YCu(TeO3)2(NO3)(H2O)3: a novel layered tellurite.

A new hydrated yttrium copper tellurite nitrate, yttrium(III) copper(II) bis-[trioxidotellurate(IV)] nitrate trihydrate, has been synthesized hydro-thermally in a Teflon-lined autoclave and structurally determined using synchrotron radiation. The new phase is the first example containing yttrium, copper and tellurium in one structure. Its crystal structure is unique, with relatively strongly bound layers extending parallel to (020), defined by YO8, CuO4 and TeO3 polyhedra, while the NO3 (-) anions and one third of the water mol-ecules lie between those layers. The structural unit consists of [Cu2(TeO3)4](4-) loop-branched chains of {Cu⋯Te⋯Cu⋯Te} squares running parallel to [001], which are linked further into layers only through Y(O,H2O)8 polyhedra. Weak 'secondary' Te bonds and O-H⋯O hydrogen-bonding inter-actions, involving water mol-ecules and layer O atoms, link the layers and inter-layer species. IR spectroscopic data are also presented.

Chemical context

Recent discoveries of a wide range of novel tellurium minerals have prompted numerous structural studies of tellurium oxysalts (Kampf et al., 2013 ▸; Christy et al., 2016a ▸). As well as the characterization of these naturally occurring minerals, various syntheses have also been undertaken as part of this ongoing study, yielding an array of new structures, including that of novel Na11H[Te(OH)3]8[SO4]10(H2O)13 (Mills et al., 2016 ▸). Several tellurium oxide species with various yttrium oxide polyhedra present in the structure have been synthesized in the past, including compounds with both TeIV and TeVI atoms. Tellurium is stable in numerous oxidation states and shows large diversity in bonding (Christy & Mills, 2013 ▸). Its +IV and +VI oxidation states are of greatest inter­est in relation to naturally occurring weathering products of minerals, and are able to form a wide variety of oxide polyhedra, with TeO3 2− most prevalent (Song et al., 2014 ▸). The TeO3 2− anion shows a wide variety of connectivities, with three oxido ligands and the 5s 2 electron lone pair occupying the vertices of the distorted polyhedra, and are found in a variety of layer and chain structures in inorganic compounds (Johansson & Lindqvist, 1978 ▸). This is demonstrated in compounds such as NaYTe4O10 with YO8 and TeO4 polyhedra, KY(TeO3)2 and RbY(TeO3)2 with YO6 octa­hedra and trigonal–pyramidal TeO3 2− anions, CsYTe3O8 with YO6 and TeO4 polyhedra (Kim et al., 2014 ▸), as well as yttrium tellurium oxides with TeVI atoms (Kasper, 1969 ▸; Höss & Schleid, 2007 ▸; Noguera et al., 2012 ▸). As a consequence of this range of chemistry, tellurium is the most anomalously diverse element found in minerals compared to its scarcity in the earth’s crust (Christy, 2015 ▸). Many copper-containing tellurium oxides have been successfully synthesized (Feger et al., 1999 ▸; Koteswararao et al., 2013 ▸; Sedello & Müller-Buschbaum, 1996 ▸), and copper is also present in many tellurium-containing minerals; indeed, out of the unusually large inventory of tellurium secondary minerals at Otto Mountain, the majority contains copper (Christy et al., 2016a ▸). Despite this, there are very few synthetic rare earth copper tellurium oxides known, and to the best of our knowledge a compound containing all three of copper, yttrium and tellurium has not been characterized so far. Although layered structures with inter­stitial ions are common for TeIV compounds, nitrate is found as an anion in very few, which motivates the use of metal nitrates in the synthesis of novel tellurium oxides. The only other compounds with simple tellurite and nitrate anions whose structures have been reported to date are the layered compounds Ca6(TeO3)5(NO3)2 and Ca5(TeO3)4(NO3)2(H2O)2 (Stöger & Weil, 2013 ▸). Nitrates of polymerized Te(IV) complexes are also known. The compound AgTeO2(NO3) (Olsson et al., 1988 ▸) contains an electrically neutral [Te2O4]0 chain (Christy et al., 2016b ▸), while [Te2O3OH](NO3) contains a cationic [Te2O3OH]+ layer (Anderson et al., 1980 ▸; Christy et al., 2016b ▸).

Structural commentary

Bond-valence sums are given in Table 1 ▸. In general, the bond-valence data of Table 1 ▸ were calculated using the bond-valence parameters of Brown & Altermatt (1985 ▸), except that the Te—O data were from Mills & Christy (2013 ▸). However, Brown (2009 ▸) noted that no single pair of r 0 and b values is adequate for O—H bonds, since O⋯O repulsion increases the length of weak O—H bonds relative to strong ones. Here, the parameterization of Yu et al. (2006 ▸) was used, with r 0 = 0.79 Å for bond valence < 0.5 valence units, r 0 = 1.409 Å for bond valence > 0.5 v.u., and b = 0.37 Å in both cases.

Table 1

Bond-valence sums (in valence units) for YCu(TeO3)2(NO3)(H2O)3

	Y1	Cu1	Te1	Te2	N1	H11	H12	H21	H22	H31	H32	Σ	Σ(excluding H)
O1	0.401	0.544, 0.047	1.128									2.12	2.12
O2	0.478, 0.275		1.145	0.130								2.03	2.03
O3		0.436	1.208	0.173					0.232			2.05	1.82
O4	0.399	0.534, 0.046		1.148			0.041					2.17	2.13
O5	0.481, 0.316	0.421	0.118	1.165								2.08	2.08
O6			0.183	1.179			0.279					2.06	1.78
O7			0.156		1.562							1.72	1.72
O8				0.156	1.609			0.068		0.047		1.88	1.77
O9					1.712						0.062, 0.036	1.81	1.71
OW1	0.384					0.755	0.755					1.89	0.38
OW2	0.389							0.771	0.769			1.93	0.39
OW3						0.224		0.110		0.743	0.761	1.84	0.00
Σ	3.12	2.03	3.93	3.94	4.88	0.98	1.08	0.95	1.00	0.79	0.86

The structure of the title compound is strongly layered. Layers parallel to (020) are defined by YO8, CuO4 and TeO3 polyhedra, while NO3 − anions and one third of the water mol­ecules (OW1) lie between those layers. Tellurite and nitrate anions (involving atoms O1–O9) are clearly distinguished from water mol­ecules OW1–OW3 by their bond-valence sums (Table 1 ▸). Within the layers, Y is eightfold coordinated in a distorted snub disphenoidal (triangular dodeca­hedral) arrangement by 6 × O2− and 2 × H2O at 2.290 (3)–2.497 (3) Å. Cu is in square-planar coordination, with four close oxygen neighbours at 1.904 (3)–1.999 (3) Å. Two more oxygen ligands at 2.811 (4) and 2.817 (4) Å complete an octa­hedron that is very elongated due to the Jahn-Teller distortion. Te1 is trigonal–pyramidally coordin­ated by three oxygen atoms at 1.883 (3)–1.911 (3) Å. Three ‘secondary bonds’ to O atoms at 2.657 (3)–2.837 (3) Å complete a polyhedron that can be described as an octa­hedron that is very distorted due to the lone-pair stereoactivity. Te2 has very similar coordination, with three primary Te—O bonds of 1.893 (3)–1.905 (3) Å and three secondary bonds of 2.681 (4)–2.798 (3) Å. In each case, two of the secondary bonds provide additional bracing within the {Y⋯Cu⋯Te} layer, while the third is to a nitrate oxygen (Te1—O7 and Te2—O8, both ≃ 2.72 Å), and thus provides weak bridging between the layers and inter­layer species. The nitrate oxygen atom O9 makes a seventh very distant ligand for both Te1 [3.231 (4) Å] and Te2 [3.350 (4) Å], further than the shortest Te⋯Cu distances and with bond valences < 0.05 valence units, using the parameters of Mills & Christy (2013 ▸).

The identification and classification of a strongly bonded ‘structural unit’ (Hawthorne, 2014 ▸) in the structure of this compound depends crucially on which bonds are regarded as strong enough to define such a unit. The classification of Te oxycompound structures by Christy et al. (2016b ▸) in general used thresholds of about 2.45 Å for Te—O and 2.20 Å for Cu—O bonds, while no bonds to 8-fold coordinated cations were considered to be part of the structural unit. The same criteria applied to the current structure would regard the CuO4 squares as isolated from one another, although inclusion of the long Cu—O bonds would link CuO4+2 polyhedra to form trans edge-sharing chains parallel to [001]. Without the long bonds, CuO4 squares are linked to their neighbours most strongly via TeO3 pyramids, to produce loop-branched chains [Cu2(TeO3)4]4− of {Cu⋯Te⋯Cu⋯Te} squares running parallel to [001] (Fig. 1 ▸). These chains are the structural units, since they are linked further into layers only through Y(O,H2O)8 polyhedra (Fig. 2 ▸). It is noteworthy that this chain is similar in topology but not in geometrical configuration to the structural unit of Dy[CuCl(TeO3)2] and its Er—Cl and Er—Br analogues (Shen & Mao, 2005 ▸). However, in the current compound, the {Cu⋯Te} squares are non-planar, so that the chain periodicity is doubled, and Cu does not have chloride as an additional ligand. Furthermore, in the structures of the compounds of Shen and Mao (2005 ▸), rare earth cations link the chains into a three-dimensional framework rather than into layers.

Figure 1

View in polyhedral mode of the [Cu2(TeO3)4]4− loop-branched chains running parallel to [001]. CuO4 polyhedra are cyan, TeO3 polyhedra are green

Figure 2

The crystal structure of YCu(TeO3)2(NO3)(H2O)3 viewed down [100]. O atoms are red, Y yellow, Cu cyan, Te green, N light-blue and O atoms of water mol­ecules pink. Displacement ellipsoids are drawn at the 50% probability level.

H11, H12, H22 and H31 were found to make relatively strong hydrogen bonds (Table 2 ▸) to respectively OW3, O6, O3 and O7 at distances between 1.88–1.96 Å. H12 and H31 have additional acceptor O atoms at greater distances, respectively O4 at 2.59 Å and O8 at 2.54 Å. The remaining H atoms each have two oxygen neighbours at greater distances, suggesting weak bifurcated hydrogen bonding: OW3 at 2.23 Å and O8 at 2.40 Å for H21, and O8 at 2.44 Å, O9 at 2.64 Å for H32.

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW1—H11⋯OW3	0.89 (3)	1.96 (3)	2.854 (6)	174 (7)
OW1—H12⋯O6i	0.89 (3)	1.88 (4)	2.729 (5)	157 (7)
OW2—H21⋯O8i	0.89 (3)	2.41 (6)	3.074 (5)	132 (6)
OW2—H21⋯OW3ii	0.89 (3)	2.22 (5)	2.949 (6)	139 (6)
OW2—H22⋯O3	0.89 (3)	1.95 (5)	2.745 (5)	149 (7)
OW3—H31⋯O7	0.90 (3)	1.97 (4)	2.834 (7)	162 (9)
OW3—H31⋯O8iii	0.90 (3)	2.53 (8)	3.141 (7)	126 (7)
OW3—H32⋯O9iv	0.89 (3)	2.49 (4)	3.360 (7)	166 (9)
OW3—H32⋯O9v	0.89 (3)	2.64 (9)	3.253 (8)	127 (8)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

The layers of the structure are linked by only weak bonds. The bridges Te1⋯O7—N—O8⋯Te2 mentioned above have Te⋯O ≃ 2.72 Å, implying a bond of 0.15 valence units (Mills & Christy, 2013 ▸). The hydrogen bonds in the bridges OW1—H11⋯OW3⋯H21—OW2 are of comparable bond valence.

It is noteworthy that the IR spectrum shows three distinct O—H bands at 3460, 3145 and 2900 cm−1. According to Libowitzky (1999 ▸), this would be typical for O—H⋯O distances of ∼ 2.83, 2.69 and 2.63 Å. The first two of these are broadly consistent with the O⋯O distances for the strongest hydrogen bonds indicated by the refinement: OW1—H12⋯OW3 = 2.85 Å, OW2—H12⋯O3 = 2.74 Å and OW1—H11⋯O6 = 2.73 Å. However, the band at 2900 cm−1 is lower in frequency than would be expected.

Spectroscopy

The infrared spectrum was obtained using a Bruker Alpha FTIR with a diamond Attenuated Total Reflectance attachment (ATR), DTGS (Deuterated Triglycine Sulfate) detector, 4 cm−1 resolution and 4000–450 cm−1 range. The samples were placed on the ATR crystal and pressure exerted by screwing the pressure clamp onto the sample to ensure maximum contact with the ATR crystal. 128 scans were taken for each item and co-added. Band assignments are consistent with those given in Kampf et al. (2013 ▸). Numerical values of the spectrum and assignments of the vibration bands are given in Table 3 ▸; the spectrum is deposited as a supplementary figure.

Table 3

IR band assignments (cm−1) for YCu(TeO3)2(NO3)(H2O)3

Absorption bands	Assignment
3460w	O—H stretch
3145w	O—H stretch
∼2900w	O—H stretch
1755	H—O—H bend
1645	H—O—H bend
1605	H—O—H bend
1345	ν3 anti­symmetric stretch NO3 −
1044	ν1 symmetric stretch NO3 −
734	ν1 (TeO3)2− symmetric stretch
636	ν3 (TeO3)2− anti­symmetric stretch
547	M—O lattice modes
447	M—O lattice modes

Synthesis and crystallization

Dark blue prisms of YCu(TeO3)2(NO3)(H2O)3 were synthesized hydro­thermally. For the synthesis, Y(NO3)3·6H2O (Aldrich, 99.8%), Cu(NO3)2·3H2O (Sigma–Aldrich ≥99%) and Te 200 mm mesh (Aldrich, 99.8%) were used as starting materials. A 1:1:1 molar ratio of the reagents in 20 ml water was reacted in a Teflon autoclave bomb at 473 K for 3 days. Crystals of YCu(TeO3)2(NO3)(H2O)3 were separated manually from a blue powder of undetermined composition in a few percent yield. Several unsuccessful attempts were made to synthesize YCu(TeO3)2(NO3)(H2O)3 from a stoichiometric mixture of the reagents, using the molar ratio 1:1:2. We also were unsuccessful in producing new compounds, with the same structure type or not, using La, Ce, Nd or Gd in place of Y.

Refinement

Single crystal X-ray diffraction experiments were carried out on the micro-focus macromolecular beam line MX2 of the Australian Synchrotron. Details of data collection and structure refinement are provided in Table 4 ▸. Hydrogen atoms H11, H12 and H21 were located during refinement as difference peaks of about one e− / Å3 occurring at a distance of ca. 0.9–1.0 Å from their nearest oxygen atom. In all cases, short O—H bonds were directed towards another oxygen atom, indicating the existence of hydrogen bonds. Positions were estimated for the remaining hydrogen atoms, assuming water mol­ecule O—H distance near 0.9 Å, H—O—H bond angle near 104°, that O—H vectors were directed to make hydrogen bonds to nearby oxygen atoms, if possible, and that the arrangement of O—H and O⋯H around OW3 was approximately tetra­hedral. In all cases, residuals of > 0.6 electrons were found close to the expected positions, that could be identified with the H atoms. H positions were finally included in the refinement, assuming full occupancy, isotropic displacement parameters were fixed to 1.5× of their corresponding O atom and the O—H distance was restrained at 0.90 (3) Å.

Table 4

Experimental details

Crystal data
Chemical formula	YCu(TeO3)2(NO3)(H2O)3
M r	619.71
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	100
a, b, c (Å)	7.2560 (15), 20.654 (4), 7.0160 (14)
β (°)	94.63 (3)
V (Å3)	1048.0 (4)
Z	4
Radiation type	Synchrotron, λ = 0.71073 Å
μ (mm−1)	13.06
Crystal size (mm)	0.02 × 0.02 × 0.01
Data collection
Diffractometer	ADSC Quantum 315r detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001 ▸)
T min, T max	0.295, 0.433
No. of measured, independent and observed [I > 2σ(I)] reflections	20336, 2901, 2810
R int	0.054
(sin θ/λ)max (Å−1)	0.704
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.033, 0.074, 1.14
No. of reflections	2901
No. of parameters	173
No. of restraints	6
H-atom treatment	Only H-atom coordinates refined
Δρmax, Δρmin (e Å−3)	1.45, −1.56

Computer programs: local program, XDS (Kabsch, 2010 ▸), XPREP (Bruker, 2001 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), CrystalMaker (Palmer, 2009 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016011464/wm5307sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016011464/wm5307Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989016011464/wm5307sup3.pdf

CCDC reference: 1493330

Additional supporting information: crystallographic information; 3D view; checkCIF report

YCu(TeO3)2(NO3)(H2O)3	F(000) = 1124
Mr = 619.71	Dx = 3.928 Mg m−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.71073 Å
a = 7.2560 (15) Å	Cell parameters from 20243 reflections
b = 20.654 (4) Å	θ = 2.8–30.0°
c = 7.0160 (14) Å	µ = 13.06 mm−1
β = 94.63 (3)°	T = 100 K
V = 1048.0 (4) Å3	Prism, dark blue
Z = 4	0.02 × 0.02 × 0.01 mm

ADSC Quantum 315r detector diffractometer	2810 reflections with I > 2σ(I)
Radiation source: synchrotron	Rint = 0.054
φ scan	θmax = 30.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
Tmin = 0.295, Tmax = 0.433	k = −29→29
20336 measured reflections	l = −9→9
2901 independent reflections	360 standard reflections every 1 reflections

Refinement on F2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	Only H-atom coordinates refined
R[F2 > 2σ(F2)] = 0.033	w = 1/[σ2(Fo2) + 11.0043P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.074	(Δ/σ)max = 0.001
S = 1.14	Δρmax = 1.45 e Å−3
2901 reflections	Δρmin = −1.56 e Å−3
173 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
6 restraints	Extinction coefficient: 0.0094 (5)

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.

	x	y	z	Uiso*/Ueq
Te1	0.21415 (4)	0.34749 (2)	0.49104 (4)	0.00849 (9)
Te2	0.71124 (4)	0.15281 (2)	1.03341 (4)	0.00846 (9)
Y1	−0.03880 (6)	0.28786 (2)	0.01247 (6)	0.00865 (11)
Cu1	0.46115 (7)	0.24947 (2)	0.76001 (8)	0.00911 (12)
N1	0.8271 (7)	0.0010 (2)	1.1795 (7)	0.0209 (9)
O1	0.2531 (4)	0.26068 (15)	0.5797 (5)	0.0105 (6)
O2	0.0133 (4)	0.31345 (15)	0.3301 (5)	0.0106 (6)
O3	0.3929 (4)	0.34159 (15)	0.3116 (5)	0.0112 (6)
O4	0.6704 (4)	0.23870 (15)	0.9406 (5)	0.0114 (6)
O5	0.9077 (4)	0.18938 (15)	1.1933 (5)	0.0106 (6)
O6	0.5292 (5)	0.15853 (15)	1.2113 (5)	0.0099 (6)
O7	0.0622 (7)	0.45346 (18)	0.3091 (7)	0.0279 (10)
O8	0.8860 (6)	0.05534 (18)	1.2373 (6)	0.0233 (8)
O9	0.3327 (6)	0.49362 (19)	0.3909 (7)	0.0284 (9)
OW1	−0.2697 (5)	0.36731 (17)	0.0483 (5)	0.0134 (6)
H11	−0.266 (10)	0.4092 (16)	0.080 (10)	0.020*
H12	−0.360 (8)	0.364 (4)	−0.046 (8)	0.020*
OW2	0.1872 (5)	0.36858 (17)	−0.0246 (5)	0.0153 (7)
H21	0.155 (10)	0.407 (2)	−0.070 (10)	0.023*
H22	0.279 (8)	0.371 (4)	0.066 (8)	0.023*
OW3	−0.2844 (7)	0.5007 (2)	0.1525 (8)	0.0317 (10)
H31	−0.182 (9)	0.490 (4)	0.225 (12)	0.048*
H32	−0.374 (10)	0.503 (4)	0.232 (12)	0.048*

	U11	U22	U33	U12	U13	U23
Te1	0.00827 (14)	0.00782 (13)	0.00912 (16)	−0.00013 (8)	−0.00084 (9)	−0.00064 (9)
Te2	0.00858 (14)	0.00783 (14)	0.00876 (16)	0.00007 (8)	−0.00061 (9)	−0.00066 (9)
Y1	0.00832 (19)	0.00855 (19)	0.0089 (2)	0.00012 (13)	−0.00055 (14)	0.00008 (13)
Cu1	0.0081 (2)	0.0088 (2)	0.0100 (3)	−0.00025 (17)	−0.00157 (18)	0.00098 (18)
N1	0.027 (2)	0.0128 (19)	0.022 (2)	−0.0008 (16)	−0.0056 (18)	0.0026 (16)
O1	0.0103 (14)	0.0089 (13)	0.0119 (16)	0.0001 (11)	−0.0018 (11)	0.0007 (11)
O2	0.0089 (14)	0.0102 (14)	0.0125 (16)	−0.0020 (11)	−0.0009 (11)	0.0003 (11)
O3	0.0080 (14)	0.0096 (13)	0.0163 (17)	0.0003 (11)	0.0032 (12)	0.0002 (11)
O4	0.0098 (14)	0.0093 (13)	0.0147 (17)	0.0005 (11)	−0.0018 (12)	0.0038 (11)
O5	0.0109 (14)	0.0095 (13)	0.0109 (16)	−0.0014 (11)	−0.0015 (11)	−0.0007 (11)
O6	0.0115 (14)	0.0116 (14)	0.0067 (15)	0.0012 (11)	0.0017 (11)	−0.0014 (11)
O7	0.038 (2)	0.0108 (16)	0.032 (2)	−0.0057 (16)	−0.0148 (19)	0.0042 (15)
O8	0.034 (2)	0.0136 (16)	0.020 (2)	0.0006 (15)	−0.0072 (16)	−0.0014 (14)
O9	0.026 (2)	0.0194 (18)	0.038 (3)	0.0027 (15)	−0.0085 (18)	0.0027 (17)
OW1	0.0137 (15)	0.0128 (15)	0.0128 (17)	0.0022 (12)	−0.0036 (12)	−0.0031 (12)
OW2	0.0176 (16)	0.0140 (15)	0.0137 (18)	−0.0029 (13)	−0.0016 (13)	0.0024 (12)
OW3	0.039 (3)	0.025 (2)	0.031 (3)	0.0023 (19)	0.000 (2)	0.0002 (18)

Te1—O3	1.883 (3)	O2—Cu1i	3.571 (3)
Te1—O2	1.905 (3)	O3—Cu1i	1.986 (3)
Te1—O1	1.911 (3)	O3—Te2i	2.681 (3)
Te1—O6i	2.657 (3)	O4—Y1ix	2.359 (3)
Te1—O7	2.722 (4)	O4—Cu1iii	2.817 (4)
Te1—O5ii	2.837 (3)	O4—Te2i	3.661 (3)
Te2—O6	1.893 (3)	O4—Te1iii	3.801 (3)
Te2—O5	1.898 (3)	O4—Y1iv	3.847 (4)
Te2—O4	1.905 (3)	O5—Y1x	2.290 (3)
Te2—O3iii	2.681 (4)	O5—Y1ix	2.445 (3)
Te2—O8	2.723 (4)	O5—Te1iv	2.837 (3)
Te2—O2iv	2.798 (3)	O5—Cu1iii	3.543 (3)
Y1—O5v	2.290 (3)	O6—Cu1iii	1.999 (3)
Y1—O2	2.292 (3)	O6—Te1iii	2.657 (3)
Y1—O1i	2.357 (3)	O6—Y1x	3.801 (3)
Y1—O4vi	2.359 (3)	O7—N1xi	1.267 (6)
Y1—OW2	2.367 (4)	O7—Te2ii	3.798 (5)
Y1—OW1	2.373 (3)	O8—Te1iv	3.653 (5)
Y1—O5vi	2.445 (3)	O8—Y1x	3.787 (4)
Y1—O2i	2.497 (3)	O9—N1xi	1.233 (6)
Cu1—O1	1.904 (3)	O9—Te2xi	3.350 (4)
Cu1—O4	1.910 (3)	O9—Te2i	4.153 (4)
Cu1—O3iii	1.986 (3)	OW1—Te2ii	3.442 (4)
Cu1—O6i	1.999 (3)	OW1—Cu1ii	3.508 (4)
Cu1—O1iii	2.811 (4)	OW1—Te2v	3.628 (4)
Cu1—O4i	2.817 (4)	OW1—Cu1vi	3.632 (4)
N1—O9vii	1.233 (6)	OW1—H11	0.89 (3)
N1—O8	1.256 (6)	OW1—H12	0.89 (3)
N1—O7vii	1.267 (6)	OW2—Te1xii	3.447 (4)
N1—Te1vii	3.394 (4)	OW2—Cu1xii	3.574 (4)
O1—Y1iii	2.357 (3)	OW2—Cu1i	3.639 (4)
O1—Cu1i	2.811 (4)	OW2—H21	0.89 (3)
O1—Te1iii	3.679 (3)	OW2—H22	0.89 (3)
O1—Te2i	3.811 (3)	OW3—Te1xiii	4.018 (5)
O1—Y1viii	3.881 (4)	OW3—Te2ii	4.148 (5)
O2—Y1iii	2.497 (3)	OW3—H31	0.90 (3)
O2—Te2ii	2.798 (3)	OW3—H32	0.89 (3)
O3—Te1—O2	96.62 (15)	Cu1i—O3—Te2i	86.04 (11)
O3—Te1—O1	93.73 (14)	Te1—O3—Cu1	60.91 (10)
O2—Te1—O1	86.15 (14)	Cu1i—O3—Cu1	69.36 (10)
O3—Te1—O6i	77.24 (13)	Te2i—O3—Cu1	58.36 (7)
O2—Te1—O6i	155.35 (12)	Te1—O3—Y1	78.82 (10)
O1—Te1—O6i	70.67 (12)	Cu1i—O3—Y1	80.15 (10)
O3—Te1—O7	90.77 (15)	Te2i—O3—Y1	165.46 (11)
O2—Te1—O7	75.93 (13)	Cu1—O3—Y1	111.74 (8)
O1—Te1—O7	161.92 (13)	Te2—O4—Cu1	115.38 (17)
O6i—Te1—O7	127.41 (11)	Te2—O4—Y1ix	102.48 (14)
O3—Te1—O5ii	157.99 (12)	Cu1—O4—Y1ix	137.81 (17)
O2—Te1—O5ii	66.69 (13)	Te2—O4—Cu1iii	83.55 (12)
O1—Te1—O5ii	71.75 (12)	Cu1—O4—Cu1iii	93.83 (13)
O6i—Te1—O5ii	111.64 (10)	Y1ix—O4—Cu1iii	108.82 (13)
O7—Te1—O5ii	98.40 (13)	Te2—O4—Te2i	144.76 (16)
O6—Te2—O5	96.67 (15)	Cu1—O4—Te2i	61.40 (9)
O6—Te2—O4	94.00 (14)	Y1ix—O4—Te2i	77.07 (9)
O5—Te2—O4	85.42 (14)	Cu1iii—O4—Te2i	130.56 (10)
O6—Te2—O3iii	76.45 (13)	Te2—O4—Te1iii	69.18 (9)
O5—Te2—O3iii	153.70 (12)	Cu1—O4—Te1iii	57.63 (9)
O4—Te2—O3iii	70.03 (12)	Y1ix—O4—Te1iii	162.26 (14)
O6—Te2—O8	91.15 (14)	Cu1iii—O4—Te1iii	55.74 (6)
O5—Te2—O8	71.82 (13)	Te2i—O4—Te1iii	119.03 (9)
O4—Te2—O8	157.11 (13)	Te2—O4—Y1iv	93.11 (12)
O3iii—Te2—O8	132.81 (11)	Cu1—O4—Y1iv	87.45 (12)
O6—Te2—O2iv	159.67 (12)	Y1ix—O4—Y1iv	72.00 (9)
O5—Te2—O2iv	67.71 (13)	Cu1iii—O4—Y1iv	176.66 (11)
O4—Te2—O2iv	72.56 (12)	Te2i—O4—Y1iv	52.71 (5)
O3iii—Te2—O2iv	111.52 (10)	Te1iii—O4—Y1iv	122.87 (9)
O8—Te2—O2iv	95.81 (12)	Te2—O5—Y1x	136.03 (17)
O5v—Y1—O2	154.82 (12)	Te2—O5—Y1ix	99.64 (14)
O5v—Y1—O1i	111.21 (12)	Y1x—O5—Y1ix	108.37 (12)
O2—Y1—O1i	80.12 (12)	Te2—O5—Te1iv	100.31 (13)
O5v—Y1—O4vi	78.52 (12)	Y1x—O5—Te1iv	117.78 (13)
O2—Y1—O4vi	112.44 (12)	Y1ix—O5—Te1iv	78.46 (10)
O1i—Y1—O4vi	129.31 (11)	Te2—O5—Cu1iii	64.46 (9)
O5v—Y1—OW2	79.18 (12)	Y1x—O5—Cu1iii	83.26 (10)
O2—Y1—OW2	83.29 (12)	Y1ix—O5—Cu1iii	87.55 (9)
O1i—Y1—OW2	72.67 (12)	Te1iv—O5—Cu1iii	157.47 (12)
O4vi—Y1—OW2	153.52 (12)	Te2—O6—Cu1iii	111.53 (16)
O5v—Y1—OW1	84.04 (12)	Te2—O6—Te1iii	103.11 (14)
O2—Y1—OW1	78.45 (12)	Cu1iii—O6—Te1iii	86.06 (11)
O1i—Y1—OW1	154.67 (12)	Te2—O6—Cu1	61.11 (9)
O4vi—Y1—OW1	72.15 (12)	Cu1iii—O6—Cu1	69.15 (9)
OW2—Y1—OW1	91.49 (13)	Te1iii—O6—Cu1	58.27 (7)
O5v—Y1—O5vi	131.04 (10)	Te2—O6—Y1x	78.26 (10)
O2—Y1—O5vi	73.01 (11)	Cu1iii—O6—Y1x	80.34 (10)
O1i—Y1—O5vi	73.74 (11)	Te1iii—O6—Y1x	165.75 (11)
O4vi—Y1—O5vi	64.91 (11)	Cu1—O6—Y1x	112.14 (9)
OW2—Y1—O5vi	141.57 (12)	N1xi—O7—Te1	111.3 (3)
OW1—Y1—O5vi	112.16 (12)	N1xi—O7—Te2ii	149.8 (4)
O5v—Y1—O2i	72.04 (11)	Te1—O7—Te2ii	66.47 (9)
O2—Y1—O2i	132.19 (10)	N1xi—O7—Y1	140.9 (4)
O1i—Y1—O2i	64.87 (11)	Te1—O7—Y1	67.08 (8)
O4vi—Y1—O2i	72.51 (11)	Te2ii—O7—Y1	67.94 (6)
OW2—Y1—O2i	113.51 (12)	N1—O8—Te2	111.0 (3)
OW1—Y1—O2i	140.45 (11)	N1—O8—Te1iv	123.8 (4)
O5vi—Y1—O2i	66.79 (12)	Te2—O8—Te1iv	68.84 (9)
O1—Cu1—O4	179.67 (14)	N1—O8—Y1x	163.7 (4)
O1—Cu1—O3iii	92.32 (14)	Te2—O8—Y1x	71.18 (8)
O4—Cu1—O3iii	88.01 (14)	Te1iv—O8—Y1x	72.46 (7)
O1—Cu1—O6i	87.95 (13)	N1xi—O9—Te1	86.8 (3)
O4—Cu1—O6i	91.72 (14)	N1xi—O9—Te2xi	81.0 (3)
O3iii—Cu1—O6i	179.29 (14)	Te1—O9—Te2xi	148.43 (17)
O1—Cu1—O1iii	95.24 (13)	N1xi—O9—Te2i	140.3 (3)
O4—Cu1—O1iii	84.92 (13)	Te1—O9—Te2i	56.63 (6)
O3iii—Cu1—O1iii	68.03 (12)	Te2xi—O9—Te2i	138.25 (13)
O6i—Cu1—O1iii	111.29 (12)	Y1—OW1—Te2ii	96.11 (11)
O1—Cu1—O4i	84.84 (13)	Y1—OW1—Cu1ii	89.51 (11)
O4—Cu1—O4i	94.99 (13)	Te2ii—OW1—Cu1ii	55.27 (6)
O3iii—Cu1—O4i	112.68 (12)	Y1—OW1—Te2v	77.63 (10)
O6i—Cu1—O4i	68.00 (12)	Te2ii—OW1—Te2v	165.76 (11)
O1iii—Cu1—O4i	179.28 (9)	Cu1ii—OW1—Te2v	111.41 (9)
O9vii—N1—O8	121.6 (5)	Y1—OW1—Cu1vi	80.22 (9)
O9vii—N1—O7vii	120.0 (4)	Te2ii—OW1—Cu1vi	114.02 (10)
O8—N1—O7vii	118.3 (5)	Cu1ii—OW1—Cu1vi	58.82 (6)
O9vii—N1—Te2	77.9 (3)	Te2v—OW1—Cu1vi	52.63 (5)
O8—N1—Te2	48.7 (2)	Y1—OW1—H11	134 (5)
O7vii—N1—Te2	151.4 (4)	Te2ii—OW1—H11	83 (5)
O9vii—N1—Te1vii	71.9 (3)	Cu1ii—OW1—H11	125 (5)
O8—N1—Te1vii	165.1 (4)	Te2v—OW1—H11	111 (5)
O7vii—N1—Te1vii	48.4 (2)	Cu1vi—OW1—H11	142 (5)
Te2—N1—Te1vii	138.27 (15)	Y1—OW1—H12	110 (5)
Cu1—O1—Te1	114.77 (16)	Te2ii—OW1—H12	129 (5)
Cu1—O1—Y1iii	137.13 (17)	Cu1ii—OW1—H12	82 (5)
Te1—O1—Y1iii	103.12 (14)	Te2v—OW1—H12	45 (5)
Cu1—O1—Cu1i	94.20 (13)	Cu1vi—OW1—H12	37 (5)
Te1—O1—Cu1i	83.41 (12)	H11—OW1—H12	106 (6)
Y1iii—O1—Cu1i	109.90 (13)	Y1—OW2—Te1xii	96.56 (11)
Cu1—O1—Te1iii	60.78 (9)	Y1—OW2—Cu1xii	88.60 (11)
Te1—O1—Te1iii	143.74 (15)	Te1xii—OW2—Cu1xii	54.44 (6)
Y1iii—O1—Te1iii	76.93 (9)	Y1—OW2—Te1	77.77 (10)
Cu1i—O1—Te1iii	131.38 (10)	Te1xii—OW2—Te1	164.50 (12)
Cu1—O1—Te2i	57.54 (9)	Cu1xii—OW2—Te1	110.57 (10)
Te1—O1—Te2i	68.88 (9)	Y1—OW2—Cu1i	79.66 (10)
Y1iii—O1—Te2i	163.46 (14)	Te1xii—OW2—Cu1i	112.61 (10)
Cu1i—O1—Te2i	55.85 (6)	Cu1xii—OW2—Cu1i	58.20 (6)
Te1iii—O1—Te2i	118.32 (9)	Te1—OW2—Cu1i	52.42 (5)
Cu1—O1—Y1viii	87.20 (12)	Y1—OW2—H21	121 (5)
Te1—O1—Y1viii	92.47 (11)	Te1xii—OW2—H21	78 (5)
Y1iii—O1—Y1viii	71.31 (9)	Cu1xii—OW2—H21	128 (5)
Cu1i—O1—Y1viii	175.87 (11)	Te1—OW2—H21	117 (5)
Te1iii—O1—Y1viii	52.60 (5)	Cu1i—OW2—H21	157 (5)
Te2i—O1—Y1viii	122.26 (9)	Y1—OW2—H22	117 (5)
Te1—O2—Y1	136.04 (17)	Te1xii—OW2—H22	128 (5)
Te1—O2—Y1iii	98.37 (14)	Cu1xii—OW2—H22	86 (5)
Y1—O2—Y1iii	106.57 (12)	Te1—OW2—H22	47 (5)
Te1—O2—Te2ii	101.48 (14)	Cu1i—OW2—H22	46 (5)
Y1—O2—Te2ii	118.61 (13)	H21—OW2—H22	112 (7)
Y1iii—O2—Te2ii	77.90 (9)	Te1xiii—OW3—Te2ii	101.69 (12)
Te1—O2—Cu1i	63.55 (9)	Te1xiii—OW3—H31	77 (6)
Y1—O2—Cu1i	82.11 (10)	Te2ii—OW3—H31	59 (6)
Y1iii—O2—Cu1i	86.71 (9)	Te1xiii—OW3—H32	69 (6)
Te2ii—O2—Cu1i	156.91 (12)	Te2ii—OW3—H32	66 (6)
Te1—O3—Cu1i	112.24 (16)	H31—OW3—H32	106 (9)
Te1—O3—Te2i	102.52 (15)

D—H···A	D—H	H···A	D···A	D—H···A
OW1—H11···OW3	0.89 (3)	1.96 (3)	2.854 (6)	174 (7)
OW1—H12···O6v	0.89 (3)	1.88 (4)	2.729 (5)	157 (7)
OW2—H21···O8v	0.89 (3)	2.41 (6)	3.074 (5)	132 (6)
OW2—H21···OW3xiv	0.89 (3)	2.22 (5)	2.949 (6)	139 (6)
OW2—H22···O3	0.89 (3)	1.95 (5)	2.745 (5)	149 (7)
OW3—H31···O7	0.90 (3)	1.97 (4)	2.834 (7)	162 (9)
OW3—H31···O8xi	0.90 (3)	2.53 (8)	3.141 (7)	126 (7)
OW3—H32···O9xv	0.89 (3)	2.49 (4)	3.360 (7)	166 (9)
OW3—H32···O9xiii	0.89 (3)	2.64 (9)	3.253 (8)	127 (8)