Dipotassium tristrontium dimanganese tris­(diphosphate)

The structure of the title mixed trimetallic diphosphate, K₂Sr₃Mn₂(P₂O₇)₃, is constructed of a three-dimensional matrix composed of SrO_8-10, MnO₅ and PO₄ polyhedra. The sharing of O atoms between these polyhedra creates tunnels of large dimensions parallel to (010), in which are found columns of K⁺ ions. Thus, the presence of several cations differing in size in the solid matrix leads to the formation of large tunnels and potential conductivity.

S1. Comment

There is extensive structural work reported in the literature in the domain of A^IIB^IIP₂O₇ and A^I₂B^IIP₂O₇ complexes. For complexes of this type, which are of interest for their conductive properties, it is apparent that transition metals plus larger alkali and alkaline earth elements form bonds with more covalent character with the O atoms of diphosphate groups and thus a relatively rigid matrix. Smaller and more electropositive elements (forming interactions with oxygen which is more ionic in nature) allow movement through the channels or tunnels in these matrices, giving rise to conductivity.

For example, the structure of K_3.5Pd_2.25(P₂O₇)₂ may be viewed as a matrix composed of Pd_2.25(P₂O₇)₂ groups. Corner-sharing PO₄ polyhedra and square-planar PdO₄ units are linked in a three-dimensional array, forming large parallel tunnels. These tunnels are of three types, viz. of dimensions 3.21 × 8.36, 3.84 × 8.14 and 3.55 × 10.65 Å in which are found two, two and three columns, respectively, of K⁺ ions. These columns are of sufficient diameter to allow movement of K⁺ ions and thus conductivity of the solid (σ_{673 K} = 2.3 × 10^-4 Ω^-1 cm^-1) (El Maadi et al., 2002).

Similarly, the isostructural complexes A^IB^II₆(P₂O₇)₂P₃O₁₀, with A = K and B = Mn, A = Ag and B = Mn, and A = Na and B = Mn (Bennazha et al., 2001, 2002) lead to the conclusion that the Mn₆(P₂O₇)₂P₃O₁₀ matrix is rigid, providing a stable host solid into which the K⁺, Ag⁺ or Na⁺ cations fit. One may conclude that the Mn₆(P₂O₇)₂P₃O₁₀ matrix is analogous to the zeolite-type matrices, which are rigid and solid, resisting conformational changes due to the presence of guest atoms or molecules in their cavities. In these three structures, the tunnels are of smaller dimensions (2.98 × 4.99 Å) and the Ag and Na atoms show valence-bond totals less than the ionic charge.

Another approach to creating a host matrix with tunnels and thus conducting properties may be to build the host matrix from P₂O₇ and two different cations, both of which tend to more covalent bonding character, but which differ in size. There is only one example in the literature of a trimetallic diphosphate, i.e. K₆Sr₂Ni₅(P₂O₇)₅ (El Maadi et al., 1995a). In this structure, the Sr₂Ni₅(P₂O₇)₅ matrix forms tunnels of large dimension (3.64 × 9.28 Å) in which are found four individual columns of K⁺ ions. The conductivity of this material has not been established.

The structure of K₂Sr₃Mn₂(P₂O₇)₃ described here (Fig. 1 and 2) does not resemble any of its known mono- or bimetallic parents, e.g. Sr₂P₂O₇ (Grenier & Masse, 1969), Mn₂P₂O₇ (Lukaszewicz & Smajkiewicz, 1961), K₂SrP₂O₇ (Trunov et al., 1991) or K₂MnP₂O₇ (El Maadi et al., 1994); SrMnP₂O₇ and K₄P₂O₇ are unknown. Thus, one cannot view the structure of K₂Mn₂Sr₃(P₂O₇)₃ as a simple substitution of potassium and manganese into an Sr₂P₂O₇ matrix, for example.

The structure of K₂Sr₃Mn₂(P₂O₇)₃ is built up from [Sr₃Mn₂P₄O₁₆] ∞ units in the form of SrO_8–10, MnO₅ and PO₄ coordination polyhedra, which create tunnels parallel to the [010] direction. Each tunnel is of dimensions, 5.43 × 9.28 Å. In each of these tunnels are found two columns of K⁺ ions. Tunnels, centered about (1/2, y, 1/2) and (1/2, y, 0), are delimited by four PO₄ tetrahedra, two MnO₅ square pyramids and two SrO_8–10 polyhedra. Fig. 1, a projection on the (010) plane, shows these tunnels. Within the [Sr₃Mn₂P₄O₁₆] ∞ units, (Sr₃O₂₁) ∞ repeat units in the form of ribbons extend in the [010] direction.

Atoms Sr1, Sr2 and Sr3 display nine-, eight- or ten-coordination, with average Sr—O distances of 2.717 (11), 2.601 (12) and 2.783 (12) Å, respectively. Atoms K1 and K2 display nine- and seven-coordination, respectively. The average K—O distances of 2.983 (15) and 2.933 (15) Å comparable to those in K₂SrP₂O₇ (Trunov et al., 1991), K₂CuP₂O₇ (El Maadi et al., 1995b) and K₂CdP₂O₇ (Faggiani et al., 1976). Both Mn atoms have square-pyramidal geometry, with Mn—O distances of 2.112 (15) and 2.120 (14) Å.

The valence-bond sums (Brown, 1981) for the cations are: Sr1 1.927, Sr2 2.48, Sr3 1.819, Mn1 2.01, Mn2, 2.05, K1 0.98 and K2 0.87. These sums are normal for Mn atoms and for Sr1 and Sr3. The high total for Sr2, which has the lowest coordination number of the three Sr atoms, is puzzling. We have often noted low totals (as seen for K2) for atoms which are mobile in their environment and thus involved in conductivity.

The space group is correctly chosen as P2₁. While the metal atoms and two of the diphosphate groups may be placed on positions of mirror symmetry in the centric space group P2₁/m (mandating an eclipsed conformation of the P₂O₇ groups), the third diphosphate group is disordered when forced to have the bonded O—P—O—P—O atoms on a mirror plane. This disorder is completely resolved in the non-centrosymmetric space group P2₁. This diphosphate group is seen in a pseudo-eclipsed conformation (the average O—P—P—O angle is 69.8°).

Thus, the transition from host matrices built up of one cation with `covalent tendencies' and diphosphate groups to matrices built of two such cations of different sizes and diphosphate groups appears to lead to matrices with tunnels of larger size. Evidence suggests that the presence of strontium or palladium in the solid matrix is of particular importance in the construction of large tunnels.

S2. Experimental

Crystals of K₂Sr₃Mn₂(P₂O₇)₃ were prepared by fusing a stoichiometric mixture of K₂CO₃, SrCO₃, MnCO₃ and (NH₄)₂HPO₄ according to the equation

K₂CO₃ + 2MnCO₃ + 3SrCO₃ + 6(NH₄)₂HPO₄ → K₂Mn₂Sr₃(P₂O₇)₃ + 6CO₂ + 12NH₃ + 9H₂O.

The reaction mixture was ground together and heated slowly, with intermittent grinding, to the temperature of fusion, 1073 K, in a porcelain crucible. The molten material obtained was held at this temperature for 24 h and then subjected to controlled cooling (6 K h^-1) to 473 K after which, the furnace was turned off. Violet crystals were obtained.

Computing details

Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997).

Figures

	Fig. 1. View of the asymmetric unit of K2Sr3Mn2(P2O7)3. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. Projection of K2Sr3Mn2(P2O7)3 on the (010) plane. The Sr–O polyhedra, MnO5 pentagonal pyramids and PO4 tetrahedra are shown as solid forms surrounding the tunnels in each of which are seen two columns of K^+ ions. The c axis is horizontal, with the a axis subtending an angle of 100.19°.

Dipotassium dimanganese tristrontium tris(diphosphate)

Crystal data

K2Sr3Mn2(P2O7)3	F(000) = 920
Mr = 972.76	Dx = 3.331 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 13.285 (6) Å	Cell parameters from 47 reflections
b = 5.394 (2) Å	θ = 3.5–9.6°
c = 13.750 (6) Å	µ = 10.49 mm^−1
β = 100.19 (3)°	T = 293 K
V = 969.8 (7) Å^3	Chunk, violet
Z = 2	0.1 × 0.1 × 0.1 mm

Data collection

Syntex P4 four-circle diffractometer	2492 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.082
Graphite monochromator	θmax = 30.0°, θmin = 2.0°
θ/2θ scans	h = −18→1
Absorption correction: ψ scan (XEMP; Siemens, 1991)	k = −1→7
Tmin = 0.87, Tmax = 0.91	l = −19→19
4061 measured reflections	3 standard reflections every 97 reflections
3650 independent reflections	intensity decay: 0.0%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0843P)^2 + 3.6291P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.066	(Δ/σ)max = 0.015
wR(F^2) = 0.174	Δρmax = 0.07 e Å^−3
S = 1.01	Δρmin = −0.05 e Å^−3
3650 reflections	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
307 parameters	Extinction coefficient: 0.0018 (5)
0 restraints	Absolute structure: Flack (1983), 0000 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.22 (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. The y coordinate of Sr1 was fixed to establish the origin of the space group. Refinement of the structure in both enantiomorphic forms did not lead to determination of the absolute structure as reflected in the Friedel parameter.

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

	x	y	z	Uiso*/Ueq
Sr1	0.77594 (9)	0.3794	0.16320 (9)	0.0152 (3)
Sr2	0.00802 (10)	0.8596 (8)	0.25110 (10)	0.0241 (3)
Sr3	0.24486 (9)	0.3217 (4)	0.35145 (9)	0.0169 (4)
Mn1	0.77690 (16)	0.3731 (9)	−0.11841 (14)	0.0188 (5)
Mn2	0.20860 (16)	0.3433 (8)	0.62390 (15)	0.0187 (6)
K1	0.5683 (2)	0.3732 (13)	0.3981 (2)	0.0284 (9)
K2	0.4392 (2)	0.3345 (13)	0.0878 (3)	0.0328 (10)
P1	0.0706 (2)	0.3773 (12)	0.1296 (2)	0.0130 (7)
O11	0.1205 (14)	0.136 (3)	0.1733 (10)	0.032 (4)
O12	0.1356 (13)	0.594 (3)	0.1779 (12)	0.035 (4)
O13	−0.0387 (7)	0.401 (5)	0.1386 (7)	0.041 (5)
O14	0.0797 (6)	0.382 (4)	0.0147 (6)	0.019 (2)
P2	0.1863 (3)	0.3778 (14)	−0.0283 (2)	0.0169 (9)
O21	0.2431 (10)	0.136 (3)	0.0039 (10)	0.020 (3)
O22	0.1558 (8)	0.385 (4)	−0.1392 (6)	0.031 (3)
O23	0.2464 (12)	0.612 (3)	0.0113 (11)	0.027 (4)
P3	0.1866 (3)	0.8382 (12)	0.4787 (2)	0.0145 (9)
O31	0.2461 (10)	0.605 (3)	0.5197 (10)	0.017 (3)
O32	0.2381 (10)	1.077 (3)	0.5219 (10)	0.018 (3)
O33	0.1666 (8)	0.833 (4)	0.3670 (7)	0.029 (3)
O34	0.0737 (7)	0.834 (3)	0.5105 (6)	0.021 (3)
P4	0.0550 (2)	0.8463 (12)	0.6230 (2)	0.0142 (9)
O41	−0.0570 (7)	0.817 (4)	0.6235 (7)	0.033 (4)
O42	0.1175 (12)	0.627 (3)	0.6770 (10)	0.019 (3)
O43	0.1004 (12)	1.090 (3)	0.6667 (11)	0.030 (4)
P5	0.5921 (3)	0.3766 (13)	0.6916 (3)	0.0183 (8)
O51	0.6570 (9)	0.503 (3)	0.7808 (9)	0.038 (4)
O52	0.5955 (9)	0.525 (3)	0.5987 (9)	0.028 (3)
O53	0.6172 (10)	0.103 (3)	0.6877 (11)	0.040 (4)
O54	0.4739 (7)	0.394 (3)	0.7045 (7)	0.033 (3)
P6	0.4053 (3)	0.3856 (13)	0.7918 (3)	0.0177 (8)
O61	0.3734 (8)	0.654 (3)	0.8014 (9)	0.030 (3)
O62	0.4654 (8)	0.276 (3)	0.8850 (8)	0.035 (3)
O63	0.3165 (8)	0.219 (3)	0.7426 (8)	0.025 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sr1	0.0144 (5)	0.0154 (8)	0.0161 (5)	−0.0015 (7)	0.0035 (4)	−0.0001 (7)
Sr2	0.0187 (6)	0.0287 (8)	0.0254 (6)	−0.0025 (8)	0.0054 (4)	−0.0027 (7)
Sr3	0.0133 (5)	0.0196 (10)	0.0183 (5)	0.0005 (7)	0.0045 (4)	0.0007 (7)
Mn1	0.0260 (10)	0.0123 (14)	0.0177 (9)	0.0020 (15)	0.0030 (7)	0.0022 (13)
Mn2	0.0253 (10)	0.0117 (16)	0.0194 (9)	0.0022 (13)	0.0050 (8)	−0.0013 (13)
K1	0.0182 (13)	0.028 (2)	0.0362 (16)	−0.001 (2)	−0.0041 (11)	−0.003 (2)
K2	0.0256 (15)	0.029 (3)	0.0398 (18)	−0.002 (2)	−0.0047 (13)	0.005 (2)
P1	0.0173 (14)	0.009 (2)	0.0130 (13)	0.004 (2)	0.0026 (11)	−0.003 (2)
O11	0.066 (11)	0.021 (9)	0.010 (5)	0.020 (8)	0.007 (6)	0.005 (6)
O12	0.044 (9)	0.025 (10)	0.041 (9)	−0.018 (8)	0.021 (7)	−0.008 (8)
O13	0.016 (4)	0.083 (15)	0.026 (5)	0.011 (9)	0.009 (4)	0.005 (10)
O14	0.018 (4)	0.023 (7)	0.014 (4)	0.007 (7)	−0.002 (3)	0.000 (7)
P2	0.0211 (15)	0.016 (3)	0.0142 (13)	0.000 (2)	0.0062 (12)	0.000 (2)
O21	0.017 (6)	0.021 (8)	0.027 (7)	−0.004 (6)	0.014 (5)	0.001 (6)
O22	0.038 (6)	0.044 (10)	0.012 (4)	0.001 (10)	0.009 (4)	0.003 (9)
O23	0.029 (8)	0.027 (9)	0.027 (7)	0.000 (7)	0.011 (6)	−0.009 (7)
P3	0.0187 (14)	0.010 (3)	0.0156 (14)	0.003 (2)	0.0065 (11)	0.001 (2)
O31	0.013 (6)	0.013 (7)	0.028 (7)	−0.001 (5)	0.011 (5)	0.000 (6)
O32	0.016 (6)	0.018 (7)	0.020 (6)	−0.009 (5)	0.007 (5)	−0.004 (5)
O33	0.034 (5)	0.036 (10)	0.017 (4)	−0.005 (8)	0.007 (4)	0.006 (7)
O34	0.017 (4)	0.026 (9)	0.018 (4)	0.000 (6)	0.000 (3)	0.004 (7)
P4	0.0134 (13)	0.015 (3)	0.0152 (13)	−0.002 (2)	0.0037 (11)	−0.002 (2)
O41	0.016 (4)	0.063 (13)	0.022 (4)	−0.006 (7)	0.011 (4)	−0.015 (8)
O42	0.015 (8)	0.017 (7)	0.016 (6)	−0.005 (6)	0.008 (5)	−0.004 (6)
O43	0.042 (9)	0.024 (9)	0.022 (6)	−0.020 (7)	0.006 (6)	−0.009 (6)
P5	0.0147 (14)	0.015 (2)	0.0259 (16)	0.001 (2)	0.0061 (12)	0.000 (2)
O51	0.025 (6)	0.059 (12)	0.022 (6)	−0.002 (7)	−0.012 (5)	0.004 (7)
O52	0.030 (6)	0.026 (7)	0.029 (6)	0.004 (6)	0.006 (5)	0.001 (6)
O53	0.031 (7)	0.026 (9)	0.060 (9)	0.012 (7)	0.003 (7)	−0.009 (8)
O54	0.021 (5)	0.054 (10)	0.025 (5)	−0.001 (8)	0.009 (4)	0.006 (8)
P6	0.0159 (14)	0.017 (2)	0.0200 (15)	−0.001 (2)	0.0032 (11)	−0.002 (2)
O61	0.016 (5)	0.032 (9)	0.044 (7)	−0.012 (6)	0.011 (5)	−0.012 (7)
O62	0.029 (6)	0.041 (9)	0.032 (6)	0.011 (7)	−0.003 (5)	0.008 (7)
O63	0.025 (6)	0.016 (7)	0.031 (6)	−0.011 (5)	0.003 (5)	0.004 (6)

Geometric parameters (Å, º)

Sr1—O61^i	2.449 (13)	K1—O52	2.839 (13)
Sr1—O13^ii	2.547 (10)	K1—O52^i	2.882 (14)
Sr1—O21^iii	2.655 (14)	K1—O31^i	2.908 (14)
Sr1—O63^iv	2.667 (12)	K1—O54^i	2.951 (18)
Sr1—O42^i	2.753 (17)	K1—O54^iv	3.149 (19)
Sr1—O23^v	2.771 (16)	K1—O61^i	3.206 (14)
Sr1—O43^i	2.847 (16)	K1—O63^iv	3.258 (14)
Sr1—O22^v	2.86 (2)	K2—O62^iv	2.693 (16)
Sr1—O22^iii	2.91 (2)	K2—O61^i	2.851 (12)
Sr2—O33	2.410 (10)	K2—O21	2.864 (14)
Sr2—O22^vi	2.437 (10)	K2—O62^xi	2.888 (12)
Sr2—O43^vii	2.457 (18)	K2—O51^i	2.985 (16)
Sr2—O11^viii	2.483 (19)	K2—O23	2.991 (17)
Sr2—O42^ix	2.536 (17)	K2—O62^i	3.264 (17)
Sr2—O12	2.557 (19)	P1—O13	1.485 (10)
Sr2—O13	2.92 (2)	P1—O12	1.533 (17)
Sr2—O41^ix	3.015 (19)	P1—O11	1.536 (16)
Sr3—O53^iv	2.509 (15)	P1—O14	1.605 (9)
Sr3—O41^vii	2.579 (9)	O14—P2	1.628 (9)
Sr3—O52^i	2.650 (13)	P2—O22	1.506 (9)
Sr3—O32^x	2.705 (13)	P2—O21	1.534 (16)
Sr3—O31	2.771 (14)	P2—O23	1.540 (17)
Sr3—O33^x	2.85 (2)	P3—O33	1.512 (10)
Sr3—O11	2.882 (16)	P3—O32	1.530 (14)
Sr3—O12	2.955 (18)	P3—O31	1.538 (15)
Sr3—O51^i	2.967 (15)	P3—O34	1.636 (10)
Sr3—O33	2.97 (2)	O34—P4	1.611 (10)
Mn1—O51^xi	2.042 (12)	P4—O41	1.497 (10)
Mn1—O23^v	2.101 (16)	P4—O43	1.525 (16)
Mn1—O12^v	2.151 (17)	P4—O42	1.554 (14)
Mn1—O21^iii	2.169 (15)	P5—O52	1.514 (13)
Mn1—O11^iii	2.190 (17)	P5—O53	1.516 (18)
Mn2—O63	2.082 (11)	P5—O51	1.528 (13)
Mn2—O32^x	2.092 (14)	P5—O54	1.614 (10)
Mn2—O31	2.133 (14)	O54—P6	1.631 (10)
Mn2—O43^x	2.139 (16)	P6—O62	1.506 (11)
Mn2—O42	2.158 (15)	P6—O61	1.519 (18)
K1—O53^iv	2.824 (16)	P6—O63	1.539 (12)
K1—O32^i	2.834 (15)
O61^i—Sr1—O13^ii	152.3 (7)	O23^v—Mn1—O21^iii	82.9 (5)
O61^i—Sr1—O21^iii	118.3 (4)	O12^v—Mn1—O21^iii	151.3 (6)
O13^ii—Sr1—O21^iii	78.9 (5)	O51^xi—Mn1—O11^iii	90.2 (6)
O61^i—Sr1—O63^iv	77.7 (5)	O23^v—Mn1—O11^iii	148.6 (6)
O13^ii—Sr1—O63^iv	124.9 (6)	O12^v—Mn1—O11^iii	84.9 (5)
O21^iii—Sr1—O63^iv	94.6 (4)	O21^iii—Mn1—O11^iii	89.5 (6)
O61^i—Sr1—O42^i	85.2 (4)	O63—Mn2—O32^x	96.9 (5)
O13^ii—Sr1—O42^i	75.9 (5)	O63—Mn2—O31	121.9 (5)
O21^iii—Sr1—O42^i	154.8 (4)	O32^x—Mn2—O31	84.9 (4)
O63^iv—Sr1—O42^i	99.6 (4)	O63—Mn2—O43^x	89.0 (5)
O61^i—Sr1—O23^v	86.9 (5)	O32^x—Mn2—O43^x	87.8 (6)
O13^ii—Sr1—O23^v	82.4 (5)	O31—Mn2—O43^x	148.8 (5)
O21^iii—Sr1—O23^v	62.8 (4)	O63—Mn2—O42	108.2 (5)
O63^iv—Sr1—O23^v	142.3 (4)	O32^x—Mn2—O42	153.7 (5)
O42^i—Sr1—O23^v	113.3 (5)	O31—Mn2—O42	88.2 (6)
O61^i—Sr1—O43^i	113.9 (5)	O43^x—Mn2—O42	85.2 (5)
O13^ii—Sr1—O43^i	70.1 (5)	O53^iv—K1—O32^i	131.0 (5)
O21^iii—Sr1—O43^i	117.1 (5)	O53^iv—K1—O52	103.3 (4)
O63^iv—Sr1—O43^i	64.8 (4)	O32^i—K1—O52	63.9 (4)
O42^i—Sr1—O43^i	53.2 (4)	O53^iv—K1—O52^i	71.8 (4)
O23^v—Sr1—O43^i	151.4 (5)	O32^i—K1—O52^i	152.0 (4)
O61^i—Sr1—O22^v	81.0 (4)	O52—K1—O52^i	98.0 (3)
O13^ii—Sr1—O22^v	72.1 (6)	O53^iv—K1—O31^i	176.1 (5)
O21^iii—Sr1—O22^v	111.7 (4)	O32^i—K1—O31^i	52.7 (3)
O63^iv—Sr1—O22^v	151.8 (4)	O52—K1—O31^i	79.2 (4)
O42^i—Sr1—O22^v	60.1 (4)	O52^i—K1—O31^i	105.1 (4)
O23^v—Sr1—O22^v	53.2 (4)	O53^iv—K1—O54^i	96.1 (4)
O43^i—Sr1—O22^v	108.6 (4)	O32^i—K1—O54^i	127.5 (4)
O61^i—Sr1—O22^iii	140.2 (4)	O52—K1—O54^i	134.2 (4)
O13^ii—Sr1—O22^iii	67.3 (6)	O52^i—K1—O54^i	49.9 (3)
O21^iii—Sr1—O22^iii	53.0 (4)	O31^i—K1—O54^i	80.0 (4)
O63^iv—Sr1—O22^iii	65.8 (4)	O53^iv—K1—O54^iv	49.3 (4)
O42^i—Sr1—O22^iii	115.2 (3)	O32^i—K1—O54^iv	84.6 (4)
O23^v—Sr1—O22^iii	112.2 (4)	O52—K1—O54^iv	99.2 (4)
O43^i—Sr1—O22^iii	64.7 (4)	O52^i—K1—O54^iv	120.9 (3)
O22^v—Sr1—O22^iii	138.6 (4)	O31^i—K1—O54^iv	133.6 (4)
O33—Sr2—O22^vi	177.8 (3)	O54^i—K1—O54^iv	124.3 (4)
O33—Sr2—O43^vii	100.1 (5)	O53^iv—K1—O61^i	97.5 (4)
O22^vi—Sr2—O43^vii	78.1 (5)	O32^i—K1—O61^i	97.8 (4)
O33—Sr2—O11^viii	78.3 (5)	O52—K1—O61^i	158.4 (3)
O22^vi—Sr2—O11^viii	103.5 (5)	O52^i—K1—O61^i	94.0 (4)
O43^vii—Sr2—O11^viii	178.2 (6)	O31^i—K1—O61^i	80.4 (4)
O33—Sr2—O42^ix	109.5 (5)	O54^i—K1—O61^i	47.3 (4)
O22^vi—Sr2—O42^ix	68.9 (5)	O54^iv—K1—O61^i	89.8 (3)
O43^vii—Sr2—O42^ix	71.2 (4)	O53^iv—K1—O63^iv	88.1 (4)
O11^viii—Sr2—O42^ix	108.3 (6)	O32^i—K1—O63^iv	61.2 (3)
O33—Sr2—O12	70.4 (5)	O52—K1—O63^iv	114.8 (4)
O22^vi—Sr2—O12	111.3 (5)	O52^i—K1—O63^iv	144.9 (3)
O43^vii—Sr2—O12	109.4 (6)	O31^i—K1—O63^iv	93.5 (3)
O11^viii—Sr2—O12	71.0 (4)	O54^i—K1—O63^iv	106.7 (3)
O42^ix—Sr2—O12	179.3 (6)	O54^iv—K1—O63^iv	44.6 (3)
O33—Sr2—O13	112.3 (6)	O61^i—K1—O63^iv	59.6 (4)
O22^vi—Sr2—O13	68.3 (6)	O62^iv—K2—O61^i	83.3 (4)
O43^vii—Sr2—O13	69.9 (5)	O62^iv—K2—O21	139.4 (5)
O11^viii—Sr2—O13	111.5 (4)	O61^i—K2—O21	137.2 (5)
O42^ix—Sr2—O13	126.5 (4)	O62^iv—K2—O62^xi	95.6 (4)
O12—Sr2—O13	54.0 (4)	O61^i—K2—O62^xi	103.6 (4)
O33—Sr2—O41^ix	66.1 (5)	O21—K2—O62^xi	80.0 (4)
O22^vi—Sr2—O41^ix	113.2 (6)	O62^iv—K2—O51^i	133.4 (4)
O43^vii—Sr2—O41^ix	107.8 (4)	O61^i—K2—O51^i	84.2 (4)
O11^viii—Sr2—O41^ix	70.7 (4)	O21—K2—O51^i	64.1 (4)
O42^ix—Sr2—O41^ix	53.2 (4)	O62^xi—K2—O51^i	131.1 (5)
O12—Sr2—O41^ix	126.3 (4)	O62^iv—K2—O23	87.7 (5)
O13—Sr2—O41^ix	177.1 (5)	O61^i—K2—O23	166.2 (5)
O53^iv—Sr3—O41^vii	142.6 (6)	O21—K2—O23	52.0 (4)
O53^iv—Sr3—O52^i	80.8 (5)	O62^xi—K2—O23	87.6 (4)
O41^vii—Sr3—O52^i	135.2 (5)	O51^i—K2—O23	94.6 (4)
O53^iv—Sr3—O32^x	128.2 (4)	O62^iv—K2—O62^i	129.5 (4)
O41^vii—Sr3—O32^x	72.5 (4)	O61^i—K2—O62^i	48.6 (4)
O52^i—Sr3—O32^x	68.2 (4)	O21—K2—O62^i	90.4 (4)
O53^iv—Sr3—O31	87.0 (5)	O62^xi—K2—O62^i	84.2 (4)
O41^vii—Sr3—O31	75.9 (4)	O51^i—K2—O62^i	65.0 (4)
O52^i—Sr3—O31	103.4 (4)	O23—K2—O62^i	142.4 (4)
O32^x—Sr3—O31	62.7 (3)	O13—P1—O12	112.4 (12)
O53^iv—Sr3—O33^x	149.7 (5)	O13—P1—O11	113.7 (12)
O41^vii—Sr3—O33^x	66.9 (5)	O12—P1—O11	107.8 (8)
O52^i—Sr3—O33^x	73.0 (4)	O13—P1—O14	109.0 (5)
O32^x—Sr3—O33^x	54.3 (3)	O12—P1—O14	106.3 (9)
O31—Sr3—O33^x	113.3 (4)	O11—P1—O14	107.2 (9)
O53^iv—Sr3—O11	111.0 (5)	P1—O14—P2	125.4 (5)
O41^vii—Sr3—O11	71.8 (4)	O22—P2—O21	110.1 (10)
O52^i—Sr3—O11	108.8 (4)	O22—P2—O23	111.6 (10)
O32^x—Sr3—O11	117.7 (5)	O21—P2—O23	113.4 (6)
O31—Sr3—O11	145.1 (5)	O22—P2—O14	105.8 (5)
O33^x—Sr3—O11	65.2 (4)	O21—P2—O14	108.7 (8)
O53^iv—Sr3—O12	78.4 (5)	O23—P2—O14	106.9 (9)
O41^vii—Sr3—O12	76.3 (4)	O33—P3—O32	113.3 (9)
O52^i—Sr3—O12	140.0 (4)	O33—P3—O31	110.1 (9)
O32^x—Sr3—O12	148.8 (5)	O32—P3—O31	112.3 (6)
O31—Sr3—O12	109.2 (5)	O33—P3—O34	105.5 (5)
O33^x—Sr3—O12	112.7 (4)	O32—P3—O34	106.0 (8)
O11—Sr3—O12	50.3 (4)	O31—P3—O34	109.1 (8)
O53^iv—Sr3—O51^i	78.6 (5)	P4—O34—P3	124.1 (5)
O41^vii—Sr3—O51^i	128.1 (5)	O41—P4—O43	114.4 (10)
O52^i—Sr3—O51^i	52.4 (3)	O41—P4—O42	111.4 (10)
O32^x—Sr3—O51^i	109.5 (4)	O43—P4—O42	109.1 (7)
O31—Sr3—O51^i	153.3 (3)	O41—P4—O34	108.8 (5)
O33^x—Sr3—O51^i	73.5 (4)	O43—P4—O34	107.2 (9)
O11—Sr3—O51^i	61.7 (4)	O42—P4—O34	105.4 (8)
O12—Sr3—O51^i	90.0 (4)	O52—P5—O53	116.4 (9)
O53^iv—Sr3—O33	74.4 (5)	O52—P5—O51	110.2 (9)
O41^vii—Sr3—O33	68.9 (5)	O53—P5—O51	111.5 (9)
O52^i—Sr3—O33	144.9 (4)	O52—P5—O54	103.7 (7)
O32^x—Sr3—O33	109.0 (4)	O53—P5—O54	106.6 (9)
O31—Sr3—O33	51.5 (3)	O51—P5—O54	107.9 (7)
O33^x—Sr3—O33	135.7 (4)	P5—O54—P6	139.5 (7)
O11—Sr3—O33	103.3 (4)	O62—P6—O61	114.4 (8)
O12—Sr3—O33	57.9 (4)	O62—P6—O63	113.3 (8)
O51^i—Sr3—O33	141.3 (4)	O61—P6—O63	112.9 (7)
O51^xi—Mn1—O23^v	120.8 (6)	O62—P6—O54	110.8 (7)
O51^xi—Mn1—O12^v	113.0 (6)	O61—P6—O54	103.8 (9)
O23^v—Mn1—O12^v	87.3 (7)	O63—P6—O54	100.2 (7)
O51^xi—Mn1—O21^iii	95.0 (6)

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