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The crystal structure of the lanthanum titanium bismuthide La3TiBi5 (Pearson code hP18, Wyckoff sequence b d g2) has been established from single-crystal X-ray diffraction data and analyzed in detail using first-principles calculations. There are no anomalies pertaining to the atomic displacement parameter of the Ti site, previously reported based on a powder X-ray diffraction analysis of this compound. The anionic substructure contains columns of face-sharing TiBi6 octahedra and linear Bi chains. Due to a significant La(5d) and Bi(6p) orbital mixing, a perfectly one-dimensional character of the Bi chains is not realised, while a three-dimensional electronic structure is established instead. The latter fact explains the stability of the polyanionic pnictide units against Peierls distortions. The hypervalent bonding in the Bi chains is reflected in a rather long Bi—Bi distance of 3.2264 (4) Å and a typical pattern of bonding and antibonding interactions, as revealed by electronic structure calculations.
Supporting information
CCDC reference: 1836277
Data collection: SMART (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).
Trilanthanum titanium pentabismuthide
top
Crystal data top
La3TiBi5 | Dx = 9.560 Mg m−3 |
Mr = 1509.53 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P63/mcm | Cell parameters from 861 reflections |
a = 9.6871 (13) Å | θ = 4.9–26.9° |
c = 6.4528 (8) Å | µ = 96.13 mm−1 |
V = 524.40 (16) Å3 | T = 200 K |
Z = 2 | Block, black |
F(000) = 1216 | 0.12 × 0.07 × 0.05 mm |
Data collection top
CCD area detector diffractometer | 217 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.074 |
phi and ω scans | θmax = 26.9°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −10→12 |
Tmin = 0.008, Tmax = 0.046 | k = −12→11 |
4569 measured reflections | l = −8→8 |
233 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0129P)2 + 1.9223P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.019 | (Δ/σ)max < 0.001 |
wR(F2) = 0.037 | Δρmax = 1.27 e Å−3 |
S = 1.08 | Δρmin = −1.10 e Å−3 |
233 reflections | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
14 parameters | Extinction coefficient: 0.00126 (9) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
La1 | 0.61818 (9) | 0.0000 | 0.2500 | 0.0157 (2) | |
Ti1 | 0.0000 | 0.0000 | 0.0000 | 0.0169 (10) | |
Bi1 | 0.25353 (6) | 0.0000 | 0.2500 | 0.0152 (2) | |
Bi2 | 0.3333 | 0.6667 | 0.0000 | 0.0154 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
La1 | 0.0152 (4) | 0.0163 (5) | 0.0161 (4) | 0.0082 (3) | 0.000 | 0.000 |
Ti1 | 0.0163 (15) | 0.0163 (15) | 0.018 (2) | 0.0082 (7) | 0.000 | 0.000 |
Bi1 | 0.0144 (3) | 0.0153 (3) | 0.0163 (3) | 0.00764 (17) | 0.000 | 0.000 |
Bi2 | 0.0152 (3) | 0.0152 (3) | 0.0158 (4) | 0.00758 (13) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
La1—Bi1i | 3.2602 (8) | Ti1—Bi1 | 2.9384 (6) |
La1—Bi1ii | 3.2602 (7) | Ti1—Ti1xiv | 3.2264 (4) |
La1—Bi2iii | 3.4253 (3) | Ti1—Ti1xv | 3.2264 (4) |
La1—Bi2iv | 3.4253 (3) | Bi1—Ti1xiv | 2.9384 (6) |
La1—Bi2v | 3.4254 (3) | Bi1—La1xvi | 3.2601 (7) |
La1—Bi2vi | 3.4254 (3) | Bi1—La1xvii | 3.2601 (7) |
La1—Bi1vii | 3.4575 (6) | Bi1—La1vii | 3.4575 (6) |
La1—Bi1viii | 3.4575 (6) | Bi1—La1viii | 3.4575 (6) |
La1—Bi1 | 3.5323 (11) | Bi2—Bi2xviii | 3.2264 (4) |
La1—La1viii | 3.9563 (11) | Bi2—Bi2xix | 3.2264 (4) |
La1—La1vii | 3.9563 (11) | Bi2—La1xx | 3.4253 (4) |
Ti1—Bi1ix | 2.9384 (5) | Bi2—La1xxi | 3.4253 (3) |
Ti1—Bi1x | 2.9384 (5) | Bi2—La1x | 3.4253 (5) |
Ti1—Bi1xi | 2.9384 (6) | Bi2—La1vi | 3.4253 (3) |
Ti1—Bi1xii | 2.9384 (5) | Bi2—La1xvii | 3.4253 (3) |
Ti1—Bi1xiii | 2.9384 (5) | Bi2—La1xii | 3.4253 (4) |
| | | |
Bi1i—La1—Bi1ii | 81.45 (3) | Bi1x—Ti1—Bi1 | 92.745 (10) |
Bi1i—La1—Bi2iii | 141.80 (2) | Bi1xi—Ti1—Bi1 | 180.0 |
Bi1ii—La1—Bi2iii | 73.779 (12) | Bi1xii—Ti1—Bi1 | 87.255 (13) |
Bi1i—La1—Bi2iv | 141.80 (2) | Bi1xiii—Ti1—Bi1 | 92.745 (13) |
Bi1ii—La1—Bi2iv | 73.779 (12) | Bi1ix—Ti1—Ti1xiv | 123.299 (7) |
Bi2iii—La1—Bi2iv | 56.193 (8) | Bi1x—Ti1—Ti1xiv | 56.701 (7) |
Bi1i—La1—Bi2v | 73.780 (10) | Bi1xi—Ti1—Ti1xiv | 123.299 (8) |
Bi1ii—La1—Bi2v | 141.81 (2) | Bi1xii—Ti1—Ti1xiv | 123.299 (8) |
Bi2iii—La1—Bi2v | 140.95 (3) | Bi1xiii—Ti1—Ti1xiv | 56.701 (8) |
Bi2iv—La1—Bi2v | 109.451 (15) | Bi1—Ti1—Ti1xiv | 56.701 (8) |
Bi1i—La1—Bi2vi | 73.780 (10) | Bi1ix—Ti1—Ti1xv | 56.701 (7) |
Bi1ii—La1—Bi2vi | 141.81 (2) | Bi1x—Ti1—Ti1xv | 123.299 (7) |
Bi2iii—La1—Bi2vi | 109.451 (15) | Bi1xi—Ti1—Ti1xv | 56.701 (8) |
Bi2iv—La1—Bi2vi | 140.95 (3) | Bi1xii—Ti1—Ti1xv | 56.701 (8) |
Bi2v—La1—Bi2vi | 56.193 (8) | Bi1xiii—Ti1—Ti1xv | 123.299 (8) |
Bi1i—La1—Bi1vii | 74.192 (17) | Bi1—Ti1—Ti1xv | 123.299 (8) |
Bi1ii—La1—Bi1vii | 74.192 (17) | Ti1xiv—Ti1—Ti1xv | 180.0 |
Bi2iii—La1—Bi1vii | 124.029 (4) | Ti1—Bi1—Ti1xiv | 66.597 (16) |
Bi2iv—La1—Bi1vii | 71.376 (8) | Ti1—Bi1—La1xvi | 81.053 (15) |
Bi2v—La1—Bi1vii | 71.377 (6) | Ti1xiv—Bi1—La1xvi | 81.053 (15) |
Bi2vi—La1—Bi1vii | 124.029 (3) | Ti1—Bi1—La1xvii | 81.053 (14) |
Bi1i—La1—Bi1viii | 74.192 (18) | Ti1xiv—Bi1—La1xvii | 81.053 (14) |
Bi1ii—La1—Bi1viii | 74.192 (17) | La1xvi—Bi1—La1xvii | 158.55 (3) |
Bi2iii—La1—Bi1viii | 71.376 (7) | Ti1—Bi1—La1vii | 144.36 (2) |
Bi2iv—La1—Bi1viii | 124.029 (3) | Ti1xiv—Bi1—La1vii | 77.767 (17) |
Bi2v—La1—Bi1viii | 124.029 (3) | La1xvi—Bi1—La1vii | 93.835 (4) |
Bi2vi—La1—Bi1viii | 71.377 (6) | La1xvii—Bi1—La1vii | 93.835 (3) |
Bi1vii—La1—Bi1viii | 137.87 (4) | Ti1—Bi1—La1viii | 77.767 (17) |
Bi1i—La1—Bi1 | 139.276 (17) | Ti1xiv—Bi1—La1viii | 144.36 (2) |
Bi1ii—La1—Bi1 | 139.276 (16) | La1xvi—Bi1—La1viii | 93.835 (3) |
Bi2iii—La1—Bi1 | 70.476 (15) | La1xvii—Bi1—La1viii | 93.835 (3) |
Bi2iv—La1—Bi1 | 70.476 (15) | La1vii—Bi1—La1viii | 137.87 (4) |
Bi2v—La1—Bi1 | 70.475 (14) | Ti1—Bi1—La1 | 146.701 (8) |
Bi2vi—La1—Bi1 | 70.475 (14) | Ti1xiv—Bi1—La1 | 146.701 (8) |
Bi1vii—La1—Bi1 | 111.066 (18) | La1xvi—Bi1—La1 | 100.724 (17) |
Bi1viii—La1—Bi1 | 111.066 (18) | La1xvii—Bi1—La1 | 100.724 (16) |
Bi1i—La1—La1viii | 116.015 (12) | La1vii—Bi1—La1 | 68.934 (18) |
Bi1ii—La1—La1viii | 116.015 (11) | La1viii—Bi1—La1 | 68.935 (18) |
Bi2iii—La1—La1viii | 54.726 (8) | Bi2xviii—Bi2—Bi2xix | 180.0 |
Bi2iv—La1—La1viii | 100.99 (2) | Bi2xviii—Bi2—La1xx | 118.097 (4) |
Bi2v—La1—La1viii | 100.99 (2) | Bi2xix—Bi2—La1xx | 61.904 (4) |
Bi2vi—La1—La1viii | 54.725 (7) | Bi2xviii—Bi2—La1xxi | 61.904 (4) |
Bi1vii—La1—La1viii | 165.70 (4) | Bi2xix—Bi2—La1xxi | 118.097 (4) |
Bi1viii—La1—La1viii | 56.427 (14) | La1xx—Bi2—La1xxi | 166.36 (3) |
Bi1—La1—La1viii | 54.64 (2) | Bi2xviii—Bi2—La1x | 61.904 (5) |
Bi1i—La1—La1vii | 116.015 (12) | Bi2xix—Bi2—La1x | 118.097 (5) |
Bi1ii—La1—La1vii | 116.015 (11) | La1xx—Bi2—La1x | 70.550 (16) |
Bi2iii—La1—La1vii | 100.99 (2) | La1xxi—Bi2—La1x | 99.631 (8) |
Bi2iv—La1—La1vii | 54.726 (8) | Bi2xviii—Bi2—La1vi | 118.097 (3) |
Bi2v—La1—La1vii | 54.725 (8) | Bi2xix—Bi2—La1vi | 61.904 (4) |
Bi2vi—La1—La1vii | 100.99 (2) | La1xx—Bi2—La1vi | 99.631 (5) |
Bi1vii—La1—La1vii | 56.427 (14) | La1xxi—Bi2—La1vi | 70.550 (15) |
Bi1viii—La1—La1vii | 165.70 (4) | La1x—Bi2—La1vi | 91.52 (3) |
Bi1—La1—La1vii | 54.64 (2) | Bi2xviii—Bi2—La1xvii | 61.903 (4) |
La1viii—La1—La1vii | 109.28 (4) | Bi2xix—Bi2—La1xvii | 118.096 (3) |
Bi1ix—Ti1—Bi1x | 180.000 (13) | La1xx—Bi2—La1xvii | 91.52 (3) |
Bi1ix—Ti1—Bi1xi | 92.745 (10) | La1xxi—Bi2—La1xvii | 99.631 (6) |
Bi1x—Ti1—Bi1xi | 87.255 (10) | La1x—Bi2—La1xvii | 99.631 (6) |
Bi1ix—Ti1—Bi1xii | 92.745 (11) | La1vi—Bi2—La1xvii | 166.36 (3) |
Bi1x—Ti1—Bi1xii | 87.255 (11) | Bi2xviii—Bi2—La1xii | 118.096 (4) |
Bi1xi—Ti1—Bi1xii | 92.745 (12) | Bi2xix—Bi2—La1xii | 61.903 (5) |
Bi1ix—Ti1—Bi1xiii | 87.255 (11) | La1xx—Bi2—La1xii | 99.631 (9) |
Bi1x—Ti1—Bi1xiii | 92.745 (11) | La1xxi—Bi2—La1xii | 91.52 (3) |
Bi1xi—Ti1—Bi1xiii | 87.255 (12) | La1x—Bi2—La1xii | 166.36 (3) |
Bi1xii—Ti1—Bi1xiii | 180.00 (2) | La1vi—Bi2—La1xii | 99.631 (5) |
Bi1ix—Ti1—Bi1 | 87.255 (10) | La1xvii—Bi2—La1xii | 70.550 (15) |
Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x, z; (iii) x, y−1, z; (iv) x, y−1, −z+1/2; (v) −x+1, −y+1, z+1/2; (vi) −x+1, −y+1, −z; (vii) −x+1, −y, −z+1; (viii) −x+1, −y, −z; (ix) y, −x+y, −z; (x) −y, x−y, z; (xi) −x, −y, −z; (xii) x−y, x, −z; (xiii) −x+y, −x, z; (xiv) −x, −y, z+1/2; (xv) −x, −y, z−1/2; (xvi) −y, x−y−1, z; (xvii) −x+y+1, −x+1, z; (xviii) x, y, −z+1/2; (xix) x, y, −z−1/2; (xx) y, −x+y+1, −z; (xxi) x, y+1, z. |
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