Nanoscale order in the frustrated mixed conductor La_5.6WO_12−δ

This article reports a comprehensive investigation of the average and local structure of La_5.6WO_12−δ, which has excellent mixed proton, electron and oxide ion conduction suitable for device applications. Synchrotron X-ray and neutron powder diffraction show that a cubic fluorite supercell describes the average structure, with highly disordered lanthanum and oxide positions. On average, the tungsten sites are sixfold coordinated and a trace [3.7 (1.3)%] of anti-site disorder is detected. In addition to sharp Bragg reflections, strong diffuse neutron scattering is observed, which hints at short-range order. Plausible local configurations are considered and it is shown that the defect chemistry implies a simple `chemical exchange' interaction that favours ordered WO<sub>6</sub> octahedra. The local model is confirmed by synchrotron X-ray pair distribution function analysis and EXAFS experiments performed at the La K and W L<sub>3</sub> edges. It is shown that ordered domains of ∼3.5 nm are found, implying that mixed conduction in La<sub>5.6</sub>WO<sub>12−δ</sub> is associated with a defective glassy-like anion sublattice. The origins of this ground state are proposed to lie in the non-bipartite nature of the face-centred cubic lattice and the pairwise interactions which link the orientation of neighbouring octahedral WO<sub>6</sub> sites. This `function through frustration' could provide a means of designing new mixed conductors.

Computing details

Program(s) used to refine structure: GSAS.

Lanthanum tungstate

Crystal data

O23.33W4.14·La4.05O31.01·La23.14·W0.86	Dx = 6.626 Mg m^−3
Mr = 5567.17	Melting point: 2230 K
Cubic, Fm3m	Neutron radiation, λ = 1.594657 Å
Hall symbol: -F 4 2 3	µ = 0.02 mm^−1
a = 11.17434 (5) Å	T = 298 K
V = 1395.29 (2) Å^3	white
Z = 1	cylinder, 40 × 6 mm
F(000) = 563.68	Specimen preparation: Prepared at 1673 K

Data collection

D2B diffractometer	Scan method: step
Radiation source: nuclear reactor, ILL	Absorption correction: for a cylinder mounted on the φ axis GSAS Absorption/surface roughness correction: function number 0 Debye-Scherrer absorption correction Term (= MU.r/wave) = 0.30000E-01 Correction is not refined.
Specimen mounting: vanadium can	Tmin = 0.922, Tmax = 0.923
Data collection mode: transmission	2θmin = 10°, 2θmax = 158°, 2θstep = 0.05°

Refinement

Refinement on F^2	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 55.958 #2(GV) = -128.612 #3(GW) = 125.664 #4(LX) = 2.776 #5(LY) = 0.000 #6(trns) = 0.000 #7(asym) = 11.3942 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0050 times the peak Aniso. broadening axis 0.0 0.0 1.0
Least-squares matrix: full	23 parameters
Rp = 0.040	0 restraints
Rwp = 0.055	10 constraints
Rexp = 0.033	Primary atom site location: heavy-atom method
R(F^2) = 0.02636	Secondary atom site location: difference Fourier map
2959 data points	(Δ/σ)max = 0.01
Excluded region(s): <10 deg and >158 deg	Background function: GSAS Background function number 1 with 36 terms. Shifted Chebyshev function of 1st kind 1: 76.6373 2: 6.84654 3: 0.486319 4: -1.42335 5: 3.11095 6: -0.840511 7: 1.58166 8: -2.73080 9: 1.82030 10: 3.04676 11: -3.06427 12: -1.07405 13: 2.83221 14: -0.665111 15: -0.814509 16: 0.723053 17: -0.344677 18: 0.510620 19: 0.241048 20: -0.528622 21: 0.609720 22: -4.899330E-0223: -1.02585 24: 0.679135 25: 0.102287 26: -0.340689 27: 0.175041 28: -0.632512 29: 7.004350E-0230: 0.280029 31: -0.446801 32: 0.375308 33: 0.238395 34: -0.167648 35: -0.279012 36: -6.408910E-02

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
W1	0.0	0.0	0.0	0.00826	1.036 (21)
LA1	0.5	0.5	0.5	0.01162	1.013 (13)
LA2	0.0	0.23573 (18)	0.23573 (18)	0.00789	0.482 (6)
W2	0.0	0.23573 (18)	0.23573 (18)	0.00789	0.018 (6)
O1	0.1120 (2)	0.1120 (2)	0.0646 (3)	0.02483	0.243 (4)
O2	0.36644 (10)	0.36644 (10)	0.36644 (10)	0.01841	0.969 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.0083 (14)	0.0083 (14)	0.0083 (14)	0.0	0.0	0.0
LA1	0.0116 (9)	0.0116 (9)	0.0116 (9)	0.0	0.0	0.0
LA2	0.0087 (9)	0.0075 (13)	0.0075 (13)	0.0	0.0	0.0016 (12)
W2	0.0087 (9)	0.0075 (13)	0.0075 (13)	0.0	0.0	0.0016 (12)
O1	0.0160 (18)	0.0160 (18)	0.042 (3)	−0.0034 (9)	−0.0093 (11)	−0.0093 (11)
O2	0.0184 (4)	0.0184 (4)	0.0184 (4)	0.0017 (4)	0.0017 (4)	0.0017 (4)

Geometric parameters (Å, º)

W1—O1	1.912 (3)	LA2—LA2^lxi	3.9700 (5)
W1—O1^i	1.912 (3)	LA2—LA2^lxii	3.9700 (5)
W1—O1^ii	1.912 (3)	LA2—LA2^lxiii	3.9700 (5)
W1—O1^iii	1.912 (3)	LA2—LA2^lxiv	3.9700 (5)
W1—O1^iv	1.912 (3)	LA2—W2^lx	0.451 (6)
W1—O1^v	1.912 (3)	LA2—O1	2.671 (3)
W1—O1^vi	1.912 (3)	LA2—O1^i	2.084 (5)
W1—O1^vii	1.912 (3)	LA2—O1^ii	2.671 (3)
W1—O1^viii	1.912 (3)	LA2—O1^iv	2.084 (5)
W1—O1^ix	1.912 (3)	LA2—O1^xx	2.671 (3)
W1—O1^x	1.912 (3)	LA2—O1^xxiii	2.671 (3)
W1—O1^xi	1.912 (3)	LA2—O1^lxv	3.073 (3)
W1—O1^xii	1.912 (3)	LA2—O1^lx	3.073 (3)
W1—O1^xiii	1.912 (3)	LA2—O1^lxvi	3.073 (3)
W1—O1^xiv	1.912 (3)	LA2—O1^lxvii	2.512 (3)
W1—O1^xv	1.912 (3)	LA2—O1^lxviii	3.073 (3)
W1—O1^xvi	1.912 (3)	LA2—O1^lxix	2.512 (3)
W1—O1^xvii	1.912 (3)	LA2—O2^lxx	2.3799 (6)
W1—O1^xviii	1.912 (3)	LA2—O2^lxi	2.3799 (6)
W1—O1^xix	1.912 (3)	LA2—O2^lxiii	2.3799 (6)
W1—O1^xx	1.912 (3)	LA2—O2^lxiv	2.3799 (6)
W1—O1^xxi	1.912 (3)	W2—LA2^lx	0.451 (6)
W1—O1^xxii	1.912 (3)	W2—W2^lx	0.451 (6)
W1—O1^xxiii	1.912 (3)	W2—O1	2.671 (3)
LA1—LA2^xxiv	3.9572 (2)	W2—O1^i	2.084 (5)
LA1—LA2^xxv	3.9572 (2)	W2—O1^ii	2.671 (3)
LA1—LA2^xxvi	3.9572 (2)	W2—O1^iv	2.084 (5)
LA1—LA2^xxvii	3.9572 (2)	W2—O1^xx	2.671 (3)
LA1—LA2^xxviii	3.9572 (2)	W2—O1^xxiii	2.671 (3)
LA1—LA2^xxix	3.9572 (2)	W2—O1^lxvii	2.512 (3)
LA1—LA2^xxx	3.9572 (2)	W2—O1^lxix	2.512 (3)
LA1—LA2^xxxi	3.9572 (2)	W2—O2^lxx	2.3799 (6)
LA1—LA2^xxxii	3.9572 (2)	W2—O2^lxi	2.3799 (6)
LA1—LA2^xxxiii	3.9572 (2)	W2—O2^lxiii	2.3799 (6)
LA1—LA2^xxxiv	3.9572 (2)	W2—O2^lxiv	2.3799 (6)
LA1—LA2^xxxv	3.9572 (2)	O1—W1	1.912 (3)
LA1—LA2^xxxvi	3.9572 (2)	O1—LA2	2.671 (3)
LA1—LA2^xxxvii	3.9572 (2)	O1—LA2^i	2.671 (3)
LA1—LA2^xxxviii	3.9572 (2)	O1—LA2^ii	2.084 (5)
LA1—LA2^xxxix	3.9572 (2)	O1—LA2^lx	3.073 (3)
LA1—LA2^xl	3.9572 (2)	O1—LA2^lxi	3.073 (3)
LA1—LA2^xli	3.9572 (2)	O1—LA2^lxiv	2.512 (3)
LA1—LA2^xlii	3.9572 (2)	O1—W2	2.671 (3)
LA1—LA2^xliii	3.9572 (2)	O1—W2^i	2.671 (3)
LA1—LA2^xliv	3.9572 (2)	O1—W2^ii	2.084 (5)
LA1—LA2^xlv	3.9572 (2)	O1—W2^lxiv	2.512 (3)
LA1—LA2^xlvi	3.9572 (2)	O1—O1^i	0.750 (5)
LA1—LA2^xlvii	3.9572 (2)	O1—O1^ii	0.750 (5)
LA1—O2	2.5851 (18)	O1—O1^iii	1.443 (6)
LA1—O2^xlviii	2.5851 (18)	O1—O1^iv	2.043 (4)
LA1—O2^xlix	2.5851 (18)	O1—O1^v	2.043 (4)
LA1—O2^l	2.5851 (18)	O1—O1^xix	2.043 (4)
LA1—O2^li	2.5851 (18)	O1—O1^xxii	2.043 (4)
LA1—O2^lii	2.5851 (18)	O2—LA1	2.5851 (18)
LA1—O2^liii	2.5851 (18)	O2—LA2^xxvii	2.3799 (6)
LA1—O2^liv	2.5851 (18)	O2—LA2^xxx	2.3799 (6)
LA2—LA1^lv	3.9572 (2)	O2—LA2^xxxiv	2.3799 (6)
LA2—LA1^lvi	3.9572 (2)	O2—LA2^xxxviii	2.3799 (6)
LA2—LA2^i	3.725 (3)	O2—LA2^xliii	2.3799 (6)
LA2—LA2^ii	3.725 (3)	O2—LA2^xlvii	2.3799 (6)
LA2—LA2^iv	3.725 (3)	O2—W2^xxvii	2.3799 (6)
LA2—LA2^lvii	3.725 (3)	O2—W2^xxx	2.3799 (6)
LA2—LA2^xxvii	3.9700 (5)	O2—W2^xxxiv	2.3799 (6)
LA2—LA2^lviii	3.9700 (5)	O2—W2^xxxviii	2.3799 (6)
LA2—LA2^lix	3.9700 (5)	O2—W2^xliii	2.3799 (6)
LA2—LA2^lx	0.451 (6)	O2—W2^xlvii	2.3799 (6)
LA2—LA2^xxx	3.9700 (5)
O1—W1—O1^i	22.62 (16)	O1^xvii—W1—O1^xxiii	64.61 (4)
O1—W1—O1^ii	22.62 (16)	O1^xviii—W1—O1^xix	115.39 (4)
O1—W1—O1^iii	44.35 (19)	O1^xviii—W1—O1^xx	93.75 (13)
O1—W1—O1^iv	64.61 (4)	O1^xviii—W1—O1^xxi	22.62 (16)
O1—W1—O1^v	64.61 (4)	O1^xviii—W1—O1^xxii	135.65 (19)
O1—W1—O1^vi	93.75 (13)	O1^xviii—W1—O1^xxiii	115.39 (4)
O1—W1—O1^vii	115.39 (4)	O1^xix—W1—O1^xx	135.65 (19)
O1—W1—O1^viii	93.75 (13)	O1^xix—W1—O1^xxi	93.75 (13)
O1—W1—O1^ix	98.19 (7)	O1^xix—W1—O1^xxii	22.62 (16)
O1—W1—O1^x	115.39 (4)	O1^xix—W1—O1^xxiii	115.39 (4)
O1—W1—O1^xi	98.19 (7)	O1^xx—W1—O1^xxi	115.39 (4)
O1—W1—O1^xii	180.0	O1^xx—W1—O1^xxii	115.39 (4)
O1—W1—O1^xiii	157.38 (16)	O1^xx—W1—O1^xxiii	22.62 (16)
O1—W1—O1^xiv	157.38 (16)	O1^xxi—W1—O1^xxii	115.39 (4)
O1—W1—O1^xv	135.65 (19)	O1^xxi—W1—O1^xxiii	135.65 (19)
O1—W1—O1^xvi	115.39 (4)	O1^xxii—W1—O1^xxiii	93.75 (13)
O1—W1—O1^xvii	115.39 (4)	O2—LA1—O2^xlviii	70.5288 (4)
O1—W1—O1^xviii	86.25 (13)	O2—LA1—O2^xlix	70.5288 (2)
O1—W1—O1^xix	64.61 (4)	O2—LA1—O2^l	70.5288 (2)
O1—W1—O1^xx	86.25 (13)	O2—LA1—O2^li	109.4712 (2)
O1—W1—O1^xxi	81.81 (7)	O2—LA1—O2^lii	109.4712 (4)
O1—W1—O1^xxii	64.61 (4)	O2—LA1—O2^liii	109.4712 (2)
O1—W1—O1^xxiii	81.81 (7)	O2—LA1—O2^liv	180.0
O1^i—W1—O1^ii	22.62 (16)	O2^xlviii—LA1—O2^xlix	109.4712 (2)
O1^i—W1—O1^iii	64.61 (4)	O2^xlviii—LA1—O2^l	109.4712 (2)
O1^i—W1—O1^iv	44.35 (19)	O2^xlviii—LA1—O2^li	70.5288 (2)
O1^i—W1—O1^v	64.61 (4)	O2^xlviii—LA1—O2^lii	180.0
O1^i—W1—O1^vi	98.19 (7)	O2^xlviii—LA1—O2^liii	70.5288 (2)
O1^i—W1—O1^vii	93.75 (13)	O2^xlviii—LA1—O2^liv	109.4712 (4)
O1^i—W1—O1^viii	115.39 (4)	O2^xlix—LA1—O2^l	109.4712 (4)
O1^i—W1—O1^ix	93.75 (13)	O2^xlix—LA1—O2^li	70.5288 (4)
O1^i—W1—O1^x	98.19 (7)	O2^xlix—LA1—O2^lii	70.5288 (2)
O1^i—W1—O1^xi	115.39 (4)	O2^xlix—LA1—O2^liii	180.0
O1^i—W1—O1^xii	157.38 (16)	O2^xlix—LA1—O2^liv	109.4712 (2)
O1^i—W1—O1^xiii	180.0	O2^l—LA1—O2^li	180.0
O1^i—W1—O1^xiv	157.38 (16)	O2^l—LA1—O2^lii	70.5288 (2)
O1^i—W1—O1^xv	115.39 (4)	O2^l—LA1—O2^liii	70.5288 (4)
O1^i—W1—O1^xvi	135.65 (19)	O2^l—LA1—O2^liv	109.4712 (2)
O1^i—W1—O1^xvii	115.39 (4)	O2^li—LA1—O2^lii	109.4712 (2)
O1^i—W1—O1^xviii	81.81 (7)	O2^li—LA1—O2^liii	109.4712 (4)
O1^i—W1—O1^xix	86.25 (13)	O2^li—LA1—O2^liv	70.5288 (2)
O1^i—W1—O1^xx	64.61 (4)	O2^lii—LA1—O2^liii	109.4712 (2)
O1^i—W1—O1^xxi	86.25 (13)	O2^lii—LA1—O2^liv	70.5288 (4)
O1^i—W1—O1^xxii	81.81 (7)	O2^liii—LA1—O2^liv	70.5288 (2)
O1^i—W1—O1^xxiii	64.61 (4)	LA2^i—LA2—LA2^ii	60.0000 (1)
O1^ii—W1—O1^iii	64.61 (4)	LA2^i—LA2—LA2^iv	90.0
O1^ii—W1—O1^iv	64.61 (4)	LA2^i—LA2—LA2^lvii	120.0000 (1)
O1^ii—W1—O1^v	44.35 (19)	LA2^i—LA2—LA2^lx	120.0000 (1)
O1^ii—W1—O1^vi	115.39 (4)	LA2^i—LA2—W2^lx	120.0000 (1)
O1^ii—W1—O1^vii	98.19 (7)	LA2^i—LA2—O1	45.79 (5)
O1^ii—W1—O1^viii	98.19 (7)	LA2^i—LA2—O1^i	44.45 (7)
O1^ii—W1—O1^ix	115.39 (4)	LA2^i—LA2—O1^ii	33.11 (8)
O1^ii—W1—O1^x	93.75 (13)	LA2^i—LA2—O1^iv	77.04 (8)
O1^ii—W1—O1^xi	93.75 (13)	LA2^i—LA2—O1^xx	79.92 (6)
O1^ii—W1—O1^xii	157.38 (16)	LA2^i—LA2—O1^xxiii	88.02 (8)
O1^ii—W1—O1^xiii	157.38 (16)	LA2^i—LA2—O1^lxvii	133.00 (5)
O1^ii—W1—O1^xiv	180.0	LA2^i—LA2—O1^lxix	106.01 (6)
O1^ii—W1—O1^xv	115.39 (4)	LA2^i—LA2—O2^lxx	151.33 (6)
O1^ii—W1—O1^xvi	115.39 (4)	LA2^i—LA2—O2^lxi	89.46 (6)
O1^ii—W1—O1^xvii	135.65 (19)	LA2^i—LA2—O2^lxiii	95.98 (4)
O1^ii—W1—O1^xviii	64.61 (4)	LA2^i—LA2—O2^lxiv	38.50 (7)
O1^ii—W1—O1^xix	81.81 (7)	LA2^ii—LA2—LA2^iv	120.0000 (1)
O1^ii—W1—O1^xx	81.81 (7)	LA2^ii—LA2—LA2^lvii	90.0000 (4)
O1^ii—W1—O1^xxi	64.61 (4)	LA2^ii—LA2—LA2^lx	120.0000 (2)
O1^ii—W1—O1^xxii	86.25 (13)	LA2^ii—LA2—W2^lx	120.0000 (2)
O1^ii—W1—O1^xxiii	86.25 (13)	LA2^ii—LA2—O1	33.11 (8)
O1^iii—W1—O1^iv	93.75 (13)	LA2^ii—LA2—O1^i	44.45 (7)
O1^iii—W1—O1^v	93.75 (13)	LA2^ii—LA2—O1^ii	45.79 (5)
O1^iii—W1—O1^vi	64.61 (4)	LA2^ii—LA2—O1^iv	77.04 (8)
O1^iii—W1—O1^vii	157.38 (16)	LA2^ii—LA2—O1^xx	88.02 (8)
O1^iii—W1—O1^viii	64.61 (4)	LA2^ii—LA2—O1^xxiii	79.92 (6)
O1^iii—W1—O1^ix	81.81 (7)	LA2^ii—LA2—O1^lxvii	133.00 (5)
O1^iii—W1—O1^x	157.38 (16)	LA2^ii—LA2—O1^lxix	106.01 (6)
O1^iii—W1—O1^xi	81.81 (7)	LA2^ii—LA2—O2^lxx	95.98 (4)
O1^iii—W1—O1^xii	135.65 (19)	LA2^ii—LA2—O2^lxi	38.50 (7)
O1^iii—W1—O1^xiii	115.39 (4)	LA2^ii—LA2—O2^lxiii	151.33 (6)
O1^iii—W1—O1^xiv	115.39 (4)	LA2^ii—LA2—O2^lxiv	89.46 (6)
O1^iii—W1—O1^xv	180.0	LA2^iv—LA2—LA2^lvii	60.0000 (1)
O1^iii—W1—O1^xvi	86.25 (13)	LA2^iv—LA2—LA2^lx	120.0000 (1)
O1^iii—W1—O1^xvii	86.25 (13)	LA2^iv—LA2—W2^lx	120.0000 (1)
O1^iii—W1—O1^xviii	115.39 (4)	LA2^iv—LA2—O1	88.02 (8)
O1^iii—W1—O1^xix	22.62 (16)	LA2^iv—LA2—O1^i	77.04 (8)
O1^iii—W1—O1^xx	115.39 (4)	LA2^iv—LA2—O1^ii	79.92 (6)
O1^iii—W1—O1^xxi	98.19 (7)	LA2^iv—LA2—O1^iv	44.45 (7)
O1^iii—W1—O1^xxii	22.62 (16)	LA2^iv—LA2—O1^xx	33.11 (8)
O1^iii—W1—O1^xxiii	98.19 (7)	LA2^iv—LA2—O1^xxiii	45.79 (5)
O1^iv—W1—O1^v	93.75 (13)	LA2^iv—LA2—O1^lxvii	106.01 (6)
O1^iv—W1—O1^vi	81.81 (7)	LA2^iv—LA2—O1^lxix	133.00 (5)
O1^iv—W1—O1^vii	64.61 (4)	LA2^iv—LA2—O2^lxx	89.46 (6)
O1^iv—W1—O1^viii	157.38 (16)	LA2^iv—LA2—O2^lxi	151.33 (6)
O1^iv—W1—O1^ix	64.61 (4)	LA2^iv—LA2—O2^lxiii	38.50 (7)
O1^iv—W1—O1^x	81.81 (7)	LA2^iv—LA2—O2^lxiv	95.98 (4)
O1^iv—W1—O1^xi	157.38 (16)	LA2^lvii—LA2—LA2^lx	120.0000 (2)
O1^iv—W1—O1^xii	115.39 (4)	LA2^lvii—LA2—W2^lx	120.0000 (2)
O1^iv—W1—O1^xiii	135.65 (19)	LA2^lvii—LA2—O1	79.92 (6)
O1^iv—W1—O1^xiv	115.39 (4)	LA2^lvii—LA2—O1^i	77.04 (8)
O1^iv—W1—O1^xv	86.25 (13)	LA2^lvii—LA2—O1^ii	88.02 (8)
O1^iv—W1—O1^xvi	180.0	LA2^lvii—LA2—O1^iv	44.45 (7)
O1^iv—W1—O1^xvii	86.25 (13)	LA2^lvii—LA2—O1^xx	45.79 (5)
O1^iv—W1—O1^xviii	98.19 (7)	LA2^lvii—LA2—O1^xxiii	33.11 (8)
O1^iv—W1—O1^xix	115.39 (4)	LA2^lvii—LA2—O1^lxvii	106.01 (6)
O1^iv—W1—O1^xx	22.62 (16)	LA2^lvii—LA2—O1^lxix	133.00 (5)
O1^iv—W1—O1^xxi	115.39 (4)	LA2^lvii—LA2—O2^lxx	38.50 (7)
O1^iv—W1—O1^xxii	98.19 (7)	LA2^lvii—LA2—O2^lxi	95.98 (4)
O1^iv—W1—O1^xxiii	22.62 (16)	LA2^lvii—LA2—O2^lxiii	89.46 (6)
O1^v—W1—O1^vi	157.38 (16)	LA2^lvii—LA2—O2^lxiv	151.33 (6)
O1^v—W1—O1^vii	81.81 (7)	LA2^lx—LA2—W2^lx	0.0
O1^v—W1—O1^viii	81.81 (7)	LA2^lx—LA2—O1	150.72 (8)
O1^v—W1—O1^ix	157.38 (16)	LA2^lx—LA2—O1^i	159.74 (10)
O1^v—W1—O1^x	64.61 (4)	LA2^lx—LA2—O1^ii	150.72 (8)
O1^v—W1—O1^xi	64.61 (4)	LA2^lx—LA2—O1^iv	159.74 (10)
O1^v—W1—O1^xii	115.39 (4)	LA2^lx—LA2—O1^xx	150.72 (8)
O1^v—W1—O1^xiii	115.39 (4)	LA2^lx—LA2—O1^xxiii	150.72 (8)
O1^v—W1—O1^xiv	135.65 (19)	LA2^lx—LA2—O1^lxvii	16.69 (8)
O1^v—W1—O1^xv	86.25 (13)	LA2^lx—LA2—O1^lxix	16.69 (8)
O1^v—W1—O1^xvi	86.25 (13)	LA2^lx—LA2—O2^lxx	84.56 (7)
O1^v—W1—O1^xvii	180.0	LA2^lx—LA2—O2^lxi	84.56 (7)
O1^v—W1—O1^xviii	22.62 (16)	LA2^lx—LA2—O2^lxiii	84.56 (7)
O1^v—W1—O1^xix	98.19 (7)	LA2^lx—LA2—O2^lxiv	84.56 (7)
O1^v—W1—O1^xx	98.19 (7)	W2^lx—LA2—O1	150.72 (8)
O1^v—W1—O1^xxi	22.62 (16)	W2^lx—LA2—O1^i	159.74 (10)
O1^v—W1—O1^xxii	115.39 (4)	W2^lx—LA2—O1^ii	150.72 (8)
O1^v—W1—O1^xxiii	115.39 (4)	W2^lx—LA2—O1^iv	159.74 (10)
O1^vi—W1—O1^vii	115.39 (4)	W2^lx—LA2—O1^xx	150.72 (8)
O1^vi—W1—O1^viii	93.75 (13)	W2^lx—LA2—O1^xxiii	150.72 (8)
O1^vi—W1—O1^ix	22.62 (16)	W2^lx—LA2—O1^lxvii	16.69 (8)
O1^vi—W1—O1^x	135.65 (19)	W2^lx—LA2—O1^lxix	16.69 (8)
O1^vi—W1—O1^xi	115.39 (4)	W2^lx—LA2—O2^lxx	84.56 (7)
O1^vi—W1—O1^xii	86.25 (13)	W2^lx—LA2—O2^lxi	84.56 (7)
O1^vi—W1—O1^xiii	81.81 (7)	W2^lx—LA2—O2^lxiii	84.56 (7)
O1^vi—W1—O1^xiv	64.61 (4)	W2^lx—LA2—O2^lxiv	84.56 (7)
O1^vi—W1—O1^xv	115.39 (4)	O1—LA2—O1^i	11.34 (8)
O1^vi—W1—O1^xvi	98.19 (7)	O1—LA2—O1^ii	16.14 (11)
O1^vi—W1—O1^xvii	22.62 (16)	O1—LA2—O1^iv	49.00 (16)
O1^vi—W1—O1^xviii	180.0	O1—LA2—O1^xx	58.57 (16)
O1^vi—W1—O1^xix	64.61 (4)	O1—LA2—O1^xxiii	55.88 (15)
O1^vi—W1—O1^xx	86.25 (13)	O1—LA2—O1^lxvii	165.94 (10)
O1^vi—W1—O1^xxi	157.38 (16)	O1—LA2—O1^lxix	134.49 (12)
O1^vi—W1—O1^xxii	44.35 (19)	O1—LA2—O2^lxx	105.54 (8)
O1^vi—W1—O1^xxiii	64.61 (4)	O1—LA2—O2^lxi	71.35 (6)
O1^vii—W1—O1^viii	135.65 (19)	O1—LA2—O2^lxiii	119.01 (12)
O1^vii—W1—O1^ix	93.75 (13)	O1—LA2—O2^lxiv	84.10 (7)
O1^vii—W1—O1^x	22.62 (16)	O1^i—LA2—O1^ii	11.34 (8)
O1^vii—W1—O1^xi	115.39 (4)	O1^i—LA2—O1^iv	40.51 (19)
O1^vii—W1—O1^xii	64.61 (4)	O1^i—LA2—O1^xx	49.00 (16)
O1^vii—W1—O1^xiii	86.25 (13)	O1^i—LA2—O1^xxiii	49.00 (16)
O1^vii—W1—O1^xiv	81.81 (7)	O1^i—LA2—O1^lxvii	176.44 (5)
O1^vii—W1—O1^xv	22.62 (16)	O1^i—LA2—O1^lxix	143.05 (17)
O1^vii—W1—O1^xvi	115.39 (4)	O1^i—LA2—O2^lxx	107.82 (10)
O1^vii—W1—O1^xvii	98.19 (7)	O1^i—LA2—O2^lxi	82.63 (7)
O1^vii—W1—O1^xviii	64.61 (4)	O1^i—LA2—O2^lxiii	107.82 (10)
O1^vii—W1—O1^xix	180.0	O1^i—LA2—O2^lxiv	82.63 (7)
O1^vii—W1—O1^xx	44.35 (19)	O1^ii—LA2—O1^iv	49.00 (16)
O1^vii—W1—O1^xxi	86.25 (13)	O1^ii—LA2—O1^xx	55.88 (15)
O1^vii—W1—O1^xxii	157.38 (16)	O1^ii—LA2—O1^xxiii	58.57 (16)
O1^vii—W1—O1^xxiii	64.61 (4)	O1^ii—LA2—O1^lxvii	165.94 (10)
O1^viii—W1—O1^ix	115.39 (4)	O1^ii—LA2—O1^lxix	134.49 (12)
O1^viii—W1—O1^x	115.39 (4)	O1^ii—LA2—O2^lxx	119.01 (12)
O1^viii—W1—O1^xi	22.62 (16)	O1^ii—LA2—O2^lxi	84.10 (7)
O1^viii—W1—O1^xii	86.25 (13)	O1^ii—LA2—O2^lxiii	105.54 (8)
O1^viii—W1—O1^xiii	64.61 (4)	O1^ii—LA2—O2^lxiv	71.35 (6)
O1^viii—W1—O1^xiv	81.81 (7)	O1^iv—LA2—O1^xx	11.34 (8)
O1^viii—W1—O1^xv	115.39 (4)	O1^iv—LA2—O1^xxiii	11.34 (8)
O1^viii—W1—O1^xvi	22.62 (16)	O1^iv—LA2—O1^lxvii	143.05 (17)
O1^viii—W1—O1^xvii	98.19 (7)	O1^iv—LA2—O1^lxix	176.44 (5)
O1^viii—W1—O1^xviii	86.25 (13)	O1^iv—LA2—O2^lxx	82.63 (7)
O1^viii—W1—O1^xix	44.35 (19)	O1^iv—LA2—O2^lxi	107.82 (10)
O1^viii—W1—O1^xx	180.0	O1^iv—LA2—O2^lxiii	82.63 (7)
O1^viii—W1—O1^xxi	64.61 (4)	O1^iv—LA2—O2^lxiv	107.82 (10)
O1^viii—W1—O1^xxii	64.61 (4)	O1^xx—LA2—O1^xxiii	16.14 (11)
O1^viii—W1—O1^xxiii	157.38 (16)	O1^xx—LA2—O1^lxvii	134.49 (12)
O1^ix—W1—O1^x	115.39 (4)	O1^xx—LA2—O1^lxix	165.94 (10)
O1^ix—W1—O1^xi	135.65 (19)	O1^xx—LA2—O2^lxx	84.10 (7)
O1^ix—W1—O1^xii	81.81 (7)	O1^xx—LA2—O2^lxi	119.01 (12)
O1^ix—W1—O1^xiii	86.25 (13)	O1^xx—LA2—O2^lxiii	71.35 (6)
O1^ix—W1—O1^xiv	64.61 (4)	O1^xx—LA2—O2^lxiv	105.54 (8)
O1^ix—W1—O1^xv	98.19 (7)	O1^xxiii—LA2—O1^lxvii	134.49 (12)
O1^ix—W1—O1^xvi	115.39 (4)	O1^xxiii—LA2—O1^lxix	165.94 (10)
O1^ix—W1—O1^xvii	22.62 (16)	O1^xxiii—LA2—O2^lxx	71.35 (6)
O1^ix—W1—O1^xviii	157.38 (16)	O1^xxiii—LA2—O2^lxi	105.54 (8)
O1^ix—W1—O1^xix	86.25 (13)	O1^xxiii—LA2—O2^lxiii	84.10 (7)
O1^ix—W1—O1^xx	64.61 (4)	O1^xxiii—LA2—O2^lxiv	119.01 (12)
O1^ix—W1—O1^xxi	180.0	O1^lxvii—LA2—O1^lxix	33.39 (15)
O1^ix—W1—O1^xxii	64.61 (4)	O1^lxvii—LA2—O2^lxx	74.28 (7)
O1^ix—W1—O1^xxiii	44.35 (19)	O1^lxvii—LA2—O2^lxi	95.13 (9)
O1^x—W1—O1^xi	93.75 (13)	O1^lxvii—LA2—O2^lxiii	74.28 (7)
O1^x—W1—O1^xii	64.61 (4)	O1^lxvii—LA2—O2^lxiv	95.13 (9)
O1^x—W1—O1^xiii	81.81 (7)	O1^lxix—LA2—O2^lxx	95.13 (9)
O1^x—W1—O1^xiv	86.25 (13)	O1^lxix—LA2—O2^lxi	74.28 (7)
O1^x—W1—O1^xv	22.62 (16)	O1^lxix—LA2—O2^lxiii	95.13 (9)
O1^x—W1—O1^xvi	98.19 (7)	O1^lxix—LA2—O2^lxiv	74.28 (7)
O1^x—W1—O1^xvii	115.39 (4)	O2^lxx—LA2—O2^lxi	77.68 (9)
O1^x—W1—O1^xviii	44.35 (19)	O2^lxx—LA2—O2^lxiii	101.27 (8)
O1^x—W1—O1^xix	157.38 (16)	O2^lxx—LA2—O2^lxiv	169.13 (14)
O1^x—W1—O1^xx	64.61 (4)	O2^lxi—LA2—O2^lxiii	169.13 (14)
O1^x—W1—O1^xxi	64.61 (4)	O2^lxi—LA2—O2^lxiv	101.27 (8)
O1^x—W1—O1^xxii	180.0	O2^lxiii—LA2—O2^lxiv	77.68 (9)
O1^x—W1—O1^xxiii	86.25 (13)	LA2^lx—W2—W2^lx	0.0
O1^xi—W1—O1^xii	81.81 (7)	LA2^lx—W2—O1^i	159.74 (10)
O1^xi—W1—O1^xiii	64.61 (4)	LA2^lx—W2—O1^iv	159.74 (10)
O1^xi—W1—O1^xiv	86.25 (13)	W2^lx—W2—O1^i	159.74 (10)
O1^xi—W1—O1^xv	98.19 (7)	W2^lx—W2—O1^iv	159.74 (10)
O1^xi—W1—O1^xvi	22.62 (16)	O1^i—W2—O1^iv	40.51 (19)
O1^xi—W1—O1^xvii	115.39 (4)	W1—O1—LA2	107.59 (11)
O1^xi—W1—O1^xviii	64.61 (4)	W1—O1—LA2^i	107.59 (11)
O1^xi—W1—O1^xix	64.61 (4)	W1—O1—LA2^ii	137.57 (18)
O1^xi—W1—O1^xx	157.38 (16)	W1—O1—LA2^lxiv	141.13 (16)
O1^xi—W1—O1^xxi	44.35 (19)	W1—O1—W2^ii	137.57 (18)
O1^xi—W1—O1^xxii	86.25 (13)	W1—O1—O1^i	78.69 (8)
O1^xi—W1—O1^xxiii	180.0	W1—O1—O1^ii	78.69 (8)
O1^xii—W1—O1^xiii	22.62 (16)	W1—O1—O1^iii	67.83 (10)
O1^xii—W1—O1^xiv	22.62 (16)	LA2—O1—LA2^i	88.41 (10)
O1^xii—W1—O1^xv	44.35 (19)	LA2—O1—LA2^ii	102.44 (12)
O1^xii—W1—O1^xvi	64.61 (4)	LA2—O1—LA2^lxiv	99.94 (9)
O1^xii—W1—O1^xvii	64.61 (4)	LA2—O1—W2^ii	102.44 (12)
O1^xii—W1—O1^xviii	93.75 (13)	LA2—O1—O1^i	33.11 (8)
O1^xii—W1—O1^xix	115.39 (4)	LA2—O1—O1^ii	81.93 (6)
O1^xii—W1—O1^xx	93.75 (13)	LA2—O1—O1^iii	135.72 (5)
O1^xii—W1—O1^xxi	98.19 (7)	LA2^i—O1—LA2^ii	102.44 (12)
O1^xii—W1—O1^xxii	115.39 (4)	LA2^i—O1—LA2^lxiv	99.94 (9)
O1^xii—W1—O1^xxiii	98.19 (7)	LA2^i—O1—W2^ii	102.44 (12)
O1^xiii—W1—O1^xiv	22.62 (16)	LA2^i—O1—O1^i	81.93 (6)
O1^xiii—W1—O1^xv	64.61 (4)	LA2^i—O1—O1^ii	33.11 (8)
O1^xiii—W1—O1^xvi	44.35 (19)	LA2^i—O1—O1^iii	135.72 (5)
O1^xiii—W1—O1^xvii	64.61 (4)	LA2^ii—O1—LA2^lxiv	3.56 (5)
O1^xiii—W1—O1^xviii	98.19 (7)	LA2^ii—O1—W2^ii	0.0
O1^xiii—W1—O1^xix	93.75 (13)	LA2^ii—O1—O1^i	135.55 (7)
O1^xiii—W1—O1^xx	115.39 (4)	LA2^ii—O1—O1^ii	135.55 (7)
O1^xiii—W1—O1^xxi	93.75 (13)	LA2^ii—O1—O1^iii	69.74 (10)
O1^xiii—W1—O1^xxii	98.19 (7)	LA2^lxiv—O1—W2^ii	3.56 (5)
O1^xiii—W1—O1^xxiii	115.39 (4)	LA2^lxiv—O1—O1^i	133.00 (5)
O1^xiv—W1—O1^xv	64.61 (4)	LA2^lxiv—O1—O1^ii	133.00 (5)
O1^xiv—W1—O1^xvi	64.61 (4)	LA2^lxiv—O1—O1^iii	73.31 (8)
O1^xiv—W1—O1^xvii	44.35 (19)	W2^ii—O1—O1^i	135.55 (7)
O1^xiv—W1—O1^xviii	115.39 (4)	W2^ii—O1—O1^ii	135.55 (7)
O1^xiv—W1—O1^xix	98.19 (7)	W2^ii—O1—O1^iii	69.74 (10)
O1^xiv—W1—O1^xx	98.19 (7)	O1^i—O1—O1^ii	60.0000 (2)
O1^xiv—W1—O1^xxi	115.39 (4)	O1^i—O1—O1^iii	135.0000 (2)
O1^xiv—W1—O1^xxii	93.75 (13)	O1^ii—O1—O1^iii	135.0000 (2)
O1^xiv—W1—O1^xxiii	93.75 (13)	LA1—O2—LA2^xxvii	105.62 (4)
O1^xv—W1—O1^xvi	93.75 (13)	LA1—O2—LA2^xxx	105.62 (4)
O1^xv—W1—O1^xvii	93.75 (13)	LA1—O2—LA2^xxxiv	105.62 (4)
O1^xv—W1—O1^xviii	64.61 (4)	LA1—O2—LA2^xxxviii	105.62 (4)
O1^xv—W1—O1^xix	157.38 (16)	LA1—O2—LA2^xliii	105.62 (4)
O1^xv—W1—O1^xx	64.61 (4)	LA1—O2—LA2^xlvii	105.62 (4)
O1^xv—W1—O1^xxi	81.81 (7)	LA2^xxvii—O2—LA2^xxx	103.01 (14)
O1^xv—W1—O1^xxii	157.38 (16)	LA2^xxvii—O2—LA2^xxxiv	113.04 (4)
O1^xv—W1—O1^xxiii	81.81 (7)	LA2^xxvii—O2—LA2^xxxviii	10.87 (14)
O1^xvi—W1—O1^xvii	93.75 (13)	LA2^xxvii—O2—LA2^xliii	113.04 (4)
O1^xvi—W1—O1^xviii	81.81 (7)	LA2^xxvii—O2—LA2^xlvii	122.65 (11)
O1^xvi—W1—O1^xix	64.61 (4)	LA2^xxx—O2—LA2^xxxiv	122.65 (11)
O1^xvi—W1—O1^xx	157.38 (16)	LA2^xxx—O2—LA2^xxxviii	113.04 (4)
O1^xvi—W1—O1^xxi	64.61 (4)	LA2^xxx—O2—LA2^xliii	10.87 (14)
O1^xvi—W1—O1^xxii	81.81 (7)	LA2^xxx—O2—LA2^xlvii	113.04 (4)
O1^xvi—W1—O1^xxiii	157.38 (16)	LA2^xxxiv—O2—LA2^xxxviii	103.01 (14)
O1^xvii—W1—O1^xviii	157.38 (16)	LA2^xxxiv—O2—LA2^xliii	113.04 (4)
O1^xvii—W1—O1^xix	81.81 (7)	LA2^xxxiv—O2—LA2^xlvii	10.87 (14)
O1^xvii—W1—O1^xx	81.81 (7)	LA2^xxxviii—O2—LA2^xliii	122.65 (11)
O1^xvii—W1—O1^xxi	157.38 (16)	LA2^xxxviii—O2—LA2^xlvii	113.04 (4)
O1^xvii—W1—O1^xxii	64.61 (4)	LA2^xliii—O2—LA2^xlvii	103.01 (14)

Symmetry codes: (i) z, x, y; (ii) y, z, x; (iii) x, y, −z; (iv) −z, x, y; (v) y, −z, x; (vi) −z, x, −y; (vii) −y, −z, x; (viii) y, −z, −x; (ix) −x, y, −z; (x) −z, −x, y; (xi) x, −y, −z; (xii) −x, −y, −z; (xiii) −z, −x, −y; (xiv) −y, −z, −x; (xv) −x, −y, z; (xvi) z, −x, −y; (xvii) −y, z, −x; (xviii) z, −x, y; (xix) y, z, −x; (xx) −y, z, x; (xxi) x, −y, z; (xxii) z, x, −y; (xxiii) −x, y, z; (xxiv) z, x+1/2, y+1/2; (xxv) y, z+1/2, x+1/2; (xxvi) −z+1, x+1/2, y+1/2; (xxvii) y, −z+1/2, x+1/2; (xxviii) −z+1, x+1/2, −y+1/2; (xxix) −y+1, −z+1/2, x+1/2; (xxx) y, x+1/2, −z+1/2; (xxxi) −z+1, y+1/2, x+1/2; (xxxii) x+1/2, y, z+1/2; (xxxiii) y+1/2, z, x+1/2; (xxxiv) x+1/2, y, −z+1/2; (xxxv) y+1/2, −z+1, x+1/2; (xxxvi) −y+1/2, −z+1, x+1/2; (xxxvii) x+1/2, −y+1, −z+1/2; (xxxviii) −z+1/2, y, x+1/2; (xxxix) x+1/2, −z+1, y+1/2; (xl) x+1/2, y+1/2, z; (xli) z+1/2, x+1/2, y; (xlii) x+1/2, y+1/2, −z+1; (xliii) −z+1/2, x+1/2, y; (xliv) −z+1/2, x+1/2, −y+1; (xlv) x+1/2, −y+1/2, −z+1; (xlvi) y+1/2, x+1/2, −z+1; (xlvii) x+1/2, −z+1/2, y; (xlviii) x, y, −z+1; (xlix) −z+1, x, y; (l) y, −z+1, x; (li) −z+1, x, −y+1; (lii) −y+1, −z+1, x; (liii) y, −z+1, −x+1; (liv) −x+1, −y+1, −z+1; (lv) x−1/2, y, z−1/2; (lvi) x−1/2, y−1/2, z; (lvii) −z, y, x; (lviii) −z, x+1/2, −y+1/2; (lix) −y, −z+1/2, x+1/2; (lx) x, −y+1/2, −z+1/2; (lxi) −z+1/2, x, −y+1/2; (lxii) y−1/2, x, −z+1/2; (lxiii) y−1/2, −z+1/2, x; (lxiv) −y+1/2, −z+1/2, x; (lxv) y, −z+1/2, −x+1/2; (lxvi) −x, −y−1/2, −z−1/2; (lxvii) −z, −x−1/2, −y−1/2; (lxviii) −y, −z−1/2, −x−1/2; (lxix) z, −x−1/2, −y−1/2; (lxx) x−1/2, y, −z+1/2.