To investigate the influence of P/As substitution on structures and electrical properties, e.g. the effect on material densities, two new solid P/As-doped solutions, Na2CoP1.60As0.40O7 (disodium cobalt diphosphorus arsenic heptaoxide) and Na2CoP1.07As0.93O7 (disodium cobalt phosphorus arsenic heptaoxide), with melilite-like structures have been synthesized by solid-state reactions. Their unit-cell parameters are in agreement with Vegard's law. The obtained structural models were investigated by the bond valence sum (BVS) and charge distribution (CHARDI) validation tools and, for the latter, the structures are described as being built on anion-centred polyhedra. The frameworks can be described as layered and formed by {[Co(P,As)2O7]2−}∞ slabs, with alkali cations sandwiched between the layers and with the interlayer spaces increased due to P/As substitution. The BVS model was extended to a preliminary simulation of the sodium conduction properties in the studied structural type and suggests that the most probable sodium conduction pathways are bidimensional, at the (002) planes.
Supporting information
CCDC references: 1516121; 1516114
For both compounds, data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).
(I) Disodium cobalt diphosphorus arsenic heptaoxide
top
Crystal data top
Na2CoP1.60As0.40O7 | Dx = 3.184 Mg m−3 |
Mr = 296.43 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P42/mnm | Cell parameters from 25 reflections |
a = 7.737 (2) Å | θ = 12.5–14.9° |
c = 10.331 (4) Å | µ = 5.44 mm−1 |
V = 618.3 (4) Å3 | T = 293 K |
Z = 4 | Parallelepiped, blue |
F(000) = 569 | 0.24 × 0.24 × 0.10 mm |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 318 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.057 |
Graphite monochromator | θmax = 27.0°, θmin = 3.3° |
w/2θ scans | h = −9→1 |
Absorption correction: ψ scan (North et al., 1968) | k = −9→1 |
Tmin = 0.642, Tmax = 0.999 | l = −13→1 |
1008 measured reflections | 2 standard reflections every 120 min |
394 independent reflections | intensity decay: 1.0% |
Refinement top
Refinement on F2 | 1 restraint |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.040 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.112 | w = 1/[σ2(Fo2) + (0.0586P)2 + 0.4834P] where P = (Fo2 + 2Fc2)/3 |
S = 1.22 | (Δ/σ)max < 0.001 |
394 reflections | Δρmax = 1.00 e Å−3 |
48 parameters | Δρmin = −0.50 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Co1 | 0.0000 | 0.5000 | 0.2500 | 0.0244 (5) | |
P1 | 0.36320 (11) | 0.36320 (11) | 0.28845 (11) | 0.0194 (5) | 0.797 (6) |
As1 | 0.36320 (11) | 0.36320 (11) | 0.28845 (11) | 0.0194 (5) | 0.203 (6) |
Na1 | 0.1986 (3) | 0.1986 (3) | 0.0000 | 0.0346 (10) | |
Na2 | 0.3592 (4) | 0.6408 (4) | 0.0000 | 0.0288 (9) | |
O1 | 0.3651 (4) | 0.3651 (4) | 0.1413 (5) | 0.0317 (12) | |
O2 | 0.4653 (7) | 0.5347 (7) | 0.3444 (8) | 0.024 (2) | 0.5 |
O3A | 0.213 (2) | 0.458 (2) | 0.3525 (16) | 0.026 (2) | 0.44 (2) |
O3B | 0.179 (2) | 0.376 (3) | 0.344 (2) | 0.026 (2) | 0.34 (3) |
O3C | 0.180 (5) | 0.418 (6) | 0.366 (4) | 0.026 (2) | 0.22 (3) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0254 (5) | 0.0254 (5) | 0.0223 (8) | 0.000 | 0.000 | 0.000 |
P1 | 0.0201 (5) | 0.0201 (5) | 0.0180 (7) | 0.0008 (5) | 0.0010 (4) | 0.0010 (4) |
As1 | 0.0201 (5) | 0.0201 (5) | 0.0180 (7) | 0.0008 (5) | 0.0010 (4) | 0.0010 (4) |
Na1 | 0.0372 (14) | 0.0372 (14) | 0.029 (2) | −0.0192 (18) | 0.000 | 0.000 |
Na2 | 0.0300 (12) | 0.0300 (12) | 0.0264 (19) | 0.0043 (17) | 0.000 | 0.000 |
O1 | 0.0355 (17) | 0.0355 (17) | 0.024 (3) | −0.012 (2) | −0.0030 (14) | −0.0030 (14) |
O2 | 0.027 (3) | 0.027 (3) | 0.017 (4) | 0.002 (4) | 0.004 (2) | −0.004 (2) |
O3A | 0.016 (4) | 0.040 (7) | 0.023 (4) | −0.002 (4) | 0.002 (3) | 0.000 (5) |
O3B | 0.016 (4) | 0.040 (7) | 0.023 (4) | −0.002 (4) | 0.002 (3) | 0.000 (5) |
O3C | 0.016 (4) | 0.040 (7) | 0.023 (4) | −0.002 (4) | 0.002 (3) | 0.000 (5) |
Geometric parameters (Å, º) top
Co1—O3Bi | 1.94 (2) | Na1—O3Cix | 2.74 (5) |
Co1—O3Bii | 1.94 (2) | Na1—O3Cvii | 2.74 (5) |
Co1—O3Biii | 1.94 (2) | Na1—O3Cviii | 2.74 (5) |
Co1—O3B | 1.94 (2) | Na1—O3Ci | 2.74 (5) |
Co1—O3C | 1.95 (3) | Na2—O3Bx | 2.45 (2) |
Co1—O3Ci | 1.95 (3) | Na2—O3Bxi | 2.45 (2) |
Co1—O3Cii | 1.95 (3) | Na2—O3Bii | 2.45 (2) |
Co1—O3Ciii | 1.95 (3) | Na2—O3Bxii | 2.45 (2) |
Co1—O3Ai | 1.985 (16) | Na2—O3Cxi | 2.57 (4) |
Co1—O3Aii | 1.985 (16) | Na2—O3Cx | 2.57 (4) |
Co1—O3Aiii | 1.985 (16) | Na2—O3Cxii | 2.57 (4) |
Co1—O3A | 1.985 (16) | Na2—O3Cii | 2.57 (4) |
P1—O1 | 1.521 (5) | Na2—O1 | 2.585 (5) |
P1—O3Aiv | 1.526 (16) | Na2—O1vi | 2.585 (5) |
P1—O3A | 1.526 (16) | Na2—O1v | 2.585 (5) |
P1—O3Biv | 1.538 (19) | Na2—O1xiii | 2.585 (5) |
P1—O3B | 1.538 (19) | O1—Na2xiii | 2.585 (5) |
P1—O2v | 1.649 (3) | O2—O2v | 0.760 (14) |
P1—O2 | 1.649 (3) | O2—As1v | 1.649 (3) |
P1—O3Civ | 1.68 (4) | O2—P1v | 1.649 (3) |
P1—O3C | 1.68 (4) | O2—Na1xiv | 2.408 (8) |
Na1—O1vi | 2.334 (5) | O2—Na1xv | 3.016 (8) |
Na1—O1 | 2.334 (5) | O3A—O3B | 0.69 (2) |
Na1—O2vii | 2.408 (8) | O3A—Na1xiv | 2.499 (15) |
Na1—O2viii | 2.408 (8) | O3A—Na2xvi | 2.944 (17) |
Na1—O3Aix | 2.499 (15) | O3B—Na2xvi | 2.45 (2) |
Na1—O3Avii | 2.499 (15) | O3C—Na2xvi | 2.57 (4) |
Na1—O3Ai | 2.499 (15) | O3C—Na1xiv | 2.74 (5) |
Na1—O3Aviii | 2.499 (15) | | |
| | | |
O3Bi—Co1—O3Bii | 120.2 (13) | O3Aix—Na1—O3Cix | 7.7 (10) |
O3Bi—Co1—O3Biii | 104.4 (6) | O3Avii—Na1—O3Cix | 99.4 (10) |
O3Bii—Co1—O3Biii | 104.4 (6) | O3Ai—Na1—O3Cix | 68.0 (10) |
O3Bi—Co1—O3B | 104.4 (6) | O3Aviii—Na1—O3Cix | 141.2 (6) |
O3Bii—Co1—O3B | 104.4 (6) | O1vi—Na1—O3Cvii | 86.1 (8) |
O3Biii—Co1—O3B | 120.2 (13) | O1—Na1—O3Cvii | 124.3 (9) |
O3Bi—Co1—O3C | 115.4 (16) | O2vii—Na1—O3Cvii | 55.0 (9) |
O3Bii—Co1—O3C | 100.8 (14) | O2viii—Na1—O3Cvii | 95.8 (8) |
O3Biii—Co1—O3C | 111.4 (15) | O3Aix—Na1—O3Cvii | 99.4 (10) |
O3B—Co1—O3C | 11.7 (12) | O3Avii—Na1—O3Cvii | 7.7 (10) |
O3Bi—Co1—O3Ci | 11.7 (12) | O3Ai—Na1—O3Cvii | 141.2 (6) |
O3Bii—Co1—O3Ci | 111.4 (15) | O3Aviii—Na1—O3Cvii | 68.0 (10) |
O3Biii—Co1—O3Ci | 115.3 (16) | O3Cix—Na1—O3Cvii | 106.7 (19) |
O3B—Co1—O3Ci | 100.8 (14) | O1vi—Na1—O3Cviii | 124.3 (9) |
O3C—Co1—O3Ci | 112.3 (14) | O1—Na1—O3Cviii | 86.1 (8) |
O3Bi—Co1—O3Cii | 111.4 (15) | O2vii—Na1—O3Cviii | 95.8 (8) |
O3Bii—Co1—O3Cii | 11.7 (12) | O2viii—Na1—O3Cviii | 55.0 (9) |
O3Biii—Co1—O3Cii | 100.8 (14) | O3Aix—Na1—O3Cviii | 141.2 (6) |
O3B—Co1—O3Cii | 115.4 (16) | O3Avii—Na1—O3Cviii | 68.0 (10) |
O3C—Co1—O3Cii | 112.3 (14) | O3Ai—Na1—O3Cviii | 99.4 (10) |
O3Ci—Co1—O3Cii | 104 (3) | O3Aviii—Na1—O3Cviii | 7.7 (10) |
O3Bi—Co1—O3Ciii | 100.8 (14) | O3Cix—Na1—O3Cviii | 142.9 (15) |
O3Bii—Co1—O3Ciii | 115.3 (16) | O3Cvii—Na1—O3Cviii | 60.7 (18) |
O3Biii—Co1—O3Ciii | 11.7 (12) | O1vi—Na1—O3Ci | 124.3 (9) |
O3B—Co1—O3Ciii | 111.4 (15) | O1—Na1—O3Ci | 86.1 (8) |
O3C—Co1—O3Ciii | 104 (3) | O2vii—Na1—O3Ci | 95.8 (8) |
O3Ci—Co1—O3Ciii | 112.3 (14) | O2viii—Na1—O3Ci | 55.0 (9) |
O3Cii—Co1—O3Ciii | 112.3 (14) | O3Aix—Na1—O3Ci | 68.0 (10) |
O3Bi—Co1—O3Ai | 20.3 (7) | O3Avii—Na1—O3Ci | 141.2 (6) |
O3Bii—Co1—O3Ai | 113.9 (6) | O3Ai—Na1—O3Ci | 7.7 (10) |
O3Biii—Co1—O3Ai | 124.0 (7) | O3Aviii—Na1—O3Ci | 99.4 (10) |
O3B—Co1—O3Ai | 88.4 (7) | O3Cix—Na1—O3Ci | 60.7 (18) |
O3C—Co1—O3Ai | 100.0 (13) | O3Cvii—Na1—O3Ci | 142.9 (15) |
O3Ci—Co1—O3Ai | 12.4 (12) | O3Cviii—Na1—O3Ci | 106.7 (19) |
O3Cii—Co1—O3Ai | 108.6 (12) | O3Bx—Na2—O3Bxi | 104.7 (9) |
O3Ciii—Co1—O3Ai | 118.9 (13) | O3Bx—Na2—O3Bii | 82.4 (10) |
O3Bi—Co1—O3Aii | 113.9 (6) | O3Bxi—Na2—O3Bii | 52.2 (10) |
O3Bii—Co1—O3Aii | 20.3 (7) | O3Bx—Na2—O3Bxii | 52.2 (10) |
O3Biii—Co1—O3Aii | 88.4 (7) | O3Bxi—Na2—O3Bxii | 82.4 (10) |
O3B—Co1—O3Aii | 124.0 (7) | O3Bii—Na2—O3Bxii | 104.7 (9) |
O3C—Co1—O3Aii | 118.9 (13) | O3Bx—Na2—O3Cxi | 99.5 (9) |
O3Ci—Co1—O3Aii | 108.6 (12) | O3Bxi—Na2—O3Cxi | 8.7 (9) |
O3Cii—Co1—O3Aii | 12.4 (12) | O3Bii—Na2—O3Cxi | 57.1 (10) |
O3Ciii—Co1—O3Aii | 100.0 (13) | O3Bxii—Na2—O3Cxi | 73.8 (14) |
O3Ai—Co1—O3Aii | 115.5 (10) | O3Bx—Na2—O3Cx | 8.7 (9) |
O3Bi—Co1—O3Aiii | 88.4 (7) | O3Bxi—Na2—O3Cx | 99.5 (9) |
O3Bii—Co1—O3Aiii | 124.0 (7) | O3Bii—Na2—O3Cx | 73.8 (14) |
O3Biii—Co1—O3Aiii | 20.3 (7) | O3Bxii—Na2—O3Cx | 57.1 (10) |
O3B—Co1—O3Aiii | 113.9 (6) | O3Cxi—Na2—O3Cx | 95.3 (17) |
O3C—Co1—O3Aiii | 108.6 (12) | O3Bx—Na2—O3Cxii | 57.1 (10) |
O3Ci—Co1—O3Aiii | 100.0 (13) | O3Bxi—Na2—O3Cxii | 73.8 (14) |
O3Cii—Co1—O3Aiii | 118.9 (13) | O3Bii—Na2—O3Cxii | 99.5 (9) |
O3Ciii—Co1—O3Aiii | 12.4 (12) | O3Bxii—Na2—O3Cxii | 8.7 (9) |
O3Ai—Co1—O3Aiii | 106.5 (5) | O3Cxi—Na2—O3Cxii | 65 (2) |
O3Aii—Co1—O3Aiii | 106.5 (5) | O3Cx—Na2—O3Cxii | 60.8 (18) |
O3Bi—Co1—O3A | 124.0 (7) | O3Bx—Na2—O3Cii | 73.8 (14) |
O3Bii—Co1—O3A | 88.4 (7) | O3Bxi—Na2—O3Cii | 57.1 (10) |
O3Biii—Co1—O3A | 113.9 (6) | O3Bii—Na2—O3Cii | 8.7 (9) |
O3B—Co1—O3A | 20.3 (7) | O3Bxii—Na2—O3Cii | 99.5 (9) |
O3C—Co1—O3A | 12.4 (12) | O3Cxi—Na2—O3Cii | 60.8 (18) |
O3Ci—Co1—O3A | 118.9 (13) | O3Cx—Na2—O3Cii | 65 (2) |
O3Cii—Co1—O3A | 100.0 (13) | O3Cxii—Na2—O3Cii | 95.3 (17) |
O3Ciii—Co1—O3A | 108.6 (12) | O3Bx—Na2—O1 | 119.0 (5) |
O3Ai—Co1—O3A | 106.5 (5) | O3Bxi—Na2—O1 | 104.1 (5) |
O3Aii—Co1—O3A | 106.5 (5) | O3Bii—Na2—O1 | 75.0 (4) |
O3Aiii—Co1—O3A | 115.5 (10) | O3Bxii—Na2—O1 | 170.7 (5) |
O1—P1—O3Aiv | 115.8 (6) | O3Cxi—Na2—O1 | 112.7 (11) |
O1—P1—O3A | 115.8 (6) | O3Cx—Na2—O1 | 114.6 (9) |
O3Aiv—P1—O3A | 123.1 (13) | O3Cxii—Na2—O1 | 174.0 (8) |
O1—P1—O3Biv | 112.4 (8) | O3Cii—Na2—O1 | 79.0 (8) |
O3Aiv—P1—O3Biv | 26.2 (9) | O3Bx—Na2—O1vi | 75.0 (4) |
O3A—P1—O3Biv | 109.5 (9) | O3Bxi—Na2—O1vi | 170.7 (5) |
O1—P1—O3B | 112.4 (8) | O3Bii—Na2—O1vi | 119.0 (5) |
O3Aiv—P1—O3B | 109.5 (9) | O3Bxii—Na2—O1vi | 104.1 (5) |
O3A—P1—O3B | 26.2 (9) | O3Cxi—Na2—O1vi | 174.0 (8) |
O3Biv—P1—O3B | 89.0 (15) | O3Cx—Na2—O1vi | 79.0 (8) |
O1—P1—O2v | 109.8 (3) | O3Cxii—Na2—O1vi | 112.8 (11) |
O3Aiv—P1—O2v | 79.9 (6) | O3Cii—Na2—O1vi | 114.6 (9) |
O3A—P1—O2v | 103.3 (6) | O1—Na2—O1vi | 68.7 (2) |
O3Biv—P1—O2v | 105.1 (8) | O3Bx—Na2—O1v | 170.7 (5) |
O3B—P1—O2v | 125.7 (8) | O3Bxi—Na2—O1v | 75.0 (4) |
O1—P1—O2 | 109.8 (3) | O3Bii—Na2—O1v | 104.1 (5) |
O3Aiv—P1—O2 | 103.3 (6) | O3Bxii—Na2—O1v | 119.0 (5) |
O3A—P1—O2 | 79.9 (6) | O3Cxi—Na2—O1v | 79.0 (8) |
O3Biv—P1—O2 | 125.7 (8) | O3Cx—Na2—O1v | 174.0 (8) |
O3B—P1—O2 | 105.1 (8) | O3Cxii—Na2—O1v | 114.6 (9) |
O2v—P1—O2 | 26.6 (5) | O3Cii—Na2—O1v | 112.8 (11) |
O1—P1—O3Civ | 118.9 (13) | O1—Na2—O1v | 69.64 (19) |
O3Aiv—P1—O3Civ | 14.2 (14) | O1vi—Na2—O1v | 106.83 (18) |
O3A—P1—O3Civ | 113.0 (16) | O3Bx—Na2—O1xiii | 104.1 (5) |
O3Biv—P1—O3Civ | 13.2 (14) | O3Bxi—Na2—O1xiii | 119.0 (5) |
O3B—P1—O3Civ | 96.3 (15) | O3Bii—Na2—O1xiii | 170.7 (5) |
O2v—P1—O3Civ | 91.9 (17) | O3Bxii—Na2—O1xiii | 75.0 (4) |
O2—P1—O3Civ | 112.9 (16) | O3Cxi—Na2—O1xiii | 114.6 (9) |
O1—P1—O3C | 118.9 (13) | O3Cx—Na2—O1xiii | 112.8 (11) |
O3Aiv—P1—O3C | 113.0 (16) | O3Cxii—Na2—O1xiii | 79.0 (8) |
O3A—P1—O3C | 14.2 (14) | O3Cii—Na2—O1xiii | 174.0 (8) |
O3Biv—P1—O3C | 96.3 (15) | O1—Na2—O1xiii | 106.83 (18) |
O3B—P1—O3C | 13.2 (14) | O1vi—Na2—O1xiii | 69.64 (19) |
O2v—P1—O3C | 112.9 (16) | O1v—Na2—O1xiii | 68.7 (2) |
O2—P1—O3C | 91.9 (16) | P1—O1—Na1 | 127.9 (3) |
O3Civ—P1—O3C | 101 (3) | P1—O1—Na2xiii | 124.91 (18) |
O3Aiv—P1—Na1xv | 41.6 (6) | Na1—O1—Na2xiii | 95.32 (15) |
O3A—P1—Na1xv | 111.6 (6) | P1—O1—Na2 | 124.91 (18) |
O3Biv—P1—Na1xv | 65.4 (8) | Na1—O1—Na2 | 95.32 (15) |
O3B—P1—Na1xv | 118.2 (8) | Na2xiii—O1—Na2 | 73.17 (18) |
O2v—P1—Na1xv | 40.0 (2) | O2v—O2—As1v | 76.7 (2) |
O2—P1—Na1xv | 61.7 (3) | O2v—O2—P1v | 76.7 (2) |
O3Civ—P1—Na1xv | 52.2 (16) | As1v—O2—P1v | 0.00 (9) |
O3C—P1—Na1xv | 111.6 (13) | O2v—O2—P1 | 76.7 (2) |
Na2xvi—P1—Na1xv | 84.19 (5) | As1v—O2—P1 | 130.4 (5) |
Na1xiv—P1—Na1xv | 78.72 (10) | P1v—O2—P1 | 130.4 (5) |
O1vi—Na1—O1 | 77.4 (3) | O2v—O2—Na1xiv | 138.1 (2) |
O1vi—Na1—O2vii | 99.4 (2) | As1v—O2—Na1xiv | 113.9 (2) |
O1—Na1—O2vii | 176.8 (3) | P1v—O2—Na1xiv | 113.9 (2) |
O1vi—Na1—O2viii | 176.8 (2) | P1—O2—Na1xiv | 113.9 (2) |
O1—Na1—O2viii | 99.4 (2) | O2v—O2—Na1xv | 32.20 (15) |
O2vii—Na1—O2viii | 83.8 (4) | As1v—O2—Na1xv | 89.5 (3) |
O1vi—Na1—O3Aix | 83.0 (4) | P1v—O2—Na1xv | 89.5 (3) |
O1—Na1—O3Aix | 129.8 (4) | P1—O2—Na1xv | 89.5 (3) |
O2vii—Na1—O3Aix | 49.1 (4) | Na1xiv—O2—Na1xv | 105.9 (3) |
O2viii—Na1—O3Aix | 99.2 (4) | O3B—O3A—P1 | 78 (2) |
O1vi—Na1—O3Avii | 83.0 (4) | O3B—O3A—Co1 | 77 (2) |
O1—Na1—O3Avii | 129.8 (4) | P1—O3A—Co1 | 118.6 (9) |
O2vii—Na1—O3Avii | 49.1 (4) | O3B—O3A—Na1xiv | 150 (3) |
O2viii—Na1—O3Avii | 99.2 (4) | P1—O3A—Na1xiv | 114.5 (8) |
O3Aix—Na1—O3Avii | 92.0 (8) | Co1—O3A—Na1xiv | 115.6 (7) |
O1vi—Na1—O3Ai | 129.8 (4) | O3B—O3A—Na2xvi | 40 (2) |
O1—Na1—O3Ai | 83.0 (4) | P1—O3A—Na2xvi | 88.1 (7) |
O2vii—Na1—O3Ai | 99.2 (4) | Co1—O3A—Na2xvi | 104.7 (6) |
O2viii—Na1—O3Ai | 49.1 (4) | Na1xiv—O3A—Na2xvi | 110.9 (6) |
O3Aix—Na1—O3Ai | 75.1 (8) | O3A—O3B—P1 | 76 (2) |
O3Avii—Na1—O3Ai | 141.2 (8) | O3A—O3B—Co1 | 83 (2) |
O1vi—Na1—O3Aviii | 129.8 (4) | P1—O3B—Co1 | 120.4 (12) |
O1—Na1—O3Aviii | 83.0 (4) | O3A—O3B—Na2xvi | 130 (3) |
O2vii—Na1—O3Aviii | 99.2 (4) | P1—O3B—Na2xvi | 108.0 (10) |
O2viii—Na1—O3Aviii | 49.1 (4) | Co1—O3B—Na2xvi | 127.5 (8) |
O3Aix—Na1—O3Aviii | 141.2 (8) | P1—O3C—Co1 | 113 (2) |
O3Avii—Na1—O3Aviii | 75.1 (8) | P1—O3C—Na2xvi | 98.4 (18) |
O3Ai—Na1—O3Aviii | 92.0 (8) | Co1—O3C—Na2xvi | 121 (2) |
O1vi—Na1—O3Cix | 86.1 (8) | P1—O3C—Na1xiv | 98.7 (19) |
O1—Na1—O3Cix | 124.3 (9) | Co1—O3C—Na1xiv | 107.3 (18) |
O2vii—Na1—O3Cix | 55.0 (9) | Na2xvi—O3C—Na1xiv | 115.5 (15) |
O2viii—Na1—O3Cix | 95.8 (8) | | |
Symmetry codes: (i) y−1/2, −x+1/2, −z+1/2; (ii) −y+1/2, x+1/2, −z+1/2; (iii) −x, −y+1, z; (iv) y, x, z; (v) −x+1, −y+1, z; (vi) x, y, −z; (vii) −x+1/2, y−1/2, z−1/2; (viii) −x+1/2, y−1/2, −z+1/2; (ix) y−1/2, −x+1/2, z−1/2; (x) −y+1/2, x+1/2, z−1/2; (xi) −x+1/2, y+1/2, −z+1/2; (xii) −x+1/2, y+1/2, z−1/2; (xiii) −x+1, −y+1, −z; (xiv) −x+1/2, y+1/2, z+1/2; (xv) x+1/2, −y+1/2, −z+1/2; (xvi) −x+1/2, y−1/2, z+1/2. |
(II) Disodium cobalt phosphorus arsenic heptaoxide
top
Crystal data top
Na2CoP1.07As0.93O7 | Dx = 3.340 Mg m−3 |
Mr = 319.83 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P42/mnm | Cell parameters from 25 reflections |
a = 7.8084 (10) Å | θ = 11.4–14.7° |
c = 10.4329 (12) Å | µ = 7.91 mm−1 |
V = 636.11 (18) Å3 | T = 293 K |
Z = 4 | Parallelepiped, blue |
F(000) = 607 | 0.17 × 0.11 × 0.07 mm |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 305 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.129 |
Graphite monochromator | θmax = 27.0°, θmin = 3.3° |
w/2θ scans | h = −9→1 |
Absorption correction: ψ scan (North et al., 1968) | k = −9→1 |
Tmin = 0.797, Tmax = 0.998 | l = −13→13 |
1826 measured reflections | 2 standard reflections every 120 min |
404 independent reflections | intensity decay: 1.0% |
Refinement top
Refinement on F2 | 48 parameters |
Least-squares matrix: full | 1 restraint |
R[F2 > 2σ(F2)] = 0.046 | w = 1/[σ2(Fo2) + (0.0503P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.100 | (Δ/σ)max < 0.001 |
S = 1.09 | Δρmax = 0.83 e Å−3 |
404 reflections | Δρmin = −1.05 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Co1 | 0.0000 | 0.5000 | 0.2500 | 0.0287 (5) | |
As1 | 0.36231 (8) | 0.36231 (8) | 0.28780 (11) | 0.0236 (4) | 0.467 (6) |
P1 | 0.36231 (8) | 0.36231 (8) | 0.28780 (11) | 0.0236 (4) | 0.533 (6) |
Na1 | 0.2007 (3) | 0.2007 (3) | 0.0000 | 0.0403 (11) | |
Na2 | 0.3604 (3) | 0.6396 (3) | 0.0000 | 0.0314 (11) | |
O1 | 0.3659 (4) | 0.3659 (4) | 0.1393 (6) | 0.0361 (14) | |
O2 | 0.4630 (7) | 0.5370 (7) | 0.3463 (10) | 0.029 (3) | 0.5 |
O3A | 0.196 (7) | 0.425 (8) | 0.393 (6) | 0.033 (2) | 0.11 (2) |
O3B | 0.181 (2) | 0.3809 (19) | 0.3458 (16) | 0.033 (2) | 0.432 (17) |
O3C | 0.200 (2) | 0.4574 (19) | 0.3540 (19) | 0.033 (2) | 0.45 (2) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0268 (5) | 0.0268 (5) | 0.0325 (11) | 0.000 | 0.000 | 0.000 |
As1 | 0.0221 (4) | 0.0221 (4) | 0.0265 (8) | 0.0026 (4) | 0.0008 (3) | 0.0008 (3) |
P1 | 0.0221 (4) | 0.0221 (4) | 0.0265 (8) | 0.0026 (4) | 0.0008 (3) | 0.0008 (3) |
Na1 | 0.0389 (15) | 0.0389 (15) | 0.043 (3) | −0.0259 (19) | 0.000 | 0.000 |
Na2 | 0.0283 (13) | 0.0283 (13) | 0.038 (3) | 0.0063 (16) | 0.000 | 0.000 |
O1 | 0.0346 (17) | 0.0346 (17) | 0.039 (4) | −0.013 (2) | −0.0024 (15) | −0.0024 (15) |
O2 | 0.026 (3) | 0.026 (3) | 0.034 (7) | −0.003 (4) | 0.008 (2) | −0.008 (2) |
O3A | 0.037 (4) | 0.046 (7) | 0.014 (5) | 0.022 (6) | −0.002 (3) | 0.001 (6) |
O3B | 0.037 (4) | 0.046 (7) | 0.014 (5) | 0.022 (6) | −0.002 (3) | 0.001 (6) |
O3C | 0.037 (4) | 0.046 (7) | 0.014 (5) | 0.022 (6) | −0.002 (3) | 0.001 (6) |
Geometric parameters (Å, º) top
Co1—O3C | 1.933 (19) | Na1—O3Axi | 2.55 (6) |
Co1—O3Ci | 1.933 (19) | Na1—O3Ai | 2.55 (6) |
Co1—O3Cii | 1.933 (19) | Na1—O3Cxii | 2.554 (16) |
Co1—O3Ciii | 1.933 (19) | Na1—O3Cx | 2.554 (16) |
Co1—O3Bi | 1.965 (16) | Na1—O3Ci | 2.554 (16) |
Co1—O3Bii | 1.965 (16) | Na1—O3Cxi | 2.554 (16) |
Co1—O3Biii | 1.965 (16) | Na2—O3Bxiii | 2.499 (17) |
Co1—O3B | 1.965 (16) | Na2—O3Bxiv | 2.499 (17) |
Co1—O3A | 2.21 (5) | Na2—O3Bii | 2.499 (17) |
Co1—O3Ai | 2.21 (5) | Na2—O3Bxv | 2.499 (17) |
Co1—O3Aii | 2.21 (5) | Na2—O3Axiii | 2.53 (6) |
Co1—O3Aiii | 2.21 (5) | Na2—O3Axiv | 2.53 (6) |
As1—O3B | 1.546 (17) | Na2—O3Aii | 2.53 (6) |
As1—O3Biv | 1.546 (17) | Na2—O3Axv | 2.53 (6) |
As1—O1 | 1.549 (6) | Na2—O1ix | 2.585 (5) |
As1—O3C | 1.621 (17) | Na2—O1v | 2.585 (5) |
As1—O3Civ | 1.621 (17) | Na2—O1xvi | 2.585 (5) |
As1—O2v | 1.688 (4) | Na2—O1 | 2.585 (5) |
As1—O2 | 1.688 (4) | O1—Na2xvi | 2.585 (5) |
As1—O3A | 1.77 (6) | O2—O2v | 0.817 (15) |
As1—O3Aiv | 1.77 (6) | O2—As1v | 1.688 (4) |
As1—Na2vi | 3.309 (3) | O2—P1v | 1.688 (4) |
As1—Na1vii | 3.482 (2) | O2—Na1viii | 2.417 (9) |
As1—Na1viii | 3.482 (2) | O3A—O3B | 0.61 (5) |
Na1—O1ix | 2.332 (6) | O3A—Na2vi | 2.53 (6) |
Na1—O1 | 2.332 (6) | O3A—Na1viii | 2.55 (6) |
Na1—O2x | 2.417 (9) | O3B—O3C | 0.623 (18) |
Na1—O2xi | 2.417 (9) | O3B—Na2vi | 2.499 (17) |
Na1—O3Ax | 2.55 (6) | O3C—Na1viii | 2.554 (16) |
Na1—O3Axii | 2.55 (6) | O3C—Na2vi | 2.950 (18) |
| | | |
O3C—Co1—O3Ci | 108.4 (6) | O2x—Na1—O3Ai | 90.7 (13) |
O3C—Co1—O3Cii | 108.4 (6) | O2xi—Na1—O3Ai | 55.4 (13) |
O3Ci—Co1—O3Cii | 111.7 (11) | O3Ax—Na1—O3Ai | 136 (2) |
O3C—Co1—O3Ciii | 111.7 (11) | O3Axii—Na1—O3Ai | 52 (3) |
O3Ci—Co1—O3Ciii | 108.4 (6) | O3Axi—Na1—O3Ai | 110 (3) |
O3Cii—Co1—O3Ciii | 108.4 (6) | O1ix—Na1—O3Cxii | 82.7 (4) |
O3C—Co1—O3Bi | 123.0 (5) | O1—Na1—O3Cxii | 128.0 (4) |
O3Ci—Co1—O3Bi | 18.4 (5) | O2x—Na1—O3Cxii | 51.0 (4) |
O3Cii—Co1—O3Bi | 112.2 (5) | O2xi—Na1—O3Cxii | 99.3 (4) |
O3Ciii—Co1—O3Bi | 91.5 (7) | O3Ax—Na1—O3Cxii | 103.3 (15) |
O3C—Co1—O3Bii | 91.5 (7) | O3Axii—Na1—O3Cxii | 10.7 (12) |
O3Ci—Co1—O3Bii | 112.2 (5) | O3Axi—Na1—O3Cxii | 138.6 (11) |
O3Cii—Co1—O3Bii | 18.4 (5) | O3Ai—Na1—O3Cxii | 62.5 (16) |
O3Ciii—Co1—O3Bii | 123.0 (5) | O1ix—Na1—O3Cx | 82.7 (4) |
O3Bi—Co1—O3Bii | 118.9 (10) | O1—Na1—O3Cx | 128.0 (4) |
O3C—Co1—O3Biii | 112.2 (5) | O2x—Na1—O3Cx | 51.0 (4) |
O3Ci—Co1—O3Biii | 123.0 (5) | O2xi—Na1—O3Cx | 99.3 (4) |
O3Cii—Co1—O3Biii | 91.5 (7) | O3Ax—Na1—O3Cx | 10.7 (12) |
O3Ciii—Co1—O3Biii | 18.4 (5) | O3Axii—Na1—O3Cx | 103.3 (15) |
O3Bi—Co1—O3Biii | 105.0 (4) | O3Axi—Na1—O3Cx | 62.5 (16) |
O3Bii—Co1—O3Biii | 105.0 (4) | O3Ai—Na1—O3Cx | 138.6 (11) |
O3C—Co1—O3B | 18.4 (5) | O3Cxii—Na1—O3Cx | 95.4 (9) |
O3Ci—Co1—O3B | 91.5 (7) | O1ix—Na1—O3Ci | 128.0 (4) |
O3Cii—Co1—O3B | 123.0 (5) | O1—Na1—O3Ci | 82.7 (4) |
O3Ciii—Co1—O3B | 112.2 (5) | O2x—Na1—O3Ci | 99.3 (4) |
O3Bi—Co1—O3B | 105.0 (4) | O2xi—Na1—O3Ci | 51.0 (4) |
O3Bii—Co1—O3B | 105.0 (4) | O3Ax—Na1—O3Ci | 138.6 (11) |
O3Biii—Co1—O3B | 118.9 (10) | O3Axii—Na1—O3Ci | 62.5 (16) |
O3C—Co1—O3A | 10.8 (17) | O3Axi—Na1—O3Ci | 103.3 (15) |
O3Ci—Co1—O3A | 106.5 (16) | O3Ai—Na1—O3Ci | 10.7 (12) |
O3Cii—Co1—O3A | 118.2 (19) | O3Cxii—Na1—O3Ci | 73.2 (9) |
O3Ciii—Co1—O3A | 103.1 (16) | O3Cx—Na1—O3Ci | 143.6 (8) |
O3Bi—Co1—O3A | 118.7 (17) | O1ix—Na1—O3Cxi | 128.0 (4) |
O3Bii—Co1—O3A | 101.8 (17) | O1—Na1—O3Cxi | 82.7 (4) |
O3Biii—Co1—O3A | 106.2 (16) | O2x—Na1—O3Cxi | 99.3 (4) |
O3B—Co1—O3A | 15.5 (13) | O2xi—Na1—O3Cxi | 51.0 (4) |
O3C—Co1—O3Ai | 118.2 (18) | O3Ax—Na1—O3Cxi | 62.5 (16) |
O3Ci—Co1—O3Ai | 10.8 (17) | O3Axii—Na1—O3Cxi | 138.6 (11) |
O3Cii—Co1—O3Ai | 103.1 (16) | O3Axi—Na1—O3Cxi | 10.7 (12) |
O3Ciii—Co1—O3Ai | 106.5 (16) | O3Ai—Na1—O3Cxi | 103.3 (15) |
O3Bi—Co1—O3Ai | 15.5 (13) | O3Cxii—Na1—O3Cxi | 143.6 (8) |
O3Bii—Co1—O3Ai | 106.2 (16) | O3Cx—Na1—O3Cxi | 73.2 (9) |
O3Biii—Co1—O3Ai | 118.7 (17) | O3Ci—Na1—O3Cxi | 95.4 (9) |
O3B—Co1—O3Ai | 101.8 (17) | O3Bxiii—Na2—O3Bxiv | 102.7 (8) |
O3A—Co1—O3Ai | 117.0 (16) | O3Bxiii—Na2—O3Bii | 80.2 (7) |
O3C—Co1—O3Aii | 106.5 (16) | O3Bxiv—Na2—O3Bii | 52.4 (7) |
O3Ci—Co1—O3Aii | 103.1 (16) | O3Bxiii—Na2—O3Bxv | 52.4 (7) |
O3Cii—Co1—O3Aii | 10.8 (17) | O3Bxiv—Na2—O3Bxv | 80.2 (7) |
O3Ciii—Co1—O3Aii | 118.2 (18) | O3Bii—Na2—O3Bxv | 102.7 (8) |
O3Bi—Co1—O3Aii | 106.2 (16) | O3Bxiii—Na2—O3Axiii | 14.0 (12) |
O3Bii—Co1—O3Aii | 15.5 (13) | O3Bxiv—Na2—O3Axiii | 92.3 (14) |
O3Biii—Co1—O3Aii | 101.8 (17) | O3Bii—Na2—O3Axiii | 66.3 (14) |
O3B—Co1—O3Aii | 118.7 (17) | O3Bxv—Na2—O3Axiii | 58.1 (13) |
O3A—Co1—O3Aii | 117.0 (17) | O3Bxiii—Na2—O3Axiv | 92.3 (14) |
O3Ai—Co1—O3Aii | 95 (3) | O3Bxiv—Na2—O3Axiv | 14.0 (12) |
O3C—Co1—O3Aiii | 103.1 (16) | O3Bii—Na2—O3Axiv | 58.1 (13) |
O3Ci—Co1—O3Aiii | 118.2 (19) | O3Bxv—Na2—O3Axiv | 66.3 (14) |
O3Cii—Co1—O3Aiii | 106.5 (16) | O3Axiii—Na2—O3Axiv | 84 (3) |
O3Ciii—Co1—O3Aiii | 10.8 (17) | O3Bxiii—Na2—O3Aii | 66.3 (14) |
O3Bi—Co1—O3Aiii | 101.8 (17) | O3Bxiv—Na2—O3Aii | 58.1 (13) |
O3Bii—Co1—O3Aiii | 118.7 (17) | O3Bii—Na2—O3Aii | 14.0 (12) |
O3Biii—Co1—O3Aiii | 15.5 (13) | O3Bxv—Na2—O3Aii | 92.3 (14) |
O3B—Co1—O3Aiii | 106.2 (16) | O3Axiii—Na2—O3Aii | 52 (3) |
O3A—Co1—O3Aiii | 95 (3) | O3Axiv—Na2—O3Aii | 60 (2) |
O3Ai—Co1—O3Aiii | 117.0 (17) | O3Bxiii—Na2—O3Axv | 58.1 (13) |
O3Aii—Co1—O3Aiii | 117.0 (17) | O3Bxiv—Na2—O3Axv | 66.3 (14) |
O3B—As1—O3Biv | 91.1 (11) | O3Bii—Na2—O3Axv | 92.3 (14) |
O3B—As1—O1 | 113.9 (6) | O3Bxv—Na2—O3Axv | 14.0 (12) |
O3Biv—As1—O1 | 113.9 (6) | O3Axiii—Na2—O3Axv | 60 (2) |
O3B—As1—O3C | 22.5 (7) | O3Axiv—Na2—O3Axv | 52 (3) |
O3Biv—As1—O3C | 109.0 (8) | O3Aii—Na2—O3Axv | 84 (3) |
O1—As1—O3C | 115.6 (7) | O3Bxiii—Na2—O1ix | 76.0 (4) |
O3B—As1—O3Civ | 109.0 (8) | O3Bxiv—Na2—O1ix | 171.0 (4) |
O3Biv—As1—O3Civ | 22.5 (7) | O3Bii—Na2—O1ix | 118.8 (4) |
O1—As1—O3Civ | 115.6 (7) | O3Bxv—Na2—O1ix | 105.3 (4) |
O3C—As1—O3Civ | 122.2 (14) | O3Axiii—Na2—O1ix | 84.8 (13) |
O3B—As1—O2v | 123.7 (7) | O3Axiv—Na2—O1ix | 168.2 (13) |
O3Biv—As1—O2v | 102.1 (6) | O3Aii—Na2—O1ix | 113.9 (12) |
O1—As1—O2v | 109.8 (4) | O3Axv—Na2—O1ix | 118.9 (13) |
O3C—As1—O2v | 105.2 (7) | O3Bxiii—Na2—O1v | 171.0 (4) |
O3Civ—As1—O2v | 80.7 (6) | O3Bxiv—Na2—O1v | 76.0 (4) |
O3B—As1—O2 | 102.1 (6) | O3Bii—Na2—O1v | 105.3 (4) |
O3Biv—As1—O2 | 123.7 (7) | O3Bxv—Na2—O1v | 118.8 (4) |
O1—As1—O2 | 109.8 (4) | O3Axiii—Na2—O1v | 168.2 (13) |
O3C—As1—O2 | 80.7 (6) | O3Axiv—Na2—O1v | 84.8 (13) |
O3Civ—As1—O2 | 105.2 (7) | O3Aii—Na2—O1v | 118.9 (13) |
O2v—As1—O2 | 28.0 (5) | O3Axv—Na2—O1v | 113.9 (12) |
O3B—As1—O3A | 19.9 (18) | O1ix—Na2—O1v | 106.79 (18) |
O3Biv—As1—O3A | 95 (2) | O3Bxiii—Na2—O1xvi | 105.3 (4) |
O1—As1—O3A | 128.9 (18) | O3Bxiv—Na2—O1xvi | 118.8 (4) |
O3C—As1—O3A | 15.4 (17) | O3Bii—Na2—O1xvi | 171.0 (4) |
O3Civ—As1—O3A | 107 (2) | O3Bxv—Na2—O1xvi | 76.0 (4) |
O2v—As1—O3A | 104 (2) | O3Axiii—Na2—O1xvi | 118.9 (13) |
O2—As1—O3A | 84 (2) | O3Axiv—Na2—O1xvi | 113.9 (12) |
O3B—As1—O3Aiv | 95 (2) | O3Aii—Na2—O1xvi | 168.2 (13) |
O3Biv—As1—O3Aiv | 19.9 (18) | O3Axv—Na2—O1xvi | 84.8 (13) |
O1—As1—O3Aiv | 128.9 (18) | O1ix—Na2—O1xvi | 69.92 (18) |
O3C—As1—O3Aiv | 107 (2) | O1v—Na2—O1xvi | 68.4 (2) |
O3Civ—As1—O3Aiv | 15.4 (17) | O3Bxiii—Na2—O1 | 118.8 (4) |
O2v—As1—O3Aiv | 84 (2) | O3Bxiv—Na2—O1 | 105.3 (4) |
O2—As1—O3Aiv | 104 (2) | O3Bii—Na2—O1 | 76.0 (4) |
O3A—As1—O3Aiv | 91 (4) | O3Bxv—Na2—O1 | 171.0 (4) |
O3B—As1—Na2vi | 46.1 (6) | O3Axiii—Na2—O1 | 113.9 (12) |
O3Biv—As1—Na2vi | 46.1 (6) | O3Axiv—Na2—O1 | 118.9 (13) |
O1—As1—Na2vi | 133.44 (16) | O3Aii—Na2—O1 | 84.8 (13) |
O3C—As1—Na2vi | 63.0 (6) | O3Axv—Na2—O1 | 168.2 (13) |
O3Civ—As1—Na2vi | 63.0 (6) | O1ix—Na2—O1 | 68.4 (2) |
O2v—As1—Na2vi | 115.3 (3) | O1v—Na2—O1 | 69.92 (18) |
O2—As1—Na2vi | 115.3 (3) | O1xvi—Na2—O1 | 106.79 (18) |
O3A—As1—Na2vi | 49 (2) | As1—O1—Na1 | 127.1 (3) |
O3Aiv—As1—Na2vi | 49 (2) | As1—O1—Na2 | 125.21 (18) |
O3B—As1—Na1vii | 117.3 (6) | Na1—O1—Na2 | 95.60 (19) |
O3Biv—As1—Na1vii | 63.3 (6) | As1—O1—Na2xvi | 125.21 (18) |
O1—As1—Na1vii | 128.65 (10) | Na1—O1—Na2xvi | 95.60 (19) |
O3C—As1—Na1vii | 112.7 (7) | Na2—O1—Na2xvi | 73.21 (18) |
O3Civ—As1—Na1vii | 43.2 (6) | O2v—O2—As1 | 76.0 (2) |
O2v—As1—Na1vii | 39.0 (2) | O2v—O2—As1v | 76.0 (2) |
O2—As1—Na1vii | 62.0 (3) | As1—O2—As1v | 128.5 (6) |
O3A—As1—Na1vii | 101.7 (18) | O2v—O2—P1v | 76.0 (2) |
O3Aiv—As1—Na1vii | 45 (2) | As1—O2—P1v | 128.5 (6) |
Na2vi—As1—Na1vii | 84.21 (4) | As1v—O2—P1v | 0.00 (8) |
O3B—As1—Na1viii | 63.3 (6) | O2v—O2—Na1viii | 138.4 (2) |
O3Biv—As1—Na1viii | 117.3 (6) | As1—O2—Na1viii | 114.9 (2) |
O1—As1—Na1viii | 128.65 (10) | As1v—O2—Na1viii | 114.9 (2) |
O3C—As1—Na1viii | 43.2 (6) | P1v—O2—Na1viii | 114.9 (2) |
O3Civ—As1—Na1viii | 112.7 (7) | O3B—O3A—As1 | 59 (5) |
O2v—As1—Na1viii | 62.0 (3) | O3B—O3A—Co1 | 59 (5) |
O2—As1—Na1viii | 39.0 (2) | As1—O3A—Co1 | 99 (3) |
O3A—As1—Na1viii | 45 (2) | O3B—O3A—Na2vi | 80 (6) |
O3Aiv—As1—Na1viii | 101.7 (18) | As1—O3A—Na2vi | 99 (2) |
Na2vi—As1—Na1viii | 84.21 (4) | Co1—O3A—Na2vi | 114 (3) |
Na1vii—As1—Na1viii | 79.06 (10) | O3B—O3A—Na1viii | 152 (8) |
O1ix—Na1—O1 | 77.1 (3) | As1—O3A—Na1viii | 106 (3) |
O1ix—Na1—O2x | 99.9 (3) | Co1—O3A—Na1viii | 107 (2) |
O1—Na1—O2x | 177.0 (3) | Na2vi—O3A—Na1viii | 127 (2) |
O1ix—Na1—O2xi | 177.0 (3) | O3A—O3B—O3C | 46 (5) |
O1—Na1—O2xi | 99.9 (3) | O3A—O3B—As1 | 101 (6) |
O2x—Na1—O2xi | 83.2 (5) | O3C—O3B—As1 | 86 (3) |
O1ix—Na1—O3Ax | 91.0 (12) | O3A—O3B—Co1 | 106 (5) |
O1—Na1—O3Ax | 124.3 (13) | O3C—O3B—Co1 | 78 (3) |
O2x—Na1—O3Ax | 55.4 (13) | As1—O3B—Co1 | 120.3 (10) |
O2xi—Na1—O3Ax | 90.7 (13) | O3A—O3B—Na2vi | 86 (6) |
O1ix—Na1—O3Axii | 91.0 (12) | O3C—O3B—Na2vi | 132 (3) |
O1—Na1—O3Axii | 124.3 (13) | As1—O3B—Na2vi | 107.4 (7) |
O2x—Na1—O3Axii | 55.4 (13) | Co1—O3B—Na2vi | 126.2 (8) |
O2xi—Na1—O3Axii | 90.7 (13) | O3B—O3C—As1 | 72 (3) |
O3Ax—Na1—O3Axii | 110 (3) | O3B—O3C—Co1 | 84 (3) |
O1ix—Na1—O3Axi | 124.3 (13) | As1—O3C—Co1 | 118.1 (10) |
O1—Na1—O3Axi | 91.0 (12) | O3B—O3C—Na1viii | 150 (3) |
O2x—Na1—O3Axi | 90.7 (13) | As1—O3C—Na1viii | 111.1 (9) |
O2xi—Na1—O3Axi | 55.4 (13) | Co1—O3C—Na1viii | 116.8 (7) |
O3Ax—Na1—O3Axi | 52 (3) | O3B—O3C—Na2vi | 39 (3) |
O3Axii—Na1—O3Axi | 136 (2) | As1—O3C—Na2vi | 87.7 (6) |
O1ix—Na1—O3Ai | 124.3 (13) | Co1—O3C—Na2vi | 107.7 (7) |
O1—Na1—O3Ai | 91.0 (12) | Na1viii—O3C—Na2vi | 111.5 (7) |
Symmetry codes: (i) y−1/2, −x+1/2, −z+1/2; (ii) −y+1/2, x+1/2, −z+1/2; (iii) −x, −y+1, z; (iv) y, x, z; (v) −x+1, −y+1, z; (vi) −x+1/2, y−1/2, z+1/2; (vii) x+1/2, −y+1/2, −z+1/2; (viii) −x+1/2, y+1/2, z+1/2; (ix) x, y, −z; (x) −x+1/2, y−1/2, z−1/2; (xi) −x+1/2, y−1/2, −z+1/2; (xii) y−1/2, −x+1/2, z−1/2; (xiii) −y+1/2, x+1/2, z−1/2; (xiv) −x+1/2, y+1/2, −z+1/2; (xv) −x+1/2, y+1/2, z−1/2; (xvi) −x+1, −y+1, −z. |
BVS and CHARDI analysis of anion polyhedra in the studied compound
(Structure described as built on anion-centred polyhedra). topPhase (I) | q(i).sof(i) | V(i) | Q(i) |
O1 | -2.00 | -1.91 | -1.91 |
O2 | -1.00 | -1.16 | -0.97 |
O3A | -0.88 | -0.86 | -0.85 |
O3B | -0.68 | -0.70 | -0.70 |
O3C | -0.44 | -0.40 | -0.51 |
Co | 2.00 | 1.96 | 1.56 |
M(1) | 5.00 | 4.99 | 5.07 |
Na1 | 1.00 | 1.08 | 1.21 |
Na2 | 1.00 | 0.96 | 1.09 |
| | | |
Phase (II) | q(i).sof(i) | V(i) | Q(i) |
O1 | -2.00 | -1.95 | -1.96 |
O2 | -1.00 | -1.16 | -0.98 |
O3A | -0.22 | -0.16 | -0.22 |
O3B | -0.86 | -0.91 | -0.88 |
O3C | -0.90 | -0.86 | -0.93 |
Co | 2.00 | 1.89 | 1.67 |
M(2) | 5.00 | 5.03 | 5.09 |
Na1 | 1.00 | 1.04 | 1.08 |
Na2 | 1.00 | 0.94 | 0.99 |
Notes; (I) = Na2CoP1.60As0.40O7;
(II) = Na2CoP1.07As0.93O7;
M(1) = P0.80As0.20;
M(2) = P0.533As0.467;
q is the formal oxidation number;
sof is the site-occupation factor;
sodium coordination numbers for d(Na—O)max = 3.25 Å. The mean
absolute percentage deviation
(MAPD) measures the agreement between q and Q [MAPD(I) =
3.4% and
MAPD(II) = 2.2%]; for more
information, see Nespolo (2016). |