Structure of tri­aqua­tris­(1,1,1-tri­fluoro-4-oxo­pentan-2-olato)cerium(III) as a possible fluorescent compound

Koizumi, A.; Hasegawa, T.; Itadani, A.; Toda, K.; Zhu, T.; Sato, M.

doi:10.1107/S2056989018001135

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ISSN: 2056-9890

Volume 74| Part 2| February 2018| Pages 229-232

https://doi.org/10.1107/S2056989018001135

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Structure of triaquatris(1,1,1-trifluoro-4-oxopentan-2-olato)cerium(III) as a possible fluorescent compound

Atsuya Koizumi,^a Takuya Hasegawa,^b,^c Atsushi Itadani,^d Kenji Toda,^a Taoyun Zhu ^e and Mineo Sato ^f ^*

^aGraduate School of Science and Technology, Niigata University, 8050 Ikarashi 2-nocho, Niigata 950-2181, Japan, ^bDepartment of Marine Resource Science, Faculity of Agriculture and Marine Science, Kochi University, 200 Otsu, Monobe, Nankoku City, Kochi 783-8502, Japan, ^cCenter for Advanced Marine Core Research, Kochi University, Nankoku 783-8502, Japan, ^dDepartment of Human Sciences, Obihiro University of Agriculture and Veterinary Medicine, Inada-cho, Obihiro, Hokkaido 080-8555, Japan, ^eNenjiang Senior High School, Nenjiang Heihe City, Heilongjiang Province, 161400, People's Republic of China, and ^fDepartment of Chemistry and Chemical Engineering, Faculty of Engineering, Niigata University, Ikarashi 2-no-cho, Niigata City, 950-2181, Japan
^*Correspondence e-mail: msato@eng.niigata-u.ac.jp

Edited by A. Van der Lee, Université de Montpellier II, France (Received 1 December 2017; accepted 17 January 2018; online 26 January 2018)

Luminescence due to the d–f transition of Ce³⁺ is quite rare in metal–organic complexes where concentrate quenching frequently occurs. One of the possible ways to avoid this is to design an architecture with elongated metal–metal distances. In the structure of the title complex, triaquatris(1,1,1-trifluoro-4-oxopentan-2-olato-κ²O,O′)cerium(III), [Ce(C₅H₄F₃O₂)₃(H₂O)₃], the Ce^III complex is linked to neighbouring ones by hydrogen bonding. Within the complex, the Ce^III atom is coordinated by nine O atoms from three 1,1,1-trifluoro-4-oxopentan-2-olate (tfa) anions as bidentate ligands and three water molecules as monodentate ligands. Thus, the coordination number of Ce^III atom is nine in a monocapped square–antiprismatic polyhedron. The F atoms of all three independent CF₃ groups in tfa are disordered over two positions with occupancy ratios of about 0.8:0.2. The intermolecular hydrogen bonds between the ligands involve tfa–water interactions along the [110] and [1-10] directions, generating an overall two-dimensional layered network structure. The presence of the F atoms in the tfa anion is responsible for an increased intermolecular metal–metal distance compared to that in the analogous acetylacetonate (acac) derivatives. Fluorescence from Ce³⁺ is, however, not observed.

Keywords: crystal structure; 1,1,1-trifluoroacetylacetone; cerium complex; fluorescence.

CCDC reference: 1817747

1. Chemical context

β-diketonate ligands have been used widely in metal–organic complexes involving rare earth elements because of their simple usage as organic bidentate ligands (Binnemans, 2005 ). The nature of the ligand used is important for a possible enhancement of the luminescence efficiency and intensity; for example, acac is known to have a possible effect on the 4f–4f transition emission of Eu³⁺ (Kuz'mina et al., 2006 ). Tb(acac)₃ was first used as an active light-emitting layer material in LEDs based on the emission from the lanthanide complex (Kido et al., 1990 ). Recently, a lanthanide complex containing Tb³⁺ and Eu³⁺, hexafluoroacetylacetonate (hfa) and 4,4′-bis(diphenylphosphoryl)biphenyl (dpdp), [Tb_0.99Eu_0.01(hfa)₃(dpdp)]_n, was reported to exhibit an expression thermo-sensing emission, called chameleon luminophore (Miyata et al., 2013 ; Hasegawa & Nakanishi, 2015 ). The hfa anion can absorb efficiently a visible light excitation and transfer the excited energy from hfa to Tb³⁺, because the energy of the triplet state of hfa (22 000 cm⁻¹) is very close to an energy level of Tb³⁺ (20 500 cm⁻¹; Katagiri et al., 2004 ). However, the proximity of the levels causes a back-energy transfer from Tb³⁺ to hfa. The probability of three types of energy transfer from hfa to Tb³⁺, from Tb³⁺ to Eu³⁺ and from Tb³⁺ to hfa is temperature dependent. As a result, the complex can show green, yellow, orange and red emissions despite the 4f–4f transition.

The nature of the ligand is important in the design of fluorescent metal–organic complexes. The F atoms in hfa are larger than the H atoms in acac, which means that the hfa ligand can reduce the energy loss due to thermal vibrations and could increase the intermolecular distance between the central lanthanide atoms. This may control the concentration quenching.

A considerable number of metal–organic complexes containing Ce³⁺ have been reported so far, but the examples of emission based on the 5d–4f transition of Ce³⁺ in metal–organic complexes are scarce. [Ce(triRNTB)₂](CF₃SO₃)₃ [NTB = N-substituted tris(N-alkylbenzimidazol-2-ylmethyl)amine] and _∞³[Ce(Im)₃(ImH)]·ImH (Zheng et al., 2007 ; Meyer et al., 2015 ) are some of the rare cases. One of the reasons for the small number of fluorescent metal–organic complexes containing Ce³⁺ is the too short distance between the Ce³⁺ ions, causing luminescence quenching by the energy transfer between Ce³⁺ ions. [Ce(triRNTB)₂](CF₃SO₃)₃ can show a blue emission thanks to a long Ce—Ce distance of about 17–18 Å. The use of more bulky ligands such as NTB is favourable for a longer Ce—Ce distance. _∞³[Ce(Im)₃(ImH)]·ImH also shows a blue fluorescence emission despite a relatively short separation between the Ce³⁺ cations of 7 Å. Emission occurs more frequently in 3D structures with isolated complexes than in framework structures.

This study reports structural data on a newly synthesized Ce³⁺ complex with functional ligands of tfa.

2. Structural commentary

The title complex crystallizes in the orthorhombic space group Pcab with eight formula units of [Ce(C₅F₃H₄O₂)₃(H₂O)₃]. Each molecule is isolated individually, i.e. the crystal structure is not a framework structure. The central Ce atom is coordinated by nine O atoms of three hfa and three water molecules (Fig. 1). Thus, the Ce atom has a monocapped square–antiprismatic coordination. The Ce—O bond lengths can be classified into two categories; the first is involved in interactions with a bidentate hfa, and the second in interactions with monodentate water molecules. All distances are comparable with those reported for tfa complexes (Nakamura et al., 1986 ). The trifluoromethyl groups of tfa coordinating the Ce³⁺ ion are all disordered on the F atoms, as is frequently observed in trifluoroacetate and tetrafluoroborate complexes (Hamaguchi et al., 2011 ; Strehler et al., 2015 ).

Figure 1
View of the molecular structure of the title complex, with displacement ellipsoids for non-H atoms drawn at the 30% probability level.

3. Supramolecular features

The individual complexes are linked to neighbouring ones by four types of hydrogen bonds (Table 1), nearly within the ab plane. There are two types of hydrogen-bond directions; the first are parallel to [110] and the second are parallel to [1 $[\overline{1}]$ 0]. The chains consisting of the complex molecules and the hydrogen bonds, two types of which are cross-linked to each other, building up two-dimensional networks (Fig. 2). The functional hydrophobic groups of –CF₃ and –CH₃ are located on the outside of the layer, resulting in the stabilization of the stacking layers by intermolecular forces. Such a layer structure is also observed in the acetylacetonate complex, [Y(C₅H₇O₂)₃(H₂O)₃] (Cunningham et al., 1967 ) (Fig. 3). This yttrium complex also contains an isolated water in the structure, different from the title compound, but the water molecule can act as a hydrogen-bond linker because it exists within a molecular layer. As a result, the hydrogen bonds make a two-dimensional layered network, as in the title compound. The Ln—Ln distance of nearest neighbours in this complex is longer than that of [Y(C₅H₇O₂)₃(H₂O)₃], the shortest distance in the former being 6.141 Å and in the latter 6.035 Å. This difference is mainly caused by atomic size difference between F and H atoms, even taking into account the atomic size difference between La and Y. The shortest Ln—Ln distance of [La(C₅H₇O₂)₂(C₃H₄N₂)(NO₃)(H₂O)₂] (6.247 Å; Koizumi et al., 2017 ) is slightly longer than that of the title compound. The fact that the present complex does not show any luminescence from Ce³⁺ can certainly be attributed to an insufficient metal–metal separation. Based on previous studies and the present work, the minimum metal–metal separation is expected to be more than 7 Å.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O32ⁱ	0.84 (2)	2.13 (3)	2.927 (4)	158 (5)
O1W—H1WB⋯O22ⁱ	0.83 (2)	2.23 (4)	2.969 (4)	149 (6)
O2W—H2WA⋯O14ⁱⁱ	0.85 (2)	1.91 (2)	2.759 (4)	177 (6)
O3W—H3WA⋯O24ⁱⁱⁱ	0.85 (2)	1.94 (2)	2.792 (4)	176 (7)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

Figure 2
Connection of discrete complexes by intermolecular hydrogen-bonded (blue lines) chains in the ab plane, viewed in projection along the c axis. Colour code: Ce yellow, C grey, F green and O red. H atoms have been omitted. Only the major components of the disordered CF₃ groups are shown for clarity.

Figure 3
Comparison of the layered structures of the title compound and that of the [Y(C₅H₇O₂)₃(H₂O)₃] complex (Cunningham et al., 1967

). Colour code: Ce yellow, Y light blue, C grey, F green and O red. H atoms have been omitted. Only the main components of the disordered CF₃ groups are shown for clarity.

4. Database survey

Crystal structures of related complexes involving lanthanide ions have been reported with acac ligands (Berg & Acosta, 1968 ; Binnemans, 2005; Filotti et al., 1996 ; Fujinaga et al., 1981 ; Lim et al., 1996 ; Phillips et al., 1968 ; Richardson et al., 1968 ; Stites et al., 1948 ), with tfa complexes (Ilmi et al., 2015 ; Katagiri et al., 2007 ; Li et al., 2017 ; Lim et al., 1996; Nakamura et al., 1986; Yan et al., 2009 ) and with hfa complexes (Subhan et al., 2014 ; Fratini et al., 2008 ; Hasegawa et al., 2013 , 2015 ; Kataoka et al., 2016 ; Rybkin et al., 2011 ; Tsaryuk et al., 2017 ; Wang et al., 2017 ; Yuasa et al., 2011 ).

5. Synthesis and crystallization

Yellow plate-like crystals were obtained by slow evaporation from an acetone solution of Ce(NO₃)₃·6H₂O and trifluoroacetylacetone (1:3 molar ratio). The products were filtered off and dried at room temperature.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms bonded to a C atom were positioned geometrically after each cycle in idealized locations and refined as riding on their parent C atoms with C—H = 0.93 Å and U_iso(H) = 1.2U_iso(C atom). All hydrogen atoms bonded to a water O atom were located in a difference-Fourier map and refined isotropically with a distance restraint of 0.85 (2) Å and with thermal restraints U_iso(H) = 1.5U_iso(O atom). The occupancies of the disordered F atoms in the –CF₃ group were refined for the pairs F11A/F11D, F11B/F11E and F11C/F11F to be 0.829 (14)/0.171 (14), for the pairs of F21A/F21F, F21B/F21E and F21C/F21F to be 0.838 (17)/0.162 (17), and for the pairs of F31A/F31D, F31B/F31E and F31C/F31F to be 0.836 (11)/0.164 (11).

Table 2
Experimental details

Crystal data
Chemical formula	[Ce(C₅H₄F₃O₂)₃(H₂O)₃]
M_r	653.41
Crystal system, space group	Orthorhombic, Pcab
Temperature (K)	293
a, b, c (Å)	11.6347 (7), 16.5121 (9), 24.5577 (17)
V (Å³)	4717.9 (5)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	2.04
Crystal size (mm)	0.3 × 0.19 × 0.11

Data collection
Diffractometer	Rigaku XtaLAB mini
Absorption correction	Multi-scan (REQAB; Rigaku, 1998 )
T_min, T_max	0.603, 0.805
No. of measured, independent and observed [I > 2σ(I)] reflections	45156, 5404, 4309
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.092, 1.11
No. of reflections	5404
No. of parameters	367
No. of restraints	60
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.44
Computer programs: CrystalClear (Rigaku, 2006 ) and SORTAV (Blessing, 1995 ), SIR2014 (Burla et al., 2015 ), SHELXL2014 (Sheldrick, 2015 ) and ORTEP-3 for Windows and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1817747

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989018001135/vn2133sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018001135/vn2133Isup2.hkl

checkCIF report

Computing details top

Data collection: CrystalClear (Rigaku, 2006); cell refinement: CrystalClear (Rigaku, 2006); data reduction: CrystalClear (Rigaku, 2006) and SORTAV (Blessing, 1995); program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Triaquatris(1,1,1-trifluoro-4-oxopentan-2-olato-κ²O,O')cerium(III) top

Crystal data top

[Ce(C₅H₄F₃O₂)₃(H₂O)₃]	F(000) = 2552
M_r = 653.41	D_x = 1.84 Mg m⁻³
Orthorhombic, Pcab	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2bc 2ac	Cell parameters from 36866 reflections
a = 11.6347 (7) Å	θ = 3.0–27.5°
b = 16.5121 (9) Å	µ = 2.04 mm⁻¹
c = 24.5577 (17) Å	T = 293 K
V = 4717.9 (5) Å³	Prism, yellow
Z = 8	0.3 × 0.19 × 0.11 mm

Data collection top

Rigaku XtaLAB mini diffractometer	5404 independent reflections
Radiation source: sealed x-ray tube	4309 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 10 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
phi or ω oscillation scans	h = −14→15
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	k = −21→21
T_min = 0.603, T_max = 0.805	l = −31→31
45156 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)] = 0.036	Hydrogen site location: mixed
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0377P)² + 9.6633P] where P = (F_o² + 2F_c²)/3
5404 reflections	(Δ/σ)_max = 0.001
367 parameters	Δρ_max = 0.78 e Å⁻³
60 restraints	Δρ_min = −0.44 e Å⁻³
0 constraints

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	Occ. (<1)
Ce1	0.44439 (2)	0.34074 (2)	0.44106 (2)	0.02854 (8)
C11	0.4237 (6)	0.3197 (4)	0.2473 (2)	0.0778 (19)
C12	0.3779 (5)	0.3321 (3)	0.30394 (19)	0.0538 (13)
O12	0.4339 (3)	0.3049 (2)	0.34228 (12)	0.0486 (8)
C13	0.2728 (5)	0.3716 (4)	0.3061 (2)	0.0646 (15)
H13	0.2427	0.3924	0.2739	0.078*
C14	0.2092 (4)	0.3819 (4)	0.3546 (2)	0.0600 (14)
O14	0.2451 (3)	0.3617 (2)	0.40111 (12)	0.0448 (7)
C15	0.0892 (6)	0.4173 (6)	0.3520 (3)	0.113 (3)
H15A	0.0766	0.4406	0.3167	0.169*
H15B	0.0812	0.4584	0.3794	0.169*
H15C	0.0338	0.3752	0.3583	0.169*
C21	0.4510 (5)	0.5793 (3)	0.33461 (19)	0.0586 (14)
C22	0.5053 (4)	0.5033 (3)	0.35843 (18)	0.0439 (10)
O22	0.4552 (3)	0.47868 (18)	0.40133 (11)	0.0408 (7)
C23	0.5971 (5)	0.4712 (3)	0.3316 (2)	0.0536 (12)
H23	0.6201	0.496	0.2994	0.064*
C24	0.6600 (4)	0.4024 (3)	0.34943 (19)	0.0468 (11)
O24	0.6358 (2)	0.36304 (19)	0.39146 (12)	0.0429 (7)
C25	0.7622 (5)	0.3774 (4)	0.3167 (2)	0.0700 (16)
H25A	0.7489	0.3897	0.279	0.105*
H25B	0.7745	0.3203	0.3208	0.105*
H25C	0.8288	0.4063	0.3292	0.105*
C31	0.1589 (4)	0.4538 (3)	0.5562 (2)	0.0607 (14)
C32	0.2598 (4)	0.3977 (3)	0.54542 (19)	0.0430 (10)
O32	0.3247 (3)	0.42071 (18)	0.50708 (12)	0.0454 (7)
C33	0.2669 (4)	0.3297 (3)	0.5767 (2)	0.0529 (12)
H33	0.2102	0.3207	0.6027	0.063*
C34	0.3567 (4)	0.2718 (3)	0.57165 (18)	0.0467 (11)
O34	0.4301 (3)	0.27381 (19)	0.53500 (12)	0.0448 (7)
C35	0.3625 (6)	0.2034 (4)	0.6122 (3)	0.0802 (19)
H35A	0.316	0.2164	0.6433	0.12*
H35B	0.4407	0.1958	0.6236	0.12*
H35C	0.3346	0.1546	0.5957	0.12*
F11B	0.4262 (11)	0.3878 (4)	0.2185 (3)	0.166 (5)	0.829 (14)
F11A	0.3683 (6)	0.2702 (5)	0.2173 (2)	0.132 (3)	0.829 (14)
F11C	0.5308 (6)	0.2914 (7)	0.2481 (2)	0.156 (5)	0.829 (14)
F11D	0.455 (3)	0.2450 (11)	0.2438 (15)	0.131 (14)*	0.171 (14)
F11E	0.503 (2)	0.3703 (15)	0.2358 (11)	0.080 (9)*	0.171 (14)
F11F	0.336 (2)	0.330 (3)	0.2134 (15)	0.149 (17)*	0.171 (14)
F21A	0.3517 (8)	0.5668 (4)	0.3129 (5)	0.148 (4)	0.838 (17)
F21B	0.5143 (11)	0.6165 (5)	0.2974 (4)	0.160 (5)	0.838 (17)
F21C	0.4371 (7)	0.6369 (2)	0.3718 (2)	0.0713 (18)	0.838 (17)
F21D	0.4696 (19)	0.5826 (17)	0.2820 (6)	0.060 (8)*	0.162 (17)
F21E	0.483 (3)	0.6448 (16)	0.3572 (13)	0.108 (15)*	0.162 (17)
F21F	0.3356 (14)	0.5734 (15)	0.3364 (10)	0.054 (7)*	0.162 (17)
F31A	0.1248 (6)	0.4523 (5)	0.6089 (2)	0.137 (3)	0.836 (11)
F31B	0.0676 (4)	0.4319 (3)	0.5295 (3)	0.110 (3)	0.836 (11)
F31C	0.1797 (4)	0.5278 (2)	0.5457 (4)	0.115 (3)	0.836 (11)
F31E	0.129 (3)	0.487 (2)	0.5071 (8)	0.125 (13)*	0.164 (11)
F31F	0.175 (4)	0.5175 (18)	0.5874 (14)	0.16 (2)*	0.164 (11)
F31D	0.065 (2)	0.419 (2)	0.5740 (17)	0.140 (16)*	0.164 (11)
O1W	0.5906 (3)	0.4133 (2)	0.50449 (13)	0.0432 (7)
H1WA	0.627 (4)	0.455 (2)	0.495 (2)	0.065*
H1WB	0.574 (5)	0.426 (4)	0.5364 (11)	0.065*
O2W	0.5781 (3)	0.2200 (2)	0.45895 (15)	0.0536 (9)
H2WA	0.629 (4)	0.193 (4)	0.442 (2)	0.08*
H2WB	0.578 (5)	0.201 (4)	0.4904 (13)	0.08*
O3W	0.3258 (3)	0.2079 (2)	0.44205 (16)	0.0578 (9)
H3WA	0.270 (4)	0.186 (4)	0.425 (2)	0.087*
H3WB	0.346 (6)	0.161 (2)	0.451 (3)	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce1	0.02544 (11)	0.03113 (12)	0.02903 (12)	0.00204 (9)	0.00172 (9)	0.00215 (9)
C11	0.104 (6)	0.089 (5)	0.040 (3)	−0.012 (4)	−0.001 (3)	−0.008 (3)
C12	0.066 (3)	0.060 (3)	0.035 (2)	−0.015 (3)	−0.001 (2)	−0.002 (2)
O12	0.0509 (19)	0.059 (2)	0.0355 (16)	0.0012 (16)	0.0016 (14)	−0.0088 (15)
C13	0.068 (4)	0.080 (4)	0.046 (3)	0.005 (3)	−0.012 (3)	0.011 (3)
C14	0.043 (3)	0.076 (4)	0.061 (3)	0.004 (3)	−0.011 (2)	0.013 (3)
O14	0.0316 (15)	0.059 (2)	0.0437 (17)	−0.0006 (14)	−0.0022 (13)	0.0072 (14)
C15	0.066 (4)	0.174 (9)	0.097 (5)	0.054 (5)	−0.018 (4)	0.035 (6)
C21	0.089 (4)	0.046 (3)	0.041 (3)	0.010 (3)	0.004 (3)	0.011 (2)
C22	0.054 (3)	0.038 (2)	0.039 (2)	0.003 (2)	−0.003 (2)	0.0074 (18)
O22	0.0475 (17)	0.0375 (15)	0.0373 (15)	0.0058 (14)	0.0065 (13)	0.0087 (13)
C23	0.061 (3)	0.054 (3)	0.046 (3)	0.006 (2)	0.015 (2)	0.019 (2)
C24	0.036 (2)	0.060 (3)	0.044 (2)	0.004 (2)	0.008 (2)	0.011 (2)
O24	0.0314 (15)	0.0551 (18)	0.0423 (17)	0.0061 (13)	0.0063 (13)	0.0154 (14)
C25	0.055 (3)	0.093 (4)	0.062 (3)	0.014 (3)	0.027 (3)	0.014 (3)
C31	0.040 (3)	0.057 (3)	0.085 (4)	0.000 (2)	0.014 (3)	−0.019 (3)
C32	0.030 (2)	0.049 (3)	0.049 (3)	−0.0027 (19)	0.0042 (19)	−0.016 (2)
O32	0.0467 (17)	0.0472 (17)	0.0424 (16)	0.0084 (15)	0.0108 (14)	−0.0012 (14)
C33	0.046 (3)	0.061 (3)	0.051 (3)	−0.004 (2)	0.021 (2)	−0.001 (2)
C34	0.047 (3)	0.054 (3)	0.039 (2)	−0.008 (2)	0.007 (2)	0.002 (2)
O34	0.0467 (18)	0.0533 (19)	0.0343 (15)	0.0073 (15)	0.0087 (14)	0.0063 (14)
C35	0.095 (5)	0.078 (4)	0.068 (4)	0.007 (4)	0.030 (3)	0.032 (3)
F11B	0.274 (13)	0.152 (7)	0.073 (4)	0.019 (7)	0.064 (6)	0.042 (4)
F11A	0.142 (6)	0.173 (7)	0.082 (4)	−0.010 (5)	−0.013 (4)	−0.076 (4)
F11C	0.099 (5)	0.305 (13)	0.065 (3)	0.041 (7)	0.018 (3)	−0.036 (5)
F21A	0.196 (8)	0.097 (4)	0.151 (7)	0.052 (5)	−0.128 (6)	−0.018 (5)
F21B	0.238 (10)	0.096 (5)	0.146 (7)	0.068 (6)	0.108 (7)	0.087 (5)
F21C	0.105 (5)	0.040 (2)	0.069 (3)	0.012 (2)	−0.006 (3)	0.0032 (19)
F31A	0.129 (6)	0.175 (7)	0.106 (5)	0.071 (5)	0.053 (4)	−0.015 (4)
F31B	0.049 (3)	0.090 (4)	0.191 (7)	0.017 (2)	−0.034 (3)	−0.047 (4)
F31C	0.075 (3)	0.042 (2)	0.228 (9)	0.005 (2)	0.055 (4)	−0.021 (3)
O1W	0.0436 (17)	0.0465 (18)	0.0396 (17)	−0.0101 (14)	−0.0018 (14)	−0.0037 (15)
O2W	0.048 (2)	0.059 (2)	0.054 (2)	0.0261 (16)	0.0161 (16)	0.0169 (17)
O3W	0.059 (2)	0.0420 (18)	0.072 (2)	−0.0178 (17)	−0.0242 (19)	0.0094 (17)

Geometric parameters (Å, º) top

Ce1—O22	2.481 (3)	C22—O22	1.271 (5)
Ce1—O12	2.500 (3)	C22—C23	1.362 (7)
Ce1—O32	2.512 (3)	C23—C24	1.420 (7)
Ce1—O14	2.542 (3)	C23—H23	0.93
Ce1—O34	2.563 (3)	C24—O24	1.252 (5)
Ce1—O24	2.565 (3)	C24—C25	1.493 (6)
Ce1—O2W	2.566 (3)	C25—H25A	0.96
Ce1—O3W	2.592 (3)	C25—H25B	0.96
Ce1—O1W	2.599 (3)	C25—H25C	0.96
C11—F11A	1.276 (7)	C31—F31C	1.273 (7)
C11—F11E	1.280 (15)	C31—F31B	1.299 (6)
C11—F11D	1.289 (16)	C31—F31D	1.308 (17)
C11—F11B	1.328 (8)	C31—F31F	1.315 (17)
C11—F11F	1.330 (16)	C31—F31A	1.354 (7)
C11—F11C	1.331 (8)	C31—F31E	1.372 (16)
C11—C12	1.504 (8)	C31—C32	1.518 (6)
C12—O12	1.230 (6)	C32—O32	1.266 (5)
C12—C13	1.387 (8)	C32—C33	1.365 (7)
C13—C14	1.413 (8)	C33—C34	1.422 (7)
C13—H13	0.93	C33—H33	0.93
C14—O14	1.262 (6)	C34—O34	1.241 (5)
C14—C15	1.514 (8)	C34—C35	1.507 (7)
C15—H15A	0.96	C35—H35A	0.96
C15—H15B	0.96	C35—H35B	0.96
C15—H15C	0.96	C35—H35C	0.96
C21—F21E	1.273 (15)	O1W—H1WA	0.84 (2)
C21—F21A	1.289 (8)	O1W—H1WB	0.83 (2)
C21—F21D	1.312 (14)	O2W—H2WA	0.85 (2)
C21—F21B	1.324 (7)	O2W—H2WB	0.84 (2)
C21—F21C	1.329 (6)	O3W—H3WA	0.85 (2)
C21—F21F	1.347 (15)	O3W—H3WB	0.84 (2)
C21—C22	1.522 (6)

O22—Ce1—O12	80.70 (11)	F21A—C21—F21B	106.6 (7)
O22—Ce1—O32	78.42 (10)	F21A—C21—F21C	106.8 (6)
O12—Ce1—O32	136.35 (11)	F21B—C21—F21C	102.1 (6)
O22—Ce1—O14	76.68 (10)	F21E—C21—F21F	109.9 (15)
O12—Ce1—O14	67.23 (10)	F21D—C21—F21F	101.5 (12)
O32—Ce1—O14	70.85 (10)	F21E—C21—C22	114.3 (17)
O22—Ce1—O34	138.85 (10)	F21A—C21—C22	113.6 (5)
O12—Ce1—O34	140.17 (11)	F21D—C21—C22	110.2 (13)
O32—Ce1—O34	67.04 (10)	F21B—C21—C22	114.7 (5)
O14—Ce1—O34	110.31 (10)	F21C—C21—C22	112.1 (4)
O22—Ce1—O24	68.74 (10)	F21F—C21—C22	110.0 (12)
O12—Ce1—O24	67.40 (10)	O22—C22—C23	129.5 (4)
O32—Ce1—O24	135.42 (10)	O22—C22—C21	113.1 (4)
O14—Ce1—O24	126.11 (10)	C23—C22—C21	117.4 (4)
O34—Ce1—O24	123.05 (9)	C22—O22—Ce1	130.0 (3)
O22—Ce1—O2W	138.56 (11)	C22—C23—C24	124.5 (4)
O12—Ce1—O2W	90.68 (12)	C22—C23—H23	117.7
O32—Ce1—O2W	129.33 (11)	C24—C23—H23	117.7
O14—Ce1—O2W	136.45 (12)	O24—C24—C23	123.6 (4)
O34—Ce1—O2W	63.28 (10)	O24—C24—C25	118.7 (4)
O24—Ce1—O2W	70.52 (10)	C23—C24—C25	117.7 (4)
O22—Ce1—O3W	143.87 (11)	C24—O24—Ce1	131.4 (3)
O12—Ce1—O3W	77.44 (12)	C24—C25—H25A	109.5
O32—Ce1—O3W	98.26 (12)	C24—C25—H25B	109.5
O14—Ce1—O3W	68.46 (11)	H25A—C25—H25B	109.5
O34—Ce1—O3W	65.93 (11)	C24—C25—H25C	109.5
O24—Ce1—O3W	126.04 (12)	H25A—C25—H25C	109.5
O2W—Ce1—O3W	70.35 (13)	H25B—C25—H25C	109.5
O22—Ce1—O1W	77.26 (10)	F31C—C31—F31B	108.7 (6)
O12—Ce1—O1W	136.27 (11)	F31D—C31—F31F	105.9 (17)
O32—Ce1—O1W	74.57 (11)	F31C—C31—F31A	105.5 (5)
O14—Ce1—O1W	139.99 (11)	F31B—C31—F31A	103.7 (6)
O34—Ce1—O1W	72.65 (10)	F31D—C31—F31E	105.0 (16)
O24—Ce1—O1W	69.51 (10)	F31F—C31—F31E	103.0 (16)
O2W—Ce1—O1W	81.87 (12)	F31C—C31—C32	113.8 (4)
O3W—Ce1—O1W	137.14 (11)	F31B—C31—C32	112.0 (4)
F11E—C11—F11D	113.8 (16)	F31D—C31—C32	115.9 (17)
F11A—C11—F11B	104.2 (7)	F31F—C31—C32	118.7 (19)
F11E—C11—F11F	109.5 (15)	F31A—C31—C32	112.5 (5)
F11D—C11—F11F	107.7 (16)	F31E—C31—C32	106.8 (14)
F11A—C11—F11C	104.9 (7)	O32—C32—C33	129.0 (4)
F11B—C11—F11C	106.6 (8)	O32—C32—C31	114.2 (4)
F11A—C11—C12	116.3 (6)	C33—C32—C31	116.8 (4)
F11E—C11—C12	111.8 (13)	C32—O32—Ce1	130.8 (3)
F11D—C11—C12	106.9 (17)	C32—C33—C34	123.3 (4)
F11B—C11—C12	112.7 (6)	C32—C33—H33	118.4
F11F—C11—C12	106.7 (19)	C34—C33—H33	118.4
F11C—C11—C12	111.4 (5)	O34—C34—C33	123.5 (4)
O12—C12—C13	127.6 (5)	O34—C34—C35	117.9 (5)
O12—C12—C11	118.1 (5)	C33—C34—C35	118.6 (4)
C13—C12—C11	114.3 (5)	C34—O34—Ce1	135.1 (3)
C12—O12—Ce1	133.0 (3)	C34—C35—H35A	109.5
C12—C13—C14	123.4 (5)	C34—C35—H35B	109.5
C12—C13—H13	118.3	H35A—C35—H35B	109.5
C14—C13—H13	118.3	C34—C35—H35C	109.5
O14—C14—C13	123.9 (5)	H35A—C35—H35C	109.5
O14—C14—C15	116.4 (5)	H35B—C35—H35C	109.5
C13—C14—C15	119.6 (5)	Ce1—O1W—H1WA	123 (4)
C14—O14—Ce1	133.5 (3)	Ce1—O1W—H1WB	122 (4)
C14—C15—H15A	109.5	H1WA—O1W—H1WB	100 (5)
C14—C15—H15B	109.5	Ce1—O2W—H2WA	138 (4)
H15A—C15—H15B	109.5	Ce1—O2W—H2WB	117 (4)
C14—C15—H15C	109.5	H2WA—O2W—H2WB	105 (6)
H15A—C15—H15C	109.5	Ce1—O3W—H3WA	140 (5)
H15B—C15—H15C	109.5	Ce1—O3W—H3WB	129 (5)
F21E—C21—F21D	110.2 (15)	H3WA—O3W—H3WB	87 (6)

F11A_a—C11—C12—O12	109.7 (8)	F21C—C21—C22—C23	−130.5 (6)
F11E—C11—C12—O12	−79.3 (17)	F21F—C21—C22—C23	137.2 (12)
F11D—C11—C12—O12	45.9 (19)	C23—C22—O22—Ce1	−24.8 (8)
F11B—C11—C12—O12	−130.0 (8)	C21—C22—O22—Ce1	154.3 (3)
F11F—C11—C12—O12	161.0 (19)	O22—C22—C23—C24	−3.3 (9)
F11C—C11—C12—O12	−10.3 (9)	C21—C22—C23—C24	177.6 (5)
F11A—C11—C12—C13	−68.2 (9)	C22—C23—C24—O24	1.5 (9)
F11E—C11—C12—C13	102.7 (16)	C22—C23—C24—C25	−177.0 (5)
F11D—C11—C12—C13	−132.0 (19)	C23—C24—O24—Ce1	27.8 (7)
F11B—C11—C12—C13	52.0 (10)	C25—C24—O24—Ce1	−153.7 (4)
F11F—C11—C12—C13	−17.0 (19)	F31C—C31—C32—O32	−30.8 (8)
F11C—C11—C12—C13	171.7 (8)	F31B—C31—C32—O32	92.9 (7)
C13—C12—O12—Ce1	−25.9 (8)	F31D—C31—C32—O32	148 (2)
C11—C12—O12—Ce1	156.4 (4)	F31F—C31—C32—O32	−84 (2)
O12—C12—C13—C14	−4.5 (10)	F31A—C31—C32—O32	−150.7 (6)
C11—C12—C13—C14	173.2 (6)	F31E—C31—C32—O32	31.9 (18)
C12—C13—C14—O14	5.5 (10)	F31C—C31—C32—C33	150.7 (6)
C12—C13—C14—C15	−173.0 (7)	F31B—C31—C32—C33	−85.6 (7)
C13—C14—O14—Ce1	23.3 (9)	F31D—C31—C32—C33	−30 (2)
C15—C14—O14—Ce1	−158.2 (5)	F31F—C31—C32—C33	98 (2)
F21E—C21—C22—O22	82.1 (19)	F31A—C31—C32—C33	30.8 (7)
F21A—C21—C22—O22	−70.9 (8)	F31E—C31—C32—C33	−146.6 (17)
F21D—C21—C22—O22	−153.2 (11)	C33—C32—O32—Ce1	28.9 (7)
F21B—C21—C22—O22	166.1 (9)	C31—C32—O32—Ce1	−149.4 (3)
F21C—C21—C22—O22	50.2 (7)	O32—C32—C33—C34	2.2 (8)
F21F—C21—C22—O22	−42.1 (12)	C31—C32—C33—C34	−179.6 (5)
F21E—C21—C22—C23	−98.6 (19)	C32—C33—C34—O34	−7.2 (8)
F21A—C21—C22—C23	108.4 (9)	C32—C33—C34—C35	173.8 (5)
F21D—C21—C22—C23	26.1 (13)	C33—C34—O34—Ce1	−19.7 (7)
F21B—C21—C22—C23	−14.6 (11)	C35—C34—O34—Ce1	159.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O32ⁱ	0.84 (2)	2.13 (3)	2.927 (4)	158 (5)
O1W—H1WB···O22ⁱ	0.83 (2)	2.23 (4)	2.969 (4)	149 (6)
O2W—H2WA···O14ⁱⁱ	0.85 (2)	1.91 (2)	2.759 (4)	177 (6)
O3W—H3WA···O24ⁱⁱⁱ	0.85 (2)	1.94 (2)	2.792 (4)	176 (7)

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

Funding information

This work was partly supported by a Grant-in-Aid for Scientific Research (No. 17H03124 and No. 17H03386) from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

References

Berg, E. W. & Acosta, J. J. C. (1968). Anal. Chim. Acta, 40, 101–113. CrossRef CAS Web of Science Google Scholar
Binnemans, K. (2005). Handbook on the Physics and Chemistry of Rare Earths Vol. 35, edited by K. A. Gschneidner, J. C. G. Bunzli & V. K. Percharsky, ch. 225, pp. 107–272. Amsterdam: Elsevier. Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Burla, M. C., Caliandro, R., Carrozzini, B., Cascarano, G. L., Cuocci, C., Giacovazzo, C., Mallamo, M., Mazzone, A. & Polidori, G. (2015). J. Appl. Cryst. 48, 306–309. Web of Science CrossRef CAS IUCr Journals Google Scholar
Cunningham, J. A., Sands, D. E. & Wagner, W. F. (1967). Inorg. Chem. 6, 499–503. CSD CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Filotti, L., Bugli, G., Ensuque, A. & Bozon-Verduraz, F. (1996). Bull. Soc. Chim. Fr. 133, 1117–1126. CAS Google Scholar
Fratini, A., Richards, G., Larder, E. & Swavey, S. (2008). Inorg. Chem. 47, 1030–1036. CSD CrossRef PubMed CAS Google Scholar
Fujinaga, T., Kuwamoto, T., Sugiura, K. & Ichiki, S. (1981). Talanta, 28, 295–300. CrossRef PubMed CAS Web of Science Google Scholar
Hamaguchi, T., Nagata, T., Kawata, S. & Ando, I. (2011). Acta Cryst. E67, m1632. CSD CrossRef IUCr Journals Google Scholar
Hasegawa, Y. & Nakanishi, T. (2015). RSC Adv. 5, 338–353. Web of Science CrossRef CAS Google Scholar
Hasegawa, Y., Ohkubo, T., Nakanishi, T., Kobayashi, A., Kato, M., Seki, T., Ito, H. & Fushimi, K. (2013). Eur. J. Inorg. Chem. pp. 5911–5918. CSD CrossRef Google Scholar
Hasegawa, Y., Sato, N., Hirai, Y., Nakanishi, T., Kitagawa, Y., Kobayashi, A., Kato, M., Seki, T., Ito, H. & Fushimi, K. (2015). J. Phys. Chem. A, 119, 4825–4833. Web of Science CSD CrossRef CAS PubMed Google Scholar
Ilmi, R. & Iftikhar, K. (2015). Polyhedron, 102, 16–26. CSD CrossRef CAS Google Scholar
Katagiri, S., Hasegawa, Y., Wada, Y. & Yanagida, S. (2004). Chem. Lett. 33, 1438–1439. CrossRef CAS Google Scholar
Katagiri, S., Tsukahara, Y., Hasegawa, Y. & Wada, Y. (2007). Bull. Chem. Soc. Jpn, 80, 1492–1503. CrossRef CAS Google Scholar
Kataoka, H., Nakanishi, T., Omagari, S., Takabatake, Y., Kitagawa, Y. & Hasegawa, Y. (2016). Bull. Chem. Soc. Jpn, 89, 103–109. CrossRef CAS Google Scholar
Kido, J., Nagai, K. & Ohashi, Y. (1990). Chem. Lett. 19, 657–660. CrossRef Web of Science Google Scholar
Koizumi, A., Hasegawa, T., Itadani, A., Toda, K., Zhu, T. & Sato, M. (2017). Acta Cryst. E73, 1739–1742. CSD CrossRef IUCr Journals Google Scholar
Kuz'mina, N. P. & Eliseeva, S. V. (2006). Russ. J. Inorg. Chem. 51, 73–88. Google Scholar
Li, H., Sun, J., Yang, M., Sun, Z., Xie, J., Ma, Y. & Li, L. (2017). New J. Chem. 41, 10181–10188. CSD CrossRef CAS Google Scholar
Lim, J. T., Hong, S. T., Lee, J. C. & Lee, I. M. (1996). Bull. Korean Chem. Soc. 17, 1023–1031. CAS Google Scholar
Meyer, L. V., Schönfeld, F., Zurawski, A., Mai, M., Feldmann, C. & Müller-Buschbaum, K. (2015). Dalton Trans. 44, 4070–4079. Web of Science CSD CrossRef CAS PubMed Google Scholar
Miyata, K., Konno, Y., Nakanishi, T., Kobayashi, A., Kato, M., Fushimi, K. & Hasegawa, Y. (2013). Angew. Chem. Int. Ed. 52, 6413–6416. CSD CrossRef CAS Google Scholar
Nakamura, M., Nakamura, R., Nagai, K., Shimoi, M., Tomoda, S., Takeuchi, Y. & Ouchi, A. (1986). Bull. Chem. Soc. Jpn, 59, 332–334. CSD CrossRef CAS Google Scholar
Phillips, T. II, Sands, D. E. & Wagner, W. F. (1968). Inorg. Chem. 7, 2295–2299. CSD CrossRef CAS Google Scholar
Richardson, M. F., Wagner, W. F. & Sands, D. E. (1968). Inorg. Chem. 7, 2495–2500. CrossRef CAS Google Scholar
Rigaku (1998). REQAB. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2006). CrystalClear-SM. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rybkin, V. V., Tverdova, N. V., Girichev, G. V., Shlykov, S. A., Kuzmina, N. P. & Zaitseva, I. G. (2011). J. Mol. Struct. 1006, 173–179. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Stites, J. G., McCarty, C. N. & Quill, L. L. (1948). J. Am. Chem. Soc. 70, 3142–3143. CrossRef CAS Web of Science Google Scholar
Strehler, F., Korb, M. & Lang, H. (2015). Acta Cryst. E71, 244–247. CSD CrossRef IUCr Journals Google Scholar
Subhan, M. A., Rahman, M. S., Alam, K. & Hasan, M. M. (2014). Spectrochim. Acta A Mol. Biomol. Spectrosc. 118, 944-950. PubMed Google Scholar
Tsaryuk, V. I., Vologzhanina, A. V., Zhuravlev, K. P. & Kudryashova, V. A. (2017). J. Fluor. Chem. 197, 87–93. CSD CrossRef CAS Google Scholar
Wang, Z., Liu, N. N., Li, H., Chen, P. & Yan, P. (2017). Eur. J. Inorg. Chem. pp. 2211–2219. CSD CrossRef Google Scholar
Yan, B., Kong, L. L. & Zhou, B. (2009). J. Non-Cryst. Solids, 355, 1281–1284. CrossRef CAS Google Scholar
Yuasa, J., Ohno, T., Miyata, K., Tsumatori, H., Hasegawa, Y. & Kawai, T. (2011). J. Am. Chem. Soc. 133, 9892–9902. Web of Science CSD CrossRef CAS PubMed Google Scholar
Zheng, X. L., Liu, Y., Pan, M., Lü, X. Q., Zhang, J. Y., Zhao, C. Y., Tong, Y. X. & Su, C. Y. (2007). Angew. Chem. Int. Ed. 46, 7399–7403. CSD CrossRef CAS Google Scholar

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