Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108032332/ku3001sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108032332/ku3001Isup2.hkl |
A mixture of Cd(OH)2 (Alfa Products, > 99%), (NH4)2HPO4 ( Loba Chemie, > 99%) and CuCl2.2H2O (Merck, > 99%) was transferred into teflon vessels and filled to approximately 70% of the inner volume with distilled water [quantities of reagents?]. The pH of the mixture was 5. The vessel was enclosed in a stainless steel autoclave and heated from room temperature to 493 K (4h), held at 493 K for 192 h, and finally spontaneously cooled to room temperature. At the end of the reaction the pH of the solvent was 6.
The title compound crystallized as blue prismatic crystals (yield ca 55%) of up to 100 µm in length together with green prismatic crystals of Cu2(PO4)OH (yield ca 35 %) and colourless crystals of NH4Cl (yield ca 10 %). All the reaction products were filtered off, washed thoroughly with distilled water and dried in air at room temperature.
Data collection: COLLECT (Nonius, 2002); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999); molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: publCIF (Westrip, 2008).
Cd2Cu(PO4)2 | Z = 1 |
Mr = 478.31 | F(000) = 219 |
Triclinic, P1 | Dx = 4.884 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.7982 (3) Å | Cell parameters from 3683 reflections |
b = 5.5801 (3) Å | θ = 1.0–30.0° |
c = 6.7217 (3) Å | µ = 10.22 mm−1 |
α = 74.266 (3)° | T = 295 K |
β = 86.330 (3)° | Prism, blue |
γ = 69.924 (3)° | 0.09 × 0.04 × 0.02 mm |
V = 162.62 (2) Å3 |
Nonius KappaCCD diffractomer | 805 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 747 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ϕ + ω scans | θmax = 28.3°, θmin = 4.0° |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | h = −6→6 |
Tmin = 0.460, Tmax = 0.822 | k = −7→7 |
1596 measured reflections | l = −8→8 |
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)] = 0.018 | w = 1/[σ2(Fo2) + (0.0187P)2 + 0.3359P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.043 | (Δ/σ)max < 0.001 |
S = 1.09 | Δρmax = 0.79 e Å−3 |
805 reflections | Δρmin = −0.59 e Å−3 |
63 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0054 (15) |
Cd2Cu(PO4)2 | γ = 69.924 (3)° |
Mr = 478.31 | V = 162.62 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 4.7982 (3) Å | Mo Kα radiation |
b = 5.5801 (3) Å | µ = 10.22 mm−1 |
c = 6.7217 (3) Å | T = 295 K |
α = 74.266 (3)° | 0.09 × 0.04 × 0.02 mm |
β = 86.330 (3)° |
Nonius KappaCCD diffractomer | 805 independent reflections |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | 747 reflections with I > 2σ(I) |
Tmin = 0.460, Tmax = 0.822 | Rint = 0.016 |
1596 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 63 parameters |
wR(F2) = 0.043 | 0 restraints |
S = 1.09 | Δρmax = 0.79 e Å−3 |
805 reflections | Δρmin = −0.59 e Å−3 |
Experimental. Qualitative chemical analyses were performed using a JEOL JSM-6400LV and JSM-6460LV scanning electron microscopes (SEM) connected with a LINK energy-dispersive X-ray analysis (EDX) unit. The presence of Cd, Cu and P was confirmed in all investigated samples. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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 | ||
Cu1 | 0.0000 | 0.0000 | 0.0000 | 0.00974 (14) | |
Cd1 | 0.29320 (5) | 0.28014 (5) | 0.31066 (4) | 0.01168 (11) | |
P1 | 0.37203 (18) | 0.31990 (16) | 0.78682 (13) | 0.00803 (18) | |
O1 | −0.2020 (5) | 0.3928 (5) | 0.3243 (4) | 0.0135 (5) | |
O2 | 0.3110 (5) | 0.6921 (5) | 0.1636 (4) | 0.0126 (5) | |
O3 | 0.2297 (5) | 0.2256 (5) | −0.0068 (4) | 0.0099 (5) | |
O4 | 0.3801 (5) | 0.1346 (5) | 0.6523 (4) | 0.0124 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0070 (3) | 0.0087 (3) | 0.0127 (3) | −0.0027 (2) | −0.0016 (2) | −0.0010 (2) |
Cd1 | 0.01194 (15) | 0.01009 (15) | 0.01117 (16) | −0.00144 (10) | −0.00111 (9) | −0.00252 (9) |
P1 | 0.0067 (4) | 0.0079 (4) | 0.0087 (4) | −0.0014 (3) | −0.0001 (3) | −0.0022 (3) |
O1 | 0.0108 (12) | 0.0074 (11) | 0.0175 (13) | −0.0001 (9) | −0.0013 (9) | 0.0009 (9) |
O2 | 0.0080 (11) | 0.0131 (12) | 0.0160 (13) | −0.0038 (9) | −0.0011 (9) | −0.0019 (10) |
O3 | 0.0102 (11) | 0.0115 (12) | 0.0090 (11) | −0.0043 (10) | 0.0001 (9) | −0.0032 (9) |
O4 | 0.0139 (12) | 0.0110 (12) | 0.0120 (12) | −0.0018 (10) | 0.0005 (9) | −0.0057 (9) |
Cu1—O3 | 1.928 (2) | P1—O2xiv | 1.553 (2) |
Cu1—O3i | 1.928 (2) | O1—P1xi | 1.525 (3) |
Cu1—O2ii | 1.952 (3) | O1—Cd1vii | 2.716 (2) |
Cu1—O2iii | 1.952 (3) | O1—Cd1xi | 3.359 (3) |
Cu1—O4iv | 2.966 (3) | O1—Cu1xiii | 3.892 (3) |
Cu1—O4v | 2.966 (3) | O1—Cd1v | 4.038 (3) |
Cu1—O1 | 3.370 (3) | O1—Cd1ii | 4.148 (3) |
Cu1—O1i | 3.370 (3) | O1—Cu1xvii | 4.365 (3) |
Cu1—O3vi | 3.470 (2) | O1—Cu1xv | 4.480 (3) |
Cu1—O3vii | 3.470 (2) | O1—Cd1xvii | 4.684 (3) |
Cu1—Cd1i | 3.5270 (3) | O1—Cd1ix | 4.926 (3) |
Cu1—Cd1 | 3.5270 (3) | O1—Cd1xviii | 5.567 (3) |
Cu1—O4viii | 3.644 (3) | O1—Cu1vii | 5.800 (3) |
Cu1—O4ix | 3.644 (3) | O1—Cd1iii | 5.861 (3) |
Cu1—Cd1ii | 3.7977 (4) | O2—P1xiv | 1.553 (2) |
Cu1—Cd1iii | 3.7977 (4) | O2—Cu1xiii | 1.952 (3) |
Cu1—O1ii | 3.892 (3) | O2—Cd1xii | 3.599 (3) |
Cu1—O1iii | 3.892 (3) | O2—Cd1xiii | 3.648 (3) |
Cu1—Cd1vi | 3.9408 (4) | O2—Cd1xiv | 4.181 (3) |
Cu1—Cd1vii | 3.9408 (4) | O2—Cu1xix | 4.184 (3) |
Cu1—O3ii | 4.089 (3) | O2—Cd1ii | 4.381 (3) |
Cd1—O4 | 2.232 (3) | O2—Cd1xi | 4.426 (3) |
Cd1—O1 | 2.242 (2) | O2—Cu1x | 4.486 (3) |
Cd1—O4ix | 2.263 (3) | O2—Cd1x | 4.517 (3) |
Cd1—O2 | 2.271 (2) | O2—Cd1xvii | 5.072 (3) |
Cd1—O3 | 2.288 (2) | O2—Cd1ix | 5.377 (3) |
Cd1—O1x | 2.716 (2) | O2—Cd1xx | 5.772 (3) |
Cd1—O3ii | 3.306 (3) | O3—P1iv | 1.548 (2) |
Cd1—O1xi | 3.359 (3) | O3—Cd1ii | 3.306 (3) |
Cd1—Cd1ix | 3.5019 (8) | O3—Cu1x | 3.470 (2) |
Cd1—O2xii | 3.599 (3) | O3—Cd1vi | 3.933 (3) |
Cd1—O2iii | 3.648 (3) | O3—Cu1xiii | 4.089 (3) |
Cd1—O4xi | 3.776 (3) | O3—Cd1xii | 4.207 (3) |
Cd1—Cu1xiii | 3.7977 (4) | O3—Cd1iv | 4.513 (2) |
Cd1—O3vi | 3.933 (3) | O3—Cd1vii | 4.798 (3) |
Cd1—Cu1x | 3.9408 (4) | O3—Cd1ix | 4.987 (3) |
Cd1—O1v | 4.038 (3) | O3—Cd1iii | 5.035 (3) |
Cd1—O4xiv | 4.146 (3) | O3—Cd1i | 5.203 (3) |
Cd1—O1ii | 4.148 (3) | O3—Cd1v | 5.688 (3) |
Cd1—O2xiv | 4.181 (3) | O3—Cd1x | 5.787 (3) |
Cd1—O3xii | 4.207 (3) | O4—Cd1ix | 2.263 (3) |
Cd1—Cd1xi | 4.2599 (5) | O4—Cu1xv | 2.966 (3) |
Cd1—O2ii | 4.381 (3) | O4—Cu1xxi | 3.644 (3) |
Cd1—O2xi | 4.426 (3) | O4—Cd1xi | 3.776 (3) |
Cd1—O3xv | 4.513 (2) | O4—Cd1xiv | 4.146 (3) |
Cd1—O2vii | 4.517 (3) | O4—Cd1v | 4.536 (3) |
Cd1—O4v | 4.536 (3) | O4—Cd1xv | 4.680 (3) |
Cd1—O4iv | 4.680 (3) | O4—Cd1x | 5.027 (3) |
Cd1—O1xvi | 4.684 (3) | O4—Cu1x | 5.217 (3) |
Cd1—Cd1ii | 4.7525 (5) | O4—Cu1xiii | 5.418 (3) |
P1—O1xi | 1.525 (3) | O4—Cd1vii | 5.545 (3) |
P1—O4 | 1.538 (3) | O4—Cu1xxii | 5.625 (3) |
P1—O3xv | 1.548 (3) | ||
O3—Cu1—O3i | 180.00 (8) | O2xii—Cd1—O4v | 112.59 (5) |
O3—Cu1—O2ii | 88.42 (10) | O2iii—Cd1—O4v | 47.17 (5) |
O3i—Cu1—O2ii | 91.58 (10) | O4xi—Cd1—O4v | 83.81 (5) |
O3—Cu1—O2iii | 91.58 (10) | O3vi—Cd1—O4v | 85.22 (5) |
O3i—Cu1—O2iii | 88.42 (10) | O1v—Cd1—O4v | 45.13 (5) |
O2ii—Cu1—O2iii | 180.0 | O4xiv—Cd1—O4v | 157.62 (6) |
O3—Cu1—O4iv | 56.49 (8) | O1ii—Cd1—O4v | 95.71 (5) |
O3i—Cu1—O4iv | 123.51 (8) | O2xiv—Cd1—O4v | 122.55 (5) |
O2ii—Cu1—O4iv | 83.92 (9) | O3xii—Cd1—O4v | 154.60 (5) |
O2iii—Cu1—O4iv | 96.08 (9) | O2ii—Cd1—O4v | 49.27 (5) |
O3i—Cu1—O4v | 56.49 (8) | O2xi—Cd1—O4v | 63.26 (5) |
O2ii—Cu1—O4v | 96.08 (9) | O3xv—Cd1—O4v | 91.23 (5) |
O2iii—Cu1—O4v | 83.92 (9) | O2vii—Cd1—O4v | 54.97 (5) |
O4iv—Cu1—O4v | 180.00 (10) | O4—Cd1—O4iv | 151.12 (9) |
O3—Cu1—O1 | 63.73 (8) | O1—Cd1—O4iv | 96.87 (8) |
O3i—Cu1—O1 | 116.27 (8) | O4ix—Cd1—O4iv | 73.86 (8) |
O2ii—Cu1—O1 | 78.23 (9) | O2—Cd1—O4iv | 88.61 (8) |
O2iii—Cu1—O1 | 101.77 (9) | O3—Cd1—O4iv | 12.16 (6) |
O4iv—Cu1—O1 | 117.66 (6) | O1x—Cd1—O4iv | 98.83 (7) |
O4v—Cu1—O1 | 62.34 (6) | O1v—Cd1—O4iv | 103.00 (5) |
O3—Cu1—O1i | 116.27 (8) | O4xiv—Cd1—O4iv | 112.69 (4) |
O3i—Cu1—O1i | 63.73 (8) | O1ii—Cd1—O4iv | 32.52 (4) |
O2iii—Cu1—O1i | 78.23 (9) | O2xiv—Cd1—O4iv | 149.68 (5) |
O4iv—Cu1—O1i | 62.34 (6) | O3xii—Cd1—O4iv | 78.43 (5) |
O1—Cu1—O1i | 180.00 (9) | O2ii—Cd1—O4iv | 43.57 (5) |
O3—Cu1—O3vi | 57.12 (10) | O2xi—Cd1—O4iv | 141.42 (5) |
O3i—Cu1—O3vi | 122.88 (10) | O3xv—Cd1—O4iv | 167.04 (4) |
O2ii—Cu1—O3vi | 134.74 (8) | O2vii—Cd1—O4iv | 87.41 (5) |
O2iii—Cu1—O3vi | 45.26 (8) | O4v—Cd1—O4iv | 80.12 (5) |
O4iv—Cu1—O3vi | 53.56 (7) | O4—Cd1—O1xvi | 83.89 (8) |
O4v—Cu1—O3vi | 126.44 (7) | O1—Cd1—O1xvi | 114.80 (8) |
O1—Cu1—O3vi | 106.11 (6) | O2—Cd1—O1xvi | 141.00 (7) |
O1i—Cu1—O3vi | 73.89 (6) | O3—Cd1—O1xvi | 71.71 (7) |
O3i—Cu1—O3vii | 57.12 (10) | O1x—Cd1—O1xvi | 94.10 (6) |
O2ii—Cu1—O3vii | 45.26 (8) | O3ii—Cd1—O1xvi | 134.67 (5) |
O4v—Cu1—O3vii | 53.56 (7) | O1xi—Cd1—O1xvi | 131.77 (4) |
O3vi—Cu1—O3vii | 180.0 | O2xii—Cd1—O1xvi | 75.43 (6) |
O3—Cu1—O4viii | 126.63 (8) | O2iii—Cd1—O1xvi | 31.42 (5) |
O3i—Cu1—O4viii | 53.37 (8) | O4xi—Cd1—O1xvi | 154.77 (5) |
O2ii—Cu1—O4viii | 42.11 (8) | O3vi—Cd1—O1xvi | 32.94 (5) |
O2iii—Cu1—O4viii | 137.89 (8) | O1v—Cd1—O1xvi | 49.16 (6) |
O4iv—Cu1—O4viii | 92.50 (7) | O4xiv—Cd1—O1xvi | 130.08 (5) |
O4v—Cu1—O4viii | 87.50 (7) | O1ii—Cd1—O1xvi | 99.23 (5) |
O1—Cu1—O4viii | 110.35 (6) | O2xiv—Cd1—O1xvi | 99.17 (6) |
O1i—Cu1—O4viii | 69.65 (6) | O3xii—Cd1—O1xvi | 112.02 (5) |
O3vi—Cu1—O4viii | 139.12 (6) | O2ii—Cd1—O1xvi | 87.92 (6) |
O3vii—Cu1—O4viii | 40.88 (6) | O2xi—Cd1—O1xvi | 108.62 (5) |
O3—Cu1—O4ix | 53.37 (8) | O3xv—Cd1—O1xvi | 100.91 (6) |
O3i—Cu1—O4ix | 126.63 (8) | O2vii—Cd1—O1xvi | 123.78 (5) |
O2iii—Cu1—O4ix | 42.11 (8) | O4v—Cd1—O1xvi | 71.19 (5) |
O4v—Cu1—O4ix | 92.50 (7) | O4iv—Cd1—O1xvi | 67.25 (5) |
O1—Cu1—O4ix | 69.65 (6) | O1xi—P1—O4 | 111.01 (14) |
O1i—Cu1—O4ix | 110.35 (6) | O1xi—P1—O3xv | 111.94 (14) |
O4viii—Cu1—O4ix | 180.00 (8) | O4—P1—O3xv | 107.58 (14) |
O3—Cu1—O1ii | 34.42 (8) | O1xi—P1—O2xiv | 106.53 (14) |
O3i—Cu1—O1ii | 145.58 (8) | O4—P1—O2xiv | 111.58 (14) |
O2ii—Cu1—O1ii | 60.66 (8) | O3xv—P1—O2xiv | 108.22 (14) |
O2iii—Cu1—O1ii | 119.34 (8) | Cd1xi—O1—Cu1xiii | 81.65 (5) |
O4iv—Cu1—O1ii | 40.43 (6) | Cu1—O1—Cu1xiii | 100.16 (6) |
O4v—Cu1—O1ii | 139.57 (6) | Cd1—O1—Cd1v | 101.62 (8) |
O1—Cu1—O1ii | 79.84 (6) | Cd1vii—O1—Cd1v | 58.63 (5) |
O1i—Cu1—O1ii | 100.16 (6) | Cd1xi—O1—Cd1v | 97.51 (6) |
O3vi—Cu1—O1ii | 75.55 (6) | Cd1—O1—Cd1ii | 91.09 (8) |
O3vii—Cu1—O1ii | 104.45 (6) | Cd1vii—O1—Cd1ii | 88.83 (7) |
O4viii—Cu1—O1ii | 93.12 (6) | Cd1xi—O1—Cd1ii | 126.78 (7) |
O4ix—Cu1—O1ii | 86.88 (6) | Cd1v—O1—Cd1ii | 132.11 (7) |
O3—Cu1—O1iii | 145.58 (8) | Cd1—O1—Cu1xvii | 139.66 (9) |
O2ii—Cu1—O1iii | 119.34 (8) | Cd1vii—O1—Cu1xvii | 59.57 (5) |
O4v—Cu1—O1iii | 40.43 (6) | Cd1xi—O1—Cu1xvii | 89.06 (6) |
O1—Cu1—O1iii | 100.16 (6) | Cu1—O1—Cu1xvii | 100.51 (6) |
O3vi—Cu1—O1iii | 104.45 (6) | Cu1xiii—O1—Cu1xvii | 70.79 (5) |
O3vii—Cu1—O1iii | 75.55 (6) | Cd1v—O1—Cu1xvii | 117.12 (6) |
O4ix—Cu1—O1iii | 93.12 (6) | Cd1ii—O1—Cu1xvii | 55.08 (4) |
O1ii—Cu1—O1iii | 180.00 (9) | Cd1vii—O1—Cd1ix | 121.44 (7) |
O3—Cu1—O3ii | 47.27 (9) | Cd1xi—O1—Cd1ix | 90.40 (6) |
O3i—Cu1—O3ii | 132.73 (9) | Cd1v—O1—Cd1ix | 63.83 (4) |
O2ii—Cu1—O3ii | 51.57 (8) | Cd1ii—O1—Cd1ix | 124.73 (6) |
O2iii—Cu1—O3ii | 128.43 (8) | Cd1—O1—Cd1xviii | 154.39 (9) |
O4iv—Cu1—O3ii | 85.32 (6) | Cd1vii—O1—Cd1xviii | 48.03 (4) |
O4v—Cu1—O3ii | 94.68 (6) | Cd1xi—O1—Cd1xviii | 59.02 (4) |
O1—Cu1—O3ii | 38.43 (5) | Cd1v—O1—Cd1xviii | 75.16 (5) |
O1i—Cu1—O3ii | 141.57 (5) | Cd1ii—O1—Cd1xviii | 110.10 (6) |
O3vi—Cu1—O3ii | 104.31 (6) | Cd1xvii—O1—Cd1xviii | 57.58 (4) |
O3vii—Cu1—O3ii | 75.69 (6) | Cd1ix—O1—Cd1xviii | 124.69 (5) |
O4viii—Cu1—O3ii | 93.27 (6) | Cu1—O1—Cu1vii | 55.79 (4) |
O4ix—Cu1—O3ii | 86.73 (6) | Cu1xiii—O1—Cu1vii | 121.73 (6) |
O1ii—Cu1—O3ii | 44.90 (5) | Cd1—O1—Cd1iii | 71.72 (6) |
O1iii—Cu1—O3ii | 135.10 (5) | Cd1vii—O1—Cd1iii | 79.23 (6) |
O4—Cd1—O1 | 95.88 (9) | Cd1xi—O1—Cd1iii | 135.23 (6) |
O4—Cd1—O4ix | 77.67 (10) | Cd1—O2—Cd1xiv | 93.55 (8) |
O1—Cd1—O4ix | 125.88 (9) | Cd1xii—O2—Cd1xiv | 119.34 (6) |
O4—Cd1—O2 | 115.22 (9) | Cd1xiii—O2—Cd1xiv | 52.60 (4) |
O1—Cd1—O2 | 97.50 (9) | Cu1xiii—O2—Cu1xix | 96.00 (8) |
O4ix—Cd1—O2 | 134.24 (9) | Cd1—O2—Cd1ii | 84.90 (7) |
O4—Cd1—O3 | 153.16 (9) | Cd1xii—O2—Cd1ii | 73.18 (5) |
O1—Cd1—O3 | 84.75 (9) | Cd1xiii—O2—Cd1ii | 122.67 (7) |
O4ix—Cd1—O3 | 80.30 (9) | Cd1xiv—O2—Cd1ii | 166.75 (7) |
O2—Cd1—O3 | 91.18 (9) | Cu1xix—O2—Cd1ii | 120.66 (6) |
O4—Cd1—O1x | 81.89 (9) | Cd1ii—O2—Cd1xi | 99.49 (5) |
O1—Cd1—O1x | 150.70 (11) | Cu1xiii—O2—Cu1x | 132.51 (10) |
O4ix—Cd1—O1x | 82.40 (8) | Cd1—O2—Cd1x | 82.89 (7) |
O2—Cd1—O1x | 58.48 (8) | Cd1xii—O2—Cd1x | 70.66 (5) |
O3—Cd1—O1x | 110.22 (8) | Cd1xiii—O2—Cd1x | 93.60 (6) |
O4—Cd1—O3ii | 134.13 (8) | Cd1xiv—O2—Cd1x | 58.50 (4) |
O1—Cd1—O3ii | 50.31 (8) | Cu1xix—O2—Cd1x | 51.59 (3) |
O4ix—Cd1—O3ii | 144.97 (8) | Cd1ii—O2—Cd1x | 134.00 (6) |
O2—Cd1—O3ii | 54.29 (7) | Cd1xi—O2—Cd1x | 117.61 (6) |
O3—Cd1—O3ii | 64.88 (9) | Cu1xiii—O2—Cu1 | 97.41 (8) |
O1x—Cd1—O3ii | 112.20 (7) | Cu1xix—O2—Cu1 | 136.47 (6) |
O4—Cd1—O1xi | 48.71 (7) | Cd1—O2—Cd1xvii | 102.25 (8) |
O1—Cd1—O1xi | 82.99 (9) | Cd1xii—O2—Cd1xvii | 129.93 (7) |
O4ix—Cd1—O1xi | 123.05 (8) | Cd1xiii—O2—Cd1xvii | 64.36 (4) |
O2—Cd1—O1xi | 70.70 (8) | Cd1xiv—O2—Cd1xvii | 93.22 (5) |
O3—Cd1—O1xi | 156.48 (7) | Cu1xix—O2—Cd1xvii | 120.33 (5) |
O1x—Cd1—O1xi | 73.60 (8) | Cd1ii—O2—Cd1xvii | 74.32 (4) |
O4—Cd1—O2xii | 140.14 (8) | Cu1x—O2—Cd1xvii | 158.46 (6) |
O1—Cd1—O2xii | 123.63 (8) | Cd1x—O2—Cd1xvii | 151.66 (6) |
O4ix—Cd1—O2xii | 74.92 (8) | Cu1—O2—Cd1xvii | 97.84 (5) |
O2—Cd1—O2xii | 68.43 (9) | Cd1xii—O2—Cd1ix | 111.38 (6) |
O3—Cd1—O2xii | 43.87 (7) | Cd1xiii—O2—Cd1ix | 121.95 (6) |
O1x—Cd1—O2xii | 66.35 (7) | Cd1xiv—O2—Cd1ix | 70.16 (4) |
O3ii—Cd1—O2xii | 82.12 (6) | Cu1xix—O2—Cd1ix | 111.06 (5) |
O1xi—Cd1—O2xii | 133.29 (6) | Cd1ii—O2—Cd1ix | 110.68 (5) |
O4—Cd1—O2iii | 103.51 (8) | Cd1xi—O2—Cd1ix | 74.49 (5) |
O1—Cd1—O2iii | 88.32 (8) | Cd1x—O2—Cd1ix | 59.93 (4) |
O4ix—Cd1—O2iii | 43.91 (7) | Cu1—O2—Cd1ix | 63.54 (3) |
O2—Cd1—O2iii | 139.86 (10) | Cd1xvii—O2—Cd1ix | 115.27 (5) |
O3—Cd1—O2iii | 49.66 (7) | Cu1xiii—O2—Cd1xx | 50.01 (7) |
O1x—Cd1—O2iii | 120.71 (7) | Cd1—O2—Cd1xx | 131.88 (9) |
O3ii—Cd1—O2iii | 104.95 (6) | Cd1xiii—O2—Cd1xx | 88.04 (5) |
O1xi—Cd1—O2iii | 149.29 (6) | Cd1xiv—O2—Cd1xx | 130.25 (5) |
O2xii—Cd1—O2iii | 75.33 (6) | Cu1xix—O2—Cd1xx | 64.28 (4) |
O4—Cd1—O4xi | 93.73 (8) | Cd1ii—O2—Cd1xx | 57.02 (4) |
O1—Cd1—O4xi | 40.29 (7) | Cd1xi—O2—Cd1xx | 137.47 (5) |
O4ix—Cd1—O4xi | 163.60 (10) | Cu1x—O2—Cd1xx | 87.77 (5) |
O2—Cd1—O4xi | 62.07 (7) | Cd1x—O2—Cd1xx | 102.22 (6) |
O3—Cd1—O4xi | 103.53 (8) | Cu1—O2—Cd1xx | 94.45 (5) |
O1x—Cd1—O4xi | 110.48 (7) | Cd1xvii—O2—Cd1xx | 94.93 (5) |
O3ii—Cd1—O4xi | 40.49 (6) | Cd1ix—O2—Cd1xx | 143.86 (5) |
O1xi—Cd1—O4xi | 55.11 (6) | Cu1—O3—Cd1ii | 89.01 (8) |
O2xii—Cd1—O4xi | 119.01 (6) | Cd1—O3—Cd1ii | 115.12 (9) |
O2iii—Cd1—O4xi | 127.54 (6) | Cu1—O3—Cu1x | 122.88 (10) |
O4—Cd1—Cu1xiii | 125.95 (7) | Cd1—O3—Cu1x | 83.68 (7) |
O1—Cd1—Cu1xiii | 75.38 (7) | Cd1ii—O3—Cu1x | 134.32 (8) |
O4ix—Cd1—Cu1xiii | 149.34 (6) | Cu1—O3—Cd1vi | 76.05 (7) |
O2—Cd1—Cu1xiii | 23.93 (6) | Cd1—O3—Cd1vi | 132.72 (9) |
O3—Cd1—Cu1xiii | 80.27 (6) | Cd1ii—O3—Cd1vi | 111.16 (7) |
O1x—Cd1—Cu1xiii | 82.35 (6) | Cu1x—O3—Cd1vi | 56.49 (4) |
O3ii—Cd1—Cu1xiii | 30.50 (4) | Cu1—O3—Cu1xiii | 132.73 (9) |
O1xi—Cd1—Cu1xiii | 77.24 (5) | Cd1—O3—Cu1xiii | 66.25 (6) |
O4—Cd1—O3vi | 113.58 (8) | Cd1ii—O3—Cu1xiii | 55.76 (4) |
O1—Cd1—O3vi | 122.20 (8) | Cu1x—O3—Cu1xiii | 104.31 (6) |
O4ix—Cd1—O3vi | 36.07 (7) | Cd1vi—O3—Cu1xiii | 141.72 (7) |
O2—Cd1—O3vi | 111.14 (8) | Cu1—O3—Cd1xii | 153.18 (10) |
O3—Cd1—O3vi | 47.28 (9) | Cd1—O3—Cd1xii | 93.54 (7) |
O1x—Cd1—O3vi | 84.58 (7) | Cd1ii—O3—Cd1xii | 78.38 (5) |
O1xi—Cd1—O3vi | 153.06 (5) | Cu1x—O3—Cd1xii | 58.36 (4) |
O2xii—Cd1—O3vi | 43.06 (5) | Cd1vi—O3—Cd1xii | 86.48 (5) |
O2iii—Cd1—O3vi | 38.49 (5) | Cu1xiii—O3—Cd1xii | 56.70 (4) |
O4xi—Cd1—O3vi | 150.81 (5) | Cu1—O3—Cd1iv | 85.25 (8) |
O4—Cd1—O1v | 54.71 (8) | Cd1—O3—Cd1iv | 161.46 (9) |
O1—Cd1—O1v | 78.38 (8) | Cd1ii—O3—Cd1iv | 63.86 (5) |
O4ix—Cd1—O1v | 53.87 (7) | Cu1x—O3—Cd1iv | 85.34 (6) |
O2—Cd1—O1v | 168.01 (7) | Cd1vi—O3—Cd1iv | 48.39 (4) |
O3—Cd1—O1v | 99.58 (7) | Cu1xiii—O3—Cd1iv | 102.33 (6) |
O1x—Cd1—O1v | 121.37 (5) | Cd1xii—O3—Cd1iv | 67.96 (4) |
O3ii—Cd1—O1v | 126.14 (6) | Cu1—O3—Cd1vii | 52.70 (6) |
O1xi—Cd1—O1v | 97.51 (6) | Cd1—O3—Cd1vii | 76.20 (6) |
O2xii—Cd1—O1v | 123.26 (6) | Cd1ii—O3—Cd1vii | 71.96 (5) |
O2iii—Cd1—O1v | 51.81 (5) | Cu1x—O3—Cd1vii | 152.72 (6) |
O4xi—Cd1—O1v | 109.77 (6) | Cd1vi—O3—Cd1vii | 128.75 (6) |
O3vi—Cd1—O1v | 80.31 (5) | Cu1xiii—O3—Cd1vii | 84.37 (5) |
O4—Cd1—O4xiv | 84.91 (8) | Cd1xii—O3—Cd1vii | 140.12 (6) |
O1—Cd1—O4xiv | 114.66 (7) | Cd1iv—O3—Cd1vii | 118.53 (5) |
O4ix—Cd1—O4xiv | 118.05 (9) | Cu1—O3—Cd1ix | 93.79 (8) |
O2—Cd1—O4xiv | 32.90 (7) | Cd1ii—O3—Cd1ix | 151.41 (7) |
O3—Cd1—O4xiv | 119.27 (7) | Cu1x—O3—Cd1ix | 65.65 (5) |
O1x—Cd1—O4xiv | 36.11 (6) | Cd1vi—O3—Cd1ix | 97.09 (5) |
O3ii—Cd1—O4xiv | 84.27 (6) | Cu1xiii—O3—Cd1ix | 103.95 (6) |
O1xi—Cd1—O4xiv | 50.21 (6) | Cd1xii—O3—Cd1ix | 108.63 (5) |
O2xii—Cd1—O4xiv | 83.08 (6) | Cd1iv—O3—Cd1ix | 144.71 (6) |
O2iii—Cd1—O4xiv | 154.88 (5) | Cd1vii—O3—Cd1ix | 87.24 (5) |
O4xi—Cd1—O4xiv | 74.38 (5) | Cd1—O3—Cd1iii | 91.36 (7) |
O3vi—Cd1—O4xiv | 116.43 (5) | Cd1ii—O3—Cd1iii | 130.03 (6) |
O1v—Cd1—O4xiv | 139.29 (5) | Cu1x—O3—Cd1iii | 87.54 (6) |
O4—Cd1—O1ii | 172.61 (7) | Cd1vi—O3—Cd1iii | 65.07 (4) |
O1—Cd1—O1ii | 88.91 (8) | Cu1xiii—O3—Cd1iii | 152.74 (6) |
O4ix—Cd1—O1ii | 104.05 (8) | Cd1xii—O3—Cd1iii | 144.66 (6) |
O2—Cd1—O1ii | 58.38 (8) | Cd1iv—O3—Cd1iii | 103.05 (5) |
O3—Cd1—O1ii | 32.81 (7) | Cd1vii—O3—Cd1iii | 74.89 (5) |
O1x—Cd1—O1ii | 91.17 (7) | Cd1ix—O3—Cd1iii | 58.28 (4) |
O3ii—Cd1—O1ii | 46.69 (6) | Cd1—O3—Cd1i | 137.10 (8) |
O1xi—Cd1—O1ii | 126.78 (7) | Cd1ii—O3—Cd1i | 78.49 (5) |
O2xii—Cd1—O1ii | 36.27 (5) | Cu1x—O3—Cd1i | 116.79 (6) |
O2iii—Cd1—O1ii | 82.21 (6) | Cd1vi—O3—Cd1i | 61.51 (4) |
O4xi—Cd1—O1ii | 86.28 (6) | Cu1xiii—O3—Cd1i | 132.83 (6) |
O3vi—Cd1—O1ii | 68.00 (6) | Cd1xii—O3—Cd1i | 129.36 (5) |
O1v—Cd1—O1ii | 132.11 (7) | Cd1iv—O3—Cd1i | 61.42 (4) |
O4xiv—Cd1—O1ii | 87.97 (5) | Cd1vii—O3—Cd1i | 69.87 (4) |
O4—Cd1—O2xiv | 31.43 (7) | Cd1ix—O3—Cd1i | 113.13 (5) |
O1—Cd1—O2xiv | 113.43 (8) | Cd1iii—O3—Cd1i | 55.28 (3) |
O4ix—Cd1—O2xiv | 88.47 (8) | Cu1—O3—Cd1v | 52.25 (6) |
O2—Cd1—O2xiv | 86.45 (8) | Cd1—O3—Cd1v | 61.03 (5) |
O3—Cd1—O2xiv | 161.82 (7) | Cd1ii—O3—Cd1v | 109.74 (6) |
O1x—Cd1—O2xiv | 53.66 (7) | Cu1x—O3—Cd1v | 115.63 (6) |
O3ii—Cd1—O2xiv | 126.15 (6) | Cd1vi—O3—Cd1v | 111.31 (5) |
O1xi—Cd1—O2xiv | 36.16 (6) | Cu1xiii—O3—Cd1v | 106.89 (5) |
O2xii—Cd1—O2xiv | 119.34 (6) | Cd1xii—O3—Cd1v | 154.52 (5) |
O2iii—Cd1—O2xiv | 127.40 (4) | Cd1iv—O3—Cd1v | 137.50 (5) |
O4xi—Cd1—O2xiv | 91.28 (6) | Cd1ix—O3—Cd1v | 52.93 (3) |
O3vi—Cd1—O2xiv | 117.32 (5) | Cd1iii—O3—Cd1v | 46.32 (3) |
O1v—Cd1—O2xiv | 84.94 (6) | Cd1i—O3—Cd1v | 76.08 (4) |
O4xiv—Cd1—O2xiv | 54.35 (5) | Cu1—O3—Cd1x | 144.58 (9) |
O1ii—Cd1—O2xiv | 141.19 (5) | Cd1—O3—Cd1x | 53.63 (5) |
O4—Cd1—O3xii | 113.67 (8) | Cd1ii—O3—Cd1x | 126.34 (6) |
O1—Cd1—O3xii | 126.45 (7) | Cd1vi—O3—Cd1x | 91.00 (5) |
O4ix—Cd1—O3xii | 104.22 (7) | Cu1xiii—O3—Cd1x | 76.29 (5) |
O2—Cd1—O3xii | 30.05 (7) | Cd1xii—O3—Cd1x | 54.02 (3) |
O3—Cd1—O3xii | 86.46 (7) | Cd1iv—O3—Cd1x | 110.71 (5) |
O1x—Cd1—O3xii | 35.57 (6) | Cd1vii—O3—Cd1x | 129.83 (5) |
O3ii—Cd1—O3xii | 78.38 (5) | Cd1ix—O3—Cd1x | 54.66 (3) |
O1xi—Cd1—O3xii | 84.80 (5) | Cd1iii—O3—Cd1x | 103.59 (5) |
O2xii—Cd1—O3xii | 48.56 (5) | Cd1i—O3—Cd1x | 149.84 (5) |
O2iii—Cd1—O3xii | 123.24 (5) | Cd1v—O3—Cd1x | 105.77 (4) |
O4xi—Cd1—O3xii | 91.99 (5) | Cd1—O4—Cu1xv | 131.99 (10) |
O3vi—Cd1—O3xii | 86.48 (5) | Cd1ix—O4—Cu1xv | 96.89 (9) |
O1v—Cd1—O3xii | 155.06 (5) | Cd1—O4—Cu1xxi | 135.45 (10) |
O4xiv—Cd1—O3xii | 34.68 (5) | Cd1ix—O4—Cu1xxi | 68.81 (7) |
O1ii—Cd1—O3xii | 58.96 (5) | Cu1xv—O4—Cu1xxi | 92.50 (7) |
O2xiv—Cd1—O3xii | 82.47 (5) | Cd1—O4—Cd1xi | 86.27 (8) |
O4—Cd1—O2ii | 140.40 (7) | Cd1ix—O4—Cd1xi | 163.60 (10) |
O1—Cd1—O2ii | 53.32 (7) | Cu1xv—O4—Cd1xi | 67.33 (5) |
O4ix—Cd1—O2ii | 99.68 (8) | Cu1xxi—O4—Cd1xi | 114.60 (7) |
O2—Cd1—O2ii | 95.10 (7) | Cd1—O4—Cd1xiv | 95.09 (8) |
O3—Cd1—O2ii | 31.43 (7) | Cd1ix—O4—Cd1xiv | 118.05 (9) |
O1x—Cd1—O2ii | 137.44 (6) | Cu1xv—O4—Cd1xiv | 113.75 (7) |
O3ii—Cd1—O2ii | 47.65 (5) | Cu1xxi—O4—Cd1xiv | 57.92 (4) |
O1xi—Cd1—O2ii | 132.53 (5) | Cd1—O4—Cd1xiv | 95.09 (8) |
O2xii—Cd1—O2ii | 73.18 (5) | Cd1ix—O4—Cd1xiv | 118.05 (9) |
O2iii—Cd1—O2ii | 57.33 (7) | Cu1xv—O4—Cd1xiv | 113.75 (7) |
O4xi—Cd1—O2ii | 77.95 (6) | Cu1xxi—O4—Cd1xiv | 57.92 (4) |
O3vi—Cd1—O2ii | 74.40 (5) | Cd1xi—O4—Cd1xiv | 74.38 (5) |
O1v—Cd1—O2ii | 91.42 (6) | Cd1—O4—Cd1v | 88.36 (8) |
O4xiv—Cd1—O2ii | 127.98 (5) | Cd1ix—O4—Cd1v | 82.52 (7) |
O1ii—Cd1—O2ii | 46.79 (5) | Cu1xv—O4—Cd1v | 51.01 (4) |
O2xiv—Cd1—O2ii | 166.75 (7) | Cu1xxi—O4—Cd1v | 130.67 (7) |
O3xii—Cd1—O2ii | 105.34 (5) | Cd1xi—O4—Cd1v | 83.81 (5) |
O4—Cd1—O2xi | 48.12 (7) | Cd1xiv—O4—Cd1v | 157.62 (6) |
O1—Cd1—O2xi | 48.24 (7) | Cd1—O4—Cd1xv | 151.12 (9) |
O4ix—Cd1—O2xi | 110.65 (8) | Cd1ix—O4—Cd1xv | 106.14 (8) |
O2—Cd1—O2xi | 109.17 (7) | Cu1xv—O4—Cd1xv | 48.87 (4) |
O3—Cd1—O2xi | 129.72 (7) | Cu1xxi—O4—Cd1xv | 54.82 (4) |
O1x—Cd1—O2xi | 119.71 (6) | Cd1xi—O4—Cd1xv | 67.41 (5) |
O3ii—Cd1—O2xi | 90.11 (6) | Cd1xiv—O4—Cd1xv | 67.31 (4) |
O1xi—Cd1—O2xi | 49.38 (5) | Cd1v—O4—Cd1xv | 99.88 (5) |
O2xii—Cd1—O2xi | 171.73 (7) | Cd1—O4—Cd1x | 71.21 (7) |
O2iii—Cd1—O2xi | 104.20 (5) | Cd1ix—O4—Cd1x | 76.23 (7) |
O4xi—Cd1—O2xi | 54.55 (6) | Cu1xv—O4—Cd1x | 156.75 (7) |
O3vi—Cd1—O2xi | 139.59 (5) | Cu1xxi—O4—Cd1x | 64.26 (4) |
O1v—Cd1—O2xi | 59.69 (5) | Cd1xi—O4—Cd1x | 120.02 (6) |
O4xiv—Cd1—O2xi | 99.01 (5) | Cd1xiv—O4—Cd1x | 54.32 (4) |
O1ii—Cd1—O2xi | 135.55 (5) | Cd1v—O4—Cd1x | 146.20 (6) |
O2xiv—Cd1—O2xi | 67.69 (4) | Cd1xv—O4—Cd1x | 111.05 (5) |
O3xii—Cd1—O2xi | 132.56 (5) | Cd1ix—O4—Cu1 | 84.81 (7) |
O2ii—Cd1—O2xi | 99.49 (5) | Cu1xv—O4—Cu1 | 108.05 (6) |
O4—Cd1—O3xv | 18.13 (7) | Cu1xxi—O4—Cu1 | 148.46 (6) |
O1—Cd1—O3xv | 83.12 (8) | Cd1xi—O4—Cu1 | 95.64 (6) |
O4ix—Cd1—O3xv | 95.58 (8) | Cd1xiv—O4—Cu1 | 128.09 (6) |
O2—Cd1—O3xv | 104.26 (8) | Cd1v—O4—Cu1 | 58.17 (4) |
O3—Cd1—O3xv | 161.46 (9) | Cd1xv—O4—Cu1 | 154.65 (6) |
O1x—Cd1—O3xv | 86.92 (7) | Cd1x—O4—Cu1 | 93.59 (5) |
O3ii—Cd1—O3xv | 116.14 (5) | Cd1ix—O4—Cu1x | 65.76 (6) |
O2xii—Cd1—O3xv | 152.38 (5) | Cu1xv—O4—Cu1x | 155.08 (7) |
O2iii—Cd1—O3xv | 115.88 (6) | Cu1xxi—O4—Cu1x | 97.08 (5) |
O4xi—Cd1—O3xv | 75.66 (6) | Cd1xi—O4—Cu1x | 127.41 (6) |
O3vi—Cd1—O3xv | 131.61 (4) | Cd1xiv—O4—Cu1x | 90.74 (5) |
O1v—Cd1—O3xv | 64.23 (5) | Cd1v—O4—Cu1x | 106.80 (5) |
O4xiv—Cd1—O3xv | 78.70 (5) | Cd1xv—O4—Cu1x | 150.38 (6) |
O1ii—Cd1—O3xv | 159.85 (5) | Cu1—O4—Cu1x | 54.95 (3) |
O2xiv—Cd1—O3xv | 33.33 (4) | Cd1ix—O4—Cu1xiii | 133.70 (8) |
O3xii—Cd1—O3xv | 112.04 (4) | Cu1xv—O4—Cu1xiii | 123.67 (7) |
O2ii—Cd1—O3xv | 134.42 (5) | Cu1xxi—O4—Cu1xiii | 124.04 (6) |
O2xi—Cd1—O3xv | 35.22 (4) | Cd1xi—O4—Cu1xiii | 59.16 (4) |
O4—Cd1—O2vii | 110.48 (8) | Cd1xiv—O4—Cu1xiii | 68.19 (4) |
O4ix—Cd1—O2vii | 136.15 (7) | Cd1v—O4—Cu1xiii | 104.92 (5) |
O2—Cd1—O2vii | 82.89 (7) | Cd1xv—O4—Cu1xiii | 116.94 (5) |
O3—Cd1—O2vii | 75.94 (7) | Cd1x—O4—Cu1xiii | 73.32 (4) |
O1x—Cd1—O2vii | 140.47 (6) | Cu1—O4—Cu1xiii | 63.48 (3) |
O3ii—Cd1—O2vii | 33.11 (5) | Cu1x—O4—Cu1xiii | 68.42 (4) |
O1xi—Cd1—O2vii | 86.73 (6) | Cd1—O4—Cd1vii | 59.13 (6) |
O2xii—Cd1—O2vii | 109.34 (5) | Cd1ix—O4—Cd1vii | 112.81 (8) |
O2iii—Cd1—O2vii | 93.60 (6) | Cu1xv—O4—Cd1vii | 72.88 (5) |
O4xi—Cd1—O2vii | 34.46 (5) | Cu1xxi—O4—Cd1vii | 165.37 (6) |
O3vi—Cd1—O2vii | 120.18 (5) | Cd1xi—O4—Cd1vii | 59.61 (4) |
O1v—Cd1—O2vii | 94.52 (6) | Cd1xiv—O4—Cd1vii | 126.88 (6) |
O4xiv—Cd1—O2vii | 105.70 (5) | Cd1xv—O4—Cd1vii | 112.30 (5) |
O1ii—Cd1—O2vii | 73.42 (6) | Cd1x—O4—Cd1vii | 130.33 (5) |
O2xiv—Cd1—O2vii | 121.50 (4) | Cu1x—O4—Cd1vii | 96.66 (4) |
O3xii—Cd1—O2vii | 110.41 (5) | Cu1xiii—O4—Cd1vii | 66.24 (4) |
O2ii—Cd1—O2vii | 46.00 (6) | Cd1—O4—Cu1xxii | 109.40 (8) |
O2xi—Cd1—O2vii | 62.39 (6) | Cd1ix—O4—Cu1xxii | 144.31 (8) |
O3xv—Cd1—O2vii | 95.55 (6) | Cu1xv—O4—Cu1xxii | 73.82 (5) |
O4—Cd1—O4v | 91.64 (8) | Cu1xxi—O4—Cu1xxii | 77.12 (5) |
O1—Cd1—O4v | 43.61 (7) | Cd1v—O4—Cu1xxii | 113.71 (5) |
O4ix—Cd1—O4v | 82.52 (7) | Cd1x—O4—Cu1xxii | 98.65 (5) |
O2—Cd1—O4v | 136.52 (7) | Cu1—O4—Cu1xxii | 130.88 (5) |
O3—Cd1—O4v | 70.35 (7) | Cu1x—O4—Cu1xxii | 130.76 (5) |
O1x—Cd1—O4v | 164.56 (6) | Cu1xiii—O4—Cu1xxii | 74.96 (4) |
O3ii—Cd1—O4v | 82.34 (5) | Cd1vii—O4—Cu1xxii | 97.54 (5) |
O1xi—Cd1—O4v | 112.39 (5) |
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y+1, −z; (iii) x, y−1, z; (iv) x, y, z−1; (v) −x, −y, −z+1; (vi) −x+1, −y, −z; (vii) x−1, y, z; (viii) x−1, y, z−1; (ix) −x+1, −y, −z+1; (x) x+1, y, z; (xi) −x, −y+1, −z+1; (xii) −x+1, −y+1, −z; (xiii) x, y+1, z; (xiv) −x+1, −y+1, −z+1; (xv) x, y, z+1; (xvi) x+1, y−1, z; (xvii) x−1, y+1, z; (xviii) −x−1, −y+1, −z+1; (xix) x+1, y+1, z; (xx) x, y+1, z−1; (xxi) x+1, y, z+1; (xxii) x, y+1, z+1. |
Experimental details
Crystal data | |
Chemical formula | Cd2Cu(PO4)2 |
Mr | 478.31 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 4.7982 (3), 5.5801 (3), 6.7217 (3) |
α, β, γ (°) | 74.266 (3), 86.330 (3), 69.924 (3) |
V (Å3) | 162.62 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 10.22 |
Crystal size (mm) | 0.09 × 0.04 × 0.02 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractomer |
Absorption correction | Multi-scan (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.460, 0.822 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1596, 805, 747 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.018, 0.043, 1.09 |
No. of reflections | 805 |
No. of parameters | 63 |
Δρmax, Δρmin (e Å−3) | 0.79, −0.59 |
Computer programs: COLLECT (Nonius, 2002), HKL SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski et al., 2003), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999), ATOMS (Dowty, 2000), publCIF (Westrip, 2008).
Cu1—O3 | 1.928 (2) | Cd1—O1 | 2.242 (2) |
Cu1—O3i | 1.928 (2) | Cd1—O4v | 2.263 (3) |
Cu1—O2ii | 1.952 (3) | Cd1—O2 | 2.271 (2) |
Cu1—O2iii | 1.952 (3) | Cd1—O3 | 2.288 (2) |
Cu1—Cd1i | 3.5270 (3) | Cd1—O1vi | 2.716 (2) |
Cu1—Cd1ii | 3.7977 (4) | Cd1—Cd1v | 3.5019 (8) |
Cu1—Cd1iv | 3.9408 (4) | Cd1—Cd1vii | 4.2599 (5) |
Cd1—O4 | 2.232 (3) | Cd1—Cd1ii | 4.7525 (5) |
O3—Cu1—O2ii | 88.42 (10) | O3i—Cu1—O2ii | 91.58 (10) |
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, −z+1; (vi) x+1, y, z; (vii) −x, −y+1, −z+1. |
Compound | a(Å) | b(Å) | c(Å) | α(o) | β(o) | γ(o) | V(Å3) |
Cu3(PO4)21 | 4.855 (1) | 5.288 (1) | 6.184 (1) | 72.34 (1) | 86.99 (1) | 68.54 (1) | 140.49 |
Cu3(PO4)21 | 4.848 (1) | 5.280 (1) | 6.183 (1) | 72.30 (1) | 86.90 (1) | 68.59 (1) | 140.08 |
Cu3(PO4)22 | 4.8537 (7) | 5.2855 (6) | 6.1821 (8) | 72.35 (1) | 86.99 (1) | 68.54 (1) | 140.35 |
Mg0.63Cu2.37(PO4)23 | 4.845 (3) | 5.265 (3) | 6.246 (2) | 71.98 (4) | 93.04 (4) | 111.42 (4) | 140.72 |
Red. Cell# | 4.845 (3) | 5.265 (3) | 6.246 (2) | 71.98 (4) | 86.959 | 68.579 | |
Cd2Cu(PO4)24 | 4.7982 (3) | 5.5801 (3) | 6.7217 (3) | 74.266 (3) | 86.330 (3) | 69.924 (3) | 162.62 |
Cu3(VO4)25 | 5.196 (4) | 5.355 (1) | 6.505 (4) | 69.22 (3) | 88.69 (4) | 68.08 (3) | 155.73 |
Cu3(AsO4)26 | 5.046 (2) | 5.417 (2) | 6.354 (2) | 70.61 (2) | 86.52 (2) | 68.43 (2) | 151.98 |
Zn2Cu(AsO4)27 | 5.092 (2) | 6.695 (2) | 5.304 (2) | 110.16 (2) | 112.09 (2) | 86.74 (2) | 156.73 |
Red. Cell* | 5.092 (2) | 5.304 (2) | 6.695 (2) | 69.84 | 86.74 | 67.91 | |
Zn2Cu(AsO4)28 | 5.094 (1) | 6.752 (1) | 5.304 (1) | 111.0 (1) | 112.5 (1) | 86.0 (1) | 156.87 |
Red. Cell* | 5.094 (1) | 5.304 (1) | 6.752 (1) | 69 | 86 | 67.5 | |
Zn2Cu(AsO4)29 | 5.094 (5) | 6.752 (5) | 5.304 (5) | 111 | 112 | 86 | 157.47 |
Red. Cell* | 5.094 (5) | 5.304 (5) | 6.752 (5) | 69 | 86 | 68 |
Notes: (a) Transformation matrix 1: 1 0 0 / 0 -1 0 / 0 0 -1; (b) transformation matrix 2: 1 0 0 / 0 0 -1 / 0 1 0. References: (1) Forsyth et al. (1990); (2) Shoemaker et al. (1977); (3) Moqine et al. (1994); (4) this work; (5) Coing-Boyat (1982); (6) Effenberger (1988); (7) Keller et al. (1979); (8) Plieth & Sänger (1967); (9) Calvo & Leung (1969). |
Natural and synthetic metal phosphates, arsenates and vanadates often form tetrahedral–octahedral framework structures with potentially interesting properties (e.g. ion conductivity, ion exchange and catalytic activities). An ongoing comprehensive study of the hydrothermal synthesis, crystallography and properties of phosphate(V), arsenate(V) and vanadate(V) compounds in the insufficiently known system M1O–M2O–X2O5–H2O (M1 = Sr2+, Cd2+ and Ba2+; M2 = Mg2+, Co2+, Ni2+, Cu2+ and Zn2+; and X = P5+, As5+ and V5+) yielded a large number of new M12+–, M22+– and M1–M2–(H–) phosphates, arsenates and vanadates (Mihajlović & Effenberger, 2004, 2006; Mihajlović, Libowitzky & Effenberger, 2004; Mihajlović, Kolitsch & Effenberger, 2004; Đorđević, Šutović et al., 2008; Đorđević, Karanović, & Tillmanns, 2008; Đorđević & Karanović, 2008; Đordević, 2008a,b), which were characterized structurally and, in part, also by spectroscopic techniques. The present contribution reports the hydrothermal synthesis and crystal structure of the novel compound dicadmium copper(II) bis[phosphate(V)], Cd2Cu(PO4)2.
Cd2Cu(PO4)2 is isomorphous with only five compounds, namely two phosphates, two arsenates and one vanadate [structure prototype Cu3(PO4)2 (Forsyth et al., 1990; Shoemaker et al., 1977), (Mg0.21,Cu0.79)3(PO4)2 (Moqine et al., 1994), Cu3(AsO4)2 (Effenberger, 1988), Zn2Cu(AsO4)2 (mineral stranskiite; Plieth & Sänger, 1967; Calvo & Leung, 1969; Keller, et al., 1979) and Cu3(VO4)2 (mineral mcbirneyite; (Coing-Boyat, 1982)]. All compounds crystallize in the space group P1 and have the general formula M12M2(XO4)2 (M1/M2 = Cd2+, Cu2+, Mg2+ and Zn2+, and X = As5+, P5+ and V5+; Table 1). It is interesting that the crystal structure of Cd2Cu(PO4)2 is different from that of monoclinic Cd1.35Cu1.65(PO4)2, which has a very similar chemical composition (Müller-Buschbaum & Münchau, 1996). The crystal structure of Cd2Cu(PO4)2 consists of [Cu(PO4)2]n chains, running along the [100] direction, interconnected by double chains of CdO6 polyhedra extending in the same direction (Fig. 1). Very similar [Cu(PO4)2]n chains have been described in the crystal structures of Ba2Cu(PO4)2.H2O (Effenberger, 1999), Ba2Cu(PO4)2 (Etheredge & Hwu, 1996) and Sr2Cu(PO4)2 (Johannes et al., 2006).
The Cu atom, located on an inversion centre (M2 position), is coordinated by four O atoms with an average Cu1—O bond distance of 1.941 (3) Å, forming a slightly distorted square-planar coordination [the O2ii—Cu1—O3 and O2ii—Cu1—O3i bond angles are 88.42 (10) and 91.58 (10)°; symmetry codes: (i) -x, -y, -z; (ii) -x, -y + 1, -z]. All four O atoms (O2 × 2 and O3 × 2) of the CuO4 squares are triply coordinated, bridging Cd1, Cu1 and P1 atoms. The P atom exhibits the usual tetrahedral coordination, with a mean P1—O distance of 1.541 (3) Å. The CuO4 squares and PO4 tetrahedra generate [Cu(PO4)2]n chains along the a axis (Fig. 1a).
Similar to other isomorphous compounds, the M1 cation (M1 = Cd) is situated in the general position. However, it is surrounded by six not five O atoms, forming a (5+1)-coordination polyhedron, which can be described as an extremely distorted octahedron. Pairs of CdO6 polyhedra sharing an O4—O4i edge form Cd2O10 dimers (Fig. 1b) similar to the isolated M1O8 dimers in related structures. The exceptional characteristic of this structure is that the Cd2O10 dimers are further polymerized, sharing common vertices (O1 and its symmetry equivalents) in double chains [Cd2O10]n running along the a axis. In this way, every Cd polyhedron shares additionally two vertices with neighboring polyhedra. The neighboring [Cd2O10]n double chains are interconnected by PO4 tetrahedra, which are linked to both CdO6 and CuO4 polyhedra. In addition to atom P1, atoms O1 and O4 are bonded to two Cd1 atoms, and O2 and O3 to one Cd1 and one Cu1 atoms (Fig. 2).
Excluding the sixth O atom [O1vi; symmetry code: (vi) x+1, y, z] of the CdO6 polyhedron, the average Cd1—O bond length is 2.259 (2) Å. The sixth O atom, located at a Cd1—O1vi distance of 2.716 (2) Å, contributes to the bond valence by approximately 5.5%. Taking into account the contribution of the five O atoms only, atom Cd1is undersaturated, i.e. νij(Cd1) is 1.92 valence units (v.u.). Including the sixth O atom, O1viνij(Cd1) increase to 2.02 v.u. The bond valence calculated according to the formula suggested by Brown and Altermatt (1985) for O1 shows that O1 is also undersaturated, i.e. νij(O1) is 1.80 v.u. This could indicate that vacancies exist at the O1 position, but the refinement showed that no such significant vacancies are present at this site [the refined occupancy was 1.05 (1)]. Therefore, the refinement was completed with a fixed atom site occupancy value of 1. Very probably, the undersaturation of O1 is due to the unusually long distance of 2.716 (2) Å. Hypothetically, if it is assumed that both the Cd1—O1 and the Cd1—O1vi distances are equal to 2.242 (2) Å, the calculated νij(O1) was becomes 2.09 v.u.
The dissimilarity in the geometry of M1 coordination between Cd2Cu(PO4)2 and the other isomorphous compounds is mostly due to the larger ionic radius of the Cd cation in comparison with that of Cu, Mg and Zn. The increase in the polymerization of the CdO6 polyhedra is accompanied by a decrease of the M1···M1 distances along the a axis. The Cd1···Cd1 distance along the chain extension is 4.7982 (3) Å, which is identical to the unit-cell parameter a and is shorter than the Cu···Cu distances in Cu3(PO4)2, Cu(AsO4)2 and Cu3(VO4)2, as well as the Zn···Zn distance in Zn2Cu(AsO4)2. Therefore, the unit-cell parameter a in Cd2Cu(PO4)2 achieves the shortest value amongst the isomorphous compounds, although it has the largest M1 cation and unit-cell volume (Table 1). In contrast, the b parameter has the largest value, while c is longer than those obtained for Cu3(PO4)2, Cu3(AsO4)2 and Cu3(VO4)2, but similar to c in Zn2Cu(AsO4)2.
An interesting aspect of the crystal structure is that it can also be described as PO4 tetrahedra sandwiched between two metal layers, which are situated near the (101) plane (Fig. 3). The two Cd1 cations in the dimer are located in the same (101) plane and separated from each other by 3.5198 (8) Å, and the Cd1—O4—Cd1v [symmetry code: (v) -x + 1, -y, -z + 1] angle is 102.33 (10)°. As mentioned above the Cd1···Cd1 distances between neighbours along the chain direction are 4.7982 (3) Å, and the shortest Cd1···Cd1 distance between neighbouring dimers positioned in the adjacent (101) plane is 4.2599 (5) Å. The shortest Cu1···Cd1 distances in the (101) plane are 3.5270 (3) and 3.7977 (4), and between two (101) planes is 3.9408 (4) Å. Because the Cu1 atoms are situated at the origin of the unit cell, the Cu1—Cu1 distances are equal to the lengths of unit-cell parameters a, b and c. All metal–metal distances are longer than the sum of the van der Waals radii [3.16 Å (2 × rCd), 2.98 Å (rCd + rCu = 1.58 + 1.40 = 2.98 Å) and 2.80 Å (2 × rCu), respectively (Bondi, 1964)].