Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046041/fi2045sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046041/fi2045Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (e-Cu) = 0.001 Å
- R factor = 0.020
- wR factor = 0.041
- Data-to-parameter ratio = 20.2
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for La1 (3) 2.88 PLAT794_ALERT_5_G Check Predicted Bond Valency for La2 (3) 2.95 PLAT794_ALERT_5_G Check Predicted Bond Valency for In1 (9) 2.17 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (1) 0.86
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 0 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 4 ALERT type 5 Informative message, check
For the related La2CuInS5 structure, see Huch, Gulay, Olekseyuk & Pietraszko (2007). For a previous structure determination of the title compound from powder data, see Huch, Gulay & Olekseyuk (2007). For related literature, see Spek (2003).
The sample with the nominal compositions La2CuInSe5 was prepared by sintering the elemental constituents (purchased from Alfa Aesar) of the purity better than 99.9 wt.% in an evacuated quartz ampoule. The synthesis was realised in a tube furnace. The ampoule was heated with a heating rate of 30 K/h to maximal temperature 1420 K. The samples were kept at this temperature during 3 h. Afterwards they were cooled slowly (10 K/h) to 870 K and annealed at this temperature during 240 h. After annealing the ampoule with the sample was quenched in cold water. An EDAX PV9800 microanalyzer was used for the confirmation of the compositions of the crystals. Calculated for La2CuInSe5 (black crystals) % La: 32.65, Cu: 7.47, In: 13.49, Se: 46.39 and found % La: 31.74, Cu: 7.57, In: 13.65, Se: 47.04.
The crystal structure was solved by Patterson methods (Sheldrick, 1997) and refined by full matrix least squares method using SHELXL97 (Sheldrick, 1997). Space group Pnma was confirmed with PLATON (Spek, 2003) and no additional symmetry elements were found. The highest peak and deepest hole in the Fourier map are found 0.94 Å and 0.65 Å, respectively, from Cu1.
The formation of quaternary La2CuInSe5 had been established earlier during the investigation of the phase relations in the La2Se3—Cu2Se—In2Se3 system (Huch, Gulay & Olekseyuk, 2007) and the crystal structure of this compound was investigated using X-ray powder diffraction (space group Pnma). The crystal structure of La2CuInSe5 has been reinvestigated by means of X-ray single-crystal diffraction and presented here. Crystal structure of the title compound is similar to previously reported La2CuInS5 (Huch, Gulay, Olekseyuk & Pietraszko, 2007).
The unit cell and the coordination polyhedra of the La, Cu, In and Se atoms in the structure of the La2CuInSe5 compound are shown in Fig. 1. Selenium atoms create bi-capped trigonal prisms, octahedra and tetrahedra around the La, In and Cu atoms, respectively. The coordination polyhedron of the copper atom can be extended to a trigonal bipyramid. In contrast to La2CuInS5, the position of the Cu atom is fully occupied and ordered (Fig. 2). The single-crystal data for La2CuInSe5 agree well with our previous powder diffraction results (Huch, Gulay & Olekseyuk, 2007).
For the related La2CuInS5 structure, see Huch, Gulay, Olekseyuk & Pietraszko (2007). For a previous structure determination of the title compound from powder data, see Huch, Gulay & Olekseyuk (2007). For related literature, see Spek (2003).
Data collection: CrysAlis CCD (Mayer, 2006); cell refinement: CrysAlis RED (Mayer, 2006); data reduction: CrysAlis RED (Mayer, 2006); 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: publCIF (Westrip, 2007).
Fig. 1. The packing of La2CuInSe5 viewed along the b axis. | |
Fig. 2. Trigonal bi-pyramids around the Cu atom in the structures of La2CuInS5 and La2CuInSe5. |
La2CuInSe5 | F(000) = 1448 |
Mr = 850.98 | Dx = 6.472 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 1049 reflections |
a = 12.051 (2) Å | θ = 2.9–27.5° |
b = 4.1223 (8) Å | µ = 35.34 mm−1 |
c = 17.580 (4) Å | T = 295 K |
V = 873.3 (3) Å3 | Prism, black |
Z = 4 | 0.13 × 0.07 × 0.03 mm |
Kuma KM-4 diffractometer with CCD detector | 1134 independent reflections |
Radiation source: fine-focus sealed tube | 1049 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
Detector resolution: 33.133 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ω scans | h = −15→15 |
Absorption correction: numerical (CrysAlis RED; Mayer, 2006) | k = −5→4 |
Tmin = 0.076, Tmax = 0.396 | l = −22→22 |
9371 measured reflections |
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) + (0.0208P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.041 | (Δ/σ)max = 0.001 |
S = 1.12 | Δρmax = 2.03 e Å−3 |
1134 reflections | Δρmin = −1.68 e Å−3 |
56 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00141 (8) |
La2CuInSe5 | V = 873.3 (3) Å3 |
Mr = 850.98 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 12.051 (2) Å | µ = 35.34 mm−1 |
b = 4.1223 (8) Å | T = 295 K |
c = 17.580 (4) Å | 0.13 × 0.07 × 0.03 mm |
Kuma KM-4 diffractometer with CCD detector | 1134 independent reflections |
Absorption correction: numerical (CrysAlis RED; Mayer, 2006) | 1049 reflections with I > 2σ(I) |
Tmin = 0.076, Tmax = 0.396 | Rint = 0.039 |
9371 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 56 parameters |
wR(F2) = 0.041 | 0 restraints |
S = 1.12 | Δρmax = 2.03 e Å−3 |
1134 reflections | Δρmin = −1.68 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 | ||
La1 | 0.47993 (3) | 0.2500 | 0.67902 (2) | 0.00840 (10) | |
La2 | 0.13680 (3) | 0.2500 | 0.59252 (2) | 0.00889 (10) | |
In1 | 0.19371 (4) | 0.2500 | 0.35994 (3) | 0.01362 (12) | |
Cu1 | 0.58400 (8) | 0.2500 | 0.50300 (5) | 0.0222 (2) | |
Se1 | 0.39751 (5) | 0.2500 | 0.42335 (4) | 0.00954 (15) | |
Se2 | 0.24095 (5) | 0.2500 | 0.77082 (4) | 0.01086 (15) | |
Se3 | 0.38864 (5) | 0.2500 | 0.96206 (4) | 0.00997 (15) | |
Se4 | 0.48589 (5) | 0.2500 | 0.19359 (4) | 0.00883 (15) | |
Se5 | 0.18170 (5) | 0.2500 | 0.11544 (4) | 0.00930 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
La1 | 0.00886 (19) | 0.00760 (19) | 0.00873 (19) | 0.000 | −0.00046 (13) | 0.000 |
La2 | 0.00796 (19) | 0.00757 (19) | 0.0111 (2) | 0.000 | 0.00015 (14) | 0.000 |
In1 | 0.0104 (2) | 0.0147 (2) | 0.0158 (3) | 0.000 | −0.00293 (18) | 0.000 |
Cu1 | 0.0312 (6) | 0.0196 (5) | 0.0159 (5) | 0.000 | 0.0037 (4) | 0.000 |
Se1 | 0.0082 (3) | 0.0098 (3) | 0.0106 (3) | 0.000 | −0.0007 (2) | 0.000 |
Se2 | 0.0107 (3) | 0.0117 (3) | 0.0101 (3) | 0.000 | −0.0002 (2) | 0.000 |
Se3 | 0.0104 (3) | 0.0102 (3) | 0.0093 (3) | 0.000 | 0.0010 (2) | 0.000 |
Se4 | 0.0093 (3) | 0.0090 (3) | 0.0082 (3) | 0.000 | −0.0004 (2) | 0.000 |
Se5 | 0.0074 (3) | 0.0088 (3) | 0.0118 (3) | 0.000 | 0.0009 (2) | 0.000 |
La1—Se1i | 3.1094 (7) | Cu1—Se1ii | 2.4443 (7) |
La1—Se1ii | 3.1094 (7) | Cu1—Se1i | 2.4443 (7) |
La1—Se2 | 3.3013 (9) | Cu1—Se5xii | 2.3920 (12) |
La1—Se2iii | 3.2669 (10) | Cu1—Cu1i | 2.8911 (14) |
La1—Se4ii | 3.0714 (7) | Cu1—Cu1ii | 2.8911 (14) |
La1—Se4i | 3.0714 (7) | Se1—Cu1ii | 2.4443 (7) |
La1—Se5iv | 3.0482 (7) | Se1—Cu1i | 2.4443 (7) |
La1—Se5v | 3.0482 (7) | Se1—La1i | 3.1094 (7) |
La1—Cu1 | 3.3389 (12) | Se1—La1ii | 3.1094 (7) |
La1—La1vi | 4.1223 (8) | Se2—In1v | 2.7061 (6) |
La1—La1vii | 4.1223 (8) | Se2—In1iv | 2.7061 (6) |
La2—Se2 | 3.3763 (9) | Se2—La1x | 3.2669 (10) |
La2—Se3viii | 3.0988 (7) | Se3—In1iv | 2.9079 (7) |
La2—Se3ix | 3.0988 (7) | Se3—In1v | 2.9079 (7) |
La2—Se3x | 3.1407 (9) | Se3—La2v | 3.0988 (7) |
La2—Se4v | 3.0969 (7) | Se3—La2iv | 3.0988 (7) |
La2—Se4iv | 3.0969 (6) | Se3—La2iii | 3.1407 (9) |
La2—Se5v | 3.0323 (7) | Se4—In1xii | 2.6754 (9) |
La2—Se5iv | 3.0323 (7) | Se4—La1ii | 3.0714 (7) |
La2—La2vi | 4.1223 (8) | Se4—La1i | 3.0714 (7) |
La2—La2vii | 4.1223 (8) | Se4—La2viii | 3.0969 (6) |
In1—Se4xi | 2.6754 (9) | Se4—La2ix | 3.0969 (6) |
In1—Se1 | 2.6972 (9) | Se5—Cu1xi | 2.3920 (12) |
In1—Se2viii | 2.7061 (6) | Se5—La2ix | 3.0323 (7) |
In1—Se2ix | 2.7061 (6) | Se5—La2viii | 3.0323 (7) |
In1—Se3ix | 2.9079 (7) | Se5—La1viii | 3.0482 (7) |
In1—Se3viii | 2.9079 (7) | Se5—La1ix | 3.0482 (7) |
Cu1—Se1 | 2.6479 (13) | ||
Se5iv—La1—Se5v | 85.09 (2) | Se3ix—La2—La2vii | 131.694 (12) |
Se5iv—La1—Se4ii | 143.79 (2) | Se3x—La2—La2vii | 90.0 |
Se5v—La1—Se4ii | 84.221 (18) | Se2—La2—La2vii | 90.0 |
Se5iv—La1—Se4i | 84.221 (18) | La2vi—La2—La2vii | 180.00 (2) |
Se5v—La1—Se4i | 143.79 (2) | Se4xi—In1—Se1 | 176.18 (3) |
Se4ii—La1—Se4i | 84.30 (2) | Se4xi—In1—Se2viii | 93.94 (2) |
Se5iv—La1—Se1i | 69.09 (2) | Se1—In1—Se2viii | 88.53 (2) |
Se5v—La1—Se1i | 122.65 (2) | Se4xi—In1—Se2ix | 93.94 (2) |
Se4ii—La1—Se1i | 143.43 (2) | Se1—In1—Se2ix | 88.53 (2) |
Se4i—La1—Se1i | 85.03 (2) | Se2viii—In1—Se2ix | 99.22 (3) |
Se5iv—La1—Se1ii | 122.65 (2) | Se4xi—In1—Se3ix | 84.12 (2) |
Se5v—La1—Se1ii | 69.09 (2) | Se1—In1—Se3ix | 93.19 (2) |
Se4ii—La1—Se1ii | 85.03 (2) | Se2viii—In1—Se3ix | 175.27 (2) |
Se4i—La1—Se1ii | 143.43 (2) | Se2ix—In1—Se3ix | 85.23 (2) |
Se1i—La1—Se1ii | 83.04 (2) | Se4xi—In1—Se3viii | 84.12 (2) |
Se5iv—La1—Se2iii | 135.583 (13) | Se1—In1—Se3viii | 93.19 (2) |
Se5v—La1—Se2iii | 135.583 (13) | Se2viii—In1—Se3viii | 85.23 (2) |
Se4ii—La1—Se2iii | 70.975 (16) | Se2ix—In1—Se3viii | 175.27 (2) |
Se4i—La1—Se2iii | 70.975 (16) | Se3ix—In1—Se3viii | 90.28 (3) |
Se1i—La1—Se2iii | 72.473 (18) | Se5xii—Cu1—Se1ii | 114.60 (3) |
Se1ii—La1—Se2iii | 72.473 (18) | Se5xii—Cu1—Se1i | 114.60 (3) |
Se5iv—La1—Se2 | 67.777 (19) | Se1ii—Cu1—Se1i | 114.97 (5) |
Se5v—La1—Se2 | 67.777 (19) | Se5xii—Cu1—Se1 | 87.56 (4) |
Se4ii—La1—Se2 | 76.149 (19) | Se1ii—Cu1—Se1 | 110.95 (3) |
Se4i—La1—Se2 | 76.149 (19) | Se1i—Cu1—Se1 | 110.95 (3) |
Se1i—La1—Se2 | 134.211 (13) | Se5xii—Cu1—Cu1i | 108.24 (4) |
Se1ii—La1—Se2 | 134.211 (13) | Se1ii—Cu1—Cu1i | 133.18 (6) |
Se2iii—La1—Se2 | 135.077 (17) | Se1i—Cu1—Cu1i | 58.80 (2) |
Se5iv—La1—Cu1 | 84.27 (2) | Se1—Cu1—Cu1i | 52.15 (3) |
Se5v—La1—Cu1 | 84.27 (2) | Se5xii—Cu1—Cu1ii | 108.24 (4) |
Se4ii—La1—Cu1 | 128.709 (18) | Se1ii—Cu1—Cu1ii | 58.80 (2) |
Se4i—La1—Cu1 | 128.709 (18) | Se1i—Cu1—Cu1ii | 133.18 (6) |
Se1i—La1—Cu1 | 44.373 (13) | Se1—Cu1—Cu1ii | 52.15 (3) |
Se1ii—La1—Cu1 | 44.373 (13) | Cu1i—Cu1—Cu1ii | 90.95 (6) |
Se2iii—La1—Cu1 | 83.60 (2) | Se5xii—Cu1—La1 | 172.58 (4) |
Se2—La1—Cu1 | 141.33 (2) | Se1ii—Cu1—La1 | 62.83 (3) |
Se5iv—La1—La1vi | 132.546 (12) | Se1i—Cu1—La1 | 62.83 (3) |
Se5v—La1—La1vi | 47.454 (12) | Se1—Cu1—La1 | 99.86 (4) |
Se4ii—La1—La1vi | 47.849 (12) | Cu1i—Cu1—La1 | 76.75 (4) |
Se4i—La1—La1vi | 132.151 (12) | Cu1ii—Cu1—La1 | 76.75 (4) |
Se1i—La1—La1vi | 131.520 (11) | Cu1ii—Se1—Cu1i | 114.97 (5) |
Se1ii—La1—La1vi | 48.480 (11) | Cu1ii—Se1—Cu1 | 69.05 (3) |
Se2iii—La1—La1vi | 90.0 | Cu1i—Se1—Cu1 | 69.05 (3) |
Se2—La1—La1vi | 90.0 | Cu1ii—Se1—In1 | 107.57 (3) |
Cu1—La1—La1vi | 90.0 | Cu1i—Se1—In1 | 107.57 (3) |
Se5iv—La1—La1vii | 47.454 (12) | Cu1—Se1—In1 | 172.49 (4) |
Se5v—La1—La1vii | 132.546 (12) | Cu1ii—Se1—La1i | 145.31 (3) |
Se4ii—La1—La1vii | 132.151 (12) | Cu1i—Se1—La1i | 72.80 (3) |
Se4i—La1—La1vii | 47.849 (12) | Cu1—Se1—La1i | 84.43 (2) |
Se1i—La1—La1vii | 48.480 (11) | In1—Se1—La1i | 101.15 (2) |
Se1ii—La1—La1vii | 131.520 (11) | Cu1ii—Se1—La1ii | 72.80 (3) |
Se2iii—La1—La1vii | 90.0 | Cu1i—Se1—La1ii | 145.31 (3) |
Se2—La1—La1vii | 90.0 | Cu1—Se1—La1ii | 84.43 (2) |
Cu1—La1—La1vii | 90.0 | In1—Se1—La1ii | 101.15 (2) |
La1vi—La1—La1vii | 180.00 (2) | La1i—Se1—La1ii | 83.04 (2) |
Se5v—La2—Se5iv | 85.65 (2) | In1v—Se2—In1iv | 99.22 (3) |
Se5v—La2—Se4v | 79.38 (2) | In1v—Se2—La1x | 97.12 (2) |
Se5iv—La2—Se4v | 136.10 (2) | In1iv—Se2—La1x | 97.12 (2) |
Se5v—La2—Se4iv | 136.10 (2) | In1v—Se2—La1 | 91.67 (2) |
Se5iv—La2—Se4iv | 79.382 (19) | In1iv—Se2—La1 | 91.67 (2) |
Se4v—La2—Se4iv | 83.45 (2) | La1x—Se2—La1 | 166.40 (2) |
Se5v—La2—Se3viii | 128.45 (2) | In1v—Se2—La2 | 130.213 (15) |
Se5iv—La2—Se3viii | 73.595 (18) | In1iv—Se2—La2 | 130.213 (15) |
Se4v—La2—Se3viii | 145.09 (2) | La1x—Se2—La2 | 83.84 (2) |
Se4iv—La2—Se3viii | 86.26 (2) | La1—Se2—La2 | 82.56 (2) |
Se5v—La2—Se3ix | 73.595 (18) | In1iv—Se3—In1v | 90.28 (3) |
Se5iv—La2—Se3ix | 128.45 (2) | In1iv—Se3—La2v | 153.46 (3) |
Se4v—La2—Se3ix | 86.26 (2) | In1v—Se3—La2v | 87.232 (18) |
Se4iv—La2—Se3ix | 145.09 (2) | In1iv—Se3—La2iv | 87.232 (18) |
Se3viii—La2—Se3ix | 83.39 (2) | In1v—Se3—La2iv | 153.46 (3) |
Se5v—La2—Se3x | 136.672 (12) | La2v—Se3—La2iv | 83.39 (2) |
Se5iv—La2—Se3x | 136.672 (12) | In1iv—Se3—La2iii | 97.84 (2) |
Se4v—La2—Se3x | 73.779 (19) | In1v—Se3—La2iii | 97.84 (2) |
Se4iv—La2—Se3x | 73.779 (19) | La2v—Se3—La2iii | 108.680 (18) |
Se3viii—La2—Se3x | 71.320 (18) | La2iv—Se3—La2iii | 108.680 (18) |
Se3ix—La2—Se3x | 71.320 (18) | In1xii—Se4—La1ii | 97.52 (2) |
Se5v—La2—Se2 | 66.952 (16) | In1xii—Se4—La1i | 97.52 (2) |
Se5iv—La2—Se2 | 66.952 (16) | La1ii—Se4—La1i | 84.30 (2) |
Se4v—La2—Se2 | 69.200 (18) | In1xii—Se4—La2viii | 104.19 (2) |
Se4iv—La2—Se2 | 69.200 (18) | La1ii—Se4—La2viii | 158.28 (3) |
Se3viii—La2—Se2 | 136.374 (13) | La1i—Se4—La2viii | 92.046 (16) |
Se3ix—La2—Se2 | 136.374 (13) | In1xii—Se4—La2ix | 104.19 (2) |
Se3x—La2—Se2 | 129.61 (2) | La1ii—Se4—La2ix | 92.046 (16) |
Se5v—La2—La2vi | 47.177 (12) | La1i—Se4—La2ix | 158.28 (3) |
Se5iv—La2—La2vi | 132.823 (12) | La2viii—Se4—La2ix | 83.45 (2) |
Se4v—La2—La2vi | 48.276 (11) | Cu1xi—Se5—La2ix | 103.85 (3) |
Se4iv—La2—La2vi | 131.724 (11) | Cu1xi—Se5—La2viii | 103.85 (3) |
Se3viii—La2—La2vi | 131.694 (12) | La2ix—Se5—La2viii | 85.65 (2) |
Se3ix—La2—La2vi | 48.306 (12) | Cu1xi—Se5—La1viii | 90.27 (3) |
Se3x—La2—La2vi | 90.0 | La2ix—Se5—La1viii | 165.76 (3) |
Se2—La2—La2vi | 90.0 | La2viii—Se5—La1viii | 92.868 (17) |
Se5v—La2—La2vii | 132.823 (12) | Cu1xi—Se5—La1ix | 90.27 (3) |
Se5iv—La2—La2vii | 47.177 (12) | La2ix—Se5—La1ix | 92.868 (17) |
Se4v—La2—La2vii | 131.724 (11) | La2viii—Se5—La1ix | 165.76 (3) |
Se4iv—La2—La2vii | 48.276 (11) | La1viii—Se5—La1ix | 85.09 (2) |
Se3viii—La2—La2vii | 48.306 (12) | ||
Se5iv—La1—Cu1—Se1ii | 151.39 (3) | Se2viii—In1—Se1—La1i | 7.132 (18) |
Se5v—La1—Cu1—Se1ii | 65.77 (3) | Se2ix—In1—Se1—La1i | −92.14 (2) |
Se4ii—La1—Cu1—Se1ii | −12.10 (4) | Se3ix—In1—Se1—La1i | −177.276 (16) |
Se4i—La1—Cu1—Se1ii | −130.74 (3) | Se3viii—In1—Se1—La1i | 92.27 (2) |
Se1i—La1—Cu1—Se1ii | −142.84 (5) | Se2viii—In1—Se1—La1ii | 92.14 (2) |
Se2iii—La1—Cu1—Se1ii | −71.42 (2) | Se2ix—In1—Se1—La1ii | −7.132 (18) |
Se2—La1—Cu1—Se1ii | 108.58 (2) | Se3ix—In1—Se1—La1ii | −92.27 (2) |
La1vi—La1—Cu1—Se1ii | 18.58 (2) | Se3viii—In1—Se1—La1ii | 177.276 (16) |
La1vii—La1—Cu1—Se1ii | −161.42 (2) | Se5iv—La1—Se2—In1v | −177.282 (19) |
Se5iv—La1—Cu1—Se1i | −65.77 (3) | Se5v—La1—Se2—In1v | −83.44 (2) |
Se5v—La1—Cu1—Se1i | −151.39 (3) | Se4ii—La1—Se2—In1v | 5.917 (15) |
Se4ii—La1—Cu1—Se1i | 130.74 (3) | Se4i—La1—Se2—In1v | 93.36 (2) |
Se4i—La1—Cu1—Se1i | 12.10 (4) | Se1i—La1—Se2—In1v | 162.00 (2) |
Se1ii—La1—Cu1—Se1i | 142.84 (5) | Se1ii—La1—Se2—In1v | −62.72 (3) |
Se2iii—La1—Cu1—Se1i | 71.42 (2) | Se2iii—La1—Se2—In1v | 49.641 (15) |
Se2—La1—Cu1—Se1i | −108.58 (2) | Cu1—La1—Se2—In1v | −130.359 (15) |
La1vi—La1—Cu1—Se1i | 161.42 (2) | La1vi—La1—Se2—In1v | −40.359 (15) |
La1vii—La1—Cu1—Se1i | −18.58 (2) | La1vii—La1—Se2—In1v | 139.641 (15) |
Se5iv—La1—Cu1—Se1 | 42.810 (12) | Se5iv—La1—Se2—In1iv | 83.44 (2) |
Se5v—La1—Cu1—Se1 | −42.810 (12) | Se5v—La1—Se2—In1iv | 177.282 (19) |
Se4ii—La1—Cu1—Se1 | −120.68 (2) | Se4ii—La1—Se2—In1iv | −93.36 (2) |
Se4i—La1—Cu1—Se1 | 120.68 (2) | Se4i—La1—Se2—In1iv | −5.917 (15) |
Se1i—La1—Cu1—Se1 | 108.58 (2) | Se1i—La1—Se2—In1iv | 62.72 (3) |
Se1ii—La1—Cu1—Se1 | −108.58 (2) | Se1ii—La1—Se2—In1iv | −162.00 (2) |
Se2iii—La1—Cu1—Se1 | 180.0 | Se2iii—La1—Se2—In1iv | −49.641 (15) |
Se2—La1—Cu1—Se1 | 0.0 | Cu1—La1—Se2—In1iv | 130.359 (15) |
Se5iv—La1—Cu1—Cu1i | −4.28 (3) | La1vi—La1—Se2—In1iv | −139.641 (15) |
Se5v—La1—Cu1—Cu1i | −89.90 (3) | La1vii—La1—Se2—In1iv | 40.359 (15) |
Se4ii—La1—Cu1—Cu1i | −167.78 (2) | Se5iv—La1—Se2—La1x | −46.923 (13) |
Se4i—La1—Cu1—Cu1i | 73.59 (4) | Se5v—La1—Se2—La1x | 46.923 (13) |
Se1i—La1—Cu1—Cu1i | 61.49 (2) | Se4ii—La1—Se2—La1x | 136.276 (12) |
Se1ii—La1—Cu1—Cu1i | −155.67 (5) | Se4i—La1—Se2—La1x | −136.276 (12) |
Se2iii—La1—Cu1—Cu1i | 132.91 (3) | Se1i—La1—Se2—La1x | −67.64 (2) |
Se2—La1—Cu1—Cu1i | −47.09 (3) | Se1ii—La1—Se2—La1x | 67.64 (2) |
La1vi—La1—Cu1—Cu1i | −137.09 (3) | Se2iii—La1—Se2—La1x | 180.0 |
La1vii—La1—Cu1—Cu1i | 42.91 (3) | Cu1—La1—Se2—La1x | 0.0 |
Se5iv—La1—Cu1—Cu1ii | 89.90 (3) | Se5iv—La1—Se2—La2 | −46.923 (13) |
Se5v—La1—Cu1—Cu1ii | 4.28 (3) | Se5v—La1—Se2—La2 | 46.923 (13) |
Se4ii—La1—Cu1—Cu1ii | −73.59 (4) | Se4ii—La1—Se2—La2 | 136.276 (12) |
Se4i—La1—Cu1—Cu1ii | 167.78 (2) | Se4i—La1—Se2—La2 | −136.276 (12) |
Se1i—La1—Cu1—Cu1ii | 155.67 (5) | Se1i—La1—Se2—La2 | −67.64 (2) |
Se1ii—La1—Cu1—Cu1ii | −61.49 (2) | Se1ii—La1—Se2—La2 | 67.64 (2) |
Se2iii—La1—Cu1—Cu1ii | −132.91 (3) | Se2iii—La1—Se2—La2 | 180.0 |
Se2—La1—Cu1—Cu1ii | 47.09 (3) | Cu1—La1—Se2—La2 | 0.0 |
La1vi—La1—Cu1—Cu1ii | −42.91 (3) | Se5v—La2—Se2—In1v | 38.26 (3) |
La1vii—La1—Cu1—Cu1ii | 137.09 (3) | Se5iv—La2—Se2—In1v | 133.50 (4) |
Se5xii—Cu1—Se1—Cu1ii | −115.45 (3) | Se4v—La2—Se2—In1v | −48.73 (3) |
Se1ii—Cu1—Se1—Cu1ii | 0.0 | Se4iv—La2—Se2—In1v | −139.52 (4) |
Se1i—Cu1—Se1—Cu1ii | 129.09 (6) | Se3viii—La2—Se2—In1v | 160.47 (3) |
Cu1i—Cu1—Se1—Cu1ii | 129.09 (6) | Se3ix—La2—Se2—In1v | 11.28 (5) |
La1—Cu1—Se1—Cu1ii | 64.55 (3) | Se3x—La2—Se2—In1v | −94.12 (3) |
Se5xii—Cu1—Se1—Cu1i | 115.45 (3) | La2vi—La2—Se2—In1v | −4.12 (3) |
Se1ii—Cu1—Se1—Cu1i | −129.09 (6) | La2vii—La2—Se2—In1v | 175.88 (3) |
Se1i—Cu1—Se1—Cu1i | 0.0 | Se5v—La2—Se2—In1iv | −133.50 (4) |
Cu1ii—Cu1—Se1—Cu1i | −129.09 (6) | Se5iv—La2—Se2—In1iv | −38.26 (3) |
La1—Cu1—Se1—Cu1i | −64.55 (3) | Se4v—La2—Se2—In1iv | 139.52 (4) |
Se5xii—Cu1—Se1—La1i | 41.761 (11) | Se4iv—La2—Se2—In1iv | 48.73 (3) |
Se1ii—Cu1—Se1—La1i | 157.22 (3) | Se3viii—La2—Se2—In1iv | −11.28 (5) |
Se1i—Cu1—Se1—La1i | −73.69 (3) | Se3ix—La2—Se2—In1iv | −160.47 (3) |
Cu1i—Cu1—Se1—La1i | −73.69 (3) | Se3x—La2—Se2—In1iv | 94.12 (3) |
Cu1ii—Cu1—Se1—La1i | 157.22 (3) | La2vi—La2—Se2—In1iv | −175.88 (3) |
La1—Cu1—Se1—La1i | −138.239 (11) | La2vii—La2—Se2—In1iv | 4.12 (3) |
Se5xii—Cu1—Se1—La1ii | −41.761 (11) | Se5v—La2—Se2—La1x | 132.380 (13) |
Se1ii—Cu1—Se1—La1ii | 73.69 (3) | Se5iv—La2—Se2—La1x | −132.380 (13) |
Se1i—Cu1—Se1—La1ii | −157.22 (3) | Se4v—La2—Se2—La1x | 45.394 (13) |
Cu1i—Cu1—Se1—La1ii | −157.22 (3) | Se4iv—La2—Se2—La1x | −45.394 (13) |
Cu1ii—Cu1—Se1—La1ii | 73.69 (3) | Se3viii—La2—Se2—La1x | −105.41 (3) |
La1—Cu1—Se1—La1ii | 138.239 (11) | Se3ix—La2—Se2—La1x | 105.41 (3) |
Se2viii—In1—Se1—Cu1ii | 167.44 (3) | Se3x—La2—Se2—La1x | 0.0 |
Se2ix—In1—Se1—Cu1ii | 68.17 (3) | Se5v—La2—Se2—La1 | −47.620 (13) |
Se3ix—In1—Se1—Cu1ii | −16.97 (3) | Se5iv—La2—Se2—La1 | 47.620 (13) |
Se3viii—In1—Se1—Cu1ii | −107.42 (3) | Se4v—La2—Se2—La1 | −134.606 (13) |
Se2viii—In1—Se1—Cu1i | −68.17 (3) | Se4iv—La2—Se2—La1 | 134.606 (13) |
Se2ix—In1—Se1—Cu1i | −167.44 (3) | Se3viii—La2—Se2—La1 | 74.59 (3) |
Se3ix—In1—Se1—Cu1i | 107.42 (3) | Se3ix—La2—Se2—La1 | −74.59 (3) |
Se3viii—In1—Se1—Cu1i | 16.97 (3) | Se3x—La2—Se2—La1 | 180.0 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1/2, y, −z+3/2; (iv) −x+1/2, −y, z+1/2; (v) −x+1/2, −y+1, z+1/2; (vi) x, y+1, z; (vii) x, y−1, z; (viii) −x+1/2, −y, z−1/2; (ix) −x+1/2, −y+1, z−1/2; (x) x−1/2, y, −z+3/2; (xi) x−1/2, y, −z+1/2; (xii) x+1/2, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | La2CuInSe5 |
Mr | 850.98 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 295 |
a, b, c (Å) | 12.051 (2), 4.1223 (8), 17.580 (4) |
V (Å3) | 873.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 35.34 |
Crystal size (mm) | 0.13 × 0.07 × 0.03 |
Data collection | |
Diffractometer | Kuma KM-4 diffractometer with CCD detector |
Absorption correction | Numerical (CrysAlis RED; Mayer, 2006) |
Tmin, Tmax | 0.076, 0.396 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9371, 1134, 1049 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.041, 1.12 |
No. of reflections | 1134 |
No. of parameters | 56 |
Δρmax, Δρmin (e Å−3) | 2.03, −1.68 |
Computer programs: CrysAlis CCD (Mayer, 2006), CrysAlis RED (Mayer, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2005), publCIF (Westrip, 2007).
La1—Se1i | 3.1094 (7) | La2—Se5iv | 3.0323 (7) |
La1—Se2 | 3.3013 (9) | In1—Se4vii | 2.6754 (9) |
La1—Se2ii | 3.2669 (10) | In1—Se1 | 2.6972 (9) |
La1—Se4iii | 3.0714 (7) | In1—Se2v | 2.7061 (6) |
La1—Se5iv | 3.0482 (7) | In1—Se3viii | 2.9079 (7) |
La2—Se2 | 3.3763 (9) | Cu1—Se1 | 2.6479 (13) |
La2—Se3v | 3.0988 (7) | Cu1—Se1iii | 2.4443 (7) |
La2—Se3vi | 3.1407 (9) | Cu1—Se1i | 2.4443 (7) |
La2—Se4iv | 3.0969 (6) | Cu1—Se5ix | 2.3920 (12) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, y, −z+3/2; (iii) −x+1, −y+1, −z+1; (iv) −x+1/2, −y, z+1/2; (v) −x+1/2, −y, z−1/2; (vi) x−1/2, y, −z+3/2; (vii) x−1/2, y, −z+1/2; (viii) −x+1/2, −y+1, z−1/2; (ix) x+1/2, y, −z+1/2. |
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The formation of quaternary La2CuInSe5 had been established earlier during the investigation of the phase relations in the La2Se3—Cu2Se—In2Se3 system (Huch, Gulay & Olekseyuk, 2007) and the crystal structure of this compound was investigated using X-ray powder diffraction (space group Pnma). The crystal structure of La2CuInSe5 has been reinvestigated by means of X-ray single-crystal diffraction and presented here. Crystal structure of the title compound is similar to previously reported La2CuInS5 (Huch, Gulay, Olekseyuk & Pietraszko, 2007).
The unit cell and the coordination polyhedra of the La, Cu, In and Se atoms in the structure of the La2CuInSe5 compound are shown in Fig. 1. Selenium atoms create bi-capped trigonal prisms, octahedra and tetrahedra around the La, In and Cu atoms, respectively. The coordination polyhedron of the copper atom can be extended to a trigonal bipyramid. In contrast to La2CuInS5, the position of the Cu atom is fully occupied and ordered (Fig. 2). The single-crystal data for La2CuInSe5 agree well with our previous powder diffraction results (Huch, Gulay & Olekseyuk, 2007).