Crystals of lithium niobium disulfide [LiyNbS2; y = 0.70 (9)] have been prepared by separated reactants metathesis (SRM) at 1073 K. Single-crystal data collected at reduced temperature [150 (2) K] indicate that the compound is isostructural with Li0.63NbS2 [Salyer, Barker, Blake, Gregory & Wilson (2003). Acta Cryst. C59, i4-i6], crystallizing in the hexagonal space group P63/mmc (No. 194). Li0.7NbS2 shows an expansion of both the a and c lattice parameters when compared with previously reported results on LiyNbS2 intercalation compounds with y < 0.70. This provides the first single-crystal structural evidence of unit cell expansion with increasing lithium content in LiyNbS2, where y > 0.5.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (Nb-S) = 0.001 Å
- Disorder in solvent or counterion
- R factor = 0.016
- wR factor = 0.047
- Data-to-parameter ratio = 9.4
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
CRYSC_01 Alert C There is an ordering error in _exptl_crystal_colour.
It should be (QUALIFIER) (INTENSITY) (BASE_COLOUR).
PLAT_302 Alert C Anion/Solvent Disorder ......................... 3.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT and SHELXTL (Bruker, 1997); program(s) used to solve structure: SIR92 (Altomare, 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS 4.1 (Dowty, 1998); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 1990, 2002).
Crystal data top
Li0.70NbS2 | Dx = 4.260 Mg m−3 |
Mr = 161.89 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P63/mmc | Cell parameters from 778 reflections |
Hall symbol: -p 6c 2c | θ = 3.2–28.9° |
a = 3.3572 (5) Å | µ = 6.02 mm−1 |
c = 12.912 (3) Å | T = 150 K |
V = 126.03 (4) Å3 | Hexagonal tablet, metallic grey |
Z = 2 | 0.10 × 0.10 × 0.04 mm |
F(000) = 150 | |
Data collection top
Bruker SMART1000 CCD area-detector diffractometer | 85 independent reflections |
Radiation source: normal-focus sealed tube | 83 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scans | θmax = 28.8°, θmin = 3.2° |
Absorption correction: integration (SHELXTL; Bruker, 2001) | h = −4→4 |
Tmin = 0.600, Tmax = 0.789 | k = −4→4 |
974 measured reflections | l = −17→17 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.016 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.047 | w = 1/[σ2(Fo2) + (0.0212P)2 + 0.2307P] where P = (Fo2 + 2Fc2)/3 |
S = 1.58 | (Δ/σ)max < 0.001 |
85 reflections | Δρmax = 0.69 e Å−3 |
9 parameters | Δρmin = −0.60 e Å−3 |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Nb1 | 0.0000 | 0.0000 | 0.2500 | 0.0050 (3) | |
S1 | 0.3333 | 0.6667 | 0.12828 (10) | 0.0061 (4) | |
Li1 | 0.0000 | 0.0000 | 0.0000 | 0.012 (8) | 0.70 (9) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Nb1 | 0.0041 (3) | 0.0041 (3) | 0.0068 (4) | 0.00207 (16) | 0.000 | 0.000 |
S1 | 0.0052 (5) | 0.0052 (5) | 0.0077 (6) | 0.0026 (2) | 0.000 | 0.000 |
Li1 | 0.015 (10) | 0.015 (10) | 0.006 (11) | 0.007 (5) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Nb1—S1i | 2.4954 (9) | S1—Li1 | 2.5495 (9) |
Nb1—S1ii | 2.4954 (9) | S1—Li1viii | 2.5495 (9) |
Nb1—S1iii | 2.4954 (9) | S1—Li1vii | 2.5495 (9) |
Nb1—S1iv | 2.4954 (9) | Li1—S1x | 2.5495 (9) |
Nb1—S1 | 2.4954 (9) | Li1—S1xi | 2.5495 (9) |
Nb1—S1v | 2.4954 (9) | Li1—S1iv | 2.5495 (9) |
Nb1—Li1vi | 3.2279 (6) | Li1—S1xii | 2.5495 (9) |
Nb1—Li1 | 3.2279 (6) | Li1—S1ii | 2.5495 (9) |
Nb1—Nb1ii | 3.3572 (5) | Li1—Nb1x | 3.2279 (6) |
Nb1—Nb1vii | 3.3572 (5) | Li1—Li1vii | 3.3572 (5) |
Nb1—Nb1viii | 3.3572 (5) | Li1—Li1ii | 3.3572 (5) |
Nb1—Nb1ix | 3.3572 (5) | Li1—Li1iv | 3.3572 (5) |
S1—Nb1vii | 2.4954 (9) | Li1—Li1xiii | 3.3572 (5) |
S1—Nb1viii | 2.4954 (9) | | |
| | | |
S1i—Nb1—S1ii | 134.294 (17) | Nb1viii—S1—Li1viii | 79.550 (14) |
S1i—Nb1—S1iii | 84.55 (4) | Nb1—S1—Li1viii | 134.782 (5) |
S1ii—Nb1—S1iii | 134.294 (17) | Li1—S1—Li1viii | 82.36 (4) |
S1i—Nb1—S1iv | 134.294 (17) | Nb1vii—S1—Li1vii | 79.550 (14) |
S1ii—Nb1—S1iv | 84.55 (4) | Nb1viii—S1—Li1vii | 134.782 (5) |
S1iii—Nb1—S1iv | 78.07 (5) | Nb1—S1—Li1vii | 134.782 (5) |
S1i—Nb1—S1 | 78.07 (5) | Li1—S1—Li1vii | 82.36 (4) |
S1ii—Nb1—S1 | 84.55 (4) | Li1viii—S1—Li1vii | 82.36 (4) |
S1iii—Nb1—S1 | 134.294 (17) | S1x—Li1—S1 | 180.00 (5) |
S1iv—Nb1—S1 | 84.55 (4) | S1x—Li1—S1xi | 82.36 (4) |
S1i—Nb1—S1v | 84.55 (4) | S1—Li1—S1xi | 97.64 (4) |
S1ii—Nb1—S1v | 78.07 (5) | S1x—Li1—S1iv | 97.64 (4) |
S1iii—Nb1—S1v | 84.55 (4) | S1—Li1—S1iv | 82.36 (4) |
S1iv—Nb1—S1v | 134.294 (17) | S1xi—Li1—S1iv | 180.00 (5) |
S1—Nb1—S1v | 134.294 (17) | S1x—Li1—S1xii | 82.36 (4) |
Li1vi—Nb1—Li1 | 180.0 | S1—Li1—S1xii | 97.64 (4) |
Nb1vii—S1—Nb1viii | 84.55 (4) | S1xi—Li1—S1xii | 82.36 (4) |
Nb1vii—S1—Nb1 | 84.55 (4) | S1iv—Li1—S1xii | 97.64 (4) |
Nb1viii—S1—Nb1 | 84.55 (4) | S1x—Li1—S1ii | 97.64 (4) |
Nb1vii—S1—Li1 | 134.782 (5) | S1—Li1—S1ii | 82.36 (4) |
Nb1viii—S1—Li1 | 134.782 (5) | S1xi—Li1—S1ii | 97.64 (4) |
Nb1—S1—Li1 | 79.550 (14) | S1iv—Li1—S1ii | 82.36 (4) |
Nb1vii—S1—Li1viii | 134.782 (5) | S1xii—Li1—S1ii | 180.00 (5) |
Symmetry codes: (i) x, y, −z+1/2; (ii) x−1, y−1, z; (iii) x, y−1, −z+1/2; (iv) x, y−1, z; (v) x−1, y−1, −z+1/2; (vi) −x, −y, z+1/2; (vii) x+1, y+1, z; (viii) x, y+1, z; (ix) x+1, y, z; (x) −x, −y, −z; (xi) −x, −y+1, −z; (xii) −x+1, −y+1, −z; (xiii) x−1, y, z. |