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For the first time, large single crystals of lithium divanadate spinel, LiV2O4, showing heavy-fermion behavior down to 20 K, have been grown by a flux method using an effective LiCl–Li2MoO4–LiBO2 solvent system. LiV2O4 belongs to the normal spinel structure type. The V atoms (16d) have octa­hedral coordination [V—O = 1.9709 (7) Å] and are arranged in a pyrochlore-type sublattice [V...V = 2.9147 (4) Å]. The Li atoms (8a) have tetra­hedral coordination [Li—O = 1.9487 (5) Å] and are located in channels running parallel to [110].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805020155/mg6039sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805020155/mg6039Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](V-O) = 0.000 Å
  • R factor = 0.026
  • wR factor = 0.076
  • Data-to-parameter ratio = 24.3

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT731_ALERT_1_B Bond Calc 1.97090(10), Rep 1.9709(7) ...... 7.00 su-Rat V -O 1.555 100.666 PLAT731_ALERT_1_B Bond Calc 1.97090(10), Rep 1.9709(7) ...... 7.00 su-Rat V -O 1.555 27.554 PLAT731_ALERT_1_B Bond Calc 1.97090(10), Rep 1.9709(7) ...... 7.00 su-Rat O -V 1.555 27.554 PLAT731_ALERT_1_B Bond Calc 1.97090(10), Rep 1.9709(7) ...... 7.00 su-Rat O -V 1.555 4.555 PLAT731_ALERT_1_B Bond Calc 1.97090(10), Rep 1.9709(7) ...... 7.00 su-Rat V -O 1.555 100.666 PLAT731_ALERT_1_B Bond Calc 1.97090(10), Rep 1.9709(7) ...... 7.00 su-Rat V -O 1.555 27.554 PLAT731_ALERT_1_B Bond Calc 1.97090(10), Rep 1.9709(7) ...... 7.00 su-Rat V -O 1.555 4.555 PLAT731_ALERT_1_B Bond Calc 1.97090(10), Rep 1.9709(7) ...... 7.00 su-Rat V -O 1.555 123.656
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.25 Ratio PLAT731_ALERT_1_C Bond Calc 2.91460(10), Rep 2.9147(4) ...... 4.00 su-Rat V -V 1.555 2.566 PLAT731_ALERT_1_C Bond Calc 2.91460(10), Rep 2.9147(4) ...... 4.00 su-Rat V -V 1.555 27.554 PLAT731_ALERT_1_C Bond Calc 2.91460(10), Rep 2.9147(4) ...... 4.00 su-Rat V -V 1.555 26.555 PLAT731_ALERT_1_C Bond Calc 2.91460(10), Rep 2.9147(4) ...... 4.00 su-Rat V -V 1.555 4.555 PLAT731_ALERT_1_C Bond Calc 2.91460(10), Rep 2.9147(4) ...... 4.00 su-Rat V -V 1.555 51.564 PLAT731_ALERT_1_C Bond Calc 2.91460(10), Rep 2.9147(4) ...... 4.00 su-Rat V -V 1.555 2.566 PLAT731_ALERT_1_C Bond Calc 2.91460(10), Rep 2.9147(4) ...... 4.00 su-Rat V -V 1.555 26.555 PLAT731_ALERT_1_C Bond Calc 2.91460(10), Rep 2.9147(4) ...... 4.00 su-Rat V -V 1.555 27.554 PLAT731_ALERT_1_C Bond Calc 2.91460(10), Rep 2.9147(4) ...... 4.00 su-Rat V -V 1.555 51.564 PLAT731_ALERT_1_C Bond Calc 2.91460(10), Rep 2.9147(4) ...... 4.00 su-Rat V -V 1.555 4.555
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 53.17 From the CIF: _reflns_number_total 194 Count of symmetry unique reflns 1 Completeness (_total/calc) 19400.00% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 193 Fraction of Friedel pairs measured 193.000 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 8 ALERT level B = Potentially serious problem 13 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 21 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 1 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT and? TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: TEXSAN; molecular graphics: CrystalMaker (Palmer, 2005); software used to prepare material for publication: TEXSAN.

(I) top
Crystal data top
LiO4V2Dx = 4.098 Mg m3
Mr = 172.82Mo Kα radiation, λ = 0.71073 Å
Cubic, Fd3mCell parameters from 2848 reflections
Hall symbol: -F 4vw 2vw 3θ = 9.3–53.2°
a = 8.2437 (2) ŵ = 6.47 mm1
V = 560.23 (2) Å3T = 295 K
Z = 8Octahedron, black
F(000) = 648.000.01 × 0.01 × 0.01 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
183 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
φ and ω scansθmax = 53.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1718
Tmin = 0.878, Tmax = 0.937k = 1718
2848 measured reflectionsl = 1813
194 independent reflections
Refinement top
Refinement on F2 w = 1/(σ2(Fo2) + {0.07[Max(Fo2,0) + 2Fc2]/3}2)
R[F2 > 2σ(F2)] = 0.026(Δ/σ)max < 0.001
wR(F2) = 0.076Δρmax = 0.94 e Å3
S = 0.85Δρmin = 1.11 e Å3
194 reflectionsExtinction correction: Zachariasen (1968) type 2 Gaussian isotropic
8 parametersExtinction coefficient: 0.009 (1)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
V0.50000.50000.50000.00625 (2)
O0.26147 (9)0.261470.261470.00663 (3)
Li0.12500.12500.12500.0074 (1)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V0.0063 (1)0.00630.00630.00024 (3)0.00020.0002
O0.0066 (2)0.00660.00660.0003 (4)0.00030.0003
Li0.0074 (8)0.00740.00740.00000.00000.0000
Geometric parameters (Å, º) top
V—Vi2.9147 (4)V—Oii1.9709 (7)
V—Vii2.9147 (4)V—Oiii1.9709 (7)
V—Viii2.9147 (4)V—Oiv1.9709 (7)
V—Viv2.9147 (4)V—Oix1.9709 (7)
V—Vv2.9147 (4)V—Vi2.9147 (4)
V—Ovi1.9709 (7)V—Viii2.9147 (4)
V—Ovii1.9709 (7)V—Vii2.9147 (4)
V—Oii1.9709 (7)V—Vv2.9147 (4)
Li—Oviii1.9487 (5)V—Viv2.9147 (4)
O—Vii1.9709 (7)Li—Ox1.9487 (5)
O—Viv1.9709 (7)Li—Oviii1.9487 (5)
V—Ovi1.9709 (7)Li—Oxi1.9487 (5)
V—Ovii1.9709 (7)
Viii—O—Vii95.36 (4)Oiii—V—Vii42.32 (2)
Viii—O—Viv95.36 (4)Oiv—V—Vii42.32 (2)
Vii—O—Viv95.36 (4)Oix—V—Vii93.89 (3)
Viii—O—Li121.38 (3)Vi—V—Vii120.0
Vii—O—Li121.38 (3)Viii—V—Vii60.0
Viv—O—Li121.38 (3)Ovi—V—Vv42.32 (2)
Ovii—V—Oiii180.0Ovii—V—Vv42.32 (2)
Oii—V—Oiii84.38 (5)Oii—V—Vv93.89 (3)
Oii—V—Oiv84.38 (5)Oiii—V—Vv137.68 (2)
Oiii—V—Oiv84.38 (5)Oiv—V—Vv137.68 (2)
Ovi—V—Oix84.38 (5)Oix—V—Vv86.11 (3)
Ovii—V—Oix84.38 (5)Vi—V—Vv60.0
Oii—V—Oix180.0Viii—V—Vv120.0
Ovi—V—Vi42.32 (2)Vii—V—Vv180.0
Ovii—V—Vi86.11 (3)Ovi—V—Viv93.89 (3)
Oii—V—Vi137.68 (2)Ovii—V—Viv137.68 (2)
Oiii—V—Vi93.89 (3)Oii—V—Viv42.32 (2)
Oiv—V—Vi137.68 (2)Oiii—V—Viv42.32 (2)
Oix—V—Vi42.32 (2)Oiv—V—Viv86.11 (3)
Ovi—V—Viii137.68 (2)Oix—V—Viv137.68 (2)
Ovii—V—Viii93.89 (3)Vi—V—Viv120.0
Oii—V—Viii42.32 (2)Viii—V—Viv60.0
Oiii—V—Viii86.11 (3)Vii—V—Viv60.0
Oiv—V—Viii42.32 (2)Vv—V—Viv120.0
Oix—V—Viii137.68 (2)O—Li—Ox109.5
Vi—V—Viii180.0Ox—Li—Oviii109.5
Ovi—V—Vii137.68 (2)O—Li—Oxi109.5
Ovii—V—Vii137.68 (2)Ox—Li—Oxi109.5
Oii—V—Vii86.11 (3)Oviii—Li—Oxi109.5
Symmetry codes: (i) x, y+5/4, z+5/4; (ii) x+3/4, y+3/4, z; (iii) x, y+3/4, z+3/4; (iv) x+3/4, y, z+3/4; (v) x+5/4, y+5/4, z; (vi) x+1/4, y+1, z+1/4; (vii) x+1, y+1/4, z+1/4; (viii) x, y+1/4, z+1/4; (ix) x+1/4, y+1/4, z+1; (x) x+1/4, y, z+1/4; (xi) x+1/4, y+1/4, z.
 

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