Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768104011644/na5017sup1.cif | |
Text file https://doi.org/10.1107/S0108768104011644/na5017sup2.txt | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768104011644/na5017bcso293sup3.fcf | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768104011644/na5017bcso640sup4.fcf |
For both compounds, data reduction: STOE X-RED; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS v5.1; software used to prepare material for publication: WinGX v1.64.05 (Farrugia, 1999).
CuO6Si2·Ba | Dx = 4.167 Mg m−3 |
Mr = 353.06 | Mo Kα radiation, λ = 0.71069 Å |
Tetragonal, I41/acd | Cell parameters from 1214 reflections |
Hall symbol: -I 4bd 2c | θ = 3.6–32.8° |
a = 10.0091 (16) Å | µ = 11.12 mm−1 |
c = 22.467 (6) Å | T = 293 K |
V = 2250.8 (8) Å3 | Cuboid, purple |
Z = 16 | 0.17 × 0.16 × 0.11 mm |
F(000) = 2575 |
STOE IPDS diffractometer | 1056 independent reflections |
Radiation source: fine-focus sealed tube | 523 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
rotation method scans | θmax = 32.8°, θmin = 3.6° |
Absorption correction: numerical via equivalents using STOE X-SHAPE and X-RED (Stoe & Cie, 1996) | h = 0→15 |
Tmin = 0.179, Tmax = 0.288 | k = 0→15 |
1056 measured reflections | l = 0→34 |
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)] = 0.028 | w = 1/[σ2(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.042 | (Δ/σ)max = 0.001 |
S = 1.26 | Δρmax = 1.12 e Å−3 |
1056 reflections | Δρmin = −2.04 e Å−3 |
48 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.000065 (7) |
CuO6Si2·Ba | Z = 16 |
Mr = 353.06 | Mo Kα radiation |
Tetragonal, I41/acd | µ = 11.12 mm−1 |
a = 10.0091 (16) Å | T = 293 K |
c = 22.467 (6) Å | 0.17 × 0.16 × 0.11 mm |
V = 2250.8 (8) Å3 |
STOE IPDS diffractometer | 1056 independent reflections |
Absorption correction: numerical via equivalents using STOE X-SHAPE and X-RED (Stoe & Cie, 1996) | 523 reflections with I > 2σ(I) |
Tmin = 0.179, Tmax = 0.288 | Rint = 0.000 |
1056 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 48 parameters |
wR(F2) = 0.042 | 0 restraints |
S = 1.26 | Δρmax = 1.12 e Å−3 |
1056 reflections | Δρmin = −2.04 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 | ||
Ba1 | 0.2500 | 0.98870 (9) | 0.5000 | 0.01258 (12) | |
Cu1 | 0.0000 | 0.2500 | 0.06374 (3) | 0.01012 (16) | |
Si1 | 0.27554 (11) | 0.7511 (2) | 0.8760 (4) | 0.0096 (3) | |
O1 | 0.1916 (9) | 0.7218 (11) | 0.8166 (4) | 0.0139 (17) | |
O2 | 0.3725 (8) | 0.8786 (8) | 0.85939 (16) | 0.0226 (10) | |
O3 | 0.3075 (9) | 0.7813 (11) | 0.0639 (5) | 0.0139 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ba1 | 0.0132 (5) | 0.0120 (4) | 0.01251 (15) | 0.000 | −0.0018 (3) | 0.000 |
Cu1 | 0.0089 (15) | 0.0092 (16) | 0.0123 (3) | 0.0000 (6) | 0.000 | 0.000 |
Si1 | 0.0078 (6) | 0.0069 (5) | 0.0140 (6) | 0.0002 (10) | −0.007 (3) | −0.0008 (10) |
O1 | 0.010 (4) | 0.016 (3) | 0.017 (4) | 0.005 (4) | 0.003 (3) | 0.002 (4) |
O2 | 0.016 (4) | 0.015 (4) | 0.037 (3) | −0.0024 (14) | −0.003 (4) | 0.002 (4) |
O3 | 0.008 (3) | 0.015 (3) | 0.019 (4) | −0.004 (4) | 0.002 (3) | 0.012 (4) |
Ba1—O1i | 2.719 (10) | Si1—O1xxxi | 3.813 (11) |
Ba1—O1ii | 2.719 (10) | O1—Cu1xxxii | 1.939 (9) |
Ba1—O3iii | 2.773 (10) | O1—O2 | 2.582 (14) |
Ba1—O3iv | 2.773 (10) | O1—O2xxiii | 2.644 (13) |
Ba1—O2v | 2.959 (4) | O1—Ba1xxx | 2.719 (10) |
Ba1—O2vi | 2.959 (4) | O1—O3xxv | 2.731 (15) |
Ba1—O3vii | 3.114 (12) | O1—O3xxii | 2.750 (5) |
Ba1—O3viii | 3.114 (12) | O1—O3xxxiii | 2.772 (16) |
Ba1—O1v | 3.237 (11) | O1—Ba1xxix | 3.237 (11) |
Ba1—O1vi | 3.237 (11) | O1—O1xxvi | 3.26 (2) |
Ba1—O2ix | 3.640 (4) | O1—Cu1xvi | 3.314 (10) |
Ba1—O2x | 3.640 (4) | O1—Si1xxiv | 3.392 (11) |
Cu1—O1xi | 1.939 (9) | O2—Si1xxvii | 1.638 (11) |
Cu1—O1xii | 1.939 (9) | O2—O3xxxii | 2.604 (13) |
Cu1—O3xiii | 1.952 (9) | O2—O1xxvii | 2.644 (13) |
Cu1—O3xiv | 1.952 (9) | O2—O2xxvii | 2.657 (6) |
Cu1—O1xv | 3.314 (10) | O2—O2xxiii | 2.657 (6) |
Cu1—O1xvi | 3.314 (10) | O2—O3xxii | 2.677 (13) |
Cu1—O3xvii | 3.372 (10) | O2—Ba1xxix | 2.959 (4) |
Cu1—O3xviii | 3.372 (10) | O2—O2xxxi | 3.523 (9) |
Cu1—Ba1xix | 3.7444 (8) | O2—O3xxv | 3.622 (13) |
Cu1—Ba1xx | 3.7444 (8) | O2—O1xxxiv | 3.624 (13) |
Cu1—Ba1xxi | 3.8926 (9) | O3—Si1xxii | 1.614 (13) |
Cu1—Ba1vii | 3.8926 (9) | O3—Cu1xxxiv | 1.952 (9) |
Si1—O1 | 1.605 (13) | O3—O2xi | 2.604 (13) |
Si1—O3xxii | 1.614 (13) | O3—O2xxii | 2.677 (13) |
Si1—O2xxiii | 1.638 (11) | O3—O1xxxv | 2.731 (15) |
Si1—O2 | 1.646 (11) | O3—O1xxii | 2.750 (5) |
Si1—O1xxiv | 3.392 (11) | O3—O1xxxvi | 2.772 (16) |
Si1—O3xxv | 3.405 (11) | O3—Ba1ix | 2.773 (10) |
Si1—Ba1xxvi | 3.685 (7) | O3—O3xxxvii | 3.09 (2) |
Si1—O2xxvii | 3.767 (6) | O3—Ba1vii | 3.114 (12) |
Si1—O2xxviii | 3.773 (6) | O3—Cu1xxxviii | 3.372 (10) |
Si1—Ba1xxix | 3.774 (7) | O3—Si1xxxv | 3.405 (11) |
Si1—Ba1xxx | 3.804 (7) | ||
O1i—Ba1—O1ii | 160.0 (4) | O3xvii—Cu1—Ba1xxi | 138.04 (19) |
O1i—Ba1—O3iii | 105.0 (3) | O3xviii—Cu1—Ba1xxi | 81.74 (19) |
O1ii—Ba1—O3iii | 91.63 (11) | Ba1xix—Cu1—Ba1xxi | 81.962 (8) |
O1i—Ba1—O3iv | 91.64 (11) | Ba1xx—Cu1—Ba1xxi | 81.861 (8) |
O1ii—Ba1—O3iv | 105.0 (3) | O1xi—Cu1—Ba1vii | 56.0 (3) |
O3iii—Ba1—O3iv | 67.8 (5) | O1xii—Cu1—Ba1vii | 125.7 (3) |
O1i—Ba1—O2v | 79.2 (3) | O3xiii—Cu1—Ba1vii | 138.0 (3) |
O1ii—Ba1—O2v | 93.2 (3) | O3xiv—Cu1—Ba1vii | 42.1 (3) |
O3iii—Ba1—O2v | 145.8 (3) | O1xv—Cu1—Ba1vii | 89.07 (17) |
O3iv—Ba1—O2v | 78.3 (3) | O1xvi—Cu1—Ba1vii | 127.82 (19) |
O1i—Ba1—O2vi | 93.2 (3) | O3xvii—Cu1—Ba1vii | 81.74 (19) |
O1ii—Ba1—O2vi | 79.2 (3) | O3xviii—Cu1—Ba1vii | 138.04 (19) |
O3iii—Ba1—O2vi | 78.3 (3) | Ba1xix—Cu1—Ba1vii | 81.861 (8) |
O3iv—Ba1—O2vi | 145.8 (3) | Ba1xx—Cu1—Ba1vii | 81.962 (8) |
O2v—Ba1—O2vi | 135.8 (3) | Ba1xxi—Cu1—Ba1vii | 136.83 (2) |
O1i—Ba1—O3vii | 56.27 (19) | O1—Si1—O3xxii | 117.4 (2) |
O1ii—Ba1—O3vii | 104.7 (3) | O1—Si1—O2xxiii | 109.2 (5) |
O3iii—Ba1—O3vii | 157.0 (3) | O3xxii—Si1—O2xxiii | 106.4 (6) |
O3iv—Ba1—O3vii | 121.3 (4) | O1—Si1—O2 | 105.2 (6) |
O2v—Ba1—O3vii | 50.7 (3) | O3xxii—Si1—O2 | 110.4 (5) |
O2vi—Ba1—O3vii | 88.9 (2) | O2xxiii—Si1—O2 | 108.0 (3) |
O1i—Ba1—O3viii | 104.7 (3) | O1—Si1—O1xxiv | 80.2 (4) |
O1ii—Ba1—O3viii | 56.27 (19) | O3xxii—Si1—O1xxiv | 54.1 (4) |
O3iii—Ba1—O3viii | 121.3 (4) | O2xxiii—Si1—O1xxiv | 84.6 (3) |
O3iv—Ba1—O3viii | 157.0 (3) | O2—Si1—O1xxiv | 163.2 (3) |
O2v—Ba1—O3viii | 88.9 (2) | O1—Si1—O3xxv | 52.1 (4) |
O2vi—Ba1—O3viii | 50.7 (3) | O3xxii—Si1—O3xxv | 82.4 (5) |
O3vii—Ba1—O3viii | 59.6 (4) | O2xxiii—Si1—O3xxv | 160.8 (4) |
O1i—Ba1—O1v | 119.0 (3) | O2—Si1—O3xxv | 83.9 (3) |
O1ii—Ba1—O1v | 65.8 (3) | O1xxiv—Si1—O3xxv | 87.23 (9) |
O3iii—Ba1—O1v | 103.8 (3) | O1—Si1—Ba1xxvi | 118.3 (4) |
O3iv—Ba1—O1v | 53.36 (17) | O3xxii—Si1—Ba1xxvi | 56.9 (5) |
O2v—Ba1—O1v | 49.0 (3) | O2xxiii—Si1—Ba1xxvi | 51.5 (3) |
O2vi—Ba1—O1v | 144.9 (2) | O2—Si1—Ba1xxvi | 135.8 (3) |
O3vii—Ba1—O1v | 97.64 (10) | O1xxiv—Si1—Ba1xxvi | 44.94 (18) |
O3viii—Ba1—O1v | 104.0 (3) | O3xxv—Si1—Ba1xxvi | 128.8 (2) |
O1i—Ba1—O1vi | 65.8 (3) | O1—Si1—O2xxvii | 128.7 (5) |
O1ii—Ba1—O1vi | 119.0 (3) | O3xxii—Si1—O2xxvii | 110.3 (4) |
O3iii—Ba1—O1vi | 53.36 (17) | O2xxiii—Si1—O2xxvii | 72.4 (2) |
O3iv—Ba1—O1vi | 103.8 (3) | O2—Si1—O2xxvii | 37.48 (16) |
O2v—Ba1—O1vi | 144.9 (2) | O1xxiv—Si1—O2xxvii | 147.4 (3) |
O2vi—Ba1—O1vi | 49.0 (3) | O3xxv—Si1—O2xxvii | 121.3 (2) |
O3vii—Ba1—O1vi | 104.0 (3) | Ba1xxvi—Si1—O2xxvii | 102.60 (17) |
O3viii—Ba1—O1vi | 97.64 (10) | O1—Si1—O2xxviii | 110.1 (4) |
O1v—Ba1—O1vi | 155.1 (3) | O3xxii—Si1—O2xxviii | 128.9 (5) |
O1i—Ba1—O2ix | 46.4 (3) | O2xxiii—Si1—O2xxviii | 37.12 (16) |
O1ii—Ba1—O2ix | 144.7 (3) | O2—Si1—O2xxviii | 72.2 (2) |
O3iii—Ba1—O2ix | 94.4 (2) | O1xxiv—Si1—O2xxviii | 121.6 (2) |
O3iv—Ba1—O2ix | 47.0 (3) | O3xxv—Si1—O2xxviii | 145.4 (3) |
O2v—Ba1—O2ix | 63.56 (13) | Ba1xxvi—Si1—O2xxviii | 85.16 (13) |
O2vi—Ba1—O2ix | 136.04 (9) | O2xxvii—Si1—O2xxviii | 41.27 (6) |
O3vii—Ba1—O2ix | 81.6 (2) | O1—Si1—Ba1xxix | 58.4 (5) |
O3viii—Ba1—O2ix | 141.2 (2) | O3xxii—Si1—Ba1xxix | 119.0 (4) |
O1v—Ba1—O2ix | 79.0 (2) | O2xxiii—Si1—Ba1xxix | 133.7 (4) |
O1vi—Ba1—O2ix | 91.9 (2) | O2—Si1—Ba1xxix | 48.7 (3) |
O1i—Ba1—O2x | 144.7 (3) | O1xxiv—Si1—Ba1xxix | 129.24 (19) |
O1ii—Ba1—O2x | 46.4 (3) | O3xxv—Si1—Ba1xxix | 45.08 (18) |
O3iii—Ba1—O2x | 47.0 (3) | Ba1xxvi—Si1—Ba1xxix | 173.83 (4) |
O3iv—Ba1—O2x | 94.4 (3) | O2xxvii—Si1—Ba1xxix | 83.05 (14) |
O2v—Ba1—O2x | 136.04 (9) | O2xxviii—Si1—Ba1xxix | 100.83 (17) |
O2vi—Ba1—O2x | 63.56 (13) | O1—Si1—Ba1xxx | 37.7 (4) |
O3vii—Ba1—O2x | 141.2 (2) | O3xxii—Si1—Ba1xxx | 134.2 (4) |
O3viii—Ba1—O2x | 81.6 (2) | O2xxiii—Si1—Ba1xxx | 71.7 (2) |
O1v—Ba1—O2x | 91.9 (2) | O2—Si1—Ba1xxx | 113.6 (4) |
O1vi—Ba1—O2x | 79.0 (2) | O1xxiv—Si1—Ba1xxx | 80.59 (17) |
O2ix—Ba1—O2x | 137.2 (3) | O3xxv—Si1—Ba1xxx | 89.8 (2) |
O1xi—Cu1—O1xii | 176.2 (6) | Ba1xxvi—Si1—Ba1xxx | 97.21 (6) |
O1xi—Cu1—O3xiii | 90.9 (6) | O2xxvii—Si1—Ba1xxx | 112.18 (17) |
O1xii—Cu1—O3xiii | 89.1 (6) | O2xxviii—Si1—Ba1xxx | 77.85 (15) |
O1xi—Cu1—O3xiv | 89.1 (6) | Ba1xxix—Si1—Ba1xxx | 82.76 (17) |
O1xii—Cu1—O3xiv | 90.9 (6) | O1—Si1—O1xxxi | 87.4 (4) |
O3xiii—Cu1—O3xiv | 179.8 (6) | O3xxii—Si1—O1xxxi | 38.1 (5) |
O1xi—Cu1—O1xv | 98.1 (4) | O2xxiii—Si1—O1xxxi | 142.4 (4) |
O1xii—Cu1—O1xv | 78.7 (5) | O2—Si1—O1xxxi | 99.2 (2) |
O3xiii—Cu1—O1xv | 123.8 (4) | O1xxiv—Si1—O1xxxi | 64.8 (3) |
O3xiv—Cu1—O1xv | 56.0 (3) | O3xxv—Si1—O1xxxi | 44.34 (14) |
O1xi—Cu1—O1xvi | 78.7 (5) | Ba1xxvi—Si1—O1xxxi | 90.9 (2) |
O1xii—Cu1—O1xvi | 98.1 (4) | O2xxvii—Si1—O1xxxi | 123.4 (2) |
O3xiii—Cu1—O1xvi | 56.0 (3) | O2xxviii—Si1—O1xxxi | 161.8 (3) |
O3xiv—Cu1—O1xvi | 123.8 (4) | Ba1xxix—Si1—O1xxxi | 83.88 (15) |
O1xv—Cu1—O1xvi | 71.6 (3) | Ba1xxx—Si1—O1xxxi | 120.31 (18) |
O1xi—Cu1—O3xvii | 54.6 (3) | Si1—O1—Cu1xxxii | 121.3 (6) |
O1xii—Cu1—O3xvii | 121.6 (4) | Si1—O1—Ba1xxx | 121.1 (5) |
O3xiii—Cu1—O3xvii | 100.5 (4) | Cu1xxxii—O1—Ba1xxx | 105.8 (4) |
O3xiv—Cu1—O3xvii | 79.3 (5) | Si1—O1—Ba1xxix | 96.6 (5) |
O1xv—Cu1—O3xvii | 48.2 (3) | Cu1xxxii—O1—Ba1xxix | 94.2 (4) |
O1xvi—Cu1—O3xvii | 49.0 (3) | Ba1xxx—O1—Ba1xxix | 114.2 (3) |
O1xi—Cu1—O3xviii | 121.6 (4) | Ba1xxix—O1—O1xxvi | 49.4 (3) |
O1xii—Cu1—O3xviii | 54.6 (3) | Si1—O1—Cu1xvi | 67.2 (4) |
O3xiii—Cu1—O3xviii | 79.3 (5) | Cu1xxxii—O1—Cu1xvi | 56.1 (2) |
O3xiv—Cu1—O3xviii | 100.5 (4) | Ba1xxx—O1—Cu1xvi | 128.1 (4) |
O1xv—Cu1—O3xviii | 49.0 (3) | Ba1xxix—O1—Cu1xvi | 115.2 (3) |
O1xvi—Cu1—O3xviii | 48.2 (3) | Si1—O1—Si1xxiv | 96.6 (5) |
O3xvii—Cu1—O3xviii | 70.8 (3) | Cu1xxxii—O1—Si1xxiv | 63.7 (3) |
O1xi—Cu1—Ba1xix | 137.8 (3) | Ba1xxx—O1—Si1xxiv | 73.3 (3) |
O1xii—Cu1—Ba1xix | 44.3 (3) | Ba1xxix—O1—Si1xxiv | 157.8 (3) |
O3xiii—Cu1—Ba1xix | 123.9 (3) | Cu1xvi—O1—Si1xxiv | 54.91 (18) |
O3xiv—Cu1—Ba1xix | 56.2 (3) | Si1xxvii—O2—Si1 | 150.7 (3) |
O1xv—Cu1—Ba1xix | 82.49 (18) | Si1xxvii—O2—Ba1xxix | 102.8 (4) |
O1xvi—Cu1—Ba1xix | 138.70 (19) | Si1—O2—Ba1xxix | 106.6 (4) |
O3xvii—Cu1—Ba1xix | 127.90 (17) | Si1xxii—O3—Cu1xxxiv | 118.7 (6) |
O3xviii—Cu1—Ba1xix | 90.53 (15) | Si1xxii—O3—Ba1ix | 118.8 (5) |
O1xi—Cu1—Ba1xx | 44.3 (3) | Cu1xxxiv—O3—Ba1ix | 109.7 (4) |
O1xii—Cu1—Ba1xx | 137.8 (3) | Ba1ix—O3—O3xxxvii | 56.1 (2) |
O3xiii—Cu1—Ba1xx | 56.2 (3) | Si1xxii—O3—Ba1vii | 97.3 (5) |
O3xiv—Cu1—Ba1xx | 123.9 (3) | Cu1xxxiv—O3—Ba1vii | 92.4 (4) |
O1xv—Cu1—Ba1xx | 138.70 (19) | Ba1ix—O3—Ba1vii | 116.3 (3) |
O1xvi—Cu1—Ba1xx | 82.49 (18) | Si1xxii—O3—Cu1xxxviii | 66.1 (4) |
O3xvii—Cu1—Ba1xx | 90.53 (15) | Cu1xxxiv—O3—Cu1xxxviii | 54.7 (2) |
O3xviii—Cu1—Ba1xx | 127.90 (17) | Ba1ix—O3—Cu1xxxviii | 128.2 (4) |
Ba1xix—Cu1—Ba1xx | 135.03 (2) | Ba1vii—O3—Cu1xxxviii | 113.6 (3) |
O1xi—Cu1—Ba1xxi | 125.7 (3) | Si1xxii—O3—Si1xxxv | 94.7 (5) |
O1xii—Cu1—Ba1xxi | 56.0 (3) | Cu1xxxiv—O3—Si1xxxv | 63.9 (3) |
O3xiii—Cu1—Ba1xxi | 42.1 (3) | Ba1ix—O3—Si1xxxv | 74.5 (3) |
O3xiv—Cu1—Ba1xxi | 138.0 (3) | Ba1vii—O3—Si1xxxv | 156.4 (3) |
O1xv—Cu1—Ba1xxi | 127.82 (19) | Cu1xxxviii—O3—Si1xxxv | 53.91 (18) |
O1xvi—Cu1—Ba1xxi | 89.07 (17) |
Symmetry codes: (i) −y+3/4, x+3/4, −z+5/4; (ii) y−1/4, x+3/4, z−1/4; (iii) −x+1/2, −y+2, z+1/2; (iv) x, −y+2, −z+1/2; (v) −y+5/4, −x+5/4, −z+5/4; (vi) y−3/4, −x+5/4, z−1/4; (vii) −x+1/2, −y+3/2, −z+1/2; (viii) x, −y+3/2, z+1/2; (ix) −x+1/2, −y+2, z−1/2; (x) x, −y+2, −z+3/2; (xi) y−3/4, x+1/4, z−3/4; (xii) −y+3/4, −x+1/4, z−3/4; (xiii) x−1/2, −y+1, z; (xiv) −x+1/2, y−1/2, z; (xv) x, y−1/2, −z+1; (xvi) −x, −y+1, −z+1; (xvii) y−3/4, −x+3/4, −z+1/4; (xviii) −y+3/4, x−1/4, −z+1/4; (xix) −x+1/2, −y+1, z−1/2; (xx) x−1/2, y−1/2, z−1/2; (xxi) x−1/2, y−1, −z+1/2; (xxii) −x+1/2, y, −z+1; (xxiii) −y+5/4, x+1/4, −z+7/4; (xxiv) −y+3/4, −x+3/4, −z+7/4; (xxv) y−3/4, −x+5/4, z+3/4; (xxvi) −x+1/2, −y+3/2, −z+3/2; (xxvii) y−1/4, −x+5/4, −z+7/4; (xxviii) −x+1, −y+3/2, z; (xxix) −y+5/4, x+3/4, z+1/4; (xxx) y−3/4, −x+3/4, −z+5/4; (xxxi) y−3/4, x+3/4, −z+7/4; (xxxii) y−1/4, x+3/4, z+3/4; (xxxiii) −y+3/4, x+1/4, z+3/4; (xxxiv) −x+1/2, y+1/2, z; (xxxv) −y+5/4, x+3/4, z−3/4; (xxxvi) y−1/4, −x+3/4, z−3/4; (xxxvii) −x+1/2, y, −z; (xxxviii) y+1/4, −x+3/4, −z+1/4. |
CuO6Si2·Ba | Dx = 4.151 Mg m−3 |
Mr = 353.06 | Mo Kα radiation, λ = 0.71069 Å |
Tetragonal, I4/mmm | Cell parameters from 988 reflections |
Hall symbol: -I 4 2 | θ = 3.4–24.8° |
a = 7.1104 (13) Å | µ = 11.08 mm−1 |
c = 11.175 (3) Å | T = 640 K |
V = 565.0 (2) Å3 | Cuboid, purple |
Z = 4 | 0.27 × 0.24 × 0.17 mm |
F(000) = 644 |
STOE IPDS diffractometer | 170 independent reflections |
Radiation source: fine-focus sealed tube | 135 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
rotation method scans | θmax = 24.8°, θmin = 3.4° |
Absorption correction: numerical via equivalents using STOE X-SHAPE and X-RED (Stoe & Cie, 1996) | h = 0→8 |
Tmin = 0.050, Tmax = 0.144 | k = 0→8 |
170 measured reflections | l = 0→13 |
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)] = 0.015 | w = 1/[σ2(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.025 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.53 e Å−3 |
170 reflections | Δρmin = −0.51 e Å−3 |
23 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0021 (2) |
CuO6Si2·Ba | Z = 4 |
Mr = 353.06 | Mo Kα radiation |
Tetragonal, I4/mmm | µ = 11.08 mm−1 |
a = 7.1104 (13) Å | T = 640 K |
c = 11.175 (3) Å | 0.27 × 0.24 × 0.17 mm |
V = 565.0 (2) Å3 |
STOE IPDS diffractometer | 170 independent reflections |
Absorption correction: numerical via equivalents using STOE X-SHAPE and X-RED (Stoe & Cie, 1996) | 135 reflections with I > 2σ(I) |
Tmin = 0.050, Tmax = 0.144 | Rint = 0.000 |
170 measured reflections |
R[F2 > 2σ(F2)] = 0.015 | 23 parameters |
wR(F2) = 0.025 | 0 restraints |
S = 1.02 | Δρmax = 0.53 e Å−3 |
170 reflections | Δρmin = −0.51 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) | |
Ba | 0.0000 | 0.5000 | 0.2500 | 0.0242 (3) | |
Cu | 0.0000 | 0.0000 | 0.12341 (16) | 0.0200 (5) | |
Si | 0.2756 (2) | 0.2756 (2) | 0.0000 | 0.0157 (7) | |
O1 | 0.2415 (14) | 0.5000 | 0.0239 (18) | 0.034 (6) | 0.50 |
O2 | 0.1916 (5) | 0.1916 (5) | 0.1209 (4) | 0.0392 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ba | 0.0238 (4) | 0.0238 (4) | 0.0250 (5) | 0.000 | 0.000 | 0.000 |
Cu | 0.0190 (7) | 0.0190 (7) | 0.0220 (11) | 0.000 | 0.000 | 0.000 |
Si | 0.0101 (9) | 0.0101 (9) | 0.0269 (14) | −0.0010 (14) | 0.000 | 0.000 |
O1 | 0.049 (5) | 0.010 (3) | 0.043 (19) | 0.000 | 0.022 (8) | 0.000 |
O2 | 0.0478 (19) | 0.0478 (19) | 0.022 (2) | −0.021 (2) | 0.0004 (17) | 0.0004 (17) |
Ba—O2i | 2.958 (2) | Si—O1x | 1.636 (4) |
Ba—O2ii | 2.958 (2) | Si—O1xii | 1.636 (4) |
Ba—O2 | 2.958 (2) | O1—O1x | 0.53 (4) |
Ba—O2iii | 2.958 (2) | O1—Sixiii | 1.636 (4) |
Ba—O2iv | 2.958 (2) | O1—O2iv | 2.472 (10) |
Ba—O2v | 2.958 (2) | O1—O2 | 2.472 (10) |
Ba—O2vi | 2.958 (2) | O1—O1iv | 2.599 (14) |
Ba—O2vii | 2.958 (2) | O1—O1xi | 2.599 (14) |
Ba—O1vii | 3.056 (18) | O1—O1xiii | 2.653 (17) |
Ba—O1i | 3.056 (18) | O1—O1xii | 2.653 (17) |
Ba—O1v | 3.056 (18) | O1—O2x | 2.748 (13) |
Ba—O1 | 3.056 (18) | O1—O2xiii | 2.748 (13) |
Cu—O2viii | 1.927 (5) | O2—O1xi | 2.472 (10) |
Cu—O2 | 1.927 (5) | O2—O2x | 2.701 (9) |
Cu—O2ix | 1.927 (5) | O2—O2ix | 2.725 (7) |
Cu—O2ii | 1.927 (5) | O2—O2ii | 2.725 (7) |
Si—O2x | 1.593 (5) | O2—O1x | 2.748 (13) |
Si—O2 | 1.593 (5) | O2—O1xii | 2.748 (13) |
Si—O1 | 1.636 (4) | O2—Baiii | 2.958 (2) |
Si—O1xi | 1.636 (4) | O2—O2iii | 3.116 (9) |
O2i—Ba—O2ii | 157.09 (18) | O2iii—Ba—O1v | 48.51 (10) |
O2i—Ba—O2 | 103.77 (7) | O2iv—Ba—O1v | 145.12 (17) |
O2ii—Ba—O2 | 54.85 (17) | O2v—Ba—O1v | 48.51 (10) |
O2i—Ba—O2iii | 54.85 (17) | O2vi—Ba—O1v | 81.68 (18) |
O2ii—Ba—O2iii | 103.77 (7) | O2vii—Ba—O1v | 145.12 (17) |
O2—Ba—O2iii | 63.58 (15) | O1vii—Ba—O1v | 133.2 (3) |
O2i—Ba—O2iv | 63.58 (15) | O1i—Ba—O1v | 68.4 (5) |
O2ii—Ba—O2iv | 121.59 (16) | O2i—Ba—O1 | 89.2 (2) |
O2—Ba—O2iv | 95.71 (18) | O2ii—Ba—O1 | 81.68 (18) |
O2iii—Ba—O2iv | 103.77 (7) | O2—Ba—O1 | 48.51 (10) |
O2i—Ba—O2v | 121.59 (16) | O2iii—Ba—O1 | 89.2 (2) |
O2ii—Ba—O2v | 63.58 (15) | O2iv—Ba—O1 | 48.51 (10) |
O2—Ba—O2v | 103.77 (7) | O2v—Ba—O1 | 145.12 (17) |
O2iii—Ba—O2v | 95.71 (18) | O2vi—Ba—O1 | 145.12 (17) |
O2iv—Ba—O2v | 157.09 (18) | O2vii—Ba—O1 | 81.68 (18) |
O2i—Ba—O2vi | 95.71 (18) | O1vii—Ba—O1 | 68.4 (5) |
O2ii—Ba—O2vi | 103.77 (7) | O1i—Ba—O1 | 133.2 (3) |
O2—Ba—O2vi | 157.09 (18) | O1v—Ba—O1 | 133.2 (3) |
O2iii—Ba—O2vi | 121.59 (16) | O2viii—Cu—O2 | 178.3 (3) |
O2iv—Ba—O2vi | 103.77 (7) | O2viii—Cu—O2ix | 89.988 (5) |
O2v—Ba—O2vi | 54.85 (17) | O2—Cu—O2ix | 89.988 (5) |
O2i—Ba—O2vii | 103.77 (7) | O2viii—Cu—O2ii | 89.988 (5) |
O2ii—Ba—O2vii | 95.71 (18) | O2—Cu—O2ii | 89.988 (5) |
O2—Ba—O2vii | 121.59 (16) | O2ix—Cu—O2ii | 178.3 (3) |
O2iii—Ba—O2vii | 157.09 (18) | O2x—Si—O2 | 116.0 (3) |
O2iv—Ba—O2vii | 54.85 (17) | O2x—Si—O1 | 116.6 (6) |
O2v—Ba—O2vii | 103.77 (7) | O2—Si—O1 | 99.9 (7) |
O2vi—Ba—O2vii | 63.58 (15) | O2x—Si—O1xi | 116.6 (6) |
O2i—Ba—O1vii | 145.12 (17) | O2—Si—O1xi | 99.9 (7) |
O2ii—Ba—O1vii | 48.51 (10) | O1—Si—O1xi | 105.2 (7) |
O2—Ba—O1vii | 81.68 (18) | O2x—Si—O1x | 99.9 (7) |
O2iii—Ba—O1vii | 145.12 (17) | O2—Si—O1x | 116.6 (6) |
O2iv—Ba—O1vii | 81.68 (18) | O1—Si—O1x | 18.8 (14) |
O2v—Ba—O1vii | 89.2 (2) | O1xi—Si—O1x | 108.4 (7) |
O2vi—Ba—O1vii | 89.2 (2) | O2x—Si—O1xii | 99.9 (7) |
O2vii—Ba—O1vii | 48.51 (10) | O2—Si—O1xii | 116.6 (6) |
O2i—Ba—O1i | 48.51 (10) | O1—Si—O1xii | 108.4 (7) |
O2ii—Ba—O1i | 145.12 (17) | O1xi—Si—O1xii | 18.8 (14) |
O2—Ba—O1i | 145.12 (17) | O1x—Si—O1xii | 105.2 (7) |
O2iii—Ba—O1i | 81.68 (18) | Sixiii—O1—Si | 154.6 (12) |
O2iv—Ba—O1i | 89.2 (2) | Sixiii—O1—Ba | 102.6 (6) |
O2v—Ba—O1i | 81.68 (18) | Si—O1—Ba | 102.6 (6) |
O2vi—Ba—O1i | 48.51 (10) | Si—O2—Cu | 122.9 (3) |
O2vii—Ba—O1i | 89.2 (2) | Si—O2—Ba | 107.96 (13) |
O1vii—Ba—O1i | 133.2 (3) | Cu—O2—Ba | 101.03 (13) |
O2i—Ba—O1v | 81.68 (18) | Si—O2—Baiii | 107.96 (13) |
O2ii—Ba—O1v | 89.2 (2) | Cu—O2—Baiii | 101.03 (13) |
O2—Ba—O1v | 89.2 (2) | Ba—O2—Baiii | 116.42 (15) |
Symmetry codes: (i) −y+1/2, x+1/2, −z+1/2; (ii) −y, x, z; (iii) −x+1/2, −y+1/2, −z+1/2; (iv) y, −x+1, z; (v) y−1/2, −x+1/2, −z+1/2; (vi) x−1/2, y+1/2, −z+1/2; (vii) −x, −y+1, z; (viii) −x, −y, z; (ix) y, −x, z; (x) x, y, −z; (xi) −y+1, x, z; (xii) −y+1, x, −z; (xiii) y, −x+1, −z. |
Experimental details
(bcso293) | (bcso640) | |
Crystal data | ||
Chemical formula | CuO6Si2·Ba | CuO6Si2·Ba |
Mr | 353.06 | 353.06 |
Crystal system, space group | Tetragonal, I41/acd | Tetragonal, I4/mmm |
Temperature (K) | 293 | 640 |
a, c (Å) | 10.0091 (16), 22.467 (6) | 7.1104 (13), 11.175 (3) |
V (Å3) | 2250.8 (8) | 565.0 (2) |
Z | 16 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 11.12 | 11.08 |
Crystal size (mm) | 0.17 × 0.16 × 0.11 | 0.27 × 0.24 × 0.17 |
Data collection | ||
Diffractometer | STOE IPDS diffractometer | STOE IPDS diffractometer |
Absorption correction | Numerical via equivalents using STOE X-SHAPE and X-RED (Stoe & Cie, 1996) | Numerical via equivalents using STOE X-SHAPE and X-RED (Stoe & Cie, 1996) |
Tmin, Tmax | 0.179, 0.288 | 0.050, 0.144 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1056, 1056, 523 | 170, 170, 135 |
Rint | 0.000 | 0.000 |
(sin θ/λ)max (Å−1) | 0.763 | 0.590 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.042, 1.26 | 0.015, 0.025, 1.02 |
No. of reflections | 1056 | 170 |
No. of parameters | 48 | 23 |
Δρmax, Δρmin (e Å−3) | 1.12, −2.04 | 0.53, −0.51 |
Computer programs: STOE X-RED, SHELXL97 (Sheldrick, 1997), ATOMS v5.1, WinGX v1.64.05 (Farrugia, 1999).