl₄ (20 mmol, 10 equiv). After 1–3 h (until TLC analysis showed complete consumption of the corresponding Schiff base), the reaction mixture was poured into a 0.01 M solution of HCl (100 mL, pH 2–3), and extracted with di­chloro­methane (3 × 20 mL). The combined organic phase was washed with water (3 × 20 mL), brine (30 mL), dried over anhydrous Na₂SO₄ and concentrated in vacuo using a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and di­chloro­methane (3/1–1/1). Then the substance was refluxed in methanol for 30 min, and left for evaporation. After three days, single crystals of the title compound suitable for X-ray analysis were obtained. Colorless solid (65%); m.p. 475 K. Analysis calculated for C₁₆H₁₄N₂O₂ (M = 266.30): C 72.17, H 5.30, N 10.52; found: C 72.13, H 5.26, N 10.48%. ¹H NMR (300 MHz, CDCl₃) δ 12.04 (1H, NH), 6.79–7.69 (7H, Ar), 2.37 (6H, 2CH₃). ¹³C NMR (75 MHz, CDCl₃) δ 160.47, 157.77, 134.91, 125.14, 124.12, 121.77, 121.56, 119.86, 118.21, 114.55, 108.16, 106.59, 16.85 and 16.52. ESI–MS: m/z: 267.23 [M + H]⁺.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The amine H atom was located in a difference-Fourier map and refined freely [N2—H2 = 0.93 (2) Å]. All C-bound H atoms were placed at calculated positions using a riding model, with C—H = 0.93 or 0.96 Å, and with U _iso(H) = 1.2 or 1.5U _eq(C). The methyl group with the C16 atom attached to the atom C13 is disordered over two orientations, with occupancies of 0.67 (4) and 0.33 (4). Owing to poor agreement, nine reflections ( 14 10, 7 13 0, 6 5, 12 4, 11 1 0, 1 1, 19 6, 0 8 and 17 4) were omitted during the final refinement cycle.

Table 3. Experimental details.

Crystal data
Chemical formula	C16H14N2O2
M r	266.29
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	296
a, b, c (Å)	8.8644 (4), 19.9222 (8), 8.1736 (3)
β (°)	107.240 (1)
V (Å3)	1378.59 (10)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.09
Crystal size (mm)	0.40 × 0.21 × 0.06
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2003 ▸)
T min, T max	0.684, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	22343, 4176, 2332
R int	0.058
(sin θ/λ)max (Å−1)	0.714
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.062, 0.146, 1.04
No. of reflections	4176
No. of parameters	188
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.15, −0.14

Computer programs: APEX2 (Bruker, 2003 ▸), SAINT (Bruker, 2003 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸), PLATON (Spek, 2020 ▸).

Supplementary Material

CCDC reference: 1983650

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

supplementary crystallographic information

Crystal data

C16H14N2O2	F(000) = 560
Mr = 266.29	Dx = 1.283 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.8644 (4) Å	Cell parameters from 3738 reflections
b = 19.9222 (8) Å	θ = 2.4–30.5°
c = 8.1736 (3) Å	µ = 0.09 mm−1
β = 107.240 (1)°	T = 296 K
V = 1378.59 (10) Å3	Prism, colourless
Z = 4	0.40 × 0.21 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer	2332 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.058
Absorption correction: multi-scan (SADABS; Bruker, 2003)	θmax = 30.5°, θmin = 2.4°
Tmin = 0.684, Tmax = 0.746	h = −12→12
22343 measured reflections	k = −28→28
4176 independent reflections	l = −11→11

Refinement

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.062	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.146	w = 1/[σ2(Fo2) + (0.0465P)2 + 0.2174P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
4176 reflections	Δρmax = 0.15 e Å−3
188 parameters	Δρmin = −0.14 e Å−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.7095 (2)	0.56971 (8)	0.9270 (2)	0.0519 (4)
C2	0.76884 (18)	0.52981 (8)	0.8095 (2)	0.0482 (4)
C3	0.92693 (18)	0.55352 (8)	0.8274 (2)	0.0493 (4)
C4	1.0448 (2)	0.53565 (9)	0.7563 (3)	0.0624 (5)
H4	1.028478	0.502040	0.673914	0.075*
C5	1.1879 (2)	0.56929 (11)	0.8114 (3)	0.0728 (6)
H5	1.268324	0.558312	0.764500	0.087*
C6	1.2129 (2)	0.61884 (11)	0.9347 (3)	0.0749 (6)
H6	1.310276	0.640405	0.969456	0.090*
C7	1.0974 (2)	0.63715 (10)	1.0075 (3)	0.0673 (5)
H7	1.114142	0.670299	1.091089	0.081*
C8	0.95594 (19)	0.60361 (8)	0.9495 (2)	0.0538 (4)
C9	0.4768 (2)	0.40926 (8)	0.6127 (2)	0.0530 (4)
C10	0.5476 (2)	0.37321 (9)	0.5108 (2)	0.0603 (5)
H10	0.648784	0.384407	0.508401	0.072*
C11	0.4678 (3)	0.32049 (9)	0.4125 (2)	0.0702 (6)
C12	0.3181 (3)	0.30497 (10)	0.4188 (3)	0.0779 (6)
H12	0.263853	0.269826	0.351887	0.093*
C13	0.2457 (2)	0.33984 (10)	0.5213 (3)	0.0693 (6)
C14	0.3266 (2)	0.39267 (9)	0.6189 (2)	0.0598 (5)
H14	0.280284	0.416993	0.688386	0.072*
C15	0.5458 (3)	0.28029 (12)	0.3040 (3)	0.1039 (9)
H15A	0.513973	0.234174	0.302284	0.156*
H15B	0.658448	0.283384	0.351251	0.156*
H15C	0.514651	0.297710	0.189347	0.156*
C16	0.0820 (3)	0.32121 (12)	0.5296 (3)	0.0972 (8)
H16D	0.052299	0.350758	0.607547	0.146*	0.67 (4)
H16E	0.082700	0.275746	0.568674	0.146*	0.67 (4)
H16F	0.007489	0.325362	0.417644	0.146*	0.67 (4)
H16A	0.013993	0.359673	0.500891	0.146*	0.33 (4)
H16B	0.088531	0.306500	0.643291	0.146*	0.33 (4)
H16C	0.039964	0.285692	0.449682	0.146*	0.33 (4)
N1	0.69683 (16)	0.48115 (7)	0.70999 (18)	0.0508 (3)
N2	0.55439 (17)	0.46316 (7)	0.7133 (2)	0.0545 (4)
H2	0.513 (2)	0.4843 (10)	0.792 (3)	0.077 (6)*
O1	0.82605 (14)	0.61480 (6)	1.00954 (16)	0.0609 (3)
O2	0.58433 (14)	0.56775 (7)	0.95705 (17)	0.0666 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0428 (9)	0.0531 (9)	0.0561 (10)	−0.0041 (7)	0.0089 (8)	−0.0012 (8)
C2	0.0422 (9)	0.0501 (9)	0.0482 (9)	−0.0004 (7)	0.0073 (7)	0.0016 (7)
C3	0.0403 (8)	0.0503 (9)	0.0546 (10)	0.0026 (7)	0.0100 (7)	0.0083 (7)
C4	0.0525 (11)	0.0673 (11)	0.0680 (12)	0.0056 (9)	0.0186 (9)	0.0090 (9)
C5	0.0459 (11)	0.0842 (14)	0.0898 (16)	0.0066 (10)	0.0223 (11)	0.0224 (12)
C6	0.0445 (11)	0.0770 (13)	0.0958 (16)	−0.0094 (9)	0.0092 (11)	0.0179 (12)
C7	0.0512 (11)	0.0607 (11)	0.0808 (14)	−0.0092 (9)	0.0053 (10)	0.0015 (10)
C8	0.0409 (9)	0.0531 (9)	0.0630 (11)	−0.0004 (7)	0.0088 (8)	0.0055 (8)
C9	0.0536 (10)	0.0501 (9)	0.0461 (9)	−0.0056 (8)	0.0005 (8)	0.0030 (7)
C10	0.0700 (12)	0.0553 (10)	0.0511 (10)	−0.0063 (9)	0.0109 (9)	0.0003 (8)
C11	0.0950 (16)	0.0537 (11)	0.0542 (11)	−0.0090 (10)	0.0102 (11)	−0.0011 (9)
C12	0.0988 (17)	0.0575 (12)	0.0572 (12)	−0.0205 (11)	−0.0078 (12)	−0.0005 (10)
C13	0.0649 (12)	0.0635 (12)	0.0621 (12)	−0.0153 (9)	−0.0080 (10)	0.0156 (10)
C14	0.0534 (10)	0.0616 (11)	0.0553 (10)	−0.0066 (8)	0.0020 (8)	0.0065 (8)
C15	0.150 (2)	0.0746 (15)	0.0865 (17)	−0.0083 (15)	0.0348 (17)	−0.0243 (13)
C16	0.0724 (15)	0.0949 (17)	0.1019 (18)	−0.0327 (12)	−0.0085 (13)	0.0192 (14)
N1	0.0466 (8)	0.0525 (8)	0.0497 (8)	−0.0017 (6)	0.0086 (6)	0.0028 (6)
N2	0.0475 (8)	0.0574 (9)	0.0553 (9)	−0.0059 (7)	0.0100 (7)	−0.0065 (7)
O1	0.0496 (7)	0.0610 (7)	0.0690 (8)	−0.0061 (6)	0.0127 (6)	−0.0130 (6)
O2	0.0473 (7)	0.0790 (9)	0.0757 (9)	−0.0041 (6)	0.0213 (6)	−0.0101 (7)

Geometric parameters (Å, º)

C1—O2	1.2064 (19)	C10—H10	0.9300
C1—O1	1.3842 (19)	C11—C12	1.378 (3)
C1—C2	1.459 (2)	C11—C15	1.506 (3)
C2—N1	1.304 (2)	C12—C13	1.384 (3)
C2—C3	1.445 (2)	C12—H12	0.9300
C3—C8	1.380 (2)	C13—C14	1.385 (2)
C3—C4	1.385 (2)	C13—C16	1.519 (3)
C4—C5	1.386 (3)	C14—H14	0.9300
C4—H4	0.9300	C15—H15A	0.9600
C5—C6	1.381 (3)	C15—H15B	0.9600
C5—H5	0.9300	C15—H15C	0.9600
C6—C7	1.377 (3)	C16—H16D	0.9600
C6—H6	0.9300	C16—H16E	0.9600
C7—C8	1.375 (2)	C16—H16F	0.9600
C7—H7	0.9300	C16—H16A	0.9600
C8—O1	1.397 (2)	C16—H16B	0.9600
C9—C10	1.383 (2)	C16—H16C	0.9600
C9—C14	1.387 (2)	N1—N2	1.3206 (19)
C9—N2	1.402 (2)	N2—H2	0.93 (2)
C10—C11	1.383 (2)
O2—C1—O1	121.34 (16)	C11—C12—C13	122.29 (18)
O2—C1—C2	130.48 (16)	C11—C12—H12	118.9
O1—C1—C2	108.18 (14)	C13—C12—H12	118.9
N1—C2—C3	125.97 (16)	C12—C13—C14	118.4 (2)
N1—C2—C1	127.59 (15)	C12—C13—C16	121.7 (2)
C3—C2—C1	106.43 (14)	C14—C13—C16	119.9 (2)
C8—C3—C4	119.17 (16)	C13—C14—C9	119.93 (19)
C8—C3—C2	106.10 (15)	C13—C14—H14	120.0
C4—C3—C2	134.70 (17)	C9—C14—H14	120.0
C3—C4—C5	118.10 (19)	C11—C15—H15A	109.5
C3—C4—H4	121.0	C11—C15—H15B	109.5
C5—C4—H4	121.0	H15A—C15—H15B	109.5
C6—C5—C4	121.07 (19)	C11—C15—H15C	109.5
C6—C5—H5	119.5	H15A—C15—H15C	109.5
C4—C5—H5	119.5	H15B—C15—H15C	109.5
C7—C6—C5	121.71 (19)	C13—C16—H16D	109.5
C7—C6—H6	119.1	C13—C16—H16E	109.5
C5—C6—H6	119.1	H16D—C16—H16E	109.5
C8—C7—C6	116.17 (19)	C13—C16—H16F	109.5
C8—C7—H7	121.9	H16D—C16—H16F	109.5
C6—C7—H7	121.9	H16E—C16—H16F	109.5
C7—C8—C3	123.77 (18)	C13—C16—H16A	109.5
C7—C8—O1	124.32 (17)	C13—C16—H16B	109.5
C3—C8—O1	111.89 (14)	H16A—C16—H16B	109.5
C10—C9—C14	120.63 (16)	C13—C16—H16C	109.5
C10—C9—N2	121.31 (16)	H16A—C16—H16C	109.5
C14—C9—N2	118.05 (17)	H16B—C16—H16C	109.5
C11—C10—C9	119.94 (19)	C2—N1—N2	118.89 (15)
C11—C10—H10	120.0	N1—N2—C9	120.08 (15)
C9—C10—H10	120.0	N1—N2—H2	117.9 (13)
C12—C11—C10	118.8 (2)	C9—N2—H2	121.7 (13)
C12—C11—C15	121.18 (19)	C1—O1—C8	107.39 (13)
C10—C11—C15	120.0 (2)
O2—C1—C2—N1	−1.0 (3)	N2—C9—C10—C11	−179.74 (16)
O1—C1—C2—N1	178.73 (15)	C9—C10—C11—C12	−0.1 (3)
O2—C1—C2—C3	−179.52 (18)	C9—C10—C11—C15	−178.83 (18)
O1—C1—C2—C3	0.23 (17)	C10—C11—C12—C13	−0.7 (3)
N1—C2—C3—C8	−178.02 (16)	C15—C11—C12—C13	178.06 (19)
C1—C2—C3—C8	0.52 (17)	C11—C12—C13—C14	0.8 (3)
N1—C2—C3—C4	−0.4 (3)	C11—C12—C13—C16	−178.75 (19)
C1—C2—C3—C4	178.17 (19)	C12—C13—C14—C9	−0.3 (3)
C8—C3—C4—C5	−0.1 (3)	C16—C13—C14—C9	179.33 (17)
C2—C3—C4—C5	−177.49 (18)	C10—C9—C14—C13	−0.5 (3)
C3—C4—C5—C6	0.5 (3)	N2—C9—C14—C13	179.91 (15)
C4—C5—C6—C7	−0.3 (3)	C3—C2—N1—N2	176.94 (15)
C5—C6—C7—C8	−0.4 (3)	C1—C2—N1—N2	−1.3 (2)
C6—C7—C8—C3	0.9 (3)	C2—N1—N2—C9	−177.48 (14)
C6—C7—C8—O1	179.25 (16)	C10—C9—N2—N1	1.1 (2)
C4—C3—C8—C7	−0.7 (3)	C14—C9—N2—N1	−179.26 (15)
C2—C3—C8—C7	177.41 (16)	O2—C1—O1—C8	178.89 (16)
C4—C3—C8—O1	−179.19 (14)	C2—C1—O1—C8	−0.88 (17)
C2—C3—C8—O1	−1.11 (19)	C7—C8—O1—C1	−177.24 (17)
C14—C9—C10—C11	0.6 (3)	C3—C8—O1—C1	1.27 (19)

Hydrogen-bond geometry (Å, º)

Cg2 and Cg3 are the centroids of the C3–C8 and C9–C14 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.93 (2)	2.12 (2)	2.840 (2)	133.8 (16)
C15—H15A···Cg3i	0.96	2.90	3.591 (3)	130
C16—H16F···Cg2ii	0.96	2.92	3.715 (3)	141

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

Funding Statement

This work was funded by Science Development Foundation Azerbaijan grant EIF-BGM-4- RFTF-1/2017–21/13/4.