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inorganic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 1| January 2011| Page i1
https://doi.org/10.1107/S1600536810051238

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

Mourad Hidouria* and Mongi Ben Amaraa

aFaculté des Sciences de Monastir, 5019 Monastir, Tunisia
*Correspondence e-mail: mourad_hidouri@yahoo.fr

(Received 3 November 2010; accepted 6 December 2010; online 11 December 2010)

During an attempt to crystallize potassium manganese diiron phosphate KMnFe2(PO4)3 by the flux method, a new phase, potassium dimanganese iron triphosphate, K0.53Mn2.37Fe1.24(PO4)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(PO4)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 M1O6 and M2O6 octa­hedra. These chains run along [10[\overline{1}]] and are connected by two different PO4 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 Mn2+ cations.

Related literature

For the alluaudite structure, see: Fisher (1955[Fisher, D. J. (1955). Am. Mineral. 40, 1100-1109.]); Moore (1971[Moore, P. B. (1971). Am. Mineral. 56, 1955-1975.]); Chouaibi et al. (2001[Chouaibi, N., Daidouh, A., Pico, C., Strantrich, A. & Veiga, M. L. (2001). J. Solid State Chem. 159, 46-50.]); Corbin et al. (1986[Corbin, D. R., Whitney, J. F., Fulz, W. C., Stucky, G. D., Eddy, M. M. & Cheetham, A. K. (1986). Inorg. Chem. 25, 2279-2280.]); Lee & Ye (1997[Lee, K.-H. & Ye, J. (1997). J. Solid State Chem. 131, 131-137.]); Hidouri et al. (2003[Hidouri, M., Lajmi, B., Driss, A. & Ben Amara, M. (2003). Acta Cryst. E59, i7-i9.], 2004[Hidouri, M., Lajmi, B., Wattiaux, A., Fournes, L., Darriet, J. & Amara, M. B. (2004). J. Solid State Chem. 177, 55-60.], 2008[Hidouri, M., Lajmi, B., Wattiaux, A., Fournes, L., Darriet, J. & Amara, M. B. (2008). J. Alloys Compd, 450, 301-305.]) Antenucci et al. (1993[Antenucci, D., Miehe, G., Tarte, P., Shmahl, W. W. & Fransolet, A. M. (1993). Eur. J. Mineral. 5, 207-213.], 1995[Antenucci, D., Fransolet, A. M., Miehe, G. & Tarte, P. (1995). Eur. J. Mineral. 7, 175-181.]); For P—O distances, see: Baur (1974[Baur, W. H. (1974). Acta Cryst. B30, 1195-1215.]). For bond-valence sums, see: Brown & Altermatt (1985[Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244-247.]). For ionic radii, see: Shannon (1976[Shannon, R. D. (1976). Acta Cryst. A32, 751-767.]).

Experimental

Crystal data

  • K0.53Mn2.37Fe1.24(PO4)3

  • Mr = 505.28

  • Monoclinic, C 2/c

  • 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[Parkin, S., Moezzi, B. & Hope, H. (1995). J. Appl. Cryst. 28, 53-56.]) Tmin = 0.42, Tmax = 0.81

  • 1754 measured reflections

  • 1308 independent reflections

  • 1047 reflections with I > 2σ(I)

  • Rint = 0.042

  • 2 standard reflections every 120 min intensity decay: 1%
Refinement

  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 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[Enraf-Nonius (1994). CAD-4 EXPRESS. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); program(s) used to solve structure: SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051238/br2150Isup2.hkl

checkCIF report


Comment top

The term alluaudite is referred to both natural and synthetic phosphates of compositions (Na+)(Na+, Ca2+)(M2+)(Fe2+,Fe3+)2(PO4)3 where M2+ is a divalent cation. The first detailed structural description was reported in 1971 by Moore (Moore, 1971) who proposed the structural formula (X2)(X1)(M1)(M2)2(PO4)3. X1 and X2 are cationic sites available to large monovalent and divalent cations such as Na+ and Ca2+ while M1 and M2 are octahedral sites containing a distribution of divalent and trivalent cations of moderate size such as Mn2+, Fe2+ or Fe3+. More recently, detailed structural analysis of several alluaudites demonstrated that the X2 site has two distinct positions labeled A2 (0, 0, 0) and A'2 (0,~0, 1/4) in a tunnel at (0, 0, z) and X1 has three distinct positions, labeled A1 (1/2, 0, 0), A'1 (0,~1/2, 1/4) and A''1 (x, y, z) in a tunnel at (1/2, 0, z). The general formula of Moore was then reformulated as [(A2)(A'2)][(A1)(A'1)(A''1)](M1)(M2)2(PO4)3. The crystal structure consists of M22O10 bioctahedral units of edge-sharing M2O6 octahedra, sharing opposite edges with M1O6 octahedra that form zigzag chains of a sequence –M(2)—M(2)—M(1)-, running along the [1 0 - 1] direction. Adjacent chains are linked by the phosphate tetrahedra leading to what have been described as "pleated sheets" perpendicular to the [0 1 0] direction (Fig. 1(b)). These sheets are connected by the phosphate groups giving rise to a three-dimensional framework with two sets of tunnels parallel to [001] (Fig. 1(b)).

The title phase K0.53Mn2.37Fe1.24(PO4)3 was isolated during an attempt to synthesize KMnFe2(PO4)3 and its structure has shown to be of the alluaudite type. The site occupancy factors indicated to the following cation distribution: 0.53 K on A'2, 0.31 Mn on A''1, 1.0 Mn on M1 and (0.62 Fe + 0.38 Mn) on M2. The partial occupancy of the large A sites has already been observed in several alluaudites being attributed to the great flexibility of these sites which allows them to be filled totally, partially or left vacant without significant influence on the alluaudite framework. Assuming a maximum gap in the cation-oxygen distances, the envronment of the A'2 site (figure 2) consists of eight oxygen atoms forming what has been called by Moore as a gable desphenoid (Moore, 1971). That of the A''1 site (figure 2) onsists of five O atoms forming a distorted trigonal bipyramid. The fivefold coordination of this site which is, to the best of our knowledge, observed for the first time in an alluaudite-like compound can be attributed to the small size of the Mn2+ cation. Both the M1 and M2 sites are octahedrally coordinated (figure 2). From the M1—O distances and cis O—M1—O angles, one can deduce that the M1O6 octahedron is strongly distorted. However, the mean M1—O> mean distance of 2.238 Å is close to that 2.23 Å predicted by Shannon for octahedral Mn2+ cations (Shannon, 1976). The M2—O distances and cis O—M2—O angles show the M2O6 octahedron to be less distorted than M1O6. The <M(2)—O> mean distance (2.068 Å) is between 2.03 Å and 2.23 Å, calculated by Shannon (Shannon, 1976) for the Fe3+ and Mn2+ cations, respectively. This result confirms the presence of both atoms on the M(2) site. The PO4 tetrahedra have classical P—O distances with an overall value of 1.537 Å close to that 1.537 Å, assigned by Baur for the monophosphate groups (Baur, 1974). The Bond Valence Sums (BVS) were calculated for all cationic sites by the Brown and Altermatt method (Brown et al., 1985). The analysis of the sums for the M2 site, around Fe3+ and Mn2+ led to valence sums of 2.87 and 2.64, respectively which corresponds to occupation numbers of 0.71 and 0.29, very close to the x-ray values of 0.62 and 0.38. The sum around Mn3 is 1.34 and around K is 0.42. These are poor because of the partial occupancy but unfortunately these values cannot be used to estimate the occupancy. The sums around P1 and P2 of 4.92 and 4.98, respectively around the O sites (from 1.91 to 2.12) are consistent with the predicted ones of 5 for P and 2 for O. In summery, the valence calculation results gave a good confirmation of the structure, including the assigned oxidation states which cannot be determined by x-ray analysis.

Related literature top

For the alluaudite structure, see: Fisher (1955); Moore (1971); Chouaibi et al. (20016); Corbin et al. (19867); Lee & Ye (19974); Hidouri et al. (20031, 20042, 20083). For related literature [on what subject?], see: 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).

For related literature, see: Hidouri et al. (2004, 2008).

Experimental top

Single crystals of the title phase were extracted from a mixture of nominal composition KMnFe2(PO4)3. The latter was prepared by the flux method starting from a mixture of 2.042 g of KNO3, 2.589 g of Mn(NO3)2.6H2O, 8.245 g of Fe(NO3)3.9H2O, 4.002 g of (NH4)2HPO4 and 0.719 g of MoO3. These reactants were dissolved in nitric acid and the solution obtained was dried for 24 h at 353 K. The obtained dry residue was ground in an agate mortar to ensure its best homogeneity, then heated in a platinum crucible to 673 K for 24 h in order to remove the decomposition products: NH3 and H2O. The sample was then reground, melted at 1173 K for 1 h and subsequently cooled at a 10 °.h-1 rate to 673 K. The final product was washed with warm water in order to dissolve the flux. From the mixture, dark brown and hexagonally shaped crystals were extracted. Their analysis using ICP confirmed the presence of only K, Mn, Fe and P in atomic ratio of 0.53:2.37:1.24:3, in accordance with the K0.53Mn2.37Fe1.24(PO4)3 composition.

Structure description top

The term alluaudite is referred to both natural and synthetic phosphates of compositions (Na+)(Na+, Ca2+)(M2+)(Fe2+,Fe3+)2(PO4)3 where M2+ is a divalent cation. The first detailed structural description was reported in 1971 by Moore (Moore, 1971) who proposed the structural formula (X2)(X1)(M1)(M2)2(PO4)3. X1 and X2 are cationic sites available to large monovalent and divalent cations such as Na+ and Ca2+ while M1 and M2 are octahedral sites containing a distribution of divalent and trivalent cations of moderate size such as Mn2+, Fe2+ or Fe3+. More recently, detailed structural analysis of several alluaudites demonstrated that the X2 site has two distinct positions labeled A2 (0, 0, 0) and A'2 (0,~0, 1/4) in a tunnel at (0, 0, z) and X1 has three distinct positions, labeled A1 (1/2, 0, 0), A'1 (0,~1/2, 1/4) and A''1 (x, y, z) in a tunnel at (1/2, 0, z). The general formula of Moore was then reformulated as [(A2)(A'2)][(A1)(A'1)(A''1)](M1)(M2)2(PO4)3. The crystal structure consists of M22O10 bioctahedral units of edge-sharing M2O6 octahedra, sharing opposite edges with M1O6 octahedra that form zigzag chains of a sequence –M(2)—M(2)—M(1)-, running along the [1 0 - 1] direction. Adjacent chains are linked by the phosphate tetrahedra leading to what have been described as "pleated sheets" perpendicular to the [0 1 0] direction (Fig. 1(b)). These sheets are connected by the phosphate groups giving rise to a three-dimensional framework with two sets of tunnels parallel to [001] (Fig. 1(b)).

The title phase K0.53Mn2.37Fe1.24(PO4)3 was isolated during an attempt to synthesize KMnFe2(PO4)3 and its structure has shown to be of the alluaudite type. The site occupancy factors indicated to the following cation distribution: 0.53 K on A'2, 0.31 Mn on A''1, 1.0 Mn on M1 and (0.62 Fe + 0.38 Mn) on M2. The partial occupancy of the large A sites has already been observed in several alluaudites being attributed to the great flexibility of these sites which allows them to be filled totally, partially or left vacant without significant influence on the alluaudite framework. Assuming a maximum gap in the cation-oxygen distances, the envronment of the A'2 site (figure 2) consists of eight oxygen atoms forming what has been called by Moore as a gable desphenoid (Moore, 1971). That of the A''1 site (figure 2) onsists of five O atoms forming a distorted trigonal bipyramid. The fivefold coordination of this site which is, to the best of our knowledge, observed for the first time in an alluaudite-like compound can be attributed to the small size of the Mn2+ cation. Both the M1 and M2 sites are octahedrally coordinated (figure 2). From the M1—O distances and cis O—M1—O angles, one can deduce that the M1O6 octahedron is strongly distorted. However, the mean M1—O> mean distance of 2.238 Å is close to that 2.23 Å predicted by Shannon for octahedral Mn2+ cations (Shannon, 1976). The M2—O distances and cis O—M2—O angles show the M2O6 octahedron to be less distorted than M1O6. The <M(2)—O> mean distance (2.068 Å) is between 2.03 Å and 2.23 Å, calculated by Shannon (Shannon, 1976) for the Fe3+ and Mn2+ cations, respectively. This result confirms the presence of both atoms on the M(2) site. The PO4 tetrahedra have classical P—O distances with an overall value of 1.537 Å close to that 1.537 Å, assigned by Baur for the monophosphate groups (Baur, 1974). The Bond Valence Sums (BVS) were calculated for all cationic sites by the Brown and Altermatt method (Brown et al., 1985). The analysis of the sums for the M2 site, around Fe3+ and Mn2+ led to valence sums of 2.87 and 2.64, respectively which corresponds to occupation numbers of 0.71 and 0.29, very close to the x-ray values of 0.62 and 0.38. The sum around Mn3 is 1.34 and around K is 0.42. These are poor because of the partial occupancy but unfortunately these values cannot be used to estimate the occupancy. The sums around P1 and P2 of 4.92 and 4.98, respectively around the O sites (from 1.91 to 2.12) are consistent with the predicted ones of 5 for P and 2 for O. In summery, the valence calculation results gave a good confirmation of the structure, including the assigned oxidation states which cannot be determined by x-ray analysis.

For the alluaudite structure, see: Fisher (1955); Moore (1971); Chouaibi et al. (20016); Corbin et al. (19867); Lee & Ye (19974); Hidouri et al. (20031, 20042, 20083). For related literature [on what subject?], see: 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).

For related literature, see: Hidouri et al. (2004, 2008).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Polyhedral representations of the K0.53Mn2.37Fe1.24(PO4)3 structure as projected along [010] (a) and along [001] (b). M1O6, M2O6 are represented by yellow and red octahedra,respectively and PO4 by crossed tetrahedra.
[Figure 2] Fig. 2. The environments of the A'1, A"2, M1, M2, P1 and P2 sites showing the anisotropic atomic displacements. The thermal ellipsoids are drown at 50 % probability level.
Potassium dimanganese iron triphosphate top
Crystal data top
K0.53Mn2.37Fe1.24(PO4)3F(000) = 957
Mr = 505.28Dx = 3.727 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 12.272 (2) Åθ = 9.8–14.4°
b = 12.606 (2) ŵ = 6.07 mm−1
c = 6.416 (4) ÅT = 293 K
β = 114.87 (2)°Hexagonal, brown
V = 900.5 (6) Å30.43 × 0.09 × 0.02 mm
Z = 4
Data collection top
Enraf–Nonius TurboCAD-4
diffractometer		1047 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.042
Graphite monochromatorθmax = 30.0°, θmin = 2.4°
non–profiled ω/2θ scansh = −17→15
Absorption correction: part of the refinement model (ΔF)
(Parkin et al., 1995)		k = 0→17
Tmin = 0.42, Tmax = 0.81l = 0→9
1754 measured reflections2 standard reflections every 120 min
1308 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary 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 = 1.07Δρmax = 0.78 e Å−3
1308 reflectionsΔρmin = −0.68 e Å−3
102 parametersExtinction correction: SHELXL97 (Sheldrick, 2008)
2 restraintsExtinction coefficient: 0.0009 (4)
Crystal data top
K0.53Mn2.37Fe1.24(PO4)3V = 900.5 (6) Å3
Mr = 505.28Z = 4
Monoclinic, C2/cMo Kα radiation
a = 12.272 (2) ŵ = 6.07 mm−1
b = 12.606 (2) ÅT = 293 K
c = 6.416 (4) Å0.43 × 0.09 × 0.02 mm
β = 114.87 (2)°
Data collection top
Enraf–Nonius TurboCAD-4
diffractometer		1047 reflections with I > 2σ(I)
Absorption correction: part of the refinement model (ΔF)
(Parkin et al., 1995)		Rint = 0.042
Tmin = 0.42, Tmax = 0.812 standard reflections every 120 min
1754 measured reflections intensity decay: 1%
1308 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037102 parameters
wR(F2) = 0.0892 restraints
S = 1.07Δρmax = 0.78 e Å−3
1308 reflectionsΔρmin = −0.68 e Å−3
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
K0.0000−0.0116 (2)0.25000.0229 (7)0.531 (5)
Mn10.00000.26376 (7)0.25000.0156 (2)
Fe20.22489 (4)0.15521 (4)0.13977 (8)0.01004 (16)0.6217 (6)
Mn20.22489 (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)
P10.00000.28642 (11)−0.25000.0096 (3)
O110.0479 (2)0.2160 (2)−0.0331 (4)0.0138 (5)
O12−0.0942 (3)0.3615 (2)−0.2314 (6)0.0251 (7)
P20.24436 (8)0.10810 (7)0.63905 (15)0.0093 (2)
O210.2272 (2)0.1782 (2)0.8220 (4)0.0156 (6)
O220.1735 (3)0.1629 (2)0.4048 (4)0.0169 (6)
O230.3783 (2)0.1019 (2)0.6976 (6)0.0255 (7)
O240.1930 (2)−0.0019 (2)0.6349 (5)0.0178 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K0.0093 (10)0.0218 (13)0.0260 (13)0.000−0.0040 (9)0.000
Mn10.0115 (4)0.0202 (4)0.0154 (4)0.0000.0058 (3)0.000
Fe20.0065 (2)0.0138 (3)0.0065 (3)0.00016 (18)−0.00043 (19)0.0008 (2)
Mn20.0065 (2)0.0138 (3)0.0065 (3)0.00016 (18)−0.00043 (19)0.0008 (2)
Mn30.0156 (12)0.0164 (9)0.0165 (11)−0.0002 (9)−0.0070 (7)0.0014 (9)
P10.0060 (5)0.0140 (6)0.0038 (5)0.000−0.0028 (4)0.000
O110.0087 (11)0.0193 (13)0.0066 (11)−0.0027 (10)−0.0033 (9)0.0028 (10)
O120.0149 (13)0.0245 (15)0.0301 (17)0.0025 (12)0.0037 (13)−0.0119 (14)
P20.0065 (4)0.0123 (4)0.0050 (4)0.0004 (3)−0.0016 (3)0.0012 (3)
O210.0128 (12)0.0235 (14)0.0078 (11)−0.0030 (11)0.0017 (10)−0.0038 (11)
O220.0244 (14)0.0141 (14)0.0048 (11)0.0003 (11)−0.0010 (10)−0.0007 (10)
O230.0114 (13)0.0189 (15)0.047 (2)0.0003 (11)0.0132 (14)−0.0018 (15)
O240.0127 (12)0.0184 (14)0.0171 (13)−0.0013 (11)0.0012 (11)0.0030 (11)
Geometric parameters (Å, º) top
K—O242.608 (3)Mn1—O22i2.315 (3)
K—O24i2.608 (3)Mn1—O222.315 (3)
K—O24ii2.767 (3)Fe2—O24ii1.970 (3)
K—O24iii2.767 (3)Fe2—O12x2.027 (3)
K—O11iv2.869 (4)Fe2—O222.049 (3)
K—O11v2.869 (4)Fe2—O21xi2.071 (3)
K—O222.929 (3)Fe2—O112.123 (3)
K—O22i2.929 (3)Fe2—O21vi2.167 (3)
Mn3—O23vi2.253 (4)P1—O12xii1.537 (3)
Mn3—O23vii2.256 (4)P1—O121.537 (3)
Mn3—O12viii2.294 (4)P1—O11xii1.544 (3)
Mn3—O122.335 (4)P1—O111.544 (3)
Mn3—O23ix2.400 (4)P2—O241.519 (3)
Mn1—O23vi2.189 (3)P2—O231.526 (3)
Mn1—O23vii2.189 (3)P2—O221.547 (3)
Mn1—O112.215 (3)P2—O211.553 (3)
Mn1—O11i2.215 (3)
O24—K—O24i174.63 (16)O23vi—Mn1—O1186.39 (11)
O24—K—O24ii73.24 (8)O23vii—Mn1—O11118.95 (12)
O24i—K—O24ii106.42 (8)O23vi—Mn1—O11i118.95 (12)
O24—K—O24iii106.42 (8)O23vii—Mn1—O11i86.39 (11)
O24i—K—O24iii73.24 (8)O11—Mn1—O11i148.43 (15)
O24ii—K—O24iii172.95 (16)O23vi—Mn1—O22i159.42 (10)
O24—K—O11iv114.87 (10)O23vii—Mn1—O22i85.06 (10)
O24i—K—O11iv70.34 (8)O11—Mn1—O22i90.70 (10)
O24ii—K—O11iv87.10 (9)O11i—Mn1—O22i71.87 (10)
O24iii—K—O11iv99.26 (10)O23vi—Mn1—O2285.06 (10)
O24—K—O11v70.34 (8)O23vii—Mn1—O22159.42 (10)
O24i—K—O11v114.87 (10)O11—Mn1—O2271.87 (10)
O24ii—K—O11v99.26 (10)O11i—Mn1—O2290.70 (10)
O24iii—K—O11v87.10 (9)O22i—Mn1—O22113.36 (14)
O11iv—K—O11v52.22 (11)O24ii—Fe2—O12x94.65 (12)
O24—K—O2253.32 (8)O24ii—Fe2—O2286.05 (12)
O24i—K—O22121.80 (11)O12x—Fe2—O22109.44 (13)
O24ii—K—O2257.49 (9)O24ii—Fe2—O21xi101.92 (12)
O24iii—K—O22116.43 (11)O12x—Fe2—O21xi87.13 (12)
O11iv—K—O22144.11 (8)O22—Fe2—O21xi161.16 (11)
O11v—K—O22122.58 (8)O24ii—Fe2—O11101.11 (11)
O24—K—O22i121.80 (11)O12x—Fe2—O11162.62 (11)
O24i—K—O22i53.32 (8)O22—Fe2—O1179.18 (11)
O24ii—K—O22i116.43 (11)O21xi—Fe2—O1182.52 (11)
O24iii—K—O22i57.49 (9)O24ii—Fe2—O21vi174.59 (11)
O11iv—K—O22i122.58 (8)O12x—Fe2—O21vi81.71 (11)
O11v—K—O22i144.11 (8)O22—Fe2—O21vi91.37 (11)
O22—K—O22i82.66 (13)O21xi—Fe2—O21vi81.97 (11)
O23vi—Mn3—O23vii75.91 (14)O11—Fe2—O21vi83.04 (10)
O23vi—Mn3—O12viii84.68 (13)O12xii—P1—O12104.0 (3)
O23vii—Mn3—O12viii121.62 (16)O12xii—P1—O11xii107.33 (17)
Mn1viii—Mn3—O1276.0 (3)O12—P1—O11xii114.23 (15)
O23vi—Mn3—O1294.38 (14)O12xii—P1—O11114.23 (15)
O23vii—Mn3—O1279.85 (14)O12—P1—O11107.33 (17)
O12viii—Mn3—O12157.20 (11)O11xii—P1—O11109.7 (2)
Mn1viii—Mn3—O23ix69.7 (3)O24—P2—O23110.71 (16)
O23vi—Mn3—O23ix157.58 (11)O24—P2—O22109.32 (15)
O23vii—Mn3—O23ix123.93 (15)O23—P2—O22111.67 (18)
O12viii—Mn3—O23ix91.62 (14)O24—P2—O21110.22 (17)
O12—Mn3—O23ix80.58 (13)O23—P2—O21108.50 (16)
O23vi—Mn1—O23vii78.61 (15)O22—P2—O21106.32 (16)
Symmetry codes: (i) −x, y, −z+1/2; (ii) x, −y, z−1/2; (iii) −x, −y, −z+1; (iv) −x, −y, −z; (v) x, −y, z+1/2; (vi) −x+1/2, −y+1/2, −z+1; (vii) x−1/2, −y+1/2, z−1/2; (viii) −x, −y+1, −z; (ix) x−1/2, y+1/2, z−1; (x) x+1/2, −y+1/2, z+1/2; (xi) x, y, z−1; (xii) −x, y, −z−1/2.

Experimental details

Crystal data
Chemical formulaK0.53Mn2.37Fe1.24(PO4)3
Mr505.28
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)12.272 (2), 12.606 (2), 6.416 (4)
β (°) 114.87 (2)
V (Å3)900.5 (6)
Z4
Radiation typeMo Kα
µ (mm−1)6.07
Crystal size (mm)0.43 × 0.09 × 0.02
Data collection
DiffractometerEnraf–Nonius TurboCAD-4
Absorption correctionPart of the refinement model (ΔF)
(Parkin et al., 1995)
Tmin, Tmax0.42, 0.81
No. of measured, independent and
observed [I > 2σ(I)] reflections		1754, 1308, 1047
Rint0.042
(sin θ/λ)max (Å−1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.089, 1.07
No. of reflections1308
No. of parameters102
No. of restraints2
Δρmax, Δρmin (e Å−3)0.78, −0.68

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

 

References

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ISSN: 2056-9890
Volume 67| Part 1| January 2011| Page i1
https://doi.org/10.1107/S1600536810051238
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