Twinned [alpha]-LiRb₂(CF₃SO₃)₃

The investigated crystal of [alpha]-LiRb₂(CF₃SO₃)₃ [lithium dirubidium tris­(tri­fluoro­methane­sulfonate)] was a twin, with the twin matrix given by (00/010/001). The structure consists of channel-like patterns built up of lipophilic CF₃ groups pointing towards each other. The polar interstices are occupied by cations. One Rb atom is coordinated by O atoms in the form of a distorted square antiprism, while the coordination around the second Rb atom is best described as a distorted pentagonal plane, with one O atom and one F atom situated above and an additional F atom below this plane. The O atoms around the Li atom form a strongly distorted tetrahedron.

S1. Comment

Salts consisting of complex anions often show phase transitions to rotationally disordered modifications. As a rule, these phase transitions are accompanied by an increase of the ionic conductivity (Jansen, 1991). Alkali metal salts of the trifluoromethylsulfonate (trifluoromethanesulfonate) ion belong to these so-called rotator phases. Due to their interesting properties, the ionic conductivities and crystal structures of, for example, β-LiSO₃CF₃ (Tremayne et al., 1992; Bolte & Lerner, 2001), α-NaSO₃CF₃ (Sofina et al., 2003) and RT-KSO₃CF₃ (Korus & Jansen, 2001) have been studied in detail. Furthermore, mixed alkali trifluoromethanesulfonates offer the possibility of exploring the `mixed cation effect', which can be observed in ion-conducting systems containing more than one mobile cation (Yanija & Secco, 1995). The ionic conductivity of compounds in such systems can generally be varied by adjusting the ratio of the cations.

Against this background, we have carried out systematic investigations of the phase diagram of the LiSO₃CF₃/RbSO₃CF₃ system. In the course of these investigations, crystals of α-LiRb₂(SO₃CF₃)₃ were found and the structure is presented here. The structure determination was rendered complicated due to underlying twinning.

In the structure of α-LiRb₂(SO₃CF₃)₃, three crystallographically independent trifluoromethanesulfonate ions can be distinguished. Their conformation is staggered and the observed bond lengths and angles are comparable to those in β-LiSO₃CF₃ (Bolte & Lerner, 2001), α-NaSO₃CF₃(Sofina et al., 2003), the low- and room-temperature modifications of NaSO₃CF₃·H₂O (Korus & Jansen, 1997), NaSO₃CF₃·3HSO₃CF₃ (Korus & Jansen, 1998) and RT-KSO₃CF₃ (Korus & Jansen, 2001).

In α-LiRb₂(SO₃CF₃)₃, atom Rb1 is coordinated by O atoms in the form of a distorted square antiprism (Fig. 1). The cation is displaced towards the plane formed by atoms O1, O4, O7^iv and O9ⁱⁱ [symmetry codes: (ii) 1 + x, y, z; (iv) −x, 2 − y, −z]. Atom O5ⁱⁱⁱ is shifted from the ideal position and approaches atom O6ⁱⁱⁱ, as both atoms are bridged by an S atom [symmetry code: (iii) x − 1, y, z]. Each of the remaining O atoms forms part of a different trifluoromethanesulfonate ion. Please check that added symmetry codes, here and elsewhere, are correct.

Atom Rb2 is coordinated by five O atoms to form a distorted pentagonal plane (Fig. 1). The O2^vi—Rb2—O4^iv angle is widened, as the atoms O2^vi and O4^iv are again bridged by an S atom [symmetry code: (vi) 1/2 − x, 1/2 + y, −1/2 − z]. The nearest atoms above the pentagonal plane are O7 and F1ⁱⁱ; below the plane is atom F7, with a large distance to the central atom (4.20 Å).

The Li atom is surrounded by O atoms in the form of a strongly distorted tetrahedron, with Li—O distances as large as 1.95 Å on average (Fig. 1). This value is only slightly different from that observed in β-LiSO₃CF₃ (1.94 Å; Bolte & Lerner, 2001).

In the structures of the pure alkali trifluoromethanesulfonates MSO₃CF₃ (M is Li or Na) which have been characterized to date (Bolte & Lerner, 2001; Sofina et al., 2003), as well as in the structure of NaSO₃CF₃·H₂O; (Korus & Jansen, 1997), the nonpolar CF₃ groups point towards each other and form double layers which are linked by cations. In α-LiRb₂(SO₃CF₃)₃ and RT-KSO₃CF₃ (Korus & Jansen, 2001), on the other hand, the CF₃ groups build up channel-like patterns along the crystallographic a axis (Fig. 2) and the polar interstices between these channels are filled with cations (Fig. 3).

S2. Experimental

α-LiRb₂(SO₃CF₃)₃ was prepared from mixtures of solid LiSO₃CF₃ (Aldrich, 99.995%) and RbSO₃CF₃. Details concerning the synthesis are given in Pompetzki et al. (2003). The `single-crystal' investigated in the present work was found within a diphasic product consisting of LiRb₂(SO₃CF₃)₃ and Li_0.55Rb_0.45SO₃CF₃, which had formed on annealing (533 K, 7 d, cooling rate 5 K h⁻¹) a mixture of LiSO₃CF₃ (40 mol%) and RbSO₃CF₃ (60 mol%). The crystal was selected in a glove box under dry argon.

S3. Refinement

The structure was solved in space group P2₁/n via direct methods and the solution yielded the positions of the heavy atoms. The positions of the light atoms were found using a difference Fourier synthesis. Refinement as a single-crystal stuck at an overall agreement factor of about 23%, and no satisfactory structural model could be obtained. Of course, the pseudo-orthorhombic metrics implied the possibility of twinning. Furthermore, the fact that differential scanning calorimetry measurements and X-ray powder diffraction studies confirmed a phase transition at approximately 383 K to a β phase with orthorhombic metrics (a = 5.476 (2), b = 16.554 (18) and c = 20.177 (11) Å) suggested the introduction of an additional mirror plane from the orthorhombic system as a twinning operation. Consequently, we chose a mirror plane perpendicular to the a axis and introduced the corresponding twin matrix. The refinement converged satisfactorily after taking the twinning into account. The twin matrix was given by (100/010/001). The volume fractions of the twin individuals are t_I = 0.515 (2) and t_II = 0.485 (2).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: JANA2000 (Petřiček & Dušek, 2000); molecular graphics: DIAMOND (Bergerhoff et al., 1996) and ORTEP-3 for Windows (Farrugia, 1996); software used to prepare material for publication: Details?.

Figures

	Fig. 1. View of the coordination around the cations in α-LiRb2(SO3CF3)3. Displacement ellipsoids are drawn at the 50% probability level [symmetry codes: (i) −1 − x, 2 − y, −z; (ii) 1 + x, y, z; (iii) x − 1, y, z; (iv) −x, 2 − y, −z; (v) 1 − x, 2 − y, −z; (vi) 1/2 − x, 1/2 + y, −1/2 − z; (vii) −1/2 − x, 1/2 + y, −1/2 − z].
	Fig. 2. A perspective view of the channel-like pattern formed by the CF3 groups in α-LiRb2(SO3CF3)3.
	Fig. 3. A projection on the bc plane of the structure of α-LiRb2(SO3CF3)3.

Lithium dirubidium tris(trifluoromethylsulfonate)

Crystal data

LiRb2(SO3CF3)3	F(000) = 1184
Mr = 625.12	Dx = 2.42 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 3752 reflections
a = 5.3408 (9) Å	θ = 4.8–59.1°
b = 16.286 (2) Å	µ = 6.20 mm^−1
c = 19.721 (3) Å	T = 293 K
β = 90.48 (1)°	Irregular, colourless
V = 1715.3 (4) Å^3	0.15 × 0.12 × 0.08 mm
Z = 4

Data collection

Bruker SMART-APEX CCD area-detector diffractometer	5010 independent reflections
Radiation source: fine-focus sealed tube	2625 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.114
ω scans	θmax = 30.1°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −7→7
Tmin = 0.062, Tmax = 0.155	k = −22→22
21958 measured reflections	l = −27→27

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.068	Secondary atom site location: difference Fourier map
wR(F^2) = 0.061	w = 1/[σ^2(Fo^2)]
S = 4.17	(Δ/σ)max = 0.0004
5010 reflections	Δρmax = 1.86 e Å^−3
245 parameters	Δρmin = −2.05 e Å^−3

Special details

Experimental. δω=0.3° per frame; 1800 frames; 45 sec per frame.

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 as twin. Twin matrix (100/010/001). Twin volumes t_I = 0.515 (2), t_II = 0.485 (2). Maximum angular difference for twin overlap = 0.2.

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

	x	y	z	Uiso*/Ueq
Rb1	0.0264 (3)	0.87556 (9)	0.01184 (7)	0.0367 (5)
Rb2	−0.1026 (4)	1.15805 (12)	−0.22444 (9)	0.0654 (8)
S1	0.0316 (8)	0.6932 (2)	−0.13409 (19)	0.0310 (14)
S2	0.5460 (8)	0.7516 (3)	0.09017 (19)	0.0344 (15)
S3	−0.4912 (9)	0.9677 (2)	−0.10632 (18)	0.0320 (14)
O1	0.180 (2)	0.7391 (6)	−0.0899 (5)	0.038 (4)
O2	0.124 (2)	0.6834 (7)	−0.1986 (5)	0.053 (4)
O3	−0.2256 (18)	0.7116 (6)	−0.1317 (5)	0.037 (4)
O4	0.282 (2)	0.7632 (7)	0.1033 (7)	0.066 (6)
O5	0.713 (2)	0.7910 (7)	0.1325 (6)	0.044 (4)
O6	0.6150 (19)	0.7502 (6)	0.0198 (5)	0.049 (4)
O7	−0.292 (2)	1.0237 (8)	−0.1186 (6)	0.066 (6)
O8	−0.420 (2)	0.8854 (6)	−0.0847 (5)	0.054 (4)
O9	−0.698 (2)	0.9992 (7)	−0.0719 (5)	0.052 (5)
C1	−0.595 (4)	0.9478 (13)	−0.1964 (8)	0.061 (9)
C2	−0.548 (4)	1.0889 (10)	−0.4053 (11)	0.068 (9)
C3	0.577 (4)	0.6385 (12)	0.1075 (9)	0.060 (8)
F1	−0.679 (2)	1.0173 (7)	−0.2233 (6)	0.118 (7)
F2	−0.426 (3)	0.9161 (9)	−0.2327 (6)	0.146 (8)
F3	−0.791 (3)	0.9015 (8)	−0.1917 (6)	0.113 (7)
F4	−0.780 (2)	1.0659 (7)	−0.4022 (7)	0.098 (7)
F5	−0.468 (4)	1.0886 (6)	−0.4642 (5)	0.126 (7)
F6	−0.412 (3)	1.0404 (6)	−0.3659 (6)	0.103 (6)
F7	0.502 (3)	0.6303 (6)	0.1696 (5)	0.117 (6)
F8	0.457 (3)	0.5964 (7)	0.0681 (6)	0.110 (6)
F9	0.8187 (19)	0.6242 (8)	0.1085 (7)	0.114 (7)
Li1	0.534 (5)	0.7604 (12)	−0.0743 (11)	0.027 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.0342 (9)	0.0356 (9)	0.0403 (9)	−0.0022 (9)	0.0000 (9)	−0.0031 (8)
Rb2	0.0454 (12)	0.1113 (18)	0.0393 (10)	−0.0068 (11)	−0.0093 (10)	0.0037 (12)
S1	0.030 (3)	0.034 (2)	0.029 (2)	0.001 (2)	0.002 (2)	−0.0091 (17)
S2	0.031 (3)	0.046 (3)	0.026 (2)	0.003 (2)	−0.004 (2)	0.0054 (19)
S3	0.033 (3)	0.026 (2)	0.038 (2)	0.001 (2)	−0.001 (2)	−0.0018 (18)
O1	0.037 (8)	0.029 (7)	0.048 (8)	0.007 (5)	−0.010 (6)	−0.026 (6)
O2	0.061 (8)	0.061 (8)	0.038 (7)	−0.001 (7)	0.013 (6)	−0.022 (6)
O3	0.025 (7)	0.045 (8)	0.042 (7)	0.001 (5)	−0.002 (6)	−0.004 (6)
O4	0.022 (8)	0.080 (12)	0.096 (13)	0.009 (6)	0.005 (7)	0.002 (9)
O5	0.042 (7)	0.042 (8)	0.047 (8)	−0.009 (6)	−0.008 (6)	−0.004 (7)
O6	0.067 (8)	0.045 (7)	0.036 (6)	−0.029 (6)	0.012 (7)	0.008 (6)
O7	0.036 (8)	0.072 (10)	0.091 (11)	−0.002 (7)	−0.010 (8)	−0.019 (9)
O8	0.067 (9)	0.039 (7)	0.055 (7)	0.008 (7)	−0.038 (6)	−0.005 (6)
O9	0.039 (7)	0.078 (10)	0.040 (8)	−0.002 (7)	0.002 (6)	0.008 (7)
C1	0.079 (17)	0.071 (17)	0.031 (11)	−0.020 (13)	−0.034 (11)	−0.001 (11)
C2	0.064 (16)	0.028 (11)	0.112 (18)	0.000 (11)	−0.002 (16)	0.026 (12)
C3	0.086 (17)	0.054 (15)	0.040 (12)	0.000 (12)	0.025 (12)	0.037 (10)
F1	0.186 (14)	0.081 (10)	0.087 (9)	0.032 (9)	−0.037 (10)	0.029 (8)
F2	0.146 (14)	0.213 (17)	0.078 (9)	0.092 (12)	−0.037 (11)	−0.079 (10)
F3	0.151 (14)	0.111 (12)	0.077 (9)	−0.026 (10)	−0.079 (9)	0.004 (8)
F4	0.087 (10)	0.060 (9)	0.146 (14)	−0.029 (7)	−0.014 (9)	0.000 (8)
F5	0.233 (17)	0.081 (9)	0.063 (8)	−0.031 (12)	0.030 (12)	−0.037 (6)
F6	0.138 (12)	0.040 (7)	0.133 (11)	0.030 (8)	0.018 (10)	0.025 (7)
F7	0.162 (13)	0.093 (9)	0.098 (9)	−0.003 (11)	−0.008 (11)	0.050 (8)
F8	0.137 (13)	0.075 (9)	0.118 (10)	−0.011 (10)	−0.027 (12)	−0.017 (7)
F9	0.078 (9)	0.075 (10)	0.189 (15)	0.042 (8)	−0.011 (9)	0.043 (10)
Li1	0.031 (17)	0.016 (13)	0.033 (14)	0.006 (13)	0.011 (13)	0.007 (10)

Geometric parameters (Å, º)

Rb1—O4	2.904 (12)	S2—O5	1.376 (12)
Rb1—O9^i	2.944 (11)	S2—O6	1.439 (11)
Rb1—O9^ii	2.998 (11)	S2—O4	1.445 (12)
Rb1—O6^iii	3.004 (10)	S2—C3	1.88 (2)
Rb1—O7^iv	3.014 (12)	S2—Rb1^ii	3.620 (5)
Rb1—O8	3.043 (10)	S2—Rb2^iv	3.859 (5)
Rb1—O1	3.108 (10)	S3—O9	1.400 (12)
Rb1—O5^iii	3.228 (11)	S3—O7	1.425 (13)
Rb1—S2^iii	3.620 (5)	S3—O8	1.456 (10)
Rb1—Li1^iii	3.64 (2)	S3—C1	1.885 (18)
Rb1—Li1	3.72 (2)	S3—Rb1^iii	3.798 (4)
Rb2—O5^v	2.870 (11)	S3—Rb1^iv	4.009 (4)
Rb2—O4^iv	2.883 (13)	C1—F2	1.27 (3)
Rb2—O2^vi	3.011 (11)	C1—F3	1.29 (3)
Rb2—O3^vii	3.100 (11)	C1—F1	1.33 (2)
Rb2—O2^vii	3.188 (11)	C2—F5	1.24 (2)
Rb2—O7	3.193 (13)	C2—F4	1.29 (2)
Rb2—F1^ii	3.221 (12)	C2—F6	1.32 (2)
Rb2—S1^vii	3.641 (4)	C3—F8	1.21 (2)
Rb2—S2^iv	3.859 (5)	C3—F7	1.30 (2)
Rb2—Rb1^iv	4.244 (2)	C3—F9	1.31 (2)
S1—O2	1.378 (10)	Li1—O3^ii	1.89 (3)
S1—O1	1.390 (11)	Li1—O6	1.91 (2)
S1—O3	1.407 (11)	Li1—O1	1.94 (3)
S1—C2^viii	1.870 (18)	Li1—O8^ii	2.06 (2)
S1—Rb2^viii	3.641 (4)	Li1—Rb1^ii	3.64 (2)
O4—Rb1—O9^i	117.7 (3)	O2—S1—C2^viii	105.3 (8)
O4—Rb1—O9^ii	122.3 (3)	O1—S1—C2^viii	101.8 (8)
O9^i—Rb1—O9^ii	93.0 (3)	O3—S1—C2^viii	102.9 (8)
O4—Rb1—O6^iii	83.1 (3)	O2—S1—Rb2^viii	60.2 (5)
O9^i—Rb1—O6^iii	90.7 (3)	O1—S1—Rb2^viii	156.3 (4)
O9^ii—Rb1—O6^iii	148.0 (3)	O3—S1—Rb2^viii	56.7 (4)
O4—Rb1—O7^iv	72.1 (3)	C2^viii—S1—Rb2^viii	101.7 (7)
O9^i—Rb1—O7^iv	67.7 (3)	O5—S2—O6	115.0 (7)
O9^ii—Rb1—O7^iv	77.8 (3)	O5—S2—O4	117.3 (7)
O6^iii—Rb1—O7^iv	132.3 (3)	O6—S2—O4	115.7 (7)
O4—Rb1—O8	141.7 (3)	O5—S2—C3	106.9 (8)
O9^i—Rb1—O8	75.5 (3)	O6—S2—C3	97.8 (7)
O9^ii—Rb1—O8	90.3 (3)	O4—S2—C3	100.4 (8)
O6^iii—Rb1—O8	59.9 (3)	O5—S2—Rb1^ii	62.6 (5)
O7^iv—Rb1—O8	140.4 (3)	O6—S2—Rb1^ii	53.8 (4)
O4—Rb1—O1	80.0 (3)	O4—S2—Rb1^ii	134.3 (5)
O9^i—Rb1—O1	156.3 (3)	C3—S2—Rb1^ii	124.1 (7)
O9^ii—Rb1—O1	89.5 (3)	O5—S2—Rb1	118.2 (5)
O6^iii—Rb1—O1	75.2 (3)	O6—S2—Rb1	78.8 (4)
O7^iv—Rb1—O1	135.7 (3)	C3—S2—Rb1	131.7 (7)
O8—Rb1—O1	80.9 (3)	Rb1^ii—S2—Rb1	92.80 (10)
O4—Rb1—O5^iii	61.2 (3)	O5—S2—Rb2^iv	78.8 (5)
O9^i—Rb1—O5^iii	71.6 (3)	O6—S2—Rb2^iv	146.3 (5)
O9^ii—Rb1—O5^iii	162.2 (3)	C3—S2—Rb2^iv	107.6 (6)
O6^iii—Rb1—O5^iii	44.6 (3)	Rb1^ii—S2—Rb2^iv	121.43 (12)
O7^iv—Rb1—O5^iii	87.7 (3)	Rb1—S2—Rb2^iv	67.76 (8)
O8—Rb1—O5^iii	94.3 (3)	O9—S3—O7	116.2 (7)
O1—Rb1—O5^iii	108.2 (3)	O9—S3—O8	113.6 (7)
O4—Rb1—O8^ii	88.4 (3)	O7—S3—O8	116.5 (7)
O9^i—Rb1—O8^ii	133.5 (3)	O9—S3—C1	107.0 (9)
O9^ii—Rb1—O8^ii	41.9 (3)	O7—S3—C1	99.4 (9)
O6^iii—Rb1—O8^ii	132.4 (3)	O8—S3—C1	101.1 (8)
O7^iv—Rb1—O8^ii	87.8 (3)	O9—S3—Rb1^iii	45.9 (5)
O8—Rb1—O8^ii	108.4 (2)	O7—S3—Rb1^iii	150.4 (5)
O1—Rb1—O8^ii	57.2 (2)	O8—S3—Rb1^iii	68.5 (4)
O5^iii—Rb1—O8^ii	149.0 (2)	C1—S3—Rb1^iii	108.3 (7)
O4—Rb1—S2^iii	73.5 (2)	O9—S3—Rb1	114.2 (5)
O9^i—Rb1—S2^iii	77.8 (2)	O7—S3—Rb1	79.7 (5)
O9^ii—Rb1—S2^iii	164.2 (2)	C1—S3—Rb1	134.3 (7)
O6^iii—Rb1—S2^iii	22.7 (2)	Rb1^iii—S3—Rb1	87.85 (8)
O7^iv—Rb1—S2^iii	109.6 (2)	S1—O1—Li1	137.9 (9)
O8—Rb1—S2^iii	75.1 (2)	S1—O1—Rb1	129.7 (6)
O1—Rb1—S2^iii	93.9 (2)	Li1—O1—Rb1	91.8 (7)
O5^iii—Rb1—S2^iii	22.2 (2)	S1—O2—Rb2^ix	142.5 (6)
O8^ii—Rb1—S2^iii	148.7 (2)	S1—O2—Rb2^viii	97.8 (5)
O4—Rb1—Li1^iii	107.5 (4)	Rb2^ix—O2—Rb2^viii	118.9 (3)
O9^i—Rb1—Li1^iii	96.6 (4)	S1—O3—Li1^iii	141.0 (10)
O9^ii—Rb1—Li1^iii	116.4 (4)	S1—O3—Rb2^viii	101.0 (5)
O6^iii—Rb1—Li1^iii	31.6 (4)	Li1^iii—O3—Rb2^viii	117.8 (8)
O7^iv—Rb1—Li1^iii	160.1 (4)	S2—O4—Rb2^iv	122.6 (7)
O8—Rb1—Li1^iii	34.5 (4)	S2—O4—Rb1	115.1 (7)
O1—Rb1—Li1^iii	61.5 (4)	Rb2^iv—O4—Rb1	94.3 (3)
O5^iii—Rb1—Li1^iii	75.4 (4)	S2—O5—Rb2^v	168.9 (7)
O8^ii—Rb1—Li1^iii	112.1 (4)	S2—O5—Rb1^ii	95.1 (5)
S2^iii—Rb1—Li1^iii	53.1 (4)	Rb2^v—O5—Rb1^ii	88.0 (3)
O4—Rb1—Li1	68.0 (4)	S2—O6—Li1	151.4 (11)
O9^i—Rb1—Li1	166.4 (4)	S2—O6—Rb1^ii	103.5 (5)
O9^ii—Rb1—Li1	74.0 (4)	Li1—O6—Rb1^ii	92.9 (8)
O6^iii—Rb1—Li1	102.5 (4)	S3—O7—Rb1^iv	125.3 (7)
O7^iv—Rb1—Li1	104.7 (4)	S3—O7—Rb2	142.3 (7)
O8—Rb1—Li1	108.1 (4)	Rb1^iv—O7—Rb2	86.2 (3)
O1—Rb1—Li1	31.5 (4)	S3—O8—Li1^iii	155.1 (10)
O5^iii—Rb1—Li1	120.4 (4)	S3—O8—Rb1	115.7 (5)
O8^ii—Rb1—Li1	32.9 (4)	Li1^iii—O8—Rb1	88.9 (8)
S2^iii—Rb1—Li1	115.8 (3)	S3—O8—Rb1^iii	89.0 (5)
Li1^iii—Rb1—Li1	93.1 (5)	Li1^iii—O8—Rb1^iii	78.5 (8)
O5^v—Rb2—O4^iv	66.0 (3)	Rb1—O8—Rb1^iii	108.4 (3)
O5^v—Rb2—O2^vi	70.5 (3)	S3—O9—Rb1^i	157.6 (7)
O4^iv—Rb2—O2^vi	130.3 (3)	S3—O9—Rb1^iii	114.5 (6)
O5^v—Rb2—O3^vii	134.8 (3)	Rb1^i—O9—Rb1^iii	87.0 (3)
O4^iv—Rb2—O3^vii	122.3 (3)	F2—C1—F3	112.5 (18)
O2^vi—Rb2—O3^vii	75.3 (3)	F2—C1—F1	111.3 (16)
O5^v—Rb2—O2^vii	152.7 (3)	F3—C1—F1	104.8 (18)
O4^iv—Rb2—O2^vii	92.3 (3)	F2—C1—S3	113.4 (16)
O2^vi—Rb2—O2^vii	118.9 (3)	F3—C1—S3	105.3 (12)
O3^vii—Rb2—O2^vii	43.7 (3)	F1—C1—S3	109.0 (13)
O5^v—Rb2—O7	91.0 (3)	F5—C2—F4	112.4 (19)
O4^iv—Rb2—O7	69.8 (3)	F5—C2—F6	110.9 (18)
O2^vi—Rb2—O7	134.3 (3)	F4—C2—F6	108.7 (16)
O3^vii—Rb2—O7	134.3 (3)	F5—C2—S1^vii	112.2 (13)
O2^vii—Rb2—O7	96.9 (3)	F4—C2—S1^vii	106.5 (13)
O5^v—Rb2—F1^ii	72.3 (3)	F6—C2—S1^vii	105.9 (14)
O4^iv—Rb2—F1^ii	123.3 (3)	F8—C3—F7	112.3 (18)
O2^vi—Rb2—F1^ii	60.1 (3)	F8—C3—F9	115.1 (17)
O3^vii—Rb2—F1^ii	114.2 (3)	F7—C3—F9	106.2 (16)
O2^vii—Rb2—F1^ii	135.0 (3)	F8—C3—S2	113.0 (14)
O7—Rb2—F1^ii	74.6 (3)	F7—C3—S2	104.1 (12)
O5^v—Rb2—S1^vii	152.5 (2)	F9—C3—S2	105.2 (13)
O4^iv—Rb2—S1^vii	110.7 (2)	C1—F1—Rb2^iii	147.7 (12)
O2^vi—Rb2—S1^vii	97.1 (2)	O3^ii—Li1—O6	113.2 (13)
O3^vii—Rb2—S1^vii	22.30 (19)	O3^ii—Li1—O1	119.7 (12)
O2^vii—Rb2—S1^vii	22.02 (19)	O6—Li1—O1	110.6 (12)
O7—Rb2—S1^vii	114.1 (2)	O3^ii—Li1—O8^ii	105.8 (12)
F1^ii—Rb2—S1^vii	123.7 (2)	O6—Li1—O8^ii	99.0 (10)
O5^v—Rb2—S2^iv	84.4 (2)	O1—Li1—O8^ii	106.1 (11)
O4^iv—Rb2—S2^iv	18.4 (2)	O3^ii—Li1—Rb1^ii	90.2 (9)
O2^vi—Rb2—S2^iv	145.3 (2)	O6—Li1—Rb1^ii	55.5 (7)
O3^vii—Rb2—S2^iv	110.0 (2)	O1—Li1—Rb1^ii	149.7 (10)
O2^vii—Rb2—S2^iv	74.84 (19)	O8^ii—Li1—Rb1^ii	56.7 (6)
O7—Rb2—S2^iv	67.2 (2)	O3^ii—Li1—Rb1	170.2 (10)
F1^ii—Rb2—S2^iv	134.5 (2)	O6—Li1—Rb1	76.1 (8)
S1^vii—Rb2—S2^iv	94.60 (10)	O1—Li1—Rb1	56.7 (7)
O2—S1—O1	115.7 (7)	O8^ii—Li1—Rb1	68.6 (7)
O2—S1—O3	114.4 (7)	Rb1^ii—Li1—Rb1	93.1 (5)
O1—S1—O3	114.4 (6)

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