Crystal structure of 7,15-bis­(4-tert-butyl­phen­yl)-1,9-di­methyl­hepta­zethrene

Kamata, S.; Sato, S.; Wu, J.; Isobe, H.

doi:10.1107/S2056989016020247

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 73| Part 2| February 2017| Pages 99-102

https://doi.org/10.1107/S2056989016020247

Open

access

Crystal structure of 7,15-bis(4-tert-butylphenyl)-1,9-dimethylheptazethrene

Sho Kamata,^a Sota Sato,^a,^b Jishan Wu ^c ^* and Hiroyuki Isobe ^a,^b,^d ^*

^aAdvanced Institute for Materials Research, Tohoku University, Aoba-ku, Sendai 980-8577, Japan, ^bJST, ERATO, Isobe Degenerate π-Integration Project, Aoba-ku, Sendai 980-8577, Japan, ^cDepartment of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore, and ^dDepartment of Chemistry, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
^*Correspondence e-mail: chmwuj@nus.edu.sg, isobe@chem.s.u-tokyo.ac.jp

Edited by H. Ishida, Okayama University, Japan (Received 8 December 2016; accepted 20 December 2016; online 6 January 2017)

The title compound, C₅₀H₄₄, 1, was synthesized as a derivative of heptazethrene bearing two methyl and two tert-butylphenyl substituents, respectively, at the 1,9- and 7,15-positions. The asymmetric unit consists of one half of the molecule, which lies about an inversion centre. Albeit remotely located, the substituents contort the heptazethrene plane. The tert-butylphenyl substituents stand approximately perpendicular to the core plane, with a dihedral angle of 79.09 (5)° between the phenalene ring system and the substituted benzene ring, and prevent direct intermolecular contacts of the heptazethrene cores.

Keywords: crystal structure; heptazethrene; substituent effect.

CCDC reference: 1523781

1. Chemical context

Heptazethrene is a polycyclic aromatic hydrocarbon with a characteristic Z-shaped molecular structure. A series of heptazethrene derivatives have been synthesized by one of the authors, and a derivative, 2, with methyl and silylethynyl substituents at the 1,9- and 7,15-positions has been reported as the first closed-shell congener (Li et al., 2012 ). In the crystal structure of 2, we noticed that the silylethynyl substituents are distorted into a non-linear geometry. Considering that the distorted structure originated from steric interactions between the 1,9- and 7,15-positions, we investigated substituent effects on the molecular structure. Replacing the silylethynyl groups with tert-butylphenyl groups, we designed the title compound, 1, and synthesized it via a route recently established for other heptazethrene derivatives (Hu et al., 2016 ).

2. Structural commentary

The molecular structure of 1 (Fig. 1) consists of a heptazethrene unit at the core, two methyl substituents at the 1,9-positions and two tert-butylphenyl substituents at the 7,15-positions. One-half of the molecule is generated by the symmetry operation (1 − x, 1 − y, 1 − z), and carbon atoms at the 1/9-, 7/15- or 8/16-positions, for instance, are symmetrically equivalent (Fig. 2a). As is the case with 2, a typical bond-length alternation in the central hexagon is observed, indicating a quinoidal character for 1 (Li et al., 2012). Unlike 2, however, the heptazethrene core of 1 is not flat but contorted. The mean plane of the heptazethrene core is generated by adopting 28 carbon atoms of the core (OLEX2; Dolomanov et al., 2009 ) and the deviation of the atoms from the mean plane is visualized in Fig. 2b. The maximum deviation of 0.2969 (10) Å is recorded (by using OLEX2) for the carbon atoms at the 7- and 15-positions. The same analysis was applied to 2 (Fig. 2c), and the maximum distance from the mean plane is 0.103 (3) Å for the carbon atoms at the 8- and 16-positions. The contorted structure of 1 is also evidenced by the torsion angle at the 1–16b–16a–16 (see Fig. 1) positions, is −16.91 (19)°. For 2, the torsion angle at the same position is 5.8 (3)°, which indicates that steric interactions between the 1-methyl and 7-phenyl groups may result in the contorted structure.

Figure 1
Chemical structures of heptazethrene derivatives. Numbers of positions are displayed for 1.

Figure 2
The molecular structures of heptazethrene derivatives. Displacement ellipsoids are drawn at the 50% probability level. (a) 1 with the atom-numbering scheme [symmetry code: (i) 1 − x, 1 − y, 1 − z]. (b) 1 with a mean plane of 28 C atoms, viewed perpendicular to the plane shown in red. (c) 2 with a mean plane of 28 C atoms, viewed perpendicular to the plane shown in red.

3. Supramolecular features

As is the case of 2 (Li et al., 2012), the molecules of 1 form layers with the heptazethrene cores assembled in a parallel manner (Fig. 3). However, due to the bulky phenyl groups at the 7,15-positions, the heptazethrene cores do not directly contact each other. C—H⋯π interactions are instead observed between the heptazethrene core and the phenyl substituent (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C3/C3A/C3A1/C8B and C3A1/C3A/C4–C6/C6A rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3P—H3P⋯Cg1ⁱ	0.95	2.80	3.6278 (15)	147
C3T—H3T2⋯Cg2ⁱ	0.98	2.97	3.7929 (17)	143
Symmetry code: (i) x, y+1, z.

Figure 3
Packing diagram of 1, viewed along the c axis.

4. Database survey

A search of the Cambridge Structural Database (version 5.37 Update 2; Groom et al., 2016 ) for heptazethrene derivatives returns one result, compound 2 (Li et al., 2012). Two newer derivatives, 1,9-bis(hexyloxy)-7,15-dimesityl-heptazethrene and 1,9-bis(hexyloxy)-7,15-bis(pentafluorophenyl)-heptazethrene, have recently been reported (Hu et al., 2016). Detailed comparisons with compound 2 are described above. The other two derivatives possessing 7,15-phenyl groups and 1,9-alkoxy substituents are also contorted. Two crystallographically independent molecules are observed in 1,9-bis(hexyloxy)-7,15-dimesityl-heptazethrene, and the 1–16b–16a–16 torsion angles are 2.55 (19) and 13.94 (19)°. One molecule is observed in 1,9-bis(hexyloxy)-7,15-bis(pentafluorophenyl)-heptazethrene, and the corresponding torsion angle is 6.44 (18)°.

5. Synthesis and crystallization

The title compound 1 was synthesized by a method reported in a literature (Hu et al., 2016) with different starting materials for the introduction of different substituents (Fig. 4). A mixture of 2,5-dibromo-terephthalaldehyde 3 (2.30 g, 7.89 mmol), 2-methylnaphthylboronic acid 4 (4.41 g, 23.7 mmol), Pd₂(dba)₃·CHCl₃ (407 mg, 0.393 mmol), SPhos (648 mg, 1.58 mmol) and K₂CO₃ (5.46 g, 39.4 mmol) was stirred in a deaerated solvent composed of toluene (70.8 ml), ethanol (17.2 ml) and water (19.0 ml) at 363 K for 24 h. The reaction was quenched by addition of saturated aqueous NH₄Cl (50 ml). Organic materials were extracted with CHCl₃ (30 ml × 4), and the combined organic phase was washed with brine, dried over MgSO₄ and concentrated in vacuo. Crude materials were purified by silica gel column chromatography (eluent: 30% CHCl₃/hexane) to afford the coupling product 5 in 2.02 g (4.87 mmol, 62% yield) as a yellow powder. The compound 5 (1.64 g, 3.97 mmol) was dissolved in THF (80.0 mL), and to the solution was added 4-tert-butylphenylmagnesium bromide (30.0 ml, 0.66 M in diethyl ether, 19.8 mmol) at 273 K. The mixture was stirred for 2 h, and saturated aqueous NH₄Cl (20 ml) was added. Organic materials were extracted with ethyl acetate (50 ml × 3), and the combined organic phase was washed with brine, dried over Na₂SO₄ and concentrated in vacuo to give a yellow oil containing diol 6. Without purification, the crude material was dissolved in CH₂Cl₂ (200 ml), and BF₃·Et₂O (5.10 ml, 39.5 mmol) was added at ambient temperature. After 10 min, methanol (10 ml) was added, and volatile materials were removed in vacuo. The crude material was washed with methanol (50 ml), and a purple solid containing the cyclized compound 7 was obtained. Without purification, the crude material was dissolved in toluene (400 ml), and to the solution was added a solution of 2,3-dichloro-5,6-dicyano-para-benzoquinone (DDQ; 70.0 ml, 79.5 mM in toluene, 5.57 mmol) at ambient temperature. After 1 h, the mixture was poured onto a pad of silica gel (250 g) and eluted with toluene to afford the title compound 1. A small amount of contaminants was noted and was removed by washing the compound with methanol (50 ml) to afford the title compound 1 (1.33 g, 2.06 mmol, 52% in three steps from 5) as a purple solid. Suitable single crystals were grown from slow liquid–liquid diffusion of acetonitrile into a toluene solution of 1.

Figure 4
Synthesis of the title compound, 1.

Physical data: m.p. ca 643 K (decomposed); IR (ATR, neat): 567, 587, 764, 803, 825, 837, 1017, 1108, 1269, 1362, 1447, 1461, 2864, 2901, 2951 cm⁻¹; ¹H NMR (400 MHz, C₆D₆) δ 1.32 (s, 18H), 2.36 (s, 6H), 7.03 (t, J = 8.0Hz, 2H), 7.09 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 7.8 Hz, 2H), 7.28 (dt, J = 8.4 Hz, 2.0 Hz, 4H), 7.36 (d, J = 8.0 Hz, 2H), 7.37 (dt, J = 8.4 Hz, 2.0 Hz, 4H), 7.38 (d, J = 8.4 Hz, 2.0 Hz, 4H), 7.72 (s, 2H); ¹³C NMR (100 MHz, C₆D₆) δ 26.0 (CH₃), 31.5 (CH₃), 34.6, 125.6 (CH), 126.1* (CH), 127.1 (CH), 127.4 (CH), 129.2 (CH), 129.7, 130.3, 131.0* (CH), 131.7, 132.6 (CH), 133.2, 133.6, 134.7, 136.0, 136.7, 150.3 (Resonances with * appeared with twofold intensities and should contain two overlapping resonances.); HR–MS (DART–TOF, positive) calculated for C₅₀H₄₄ [M+H]⁺ 645.3521, found 645.3545.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned geometrically and refined as riding, allowing for rotation of the methyl group, with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for aromatic H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₅₀H₄₄
M_r	644.90
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	93
a, b, c (Å)	8.7644 (2), 9.2002 (3), 13.1212 (3)
α, β, γ (°)	105.874 (2), 95.080 (2), 115.249 (3)
V (Å³)	894.47 (5)
Z	1
Radiation type	Cu Kα
μ (mm⁻¹)	0.51
Crystal size (mm)	0.15 × 0.08 × 0.03

Data collection
Diffractometer	Rigaku XtaLAB P200
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Corporation, Tokyo, Japan.]$ )
T_min, T_max	0.878, 0.985
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	22866, 3256, 2930
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.131, 1.08
No. of reflections	3256
No. of parameters	230
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.23
Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Corporation, Tokyo, Japan.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), CrystalStructure (Rigaku, 2016 ), Mercury (Macrae et al., 2008 ), OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1523781

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989016020247/is5468sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016020247/is5468Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016020247/is5468Isup3.mol

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: CrystalStructure (Rigaku, 2016) and Mercury (Macrae et al., 2008); software used to prepare material for publication: CrystalStructure (Rigaku, 2016), OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

7,15-Bis(4-tert-butylphenyl)-1,9-dimethylheptazethrene top

Crystal data top

C₅₀H₄₄	Z = 1
M_r = 644.90	F(000) = 344.00
Triclinic, P1	D_x = 1.197 Mg m⁻³
a = 8.7644 (2) Å	Cu Kα radiation, λ = 1.54187 Å
b = 9.2002 (3) Å	Cell parameters from 15939 reflections
c = 13.1212 (3) Å	θ = 3.6–68.2°
α = 105.874 (2)°	µ = 0.51 mm⁻¹
β = 95.080 (2)°	T = 93 K
γ = 115.249 (3)°	Block, purple
V = 894.47 (5) Å³	0.15 × 0.08 × 0.03 mm

Data collection top

Rigaku XtaLAB P200 diffractometer	2930 reflections with F² > 2.0σ(F²)
Detector resolution: 5.811 pixels mm^-1	R_int = 0.026
ω scans	θ_max = 68.3°, θ_min = 3.6°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	h = −10→10
T_min = 0.878, T_max = 0.985	k = −9→10
22866 measured reflections	l = −15→15
3256 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0807P)² + 0.1872P] where P = (F_o² + 2F_c²)/3
3256 reflections	(Δ/σ)_max < 0.001
230 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³
Primary atom site location: structure-invariant direct methods

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. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
C1	0.77143 (15)	0.27792 (16)	0.37967 (10)	0.0282 (3)
C2	0.82438 (16)	0.19027 (16)	0.29671 (11)	0.0304 (3)
H2	0.901044	0.149216	0.316696	0.036*
C3	0.77086 (16)	0.16138 (16)	0.18882 (11)	0.0294 (3)
H3	0.802444	0.093561	0.135216	0.035*
C3A	0.66842 (15)	0.23267 (15)	0.15725 (10)	0.0270 (3)
C3A1	0.61706 (14)	0.32728 (14)	0.23942 (10)	0.0247 (3)
C4	0.61937 (16)	0.21352 (16)	0.04656 (10)	0.0299 (3)
H4	0.651358	0.147501	−0.007973	0.036*
C5	0.52627 (16)	0.28945 (16)	0.01768 (10)	0.0308 (3)
H5	0.492798	0.274895	−0.056770	0.037*
C6	0.48038 (16)	0.38832 (16)	0.09751 (10)	0.0284 (3)
H6	0.418515	0.442753	0.076400	0.034*
C6A	0.52289 (15)	0.40922 (15)	0.20719 (10)	0.0254 (3)
C7	0.47383 (15)	0.51085 (15)	0.28851 (10)	0.0253 (3)
C7A	0.49880 (15)	0.51364 (15)	0.39461 (10)	0.0255 (3)
C8	0.42937 (15)	0.59605 (15)	0.47208 (10)	0.0261 (3)
H8	0.386896	0.666232	0.452300	0.031*
C8A	0.57990 (15)	0.41936 (15)	0.42770 (10)	0.0249 (3)
C8B	0.65887 (15)	0.34037 (15)	0.35078 (10)	0.0255 (3)
C1M	0.84692 (17)	0.29973 (19)	0.49464 (11)	0.0359 (3)
H1M1	0.953456	0.288760	0.496403	0.054*
H1M2	0.762462	0.211359	0.517639	0.054*
H1M3	0.873653	0.413186	0.544212	0.054*
C1P	0.37768 (15)	0.59823 (15)	0.25632 (9)	0.0257 (3)
C2P	0.45677 (15)	0.77354 (16)	0.27639 (10)	0.0275 (3)
H2P	0.578450	0.840095	0.305958	0.033*
C3P	0.36053 (16)	0.85288 (16)	0.25386 (10)	0.0278 (3)
H3P	0.418003	0.972795	0.268045	0.033*
C4P	0.18176 (15)	0.76070 (15)	0.21096 (10)	0.0273 (3)
C5P	0.10460 (16)	0.58447 (16)	0.18943 (11)	0.0329 (3)
H5P	−0.016815	0.517320	0.158986	0.039*
C6P	0.19987 (16)	0.50500 (16)	0.21115 (11)	0.0317 (3)
H6P	0.142991	0.384575	0.194958	0.038*
C1T	0.06794 (16)	0.84316 (17)	0.19069 (11)	0.0333 (3)
C2T	−0.05461 (19)	0.8203 (2)	0.26853 (15)	0.0468 (4)
H2T1	−0.118334	0.698859	0.259859	0.070*
H2T2	−0.137001	0.861074	0.251474	0.070*
H2T3	0.013342	0.886463	0.343903	0.070*
C3T	0.17399 (17)	1.03289 (17)	0.20891 (13)	0.0401 (3)
H3T1	0.096047	1.078314	0.191671	0.060*
H3T2	0.255721	1.048167	0.161518	0.060*
H3T3	0.238494	1.094359	0.285279	0.060*
C4T	−0.04149 (19)	0.7524 (2)	0.07259 (13)	0.0465 (4)
H4T1	−0.118581	0.631892	0.061158	0.070*
H4T2	0.035486	0.759603	0.022257	0.070*
H4T3	−0.111104	0.807899	0.059085	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0275 (6)	0.0267 (6)	0.0350 (6)	0.0137 (5)	0.0094 (5)	0.0150 (5)
C2	0.0297 (6)	0.0289 (6)	0.0402 (7)	0.0168 (5)	0.0122 (5)	0.0169 (5)
C3	0.0297 (6)	0.0253 (6)	0.0382 (7)	0.0147 (5)	0.0143 (5)	0.0130 (5)
C3A	0.0256 (6)	0.0229 (6)	0.0331 (6)	0.0092 (5)	0.0105 (5)	0.0129 (5)
C3A1	0.0226 (5)	0.0204 (6)	0.0323 (6)	0.0087 (5)	0.0088 (5)	0.0124 (5)
C4	0.0327 (6)	0.0255 (6)	0.0324 (6)	0.0129 (5)	0.0126 (5)	0.0112 (5)
C5	0.0357 (7)	0.0287 (7)	0.0286 (6)	0.0132 (5)	0.0095 (5)	0.0131 (5)
C6	0.0306 (6)	0.0263 (6)	0.0319 (6)	0.0130 (5)	0.0088 (5)	0.0153 (5)
C6A	0.0239 (6)	0.0221 (6)	0.0312 (6)	0.0088 (5)	0.0082 (5)	0.0132 (5)
C7	0.0248 (6)	0.0223 (6)	0.0309 (6)	0.0106 (5)	0.0074 (5)	0.0128 (5)
C7A	0.0256 (6)	0.0229 (6)	0.0307 (6)	0.0114 (5)	0.0077 (5)	0.0131 (5)
C8	0.0272 (6)	0.0247 (6)	0.0320 (6)	0.0145 (5)	0.0078 (5)	0.0137 (5)
C8A	0.0247 (6)	0.0224 (6)	0.0290 (6)	0.0112 (5)	0.0058 (4)	0.0110 (5)
C8B	0.0239 (6)	0.0218 (6)	0.0315 (6)	0.0093 (5)	0.0078 (5)	0.0124 (5)
C1M	0.0378 (7)	0.0472 (8)	0.0390 (7)	0.0293 (6)	0.0127 (6)	0.0218 (6)
C1P	0.0294 (6)	0.0279 (6)	0.0255 (6)	0.0152 (5)	0.0097 (5)	0.0137 (5)
C2P	0.0245 (6)	0.0276 (6)	0.0327 (6)	0.0117 (5)	0.0083 (5)	0.0144 (5)
C3P	0.0283 (6)	0.0237 (6)	0.0351 (6)	0.0123 (5)	0.0098 (5)	0.0144 (5)
C4P	0.0277 (6)	0.0269 (6)	0.0315 (6)	0.0142 (5)	0.0091 (5)	0.0135 (5)
C5P	0.0256 (6)	0.0279 (7)	0.0434 (7)	0.0104 (5)	0.0041 (5)	0.0146 (6)
C6P	0.0311 (6)	0.0229 (6)	0.0409 (7)	0.0114 (5)	0.0055 (5)	0.0139 (5)
C1T	0.0261 (6)	0.0300 (7)	0.0477 (7)	0.0144 (5)	0.0088 (5)	0.0171 (6)
C2T	0.0397 (8)	0.0401 (8)	0.0768 (11)	0.0247 (7)	0.0285 (7)	0.0292 (8)
C3T	0.0315 (7)	0.0308 (7)	0.0654 (9)	0.0172 (6)	0.0110 (6)	0.0232 (7)
C4T	0.0373 (7)	0.0427 (8)	0.0607 (9)	0.0206 (7)	−0.0017 (7)	0.0205 (7)

Geometric parameters (Å, º) top

C1—C2	1.4068 (18)	C1M—H1M2	0.9800
C1—C8B	1.4084 (17)	C1M—H1M3	0.9800
C1—C1M	1.5159 (17)	C1P—C2P	1.3902 (17)
C2—C3	1.3655 (18)	C1P—C6P	1.3905 (17)
C2—H2	0.9500	C2P—C3P	1.3896 (17)
C3—C3A	1.4117 (17)	C2P—H2P	0.9500
C3—H3	0.9500	C3P—C4P	1.3928 (17)
C3A—C4	1.4178 (17)	C3P—H3P	0.9500
C3A—C3A1	1.4247 (17)	C4P—C5P	1.3950 (17)
C3A1—C8B	1.4335 (17)	C4P—C1T	1.5331 (17)
C3A1—C6A	1.4394 (17)	C5P—C6P	1.3804 (17)
C4—C5	1.3689 (18)	C5P—H5P	0.9500
C4—H4	0.9500	C6P—H6P	0.9500
C5—C6	1.3970 (18)	C1T—C3T	1.5220 (18)
C5—H5	0.9500	C1T—C2T	1.5361 (19)
C6—C6A	1.3926 (17)	C1T—C4T	1.538 (2)
C6—H6	0.9500	C2T—H2T1	0.9800
C6A—C7	1.4409 (17)	C2T—H2T2	0.9800
C7—C7A	1.3813 (17)	C2T—H2T3	0.9800
C7—C1P	1.4952 (16)	C3T—H3T1	0.9800
C7A—C8	1.4353 (17)	C3T—H3T2	0.9800
C7A—C8A	1.4572 (16)	C3T—H3T3	0.9800
C8—C8Aⁱ	1.3664 (17)	C4T—H4T1	0.9800
C8—H8	0.9500	C4T—H4T2	0.9800
C8A—C8B	1.4756 (17)	C4T—H4T3	0.9800
C1M—H1M1	0.9800

C2—C1—C8B	118.76 (11)	C1—C1M—H1M3	109.5
C2—C1—C1M	115.40 (11)	H1M1—C1M—H1M3	109.5
C8B—C1—C1M	125.82 (11)	H1M2—C1M—H1M3	109.5
C3—C2—C1	123.15 (12)	C2P—C1P—C6P	117.68 (11)
C3—C2—H2	118.4	C2P—C1P—C7	122.52 (11)
C1—C2—H2	118.4	C6P—C1P—C7	119.66 (11)
C2—C3—C3A	119.76 (12)	C3P—C2P—C1P	121.00 (11)
C2—C3—H3	120.1	C3P—C2P—H2P	119.5
C3A—C3—H3	120.1	C1P—C2P—H2P	119.5
C3—C3A—C4	121.12 (11)	C2P—C3P—C4P	121.54 (11)
C3—C3A—C3A1	118.58 (11)	C2P—C3P—H3P	119.2
C4—C3A—C3A1	120.30 (11)	C4P—C3P—H3P	119.2
C3A—C3A1—C8B	120.68 (11)	C3P—C4P—C5P	116.84 (11)
C3A—C3A1—C6A	118.01 (11)	C3P—C4P—C1T	123.67 (11)
C8B—C3A1—C6A	121.30 (11)	C5P—C4P—C1T	119.45 (11)
C5—C4—C3A	120.49 (11)	C6P—C5P—C4P	121.80 (11)
C5—C4—H4	119.8	C6P—C5P—H5P	119.1
C3A—C4—H4	119.8	C4P—C5P—H5P	119.1
C4—C5—C6	120.12 (11)	C5P—C6P—C1P	121.12 (12)
C4—C5—H5	119.9	C5P—C6P—H6P	119.4
C6—C5—H5	119.9	C1P—C6P—H6P	119.4
C6A—C6—C5	121.78 (12)	C3T—C1T—C4P	112.58 (10)
C6A—C6—H6	119.1	C3T—C1T—C2T	109.31 (12)
C5—C6—H6	119.1	C4P—C1T—C2T	108.22 (11)
C6—C6A—C3A1	119.22 (11)	C3T—C1T—C4T	108.22 (11)
C6—C6A—C7	121.14 (11)	C4P—C1T—C4T	109.63 (11)
C3A1—C6A—C7	119.64 (11)	C2T—C1T—C4T	108.82 (12)
C7A—C7—C6A	120.21 (11)	C1T—C2T—H2T1	109.5
C7A—C7—C1P	119.24 (11)	C1T—C2T—H2T2	109.5
C6A—C7—C1P	120.20 (10)	H2T1—C2T—H2T2	109.5
C7—C7A—C8	120.18 (11)	C1T—C2T—H2T3	109.5
C7—C7A—C8A	121.18 (11)	H2T1—C2T—H2T3	109.5
C8—C7A—C8A	118.35 (11)	H2T2—C2T—H2T3	109.5
C8Aⁱ—C8—C7A	124.58 (11)	C1T—C3T—H3T1	109.5
C8Aⁱ—C8—H8	117.7	C1T—C3T—H3T2	109.5
C7A—C8—H8	117.7	H3T1—C3T—H3T2	109.5
C8ⁱ—C8A—C7A	116.82 (11)	C1T—C3T—H3T3	109.5
C8ⁱ—C8A—C8B	124.06 (11)	H3T1—C3T—H3T3	109.5
C7A—C8A—C8B	119.05 (11)	H3T2—C3T—H3T3	109.5
C1—C8B—C3A1	118.48 (11)	C1T—C4T—H4T1	109.5
C1—C8B—C8A	124.42 (11)	C1T—C4T—H4T2	109.5
C3A1—C8B—C8A	117.10 (11)	H4T1—C4T—H4T2	109.5
C1—C1M—H1M1	109.5	C1T—C4T—H4T3	109.5
C1—C1M—H1M2	109.5	H4T1—C4T—H4T3	109.5
H1M1—C1M—H1M2	109.5	H4T2—C4T—H4T3	109.5

C8B—C1—C2—C3	−0.49 (19)	C2—C1—C8B—C3A1	−6.23 (17)
C1M—C1—C2—C3	−179.09 (12)	C1M—C1—C8B—C3A1	172.20 (11)
C1—C2—C3—C3A	5.13 (19)	C2—C1—C8B—C8A	173.80 (11)
C2—C3—C3A—C4	176.25 (11)	C1M—C1—C8B—C8A	−7.76 (19)
C2—C3—C3A—C3A1	−2.76 (17)	C3A—C3A1—C8B—C1	8.50 (17)
C3—C3A—C3A1—C8B	−4.01 (17)	C6A—C3A1—C8B—C1	−171.30 (10)
C4—C3A—C3A1—C8B	176.97 (10)	C3A—C3A1—C8B—C8A	−171.53 (10)
C3—C3A—C3A1—C6A	175.79 (10)	C6A—C3A1—C8B—C8A	8.67 (16)
C4—C3A—C3A1—C6A	−3.22 (17)	C8ⁱ—C8A—C8B—C1	−16.91 (19)
C3—C3A—C4—C5	−177.21 (11)	C7A—C8A—C8B—C1	166.07 (11)
C3A1—C3A—C4—C5	1.78 (18)	C8ⁱ—C8A—C8B—C3A1	163.12 (11)
C3A—C4—C5—C6	0.71 (18)	C7A—C8A—C8B—C3A1	−13.90 (16)
C4—C5—C6—C6A	−1.71 (19)	C7A—C7—C1P—C2P	81.89 (15)
C5—C6—C6A—C3A1	0.18 (18)	C6A—C7—C1P—C2P	−104.89 (14)
C5—C6—C6A—C7	−179.66 (11)	C7A—C7—C1P—C6P	−93.64 (14)
C3A—C3A1—C6A—C6	2.25 (16)	C6A—C7—C1P—C6P	79.58 (14)
C8B—C3A1—C6A—C6	−177.94 (10)	C6P—C1P—C2P—C3P	1.16 (17)
C3A—C3A1—C6A—C7	−177.91 (10)	C7—C1P—C2P—C3P	−174.46 (10)
C8B—C3A1—C6A—C7	1.89 (17)	C1P—C2P—C3P—C4P	0.31 (18)
C6—C6A—C7—C7A	172.31 (11)	C2P—C3P—C4P—C5P	−1.40 (18)
C3A1—C6A—C7—C7A	−7.52 (17)	C2P—C3P—C4P—C1T	176.39 (11)
C6—C6A—C7—C1P	−0.83 (17)	C3P—C4P—C5P—C6P	1.05 (19)
C3A1—C6A—C7—C1P	179.33 (10)	C1T—C4P—C5P—C6P	−176.83 (12)
C6A—C7—C7A—C8	−171.72 (10)	C4P—C5P—C6P—C1P	0.4 (2)
C1P—C7—C7A—C8	1.50 (17)	C2P—C1P—C6P—C5P	−1.51 (18)
C6A—C7—C7A—C8A	2.04 (17)	C7—C1P—C6P—C5P	174.24 (11)
C1P—C7—C7A—C8A	175.25 (10)	C3P—C4P—C1T—C3T	7.25 (18)
C7—C7A—C8—C8Aⁱ	168.00 (12)	C5P—C4P—C1T—C3T	−175.02 (12)
C8A—C7A—C8—C8Aⁱ	−5.93 (19)	C3P—C4P—C1T—C2T	−113.67 (14)
C7—C7A—C8A—C8ⁱ	−168.40 (12)	C5P—C4P—C1T—C2T	64.06 (15)
C8—C7A—C8A—C8ⁱ	5.47 (18)	C3P—C4P—C1T—C4T	127.77 (13)
C7—C7A—C8A—C8B	8.83 (17)	C5P—C4P—C1T—C4T	−54.50 (15)
C8—C7A—C8A—C8B	−177.30 (10)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C3/C3A/C3A1/C8B and C3A1/C3A/C4–C6/C6A rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C3P—H3P···Cg1ⁱⁱ	0.95	2.80	3.6278 (15)	147
C3T—H3T2···Cg2ⁱⁱ	0.98	2.97	3.7929 (17)	143

Symmetry code: (ii) x, y+1, z.

Acknowledgements

This work was partly supported by KAKENHI (24241036, 16K04864, 25102007). SK thanks JSPS for a predoctoral fellowship. The following funding is acknowledged: Japan Society for the Promotion of Science (award No. 24241036, 16K04864, 25102007).

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals 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
Hu, P., Lee, S., Herng, T. S., Aratani, N., Gonçalves, T. P., Qi, Q., Shi, X., Yamada, H., Huang, K.-H., Ding, J., Kim, D. & Wu, J. (2016). J. Am. Chem. Soc. 138, 1065–1077. Web of Science CSD CrossRef CAS Google Scholar
Li, Y., Heng, W.-K., Lee, B. S., Aratani, N., Zafra, J. L., Bao, N., Lee, R., Sung, Y. M., Sun, Z., Huang, K.-H., Webster, R. R., López Navarrete, J. T., Kim, D., Osuka, A., Casado, J., Ding, J. & Wu, J. (2012). J. Am. Chem. Soc. 134, 14913–14922. Web of Science CSD CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku (2016). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.