research communications
Synthesis and 4Ni7(AsO4)6
of NaaLaboratoire de Réactivité et Chimie des Solides, Université de Picardie Jules Verne, CNRS UMR 7314, 33 rue Saint Leu, 80039 Amiens, France
*Correspondence e-mail: renald.david@u-picardie.fr
The title compound, tetrasodium heptanickel hexaarsenate, was obtained by ceramic synthesis and crystallizes in the monoclinic C2/m. The contains seven Ni atoms of which two have 2/m and three 2, four As atoms of which two have m and two 2, three Na atoms of which two have 2, and fifteen O atoms of which four have m. The structure of Na4Ni7(AsO4)6 is made of layers of Ni octahedra and As tetrahedra assembled in sheets parallel to the bc plane. These layers are interconnected by corner-sharing between NiO6 octahedra and AsO4 tetrahedra. This linkage creates tunnels running along the c axis in which the Na atoms are located. This arrangement is similar to the one observed in Na4Ni7(PO4)6, but the layers of the two compounds are slightly different because of the disorder of one of the Ni sites in the structure of the title compound.
Keywords: crystal structure; nickel arsenate; ceramic synthesis.
CCDC reference: 1471603
1. Chemical context
Although the structures of transition metal phosphates have been widely investigated during the last decades, very little work has been done on comparable arsenates due to the toxicity of arsenic. The latter phases can exhibit, however, peculiar properties. BaCo2(AsO4)2 is a good example of a quasi-2D system with a magnetically frustrated honeycomb lattice (Regnault et al., 1977). BaCoAs2O7 appears as the first example of a magnetization step promoted by a structural modulation (David et al., 2013a). LiCoAsO4 shows reversible electrochemical activity at high potential (Satya Kishore & Varadaraju, 2006). Moreover, a recent study reveals the interest of arsenate groups in playing the role of efficient disconnecting units in the magnetic compound BaCo2(As3O6)2·H2O, being the first pure inorganic compound with slow spin dynamics (David et al., 2013b). From the crystal chemistry point of view, substitution of phosphate by arsenate gives the possibility of stabilizing new phases. For example, NaNiPO4 crystallizes with the maricite structure (Senthilkumar et al., 2014), whereas NaNiAsO4 has a honeycomb layer structure (Range & Meister, 1984). In this study, we describe the structure of Na4Ni7(AsO4)6 and compare it with its phosphate analogue.
2. Structural commentary
The structure of the title compound Na4Ni7(AsO4)6 is quite similar to the one of the phosphate homologue Na4Ni7(PO4)6. Both are made of interconnected Ni7(XO4)6 layers with tunnels in between where the Na atoms are located, as shown in Fig. 1a. The arrangement of NiO6 and XO4 in the layer is, however, slightly different, as evidenced in Fig. 2. As described by Moring & Kostiner (1986), Na4Ni7(PO4)6 layers are made of parallel ribbons (called ribbon 1) containing Ni1, Ni2, P3 and P4 polyhedra. These ribbons 1 are interconnected by another kind of ribbon (called ribbon 2) made of dimers consisting of edge-sharing NiO6 octahedra (Ni3 and Ni4). The latter are linked to PO4 tetrahedra (P1 and P2) by edge- and corner-sharing. The difference between the two compounds is associated with the possibility of the Ni2 atom in Na4Ni7(PO4)6 occupying two octahedral sites. The first site, belonging to ribbon 1, is equivalent to the Ni2a site in Na4Ni7(AsO4)6. The other, equivalent to the Ni2b and Ni5 sites in Na4Ni7(AsO4)6, belongs to ribbon 2, forming pentamers of edge-sharing NiO6 octahedra. The layers of the title compound Na4Ni7(AsO4)6 can thus be described with three kinds of ribbons, as shown in Fig. 2. The linkage between the layers is done by corner-sharing between NiO6 and AsO4 units of two consecutive ribbons 2 along the stacking axis (Fig. 1a). This linkage is identical to the one of the phosphorus homologue. However, since in Na4Ni7(AsO4)6 layers are made of three different kinds of ribbons, two adjacent layers are shifted to align ribbon 1 with ribbon 1′. That is why in Na4Ni7(AsO4)6 the stacking axis is roughly doubled compared to Na4Ni7(PO4)6 [c = 6.398 (2) Å versus a = 14.5383 (11) Å in the title structure]. It implies two different kinds of Na layers, as shown in Fig. 1b.
3. Synthesis and crystallization
Sodium carbonate (>99.5%), arsenic oxide (99%) and nickel sulfate hexahydrate (>99.9%) were purchased from Sigma–Aldrich. They were used as received without further purification. Reagents were ground together in stoichiometric ratio in an agate mortar. The obtained mixture was pelletized, placed in an alumina boat and annealed at 573 K for 1h. The obtained mixture was reground, pelletized and heated at 1073 K (5 K min−1) for 48 h, after which the alumina boat was removed from the furnace and cooled to room temperature. The brown crystals of the title compound were isolated by hand.
4. details
Crystal data, data collection and structure . The (001) reflection, affected by the beamstop, has been removed from the Another reflection (01), flagged as potentially affected by the beamstop, was in fact not and was kept in the After positioning and refining all the atom positions except Ni2b, the difference Fourier map revealed residual density (≃8 e Å−3) near Ni2a (at ≃0.6 Å). It was refined introducing a second position Ni2b with complementary occupation. The occupancy ratio was refined to 0.80 (4):0.20 (4) for the Ni2a/Ni2b site, constraining the sum to be equal to 1.
details are summarized in Table 1Supporting information
CCDC reference: 1471603
10.1107/S2056989016005417/vn2109sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016005417/vn2109Isup2.hkl
Although the structures of transition metal phosphates have been widely investigated during the last decades, very little work has been done on comparable arsenates due to the toxicity of arsenic. The latter phases can exhibit, however, peculiar properties. BaCo2(AsO4)2 is a good example of a quasi-2D system with a magnetically frustrated honeycomb lattice (Regnault et al., 1977). BaCoAs2O7 appears as the first example of a magnetization step promoted by a structural modulation (David et al., 2013a). LiCoAsO4 shows reversible electrochemical activity at high potential (Satya Kishore & Varadaraju, 2006). Moreover, a recent study reveals the interest of arseniate groups in playing the role of efficient disconnecting units in the magnetic compound BaCo2(As3O6)2·H2O, being the first pure inorganic compound with slow spin dynamics (David et al., 2013b). From the crystal chemistry point of view, substitution of phosphate by arsenate gives the possibility of stabilizing new phases. For example, NaNiPO4 crystallizes with the maricite structure (Senthilkumar et al., 2014), whereas NaNiAsO4 has a honeycomb layer structure (Range & Meister, 2014). In this study, we describe the structure of Na4Ni7(AsO4)6 and compare it with its phosphate analogue.
The structure of the title compound Na4Ni7(AsO4)6 is quite similar to the one of the phosphate homologue Na4Ni7(PO4)6. Both are made of interconnected Ni7(XO4)6 layers with Na tunnels in between, as shown in Fig. 1a. The arrangement of NiO6 and XO4 in the layer is, however, slightly different, as evidenced in Fig. 2. As described by Moring & Kostiner (1986), Na4Ni7(PO4)6 layers are made of parallel ribbons (called ribbon 1) containing Ni1, Ni2, P3 and P4 polyhedra. These ribbons 1 are interconnected by another kind of ribbon (called ribbon 2) made of dimers edge-sharing Ni3 and Ni4 octahedra linked. The latter octahedra are linked to P1 and P2 tetrahedra by edge- and corner-sharing. The difference between the two compounds is associated with the possibility of the Ni2 atom in Na4Ni7(PO4)6 occupying two octahedral sites. The first site, belonging to ribbon 1, is equivalent to the Ni2a site in Na4Ni7(AsO4)6. The other, equivalent to the Ni2b and Ni5 sites in Na4Ni7(AsO4)6 , belongs to ribbon 2, forming pentamers of edge-sharing NiO6 octahedra. The layers of the title compound Na4Ni7(AsO4)6 can thus be described with three kinds of ribbons, as shown in Fig. 2. The linkage between the layers is done by corner-sharing between NiO6 and AsO4 units of two consecutive ribbons 2 along the stacking axis (Fig. 1a). This linkage is identical to the one of the phosphorous homologue. However, since in Na4Ni7(AsO4)6 layers are made of three different kinds of ribbons, two adjacent layers are shifted to align ribbon 1 with ribbon 1'. That is why in Na4Ni7(AsO4)6 the stacking axis is roughly doubled compared to Na4Ni7(PO4)6 [a =14.534 (4) vs c = 6.398 (2) Å in the title structure]. It implies two different kinds of Na layers, as shown in Fig. 1b.
Sodium carbonate (>99.5%), arsenic oxide (99%) and nickel sulfate hexahydrate (>99.9%) were purchased from Sigma–Aldrich. They were used as received without further purification. Reagents were ground together in stoichiometric ratio in an agate mortar. The obtained mixture was pelletized, placed in an alumina boat and annealed at 573 K for 1h. The obtained mixture was reground, pelletized and heated at 1073 K (5 K min-1) for 48 h, after which the alumina boat was removed from the furnace and cooled to room temperature. The brown crystals of the title compound were isolated by hand.
The (001) reflection, affected by the beamstop, was been removed from the 2 0 1), flagged as potentially affected by the beamstop, was in fact not and was kept in the After positioning and refining all the atom positions except Ni2b, the difference Fourier map revealed residual density (≈8 e Å-3) near Ni2a (at ≈0.6 Å). It was refined introducing a second position Ni2b with complementary occupation. The occupancy ratio was refined to 0.80 (4):0.20 (4) for the Ni2a/Ni2b site, constraining the sum to be equal to 1.
Another reflection (Although the structures of transition metal phosphates have been widely investigated during the last decades, very little work has been done on comparable arsenates due to the toxicity of arsenic. The latter phases can exhibit, however, peculiar properties. BaCo2(AsO4)2 is a good example of a quasi-2D system with a magnetically frustrated honeycomb lattice (Regnault et al., 1977). BaCoAs2O7 appears as the first example of a magnetization step promoted by a structural modulation (David et al., 2013a). LiCoAsO4 shows reversible electrochemical activity at high potential (Satya Kishore & Varadaraju, 2006). Moreover, a recent study reveals the interest of arseniate groups in playing the role of efficient disconnecting units in the magnetic compound BaCo2(As3O6)2·H2O, being the first pure inorganic compound with slow spin dynamics (David et al., 2013b). From the crystal chemistry point of view, substitution of phosphate by arsenate gives the possibility of stabilizing new phases. For example, NaNiPO4 crystallizes with the maricite structure (Senthilkumar et al., 2014), whereas NaNiAsO4 has a honeycomb layer structure (Range & Meister, 2014). In this study, we describe the structure of Na4Ni7(AsO4)6 and compare it with its phosphate analogue.
The structure of the title compound Na4Ni7(AsO4)6 is quite similar to the one of the phosphate homologue Na4Ni7(PO4)6. Both are made of interconnected Ni7(XO4)6 layers with Na tunnels in between, as shown in Fig. 1a. The arrangement of NiO6 and XO4 in the layer is, however, slightly different, as evidenced in Fig. 2. As described by Moring & Kostiner (1986), Na4Ni7(PO4)6 layers are made of parallel ribbons (called ribbon 1) containing Ni1, Ni2, P3 and P4 polyhedra. These ribbons 1 are interconnected by another kind of ribbon (called ribbon 2) made of dimers edge-sharing Ni3 and Ni4 octahedra linked. The latter octahedra are linked to P1 and P2 tetrahedra by edge- and corner-sharing. The difference between the two compounds is associated with the possibility of the Ni2 atom in Na4Ni7(PO4)6 occupying two octahedral sites. The first site, belonging to ribbon 1, is equivalent to the Ni2a site in Na4Ni7(AsO4)6. The other, equivalent to the Ni2b and Ni5 sites in Na4Ni7(AsO4)6 , belongs to ribbon 2, forming pentamers of edge-sharing NiO6 octahedra. The layers of the title compound Na4Ni7(AsO4)6 can thus be described with three kinds of ribbons, as shown in Fig. 2. The linkage between the layers is done by corner-sharing between NiO6 and AsO4 units of two consecutive ribbons 2 along the stacking axis (Fig. 1a). This linkage is identical to the one of the phosphorous homologue. However, since in Na4Ni7(AsO4)6 layers are made of three different kinds of ribbons, two adjacent layers are shifted to align ribbon 1 with ribbon 1'. That is why in Na4Ni7(AsO4)6 the stacking axis is roughly doubled compared to Na4Ni7(PO4)6 [a =14.534 (4) vs c = 6.398 (2) Å in the title structure]. It implies two different kinds of Na layers, as shown in Fig. 1b.
Sodium carbonate (>99.5%), arsenic oxide (99%) and nickel sulfate hexahydrate (>99.9%) were purchased from Sigma–Aldrich. They were used as received without further purification. Reagents were ground together in stoichiometric ratio in an agate mortar. The obtained mixture was pelletized, placed in an alumina boat and annealed at 573 K for 1h. The obtained mixture was reground, pelletized and heated at 1073 K (5 K min-1) for 48 h, after which the alumina boat was removed from the furnace and cooled to room temperature. The brown crystals of the title compound were isolated by hand.
detailsThe (001) reflection, affected by the beamstop, was been removed from the 2 0 1), flagged as potentially affected by the beamstop, was in fact not and was kept in the After positioning and refining all the atom positions except Ni2b, the difference Fourier map revealed residual density (≈8 e Å-3) near Ni2a (at ≈0.6 Å). It was refined introducing a second position Ni2b with complementary occupation. The occupancy ratio was refined to 0.80 (4):0.20 (4) for the Ni2a/Ni2b site, constraining the sum to be equal to 1.
Another reflection (Data collection: APEX3 (Bruker, 2015); cell
SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříčcek et al., 2014; molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. Description of the crystal structure of Na4Ni7(AsO4)6 with (a) a view of the stacking and (b) a view of the Na layers. The dotted lines show the cell edges. | |
Fig. 2. Description of the layers (top) and the ribbon 2 (bottom) of (a) Na4Ni7(AsO4)6 and (b) Na4Ni7(PO4)6. The dotted lines show the cell edges. |
Na4Ni7(AsO4)6 | F(000) = 2520 |
Mr = 1336.3 | Dx = 4.505 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2y | Cell parameters from 38754 reflections |
a = 14.5383 (11) Å | θ = 2.1–33.3° |
b = 14.5047 (11) Å | µ = 16.76 mm−1 |
c = 10.6120 (8) Å | T = 293 K |
β = 118.299 (2)° | Irregular, brown |
V = 1970.3 (3) Å3 | 0.07 × 0.06 × 0.04 mm |
Z = 4 |
Bruker D8 Venture diffractometer | 2901 reflections with I > 3σ(I) |
Radiation source: X-ray tube | Rint = 0.036 |
phi scan | θmax = 33.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | h = −21→20 |
Tmin = 0.640, Tmax = 0.747 | k = −22→21 |
48075 measured reflections | l = −16→16 |
3773 independent reflections |
Refinement on F | 0 restraints |
R[F2 > 2σ(F2)] = 0.039 | 0 constraints |
wR(F2) = 0.052 | Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2) |
S = 2.73 | (Δ/σ)max = 0.015 |
3773 reflections | Δρmax = 3.34 e Å−3 |
146 parameters | Δρmin = −2.22 e Å−3 |
Na4Ni7(AsO4)6 | V = 1970.3 (3) Å3 |
Mr = 1336.3 | Z = 4 |
Monoclinic, C2/m | Mo Kα radiation |
a = 14.5383 (11) Å | µ = 16.76 mm−1 |
b = 14.5047 (11) Å | T = 293 K |
c = 10.6120 (8) Å | 0.07 × 0.06 × 0.04 mm |
β = 118.299 (2)° |
Bruker D8 Venture diffractometer | 3773 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | 2901 reflections with I > 3σ(I) |
Tmin = 0.640, Tmax = 0.747 | Rint = 0.036 |
48075 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 146 parameters |
wR(F2) = 0.052 | 0 restraints |
S = 2.73 | Δρmax = 3.34 e Å−3 |
3773 reflections | Δρmin = −2.22 e Å−3 |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.5 | 0 | 0 | 0.0068 (4) | |
Ni2a | 0.5 | 0.1306 (6) | 0.5 | 0.0078 (8) | 0.80 (4) |
Ni2b | 0.5 | 0.166 (5) | 0.5 | 0.027 (7) | 0.20 (4) |
Ni3 | 0.91312 (4) | 0.18257 (3) | 0.23065 (6) | 0.00542 (19) | |
Ni4 | 0.59336 (4) | 0.18693 (3) | 0.26615 (6) | 0.00530 (19) | |
Ni5 | 0.5 | 0.32688 (6) | 0 | 0.0112 (3) | |
Ni6 | 0 | 0 | 0.5 | 0.0061 (4) | |
As1 | 0.85957 (3) | 0.18473 (3) | 0.45674 (4) | 0.00503 (16) | |
As2 | 0.65106 (3) | 0.18354 (3) | 0.05278 (4) | 0.00470 (15) | |
As3 | 0.47038 (5) | 0 | 0.28662 (6) | 0.0062 (2) | |
As4 | 0.45990 (5) | 0.5 | −0.20991 (6) | 0.0056 (2) | |
Na1 | 0.2934 (2) | 0.5 | −0.0189 (3) | 0.0304 (13) | |
Na2 | 0.25173 (16) | 0.11586 (14) | 0.3367 (2) | 0.0305 (9) | |
Na3 | 0.7399 (2) | 0 | 0.3103 (4) | 0.0435 (15) | |
O1 | 0.6079 (2) | 0.09855 (19) | 0.1237 (3) | 0.0067 (5)* | |
O2 | 0.8783 (2) | 0.2776 (2) | 0.3717 (3) | 0.0125 (6)* | |
O3 | 0.4137 (3) | 0 | 0.1101 (4) | 0.0104 (8)* | |
O4 | 0.4391 (2) | 0.21767 (19) | 0.1132 (3) | 0.0090 (6)* | |
O5 | 0.7665 (2) | 0.1552 (2) | 0.0682 (3) | 0.0097 (6)* | |
O6 | 0.5380 (2) | 0.4081 (2) | −0.1240 (3) | 0.0096 (6)* | |
O8 | 0.3535 (3) | 0.5 | −0.1899 (5) | 0.0140 (9)* | |
O9 | 0.3901 (4) | 0 | 0.3581 (5) | 0.0232 (11)* | |
O10 | 0.9333 (2) | 0.20454 (19) | 0.6329 (3) | 0.0089 (6)* | |
O11 | 0.5468 (2) | 0.0939 (2) | 0.3604 (3) | 0.0115 (6)* | |
O12 | 0.7395 (2) | 0.1588 (2) | 0.4274 (3) | 0.0096 (6)* | |
O13 | 0.6448 (2) | 0.27433 (19) | 0.1522 (3) | 0.0092 (6)* | |
O14 | 0.4220 (3) | 0.5 | −0.3841 (4) | 0.0108 (9)* | |
O15 | 0.8965 (2) | 0.10027 (18) | 0.3788 (3) | 0.0062 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0070 (5) | 0.0067 (5) | 0.0068 (5) | 0 | 0.0032 (4) | 0 |
Ni2a | 0.0102 (7) | 0.006 (2) | 0.0096 (7) | 0 | 0.0068 (5) | 0 |
Ni2b | 0.021 (3) | 0.04 (2) | 0.019 (3) | 0 | 0.010 (2) | 0 |
Ni3 | 0.0047 (2) | 0.0062 (3) | 0.0048 (3) | −0.00029 (18) | 0.0018 (2) | 0.00088 (18) |
Ni4 | 0.0050 (2) | 0.0057 (3) | 0.0048 (3) | 0.00053 (18) | 0.0020 (2) | −0.00048 (18) |
Ni5 | 0.0097 (4) | 0.0149 (4) | 0.0084 (4) | 0 | 0.0039 (3) | 0 |
Ni6 | 0.0070 (5) | 0.0048 (5) | 0.0066 (5) | 0 | 0.0033 (4) | 0 |
As1 | 0.0049 (2) | 0.0058 (2) | 0.0047 (2) | 0.00044 (14) | 0.00248 (16) | 0.00007 (14) |
As2 | 0.00360 (19) | 0.0057 (2) | 0.0046 (2) | 0.00079 (14) | 0.00184 (16) | 0.00099 (14) |
As3 | 0.0082 (3) | 0.0051 (3) | 0.0054 (3) | 0 | 0.0032 (2) | 0 |
As4 | 0.0061 (3) | 0.0044 (3) | 0.0058 (3) | 0 | 0.0024 (2) | 0 |
Na1 | 0.0270 (17) | 0.0353 (17) | 0.0297 (17) | 0 | 0.0141 (14) | 0 |
Na2 | 0.0251 (11) | 0.0240 (11) | 0.0399 (14) | −0.0090 (9) | 0.0134 (10) | −0.0080 (10) |
Na3 | 0.0236 (17) | 0.0179 (15) | 0.061 (2) | 0 | −0.0026 (16) | 0 |
Ni1—O1 | 2.068 (2) | Ni6—O15iv | 2.049 (2) |
Ni1—O1i | 2.068 (2) | Ni6—O15xiii | 2.049 (2) |
Ni1—O1ii | 2.068 (2) | Ni6—O15xiv | 2.049 (2) |
Ni1—O1iii | 2.068 (2) | As1—Na2vii | 3.249 (2) |
Ni1—O3 | 2.081 (6) | As1—Na3 | 3.1713 (16) |
Ni1—O3i | 2.081 (6) | As1—O2 | 1.714 (3) |
Ni2a—Ni2b | 0.51 (7) | As1—O10 | 1.681 (3) |
Ni2a—Na2 | 3.185 (2) | As1—O12 | 1.664 (3) |
Ni2a—Na2iv | 3.185 (2) | As1—O15 | 1.702 (3) |
Ni2a—O11 | 1.974 (4) | As2—O1 | 1.711 (3) |
Ni2a—O11iv | 1.974 (4) | As2—O4i | 1.696 (3) |
Ni2b—Na2 | 3.260 (17) | As2—O5 | 1.659 (3) |
Ni2b—Na2iv | 3.260 (17) | As2—O13 | 1.716 (3) |
Ni2b—O2v | 1.83 (3) | As3—O3 | 1.650 (4) |
Ni2b—O2vi | 1.83 (3) | As3—O9 | 1.667 (7) |
Ni3—O4vii | 2.058 (3) | As3—O11 | 1.697 (3) |
Ni3—O5 | 2.047 (3) | As3—O11iii | 1.697 (3) |
Ni3—O6viii | 2.069 (3) | As4—Na1i | 3.240 (3) |
Ni3—O10ix | 2.029 (3) | As4—Na2xv | 3.190 (2) |
Ni3—O15 | 2.077 (3) | As4—Na2xvi | 3.190 (2) |
Ni4—O1 | 2.068 (3) | As4—O6 | 1.707 (3) |
Ni4—O4 | 2.101 (3) | As4—O6xvii | 1.707 (3) |
Ni4—O10v | 2.042 (3) | As4—O8 | 1.658 (6) |
Ni4—O11 | 1.980 (4) | As4—O14 | 1.660 (5) |
Ni4—O12 | 2.041 (3) | Na1—Na2xv | 3.540 (4) |
Ni5—O6 | 2.029 (3) | Na1—Na2xvi | 3.540 (4) |
Ni5—O6i | 2.029 (3) | Na1—Na3xviii | 3.923 (6) |
Ni5—O13 | 2.097 (3) | Na1—O8 | 2.358 (7) |
Ni5—O13i | 2.097 (3) | Na2—Na2iii | 3.361 (3) |
Ni6—O14x | 2.030 (6) | Na2—O2vi | 2.294 (4) |
Ni6—O14xi | 2.030 (6) | Na2—O8xi | 2.309 (3) |
Ni6—O15xii | 2.049 (2) | Na2—O13vi | 2.429 (3) |
O1—Ni1—O1i | 92.53 (10) | Na1i—As4—Na2xvi | 145.04 (5) |
O1—Ni1—O1ii | 180.0 (5) | Na1i—As4—O6 | 51.71 (9) |
O1—Ni1—O1iii | 87.47 (10) | Na1i—As4—O6xvii | 51.71 (9) |
O1—Ni1—O3 | 96.97 (12) | Na1i—As4—O8 | 132.24 (16) |
O1—Ni1—O3i | 83.03 (12) | Na1i—As4—O14 | 119.95 (18) |
O1i—Ni1—O1ii | 87.47 (10) | Na2xv—As4—Na2xvi | 63.58 (5) |
O1i—Ni1—O1iii | 180.0 (5) | Na2xv—As4—O6 | 154.25 (13) |
O1i—Ni1—O3 | 83.03 (12) | Na2xv—As4—O6xvii | 94.48 (10) |
O1i—Ni1—O3i | 96.97 (12) | Na2xv—As4—O8 | 44.13 (10) |
O1ii—Ni1—O1iii | 92.53 (10) | Na2xv—As4—O14 | 77.65 (15) |
O1ii—Ni1—O3 | 83.03 (12) | Na2xvi—As4—O6 | 94.48 (10) |
O1ii—Ni1—O3i | 96.97 (12) | Na2xvi—As4—O6xvii | 154.25 (13) |
O1iii—Ni1—O3 | 96.97 (12) | Na2xvi—As4—O8 | 44.13 (10) |
O1iii—Ni1—O3i | 83.03 (12) | Na2xvi—As4—O14 | 77.65 (15) |
O3—Ni1—O3i | 180.0 (5) | O6—As4—O6xvii | 102.64 (12) |
Ni2b—Ni2a—Na2 | 93.85 (16) | O6—As4—O8 | 110.86 (15) |
Ni2b—Ni2a—Na2iv | 93.85 (16) | O6—As4—O14 | 112.34 (14) |
Ni2b—Ni2a—O11 | 105.6 (3) | O6xvii—As4—O8 | 110.86 (15) |
Ni2b—Ni2a—O11iv | 105.6 (3) | O6xvii—As4—O14 | 112.34 (14) |
Na2—Ni2a—Na2iv | 172.3 (3) | O8—As4—O14 | 107.8 (2) |
Na2—Ni2a—O11 | 106.17 (12) | As4i—Na1—Na2xv | 110.70 (11) |
Na2—Ni2a—O11iv | 71.66 (9) | As4i—Na1—Na2xvi | 110.70 (11) |
Na2iv—Ni2a—O11 | 71.66 (9) | As4i—Na1—Na3xviii | 87.08 (8) |
Na2iv—Ni2a—O11iv | 106.17 (12) | As4i—Na1—O8 | 83.94 (14) |
O11—Ni2a—O11iv | 148.7 (5) | Na2xv—Na1—Na2xvi | 56.69 (7) |
Ni2a—Ni2b—Na2 | 77.1 (13) | Na2xv—Na1—Na3xviii | 145.38 (8) |
Ni2a—Ni2b—Na2iv | 77.1 (13) | Na2xv—Na1—O8 | 40.16 (9) |
Ni2a—Ni2b—O2v | 116 (2) | Na2xvi—Na1—Na3xviii | 145.38 (8) |
Ni2a—Ni2b—O2vi | 116 (2) | Na2xvi—Na1—O8 | 40.16 (9) |
Na2—Ni2b—Na2iv | 154 (3) | Na3xviii—Na1—O8 | 171.02 (14) |
Na2—Ni2b—O2v | 158 (2) | Ni2a—Na2—Ni2b | 9.1 (13) |
Na2—Ni2b—O2vi | 43.1 (7) | Ni2a—Na2—As1vi | 61.00 (16) |
Na2iv—Ni2b—O2v | 43.1 (7) | Ni2a—Na2—As4xi | 151.93 (17) |
Na2iv—Ni2b—O2vi | 158 (2) | Ni2a—Na2—Na1xi | 101.59 (12) |
O2v—Ni2b—O2vi | 127 (4) | Ni2a—Na2—Na2iii | 93.85 (17) |
O4vii—Ni3—O5 | 92.46 (12) | Ni2a—Na2—O2vi | 41.55 (17) |
O4vii—Ni3—O6viii | 84.64 (13) | Ni2a—Na2—O8xi | 129.3 (2) |
O4vii—Ni3—O10ix | 82.32 (12) | Ni2a—Na2—O13vi | 121.44 (17) |
O4vii—Ni3—O15 | 169.39 (11) | Ni2b—Na2—As1vi | 52.1 (12) |
O5—Ni3—O6viii | 84.66 (12) | Ni2b—Na2—As4xi | 160.9 (13) |
O5—Ni3—O10ix | 170.33 (16) | Ni2b—Na2—Na1xi | 105.7 (6) |
O5—Ni3—O15 | 94.46 (12) | Ni2b—Na2—Na2iii | 102.9 (13) |
O6viii—Ni3—O10ix | 86.74 (12) | Ni2b—Na2—O2vi | 33.1 (12) |
O6viii—Ni3—O15 | 103.99 (12) | Ni2b—Na2—O8xi | 137.2 (11) |
O10ix—Ni3—O15 | 91.91 (12) | Ni2b—Na2—O13vi | 114.0 (11) |
O1—Ni4—O4 | 90.49 (11) | As1vi—Na2—As4xi | 145.50 (8) |
O1—Ni4—O10v | 166.43 (12) | As1vi—Na2—Na1xi | 129.31 (10) |
O1—Ni4—O11 | 97.17 (13) | As1vi—Na2—Na2iii | 152.92 (7) |
O1—Ni4—O12 | 93.57 (12) | As1vi—Na2—O2vi | 30.22 (10) |
O4—Ni4—O10v | 80.96 (11) | As1vi—Na2—O8xi | 162.71 (11) |
O4—Ni4—O11 | 92.27 (12) | As1vi—Na2—O13vi | 74.79 (8) |
O4—Ni4—O12 | 175.26 (15) | As4xi—Na2—Na1xi | 69.02 (7) |
O10v—Ni4—O11 | 93.70 (14) | As4xi—Na2—Na2iii | 58.21 (5) |
O10v—Ni4—O12 | 95.48 (12) | As4xi—Na2—O2vi | 164.23 (11) |
O11—Ni4—O12 | 84.81 (12) | As4xi—Na2—O8xi | 30.00 (15) |
O6—Ni5—O6i | 108.95 (13) | As4xi—Na2—O13vi | 83.39 (9) |
O6—Ni5—O13 | 103.20 (12) | Na1xi—Na2—Na2iii | 61.65 (6) |
O6—Ni5—O13i | 101.19 (12) | Na1xi—Na2—O2vi | 104.27 (14) |
O6i—Ni5—O13 | 101.19 (12) | Na1xi—Na2—O8xi | 41.18 (16) |
O6i—Ni5—O13i | 103.20 (12) | Na1xi—Na2—O13vi | 77.57 (10) |
O13—Ni5—O13i | 137.37 (11) | Na2iii—Na2—O2vi | 132.33 (13) |
O14x—Ni6—O14xi | 180.0 (5) | Na2iii—Na2—O8xi | 43.30 (8) |
O14x—Ni6—O15xii | 85.74 (12) | Na2iii—Na2—O13vi | 130.98 (10) |
O14x—Ni6—O15iv | 94.26 (12) | O2vi—Na2—O8xi | 145.4 (2) |
O14x—Ni6—O15xiii | 94.26 (12) | O2vi—Na2—O13vi | 81.18 (12) |
O14x—Ni6—O15xiv | 85.74 (12) | O8xi—Na2—O13vi | 88.13 (11) |
O14xi—Ni6—O15xii | 94.26 (12) | As1—Na3—As1iii | 115.32 (9) |
O14xi—Ni6—O15iv | 85.74 (12) | As1—Na3—Na1xix | 98.15 (10) |
O14xi—Ni6—O15xiii | 85.74 (12) | As1iii—Na3—Na1xix | 98.15 (10) |
O14xi—Ni6—O15xiv | 94.26 (12) | Ni1—O1—Ni4 | 125.67 (17) |
O15xii—Ni6—O15iv | 89.57 (10) | Ni1—O1—As2 | 123.00 (15) |
O15xii—Ni6—O15xiii | 180.0 (5) | Ni4—O1—As2 | 93.49 (12) |
O15xii—Ni6—O15xiv | 90.43 (10) | Ni2bv—O2—As1 | 107.3 (16) |
O15iv—Ni6—O15xiii | 90.43 (10) | Ni2bv—O2—Na2vii | 103.8 (19) |
O15iv—Ni6—O15xiv | 180.0 (5) | As1—O2—Na2vii | 107.4 (2) |
O15xiii—Ni6—O15xiv | 89.57 (10) | Ni1—O3—As3 | 121.8 (2) |
Na2vii—As1—Na3 | 120.62 (5) | Ni3vi—O4—Ni4 | 96.68 (11) |
Na2vii—As1—O2 | 42.36 (13) | Ni3vi—O4—As2i | 124.13 (16) |
Na2vii—As1—O10 | 102.64 (10) | Ni4—O4—As2i | 139.19 (19) |
Na2vii—As1—O12 | 81.93 (11) | Ni3—O5—As2 | 129.51 (19) |
Na2vii—As1—O15 | 130.93 (11) | Ni3viii—O6—Ni5 | 104.78 (13) |
Na3—As1—O2 | 126.42 (12) | Ni3viii—O6—As4 | 121.23 (17) |
Na3—As1—O10 | 127.00 (12) | Ni5—O6—As4 | 118.91 (19) |
Na3—As1—O12 | 55.54 (13) | As4—O8—Na1 | 143.8 (2) |
Na3—As1—O15 | 51.68 (13) | As4—O8—Na2xv | 105.9 (2) |
O2—As1—O10 | 105.90 (14) | As4—O8—Na2xvi | 105.9 (2) |
O2—As1—O12 | 119.59 (14) | Na1—O8—Na2xv | 98.65 (19) |
O2—As1—O15 | 98.30 (17) | Na1—O8—Na2xvi | 98.65 (19) |
O10—As1—O12 | 107.84 (17) | Na2xv—O8—Na2xvi | 93.40 (14) |
O10—As1—O15 | 118.79 (13) | Ni3ix—O10—Ni4v | 99.49 (11) |
O12—As1—O15 | 106.93 (14) | Ni3ix—O10—As1 | 132.3 (2) |
O1—As2—O4i | 113.78 (13) | Ni4v—O10—As1 | 122.37 (14) |
O1—As2—O5 | 110.07 (15) | Ni2a—O11—Ni4 | 121.2 (3) |
O1—As2—O13 | 98.34 (16) | Ni2a—O11—As3 | 100.3 (3) |
O4i—As2—O5 | 114.98 (17) | Ni4—O11—As3 | 128.29 (18) |
O4i—As2—O13 | 100.05 (14) | Ni4—O12—As1 | 134.0 (2) |
O5—As2—O13 | 118.36 (14) | Ni5—O13—As2 | 97.57 (12) |
O3—As3—O9 | 115.8 (2) | Ni5—O13—Na2vii | 114.05 (13) |
O3—As3—O11 | 112.91 (14) | As2—O13—Na2vii | 142.98 (18) |
O3—As3—O11iii | 112.91 (14) | Ni6xx—O14—As4 | 133.6 (2) |
O9—As3—O11 | 103.68 (16) | Ni3—O15—Ni6xxi | 124.68 (17) |
O9—As3—O11iii | 103.68 (16) | Ni3—O15—As1 | 97.52 (13) |
O11—As3—O11iii | 106.83 (13) | Ni6xxi—O15—As1 | 120.85 (15) |
Na1i—As4—Na2xv | 145.04 (5) |
Symmetry codes: (i) −x+1, y, −z; (ii) −x+1, −y, −z; (iii) x, −y, z; (iv) −x+1, y, −z+1; (v) −x+3/2, −y+1/2, −z+1; (vi) x−1/2, −y+1/2, z; (vii) x+1/2, −y+1/2, z; (viii) −x+3/2, −y+1/2, −z; (ix) −x+2, y, −z+1; (x) x−1/2, y−1/2, z+1; (xi) −x+1/2, y−1/2, −z; (xii) x−1, y, z; (xiii) −x+1, −y, −z+1; (xiv) x−1, −y, z; (xv) −x+1/2, y+1/2, −z; (xvi) −x+1/2, −y+1/2, −z; (xvii) x, −y+1, z; (xviii) x−1/2, y+1/2, z; (xix) x+1/2, y−1/2, z; (xx) x+1/2, y+1/2, z−1; (xxi) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | Na4Ni7(AsO4)6 |
Mr | 1336.3 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 293 |
a, b, c (Å) | 14.5383 (11), 14.5047 (11), 10.6120 (8) |
β (°) | 118.299 (2) |
V (Å3) | 1970.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 16.76 |
Crystal size (mm) | 0.07 × 0.06 × 0.04 |
Data collection | |
Diffractometer | Bruker D8 Venture |
Absorption correction | Multi-scan (SADABS; Bruker, 2015) |
Tmin, Tmax | 0.640, 0.747 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 48075, 3773, 2901 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.772 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.052, 2.73 |
No. of reflections | 3773 |
No. of parameters | 146 |
Δρmax, Δρmin (e Å−3) | 3.34, −2.22 |
Computer programs: APEX3 (Bruker, 2015), SAINT (Bruker, 2015), SUPERFLIP (Palatinus & Chapuis, 2007), JANA2006 (Petříčcek et al., 2014, DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
Acknowledgements
The RS2E (French Network on Electrochemical Energy Storage) and ANR (Labex STORE-EX: grant ANR-10-LABX-0076) are acknowledged for funding of the X-ray diffractometer.
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