Crystal structures of the penta- and hexa­hydrate of thulium nitrate

Klein, W.

doi:10.1107/S2056989020015388

research communications

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ISSN: 2056-9890

Volume 76| Part 12| December 2020| Pages 1863-1867

https://doi.org/10.1107/S2056989020015388

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Crystal structures of the penta- and hexahydrate of thulium nitrate

Wilhelm Klein ^a ^*

^aTechnische Universität München, Department of Chemistry, Lichtenbergstr. 4, 85747 Garching, Germany
^*Correspondence e-mail: wilhelm.klein@tum.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 5 November 2020; accepted 20 November 2020; online 24 November 2020)

Tm(NO₃)₃·5H₂O and Tm(NO₃)₃·6H₂O, or more precisely [Tm(NO₃)₃(H₂O)₄]·H₂O and [Tm(NO₃)₃(H₂O)₄]·2H₂O, respectively, have been obtained from a concentrated solution of Tm₂O₃ in HNO₃. The crystal structures of the two hydrates show strong similarities as both crystallize in space group P $[\overline{1}]$ with all atoms at general positions and contain neutral, molecular [Tm(NO₃)₃(H₂O)₄] complexes, i.e. ten-coordinated Tm^III cations with three nitrate anions as bidentate ligands and four coordinating water molecules, and one or two additional crystal water molecules, respectively. All building units are connected by medium–strong to weak O—H⋯O hydrogen bonds. Tm(NO₃)₃·6H₂O represents the maximally hydrated thulium nitrate as well as the heaviest rare earth nitrate hexahydrate known to date.

Keywords: crystal structure; thulium; nitrate; hydrate; hydrogen bonding.

CCDC references: 2045553; 2045552

1. Chemical context

The nitrates of the rare earth metals have long been used to separate and purify these elements. For example, when thulium was discovered (Cleve, 1897 ), fusion of nitrates was already used to separate the element from the erbium-containing earth, and a hydrate of thulium nitrate in substance was already described more than 100 years ago with four equivalents of water of crystallization and of highly hygroscopic nature (James, 1911 ). Later, among others, double nitrates like Mg₃Ln₂(NO₃)₁₂·24H₂O and (NH₄)₂Ln(NO₃)₅·4H₂O (Ln = rare earth element) were used to separate the elements by means of fractional crystallization (Prandtl, 1938 ). Also, when more sophisticated separation procedures such as chromatographic methods and solvent extraction were developed (Bock, 1950 ), there was still considerable interest in these complex nitrates because of their high solubility even in organic solvents. Numerous structural investigations have been reported for this family, not least for the hydrated compounds (Wickleder, 2002 ).

Considering the structural information for the maximally hydrated rare earth nitrates, a general tendency of a decreasing amount of water with increasing atomic number is obvious: for the lighter homologues La–Nd and Sm–Tb, the hexahydrates are found as maximally hydrated compounds for the nitrates (La: Eriksson et al., 1980 ; Ce: Milinski et al., 1980 ; Pr: Decadt et al., 2012 ; Nd: Rogers et al., 1983 ; Sm: Kawashima et al., 2000 ; Eu: Stumpf & Bolte, 2001 ; Gd: Taha et al., 2012 ; Tb: Moret et al., 1990 ) while for the heavier elements Dy–Er and Yb, only pentahydrates have been reported (Ho: Rincke et al., 2017 ; other: Junk et al., 1999 ). Confirming this trend, the highest hydrate of Lu nitrate is the tetrahydrate (Junk et al., 1999), and for Tm the trihydrate exhibits the highest number of water molecules reported so far (Riess, 2012 ).

In the present research communication, the new penta- and hexahydrates of Tm(NO₃)₃ are reported. While the pentahydrate of Tm(NO₃)₃ fills the gap within the known compounds containing Er and Yb, the hexahydrate indeed represents the highest hydrated nitrate including Tm and shifts the border of known stable compounds notably to heavier rare earth elements.

2. Structural commentary

Tm(NO₃)₃·5H₂O crystallizes in the Y(NO₃)₃·5H₂O type of structure (Eriksson, 1982 ) in space group P $[\overline{1}]$ with all atoms at general positions. The structure consists of isolated molecular [Tm(NO₃)₃(H₂O)₄] complexes and one additional free water molecule per formula unit (Fig. 1). The nitrate anions act as bidentate ligands so the Tm^III atom is tenfold coordinated. The nitrate ions form an equatorial belt separating one aqua ligand from the other three, and are slightly inclined in the same sense and form a propeller-like shape. The nitrate anions coordinate asymmetrically at one shorter [2.3980 (17)–2.4479 (16) Å] and one slightly longer distance [2.5081 (16)–2.6193 (18) Å] each. The shortest Tm—O bonds [2.3235 (17)–2.3526 (18) Å] are formed with the three aqua ligands on the same side of the plane, while the remaining Tm—O(H2) bond is in the range of the shorter bonds to the nitrate ions. The anions are almost planar with an O—N—O angular sum of 360.0° where the angle formed by the coordinating O atoms is significantly reduced. The N—O bond lengths are between 1.256 (3) and 1.290 (3) Å for coordinating and 1.213 (3) and 1.220 (3) Å for non-coordinating O atoms. Within the water molecules, the O—H bond lengths are between 0.68 (6) and 0.86 (4) Å, and the H—O—H angles between 102 (4) and 111 (4)°. The structural entities, i.e. the molecular [Tm(NO₃)₃(H₂O)₄] complexes and H₂O molecules, are interconnected by almost linear hydrogen bonds (see Fig. 2) of medium–strong to weak strength. In detail, eight of ten independent H atoms form hydrogen bonds shorter than 2.30 Å with O—H⋯O angles greater than 163°, while atoms H2 and H10 are part of bifurcated and slightly longer hydrogen bonds (Table 1).

Table 1
Hydrogen-bond geometry (Å, °) for Tm(NO₃)₃·5H₂O

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H1⋯O1ⁱ	0.82 (4)	2.03 (4)	2.849 (2)	174 (3)
O10—H2⋯O13ⁱⁱ	0.78 (4)	2.32 (4)	2.996 (3)	145 (3)
O10—H2⋯O2ⁱⁱ	0.78 (4)	2.48 (4)	3.035 (3)	129 (3)
O11—H3⋯O14ⁱ	0.77 (5)	1.98 (5)	2.739 (3)	167 (5)
O11—H4⋯O2ⁱⁱⁱ	0.85 (4)	2.03 (4)	2.874 (2)	171 (4)
O12—H5⋯O14^iv	0.83 (4)	1.90 (4)	2.715 (3)	165 (4)
O12—H6⋯O7^v	0.83 (4)	1.95 (4)	2.776 (2)	174 (4)
O13—H7⋯O5^vi	0.82 (5)	1.98 (5)	2.784 (2)	166 (4)
O13—H8⋯O3^vii	0.86 (4)	2.12 (4)	2.953 (3)	163 (4)
O14—H9⋯O3^vii	0.84 (4)	2.27 (5)	3.095 (3)	167 (4)
O14—H10⋯O9	0.68 (6)	2.44 (6)	3.040 (3)	148 (5)
O14—H10⋯O6^viii	0.68 (6)	2.62 (6)	3.132 (4)	134 (5)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Figure 1
Asymmetric unit of Tm(NO₃)₃·5H₂O with the atom-numbering scheme. Anisotropic displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

Figure 2
Crystal structure of Tm(NO₃)₃·5H₂O in a view along [100]. Hydrogen bonds are shown as dotted lines up to an O⋯H distance of 2.45 Å. Anisotropic displacement ellipsoids of non-H atoms are drawn at the 50% probability level.

Tm(NO₃)₃·6H₂O also crystallizes in space group P $[\overline{1}]$ without occupying special positions and is isotypic with the respective Pr compound (Decadt et al., 2012). In comparison with Tm(NO₃)₃·5H₂O the volume (as determined at 223 K) increases by 34.4 Å³ for the two additional H₂O molecules per unit cell. Further structural similarities to the pentahydrate include the presence of molecular [Tm(NO₃)₃(H₂O)₄] complexes and free water molecules, but here two per formula unit. The [Tm(NO₃)₃(H₂O)₄] complexes of the penta- and hexahydrates differ slightly, since in the latter the four water molecules and the three nitrate ligands accumulate on opposite sides of the complex (Fig. 3). With the nitrate anions as more or less bidentate ligands, again ten atoms are found in the first coordination sphere of the Tm^III atom in Tm(NO₃)₃·6H₂O. The resulting polyhedron can be described as a strongly distorted bicapped square antiprism. The shortest Tm—O bonds are observed to the aqua ligands [2.2897 (18)–2.3360 (16) Å]. Similar to the pentahydrate, the nitrate anions show an asymmetric coordination with one shorter [2.4039 (17)–2.4677 (17) Å] and one longer Tm—O distance [2.5034 (18), 2.5252 (18), 2.991 (2) Å] each. In one case, this is so severe that the corresponding Tm—O distance is even larger than the distance between the Tm^III atom and the central N atoms of the two remaining anions, and the arrangement should therefore rather be described as a [9 + 1] coordination. The reason for this is probably the missing space in the coordination sphere of the Tm^III atom, which makes such a distance increase necessary. A qualitatively analogous observation of a single extended Ln—N distance was made for all isotypic compounds of other rare earth elements, but the relative extension of the distance in the structure described here is much larger than in all other examples, as can be expected for the representative with the smallest ion radius so far. The consideration including a reduced coordination number for the Tm^III atom is supported by the different shape of the respective nitrate ion. While two anions are very similar with two longer and one shorter N—O bonds for coordinating and non-coordinating O atoms, respectively, and one reduced O—N—O angle between the coordinating O atoms, the third anion exhibits only one longer N—O bond of 1.275 (2) Å, indicating the coordinating O atom, and two shorter and almost equal N—O distances of 1.232 (3) Å and 1.236 (3) Å with more regular O—N—O angles. However, all nitrate ions are planar with an O—N—O angular sum of 360.0°. The water molecules show O—H bond lengths between 0.73 (5)and 0.85 (4) Å and H—O—H angles between 105 (5) and 112 (4)°. The metal complexes and the water molecules build a three-dimensional network of hydrogen bonds, again of medium–strong to weak character (Table 2, Fig. 4). Nine of twelve independent H atoms form hydrogen bonds shorter than 2.2 Å with O—H⋯O angles greater than 164° while H6, H10, and H12 are involved in weak and bifurcated hydrogen bonds.

Table 2
Hydrogen-bond geometry (Å, °) for Tm(NO₃)₃·6H₂O

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H1⋯O14	0.85 (4)	1.89 (4)	2.730 (3)	170 (4)
O10—H2⋯O15	0.73 (5)	2.00 (5)	2.714 (3)	164 (5)
O11—H4⋯O15ⁱ	0.74 (4)	1.93 (4)	2.666 (2)	174 (4)
O11—H3⋯O7ⁱⁱ	0.81 (4)	2.20 (4)	3.006 (2)	175 (4)
O12—H5⋯O8ⁱⁱⁱ	0.80 (4)	2.15 (4)	2.943 (3)	172 (4)
O12—H6⋯O5^iv	0.79 (4)	2.57 (4)	3.260 (3)	147 (4)
O12—H6⋯O7^iv	0.79 (4)	2.61 (4)	3.269 (3)	142 (4)
O13—H7⋯O14^v	0.78 (4)	1.93 (4)	2.713 (3)	174 (4)
O13—H8⋯O5^vi	0.83 (5)	2.13 (5)	2.963 (2)	179 (5)
O14—H9⋯O6^vi	0.80 (4)	2.01 (4)	2.804 (3)	176 (4)
O14—H10⋯O3^iv	0.80 (5)	2.64 (5)	3.111 (3)	119 (4)
O14—H10⋯O3^vii	0.80 (5)	2.24 (5)	2.885 (2)	138 (4)
O15—H11⋯O9ⁱⁱ	0.79 (5)	2.01 (5)	2.782 (3)	168 (4)
O15—H12⋯O4^viii	0.79 (5)	2.29 (5)	2.926 (2)	137 (4)
O15—H12⋯O3^iv	0.79 (5)	2.47 (5)	2.992 (3)	125 (4)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) x+1, y, z; (v) ; (vi) ; (vii) ; (viii) x, y+1, z.

Figure 3
Asymmetric unit of Tm(NO₃)₃·6H₂O with the atom-numbering scheme. Anisotropic displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

Figure 4
Crystal structure of Tm(NO₃)₃·6H₂O in a view along [100]. Hydrogen bonds are shown as dotted lines up to an O⋯H distance of 2.5 Å. Anisotropic displacement ellipsoids of non-H atoms are drawn at the 50% probability level.

Interestingly, the molecular Tm complexes in both crystal structures exhibit an alleged higher symmetry, viz. a threefold rotation axis in the pentahydrate and a mirror plane in the hexahydrate, as illustrated in Fig. 5. However, these are pseudo-symmetries, with the higher symmetry violated at a molecular level and in the first coordination sphere, and incompatible with the space-group symmetry.

Figure 5
Structural details to emphasize the molecular pseudo-symmetry in the title compounds: (a) a pseudo-threefold rotation axis in the molecular complex present in Tm(NO₃)₃·5H₂O; (b) a pseudo-mirror plane in the molecular complex present in Tm(NO₃)₃·6H₂O. Anisotropic displacement ellipsoids of non-H atoms are drawn at the 50% probability level.

3. Database survey

The crystal structure of anhydrous Tm(NO₃)₃ was determined quite recently (Heinrichs, 2013 ), and one hydrated phase has been reported so far, i.e. the trihydrate (Riess, 2012). In addition, basic oxo-hydroxo-nitrate hydrates are known with Tm (Giester et al., 2009 ). The thulium nitrate pentahydrate adopts the Y(NO₃)₃·5H₂O type of structure (Eriksson, 1982; Klein, 2020 ), and is isotypic with the respective Eu (Ribár et al., 1986 ), Gd (Stockhause & Meyer, 1997 ), Dy, Er, Yb (Junk et al., 1999) and Ho compounds (Rincke et al., 2017). Tm(NO₃)₃·6H₂O is isotypic with the nitrate hexahydrates of Y (Ribár et al., 1980 ), Pr (Rumanova et al., 1964 ; Fuller & Jacobsen, 1976 ; Decadt et al., 2012), Nd (Rogers et al., 1983; Shi & Wang, 1991 ), Sm (Shi & Wang, 1990 ; Kawashima et al., 2000), Eu (Stumpf & Bolte, 2001; Ananyev et al., 2016 ), Gd (Ma et al., 1991 ; Taha et al., 2012) and Tb (Moret et al., 1990).

4. Synthesis and crystallization

[Tm(NO₃)₃(H₂O)₄]·H₂O was prepared by dissolving Tm₂O₃ (Fluka AG; 99.9%) in hot aqueous nitric acid (65%_wt). From saturated solutions, crystals with sizes up to the millimetre range were grown at room temperature within one day. Single crystals were removed, cleansed from the mother liquor and placed on a microscope slide in air. For the single-crystal data collection, crystals were immersed into perfluoroalkyl ether, which also acts as glue on a glass tip during the measurement. The remaining crystals were carefully ground to measure an X-ray powder pattern that, according to a comparison with the pattern simulated from the single-crystal structure determination, showed exclusively reflections of the pentahydrate. The crystals are hygroscopic and usually deliquesce within hours under ambient conditions depending on air humidity. Rapid re-crystallization within minutes can be induced by scratching on the glass slide. Surprisingly, from one recrystallization the hexahydrate [Tm(NO₃)₃(H₂O)₄]·2H₂O was obtained. All investigated crystals from this batch revealed the unit cell of the hexahydrate, so the crystallization seemed to result in a pure product in this case as well. Optically indistinguishable, the crystals of the hexahydrate showed the same deliquescence behaviour. It has not been possible to determine the exact conditions required to obtain the hexahydrate so far. According to EDX measurements, the crystals contain Tm as the only element heavier than oxygen.

5. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 3. In both structure refinements, all hydrogen atoms have been located from difference Fourier maps and refined with free atomic coordinates and isotropic displacement parameters.

Table 3
Experimental details

	Tm(NO₃)₃·5H₂O	Tm(NO₃)₃·6H₂O
Crystal data
Chemical formula	[Tm(NO₃)₃(H₂O)₄]·H₂O	[Tm(NO₃)₃(H₂O)₄]·2H₂O
M_r	445.04	463.06
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	223	223
a, b, c (Å)	6.5782 (4), 9.5213 (5), 10.4848 (6)	6.7050 (3), 8.9733 (4), 11.4915 (6)
α, β, γ (°)	63.696 (4), 84.656 (5), 76.146 (4)	70.924 (4), 88.908 (4), 68.923 (4)
V (Å³)	571.51 (6)	605.90 (5)
Z	2	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	7.85	7.41
Crystal size (mm)	0.25 × 0.2 × 0.2	0.4 × 0.2 × 0.15

Data collection
Diffractometer	Stoe StadiVari	Stoe StadiVari
Absorption correction	Empirical (using intensity measurements) (X-AREA; Stoe, 2015 )	Empirical (using intensity measurements) (X-AREA; Stoe, 2015)
T_min, T_max	0.798, 1.000	0.615, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	18549, 4113, 3394	29880, 4385, 3899
R_int	0.038	0.031
(sin θ/λ)_max (Å⁻¹)	0.756	0.756

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.029, 0.65	0.016, 0.035, 0.91
No. of reflections	4113	4385
No. of parameters	204	221
H-atom treatment	All H-atom parameters refined	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.94, −0.92	1.11, −1.19
Computer programs: X-AREA (Stoe, 2015), SHELXS97 (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), DIAMOND (Brandenburg & Putz, 2012 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2045553; 2045552

Crystal structure: contains datablocks global, TONi-2_223K, TONii-3_223K. DOI: https://doi.org/10.1107/S2056989020015388/wm5589sup1.cif

Structure factors: contains datablock TONi-2_223K. DOI: https://doi.org/10.1107/S2056989020015388/wm5589TONi-2_223Ksup2.hkl

Structure factors: contains datablock TONii-3_223K. DOI: https://doi.org/10.1107/S2056989020015388/wm5589TONii-3_223Ksup3.hkl

checkCIF report

Computing details top

For both structures, data collection: X-AREA (Stoe, 2015); cell refinement: X-AREA (Stoe, 2015); data reduction: X-AREA (Stoe, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Thulium nitrate (TONi-2_223K) top

Crystal data top

[Tm(NO₃)₃(H₂O)₄]·H₂O	Z = 2
M_r = 445.04	F(000) = 424
Triclinic, P1	D_x = 2.586 Mg m⁻³
a = 6.5782 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5213 (5) Å	Cell parameters from 15951 reflections
c = 10.4848 (6) Å	θ = 3.2–36.9°
α = 63.696 (4)°	µ = 7.85 mm⁻¹
β = 84.656 (5)°	T = 223 K
γ = 76.146 (4)°	Block, colourless
V = 571.51 (6) Å³	0.25 × 0.2 × 0.2 mm

Data collection top

STOE StadiVari diffractometer	4113 independent reflections
Radiation source: Genix 3D HF Mo	3394 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.038
Detector resolution: 5.81 pixels mm^-1	θ_max = 32.5°, θ_min = 3.2°
ω scans	h = −9→9
Absorption correction: empirical (using intensity measurements) (X-AREA; Stoe, 2015)	k = −13→14
T_min = 0.798, T_max = 1.000	l = −14→15
18549 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.017	All H-atom parameters refined
wR(F²) = 0.029	w = 1/[σ²(F_o²)] where P = (F_o² + 2F_c²)/3
S = 0.65	(Δ/σ)_max = 0.001
4113 reflections	Δρ_max = 0.94 e Å⁻³
204 parameters	Δρ_min = −0.92 e Å⁻³
0 restraints	Extinction correction: SHELXL-2014/7 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0130 (4)

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
Tm	0.24261 (2)	0.34935 (2)	0.29463 (2)	0.01335 (4)
N1	0.4678 (3)	0.2804 (2)	0.5557 (2)	0.0181 (4)
O1	0.2946 (3)	0.38136 (19)	0.50762 (18)	0.0237 (3)
O2	0.5532 (3)	0.21177 (19)	0.47971 (17)	0.0235 (3)
O3	0.5463 (4)	0.2559 (3)	0.6667 (2)	0.0334 (5)
N2	0.5187 (3)	0.2148 (2)	0.1245 (2)	0.0224 (4)
O4	0.4995 (3)	0.1419 (2)	0.25849 (18)	0.0281 (4)
O5	0.4049 (3)	0.35678 (19)	0.06621 (17)	0.0235 (3)
O6	0.6366 (4)	0.1552 (2)	0.0567 (2)	0.0393 (5)
N3	0.0240 (3)	0.6856 (2)	0.1466 (2)	0.0207 (4)
O7	0.0612 (3)	0.58072 (19)	0.09609 (18)	0.0229 (4)
O8	0.1039 (3)	0.63874 (19)	0.26683 (17)	0.0232 (3)
O9	−0.0817 (4)	0.8199 (2)	0.0805 (2)	0.0371 (5)
O10	−0.0906 (3)	0.3864 (2)	0.39356 (19)	0.0222 (3)
H1	−0.150 (6)	0.447 (4)	0.428 (4)	0.034 (8)*
H2	−0.182 (6)	0.374 (4)	0.360 (4)	0.028 (8)*
O11	0.1965 (3)	0.1013 (2)	0.46732 (19)	0.0221 (3)
H3	0.124 (7)	0.088 (5)	0.532 (5)	0.047 (11)*
H4	0.278 (6)	0.014 (5)	0.475 (4)	0.035 (9)*
O12	0.0243 (3)	0.2649 (2)	0.19433 (18)	0.0229 (3)
H5	0.038 (6)	0.169 (5)	0.212 (4)	0.041 (10)*
H6	0.009 (6)	0.311 (4)	0.106 (4)	0.035 (9)*
O13	0.5125 (3)	0.5005 (2)	0.22335 (18)	0.0207 (3)
H7	0.556 (8)	0.530 (5)	0.141 (5)	0.059 (12)*
H8	0.495 (7)	0.586 (5)	0.237 (4)	0.045 (10)*
O14	0.0035 (5)	0.9548 (2)	0.2793 (2)	0.0322 (5)
H9	0.120 (7)	0.892 (5)	0.285 (4)	0.038 (9)*
H10	−0.046 (9)	0.956 (6)	0.224 (6)	0.066 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tm	0.01449 (5)	0.01318 (5)	0.01242 (4)	−0.00290 (3)	−0.00004 (3)	−0.00565 (3)
N1	0.0201 (10)	0.0177 (8)	0.0181 (8)	−0.0059 (7)	−0.0007 (7)	−0.0082 (7)
O1	0.0221 (9)	0.0251 (8)	0.0241 (8)	0.0038 (7)	−0.0053 (6)	−0.0142 (7)
O2	0.0262 (9)	0.0215 (7)	0.0233 (8)	−0.0017 (7)	0.0005 (7)	−0.0118 (6)
O3	0.0384 (12)	0.0372 (10)	0.0277 (10)	−0.0024 (9)	−0.0141 (9)	−0.0170 (8)
N2	0.0248 (11)	0.0220 (9)	0.0214 (9)	−0.0042 (8)	0.0040 (8)	−0.0117 (8)
O4	0.0330 (10)	0.0251 (8)	0.0171 (8)	0.0029 (7)	0.0007 (7)	−0.0059 (6)
O5	0.0291 (10)	0.0197 (7)	0.0214 (8)	−0.0053 (7)	0.0058 (7)	−0.0097 (6)
O6	0.0454 (13)	0.0381 (10)	0.0335 (10)	0.0016 (9)	0.0120 (9)	−0.0224 (8)
N3	0.0231 (10)	0.0150 (8)	0.0220 (9)	−0.0010 (7)	−0.0039 (7)	−0.0072 (7)
O7	0.0329 (10)	0.0166 (7)	0.0192 (8)	−0.0016 (7)	−0.0056 (7)	−0.0084 (6)
O8	0.0266 (9)	0.0240 (8)	0.0225 (8)	−0.0042 (7)	−0.0037 (7)	−0.0131 (6)
O9	0.0451 (13)	0.0182 (8)	0.0380 (10)	0.0105 (8)	−0.0137 (9)	−0.0093 (8)
O10	0.0165 (9)	0.0288 (8)	0.0288 (9)	−0.0047 (7)	0.0026 (7)	−0.0198 (7)
O11	0.0238 (9)	0.0172 (7)	0.0205 (8)	−0.0036 (7)	0.0038 (7)	−0.0051 (6)
O12	0.0371 (10)	0.0185 (8)	0.0152 (8)	−0.0110 (7)	−0.0035 (7)	−0.0062 (6)
O13	0.0257 (9)	0.0196 (7)	0.0170 (8)	−0.0078 (6)	0.0028 (6)	−0.0073 (6)
O14	0.0520 (15)	0.0212 (9)	0.0236 (10)	−0.0045 (9)	0.0004 (9)	−0.0117 (8)

Geometric parameters (Å, º) top

Tm—O12	2.3235 (18)	N3—O9	1.216 (3)
Tm—O11	2.3235 (17)	N3—O8	1.256 (3)
Tm—O10	2.3526 (18)	N3—O7	1.290 (2)
Tm—O7	2.3980 (17)	O7—O8	2.153 (2)
Tm—O13	2.4089 (18)	O7—O9	2.184 (2)
Tm—O4	2.4181 (17)	O7—O12^vii	2.776 (2)
Tm—O1	2.4479 (16)	O7—O12	2.778 (2)
Tm—O5	2.5081 (16)	O7—O10	3.056 (3)
Tm—O8	2.5776 (15)	O7—O13	3.150 (3)
Tm—O2	2.6193 (18)	O8—O9	2.175 (2)
Tm—N2	2.9035 (19)	O8—O10	2.738 (3)
Tm—N3	2.9212 (18)	O8—O13	2.788 (2)
Tm—N1	2.9690 (19)	O8—O3^iv	2.969 (3)
N1—O3	1.220 (3)	O8—O14	2.982 (3)
N1—O2	1.257 (2)	O9—O14	3.040 (3)
N1—O1	1.276 (3)	O9—O6^v	3.153 (3)
O1—O2	2.144 (2)	O9—O6^viii	3.199 (2)
O1—O3	2.180 (3)	O10—O11	2.736 (2)
O1—O8	2.755 (2)	O10—O12	2.775 (2)
O1—O10ⁱ	2.849 (2)	O10—O1ⁱ	2.849 (2)
O1—O10	2.882 (3)	O10—O13^ix	2.996 (3)
O1—O13	3.035 (2)	O10—O2^ix	3.035 (3)
O1—O11	3.095 (2)	O10—H1	0.82 (4)
O2—O3	2.174 (2)	O10—H2	0.78 (4)
O2—O4	2.753 (2)	O11—O14ⁱ	2.739 (3)
O2—O11	2.827 (3)	O11—O12	2.777 (2)
O2—O13	2.844 (2)	O11—O2ⁱⁱ	2.874 (2)
O2—O11ⁱⁱ	2.874 (2)	O11—O4ⁱⁱ	3.253 (2)
O2—O10ⁱⁱⁱ	3.035 (3)	O11—H3	0.77 (5)
O3—O13^iv	2.953 (3)	O11—H4	0.85 (4)
O3—O8^iv	2.969 (3)	O12—O14^x	2.715 (3)
O3—O14^iv	3.095 (3)	O12—O7^vii	2.776 (2)
N2—O6	1.213 (3)	O12—O9^vii	3.288 (3)
N2—O4	1.271 (3)	O12—H5	0.83 (4)
N2—O5	1.277 (3)	O12—H6	0.83 (4)
O4—O5	2.146 (2)	O13—O5^v	2.784 (2)
O4—O6	2.184 (2)	O13—O3^iv	2.953 (3)
O4—O11	2.779 (3)	O13—O10ⁱⁱⁱ	2.996 (3)
O4—O12	3.088 (3)	O13—O6^v	3.286 (3)
O5—O6	2.181 (2)	O13—H7	0.82 (5)
O5—O13^v	2.784 (2)	O13—H8	0.86 (4)
O5—O13	2.786 (2)	O14—O12^xi	2.715 (3)
O5—O7	2.812 (2)	O14—O11ⁱ	2.739 (3)
O5—O12	2.867 (3)	O14—O3^iv	3.095 (3)
O5—O5^v	2.981 (3)	O14—O6^viii	3.132 (4)
O6—O14^vi	3.132 (4)	O14—H9	0.84 (4)
O6—O9^v	3.153 (3)	O14—H10	0.68 (6)
O6—O9^vi	3.199 (2)

O12—Tm—O11	73.38 (6)	N3—O8—O1	146.83 (13)
O12—Tm—O10	72.80 (7)	O7—O8—O1	114.60 (8)
O11—Tm—O10	71.63 (6)	O9—O8—O1	171.15 (11)
O12—Tm—O7	72.07 (6)	Tm—O8—O1	54.53 (5)
O11—Tm—O7	140.36 (7)	O10—O8—O1	63.30 (7)
O10—Tm—O7	80.06 (7)	N3—O8—O13	100.19 (13)
O12—Tm—O13	139.17 (6)	O7—O8—O13	78.06 (8)
O11—Tm—O13	137.72 (6)	O9—O8—O13	117.62 (10)
O10—Tm—O13	133.41 (6)	Tm—O8—O13	53.17 (5)
O7—Tm—O13	81.90 (6)	O10—O8—O13	104.61 (7)
O12—Tm—O4	81.26 (7)	O1—O8—O13	66.39 (6)
O11—Tm—O4	71.73 (6)	N3—O8—O3^iv	127.07 (15)
O10—Tm—O4	139.74 (7)	O7—O8—O3^iv	130.96 (11)
O7—Tm—O4	120.66 (6)	O9—O8—O3^iv	113.90 (10)
O13—Tm—O4	85.91 (6)	Tm—O8—O3^iv	107.97 (7)
O12—Tm—O1	142.71 (7)	O10—O8—O3^iv	137.66 (9)
O11—Tm—O1	80.83 (6)	O1—O8—O3^iv	74.92 (7)
O10—Tm—O1	73.77 (7)	O13—O8—O3^iv	61.63 (7)
O7—Tm—O1	117.47 (5)	N3—O8—O14	97.81 (13)
O13—Tm—O1	77.34 (6)	O7—O8—O14	130.15 (10)
O4—Tm—O1	115.79 (6)	O9—O8—O14	70.27 (8)
O12—Tm—O5	72.69 (6)	Tm—O8—O14	168.88 (9)
O11—Tm—O5	116.78 (6)	O10—O8—O14	129.72 (9)
O10—Tm—O5	139.64 (7)	O1—O8—O14	115.20 (8)
O7—Tm—O5	69.91 (6)	O13—O8—O14	120.95 (9)
O13—Tm—O5	69.01 (6)	O3^iv—O8—O14	62.67 (8)
O4—Tm—O5	51.62 (5)	N3—O9—O8	28.84 (12)
O1—Tm—O5	144.29 (6)	N3—O9—O7	30.33 (11)
O12—Tm—O8	113.85 (6)	O8—O9—O7	59.18 (7)
O11—Tm—O8	132.83 (6)	N3—O9—O14	95.93 (15)
O10—Tm—O8	67.31 (6)	O8—O9—O14	67.39 (8)
O7—Tm—O8	51.11 (5)	O7—O9—O14	125.90 (11)
O13—Tm—O8	67.90 (6)	N3—O9—O6^v	76.99 (16)
O4—Tm—O8	152.92 (6)	O8—O9—O6^v	82.55 (9)
O1—Tm—O8	66.42 (5)	O7—O9—O6^v	74.67 (9)
O5—Tm—O8	109.44 (5)	O14—O9—O6^v	91.35 (9)
O12—Tm—O2	136.38 (6)	N3—O9—O6^viii	152.81 (17)
O11—Tm—O2	69.47 (6)	O8—O9—O6^viii	124.77 (10)
O10—Tm—O2	114.60 (6)	O7—O9—O6^viii	170.46 (13)
O7—Tm—O2	149.67 (6)	O14—O9—O6^viii	60.20 (7)
O13—Tm—O2	68.73 (6)	O6^v—O9—O6^viii	113.72 (8)
O4—Tm—O2	66.13 (6)	Tm—O10—O11	53.69 (5)
O1—Tm—O2	49.93 (5)	Tm—O10—O8	60.27 (6)
O5—Tm—O2	104.73 (6)	O11—O10—O8	110.30 (8)
O8—Tm—O2	108.01 (5)	Tm—O10—O12	53.11 (5)
O12—Tm—N2	75.56 (6)	O11—O10—O12	60.49 (6)
O11—Tm—N2	94.20 (6)	O8—O10—O12	96.36 (7)
O10—Tm—N2	147.88 (7)	Tm—O10—O1ⁱ	130.59 (9)
O7—Tm—N2	95.49 (6)	O11—O10—O1ⁱ	143.50 (9)
O13—Tm—N2	76.27 (6)	O8—O10—O1ⁱ	73.51 (7)
O4—Tm—N2	25.62 (6)	O12—O10—O1ⁱ	155.76 (9)
O1—Tm—N2	133.73 (6)	Tm—O10—O1	54.63 (5)
O5—Tm—N2	26.00 (6)	O11—O10—O1	66.79 (7)
O8—Tm—N2	132.96 (6)	O8—O10—O1	58.62 (6)
O2—Tm—N2	85.07 (6)	O12—O10—O1	106.09 (8)
O12—Tm—N3	92.45 (6)	O1ⁱ—O10—O1	87.67 (7)
O11—Tm—N3	142.15 (6)	Tm—O10—O13^ix	122.60 (8)
O10—Tm—N3	70.66 (6)	O11—O10—O13^ix	128.05 (9)
O7—Tm—N3	25.75 (6)	O8—O10—O13^ix	103.81 (7)
O13—Tm—N3	74.57 (6)	O12—O10—O13^ix	78.12 (7)
O4—Tm—N3	141.95 (6)	O1ⁱ—O10—O13^ix	82.96 (7)
O1—Tm—N3	91.72 (5)	O1—O10—O13^ix	162.00 (8)
O5—Tm—N3	90.60 (5)	Tm—O10—O2^ix	135.89 (8)
O8—Tm—N3	25.43 (5)	O11—O10—O2^ix	90.74 (7)
O2—Tm—N3	131.08 (5)	O8—O10—O2^ix	158.09 (8)
N2—Tm—N3	116.50 (6)	O12—O10—O2^ix	88.57 (7)
O12—Tm—N1	145.99 (6)	O1ⁱ—O10—O2^ix	93.44 (7)
O11—Tm—N1	72.73 (6)	O1—O10—O2^ix	140.06 (8)
O10—Tm—N1	93.76 (6)	O13^ix—O10—O2^ix	56.26 (6)
O7—Tm—N1	137.60 (5)	Tm—O10—O7	50.62 (5)
O13—Tm—N1	72.24 (6)	O11—O10—O7	100.01 (7)
O4—Tm—N1	90.89 (6)	O8—O10—O7	43.18 (5)
O1—Tm—N1	24.96 (5)	O12—O10—O7	56.67 (6)
O5—Tm—N1	126.60 (6)	O1ⁱ—O10—O7	105.10 (7)
O8—Tm—N1	87.63 (5)	O1—O10—O7	88.42 (7)
O2—Tm—N1	25.01 (5)	O13^ix—O10—O7	79.30 (7)
N2—Tm—N1	109.73 (6)	O2^ix—O10—O7	129.22 (8)
N3—Tm—N1	112.83 (5)	Tm—O10—H1	133 (3)
O3—N1—O2	122.7 (2)	O11—O10—H1	140 (2)
O3—N1—O1	121.65 (19)	O8—O10—H1	77 (3)
O2—N1—O1	115.65 (18)	O12—O10—H1	159 (2)
O3—N1—Tm	175.24 (17)	O1ⁱ—O10—H1	5 (2)
O2—N1—Tm	61.74 (11)	O1—O10—H1	88 (3)
O1—N1—Tm	54.03 (10)	O13^ix—O10—H1	84 (3)
N1—O1—O2	31.90 (10)	O2^ix—O10—H1	91 (3)
N1—O1—O3	28.46 (11)	O7—O10—H1	110 (2)
O2—O1—O3	60.35 (8)	Tm—O10—H2	117 (2)
N1—O1—Tm	101.01 (12)	O11—O10—H2	103 (2)
O2—O1—Tm	69.19 (6)	O8—O10—H2	125 (3)
O3—O1—Tm	129.44 (9)	O12—O10—H2	64 (2)
N1—O1—O8	142.91 (14)	O1ⁱ—O10—H2	103 (2)
O2—O1—O8	117.71 (9)	O1—O10—H2	169 (2)
O3—O1—O8	152.42 (12)	O13^ix—O10—H2	26 (2)
Tm—O1—O8	59.05 (5)	O2^ix—O10—H2	39 (3)
N1—O1—O10ⁱ	125.68 (13)	O7—O10—H2	90 (3)
O2—O1—O10ⁱ	155.65 (10)	H1—O10—H2	103 (4)
O3—O1—O10ⁱ	97.77 (9)	Tm—O11—O10	54.68 (5)
Tm—O1—O10ⁱ	132.31 (7)	Tm—O11—O14ⁱ	126.09 (8)
O8—O1—O10ⁱ	76.13 (6)	O10—O11—O14ⁱ	79.46 (8)
N1—O1—O10	136.42 (14)	Tm—O11—O12	53.31 (5)
O2—O1—O10	111.95 (9)	O10—O11—O12	60.44 (6)
O3—O1—O10	149.48 (11)	O14ⁱ—O11—O12	128.28 (10)
Tm—O1—O10	51.60 (5)	Tm—O11—O4	55.71 (5)
O8—O1—O10	58.08 (6)	O10—O11—O4	108.60 (8)
O10ⁱ—O1—O10	92.33 (7)	O14ⁱ—O11—O4	163.22 (11)
N1—O1—O13	85.66 (12)	O12—O11—O4	67.54 (7)
O2—O1—O13	63.91 (7)	Tm—O11—O2	60.20 (5)
O3—O1—O13	105.20 (10)	O10—O11—O2	97.60 (7)
Tm—O1—O13	50.75 (5)	O14ⁱ—O11—O2	106.22 (9)
O8—O1—O13	57.34 (6)	O12—O11—O2	110.01 (8)
O10ⁱ—O1—O13	117.55 (8)	O4—O11—O2	58.83 (7)
O10—O1—O13	95.28 (7)	Tm—O11—O2ⁱⁱ	128.10 (9)
N1—O1—O11	82.07 (12)	O10—O11—O2ⁱⁱ	169.77 (9)
O2—O1—O11	62.22 (7)	O14ⁱ—O11—O2ⁱⁱ	102.25 (8)
O3—O1—O11	101.73 (9)	O12—O11—O2ⁱⁱ	112.15 (8)
Tm—O1—O11	47.83 (4)	O4—O11—O2ⁱⁱ	72.52 (7)
O8—O1—O11	100.20 (7)	O2—O11—O2ⁱⁱ	91.62 (7)
O10ⁱ—O1—O11	138.47 (9)	Tm—O11—O1	51.34 (5)
O10—O1—O11	54.35 (6)	O10—O11—O1	58.86 (6)
O13—O1—O11	92.12 (6)	O14ⁱ—O11—O1	82.73 (7)
N1—O2—O1	32.45 (11)	O12—O11—O1	100.57 (7)
N1—O2—O3	28.19 (11)	O4—O11—O1	88.96 (7)
O1—O2—O3	60.63 (8)	O2—O11—O1	42.16 (5)
N1—O2—Tm	93.26 (12)	O2ⁱⁱ—O11—O1	131.25 (8)
O1—O2—Tm	60.88 (6)	Tm—O11—O4ⁱⁱ	126.48 (8)
O3—O2—Tm	121.43 (9)	O10—O11—O4ⁱⁱ	135.39 (8)
N1—O2—O4	145.77 (15)	O14ⁱ—O11—O4ⁱⁱ	67.19 (8)
O1—O2—O4	114.04 (9)	O12—O11—O4ⁱⁱ	163.11 (9)
O3—O2—O4	170.50 (12)	O4—O11—O4ⁱⁱ	98.00 (7)
Tm—O2—O4	53.43 (5)	O2—O11—O4ⁱⁱ	66.31 (6)
N1—O2—O11	94.41 (14)	O2ⁱⁱ—O11—O4ⁱⁱ	52.98 (5)
O1—O2—O11	75.62 (8)	O1—O11—O4ⁱⁱ	87.35 (6)
O3—O2—O11	110.77 (10)	Tm—O11—H3	125 (3)
Tm—O2—O11	50.33 (5)	O10—O11—H3	75 (3)
O4—O2—O11	59.72 (7)	O14ⁱ—O11—H3	9 (3)
N1—O2—O13	94.71 (12)	O12—O11—H3	120 (3)
O1—O2—O13	73.45 (7)	O4—O11—H3	172 (3)
O3—O2—O13	111.95 (9)	O2—O11—H3	114 (3)
Tm—O2—O13	52.13 (5)	O2ⁱⁱ—O11—H3	105 (3)
O4—O2—O13	71.96 (6)	O1—O11—H3	87 (3)
O11—O2—O13	102.24 (7)	O4ⁱⁱ—O11—H3	75 (3)
N1—O2—O11ⁱⁱ	135.37 (13)	Tm—O11—H4	122 (3)
O1—O2—O11ⁱⁱ	156.10 (10)	O10—O11—H4	169 (2)
O3—O2—O11ⁱⁱ	110.89 (9)	O14ⁱ—O11—H4	108 (2)
Tm—O2—O11ⁱⁱ	121.11 (7)	O12—O11—H4	109 (2)
O4—O2—O11ⁱⁱ	70.59 (6)	O4—O11—H4	66 (2)
O11—O2—O11ⁱⁱ	88.37 (7)	O2—O11—H4	88 (3)
O13—O2—O11ⁱⁱ	128.19 (8)	O2ⁱⁱ—O11—H4	6 (3)
N1—O2—O10ⁱⁱⁱ	93.92 (13)	O1—O11—H4	129 (3)
O1—O2—O10ⁱⁱⁱ	103.88 (9)	O4ⁱⁱ—O11—H4	56 (2)
O3—O2—O10ⁱⁱⁱ	83.51 (9)	H3—O11—H4	111 (4)
Tm—O2—O10ⁱⁱⁱ	113.27 (7)	Tm—O12—O14^x	125.11 (10)
O4—O2—O10ⁱⁱⁱ	105.78 (8)	Tm—O12—O10	54.08 (5)
O11—O2—O10ⁱⁱⁱ	162.02 (8)	O14^x—O12—O10	116.16 (9)
O13—O2—O10ⁱⁱⁱ	61.18 (6)	Tm—O12—O7^vii	120.70 (8)
O11ⁱⁱ—O2—O10ⁱⁱⁱ	96.80 (7)	O14^x—O12—O7^vii	105.94 (8)
N1—O3—O2	29.13 (11)	O10—O12—O7^vii	128.10 (8)
N1—O3—O1	29.90 (11)	Tm—O12—O11	53.31 (5)
O2—O3—O1	59.02 (8)	O14^x—O12—O11	75.07 (8)
N1—O3—O13^iv	123.70 (15)	O10—O12—O11	59.06 (6)
O2—O3—O13^iv	146.33 (11)	O7^vii—O12—O11	167.99 (10)
O1—O3—O13^iv	96.81 (9)	Tm—O12—O7	55.21 (5)
N1—O3—O8^iv	133.41 (18)	O14^x—O12—O7	176.85 (10)
O2—O3—O8^iv	120.98 (12)	O10—O12—O7	66.77 (6)
O1—O3—O8^iv	132.24 (11)	O7^vii—O12—O7	72.20 (7)
O13^iv—O3—O8^iv	56.18 (6)	O11—O12—O7	106.19 (8)
N1—O3—O14^iv	113.40 (16)	Tm—O12—O5	56.63 (5)
O2—O3—O14^iv	84.49 (9)	O14^x—O12—O5	117.49 (9)
O1—O3—O14^iv	142.73 (10)	O10—O12—O5	107.92 (8)
O13^iv—O3—O14^iv	112.24 (8)	O7^vii—O12—O5	75.17 (7)
O8^iv—O3—O14^iv	58.87 (6)	O11—O12—O5	93.64 (8)
O6—N2—O4	122.98 (19)	O7—O12—O5	59.73 (6)
O6—N2—O5	122.2 (2)	Tm—O12—O4	50.70 (5)
O4—N2—O5	114.76 (17)	O14^x—O12—O4	87.49 (9)
O6—N2—Tm	178.28 (17)	O10—O12—O4	99.49 (7)
O4—N2—Tm	55.33 (10)	O7^vii—O12—O4	111.72 (8)
O5—N2—Tm	59.44 (10)	O11—O12—O4	56.27 (6)
N2—O4—O5	32.70 (10)	O7—O12—O4	90.85 (7)
N2—O4—O6	27.78 (11)	O5—O12—O4	42.04 (5)
O5—O4—O6	60.48 (8)	Tm—O12—O9^vii	131.81 (9)
N2—O4—Tm	99.05 (12)	O14^x—O12—O9^vii	70.05 (7)
O5—O4—Tm	66.35 (6)	O10—O12—O9^vii	168.34 (9)
O6—O4—Tm	126.84 (9)	O7^vii—O12—O9^vii	41.15 (5)
N2—O4—O2	133.14 (15)	O11—O12—O9^vii	132.43 (8)
O5—O4—O2	111.36 (9)	O7—O12—O9^vii	107.30 (7)
O6—O4—O2	141.71 (12)	O5—O12—O9^vii	75.57 (7)
Tm—O4—O2	60.45 (5)	O4—O12—O9^vii	90.46 (7)
N2—O4—O11	140.81 (15)	Tm—O12—H5	123 (3)
O5—O4—O11	112.74 (9)	O14^x—O12—H5	10 (3)
O6—O4—O11	156.42 (13)	O10—O12—H5	124 (3)
Tm—O4—O11	52.55 (5)	O7^vii—O12—H5	102 (3)
O2—O4—O11	61.45 (6)	O11—O12—H5	77 (3)
N2—O4—O12	84.97 (14)	O7—O12—H5	166 (3)
O5—O4—O12	63.46 (7)	O5—O12—H5	107 (3)
O6—O4—O12	104.30 (10)	O4—O12—H5	80 (3)
Tm—O4—O12	48.04 (5)	O9^vii—O12—H5	63 (3)
O2—O4—O12	103.44 (7)	Tm—O12—H6	118 (3)
O11—O4—O12	56.19 (6)	O14^x—O12—H6	107 (2)
N2—O5—O4	32.54 (11)	O10—O12—H6	130 (2)
N2—O5—O6	28.07 (11)	O7^vii—O12—H6	4 (3)
O4—O5—O6	60.61 (8)	O11—O12—H6	164 (3)
N2—O5—Tm	94.56 (12)	O7—O12—H6	71 (2)
O4—O5—Tm	62.03 (6)	O5—O12—H6	71 (3)
O6—O5—Tm	122.63 (9)	O4—O12—H6	107 (3)
N2—O5—O13^v	109.94 (13)	O9^vii—O12—H6	40 (2)
O4—O5—O13^v	142.41 (9)	H5—O12—H6	102 (4)
O6—O5—O13^v	81.90 (8)	Tm—O13—O5^v	116.85 (8)
Tm—O5—O13^v	155.31 (8)	Tm—O13—O5	57.18 (5)
N2—O5—O13	102.32 (14)	O5^v—O13—O5	64.70 (7)
O4—O5—O13	82.54 (8)	Tm—O13—O8	58.93 (5)
O6—O5—O13	117.15 (11)	O5^v—O13—O8	108.57 (8)
Tm—O5—O13	53.82 (5)	O5—O13—O8	96.27 (7)
O13^v—O5—O13	115.30 (7)	Tm—O13—O2	59.14 (5)
N2—O5—O7	146.29 (14)	O5^v—O13—O2	147.07 (8)
O4—O5—O7	114.45 (9)	O5—O13—O2	92.32 (7)
O6—O5—O7	170.40 (11)	O8—O13—O2	96.59 (7)
Tm—O5—O7	53.21 (5)	Tm—O13—O3^iv	113.42 (8)
O13^v—O5—O7	103.03 (7)	O5^v—O13—O3^iv	108.73 (8)
O13—O5—O7	68.48 (6)	O5—O13—O3^iv	155.31 (9)
N2—O5—O12	94.81 (14)	O8—O13—O3^iv	62.20 (7)
O4—O5—O12	74.50 (8)	O2—O13—O3^iv	101.59 (7)
O6—O5—O12	111.87 (10)	Tm—O13—O10ⁱⁱⁱ	121.66 (7)
Tm—O5—O12	50.68 (5)	O5^v—O13—O10ⁱⁱⁱ	110.19 (8)
O13^v—O5—O12	126.93 (9)	O5—O13—O10ⁱⁱⁱ	124.94 (8)
O13—O5—O12	103.34 (7)	O8—O13—O10ⁱⁱⁱ	132.34 (8)
O7—O5—O12	58.56 (6)	O2—O13—O10ⁱⁱⁱ	62.57 (6)
N2—O5—O5^v	121.20 (17)	O3^iv—O13—O10ⁱⁱⁱ	79.74 (7)
O4—O5—O5^v	128.22 (13)	Tm—O13—O1	51.90 (5)
O6—O5—O5^v	107.16 (11)	O5^v—O13—O1	163.64 (9)
Tm—O5—O5^v	107.25 (8)	O5—O13—O1	108.19 (7)
O13^v—O5—O5^v	57.69 (6)	O8—O13—O1	56.27 (6)
O13—O5—O5^v	57.60 (7)	O2—O13—O1	42.63 (5)
O7—O5—O5^v	82.40 (7)	O3^iv—O13—O1	71.17 (7)
O12—O5—O5^v	140.96 (9)	O10ⁱⁱⁱ—O13—O1	86.04 (6)
N2—O6—O5	29.68 (12)	Tm—O13—O7	48.90 (5)
N2—O6—O4	29.23 (11)	O5^v—O13—O7	79.82 (7)
O5—O6—O4	58.91 (7)	O5—O13—O7	56.15 (6)
N2—O6—O14^vi	99.61 (16)	O8—O13—O7	41.95 (5)
O5—O6—O14^vi	122.89 (10)	O2—O13—O7	107.68 (8)
O4—O6—O14^vi	75.58 (9)	O3^iv—O13—O7	99.84 (7)
N2—O6—O9^v	136.91 (18)	O10ⁱⁱⁱ—O13—O7	169.66 (8)
O5—O6—O9^v	124.28 (11)	O1—O13—O7	84.06 (7)
O4—O6—O9^v	134.81 (12)	Tm—O13—O6^v	111.12 (7)
O14^vi—O6—O9^v	67.17 (7)	O5^v—O13—O6^v	41.08 (5)
N2—O6—O9^vi	142.10 (16)	O5—O13—O6^v	86.61 (7)
O5—O6—O9^vi	169.33 (12)	O8—O13—O6^v	71.96 (6)
O4—O6—O9^vi	113.34 (10)	O2—O13—O6^v	168.28 (9)
O14^vi—O6—O9^vi	57.38 (6)	O3^iv—O13—O6^v	75.62 (6)
O9^v—O6—O9^vi	66.27 (8)	O10ⁱⁱⁱ—O13—O6^v	127.02 (8)
O9—N3—O8	123.31 (19)	O1—O13—O6^v	126.97 (7)
O9—N3—O7	121.3 (2)	O7—O13—O6^v	62.22 (6)
O8—N3—O7	115.44 (17)	Tm—O13—H7	119 (3)
O9—N3—Tm	173.32 (18)	O5^v—O13—H7	10 (3)
O8—N3—Tm	61.80 (10)	O5—O13—H7	64 (3)
O7—N3—Tm	53.84 (10)	O8—O13—H7	119 (3)
N3—O7—O8	31.79 (10)	O2—O13—H7	138 (3)
N3—O7—O9	28.42 (11)	O3^iv—O13—H7	114 (3)
O8—O7—O9	60.21 (8)	O10ⁱⁱⁱ—O13—H7	102 (3)
N3—O7—Tm	100.41 (12)	O1—O13—H7	171 (3)
O8—O7—Tm	68.76 (6)	O7—O13—H7	88 (3)
O9—O7—Tm	128.67 (10)	O6^v—O13—H7	51 (3)
N3—O7—O12^vii	109.38 (13)	Tm—O13—H8	119 (3)
O8—O7—O12^vii	139.23 (9)	O5^v—O13—H8	97 (3)
O9—O7—O12^vii	82.11 (8)	O5—O13—H8	148 (3)
Tm—O7—O12^vii	148.08 (8)	O8—O13—H8	63 (3)
N3—O7—O12	135.69 (15)	O2—O13—H8	114 (3)
O8—O7—O12	112.27 (9)	O3^iv—O13—H8	12 (3)
O9—O7—O12	146.72 (12)	O10ⁱⁱⁱ—O13—H8	86 (3)
Tm—O7—O12	52.72 (5)	O1—O13—H8	82 (3)
O12^vii—O7—O12	107.80 (7)	O7—O13—H8	96 (3)
N3—O7—O5	138.14 (16)	O6^v—O13—H8	64 (3)
O8—O7—O5	112.81 (9)	H7—O13—H8	103 (4)
O9—O7—O5	151.26 (12)	O12^xi—O14—O11ⁱ	99.62 (8)
Tm—O7—O5	56.88 (5)	O12^xi—O14—O8	155.24 (10)
O12^vii—O7—O5	92.35 (7)	O11ⁱ—O14—O8	104.73 (8)
O12—O7—O5	61.71 (6)	O12^xi—O14—O9	124.30 (10)
N3—O7—O10	79.13 (13)	O11ⁱ—O14—O9	123.04 (11)
O8—O7—O10	60.53 (7)	O8—O14—O9	42.34 (5)
O9—O7—O10	97.66 (9)	O12^xi—O14—O3^iv	108.74 (10)
Tm—O7—O10	49.32 (5)	O11ⁱ—O14—O3^iv	109.99 (9)
O12^vii—O7—O10	146.96 (10)	O8—O14—O3^iv	58.46 (7)
O12—O7—O10	56.57 (6)	O9—O14—O3^iv	89.88 (8)
O5—O7—O10	101.99 (7)	O12^xi—O14—O6^viii	75.69 (8)
N3—O7—O13	82.94 (13)	O11ⁱ—O14—O6^viii	102.46 (10)
O8—O7—O13	59.99 (7)	O8—O14—O6^viii	103.01 (9)
O9—O7—O13	104.46 (10)	O9—O14—O6^viii	62.42 (7)
Tm—O7—O13	49.20 (5)	O3^iv—O14—O6^viii	145.65 (9)
O12^vii—O7—O13	122.65 (9)	O12^xi—O14—H9	114 (3)
O12—O7—O13	96.65 (7)	O11ⁱ—O14—H9	115 (3)
O5—O7—O13	55.37 (6)	O8—O14—H9	50 (3)
O10—O7—O13	89.60 (7)	O9—O14—H9	80 (3)
N3—O8—O7	32.77 (10)	O3^iv—O14—H9	10 (3)
N3—O8—O9	27.84 (10)	O6^viii—O14—H9	137 (3)
O7—O8—O9	60.61 (8)	O12^xi—O14—H10	104 (5)
N3—O8—Tm	92.77 (11)	O11ⁱ—O14—H10	120 (5)
O7—O8—Tm	60.13 (6)	O8—O14—H10	67 (4)
O9—O8—Tm	120.49 (8)	O9—O14—H10	25 (4)
N3—O8—O10	93.66 (14)	O3^iv—O14—H10	112 (5)
O7—O8—O10	76.28 (8)	O6^viii—O14—H10	37 (4)
O9—O8—O10	107.87 (10)	H9—O14—H10	103 (5)
Tm—O8—O10	52.43 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H1···O1ⁱ	0.82 (4)	2.03 (4)	2.849 (2)	174 (3)
O10—H2···O13^ix	0.78 (4)	2.32 (4)	2.996 (3)	145 (3)
O10—H2···O2^ix	0.78 (4)	2.48 (4)	3.035 (3)	129 (3)
O11—H3···O14ⁱ	0.77 (5)	1.98 (5)	2.739 (3)	167 (5)
O11—H4···O2ⁱⁱ	0.85 (4)	2.03 (4)	2.874 (2)	171 (4)
O12—H5···O14^x	0.83 (4)	1.90 (4)	2.715 (3)	165 (4)
O12—H6···O7^vii	0.83 (4)	1.95 (4)	2.776 (2)	174 (4)
O13—H7···O5^v	0.82 (5)	1.98 (5)	2.784 (2)	166 (4)
O13—H8···O3^iv	0.86 (4)	2.12 (4)	2.953 (3)	163 (4)
O14—H9···O3^iv	0.84 (4)	2.27 (5)	3.095 (3)	167 (4)
O14—H10···O9	0.68 (6)	2.44 (6)	3.040 (3)	148 (5)
O14—H10···O6^viii	0.68 (6)	2.62 (6)	3.132 (4)	134 (5)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+1, −z; (vii) −x, −y+1, −z; (viii) x−1, y+1, z; (ix) x−1, y, z; (x) x, y−1, z.

Thulium nitrate (TONii-3_223K) top

Crystal data top

[Tm(NO₃)₃(H₂O)₄]·2H₂O	Z = 2
M_r = 463.06	F(000) = 444
Triclinic, P1	D_x = 2.538 Mg m⁻³
a = 6.7050 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9733 (4) Å	Cell parameters from 47483 reflections
c = 11.4915 (6) Å	θ = 2.6–36.6°
α = 70.924 (4)°	µ = 7.41 mm⁻¹
β = 88.908 (4)°	T = 223 K
γ = 68.923 (4)°	Block, colourless
V = 605.90 (5) Å³	0.4 × 0.2 × 0.15 mm

Data collection top

STOE StadiVari diffractometer	4385 independent reflections
Radiation source: Genix 3D HF Mo	3899 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.031
Detector resolution: 5.81 pixels mm^-1	θ_max = 32.5°, θ_min = 3.3°
ω scans	h = −10→10
Absorption correction: empirical (using intensity measurements) (X-AREA; Stoe, 2015)	k = −13→13
T_min = 0.615, T_max = 1.000	l = −17→17
29880 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.016	All H-atom parameters refined
wR(F²) = 0.035	w = 1/[σ²(F_o²) + (0.020P)²] where P = (F_o² + 2F_c²)/3
S = 0.91	(Δ/σ)_max < 0.001
4385 reflections	Δρ_max = 1.11 e Å⁻³
221 parameters	Δρ_min = −1.18 e Å⁻³
0 restraints	Extinction correction: SHELXL-2014/7 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0687 (8)

Special details top

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

	x	y	z	U_iso*/U_eq
Tm	0.19543 (2)	0.41275 (2)	0.27232 (2)	0.01566 (4)
N1	−0.1763 (3)	0.7245 (2)	0.18627 (18)	0.0219 (3)
O1	−0.1088 (3)	0.6386 (2)	0.29939 (16)	0.0306 (4)
O2	−0.0716 (3)	0.6650 (2)	0.10973 (17)	0.0332 (4)
O3	−0.3348 (3)	0.8577 (2)	0.15483 (19)	0.0338 (4)
N2	0.0790 (3)	0.1833 (2)	0.18432 (18)	0.0239 (4)
O4	0.2565 (3)	0.1444 (2)	0.24492 (17)	0.0283 (3)
O5	−0.0588 (3)	0.3320 (2)	0.16876 (17)	0.0282 (3)
O6	0.0422 (4)	0.0843 (2)	0.14426 (19)	0.0358 (4)
N3	0.0931 (3)	0.1599 (2)	0.50588 (18)	0.0216 (3)
O7	−0.0255 (3)	0.2987 (2)	0.42350 (16)	0.0267 (3)
O8	0.2889 (3)	0.1045 (3)	0.4993 (2)	0.0356 (4)
O9	0.0120 (3)	0.0838 (2)	0.59033 (18)	0.0367 (4)
O10	0.3559 (3)	0.6083 (2)	0.22157 (17)	0.0282 (4)
H1	0.361 (6)	0.677 (5)	0.151 (4)	0.049 (10)*
H2	0.385 (7)	0.637 (6)	0.269 (4)	0.051 (11)*
O11	0.2745 (3)	0.4539 (2)	0.45290 (15)	0.0234 (3)
H3	0.200 (7)	0.521 (5)	0.484 (4)	0.048 (11)*
H4	0.367 (6)	0.390 (5)	0.499 (3)	0.034 (9)*
O12	0.5603 (3)	0.2458 (2)	0.32343 (18)	0.0251 (3)
H5	0.606 (6)	0.147 (5)	0.366 (3)	0.037 (9)*
H6	0.652 (7)	0.283 (5)	0.310 (4)	0.049 (11)*
O13	0.3038 (3)	0.4359 (2)	0.07487 (15)	0.0230 (3)
H7	0.400 (7)	0.363 (5)	0.063 (4)	0.046 (10)*
H8	0.236 (7)	0.500 (6)	0.006 (4)	0.059 (12)*
O14	0.3663 (3)	0.8009 (2)	−0.01622 (17)	0.0272 (3)
H9	0.252 (7)	0.832 (5)	−0.055 (4)	0.039 (10)*
H10	0.391 (7)	0.883 (6)	−0.019 (4)	0.058 (12)*
O15	0.4146 (3)	0.7754 (2)	0.36863 (17)	0.0244 (3)
H11	0.301 (7)	0.813 (6)	0.390 (4)	0.052 (12)*
H12	0.439 (8)	0.856 (6)	0.327 (4)	0.066 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tm	0.01512 (5)	0.01444 (4)	0.01475 (5)	−0.00368 (3)	0.00155 (2)	−0.00370 (3)
N1	0.0208 (8)	0.0134 (7)	0.0251 (9)	−0.0038 (6)	0.0013 (7)	−0.0012 (6)
O1	0.0303 (9)	0.0238 (8)	0.0203 (8)	0.0029 (7)	0.0054 (6)	−0.0003 (6)
O2	0.0341 (9)	0.0324 (9)	0.0227 (8)	0.0000 (7)	0.0010 (7)	−0.0103 (7)
O3	0.0260 (8)	0.0168 (7)	0.0389 (10)	0.0031 (6)	0.0023 (7)	0.0028 (7)
N2	0.0287 (9)	0.0200 (8)	0.0211 (8)	−0.0114 (7)	−0.0005 (7)	−0.0019 (7)
O4	0.0266 (8)	0.0189 (7)	0.0328 (9)	−0.0058 (6)	−0.0084 (7)	−0.0028 (6)
O5	0.0235 (8)	0.0266 (8)	0.0298 (8)	−0.0052 (6)	−0.0022 (6)	−0.0081 (7)
O6	0.0485 (12)	0.0275 (9)	0.0345 (10)	−0.0192 (8)	−0.0063 (8)	−0.0084 (7)
N3	0.0214 (8)	0.0162 (7)	0.0242 (9)	−0.0049 (6)	0.0059 (7)	−0.0056 (6)
O7	0.0282 (8)	0.0178 (7)	0.0252 (8)	−0.0058 (6)	0.0035 (6)	0.0004 (6)
O8	0.0191 (8)	0.0347 (10)	0.0532 (12)	−0.0060 (7)	0.0103 (8)	−0.0200 (9)
O9	0.0394 (10)	0.0256 (8)	0.0320 (9)	−0.0102 (8)	0.0145 (8)	0.0039 (7)
O10	0.0495 (11)	0.0276 (8)	0.0170 (7)	−0.0257 (8)	0.0066 (7)	−0.0073 (6)
O11	0.0259 (8)	0.0216 (7)	0.0160 (7)	−0.0025 (6)	−0.0007 (6)	−0.0050 (6)
O12	0.0169 (7)	0.0180 (7)	0.0331 (9)	−0.0032 (6)	−0.0001 (6)	−0.0029 (6)
O13	0.0257 (8)	0.0220 (7)	0.0165 (7)	−0.0040 (6)	0.0027 (6)	−0.0061 (6)
O14	0.0336 (9)	0.0208 (8)	0.0258 (8)	−0.0112 (7)	0.0027 (7)	−0.0049 (6)
O15	0.0267 (8)	0.0183 (7)	0.0249 (8)	−0.0065 (6)	−0.0009 (7)	−0.0050 (6)

Geometric parameters (Å, º) top

Tm—O10	2.2897 (18)	O7—O8	2.162 (3)
Tm—O11	2.3255 (17)	O7—O9	2.171 (2)
Tm—O12	2.3276 (17)	O7—O11	2.907 (3)
Tm—O13	2.3360 (16)	O7—O11ⁱ	3.006 (2)
Tm—O1	2.4039 (17)	O8—O9	2.151 (3)
Tm—O4	2.4179 (18)	O8—O8^vii	2.774 (4)
Tm—O7	2.4677 (17)	O8—O12^vii	2.943 (3)
Tm—O2	2.5034 (18)	O8—O11	2.969 (3)
Tm—O5	2.5252 (18)	O8—O12	2.974 (3)
Tm—N1	2.8787 (18)	O8—O15^viii	3.184 (3)
Tm—N2	2.902 (2)	O9—O15ⁱ	2.782 (3)
Tm—O8	2.991 (2)	O9—O9^vi	2.970 (5)
Tm—N3	3.1452 (18)	O9—O6^vi	3.009 (3)
N1—O3	1.227 (2)	O10—O11	2.714 (2)
N1—O2	1.251 (3)	O10—O15	2.714 (3)
N1—O1	1.267 (2)	O10—O14	2.730 (3)
O1—O2	2.134 (2)	O10—O13	2.734 (2)
O1—O3	2.177 (2)	O10—O12	2.863 (3)
O1—O7	2.758 (2)	O10—H1	0.85 (4)
O1—O11	2.768 (3)	O10—H2	0.73 (5)
O1—O11ⁱ	3.004 (2)	O11—O15^viii	2.666 (2)
O1—O10	3.166 (3)	O11—O12	2.917 (3)
O1—O15ⁱⁱ	3.174 (3)	O11—O1ⁱ	3.004 (2)
O2—O3	2.175 (3)	O11—O7ⁱ	3.006 (2)
O2—O13	2.738 (3)	O11—O15	3.199 (3)
O2—O5	2.809 (3)	O11—H3	0.81 (4)
O2—O10	2.965 (3)	O11—H4	0.74 (4)
O2—O6ⁱⁱⁱ	3.102 (3)	O12—O8^vii	2.943 (3)
O2—O13ⁱⁱⁱ	3.184 (3)	O12—O13	2.986 (3)
O3—O14^iv	2.885 (2)	O12—O9^vii	3.170 (3)
O3—O15ⁱⁱ	2.992 (3)	O12—H5	0.80 (4)
O3—O14ⁱⁱ	3.111 (3)	O12—H6	0.79 (4)
N2—O6	1.221 (3)	O13—O14^ix	2.713 (3)
N2—O4	1.263 (3)	O13—O5ⁱⁱⁱ	2.963 (2)
N2—O5	1.277 (3)	O13—O2ⁱⁱⁱ	3.184 (3)
O4—O5	2.148 (2)	O13—H7	0.78 (4)
O4—O6	2.173 (3)	O13—H8	0.83 (5)
O4—O12	2.781 (3)	O14—O13^ix	2.713 (3)
O4—O13	2.827 (2)	O14—O6ⁱⁱⁱ	2.804 (3)
O4—O8	2.829 (3)	O14—O3^iv	2.885 (2)
O4—O15^v	2.926 (2)	O14—O3^x	3.111 (3)
O4—O7	3.087 (3)	O14—H9	0.80 (4)
O5—O6	2.190 (3)	O14—H10	0.80 (5)
O5—O7	2.849 (3)	O15—O11^viii	2.666 (2)
O5—O13ⁱⁱⁱ	2.963 (2)	O15—O9ⁱ	2.782 (3)
O5—O13	2.969 (2)	O15—O4^xi	2.926 (2)
O6—O14ⁱⁱⁱ	2.804 (3)	O15—O3^x	2.992 (3)
O6—O9^vi	3.009 (3)	O15—O1^x	3.174 (3)
O6—O2ⁱⁱⁱ	3.102 (3)	O15—O8^viii	3.184 (3)
N3—O9	1.232 (2)	O15—H11	0.79 (5)
N3—O8	1.236 (3)	O15—H12	0.79 (5)
N3—O7	1.275 (2)

O10—Tm—O11	72.03 (6)	O7—O8—O12	100.29 (9)
O10—Tm—O12	76.62 (7)	O8^vii—O8—O12	61.49 (8)
O11—Tm—O12	77.63 (7)	O4—O8—O12	57.20 (6)
O10—Tm—O13	72.46 (6)	O12^vii—O8—O12	124.10 (7)
O11—Tm—O13	141.28 (6)	O11—O8—O12	58.78 (6)
O12—Tm—O13	79.64 (7)	N3—O8—Tm	85.50 (14)
O10—Tm—O1	84.81 (7)	O9—O8—Tm	114.83 (9)
O11—Tm—O1	71.62 (6)	O7—O8—Tm	54.39 (6)
O12—Tm—O1	147.76 (7)	O8^vii—O8—Tm	106.06 (10)
O13—Tm—O1	119.66 (6)	O4—O8—Tm	49.00 (5)
O10—Tm—O4	136.37 (7)	O12^vii—O8—Tm	164.48 (8)
O11—Tm—O4	127.07 (6)	O11—O8—Tm	45.93 (4)
O12—Tm—O4	71.71 (6)	O12—O8—Tm	45.93 (5)
O13—Tm—O4	72.95 (6)	N3—O8—O15^viii	118.44 (15)
O1—Tm—O4	136.08 (7)	O9—O8—O15^viii	114.99 (11)
O10—Tm—O7	142.62 (6)	O7—O8—O15^viii	113.47 (9)
O11—Tm—O7	74.59 (6)	O8^vii—O8—O15^viii	73.26 (9)
O12—Tm—O7	112.05 (6)	O4—O8—O15^viii	125.89 (8)
O13—Tm—O7	143.65 (6)	O12^vii—O8—O15^viii	95.36 (8)
O1—Tm—O7	68.96 (6)	O11—O8—O15^viii	51.20 (6)
O4—Tm—O7	78.37 (6)	O12—O8—O15^viii	68.83 (7)
O10—Tm—O2	76.28 (7)	Tm—O8—O15^viii	90.93 (6)
O11—Tm—O2	116.27 (6)	N3—O9—O8	29.45 (12)
O12—Tm—O2	143.26 (7)	N3—O9—O7	30.60 (11)
O13—Tm—O2	68.82 (6)	O8—O9—O7	60.05 (9)
O1—Tm—O2	51.50 (6)	N3—O9—O15ⁱ	122.54 (15)
O4—Tm—O2	114.16 (6)	O8—O9—O15ⁱ	151.29 (11)
O7—Tm—O2	104.56 (6)	O7—O9—O15ⁱ	92.26 (9)
O10—Tm—O5	138.32 (6)	N3—O9—O9^vi	81.16 (15)
O11—Tm—O5	143.50 (6)	O8—O9—O9^vi	81.92 (10)
O12—Tm—O5	122.22 (6)	O7—O9—O9^vi	82.92 (10)
O13—Tm—O5	75.17 (6)	O15ⁱ—O9—O9^vi	103.45 (11)
O1—Tm—O5	89.05 (6)	N3—O9—O6^vi	155.54 (18)
O4—Tm—O5	51.46 (6)	O8—O9—O6^vi	132.39 (12)
O7—Tm—O5	69.56 (6)	O7—O9—O6^vi	154.89 (11)
O2—Tm—O5	67.92 (6)	O15ⁱ—O9—O6^vi	70.34 (7)
O10—Tm—N1	79.34 (6)	O9^vi—O9—O6^vi	117.98 (10)
O11—Tm—N1	94.01 (6)	Tm—O10—O11	54.60 (5)
O12—Tm—N1	155.94 (6)	Tm—O10—O15	125.53 (8)
O13—Tm—N1	94.17 (6)	O11—O10—O15	72.21 (7)
O1—Tm—N1	25.80 (6)	Tm—O10—O14	123.63 (9)
O4—Tm—N1	128.96 (6)	O11—O10—O14	170.18 (10)
O7—Tm—N1	86.74 (5)	O15—O10—O14	106.61 (8)
O2—Tm—N1	25.70 (6)	Tm—O10—O13	54.55 (5)
O5—Tm—N1	77.55 (6)	O11—O10—O13	107.65 (8)
O10—Tm—N2	143.67 (6)	O15—O10—O13	179.02 (11)
O11—Tm—N2	142.17 (6)	O14—O10—O13	73.69 (7)
O12—Tm—N2	96.51 (6)	Tm—O10—O12	52.28 (5)
O13—Tm—N2	71.21 (6)	O11—O10—O12	63.00 (7)
O1—Tm—N2	113.66 (7)	O15—O10—O12	114.74 (9)
O4—Tm—N2	25.46 (6)	O14—O10—O12	124.80 (9)
O7—Tm—N2	73.26 (6)	O13—O10—O12	64.45 (7)
O2—Tm—N2	90.88 (6)	Tm—O10—O2	55.11 (6)
O5—Tm—N2	26.04 (6)	O11—O10—O2	92.39 (8)
N1—Tm—N2	103.50 (6)	O15—O10—O2	123.68 (9)
O10—Tm—O8	128.95 (6)	O14—O10—O2	80.12 (8)
O11—Tm—O8	66.54 (6)	O13—O10—O2	57.26 (6)
O12—Tm—O8	66.66 (6)	O12—O10—O2	103.77 (8)
O13—Tm—O8	129.82 (6)	Tm—O10—O1	49.12 (5)
O1—Tm—O8	108.14 (5)	O11—O10—O1	55.52 (6)
O4—Tm—O8	62.01 (6)	O15—O10—O1	93.03 (8)
O7—Tm—O8	45.43 (5)	O14—O10—O1	115.31 (9)
O2—Tm—O8	149.59 (6)	O13—O10—O1	87.66 (7)
O5—Tm—O8	92.10 (6)	O12—O10—O1	97.74 (7)
N1—Tm—O8	130.80 (5)	O2—O10—O1	40.57 (5)
N2—Tm—O8	76.75 (5)	Tm—O10—H1	130 (3)
O10—Tm—N3	140.57 (6)	O11—O10—H1	167 (3)
O11—Tm—N3	68.94 (6)	O15—O10—H1	100 (3)
O12—Tm—N3	89.70 (6)	O14—O10—H1	7 (3)
O13—Tm—N3	141.77 (6)	O13—O10—H1	81 (3)
O1—Tm—N3	88.19 (5)	O12—O10—H1	130 (3)
O4—Tm—N3	68.85 (6)	O2—O10—H1	84 (3)
O7—Tm—N3	22.36 (5)	O1—O10—H1	116 (3)
O2—Tm—N3	126.79 (6)	Tm—O10—H2	120 (3)
O5—Tm—N3	80.10 (6)	O11—O10—H2	65 (3)
N1—Tm—N3	108.51 (5)	O15—O10—H2	11 (3)
N2—Tm—N3	73.74 (5)	O14—O10—H2	115 (3)
O8—Tm—N3	23.07 (5)	O13—O10—H2	168 (3)
O3—N1—O2	122.6 (2)	O12—O10—H2	103 (3)
O3—N1—O1	121.5 (2)	O2—O10—H2	131 (3)
O2—N1—O1	115.82 (18)	O1—O10—H2	96 (3)
O3—N1—Tm	177.14 (17)	H1—O10—H2	108 (4)
O2—N1—Tm	60.15 (11)	Tm—O11—O15^viii	123.70 (8)
O1—N1—Tm	55.68 (10)	Tm—O11—O10	53.37 (5)
N1—O1—O2	31.87 (11)	O15^viii—O11—O10	122.60 (9)
N1—O1—O3	28.72 (11)	Tm—O11—O1	55.51 (5)
O2—O1—O3	60.58 (9)	O15^viii—O11—O1	164.63 (9)
N1—O1—Tm	98.52 (12)	O10—O11—O1	70.56 (7)
O2—O1—Tm	66.66 (7)	Tm—O11—O7	54.93 (5)
O3—O1—Tm	127.24 (9)	O15^viii—O11—O7	107.83 (8)
N1—O1—O7	128.53 (15)	O10—O11—O7	106.57 (8)
O2—O1—O7	106.29 (10)	O1—O11—O7	58.11 (6)
O3—O1—O7	140.60 (12)	Tm—O11—O12	51.22 (5)
Tm—O1—O7	56.61 (5)	O15^viii—O11—O12	77.11 (7)
N1—O1—O11	139.90 (14)	O10—O11—O12	60.99 (6)
O2—O1—O11	112.99 (9)	O1—O11—O12	106.16 (7)
O3—O1—O11	155.01 (11)	O7—O11—O12	86.16 (7)
Tm—O1—O11	52.87 (5)	Tm—O11—O8	67.52 (6)
O7—O1—O11	63.47 (6)	O15^viii—O11—O8	68.58 (7)
N1—O1—O11ⁱ	140.49 (14)	O10—O11—O8	114.24 (8)
O2—O1—O11ⁱ	158.78 (12)	O1—O11—O8	99.54 (8)
O3—O1—O11ⁱ	115.14 (9)	O7—O11—O8	43.17 (6)
Tm—O1—O11ⁱ	114.13 (7)	O12—O11—O8	60.70 (6)
O7—O1—O11ⁱ	62.71 (6)	Tm—O11—O1ⁱ	129.79 (8)
O11—O1—O11ⁱ	79.48 (7)	O15^viii—O11—O1ⁱ	67.77 (7)
N1—O1—O10	86.14 (13)	O10—O11—O1ⁱ	167.02 (9)
O2—O1—O10	64.64 (8)	O1—O11—O1ⁱ	100.52 (7)
O3—O1—O10	106.16 (9)	O7—O11—O1ⁱ	74.86 (7)
Tm—O1—O10	46.07 (5)	O12—O11—O1ⁱ	131.78 (8)
O7—O1—O10	98.82 (7)	O8—O11—O1ⁱ	75.93 (7)
O11—O1—O10	53.92 (6)	Tm—O11—O7ⁱ	132.35 (8)
O11ⁱ—O1—O10	132.50 (8)	O15^viii—O11—O7ⁱ	102.34 (7)
N1—O1—O15ⁱⁱ	89.65 (13)	O10—O11—O7ⁱ	113.06 (8)
O2—O1—O15ⁱⁱ	117.05 (9)	O1—O11—O7ⁱ	76.86 (7)
O3—O1—O15ⁱⁱ	64.92 (7)	O7—O11—O7ⁱ	102.68 (7)
Tm—O1—O15ⁱⁱ	150.29 (9)	O12—O11—O7ⁱ	170.75 (9)
O7—O1—O15ⁱⁱ	96.18 (7)	O8—O11—O7ⁱ	127.94 (8)
O11—O1—O15ⁱⁱ	129.57 (8)	O1ⁱ—O11—O7ⁱ	54.64 (5)
O11ⁱ—O1—O15ⁱⁱ	51.03 (5)	Tm—O11—O15	106.37 (7)
O10—O1—O15ⁱⁱ	163.64 (8)	O15^viii—O11—O15	102.98 (7)
N1—O2—O1	32.31 (11)	O10—O11—O15	53.90 (6)
N1—O2—O3	28.38 (11)	O1—O11—O15	91.32 (7)
O1—O2—O3	60.69 (8)	O7—O11—O15	149.18 (8)
N1—O2—Tm	94.15 (13)	O12—O11—O15	100.27 (7)
O1—O2—Tm	61.84 (6)	O8—O11—O15	160.04 (8)
O3—O2—Tm	122.53 (9)	O1ⁱ—O11—O15	118.68 (7)
N1—O2—O13	145.64 (15)	O7ⁱ—O11—O15	70.75 (6)
O1—O2—O13	113.94 (9)	Tm—O11—H3	129 (3)
O3—O2—O13	170.33 (12)	O15^viii—O11—H3	105 (3)
Tm—O2—O13	52.70 (5)	O10—O11—H3	113 (3)
N1—O2—O5	107.14 (15)	O1—O11—H3	74 (3)
O1—O2—O5	87.66 (9)	O7—O11—H3	99 (3)
O3—O2—O5	121.17 (11)	O12—O11—H3	173 (3)
Tm—O2—O5	56.41 (5)	O8—O11—H3	126 (3)
O13—O2—O5	64.70 (7)	O1ⁱ—O11—H3	54 (3)
N1—O2—O10	95.68 (14)	O7ⁱ—O11—H3	4 (3)
O1—O2—O10	74.80 (8)	O15—O11—H3	73 (3)
O3—O2—O10	113.21 (10)	Tm—O11—H4	121 (3)
Tm—O2—O10	48.61 (5)	O15^viii—O11—H4	4 (3)
O13—O2—O10	57.13 (6)	O10—O11—H4	118 (3)
O5—O2—O10	102.39 (8)	O1—O11—H4	168 (3)
N1—O2—O6ⁱⁱⁱ	118.54 (14)	O7—O11—H4	110 (3)
O1—O2—O6ⁱⁱⁱ	143.35 (11)	O12—O11—H4	74 (3)
O3—O2—O6ⁱⁱⁱ	93.77 (9)	O8—O11—H4	69 (3)
Tm—O2—O6ⁱⁱⁱ	134.73 (9)	O1ⁱ—O11—H4	72 (3)
O13—O2—O6ⁱⁱⁱ	86.94 (7)	O7ⁱ—O11—H4	105 (3)
O5—O2—O6ⁱⁱⁱ	128.98 (8)	O15—O11—H4	101 (3)
O10—O2—O6ⁱⁱⁱ	94.82 (8)	H3—O11—H4	108 (4)
N1—O2—O13ⁱⁱⁱ	119.36 (15)	Tm—O12—O4	55.65 (5)
O1—O2—O13ⁱⁱⁱ	129.73 (11)	Tm—O12—O10	51.09 (5)
O3—O2—O13ⁱⁱⁱ	103.41 (9)	O4—O12—O10	101.51 (7)
Tm—O2—O13ⁱⁱⁱ	113.12 (7)	Tm—O12—O11	51.15 (5)
O13—O2—O13ⁱⁱⁱ	86.20 (7)	O4—O12—O11	96.35 (7)
O5—O2—O13ⁱⁱⁱ	58.87 (6)	O10—O12—O11	56.01 (6)
O10—O2—O13ⁱⁱⁱ	143.20 (8)	Tm—O12—O8^vii	121.45 (8)
O6ⁱⁱⁱ—O2—O13ⁱⁱⁱ	78.86 (6)	O4—O12—O8^vii	81.85 (7)
N1—O3—O2	28.99 (12)	O10—O12—O8^vii	161.11 (9)
N1—O3—O1	29.74 (11)	O11—O12—O8^vii	105.28 (8)
O2—O3—O1	58.73 (8)	Tm—O12—O8	67.41 (6)
N1—O3—O14^iv	129.45 (15)	O4—O12—O8	58.77 (7)
O2—O3—O14^iv	112.88 (10)	O10—O12—O8	109.76 (8)
O1—O3—O14^iv	136.24 (11)	O11—O12—O8	60.52 (6)
N1—O3—O15ⁱⁱ	99.15 (14)	O8^vii—O12—O8	55.90 (7)
O2—O3—O15ⁱⁱ	123.07 (9)	Tm—O12—O13	50.30 (5)
O1—O3—O15ⁱⁱ	73.86 (8)	O4—O12—O13	58.57 (6)
O14^iv—O3—O15ⁱⁱ	123.21 (8)	O10—O12—O13	55.69 (6)
N1—O3—O14ⁱⁱ	103.78 (16)	O11—O12—O13	96.31 (7)
O2—O3—O14ⁱⁱ	86.31 (9)	O8^vii—O12—O13	136.79 (9)
O1—O3—O14ⁱⁱ	119.12 (10)	O8—O12—O13	108.33 (8)
O14^iv—O3—O14ⁱⁱ	101.62 (7)	Tm—O12—O9^vii	159.42 (9)
O15ⁱⁱ—O3—O14ⁱⁱ	91.31 (7)	O4—O12—O9^vii	105.31 (8)
O6—N2—O4	122.0 (2)	O10—O12—O9^vii	149.31 (9)
O6—N2—O5	122.5 (2)	O11—O12—O9^vii	133.55 (8)
O4—N2—O5	115.49 (19)	O8^vii—O12—O9^vii	40.99 (5)
O6—N2—Tm	175.95 (18)	O8—O12—O9^vii	96.86 (7)
O4—N2—Tm	55.34 (11)	O13—O12—O9^vii	130.07 (8)
O5—N2—Tm	60.28 (11)	Tm—O12—H5	124 (3)
N2—O4—O5	32.44 (11)	O4—O12—H5	80 (3)
N2—O4—O6	28.47 (12)	O10—O12—H5	167 (3)
O5—O4—O6	60.91 (9)	O11—O12—H5	111 (3)
N2—O4—Tm	99.20 (13)	O8^vii—O12—H5	6 (3)
O5—O4—Tm	66.85 (7)	O8—O12—H5	60 (3)
O6—O4—Tm	127.60 (9)	O13—O12—H5	133 (3)
N2—O4—O12	149.28 (14)	O9^vii—O12—H5	38 (3)
O5—O4—O12	118.57 (9)	Tm—O12—H6	124 (3)
O6—O4—O12	167.51 (11)	O4—O12—H6	151 (3)
Tm—O4—O12	52.63 (5)	O10—O12—H6	73 (3)
N2—O4—O13	89.39 (12)	O11—O12—H6	103 (3)
O5—O4—O13	71.81 (8)	O8^vii—O12—H6	113 (3)
O6—O4—O13	105.26 (9)	O8—O12—H6	150 (3)
Tm—O4—O13	52.19 (5)	O13—O12—H6	98 (3)
O12—O4—O13	64.35 (6)	O9^vii—O12—H6	76 (3)
N2—O4—O8	121.99 (15)	H5—O12—H6	112 (4)
O5—O4—O8	105.54 (10)	Tm—O13—O14^ix	126.06 (8)
O6—O4—O8	128.45 (10)	Tm—O13—O10	52.99 (5)
Tm—O4—O8	68.99 (6)	O14^ix—O13—O10	123.85 (9)
O12—O4—O8	64.03 (7)	Tm—O13—O2	58.48 (5)
O13—O4—O8	117.39 (8)	O14^ix—O13—O2	170.54 (10)
N2—O4—O15^v	105.48 (13)	O10—O13—O2	65.61 (7)
O5—O4—O15^v	132.47 (10)	Tm—O13—O4	54.86 (5)
O6—O4—O15^v	80.38 (8)	O14^ix—O13—O4	82.46 (7)
Tm—O4—O15^v	144.77 (8)	O10—O13—O4	103.61 (7)
O12—O4—O15^v	105.17 (7)	O2—O13—O4	95.85 (8)
O13—O4—O15^v	150.26 (9)	Tm—O13—O5ⁱⁱⁱ	128.52 (8)
O8—O4—O15^v	76.65 (7)	O14^ix—O13—O5ⁱⁱⁱ	103.47 (7)
N2—O4—O7	84.55 (14)	O10—O13—O5ⁱⁱⁱ	112.21 (8)
O5—O4—O7	62.95 (8)	O2—O13—O5ⁱⁱⁱ	70.49 (7)
O6—O4—O7	104.27 (9)	O4—O13—O5ⁱⁱⁱ	130.25 (8)
Tm—O4—O7	51.53 (5)	Tm—O13—O5	55.31 (5)
O12—O4—O7	85.18 (7)	O14^ix—O13—O5	115.55 (8)
O13—O4—O7	100.94 (7)	O10—O13—O5	104.14 (7)
O8—O4—O7	42.60 (6)	O2—O13—O5	58.80 (7)
O15^v—O4—O7	105.93 (7)	O4—O13—O5	43.43 (6)
N2—O5—O4	32.07 (11)	O5ⁱⁱⁱ—O13—O5	93.63 (7)
N2—O5—O6	28.04 (11)	Tm—O13—O12	50.06 (5)
O4—O5—O6	60.10 (8)	O14^ix—O13—O12	80.61 (7)
N2—O5—Tm	93.68 (13)	O10—O13—O12	59.86 (6)
O4—O5—Tm	61.69 (7)	O2—O13—O12	106.36 (7)
O6—O5—Tm	121.66 (9)	O4—O13—O12	57.07 (6)
N2—O5—O2	138.74 (15)	O5ⁱⁱⁱ—O13—O12	171.66 (8)
O4—O5—O2	112.22 (9)	O5—O13—O12	91.06 (7)
O6—O5—O2	153.44 (11)	Tm—O13—O2ⁱⁱⁱ	119.90 (8)
Tm—O5—O2	55.67 (5)	O14^ix—O13—O2ⁱⁱⁱ	76.74 (7)
N2—O5—O7	95.06 (13)	O10—O13—O2ⁱⁱⁱ	159.18 (9)
O4—O5—O7	74.85 (8)	O2—O13—O2ⁱⁱⁱ	93.80 (7)
O6—O5—O7	111.87 (9)	O4—O13—O2ⁱⁱⁱ	80.58 (7)
Tm—O5—O7	54.27 (5)	O5ⁱⁱⁱ—O13—O2ⁱⁱⁱ	54.24 (6)
O2—O5—O7	88.06 (7)	O5—O13—O2ⁱⁱⁱ	64.66 (6)
N2—O5—O13ⁱⁱⁱ	122.46 (14)	O12—O13—O2ⁱⁱⁱ	134.09 (8)
O4—O5—O13ⁱⁱⁱ	139.71 (10)	Tm—O13—H7	122 (3)
O6—O5—O13ⁱⁱⁱ	101.74 (9)	O14^ix—O13—H7	5 (3)
Tm—O5—O13ⁱⁱⁱ	120.11 (8)	O10—O13—H7	122 (3)
O2—O5—O13ⁱⁱⁱ	66.89 (6)	O2—O13—H7	171 (3)
O7—O5—O13ⁱⁱⁱ	142.29 (8)	O4—O13—H7	78 (3)
N2—O5—O13	82.93 (13)	O5ⁱⁱⁱ—O13—H7	108 (3)
O4—O5—O13	64.76 (7)	O5—O13—H7	113 (3)
O6—O5—O13	100.34 (9)	O12—O13—H7	77 (3)
Tm—O5—O13	49.52 (5)	O2ⁱⁱⁱ—O13—H7	78 (3)
O2—O5—O13	56.50 (6)	Tm—O13—H8	129 (3)
O7—O5—O13	103.35 (7)	O14^ix—O13—H8	103 (3)
O13ⁱⁱⁱ—O5—O13	86.37 (7)	O10—O13—H8	113 (3)
N2—O6—O4	29.55 (12)	O2—O13—H8	71 (3)
N2—O6—O5	29.44 (12)	O4—O13—H8	130 (3)
O4—O6—O5	58.99 (8)	O5ⁱⁱⁱ—O13—H8	1 (3)
N2—O6—O14ⁱⁱⁱ	116.45 (16)	O5—O13—H8	94 (3)
O4—O6—O14ⁱⁱⁱ	146.00 (11)	O12—O13—H8	172 (3)
O5—O6—O14ⁱⁱⁱ	87.01 (9)	O2ⁱⁱⁱ—O13—H8	54 (3)
N2—O6—O9^vi	83.84 (14)	H7—O13—H8	107 (4)
O4—O6—O9^vi	77.76 (9)	O13^ix—O14—O10	98.12 (8)
O5—O6—O9^vi	91.17 (9)	O13^ix—O14—O6ⁱⁱⁱ	118.03 (9)
O14ⁱⁱⁱ—O6—O9^vi	104.35 (9)	O10—O14—O6ⁱⁱⁱ	107.66 (9)
N2—O6—O2ⁱⁱⁱ	83.25 (14)	O13^ix—O14—O3^iv	112.05 (8)
O4—O6—O2ⁱⁱⁱ	93.56 (9)	O10—O14—O3^iv	139.09 (9)
O5—O6—O2ⁱⁱⁱ	74.80 (8)	O6ⁱⁱⁱ—O14—O3^iv	82.46 (7)
O14ⁱⁱⁱ—O6—O2ⁱⁱⁱ	76.63 (7)	O13^ix—O14—O3^x	93.53 (8)
O9^vi—O6—O2ⁱⁱⁱ	165.92 (9)	O10—O14—O3^x	72.61 (7)
O9—N3—O8	121.2 (2)	O6ⁱⁱⁱ—O14—O3^x	147.52 (9)
O9—N3—O7	119.94 (19)	O3^iv—O14—O3^x	78.38 (7)
O8—N3—O7	118.84 (19)	O13^ix—O14—O13	69.68 (7)
O9—N3—Tm	167.34 (15)	O10—O14—O13	53.22 (6)
O8—N3—Tm	71.43 (13)	O6ⁱⁱⁱ—O14—O13	82.55 (7)
O7—N3—Tm	47.41 (10)	O3^iv—O14—O13	163.54 (9)
N3—O7—O8	30.06 (11)	O3^x—O14—O13	118.06 (7)
N3—O7—O9	29.46 (11)	O13^ix—O14—H9	116 (3)
O8—O7—O9	59.52 (9)	O10—O14—H9	109 (3)
N3—O7—Tm	110.23 (13)	O6ⁱⁱⁱ—O14—H9	3 (3)
O8—O7—Tm	80.17 (8)	O3^iv—O14—H9	83 (3)
O9—O7—Tm	139.69 (10)	O3^x—O14—H9	150 (3)
N3—O7—O1	147.87 (15)	O13—O14—H9	82 (3)
O8—O7—O1	125.43 (10)	O13^ix—O14—H10	114 (3)
O9—O7—O1	152.51 (11)	O10—O14—H10	111 (3)
Tm—O7—O1	54.43 (5)	O6ⁱⁱⁱ—O14—H10	108 (3)
N3—O7—O5	121.52 (14)	O3^iv—O14—H10	31 (3)
O8—O7—O5	104.49 (9)	O3^x—O14—H10	48 (3)
O9—O7—O5	130.94 (10)	O13—O14—H10	164 (3)
Tm—O7—O5	56.17 (5)	H9—O14—H10	109 (4)
O1—O7—O5	76.12 (7)	O11^viii—O15—O10	105.91 (8)
N3—O7—O11	89.75 (13)	O11^viii—O15—O9ⁱ	123.52 (9)
O8—O7—O11	69.95 (8)	O10—O15—O9ⁱ	97.93 (9)
O9—O7—O11	109.13 (10)	O11^viii—O15—O4^xi	135.84 (8)
Tm—O7—O11	50.47 (5)	O10—O15—O4^xi	113.20 (8)
O1—O7—O11	58.42 (6)	O9ⁱ—O15—O4^xi	71.01 (7)
O5—O7—O11	106.35 (7)	O11^viii—O15—O3^x	101.79 (8)
N3—O7—O11ⁱ	109.28 (13)	O10—O15—O3^x	74.76 (7)
O8—O7—O11ⁱ	123.31 (10)	O9ⁱ—O15—O3^x	133.98 (8)
O9—O7—O11ⁱ	91.56 (9)	O4^xi—O15—O3^x	70.82 (7)
Tm—O7—O11ⁱ	112.11 (7)	O11^viii—O15—O1^x	61.19 (6)
O1—O7—O11ⁱ	62.65 (6)	O10—O15—O1^x	80.98 (7)
O5—O7—O11ⁱ	128.92 (7)	O9ⁱ—O15—O1^x	175.19 (8)
O11—O7—O11ⁱ	77.32 (7)	O4^xi—O15—O1^x	105.04 (8)
N3—O7—O4	83.39 (12)	O3^x—O15—O1^x	41.22 (5)
O8—O7—O4	62.31 (8)	O11^viii—O15—O8^viii	60.23 (6)
O9—O7—O4	105.04 (9)	O10—O15—O8^viii	151.59 (9)
Tm—O7—O4	50.10 (4)	O9ⁱ—O15—O8^viii	110.39 (8)
O1—O7—O4	99.67 (7)	O4^xi—O15—O8^viii	75.62 (6)
O5—O7—O4	42.20 (5)	O3^x—O15—O8^viii	83.73 (7)
O11—O7—O4	90.17 (7)	O1^x—O15—O8^viii	70.61 (6)
O11ⁱ—O7—O4	161.88 (7)	O11^viii—O15—O11	77.02 (7)
N3—O8—O9	29.33 (11)	O10—O15—O11	53.89 (6)
N3—O8—O7	31.10 (11)	O9ⁱ—O15—O11	77.44 (7)
O9—O8—O7	60.43 (8)	O4^xi—O15—O11	143.83 (8)
N3—O8—O8^vii	164.0 (2)	O3^x—O15—O11	124.74 (8)
O9—O8—O8^vii	137.71 (14)	O1^x—O15—O11	105.40 (7)
O7—O8—O8^vii	157.96 (15)	O8^viii—O15—O11	133.51 (8)
N3—O8—O4	95.90 (15)	O11^viii—O15—H11	116 (3)
O9—O8—O4	114.74 (11)	O10—O15—H11	105 (3)
O7—O8—O4	75.09 (9)	O9ⁱ—O15—H11	8 (3)
O8^vii—O8—O4	84.07 (10)	O4^xi—O15—H11	73 (3)
N3—O8—O12^vii	103.77 (15)	O3^x—O15—H11	140 (3)
O9—O8—O12^vii	75.16 (9)	O1^x—O15—H11	174 (3)
O7—O8—O12^vii	133.87 (10)	O8^viii—O15—H11	104 (3)
O8^vii—O8—O12^vii	62.61 (9)	O11—O15—H11	78 (3)
O4—O8—O12^vii	116.75 (8)	O11^viii—O15—H12	116 (3)
N3—O8—O11	87.65 (14)	O10—O15—H12	108 (3)
O9—O8—O11	107.57 (9)	O9ⁱ—O15—H12	103 (3)
O7—O8—O11	66.87 (8)	O4^xi—O15—H12	32 (3)
O8^vii—O8—O11	108.35 (11)	O3^x—O15—H12	43 (3)
O4—O8—O11	94.14 (8)	O1^x—O15—H12	73 (3)
O12^vii—O8—O11	145.13 (10)	O8^viii—O15—H12	64 (3)
N3—O8—O12	131.37 (16)	O11—O15—H12	162 (3)
O9—O8—O12	160.61 (11)	H11—O15—H12	105 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H1···O14	0.85 (4)	1.89 (4)	2.730 (3)	170 (4)
O10—H2···O15	0.73 (5)	2.00 (5)	2.714 (3)	164 (5)
O11—H4···O15^viii	0.74 (4)	1.93 (4)	2.666 (2)	174 (4)
O11—H3···O7ⁱ	0.81 (4)	2.20 (4)	3.006 (2)	175 (4)
O12—H5···O8^vii	0.80 (4)	2.15 (4)	2.943 (3)	172 (4)
O12—H6···O5^x	0.79 (4)	2.57 (4)	3.260 (3)	147 (4)
O12—H6···O7^x	0.79 (4)	2.61 (4)	3.269 (3)	142 (4)
O13—H7···O14^ix	0.78 (4)	1.93 (4)	2.713 (3)	174 (4)
O13—H8···O5ⁱⁱⁱ	0.83 (5)	2.13 (5)	2.963 (2)	179 (5)
O14—H9···O6ⁱⁱⁱ	0.80 (4)	2.01 (4)	2.804 (3)	176 (4)
O14—H10···O3^x	0.80 (5)	2.64 (5)	3.111 (3)	119 (4)
O14—H10···O3^iv	0.80 (5)	2.24 (5)	2.885 (2)	138 (4)
O15—H11···O9ⁱ	0.79 (5)	2.01 (5)	2.782 (3)	168 (4)
O15—H12···O4^xi	0.79 (5)	2.29 (5)	2.926 (2)	137 (4)
O15—H12···O3^x	0.79 (5)	2.47 (5)	2.992 (3)	125 (4)

Symmetry codes: (i) −x, −y+1, −z+1; (iii) −x, −y+1, −z; (iv) −x, −y+2, −z; (vii) −x+1, −y, −z+1; (viii) −x+1, −y+1, −z+1; (ix) −x+1, −y+1, −z; (x) x+1, y, z; (xi) x, y+1, z.

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