4,4′-{[(2,2′-Bi­pyridine)-5,5′-dicarbon­yl]bis­(aza­nedi­yl)}bis­(1-methyl­pyridin-1-ium) bis­[hexa­fluorido­phosphate(V)] acetonitrile disolvate

Sueyoshi, F.; Sakai, K.

doi:10.1107/S2414314625005176

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 6| June 2025| x250517

https://doi.org/10.1107/S2414314625005176

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4,4′-{[(2,2′-Bipyridine)-5,5′-dicarbonyl]bis(azanediyl)}bis(1-methylpyridin-1-ium) bis[hexafluoridophosphate(V)] acetonitrile disolvate

Fumika Sueyoshi ^a ^* and Ken Sakai ^a

^aDepartment of Chemistry, Faculty of Science, Kyushu University, Motooka 744, Nishi-ku, Fukuoka 819-0395, Japan
^*Correspondence e-mail: [email protected]

Edited by M. Zeller, Purdue University, USA (Received 21 May 2025; accepted 6 June 2025; online 12 June 2025)

The new redox-active title compound, C₂₄H₂₂N₆O₂²⁺·2PF₆⁻·2C₂H₃N, a 2,2-bipyridine derivative tethered to two N-methylpyridinium moieties as electron reservoirs, was synthesized and structurally characterized by ¹H NMR spectroscopy and single-crystal X-ray diffractometry. The asymmetric unit comprises one half of the divalent bpy cation together with a [PF₆]⁻ anion and a CH₃CN molecule. The cation is completed by inversion symmetry. The crystal structure features hydrogen-bonding and π–π interactions.

Keywords: crystal structure; redox-active 2,2-bipyridine derivative.

CCDC reference: 2457228

Structure description

2,2′-Bipyridine (bpy) or 1,10-phenanthroline (phen) derivatives have been widely adopted to study various bpy- or phen-ligated transition-metal complexes for a variety of purposes. One of their most remarkable properties lies in the suitably energy.-leveled π*(bpy or phen)-based LUMO, resulting in attractive photochemical and electrochemical properties derived from the redox-active bpy or phen moieties. The [Ru(bpy or phen)₃]²⁺ family is an important example allowing researchers to advance the knowledge of photochemical and photophysical properties of the ³MLCT (triplet metal-to-ligand charge transfer) excited states and their applications to photo-induced electron transfer reactions, especially artificial photosynthetic reactions driven by such photosensitizers.

For example, our previous studies on hybrid molecular systems consisting of an [Ru(bpy)₂(phen)]²⁺ chromophore and an H₂-evolving Pt(bpy) catalyst demonstrated a rational strategy to finely tune intramolecular electron-transfer efficiency together with the associated photocatalytic H₂ evolution performance (Ozawa et al., 2006 ; Masaoka et al., 2010 ; Suneesh et al., 2014 ). Our studies on the homogeneous water or CO₂ reduction catalysis have highlighted the importance of raising the electron density at the metal d orbitals based on such ligand-based reduction. For example, the Ni(bpy)(dithiolene) H₂ evolution catalyst was shown to significantly accelerate its proton abstraction rate upon bpy-based reduction (Koshiba et al., 2019 ). In general, the performance of cobalt porphyrin CO₂ reduction catalysts was found to largely rely on the porphyrin-based reductions in order to trigger the CO₂-binding step, which requires a formal two-electron reduction of CO₂ to afford a CO₂²⁻-ligated intermediate (Call et al., 2019 ; Zhang et al., 2019 , 2021 ). A more recent study on Rh(Cp*)(bpy) CO₂ reduction catalysts further evidenced the inevitable role of an Rh(H)(Cp*)(bpy^.−) intermediate in order to gain a great enhancement in its hydricity to transfer a hydride to CO₂ to yield a formate anion (Lee et al., 2024 ).

In addition to the role of ligand-based reductions, we have also investigated the rate enhancement factors by tethering multiple electron reservoir sites to the ligand coordinated to the catalytically active metal. The Pt(bpy)Cl₂ catalysts tethered to multiple methyl viologen (i.e., N,N′-dimethyl-4,4′-bipyridinium) pendants were shown to accelerate the overall photocatalytic H₂ evolution performance (Kitamoto et al., 2014 , 2016 ). The cobalt tetrakis(N-methylpyridinium-n-yl)porphyrin (n = 2,4) CO₂ reduction catalysts were also found to exhibit high catalytic efficiencies by accumulation of multiple electrons (Zhang et al., 2019, 2021).

With the above issues in mind, a new bpy ligand was designed and synthesized to further explore the role of tethered electron reservoir sites. The two methylpyridinium moieties covalently bonded at the 5,5′-positions of the 2,2′-bipyridine unit in the title solvated salt, I, are expected to serve as additional redox-active sites upon coordinating a catalytically active metal, such as platinum, rhodium, etc. As previously described for the cobalt tetrakis(N-methylpyridinium-4-yl)porphyrin catalyst, the two pyridinium moieties linked at both ends of I are expected to cooperatively accept electrons using the π-conjugated system. Methylpyridinium pendants as cationic moieties will also facilitate water solubility of catalysts fabricated from I. Indeed, a preliminary study on the single-molecular photocatalytic H₂ evolution activity of Pt(I)Cl₂ revealed that it exhibits a higher catalytic rate compared to a control having no methylpyridinium pendants (i.e., Pt(5,5′-dicarboxy-2,2′-bipyridine), the details of which will be separately reported elsewhere.

One half of the divalent bpy cation together with a [PF₆]⁻ anion and a CH₃CN molecule is found in the asymmetric unit of I. The half cationic fragment is bonded to the neighboring fragment through a crystallographic inversion center to give the whole cationic part of the ligand (Fig. 1), resulting in an almost planar geometry of the central bipyridyl moiety. The central bond distance is expressed by C1—C1ⁱ = 1.491 (4) Å [symmetry code: (i) −x + 1, −y + 1, −z] (Table 1). The two independent pyridyl planes possess a planar geometry with an r.m.s. deviation of 0.011 Å for the N1/C1–C5 plane and 0.006 Å for the N3/C7–C11 plane. Although the dihedral angle between these two pyridyl planes is relatively small [i.e., 1.1 (1)°], they do not form a coplanar geometry because of the twists given by the –C(=O)N– plane connecting the two planes. The dihedral angles of the –C(=O)N– plane with regard to the N1/C1–C5 and N3/C7–C11 planes are 11.2 (2) and −12.3 (2)°, respectively. In other words, the six atoms in one pyridyl plane (e.g., N1/C1–C5) are on average shifted out from the other pyridyl plane (e.g., N3/C7–C11) by 0.33 (2) Å.

Table 1
Selected bond lengths (Å)

O1—C6	1.215 (2)	C1—C1ⁱ	1.491 (4)
N1—C4	1.335 (3)	C2—C3	1.386 (3)
N1—C1	1.342 (3)	C3—C5	1.391 (3)
N2—C6	1.373 (2)	C4—C5	1.388 (3)
N2—C7	1.387 (2)	C5—C6	1.500 (3)
N3—C11	1.339 (2)	C7—C8	1.392 (3)
N3—C10	1.352 (3)	C7—C9	1.400 (3)
N3—C12	1.477 (3)	C8—C10	1.362 (3)
N4—C13	1.133 (3)	C9—C11	1.366 (3)
C1—C2	1.390 (3)	C13—C14	1.461 (3)
Symmetry code: (i) .

Figure 1
ORTEP diagram of I with the atom-labeling scheme, where atoms are drawn using the 50% probability displacement ellipsoids for the non-hydrogen atoms. Labels for the minor component of the disordered atoms were omitted for clarity. Symmetry code: (i) −x + 1, −y + 1, -z.

On the other hand, the crystal packing mode is somewhat unique in that the cationic and anionic components respectively form two-dimensional slabs growing parallel to the ab plane, electrostatically consolidating the crystal based on the alternate stacks of oppositely charged two-dimensional slabs (Fig. 2). The acetonitrile molecules are involved in the anionic slabs comprised of the [PF₆]⁻ anions (Fig. 3). The cationic slabs are consolidated by one-dimensional π–π stacking of the divalent cations together with the hydrophobic interactions formed among the 1-D chains (Fig. 4). The 1-D chains grow along the [110] direction, while the inter-chain associations perpendicularly grow along the [1 $[\overline{1}]$ 0] direction. The separation between π-stacked planes between the one-dimensionally aligned cations is estimated as 3.45 (2) Å by the results of mean-plane calculations.

Figure 2
Crystal packing of I, viewed along the a axis in the range −1 < a < 2. Minor disordered PF₆ moieties are omitted for clarity.

Figure 3
The anionic slab including the acetonitrile molecules, viewed along the c axis, where the a and b axes are given in the vertical and horizontal directions. Minor disordered PF₆ moieties are omitted for clarity.

Figure 4
The cationic slab viewed along [110], showing that the 1-D chains are gown by the π–π stacking along this vector with the inter-chain interactions formed along [1 $[\overline{1}]$ 0].

The O atom of the amide is involved in two hydrogen bonds with C8—H8 and C10ⁱⁱⁱ—H10ⁱⁱⁱ [symmetry code: (iii) −x + 3, −y + 2, z], exhibiting C⋯O distances of 2.838 (3) and 3.176 (2) Å, respectively (Table 2, Fig. 5). The N atom of the acetonitrile is involved in three hydrogen bonds with N2—H2N, C4—H4, and C9—H9 with N⋯N and C⋯N distances of 3.309 (2), 3.389 (3) and 3.440 (3) Å, respectively (Table 2, Fig. 5).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯F3Cⁱⁱ	0.89 (3)	2.11 (3)	2.70 (2)	123 (3)
N2—H2N⋯N4	0.89 (3)	2.47 (3)	3.309 (2)	157 (3)
C2—H2⋯F6Bⁱ	0.95	2.25	3.037 (7)	139
C4—H4⋯N4	0.95	2.45	3.389 (3)	172
C8—H8⋯O1	0.95	2.26	2.838 (3)	118
C9—H9⋯N4	0.95	2.59	3.440 (3)	150
C10—H10⋯O1ⁱⁱⁱ	0.95	2.26	3.176 (2)	162
C11—H11⋯F1A^iv	0.95	2.29	2.981 (4)	129
C11—H11⋯F4A^v	0.95	2.48	3.020 (6)	116
C11—H11⋯F6A^v	0.95	2.48	2.957 (4)	111
C11—H11⋯F1B^iv	0.95	2.46	3.268 (8)	143
C11—H11⋯F1C^v	0.95	2.36	3.21 (2)	150
C12—H12A⋯F4C^vi	0.98	2.46	3.19 (2)	131
C12—H12B⋯F1A^iv	0.98	2.54	3.348 (4)	139
C12—H12B⋯F5B^iv	0.98	2.33	3.272 (7)	160
C14—H14A⋯F6A	0.98	2.53	3.465 (4)	161
C14—H14A⋯F1B	0.98	2.50	3.264 (10)	134
C14—H14A⋯F6C	0.98	2.27	3.24 (2)	172
C14—H14B⋯F2A^vii	0.98	2.43	3.397 (5)	171
C14—H14B⋯F2B^vii	0.98	2.36	3.334 (13)	176
C14—H14B⋯F2C^vii	0.98	2.05	2.941 (14)	151
C14—H14C⋯F5Aⁱⁱ	0.98	2.47	3.176 (4)	129
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Figure 5
Partial crystal packing of I, viewed along the b axis, showing hydrogen-bonding interactions as dotted lines. Minor disordered PF₆ moieties are omitted for clarity.

Synthesis and crystallization

Synthesis of I: N⁵,N^5′-Di(pyridin-4-yl)-2,2′-bipyridine-5,5′-dicarboxamide was prepared by following a literature procedure (Jacobs & Hardie, 2012 ). A solution of N⁵,N^5′-di(pyridin-4-yl)-2,2′-bipyridine-5,5′-dicarboxamide (0.16 g, 0.39 mmol) and iodomethane (0.19 ml, 3.0 mmol) in acetonitrile (70 ml) was refluxed for 24 h. The resulting pale-brown precipitate was collected by filtration, washed with acetonitrile (3 × 6 ml), and dried in vacuo. The iodide salt of the product was then dissolved in water (ca 50 ml) followed by addition of an excess of (NH₄)[PF₆] (0.68 g, 4.2 mmol) to give the final product in the form of its hemihydrate as a pale-brown solid, which was collected by filtration, washed with water (3 × 17 ml), and dried in vacuo (yield: 0.20 g, 70%). ¹H NMR (400 MHz, CD₃CN): δ/p.p.m. = 4.18 (s, 6H), 8.28 (d, 4H, J = 7.0 Hz), 8.45 (d, 4H, J = 7.4 Hz), 8.48 (dd, 2H, J = 8.3, 2.4 Hz), 8.70 (d, 2H, J = 8.3 Hz), 9.27 (d, 2H, J = 2.4 Hz), 10.01 (s, 2H). Analysis calculated for C₂₄H₂₂N₆O₂F₁₂P₂·0.5H₂O (725.42): C 39.74, H 3.20, N 11.59; found: C 39.63, H 3.01, N 11.51 (%).

Single crystals suitable for the single-crystal X-ray diffractometry were grown by vapor diffusion. The above hemihydrate form of the [PF₆]⁻ salt dissolved in a minimum amount of acetonitrile was sealed within a screw vial under the vapor of diisopropylether. Upon standing overnight at room temperature, dark-brown plates gradually formed and were collected by filtration. The crystals filtered were relatively stable under ambient conditions and did not lose luster for at least several days.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The [PF₆]⁻ ion was found to be disordered over three sites with site occupation factors of 0.654 (3), 0.291 (3) and 0.0546 (18). Since there was no disorder problem at the central P atom, only the six F atoms were located over three sites (F1A–F6A, F1B–F6B, and F1C–F6C) and refined anisotropically. The refinement of these 18 disordered F atoms were carried out using SADI and SIMU commands of SHELXL. The adjacent F—F distances within the individual site were restrained to be equal using SADI, and the P—F distances were restrained to be common. Moreover, the anisotropic displacement parameters of the disordered atoms were restrained to be similar using SIMU.

Table 3
Experimental details

Crystal data
Chemical formula	C₂₄H₂₂N₆O₂²⁺·2PF₆⁻·2C₂H₃N
M_r	798.52
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.7661 (2), 8.1535 (3), 13.3262 (5)
α, β, γ (°)	93.392 (3), 102.488 (3), 95.435 (3)
V (Å³)	817.40 (5)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.25
Crystal size (mm)	0.41 × 0.38 × 0.14

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2024 )
T_min, T_max	0.471, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10914, 3677, 2834
R_int	0.044

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.123, 1.09
No. of reflections	3677
No. of parameters	351
No. of restraints	1144
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.35
Computer programs: CrysAlis PRO (Rigaku OD, 2024), SHELXT2018/2 (Sheldrick, 2015a ), KENX (Sakai, 2025 ), SHELXL2019/2 (Sheldrick, 2015b ), KENX (Sakai, 2025), ORTEPII (Johnson, 1976 ), TEXSAN (Molecular Structure Corporation, 2001 ) and Mercury (Macrae et al., 2020 ).

Structural data

CCDC reference: 2457228

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314625005176/zl4084sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625005176/zl4084Isup2.hkl

checkCIF report

Computing details top

4,4'-{[(2,2'-Bipyridine)-5,5'-dicarbonyl]bis(azanediyl)}bis(1-methylpyridin-1-ium) bis[hexafluoridophosphate(V)] acetonitrile disolvate top

Crystal data top

C₂₄H₂₂N₆O₂²⁺·2PF⁶⁻·2C₂H₃N	Z = 1
M_r = 798.52	F(000) = 406
Triclinic, P1	D_x = 1.622 Mg m⁻³
a = 7.7661 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1535 (3) Å	Cell parameters from 4689 reflections
c = 13.3262 (5) Å	θ = 2.7–28.3°
α = 93.392 (3)°	µ = 0.25 mm⁻¹
β = 102.488 (3)°	T = 100 K
γ = 95.435 (3)°	Prism, brown
V = 817.40 (5) Å³	0.41 × 0.38 × 0.14 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	3677 independent reflections
Radiation source: micro-focus sealed X-ray tube	2834 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.044
Detector resolution: 10.0000 pixels mm^-1	θ_max = 29.6°, θ_min = 2.5°
ω scans	h = −9→10
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2024)	k = −10→10
T_min = 0.471, T_max = 1.000	l = −14→18
10914 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: difference Fourier map
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0695P)² + 0.5331P] where P = (F_o² + 2F_c²)/3
3677 reflections	(Δ/σ)_max < 0.001
351 parameters	Δρ_max = 0.37 e Å⁻³
1144 restraints	Δρ_min = −0.35 e Å⁻³

Special details top

Refinement. All H atoms, except for H2N, were placed in idealized positions (methyl C—H = 0.98 Å and aromatic C—H = 0.95 Å) and included in the refinement in a riding-model approximation, with U_iso(H) = 1.5U_eq(methyl C) and U_iso(H) = 1.2U_eq(aromatic C). Only nitrogen-bound H atom (H2N) was refined isotropically with a fixed isotropic displacement parameter (U_iso(H) = 1.2U_eq(N)).

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
P1	0.21563 (6)	0.64060 (6)	0.37256 (4)	0.02504 (17)
F1A	0.3516 (5)	0.6623 (6)	0.4791 (3)	0.0672 (13)	0.654 (3)
F2A	0.2511 (8)	0.8319 (5)	0.3589 (4)	0.0421 (11)	0.654 (3)
F3A	0.0840 (4)	0.6143 (4)	0.2600 (2)	0.0609 (9)	0.654 (3)
F4A	0.1824 (8)	0.4450 (5)	0.3815 (5)	0.0482 (12)	0.654 (3)
F5A	0.0563 (4)	0.6665 (4)	0.4234 (3)	0.0514 (8)	0.654 (3)
F6A	0.3769 (4)	0.6091 (4)	0.3167 (3)	0.0464 (8)	0.654 (3)
F1B	0.3948 (10)	0.6197 (12)	0.4536 (6)	0.057 (2)	0.291 (3)
F2B	0.2841 (17)	0.8322 (11)	0.3722 (11)	0.055 (3)	0.291 (3)
F3B	0.0365 (7)	0.6698 (8)	0.2980 (5)	0.0461 (15)	0.291 (3)
F4B	0.1475 (16)	0.4554 (11)	0.3801 (10)	0.054 (3)	0.291 (3)
F5B	0.1342 (11)	0.6971 (10)	0.4707 (5)	0.0646 (19)	0.291 (3)
F6B	0.3012 (11)	0.5969 (12)	0.2820 (5)	0.065 (2)	0.291 (3)
F1C	0.342 (3)	0.539 (3)	0.4504 (15)	0.063 (5)	0.0546 (18)
F2C	0.285 (3)	0.802 (2)	0.4481 (15)	0.060 (4)	0.0546 (18)
F3C	0.088 (3)	0.741 (3)	0.2974 (15)	0.065 (5)	0.0546 (18)
F4C	0.152 (3)	0.479 (2)	0.2969 (15)	0.055 (4)	0.0546 (18)
F5C	0.064 (2)	0.596 (3)	0.4324 (17)	0.057 (5)	0.0546 (18)
F6C	0.370 (2)	0.684 (3)	0.3140 (17)	0.061 (5)	0.0546 (18)
O1	1.16857 (18)	0.84347 (18)	−0.01190 (11)	0.0331 (4)
N1	0.6300 (2)	0.6666 (2)	0.08593 (13)	0.0313 (4)
N2	1.1375 (2)	0.9356 (2)	0.14668 (13)	0.0283 (4)
N3	1.5859 (2)	1.2694 (2)	0.25358 (13)	0.0276 (4)
N4	0.8997 (2)	1.0188 (3)	0.31784 (15)	0.0381 (5)
C1	0.5868 (2)	0.5513 (2)	0.00584 (14)	0.0245 (4)
C2	0.6944 (3)	0.5290 (2)	−0.06365 (15)	0.0267 (4)
H2	0.657801	0.448885	−0.120957	0.032*
C3	0.8559 (3)	0.6259 (2)	−0.04778 (15)	0.0259 (4)
H3	0.931993	0.613397	−0.094126	0.031*
C4	0.7863 (3)	0.7586 (3)	0.10044 (16)	0.0311 (5)
H4	0.817968	0.840171	0.157134	0.037*
C5	0.9049 (3)	0.7416 (2)	0.03710 (14)	0.0247 (4)
C6	1.0819 (3)	0.8428 (2)	0.05392 (14)	0.0250 (4)
C7	1.2920 (3)	1.0428 (2)	0.17970 (15)	0.0258 (4)
C8	1.4345 (3)	1.0520 (3)	0.13156 (16)	0.0292 (4)
H8	1.431905	0.979342	0.072716	0.035*
C9	1.3044 (3)	1.1501 (3)	0.26752 (15)	0.0292 (5)
H9	1.210315	1.146108	0.302866	0.035*
C10	1.5775 (3)	1.1657 (3)	0.16923 (16)	0.0305 (5)
H10	1.673548	1.172358	0.135459	0.037*
C11	1.4520 (3)	1.2606 (3)	0.30231 (15)	0.0292 (4)
H11	1.459698	1.332626	0.362209	0.035*
C12	1.7409 (3)	1.3945 (3)	0.29059 (18)	0.0357 (5)
H12A	1.838140	1.366523	0.258886	0.054*
H12B	1.779023	1.396335	0.365756	0.054*
H12C	1.708218	1.503564	0.271681	0.054*
C13	0.8309 (3)	0.9568 (3)	0.37464 (17)	0.0325 (5)
C14	0.7408 (3)	0.8760 (3)	0.44701 (19)	0.0457 (6)
H14A	0.622944	0.825099	0.410193	0.069*
H14B	0.728513	0.958103	0.501048	0.069*
H14C	0.810483	0.790600	0.478350	0.069*
H2N	1.068 (4)	0.925 (4)	0.192 (2)	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0254 (3)	0.0250 (3)	0.0236 (3)	0.0021 (2)	0.0033 (2)	0.0018 (2)
F1A	0.059 (2)	0.094 (4)	0.0334 (16)	−0.018 (2)	−0.0151 (14)	0.0217 (18)
F2A	0.052 (2)	0.0252 (18)	0.053 (2)	0.0034 (13)	0.0191 (19)	0.0070 (14)
F3A	0.0591 (19)	0.071 (2)	0.0362 (15)	−0.0266 (16)	−0.0125 (12)	0.0090 (13)
F4A	0.045 (2)	0.0259 (16)	0.085 (3)	0.0057 (13)	0.036 (2)	0.0163 (16)
F5A	0.0469 (16)	0.0370 (15)	0.080 (2)	0.0065 (13)	0.0356 (15)	0.0024 (15)
F6A	0.0506 (16)	0.0312 (13)	0.066 (2)	−0.0042 (13)	0.0376 (15)	−0.0025 (15)
F1B	0.052 (4)	0.040 (4)	0.062 (5)	0.005 (3)	−0.023 (3)	0.001 (3)
F2B	0.045 (4)	0.037 (5)	0.075 (6)	0.002 (3)	−0.001 (4)	−0.004 (4)
F3B	0.035 (3)	0.033 (3)	0.058 (4)	−0.007 (2)	−0.015 (3)	0.010 (3)
F4B	0.036 (4)	0.043 (5)	0.075 (5)	0.003 (3)	−0.007 (4)	0.013 (4)
F5B	0.088 (5)	0.067 (4)	0.056 (4)	0.028 (4)	0.045 (4)	0.011 (3)
F6B	0.102 (6)	0.064 (4)	0.036 (4)	0.018 (5)	0.030 (4)	−0.002 (3)
F1C	0.062 (8)	0.052 (8)	0.065 (8)	0.007 (8)	−0.005 (8)	0.000 (8)
F2C	0.066 (7)	0.054 (7)	0.059 (7)	−0.001 (7)	0.011 (7)	0.012 (7)
F3C	0.064 (8)	0.055 (8)	0.068 (8)	−0.003 (8)	0.002 (8)	0.003 (8)
F4C	0.054 (7)	0.055 (7)	0.051 (7)	−0.009 (7)	0.008 (7)	0.003 (7)
F5C	0.057 (8)	0.043 (8)	0.069 (8)	−0.002 (8)	0.012 (8)	0.000 (8)
F6C	0.065 (8)	0.054 (8)	0.063 (8)	−0.002 (8)	0.015 (8)	−0.006 (8)
O1	0.0314 (8)	0.0376 (9)	0.0294 (8)	−0.0029 (6)	0.0096 (6)	−0.0037 (6)
N1	0.0289 (9)	0.0338 (10)	0.0265 (9)	−0.0054 (7)	0.0015 (7)	−0.0051 (7)
N2	0.0252 (8)	0.0331 (10)	0.0242 (9)	−0.0057 (7)	0.0047 (7)	−0.0002 (7)
N3	0.0249 (8)	0.0269 (9)	0.0283 (9)	−0.0017 (7)	0.0017 (7)	0.0031 (7)
N4	0.0350 (10)	0.0433 (11)	0.0353 (10)	0.0047 (8)	0.0073 (8)	−0.0016 (9)
C1	0.0269 (10)	0.0223 (10)	0.0207 (9)	0.0016 (8)	−0.0018 (7)	0.0022 (7)
C2	0.0309 (10)	0.0232 (10)	0.0231 (10)	0.0024 (8)	0.0008 (8)	−0.0003 (8)
C3	0.0271 (10)	0.0264 (10)	0.0240 (10)	0.0050 (8)	0.0039 (8)	0.0030 (8)
C4	0.0315 (11)	0.0313 (11)	0.0268 (11)	−0.0031 (9)	0.0031 (8)	−0.0042 (8)
C5	0.0278 (10)	0.0219 (10)	0.0224 (10)	0.0019 (8)	0.0009 (8)	0.0039 (7)
C6	0.0283 (10)	0.0218 (10)	0.0229 (10)	0.0034 (8)	0.0011 (8)	0.0027 (7)
C7	0.0270 (10)	0.0249 (10)	0.0232 (10)	0.0004 (8)	0.0009 (8)	0.0037 (8)
C8	0.0277 (10)	0.0307 (11)	0.0289 (11)	0.0045 (8)	0.0053 (8)	0.0011 (8)
C9	0.0275 (10)	0.0324 (11)	0.0261 (10)	−0.0024 (8)	0.0056 (8)	0.0007 (8)
C10	0.0263 (10)	0.0346 (12)	0.0310 (11)	0.0034 (9)	0.0071 (8)	0.0028 (9)
C11	0.0310 (10)	0.0317 (11)	0.0237 (10)	−0.0005 (9)	0.0051 (8)	0.0017 (8)
C12	0.0295 (11)	0.0345 (12)	0.0395 (12)	−0.0075 (9)	0.0049 (9)	0.0024 (9)
C13	0.0258 (10)	0.0359 (12)	0.0327 (11)	0.0039 (9)	0.0024 (9)	−0.0076 (9)
C14	0.0398 (13)	0.0549 (16)	0.0428 (14)	−0.0025 (11)	0.0144 (11)	−0.0008 (11)

Geometric parameters (Å, º) top

O1—C6	1.215 (2)	C7—C9	1.400 (3)
N1—C4	1.335 (3)	C8—C10	1.362 (3)
N1—C1	1.342 (3)	C9—C11	1.366 (3)
N2—C6	1.373 (2)	C13—C14	1.461 (3)
N2—C7	1.387 (2)	P1—F6B	1.538 (7)
N2—H2N	0.89 (3)	P1—F5A	1.559 (3)
N3—C11	1.339 (2)	P1—F1A	1.565 (3)
N3—C10	1.352 (3)	P1—F4B	1.568 (8)
N3—C12	1.477 (3)	P1—F3B	1.573 (5)
N4—C13	1.133 (3)	P1—F3C	1.574 (11)
C1—C2	1.390 (3)	P1—F4C	1.580 (11)
C1—C1ⁱ	1.491 (4)	P1—F5C	1.585 (11)
C2—C3	1.386 (3)	P1—F2A	1.586 (4)
C3—C5	1.391 (3)	P1—F2C	1.587 (11)
C4—C5	1.388 (3)	P1—F6C	1.590 (11)
C5—C6	1.500 (3)	P1—F1B	1.596 (7)
C7—C8	1.392 (3)

C4—N1—C1	117.76 (17)	C11—C9—C7	119.88 (18)
C6—N2—C7	127.37 (16)	N3—C10—C8	121.53 (18)
C6—N2—H2N	117 (2)	N3—C11—C9	121.25 (18)
C7—N2—H2N	115.5 (19)	N4—C13—C14	179.4 (2)
C11—N3—C10	119.84 (17)	F5A—P1—F1A	92.52 (19)
C11—N3—C12	120.07 (17)	F6B—P1—F4B	92.8 (5)
C10—N3—C12	120.08 (17)	F6B—P1—F3B	92.3 (4)
N1—C1—C2	122.80 (17)	F4B—P1—F3B	91.9 (5)
N1—C1—C1ⁱ	115.9 (2)	F3C—P1—F4C	90.4 (7)
C2—C1—C1ⁱ	121.3 (2)	F3C—P1—F5C	90.3 (7)
C3—C2—C1	118.74 (18)	F4C—P1—F5C	91.0 (7)
C2—C3—C5	118.93 (18)	F5A—P1—F2A	92.5 (2)
N1—C4—C5	123.50 (19)	F1A—P1—F2A	90.6 (2)
C4—C5—C3	118.20 (18)	F3C—P1—F2C	90.4 (7)
C4—C5—C6	123.78 (17)	F4C—P1—F2C	178.4 (8)
C3—C5—C6	118.01 (17)	F5C—P1—F2C	90.3 (7)
O1—C6—N2	122.54 (17)	F3C—P1—F6C	90.6 (8)
O1—C6—C5	121.43 (17)	F4C—P1—F6C	89.2 (7)
N2—C6—C5	116.03 (16)	F5C—P1—F6C	179.1 (9)
N2—C7—C8	124.85 (18)	F2C—P1—F6C	89.4 (7)
N2—C7—C9	117.34 (17)	F6B—P1—F1B	90.9 (4)
C8—C7—C9	117.81 (18)	F4B—P1—F1B	89.8 (5)
C10—C8—C7	119.68 (19)	F3B—P1—F1B	176.3 (4)

C4—N1—C1—C2	−2.5 (3)	C4—C5—C6—N2	11.2 (3)
C4—N1—C1—C1ⁱ	178.6 (2)	C3—C5—C6—N2	−169.84 (17)
N1—C1—C2—C3	2.3 (3)	C6—N2—C7—C8	−12.5 (3)
C1ⁱ—C1—C2—C3	−178.8 (2)	C6—N2—C7—C9	166.98 (19)
C1—C2—C3—C5	0.1 (3)	N2—C7—C8—C10	178.0 (2)
C1—N1—C4—C5	0.3 (3)	C9—C7—C8—C10	−1.5 (3)
N1—C4—C5—C3	2.0 (3)	N2—C7—C9—C11	−178.67 (19)
N1—C4—C5—C6	−179.0 (2)	C8—C7—C9—C11	0.9 (3)
C2—C3—C5—C4	−2.1 (3)	C11—N3—C10—C8	0.4 (3)
C2—C3—C5—C6	178.83 (17)	C12—N3—C10—C8	−178.3 (2)
C7—N2—C6—O1	1.0 (3)	C7—C8—C10—N3	0.8 (3)
C7—N2—C6—C5	−177.87 (18)	C10—N3—C11—C9	−1.1 (3)
C4—C5—C6—O1	−167.70 (19)	C12—N3—C11—C9	177.6 (2)
C3—C5—C6—O1	11.3 (3)	C7—C9—C11—N3	0.4 (3)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···F3Cⁱⁱ	0.89 (3)	2.11 (3)	2.70 (2)	123 (3)
N2—H2N···N4	0.89 (3)	2.47 (3)	3.309 (2)	157 (3)
C2—H2···F6Bⁱ	0.95	2.25	3.037 (7)	139
C4—H4···N4	0.95	2.45	3.389 (3)	172
C8—H8···O1	0.95	2.26	2.838 (3)	118
C9—H9···N4	0.95	2.59	3.440 (3)	150
C10—H10···O1ⁱⁱⁱ	0.95	2.26	3.176 (2)	162
C11—H11···F1A^iv	0.95	2.29	2.981 (4)	129
C11—H11···F4A^v	0.95	2.48	3.020 (6)	116
C11—H11···F6A^v	0.95	2.48	2.957 (4)	111
C11—H11···F1B^iv	0.95	2.46	3.268 (8)	143
C11—H11···F1C^v	0.95	2.36	3.21 (2)	150
C12—H12A···F4C^vi	0.98	2.46	3.19 (2)	131
C12—H12B···F1A^iv	0.98	2.54	3.348 (4)	139
C12—H12B···F5B^iv	0.98	2.33	3.272 (7)	160
C14—H14A···F6A	0.98	2.53	3.465 (4)	161
C14—H14A···F1B	0.98	2.50	3.264 (10)	134
C14—H14A···F6C	0.98	2.27	3.24 (2)	172
C14—H14B···F2A^vii	0.98	2.43	3.397 (5)	171
C14—H14B···F2B^vii	0.98	2.36	3.334 (13)	176
C14—H14B···F2C^vii	0.98	2.05	2.941 (14)	151
C14—H14C···F5Aⁱⁱ	0.98	2.47	3.176 (4)	129

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

Acknowledgements

This work was supported by JSPS KAKENHI grant Nos. JP22KK0074 and JP24KJ1799.

Funding information

Funding for this research was provided by: Japan Society for the Promotion of Science (grant No. JP24KJ1799 to Fumika Sueyoshi); JSPS KAKENHI (grant No. JP22KK0074 to Ken Sakai).

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