Crystal structure of strontium dicobalt iron(III) tris-(orthophosphate): SrCo2Fe(PO4)3.

The title compound, SrCo2Fe(PO4)3, has been synthesized by a solid-state reaction. It crystallizes with the α-CrPO4 type structure. In this structure, all atoms are on special positions of the Imma space group, except for two O atoms which are located on general positions. The three-dimensional network in the crystal structure is made up of two types of layers stacked normal to (100). The first layer is built from two edge-sharing CoO6 octa-hedra, leading to the formation of Co2O10 dimers that are connected to two PO4 tetra-hedra by a common edge and corners. The second layer results from apex-sharing FeO6 octa-hedra and PO4 tetra-hedra, which form linear chains alternating with a zigzag chain of Sr(II) cations. These layers are linked together by common vertices of PO4 tetra-hedra and FeO6 octa-hedra to form an open three-dimensional framework that delimits two types of channels parallel to [100] and [010] where the Sr(II) cations are located. Each Sr(II) cation is surrounded by eight O atoms.

Chemical context

The phosphate literature includes important works on the structural study of transition metal phosphates. The basic framework is built from tetra­hedrally coordinated phospho­rus linked to transition metals M in various environments, such as MO (n = 4, 5 or 6). The manner in which polyhedra are inter­connected generates important structure types with porous or lamellar set-ups that can exhibit inter­esting physical properties. Accordingly, widespread studies have been devoted to this family of compounds, stimulated by the wide range of potential and commercial applications of these materials. Examples include applications in catalysis, as ion exchangers and in the manufacture of lithium and sodium rechargeable batteries. One particular scientific area in our laboratory is focused on investigating new functional phosphates belonging to the alluaudite (Moore, 1971 ▸) or α-CrPO4 (Attfield et al., 1988 ▸) structure types, owing to their potential use as new cathode materials for battery devices (Trad et al., 2010 ▸; Kim et al., 2014 ▸; Huang et al., 2015 ▸).

Our earlier hydro­thermal investigations were undertaken with the A 2O–MO–P2O5 and M′O–MO–P2O5 systems (A = monovalent cations, M and M′ = divalent cations) with approximate molar ratios A:M:P = 2:3:3 and M′:M:P = 1:3:3, which characterize the alluaudite or α-CrPO4 phases. Those studies involved the synthesis and structural characterization of new phosphates such as Na2Co2Fe(PO4)3 (Bouraima et al., 2015 ▸) and Na1.67Zn1.67Fe1.33(PO4)3 (Khmiyas et al., 2015 ▸) belonging to the alluaudite-type structure group. In addition, divalent and trivalent transition-metal-based phosphates, such as SrNi2Fe(PO4)3 (Ouaatta et al., 2015 ▸) and MMnII 2MnIII(PO4)3 (M = Pb, Sr, Ba) (Alhakmi et al., 2013a ▸, Assani et al., 2013 ▸) have been shown to adopt the α-CrPO4 structure type.

In search of a new promising phosphate, a solid-state chemistry investigation of A 2O–MO–M′2O3–P2O5 systems was undertaken. The present work reports on synthesis and crystal structure of the new strontium cobalt iron phosphate, SrCo2Fe(PO4)3, which has the α-CrPO4 type structure.

Structural commentary

In the title phosphate, SrCo2Fe(PO4)3, all atoms are on special positions, except two oxygen atoms (O3, O4) which are on general positions of the Imma space group. Its three-dimensional structure is constructed on the basis of PO4 tetra­hedra, FeO6 and CoO6 octa­hedra, as shown in Fig. 1 ▸. The connection between these polyhedra produces two types of layers stacked normal to (100). The first layer is built from two edge-sharing CoO6 octa­hedra, leading to the formation of Co2O10 dimers, which are connected to two PO4 tetra­hedra by a common edge and vertex, as shown in Fig. 2 ▸. The second layer is formed by alternating FeO6 octa­hedra and PO4 tetra­hedra, which share corners, building linear chains that surround a zigzag chain of SrII cations (see Fig. 3 ▸). The layers are joined by the apices of PO4 tetra­hedra and FeO6 octa­hedra, giving rise to an open three-dimensional framework that delimits two types of channels parallel to [100] and [010] where the SrII cations are located, as shown in Fig. 4 ▸ and Fig. 5 ▸. This structure is characterized by a stoichiometric composition in which the Sr atom is surrounded by eight oxygen atoms with Sr—O bond lengths that vary between 2.6561 (13) and 2.6690 (9)Å. The same Sr environment is observed in the manganese homologue phosphates, namely MMnII 2MnIII(PO4)3 (M = Pb, Sr, Ba).

Figure 1

The principal building units in the structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −x + 2, −y + , z + 1; (ii) x, y, z + 1; (iii) −x + 2, −y + , z; (iv) −x + , −y + 1, z + ; (v) x + , y + , z + ; (vi) −x + , y + , z + ; (ix) −x + , y, −z + ; (x) x, −y + 1, −z; (xi) −x + 1, y, z; (xii) x, −y + 1, −z + 1; (xiii) −x + 1, −y + 1, −z + 1;(xiv) x − , y, −z + .]

Figure 2

Edge-sharing [CoO6] octa­hedra forming a layer parallel to (100).

Figure 3

A view along the a axis, showing a layer resulting from chains connected via vertices of PO4 tetra­hedra and FeO6 octa­hedra, alternating with a zigzag chain of Sr atoms.

Figure 4

Polyhedral representation of SrCo2Fe(PO4)3, showing channels running along [100].

Figure 5

Polyhedral representation of SrCo2Fe(PO4)3, showing channels running along [010].

Synthesis and crystallization

The title phosphate, SrCo2Fe(PO4)3, was synthesized in a solid-state reaction by mixing nitrates of strontium, cobalt and iron along with NH4H2PO4, taken in the molar proportions Sr:Co:Fe:P = 1:2:1:3. After a series of heat treatments up to 873 K in a platinum crucible, inter­spersed with grinding, the reaction mixture was heated to the melt (1343 K). The molten product was then cooled to room temperature at 5 K/h. The resulting solid contained brown crystals of a suitable size for X-ray diffraction.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1 ▸. The highest peak and the deepest hole in the final Fourier map are at 0.63 and 0.68 Å from Sr1 and P2, respectively.

Table 1

Experimental details

Crystal data
Chemical formula	SrCo2Fe(PO4)3
M r	546.24
Crystal system, space group	Orthorhombic, I m m a
Temperature (K)	296
a, b, c (Å)	10.4097 (2), 13.2714 (3), 6.5481 (2)
V (Å3)	904.63 (4)
Z	4
Radiation type	Mo Kα
μ (mm−1)	11.64
Crystal size (mm)	0.30 × 0.27 × 0.21
Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max	0.595, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	10008, 1297, 1243
R int	0.030
(sin θ/λ)max (Å−1)	0.858
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.017, 0.046, 1.16
No. of reflections	1297
No. of parameters	54
Δρmax, Δρmin (e Å−3)	1.00, −0.74

Computer programs: APEX2 and SAINT (Bruker, 2009 ▸), SHELXT2014 (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸), DIAMOND (Brandenburg, 2006 ▸) and publCIF (Westrip, 2010 ▸).

The distinction between cobalt and iron by X-ray diffraction is nearly impossible. Therefore we have examined several crystallographic models during the crystal structure refinements of the title compound. Based on the stoichiometric ratio of 1:2 for iron and cobalt in the starting materials, we assumed the same ratio in the crystal structures with oxidation states of +II for cobalt and and +III for iron. The best model is obtained with Fe1 and Co1 atoms in the Wyckoff positions 4a (2/m) and 8g (2), respectively. This cationic distribution in this model corresponds to the stoichiometry of the expected compound, in addition to the electric neutrality in the structure in reasonable agreement with the final model.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016011373/pk2584sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016011373/pk2584Isup2.hkl

CCDC reference: 1492743

Additional supporting information: crystallographic information; 3D view; checkCIF report

SrCo2Fe(PO4)3	Dx = 4.011 Mg m−3
Mr = 546.24	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Imma	Cell parameters from 1297 reflections
a = 10.4097 (2) Å	θ = 3.1–37.6°
b = 13.2714 (3) Å	µ = 11.64 mm−1
c = 6.5481 (2) Å	T = 296 K
V = 904.63 (4) Å3	Block, brown
Z = 4	0.30 × 0.27 × 0.21 mm
F(000) = 1036

Bruker X8 APEX diffractometer	1297 independent reflections
Radiation source: fine-focus sealed tube	1243 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 37.6°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −17→17
Tmin = 0.595, Tmax = 0.747	k = −22→19
10008 measured reflections	l = −11→11

Refinement on F2	0 restraints
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0245P)2 + 0.761P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.017	(Δ/σ)max < 0.001
wR(F2) = 0.046	Δρmax = 1.00 e Å−3
S = 1.16	Δρmin = −0.74 e Å−3
1297 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2014b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
54 parameters	Extinction coefficient: 0.0131 (4)

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.

	x	y	z	Uiso*/Ueq
Sr1	1.0000	0.7500	0.59715 (3)	0.00785 (6)
Co1	0.7500	0.63284 (2)	0.2500	0.00537 (6)
Fe1	0.5000	0.5000	0.5000	0.00392 (7)
P1	1.0000	0.7500	0.09098 (8)	0.00336 (9)
P2	0.7500	0.42747 (3)	0.2500	0.00388 (7)
O1	1.0000	0.65633 (9)	−0.04439 (19)	0.00660 (18)
O2	0.88277 (11)	0.7500	0.23618 (18)	0.00607 (18)
O3	0.71075 (8)	0.36360 (6)	0.06735 (14)	0.00776 (14)
O4	0.63833 (7)	0.50376 (6)	0.29533 (14)	0.00600 (13)

	U11	U22	U33	U12	U13	U23
Sr1	0.00819 (9)	0.01003 (10)	0.00534 (9)	0.000	0.000	0.000
Co1	0.00533 (9)	0.00376 (10)	0.00704 (10)	0.000	0.00073 (6)	0.000
Fe1	0.00292 (11)	0.00439 (13)	0.00443 (12)	0.000	0.000	0.00015 (9)
P1	0.00344 (18)	0.0029 (2)	0.0038 (2)	0.000	0.000	0.000
P2	0.00410 (14)	0.00365 (17)	0.00388 (14)	0.000	0.00051 (10)	0.000
O1	0.0081 (4)	0.0045 (5)	0.0073 (4)	0.000	0.000	−0.0017 (4)
O2	0.0046 (4)	0.0073 (5)	0.0063 (4)	0.000	0.0020 (3)	0.000
O3	0.0094 (3)	0.0075 (3)	0.0064 (3)	−0.0017 (3)	0.0003 (3)	−0.0023 (2)
O4	0.0050 (3)	0.0057 (3)	0.0074 (3)	0.0013 (2)	0.0021 (2)	0.0006 (2)

Sr1—O1i	2.6561 (13)	Fe1—O4	1.9678 (8)
Sr1—O1ii	2.6561 (13)	Fe1—O4xi	1.9678 (8)
Sr1—O2iii	2.6600 (12)	Fe1—O4xii	1.9678 (8)
Sr1—O2	2.6600 (12)	Fe1—O4xiii	1.9678 (8)
Sr1—O3iv	2.6690 (9)	Fe1—O1iv	2.0950 (12)
Sr1—O3v	2.6690 (9)	Fe1—O1xiv	2.0950 (12)
Sr1—O3vi	2.6690 (9)	P1—O1iii	1.5268 (12)
Sr1—O3vii	2.6690 (9)	P1—O1	1.5268 (12)
Co1—O2	2.0824 (8)	P1—O2iii	1.5470 (12)
Co1—O2viii	2.0824 (8)	P1—O2	1.5470 (12)
Co1—O4ix	2.0913 (8)	P2—O3	1.5219 (9)
Co1—O4	2.0914 (8)	P2—O3ix	1.5219 (9)
Co1—O3x	2.1183 (9)	P2—O4	1.5698 (8)
Co1—O3iv	2.1183 (9)	P2—O4ix	1.5698 (8)
O1i—Sr1—O1ii	55.81 (5)	O2viii—Co1—O3x	84.14 (4)
O1i—Sr1—O2iii	141.74 (2)	O4ix—Co1—O3x	89.21 (3)
O1ii—Sr1—O2iii	141.74 (2)	O4—Co1—O3x	92.88 (3)
O1i—Sr1—O2	141.74 (2)	O2—Co1—O3iv	84.14 (4)
O1ii—Sr1—O2	141.74 (2)	O2viii—Co1—O3iv	93.94 (4)
O2iii—Sr1—O2	54.61 (5)	O4ix—Co1—O3iv	92.89 (3)
O1i—Sr1—O3iv	109.21 (2)	O4—Co1—O3iv	89.21 (3)
O1ii—Sr1—O3iv	78.48 (2)	O3x—Co1—O3iv	177.44 (5)
O2iii—Sr1—O3iv	108.19 (3)	O4—Fe1—O4xi	94.07 (5)
O2—Sr1—O3iv	63.77 (3)	O4—Fe1—O4xii	85.93 (5)
O1i—Sr1—O3v	78.48 (2)	O4xi—Fe1—O4xii	180.0
O1ii—Sr1—O3v	109.21 (2)	O4—Fe1—O4xiii	180.0
O2iii—Sr1—O3v	63.77 (3)	O4xi—Fe1—O4xiii	85.93 (5)
O2—Sr1—O3v	108.19 (3)	O4xii—Fe1—O4xiii	94.07 (5)
O3iv—Sr1—O3v	171.61 (4)	O4—Fe1—O1iv	86.02 (3)
O1i—Sr1—O3vi	78.48 (2)	O4xi—Fe1—O1iv	86.02 (3)
O1ii—Sr1—O3vi	109.21 (2)	O4xii—Fe1—O1iv	93.98 (3)
O2iii—Sr1—O3vi	108.19 (3)	O4xiii—Fe1—O1iv	93.98 (3)
O2—Sr1—O3vi	63.77 (3)	O4—Fe1—O1xiv	93.98 (3)
O3iv—Sr1—O3vi	68.78 (4)	O4xi—Fe1—O1xiv	93.98 (3)
O3v—Sr1—O3vi	110.56 (4)	O4xii—Fe1—O1xiv	86.02 (3)
O1i—Sr1—O3vii	109.21 (2)	O4xiii—Fe1—O1xiv	86.02 (3)
O1ii—Sr1—O3vii	78.48 (2)	O1iv—Fe1—O1xiv	180.0
O2iii—Sr1—O3vii	63.77 (3)	O1iii—P1—O1	109.01 (10)
O2—Sr1—O3vii	108.19 (3)	O1iii—P1—O2iii	110.91 (3)
O3iv—Sr1—O3vii	110.56 (4)	O1—P1—O2iii	110.91 (3)
O3v—Sr1—O3vii	68.78 (4)	O1iii—P1—O2	110.91 (3)
O3vi—Sr1—O3vii	171.61 (4)	O1—P1—O2	110.91 (3)
O2—Co1—O2viii	83.39 (5)	O2iii—P1—O2	104.15 (9)
O2—Co1—O4ix	103.68 (3)	O3—P2—O3ix	112.30 (7)
O2viii—Co1—O4ix	170.65 (4)	O3—P2—O4	108.00 (5)
O2—Co1—O4	170.65 (4)	O3ix—P2—O4	114.17 (5)
O2viii—Co1—O4	103.68 (3)	O3—P2—O4ix	114.17 (5)
O4ix—Co1—O4	70.01 (4)	O3ix—P2—O4ix	108.00 (5)
O2—Co1—O3x	93.94 (4)	O4—P2—O4ix	99.68 (6)