Crystal structure of calcium dinickel(II) iron(III) tris-(orthophosphate): CaNi2Fe(PO4)3.

The title compound, CaNi2Fe(PO4)3, was synthesized by solid-state reactions. Its structure is closely related to that of α-CrPO4 in the space group Imma. Except for two O atoms in general positions, all atoms are located in special positions. The three-dimensional framework is built up from two types of sheets extending parallel to (100). The first sheet is made up from two edge-sharing [NiO6] octa-hedra, leading to the formation of [Ni2O10] double octa-hedra that are connected to two PO4 tetra-hedra through a common edge and corners. The second sheet results from rows of corner-sharing [FeO6] octa-hedra and PO4 tetra-hedra forming an infinite linear chain. These layers are linked together through common corners of PO4 tetra-hedra and [FeO6] octa-hedra, resulting in an open three-dimensional framework that delimits two types of channels parallel to [100] and [010] in which the eightfold-coordinated CaII cations are located.

Chemical context

Phosphates belonging to the alluaudite (Moore, 1971 ▸) or to the α-CrPO4 (Attfield et al., 1988 ▸) structure type exhibit inter­esting physical and chemical properties. Consequently, these compounds have many promising applications such as use as positive electrodes in lithium and sodium batteries (Kim et al., 2014 ▸; Huang et al., 2015 ▸) or as catalysts (Kacimi et al., 2005 ▸). Over the last few years, phosphate-based compounds crystallizing in the α-CrPO4 or alluaudite structure types have been investigated by us. In this context, new phosphates adopting the alluaudite or α-CrPO4 structure type have been synthesized and structurally characterized. For example, the mixed-valence manganese phosphates PbMnII 2MnIII(PO4)3 (Alhakmi et al., 2013 ▸) and PbMnII 2MnIII(PO4)3 (Assani et al., 2013 ▸), the magnesium phosphate NaMg3(PO4)(HPO4)2 (Ould Saleck et al., 2015 ▸) and silver nickel phosphate Ag2Ni3(HPO4)(PO4)2 (Assani et al., 2011 ▸) were synthesized by hydro­thermal methods, while solid-state reactions were applied to synthesize SrNi2Fe(PO4)3 (Ouaatta et al., 2015 ▸) and Na2Co2Fe(PO4)3 (Bouraima et al., 2015 ▸). In a continuation of the latter preparation route, we have investigated pseudo-quaternary systems MO–NiO–Fe2O3–P2O5 (M represents a divalent cation) and report here on the synthesis and crystal structure of the title compound, CaNi2Fe(PO4)3.

Structural commentary

CaNi2Fe(PO4)3 crystallizes in the α-CrPO4 structure type. The principal building units of the crystal structure are one [CaO8] polyhedron, [FeO6] and [NiO6] octa­hedra and PO4 tetra­hedra, as shown in Fig. 1 ▸.The octa­hedral coordination sphere of the iron(III) cation is more distorted than that of nickel(II), with Fe—O bond lengths in the range 1.9504 (7)–2.0822 (11) Å and Ni—O bond lengths in the range 2.0498 (8)–2.0841 (8) Å. In the title structure, all atoms are on special positions, except for the two oxygen atoms O1 and O2, which are on general positions. The structure can be described by the stacking of two types of sheets extending parallel to (100). The first sheet is formed by alternating [FeO6] octa­hedra and PO4 tetra­hedra sharing corners to build a linear infinite chain surrounding a zigzag chain of CaII+ cations (Fig. 2 ▸). The second sheet is built up from two edge-sharing [NiO6] octa­hedra leading to the formation of [Ni2O10] double octa­hedra, which are connected to two PO4 tetra­hedra by a common edge and a common corner, as shown in Fig. 3 ▸. The linkage of both layers, through vertices of PO4 tetra­hedra and [FeO6] octa­hedra, gives rise to the formation of an open three-dimensional framework that delimits two types of channels parallel to [100] and [010] in which the CaII cations are located with eight neighbouring O atoms, as shown in Fig. 4 ▸. The title compound has a stoichiometric composition like that of the related strontium homologue SrNi2Fe(PO4)3.

Figure 1

The principal building units in the crystal 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 + ; (vii) x + , −y + 1, z + ; (viii) −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

A chain formed by sharing corners of PO4 tetra­hedra and [FeO6] octa­hedra, alternating with a zigzag chain of calcium cations.

Figure 3

Edge-sharing [NiO6] octa­hedra linked by PO4 tetra­hedra, forming a sheet parallel to (100).

Figure 4

Polyhedral representation of CaNiO2Fe(PO4)3, showing channels running parallel to [100].

Synthesis and crystallization

CaNi2Fe(PO4)3 was prepared by solid-state reactions in air. Stoichiometric mixtures of calcium, nickel and iron precursors were dissolved in water to which 85%wt phospho­ric acid was added. The obtained mixture was stirred without heating for 24 h and was subsequently evaporated to dryness at 343 K. The resulting dry residue was ground in an agate mortar until homogeneity, progressively heated in a platinum crucible up to 873 K to remove the volatile decomposition products, and then melted at 1433 K. The molten product was cooled down slowly with a 5 K h−1 rate and then to room temperature. The crystals obtained after washing with water were orange with parallelepipedal forms.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1 ▸. The maximum and minimum remaining electron densities are 0.68 and 0.41 Å, respectively, away from the Ni1 site.

Table 1

Experimental details

Crystal data
Chemical formula	CaNi2Fe(PO4)3
M r	498.26
Crystal system, space group	Orthorhombic, I m m a
Temperature (K)	296
a, b, c (Å)	10.3126 (3), 13.1138 (3), 6.4405 (2)
V (Å3)	871.00 (4)
Z	4
Radiation type	Mo Kα
μ (mm−1)	7.14
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	0.596, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	8446, 1171, 1153
R int	0.020
(sin θ/λ)max (Å−1)	0.840
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.017, 0.044, 1.17
No. of reflections	1171
No. of parameters	54
Δρmax, Δρmin (e Å−3)	0.76, −0.63

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 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017007411/wm5390sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017007411/wm5390Isup2.hkl

CCDC reference: 1551182

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

CaNi2Fe(PO4)3	Dx = 3.800 Mg m−3
Mr = 498.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Imma	Cell parameters from 1171 reflections
a = 10.3126 (3) Å	θ = 3.1–36.6°
b = 13.1138 (3) Å	µ = 7.14 mm−1
c = 6.4405 (2) Å	T = 296 K
V = 871.00 (4) Å3	Parallelepiped, orange
Z = 4	0.30 × 0.27 × 0.21 mm
F(000) = 972

Bruker X8 APEX diffractometer	1171 independent reflections
Radiation source: fine-focus sealed tube	1153 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
φ and ω scans	θmax = 36.6°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −16→17
Tmin = 0.596, Tmax = 0.748	k = −20→22
8446 measured reflections	l = −10→10

Refinement on F2	0 restraints
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0216P)2 + 1.467P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.017	(Δ/σ)max = 0.001
wR(F2) = 0.044	Δρmax = 0.76 e Å−3
S = 1.17	Δρmin = −0.63 e Å−3
1171 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
54 parameters	Extinction coefficient: 0.0033 (2)

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
Ni1	0.7500	0.36655 (2)	0.7500	0.00475 (5)
Fe1	0.5000	0.0000	0.5000	0.00372 (6)
Ca1	0.5000	0.2500	0.08981 (7)	0.01187 (8)
P1	0.7500	0.57298 (3)	0.7500	0.00385 (7)
P2	0.5000	0.2500	0.58291 (8)	0.00327 (8)
O1	0.86146 (7)	0.49415 (6)	0.79418 (13)	0.00590 (12)
O4	0.61754 (11)	0.2500	0.73284 (17)	0.00587 (16)
O3	0.5000	0.15625 (8)	0.44256 (18)	0.00672 (17)
O2	0.70724 (8)	0.63786 (6)	0.93385 (12)	0.00762 (13)

	U11	U22	U33	U12	U13	U23
Ni1	0.00486 (9)	0.00326 (8)	0.00613 (9)	0.000	−0.00056 (5)	0.000
Fe1	0.00264 (10)	0.00397 (11)	0.00455 (11)	0.000	0.000	−0.00016 (8)
Ca1	0.01508 (18)	0.01319 (18)	0.00735 (16)	0.000	0.000	0.000
P1	0.00450 (14)	0.00307 (14)	0.00398 (14)	0.000	−0.00041 (9)	0.000
P2	0.00320 (17)	0.00246 (17)	0.00414 (18)	0.000	0.000	0.000
O1	0.0045 (3)	0.0054 (3)	0.0079 (3)	0.0006 (2)	−0.0021 (2)	−0.0004 (2)
O4	0.0049 (4)	0.0057 (4)	0.0070 (4)	0.000	−0.0023 (3)	0.000
O3	0.0082 (4)	0.0045 (4)	0.0075 (4)	0.000	0.000	−0.0024 (3)
O2	0.0102 (3)	0.0069 (3)	0.0057 (3)	0.0018 (2)	0.0001 (2)	−0.0020 (2)

Ni1—O1	2.0498 (8)	Ca1—O2xi	2.5987 (8)
Ni1—O1i	2.0499 (8)	Ca1—O2xii	2.5987 (8)
Ni1—O4	2.0529 (8)	Ca1—O2xiii	2.5987 (8)
Ni1—O4ii	2.0529 (8)	Ca1—O4xiv	2.5990 (12)
Ni1—O2iii	2.0841 (8)	Ca1—O4xv	2.5990 (12)
Ni1—O2iv	2.0841 (8)	Ca1—P2	3.1758 (7)
Fe1—O1ii	1.9504 (7)	Ca1—P2xv	3.2647 (7)
Fe1—O1v	1.9504 (7)	P1—O2i	1.5233 (8)
Fe1—O1vi	1.9504 (7)	P1—O2	1.5233 (8)
Fe1—O1vii	1.9504 (7)	P1—O1i	1.5719 (8)
Fe1—O3viii	2.0822 (11)	P1—O1	1.5719 (8)
Fe1—O3	2.0822 (11)	P2—O3	1.5259 (11)
Ca1—O3	2.5832 (12)	P2—O3ix	1.5259 (11)
Ca1—O3ix	2.5832 (12)	P2—O4ix	1.5498 (11)
Ca1—O2x	2.5987 (8)	P2—O4	1.5498 (11)
O1—Ni1—O1i	70.58 (4)	O2x—Ca1—O2xi	173.27 (4)
O1—Ni1—O4	171.24 (3)	O3—Ca1—O2xii	77.42 (2)
O1i—Ni1—O4	103.13 (3)	O3ix—Ca1—O2xii	108.72 (2)
O1—Ni1—O4ii	103.13 (3)	O2x—Ca1—O2xii	110.65 (3)
O1i—Ni1—O4ii	171.24 (3)	O2xi—Ca1—O2xii	68.92 (3)
O4—Ni1—O4ii	83.76 (5)	O3—Ca1—O2xiii	108.72 (2)
O1—Ni1—O2iii	90.33 (3)	O3ix—Ca1—O2xiii	77.42 (2)
O1i—Ni1—O2iii	92.27 (3)	O2x—Ca1—O2xiii	68.92 (3)
O4—Ni1—O2iii	83.75 (4)	O2xi—Ca1—O2xiii	110.65 (3)
O4ii—Ni1—O2iii	93.87 (4)	O2xii—Ca1—O2xiii	173.27 (4)
O1—Ni1—O2iv	92.27 (3)	O3—Ca1—O4xiv	141.08 (2)
O1i—Ni1—O2iv	90.33 (3)	O3ix—Ca1—O4xiv	141.08 (2)
O4—Ni1—O2iv	93.87 (4)	O2x—Ca1—O4xiv	64.19 (3)
O4ii—Ni1—O2iv	83.75 (4)	O2xi—Ca1—O4xiv	109.37 (3)
O2iii—Ni1—O2iv	176.81 (4)	O2xii—Ca1—O4xiv	109.37 (3)
O1ii—Fe1—O1v	180.0	O2xiii—Ca1—O4xiv	64.19 (3)
O1ii—Fe1—O1vi	85.81 (5)	O3—Ca1—O4xv	141.08 (2)
O1v—Fe1—O1vi	94.19 (5)	O3ix—Ca1—O4xv	141.08 (2)
O1ii—Fe1—O1vii	94.19 (5)	O2x—Ca1—O4xv	109.37 (3)
O1v—Fe1—O1vii	85.81 (5)	O2xi—Ca1—O4xv	64.19 (3)
O1vi—Fe1—O1vii	180.0	O2xii—Ca1—O4xv	64.19 (3)
O1ii—Fe1—O3viii	85.29 (3)	O2xiii—Ca1—O4xv	109.37 (3)
O1v—Fe1—O3viii	94.71 (3)	O4xiv—Ca1—O4xv	55.60 (5)
O1vi—Fe1—O3viii	94.71 (3)	O2i—P1—O2	112.08 (6)
O1vii—Fe1—O3viii	85.29 (3)	O2i—P1—O1i	116.00 (4)
O1ii—Fe1—O3	94.71 (3)	O2—P1—O1i	107.24 (4)
O1v—Fe1—O3	85.29 (3)	O2i—P1—O1	107.24 (4)
O1vi—Fe1—O3	85.29 (3)	O2—P1—O1	116.00 (4)
O1vii—Fe1—O3	94.71 (3)	O1i—P1—O1	97.76 (6)
O3viii—Fe1—O3	180.000 (10)	O3—P2—O3ix	107.35 (9)
O3—Ca1—O3ix	56.84 (5)	O3—P2—O4ix	111.66 (3)
O3—Ca1—O2x	77.42 (2)	O3ix—P2—O4ix	111.66 (3)
O3ix—Ca1—O2x	108.72 (2)	O3—P2—O4	111.66 (3)
O3—Ca1—O2xi	108.72 (2)	O3ix—P2—O4	111.66 (3)
O3ix—Ca1—O2xi	77.42 (2)	O4ix—P2—O4	102.91 (9)