Ba₃Li₂V₂O₇Cl₄, a new vanadate with a channel structure

The tribarium dilithium divanadate tetra­chloride Ba₃Li₂V₂O₇Cl₄ is a new vanadate with a channel structure and the first known vanadate containing both Ba and Li atoms. The structure contains four non-equivalent Ba²⁺ sites (two with m and two with 2/m site symmetry), two Li⁺ sites, two nonmagnetic V⁵⁺ sites, five O^2- sites (three with m site symmetry) and four Cl^- sites (m site symmetry). One type of Li atom lies in LiO₄ tetra­hedra (m site symmetry) and shares corners with VO₄ tetra­hedra to form eight-tetra­hedron Li₃V₅O₂₄ rings and six-tetra­hedron Li₂V₄O₁₈ rings; these rings are linked within porous layers parallel to the ab plane and contain Ba²⁺ and Cl^- ions. The other Li atoms are located on inversion centres and form isolated chains of face-sharing LiCl₆ octa­hedra.

S1. Comment

Porous crystalline structures containing large cages or channels have been widely investigated, since they are good candidates for shape-selective molecular sieves, as in the well known case of zeolites, or can exhibit interesting ionic transport properties. The title compound contains channels delimited by LiO₄ and VO₄ tetrahedra and shows an unusual linkage pattern of tetrahedron rings, never observed in silicates so far due to the very rare T:O ratio of 3:7 (where T is the number of cations in tetrahedral coordination and O is the number of O atoms).

The structure contains Li1O₄ and VO₄ tetrahedra (Fig. 1), which share corners to form eight-tetrahedra Li₃V₅O₂₄ heterorings connected into infinite layers parallel to the ab plane (Fig. 2). These layers are stacked in pairs along the c direction, giving rise to puckered chains of four-tetrahedra Li₂V₂O₁₂ rings parallel to b and six-tetrahedra Li₂V₄O₁₂ rings within the ac plane (Fig. 3). Thus, the linkage of the LiO₄ and VO₄ tetrahedra produces porous LiV₂O₇ double layers parallel to the ab plane. The only occurrence of six-tetrahedra rings in V⁵⁺ compounds has been reported for LiZnVO₄ (Capsoni et al., 2006), but in that case the central cations of the tetrahedra do not lie on the same plane. From the directedness of the tetrahedra and the ordering of the Li1 and V atoms, the six-tetrahedra Li₂V₄O₁₂ rings bear a resemblance to the Al₂Si₄O₁₈ rings found in ordered cordierites (Knorr et al., 1999; Malcherek et al., 2001).

Two channels can be distinguished that are parallel to the monoclinic b axis. The smaller one is delimited by the puckered Li₂V₂O₁₀ chain of four-tetrahedra Li₂V₂O₁₂ rings within an LiV₂O₇ layer and is empty. The larger one is formed by the six-tetrahedra Li₂V₄O₁₈ rings and is filled by atoms Ba3 and Cl2. The interlayer space is filled by atoms Ba1, Ba2 and Ba4 and infinite chains of face-sharing Li2Cl₆ octahedra. No other instance of such infinite Li₂Cl₆ chains has been found in the literature.

Within the largest channel, the Ba3 atoms have a planar sixfold coordination of O atoms in the ac plane (Fig. 4a). Along the direction of the channels, four Cl2 atoms surround Ba3 in a rectangular planar coordination. This is the first occurrence of a BaO₆Cl₄ group with a planar hexagonal arrangement of O atoms to date; the only known compound with an approaching [similar?] environment for Ba is Ba₉Cu₇O₁₅Cl₂ (Kipka & Müller-Buschbaum, 1976), containing a BaO₆Cl₂ group, where the two Cl atoms are located on opposite sides of the BaO₆ plane. The displacement ellipsoid of Ba3 is elongated in the b direction, towards the Cl atoms. The other three Ba atoms fill the interlayer space and surround the Li₂O₆ chains. The environments of atoms Ba1 and Ba2 are very similar to each other: both are surrounded by six O atoms and five Cl atoms. However, while Ba1 is connected via O atoms to two VO₄ tetrahedra of an Li₂V₄O₁₈ ring, Ba2 is linked to a V2O₄ tetrahedron and an Li1O₄ tetrahedron of a neighbouring ring. BaO₆Cl₅ groups have also been observed in verplanckite (Kampf et al., 1973). On the other hand, Ba4 is surrounded by four O atoms in a rectangular planar coordination parallel to the bc plane and is also eightfold coordinated by Cl atoms. This environment is similar to that of the Ba1 atom in Ba₅(Mg_0.4Mn_0.6)Mn(V₂O₇)₂Cl₆ (Müller-Buschbaum & Rettich, 1997). The displacement ellipsoids of Ba1, Ba2 and Ba4 are also elongated along the monoclinic b direction; within the ac plane, they all point towards the Li₂Cl₆ chain.

The V1O₄ and V2O₄ tetrahedra possess very similar bond lengths, although their connectedness is different. The V1O₄ tetrahedron shares all its corners with one V2O₄ and three Li1O₄ tetrahedra, while two O atoms in the V2O₄ tetrahedron point towards the Ba4 atom in the interlayer space. The Li1O₄ tetrahedron shares all its corners solely with VO₄ tetrahedra. The Li2Cl₆ octahedron possesses four Li2—Cl bonds with similar lengths, pointing towards the Ba1 and Ba2 atoms, and two longer Li2—Cl4 bonds pointing towards Ba4. The equivalent isotropic displacement parameter for the Li2 atoms within the Li₂Cl₆ chains is twice as large as for the tetrahedrally coordinated Li1 atoms.

The displacement ellipsoids of atoms O1, O2 and O4 at the corners of the Li1O₄ tetrahedron show a pronounced elongation perpendicular to the Li1—O bonds, indicating a possible rigid body rotation of the Li1O₄ tetrahedron within the Li₂V₄O₁₈ ring. Atoms Cl1, Cl3 and Cl4 have quasi-isotropic displacement parameters; they are sixfold coordinated by four Ba and two Li2 atoms. The displacement ellipsoid of Cl2 is strongly elongated in the a direction, with an equivalent isotropic displacement parameter almost twice as large as for the other Cl atoms, due to a weaker interatomic potential and repulsive forces from the closest anions (Fig. 4 b), rather than from a possible ionic conductivity. Atom Cl2 is tetrahedrally coordinated by four Ba atoms. There are two V2 atoms close to Cl2, but their influence is screened by atoms O2, O3 and O5 of the V2O₄ tetrahedron between V2 and Cl2. These O atoms should force the largest axis of the displacement tensor of Cl2 towards the middle of the oxygen-free faces of Cl2Ba₄ (parallel to a). The Cl2Ba₄ tetrahedron shares an edge with a second Cl2Ba₄ group along c, resulting in a short Cl2···Cl2 distance of 3.3133 (17) Å.

Related literature

For related literature, see: Capsoni et al. (2006); Kampf et al. (1973); Kipka & Müller-Buschbaum (1976); Knorr et al. (1999); Müller-Buschbaum & Rettich (1997); Malcherek et al. (2001); Reeswinkel et al. (2007).

S2. Experimental

Ba₃Li₂V₂O₇Cl₄ was prepared via a molten salt reaction as a by-product during the synthesis of the V⁴⁺ compound BaV₄O₉ (Reeswinkel et al., 2007). A mixture of LiCl, RbCl and BaCl₂ was first prepared by drying the components separately at 413 K and mixing them in the molar ratio 2:1:1. VO₂ powder was added to the mixture in a flux to a VO₂ molar ratio of 10:1. The sample was ground, placed in an Al₂O₃ crucible and briefly dried to remove water from the hygroscopic BaCl₂. The crucible was then placed in a glass test tube within a glass gas-washing bottle. The sample was heat treated at 713 K for 24 d in a vertical tube furnace. During that time, argon gas (Ar 5.0) was flushed through the bottle. At the end of the growth process, the sample was slowly cooled down to room temperature.

S3. Refinement

Despite the fact that the unit-cell metric and the positions of the Ba, Li, Cl and O atoms suggest the orthorhombic space group Cmmm, the structure has to be described in the monoclinic crystal system. The internal R value of the data set before absorption correction is 9% for the 2/m Laue class and 24.9% for the mmm Laue class. Furthermore, the Cmmm symmetry would not allow the ordering of the V (Z = 23) and Li (Z = 3) atoms within the Li₂V₄O₁₈ rings, although it is clearly visible in the monoclinic symmetry.

Structure solution using direct methods gave the positions of the Ba, V, O and Cl atoms. The Li atoms were located subsequently from a residual electron-density analysis after refinement of the structure. All atoms could be refined with anisotropic displacement parameters. A possible presence of Rb from the salt mixture on the Ba sites was tested by site-occupancy refinement and proved to be insignificant.

Computing details

Data collection: X-AREA (Stoe & Cie, 2000); cell refinement: X-AREA (Stoe & Cie, 2000); data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: WinGX (Version 1.70.01; Farrugia, 1999).

Figures

	Fig. 1. A view of the asymmetric unit of Ba3Li2V2O7Cl4, projected onto the ac plane. Displacement ellipsoids are drawn at the 50% probability level. Symmetry-related atoms have been added to show the coordination environments and some polyhedral connectivities. [Symmetry codes: (i) x - 1/2, y - 1/2, z; (ii) -x + 1/2, y - 1/2, -z + 1; (iv) -x, -y, -z + 1; (v) -x + 1, -y, -z + 1; (vii) x, y, z - 1; (viii) -x + 1/2, -y + 1/2, -z + 1; (ix) x, -y, z; (x) -x + 1/2, y + 1/2, -z + 1; (xi) x + 1/2, y + 1/2, z; (xii) x + 1/2, y - 1/2, z; (xiii) -x + 1/2, y + 1/2, -z; (xiv) -x + 1, y, -z; (xv) x - 1/2, -y + 1/2, z; (xvi) -x + 1, y, -z + 1.]
	Fig. 2. A perspective polyhedral representation of the crystal structure of Ba3Li2V2O7Cl4, projected onto the ab plane. Displacement ellipsoids are drawn at the 80% probability level. Within the eight-tetrahedra rings, the VO4 tetrahedra are the darker polyhedra and the LiO4 tetrahedra the lighter ones. The chains of face-sharing LiO6 octahedra are seen in the background.
	Fig. 3. (a) A perspective polyhedral representation of the crystal structure of Ba3Li2V2O7Cl4, projected onto the ac plane. Displacement ellipsoids are drawn at the 80% probability level. (b) Puckered chains of four-tetrahedra Li2V2O12 rings parallel to b.
	Fig. 4. (a) The environment of atom Ba3. Displacement ellipsoids are drawn at the 50% probability level. (b) The environment of atom Cl2. Displacement ellipsoids are drawn at the 80% probability level. [Symmetry codes: (i) x - 1/2, y - 1/2, z; (ii) -x + 1/2, y - 1/2, -z + 1; (iv) -x, -y, -z + 1; (v) -x + 1, -y, -z + 1; (vi) -x + 1/2, -y - 1/2, -z; (vii) x, y, z - 1; (viii) -x + 1/2, -y + 1/2, -z + 1; (xi) x + 1/2, y + 1/2, z; (xii) x + 1/2, y - 1/2, z; (xiii) -x + 1/2, y + 1/2, -z; (xiv) -x + 1, y, -z; (xv) x - 1/2, -y + 1/2, z; (xvii) -x, y, -z.]

tribarium dilithium divanadate tetrachloride

Crystal data

Ba3Li2V2O7Cl4	F(000) = 1376
Mr = 781.58	Dx = 3.886 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 20576 reflections
a = 16.1215 (14) Å	θ = 2.8–35.2°
b = 5.7630 (3) Å	µ = 10.87 mm^−1
c = 14.3795 (13) Å	T = 293 K
β = 90.592 (7)°	Parallelepiped, blue
V = 1335.90 (18) Å^3	0.19 × 0.15 × 0.12 mm
Z = 4

Data collection

Stoe IPDSII diffractometer	2763 reflections with I > 2σ(I)
Rotation method, ω scans	Rint = 0.051
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1996)	θmax = 35.0°, θmin = 2.8°
Tmin = 0.141, Tmax = 0.295	h = −26→25
22838 measured reflections	k = −9→7
3141 independent reflections	l = −22→23

Refinement

Refinement on F^2	0 constraints
Least-squares matrix: full	w = 1/σ^2(Fo^2)
R[F^2 > 2σ(F^2)] = 0.024	(Δ/σ)max < 0.001
wR(F^2) = 0.035	Δρmax = 1.02 e Å^−3
S = 1.61	Δρmin = −1.27 e Å^−3
3141 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
106 parameters	Extinction coefficient: 0.00627 (10)
0 restraints

Special details

Experimental. The single-crystal X-ray diffraction measurement was performed on a two-circle imaging plate diffractometer (Stoe IPDSII, Mo Kα-radiation, tube setting 50 kV and 25 mA, pyrolytic graphite monochromator). The data were collected using a crystal-detector distance of 6 cm, an exposure time of 2.5 min per frame, an ω-scan between 0° and 180° for ϕ = 0° and ω-scans between 0° and 120° for ϕ = 45° and ϕ = 90°, with the rotation step Δω = 1.5° 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.

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

	x	y	z	Uiso*/Ueq
Ba1	0.133937 (10)	0	0.279261 (13)	0.01316 (4)
Ba2	0.136184 (10)	0	0.726277 (13)	0.01414 (4)
Ba3	0.5	0	0	0.01659 (6)
Ba4	0.5	0	0.5	0.01711 (6)
V1	0.31140 (3)	0	0.87285 (3)	0.00853 (8)
V2	0.49634 (3)	0	0.25169 (3)	0.00830 (8)
Cl1	0.31137 (4)	0	0.37832 (5)	0.01569 (13)
Cl2	0.00143 (6)	0	0.11521 (6)	0.02670 (18)
Cl3	0.31537 (4)	0	0.62089 (5)	0.01562 (13)
Cl4	0.11507 (5)	0	0.50133 (5)	0.01677 (13)
O1	0.32993 (14)	0	0.98736 (15)	0.0177 (5)
O2	0.41184 (13)	0	0.18266 (16)	0.0185 (5)
O3	0.49752 (9)	0.2336 (3)	0.32264 (11)	0.0132 (3)
O4	0.25850 (9)	0.2358 (3)	0.83436 (11)	0.0153 (3)
O5	0.41276 (13)	0	0.82120 (17)	0.0178 (5)
Li1	0.3017 (3)	0	0.1166 (4)	0.0130 (10)
Li2	0.25	0.25	0.5	0.0280 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.01104 (7)	0.01398 (8)	0.01448 (9)	0	0.00141 (5)	0
Ba2	0.00985 (7)	0.01665 (9)	0.01588 (9)	0	−0.00218 (5)	0
Ba3	0.01104 (9)	0.02688 (14)	0.01181 (11)	0	−0.00209 (7)	0
Ba4	0.01941 (11)	0.02040 (13)	0.01153 (11)	0	0.00064 (8)	0
V1	0.00700 (16)	0.01017 (19)	0.0084 (2)	0	0.00044 (13)	0
V2	0.00686 (16)	0.00952 (19)	0.00852 (17)	0	0.00053 (13)	0
Cl1	0.0145 (3)	0.0158 (3)	0.0168 (3)	0	0.0017 (2)	0
Cl2	0.0419 (5)	0.0238 (4)	0.0144 (3)	0	−0.0009 (3)	0
Cl3	0.0156 (3)	0.0157 (3)	0.0155 (3)	0	−0.0013 (2)	0
Cl4	0.0174 (3)	0.0185 (3)	0.0144 (3)	0	0.0003 (2)	0
O1	0.0163 (9)	0.0288 (13)	0.0080 (9)	0	−0.0002 (7)	0
O2	0.0098 (8)	0.0297 (13)	0.0159 (10)	0	−0.0028 (7)	0
O3	0.0128 (6)	0.0131 (7)	0.0137 (7)	−0.0004 (5)	0.0010 (5)	−0.0021 (6)
O4	0.0138 (6)	0.0140 (7)	0.0181 (7)	0.0049 (6)	0.0002 (5)	−0.0006 (6)
O5	0.0094 (8)	0.0275 (13)	0.0166 (10)	0	0.0037 (7)	0
Li1	0.014 (2)	0.013 (2)	0.012 (2)	0	0.0034 (17)	0
Li2	0.037 (4)	0.022 (3)	0.025 (3)	0.003 (3)	0.000 (2)	0.003 (3)

Bond lengths (Å)

Ba1—O3^i	2.7589 (16)	V1—Cl2^iv	4.1746 (8)
Ba1—O3^ii	2.7589 (16)	V1—Cl2^v	4.1746 (8)
Ba1—O4^iii	2.8377 (18)	V1—V1^xx	5.0737 (8)
Ba1—O4^iv	2.8377 (18)	V1—V1^xxi	5.0737 (8)
Ba1—Cl2	3.1660 (9)	V1—Li2^iii	5.6294 (6)
Ba1—Cl1	3.1824 (8)	V1—Li2	5.6294 (6)
Ba1—Cl4	3.2108 (8)	V1—V1^xxii	5.7630 (3)
Ba1—O5^v	3.3067 (11)	V2—O2	1.677 (2)
Ba1—O5^iv	3.3067 (11)	V2—O3	1.6891 (16)
Ba1—Cl3^iv	3.3179 (4)	V2—O3^viii	1.6891 (16)
Ba1—Cl3^v	3.3179 (4)	V2—O5^ix	1.810 (2)
Ba1—Li1	3.594 (5)	V2—Cl2^xv	3.4877 (6)
Ba1—V2^i	3.6555 (3)	V2—Cl2^xiii	3.4877 (6)
Ba1—V2^vi	3.6555 (3)	V2—Cl1	3.5099 (9)
Ba1—V1^v	3.7288 (4)	V2—Cl3^ix	3.5295 (9)
Ba1—V1^iv	3.7288 (4)	V2—V1^ix	3.5957 (7)
Ba1—Li2	3.9407 (3)	V2—Ba2^v	3.6030 (3)
Ba1—Li2^iii	3.9407 (3)	V2—Ba2^iv	3.6030 (3)
Ba1—Ba2^vii	4.3547 (4)	V2—Ba1^xiii	3.6555 (3)
Ba1—Ba2^iv	4.6957 (3)	V2—Ba1^xv	3.6555 (3)
Ba2—O3^iii	2.7325 (16)	V2—Li1	3.673 (5)
Ba2—O3^iv	2.7325 (15)	V2—Li2^iii	5.5579 (6)
Ba2—O4	2.8439 (16)	V2—Li2	5.5579 (6)
Ba2—O4^viii	2.8439 (16)	V2—Li2^xviii	5.5899 (6)
Ba2—Cl2^vii	3.1971 (11)	V2—Li2^xv	5.5899 (6)
Ba2—Cl4	3.2490 (8)	Cl1—Li2	2.4803 (6)
Ba2—O2^iv	3.2616 (12)	Cl1—Li2^iii	2.4803 (6)
Ba2—O2^v	3.2616 (12)	Cl1—Ba2^v	3.3625 (4)
Ba2—Cl3	3.2759 (8)	Cl1—Ba2^iv	3.3625 (4)
Ba2—Cl1^v	3.3625 (4)	Cl1—Li1	3.765 (5)
Ba2—Cl1^iv	3.3625 (4)	Cl2—Ba2^vii	3.1971 (11)
Ba2—V1	3.5069 (5)	Cl2—Ba3^i	3.3238 (5)
Ba2—V2^v	3.6030 (3)	Cl2—Ba3^vi	3.3238 (5)
Ba2—V2^iv	3.6030 (3)	Cl2—V2^vi	3.4877 (6)
Ba2—Li1^iv	3.790 (3)	Cl2—V2^i	3.4877 (6)
Ba2—Li1^v	3.790 (3)	Cl2—V1^iv	4.1746 (8)
Ba2—Li2^iii	4.0191 (4)	Cl2—V1^v	4.1746 (8)
Ba2—Li2	4.0191 (4)	Cl2—Li1^i	4.321 (4)
Ba2—Ba1^vii	4.3547 (5)	Cl2—Li1^vi	4.321 (4)
Ba2—Ba1^iv	4.6957 (3)	Cl3—Li2^iii	2.4840 (6)
Ba3—O1^ix	2.746 (2)	Cl3—Li2	2.4840 (6)
Ba3—O1^x	2.746 (2)	Cl3—Ba1^iv	3.3179 (4)
Ba3—O5^ix	2.918 (2)	Cl3—Ba1^v	3.3179 (4)
Ba3—O5^x	2.918 (2)	Cl3—V2^ix	3.5295 (9)
Ba3—O2^xi	2.999 (2)	Cl4—Li2	2.6094 (6)
Ba3—O2	2.999 (2)	Cl4—Li2^iii	2.6094 (6)
Ba3—Cl2^xii	3.3238 (5)	Cl4—Ba4^i	3.4269 (4)
Ba3—Cl2^xiii	3.3238 (5)	Cl4—Ba4^vi	3.4269 (4)
Ba3—Cl2^xiv	3.3238 (5)	O1—Li1^xix	1.918 (6)
Ba3—Cl2^xv	3.3238 (5)	O1—Ba3^xix	2.746 (2)
Ba3—V1^x	3.5317 (5)	O1—Li1^v	3.870 (4)
Ba3—V1^ix	3.5317 (5)	O1—Li1^iv	3.870 (4)
Ba3—V2	3.6202 (6)	O2—Li1	2.005 (6)
Ba3—V2^xi	3.6202 (6)	O2—Ba2^iv	3.2616 (12)
Ba3—Li1^xi	3.625 (5)	O2—Ba2^v	3.2616 (12)
Ba3—Li1	3.625 (5)	O3—Ba2^iv	2.7325 (15)
Ba3—Ba2^xvi	5.3660 (4)	O3—Ba1^xiii	2.7589 (16)
Ba3—Ba2^iv	5.3660 (4)	O4—Li1^iv	1.942 (4)
Ba3—Ba2^xvii	5.3660 (4)	O4—Ba1^iv	2.8377 (18)
Ba3—Ba2^v	5.3660 (4)	O5—V2^ix	1.810 (2)
Ba4—O3^viii	2.8838 (16)	O5—Ba3^xix	2.918 (2)
Ba4—O3^xviii	2.8838 (16)	O5—Ba1^v	3.3067 (11)
Ba4—O3^ix	2.8838 (16)	O5—Ba1^iv	3.3067 (11)
Ba4—O3	2.8838 (16)	Li1—O1^x	1.918 (6)
Ba4—Cl4^v	3.4269 (4)	Li1—O4^iii	1.942 (4)
Ba4—Cl4^xiii	3.4269 (4)	Li1—O4^iv	1.942 (4)
Ba4—Cl4^iv	3.4269 (4)	Li1—O2	2.005 (6)
Ba4—Cl4^xv	3.4269 (4)	Li1—V1^v	3.414 (3)
Ba4—Cl3	3.4624 (8)	Li1—V1^iv	3.414 (3)
Ba4—Cl3^ix	3.4624 (8)	Li1—V1^x	3.510 (5)
Ba4—Cl1	3.4927 (8)	Li1—Ba2^iv	3.790 (3)
Ba4—Cl1^ix	3.4927 (8)	Li1—Ba2^v	3.790 (3)
Ba4—V2^ix	3.5705 (6)	Li1—O1^v	3.870 (4)
Ba4—V2	3.5705 (6)	Li1—O1^iv	3.870 (4)
Ba4—Li2^iii	4.2801 (3)	Li1—Cl2^xiii	4.321 (4)
Ba4—Li2^xviii	4.2802 (3)	Li1—Cl2^xv	4.321 (4)
Ba4—Li2^xv	4.2801 (3)	Li1—Li1^xii	4.713 (8)
Ba4—Li2	4.2801 (3)	Li1—Li1^xiv	4.713 (8)
Ba4—Ba1^iv	4.8148 (3)	Li1—Li1^xxii	5.7630 (3)
Ba4—Ba1^v	4.8148 (3)	Li2—Cl1^iv	2.4803 (6)
V1—O1	1.670 (2)	Li2—Cl3^iv	2.4840 (6)
V1—O4^viii	1.6945 (16)	Li2—Cl4^iv	2.6094 (6)
V1—O4	1.6945 (16)	Li2—Li2^xxiii	2.8815 (2)
V1—O5	1.802 (2)	Li2—Li2^iii	2.8815 (2)
V1—Li1^v	3.414 (3)	Li2—Ba1^iv	3.9407 (3)
V1—Li1^iv	3.414 (3)	Li2—Ba2^iv	4.0191 (4)
V1—Li1^xix	3.510 (5)	Li2—Ba4^vi	4.2801 (3)
V1—Ba3^xix	3.5317 (5)	Li2—V2^iv	5.5579 (6)
V1—V2^ix	3.5957 (7)	Li2—V2^ix	5.5899 (6)
V1—Cl3	3.6243 (9)	Li2—V2^vi	5.5899 (6)
V1—Ba1^v	3.7288 (4)	Li2—V1^iv	5.6294 (6)
V1—Ba1^iv	3.7288 (4)

Symmetry codes: (i) x−1/2, y−1/2, z; (ii) x−1/2, −y+1/2, z; (iii) −x+1/2, y−1/2, −z+1; (iv) −x+1/2, −y+1/2, −z+1; (v) −x+1/2, −y−1/2, −z+1; (vi) x−1/2, y+1/2, z; (vii) −x, −y, −z+1; (viii) x, −y, z; (ix) −x+1, −y, −z+1; (x) x, y, z−1; (xi) −x+1, −y, −z; (xii) −x+1/2, −y−1/2, −z; (xiii) x+1/2, y+1/2, z; (xiv) −x+1/2, −y+1/2, −z; (xv) x+1/2, y−1/2, z; (xvi) x+1/2, y−1/2, z−1; (xvii) x+1/2, y+1/2, z−1; (xviii) −x+1, y, −z+1; (xix) x, y, z+1; (xx) −x+1/2, −y+1/2, −z+2; (xxi) −x+1/2, −y−1/2, −z+2; (xxii) x, y+1, z; (xxiii) −x+1/2, y+1/2, −z+1.