K(0.53)Mn(2.37)Fe(1.24)(PO(4))(3).

During an attempt to crystallize potassium manganese diiron phosphate KMnFe(2)(PO(4))(3) by the flux method, a new phase, potassium dimanganese iron triphosphate, K(0.53)Mn(2.37)Fe(1.24)(PO(4))(3), was isolated. This phase, whose composition was confirmed by ICP analysis, is isotypic with the alluaudite-like phosphates, thus it exhibits the (A2)(A'2)(A1)(A'1)(A''1)(M1)(M2)(2)(PO(4))(3) general formula. The site occupancies led to the following cation distribution: 0.53 K on A'2 (site symmetry 2), 0.31 Mn on A''1, 1.0 Mn on M1 (site symmetry 2) and (0.62 Fe + 0.38 Mn) on M2. The structure is built up from infinite chains of edge-sharing M1O(6) and M2O(6) octa-hedra. These chains run along [10] and are connected by two different PO(4) tetrahedra, one of which exhibits 2 symmetry. The resulting three-dimensional framework delimits large tunnels parallel to [001], which are partially occupied by the K(+) and Mn(2+) cations.

Related literature

For the alluaudite structure, see: Fisher (1955 ▶); Moore (1971 ▶); Chouaibi et al. (2001 ▶); Corbin et al. (1986 ▶); Lee & Ye (1997 ▶); Hidouri et al. (2003 ▶, 2004 ▶, 2008 ▶) Antenucci et al. (1993 ▶, 1995 ▶); For P—O distances, see: Baur (1974 ▶). For bond-valence sums, see: Brown & Altermatt (1985 ▶). For ionic radii, see: Shannon (1976 ▶).

Experimental

Crystal data

K0.53Mn2.37Fe1.24(PO4)3

M = 505.28

Monoclinic,

a = 12.272 (2) Å

b = 12.606 (2) Å

c = 6.416 (4) Å

β = 114.87 (2)°

V = 900.5 (6) Å3

Z = 4

Mo Kα radiation

μ = 6.07 mm−1

T = 293 K

0.43 × 0.09 × 0.02 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer

Absorption correction: refined from ΔF (Parkin et al., 1995 ▶) T min = 0.42, T max = 0.81

1754 measured reflections

1308 independent reflections

1047 reflections with I > 2σ(I)

R int = 0.042

2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.089

S = 1.07

1308 reflections

102 parameters

2 restraints

Δρmax = 0.78 e Å−3

Δρmin = −0.68 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810051238/br2150sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051238/br2150Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

K0.53Mn2.37Fe1.24(PO4)3	F(000) = 957
Mr = 505.28	Dx = 3.727 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 12.272 (2) Å	θ = 9.8–14.4°
b = 12.606 (2) Å	µ = 6.07 mm−1
c = 6.416 (4) Å	T = 293 K
β = 114.87 (2)°	Hexagonal, brown
V = 900.5 (6) Å3	0.43 × 0.09 × 0.02 mm
Z = 4

Enraf–Nonius TurboCAD-4 diffractometer	1047 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.042
graphite	θmax = 30.0°, θmin = 2.4°
non–profiled ω/2θ scans	h = −17→15
Absorption correction: part of the refinement model (ΔF) (Parkin et al., 1995)	k = 0→17
Tmin = 0.42, Tmax = 0.81	l = 0→9
1754 measured reflections	2 standard reflections every 120 min
1308 independent reflections	intensity decay: 1%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	w = 1/[σ2(Fo2) + (0.0451P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.089	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 0.78 e Å−3
1308 reflections	Δρmin = −0.68 e Å−3
102 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
2 restraints	Extinction coefficient: 0.0009 (4)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
K	0.0000	−0.0116 (2)	0.2500	0.0229 (7)	0.531 (5)
Mn1	0.0000	0.26376 (7)	0.2500	0.0156 (2)
Fe2	0.22489 (4)	0.15521 (4)	0.13977 (8)	0.01004 (16)	0.6217 (6)
Mn2	0.22489 (4)	0.15521 (4)	0.13977 (8)	0.01004 (16)	0.3783 (7)
Mn3	−0.02360 (17)	0.49774 (17)	0.0393 (4)	0.0209 (5)	0.3064 (12)
P1	0.0000	0.28642 (11)	−0.2500	0.0096 (3)
O11	0.0479 (2)	0.2160 (2)	−0.0331 (4)	0.0138 (5)
O12	−0.0942 (3)	0.3615 (2)	−0.2314 (6)	0.0251 (7)
P2	0.24436 (8)	0.10810 (7)	0.63905 (15)	0.0093 (2)
O21	0.2272 (2)	0.1782 (2)	0.8220 (4)	0.0156 (6)
O22	0.1735 (3)	0.1629 (2)	0.4048 (4)	0.0169 (6)
O23	0.3783 (2)	0.1019 (2)	0.6976 (6)	0.0255 (7)
O24	0.1930 (2)	−0.0019 (2)	0.6349 (5)	0.0178 (6)

	U11	U22	U33	U12	U13	U23
K	0.0093 (10)	0.0218 (13)	0.0260 (13)	0.000	−0.0040 (9)	0.000
Mn1	0.0115 (4)	0.0202 (4)	0.0154 (4)	0.000	0.0058 (3)	0.000
Fe2	0.0065 (2)	0.0138 (3)	0.0065 (3)	0.00016 (18)	−0.00043 (19)	0.0008 (2)
Mn2	0.0065 (2)	0.0138 (3)	0.0065 (3)	0.00016 (18)	−0.00043 (19)	0.0008 (2)
Mn3	0.0156 (12)	0.0164 (9)	0.0165 (11)	−0.0002 (9)	−0.0070 (7)	0.0014 (9)
P1	0.0060 (5)	0.0140 (6)	0.0038 (5)	0.000	−0.0028 (4)	0.000
O11	0.0087 (11)	0.0193 (13)	0.0066 (11)	−0.0027 (10)	−0.0033 (9)	0.0028 (10)
O12	0.0149 (13)	0.0245 (15)	0.0301 (17)	0.0025 (12)	0.0037 (13)	−0.0119 (14)
P2	0.0065 (4)	0.0123 (4)	0.0050 (4)	0.0004 (3)	−0.0016 (3)	0.0012 (3)
O21	0.0128 (12)	0.0235 (14)	0.0078 (11)	−0.0030 (11)	0.0017 (10)	−0.0038 (11)
O22	0.0244 (14)	0.0141 (14)	0.0048 (11)	0.0003 (11)	−0.0010 (10)	−0.0007 (10)
O23	0.0114 (13)	0.0189 (15)	0.047 (2)	0.0003 (11)	0.0132 (14)	−0.0018 (15)
O24	0.0127 (12)	0.0184 (14)	0.0171 (13)	−0.0013 (11)	0.0012 (11)	0.0030 (11)

K—O24	2.608 (3)	Mn1—O22i	2.315 (3)
K—O24i	2.608 (3)	Mn1—O22	2.315 (3)
K—O24ii	2.767 (3)	Fe2—O24ii	1.970 (3)
K—O24iii	2.767 (3)	Fe2—O12x	2.027 (3)
K—O11iv	2.869 (4)	Fe2—O22	2.049 (3)
K—O11v	2.869 (4)	Fe2—O21xi	2.071 (3)
K—O22	2.929 (3)	Fe2—O11	2.123 (3)
K—O22i	2.929 (3)	Fe2—O21vi	2.167 (3)
Mn3—O23vi	2.253 (4)	P1—O12xii	1.537 (3)
Mn3—O23vii	2.256 (4)	P1—O12	1.537 (3)
Mn3—O12viii	2.294 (4)	P1—O11xii	1.544 (3)
Mn3—O12	2.335 (4)	P1—O11	1.544 (3)
Mn3—O23ix	2.400 (4)	P2—O24	1.519 (3)
Mn1—O23vi	2.189 (3)	P2—O23	1.526 (3)
Mn1—O23vii	2.189 (3)	P2—O22	1.547 (3)
Mn1—O11	2.215 (3)	P2—O21	1.553 (3)
Mn1—O11i	2.215 (3)
O24—K—O24i	174.63 (16)	O23vi—Mn1—O11	86.39 (11)
O24—K—O24ii	73.24 (8)	O23vii—Mn1—O11	118.95 (12)
O24i—K—O24ii	106.42 (8)	O23vi—Mn1—O11i	118.95 (12)
O24—K—O24iii	106.42 (8)	O23vii—Mn1—O11i	86.39 (11)
O24i—K—O24iii	73.24 (8)	O11—Mn1—O11i	148.43 (15)
O24ii—K—O24iii	172.95 (16)	O23vi—Mn1—O22i	159.42 (10)
O24—K—O11iv	114.87 (10)	O23vii—Mn1—O22i	85.06 (10)
O24i—K—O11iv	70.34 (8)	O11—Mn1—O22i	90.70 (10)
O24ii—K—O11iv	87.10 (9)	O11i—Mn1—O22i	71.87 (10)
O24iii—K—O11iv	99.26 (10)	O23vi—Mn1—O22	85.06 (10)
O24—K—O11v	70.34 (8)	O23vii—Mn1—O22	159.42 (10)
O24i—K—O11v	114.87 (10)	O11—Mn1—O22	71.87 (10)
O24ii—K—O11v	99.26 (10)	O11i—Mn1—O22	90.70 (10)
O24iii—K—O11v	87.10 (9)	O22i—Mn1—O22	113.36 (14)
O11iv—K—O11v	52.22 (11)	O24ii—Fe2—O12x	94.65 (12)
O24—K—O22	53.32 (8)	O24ii—Fe2—O22	86.05 (12)
O24i—K—O22	121.80 (11)	O12x—Fe2—O22	109.44 (13)
O24ii—K—O22	57.49 (9)	O24ii—Fe2—O21xi	101.92 (12)
O24iii—K—O22	116.43 (11)	O12x—Fe2—O21xi	87.13 (12)
O11iv—K—O22	144.11 (8)	O22—Fe2—O21xi	161.16 (11)
O11v—K—O22	122.58 (8)	O24ii—Fe2—O11	101.11 (11)
O24—K—O22i	121.80 (11)	O12x—Fe2—O11	162.62 (11)
O24i—K—O22i	53.32 (8)	O22—Fe2—O11	79.18 (11)
O24ii—K—O22i	116.43 (11)	O21xi—Fe2—O11	82.52 (11)
O24iii—K—O22i	57.49 (9)	O24ii—Fe2—O21vi	174.59 (11)
O11iv—K—O22i	122.58 (8)	O12x—Fe2—O21vi	81.71 (11)
O11v—K—O22i	144.11 (8)	O22—Fe2—O21vi	91.37 (11)
O22—K—O22i	82.66 (13)	O21xi—Fe2—O21vi	81.97 (11)
O23vi—Mn3—O23vii	75.91 (14)	O11—Fe2—O21vi	83.04 (10)
O23vi—Mn3—O12viii	84.68 (13)	O12xii—P1—O12	104.0 (3)
O23vii—Mn3—O12viii	121.62 (16)	O12xii—P1—O11xii	107.33 (17)
Mn1viii—Mn3—O12	76.0 (3)	O12—P1—O11xii	114.23 (15)
O23vi—Mn3—O12	94.38 (14)	O12xii—P1—O11	114.23 (15)
O23vii—Mn3—O12	79.85 (14)	O12—P1—O11	107.33 (17)
O12viii—Mn3—O12	157.20 (11)	O11xii—P1—O11	109.7 (2)
Mn1viii—Mn3—O23ix	69.7 (3)	O24—P2—O23	110.71 (16)
O23vi—Mn3—O23ix	157.58 (11)	O24—P2—O22	109.32 (15)
O23vii—Mn3—O23ix	123.93 (15)	O23—P2—O22	111.67 (18)
O12viii—Mn3—O23ix	91.62 (14)	O24—P2—O21	110.22 (17)
O12—Mn3—O23ix	80.58 (13)	O23—P2—O21	108.50 (16)
O23vi—Mn1—O23vii	78.61 (15)	O22—P2—O21	106.32 (16)