Ba₅Cl₄(H₂O)₈(VPO₅)₈: a novel three-dimensional framework solid

The novel hydro­thermally synthesized title compound, penta­barium tetra­chloride octa­hydrate octa­kis(oxovanadium phosphate), Ba₅Cl₄(H₂O)₈(VPO₅)₈, crystallizes in the ortho­­rhom­bic space group Cmca with a unit cell containing four formula units. Two Ba²⁺ cations, two Cl^- anions and the O atoms of four water mol­ecules are situated on the (100) mirror plane, while the third independent Ba²⁺ cation is on the inter­section of the (100) plane and the twofold axis parallel to a. Two phosphate P atoms are on twofold axes, while the remaining independent P atom and both V atoms are in general positions. The structure is characterized by two kinds of layers, namely anionic oxovanadium phosphate (VPO₅), composed of corner-sharing VO₅ square pyramids and PO₄ tetra­hedra, and cationic barium chloride hydrate clusters, Ba₅Cl₄(H₂O)₈, composed of three Ba²⁺ cations linked by bridging chloride anions. The layers are connected by Ba-O bonds to generate a three-dimensional structure.

S1. Comment

The V–P–O system has received considerable attention, not only because of its application to catalysis, but also due to its rich and impressive structural chemistry associated with the ability of vanadium to have tetrahedral, square-pyramidal and octahedral coordination environments in various oxidation states. The introduction of pyridinium cations into the V–P–O system leads to rather complicated structures (Huang et al., 2001; Luan et al., 2001). Several structures have also been reported with the introduction of organic ammonium cations into the V–P–O system (Zhang et al., 1995; Soghomonian et al., 1996; Luan et al., 2003). A few structures with introduction of inorganic cations into the P—V—O system have also been reported (Soghomonian et al., 1998; Khan et al., 1996; Tian & Wu, 2002). In the present paper, we report a new compound, Ba₅Cl₄(H₂O)₈(PVO₅)₈, in which the oxovanadium phosphate framework is templated by an unusual cationic barium chloride hydrate cluster of composition Ba₅Cl₄(H₂O)₈.

Ba₅Cl₄(H₂O)₈(VPO₅)₈ crystallizes in the orthorhombic space group Cmca with a unit cell consisting of four asymmetric units. The coordination environments of the V, P and Ba atoms are shown in Fig. 1. Each of the two independent V sites in the asymmetric unit exhibits a distorted square-pyramidal [VO₅] geometry. The basal positions are defined by O donors from four adjacent phosphate groups and the apical O atoms (O1 and O2) are coordinated to adjacent Ba²⁺ cations. Based on the stoichiometry of the compound and assuming normal oxidation states for Ba, Cl, P and O, the oxidation states of vanadium are V^IV and V^V in a ratio of 3:1, i.e. two of the eight V atoms are V^V and six are V^IV. The bond-valence sum calculations (Standard reference?) for V1 and V2 give values of 4.42 and 4.35, respectively. The mean valence, 4.385, is reasonably close to 4.25 for V^IV:V^V = 3:1. Similar mixed bond-valence sums for V atoms have been reported in other oxovanadium phosphates (Zhang et al., 1999; Le Fur et al., 2001). Atoms Ba1, Ba2, Cl1, Cl2 and O11–O14 are situated on the (100) mirror plane, while atom Ba3 is on the intersection of the (100) plane and the twofold axis parallel to a. Atom P1 is on the twofold axis parallel to b and atom P3 is on the twofold axis parallel to a. All other atoms, i.e. V1, V2, P2 and O1–10, are on general positions.

Atoms Ba1 and Ba2 are both 11-coordinate, with four phosphate O atoms, two vanadyl oxo atoms, three water molecules and two bridging Cl^- anions. Atom Ba3 is ten-coordinate, with four phosphate O atoms, four water molecules and two bridging Cl^- anions. The Ba—O bond lengths range from 2.725 (4) to 3.086 (7) Å, while the O—Ba—O angles span 46.72 (10)–180.00 (15)°. The Ba—Cl bond lengths vary from 3.224 (2) to 3.362 (2) Å, with the Cl—Ba—Cl angles in the range 131.61 (5)–180.00 (5)°.

There are two kinds of layer in the structure, namely anionic oxovanadium phosphate (VPO₅) and cationic barium chloride hydrate, Ba₅Cl₄(H₂O)₈. The (VPO₅) layers consist of a checkerboard pattern of corner-sharing VO₅ square pyramids and PO₄ tetrahedra in the bc plane, and are similar to those found in Na₃V₂O₂F(PO₄)₂ (Massa et al., 2002) (Fig. 2). In the layers of barium chloride hydrate, clusters of three Ba²⁺ cations are linked via additional bridging of the Cl^- anions and water molecules to form a two-dimensional network in the bc plane (Fig. 3). To our knowledge, this barium chloride hydrate structural unit is unprecedented. Adjacent VPO₅ and Ba₅Cl₄(H₂O)₈ layers are connected by Ba—O bonds involving both phosphate and vanadyl O atoms of the anionic layers, and the layers alternate along the a axis to generate the three-dimensional structure (Fig. 4).

S2. Experimental

Single crystals of the title compound were prepared from a mixture of NH₄VO₃ (2 mmol, 0.234 g), BaCl₂ (2 mmol, 0.4886 g), H₃BO₃ (2.5 mmol, 0.1758 g), H₃PO₄ (2 ml) and H₂O (2 ml). The mixture was sealed in a 30 ml Teflon-lined stainless steel vessel and heated at 443 K for 6 d under autogenous pressure, then cooled to room temperature. The resulting dark-green crystals were collected and dried in air at ambient temperature.

S3. Refinement

The H atoms were located in a difference map and included in the model with O—H constrained to 0.85 Å and U_iso(H) = 1.2U_eq(O). The highest peak in the difference map is 1.63 e Å^-3, 1.82 Å from atom H11, and the deepest hole is -1.2 e Å^-3, 0.66 Å from atom Ba1.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The asymmetric unit and the complete coordination environments of the V, Ba and P atoms in the structure of Ba5Cl4(H2O)8(VPO5)8. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x, -1/2 + y, 1/2 - z; (ii) -x, y, z; (iii) x, -y + 1, -z + 1; (iv) x - 1/2, y - 1/2, z; (v) x, 1 - y, z; (vi) -x, 1/2 + y, 1/2 - z; (vii) -x + 1/2, y, -z + 1/2; (viii) -x - 1/2, -y + 3/2, -z + 1; (ix) x, 2 - y, 1 - z; (x) x, -1 + y, z; (xi) -1/2 - x, 1/2 + y, z; (xii) - x, 1 - y, 1 - z; (xiii) 1/2 + x, 1/2 + y, z; (xiv) -1/2 + x, y, 1/2 - z.]
	Fig. 2. A view of the VPO5 layers, along the a axis. The VO5 square pyramids are larger and the PO4 tetrahedra are smaller.
	Fig. 3. A view of the Ba5Cl4(H2O)8 layers, along the a axis.
	Fig. 4. The three-dimensional structure of Ba5Cl4(H2O)8(VPO5)8, as seen along the b axis. The layers parallel to the bc plane can be seen to stack along the a axis.

pentabarium tetrachloride octahydrate octakis(oxovanadium phosphate)

Crystal data

Ba5Cl4(H2O)8(VPO5)8	F(000) = 4208
Mr = 2267.91	Dx = 3.539 Mg m^−3
Orthorhombic, Cmca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2	Cell parameters from 1819 reflections
a = 13.5073 (8) Å	θ = 2.3–27.4°
b = 8.8803 (5) Å	µ = 6.90 mm^−1
c = 35.482 (2) Å	T = 295 K
V = 4256.1 (4) Å^3	Block, green
Z = 4	0.20 × 0.12 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1993 independent reflections
Radiation source: fine-focus sealed tube	1614 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ϕ and ω scans	θmax = 25.1°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −16→8
Tmin = 0.339, Tmax = 0.492	k = −10→10
10601 measured reflections	l = −42→39

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)] = 0.031	Hydrogen site location: constr
wR(F^2) = 0.078	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0283P)^2 + 42.1779P] where P = (Fo^2 + 2Fc^2)/3
1993 reflections	(Δ/σ)max = 0.001
180 parameters	Δρmax = 1.63 e Å^−3
0 restraints	Δρmin = −1.20 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ba1	0.0000	0.90019 (6)	0.273505 (16)	0.01910 (17)
Ba2	0.0000	1.11287 (6)	0.399827 (15)	0.01737 (16)
Ba3	0.0000	0.5000	0.5000	0.0212 (2)
V2	−0.29225 (7)	0.75070 (10)	0.31245 (3)	0.0059 (2)
V1	−0.20641 (7)	0.75085 (10)	0.43692 (3)	0.0060 (2)
Cl1	0.0000	1.2307 (2)	0.31120 (6)	0.0131 (4)
Cl2	0.0000	0.7680 (2)	0.43684 (6)	0.0126 (4)
P1	0.2500	0.9938 (2)	0.2500	0.0057 (4)
P2	0.25414 (11)	1.00478 (15)	0.37464 (4)	0.0066 (3)
P3	−0.25119 (15)	0.5000	0.5000	0.0051 (4)
O1	−0.3239 (3)	0.7444 (4)	0.43569 (12)	0.0152 (10)
O2	−0.1750 (3)	0.7565 (4)	0.31098 (12)	0.0143 (10)
O3	0.1765 (3)	0.8948 (4)	0.22787 (11)	0.0095 (9)
O4	0.1837 (3)	1.0867 (4)	0.27602 (11)	0.0106 (9)
O5	0.1827 (3)	1.1072 (4)	0.35273 (11)	0.0097 (9)
O6	0.1848 (3)	0.9093 (4)	0.39913 (11)	0.0112 (9)
O7	0.3185 (3)	0.9110 (4)	0.34854 (12)	0.0109 (9)
O8	0.3251 (3)	1.0986 (4)	0.39872 (11)	0.0100 (9)
O9	−0.3193 (3)	0.6002 (4)	0.52346 (11)	0.0109 (9)
O10	−0.1808 (3)	0.5936 (4)	0.47527 (11)	0.0092 (9)
O11	0.0000	0.5878 (6)	0.29195 (19)	0.0210 (15)
H11	−0.0412	0.5376	0.3050	0.025*
O12	0.0000	0.8572 (8)	0.35111 (17)	0.0217 (15)
H12	−0.0386	0.8103	0.3660	0.026*
O13	0.0000	1.1692 (8)	0.47768 (18)	0.0258 (16)
H13	0.0496	1.1374	0.4901	0.031*
O14	0.0000	1.4209 (6)	0.4153 (2)	0.0241 (16)
H14	0.0520	1.4746	0.4139	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.0190 (3)	0.0198 (3)	0.0186 (3)	0.000	0.000	0.0002 (2)
Ba2	0.0179 (3)	0.0198 (3)	0.0144 (3)	0.000	0.000	−0.0032 (2)
Ba3	0.0081 (4)	0.0269 (5)	0.0286 (5)	0.000	0.000	0.0163 (4)
V2	0.0081 (5)	0.0050 (5)	0.0045 (5)	−0.0003 (4)	−0.0002 (4)	−0.0001 (4)
V1	0.0075 (5)	0.0057 (5)	0.0048 (5)	0.0005 (4)	0.0001 (4)	−0.0002 (4)
Cl1	0.0104 (11)	0.0129 (10)	0.0161 (11)	0.000	0.000	0.0020 (8)
Cl2	0.0104 (10)	0.0143 (10)	0.0132 (11)	0.000	0.000	0.0018 (8)
P1	0.0075 (10)	0.0035 (9)	0.0061 (10)	0.000	−0.0009 (8)	0.000
P2	0.0106 (8)	0.0047 (7)	0.0046 (7)	−0.0002 (6)	−0.0007 (6)	−0.0001 (5)
P3	0.0062 (10)	0.0047 (10)	0.0045 (10)	0.000	0.000	−0.0002 (8)
O1	0.012 (2)	0.015 (2)	0.018 (3)	0.0009 (18)	−0.0013 (18)	−0.0004 (18)
O2	0.007 (2)	0.017 (2)	0.019 (3)	−0.0006 (17)	−0.0023 (18)	−0.0014 (18)
O3	0.007 (2)	0.012 (2)	0.009 (2)	−0.0024 (17)	−0.0018 (16)	−0.0019 (17)
O4	0.014 (2)	0.010 (2)	0.008 (2)	0.0014 (17)	0.0024 (17)	−0.0039 (16)
O5	0.011 (2)	0.007 (2)	0.011 (2)	0.0016 (16)	0.0000 (17)	0.0031 (17)
O6	0.014 (2)	0.010 (2)	0.009 (2)	−0.0037 (17)	0.0019 (17)	0.0066 (17)
O7	0.013 (2)	0.009 (2)	0.010 (2)	0.0037 (17)	0.0013 (18)	−0.0027 (17)
O8	0.012 (2)	0.009 (2)	0.009 (2)	−0.0001 (17)	−0.0023 (16)	−0.0041 (17)
O9	0.013 (2)	0.010 (2)	0.010 (2)	0.0021 (17)	0.0008 (17)	−0.0035 (17)
O10	0.010 (2)	0.007 (2)	0.010 (2)	0.0000 (16)	0.0010 (16)	0.0033 (17)
O11	0.019 (4)	0.007 (3)	0.037 (4)	0.000	0.000	−0.002 (3)
O12	0.018 (3)	0.045 (4)	0.003 (3)	0.000	0.000	−0.006 (3)
O13	0.015 (4)	0.042 (4)	0.021 (4)	0.000	0.000	0.007 (3)
O14	0.014 (3)	0.007 (3)	0.052 (5)	0.000	0.000	0.004 (3)

Geometric parameters (Å, º)

Ba1—O12	2.780 (6)	V2—O3^iv	1.965 (4)
Ba1—O11	2.850 (6)	V2—O4^xi	1.974 (4)
Ba1—O11^i	2.858 (6)	V1—O1	1.589 (4)
Ba1—O3^ii	2.882 (4)	V1—O8^xi	1.961 (4)
Ba1—O3	2.882 (4)	V1—O9^xii	1.962 (4)
Ba1—O4	2.984 (4)	V1—O6^ii	1.966 (4)
Ba1—O4^ii	2.984 (4)	V1—O10	1.980 (4)
Ba1—O2	2.997 (4)	V1—Cl2	2.7922 (10)
Ba1—O2^ii	2.997 (4)	Cl1—Ba1^i	3.362 (2)
Ba1—Cl1	3.225 (2)	Cl2—V1^ii	2.7922 (10)
Ba1—Cl1^iii	3.362 (2)	P1—O4^xiii	1.529 (4)
Ba1—P1^iv	3.5762 (5)	P1—O4	1.529 (4)
Ba2—O14	2.790 (6)	P1—O3	1.541 (4)
Ba2—O13	2.807 (7)	P1—O3^xiii	1.541 (4)
Ba2—O12	2.854 (6)	P1—Ba1^xiv	3.5762 (5)
Ba2—O1^v	2.939 (4)	P2—O7	1.519 (4)
Ba2—O1^vi	2.939 (4)	P2—O8	1.530 (4)
Ba2—O5^ii	2.981 (4)	P2—O6	1.533 (4)
Ba2—O5	2.981 (4)	P2—O5	1.537 (4)
Ba2—O6^ii	3.082 (4)	P3—O9^vii	1.526 (4)
Ba2—O6	3.082 (4)	P3—O9	1.526 (4)
Ba2—Cl1	3.314 (2)	P3—O10	1.538 (4)
Ba2—Cl2	3.332 (2)	P3—O10^vii	1.538 (4)
Ba2—P2^ii	3.6748 (15)	O1—Ba2^xi	2.939 (4)
Ba3—O10^vii	2.725 (4)	O3—V2^xiv	1.965 (4)
Ba3—O10	2.725 (4)	O4—V2^v	1.974 (4)
Ba3—O10^ii	2.725 (4)	O5—V2^v	1.945 (4)
Ba3—O10^viii	2.725 (4)	O6—V1^ii	1.966 (4)
Ba3—O13^ix	3.043 (7)	O7—V2^ii	1.947 (4)
Ba3—O13^x	3.043 (7)	O8—V1^v	1.961 (4)
Ba3—O14^ix	3.086 (7)	O9—V1^xii	1.962 (4)
Ba3—O14^x	3.086 (7)	O11—Ba1^iii	2.858 (6)
Ba3—Cl2	3.269 (2)	O11—H11	0.8500
Ba3—Cl2^viii	3.269 (2)	O12—H12	0.8499
Ba3—P3^viii	3.393 (2)	O13—Ba3^xv	3.043 (7)
Ba3—P3	3.393 (2)	O13—H13	0.8499
V2—O2	1.585 (4)	O14—Ba3^xv	3.086 (7)
V2—O7^ii	1.947 (4)	O14—H14	0.8500
V2—O5^xi	1.945 (4)
O12—Ba1—O11	68.83 (19)	O10^viii—Ba3—O14^ix	104.13 (9)
O12—Ba1—O11^i	152.24 (19)	O13^ix—Ba3—O14^ix	61.76 (16)
O11—Ba1—O11^i	138.93 (13)	O13^x—Ba3—O14^ix	118.24 (16)
O12—Ba1—O3^ii	123.65 (8)	O10^vii—Ba3—O14^x	75.87 (9)
O11—Ba1—O3^ii	96.48 (11)	O10—Ba3—O14^x	104.13 (9)
O11^i—Ba1—O3^ii	63.46 (9)	O10^ii—Ba3—O14^x	104.13 (9)
O12—Ba1—O3	123.65 (8)	O10^viii—Ba3—O14^x	75.87 (9)
O11—Ba1—O3	96.48 (11)	O13^ix—Ba3—O14^x	118.24 (16)
O11^i—Ba1—O3	63.46 (9)	O13^x—Ba3—O14^x	61.76 (16)
O3^ii—Ba1—O3	111.61 (15)	O14^ix—Ba3—O14^x	180.000 (1)
O12—Ba1—O4	92.67 (11)	O10^vii—Ba3—Cl2	116.28 (8)
O11—Ba1—O4	122.23 (8)	O10—Ba3—Cl2	63.72 (8)
O11^i—Ba1—O4	72.59 (10)	O10^ii—Ba3—Cl2	63.72 (8)
O3^ii—Ba1—O4	135.53 (11)	O10^viii—Ba3—Cl2	116.28 (8)
O3—Ba1—O4	48.58 (10)	O13^ix—Ba3—Cl2	121.64 (13)
O12—Ba1—O4^ii	92.67 (11)	O13^x—Ba3—Cl2	58.36 (13)
O11—Ba1—O4^ii	122.23 (8)	O14^ix—Ba3—Cl2	59.88 (11)
O11^i—Ba1—O4^ii	72.59 (10)	O14^x—Ba3—Cl2	120.12 (11)
O3^ii—Ba1—O4^ii	48.58 (10)	O10^vii—Ba3—Cl2^viii	63.72 (8)
O3—Ba1—O4^ii	135.53 (11)	O10—Ba3—Cl2^viii	116.28 (8)
O4—Ba1—O4^ii	112.46 (15)	O10^ii—Ba3—Cl2^viii	116.28 (8)
O12—Ba1—O2	60.14 (10)	O10^viii—Ba3—Cl2^viii	63.72 (8)
O11—Ba1—O2	58.92 (9)	O13^ix—Ba3—Cl2^viii	58.36 (13)
O11^i—Ba1—O2	127.49 (8)	O13^x—Ba3—Cl2^viii	121.64 (13)
O3^ii—Ba1—O2	65.79 (11)	O14^ix—Ba3—Cl2^viii	120.12 (11)
O3—Ba1—O2	153.43 (11)	O14^x—Ba3—Cl2^viii	59.88 (11)
O4—Ba1—O2	151.48 (11)	Cl2—Ba3—Cl2^viii	180.0
O4^ii—Ba1—O2	64.37 (11)	O10^vii—Ba3—P3^viii	153.67 (8)
O12—Ba1—O2^ii	60.14 (10)	O10—Ba3—P3^viii	153.67 (8)
O11—Ba1—O2^ii	58.92 (9)	O10^ii—Ba3—P3^viii	26.33 (8)
O11^i—Ba1—O2^ii	127.49 (8)	O10^viii—Ba3—P3^viii	26.33 (8)
O3^ii—Ba1—O2^ii	153.43 (11)	O13^ix—Ba3—P3^viii	90.000 (1)
O3—Ba1—O2^ii	65.79 (11)	O13^x—Ba3—P3^viii	90.000 (1)
O4—Ba1—O2^ii	64.37 (11)	O14^ix—Ba3—P3^viii	90.000 (1)
O4^ii—Ba1—O2^ii	151.48 (11)	O14^x—Ba3—P3^viii	90.000 (1)
O2—Ba1—O2^ii	104.11 (16)	Cl2—Ba3—P3^viii	90.0
O12—Ba1—Cl1	73.39 (14)	Cl2^viii—Ba3—P3^viii	90.0
O11—Ba1—Cl1	142.22 (14)	O10^vii—Ba3—P3	26.33 (8)
O11^i—Ba1—Cl1	78.85 (13)	O10—Ba3—P3	26.33 (8)
O3^ii—Ba1—Cl1	104.37 (8)	O10^ii—Ba3—P3	153.67 (8)
O3—Ba1—Cl1	104.37 (8)	O10^viii—Ba3—P3	153.67 (8)
O4—Ba1—Cl1	58.84 (7)	O13^ix—Ba3—P3	90.000 (1)
O4^ii—Ba1—Cl1	58.84 (7)	O13^x—Ba3—P3	90.000 (1)
O2—Ba1—Cl1	101.74 (8)	O14^ix—Ba3—P3	90.000 (1)
O2^ii—Ba1—Cl1	101.74 (8)	O14^x—Ba3—P3	90.000 (1)
O12—Ba1—Cl1^iii	145.50 (14)	Cl2—Ba3—P3	90.0
O11—Ba1—Cl1^iii	76.67 (14)	Cl2^viii—Ba3—P3	90.0
O11^i—Ba1—Cl1^iii	62.26 (13)	P3^viii—Ba3—P3	180.0
O3^ii—Ba1—Cl1^iii	59.35 (8)	O2—V2—O7^ii	100.4 (2)
O3—Ba1—Cl1^iii	59.35 (8)	O2—V2—O5^xi	102.7 (2)
O4—Ba1—Cl1^iii	105.98 (8)	O7^ii—V2—O5^xi	87.96 (17)
O4^ii—Ba1—Cl1^iii	105.98 (8)	O2—V2—O3^iv	99.8 (2)
O2—Ba1—Cl1^iii	101.88 (8)	O7^ii—V2—O3^iv	87.91 (17)
O2^ii—Ba1—Cl1^iii	101.88 (8)	O5^xi—V2—O3^iv	157.58 (17)
Cl1—Ba1—Cl1^iii	141.11 (5)	O2—V2—O4^xi	99.6 (2)
O12—Ba1—P1^iv	105.24 (3)	O7^ii—V2—O4^xi	160.02 (18)
O11—Ba1—P1^iv	106.25 (4)	O5^xi—V2—O4^xi	88.22 (17)
O11^i—Ba1—P1^iv	71.04 (2)	O3^iv—V2—O4^xi	88.18 (17)
O3^ii—Ba1—P1^iv	24.75 (8)	O1—V1—O8^xi	100.0 (2)
O3—Ba1—P1^iv	130.83 (8)	O1—V1—O9^xii	102.8 (2)
O4—Ba1—P1^iv	131.52 (8)	O8^xi—V1—O9^xii	157.21 (18)
O4^ii—Ba1—P1^iv	24.91 (8)	O1—V1—O6^ii	99.0 (2)
O2—Ba1—P1^iv	57.16 (8)	O8^xi—V1—O6^ii	89.43 (17)
O2^ii—Ba1—P1^iv	161.27 (8)	O9^xii—V1—O6^ii	88.84 (17)
Cl1—Ba1—P1^iv	83.41 (3)	O1—V1—O10	99.7 (2)
Cl1^iii—Ba1—P1^iv	84.01 (2)	O8^xi—V1—O10	87.18 (16)
O14—Ba2—O13	68.4 (2)	O9^xii—V1—O10	87.26 (17)
O14—Ba2—O12	154.1 (2)	O6^ii—V1—O10	161.39 (18)
O13—Ba2—O12	137.54 (19)	O1—V1—Cl2	178.06 (18)
O14—Ba2—O1^v	61.65 (10)	O8^xi—V1—Cl2	79.65 (13)
O13—Ba2—O1^v	60.21 (10)	O9^xii—V1—Cl2	77.71 (13)
O12—Ba2—O1^v	125.34 (8)	O6^ii—V1—Cl2	79.16 (13)
O14—Ba2—O1^vi	61.65 (10)	O10—V1—Cl2	82.23 (12)
O13—Ba2—O1^vi	60.21 (10)	Ba1—Cl1—Ba2	96.11 (5)
O12—Ba2—O1^vi	125.34 (8)	Ba1—Cl1—Ba1^i	92.10 (5)
O1^v—Ba2—O1^vi	108.02 (17)	Ba2—Cl1—Ba1^i	171.79 (7)
O14—Ba2—O5^ii	97.30 (11)	V1^ii—Cl2—V1	173.74 (9)
O13—Ba2—O5^ii	123.69 (8)	V1^ii—Cl2—Ba3	87.68 (5)
O12—Ba2—O5^ii	69.32 (10)	V1—Cl2—Ba3	87.68 (5)
O1^v—Ba2—O5^ii	156.83 (11)	V1^ii—Cl2—Ba2	92.90 (5)
O1^vi—Ba2—O5^ii	65.14 (11)	V1—Cl2—Ba2	92.90 (5)
O14—Ba2—O5	97.30 (11)	Ba3—Cl2—Ba2	159.94 (7)
O13—Ba2—O5	123.69 (8)	O4^xiii—P1—O4	114.7 (3)
O12—Ba2—O5	69.32 (10)	O4^xiii—P1—O3	112.2 (2)
O1^v—Ba2—O5	65.14 (11)	O4—P1—O3	103.8 (2)
O1^vi—Ba2—O5	156.83 (11)	O4^xiii—P1—O3^xiii	103.8 (2)
O5^ii—Ba2—O5	111.76 (15)	O4—P1—O3^xiii	112.2 (2)
O14—Ba2—O6^ii	125.21 (8)	O3—P1—O3^xiii	110.4 (3)
O13—Ba2—O6^ii	96.45 (11)	O4^xiii—P1—Ba1	145.08 (16)
O12—Ba2—O6^ii	61.86 (9)	O4—P1—Ba1	55.32 (15)
O1^v—Ba2—O6^ii	153.10 (11)	O3—P1—Ba1	51.53 (15)
O1^vi—Ba2—O6^ii	65.24 (11)	O3^xiii—P1—Ba1	110.91 (16)
O5^ii—Ba2—O6^ii	46.77 (10)	O4^xiii—P1—Ba1^xiv	55.32 (15)
O5—Ba2—O6^ii	131.00 (11)	O4—P1—Ba1^xiv	145.08 (16)
O14—Ba2—O6	125.21 (8)	O3—P1—Ba1^xiv	110.91 (15)
O13—Ba2—O6	96.45 (11)	O3^xiii—P1—Ba1^xiv	51.53 (15)
O12—Ba2—O6	61.86 (9)	Ba1—P1—Ba1^xiv	153.12 (6)
O1^v—Ba2—O6	65.24 (11)	O7—P2—O8	106.3 (2)
O1^vi—Ba2—O6	153.10 (11)	O7—P2—O6	113.1 (2)
O5^ii—Ba2—O6	131.00 (11)	O8—P2—O6	111.5 (2)
O5—Ba2—O6	46.77 (10)	O7—P2—O5	112.0 (2)
O6^ii—Ba2—O6	108.18 (14)	O8—P2—O5	110.7 (2)
O14—Ba2—Cl1	82.96 (15)	O6—P2—O5	103.3 (2)
O13—Ba2—Cl1	151.34 (14)	O7—P2—Ba2	145.71 (17)
O12—Ba2—Cl1	71.12 (14)	O8—P2—Ba2	107.88 (16)
O1^v—Ba2—Cl1	106.59 (9)	O6—P2—Ba2	55.66 (16)
O1^vi—Ba2—Cl1	106.59 (9)	O5—P2—Ba2	51.83 (15)
O5^ii—Ba2—Cl1	58.22 (8)	O9^vii—P3—O9	105.9 (3)
O5—Ba2—Cl1	58.22 (7)	O9^vii—P3—O10	112.1 (2)
O6^ii—Ba2—Cl1	100.22 (8)	O9—P3—O10	111.6 (2)
O6—Ba2—Cl1	100.22 (8)	O9^vii—P3—O10^vii	111.6 (2)
O14—Ba2—Cl2	145.43 (16)	O9—P3—O10^vii	112.1 (2)
O13—Ba2—Cl2	77.05 (15)	O10—P3—O10^vii	103.6 (3)
O12—Ba2—Cl2	60.49 (14)	O9^vii—P3—Ba3	127.06 (16)
O1^v—Ba2—Cl2	101.22 (8)	O9—P3—Ba3	127.06 (16)
O1^vi—Ba2—Cl2	101.22 (8)	O10—P3—Ba3	51.82 (15)
O5^ii—Ba2—Cl2	101.85 (7)	O10^vii—P3—Ba3	51.82 (16)
O5—Ba2—Cl2	101.85 (7)	V1—O1—Ba2^xi	146.6 (2)
O6^ii—Ba2—Cl2	57.60 (7)	V2—O2—Ba1	144.7 (2)
O6—Ba2—Cl2	57.60 (7)	P1—O3—V2^xiv	127.2 (2)
Cl1—Ba2—Cl2	131.61 (5)	P1—O3—Ba1	103.72 (18)
O14—Ba2—P2^ii	107.70 (4)	V2^xiv—O3—Ba1	126.69 (17)
O13—Ba2—P2^ii	106.61 (4)	P1—O4—V2^v	134.2 (2)
O12—Ba2—P2^ii	69.20 (2)	P1—O4—Ba1	99.77 (18)
O1^v—Ba2—P2^ii	164.78 (9)	V2^v—O4—Ba1	124.48 (17)
O1^vi—Ba2—P2^ii	56.86 (8)	P2—O5—V2^v	130.6 (2)
O5^ii—Ba2—P2^ii	23.92 (8)	P2—O5—Ba2	104.25 (19)
O5—Ba2—P2^ii	129.24 (8)	V2^v—O5—Ba2	123.02 (16)
O6^ii—Ba2—P2^ii	24.25 (7)	P2—O6—V1^ii	133.8 (3)
O6—Ba2—P2^ii	126.97 (8)	P2—O6—Ba2	100.09 (18)
Cl1—Ba2—P2^ii	81.47 (3)	V1^ii—O6—Ba2	122.33 (17)
Cl2—Ba2—P2^ii	81.71 (3)	P2—O7—V2^ii	134.2 (3)
O10^vii—Ba3—O10	52.66 (16)	P2—O8—V1^v	128.7 (2)
O10^vii—Ba3—O10^ii	180.00 (7)	P3—O9—V1^xii	132.6 (3)
O10—Ba3—O10^ii	127.34 (16)	P3—O10—V1	131.7 (2)
O10^vii—Ba3—O10^viii	127.34 (16)	P3—O10—Ba3	101.85 (19)
O10—Ba3—O10^viii	180.00 (16)	V1—O10—Ba3	126.36 (17)
O10^ii—Ba3—O10^viii	52.66 (16)	Ba1—O11—Ba1^iii	112.4 (2)
O10^vii—Ba3—O13^ix	77.84 (9)	Ba1—O11—H11	129.5
O10—Ba3—O13^ix	102.16 (9)	Ba1^iii—O11—H11	97.8
O10^ii—Ba3—O13^ix	102.16 (9)	Ba1—O12—Ba2	119.4 (2)
O10^viii—Ba3—O13^ix	77.84 (9)	Ba1—O12—H12	132.9
O10^vii—Ba3—O13^x	102.16 (9)	Ba2—O12—H12	90.8
O10—Ba3—O13^x	77.84 (9)	Ba2—O13—Ba3^xv	115.3 (2)
O10^ii—Ba3—O13^x	77.84 (9)	Ba2—O13—H13	116.8
O10^viii—Ba3—O13^x	102.16 (9)	Ba3^xv—O13—H13	100.7
O13^ix—Ba3—O13^x	180.0 (2)	Ba2—O14—Ba3^xv	114.5 (2)
O10^vii—Ba3—O14^ix	104.13 (9)	Ba2—O14—H14	122.6
O10—Ba3—O14^ix	75.87 (9)	Ba3^xv—O14—H14	85.9
O10^ii—Ba3—O14^ix	75.87 (9)
O3^ii—Ba1—Cl1—Ba2	121.37 (8)	O13^ix—Ba3—P3—O10^vii	61.6 (2)
O3—Ba1—Cl1—Ba2	−121.37 (8)	O13^x—Ba3—P3—O10^vii	−118.4 (2)
O4—Ba1—Cl1—Ba2	−103.72 (9)	O14^ix—Ba3—P3—O10^vii	123.4 (2)
O4^ii—Ba1—Cl1—Ba2	103.72 (9)	O14^x—Ba3—P3—O10^vii	−56.6 (2)
O2—Ba1—Cl1—Ba2	53.66 (8)	Cl2—Ba3—P3—O10^vii	−176.72 (19)
O2^ii—Ba1—Cl1—Ba2	−53.66 (8)	Cl2^viii—Ba3—P3—O10^vii	3.28 (19)
P1^iv—Ba1—Cl1—Ba2	108.099 (15)	O8^xi—V1—O1—Ba2^xi	−3.2 (4)
O3^ii—Ba1—Cl1—Ba1^i	−58.63 (8)	O9^xii—V1—O1—Ba2^xi	178.7 (4)
O3—Ba1—Cl1—Ba1^i	58.63 (8)	O6^ii—V1—O1—Ba2^xi	87.8 (4)
O4—Ba1—Cl1—Ba1^i	76.28 (9)	O10—V1—O1—Ba2^xi	−92.0 (4)
O4^ii—Ba1—Cl1—Ba1^i	−76.28 (9)	Cl2—V1—O1—Ba2^xi	75 (5)
O2—Ba1—Cl1—Ba1^i	−126.34 (8)	O7^ii—V2—O2—Ba1	−87.7 (4)
O2^ii—Ba1—Cl1—Ba1^i	126.34 (8)	O5^xi—V2—O2—Ba1	−177.9 (3)
P1^iv—Ba1—Cl1—Ba1^i	−71.901 (15)	O3^iv—V2—O2—Ba1	2.0 (4)
O1^v—Ba2—Cl1—Ba1	122.41 (8)	O4^xi—V2—O2—Ba1	91.8 (4)
O1^vi—Ba2—Cl1—Ba1	−122.41 (8)	O12—Ba1—O2—V2	137.5 (4)
O5^ii—Ba2—Cl1—Ba1	−76.87 (9)	O11—Ba1—O2—V2	−140.6 (4)
O5—Ba2—Cl1—Ba1	76.87 (9)	O11^i—Ba1—O2—V2	−10.3 (5)
O6^ii—Ba2—Cl1—Ba1	−55.38 (7)	O3^ii—Ba1—O2—V2	−26.0 (4)
O6—Ba2—Cl1—Ba1	55.38 (7)	O3—Ba1—O2—V2	−116.2 (4)
P2^ii—Ba2—Cl1—Ba1	−70.84 (2)	O4—Ba1—O2—V2	118.2 (4)
O1^v—Ba2—Cl1—Ba1^i	−57.59 (8)	O4^ii—Ba1—O2—V2	27.9 (4)
O1^vi—Ba2—Cl1—Ba1^i	57.59 (8)	O2^ii—Ba1—O2—V2	−179.9 (3)
O5^ii—Ba2—Cl1—Ba1^i	103.13 (9)	Cl1—Ba1—O2—V2	74.6 (4)
O5—Ba2—Cl1—Ba1^i	−103.13 (9)	Cl1^iii—Ba1—O2—V2	−74.3 (4)
O6^ii—Ba2—Cl1—Ba1^i	124.62 (7)	P1^iv—Ba1—O2—V2	0.5 (3)
O6—Ba2—Cl1—Ba1^i	−124.62 (7)	O4^xiii—P1—O3—V2^xiv	53.2 (4)
P2^ii—Ba2—Cl1—Ba1^i	109.16 (2)	O4—P1—O3—V2^xiv	177.5 (3)
O1—V1—Cl2—V1^ii	−124 (5)	O3^xiii—P1—O3—V2^xiv	−62.1 (2)
O8^xi—V1—Cl2—V1^ii	−45.6 (9)	Ba1—P1—O3—V2^xiv	−163.0 (4)
O9^xii—V1—Cl2—V1^ii	131.8 (9)	Ba1^xiv—P1—O3—V2^xiv	−6.7 (3)
O6^ii—V1—Cl2—V1^ii	−137.0 (9)	O4^xiii—P1—O3—Ba1	−143.79 (19)
O10—V1—Cl2—V1^ii	42.9 (9)	O4—P1—O3—Ba1	−19.5 (2)
O1—V1—Cl2—Ba3	−166 (5)	O3^xiii—P1—O3—Ba1	100.97 (17)
O8^xi—V1—Cl2—Ba3	−87.93 (12)	Ba1^xiv—P1—O3—Ba1	156.35 (7)
O9^xii—V1—Cl2—Ba3	89.48 (13)	O12—Ba1—O3—P1	−46.4 (3)
O6^ii—V1—Cl2—Ba3	−179.34 (13)	O11—Ba1—O3—P1	−115.2 (2)
O10—V1—Cl2—Ba3	0.61 (12)	O11^i—Ba1—O3—P1	102.5 (2)
O1—V1—Cl2—Ba2	34 (5)	O3^ii—Ba1—O3—P1	145.15 (12)
O8^xi—V1—Cl2—Ba2	112.15 (13)	O4—Ba1—O3—P1	12.76 (16)
O9^xii—V1—Cl2—Ba2	−70.44 (13)	O4^ii—Ba1—O3—P1	92.9 (2)
O6^ii—V1—Cl2—Ba2	20.73 (13)	O2—Ba1—O3—P1	−136.1 (2)
O10—V1—Cl2—Ba2	−159.32 (13)	O2^ii—Ba1—O3—P1	−63.60 (19)
O10^vii—Ba3—Cl2—V1^ii	−179.51 (10)	Cl1—Ba1—O3—P1	33.0 (2)
O10—Ba3—Cl2—V1^ii	−176.27 (11)	Cl1^iii—Ba1—O3—P1	174.5 (2)
O10^ii—Ba3—Cl2—V1^ii	0.49 (10)	P1^iv—Ba1—O3—P1	126.72 (17)
O10^viii—Ba3—Cl2—V1^ii	3.73 (11)	O12—Ba1—O3—V2^xiv	116.8 (2)
O13^ix—Ba3—Cl2—V1^ii	−87.89 (5)	O11—Ba1—O3—V2^xiv	47.9 (2)
O13^x—Ba3—Cl2—V1^ii	92.11 (5)	O11^i—Ba1—O3—V2^xiv	−94.4 (2)
O14^ix—Ba3—Cl2—V1^ii	−87.89 (5)	O3^ii—Ba1—O3—V2^xiv	−51.7 (3)
O14^x—Ba3—Cl2—V1^ii	92.11 (5)	O4—Ba1—O3—V2^xiv	175.9 (3)
Cl2^viii—Ba3—Cl2—V1^ii	−87.9 (6)	O4^ii—Ba1—O3—V2^xiv	−103.9 (2)
P3^viii—Ba3—Cl2—V1^ii	2.11 (5)	O2—Ba1—O3—V2^xiv	27.1 (4)
P3—Ba3—Cl2—V1^ii	−177.89 (5)	O2^ii—Ba1—O3—V2^xiv	99.6 (2)
O10^vii—Ba3—Cl2—V1	−3.73 (11)	Cl1—Ba1—O3—V2^xiv	−163.84 (18)
O10—Ba3—Cl2—V1	−0.49 (10)	Cl1^iii—Ba1—O3—V2^xiv	−22.38 (16)
O10^ii—Ba3—Cl2—V1	176.27 (11)	P1^iv—Ba1—O3—V2^xiv	−70.1 (2)
O10^viii—Ba3—Cl2—V1	179.51 (10)	O4^xiii—P1—O4—V2^v	−53.2 (3)
O13^ix—Ba3—Cl2—V1	87.89 (5)	O3—P1—O4—V2^v	−175.9 (3)
O13^x—Ba3—Cl2—V1	−92.11 (5)	O3^xiii—P1—O4—V2^v	64.8 (4)
O14^ix—Ba3—Cl2—V1	87.89 (5)	Ba1—P1—O4—V2^v	165.6 (4)
O14^x—Ba3—Cl2—V1	−92.11 (5)	Ba1^xiv—P1—O4—V2^v	10.9 (5)
Cl2^viii—Ba3—Cl2—V1	87.9 (7)	O4^xiii—P1—O4—Ba1	141.21 (19)
P3^viii—Ba3—Cl2—V1	177.89 (5)	O3—P1—O4—Ba1	18.5 (2)
P3—Ba3—Cl2—V1	−2.11 (5)	O3^xiii—P1—O4—Ba1	−100.7 (2)
O10^vii—Ba3—Cl2—Ba2	88.38 (9)	Ba1^xiv—P1—O4—Ba1	−154.65 (17)
O10—Ba3—Cl2—Ba2	91.62 (9)	O12—Ba1—O4—P1	121.6 (2)
O10^ii—Ba3—Cl2—Ba2	−91.62 (9)	O11—Ba1—O4—P1	55.1 (3)
O10^viii—Ba3—Cl2—Ba2	−88.38 (9)	O11^i—Ba1—O4—P1	−82.3 (2)
P3^viii—Ba3—Cl2—Ba2	−90.0	O3^ii—Ba1—O4—P1	−91.3 (2)
P3—Ba3—Cl2—Ba2	90.0	O3—Ba1—O4—P1	−12.69 (15)
O14—Ba2—Cl2—V1^ii	−91.18 (5)	O4^ii—Ba1—O4—P1	−144.37 (10)
O13—Ba2—Cl2—V1^ii	−91.18 (5)	O2—Ba1—O4—P1	138.3 (2)
O12—Ba2—Cl2—V1^ii	88.82 (5)	O2^ii—Ba1—O4—P1	66.75 (18)
O1^v—Ba2—Cl2—V1^ii	−35.61 (10)	Cl1—Ba1—O4—P1	−169.6 (2)
O1^vi—Ba2—Cl2—V1^ii	−146.76 (10)	Cl1^iii—Ba1—O4—P1	−29.01 (19)
O5^ii—Ba2—Cl2—V1^ii	146.59 (9)	P1^iv—Ba1—O4—P1	−125.24 (14)
O5—Ba2—Cl2—V1^ii	31.05 (9)	O12—Ba1—O4—V2^v	−45.9 (2)
O6^ii—Ba2—Cl2—V1^ii	162.40 (11)	O11—Ba1—O4—V2^v	−112.4 (2)
O6—Ba2—Cl2—V1^ii	15.23 (9)	O11^i—Ba1—O4—V2^v	110.2 (2)
Cl1—Ba2—Cl2—V1^ii	88.82 (5)	O3^ii—Ba1—O4—V2^v	101.2 (2)
P2^ii—Ba2—Cl2—V1^ii	159.55 (6)	O3—Ba1—O4—V2^v	179.8 (3)
O14—Ba2—Cl2—V1	91.18 (5)	O4^ii—Ba1—O4—V2^v	48.1 (3)
O13—Ba2—Cl2—V1	91.18 (5)	O2—Ba1—O4—V2^v	−29.2 (4)
O12—Ba2—Cl2—V1	−88.82 (5)	O2^ii—Ba1—O4—V2^v	−100.7 (2)
O1^v—Ba2—Cl2—V1	146.76 (10)	Cl1—Ba1—O4—V2^v	22.89 (16)
O1^vi—Ba2—Cl2—V1	35.61 (10)	Cl1^iii—Ba1—O4—V2^v	163.51 (18)
O5^ii—Ba2—Cl2—V1	−31.05 (9)	P1^iv—Ba1—O4—V2^v	67.3 (2)
O5—Ba2—Cl2—V1	−146.59 (9)	O7—P2—O5—V2^v	−52.1 (4)
O6^ii—Ba2—Cl2—V1	−15.23 (9)	O8—P2—O5—V2^v	66.3 (4)
O6—Ba2—Cl2—V1	−162.40 (11)	O6—P2—O5—V2^v	−174.2 (3)
Cl1—Ba2—Cl2—V1	−88.82 (5)	Ba2—P2—O5—V2^v	163.2 (4)
P2^ii—Ba2—Cl2—V1	−18.08 (5)	O7—P2—O5—Ba2	144.64 (19)
O1^v—Ba2—Cl2—Ba3	55.57 (9)	O8—P2—O5—Ba2	−96.9 (2)
O1^vi—Ba2—Cl2—Ba3	−55.57 (9)	O6—P2—O5—Ba2	22.6 (2)
O5^ii—Ba2—Cl2—Ba3	−122.23 (8)	O14—Ba2—O5—P2	117.8 (2)
O5—Ba2—Cl2—Ba3	122.23 (8)	O13—Ba2—O5—P2	49.0 (3)
O6^ii—Ba2—Cl2—Ba3	−106.41 (9)	O12—Ba2—O5—P2	−85.1 (2)
O6—Ba2—Cl2—Ba3	106.41 (9)	O1^v—Ba2—O5—P2	63.79 (18)
Cl1—Ba2—Cl2—Ba3	180.0	O1^vi—Ba2—O5—P2	141.3 (3)
P2^ii—Ba2—Cl2—Ba3	−109.26 (2)	O5^ii—Ba2—O5—P2	−141.25 (12)
O12—Ba1—P1—O4^xiii	−145.8 (3)	O6^ii—Ba2—O5—P2	−90.3 (2)
O11—Ba1—P1—O4^xiii	142.3 (3)	O6—Ba2—O5—P2	−14.80 (15)
O11^i—Ba1—P1—O4^xiii	5.4 (3)	Cl1—Ba2—O5—P2	−165.1 (2)
O3^ii—Ba1—P1—O4^xiii	28.2 (3)	Cl2—Ba2—O5—P2	−33.21 (19)
O3—Ba1—P1—O4^xiii	72.8 (3)	P2^ii—Ba2—O5—P2	−122.13 (17)
O4—Ba1—P1—O4^xiii	−84.0 (5)	O14—Ba2—O5—V2^v	−47.0 (2)
O4^ii—Ba1—P1—O4^xiii	−38.0 (4)	O13—Ba2—O5—V2^v	−115.8 (2)
O2—Ba1—P1—O4^xiii	177.6 (4)	O12—Ba2—O5—V2^v	110.0 (2)
O2^ii—Ba1—P1—O4^xiii	176.4 (3)	O1^v—Ba2—O5—V2^v	−101.1 (2)
Cl1—Ba1—P1—O4^xiii	−75.1 (3)	O1^vi—Ba2—O5—V2^v	−23.5 (4)
Cl1^iii—Ba1—P1—O4^xiii	68.1 (3)	O5^ii—Ba2—O5—V2^v	53.9 (3)
P1^iv—Ba1—P1—O4^xiii	−4.4 (3)	O6^ii—Ba2—O5—V2^v	104.8 (2)
O12—Ba1—P1—O4	−61.8 (2)	O6—Ba2—O5—V2^v	−179.6 (3)
O11—Ba1—P1—O4	−133.7 (2)	Cl1—Ba2—O5—V2^v	30.01 (16)
O11^i—Ba1—P1—O4	89.4 (2)	Cl2—Ba2—O5—V2^v	161.93 (18)
O3^ii—Ba1—P1—O4	112.2 (2)	P2^ii—Ba2—O5—V2^v	73.0 (2)
O3—Ba1—P1—O4	156.8 (3)	O7—P2—O6—V1^ii	59.9 (4)
O4^ii—Ba1—P1—O4	45.98 (15)	O8—P2—O6—V1^ii	−59.8 (4)
O2—Ba1—P1—O4	−98.4 (3)	O5—P2—O6—V1^ii	−178.7 (3)
O2^ii—Ba1—P1—O4	−99.6 (2)	Ba2—P2—O6—V1^ii	−157.3 (4)
Cl1—Ba1—P1—O4	8.92 (19)	O7—P2—O6—Ba2	−142.79 (19)
Cl1^iii—Ba1—P1—O4	152.05 (19)	O8—P2—O6—Ba2	97.5 (2)
P1^iv—Ba1—P1—O4	79.58 (19)	O5—P2—O6—Ba2	−21.5 (2)
O12—Ba1—P1—O3	141.3 (2)	O14—Ba2—O6—P2	−48.7 (3)
O11—Ba1—P1—O3	69.4 (2)	O13—Ba2—O6—P2	−116.7 (2)
O11^i—Ba1—P1—O3	−67.5 (2)	O12—Ba2—O6—P2	101.9 (2)
O3^ii—Ba1—P1—O3	−44.60 (17)	O1^v—Ba2—O6—P2	−63.76 (19)
O4—Ba1—P1—O3	−156.8 (3)	O1^vi—Ba2—O6—P2	−144.8 (2)
O4^ii—Ba1—P1—O3	−110.9 (2)	O5^ii—Ba2—O6—P2	96.4 (2)
O2—Ba1—P1—O3	104.8 (3)	O5—Ba2—O6—P2	14.60 (15)
O2^ii—Ba1—P1—O3	103.5 (2)	O6^ii—Ba2—O6—P2	144.32 (11)
Cl1—Ba1—P1—O3	−147.9 (2)	Cl1—Ba2—O6—P2	39.90 (19)
Cl1^iii—Ba1—P1—O3	−4.79 (19)	Cl2—Ba2—O6—P2	173.1 (2)
P1^iv—Ba1—P1—O3	−77.3 (2)	P2^ii—Ba2—O6—P2	126.87 (16)
O12—Ba1—P1—O3^xiii	41.3 (2)	O14—Ba2—O6—V1^ii	112.1 (3)
O11—Ba1—P1—O3^xiii	−30.6 (2)	O13—Ba2—O6—V1^ii	44.0 (2)
O11^i—Ba1—P1—O3^xiii	−167.5 (2)	O12—Ba2—O6—V1^ii	−97.4 (2)
O3^ii—Ba1—P1—O3^xiii	−144.6 (2)	O1^v—Ba2—O6—V1^ii	97.0 (2)
O3—Ba1—P1—O3^xiii	−100.0 (3)	O1^vi—Ba2—O6—V1^ii	15.9 (4)
O4—Ba1—P1—O3^xiii	103.1 (2)	O5^ii—Ba2—O6—V1^ii	−102.9 (2)
O4^ii—Ba1—P1—O3^xiii	149.13 (19)	O5—Ba2—O6—V1^ii	175.3 (3)
O2—Ba1—P1—O3^xiii	4.8 (3)	O6^ii—Ba2—O6—V1^ii	−55.0 (3)
O2^ii—Ba1—P1—O3^xiii	3.51 (18)	Cl1—Ba2—O6—V1^ii	−159.38 (18)
Cl1—Ba1—P1—O3^xiii	112.07 (17)	Cl2—Ba2—O6—V1^ii	−26.17 (15)
Cl1^iii—Ba1—P1—O3^xiii	−104.80 (17)	P2^ii—Ba2—O6—V1^ii	−72.4 (2)
P1^iv—Ba1—P1—O3^xiii	−177.28 (16)	O8—P2—O7—V2^ii	173.5 (3)
O12—Ba1—P1—Ba1^xiv	85.34 (14)	O6—P2—O7—V2^ii	50.8 (4)
O11—Ba1—P1—Ba1^xiv	13.42 (14)	O5—P2—O7—V2^ii	−65.4 (4)
O11^i—Ba1—P1—Ba1^xiv	−123.48 (13)	Ba2—P2—O7—V2^ii	−11.6 (6)
O3^ii—Ba1—P1—Ba1^xiv	−100.60 (11)	O7—P2—O8—V1^v	177.2 (3)
O3—Ba1—P1—Ba1^xiv	−56.00 (19)	O6—P2—O8—V1^v	−59.1 (4)
O4—Ba1—P1—Ba1^xiv	147.17 (19)	O5—P2—O8—V1^v	55.3 (4)
O4^ii—Ba1—P1—Ba1^xiv	−166.86 (10)	Ba2—P2—O8—V1^v	0.2 (3)
O2—Ba1—P1—Ba1^xiv	48.8 (3)	O9^vii—P3—O9—V1^xii	175.1 (4)
O2^ii—Ba1—P1—Ba1^xiv	47.53 (9)	O10—P3—O9—V1^xii	−62.6 (4)
Cl1—Ba1—P1—Ba1^xiv	156.09 (4)	O10^vii—P3—O9—V1^xii	53.2 (4)
Cl1^iii—Ba1—P1—Ba1^xiv	−60.79 (3)	Ba3—P3—O9—V1^xii	−4.9 (4)
P1^iv—Ba1—P1—Ba1^xiv	−133.26 (7)	O9^vii—P3—O10—V1	62.5 (4)
O14—Ba2—P2—O7	−139.2 (3)	O9—P3—O10—V1	−56.1 (4)
O13—Ba2—P2—O7	148.8 (3)	O10^vii—P3—O10—V1	−177.0 (4)
O12—Ba2—P2—O7	13.5 (3)	Ba3—P3—O10—V1	−177.0 (4)
O1^v—Ba2—P2—O7	−175.7 (3)	O9^vii—P3—O10—Ba3	−120.5 (2)
O1^vi—Ba2—P2—O7	177.3 (4)	O9—P3—O10—Ba3	120.8 (2)
O5^ii—Ba2—P2—O7	−23.6 (3)	O10^vii—P3—O10—Ba3	0.0
O5—Ba2—P2—O7	−72.2 (3)	O1—V1—O10—P3	−5.0 (4)
O6^ii—Ba2—P2—O7	37.0 (3)	O8^xi—V1—O10—P3	−104.7 (3)
O6—Ba2—P2—O7	80.9 (4)	O9^xii—V1—O10—P3	97.5 (3)
Cl1—Ba2—P2—O7	−59.5 (3)	O6^ii—V1—O10—P3	175.6 (4)
Cl2—Ba2—P2—O7	75.0 (3)	Cl2—V1—O10—P3	175.4 (3)
P2^ii—Ba2—P2—O7	7.4 (3)	O1—V1—O10—Ba3	178.7 (2)
O14—Ba2—P2—O8	35.6 (2)	O8^xi—V1—O10—Ba3	79.0 (2)
O13—Ba2—P2—O8	−36.4 (2)	O9^xii—V1—O10—Ba3	−78.9 (2)
O12—Ba2—P2—O8	−171.7 (2)	O6^ii—V1—O10—Ba3	−0.7 (7)
O1^v—Ba2—P2—O8	−0.89 (19)	Cl2—V1—O10—Ba3	−0.90 (18)
O1^vi—Ba2—P2—O8	−7.8 (4)	O10^viii—Ba3—O10—P3	−163 (100)
O5^ii—Ba2—P2—O8	151.28 (19)	O13^ix—Ba3—O10—P3	64.2 (2)
O5—Ba2—P2—O8	102.6 (3)	O13^x—Ba3—O10—P3	−115.8 (2)
O6^ii—Ba2—P2—O8	−148.20 (18)	O14^ix—Ba3—O10—P3	120.6 (2)
O6—Ba2—P2—O8	−104.3 (3)	O14^x—Ba3—O10—P3	−59.4 (2)
Cl1—Ba2—P2—O8	115.38 (17)	Cl2—Ba3—O10—P3	−176.3 (2)
Cl2—Ba2—P2—O8	−110.15 (17)	Cl2^viii—Ba3—O10—P3	3.7 (2)
P2^ii—Ba2—P2—O8	−177.73 (16)	P3^viii—Ba3—O10—P3	180.0
O14—Ba2—P2—O6	139.9 (2)	O10^vii—Ba3—O10—V1	177.2 (4)
O13—Ba2—P2—O6	67.9 (2)	O10^ii—Ba3—O10—V1	−2.8 (4)
O12—Ba2—P2—O6	−67.4 (2)	O10^viii—Ba3—O10—V1	14 (100)
O1^v—Ba2—P2—O6	103.4 (2)	O13^ix—Ba3—O10—V1	−118.6 (2)
O1^vi—Ba2—P2—O6	96.4 (4)	O13^x—Ba3—O10—V1	61.4 (2)
O5^ii—Ba2—P2—O6	−104.4 (2)	O14^ix—Ba3—O10—V1	−62.2 (2)
O5—Ba2—P2—O6	−153.1 (3)	O14^x—Ba3—O10—V1	117.8 (2)
O6^ii—Ba2—P2—O6	−43.92 (16)	Cl2—Ba3—O10—V1	0.85 (17)
Cl1—Ba2—P2—O6	−140.33 (19)	Cl2^viii—Ba3—O10—V1	−179.15 (17)
Cl2—Ba2—P2—O6	−5.87 (19)	P3^viii—Ba3—O10—V1	−2.8 (4)
P2^ii—Ba2—P2—O6	−73.4 (2)	P3—Ba3—O10—V1	177.2 (4)
O14—Ba2—P2—O5	−67.0 (2)	O3^ii—Ba1—O11—Ba1^iii	56.35 (8)
O13—Ba2—P2—O5	−139.0 (2)	O3—Ba1—O11—Ba1^iii	−56.35 (8)
O12—Ba2—P2—O5	85.7 (2)	O4—Ba1—O11—Ba1^iii	−100.67 (12)
O1^v—Ba2—P2—O5	−103.5 (2)	O4^ii—Ba1—O11—Ba1^iii	100.67 (12)
O1^vi—Ba2—P2—O5	−110.5 (4)	O2—Ba1—O11—Ba1^iii	112.95 (12)
O5^ii—Ba2—P2—O5	48.63 (17)	O2^ii—Ba1—O11—Ba1^iii	−112.95 (12)
O6^ii—Ba2—P2—O5	109.2 (2)	Cl1—Ba1—O11—Ba1^iii	180.0
O6—Ba2—P2—O5	153.1 (3)	Cl1^iii—Ba1—O11—Ba1^iii	0.0
Cl1—Ba2—P2—O5	12.74 (19)	P1^iv—Ba1—O11—Ba1^iii	79.58 (4)
Cl2—Ba2—P2—O5	147.20 (19)	O3^ii—Ba1—O12—Ba2	−96.46 (13)
P2^ii—Ba2—P2—O5	79.6 (2)	O3—Ba1—O12—Ba2	96.46 (13)
O10^vii—Ba3—P3—O9^vii	−89.7 (3)	O4—Ba1—O12—Ba2	56.32 (7)
O10—Ba3—P3—O9^vii	90.3 (3)	O4^ii—Ba1—O12—Ba2	−56.32 (7)
O10^ii—Ba3—P3—O9^vii	90.3 (3)	O2—Ba1—O12—Ba2	−114.58 (11)
O10^viii—Ba3—P3—O9^vii	−89.7 (3)	O2^ii—Ba1—O12—Ba2	114.58 (11)
O13^ix—Ba3—P3—O9^vii	−28.0 (2)	P1^iv—Ba1—O12—Ba2	−78.15 (5)
O13^x—Ba3—P3—O9^vii	152.0 (2)	O1^v—Ba2—O12—Ba1	−97.31 (14)
O14^ix—Ba3—P3—O9^vii	33.7 (2)	O1^vi—Ba2—O12—Ba1	97.31 (14)
O14^x—Ba3—P3—O9^vii	−146.3 (2)	O5^ii—Ba2—O12—Ba1	62.24 (9)
Cl2—Ba3—P3—O9^vii	93.62 (19)	O5—Ba2—O12—Ba1	−62.24 (9)
Cl2^viii—Ba3—P3—O9^vii	−86.38 (19)	O6^ii—Ba2—O12—Ba1	113.30 (10)
P3^viii—Ba3—P3—O9^vii	0 (85)	O6—Ba2—O12—Ba1	−113.30 (10)
O10^vii—Ba3—P3—O9	90.3 (3)	P2^ii—Ba2—O12—Ba1	87.84 (6)
O10—Ba3—P3—O9	−89.7 (3)	O1^v—Ba2—O13—Ba3^xv	68.80 (12)
O10^ii—Ba3—P3—O9	−89.7 (3)	O1^vi—Ba2—O13—Ba3^xv	−68.80 (12)
O10^viii—Ba3—P3—O9	90.3 (3)	O5^ii—Ba2—O13—Ba3^xv	−84.26 (13)
O13^ix—Ba3—P3—O9	152.0 (2)	O5—Ba2—O13—Ba3^xv	84.26 (13)
O13^x—Ba3—P3—O9	−28.0 (2)	O6^ii—Ba2—O13—Ba3^xv	−125.40 (7)
O14^ix—Ba3—P3—O9	−146.3 (2)	O6—Ba2—O13—Ba3^xv	125.40 (7)
O14^x—Ba3—P3—O9	33.7 (2)	P2^ii—Ba2—O13—Ba3^xv	−102.89 (5)
Cl2—Ba3—P3—O9	−86.38 (19)	O1^v—Ba2—O14—Ba3^xv	−66.83 (12)
Cl2^viii—Ba3—P3—O9	93.62 (19)	O1^vi—Ba2—O14—Ba3^xv	66.83 (12)
O13^ix—Ba3—P3—O10	−118.4 (2)	O5^ii—Ba2—O14—Ba3^xv	123.42 (8)
O13^x—Ba3—P3—O10	61.6 (2)	O5—Ba2—O14—Ba3^xv	−123.42 (8)
O14^ix—Ba3—P3—O10	−56.6 (2)	O6^ii—Ba2—O14—Ba3^xv	82.43 (14)
O14^x—Ba3—P3—O10	123.4 (2)	O6—Ba2—O14—Ba3^xv	−82.43 (14)
Cl2—Ba3—P3—O10	3.28 (19)	P2^ii—Ba2—O14—Ba3^xv	101.32 (5)
Cl2^viii—Ba3—P3—O10	−176.72 (19)

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