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The two title trialkaline trioxoantimonates(III), tripotassium trioxoantimonate(III), K3[SbO3], (I), and tricaesium trioxoantimonate(III), Cs3[SbO3], (II), crystallize in the cubic Na3[AsS3] structure type in space group P213. The structures show discrete Ψ-tetrahedral [SbO3]3− anions with C3v point-group symmetry. The Sb—O distances are 1.923 (4) Å in (I) and 1.928 (2) Å in (II), and the O—Sb—O bond angles are 99.5 (2)° in (I) and 100.4 (1)° in (II).
Supporting information
Crystals of (I) were grown from a mixture containing KO2 (Fluka AG, 99.0%), K
(Alkali-Metallhandel GmbH Bonn, 98.0%) and Sb powder (Sigma-Aldrich, 99.8%) in
a molar ratio of 0.5:1.5:2. The mixture was heated up to 973 K and then cooled
down to 573 K at a rate of 5 K h-1. Then the furnace was turned off. For
(II), CsO2 (803 mg, 4.87 mmol) was reacted with powdered Sb (198 mg, 1.62 mmol) in a corundum crucible under an argon atmosphere. The mixture was heated
up to 973 K within 3.5 h and then cooled down to room temperature at a rate of
5 K h-1. The X-ray powder pattern of the sample (Stadi P diffractometer with
linear PSD; Stoe & Cie, Darmstadt) could be indexed with the single-crystal
data of (II) and showed weak reflections of Cs3[SbO4] and elemental Sb.
Both title compounds formed hydroscopic colourless crystals, which were
handled in a dry box under argon and prepared in capillaries filled with dried
oil.
For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989) Query; cell refinement: CAD-4 Software Query; data reduction: HELENA (Spek, 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1968) and DRAWxtl (Finger & Kroeker, 1999); software used to prepare material for publication: SHELXL97.
(I) Tripotassium trioxoantimonate(III)
top
Crystal data top
K3[SbO3] | Dx = 3.272 Mg m−3 |
Mr = 287.05 | Mo Kα radiation, λ = 0.71070 Å |
Cubic, P213 | Cell parameters from 25 reflections |
Hall symbol: P 2ac 2ab 3 | θ = 3.8–29.3° |
a = 8.352 (5) Å | µ = 6.77 mm−1 |
V = 582.7 (5) Å3 | T = 293 K |
Z = 4 | Prism, colourless |
F(000) = 528 | 0.1 × 0.1 × 0.1 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 377 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.090 |
Graphite monochromator | θmax = 27.4°, θmin = 4.2° |
ω/2θ scans | h = 0→10 |
Absorption correction: ψ scan (North et al., 1968) | k = −10→10 |
Tmin = 0.497, Tmax = 0.508 | l = −10→0 |
1510 measured reflections | 3 standard reflections every 120 min |
455 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0219P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.026 | (Δ/σ)max < 0.001 |
wR(F2) = 0.054 | Δρmax = 0.72 e Å−3 |
S = 1.04 | Δρmin = −1.03 e Å−3 |
455 reflections | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
20 parameters | Extinction coefficient: 0.0025 (9) |
0 restraints | Absolute structure: Flack (1983), 189 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (11) |
Crystal data top
K3[SbO3] | Z = 4 |
Mr = 287.05 | Mo Kα radiation |
Cubic, P213 | µ = 6.77 mm−1 |
a = 8.352 (5) Å | T = 293 K |
V = 582.7 (5) Å3 | 0.1 × 0.1 × 0.1 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 377 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.090 |
Tmin = 0.497, Tmax = 0.508 | 3 standard reflections every 120 min |
1510 measured reflections | intensity decay: none |
455 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.054 | Δρmax = 0.72 e Å−3 |
S = 1.04 | Δρmin = −1.03 e Å−3 |
455 reflections | Absolute structure: Flack (1983), 189 Friedel pairs |
20 parameters | Absolute structure parameter: −0.03 (11) |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Sb | 0.51456 (4) | 0.51456 (4) | 0.51456 (4) | 0.01377 (18) | |
K1 | 0.7890 (2) | 0.7890 (2) | 0.7890 (2) | 0.0192 (5) | |
K2 | 0.2839 (2) | 0.2839 (2) | 0.2839 (2) | 0.0177 (5) | |
K3 | 0.02565 (16) | 0.02565 (16) | 0.02565 (16) | 0.0242 (4) | |
O1 | 0.0051 (5) | 0.2108 (4) | 0.4391 (4) | 0.0206 (8) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sb | 0.01377 (18) | 0.01377 (18) | 0.01377 (18) | −0.00078 (16) | −0.00078 (16) | −0.00078 (16) |
K1 | 0.0192 (5) | 0.0192 (5) | 0.0192 (5) | 0.0025 (8) | 0.0025 (8) | 0.0025 (8) |
K2 | 0.0177 (5) | 0.0177 (5) | 0.0177 (5) | −0.0006 (7) | −0.0006 (7) | −0.0006 (7) |
K3 | 0.0242 (4) | 0.0242 (4) | 0.0242 (4) | −0.0008 (5) | −0.0008 (5) | −0.0008 (5) |
O1 | 0.0165 (19) | 0.0179 (17) | 0.0274 (17) | −0.003 (2) | −0.0001 (19) | 0.0076 (13) |
Geometric parameters (Å, º) top
Sb—O1i | 1.923 (4) | K2—O1i | 2.961 (5) |
Sb—O1ii | 1.923 (4) | K2—O1iii | 2.961 (5) |
Sb—O1iii | 1.923 (4) | K2—O1ii | 2.961 (5) |
K1—O1iv | 2.758 (5) | K3—O1xii | 2.659 (4) |
K1—O1v | 2.758 (5) | K3—O1xiii | 2.659 (4) |
K1—O1vi | 2.758 (5) | K3—O1xiv | 2.659 (4) |
K1—O1vii | 2.922 (5) | O1—Sbxv | 1.923 (4) |
K1—O1viii | 2.922 (5) | O1—K3xvi | 2.659 (4) |
K1—O1ix | 2.922 (5) | O1—K1xvii | 2.758 (5) |
K2—O1x | 2.734 (4) | O1—K1xviii | 2.922 (5) |
K2—O1xi | 2.734 (4) | O1—K2xv | 2.961 (5) |
K2—O1 | 2.734 (4) | | |
| | | |
O1i—Sb—O1ii | 99.50 (15) | O1ii—Sb—O1iii | 99.51 (15) |
O1i—Sb—O1iii | 99.50 (15) | | |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −z+1, x+1/2, −y+1/2; (iii) −y+1/2, −z+1, x+1/2; (iv) z+1/2, −x+1/2, −y+1; (v) −y+1, z+1/2, −x+1/2; (vi) −x+1/2, −y+1, z+1/2; (vii) −x+1, y+1/2, −z+3/2; (viii) y+1/2, −z+3/2, −x+1; (ix) −z+3/2, −x+1, y+1/2; (x) z, x, y; (xi) y, z, x; (xii) −x, y−1/2, −z+1/2; (xiii) −z+1/2, −x, y−1/2; (xiv) y−1/2, −z+1/2, −x; (xv) x−1/2, −y+1/2, −z+1; (xvi) −x, y+1/2, −z+1/2; (xvii) −x+1/2, −y+1, z−1/2; (xviii) −x+1, y−1/2, −z+3/2. |
(II) Tricaesium trioxoantimonate(III)
top
Crystal data top
Cs3[SbO3] | Dx = 4.950 Mg m−3 |
Mr = 568.48 | Mo Kα radiation, λ = 0.71070 Å |
Cubic, P213 | Cell parameters from 25 reflections |
Hall symbol: P 2ac 2ab 3 | θ = 2.3–32.8° |
a = 9.1369 (10) Å | µ = 17.65 mm−1 |
V = 762.78 (14) Å3 | T = 293 K |
Z = 4 | Prism, colourless |
F(000) = 960 | 0.11 × 0.08 × 0.06 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 540 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.063 |
Graphite monochromator | θmax = 27.4°, θmin = 4.5° |
ω/2θ scans | h = −11→11 |
Absorption correction: ψ scan (North et al., 1968) | k = −11→11 |
Tmin = 0.197, Tmax = 0.347 | l = 0→11 |
3665 measured reflections | 3 standard reflections every 120 min |
586 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | w = 1/[σ2(Fo2) + 0.2365P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.014 | (Δ/σ)max = 0.001 |
wR(F2) = 0.036 | Δρmax = 0.68 e Å−3 |
S = 1.07 | Δρmin = −0.59 e Å−3 |
750 reflections | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
23 parameters | Extinction coefficient: 0.00079 (8) |
0 restraints | Absolute structure: Flack (1983), 240 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.06 (6) |
Crystal data top
Cs3[SbO3] | Z = 4 |
Mr = 568.48 | Mo Kα radiation |
Cubic, P213 | µ = 17.65 mm−1 |
a = 9.1369 (10) Å | T = 293 K |
V = 762.78 (14) Å3 | 0.11 × 0.08 × 0.06 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 540 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.063 |
Tmin = 0.197, Tmax = 0.347 | 3 standard reflections every 120 min |
3665 measured reflections | intensity decay: none |
586 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.014 | 0 restraints |
wR(F2) = 0.036 | Δρmax = 0.68 e Å−3 |
S = 1.07 | Δρmin = −0.59 e Å−3 |
750 reflections | Absolute structure: Flack (1983), 240 Friedel pairs |
23 parameters | Absolute structure parameter: 0.06 (6) |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cs1 | 0.77732 (3) | 0.77732 (3) | 0.77732 (3) | 0.02308 (10) | |
Cs2 | 0.27318 (3) | 0.27318 (3) | 0.27318 (3) | 0.02379 (11) | |
Cs3 | 0.01855 (3) | 0.01855 (3) | 0.01855 (3) | 0.02933 (10) | |
Sb1 | 0.50362 (2) | 0.50362 (2) | 0.50362 (2) | 0.01958 (8) | |
O1 | 0.0055 (3) | 0.2041 (3) | 0.4592 (3) | 0.0295 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cs1 | 0.02308 (10) | 0.02308 (10) | 0.02308 (10) | 0.00097 (10) | 0.00097 (10) | 0.00097 (10) |
Cs2 | 0.02379 (11) | 0.02379 (11) | 0.02379 (11) | −0.00051 (9) | −0.00051 (9) | −0.00051 (9) |
Cs3 | 0.02933 (10) | 0.02933 (10) | 0.02933 (10) | −0.00225 (10) | −0.00225 (10) | −0.00225 (10) |
Sb1 | 0.01958 (8) | 0.01958 (8) | 0.01958 (8) | −0.00125 (9) | −0.00125 (9) | −0.00125 (9) |
O1 | 0.0282 (13) | 0.0266 (11) | 0.0336 (12) | −0.0037 (10) | −0.0021 (12) | 0.0089 (11) |
Geometric parameters (Å, º) top
Cs1—O1i | 3.077 (2) | Cs3—O1xii | 2.888 (2) |
Cs1—O1ii | 3.077 (2) | Cs3—O1xiii | 2.888 (2) |
Cs1—O1iii | 3.077 (2) | Cs3—O1xiv | 2.888 (2) |
Cs1—O1iv | 3.191 (3) | Sb1—O1ix | 1.928 (2) |
Cs1—O1v | 3.191 (2) | Sb1—O1x | 1.928 (2) |
Cs1—O1vi | 3.191 (2) | Sb1—O1xi | 1.928 (2) |
Cs2—O1vii | 3.044 (3) | O1—Sb1xv | 1.928 (2) |
Cs2—O1viii | 3.044 (3) | O1—Cs3xvi | 2.888 (2) |
Cs2—O1 | 3.044 (3) | O1—Cs1xvii | 3.077 (2) |
Cs2—O1ix | 3.245 (3) | O1—Cs1xviii | 3.191 (2) |
Cs2—O1x | 3.245 (3) | O1—Cs2xv | 3.245 (3) |
Cs2—O1xi | 3.245 (3) | | |
| | | |
O1ix—Sb1—O1x | 100.43 (9) | | |
Symmetry codes: (i) z+1/2, −x+1/2, −y+1; (ii) −y+1, z+1/2, −x+1/2; (iii) −x+1/2, −y+1, z+1/2; (iv) −z+3/2, −x+1, y+1/2; (v) −x+1, y+1/2, −z+3/2; (vi) y+1/2, −z+3/2, −x+1; (vii) z, x, y; (viii) y, z, x; (ix) −z+1, x+1/2, −y+1/2; (x) x+1/2, −y+1/2, −z+1; (xi) −y+1/2, −z+1, x+1/2; (xii) −z+1/2, −x, y−1/2; (xiii) −x, y−1/2, −z+1/2; (xiv) y−1/2, −z+1/2, −x; (xv) x−1/2, −y+1/2, −z+1; (xvi) −x, y+1/2, −z+1/2; (xvii) −x+1/2, −y+1, z−1/2; (xviii) −x+1, y−1/2, −z+3/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | K3[SbO3] | Cs3[SbO3] |
Mr | 287.05 | 568.48 |
Crystal system, space group | Cubic, P213 | Cubic, P213 |
Temperature (K) | 293 | 293 |
a (Å) | 8.352 (5) | 9.1369 (10) |
V (Å3) | 582.7 (5) | 762.78 (14) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 6.77 | 17.65 |
Crystal size (mm) | 0.1 × 0.1 × 0.1 | 0.11 × 0.08 × 0.06 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.497, 0.508 | 0.197, 0.347 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1510, 455, 377 | 3665, 586, 540 |
Rint | 0.090 | 0.063 |
(sin θ/λ)max (Å−1) | 0.648 | 0.648 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.054, 1.04 | 0.014, 0.036, 1.07 |
No. of reflections | 455 | 750 |
No. of parameters | 20 | 23 |
Δρmax, Δρmin (e Å−3) | 0.72, −1.03 | 0.68, −0.59 |
Absolute structure | Flack (1983), 189 Friedel pairs | Flack (1983), 240 Friedel pairs |
Absolute structure parameter | −0.03 (11) | 0.06 (6) |
Selected geometric parameters (Å, º) for (I) topSb—O1i | 1.923 (4) | K2—O1iv | 2.734 (4) |
K1—O1ii | 2.758 (5) | K2—O1i | 2.961 (5) |
K1—O1iii | 2.922 (5) | K3—O1v | 2.659 (4) |
| | | |
O1i—Sb—O1vi | 99.50 (15) | | |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) z+1/2, −x+1/2, −y+1; (iii) −x+1, y+1/2, −z+3/2; (iv) z, x, y; (v) −x, y−1/2, −z+1/2; (vi) −z+1, x+1/2, −y+1/2. |
Selected geometric parameters (Å, º) for (II) topCs1—O1i | 3.077 (2) | Cs2—O1iii | 3.245 (3) |
Cs1—O1ii | 3.191 (3) | Cs3—O1iv | 2.888 (2) |
Cs2—O1 | 3.044 (3) | Sb1—O1iii | 1.928 (2) |
| | | |
O1iii—Sb1—O1v | 100.43 (9) | | |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) −z+3/2, −x+1, y+1/2; (iii) −z+1, x+1/2, −y+1/2; (iv) y−1/2, −z+1/2, −x; (v) x+1/2, −y+1/2, −z+1. |
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The oxoantimonates(III), ASbO2 [A = K, Rb (Hirschle & Röhr, 2000) or Cs (Hirschle & Röhr, 1998)], are isotypic with the corresponding bismuthates [A = K, Rb or Cs (Zoche & Jansen, 1998)] and contain, in accordance with the lone pair on SbIII/BiIII, the group V atoms coordinated by four O atoms in a Ψ-trigonal bipyramidal geometry. In the compounds A4[Sb2O5] [A = K, Rb or Cs (Hirschle & Röhr, 2000)], two [SbO3] Ψ tetrahedra are connected via an oxygen ligand to form [O2Sb—O-SbO2]4- `butterfly' anions. In contrast, K4[Bi2O5] (Zoche et al., 1998) contains [Bi4O10]8- anions, with Bi both in Ψ-trigonal bipyramidal and Ψ-tetrahedral coordination by oxygen. The bismuthates A3[BiO3], with Ψ-tetrahedral anions as characteristic building blocks, are known for the whole series of alkaline metals A. The isotypic sodium (Stöver & Hoppe, 1980) and potassium (Zoche & Jansen, 1997b) compounds can be described as defect NaCl variants, [A3Bi][O3], i.e. the cations A and Bi form a face-centred cubic sublattice (Cu3Al type). In the rubidium (Zoche & Jansen, 1997b) and caesium (Zoche & Jansen, 1997a) phases, the cations are arranged in a body-centered cubic sublattice (Fe3Al type). For the corresponding oxoantimonate series A3[SbO3], only the sodium compound has been described in the literature to date (Stöver & Hoppe, 1980): Na3[SbO3] is isotypic with the Na and K bismuthates mentioned above. We present here the structures of two further oxoantimonates, K3[SbO3], (I), and Cs3[SbO3], (II). \sch
The isotypic compounds (I) and (II) crystallize in the cubic spacegroup P213 with the Na3[AsS3] structure type (Palazzi, 1976), and are thus isotypic with the Rb and Cs oxobismuthates and most alkaline metal thio- and selenoarsenates, -antimonates and -bismuthates. Rb3[SbO3] forms the same structure type, with a lattice constant (refined from X-ray powder data) of 8.9523 (6) Å.
The crystal structures of (I) and (II) contain [SbO3]3- anions with crystallographic C3v point group symmetry and nearly equal Sb—O distances for the two compounds; the O—Sb—O bond angles are also very similar. The bond lengths are thus slightly longer than those observed in the sodium phase (Sb—O 1.890 Å).
The oxygen ligands are octahedrally coordinated by one Sb atom and five A cations (Fig. 1). The oxoantimonate ions form a face-centred cubic arrangement (Fig. 2), in which the alkaline metal cations occupy all tetrahedral and octahedral interstices. In an alternative description of the structure according to the concept of O'Keeffe & Hyde (1985), the A and Sb atoms form a 3:1 superstructure of a body-centred cubic lattice, the Fe3Al structure type. Whereas the corresponding K3Sb phase (Emmerling & Röhr, 2001) crystallizes with a superstructure of the hexagonal Cu3P type, the direct analogy of the metal atom arrangement in the intermetallic phase and the oxide is observed for Cs3Sb (Emmerling & Röhr, 2001) and (II). The unit cell volumes are also comparable [762.8 (1) Å3 in (II) and 763.7 (1) Å3 in Cs3Sb].