A 1:1 flavone cocrystal with cyclic trimeric perfluoro-o-phenyl­enemercury

Novikov, E.M.; Castañeda, R.; Fonari, M.S.; Timofeeva, T.V.

doi:10.1107/S2056989024005346

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ISSN: 2056-9890

Volume 80| Part 7| July 2024| Pages 717-720

https://doi.org/10.1107/S2056989024005346

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A 1:1 flavone cocrystal with cyclic trimeric perfluoro-o-phenylenemercury

Egor M. Novikov,^a ^* Raúl Castañeda,^a Marina S. Fonari ^b and Tatiana V. Timofeeva ^a

^aDepartment of Chemistry, New Mexico Highlands University, Las Vegas, New Mexico, 87701, USA, and ^bInstitute of Applied Physics, Moldova State University, Academy str., 5 MD2028, Chisinau, Moldova
^*Correspondence e-mail: enovikov@live.nmhu.edu

Edited by G. Diaz de Delgado, Universidad de Los Andes Mérida, Venezuela (Received 18 March 2024; accepted 5 June 2024; online 14 June 2024)

The title compound, systematic name tris(μ₂-perfluoro-o-phenylene)(μ₂-3-phenyl-4H-chromen-4-one)-triangulo-trimercury, [Hg₃(C₆F₄)₃(C₁₅H₁₀O₂)], crystallizes in the monoclinic P2₁/n space group with one flavone (FLA) and one cyclic trimeric perfluoro-o-phenylenemercury (TPPM) molecule per asymmetric unit. The FLA molecule is located on one face of the TPPM acceptor and is linked in an asymmetric coordination of its carbonyl oxygen atom with two Hg centers of the TPPM macrocycle. The angular-shaped complexes pack in zigzag chains where they stack via two alternating TPPM–TPPM and FLA–FLA stacking patterns. The distance between the mean planes of the neighboring TPPM macrocycles in the stack is 3.445 (2) Å, and that between the benzo-γ-pyrone moieties of FLA is 3.328 (2) Å. The neighboring stacks are interdigitated through the shortened F⋯F, CH⋯F and CH⋯π contacts, forming a dense crystal structure.

Keywords: cocrystal; flavone; cyclic trimeric perfluoro-o-phenylenemercury; crystal structure; weak interactions.

CCDC reference: 2360864

1. Chemical context

Macrocyclic trimeric perfluoro-o-phenylenemercury [TPPM, (o-C₆F₄Hg)₃] Lewis acid containing three Hg atoms in a planar nine-membered cycle has been used successfully in recent decades as a multidentate Lewis acid host. Numerous studies registered an excellent oxo- and thiophilicity of this strong electron acceptor manifested in its reactions with various anions and neutral Lewis bases to give complexes wherein the Lewis bases were easily cooperatively coordinated by multiple TPPM binding sites (King et al., 2002a ,b ; Tikhonova et al., 2005 ; Castañeda et al., 2015 , 2016 ; Loveday et al., 2022 ). In particular, the oxophilicity of TPPM is well-documented, and the reported examples revealed variable molar ratios and packing arrangements of the TPPM acceptor and O-containing Lewis bases in the crystals (King et al., 2002a,b; Tikhonova et al., 2005; Castañeda et al., 2016). The O⋯Hg coordination bonds were the primary interactions in those crystals that involved two or three Hg atoms of TPPM and the O-donor molecules situated on one or both faces of the TPPM macrocycle.

Flavonoids are a family of polyphenolic compounds broadly produced in plants and found in the human diet. They are generally recognized as active pharmaceutical ingredients (API) with health-prolonging effects attributed to their antibacterial, antioxidant, antitumor, and anti-inflammatory properties (Cushnie & Lamb, 2005 , 2011 ). Flavone (FLA), the simplest member of the class of flavones, can be tailored for significant modulation of its pharmacological activity and therefore serves as an effective scaffold in medicinal chemistry (Singh et al., 2014 ). While the crystal chemistry of the TPPM acceptor is rather rich, only single examples have been reported for the crystalline forms of FLA (Waller et al., 2003 ; van Tonder et al., 2009a ,b ; Jiang et al., 2014 ; Khandavilli et al., 2018 ; Li et al., 2019 ; He et al., 2015 ). To fill this gap, we decided to cocrystallize FLA with TPPM. From a crystal-engineering perspective, it might be predicted that FLA, containing a benzo-γ-pyrone moiety bearing a phenyl substituent at position 2 and having a carbonyl group, would be predisposed for association with TPPM via oxophilic and stacking interactions. The crystal structure of the product of these interactions, the cocrystal (FLA)·(TPPM), is reported.

2. Structural commentary

The title compound, (FLA)·(TPPM) in a 1:1 molar ratio, crystallizes in the monoclinic space group P2₁/n. The asymmetric unit comprises one FLA and one TPPM molecule (Fig. 1). The principal geometric parameters for both components are in good agreement with the literature values (Groom et al., 2016 ). The components are held together via two Hg—O contacts, Hg1⋯O1 = 2.829 (3) and Hg2⋯O1 = 2.947 (4) Å, that are considerably shorter than the sum of the van der Waals radii of mercury (2.1 Å) and oxygen (1.5 Å) atoms (Batsanov, 2001 ; Yakovenko et al., 2011 ). The Hg3⋯O1 distance is 3.097 (3) Å. Thus, an asymmetrical coordination of the FLA carbonyl oxygen atom, which is bonded to two Hg centers, is observed. The tilting angle between the virtually planar benzo-γ-pyrone residue (the r.m.s. deviation of the 11 fitted atoms is 0.0243 Å) and the mean plane of TPPM is 49.97 (5)°. The FLA molecule has an angular shape indicated by the twisted angle between the benzo-γ-pyrone moiety and the anchored phenyl ring of 23.3 (2)°, contrary to the practically planar geometry of FLA in its pure form (WADRAV; Waller et al., 2003) and in (η⁶-flavone)tricarbonylchromium(0) (FUGBEP; van Tonder et al., 2009b).

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

The complexes pack in zigzag chains along the crystallographic a axis (Fig. 2), where they stack via two alternating TPPM–TPPM and FLA–FLA stacking patterns. The distance between the mean planes of the neighboring TPPM macrocycles in the stack is 3.445 (2) Å, and the macrocycles related by inversion are in a staggered conformation. The structure contains some intermetallic Hg⋯Hg distances, shorter than sum of the van der Waals radii (Batsanov, 2001; Yakovenko et al., 2011; Echeverría et al., 2017 ). They include: Hg1⋯Hg2(2 − x, 1 − y, 1 − z) = 3.6305 (4) Å; Hg1⋯Hg3(2 − x, 1 − y, 1 − z) = 4.7390 (5) Å; Hg2⋯Hg2(2 − x, 1 − y, 1 − z) = 4.7514 (5) Å; Hg2⋯Hg3(2 − x, 1 − y, 1 − z) = 4.3423 (5) Å. The interplanar separation between the two consecutive benzo-γ-pyrone moieties of FLA in the stack is equal to 3.328 (2) Å with only the pyrone rings overlapping, Cg(O2/C19–C27)⋯Cg(O2/C19–C27)(1 − x, 1 − y, 1 − z) = 3.996 (3) Å, slippage 2.211 Å. The neighboring stacks are interconnected in an interdigitated mode (Fig. 3) through the side F1⋯F11( $[{3\over 2}]$ − x, y − $[{1\over 2}]$ , $[{3\over 2}]$ − z) 2.875 (5) Å, and CH⋯F shortened contacts, C24—H24⋯F1(x − $[{1\over 2}]$ , $[{1\over 2}]$ − y, z − $[{1\over 2}]$ ) = 2.68 Å; C31—H31⋯F5(x − $[{1\over 2}]$ , $[{1\over 2}]$ − y, $[{1\over 2}]$ + z) = 2.62 Å; C32—H32⋯F5(x − $[{1\over 2}]$ , $[{1\over 2}]$ − y, $[{1\over 2}]$ + z) = 2.50 Å; C30—H30⋯F11(x − $[{1\over 2}]$ , $[{1\over 2}]$ − y, z − $[{1\over 2}]$ ) = 2.57 Å and C—H⋯π weak interactions (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C22—H22⋯F4ⁱ	0.95	2.54	3.486 (6)	173
C24—H24⋯F1ⁱⁱ	0.95	2.68	3.342 (6)	127
C30—H30⋯F11ⁱⁱ	0.95	2.57	3.473 (7)	160
C31—H31⋯F5ⁱⁱⁱ	0.95	2.62	3.200 (8)	120
C32—H32⋯F5ⁱⁱⁱ	0.95	2.50	3.149 (6)	126
C21—H21⋯C7	0.95	2.78	3.456 (7)	129
C24—H24⋯C16^iv	0.95	2.82	3.621 (7)	142
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) .

Figure 2
Supramolecular chain in the title compound generated through alternation of TPPM–TPPM and FLA–FLA stacking patterns.

Figure 3
View of the crystal packing. The central stacking chain is shown in red.

4. Database survey

A search in the Cambridge Structural Database (version 5.45, updated on 01/01/2024; Groom et al., 2016) gave very few hits for FLA crystal forms. The pure form (WADRAV; Waller et al., 2003) crystallizes in the P2₁2₁2₁ space group with two crystallographically unique molecules. In compound [Cr(FLA)(CO)₃] (FUGBEP; van Tonder et al., 2009b), the Cr^III metal center coordinates the phenyl ring of FLA. In both cases, the FLA molecule is significantly planar. In the case of the dapsone drug DAP–FLA 1:1 cocrystal (VOHKEK; Jiang et al., 2014, P2₁/n space group), the carbonyl group of FLA forms hydrogen-bonding interactions with the amino groups of DAP to form a tetrameric aggregation. Furthermore, DAP–FLA was documented as another polymorph (Form B, VOHKEK01, Fdd2 space group) and another crystal form (RUHDOP, P $[\overline{1}]$ space group, He et al., 2015) with a 1:2 ratio of component molecules. In the drug cocrystal Naringenin–FLA (JILSIJ, 1:1 molar ratio; Khandavilli et al., 2018) FLA molecules are bridging between naringenin dimers via O—H⋯O interactions. The polymorphic diversity was also registered for the diethylstilbestrol–bis(FLA) cocrystal (NOCTIL, P $[\overline{1}]$ and NOCTIL01, C2/c; Li et al., 2019). The high propensity of TPPM for carbonyl-containing compounds was demonstrated for: ethylacetate (CAMFIG; Tikhonova et al., 2002 ; 3:1 donor–acceptor molar ratio), ethyl 3-oxobutanoate (KIRDIA; Tikhonova et al., 2013 ), 4-(dimethylamino)phenylmethanone (OGANIV; Fisher & Reinheimer, 2013 ; 1:1 molar ratio), acetone (PABLUA; King et al., 2002a,b; 1:1 molar ratio), N,N-dimethylacetamide (XINMAI; Tikhonova et al., 2001 ; 2:1 molar ratio), dimethyl formamide (XOJFEH; Baldamus et al., 2002 and XOJFEH01; Tikhonova et al., 2002; 2:1 molar ratio).

5. Synthesis and crystallization

FLA (11.212 mg, 0.05 mmol) was dissolved in 5 mL of DCM and TPPM (52.290 mg, 0.05 mmol) was added to the solution. The mixture was sonicated for 10 min at ambient conditions (room temperature), and after that the solution was transferred to a 15 mL test tube and covered with a cotton cap. In 10 days transparent colorless crystals (mass of crystals collected 54.205 mg, 0.0427 mmol, 85.35%) were obtained.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All non-hydrogen atoms were refined in anisotropic approximation. The H atoms were refined as riding in idealized positions, with U_iso(H) = 1.2Ueq of the bearing C atom.

Table 2
Experimental details

Crystal data
Chemical formula	[Hg₃(C₆F₄)₃(C₁₅H₁₀O₂)]
M_r	1268.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	12.4181 (8), 13.8092 (8), 17.6498 (11)
β (°)	93.360 (2)
V (Å³)	3021.5 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	15.31
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.372, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	38196, 5894, 5069
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.052, 1.05
No. of reflections	5894
No. of parameters	451
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −1.19
Computer programs: APEX2 (Bruker, 2019 ), SAINT-Plus (Bruker, 2020 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2360864

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024005346/dj2077sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024005346/dj2077Isup2.hkl

checkCIF report

Computing details top

Tris(µ₂-perfluoro-o-phenylene)(µ₂-3-phenyl-4H-chromen-4-one)-triangulo-trimercury top

Crystal data top

[Hg₃(C₆F₄)₃(C₁₅H₁₀O₂)]	F(000) = 2288
M_r = 1268.18	D_x = 2.788 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.4181 (8) Å	Cell parameters from 9132 reflections
b = 13.8092 (8) Å	θ = 2.2–26.7°
c = 17.6498 (11) Å	µ = 15.31 mm⁻¹
β = 93.360 (2)°	T = 100 K
V = 3021.5 (3) Å³	Plate, clear colourless
Z = 4	0.20 × 0.20 × 0.10 mm

Data collection top

Bruker SMART APEXII diffractometer	5894 independent reflections
Radiation source: sealed X-ray tube, EIGENMANN GmbH	5069 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 7.9 pixels mm^-1	θ_max = 26.0°, θ_min = 1.9°
ω and φ scans	h = −15→15
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −15→17
T_min = 0.372, T_max = 0.746	l = −21→16
38196 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.052	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0252P)² + 1.6597P] where P = (F_o² + 2F_c²)/3
5894 reflections	(Δ/σ)_max = 0.003
451 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −1.19 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Hg1	0.85812 (2)	0.44283 (2)	0.60352 (2)	0.03572 (6)
Hg2	0.86702 (2)	0.46865 (2)	0.40075 (2)	0.03547 (6)
Hg3	0.84037 (2)	0.68004 (2)	0.51822 (2)	0.03658 (6)
F1	0.8927 (3)	0.2205 (2)	0.63984 (17)	0.0536 (8)
F2	0.9080 (3)	0.0628 (2)	0.5516 (2)	0.0729 (11)
F3	0.9084 (3)	0.0823 (2)	0.3984 (2)	0.0777 (12)
F4	0.8941 (3)	0.2590 (2)	0.33427 (17)	0.0561 (9)
F5	0.8718 (3)	0.5418 (2)	0.23224 (18)	0.0688 (10)
F6	0.8452 (3)	0.7185 (3)	0.16752 (18)	0.0751 (11)
F7	0.8183 (3)	0.8760 (2)	0.2553 (2)	0.0702 (10)
F8	0.8354 (3)	0.8603 (2)	0.4079 (2)	0.0646 (10)
F9	0.8232 (3)	0.8296 (2)	0.65175 (18)	0.0565 (9)
F10	0.8092 (3)	0.8092 (2)	0.80319 (17)	0.0571 (9)
F11	0.8165 (3)	0.6306 (2)	0.86695 (16)	0.0552 (8)
F12	0.8461 (3)	0.4725 (2)	0.78054 (18)	0.0583 (9)
O1	0.6883 (3)	0.5027 (2)	0.50025 (18)	0.0383 (8)
O2	0.4563 (3)	0.3256 (2)	0.40217 (19)	0.0379 (8)
C1	0.8790 (4)	0.3342 (3)	0.4535 (3)	0.0365 (12)
C2	0.8910 (4)	0.2518 (4)	0.4107 (3)	0.0404 (12)
C3	0.8998 (5)	0.1606 (4)	0.4419 (3)	0.0470 (14)
C4	0.8998 (5)	0.1504 (4)	0.5191 (3)	0.0491 (14)
C5	0.8890 (4)	0.2323 (4)	0.5636 (3)	0.0395 (12)
C6	0.8776 (4)	0.3242 (3)	0.5331 (3)	0.0345 (11)
C7	0.8593 (4)	0.6074 (3)	0.3557 (3)	0.0352 (11)
C8	0.8596 (4)	0.6197 (4)	0.2781 (3)	0.0438 (13)
C9	0.8465 (4)	0.7088 (4)	0.2435 (3)	0.0469 (14)
C10	0.8346 (4)	0.7894 (4)	0.2882 (3)	0.0451 (14)
C11	0.8394 (4)	0.7791 (4)	0.3655 (3)	0.0443 (13)
C12	0.8482 (4)	0.6903 (4)	0.4009 (3)	0.0348 (11)
C13	0.8368 (4)	0.6593 (4)	0.6347 (3)	0.0359 (11)
C14	0.8278 (4)	0.7389 (4)	0.6815 (3)	0.0398 (12)
C15	0.8211 (4)	0.7302 (4)	0.7593 (3)	0.0411 (13)
C16	0.8264 (4)	0.6408 (4)	0.7915 (3)	0.0422 (13)
C17	0.8405 (4)	0.5607 (4)	0.7459 (3)	0.0406 (12)
C18	0.8448 (4)	0.5670 (4)	0.6683 (3)	0.0391 (12)
C19	0.6156 (4)	0.4494 (3)	0.4705 (3)	0.0304 (10)
C20	0.5632 (4)	0.4696 (3)	0.3954 (3)	0.0307 (10)
C21	0.5875 (4)	0.5526 (3)	0.3525 (3)	0.0361 (12)
H21	0.6385	0.5985	0.3727	0.043*
C22	0.5381 (4)	0.5673 (4)	0.2823 (3)	0.0463 (14)
H22	0.5544	0.6234	0.2541	0.056*
C23	0.4647 (5)	0.5010 (4)	0.2524 (3)	0.0479 (14)
H23	0.4318	0.5114	0.2031	0.058*
C24	0.4380 (4)	0.4199 (4)	0.2926 (3)	0.0431 (13)
H24	0.3870	0.3744	0.2719	0.052*
C25	0.4880 (4)	0.4066 (3)	0.3643 (3)	0.0328 (11)
C26	0.5780 (4)	0.3633 (3)	0.5056 (3)	0.0335 (11)
H26	0.6081	0.3460	0.5545	0.040*
C27	0.5022 (4)	0.3063 (3)	0.4723 (3)	0.0346 (11)
C28	0.4558 (4)	0.2176 (3)	0.5049 (3)	0.0378 (12)
C29	0.4084 (5)	0.1470 (4)	0.4570 (3)	0.0544 (15)
H29	0.4040	0.1560	0.4036	0.065*
C30	0.3682 (6)	0.0639 (4)	0.4884 (4)	0.0685 (19)
H30	0.3353	0.0161	0.4560	0.082*
C31	0.3747 (5)	0.0488 (4)	0.5655 (4)	0.0621 (17)
H31	0.3485	−0.0096	0.5861	0.075*
C32	0.4189 (5)	0.1186 (4)	0.6118 (3)	0.0548 (15)
H32	0.4214	0.1097	0.6653	0.066*
C33	0.4605 (4)	0.2024 (4)	0.5820 (3)	0.0451 (13)
H33	0.4926	0.2499	0.6151	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.03653 (11)	0.03970 (11)	0.03063 (12)	−0.00036 (8)	−0.00069 (9)	−0.00388 (8)
Hg2	0.03836 (12)	0.03602 (11)	0.03231 (12)	0.00085 (8)	0.00439 (9)	−0.00019 (8)
Hg3	0.03959 (12)	0.04065 (11)	0.02955 (12)	−0.00449 (8)	0.00228 (9)	−0.00388 (8)
F1	0.064 (2)	0.0567 (19)	0.0405 (19)	0.0088 (16)	0.0019 (16)	0.0120 (15)
F2	0.102 (3)	0.0436 (19)	0.074 (3)	0.0153 (18)	0.010 (2)	0.0131 (17)
F3	0.122 (3)	0.0389 (18)	0.074 (3)	0.012 (2)	0.017 (2)	−0.0130 (17)
F4	0.077 (2)	0.0521 (19)	0.0403 (19)	0.0064 (17)	0.0113 (17)	−0.0080 (14)
F5	0.106 (3)	0.064 (2)	0.038 (2)	0.003 (2)	0.015 (2)	−0.0125 (16)
F6	0.096 (3)	0.094 (3)	0.036 (2)	0.001 (2)	0.0106 (19)	0.0207 (18)
F7	0.079 (3)	0.054 (2)	0.079 (3)	0.0043 (18)	0.017 (2)	0.0299 (18)
F8	0.080 (2)	0.0400 (18)	0.075 (2)	−0.0009 (17)	0.015 (2)	−0.0028 (16)
F9	0.081 (2)	0.0413 (18)	0.047 (2)	−0.0048 (16)	−0.0001 (18)	−0.0047 (14)
F10	0.072 (2)	0.057 (2)	0.0425 (19)	−0.0012 (16)	0.0048 (17)	−0.0203 (15)
F11	0.061 (2)	0.076 (2)	0.0272 (17)	0.0027 (17)	−0.0009 (15)	−0.0049 (15)
F12	0.080 (2)	0.0523 (19)	0.0422 (19)	0.0006 (17)	−0.0017 (18)	0.0052 (15)
O1	0.0331 (19)	0.043 (2)	0.038 (2)	−0.0075 (16)	−0.0073 (16)	−0.0013 (16)
O2	0.041 (2)	0.0398 (19)	0.032 (2)	−0.0084 (15)	−0.0041 (16)	0.0024 (14)
C1	0.031 (3)	0.034 (3)	0.045 (3)	0.003 (2)	0.002 (2)	0.001 (2)
C2	0.046 (3)	0.044 (3)	0.032 (3)	0.004 (2)	0.005 (2)	−0.004 (2)
C3	0.061 (4)	0.033 (3)	0.047 (4)	0.003 (3)	0.006 (3)	−0.010 (2)
C4	0.052 (3)	0.033 (3)	0.062 (4)	0.008 (3)	0.001 (3)	0.005 (3)
C5	0.035 (3)	0.051 (3)	0.032 (3)	0.000 (2)	−0.003 (2)	0.003 (2)
C6	0.031 (3)	0.038 (3)	0.035 (3)	0.001 (2)	0.000 (2)	−0.003 (2)
C7	0.032 (3)	0.042 (3)	0.032 (3)	−0.002 (2)	0.004 (2)	0.001 (2)
C8	0.050 (3)	0.047 (3)	0.035 (3)	−0.003 (2)	0.014 (3)	−0.003 (2)
C9	0.042 (3)	0.067 (4)	0.033 (3)	−0.001 (3)	0.003 (3)	0.011 (3)
C10	0.040 (3)	0.042 (3)	0.053 (4)	−0.001 (2)	0.007 (3)	0.021 (3)
C11	0.043 (3)	0.035 (3)	0.056 (4)	−0.006 (2)	0.011 (3)	−0.002 (3)
C12	0.025 (2)	0.046 (3)	0.034 (3)	−0.003 (2)	0.001 (2)	0.003 (2)
C13	0.032 (3)	0.047 (3)	0.029 (3)	−0.006 (2)	0.002 (2)	−0.006 (2)
C14	0.038 (3)	0.044 (3)	0.037 (3)	−0.007 (2)	0.001 (2)	−0.003 (2)
C15	0.038 (3)	0.047 (3)	0.038 (3)	−0.003 (2)	0.001 (2)	−0.017 (2)
C16	0.040 (3)	0.060 (3)	0.026 (3)	−0.004 (3)	−0.002 (2)	−0.010 (2)
C17	0.038 (3)	0.045 (3)	0.038 (3)	−0.002 (2)	−0.005 (2)	0.000 (2)
C18	0.036 (3)	0.052 (3)	0.029 (3)	−0.004 (2)	−0.001 (2)	−0.008 (2)
C19	0.026 (2)	0.039 (3)	0.026 (3)	0.004 (2)	−0.001 (2)	−0.003 (2)
C20	0.023 (2)	0.040 (3)	0.029 (3)	0.001 (2)	0.000 (2)	0.000 (2)
C21	0.031 (3)	0.037 (3)	0.040 (3)	0.000 (2)	0.005 (2)	0.003 (2)
C22	0.051 (3)	0.046 (3)	0.042 (3)	0.006 (3)	0.006 (3)	0.013 (2)
C23	0.052 (4)	0.058 (4)	0.032 (3)	0.001 (3)	−0.007 (3)	0.006 (3)
C24	0.040 (3)	0.054 (3)	0.034 (3)	−0.006 (2)	−0.008 (2)	0.000 (2)
C25	0.024 (2)	0.042 (3)	0.033 (3)	0.000 (2)	0.004 (2)	0.003 (2)
C26	0.035 (3)	0.042 (3)	0.024 (3)	−0.001 (2)	−0.001 (2)	0.003 (2)
C27	0.036 (3)	0.043 (3)	0.024 (3)	0.002 (2)	−0.004 (2)	0.003 (2)
C28	0.036 (3)	0.035 (3)	0.043 (3)	−0.001 (2)	0.001 (2)	0.002 (2)
C29	0.065 (4)	0.050 (3)	0.049 (4)	−0.016 (3)	0.001 (3)	0.001 (3)
C30	0.084 (5)	0.053 (4)	0.069 (5)	−0.024 (3)	0.005 (4)	−0.008 (3)
C31	0.068 (4)	0.049 (4)	0.071 (5)	−0.013 (3)	0.007 (4)	0.015 (3)
C32	0.060 (4)	0.055 (4)	0.049 (4)	−0.004 (3)	0.007 (3)	0.018 (3)
C33	0.042 (3)	0.045 (3)	0.048 (4)	−0.001 (2)	−0.003 (3)	0.006 (2)

Geometric parameters (Å, º) top

Hg1—C18	2.072 (5)	C13—C14	1.383 (7)
Hg1—C6	2.079 (5)	C13—C18	1.407 (7)
Hg2—C7	2.074 (5)	C14—C15	1.387 (7)
Hg2—C1	2.079 (5)	C15—C16	1.358 (7)
Hg3—C13	2.079 (5)	C16—C17	1.385 (7)
Hg3—C12	2.084 (5)	C17—C18	1.377 (7)
F1—C5	1.355 (6)	C19—C26	1.432 (6)
F2—C4	1.338 (6)	C19—C20	1.468 (6)
F3—C3	1.335 (6)	C20—C25	1.368 (6)
F4—C2	1.356 (6)	C20—C21	1.416 (6)
F5—C8	1.359 (6)	C21—C22	1.364 (7)
F6—C9	1.347 (6)	C21—H21	0.9500
F7—C10	1.339 (6)	C22—C23	1.374 (8)
F8—C11	1.351 (6)	C22—H22	0.9500
F9—C14	1.358 (6)	C23—C24	1.377 (7)
F10—C15	1.352 (5)	C23—H23	0.9500
F11—C16	1.352 (6)	C24—C25	1.388 (7)
F12—C17	1.363 (6)	C24—H24	0.9500
O1—C19	1.256 (5)	C26—C27	1.337 (7)
O2—C27	1.358 (6)	C26—H26	0.9500
O2—C25	1.373 (5)	C27—C28	1.484 (6)
C1—C2	1.378 (6)	C28—C33	1.374 (7)
C1—C6	1.413 (7)	C28—C29	1.397 (7)
C2—C3	1.376 (7)	C29—C30	1.380 (8)
C3—C4	1.371 (8)	C29—H29	0.9500
C4—C5	1.388 (7)	C30—C31	1.374 (9)
C5—C6	1.382 (7)	C30—H30	0.9500
C7—C8	1.381 (7)	C31—C32	1.358 (8)
C7—C12	1.406 (7)	C31—H31	0.9500
C8—C9	1.379 (7)	C32—C33	1.385 (7)
C9—C10	1.376 (8)	C32—H32	0.9500
C10—C11	1.370 (8)	C33—H33	0.9500
C11—C12	1.377 (7)

C18—Hg1—C6	175.85 (19)	F12—C17—C18	119.9 (4)
C7—Hg2—C1	175.8 (2)	F12—C17—C16	117.3 (5)
C13—Hg3—C12	175.7 (2)	C18—C17—C16	122.8 (5)
C27—O2—C25	119.1 (4)	C17—C18—C13	118.0 (4)
C2—C1—C6	118.2 (4)	C17—C18—Hg1	120.4 (4)
C2—C1—Hg2	120.0 (4)	C13—C18—Hg1	121.5 (4)
C6—C1—Hg2	121.8 (3)	O1—C19—C26	123.4 (4)
F4—C2—C3	117.3 (4)	O1—C19—C20	122.4 (4)
F4—C2—C1	119.6 (4)	C26—C19—C20	114.2 (4)
C3—C2—C1	123.1 (5)	C25—C20—C21	117.5 (4)
F3—C3—C4	119.6 (5)	C25—C20—C19	119.8 (4)
F3—C3—C2	121.3 (5)	C21—C20—C19	122.7 (4)
C4—C3—C2	119.2 (5)	C22—C21—C20	120.4 (5)
F2—C4—C3	120.9 (5)	C22—C21—H21	119.8
F2—C4—C5	120.2 (5)	C20—C21—H21	119.8
C3—C4—C5	118.9 (5)	C21—C22—C23	120.2 (5)
F1—C5—C6	119.7 (4)	C21—C22—H22	119.9
F1—C5—C4	117.6 (5)	C23—C22—H22	119.9
C6—C5—C4	122.7 (5)	C22—C23—C24	121.2 (5)
C5—C6—C1	118.0 (4)	C22—C23—H23	119.4
C5—C6—Hg1	120.2 (4)	C24—C23—H23	119.4
C1—C6—Hg1	121.8 (3)	C23—C24—C25	117.9 (5)
C8—C7—C12	117.9 (4)	C23—C24—H24	121.0
C8—C7—Hg2	119.4 (4)	C25—C24—H24	121.0
C12—C7—Hg2	122.6 (3)	C20—C25—O2	122.1 (4)
F5—C8—C9	117.2 (5)	C20—C25—C24	122.7 (4)
F5—C8—C7	120.0 (5)	O2—C25—C24	115.2 (4)
C9—C8—C7	122.8 (5)	C27—C26—C19	122.5 (5)
F6—C9—C10	119.6 (5)	C27—C26—H26	118.7
F6—C9—C8	121.5 (5)	C19—C26—H26	118.7
C10—C9—C8	118.8 (5)	C26—C27—O2	122.2 (4)
F7—C10—C11	121.4 (5)	C26—C27—C28	126.5 (5)
F7—C10—C9	119.5 (5)	O2—C27—C28	111.3 (4)
C11—C10—C9	119.1 (5)	C33—C28—C29	118.9 (5)
F8—C11—C10	117.7 (5)	C33—C28—C27	120.9 (5)
F8—C11—C12	119.5 (5)	C29—C28—C27	120.1 (5)
C10—C11—C12	122.8 (5)	C30—C29—C28	119.2 (6)
C11—C12—C7	118.4 (5)	C30—C29—H29	120.4
C11—C12—Hg3	120.2 (4)	C28—C29—H29	120.4
C7—C12—Hg3	121.3 (3)	C31—C30—C29	121.5 (6)
C14—C13—C18	118.3 (4)	C31—C30—H30	119.3
C14—C13—Hg3	119.2 (4)	C29—C30—H30	119.3
C18—C13—Hg3	122.5 (3)	C32—C31—C30	119.1 (5)
F9—C14—C13	120.4 (4)	C32—C31—H31	120.4
F9—C14—C15	117.3 (4)	C30—C31—H31	120.4
C13—C14—C15	122.3 (5)	C31—C32—C33	120.7 (6)
F10—C15—C16	119.9 (5)	C31—C32—H32	119.6
F10—C15—C14	120.8 (5)	C33—C32—H32	119.6
C16—C15—C14	119.2 (4)	C28—C33—C32	120.6 (5)
F11—C16—C15	120.1 (4)	C28—C33—H33	119.7
F11—C16—C17	120.7 (5)	C32—C33—H33	119.7
C15—C16—C17	119.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···F4ⁱ	0.95	2.54	3.486 (6)	173
C24—H24···F1ⁱⁱ	0.95	2.68	3.342 (6)	127
C30—H30···F11ⁱⁱ	0.95	2.57	3.473 (7)	160
C31—H31···F5ⁱⁱⁱ	0.95	2.62	3.200 (8)	120
C32—H32···F5ⁱⁱⁱ	0.95	2.50	3.149 (6)	126
C21—H21···C7	0.95	2.78	3.456 (7)	129
C24—H24···C16^iv	0.95	2.82	3.621 (7)	142

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

Acknowledgements

The authors thank Dr A. Yakovenko for fruitful discussions.

Funding information

Funding for this research was provided by: NSF PREM (grant No. DMR-2122108).

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