Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520613029351/bp5058sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2052520613029351/bp50581sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2052520613029351/bp50582sup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2052520613029351/bp50583sup4.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2052520613029351/bp5058sup5.pdf |
CCDC references: 968425; 968426; 968427
Data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) for (2), (3). Cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) for (2), (3). Data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) for (2), (3). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
Ba2Ca0.07Cu3O6.85Y0.93 | Z = 1 |
Mr = 660.39 | F(000) = 291 |
Orthorhombic, Pmmm | Dx = 6.362 Mg m−3 |
a = 3.8114 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 3.8712 (3) Å | µ = 28.11 mm−1 |
c = 11.6824 (7) Å | T = 293 K |
V = 172.37 (2) Å3 | 0.18 × 0.07 × 0.01 mm |
Xcalibur, Ruby, Gemini ultra diffractometer | Rint = 0.044 |
Radiation source: fine-focus sealed tube | θmax = 26.3°, θmin = 7.0° |
Graphite monochromator | h = −4→4 |
1081 measured reflections | k = −4→4 |
234 independent reflections | l = −12→14 |
220 reflections with I > 2σ(I) |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.0609P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.083 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 1.94 e Å−3 |
234 reflections | Δρmin = −1.32 e Å−3 |
34 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.007 (2) |
Ba2Ca0.07Cu3O6.85Y0.93 | V = 172.37 (2) Å3 |
Mr = 660.39 | Z = 1 |
Orthorhombic, Pmmm | Mo Kα radiation |
a = 3.8114 (3) Å | µ = 28.11 mm−1 |
b = 3.8712 (3) Å | T = 293 K |
c = 11.6824 (7) Å | 0.18 × 0.07 × 0.01 mm |
Xcalibur, Ruby, Gemini ultra diffractometer | 220 reflections with I > 2σ(I) |
1081 measured reflections | Rint = 0.044 |
234 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | 34 parameters |
wR(F2) = 0.083 | 0 restraints |
S = 1.03 | Δρmax = 1.94 e Å−3 |
234 reflections | Δρmin = −1.32 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. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.0000 | 0.0000 | 0.0000 | 0.0133 (6) | |
Cu2 | 0.0000 | 0.0000 | 0.35530 (14) | 0.0100 (5) | |
Ba1 | 0.5000 | 0.5000 | 0.18455 (7) | 0.0137 (5) | |
Y1 | 0.5000 | 0.5000 | 0.5000 | 0.0113 (8) | 0.935 (9) |
Ca1 | 0.5000 | 0.5000 | 0.5000 | 0.0113 (8) | 0.07 |
O1 | 0.0000 | 0.0000 | 0.1578 (8) | 0.020 (2) | |
O2 | 0.5000 | 0.0000 | 0.3778 (8) | 0.0153 (17) | |
O3 | 0.0000 | 0.5000 | 0.3777 (8) | 0.0161 (18) | |
O4 | 0.0000 | 0.5000 | 0.0000 | 0.024 (6) | 0.85 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0208 (12) | 0.0145 (11) | 0.0045 (12) | 0.000 | 0.000 | 0.000 |
Cu2 | 0.0124 (9) | 0.0104 (9) | 0.0072 (9) | 0.000 | 0.000 | 0.000 |
Ba1 | 0.0186 (6) | 0.0148 (6) | 0.0078 (6) | 0.000 | 0.000 | 0.000 |
Y1 | 0.0153 (11) | 0.0119 (10) | 0.0067 (12) | 0.000 | 0.000 | 0.000 |
Ca1 | 0.0153 (11) | 0.0119 (10) | 0.0067 (12) | 0.000 | 0.000 | 0.000 |
O1 | 0.026 (5) | 0.023 (4) | 0.010 (5) | 0.000 | 0.000 | 0.000 |
O2 | 0.017 (4) | 0.023 (4) | 0.007 (4) | 0.000 | 0.000 | 0.000 |
O3 | 0.027 (4) | 0.015 (4) | 0.006 (4) | 0.000 | 0.000 | 0.000 |
O4 | 0.031 (9) | 0.007 (8) | 0.034 (12) | 0.000 | 0.000 | 0.000 |
Cu1—O1i | 1.843 (9) | Ba1—O2ix | 2.974 (7) |
Cu1—O1 | 1.843 (9) | Ba1—O2 | 2.974 (7) |
Cu1—O4ii | 1.9356 (2) | Ba1—Cu2viii | 3.3700 (9) |
Cu1—O4 | 1.9356 (2) | Ba1—Cu2ix | 3.3700 (9) |
Cu1—Ba1i | 3.4680 (5) | Y1—O3 | 2.382 (6) |
Cu1—Ba1 | 3.4680 (5) | Y1—O3xi | 2.382 (6) |
Cu1—Ba1iii | 3.4680 (5) | Y1—O3x | 2.382 (6) |
Cu1—Ba1iv | 3.4680 (5) | Y1—O3xii | 2.382 (6) |
Cu1—Ba1v | 3.4680 (5) | Y1—O2 | 2.405 (5) |
Cu1—Ba1vi | 3.4680 (5) | Y1—O2xi | 2.405 (5) |
Cu1—Ba1ii | 3.4680 (5) | Y1—O2xiii | 2.405 (5) |
Cu1—Ba1vii | 3.4680 (5) | Y1—O2ix | 2.405 (5) |
Cu2—O2 | 1.9237 (13) | Y1—Cu2xi | 3.1994 (9) |
Cu2—O2vi | 1.9237 (13) | Y1—Cu2viii | 3.1994 (9) |
Cu2—O3 | 1.9533 (13) | Y1—Cu2xiv | 3.1994 (9) |
Cu2—O3ii | 1.9533 (13) | O1—Ba1vii | 2.7342 (10) |
Cu2—O1 | 2.307 (9) | O1—Ba1vi | 2.7342 (10) |
Cu2—Y1 | 3.1994 (9) | O1—Ba1ii | 2.7342 (10) |
Cu2—Ca1vii | 3.1994 (9) | O2—Cu2x | 1.9237 (13) |
Cu2—Y1vii | 3.1994 (9) | O2—Ca1ii | 2.405 (5) |
Cu2—Ca1vi | 3.1994 (9) | O2—Y1ii | 2.405 (5) |
Cu2—Ca1ii | 3.1994 (9) | O2—Ba1ii | 2.974 (7) |
Cu2—Y1ii | 3.1994 (9) | O3—Cu2ix | 1.9533 (13) |
Ba1—O1 | 2.7342 (10) | O3—Ca1vi | 2.382 (6) |
Ba1—O1viii | 2.7342 (10) | O3—Y1vi | 2.382 (6) |
Ba1—O1ix | 2.7342 (10) | O3—Ba1vi | 2.954 (7) |
Ba1—O1x | 2.7342 (10) | O4—Cu1ix | 1.9356 (2) |
Ba1—O4 | 2.8775 (6) | O4—Ba1iii | 2.8775 (6) |
Ba1—O4x | 2.8775 (6) | O4—Ba1v | 2.8775 (6) |
Ba1—O3x | 2.954 (7) | O4—Ba1vi | 2.8775 (6) |
Ba1—O3 | 2.954 (7) | ||
O1i—Cu1—O1 | 180.0 | O3x—Ba1—O2 | 54.55 (11) |
O1i—Cu1—O4ii | 90.0 | O3—Ba1—O2 | 54.55 (11) |
O1—Cu1—O4ii | 90.0 | O2ix—Ba1—O2 | 81.2 (2) |
O1i—Cu1—O4 | 90.0 | O1—Ba1—Cu2viii | 150.27 (19) |
O1—Cu1—O4 | 90.0 | O1viii—Ba1—Cu2viii | 42.86 (19) |
O4ii—Cu1—O4 | 180.0 | O1ix—Ba1—Cu2viii | 93.16 (11) |
O1i—Cu1—Ba1i | 51.560 (11) | O1x—Ba1—Cu2viii | 94.60 (11) |
O1—Cu1—Ba1i | 128.440 (11) | O4—Ba1—Cu2viii | 144.884 (12) |
O4ii—Cu1—Ba1i | 56.073 (6) | O4x—Ba1—Cu2viii | 93.96 (2) |
O4—Cu1—Ba1i | 123.927 (6) | O3x—Ba1—Cu2viii | 35.208 (17) |
O1i—Cu1—Ba1 | 128.440 (11) | O3—Ba1—Cu2viii | 84.99 (10) |
O1—Cu1—Ba1 | 51.560 (11) | O2ix—Ba1—Cu2viii | 34.594 (16) |
O4ii—Cu1—Ba1 | 123.927 (6) | O2—Ba1—Cu2viii | 85.67 (10) |
O4—Cu1—Ba1 | 56.073 (6) | O1—Ba1—Cu2ix | 94.60 (11) |
Ba1i—Cu1—Ba1 | 180.00 (2) | O1viii—Ba1—Cu2ix | 93.16 (11) |
O1i—Cu1—Ba1iii | 51.560 (11) | O1ix—Ba1—Cu2ix | 42.86 (19) |
O1—Cu1—Ba1iii | 128.440 (11) | O1x—Ba1—Cu2ix | 150.27 (19) |
O4ii—Cu1—Ba1iii | 123.927 (6) | O4—Ba1—Cu2ix | 93.96 (2) |
O4—Cu1—Ba1iii | 56.073 (6) | O4x—Ba1—Cu2ix | 144.884 (12) |
Ba1i—Cu1—Ba1iii | 67.854 (12) | O3x—Ba1—Cu2ix | 84.99 (10) |
Ba1—Cu1—Ba1iii | 112.146 (12) | O3—Ba1—Cu2ix | 35.208 (17) |
O1i—Cu1—Ba1iv | 51.560 (11) | O2ix—Ba1—Cu2ix | 34.594 (17) |
O1—Cu1—Ba1iv | 128.440 (11) | O2—Ba1—Cu2ix | 85.67 (10) |
O4ii—Cu1—Ba1iv | 56.073 (6) | Cu2viii—Ba1—Cu2ix | 68.87 (2) |
O4—Cu1—Ba1iv | 123.927 (6) | O3—Y1—O3xi | 180.0000 (10) |
Ba1i—Cu1—Ba1iv | 66.668 (12) | O3—Y1—O3x | 106.3 (4) |
Ba1—Cu1—Ba1iv | 113.332 (12) | O3xi—Y1—O3x | 73.7 (4) |
Ba1iii—Cu1—Ba1iv | 103.12 (2) | O3—Y1—O3xii | 73.7 (4) |
O1i—Cu1—Ba1v | 51.560 (11) | O3xi—Y1—O3xii | 106.3 (4) |
O1—Cu1—Ba1v | 128.440 (11) | O3x—Y1—O3xii | 180.0 |
O4ii—Cu1—Ba1v | 123.927 (6) | O3—Y1—O2 | 69.14 (14) |
O4—Cu1—Ba1v | 56.073 (6) | O3xi—Y1—O2 | 110.86 (14) |
Ba1i—Cu1—Ba1v | 103.12 (2) | O3x—Y1—O2 | 69.14 (14) |
Ba1—Cu1—Ba1v | 76.88 (2) | O3xii—Y1—O2 | 110.86 (14) |
Ba1iii—Cu1—Ba1v | 66.668 (12) | O3—Y1—O2xi | 110.86 (14) |
Ba1iv—Cu1—Ba1v | 67.854 (12) | O3xi—Y1—O2xi | 69.14 (14) |
O1i—Cu1—Ba1vi | 128.440 (11) | O3x—Y1—O2xi | 110.86 (14) |
O1—Cu1—Ba1vi | 51.560 (11) | O3xii—Y1—O2xi | 69.14 (14) |
O4ii—Cu1—Ba1vi | 123.927 (6) | O2—Y1—O2xi | 180.0000 (10) |
O4—Cu1—Ba1vi | 56.073 (6) | O3—Y1—O2xiii | 110.86 (14) |
Ba1i—Cu1—Ba1vi | 113.332 (12) | O3xi—Y1—O2xiii | 69.14 (14) |
Ba1—Cu1—Ba1vi | 66.668 (12) | O3x—Y1—O2xiii | 110.86 (14) |
Ba1iii—Cu1—Ba1vi | 76.88 (2) | O3xii—Y1—O2xiii | 69.14 (14) |
Ba1iv—Cu1—Ba1vi | 180.0 | O2—Y1—O2xiii | 72.8 (4) |
Ba1v—Cu1—Ba1vi | 112.146 (12) | O2xi—Y1—O2xiii | 107.2 (4) |
O1i—Cu1—Ba1ii | 128.440 (11) | O3—Y1—O2ix | 69.14 (14) |
O1—Cu1—Ba1ii | 51.560 (11) | O3xi—Y1—O2ix | 110.86 (14) |
O4ii—Cu1—Ba1ii | 56.073 (6) | O3x—Y1—O2ix | 69.14 (14) |
O4—Cu1—Ba1ii | 123.927 (6) | O3xii—Y1—O2ix | 110.86 (14) |
Ba1i—Cu1—Ba1ii | 112.146 (12) | O2—Y1—O2ix | 107.2 (4) |
Ba1—Cu1—Ba1ii | 67.854 (12) | O2xi—Y1—O2ix | 72.8 (4) |
Ba1iii—Cu1—Ba1ii | 180.0 | O2xiii—Y1—O2ix | 180.0 |
Ba1iv—Cu1—Ba1ii | 76.88 (2) | O3—Y1—Cu2 | 37.48 (2) |
Ba1v—Cu1—Ba1ii | 113.332 (12) | O3xi—Y1—Cu2 | 142.52 (2) |
Ba1vi—Cu1—Ba1ii | 103.12 (2) | O3x—Y1—Cu2 | 99.19 (14) |
O1i—Cu1—Ba1vii | 128.440 (11) | O3xii—Y1—Cu2 | 80.81 (14) |
O1—Cu1—Ba1vii | 51.560 (11) | O2—Y1—Cu2 | 36.82 (2) |
O4ii—Cu1—Ba1vii | 56.073 (6) | O2xi—Y1—Cu2 | 143.18 (2) |
O4—Cu1—Ba1vii | 123.927 (6) | O2xiii—Y1—Cu2 | 80.03 (14) |
Ba1i—Cu1—Ba1vii | 76.88 (2) | O2ix—Y1—Cu2 | 99.97 (14) |
Ba1—Cu1—Ba1vii | 103.12 (2) | O3—Y1—Cu2xi | 142.52 (2) |
Ba1iii—Cu1—Ba1vii | 113.332 (12) | O3xi—Y1—Cu2xi | 37.48 (2) |
Ba1iv—Cu1—Ba1vii | 112.146 (12) | O3x—Y1—Cu2xi | 80.81 (14) |
Ba1v—Cu1—Ba1vii | 180.0 | O3xii—Y1—Cu2xi | 99.19 (14) |
Ba1vi—Cu1—Ba1vii | 67.854 (12) | O2—Y1—Cu2xi | 143.18 (2) |
Ba1ii—Cu1—Ba1vii | 66.668 (12) | O2xi—Y1—Cu2xi | 36.82 (2) |
O2—Cu2—O2vi | 164.3 (5) | O2xiii—Y1—Cu2xi | 99.97 (14) |
O2—Cu2—O3 | 88.95 (6) | O2ix—Y1—Cu2xi | 80.03 (14) |
O2vi—Cu2—O3 | 88.95 (6) | Cu2—Y1—Cu2xi | 180.0 |
O2—Cu2—O3ii | 88.95 (6) | O3—Y1—Cu2viii | 99.19 (14) |
O2vi—Cu2—O3ii | 88.95 (6) | O3xi—Y1—Cu2viii | 80.81 (15) |
O3—Cu2—O3ii | 164.6 (6) | O3x—Y1—Cu2viii | 37.48 (2) |
O2—Cu2—O1 | 97.8 (3) | O3xii—Y1—Cu2viii | 142.52 (2) |
O2vi—Cu2—O1 | 97.8 (3) | O2—Y1—Cu2viii | 99.97 (14) |
O3—Cu2—O1 | 97.7 (3) | O2xi—Y1—Cu2viii | 80.03 (14) |
O3ii—Cu2—O1 | 97.7 (3) | O2xiii—Y1—Cu2viii | 143.18 (2) |
O2—Cu2—Y1 | 48.53 (16) | O2ix—Y1—Cu2viii | 36.82 (2) |
O2vi—Cu2—Y1 | 121.2 (2) | Cu2—Y1—Cu2viii | 116.21 (5) |
O3—Cu2—Y1 | 47.90 (16) | Cu2xi—Y1—Cu2viii | 63.79 (5) |
O3ii—Cu2—Y1 | 121.9 (2) | O3—Y1—Cu2xiv | 80.81 (14) |
O1—Cu2—Y1 | 121.90 (3) | O3xi—Y1—Cu2xiv | 99.19 (15) |
O2—Cu2—Ca1vii | 121.2 (2) | O3x—Y1—Cu2xiv | 142.52 (2) |
O2vi—Cu2—Ca1vii | 48.53 (16) | O3xii—Y1—Cu2xiv | 37.48 (2) |
O3—Cu2—Ca1vii | 121.9 (2) | O2—Y1—Cu2xiv | 80.03 (14) |
O3ii—Cu2—Ca1vii | 47.90 (17) | O2xi—Y1—Cu2xiv | 99.97 (14) |
O1—Cu2—Ca1vii | 121.90 (3) | O2xiii—Y1—Cu2xiv | 36.82 (2) |
Y1—Cu2—Ca1vii | 116.21 (5) | O2ix—Y1—Cu2xiv | 143.18 (2) |
O2—Cu2—Y1vii | 121.2 (2) | Cu2—Y1—Cu2xiv | 63.79 (5) |
O2vi—Cu2—Y1vii | 48.53 (16) | Cu2xi—Y1—Cu2xiv | 116.21 (5) |
O3—Cu2—Y1vii | 121.9 (2) | Cu2viii—Y1—Cu2xiv | 180.0 |
O3ii—Cu2—Y1vii | 47.90 (17) | Cu1—O1—Cu2 | 180.0 |
O1—Cu2—Y1vii | 121.90 (3) | Cu1—O1—Ba1 | 96.56 (18) |
Y1—Cu2—Y1vii | 116.21 (5) | Cu2—O1—Ba1 | 83.44 (18) |
Ca1vii—Cu2—Y1vii | 0.0 | Cu1—O1—Ba1vii | 96.56 (18) |
O2—Cu2—Ca1vi | 121.2 (2) | Cu2—O1—Ba1vii | 83.44 (18) |
O2vi—Cu2—Ca1vi | 48.53 (16) | Ba1—O1—Ba1vii | 166.9 (4) |
O3—Cu2—Ca1vi | 47.90 (17) | Cu1—O1—Ba1vi | 96.56 (18) |
O3ii—Cu2—Ca1vi | 121.9 (2) | Cu2—O1—Ba1vi | 83.44 (18) |
O1—Cu2—Ca1vi | 121.90 (3) | Ba1—O1—Ba1vi | 88.37 (4) |
Y1—Cu2—Ca1vi | 73.12 (2) | Ba1vii—O1—Ba1vi | 90.13 (4) |
Ca1vii—Cu2—Ca1vi | 74.46 (2) | Cu1—O1—Ba1ii | 96.56 (18) |
Y1vii—Cu2—Ca1vi | 74.46 (2) | Cu2—O1—Ba1ii | 83.44 (18) |
O2—Cu2—Ca1ii | 48.53 (16) | Ba1—O1—Ba1ii | 90.13 (4) |
O2vi—Cu2—Ca1ii | 121.2 (2) | Ba1vii—O1—Ba1ii | 88.37 (4) |
O3—Cu2—Ca1ii | 121.9 (2) | Ba1vi—O1—Ba1ii | 166.9 (4) |
O3ii—Cu2—Ca1ii | 47.90 (17) | Cu2—O2—Cu2x | 164.3 (5) |
O1—Cu2—Ca1ii | 121.90 (3) | Cu2—O2—Y1 | 94.65 (14) |
Y1—Cu2—Ca1ii | 74.46 (2) | Cu2x—O2—Y1 | 94.65 (14) |
Ca1vii—Cu2—Ca1ii | 73.12 (2) | Cu2—O2—Ca1ii | 94.65 (14) |
Y1vii—Cu2—Ca1ii | 73.12 (2) | Cu2x—O2—Ca1ii | 94.65 (14) |
Ca1vi—Cu2—Ca1ii | 116.21 (5) | Y1—O2—Ca1ii | 107.2 (4) |
O2—Cu2—Y1ii | 48.53 (16) | Cu2—O2—Y1ii | 94.65 (14) |
O2vi—Cu2—Y1ii | 121.2 (2) | Cu2x—O2—Y1ii | 94.65 (14) |
O3—Cu2—Y1ii | 121.9 (2) | Y1—O2—Y1ii | 107.2 (4) |
O3ii—Cu2—Y1ii | 47.90 (17) | Ca1ii—O2—Y1ii | 0.0 |
O1—Cu2—Y1ii | 121.90 (3) | Cu2—O2—Ba1ii | 84.1 (2) |
Y1—Cu2—Y1ii | 74.46 (2) | Cu2x—O2—Ba1ii | 84.1 (2) |
Ca1vii—Cu2—Y1ii | 73.12 (2) | Y1—O2—Ba1ii | 167.0 (3) |
Y1vii—Cu2—Y1ii | 73.12 (2) | Ca1ii—O2—Ba1ii | 85.80 (6) |
Ca1vi—Cu2—Y1ii | 116.21 (5) | Y1ii—O2—Ba1ii | 85.80 (6) |
Ca1ii—Cu2—Y1ii | 0.0 | Cu2—O2—Ba1 | 84.1 (2) |
O1—Ba1—O1viii | 166.9 (4) | Cu2x—O2—Ba1 | 84.1 (2) |
O1—Ba1—O1ix | 90.13 (4) | Y1—O2—Ba1 | 85.80 (6) |
O1viii—Ba1—O1ix | 88.37 (4) | Ca1ii—O2—Ba1 | 167.0 (3) |
O1—Ba1—O1x | 88.37 (4) | Y1ii—O2—Ba1 | 167.0 (3) |
O1viii—Ba1—O1x | 90.13 (4) | Ba1ii—O2—Ba1 | 81.2 (2) |
O1ix—Ba1—O1x | 166.9 (4) | Cu2—O3—Cu2ix | 164.6 (6) |
O1—Ba1—O4 | 56.82 (15) | Cu2—O3—Y1 | 94.62 (15) |
O1viii—Ba1—O4 | 112.08 (16) | Cu2ix—O3—Y1 | 94.62 (15) |
O1ix—Ba1—O4 | 56.82 (15) | Cu2—O3—Ca1vi | 94.62 (15) |
O1x—Ba1—O4 | 112.08 (16) | Cu2ix—O3—Ca1vi | 94.62 (15) |
O1—Ba1—O4x | 112.08 (16) | Y1—O3—Ca1vi | 106.3 (4) |
O1viii—Ba1—O4x | 56.82 (15) | Cu2—O3—Y1vi | 94.62 (15) |
O1ix—Ba1—O4x | 112.08 (16) | Cu2ix—O3—Y1vi | 94.62 (15) |
O1x—Ba1—O4x | 56.82 (15) | Y1—O3—Y1vi | 106.3 (4) |
O4—Ba1—O4x | 82.95 (2) | Ca1vi—O3—Y1vi | 0.0 |
O1—Ba1—O3x | 122.48 (17) | Cu2—O3—Ba1vi | 84.1 (2) |
O1viii—Ba1—O3x | 68.76 (18) | Cu2ix—O3—Ba1vi | 84.1 (2) |
O1ix—Ba1—O3x | 122.48 (17) | Y1—O3—Ba1vi | 167.0 (3) |
O1x—Ba1—O3x | 68.76 (18) | Ca1vi—O3—Ba1vi | 86.67 (7) |
O4—Ba1—O3x | 178.71 (12) | Y1vi—O3—Ba1vi | 86.67 (7) |
O4x—Ba1—O3x | 98.35 (12) | Cu2—O3—Ba1 | 84.1 (2) |
O1—Ba1—O3 | 68.76 (18) | Cu2ix—O3—Ba1 | 84.1 (2) |
O1viii—Ba1—O3 | 122.48 (17) | Y1—O3—Ba1 | 86.67 (7) |
O1ix—Ba1—O3 | 68.76 (18) | Ca1vi—O3—Ba1 | 167.0 (3) |
O1x—Ba1—O3 | 122.48 (17) | Y1vi—O3—Ba1 | 167.0 (3) |
O4—Ba1—O3 | 98.35 (12) | Ba1vi—O3—Ba1 | 80.4 (2) |
O4x—Ba1—O3 | 178.71 (12) | Cu1ix—O4—Cu1 | 180.0 |
O3x—Ba1—O3 | 80.4 (2) | Cu1ix—O4—Ba1iii | 90.0 |
O1—Ba1—O2ix | 123.20 (17) | Cu1—O4—Ba1iii | 90.0 |
O1viii—Ba1—O2ix | 68.04 (17) | Cu1ix—O4—Ba1 | 90.0 |
O1ix—Ba1—O2ix | 68.04 (17) | Cu1—O4—Ba1 | 90.0 |
O1x—Ba1—O2ix | 123.20 (17) | Ba1iii—O4—Ba1 | 180.00 (2) |
O4—Ba1—O2ix | 124.67 (7) | Cu1ix—O4—Ba1v | 90.0 |
O4x—Ba1—O2ix | 124.67 (7) | Cu1—O4—Ba1v | 90.0 |
O3x—Ba1—O2ix | 54.55 (11) | Ba1iii—O4—Ba1v | 82.95 (2) |
O3—Ba1—O2ix | 54.55 (11) | Ba1—O4—Ba1v | 97.05 (2) |
O1—Ba1—O2 | 68.04 (17) | Cu1ix—O4—Ba1vi | 90.0 |
O1viii—Ba1—O2 | 123.20 (17) | Cu1—O4—Ba1vi | 90.0 |
O1ix—Ba1—O2 | 123.20 (17) | Ba1iii—O4—Ba1vi | 97.05 (2) |
O1x—Ba1—O2 | 68.04 (17) | Ba1—O4—Ba1vi | 82.95 (2) |
O4—Ba1—O2 | 124.67 (7) | Ba1v—O4—Ba1vi | 180.0 |
O4x—Ba1—O2 | 124.67 (7) |
Symmetry codes: (i) −x, −y, −z; (ii) x, y−1, z; (iii) −x, −y+1, −z; (iv) −x+1, −y, −z; (v) −x+1, −y+1, −z; (vi) x−1, y, z; (vii) x−1, y−1, z; (viii) x+1, y+1, z; (ix) x, y+1, z; (x) x+1, y, z; (xi) −x+1, −y+1, −z+1; (xii) −x, −y+1, −z+1; (xiii) −x+1, −y, −z+1; (xiv) −x, −y, −z+1. |
Al0.06Cu2.94O6Y0.94·0.81(O)·2(Ba)·0.06(Ca) | F(000) = 290 |
Mr = 657.80 | Dx = 6.285 Mg m−3 |
Orthorhombic, Pmmm | Mo Kα radiation, λ = 0.71073 Å |
a = 3.8380 (2) Å | Cell parameters from 1360 reflections |
b = 3.8735 (2) Å | θ = 6.3–30.4° |
c = 11.6947 (5) Å | µ = 27.77 mm−1 |
V = 173.86 (2) Å3 | T = 293 K |
Z = 1 | 0.21 × 0.04 × 0.02 mm |
Xcalibur, Ruby, Gemini ultra diffractometer | 353 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 337 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 10.2890 pixels mm-1 | θmax = 30.5°, θmin = 6.3° |
Absorption correction: analytical ? | h = −4→5 |
Tmin = 0.326, Tmax = 0.639 | k = −5→5 |
1677 measured reflections | l = −16→16 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.018 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.051 | w = 1/[σ2(Fo2) + (0.0361P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
353 reflections | Δρmax = 0.90 e Å−3 |
34 parameters | Δρmin = −0.86 e Å−3 |
Al0.06Cu2.94O6Y0.94·0.81(O)·2(Ba)·0.06(Ca) | V = 173.86 (2) Å3 |
Mr = 657.80 | Z = 1 |
Orthorhombic, Pmmm | Mo Kα radiation |
a = 3.8380 (2) Å | µ = 27.77 mm−1 |
b = 3.8735 (2) Å | T = 293 K |
c = 11.6947 (5) Å | 0.21 × 0.04 × 0.02 mm |
Xcalibur, Ruby, Gemini ultra diffractometer | 353 independent reflections |
Absorption correction: analytical ? | 337 reflections with I > 2σ(I) |
Tmin = 0.326, Tmax = 0.639 | Rint = 0.026 |
1677 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 34 parameters |
wR(F2) = 0.051 | 0 restraints |
S = 1.08 | Δρmax = 0.90 e Å−3 |
353 reflections | Δρmin = −0.86 e Å−3 |
Experimental. CrysAlis PRO, Agilent Technologies, Version 1.171.35.21 (release 20–01-2012 CrysAlis171. NET) (compiled Jan 23 2012,18:06:46) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R·C. Clark & J·S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897) |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.0000 | 0.0000 | 0.0000 | 0.0113 (3) | 0.943 (5) |
Cu2 | 0.0000 | 0.0000 | 0.35628 (6) | 0.00776 (17) | |
Y1 | −0.5000 | 0.5000 | 0.5000 | 0.0081 (2) | 0.935 (4) |
Ba1 | 0.5000 | −0.5000 | 0.18585 (3) | 0.01198 (14) | |
Ca1 | −0.5000 | 0.5000 | 0.5000 | 0.0081 (2) | 0.06 |
Al1 | 0.0000 | 0.0000 | 0.35628 (6) | 0.00776 (17) | 0.03 |
O1 | 0.0000 | 0.0000 | 0.1584 (4) | 0.0212 (8) | |
O2 | −0.5000 | 0.0000 | 0.3777 (4) | 0.0098 (6) | |
O3 | 0.0000 | 0.5000 | 0.3775 (4) | 0.0106 (7) | |
O4 | 0.0000 | 0.5000 | 0.0000 | 0.017 (3) | 0.65 (2) |
O5 | 0.5000 | 0.0000 | 0.0000 | 0.012 (6)* | 0.16 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0136 (5) | 0.0126 (5) | 0.0079 (5) | 0.000 | 0.000 | 0.000 |
Cu2 | 0.0059 (3) | 0.0062 (3) | 0.0112 (4) | 0.000 | 0.000 | 0.000 |
Y1 | 0.0074 (3) | 0.0072 (3) | 0.0097 (4) | 0.000 | 0.000 | 0.000 |
Ba1 | 0.01263 (19) | 0.01116 (19) | 0.0122 (2) | 0.000 | 0.000 | 0.000 |
Ca1 | 0.0074 (3) | 0.0072 (3) | 0.0097 (4) | 0.000 | 0.000 | 0.000 |
Al1 | 0.0059 (3) | 0.0062 (3) | 0.0112 (4) | 0.000 | 0.000 | 0.000 |
O1 | 0.027 (2) | 0.0262 (19) | 0.011 (2) | 0.000 | 0.000 | 0.000 |
O2 | 0.0065 (12) | 0.0117 (13) | 0.0113 (17) | 0.000 | 0.000 | 0.000 |
O3 | 0.0117 (13) | 0.0061 (13) | 0.0141 (19) | 0.000 | 0.000 | 0.000 |
O4 | 0.027 (4) | 0.007 (4) | 0.018 (5) | 0.000 | 0.000 | 0.000 |
Cu1—O1 | 1.852 (5) | Ba1—O1viii | 2.7453 (5) |
Cu1—O1i | 1.852 (5) | Ba1—O1ix | 2.7453 (5) |
Cu1—O5ii | 1.9190 | Ba1—O1 | 2.7453 (5) |
Cu1—O5 | 1.9190 | Ba1—O4iii | 2.8994 (3) |
Cu1—O4 | 1.9367 | Ba1—O4ix | 2.8994 (3) |
Cu1—O4iii | 1.9367 | Ba1—O5iii | 2.9112 (3) |
Cu1—Ba1iv | 3.4868 (2) | Ba1—O5 | 2.9112 (3) |
Cu1—Ba1v | 3.4868 (2) | Ba1—O3ix | 2.950 (3) |
Cu1—Ba1i | 3.4868 (2) | Ba1—O3iii | 2.950 (3) |
Cu1—Ba1vi | 3.4868 (2) | Ba1—O2viii | 2.964 (3) |
Cu1—Ba1vii | 3.4868 (2) | Ba1—O2ix | 2.964 (3) |
Cu1—Ba1 | 3.4868 (2) | O1—Ba1v | 2.7453 (5) |
Cu2—O2viii | 1.9352 (6) | O1—Ba1ii | 2.7453 (5) |
Cu2—O2 | 1.9352 (5) | O1—Ba1xiii | 2.7453 (5) |
Cu2—O3 | 1.9525 (6) | O2—Al1ii | 1.9352 (5) |
Cu2—O3iii | 1.9525 (6) | O2—Cu2ii | 1.9352 (5) |
Cu2—O1 | 2.314 (5) | O2—Y1iii | 2.408 (2) |
Cu2—Ca1viii | 3.2029 (4) | O2—Ca1iii | 2.408 (2) |
Cu2—Y1viii | 3.2029 (4) | O2—Ba1ii | 2.964 (3) |
Cu2—Ca1iii | 3.2029 (4) | O2—Ba1xiii | 2.964 (3) |
Cu2—Y1iii | 3.2029 (4) | O3—Al1v | 1.9525 (6) |
Cu2—Y1 | 3.2029 (4) | O3—Cu2v | 1.9525 (6) |
Cu2—Ca1ix | 3.2029 (4) | O3—Ca1viii | 2.395 (3) |
Y1—O3ii | 2.395 (3) | O3—Y1viii | 2.395 (3) |
Y1—O3x | 2.395 (3) | O3—Ba1xiii | 2.950 (3) |
Y1—O3 | 2.395 (3) | O3—Ba1v | 2.950 (3) |
Y1—O3xi | 2.395 (3) | O4—Cu1v | 1.9367 |
Y1—O2 | 2.408 (2) | O4—Ba1i | 2.8994 (3) |
Y1—O2xi | 2.408 (2) | O4—Ba1v | 2.8994 (3) |
Y1—O2v | 2.408 (2) | O4—Ba1vii | 2.8994 (3) |
Y1—O2xii | 2.408 (2) | O4—Ba1xiii | 2.8994 (3) |
Y1—Cu2ii | 3.2029 (4) | O5—Cu1viii | 1.9190 |
Y1—Al1x | 3.2029 (4) | O5—Ba1vi | 2.9112 (3) |
Y1—Al1ii | 3.2029 (4) | O5—Ba1v | 2.9112 (3) |
Y1—Cu2x | 3.2029 (4) | O5—Ba1vii | 2.9112 (3) |
Ba1—O1iii | 2.7453 (5) | ||
O1—Cu1—O1i | 180.0 | O3x—Y1—Cu2x | 37.434 (9) |
O1—Cu1—O5ii | 90.0 | O3—Y1—Cu2x | 80.44 (7) |
O1i—Cu1—O5ii | 90.0 | O3xi—Y1—Cu2x | 99.56 (7) |
O1—Cu1—O5 | 90.0 | O2—Y1—Cu2x | 142.956 (9) |
O1i—Cu1—O5 | 90.0 | O2xi—Y1—Cu2x | 37.044 (9) |
O5ii—Cu1—O5 | 180.0 | O2v—Y1—Cu2x | 79.95 (6) |
O1—Cu1—O4 | 90.0 | O2xii—Y1—Cu2x | 100.05 (6) |
O1i—Cu1—O4 | 90.0 | Cu2ii—Y1—Cu2x | 180.0 |
O5ii—Cu1—O4 | 90.0 | Al1x—Y1—Cu2x | 0.00 (2) |
O5—Cu1—O4 | 90.0 | Al1ii—Y1—Cu2x | 180.0 |
O1—Cu1—O4iii | 90.0 | O1iii—Ba1—O1viii | 166.56 (19) |
O1i—Cu1—O4iii | 90.0 | O1iii—Ba1—O1ix | 88.70 (2) |
O5ii—Cu1—O4iii | 90.0 | O1viii—Ba1—O1ix | 89.74 (2) |
O5—Cu1—O4iii | 90.0 | O1iii—Ba1—O1 | 89.74 (2) |
O4—Cu1—O4iii | 180.0 | O1viii—Ba1—O1 | 88.70 (2) |
O1—Cu1—Ba1iv | 128.561 (5) | O1ix—Ba1—O1 | 166.56 (19) |
O1i—Cu1—Ba1iv | 51.439 (5) | O1iii—Ba1—O4iii | 56.61 (8) |
O5ii—Cu1—Ba1iv | 56.608 (3) | O1viii—Ba1—O4iii | 112.02 (8) |
O5—Cu1—Ba1iv | 123.392 (3) | O1ix—Ba1—O4iii | 112.02 (8) |
O4—Cu1—Ba1iv | 123.742 (3) | O1—Ba1—O4iii | 56.61 (8) |
O4iii—Cu1—Ba1iv | 56.258 (3) | O1iii—Ba1—O4ix | 112.02 (8) |
O1—Cu1—Ba1v | 51.439 (5) | O1viii—Ba1—O4ix | 56.61 (8) |
O1i—Cu1—Ba1v | 128.561 (5) | O1ix—Ba1—O4ix | 56.61 (8) |
O5ii—Cu1—Ba1v | 123.392 (3) | O1—Ba1—O4ix | 112.02 (8) |
O5—Cu1—Ba1v | 56.608 (3) | O4iii—Ba1—O4ix | 82.884 (10) |
O4—Cu1—Ba1v | 56.258 (3) | O1iii—Ba1—O5iii | 56.17 (8) |
O4iii—Cu1—Ba1v | 123.742 (3) | O1viii—Ba1—O5iii | 112.46 (8) |
Ba1iv—Cu1—Ba1v | 180.0 | O1ix—Ba1—O5iii | 56.17 (8) |
O1—Cu1—Ba1i | 128.561 (5) | O1—Ba1—O5iii | 112.46 (8) |
O1i—Cu1—Ba1i | 51.439 (5) | O4iii—Ba1—O5iii | 55.967 (6) |
O5ii—Cu1—Ba1i | 56.608 (3) | O4ix—Ba1—O5iii | 55.967 (6) |
O5—Cu1—Ba1i | 123.392 (3) | O1iii—Ba1—O5 | 112.46 (8) |
O4—Cu1—Ba1i | 56.258 (3) | O1viii—Ba1—O5 | 56.17 (8) |
O4iii—Cu1—Ba1i | 123.742 (3) | O1ix—Ba1—O5 | 112.46 (8) |
Ba1iv—Cu1—Ba1i | 67.485 (6) | O1—Ba1—O5 | 56.17 (8) |
Ba1v—Cu1—Ba1i | 112.515 (6) | O4iii—Ba1—O5 | 55.967 (6) |
O1—Cu1—Ba1vi | 128.561 (5) | O4ix—Ba1—O5 | 55.967 (6) |
O1i—Cu1—Ba1vi | 51.439 (5) | O5iii—Ba1—O5 | 83.408 (10) |
O5ii—Cu1—Ba1vi | 123.392 (3) | O1iii—Ba1—O3ix | 122.93 (9) |
O5—Cu1—Ba1vi | 56.608 (3) | O1viii—Ba1—O3ix | 68.54 (9) |
O4—Cu1—Ba1vi | 123.742 (3) | O1ix—Ba1—O3ix | 68.54 (9) |
O4iii—Cu1—Ba1vi | 56.258 (3) | O1—Ba1—O3ix | 122.93 (9) |
Ba1iv—Cu1—Ba1vi | 66.784 (6) | O4iii—Ba1—O3ix | 179.13 (5) |
Ba1v—Cu1—Ba1vi | 113.216 (6) | O4ix—Ba1—O3ix | 97.98 (5) |
Ba1i—Cu1—Ba1vi | 102.878 (10) | O5iii—Ba1—O3ix | 124.55 (3) |
O1—Cu1—Ba1vii | 128.561 (5) | O5—Ba1—O3ix | 124.55 (3) |
O1i—Cu1—Ba1vii | 51.439 (5) | O1iii—Ba1—O3iii | 68.54 (9) |
O5ii—Cu1—Ba1vii | 123.392 (3) | O1viii—Ba1—O3iii | 122.93 (9) |
O5—Cu1—Ba1vii | 56.608 (3) | O1ix—Ba1—O3iii | 122.93 (9) |
O4—Cu1—Ba1vii | 56.258 (3) | O1—Ba1—O3iii | 68.54 (9) |
O4iii—Cu1—Ba1vii | 123.742 (3) | O4iii—Ba1—O3iii | 97.98 (5) |
Ba1iv—Cu1—Ba1vii | 102.878 (10) | O4ix—Ba1—O3iii | 179.13 (5) |
Ba1v—Cu1—Ba1vii | 77.122 (10) | O5iii—Ba1—O3iii | 124.55 (3) |
Ba1i—Cu1—Ba1vii | 66.784 (6) | O5—Ba1—O3iii | 124.55 (3) |
Ba1vi—Cu1—Ba1vii | 67.485 (6) | O3ix—Ba1—O3iii | 81.15 (11) |
O1—Cu1—Ba1 | 51.439 (5) | O1iii—Ba1—O2viii | 123.34 (8) |
O1i—Cu1—Ba1 | 128.561 (5) | O1viii—Ba1—O2viii | 68.13 (9) |
O5ii—Cu1—Ba1 | 123.392 (3) | O1ix—Ba1—O2viii | 123.34 (8) |
O5—Cu1—Ba1 | 56.608 (3) | O1—Ba1—O2viii | 68.13 (9) |
O4—Cu1—Ba1 | 123.742 (3) | O4iii—Ba1—O2viii | 124.57 (3) |
O4iii—Cu1—Ba1 | 56.258 (3) | O4ix—Ba1—O2viii | 124.57 (3) |
Ba1iv—Cu1—Ba1 | 112.515 (6) | O5iii—Ba1—O2viii | 179.10 (5) |
Ba1v—Cu1—Ba1 | 67.485 (6) | O5—Ba1—O2viii | 97.49 (5) |
Ba1i—Cu1—Ba1 | 180.0 | O3ix—Ba1—O2viii | 54.91 (5) |
Ba1vi—Cu1—Ba1 | 77.122 (10) | O3iii—Ba1—O2viii | 54.91 (5) |
Ba1vii—Cu1—Ba1 | 113.216 (6) | O1iii—Ba1—O2ix | 68.13 (9) |
O2viii—Cu2—O2 | 165.2 (2) | O1viii—Ba1—O2ix | 123.34 (8) |
O2viii—Cu2—O3 | 89.06 (2) | O1ix—Ba1—O2ix | 68.13 (9) |
O2—Cu2—O3 | 89.06 (2) | O1—Ba1—O2ix | 123.34 (8) |
O2viii—Cu2—O3iii | 89.06 (2) | O4iii—Ba1—O2ix | 124.57 (3) |
O2—Cu2—O3iii | 89.06 (2) | O4ix—Ba1—O2ix | 124.57 (3) |
O3—Cu2—O3iii | 165.4 (3) | O5iii—Ba1—O2ix | 97.49 (5) |
O2viii—Cu2—O1 | 97.42 (12) | O5—Ba1—O2ix | 179.10 (5) |
O2—Cu2—O1 | 97.42 (12) | O3ix—Ba1—O2ix | 54.91 (5) |
O3—Cu2—O1 | 97.29 (13) | O3iii—Ba1—O2ix | 54.91 (5) |
O3iii—Cu2—O1 | 97.29 (13) | O2viii—Ba1—O2ix | 81.62 (10) |
O2viii—Cu2—Ca1viii | 48.55 (7) | Cu1—O1—Cu2 | 180.0 |
O2—Cu2—Ca1viii | 121.76 (9) | Cu1—O1—Ba1v | 96.72 (9) |
O3—Cu2—Ca1viii | 48.21 (7) | Cu2—O1—Ba1v | 83.28 (9) |
O3iii—Cu2—Ca1viii | 122.22 (9) | Cu1—O1—Ba1ii | 96.72 (9) |
O1—Cu2—Ca1viii | 121.652 (11) | Cu2—O1—Ba1ii | 83.28 (9) |
O2viii—Cu2—Y1viii | 48.55 (7) | Ba1v—O1—Ba1ii | 166.56 (19) |
O2—Cu2—Y1viii | 121.76 (9) | Cu1—O1—Ba1 | 96.72 (9) |
O3—Cu2—Y1viii | 48.21 (7) | Cu2—O1—Ba1 | 83.28 (9) |
O3iii—Cu2—Y1viii | 122.22 (9) | Ba1v—O1—Ba1 | 89.74 (2) |
O1—Cu2—Y1viii | 121.652 (11) | Ba1ii—O1—Ba1 | 88.70 (2) |
Ca1viii—Cu2—Y1viii | 0.0 | Cu1—O1—Ba1xiii | 96.72 (9) |
O2viii—Cu2—Ca1iii | 121.76 (9) | Cu2—O1—Ba1xiii | 83.28 (9) |
O2—Cu2—Ca1iii | 48.55 (7) | Ba1v—O1—Ba1xiii | 88.70 (2) |
O3—Cu2—Ca1iii | 122.22 (9) | Ba1ii—O1—Ba1xiii | 89.74 (2) |
O3iii—Cu2—Ca1iii | 48.21 (7) | Ba1—O1—Ba1xiii | 166.56 (19) |
O1—Cu2—Ca1iii | 121.652 (11) | Al1ii—O2—Cu2ii | 0.00 (4) |
Ca1viii—Cu2—Ca1iii | 116.70 (2) | Al1ii—O2—Cu2 | 165.2 (2) |
Y1viii—Cu2—Ca1iii | 116.70 (2) | Cu2ii—O2—Cu2 | 165.2 (2) |
O2viii—Cu2—Y1iii | 121.76 (9) | Al1ii—O2—Y1 | 94.40 (6) |
O2—Cu2—Y1iii | 48.55 (7) | Cu2ii—O2—Y1 | 94.40 (6) |
O3—Cu2—Y1iii | 122.22 (9) | Cu2—O2—Y1 | 94.40 (6) |
O3iii—Cu2—Y1iii | 48.21 (7) | Al1ii—O2—Y1iii | 94.40 (6) |
O1—Cu2—Y1iii | 121.652 (11) | Cu2ii—O2—Y1iii | 94.40 (6) |
Ca1viii—Cu2—Y1iii | 116.70 (2) | Cu2—O2—Y1iii | 94.40 (6) |
Y1viii—Cu2—Y1iii | 116.70 (2) | Y1—O2—Y1iii | 107.09 (16) |
Ca1iii—Cu2—Y1iii | 0.0 | Al1ii—O2—Ca1iii | 94.40 (6) |
O2viii—Cu2—Y1 | 121.76 (9) | Cu2ii—O2—Ca1iii | 94.40 (6) |
O2—Cu2—Y1 | 48.55 (7) | Cu2—O2—Ca1iii | 94.40 (6) |
O3—Cu2—Y1 | 48.21 (7) | Y1—O2—Ca1iii | 107.09 (16) |
O3iii—Cu2—Y1 | 122.22 (9) | Y1iii—O2—Ca1iii | 0.0 |
O1—Cu2—Y1 | 121.652 (11) | Al1ii—O2—Ba1ii | 84.39 (10) |
Ca1viii—Cu2—Y1 | 73.617 (11) | Cu2ii—O2—Ba1ii | 84.39 (10) |
Y1viii—Cu2—Y1 | 73.617 (11) | Cu2—O2—Ba1ii | 84.39 (10) |
Ca1iii—Cu2—Y1 | 74.413 (11) | Y1—O2—Ba1ii | 167.26 (13) |
Y1iii—Cu2—Y1 | 74.413 (11) | Y1iii—O2—Ba1ii | 85.65 (3) |
O2viii—Cu2—Ca1ix | 48.55 (7) | Ca1iii—O2—Ba1ii | 85.65 (3) |
O2—Cu2—Ca1ix | 121.76 (9) | Al1ii—O2—Ba1xiii | 84.39 (10) |
O3—Cu2—Ca1ix | 122.22 (9) | Cu2ii—O2—Ba1xiii | 84.39 (10) |
O3iii—Cu2—Ca1ix | 48.21 (7) | Cu2—O2—Ba1xiii | 84.39 (10) |
O1—Cu2—Ca1ix | 121.652 (11) | Y1—O2—Ba1xiii | 85.65 (3) |
Ca1viii—Cu2—Ca1ix | 74.413 (11) | Y1iii—O2—Ba1xiii | 167.26 (13) |
Y1viii—Cu2—Ca1ix | 74.413 (11) | Ca1iii—O2—Ba1xiii | 167.26 (13) |
Ca1iii—Cu2—Ca1ix | 73.617 (11) | Ba1ii—O2—Ba1xiii | 81.62 (10) |
Y1iii—Cu2—Ca1ix | 73.617 (11) | Cu2—O3—Al1v | 165.4 (3) |
Y1—Cu2—Ca1ix | 116.70 (2) | Cu2—O3—Cu2v | 165.4 (3) |
O3ii—Y1—O3x | 180.00 (16) | Al1v—O3—Cu2v | 0.00 (4) |
O3ii—Y1—O3 | 106.50 (16) | Cu2—O3—Ca1viii | 94.35 (7) |
O3x—Y1—O3 | 73.50 (16) | Al1v—O3—Ca1viii | 94.35 (7) |
O3ii—Y1—O3xi | 73.50 (16) | Cu2v—O3—Ca1viii | 94.35 (7) |
O3x—Y1—O3xi | 106.50 (16) | Cu2—O3—Y1viii | 94.35 (7) |
O3—Y1—O3xi | 180.0 | Al1v—O3—Y1viii | 94.35 (7) |
O3ii—Y1—O2 | 69.17 (6) | Cu2v—O3—Y1viii | 94.35 (7) |
O3x—Y1—O2 | 110.83 (6) | Ca1viii—O3—Y1viii | 0.0 |
O3—Y1—O2 | 69.17 (6) | Cu2—O3—Y1 | 94.35 (7) |
O3xi—Y1—O2 | 110.83 (6) | Al1v—O3—Y1 | 94.35 (7) |
O3ii—Y1—O2xi | 110.83 (6) | Cu2v—O3—Y1 | 94.35 (7) |
O3x—Y1—O2xi | 69.17 (6) | Ca1viii—O3—Y1 | 106.50 (16) |
O3—Y1—O2xi | 110.83 (6) | Y1viii—O3—Y1 | 106.50 (16) |
O3xi—Y1—O2xi | 69.17 (6) | Cu2—O3—Ba1xiii | 84.47 (10) |
O2—Y1—O2xi | 180.00 (16) | Al1v—O3—Ba1xiii | 84.47 (10) |
O3ii—Y1—O2v | 69.17 (6) | Cu2v—O3—Ba1xiii | 84.47 (10) |
O3x—Y1—O2v | 110.83 (6) | Ca1viii—O3—Ba1xiii | 167.33 (14) |
O3—Y1—O2v | 69.17 (6) | Y1viii—O3—Ba1xiii | 167.33 (14) |
O3xi—Y1—O2v | 110.83 (6) | Y1—O3—Ba1xiii | 86.18 (3) |
O2—Y1—O2v | 107.09 (16) | Cu2—O3—Ba1v | 84.47 (10) |
O2xi—Y1—O2v | 72.91 (16) | Al1v—O3—Ba1v | 84.47 (10) |
O3ii—Y1—O2xii | 110.83 (6) | Cu2v—O3—Ba1v | 84.47 (10) |
O3x—Y1—O2xii | 69.17 (6) | Ca1viii—O3—Ba1v | 86.18 (3) |
O3—Y1—O2xii | 110.83 (6) | Y1viii—O3—Ba1v | 86.18 (3) |
O3xi—Y1—O2xii | 69.17 (6) | Y1—O3—Ba1v | 167.33 (14) |
O2—Y1—O2xii | 72.91 (16) | Ba1xiii—O3—Ba1v | 81.15 (11) |
O2xi—Y1—O2xii | 107.09 (16) | Cu1v—O4—Cu1 | 180.0 |
O2v—Y1—O2xii | 180.0 | Cu1v—O4—Ba1i | 90.0 |
O3ii—Y1—Cu2ii | 37.434 (10) | Cu1—O4—Ba1i | 90.0 |
O3x—Y1—Cu2ii | 142.566 (9) | Cu1v—O4—Ba1v | 90.0 |
O3—Y1—Cu2ii | 99.56 (7) | Cu1—O4—Ba1v | 90.0 |
O3xi—Y1—Cu2ii | 80.44 (7) | Ba1i—O4—Ba1v | 180.000 (9) |
O2—Y1—Cu2ii | 37.044 (9) | Cu1v—O4—Ba1vii | 90.0 |
O2xi—Y1—Cu2ii | 142.956 (9) | Cu1—O4—Ba1vii | 90.0 |
O2v—Y1—Cu2ii | 100.05 (6) | Ba1i—O4—Ba1vii | 82.884 (10) |
O2xii—Y1—Cu2ii | 79.95 (6) | Ba1v—O4—Ba1vii | 97.116 (10) |
O3ii—Y1—Al1x | 142.566 (10) | Cu1v—O4—Ba1xiii | 90.0 |
O3x—Y1—Al1x | 37.434 (9) | Cu1—O4—Ba1xiii | 90.0 |
O3—Y1—Al1x | 80.44 (7) | Ba1i—O4—Ba1xiii | 97.116 (10) |
O3xi—Y1—Al1x | 99.56 (7) | Ba1v—O4—Ba1xiii | 82.884 (10) |
O2—Y1—Al1x | 142.956 (9) | Ba1vii—O4—Ba1xiii | 180.0 |
O2xi—Y1—Al1x | 37.044 (9) | Cu1viii—O5—Cu1 | 180.0 |
O2v—Y1—Al1x | 79.95 (6) | Cu1viii—O5—Ba1vi | 90.0 |
O2xii—Y1—Al1x | 100.05 (6) | Cu1—O5—Ba1vi | 90.0 |
Cu2ii—Y1—Al1x | 180.0 | Cu1viii—O5—Ba1v | 90.0 |
O3ii—Y1—Al1ii | 37.434 (10) | Cu1—O5—Ba1v | 90.0 |
O3x—Y1—Al1ii | 142.566 (9) | Ba1vi—O5—Ba1v | 180.000 (9) |
O3—Y1—Al1ii | 99.56 (7) | Cu1viii—O5—Ba1vii | 90.0 |
O3xi—Y1—Al1ii | 80.44 (7) | Cu1—O5—Ba1vii | 90.0 |
O2—Y1—Al1ii | 37.044 (9) | Ba1vi—O5—Ba1vii | 83.408 (10) |
O2xi—Y1—Al1ii | 142.956 (9) | Ba1v—O5—Ba1vii | 96.592 (10) |
O2v—Y1—Al1ii | 100.05 (6) | Cu1viii—O5—Ba1 | 90.0 |
O2xii—Y1—Al1ii | 79.95 (6) | Cu1—O5—Ba1 | 90.0 |
Cu2ii—Y1—Al1ii | 0.0 | Ba1vi—O5—Ba1 | 96.592 (10) |
Al1x—Y1—Al1ii | 180.0 | Ba1v—O5—Ba1 | 83.408 (10) |
O3ii—Y1—Cu2x | 142.566 (10) | Ba1vii—O5—Ba1 | 180.000 (9) |
Symmetry codes: (i) −x, −y, −z; (ii) x−1, y, z; (iii) x, y−1, z; (iv) −x, −y−1, −z; (v) x, y+1, z; (vi) −x+1, −y−1, −z; (vii) −x+1, −y, −z; (viii) x+1, y, z; (ix) x+1, y−1, z; (x) −x, −y+1, −z+1; (xi) −x−1, −y+1, −z+1; (xii) −x−1, −y, −z+1; (xiii) x−1, y+1, z. |
Cu2O5.92Y0.88·0.84(O)·1.93(Ba)·0.69(Cu)·2.12(Ca0.04) | Dx = 6.119 Mg m−3 |
Mr = 639.18 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P4/mmm | Cell parameters from 2189 reflections |
a = 3.8595 (2) Å | θ = 6.3–32.7° |
c = 11.6456 (8) Å | µ = 26.38 mm−1 |
V = 173.47 (2) Å3 | T = 293 K |
Z = 1 | 0.24 × 0.04 × 0.02 mm |
F(000) = 282.7 |
Xcalibur, Ruby, Gemini ultra diffractometer | 244 independent reflections |
Radiation source: fine-focus sealed tube | 228 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 10.2890 pixels mm-1 | θmax = 32.8°, θmin = 6.3° |
Absorption correction: analytical CrysAlis PRO, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) | h = −5→5 |
Tmin = 0.304, Tmax = 0.642 | k = −5→5 |
3659 measured reflections | l = −16→17 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.016 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.039 | w = 1/[σ2(Fo2) + (0.015P)2 + 0.187P] where P = (Fo2 + 2Fc2)/3 |
S = 1.38 | (Δ/σ)max < 0.001 |
233 reflections | Δρmax = 0.95 e Å−3 |
26 parameters | Δρmin = −1.19 e Å−3 |
Cu2O5.92Y0.88·0.84(O)·1.93(Ba)·0.69(Cu)·2.12(Ca0.04) | Z = 1 |
Mr = 639.18 | Mo Kα radiation |
Tetragonal, P4/mmm | µ = 26.38 mm−1 |
a = 3.8595 (2) Å | T = 293 K |
c = 11.6456 (8) Å | 0.24 × 0.04 × 0.02 mm |
V = 173.47 (2) Å3 |
Xcalibur, Ruby, Gemini ultra diffractometer | 244 independent reflections |
Absorption correction: analytical CrysAlis PRO, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) | 228 reflections with I > 2σ(I) |
Tmin = 0.304, Tmax = 0.642 | Rint = 0.040 |
3659 measured reflections |
R[F2 > 2σ(F2)] = 0.016 | 26 parameters |
wR(F2) = 0.039 | 0 restraints |
S = 1.38 | Δρmax = 0.95 e Å−3 |
233 reflections | Δρmin = −1.19 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. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Y1 | 0.0000 | 0.0000 | 0.5000 | 0.0086 (3) | 0.884 (6) |
Ca1 | 0.0000 | 0.0000 | 0.5000 | 0.0086 (3) | 0.12 |
Cu2 | 0.5000 | 0.5000 | 0.35723 (6) | 0.0088 (2) | |
Cu1 | 0.5000 | 0.5000 | 0.0000 | 0.0172 (5) | 0.695 (6) |
Al1 | 0.5000 | 0.5000 | 0.0000 | 0.0172 (5) | 0.31 |
Ba1 | 0.0000 | 0.0000 | 0.18690 (3) | 0.01424 (13) | 0.964 (4) |
Ca2 | 0.0000 | 0.0000 | 0.18690 (3) | 0.01424 (13) | 0.04 |
O1 | 0.5000 | 0.5000 | −0.1560 (5) | 0.032 (2) | 0.96 (3) |
O2 | 0.5000 | 0.0000 | 0.0000 | 0.020 (3) | 0.42 (2) |
O3 | 0.0000 | 0.5000 | 0.3767 (3) | 0.0123 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Y1 | 0.0071 (3) | 0.0071 (3) | 0.0115 (4) | 0.000 | 0.000 | 0.000 |
Ca1 | 0.0071 (3) | 0.0071 (3) | 0.0115 (4) | 0.000 | 0.000 | 0.000 |
Cu2 | 0.0061 (3) | 0.0061 (3) | 0.0142 (4) | 0.000 | 0.000 | 0.000 |
Cu1 | 0.0207 (6) | 0.0207 (6) | 0.0102 (6) | 0.000 | 0.000 | 0.000 |
Al1 | 0.0207 (6) | 0.0207 (6) | 0.0102 (6) | 0.000 | 0.000 | 0.000 |
Ba1 | 0.01422 (15) | 0.01422 (15) | 0.0143 (2) | 0.000 | 0.000 | 0.000 |
Ca2 | 0.01422 (15) | 0.01422 (15) | 0.0143 (2) | 0.000 | 0.000 | 0.000 |
O1 | 0.038 (3) | 0.038 (3) | 0.020 (3) | 0.000 | 0.000 | 0.000 |
O2 | 0.035 (7) | 0.011 (5) | 0.015 (5) | 0.000 | 0.000 | 0.000 |
O3 | 0.0059 (12) | 0.0121 (13) | 0.0188 (13) | 0.000 | 0.000 | 0.000 |
Y1—O3i | 2.4053 (19) | Ba1—O1xvi | 2.7526 (8) |
Y1—O3ii | 2.4053 (19) | Ba1—O1xiii | 2.7526 (8) |
Y1—O3iii | 2.4053 (19) | Ba1—O1xvii | 2.7526 (8) |
Y1—O3iv | 2.4053 (19) | Ba1—O1xviii | 2.7526 (8) |
Y1—O3v | 2.4053 (19) | Ba1—O2xix | 2.9088 (3) |
Y1—O3 | 2.4053 (19) | Ba1—O2x | 2.9088 (3) |
Y1—O3vi | 2.4053 (19) | Ba1—O2i | 2.9088 (3) |
Y1—O3vii | 2.4053 (19) | Ba1—O2 | 2.9088 (3) |
Y1—Cu2viii | 3.1956 (4) | Ba1—O3 | 2.934 (2) |
Y1—Cu2ix | 3.1956 (4) | Ba1—O3iii | 2.934 (2) |
Y1—Cu2x | 3.1956 (4) | Ba1—O3i | 2.934 (2) |
Y1—Cu2ii | 3.1956 (4) | Ba1—O3ii | 2.934 (2) |
Cu2—O3xi | 1.9430 (4) | O1—Cu2xiii | 2.343 (6) |
Cu2—O3xii | 1.9430 (4) | O1—Ca2xvi | 2.7526 (8) |
Cu2—O3 | 1.9430 (4) | O1—Ba1xvi | 2.7526 (8) |
Cu2—O3iii | 1.9430 (4) | O1—Ca2xiii | 2.7526 (8) |
Cu2—O1xiii | 2.343 (6) | O1—Ba1xiii | 2.7526 (8) |
Cu2—Ca1xiv | 3.1956 (4) | O1—Ba1xvii | 2.7526 (8) |
Cu2—Y1xiv | 3.1956 (4) | O1—Ba1xviii | 2.7526 (8) |
Cu2—Y1xv | 3.1956 (4) | O1—Ca2xviii | 2.7526 (8) |
Cu2—Ca1xv | 3.1956 (4) | O1—Ca2xvii | 2.7526 (8) |
Cu2—Y1xii | 3.1956 (4) | O2—Al1ii | 1.9297 |
Cu1—O1 | 1.817 (6) | O2—Cu1ii | 1.9297 |
Cu1—O1xiii | 1.817 (6) | O2—Ca2xvi | 2.9088 (3) |
Cu1—O2iii | 1.9297 | O2—Ba1xvi | 2.9088 (3) |
Cu1—O2i | 1.9297 | O2—Ca2xviii | 2.9088 (3) |
Cu1—O2 | 1.9297 | O2—Ba1xviii | 2.9088 (3) |
Cu1—O2xv | 1.9297 | O2—Ba1xii | 2.9088 (3) |
Cu1—Ca2xvi | 3.4907 (3) | O2—Ca2xii | 2.9088 (3) |
Cu1—Ba1xvi | 3.4907 (3) | O3—Cu2x | 1.9430 (4) |
Cu1—Ba1xiv | 3.4907 (3) | O3—Ca1xv | 2.4053 (19) |
Cu1—Ca2xiv | 3.4907 (3) | O3—Y1xv | 2.4053 (19) |
Cu1—Ca2xvii | 3.4907 (3) | O3—Ca2xv | 2.934 (2) |
Cu1—Ca2xviii | 3.4907 (3) | O3—Ba1xv | 2.934 (2) |
O3i—Y1—O3ii | 69.12 (6) | Ca2xvii—Cu1—Ca2xviii | 102.851 (10) |
O3i—Y1—O3iii | 106.70 (12) | O1xvi—Ba1—O1xiii | 165.0 (2) |
O3ii—Y1—O3iii | 69.12 (6) | O1xvi—Ba1—O1xvii | 89.02 (3) |
O3i—Y1—O3iv | 180.00 (12) | O1xiii—Ba1—O1xvii | 89.02 (3) |
O3ii—Y1—O3iv | 110.88 (6) | O1xvi—Ba1—O1xviii | 89.02 (3) |
O3iii—Y1—O3iv | 73.30 (12) | O1xiii—Ba1—O1xviii | 89.02 (3) |
O3i—Y1—O3v | 110.88 (6) | O1xvii—Ba1—O1xviii | 165.0 (2) |
O3ii—Y1—O3v | 180.00 (12) | O1xvi—Ba1—O2xix | 55.75 (10) |
O3iii—Y1—O3v | 110.88 (6) | O1xiii—Ba1—O2xix | 111.56 (10) |
O3iv—Y1—O3v | 69.12 (6) | O1xvii—Ba1—O2xix | 111.56 (10) |
O3i—Y1—O3 | 69.12 (6) | O1xviii—Ba1—O2xix | 55.75 (10) |
O3ii—Y1—O3 | 106.70 (12) | O1xvi—Ba1—O2x | 55.75 (10) |
O3iii—Y1—O3 | 69.12 (6) | O1xiii—Ba1—O2x | 111.56 (10) |
O3iv—Y1—O3 | 110.88 (6) | O1xvii—Ba1—O2x | 55.75 (10) |
O3v—Y1—O3 | 73.30 (12) | O1xviii—Ba1—O2x | 111.56 (10) |
O3i—Y1—O3vi | 73.30 (12) | O2xix—Ba1—O2x | 55.951 (6) |
O3ii—Y1—O3vi | 110.88 (6) | O1xvi—Ba1—O2i | 111.56 (10) |
O3iii—Y1—O3vi | 180.0 | O1xiii—Ba1—O2i | 55.75 (10) |
O3iv—Y1—O3vi | 106.70 (12) | O1xvii—Ba1—O2i | 55.75 (10) |
O3v—Y1—O3vi | 69.12 (6) | O1xviii—Ba1—O2i | 111.56 (10) |
O3—Y1—O3vi | 110.88 (6) | O2xix—Ba1—O2i | 83.120 (10) |
O3i—Y1—O3vii | 110.88 (6) | O2x—Ba1—O2i | 55.951 (6) |
O3ii—Y1—O3vii | 73.30 (12) | O1xvi—Ba1—O2 | 111.56 (10) |
O3iii—Y1—O3vii | 110.88 (6) | O1xiii—Ba1—O2 | 55.75 (10) |
O3iv—Y1—O3vii | 69.12 (6) | O1xvii—Ba1—O2 | 111.56 (10) |
O3v—Y1—O3vii | 106.70 (12) | O1xviii—Ba1—O2 | 55.75 (10) |
O3—Y1—O3vii | 180.0 | O2xix—Ba1—O2 | 55.951 (6) |
O3vi—Y1—O3vii | 69.12 (6) | O2x—Ba1—O2 | 83.120 (10) |
O3i—Y1—Cu2viii | 37.340 (7) | O2i—Ba1—O2 | 55.951 (6) |
O3ii—Y1—Cu2viii | 37.340 (7) | O1xvi—Ba1—O3 | 124.01 (10) |
O3iii—Y1—Cu2viii | 100.01 (5) | O1xiii—Ba1—O3 | 68.73 (11) |
O3iv—Y1—Cu2viii | 142.660 (7) | O1xvii—Ba1—O3 | 68.73 (11) |
O3v—Y1—Cu2viii | 142.660 (7) | O1xviii—Ba1—O3 | 124.01 (10) |
O3—Y1—Cu2viii | 100.01 (5) | O2xix—Ba1—O3 | 179.56 (4) |
O3vi—Y1—Cu2viii | 79.99 (5) | O2x—Ba1—O3 | 124.31 (2) |
O3vii—Y1—Cu2viii | 79.99 (5) | O2i—Ba1—O3 | 97.32 (4) |
O3i—Y1—Cu2ix | 142.660 (7) | O2—Ba1—O3 | 124.31 (2) |
O3ii—Y1—Cu2ix | 142.660 (7) | O1xvi—Ba1—O3iii | 124.01 (10) |
O3iii—Y1—Cu2ix | 79.99 (5) | O1xiii—Ba1—O3iii | 68.73 (11) |
O3iv—Y1—Cu2ix | 37.340 (7) | O1xvii—Ba1—O3iii | 124.01 (10) |
O3v—Y1—Cu2ix | 37.340 (7) | O1xviii—Ba1—O3iii | 68.73 (11) |
O3—Y1—Cu2ix | 79.99 (5) | O2xix—Ba1—O3iii | 124.31 (2) |
O3vi—Y1—Cu2ix | 100.01 (5) | O2x—Ba1—O3iii | 179.56 (4) |
O3vii—Y1—Cu2ix | 100.01 (5) | O2i—Ba1—O3iii | 124.31 (2) |
Cu2viii—Y1—Cu2ix | 180.00 (2) | O2—Ba1—O3iii | 97.32 (4) |
O3i—Y1—Cu2x | 37.340 (7) | O3—Ba1—O3iii | 55.43 (5) |
O3ii—Y1—Cu2x | 100.01 (5) | O1xvi—Ba1—O3i | 68.73 (11) |
O3iii—Y1—Cu2x | 100.01 (5) | O1xiii—Ba1—O3i | 124.01 (10) |
O3iv—Y1—Cu2x | 142.660 (7) | O1xvii—Ba1—O3i | 68.73 (11) |
O3v—Y1—Cu2x | 79.99 (5) | O1xviii—Ba1—O3i | 124.01 (10) |
O3—Y1—Cu2x | 37.340 (7) | O2xix—Ba1—O3i | 124.31 (2) |
O3vi—Y1—Cu2x | 79.99 (5) | O2x—Ba1—O3i | 97.32 (4) |
O3vii—Y1—Cu2x | 142.660 (7) | O2i—Ba1—O3i | 124.31 (2) |
Cu2viii—Y1—Cu2x | 74.295 (10) | O2—Ba1—O3i | 179.56 (4) |
Cu2ix—Y1—Cu2x | 105.705 (10) | O3—Ba1—O3i | 55.43 (5) |
O3i—Y1—Cu2ii | 100.01 (5) | O3iii—Ba1—O3i | 82.24 (8) |
O3ii—Y1—Cu2ii | 37.340 (7) | O1xvi—Ba1—O3ii | 68.73 (11) |
O3iii—Y1—Cu2ii | 37.340 (7) | O1xiii—Ba1—O3ii | 124.01 (10) |
O3iv—Y1—Cu2ii | 79.99 (5) | O1xvii—Ba1—O3ii | 124.01 (10) |
O3v—Y1—Cu2ii | 142.660 (7) | O1xviii—Ba1—O3ii | 68.73 (11) |
O3—Y1—Cu2ii | 100.01 (5) | O2xix—Ba1—O3ii | 97.32 (4) |
O3vi—Y1—Cu2ii | 142.660 (7) | O2x—Ba1—O3ii | 124.31 (2) |
O3vii—Y1—Cu2ii | 79.99 (5) | O2i—Ba1—O3ii | 179.56 (4) |
Cu2viii—Y1—Cu2ii | 74.295 (10) | O2—Ba1—O3ii | 124.31 (2) |
Cu2ix—Y1—Cu2ii | 105.705 (10) | O3—Ba1—O3ii | 82.24 (8) |
Cu2x—Y1—Cu2ii | 117.30 (2) | O3iii—Ba1—O3ii | 55.43 (5) |
O3xi—Cu2—O3xii | 89.22 (2) | O3i—Ba1—O3ii | 55.43 (5) |
O3xi—Cu2—O3 | 89.22 (2) | Cu1—O1—Cu2xiii | 180.0 |
O3xii—Cu2—O3 | 166.60 (19) | Cu1—O1—Ca2xvi | 97.50 (12) |
O3xi—Cu2—O3iii | 166.60 (19) | Cu2xiii—O1—Ca2xvi | 82.50 (12) |
O3xii—Cu2—O3iii | 89.22 (2) | Cu1—O1—Ba1xvi | 97.50 (12) |
O3—Cu2—O3iii | 89.22 (2) | Cu2xiii—O1—Ba1xvi | 82.50 (12) |
O3xi—Cu2—O1xiii | 96.70 (9) | Ca2xvi—O1—Ba1xvi | 0.000 (14) |
O3xii—Cu2—O1xiii | 96.70 (9) | Cu1—O1—Ca2xiii | 97.50 (12) |
O3—Cu2—O1xiii | 96.70 (9) | Cu2xiii—O1—Ca2xiii | 82.50 (12) |
O3iii—Cu2—O1xiii | 96.70 (9) | Ca2xvi—O1—Ca2xiii | 165.0 (2) |
O3xi—Cu2—Ca1xiv | 48.66 (5) | Ba1xvi—O1—Ca2xiii | 165.0 (2) |
O3xii—Cu2—Ca1xiv | 48.66 (5) | Cu1—O1—Ba1xiii | 97.50 (12) |
O3—Cu2—Ca1xiv | 122.62 (7) | Cu2xiii—O1—Ba1xiii | 82.50 (12) |
O3iii—Cu2—Ca1xiv | 122.62 (7) | Ca2xvi—O1—Ba1xiii | 165.0 (2) |
O1xiii—Cu2—Ca1xiv | 121.351 (11) | Ba1xvi—O1—Ba1xiii | 165.0 (2) |
O3xi—Cu2—Y1xiv | 48.66 (5) | Ca2xiii—O1—Ba1xiii | 0.000 (14) |
O3xii—Cu2—Y1xiv | 48.66 (5) | Cu1—O1—Ba1xvii | 97.50 (12) |
O3—Cu2—Y1xiv | 122.62 (7) | Cu2xiii—O1—Ba1xvii | 82.50 (12) |
O3iii—Cu2—Y1xiv | 122.62 (7) | Ca2xvi—O1—Ba1xvii | 89.02 (3) |
O1xiii—Cu2—Y1xiv | 121.351 (11) | Ba1xvi—O1—Ba1xvii | 89.02 (3) |
Ca1xiv—Cu2—Y1xiv | 0.0 | Ca2xiii—O1—Ba1xvii | 89.02 (3) |
O3xi—Cu2—Y1 | 122.62 (7) | Ba1xiii—O1—Ba1xvii | 89.02 (3) |
O3xii—Cu2—Y1 | 122.62 (7) | Cu1—O1—Ba1xviii | 97.50 (12) |
O3—Cu2—Y1 | 48.66 (5) | Cu2xiii—O1—Ba1xviii | 82.50 (12) |
O3iii—Cu2—Y1 | 48.66 (5) | Ca2xvi—O1—Ba1xviii | 89.02 (3) |
O1xiii—Cu2—Y1 | 121.351 (11) | Ba1xvi—O1—Ba1xviii | 89.02 (3) |
Ca1xiv—Cu2—Y1 | 117.30 (2) | Ca2xiii—O1—Ba1xviii | 89.02 (3) |
Y1xiv—Cu2—Y1 | 117.30 (2) | Ba1xiii—O1—Ba1xviii | 89.02 (3) |
O3xi—Cu2—Y1xv | 48.66 (6) | Ba1xvii—O1—Ba1xviii | 165.0 (2) |
O3xii—Cu2—Y1xv | 122.62 (7) | Cu1—O1—Ca2xviii | 97.50 (12) |
O3—Cu2—Y1xv | 48.66 (5) | Cu2xiii—O1—Ca2xviii | 82.50 (12) |
O3iii—Cu2—Y1xv | 122.62 (7) | Ca2xvi—O1—Ca2xviii | 89.02 (3) |
O1xiii—Cu2—Y1xv | 121.351 (11) | Ba1xvi—O1—Ca2xviii | 89.02 (3) |
Ca1xiv—Cu2—Y1xv | 74.295 (10) | Ca2xiii—O1—Ca2xviii | 89.02 (3) |
Y1xiv—Cu2—Y1xv | 74.295 (10) | Ba1xiii—O1—Ca2xviii | 89.02 (3) |
Y1—Cu2—Y1xv | 74.295 (10) | Ba1xvii—O1—Ca2xviii | 165.0 (2) |
O3xi—Cu2—Ca1xv | 48.66 (6) | Ba1xviii—O1—Ca2xviii | 0.000 (14) |
O3xii—Cu2—Ca1xv | 122.62 (7) | Cu1—O1—Ca2xvii | 97.50 (12) |
O3—Cu2—Ca1xv | 48.66 (5) | Cu2xiii—O1—Ca2xvii | 82.50 (12) |
O3iii—Cu2—Ca1xv | 122.62 (7) | Ca2xvi—O1—Ca2xvii | 89.02 (3) |
O1xiii—Cu2—Ca1xv | 121.351 (11) | Ba1xvi—O1—Ca2xvii | 89.02 (3) |
Ca1xiv—Cu2—Ca1xv | 74.295 (10) | Ca2xiii—O1—Ca2xvii | 89.02 (3) |
Y1xiv—Cu2—Ca1xv | 74.295 (10) | Ba1xiii—O1—Ca2xvii | 89.02 (3) |
Y1—Cu2—Ca1xv | 74.295 (10) | Ba1xvii—O1—Ca2xvii | 0.000 (14) |
Y1xv—Cu2—Ca1xv | 0.0 | Ba1xviii—O1—Ca2xvii | 165.0 (2) |
O3xi—Cu2—Y1xii | 122.62 (7) | Ca2xviii—O1—Ca2xvii | 165.0 (2) |
O3xii—Cu2—Y1xii | 48.66 (5) | Al1ii—O2—Cu1 | 180.0 |
O3—Cu2—Y1xii | 122.62 (7) | Al1ii—O2—Cu1ii | 0.0 |
O3iii—Cu2—Y1xii | 48.66 (5) | Cu1—O2—Cu1ii | 180.0 |
O1xiii—Cu2—Y1xii | 121.351 (11) | Al1ii—O2—Ca2xvi | 90.0 |
Ca1xiv—Cu2—Y1xii | 74.295 (10) | Cu1—O2—Ca2xvi | 90.0 |
Y1xiv—Cu2—Y1xii | 74.295 (10) | Cu1ii—O2—Ca2xvi | 90.0 |
Y1—Cu2—Y1xii | 74.295 (10) | Al1ii—O2—Ba1xvi | 90.0 |
Y1xv—Cu2—Y1xii | 117.30 (2) | Cu1—O2—Ba1xvi | 90.0 |
Ca1xv—Cu2—Y1xii | 117.30 (2) | Cu1ii—O2—Ba1xvi | 90.0 |
O1—Cu1—O1xiii | 180.0 | Ca2xvi—O2—Ba1xvi | 0.000 (9) |
O1—Cu1—O2iii | 90.0 | Al1ii—O2—Ca2xviii | 90.0 |
O1xiii—Cu1—O2iii | 90.0 | Cu1—O2—Ca2xviii | 90.0 |
O1—Cu1—O2i | 90.0 | Cu1ii—O2—Ca2xviii | 90.0 |
O1xiii—Cu1—O2i | 90.0 | Ca2xvi—O2—Ca2xviii | 83.120 (10) |
O2iii—Cu1—O2i | 180.0 | Ba1xvi—O2—Ca2xviii | 83.120 (10) |
O1—Cu1—O2 | 90.0 | Al1ii—O2—Ba1xviii | 90.0 |
O1xiii—Cu1—O2 | 90.0 | Cu1—O2—Ba1xviii | 90.0 |
O2iii—Cu1—O2 | 90.0 | Cu1ii—O2—Ba1xviii | 90.0 |
O2i—Cu1—O2 | 90.0 | Ca2xvi—O2—Ba1xviii | 83.120 (10) |
O1—Cu1—O2xv | 90.0 | Ba1xvi—O2—Ba1xviii | 83.120 (10) |
O1xiii—Cu1—O2xv | 90.0 | Ca2xviii—O2—Ba1xviii | 0.0 |
O2iii—Cu1—O2xv | 90.0 | Al1ii—O2—Ba1xii | 90.0 |
O2i—Cu1—O2xv | 90.0 | Cu1—O2—Ba1xii | 90.0 |
O2—Cu1—O2xv | 180.0 | Cu1ii—O2—Ba1xii | 90.0 |
O1—Cu1—Ca2xvi | 51.426 (5) | Ca2xvi—O2—Ba1xii | 180.0 |
O1xiii—Cu1—Ca2xvi | 128.574 (5) | Ba1xvi—O2—Ba1xii | 180.0 |
O2iii—Cu1—Ca2xvi | 123.560 (3) | Ca2xviii—O2—Ba1xii | 96.880 (10) |
O2i—Cu1—Ca2xvi | 56.440 (3) | Ba1xviii—O2—Ba1xii | 96.880 (10) |
O2—Cu1—Ca2xvi | 56.440 (3) | Al1ii—O2—Ca2xii | 90.0 |
O2xv—Cu1—Ca2xvi | 123.560 (3) | Cu1—O2—Ca2xii | 90.0 |
O1—Cu1—Ba1xvi | 51.426 (5) | Cu1ii—O2—Ca2xii | 90.0 |
O1xiii—Cu1—Ba1xvi | 128.574 (5) | Ca2xvi—O2—Ca2xii | 180.0 |
O2iii—Cu1—Ba1xvi | 123.560 (3) | Ba1xvi—O2—Ca2xii | 180.0 |
O2i—Cu1—Ba1xvi | 56.440 (3) | Ca2xviii—O2—Ca2xii | 96.880 (10) |
O2—Cu1—Ba1xvi | 56.440 (3) | Ba1xviii—O2—Ca2xii | 96.880 (10) |
O2xv—Cu1—Ba1xvi | 123.560 (3) | Ba1xii—O2—Ca2xii | 0.000 (9) |
Ca2xvi—Cu1—Ba1xvi | 0.000 (9) | Al1ii—O2—Ba1 | 90.0 |
O1—Cu1—Ba1xiv | 128.574 (5) | Cu1—O2—Ba1 | 90.0 |
O1xiii—Cu1—Ba1xiv | 51.426 (5) | Cu1ii—O2—Ba1 | 90.0 |
O2iii—Cu1—Ba1xiv | 56.440 (3) | Ca2xvi—O2—Ba1 | 96.880 (10) |
O2i—Cu1—Ba1xiv | 123.560 (3) | Ba1xvi—O2—Ba1 | 96.880 (10) |
O2—Cu1—Ba1xiv | 123.560 (3) | Ca2xviii—O2—Ba1 | 180.000 (9) |
O2xv—Cu1—Ba1xiv | 56.440 (3) | Ba1xviii—O2—Ba1 | 180.000 (9) |
Ca2xvi—Cu1—Ba1xiv | 180.000 (9) | Ba1xii—O2—Ba1 | 83.120 (10) |
Ba1xvi—Cu1—Ba1xiv | 180.000 (9) | Ca2xii—O2—Ba1 | 83.120 (10) |
O1—Cu1—Ca2xiv | 128.574 (5) | Cu2x—O3—Cu2 | 166.60 (19) |
O1xiii—Cu1—Ca2xiv | 51.426 (5) | Cu2x—O3—Ca1xv | 93.99 (5) |
O2iii—Cu1—Ca2xiv | 56.440 (3) | Cu2—O3—Ca1xv | 93.99 (5) |
O2i—Cu1—Ca2xiv | 123.560 (3) | Cu2x—O3—Y1xv | 93.99 (5) |
O2—Cu1—Ca2xiv | 123.560 (3) | Cu2—O3—Y1xv | 93.99 (5) |
O2xv—Cu1—Ca2xiv | 56.440 (3) | Ca1xv—O3—Y1xv | 0.0 |
Ca2xvi—Cu1—Ca2xiv | 180.000 (9) | Cu2x—O3—Y1 | 93.99 (5) |
Ba1xvi—Cu1—Ca2xiv | 180.000 (9) | Cu2—O3—Y1 | 93.99 (5) |
Ba1xiv—Cu1—Ca2xiv | 0.000 (9) | Ca1xv—O3—Y1 | 106.70 (12) |
O1—Cu1—Ca2xvii | 51.426 (5) | Y1xv—O3—Y1 | 106.70 (12) |
O1xiii—Cu1—Ca2xvii | 128.574 (5) | Cu2x—O3—Ba1 | 84.96 (7) |
O2iii—Cu1—Ca2xvii | 123.560 (3) | Cu2—O3—Ba1 | 84.96 (7) |
O2i—Cu1—Ca2xvii | 56.440 (3) | Ca1xv—O3—Ba1 | 167.77 (10) |
O2—Cu1—Ca2xvii | 123.560 (3) | Y1xv—O3—Ba1 | 167.77 (10) |
O2xv—Cu1—Ca2xvii | 56.440 (3) | Y1—O3—Ba1 | 85.53 (2) |
Ca2xvi—Cu1—Ca2xvii | 67.121 (5) | Cu2x—O3—Ca2xv | 84.96 (7) |
Ba1xvi—Cu1—Ca2xvii | 67.121 (5) | Cu2—O3—Ca2xv | 84.96 (7) |
Ba1xiv—Cu1—Ca2xvii | 112.879 (5) | Ca1xv—O3—Ca2xv | 85.53 (2) |
Ca2xiv—Cu1—Ca2xvii | 112.879 (5) | Y1xv—O3—Ca2xv | 85.53 (2) |
O1—Cu1—Ca2xviii | 51.426 (5) | Y1—O3—Ca2xv | 167.77 (10) |
O1xiii—Cu1—Ca2xviii | 128.574 (5) | Ba1—O3—Ca2xv | 82.24 (8) |
O2iii—Cu1—Ca2xviii | 56.440 (3) | Cu2x—O3—Ba1xv | 84.96 (7) |
O2i—Cu1—Ca2xviii | 123.560 (3) | Cu2—O3—Ba1xv | 84.96 (7) |
O2—Cu1—Ca2xviii | 56.440 (3) | Ca1xv—O3—Ba1xv | 85.53 (2) |
O2xv—Cu1—Ca2xviii | 123.560 (3) | Y1xv—O3—Ba1xv | 85.53 (2) |
Ca2xvi—Cu1—Ca2xviii | 67.121 (5) | Y1—O3—Ba1xv | 167.77 (10) |
Ba1xvi—Cu1—Ca2xviii | 67.121 (5) | Ba1—O3—Ba1xv | 82.24 (8) |
Ba1xiv—Cu1—Ca2xviii | 112.879 (5) | Ca2xv—O3—Ba1xv | 0.000 (9) |
Ca2xiv—Cu1—Ca2xviii | 112.879 (5) |
Symmetry codes: (i) −y, x, z; (ii) x, y−1, z; (iii) −y+1, x, z; (iv) y, −x, −z+1; (v) −x, −y+1, −z+1; (vi) y−1, −x, −z+1; (vii) −x, −y, −z+1; (viii) x−1, y−1, z; (ix) −x+1, −y+1, −z+1; (x) x−1, y, z; (xi) −y+1, x+1, z; (xii) x+1, y, z; (xiii) −x+1, −y+1, −z; (xiv) x+1, y+1, z; (xv) x, y+1, z; (xvi) −x, −y, −z; (xvii) −x, −y+1, −z; (xviii) −x+1, −y, −z; (xix) −y, x−1, z. |
Experimental details
(1) | (2) | (3) | |
Crystal data | |||
Chemical formula | Ba2Ca0.07Cu3O6.85Y0.93 | Al0.06Cu2.94O6Y0.94·0.81(O)·2(Ba)·0.06(Ca) | Cu2O5.92Y0.88·0.84(O)·1.93(Ba)·0.69(Cu)·2.12(Ca0.04) |
Mr | 660.39 | 657.80 | 639.18 |
Crystal system, space group | Orthorhombic, Pmmm | Orthorhombic, Pmmm | Tetragonal, P4/mmm |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 3.8114 (3), 3.8712 (3), 11.6824 (7) | 3.8380 (2), 3.8735 (2), 11.6947 (5) | 3.8595 (2), 3.8595 (2), 11.6456 (8) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 172.37 (2) | 173.86 (2) | 173.47 (2) |
Z | 1 | 1 | 1 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 28.11 | 27.77 | 26.38 |
Crystal size (mm) | 0.18 × 0.07 × 0.01 | 0.21 × 0.04 × 0.02 | 0.24 × 0.04 × 0.02 |
Data collection | |||
Diffractometer | Xcalibur, Ruby, Gemini ultra diffractometer | Xcalibur, Ruby, Gemini ultra diffractometer | Xcalibur, Ruby, Gemini ultra diffractometer |
Absorption correction | – | Analytical | Analytical CrysAlis PRO, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) |
Tmin, Tmax | – | 0.326, 0.639 | 0.304, 0.642 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1081, 234, 220 | 1677, 353, 337 | 3659, 244, 228 |
Rint | 0.044 | 0.026 | 0.040 |
(sin θ/λ)max (Å−1) | 0.624 | 0.714 | 0.761 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.083, 1.03 | 0.018, 0.051, 1.08 | 0.016, 0.039, 1.38 |
No. of reflections | 234 | 353 | 233 |
No. of parameters | 34 | 34 | 26 |
Δρmax, Δρmin (e Å−3) | 1.94, −1.32 | 0.90, −0.86 | 0.95, −1.19 |
Computer programs: CrysAlis PRO, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).