Structures and thermal stability of the α-LiNH₄SO₄ polytypes doped with Er³⁺ and Yb³⁺

In order to clarify the polymorphism in the lithium sulfate family, LiRE_x(NH₄)_1 − xSO₄ (0.5 ≤ x ≤ 4.0 mol%, nominal value; RE = Er³⁺, Yb³⁺ and Dy³⁺) crystals were grown from aqueous solution by slow evaporation between 298 and 313 K. The doping of the samples allowed us to obtain two polymorphic forms, α and β, of LiNH₄SO₄ (LAS). By means of X-ray diffraction (XRD) in single crystals, we determined the crystal structures of two new α-polytypes, which we have named α₁- and α₂-LAS. They present the same space group P2₁/c and the following relation among their lattice parameters: a₂ = −c₁, b₂ = −b₁, c₂ = −2a₁ − c₁. In order to evaluate the stability of the new α-polytypes, we performed thermal analysis, X-ray diffraction and dielectric spectroscopy on single crystals and polycrystalline samples over the cyclic temperature range: 190 → 575  → 190 K. The results obtained by all the techniques used in this study demonstrate that α-polytypes are stable across a wide range of temperatures and they show an irreversible phase transition to the paraelectric β-phase above 500 K. In addition, a comparative study of α- and β-polytypes shows that both polymorphic structures have a common axis, with a possible intergrowth that facilitates their coexistence and promotes the reconstructive α → β transition. This intergrowth was related to small anomalies detected between 240 and 260 K, in crystals with an α-habit.

Computing details

For both compounds, program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014). Molecular graphics: Diamond 4.0 for alpha1_LAS.

(alpha1_LAS)

Crystal data

O4SYb0.005·0.984(H4N)·Li	F(000) = 497
Mr = 121.54	Dx = 1.836 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.856 (8) Å	Cell parameters from 25 reflections
b = 5.008 (3) Å	θ = 9–21°
c = 10.264 (13) Å	µ = 0.73 mm^−1
β = 106.46 (5)°	T = 293 K
V = 880.2 (13) Å^3	Prism, colourless
Z = 8	0.18 × 0.14 × 0.09 mm

Data collection

ENRAF-NONIUS CAD4 diffractometer	θmax = 30.0°, θmin = 2.4°
ω/2Θ–scan	h = −25→0
4811 measured reflections	k = −7→7
2549 independent reflections	l = −13→14
2020 reflections with I > 2σ(I)	3 standard reflections every 120 min
Rint = 0.131	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.143	Only H-atom coordinates refined
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0484P)^2 + 0.6832P] where P = (Fo^2 + 2Fc^2)/3
2549 reflections	(Δ/σ)max < 0.001
153 parameters	Δρmax = 1.05 e Å^−3
74 restraints	Δρmin = −0.68 e Å^−3

Special details

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.

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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.40189 (3)	0.78809 (13)	0.35009 (6)	0.01614 (17)
O11	0.40752 (12)	0.7062 (5)	0.4897 (2)	0.0276 (5)
O12	0.41093 (12)	1.0821 (4)	0.3465 (2)	0.0309 (5)
O13	0.32607 (11)	0.7155 (5)	0.2583 (2)	0.0364 (6)
O14	0.46492 (11)	0.6618 (4)	0.3038 (2)	0.0240 (4)
S2	0.09813 (3)	0.28838 (12)	0.44726 (6)	0.01509 (16)
O21	0.09248 (11)	0.2049 (5)	0.58194 (19)	0.0265 (4)
O22	0.08937 (11)	0.5822 (4)	0.4341 (2)	0.0285 (5)
O23	0.03490 (10)	0.1605 (4)	0.33889 (18)	0.0220 (4)
O24	0.17400 (11)	0.2124 (5)	0.4303 (2)	0.0339 (5)
Yb1	0.33292 (13)	0.2738 (5)	0.0677 (3)	0.0311 (11)	0.0051 (12)
N1	0.33292 (13)	0.2738 (5)	0.0677 (3)	0.0311 (11)	0.985 (4)
H11	0.2772 (6)	0.290 (6)	0.031 (3)	0.047*	0.985 (4)
H12	0.3512 (16)	0.137 (5)	0.016 (3)	0.047*	0.985 (4)
H13	0.3573 (15)	0.439 (4)	0.055 (3)	0.047*	0.985 (4)
H14	0.3461 (17)	0.224 (6)	0.1612 (13)	0.047*	0.985 (4)
Yb2	0.16725 (13)	0.7751 (5)	0.2335 (3)	0.0306 (10)	0.0054 (12)
N2	0.16725 (13)	0.7751 (5)	0.2335 (3)	0.0306 (10)	0.984 (4)
H21	0.2230 (6)	0.773 (6)	0.255 (3)	0.046*	0.984 (4)
H22	0.1446 (16)	0.660 (5)	0.157 (2)	0.046*	0.984 (4)
H23	0.1509 (17)	0.713 (6)	0.310 (2)	0.046*	0.984 (4)
H24	0.1476 (16)	0.953 (3)	0.209 (3)	0.046*	0.984 (4)
Li1	0.0011 (2)	0.2967 (10)	0.1505 (5)	0.0202 (8)
Li2	0.5016 (2)	0.2965 (10)	0.3519 (5)	0.0226 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0186 (3)	0.0195 (3)	0.0119 (3)	0.0004 (2)	0.00700 (19)	0.0006 (2)
O11	0.0352 (9)	0.0369 (12)	0.0142 (8)	0.0014 (8)	0.0125 (7)	0.0070 (10)
O12	0.0404 (10)	0.0197 (9)	0.0394 (13)	0.0025 (8)	0.0223 (9)	0.0033 (10)
O13	0.0224 (8)	0.0535 (15)	0.0296 (11)	−0.0027 (9)	0.0015 (7)	−0.0163 (12)
O14	0.0313 (8)	0.0232 (10)	0.0235 (9)	0.0072 (7)	0.0178 (7)	0.0024 (9)
S2	0.0180 (3)	0.0167 (3)	0.0109 (3)	−0.00004 (19)	0.00455 (18)	0.0003 (2)
O21	0.0346 (9)	0.0341 (11)	0.0116 (8)	−0.0002 (8)	0.0076 (7)	0.0051 (9)
O22	0.0368 (10)	0.0144 (9)	0.0292 (11)	−0.0016 (7)	0.0009 (8)	0.0019 (9)
O23	0.0282 (8)	0.0196 (9)	0.0152 (8)	−0.0050 (7)	0.0012 (6)	−0.0003 (8)
O24	0.0214 (8)	0.0491 (14)	0.0339 (12)	0.0053 (8)	0.0122 (8)	−0.0118 (11)
Yb1	0.0309 (14)	0.0371 (16)	0.0259 (15)	0.0004 (9)	0.0087 (8)	0.0005 (11)
N1	0.0309 (14)	0.0371 (16)	0.0259 (15)	0.0004 (9)	0.0087 (8)	0.0005 (11)
Yb2	0.0344 (14)	0.0325 (15)	0.0266 (15)	−0.0006 (9)	0.0113 (9)	−0.0024 (11)
N2	0.0344 (14)	0.0325 (15)	0.0266 (15)	−0.0006 (9)	0.0113 (9)	−0.0024 (11)
Li1	0.0261 (18)	0.021 (2)	0.0142 (19)	0.0014 (16)	0.0060 (15)	−0.0006 (19)
Li2	0.0269 (19)	0.023 (2)	0.020 (2)	0.0022 (17)	0.0094 (16)	0.004 (2)

Geometric parameters (Å, º)

S1—O13	1.459 (2)	Yb1—Li2	3.551 (6)
S1—O11	1.466 (3)	Yb1—Li2^xi	3.707 (5)
S1—O14	1.482 (2)	Yb1—Li2^i	3.858 (5)
S1—O12	1.483 (2)	Yb1—H11	0.962 (9)
S1—Li2	3.035 (5)	Yb1—H12	0.976 (9)
S1—Li2^i	3.049 (5)	Yb1—H13	0.963 (9)
O11—Li2^ii	1.945 (5)	Yb1—H14	0.954 (9)
O11—Yb1^iii	2.966 (4)	Yb2—O24^iv	2.958 (4)
O12—Li2^iv	1.930 (5)	Yb2—O21^ix	2.967 (4)
O12—Yb1^iv	2.965 (5)	Yb2—O22^x	3.077 (5)
O12—Yb1^v	3.067 (4)	Yb2—Li1^vii	3.534 (5)
O13—Yb2	2.791 (3)	Yb2—Li1	3.720 (5)
O13—Yb1	2.978 (4)	Yb2—Li1^iv	3.863 (5)
O14—Li2	1.958 (5)	Yb2—H21	0.957 (9)
O14—Li2^i	1.976 (6)	Yb2—H22	0.968 (9)
S2—O24	1.464 (2)	Yb2—H23	0.963 (9)
S2—O21	1.475 (3)	Yb2—H24	0.966 (9)
S2—O22	1.482 (2)	Li1—O22^vi	1.929 (5)
S2—O23	1.487 (2)	Li1—O23^vii	1.945 (5)
S2—Li1^vi	3.033 (5)	Li1—O21^ix	1.952 (5)
S2—Li1	3.048 (6)	Li1—S2^vii	3.033 (5)
O21—Li1^iii	1.952 (5)	Li1—Li1^vi	3.238 (6)
O21—Yb2^iii	2.967 (4)	Li1—Li1^vii	3.238 (6)
O22—Li1^vii	1.929 (5)	Li1—Yb2^vi	3.534 (5)
O22—Yb2	2.955 (4)	Li1—Yb2^viii	3.863 (5)
O22—Yb2^v	3.077 (5)	Li2—O12^viii	1.930 (5)
O23—Li1^vi	1.945 (5)	Li2—O11^ii	1.945 (5)
O23—Li1	1.976 (5)	Li2—O14^xi	1.976 (6)
O24—Yb1^iii	2.789 (3)	Li2—S1^xi	3.049 (5)
O24—Yb2^viii	2.958 (4)	Li2—Li2^i	3.253 (7)
Yb1—O24^ix	2.789 (3)	Li2—Li2^xi	3.253 (7)
Yb1—O12^viii	2.965 (5)	Li2—Yb1^i	3.707 (5)
Yb1—O11^ix	2.966 (4)	Li2—Yb1^xi	3.858 (5)
Yb1—O12^x	3.067 (4)
O13—S1—O11	110.81 (15)	O22^x—Yb2—Li1^iv	61.38 (10)
O13—S1—O14	109.66 (14)	Li1^vii—Yb2—Li1^iv	51.69 (10)
O11—S1—O14	110.26 (13)	Li1—Yb2—Li1^iv	82.64 (10)
O13—S1—O12	108.61 (14)	O13—Yb2—H21	9.4 (18)
O11—S1—O12	108.90 (14)	O22—Yb2—H21	120.3 (18)
O14—S1—O12	108.54 (13)	O24^iv—Yb2—H21	90.8 (18)
O13—S1—Li2	103.71 (14)	O21^ix—Yb2—H21	113.3 (18)
O11—S1—Li2	83.67 (14)	O22^x—Yb2—H21	112.0 (18)
O14—S1—Li2	32.67 (13)	Li1^vii—Yb2—H21	148.6 (18)
O12—S1—Li2	137.54 (13)	Li1—Yb2—H21	139.2 (18)
O13—S1—Li2^i	99.45 (15)	Li1^iv—Yb2—H21	137.8 (18)
O11—S1—Li2^i	140.63 (13)	O13—Yb2—H22	100.9 (18)
O14—S1—Li2^i	32.93 (12)	O22—Yb2—H22	101.6 (19)
O12—S1—Li2^i	83.28 (13)	O24^iv—Yb2—H22	157.5 (18)
Li2—S1—Li2^i	64.64 (12)	O21^ix—Yb2—H22	21.2 (19)
S1—O11—Li2^ii	128.97 (19)	O22^x—Yb2—H22	50.2 (19)
S1—O11—Yb1^iii	125.36 (13)	Li1^vii—Yb2—H22	95.3 (18)
Li2^ii—O11—Yb1^iii	95.78 (17)	Li1—Yb2—H22	46.2 (18)
S1—O12—Li2^iv	130.39 (19)	Li1^iv—Yb2—H22	96.1 (18)
S1—O12—Yb1^iv	108.70 (13)	H21—Yb2—H22	110.3 (15)
Li2^iv—O12—Yb1^iv	90.47 (17)	O13—Yb2—H23	115.2 (18)
S1—O12—Yb1^v	98.04 (12)	O22—Yb2—H23	10.0 (18)
Li2^iv—O12—Yb1^v	113.64 (19)	O24^iv—Yb2—H23	69.4 (19)
Yb1^iv—O12—Yb1^v	116.77 (11)	O21^ix—Yb2—H23	88.2 (19)
S1—O13—Yb2	139.91 (15)	O22^x—Yb2—H23	137.1 (18)
S1—O13—Yb1	113.95 (13)	Li1^vii—Yb2—H23	41.6 (18)
Yb2—O13—Yb1	104.44 (10)	Li1—Yb2—H23	64.6 (18)
S1—O14—Li2	123.22 (19)	Li1^iv—Yb2—H23	90.4 (18)
S1—O14—Li2^i	123.01 (19)	H21—Yb2—H23	110.4 (15)
Li2—O14—Li2^i	111.50 (19)	H22—Yb2—H23	108.4 (15)
O24—S2—O21	110.42 (14)	O13—Yb2—H24	114.0 (17)
O24—S2—O22	108.95 (14)	O22—Yb2—H24	106.0 (18)
O21—S2—O22	109.47 (14)	O24^iv—Yb2—H24	55.6 (18)
O24—S2—O23	109.34 (14)	O21^ix—Yb2—H24	122.4 (18)
O21—S2—O23	109.88 (14)	O22^x—Yb2—H24	59.8 (18)
O22—S2—O23	108.75 (12)	Li1^vii—Yb2—H24	77.2 (18)
O24—S2—Li1^vi	102.87 (14)	Li1—Yb2—H24	109.1 (17)
O21—S2—Li1^vi	83.77 (14)	Li1^iv—Yb2—H24	28.1 (17)
O22—S2—Li1^vi	137.68 (12)	H21—Yb2—H24	110.2 (15)
O23—S2—Li1^vi	32.26 (12)	H22—Yb2—H24	107.5 (14)
O24—S2—Li1	99.68 (14)	H23—Yb2—H24	109.9 (15)
O21—S2—Li1	140.35 (13)	O22^vi—Li1—O23^vii	107.4 (2)
O22—S2—Li1	83.12 (12)	O22^vi—Li1—O21^ix	120.9 (3)
O23—S2—Li1	33.07 (12)	O23^vii—Li1—O21^ix	110.3 (2)
Li1^vi—S2—Li1	64.34 (11)	O22^vi—Li1—O23	103.5 (2)
S2—O21—Li1^iii	128.71 (17)	O23^vii—Li1—O23	106.4 (2)
S2—O21—Yb2^iii	125.53 (13)	O21^ix—Li1—O23	107.2 (2)
Li1^iii—O21—Yb2^iii	96.06 (17)	O22^vi—Li1—S2^vii	88.12 (16)
S2—O22—Li1^vii	130.33 (18)	O23^vii—Li1—S2^vii	24.07 (8)
S2—O22—Yb2	109.24 (13)	O21^ix—Li1—S2^vii	110.7 (2)
Li1^vii—O22—Yb2	90.18 (17)	O23—Li1—S2^vii	126.3 (2)
S2—O22—Yb2^v	97.69 (11)	O22^vi—Li1—S2	127.5 (2)
Li1^vii—O22—Yb2^v	113.85 (18)	O23^vii—Li1—S2	93.46 (17)
Yb2—O22—Yb2^v	116.82 (11)	O21^ix—Li1—S2	93.64 (17)
S2—O23—Li1^vi	123.67 (17)	O23—Li1—S2	24.23 (9)
S2—O23—Li1	122.70 (19)	S2^vii—Li1—S2	117.07 (15)
Li1^vi—O23—Li1	111.31 (18)	O22^vi—Li1—Li1^vi	72.28 (16)
S2—O24—Yb1^iii	140.94 (15)	O23^vii—Li1—Li1^vi	128.8 (3)
S2—O24—Yb2^viii	114.43 (13)	O21^ix—Li1—Li1^vi	112.6 (2)
Yb1^iii—O24—Yb2^viii	101.68 (10)	O23—Li1—Li1^vi	34.03 (16)
O24^ix—Yb1—O12^viii	128.95 (12)	S2^vii—Li1—Li1^vi	136.6 (2)
O24^ix—Yb1—O11^ix	110.73 (11)	S2—Li1—Li1^vi	57.61 (16)
O12^viii—Yb1—O11^ix	82.76 (10)	O22^vi—Li1—Li1^vii	123.8 (3)
O24^ix—Yb1—O13	95.07 (11)	O23^vii—Li1—Li1^vii	34.65 (7)
O12^viii—Yb1—O13	72.67 (11)	O21^ix—Li1—Li1^vii	113.0 (2)
O11^ix—Yb1—O13	152.18 (10)	O23—Li1—Li1^vii	72.8 (2)
O24^ix—Yb1—O12^x	103.30 (12)	S2^vii—Li1—Li1^vii	58.05 (10)
O12^viii—Yb1—O12^x	127.07 (12)	S2—Li1—Li1^vii	59.03 (16)
O11^ix—Yb1—O12^x	70.00 (9)	Li1^vi—Li1—Li1^vii	101.3 (3)
O13—Yb1—O12^x	115.03 (12)	O22^vi—Li1—Yb2^vi	56.74 (15)
O24^ix—Yb1—Li2	156.80 (13)	O23^vii—Li1—Yb2^vi	71.59 (15)
O12^viii—Yb1—Li2	32.93 (10)	O21^ix—Li1—Yb2^vi	177.6 (2)
O11^ix—Yb1—Li2	84.64 (11)	O23—Li1—Yb2^vi	73.35 (16)
O13—Yb1—Li2	67.66 (11)	S2^vii—Li1—Yb2^vi	70.35 (10)
O12^x—Yb1—Li2	98.22 (13)	S2—Li1—Yb2^vi	87.72 (14)
O24^ix—Yb1—Li2^xi	139.57 (13)	Li1^vi—Li1—Yb2^vi	66.48 (17)
O12^viii—Yb1—Li2^xi	56.60 (10)	Li1^vii—Li1—Yb2^vi	69.41 (17)
O11^ix—Yb1—Li2^xi	31.46 (9)	O22^vi—Li1—Yb2	166.7 (2)
O13—Yb1—Li2^xi	120.74 (12)	O23^vii—Li1—Yb2	68.81 (14)
O12^x—Yb1—Li2^xi	79.39 (11)	O21^ix—Li1—Yb2	52.48 (13)
Li2—Yb1—Li2^xi	53.19 (11)	O23—Li1—Yb2	89.73 (16)
O24^ix—Yb1—Li2^i	134.36 (13)	S2^vii—Li1—Yb2	84.61 (13)
O12^viii—Yb1—Li2^i	83.77 (11)	S2—Li1—Yb2	65.74 (10)
O11^ix—Yb1—Li2^i	103.43 (11)	Li1^vi—Li1—Yb2	120.3 (2)
O13—Yb1—Li2^i	61.78 (10)	Li1^vii—Li1—Yb2	60.57 (12)
O12^x—Yb1—Li2^i	61.16 (11)	Yb2^vi—Li1—Yb2	129.94 (15)
Li2—Yb1—Li2^i	51.88 (10)	O22^vi—Li1—Yb2^viii	102.44 (19)
Li2^xi—Yb1—Li2^i	82.88 (10)	O23^vii—Li1—Yb2^viii	150.02 (19)
O24^ix—Yb1—H11	7.4 (18)	O21^ix—Li1—Yb2^viii	53.72 (13)
O12^viii—Yb1—H11	124.0 (17)	O23—Li1—Yb2^viii	63.13 (14)
O11^ix—Yb1—H11	117.0 (18)	S2^vii—Li1—Yb2^viii	164.14 (16)
O13—Yb1—H11	88.1 (18)	S2—Li1—Yb2^viii	65.58 (9)
O12^x—Yb1—H11	108.8 (17)	Li1^vi—Li1—Yb2^viii	58.90 (12)
Li2—Yb1—H11	149.7 (18)	Li1^vii—Li1—Yb2^viii	122.0 (2)
Li2^xi—Yb1—H11	144.2 (18)	Yb2^vi—Li1—Yb2^viii	125.35 (15)
Li2^i—Yb1—H11	132.1 (18)	Yb2—Li1—Yb2^viii	82.64 (10)
O24^ix—Yb1—H12	101.1 (17)	O12^viii—Li2—O11^ii	120.9 (3)
O12^viii—Yb1—H12	99.1 (18)	O12^viii—Li2—O14	107.1 (2)
O11^ix—Yb1—H12	16.4 (18)	O11^ii—Li2—O14	111.0 (3)
O13—Yb1—H12	163.5 (17)	O12^viii—Li2—O14^xi	103.3 (2)
O12^x—Yb1—H12	58.1 (19)	O11^ii—Li2—O14^xi	107.5 (2)
Li2—Yb1—H12	97.6 (17)	O14—Li2—O14^xi	105.7 (2)
Li2^xi—Yb1—H12	45.7 (18)	O12^viii—Li2—S1	88.02 (17)
Li2^i—Yb1—H12	103.8 (18)	O11^ii—Li2—S1	111.1 (2)
H11—Yb1—H12	108.1 (14)	O14—Li2—S1	24.11 (9)
O24^ix—Yb1—H13	110.1 (17)	O14^xi—Li2—S1	125.7 (2)
O12^viii—Yb1—H13	107.7 (18)	O12^viii—Li2—S1^xi	127.2 (2)
O11^ix—Yb1—H13	114.0 (18)	O11^ii—Li2—S1^xi	94.00 (19)
O13—Yb1—H13	63.5 (18)	O14—Li2—S1^xi	93.13 (19)
O12^x—Yb1—H13	51.6 (18)	O14^xi—Li2—S1^xi	24.06 (9)
Li2—Yb1—H13	76.9 (18)	S1—Li2—S1^xi	116.79 (16)
Li2^xi—Yb1—H13	102.9 (17)	O12^viii—Li2—Li2^i	123.2 (3)
Li2^i—Yb1—H13	25.4 (17)	O11^ii—Li2—Li2^i	113.7 (2)
H11—Yb1—H13	109.2 (15)	O14—Li2—Li2^i	34.43 (7)
H12—Yb1—H13	107.2 (14)	O14^xi—Li2—Li2^i	72.4 (2)
O24^ix—Yb1—H14	116.2 (18)	S1—Li2—Li2^i	57.88 (9)
O12^viii—Yb1—H14	14.1 (18)	S1^xi—Li2—Li2^i	58.92 (17)
O11^ix—Yb1—H14	93.3 (19)	O12^viii—Li2—Li2^xi	72.04 (16)
O13—Yb1—H14	65.1 (19)	O11^ii—Li2—Li2^xi	113.0 (2)
O12^x—Yb1—H14	140.5 (18)	O14—Li2—Li2^xi	127.8 (3)
Li2—Yb1—H14	43.3 (18)	O14^xi—Li2—Li2^xi	34.07 (17)
Li2^xi—Yb1—H14	69.7 (18)	S1—Li2—Li2^xi	135.8 (2)
Li2^i—Yb1—H14	90.4 (18)	S1^xi—Li2—Li2^xi	57.48 (17)
H11—Yb1—H14	110.7 (15)	Li2^i—Li2—Li2^xi	100.7 (3)
H12—Yb1—H14	109.7 (15)	O12^viii—Li2—Yb1	56.60 (14)
H13—Yb1—H14	111.8 (15)	O11^ii—Li2—Yb1	177.4 (2)
O13—Yb2—O22	124.64 (12)	O14—Li2—Yb1	71.20 (14)
O13—Yb2—O24^iv	99.98 (10)	O14^xi—Li2—Yb1	72.88 (17)
O22—Yb2—O24^iv	72.69 (10)	S1—Li2—Yb1	70.22 (10)
O13—Yb2—O21^ix	104.82 (11)	S1^xi—Li2—Yb1	87.27 (15)
O22—Yb2—O21^ix	82.52 (10)	Li2^i—Li2—Yb1	68.93 (17)
O24^iv—Yb2—O21^ix	152.00 (11)	Li2^xi—Li2—Yb1	65.86 (17)
O13—Yb2—O22^x	106.02 (11)	O12^viii—Li2—Yb1^i	166.9 (2)
O22—Yb2—O22^x	127.10 (12)	O11^ii—Li2—Yb1^i	52.76 (14)
O24^iv—Yb2—O22^x	115.42 (12)	O14—Li2—Yb1^i	69.04 (15)
O21^ix—Yb2—O22^x	69.85 (9)	O14^xi—Li2—Yb1^i	89.74 (17)
O13—Yb2—Li1^vii	155.77 (13)	S1—Li2—Yb1^i	84.70 (13)
O22—Yb2—Li1^vii	33.09 (9)	S1^xi—Li2—Yb1^i	65.90 (11)
O24^iv—Yb2—Li1^vii	67.76 (10)	Li2^i—Li2—Yb1^i	60.94 (13)
O21^ix—Yb2—Li1^vii	84.38 (11)	Li2^xi—Li2—Yb1^i	120.5 (2)
O22^x—Yb2—Li1^vii	98.18 (12)	Yb1—Li2—Yb1^i	129.83 (15)
O13—Yb2—Li1	132.54 (13)	O12^viii—Li2—Yb1^xi	102.3 (2)
O22—Yb2—Li1	56.40 (10)	O11^ii—Li2—Yb1^xi	53.79 (14)
O24^iv—Yb2—Li1	120.57 (11)	O14—Li2—Yb1^xi	150.3 (2)
O21^ix—Yb2—Li1	31.46 (9)	O14^xi—Li2—Yb1^xi	63.41 (15)
O22^x—Yb2—Li1	79.36 (10)	S1—Li2—Yb1^xi	164.60 (16)
Li1^vii—Yb2—Li1	52.95 (10)	S1^xi—Li2—Yb1^xi	65.78 (10)
O13—Yb2—Li1^iv	142.16 (13)	Li2^i—Li2—Yb1^xi	122.2 (2)
O22—Yb2—Li1^iv	83.74 (10)	Li2^xi—Li2—Yb1^xi	59.19 (12)
O24^iv—Yb2—Li1^iv	61.97 (10)	Yb1—Li2—Yb1^xi	125.02 (16)
O21^ix—Yb2—Li1^iv	103.22 (11)	Yb1^i—Li2—Yb1^xi	82.88 (10)

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z+1/2; (iv) x, y+1, z; (v) x, −y+3/2, z+1/2; (vi) −x, y−1/2, −z+1/2; (vii) −x, y+1/2, −z+1/2; (viii) x, y−1, z; (ix) x, −y+1/2, z−1/2; (x) x, −y+3/2, z−1/2; (xi) −x+1, y−1/2, −z+1/2.

(alpha2_LAS)

Crystal data

O4SYb0.013·0.961(H4N)·Li	F(000) = 1000.0
Mr = 122.51	Dx = 1.831 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.177 (15) Å	Cell parameters from 25 reflections
b = 5.106 (4) Å	θ = 9–19°
c = 34.234 (16) Å	µ = 0.89 mm^−1
β = 90.2 (1)°	T = 293 K
V = 1779 (3) Å^3	Prism, colourless
Z = 16	0.17 × 0.11 × 0.09 mm

Data collection

ENRAF-Nonius CAD4 diffractometer	θmax = 30.0°, θmin = 2.0°
ω/2Θ–scan	h = −14→14
9573 measured reflections	k = −7→7
5071 independent reflections	l = −48→0
3231 reflections with I > 2σ(I)	3 standard reflections every 120 min
Rint = 0.068

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: notdet
wR(F^2) = 0.163	H-atom parameters not defined
S = 1.20	w = 1/[σ^2(Fo^2) + (0.0263P)^2 + 6.4506P] where P = (Fo^2 + 2Fc^2)/3
5071 reflections	(Δ/σ)max < 0.001
256 parameters	Δρmax = 1.89 e Å^−3
0 restraints	Δρmin = −1.04 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.64805 (7)	0.73307 (14)	0.20089 (2)	0.00608 (14)
O11	0.6399 (4)	0.4374 (5)	0.20610 (11)	0.0406 (9)
O12	0.7859 (3)	0.8058 (10)	0.20413 (11)	0.0521 (12)
O13	0.5709 (3)	0.8568 (6)	0.23235 (9)	0.0274 (7)
O14	0.5950 (4)	0.7924 (10)	0.16305 (10)	0.0566 (13)
S2	0.89820 (8)	0.28368 (18)	0.04920 (3)	0.01657 (19)
O21	0.8934 (3)	0.5828 (6)	0.04414 (10)	0.0324 (8)
O22	1.0370 (3)	0.2110 (6)	0.04620 (9)	0.0298 (7)
O23	0.8456 (3)	0.2180 (7)	0.08669 (9)	0.0368 (8)
O24	0.8213 (3)	0.1630 (6)	0.01798 (9)	0.0280 (7)
S3	0.39959 (8)	0.21622 (18)	0.04902 (3)	0.01718 (19)
O31	0.5355 (3)	0.2891 (6)	0.04630 (10)	0.0304 (7)
O32	0.3211 (3)	0.3371 (6)	0.01735 (9)	0.0273 (7)
O33	0.3916 (3)	−0.0811 (6)	0.04468 (10)	0.0330 (8)
O34	0.3434 (3)	0.2813 (7)	0.08748 (9)	0.0324 (7)
S4	0.14878 (11)	0.8032 (3)	0.20093 (4)	0.0364 (3)
O41	0.1414 (3)	1.1054 (7)	0.20461 (9)	0.0314 (7)
O42	0.2864 (2)	0.7278 (5)	0.20357 (8)	0.0211 (5)
O43	0.0927 (3)	0.7312 (6)	0.16299 (9)	0.0272 (6)
O44	0.0714 (3)	0.6850 (7)	0.23248 (9)	0.0292 (7)
N1	0.4006 (3)	0.2369 (6)	0.16624 (10)	0.0417 (11)	0.907 (4)
N2	0.6508 (3)	0.7697 (7)	0.08377 (10)	0.0364 (13)	0.959 (4)
N3	0.1517 (3)	0.7309 (7)	0.08326 (11)	0.0331 (14)	0.978 (4)
N4	0.9005 (4)	0.2744 (9)	0.16666 (12)	0.0381 (10)
Yb1	0.4006 (3)	0.2369 (6)	0.16624 (10)	0.0417 (11)	0.0311 (15)
Yb2	0.6508 (3)	0.7697 (7)	0.08377 (10)	0.0364 (13)	0.0137 (15)
Yb3	0.1517 (3)	0.7309 (7)	0.08326 (11)	0.0331 (14)	0.0074 (14)
Li1	0.3992 (7)	0.7198 (14)	0.2497 (2)	0.0237 (14)
Li2	0.1017 (7)	0.3041 (15)	0.2508 (2)	0.0278 (16)
Li3	0.1488 (7)	0.2123 (13)	0.0001 (2)	0.0218 (14)
Li4	0.6491 (6)	0.2976 (12)	0.0013 (2)	0.0190 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0035 (3)	0.0084 (3)	0.0063 (3)	−0.0004 (3)	−0.0014 (2)	−0.0003 (3)
O11	0.065 (2)	0.0118 (13)	0.045 (2)	−0.0014 (14)	0.0142 (18)	−0.0014 (13)
O12	0.0098 (13)	0.114 (4)	0.0322 (19)	−0.0037 (18)	0.0014 (12)	−0.005 (2)
O13	0.0287 (15)	0.0257 (14)	0.0279 (17)	−0.0020 (12)	0.0078 (13)	−0.0013 (12)
O14	0.0377 (19)	0.122 (4)	0.0099 (14)	0.016 (2)	−0.0061 (13)	0.001 (2)
S2	0.0104 (3)	0.0249 (4)	0.0144 (4)	0.0028 (3)	−0.0027 (3)	−0.0003 (3)
O21	0.0384 (18)	0.0255 (14)	0.0332 (19)	0.0041 (13)	−0.0138 (14)	−0.0020 (13)
O22	0.0117 (11)	0.051 (2)	0.0270 (16)	0.0109 (12)	−0.0030 (11)	−0.0023 (14)
O23	0.0348 (17)	0.060 (2)	0.0155 (14)	−0.0126 (16)	0.0031 (12)	−0.0080 (15)
O24	0.0218 (14)	0.0364 (16)	0.0257 (17)	0.0053 (12)	−0.0079 (12)	−0.0079 (13)
S3	0.0114 (3)	0.0266 (5)	0.0135 (4)	0.0016 (3)	−0.0026 (3)	−0.0019 (3)
O31	0.0112 (11)	0.0487 (19)	0.0313 (17)	−0.0048 (12)	−0.0051 (11)	−0.0013 (14)
O32	0.0209 (14)	0.0369 (15)	0.0238 (16)	0.0019 (12)	−0.0116 (12)	0.0060 (13)
O33	0.0323 (17)	0.0259 (15)	0.041 (2)	−0.0004 (12)	−0.0165 (15)	0.0033 (14)
O34	0.0259 (14)	0.0484 (19)	0.0230 (15)	0.0146 (14)	0.0050 (12)	−0.0002 (14)
S4	0.0179 (4)	0.0704 (9)	0.0209 (5)	−0.0018 (5)	0.0000 (4)	−0.0005 (6)
O41	0.0173 (13)	0.057 (2)	0.0205 (15)	0.0063 (14)	0.0055 (11)	0.0008 (15)
O42	0.0074 (10)	0.0309 (14)	0.0249 (14)	0.0036 (10)	−0.0002 (9)	−0.0053 (12)
O43	0.0234 (13)	0.0381 (16)	0.0200 (14)	−0.0162 (13)	−0.0093 (11)	−0.0002 (13)
O44	0.0111 (12)	0.056 (2)	0.0207 (15)	0.0053 (12)	0.0038 (11)	0.0073 (13)
N1	0.0405 (18)	0.0413 (17)	0.0432 (19)	−0.0032 (13)	−0.0030 (12)	−0.0037 (14)
N2	0.034 (2)	0.043 (2)	0.032 (2)	0.0015 (15)	0.0024 (13)	−0.0043 (15)
N3	0.0247 (18)	0.043 (2)	0.032 (2)	−0.0003 (15)	−0.0039 (13)	−0.0048 (16)
N4	0.0216 (16)	0.067 (3)	0.0252 (19)	−0.0026 (19)	−0.0052 (14)	0.002 (2)
Yb1	0.0405 (18)	0.0413 (17)	0.0432 (19)	−0.0032 (13)	−0.0030 (12)	−0.0037 (14)
Yb2	0.034 (2)	0.043 (2)	0.032 (2)	0.0015 (15)	0.0024 (13)	−0.0043 (15)
Yb3	0.0247 (18)	0.043 (2)	0.032 (2)	−0.0003 (15)	−0.0039 (13)	−0.0048 (16)
Li1	0.019 (3)	0.034 (4)	0.018 (3)	−0.001 (3)	0.004 (2)	0.002 (3)
Li2	0.018 (3)	0.040 (4)	0.025 (4)	0.003 (3)	−0.006 (3)	0.000 (3)
Li3	0.024 (3)	0.021 (3)	0.021 (3)	0.002 (2)	−0.002 (3)	−0.006 (3)
Li4	0.011 (3)	0.023 (3)	0.023 (3)	0.000 (2)	−0.002 (2)	−0.006 (2)

Geometric parameters (Å, º)

S1—O14	1.434 (3)	S4—O43	1.464 (3)
S1—O12	1.455 (4)	S4—O44	1.469 (3)
S1—O13	1.477 (3)	S4—O41	1.550 (4)
S1—O11	1.522 (3)	S4—Li2^ix	3.043 (9)
S1—Li1	3.040 (8)	O41—Li2^iii	1.922 (9)
S1—Li1^i	3.045 (7)	O41—Yb1^iii	3.027 (6)
O11—Li1^ii	1.920 (8)	O42—Li1	1.950 (8)
O12—Li2^i	1.918 (8)	O44—Li2^ix	1.951 (8)
O13—Li1^i	1.976 (8)	O44—Li2	2.066 (8)
O13—Li1	1.976 (8)	Li1—O11^i	1.920 (8)
O14—Yb1^iii	3.013 (6)	Li1—O13^ii	1.976 (8)
S2—O23	1.432 (3)	Li1—S1^ii	3.045 (7)
S2—O24	1.459 (3)	Li1—Li1^ii	3.275 (9)
S2—O22	1.464 (3)	Li1—Li1^i	3.275 (9)
S2—O21	1.538 (3)	Li1—Yb1^i	3.520 (8)
S2—Li4	3.016 (7)	Li1—Yb1^iii	3.891 (8)
O21—Li3^iv	1.890 (8)	Li2—O12^ii	1.918 (8)
O21—Yb3^v	3.042 (6)	Li2—O41^vii	1.922 (9)
O22—Li3^v	1.948 (8)	Li2—O44^x	1.951 (8)
O22—Yb3^vi	2.996 (5)	Li2—S4^x	3.043 (9)
O23—Yb2^vii	3.030 (5)	Li2—Li2^ix	3.287 (9)
O24—Li4	1.966 (7)	Li2—Li2^x	3.287 (9)
O24—Li3^viii	2.037 (7)	Li3—O21^iv	1.890 (8)
S3—O31	1.436 (3)	Li3—O22^xi	1.948 (8)
S3—O34	1.475 (3)	Li3—O24^viii	2.037 (7)
S3—O32	1.479 (3)	Li3—Li4^iv	3.239 (9)
S3—O33	1.527 (3)	Li3—Li4^viii	3.319 (9)
S3—Li3	3.047 (8)	Li3—Yb2^iv	3.530 (9)
O31—Li4	1.930 (8)	Li3—Yb3^vii	3.760 (8)
O32—Li3	1.954 (8)	Li4—O33^viii	1.966 (7)
O32—Li4^iv	1.995 (7)	Li4—O32^iv	1.995 (7)
O33—Li4^viii	1.966 (7)	Li4—Li3^iv	3.239 (9)
O33—Yb3^vii	2.941 (6)	Li4—Li3^viii	3.319 (9)
O33—Yb2^vii	3.050 (6)	Li4—Yb3^iv	3.542 (9)
S4—O42	1.455 (3)	Li4—Yb2^vii	3.904 (8)
O14—S1—O12	112.0 (2)	O13^ii—Li1—Yb1^i	71.4 (2)
O14—S1—O13	111.7 (2)	O13—Li1—Yb1^i	74.2 (2)
O12—S1—O13	110.5 (2)	S1—Li1—Yb1^i	88.2 (2)
O14—S1—O11	107.2 (3)	S1^ii—Li1—Yb1^i	70.03 (16)
O12—S1—O11	107.3 (3)	Li1^ii—Li1—Yb1^i	69.8 (3)
O13—S1—O11	108.0 (2)	Li1^i—Li1—Yb1^i	67.4 (3)
O14—S1—Li1	101.0 (2)	O11^i—Li1—Yb1^iii	100.8 (3)
O12—S1—Li1	140.2 (2)	O42—Li1—Yb1^iii	52.7 (2)
O13—S1—Li1	33.14 (19)	O13^ii—Li1—Yb1^iii	149.8 (3)
O11—S1—Li1	82.4 (2)	O13—Li1—Yb1^iii	62.2 (2)
O14—S1—Li1^i	105.6 (2)	S1—Li1—Yb1^iii	64.90 (15)
O12—S1—Li1^i	84.5 (2)	S1^ii—Li1—Yb1^iii	164.3 (2)
O13—S1—Li1^i	32.91 (18)	Li1^ii—Li1—Yb1^iii	122.0 (3)
O11—S1—Li1^i	137.4 (2)	Li1^i—Li1—Yb1^iii	58.09 (19)
Li1—S1—Li1^i	65.12 (16)	Yb1^i—Li1—Yb1^iii	125.4 (2)
S1—O11—Li1^ii	132.7 (3)	O12^ii—Li2—O41^vii	122.5 (4)
S1—O12—Li2^i	129.2 (3)	O12^ii—Li2—O44^x	107.6 (4)
S1—O13—Li1^i	123.1 (3)	O41^vii—Li2—O44^x	105.6 (4)
S1—O13—Li1	122.7 (3)	O12^ii—Li2—O44	109.1 (4)
Li1^i—O13—Li1	112.0 (3)	O41^vii—Li2—O44	106.2 (4)
S1—O14—Yb1^iii	111.8 (2)	O44^x—Li2—O44	104.4 (3)
O23—S2—O24	110.9 (2)	O12^ii—Li2—S4^x	93.5 (3)
O23—S2—O22	111.5 (2)	O41^vii—Li2—S4^x	128.7 (3)
O24—S2—O22	110.9 (2)	O44^x—Li2—S4^x	23.27 (15)
O23—S2—O21	108.8 (2)	O44—Li2—S4^x	92.4 (3)
O24—S2—O21	108.67 (18)	O12^ii—Li2—Li2^ix	112.5 (4)
O22—S2—O21	105.90 (19)	O41^vii—Li2—Li2^ix	122.1 (4)
O23—S2—Li4	100.2 (2)	O44^x—Li2—Li2^ix	71.2 (4)
O24—S2—Li4	33.25 (17)	O44—Li2—Li2^ix	33.96 (10)
O22—S2—Li4	140.99 (19)	S4^x—Li2—Li2^ix	58.8 (3)
O21—S2—Li4	83.62 (17)	O12^ii—Li2—Li2^x	113.0 (4)
S2—O21—Li3^iv	130.3 (3)	O41^vii—Li2—Li2^x	73.2 (3)
S2—O21—Yb3^v	99.80 (16)	O44^x—Li2—Li2^x	36.3 (3)
Li3^iv—O21—Yb3^v	114.2 (3)	O44—Li2—Li2^x	129.3 (4)
S2—O22—Li3^v	128.5 (3)	S4^x—Li2—Li2^x	58.6 (3)
S2—O22—Yb3^vi	123.5 (2)	Li2^ix—Li2—Li2^x	101.9 (4)
Li3^v—O22—Yb3^vi	96.8 (2)	O21^iv—Li3—O22^xi	121.3 (4)
S2—O23—Yb2^vii	113.19 (18)	O21^iv—Li3—O32	105.2 (4)
S2—O24—Li4	122.7 (3)	O22^xi—Li3—O32	106.4 (4)
S2—O24—Li3^viii	122.7 (3)	O21^iv—Li3—O24^viii	108.1 (3)
Li4—O24—Li3^viii	112.0 (3)	O22^xi—Li3—O24^viii	109.4 (4)
O31—S3—O34	112.1 (2)	O32—Li3—O24^viii	105.3 (3)
O31—S3—O32	111.2 (2)	O21^iv—Li3—S3	128.6 (3)
O34—S3—O32	110.49 (19)	O22^xi—Li3—S3	92.6 (3)
O31—S3—O33	107.58 (19)	O32—Li3—S3	23.58 (14)
O34—S3—O33	106.9 (2)	O24^viii—Li3—S3	92.7 (2)
O32—S3—O33	108.37 (18)	O21^iv—Li3—Li4^iv	72.7 (3)
O31—S3—Li3	140.5 (2)	O22^xi—Li3—Li4^iv	112.8 (3)
O34—S3—Li3	99.5 (2)	O32—Li3—Li4^iv	35.30 (19)
O32—S3—Li3	31.90 (19)	O24^viii—Li3—Li4^iv	128.8 (3)
O33—S3—Li3	84.04 (17)	S3—Li3—Li4^iv	58.17 (16)
S3—O31—Li4	129.6 (3)	O21^iv—Li3—Li4^viii	124.2 (3)
S3—O32—Li3	124.5 (3)	O22^xi—Li3—Li4^viii	111.9 (3)
S3—O32—Li4^iv	122.8 (3)	O32—Li3—Li4^viii	72.8 (2)
Li3—O32—Li4^iv	110.2 (3)	O24^viii—Li3—Li4^viii	33.33 (19)
S3—O33—Li4^viii	130.4 (3)	S3—Li3—Li4^viii	59.68 (16)
S3—O33—Yb3^vii	108.95 (19)	Li4^iv—Li3—Li4^viii	102.3 (2)
Li4^viii—O33—Yb3^vii	90.2 (2)	O21^iv—Li3—Yb2^iv	57.5 (2)
S3—O33—Yb2^vii	99.22 (15)	O22^xi—Li3—Yb2^iv	178.6 (3)
Li4^viii—O33—Yb2^vii	113.0 (2)	O32—Li3—Yb2^iv	73.5 (3)
Yb3^vii—O33—Yb2^vii	116.06 (16)	O24^viii—Li3—Yb2^iv	71.9 (2)
O42—S4—O43	111.2 (2)	S3—Li3—Yb2^iv	87.8 (2)
O42—S4—O44	111.4 (2)	Li4^iv—Li3—Yb2^iv	66.37 (18)
O43—S4—O44	109.9 (2)	Li4^viii—Li3—Yb2^iv	69.43 (18)
O42—S4—O41	107.78 (18)	O21^iv—Li3—Yb3^vii	165.9 (3)
O43—S4—O41	107.7 (2)	O22^xi—Li3—Yb3^vii	52.3 (2)
O44—S4—O41	108.9 (2)	O32—Li3—Yb3^vii	88.9 (3)
O42—S4—Li2^ix	140.8 (2)	O24^viii—Li3—Yb3^vii	67.3 (2)
O43—S4—Li2^ix	99.1 (2)	S3—Li3—Yb3^vii	65.44 (15)
O44—S4—Li2^ix	31.65 (19)	Li4^iv—Li3—Yb3^vii	120.9 (2)
O41—S4—Li2^ix	85.04 (19)	Li4^viii—Li3—Yb3^vii	59.66 (18)
S4—O41—Li2^iii	127.1 (3)	Yb2^iv—Li3—Yb3^vii	129.0 (2)
S4—O41—Yb1^iii	98.23 (15)	O31—Li4—O33^viii	120.1 (3)
Li2^iii—O41—Yb1^iii	115.2 (3)	O31—Li4—O24	107.2 (4)
S4—O42—Li1	128.3 (3)	O33^viii—Li4—O24	102.8 (3)
S4—O44—Li2^ix	125.1 (3)	O31—Li4—O32^iv	111.6 (3)
S4—O44—Li2	122.0 (3)	O33^viii—Li4—O32^iv	107.6 (4)
Li2^ix—O44—Li2	109.8 (3)	O24—Li4—O32^iv	106.5 (3)
O11^i—Li1—O42	120.2 (4)	O31—Li4—S2	94.0 (3)
O11^i—Li1—O13^ii	109.3 (4)	O33^viii—Li4—S2	126.6 (3)
O42—Li1—O13^ii	111.2 (4)	O24—Li4—S2	24.01 (13)
O11^i—Li1—O13	102.6 (4)	O32^iv—Li4—S2	93.9 (2)
O42—Li1—O13	105.5 (4)	O31—Li4—Li3^iv	114.3 (3)
O13^ii—Li1—O13	106.9 (3)	O33^viii—Li4—Li3^iv	123.7 (3)
O11^i—Li1—S1	126.6 (3)	O24—Li4—Li3^iv	73.1 (2)
O42—Li1—S1	92.5 (3)	O32^iv—Li4—Li3^iv	34.47 (19)
O13^ii—Li1—S1	93.7 (3)	S2—Li4—Li3^iv	59.59 (16)
O13—Li1—S1	24.12 (14)	O31—Li4—Li3^viii	111.5 (3)
O11^i—Li1—S1^ii	90.1 (3)	O33^viii—Li4—Li3^viii	71.1 (2)
O42—Li1—S1^ii	111.9 (3)	O24—Li4—Li3^viii	34.71 (18)
O13^ii—Li1—S1^ii	23.96 (13)	O32^iv—Li4—Li3^viii	129.3 (3)
O13—Li1—S1^ii	126.7 (3)	S2—Li4—Li3^viii	57.96 (15)
S1—Li1—S1^ii	117.2 (2)	Li3^iv—Li4—Li3^viii	102.3 (2)
O11^i—Li1—Li1^ii	125.3 (4)	O31—Li4—Yb3^iv	175.9 (3)
O42—Li1—Li1^ii	112.8 (4)	O33^viii—Li4—Yb3^iv	56.1 (2)
O13^ii—Li1—Li1^ii	34.03 (11)	O24—Li4—Yb3^iv	73.2 (2)
O13—Li1—Li1^ii	73.9 (3)	O32^iv—Li4—Yb3^iv	71.9 (2)
S1—Li1—Li1^ii	59.8 (2)	S2—Li4—Yb3^iv	87.77 (18)
S1^ii—Li1—Li1^ii	57.36 (15)	Li3^iv—Li4—Yb3^iv	69.78 (18)
O11^i—Li1—Li1^i	71.1 (2)	Li3^viii—Li4—Yb3^iv	66.38 (18)
O42—Li1—Li1^i	110.8 (3)	O31—Li4—Yb2^vii	53.7 (2)
O13^ii—Li1—Li1^i	129.3 (4)	O33^viii—Li4—Yb2^vii	101.0 (3)
O13—Li1—Li1^i	34.0 (2)	O24—Li4—Yb2^vii	63.0 (2)
S1—Li1—Li1^i	57.5 (2)	O32^iv—Li4—Yb2^vii	151.2 (3)
S1^ii—Li1—Li1^i	137.1 (4)	S2—Li4—Yb2^vii	65.70 (15)
Li1^ii—Li1—Li1^i	102.4 (4)	Li3^iv—Li4—Yb2^vii	122.9 (2)
O11^i—Li1—Yb1^i	57.5 (2)	Li3^viii—Li4—Yb2^vii	57.83 (17)
O42—Li1—Yb1^i	177.3 (3)	Yb3^iv—Li4—Yb2^vii	124.17 (19)

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