Li3+δV6O13: a short-range-ordered lithium insertion mechanism

Höwing, J.; Gustafsson, T.; Thomas, J.O.

doi:10.1107/S0108768104013096

Li_3+δV₆O₁₃: a short-range-ordered lithium insertion mechanism

J. Höwing, T. Gustafsson and J. O. Thomas

The structures of Li₃V₆O₁₃ and Li_3+δV₆O₁₃, δ ≃ 0.3, have been determined by single-crystal X-ray diffraction. Both compounds have the space group C2/m, with very similar cell parameters. In Li₃V₆O₁₃, the Li atoms are found in the Wyckoff positions 4(i) and 2(b) with multiplicities of four and two, respectively. Since Li₃V₆O₁₃ exhibits no superstructure reflections, it is concluded that Li₃V₆O₁₃ contains one disordered lithium ion in an otherwise ordered centrosymmetric structure. On inserting more lithium into the structure, the Li_3+δV₆O₁₃ phase is formed with the homogeneity range 0 < δ < 1. It is concluded that the site for the extra inserted lithium ion is closely coupled to the position of the disordered lithium ion in Li₃V₆O₁₃. A mechanism for this behaviour and for the further formation of the Li₆V₆O₁₃ end-phase in the Li_xV₆O₁₃ system is proposed.

Keywords: lithium-ion battery; vanadium oxide; insertion mechanism; disorder.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768104013096/bm5009sup1.cif Contains datablocks global, Li3V6O13, Li3+dV6O13
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768104013096/bm5009Li3V6O13sup2.hkl Contains datablock Li3V6O13
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768104013096/bm5009Li3+dV6O13sup3.hkl Contains datablock Li3+dV6O13

Computing details top

For both compounds, data collection: SMART (Bruker 2003); cell refinement: SAINT+ (Bruker 2003); data reduction: SAINT+ (Bruker 2003); program(s) used to refine structure: Jana2000 (Petricek and Dusek, 2000); molecular graphics: Diamond Version 2.1c; software used to prepare material for publication: Jana2000 (Petricek and Dusek, 2000).

Figures top

(Li3V6O13) top

Crystal data top

Li₃O₁₃V₆	F(000) = 502
M_r = 534.5	D_x = 3.831 (1) Mg m⁻³
Monoclinic, C2/m	Ag Kα radiation, λ = 0.56083 Å
Hall symbol: -C 2y	Cell parameters from 855 reflections
a = 11.792 (1) Å	θ = 5.5–54.7°
b = 3.9214 (4) Å	µ = 3.01 mm⁻¹
c = 10.189 (1) Å	T = 295 K
β = 100.596 (2)°	Brick, black
V = 463.12 (8) Å³	0.20 × 0.14 × 0.04 mm
Z = 2

Data collection top

CCD area detector diffractometer	1179 independent reflections
Radiation source: fine-focus sealed tube	1179 reflections with I > −15σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 1024*1024 pixels mm^-1	θ_max = 28.2°, θ_min = 1.6°
ω scans	h = −18→15
Absorption correction: empirical (using intensity measurements) SADABS (Bruker 2003)	k = −5→6
T_min = 1.000, T_max = 1.000	l = −16→16
2830 measured reflections

Refinement top

Refinement on F²	69 parameters
R[F² > 2σ(F²)] = 0.057	Weighting scheme based on measured s.u.'s w = 1/σ²(I)
wR(F²) = 0.059	(Δ/σ)_max = 0.028
S = 2.09	Δρ_max = 2.14 e Å⁻³
1179 reflections	Δρ_min = −1.30 e Å⁻³

Crystal data top

Li₃O₁₃V₆	V = 463.12 (8) Å³
M_r = 534.5	Z = 2
Monoclinic, C2/m	Ag Kα radiation, λ = 0.56083 Å
a = 11.792 (1) Å	µ = 3.01 mm⁻¹
b = 3.9214 (4) Å	T = 295 K
c = 10.189 (1) Å	0.20 × 0.14 × 0.04 mm
β = 100.596 (2)°

Data collection top

CCD area detector diffractometer	1179 independent reflections
Absorption correction: empirical (using intensity measurements) SADABS (Bruker 2003)	1179 reflections with I > −15σ(I)
T_min = 1.000, T_max = 1.000	R_int = 0.027
2830 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	69 parameters
wR(F²) = 0.059	Δρ_max = 2.14 e Å⁻³
S = 2.09	Δρ_min = −1.30 e Å⁻³
1179 reflections

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
V1	0.34311 (6)	0	0.00141 (6)	0.00974 (16)
V2	0.40032 (5)	0	0.36633 (5)	0.00720 (17)
V3	0.72145 (5)	0	0.36421 (5)	0.00678 (17)
O1	0.1729 (2)	0	0.9992 (2)	0.0108 (7)
O2	0.8923 (2)	0	0.3918 (2)	0.0076 (7)
O3	0.23911 (19)	0	0.4050 (2)	0.0082 (7)
O4	0.5	0	0	0.0121 (11)
O5	0.3788 (2)	0	0.2006 (2)	0.0104 (7)
O6	0.6856 (2)	0	0.2008 (2)	0.0101 (7)
O7	0.5693 (2)	0	0.4150 (2)	0.0082 (7)
Li1	0.5683 (5)	0.5	0.4093 (6)	0.0128 (18)
Li2	0.5	0.5	0	0.115 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.0101 (3)	0.0074 (3)	0.0115 (2)	0	0.0015 (2)	0
V2	0.0069 (3)	0.0059 (3)	0.0089 (3)	0	0.0017 (2)	0
V3	0.0066 (3)	0.0049 (3)	0.0088 (3)	0	0.0012 (2)	0
O1	0.0125 (14)	0.0057 (12)	0.0140 (11)	0	0.0015 (10)	0
O2	0.0067 (11)	0.0041 (11)	0.0118 (10)	0	0.0010 (9)	0
O3	0.0052 (11)	0.0065 (12)	0.0129 (11)	0	0.0019 (9)	0
O4	0.0127 (19)	0.0112 (19)	0.0128 (16)	0	0.0033 (14)	0
O5	0.0112 (12)	0.0088 (13)	0.0112 (11)	0	0.0018 (9)	0
O6	0.0111 (12)	0.0074 (13)	0.0117 (11)	0	0.0020 (9)	0
O7	0.0073 (12)	0.0052 (12)	0.0123 (11)	0	0.0027 (9)	0
Li1	0.010 (3)	0.005 (3)	0.024 (3)	0	0.006 (3)	0
Li2	0.034 (9)	0.069 (13)	0.26 (3)	0	0.063 (13)	0

Geometric parameters (Å, º) top

V1—O1ⁱ	2.003 (3)	V3—O3^ix	2.0072 (5)
V1—O1ⁱⁱ	1.9696 (3)	V3—O3^vii	2.312 (2)
V1—O1ⁱⁱⁱ	1.9696 (3)	V3—O6	1.641 (2)
V1—O4	1.8529 (7)	V3—O7	1.957 (3)
V1—O5	1.995 (2)	Li1—O2^vi	2.050 (7)
V1—O6^iv	2.025 (2)	Li1—O2^x	1.994 (6)
V2—O2^v	1.9823 (4)	Li1—O3^ix	2.022 (7)
V2—O2^vi	1.9823 (4)	Li1—O7	1.9615 (2)
V2—O3	2.011 (3)	Li1—O7^xi	1.9615 (2)
V2—O5	1.661 (2)	Li2—O1^xii	2.040 (3)
V2—O7	1.963 (2)	Li2—O1ⁱⁱⁱ	2.040 (3)
V2—O7^vii	2.191 (2)	Li2—O4	1.9607 (2)
V3—O2	1.983 (3)	Li2—O4^xi	1.9607 (2)
V3—O3^viii	2.0072 (5)

O1ⁱ—V1—O1ⁱⁱ	84.54 (8)	O2—V3—O3^vii	81.17 (9)
O1ⁱ—V1—O1ⁱⁱⁱ	84.54 (8)	O2—V3—O6	102.11 (11)
O1ⁱ—V1—O4	178.93 (8)	O2—V3—O7	156.92 (9)
O1ⁱ—V1—O5	92.00 (10)	O3^viii—V3—O3^ix	155.29 (9)
O1ⁱ—V1—O6^iv	90.52 (10)	O3^viii—V3—O3^vii	78.20 (6)
O1ⁱⁱ—V1—O1ⁱ	84.54 (8)	O3^viii—V3—O6	101.99 (6)
O1ⁱⁱ—V1—O1ⁱⁱⁱ	169.08 (11)	O3^viii—V3—O7	90.60 (7)
O1ⁱⁱ—V1—O4	95.46 (8)	O3^ix—V3—O3^viii	155.29 (9)
O1ⁱⁱ—V1—O5	90.31 (7)	O3^ix—V3—O3^vii	78.20 (6)
O1ⁱⁱ—V1—O6^iv	89.93 (7)	O3^ix—V3—O6	101.99 (6)
O1ⁱⁱⁱ—V1—O1ⁱ	84.54 (8)	O3^ix—V3—O7	90.60 (7)
O1ⁱⁱⁱ—V1—O1ⁱⁱ	169.08 (11)	O3^vii—V3—O3^viii	78.20 (6)
O1ⁱⁱⁱ—V1—O4	95.46 (8)	O3^vii—V3—O3^ix	78.20 (6)
O1ⁱⁱⁱ—V1—O5	90.31 (7)	O3^vii—V3—O6	176.72 (11)
O1ⁱⁱⁱ—V1—O6^iv	89.93 (7)	O3^vii—V3—O7	75.74 (9)
O4—V1—O5	89.07 (7)	O6—V3—O7	100.98 (11)
O4—V1—O6^iv	88.41 (7)	O2^vi—Li1—O2^x	97.5 (3)
O5—V1—O6^iv	177.48 (11)	O2^vi—Li1—O3^ix	173.9 (3)
O2^v—V2—O2^vi	163.05 (10)	O2^vi—Li1—O7	90.2 (2)
O2^v—V2—O3	84.54 (8)	O2^vi—Li1—O7^xi	90.2 (2)
O2^v—V2—O5	97.54 (7)	O2^x—Li1—O2^vi	97.5 (3)
O2^v—V2—O7	92.14 (7)	O2^x—Li1—O3^ix	88.6 (2)
O2^v—V2—O7^vii	82.51 (7)	O2^x—Li1—O7	88.34 (18)
O2^vi—V2—O2^v	163.05 (10)	O2^x—Li1—O7^xi	88.34 (18)
O2^vi—V2—O3	84.54 (8)	O3^ix—Li1—O7	90.0 (2)
O2^vi—V2—O5	97.54 (7)	O3^ix—Li1—O7^xi	90.0 (2)
O2^vi—V2—O7	92.14 (7)	O7—Li1—O7^xi	176.7 (4)
O2^vi—V2—O7^vii	82.51 (7)	O7^xi—Li1—O7	176.7 (4)
O3—V2—O5	103.06 (10)	O1^xii—Li2—O1ⁱⁱⁱ	180
O3—V2—O7	154.51 (9)	O1^xii—Li2—O4	90
O3—V2—O7^vii	77.55 (9)	O1^xii—Li2—O4^xi	90
O5—V2—O7	102.43 (11)	O1ⁱⁱⁱ—Li2—O1^xii	180
O5—V2—O7^vii	179.39 (11)	O1ⁱⁱⁱ—Li2—O4	90
O7—V2—O7^vii	76.97 (9)	O1ⁱⁱⁱ—Li2—O4^xi	90
O7^vii—V2—O7	76.97 (9)	O4—Li2—O4^xi	180
O2—V3—O3^viii	84.64 (7)	O4^xi—Li2—O4	180
O2—V3—O3^ix	84.64 (7)

Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, −y−1/2, −z+1; (iii) −x+1/2, −y+1/2, −z+1; (iv) −x+1, −y, −z; (v) x−1/2, y−1/2, z; (vi) x−1/2, y+1/2, z; (vii) −x+1, −y, −z+1; (viii) x+1/2, y−1/2, z; (ix) x+1/2, y+1/2, z; (x) −x+3/2, −y+1/2, −z+1; (xi) x, y+1, z; (xii) x+1/2, y+1/2, z−1.

(Li3+dV6O13) top

Crystal data top

Li_3.25V₆O₁₃	F(000) = 503
M_r = 536.2	D_x = 3.886 (1) Mg m⁻³
Monoclinic, C2/m	Synchrotron radiation, λ = 0.872 Å
Hall symbol: -C 2y	Cell parameters from 594 reflections
a = 11.7236 (6) Å	θ = 9.2–63.8°
b = 3.9155 (2) Å	µ = 10.35 mm⁻¹
c = 10.1521 (5) Å	T = 295 K
β = 100.592 (2)°	Shard, black
V = 458.08 (4) Å³	0.05 × 0.02 × 0.01 mm
Z = 2

Data collection top

CCD area detector diffractometer	1372 independent reflections
Radiation source: synchrotron	1365 reflections with I > −15σ(I)
Si(111) monochromator	R_int = 0.040
Detector resolution: 512*512 pixels mm^-1	θ_max = 50.6°, θ_min = 2.5°
ω scans	h = −15→20
Absorption correction: empirical (using intensity measurements) SADABS (Bruker, 2003)	k = −4→6
T_min = 1.000, T_max = 1.000	l = −17→14
5374 measured reflections

Refinement top

Refinement on F²	71 parameters
R[F² > 2σ(F²)] = 0.029	Weighting scheme based on measured s.u.'s w = 1/σ²(I)
wR(F²) = 0.048	(Δ/σ)_max = 0.004
S = 3.24	Δρ_max = 1.34 e Å⁻³
1365 reflections	Δρ_min = −1.17 e Å⁻³

Crystal data top

Li_3.25V₆O₁₃	V = 458.08 (4) Å³
M_r = 536.2	Z = 2
Monoclinic, C2/m	Synchrotron radiation, λ = 0.872 Å
a = 11.7236 (6) Å	µ = 10.35 mm⁻¹
b = 3.9155 (2) Å	T = 295 K
c = 10.1521 (5) Å	0.05 × 0.02 × 0.01 mm
β = 100.592 (2)°

Data collection top

CCD area detector diffractometer	1372 independent reflections
Absorption correction: empirical (using intensity measurements) SADABS (Bruker, 2003)	1365 reflections with I > −15σ(I)
T_min = 1.000, T_max = 1.000	R_int = 0.040
5374 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	71 parameters
wR(F²) = 0.048	Δρ_max = 1.34 e Å⁻³
S = 3.24	Δρ_min = −1.17 e Å⁻³
1365 reflections

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
V1	0.34224 (3)	0	0.00123 (4)	0.00696 (6)
V2	0.40029 (2)	0	0.36658 (3)	0.00578 (6)
V3	0.72165 (2)	0	0.36435 (3)	0.00548 (6)
O1	0.17147 (11)	0	0.99929 (16)	0.0080 (3)
O2	0.89293 (10)	0	0.39131 (15)	0.0065 (3)
O3	0.23889 (10)	0	0.40451 (15)	0.0063 (3)
O4	0.5	0	0	0.0088 (4)
O5	0.37866 (12)	0	0.20022 (15)	0.0086 (3)
O6	0.68596 (11)	0	0.20038 (16)	0.0091 (3)
O7	0.56898 (10)	0	0.41478 (15)	0.0066 (3)
Li1	0.5676 (3)	0.5	0.4096 (5)	0.0107 (8)
Li2	0.5	0.5	0	0.057 (5)
Li3	0.868 (2)	0	0.197 (4)	0.0102*	0.1239

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.00557 (9)	0.00624 (7)	0.00892 (13)	0	0.00094 (7)	0
V2	0.00395 (8)	0.00612 (7)	0.00727 (13)	0	0.00099 (7)	0
V3	0.00416 (8)	0.00522 (7)	0.00704 (12)	0	0.00095 (7)	0
O1	0.0079 (4)	0.0045 (3)	0.0114 (6)	0	0.0014 (4)	0
O2	0.0045 (4)	0.0041 (3)	0.0106 (6)	0	0.0009 (3)	0
O3	0.0048 (4)	0.0044 (3)	0.0098 (6)	0	0.0014 (3)	0
O4	0.0067 (6)	0.0078 (4)	0.0120 (9)	0	0.0020 (5)	0
O5	0.0097 (4)	0.0083 (3)	0.0075 (6)	0	0.0009 (3)	0
O6	0.0094 (4)	0.0100 (3)	0.0077 (6)	0	0.0011 (4)	0
O7	0.0035 (3)	0.0062 (3)	0.0103 (6)	0	0.0016 (3)	0
Li1	0.0100 (13)	0.0088 (9)	0.0138 (19)	0	0.0035 (11)	0
Li2	0.018 (3)	0.0115 (19)	0.146 (15)	0	0.029 (6)	0

Geometric parameters (Å, º) top

V1—O1ⁱ	1.998 (1)	V3—O6	1.640 (2)
V1—O1ⁱⁱ	1.9643 (1)	V3—O7	1.949 (1)
V1—O1ⁱⁱⁱ	1.9643 (1)	Li1—O2^vi	2.022 (4)
V1—O4	1.8518 (3)	Li1—O2^x	1.988 (5)
V1—O5	1.986 (2)	Li1—O3^ix	2.018 (4)
V1—O6^iv	2.012 (2)	Li1—O7	1.9584 (1)
V2—O2^v	1.9777 (2)	Li1—O7^xi	1.9584 (1)
V2—O2^vi	1.9777 (2)	Li2—O1^xii	2.011 (1)
V2—O3	1.999 (1)	Li2—O1ⁱⁱⁱ	2.011 (1)
V2—O5	1.661 (2)	Li2—O4	1.9577
V2—O7	1.948 (1)	Li2—O4^xi	1.9577
V2—O7^vii	2.182 (2)	Li3—O1^vii	1.96 (3)
V3—O2	1.976 (1)	Li3—O2	1.94 (4)
V3—O3^viii	2.0024 (3)	Li3—O5^viii	1.961 (2)
V3—O3^ix	2.0024 (3)	Li3—O5^ix	1.961 (2)
V3—O3^vii	2.306 (2)	Li3—O6	2.14 (3)

O1ⁱ—V1—O1ⁱⁱ	85.33 (4)	O3^viii—V3—O6	101.77 (4)
O1ⁱ—V1—O1ⁱⁱⁱ	85.33 (4)	O3^viii—V3—O7	90.56 (4)
O1ⁱ—V1—O4	179.06 (5)	O3^ix—V3—O3^viii	155.76 (6)
O1ⁱ—V1—O5	92.16 (6)	O3^ix—V3—O3^vii	78.40 (4)
O1ⁱ—V1—O6^iv	90.74 (6)	O3^ix—V3—O6	101.77 (4)
O1ⁱⁱ—V1—O1ⁱ	85.33 (4)	O3^ix—V3—O7	90.56 (4)
O1ⁱⁱ—V1—O1ⁱⁱⁱ	170.66 (6)	O3^vii—V3—O3^viii	78.40 (4)
O1ⁱⁱ—V1—O4	94.67 (4)	O3^vii—V3—O3^ix	78.40 (4)
O1ⁱⁱ—V1—O5	90.28 (5)	O3^vii—V3—O6	176.85 (6)
O1ⁱⁱ—V1—O6^iv	89.95 (5)	O3^vii—V3—O7	75.82 (5)
O1ⁱⁱⁱ—V1—O1ⁱ	85.33 (4)	O6—V3—O7	101.03 (6)
O1ⁱⁱⁱ—V1—O1ⁱⁱ	170.66 (6)	O2^vi—Li1—O2^x	97.8 (2)
O1ⁱⁱⁱ—V1—O4	94.67 (4)	O2^vi—Li1—O3^ix	173.4 (3)
O1ⁱⁱⁱ—V1—O5	90.28 (5)	O2^vi—Li1—O7	90.33 (12)
O1ⁱⁱⁱ—V1—O6^iv	89.95 (5)	O2^vi—Li1—O7^xi	90.33 (12)
O4—V1—O5	88.78 (4)	O2^x—Li1—O2^vi	97.8 (2)
O4—V1—O6^iv	88.32 (4)	O2^x—Li1—O3^ix	88.82 (16)
O5—V1—O6^iv	177.10 (6)	O2^x—Li1—O7	88.49 (14)
O2^v—V2—O2^vi	163.72 (7)	O2^x—Li1—O7^xi	88.49 (14)
O2^v—V2—O3	84.87 (4)	O3^ix—Li1—O7	89.85 (12)
O2^v—V2—O5	97.29 (4)	O3^ix—Li1—O7^xi	89.85 (12)
O2^v—V2—O7	91.95 (3)	O7—Li1—O7^xi	177.0 (3)
O2^v—V2—O7^vii	82.75 (4)	O7^xi—Li1—O7	177.0 (3)
O2^vi—V2—O2^v	163.72 (7)	O1^xii—Li2—O1ⁱⁱⁱ	180
O2^vi—V2—O3	84.87 (4)	O1^xii—Li2—O4	90
O2^vi—V2—O5	97.29 (4)	O1^xii—Li2—O4^xi	90
O2^vi—V2—O7	91.95 (3)	O1ⁱⁱⁱ—Li2—O1^xii	180
O2^vi—V2—O7^vii	82.75 (4)	O1ⁱⁱⁱ—Li2—O4	90
O3—V2—O5	102.88 (6)	O1ⁱⁱⁱ—Li2—O4^xi	90
O3—V2—O7	154.80 (6)	O4—Li2—O4^xi	180
O3—V2—O7^vii	77.83 (5)	O4^xi—Li2—O4	180
O5—V2—O7	102.33 (7)	O1^vii—Li3—O2	174.9 (18)
O5—V2—O7^vii	179.29 (6)	O1^vii—Li3—O5^viii	91.1 (10)
O7—V2—O7^vii	76.96 (6)	O1^vii—Li3—O5^ix	91.1 (10)
O7^vii—V2—O7	76.96 (6)	O1^vii—Li3—O6	88.0 (11)
O2—V3—O3^viii	84.83 (3)	O2—Li3—O5^viii	89.2 (10)
O2—V3—O3^ix	84.83 (3)	O2—Li3—O5^ix	89.2 (10)
O2—V3—O3^vii	81.40 (5)	O2—Li3—O6	86.9 (14)
O2—V3—O6	101.75 (7)	O5^viii—Li3—O5^ix	173.0 (16)
O2—V3—O7	157.22 (6)	O5^viii—Li3—O6	93.3 (9)
O3^viii—V3—O3^ix	155.76 (6)	O5^ix—Li3—O5^viii	173.0 (16)
O3^viii—V3—O3^vii	78.40 (4)	O5^ix—Li3—O6	93.3 (9)

Experimental details

	(Li3V6O13)	(Li3+dV6O13)
Crystal data
Chemical formula	Li₃O₁₃V₆	Li_3.25V₆O₁₃
M_r	534.5	536.2
Crystal system, space group	Monoclinic, C2/m	Monoclinic, C2/m
Temperature (K)	295	295
a, b, c (Å)	11.792 (1), 3.9214 (4), 10.189 (1)	11.7236 (6), 3.9155 (2), 10.1521 (5)
β (°)	100.596 (2)	100.592 (2)
V (Å³)	463.12 (8)	458.08 (4)
Z	2	2
Radiation type	Ag Kα, λ = 0.56083 Å	Synchrotron, λ = 0.872 Å
µ (mm⁻¹)	3.01	10.35
Crystal size (mm)	0.20 × 0.14 × 0.04	0.05 × 0.02 × 0.01

Data collection
Diffractometer	CCD area detector diffractometer	CCD area detector diffractometer
Absorption correction	Empirical (using intensity measurements) SADABS (Bruker 2003)	Empirical (using intensity measurements) SADABS (Bruker, 2003)
T_min, T_max	1.000, 1.000	1.000, 1.000
No. of measured, independent and observed [I > −15σ(I)] reflections	2830, 1179, 1179	5374, 1372, 1365
R_int	0.027	0.040
(sin θ/λ)_max (Å⁻¹)	0.841	0.886

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.059, 2.09	0.029, 0.048, 3.24
No. of reflections	1179	1365
No. of parameters	69	71
No. of restraints	?	?
Δρ_max, Δρ_min (e Å⁻³)	2.14, −1.30	1.34, −1.17

Computer programs: SMART (Bruker 2003), SAINT+ (Bruker 2003), Jana2000 (Petricek and Dusek, 2000), Diamond Version 2.1c.

Selected geometric parameters (Å, º) for (Li3V6O13) top

V1—O1ⁱ	2.003 (3)	V3—O3^ix	2.0072 (5)
V1—O1ⁱⁱ	1.9696 (3)	V3—O3^vii	2.312 (2)
V1—O1ⁱⁱⁱ	1.9696 (3)	V3—O6	1.641 (2)
V1—O4	1.8529 (7)	V3—O7	1.957 (3)
V1—O5	1.995 (2)	Li1—O2^vi	2.050 (7)
V1—O6^iv	2.025 (2)	Li1—O2^x	1.994 (6)
V2—O2^v	1.9823 (4)	Li1—O3^ix	2.022 (7)
V2—O2^vi	1.9823 (4)	Li1—O7	1.9615 (2)
V2—O3	2.011 (3)	Li1—O7^xi	1.9615 (2)
V2—O5	1.661 (2)	Li2—O1^xii	2.040 (3)
V2—O7	1.963 (2)	Li2—O1ⁱⁱⁱ	2.040 (3)
V2—O7^vii	2.191 (2)	Li2—O4	1.9607 (2)
V3—O2	1.983 (3)	Li2—O4^xi	1.9607 (2)
V3—O3^viii	2.0072 (5)

O1ⁱ—V1—O1ⁱⁱ	84.54 (8)	O2—V3—O3^vii	81.17 (9)
O1ⁱ—V1—O1ⁱⁱⁱ	84.54 (8)	O2—V3—O6	102.11 (11)
O1ⁱ—V1—O4	178.93 (8)	O2—V3—O7	156.92 (9)
O1ⁱ—V1—O5	92.00 (10)	O3^viii—V3—O3^ix	155.29 (9)
O1ⁱ—V1—O6^iv	90.52 (10)	O3^viii—V3—O3^vii	78.20 (6)
O1ⁱⁱ—V1—O1ⁱ	84.54 (8)	O3^viii—V3—O6	101.99 (6)
O1ⁱⁱ—V1—O1ⁱⁱⁱ	169.08 (11)	O3^viii—V3—O7	90.60 (7)
O1ⁱⁱ—V1—O4	95.46 (8)	O3^ix—V3—O3^viii	155.29 (9)
O1ⁱⁱ—V1—O5	90.31 (7)	O3^ix—V3—O3^vii	78.20 (6)
O1ⁱⁱ—V1—O6^iv	89.93 (7)	O3^ix—V3—O6	101.99 (6)
O1ⁱⁱⁱ—V1—O1ⁱ	84.54 (8)	O3^ix—V3—O7	90.60 (7)
O1ⁱⁱⁱ—V1—O1ⁱⁱ	169.08 (11)	O3^vii—V3—O3^viii	78.20 (6)
O1ⁱⁱⁱ—V1—O4	95.46 (8)	O3^vii—V3—O3^ix	78.20 (6)
O1ⁱⁱⁱ—V1—O5	90.31 (7)	O3^vii—V3—O6	176.72 (11)
O1ⁱⁱⁱ—V1—O6^iv	89.93 (7)	O3^vii—V3—O7	75.74 (9)
O4—V1—O5	89.07 (7)	O6—V3—O7	100.98 (11)
O4—V1—O6^iv	88.41 (7)	O2^vi—Li1—O2^x	97.5 (3)
O5—V1—O6^iv	177.48 (11)	O2^vi—Li1—O3^ix	173.9 (3)
O2^v—V2—O2^vi	163.05 (10)	O2^vi—Li1—O7	90.2 (2)
O2^v—V2—O3	84.54 (8)	O2^vi—Li1—O7^xi	90.2 (2)
O2^v—V2—O5	97.54 (7)	O2^x—Li1—O2^vi	97.5 (3)
O2^v—V2—O7	92.14 (7)	O2^x—Li1—O3^ix	88.6 (2)
O2^v—V2—O7^vii	82.51 (7)	O2^x—Li1—O7	88.34 (18)
O2^vi—V2—O2^v	163.05 (10)	O2^x—Li1—O7^xi	88.34 (18)
O2^vi—V2—O3	84.54 (8)	O3^ix—Li1—O7	90.0 (2)
O2^vi—V2—O5	97.54 (7)	O3^ix—Li1—O7^xi	90.0 (2)
O2^vi—V2—O7	92.14 (7)	O7—Li1—O7^xi	176.7 (4)
O2^vi—V2—O7^vii	82.51 (7)	O7^xi—Li1—O7	176.7 (4)
O3—V2—O5	103.06 (10)	O1^xii—Li2—O1ⁱⁱⁱ	180
O3—V2—O7	154.51 (9)	O1^xii—Li2—O4	90
O3—V2—O7^vii	77.55 (9)	O1^xii—Li2—O4^xi	90
O5—V2—O7	102.43 (11)	O1ⁱⁱⁱ—Li2—O1^xii	180
O5—V2—O7^vii	179.39 (11)	O1ⁱⁱⁱ—Li2—O4	90
O7—V2—O7^vii	76.97 (9)	O1ⁱⁱⁱ—Li2—O4^xi	90
O7^vii—V2—O7	76.97 (9)	O4—Li2—O4^xi	180
O2—V3—O3^viii	84.64 (7)	O4^xi—Li2—O4	180
O2—V3—O3^ix	84.64 (7)

Selected bond lengths (Å) for (Li3+dV6O13) top

V1—O1ⁱ	1.998 (1)	V3—O6	1.640 (2)
V1—O1ⁱⁱ	1.9643 (1)	V3—O7	1.949 (1)
V1—O1ⁱⁱⁱ	1.9643 (1)	Li1—O2^vi	2.022 (4)
V1—O4	1.8518 (3)	Li1—O2^x	1.988 (5)
V1—O5	1.986 (2)	Li1—O3^ix	2.018 (4)
V1—O6^iv	2.012 (2)	Li1—O7	1.9584 (1)
V2—O2^v	1.9777 (2)	Li1—O7^xi	1.9584 (1)
V2—O2^vi	1.9777 (2)	Li2—O1^xii	2.011 (1)
V2—O3	1.999 (1)	Li2—O1ⁱⁱⁱ	2.011 (1)
V2—O5	1.661 (2)	Li2—O4	1.9577
V2—O7	1.948 (1)	Li2—O4^xi	1.9577
V2—O7^vii	2.182 (2)	Li3—O1^vii	1.96 (3)
V3—O2	1.976 (1)	Li3—O2	1.94 (4)
V3—O3^viii	2.0024 (3)	Li3—O5^viii	1.961 (2)
V3—O3^ix	2.0024 (3)	Li3—O5^ix	1.961 (2)
V3—O3^vii	2.306 (2)	Li3—O6	2.14 (3)

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page