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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, \overline{4}m2 and 4mm symmetry, respectively.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705283X/wm2159sup1.cif
Contains datablocks global_, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680705283X/wm2159Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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

Comment top

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).

Related literature top

For a previous powder study of LuOI, see: Batsanov et al. (1983); Meyer (1993). Syntheses of lanthanide compounds have been compiled by Meyer (1991).

Experimental top

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).

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] 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] 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.
Lutetium(III) oxide iodide top
Crystal data top
LuOIDx = 7.717 Mg m3
Mr = 317.87Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/nmmCell parameters from 1205 reflections
Hall symbol: -P 4a 2aθ = 1.9–28.2°
a = 3.8585 (7) ŵ = 47.02 mm1
c = 9.189 (2) ÅT = 293 K
V = 136.81 (5) Å3Plate, orange
Z = 20.20 × 0.10 × 0.05 mm
F(000) = 264
Data collection top
Stoe IPDS-I
diffractometer
126 independent reflections
Radiation source: fine-focus sealed tube121 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.093
ϕ scansθmax = 27.8°, θmin = 4.4°
Absorption correction: numerical
[X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]
h = 45
Tmin = 0.008, Tmax = 0.092k = 55
1249 measured reflectionsl = 1212
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.034Secondary 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 reflectionsΔρmax = 2.82 e Å3
9 parametersΔρmin = 3.05 e Å3
Crystal data top
LuOIZ = 2
Mr = 317.87Mo Kα radiation
Tetragonal, P4/nmmµ = 47.02 mm1
a = 3.8585 (7) ÅT = 293 K
c = 9.189 (2) Å0.20 × 0.10 × 0.05 mm
V = 136.81 (5) Å3
Data collection top
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 = 0.092Rint = 0.093
1249 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0349 parameters
wR(F2) = 0.0940 restraints
S = 1.20Δρmax = 2.82 e Å3
126 reflectionsΔρmin = 3.05 e Å3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Lu0.25000.75000.38386 (8)0.0147 (5)
I0.25001.25000.17918 (15)0.0235 (5)
O0.25000.25000.50000.015 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Lu0.0104 (5)0.0104 (5)0.0232 (6)0.0000.0000.000
I0.0222 (6)0.0222 (6)0.0260 (8)0.0000.0000.000
O0.010 (4)0.010 (4)0.024 (5)0.0000.0000.000
Geometric parameters (Å, º) top
Lu—Oi2.2048 (5)Lu—Lui3.4641 (10)
Lu—Oii2.2048 (5)Lu—Luviii3.4641 (10)
Lu—Oiii2.2048 (5)Lu—Luiii3.4641 (10)
Lu—O2.2048 (5)I—Luix3.3138 (10)
Lu—Iiv3.3138 (10)I—Luii3.3138 (10)
Lu—I3.3138 (10)I—Lux3.3138 (10)
Lu—Iv3.3138 (10)O—Lui2.2048 (5)
Lu—Ivi3.3138 (10)O—Luvi2.2048 (5)
Lu—Luvii3.4641 (10)O—Luiii2.2048 (5)
Oi—Lu—Oii76.449 (15)O—Lu—Lui38.225 (8)
Oi—Lu—Oiii122.10 (3)Iiv—Lu—Lui110.470 (13)
Oii—Lu—Oiii76.449 (15)I—Lu—Lui110.470 (13)
Oi—Lu—O76.449 (15)Iv—Lu—Lui176.54 (4)
Oii—Lu—O122.10 (3)Ivi—Lu—Lui72.62 (3)
Oiii—Lu—O76.449 (15)Luvii—Lu—Lui67.69 (2)
Oi—Lu—Iiv141.643 (6)Oi—Lu—Luviii100.90 (3)
Oii—Lu—Iiv141.643 (6)Oii—Lu—Luviii38.225 (8)
Oiii—Lu—Iiv76.426 (19)Oiii—Lu—Luviii38.225 (8)
O—Lu—Iiv76.426 (19)O—Lu—Luviii100.90 (3)
Oi—Lu—I76.426 (19)Iiv—Lu—Luviii110.470 (13)
Oii—Lu—I76.426 (19)I—Lu—Luviii110.470 (13)
Oiii—Lu—I141.643 (6)Iv—Lu—Luviii72.62 (3)
O—Lu—I141.643 (6)Ivi—Lu—Luviii176.54 (4)
Iiv—Lu—I110.84 (5)Luvii—Lu—Luviii67.69 (2)
Oi—Lu—Iv141.643 (6)Lui—Lu—Luviii103.93 (4)
Oii—Lu—Iv76.426 (19)Oi—Lu—Luiii100.90 (3)
Oiii—Lu—Iv76.426 (19)Oii—Lu—Luiii100.90 (3)
O—Lu—Iv141.643 (6)Oiii—Lu—Luiii38.225 (8)
Iiv—Lu—Iv71.21 (2)O—Lu—Luiii38.225 (8)
I—Lu—Iv71.21 (2)Iiv—Lu—Luiii72.62 (3)
Oi—Lu—Ivi76.426 (19)I—Lu—Luiii176.54 (4)
Oii—Lu—Ivi141.643 (6)Iv—Lu—Luiii110.470 (13)
Oiii—Lu—Ivi141.643 (6)Ivi—Lu—Luiii110.470 (13)
O—Lu—Ivi76.426 (19)Luvii—Lu—Luiii103.93 (4)
Iiv—Lu—Ivi71.21 (2)Lui—Lu—Luiii67.69 (2)
I—Lu—Ivi71.21 (2)Luviii—Lu—Luiii67.69 (2)
Iv—Lu—Ivi110.84 (5)Luix—I—Luii71.21 (2)
Oi—Lu—Luvii38.225 (8)Luix—I—Lux71.21 (2)
Oii—Lu—Luvii38.225 (7)Luii—I—Lux110.84 (5)
Oiii—Lu—Luvii100.90 (3)Luix—I—Lu110.84 (5)
O—Lu—Luvii100.90 (3)Luii—I—Lu71.21 (2)
Iiv—Lu—Luvii176.54 (4)Lux—I—Lu71.21 (2)
I—Lu—Luvii72.62 (3)Lui—O—Luvi103.551 (15)
Iv—Lu—Luvii110.470 (13)Lui—O—Luiii122.10 (3)
Ivi—Lu—Luvii110.470 (13)Luvi—O—Luiii103.551 (15)
Oi—Lu—Lui38.225 (8)Lui—O—Lu103.551 (15)
Oii—Lu—Lui100.90 (3)Luvi—O—Lu122.10 (3)
Oiii—Lu—Lui100.90 (3)Luiii—O—Lu103.551 (15)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+1, z; (iii) x1, y+1, z+1; (iv) x1, y1, z; (v) x1, y, z; (vi) x, y1, z; (vii) x, y+2, z+1; (viii) x1, y+2, z+1; (ix) x+1, y+1, z; (x) x+1, y, z.

Experimental details

Crystal data
Chemical formulaLuOI
Mr317.87
Crystal system, space groupTetragonal, P4/nmm
Temperature (K)293
a, c (Å)3.8585 (7), 9.189 (2)
V3)136.81 (5)
Z2
Radiation typeMo Kα
µ (mm1)47.02
Crystal size (mm)0.20 × 0.10 × 0.05
Data collection
DiffractometerStoe IPDS-I
diffractometer
Absorption correctionNumerical
[X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]
Tmin, Tmax0.008, 0.092
No. of measured, independent and
observed [I > 2σ(I)] reflections
1249, 126, 121
Rint0.093
(sin θ/λ)max1)0.657
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.094, 1.20
No. of reflections126
No. of parameters9
Δρmax, Δρmin (e Å3)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).

Selected bond lengths (Å) top
Lu—O2.2048 (5)Lu—Lui3.4641 (10)
Lu—I3.3138 (10)
Symmetry code: (i) x, y+2, z+1.
 

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