KZn(HP₂O₇)·2H₂O and KMn(HP₂O₇)·2H₂O: acid pyrophosphate metallates(II) with layer structures

The crystal structures of the isomorphous title compounds, namely potassium zinc hydrogen pyrophosphate dihydrate and potassium manganese hydrogen pyrophosphate dihydrate, consist of acidic pyrophosphate-metallate(II) layers joined by K⁺ ions and hydrogen-bridging bonds. The Zn²⁺/Mn²⁺ ions are octahedrally surrounded by four pyrophosphate O atoms and by two water mol­ecules. The (HP₂O₇)^3- anions exhibit eclipsed conformations. The metal ions and water O atoms lie on mirror planes, as does the central O atom of the (HP₂O₇)^3- anion.

S1. Comment

Compared to anhydrous diphosphates (El Bali et al., 2001, and references therein), little information is available in the literature concerning the crystal structures of acidic metal diphosphates and hydrated metal diphosphates. Structural data have only been reported for the following compounds: CaNH₄HP₂O₇ (Mathew & Schroeder, 1977), Cr(NH₃)₄HP₂O₇·2H₂O (Haromy et al., 1984), K₃Cu₂[(P₂O₇)(HP₂O₇)] (Effenberger, 1987), Ca₂KH₃(P₂O₇)₂·2H₂O (Mathew et al., 1993) and Cr(HP₂O₇)(NH₃)₃ (Haromy et al., 1999). The biological applications of acidic metal diphosphates are well known, viz. their role in some enzyme-catalyzed reaction processes (Haromy et al., 1984) and their use as inhibitors in the formation and dissolution of apatite crystals in vitro (Mathew et al., 1993). The title compounds, KHZnP₂O₇·2H₂O, (I), and KHMnP₂O₇·2H₂O, (II), are isotypic. The octahedral coordination around the Mn/Zn atoms and the pyrophosphate groups in (I) and (II) are shown in Fig. 1, together with the atom-numbering schemes. The three-dimensional structure is built from acidic pyrophosphate–metallate(II) [M = Zn in (I) and Mn in (II)] layers stacked along the c axis (Fig. 2), alternating with layers of K⁺ cations. The Zn²⁺/Mn²⁺ ions are octahedrally surrounded by four O atoms from three different pyrophosphate anions, and by two water molecules. The angle between the plane through water molecule OW5 and the M²⁺—OW5 bond is about 141.8° (143.3°), while the corresponding angle involving OW6 is significantly smaller, ϕ = 107.8° (108.6°) [items in parentheses are for the manganese compound, (II)]. We attribute these quite different values to differences in the hydrogen-bridging bonds from H5W (H6W) to O2 (O4) of the diphosphate anions, which basically result from a slightly longer O5W—O2 distance of ~2.83 Å compared to O6W—O4 of ~2.67 Å. Apparently, the coordination mode of water to a transition metal ion, expressed by the angle between the plane through the water molecule and the M²⁺—OH₂ bond, is quite flexible.

The powder reflectance spectrum of KHMnP₂O₇·2H₂O, (II) (Fig. 3a), shows the spin-forbidden absorption bands typically found for Mn²⁺. The transitions ⁶A_{1 g} → ⁴T_{1 g}, ⁶A_{1 g} → ⁴T_{2 g}, ⁶A_{1 g} → (⁴E_g,⁴A_{1 g}) and ⁶A_{1 g} → ⁴T_{2 g}(D) can be recognized. Thus, the spectrum provides, in addition to the X-ray study, clear evidence for a manganese(II) hydrogen pyrophosphate instead of a manganese(III) compound. The band positions are similar to those found for anhydrous manganese(II) phosphates, such as Mn₂P₂O₇, Mn₂P₄O₁₂ and Mn₂Si(P₂O₇)₂ (Glaum et al., 2002), and for the hexaqua complex of Mn²⁺ (Figgis & Hitchman, 2000). The Raman spectrum of (II) (Fig. 3 b) is in agreement with the different P—O bond distances found in the pyrophosphate anions (Table 2). We attribute the strong emission at ν = 1015 cm^-1 to the symmetric stretching vibration of the external PO₃ groups, while the weaker signals at ν = 1123 and 1183 cm^-1 most likely belong to asymmetric stretches of the external PO₃ groups (Rulmont et al., 1991). The signal at 787 cm^-1 might be assigned to the symmetric stretch of the P—O—P bridge.

S2. Experimental

The title compounds were obtained by mixing equimolar quantities of K₄P₂O₇ and ZnCl₂·4H₂O [or MnCl₂·4H₂O in the case of (II)] in a few ml of concentrated HCl. The former reactant was obtained by heating K₂HPO₄ at 873 K for 6 h. From the solution left at room temperature, well shaped colourless [or rose coloured in the case of (II)] crystals with edge-lengths up to 1 mm were deposited after 2–3 d.

S3. Refinement

All H atoms were located from difference Fourier maps. Within the limits of the method, the positions of the H atoms were refined allowing for isotropic displacement parameters. A split position with half-occupancy (around a center of inversion) was introduced for the acid H2 atom. Attempts to resolve this splitting in non-centrosymmetric subgroups of Pnma did not lead to an improved refinement.

Computing details

Data collection: XSCANS (Siemens, 1996) for (I); CAD-4 EXPRESS (Enraf-Nonius, 1994) for (II). Cell refinement: XSCANS for (I); CAD-4 EXPRESS for (II). Data reduction: SHELXTL (Siemens, 1991) for (I); XCAD4 (Harms & Wocadlo, 1995) for (II). Program(s) used to solve structure: SHELXTL for (I); SHELXS97 (Sheldrick, 1997) for (II). Program(s) used to refine structure: SHELXTL for (I); SHELXL97 (Sheldrick, 1997) for (II). Molecular graphics: SHELXTL for (I); ATOMS (Dowty, 1998) for (II). Software used to prepare material for publication: SHELXTL for (I).

Figures

	Fig. 1. View of the [MO4(H2O)2]^2+ coordination polyhedra for (a) M = Zn and (b) M = Mn, and the pyrophosphate groups for (c) M = Zn and (d) M = Mn in KMHP2O7·2H2O. Ellipsoids are shown at the 75% probability level.
	Fig. 2. Projections of the crystal structure of KHMP2O7·2H2O (M = Zn, Mn) (a) along the b axis and (b) along the c axis, with schematic coordination polyhedra. Key: dark grey polyhedra = [MO6], light grey polyhedra = [P2O7] groups, large grey circles = K^+ ions, small black circles = H^+ ions, O—H bonds are bold black bonds and hydrogen-bridging bonds are thin lines.
	Fig. 3. (a) Powder reflectance spectrum and (b) the Raman spectrum for KHMnP2O7·2H2O. Assignement of the electronic transitions in (a): (I) ^6A1 g → ^4T1 g, (II) ^6A1 g → ^4T2 g, (III) ^6A1 g → (^4Eg,^4A1 g), (IV) ^6A1 g → ^4T2 g(D).

(I) potassium zinc hydrogen pyrophosphate dihydrate

Crystal data

KZn(HP2O7)(H2O)2	Dx = 2.677 Mg m^−3
Mr = 315.45	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 40 reflections
a = 15.4727 (12) Å	θ = 5.3–17.5°
b = 7.7820 (9) Å	µ = 4.10 mm^−1
c = 6.5009 (7) Å	T = 293 K
V = 782.76 (14) Å^3	Prismatic, colourless
Z = 4	0.4 × 0.4 × 0.3 mm
F(000) = 624

Data collection

Bruker P4 diffractometer	692 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.025
Graphite monochromator	θmax = 25.0°, θmin = 2.6°
2θ/ω scans	h = −1→18
Absorption correction: ψ scan (North et al., 1968)	k = −9→1
Tmin = 0.589, Tmax = 0.986	l = −1→7
1080 measured reflections	3 standard reflections every 97 reflections
738 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	All H-atom parameters refined
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0335P)^2 + 0.9013P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
738 reflections	Δρmax = 0.43 e Å^−3
77 parameters	Δρmin = −0.38 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0275 (18)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.69589 (3)	0.2500	0.56130 (7)	0.0102 (2)
K1	0.96483 (6)	0.2500	−0.11827 (15)	0.0195 (3)
P1	0.86388 (5)	0.06111 (9)	0.36065 (11)	0.0088 (2)
O1	0.88760 (19)	0.2500	0.2742 (5)	0.0124 (6)
O2	0.92463 (13)	0.0311 (3)	0.5454 (3)	0.0148 (5)
H2	0.9717	−0.0006	0.4944	0.02 (2)*	0.50
O3	0.88466 (13)	−0.0567 (3)	0.1842 (3)	0.0141 (5)
O4	0.77097 (13)	0.0615 (3)	0.4290 (3)	0.0140 (5)
O5W	0.8937 (2)	−0.2500	0.8113 (5)	0.0173 (7)
H5W	0.895 (3)	−0.158 (6)	0.733 (7)	0.041 (12)*
O6W	0.7156 (2)	−0.2500	0.3182 (5)	0.0158 (7)
H6W	0.734 (3)	−0.168 (6)	0.386 (7)	0.045 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0093 (3)	0.0096 (3)	0.0117 (3)	0.000	0.00099 (19)	0.000
K1	0.0153 (5)	0.0267 (6)	0.0165 (5)	0.000	0.0003 (4)	0.000
P1	0.0087 (4)	0.0076 (4)	0.0101 (4)	−0.0001 (3)	0.0008 (3)	−0.0023 (3)
O1	0.0161 (15)	0.0079 (14)	0.0131 (14)	0.000	0.0050 (12)	0.000
O2	0.0131 (11)	0.0194 (11)	0.0120 (11)	0.0023 (9)	−0.0017 (9)	0.0015 (9)
O3	0.0115 (10)	0.0139 (10)	0.0170 (11)	0.0003 (8)	0.0007 (9)	−0.0053 (9)
O4	0.0095 (11)	0.0117 (10)	0.0208 (12)	−0.0011 (9)	0.0024 (9)	−0.0048 (9)
O5W	0.0237 (17)	0.0164 (15)	0.0118 (15)	0.000	0.0053 (14)	0.000
O6W	0.0179 (16)	0.0121 (15)	0.0173 (17)	0.000	0.0037 (14)	0.000

Geometric parameters (Å, º)

Zn1—O4^i	2.059 (2)	K1—Zn1^xi	3.5942 (11)
Zn1—O4	2.059 (2)	K1—P1	3.7807 (12)
Zn1—O3^ii	2.111 (2)	K1—P1^i	3.7807 (12)
Zn1—O3^iii	2.111 (2)	P1—O3	1.503 (2)
Zn1—O5W^iv	2.136 (3)	P1—O4	1.505 (2)
Zn1—O6W^ii	2.160 (3)	P1—O2	1.543 (2)
Zn1—K1^v	3.5942 (11)	P1—O1	1.6160 (14)
K1—O3^vi	2.805 (2)	O1—P1^i	1.6160 (14)
K1—O3^vii	2.805 (2)	O2—K1^xii	2.841 (2)
K1—O1	2.817 (3)	O3—Zn1^iv	2.111 (2)
K1—O6W^iv	2.822 (3)	O3—K1^vii	2.805 (2)
K1—O2^viii	2.841 (2)	O5W—Zn1^ii	2.136 (3)
K1—O2^ix	2.841 (2)	O5W—K1^x	2.963 (4)
K1—O5W^x	2.963 (4)	O6W—Zn1^iv	2.160 (3)
K1—O3^i	3.332 (2)	O6W—K1^ii	2.822 (3)
K1—O3	3.332 (2)
O4^i—Zn1—O4	90.82 (11)	O5W^x—K1—O3	82.97 (6)
O4^i—Zn1—O3^ii	177.29 (8)	O3^i—K1—O3	91.50 (7)
O4—Zn1—O3^ii	89.06 (8)	O3^vi—K1—Zn1^xi	35.91 (4)
O4^i—Zn1—O3^iii	89.06 (8)	O3^vii—K1—Zn1^xi	35.91 (4)
O4—Zn1—O3^iii	177.29 (8)	O1—K1—Zn1^xi	109.18 (7)
O3^ii—Zn1—O3^iii	90.93 (11)	O6W^iv—K1—Zn1^xi	177.50 (8)
O4^i—Zn1—O5W^iv	92.75 (9)	O2^viii—K1—Zn1^xi	107.28 (5)
O4—Zn1—O5W^iv	92.75 (9)	O2^ix—K1—Zn1^xi	107.28 (5)
O3^ii—Zn1—O5W^iv	84.55 (9)	O5W^x—K1—Zn1^xi	36.44 (6)
O3^iii—Zn1—O5W^iv	84.55 (9)	O3^i—K1—Zn1^xi	108.03 (4)
O4^i—Zn1—O6W^ii	88.02 (9)	O3—K1—Zn1^xi	108.03 (4)
O4—Zn1—O6W^ii	88.02 (9)	O3^vi—K1—P1	132.63 (6)
O3^ii—Zn1—O6W^ii	94.68 (9)	O3^vii—K1—P1	105.08 (5)
O3^iii—Zn1—O6W^ii	94.68 (9)	O1—K1—P1	22.929 (13)
O5W^iv—Zn1—O6W^ii	178.90 (13)	O6W^iv—K1—P1	73.25 (7)
O4^i—Zn1—K1^v	127.17 (6)	O2^viii—K1—P1	108.07 (5)
O4—Zn1—K1^v	127.17 (6)	O2^ix—K1—P1	140.94 (5)
O3^ii—Zn1—K1^v	51.22 (5)	O5W^x—K1—P1	75.55 (6)
O3^iii—Zn1—K1^v	51.22 (5)	O3^i—K1—P1	68.82 (4)
O5W^iv—Zn1—K1^v	55.47 (9)	O3—K1—P1	23.32 (4)
O6W^ii—Zn1—K1^v	123.43 (9)	Zn1^xi—K1—P1	109.03 (3)
O3^vi—K1—O3^vii	64.86 (9)	O3^vi—K1—P1^i	105.08 (5)
O3^vi—K1—O1	119.37 (7)	O3^vii—K1—P1^i	132.63 (6)
O3^vii—K1—O1	119.37 (7)	O1—K1—P1^i	22.929 (13)
O3^vi—K1—O6W^iv	143.02 (6)	O6W^iv—K1—P1^i	73.25 (7)
O3^vii—K1—O6W^iv	143.02 (6)	O2^viii—K1—P1^i	140.94 (5)
O1—K1—O6W^iv	73.32 (10)	O2^ix—K1—P1^i	108.07 (5)
O3^vi—K1—O2^viii	112.69 (7)	O5W^x—K1—P1^i	75.55 (6)
O3^vii—K1—O2^viii	75.08 (6)	O3^i—K1—P1^i	23.32 (4)
O1—K1—O2^viii	127.17 (6)	O3—K1—P1^i	68.82 (4)
O6W^iv—K1—O2^viii	70.78 (7)	Zn1^xi—K1—P1^i	109.03 (3)
O3^vi—K1—O2^ix	75.08 (6)	P1—K1—P1^i	45.76 (2)
O3^vii—K1—O2^ix	112.69 (7)	O3—P1—O4	115.53 (12)
O1—K1—O2^ix	127.17 (6)	O3—P1—O2	111.80 (12)
O6W^iv—K1—O2^ix	70.78 (7)	O4—P1—O2	110.65 (12)
O2^viii—K1—O2^ix	73.70 (9)	O3—P1—O1	103.93 (13)
O3^vi—K1—O5W^x	59.30 (7)	O4—P1—O1	108.52 (13)
O3^vii—K1—O5W^x	59.30 (7)	O2—P1—O1	105.67 (14)
O1—K1—O5W^x	72.74 (9)	O3—P1—K1	61.33 (8)
O6W^iv—K1—O5W^x	146.06 (10)	O4—P1—K1	129.56 (9)
O2^viii—K1—O5W^x	132.87 (6)	O2—P1—K1	116.63 (9)
O2^ix—K1—O5W^x	132.87 (6)	O1—P1—K1	42.78 (10)
O3^vi—K1—O3^i	90.86 (6)	P1—O1—P1^i	130.91 (19)
O3^vii—K1—O3^i	141.57 (4)	P1—O1—K1	114.29 (10)
O1—K1—O3^i	46.18 (4)	P1^i—O1—K1	114.29 (10)
O6W^iv—K1—O3^i	73.62 (6)	P1—O2—K1^xii	129.92 (12)
O2^viii—K1—O3^i	143.35 (6)	P1—O3—Zn1^iv	126.67 (12)
O2^ix—K1—O3^i	86.74 (6)	P1—O3—K1^vii	128.40 (11)
O5W^x—K1—O3^i	82.97 (6)	Zn1^iv—O3—K1^vii	92.87 (7)
O3^vi—K1—O3	141.57 (4)	P1—O3—K1	95.35 (9)
O3^vii—K1—O3	90.86 (6)	Zn1^iv—O3—K1	120.46 (8)
O1—K1—O3	46.18 (4)	K1^vii—O3—K1	89.14 (6)
O6W^iv—K1—O3	73.62 (6)	P1—O4—Zn1	131.60 (12)
O2^viii—K1—O3	86.74 (6)	Zn1^ii—O5W—K1^x	88.09 (11)
O2^ix—K1—O3	143.35 (6)	Zn1^iv—O6W—K1^ii	137.76 (15)

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

(II) potassium manganese(II) hydrogenpyrophosphate dihydrate

Crystal data

KMn(HP2O7)(H2O)2	F(000) = 604
Mr = 305.02	Dx = 2.508 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 21 reflections
a = 15.7186 (5) Å	θ = 5.0–25.0°
b = 7.8706 (5) Å	µ = 2.57 mm^−1
c = 6.5297 (5) Å	T = 293 K
V = 807.82 (8) Å^3	Prismatic, pink
Z = 4	0.30 × 0.30 × 0.30 mm

Data collection

Enraf Nonius CAD-4 diffractometer	2278 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Graphite monochromator	θmax = 40.0°, θmin = 2.6°
non–profiled ω scans	h = −22→28
Absorption correction: ψ scan Number of ψ scan sets used was 9. Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied 'North & al. (1968)'	k = −14→14
Tmin = 0.532, Tmax = 0.602	l = −11→11
17404 measured reflections	3 standard reflections every 60 min
2633 independent reflections	intensity decay: none

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)] = 0.024	Hydrogen site location: difference Fourier map
wR(F^2) = 0.061	All H-atom parameters refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0305P)^2 + 0.244P] where P = (Fo^2 + 2Fc^2)/3
2633 reflections	(Δ/σ)max = 0.002
79 parameters	Δρmax = 0.73 e Å^−3
0 restraints	Δρmin = −0.46 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
K	0.96310 (2)	0.2500	−0.11760 (5)	0.02138 (6)
Mn	0.694614 (11)	0.2500	0.55922 (3)	0.01119 (4)
P	0.866688 (13)	0.06286 (3)	0.36102 (3)	0.01013 (5)
O1	0.88963 (6)	0.2500	0.27658 (14)	0.01411 (15)
O2	0.92618 (5)	0.03270 (10)	0.54532 (10)	0.01680 (12)
H2	0.968 (2)	0.008 (6)	0.509 (6)	0.032 (9)*	0.50
O3	0.88784 (5)	−0.05244 (9)	0.18429 (11)	0.01651 (12)
O4	0.77556 (4)	0.06125 (8)	0.42890 (11)	0.01586 (12)
O5W	0.89678 (8)	−0.2500	0.80036 (17)	0.02169 (19)
H5W	0.8989 (13)	−0.174 (2)	0.721 (3)	0.038 (5)*
O6W	0.71626 (7)	−0.2500	0.33230 (17)	0.01878 (17)
H6W	0.7320 (13)	−0.167 (2)	0.390 (3)	0.039 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K	0.01792 (12)	0.02820 (14)	0.01803 (11)	0.000	0.00050 (9)	0.000
Mn	0.00991 (7)	0.01041 (7)	0.01323 (7)	0.000	0.00147 (5)	0.000
P	0.00958 (8)	0.00877 (8)	0.01204 (8)	0.00040 (6)	0.00046 (6)	−0.00204 (6)
O1	0.0171 (4)	0.0103 (3)	0.0149 (4)	0.000	0.0045 (3)	0.000
O2	0.0159 (3)	0.0210 (3)	0.0135 (2)	0.0030 (2)	−0.0022 (2)	0.0016 (2)
O3	0.0142 (2)	0.0155 (3)	0.0198 (3)	0.0003 (2)	0.0011 (2)	−0.0091 (2)
O4	0.0114 (2)	0.0127 (2)	0.0234 (3)	−0.00065 (19)	0.0044 (2)	−0.0040 (2)
O5W	0.0293 (5)	0.0195 (4)	0.0162 (4)	0.000	0.0069 (4)	0.000
O6W	0.0208 (4)	0.0138 (4)	0.0217 (4)	0.000	0.0031 (4)	0.000

Geometric parameters (Å, º)

K—O1	2.8211 (10)	Mn—O6W^ix	2.2676 (11)
K—O6W^i	2.8382 (12)	Mn—K^xi	3.6590 (4)
K—O3^ii	2.8456 (7)	P—O4	1.4995 (7)
K—O3^iii	2.8456 (7)	P—O3	1.5052 (7)
K—O2^iv	2.8472 (8)	P—O2	1.5424 (7)
K—O2^v	2.8472 (8)	P—O1	1.6136 (4)
K—O5W^vi	3.0236 (13)	P—H2	1.91 (4)
K—O3^vii	3.3093 (8)	O1—P^vii	1.6136 (4)
K—O3	3.3093 (8)	O2—K^xii	2.8472 (8)
K—Mn^viii	3.6590 (4)	O2—H2	0.72 (4)
K—P^vii	3.7727 (4)	O3—Mn^i	2.1828 (7)
K—P	3.7727 (4)	O3—K^iii	2.8456 (7)
Mn—O4^vii	2.1330 (7)	O5W—Mn^ix	2.2183 (11)
Mn—O4	2.1330 (7)	O5W—K^vi	3.0236 (13)
Mn—O3^ix	2.1828 (7)	O6W—Mn^i	2.2676 (11)
Mn—O3^x	2.1828 (7)	O6W—K^ix	2.8382 (12)
Mn—O5W^i	2.2183 (11)
O1—K—O6W^i	72.45 (3)	O3^iii—K—P	104.133 (17)
O1—K—O3^ii	118.47 (2)	O2^iv—K—P	108.904 (17)
O6W^i—K—O3^ii	143.156 (18)	O2^v—K—P	142.470 (19)
O1—K—O3^iii	118.47 (2)	O5W^vi—K—P	74.04 (2)
O6W^i—K—O3^iii	143.156 (18)	O3^vii—K—P	69.133 (13)
O3^ii—K—O3^iii	66.25 (3)	Mn^viii—K—P	108.252 (9)
O1—K—O2^iv	128.45 (2)	O4^vii—Mn—O4	88.29 (4)
O6W^i—K—O2^iv	73.05 (2)	O4^vii—Mn—O3^ix	178.31 (3)
O3^ii—K—O2^iv	112.20 (2)	O4—Mn—O3^ix	90.42 (3)
O3^iii—K—O2^iv	73.82 (2)	O4^vii—Mn—O3^x	90.42 (3)
O1—K—O2^v	128.45 (2)	O4—Mn—O3^x	178.31 (3)
O6W^i—K—O2^v	73.05 (2)	O3^ix—Mn—O3^x	90.86 (4)
O3^ii—K—O2^v	73.82 (2)	O4^vii—Mn—O5W^i	94.72 (3)
O3^iii—K—O2^v	112.20 (2)	O4—Mn—O5W^i	94.72 (3)
O2^iv—K—O2^v	73.84 (3)	O3^ix—Mn—O5W^i	84.29 (3)
O1—K—O5W^vi	70.92 (3)	O3^x—Mn—O5W^i	84.29 (3)
O6W^i—K—O5W^vi	143.38 (3)	O4^vii—Mn—O6W^ix	86.86 (3)
O3^ii—K—O5W^vi	60.33 (2)	O4—Mn—O6W^ix	86.86 (3)
O3^iii—K—O5W^vi	60.33 (2)	O3^ix—Mn—O6W^ix	94.16 (3)
O2^iv—K—O5W^vi	132.70 (2)	O3^x—Mn—O6W^ix	94.16 (3)
O2^v—K—O5W^vi	132.70 (2)	O5W^i—Mn—O6W^ix	177.79 (4)
O6W^i—K—O3^vii	73.36 (2)	O4^vii—Mn—K^xi	129.404 (19)
O3^ii—K—O3^vii	89.57 (2)	O4—Mn—K^xi	129.404 (19)
O3^iii—K—O3^vii	141.128 (14)	O3^ix—Mn—K^xi	50.986 (18)
O2^iv—K—O3^vii	145.06 (2)	O3^x—Mn—K^xi	50.986 (18)
O2^v—K—O3^vii	87.45 (2)	O5W^i—Mn—K^xi	55.62 (3)
O5W^vi—K—O3^vii	81.51 (2)	O6W^ix—Mn—K^xi	122.17 (3)
O6W^i—K—O3	73.36 (2)	O4—P—O3	115.63 (4)
O3^ii—K—O3	141.128 (14)	O4—P—O2	110.32 (4)
O3^iii—K—O3	89.57 (2)	O3—P—O2	111.81 (4)
O2^iv—K—O3	87.45 (2)	O4—P—O1	108.80 (4)
O2^v—K—O3	145.06 (2)	O3—P—O1	103.82 (4)
O5W^vi—K—O3	81.51 (2)	O2—P—O1	105.76 (5)
O3^vii—K—O3	91.99 (2)	O4—P—K	129.19 (3)
O1—K—Mn^viii	108.18 (2)	O3—P—K	60.76 (3)
O6W^i—K—Mn^viii	179.36 (3)	O2—P—K	117.57 (3)
O2^iv—K—Mn^viii	106.455 (17)	P^vii—O1—P	131.80 (6)
O2^v—K—Mn^viii	106.455 (17)	P^vii—O1—K	113.78 (3)
O3^vii—K—Mn^viii	107.066 (14)	P—O1—K	113.78 (3)
O3—K—Mn^viii	107.066 (14)	P—O2—K^xii	129.37 (4)
O6W^i—K—P^vii	72.33 (2)	P—O3—Mn^i	125.81 (4)
O3^ii—K—P^vii	104.133 (17)	P—O3—K^iii	128.95 (4)
O3^iii—K—P^vii	132.133 (18)	Mn^i—O3—K^iii	92.43 (2)
O2^iv—K—P^vii	142.470 (19)	P—O3—K	95.86 (3)
O2^v—K—P^vii	108.904 (17)	Mn^i—O3—K	120.12 (3)
O5W^vi—K—P^vii	74.04 (2)	K^iii—O3—K	90.43 (2)
O3^vii—K—P^vii	23.384 (12)	P—O4—Mn	132.99 (4)
O3—K—P^vii	69.133 (13)	Mn^ix—O5W—K^vi	87.12 (4)
Mn^viii—K—P^vii	108.252 (9)	Mn^i—O6W—K^ix	134.77 (5)
O6W^i—K—P	72.33 (2)	Mn^i—O6W—H6W	100.5 (15)
O3^ii—K—P	132.133 (18)

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