Crystal structures of two alkaline earth (M = Ba and Sr) dimanganese(II) iron(III) tris­(orthophosphates)

Alhakmi, G.; Assani, A.; Saadi, M.; El Ammari, L.

doi:10.1107/S2056989017006120

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Volume 73| Part 5| May 2017| Pages 767-770

https://doi.org/10.1107/S2056989017006120

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Crystal structures of two alkaline earth (M = Ba and Sr) dimanganese(II) iron(III) tris(orthophosphates)

Ghaleb Alhakmi,^a ^* Abderrazzak Assani,^a Mohamed Saadi ^a and Lahcen El Ammari ^a

^aLaboratoire de Chimie du Solide Appliquée, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: g_alhakmi@yahoo.fr

Edited by M. Weil, Vienna University of Technology, Austria (Received 10 April 2017; accepted 23 April 2017; online 28 April 2017)

Two new orthophosphates, BaMn₂Fe(PO₄)₃ [barium dimanganese(II) iron(III) tris(orthophosphate)] and SrMn₂Fe(PO₄)₃ [strontium dimanganese(II) iron(III) tris(orthophosphate)], were synthesized by solid-state reactions. They are isotypic and crystallize in the orthorhombic system with space group type Pbcn. Their crystal structures comprise infinite zigzag chains of edge-sharing FeO₆ octahedra (point group symmetry .2.) and Mn₂O₁₀ double octahedra running parallel to [001], linked by two types of PO₄ tetrahedra. The so-formed three-dimensional framework delineates channels running along [001], in which the alkaline earth cations (site symmetry .2.) are located within a neighbourhood of eight O atoms.

Keywords: crystal structure; BaMn₂Fe(PO₄)₃; SrMn₂Fe(PO₄)₃; transition metal; phosphates; solid-state reaction synthesis.

CCDC references: 1545505; 1545504

1. Chemical context

Considerable attention has been devoted to the preparation of new inorganic materials with open-framework structures (Rao et al., 2001 ; Bouzidi et al., 2015 ) due to their structural diversity covering a wide range of chemical compositions (Zhou et al., 2002 ). In particular, transition-metal-based open-framework phosphates represent a highly attractive class of materials in industrial processes. In fact, their special framework structures lead to interesting properties that depend not only on the inclusion guest in the pores, but also on the chosen transition metal (Durio et al., 2002 ; López et al., 2004 ; Férey et al., 2005 ). Typical examples are ion-exchangers (Jignasa et al., 2006 ; Kullberg & Clearfield, 1981 ) and compounds with special magnetic (Chouaibi et al., 2001 ; Ferdov et al., 2008 ) and catalytic properties (Weng et al., 2009 ).

In this context, our group focuses on the synthesis and characterization of new transition-metal phosphates crystallizing either in alluaudite- (Moore, 1971 ) or α-CrPO₄-type structures (Attfield et al., 1988 ). In attempts to obtain new compounds belonging to the latter structure type, we have synthesized and structurally characterized several new phosphates, including those with oxidation states of both +II and +III for manganese. These compounds have the general formula MMn^IIIMn₂^II(PO₄)₃ (M = Pb, Sr, Ba) (Alhakmi et al., 2013a ,b ; Assani et al., 2013 ) and adopt the α-CrPO₄ structure type. Recently, the phosphates Na₂Co₂Fe(PO₄)₃ (Bouraima et al., 2015 ) and Na_1.67Zn_1.67Fe_1.33(PO₄)₃ (Khmiyas et al., 2015 ) with an alluaudite-like structure were also reported. As a continuation in this regard, we have now extended our investigations to the quaternary system MO/MnO/Fe₂O₃/P₂O₅, where M is a divalent cation. The present work deals with the synthesis and the crystal structures of two new isotypic alkaline earth manganese iron phosphates, namely, BaMn₂Fe(PO₄)₃ and SrMn₂Fe(PO₄)₃. Their structures show a similarity with that of AM₄(PO₄)₃ phosphates where A is a monovalent cation and M a divalent cation (Daidouh et al., 1999 ; Assaaoudi et al., 2006 ).

2. Structural commentary

The principal building units in the crystal structures of both phosphates are distorted FeO₆ and MnO₆ octahedra, PO₄ tetrahedra and Ba²⁺ or Sr²⁺ cations as shown in Figs. 1 and 2. In each structure, two MnO₆ octahedra are linked together by a common edge to give a Mn₂O₁₀ dimer to which FeO₆ octahedra (point group symmetry .2.) are alternately connected on both sides. In this way, infinite zigzag chains parallel to [001] are formed (Fig. 3). Adjacent chains are linked together by sharing corners with two types of PO₄ tetrahedra, forming a layer-like arrangement parallel to (010) as shown in Fig. 4. Such layers are stacked along [010] to form a three-dimensional framework (Fig. 5) with two types of channels running parallel to [001] in which the alkaline earth cations are located on a twofold rotation axis. They are coordinated by eight oxygen atoms (Figs. 1 and 6), with bond lengths ranging from 2.6803 (10) to 2.8722 (11) Å for the BaO₈ polyhedron and of 2.6020 (9) to 2.7358 (11) Å for the SrO₈ polyhedron.

Figure 1
The principal building units in the structure of BaMn₂Fe(PO₄)₃. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x, −y + 1, z + $[{1\over 2}]$ ; (ii) −x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z + 2; (iii) x, y, z + 1; (iv) −x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1; (v) −x + 1, y, −z + $[{3\over 2}]$ ; (vi) x, y, z − 1; (vii) −x + 1, y, −z + $[{1\over 2}]$ ; (viii) x − $[{1\over 2}]$ , −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ ; (ix) −x + 1, −y + 1, −z + 1; (x) x, −y + 1, z − $[{1\over 2}]$ ; (xi) −x + 2, y, −z + $[{3\over 2}]$ ; (xii) −x + 2, −y + 1, −z + 1.]

Figure 2
The principal building units in the structure of SrMn₂Fe(PO₄)₃. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x, −y + 1, z + $[{1\over 2}]$ ; (ii) −x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z + 2; (iii) x, y, z + 1; (iv) −x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1; (v) −x + 1, y, −z + $[{3\over 2}]$ ; (vi) x, y, z − 1; (vii) −x + 1, y, −z + $[{1\over 2}]$ ; (viii) x − $[{1\over 2}]$ , −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ ; (ix) −x + 1, −y + 1, −z + 1; (x) x, −y + 1, z − $[{1\over 2}]$ ; (xi) −x + 2, y, −z + $[{3\over 2}]$ ; (xii) −x + 2, −y + 1, −z + 1.]

Figure 3
Edge-sharing [FeO₆] octahedra and Mn₂O₁₀ dimers forming an infinite zigzag chain running parallel to [001]. Data are from BaMn₂Fe(PO₄)₃.

Figure 4
A layer perpendicular to (010), resulting from the connection of metal oxide chains through PO₄ tetrahedra. Data are from BaMn₂Fe(PO₄)₃.

Figure 5
A view of stacked layers along [010]. Data are from BaMn₂Fe(PO₄)₃.

Figure 6
Polyhedral representation of the BaMn₂Fe(PO₄)₃ structure showing Ba²⁺ cations situated in channels running along [001].

Bond-valence-sum calculations (Brown & Altermatt, 1985 ) are in good agreement with the expected values for alkaline earth, manganese(II) and iron(III) cations and the phosphorus(V) atom. BaMn₂Fe(PO₄)₃ (values in valence units): Ba²⁺ 2.10; Mn²⁺ 2.00; Fe³⁺ 3.12; P^V 4.94. SrMn₂Fe(PO₄)₃: Sr²⁺ 1.80; Mn²⁺ 2.07; Fe³⁺ 3.18; P^V 5.00.

3. Database survey

A comparison between the structures of the title compounds and those of other phosphates such as the AM₄(PO₄)₃ compounds (A = monovalent cation and M = divalent cation) (Im et al., 2014 ), reveals that all these compounds crystallize with orthorhombic symmetry and nearly the same unit-cell parameters despite the differences between their chemical formulae and space groups. In order to give an illustrative picture of the similarity between these two formula types, we can write the general formula of AM₄(PO₄)₃ compounds as follows: M′²⁺(A⁺M²⁺)M₂²⁺(PO₄)₃ and that of the title compounds as M′²⁺Fe³⁺Mn₂²⁺(PO₄)₃. The principal structures of the title compounds and that of the AM₄(PO₄)₃ compounds are formed by stacking of the same infinite zigzag chains of edge-sharing octahedra. Furthermore, these structures are characterized by the presence of two types of channels in which the large cations are located.

4. Synthesis and crystallization

Single crystals of the title compounds were isolated as a result of solid-state reactions. Stoichiometric amounts of alkaline earth (M = Ba, Sr), manganese, iron and phosphate precursors in a molar ratio M:Mn:Fe:P = 1:2:1:3, were dissolved in 40 ml water that was placed into a 100 ml capacity pyrex glass beaker. The mixture was stirred at room temperature for 20 h and was evaporated under stirring at 363 K until dryness. The obtained black powder was ground in an agate mortar and pre-heated at 573 K in a platinum crucible for 24 h to eliminate gaseous materials. Subsequently, the resulting residue was reground and melted for 30 min at 1293 K, followed by slow cooling down to 1093 K at a rate 5K h⁻¹ and a rapid cooling to room temperature by switching off the furnace. In the case of the BaO–MnO–Fe₂O₃–P₂O₅ system, the reaction product consisted of two types of crystals, viz. orange crystals of the title compound, BaMn₂Fe(PO₄)₃, and dark-violet crystals that were identified to be another new phase. In the case of the SrO–MnO–Fe₂O₃–P₂O₅ system, the reaction product contained dark-brown crystals corresponding to the title compound, SrMn₂Fe(PO₄)₃.

5. Refinement

Crystal data, data collection and structure refinement details for the two compounds are summarized in Table 1. For BaMn₂Fe(PO₄)₃, the maximum and minimum remaining electron densities are located 0.60 and 0.42 Å from atom Ba1. For SrMn₂Fe(PO₄)₃, they are 0.58 and 0.31 Å from Sr1.

Table 1
Experimental details

	(I)	(II)
Crystal data
Chemical formula	BaMn₂Fe(PO₄)₃	SrMn₂Fe(PO₄)₃
M_r	587.98	538.25
Crystal system, space group	Orthorhombic, Pbcn	Orthorhombic, Pbcn
Temperature (K)	296	296
a, b, c (Å)	6.5899 (2), 17.6467 (4), 8.5106 (2)	6.4304 (3), 17.8462 (7), 8.4906 (3)
V (Å³)	989.70 (4)	974.37 (7)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	8.41	10.00
Crystal size (mm)	0.32 × 0.25 × 0.22	0.30 × 0.27 × 0.23

Data collection
Diffractometer	Bruker X8 APEX	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.596, 0.748	0.404, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	29422, 3088, 2731	23889, 2843, 2564
R_int	0.033	0.031
(sin θ/λ)_max (Å⁻¹)	0.907	0.887

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.044, 1.05	0.021, 0.048, 1.08
No. of reflections	3088	2843
No. of parameters	89	89
Δρ_max, Δρ_min (e Å⁻³)	1.29, −1.11	1.19, −0.81
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1545505; 1545504

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S2056989017006120/wm5384sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017006120/wm5384Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989017006120/wm5384IIsup3.hkl

checkCIF report

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b). Molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006) for (I); ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006) for (II). For both compounds, software used to prepare material for publication: publCIF (Westrip, 2010).

(I) Barium dimanganese(II) iron(III) tris(orthophosphate) top

Crystal data top

BaMn₂Fe(PO₄)₃	D_x = 3.946 Mg m⁻³
M_r = 587.98	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 3088 reflections
a = 6.5899 (2) Å	θ = 3.3–40.1°
b = 17.6467 (4) Å	µ = 8.41 mm⁻¹
c = 8.5106 (2) Å	T = 296 K
V = 989.70 (4) Å³	Block, orange
Z = 4	0.32 × 0.25 × 0.22 mm
F(000) = 1092

Data collection top

Bruker X8 APEX diffractometer	3088 independent reflections
Radiation source: fine-focus sealed tube	2731 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
φ and ω scans	θ_max = 40.1°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −8→11
T_min = 0.596, T_max = 0.748	k = −31→32
29422 measured reflections	l = −15→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0178P)² + 1.2088P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.018	(Δ/σ)_max = 0.002
wR(F²) = 0.044	Δρ_max = 1.29 e Å⁻³
S = 1.05	Δρ_min = −1.11 e Å⁻³
3088 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
89 parameters	Extinction coefficient: 0.00278 (15)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ba1	0.5000	0.44269 (2)	0.7500	0.01037 (3)
Fe1	1.0000	0.31799 (2)	0.7500	0.00461 (4)
Mn1	0.83899 (3)	0.36570 (2)	0.39874 (2)	0.00647 (4)
P1	0.83270 (5)	0.17935 (2)	0.53771 (3)	0.00490 (5)
P2	1.0000	0.47123 (2)	0.7500	0.00513 (7)
O1	1.01958 (15)	0.12822 (6)	0.55338 (13)	0.01186 (16)
O2	0.66250 (15)	0.15480 (5)	0.64868 (11)	0.00865 (14)
O3	0.76365 (15)	0.17592 (5)	0.36487 (10)	0.00794 (14)
O4	0.88706 (16)	0.26335 (5)	0.57277 (11)	0.01031 (15)
O5	0.89269 (15)	0.41422 (5)	0.63609 (10)	0.00656 (13)
O6	0.83805 (16)	0.51729 (5)	0.83211 (12)	0.00988 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.00562 (5)	0.01428 (5)	0.01119 (5)	0.000	−0.00082 (3)	0.000
Fe1	0.00537 (9)	0.00435 (8)	0.00411 (8)	0.000	0.00015 (7)	0.000
Mn1	0.00598 (7)	0.00785 (6)	0.00559 (7)	−0.00021 (5)	0.00041 (6)	0.00013 (5)
P1	0.00360 (11)	0.00666 (10)	0.00443 (10)	−0.00050 (9)	−0.00036 (9)	−0.00071 (8)
P2	0.00571 (17)	0.00355 (13)	0.00611 (15)	0.000	0.00000 (13)	0.000
O1	0.0058 (4)	0.0170 (4)	0.0128 (4)	0.0047 (3)	−0.0016 (3)	−0.0004 (3)
O2	0.0064 (3)	0.0126 (3)	0.0070 (3)	−0.0017 (3)	0.0007 (3)	0.0021 (3)
O3	0.0066 (4)	0.0127 (3)	0.0045 (3)	0.0002 (3)	−0.0018 (3)	−0.0017 (3)
O4	0.0136 (4)	0.0087 (3)	0.0086 (3)	−0.0047 (3)	−0.0002 (3)	−0.0028 (3)
O5	0.0084 (3)	0.0058 (3)	0.0055 (3)	−0.0007 (3)	−0.0009 (3)	−0.0003 (2)
O6	0.0091 (4)	0.0071 (3)	0.0134 (4)	0.0017 (3)	0.0011 (3)	−0.0031 (3)

Geometric parameters (Å, º) top

Ba1—O6	2.6803 (10)	Mn1—O6^vi	2.1413 (9)
Ba1—O6ⁱ	2.6803 (10)	Mn1—O1ⁱⁱ	2.1466 (10)
Ba1—O3ⁱⁱ	2.7861 (9)	Mn1—O2^vii	2.1587 (9)
Ba1—O3ⁱⁱⁱ	2.7861 (9)	Mn1—O2^v	2.1997 (10)
Ba1—O5	2.8087 (10)	Mn1—O5	2.2223 (9)
Ba1—O5ⁱ	2.8087 (10)	Mn1—O4	2.3572 (10)
Ba1—O1ⁱⁱ	2.8722 (11)	P1—O2	1.5289 (10)
Ba1—O1ⁱⁱⁱ	2.8722 (11)	P1—O1	1.5325 (10)
Fe1—O4	1.9387 (9)	P1—O3	1.5409 (9)
Fe1—O4^iv	1.9387 (9)	P1—O4	1.5540 (9)
Fe1—O3^v	1.9965 (9)	P2—O6	1.5126 (10)
Fe1—O3ⁱⁱⁱ	1.9965 (9)	P2—O6^iv	1.5126 (10)
Fe1—O5^iv	2.0792 (9)	P2—O5	1.5659 (9)
Fe1—O5	2.0793 (9)	P2—O5^iv	1.5660 (9)

O6—Ba1—O6ⁱ	121.17 (4)	O4^iv—Fe1—O5^iv	85.00 (4)
O6—Ba1—O3ⁱⁱ	157.68 (3)	O3^v—Fe1—O5^iv	83.59 (4)
O6ⁱ—Ba1—O3ⁱⁱ	79.21 (3)	O3ⁱⁱⁱ—Fe1—O5^iv	91.36 (4)
O6—Ba1—O3ⁱⁱⁱ	79.21 (3)	O4—Fe1—O5	85.00 (4)
O6ⁱ—Ba1—O3ⁱⁱⁱ	157.68 (3)	O4^iv—Fe1—O5	154.09 (4)
O3ⁱⁱ—Ba1—O3ⁱⁱⁱ	82.60 (4)	O3^v—Fe1—O5	91.36 (4)
O6—Ba1—O5	53.99 (3)	O3ⁱⁱⁱ—Fe1—O5	83.59 (4)
O6ⁱ—Ba1—O5	139.79 (3)	O5^iv—Fe1—O5	70.50 (5)
O3ⁱⁱ—Ba1—O5	105.04 (3)	O6^vi—Mn1—O1ⁱⁱ	89.96 (4)
O3ⁱⁱⁱ—Ba1—O5	58.11 (3)	O6^vi—Mn1—O2^vii	84.29 (4)
O6—Ba1—O5ⁱ	139.79 (3)	O1ⁱⁱ—Mn1—O2^vii	101.01 (4)
O6ⁱ—Ba1—O5ⁱ	53.99 (3)	O6^vi—Mn1—O2^v	96.48 (4)
O3ⁱⁱ—Ba1—O5ⁱ	58.11 (3)	O1ⁱⁱ—Mn1—O2^v	173.39 (4)
O3ⁱⁱⁱ—Ba1—O5ⁱ	105.04 (3)	O2^vii—Mn1—O2^v	78.23 (4)
O5—Ba1—O5ⁱ	159.39 (3)	O6^vi—Mn1—O5	82.51 (4)
O6—Ba1—O1ⁱⁱ	114.27 (3)	O1ⁱⁱ—Mn1—O5	87.96 (4)
O6ⁱ—Ba1—O1ⁱⁱ	90.97 (3)	O2^vii—Mn1—O5	164.03 (4)
O3ⁱⁱ—Ba1—O1ⁱⁱ	51.86 (3)	O2^v—Mn1—O5	94.35 (4)
O3ⁱⁱⁱ—Ba1—O1ⁱⁱ	87.88 (3)	O6^vi—Mn1—O4	154.91 (4)
O5—Ba1—O1ⁱⁱ	64.56 (3)	O1ⁱⁱ—Mn1—O4	92.91 (4)
O5ⁱ—Ba1—O1ⁱⁱ	105.89 (3)	O2^vii—Mn1—O4	119.45 (3)
O6—Ba1—O1ⁱⁱⁱ	90.97 (3)	O2^v—Mn1—O4	81.90 (4)
O6ⁱ—Ba1—O1ⁱⁱⁱ	114.27 (3)	O5—Mn1—O4	72.70 (3)
O3ⁱⁱ—Ba1—O1ⁱⁱⁱ	87.88 (3)	O2—P1—O1	111.65 (6)
O3ⁱⁱⁱ—Ba1—O1ⁱⁱⁱ	51.86 (3)	O2—P1—O3	111.22 (5)
O5—Ba1—O1ⁱⁱⁱ	105.89 (3)	O1—P1—O3	107.29 (6)
O5ⁱ—Ba1—O1ⁱⁱⁱ	64.55 (3)	O2—P1—O4	108.71 (5)
O1ⁱⁱ—Ba1—O1ⁱⁱⁱ	128.34 (4)	O1—P1—O4	111.08 (6)
O4—Fe1—O4^iv	120.35 (6)	O3—P1—O4	106.79 (5)
O4—Fe1—O3^v	88.85 (4)	O6—P2—O6^iv	115.00 (8)
O4^iv—Fe1—O3^v	94.22 (4)	O6—P2—O5	108.22 (5)
O4—Fe1—O3ⁱⁱⁱ	94.22 (4)	O6^iv—P2—O5	112.20 (5)
O4^iv—Fe1—O3ⁱⁱⁱ	88.85 (4)	O6—P2—O5^iv	112.20 (5)
O3^v—Fe1—O3ⁱⁱⁱ	173.83 (5)	O6^iv—P2—O5^iv	108.22 (5)
O4—Fe1—O5^iv	154.09 (4)	O5—P2—O5^iv	100.05 (7)

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

(II) Strontium dimanganese(II) iron(III) tris(orthophosphate) top

Crystal data top

SrMn₂Fe(PO₄)₃	D_x = 3.669 Mg m⁻³
M_r = 538.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 2843 reflections
a = 6.4304 (3) Å	θ = 3.3–39.1°
b = 17.8462 (7) Å	µ = 10.00 mm⁻¹
c = 8.4906 (3) Å	T = 296 K
V = 974.37 (7) Å³	Block, dark brown
Z = 4	0.30 × 0.27 × 0.23 mm
F(000) = 1020

Data collection top

Bruker X8 APEX diffractometer	2843 independent reflections
Radiation source: fine-focus sealed tube	2564 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
φ and ω scans	θ_max = 39.1°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −11→10
T_min = 0.404, T_max = 0.748	k = −31→31
23889 measured reflections	l = −8→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0183P)² + 1.2279P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.021	(Δ/σ)_max = 0.001
wR(F²) = 0.048	Δρ_max = 1.19 e Å⁻³
S = 1.08	Δρ_min = −0.81 e Å⁻³
2843 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
89 parameters	Extinction coefficient: 0.0072 (3)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sr1	0.5000	0.43233 (2)	0.7500	0.00986 (4)
Fe1	1.0000	0.31546 (2)	0.7500	0.00485 (4)
Mn1	0.83818 (3)	0.37163 (2)	0.39547 (2)	0.00679 (4)
P1	0.83555 (5)	0.17749 (2)	0.53581 (3)	0.00571 (5)
P2	1.0000	0.46759 (2)	0.7500	0.00485 (7)
O1	1.02378 (15)	0.12570 (6)	0.54770 (13)	0.01473 (18)
O2	0.66091 (14)	0.15203 (5)	0.64550 (11)	0.00922 (14)
O3	0.76936 (14)	0.17505 (5)	0.36165 (10)	0.00794 (14)
O4	0.89115 (17)	0.25971 (6)	0.57468 (12)	0.01448 (18)
O5	0.89256 (14)	0.41164 (5)	0.63388 (10)	0.00662 (13)
O6	0.82775 (15)	0.51251 (5)	0.82684 (12)	0.00991 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sr1	0.00601 (7)	0.01296 (7)	0.01060 (7)	0.000	−0.00134 (5)	0.000
Fe1	0.00567 (9)	0.00423 (8)	0.00466 (8)	0.000	0.00026 (7)	0.000
Mn1	0.00547 (7)	0.00927 (7)	0.00563 (7)	−0.00023 (5)	0.00064 (5)	−0.00056 (5)
P1	0.00382 (10)	0.00858 (11)	0.00473 (10)	−0.00077 (9)	−0.00010 (9)	−0.00167 (8)
P2	0.00502 (15)	0.00357 (13)	0.00597 (15)	0.000	−0.00017 (12)	0.000
O1	0.0066 (4)	0.0237 (5)	0.0139 (4)	0.0062 (3)	−0.0013 (3)	0.0010 (4)
O2	0.0061 (3)	0.0149 (4)	0.0067 (3)	−0.0015 (3)	0.0009 (3)	0.0025 (3)
O3	0.0067 (3)	0.0125 (3)	0.0046 (3)	0.0001 (3)	−0.0012 (3)	−0.0013 (3)
O4	0.0174 (4)	0.0133 (4)	0.0128 (4)	−0.0084 (3)	0.0029 (3)	−0.0074 (3)
O5	0.0085 (3)	0.0062 (3)	0.0052 (3)	−0.0009 (3)	−0.0016 (3)	−0.0006 (2)
O6	0.0085 (3)	0.0073 (3)	0.0140 (4)	0.0019 (3)	0.0015 (3)	−0.0032 (3)

Geometric parameters (Å, º) top

Sr1—O3ⁱ	2.6020 (9)	Mn1—O1ⁱ	2.0790 (10)
Sr1—O3ⁱⁱ	2.6020 (9)	Mn1—O2^v	2.1462 (9)
Sr1—O6ⁱⁱⁱ	2.6296 (9)	Mn1—O6^vi	2.1494 (9)
Sr1—O6	2.6296 (10)	Mn1—O2^vii	2.1641 (9)
Sr1—O5	2.7351 (9)	Mn1—O5	2.1748 (9)
Sr1—O5ⁱⁱⁱ	2.7351 (9)	Mn1—O4	2.5338 (12)
Sr1—O1ⁱ	2.7358 (11)	P1—O1	1.5263 (10)
Sr1—O1ⁱⁱ	2.7358 (11)	P1—O2	1.5281 (9)
Fe1—O4	1.9224 (10)	P1—O3	1.5394 (9)
Fe1—O4^iv	1.9224 (10)	P1—O4	1.5459 (10)
Fe1—O3^v	1.9818 (9)	P2—O6	1.5149 (9)
Fe1—O3ⁱⁱ	1.9818 (9)	P2—O6^iv	1.5149 (9)
Fe1—O5	2.0966 (9)	P2—O5^iv	1.5641 (9)
Fe1—O5^iv	2.0966 (9)	P2—O5	1.5641 (9)

O3ⁱ—Sr1—O3ⁱⁱ	85.14 (4)	O4^iv—Fe1—O5	155.20 (4)
O3ⁱ—Sr1—O6ⁱⁱⁱ	81.58 (3)	O3^v—Fe1—O5	89.60 (4)
O3ⁱⁱ—Sr1—O6ⁱⁱⁱ	161.43 (3)	O3ⁱⁱ—Fe1—O5	82.35 (4)
O3ⁱ—Sr1—O6	161.43 (3)	O4—Fe1—O5^iv	155.20 (4)
O3ⁱⁱ—Sr1—O6	81.58 (3)	O4^iv—Fe1—O5^iv	86.54 (4)
O6ⁱⁱⁱ—Sr1—O6	114.07 (4)	O3^v—Fe1—O5^iv	82.35 (4)
O3ⁱ—Sr1—O5	107.18 (3)	O3ⁱⁱ—Fe1—O5^iv	89.60 (4)
O3ⁱⁱ—Sr1—O5	60.39 (3)	O5—Fe1—O5^iv	70.09 (5)
O6ⁱⁱⁱ—Sr1—O5	136.36 (3)	O1ⁱ—Mn1—O2^v	169.25 (4)
O6—Sr1—O5	54.77 (3)	O1ⁱ—Mn1—O6^vi	90.60 (4)
O3ⁱ—Sr1—O5ⁱⁱⁱ	60.39 (3)	O2^v—Mn1—O6^vi	100.11 (4)
O3ⁱⁱ—Sr1—O5ⁱⁱⁱ	107.18 (3)	O1ⁱ—Mn1—O2^vii	103.58 (4)
O6ⁱⁱⁱ—Sr1—O5ⁱⁱⁱ	54.77 (3)	O2^v—Mn1—O2^vii	78.47 (4)
O6—Sr1—O5ⁱⁱⁱ	136.36 (3)	O6^vi—Mn1—O2^vii	85.52 (4)
O5—Sr1—O5ⁱⁱⁱ	164.49 (4)	O1ⁱ—Mn1—O5	86.15 (4)
O3ⁱ—Sr1—O1ⁱ	54.30 (3)	O2^v—Mn1—O5	93.44 (4)
O3ⁱⁱ—Sr1—O1ⁱ	91.49 (3)	O6^vi—Mn1—O5	86.65 (4)
O6ⁱⁱⁱ—Sr1—O1ⁱ	91.23 (3)	O2^vii—Mn1—O5	167.55 (4)
O6—Sr1—O1ⁱ	112.98 (3)	O1ⁱ—Mn1—O4	90.54 (4)
O5—Sr1—O1ⁱ	64.17 (3)	O2^v—Mn1—O4	79.18 (4)
O5ⁱⁱⁱ—Sr1—O1ⁱ	109.48 (3)	O6^vi—Mn1—O4	157.72 (4)
O3ⁱ—Sr1—O1ⁱⁱ	91.49 (3)	O2^vii—Mn1—O4	115.78 (3)
O3ⁱⁱ—Sr1—O1ⁱⁱ	54.30 (3)	O5—Mn1—O4	71.23 (3)
O6ⁱⁱⁱ—Sr1—O1ⁱⁱ	112.98 (3)	O1—P1—O2	111.25 (6)
O6—Sr1—O1ⁱⁱ	91.23 (3)	O1—P1—O3	105.40 (6)
O5—Sr1—O1ⁱⁱ	109.48 (3)	O2—P1—O3	111.95 (5)
O5ⁱⁱⁱ—Sr1—O1ⁱⁱ	64.17 (3)	O1—P1—O4	112.17 (6)
O1ⁱ—Sr1—O1ⁱⁱ	135.52 (5)	O2—P1—O4	108.80 (6)
O4—Fe1—O4^iv	117.67 (7)	O3—P1—O4	107.21 (6)
O4—Fe1—O3^v	89.54 (4)	O6—P2—O6^iv	116.11 (7)
O4^iv—Fe1—O3^v	95.53 (4)	O6—P2—O5^iv	112.91 (5)
O4—Fe1—O3ⁱⁱ	95.53 (4)	O6^iv—P2—O5^iv	106.63 (5)
O4^iv—Fe1—O3ⁱⁱ	89.54 (4)	O6—P2—O5	106.64 (5)
O3^v—Fe1—O3ⁱⁱ	170.19 (5)	O6^iv—P2—O5	112.91 (5)
O4—Fe1—O5	86.54 (4)	O5^iv—P2—O5	100.66 (7)

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

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements and Mohammed V University in Rabat, Morocco, for financial support.

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of two alkaline earth (M = Ba and Sr) dimanganese(II) iron(III) tris­­(orthophosphates)

1. Chemical context

2. Structural commentary

3. Database survey

4. Synthesis and crystallization

5. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structures of two alkaline earth (M = Ba and Sr) dimanganese(II) iron(III) tris(orthophosphates)