research communications
0.70)(Na0.70,Mn0.30)(Fe3+,Fe2+)2Fe2+(VO4)3, a sodium-, iron- and manganese-based vanadate with the alluaudite-type structure
of (NaaLaboratoire 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
The title compound, sodium (sodium,manganese) triiron(II,III) tris[vanadate(V)], (Na0.70)(Na0.70,Mn0.30)(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 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 Li0.78Na0.22MnPO4 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, Na2Fe3-xMnx(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 Na1.67Zn1.67Fe1.33(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. (Na0.70)(Na0.70,Mn0.30)(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. . 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.
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. 1The 6] octahedra, leading to the formation of kinked chains running along [10] (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.
of the title compound is built up from edge-sharing [FeO3. 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 . 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 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 The remaining maximum and minimum electron density peaks are located 0.59 and 0.41 Å from Fe2 and V2, respectively.
details are summarized in Table 1Supporting information
CCDC reference: 1447912
10.1107/S2056989016000931/wm5259sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016000931/wm5259Isup2.hkl
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 Li0.78Na0.22MnPO4 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, Na2Fe3 − xMnx(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 Na1.67Zn1.67Fe1.33(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. (Na0.70)(Na0.70,Mn0.30)(Fe3+,Fe2+)2Fe2+(VO4)3.
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.
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 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.
of the title compound is built up from edge-sharing [FeO6] octahedra, leading to the formation of kinked chains running along [10The 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.
Crystal data, data collection and structure
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 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 The remaining maximum and minimum electron density peaks are located 0.59 and 0.41 Å from Fe2 and V2, respectively.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 Li0.78Na0.22MnPO4 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, Na2Fe3 − xMnx(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 Na1.67Zn1.67Fe1.33(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. (Na0.70)(Na0.70,Mn0.30)(Fe3+,Fe2+)2Fe2+(VO4)3.
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.
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 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.
of the title compound is built up from edge-sharing [FeO6] octahedra, leading to the formation of kinked chains running along [10The 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.
detailsCrystal data, data collection and structure
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 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 The remaining maximum and minimum electron density peaks are located 0.59 and 0.41 Å from Fe2 and V2, respectively.Data collection: APEX2 (Bruker, 2009); cell
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).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 (Na0.70)(Na0.70Mn0.30)(Fe3+/Fe2+)2Fe2+(VO4)3, showing channels running along and parallel to [001]. |
Na1.40Mn0.30Fe3(VO4)3 | F(000) = 1064 |
Mr = 561.04 | Dx = 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 |
Bruker X8 APEX diffractometer | 1768 independent reflections |
Radiation source: fine-focus sealed tube | 1595 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
φ and ω scans | θmax = 32.6°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −18→18 |
Tmin = 0.545, Tmax = 0.747 | k = −19→19 |
17759 measured reflections | l = −7→10 |
Refinement on F2 | 100 parameters |
Least-squares matrix: full | 0 restraints |
R[F2 > 2σ(F2)] = 0.020 | w = 1/[σ2(Fo2) + (0.0252P)2 + 2.9028P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.056 | (Δ/σ)max = 0.001 |
S = 1.12 | Δρmax = 0.74 e Å−3 |
1768 reflections | Δρmin = −0.99 e Å−3 |
Na1.40Mn0.30Fe3(VO4)3 | V = 970.88 (7) Å3 |
Mr = 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)° |
Bruker X8 APEX diffractometer | 1768 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1595 reflections with I > 2σ(I) |
Tmin = 0.545, Tmax = 0.747 | Rint = 0.030 |
17759 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 100 parameters |
wR(F2) = 0.056 | 0 restraints |
S = 1.12 | Δρmax = 0.74 e Å−3 |
1768 reflections | Δρmin = −0.99 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | 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) |
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) |
Fe1—O4 | 2.0167 (18) | Mn1—O4ix | 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—O1viii | 2.4941 (16) |
Fe1—O5iii | 2.0599 (16) | Mn1—O1 | 2.5115 (15) |
Fe1—O2iv | 2.1841 (16) | Mn1—O1ix | 2.5115 (15) |
Fe2—O5v | 2.1540 (15) | Na1—O4ix | 2.4181 (16) |
Fe2—O5vi | 2.1540 (15) | Na1—O4 | 2.4181 (16) |
Fe2—O3iv | 2.1915 (15) | Na1—O1i | 2.4941 (16) |
Fe2—O3vii | 2.1915 (15) | Na1—O1viii | 2.4941 (16) |
Fe2—O1viii | 2.2136 (15) | Na1—O1 | 2.5115 (15) |
Fe2—O1 | 2.2136 (15) | Na1—O1ix | 2.5115 (15) |
V1—O1 | 1.6647 (15) | Na1—O4x | 2.9698 (18) |
V1—O6 | 1.6878 (16) | Na1—O4v | 2.9698 (18) |
V1—O3 | 1.7351 (16) | Na2—O6xi | 2.4879 (18) |
V1—O2 | 1.7420 (16) | Na2—O6 | 2.4879 (18) |
V2—O4 | 1.6726 (17) | Na2—O6xii | 2.5627 (18) |
V2—O4v | 1.6726 (17) | Na2—O6i | 2.5627 (18) |
V2—O5 | 1.7147 (15) | Na2—O3xi | 2.982 (3) |
V2—O5v | 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) | O1viii—Mn1—O1 | 64.50 (6) |
O3—Fe1—O6i | 88.77 (7) | O4ix—Mn1—O1ix | 74.67 (6) |
O4—Fe1—O2ii | 90.31 (7) | O4—Mn1—O1ix | 105.33 (6) |
O3—Fe1—O2ii | 162.33 (6) | O1i—Mn1—O1ix | 64.50 (6) |
O6i—Fe1—O2ii | 100.04 (7) | O1viii—Mn1—O1ix | 115.50 (6) |
O4—Fe1—O5iii | 169.09 (6) | O1—Mn1—O1ix | 180.00 (6) |
O3—Fe1—O5iii | 80.18 (6) | O4ix—Na1—O4 | 180.0 |
O6i—Fe1—O5iii | 97.36 (7) | O4ix—Na1—O1i | 105.66 (5) |
O2ii—Fe1—O5iii | 83.50 (6) | O4—Na1—O1i | 74.34 (5) |
O4—Fe1—O2iv | 80.83 (6) | O4ix—Na1—O1viii | 74.34 (5) |
O3—Fe1—O2iv | 90.51 (6) | O4—Na1—O1viii | 105.66 (5) |
O6i—Fe1—O2iv | 172.94 (7) | O1i—Na1—O1viii | 180.0 |
O2ii—Fe1—O2iv | 82.57 (6) | O4ix—Na1—O1 | 105.33 (6) |
O5iii—Fe1—O2iv | 89.43 (6) | O4—Na1—O1 | 74.67 (6) |
O5v—Fe2—O5vi | 146.82 (8) | O1i—Na1—O1 | 115.50 (6) |
O5v—Fe2—O3iv | 87.45 (6) | O1viii—Na1—O1 | 64.50 (6) |
O5vi—Fe2—O3iv | 74.36 (6) | O4ix—Na1—O1ix | 74.67 (6) |
O5v—Fe2—O3vii | 74.36 (6) | O4—Na1—O1ix | 105.33 (6) |
O5vi—Fe2—O3vii | 87.45 (6) | O1i—Na1—O1ix | 64.50 (6) |
O3iv—Fe2—O3vii | 113.28 (8) | O1viii—Na1—O1ix | 115.50 (6) |
O5v—Fe2—O1viii | 95.65 (6) | O1—Na1—O1ix | 180.00 (6) |
O5vi—Fe2—O1viii | 110.91 (6) | O4ix—Na1—O4x | 56.55 (7) |
O3iv—Fe2—O1viii | 160.16 (6) | O4—Na1—O4x | 123.45 (7) |
O3vii—Fe2—O1viii | 86.35 (6) | O1i—Na1—O4x | 88.74 (5) |
O5v—Fe2—O1 | 110.91 (6) | O1viii—Na1—O4x | 91.26 (5) |
O5vi—Fe2—O1 | 95.65 (6) | O1—Na1—O4x | 64.95 (5) |
O3iv—Fe2—O1 | 86.35 (6) | O1ix—Na1—O4x | 115.05 (5) |
O3vii—Fe2—O1 | 160.16 (6) | O4ix—Na1—O4v | 123.45 (7) |
O1viii—Fe2—O1 | 74.22 (8) | O4—Na1—O4v | 56.55 (7) |
O1—V1—O6 | 110.59 (8) | O1i—Na1—O4v | 91.26 (5) |
O1—V1—O3 | 109.68 (8) | O1viii—Na1—O4v | 88.74 (5) |
O6—V1—O3 | 107.22 (8) | O1—Na1—O4v | 115.05 (5) |
O1—V1—O2 | 106.29 (8) | O1ix—Na1—O4v | 64.95 (5) |
O6—V1—O2 | 110.84 (8) | O4x—Na1—O4v | 180.0 |
O3—V1—O2 | 112.27 (7) | O6xi—Na2—O6 | 177.75 (17) |
O4—V2—O4v | 101.92 (12) | O6xi—Na2—O6xii | 84.40 (5) |
O4—V2—O5 | 111.28 (8) | O6—Na2—O6xii | 95.40 (5) |
O4v—V2—O5 | 108.67 (8) | O6xi—Na2—O6i | 95.40 (5) |
O4—V2—O5v | 108.67 (8) | O6—Na2—O6i | 84.40 (5) |
O4v—V2—O5v | 111.28 (8) | O6xii—Na2—O6i | 169.46 (16) |
O5—V2—O5v | 114.33 (10) | O6xi—Na2—O3xi | 59.69 (6) |
O4ix—Mn1—O4 | 180.0 | O6—Na2—O3xi | 118.28 (11) |
O4ix—Mn1—O1i | 105.66 (5) | O6xii—Na2—O3xi | 60.86 (6) |
O4—Mn1—O1i | 74.34 (5) | O6i—Na2—O3xi | 109.99 (10) |
O4ix—Mn1—O1viii | 74.34 (5) | O6xi—Na2—O3 | 118.28 (11) |
O4—Mn1—O1viii | 105.66 (5) | O6—Na2—O3 | 59.69 (6) |
O1i—Mn1—O1viii | 180.0 | O6xii—Na2—O3 | 109.99 (10) |
O4ix—Mn1—O1 | 105.33 (6) | O6i—Na2—O3 | 60.86 (6) |
O4—Mn1—O1 | 74.67 (6) | O3xi—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 | Na1.40Mn0.30Fe3(VO4)3 |
Mr | 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) |
Tmin, Tmax | 0.545, 0.747 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17759, 1768, 1595 |
Rint | 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 |
Δρmax, Δρmin (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.
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