Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705283X/wm2159sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680705283X/wm2159Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (u-O) = 0.001 Å
- R factor = 0.034
- wR factor = 0.094
- Data-to-parameter ratio = 14.0
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Lu (3) 2.95 PLAT804_ALERT_5_G ARU-Pack Problem in PLATON Analysis ............ 128 Times
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 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 0 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
For a previous powder study of LuOI, see: Batsanov et al. (1983); Meyer (1993). Syntheses of lanthanide compounds have been compiled by Meyer (1991).
Light orange, transparent plates of LuOI were obtained as a by-product (ca 30%) from the reaction of lutetium powder (0.066 g, 0.37 mmol, Smart Elements, 99.99%), rhenium powder (0.030 g, 0.16 mmol, Merck, 99.9%) and LuI3 (0.150 g, 0.4 mmol). Most of LuI3 and apparently all rhenium powder remained unreacted. LuI3 was prepared by the direct reaction of Lu chips (Chempur, 99.9%) with I2 (Acros, 95%) in a sealed silica tube at 503 K and subsequent purification of the product by high-vacuum sublimation. The reaction was carried out in a He-arc welded tantalum container within a silica jacket at 1223 K for 17 d. Due to their moisture and air sensitivity, reagents and products were handled in an argon-filled glove box (M. Braun, Garching, Germany).
For the present refinement, origin choice 2 for space group P4/nmm was chosen. The highest peak in the final difference Fourier map is 0.90 Å from atom Lu and the deepest hole is 0.81 Å from the same atom.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-RED (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
LuOI | Dx = 7.717 Mg m−3 |
Mr = 317.87 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P4/nmm | Cell parameters from 1205 reflections |
Hall symbol: -P 4a 2a | θ = 1.9–28.2° |
a = 3.8585 (7) Å | µ = 47.02 mm−1 |
c = 9.189 (2) Å | T = 293 K |
V = 136.81 (5) Å3 | Plate, orange |
Z = 2 | 0.20 × 0.10 × 0.05 mm |
F(000) = 264 |
Stoe IPDS-I diffractometer | 126 independent reflections |
Radiation source: fine-focus sealed tube | 121 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.093 |
ϕ scans | θmax = 27.8°, θmin = 4.4° |
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)] | h = −4→5 |
Tmin = 0.008, Tmax = 0.092 | k = −5→5 |
1249 measured reflections | l = −12→12 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.034 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.094 | w = 1/[σ2(Fo2) + (0.0633P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.20 | (Δ/σ)max < 0.001 |
126 reflections | Δρmax = 2.82 e Å−3 |
9 parameters | Δρmin = −3.05 e Å−3 |
LuOI | Z = 2 |
Mr = 317.87 | Mo Kα radiation |
Tetragonal, P4/nmm | µ = 47.02 mm−1 |
a = 3.8585 (7) Å | T = 293 K |
c = 9.189 (2) Å | 0.20 × 0.10 × 0.05 mm |
V = 136.81 (5) Å3 |
Stoe IPDS-I diffractometer | 126 independent reflections |
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)] | 121 reflections with I > 2σ(I) |
Tmin = 0.008, Tmax = 0.092 | Rint = 0.093 |
1249 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 9 parameters |
wR(F2) = 0.094 | 0 restraints |
S = 1.20 | Δρmax = 2.82 e Å−3 |
126 reflections | Δρmin = −3.05 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 | ||
Lu | −0.2500 | 0.7500 | 0.38386 (8) | 0.0147 (5) | |
I | 0.2500 | 1.2500 | 0.17918 (15) | 0.0235 (5) | |
O | −0.2500 | 0.2500 | 0.5000 | 0.015 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Lu | 0.0104 (5) | 0.0104 (5) | 0.0232 (6) | 0.000 | 0.000 | 0.000 |
I | 0.0222 (6) | 0.0222 (6) | 0.0260 (8) | 0.000 | 0.000 | 0.000 |
O | 0.010 (4) | 0.010 (4) | 0.024 (5) | 0.000 | 0.000 | 0.000 |
Lu—Oi | 2.2048 (5) | Lu—Lui | 3.4641 (10) |
Lu—Oii | 2.2048 (5) | Lu—Luviii | 3.4641 (10) |
Lu—Oiii | 2.2048 (5) | Lu—Luiii | 3.4641 (10) |
Lu—O | 2.2048 (5) | I—Luix | 3.3138 (10) |
Lu—Iiv | 3.3138 (10) | I—Luii | 3.3138 (10) |
Lu—I | 3.3138 (10) | I—Lux | 3.3138 (10) |
Lu—Iv | 3.3138 (10) | O—Lui | 2.2048 (5) |
Lu—Ivi | 3.3138 (10) | O—Luvi | 2.2048 (5) |
Lu—Luvii | 3.4641 (10) | O—Luiii | 2.2048 (5) |
Oi—Lu—Oii | 76.449 (15) | O—Lu—Lui | 38.225 (8) |
Oi—Lu—Oiii | 122.10 (3) | Iiv—Lu—Lui | 110.470 (13) |
Oii—Lu—Oiii | 76.449 (15) | I—Lu—Lui | 110.470 (13) |
Oi—Lu—O | 76.449 (15) | Iv—Lu—Lui | 176.54 (4) |
Oii—Lu—O | 122.10 (3) | Ivi—Lu—Lui | 72.62 (3) |
Oiii—Lu—O | 76.449 (15) | Luvii—Lu—Lui | 67.69 (2) |
Oi—Lu—Iiv | 141.643 (6) | Oi—Lu—Luviii | 100.90 (3) |
Oii—Lu—Iiv | 141.643 (6) | Oii—Lu—Luviii | 38.225 (8) |
Oiii—Lu—Iiv | 76.426 (19) | Oiii—Lu—Luviii | 38.225 (8) |
O—Lu—Iiv | 76.426 (19) | O—Lu—Luviii | 100.90 (3) |
Oi—Lu—I | 76.426 (19) | Iiv—Lu—Luviii | 110.470 (13) |
Oii—Lu—I | 76.426 (19) | I—Lu—Luviii | 110.470 (13) |
Oiii—Lu—I | 141.643 (6) | Iv—Lu—Luviii | 72.62 (3) |
O—Lu—I | 141.643 (6) | Ivi—Lu—Luviii | 176.54 (4) |
Iiv—Lu—I | 110.84 (5) | Luvii—Lu—Luviii | 67.69 (2) |
Oi—Lu—Iv | 141.643 (6) | Lui—Lu—Luviii | 103.93 (4) |
Oii—Lu—Iv | 76.426 (19) | Oi—Lu—Luiii | 100.90 (3) |
Oiii—Lu—Iv | 76.426 (19) | Oii—Lu—Luiii | 100.90 (3) |
O—Lu—Iv | 141.643 (6) | Oiii—Lu—Luiii | 38.225 (8) |
Iiv—Lu—Iv | 71.21 (2) | O—Lu—Luiii | 38.225 (8) |
I—Lu—Iv | 71.21 (2) | Iiv—Lu—Luiii | 72.62 (3) |
Oi—Lu—Ivi | 76.426 (19) | I—Lu—Luiii | 176.54 (4) |
Oii—Lu—Ivi | 141.643 (6) | Iv—Lu—Luiii | 110.470 (13) |
Oiii—Lu—Ivi | 141.643 (6) | Ivi—Lu—Luiii | 110.470 (13) |
O—Lu—Ivi | 76.426 (19) | Luvii—Lu—Luiii | 103.93 (4) |
Iiv—Lu—Ivi | 71.21 (2) | Lui—Lu—Luiii | 67.69 (2) |
I—Lu—Ivi | 71.21 (2) | Luviii—Lu—Luiii | 67.69 (2) |
Iv—Lu—Ivi | 110.84 (5) | Luix—I—Luii | 71.21 (2) |
Oi—Lu—Luvii | 38.225 (8) | Luix—I—Lux | 71.21 (2) |
Oii—Lu—Luvii | 38.225 (7) | Luii—I—Lux | 110.84 (5) |
Oiii—Lu—Luvii | 100.90 (3) | Luix—I—Lu | 110.84 (5) |
O—Lu—Luvii | 100.90 (3) | Luii—I—Lu | 71.21 (2) |
Iiv—Lu—Luvii | 176.54 (4) | Lux—I—Lu | 71.21 (2) |
I—Lu—Luvii | 72.62 (3) | Lui—O—Luvi | 103.551 (15) |
Iv—Lu—Luvii | 110.470 (13) | Lui—O—Luiii | 122.10 (3) |
Ivi—Lu—Luvii | 110.470 (13) | Luvi—O—Luiii | 103.551 (15) |
Oi—Lu—Lui | 38.225 (8) | Lui—O—Lu | 103.551 (15) |
Oii—Lu—Lui | 100.90 (3) | Luvi—O—Lu | 122.10 (3) |
Oiii—Lu—Lui | 100.90 (3) | Luiii—O—Lu | 103.551 (15) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z; (iii) −x−1, −y+1, −z+1; (iv) x−1, y−1, z; (v) x−1, y, z; (vi) x, y−1, z; (vii) −x, −y+2, −z+1; (viii) −x−1, −y+2, −z+1; (ix) x+1, y+1, z; (x) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | LuOI |
Mr | 317.87 |
Crystal system, space group | Tetragonal, P4/nmm |
Temperature (K) | 293 |
a, c (Å) | 3.8585 (7), 9.189 (2) |
V (Å3) | 136.81 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 47.02 |
Crystal size (mm) | 0.20 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Stoe IPDS-I diffractometer |
Absorption correction | Numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)] |
Tmin, Tmax | 0.008, 0.092 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1249, 126, 121 |
Rint | 0.093 |
(sin θ/λ)max (Å−1) | 0.657 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.094, 1.20 |
No. of reflections | 126 |
No. of parameters | 9 |
Δρmax, Δρmin (e Å−3) | 2.82, −3.05 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-RED (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2005).
Lu—O | 2.2048 (5) | Lu—Lui | 3.4641 (10) |
Lu—I | 3.3138 (10) |
Symmetry code: (i) −x, −y+2, −z+1. |
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In conproportionation reactions of rare-earth halides with their respective metals (frequently with the addition of a transition metal), the oxide halides REOX (RE = rare earth metal, X = halogen) often appear as a few single crystals as by-products. Except for impurities from the reaction containers, e.g. tantalum, this may be due to impure anhydrous rare-earth trihalides MX3.
LuOI was obtained in a reaction of lutetium metal, rhenium powder and nominally pure lutetium triiodide, LuI3, in a tantalum container at 1223 K. It crystallizes with the tetragonal PbFCl type of structure, in which Lu3+ is surrounded by four oxygen and four iodine atoms in a distorted square antiprismatic coordination with Lu—O distances of 2.2048 (5) Å and Lu—I distances of 3.3138 (10) Å. An additional iodide ion is capping one of the square faces at a distance of 4.0152 (18) Å (Figs. 1, 2). The cell parameters obtained from the present single-crystal study show no significant differences to those of a previous powder study (a = 3.850, c = 9.179 Å; Batsanov et al., 1983; Meyer, 1993).