(Acetato-κ²O,O′)dihydroxido­ytterbium(III) hemihydrate

The title compound, [Yb(C₂H₃O₂)(OH)₂]·0.5H₂O, was ob­tained via hydro­thermal reaction of Yb(CH₃COO)₃·H₂O with NaOH at 443 K. The compound forms two-dimensional layers with six crystallographically independent Yb^III atoms. Four of these form YbO₈ coordination polyhedra, while the coordination number of the remaining two Yb^III atoms is 7. Five of these coordination polyhedra are inter­connected mainly via hy­droxide groups, as they build a narrow inner layer that extends infinitely within the ab plane. The sixth Yb^III atom resides outside this inner layer and builds a terminal YbO₈ coordination polyhedron on the layer surface. Its coordination environment comprises four carboxyl­ate O atoms belonging to three different acetate entities, three hydroxide groups and one water mol­ecule. Adjacent layers experience weak inter­actions via hydrogen bonds. The Yb—O distances lie in the range 2.232 (4)–2.613 (5) Å.

S1. Comment

The creation of open frameworks has increased considerably over the last decade due to their widespread potential applications in electronic applications (Férey et al., 2007), drug delivery (Horcajada et al., 2008; Vallet-Regi et al., 2007), catalytic systems (Gándara et al., 2008; Mueller et al., 2008) etc. We recently discussed the structural trends within an extended series of lanthanide bis-hydroxychlorides [Ln(OH)₂Cl; Zehnder et al., 2010], which represent purely inorganic three-dimensional open frameworks, as they may have potential implications for the long-term isolation and storage of radioactive waste materials. Other purely inorganic three-dimensional networks, assembling to various forms of zeolite structures, have become very useful as molecular sieves (Meier et al., 1996). In more recent years, these purely inorganic three-dimensional extended lattices have evolved into frameworks incorporating organic building units (Li et al., 2007). The replacement of inorganic entities with larger organic spacer entities has led to a large number of new materials with significantly larger pore sizes and unique properties. These new materials, mainly integrating organic ligand systems into three-dimensional coordination polymers, are known as metal organic frameworks (MOFs) (Bradshaw et al., 2005; Kawano et al., 2007).

We are currently extending our work from exclusively inorganic lanthanide mixed-ligand compounds to MOF materials, and therefore consider the acetate ligand as one of the possible organic entities. We were curious to see if we could construct the acetate analogues of the Ln(OH)₂Cl compounds that we recently investigated. We were able to obtain single crystals of the title compound, (I), of sufficiently high quality for a single-crystal X-ray structural analysis. Compound (I) is an excellent candidate for demonstrating the feasibility of replacing inorganic ligand systems with organic entities in order to obtain hybrid frameworks. In such frameworks, inorganic ligands and organic entities are part of the resulting coordination environment. Moreover, (I) shows that organic entities with one major coordination site will rather lead to the creation of frameworks with limited dimensionality. As we illustrate here, (I) assembles as a two-dimensional layered framework, in which individual layers interact through hydrogen bonds.

To our knowledge, the single-crystal X-ray structural characterization of a lanthanide bis(hydroxide) acetate is unprecedented. However, a small number of related lanthanide compounds have been under investigation. Sakagami and co-workers discussed the structure of a heteronuclear Cr^III–Nd^III complex, which incorporates hydroxide and acetate groups in the coordination environment. These researchers point out that compounds such as [Cr₂Nd₃(µ-OOCCH₃)₆(µ-OH)₆(H₂O)₉]Br₃(NaBr)(H₂O)₈ may have unusual electronic and magnetic properties (Sakagami et al., 1997). Another research team reported the synthesis and structural characterization of CsLu(CH₃COO)₄ and Cs₂[Lu₃(CH₃COO)₁₀(OH)(H₂O)], and the changes these compounds undergo during thermal decomposition. Cs₂[Lu₃(CH₃COO)₁₀(OH)(H₂O)] assembles to form trimers of Lu centres that are linked by Cs⁺ cations (Lossin & Meyer, 1993). More recently, a group of investigators assessed the structural and magnetic properties of Tb₄ spin clusters incorporating acetate anions and various organic ligands with hydroxyl groups that possess chelating as well as linking capacities. The coordination of the acetate entities in these Tb compounds seems to prevent the formation of a three-dimensional linked crystal structure. Therefore, the trimers integrating carboxylate O atoms and OH groups into the coordination environment remain as isolated individual clusters (Bircher et al., 2007).

In various other experiments, we extended the organic part of the ligand by exchanging acetate with phenyl acetate. We obtained a small number of lanthanide phenylacetates that have been discussed previously (Hasegawa, Ikeuchi et al., 1989; Hasegawa, Morita et al., 1989; Hasegawa et al., 1990). These compounds assemble in one-dimensional channels of lanthanide metal centres that are linked by carboxylate groups and stretch infinitely along the a axis. The bulky hydrophobic parts of the phenylacetate entities are oriented in all directions surrounding the metal–carboxylate channels. In order to obtain an extended structure that is linked via strong coordination bonds in three dimensions, it is essential to employ spacer units that contain two or more major coordination sites. This has been established by a number of researchers who have made use of organic entities, e.g. terephthalic acid (Daiguebonne et al., 2006, 2008; Haquin et al., 2009; Kerbellec et al., 2009; Long et al., 2001), phthalic acid (Li et al., 2009) and glutaric acid (Serpaggi & Férey, 1998). We recently obtained various MOF materials incorporating these types of organic ligands, which will be discussed elsewhere.

Here we present the synthesis and characterization of the title compound, (I), a lanthanide mixed-ligand complex comprised of inorganic and organic components. Compound (I) crystallizes in the triclinic crystal system, space group P1, and it assembles as a two-dimensional layered framework. Individual layers are composed of highly linked Yb^III centres, hydroxy groups and acetate entities that stretch infinitely along the a and b axes. Each layer is segmented into an inner layer that accommodates a dense network of Yb^III cations and hydroxy groups, while the outer layer also includes carboxylate groups and water molecules. The layers exhibit six crystallographically independent Yb^III atoms as the centres of four eight- and two seven-coordinate Yb–O polyhedra. Three of the four YbO₈ and the two YbO₇ polyhedra contain Yb^III centres that are narrowly interlinked within the inner layer of the ab plane. The other YbO₈ polyhedra feature the terminal Yb^III cations, which stick out from the surface of the outer layer on both sides, pointing towards adjacent layers in the c direction. The Yb^III centres of the five coordination polyhedra in the inner layer comprise only hydroxide groups and one carboxylate O atom, respectively [Which is which?]. The Yb—O bond distances within these five polyhedra vary between 2.232 (4) and 2.418 (4) Å. The corresponding bond distances in the YbO₈ polyhedra of the terminal Yb^III cations are somewhat longer and range between 2.257 (4) and 2.613 (5) Å. The coordination polyhedra are interlinked via edge sharing, utilizing two hydroxy groups. Hydroxy groups bind in both µ³- and µ²-fashion, connecting to three and two Yb³⁺ cations, respectively.

The carboxylate O atoms bind in an exclusively µ¹-fashion to the Yb^III atoms. Fig. 1 emphasizes the arrangement of the six different coordination polyhedra, in a view along the a axis utilizing different shaded patterns. The acetate anions are arranged with their carboxylate groups oriented towards the Yb^III atoms, while their CH₃ groups point towards the adjacent layer in the c direction. Fig. 2 illustrates the layered system of (I) in a view along the b axis, demonstrating that the individual layers interact via hydrogen bonding between coordinating water molecules and carboxylate O atoms. One can also recognize two different kinds of interstitial water molecules.

Two groups of acetate anions coordinate in a monodentate fashion to two Yb^III atoms of the inner layer, with bond distances of Yb4—O8 = 2.261 (5) and Yb2—O7 = 2.279 (4) Å for one, and Yb3—O9 = 2.265 (5) and Yb5—O10 = 2.271 (5) Å for the other. One group of acetate units does not coordinate to any metal centre whatsoever. In these cases, both carboxylate O atoms are held in place via hydrogen bonds originating from the hydroxy groups, with hydrogen-bond distances of 1.77 and 1.78 Å. The terminal Yb^III atom is linked to one bidentate carboxylate group [Yb1—O1 = 2.333 (4) and Yb1—O2 = 2.613 (5) Å] and two different carboxylate groups, of which only one O atom coordinates to the terminal Yb^III atom. One of these two carboxylate units possesses an O atom that remains uncoordinated which is the receiver of a hydrogen bond (2.285 Å) from one hydroxy group. The Yb1—O5 distance of the coordinated O atom is 2.257 (4) Å. The second O atom of the other carboxylate group coordinates to one of the Yb^III atoms within the inner layer, with Yb6—O4 = 2.308 (4) Å. The coordination bond to the external Yb^III atom is Yb1—O3 = 2.276 (4) Å.

Thus, the terminal Yb^III atoms exhibit the most diverse coordination environments, as their YbO₈ polyhedra also accommodate one water molecule. These are the only coordinating water O atoms, with Yb1—O25 = 2.333 (4) Å. One of the water H atoms connects via a hydrogen bond (2.00 Å) to one of the carboxylate groups within the adjacent layer that coordinate in bidentate fashion to the terminal Yb^III atoms of that layer. Fig. 3 illustrates the ligand environment of the terminal Yb^III atom, in the form of displacement ellipsoids for each atom at a probability level of 50%.

S2. Experimental

Ytterbium acetate hydrate (Acros Organics, 99.90%) (1.0 g, 2.9 mmol) was mixed with 0.19 M sodium acetate solution (15.6 ml, 3.0 mmol). The mixture was placed in a Teflon liner inside a Parr acid-digestion vessel (Model 4744; 45 ml). The vessel was sealed and heated to a temperature of 443 K inside a conventional laboratory oven. After two weeks, the vessel was removed from the hot oven and allowed to cool to room temperature on the laboratory bench before opening. A white solid material was obtained that was submerged in liquid [Specify liquid?] and rinsed four times with deionised water in order to remove any water-soluble starting materials. Most of the product had formed crystals in the form of long needles. Small amounts of the product were stored in a scintillation vial with small quantities of deionised water until a single crystal was chosen for X-ray structural analysis.

S3. Refinement

The H atoms on water molecule O27 could not be located. All other H atoms were visible in difference maps. Hydroxide H atoms were idealized to yield three equal Yb—O—H angles and O—H distances of 1.00 Å, and were treated as riding. The H atoms of the acetate methyl groups were idealized with C—H distances of 0.98 Å based on electron density in the expected circles, and a torsional parameter was refined for each methyl group. Water H atoms were placed based on difference maps and treated as riding in the refinement, after adjusting the O—H distances to 0.84 Å. U_iso values were assigned as 1.2U_eq of the attached atom for OH groups and as 1.5U_eq of the attached atom for methyl groups and water molecules.

The largest difference peak is 0.72 Å from atom Yb6, and the top 30 peaks are within 1.08 Å of Yb positions. The deepest hole is 0.65 Å from atom Yb2. The deepest hole which is not near a Yb position is 1.18 Å from atom O4, with a depth of -2.96 e Å^-3. This is about 10% of the magnitude of the electron density at the O4 site, 28.8 e Å^-3. The r.m.s. deviation from the mean in the final difference map is 0.59 e Å^-3.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Version 8.3.1 for Mac; Palmer, 2010); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The packing of the YbO8 and YbO7 polyhedra in (I), with interstitial water molecules, viewed along the a axis. Large light-grey spheres denote water molecules, small light-grey spheres hydroxy groups, small dark-grey spheres carboxylate O atoms, grey and light-grey polyhedra [YbO8] units, dark-grey polyhedra [YbO7] units, and interlaced black triangles [CH3COO] groups.
	Fig. 2. The highly interlinked two-dimensional layers in (I) that experience weak interactions via hydrogen bonds originating from coordinating water molecules. Light-grey spheres denote water and hydroxy O atoms, dark-grey spheres carboxylate O atoms, black spheres C atoms, white spheres H atoms, grey and light-grey polyhedra [YbO8] units, and dark-grey polyhedra [YbO7] units.
	Fig. 3. The asymmetric unit in (I), showing the atom-numbering scheme and with displacement ellipsoids drawn at the 80% probability level. H atoms are drawn as circles of arbitrary radius and dashed lines represent hydrogen bonds.

(Acetato-κ²O,O')dihydroxidoytterbium(III) hemihydrate

Crystal data

[Yb(C2H3O2)(OH)2]·0.5H2O	Z = 12
Mr = 275.11	F(000) = 1488
Triclinic, P1	Dx = 3.539 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3235 (10) Å	Cell parameters from 13849 reflections
b = 12.1765 (14) Å	θ = 2.5–35.6°
c = 15.5502 (15) Å	µ = 18.03 mm^−1
α = 109.796 (5)°	T = 90 K
β = 92.666 (6)°	Lath, colourless
γ = 108.745 (5)°	0.15 × 0.10 × 0.07 mm
V = 1548.9 (3) Å^3

Data collection

Nonius KappaCCD with Oxford Cryostream diffractometer	14105 independent reflections
Radiation source: fine-focus sealed tube	11613 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω and ϕ scans	θmax = 35.6°, θmin = 2.6°
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997)	h = −15→15
Tmin = 0.173, Tmax = 0.365	k = −19→19
56149 measured reflections	l = −25→25

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.120	w = 1/[σ^2(Fo^2) + (0.080P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.002
14105 reflections	Δρmax = 5.71 e Å^−3
413 parameters	Δρmin = −5.73 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00105 (9)

Special details

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. H atoms on water molecule O27 could not be located. The largest difference peak is 0.72 Å from Yb6, and the top 30 peaks are within 1.08 Å of Yb positions. The deepest hole is 0.65 Å from Yb2. The deepest hole which is not near a Yb position is 1.18 Å from O4, with a depth of -2.96 e Å^-3. This is about 10% of the magnitude of the electron density at the O4 site, 28.8 e Å^-3. The r.m.s. deviation from the mean in the final difference map is 0.59 e Å^-3.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Yb1	0.49629 (3)	0.66955 (2)	0.221061 (17)	0.00577 (5)
Yb2	0.78616 (3)	0.92281 (2)	0.433478 (17)	0.00506 (5)
Yb3	0.57975 (3)	0.60690 (2)	0.432760 (17)	0.00505 (5)
Yb4	0.99763 (3)	0.76052 (2)	0.527080 (17)	0.00515 (5)
Yb5	0.78609 (3)	0.43045 (2)	0.474671 (17)	0.00524 (5)
Yb6	0.62550 (3)	0.17451 (2)	0.555417 (17)	0.00491 (5)
O1	0.3519 (5)	0.4564 (4)	0.1714 (3)	0.0100 (8)
O2	0.3642 (5)	0.5147 (4)	0.0521 (3)	0.0112 (8)
O3	0.2685 (5)	0.6943 (4)	0.1948 (3)	0.0090 (7)
O4	0.2070 (5)	0.8096 (4)	0.3231 (3)	0.0089 (7)
O5	0.5618 (5)	0.8118 (4)	0.1534 (3)	0.0109 (8)
O6	0.5164 (6)	0.9833 (5)	0.2364 (4)	0.0144 (9)
O7	0.8945 (5)	0.9595 (5)	0.3128 (4)	0.0132 (9)
O8	0.9864 (5)	1.1546 (4)	0.3174 (3)	0.0100 (8)
O9	0.5511 (5)	0.4219 (4)	0.3195 (4)	0.0123 (8)
O10	0.7087 (5)	0.3183 (4)	0.3199 (3)	0.0107 (8)
O11	1.0490 (5)	0.4746 (4)	0.2721 (3)	0.0109 (8)
O12	0.8695 (5)	0.5471 (5)	0.2417 (3)	0.0125 (8)
O13	0.6967 (5)	0.7100 (4)	0.3340 (3)	0.0071 (7)
H13	0.7806	0.6822	0.3078	0.009*
O14	0.5458 (5)	0.8572 (4)	0.3468 (3)	0.0071 (7)
H14	0.5372	0.9231	0.3243	0.009*
O15	0.3974 (5)	0.6328 (4)	0.3448 (3)	0.0073 (7)
H15	0.2974	0.5606	0.3254	0.009*
O16	0.7731 (5)	0.7995 (4)	0.5244 (3)	0.0080 (7)
H16	0.7508	0.8377	0.5877	0.010*
O17	1.0272 (5)	0.8961 (4)	0.4520 (3)	0.0072 (7)
H17	1.0642	0.8679	0.3919	0.009*
O18	0.6157 (5)	0.9696 (4)	0.5337 (3)	0.0059 (7)
H18	0.6377	0.9597	0.5937	0.007*
O19	0.7492 (5)	1.1080 (4)	0.4293 (3)	0.0071 (7)
H19	0.6977	1.0986	0.3680	0.009*
O20	0.8224 (5)	0.5875 (4)	0.4221 (3)	0.0068 (7)
H20	0.8467	0.5671	0.3579	0.008*
O21	0.9950 (5)	0.6010 (4)	0.5750 (3)	0.0077 (7)
H21	0.9934	0.6194	0.6426	0.009*
O22	0.6434 (5)	0.5412 (4)	0.5500 (3)	0.0061 (7)
H22	0.7011	0.6115	0.6095	0.007*
O23	0.5555 (5)	0.2835 (4)	0.4718 (3)	0.0075 (7)
H23	0.4966	0.2286	0.4079	0.009*
O24	0.8515 (5)	0.3315 (4)	0.5607 (3)	0.0061 (7)
H24	0.9053	0.3888	0.6252	0.007*
O25	0.6682 (5)	0.5906 (4)	0.1399 (3)	0.0123 (8)
H25A	0.6325	0.5637	0.0831	0.018*
H25B	0.7373	0.5717	0.1612	0.018*
O26	0.7653 (5)	0.7131 (5)	0.7411 (4)	0.0141 (9)
H26A	0.7252	0.6577	0.7625	0.021*
H26B	0.7787	0.7890	0.7700	0.021*
O27	0.6610 (5)	0.8794 (5)	0.6952 (4)	0.0136 (9)
C1	0.3228 (7)	0.4288 (6)	0.0847 (4)	0.0109 (10)
C2	0.2448 (7)	0.2948 (6)	0.0213 (5)	0.0137 (11)
H2A	0.1734	0.2895	−0.0295	0.021*
H2B	0.1879	0.2468	0.0561	0.021*
H2C	0.3222	0.2606	−0.0043	0.021*
C3	0.1914 (7)	0.7564 (6)	0.2346 (4)	0.0089 (10)
C4	0.0770 (8)	0.7763 (7)	0.1759 (5)	0.0150 (12)
H4A	0.1276	0.8519	0.1632	0.023*
H4B	−0.0077	0.7861	0.2090	0.023*
H4C	0.0366	0.7041	0.1172	0.023*
C5	0.5133 (7)	0.8994 (6)	0.1606 (5)	0.0124 (11)
C6	0.4453 (11)	0.9005 (8)	0.0711 (6)	0.0271 (17)
H6A	0.4077	0.9700	0.0848	0.041*
H6B	0.3597	0.8214	0.0382	0.041*
H6C	0.5243	0.9108	0.0321	0.041*
C7	0.9324 (6)	1.0375 (6)	0.2734 (4)	0.0081 (9)
C8	0.9117 (8)	0.9940 (6)	0.1697 (4)	0.0134 (11)
H8A	0.8591	1.0404	0.1484	0.020*
H8B	0.8500	0.9044	0.1423	0.020*
H8C	1.0126	1.0086	0.1504	0.020*
C9	0.6108 (7)	0.3434 (5)	0.2781 (4)	0.0083 (9)
C10	0.5659 (7)	0.2777 (6)	0.1743 (5)	0.0132 (11)
H10A	0.6330	0.2307	0.1511	0.020*
H10B	0.5765	0.3395	0.1456	0.020*
H10C	0.4588	0.2200	0.1587	0.020*
C11	0.9558 (6)	0.4845 (6)	0.2168 (5)	0.0102 (10)
C12	0.9491 (7)	0.4201 (7)	0.1130 (5)	0.0144 (11)
H12A	0.8547	0.4149	0.0788	0.022*
H12B	0.9498	0.3357	0.1000	0.022*
H12C	1.0386	0.4684	0.0937	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Yb1	0.00629 (10)	0.00545 (10)	0.00607 (10)	0.00274 (8)	0.00109 (8)	0.00215 (8)
Yb2	0.00457 (10)	0.00432 (10)	0.00679 (10)	0.00197 (7)	0.00097 (7)	0.00234 (8)
Yb3	0.00482 (10)	0.00466 (10)	0.00673 (10)	0.00237 (7)	0.00146 (7)	0.00271 (8)
Yb4	0.00466 (10)	0.00412 (10)	0.00744 (11)	0.00204 (8)	0.00118 (8)	0.00262 (8)
Yb5	0.00474 (10)	0.00436 (10)	0.00760 (11)	0.00221 (7)	0.00129 (7)	0.00284 (8)
Yb6	0.00463 (10)	0.00428 (10)	0.00648 (10)	0.00201 (7)	0.00134 (7)	0.00234 (8)
O1	0.014 (2)	0.0068 (18)	0.0091 (19)	0.0021 (15)	0.0016 (15)	0.0048 (15)
O2	0.0101 (18)	0.0101 (19)	0.014 (2)	0.0030 (16)	0.0008 (16)	0.0058 (17)
O3	0.0091 (18)	0.0097 (19)	0.0096 (19)	0.0065 (15)	0.0029 (15)	0.0023 (16)
O4	0.0063 (17)	0.0122 (19)	0.0097 (19)	0.0032 (15)	0.0003 (14)	0.0063 (16)
O5	0.0135 (19)	0.0101 (19)	0.015 (2)	0.0075 (16)	0.0069 (17)	0.0081 (17)
O6	0.023 (2)	0.010 (2)	0.012 (2)	0.0090 (18)	0.0042 (18)	0.0032 (17)
O7	0.016 (2)	0.016 (2)	0.017 (2)	0.0093 (18)	0.0108 (18)	0.0132 (19)
O8	0.0127 (19)	0.0057 (17)	0.0078 (19)	0.0022 (15)	−0.0003 (15)	−0.0007 (15)
O9	0.0085 (18)	0.0077 (19)	0.016 (2)	0.0029 (15)	0.0043 (16)	−0.0010 (17)
O10	0.0119 (19)	0.012 (2)	0.0083 (19)	0.0052 (16)	0.0000 (15)	0.0028 (16)
O11	0.0116 (19)	0.017 (2)	0.0064 (18)	0.0074 (17)	0.0005 (15)	0.0059 (17)
O12	0.0110 (19)	0.018 (2)	0.011 (2)	0.0080 (17)	0.0034 (16)	0.0048 (18)
O13	0.0065 (16)	0.0081 (18)	0.0098 (19)	0.0048 (14)	0.0022 (14)	0.0047 (15)
O14	0.0066 (16)	0.0072 (17)	0.0082 (18)	0.0037 (14)	0.0006 (14)	0.0027 (15)
O15	0.0094 (17)	0.0063 (17)	0.0061 (17)	0.0029 (14)	0.0014 (14)	0.0022 (14)
O16	0.0071 (17)	0.0068 (17)	0.0112 (19)	0.0041 (14)	0.0016 (14)	0.0032 (15)
O17	0.0059 (16)	0.0043 (16)	0.0120 (19)	0.0017 (13)	0.0018 (14)	0.0039 (15)
O18	0.0096 (17)	0.0017 (15)	0.0041 (16)	−0.0001 (13)	−0.0010 (13)	0.0004 (13)
O19	0.0066 (16)	0.0057 (17)	0.0096 (19)	0.0042 (14)	0.0023 (14)	0.0015 (15)
O20	0.0054 (16)	0.0036 (16)	0.0126 (19)	0.0012 (13)	0.0020 (14)	0.0049 (15)
O21	0.0089 (17)	0.0064 (17)	0.0112 (19)	0.0034 (14)	0.0029 (15)	0.0064 (15)
O22	0.0082 (17)	0.0046 (16)	0.0060 (17)	0.0034 (14)	0.0022 (14)	0.0014 (14)
O23	0.0093 (17)	0.0080 (18)	0.0065 (18)	0.0051 (15)	−0.0005 (14)	0.0029 (15)
O24	0.0060 (16)	0.0051 (16)	0.0073 (18)	0.0020 (13)	0.0010 (14)	0.0023 (14)
O25	0.013 (2)	0.016 (2)	0.0075 (19)	0.0100 (17)	0.0002 (16)	0.0003 (17)
O26	0.016 (2)	0.012 (2)	0.018 (2)	0.0044 (17)	0.0041 (18)	0.0098 (19)
O27	0.017 (2)	0.016 (2)	0.013 (2)	0.0104 (18)	0.0040 (17)	0.0064 (18)
C1	0.010 (2)	0.011 (3)	0.008 (2)	0.003 (2)	0.0002 (19)	0.000 (2)
C2	0.016 (3)	0.010 (3)	0.011 (3)	0.001 (2)	0.000 (2)	0.002 (2)
C3	0.009 (2)	0.010 (2)	0.009 (2)	0.0033 (19)	0.0034 (19)	0.004 (2)
C4	0.018 (3)	0.018 (3)	0.011 (3)	0.013 (2)	−0.002 (2)	0.004 (2)
C5	0.013 (3)	0.010 (3)	0.018 (3)	0.005 (2)	0.005 (2)	0.008 (2)
C6	0.048 (5)	0.025 (4)	0.016 (3)	0.021 (4)	0.002 (3)	0.011 (3)
C7	0.008 (2)	0.010 (2)	0.007 (2)	0.0041 (19)	0.0021 (18)	0.0025 (19)
C8	0.018 (3)	0.010 (3)	0.009 (3)	0.002 (2)	0.001 (2)	0.001 (2)
C9	0.009 (2)	0.006 (2)	0.010 (2)	0.0013 (18)	0.0025 (19)	0.0039 (19)
C10	0.012 (3)	0.013 (3)	0.010 (3)	0.005 (2)	−0.001 (2)	0.000 (2)
C11	0.003 (2)	0.015 (3)	0.012 (3)	0.0017 (19)	0.0027 (18)	0.005 (2)
C12	0.014 (3)	0.019 (3)	0.009 (3)	0.006 (2)	0.004 (2)	0.002 (2)

Geometric parameters (Å, º)

Yb1—O5	2.257 (4)	O9—C9	1.263 (7)
Yb1—O3	2.276 (4)	O10—C9	1.268 (7)
Yb1—O15	2.288 (4)	O11—C11	1.256 (7)
Yb1—O13	2.310 (4)	O12—C11	1.265 (7)
Yb1—O25	2.333 (4)	O13—H13	1.0000
Yb1—O1	2.333 (4)	O14—Yb6^ii	2.289 (4)
Yb1—O14	2.338 (4)	O14—H14	1.0000
Yb1—O2	2.613 (5)	O15—Yb6^ii	2.418 (4)
Yb2—O7	2.279 (4)	O15—H15	1.0000
Yb2—O14	2.306 (4)	O16—H16	1.0000
Yb2—O18	2.343 (4)	O17—Yb2^i	2.377 (4)
Yb2—O13	2.362 (4)	O17—H17	1.0000
Yb2—O16	2.367 (4)	O18—Yb6^ii	2.363 (4)
Yb2—O17^i	2.377 (4)	O18—Yb6^v	2.373 (4)
Yb2—O17	2.390 (4)	O18—H18	1.0000
Yb2—O19	2.409 (4)	O19—Yb4^i	2.298 (4)
Yb3—O9	2.265 (5)	O19—Yb6^v	2.360 (4)
Yb3—O15	2.298 (4)	O19—H19	1.0000
Yb3—O23^ii	2.342 (4)	O20—H20	1.0000
Yb3—O22	2.346 (4)	O21—Yb5^iii	2.314 (4)
Yb3—O20	2.357 (4)	O21—H21	1.0000
Yb3—O16	2.358 (4)	O22—Yb3^ii	2.371 (4)
Yb3—O22^ii	2.371 (4)	O22—H22	1.0000
Yb3—O13	2.388 (4)	O23—Yb3^ii	2.342 (4)
Yb4—O20	2.232 (4)	O23—H23	1.0000
Yb4—O8^i	2.261 (5)	O24—Yb4^iii	2.292 (4)
Yb4—O17	2.282 (4)	O24—H24	1.0000
Yb4—O16	2.291 (4)	O25—H25A	0.8400
Yb4—O24^iii	2.292 (4)	O25—H25B	0.8400
Yb4—O21	2.298 (4)	O26—H26A	0.8402
Yb4—O19^i	2.298 (4)	O26—H26B	0.8435
Yb5—O24	2.258 (4)	C1—C2	1.498 (9)
Yb5—O20	2.260 (4)	C2—H2A	0.9800
Yb5—O10	2.271 (5)	C2—H2B	0.9800
Yb5—O22	2.278 (4)	C2—H2C	0.9800
Yb5—O23	2.300 (4)	C3—C4	1.502 (9)
Yb5—O21^iii	2.314 (4)	C4—H4A	0.9800
Yb5—O21	2.338 (5)	C4—H4B	0.9800
Yb6—O14^ii	2.289 (4)	C4—H4C	0.9800
Yb6—O4^ii	2.308 (4)	C5—C6	1.508 (10)
Yb6—O24	2.322 (4)	C6—H6A	0.9800
Yb6—O23	2.350 (4)	C6—H6B	0.9800
Yb6—O19^iv	2.360 (4)	C6—H6C	0.9800
Yb6—O18^ii	2.363 (4)	C7—C8	1.499 (9)
Yb6—O18^iv	2.373 (4)	C8—H8A	0.9800
Yb6—O15^ii	2.418 (4)	C8—H8B	0.9800
O1—C1	1.267 (8)	C8—H8C	0.9800
O2—C1	1.272 (7)	C9—C10	1.505 (9)
O3—C3	1.243 (7)	C10—H10A	0.9800
O4—C3	1.285 (8)	C10—H10B	0.9800
O4—Yb6^ii	2.308 (4)	C10—H10C	0.9800
O5—C5	1.261 (7)	C11—C12	1.525 (9)
O6—C5	1.264 (8)	C12—H12A	0.9800
O7—C7	1.265 (7)	C12—H12B	0.9800
O8—C7	1.265 (7)	C12—H12C	0.9800
O8—Yb4^i	2.261 (5)
O5—Yb1—O3	78.42 (16)	O4^ii—Yb6—O15^ii	88.04 (15)
O5—Yb1—O15	143.46 (16)	O24—Yb6—O15^ii	74.67 (14)
O3—Yb1—O15	81.87 (15)	O23—Yb6—O15^ii	67.34 (15)
O5—Yb1—O13	110.23 (16)	O19^iv—Yb6—O15^ii	137.91 (14)
O3—Yb1—O13	144.55 (16)	O18^ii—Yb6—O15^ii	110.92 (14)
O15—Yb1—O13	71.19 (15)	O18^iv—Yb6—O15^ii	148.26 (14)
O5—Yb1—O25	85.09 (16)	C1—O1—Yb1	100.5 (4)
O3—Yb1—O25	140.34 (16)	C1—O2—Yb1	87.3 (4)
O15—Yb1—O25	128.09 (16)	C3—O3—Yb1	140.3 (4)
O13—Yb1—O25	75.06 (16)	C3—O4—Yb6^ii	132.4 (4)
O5—Yb1—O1	135.62 (17)	C5—O5—Yb1	128.9 (4)
O3—Yb1—O1	86.02 (16)	C7—O7—Yb2	143.8 (4)
O15—Yb1—O1	72.37 (16)	C7—O8—Yb4^i	121.6 (4)
O13—Yb1—O1	106.46 (15)	C9—O9—Yb3	148.3 (4)
O25—Yb1—O1	81.02 (16)	C9—O10—Yb5	116.9 (4)
O5—Yb1—O14	77.83 (16)	Yb1—O13—Yb2	109.94 (16)
O3—Yb1—O14	81.96 (15)	Yb1—O13—Yb3	104.86 (16)
O15—Yb1—O14	69.12 (15)	Yb2—O13—Yb3	102.42 (17)
O13—Yb1—O14	67.33 (15)	Yb1—O13—H13	112.9
O25—Yb1—O14	129.42 (15)	Yb2—O13—H13	112.9
O1—Yb1—O14	140.86 (15)	Yb3—O13—H13	112.9
O5—Yb1—O2	83.34 (16)	Yb6^ii—O14—Yb2	105.86 (17)
O3—Yb1—O2	73.63 (15)	Yb6^ii—O14—Yb1	109.38 (17)
O15—Yb1—O2	119.94 (15)	Yb2—O14—Yb1	110.93 (16)
O13—Yb1—O2	140.07 (14)	Yb6^ii—O14—H14	110.2
O25—Yb1—O2	68.76 (15)	Yb2—O14—H14	110.2
O1—Yb1—O2	52.33 (15)	Yb1—O14—H14	110.2
O14—Yb1—O2	151.70 (14)	Yb1—O15—Yb3	108.59 (17)
O7—Yb2—O14	89.42 (17)	Yb1—O15—Yb6^ii	106.69 (16)
O7—Yb2—O18	143.95 (15)	Yb3—O15—Yb6^ii	103.69 (17)
O14—Yb2—O18	71.08 (15)	Yb1—O15—H15	112.4
O7—Yb2—O13	85.21 (16)	Yb3—O15—H15	112.4
O14—Yb2—O13	66.98 (14)	Yb6^ii—O15—H15	112.4
O18—Yb2—O13	112.51 (14)	Yb4—O16—Yb3	105.81 (17)
O7—Yb2—O16	140.88 (15)	Yb4—O16—Yb2	107.38 (16)
O14—Yb2—O16	108.25 (14)	Yb3—O16—Yb2	103.19 (17)
O18—Yb2—O16	75.06 (14)	Yb4—O16—H16	113.2
O13—Yb2—O16	71.19 (15)	Yb3—O16—H16	113.2
O7—Yb2—O17^i	93.85 (17)	Yb2—O16—H16	113.2
O14—Yb2—O17^i	140.76 (14)	Yb4—O17—Yb2^i	99.23 (17)
O18—Yb2—O17^i	84.11 (14)	Yb4—O17—Yb2	106.93 (16)
O13—Yb2—O17^i	152.25 (14)	Yb2^i—O17—Yb2	111.34 (17)
O16—Yb2—O17^i	93.40 (15)	Yb4—O17—H17	112.8
O7—Yb2—O17	76.19 (16)	Yb2^i—O17—H17	112.8
O14—Yb2—O17	148.94 (15)	Yb2—O17—H17	112.8
O18—Yb2—O17	134.30 (15)	Yb2—O18—Yb6^ii	102.35 (16)
O13—Yb2—O17	84.28 (14)	Yb2—O18—Yb6^v	107.75 (15)
O16—Yb2—O17	70.91 (14)	Yb6^ii—O18—Yb6^v	108.55 (16)
O17^i—Yb2—O17	68.66 (17)	Yb2—O18—H18	112.5
O7—Yb2—O19	73.97 (15)	Yb6^ii—O18—H18	112.5
O14—Yb2—O19	73.51 (14)	Yb6^v—O18—H18	112.5
O18—Yb2—O19	71.56 (14)	Yb4^i—O19—Yb6^v	106.54 (17)
O13—Yb2—O19	135.24 (15)	Yb4^i—O19—Yb2	97.84 (15)
O16—Yb2—O19	143.86 (15)	Yb6^v—O19—Yb2	106.01 (16)
O17^i—Yb2—O19	69.95 (14)	Yb4^i—O19—H19	114.9
O17—Yb2—O19	126.27 (14)	Yb6^v—O19—H19	114.9
O9—Yb3—O15	90.69 (16)	Yb2—O19—H19	114.9
O9—Yb3—O23^ii	143.01 (15)	Yb4—O20—Yb5	108.24 (18)
O15—Yb3—O23^ii	69.45 (15)	Yb4—O20—Yb3	107.82 (17)
O9—Yb3—O22	92.37 (16)	Yb5—O20—Yb3	98.48 (15)
O15—Yb3—O22	149.26 (14)	Yb4—O20—H20	113.7
O23^ii—Yb3—O22	90.49 (14)	Yb5—O20—H20	113.7
O9—Yb3—O20	70.83 (16)	Yb3—O20—H20	113.7
O15—Yb3—O20	137.84 (15)	Yb4—O21—Yb5^iii	99.82 (15)
O23^ii—Yb3—O20	143.75 (15)	Yb4—O21—Yb5	103.46 (17)
O22—Yb3—O20	71.32 (14)	Yb5^iii—O21—Yb5	106.32 (18)
O9—Yb3—O16	140.41 (15)	Yb4—O21—H21	115.2
O15—Yb3—O16	111.82 (15)	Yb5^iii—O21—H21	115.2
O23^ii—Yb3—O16	76.56 (15)	Yb5—O21—H21	115.2
O22—Yb3—O16	84.26 (15)	Yb5—O22—Yb3	98.27 (16)
O20—Yb3—O16	70.76 (15)	Yb5—O22—Yb3^ii	106.16 (16)
O9—Yb3—O22^ii	74.37 (15)	Yb3—O22—Yb3^ii	109.55 (17)
O15—Yb3—O22^ii	81.02 (14)	Yb5—O22—H22	113.9
O23^ii—Yb3—O22^ii	71.96 (14)	Yb3—O22—H22	113.9
O22—Yb3—O22^ii	70.45 (17)	Yb3^ii—O22—H22	113.9
O20—Yb3—O22^ii	126.14 (13)	Yb5—O23—Yb3^ii	106.37 (17)
O16—Yb3—O22^ii	138.89 (15)	Yb5—O23—Yb6	103.61 (16)
O9—Yb3—O13	88.63 (16)	Yb3^ii—O23—Yb6	104.45 (16)
O15—Yb3—O13	69.62 (14)	Yb5—O23—H23	113.8
O23^ii—Yb3—O13	111.37 (14)	Yb3^ii—O23—H23	113.8
O22—Yb3—O13	141.01 (14)	Yb6—O23—H23	113.8
O20—Yb3—O13	72.30 (14)	Yb5—O24—Yb4^iii	101.70 (16)
O16—Yb3—O13	70.90 (15)	Yb5—O24—Yb6	105.88 (16)
O22^ii—Yb3—O13	145.87 (15)	Yb4^iii—O24—Yb6	108.04 (17)
O20—Yb4—O8^i	129.82 (16)	Yb5—O24—H24	113.4
O20—Yb4—O17	100.84 (15)	Yb4^iii—O24—H24	113.4
O8^i—Yb4—O17	115.41 (16)	Yb6—O24—H24	113.4
O20—Yb4—O16	74.23 (15)	Yb1—O25—H25A	107.3
O8^i—Yb4—O16	83.24 (16)	Yb1—O25—H25B	126.9
O17—Yb4—O16	74.23 (15)	H25A—O25—H25B	123.5
O20—Yb4—O24^iii	78.00 (15)	H26A—O26—H26B	122.2
O8^i—Yb4—O24^iii	131.21 (16)	O1—C1—O2	119.6 (6)
O17—Yb4—O24^iii	91.12 (15)	O1—C1—C2	119.7 (6)
O16—Yb4—O24^iii	145.22 (16)	O2—C1—C2	120.6 (6)
O20—Yb4—O21	74.24 (16)	O1—C1—Yb1	53.6 (3)
O8^i—Yb4—O21	76.42 (16)	O2—C1—Yb1	66.2 (3)
O17—Yb4—O21	166.26 (16)	C2—C1—Yb1	171.2 (5)
O16—Yb4—O21	115.65 (15)	C1—C2—H2A	109.5
O24^iii—Yb4—O21	75.37 (15)	C1—C2—H2B	109.5
O20—Yb4—O19^i	146.93 (15)	H2A—C2—H2B	109.5
O8^i—Yb4—O19^i	79.25 (16)	C1—C2—H2C	109.5
O17—Yb4—O19^i	73.61 (15)	H2A—C2—H2C	109.5
O16—Yb4—O19^i	131.77 (15)	H2B—C2—H2C	109.5
O24^iii—Yb4—O19^i	69.67 (15)	O3—C3—O4	124.5 (6)
O21—Yb4—O19^i	103.29 (15)	O3—C3—C4	118.3 (6)
O24—Yb5—O20	155.16 (15)	O4—C3—C4	117.2 (5)
O24—Yb5—O10	116.35 (16)	C3—C4—H4A	109.5
O20—Yb5—O10	79.96 (16)	C3—C4—H4B	109.5
O24—Yb5—O22	109.70 (15)	H4A—C4—H4B	109.5
O20—Yb5—O22	74.35 (15)	C3—C4—H4C	109.5
O10—Yb5—O22	118.13 (16)	H4A—C4—H4C	109.5
O24—Yb5—O23	76.28 (14)	H4B—C4—H4C	109.5
O20—Yb5—O23	127.24 (14)	O5—C5—O6	124.6 (6)
O10—Yb5—O23	78.72 (16)	O5—C5—C6	116.3 (6)
O22—Yb5—O23	74.44 (15)	O6—C5—C6	119.0 (6)
O24—Yb5—O21^iii	75.69 (14)	C5—C6—H6A	109.5
O20—Yb5—O21^iii	91.52 (14)	C5—C6—H6B	109.5
O10—Yb5—O21^iii	76.26 (16)	H6A—C6—H6B	109.5
O22—Yb5—O21^iii	156.61 (15)	C5—C6—H6C	109.5
O23—Yb5—O21^iii	128.38 (14)	H6A—C6—H6C	109.5
O24—Yb5—O21	82.93 (14)	H6B—C6—H6C	109.5
O20—Yb5—O21	72.97 (15)	O7—C7—O8	123.2 (6)
O10—Yb5—O21	138.49 (16)	O7—C7—C8	120.6 (6)
O22—Yb5—O21	84.25 (15)	O8—C7—C8	116.2 (5)
O23—Yb5—O21	142.78 (15)	C7—C8—H8A	109.5
O21^iii—Yb5—O21	73.68 (18)	C7—C8—H8B	109.5
O14^ii—Yb6—O4^ii	81.56 (15)	H8A—C8—H8B	109.5
O14^ii—Yb6—O24	136.47 (15)	C7—C8—H8C	109.5
O4^ii—Yb6—O24	75.92 (15)	H8A—C8—H8C	109.5
O14^ii—Yb6—O23	108.99 (14)	H8B—C8—H8C	109.5
O4^ii—Yb6—O23	145.22 (15)	O9—C9—O10	122.9 (6)
O24—Yb6—O23	74.12 (14)	O9—C9—C10	118.9 (6)
O14^ii—Yb6—O19^iv	153.93 (15)	O10—C9—C10	118.2 (5)
O4^ii—Yb6—O19^iv	100.99 (15)	C9—C10—H10A	109.5
O24—Yb6—O19^iv	68.11 (14)	C9—C10—H10B	109.5
O23—Yb6—O19^iv	83.83 (14)	H10A—C10—H10B	109.5
O14^ii—Yb6—O18^ii	71.02 (15)	C9—C10—H10C	109.5
O4^ii—Yb6—O18^ii	136.21 (14)	H10A—C10—H10C	109.5
O24—Yb6—O18^ii	145.95 (14)	H10B—C10—H10C	109.5
O23—Yb6—O18^ii	77.47 (14)	O11—C11—O12	124.2 (6)
O19^iv—Yb6—O18^ii	90.67 (14)	O11—C11—C12	118.0 (5)
O14^ii—Yb6—O18^iv	84.43 (14)	O12—C11—C12	117.8 (6)
O4^ii—Yb6—O18^iv	72.51 (15)	C11—C12—H12A	109.5
O24—Yb6—O18^iv	122.07 (14)	C11—C12—H12B	109.5
O23—Yb6—O18^iv	139.82 (15)	H12A—C12—H12B	109.5
O19^iv—Yb6—O18^iv	71.92 (14)	C11—C12—H12C	109.5
O18^ii—Yb6—O18^iv	71.45 (16)	H12A—C12—H12C	109.5
O14^ii—Yb6—O15^ii	67.72 (14)	H12B—C12—H12C	109.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···O12	1.00	2.06	2.989 (6)	153
O14—H14···O6	1.00	1.79	2.718 (6)	154
O15—H15···O11^vi	1.00	2.20	3.115 (6)	152
O16—H16···O27	1.00	1.89	2.873 (7)	166
O17—H17···O4^vii	1.00	1.91	2.820 (6)	150
O18—H18···O27	1.00	2.16	3.124 (6)	163
O19—H19···O6	1.00	2.29	3.194 (7)	151
O20—H20···O12	1.00	1.77	2.762 (6)	170
O21—H21···O11^iii	1.00	2.00	2.829 (6)	138
O22—H22···O26	1.00	1.94	2.906 (7)	161
O23—H23···O27^ii	1.00	1.89	2.864 (7)	164
O24—H24···O11^iii	1.00	1.78	2.722 (6)	155
O25—H25A···O2^viii	0.84	2.00	2.779 (7)	154
O25—H25A···O2	0.84	2.36	2.802 (6)	113
O25—H25B···O12	0.84	1.88	2.691 (6)	163
O26—H26A···O1^ii	0.84	1.97	2.810 (6)	173
O26—H26B···O27	0.84	2.30	2.781 (6)	116

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+1, −z+1; (vi) x−1, y, z; (vii) x+1, y, z; (viii) −x+1, −y+1, −z.