Crystal structure of 2,3-bis­(4-methyl­phen­yl)benzo[g]quinoxaline

Kim, Y.-I.; Yun, S.-J.; Kang, S.K.

doi:10.1107/S2056989018004413

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ISSN: 2056-9890

Volume 74| Part 4| April 2018| Pages 548-550

https://doi.org/10.1107/S2056989018004413

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Crystal structure of 2,3-bis(4-methylphenyl)benzo[g]quinoxaline

Young-Inn Kim,^a Seong-Jae Yun ^a and Sung Kwon Kang ^b ^*

^aDepartment of Chemistry Education and Department of Chemical Materials, Graduate School, Pusan National University, Busan 46241, South Korea, and ^bDepartment of Chemistry, Chungnam National University, Daejeon 34134, South Korea
^*Correspondence e-mail: skkang@cnu.ac.kr

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 7 March 2018; accepted 16 March 2018; online 23 March 2018)

The title compound, C₂₆H₂₀N₂, was obtained during a search for new π-extended ligands with the potential to generate efficient phosphors with iridium(III) for organic light-emitting devices (OLEDs). The benzoquinoxaline ring system is almost planar (r.m.s. deviation = 0.076 Å). A pseudo-twofold rotation axis runs through the midpoints of the C2—C3 and C9—C10 bonds. The two phenyl rings are twisted relative to the benzoquinoxaline ring system, making dihedral angles of 53.91 (4) and 36.86 (6)°. In the crystal, C—H⋯π (arene) interactions link the molecules, but no π–π interactions between aromatic rings are observed.

Keywords: crystal structure; 2,3-di-p-tolylbenzo[g]quinoxaline; N-heterocyclic compound; C—H⋯π interaction.

CCDC reference: 1543571

1. Chemical context

Quinoxalines are well-known nitrogen-containing heterocyclic compounds, and substituted quinoxalines are important ligands with transition metals (Achelle et al., 2013 ; Floris et al., 2017 ; Tariq et al., 2018 ). They act as chelating agents bearing ring complexes bounded by a benzene ring and a pyrazine ring. We have reported, for example, deep-red emissive iridium(III) complexes containing 2,3-diphenylquinoxaline (dpqH), in which red emissions contributed to the conjugated structure of the dpq ligand (Song et al., 2015 ). The use of long conjugated compounds as metal coordination ligands could be an approach to develop novel emitters toward red-shift emission up to near-infrared (NIR) wavelengths due to intersystem crossing (Ahn et al., 2009 ). Recently, 2,3-diphenylbenzoquinoxaline (dpbqH), a more π-extended ligand than dpqH, has been introduced, and its iridium(III) complex showed bathochromic shifted emission at 763 nm (Kim et al., 2018 ). The aromatic rings in dpqH formed dimeric aggregates by π–π interactions, and these dimers interact via van der Waals interactions in the solid state (Cantalupo et al., 2006 ; Kim et al., 2018). In this work, we have synthesized 2,3-di-p-tolylbenzo[g]quinoxaline (dmpbqH) from the reaction of 4,4-dimethylbenzil with 2,3-diaminonaphthalene, and investigated its single crystal structure.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The benzoquinoxaline ring system (atoms N1/C2/C3/N4/C5–C14) is almost planar, with an r.m.s. deviation of 0.076 Å from the corresponding least-squares plane defined by the 14 constituent atoms. In the pyrazine heterocyclic ring, the N1—C2 [1.310 (2) Å] and C3—N4 [1.310 (2) Å] bonds are shorter than the N1—C14 [1.381 (2) Å] and N4—C5 [1.379 (2) Å] bonds, even though the pyrazine ring has a delocalized π-system. There is a pseudo-twofold rotation axis passing through the midpoints of the C2—C3, C5—C14, C7—C12, and C9—C10 bonds. The two phenyl rings (atoms C15–C20 and C22–C25) are twisted relative to the benzoquinoxaline ring system, making dihedral angles of 53.91 (4) and 36.86 (6)°, respectively. The dihedral angle between the phenyl rings is 65.22 (6)°.

Figure 1
Molecular structure of the title compound, showing the atom-numbering scheme and 30% probability ellipsoids for non-H atoms.

3. Supramolecular features

In the crystal, there are two C—H⋯π interactions: C19—H19⋯Cg1ⁱ and C27—H27⋯Cg2ⁱⁱ (Table 1, Fig. 2) which stabilize the crystal packing (Fig. 3). There are no π–π interactions between the aromatic rings.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of atoms C7–C12 and N1/C2/C3/N4/C5–C7/C12–C14, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19⋯Cg1ⁱ	0.93	2.88	3.488 (3)	124
C27—H27⋯Cg2ⁱⁱ	0.93	2.91	3.601 (3)	132
Symmetry codes: (i) -x+1, -y, -z; (ii) x-1, y, z.

Figure 2
Part of the crystal packing showing molecules linked by intermolecular C—H⋯π interactions (Table 1

; shown as dashed lines). Cg1 and Cg2 are the centroids of the C7–C12 and the N1/C2/C3/N4/C5–C7/C12–C14 rings, respectively. [Symmetry codes: (i) −x + 1, −y, −z, (ii) x − 1, y, z].

Figure 3
Crystal packing of the title compound, showing molecules linked by intermolecular C—H⋯π bonds (dashed lines).

4. Database survey

A search of the Cambridge Structural Database (CSD; Groom et al., 2016 ) via the WebCSD interface in February 2018 returned several entries for crystal structures related to 2,3-disubstituted benzoquinoxalines. In 2,3-diphenylbenzoquinoxaline, the two phenyl rings form dihedral angles of 43.42 (3) and 46.89 (3)° with the benzoquinoxaline plane, a little larger than those of the title compound. The packing in the crystals is described as having a herringbone motif (REKDIV, Cantalupo et al., 2006; REKDIV01, Chan & Chang, 2016 ). There are three entries for metal complexes with this ligand. In the crystal lattice of a bis-cyclomanganese complex, the molecules are π-stacked in a parallel head-to-tail pattern with a mean inter-planar distance between the benzoquinoxaline planes of 3.5 Å (DECTAH; Djukic et al., 2005 ). In addition we also found two octahedral Ir^III complexes (VEHCAN and VEHCER; Chen et al., 2006 ).

There are three entries for crystal structures related to 2,3-bis(2-pyridyl)benzoquinoxaline. In the distorted octahedral Co^III complex (JUHVIR; Escuer et al., 1991 ), the Co^III atom is situated in the benzoquinoxaline plane, coordinated by one pyridyl N atom and one quinoxaline N atom. In the octahedral Re^V complex (HAYSAB; Bandoli et al., 1994 ), the Re^V atom is chelated by two pyridyl N atoms of the bis(2-pyridyl)benzoquinoxaline ligand. Finally, in the square-planar Pt^II complex (AYAMIW; Cusumano et al., 2004 ), the benzoquinoxaline moiety lies almost perpendicular to the square plane giving the molecule an unusual L-shaped geometry.

5. Synthesis and crystallization

Chemicals were obtained commercially in reagent grade and used as received. Solvents were dried using standard procedures as described in the literature. ¹H NMR spectra were recorded with a 300 MHz Varian Mercury model in CDCl₃. 4,4-Dimethylbenzil (3 mmol), 2,3-diaminonaphthalene (4.4 mmol), and iodine (0.37 mmol) were dissolved slowly in acetonitrile (10 ml), and stirred for 10 minutes at room temperature. The reaction mixture was poured into water, extracted with ether and dried over anhydrous MgSO₄. After volatiles had been removed under reduced pressure, the product was purified by silica gel chromatography using an eluent of hexane/ethyl acetate (20:1). Pale-yellow single crystals of the title compound were obtained from dichloromethane/hexane (1:1) solution within a few days by slow evaporation of the solvent at 298 K, yield: 48%. ¹H NMR (300 MHz, CDCl₃): 8.72 (s, 2H), 8.12 (m, 2H), 7.56 (m, 2H), 7.49 (d, 2H, J = 8.1Hz), 7.18 (d, 2H, J = 7.8Hz), 2.40 (s, 6H).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were positioned geometrically and refined using a riding model, with d(C—H) = 0.93–0.96 Å, and with U_iso(H) = 1.2U_eq(C) for aromatic-H and 1.5U_eq(C) for methyl-H atoms, respectively.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₆H₂₀N₂
M_r	360.44
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	6.0814 (1), 21.5212 (4), 14.8312 (3)
β (°)	91.2496 (11)
V (Å³)	1940.63 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.07
Crystal size (mm)	0.15 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector
No. of measured, independent and observed [I > 2σ(I)] reflections	29811, 4805, 2628
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.124, 1.01
No. of reflections	4805
No. of parameters	255
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16
Computer programs: SMART and SAINT (Bruker, 2012 ), SHELXS2013 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and ORTEP-3 for Windows and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1543571

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018004413/vm2210sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018004413/vm2210Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018004413/vm2210Isup3.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

2,3-Bis(4-methylphenyl)benzo[g]quinoxaline top

Crystal data top

C₂₆H₂₀N₂	F(000) = 760
M_r = 360.44	D_x = 1.234 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.0814 (1) Å	Cell parameters from 3900 reflections
b = 21.5212 (4) Å	θ = 2.3–21.9°
c = 14.8312 (3) Å	µ = 0.07 mm⁻¹
β = 91.2496 (11)°	T = 296 K
V = 1940.63 (6) Å³	Block, yellow
Z = 4	0.15 × 0.12 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	R_int = 0.050
Radiation source: fine-focus sealed tube	θ_max = 28.3°, θ_min = 1.7°
φ and ω scans	h = −8→8
29811 measured reflections	k = −26→28
4805 independent reflections	l = −19→19
2628 reflections with I > 2σ(I)

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0451P)² + 0.2858P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
4805 reflections	Δρ_max = 0.17 e Å⁻³
255 parameters	Δρ_min = −0.16 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
N1	0.7331 (2)	0.02999 (6)	0.12787 (9)	0.0539 (4)
C2	0.5746 (3)	0.02628 (7)	0.18606 (11)	0.0496 (4)
C3	0.4315 (3)	0.07859 (8)	0.20406 (11)	0.0496 (4)
N4	0.4398 (2)	0.12958 (7)	0.15602 (9)	0.0551 (4)
C5	0.5980 (3)	0.13326 (8)	0.09102 (11)	0.0513 (4)
C6	0.6102 (3)	0.18621 (8)	0.03848 (12)	0.0595 (5)
H6	0.5033	0.2169	0.0436	0.071*
C7	0.7797 (3)	0.19434 (8)	−0.02186 (11)	0.0549 (4)
C8	0.7963 (3)	0.24860 (9)	−0.07635 (13)	0.0683 (5)
H8	0.6866	0.2787	−0.0744	0.082*
C9	0.9686 (3)	0.25701 (10)	−0.13079 (13)	0.0728 (6)
H9	0.9765	0.2926	−0.1661	0.087*
C10	1.1356 (3)	0.21237 (10)	−0.13438 (13)	0.0728 (6)
H10	1.2561	0.2195	−0.1706	0.087*
C11	1.1252 (3)	0.15891 (9)	−0.08612 (12)	0.0647 (5)
H11	1.2362	0.1294	−0.0908	0.078*
C12	0.9451 (3)	0.14766 (8)	−0.02829 (11)	0.0529 (4)
C13	0.9257 (3)	0.09318 (8)	0.02196 (11)	0.0558 (4)
H13	1.0299	0.0619	0.0160	0.067*
C14	0.7539 (3)	0.08485 (8)	0.08053 (11)	0.0499 (4)
C15	0.5403 (3)	−0.03522 (7)	0.22942 (10)	0.0495 (4)
C16	0.7057 (3)	−0.06426 (9)	0.27877 (12)	0.0620 (5)
H16	0.8411	−0.0447	0.2868	0.074*
C17	0.6716 (3)	−0.12205 (9)	0.31627 (12)	0.0659 (5)
H17	0.7840	−0.1404	0.3504	0.079*
C18	0.4750 (3)	−0.15320 (8)	0.30446 (11)	0.0586 (5)
C19	0.3114 (3)	−0.12401 (9)	0.25490 (12)	0.0614 (5)
H19	0.1773	−0.1441	0.2457	0.074*
C20	0.3415 (3)	−0.06556 (8)	0.21842 (11)	0.0572 (4)
H20	0.2271	−0.0466	0.1863	0.069*
C21	0.4416 (4)	−0.21754 (9)	0.34221 (15)	0.0851 (6)
H21A	0.3101	−0.2353	0.3161	0.128*
H21B	0.4281	−0.2151	0.4065	0.128*
H21C	0.5654	−0.2432	0.3281	0.128*
C22	0.2735 (3)	0.08010 (8)	0.27948 (11)	0.0509 (4)
C23	0.3194 (3)	0.05472 (9)	0.36372 (12)	0.0622 (5)
H23	0.4479	0.0320	0.3730	0.075*
C24	0.1768 (3)	0.06271 (9)	0.43408 (12)	0.0671 (5)
H24	0.2127	0.0459	0.4902	0.080*
C25	−0.0174 (3)	0.09511 (9)	0.42289 (13)	0.0638 (5)
C26	−0.0646 (3)	0.11931 (9)	0.33862 (13)	0.0641 (5)
H26	−0.1963	0.1405	0.3289	0.077*
C27	0.0785 (3)	0.11292 (8)	0.26840 (12)	0.0571 (4)
H27	0.0439	0.1309	0.2128	0.068*
C28	−0.1697 (3)	0.10576 (11)	0.50077 (14)	0.0894 (7)
H28A	−0.1592	0.1483	0.5200	0.134*
H28B	−0.1282	0.0789	0.5499	0.134*
H28C	−0.3183	0.0969	0.4818	0.134*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0563 (9)	0.0479 (9)	0.0578 (8)	0.0029 (7)	0.0064 (7)	−0.0033 (7)
C2	0.0513 (9)	0.0470 (10)	0.0504 (9)	0.0003 (8)	0.0000 (8)	−0.0053 (7)
C3	0.0481 (9)	0.0491 (10)	0.0516 (9)	−0.0002 (8)	0.0015 (7)	−0.0062 (8)
N4	0.0543 (8)	0.0508 (9)	0.0603 (8)	0.0030 (7)	0.0080 (7)	−0.0010 (7)
C5	0.0501 (10)	0.0492 (10)	0.0548 (10)	0.0015 (8)	0.0030 (8)	−0.0033 (8)
C6	0.0592 (11)	0.0513 (11)	0.0682 (11)	0.0062 (9)	0.0067 (9)	0.0008 (9)
C7	0.0580 (11)	0.0516 (11)	0.0552 (10)	−0.0047 (8)	0.0011 (8)	−0.0020 (8)
C8	0.0749 (13)	0.0567 (12)	0.0736 (12)	−0.0015 (10)	0.0065 (10)	0.0068 (10)
C9	0.0868 (15)	0.0592 (13)	0.0727 (13)	−0.0142 (11)	0.0065 (11)	0.0076 (10)
C10	0.0758 (14)	0.0766 (14)	0.0666 (12)	−0.0194 (12)	0.0157 (10)	−0.0011 (11)
C11	0.0625 (12)	0.0691 (13)	0.0628 (11)	−0.0042 (10)	0.0099 (9)	−0.0067 (10)
C12	0.0566 (10)	0.0543 (11)	0.0480 (9)	−0.0059 (8)	0.0029 (8)	−0.0070 (8)
C13	0.0570 (10)	0.0534 (10)	0.0573 (10)	0.0060 (8)	0.0055 (8)	−0.0058 (8)
C14	0.0528 (10)	0.0468 (10)	0.0501 (9)	−0.0015 (8)	0.0031 (7)	−0.0053 (8)
C15	0.0517 (10)	0.0472 (10)	0.0496 (9)	0.0032 (8)	0.0039 (7)	−0.0053 (8)
C16	0.0535 (11)	0.0614 (12)	0.0709 (12)	0.0014 (9)	−0.0013 (9)	−0.0010 (10)
C17	0.0686 (13)	0.0642 (12)	0.0647 (11)	0.0130 (10)	−0.0037 (9)	0.0066 (10)
C18	0.0726 (13)	0.0516 (11)	0.0519 (10)	0.0035 (9)	0.0108 (9)	−0.0012 (8)
C19	0.0624 (12)	0.0572 (11)	0.0646 (11)	−0.0114 (9)	0.0025 (9)	−0.0047 (9)
C20	0.0581 (11)	0.0534 (11)	0.0597 (10)	−0.0003 (9)	−0.0061 (8)	−0.0009 (8)
C21	0.1156 (18)	0.0598 (13)	0.0806 (14)	0.0034 (12)	0.0196 (13)	0.0129 (11)
C22	0.0508 (10)	0.0469 (10)	0.0551 (10)	−0.0011 (8)	0.0045 (8)	−0.0082 (8)
C23	0.0620 (11)	0.0645 (12)	0.0604 (11)	0.0082 (9)	0.0059 (9)	−0.0029 (9)
C24	0.0761 (13)	0.0709 (13)	0.0546 (10)	0.0037 (11)	0.0111 (9)	−0.0033 (9)
C25	0.0612 (11)	0.0618 (12)	0.0690 (12)	−0.0062 (9)	0.0148 (9)	−0.0163 (10)
C26	0.0503 (10)	0.0659 (12)	0.0762 (13)	0.0038 (9)	0.0048 (9)	−0.0152 (10)
C27	0.0557 (10)	0.0563 (11)	0.0592 (10)	0.0002 (8)	0.0013 (8)	−0.0070 (8)
C28	0.0821 (15)	0.1055 (18)	0.0821 (14)	−0.0039 (13)	0.0310 (12)	−0.0222 (13)

Geometric parameters (Å, º) top

N1—C2	1.3102 (19)	C16—C17	1.380 (3)
N1—C14	1.381 (2)	C16—H16	0.9300
C2—C3	1.451 (2)	C17—C18	1.378 (2)
C2—C15	1.488 (2)	C17—H17	0.9300
C3—N4	1.310 (2)	C18—C19	1.376 (2)
C3—C22	1.491 (2)	C18—C21	1.509 (3)
N4—C5	1.379 (2)	C19—C20	1.383 (2)
C5—C6	1.383 (2)	C19—H19	0.9300
C5—C14	1.419 (2)	C20—H20	0.9300
C6—C7	1.391 (2)	C21—H21A	0.9600
C6—H6	0.9300	C21—H21B	0.9600
C7—C8	1.425 (2)	C21—H21C	0.9600
C7—C12	1.426 (2)	C22—C23	1.386 (2)
C8—C9	1.349 (2)	C22—C27	1.387 (2)
C8—H8	0.9300	C23—C24	1.382 (2)
C9—C10	1.400 (3)	C23—H23	0.9300
C9—H9	0.9300	C24—C25	1.378 (3)
C10—C11	1.357 (3)	C24—H24	0.9300
C10—H10	0.9300	C25—C26	1.378 (3)
C11—C12	1.427 (2)	C25—C28	1.514 (2)
C11—H11	0.9300	C26—C27	1.379 (2)
C12—C13	1.396 (2)	C26—H26	0.9300
C13—C14	1.385 (2)	C27—H27	0.9300
C13—H13	0.9300	C28—H28A	0.9600
C15—C20	1.380 (2)	C28—H28B	0.9600
C15—C16	1.380 (2)	C28—H28C	0.9600

C2—N1—C14	117.63 (14)	C15—C16—H16	119.7
N1—C2—C3	121.78 (15)	C18—C17—C16	121.64 (17)
N1—C2—C15	116.81 (14)	C18—C17—H17	119.2
C3—C2—C15	121.33 (14)	C16—C17—H17	119.2
N4—C3—C2	121.30 (14)	C19—C18—C17	117.44 (17)
N4—C3—C22	115.02 (14)	C19—C18—C21	121.03 (18)
C2—C3—C22	123.63 (15)	C17—C18—C21	121.51 (18)
C3—N4—C5	117.64 (14)	C18—C19—C20	121.59 (17)
N4—C5—C6	119.19 (15)	C18—C19—H19	119.2
N4—C5—C14	120.82 (15)	C20—C19—H19	119.2
C6—C5—C14	119.93 (15)	C15—C20—C19	120.46 (17)
C5—C6—C7	121.02 (16)	C15—C20—H20	119.8
C5—C6—H6	119.5	C19—C20—H20	119.8
C7—C6—H6	119.5	C18—C21—H21A	109.5
C6—C7—C8	122.04 (17)	C18—C21—H21B	109.5
C6—C7—C12	119.22 (16)	H21A—C21—H21B	109.5
C8—C7—C12	118.73 (16)	C18—C21—H21C	109.5
C9—C8—C7	120.99 (19)	H21A—C21—H21C	109.5
C9—C8—H8	119.5	H21B—C21—H21C	109.5
C7—C8—H8	119.5	C23—C22—C27	117.51 (15)
C8—C9—C10	120.29 (19)	C23—C22—C3	123.20 (15)
C8—C9—H9	119.9	C27—C22—C3	119.05 (15)
C10—C9—H9	119.9	C24—C23—C22	120.96 (17)
C11—C10—C9	121.31 (18)	C24—C23—H23	119.5
C11—C10—H10	119.3	C22—C23—H23	119.5
C9—C10—H10	119.3	C25—C24—C23	121.47 (18)
C10—C11—C12	120.39 (18)	C25—C24—H24	119.3
C10—C11—H11	119.8	C23—C24—H24	119.3
C12—C11—H11	119.8	C26—C25—C24	117.47 (16)
C13—C12—C7	119.21 (15)	C26—C25—C28	121.05 (19)
C13—C12—C11	122.58 (17)	C24—C25—C28	121.44 (19)
C7—C12—C11	118.21 (16)	C25—C26—C27	121.64 (17)
C14—C13—C12	121.16 (16)	C25—C26—H26	119.2
C14—C13—H13	119.4	C27—C26—H26	119.2
C12—C13—H13	119.4	C26—C27—C22	120.91 (17)
N1—C14—C13	120.54 (15)	C26—C27—H27	119.5
N1—C14—C5	120.22 (14)	C22—C27—H27	119.5
C13—C14—C5	119.24 (16)	C25—C28—H28A	109.5
C20—C15—C16	118.33 (16)	C25—C28—H28B	109.5
C20—C15—C2	120.02 (15)	H28A—C28—H28B	109.5
C16—C15—C2	121.62 (16)	C25—C28—H28C	109.5
C17—C16—C15	120.51 (17)	H28A—C28—H28C	109.5
C17—C16—H16	119.7	H28B—C28—H28C	109.5

C14—N1—C2—C3	−3.0 (2)	C6—C5—C14—N1	−175.17 (16)
C14—N1—C2—C15	173.87 (14)	N4—C5—C14—C13	−172.58 (15)
N1—C2—C3—N4	7.3 (2)	C6—C5—C14—C13	4.4 (2)
C15—C2—C3—N4	−169.37 (15)	N1—C2—C15—C20	−119.48 (17)
N1—C2—C3—C22	−169.84 (15)	C3—C2—C15—C20	57.4 (2)
C15—C2—C3—C22	13.5 (2)	N1—C2—C15—C16	58.5 (2)
C2—C3—N4—C5	−3.6 (2)	C3—C2—C15—C16	−124.69 (17)
C22—C3—N4—C5	173.74 (14)	C20—C15—C16—C17	−0.3 (3)
C3—N4—C5—C6	179.40 (16)	C2—C15—C16—C17	−178.24 (16)
C3—N4—C5—C14	−3.6 (2)	C15—C16—C17—C18	1.4 (3)
N4—C5—C6—C7	173.89 (16)	C16—C17—C18—C19	−1.1 (3)
C14—C5—C6—C7	−3.2 (3)	C16—C17—C18—C21	177.36 (17)
C5—C6—C7—C8	−179.68 (17)	C17—C18—C19—C20	−0.2 (3)
C5—C6—C7—C12	−1.0 (3)	C21—C18—C19—C20	−178.70 (17)
C6—C7—C8—C9	176.35 (18)	C16—C15—C20—C19	−1.0 (2)
C12—C7—C8—C9	−2.3 (3)	C2—C15—C20—C19	176.97 (15)
C7—C8—C9—C10	−0.3 (3)	C18—C19—C20—C15	1.3 (3)
C8—C9—C10—C11	2.3 (3)	N4—C3—C22—C23	−139.82 (17)
C9—C10—C11—C12	−1.7 (3)	C2—C3—C22—C23	37.5 (2)
C6—C7—C12—C13	4.0 (2)	N4—C3—C22—C27	34.4 (2)
C8—C7—C12—C13	−177.35 (16)	C2—C3—C22—C27	−148.26 (16)
C6—C7—C12—C11	−175.84 (16)	C27—C22—C23—C24	−0.9 (3)
C8—C7—C12—C11	2.9 (2)	C3—C22—C23—C24	173.46 (17)
C10—C11—C12—C13	179.29 (17)	C22—C23—C24—C25	1.2 (3)
C10—C11—C12—C7	−0.9 (3)	C23—C24—C25—C26	0.0 (3)
C7—C12—C13—C14	−2.7 (2)	C23—C24—C25—C28	−177.85 (18)
C11—C12—C13—C14	177.09 (16)	C24—C25—C26—C27	−1.6 (3)
C2—N1—C14—C13	176.18 (15)	C28—C25—C26—C27	176.32 (18)
C2—N1—C14—C5	−4.2 (2)	C25—C26—C27—C22	1.9 (3)
C12—C13—C14—N1	178.13 (15)	C23—C22—C27—C26	−0.7 (3)
C12—C13—C14—C5	−1.5 (2)	C3—C22—C27—C26	−175.22 (16)
N4—C5—C14—N1	7.8 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C7–C12 and the N1/C2/C3/N4/C5–C7/C12–C14 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···Cg1ⁱ	0.93	2.88	3.488 (3)	124
C27—H27···Cg2ⁱⁱ	0.93	2.91	3.601 (3)	132

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

Funding information

This work was supported by a two-year research grant of Pusan National University.

References

Achelle, S., Baudequin, C. & Plé, N. (2013). Dyes Pigments, 98, 575–600. CrossRef CAS Google Scholar
Ahn, S. Y., Lee, H. S., Seo, J.-H., Kim, Y. K. & Ha, Y. (2009). Thin Solid Films, 517, 4111–4114. CrossRef CAS Google Scholar
Bandoli, G., Gerber, T. I. A., Jacobs, R. & du Preez, J. G. H. (1994). Inorg. Chem. 33, 178–179. CrossRef CAS Google Scholar
Bruker (2012). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cantalupo, S. A., Salvati, H., McBurney, B., Raju, R., Glagovich, N. M. & Crundwell, G. (2006). J. Chem. Crystallogr. 36, 17–24. Web of Science CSD CrossRef CAS Google Scholar
Chan, C. K. & Chang, M. Y. (2016). Synthesis, 48, 3785–3793. CAS Google Scholar
Chen, H. Y., Yang, C. H., Chi, Y., Cheng, Y. M., Yeh, Y. S., Chou, P. T., Hsieh, H. Y., Liu, C. S., Peng, S. M. & Lee, G. H. (2006). Can. J. Chem. 84, 309–318. CrossRef CAS Google Scholar
Cusumano, M., Di Pietro, M. L., Giannetto, A., Nicolò, F., Nordén, B. & Lincoln, P. (2004). Inorg. Chem. 43, 2416–2421. CrossRef CAS Google Scholar
Djukic, J. P., de Cian, A. & Gruber, N. K. (2005). J. Organomet. Chem. 690, 4822–4827. CrossRef CAS Google Scholar
Escuer, A., Vicente, R., Comas, T., Ribas, J., Gomez, M., Solans, X., Gatteschi, D. & Zanchini, C. (1991). Inorg. Chim. Acta, 181, 51–60. CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Floris, B., Donzello, M. P., Ercolani, C. & Viola, E. (2017). Coord. Chem. Rev. 347, 115–140. CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kim, Y.-I., Yun, S.-J., Kim, D. & Kang, S. K. (2018). Bull. Korean Chem. Soc. 39, 133–136. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Song, M., Yun, S.-J., Nam, K.-S., Liu, H., Gal, Y.-S., Lee, J. W., Jin, S.-H., Lee, J. Y., Kang, S. K. & Kim, Y. I. (2015). J. Organomet. Chem. 794, 197–205. CrossRef CAS Google Scholar
Tariq, S., Somakala, K. & Amir, M. (2018). Eur. J. Med. Chem. 143, 542–557. CrossRef CAS Google Scholar