Na_1.50Mn_2.48Al_0.85(PO₄)₃, a new synthetic alluaudite-type compound

The first hydro­thermal synthesis of an Al-rich alluaudite-type compound, namely disodium dimanganese aluminium tris­(phosphate), which has been obtained at 1073 K and 0.1 GPa starting from the composition Na₂Mn₂Al(PO₄)₃, is reported. The crystal structure, which has been refined in the monoclinic C2/c space group, is identical to that of natural alluaudite. The structure consists of kinked chains of edge-sharing M1 and M2 octa­hedra, which contain Mn²⁺ and Al³⁺ ions. The chains are stacked parallel to {101} and are connected in the b direction by the P1 and P2 tetra­hedra. These inter­connected chains produce channels parallel to c, which contain the large A1 and A2' sites occupied by Na⁺ and Mn²⁺ ions.

S1. Comment

In the natural geological environment of granitic pegmatites, alluaudite-type phosphates generally show chemical compositions comprised between Na₂MnFe²⁺Fe³⁺(PO₄)₃ and NaMnFe³⁺₂(PO₄)₃. The incorporation of significant amounts of aluminium into the crystal structure of these minerals produces a splitting of the M2 site of alluaudite into the M2a and M2b positions, thus leading to the more ordered wyllieite-type phosphates (Moore & Molin-Case, 1974; Hatert, Lefèvre et al., 2005). Consequently, the C2/c space group of alluaudite transforms into P2₁/n in wyllieite, with no significant change in the unit-cell parameters.

During the past 20 years, numerous alluaudite-type phosphates have been synthesized, and the crystal chemistry of this structure type is now well known (Hatert, 2004; Hatert, Rebbouh et al., 2005). Nevertheless, the structural descriptions of natural or synthetic wyllieite-type phosphates are rather scarce (Moore & Molin-Case, 1974; Zhesheng et al., 1983; Brier, 2000; Hatert, Lefèvre et al., 2005). In order to understand better the crystal chemistry of wyllieite-type phosphates, we attempted to obtain a single-crystal of wyllieite by hydrothermal synthesis at 1073 K and 0.1 GPa, starting from the composition Na₂Mn₂Al(PO₄)₃ (Hatert, 2002). The synthesized crystals were investigated by single-crystal X-ray diffraction techniques, and a careful examination of systematic absences indicated the C2/c space group, characteristic of alluaudite-type phosphates. The crystal structure of this Al-rich alluaudite-type compound is reported here.

The structure is similar to that of natural alluaudite, described by Moore (1971), and consists of kinked chains of edge-sharing octahedra stacked parallel to {101}. These chains are formed by a succession of M2–M2 octahedral pairs, linked by highly distorted M1 octahedra (Fig. 1). Equivalent chains are connected in the b direction by the P1 and P2 phosphate tetrahedra to form sheets oriented perpendicular to [010] (Fig. 2). These interconnected chains produce channels parallel to c, which contain the large distorted cubic A1 site and the A2' site with a morphology of a gabled disphenoid (Fig. 2). The site-occupancy factors indicate the following cationic distribution: 0.891 (10) Na⁺ in A2', 0.619 (8) Na⁺ + 0.381 (7) Mn²⁺ in A1, 0.908 (4) Mn²⁺ in M1, and 0.573 (6) Mn²⁺ + 0.427 (6) A l³⁺ in M2. This cationic distribution is in very good agreement with the chemical composition.

Bond-valence sums were calculated for each ion using the parameters of Brown & Altermatt (1985). The P1 and P2 bond-valence sums are 4.99 and 4.98, respectively, and the O-atom bond-valence sums are within the normal acceptable range (1.89–2.10). For the M1 site, the low bond-valence sum obtained in the preliminary calculations indicates an occupancy by ca 0.150 Na⁺ + 0.850 Mn²⁺.

S2. Experimental

The title compound was synthesized under hydrothermal conditions. The starting material was prepared by mixing NaH₂PO₄·H₂O, MnO and Al₂O₃ in the appropriate proportions. An H₃PO₄ solution was added in order to achieve stoichiometry, and the mixture was homogenized in a mortar after evaporation. About 25 mg of the resulting residue was sealed into a gold tube with an outer diameter of 2 mm and a length of 25 mm, containing 2 mg of distilled water. The gold capsule was then inserted in a Tuttle-type pressure vessel (Tuttle, 1949) and maintained at a temperature of 1073 K and a pressure of 0.1 GPa. After 7 d, the sample, still in the gold tube in the autoclave, was quenched to room temperature in a stream of cold air. The synthesized compounds consisted of colourless needles of the title alluaudite-type compound, associated with irregular colourless crystals of Na₃Al₂(PO₄)₃ and with an amorphous matrix. Chemical analysis of the title compound was carried out with a CAMEBAX SX-50 electron microprobe (15 kV acceleration voltage, 20 nA beam current). The standards used were graftonite from Kabira (sample KF16; Fransolet, 1975) (Mn, P), oligoclase (Na) and corundum (Al). The average of six point analyses gives P₂O₅ 45.33, Al₂O₃ 8.27, MnO 37.53 and Na₂O 9.46, total 100.59 wt.%. The chemical composition, calculated on the basis of 12 O, corresponds to Na_1.453Mn_2.518Al_0.772(P_1.01O₄)₃.

S3. Refinement

Atomic coordinates similar to those given by Moore (1971) and by Hatert et al. (2000) were used during the refinement procedure. The site-occupancy factors indicated, in the early stages of the refinement, that the M2 site was occupied by Al³⁺ and Mn²⁺ ions, and that A1 was occupied by Mn²⁺ and Na⁺ ions. Consequently, the site-occupancy factors of both atoms were refined simultaneously on each site, and the sums of the site-occupancy factors were constrained to 1.0. The positions of these atoms and their temperature factors were constrained to be identical with the EXYZ and EADP instructions of SHELXL97 (Sheldrick, 1997).

Computing details

Data collection: XSCANS in SHELXTL-Plus (Sheldrick, 1991); cell refinement: XSCANS; data reduction: SHELXTL-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Dowty, 1993); software used to prepare material for publication: SHELXTL-Plus.

Figures

	Fig. 1. The M1–M2 octahedral chain in Na1.50Mn2.48Al0.85(PO4)3, projected along the b axis. Symmetry code: (i) x - 1/2, y - 1/2, z
	Fig. 2. The crystal structure of Na1.50Mn2.48Al0.85(PO4)3, projected approximately along the c axis.

Disodium dimanganese aluminium tris(phosphate)

Crystal data

Na1.50Mn2.48Al0.85(PO4)3	F(000) = 922
Mr = 468.76	Dx = 3.614 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.9816 (10) Å	Cell parameters from 34 reflections
b = 12.5387 (13) Å	θ = 5.8–12.5°
c = 6.4407 (10) Å	µ = 4.31 mm^−1
β = 114.621 (8)°	T = 293 K
V = 879.64 (18) Å^3	Acicular, elongated along the c axis, colourless
Z = 4	0.23 × 0.07 × 0.05 mm

Data collection

Bruker P4 diffractometer	894 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, Bruker P4	Rint = 0.024
Graphite monochromator	θmax = 27.5°, θmin = 2.5°
Profile data from ω scans	h = −15→1
Absorption correction: ψ scan XSCANS in SHELXTL-Plus (Sheldrick, 1991)	k = −16→1
Tmin = 0.761, Tmax = 0.806	l = −7→8
1271 measured reflections	3 standard reflections every 97 reflections
1019 independent reflections	intensity decay: 2.3%

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.032	Secondary atom site location: difference Fourier map
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.0344P)^2 + 2.4705P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1019 reflections	Δρmax = 0.52 e Å^−3
100 parameters	Δρmin = −0.65 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	Occ. (<1)
Na1	0.5000	0.0000	0.0000	0.0268 (5)	0.619 (8)
Mn1	0.5000	0.0000	0.0000	0.0268 (5)	0.381 (7)
Na2	0.0000	−0.0207 (2)	0.2500	0.0329 (9)	0.891 (10)
Mn3	0.0000	0.26627 (6)	0.2500	0.0144 (3)	0.908 (4)
Mn4	0.27572 (5)	0.65456 (5)	0.35763 (10)	0.0137 (2)	0.573 (6)
Al4	0.27572 (5)	0.65456 (5)	0.35763 (10)	0.0137 (2)	0.427 (6)
P1	0.0000	−0.28457 (9)	0.2500	0.0158 (3)
P2	0.23711 (7)	−0.10611 (7)	0.13087 (13)	0.0154 (2)
O1	0.4524 (2)	0.71353 (19)	0.5356 (4)	0.0183 (5)
O2	0.0959 (3)	0.6397 (2)	0.2321 (5)	0.0422 (9)
O3	0.3317 (3)	0.6633 (2)	0.0992 (4)	0.0290 (7)
O4	0.1268 (2)	0.4078 (2)	0.3175 (5)	0.0266 (6)
O5	0.2279 (2)	0.8255 (2)	0.3217 (4)	0.0282 (6)
O6	0.3272 (3)	0.5010 (2)	0.3849 (5)	0.0291 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0365 (9)	0.0114 (7)	0.0133 (7)	0.0006 (5)	−0.0087 (5)	0.0001 (4)
Mn1	0.0365 (9)	0.0114 (7)	0.0133 (7)	0.0006 (5)	−0.0087 (5)	0.0001 (4)
Na2	0.0203 (13)	0.0427 (17)	0.0256 (14)	0.000	−0.0004 (10)	0.000
Mn3	0.0138 (4)	0.0111 (4)	0.0198 (4)	0.000	0.0085 (3)	0.000
Mn4	0.0114 (3)	0.0172 (3)	0.0119 (3)	0.0032 (2)	0.0043 (2)	−0.0002 (2)
Al4	0.0114 (3)	0.0172 (3)	0.0119 (3)	0.0032 (2)	0.0043 (2)	−0.0002 (2)
P1	0.0201 (6)	0.0129 (5)	0.0087 (5)	0.000	0.0005 (4)	0.000
P2	0.0124 (4)	0.0194 (4)	0.0104 (4)	0.0005 (3)	0.0007 (3)	−0.0044 (3)
O1	0.0181 (11)	0.0202 (12)	0.0129 (10)	0.0059 (10)	0.0028 (9)	−0.0034 (9)
O2	0.051 (2)	0.0318 (16)	0.0305 (16)	0.0162 (14)	0.0036 (15)	−0.0178 (13)
O3	0.0380 (16)	0.0233 (14)	0.0157 (12)	−0.0103 (12)	0.0011 (11)	−0.0062 (10)
O4	0.0155 (12)	0.0193 (12)	0.0413 (16)	0.0034 (10)	0.0083 (11)	0.0074 (11)
O5	0.0226 (13)	0.0408 (16)	0.0183 (13)	0.0028 (12)	0.0056 (10)	0.0036 (11)
O6	0.0230 (14)	0.0337 (15)	0.0218 (13)	−0.0123 (12)	0.0006 (10)	0.0083 (11)

Geometric parameters (Å, º)

Na1—O2^i	2.278 (3)	Mn4—O5	2.206 (3)
Na1—O2^ii	2.278 (3)	Mn4—Mn4^xvii	3.2268 (12)
Na1—O4^i	2.288 (2)	Mn4—Na2^ix	3.2814 (16)
Na1—O4^ii	2.288 (2)	Mn4—Na1^xvi	3.6925 (7)
Na1—O4^iii	2.552 (3)	P1—O2^xviii	1.531 (3)
Na1—O4^iv	2.552 (3)	P1—O2^xix	1.531 (3)
Na1—O2^iii	3.003 (4)	P1—O1^ix	1.539 (2)
Na1—O2^iv	3.003 (4)	P1—O1^x	1.539 (2)
Na1—P1^v	3.1447 (10)	P1—Na1^xi	3.1447 (10)
Na1—P1^vi	3.1447 (10)	P1—Na1^iv	3.1447 (10)
Na1—Mn1^vii	3.2204 (5)	P2—O6^iv	1.531 (3)
Na1—Mn1^viii	3.2204 (5)	P2—O4^iv	1.533 (3)
Na2—O6^ix	2.413 (3)	P2—O5^xix	1.540 (3)
Na2—O6^x	2.413 (3)	P2—O3^i	1.540 (2)
Na2—O6^iv	2.572 (3)	P2—Na2^xiii	3.2877 (16)
Na2—O6^xi	2.572 (3)	P2—Na1^viii	3.3323 (9)
Na2—O1^x	2.725 (3)	O1—P1^ix	1.539 (2)
Na2—O1^ix	2.725 (3)	O1—Mn3^vi	2.241 (2)
Na2—O3^iv	2.949 (4)	O1—Na2^ix	2.725 (3)
Na2—O3^xi	2.949 (4)	O2—P1^xx	1.531 (3)
Na2—Na2^xii	3.2618 (10)	O2—Na1^xvi	2.278 (3)
Na2—Na2^xiii	3.2618 (10)	O2—Mn1^xvi	2.278 (3)
Na2—Mn4^x	3.2814 (16)	O2—Na1^xv	3.003 (4)
Na2—Al4^x	3.2814 (16)	O3—P2^i	1.540 (2)
Mn3—O1^xi	2.241 (2)	O3—Mn3^vi	2.246 (3)
Mn3—O1^iv	2.241 (2)	O3—Na2^vi	2.949 (4)
Mn3—O3^xi	2.246 (3)	O4—P2^xv	1.533 (3)
Mn3—O3^iv	2.246 (3)	O4—Na1^xvi	2.288 (2)
Mn3—O4	2.257 (3)	O4—Mn1^xvi	2.288 (2)
Mn3—O4^xiv	2.257 (3)	O4—Na1^xv	2.552 (3)
Mn3—Na1^xv	3.3439 (7)	O5—P2^xx	1.540 (3)
Mn3—Na1^xvi	3.3439 (7)	O5—Al4^xvii	2.098 (3)
Mn4—O2	1.970 (3)	O5—Mn4^xvii	2.098 (3)
Mn4—O6	2.007 (3)	O6—P2^xv	1.531 (3)
Mn4—O3	2.041 (3)	O6—Na2^ix	2.413 (3)
Mn4—O1	2.078 (2)	O6—Na2^vi	2.572 (3)
Mn4—O5^xvii	2.098 (3)
O2^i—Na1—O2^ii	180.00 (15)	O3^iv—Mn3—O4^xiv	161.10 (9)
O2^i—Na1—O4^i	80.59 (10)	O4—Mn3—O4^xiv	76.32 (13)
O2^ii—Na1—O4^i	99.41 (10)	O1^xi—Mn3—Na1^xv	79.18 (6)
O2^i—Na1—O4^ii	99.41 (10)	O1^iv—Mn3—Na1^xv	134.83 (6)
O2^ii—Na1—O4^ii	80.59 (10)	O3^xi—Mn3—Na1^xv	122.15 (7)
O4^i—Na1—O4^ii	180.00 (11)	O3^iv—Mn3—Na1^xv	118.42 (7)
O2^i—Na1—O4^iii	106.26 (11)	O4—Mn3—Na1^xv	49.69 (7)
O2^ii—Na1—O4^iii	73.74 (11)	O4^xiv—Mn3—Na1^xv	43.00 (6)
O4^i—Na1—O4^iii	70.15 (10)	O1^xi—Mn3—Na1^xvi	134.83 (6)
O4^ii—Na1—O4^iii	109.85 (10)	O1^iv—Mn3—Na1^xvi	79.18 (6)
O2^i—Na1—O4^iv	73.74 (11)	O3^xi—Mn3—Na1^xvi	118.42 (7)
O2^ii—Na1—O4^iv	106.26 (11)	O3^iv—Mn3—Na1^xvi	122.15 (7)
O4^i—Na1—O4^iv	109.85 (10)	O4—Mn3—Na1^xvi	43.00 (6)
O4^ii—Na1—O4^iv	70.15 (10)	O4^xiv—Mn3—Na1^xvi	49.69 (7)
O4^iii—Na1—O4^iv	180.00 (12)	Na1^xv—Mn3—Na1^xvi	57.571 (15)
O2^i—Na1—O2^iii	51.94 (13)	O1^xi—Mn3—Na2	72.84 (6)
O2^ii—Na1—O2^iii	128.06 (13)	O1^iv—Mn3—Na2	72.84 (6)
O4^i—Na1—O2^iii	92.95 (9)	O3^xi—Mn3—Na2	54.89 (7)
O4^ii—Na1—O2^iii	87.05 (9)	O3^iv—Mn3—Na2	54.89 (7)
O4^iii—Na1—O2^iii	63.63 (8)	O4—Mn3—Na2	141.84 (6)
O4^iv—Na1—O2^iii	116.37 (8)	O4^xiv—Mn3—Na2	141.84 (6)
O2^i—Na1—O2^iv	128.06 (13)	Na1^xv—Mn3—Na2	151.214 (8)
O2^ii—Na1—O2^iv	51.94 (13)	Na1^xvi—Mn3—Na2	151.214 (8)
O4^i—Na1—O2^iv	87.05 (9)	O2—Mn4—O6	100.89 (12)
O4^ii—Na1—O2^iv	92.95 (9)	O2—Mn4—O3	110.21 (12)
O4^iii—Na1—O2^iv	116.37 (8)	O6—Mn4—O3	85.92 (11)
O4^iv—Na1—O2^iv	63.63 (8)	O2—Mn4—O1	161.56 (10)
O2^iii—Na1—O2^iv	180.00 (17)	O6—Mn4—O1	95.04 (10)
O2^i—Na1—P1^v	27.28 (8)	O3—Mn4—O1	79.95 (10)
O2^ii—Na1—P1^v	152.72 (8)	O2—Mn4—O5^xvii	87.01 (12)
O4^i—Na1—P1^v	96.77 (7)	O6—Mn4—O5^xvii	99.19 (11)
O4^ii—Na1—P1^v	83.23 (7)	O3—Mn4—O5^xvii	160.92 (11)
O4^iii—Na1—P1^v	91.50 (6)	O1—Mn4—O5^xvii	81.29 (10)
O4^iv—Na1—P1^v	88.50 (6)	O2—Mn4—O5	81.77 (11)
O2^iii—Na1—P1^v	28.73 (6)	O6—Mn4—O5	176.65 (11)
O2^iv—Na1—P1^v	151.27 (6)	O3—Mn4—O5	91.26 (10)
O2^i—Na1—P1^vi	152.72 (8)	O1—Mn4—O5	82.68 (10)
O2^ii—Na1—P1^vi	27.28 (8)	O5^xvii—Mn4—O5	82.92 (11)
O4^i—Na1—P1^vi	83.23 (7)	O2—Mn4—Mn4^xvii	82.43 (8)
O4^ii—Na1—P1^vi	96.77 (7)	O6—Mn4—Mn4^xvii	141.85 (9)
O4^iii—Na1—P1^vi	88.50 (6)	O3—Mn4—Mn4^xvii	129.02 (8)
O4^iv—Na1—P1^vi	91.50 (6)	O1—Mn4—Mn4^xvii	79.30 (7)
O2^iii—Na1—P1^vi	151.27 (6)	O5^xvii—Mn4—Mn4^xvii	42.73 (8)
O2^iv—Na1—P1^vi	28.73 (6)	O5—Mn4—Mn4^xvii	40.19 (7)
P1^v—Na1—P1^vi	180.0	O2—Mn4—Na2^ix	132.26 (10)
O2^i—Na1—Mn1^vii	63.51 (9)	O6—Mn4—Na2^ix	47.05 (8)
O2^ii—Na1—Mn1^vii	116.49 (9)	O3—Mn4—Na2^ix	102.32 (8)
O4^i—Na1—Mn1^vii	51.89 (7)	O1—Mn4—Na2^ix	55.81 (8)
O4^ii—Na1—Mn1^vii	128.11 (7)	O5^xvii—Mn4—Na2^ix	69.44 (8)
O4^iii—Na1—Mn1^vii	44.88 (6)	O5—Mn4—Na2^ix	132.19 (8)
O4^iv—Na1—Mn1^vii	135.12 (6)	Mn4^xvii—Mn4—Na2^ix	103.34 (4)
O2^iii—Na1—Mn1^vii	42.77 (5)	O2—Mn4—Na1^xvi	32.10 (8)
O2^iv—Na1—Mn1^vii	137.23 (5)	O6—Mn4—Na1^xvi	73.35 (8)
P1^v—Na1—Mn1^vii	59.201 (12)	O3—Mn4—Na1^xvi	91.83 (7)
P1^vi—Na1—Mn1^vii	120.799 (12)	O1—Mn4—Na1^xvi	166.34 (7)
O2^i—Na1—Mn1^viii	116.49 (9)	O5^xvii—Mn4—Na1^xvi	107.25 (8)
O2^ii—Na1—Mn1^viii	63.51 (9)	O5—Mn4—Na1^xvi	108.58 (7)
O4^i—Na1—Mn1^viii	128.11 (7)	Mn4^xvii—Mn4—Na1^xvi	114.25 (3)
O4^ii—Na1—Mn1^viii	51.89 (7)	Na2^ix—Mn4—Na1^xvi	116.40 (4)
O4^iii—Na1—Mn1^viii	135.12 (6)	O2^xviii—P1—O2^xix	103.3 (3)
O4^iv—Na1—Mn1^viii	44.88 (6)	O2^xviii—P1—O1^ix	107.51 (15)
O2^iii—Na1—Mn1^viii	137.23 (5)	O2^xix—P1—O1^ix	114.65 (13)
O2^iv—Na1—Mn1^viii	42.77 (5)	O2^xviii—P1—O1^x	114.65 (13)
P1^v—Na1—Mn1^viii	120.799 (12)	O2^xix—P1—O1^x	107.51 (15)
P1^vi—Na1—Mn1^viii	59.201 (12)	O1^ix—P1—O1^x	109.28 (19)
Mn1^vii—Na1—Mn1^viii	180.0	O2^xviii—P1—Na1^xi	70.48 (14)
O6^ix—Na2—O6^x	168.26 (19)	O2^xix—P1—Na1^xi	43.00 (12)
O6^ix—Na2—O6^iv	80.43 (8)	O1^ix—P1—Na1^xi	151.32 (9)
O6^x—Na2—O6^iv	98.32 (9)	O1^x—P1—Na1^xi	96.71 (9)
O6^ix—Na2—O6^xi	98.32 (9)	O2^xviii—P1—Na1^iv	43.00 (12)
O6^x—Na2—O6^xi	80.43 (8)	O2^xix—P1—Na1^iv	70.48 (14)
O6^iv—Na2—O6^xi	167.88 (17)	O1^ix—P1—Na1^iv	96.71 (9)
O6^ix—Na2—O1^x	119.89 (12)	O1^x—P1—Na1^iv	151.32 (9)
O6^x—Na2—O1^x	71.53 (9)	Na1^xi—P1—Na1^iv	61.60 (2)
O6^iv—Na2—O1^x	87.18 (9)	O2^xviii—P1—Na2	128.33 (14)
O6^xi—Na2—O1^x	103.69 (10)	O2^xix—P1—Na2	128.33 (14)
O6^ix—Na2—O1^ix	71.53 (9)	O1^ix—P1—Na2	54.64 (9)
O6^x—Na2—O1^ix	119.89 (12)	O1^x—P1—Na2	54.64 (9)
O6^iv—Na2—O1^ix	103.69 (10)	Na1^xi—P1—Na2	149.201 (12)
O6^xi—Na2—O1^ix	87.18 (9)	Na1^iv—P1—Na2	149.201 (12)
O1^x—Na2—O1^ix	54.87 (11)	O6^iv—P2—O4^iv	112.03 (16)
O6^ix—Na2—O3^iv	53.67 (8)	O6^iv—P2—O5^xix	109.85 (16)
O6^x—Na2—O3^iv	115.62 (12)	O4^iv—P2—O5^xix	108.32 (15)
O6^iv—Na2—O3^iv	59.50 (9)	O6^iv—P2—O3^i	106.95 (15)
O6^xi—Na2—O3^iv	110.02 (11)	O4^iv—P2—O3^i	110.91 (16)
O1^x—Na2—O3^iv	146.22 (8)	O5^xix—P2—O3^i	108.74 (15)
O1^ix—Na2—O3^iv	123.85 (7)	O6^iv—P2—Na2^xiii	43.25 (11)
O6^ix—Na2—O3^xi	115.62 (12)	O4^iv—P2—Na2^xiii	128.12 (12)
O6^x—Na2—O3^xi	53.67 (8)	O5^xix—P2—Na2^xiii	122.51 (11)
O6^iv—Na2—O3^xi	110.02 (11)	O3^i—P2—Na2^xiii	63.70 (11)
O6^xi—Na2—O3^xi	59.50 (9)	O6^iv—P2—Na1^viii	89.83 (11)
O1^x—Na2—O3^xi	123.85 (7)	O4^iv—P2—Na1^viii	36.44 (10)
O1^ix—Na2—O3^xi	146.22 (8)	O5^xix—P2—Na1^viii	90.79 (10)
O3^iv—Na2—O3^xi	77.10 (12)	O3^i—P2—Na1^viii	147.20 (12)
O6^ix—Na2—Na2^xii	51.27 (7)	Na2^xiii—P2—Na1^viii	127.26 (5)
O6^x—Na2—Na2^xii	126.38 (8)	O6^iv—P2—Na2	45.20 (13)
O6^iv—Na2—Na2^xii	130.38 (7)	O4^iv—P2—Na2	145.73 (11)
O6^xi—Na2—Na2^xii	47.05 (6)	O5^xix—P2—Na2	69.60 (11)
O1^x—Na2—Na2^xii	123.72 (13)	O3^i—P2—Na2	101.55 (12)
O1^ix—Na2—Na2^xii	74.15 (8)	Na2^xiii—P2—Na2	58.26 (2)
O3^iv—Na2—Na2^xii	80.31 (9)	Na1^viii—P2—Na2	110.03 (3)
O3^xi—Na2—Na2^xii	85.39 (10)	P1^ix—O1—Mn4	127.78 (14)
O6^ix—Na2—Na2^xiii	126.38 (8)	P1^ix—O1—Mn3^vi	116.07 (14)
O6^x—Na2—Na2^xiii	51.27 (7)	Mn4—O1—Mn3^vi	101.62 (9)
O6^iv—Na2—Na2^xiii	47.05 (6)	P1^ix—O1—Na2^ix	97.93 (11)
O6^xi—Na2—Na2^xiii	130.38 (7)	Mn4—O1—Na2^ix	85.07 (9)
O1^x—Na2—Na2^xiii	74.15 (8)	Mn3^vi—O1—Na2^ix	127.35 (10)
O1^ix—Na2—Na2^xiii	123.72 (13)	P1^xx—O2—Mn4	129.57 (18)
O3^iv—Na2—Na2^xiii	85.39 (10)	P1^xx—O2—Na1^xvi	109.71 (17)
O3^xi—Na2—Na2^xiii	80.31 (9)	Mn4—O2—Na1^xvi	120.55 (13)
Na2^xii—Na2—Na2^xiii	161.71 (19)	P1^xx—O2—Mn1^xvi	109.71 (17)
O6^ix—Na2—Mn4^x	153.88 (12)	Mn4—O2—Mn1^xvi	120.55 (13)
O6^x—Na2—Mn4^x	37.51 (7)	Na1^xvi—O2—Mn1^xvi	0.0
O6^iv—Na2—Mn4^x	108.07 (7)	P1^xx—O2—Na1^xv	80.79 (15)
O6^xi—Na2—Mn4^x	78.34 (7)	Mn4—O2—Na1^xv	115.74 (13)
O1^x—Na2—Mn4^x	39.12 (5)	Na1^xvi—O2—Na1^xv	73.72 (10)
O1^ix—Na2—Mn4^x	82.39 (8)	Mn1^xvi—O2—Na1^xv	73.72 (10)
O3^iv—Na2—Mn4^x	151.88 (7)	P2^i—O3—Mn4	122.26 (16)
O3^xi—Na2—Mn4^x	85.31 (5)	P2^i—O3—Mn3^vi	135.09 (17)
Na2^xii—Na2—Mn4^x	120.32 (6)	Mn4—O3—Mn3^vi	102.65 (10)
Na2^xiii—Na2—Mn4^x	69.99 (4)	P2^i—O3—Na2^vi	88.38 (12)
O6^ix—Na2—Al4^x	153.88 (12)	Mn4—O3—Na2^vi	95.83 (9)
O6^x—Na2—Al4^x	37.51 (7)	Mn3^vi—O3—Na2^vi	86.56 (10)
O6^iv—Na2—Al4^x	108.07 (7)	P2^xv—O4—Mn3	121.45 (14)
O6^xi—Na2—Al4^x	78.34 (7)	P2^xv—O4—Na1^xvi	120.11 (15)
O1^x—Na2—Al4^x	39.12 (5)	Mn3—O4—Na1^xvi	94.72 (9)
O1^ix—Na2—Al4^x	82.39 (8)	P2^xv—O4—Mn1^xvi	120.11 (15)
O3^iv—Na2—Al4^x	151.88 (7)	Mn3—O4—Mn1^xvi	94.72 (9)
O3^xi—Na2—Al4^x	85.31 (5)	Na1^xvi—O4—Mn1^xvi	0.0
Na2^xii—Na2—Al4^x	120.32 (6)	P2^xv—O4—Na1^xv	137.34 (16)
Na2^xiii—Na2—Al4^x	69.99 (4)	Mn3—O4—Na1^xv	87.88 (9)
Mn4^x—Na2—Al4^x	0.00 (3)	Na1^xvi—O4—Na1^xv	83.23 (8)
O1^xi—Mn3—O1^iv	145.67 (12)	Mn1^xvi—O4—Na1^xv	83.23 (8)
O1^xi—Mn3—O3^xi	72.27 (9)	P2^xx—O5—Al4^xvii	139.22 (18)
O1^iv—Mn3—O3^xi	88.00 (9)	P2^xx—O5—Mn4^xvii	139.22 (18)
O1^xi—Mn3—O3^iv	88.00 (9)	Al4^xvii—O5—Mn4^xvii	0.00 (3)
O1^iv—Mn3—O3^iv	72.27 (9)	P2^xx—O5—Mn4	121.51 (16)
O3^xi—Mn3—O3^iv	109.79 (14)	Al4^xvii—O5—Mn4	97.08 (11)
O1^xi—Mn3—O4	117.07 (9)	Mn4^xvii—O5—Mn4	97.08 (11)
O1^iv—Mn3—O4	90.52 (9)	P2^xv—O6—Mn4	135.07 (18)
O3^xi—Mn3—O4	161.10 (9)	P2^xv—O6—Na2^ix	110.99 (15)
O3^iv—Mn3—O4	87.61 (9)	Mn4—O6—Na2^ix	95.44 (12)
O1^xi—Mn3—O4^xiv	90.52 (9)	P2^xv—O6—Na2^vi	109.82 (17)
O1^iv—Mn3—O4^xiv	117.07 (9)	Mn4—O6—Na2^vi	109.46 (12)
O3^xi—Mn3—O4^xiv	87.61 (9)	Na2^ix—O6—Na2^vi	81.68 (9)

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−1/2; (iv) −x+1/2, y−1/2, −z+1/2; (v) −x+1/2, −y−1/2, −z; (vi) x+1/2, y+1/2, z; (vii) −x+1, y, −z−1/2; (viii) −x+1, y, −z+1/2; (ix) −x+1/2, −y+1/2, −z+1; (x) x−1/2, −y+1/2, z−1/2; (xi) x−1/2, y−1/2, z; (xii) −x, −y, −z+1; (xiii) −x, −y, −z; (xiv) −x, y, −z+1/2; (xv) −x+1/2, y+1/2, −z+1/2; (xvi) x−1/2, y+1/2, z; (xvii) −x+1/2, −y+3/2, −z+1; (xviii) −x, y−1, −z+1/2; (xix) x, y−1, z; (xx) x, y+1, z.