Novel K/Mn phosphate hydrates, K₂Mn₃(H₂O)₂[P₂O₇]₂ and KMn(H₂O)₂[Al₂(PO₄)₃]: hydro­thermal synthesis and crystal chemistry

Two novel K/Mn phosphate hydrates, namely, dipotassium trimanganese dipyrophosphate dihydrate, K₂Mn₃(H₂O)₂[P₂O₇]₂, (I), and potassium manganese dialuminium triphosphate dihydrate, KMn(H₂O)₂[Al₂(PO₄)₃], (II), were obtained in the form of single crystals during a single hydro­thermal synthesis experiment. Their crystal structures were studied by X-ray diffraction. Both new com­pounds are members of the morphotropic series of phosphates with the following formulae: A₂M₃(H₂O)₂[P₂O₇]₂, where A = K, NH₄, Rb or Na and M = Mn, Fe, Co or Ni, and AM²⁺(H₂O)₂[M³⁺₂(PO₄)₃], where A = Cs, Rb, K, NH₄ or (H₃O); M²⁺ = Mn, Fe, Co or Ni; and M³⁺ = Al, Ga or Fe. A detailed crystal chemical analysis revealed correlations between the unit-cell parameters of the members of the series, their structural features and the sizes of the cations. It has been shown that a mixed type anionic framework is formed in (II) by aluminophosphate [(AlO₂)₂(PO₄)₂]_∞ layers, with a cationic topology similar to the Si/Al-topology of the crystal structures of feldspars. A study of the magnetic susceptibility of (II) demonstrates a paramagnetic behaviour of the com­pound.

Computing details

Data collection: CrysAlis PRO (Agilent, 2014) for (I); CrysAlis PRO (Rigaku OD, 2018) for (II). Cell refinement: CrysAlis PRO (Agilent, 2014) for (I); CrysAlis PRO (Rigaku OD, 2018) for (II). Data reduction: CrysAlis PRO (Agilent, 2014) for (I); CrysAlis PRO (Rigaku OD, 2018) for (II). For both structures, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: WinGX (Farrugia, 2012) and International Tables for Crystallography (2004).

Dipotassium trimanganese dipyrophosphate dihydrate (I)

Crystal data

K2[Mn3(P2O7)2(H2O)2]	F(000) = 610
Mr = 626.93	Dx = 2.940 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.1944 (1) Å	Cell parameters from 6532 reflections
b = 8.3134 (1) Å	θ = 3.3–32.3°
c = 9.3798 (2) Å	µ = 3.76 mm^−1
β = 98.924 (1)°	T = 293 K
V = 708.28 (2) Å^3	Cube, light pink
Z = 2	0.14 × 0.09 × 0.08 mm

Data collection

Agilent Xcalibur Sapphire3 diffractometer	2062 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1878 reflections with I > 2σ(I)
Detector resolution: 16.0630 pixels mm^-1	Rint = 0.043
ω scans	θmax = 30.0°, θmin = 3.3°
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014)	h = −12→12
Tmin = 0.703, Tmax = 0.787	k = −11→11
13181 measured reflections	l = −13→13

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)] = 0.023	All H-atom parameters refined
wR(F^2) = 0.051	w = 1/[σ^2(Fo^2) + (0.016P)^2 + 0.6P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
2062 reflections	Δρmax = 0.41 e Å^−3
124 parameters	Δρmin = −0.45 e Å^−3
0 restraints	Extinction correction: SHELXL2016 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0026 (5)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The X-ray experimental data necessary for the crystal structure solution were collected on an Xcalibur Sapphire3 single-crystal X-ray diffractometer (Mo Kα radiation, graphite monochromator) under normal conditions (phase I) and on Gemini AtlasS2 diffractometer at low temperature T = 150 K (phase II). The reflection intensities were collected over the full sphere of the reciprocal space and corrected for the Lorentz factor and the polarization effect. Empirical absorption corrections based on Gaussian integration over a multifaceted crystal model (I) and multi-scan of equivalent reflections (II) were applied. Atomic scattering curves and corrections for anomalous dispersion were taken from the International Tables for Crystallography (Prince, 2004). All calculations were performed within the WinGX software environment (Farrugia, 2012). Crystal structures were solved by direct methods and refined in an anisotropic approximation of thermal vibrations of atoms using the SHELX program package (Sheldrick, 2015a,b). New compounds with established structural formulae K₂Mn₃(H₂O)₂[P₂O₇]₂ (I) and KMn(H₂O)₂[Al₂(PO₄)₃] (II) are both monoclinic; their crystal structures were refined in P2₁/c and С2/c space groups to the residuals R 0.0233 and 0.0156, accordingly (Table 1).

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

	x	y	z	Uiso*/Ueq
Mn1	0.86036 (3)	0.64098 (4)	0.50150 (3)	0.00993 (8)
Mn2	1.000000	0.500000	1.000000	0.01041 (10)
K1	0.42510 (5)	0.77127 (6)	0.51866 (5)	0.02126 (11)
P1	0.89643 (5)	0.30438 (6)	0.71056 (5)	0.00783 (10)
P2	0.69390 (5)	0.56232 (6)	0.76840 (5)	0.00946 (11)
O1	0.99081 (15)	0.29720 (17)	0.85850 (14)	0.0121 (3)
O2	0.95641 (14)	0.42380 (17)	0.61190 (14)	0.0116 (3)
O3	0.86037 (15)	0.14330 (16)	0.63972 (15)	0.0121 (3)
O4	0.81499 (15)	0.62490 (17)	0.88538 (15)	0.0133 (3)
O5	0.68865 (15)	0.64677 (18)	0.62536 (15)	0.0153 (3)
O6	0.73867 (14)	0.37470 (17)	0.73998 (15)	0.0120 (3)
O7	0.54689 (15)	0.54853 (19)	0.81791 (16)	0.0164 (3)
O8	0.72027 (18)	0.5077 (2)	0.33614 (18)	0.0221 (4)
H1	0.629 (4)	0.503 (4)	0.297 (3)	0.047 (10)*
H2	0.766 (3)	0.477 (4)	0.273 (3)	0.036 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01057 (14)	0.00931 (14)	0.00987 (14)	−0.00041 (11)	0.00151 (10)	0.00045 (11)
Mn2	0.01177 (19)	0.00897 (19)	0.00956 (19)	0.00192 (15)	−0.00128 (15)	−0.00093 (15)
K1	0.0183 (2)	0.0235 (3)	0.0209 (2)	0.00230 (19)	−0.00018 (17)	−0.00139 (19)
P1	0.0088 (2)	0.0077 (2)	0.0072 (2)	−0.00006 (17)	0.00152 (16)	0.00010 (17)
P2	0.0076 (2)	0.0114 (2)	0.0092 (2)	0.00118 (17)	0.00088 (17)	−0.00069 (18)
O1	0.0150 (7)	0.0109 (6)	0.0090 (6)	0.0016 (5)	−0.0019 (5)	−0.0002 (5)
O2	0.0130 (6)	0.0111 (7)	0.0113 (6)	0.0006 (5)	0.0042 (5)	0.0029 (5)
O3	0.0138 (6)	0.0096 (6)	0.0131 (7)	−0.0005 (5)	0.0025 (5)	−0.0021 (5)
O4	0.0126 (6)	0.0128 (7)	0.0132 (7)	0.0007 (5)	−0.0020 (5)	−0.0024 (5)
O5	0.0155 (7)	0.0190 (8)	0.0117 (7)	0.0050 (6)	0.0030 (5)	0.0042 (6)
O6	0.0098 (6)	0.0105 (6)	0.0162 (7)	−0.0001 (5)	0.0037 (5)	−0.0027 (5)
O7	0.0102 (6)	0.0210 (8)	0.0188 (7)	0.0011 (6)	0.0052 (5)	−0.0016 (6)
O8	0.0146 (7)	0.0302 (9)	0.0211 (8)	−0.0001 (7)	0.0016 (6)	−0.0118 (7)

Geometric parameters (Å, º)

Mn1—O5	2.1008 (14)	K1—O6^vi	3.0314 (14)
Mn1—O8	2.1615 (16)	K1—O8^vii	3.0962 (19)
Mn1—O1^i	2.1739 (14)	K1—O7	3.4039 (16)
Mn1—O2^ii	2.1945 (13)	K1—P2^vi	3.4233 (7)
Mn1—O2	2.1974 (14)	K1—P1^vii	3.4331 (7)
Mn1—O4^iii	2.2377 (14)	K1—P2	3.5800 (7)
Mn2—O4	2.1355 (14)	K1—K1^viii	4.0781 (10)
Mn2—O4^iv	2.1355 (14)	P1—O3	1.5088 (14)
Mn2—O1^iv	2.1393 (14)	P1—O2	1.5180 (14)
Mn2—O1	2.1393 (14)	P1—O1	1.5194 (14)
Mn2—O3^i	2.3037 (13)	P1—O6	1.6267 (14)
Mn2—O3^v	2.3037 (13)	P2—O7	1.5002 (14)
K1—O5	2.6819 (15)	P2—O5	1.5084 (14)
K1—O7^vi	2.7580 (16)	P2—O4	1.5281 (14)
K1—O7^iii	2.7745 (15)	P2—O6	1.6454 (15)
K1—O3^vii	2.8967 (14)	O8—H1	0.86 (3)
K1—O6^vii	2.9141 (15)	O8—H2	0.82 (3)
O5—Mn1—O8	89.62 (6)	O7^iii—K1—P2	113.31 (3)
O5—Mn1—O1^i	96.25 (6)	O3^vii—K1—P2	158.93 (3)
O8—Mn1—O1^i	171.42 (6)	O6^vii—K1—P2	123.90 (3)
O5—Mn1—O2^ii	166.64 (6)	O6^vi—K1—P2	91.23 (3)
O8—Mn1—O2^ii	86.75 (6)	O8^vii—K1—P2	69.51 (3)
O1^i—Mn1—O2^ii	88.90 (5)	O7—K1—P2	24.64 (2)
O5—Mn1—O2	92.28 (5)	P2^vi—K1—P2	102.233 (14)
O8—Mn1—O2	93.91 (6)	P1^vii—K1—P2	139.542 (19)
O1^i—Mn1—O2	92.11 (5)	O5—K1—K1^viii	95.41 (4)
O2^ii—Mn1—O2	75.17 (5)	O7^vi—K1—K1^viii	42.67 (3)
O5—Mn1—O4^iii	98.62 (5)	O7^iii—K1—K1^viii	42.36 (3)
O8—Mn1—O4^iii	92.93 (6)	O3^vii—K1—K1^viii	91.06 (3)
O1^i—Mn1—O4^iii	80.03 (5)	O6^vii—K1—K1^viii	117.04 (3)
O2^ii—Mn1—O4^iii	94.40 (5)	O6^vi—K1—K1^viii	90.75 (3)
O2—Mn1—O4^iii	167.16 (5)	O8^vii—K1—K1^viii	155.64 (4)
O4—Mn2—O4^iv	180.00 (7)	O7—K1—K1^viii	120.39 (3)
O4—Mn2—O1^iv	83.16 (5)	P2^vi—K1—K1^viii	62.208 (15)
O4^iv—Mn2—O1^iv	96.84 (5)	P1^vii—K1—K1^viii	112.74 (2)
O4—Mn2—O1	96.84 (5)	P2—K1—K1^viii	107.494 (19)
O4^iv—Mn2—O1	83.16 (5)	O3—P1—O2	112.82 (8)
O1^iv—Mn2—O1	180.0	O3—P1—O1	115.01 (8)
O4—Mn2—O3^i	86.15 (5)	O2—P1—O1	111.87 (8)
O4^iv—Mn2—O3^i	93.85 (5)	O3—P1—O6	104.65 (7)
O1^iv—Mn2—O3^i	88.48 (5)	O2—P1—O6	106.63 (8)
O1—Mn2—O3^i	91.52 (5)	O1—P1—O6	104.90 (8)
O4—Mn2—O3^v	93.85 (5)	O3—P1—K1^vii	56.81 (5)
O4^iv—Mn2—O3^v	86.15 (5)	O2—P1—K1^vii	95.57 (6)
O1^iv—Mn2—O3^v	91.52 (5)	O1—P1—K1^vii	151.53 (6)
O1—Mn2—O3^v	88.48 (5)	O6—P1—K1^vii	57.87 (5)
O3^i—Mn2—O3^v	180.0	O7—P2—O5	113.88 (8)
O5—K1—O7^vi	96.55 (5)	O7—P2—O4	113.26 (8)
O5—K1—O7^iii	91.45 (4)	O5—P2—O4	113.54 (8)
O7^vi—K1—O7^iii	85.03 (5)	O7—P2—O6	103.75 (8)
O5—K1—O3^vii	168.64 (5)	O5—P2—O6	105.75 (8)
O7^vi—K1—O3^vii	94.54 (4)	O4—P2—O6	105.45 (8)
O7^iii—K1—O3^vii	87.05 (4)	O7—P2—K1^ix	51.72 (6)
O5—K1—O6^vii	118.05 (4)	O5—P2—K1^ix	151.51 (6)
O7^vi—K1—O6^vii	143.36 (4)	O4—P2—K1^ix	94.87 (6)
O7^iii—K1—O6^vii	82.57 (4)	O6—P2—K1^ix	62.30 (5)
O3^vii—K1—O6^vii	50.59 (4)	O7—P2—K1	71.09 (6)
O5—K1—O6^vi	110.82 (4)	O5—P2—K1	42.99 (5)
O7^vi—K1—O6^vi	50.37 (4)	O4—P2—K1	131.05 (6)
O7^iii—K1—O6^vi	130.79 (5)	O6—P2—K1	121.24 (5)
O3^vii—K1—O6^vi	78.34 (4)	K1^ix—P2—K1	118.296 (15)
O6^vii—K1—O6^vi	119.17 (5)	P1—O1—Mn2	119.85 (8)
O5—K1—O8^vii	88.48 (5)	P1—O1—Mn1^x	142.37 (9)
O7^vi—K1—O8^vii	113.02 (5)	Mn2—O1—Mn1^x	97.78 (5)
O7^iii—K1—O8^vii	161.85 (5)	P1—O2—Mn1^ii	120.92 (8)
O3^vii—K1—O8^vii	89.46 (4)	P1—O2—Mn1	131.85 (8)
O6^vii—K1—O8^vii	81.47 (4)	Mn1^ii—O2—Mn1	104.83 (5)
O6^vi—K1—O8^vii	65.52 (4)	P1—O3—Mn2^x	127.28 (8)
O5—K1—O7	47.13 (4)	P1—O3—K1^vii	97.35 (6)
O7^vi—K1—O7	90.338 (19)	Mn2^x—O3—K1^vii	112.06 (5)
O7^iii—K1—O7	137.53 (5)	P2—O4—Mn2	129.10 (8)
O3^vii—K1—O7	135.42 (4)	P2—O4—Mn1^xi	134.88 (8)
O6^vii—K1—O7	121.42 (4)	Mn2—O4—Mn1^xi	95.97 (5)
O6^vi—K1—O7	71.12 (4)	P2—O5—Mn1	123.93 (8)
O8^vii—K1—O7	48.62 (4)	P2—O5—K1	114.45 (7)
O5—K1—P2^vi	114.02 (4)	Mn1—O5—K1	121.03 (6)
O7^vi—K1—P2^vi	25.28 (3)	P1—O6—P2	128.33 (9)
O7^iii—K1—P2^vi	102.33 (4)	P1—O6—K1^vii	93.92 (6)
O3^vii—K1—P2^vi	77.27 (3)	P2—O6—K1^vii	114.82 (7)
O6^vii—K1—P2^vi	127.55 (3)	P1—O6—K1^ix	125.74 (7)
O6^vi—K1—P2^vi	28.72 (3)	P2—O6—K1^ix	88.98 (6)
O8^vii—K1—P2^vi	94.24 (3)	K1^vii—O6—K1^ix	104.55 (4)
O7—K1—P2^vi	89.85 (3)	P2—O7—K1^ix	103.00 (7)
O5—K1—P1^vii	143.46 (4)	P2—O7—K1^xi	130.29 (8)
O7^vi—K1—P1^vii	119.89 (3)	K1^ix—O7—K1^xi	94.97 (5)
O7^iii—K1—P1^vii	94.18 (3)	P2—O7—K1	84.27 (6)
O3^vii—K1—P1^vii	25.84 (3)	K1^ix—O7—K1	154.61 (6)
O6^vii—K1—P1^vii	28.21 (3)	K1^xi—O7—K1	98.64 (4)
O6^vi—K1—P1^vii	92.32 (3)	Mn1—O8—K1^vii	108.55 (7)
O8^vii—K1—P1^vii	75.50 (3)	Mn1—O8—H1	140 (2)
O7—K1—P1^vii	123.91 (3)	K1^vii—O8—H1	72 (2)
P2^vi—K1—P1^vii	99.948 (16)	Mn1—O8—H2	111 (2)
O5—K1—P2	22.55 (3)	K1^vii—O8—H2	113 (2)
O7^vi—K1—P2	92.66 (3)	H1—O8—H2	105 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H1···O7^vii	0.86 (3)	1.85 (3)	2.691 (2)	165 (3)
O8—H2···O3^xii	0.82 (3)	1.91 (3)	2.714 (2)	166 (3)

Symmetry codes: (vii) −x+1, −y+1, −z+1; (xii) x, −y+1/2, z−1/2.

Potassium manganese dialuminium triphosphate dihydrate (II)

Crystal data

K[Al2Mn(PO4)3(H2O)2]	F(000) = 924
Mr = 468.94	Dx = 2.794 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.3117 (3) Å	Cell parameters from 5410 reflections
b = 10.0949 (2) Å	θ = 2.6–34.2°
c = 8.7261 (2) Å	µ = 2.23 mm^−1
β = 108.057 (2)°	T = 152 K
V = 1114.86 (4) Å^3	Plate, light blue
Z = 4	0.23 × 0.11 × 0.07 mm

Data collection

Rigaku Xcalibur AtlasS2 Gemini diffractometer	1627 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1584 reflections with I > 2σ(I)
Detector resolution: 5.2283 pixels mm^-1	Rint = 0.012
ω scans	θmax = 30.0°, θmin = 2.6°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	h = −17→18
Tmin = 0.741, Tmax = 0.901	k = −14→14
6128 measured reflections	l = −12→9

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)] = 0.016	Hydrogen site location: difference Fourier map
wR(F^2) = 0.047	All H-atom parameters refined
S = 1.14	w = 1/[σ^2(Fo^2) + (0.024P)^2 + 1.3P] where P = (Fo^2 + 2Fc^2)/3
1627 reflections	(Δ/σ)max = 0.001
105 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The X-ray experimental data necessary for the crystal structure solution were collected on an Xcalibur Sapphire3 single-crystal X-ray diffractometer (Mo Kα radiation, graphite monochromator) under normal conditions (phase I) and on Gemini AtlasS2 diffractometer at low temperature T = 150 K (phase II). The reflection intensities were collected over the full sphere of the reciprocal space and corrected for the Lorentz factor and the polarization effect. Empirical absorption corrections based on Gaussian integration over a multifaceted crystal model (I) and multi-scan of equivalent reflections (II) were applied. Atomic scattering curves and corrections for anomalous dispersion were taken from the International Tables for Crystallography (2004). All calculations were performed within the WinGX software environment (Farrugia, 2012). Crystal structures were solved by direct methods and refined in an anisotropic approximation of thermal vibrations of atoms using the SHELX program package (Sheldrick, 2015a,b). New compounds with established structural formulae K₂Mn₃(H₂O)₂[P₂O₇]₂ (I) and KMn(H₂O)₂[Al₂(PO₄)₃] (II) are both monoclinic; their crystal structures were refined in P2₁/c and С2/c space groups to the residuals R 0.0233 and 0.0156, accordingly (Table 1).

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

	x	y	z	Uiso*/Ueq
Mn1	0.500000	0.28430 (2)	0.750000	0.00554 (7)
K1	0.500000	0.63852 (4)	0.750000	0.02254 (11)
P2	0.500000	0.00175 (4)	0.250000	0.00380 (9)
P1	0.70976 (2)	0.37648 (3)	0.67270 (4)	0.00434 (7)
Al1	0.66933 (3)	0.07620 (3)	0.57313 (4)	0.00384 (8)
O1	0.43011 (7)	−0.09455 (8)	0.30903 (11)	0.00636 (16)
O2	0.72915 (7)	0.45143 (8)	0.53130 (10)	0.00641 (16)
O3	0.79374 (7)	0.41809 (8)	0.83219 (10)	0.00607 (16)
O4	0.59939 (7)	0.40892 (9)	0.67572 (11)	0.00843 (17)
O5	0.72811 (7)	0.22753 (8)	0.65832 (11)	0.00654 (16)
O6	0.61051 (8)	0.30350 (10)	0.99766 (12)	0.01195 (18)
O7	0.56327 (7)	0.09181 (8)	0.38638 (10)	0.00625 (16)
H1	0.6484 (18)	0.244 (2)	1.051 (3)	0.027 (5)*
H2	0.645 (2)	0.364 (2)	1.008 (3)	0.030 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.00559 (12)	0.00479 (12)	0.00681 (13)	0.000	0.00274 (9)	0.000
K1	0.0281 (3)	0.00935 (19)	0.0357 (3)	0.000	0.0180 (2)	0.000
P2	0.00391 (18)	0.00419 (17)	0.00354 (18)	0.000	0.00149 (14)	0.000
P1	0.00465 (14)	0.00433 (13)	0.00445 (14)	−0.00061 (9)	0.00201 (10)	−0.00028 (9)
Al1	0.00429 (16)	0.00369 (15)	0.00357 (16)	−0.00012 (11)	0.00124 (12)	0.00008 (11)
O1	0.0065 (4)	0.0060 (4)	0.0080 (4)	−0.0001 (3)	0.0043 (3)	0.0007 (3)
O2	0.0075 (4)	0.0065 (4)	0.0063 (4)	0.0006 (3)	0.0036 (3)	0.0009 (3)
O3	0.0071 (4)	0.0056 (4)	0.0053 (4)	−0.0008 (3)	0.0017 (3)	−0.0012 (3)
O4	0.0063 (4)	0.0087 (4)	0.0114 (4)	0.0002 (3)	0.0044 (3)	0.0014 (3)
O5	0.0081 (4)	0.0047 (4)	0.0069 (4)	−0.0011 (3)	0.0024 (3)	−0.0012 (3)
O6	0.0122 (4)	0.0083 (4)	0.0120 (4)	−0.0008 (3)	−0.0011 (3)	0.0018 (3)
O7	0.0063 (4)	0.0070 (4)	0.0046 (4)	−0.0002 (3)	0.0004 (3)	−0.0009 (3)

Geometric parameters (Å, º)

Mn1—O4	2.0700 (9)	K1—P2^v	3.6314 (6)
Mn1—O4^i	2.0700 (9)	P2—O7	1.5267 (9)
Mn1—O6	2.2139 (10)	P2—O7^viii	1.5267 (9)
Mn1—O6^i	2.2139 (10)	P2—O1^viii	1.5404 (9)
Mn1—O1^ii	2.2576 (9)	P2—O1	1.5405 (9)
Mn1—O1^iii	2.2576 (9)	P1—O4	1.5135 (9)
Mn1—P2^iii	2.8876 (5)	P1—O5	1.5346 (9)
Mn1—K1	3.5758 (5)	P1—O2	1.5359 (9)
K1—O4^i	2.8415 (10)	P1—O3	1.5488 (9)
K1—O4	2.8415 (9)	Al1—O5	1.7715 (9)
K1—O7^iv	2.9858 (9)	Al1—O3^ix	1.7945 (9)
K1—O7^v	2.9858 (9)	Al1—O7	1.8021 (9)
K1—O6^vi	3.0599 (11)	Al1—O2^x	1.8702 (9)
K1—O6^vii	3.0599 (11)	Al1—O1^iii	1.9204 (9)
K1—O2^v	3.3930 (9)	O6—H1	0.83 (2)
K1—O2^iv	3.3930 (9)	O6—H2	0.75 (3)
O4—Mn1—O4^i	105.15 (5)	O2^v—K1—Mn1	74.479 (16)
O4—Mn1—O6	87.52 (4)	O2^iv—K1—Mn1	74.479 (16)
O4^i—Mn1—O6	86.38 (4)	O4^i—K1—P2^v	144.654 (19)
O4—Mn1—O6^i	86.38 (4)	O4—K1—P2^v	144.654 (19)
O4^i—Mn1—O6^i	87.52 (4)	O7^iv—K1—P2^v	24.254 (17)
O6—Mn1—O6^i	169.95 (5)	O7^v—K1—P2^v	24.254 (17)
O4—Mn1—O1^ii	159.34 (3)	O6^vi—K1—P2^v	78.97 (2)
O4^i—Mn1—O1^ii	95.49 (3)	O6^vii—K1—P2^v	78.97 (2)
O6—Mn1—O1^ii	92.73 (4)	O2^v—K1—P2^v	105.521 (16)
O6^i—Mn1—O1^ii	95.79 (3)	O2^iv—K1—P2^v	105.521 (16)
O4—Mn1—O1^iii	95.49 (3)	Mn1—K1—P2^v	180.0
O4^i—Mn1—O1^iii	159.34 (3)	O7—P2—O7^viii	106.91 (7)
O6—Mn1—O1^iii	95.79 (3)	O7—P2—O1^viii	113.08 (5)
O6^i—Mn1—O1^iii	92.73 (4)	O7^viii—P2—O1^viii	111.07 (5)
O1^ii—Mn1—O1^iii	63.91 (4)	O7—P2—O1	111.08 (5)
O4—Mn1—P2^iii	127.43 (3)	O7^viii—P2—O1	113.08 (5)
O4^i—Mn1—P2^iii	127.43 (3)	O1^viii—P2—O1	101.74 (7)
O6—Mn1—P2^iii	95.02 (3)	O7—P2—Mn1^iii	126.55 (3)
O6^i—Mn1—P2^iii	95.02 (3)	O7^viii—P2—Mn1^iii	126.55 (3)
O1^ii—Mn1—P2^iii	31.96 (2)	O1^viii—P2—Mn1^iii	50.87 (3)
O1^iii—Mn1—P2^iii	31.96 (2)	O1—P2—Mn1^iii	50.87 (3)
O4—Mn1—K1	52.57 (3)	O7—P2—K1^v	53.45 (3)
O4^i—Mn1—K1	52.57 (3)	O7^viii—P2—K1^v	53.45 (3)
O6—Mn1—K1	84.98 (3)	O1^viii—P2—K1^v	129.13 (3)
O6^i—Mn1—K1	84.98 (3)	O1—P2—K1^v	129.13 (3)
O1^ii—Mn1—K1	148.04 (2)	Mn1^iii—P2—K1^v	180.0
O1^iii—Mn1—K1	148.04 (2)	O4—P1—O5	113.17 (5)
P2^iii—Mn1—K1	180.0	O4—P1—O2	108.25 (5)
O4^i—K1—O4	70.69 (4)	O5—P1—O2	110.26 (5)
O4^i—K1—O7^iv	138.29 (3)	O4—P1—O3	111.09 (5)
O4—K1—O7^iv	137.80 (2)	O5—P1—O3	104.50 (5)
O4^i—K1—O7^v	137.80 (2)	O2—P1—O3	109.52 (5)
O4—K1—O7^v	138.29 (3)	O5—Al1—O3^ix	123.47 (4)
O7^iv—K1—O7^v	48.51 (3)	O5—Al1—O7	115.11 (4)
O4^i—K1—O6^vi	68.30 (3)	O3^ix—Al1—O7	121.34 (4)
O4—K1—O6^vi	132.99 (3)	O5—Al1—O2^x	92.36 (4)
O7^iv—K1—O6^vi	71.21 (3)	O3^ix—Al1—O2^x	87.45 (4)
O7^v—K1—O6^vi	88.47 (3)	O7—Al1—O2^x	93.11 (4)
O4^i—K1—O6^vii	132.99 (3)	O5—Al1—O1^iii	88.87 (4)
O4—K1—O6^vii	68.30 (3)	O3^ix—Al1—O1^iii	88.58 (4)
O7^iv—K1—O6^vii	88.47 (3)	O7—Al1—O1^iii	89.94 (4)
O7^v—K1—O6^vii	71.21 (3)	O2^x—Al1—O1^iii	175.87 (4)
O6^vi—K1—O6^vii	157.94 (4)	P2—O1—Al1^iii	134.92 (5)
O4^i—K1—O2^v	64.47 (2)	P2—O1—Mn1^iii	97.17 (4)
O4—K1—O2^v	89.68 (2)	Al1^iii—O1—Mn1^iii	127.25 (4)
O7^iv—K1—O2^v	127.70 (2)	P1—O2—Al1^x	130.15 (6)
O7^v—K1—O2^v	82.90 (2)	P1—O2—K1^v	96.44 (4)
O6^vi—K1—O2^v	92.68 (2)	Al1^x—O2—K1^v	103.35 (4)
O6^vii—K1—O2^v	93.18 (2)	P1—O3—Al1^xi	132.33 (6)
O4^i—K1—O2^iv	89.68 (2)	P1—O4—Mn1	126.30 (5)
O4—K1—O2^iv	64.47 (2)	P1—O4—K1	134.72 (5)
O7^iv—K1—O2^iv	82.90 (2)	Mn1—O4—K1	92.08 (3)
O7^v—K1—O2^iv	127.71 (2)	P1—O5—Al1	144.93 (6)
O6^vi—K1—O2^iv	93.18 (2)	Mn1—O6—K1^vi	113.39 (4)
O6^vii—K1—O2^iv	92.68 (2)	Mn1—O6—H1	126.4 (16)
O2^v—K1—O2^iv	148.96 (3)	K1^vi—O6—H1	94.4 (15)
O4^i—K1—Mn1	35.346 (19)	Mn1—O6—H2	112.8 (19)
O4—K1—Mn1	35.346 (19)	K1^vi—O6—H2	99.5 (19)
O7^iv—K1—Mn1	155.746 (17)	H1—O6—H2	106 (2)
O7^v—K1—Mn1	155.746 (17)	P2—O7—Al1	137.83 (6)
O6^vi—K1—Mn1	101.03 (2)	P2—O7—K1^v	102.29 (4)
O6^vii—K1—Mn1	101.03 (2)	Al1—O7—K1^v	119.03 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H1···O3^xii	0.83 (2)	1.96 (3)	2.7675 (13)	166 (2)
O6—H1···O5^xii	0.83 (2)	2.57 (2)	3.1188 (13)	125 (2)
O6—H2···O2^iv	0.75 (3)	2.15 (3)	2.9007 (13)	174 (2)

Symmetry codes: (iv) x, −y+1, z+1/2; (xii) −x+3/2, −y+1/2, −z+2.