Acta Cryst. (2007). E63, i193 [ doi:10.1107/S160053680705283X ]
Single crystals of lutetium oxide iodide, LuOI, were obtained as a by-product of the reaction of lutetium metal, rhenium powder and lutetium triiodide, LuI3, in a sealed tantalum container. LuOI crystallizes in the tetragonal PbFCl-type of structure (matlockite), where Lu, O and I are situated on positions with 4mm, 
m2 and 4mm symmetry, respectively.
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).
![[Figure 1]](./wm2159fig1thm.gif)
| Fig. 1. : The surrounding of Lu3+ in LuOI with displacement ellipsoids drawn at the 75% probability level. [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.] |
![[Figure 2]](./wm2159fig2thm.gif)
| Fig. 2. : Part of the crystal structure of LuOI, viewed approximately along the a axis. Lu atoms are represented as black, O as blue and I as pink spheres. |
| LuOI | Z = 2 |
| Mr = 317.87 | F000 = 264 |
| Tetragonal, P4/nmm | Dx = 7.717 Mg m−3 |
| Hall symbol: -P 4a 2a | Mo Kα radiation λ = 0.71073 Å |
| a = 3.8585 (7) Å | Cell parameters from 1205 reflections |
| b = 3.8585 (7) Å | θ = 1.9–28.2º |
| c = 9.189 (2) Å | µ = 47.02 mm−1 |
| α = 90º | T = 293 (2) K |
| β = 90º | Plate, orange |
| γ = 90º | 0.20 × 0.10 × 0.05 mm |
| V = 136.81 (5) Å3 |
| Stoe IPDS-I diffractometer | 126 independent reflections |
| Radiation source: fine-focus sealed tube | 121 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.093 |
| T = 293(2) K | θmax = 27.8º |
| φ scans | θmin = 4.4º |
| 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 | w = 1/[σ2(Fo2) + (0.0633P)2] where P = (Fo2 + 2Fc2)/3 |
| Least-squares matrix: full | (Δ/σ)max < 0.001 |
| R[F2 > 2σ(F2)] = 0.034 | Δρmax = 2.82 e Å−3 |
| wR(F2) = 0.094 | Δρmin = −3.05 e Å−3 |
| S = 1.20 | Extinction correction: none |
| 126 reflections | |
| 9 parameters | |
| Primary atom site location: structure-invariant direct methods | |
| Secondary atom site location: difference Fourier map |
| LuOI | γ = 90º |
| Mr = 317.87 | V = 136.81 (5) Å3 |
| Tetragonal, P4/nmm | Z = 2 |
| a = 3.8585 (7) Å | Mo Kα |
| b = 3.8585 (7) Å | µ = 47.02 mm−1 |
| c = 9.189 (2) Å | T = 293 (2) K |
| α = 90º | 0.20 × 0.10 × 0.05 mm |
| β = 90º |
| 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 | Δρmax = 2.82 e Å−3 |
| wR(F2) = 0.094 | Δρmin = −3.05 e Å−3 |
| S = 1.20 | Absolute structure: ? |
| 126 reflections | Flack parameter: ? |
| 9 parameters | Rogers parameter: ? |
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 > 2sigma(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. |
| Lu—O | 2.2048 (5) | Lu—Lui | 3.4641 (10) |
| Lu—I | 3.3138 (10) |
| Symmetry codes: (i) −x, −y+2, −z+1. |
This work was supported by the Deutsche Forschungsgemeinschaft (DFG), SFB 608 (Complex transition metal compounds with spin and charge degrees of freedom and disorder).
Batsanov, S. S., Kopaneva, L. I. & Dorogova, G. V. (1983). Zh. Neorg. Khim. 28, 2150–2152.
Brandenburg, K. (2005). DIAMOND. Version 3.0d. Crystal Impact GbR, Bonn, Germany.
Meyer, G. (1991). Synthesis of Lanthanide and Actinide Compounds, edited by G. Meyer & L. R. Morss, pp. 135–144. Dordrecht: Kluwer.
Meyer, G. (1993). ICDD entry [42-981]. International Centre for Diffraction Data, Newton Square, PA, USA.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Stoe & Cie (1999). X-SHAPE. Version 1.06. Stoe & Cie, Darmstadt, Germany.
Stoe & Cie (2001). X-AREA (Version 1.15) and X-RED (Version 1.22). Stoe & Cie, Darmstadt, Germany.
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).