metal-organic compounds
The Ca and Zr atoms in the title compound, poly[octaaquatetra-μ-oxalato-calciumdipotassiumzirconate(IV)], [CaK2Zr(C2O4)4(H2O)8], are chelated by bridging oxalate groups to form a three-dimensional network; the two independent water-coordinated K atoms occupy the space within the network and also interact with the oxalate O atoms to result in eight-coordination for the K atoms. The title compound is isostructural with [CdK2Zr(C2O4)4(H2O)8] [Jeanneau, Audebrand & Louer (2002). J. Mater. Chem. 12, 2383–2389]. All the metal ions occupy special positions with site symmetry.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806034714/hb2129sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536806034714/hb2129Isup2.hkl |
CCDC reference: 624606
Computing details top
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97.
poly[octaaquatetra-µ-oxalato-calciumdipotassiumzirconium(IV)] top
Crystal data top
[CaK2Zr(C2O4)4(H2O)8] | Dx = 2.042 Mg m−3 |
Mr = 705.71 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I4 | Cell parameters from 1316 reflections |
Hall symbol: I -4 | θ = 2.5–24.6° |
a = 11.342 (1) Å | µ = 1.18 mm−1 |
c = 8.920 (1) Å | T = 293 K |
V = 1147.56 (16) Å3 | Block, colorless |
Z = 2 | 0.28 × 0.20 × 0.18 mm |
F(000) = 708 |
Data collection top
Bruker APEX CCD diffractometer | 1302 independent reflections |
Radiation source: fine-focus sealed tube | 1199 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ω scans | θmax = 27.4°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→13 |
Tmin = 0.681, Tmax = 0.816 | k = −14→14 |
6454 measured reflections | l = −11→11 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0434P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
1302 reflections | Δρmax = 0.72 e Å−3 |
83 parameters | Δρmin = −0.36 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 603 Fridel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.06 (8) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
Zr1 | 1.0000 | 1.0000 | 0.0000 | 0.01056 (17) | |
Ca1 | 0.5000 | 1.0000 | 0.2500 | 0.0136 (4) | |
K1 | 1.0000 | 1.0000 | 0.5000 | 0.0343 (4) | |
K2 | 0.5000 | 1.0000 | −0.2500 | 0.0262 (5) | |
O1 | 0.8908 (2) | 1.0048 (2) | 0.2084 (3) | 0.0221 (6) | |
O2 | 0.8145 (2) | 0.9963 (2) | −0.0618 (3) | 0.0234 (6) | |
O3 | 0.7077 (2) | 1.0040 (2) | 0.3035 (3) | 0.0255 (7) | |
O4 | 0.6264 (2) | 0.9891 (2) | 0.0179 (4) | 0.0264 (7) | |
O1w | 0.7946 (3) | 1.1433 (3) | 0.5421 (3) | 0.055 (1) | |
O2w | 0.6431 (3) | 1.2079 (3) | −0.2090 (4) | 0.056 (1) | |
C1 | 0.7799 (3) | 1.0019 (3) | 0.1995 (4) | 0.0173 (7) | |
C2 | 0.7334 (3) | 0.9952 (3) | 0.0376 (4) | 0.0196 (8) | |
H1w1 | 0.7353 | 1.1095 | 0.5028 | 0.050* | |
H1w2 | 0.7824 | 1.1529 | 0.6354 | 0.050* | |
H2w1 | 0.6474 | 1.2242 | −0.1162 | 0.050* | |
H2w2 | 0.6122 | 1.2654 | −0.2557 | 0.050* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
Zr1 | 0.0109 (2) | 0.0109 (2) | 0.0098 (3) | 0.000 | 0.000 | 0.000 |
Ca1 | 0.0120 (5) | 0.0120 (5) | 0.0167 (9) | 0.000 | 0.000 | 0.000 |
K1 | 0.0404 (6) | 0.0404 (6) | 0.0222 (7) | 0.000 | 0.000 | 0.000 |
K2 | 0.0303 (8) | 0.0303 (8) | 0.018 (1) | 0.000 | 0.000 | 0.000 |
O1 | 0.012 (1) | 0.035 (2) | 0.019 (1) | −0.001 (1) | 0.0002 (1) | −0.001 (1) |
O2 | 0.017 (1) | 0.039 (2) | 0.015 (1) | 0.001 (1) | −0.001 (1) | −0.001 (1) |
O3 | 0.014 (1) | 0.044 (2) | 0.018 (1) | −0.001 (1) | −0.001 (1) | −0.003 (1) |
O4 | 0.012 (1) | 0.045 (2) | 0.022 (2) | 0.000 (1) | −0.002 (1) | −0.001 (1) |
O1w | 0.040 (2) | 0.083 (3) | 0.042 (2) | −0.011 (2) | −0.006 (2) | −0.014 (2) |
O2w | 0.081 (3) | 0.043 (2) | 0.045 (2) | 0.009 (2) | −0.019 (2) | 0.005 (2) |
C1 | 0.016 (2) | 0.019 (2) | 0.017 (2) | −0.001 (1) | −0.001 (1) | 0.002 (2) |
C2 | 0.021 (2) | 0.019 (2) | 0.019 (2) | −0.001 (2) | −0.001 (1) | −0.003 (1) |
Geometric parameters (Å, º) top
Zr1—O1 | 2.234 (2) | K1—O1wi | 2.866 (3) |
Zr1—O1i | 2.234 (2) | K1—O1wvii | 2.866 (3) |
Zr1—O1ii | 2.234 (2) | K1—O1wviii | 2.866 (3) |
Zr1—O1iii | 2.234 (2) | K2—O4 | 2.789 (3) |
Zr1—O2 | 2.175 (3) | K2—O4iv | 2.789 (3) |
Zr1—O2i | 2.175 (3) | K2—O4ix | 2.789 (3) |
Zr1—O2ii | 2.175 (3) | K2—O4x | 2.789 (3) |
Zr1—O2iii | 2.175 (3) | K2—O2w | 2.886 (3) |
Ca1—O3 | 2.404 (2) | K2—O2wiv | 2.886 (3) |
Ca1—O3iv | 2.404 (2) | K2—O2wix | 2.886 (3) |
Ca1—O3v | 2.404 (2) | K2—O2wx | 2.886 (3) |
Ca1—O3vi | 2.404 (2) | C1—O1 | 1.260 (4) |
Ca1—O4 | 2.521 (3) | C1—O3 | 1.239 (4) |
Ca1—O4iv | 2.521 (3) | C2—O2 | 1.277 (4) |
Ca1—O4v | 2.521 (3) | C2—O4 | 1.228 (4) |
Ca1—O4vi | 2.521 (3) | C1—C2 | 1.539 (5) |
K1—O1 | 2.882 (2) | O1w—H1w1 | 0.85 |
K1—O1i | 2.882 (2) | O1w—H1w2 | 0.85 |
K1—O1vii | 2.882 (2) | O2w—H2w1 | 0.85 |
K1—O1viii | 2.882 (2) | O2w—H2w2 | 0.85 |
K1—O1w | 2.866 (3) | ||
O2—Zr1—O2ii | 93.7 (1) | O1wvii—K1—O1vii | 76.0 (1) |
O2—Zr1—O2i | 150.7 (1) | O1wviii—K1—O1vii | 118.6 (1) |
O2ii—Zr1—O2i | 93.7 (1) | O1wi—K1—O1vii | 96.3 (1) |
O2—Zr1—O2iii | 93.7 (1) | O1w—K1—O1vii | 69.7 (1) |
O2ii—Zr1—O2iii | 150.7 (1) | O1—K1—O1vii | 144.6 (1) |
O2i—Zr1—O2iii | 93.7 (1) | O1wvii—K1—O1i | 69.7 (1) |
O2—Zr1—O1ii | 79.8 (1) | O1wviii—K1—O1i | 96.3 (1) |
O2ii—Zr1—O1ii | 71.0 (1) | O1wi—K1—O1i | 76.0 (1) |
O2i—Zr1—O1ii | 75.8 (1) | O1w—K1—O1i | 118.6 (1) |
O2iii—Zr1—O1ii | 138.1 (1) | O1—K1—O1i | 51.0 (1) |
O2—Zr1—O1iii | 75.8 (1) | O1vii—K1—O1i | 144.6 (1) |
O2ii—Zr1—O1iii | 138.3 (1) | O1wvii—K1—O1viii | 118.6 (1) |
O2i—Zr1—O1iii | 79.8 (1) | O1wviii—K1—O1viii | 76.0 (1) |
O2iii—Zr1—O1iii | 71.0 (1) | O1wi—K1—O1viii | 69.7 (1) |
O1ii—Zr1—O1iii | 67.4 (1) | O1w—K1—O1viii | 96.3 (1) |
O2—Zr1—O1i | 138.3 (1) | O1—K1—O1viii | 144.6 (1) |
O2ii—Zr1—O1i | 79.8 (1) | O1vii—K1—O1viii | 51 (1) |
O2i—Zr1—O1i | 71.0 (1) | O1i—K1—O1viii | 144.6 (1) |
O2iii—Zr1—O1i | 75.8 (1) | O4ix—K2—O4 | 137.2 (1) |
O1ii—Zr1—O1i | 133.8 (1) | O4ix—K2—O4iv | 137.2 (1) |
O1iii—Zr1—O1i | 133.8 (1) | O4—K2—O4iv | 62.1 (1) |
O2—Zr1—O1 | 71.0 (1) | O4ix—K2—O4x | 62.1 (1) |
O2ii—Zr1—O1 | 75.8 (1) | O4—K2—O4x | 137.2 (1) |
O2i—Zr1—O1 | 138.3 (1) | O4iv—K2—O4x | 137.2 (1) |
O2iii—Zr1—O1 | 79.8 (1) | O4ix—K2—O2w | 123.6 (1) |
O1ii—Zr1—O1 | 133.8 (1) | O4—K2—O2w | 68.8 (1) |
O1iii—Zr1—O1 | 133.8 (1) | O4iv—K2—O2w | 98.3 (1) |
O1i—Zr1—O1 | 67.4 (1) | O4x—K2—O2w | 70.4 (1) |
O3vi—Ca1—O3 | 92.3 (1) | O4ix—K2—O2wiv | 70.4 (1) |
O3vi—Ca1—O3iv | 92.3 (1) | O4—K2—O2wiv | 98.3 (1) |
O3—Ca1—O3iv | 157.1 (1) | O4iv—K2—O2wiv | 68.8 (1) |
O3vi—Ca1—O3v | 157.1 (1) | O4x—K2—O2wiv | 123.6 (1) |
O3—Ca1—O3v | 92.3 (1) | O2w—K2—O2wiv | 165.42 (2) |
O3iv—Ca1—O3v | 92.3 (1) | O4ix—K2—O2wx | 98.3 (1) |
O3vi—Ca1—O4vi | 66.9 (1) | O4—K2—O2wx | 123.6 (1) |
O3—Ca1—O4vi | 77.2 (1) | O4iv—K2—O2wx | 70.4 (1) |
O3iv—Ca1—O4vi | 84.0 (1) | O4x—K2—O2wx | 68.8 (1) |
O3v—Ca1—O4vi | 136.0 (1) | O2w—K2—O2wx | 90.9 (1) |
O3vi—Ca1—O4iv | 77.2 (1) | O2wiv—K2—O2wx | 90.9 (1) |
O3—Ca1—O4iv | 136.0 (1) | O4ix—K2—O2wix | 68.8 (1) |
O3iv—Ca1—O4iv | 66.9 (1) | O4—K2—O2wix | 70.4 (1) |
O3v—Ca1—O4iv | 84.0 (1) | O4iv—K2—O2wix | 123.6 (1) |
O4vi—Ca1—O4iv | 132.4 (1) | O4x—K2—O2wix | 98.3 (1) |
O3vi—Ca1—O4 | 84.0 (1) | O2w—K2—O2wix | 90.9 (1) |
O3—Ca1—O4 | 66.9 (1) | O2wiv—K2—O2wix | 90.9 (1) |
O3iv—Ca1—O4 | 136.0 (1) | O2wx—K2—O2wix | 165.4 (2) |
O3v—Ca1—O4 | 77.2 (1) | C1—O1—Zr1 | 120.0 (2) |
O4vi—Ca1—O4 | 132.4 (1) | C1—O1—K1 | 119.0 (2) |
O4iv—Ca1—O4 | 69.6 (1) | Zr1—O1—K1 | 120.8 (1) |
O3vi—Ca1—O4v | 136.0 (1) | C2—O2—Zr1 | 121.4 (2) |
O3—Ca1—O4v | 84.0 (1) | C1—O3—Ca1 | 119.9 (2) |
O3iv—Ca1—O4v | 77.2 (1) | C2—O4—Ca1 | 116.2 (3) |
O3v—Ca1—O4v | 66.9 (1) | C2—O4—K2 | 128.9 (3) |
O4vi—Ca1—O4v | 69.6 (1) | Ca1—O4—K2 | 114.2 (1) |
O4iv—Ca1—O4v | 132.4 (1) | O3—C1—O1 | 127.8 (3) |
O4—Ca1—O4v | 132.4 (1) | O3—C1—C2 | 118.5 (3) |
O1wvii—K1—O1wviii | 164.9 (1) | O1—C1—C2 | 113.7 (3) |
O1wvii—K1—O1wi | 91.0 (1) | O4—C2—O2 | 127.8 (3) |
O1wviii—K1—O1wi | 91.0 (1) | O4—C2—C1 | 118.4 (3) |
O1wvii—K1—O1w | 91.0 (1) | O2—C2—C1 | 113.8 (3) |
O1wviii—K1—O1w | 91.0 (1) | K1—O1w—H1w1 | 109.5 |
O1wi—K1—O1w | 164.9 (1) | K1—O1w—H1w2 | 109.5 |
O1wvii—K1—O1 | 96.3 (1) | H1w1—O1w—H1w2 | 109.5 |
O1wviii—K1—O1 | 69.7 (1) | K2—O2w—H2w1 | 109.5 |
O1wi—K1—O1 | 118.6 (1) | K2—O2w—H2w2 | 109.5 |
O1w—K1—O1 | 76.0 (1) | H2w1—O2w—H2w2 | 109.5 |
O2—Zr1—O1—C1 | 0.9 (2) | O3iv—Ca1—O4—C2 | 179.5 (2) |
O2ii—Zr1—O1—C1 | 99.9 (3) | O3v—Ca1—O4—C2 | −100.7 (3) |
O2i—Zr1—O1—C1 | 179.3 (2) | O4vi—Ca1—O4—C2 | 41.6 (3) |
O2iii—Zr1—O1—C1 | −96.6 (3) | O4iv—Ca1—O4—C2 | 171.0 (3) |
O1ii—Zr1—O1—C1 | 54.9 (3) | O4v—Ca1—O4—C2 | −59.6 (3) |
O1iii—Zr1—O1—C1 | −45.6 (3) | O3vi—Ca1—O4—K2 | −78.5 (1) |
O1i—Zr1—O1—C1 | −175.4 (3) | O3—Ca1—O4—K2 | −173.6 (1) |
O2—Zr1—O1—K1 | 176.2 (1) | O3iv—Ca1—O4—K2 | 8.5 (2) |
O2ii—Zr1—O1—K1 | −84.7 (1) | O3v—Ca1—O4—K2 | 88.3 (1) |
O2i—Zr1—O1—K1 | −5.3 (2) | O4vi—Ca1—O4—K2 | −129.39 (2) |
O2iii—Zr1—O1—K1 | 78.7 (1) | O4v—Ca1—O4—K2 | 129.39 (2) |
O1ii—Zr1—O1—K1 | −129.76 (2) | O4ix—K2—O4—C2 | 59.8 (4) |
O1iii—Zr1—O1—K1 | 129.76 (2) | O4iv—K2—O4—C2 | −169.6 (3) |
O1wvii—K1—O1—C1 | −127.2 (2) | O4x—K2—O4—C2 | −39.0 (3) |
O1wviii—K1—O1—C1 | 58.6 (2) | O2w—K2—O4—C2 | −57.2 (3) |
O1wi—K1—O1—C1 | 138.2 (2) | O2wiv—K2—O4—C2 | 129.8 (3) |
O1w—K1—O1—C1 | −37.8 (2) | O2wx—K2—O4—C2 | −133.5 (3) |
O1vii—K1—O1—C1 | −52.5 (3) | O2wix—K2—O4—C2 | 41.8 (3) |
O1i—K1—O1—C1 | 175.4 (3) | Ca1xi—K2—O4—C2 | 10.4 (3) |
O1viii—K1—O1—C1 | 43.3 (3) | Ca1—K2—O4—C2 | −169.6 (3) |
O1wvii—K1—O1—Zr1 | 57.4 (1) | O4ix—K2—O4—Ca1 | −130.59 (2) |
O1wviii—K1—O1—Zr1 | −116.8 (1) | O4x—K2—O4—Ca1 | 130.59 (2) |
O1wi—K1—O1—Zr1 | −37.2 (2) | O2w—K2—O4—Ca1 | 112.4 (1) |
O1w—K1—O1—Zr1 | 146.8 (1) | O2wiv—K2—O4—Ca1 | −60.6 (1) |
O1vii—K1—O1—Zr1 | 132.07 (1) | O2wx—K2—O4—Ca1 | 36.1 (2) |
O1viii—K1—O1—Zr1 | −132.07 (1) | O2wix—K2—O4—Ca1 | −148.6 (1) |
O2ii—Zr1—O2—C2 | −75.5 (3) | Ca1—O3—C1—O1 | 179.1 (3) |
O2i—Zr1—O2—C2 | −179.7 (3) | Ca1—O3—C1—C2 | −0.7 (4) |
O2iii—Zr1—O2—C2 | 76.1 (3) | Zr1—O1—C1—O3 | −179.9 (3) |
O1ii—Zr1—O2—C2 | −145.5 (3) | K1—O1—C1—O3 | 4.6 (5) |
O1iii—Zr1—O2—C2 | 145.5 (3) | Zr1—O1—C1—C2 | 0.0 (4) |
O1i—Zr1—O2—C2 | 3.4 (4) | K1—O1—C1—C2 | −175.5 (2) |
O1—Zr1—O2—C2 | −1.8 (3) | Ca1—O4—C2—O2 | −177.1 (3) |
O3vi—Ca1—O3—C1 | −80.9 (3) | K2—O4—C2—O2 | −7.7 (5) |
O3iv—Ca1—O3—C1 | 177.9 (3) | Ca1—O4—C2—C1 | 3.2 (4) |
O3v—Ca1—O3—C1 | 76.6 (3) | K2—O4—C2—C1 | 172.6 (2) |
O4vi—Ca1—O3—C1 | −146.5 (3) | Zr1—O2—C2—O4 | −177.3 (3) |
O4iv—Ca1—O3—C1 | −7.1 (3) | Zr1—O2—C2—C1 | 2.4 (4) |
O4—Ca1—O3—C1 | 1.6 (3) | O3—C1—C2—O4 | −1.8 (5) |
O4v—Ca1—O3—C1 | 143.1 (3) | O1—C1—C2—O4 | 178.3 (3) |
O3vi—Ca1—O4—C2 | 92.5 (3) | O3—C1—C2—O2 | 178.4 (3) |
O3—Ca1—O4—C2 | −2.6 (2) | O1—C1—C2—O2 | −1.5 (5) |
Symmetry codes: (i) −x+2, −y+2, z; (ii) y, −x+2, −z; (iii) −y+2, x, −z; (iv) −x+1, −y+2, z; (v) y−1/2, −x+3/2, −z+1/2; (vi) −y+3/2, x+1/2, −z+1/2; (vii) y, −x+2, −z+1; (viii) −y+2, x, −z+1; (ix) y−1/2, −x+3/2, −z−1/2; (x) −y+3/2, x+1/2, −z−1/2; (xi) x, y, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1w—H1w1···O3 | 0.85 | 2.16 | 2.828 (4) | 135 |
O1w—H1w2···O2wxii | 0.85 | 2.19 | 2.901 (5) | 141 |
O2w—H2w1···O1wxiii | 0.85 | 2.16 | 2.893 (5) | 144 |
O2w—H2w2···O2x | 0.85 | 2.12 | 2.854 (4) | 145 |
Symmetry codes: (x) −y+3/2, x+1/2, −z−1/2; (xii) x, y, z+1; (xiii) −x+3/2, −y+5/2, z−1/2. |