Crystal structure of (Na0.70)(Na0.70,Mn0.30)(Fe3+,Fe2+)2Fe2+(VO4)3, a sodium-, iron- and manganese-based vanadate with the alluaudite-type structure

Benhsina, E.; Assani, A.; Saadi, M.; El Ammari, L.

doi:10.1107/S2056989016000931

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ISSN: 2056-9890

Volume 72| Part 2| February 2016| Pages 220-222

doi:10.1107/S2056989016000931

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Crystal structure of (Na_0.70)(Na_0.70,Mn_0.30)(Fe³⁺,Fe²⁺)₂Fe²⁺(VO₄)₃, a sodium-, iron- and manganese-based vanadate with the alluaudite-type structure

Elhassan Benhsina,^a ^* Abderrazzak Assani,^a Mohamed Saadi ^a and Lahcen El Ammari ^a

^aLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V de Rabat, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: el_benhsina@yahoo.fr

Edited by M. Weil, Vienna University of Technology, Austria (Received 21 December 2015; accepted 15 January 2016; online 23 January 2016)

The title compound, sodium (sodium,manganese) triiron(II,III) tris[vanadate(V)], (Na_0.70)(Na_0.70,Mn_0.30)(Fe³⁺,Fe²⁺)₂Fe²⁺(VO₄)₃, was prepared by solid-state reactions. It crystallizes in an alluaudite-like structure, characterized by a partial cationic disorder. In the structure, four of the 12 sites in the asymmetric unit are located on special positions, three on a twofold rotation axis (Wyckoff position 4e) and one on an inversion centre (4b). Two sites on the twofold rotation axis are entirely filled by Fe²⁺ and V⁵⁺, whereas the third site has a partial occupancy of 70% by Na⁺. The site on the inversion centre is occupied by Na⁺ and Mn²⁺ cations in a 0.7:0.3 ratio. The remaining Fe²⁺ and Fe³⁺ atoms are statistically distributed on a general position. The three-dimensional framework of this structure is made up of kinked chains of edge-sharing [FeO₆] octahedra stacked parallel to [10-1]. These chains are held together by VO₄ tetrahedral groups, forming polyhedral sheets perpendicular to [010]. Within this framework, two types of channels extending along [001] are present. One is occupied by (Na⁺/Mn²⁺) while the second is partially occupied by Na⁺. The mixed site containing (Na⁺/Mn²⁺) has an octahedral coordination sphere, while the Na⁺ cations in the second channel are coordinated by eight O atoms.

Keywords: crystal structure; transition metal vanadate; solid-state reaction synthesis; alluaudite-type structure.

CCDC reference: 1447912

1. Chemical context

Over recent decades, the synthesis and structural characterization of transition-metal-based functional materials adopting layered or channel structures has been the focus of much scientific work. In accordance with widespread studies devoted to the improvement of those materials, we have contributed to the search for new functional materials by undertaking synthesis and structural characterization of new transition and alkali metal phosphates exhibiting channel structures and belonging to the well-known alluaudite structure type (Moore, 1971 ) that can be represented by the general formula A(1)A(2)M(1)M(2)₂(XO₄)₃. The M(1) and M(2) sites accommodate di- or trivalent cations in an octahedral environment and are connected to the tetrahedral XO₄ groups, leading to an open-framework structure. Alluaudite-type phosphates are of special interest as positive electrode materials in lithium and sodium batteries. For instance, the alluaudite-type lithium manganese phosphate Li_0.78Na_0.22MnPO₄ is proposed by Kim et al. (2014 ) as a promising new positive electrode for Li rechargeable batteries. Furthermore, in the more active alluaudite-type cathode material for sodium-ion batteries, Na₂Fe_3-xMn_x(PO₄)₃, the electrochemical performance is associated either with morphology or with the electronic and crystalline structure (Huang et al., 2015 ).

Responding to the growing demand for this type of functional materials, we were able to prepare new alluaudite-type phosphates within pseudo-ternary A₂O/MO/P₂O₅ or pseudo-quaternary A₂O/MO/Fe₂O₃/P₂O₅ systems by means of hydrothermal or solid-state reactions: AgMg₃(HPO₄)₂PO₄ (Assani et al., 2011 ), NaMg₃(HPO₄)₂PO₄ (Ould Saleck et al., 2015 ), Na₂Co₂Fe(PO₄)₃ (Bouraima et al., 2015 ) and Na_1.67Zn_1.67Fe_1.33(PO₄)₃ (Khmiyas et al., 2015 ).

Besides well-known phosphate phases, arsenates (Đorđević et al., 2015 ; Stock & Bein, 2003 ) and more recently molybdates (Nasri et al., 2014 ; Savina et al., 2014 ) and sulfates (Oyama et al., 2015 ; Ming et al., 2015 ) have been reported to crystallize with alluaudite-type structures. However, to the best of our knowledge, no vanadate adopting this type of structure has been reported so far. Therefore we performed hydrothermal and solid-state reaction investigations within the A₂O/MO/M′₂O₃/V₂O₅ system (A = monovalent cation, M = bivalent cation and M′ = trivalent cation) with approximate molar ratios of A:M:M′:V = 2:2:1:3 and report here details of the preparation and structural characterization of the first sodium- manganese- and iron-based vanadate with an alluaudite-type structure, viz. (Na_0.70)(Na_0.70,Mn_0.30)(Fe³⁺,Fe²⁺)₂Fe²⁺(VO₄)₃.

2. Structural commentary

The preparation of this compound by melting a mixture of three metal oxide precursors in addition to vanadium oxide forced us to explore several crystallographic models. Refinement of the occupancy ratios, bond-valence analysis and the electrical neutrality requirement of the structure lead to the given composition for the title compound. The basic building units of the structure are shown in Fig. 1. The structure is characterized by disorder in three positions. Fe1²⁺ and Fe1³⁺ are statistically distributed on a general site (Wyckoff position 8f); Na1⁺ and Mn1²⁺ are disordered in a 0.7:0.3 ratio on a site located on an inversion centre (4b), and Na2⁺ is present at a site on a twofold rotation axis (4e) with 70% occupancy. All other sites are fully occupied. Nearly the same cationic distribution was reported by Yakubovich et al. (1977 ) for the alluaudite-type phosphate Na₂(Fe³⁺,Fe²⁺)₂Fe²⁺(PO₄)₃.

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, −y + 1, z + $[{1\over 2}]$ ; (ii) x, y, z + 1; (iii) −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 2; (iv) −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1; (v) −x, y, −z + $[{3\over 2}]$ ; (vi) x, y, z − 1; (vii) x − $[{1\over 2}]$ , −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ ; (viii) −x, y, −z + $[{1\over 2}]$ ; (ix) −x, −y + 1, −z + 1; (x) x, −y + 1, z − $[{1\over 2}]$ ; (xi) −x + 1, y, −z + $[{3\over 2}]$ ; (xii) −x + 1, −y + 1, −z + 1.]

The crystal structure of the title compound is built up from edge-sharing [FeO₆] octahedra, leading to the formation of kinked chains running along [10 $[\overline{1}]$ ] (Fig. 2). These chains are held together through the vertices of VO₄ tetrahedra, generating layers perpendicular to [010] (Fig. 3). Thereby an open three-dimensional framework is formed that delimits two types of channels parallel to [001] in which the disordered (Na1⁺/Mn1²⁺) and statistically occupied Na2⁺ cations are accommodated (Fig. 4). The (Na1⁺,Mn1²⁺) site has a distorted octahedral oxygen environment, with (Na1⁺,Mn1²⁺)—O bond lengths between 2.4181 (16) and 2.5115 (15) Å. The Na2⁺ cation is coordinated by eight oxygen atoms with Na2—O distances in the range 2.4879 (18) to 2.982 (3) Å. The disorder of Na⁺ in the channels might admit ionic mobility for this material.

Figure 2
Edge-sharing [FeO₆] octahedra forming a kinked chain running parallel to [10 $[\overline{1}]$ ].

Figure 3
A layer perpendicular to [010], resulting from the connection of chains via vertices of VO₄ tetrahedra.

Figure 4
Polyhedral representation of (Na_0.70)(Na_0.70Mn_0.30)(Fe³⁺/Fe²⁺)₂Fe²⁺(VO₄)₃, showing channels running along and parallel to [001].

3. Synthesis and crystallization

The title compound was prepared by solid-state reactions in air. Sodium nitrate, metallic manganese and iron were mixed with vanadium oxide in proportions corresponding to the molar ratios Na:Mn:Fe:V = 2:2:1:3. The reaction mixture underwent several heat treatments in a platinum crucible until the melting temperature situated at about 1030 K was reached. Each thermal treatment was interspersed with grinding in an agate mortar. The resulting product contained black single crystals crystals of a suitable size for the X-ray diffraction study.

4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. For the (Na1⁺,Mn1²⁺) site, full occupation was assumed, with the sum of the site occupation factors constrained to be 1. The site-occupation factor of Na2⁺ was refined freely. In the last step of the refinement, the site occupation factors were fixed to fulfill electro-neutrality. Reflection (1 5 0) was probably affected by the beam-stop and was omitted from the refinement. The remaining maximum and minimum electron density peaks are located 0.59 and 0.41 Å from Fe2 and V2, respectively.

Table 1
Experimental details

Crystal data
Chemical formula	Na_1.40Mn_0.30Fe₃(VO₄)₃
M_r	561.04
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	11.9512 (5), 12.9022 (5), 6.7756 (3)
β (°)	111.678 (1)
V (Å³)	970.88 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	7.63
Crystal size (mm)	0.30 × 0.26 × 0.18

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.545, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	17759, 1768, 1595
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.757

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.056, 1.12
No. of reflections	1768
No. of parameters	100
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.99
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1447912

Crystal structure: contains datablock I. DOI: 10.1107/S2056989016000931/wm5259sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016000931/wm5259Isup2.hkl

checkCIF report

Chemical context top

Over recent decades, the synthesis and structural characterization of transition-metal-based functional materials adopting layered or channel structures has been the focus of much scientific work. In accordance with widespread studies devoted to the improvement of those materials, we have contributed to the search for new functional materials by undertaking synthesis and structural characterization of new transition and alkali metal phosphates exhibiting channel structures and belonging to the well known alluaudite structure type (Moore, 1971) that can be represented by the general formula A(1)A(2)M(1)M(2)₂(XO₄)₃. The M(1) and M(2) sites accommodate di- or trivalent cations in an octahedral environment and are connected to the tetrahedral XO₄ groups, leading to an open-framework structure. Alluaudite-type phosphates are of special interest as positive electrode materials in lithium and sodium batteries. For instance, the alluaudite-type lithium manganese phosphate Li_0.78Na_0.22MnPO₄ is proposed by Kim et al. (2014) as a promising new positive electrode for Li rechargeable batteries. Furthermore, in the more active alluaudite-type cathode material for sodium-ion batteries, Na₂Fe_{3 − x}Mn_x(PO₄)₃, the electrochemical performance is associated either with morphology or with the electronic and crystalline structure (Huang et al., 2015).

Responding to the growing demand for this type of functional materials, we were able to prepare new alluaudite-type phosphates within pseudo-ternary A₂O/MO/P₂O₅ or pseudo-quaternary A₂O/MO/Fe₂O₃—P₂O₅ systems by means of hydrothermal or solid-state reactions: AgMg₃(HPO₄)₂PO₄ (Assani et al., 2011), NaMg₃(HPO₄)₂PO₄ (Ould Saleck et al., 2015), Na₂Co₂Fe (PO₄)₃ (Bouraima et al., 2015) and Na_1.67Zn_1.67Fe_1.33(PO₄)₃ (Khmiyas et al., 2015).

Besides well known phosphate phases, arsenates (Đorđević et al., 2015; Stock & Bein, 2003) and more recently molybdates (Nasri et al., 2014; Savina et al., 2014) and sulfates (Oyama et al., 2015; Ming et al., 2015) have been reported to crystallize with alluaudite-type structures. However, to the best of our knowledge, no vanadate adopting this type of structure has been reported so far. Therefore we performed hydrothermal and solid-state reaction investigations within the A₂O/MO/M'₂O₃/V₂O₅ system (A = monovalent cation, M = bivalent cation and M' = trivalent cation) with approximate molar ratios of A:M:M':V = 2:2:1:3 and report here details of the preparation and structural characterization of the first sodium-, manganese- and iron-based vanadate with an alluaudite-type structure, viz. (Na_0.70)(Na_0.70,Mn_0.30)(Fe³⁺,Fe²⁺)₂Fe²⁺(VO₄)₃.

Structural commentary top

The preparation of this compound by melting a mixture of three metal oxide precursors in addition to vanadium oxide forced us to explore several crystallographic models. Refinement of the occupancy ratios, bond-valence analysis and the electrical neutrality requirement of the structure lead to the given composition for the title compound. The basic building units of the structure are shown in Fig. 1. The structure is characterized by disorder in three positions. Fe1²⁺ and Fe1³⁺ are statistically distributed on a general site (Wyckoff position 8f); Na1⁺ and Mn1²⁺ are disordered in a 0.7:0.3 ratio on a site located on an inversion centre (4b), and Na2⁺ is present at a site on a twofold rotation axis (4e) with 70% occupancy. All other sites are fully occupied. Nearly the same cationic distribution was reported by Yakubovich et al. (1977) for the alluaudite-type phosphate Na₂(Fe³⁺,Fe²⁺)₂Fe²⁺(PO₄)₃.

The crystal structure of the title compound is built up from edge-sharing [FeO₆] octahedra, leading to the formation of kinked chains running along [101] (Fig. 2). These chains are held together through the vertices of VO₄ tetrahedra, generating layers perpendicular to [010] (Fig. 3). Thereby an open three-dimensional framework is formed that delimits two types of channels parallel to [001] in which the disordered (Na1⁺/Mn1²⁺) and statistically occupied Na2⁺ cations are accommodated (Fig. 4). The (Na1⁺,Mn1²⁺) site has a distorted octahedral oxygen environment, with (Na1⁺,Mn1²⁺)—O bond lengths between 2.4181 (16) and 2.5115 (15) Å. The Na2⁺ cation is coordinated by eight oxygen atoms with Na2—O distances in the range 2.4879 (18) to 2.982 (3) Å. The disorder of Na⁺ in the channels might admit ionic mobility for this material.

Synthesis and crystallization top

Refinement top

Structure description top

Over recent decades, the synthesis and structural characterization of transition-metal-based functional materials adopting layered or channel structures has been the focus of much scientific work. In accordance with widespread studies devoted to the improvement of those materials, we have contributed to the search for new functional materials by undertaking synthesis and structural characterization of new transition and alkali metal phosphates exhibiting channel structures and belonging to the well known alluaudite structure type (Moore, 1971) that can be represented by the general formula A(1)A(2)M(1)M(2)₂(XO₄)₃. The M(1) and M(2) sites accommodate di- or trivalent cations in an octahedral environment and are connected to the tetrahedral XO₄ groups, leading to an open-framework structure. Alluaudite-type phosphates are of special interest as positive electrode materials in lithium and sodium batteries. For instance, the alluaudite-type lithium manganese phosphate Li_0.78Na_0.22MnPO₄ is proposed by Kim et al. (2014) as a promising new positive electrode for Li rechargeable batteries. Furthermore, in the more active alluaudite-type cathode material for sodium-ion batteries, Na₂Fe_{3 − x}Mn_x(PO₄)₃, the electrochemical performance is associated either with morphology or with the electronic and crystalline structure (Huang et al., 2015).

Responding to the growing demand for this type of functional materials, we were able to prepare new alluaudite-type phosphates within pseudo-ternary A₂O/MO/P₂O₅ or pseudo-quaternary A₂O/MO/Fe₂O₃—P₂O₅ systems by means of hydrothermal or solid-state reactions: AgMg₃(HPO₄)₂PO₄ (Assani et al., 2011), NaMg₃(HPO₄)₂PO₄ (Ould Saleck et al., 2015), Na₂Co₂Fe (PO₄)₃ (Bouraima et al., 2015) and Na_1.67Zn_1.67Fe_1.33(PO₄)₃ (Khmiyas et al., 2015).

The preparation of this compound by melting a mixture of three metal oxide precursors in addition to vanadium oxide forced us to explore several crystallographic models. Refinement of the occupancy ratios, bond-valence analysis and the electrical neutrality requirement of the structure lead to the given composition for the title compound. The basic building units of the structure are shown in Fig. 1. The structure is characterized by disorder in three positions. Fe1²⁺ and Fe1³⁺ are statistically distributed on a general site (Wyckoff position 8f); Na1⁺ and Mn1²⁺ are disordered in a 0.7:0.3 ratio on a site located on an inversion centre (4b), and Na2⁺ is present at a site on a twofold rotation axis (4e) with 70% occupancy. All other sites are fully occupied. Nearly the same cationic distribution was reported by Yakubovich et al. (1977) for the alluaudite-type phosphate Na₂(Fe³⁺,Fe²⁺)₂Fe²⁺(PO₄)₃.

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 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, −y + 1, z + 1/2; (ii) x, y, z + 1; (iii) −x + 1/2, −y + 3/2, −z + 2; (iv) −x + 1/2, −y + 3/2, −z + 1; (v) −x, y, −z + 3/2; (vi) x, y, z − 1; (vii) x − 1/2, −y + 3/2, z − 1/2; (viii) −x, y, −z + 1/2; (ix) −x, −y + 1, −z + 1; (x) x, −y + 1, z − 1/2; (xi) −x + 1, y, −z + 3/2; (xii) −x + 1, −y + 1, −z + 1.]
	Fig. 2. Edge-sharing [FeO₆] octahedra forming a kinked chain running parallel to [101].
	Fig. 3. A layer perpendicular to [010], resulting from the connection of chains via vertices of VO₄ tetrahedra.
	Fig. 4. Polyhedral representation of (Na_0.70)(Na_0.70Mn_0.30)(Fe³⁺/Fe²⁺)₂Fe²⁺(VO₄)₃, showing channels running along and parallel to [001].

Sodium (sodium,manganese) triiron(II,III) tris[vanadate(V)] top

Crystal data top

Na_1.40Mn_0.30Fe₃(VO₄)₃	F(000) = 1064
M_r = 561.04	D_x = 3.838 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.9512 (5) Å	Cell parameters from 1768 reflections
b = 12.9022 (5) Å	θ = 2.4–32.6°
c = 6.7756 (3) Å	µ = 7.63 mm⁻¹
β = 111.678 (1)°	T = 296 K
V = 970.88 (7) Å³	Block, black
Z = 4	0.30 × 0.26 × 0.18 mm

Data collection top

Bruker X8 APEX diffractometer	1768 independent reflections
Radiation source: fine-focus sealed tube	1595 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 32.6°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −18→18
T_min = 0.545, T_max = 0.747	k = −19→19
17759 measured reflections	l = −7→10

Refinement top

Refinement on F²	100 parameters
Least-squares matrix: full	0 restraints
R[F² > 2σ(F²)] = 0.020	w = 1/[σ²(F_o²) + (0.0252P)² + 2.9028P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.056	(Δ/σ)_max = 0.001
S = 1.12	Δρ_max = 0.74 e Å⁻³
1768 reflections	Δρ_min = −0.99 e Å⁻³

Crystal data top

Na_1.40Mn_0.30Fe₃(VO₄)₃	V = 970.88 (7) Å³
M_r = 561.04	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 11.9512 (5) Å	µ = 7.63 mm⁻¹
b = 12.9022 (5) Å	T = 296 K
c = 6.7756 (3) Å	0.30 × 0.26 × 0.18 mm
β = 111.678 (1)°

Data collection top

Bruker X8 APEX diffractometer	1768 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1595 reflections with I > 2σ(I)
T_min = 0.545, T_max = 0.747	R_int = 0.030
17759 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	100 parameters
wR(F²) = 0.056	0 restraints
S = 1.12	Δρ_max = 0.74 e Å⁻³
1768 reflections	Δρ_min = −0.99 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe1	0.28812 (3)	0.65986 (2)	0.87842 (4)	0.00988 (7)
Fe2	0.0000	0.73519 (3)	0.2500	0.01105 (9)
V1	0.26720 (3)	0.61038 (2)	0.37946 (5)	0.00884 (7)
V2	0.0000	0.71081 (4)	0.7500	0.01126 (10)
Mn1	0.0000	0.5000	0.5000	0.0136 (8)	0.3
Na1	0.0000	0.5000	0.5000	0.0420 (18)	0.7
Na2	0.5000	0.4890 (3)	0.7500	0.0432 (7)	0.7
O1	0.12025 (14)	0.59837 (11)	0.3264 (3)	0.0151 (3)
O2	0.28070 (14)	0.68158 (12)	0.1709 (2)	0.0160 (3)
O3	0.33564 (14)	0.67141 (12)	0.6228 (2)	0.0148 (3)
O4	0.11010 (16)	0.62915 (12)	0.7570 (3)	0.0194 (3)
O5	0.03980 (14)	0.78286 (12)	0.9783 (2)	0.0138 (3)
O6	0.33208 (16)	0.49277 (13)	0.3977 (3)	0.0189 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.01049 (13)	0.01185 (12)	0.00849 (13)	−0.00026 (9)	0.00491 (10)	−0.00052 (9)
Fe2	0.00964 (17)	0.01269 (17)	0.01294 (19)	0.000	0.00665 (14)	0.000
V1	0.00876 (14)	0.01060 (14)	0.00697 (15)	−0.00061 (10)	0.00267 (11)	−0.00072 (10)
V2	0.0160 (2)	0.00896 (18)	0.0073 (2)	0.000	0.00244 (16)	0.000
Mn1	0.0196 (17)	0.0093 (18)	0.0073 (18)	−0.0076 (13)	−0.0005 (14)	0.0011 (13)
Na1	0.059 (4)	0.027 (4)	0.033 (4)	−0.001 (3)	0.009 (3)	−0.001 (3)
Na2	0.0216 (12)	0.0687 (19)	0.0345 (14)	0.000	0.0047 (10)	0.000
O1	0.0108 (6)	0.0137 (6)	0.0201 (8)	−0.0008 (5)	0.0049 (6)	−0.0013 (5)
O2	0.0160 (7)	0.0203 (7)	0.0119 (7)	−0.0020 (5)	0.0053 (6)	−0.0005 (5)
O3	0.0176 (7)	0.0142 (6)	0.0117 (7)	−0.0049 (5)	0.0043 (5)	−0.0007 (5)
O4	0.0234 (8)	0.0136 (6)	0.0163 (7)	0.0027 (6)	0.0015 (6)	−0.0045 (5)
O5	0.0116 (6)	0.0177 (6)	0.0124 (7)	0.0003 (5)	0.0048 (5)	0.0003 (5)
O6	0.0173 (7)	0.0200 (7)	0.0191 (8)	0.0024 (6)	0.0063 (6)	−0.0056 (6)

Geometric parameters (Å, º) top

Fe1—O4	2.0167 (18)	Mn1—O4^ix	2.4181 (16)
Fe1—O3	2.0180 (16)	Mn1—O4	2.4181 (16)
Fe1—O6ⁱ	2.0299 (17)	Mn1—O1ⁱ	2.4941 (16)
Fe1—O2ⁱⁱ	2.0358 (16)	Mn1—O1^viii	2.4941 (16)
Fe1—O5ⁱⁱⁱ	2.0599 (16)	Mn1—O1	2.5115 (15)
Fe1—O2^iv	2.1841 (16)	Mn1—O1^ix	2.5115 (15)
Fe2—O5^v	2.1540 (15)	Na1—O4^ix	2.4181 (16)
Fe2—O5^vi	2.1540 (15)	Na1—O4	2.4181 (16)
Fe2—O3^iv	2.1915 (15)	Na1—O1ⁱ	2.4941 (16)
Fe2—O3^vii	2.1915 (15)	Na1—O1^viii	2.4941 (16)
Fe2—O1^viii	2.2136 (15)	Na1—O1	2.5115 (15)
Fe2—O1	2.2136 (15)	Na1—O1^ix	2.5115 (15)
V1—O1	1.6647 (15)	Na1—O4^x	2.9698 (18)
V1—O6	1.6878 (16)	Na1—O4^v	2.9698 (18)
V1—O3	1.7351 (16)	Na2—O6^xi	2.4879 (18)
V1—O2	1.7420 (16)	Na2—O6	2.4879 (18)
V2—O4	1.6726 (17)	Na2—O6^xii	2.5627 (18)
V2—O4^v	1.6726 (17)	Na2—O6ⁱ	2.5627 (18)
V2—O5	1.7147 (15)	Na2—O3^xi	2.982 (3)
V2—O5^v	1.7147 (15)	Na2—O3	2.982 (3)

O4—Fe1—O3	104.67 (7)	O1ⁱ—Mn1—O1	115.50 (6)
O4—Fe1—O6ⁱ	92.56 (7)	O1^viii—Mn1—O1	64.50 (6)
O3—Fe1—O6ⁱ	88.77 (7)	O4^ix—Mn1—O1^ix	74.67 (6)
O4—Fe1—O2ⁱⁱ	90.31 (7)	O4—Mn1—O1^ix	105.33 (6)
O3—Fe1—O2ⁱⁱ	162.33 (6)	O1ⁱ—Mn1—O1^ix	64.50 (6)
O6ⁱ—Fe1—O2ⁱⁱ	100.04 (7)	O1^viii—Mn1—O1^ix	115.50 (6)
O4—Fe1—O5ⁱⁱⁱ	169.09 (6)	O1—Mn1—O1^ix	180.00 (6)
O3—Fe1—O5ⁱⁱⁱ	80.18 (6)	O4^ix—Na1—O4	180.0
O6ⁱ—Fe1—O5ⁱⁱⁱ	97.36 (7)	O4^ix—Na1—O1ⁱ	105.66 (5)
O2ⁱⁱ—Fe1—O5ⁱⁱⁱ	83.50 (6)	O4—Na1—O1ⁱ	74.34 (5)
O4—Fe1—O2^iv	80.83 (6)	O4^ix—Na1—O1^viii	74.34 (5)
O3—Fe1—O2^iv	90.51 (6)	O4—Na1—O1^viii	105.66 (5)
O6ⁱ—Fe1—O2^iv	172.94 (7)	O1ⁱ—Na1—O1^viii	180.0
O2ⁱⁱ—Fe1—O2^iv	82.57 (6)	O4^ix—Na1—O1	105.33 (6)
O5ⁱⁱⁱ—Fe1—O2^iv	89.43 (6)	O4—Na1—O1	74.67 (6)
O5^v—Fe2—O5^vi	146.82 (8)	O1ⁱ—Na1—O1	115.50 (6)
O5^v—Fe2—O3^iv	87.45 (6)	O1^viii—Na1—O1	64.50 (6)
O5^vi—Fe2—O3^iv	74.36 (6)	O4^ix—Na1—O1^ix	74.67 (6)
O5^v—Fe2—O3^vii	74.36 (6)	O4—Na1—O1^ix	105.33 (6)
O5^vi—Fe2—O3^vii	87.45 (6)	O1ⁱ—Na1—O1^ix	64.50 (6)
O3^iv—Fe2—O3^vii	113.28 (8)	O1^viii—Na1—O1^ix	115.50 (6)
O5^v—Fe2—O1^viii	95.65 (6)	O1—Na1—O1^ix	180.00 (6)
O5^vi—Fe2—O1^viii	110.91 (6)	O4^ix—Na1—O4^x	56.55 (7)
O3^iv—Fe2—O1^viii	160.16 (6)	O4—Na1—O4^x	123.45 (7)
O3^vii—Fe2—O1^viii	86.35 (6)	O1ⁱ—Na1—O4^x	88.74 (5)
O5^v—Fe2—O1	110.91 (6)	O1^viii—Na1—O4^x	91.26 (5)
O5^vi—Fe2—O1	95.65 (6)	O1—Na1—O4^x	64.95 (5)
O3^iv—Fe2—O1	86.35 (6)	O1^ix—Na1—O4^x	115.05 (5)
O3^vii—Fe2—O1	160.16 (6)	O4^ix—Na1—O4^v	123.45 (7)
O1^viii—Fe2—O1	74.22 (8)	O4—Na1—O4^v	56.55 (7)
O1—V1—O6	110.59 (8)	O1ⁱ—Na1—O4^v	91.26 (5)
O1—V1—O3	109.68 (8)	O1^viii—Na1—O4^v	88.74 (5)
O6—V1—O3	107.22 (8)	O1—Na1—O4^v	115.05 (5)
O1—V1—O2	106.29 (8)	O1^ix—Na1—O4^v	64.95 (5)
O6—V1—O2	110.84 (8)	O4^x—Na1—O4^v	180.0
O3—V1—O2	112.27 (7)	O6^xi—Na2—O6	177.75 (17)
O4—V2—O4^v	101.92 (12)	O6^xi—Na2—O6^xii	84.40 (5)
O4—V2—O5	111.28 (8)	O6—Na2—O6^xii	95.40 (5)
O4^v—V2—O5	108.67 (8)	O6^xi—Na2—O6ⁱ	95.40 (5)
O4—V2—O5^v	108.67 (8)	O6—Na2—O6ⁱ	84.40 (5)
O4^v—V2—O5^v	111.28 (8)	O6^xii—Na2—O6ⁱ	169.46 (16)
O5—V2—O5^v	114.33 (10)	O6^xi—Na2—O3^xi	59.69 (6)
O4^ix—Mn1—O4	180.0	O6—Na2—O3^xi	118.28 (11)
O4^ix—Mn1—O1ⁱ	105.66 (5)	O6^xii—Na2—O3^xi	60.86 (6)
O4—Mn1—O1ⁱ	74.34 (5)	O6ⁱ—Na2—O3^xi	109.99 (10)
O4^ix—Mn1—O1^viii	74.34 (5)	O6^xi—Na2—O3	118.28 (11)
O4—Mn1—O1^viii	105.66 (5)	O6—Na2—O3	59.69 (6)
O1ⁱ—Mn1—O1^viii	180.0	O6^xii—Na2—O3	109.99 (10)
O4^ix—Mn1—O1	105.33 (6)	O6ⁱ—Na2—O3	60.86 (6)
O4—Mn1—O1	74.67 (6)	O3^xi—Na2—O3	75.74 (10)

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

Experimental details

Crystal data
Chemical formula	Na_1.40Mn_0.30Fe₃(VO₄)₃
M_r	561.04
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	11.9512 (5), 12.9022 (5), 6.7756 (3)
β (°)	111.678 (1)
V (Å³)	970.88 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.63
Crystal size (mm)	0.30 × 0.26 × 0.18

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.545, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	17759, 1768, 1595
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.757

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.056, 1.12
No. of reflections	1768
No. of parameters	100
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.99

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

Acknowledgements

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

References

Assani, A., Saadi, M., Zriouil, M. & El Ammari, L. (2011). Acta Cryst. E67, i5. Web of Science CrossRef IUCr Journals Google Scholar
Bouraima, A., Assani, A., Saadi, M., Makani, T. & El Ammari, L. (2015). Acta Cryst. E71, 558–560. CSD CrossRef IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Đorđević, T., Wittwer, A. & Krivovichev, S. (2015). Eur. J. Mineral. 27, 559–573. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Huang, W., Li, B., Saleem, M. F., Wu, X., Li, J., Lin, J., Xia, D., Chu, W. & Wu, Z. (2015). Chem. Eur. J. 21, 851–860. Web of Science CrossRef CAS PubMed Google Scholar
Khmiyas, J., Assani, A., Saadi, M. & El Ammari, L. (2015). Acta Cryst. E71, 690–692. CSD CrossRef IUCr Journals Google Scholar
Kim, J., Kim, H., Park, K.-Y., Park, Y.-U., Lee, S., Kwon, H.-S., Yoo, H.-I. & Kang, K. (2014). J. Mater. Chem. A, 2, 8632–8636. Web of Science CrossRef CAS Google Scholar
Ming, J., Barpanda, P., Nishimura, S., Okubo, M. & Yamada, A. (2015). Electrochem. Commun. 51, 19–22. CrossRef CAS Google Scholar
Moore, P. B. (1971). Am. Mineral. 56, 1955–1975. CAS Google Scholar
Nasri, R., Fakhar Bourguiba, N., Zid, M. F. & Driss, A. (2014). Acta Cryst. E70, i47–i48. CSD CrossRef IUCr Journals Google Scholar
Ould Saleck, A., Assani, A., Saadi, M., Mercier, C., Follet, C. & El Ammari, L. (2015). Acta Cryst. E71, 813–815. CSD CrossRef IUCr Journals Google Scholar
Oyama, G., Nishimura, S., Suzuki, Y., Okubo, M. & Yamada, A. (2015). ChemElectroChem, 2, 1019–1023. CrossRef CAS Google Scholar
Savina, A., Solodovnikov, S., Belov, D., Basovich, O., Solodovnikova, Z., Pokholok, K., Stefanovich, S., Lazoryak, B. & Khaikina, E. (2014). J. Solid State Chem. 220, 217–220. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Stock, N. & Bein, T. (2003). Solid State Sci. 5, 1207–1210. Web of Science CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yakubovich, O. V., Simonov, M. A., Egorov-Tismenko, Yu. K. & Belov, N. V. (1977). Sov. Phys. Dokl. 22, 550–552. Google Scholar

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Volume 72| Part 2| February 2016| Pages 220-222

doi:10.1107/S2056989016000931

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