Lithium divanadate spinel, LiV₂O₄

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].

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

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Computing details

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)

Crystal data

LiO4V2	Dx = 4.098 Mg m^−3
Mr = 172.82	Mo Kα radiation, λ = 0.71073 Å
Cubic, Fd3m	Cell parameters from 2848 reflections
Hall symbol: -F 4vw 2vw 3	θ = 9.3–53.2°
a = 8.2437 (2) Å	µ = 6.47 mm^−1
V = 560.23 (2) Å^3	T = 295 K
Z = 8	Octahedron, black
F(000) = 648.00	0.01 × 0.01 × 0.01 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	183 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
φ and ω scans	θmax = 53.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→18
Tmin = 0.878, Tmax = 0.937	k = −17→18
2848 measured reflections	l = −18→13
194 independent reflections

Refinement

Refinement on F^2	w = 1/(σ^2(Fo^2) + {0.07[Max(Fo^2,0) + 2Fc^2]/3}^2)
R[F^2 > 2σ(F^2)] = 0.026	(Δ/σ)max < 0.001
wR(F^2) = 0.076	Δρmax = 0.94 e Å^−3
S = 0.85	Δρmin = −1.11 e Å^−3
194 reflections	Extinction correction: Zachariasen (1968) type 2 Gaussian isotropic
8 parameters	Extinction coefficient: 0.009 (1)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
V	0.5000	0.5000	0.5000	0.00625 (2)
O	0.26147 (9)	0.26147	0.26147	0.00663 (3)
Li	0.1250	0.1250	0.1250	0.0074 (1)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V	0.0063 (1)	0.0063	0.0063	−0.00024 (3)	−0.0002	−0.0002
O	0.0066 (2)	0.0066	0.0066	0.0003 (4)	−0.0003	−0.0003
Li	0.0074 (8)	0.0074	0.0074	0.0000	0.0000	0.0000

Geometric parameters (Å, º)

V—V^i	2.9147 (4)	V—O^ii	1.9709 (7)
V—V^ii	2.9147 (4)	V—O^iii	1.9709 (7)
V—V^iii	2.9147 (4)	V—O^iv	1.9709 (7)
V—V^iv	2.9147 (4)	V—O^ix	1.9709 (7)
V—V^v	2.9147 (4)	V—V^i	2.9147 (4)
V—O^vi	1.9709 (7)	V—V^iii	2.9147 (4)
V—O^vii	1.9709 (7)	V—V^ii	2.9147 (4)
V—O^ii	1.9709 (7)	V—V^v	2.9147 (4)
Li—O^viii	1.9487 (5)	V—V^iv	2.9147 (4)
O—V^ii	1.9709 (7)	Li—O^x	1.9487 (5)
O—V^iv	1.9709 (7)	Li—O^viii	1.9487 (5)
V—O^vi	1.9709 (7)	Li—O^xi	1.9487 (5)
V—O^vii	1.9709 (7)
V^iii—O—V^ii	95.36 (4)	O^iii—V—V^ii	42.32 (2)
V^iii—O—V^iv	95.36 (4)	O^iv—V—V^ii	42.32 (2)
V^ii—O—V^iv	95.36 (4)	O^ix—V—V^ii	93.89 (3)
V^iii—O—Li	121.38 (3)	V^i—V—V^ii	120.0
V^ii—O—Li	121.38 (3)	V^iii—V—V^ii	60.0
V^iv—O—Li	121.38 (3)	O^vi—V—V^v	42.32 (2)
O^vii—V—O^iii	180.0	O^vii—V—V^v	42.32 (2)
O^ii—V—O^iii	84.38 (5)	O^ii—V—V^v	93.89 (3)
O^ii—V—O^iv	84.38 (5)	O^iii—V—V^v	137.68 (2)
O^iii—V—O^iv	84.38 (5)	O^iv—V—V^v	137.68 (2)
O^vi—V—O^ix	84.38 (5)	O^ix—V—V^v	86.11 (3)
O^vii—V—O^ix	84.38 (5)	V^i—V—V^v	60.0
O^ii—V—O^ix	180.0	V^iii—V—V^v	120.0
O^vi—V—V^i	42.32 (2)	V^ii—V—V^v	180.0
O^vii—V—V^i	86.11 (3)	O^vi—V—V^iv	93.89 (3)
O^ii—V—V^i	137.68 (2)	O^vii—V—V^iv	137.68 (2)
O^iii—V—V^i	93.89 (3)	O^ii—V—V^iv	42.32 (2)
O^iv—V—V^i	137.68 (2)	O^iii—V—V^iv	42.32 (2)
O^ix—V—V^i	42.32 (2)	O^iv—V—V^iv	86.11 (3)
O^vi—V—V^iii	137.68 (2)	O^ix—V—V^iv	137.68 (2)
O^vii—V—V^iii	93.89 (3)	V^i—V—V^iv	120.0
O^ii—V—V^iii	42.32 (2)	V^iii—V—V^iv	60.0
O^iii—V—V^iii	86.11 (3)	V^ii—V—V^iv	60.0
O^iv—V—V^iii	42.32 (2)	V^v—V—V^iv	120.0
O^ix—V—V^iii	137.68 (2)	O—Li—O^x	109.5
V^i—V—V^iii	180.0	O^x—Li—O^viii	109.5
O^vi—V—V^ii	137.68 (2)	O—Li—O^xi	109.5
O^vii—V—V^ii	137.68 (2)	O^x—Li—O^xi	109.5
O^ii—V—V^ii	86.11 (3)	O^viii—Li—O^xi	109.5

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.