Low-temperature structure of V₆O₁₃

The structure of the transition metal oxide V₆O₁₃, a potential cathode material in lithium-polymer batteries, has been studied at 95 K using single-crystal X-ray diffraction (XRD). A phase transition has been determined by differential scanning calorimetry (DSC) measurements to occur at 153 K, with a heat of transition of -1.98 kJ mol^-1. In this low-temperature phase, the V and O atoms move by up to 0.21 Å out of the mirror plane they occupy in the room-temperature structure. It is concluded that the earlier reported space group P2₁/a [Kawada et al. (1978). Acta Cryst. B34, 1037-1039] is incorrect and that a more appropriate choice of space group is Pc.

Computing details

Data collection: DIF4 (Stoe, 1988) for Stoe_data. Cell refinement: LATCON (Lundgren, 1983) for Stoe_data; SAINT+ (Bruker 2001) for Bruker_data. Data reduction: STOEDATRED, LSQLIN AND ABSSTOE (Lundgren, 1983) for Stoe_data; SAINT+ (Bruker 2001) for Bruker_data. Program(s) used to solve structure: JANA2000 (Petricek,V. & Dusek,M., 2000) for Bruker_data. Program(s) used to refine structure: DUPALS (Lundgren, 1983) for Stoe_data; JANA2000 (Petricek,V. & Dusek,M., 2000) for Bruker_data. For both compounds, molecular graphics: Diamond Version 2.1c. Software used to prepare material for publication: DISTAN (Lundgren, 1983) for Stoe_data; JANA2000 (Petricek,V. & Dusek,M., 2000) for Bruker_data.

(Stoe_data) ? #Insert the chemical name here.

Crystal data

V6O13	F(000) = 484.00
Mr = 513.64	Dx = 3.890 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
a = 10.0605 (4) Å	Cell parameters from 70 reflections
b = 3.7108 (3) Å	θ = 27.9–37.6°
c = 11.9633 (6) Å	µ = 6.06 mm^−1
β = 100.927 (4)°	T = 95 K
V = 438.52 (5) Å^3	Brick, black
Z = 2	0.21 × 0.10 × 0.10 mm

Data collection

STOE 4-circle diffractometer	9436 reflections with Inet > −15.0σ(Inet)
Radiation source: xray tube	Rint = 0.016
Graphite monochromator	θmax = 50.0°, θmin = 0.0°
ω/2θ scan	h = −21→21
Absorption correction: integration ABSSTOE, (Lundgren, 1983)	k = −3→8
Tmin = 0.499, Tmax = 0.609	l = −25→25
9436 measured reflections	6 standard reflections every 240 min
4604 independent reflections	intensity decay: 1.7%

Refinement

Refinement on F^2	Weighting scheme based on measured s.u.'s w = 1/σ^2(I)
Least-squares matrix: full	(Δ/σ)max = 0.027
R[F^2 > 2σ(F^2)] = 0.034	Δρmax = 2.26 e Å^−3
wR(F^2) = 0.058	Δρmin = −1.80 e Å^−3
S = 2.60	Extinction correction: B-C type 1 Gaussian isotropic
9436 reflections	Extinction coefficient: 2566 (51)
191 parameters

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

	x	y	z	Uiso*/Ueq
V1a	−0.006112	0.30547 (10)	0.345635	0.00427 (4)
V1b	−0.00318 (4)	0.23442 (10)	0.64159 (4)	0.00333 (4)
V2a	0.35945 (6)	0.25075 (15)	0.41726 (4)	0.00180 (3)
V2b	0.63137 (6)	0.24770 (8)	0.59109 (4)	0.00166 (3)
V3a	0.36290 (6)	0.24845 (8)	0.71952 (5)	0.00190 (4)
V3b	0.62975 (6)	0.25116 (15)	0.28889 (4)	0.00172 (3)
O1a	−0.00338 (13)	0.2560 (6)	0.18496 (9)	0.00379 (18)
O2a	0.38429 (12)	0.2489 (3)	0.88711 (9)	0.00325 (18)
O3a	0.40576 (13)	0.2512 (7)	0.25536 (9)	0.00316 (18)
O4a	−0.00355 (15)	0.2428 (9)	0.50362 (10)	0.00579 (16)
O5a	0.19198 (12)	0.2528 (6)	0.38814 (9)	0.0042 (2)
O6a	0.19615 (13)	0.2456 (3)	0.68354 (10)	0.0043 (2)
O7a	0.40316 (13)	0.2499 (6)	0.56668 (9)	0.00381 (19)
O1b	−0.00447 (13)	0.2405 (3)	0.83018 (9)	0.00434 (18)
O2b	0.60862 (12)	0.2512 (6)	0.12271 (9)	0.00328 (18)
O3b	0.58680 (13)	0.2484 (3)	0.75362 (9)	0.00310 (18)
O5b	0.79887 (12)	0.2457 (3)	0.61930 (10)	0.0043 (2)
O6b	0.79785 (13)	0.2545 (6)	0.32391 (9)	0.0042 (2)
O7b	0.58849 (13)	0.2499 (7)	0.44333 (9)	0.0039 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1a	0.00280 (7)	0.00449 (6)	0.00536 (7)	0.00000 (6)	0.00032 (5)	−0.00182 (6)
V1b	0.00273 (7)	0.00269 (6)	0.00445 (7)	−0.00004 (7)	0.00038 (5)	−0.00210 (7)
V2a	0.00193 (7)	0.00166 (5)	0.00183 (6)	0.00000 (7)	0.00041 (5)	0.00004 (9)
V2b	0.00172 (7)	0.00182 (6)	0.00149 (5)	0.00004 (6)	0.00044 (5)	−0.00001 (7)
V3a	0.00162 (7)	0.00150 (6)	0.00249 (6)	−0.00003 (6)	0.00013 (5)	0.00000 (7)
V3b	0.00177 (7)	0.00137 (5)	0.00198 (6)	−0.00003 (7)	0.00026 (5)	0.00006 (9)
O1a	0.0042 (3)	0.0033 (3)	0.0038 (2)	0.0004 (5)	0.0008 (2)	−0.0027 (4)
O2a	0.0044 (3)	0.0021 (2)	0.0033 (2)	0.0002 (3)	0.0009 (2)	0.0001 (3)
O3a	0.0041 (3)	0.0018 (2)	0.0035 (2)	−0.0001 (4)	0.0005 (2)	0.0001 (4)
O4a	0.0048 (2)	0.0098 (3)	0.0029 (2)	−0.0002 (4)	0.00111 (17)	−0.0037 (5)
O5a	0.0030 (3)	0.0046 (3)	0.0052 (2)	0.0003 (3)	0.0012 (2)	−0.0004 (4)
O6a	0.0032 (4)	0.0043 (3)	0.0054 (3)	0.0001 (3)	0.0005 (2)	−0.0001 (3)
O7a	0.0042 (3)	0.0038 (3)	0.0034 (2)	−0.0003 (4)	0.0008 (2)	0.0000 (4)
O1b	0.0057 (3)	0.0017 (2)	0.0057 (3)	−0.0005 (3)	0.0012 (2)	0.0005 (3)
O2b	0.0049 (3)	0.0022 (2)	0.0028 (2)	0.0005 (4)	0.0009 (2)	0.0003 (3)
O3b	0.0038 (3)	0.0022 (2)	0.0035 (2)	−0.0001 (3)	0.0010 (2)	0.0001 (3)
O5b	0.0023 (4)	0.0048 (3)	0.0058 (3)	−0.0002 (3)	0.0004 (2)	−0.0003 (3)
O6b	0.0018 (3)	0.0055 (3)	0.0050 (2)	−0.0005 (3)	0.0000 (2)	−0.0003 (4)
O7b	0.0050 (3)	0.0042 (3)	0.0028 (2)	0.0004 (4)	0.0012 (2)	0.0001 (4)

Geometric parameters (Å, º)

V1a—O1a	1.9363 (12)	O2a—V2a^v	1.9169 (14)
V1a—O4a	1.8996 (13)	O2a—V3a	1.9755 (13)
V1a—O5a	1.9708 (13)	O2a—O3a^iv	2.471 (2)
V1a—O1b^i	2.0346 (12)	O2a—O3a^v	2.470 (2)
V1a—O1b^ii	1.6955 (12)	O3a—V2a	2.0763 (14)
V1a—O6b^iii	1.9491 (13)	O3a—V3a^i	1.933 (2)
V1b—O1a^iv	1.892 (2)	O3a—V3a^ii	1.936 (2)
V1b—O1a^v	1.961 (2)	O3a—V3b	2.2127 (15)
V1b—O4a	1.6501 (14)	O3a—O2a^i	2.471 (2)
V1b—O6a	1.9731 (14)	O3a—O2a^ii	2.470 (2)
V1b—O1b	2.2587 (14)	O4a—V1a	1.8996 (13)
V1b—O5b^iii	1.9590 (14)	O4a—V1b	1.6501 (14)
V2a—O2a^i	1.9141 (14)	O5a—V1a	1.9708 (13)
V2a—O2a^ii	1.9169 (14)	O5a—V2a	1.6545 (14)
V2a—O3a	2.0763 (14)	O6a—V1b	1.9731 (14)
V2a—O5a	1.6545 (14)	O6a—V3a	1.6510 (14)
V2a—O7a	1.7580 (12)	O7a—V2a	1.7580 (12)
V2a—O7b	2.2659 (14)	O7a—V2b	2.2589 (14)
V2b—O7a	2.2589 (14)	O7a—V3a	1.9464 (13)
V2b—O2b^iv	1.912 (2)	O1b—V1a^iv	2.0346 (12)
V2b—O2b^v	1.920 (2)	O1b—V1a^v	1.6955 (12)
V2b—O3b	2.0766 (14)	O1b—V1b	2.2587 (14)
V2b—O5b	1.6547 (14)	O2b—V2b^i	1.912 (2)
V2b—O7b	1.7383 (12)	O2b—V2b^ii	1.920 (2)
V3a—O2a	1.9755 (13)	O2b—V3b	1.9589 (12)
V3a—O3a^iv	1.933 (2)	O2b—O3b^i	2.463 (2)
V3a—O3a^v	1.936 (2)	O2b—O3b^ii	2.466 (2)
V3a—O6a	1.6510 (14)	O3b—V2b	2.0766 (14)
V3a—O7a	1.9464 (13)	O3b—V3a	2.2119 (15)
V3a—O3b	2.2119 (15)	O3b—V3b^iv	1.9317 (15)
V3b—O3a	2.2127 (15)	O3b—V3b^v	1.9351 (15)
V3b—O2b	1.9589 (12)	O3b—O2b^iv	2.463 (2)
V3b—O3b^i	1.9317 (15)	O3b—O2b^v	2.466 (2)
V3b—O3b^ii	1.9351 (15)	O5b—V1b^vi	1.9590 (14)
V3b—O6b	1.6635 (14)	O5b—V2b	1.6547 (14)
V3b—O7b	1.9690 (13)	O6b—V1a^vi	1.9491 (13)
O1a—V1a	1.9363 (12)	O6b—V3b	1.6635 (14)
O1a—V1b^i	1.892 (2)	O7b—V2a	2.2659 (14)
O1a—V1b^ii	1.961 (2)	O7b—V2b	1.7383 (12)
O2a—V2a^iv	1.9141 (14)	O7b—V3b	1.9690 (13)
O1a—V1a—O4a	167.43 (12)	O2b—V3b—O6b	99.51 (6)
O1a—V1a—O5a	92.45 (5)	O2b—V3b—O7b	161.94 (6)
O1a—V1a—O1b^i	79.25 (7)	O3b^i—V3b—O3b^ii	147.34 (5)
O1a—V1a—O1b^ii	89.07 (8)	O3b^i—V3b—O6b	103.70 (9)
O1a—V1a—O6b^iii	93.60 (5)	O3b^i—V3b—O7b	97.15 (8)
O4a—V1a—O5a	84.77 (6)	O3b^ii—V3b—O3b^i	147.34 (5)
O4a—V1a—O1b^i	88.27 (10)	O3b^ii—V3b—O6b	102.82 (9)
O4a—V1a—O1b^ii	103.39 (10)	O3b^ii—V3b—O7b	97.40 (8)
O4a—V1a—O6b^iii	86.75 (5)	O6b—V3b—O7b	98.55 (6)
O5a—V1a—O1b^i	84.23 (7)	V1a—O1a—V1b^i	111.37 (10)
O5a—V1a—O1b^ii	95.53 (8)	V1a—O1a—V1b^ii	99.91 (9)
O5a—V1a—O6b^iii	166.65 (8)	V1b^i—O1a—V1b^ii	148.72 (7)
O1b^i—V1a—O1b^ii	168.28 (5)	V1b^ii—O1a—V1b^i	148.72 (7)
O1b^i—V1a—O6b^iii	85.23 (8)	V2a^iv—O2a—V2a^v	151.21 (7)
O1b^ii—V1a—O1b^i	168.28 (5)	V2a^iv—O2a—V3a	101.39 (5)
O1b^ii—V1a—O6b^iii	96.45 (8)	V2a^iv—O2a—O3a^iv	54.76 (5)
O1a^iv—V1b—O1a^v	148.72 (6)	V2a^iv—O2a—O3a^v	151.40 (7)
O1a^iv—V1b—O4a	107.01 (12)	V2a^v—O2a—V2a^iv	151.21 (7)
O1a^iv—V1b—O6a	90.25 (5)	V2a^v—O2a—V3a	101.46 (5)
O1a^iv—V1b—O1b	74.64 (5)	V2a^v—O2a—O3a^iv	151.39 (7)
O1a^iv—V1b—O5b^iii	90.22 (5)	V2a^v—O2a—O3a^v	54.75 (5)
O1a^v—V1b—O1a^iv	148.72 (6)	V3a—O2a—O3a^iv	50.04 (5)
O1a^v—V1b—O4a	104.27 (12)	V3a—O2a—O3a^v	50.12 (5)
O1a^v—V1b—O6a	87.96 (5)	O3a^iv—O2a—O3a^v	97.36 (7)
O1a^v—V1b—O1b	74.08 (5)	O3a^v—O2a—O3a^iv	97.36 (7)
O1a^v—V1b—O5b^iii	87.90 (5)	V2a—O3a—V3a^i	97.23 (9)
O4a—V1b—O6a	93.64 (7)	V2a—O3a—V3a^ii	97.32 (9)
O4a—V1b—O1b	178.28 (11)	V2a—O3a—V3b	103.40 (5)
O4a—V1b—O5b^iii	93.09 (6)	V2a—O3a—O2a^i	48.85 (5)
O6a—V1b—O1b	86.78 (5)	V2a—O3a—O2a^ii	48.94 (5)
O6a—V1b—O5b^iii	172.80 (6)	V3a^i—O3a—V3a^ii	147.13 (6)
O1b—V1b—O5b^iii	86.42 (5)	V3a^i—O3a—V3b	102.52 (9)
O2a^i—V2a—O2a^ii	151.21 (6)	V3a^i—O3a—O2a^i	51.56 (6)
O2a^i—V2a—O3a	76.39 (8)	V3a^i—O3a—O2a^ii	144.98 (8)
O2a^i—V2a—O5a	97.40 (9)	V3a^ii—O3a—V3a^i	147.13 (6)
O2a^i—V2a—O7a	99.98 (8)	V3a^ii—O3a—V3b	102.52 (9)
O2a^i—V2a—O7b	81.89 (8)	V3a^ii—O3a—O2a^i	144.99 (8)
O2a^ii—V2a—O2a^i	151.21 (6)	V3a^ii—O3a—O2a^ii	51.56 (6)
O2a^ii—V2a—O3a	76.31 (8)	V3b—O3a—O2a^i	95.36 (7)
O2a^ii—V2a—O5a	96.88 (9)	V3b—O3a—O2a^ii	95.37 (7)
O2a^ii—V2a—O7a	100.18 (8)	O2a^i—O3a—O2a^ii	97.36 (5)
O2a^ii—V2a—O7b	82.06 (8)	O2a^ii—O3a—O2a^i	97.36 (5)
O3a—V2a—O5a	101.72 (6)	V1a—O4a—V1b	174.0 (2)
O3a—V2a—O7a	153.05 (6)	V1a—O5a—V2a	173.88 (14)
O3a—V2a—O7b	74.11 (5)	V1b—O6a—V3a	179.08 (8)
O5a—V2a—O7a	105.22 (6)	V2a—O7a—V2b	100.58 (6)
O5a—V2a—O7b	175.83 (6)	V2a—O7a—V3a	153.99 (8)
O7a—V2a—O7b	78.94 (5)	V2b—O7a—V3a	105.43 (5)
O7a—V2b—O2b^iv	82.65 (7)	V1a^iv—O1b—V1a^v	168.28 (7)
O7a—V2b—O2b^v	82.29 (7)	V1a^iv—O1b—V1b	94.74 (4)
O7a—V2b—O3b	74.12 (5)	V1a^v—O1b—V1a^iv	168.28 (7)
O7a—V2b—O5b	175.74 (6)	V1a^v—O1b—V1b	96.94 (5)
O7a—V2b—O7b	79.53 (5)	V2b^i—O2b—V2b^ii	151.12 (7)
O2b^iv—V2b—O2b^v	151.12 (6)	V2b^i—O2b—V3b	101.93 (8)
O2b^iv—V2b—O3b	76.15 (5)	V2b^i—O2b—O3b^i	54.94 (6)
O2b^iv—V2b—O5b	96.36 (6)	V2b^i—O2b—O3b^ii	152.05 (7)
O2b^iv—V2b—O7b	100.94 (9)	V2b^ii—O2b—V2b^i	151.12 (7)
O2b^v—V2b—O2b^iv	151.12 (6)	V2b^ii—O2b—V3b	101.89 (8)
O2b^v—V2b—O3b	76.08 (5)	V2b^ii—O2b—O3b^i	151.94 (7)
O2b^v—V2b—O5b	96.84 (6)	V2b^ii—O2b—O3b^ii	54.83 (6)
O2b^v—V2b—O7b	100.36 (9)	V3b—O2b—O3b^i	50.23 (5)
O3b—V2b—O5b	101.61 (6)	V3b—O2b—O3b^ii	50.29 (5)
O3b—V2b—O7b	153.65 (6)	O3b^i—O2b—O3b^ii	97.68 (5)
O5b—V2b—O7b	104.73 (7)	O3b^ii—O2b—O3b^i	97.68 (5)
O2a—V3a—O3a^iv	78.40 (5)	V2b—O3b—V3a	102.74 (5)
O2a—V3a—O3a^v	78.33 (5)	V2b—O3b—V3b^iv	97.14 (6)
O2a—V3a—O6a	100.05 (6)	V2b—O3b—V3b^v	97.26 (6)
O2a—V3a—O7a	162.07 (6)	V2b—O3b—O2b^iv	48.91 (4)
O2a—V3a—O3b	84.36 (5)	V2b—O3b—O2b^v	49.09 (4)
O3a^iv—V3a—O3a^v	147.13 (6)	V3a—O3b—V3b^iv	102.60 (6)
O3a^iv—V3a—O6a	102.98 (6)	V3a—O3b—V3b^v	102.56 (6)
O3a^iv—V3a—O7a	97.67 (8)	V3a—O3b—O2b^iv	95.35 (5)
O3a^iv—V3a—O3b	77.43 (5)	V3a—O3b—O2b^v	95.33 (5)
O3a^v—V3a—O3a^iv	147.13 (6)	V3b^iv—O3b—V3b^v	147.34 (6)
O3a^v—V3a—O6a	103.68 (6)	V3b^iv—O3b—O2b^iv	51.21 (5)
O3a^v—V3a—O7a	97.36 (8)	V3b^iv—O3b—O2b^v	144.91 (8)
O3a^v—V3a—O3b	77.46 (5)	V3b^v—O3b—V3b^iv	147.34 (6)
O6a—V3a—O7a	97.89 (6)	V3b^v—O3b—O2b^iv	144.86 (8)
O6a—V3a—O3b	175.58 (6)	V3b^v—O3b—O2b^v	51.14 (5)
O7a—V3a—O3b	77.71 (5)	O2b^iv—O3b—O2b^v	97.68 (7)
O3a—V3b—O2b	84.56 (5)	O2b^v—O3b—O2b^iv	97.68 (7)
O3a—V3b—O3b^i	77.44 (8)	V1b^vi—O5b—V2b	176.01 (8)
O3a—V3b—O3b^ii	77.45 (8)	V1a^vi—O6b—V3b	171.52 (11)
O3a—V3b—O6b	175.91 (6)	V2a—O7b—V2b	100.95 (6)
O3a—V3b—O7b	77.38 (5)	V2a—O7b—V3b	105.11 (5)
O2b—V3b—O3b^i	78.56 (7)	V2b—O7b—V3b	153.95 (8)
O2b—V3b—O3b^ii	78.57 (7)

Symmetry codes: (i) x, −y, z−1/2; (ii) x, −y+1, z−1/2; (iii) x−1, y, z; (iv) x, −y, z+1/2; (v) x, −y+1, z+1/2; (vi) x+1, y, z.

(Bruker_data)

Crystal data

V6O13	F(000) = 484
Mr = 513.64	Dx = 3.896 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
a = 10.0543 (1) Å	Cell parameters from 4122 reflections
b = 3.7080 (1) Å	θ = 3.5–49.4°
c = 11.9554 (1) Å	µ = 6.23 mm^−1
β = 100.914 (1)°	T = 95 K
V = 437.65 (1) Å^3	Brick, black
Z = 2	0.12 × 0.07 × 0.05 mm

Data collection

CCD area detector diffractometer	8245 independent reflections
Radiation source: fine-focus sealed tube	26501 reflections with > −15σ(I)
Graphite monochromator	Rint = 0.058
Detector resolution: 512*512 pixels mm^-1	θmax = 49.6°, θmin = 2.1°
ω scans	h = −21→21
Absorption correction: integration	k = −7→6
Tmin = 0.580, Tmax = 0.775	l = −25→24
26501 measured reflections

Refinement

Refinement on F^2	Weighting scheme based on measured s.u.'s w = 1/σ^2(I)
R[F > 3σ(F)] = 0.078	(Δ/σ)max = 0.023
wR(F) = 0.083	Δρmax = 4.46 e Å^−3
S = 0.58	Δρmin = −4.75 e Å^−3
26501 reflections	Extinction correction: B-C type 1 Gaussian isotropic
191 parameters	Extinction coefficient: 683 (5)

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

	x	y	z	Uiso*/Ueq
V1a	−0.006112	0.2974 (2)	0.345635	0.00876 (12)
V1b	−0.00300 (8)	0.2358 (2)	0.64163 (8)	0.00432 (10)
V2a	0.36020 (10)	0.2503 (3)	0.41711 (8)	0.00272 (10)
V2b	0.63220 (10)	0.24780 (10)	0.59099 (8)	0.00235 (10)
V3a	0.36370 (10)	0.24890 (10)	0.71932 (8)	0.00247 (10)
V3b	0.63060 (10)	0.2515 (3)	0.28868 (8)	0.00264 (10)
O1a	−0.0034 (3)	0.2560 (10)	0.1835 (2)	0.0050 (4)
O2a	0.3854 (3)	0.2497 (6)	0.8859 (2)	0.0038 (4)
O3a	0.4068 (3)	0.2520 (10)	0.2540 (2)	0.0040 (4)
O4a	−0.0032 (3)	0.2400 (10)	0.5019 (2)	0.0056 (3)
O5a	0.1923 (3)	0.2520 (10)	0.3865 (2)	0.0051 (5)
O6a	0.1965 (3)	0.2464 (6)	0.6818 (2)	0.0046 (5)
O7a	0.4037 (3)	0.2510 (10)	0.5647 (2)	0.0040 (4)
O1b	−0.0041 (3)	0.2411 (5)	0.8289 (2)	0.0051 (4)
O2b	0.6094 (3)	0.2510 (10)	0.1219 (2)	0.0046 (4)
O3b	0.5878 (3)	0.2489 (6)	0.7520 (2)	0.0038 (4)
O5b	0.7991 (3)	0.2469 (6)	0.6173 (2)	0.0049 (5)
O6b	0.7987 (3)	0.2540 (10)	0.3223 (2)	0.0052 (5)
O7b	0.5886 (3)	0.2510 (10)	0.4416 (2)	0.0049 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1a	0.0035 (2)	0.0149 (2)	0.0075 (2)	0.00162 (19)	0.00013 (15)	−0.0057 (2)
V1b	0.00295 (18)	0.00396 (15)	0.0059 (2)	−0.00099 (14)	0.00033 (14)	−0.00054 (14)
V2a	0.00240 (18)	0.00294 (15)	0.00284 (17)	−0.00007 (13)	0.00053 (13)	0.0003 (2)
V2b	0.00234 (17)	0.00300 (15)	0.00182 (16)	−0.00013 (12)	0.00065 (13)	0.00035 (13)
V3a	0.00203 (17)	0.00222 (15)	0.00318 (17)	−0.00021 (11)	0.00050 (13)	0.00001 (13)
V3b	0.00253 (18)	0.00262 (15)	0.00257 (16)	0.00001 (13)	0.00000 (13)	−0.00026 (19)
O1a	0.0040 (8)	0.0040 (7)	0.0068 (7)	−0.0015 (10)	0.0002 (5)	−0.0038 (10)
O2a	0.0040 (8)	0.0035 (6)	0.0038 (6)	−0.0005 (5)	0.0002 (5)	−0.0004 (6)
O3a	0.0038 (8)	0.0032 (7)	0.0048 (7)	−0.0008 (7)	0.0003 (6)	0.0000 (8)
O4a	0.0046 (3)	0.0087 (6)	0.0035 (4)	−0.0019 (8)	0.0005 (3)	−0.0009 (10)
O5a	0.0025 (8)	0.0066 (8)	0.0066 (7)	0.0011 (6)	0.0019 (6)	−0.0006 (9)
O6a	0.0035 (9)	0.0049 (7)	0.0056 (7)	−0.0001 (5)	0.0017 (6)	0.0005 (6)
O7a	0.0031 (8)	0.0042 (7)	0.0051 (7)	−0.0001 (7)	0.0018 (6)	−0.0007 (7)
O1b	0.0055 (8)	0.0055 (7)	0.0042 (7)	0.0008 (8)	0.0007 (5)	0.0007 (6)
O2b	0.0067 (9)	0.0032 (7)	0.0041 (6)	0.0015 (7)	0.0019 (5)	−0.0006 (7)
O3b	0.0045 (8)	0.0036 (7)	0.0034 (7)	0.0003 (5)	0.0008 (6)	0.0002 (6)
O5b	0.0037 (9)	0.0039 (7)	0.0064 (7)	−0.0009 (5)	−0.0007 (6)	0.0002 (6)
O6b	0.0022 (8)	0.0057 (8)	0.0072 (8)	−0.0003 (6)	−0.0002 (6)	−0.0009 (9)
O7b	0.0066 (9)	0.0037 (7)	0.0047 (7)	−0.0006 (8)	0.0013 (6)	0.0005 (8)

Geometric parameters (Å, º)

V1a—O1a	1.950 (2)	O1a—V1a	1.950 (2)
V1a—O4a	1.875 (2)	O1a—V1b^i	1.891 (3)
V1a—O5a	1.969 (2)	O1a—V1b^ii	1.950 (3)
V1a—O1b^i	2.007 (2)	O2a—V2a^iv	1.917 (2)
V1a—O1b^ii	1.724 (2)	O2a—V2a^v	1.917 (2)
V1a—O6b^iii	1.936 (3)	O2a—V3a	1.962 (2)
V1b—O1a^iv	1.891 (3)	O3a—V2a	2.090 (2)
V1b—O1a^v	1.950 (3)	O3a—V3a^i	1.934 (3)
V1b—O4a	1.670 (2)	O3a—V3a^ii	1.928 (3)
V1b—O6a	1.972 (3)	O3a—V3b	2.210 (3)
V1b—O1b	2.241 (2)	O4a—V1a	1.875 (2)
V1b—O5b^iii	1.956 (3)	O4a—V1b	1.670 (2)
V2a—O2a^i	1.917 (2)	O5a—V1a	1.969 (2)
V2a—O2a^ii	1.917 (2)	O5a—V2a	1.658 (3)
V2a—O3a	2.090 (2)	O6a—V1b	1.972 (3)
V2a—O5a	1.658 (3)	O6a—V3a	1.656 (3)
V2a—O7a	1.736 (2)	O7a—V2a	1.736 (2)
V2a—O7b	2.259 (3)	O7a—V2b	2.259 (3)
V2b—O7a	2.259 (3)	O7a—V3a	1.965 (2)
V2b—O2b^iv	1.908 (3)	O1b—V1a^iv	2.007 (2)
V2b—O2b^v	1.917 (3)	O1b—V1a^v	1.724 (2)
V2b—O3b	2.057 (2)	O1b—V1b	2.241 (2)
V2b—O5b	1.648 (3)	O2b—V2b^i	1.908 (3)
V2b—O7b	1.757 (2)	O2b—V2b^ii	1.917 (3)
V3a—O2a	1.962 (2)	O2b—V3b	1.965 (2)
V3a—O3a^iv	1.934 (3)	O3b—V2b	2.057 (2)
V3a—O3a^v	1.928 (3)	O3b—V3a	2.213 (3)
V3a—O6a	1.656 (3)	O3b—V3b^iv	1.936 (2)
V3a—O7a	1.965 (2)	O3b—V3b^v	1.933 (2)
V3a—O3b	2.213 (3)	O5b—V1b^vi	1.956 (3)
V3b—O3a	2.210 (3)	O5b—V2b	1.648 (3)
V3b—O2b	1.965 (2)	O6b—V1a^vi	1.936 (3)
V3b—O3b^i	1.936 (2)	O6b—V3b	1.662 (3)
V3b—O3b^ii	1.933 (2)	O7b—V2a	2.259 (3)
V3b—O6b	1.662 (3)	O7b—V2b	1.757 (2)
V3b—O7b	1.953 (2)	O7b—V3b	1.953 (2)
O1a—V1a—O4a	168.84 (16)	O3a^iv—V3a—O3a^v	147.52 (12)
O1a—V1a—O5a	92.05 (11)	O3a^iv—V3a—O6a	103.15 (12)
O1a—V1a—O1b^i	79.65 (13)	O3a^iv—V3a—O7a	97.36 (13)
O1a—V1a—O1b^ii	87.71 (13)	O3a^iv—V3a—O3b	77.46 (11)
O1a—V1a—O6b^iii	93.14 (11)	O3a^v—V3a—O3a^iv	147.52 (12)
O4a—V1a—O5a	85.36 (11)	O3a^v—V3a—O6a	103.83 (12)
O4a—V1a—O1b^i	89.30 (13)	O3a^v—V3a—O7a	96.94 (13)
O4a—V1a—O1b^ii	103.30 (14)	O3a^v—V3a—O3b	77.42 (11)
O4a—V1a—O6b^iii	87.61 (11)	O6a—V3a—O7a	97.08 (12)
O5a—V1a—O1b^i	84.88 (13)	O6a—V3a—O3b	174.55 (12)
O5a—V1a—O1b^ii	94.59 (14)	O7a—V3a—O3b	77.48 (11)
O5a—V1a—O6b^iii	168.63 (14)	O3a—V3b—O2b	84.18 (11)
O1b^i—V1a—O1b^ii	167.32 (11)	O3a—V3b—O3b^i	77.50 (13)
O1b^i—V1a—O6b^iii	86.10 (14)	O3a—V3b—O3b^ii	77.38 (13)
O1b^ii—V1a—O1b^i	167.32 (11)	O3a—V3b—O6b	176.86 (12)
O1b^ii—V1a—O6b^iii	95.72 (14)	O3a—V3b—O7b	77.44 (11)
O1a^iv—V1b—O1a^v	149.73 (12)	O2b—V3b—O3b^i	78.02 (13)
O1a^iv—V1b—O4a	105.91 (15)	O2b—V3b—O3b^ii	78.11 (13)
O1a^iv—V1b—O6a	90.45 (11)	O2b—V3b—O6b	98.94 (13)
O1a^iv—V1b—O1b	75.13 (9)	O2b—V3b—O7b	161.62 (13)
O1a^iv—V1b—O5b^iii	90.38 (11)	O3b^i—V3b—O3b^ii	146.77 (11)
O1a^v—V1b—O1a^iv	149.73 (12)	O3b^i—V3b—O6b	103.44 (16)
O1a^v—V1b—O4a	104.36 (15)	O3b^i—V3b—O7b	97.64 (14)
O1a^v—V1b—O6a	88.26 (11)	O3b^ii—V3b—O3b^i	146.77 (11)
O1a^v—V1b—O1b	74.60 (9)	O3b^ii—V3b—O6b	102.83 (16)
O1a^v—V1b—O5b^iii	88.07 (11)	O3b^ii—V3b—O7b	97.76 (14)
O4a—V1b—O6a	92.98 (13)	O6b—V3b—O7b	99.43 (12)
O4a—V1b—O1b	178.91 (14)	V1a—O1a—V1b^i	109.89 (16)
O4a—V1b—O5b^iii	92.44 (12)	V1a—O1a—V1b^ii	100.38 (15)
O6a—V1b—O1b	87.35 (10)	V1b^i—O1a—V1b^ii	149.73 (14)
O6a—V1b—O5b^iii	174.08 (11)	V1b^ii—O1a—V1b^i	149.73 (14)
O1b—V1b—O5b^iii	87.20 (11)	V2a^iv—O2a—V2a^v	150.44 (17)
O2a^i—V2a—O2a^ii	150.44 (13)	V2a^iv—O2a—V3a	101.69 (10)
O2a^i—V2a—O3a	76.12 (13)	V2a^v—O2a—V2a^iv	150.44 (17)
O2a^i—V2a—O5a	97.31 (16)	V2a^v—O2a—V3a	101.86 (10)
O2a^i—V2a—O7a	100.49 (14)	V2a—O3a—V3a^i	96.68 (14)
O2a^i—V2a—O7b	81.83 (13)	V2a—O3a—V3a^ii	97.04 (14)
O2a^ii—V2a—O2a^i	150.44 (13)	V2a—O3a—V3b	103.01 (10)
O2a^ii—V2a—O3a	75.78 (13)	V3a^i—O3a—V3a^ii	147.52 (14)
O2a^ii—V2a—O5a	96.89 (16)	V3a^i—O3a—V3b	102.61 (15)
O2a^ii—V2a—O7a	100.33 (14)	V3a^ii—O3a—V3a^i	147.52 (14)
O2a^ii—V2a—O7b	81.70 (13)	V3a^ii—O3a—V3b	102.75 (15)
O3a—V2a—O5a	101.11 (12)	V1a—O4a—V1b	174.0 (2)
O3a—V2a—O7a	152.96 (14)	V1a—O5a—V2a	175.0 (2)
O3a—V2a—O7b	73.68 (10)	V1b—O6a—V3a	178.21 (16)
O5a—V2a—O7a	105.93 (14)	V2a—O7a—V2b	101.26 (14)
O5a—V2a—O7b	174.79 (12)	V2a—O7a—V3a	154.08 (18)
O7a—V2a—O7b	79.28 (12)	V2b—O7a—V3a	104.66 (10)
O7a—V2b—O2b^iv	82.86 (13)	V1a^iv—O1b—V1a^v	167.32 (15)
O7a—V2b—O2b^v	82.31 (13)	V1a^iv—O1b—V1b	95.33 (8)
O7a—V2b—O3b	74.63 (10)	V1a^v—O1b—V1a^iv	167.32 (15)
O7a—V2b—O5b	177.04 (12)	V1a^v—O1b—V1b	97.30 (10)
O7a—V2b—O7b	78.88 (12)	V2b^i—O2b—V2b^ii	151.53 (17)
O2b^iv—V2b—O2b^v	151.53 (13)	V2b^i—O2b—V3b	101.74 (15)
O2b^iv—V2b—O3b	76.43 (10)	V2b^ii—O2b—V2b^i	151.53 (17)
O2b^iv—V2b—O5b	96.68 (12)	V2b^ii—O2b—V3b	101.58 (15)
O2b^iv—V2b—O7b	100.80 (14)	V2b—O3b—V3a	103.24 (10)
O2b^v—V2b—O2b^iv	151.53 (13)	V2b—O3b—V3b^iv	97.57 (11)
O2b^v—V2b—O3b	76.27 (10)	V2b—O3b—V3b^v	97.80 (11)
O2b^v—V2b—O5b	96.88 (12)	V3a—O3b—V3b^iv	102.43 (11)
O2b^v—V2b—O7b	99.99 (14)	V3a—O3b—V3b^v	102.45 (11)
O3b—V2b—O5b	102.42 (12)	V3b^iv—O3b—V3b^v	146.77 (14)
O3b—V2b—O7b	153.51 (14)	V3b^v—O3b—V3b^iv	146.77 (14)
O5b—V2b—O7b	104.07 (14)	V1b^vi—O5b—V2b	177.36 (16)
O2a—V3a—O3a^iv	78.84 (10)	V1a^vi—O6b—V3b	172.9 (2)
O2a—V3a—O3a^v	78.64 (10)	V2a—O7b—V2b	100.58 (14)
O2a—V3a—O6a	100.78 (13)	V2a—O7b—V3b	105.86 (11)
O2a—V3a—O7a	162.13 (13)	V2b—O7b—V3b	153.55 (18)
O2a—V3a—O3b	84.66 (11)

Symmetry codes: (i) x, −y, z−1/2; (ii) x, −y+1, z−1/2; (iii) x−1, y, z; (iv) x, −y, z+1/2; (v) x, −y+1, z+1/2; (vi) x+1, y, z.