4′-(3,4-Di­meth­oxy­phen­yl)-2,2′:6′,2′′-terpyridine

Takase, T.; Soga, Y.; Oyama, D.

doi:10.1107/S2414314616009500

organic compounds

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ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160950

doi:10.1107/S2414314616009500

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4′-(3,4-Dimethoxyphenyl)-2,2′:6′,2′′-terpyridine

Tsugiko Takase,^a Yuka Soga ^b and Dai Oyama ^b ^*

^aInstitute of Environmental Radioactivity, Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan, and ^bDepartment of Industrial Systems Engineering, Cluster of Science and Engineering, Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan
^*Correspondence e-mail: daio@sss.fukushima-u.ac.jp

Edited by J. Simpson, University of Otago, New Zealand (Received 13 May 2016; accepted 13 June 2016; online 21 June 2016)

In the title compound, C₂₃H₁₉N₃O₂, the terpyridine unit has a dimethoxyphenyl substituent at the 4-position of the central pyridyl ring. The three pyridyl rings are in a transoid conformation with respect to the interannular C—C bonds. In addition, the pendant dimethoxyphenyl substituent is almost coplanar with the terpyridyl unit; the dihedral angle between the central pyridyl ring and the benzene ring is 7.14 (11)°, which is much smaller than that found in the structural isomer with a 2,5-dimethoxyphenyl substituent. The C—C and C—N bond lengths within the aromatic rings are normal. One of the terminal pyridyl rings is disordered over two sets of sites with an occupancy ratio of 0.744 (7):0.256 (7). The orientation of the two methoxy groups at the 3- and 4-positions is such that the methyl groups point away from each other in opposite directions. In the crystal structure, C–H⋯N hydrogen bonds form chains along b while C—H⋯O contacts form inversion dimers, creating double chains. These combine with C—H⋯π contacts and π⋯π interactions, with a centroid-centroid distance of 3.858 (4) Å, to stack molecules along the b-axis direction.

Keywords: crystal structure; terpyridine; dimethoxyphenyl substituent; hydrogen bonds; π–π contacts.

CCDC reference: 1484781

Structure description

Polypyridines display unique photophysical and redox properties (Winter et al., 2011 ). Terpyridine analogs are also known to act as tridentate ligands using all three of the N-donor atoms.

Although the title compound, C₂₃H₁₉N₃O₂, has been obtained previously by a standard Kröhnke-type synthesis (Whittle et al., 1995 ), we have prepared it by a direct condensation reaction between 2-acetylpyridine and 3,4-dimethoxybenzaldehyde, according to a procedure reported earlier for a similar compound (Storrier et al., 1998 ).

In the molecule (Fig. 1), the terpyridine unit has a dimethoxyphenyl substituent at the 4-position of the central pyridyl ring. The three pyridyl rings adopt the expected transoid conformation with respect to the interannular C—C bonds. The pendant dimethoxyphenyl substituent lies close to the plane of the terpyridyl unit with a dihedral angle of 7.14 (11)° between the N2/C6–C10 and C16–C21 ring planes. This is comparable to that found for the related compound with a phenyl substituent (10.9°; Constable et al., 1990 ) but distinct from that of the corresponding 2,5-dimethoxyphenyl structural isomer (50.2°; Storrier et al., 1998). This difference can be ascribed in part to the intramolecular steric interactions between the ortho-substituents (either –OCH₃ or –H) on the phenyl ring and the 3- or 5-protons on the central pyridine ring. One of the terminal pyridyl rings is disordered over two sets of sites with an occupancy ratio of 0.744 (7):0.256 (7). The orientation of the two methoxy groups at the 3- and 4-positions is such that the methyl groups point away from each other in opposite directions.

Figure 1
The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms. Only the major component of the disordered pyridyl ring is shown.

In the crystal structure, a π–π contact between Cg3 and Cg4, 3.858 (4) Å, (Cg3 and Cg4 are the centroids of the N2/C6–C10 and N3/C11–C15 rings respectively; symmetry operation x, −1 + y, z) stack molecules along the b-axis direction, Fig. 2. C18—H12⋯π and C23—H19⋯π hydrogen bonds (Table 1) also contribute to this stacking. In addition C3A—H3A⋯N3 hydrogen bonds form C(10) chains along a while C23—H18 ⋯O3 contacts form inversion dimers and, together with a C23—H17⋯π contact, generate a double chain of molecules along a. The overall effect, Fig. 3, sees sheets of molecules stacked along the b-axis direction.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg5 are the centroids of the N1/C1–C5A and C16–C21 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3A—H3A⋯N3ⁱ	0.95	2.43	3.285 (7)	149
C23—H18⋯O1ⁱⁱ	0.98	2.53	3.511 (5)	174
C18—H12⋯Cg5ⁱⁱⁱ	0.95	2.87	3.648 (5)	139
C23—H17⋯Cg1^iv	098	2.90	3.432 (5)	115
C23—H19⋯Cg5^v	0.98	2.89	3.724 (5)	143
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) -x+1, -y+1, -z+2; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+2]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (v) x, y+1, z.

Figure 2
π–π contacts in the crystal packing of the title compound. Only the major component of the disordered pyridyl ring is shown.

Figure 3
Overall packing of the title compound viewed along b. Hydrogen bonds are drawn as blue dashed lines with representative π–π and C—H⋯π contacts shown as green dotted lines. Ring centroids are shown as coloured spheres.

Synthesis and crystallization

The title compound was prepared by a direct condensation reaction between 2-acetylpyridine and 3,4-dimethoxybenzaldehyde in ammonium acetate–acetamide to afford a pale-yellow solid in 23% yield, which is a modification of a literature method (Storrier et al., 1998). The crude product was purified by column chromatography and then recrystallized from a chloroform–diethyl ether (1/40) mixture at ambient temperature to give good quality crystals suitable for X-ray diffraction.

Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 2. The carbon atoms of one of the pyridyl rings were disordered over two sites and refined as (C2A, C3A, C4A, C5A) and (C2B, C3B, C4B, C5B) with occupancies that sum to unity. This disorder model converged with an occupancy ratio 0.744 (7):0.256 (7).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₃H₁₉N₃O₂
M_r	369.42
Crystal system, space group	Monoclinic, P2₁/a
Temperature (K)	93
a, b, c (Å)	18.280 (14), 5.493 (4), 18.298 (14)
β (°)	96.020 (6)
V (Å³)	1827 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.15 × 0.08

Data collection
Diffractometer	Rigaku Saturn724
Absorption correction	Multi-scan (REQAB; Rigaku, 1998 )
T_min, T_max	0.881, 0.993
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	17670, 4118, 2937
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.100, 0.224, 1.14
No. of reflections	4118
No. of parameters	270
No. of restraints	18
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.43
Computer programs: CrystalClear (Rigaku, 2008 ), SIR92 (Altomare et al., 1993 ), SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ), CrystalStructure (Rigaku, 2010 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1484781

Crystal structure: contains datablocks General, I. DOI: 10.1107/S2414314616009500/sj4034sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616009500/sj4034Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616009500/sj4034Isup3.mol

Supporting information file. DOI: 10.1107/S2414314616009500/sj4034Isup4.cml

checkCIF report

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: CrystalStructure (Rigaku, 2010), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

4'-(3,4-Dimethoxyphenyl)-2,2':6',2''-terpyridine top

Crystal data top

C₂₃H₁₉N₃O₂	F(000) = 776.00
M_r = 369.42	D_x = 1.343 Mg m⁻³
Monoclinic, P2₁/a	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2yab	Cell parameters from 3564 reflections
a = 18.280 (14) Å	θ = 3.0–27.5°
b = 5.493 (4) Å	µ = 0.09 mm⁻¹
c = 18.298 (14) Å	T = 93 K
β = 96.020 (6)°	Block, colorless
V = 1827 (3) Å³	0.20 × 0.15 × 0.08 mm
Z = 4

Data collection top

Rigaku Saturn724 diffractometer	2937 reflections with F² > 2.0σ(F²)
Detector resolution: 28.944 pixels mm^-1	R_int = 0.075
ω scans	θ_max = 27.4°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −23→23
T_min = 0.881, T_max = 0.993	k = −7→6
17670 measured reflections	l = −23→23
4118 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.100	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.224	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0698P)² + 2.0174P] where P = (F_o² + 2F_c²)/3
4118 reflections	(Δ/σ)_max < 0.001
270 parameters	Δρ_max = 0.44 e Å⁻³
18 restraints	Δρ_min = −0.43 e Å⁻³
Primary atom site location: structure-invariant direct methods

Special details top

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	Occ. (<1)
O1	0.40936 (11)	0.0742 (5)	1.03502 (12)	0.0328 (6)
O2	0.42133 (12)	0.4172 (5)	0.94160 (13)	0.0373 (6)
N1	0.01717 (16)	−0.3469 (7)	0.74911 (17)	0.0458 (9)
N2	0.09106 (15)	0.1770 (6)	0.66251 (15)	0.0391 (8)
N3	0.21225 (16)	0.6651 (6)	0.61704 (18)	0.0458 (9)
C1	−0.0454 (2)	−0.4808 (8)	0.7454 (2)	0.0482 (10)
C2B	−0.0955 (12)	−0.468 (4)	0.6835 (11)	0.045 (6)*	0.256 (7)
C2A	−0.1103 (4)	−0.4111 (14)	0.7073 (4)	0.0463 (16)	0.744 (7)
C3B	−0.0833 (9)	−0.324 (3)	0.6262 (9)	0.045 (5)*	0.256 (7)
C3A	−0.1108 (3)	−0.1923 (11)	0.6710 (3)	0.0416 (15)	0.744 (7)
C4B	−0.0222 (8)	−0.173 (3)	0.6330 (8)	0.033 (4)*	0.256 (7)
C4A	−0.0474 (3)	−0.0582 (9)	0.6719 (3)	0.0343 (13)	0.744 (7)
C5B	0.0254 (16)	−0.171 (6)	0.6961 (14)	0.031 (7)*	0.256 (7)
C5A	0.0166 (5)	−0.1472 (17)	0.7106 (5)	0.0294 (17)	0.744 (7)
C6	0.08608 (17)	0.0020 (7)	0.71429 (17)	0.0312 (8)
C7	0.13976 (16)	−0.0289 (6)	0.77322 (17)	0.0282 (7)
C8	0.20105 (16)	0.1251 (6)	0.78114 (16)	0.0282 (7)
C9	0.20605 (16)	0.3003 (6)	0.72868 (17)	0.0290 (7)
C10	0.15111 (18)	0.3231 (7)	0.66967 (17)	0.0327 (8)
C11	0.1539 (2)	0.5164 (8)	0.6129 (2)	0.0419 (9)
C12	0.0988 (4)	0.5414 (11)	0.5584 (3)	0.096 (2)
C13	0.1006 (4)	0.7274 (14)	0.5080 (4)	0.127 (3)
C14	0.1603 (3)	0.8778 (11)	0.5112 (3)	0.0791 (17)
C15	0.2144 (3)	0.8425 (8)	0.5668 (3)	0.0509 (11)
C16	0.25678 (16)	0.1036 (6)	0.84759 (17)	0.0271 (7)
C17	0.25191 (17)	−0.0796 (7)	0.89922 (18)	0.0314 (8)
C18	0.30174 (17)	−0.0968 (7)	0.96230 (18)	0.0307 (8)
C19	0.35774 (16)	0.0731 (6)	0.97494 (16)	0.0274 (7)
C20	0.36432 (16)	0.2606 (6)	0.92346 (17)	0.0269 (7)
C21	0.31479 (16)	0.2735 (6)	0.86080 (17)	0.0270 (7)
C22	0.4094 (2)	−0.1284 (7)	1.0841 (2)	0.0459 (10)
C23	0.43971 (19)	0.5865 (7)	0.88633 (19)	0.0376 (9)
H1	−0.0441	−0.6320	0.7708	0.0578*
H2A	−0.1532	−0.5095	0.7060	0.0556*	0.744 (7)
H2B	−0.1392	−0.5629	0.6811	0.0545*	0.256 (7)
H3A	−0.1551	−0.1337	0.6452	0.0499*	0.744 (7)
H3B	−0.1159	−0.3268	0.5822	0.0543*	0.256 (7)
H4A	−0.0473	0.0928	0.6467	0.0411*	0.744 (7)
H4B	−0.0133	−0.0686	0.5934	0.0391*	0.256 (7)
H5	0.1348	−0.1544	0.8081	0.0338*
H6	0.2471	0.4072	0.7323	0.0348*
H7	0.0587	0.4306	0.5547	0.1153*
H8	0.0605	0.7506	0.4712	0.1520*
H9	0.1638	1.0028	0.4759	0.0949*
H10	0.2558	0.9482	0.5703	0.0611*
H11	0.2136	−0.1965	0.8914	0.0377*
H12	0.2973	−0.2247	0.9965	0.0368*
H13	0.3199	0.3991	0.8260	0.0324*
H14	0.4415	−0.0927	1.1291	0.0551*
H15	0.4275	−0.2734	1.0605	0.0551*
H16	0.3593	−0.1579	1.0964	0.0551*
H17	0.4553	0.4966	0.8444	0.0452*
H18	0.4798	0.6925	0.9070	0.0452*
H19	0.3965	0.6857	0.8700	0.0452*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0254 (12)	0.0376 (14)	0.0326 (12)	−0.0081 (10)	−0.0100 (9)	0.0043 (11)
O2	0.0285 (12)	0.0427 (15)	0.0385 (13)	−0.0161 (11)	−0.0062 (10)	0.0035 (11)
N1	0.0304 (16)	0.064 (3)	0.0415 (17)	−0.0086 (15)	−0.0048 (13)	0.0096 (17)
N2	0.0261 (15)	0.052 (2)	0.0378 (16)	−0.0039 (14)	−0.0017 (12)	0.0015 (15)
N3	0.0301 (16)	0.048 (2)	0.060 (2)	0.0081 (14)	0.0083 (15)	0.0105 (17)
C1	0.043 (3)	0.058 (3)	0.042 (2)	−0.007 (2)	−0.0024 (17)	0.016 (2)
C2A	0.032 (3)	0.073 (5)	0.034 (3)	−0.018 (3)	0.000 (3)	0.007 (4)
C3A	0.023 (3)	0.067 (4)	0.033 (3)	−0.004 (3)	−0.0054 (19)	0.003 (3)
C4A	0.026 (3)	0.040 (3)	0.035 (3)	−0.002 (2)	−0.0054 (19)	0.004 (3)
C5A	0.020 (3)	0.048 (5)	0.020 (4)	−0.000 (3)	−0.000 (3)	−0.002 (3)
C6	0.0226 (15)	0.040 (2)	0.0302 (16)	0.0030 (14)	−0.0024 (13)	−0.0003 (15)
C7	0.0229 (15)	0.0327 (18)	0.0277 (16)	0.0018 (13)	−0.0026 (13)	−0.0017 (14)
C8	0.0203 (15)	0.0366 (19)	0.0273 (16)	0.0044 (13)	0.0011 (12)	−0.0050 (14)
C9	0.0179 (14)	0.0382 (19)	0.0306 (16)	−0.0011 (14)	0.0005 (13)	−0.0037 (15)
C10	0.0267 (17)	0.041 (2)	0.0302 (16)	−0.0003 (15)	0.0017 (13)	−0.0059 (15)
C11	0.0333 (19)	0.052 (3)	0.041 (2)	−0.0086 (17)	0.0034 (16)	0.0035 (18)
C12	0.096 (4)	0.114 (5)	0.068 (3)	−0.069 (4)	−0.038 (3)	0.048 (3)
C13	0.112 (5)	0.156 (6)	0.098 (4)	−0.079 (5)	−0.057 (4)	0.072 (4)
C14	0.072 (4)	0.097 (4)	0.065 (3)	−0.027 (3)	−0.012 (3)	0.040 (3)
C15	0.039 (3)	0.048 (3)	0.067 (3)	0.0001 (19)	0.013 (2)	0.019 (3)
C16	0.0172 (14)	0.0338 (18)	0.0298 (16)	0.0015 (13)	−0.0004 (12)	−0.0046 (14)
C17	0.0216 (15)	0.0337 (19)	0.0374 (18)	−0.0064 (14)	−0.0039 (13)	−0.0006 (15)
C18	0.0250 (16)	0.0332 (18)	0.0324 (17)	−0.0043 (14)	−0.0038 (13)	0.0032 (15)
C19	0.0199 (15)	0.0332 (18)	0.0280 (16)	−0.0006 (13)	−0.0032 (12)	−0.0040 (14)
C20	0.0194 (14)	0.0299 (18)	0.0312 (16)	−0.0018 (13)	0.0019 (12)	−0.0032 (14)
C21	0.0216 (15)	0.0301 (18)	0.0291 (16)	−0.0008 (13)	0.0014 (12)	0.0009 (14)
C22	0.043 (2)	0.046 (3)	0.044 (2)	−0.0116 (18)	−0.0174 (17)	0.0109 (18)
C23	0.0342 (18)	0.041 (2)	0.0372 (19)	−0.0146 (16)	0.0027 (15)	0.0059 (16)

Geometric parameters (Å, º) top

O1—C19	1.372 (4)	C14—C15	1.357 (7)
O1—C22	1.430 (5)	C16—C17	1.390 (5)
O2—C20	1.365 (4)	C16—C21	1.414 (5)
O2—C23	1.439 (5)	C17—C18	1.397 (5)
N1—C1	1.356 (6)	C18—C19	1.387 (5)
N1—C5B	1.39 (3)	C19—C20	1.409 (5)
N1—C5A	1.303 (10)	C20—C21	1.386 (5)
N2—C6	1.360 (5)	C1—H1	0.950
N2—C10	1.355 (5)	C2B—H2B	0.950
N3—C11	1.340 (5)	C2A—H2A	0.950
N3—C15	1.344 (6)	C3B—H3B	0.950
C1—C2B	1.38 (2)	C3A—H3A	0.950
C1—C2A	1.366 (7)	C4B—H4B	0.950
C2B—C3B	1.35 (3)	C4A—H4A	0.950
C2A—C3A	1.373 (9)	C7—H5	0.950
C3B—C4B	1.39 (2)	C9—H6	0.950
C3A—C4A	1.371 (7)	C12—H7	0.950
C4B—C5B	1.37 (3)	C13—H8	0.950
C4A—C5A	1.392 (9)	C14—H9	0.950
C5B—C6	1.47 (3)	C15—H10	0.950
C5A—C6	1.51 (1)	C17—H11	0.950
C6—C7	1.390 (5)	C18—H12	0.950
C7—C8	1.399 (5)	C21—H13	0.950
C8—C9	1.369 (5)	C22—H14	0.980
C8—C16	1.507 (4)	C22—H15	0.980
C9—C10	1.401 (5)	C22—H16	0.980
C10—C11	1.490 (6)	C23—H17	0.980
C11—C12	1.348 (7)	C23—H18	0.980
C12—C13	1.379 (9)	C23—H19	0.980
C13—C14	1.365 (9)

C19—O1—C22	117.0 (3)	C2B—C1—H1	115.146
C20—O2—C23	117.7 (3)	C2A—C1—H1	118.101
C1—N1—C5B	119.7 (12)	C1—C2B—H2B	119.442
C1—N1—C5A	118.1 (5)	C3B—C2B—H2B	119.434
C6—N2—C10	117.7 (3)	C1—C2A—H2A	121.526
C11—N3—C15	119.0 (4)	C3A—C2A—H2A	121.510
N1—C1—C2B	119.8 (10)	C2B—C3B—H3B	120.699
N1—C1—C2A	123.8 (5)	C4B—C3B—H3B	120.704
C1—C2B—C3B	121.1 (17)	C2A—C3A—H3A	119.945
C1—C2A—C3A	117.0 (6)	C4A—C3A—H3A	119.929
C2B—C3B—C4B	118.6 (15)	C3B—C4B—H4B	119.525
C2A—C3A—C4A	120.1 (5)	C5B—C4B—H4B	119.544
C3B—C4B—C5B	120.9 (17)	C3A—C4A—H4A	120.592
C3A—C4A—C5A	118.8 (6)	C5A—C4A—H4A	120.568
N1—C5B—C4B	118 (3)	C6—C7—H5	120.034
N1—C5A—C4A	121.9 (7)	C8—C7—H5	120.028
N2—C6—C7	122.2 (3)	C8—C9—H6	119.727
C6—C7—C8	119.9 (3)	C10—C9—H6	119.732
C7—C8—C9	117.6 (3)	C11—C12—H7	119.902
C7—C8—C16	120.2 (3)	C13—C12—H7	119.894
C9—C8—C16	122.1 (3)	C12—C13—H8	120.215
C8—C9—C10	120.5 (3)	C14—C13—H8	120.221
N2—C10—C9	122.0 (3)	C13—C14—H9	121.201
N2—C10—C11	116.2 (3)	C15—C14—H9	121.188
C9—C10—C11	121.8 (3)	N3—C15—H10	118.484
N3—C11—C10	118.7 (3)	C14—C15—H10	118.487
N3—C11—C12	120.5 (4)	C16—C17—H11	119.063
C10—C11—C12	120.8 (4)	C18—C17—H11	119.048
C11—C12—C13	120.2 (6)	C17—C18—H12	120.059
C12—C13—C14	119.6 (6)	C19—C18—H12	120.051
C13—C14—C15	117.6 (6)	C16—C21—H13	119.310
N3—C15—C14	123.0 (4)	C20—C21—H13	119.313
C8—C16—C17	121.3 (3)	O1—C22—H14	109.474
C8—C16—C21	121.2 (3)	O1—C22—H15	109.477
C17—C16—C21	117.5 (3)	O1—C22—H16	109.470
C16—C17—C18	121.9 (3)	H14—C22—H15	109.474
C17—C18—C19	119.9 (3)	H14—C22—H16	109.461
O1—C19—C18	124.8 (3)	H15—C22—H16	109.471
O1—C19—C20	115.6 (3)	O2—C23—H17	109.476
C18—C19—C20	119.6 (3)	O2—C23—H18	109.480
O2—C20—C19	114.5 (3)	O2—C23—H19	109.465
O2—C20—C21	125.8 (3)	H17—C23—H18	109.468
C19—C20—C21	119.7 (3)	H17—C23—H19	109.463
C16—C21—C20	121.4 (3)	H18—C23—H19	109.475
N1—C1—H1	118.105

C22—O1—C19—C18	6.5 (5)	C7—C8—C16—C17	5.0 (5)
C22—O1—C19—C20	−173.2 (3)	C7—C8—C16—C21	−173.1 (3)
C23—O2—C20—C19	169.3 (3)	C9—C8—C16—C17	−178.2 (3)
C23—O2—C20—C21	−10.8 (5)	C9—C8—C16—C21	3.6 (5)
C1—N1—C5B—C4B	−14 (3)	C16—C8—C9—C10	−176.5 (3)
C5B—N1—C1—C2B	9.9 (15)	C8—C9—C10—N2	0.8 (5)
C5B—N1—C1—C2A	−20.7 (15)	C8—C9—C10—C11	178.2 (3)
C1—N1—C5A—C4A	6.1 (10)	N2—C10—C11—N3	−179.6 (3)
C5A—N1—C1—C2B	26.3 (7)	N2—C10—C11—C12	0.4 (5)
C5A—N1—C1—C2A	−4.3 (7)	C9—C10—C11—N3	2.9 (5)
C6—N2—C10—C9	−1.1 (5)	C9—C10—C11—C12	−177.1 (3)
C6—N2—C10—C11	−178.6 (3)	N3—C11—C12—C13	−2.8 (8)
C10—N2—C6—C7	0.3 (5)	C10—C11—C12—C13	177.3 (4)
C11—N3—C15—C14	−0.6 (6)	C11—C12—C13—C14	3.5 (10)
C15—N3—C11—C10	−178.8 (4)	C12—C13—C14—C15	−2.8 (9)
C15—N3—C11—C12	1.3 (6)	C13—C14—C15—N3	1.3 (8)
N1—C1—C2B—C3B	−0 (2)	C8—C16—C17—C18	−177.8 (3)
N1—C1—C2A—C3A	0.2 (8)	C8—C16—C21—C20	177.2 (3)
C2B—C1—C2A—C3A	−89 (2)	C17—C16—C21—C20	−1.0 (5)
C2A—C1—C2B—C3B	107 (3)	C21—C16—C17—C18	0.4 (5)
C1—C2B—C3B—C4B	−5 (3)	C16—C17—C18—C19	0.4 (5)
C1—C2A—C3A—C4A	2.1 (8)	C17—C18—C19—O1	179.7 (3)
C2B—C3B—C4B—C5B	1 (3)	C17—C18—C19—C20	−0.7 (5)
C2A—C3A—C4A—C5A	−0.4 (8)	O1—C19—C20—O2	−0.4 (4)
C3B—C4B—C5B—N1	9 (4)	O1—C19—C20—C21	179.7 (3)
C3A—C4A—C5A—N1	−3.9 (10)	C18—C19—C20—O2	179.9 (3)
N2—C6—C7—C8	0.8 (5)	C18—C19—C20—C21	0.0 (5)
C6—C7—C8—C9	−1.1 (5)	O2—C20—C21—C16	−179.1 (3)
C6—C7—C8—C16	175.8 (3)	C19—C20—C21—C16	0.8 (5)
C7—C8—C9—C10	0.3 (5)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg5 are the centroids of the N1,C1–C5A and C16–C21 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C3A—H3A···N3ⁱ	0.95	2.43	3.285 (7)	149
C23—H18···O1ⁱⁱ	0.98	2.53	3.511 (5)	174
C18—H12···Cg5ⁱⁱⁱ	0.95	2.87	3.648 (5)	139
C23—H17···Cg1^iv	098	2.90	3.432 (5)	115
C23—H19···Cg5^v	0.98	2.89	3.724 (5)	143

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

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