Crystal structure of tris­[4-(3,4-di­meth­oxy­thio­phen-2-yl)phen­yl]amine

Yano, M.; Kashiwagi, Y.; Oishi, K.; Yano, M.; Mitsudo, K.

doi:10.1107/S2056989026000058

research communications

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ISSN: 2056-9890

Volume 82| Part 2| February 2026| Pages 148-151

https://doi.org/10.1107/S2056989026000058

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Crystal structure of tris[4-(3,4-dimethoxythiophen-2-yl)phenyl]amine

Masafumi Yano,^a ^* Yukiyasu Kashiwagi,^b Koki Oishi,^a Minori Yano ^a and Koichi Mitsudo ^c

^aKansai University, 3-3-35 Yamate-cho, Suita, Osaka 564-8680, Japan, ^bOsaka Research Institute of Industrial Science and Technology, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan, and ^cOkayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan
^*Correspondence e-mail: [email protected]

Edited by Y. Ozawa, University of Hyogo, Japan (Received 25 November 2025; accepted 4 January 2026; online 8 January 2026)

In the title compound tris[4-(3,4-dimethoxythiophen-2-yl)phenyl]amine (DMOT-TPA), C₃₆H₃₃NO₆S₃, the central nitrogen atom shows no pyramidalization, with the three para-phenylene rings arranged in a propeller-like geometry. Each thiophene ring is twisted by about 25–29° relative to the adjacent phenylene ring, giving a distorted π-conjugated framework. In the crystal, molecules are linked through multiple C—H⋯π interactions into two-dimensional sheets, which extend into a three-dimensional network. A Cambridge Structural Database survey revealed no prior examples of triphenylamines bearing 3,4-dimethoxythiophen units at the para positions. This unique structure provides new insights into the design of redox-active organic materials.

Keywords: crystal structure; infrared absorption dye; one-electron oxidation.

CCDC reference: 2520149

1. Chemical context

Triarylamines (TAAs) are well-known electron donors and continue to be the subject of much theoretical and experimental research. Since TAA derivatives with various substituents in the para-position give stable radical cations by one-electron oxidation in solution, they are used in the fields of positively charged purely organic high-spin systems (Sato et al., 1997 ) as well as for organic mixed-valence molecular systems (Lambert et al., 1999 ). TAAs with extra aromatic rings in the para-position have received notable attention as components of redox-active organic materials (Yen & Liou, 2012 ; Thelakkat, 2002 ). Among them, tris(4-(thiophene-2-yl)phenyl)amine and its π-extended derivatives have been developed into electroactive polymer electrodes and electrochromic polymer materials, and many derivatives continue to be reported (Golba et al., 2015 ). Thiophenes with strong electron-donating substituents at the β-position show enhanced donor properties and high stability. Consequently, a triphenylamine derivative incorporating three 3,4-dimethoxythiophene groups is expected to behave as a redox-active core that enables facile electron transfer in both solution and the solid state, with potential relevance to molecular electronic materials. We report herein on the crystal structure of the title compound.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The central N10 atom shows no pyramidalization, with a deviation from the plane of the bonded C atoms (C18, C30, and C42) of 0.025 (2) Å. The three para-phenylene rings are bonded to the N10 atom in a propeller-type fashion, which is a common arrangement for Ph₃N fragments. The torsion angles C17—C18—N10—C42, C29—C30—N10—C18 and C41—C42—N10—C30 are −49.7 (2), −30.3 (2) and −29.8 (2)°, respectively. The mean planes of the para-phenylene rings and the neighboring thiophene ring are inclined to each other by 24.19 (10)° for (C15–C20)/(S1/C11–C14), 28.73 (9)° for (C27–C32)/(S2/C23–C26) and 26.67 (9)° for (C39–C44)/(S3/C35–C38).

Figure 1
The molecular structure of the title compound with the atom labeling. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by spheres of arbitrary radius.

3. Supramolecular features

In the crystal, each molecule interacts with five others via four intermolecular C—H⋯π interactions (Table 1). The molecules are linked by complementary C—H⋯π interactions between the methoxy group and a neighboring thiophene ring [C22—H22C⋯Cg3ⁱⁱ and C45—H45A⋯Cg1ⁱⁱ; Cg3 and Cg1 are the centroids of the S3/C35–C38 and S1/C11–C14 rings, respectively; symmetry code: (ii) −x + 1, −y + 1, −z + 1], forming an inversion dimer (Fig. 2). The other two C—H⋯π interactions [C21—H21B⋯Cg5ⁱ and C32—H32⋯Cg5ⁱⁱⁱ; Cg5 is the centroid of the C27–C32 ring; symmetry code: (i) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (iii) −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ] form one-dimensional chain structures parallel to the b-axis (Figs. 3 and 4), and these interactions form two-dimensional sheets in the ac plane. As a result, the two-dimensional sheets are linked by complementary C—H⋯π interactions, forming the dimers mentioned above into a three-dimensional network. Weak intermolecular interactions [O5⋯H45C—H45^iv and O9⋯H34B—C34ⁱⁱⁱ; symmetry code: (iv) −x + 1, −y + 2, −z + 1] are also shown in Table 1. There are no significant intermolecular interactions around Cg2, Cg4 and Cg6 (the centroids of the S2/C23–C26, C15–C20 and C39–C44 rings, respectively).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg3 and Cg5 are the centroids of the S1/C11–C14,S3/C35–C38 and C27–C32 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C21—H21B⋯Cg5ⁱ	0.98	2.95	3.686 (3)	133
C22—H22C⋯Cg3ⁱⁱ	0.98	2.85	3.678 (2)	143
C32—H32⋯Cg5ⁱⁱⁱ	0.95	2.87	3.518 (2)	126
C45—H45A⋯Cg1ⁱⁱ	0.98	2.89	3.820 (2)	160
O5—H45C⋯C45^iv	0.98	2.69	3.336 (3)	123
O9—H34B⋯C34ⁱⁱⁱ	0.98	2.77	3.177 (3)	106
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) .

Figure 2
The centrosymmetric dimeric structure of the title compound. The intermolecular C—H⋯π interactions are shown as dashed lines. H atoms not involved in these interactions have been omitted for clarity. [Symmetry code: (ii) −x + 1, −y + 1, −z + 1.]

Figure 3
A portion of the crystal packing of the title compound showing the spiral chain formed via a 2₁ screw axis. The intermolecular C—H⋯π interactions are shown as dashed lines. H atoms not involved in these interactions have been omitted for clarity. [Symmetry code: (i) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ .]

Figure 4
A portion of the crystal packing of the title compound showing the spiral chain formed via a 2₁ screw axis. The intermolecular C—H⋯π interactions are shown as dashed lines. H atoms not involved in these interactions have been omitted for clarity. [Symmetry code: (iii) −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ .]

In order to further characterize the intermolecular interactions in the crystal of the title compound, a Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) was carried out using CrystalExplorer (version 21.3; Spackman et al., 2021 ). The Hirshfeld surface mapped over d_norm (Fig. 5) shows several localized red spots, which correspond to short C—H⋯O and C—H⋯S contacts between neighboring molecules. The associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) provide quantitative information on the intermolecular interactions in terms of percentage contributions (Spackman & McKinnon, 2002 ). As illustrated in Fig. 6, H⋯H contacts contribute 46.8% to the Hirshfeld surface and dominate the crystal packing, followed by H⋯O/O⋯H (12.7%) and H⋯S/S⋯H (12.8%) contacts.

Figure 5
Hirshfeld surface mapped over d_norm for the title compound. (a) Front view and (b) back view. Red spots indicate short C—H⋯O and C—H⋯S contacts.

Figure 6
Two-dimensional fingerprint plots for the title compound. (a) Full fingerprint plot showing the overall distribution of d_i and d_e. Fingerprint plots highlighting the (b) H⋯O/O⋯H contacts and (c) H⋯S/S⋯H contacts.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 6.00, update August 2025; Groom et al., 2016 ) for compounds containing triphenylamines yielded 9691 hits (including 8428 hits for non-polymeric compounds). Limiting the search to non-polymeric triphenylamines with at least one thiophene ring bonded to triphenylamine core at the 4-position of phenyl group gave 167 hits (149 compounds), which included five hits (five compounds) with the thiophene ring having oxygen atoms at the two β-positions. There was one report of TPA cores bound to EDOT units (BUSZIC; Yuan et al., 2021 ). There are five compounds with thiophene rings at the three para-positions of triphenylamine, three of which do not contain metal ions: tris(2-thiophenyl-4-phenyl)amine (AXELIZ; Wang et al., 2011 ), its triformylated compound tris[2-(5-formylthiophenyl)-4-phenlyl]amine (PAYXAQ; Parthasarathy et al., 2011 ) and tris(2-{5-[N-(butan-2-yl)-2-cyanoprop-2-enamide]thiophenyl}-4-phenlyl)amine (SODXOB; Adelizzi et al., 2019 ). These three compounds adopt a similar propeller-type TPA geometry. A search for compounds containing 2,3-dimethoxythiophene yielded nine hits of which six are non-macrocyclic compounds. Of these six compounds, only two structures contain an aryl-substituent at the α-position of thiophene [ILIWAF (Peng et al., 2025a ) and ILIWEJ Peng et al., 2025b )]. The intermolecular interactions around 2,3-dimethoxythiophene were not shown in ILIWEJ, whereas in contrast only a thiophenyl S⋯H—N interaction was suggested in ILIWAF.

5. Synthesis and crystallization

DMOT-TPA was synthesized under Negishi coupling conditions using the method we previously reported (Yano et al., 2022 ). To a solution of 3,4-dimethoxythiophene (0.10 mL, 0.91 mmol) in tetrahydrofuran (THF, 1.20 mL) were added 1.6 M of n-BuLi in hexane (0.60 mL, 0.96 mmol) at 195 K. After stirring at 195 K for 1 h, 1.0 M of ZnCl₂ in THF (0.96 mL, 0.96 mmol) was slowly added and stirred for 0.5 h at 273 K. 4,4′,4′′-Tribromotriphenylamine (0.11 g, 0.22 mmol) and tris(dibenzylideneacetone)dipalladium(0)·CHCl₃ (3.4 mg, 0.006 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos, 8.5 mg, 0.020 mmol) were added and stirred at 343 K for 1 h. The resulting solution was quenched with water, extracted with chloroform, and dried over sodium sulfate. Upon addition of an excess amount of methanol to this solution, a yellow powder was precipitated (111 mg, 76%). ¹H NMR (400 MHz, CDCl₃): δ 3.84 (s, 9H), 3.86 (s, 9H), 6.10 (s, 3H), 7.12 (d, J = 8.8 Hz, 6H), 7.60 (d, J = 8.8 Hz, 6H). Pale-yellow crystals of DMOT-TPA suitable for X-ray diffraction were obtained by slowly evaporating a solution dissolved in a mixture of acetonitrile and toluene.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were placed in geometrically calculated positions (C—H = 0.95–0.99 Å) and were constrained using a riding model with U_iso(H) = 1.2 U_eq(C) for aromatic H atoms and U_iso(H) = 1.5U_eq(C) for methyl H atoms. Anisotropic displacement parameters for the C25 and O7 were refined with enhanced rigid bond (RIGU) restraints.

Table 2
Experimental details

Crystal data
Chemical formula	C₃₆H₃₃NO₆S₃
M_r	671.81
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	15.5226 (2), 7.7010 (1), 26.7200 (3)
β (°)	91.204 (1)
V (Å³)	3193.39 (7)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	2.53
Crystal size (mm)	0.21 × 0.16 × 0.06

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 )
T_min, T_max	0.743, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	22361, 6361, 5681
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.632

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.111, 1.02
No. of reflections	6361
No. of parameters	421
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.94, −0.42
Computer programs: CrysAlis PRO (Rigaku OD, 2023), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2520149

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989026000058/ox2019sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989026000058/ox2019Isup3.hkl

checkCIF report

Computing details top

Tris[4-(3,4-dimethoxythiophen-2-yl)phenyl]amine top

Crystal data top

C₃₆H₃₃NO₆S₃	F(000) = 1408
M_r = 671.81	D_x = 1.397 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 15.5226 (2) Å	Cell parameters from 14178 reflections
b = 7.7010 (1) Å	θ = 3.3–76.6°
c = 26.7200 (3) Å	µ = 2.53 mm⁻¹
β = 91.204 (1)°	T = 100 K
V = 3193.39 (7) Å³	Block, colourless
Z = 4	0.21 × 0.16 × 0.06 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	6361 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	5681 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.033
Detector resolution: 10.0000 pixels mm^-1	θ_max = 77.2°, θ_min = 3.3°
ω scans	h = −18→13
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −8→9
T_min = 0.743, T_max = 1.000	l = −33→33
22361 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0509P)² + 3.2582P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
6361 reflections	Δρ_max = 0.94 e Å⁻³
421 parameters	Δρ_min = −0.42 e Å⁻³
3 restraints

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. 1. Fixed Uiso At 1.2 times of: All C(H) groups At 1.5 times of: All C(H,H,H) groups 2. Rigid body (RIGU) restrains C25, O7 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004 3.a Aromatic/amide H refined with riding coordinates: C11(H11), C16(H16), C17(H17), C19(H19), C20(H20), C23(H23), C28(H28), C29(H29), C31(H31), C32(H32), C35(H35), C40(H40), C41(H41), C43(H43), C44(H44) 3.b Idealised Me refined as rotating group: C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C33(H33A,H33B,H33C), C34(H34A,H34B, H34C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C)

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

	x	y	z	U_iso*/U_eq
S1	0.15454 (3)	0.61897 (6)	0.74361 (2)	0.02413 (12)
S2	0.88651 (3)	0.67913 (7)	0.84372 (2)	0.02604 (13)
S3	0.65454 (3)	0.69538 (7)	0.42247 (2)	0.02619 (13)
O4	−0.01202 (9)	0.8147 (2)	0.64844 (6)	0.0328 (4)
O5	0.15437 (8)	0.84512 (19)	0.61326 (5)	0.0249 (3)
O6	0.80763 (10)	0.6858 (2)	0.98068 (5)	0.0340 (4)
O7	0.66877 (9)	0.7054 (2)	0.91195 (5)	0.0268 (3)
O8	0.89878 (9)	0.7417 (2)	0.39631 (6)	0.0321 (3)
O9	0.86873 (8)	0.70643 (19)	0.49969 (5)	0.0267 (3)
N10	0.56623 (9)	0.6838 (2)	0.66955 (6)	0.0187 (3)
C11	0.05196 (12)	0.6737 (3)	0.72270 (8)	0.0272 (4)
H11	0.000890	0.652459	0.740695	0.033*
C12	0.05418 (12)	0.7512 (3)	0.67704 (8)	0.0253 (4)
C13	0.13939 (12)	0.7672 (3)	0.65852 (7)	0.0225 (4)
C14	0.20158 (12)	0.7025 (2)	0.69029 (7)	0.0204 (4)
C15	0.29556 (11)	0.6979 (2)	0.68452 (7)	0.0190 (4)
C16	0.33683 (12)	0.8166 (2)	0.65342 (7)	0.0198 (4)
H16	0.303730	0.900860	0.635563	0.024*
C17	0.42564 (11)	0.8124 (2)	0.64839 (7)	0.0196 (4)
H17	0.452921	0.894621	0.627473	0.024*
C18	0.47490 (11)	0.6885 (2)	0.67382 (7)	0.0179 (4)
C19	0.43444 (12)	0.5700 (3)	0.70489 (7)	0.0219 (4)
H19	0.467624	0.484914	0.722364	0.026*
C20	0.34577 (12)	0.5757 (3)	0.71040 (7)	0.0221 (4)
H20	0.318898	0.495381	0.732090	0.027*
C21	−0.09498 (13)	0.8072 (3)	0.67058 (10)	0.0395 (6)
H21A	−0.137225	0.866666	0.648867	0.059*
H21B	−0.092517	0.864110	0.703379	0.059*
H21C	−0.112074	0.685583	0.674668	0.059*
C22	0.15958 (17)	0.7259 (3)	0.57280 (9)	0.0398 (5)
H22A	0.171514	0.789302	0.541908	0.060*
H22B	0.104772	0.663664	0.568901	0.060*
H22C	0.206030	0.642531	0.579691	0.060*
C23	0.90087 (14)	0.6775 (3)	0.90789 (8)	0.0299 (4)
H23	0.955181	0.669282	0.924775	0.036*
C24	0.82440 (13)	0.6896 (3)	0.93090 (7)	0.0244 (4)
C25	0.75199 (12)	0.7020 (2)	0.89652 (7)	0.0233 (4)
C26	0.77498 (12)	0.6958 (2)	0.84772 (7)	0.0228 (4)
C27	0.71990 (12)	0.6918 (2)	0.80234 (7)	0.0200 (4)
C28	0.63873 (12)	0.7722 (3)	0.80027 (7)	0.0215 (4)
H28	0.617920	0.829520	0.829087	0.026*
C29	0.58852 (11)	0.7691 (2)	0.75675 (7)	0.0203 (4)
H29	0.533869	0.824701	0.756097	0.024*
C30	0.61729 (11)	0.6852 (2)	0.71385 (7)	0.0176 (4)
C31	0.69720 (11)	0.6013 (2)	0.71623 (7)	0.0201 (4)
H31	0.717290	0.540505	0.687819	0.024*
C32	0.74708 (11)	0.6062 (3)	0.75967 (7)	0.0214 (4)
H32	0.801441	0.549442	0.760393	0.026*
C33	0.88133 (17)	0.6453 (4)	1.01196 (9)	0.0425 (6)
H33A	0.904878	0.532511	1.002132	0.064*
H33B	0.864043	0.640395	1.046997	0.064*
H33C	0.925342	0.735222	1.008088	0.064*
C34	0.64284 (15)	0.8624 (3)	0.93519 (8)	0.0350 (5)
H34A	0.648322	0.958819	0.911527	0.053*
H34B	0.679611	0.884297	0.964782	0.053*
H34C	0.582716	0.852390	0.945285	0.053*
C35	0.74226 (14)	0.7185 (3)	0.38445 (7)	0.0276 (4)
H35	0.739170	0.723729	0.348938	0.033*
C36	0.81654 (13)	0.7282 (3)	0.41233 (8)	0.0246 (4)
C37	0.80256 (12)	0.7177 (2)	0.46504 (7)	0.0217 (4)
C38	0.71760 (12)	0.7016 (2)	0.47683 (7)	0.0203 (4)
C39	0.67883 (11)	0.6946 (2)	0.52628 (7)	0.0191 (4)
C40	0.71954 (11)	0.7724 (2)	0.56792 (7)	0.0205 (4)
H40	0.773563	0.828183	0.564031	0.025*
C41	0.68258 (11)	0.7693 (2)	0.61449 (7)	0.0190 (4)
H41	0.711357	0.823785	0.642015	0.023*
C42	0.60348 (11)	0.6873 (2)	0.62174 (7)	0.0175 (4)
C43	0.56175 (11)	0.6112 (3)	0.58047 (7)	0.0209 (4)
H43	0.507540	0.556146	0.584383	0.025*
C44	0.59910 (12)	0.6156 (3)	0.53377 (7)	0.0213 (4)
H44	0.569634	0.563537	0.506108	0.026*
C45	0.90692 (16)	0.7684 (3)	0.34378 (8)	0.0382 (5)
H45A	0.890781	0.661829	0.325859	0.057*
H45B	0.966713	0.798344	0.336488	0.057*
H45C	0.868842	0.863281	0.332921	0.057*
C46	0.91999 (14)	0.8600 (3)	0.50474 (9)	0.0358 (5)
H46A	0.943976	0.890115	0.472241	0.054*
H46B	0.967067	0.839203	0.529020	0.054*
H46C	0.884058	0.955773	0.516431	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0224 (2)	0.0272 (2)	0.0230 (2)	−0.00434 (18)	0.00633 (17)	−0.00136 (18)
S2	0.0185 (2)	0.0349 (3)	0.0245 (2)	−0.00048 (18)	−0.00314 (17)	0.00117 (19)
S3	0.0242 (2)	0.0361 (3)	0.0182 (2)	−0.00494 (19)	−0.00025 (18)	−0.00181 (19)
O4	0.0132 (6)	0.0371 (8)	0.0480 (9)	0.0029 (6)	0.0003 (6)	−0.0004 (7)
O5	0.0197 (6)	0.0288 (7)	0.0264 (7)	0.0023 (5)	0.0011 (5)	0.0050 (6)
O6	0.0402 (9)	0.0420 (9)	0.0196 (7)	0.0003 (7)	−0.0071 (6)	0.0000 (6)
O7	0.0210 (7)	0.0417 (8)	0.0178 (6)	0.0034 (6)	0.0034 (5)	0.0005 (6)
O8	0.0291 (7)	0.0366 (8)	0.0312 (8)	−0.0035 (6)	0.0155 (6)	−0.0029 (6)
O9	0.0185 (6)	0.0320 (8)	0.0295 (7)	−0.0016 (5)	−0.0001 (5)	−0.0009 (6)
N10	0.0128 (7)	0.0260 (8)	0.0172 (7)	−0.0002 (6)	−0.0005 (6)	0.0001 (6)
C11	0.0190 (9)	0.0273 (10)	0.0359 (11)	−0.0046 (8)	0.0102 (8)	−0.0074 (9)
C12	0.0152 (9)	0.0239 (10)	0.0369 (11)	−0.0006 (7)	0.0026 (8)	−0.0059 (8)
C13	0.0172 (9)	0.0222 (9)	0.0282 (10)	−0.0004 (7)	0.0029 (7)	−0.0021 (8)
C14	0.0182 (9)	0.0208 (9)	0.0223 (9)	−0.0025 (7)	0.0034 (7)	−0.0015 (7)
C15	0.0172 (9)	0.0218 (9)	0.0179 (8)	−0.0010 (7)	0.0010 (7)	−0.0023 (7)
C16	0.0178 (9)	0.0219 (9)	0.0197 (9)	0.0015 (7)	−0.0018 (7)	0.0016 (7)
C17	0.0174 (8)	0.0222 (9)	0.0191 (8)	−0.0022 (7)	−0.0002 (7)	0.0021 (7)
C18	0.0130 (8)	0.0231 (9)	0.0176 (8)	−0.0004 (7)	−0.0013 (6)	−0.0023 (7)
C19	0.0194 (9)	0.0233 (9)	0.0228 (9)	0.0008 (7)	−0.0019 (7)	0.0034 (7)
C20	0.0202 (9)	0.0241 (9)	0.0220 (9)	−0.0028 (7)	0.0013 (7)	0.0025 (7)
C21	0.0132 (9)	0.0449 (14)	0.0606 (16)	−0.0004 (9)	0.0051 (9)	−0.0135 (12)
C22	0.0530 (14)	0.0392 (13)	0.0273 (11)	−0.0008 (11)	−0.0006 (10)	0.0005 (10)
C23	0.0282 (10)	0.0326 (11)	0.0283 (10)	−0.0029 (8)	−0.0100 (8)	0.0008 (9)
C24	0.0306 (10)	0.0229 (9)	0.0196 (9)	−0.0015 (8)	−0.0054 (8)	−0.0003 (7)
C25	0.0229 (9)	0.0217 (9)	0.0253 (9)	−0.0017 (7)	−0.0010 (7)	−0.0007 (7)
C26	0.0233 (9)	0.0205 (9)	0.0242 (9)	−0.0013 (7)	−0.0044 (7)	0.0012 (7)
C27	0.0199 (9)	0.0205 (9)	0.0195 (9)	−0.0037 (7)	−0.0040 (7)	0.0041 (7)
C28	0.0226 (9)	0.0236 (9)	0.0182 (8)	−0.0025 (7)	0.0001 (7)	−0.0014 (7)
C29	0.0166 (8)	0.0232 (9)	0.0211 (9)	0.0013 (7)	0.0002 (7)	0.0014 (7)
C30	0.0146 (8)	0.0201 (9)	0.0181 (8)	−0.0018 (7)	−0.0021 (6)	0.0023 (7)
C31	0.0174 (8)	0.0219 (9)	0.0209 (9)	0.0011 (7)	−0.0004 (7)	−0.0007 (7)
C32	0.0163 (8)	0.0229 (9)	0.0249 (9)	0.0010 (7)	−0.0032 (7)	0.0030 (7)
C33	0.0535 (15)	0.0492 (15)	0.0240 (11)	−0.0042 (12)	−0.0190 (10)	0.0024 (10)
C34	0.0400 (12)	0.0367 (12)	0.0286 (11)	0.0050 (10)	0.0034 (9)	−0.0030 (9)
C35	0.0344 (11)	0.0284 (10)	0.0202 (9)	−0.0049 (8)	0.0058 (8)	−0.0013 (8)
C36	0.0266 (10)	0.0207 (9)	0.0267 (10)	−0.0023 (8)	0.0089 (8)	−0.0023 (8)
C37	0.0205 (9)	0.0204 (9)	0.0243 (9)	−0.0005 (7)	0.0029 (7)	−0.0008 (7)
C38	0.0206 (9)	0.0217 (9)	0.0185 (9)	−0.0021 (7)	0.0000 (7)	−0.0012 (7)
C39	0.0176 (8)	0.0210 (9)	0.0189 (9)	0.0014 (7)	0.0005 (7)	−0.0001 (7)
C40	0.0142 (8)	0.0238 (9)	0.0234 (9)	−0.0018 (7)	−0.0005 (7)	−0.0001 (7)
C41	0.0160 (8)	0.0213 (9)	0.0195 (9)	−0.0011 (7)	−0.0017 (7)	−0.0012 (7)
C42	0.0150 (8)	0.0210 (9)	0.0166 (8)	0.0026 (7)	−0.0008 (6)	0.0012 (7)
C43	0.0154 (8)	0.0263 (10)	0.0211 (9)	−0.0038 (7)	−0.0008 (7)	−0.0001 (7)
C44	0.0191 (8)	0.0260 (10)	0.0188 (9)	−0.0036 (7)	−0.0027 (7)	−0.0012 (7)
C45	0.0472 (13)	0.0383 (13)	0.0300 (11)	−0.0083 (11)	0.0221 (10)	−0.0078 (10)
C46	0.0248 (10)	0.0436 (13)	0.0391 (12)	−0.0110 (9)	0.0030 (9)	−0.0059 (10)

Geometric parameters (Å, º) top

S1—C11	1.729 (2)	C15—C20	1.396 (3)
S1—C14	1.7381 (19)	C16—C17	1.388 (3)
S2—C23	1.724 (2)	C17—C18	1.391 (3)
S2—C26	1.742 (2)	C18—C19	1.392 (3)
S3—C35	1.725 (2)	C19—C20	1.388 (3)
S3—C38	1.7351 (19)	C23—C24	1.351 (3)
O4—C12	1.359 (2)	C24—C25	1.440 (3)
O4—C21	1.430 (3)	C25—C26	1.360 (3)
O5—C13	1.374 (2)	C26—C27	1.469 (3)
O5—C22	1.422 (3)	C27—C28	1.404 (3)
O6—C24	1.361 (2)	C27—C32	1.390 (3)
O6—C33	1.437 (3)	C28—C29	1.386 (3)
O7—C25	1.364 (2)	C29—C30	1.397 (3)
O7—C34	1.421 (3)	C30—C31	1.399 (2)
O8—C36	1.359 (2)	C31—C32	1.382 (3)
O8—C45	1.427 (3)	C35—C36	1.362 (3)
O9—C37	1.371 (2)	C36—C37	1.432 (3)
O9—C46	1.430 (3)	C37—C38	1.368 (3)
N10—C18	1.425 (2)	C38—C39	1.464 (3)
N10—C30	1.411 (2)	C39—C40	1.402 (3)
N10—C42	1.414 (2)	C39—C44	1.397 (3)
C11—C12	1.359 (3)	C40—C41	1.381 (3)
C12—C13	1.427 (3)	C41—C42	1.398 (3)
C13—C14	1.366 (3)	C42—C43	1.396 (3)
C14—C15	1.471 (2)	C43—C44	1.387 (3)
C15—C16	1.400 (3)

S1ⁱ···H45A	2.93	C26^iv···H41	2.89
O5ⁱⁱ···H45C	2.69	C27^vii···H31	2.87
O6ⁱⁱⁱ···H22A	2.71	C28^vii···H32	2.85
O9^iv···C34	3.177 (3)	C29^vii···H32	2.80
C11^v···H19	2.83	C36ⁱ···H22C	2.88
C13ⁱⁱ···H45C	2.86	C46^viii···C46	3.303 (3)
C17^vi···H33B	2.88	H21A^ix···H41	2.38
C24^iv···C40	3.285 (3)	H44ⁱ···H44	2.39
C26^vii···H31	2.82

C11—S1—C14	92.56 (9)	O7—C25—C24	122.67 (18)
C23—S2—C26	92.71 (10)	C26—C25—O7	124.03 (17)
C35—S3—C38	92.97 (10)	C26—C25—C24	113.10 (18)
C12—O4—C21	115.45 (18)	C25—C26—S2	110.04 (14)
C13—O5—C22	113.62 (16)	C25—C26—C27	129.21 (18)
C24—O6—C33	114.01 (18)	C27—C26—S2	120.65 (15)
C25—O7—C34	115.28 (16)	C28—C27—C26	121.98 (17)
C36—O8—C45	115.09 (18)	C32—C27—C26	120.36 (17)
C37—O9—C46	114.76 (16)	C32—C27—C28	117.67 (16)
C30—N10—C18	118.36 (14)	C29—C28—C27	120.92 (17)
C30—N10—C42	121.67 (14)	C28—C29—C30	120.82 (17)
C42—N10—C18	119.88 (14)	C29—C30—N10	120.56 (16)
C12—C11—S1	110.90 (14)	C29—C30—C31	118.34 (16)
O4—C12—C11	129.03 (18)	C31—C30—N10	121.10 (16)
O4—C12—C13	117.98 (19)	C32—C31—C30	120.40 (17)
C11—C12—C13	112.98 (18)	C31—C32—C27	121.82 (17)
O5—C13—C12	121.20 (17)	C36—C35—S3	110.69 (15)
C14—C13—O5	125.14 (17)	O8—C36—C35	128.47 (19)
C14—C13—C12	113.64 (18)	O8—C36—C37	118.49 (18)
C13—C14—S1	109.92 (14)	C35—C36—C37	113.01 (17)
C13—C14—C15	129.30 (17)	O9—C37—C36	122.75 (17)
C15—C14—S1	120.78 (14)	C38—C37—O9	123.42 (17)
C16—C15—C14	120.92 (16)	C38—C37—C36	113.49 (17)
C20—C15—C14	120.61 (17)	C37—C38—S3	109.83 (14)
C20—C15—C16	118.47 (17)	C37—C38—C39	128.88 (17)
C17—C16—C15	120.67 (17)	C39—C38—S3	121.27 (14)
C16—C17—C18	120.36 (17)	C40—C39—C38	120.88 (16)
C17—C18—N10	121.06 (16)	C44—C39—C38	121.83 (17)
C17—C18—C19	119.38 (16)	C44—C39—C40	117.26 (16)
C19—C18—N10	119.54 (16)	C41—C40—C39	121.25 (17)
C20—C19—C18	120.22 (17)	C40—C41—C42	121.01 (17)
C19—C20—C15	120.89 (17)	C41—C42—N10	120.73 (16)
C24—C23—S2	110.83 (15)	C43—C42—N10	120.93 (16)
O6—C24—C25	117.53 (18)	C43—C42—C41	118.33 (16)
C23—C24—O6	129.13 (18)	C44—C43—C42	120.28 (17)
C23—C24—C25	113.30 (18)	C43—C44—C39	121.86 (17)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+3/2, y−1/2, −z+3/2; (v) −x+1/2, y+1/2, −z+3/2; (vi) x−3/2, −y+1/2, z−3/2; (vii) −x+3/2, y+1/2, −z+3/2; (viii) −x+2, −y+2, −z+1; (ix) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

Cg1, Cg3 and Cg5 are the centroids of the S1/C11–C14,S3/C35–C38 and C27–C32 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21B···Cg5^v	0.98	2.95	3.686 (3)	133
C22—H22C···Cg3ⁱ	0.98	2.85	3.678 (2)	143
C32—H32···Cg5^iv	0.95	2.87	3.518 (2)	126
C41—H41···Cg2^vii	0.95	2.96	3.2346 (17)	98
C45—H45A···Cg1ⁱ	0.98	2.89	3.820 (2)	160
S1—H20···C20^v
O5—H45C···C45ⁱⁱ	0.98	2.69	3.336 (3)	123
O9—H34B···C34^iv	0.98	2.77	3.177 (3)	106

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

Funding information

Funding for this research was provided by: KAKENHI (grant No. JP23K04711 to M. Y.); ESPEC Foundation for Global Environment Research and Technology (grant to M. Y.).

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