A new whitlockite, Ca_8.42Na_1.16V(PO₄)₇

Single crystals of a new complex phosphate, calcium sodium vanadium phosphate, Ca_8.42Na_1.16V(PO₄)₇, have been grown from a melt under an inert atmosphere. The crystal structure has rhombohedral (R3c) symmetry and belongs to the whitlockite structure type. Vanadium(III) ions occupy nearly regular octa­hedral sites (M5 with 3 point symmetry), which share corners with six PO₄ tetra­hedra to form isolated units. The calcium ions occupy eight- and nine-coordinated sites. The sodium ions partially occupy one octa­hedral position and share one nine-coordinated position with a Ca atom.

S1. Comment

The mineral whitlockite, Ca_18.19(Mg_1.17Fe_0.83)H_1.62(PO₄)₁₄ (Calvo & Gopal, 1975), is isomorphous with β-Ca₃(PO₄)₂ (Dickens et al., 1974). Some whitlockite-like phases, such as M₉A(XO₄)₇ (M = Ca and Sr, A is a rare-earth or transition metal, and X = P, V and As), show ferroelectric phase transitions or nonlinear optical properties, which make them potentially useful for practical applications. β-Ca₃(PO₄)₂ crystallizes in the rhombohedral space group R3c, with unit-cell parameters a = 10.439 Å and c = 37.375 Å. The structure contains six metal (M1–M6) and three phosphorus (P1–P3) positions; M1–M3, P2 and P3 are in general (18b) positions, while M4–M6 and P1 are in special (6a) positions with a 3 point symmetry. Different combinations of occupied and unoccupied M1–M6 positions provide a basis for the large number of compounds that belong to the whitlockite structure type.

In the rhombohedral M₉A(XO₄)₇ (M = Ca and Sr) whitlockites, M1–M3 are in eightfold coordination, M4 in ninefold coordination and M5 in octahedral coordination. The Ca and Sr atoms occupy the M1–M3 positions, while the M5 position is usually occupied by a trivalent cation (A = Al, Sc, Ga, Cr, Fe, In, Y and rare-earth metals). All P atoms are located at the centers of the PO₄ phosphate groups, and small cations, such as V⁵⁺ or As⁵⁺, may also be accommodated in the P positions (Gopal & Calvo, 1971, 1973). In the case of M = Ca, all known compounds have non-centrosymmetric rhombohedral lattices (space group R3c or R3) with unit cells similar to that of β-Ca₃(PO₄)₂ (Belik et al., 1997; Belik, Morozov, Kotov et al., 2000; Belik, Morozov, Grechkin et al., 2000; Belik, Grechkin et al., 2000; Golubev & Lazoryak, 1990, 1991; Evans et al., 2001; Lazoryak et al., 1996). The Ca₉A(PO₄)₇ compounds (A = Fe or In) exhibit a reversible phase transition to a high-temperature centrosymmetric phase (space group R3c; Lazoryak et al., 2003; Morozov et al., 2002). The Sr₉A(PO₄)₇ compounds [A = Sc, Cr, Fe, Ga and In (Belik, Izumi, Ikeda, Okui et al., 2002), or A = Y and Gd–Lu (Belik, Izumi, Ikeda, Lazoryak et al., 2002)] reveal a monoclinic distortion of the whitlockite-like structure. The corresponding vanadates all have a rhombohedral symmetry (Belik et al., 2005).

All M₉A(XO₄)₇ compounds mentioned above may be easily synthesized by annealing mixtures of the corresponding oxides and phosphates in air, since the A cation is always in its highest or most stable oxidation state. At the same time, the M5 position of the whitlockite structure may be occupied by other trivalent cations. In this work, we demonstrate that V³⁺ can be accommodated within the whitlockite structure if the synthetic conditions prevent the oxidation of vanadium. Initially, this compound was synthesized accidentally during our study of the vanadyl(IV) phosphates, Na₂MVO(PO₄)₂ (M = Ca and Sr; Chernaya et al., 2004), which melt incongruently with disproportionation of the V⁴⁺ cations.

The overall composition for the crystal investigated is Ca_8.42Na_1.16V(PO₄)₇. Its crystal structure was found to be similar to those of other Ca₉A(PO₄)₇ compounds (Fig. 1). The VO₆ octahedra share all six corners with PO₄ tetrahedra, forming isolated anionic groups. Additional isolated P1O₄ tetrahedra are also present in the structure. The Ca and Na cations randomly occupy interstices between the vanadium and phosphorus polyhedra.

All V–O distances are in the range 2.00–2.05 Å. The V atom is situated in a nearly regular octahedron that is typical for V³⁺. The calculated bond valence sum (BVS) of 2.89 is close to the estimated value of 3. The PO₄ tetrahedra are almost regular, with the P–O distances ranging from 1.5196 (16) to 1.5838 (16) Å, and the BVS values are 4.99, 5.01, and 4.90 for atoms P1, P2 and P3, respectively. Atoms Ca1 and Ca2 exhibit coordination number eight, while atom Ca3 has a ninth O-atom neighbour located at 2.9784 (16) Å. The BVS values for atoms Ca1–Ca3 are 2.12, 2.14 and 1.93, respectively. It should be rememebered that the valence values estimated from the BVS calculations (Brown & Altermatt, 1985) are slightly conservative since the diffraction experiment was performed at low temperature. The lower BVS value for atom Ca3 may be caused by the presence of sodium in the M3 position. The Na atom occupying the M4 position is surrounded by six O atoms. However, the Na–O separations are significantly different, viz. three short distances equal to 2.4741 (16) Å and three long ones at 2.830 (3) Å.

As mentioned above, there are different possibilities for distribution of the metal atoms among the M1–M6 positions of the whitlockite structure. The filling of these positions in the Ca_8.42Na_1.16V(PO₄)₇ structure is somewhat similar to that observed previously in other Ca₉M(PO₄)₇ phosphates (M = Li, Na and K, and A = Mg, Ca, Mn and Co (Morozov et al., 1997, 2000; Belik et al., 1999, 2001) or in the Ca₁₀K(VO₄)₇ vanadate (Mueller-Buschbaum & Schrandt, 1996). In the latter structures, the alkali cations fully occupy the M4 position and, therefore, the divalent cation may be accommodated in the M5 position to keep electroneutrality of the compound. On the other hand, a monovalent cation can replace calcium in one of the M1–M3 positions, similar to what is found in Ca₁₈Na₃Fe(PO₄)₁₄ (Strunenkova et al., 1997). Thus, Ca_8.42Na_1.16V(PO₄)₇ demonstrates a coexistence of both types of alkali cations incorporated in the whitlockite-type structure. The observed distribution is necessary to maintain the trivalent state of the vanadium atoms.

We attempted to prepare an Na-free calcium vanadium phosphate, Ca₉V(PO₄)₇, by annealing a stoichiometric mixture of Ca₃(PO₄)₂, Ca₂P₂O₇ and V₂O₃ in an evacuated silica tube at different temperatures (1023–1473 K). These reactions always resulted in multi-phase mixtures containing a whitlockite-like phase along with minor (5% or less) amounts of unknown species. On the other hand, an addition of even small amounts of sodium pyrophosphate to the reaction mixture resulted in the formation of a pure whitlockite phase. The latter result suggests that, in the case of A = V^III, the presence of Na atoms causes the whitlockite-type structure to be more stable than in the case of the Ca₉A(PO₄)₇ phosphate.

S2. Experimental

Na₂CaVO(PO₄)₂ was synthesized from Na₄P₂O₇, Ca₂P₂O₇ and VO₂, as described previously (Chernaya et al., 2004). Single crystals of Ca_8.42Na_1.16V(PO₄)₇ were obtained by melting a single-phase powder sample of Na₂CaVO(PO₄)₂ in an argon atmosphere at 1013 K followed by slow cooling (5 K min⁻¹). In addition to the brown crystals used for the present study, green crystals with unit-cell parameters close to those for Ca_8.42Na_1.16V(PO₄)₇ were also recovered. A refinement of the Na/Ca ratio in these crystals resulted in almost the same value (1.09/8.46) as for the brown crystals. The difference in colour may be attributed to structural defects or to an inhomogeneous distribution of Na atoms in the crystals.

S3. Refinement

The atomic positions for the Ca, V, P and O atoms were determined by direct methods. Subsequent difference Fourier syntheses and least-square refinements resulted in the Ca₉V(PO₄)₇ composition, confirming that the structure belongs to the whitlockite type.

The isotropic displacement parameter for atom Ca3 (0.015 Ų) was found to be twice as large as those for atoms Ca1 and Ca2 (0.007 Ų), despite the fact that all three positions have similar O-atom coordination. The larger displacement parameter for atom Ca3 may be indicative of a partial occupancy or of the presence of a lighter atom in this position. Furthermore, a significant residual electron density (about 7.5 e Å⁻³) was detected near the M4 position. Both discrepancies have been attributed to Na atoms, which were present in the reaction mixture and thus may have entered the structure. A simple introduction of Na cations into the Ca₉Na_xV(PO₄)₇ structure should result in the reduction of vanadium. However, it is well known that a very strong reducing agent is required to reduce vanadium below the +3 oxidation state, whereas our synthetic conditions should not allow for that. The insertion of Na into the structure must be accompanied by a decrease in the Ca content in order to keep the +3 oxidation state of vanadium. Thus, we have considered the following two models:

(i) Na randomly occupies the M4 position only, while the M3 position becomes partially occupied by Ca atoms, and the occupancy factors (g) for both cations are related by the equation g_Na(M4) = 2[1 – g_Ca(M3)].

(ii) Na is located in both the M4 and the M3 positions. Then the occupancies should be expressed as g_Na(M3) + g_Ca(M3) = 1 and g_Na(M3) = g_Na(M4).

Both models were checked carefully. Model (i) resulted in an R value of 0.025, while model (ii) led to an R value of 0.018. This value, however, is close to that (0.019) obtained for the structural model excluding Na atoms. Nevertheless, the similarity of the displacement parameters for the three Ca positions and the lower residual electron density peaks observed in the difference Fourier map indirectly confirm the correctness of our structure solution using model (ii).

During the refinement, the Flack parameter was found to be 0.47 (3). This may indicate that either the structure is centrosymmetric or the crystal is twinned. The only possible space group having particular systematic extinctions is R3c. Indeed, almost all cationic positions are placed in a centrosymmetric manner. However, this is not the case for the position of O atoms. The refinement in the R3c space group gave an R value of 0.30. Therefore, we considered the case of racemic twinning. This resulted in the R value of 0.016 and the BASF parameter of 0.47 (2). Thus, one can conclude that the crystal used in this study is a racemic mixture of two twins with a non-centrosymmetric R3c structure.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: JANA2000 (Petricek & Dusek, 2000); software used to prepare material for publication: JANA2000.

Figures

Fig. 1. A projection of the Ca8.42Na1.16V(PO4)7 structure along the [110] direction.

Calcium sodium vanadate phosphate

Crystal data

Ca8.42Na1.16V(PO4)7	Dx = 3.139 Mg m^−3
Mr = 1079.88	Mo Kα radiation, λ = 0.71069 Å
Trigonal, R3c	Cell parameters from 9009 reflections
Hall symbol: R 3 -2"c	θ = 2.5–28.1°
a = 10.3273 (3) Å	µ = 2.97 mm^−1
c = 37.098 (2) Å	T = 173 K
V = 3426.5 (2) Å^3	Irregular, transparent, brown
Z = 6	0.18 × 0.16 × 0.06 mm
F(000) = 3199

Data collection

Bruker SMART APEX CCD diffractometer	1818 independent reflections
Radiation source: fine-focus sealed tube	1808 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
0.3° ω exposures scans	θmax = 28.1°, θmin = 2.5°
Absorption correction: multi-scan ?	h = −13→13
Tmin = 0.615, Tmax = 0.841	k = −13→13
9009 measured reflections	l = −49→49

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0355P)^2 + 2.3095P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.016	(Δ/σ)max = 0.001
wR(F^2) = 0.048	Δρmax = 0.35 e Å^−3
S = 1.12	Δρmin = −0.67 e Å^−3
1818 reflections	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
143 parameters	Extinction coefficient: 0.00038 (4)
2 restraints	Absolute structure: Flack (1983), 875 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.0 (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	Occ. (<1)
V	0.3333	0.6667	0.435576 (17)	0.00602 (11)
Ca1	0.47745 (4)	0.94303 (4)	0.366928 (11)	0.00863 (10)
Ca2	0.20426 (4)	0.82509 (4)	0.499885 (10)	0.00806 (10)
Ca3	0.79266 (4)	0.60531 (5)	0.426576 (13)	0.00783 (14)	0.806 (2)
P1	0.6667	0.3333	0.36911 (2)	0.00679 (17)
P2	0.48571 (6)	0.47541 (5)	0.465697 (12)	0.00599 (11)
P3	0.17400 (6)	0.86029 (6)	0.403712 (12)	0.00643 (11)
Na1	0.0000	0.0000	0.45676 (8)	0.0116 (8)	0.582 (6)
Na2	0.79266 (4)	0.60531 (5)	0.426576 (13)	0.00783 (14)	0.194
O1	0.6667	0.3333	0.41030 (7)	0.0115 (5)
O2	0.42872 (14)	0.83736 (18)	0.47201 (4)	0.0096 (3)
O3	0.51579 (14)	0.47258 (14)	0.42569 (4)	0.0087 (3)
O4	0.27556 (15)	0.99779 (14)	0.38046 (3)	0.0085 (3)
O5	0.24821 (14)	0.75839 (14)	0.40139 (4)	0.0103 (3)
O6	0.01562 (15)	0.76711 (16)	0.38913 (3)	0.0120 (3)
O7	0.63333 (16)	0.55003 (16)	0.48613 (4)	0.0120 (3)
O8	0.52275 (14)	0.32709 (17)	0.35553 (4)	0.0140 (3)
O9	0.17915 (16)	0.91481 (17)	0.44209 (4)	0.0138 (3)
O10	0.37735 (14)	0.31579 (15)	0.47842 (4)	0.0106 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V	0.00558 (15)	0.00558 (15)	0.0069 (2)	0.00279 (8)	0.000	0.000
Ca1	0.00882 (18)	0.00833 (19)	0.0090 (2)	0.00449 (14)	0.00078 (13)	0.00014 (14)
Ca2	0.00893 (17)	0.00759 (18)	0.00776 (18)	0.00422 (15)	0.00085 (15)	−0.00043 (15)
Ca3	0.0059 (2)	0.0109 (2)	0.0074 (2)	0.00476 (16)	−0.00024 (14)	0.00287 (14)
P1	0.0055 (2)	0.0055 (2)	0.0094 (4)	0.00274 (12)	0.000	0.000
P2	0.0062 (2)	0.0061 (2)	0.0064 (2)	0.00367 (16)	0.0001 (2)	0.00009 (19)
P3	0.0060 (2)	0.0063 (2)	0.0072 (2)	0.00322 (17)	0.00003 (19)	0.00021 (18)
Na1	0.0122 (10)	0.0122 (10)	0.0105 (15)	0.0061 (5)	0.000	0.000
Na2	0.0059 (2)	0.0109 (2)	0.0074 (2)	0.00476 (16)	−0.00024 (14)	0.00287 (14)
O1	0.0124 (8)	0.0124 (8)	0.0096 (12)	0.0062 (4)	0.000	0.000
O2	0.0070 (6)	0.0070 (6)	0.0137 (7)	0.0028 (5)	0.0006 (4)	0.0019 (5)
O3	0.0091 (6)	0.0094 (6)	0.0072 (7)	0.0043 (5)	0.0002 (4)	−0.0001 (5)
O4	0.0103 (6)	0.0089 (6)	0.0071 (5)	0.0054 (5)	0.0008 (4)	0.0017 (4)
O5	0.0086 (6)	0.0071 (6)	0.0162 (7)	0.0048 (5)	0.0001 (4)	−0.0004 (4)
O6	0.0066 (6)	0.0143 (7)	0.0128 (6)	0.0033 (5)	−0.0022 (5)	0.0013 (5)
O7	0.0091 (7)	0.0147 (7)	0.0106 (6)	0.0048 (5)	−0.0031 (5)	−0.0008 (5)
O8	0.0091 (6)	0.0129 (6)	0.0214 (6)	0.0066 (6)	−0.0046 (5)	−0.0049 (5)
O9	0.0145 (7)	0.0162 (7)	0.0084 (6)	0.0059 (6)	0.0004 (5)	−0.0006 (5)
O10	0.0126 (6)	0.0080 (6)	0.0105 (6)	0.0045 (5)	0.0018 (5)	0.0001 (4)

Geometric parameters (Å, º)

V—O5	2.0276 (16)	P2—O7	1.5224 (15)
V—O5^i	2.0276 (16)	P2—O10	1.5323 (14)
V—O5^ii	2.0276 (16)	P2—O2^ii	1.5674 (16)
V—O2	2.0416 (16)	P2—Na2^xiii	3.0072 (6)
V—O2^i	2.0416 (16)	P2—Ca3^xiii	3.0072 (6)
V—O2^ii	2.0416 (16)	P2—Ca2^i	3.1158 (7)
V—Ca2	3.5109 (6)	P2—Ca2^ii	3.1438 (6)
V—Ca2^ii	3.5109 (6)	P3—O9	1.5220 (15)
V—Ca2^i	3.5109 (6)	P3—O6	1.5233 (14)
V—Ca1^i	3.5495 (6)	P3—O4	1.5399 (14)
V—Ca1	3.5495 (6)	P3—O5	1.5838 (16)
V—Ca1^ii	3.5495 (6)	P3—Na2^i	3.1023 (6)
Ca1—O7^iii	2.3131 (14)	P3—Ca3^i	3.1023 (6)
Ca1—O3^i	2.3569 (16)	P3—Ca1^i	3.2529 (6)
Ca1—O8^i	2.4071 (15)	P3—Na1^vi	3.4317 (18)
Ca1—O10^iv	2.4681 (14)	Na1—O9^xvi	2.4741 (16)
Ca1—O4	2.4694 (13)	Na1—O9^xv	2.4741 (16)
Ca1—O5^ii	2.5135 (14)	Na1—O9^i	2.4741 (16)
Ca1—O5	2.5222 (14)	Na1—O8^xvii	2.830 (3)
Ca1—O6^ii	2.7679 (15)	Na1—O8^xviii	2.830 (3)
Ca1—P3	3.1201 (6)	Na1—O8^xix	2.830 (3)
Ca1—P3^ii	3.2529 (6)	Na1—P1^xvii	2.931 (3)
Ca1—Ca2^v	3.4887 (5)	Na1—P3^xvi	3.4317 (18)
Ca1—P1^vi	3.4922 (4)	Na1—P3^xv	3.4316 (18)
Ca2—O8^vii	2.3215 (14)	Na1—P3^i	3.4316 (18)
Ca2—O4^viii	2.3735 (13)	Na1—Ca3^xx	3.7048 (10)
Ca2—O9	2.4008 (15)	Na1—Na2^xx	3.7048 (10)
Ca2—O6^ix	2.4515 (13)	O1—Na2^xi	2.5084 (8)
Ca2—O2^i	2.4582 (13)	O1—Ca3^xi	2.5084 (8)
Ca2—O2	2.4830 (13)	O1—Ca3^xiii	2.5084 (8)
Ca2—O10^ii	2.6080 (14)	O1—Na2^xiii	2.5084 (8)
Ca2—O7^i	2.6540 (15)	O2—P2^i	1.5674 (16)
Ca2—P2^ii	3.1158 (7)	O2—Ca2^ii	2.4582 (13)
Ca2—P2^i	3.1438 (6)	O3—Ca1^ii	2.3569 (16)
Ca2—Ca1^x	3.4887 (5)	O3—Na2^xiii	2.5608 (13)
Ca3—O10^xi	2.3932 (14)	O3—Ca3^xiii	2.5608 (13)
Ca3—O4^ii	2.4217 (13)	O4—Ca2^xxi	2.3735 (13)
Ca3—O3	2.4772 (13)	O4—Na2^i	2.4217 (14)
Ca3—O6^xii	2.4852 (14)	O4—Ca3^i	2.4217 (14)
Ca3—O1	2.5084 (8)	O5—Ca1^i	2.5135 (14)
Ca3—O3^xi	2.5608 (13)	O6—Ca2^xxii	2.4515 (13)
Ca3—O9^ii	2.6349 (16)	O6—Na2^xxiii	2.4852 (14)
Ca3—O7	2.6411 (15)	O6—Ca3^xxiii	2.4852 (14)
Ca3—O8^xi	2.9784 (16)	O6—Ca1^i	2.7679 (15)
Ca3—P2^xi	3.0073 (6)	O7—Ca1^xix	2.3131 (14)
Ca3—P3^ii	3.1023 (6)	O7—Ca2^ii	2.6540 (14)
Ca3—P2	3.1148 (6)	O8—Ca2^xxiv	2.3216 (14)
P1—O1	1.528 (3)	O8—Ca1^ii	2.4071 (14)
P1—O8^xiii	1.5399 (12)	O8—Na1^xiv	2.830 (3)
P1—O8^xi	1.5399 (13)	O8—Na2^xiii	2.9784 (16)
P1—O8	1.5399 (12)	O8—Ca3^xiii	2.9784 (16)
P1—Na1^xiv	2.931 (3)	O9—Na1^vi	2.4741 (16)
P1—Na2^xi	3.2361 (7)	O9—Na2^i	2.6350 (16)
P1—Ca3^xi	3.2361 (7)	O9—Ca3^i	2.6350 (16)
P1—Ca3^xiii	3.2361 (7)	O10—Na2^xiii	2.3932 (14)
P1—Na2^xiii	3.2361 (7)	O10—Ca3^xiii	2.3932 (14)
P1—Ca1^xv	3.4922 (4)	O10—Ca1^xxv	2.4681 (14)
P2—O3	1.5196 (16)	O10—Ca2^i	2.6080 (13)
O5—V—O5^i	85.02 (7)	O8^xi—P1—O8	109.83 (6)
O5—V—O5^ii	85.02 (7)	O1—P1—Na1^xiv	180.0
O5^i—V—O5^ii	85.02 (7)	O8^xiii—P1—Na1^xiv	70.89 (6)
O5—V—O2	98.36 (6)	O8^xi—P1—Na1^xiv	70.89 (6)
O5^i—V—O2	176.59 (6)	O8—P1—Na1^xiv	70.89 (6)
O5^ii—V—O2	95.66 (5)	O1—P1—Na2^xi	48.795 (14)
O5—V—O2^i	95.66 (5)	O8^xiii—P1—Na2^xi	66.51 (6)
O5^i—V—O2^i	98.36 (6)	O8^xi—P1—Na2^xi	102.29 (6)
O5^ii—V—O2^i	176.59 (7)	O8—P1—Na2^xi	146.38 (7)
O2—V—O2^i	80.94 (7)	Na1^xiv—P1—Na2^xi	131.206 (14)
O5—V—O2^ii	176.59 (6)	O1—P1—Ca3^xi	48.795 (14)
O5^i—V—O2^ii	95.66 (5)	O8^xiii—P1—Ca3^xi	66.51 (6)
O5^ii—V—O2^ii	98.36 (6)	O8^xi—P1—Ca3^xi	102.29 (6)
O2—V—O2^ii	80.94 (7)	O8—P1—Ca3^xi	146.38 (7)
O2^i—V—O2^ii	80.94 (7)	Na1^xiv—P1—Ca3^xi	131.206 (14)
O5—V—Ca2	81.54 (4)	O1—P1—Ca3	48.795 (14)
O5^i—V—Ca2	136.85 (4)	O8^xiii—P1—Ca3	146.38 (6)
O5^ii—V—Ca2	133.83 (4)	O8^xi—P1—Ca3	66.51 (6)
O2—V—Ca2	43.90 (4)	O8—P1—Ca3	102.29 (6)
O2^i—V—Ca2	43.19 (4)	Na1^xiv—P1—Ca3	131.205 (14)
O2^ii—V—Ca2	95.74 (5)	Na2^xi—P1—Ca3	81.32 (2)
O5—V—Ca2^ii	136.85 (4)	Ca3^xi—P1—Ca3	81.32 (2)
O5^i—V—Ca2^ii	133.83 (4)	O1—P1—Ca3^xiii	48.795 (14)
O5^ii—V—Ca2^ii	81.54 (4)	O8^xiii—P1—Ca3^xiii	102.29 (6)
O2—V—Ca2^ii	43.19 (4)	O8^xi—P1—Ca3^xiii	146.38 (6)
O2^i—V—Ca2^ii	95.74 (5)	O8—P1—Ca3^xiii	66.51 (6)
O2^ii—V—Ca2^ii	43.90 (4)	Na1^xiv—P1—Ca3^xiii	131.205 (14)
Ca2—V—Ca2^ii	78.893 (15)	Na2^xi—P1—Ca3^xiii	81.32 (2)
O5—V—Ca2^i	133.83 (4)	Ca3^xi—P1—Ca3^xiii	81.32 (2)
O5^i—V—Ca2^i	81.54 (4)	Ca3—P1—Ca3^xiii	81.32 (2)
O5^ii—V—Ca2^i	136.85 (4)	O1—P1—Na2^xiii	48.795 (14)
O2—V—Ca2^i	95.74 (5)	O8^xiii—P1—Na2^xiii	102.29 (6)
O2^i—V—Ca2^i	43.90 (4)	O8^xi—P1—Na2^xiii	146.38 (6)
O2^ii—V—Ca2^i	43.19 (4)	O8—P1—Na2^xiii	66.51 (6)
Ca2—V—Ca2^i	78.893 (15)	Na1^xiv—P1—Na2^xiii	131.205 (14)
Ca2^ii—V—Ca2^i	78.893 (15)	Na2^xi—P1—Na2^xiii	81.32 (2)
O5—V—Ca1^i	43.78 (4)	Ca3^xi—P1—Na2^xiii	81.32 (2)
O5^i—V—Ca1^i	44.03 (4)	O1—P1—Ca1^xv	91.329 (16)
O5^ii—V—Ca1^i	95.44 (5)	O8^xi—P1—Ca1^xv	145.10 (6)
O2—V—Ca1^i	139.05 (4)	O8—P1—Ca1^xv	88.44 (6)
O2^i—V—Ca1^i	87.33 (4)	Na1^xiv—P1—Ca1^xv	88.671 (16)
O2^ii—V—Ca1^i	135.75 (4)	Na2^xi—P1—Ca1^xv	69.849 (11)
Ca2—V—Ca1^i	104.315 (10)	Ca3^xi—P1—Ca1^xv	69.849 (11)
Ca2^ii—V—Ca1^i	176.655 (16)	Ca3—P1—Ca1^xv	140.10 (3)
Ca2^i—V—Ca1^i	102.539 (9)	Ca3^xiii—P1—Ca1^xv	67.861 (11)
O5—V—Ca1	44.03 (4)	Na2^xiii—P1—Ca1^xv	67.861 (11)
O5^i—V—Ca1	95.44 (5)	O3—P2—O7	109.48 (8)
O5^ii—V—Ca1	43.78 (4)	O3—P2—O10	109.05 (7)
O2—V—Ca1	87.33 (4)	O7—P2—O10	113.52 (8)
O2^i—V—Ca1	135.75 (4)	O3—P2—O2^ii	109.35 (8)
O2^ii—V—Ca1	139.05 (4)	O7—P2—O2^ii	107.59 (8)
Ca2—V—Ca1	102.539 (9)	O10—P2—O2^ii	107.77 (7)
Ca2^ii—V—Ca1	104.315 (10)	O3—P2—Na2^xiii	58.36 (5)
Ca2^i—V—Ca1	176.655 (16)	O7—P2—Na2^xiii	118.66 (6)
Ca1^i—V—Ca1	74.207 (15)	O10—P2—Na2^xiii	52.08 (5)
O5—V—Ca1^ii	95.44 (5)	O2^ii—P2—Na2^xiii	133.69 (6)
O5^i—V—Ca1^ii	43.78 (4)	O3—P2—Ca3^xiii	58.36 (5)
O5^ii—V—Ca1^ii	44.03 (4)	O7—P2—Ca3^xiii	118.66 (6)
O2—V—Ca1^ii	135.75 (4)	O10—P2—Ca3^xiii	52.08 (5)
O2^i—V—Ca1^ii	139.05 (4)	O2^ii—P2—Ca3^xiii	133.69 (6)
O2^ii—V—Ca1^ii	87.33 (4)	O3—P2—Ca3	51.64 (5)
Ca2—V—Ca1^ii	176.655 (16)	O7—P2—Ca3	57.87 (6)
Ca2^ii—V—Ca1^ii	102.539 (9)	O10—P2—Ca3	130.20 (6)
Ca2^i—V—Ca1^ii	104.315 (10)	O2^ii—P2—Ca3	121.77 (5)
Ca1^i—V—Ca1^ii	74.206 (15)	Na2^xiii—P2—Ca3	87.05 (2)
Ca1—V—Ca1^ii	74.207 (15)	Ca3^xiii—P2—Ca3	87.05 (2)
O7^iii—Ca1—O3^i	142.38 (5)	O3—P2—Ca2^i	125.40 (6)
O7^iii—Ca1—O8^i	84.43 (5)	O7—P2—Ca2^i	124.74 (6)
O3^i—Ca1—O8^i	78.81 (5)	O10—P2—Ca2^i	56.61 (5)
O7^iii—Ca1—O10^iv	73.56 (5)	O2^ii—P2—Ca2^i	51.19 (5)
O3^i—Ca1—O10^iv	138.50 (5)	Na2^xiii—P2—Ca2^i	96.792 (17)
O8^i—Ca1—O10^iv	88.59 (5)	Ca3^xiii—P2—Ca2^i	96.792 (17)
O7^iii—Ca1—O4	141.41 (5)	Ca3—P2—Ca2^i	172.42 (2)
O3^i—Ca1—O4	74.70 (4)	O3—P2—Ca2^ii	115.27 (5)
O8^i—Ca1—O4	97.70 (5)	O7—P2—Ca2^ii	57.40 (6)
O10^iv—Ca1—O4	68.00 (4)	O10—P2—Ca2^ii	135.16 (6)
O7^iii—Ca1—O5^ii	84.87 (5)	O2^ii—P2—Ca2^ii	51.20 (5)
O3^i—Ca1—O5^ii	77.79 (5)	Na2^xiii—P2—Ca2^ii	172.05 (2)
O8^i—Ca1—O5^ii	124.87 (5)	Ca3^xiii—P2—Ca2^ii	172.05 (2)
O10^iv—Ca1—O5^ii	138.37 (5)	Ca3—P2—Ca2^ii	85.072 (17)
O4—Ca1—O5^ii	122.49 (5)	Ca2^i—P2—Ca2^ii	90.91 (2)
O7^iii—Ca1—O5	125.07 (5)	O9—P3—O6	113.19 (8)
O3^i—Ca1—O5	77.27 (5)	O9—P3—O4	107.53 (8)
O8^i—Ca1—O5	150.46 (5)	O6—P3—O4	113.87 (8)
O10^iv—Ca1—O5	97.99 (5)	O9—P3—O5	110.95 (8)
O4—Ca1—O5	59.29 (5)	O6—P3—O5	106.52 (8)
O5^ii—Ca1—O5	65.94 (7)	O4—P3—O5	104.45 (7)
O7^iii—Ca1—O6^ii	71.60 (4)	O9—P3—Na2^i	58.05 (6)
O3^i—Ca1—O6^ii	71.00 (4)	O6—P3—Na2^i	139.22 (6)
O8^i—Ca1—O6^ii	69.29 (4)	O4—P3—Na2^i	50.08 (5)
O10^iv—Ca1—O6^ii	140.07 (5)	O5—P3—Na2^i	113.71 (5)
O4—Ca1—O6^ii	145.03 (5)	O9—P3—Ca3^i	58.05 (6)
O5^ii—Ca1—O6^ii	56.01 (5)	O6—P3—Ca3^i	139.22 (6)
O5—Ca1—O6^ii	117.82 (5)	O4—P3—Ca3^i	50.08 (5)
O7^iii—Ca1—P3	143.51 (4)	O5—P3—Ca3^i	113.71 (5)
O3^i—Ca1—P3	71.65 (3)	O9—P3—Ca1	117.60 (6)
O8^i—Ca1—P3	123.84 (4)	O6—P3—Ca1	129.19 (6)
O10^iv—Ca1—P3	83.74 (3)	O4—P3—Ca1	51.30 (5)
O4—Ca1—P3	29.12 (3)	O5—P3—Ca1	53.48 (5)
O5^ii—Ca1—P3	94.22 (4)	Na2^i—P3—Ca1	74.389 (15)
O5—Ca1—P3	30.31 (4)	Ca3^i—P3—Ca1	74.389 (15)
O6^ii—Ca1—P3	136.18 (3)	O9—P3—Ca1^i	134.53 (6)
O7^iii—Ca1—P3^ii	74.37 (4)	O6—P3—Ca1^i	58.08 (6)
O3^i—Ca1—P3^ii	74.62 (3)	O4—P3—Ca1^i	116.64 (5)
O8^i—Ca1—P3^ii	97.12 (4)	O5—P3—Ca1^i	48.91 (5)
O10^iv—Ca1—P3^ii	146.68 (4)	Na2^i—P3—Ca1^i	158.71 (2)
O4—Ca1—P3^ii	142.41 (4)	Ca3^i—P3—Ca1^i	158.71 (2)
O5^ii—Ca1—P3^ii	28.35 (4)	Ca1—P3—Ca1^i	84.412 (19)
O5—Ca1—P3^ii	93.01 (4)	O6—P3—Na1^vi	81.18 (6)
O6^ii—Ca1—P3^ii	27.85 (3)	O4—P3—Na1^vi	101.07 (6)
P3—Ca1—P3^ii	118.46 (2)	O5—P3—Na1^vi	147.09 (7)
O7^iii—Ca1—Ca2^v	49.52 (4)	Na2^i—P3—Na1^vi	68.871 (14)
O3^i—Ca1—Ca2^v	98.66 (3)	Ca3^i—P3—Na1^vi	68.871 (14)
O8^i—Ca1—Ca2^v	41.52 (3)	Ca1—P3—Na1^vi	143.230 (18)
O10^iv—Ca1—Ca2^v	97.30 (3)	Ca1^i—P3—Na1^vi	132.357 (19)
O4—Ca1—Ca2^v	138.40 (3)	O9^xvi—Na1—O9^xv	115.30 (5)
O5^ii—Ca1—Ca2^v	94.80 (4)	O9^xvi—Na1—O9^i	115.30 (5)
O5—Ca1—Ca2^v	160.72 (4)	O9^xv—Na1—O9^i	115.30 (5)
O6^ii—Ca1—Ca2^v	44.30 (3)	O9^xvi—Na1—O8^xvii	107.96 (8)
P3—Ca1—Ca2^v	165.023 (17)	O9^xv—Na1—O8^xvii	123.42 (9)
P3^ii—Ca1—Ca2^v	67.831 (14)	O9^i—Na1—O8^xvii	72.97 (6)
O7^iii—Ca1—P1^vi	105.01 (4)	O9^xvi—Na1—O8^xviii	72.97 (6)
O3^i—Ca1—P1^vi	66.33 (4)	O9^xv—Na1—O8^xviii	107.96 (8)
O8^i—Ca1—P1^vi	21.72 (3)	O9^i—Na1—O8^xviii	123.42 (9)
O10^iv—Ca1—P1^vi	87.85 (3)	O8^xvii—Na1—O8^xviii	52.88 (6)
O4—Ca1—P1^vi	77.30 (3)	O9^xvi—Na1—O8^xix	123.42 (9)
O5^ii—Ca1—P1^vi	132.66 (4)	O9^xv—Na1—O8^xix	72.97 (6)
O5—Ca1—P1^vi	129.26 (4)	O9^i—Na1—O8^xix	107.96 (8)
O6^ii—Ca1—P1^vi	82.88 (3)	O8^xvii—Na1—O8^xix	52.88 (6)
P3—Ca1—P1^vi	102.222 (15)	O8^xviii—Na1—O8^xix	52.88 (6)
P3^ii—Ca1—P1^vi	109.076 (16)	O9^xvi—Na1—P1^xvii	102.71 (8)
Ca2^v—Ca1—P1^vi	62.977 (11)	O9^xv—Na1—P1^xvii	102.71 (8)
O8^vii—Ca2—O4^viii	86.01 (5)	O9^i—Na1—P1^xvii	102.71 (8)
O8^vii—Ca2—O9	84.21 (5)	O8^xvii—Na1—P1^xvii	30.94 (4)
O4^viii—Ca2—O9	140.55 (5)	O8^xviii—Na1—P1^xvii	30.94 (4)
O8^vii—Ca2—O6^ix	76.51 (5)	O8^xix—Na1—P1^xvii	30.94 (4)
O4^viii—Ca2—O6^ix	72.49 (5)	O9^xvi—Na1—P3^xvi	23.42 (4)
O9—Ca2—O6^ix	140.54 (5)	O9^xv—Na1—P3^xvi	111.45 (8)
O8^vii—Ca2—O2^i	156.17 (6)	O9^i—Na1—P3^xvi	99.99 (7)
O4^viii—Ca2—O2^i	83.68 (5)	O8^xvii—Na1—P3^xvi	122.31 (4)
O9—Ca2—O2^i	90.21 (5)	O8^xviii—Na1—P3^xvi	96.18 (3)
O6^ix—Ca2—O2^i	120.18 (5)	O8^xix—Na1—P3^xvi	146.45 (6)
O8^vii—Ca2—O2	136.83 (5)	P1^xvii—Na1—P3^xvi	124.99 (4)
O4^viii—Ca2—O2	127.18 (5)	O9^xvi—Na1—P3^xv	99.99 (7)
O9—Ca2—O2	83.49 (5)	O9^xv—Na1—P3^xv	23.42 (4)
O6^ix—Ca2—O2	87.51 (5)	O9^i—Na1—P3^xv	111.45 (8)
O2^i—Ca2—O2	64.87 (7)	O8^xvii—Na1—P3^xv	146.45 (6)
O8^vii—Ca2—O10^ii	97.03 (5)	O8^xviii—Na1—P3^xv	122.31 (4)
O4^viii—Ca2—O10^ii	67.13 (4)	O8^xix—Na1—P3^xv	96.18 (3)
O9—Ca2—O10^ii	76.30 (5)	P1^xvii—Na1—P3^xv	124.99 (4)
O6^ix—Ca2—O10^ii	139.48 (5)	P3^xvi—Na1—P3^xv	90.38 (6)
O2^i—Ca2—O10^ii	59.15 (5)	O9^xvi—Na1—P3^i	111.45 (8)
O2—Ca2—O10^ii	119.69 (5)	O9^xv—Na1—P3^i	99.99 (7)
O8^vii—Ca2—O7^i	78.92 (5)	O9^i—Na1—P3^i	23.42 (4)
O4^viii—Ca2—O7^i	143.48 (5)	O8^xvii—Na1—P3^i	96.18 (3)
O9—Ca2—O7^i	70.98 (5)	O8^xviii—Na1—P3^i	146.45 (6)
O6^ix—Ca2—O7^i	71.71 (4)	O8^xix—Na1—P3^i	122.31 (4)
O2^i—Ca2—O7^i	121.04 (5)	P1^xvii—Na1—P3^i	124.99 (4)
O2—Ca2—O7^i	57.96 (5)	P3^xvi—Na1—P3^i	90.38 (6)
O10^ii—Ca2—O7^i	147.26 (5)	P3^xv—Na1—P3^i	90.38 (6)
O8^vii—Ca2—P2^ii	126.38 (4)	O9^xvi—Na1—Ca3^xx	45.26 (4)
O4^viii—Ca2—P2^ii	72.68 (3)	O9^xv—Na1—Ca3^xx	70.48 (4)
O9—Ca2—P2^ii	82.85 (4)	O9^i—Na1—Ca3^xx	146.99 (11)
O6^ix—Ca2—P2^ii	136.05 (4)	O8^xvii—Na1—Ca3^xx	133.31 (7)
O2^i—Ca2—P2^ii	29.79 (4)	O8^xviii—Na1—Ca3^xx	80.62 (3)
O2—Ca2—P2^ii	92.75 (4)	O8^xix—Na1—Ca3^xx	104.76 (4)
O10^ii—Ca2—P2^ii	29.38 (3)	P1^xvii—Na1—Ca3^xx	107.59 (4)
O7^i—Ca2—P2^ii	141.90 (3)	P3^xvi—Na1—Ca3^xx	51.36 (2)
O8^vii—Ca2—P2^i	107.68 (4)	P3^xv—Na1—Ca3^xx	60.01 (3)
O4^viii—Ca2—P2^i	147.07 (4)	P3^i—Na1—Ca3^xx	127.18 (9)
O9—Ca2—P2^i	71.86 (4)	O9^xvi—Na1—Na2^xx	45.26 (4)
O6^ix—Ca2—P2^i	81.61 (4)	O9^xv—Na1—Na2^xx	70.48 (4)
O2^i—Ca2—P2^i	92.40 (4)	O9^i—Na1—Na2^xx	146.99 (11)
O2—Ca2—P2^i	29.47 (4)	O8^xvii—Na1—Na2^xx	133.31 (7)
O10^ii—Ca2—P2^i	136.90 (3)	O8^xviii—Na1—Na2^xx	80.62 (3)
O7^i—Ca2—P2^i	28.90 (3)	O8^xix—Na1—Na2^xx	104.76 (4)
P2^ii—Ca2—P2^i	116.90 (2)	P1^xvii—Na1—Na2^xx	107.59 (4)
O8^vii—Ca2—Ca1^x	43.41 (4)	P3^xvi—Na1—Na2^xx	51.36 (2)
O4^viii—Ca2—Ca1^x	107.69 (3)	P3^xv—Na1—Na2^xx	60.01 (3)
O9—Ca2—Ca1^x	90.67 (4)	P3^i—Na1—Na2^xx	127.18 (9)
O6^ix—Ca2—Ca1^x	52.05 (4)	Ca3^xx—Na1—Na2^xx	0.000 (14)
O2^i—Ca2—Ca1^x	160.19 (4)	P1—O1—Na2^xi	103.93 (6)
O2—Ca2—Ca1^x	95.58 (4)	P1—O1—Ca3^xi	103.93 (6)
O10^ii—Ca2—Ca1^x	139.92 (3)	P1—O1—Ca3	103.93 (6)
O7^i—Ca2—Ca1^x	41.52 (3)	Na2^xi—O1—Ca3	114.40 (5)
P2^ii—Ca2—Ca1^x	168.808 (18)	Ca3^xi—O1—Ca3	114.40 (5)
P2^i—Ca2—Ca1^x	69.141 (13)	P1—O1—Ca3^xiii	103.93 (6)
O8^vii—Ca2—V	156.31 (4)	Na2^xi—O1—Ca3^xiii	114.40 (5)
O4^viii—Ca2—V	116.08 (4)	Ca3^xi—O1—Ca3^xiii	114.40 (5)
O9—Ca2—V	73.28 (4)	Ca3—O1—Ca3^xiii	114.40 (5)
O6^ix—Ca2—V	116.76 (4)	P1—O1—Na2^xiii	103.93 (6)
O2^i—Ca2—V	34.64 (4)	Na2^xi—O1—Na2^xiii	114.40 (5)
O2—Ca2—V	34.76 (4)	P2^i—O2—V	129.95 (9)
O10^ii—Ca2—V	84.93 (3)	P2^i—O2—Ca2^ii	99.03 (6)
O7^i—Ca2—V	86.70 (3)	V—O2—Ca2^ii	102.16 (6)
P2^ii—Ca2—V	58.902 (11)	P2^i—O2—Ca2	99.33 (7)
P2^i—Ca2—V	58.679 (12)	V—O2—Ca2	101.34 (5)
Ca1^x—Ca2—V	127.811 (13)	Ca2^ii—O2—Ca2	129.08 (6)
O10^xi—Ca3—O4^ii	150.13 (5)	P2—O3—Ca1^ii	146.06 (9)
O10^xi—Ca3—O3	124.12 (5)	P2—O3—Ca3	99.61 (7)
O4^ii—Ca3—O3	73.44 (5)	Ca1^ii—O3—Ca3	102.15 (5)
O10^xi—Ca3—O6^xii	93.57 (4)	P2—O3—Na2^xiii	91.30 (6)
O4^ii—Ca3—O6^xii	71.10 (5)	Ca1^ii—O3—Na2^xiii	103.26 (5)
O3—Ca3—O6^xii	142.16 (5)	Ca3—O3—Na2^xiii	113.65 (6)
O10^xi—Ca3—O1	103.41 (6)	P2—O3—Ca3^xiii	91.30 (6)
O4^ii—Ca3—O1	106.22 (6)	Ca1^ii—O3—Ca3^xiii	103.26 (5)
O3—Ca3—O1	64.42 (4)	Ca3—O3—Ca3^xiii	113.65 (6)
O6^xii—Ca3—O1	113.94 (6)	P3—O4—Ca2^xxi	146.26 (8)
O10^xi—Ca3—O3^xi	60.11 (5)	P3—O4—Na2^i	100.73 (7)
O4^ii—Ca3—O3^xi	132.79 (5)	Ca2^xxi—O4—Na2^i	97.40 (5)
O3—Ca3—O3^xi	126.32 (6)	P3—O4—Ca3^i	100.73 (7)
O6^xii—Ca3—O3^xi	72.80 (5)	Ca2^xxi—O4—Ca3^i	97.40 (5)
O1—Ca3—O3^xi	63.22 (3)	P3—O4—Ca1	99.58 (6)
O10^xi—Ca3—O9^ii	99.16 (5)	Ca2^xxi—O4—Ca1	104.79 (5)
O4^ii—Ca3—O9^ii	58.29 (4)	Na2^i—O4—Ca1	100.54 (5)
O3—Ca3—O9^ii	77.69 (5)	Ca3^i—O4—Ca1	100.54 (5)
O6^xii—Ca3—O9^ii	94.43 (5)	P3—O5—V	138.02 (9)
O1—Ca3—O9^ii	142.05 (4)	P3—O5—Ca1^i	102.74 (7)
O3^xi—Ca3—O9^ii	153.82 (5)	V—O5—Ca1^i	102.30 (6)
O10^xi—Ca3—O7	69.18 (5)	P3—O5—Ca1	96.22 (6)
O4^ii—Ca3—O7	112.82 (5)	V—O5—Ca1	102.00 (6)
O3—Ca3—O7	57.96 (5)	Ca1^i—O5—Ca1	116.52 (6)
O6^xii—Ca3—O7	151.72 (5)	P3—O6—Ca2^xxii	141.66 (8)
O1—Ca3—O7	92.35 (6)	P3—O6—Na2^xxiii	124.57 (7)
O3^xi—Ca3—O7	113.46 (5)	Ca2^xxii—O6—Na2^xxiii	93.73 (5)
O9^ii—Ca3—O7	67.77 (4)	P3—O6—Ca3^xxiii	124.57 (7)
O10^xi—Ca3—O8^xi	125.51 (5)	Ca2^xxii—O6—Ca3^xxiii	93.73 (5)
O4^ii—Ca3—O8^xi	71.91 (5)	P3—O6—Ca1^i	94.08 (6)
O3—Ca3—O8^xi	91.97 (4)	Ca2^xxii—O6—Ca1^i	83.66 (4)
O6^xii—Ca3—O8^xi	64.80 (4)	Na2^xxiii—O6—Ca1^i	94.35 (5)
O1—Ca3—O8^xi	53.36 (6)	Ca3^xxiii—O6—Ca1^i	94.35 (5)
O3^xi—Ca3—O8^xi	65.68 (5)	P2—O7—Ca1^xix	159.02 (9)
O9^ii—Ca3—O8^xi	130.10 (5)	P2—O7—Ca3	92.91 (6)
O7—Ca3—O8^xi	143.47 (4)	Ca1^xix—O7—Ca3	106.35 (5)
O10^xi—Ca3—P2^xi	30.34 (3)	P2—O7—Ca2^ii	93.70 (6)
O4^ii—Ca3—P2^xi	157.19 (4)	Ca1^xix—O7—Ca2^ii	88.96 (5)
O3—Ca3—P2^xi	127.42 (4)	Ca3—O7—Ca2^ii	106.08 (5)
O6^xii—Ca3—P2^xi	86.31 (3)	P1—O8—Ca2^xxiv	140.73 (9)
O1—Ca3—P2^xi	79.60 (4)	P1—O8—Ca1^ii	122.93 (8)
O3^xi—Ca3—P2^xi	30.34 (4)	Ca2^xxiv—O8—Ca1^ii	95.07 (4)
O9^ii—Ca3—P2^xi	129.09 (4)	P1—O8—Na1^xiv	78.17 (7)
O7—Ca3—P2^xi	88.54 (3)	Ca2^xxiv—O8—Na1^xiv	92.98 (5)
O8^xi—Ca3—P2^xi	95.99 (3)	Ca1^ii—O8—Na1^xiv	118.54 (6)
O10^xi—Ca3—P3^ii	127.25 (4)	P1—O8—Na2^xiii	85.19 (7)
O4^ii—Ca3—P3^ii	29.19 (3)	Ca2^xxiv—O8—Na2^xiii	84.68 (5)
O3—Ca3—P3^ii	70.62 (4)	Ca1^ii—O8—Na2^xiii	90.87 (5)
O6^xii—Ca3—P3^ii	84.41 (4)	Na1^xiv—O8—Na2^xiii	150.58 (6)
O1—Ca3—P3^ii	125.51 (4)	P1—O8—Ca3^xiii	85.19 (7)
O3^xi—Ca3—P3^ii	156.82 (4)	Ca2^xxiv—O8—Ca3^xiii	84.68 (5)
O9^ii—Ca3—P3^ii	29.35 (3)	Ca1^ii—O8—Ca3^xiii	90.87 (5)
O7—Ca3—P3^ii	88.64 (3)	Na1^xiv—O8—Ca3^xiii	150.58 (6)
O8^xi—Ca3—P3^ii	101.07 (3)	P3—O9—Ca2	133.09 (9)
P2^xi—Ca3—P3^ii	154.84 (2)	P3—O9—Na1^vi	116.32 (10)
O10^xi—Ca3—P2	97.15 (4)	Ca2—O9—Na1^vi	100.66 (9)
O4^ii—Ca3—P2	92.78 (3)	P3—O9—Na2^i	92.61 (7)
O3—Ca3—P2	28.75 (4)	Ca2—O9—Na2^i	114.25 (6)
O6^xii—Ca3—P2	162.04 (4)	Na1^vi—O9—Na2^i	92.91 (5)
O1—Ca3—P2	77.50 (4)	P3—O9—Ca3^i	92.61 (7)
O3^xi—Ca3—P2	125.12 (4)	Ca2—O9—Ca3^i	114.25 (6)
O9^ii—Ca3—P2	69.69 (3)	Na1^vi—O9—Ca3^i	92.91 (5)
O7—Ca3—P2	29.22 (3)	P2—O10—Na2^xiii	97.59 (6)
O8^xi—Ca3—P2	118.66 (3)	P2—O10—Ca3^xiii	97.59 (6)
P2^xi—Ca3—P2	110.03 (2)	P2—O10—Ca1^xxv	128.42 (7)
P3^ii—Ca3—P2	77.633 (16)	Na2^xiii—O10—Ca1^xxv	109.51 (5)
O1—P1—O8^xiii	109.11 (6)	Ca3^xiii—O10—Ca1^xxv	109.51 (5)
O1—P1—O8^xi	109.11 (6)	P2—O10—Ca2^i	94.01 (6)
O8^xiii—P1—O8^xi	109.83 (6)	Na2^xiii—O10—Ca2^i	132.53 (6)
O1—P1—O8	109.11 (6)	Ca3^xiii—O10—Ca2^i	132.53 (6)
O8^xiii—P1—O8	109.83 (6)	Ca1^xxv—O10—Ca2^i	98.17 (5)

Symmetry codes: (i) −y+1, x−y+1, z; (ii) −x+y, −x+1, z; (iii) −x+y+2/3, y+1/3, z−1/6; (iv) −y+2/3, −x+4/3, z−1/6; (v) −y+5/3, −x+4/3, z−1/6; (vi) x, y+1, z; (vii) −x+y+1/3, y+2/3, z+1/6; (viii) −x+y−2/3, y−1/3, z+1/6; (ix) x+1/3, x−y+5/3, z+1/6; (x) −y+4/3, −x+5/3, z+1/6; (xi) −x+y+1, −x+1, z; (xii) x+1, y, z; (xiii) −y+1, x−y, z; (xiv) −y+2/3, −x+1/3, z−1/6; (xv) x, y−1, z; (xvi) −x+y−1, −x, z; (xvii) −y+1/3, −x+2/3, z+1/6; (xviii) x−2/3, x−y−1/3, z+1/6; (xix) −x+y+1/3, y−1/3, z+1/6; (xx) x−1, y−1, z; (xxi) −x+y−1/3, y+1/3, z−1/6; (xxii) x−1/3, x−y+4/3, z−1/6; (xxiii) x−1, y, z; (xxiv) −x+y−1/3, y−2/3, z−1/6; (xxv) −y+4/3, −x+2/3, z+1/6.