Aqua­bis­(1,1,1,5,5,5-hexa­fluoro­acetyl­acetonato)[4′-(4-pyrid­yl)-2,2′:6′,2′′-terpyridine]­ytterbium(III) chloride methanol monosolvate monohydrate

Okawara, T.; Feng, J.; Abe, M.; Hisaeda, Y.

doi:10.1107/S1600536811052378

Aquabis(1,1,1,5,5,5-hexafluoroacetylacetonato)[4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine]ytterbium(III) chloride methanol monosolvate monohydrate

T. Okawara, J. Feng, M. Abe and Y. Hisaeda

The title compound, [Yb(C₅HF₆O₂)₂(C₂₀H₁₄N₄)(H₂O)]Cl·CH₃OH·H₂O, adopts an eight-coordinated geometry around the Yb^III atom consisting of a 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine (pytpy) ligand, two 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac) anions and an aqua ligand. In the solid state, the compound forms supramolecular chains running along the b-axis via intermolecular hydrogen bonds between the Yb—OH₂ unit and the N-atom donor of the 4-pyridyl pendant of pytpy, with an O

N distance of 2.686 (4) Å. A chloride counter-anion and lattice methanol and water solvent molecules occupy a hydrophilic columnar space along the coordination chains. O—H

Cl hydrogen bonds occur. The two water molecules and the four trifluoromethyl groups are disordered over two sets of sites, each with different occupancy ratios.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811052378/mw2026sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811052378/mw2026Isup2.hkl Contains datablock I

CCDC reference: 821984

checkCIF report

Key indicators

Single-crystal X-ray study
T = 223 K
Mean (C-C) = 0.006 Å
Disorder in main residue
R factor = 0.036
wR factor = 0.081
Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level B
            Crystal system given = triclinic
PLAT430_ALERT_2_B Short Inter D...A Contact  O7A    ..  O7A     ..       2.54 Ang.

Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT213_ALERT_2_C Atom F7A             has ADP max/min Ratio .....        3.4 prola
PLAT213_ALERT_2_C Atom F7B             has ADP max/min Ratio .....        3.4 prola
PLAT234_ALERT_4_C Large Hirshfeld Difference F1A    --  C21A    ..       0.16 Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference F9A    --  C26A    ..       0.16 Ang.
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C23
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C22
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C27
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....       >O7A
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....       <O7B
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C22    -   C23    ...       1.39 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C23    -   C24    ...       1.38 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C27    -   C28    ...       1.37 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C28    -   C29    ...       1.39 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  O7A     ..       3.12 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         39
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        114
PLAT927_ALERT_1_C Reported and Calculated  wR2 Differ by .........     0.0026

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         41
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00100 Deg.
PLAT242_ALERT_2_G Check Low       Ueq as Compared to Neighbors for       C21A
PLAT242_ALERT_2_G Check Low       Ueq as Compared to Neighbors for       C25A
PLAT242_ALERT_2_G Check Low       Ueq as Compared to Neighbors for       C26A
PLAT242_ALERT_2_G Check Low       Ueq as Compared to Neighbors for       C30A
PLAT242_ALERT_2_G Check Low       Ueq as Compared to Neighbors for       C21B
PLAT242_ALERT_2_G Check Low       Ueq as Compared to Neighbors for       C25B
PLAT242_ALERT_2_G Check Low       Ueq as Compared to Neighbors for       C26B
PLAT242_ALERT_2_G Check Low       Ueq as Compared to Neighbors for       C30B
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................         31 Perc.
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................         25 Perc.
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          !
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         34

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
  19 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  14 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  22 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

The molecular design of multidentate ligands is crucial to determining structures and functions of the resulting coordination compounds and metallo-supramolecular systems. Specifically, a tetradentate ligand 4'-(4-pyridyl)-2,2':6',2"-terpyridine (pytpy) provides a unique structural feature as a bridging ligand where two different coordination donors, the tridentate terpyridyl and monodentate pyridyl moieties, are both associated with metal coordination. Herein we report an unusual bridging mode of pytpy in a one-dimensional metallo-supramolecular system as exemplified with an X-ray crystal structure of compound (I), where the monodentate pyridyl arm in pytpy is now bound to the neighboring molecule via intermolecular hydrogen bonding to form a one-dimensional supramolecular chain. Compound (I) consists of a monocationic complex [Yb^III(pytpy)(hfac)₂(H₂O)], a Cl^- anion, and lattice solvents, CH₃OH and H₂O. The Yb^III center is surrounded by three N donors from pytpy and five O donors from two hfac chelates and one aqua ligand completing the 8-coordinate geometry as shown in Figure 1. Among structurally determined Yb^III complexes containing a single terpyridine ligand, the coordination number 8 is rather unusual and 9- and 10-coordination is more commonly observed (Hayashi et al., 1998; Ahrens et al., 2002; Fukuda et al., 2002; Przychodzen et al., 2007; Li et al., 2007; Xu et al., 2009; Stojanovic et al., 2010). The 8-coordination around lanthanide(III) ions are seen, for example, in [Ln^III(Trop)₄]^- [Trop = tropolonene (2-hydroxycyclohepta-2,4,6-trienone)] (Zhang et al., 2007a). In compound (I), the Yb—N(pytpy) lengths vary from 2.434 (3) to 2.464 (3) Å and the Yb—O(hfac) lengths from 2.262 (3) to 2.334 (3) Å; these values compare well with those observed in complexes containing the [Yb^III(tpy)(hfac)₃] entity (Li et al., 2007; Xu et al., 2009). There is a hydrogen-bonding interaction with the chloride anion with an O5···Cl1ⁱ (symmetry code: (i) 1 + x, y, z) distance of 3.054 (3) Å and an O6···Cl1 distance of 3.102 (3) Å. An additional hydrogen-bonding interaction is seen between the N atom of the dangling pyridyl group and the aqua ligand in the neighboring molecule with an O5···N4ⁱⁱ (symmetry code: (ii) x, 1 + y, z) distance of 2.686 (4) Å to form one-dimensional supramolecular chains of [Yb(pytpy)(hfac)₂(H₂O)]⁺ units running along the b-axis. Similar hydrogen bonded one-dimensional networks including pytpy moieties have been also reported (Beves et al., 2007b; Beves et al., 2008).

Related literature top

For general background to pytpy, see: Constable & Thompson (1992, 1994). For pytpy complexes, see: Sun et al. (2000); Sun & Lees (2001). For related Yb complexes, see: Fukuda et al. (2002); Hayashi et al. (1998); Przychodzen et al. (2007); Stojanovic et al. (2010); Li et al. (2007); Xu et al. (2009); Ahrens et al. (2002); Zhang et al. (2007a). For potential applications of infinite one-dimensional to three-dimensional systems, see: Hayami et al. (2004); Hou et al. (2005); Feng et al. (2006); Beves et al. (2007a); Zhang et al. (2007b); Gou et al. (2008); Leong & Vittal (2011); Moulton & Zaworotko (2001). For the binding mode of pytpy involving hydrogen-bonding, see: Beves et al. (2007b, 2008).

Experimental top

An ethanol solution (50 ml) of pytpy (600 mg, 1.94 mmol) Hhfac (1.21 g, 5.92 mmol), and YbCl₃^.6H₂O (760 mg, 1.94 mmol) was stirred for 30 min at room temperature. After evaporation, the residue was recrystallized from CH₃OH/water to give (I) as colorless crystals. Elemental analysis of the compound that was dried by vacuum pumping overnight at room temperature reveals the loss of the solvent molecules of crystallization (H₂O and CH₃OH). Transparent needle-shaped single crystals of compound (I) suitable for X-ray diffraction analysis were obtained by slow evaporation of a CH₃OH/water (95:5, v/v) solution in a few days. Yield: 637 mg, 0.67 mmol (35%). Analysis: calculated for C₃₀H₁₈ClF₁₂N₄O₅Yb ([Yb(pytpy)(hfac)₂(H₂O)]Cl): C 37.89, H 1.91, N 5.89%; found: C 37.60, H 1.96, N 5.92%. IR (KBr pellet): 1603, 1664, 3031, 3410 cm^-1. UV-vis (CH₃OH) λmax/nm (ε/M^-1cm^-1): 241 (41,300), 285 (34,300). ESI-TOF-MS (CH₃OH): m/z 898.39 (calcd: 898.04 for [M–2H₂O–CH₃OH–Cl^-]⁺).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (CrystalMaker, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. An ORTEP view of the title compound, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. The minor component of the disordered CF₃ groups and lattice water are omitted for clarity.

aquabis(1,1,1,5,5,5-hexafluoroacetylacetonato)[4'-(4-pyridyl)-2,2':6',2''- terpyridine]ytterbium(III) chloride methanol monosolvate monohydrate top

Crystal data top

[Yb(C₅HF₆O₂)₂(C₂₀H₁₄N₄)(H₂O)]Cl·CH₄O·H₂O	Z = 2
M_r = 1001.03	F(000) = 978
Triclinic, P1	D_x = 1.747 Mg m⁻³
a = 9.7559 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.4035 (7) Å	Cell parameters from 4823 reflections
c = 16.5543 (10) Å	θ = 2.6–28.9°
α = 98.870 (1)°	µ = 2.63 mm⁻¹
β = 104.717 (1)°	T = 223 K
γ = 93.559 (1)°	Prism, colourless
V = 1903.5 (2) Å³	0.46 × 0.33 × 0.16 mm

Data collection top

Bruker SMART APEX CCD diffractometer	9671 independent reflections
Radiation source: fine focus sealed tube	8205 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 8.3333 pixels mm^-1	θ_max = 28.7°, θ_min = 1.7°
phi and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −13→16
T_min = 0.53, T_max = 0.68	l = −22→20
13523 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: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.030P)² + 1.1P] where P = (F_o² + 2F_c²)/3
9671 reflections	(Δ/σ)_max = 0.001
587 parameters	Δρ_max = 1.02 e Å⁻³
34 restraints	Δρ_min = −0.88 e Å⁻³

Crystal data top

[Yb(C₅HF₆O₂)₂(C₂₀H₁₄N₄)(H₂O)]Cl·CH₄O·H₂O	γ = 93.559 (1)°
M_r = 1001.03	V = 1903.5 (2) Å³
Triclinic, P1	Z = 2
a = 9.7559 (6) Å	Mo Kα radiation
b = 12.4035 (7) Å	µ = 2.63 mm⁻¹
c = 16.5543 (10) Å	T = 223 K
α = 98.870 (1)°	0.46 × 0.33 × 0.16 mm
β = 104.717 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	9671 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	8205 reflections with I > 2σ(I)
T_min = 0.53, T_max = 0.68	R_int = 0.021
13523 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	34 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 1.02 e Å⁻³
9671 reflections	Δρ_min = −0.88 e Å⁻³
587 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O7A	0.4270 (10)	0.9463 (10)	0.5369 (8)	0.135 (6)	0.584 (19)
H7A	0.4377	0.9366	0.489	0.203*	0.58
H7B	0.4045	0.9042	0.5548	0.203*	0.58
O7B	0.4211 (17)	0.9784 (8)	0.5886 (11)	0.101 (6)	0.416 (19)
H7C	0.4744	0.9843	0.633	0.151*	0.42
H7D	0.3432	0.9793	0.5672	0.151*	0.42
F1A	0.5633 (6)	0.4015 (4)	0.0987 (6)	0.132 (3)	0.809 (7)
F2A	0.7562 (8)	0.3375 (4)	0.1479 (3)	0.115 (2)	0.809 (7)
F3A	0.6812 (8)	0.3306 (5)	0.0145 (3)	0.106 (2)	0.809 (7)
C21A	0.6903 (11)	0.3909 (7)	0.0894 (4)	0.078 (2)	0.809 (7)
F4A	0.9969 (9)	0.7609 (6)	−0.0307 (5)	0.095 (2)	0.760 (10)
F5A	0.9299 (10)	0.5959 (5)	−0.0973 (3)	0.104 (2)	0.760 (10)
F6A	0.7780 (7)	0.7104 (9)	−0.0868 (5)	0.127 (3)	0.760 (10)
C25A	0.8965 (10)	0.6797 (7)	−0.0462 (5)	0.072 (2)	0.760 (10)
F7A	0.6123 (6)	1.0312 (4)	0.1179 (4)	0.136 (3)	0.901 (7)
F8A	0.5579 (6)	0.9439 (5)	0.2082 (4)	0.133 (2)	0.901 (7)
F9A	0.5449 (5)	0.8597 (4)	0.0849 (4)	0.126 (2)	0.901 (7)
C26A	0.6202 (8)	0.9367 (7)	0.1460 (6)	0.088 (2)	0.901 (7)
F10A	1.2675 (6)	1.0106 (4)	0.2103 (4)	0.1137 (19)	0.861 (6)
F11A	1.1197 (5)	1.1250 (3)	0.1800 (3)	0.0930 (14)	0.861 (6)
F12A	1.1272 (7)	0.9944 (5)	0.0843 (3)	0.136 (3)	0.861 (6)
C30A	1.1366 (8)	1.0194 (5)	0.1657 (5)	0.0693 (18)	0.861 (6)
F1B	0.547 (2)	0.4106 (19)	0.0297 (19)	0.132 (3)	0.191 (7)
F2B	0.654 (4)	0.3824 (19)	0.1497 (14)	0.115 (2)	0.191 (7)
F3B	0.724 (3)	0.328 (3)	0.0454 (16)	0.106 (2)	0.191 (7)
C21B	0.672 (3)	0.413 (3)	0.0808 (18)	0.078 (2)	0.191 (7)
F4B	1.023 (3)	0.727 (2)	−0.0193 (17)	0.095 (2)	0.240 (10)
F5B	0.844 (3)	0.627 (2)	−0.1050 (12)	0.104 (2)	0.240 (10)
F6B	0.808 (2)	0.774 (2)	−0.0447 (14)	0.127 (3)	0.240 (10)
C25B	0.889 (3)	0.697 (2)	−0.0299 (18)	0.072 (2)	0.240 (10)
F7B	0.643 (6)	1.055 (4)	0.168 (3)	0.136 (3)	0.099 (7)
F8B	0.548 (6)	0.892 (4)	0.153 (4)	0.133 (2)	0.099 (7)
F9B	0.615 (4)	0.944 (4)	0.054 (3)	0.126 (2)	0.099 (7)
C26B	0.650 (6)	0.951 (4)	0.137 (3)	0.088 (2)	0.099 (7)
F10B	1.237 (4)	1.053 (3)	0.215 (2)	0.1137 (19)	0.139 (6)
F11B	1.095 (3)	1.080 (2)	0.109 (2)	0.0930 (14)	0.139 (6)
F12B	1.203 (4)	0.931 (3)	0.102 (2)	0.136 (3)	0.139 (6)
C30B	1.142 (5)	0.998 (3)	0.147 (2)	0.0693 (18)	0.139 (6)
C1	1.2599 (5)	0.6952 (3)	0.1920 (3)	0.0523 (10)
H1	1.2293	0.7561	0.1676	0.063*
C2	1.3902 (5)	0.6611 (3)	0.1860 (3)	0.0537 (10)
H2	1.4462	0.6976	0.1579	0.064*
C3	1.4353 (5)	0.5733 (4)	0.2220 (3)	0.0537 (10)
H3	1.5237	0.5489	0.2195	0.064*
C4	1.3497 (4)	0.5204 (3)	0.2621 (3)	0.0468 (9)
H4	1.3795	0.4598	0.2872	0.056*
C5	1.2205 (4)	0.5574 (3)	0.2650 (2)	0.0361 (8)
C6	1.1229 (4)	0.5037 (3)	0.3055 (2)	0.0342 (7)
C7	1.1385 (4)	0.3992 (3)	0.3247 (2)	0.0388 (8)
H7	1.213	0.3609	0.3123	0.047*
C8	1.0437 (4)	0.3513 (3)	0.3624 (2)	0.0383 (8)
C9	0.9384 (4)	0.4127 (3)	0.3816 (2)	0.0369 (8)
H9	0.8752	0.3845	0.4095	0.044*
C10	0.9266 (4)	0.5166 (3)	0.3593 (2)	0.0338 (7)
C11	0.8142 (4)	0.5847 (3)	0.3771 (2)	0.0347 (7)
C12	0.7307 (4)	0.5584 (3)	0.4284 (2)	0.0417 (8)
H12	0.7421	0.4944	0.4522	0.05*
C13	0.6296 (5)	0.6267 (3)	0.4449 (3)	0.0501 (10)
H13	0.5704	0.6092	0.4788	0.06*
C14	0.6188 (5)	0.7210 (3)	0.4099 (3)	0.0519 (10)
H14	0.5534	0.77	0.4208	0.062*
C15	0.7043 (5)	0.7420 (3)	0.3593 (3)	0.0474 (10)
H15	0.6955	0.8066	0.336	0.057*
C16	1.1819 (5)	0.0805 (3)	0.3982 (3)	0.0571 (12)
H16	1.2672	0.0481	0.401	0.068*
C17	1.1783 (5)	0.1875 (3)	0.3838 (3)	0.0505 (10)
H17	1.2592	0.2262	0.3768	0.061*
C18	1.0535 (4)	0.2369 (3)	0.3799 (2)	0.0399 (8)
C19	0.9383 (5)	0.1753 (3)	0.3908 (3)	0.0519 (10)
H19	0.8517	0.2055	0.3887	0.062*
C20	0.9520 (6)	0.0688 (3)	0.4049 (3)	0.0594 (12)
H20	0.8731	0.0281	0.4126	0.071*
C22	0.7704 (5)	0.5083 (3)	0.0997 (3)	0.0523 (10)
C23	0.8004 (6)	0.5427 (4)	0.0297 (3)	0.0718 (15)
H23	0.7685	0.4974	−0.0239	0.086*
C24	0.8767 (5)	0.6429 (4)	0.0383 (3)	0.0515 (10)
C27	0.7744 (5)	0.9089 (3)	0.1768 (3)	0.0569 (11)
C28	0.8842 (5)	0.9693 (4)	0.1609 (3)	0.0655 (13)
H28	0.8637	1.0278	0.1314	0.079*
C29	1.0244 (5)	0.9468 (3)	0.1870 (3)	0.0534 (11)
C31	0.4832 (7)	0.7478 (6)	0.7308 (4)	0.0958 (19)
H31A	0.5547	0.7518	0.7843	0.144*
H31B	0.397	0.7054	0.7319	0.144*
H31C	0.4623	0.8213	0.7223	0.144*
Cl1	0.30493 (11)	0.69937 (8)	0.49683 (7)	0.0517 (2)
N1	1.1748 (3)	0.6454 (2)	0.23092 (19)	0.0405 (7)
N2	1.0163 (3)	0.5603 (2)	0.32052 (17)	0.0329 (6)
N3	0.8006 (3)	0.6758 (2)	0.34053 (18)	0.0376 (7)
N4	1.0714 (5)	0.0212 (3)	0.4082 (2)	0.0552 (9)
O1	0.8032 (3)	0.5596 (2)	0.17364 (16)	0.0442 (6)
O2	0.9332 (3)	0.7075 (2)	0.10503 (16)	0.0512 (7)
O3	1.0696 (3)	0.8734 (2)	0.22719 (16)	0.0476 (7)
O4	0.7822 (3)	0.8267 (2)	0.21397 (18)	0.0505 (7)
O5	1.0781 (3)	0.8027 (2)	0.37801 (17)	0.0458 (7)
H5A	1.087 (5)	0.867 (3)	0.392 (3)	0.069*
H5B	1.134 (5)	0.775 (4)	0.405 (3)	0.069*
O6	0.5339 (4)	0.6980 (3)	0.6653 (2)	0.0727 (10)
H6	0.4737	0.6963	0.6195	0.109*
Yb1	0.953387 (18)	0.714155 (11)	0.248364 (9)	0.03543 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O7A	0.129 (9)	0.068 (7)	0.177 (13)	−0.022 (6)	−0.026 (8)	0.055 (8)
O7B	0.163 (13)	0.047 (6)	0.130 (12)	0.040 (7)	0.101 (11)	0.015 (6)
F1A	0.100 (4)	0.105 (4)	0.186 (8)	−0.051 (3)	0.076 (5)	−0.023 (5)
F2A	0.190 (7)	0.054 (3)	0.094 (3)	−0.032 (3)	0.029 (4)	0.021 (2)
F3A	0.169 (6)	0.074 (2)	0.057 (3)	−0.061 (3)	0.035 (3)	−0.024 (3)
C21A	0.109 (6)	0.064 (5)	0.052 (4)	−0.040 (4)	0.028 (3)	−0.009 (3)
F4A	0.121 (4)	0.105 (5)	0.055 (3)	−0.038 (4)	0.016 (3)	0.036 (3)
F5A	0.146 (7)	0.118 (4)	0.054 (2)	−0.003 (4)	0.048 (4)	0.003 (2)
F6A	0.104 (4)	0.196 (9)	0.085 (5)	−0.001 (5)	−0.009 (4)	0.098 (5)
C25A	0.099 (5)	0.081 (5)	0.025 (4)	−0.027 (4)	0.008 (3)	0.004 (3)
F7A	0.094 (4)	0.102 (4)	0.228 (8)	0.039 (3)	0.012 (4)	0.117 (5)
F8A	0.110 (4)	0.158 (5)	0.180 (6)	0.089 (3)	0.073 (4)	0.092 (4)
F9A	0.080 (3)	0.119 (4)	0.152 (5)	0.005 (3)	−0.029 (3)	0.044 (3)
C26A	0.072 (5)	0.078 (4)	0.133 (6)	0.026 (4)	0.025 (4)	0.075 (5)
F10A	0.069 (3)	0.105 (4)	0.187 (5)	0.001 (3)	0.032 (3)	0.092 (4)
F11A	0.126 (3)	0.047 (2)	0.105 (3)	−0.020 (2)	0.024 (3)	0.032 (2)
F12A	0.196 (7)	0.123 (6)	0.095 (4)	−0.066 (4)	0.086 (4)	−0.010 (3)
C30A	0.078 (4)	0.058 (4)	0.073 (5)	−0.010 (3)	0.015 (3)	0.031 (3)
F1B	0.100 (4)	0.105 (4)	0.186 (8)	−0.051 (3)	0.076 (5)	−0.023 (5)
F2B	0.190 (7)	0.054 (3)	0.094 (3)	−0.032 (3)	0.029 (4)	0.021 (2)
F3B	0.169 (6)	0.074 (2)	0.057 (3)	−0.061 (3)	0.035 (3)	−0.024 (3)
C21B	0.109 (6)	0.064 (5)	0.052 (4)	−0.040 (4)	0.028 (3)	−0.009 (3)
F4B	0.121 (4)	0.105 (5)	0.055 (3)	−0.038 (4)	0.016 (3)	0.036 (3)
F5B	0.146 (7)	0.118 (4)	0.054 (2)	−0.003 (4)	0.048 (4)	0.003 (2)
F6B	0.104 (4)	0.196 (9)	0.085 (5)	−0.001 (5)	−0.009 (4)	0.098 (5)
C25B	0.099 (5)	0.081 (5)	0.025 (4)	−0.027 (4)	0.008 (3)	0.004 (3)
F7B	0.094 (4)	0.102 (4)	0.228 (8)	0.039 (3)	0.012 (4)	0.117 (5)
F8B	0.110 (4)	0.158 (5)	0.180 (6)	0.089 (3)	0.073 (4)	0.092 (4)
F9B	0.080 (3)	0.119 (4)	0.152 (5)	0.005 (3)	−0.029 (3)	0.044 (3)
C26B	0.072 (5)	0.078 (4)	0.133 (6)	0.026 (4)	0.025 (4)	0.075 (5)
F10B	0.069 (3)	0.105 (4)	0.187 (5)	0.001 (3)	0.032 (3)	0.092 (4)
F11B	0.126 (3)	0.047 (2)	0.105 (3)	−0.020 (2)	0.024 (3)	0.032 (2)
F12B	0.196 (7)	0.123 (6)	0.095 (4)	−0.066 (4)	0.086 (4)	−0.010 (3)
C30B	0.078 (4)	0.058 (4)	0.073 (5)	−0.010 (3)	0.015 (3)	0.031 (3)
C1	0.066 (3)	0.045 (2)	0.054 (3)	0.006 (2)	0.025 (2)	0.0186 (19)
C2	0.062 (3)	0.052 (2)	0.052 (3)	−0.002 (2)	0.024 (2)	0.0137 (19)
C3	0.047 (2)	0.053 (2)	0.060 (3)	0.0008 (19)	0.015 (2)	0.008 (2)
C4	0.045 (2)	0.038 (2)	0.055 (2)	0.0025 (17)	0.0080 (18)	0.0101 (17)
C5	0.045 (2)	0.0238 (16)	0.0355 (18)	0.0010 (14)	0.0053 (15)	0.0042 (13)
C6	0.043 (2)	0.0243 (15)	0.0320 (17)	0.0026 (14)	0.0032 (14)	0.0056 (13)
C7	0.048 (2)	0.0264 (16)	0.042 (2)	0.0099 (15)	0.0103 (16)	0.0068 (14)
C8	0.054 (2)	0.0234 (16)	0.0355 (18)	0.0083 (15)	0.0053 (16)	0.0079 (13)
C9	0.050 (2)	0.0264 (16)	0.0368 (19)	0.0054 (15)	0.0126 (16)	0.0111 (13)
C10	0.046 (2)	0.0237 (15)	0.0304 (17)	0.0030 (14)	0.0075 (15)	0.0067 (12)
C11	0.046 (2)	0.0241 (15)	0.0325 (17)	0.0049 (14)	0.0059 (15)	0.0069 (13)
C12	0.057 (2)	0.0332 (18)	0.0369 (19)	0.0049 (16)	0.0122 (17)	0.0110 (15)
C13	0.057 (3)	0.049 (2)	0.051 (2)	0.0112 (19)	0.023 (2)	0.0108 (18)
C14	0.060 (3)	0.047 (2)	0.054 (2)	0.023 (2)	0.019 (2)	0.0112 (19)
C15	0.063 (3)	0.0336 (19)	0.049 (2)	0.0200 (18)	0.014 (2)	0.0127 (16)
C16	0.071 (3)	0.0290 (19)	0.067 (3)	0.018 (2)	0.005 (2)	0.0147 (18)
C17	0.062 (3)	0.0288 (18)	0.058 (3)	0.0116 (18)	0.008 (2)	0.0122 (17)
C18	0.061 (2)	0.0241 (16)	0.0354 (19)	0.0094 (16)	0.0108 (17)	0.0090 (13)
C19	0.072 (3)	0.0307 (19)	0.062 (3)	0.0158 (19)	0.026 (2)	0.0194 (18)
C20	0.088 (4)	0.031 (2)	0.069 (3)	0.012 (2)	0.031 (3)	0.0190 (19)
C22	0.056 (3)	0.050 (2)	0.044 (2)	−0.009 (2)	0.0093 (19)	0.0007 (18)
C23	0.095 (4)	0.071 (3)	0.037 (2)	−0.030 (3)	0.013 (2)	−0.005 (2)
C24	0.059 (3)	0.056 (3)	0.037 (2)	−0.001 (2)	0.0057 (18)	0.0138 (18)
C27	0.067 (3)	0.043 (2)	0.067 (3)	0.017 (2)	0.013 (2)	0.029 (2)
C28	0.075 (3)	0.044 (2)	0.081 (3)	0.008 (2)	0.010 (3)	0.041 (2)
C29	0.072 (3)	0.034 (2)	0.051 (2)	−0.0040 (19)	0.006 (2)	0.0188 (17)
C31	0.079 (4)	0.129 (5)	0.077 (4)	0.018 (4)	0.014 (3)	0.024 (4)
Cl1	0.0523 (6)	0.0507 (6)	0.0543 (6)	0.0140 (5)	0.0087 (5)	0.0223 (4)
N1	0.053 (2)	0.0318 (15)	0.0399 (17)	0.0038 (14)	0.0136 (14)	0.0126 (12)
N2	0.0403 (16)	0.0218 (13)	0.0337 (15)	0.0062 (11)	0.0027 (12)	0.0068 (11)
N3	0.0490 (18)	0.0259 (14)	0.0387 (16)	0.0081 (13)	0.0097 (14)	0.0095 (12)
N4	0.090 (3)	0.0249 (15)	0.050 (2)	0.0142 (17)	0.0127 (19)	0.0116 (14)
O1	0.0527 (17)	0.0392 (14)	0.0368 (14)	−0.0025 (12)	0.0065 (12)	0.0065 (11)
O2	0.071 (2)	0.0422 (15)	0.0349 (14)	−0.0060 (13)	0.0037 (13)	0.0133 (11)
O3	0.0636 (18)	0.0328 (13)	0.0442 (15)	0.0035 (12)	0.0046 (13)	0.0174 (11)
O4	0.0563 (18)	0.0412 (15)	0.0595 (18)	0.0145 (13)	0.0115 (14)	0.0283 (13)
O5	0.0644 (19)	0.0223 (12)	0.0413 (15)	0.0080 (12)	−0.0051 (13)	0.0077 (10)
O6	0.059 (2)	0.087 (2)	0.070 (2)	0.0292 (19)	0.0039 (17)	0.0225 (19)
Yb1	0.04699 (10)	0.02374 (8)	0.03358 (9)	0.00377 (6)	0.00364 (6)	0.01108 (5)

Geometric parameters (Å, º) top

O7A—H7A	0.818 (12)	C8—C9	1.387 (5)
O7A—H7B	0.689 (6)	C8—C18	1.496 (4)
O7B—H7C	0.775 (19)	C9—C10	1.397 (4)
O7B—H7D	0.754 (17)	C9—H9	0.94
F1A—C21A	1.299 (10)	C10—N2	1.344 (4)
F2A—C21A	1.313 (9)	C10—C11	1.485 (5)
F3A—C21A	1.325 (7)	C11—N3	1.359 (4)
C21A—C22	1.573 (9)	C11—C12	1.376 (5)
F4A—C25A	1.307 (8)	C12—C13	1.391 (5)
F5A—C25A	1.348 (8)	C12—H12	0.94
F6A—C25A	1.293 (9)	C13—C14	1.381 (6)
C25A—C24	1.589 (10)	C13—H13	0.94
F7A—C26A	1.327 (7)	C14—C15	1.364 (6)
F8A—C26A	1.317 (9)	C14—H14	0.94
F9A—C26A	1.309 (10)	C15—N3	1.349 (5)
C26A—C27	1.540 (8)	C15—H15	0.94
F10A—C30A	1.323 (7)	C16—N4	1.327 (6)
F11A—C30A	1.323 (7)	C16—C17	1.386 (5)
F12A—C30A	1.313 (8)	C16—H16	0.94
C30A—C29	1.518 (8)	C17—C18	1.388 (6)
F1B—C21B	1.30 (2)	C17—H17	0.94
F2B—C21B	1.31 (2)	C18—C19	1.385 (6)
F3B—C21B	1.324 (19)	C19—C20	1.385 (5)
C21B—C22	1.41 (3)	C19—H19	0.94
F4B—C25B	1.306 (17)	C20—N4	1.331 (6)
F5B—C25B	1.352 (19)	C20—H20	0.94
F6B—C25B	1.296 (19)	C22—O1	1.242 (5)
C25B—C24	1.42 (3)	C22—C23	1.385 (6)
F7B—C26B	1.33 (2)	C23—C24	1.376 (6)
F8B—C26B	1.30 (2)	C23—H23	0.94
F9B—C26B	1.31 (2)	C24—O2	1.238 (5)
C26B—C27	1.40 (5)	C27—O4	1.266 (4)
F10B—C30B	1.32 (2)	C27—C28	1.371 (6)
F11B—C30B	1.31 (2)	C28—C29	1.386 (7)
F12B—C30B	1.30 (2)	C28—H28	0.94
C30B—C29	1.61 (4)	C29—O3	1.246 (4)
C1—N1	1.347 (5)	C31—O6	1.380 (6)
C1—C2	1.387 (6)	C31—H31A	0.97
C1—H1	0.94	C31—H31B	0.97
C2—C3	1.363 (6)	C31—H31C	0.97
C2—H2	0.94	N1—Yb1	2.438 (3)
C3—C4	1.385 (6)	N2—Yb1	2.434 (3)
C3—H3	0.94	N3—Yb1	2.464 (3)
C4—C5	1.378 (5)	O1—Yb1	2.313 (2)
C4—H4	0.94	O2—Yb1	2.319 (3)
C5—N1	1.353 (4)	O3—Yb1	2.334 (3)
C5—C6	1.478 (5)	O4—Yb1	2.262 (3)
C6—N2	1.343 (4)	O5—Yb1	2.252 (3)
C6—C7	1.390 (4)	O5—H5A	0.78 (4)
C7—C8	1.391 (5)	O5—H5B	0.75 (4)
C7—H7	0.94	O6—H6	0.83

H7A—O7A—H7B	123 (2)	C14—C15—H15	118.0
H7C—O7B—H7D	142.0 (16)	N4—C16—C17	123.5 (4)
F1A—C21A—F2A	107.6 (7)	N4—C16—H16	118.3
F1A—C21A—F3A	109.7 (8)	C17—C16—H16	118.3
F2A—C21A—F3A	107.6 (8)	C16—C17—C18	119.1 (4)
F1A—C21A—C22	108.9 (7)	C16—C17—H17	120.5
F2A—C21A—C22	111.1 (6)	C18—C17—H17	120.5
F3A—C21A—C22	111.9 (6)	C19—C18—C17	117.5 (3)
F6A—C25A—F4A	108.7 (8)	C19—C18—C8	121.7 (4)
F6A—C25A—F5A	107.9 (6)	C17—C18—C8	120.9 (4)
F4A—C25A—F5A	107.8 (7)	C18—C19—C20	119.4 (4)
F6A—C25A—C24	109.1 (7)	C18—C19—H19	120.3
F4A—C25A—C24	112.3 (6)	C20—C19—H19	120.3
F5A—C25A—C24	111.0 (7)	N4—C20—C19	123.2 (5)
F9A—C26A—F8A	107.3 (7)	N4—C20—H20	118.4
F9A—C26A—F7A	108.0 (7)	C19—C20—H20	118.4
F8A—C26A—F7A	107.1 (7)	O1—C22—C23	127.1 (4)
F9A—C26A—C27	110.8 (7)	O1—C22—C21B	117.2 (12)
F8A—C26A—C27	110.5 (6)	C23—C22—C21B	114.8 (12)
F7A—C26A—C27	113.0 (6)	O1—C22—C21A	113.4 (4)
F12A—C30A—F11A	105.7 (5)	C23—C22—C21A	119.5 (4)
F12A—C30A—F10A	109.7 (7)	C24—C23—C22	120.3 (4)
F11A—C30A—F10A	105.7 (6)	C24—C23—H23	119.9
F12A—C30A—C29	109.3 (5)	C22—C23—H23	119.9
F11A—C30A—C29	113.3 (6)	O2—C24—C23	127.1 (4)
F10A—C30A—C29	112.8 (5)	O2—C24—C25B	107.4 (11)
F1B—C21B—F2B	107 (3)	C23—C24—C25B	125.1 (11)
F1B—C21B—F3B	103 (2)	O2—C24—C25A	115.9 (4)
F2B—C21B—F3B	103 (3)	C23—C24—C25A	117.0 (4)
F1B—C21B—C22	120 (2)	O4—C27—C28	127.4 (4)
F2B—C21B—C22	112 (2)	O4—C27—C26B	127 (2)
F3B—C21B—C22	111 (3)	C28—C27—C26B	106 (2)
F6B—C25B—F4B	113 (3)	O4—C27—C26A	112.4 (4)
F6B—C25B—F5B	101 (2)	C28—C27—C26A	120.2 (4)
F4B—C25B—F5B	107 (2)	C27—C28—C29	122.1 (4)
F6B—C25B—C24	117 (2)	C27—C28—H28	118.9
F4B—C25B—C24	108 (2)	C29—C28—H28	118.9
F5B—C25B—C24	111 (2)	O3—C29—C28	127.0 (4)
F8B—C26B—F9B	105 (3)	O3—C29—C30A	115.7 (5)
F8B—C26B—F7B	108 (3)	C28—C29—C30A	117.2 (4)
F9B—C26B—F7B	105 (3)	O3—C29—C30B	111.8 (11)
F8B—C26B—C27	104 (4)	C28—C29—C30B	119.7 (11)
F9B—C26B—C27	120 (4)	O6—C31—H31A	109.5
F7B—C26B—C27	114 (4)	O6—C31—H31B	109.5
F12B—C30B—F11B	113 (3)	H31A—C31—H31B	109.5
F12B—C30B—F10B	111 (3)	O6—C31—H31C	109.5
F11B—C30B—F10B	100 (3)	H31A—C31—H31C	109.5
F12B—C30B—C29	118 (3)	H31B—C31—H31C	109.5
F11B—C30B—C29	111 (3)	C1—N1—C5	117.3 (3)
F10B—C30B—C29	102 (3)	C1—N1—Yb1	122.6 (3)
N1—C1—C2	123.4 (4)	C5—N1—Yb1	120.0 (2)
N1—C1—H1	118.3	C6—N2—C10	118.8 (3)
C2—C1—H1	118.3	C6—N2—Yb1	119.5 (2)
C3—C2—C1	118.4 (4)	C10—N2—Yb1	120.0 (2)
C3—C2—H2	120.8	C15—N3—C11	116.8 (3)
C1—C2—H2	120.8	C15—N3—Yb1	123.7 (2)
C2—C3—C4	119.5 (4)	C11—N3—Yb1	119.5 (2)
C2—C3—H3	120.3	C16—N4—C20	117.4 (3)
C4—C3—H3	120.3	C22—O1—Yb1	136.0 (3)
C5—C4—C3	119.3 (4)	C24—O2—Yb1	136.7 (3)
C5—C4—H4	120.3	C29—O3—Yb1	131.4 (3)
C3—C4—H4	120.3	C27—O4—Yb1	133.3 (3)
N1—C5—C4	122.1 (3)	Yb1—O5—H5A	125 (4)
N1—C5—C6	115.7 (3)	Yb1—O5—H5B	120 (4)
C4—C5—C6	122.2 (3)	H5A—O5—H5B	113 (5)
N2—C6—C7	122.0 (3)	C31—O6—H6	109.5
N2—C6—C5	116.3 (3)	O5—Yb1—O4	101.21 (10)
C7—C6—C5	121.7 (3)	O5—Yb1—O1	145.11 (10)
C6—C7—C8	119.9 (3)	O4—Yb1—O1	92.58 (10)
C6—C7—H7	120.1	O5—Yb1—O2	142.31 (11)
C8—C7—H7	120.1	O4—Yb1—O2	78.53 (10)
C9—C8—C7	117.6 (3)	O1—Yb1—O2	71.66 (9)
C9—C8—C18	121.3 (3)	O5—Yb1—O3	73.80 (10)
C7—C8—C18	121.1 (3)	O4—Yb1—O3	74.24 (10)
C8—C9—C10	119.9 (3)	O1—Yb1—O3	141.08 (9)
C8—C9—H9	120.1	O2—Yb1—O3	69.89 (9)
C10—C9—H9	120.1	O5—Yb1—N2	79.05 (9)
N2—C10—C9	121.8 (3)	O4—Yb1—N2	143.97 (10)
N2—C10—C11	116.3 (3)	O1—Yb1—N2	71.28 (9)
C9—C10—C11	121.9 (3)	O2—Yb1—N2	122.99 (9)
N3—C11—C12	122.1 (3)	O3—Yb1—N2	137.52 (10)
N3—C11—C10	115.7 (3)	O5—Yb1—N1	87.59 (11)
C12—C11—C10	122.2 (3)	O4—Yb1—N1	149.10 (10)
C11—C12—C13	119.9 (3)	O1—Yb1—N1	96.84 (10)
C11—C12—H12	120.1	O2—Yb1—N1	76.68 (10)
C13—C12—H12	120.1	O3—Yb1—N1	80.08 (10)
C14—C13—C12	118.0 (4)	N2—Yb1—N1	66.59 (10)
C14—C13—H13	121.0	O5—Yb1—N3	76.28 (11)
C12—C13—H13	121.0	O4—Yb1—N3	78.64 (10)
C15—C14—C13	119.2 (4)	O1—Yb1—N3	75.27 (9)
C15—C14—H14	120.4	O2—Yb1—N3	138.51 (10)
C13—C14—H14	120.4	O3—Yb1—N3	134.26 (9)
N3—C15—C14	124.0 (4)	N2—Yb1—N3	66.31 (9)
N3—C15—H15	118.0	N1—Yb1—N3	132.23 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···Cl1ⁱ	0.75 (4)	2.31 (4)	3.054 (3)	175 (5)
O6—H6···Cl1	0.83	2.27	3.102 (3)	177
O5—H5A···N4ⁱⁱ	0.78 (4)	1.92 (4)	2.686 (4)	167 (5)

Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Yb(C₅HF₆O₂)₂(C₂₀H₁₄N₄)(H₂O)]Cl·CH₄O·H₂O
M_r	1001.03
Crystal system, space group	Triclinic, P1
Temperature (K)	223
a, b, c (Å)	9.7559 (6), 12.4035 (7), 16.5543 (10)
α, β, γ (°)	98.870 (1), 104.717 (1), 93.559 (1)
V (Å³)	1903.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.63
Crystal size (mm)	0.46 × 0.33 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.53, 0.68
No. of measured, independent and observed [I > 2σ(I)] reflections	13523, 9671, 8205
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.081, 1.08
No. of reflections	9671
No. of parameters	587
No. of restraints	34
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.02, −0.88

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (CrystalMaker, 2010), publCIF (Westrip, 2010).