Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811000274/mg2112sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536811000274/mg2112Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (Eu-O) = 0.003 Å Some non-H atoms missing
- R factor = 0.020
- wR factor = 0.044
- Data-to-parameter ratio = 23.7
checkCIF/PLATON results
No syntax errors found
Alert level C CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.99 <> 1.01 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_weight 1609.37 TEST: Calculate formula weight from _atom_site_* atom mass num sum Cd 112.41 2.00 224.82 Sb 121.75 5.00 608.75 Eu 151.96 5.00 759.80 O 16.00 0.00 0.00 O2- 0.00 1.00 0.00 Calculated formula weight 1593.37 PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:Cd2 Eu5 O1 Sb5 Atom count from the _atom_site data: Cd2 Eu5 Sb5 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G ALERT: Large difference may be due to a symmetry error - see SYMMG tests From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum Cd2 Eu5 O Sb5 TEST: Compare cell contents of formula and atom_site data WARNING: Unexpected atom type is in site list: O2- WARNING: Formula and atom_type_symbol element names mismatch. atom Z*formula cif sites diff Cd 8.00 8.00 0.00 Eu 20.00 20.00 0.00 O 4.00 0.00 4.00 Sb 20.00 20.00 0.00 WARNING: Site labels do not match formula elements PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large. 9.10 PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 1 PLAT794_ALERT_5_G Note: Tentative Bond Valency for Eu1 ....... 0.34 PLAT794_ALERT_5_G Note: Tentative Bond Valency for Eu2 ....... 0.51
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 7 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
The reagents were handled in an argon-filled glove box or under vacuum. All metals were with a stated purity higher than 99.9% (metal basis). They were purchased from Alfa, kept in the glove box, and were used as received.
A mixture of elemental Eu, Cd, Sb, and Pb (flux) in a molar ratio Eu:Cd:Sb:Pb = 2:1:2:10 was loaded in an alumina crucible. To prevent oxidation, the elements were weighed inside the glove box, but the mixture was accidently left in contact with ambient air for ca. 20–30 minutes, prior to sealing it under vacuum inside a silica tube. After that, the reaction mixture was put in a box-furnace and heated to 1273 K at a rate of 200 K h-1, homogenized at this temperature for 24 h, and then slowly cooled to 823 K at a rate of 5 K h-1. After an equilibration step at 823 K for 96 h, the crystals were separated from the Pb flux.
This reaction was aimed at obtaining large single-crystals of Eu11Cd6Sb12 (Saparov et al., 2008b), which was indeed the major product. However, alongside the needle crystals of Eu11Cd6Sb12, a small block-shaped crystal was also found. After the X-ray data were collected and the structure was solved, it turned out to be that of Eu5Cd2Sb5O. Other reactions using the same starting materials produced only the intermetallic phase, suggesting that the likely source of oxygen in this particular experiment was an unexpected partial oxidation. Attempts to increase the yield by using Eu2O3 as a deliberate source of oxygen were not successful and yielded multiple phases. Reactions aimed at obtaining the isostructural Eu5Cd2Sb5F (Saparov & Bobev, 2010) were successful – they were performed using CdF2 (Alfa), Eu, Cd, and Sb.
Because the determined unit-cell dimensions and space group suggested isomorphism with Ba5Cd2Sb5F (Saparov & Bobev, 2010), the diffraction data were readily refined using this model. The refinements smoothly converged to low conventional residuals and a flat difference Fourier map. The maximum peak and deepest hole were located 0.86 Å from Eu2 and 0.93 Å from O, respectively.
We note that when oxygen was excluded from the model, a residual peak of about 15 e- Å-3, located ca. 2.6–2.7 Å from Eu, remained in the difference Fourier map. Unlike the case of Ba2Cd3-δBi3O (Xia & Bobev, 2010), where the residual density lacked the typical oxoanion coordination and was modeled as a partially occupied Cd site, here the tetrahedral coordination by Eu matches very well the bonding requirements of O2-. The distances are reasonable and the oxygen site was fully occupied, as verified by freeing the site occupation factor, which led to an occupancy factor of 1.05 (2). In the final refinement cycles, all atoms were refined as fully occupied.
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Eu5Cd2Sb5O | F(000) = 2702 |
Mr = 1609.37 | Dx = 7.078 Mg m−3 |
Orthorhombic, Cmcm | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2c 2 | Cell parameters from 1092 reflections |
a = 4.7088 (5) Å | θ = 1.9–28.3° |
b = 21.965 (2) Å | µ = 31.92 mm−1 |
c = 14.5982 (15) Å | T = 120 K |
V = 1509.9 (3) Å3 | Block, black |
Z = 4 | 0.06 × 0.05 × 0.04 mm |
Bruker SMART APEX diffractometer | 1092 independent reflections |
Radiation source: fine-focus sealed tube | 1031 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ω scans | θmax = 28.3°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −6→6 |
Tmin = 0.161, Tmax = 0.279 | k = −28→28 |
10204 measured reflections | l = −19→19 |
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)] = 0.020 | w = 1/[σ2(Fo2) + (0.0174P)2 + 9.1021P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.044 | (Δ/σ)max = 0.001 |
S = 1.14 | Δρmax = 1.18 e Å−3 |
1092 reflections | Δρmin = −1.16 e Å−3 |
46 parameters | Extinction correction: SHELXTL (Bruker, 2002), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.000112 (14) |
Eu5Cd2Sb5O | V = 1509.9 (3) Å3 |
Mr = 1609.37 | Z = 4 |
Orthorhombic, Cmcm | Mo Kα radiation |
a = 4.7088 (5) Å | µ = 31.92 mm−1 |
b = 21.965 (2) Å | T = 120 K |
c = 14.5982 (15) Å | 0.06 × 0.05 × 0.04 mm |
Bruker SMART APEX diffractometer | 1092 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1031 reflections with I > 2σ(I) |
Tmin = 0.161, Tmax = 0.279 | Rint = 0.043 |
10204 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 46 parameters |
wR(F2) = 0.044 | 0 restraints |
S = 1.14 | Δρmax = 1.18 e Å−3 |
1092 reflections | Δρmin = −1.16 e Å−3 |
Experimental. Selected in the glove box, crystals were put in a Paratone N oil and cut to the desired dimensions. Chosen crystal was mounted on a tip of a glass fiber and quickly onto the goniometer. The crystal was kept under a cold nitrogen stream to protect from ambient conditions. Data collection is performed with four batch runs at ϕ = 0.00 ° (600 frames), at ϕ = 90.00 ° (600 frames), at ϕ = 180.00 ° (600 frames), and at ϕ = 270.00 (600 frames). Frame width = 0.30 ° in ω. Data are merged and treated with multi-scan absorption corrections. |
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 | ||
Eu1 | 0.0000 | 0.270509 (17) | 0.61940 (3) | 0.01436 (11) | |
Eu2 | 0.0000 | 0.10016 (3) | 0.2500 | 0.02034 (14) | |
Eu3 | 0.0000 | 0.90247 (2) | 0.2500 | 0.01461 (12) | |
Eu4 | 0.0000 | 0.0000 | 0.0000 | 0.01393 (12) | |
Sb1 | 0.0000 | 0.14937 (2) | 0.02068 (3) | 0.01333 (12) | |
Sb2 | 0.0000 | 0.49492 (2) | 0.15383 (3) | 0.01439 (12) | |
Sb3 | 0.0000 | 0.29312 (3) | 0.2500 | 0.01319 (15) | |
Cd | 0.0000 | 0.36803 (3) | 0.08509 (4) | 0.01540 (13) | |
O | 0.0000 | 0.6539 (3) | 0.2500 | 0.0058 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Eu1 | 0.01347 (18) | 0.01609 (19) | 0.01352 (19) | 0.000 | 0.000 | 0.00131 (14) |
Eu2 | 0.0283 (3) | 0.0179 (3) | 0.0148 (3) | 0.000 | 0.000 | 0.000 |
Eu3 | 0.0119 (2) | 0.0152 (3) | 0.0167 (3) | 0.000 | 0.000 | 0.000 |
Eu4 | 0.0145 (3) | 0.0151 (3) | 0.0122 (2) | 0.000 | 0.000 | −0.00009 (19) |
Sb1 | 0.0121 (2) | 0.0142 (2) | 0.0136 (2) | 0.000 | 0.000 | −0.00025 (18) |
Sb2 | 0.0137 (2) | 0.0171 (2) | 0.0123 (2) | 0.000 | 0.000 | 0.00042 (18) |
Sb3 | 0.0123 (3) | 0.0146 (3) | 0.0127 (3) | 0.000 | 0.000 | 0.000 |
Cd | 0.0137 (3) | 0.0186 (3) | 0.0140 (3) | 0.000 | 0.000 | −0.0012 (2) |
O | 0.006 (3) | 0.008 (3) | 0.003 (3) | 0.000 | 0.000 | 0.000 |
Eu1—Oi | 2.528 (4) | Sb1—Eu1xvi | 3.2738 (5) |
Eu1—Sb1ii | 3.2738 (5) | Sb1—Eu1xvii | 3.2738 (5) |
Eu1—Sb1iii | 3.2738 (5) | Sb1—Eu1vi | 3.3559 (7) |
Eu1—Sb3iv | 3.3363 (4) | Sb2—Sb2vi | 2.8078 (10) |
Eu1—Sb3v | 3.3363 (4) | Sb2—Cd | 2.9624 (8) |
Eu1—Sb1vi | 3.3559 (7) | Sb2—Eu4ix | 3.2556 (4) |
Eu2—Ovii | 2.634 (3) | Sb2—Eu4x | 3.2556 (4) |
Eu2—Oviii | 2.634 (3) | Sb2—Eu3viii | 3.4115 (5) |
Eu3—Sb3ix | 3.3634 (7) | Sb2—Eu3vii | 3.4115 (5) |
Eu3—Sb3x | 3.3634 (7) | Sb3—Cd | 2.9160 (7) |
Eu3—Sb2xi | 3.4115 (5) | Sb3—Cdvi | 2.9160 (7) |
Eu3—Sb2x | 3.4115 (5) | Sb3—Eu1xvii | 3.3363 (4) |
Eu3—Sb2ix | 3.4115 (5) | Sb3—Eu1iv | 3.3363 (4) |
Eu3—Sb2xii | 3.4115 (5) | Sb3—Eu1v | 3.3363 (4) |
Eu3—Cdix | 3.4512 (5) | Sb3—Eu1xvi | 3.3363 (4) |
Eu3—Cdxi | 3.4512 (5) | Sb3—Eu3vii | 3.3634 (7) |
Eu3—Cdxii | 3.4512 (5) | Sb3—Eu3viii | 3.3634 (7) |
Eu3—Cdx | 3.4512 (5) | Cd—Sb1xiii | 2.8413 (5) |
Eu4—Sb2xiii | 3.2556 (4) | Cd—Sb1xiv | 2.8413 (5) |
Eu4—Sb2vii | 3.2556 (4) | Cd—Eu3vii | 3.4512 (5) |
Eu4—Sb2xiv | 3.2556 (4) | Cd—Eu3viii | 3.4512 (5) |
Eu4—Sb2viii | 3.2556 (4) | O—Eu1i | 2.528 (4) |
Eu4—Sb1 | 3.2947 (6) | O—Eu1xviii | 2.528 (4) |
Eu4—Sb1xv | 3.2948 (6) | O—Eu2ix | 2.634 (3) |
Sb1—Cdxiii | 2.8413 (5) | O—Eu2x | 2.634 (3) |
Sb1—Cdxiv | 2.8413 (5) | ||
Oi—Eu1—Sb1ii | 88.79 (8) | Sb2xiii—Eu4—Sb2viii | 87.362 (15) |
Oi—Eu1—Sb1iii | 88.79 (8) | Sb2vii—Eu4—Sb2viii | 92.638 (15) |
Sb1ii—Eu1—Sb1iii | 91.972 (17) | Sb2xiv—Eu4—Sb2viii | 180.00 (2) |
Oi—Eu1—Sb3iv | 81.04 (8) | Sb2xiii—Eu4—Sb1 | 91.665 (10) |
Sb1ii—Eu1—Sb3iv | 88.237 (12) | Sb2vii—Eu4—Sb1 | 88.335 (10) |
Sb1iii—Eu1—Sb3iv | 169.821 (18) | Sb2xiv—Eu4—Sb1 | 91.665 (10) |
Oi—Eu1—Sb3v | 81.04 (8) | Sb2viii—Eu4—Sb1 | 88.335 (10) |
Sb1ii—Eu1—Sb3v | 169.821 (18) | Sb2xiii—Eu4—Sb1xv | 88.335 (10) |
Sb1iii—Eu1—Sb3v | 88.237 (12) | Sb2vii—Eu4—Sb1xv | 91.665 (10) |
Sb3iv—Eu1—Sb3v | 89.772 (15) | Sb2xiv—Eu4—Sb1xv | 88.335 (10) |
Oi—Eu1—Sb1vi | 168.60 (11) | Sb2viii—Eu4—Sb1xv | 91.665 (10) |
Sb1ii—Eu1—Sb1vi | 99.089 (14) | Sb1—Eu4—Sb1xv | 180.0 |
Sb1iii—Eu1—Sb1vi | 99.089 (14) | Sb2xiii—Eu4—Cdxiv | 100.934 (11) |
Sb3iv—Eu1—Sb1vi | 90.921 (15) | Sb2vii—Eu4—Cdxiv | 79.066 (11) |
Sb3v—Eu1—Sb1vi | 90.921 (15) | Sb2xiv—Eu4—Cdxiv | 47.500 (11) |
Oi—Eu1—Cdvi | 103.28 (11) | Sb2viii—Eu4—Cdxiv | 132.500 (11) |
Sb1ii—Eu1—Cdvi | 47.849 (9) | Sb1—Eu4—Cdxiv | 45.208 (9) |
Sb1iii—Eu1—Cdvi | 47.849 (9) | Sb1xv—Eu4—Cdxiv | 134.793 (9) |
Sb3iv—Eu1—Cdvi | 135.111 (8) | Sb2xiii—Eu4—Cdviii | 79.066 (11) |
Sb3v—Eu1—Cdvi | 135.111 (7) | Sb2vii—Eu4—Cdviii | 100.934 (11) |
Sb1vi—Eu1—Cdvi | 88.118 (17) | Sb2xiv—Eu4—Cdviii | 132.500 (11) |
Oi—Eu1—Eu1xix | 41.06 (11) | Sb2viii—Eu4—Cdviii | 47.500 (11) |
Sb1ii—Eu1—Eu1xix | 116.120 (11) | Sb1—Eu4—Cdviii | 134.792 (9) |
Sb1iii—Eu1—Eu1xix | 116.120 (11) | Sb1xv—Eu4—Cdviii | 45.207 (9) |
Sb3iv—Eu1—Eu1xix | 55.150 (8) | Cdxiv—Eu4—Cdviii | 180.000 (19) |
Sb3v—Eu1—Eu1xix | 55.150 (8) | Sb2xiii—Eu4—Cdxiii | 47.500 (11) |
Sb1vi—Eu1—Eu1xix | 127.542 (11) | Sb2vii—Eu4—Cdxiii | 132.500 (11) |
Cdvi—Eu1—Eu1xix | 144.340 (11) | Sb2xiv—Eu4—Cdxiii | 100.934 (11) |
Oi—Eu1—Cdiii | 127.77 (7) | Sb2viii—Eu4—Cdxiii | 79.066 (11) |
Sb1ii—Eu1—Cdiii | 143.242 (16) | Sb1—Eu4—Cdxiii | 45.208 (9) |
Sb1iii—Eu1—Cdiii | 85.892 (12) | Sb1xv—Eu4—Cdxiii | 134.793 (9) |
Sb3iv—Eu1—Cdiii | 99.991 (16) | Cdxiv—Eu4—Cdxiii | 73.486 (12) |
Sb3v—Eu1—Cdiii | 46.924 (12) | Cdviii—Eu4—Cdxiii | 106.514 (12) |
Sb1vi—Eu1—Cdiii | 45.530 (10) | Sb2xiii—Eu4—Cdvii | 132.500 (11) |
Cdvi—Eu1—Cdiii | 110.630 (13) | Sb2vii—Eu4—Cdvii | 47.500 (11) |
Eu1xix—Eu1—Cdiii | 97.418 (10) | Sb2xiv—Eu4—Cdvii | 79.066 (11) |
Oi—Eu1—Cdii | 127.77 (7) | Sb2viii—Eu4—Cdvii | 100.934 (11) |
Sb1ii—Eu1—Cdii | 85.892 (13) | Sb1—Eu4—Cdvii | 134.792 (9) |
Sb1iii—Eu1—Cdii | 143.242 (17) | Sb1xv—Eu4—Cdvii | 45.207 (9) |
Sb3iv—Eu1—Cdii | 46.924 (12) | Cdxiv—Eu4—Cdvii | 106.514 (12) |
Sb3v—Eu1—Cdii | 99.991 (17) | Cdviii—Eu4—Cdvii | 73.486 (12) |
Sb1vi—Eu1—Cdii | 45.530 (10) | Cdxiii—Eu4—Cdvii | 180.000 (19) |
Cdvi—Eu1—Cdii | 110.630 (13) | Sb2xiii—Eu4—Eu3xxiv | 127.751 (9) |
Eu1xix—Eu1—Cdii | 97.418 (10) | Sb2vii—Eu4—Eu3xxiv | 52.249 (9) |
Cdiii—Eu1—Cdii | 74.719 (14) | Sb2xiv—Eu4—Eu3xxiv | 127.751 (9) |
Oi—Eu1—Eu2iv | 37.31 (4) | Sb2viii—Eu4—Eu3xxiv | 52.249 (9) |
Sb1ii—Eu1—Eu2iv | 55.018 (11) | Sb1—Eu4—Eu3xxiv | 115.157 (11) |
Sb1iii—Eu1—Eu2iv | 104.009 (15) | Sb1xv—Eu4—Eu3xxiv | 64.843 (11) |
Sb3iv—Eu1—Eu2iv | 67.923 (14) | Cdxiv—Eu4—Eu3xxiv | 130.170 (8) |
Sb3v—Eu1—Eu2iv | 115.104 (14) | Cdviii—Eu4—Eu3xxiv | 49.830 (8) |
Sb1vi—Eu1—Eu2iv | 145.294 (6) | Cdxiii—Eu4—Eu3xxiv | 130.170 (8) |
Cdvi—Eu1—Eu2iv | 88.522 (13) | Cdvii—Eu4—Eu3xxiv | 49.830 (8) |
Eu1xix—Eu1—Eu2iv | 62.674 (7) | Sb2xiii—Eu4—Eu3xxv | 52.249 (9) |
Cdiii—Eu1—Eu2iv | 160.009 (14) | Sb2vii—Eu4—Eu3xxv | 127.751 (9) |
Cdii—Eu1—Eu2iv | 104.580 (11) | Sb2xiv—Eu4—Eu3xxv | 52.249 (9) |
Oi—Eu1—Eu2v | 37.31 (4) | Sb2viii—Eu4—Eu3xxv | 127.751 (9) |
Sb1ii—Eu1—Eu2v | 104.009 (15) | Sb1—Eu4—Eu3xxv | 64.843 (11) |
Sb1iii—Eu1—Eu2v | 55.018 (11) | Sb1xv—Eu4—Eu3xxv | 115.157 (11) |
Sb3iv—Eu1—Eu2v | 115.104 (13) | Cdxiv—Eu4—Eu3xxv | 49.830 (8) |
Sb3v—Eu1—Eu2v | 67.923 (14) | Cdviii—Eu4—Eu3xxv | 130.170 (8) |
Sb1vi—Eu1—Eu2v | 145.294 (6) | Cdxiii—Eu4—Eu3xxv | 49.830 (8) |
Cdvi—Eu1—Eu2v | 88.522 (12) | Cdvii—Eu4—Eu3xxv | 130.170 (8) |
Eu1xix—Eu1—Eu2v | 62.674 (6) | Eu3xxiv—Eu4—Eu3xxv | 180.000 (12) |
Cdiii—Eu1—Eu2v | 104.580 (11) | Cdxiii—Sb1—Cdxiv | 111.92 (3) |
Cdii—Eu1—Eu2v | 160.009 (14) | Cdxiii—Sb1—Eu1xvi | 155.15 (2) |
Eu2iv—Eu1—Eu2v | 69.070 (12) | Cdxiv—Sb1—Eu1xvi | 73.476 (13) |
Ovii—Eu2—Oviii | 126.7 (2) | Cdxiii—Sb1—Eu1xvii | 73.476 (13) |
Ovii—Eu2—Sb1 | 82.09 (3) | Cdxiv—Sb1—Eu1xvii | 155.15 (2) |
Oviii—Eu2—Sb1 | 82.09 (3) | Eu1xvi—Sb1—Eu1xvii | 91.971 (17) |
Ovii—Eu2—Sb1vi | 82.09 (3) | Cdxiii—Sb1—Eu4 | 79.416 (15) |
Oviii—Eu2—Sb1vi | 82.09 (3) | Cdxiv—Sb1—Eu4 | 79.416 (15) |
Sb1—Eu2—Sb1vi | 144.21 (2) | Eu1xvi—Sb1—Eu4 | 125.146 (12) |
Ovii—Eu2—Sb2viii | 151.15 (7) | Eu1xvii—Sb1—Eu4 | 125.146 (11) |
Oviii—Eu2—Sb2viii | 72.66 (11) | Cdxiii—Sb1—Eu1vi | 77.026 (16) |
Sb1—Eu2—Sb2viii | 79.950 (11) | Cdxiv—Sb1—Eu1vi | 77.026 (16) |
Sb1vi—Eu2—Sb2viii | 124.796 (11) | Eu1xvi—Sb1—Eu1vi | 80.908 (14) |
Ovii—Eu2—Sb2xx | 151.15 (7) | Eu1xvii—Sb1—Eu1vi | 80.908 (14) |
Oviii—Eu2—Sb2xx | 72.66 (11) | Eu4—Sb1—Eu1vi | 137.202 (18) |
Sb1—Eu2—Sb2xx | 124.795 (11) | Cdxiii—Sb1—Eu2 | 118.413 (15) |
Sb1vi—Eu2—Sb2xx | 79.951 (11) | Cdxiv—Sb1—Eu2 | 118.413 (15) |
Sb2viii—Eu2—Sb2xx | 46.098 (17) | Eu1xvi—Sb1—Eu2 | 75.300 (13) |
Ovii—Eu2—Sb2xxi | 72.66 (11) | Eu1xvii—Sb1—Eu2 | 75.300 (13) |
Oviii—Eu2—Sb2xxi | 151.15 (7) | Eu4—Sb1—Eu2 | 77.364 (14) |
Sb1—Eu2—Sb2xxi | 124.795 (11) | Eu1vi—Sb1—Eu2 | 145.435 (19) |
Sb1vi—Eu2—Sb2xxi | 79.951 (11) | Sb2vi—Sb2—Cd | 109.800 (15) |
Sb2viii—Eu2—Sb2xxi | 99.72 (2) | Sb2vi—Sb2—Eu4ix | 133.614 (8) |
Sb2xx—Eu2—Sb2xxi | 82.082 (16) | Cd—Sb2—Eu4ix | 78.379 (13) |
Ovii—Eu2—Sb2vii | 72.66 (11) | Sb2vi—Sb2—Eu4x | 133.614 (8) |
Oviii—Eu2—Sb2vii | 151.15 (7) | Cd—Sb2—Eu4x | 78.379 (13) |
Sb1—Eu2—Sb2vii | 79.950 (11) | Eu4ix—Sb2—Eu4x | 92.637 (15) |
Sb1vi—Eu2—Sb2vii | 124.796 (11) | Sb2vi—Sb2—Eu3viii | 65.699 (9) |
Sb2viii—Eu2—Sb2vii | 82.082 (17) | Cd—Sb2—Eu3viii | 65.122 (14) |
Sb2xx—Eu2—Sb2vii | 99.72 (2) | Eu4ix—Sb2—Eu3viii | 78.764 (8) |
Sb2xxi—Eu2—Sb2vii | 46.098 (17) | Eu4x—Sb2—Eu3viii | 143.452 (18) |
Ovii—Eu2—Eu1iv | 35.58 (8) | Sb2vi—Sb2—Eu3vii | 65.699 (9) |
Oviii—Eu2—Eu1iv | 101.55 (11) | Cd—Sb2—Eu3vii | 65.122 (14) |
Sb1—Eu2—Eu1iv | 103.103 (14) | Eu4ix—Sb2—Eu3vii | 143.452 (18) |
Sb1vi—Eu2—Eu1iv | 49.682 (9) | Eu4x—Sb2—Eu3vii | 78.764 (8) |
Sb2viii—Eu2—Eu1iv | 173.179 (9) | Eu3viii—Sb2—Eu3vii | 87.282 (17) |
Sb2xx—Eu2—Eu1iv | 129.306 (11) | Sb2vi—Sb2—Eu2x | 66.952 (9) |
Sb2xxi—Eu2—Eu1iv | 83.628 (11) | Cd—Sb2—Eu2x | 137.661 (10) |
Sb2vii—Eu2—Eu1iv | 104.387 (9) | Eu4ix—Sb2—Eu2x | 136.289 (17) |
Ovii—Eu2—Eu1xvi | 35.58 (8) | Eu4x—Sb2—Eu2x | 76.887 (8) |
Oviii—Eu2—Eu1xvi | 101.55 (11) | Eu3viii—Sb2—Eu2x | 132.515 (16) |
Sb1—Eu2—Eu1xvi | 49.683 (9) | Eu3vii—Sb2—Eu2x | 76.673 (13) |
Sb1vi—Eu2—Eu1xvi | 103.102 (15) | Sb2vi—Sb2—Eu2ix | 66.952 (8) |
Sb2viii—Eu2—Eu1xvi | 129.306 (11) | Cd—Sb2—Eu2ix | 137.661 (10) |
Sb2xx—Eu2—Eu1xvi | 173.179 (9) | Eu4ix—Sb2—Eu2ix | 76.887 (7) |
Sb2xxi—Eu2—Eu1xvi | 104.387 (10) | Eu4x—Sb2—Eu2ix | 136.289 (17) |
Sb2vii—Eu2—Eu1xvi | 83.628 (11) | Eu3viii—Sb2—Eu2ix | 76.673 (14) |
Eu1iv—Eu2—Eu1xvi | 54.653 (13) | Eu3vii—Sb2—Eu2ix | 132.515 (16) |
Ovii—Eu2—Eu1v | 101.55 (11) | Eu2x—Sb2—Eu2ix | 82.083 (17) |
Oviii—Eu2—Eu1v | 35.58 (8) | Cd—Sb3—Cdvi | 111.30 (3) |
Sb1—Eu2—Eu1v | 103.103 (15) | Cd—Sb3—Eu1xvii | 76.384 (11) |
Sb1vi—Eu2—Eu1v | 49.682 (9) | Cdvi—Sb3—Eu1xvii | 135.084 (7) |
Sb2viii—Eu2—Eu1v | 104.387 (9) | Cd—Sb3—Eu1iv | 135.084 (7) |
Sb2xx—Eu2—Eu1v | 83.628 (11) | Cdvi—Sb3—Eu1iv | 76.384 (11) |
Sb2xxi—Eu2—Eu1v | 129.306 (11) | Eu1xvii—Sb3—Eu1iv | 130.47 (3) |
Sb2vii—Eu2—Eu1v | 173.179 (9) | Cd—Sb3—Eu1v | 135.084 (7) |
Eu1iv—Eu2—Eu1v | 69.069 (12) | Cdvi—Sb3—Eu1v | 76.384 (12) |
Eu1xvi—Eu2—Eu1v | 93.682 (16) | Eu1xvii—Sb3—Eu1v | 69.701 (15) |
Ovii—Eu2—Eu1xvii | 101.55 (11) | Eu1iv—Sb3—Eu1v | 89.770 (15) |
Oviii—Eu2—Eu1xvii | 35.58 (8) | Cd—Sb3—Eu1xvi | 76.384 (11) |
Sb1—Eu2—Eu1xvii | 49.683 (9) | Cdvi—Sb3—Eu1xvi | 135.084 (7) |
Sb1vi—Eu2—Eu1xvii | 103.102 (14) | Eu1xvii—Sb3—Eu1xvi | 89.770 (15) |
Sb2viii—Eu2—Eu1xvii | 83.628 (11) | Eu1iv—Sb3—Eu1xvi | 69.701 (15) |
Sb2xx—Eu2—Eu1xvii | 104.387 (9) | Eu1v—Sb3—Eu1xvi | 130.47 (3) |
Sb2xxi—Eu2—Eu1xvii | 173.179 (9) | Cd—Sb3—Eu3vii | 66.237 (13) |
Sb2vii—Eu2—Eu1xvii | 129.306 (11) | Cdvi—Sb3—Eu3vii | 66.236 (13) |
Eu1iv—Eu2—Eu1xvii | 93.682 (16) | Eu1xvii—Sb3—Eu3vii | 142.479 (13) |
Eu1xvi—Eu2—Eu1xvii | 69.069 (12) | Eu1iv—Sb3—Eu3vii | 78.764 (10) |
Eu1v—Eu2—Eu1xvii | 54.653 (13) | Eu1v—Sb3—Eu3vii | 142.479 (13) |
Sb3ix—Eu3—Sb3x | 88.85 (2) | Eu1xvi—Sb3—Eu3vii | 78.764 (10) |
Sb3ix—Eu3—Sb2xi | 155.259 (10) | Cd—Sb3—Eu3viii | 66.237 (13) |
Sb3x—Eu3—Sb2xi | 86.675 (12) | Cdvi—Sb3—Eu3viii | 66.236 (14) |
Sb3ix—Eu3—Sb2x | 155.259 (10) | Eu1xvii—Sb3—Eu3viii | 78.764 (10) |
Sb3x—Eu3—Sb2x | 86.675 (12) | Eu1iv—Sb3—Eu3viii | 142.479 (13) |
Sb2xi—Eu3—Sb2x | 48.601 (18) | Eu1v—Sb3—Eu3viii | 78.764 (10) |
Sb3ix—Eu3—Sb2ix | 86.675 (12) | Eu1xvi—Sb3—Eu3viii | 142.479 (13) |
Sb3x—Eu3—Sb2ix | 155.259 (10) | Eu3vii—Sb3—Eu3viii | 88.86 (2) |
Sb2xi—Eu3—Sb2ix | 106.94 (2) | Sb1xiii—Cd—Sb1xiv | 111.92 (3) |
Sb2x—Eu3—Sb2ix | 87.283 (17) | Sb1xiii—Cd—Sb3 | 111.885 (17) |
Sb3ix—Eu3—Sb2xii | 86.675 (12) | Sb1xiv—Cd—Sb3 | 111.885 (17) |
Sb3x—Eu3—Sb2xii | 155.259 (10) | Sb1xiii—Cd—Sb2 | 108.095 (17) |
Sb2xi—Eu3—Sb2xii | 87.283 (17) | Sb1xiv—Cd—Sb2 | 108.095 (17) |
Sb2x—Eu3—Sb2xii | 106.94 (2) | Sb3—Cd—Sb2 | 104.55 (2) |
Sb2ix—Eu3—Sb2xii | 48.601 (18) | Sb1xiii—Cd—Eu3vii | 166.858 (18) |
Sb3ix—Eu3—Cdix | 50.649 (11) | Sb1xiv—Cd—Eu3vii | 80.981 (12) |
Sb3x—Eu3—Cdix | 108.724 (16) | Sb3—Cd—Eu3vii | 63.115 (14) |
Sb2xi—Eu3—Cdix | 152.666 (19) | Sb2—Cd—Eu3vii | 63.735 (14) |
Sb2x—Eu3—Cdix | 108.315 (13) | Sb1xiii—Cd—Eu3viii | 80.981 (12) |
Sb2ix—Eu3—Cdix | 51.142 (13) | Sb1xiv—Cd—Eu3viii | 166.858 (18) |
Sb2xii—Eu3—Cdix | 86.946 (12) | Sb3—Cd—Eu3viii | 63.115 (14) |
Sb3ix—Eu3—Cdxi | 108.724 (17) | Sb2—Cd—Eu3viii | 63.735 (14) |
Sb3x—Eu3—Cdxi | 50.649 (11) | Eu3vii—Cd—Eu3viii | 86.030 (15) |
Sb2xi—Eu3—Cdxi | 51.142 (13) | Sb1xiii—Cd—Eu1vi | 58.674 (13) |
Sb2x—Eu3—Cdxi | 86.946 (12) | Sb1xiv—Cd—Eu1vi | 58.674 (13) |
Sb2ix—Eu3—Cdxi | 152.666 (19) | Sb3—Cd—Eu1vi | 109.99 (2) |
Sb2xii—Eu3—Cdxi | 108.315 (14) | Sb2—Cd—Eu1vi | 145.46 (2) |
Cdix—Eu3—Cdxi | 154.68 (3) | Eu3vii—Cd—Eu1vi | 133.990 (11) |
Sb3ix—Eu3—Cdxii | 50.649 (11) | Eu3viii—Cd—Eu1vi | 133.990 (11) |
Sb3x—Eu3—Cdxii | 108.724 (17) | Sb1xiii—Cd—Eu1xvii | 57.443 (13) |
Sb2xi—Eu3—Cdxii | 108.315 (13) | Sb1xiv—Cd—Eu1xvii | 117.87 (2) |
Sb2x—Eu3—Cdxii | 152.666 (19) | Sb3—Cd—Eu1xvii | 56.693 (13) |
Sb2ix—Eu3—Cdxii | 86.946 (12) | Sb2—Cd—Eu1xvii | 133.962 (13) |
Sb2xii—Eu3—Cdxii | 51.142 (13) | Eu3vii—Cd—Eu1xvii | 119.724 (18) |
Cdix—Eu3—Cdxii | 88.461 (16) | Eu3viii—Cd—Eu1xvii | 70.603 (12) |
Cdxi—Eu3—Cdxii | 86.030 (15) | Eu1vi—Cd—Eu1xvii | 69.370 (13) |
Sb3ix—Eu3—Cdx | 108.724 (16) | Sb1xiii—Cd—Eu1xvi | 117.87 (2) |
Sb3x—Eu3—Cdx | 50.649 (11) | Sb1xiv—Cd—Eu1xvi | 57.443 (13) |
Sb2xi—Eu3—Cdx | 86.946 (12) | Sb3—Cd—Eu1xvi | 56.693 (13) |
Sb2x—Eu3—Cdx | 51.142 (13) | Sb2—Cd—Eu1xvi | 133.962 (13) |
Sb2ix—Eu3—Cdx | 108.315 (13) | Eu3vii—Cd—Eu1xvi | 70.603 (12) |
Sb2xii—Eu3—Cdx | 152.666 (19) | Eu3viii—Cd—Eu1xvi | 119.724 (18) |
Cdix—Eu3—Cdx | 86.030 (15) | Eu1vi—Cd—Eu1xvi | 69.370 (13) |
Cdxi—Eu3—Cdx | 88.461 (16) | Eu1xvii—Cd—Eu1xvi | 74.720 (15) |
Cdxii—Eu3—Cdx | 154.68 (3) | Sb1xiii—Cd—Eu4x | 115.04 (2) |
Sb3ix—Eu3—Eu4xxii | 111.194 (5) | Sb1xiv—Cd—Eu4x | 55.378 (13) |
Sb3x—Eu3—Eu4xxii | 111.194 (5) | Sb3—Cd—Eu4x | 132.546 (13) |
Sb2xi—Eu3—Eu4xxii | 48.986 (9) | Sb2—Cd—Eu4x | 54.120 (12) |
Sb2x—Eu3—Eu4xxii | 93.069 (14) | Eu3vii—Cd—Eu4x | 69.550 (10) |
Sb2ix—Eu3—Eu4xxii | 93.069 (14) | Eu3viii—Cd—Eu4x | 117.827 (18) |
Sb2xii—Eu3—Eu4xxii | 48.986 (8) | Eu1vi—Cd—Eu4x | 99.961 (13) |
Cdix—Eu3—Eu4xxii | 135.440 (10) | Eu1xvii—Cd—Eu4x | 168.941 (17) |
Cdxi—Eu3—Eu4xxii | 60.620 (10) | Eu1xvi—Cd—Eu4x | 104.797 (9) |
Cdxii—Eu3—Eu4xxii | 60.620 (10) | Sb1xiii—Cd—Eu4ix | 55.378 (13) |
Cdx—Eu3—Eu4xxii | 135.440 (10) | Sb1xiv—Cd—Eu4ix | 115.04 (2) |
Sb3ix—Eu3—Eu4xxiii | 111.194 (5) | Sb3—Cd—Eu4ix | 132.546 (13) |
Sb3x—Eu3—Eu4xxiii | 111.194 (5) | Sb2—Cd—Eu4ix | 54.120 (12) |
Sb2xi—Eu3—Eu4xxiii | 93.069 (14) | Eu3vii—Cd—Eu4ix | 117.827 (18) |
Sb2x—Eu3—Eu4xxiii | 48.986 (8) | Eu3viii—Cd—Eu4ix | 69.550 (10) |
Sb2ix—Eu3—Eu4xxiii | 48.986 (8) | Eu1vi—Cd—Eu4ix | 99.961 (13) |
Sb2xii—Eu3—Eu4xxiii | 93.069 (14) | Eu1xvii—Cd—Eu4ix | 104.797 (9) |
Cdix—Eu3—Eu4xxiii | 60.620 (10) | Eu1xvi—Cd—Eu4ix | 168.941 (17) |
Cdxi—Eu3—Eu4xxiii | 135.440 (10) | Eu4x—Cd—Eu4ix | 73.485 (12) |
Cdxii—Eu3—Eu4xxiii | 135.440 (10) | Eu1i—O—Eu1xviii | 97.9 (2) |
Cdx—Eu3—Eu4xxiii | 60.620 (10) | Eu1i—O—Eu2ix | 107.12 (4) |
Eu4xxii—Eu3—Eu4xxiii | 119.173 (14) | Eu1xviii—O—Eu2ix | 107.12 (4) |
Sb2xiii—Eu4—Sb2vii | 180.00 (2) | Eu1i—O—Eu2x | 107.12 (4) |
Sb2xiii—Eu4—Sb2xiv | 92.638 (15) | Eu1xviii—O—Eu2x | 107.12 (4) |
Sb2vii—Eu4—Sb2xiv | 87.362 (15) | Eu2ix—O—Eu2x | 126.7 (2) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, −y+1/2, z+1/2; (iii) −x−1/2, −y+1/2, z+1/2; (iv) −x+1/2, −y+1/2, −z+1; (v) −x−1/2, −y+1/2, −z+1; (vi) x, y, −z+1/2; (vii) x+1/2, y−1/2, z; (viii) x−1/2, y−1/2, z; (ix) x−1/2, y+1/2, z; (x) x+1/2, y+1/2, z; (xi) x+1/2, y+1/2, −z+1/2; (xii) x−1/2, y+1/2, −z+1/2; (xiii) −x−1/2, −y+1/2, −z; (xiv) −x+1/2, −y+1/2, −z; (xv) −x, −y, −z; (xvi) −x+1/2, −y+1/2, z−1/2; (xvii) −x−1/2, −y+1/2, z−1/2; (xviii) −x, −y+1, z−1/2; (xix) x, y, −z+3/2; (xx) x−1/2, y−1/2, −z+1/2; (xxi) x+1/2, y−1/2, −z+1/2; (xxii) −x, −y+1, z+1/2; (xxiii) x, y+1, z; (xxiv) x, y−1, z; (xxv) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | Eu5Cd2Sb5O |
Mr | 1609.37 |
Crystal system, space group | Orthorhombic, Cmcm |
Temperature (K) | 120 |
a, b, c (Å) | 4.7088 (5), 21.965 (2), 14.5982 (15) |
V (Å3) | 1509.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 31.92 |
Crystal size (mm) | 0.06 × 0.05 × 0.04 |
Data collection | |
Diffractometer | Bruker SMART APEX diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.161, 0.279 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10204, 1092, 1031 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.044, 1.14 |
No. of reflections | 1092 |
No. of parameters | 46 |
Δρmax, Δρmin (e Å−3) | 1.18, −1.16 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), XP in SHELXTL (Sheldrick, 2008).
The title compound, Eu5Cd2Sb5O, is isostructural to Ba5Cd2Sb5F, recently reported (Saparov & Bobev, 2010). The structure contains one-dimensional [Cd2Sb5]9- polyanions and isolated O2- ions surrounded tetrahedrally by Eu cations (Fig. 1). The polyanions are constructed from two chains of corner-sharing CdSb4 tetrahedra connected through Sb3 atoms and Sb2–Sb2 bonds [2.8078 (10) Å]. Similar strong homoatomic Sb–Sb interactions are found in related polyanionic Zn–Sb and Cd–Sb substructures [Ba3Cd2Sb4 (Saparov et al., 2008a), Sr11Cd6Sb12 (Park & Kim, 2004; Xia & Bobev, 2008a), Eu11Cd6Sb12 and Eu11Cd6Sb12 (Saparov et al., 2008b), Ba2Cd2Sb3 (Saparov et al., 2010)]. The Cd–Sb interactions [2.8413 (5) Å to 2.9624 (8) Å] are comparable to the sum of the covalent radii (Pauling, 1960) and to distances found in other structures based on CdSb4 tetrahedra [Ba3Cd2Sb4 (Saparov et al., 2008a), Ba21Cd4Sb18 (Xia and Bobev, 2008b), Eu11Cd6Sb12 (Saparov et al., 2008b), A2CdSb2 (Xia & Bobev, 2007a; Saparov et al., 2011), Sr9Cd4.49 (1)Sb9 (Xia & Bobev, 2007b)].
Band structure calculations highlight the importance of ionic Ba–F interations near the Fermi level to optimize bonding in Ba5Cd2Sb5F, but exact electron balance is achieved in the corresponding oxide Ba5Cd2Sb5Ox only when x = 0.5 (Saparov & Bobev, 2010). Whereas the fluoride is free of disorder, the oxide exhibits underoccupancy of the oxygen site, causing positional disorder of the next-nearest Ba atoms, as revealed by elongated atomic displacement parameters on the Ba2 site (modeled as a split position) in Ba5Cd2Sb5O0.59 (3). The Ba2 atoms move away from their equilibrium positions towards the empty space that results when the oxygen site is vacant. Thus, it is surprising that the present structure of Eu5Cd2Sb5O contains a fully occupied oxygen site, because the formula would show a one-electron deficiency, viz. (Eu2+)5(Cd2+)2(Sb3-)3(Sb2-)2(O2-). A possible resolution is to propose the occurrence of Eu in both +2 and +3 oxidation states. Because phase-pure samples were unavailable, magnetic measurements could not be performed to verify this proposal. Nevertheless, we note that the Eu1–O distance [2.528 (4) Å] is only 0.4% longer than the Eu1–F distance in Eu5Cd2Sb5F (Saparov & Bobev, 2010); this increase does not scale with the difference between the ionic radii of O2- and F-, the former being nearly 5% bigger than the latter (Shannon, 1976). A similar conclusion can be drawn by comparing the Eu2–O [2.634 (3) Å] and Eu2–F [2.635 (3) Å] distances.