The low-symmetry lanthanum(III) oxotellurate(IV), La10Te12O39

Wang, P.L.; Mozharivskyj, Y.

doi:10.1107/S1600536813012191

inorganic compounds

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Volume 69| Part 6| June 2013| Page i36

doi:10.1107/S1600536813012191

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The low-symmetry lanthanum(III) oxotellurate(IV), La₁₀Te₁₂O₃₉

Peng Li Wang ^a and Yurij Mozharivskyj ^a ^*

^aDepartment of Chemistry and Chemical Biology, McMaster University, 1280 Main Street West, Hamilton, Ontario, L8S 4M1, Canada
^*Correspondence e-mail: mozhar@mcmaster.ca

(Received 10 April 2013; accepted 3 May 2013; online 18 May 2013)

Single crystals of decalanthanum(III) dodecaoxotellurate(IV), La₁₀Te₁₂O₃₉, were obtained by reacting La₂O₃ and TeO₂ in a CsCl flux. Its crystal structure can be viewed as a three-dimensional network of corner- and edge-sharing LaO₈ polyhedra with Te^IV atoms filling the interstitial sites. The Te^IV atoms with their 5s² electron lone pairs distort the LaO₈ polyhedra through variable Te—O bonds. Among the six unique Te sites, four of them define empty channels extending parallel to the a axis. The formation of these channels is a result of the stereochemically active electron lone pairs on the Te^IV atoms. The atomic arrangement of the Te—O units can be understood on the basis of the valence shell electron pair repulsion (VSEPR) model. A certain degree of disorder is observed in the crystal structure. As a result, one of the five different La sites is split into two positions with an occupancy ratio of 0.875 (2):0.125 (2). Also, one of the oxygen sites is split into two positions in a 0.559 (13):0.441 (13) ratio, and one O site is half-occupied. Such disorder was observed in all measured La₁₀Te₁₂O₃₉ crystals.

Related literature

For the structures of related rare-earth oxotellurates(IV), see: Castro et al. (1990 ); Weber et al. (2001 ); Meier et al. (2009 ). For synthetic details, see: Weber & Schleid (2000 ). For standardization of structural data, see: Gelato & Parthé (1987 ). For the VSEPR model, see: Gillespie (1970 ). For the bond-valence method, see: Brown (2009 ).

Experimental

Crystal data

La₁₀Te₁₂O₃₉
M_r = 3544.30
Triclinic, $[P \overline 1]$
a = 5.6856 (11) Å
b = 12.621 (3) Å
c = 14.402 (3) Å
α = 95.53 (3)°
β = 100.88 (3)°
γ = 93.13 (3)°
V = 1007.3 (3) Å³
Z = 1
Mo Kα radiation
μ = 18.98 mm⁻¹
T = 293 K
0.12 × 0.04 × 0.02 mm

Data collection

Stoe IPDSII diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2004 ) T_min = 0.256, T_max = 0.702
18743 measured reflections
8922 independent reflections
5110 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.064
S = 0.77
8922 reflections
289 parameters
Δρ_max = 3.71 e Å⁻³
Δρ_min = −3.98 e Å⁻³

Data collection: X-AREA (Stoe, 2004); cell refinement: X-AREA; data reduction: X-RED32 (Stoe, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Crystal Impact, 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813012191/wm2737sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813012191/wm2737Isup2.hkl

checkCIF report

Comment top

A number of rare-earth(III) oxotellurates(IV), including Dy₂Te₃O₉ (Meier et al., 2009), Nd₂Te₄O₁₁ (Castro et al., 1990) and Ho₂Te₅O₁₃ (Weber et al., 2001), have been prepared and structurally characterized. Despite their different compositions, these compounds all contain tellurium atoms in the oxidation state +IV. The remaining two electrons on the Te^IV atoms usually form stereo-chemically active but chemically non-bonding electron lone pairs. The local atomic arrangements around these Te^IV atoms with electron lone pairs can be understood on basis of the 'Valence Shell Electron Pair Repulsion' (VSEPR) model (Gillespie, 1970). As the local symmetry of the Te^IV sites is reduced by the lone pairs, these compounds usually adopt low-symmetry space groups, e.g. C2/c for Nd₂Te₄O₁₁, P1 for Ho₂Te₅O₁₃ or P2₁/c for Dy₂Te₃O₉. The title compound, La₁₀Te₁₂O₃₉, can be considered as another member of the rare-earth(III) oxotellurates(IV) family. Structural similarities can be observed between La₁₀Te₁₂O₃₉ and other rare-earth(III) oxotellurates(IV), including the distorted LaO₈ polyhedra and a number of different Te–O structural motifs. Among the six Te atoms in the unit cell, four of them define empty channels parallel to the a-axis, while the other two fill the interstitial positions between the LaO₈ polyhedra (Fig. 1).

If Te–O distances ≤ 2.03 Å (sum of the Te and O covalent radii) are considered as primary Te–O bonds, three TeO₃ units (for Te1, Te4 and Te6) can be identified. Also, a fourth long Te–O interaction is observed for each of these three Te atoms (the fourth oxygen atoms is 2.852 (6) Å from Te1, 2.923 (8) Å from Te4 and 2.802 (6) Å from Te6). Bond valence sum calculations (Brown, 2009) show a minimal contribution from these long interactions; when these interactions are discarded, the bond valence sums for the 3-coordinated Te1, Te4 and Te6 atoms are close to 4.0 valence units (v.u.). The other three Te atoms (Te2, Te3 and Te5) display shorter secondary Te–O interactions (≤ 2.5 Å), which allow them to form TeO₄ units in distorted seesaw configurations. The bond valence sums indicate significant contributions from these interactions. For these TeO₄ units, bond valence sum are 3.9 v.u, 3.9 v.u and 4.4 v.u for Te2, Te3 and Te5, respectively. Such results are consistent with the assignment of oxidation state +IV for the Te atoms.

The competition between the Te2 and Te5 atoms to form stronger interactions with the bridging oxygen atom (O19) also causes disorder on the oxygen site. As a result, O19 is split into two separated oxygen positions (O191 and O192) to account for the electron density distribution. In addition to the disordered oxygen sites, one of the lanthanum sites (La5) is also described by split positions (La51 and La52). Such disorder could be a consequence of the asymmetric environment in the distorted LaO₈ polyhedron.

Related literature top

For the structures of related rare-earth oxotellurates(IV), see: Castro et al. (1990); Weber et al. (2001); Meier et al. (2009). For synthetic details, see: Weber & Schleid (2000). For standardization of structural data, see: (Gelato & Parthé, 1987). For the VSEPR model, see: Gillespie (1970). For the bond-valence method, see: Brown (2009).

Experimental top

Single crystals of La₁₀Te₁₂O₃₉ were obtained by reacting La₂O₃ (99.99 wt. %, Rhône-Poulenc, pre-fired at 1273 K for 12 h) and TeO₂ (99.99%, Johnson Matthey Electronics) in a CsCl (99.9%, Alfa-Aesar) flux (Weber & Schleid, 2000). In total, 0.1 gram of the La₂O₃ and TeO₂ powder with the 1:2 molar ratio were ground and mixed with 1.9 grams of CsCl. The sample mixture was placed in an alumina crucible, which was sealed in a silica tube under vacuum. The sample was heated to 1273 K at a rate of 50 K/h. After holding at 1273 K for 72 h, the temperature was then slowly decreased to 1073 K at a rate of 5 K/hour. After annealing at 1073 K for 20 h, the sample was quenched in air. Transparent, colorless, needle-shaped single crystals were obtained by washing away the salt flux with distilled water and ethanol.

Computing details top

Data collection: X-AREA (Stoe, 2004); cell refinement: X-AREA (Stoe, 2004); data reduction: X-RED32 (Stoe, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Crystal Impact, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The crystal structure of La₁₀Te₁₂O₃₉ represented with displacement ellipsoids at the 90% probability level.

Decalanthanum dodecatellurium triacontnonaoxide top

Crystal data top

La₁₀Te₁₂O₃₉	Z = 1
M_r = 3544.30	F(000) = 1506
Triclinic, P1	D_x = 5.843 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.6856 (11) Å	Cell parameters from 18743 reflections
b = 12.621 (3) Å	θ = 2.9–36.9°
c = 14.402 (3) Å	µ = 18.98 mm⁻¹
α = 95.53 (3)°	T = 293 K
β = 100.88 (3)°	Needle, colourless
γ = 93.13 (3)°	0.12 × 0.04 × 0.02 mm
V = 1007.3 (3) Å³

Data collection top

Stoe IPDSII diffractometer	8922 independent reflections
Radiation source: fine-focus sealed tube	5110 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ω–scan	θ_max = 36.3°, θ_min = 2.9°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2004)	h = −9→6
T_min = 0.256, T_max = 0.702	k = −21→20
18743 measured reflections	l = −23→23

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F_o²) + (0.0122P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.064	(Δ/σ)_max = 0.003
S = 0.77	Δρ_max = 3.71 e Å⁻³
8922 reflections	Δρ_min = −3.98 e Å⁻³
289 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00195 (3)

Crystal data top

La₁₀Te₁₂O₃₉	γ = 93.13 (3)°
M_r = 3544.30	V = 1007.3 (3) Å³
Triclinic, P1	Z = 1
a = 5.6856 (11) Å	Mo Kα radiation
b = 12.621 (3) Å	µ = 18.98 mm⁻¹
c = 14.402 (3) Å	T = 293 K
α = 95.53 (3)°	0.12 × 0.04 × 0.02 mm
β = 100.88 (3)°

Data collection top

Stoe IPDSII diffractometer	8922 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2004)	5110 reflections with I > 2σ(I)
T_min = 0.256, T_max = 0.702	R_int = 0.063
18743 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	289 parameters
wR(F²) = 0.064	0 restraints
S = 0.77	Δρ_max = 3.71 e Å⁻³
8922 reflections	Δρ_min = −3.98 e Å⁻³

Special details top

Experimental. A numerical absorption correction was based on the crystal shape that was originally derived from the optical face indexing but later optimized against equivalent reflections using Stoe X-SHAPE software (Stoe & Cie GmbH, 2004)

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

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

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
La1	0.42088 (10)	0.52484 (4)	0.35191 (3)	0.00809 (10)
La2	0.54271 (10)	0.15044 (4)	0.55453 (3)	0.01179 (12)
La3	0.79356 (10)	0.07556 (4)	0.08168 (3)	0.00813 (9)
La4	0.81948 (10)	0.38287 (4)	0.17100 (4)	0.01151 (11)
La51	0.93544 (12)	0.03921 (6)	0.37049 (5)	0.01013 (15)	0.875 (2)
La52	0.9564 (9)	0.0092 (4)	0.3946 (4)	0.01013 (15)	0.125 (2)
Te1	0.03902 (11)	0.34576 (4)	0.44123 (4)	0.01010 (11)
Te2	0.10966 (12)	0.29104 (6)	0.71241 (4)	0.01761 (14)
Te3	0.22321 (11)	0.24798 (5)	0.00280 (4)	0.00909 (11)
Te4	0.48089 (10)	0.20819 (4)	0.28804 (4)	0.01029 (11)
Te5	0.33718 (14)	0.55670 (7)	0.09840 (5)	0.02424 (16)
Te6	0.28887 (10)	0.90925 (4)	0.18953 (3)	0.00793 (10)
O1	0.0464 (12)	0.8560 (5)	0.3423 (5)	0.0228 (15)
O2	0.0751 (13)	0.2551 (6)	0.1077 (5)	0.0248 (15)
O3	0.0812 (11)	0.3836 (5)	0.3226 (4)	0.0165 (13)
O4	0.0853 (11)	0.1040 (5)	0.9697 (4)	0.0157 (13)
O5	0.0957 (12)	0.0194 (5)	0.2117 (4)	0.0157 (13)
O6	0.1285 (13)	0.6544 (6)	0.3738 (4)	0.0217 (14)
O7	0.1599 (13)	0.5237 (5)	0.1880 (4)	0.0202 (14)
O8	0.1863 (14)	0.2177 (6)	0.4339 (5)	0.0243 (15)
O9	0.2484 (11)	0.0094 (5)	0.4996 (4)	0.0153 (13)
O10	0.3008 (13)	0.4396 (6)	0.4992 (4)	0.0238 (16)
O11	0.3612 (12)	0.2841 (5)	0.6470 (4)	0.0193 (13)
O12	0.4366 (11)	0.9645 (5)	0.0960 (4)	0.0166 (12)
O13	0.4386 (16)	0.4258 (8)	0.0647 (5)	0.039 (2)
O14	0.4707 (11)	0.0531 (5)	0.7030 (4)	0.0195 (14)
O15	0.5313 (11)	0.2219 (5)	0.0575 (5)	0.0253 (16)
O16	0.5651 (11)	0.3536 (5)	0.2926 (4)	0.0139 (12)
O17	0.6547 (11)	0.1833 (5)	0.4068 (4)	0.0139 (12)
O18	0.7421 (12)	0.1666 (6)	0.2342 (4)	0.0207 (13)
O191	0.290 (2)	0.4482 (9)	0.7515 (8)	0.0153 (18)	0.559 (13)
O192	0.382 (3)	0.4438 (11)	0.8010 (10)	0.0153 (18)	0.441 (13)
O20	0.916 (3)	0.4450 (15)	0.0126 (8)	0.032 (4)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.0086 (2)	0.0071 (2)	0.00811 (18)	0.00113 (17)	0.00047 (17)	0.00086 (15)
La2	0.0160 (3)	0.0123 (2)	0.0099 (2)	0.0065 (2)	0.0060 (2)	0.00511 (16)
La3	0.0085 (2)	0.00864 (19)	0.00750 (17)	0.00180 (17)	0.00207 (15)	0.00023 (14)
La4	0.0087 (2)	0.0109 (2)	0.0138 (2)	0.00191 (17)	−0.00131 (18)	0.00210 (17)
La51	0.0097 (2)	0.0098 (3)	0.0121 (3)	0.0027 (2)	0.0034 (2)	0.0037 (2)
La52	0.0097 (2)	0.0098 (3)	0.0121 (3)	0.0027 (2)	0.0034 (2)	0.0037 (2)
Te1	0.0108 (2)	0.0096 (2)	0.0100 (2)	−0.0011 (2)	0.00199 (18)	0.00261 (17)
Te2	0.0136 (3)	0.0306 (4)	0.0117 (2)	0.0098 (3)	0.0051 (2)	0.0082 (2)
Te3	0.0073 (2)	0.0111 (2)	0.00840 (19)	0.0012 (2)	0.00017 (18)	0.00111 (17)
Te4	0.0113 (2)	0.0080 (2)	0.0109 (2)	−0.00019 (19)	0.00045 (18)	0.00099 (16)
Te5	0.0210 (4)	0.0329 (4)	0.0213 (3)	0.0096 (3)	0.0112 (3)	−0.0031 (3)
Te6	0.0080 (2)	0.0077 (2)	0.00793 (19)	0.00001 (18)	0.00129 (18)	0.00082 (16)
O1	0.015 (3)	0.014 (3)	0.037 (4)	0.002 (2)	−0.004 (3)	0.008 (3)
O2	0.028 (4)	0.023 (4)	0.025 (3)	−0.007 (3)	0.019 (3)	−0.011 (3)
O3	0.016 (3)	0.019 (3)	0.012 (2)	−0.008 (2)	−0.003 (2)	0.008 (2)
O4	0.012 (3)	0.014 (3)	0.019 (3)	−0.003 (2)	0.002 (2)	−0.007 (2)
O5	0.022 (3)	0.017 (3)	0.008 (2)	0.010 (3)	0.001 (2)	0.001 (2)
O6	0.026 (4)	0.026 (3)	0.015 (3)	0.014 (3)	0.003 (3)	0.004 (2)
O7	0.022 (3)	0.020 (3)	0.019 (3)	0.005 (3)	0.000 (3)	0.006 (2)
O8	0.030 (4)	0.022 (3)	0.022 (3)	0.013 (3)	−0.001 (3)	0.009 (2)
O9	0.011 (3)	0.017 (3)	0.017 (3)	0.000 (2)	−0.003 (2)	0.007 (2)
O10	0.024 (3)	0.023 (3)	0.019 (3)	−0.013 (3)	−0.007 (3)	0.008 (2)
O11	0.022 (3)	0.013 (3)	0.024 (3)	0.001 (3)	0.011 (3)	−0.004 (2)
O12	0.011 (3)	0.029 (3)	0.012 (2)	0.003 (3)	0.004 (2)	0.007 (2)
O13	0.038 (5)	0.063 (6)	0.014 (3)	0.035 (4)	−0.005 (3)	0.001 (3)
O14	0.015 (3)	0.029 (3)	0.012 (2)	−0.008 (3)	−0.005 (2)	0.008 (2)
O15	0.009 (3)	0.014 (3)	0.046 (4)	0.003 (2)	−0.011 (3)	0.002 (3)
O16	0.014 (3)	0.008 (2)	0.020 (3)	0.003 (2)	0.001 (2)	0.005 (2)
O17	0.019 (3)	0.020 (3)	0.006 (2)	0.006 (2)	0.006 (2)	0.006 (2)
O18	0.022 (3)	0.025 (3)	0.015 (2)	0.006 (3)	0.005 (2)	−0.005 (2)
O191	0.018 (5)	0.011 (4)	0.021 (4)	0.004 (4)	0.012 (4)	0.002 (3)
O192	0.018 (5)	0.011 (4)	0.021 (4)	0.004 (4)	0.012 (4)	0.002 (3)
O20	0.028 (8)	0.066 (11)	0.010 (5)	0.026 (8)	0.007 (5)	0.020 (6)

Geometric parameters (Å, º) top

La1—O10ⁱ	2.400 (6)	Te2—O191	2.156 (11)
La1—O6	2.435 (7)	Te2—O192	2.488 (14)
La1—O191ⁱ	2.448 (12)	Te3—O15	1.841 (6)
La1—O16	2.485 (6)	Te3—O2	1.861 (7)
La1—O3	2.502 (6)	Te3—O4^ix	1.919 (6)
La1—O7	2.539 (6)	Te3—O13	2.496 (10)
La1—O11ⁱ	2.647 (6)	Te4—O16	1.863 (6)
La1—O10	2.652 (7)	Te4—O17	1.871 (5)
La1—O192ⁱ	2.706 (15)	Te4—O18	1.877 (7)
La2—O9	2.345 (6)	Te5—O13	1.831 (9)
La2—O17	2.400 (6)	Te5—O7	1.845 (7)
La2—O11	2.441 (6)	Te5—O20^vi	1.936 (13)
La2—O9ⁱⁱ	2.528 (7)	Te5—O192ⁱ	1.945 (15)
La2—O1ⁱ	2.531 (6)	Te6—O5^x	1.859 (7)
La2—O8	2.643 (6)	Te6—O14ⁱ	1.866 (5)
La2—O14	2.651 (6)	Te6—O12	1.883 (6)
La2—O6ⁱ	2.985 (7)	O1—Te2^viii	2.032 (7)
La3—O15	2.447 (6)	O1—La52^xi	2.131 (9)
La3—O18	2.454 (6)	O1—La51^xi	2.446 (7)
La3—O12ⁱⁱⁱ	2.456 (6)	O1—La2ⁱ	2.531 (6)
La3—O5^iv	2.477 (6)	O2—La4^xii	2.453 (8)
La3—O4ⁱⁱ	2.489 (7)	O2—La3^xii	2.655 (7)
La3—O4^v	2.557 (7)	O3—La4^xii	2.398 (5)
La3—O12^vi	2.633 (5)	O4—Te3^xiii	1.919 (6)
La3—O2^iv	2.655 (7)	O4—La3ⁱⁱ	2.489 (7)
La4—O3^iv	2.398 (5)	O4—La3^xiv	2.557 (7)
La4—O2^iv	2.453 (8)	O5—Te6ⁱⁱⁱ	1.859 (7)
La4—O191ⁱ	2.476 (11)	O5—La3^xii	2.477 (6)
La4—O16	2.513 (7)	O5—La51^xii	2.612 (6)
La4—O7^iv	2.516 (7)	O5—La52^xii	2.902 (8)
La4—O13	2.522 (7)	O6—Te2^viii	1.866 (6)
La4—O192ⁱ	2.556 (15)	O6—La2ⁱ	2.985 (7)
La4—O20	2.626 (13)	O7—La4^xii	2.516 (7)
La4—O15	2.733 (6)	O8—La51^xii	2.589 (7)
La4—O18	2.995 (7)	O8—La52^xii	2.829 (9)
La51—O9^iv	2.393 (6)	O9—La52^xii	2.023 (7)
La51—O9ⁱⁱ	2.420 (7)	O9—La52ⁱⁱ	2.107 (9)
La51—O1^vii	2.446 (7)	O9—La51^xii	2.393 (6)
La51—O14ⁱⁱ	2.521 (6)	O9—La51ⁱⁱ	2.420 (7)
La51—O17	2.565 (7)	O9—La2ⁱⁱ	2.528 (7)
La51—O8^iv	2.589 (7)	O10—La1ⁱ	2.400 (6)
La51—O5^iv	2.612 (6)	O11—La1ⁱ	2.647 (6)
La51—O18	2.763 (7)	O12—La3^x	2.456 (6)
La52—O9^iv	2.023 (7)	O12—La3^vi	2.633 (5)
La52—O9ⁱⁱ	2.107 (9)	O14—Te6ⁱ	1.866 (5)
La52—O1^vii	2.131 (9)	O14—La51ⁱⁱ	2.521 (6)
La52—O14ⁱⁱ	2.604 (7)	O14—La52ⁱⁱ	2.604 (7)
La52—O8^iv	2.829 (9)	O191—O192	0.808 (16)
La52—O17	2.872 (8)	O191—La1ⁱ	2.448 (12)
La52—O5^iv	2.902 (8)	O191—La4ⁱ	2.476 (11)
Te1—O10	1.861 (6)	O192—Te5ⁱ	1.945 (15)
Te1—O8	1.864 (7)	O192—La4ⁱ	2.556 (15)
Te1—O3	1.872 (6)	O192—La1ⁱ	2.706 (15)
Te2—O11	1.857 (7)	O20—O20^xv	1.75 (4)
Te2—O6^viii	1.866 (6)	O20—Te5^vi	1.936 (13)
Te2—O1^viii	2.032 (7)

O10ⁱ—La1—O6	100.8 (2)	O9ⁱⁱ—La51—O5^iv	159.6 (2)
O10ⁱ—La1—O191ⁱ	97.2 (3)	O1^vii—La51—O5^iv	71.5 (2)
O6—La1—O191ⁱ	121.3 (3)	O14ⁱⁱ—La51—O5^iv	94.0 (2)
O10ⁱ—La1—O16	99.0 (2)	O17—La51—O5^iv	122.32 (18)
O6—La1—O16	156.5 (2)	O8^iv—La51—O5^iv	94.0 (2)
O191ⁱ—La1—O16	68.0 (3)	O9^iv—La51—O18	149.6 (2)
O10ⁱ—La1—O3	123.0 (2)	O9ⁱⁱ—La51—O18	125.3 (2)
O6—La1—O3	87.4 (2)	O1^vii—La51—O18	126.6 (2)
O191ⁱ—La1—O3	126.1 (3)	O14ⁱⁱ—La51—O18	75.5 (2)
O16—La1—O3	71.2 (2)	O17—La51—O18	58.70 (18)
O10ⁱ—La1—O7	168.4 (2)	O8^iv—La51—O18	79.75 (19)
O6—La1—O7	75.5 (2)	O5^iv—La51—O18	64.02 (19)
O191ⁱ—La1—O7	76.1 (3)	O9^iv—La52—O9ⁱⁱ	86.2 (3)
O16—La1—O7	87.4 (2)	O9^iv—La52—O1^vii	86.6 (3)
O3—La1—O7	68.2 (2)	O9ⁱⁱ—La52—O1^vii	108.8 (4)
O10ⁱ—La1—O11ⁱ	73.2 (2)	O9^iv—La52—O14ⁱⁱ	156.7 (4)
O6—La1—O11ⁱ	73.3 (2)	O9ⁱⁱ—La52—O14ⁱⁱ	76.7 (3)
O191ⁱ—La1—O11ⁱ	59.6 (3)	O1^vii—La52—O14ⁱⁱ	84.1 (3)
O16—La1—O11ⁱ	125.0 (2)	O9^iv—La52—O8^iv	71.1 (3)
O3—La1—O11ⁱ	157.5 (2)	O9ⁱⁱ—La52—O8^iv	106.8 (3)
O7—La1—O11ⁱ	95.2 (2)	O1^vii—La52—O8^iv	136.2 (3)
O10ⁱ—La1—O10	63.2 (3)	O14ⁱⁱ—La52—O8^iv	128.9 (3)
O6—La1—O10	86.3 (2)	O9^iv—La52—O17	117.3 (3)
O191ⁱ—La1—O10	149.8 (3)	O9ⁱⁱ—La52—O17	69.9 (3)
O16—La1—O10	91.4 (2)	O1^vii—La52—O17	155.5 (3)
O3—La1—O10	61.16 (18)	O14ⁱⁱ—La52—O17	71.7 (2)
O7—La1—O10	126.7 (2)	O8^iv—La52—O17	62.9 (2)
O11ⁱ—La1—O10	127.04 (19)	O9^iv—La52—O5^iv	110.9 (3)
O10ⁱ—La1—O192ⁱ	113.7 (4)	O9ⁱⁱ—La52—O5^iv	162.5 (3)
O6—La1—O192ⁱ	111.4 (4)	O1^vii—La52—O5^iv	70.1 (3)
O191ⁱ—La1—O192ⁱ	17.1 (4)	O14ⁱⁱ—La52—O5^iv	85.8 (2)
O16—La1—O192ⁱ	71.3 (3)	O8^iv—La52—O5^iv	83.1 (2)
O3—La1—O192ⁱ	115.1 (3)	O17—La52—O5^iv	103.5 (2)
O7—La1—O192ⁱ	59.1 (4)	O10—Te1—O8	100.6 (3)
O11ⁱ—La1—O192ⁱ	63.8 (3)	O10—Te1—O3	89.4 (3)
O10—La1—O192ⁱ	162.1 (4)	O8—Te1—O3	96.2 (3)
O10ⁱ—La1—Te1	93.63 (16)	O11—Te2—O6^viii	102.3 (3)
O9—La2—O17	99.5 (2)	O11—Te2—O1^viii	95.2 (3)
O9—La2—O11	106.8 (2)	O6^viii—Te2—O1^viii	86.7 (3)
O17—La2—O11	122.0 (2)	O11—Te2—O191	78.0 (4)
O9—La2—O9ⁱⁱ	72.4 (3)	O6^viii—Te2—O191	90.4 (4)
O17—La2—O9ⁱⁱ	72.6 (2)	O1^viii—Te2—O191	171.9 (4)
O11—La2—O9ⁱⁱ	164.7 (2)	O11—Te2—O192	79.9 (4)
O9—La2—O1ⁱ	128.0 (2)	O6^viii—Te2—O192	108.0 (4)
O17—La2—O1ⁱ	100.2 (2)	O1^viii—Te2—O192	165.2 (4)
O11—La2—O1ⁱ	102.3 (2)	O191—Te2—O192	18.3 (4)
O9ⁱⁱ—La2—O1ⁱ	68.6 (2)	O15—Te3—O2	101.3 (3)
O9—La2—O8	70.7 (2)	O15—Te3—O4^ix	99.7 (3)
O17—La2—O8	67.6 (2)	O2—Te3—O4^ix	88.2 (3)
O11—La2—O8	73.9 (2)	O15—Te3—O13	73.6 (3)
O9ⁱⁱ—La2—O8	118.8 (2)	O2—Te3—O13	89.1 (3)
O1ⁱ—La2—O8	160.4 (2)	O4^ix—Te3—O13	172.1 (2)
O9—La2—O14	72.04 (19)	O16—Te4—O17	99.0 (3)
O17—La2—O14	161.3 (2)	O16—Te4—O18	94.0 (3)
O11—La2—O14	76.7 (2)	O17—Te4—O18	88.6 (3)
O9ⁱⁱ—La2—O14	88.8 (2)	O13—Te5—O7	101.0 (4)
O1ⁱ—La2—O14	74.1 (2)	O13—Te5—O20^vi	95.8 (6)
O8—La2—O14	122.3 (2)	O7—Te5—O20^vi	100.5 (5)
O9—La2—O6ⁱ	173.5 (2)	O13—Te5—O192ⁱ	80.4 (5)
O17—La2—O6ⁱ	82.1 (2)	O7—Te5—O192ⁱ	86.2 (5)
O11—La2—O6ⁱ	67.3 (2)	O20^vi—Te5—O192ⁱ	172.9 (6)
O9ⁱⁱ—La2—O6ⁱ	114.1 (2)	O5^x—Te6—O14ⁱ	96.7 (3)
O1ⁱ—La2—O6ⁱ	57.4 (2)	O5^x—Te6—O12	99.5 (3)
O8—La2—O6ⁱ	104.5 (2)	O14ⁱ—Te6—O12	100.2 (3)
O14—La2—O6ⁱ	108.17 (17)	Te2^viii—O1—La52^xi	140.8 (4)
O15—La3—O18	68.9 (2)	Te2^viii—O1—La51^xi	139.5 (3)
O15—La3—O12ⁱⁱⁱ	87.2 (2)	La52^xi—O1—La51^xi	11.06 (15)
O18—La3—O12ⁱⁱⁱ	83.6 (2)	Te2^viii—O1—La2ⁱ	113.0 (3)
O15—La3—O5^iv	137.5 (2)	La52^xi—O1—La2ⁱ	100.1 (3)
O18—La3—O5^iv	70.7 (2)	La51^xi—O1—La2ⁱ	105.8 (2)
O12ⁱⁱⁱ—La3—O5^iv	100.8 (2)	Te3—O2—La4^xii	133.6 (4)
O15—La3—O4ⁱⁱ	150.80 (19)	Te3—O2—La3^xii	104.2 (3)
O18—La3—O4ⁱⁱ	134.4 (2)	La4^xii—O2—La3^xii	101.3 (3)
O12ⁱⁱⁱ—La3—O4ⁱⁱ	80.0 (2)	Te1—O3—La4^xii	134.1 (3)
O5^iv—La3—O4ⁱⁱ	71.1 (2)	Te1—O3—La1	107.3 (2)
O15—La3—O4^v	103.2 (2)	La4^xii—O3—La1	113.3 (2)
O18—La3—O4^v	134.4 (2)	Te3^xiii—O4—La3ⁱⁱ	139.3 (3)
O12ⁱⁱⁱ—La3—O4^v	141.94 (19)	Te3^xiii—O4—La3^xiv	106.1 (3)
O5^iv—La3—O4^v	95.7 (2)	La3ⁱⁱ—O4—La3^xiv	106.7 (2)
O4ⁱⁱ—La3—O4^v	73.3 (2)	Te6ⁱⁱⁱ—O5—La3^xii	121.3 (3)
O15—La3—O12^vi	75.3 (2)	Te6ⁱⁱⁱ—O5—La51^xii	119.3 (3)
O18—La3—O12^vi	140.1 (2)	La3^xii—O5—La51^xii	109.6 (3)
O12ⁱⁱⁱ—La3—O12^vi	77.4 (2)	Te6ⁱⁱⁱ—O5—La52^xii	109.8 (3)
O5^iv—La3—O12^vi	147.1 (2)	La3^xii—O5—La52^xii	117.1 (3)
O4ⁱⁱ—La3—O12^vi	76.3 (2)	La51^xii—O5—La52^xii	9.51 (11)
O4^v—La3—O12^vi	70.38 (19)	Te2^viii—O6—La1	131.9 (3)
O15—La3—O2^iv	72.9 (2)	Te2^viii—O6—La2ⁱ	101.1 (3)
O18—La3—O2^iv	74.6 (2)	La1—O6—La2ⁱ	100.1 (2)
O12ⁱⁱⁱ—La3—O2^iv	154.5 (2)	Te5—O7—La4^xii	128.2 (3)
O5^iv—La3—O2^iv	84.6 (2)	Te5—O7—La1	112.1 (3)
O4ⁱⁱ—La3—O2^iv	124.9 (2)	La4^xii—O7—La1	108.2 (2)
O4^v—La3—O2^iv	60.6 (2)	Te1—O8—La51^xii	120.8 (3)
O12^vi—La3—O2^iv	111.4 (2)	Te1—O8—La2	129.5 (3)
O15—La3—Te3^iv	84.65 (18)	La51^xii—O8—La2	100.7 (2)
O18—La3—Te3^iv	104.67 (17)	Te1—O8—La52^xii	127.0 (4)
O12ⁱⁱⁱ—La3—Te3^iv	165.27 (13)	La51^xii—O8—La52^xii	10.27 (10)
O5^iv—La3—Te3^iv	93.53 (16)	La2—O8—La52^xii	91.0 (2)
O4ⁱⁱ—La3—Te3^iv	101.55 (16)	La52^xii—O9—La52ⁱⁱ	93.8 (3)
O4^v—La3—Te3^iv	30.83 (13)	La52^xii—O9—La2	126.6 (3)
O12^vi—La3—Te3^iv	88.70 (14)	La52ⁱⁱ—O9—La2	108.6 (3)
O2^iv—La3—Te3^iv	30.10 (14)	La52^xii—O9—La51^xii	10.31 (16)
O3^iv—La4—O2^iv	87.2 (2)	La52ⁱⁱ—O9—La51^xii	99.6 (3)
O3^iv—La4—O191ⁱ	81.8 (3)	La2—O9—La51^xii	116.4 (3)
O2^iv—La4—O191ⁱ	158.2 (3)	La52^xii—O9—La51ⁱⁱ	101.2 (3)
O3^iv—La4—O16	71.8 (2)	La52ⁱⁱ—O9—La51ⁱⁱ	11.21 (15)
O2^iv—La4—O16	126.8 (2)	La2—O9—La51ⁱⁱ	109.7 (2)
O191ⁱ—La4—O16	67.2 (3)	La51^xii—O9—La51ⁱⁱ	108.1 (3)
O3^iv—La4—O7^iv	70.2 (2)	La52^xii—O9—La2ⁱⁱ	103.2 (3)
O2^iv—La4—O7^iv	88.0 (2)	La52ⁱⁱ—O9—La2ⁱⁱ	117.3 (3)
O191ⁱ—La4—O7^iv	70.6 (3)	La2—O9—La2ⁱⁱ	107.6 (3)
O16—La4—O7^iv	125.9 (2)	La51^xii—O9—La2ⁱⁱ	107.5 (2)
O3^iv—La4—O13	153.1 (3)	La51ⁱⁱ—O9—La2ⁱⁱ	107.1 (2)
O2^iv—La4—O13	119.0 (2)	Te1—O10—La1ⁱ	139.7 (3)
O191ⁱ—La4—O13	75.2 (3)	Te1—O10—La1	102.0 (2)
O16—La4—O13	86.4 (3)	La1ⁱ—O10—La1	116.8 (3)
O7^iv—La4—O13	113.6 (3)	Te2—O11—La2	138.5 (3)
O3^iv—La4—O192ⁱ	100.2 (4)	Te2—O11—La1ⁱ	111.5 (3)
O2^iv—La4—O192ⁱ	159.8 (4)	La2—O11—La1ⁱ	110.0 (3)
O191ⁱ—La4—O192ⁱ	18.4 (4)	Te6—O12—La3^x	140.4 (3)
O16—La4—O192ⁱ	73.4 (4)	Te6—O12—La3^vi	117.0 (3)
O7^iv—La4—O192ⁱ	77.0 (4)	La3^x—O12—La3^vi	102.6 (2)
O13—La4—O192ⁱ	57.4 (4)	Te5—O13—Te3	133.3 (4)
O3^iv—La4—O20	129.1 (4)	Te5—O13—La4	113.8 (4)
O2^iv—La4—O20	71.6 (4)	Te3—O13—La4	104.4 (3)
O191ⁱ—La4—O20	101.1 (5)	Te6ⁱ—O14—La51ⁱⁱ	149.0 (3)
O16—La4—O20	155.9 (3)	Te6ⁱ—O14—La52ⁱⁱ	157.7 (4)
O7^iv—La4—O20	63.5 (4)	La51ⁱⁱ—O14—La52ⁱⁱ	11.98 (12)
O13—La4—O20	70.0 (4)	Te6ⁱ—O14—La2	112.9 (3)
O192ⁱ—La4—O20	89.4 (5)	La51ⁱⁱ—O14—La2	97.73 (17)
O3^iv—La4—O15	131.0 (2)	La52ⁱⁱ—O14—La2	87.0 (2)
O2^iv—La4—O15	71.4 (2)	Te3—O15—La3	141.2 (3)
O191ⁱ—La4—O15	129.5 (3)	Te3—O15—La4	119.0 (3)
O16—La4—O15	86.3 (2)	La3—O15—La4	99.34 (19)
O7^iv—La4—O15	147.7 (2)	Te4—O16—La1	137.7 (3)
O13—La4—O15	60.4 (3)	Te4—O16—La4	109.3 (3)
O192ⁱ—La4—O15	115.1 (4)	La1—O16—La4	110.7 (2)
O20—La4—O15	85.9 (4)	Te4—O17—La2	133.5 (3)
O3^iv—La4—O18	73.59 (18)	Te4—O17—La51	105.0 (2)
O2^iv—La4—O18	68.6 (2)	La2—O17—La51	106.5 (2)
O191ⁱ—La4—O18	125.1 (3)	Te4—O17—La52	112.6 (3)
O16—La4—O18	58.79 (19)	La2—O17—La52	97.1 (2)
O7^iv—La4—O18	137.49 (19)	La51—O17—La52	9.40 (11)
O13—La4—O18	108.8 (3)	Te4—O18—La3	135.8 (3)
O192ⁱ—La4—O18	131.5 (4)	Te4—O18—La51	97.8 (3)
O20—La4—O18	132.5 (4)	La3—O18—La51	105.6 (2)
O15—La4—O18	57.66 (18)	Te4—O18—La4	92.0 (3)
O9^iv—La51—O9ⁱⁱ	71.9 (3)	La3—O18—La4	92.5 (2)
La52—La51—O1^vii	49.1 (5)	La51—O18—La4	141.2 (2)
O9^iv—La51—O1^vii	72.2 (2)	O192—O191—Te2	104.8 (14)
O9ⁱⁱ—La51—O1^vii	90.2 (2)	O192—O191—La1ⁱ	99.9 (15)
La52—La51—O14ⁱⁱ	92.8 (5)	Te2—O191—La1ⁱ	108.9 (5)
O9^iv—La51—O14ⁱⁱ	134.6 (2)	O192—O191—La4ⁱ	86.4 (13)
O9ⁱⁱ—La51—O14ⁱⁱ	73.25 (19)	Te2—O191—La4ⁱ	133.7 (6)
O1^vii—La51—O14ⁱⁱ	79.9 (2)	La1ⁱ—O191—La4ⁱ	113.2 (4)
La52—La51—O17	119.8 (6)	O191—O192—Te5ⁱ	165.3 (18)
O9^iv—La51—O17	115.9 (2)	O191—O192—Te2	56.9 (12)
O9ⁱⁱ—La51—O17	71.7 (2)	Te5ⁱ—O192—Te2	129.3 (7)
O1^vii—La51—O17	155.0 (2)	O191—O192—La4ⁱ	75.2 (13)
O14ⁱⁱ—La51—O17	78.4 (2)	Te5ⁱ—O192—La4ⁱ	108.3 (6)
La52—La51—O8^iv	111.1 (5)	Te2—O192—La4ⁱ	115.3 (6)
O9^iv—La51—O8^iv	71.0 (2)	O191—O192—La1ⁱ	63.0 (14)
O9ⁱⁱ—La51—O8^iv	105.4 (2)	Te5ⁱ—O192—La1ⁱ	102.4 (6)
O1^vii—La51—O8^iv	132.6 (2)	Te2—O192—La1ⁱ	92.3 (5)
O14ⁱⁱ—La51—O8^iv	147.3 (2)	La4ⁱ—O192—La1ⁱ	102.7 (5)
O17—La51—O8^iv	70.5 (2)	O20^xv—O20—Te5^vi	95.3 (9)
La52—La51—O5^iv	117.6 (5)	O20^xv—O20—La4	133.2 (12)
O9^iv—La51—O5^iv	109.5 (2)	Te5^vi—O20—La4	120.3 (8)

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

Experimental details

Crystal data
Chemical formula	La₁₀Te₁₂O₃₉
M_r	3544.30
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.6856 (11), 12.621 (3), 14.402 (3)
α, β, γ (°)	95.53 (3), 100.88 (3), 93.13 (3)
V (Å³)	1007.3 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	18.98
Crystal size (mm)	0.12 × 0.04 × 0.02

Data collection
Diffractometer	Stoe IPDSII diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe, 2004)
T_min, T_max	0.256, 0.702
No. of measured, independent and observed [I > 2σ(I)] reflections	18743, 8922, 5110
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.834

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.064, 0.77
No. of reflections	8922
No. of parameters	289
Δρ_max, Δρ_min (e Å⁻³)	3.71, −3.98

Computer programs: X-AREA (Stoe, 2004), X-RED32 (Stoe, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Crystal Impact, 2008).

Acknowledgements

This work was supported by a Discovery Grant from the Natural Sciences and Engineering Research Council of Canada and by a grant from the ACS Petroleum Research Fund.

References

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