BaMn(II) 2Mn(III)(PO4)3.

The title compound, barium trimanganese tris-(ortho-phosphate), was synthesized hydro-thermally. Its structure is isotypic with the lead and strontium analogues AMn(II) 2Mn(III)(PO4)3 (A = Pb, Sr). Except for two O atoms on general positions, all atoms are located on special positions. The Ba and one P atom exhibit mm2 symmetry, the Mn(II) atom 2/m symmetry, the Mn(III) atom and the other P atom .2. symmetry and two O atoms are located on mirror planes. The crystal structure contains two types of chains running parallel to [010]. One chain is linear and is composed of alternating Mn(III)O6 octa-hedra and PO4 tetra-hedra sharing vertices; the other chain has a zigzag arrangement and is built up from two edge-sharing Mn(II)O6 octa-hedra connected to PO4 tetra-hedra by edges and vertices. The two types of chains are linked through PO4 tetra-hedra into an open three-dimensional framework which contains channels parallel to [100] and [010] in which the Ba(II) ions are located. The alkaline earth cation is surrounded by eight O atoms in the form of a slightly distorted bicapped trigonal prism.

Related literature

For the isotypic lead and strontium analogues, see: Alhakmi et al. (2013a ▶) and (2013b ▶), respectively. For related structures, see: Adam et al. (2009 ▶); Assani et al. (2011a ▶,b ▶). For bond-valence analysis, see: Brown & Altermatt (1985 ▶). For the by- product phase, see: Moore & Araki (1973 ▶).

Experimental

Crystal data

BaMn3(PO4)3

M = 587.07

Orthorhombic,

a = 10.3038 (7) Å

b = 14.0163 (11) Å

c = 6.7126 (4) Å

V = 969.44 (12) Å3

Z = 4

Mo Kα radiation

μ = 8.39 mm−1

T = 296 K

0.29 × 0.17 × 0.13 mm

Data collection

Bruker X8 APEX diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.164, T max = 0.376

3968 measured reflections

811 independent reflections

732 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.055

S = 1.09

811 reflections

53 parameters

Δρmax = 1.86 e Å−3

Δρmin = −0.78 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813023106/wm2767sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813023106/wm2767Isup2.hkl

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

BaMn3(PO4)3	F(000) = 1088
Mr = 587.07	Dx = 4.022 Mg m−3
Orthorhombic, Imma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2b 2	Cell parameters from 811 reflections
a = 10.3038 (7) Å	θ = 3.4–30.5°
b = 14.0163 (11) Å	µ = 8.39 mm−1
c = 6.7126 (4) Å	T = 296 K
V = 969.44 (12) Å3	Block, brown
Z = 4	0.29 × 0.17 × 0.13 mm

Bruker X8 APEX diffractometer	811 independent reflections
Radiation source: fine-focus sealed tube	732 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ and ω scans	θmax = 30.5°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→13
Tmin = 0.164, Tmax = 0.376	k = −19→20
3968 measured reflections	l = −9→7

Refinement on F2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.020	Secondary atom site location: difference Fourier map
wR(F2) = 0.055	w = 1/[σ2(Fo2) + (0.0353P)2] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
811 reflections	Δρmax = 1.86 e Å−3
53 parameters	Δρmin = −0.78 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
Ba1	0.0000	0.2500	−0.11499 (4)	0.01125 (10)
Mn1	0.0000	0.5000	0.5000	0.00794 (15)
Mn2	0.2500	0.36758 (4)	0.2500	0.01092 (13)
P1	0.0000	0.2500	0.39677 (16)	0.0078 (2)
P2	0.2500	0.57094 (6)	0.2500	0.00851 (17)
O1	0.0000	0.15998 (16)	0.5237 (4)	0.0115 (5)
O2	0.1185 (2)	0.2500	0.2553 (3)	0.0107 (4)
O3	0.21046 (19)	0.63040 (12)	0.0721 (3)	0.0133 (3)
O4	0.36337 (16)	0.49927 (12)	0.1983 (2)	0.0103 (3)

	U11	U22	U33	U12	U13	U23
Ba1	0.01480 (16)	0.01187 (15)	0.00707 (14)	0.000	0.000	0.000
Mn1	0.0102 (3)	0.0081 (3)	0.0056 (3)	0.000	0.000	−0.0001 (2)
Mn2	0.0154 (3)	0.0063 (2)	0.0110 (2)	0.000	−0.00074 (18)	0.000
P1	0.0104 (5)	0.0065 (5)	0.0066 (5)	0.000	0.000	0.000
P2	0.0121 (4)	0.0064 (4)	0.0071 (3)	0.000	0.0010 (3)	0.000
O1	0.0166 (12)	0.0049 (9)	0.0129 (11)	0.000	0.000	0.0014 (8)
O2	0.0121 (11)	0.0103 (11)	0.0098 (10)	0.000	0.0035 (8)	0.000
O3	0.0183 (8)	0.0114 (8)	0.0100 (7)	0.0027 (6)	0.0006 (7)	0.0033 (6)
O4	0.0123 (8)	0.0087 (7)	0.0100 (7)	0.0014 (6)	0.0016 (6)	0.0009 (5)

Ba1—O1i	2.734 (2)	Mn2—O2	2.1337 (16)
Ba1—O1ii	2.734 (2)	Mn2—O2xiii	2.1337 (16)
Ba1—O3iii	2.7560 (18)	Mn2—O3iii	2.2006 (17)
Ba1—O3iv	2.7560 (18)	Mn2—O3ix	2.2006 (17)
Ba1—O3v	2.7560 (18)	Mn2—O4	2.2117 (17)
Ba1—O3vi	2.7560 (18)	Mn2—O4x	2.2117 (17)
Ba1—O2	2.769 (2)	P1—O1	1.523 (2)
Ba1—O2vii	2.769 (2)	P1—O1vii	1.523 (2)
Mn1—O4viii	1.9377 (17)	P1—O2vii	1.547 (2)
Mn1—O4ix	1.9377 (17)	P1—O2	1.547 (2)
Mn1—O4x	1.9377 (17)	P2—O3x	1.5119 (17)
Mn1—O4xi	1.9377 (17)	P2—O3	1.5119 (17)
Mn1—O1vii	2.248 (2)	P2—O4x	1.5792 (17)
Mn1—O1xii	2.248 (2)	P2—O4	1.5792 (17)
O1i—Ba1—O1ii	54.97 (9)	O4ix—Mn1—O1vii	87.51 (6)
O1i—Ba1—O3iii	111.92 (5)	O4x—Mn1—O1vii	92.49 (6)
O1ii—Ba1—O3iii	79.16 (5)	O4xi—Mn1—O1vii	87.51 (6)
O1i—Ba1—O3iv	79.16 (5)	O4viii—Mn1—O1xii	87.51 (6)
O1ii—Ba1—O3iv	111.92 (5)	O4ix—Mn1—O1xii	92.49 (6)
O3iii—Ba1—O3iv	168.02 (7)	O4x—Mn1—O1xii	87.51 (6)
O1i—Ba1—O3v	79.16 (5)	O4xi—Mn1—O1xii	92.49 (6)
O1ii—Ba1—O3v	111.92 (5)	O1vii—Mn1—O1xii	180.0
O3iii—Ba1—O3v	74.93 (8)	O2—Mn2—O2xiii	78.86 (10)
O3iv—Ba1—O3v	103.78 (8)	O2—Mn2—O3iii	84.77 (8)
O1i—Ba1—O3vi	111.92 (5)	O2xiii—Mn2—O3iii	96.38 (8)
O1ii—Ba1—O3vi	79.16 (5)	O2—Mn2—O3ix	96.38 (8)
O3iii—Ba1—O3vi	103.78 (8)	O2xiii—Mn2—O3ix	84.77 (8)
O3iv—Ba1—O3vi	74.93 (8)	O3iii—Mn2—O3ix	178.52 (9)
O3v—Ba1—O3vi	168.02 (7)	O2—Mn2—O4	169.28 (7)
O1i—Ba1—O2	142.77 (4)	O2xiii—Mn2—O4	107.86 (7)
O1ii—Ba1—O2	142.77 (4)	O3iii—Mn2—O4	86.16 (6)
O3iii—Ba1—O2	63.86 (5)	O3ix—Mn2—O4	92.61 (7)
O3iv—Ba1—O2	104.67 (5)	O2—Mn2—O4x	107.86 (7)
O3v—Ba1—O2	63.86 (5)	O2xiii—Mn2—O4x	169.28 (7)
O3vi—Ba1—O2	104.67 (5)	O3iii—Mn2—O4x	92.61 (7)
O1i—Ba1—O2vii	142.77 (4)	O3ix—Mn2—O4x	86.16 (6)
O1ii—Ba1—O2vii	142.77 (4)	O4—Mn2—O4x	66.86 (9)
O3iii—Ba1—O2vii	104.67 (5)	O1—P1—O1vii	111.94 (19)
O3iv—Ba1—O2vii	63.86 (5)	O1—P1—O2vii	110.09 (7)
O3v—Ba1—O2vii	104.67 (5)	O1vii—P1—O2vii	110.09 (7)
O3vi—Ba1—O2vii	63.86 (5)	O1—P1—O2	110.09 (7)
O2—Ba1—O2vii	52.33 (10)	O1vii—P1—O2	110.09 (7)
O4viii—Mn1—O4ix	180.0	O2vii—P1—O2	104.27 (19)
O4viii—Mn1—O4x	93.19 (10)	O3x—P2—O3	113.10 (14)
O4ix—Mn1—O4x	86.81 (10)	O3x—P2—O4x	112.12 (9)
O4viii—Mn1—O4xi	86.81 (10)	O3—P2—O4x	108.95 (10)
O4ix—Mn1—O4xi	93.19 (10)	O3x—P2—O4	108.95 (10)
O4x—Mn1—O4xi	180.0	O3—P2—O4	112.12 (9)
O4viii—Mn1—O1vii	92.49 (6)	O4x—P2—O4	100.99 (13)