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Single crystals of lutetium oxide bromide, LuOBr, were obtained accidentally as a by-product of the reaction of lutetium metal, ruthenium powder and lutetium tribromide, LuBr3, in a sealed tantalum container. As is typical for rare-earth oxide halides of the type REOX (RE = rare-earth metal and X = halogen), LuOBr crystallizes in the tetra­gonal PbFCl structure type (matlockite), where Lu, O and Br 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/S1600536807027821/wm2121sup1.cif
Contains datablocks global_, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027821/wm2121Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](u-O) = 0.001 Å
  • R factor = 0.023
  • wR factor = 0.054
  • Data-to-parameter ratio = 10.7

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) 2.99 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 trihalides REX3 with their respective metals (frequently with the addition of a transition metal), the oxide halides REOX 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 REX3 which are generated by the so-called ammonium halide route (Meyer, 1991).

LuOBr was obtained in a reaction of lutetium metal, ruthenium powder and nominally pure lutetium tribromide, LuBr3, in a tantalum container at 1273 K. It crystallizes with the tetragonal PbFCl- (matlockite) type of structure, in which a central sheet of oxygen atoms is flanked by two sheets of bromine atoms. Between these Br—O—Br sheets, Lu3+ is surrounded by four oxygen and four bromine atoms in a distorted square antiprism with Lu—O distances of 2.1847 (7) Å and Lu—Br distances of 3.1228 (15) Å (Figs. 1, 2). There is an additional bromine atom capping one of the square faces at a distance of 3.851 (3) Å. The cell parameters obtained from the single-crystal study show no significant differences to those of a previous powder work (a = 3.770, c = 8.387 Å; Mayer et al., 1965).

Related literature top

For a previous powder study of LuOBr, see Mayer et al. (1965). Preparation of lanthanide compounds are compiled by Meyer (1991).

Experimental top

Light-orange, transparent plates of LuOBr were obtained in this special case as a major by-product (35%) from the reaction of lutetium powder (0.092 g, 0.5 mmol; Smart Elements, 99.99%), ruthenium powder (0.022 g, 0.2 mmol; Merck, 99%) and nominally pure LuBr3 (0.150 g, 0.4 mmol). Except for excess starting materials, other products were not identified so far. LuBr3 was prepared by the reaction of Lu2O3 (Chempur, 99.9%) with NH4Br (KMF, 99.5%) (Meyer, 1991), followed by the decomposition of the resulting (NH4)3LuBr6 at 693 K and subsequent sublimation. The reaction was carried out in a He-arc welded tantalum container within a silica jacket at 1273 K for 3 d and tempering at 1073 K for 10 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 1.03 Å from atom Lu and the deepest hole is 1.14 Å from the same atom.

Structure description top

In conproportionation reactions of rare-earth trihalides REX3 with their respective metals (frequently with the addition of a transition metal), the oxide halides REOX 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 REX3 which are generated by the so-called ammonium halide route (Meyer, 1991).

LuOBr was obtained in a reaction of lutetium metal, ruthenium powder and nominally pure lutetium tribromide, LuBr3, in a tantalum container at 1273 K. It crystallizes with the tetragonal PbFCl- (matlockite) type of structure, in which a central sheet of oxygen atoms is flanked by two sheets of bromine atoms. Between these Br—O—Br sheets, Lu3+ is surrounded by four oxygen and four bromine atoms in a distorted square antiprism with Lu—O distances of 2.1847 (7) Å and Lu—Br distances of 3.1228 (15) Å (Figs. 1, 2). There is an additional bromine atom capping one of the square faces at a distance of 3.851 (3) Å. The cell parameters obtained from the single-crystal study show no significant differences to those of a previous powder work (a = 3.770, c = 8.387 Å; Mayer et al., 1965).

For a previous powder study of LuOBr, see Mayer et al. (1965). Preparation of lanthanide compounds are compiled by Meyer (1991).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The surrounding of Lu3+ in LuOBr with displacement ellipsoids drawn at the 75% (O, Br) and 80% (Lu) 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 LuOBr, viewed along the a axis. Lu atoms are represented as grey, O as red and Br as brown spheres.
Lutetium(III) oxide bromide top
Crystal data top
LuOBrDx = 7.598 Mg m3
Mr = 270.88Melting point: no K
Tetragonal, P4/nmmMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 4a 2aCell parameters from 1168 reflections
a = 3.7646 (13) Åθ = 1.9–28.2°
c = 8.354 (4) ŵ = 58.17 mm1
V = 118.39 (8) Å3T = 293 K
Z = 2Plate, light-orange
F(000) = 2280.20 × 0.10 × 0.05 mm
Data collection top
Stoe IPDS I
diffractometer
107 independent reflections
Radiation source: fine-focus sealed tube107 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.099
φ scansθmax = 27.7°, θmin = 4.9°
Absorption correction: numerical
[X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]
h = 44
Tmin = 0.004, Tmax = 0.057k = 44
1046 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023 w = 1/[σ2(Fo2) + (0.0199P)2 + 0.8289P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.054(Δ/σ)max < 0.001
S = 1.29Δρmax = 1.55 e Å3
107 reflectionsΔρmin = 2.54 e Å3
10 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.019 (3)
Crystal data top
LuOBrZ = 2
Mr = 270.88Mo Kα radiation
Tetragonal, P4/nmmµ = 58.17 mm1
a = 3.7646 (13) ÅT = 293 K
c = 8.354 (4) Å0.20 × 0.10 × 0.05 mm
V = 118.39 (8) Å3
Data collection top
Stoe IPDS I
diffractometer
107 independent reflections
Absorption correction: numerical
[X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]
107 reflections with I > 2σ(I)
Tmin = 0.004, Tmax = 0.057Rint = 0.099
1046 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02310 parameters
wR(F2) = 0.0540 restraints
S = 1.29Δρmax = 1.55 e Å3
107 reflectionsΔρmin = 2.54 e Å3
Special details top

Experimental. The absorption correction (X-RED; Stoe & Cie, 2001) was performed after optimizing the crystal shape using X-SHAPE (Stoe & Cie, 1999).

A suitable single-crystal was carefully selected under a polarizing microscope and mounted in a glass capillary. The scattering intensities were collected on an imaging plate diffractometer (IPDS I, Stoe & Cie) equipped with a fine focus sealed tube X-ray source (Mo Kα, λ = 0.71073 Å) operating at 50 kV and 40 mA. Intensity data for the title compound were collected at room temperature by φ scans in 100 frames (0 < φ < 200°, Δφ = 2°, exposure time of 10 min) in the 2 Θ range 3.8 to 56.3°. Structure solution and refinement were carried out using the programs SIR92 (Altomare et al., 1993) and SHELXL97 (Sheldrick, 1997). A numerical absorption correction (X-RED (Stoe & Cie, 2001) was applied after optimization of the crystal shape (X-SHAPE (Stoe & Cie, 1999)). The last cycles of refinement included atomic positions and anisotropic parameters for all atoms. The final difference maps were free of any chemically significant features. The refinement was based on F2 for ALL reflections.

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
Lu0.25000.75000.36724 (9)0.0082 (4)
Br0.25001.25000.1718 (3)0.0158 (5)
O0.25000.25000.50000.009 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Lu0.0034 (4)0.0034 (4)0.0178 (5)0.0000.0000.000
Br0.0142 (6)0.0142 (6)0.0190 (9)0.0000.0000.000
O0.005 (3)0.005 (3)0.016 (5)0.0000.0000.000
Geometric parameters (Å, º) top
Lu—Oi2.1847 (7)Lu—Lui3.4650 (14)
Lu—Oii2.1847 (7)Lu—Luviii3.4650 (13)
Lu—Oiii2.1847 (7)Lu—Luiii3.4650 (14)
Lu—O2.1847 (7)Br—Luix3.1228 (15)
Lu—Briv3.1228 (15)Br—Luii3.1228 (15)
Lu—Br3.1228 (15)Br—Lux3.1228 (15)
Lu—Brv3.1228 (15)O—Lui2.1847 (7)
Lu—Brvi3.1228 (15)O—Luvi2.1847 (7)
Lu—Luvii3.4650 (14)O—Luiii2.1847 (7)
Oi—Lu—Oii75.07 (2)O—Lu—Lui37.533 (10)
Oi—Lu—Oiii118.99 (4)Briv—Lu—Lui109.55 (3)
Oii—Lu—Oiii75.07 (2)Br—Lu—Lui109.55 (3)
Oi—Lu—O75.07 (2)Brv—Lu—Lui171.72 (5)
Oii—Lu—O118.99 (4)Brvi—Lu—Lui71.33 (5)
Oiii—Lu—O75.07 (2)Luvii—Lu—Lui65.81 (3)
Oi—Lu—Briv141.696 (9)Oi—Lu—Luviii98.23 (4)
Oii—Lu—Briv141.696 (9)Oii—Lu—Luviii37.533 (10)
Oiii—Lu—Briv75.29 (3)Oiii—Lu—Luviii37.533 (10)
O—Lu—Briv75.29 (3)O—Lu—Luviii98.23 (4)
Oi—Lu—Br75.29 (3)Briv—Lu—Luviii109.55 (3)
Oii—Lu—Br75.29 (3)Br—Lu—Luviii109.55 (3)
Oiii—Lu—Br141.696 (9)Brv—Lu—Luviii71.33 (5)
O—Lu—Br141.696 (9)Brvi—Lu—Luviii171.72 (5)
Briv—Lu—Br116.95 (8)Luvii—Lu—Luviii65.81 (3)
Oi—Lu—Brv141.696 (9)Lui—Lu—Luviii100.39 (5)
Oii—Lu—Brv75.29 (3)Oi—Lu—Luiii98.23 (4)
Oiii—Lu—Brv75.29 (3)Oii—Lu—Luiii98.23 (4)
O—Lu—Brv141.696 (9)Oiii—Lu—Luiii37.533 (10)
Briv—Lu—Brv74.13 (4)O—Lu—Luiii37.533 (10)
Br—Lu—Brv74.13 (4)Briv—Lu—Luiii71.33 (5)
Oi—Lu—Brvi75.29 (3)Br—Lu—Luiii171.72 (5)
Oii—Lu—Brvi141.696 (9)Brv—Lu—Luiii109.55 (3)
Oiii—Lu—Brvi141.696 (9)Brvi—Lu—Luiii109.55 (3)
O—Lu—Brvi75.29 (3)Luvii—Lu—Luiii100.39 (5)
Briv—Lu—Brvi74.13 (4)Lui—Lu—Luiii65.81 (3)
Br—Lu—Brvi74.13 (4)Luviii—Lu—Luiii65.81 (3)
Brv—Lu—Brvi116.95 (8)Luix—Br—Luii74.13 (4)
Oi—Lu—Luvii37.533 (10)Luix—Br—Lux74.13 (4)
Oii—Lu—Luvii37.533 (10)Luii—Br—Lux116.95 (8)
Oiii—Lu—Luvii98.23 (4)Luix—Br—Lu116.95 (8)
O—Lu—Luvii98.23 (4)Luii—Br—Lu74.13 (4)
Briv—Lu—Luvii171.72 (5)Lux—Br—Lu74.13 (4)
Br—Lu—Luvii71.33 (5)Lui—O—Luvi104.93 (2)
Brv—Lu—Luvii109.55 (3)Lui—O—Luiii118.99 (4)
Brvi—Lu—Luvii109.55 (3)Luvi—O—Luiii104.93 (2)
Oi—Lu—Lui37.533 (10)Lui—O—Lu104.93 (2)
Oii—Lu—Lui98.23 (4)Luvi—O—Lu118.99 (4)
Oiii—Lu—Lui98.23 (4)Luiii—O—Lu104.93 (2)
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 formulaLuOBr
Mr270.88
Crystal system, space groupTetragonal, P4/nmm
Temperature (K)293
a, c (Å)3.7646 (13), 8.354 (4)
V3)118.39 (8)
Z2
Radiation typeMo Kα
µ (mm1)58.17
Crystal size (mm)0.20 × 0.10 × 0.05
Data collection
DiffractometerStoe IPDS I
Absorption correctionNumerical
[X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]
Tmin, Tmax0.004, 0.057
No. of measured, independent and
observed [I > 2σ(I)] reflections
1046, 107, 107
Rint0.099
(sin θ/λ)max1)0.655
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.054, 1.29
No. of reflections107
No. of parameters10
Δρmax, Δρmin (e Å3)1.55, 2.54

Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2005), SHELXL97.

Selected bond lengths (Å) top
Lu—O2.1847 (7)Lu—Lui3.4650 (14)
Lu—Br3.1228 (15)
Symmetry code: (i) x, y+2, z+1.
 

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