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The crystal structures of dimagnesium disodium decavanadate icosahydrate, Mg2Na2V10O28·20H2O, (I), and trimagnesium decavanadate octacosahydrate, Mg3V10O28·28H2O, (II), have been determined by single-crystal X-ray diffraction. They crystallize with monoclinic (C2/c) and triclinic (P\overline 1) symmetry, respectively. All the Mg2+ cations in (I) and (II) are octahedrally coordinated by six water mol­ecules. The Na+ cations in (I) are coordinated by three water mol­ecules and three O atoms of the decavanadate anions, and link the latter into a three-dimensional network. The decavanadate anions in (II) are not linked to one another.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104004676/bc1038sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104004676/bc1038Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104004676/bc1038IIsup3.hkl
Contains datablock II

Comment top

When precipitated with more than one cationic species, the decavanadate anion, [V10O28]6−, crystallizes into double salts with various kinds of three- dimensional arrangements of the constituent ions. Typical examples are the mineral hummerite, K2Mg2[V10O28].16H2O (Avtamonova et al., 1988), and its isomorphous compounds K2Zn2[V10O28].16H2O (Evans, 1966), (NH4)2Mg2[V10O28].16H2O and Rb2Mg2[V10O28].16H2O (Avtamonova et al., 1988) where the monovalent cations link the decavanadate anions into layers that sandwich the hydrated M(H2O)62+ cations. Recently, various new extended structures have been observed in some double decavanadate salts, such as one-dimensional chains in [Ni(H2O)6]2[Na(H2O)3]2[V10O28]·4H2O (Higami et al., 2002), two-dimensional networks in Na4Ni[V10O28].23H2O (Sun et al., 2002) and three-dimensional structures in K2Ba2[V10O28]·8H2O (Rastsvetaeva, 1999), CuNa4V10O28.23H2O (Iida & Ozeki, 2003) and K4Na2[V10O28].10H2O (Lee & Joo, 2003). We report here the crystal structure of Mg2Na2V10O28.20H2O, (I), as a new addition to the family of alkali magnesium decavanadates. In the structure of (I), the decavanadate anions are linked into a three-dimensional structure by the Na+ cations. Also reported here is the crystal structure of Mg3V10O28.28H2O, (II), which complements the known alkaline earth decavanadates, including Ca3V10O28.17H2O (Swallow et al., 1966), Ca2(H3O)2[V10O28].16H2O (Strukan et al., 1999), Sr3V10O28.22H2O (Nieto et al., 1993) and Ba3V10O28.19H2O (Kamenar et al., 1996).

From solutions containing Mg2+ and Na+ cations, the decavanadate anion crystallizes with both cations to produce (I). An asymmetric unit of (I) includes one-half of a [V10O28]6− anion, an Mg2+ cation, an Na+ cation and water molecules. The decavanadate anion is located on a twofold axis and has a metal–oxygen framework the same as that reported by Evans (1966) (Fig. 1). The Mg2+ cation is octahedrally coordinated by six water molecules, with Mg—O distances of 2.0234 (15)–2.1398 (15) Å. The coordination environment of the Na+ cation consists of two O atoms from two separate [V10O28]6− anions (at 2.6264 and 2.6620 Å) and three water molecules (at 2.3481–2.5864 Å), yielding a coordination geometry between square-pyramidal and trigonal-bipyramidal, with a τ parameter of 0.466 [τ is defined as the difference of the two largest bond angles at the metal center divided by 60 and is expected to be 1 for the ideal trigonal-bipyramidal geometry and 0 for the ideal square-pyramidal geometry (Addison et al., 1984)]. The sixth O atom approaches Na+ at a distance of 2.9714 Å, capping a triangular face of the square pyramid. Each Na+ cation shares two water molecules with its symmetry equivalent, forming a dimeric cation, [Na2(H2O)4]2+, that links the decavanadate anions into a three-dimensional array (Fig. 2). The structure of this array is different from that in other decavanadates, such as (K2Mg2[V10O28].16H2O, (NH4)2Mg2[V10O28].16H2O and Rb2Mg2[V10O28].16H2O (Avtamonova et al., 1988), reflecting the different ionic radius and coordination requirement of the Na+ ion.

From solutions containing only Mg2+ as the cationic species, crystallization with the decavanadate anion gives (II). An asymmetric unit of (II) consists of two half [V10O28]6− anions, each located on an inversion center, three Mg2+ cations and water molecules of crystallization. The metal–oxygen framework of the decavanadate anion is also identical to that reported by Evans (1966) (Fig. 3). Each Mg2+ cation is octahedrally coordinated by six water molecules, with Mg—O distances ranging from 2.0351 (17) to 2.1165 (17) Å. The hydrated Mg+ cations do not bind to the decavanadate anions; this situation is unlike that observed in other alkaline earth decavanadates or in the para-dodecatungstates Mg5[H2W12O42].38H2O (Tsay & Silverton, 1973) and (NH4)2[Mg4(H2O)18(H2W12O42)].10H2O (Li et al., 1999). In contrast, the hydrated Cu2+ cation binds to the decavanadate anion in its simple salt but not in its double salt with Na+ (Iida & Ozeki, 2003). The three [Mg(OH2)6]2+ octahedra in (II) are linked together by hydrogen bonds. The coordination geometry of the water molecules around the Mg2+ cations is summarized in Table 1. According to the classification of Ferraris & Franchini-Angela (1972), most of the H2O molecules adopt a Class 1 Type D geometry (coordinating only the Mg2+ cation approximately along the bisectrix of the lone-pair orbitals) or a Class 2 Type H geometry (coordinating the Mg2+ cation and accepting a hydrogen bond). However, atoms O30 and O46 adopt a Class 1' Type J geometry (coordinating the Mg2+ cation along a lone-pair orbital), which was not found in MgSO4·7H2O (Ferraris & Jones, 1973) or MgSO4·4H2O (Baur, 1964).

Experimental top

NaVO3 (1.22 g) was dissolved in hot water (100 ml) and the pH was adjusted to 3.70 by adding CH3COOH. An aqueous solution of Mg(CH3COO)2·4H2O (0.65 g in 10 ml of water) was then added. The crude product, (I) (1.12 g), was obtained by adding acetone (100 ml) dropwise to the reaction mixture. Diffraction-quality crystals of (I) were obtained by vapor-phase diffusion of acetone into an aqueous solution (15 ml) containing the dissolved crude product (0.1 g). A solution of decavanadic acid was prepared according to Jahr & Preuss (1965): V2O5 (3.64 g) was dissolved in aqueous H2O2 (50 ml of 30% aqueous H2O2 diluted with 400 ml of water). An aqueous solution of Mg(CH3COO)2·4H2O (2.68 g in 10 ml of water) was added to the decavanadic acid solution. After the volume of the resulting solution was reduced to 100 ml by heating, acetone (100 ml) was added dropwise to obtain the crude product, (II) (4.50 g). Diffraction-quality crystals of (II) were obtained by vapor-phase diffusion of acetone into an aqueous solution (15 ml) containing the crude product (0.1 g).

Refinement top

All H atoms were located from difference Fourier syntheses. For (I), the positional and displacement parameters of the H atoms were fully refined. For (II), the positional parameters of the H atoms were fixed and their Uiso parameters were fixed at 1.5Ueq of the O atom of the corresponding H2O molecule. Thus the geometrical parameters involving the H atoms in (II) are less reliable and show some discrepancies with normal values. They are nevertheless included in the current structure analysis because they provide sufficient information on the hydrogen-bond networks. Two H2O molecules in (II) are disordered, viz. O55A/O55B, with site occupancies of 0.685 (12) and 0.315 (12), and O56A/O56B, with occupancies of 0.657 (6) and 0.343 (6). The H atoms bonded to the minor O-atom positions could not be located from Fourier maps. A short contact between atoms O12 and O55B (2.86 Å) may be attributed to the hydrogen bond via the undetermined H atom.

Computing details top

For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Dowty, 1999) and ORTEPIII (Burnett & Johnson, 1996).

Figures top
[Figure 1] Fig. 1. A perspective view of an asymmetric unit and selected neighbors of (I). Displacement ellipsoids are drawn at the 50% probability level. Na···O contacts longer than 2.7 Å are shown as broken lines. [Symmetry codes: (i) −x, y, 1/2 − z; (ii) 1/2 − x, 3/2 − y, 1 − z; (iii) x, 1 − y, 1/2 + z; (iv) 1/2 − x, 1/2 + y, 1/2 − z.]
[Figure 2] Fig. 2. A packing diagram of (I), viewed along the c axis. Open octahedra, filled octahedra and filled circles represent VO6, MgO6 and Na+, respectively. Open circles represent the O atoms of water molecules that do not coordinate Mg2+.
[Figure 3] Fig. 3. A perspective view of an asymmetric unit and selected neighbors of (II). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −x, −y, −z; (ii) 1 − x, 1 − y, 1 − z.]
(I) dimagnesium disodium decavanadate icosahydrate top
Crystal data top
Mg2Na2V10O28·20H2OF(000) = 2800
Mr = 1412.32Dx = 2.387 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8192 reflections
a = 23.8384 (6) Åθ = 1.9–30.0°
b = 11.0248 (2) ŵ = 2.46 mm1
c = 16.9332 (4) ÅT = 93 K
β = 118.005 (1)°Plate, yellow-orange
V = 3929.18 (15) Å30.20 × 0.18 × 0.08 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector system
diffractometer
5746 independent reflections
Radiation source: Rigaku UltraX-18 rotating anode4522 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 10 pixels mm-1θmax = 30.0°, θmin = 1.9°
ω scansh = 3233
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1515
Tmin = 0.640, Tmax = 0.821l = 2318
18758 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: difference Fourier map
wR(F2) = 0.075All H-atom parameters refined
S = 1.01 w = 1/[σ2(Fo2) + (0.0404P)2]
where P = (Fo2 + 2Fc2)/3
5746 reflections(Δ/σ)max = 0.001
360 parametersΔρmax = 0.72 e Å3
0 restraintsΔρmin = 1.24 e Å3
Crystal data top
Mg2Na2V10O28·20H2OV = 3929.18 (15) Å3
Mr = 1412.32Z = 4
Monoclinic, C2/cMo Kα radiation
a = 23.8384 (6) ŵ = 2.46 mm1
b = 11.0248 (2) ÅT = 93 K
c = 16.9332 (4) Å0.20 × 0.18 × 0.08 mm
β = 118.005 (1)°
Data collection top
Bruker SMART CCD area-detector system
diffractometer
5746 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
4522 reflections with I > 2σ(I)
Tmin = 0.640, Tmax = 0.821Rint = 0.034
18758 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.075All H-atom parameters refined
S = 1.01Δρmax = 0.72 e Å3
5746 reflectionsΔρmin = 1.24 e Å3
360 parameters
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
xyzUiso*/Ueq
V10.071893 (13)0.21033 (3)0.283133 (19)0.00579 (7)
V20.073321 (13)0.61761 (3)0.286072 (19)0.00558 (7)
V30.133464 (14)0.41597 (3)0.218853 (19)0.00599 (7)
V40.155828 (14)0.41074 (3)0.412962 (19)0.00636 (7)
V50.011514 (13)0.41638 (3)0.352932 (19)0.00489 (7)
O10.07166 (6)0.06513 (12)0.28211 (9)0.0104 (3)
O20.07392 (6)0.76400 (12)0.28697 (8)0.0094 (3)
O30.17340 (6)0.41393 (12)0.16419 (9)0.0097 (2)
O40.21439 (6)0.41404 (12)0.51254 (9)0.0111 (3)
O50.04407 (6)0.41401 (11)0.11155 (8)0.0074 (2)
O60.08335 (6)0.41632 (11)0.44589 (8)0.0070 (2)
O70.19249 (6)0.41349 (11)0.33890 (8)0.0076 (2)
O80.11699 (6)0.24886 (12)0.22362 (8)0.0074 (2)
O90.13695 (6)0.24692 (12)0.39493 (8)0.0075 (2)
O100.11717 (6)0.57965 (11)0.22367 (8)0.0075 (2)
O110.13780 (6)0.58033 (11)0.39391 (8)0.0076 (2)
O120.00939 (6)0.24470 (11)0.32797 (8)0.0065 (2)
O130.00925 (6)0.58639 (11)0.32791 (8)0.0061 (2)
O140.06284 (6)0.41564 (11)0.27887 (8)0.0060 (2)
Mg0.11263 (3)0.09300 (6)0.59027 (4)0.00735 (12)
O150.11310 (7)0.09275 (13)0.59606 (10)0.0111 (3)
H15A0.1137 (12)0.127 (3)0.6325 (19)0.021 (7)*
H15B0.0996 (12)0.132 (2)0.5571 (19)0.019 (7)*
O160.04096 (7)0.09098 (14)0.46271 (9)0.0112 (3)
H16A0.0321 (15)0.132 (3)0.430 (2)0.036 (10)*
H16B0.0197 (13)0.038 (3)0.4394 (18)0.023 (7)*
O170.17754 (7)0.08550 (13)0.53848 (10)0.0094 (3)
H17A0.1732 (11)0.128 (2)0.5001 (16)0.009 (6)*
H17B0.2098 (15)0.087 (3)0.572 (2)0.032 (9)*
O180.17799 (7)0.08937 (15)0.72108 (10)0.0130 (3)
H18A0.1941 (13)0.031 (3)0.7421 (18)0.021 (7)*
H18B0.1913 (13)0.140 (3)0.7475 (19)0.024 (8)*
O190.03705 (7)0.10426 (13)0.62451 (10)0.0105 (3)
H19A0.0447 (13)0.106 (2)0.6715 (19)0.020 (7)*
H19B0.0158 (13)0.154 (3)0.6036 (18)0.021 (7)*
O200.11855 (7)0.27880 (13)0.59552 (11)0.0127 (3)
H20A0.1091 (12)0.315 (2)0.5590 (19)0.016 (7)*
H20B0.1190 (14)0.311 (3)0.633 (2)0.032 (9)*
Na0.19887 (4)0.67605 (8)0.53862 (5)0.01792 (18)
O210.19082 (8)0.85630 (15)0.45240 (11)0.0181 (3)
H21A0.1870 (17)0.913 (3)0.471 (2)0.048 (11)*
H21B0.1597 (15)0.861 (3)0.405 (2)0.036 (9)*
O220.26327 (7)0.78830 (14)0.66768 (10)0.0148 (3)
H22A0.2529 (15)0.810 (3)0.697 (2)0.036 (10)*
H22B0.2906 (14)0.830 (3)0.6721 (18)0.025 (7)*
O230.23146 (7)0.12755 (14)0.29653 (10)0.0134 (3)
H23A0.2055 (13)0.160 (3)0.2934 (18)0.020 (7)*
H23B0.2555 (15)0.141 (3)0.349 (2)0.038 (9)*
O240.05511 (8)0.72088 (14)0.47750 (11)0.0186 (3)
H24A0.0444 (15)0.687 (3)0.435 (2)0.042 (10)*
H24B0.0472 (12)0.692 (2)0.5060 (18)0.015 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V10.00634 (14)0.00436 (14)0.00689 (14)0.00063 (10)0.00328 (11)0.00035 (10)
V20.00648 (14)0.00398 (14)0.00618 (13)0.00068 (10)0.00290 (11)0.00018 (10)
V30.00583 (13)0.00621 (14)0.00645 (13)0.00001 (10)0.00330 (11)0.00013 (10)
V40.00517 (13)0.00764 (14)0.00530 (13)0.00022 (10)0.00166 (10)0.00039 (11)
V50.00573 (13)0.00466 (14)0.00435 (13)0.00004 (10)0.00243 (11)0.00021 (10)
O10.0114 (6)0.0068 (6)0.0135 (6)0.0014 (5)0.0061 (5)0.0010 (5)
O20.0116 (6)0.0066 (6)0.0107 (6)0.0012 (5)0.0057 (5)0.0002 (5)
O30.0089 (6)0.0115 (6)0.0105 (6)0.0001 (5)0.0061 (5)0.0004 (5)
O40.0084 (6)0.0151 (7)0.0077 (6)0.0008 (5)0.0021 (5)0.0008 (5)
O50.0078 (6)0.0077 (6)0.0071 (6)0.0001 (5)0.0038 (5)0.0002 (5)
O60.0071 (6)0.0081 (6)0.0050 (5)0.0006 (5)0.0022 (4)0.0008 (4)
O70.0072 (6)0.0083 (6)0.0070 (6)0.0005 (5)0.0030 (5)0.0012 (5)
O80.0086 (6)0.0059 (6)0.0084 (5)0.0005 (5)0.0045 (5)0.0003 (5)
O90.0073 (6)0.0067 (6)0.0076 (5)0.0011 (5)0.0028 (4)0.0013 (5)
O100.0086 (6)0.0066 (6)0.0082 (6)0.0010 (5)0.0048 (5)0.0002 (5)
O110.0072 (6)0.0073 (6)0.0071 (5)0.0008 (5)0.0024 (5)0.0002 (5)
O120.0074 (6)0.0055 (6)0.0064 (5)0.0003 (4)0.0031 (4)0.0004 (5)
O130.0072 (6)0.0053 (6)0.0055 (5)0.0004 (4)0.0027 (4)0.0004 (4)
O140.0072 (5)0.0050 (6)0.0057 (5)0.0002 (4)0.0028 (4)0.0005 (4)
Mg0.0082 (3)0.0069 (3)0.0064 (3)0.0005 (2)0.0030 (2)0.0003 (2)
O150.0170 (7)0.0077 (6)0.0078 (6)0.0031 (5)0.0053 (5)0.0002 (6)
O160.0117 (6)0.0100 (7)0.0076 (6)0.0028 (5)0.0010 (5)0.0030 (6)
O170.0071 (6)0.0119 (6)0.0089 (6)0.0006 (5)0.0036 (5)0.0025 (5)
O180.0152 (7)0.0082 (7)0.0085 (6)0.0005 (6)0.0002 (5)0.0003 (6)
O190.0115 (7)0.0127 (7)0.0069 (6)0.0001 (5)0.0040 (5)0.0002 (5)
O200.0246 (8)0.0074 (7)0.0077 (6)0.0019 (5)0.0089 (6)0.0008 (6)
Na0.0257 (4)0.0151 (4)0.0096 (4)0.0090 (3)0.0056 (3)0.0037 (3)
O210.0197 (8)0.0139 (8)0.0156 (7)0.0000 (6)0.0041 (6)0.0049 (6)
O220.0126 (7)0.0136 (7)0.0186 (7)0.0033 (6)0.0076 (6)0.0018 (6)
O230.0115 (7)0.0127 (7)0.0111 (7)0.0046 (5)0.0012 (6)0.0006 (5)
O240.0381 (10)0.0113 (7)0.0108 (7)0.0090 (6)0.0152 (7)0.0042 (6)
Geometric parameters (Å, º) top
V1—O11.6008 (13)O5—V5i1.6931 (13)
V1—O81.8356 (12)O12—V1i2.0036 (12)
V1—O91.8425 (12)O13—V2i2.0373 (12)
V1—O122.0005 (12)O14—V5i2.0995 (12)
V1—O12i2.0036 (12)Mg—O182.0234 (15)
V1—O142.2717 (13)Mg—O162.0298 (15)
V1—V1i3.0652 (6)Mg—O152.0500 (16)
V1—V43.0964 (4)Mg—O202.0523 (16)
V2—O21.6140 (14)Mg—O172.1082 (15)
V2—O111.7973 (13)Mg—O192.1398 (15)
V2—O101.8496 (13)O15—H15A0.72 (3)
V2—O131.9923 (13)O15—H15B0.72 (3)
V2—O13i2.0373 (12)O16—H16A0.67 (3)
V2—O142.2376 (13)O16—H16B0.75 (3)
V2—V2i3.1148 (6)O17—H17A0.77 (3)
V2—V43.1174 (4)O17—H17B0.71 (3)
V3—O31.6097 (13)O18—H18A0.74 (3)
V3—O71.8512 (13)O18—H18B0.69 (3)
V3—O101.8557 (13)O19—H19A0.73 (3)
V3—O81.8933 (13)O19—H19B0.72 (3)
V3—O52.0510 (13)O20—H20A0.68 (3)
V3—O142.3396 (12)O20—H20B0.72 (3)
V3—V43.0734 (4)Na—O222.3481 (17)
V3—V5i3.0784 (4)Na—O212.4195 (19)
V4—O41.6071 (13)Na—O112.4264 (15)
V4—O71.8349 (13)Na—O21ii2.5864 (19)
V4—O91.8516 (13)Na—O3iii2.6620 (15)
V4—O111.9117 (13)Na—O42.9714 (16)
V4—O62.0506 (13)Na—Naii3.6476 (17)
V4—O142.3120 (12)O21—Naii2.5863 (19)
V4—V53.0965 (4)O21—H21A0.72 (3)
V4—Na3.4764 (9)O21—H21B0.80 (3)
V5—O5i1.6932 (13)O22—H22A0.69 (3)
V5—O61.6967 (13)O22—H22B0.77 (3)
V5—O131.9168 (13)O23—H23A0.69 (3)
V5—O121.9349 (13)O23—H23B0.82 (3)
V5—O14i2.0995 (12)O24—H24A0.74 (3)
V5—O142.1239 (12)O24—H24B0.67 (3)
V5—V3i3.0784 (4)
O1—V1—O8103.03 (6)V1—V4—Na160.316 (19)
O1—V1—O9103.12 (6)V5—V4—Na98.462 (18)
O8—V1—O994.93 (6)V2—V4—Na73.482 (17)
O1—V1—O12101.19 (6)O5i—V5—O6106.72 (6)
O8—V1—O12153.78 (6)O5i—V5—O1398.52 (6)
O9—V1—O1289.21 (5)O6—V5—O1396.71 (6)
O1—V1—O12i100.49 (6)O5i—V5—O1296.77 (6)
O8—V1—O12i89.90 (5)O6—V5—O1296.53 (6)
O9—V1—O12i154.13 (6)O13—V5—O12155.94 (6)
O12—V1—O12i75.89 (6)O5i—V5—O14i88.09 (5)
O1—V1—O14175.01 (6)O6—V5—O14i165.19 (6)
O8—V1—O1479.82 (5)O13—V5—O14i81.19 (5)
O9—V1—O1480.56 (5)O12—V5—O14i80.88 (5)
O12—V1—O1475.33 (5)O5i—V5—O14166.81 (6)
O12i—V1—O1475.30 (5)O6—V5—O1486.42 (5)
O1—V1—V1i89.91 (5)O13—V5—O1480.65 (5)
O8—V1—V1i129.91 (4)O12—V5—O1480.24 (5)
O9—V1—V1i129.29 (4)O14i—V5—O1478.77 (5)
O12—V1—V1i40.08 (3)O5i—V5—V3i38.69 (4)
O12i—V1—V1i40.01 (4)O6—V5—V3i145.41 (4)
O14—V1—V1i85.14 (3)O13—V5—V3i90.25 (4)
O1—V1—V4135.97 (5)O12—V5—V3i90.17 (4)
O8—V1—V482.81 (4)O14i—V5—V3i49.41 (3)
O9—V1—V433.14 (4)O14—V5—V3i128.18 (3)
O12—V1—V486.76 (4)O5i—V5—V4144.81 (4)
O12i—V1—V4123.32 (4)O6—V5—V438.16 (4)
O14—V1—V448.06 (3)O13—V5—V490.22 (4)
V1i—V1—V4119.911 (11)O12—V5—V487.88 (4)
O2—V2—O11102.68 (6)O14i—V5—V4127.03 (3)
O2—V2—O10103.11 (6)O14—V5—V448.28 (3)
O11—V2—O1094.91 (6)V3i—V5—V4176.241 (13)
O2—V2—O13100.03 (6)V3—O3—Naiv151.99 (8)
O11—V2—O1391.82 (6)V4—O4—Na94.05 (6)
O10—V2—O13153.80 (6)V5i—O5—V3110.24 (6)
O2—V2—O13i100.27 (6)V5—O6—V4111.10 (6)
O11—V2—O13i155.35 (6)V4—O7—V3112.97 (7)
O10—V2—O13i88.53 (5)V1—O8—V3115.80 (7)
O13—V2—O13i75.33 (6)V1—O9—V4113.90 (7)
O2—V2—O14174.79 (6)V2—O10—V3115.55 (7)
O11—V2—O1481.26 (5)V2—O11—V4114.35 (7)
O10—V2—O1479.76 (5)V2—O11—Na138.42 (7)
O13—V2—O1476.28 (5)V4—O11—Na105.91 (6)
O13i—V2—O1475.33 (5)V5—O12—V1108.69 (6)
O2—V2—V2i90.40 (4)V5—O12—V1i107.74 (6)
O11—V2—V2i131.71 (4)V1—O12—V1i99.91 (5)
O10—V2—V2i127.38 (4)V5—O13—V2107.51 (6)
O13—V2—V2i39.91 (4)V5—O13—V2i106.80 (6)
O13i—V2—V2i38.85 (4)V2—O13—V2i101.24 (6)
O14—V2—V2i84.41 (3)V5i—O14—V5101.23 (5)
O2—V2—V4136.48 (5)V5i—O14—V294.07 (5)
O11—V2—V433.96 (4)V5—O14—V292.55 (5)
O10—V2—V483.41 (4)V5i—O14—V193.31 (5)
O13—V2—V488.25 (4)V5—O14—V193.30 (5)
O13i—V2—V4123.07 (4)V2—O14—V1169.52 (6)
O14—V2—V447.75 (3)V5i—O14—V4170.28 (6)
V2i—V2—V4119.934 (10)V5—O14—V488.44 (4)
O3—V3—O7106.34 (6)V2—O14—V486.49 (4)
O3—V3—O10103.38 (6)V1—O14—V484.98 (4)
O7—V3—O1091.89 (6)V5i—O14—V387.64 (4)
O3—V3—O8101.62 (6)V5—O14—V3171.13 (6)
O7—V3—O890.27 (5)V2—O14—V386.41 (4)
O10—V3—O8153.19 (6)V1—O14—V386.47 (4)
O3—V3—O598.01 (6)V4—O14—V382.71 (4)
O7—V3—O5155.57 (6)O18—Mg—O16174.54 (7)
O10—V3—O584.11 (5)O18—Mg—O1586.78 (7)
O8—V3—O582.97 (5)O16—Mg—O1591.31 (7)
O3—V3—O14171.99 (6)O18—Mg—O2088.30 (7)
O7—V3—O1481.60 (5)O16—Mg—O2093.64 (7)
O10—V3—O1476.95 (5)O15—Mg—O20175.05 (7)
O8—V3—O1476.94 (5)O18—Mg—O1796.68 (6)
O5—V3—O1474.01 (5)O16—Mg—O1788.42 (6)
O3—V3—V4139.67 (5)O15—Mg—O1789.55 (6)
O7—V3—V433.35 (4)O20—Mg—O1790.47 (6)
O10—V3—V484.61 (4)O18—Mg—O1991.04 (6)
O8—V3—V482.61 (4)O16—Mg—O1983.90 (6)
O5—V3—V4122.25 (4)O15—Mg—O1991.80 (6)
O14—V3—V448.26 (3)O20—Mg—O1988.84 (6)
O3—V3—V5i129.08 (5)O17—Mg—O19172.23 (6)
O7—V3—V5i124.55 (4)Mg—O15—H15A124 (2)
O10—V3—V5i78.26 (4)Mg—O15—H15B124 (2)
O8—V3—V5i78.55 (4)H15A—O15—H15B107 (3)
O5—V3—V5i31.07 (4)Mg—O16—H16A131 (3)
O14—V3—V5i42.96 (3)Mg—O16—H16B126 (2)
V4—V3—V5i91.210 (11)H16A—O16—H16B103 (3)
O4—V4—O7105.00 (6)Mg—O17—H17A119.6 (17)
O4—V4—O9102.66 (6)Mg—O17—H17B114 (2)
O7—V4—O993.46 (6)H17A—O17—H17B109 (3)
O4—V4—O1199.82 (6)Mg—O18—H18A120 (2)
O7—V4—O1190.57 (6)Mg—O18—H18B125 (2)
O9—V4—O11155.26 (6)H18A—O18—H18B114 (3)
O4—V4—O698.15 (6)Mg—O19—H19A119 (2)
O7—V4—O6156.63 (5)Mg—O19—H19B114 (2)
O9—V4—O684.47 (5)H19A—O19—H19B106 (3)
O11—V4—O682.25 (5)Mg—O20—H20A124 (2)
O4—V4—O14171.81 (6)Mg—O20—H20B120 (2)
O7—V4—O1482.71 (5)H20A—O20—H20B112 (3)
O9—V4—O1479.29 (5)O22—Na—O2187.75 (6)
O11—V4—O1477.03 (5)O22—Na—O11171.56 (6)
O6—V4—O1474.02 (5)O21—Na—O1184.71 (6)
O4—V4—V3138.65 (5)O22—Na—O21ii79.37 (6)
O7—V4—V333.68 (4)O21—Na—O21ii86.51 (6)
O9—V4—V386.29 (4)O11—Na—O21ii96.36 (6)
O11—V4—V383.62 (4)O22—Na—O3iii75.39 (5)
O6—V4—V3123.03 (4)O21—Na—O3iii143.59 (6)
O14—V4—V349.03 (3)O11—Na—O3iii113.00 (5)
O4—V4—V1135.60 (5)O21ii—Na—O3iii120.57 (6)
O7—V4—V183.28 (4)O22—Na—O4125.32 (6)
O9—V4—V132.96 (4)O21—Na—O4133.54 (6)
O11—V4—V1123.98 (4)O11—Na—O458.98 (4)
O6—V4—V182.44 (4)O21ii—Na—O471.38 (5)
O14—V4—V146.96 (3)O3iii—Na—O481.23 (4)
V3—V4—V161.595 (9)O22—Na—V4152.77 (5)
O4—V4—V5128.89 (5)O21—Na—V4113.87 (5)
O7—V4—V5125.99 (4)O11—Na—V431.93 (3)
O9—V4—V579.57 (4)O21ii—Na—V485.40 (4)
O11—V4—V578.33 (4)O3iii—Na—V493.61 (4)
O6—V4—V530.75 (3)O4—Na—V427.46 (3)
O14—V4—V543.29 (3)O22—Na—Naii80.98 (5)
V3—V4—V592.319 (11)O21—Na—Naii45.05 (4)
V1—V4—V562.181 (10)O11—Na—Naii91.00 (4)
O4—V4—V2131.50 (5)O21ii—Na—Naii41.46 (4)
O7—V4—V282.28 (4)O3iii—Na—Naii153.44 (5)
O9—V4—V2125.04 (4)O4—Na—Naii103.33 (4)
O11—V4—V231.68 (4)V4—Na—Naii102.21 (3)
O6—V4—V279.98 (4)Na—O21—Naii93.49 (6)
O14—V4—V245.76 (3)Na—O21—H21A116 (3)
V3—V4—V260.834 (9)Naii—O21—H21A115 (3)
V1—V4—V292.548 (11)Na—O21—H21B115 (2)
V5—V4—V260.980 (9)Naii—O21—H21B121 (2)
O4—V4—Na58.49 (5)H21A—O21—H21B98 (3)
O7—V4—Na107.82 (4)Na—O22—H22A124 (3)
O9—V4—Na154.24 (4)Na—O22—H22B124 (2)
O11—V4—Na42.16 (4)H22A—O22—H22B107 (3)
O6—V4—Na81.52 (4)H23A—O23—H23B98 (3)
O14—V4—Na116.92 (4)H24A—O24—H24B112 (3)
V3—V4—Na119.467 (17)
Symmetry codes: (i) x, y, z+1/2; (ii) x+1/2, y+3/2, z+1; (iii) x, y+1, z+1/2; (iv) x, y+1, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O15—H15A···O8v0.72 (3)2.02 (3)2.7291 (19)169 (3)
O15—H15B···O24vi0.72 (3)2.06 (3)2.749 (2)160 (3)
O16—H16A···O120.67 (3)1.98 (3)2.6517 (19)175 (4)
O16—H16B···O19vii0.75 (3)2.02 (3)2.774 (2)179 (3)
O17—H17A···O90.77 (3)2.05 (3)2.7933 (19)164 (2)
O17—H17B···O7viii0.71 (3)2.10 (3)2.8052 (19)174 (3)
O18—H18A···O23v0.74 (3)1.99 (3)2.729 (2)176 (3)
O18—H18B···O22ix0.69 (3)2.11 (3)2.800 (2)177 (3)
O19—H19A···O2iii0.73 (3)2.26 (3)2.8600 (19)141 (3)
O19—H19A···O1v0.73 (3)2.52 (3)3.037 (2)130 (2)
O19—H19B···O24x0.72 (3)2.11 (3)2.822 (2)170 (3)
O20—H20A···O60.68 (3)2.05 (3)2.725 (2)176 (3)
O20—H20B···O10iii0.72 (3)1.97 (3)2.686 (2)171 (3)
O21—H21A···O17xi0.72 (3)2.29 (4)3.007 (2)176 (4)
O21—H21B···O20.80 (3)2.34 (3)3.052 (2)149 (3)
O22—H22A···O23iii0.69 (3)2.09 (3)2.784 (2)174 (3)
O22—H22B···O10ii0.77 (3)2.30 (3)2.950 (2)142 (3)
O23—H23A···O80.69 (3)2.11 (3)2.756 (2)154 (3)
O23—H23B···O4viii0.82 (3)2.19 (3)2.900 (2)146 (3)
O24—H24A···O130.74 (3)1.95 (3)2.685 (2)172 (3)
O24—H24B···O5iii0.67 (3)2.17 (3)2.827 (2)167 (3)
Symmetry codes: (ii) x+1/2, y+3/2, z+1; (iii) x, y+1, z+1/2; (v) x, y, z+1/2; (vi) x, y1, z; (vii) x, y, z+1; (viii) x+1/2, y+1/2, z+1; (ix) x+1/2, y1/2, z+3/2; (x) x, y+1, z+1; (xi) x, y+1, z.
(II) trimagnesium decavanadate octacosahydrate top
Crystal data top
Mg3V10O28·28H2OZ = 2
Mr = 1534.78F(000) = 1540
Triclinic, P1Dx = 2.220 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.4834 (1) ÅCell parameters from 8192 reflections
b = 10.7309 (2) Åθ = 2.0–30.0°
c = 21.2293 (4) ŵ = 2.12 mm1
α = 90.751 (1)°T = 93 K
β = 97.866 (1)°Block, orange
γ = 103.663 (1)°0.30 × 0.18 × 0.14 mm
V = 2296.24 (6) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
13207 independent reflections
Radiation source: Rigaku UltraX-18 rotating anode10950 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
Detector resolution: 10 pixels mm-1θmax = 30.0°, θmin = 2.0°
ω scansh = 1414
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 915
Tmin = 0.518, Tmax = 0.743l = 2729
22420 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: difference Fourier map
wR(F2) = 0.086H-atom parameters not refined
S = 1.01 w = 1/[σ2(Fo2) + (0.0467P)2]
where P = (Fo2 + 2Fc2)/3
13207 reflections(Δ/σ)max = 0.002
632 parametersΔρmax = 0.99 e Å3
0 restraintsΔρmin = 0.95 e Å3
Crystal data top
Mg3V10O28·28H2Oγ = 103.663 (1)°
Mr = 1534.78V = 2296.24 (6) Å3
Triclinic, P1Z = 2
a = 10.4834 (1) ÅMo Kα radiation
b = 10.7309 (2) ŵ = 2.12 mm1
c = 21.2293 (4) ÅT = 93 K
α = 90.751 (1)°0.30 × 0.18 × 0.14 mm
β = 97.866 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
13207 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
10950 reflections with I > 2σ(I)
Tmin = 0.518, Tmax = 0.743Rint = 0.025
22420 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.086H-atom parameters not refined
S = 1.01Δρmax = 0.99 e Å3
13207 reflectionsΔρmin = 0.95 e Å3
632 parameters
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
xyzUiso*/UeqOcc. (<1)
V10.01390 (3)0.24943 (3)0.023068 (16)0.00664 (7)
V20.12606 (3)0.14660 (3)0.086083 (16)0.00743 (7)
V30.24898 (3)0.09011 (3)0.065604 (16)0.00790 (7)
V40.01812 (3)0.12080 (3)0.152868 (16)0.00824 (7)
V50.14348 (3)0.01526 (3)0.047124 (15)0.00594 (7)
O10.06339 (15)0.39143 (14)0.00221 (7)0.0118 (3)
O20.17465 (16)0.29019 (15)0.10872 (8)0.0140 (3)
O30.39140 (15)0.11831 (16)0.07086 (7)0.0129 (3)
O40.07879 (16)0.17042 (16)0.22535 (7)0.0156 (3)
O50.28150 (14)0.02503 (14)0.02698 (7)0.0094 (3)
O60.17817 (14)0.06983 (15)0.12320 (7)0.0097 (3)
O70.15061 (14)0.14006 (14)0.14536 (7)0.0096 (3)
O80.15803 (14)0.24264 (14)0.03364 (7)0.0090 (3)
O90.07406 (14)0.26798 (14)0.10794 (7)0.0095 (3)
O100.27488 (14)0.08202 (15)0.08441 (7)0.0101 (3)
O110.04116 (14)0.05820 (14)0.16011 (7)0.0097 (3)
O120.16761 (13)0.17856 (14)0.00828 (7)0.0075 (3)
O130.04842 (13)0.15684 (14)0.06161 (7)0.0073 (3)
O140.04905 (13)0.04609 (13)0.04770 (6)0.0066 (3)
V60.34035 (3)0.37841 (3)0.395074 (16)0.00610 (7)
V70.42408 (3)0.39064 (3)0.607632 (15)0.00640 (7)
V80.17308 (3)0.35497 (3)0.507868 (16)0.00697 (7)
V90.36096 (3)0.17784 (3)0.497797 (16)0.00725 (7)
V100.60101 (3)0.40431 (3)0.496502 (15)0.00539 (7)
O150.31059 (15)0.37189 (15)0.31834 (7)0.0109 (3)
O160.45553 (14)0.39772 (15)0.68425 (7)0.0108 (3)
O170.01814 (14)0.33846 (15)0.51011 (7)0.0114 (3)
O180.35272 (15)0.02545 (15)0.49510 (7)0.0120 (3)
O190.23428 (14)0.54803 (14)0.50650 (7)0.0083 (3)
O200.56095 (14)0.24272 (14)0.49581 (7)0.0076 (3)
O210.19249 (14)0.18854 (14)0.50297 (7)0.0086 (3)
O220.17835 (14)0.36437 (14)0.41832 (7)0.0081 (3)
O230.34650 (14)0.21115 (14)0.41172 (7)0.0084 (3)
O240.24568 (14)0.37590 (14)0.59340 (7)0.0087 (3)
O250.41177 (14)0.22076 (14)0.58628 (7)0.0082 (3)
O260.54268 (13)0.42214 (14)0.40752 (6)0.0070 (3)
O270.61069 (13)0.43407 (14)0.58771 (6)0.0067 (3)
O280.39959 (13)0.39754 (13)0.50125 (6)0.0068 (3)
Mg10.36814 (7)0.64111 (7)0.11116 (3)0.00893 (13)
O290.20417 (15)0.70626 (16)0.13009 (7)0.0133 (3)
H29A0.16280.75220.11370.020*
H29B0.19000.71780.16420.020*
O300.28291 (15)0.59050 (15)0.01891 (7)0.0119 (3)
H30A0.22050.52380.01310.018*
H30B0.24320.63770.00510.018*
O310.45800 (14)0.82080 (15)0.08286 (8)0.0134 (3)
H31A0.42360.88150.07030.020*
H31B0.53580.85300.08810.020*
O320.47023 (14)0.70467 (15)0.20146 (7)0.0109 (3)
H32A0.54260.74660.20380.016*
H32B0.47380.65600.23140.016*
O330.29112 (14)0.46667 (15)0.14471 (8)0.0132 (3)
H33A0.33840.42740.16810.020*
H33B0.22290.40830.13880.020*
O340.52740 (15)0.56597 (15)0.08970 (7)0.0131 (3)
H34A0.50300.49270.07400.020*
H34B0.54890.59440.05090.020*
Mg20.23696 (7)0.85624 (7)0.31211 (3)0.00920 (13)
O350.07560 (14)0.79128 (15)0.24116 (7)0.0109 (3)
H35A0.04720.84200.21680.016*
H35B0.01160.74940.25410.016*
O360.27165 (15)0.67493 (15)0.30863 (7)0.0143 (3)
H36A0.22180.60720.28890.021*
H36B0.30600.63610.34320.021*
O370.21552 (15)1.04021 (15)0.31645 (7)0.0135 (3)
H37A0.18041.07550.28800.020*
H37B0.25511.09360.34850.020*
O380.35812 (15)0.90049 (15)0.24374 (8)0.0143 (3)
H38A0.39460.97710.23040.021*
H38B0.38720.83670.23270.021*
O390.40325 (14)0.91515 (16)0.38250 (7)0.0126 (3)
H39A0.45940.87140.38810.019*
H39B0.39120.94120.42210.019*
O400.12096 (16)0.80419 (15)0.38227 (7)0.0147 (3)
H40A0.09040.86210.39850.022*
H40B0.08580.72510.38750.022*
Mg30.75884 (7)0.17655 (7)0.34686 (4)0.01084 (14)
O410.55648 (15)0.15355 (17)0.34636 (8)0.0159 (3)
H41A0.50000.18570.36130.024*
H41B0.49940.06740.35760.024*
O420.72967 (17)0.02248 (15)0.34442 (7)0.0158 (3)
H42A0.73490.04800.30950.024*
H42B0.69580.08030.36730.024*
O430.79438 (15)0.17481 (16)0.44430 (7)0.0145 (3)
H43A0.85520.24040.46840.022*
H43B0.73260.13160.46470.022*
O440.76817 (18)0.37020 (17)0.35071 (8)0.0207 (4)
H44A0.84490.38950.35100.031*
H44B0.70340.40010.37310.031*
O450.72756 (16)0.16439 (17)0.24970 (7)0.0168 (3)
H45A0.78180.17410.22460.025*
H45B0.65900.15080.23350.025*
O460.96004 (17)0.1961 (2)0.34707 (11)0.0421 (7)
H46A1.02790.26060.36810.063*
H46B0.97840.19520.31370.063*
O470.84110 (15)0.67127 (16)0.28246 (7)0.0143 (3)
H47A0.79850.60850.26180.022*
H47B0.82500.65740.31910.022*
O480.45585 (15)0.35168 (16)0.21830 (7)0.0145 (3)
H48A0.54030.39160.22030.022*
H48B0.43380.36310.25370.022*
O490.72061 (16)0.85099 (16)0.22993 (7)0.0142 (3)
H49A0.76110.88410.20260.021*
H49B0.77400.80190.24850.021*
O500.47564 (16)0.11250 (16)0.18493 (8)0.0158 (3)
H50A0.48090.09870.14650.024*
H50B0.45400.18650.19570.024*
O510.01521 (17)0.53150 (17)0.36980 (8)0.0196 (3)
H51A0.03600.52020.33200.029*
H51B0.07190.50200.39870.029*
O520.90891 (18)0.46003 (16)0.13737 (8)0.0196 (3)
H52A0.91510.52840.11730.029*
H52B0.91200.40460.11940.029*
O530.00594 (16)0.98053 (17)0.42894 (9)0.0203 (4)
H53A0.05821.06120.44130.030*
H53B0.07110.92610.45670.030*
O540.08233 (17)0.46651 (17)0.25104 (8)0.0209 (4)
H54A0.03430.47840.21600.031*
H54B0.10850.39540.24550.031*
O55A0.4295 (2)0.3204 (2)0.0293 (2)0.0140 (9)0.685 (12)
H55A0.35290.28120.03110.021*0.685
H55B0.47740.27200.03160.021*0.685
O55B0.4337 (6)0.3084 (6)0.0593 (5)0.0162 (17)*0.315 (12)
O56A0.6925 (2)0.4934 (2)0.19051 (12)0.0149 (7)0.657 (6)
H56A0.75250.45360.18590.022*0.657
H56B0.67040.54170.16050.022*0.657
O56B0.7229 (5)0.4420 (5)0.2211 (2)0.0159 (14)*0.343 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V10.00690 (14)0.00442 (15)0.00841 (15)0.00097 (11)0.00102 (11)0.00095 (12)
V20.00825 (15)0.00641 (16)0.00835 (15)0.00193 (12)0.00315 (11)0.00322 (12)
V30.00663 (14)0.00810 (16)0.00975 (16)0.00250 (12)0.00251 (12)0.00216 (12)
V40.01062 (15)0.00869 (16)0.00560 (15)0.00372 (12)0.00059 (11)0.00024 (12)
V50.00472 (13)0.00586 (15)0.00672 (15)0.00114 (11)0.00077 (11)0.00091 (11)
O10.0118 (7)0.0068 (7)0.0172 (7)0.0025 (5)0.0033 (5)0.0020 (6)
O20.0177 (7)0.0102 (7)0.0159 (8)0.0034 (6)0.0076 (6)0.0052 (6)
O30.0100 (7)0.0154 (8)0.0149 (7)0.0052 (6)0.0035 (5)0.0030 (6)
O40.0220 (8)0.0153 (8)0.0096 (7)0.0084 (6)0.0047 (6)0.0028 (6)
O50.0070 (6)0.0103 (7)0.0107 (7)0.0027 (5)0.0002 (5)0.0013 (5)
O60.0097 (6)0.0104 (7)0.0085 (7)0.0032 (5)0.0021 (5)0.0002 (5)
O70.0117 (7)0.0100 (7)0.0086 (7)0.0042 (5)0.0033 (5)0.0020 (5)
O80.0092 (6)0.0087 (7)0.0100 (7)0.0039 (5)0.0012 (5)0.0023 (5)
O90.0097 (6)0.0072 (7)0.0105 (7)0.0010 (5)0.0006 (5)0.0012 (5)
O100.0075 (6)0.0110 (7)0.0126 (7)0.0021 (5)0.0039 (5)0.0027 (6)
O110.0126 (7)0.0105 (7)0.0072 (6)0.0046 (5)0.0027 (5)0.0026 (5)
O120.0057 (6)0.0057 (6)0.0102 (7)0.0002 (5)0.0008 (5)0.0003 (5)
O130.0074 (6)0.0073 (7)0.0071 (6)0.0024 (5)0.0000 (5)0.0031 (5)
O140.0060 (6)0.0068 (7)0.0070 (6)0.0014 (5)0.0005 (5)0.0014 (5)
V60.00659 (14)0.00563 (15)0.00543 (14)0.00070 (11)0.00008 (11)0.00045 (11)
V70.00611 (14)0.00720 (16)0.00543 (15)0.00099 (11)0.00018 (11)0.00168 (11)
V80.00490 (14)0.00793 (16)0.00744 (15)0.00051 (11)0.00044 (11)0.00095 (12)
V90.00746 (14)0.00472 (15)0.00866 (15)0.00048 (11)0.00036 (11)0.00118 (12)
V100.00507 (14)0.00527 (15)0.00600 (15)0.00177 (11)0.00043 (11)0.00063 (11)
O150.0122 (7)0.0116 (7)0.0078 (7)0.0015 (6)0.0001 (5)0.0001 (5)
O160.0103 (6)0.0144 (7)0.0076 (7)0.0030 (6)0.0010 (5)0.0023 (5)
O170.0074 (6)0.0132 (8)0.0130 (7)0.0014 (5)0.0008 (5)0.0015 (6)
O180.0135 (7)0.0064 (7)0.0142 (7)0.0008 (5)0.0013 (5)0.0011 (6)
O190.0072 (6)0.0091 (7)0.0089 (7)0.0031 (5)0.0003 (5)0.0006 (5)
O200.0084 (6)0.0058 (7)0.0085 (6)0.0022 (5)0.0004 (5)0.0007 (5)
O210.0085 (6)0.0061 (7)0.0100 (7)0.0005 (5)0.0005 (5)0.0013 (5)
O220.0076 (6)0.0080 (7)0.0079 (6)0.0010 (5)0.0006 (5)0.0010 (5)
O230.0100 (6)0.0052 (6)0.0087 (7)0.0008 (5)0.0010 (5)0.0000 (5)
O240.0075 (6)0.0114 (7)0.0076 (6)0.0022 (5)0.0015 (5)0.0022 (5)
O250.0081 (6)0.0060 (7)0.0097 (7)0.0004 (5)0.0009 (5)0.0017 (5)
O260.0072 (6)0.0081 (7)0.0062 (6)0.0027 (5)0.0009 (5)0.0003 (5)
O270.0072 (6)0.0070 (7)0.0061 (6)0.0023 (5)0.0004 (5)0.0013 (5)
O280.0071 (6)0.0062 (7)0.0075 (6)0.0021 (5)0.0007 (5)0.0009 (5)
Mg10.0095 (3)0.0075 (3)0.0090 (3)0.0020 (3)0.0017 (2)0.0014 (3)
O290.0147 (7)0.0152 (8)0.0117 (7)0.0087 (6)0.0010 (5)0.0015 (6)
O300.0126 (7)0.0076 (7)0.0130 (7)0.0012 (5)0.0051 (5)0.0011 (6)
O310.0086 (7)0.0101 (7)0.0202 (8)0.0009 (5)0.0000 (6)0.0053 (6)
O320.0105 (7)0.0130 (7)0.0079 (7)0.0016 (5)0.0015 (5)0.0025 (6)
O330.0093 (7)0.0089 (7)0.0187 (8)0.0003 (5)0.0033 (6)0.0042 (6)
O340.0120 (7)0.0117 (7)0.0158 (7)0.0022 (6)0.0041 (6)0.0003 (6)
Mg20.0078 (3)0.0098 (3)0.0093 (3)0.0017 (3)0.0004 (2)0.0016 (3)
O350.0087 (6)0.0113 (7)0.0118 (7)0.0017 (5)0.0008 (5)0.0035 (6)
O360.0159 (7)0.0110 (7)0.0143 (7)0.0037 (6)0.0048 (6)0.0019 (6)
O370.0163 (7)0.0103 (7)0.0115 (7)0.0034 (6)0.0065 (6)0.0005 (6)
O380.0157 (7)0.0093 (7)0.0186 (8)0.0021 (6)0.0069 (6)0.0017 (6)
O390.0099 (7)0.0181 (8)0.0098 (7)0.0049 (6)0.0016 (5)0.0020 (6)
O400.0168 (7)0.0114 (8)0.0155 (8)0.0008 (6)0.0059 (6)0.0025 (6)
Mg30.0100 (3)0.0088 (3)0.0133 (3)0.0007 (3)0.0030 (3)0.0027 (3)
O410.0109 (7)0.0238 (9)0.0147 (8)0.0070 (6)0.0038 (6)0.0019 (6)
O420.0270 (9)0.0081 (7)0.0109 (7)0.0007 (6)0.0071 (6)0.0022 (6)
O430.0125 (7)0.0136 (8)0.0137 (7)0.0021 (6)0.0014 (6)0.0019 (6)
O440.0299 (9)0.0129 (8)0.0211 (9)0.0043 (7)0.0117 (7)0.0011 (7)
O450.0151 (7)0.0273 (9)0.0120 (7)0.0103 (7)0.0061 (6)0.0032 (7)
O460.0094 (8)0.0625 (16)0.0461 (13)0.0068 (9)0.0071 (8)0.0450 (12)
O470.0110 (7)0.0168 (8)0.0135 (7)0.0000 (6)0.0016 (5)0.0003 (6)
O480.0146 (7)0.0167 (8)0.0138 (7)0.0060 (6)0.0040 (6)0.0028 (6)
O490.0177 (7)0.0136 (8)0.0109 (7)0.0007 (6)0.0060 (6)0.0001 (6)
O500.0197 (8)0.0131 (8)0.0139 (8)0.0015 (6)0.0046 (6)0.0005 (6)
O510.0206 (8)0.0196 (9)0.0181 (8)0.0047 (7)0.0012 (6)0.0044 (7)
O520.0286 (9)0.0139 (8)0.0173 (8)0.0070 (7)0.0042 (7)0.0025 (6)
O530.0106 (7)0.0158 (8)0.0333 (10)0.0017 (6)0.0019 (7)0.0023 (7)
O540.0211 (8)0.0169 (9)0.0242 (9)0.0078 (7)0.0035 (7)0.0027 (7)
O55A0.0107 (11)0.0131 (12)0.019 (2)0.0025 (8)0.0030 (9)0.0013 (10)
O56A0.0138 (11)0.0155 (13)0.0146 (13)0.0035 (9)0.0008 (9)0.0040 (10)
Geometric parameters (Å, º) top
V1—O11.6134 (15)O26—V7ii1.9946 (15)
V1—O91.8177 (15)O27—V6ii1.9718 (15)
V1—O81.8312 (14)O28—V10ii2.1277 (14)
V1—O13i1.9927 (14)Mg1—O332.0351 (17)
V1—O121.9962 (14)Mg1—O302.0474 (16)
V1—O142.2168 (14)Mg1—O312.0721 (17)
V1—V2i3.0432 (5)Mg1—O322.0846 (16)
V1—V43.0977 (5)Mg1—O292.0868 (17)
V2—O21.6063 (16)Mg1—O342.1165 (17)
V2—O111.8279 (15)O29—H29A0.7849
V2—O101.8471 (15)O29—H29B0.7732
V2—O131.9953 (14)O30—H30A0.8426
V2—O12i1.9984 (14)O30—H30B0.8591
V2—O142.2421 (14)O31—H31A0.8454
V2—V1i3.0433 (5)O31—H31B0.7988
V2—V33.1182 (5)O32—H32A0.7799
V3—O31.6098 (15)O32—H32B0.8304
V3—O71.8587 (15)O33—H33A0.8408
V3—O101.8593 (16)O33—H33B0.8254
V3—O81.8756 (15)O34—H34A0.8182
V3—O52.0335 (15)O34—H34B0.9205
V3—O142.3327 (14)Mg2—O372.0413 (17)
V3—V5i3.0778 (5)Mg2—O382.0453 (17)
V3—V43.0838 (5)Mg2—O402.0509 (17)
V4—O41.6144 (15)Mg2—O362.0643 (18)
V4—O71.8148 (15)Mg2—O352.0818 (16)
V4—O91.8717 (15)Mg2—O392.1008 (16)
V4—O111.8892 (15)O35—H35A0.8331
V4—O62.0554 (15)O35—H35B0.7993
V4—O142.3193 (14)O36—H36A0.8540
V4—V53.0811 (5)O36—H36B0.9212
V5—O61.6725 (14)O37—H37A0.8091
V5—O5i1.7097 (14)O37—H37B0.8739
V5—O121.9236 (15)O38—H38A0.8884
V5—O131.9307 (15)O38—H38B0.8549
V5—O142.1226 (14)O39—H39A0.8329
V5—O14i2.1396 (14)O39—H39B0.9168
V5—V3i3.0778 (5)O40—H40A0.8522
O5—V5i1.7097 (14)O40—H40B0.8569
O12—V2i1.9983 (14)Mg3—O452.0414 (17)
O13—V1i1.9927 (14)Mg3—O432.0521 (17)
O14—V5i2.1397 (14)Mg3—O442.0571 (19)
V6—O151.6135 (15)Mg3—O462.0692 (19)
V6—O221.8058 (14)Mg3—O412.0756 (17)
V6—O231.8481 (15)Mg3—O422.0837 (17)
V6—O27ii1.9717 (15)Mg3—H44A2.2456
V6—O262.0402 (14)O41—H41A0.8459
V6—O282.2479 (14)O41—H41B1.0263
V6—V7ii3.0652 (5)O42—H42A0.8003
V6—V93.1062 (5)O42—H42B0.8356
V7—O161.6119 (15)O43—H43A0.9236
V7—O241.8217 (14)O43—H43B0.8731
V7—O251.8429 (15)O44—H44A0.7809
V7—O26ii1.9946 (15)O44—H44B0.9886
V7—O272.0060 (14)O45—H45A0.8212
V7—O282.2420 (14)O45—H45B0.7332
V7—V6ii3.0652 (5)O46—H46A0.9259
V7—V83.0877 (5)O46—H46B0.7594
V8—O171.5992 (15)O47—H47A0.8013
V8—O211.8478 (15)O47—H47B0.8262
V8—O241.8593 (14)O48—H48A0.8827
V8—O221.9128 (14)O48—H48B0.8317
V8—O192.0207 (15)O49—H49A0.8029
V8—O282.3340 (14)O49—H49B0.9112
V8—V93.0677 (5)O50—H50A0.8389
V8—V10ii3.0768 (5)O50—H50B0.9105
V9—O181.6169 (16)O51—H51A0.8739
V9—O211.8147 (15)O51—H51B0.9079
V9—O231.8592 (15)O52—H52A0.8468
V9—O251.9005 (14)O52—H52B0.7122
V9—O202.0537 (14)O53—H53A0.9215
V9—O282.2943 (15)O53—H53B1.1210
V9—V103.0613 (5)O54—H54A0.8680
V10—O201.6843 (15)O54—H54B0.8813
V10—O19ii1.6914 (14)O55A—H55A0.8200
V10—O261.9306 (14)O55A—H55B0.8012
V10—O271.9432 (14)O55B—H55A0.9488
V10—O282.1120 (14)O55B—H55B0.9278
V10—O28ii2.1277 (14)O56A—H56A0.8539
V10—V8ii3.0768 (5)O56A—H56B0.8683
O19—V10ii1.6914 (14)O56B—H56A0.8467
O1—V1—O9103.89 (7)O21—V8—O2492.03 (7)
O1—V1—O8102.95 (7)O17—V8—O22101.01 (7)
O9—V1—O893.88 (7)O21—V8—O2289.08 (6)
O1—V1—O13i97.56 (7)O24—V8—O22154.91 (6)
O9—V1—O13i156.66 (7)O17—V8—O19100.71 (7)
O8—V1—O13i90.15 (6)O21—V8—O19154.97 (6)
O1—V1—O1298.92 (7)O24—V8—O1985.59 (6)
O9—V1—O1290.23 (6)O22—V8—O1982.93 (6)
O8—V1—O12156.04 (6)O17—V8—O28174.82 (7)
O13i—V1—O1277.30 (6)O21—V8—O2880.71 (6)
O1—V1—O14173.59 (7)O24—V8—O2878.56 (6)
O9—V1—O1481.21 (6)O22—V8—O2876.90 (5)
O8—V1—O1480.33 (6)O19—V8—O2874.40 (5)
O13i—V1—O1476.82 (6)O17—V8—V9136.85 (6)
O12—V1—O1476.99 (5)O21—V8—V932.78 (4)
O1—V1—V2i87.98 (6)O24—V8—V984.97 (5)
O9—V1—V2i130.63 (5)O22—V8—V982.48 (5)
O8—V1—V2i130.44 (5)O19—V8—V9122.30 (4)
O13i—V1—V2i40.29 (4)O28—V8—V947.93 (4)
O12—V1—V2i40.40 (4)O17—V8—V10ii131.44 (6)
O14—V1—V2i85.73 (4)O21—V8—V10ii124.37 (5)
O1—V1—V4137.13 (6)O24—V8—V10ii80.10 (5)
O9—V1—V433.45 (5)O22—V8—V10ii78.64 (4)
O8—V1—V482.53 (5)O19—V8—V10ii30.73 (4)
O13i—V1—V4125.14 (4)O28—V8—V10ii43.68 (4)
O12—V1—V488.10 (4)V9—V8—V10ii91.609 (12)
O14—V1—V448.33 (4)O17—V8—V7135.57 (6)
V2i—V1—V4120.938 (14)O21—V8—V782.43 (5)
O2—V2—O11102.69 (8)O24—V8—V732.61 (4)
O2—V2—O10103.24 (7)O22—V8—V7123.21 (4)
O11—V2—O1094.37 (7)O19—V8—V782.25 (4)
O2—V2—O1399.44 (7)O28—V8—V746.32 (3)
O11—V2—O1390.01 (6)V9—V8—V761.183 (11)
O10—V2—O13155.31 (6)V10ii—V8—V761.864 (11)
O2—V2—O12i100.07 (7)O18—V9—O21104.43 (7)
O11—V2—O12i155.43 (6)O18—V9—O23101.12 (7)
O10—V2—O12i89.29 (6)O21—V9—O2392.99 (6)
O13—V2—O12i77.19 (6)O18—V9—O25101.73 (7)
O2—V2—O14174.62 (7)O21—V9—O2591.02 (6)
O11—V2—O1480.49 (6)O23—V9—O25155.01 (7)
O10—V2—O1480.68 (6)O18—V9—O2098.27 (7)
O13—V2—O1476.10 (5)O21—V9—O20157.24 (6)
O12i—V2—O1476.14 (5)O23—V9—O2084.04 (6)
O2—V2—V1i89.95 (6)O25—V9—O2082.79 (6)
O11—V2—V1i130.23 (5)O18—V9—O28173.07 (7)
O10—V2—V1i129.62 (5)O21—V9—O2882.49 (6)
O13—V2—V1i40.23 (4)O23—V9—O2878.42 (6)
O12i—V2—V1i40.34 (4)O25—V9—O2877.68 (6)
O14—V2—V1i84.70 (4)O20—V9—O2874.80 (5)
O2—V2—V3135.95 (6)O18—V9—V10129.49 (6)
O11—V2—V383.78 (5)O21—V9—V10126.07 (5)
O10—V2—V332.84 (5)O23—V9—V1078.87 (5)
O13—V2—V3124.31 (4)O25—V9—V1078.86 (4)
O12i—V2—V386.29 (4)O20—V9—V1031.23 (4)
O14—V2—V348.26 (4)O28—V9—V1043.59 (3)
V1i—V2—V3119.130 (14)O18—V9—V8137.88 (6)
O3—V3—O7104.53 (7)O21—V9—V833.45 (5)
O3—V3—O10102.63 (7)O23—V9—V886.20 (5)
O7—V3—O1091.08 (7)O25—V9—V883.64 (5)
O3—V3—O8102.39 (7)O20—V9—V8123.82 (4)
O7—V3—O889.42 (6)O28—V9—V849.04 (3)
O10—V3—O8154.01 (6)V10—V9—V892.622 (13)
O3—V3—O599.34 (7)O18—V9—V6133.99 (6)
O7—V3—O5156.07 (6)O21—V9—V682.15 (5)
O10—V3—O585.36 (6)O23—V9—V632.97 (5)
O8—V3—O583.74 (6)O25—V9—V6123.90 (5)
O3—V3—O14174.61 (7)O20—V9—V683.22 (4)
O7—V3—O1480.77 (6)O28—V9—V646.23 (3)
O10—V3—O1478.02 (6)V10—V9—V662.356 (11)
O8—V3—O1476.42 (6)V8—V9—V661.029 (11)
O5—V3—O1475.34 (5)O20—V10—O19ii107.46 (7)
O3—V3—V5i130.73 (6)O20—V10—O2697.62 (7)
O7—V3—V5i124.73 (5)O19ii—V10—O2696.82 (6)
O10—V3—V5i79.52 (5)O20—V10—O2796.95 (7)
O8—V3—V5i78.90 (5)O19ii—V10—O2796.94 (6)
O5—V3—V5i31.39 (4)O26—V10—O27155.94 (6)
O14—V3—V5i43.96 (3)O20—V10—O2887.70 (6)
O3—V3—V4137.00 (6)O19ii—V10—O28164.85 (7)
O7—V3—V432.48 (4)O26—V10—O2881.08 (6)
O10—V3—V484.27 (5)O27—V10—O2880.49 (6)
O8—V3—V482.29 (4)O20—V10—O28ii165.68 (6)
O5—V3—V4123.62 (4)O19ii—V10—O28ii86.86 (6)
O14—V3—V448.29 (3)O26—V10—O28ii80.43 (6)
V5i—V3—V492.252 (12)O27—V10—O28ii80.72 (6)
O3—V3—V2135.19 (6)O28—V10—O28ii77.99 (6)
O7—V3—V281.54 (5)O20—V10—V939.21 (5)
O10—V3—V232.60 (4)O19ii—V10—V9146.65 (5)
O8—V3—V2122.23 (5)O26—V10—V989.26 (4)
O5—V3—V282.81 (4)O27—V10—V990.02 (4)
O14—V3—V245.82 (4)O28—V10—V948.50 (4)
V5i—V3—V261.720 (11)O28ii—V10—V9126.48 (4)
V4—V3—V260.580 (11)O20—V10—V8ii145.06 (5)
O4—V4—O7103.53 (8)O19ii—V10—V8ii37.62 (5)
O4—V4—O9102.04 (8)O26—V10—V8ii88.50 (4)
O7—V4—O992.36 (7)O27—V10—V8ii90.44 (4)
O4—V4—O11102.49 (8)O28—V10—V8ii127.23 (4)
O7—V4—O1191.26 (7)O28ii—V10—V8ii49.25 (4)
O9—V4—O11153.61 (6)V9—V10—V8ii175.513 (15)
O4—V4—O6100.51 (7)V10ii—O19—V8111.65 (7)
O7—V4—O6155.95 (6)V10—O20—V9109.57 (7)
O9—V4—O683.33 (6)V9—O21—V8113.77 (7)
O11—V4—O682.78 (6)V6—O22—V8114.91 (7)
O4—V4—O14174.44 (7)V6—O23—V9113.83 (7)
O7—V4—O1482.03 (6)V7—O24—V8114.03 (7)
O9—V4—O1477.39 (6)V7—O25—V9113.61 (8)
O11—V4—O1477.25 (6)V10—O26—V7ii107.65 (7)
O6—V4—O1473.93 (5)V10—O26—V6107.02 (6)
O4—V4—V5130.94 (6)V7ii—O26—V698.87 (6)
O7—V4—V5125.53 (5)V10—O27—V6ii107.02 (7)
O9—V4—V578.26 (5)V10—O27—V7107.20 (6)
O11—V4—V578.40 (4)V6ii—O27—V7100.81 (6)
O6—V4—V530.43 (4)V10—O28—V10ii102.01 (6)
O14—V4—V543.50 (3)V10—O28—V793.75 (5)
O4—V4—V3136.89 (6)V10ii—O28—V792.92 (5)
O7—V4—V333.36 (5)V10—O28—V694.12 (5)
O9—V4—V384.91 (5)V10ii—O28—V691.96 (5)
O11—V4—V383.85 (5)V7—O28—V6169.68 (7)
O6—V4—V3122.59 (4)V10—O28—V987.91 (5)
O14—V4—V348.67 (3)V10ii—O28—V9170.03 (7)
V5—V4—V392.167 (12)V7—O28—V987.34 (5)
O4—V4—V1134.33 (6)V6—O28—V986.28 (5)
O7—V4—V182.60 (5)V10—O28—V8170.88 (7)
O9—V4—V132.36 (4)V10ii—O28—V887.07 (5)
O11—V4—V1122.81 (5)V7—O28—V884.85 (5)
O6—V4—V181.20 (4)V6—O28—V886.33 (5)
O14—V4—V145.56 (4)V9—O28—V883.03 (5)
V5—V4—V161.146 (11)O33—Mg1—O3094.51 (7)
V3—V4—V160.952 (11)O33—Mg1—O31175.63 (7)
O6—V5—O5i107.64 (7)O30—Mg1—O3189.47 (7)
O6—V5—O1297.94 (7)O33—Mg1—O3290.32 (7)
O5i—V5—O1297.49 (7)O30—Mg1—O32174.35 (7)
O6—V5—O1397.28 (7)O31—Mg1—O3285.61 (7)
O5i—V5—O1396.50 (7)O33—Mg1—O2990.62 (7)
O12—V5—O13155.12 (6)O30—Mg1—O2991.27 (7)
O6—V5—O1487.28 (6)O31—Mg1—O2991.10 (7)
O5i—V5—O14165.06 (6)O32—Mg1—O2991.60 (6)
O12—V5—O1480.84 (6)O33—Mg1—O3487.28 (7)
O13—V5—O1480.35 (6)O30—Mg1—O3486.69 (7)
O6—V5—O14i164.89 (6)O31—Mg1—O3491.15 (7)
O5i—V5—O14i87.45 (6)O32—Mg1—O3490.63 (6)
O12—V5—O14i80.18 (6)O29—Mg1—O34176.95 (7)
O13—V5—O14i80.00 (6)Mg1—O29—H29A135.3
O14—V5—O14i77.62 (6)Mg1—O29—H29B123.0
O6—V5—V3i145.92 (5)H29A—O29—H29B96.1
O5i—V5—V3i38.29 (5)Mg1—O30—H30A116.5
O12—V5—V3i88.72 (4)Mg1—O30—H30B124.0
O13—V5—V3i89.62 (4)H30A—O30—H30B96.0
O14—V5—V3i126.80 (4)Mg1—O31—H31A129.4
O14i—V5—V3i49.18 (4)Mg1—O31—H31B126.0
O6—V5—V438.50 (5)H31A—O31—H31B103.6
O5i—V5—V4146.15 (5)Mg1—O32—H32A117.9
O12—V5—V489.88 (4)Mg1—O32—H32B122.6
O13—V5—V489.87 (4)H32A—O32—H32B103.9
O14—V5—V448.78 (4)Mg1—O33—H33A121.9
O14i—V5—V4126.40 (4)Mg1—O33—H33B139.8
V3i—V5—V4175.553 (15)H33A—O33—H33B97.5
V5i—O5—V3110.32 (7)Mg1—O34—H34A112.8
V5—O6—V4111.06 (7)Mg1—O34—H34B108.7
V4—O7—V3114.16 (7)H34A—O34—H34B89.1
V1—O8—V3115.51 (8)O37—Mg2—O3891.00 (7)
V1—O9—V4114.19 (8)O37—Mg2—O4091.80 (7)
V2—O10—V3114.56 (7)O38—Mg2—O40176.81 (8)
V2—O11—V4114.61 (8)O37—Mg2—O36176.32 (7)
V5—O12—V1106.59 (7)O38—Mg2—O3686.78 (7)
V5—O12—V2i108.25 (7)O40—Mg2—O3690.35 (7)
V1—O12—V2i99.26 (6)O37—Mg2—O3594.97 (7)
V5—O13—V1i107.50 (7)O38—Mg2—O3589.63 (7)
V5—O13—V2107.64 (7)O40—Mg2—O3591.66 (7)
V1i—O13—V299.48 (6)O36—Mg2—O3587.95 (7)
V5—O14—V5i102.38 (6)O37—Mg2—O3987.34 (7)
V5—O14—V192.79 (5)O38—Mg2—O3989.34 (7)
V5i—O14—V193.14 (5)O40—Mg2—O3989.25 (7)
V5—O14—V293.08 (5)O36—Mg2—O3989.70 (7)
V5i—O14—V292.97 (5)O35—Mg2—O39177.49 (7)
V1—O14—V2170.43 (7)Mg2—O35—H35A121.1
V5—O14—V487.72 (5)Mg2—O35—H35B113.5
V5i—O14—V4169.90 (7)H35A—O35—H35B105.1
V1—O14—V486.11 (5)Mg2—O36—H36A127.8
V2—O14—V486.58 (5)Mg2—O36—H36B124.4
V5—O14—V3170.75 (7)H36A—O36—H36B97.6
V5i—O14—V386.86 (5)Mg2—O37—H37A125.9
V1—O14—V387.08 (5)Mg2—O37—H37B121.6
V2—O14—V385.91 (5)H37A—O37—H37B112.0
V4—O14—V383.04 (5)Mg2—O38—H38A128.9
O15—V6—O22103.15 (7)Mg2—O38—H38B112.3
O15—V6—O23101.80 (7)H38A—O38—H38B117.7
O22—V6—O2395.03 (7)Mg2—O39—H39A119.9
O15—V6—O27ii100.25 (7)Mg2—O39—H39B118.9
O22—V6—O27ii92.11 (6)H39A—O39—H39B106.7
O23—V6—O27ii154.58 (6)Mg2—O40—H40A117.4
O15—V6—O2699.81 (7)Mg2—O40—H40B121.0
O22—V6—O26155.91 (6)H40A—O40—H40B119.2
O23—V6—O2687.28 (6)O45—Mg3—O43175.38 (8)
O27ii—V6—O2676.62 (6)O45—Mg3—O4493.00 (8)
O15—V6—O28175.03 (7)O43—Mg3—O4491.41 (7)
O22—V6—O2881.27 (6)O45—Mg3—O4690.61 (8)
O23—V6—O2879.87 (6)O43—Mg3—O4687.59 (8)
O27ii—V6—O2877.15 (6)O44—Mg3—O4695.69 (9)
O26—V6—O2875.53 (5)O45—Mg3—O4189.20 (7)
O15—V6—V7ii90.30 (6)O43—Mg3—O4192.53 (7)
O22—V6—V7ii132.09 (5)O44—Mg3—O4185.30 (7)
O23—V6—V7ii127.29 (5)O46—Mg3—O41179.01 (9)
O27ii—V6—V7ii40.00 (4)O45—Mg3—O4287.78 (7)
O26—V6—V7ii40.01 (4)O43—Mg3—O4287.96 (7)
O28—V6—V7ii85.01 (4)O44—Mg3—O42174.27 (8)
O15—V6—V9134.72 (6)O46—Mg3—O4289.98 (9)
O22—V6—V982.95 (5)O41—Mg3—O4289.04 (7)
O23—V6—V933.20 (4)O45—Mg3—H44A93.1
O27ii—V6—V9124.58 (4)O43—Mg3—H44A90.5
O26—V6—V986.09 (4)O44—Mg3—H44A20.3
O28—V6—V947.48 (4)O46—Mg3—H44A75.4
V7ii—V6—V9118.923 (13)O41—Mg3—H44A105.6
O16—V7—O24102.60 (7)O42—Mg3—H44A165.3
O16—V7—O25103.35 (7)Mg3—O41—H41A142.8
O24—V7—O2594.66 (7)Mg3—O41—H41B120.0
O16—V7—O26ii99.38 (7)H41A—O41—H41B84.8
O24—V7—O26ii90.51 (6)Mg3—O42—H42A109.7
O25—V7—O26ii154.95 (6)Mg3—O42—H42B134.3
O16—V7—O2798.99 (7)H42A—O42—H42B113.7
O24—V7—O27156.53 (6)Mg3—O43—H43A121.8
O25—V7—O2789.18 (6)Mg3—O43—H43B119.2
O26ii—V7—O2776.90 (6)H43A—O43—H43B114.4
O16—V7—O28173.97 (7)Mg3—O44—H44A93.6
O24—V7—O2881.82 (6)Mg3—O44—H44B117.9
O25—V7—O2880.19 (6)H44A—O44—H44B136.2
O26ii—V7—O2876.31 (5)Mg3—O45—H45A129.4
O27—V7—O2876.03 (5)Mg3—O45—H45B118.2
O16—V7—V6ii89.17 (6)H45A—O45—H45B112.4
O24—V7—V6ii131.63 (5)Mg3—O46—H46A126.4
O25—V7—V6ii128.37 (5)Mg3—O46—H46B112.5
O26ii—V7—V6ii41.12 (4)H46A—O46—H46B102.5
O27—V7—V6ii39.19 (4)H47A—O47—H47B104.4
O28—V7—V6ii84.82 (4)H48A—O48—H48B107.1
O16—V7—V8135.88 (5)H49A—O49—H49B102.4
O24—V7—V833.37 (4)H50A—O50—H50B117.5
O25—V7—V883.95 (5)H51A—O51—H51B108.1
O26ii—V7—V887.07 (4)H52A—O52—H52B115.8
O27—V7—V8124.84 (4)H53A—O53—H53B123.7
O28—V7—V848.84 (4)H54A—O54—H54B107.8
V6ii—V7—V8120.461 (14)H55A—O55A—H55B110.3
O17—V8—O21104.09 (7)H55A—O55B—H55B90.3
O17—V8—O24103.00 (7)H56A—O56A—H56B118.7
Symmetry codes: (i) x, y, z; (ii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O29—H29A···O13iii0.781.962.734 (2)170.2
O29—H29B···O350.772.383.099 (2)154.6
O30—H30A···O10.841.892.726 (2)171.3
O30—H30B···O8iv0.861.802.631 (2)163.5
O31—H31A···O5iv0.852.102.909 (2)159.2
O31—H31B···O10v0.801.952.743 (2)168.9
O32—H32A···O490.781.942.704 (2)167.1
O32—H32B···O16ii0.831.992.767 (2)155.9
O33—H33A···O480.841.862.695 (2)174.9
O33—H33B···O90.831.932.741 (2)168.2
O34—H34A···O55B0.821.942.742 (6)164.7
O34—H34A···O55A0.822.002.813 (3)174.0
O34—H34B···O55Avi0.921.962.865 (5)167.9
O34—H34B···O55Bvi0.922.593.492 (11)168.4
O35—H35A···O11iii0.831.912.738 (2)172.1
O35—H35B···O47vii0.801.962.756 (2)170.3
O36—H36A···O540.851.912.757 (2)168.6
O36—H36B···O27ii0.921.862.782 (2)175.2
O37—H37A···O4iii0.812.032.829 (2)172.5
O37—H37B···O23iii0.871.832.701 (2)175.8
O38—H38A···O50iii0.891.862.725 (2)165.5
O38—H38B···O320.851.982.830 (2)172.8
O39—H39A···O25ii0.831.882.709 (2)171.5
O39—H39B···O18iii0.921.922.822 (2)167.3
O40—H40A···O530.851.872.715 (2)173.8
O40—H40B···O510.862.052.869 (2)160.9
O40—H40B···O17viii0.862.593.105 (2)119.6
O41—H41A···O230.852.122.934 (2)162.4
O41—H41B···O39ix1.031.832.857 (2)176.5
O42—H42A···O49ix0.801.962.748 (2)166.2
O42—H42B···O25x0.842.012.842 (2)171.3
O43—H43A···O17xi0.921.882.762 (2)160.0
O43—H43B···O18x0.871.982.775 (2)151.6
O43—H43B···O200.872.533.045 (2)118.3
O44—H44A···O51xi0.782.042.728 (2)146.5
O44—H44B···O260.991.992.956 (2)166.0
O44—H44B···O24ii0.992.413.000 (2)117.6
O44—H44B···O19ii0.992.573.150 (2)117.4
O45—H45A···O7xi0.821.972.743 (2)155.5
O45—H45B···O500.732.002.732 (2)176.9
O46—H46A···O22xi0.931.882.796 (2)168.5
O46—H46B···O4xi0.762.313.054 (2)164.9
O47—H47A···O56B0.801.922.705 (5)168.4
O47—H47A···O56A0.801.972.747 (3)162.2
O47—H47B···O24ii0.832.102.916 (2)171.1
O48—H48A···O56B0.881.862.730 (5)168.2
O48—H48A···O56A0.881.902.731 (3)156.2
O48—H48B···O150.832.022.812 (2)157.6
O49—H49A···O11v0.802.333.047 (2)149.7
O49—H49A···O10v0.802.533.185 (2)139.7
O49—H49B···O470.911.832.717 (2)165.2
O50—H50A···O3xi0.842.212.949 (2)147.2
O50—H50B···O480.911.832.716 (2)165.4
O51—H51A···O540.871.962.830 (2)170.8
O51—H51B···O220.912.072.867 (2)146.5
O52—H52A···O2v0.852.353.054 (2)140.5
O52—H52B···O8xi0.712.413.075 (2)155.3
O52—H52B···O9xi0.712.523.096 (2)138.7
O53—H53A···O21iii0.922.032.878 (2)153.1
O53—H53B···O21viii1.121.862.969 (2)170.4
O54—H54A···O52vii0.871.952.805 (2)166.0
O54—H54B···O40.882.393.207 (2)155.3
O54—H54B···O150.882.513.008 (2)116.3
O55A—H55A···O120.821.982.780 (3)163.1
O55A—H55B···O3xi0.802.473.245 (3)163.1
O56A—H56A···O520.852.042.760 (3)141.4
O56A—H56B···O340.872.042.802 (3)146.3
O56A—H56B···O2v0.872.503.097 (3)126.4
Symmetry codes: (ii) x+1, y+1, z+1; (iii) x, y+1, z; (iv) x, y+1, z; (v) x+1, y+1, z; (vi) x+1, y+1, z; (vii) x1, y, z; (viii) x, y+1, z+1; (ix) x, y1, z; (x) x+1, y, z+1; (xi) x+1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaMg2Na2V10O28·20H2OMg3V10O28·28H2O
Mr1412.321534.78
Crystal system, space groupMonoclinic, C2/cTriclinic, P1
Temperature (K)9393
a, b, c (Å)23.8384 (6), 11.0248 (2), 16.9332 (4)10.4834 (1), 10.7309 (2), 21.2293 (4)
α, β, γ (°)90, 118.005 (1), 9090.751 (1), 97.866 (1), 103.663 (1)
V3)3929.18 (15)2296.24 (6)
Z42
Radiation typeMo KαMo Kα
µ (mm1)2.462.12
Crystal size (mm)0.20 × 0.18 × 0.080.30 × 0.18 × 0.14
Data collection
DiffractometerBruker SMART CCD area-detector system
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Multi-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.640, 0.8210.518, 0.743
No. of measured, independent and
observed [I > 2σ(I)] reflections
18758, 5746, 4522 22420, 13207, 10950
Rint0.0340.025
(sin θ/λ)max1)0.7040.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.075, 1.01 0.032, 0.086, 1.01
No. of reflections574613207
No. of parameters360632
H-atom treatmentAll H-atom parameters refinedH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.72, 1.240.99, 0.95

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ATOMS (Dowty, 1999) and ORTEPIII (Burnett & Johnson, 1996).

Selected bond lengths (Å) for (I) top
V1—O11.6008 (13)V4—O111.9117 (13)
V1—O81.8356 (12)V4—O62.0506 (13)
V1—O91.8425 (12)V4—O142.3120 (12)
V1—O122.0005 (12)V5—O5i1.6932 (13)
V1—O12i2.0036 (12)V5—O61.6967 (13)
V1—O142.2717 (13)V5—O131.9168 (13)
V2—O21.6140 (14)V5—O121.9349 (13)
V2—O111.7973 (13)V5—O14i2.0995 (12)
V2—O101.8496 (13)V5—O142.1239 (12)
V2—O131.9923 (13)Mg—O182.0234 (15)
V2—O13i2.0373 (12)Mg—O162.0298 (15)
V2—O142.2376 (13)Mg—O152.0500 (16)
V3—O31.6097 (13)Mg—O202.0523 (16)
V3—O71.8512 (13)Mg—O172.1082 (15)
V3—O101.8557 (13)Mg—O192.1398 (15)
V3—O81.8933 (13)Na—O222.3481 (17)
V3—O52.0510 (13)Na—O212.4195 (19)
V3—O142.3396 (12)Na—O112.4264 (15)
V4—O41.6071 (13)Na—O21ii2.5864 (19)
V4—O71.8349 (13)Na—O3iii2.6620 (15)
V4—O91.8516 (13)Na—O42.9714 (16)
Symmetry codes: (i) x, y, z+1/2; (ii) x+1/2, y+3/2, z+1; (iii) x, y+1, z+1/2.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O15—H15A···O8iv0.72 (3)2.02 (3)2.7291 (19)169 (3)
O15—H15B···O24v0.72 (3)2.06 (3)2.749 (2)160 (3)
O16—H16A···O120.67 (3)1.98 (3)2.6517 (19)175 (4)
O16—H16B···O19vi0.75 (3)2.02 (3)2.774 (2)179 (3)
O17—H17A···O90.77 (3)2.05 (3)2.7933 (19)164 (2)
O17—H17B···O7vii0.71 (3)2.10 (3)2.8052 (19)174 (3)
O18—H18A···O23iv0.74 (3)1.99 (3)2.729 (2)176 (3)
O18—H18B···O22viii0.69 (3)2.11 (3)2.800 (2)177 (3)
O19—H19A···O2iii0.73 (3)2.26 (3)2.8600 (19)141 (3)
O19—H19A···O1iv0.73 (3)2.52 (3)3.037 (2)130 (2)
O19—H19B···O24ix0.72 (3)2.11 (3)2.822 (2)170 (3)
O20—H20A···O60.68 (3)2.05 (3)2.725 (2)176 (3)
O20—H20B···O10iii0.72 (3)1.97 (3)2.686 (2)171 (3)
O21—H21A···O17x0.72 (3)2.29 (4)3.007 (2)176 (4)
O21—H21B···O20.80 (3)2.34 (3)3.052 (2)149 (3)
O22—H22A···O23iii0.69 (3)2.09 (3)2.784 (2)174 (3)
O22—H22B···O10ii0.77 (3)2.30 (3)2.950 (2)142 (3)
O23—H23A···O80.69 (3)2.11 (3)2.756 (2)154 (3)
O23—H23B···O4vii0.82 (3)2.19 (3)2.900 (2)146 (3)
O24—H24A···O130.74 (3)1.95 (3)2.685 (2)172 (3)
O24—H24B···O5iii0.67 (3)2.17 (3)2.827 (2)167 (3)
Symmetry codes: (ii) x+1/2, y+3/2, z+1; (iii) x, y+1, z+1/2; (iv) x, y, z+1/2; (v) x, y1, z; (vi) x, y, z+1; (vii) x+1/2, y+1/2, z+1; (viii) x+1/2, y1/2, z+3/2; (ix) x, y+1, z+1; (x) x, y+1, z.
Selected bond lengths (Å) for (II) top
V1—O11.6134 (15)V7—O26ii1.9946 (15)
V1—O91.8177 (15)V7—O272.0060 (14)
V1—O81.8312 (14)V7—O282.2420 (14)
V1—O13i1.9927 (14)V8—O171.5992 (15)
V1—O121.9962 (14)V8—O211.8478 (15)
V1—O142.2168 (14)V8—O241.8593 (14)
V2—O21.6063 (16)V8—O221.9128 (14)
V2—O111.8279 (15)V8—O192.0207 (15)
V2—O101.8471 (15)V8—O282.3340 (14)
V2—O131.9953 (14)V9—O181.6169 (16)
V2—O12i1.9984 (14)V9—O211.8147 (15)
V2—O142.2421 (14)V9—O231.8592 (15)
V3—O31.6098 (15)V9—O251.9005 (14)
V3—O71.8587 (15)V9—O202.0537 (14)
V3—O101.8593 (16)V9—O282.2943 (15)
V3—O81.8756 (15)V10—O201.6843 (15)
V3—O52.0335 (15)V10—O19ii1.6914 (14)
V3—O142.3327 (14)V10—O261.9306 (14)
V4—O41.6144 (15)V10—O271.9432 (14)
V4—O71.8148 (15)V10—O282.1120 (14)
V4—O91.8717 (15)V10—O28ii2.1277 (14)
V4—O111.8892 (15)Mg1—O332.0351 (17)
V4—O62.0554 (15)Mg1—O302.0474 (16)
V4—O142.3193 (14)Mg1—O312.0721 (17)
V5—O61.6725 (14)Mg1—O322.0846 (16)
V5—O5i1.7097 (14)Mg1—O292.0868 (17)
V5—O121.9236 (15)Mg1—O342.1165 (17)
V5—O131.9307 (15)Mg2—O372.0413 (17)
V5—O142.1226 (14)Mg2—O382.0453 (17)
V5—O14i2.1396 (14)Mg2—O402.0509 (17)
V6—O151.6135 (15)Mg2—O362.0643 (18)
V6—O221.8058 (14)Mg2—O352.0818 (16)
V6—O231.8481 (15)Mg2—O392.1008 (16)
V6—O27ii1.9717 (15)Mg3—O452.0414 (17)
V6—O262.0402 (14)Mg3—O432.0521 (17)
V6—O282.2479 (14)Mg3—O442.0571 (19)
V7—O161.6119 (15)Mg3—O462.0692 (19)
V7—O241.8217 (14)Mg3—O412.0756 (17)
V7—O251.8429 (15)Mg3—O422.0837 (17)
Symmetry codes: (i) x, y, z; (ii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O29—H29A···O13iii0.781.962.734 (2)170.2
O29—H29B···O350.772.383.099 (2)154.6
O30—H30A···O10.841.892.726 (2)171.3
O30—H30B···O8iv0.861.802.631 (2)163.5
O31—H31A···O5iv0.852.102.909 (2)159.2
O31—H31B···O10v0.801.952.743 (2)168.9
O32—H32A···O490.781.942.704 (2)167.1
O32—H32B···O16ii0.831.992.767 (2)155.9
O33—H33A···O480.841.862.695 (2)174.9
O33—H33B···O90.831.932.741 (2)168.2
O34—H34A···O55B0.821.942.742 (6)164.7
O34—H34A···O55A0.822.002.813 (3)174.0
O34—H34B···O55Avi0.921.962.865 (5)167.9
O34—H34B···O55Bvi0.922.593.492 (11)168.4
O35—H35A···O11iii0.831.912.738 (2)172.1
O35—H35B···O47vii0.801.962.756 (2)170.3
O36—H36A···O540.851.912.757 (2)168.6
O36—H36B···O27ii0.921.862.782 (2)175.2
O37—H37A···O4iii0.812.032.829 (2)172.5
O37—H37B···O23iii0.871.832.701 (2)175.8
O38—H38A···O50iii0.891.862.725 (2)165.5
O38—H38B···O320.851.982.830 (2)172.8
O39—H39A···O25ii0.831.882.709 (2)171.5
O39—H39B···O18iii0.921.922.822 (2)167.3
O40—H40A···O530.851.872.715 (2)173.8
O40—H40B···O510.862.052.869 (2)160.9
O40—H40B···O17viii0.862.593.105 (2)119.6
O41—H41A···O230.852.122.934 (2)162.4
O41—H41B···O39ix1.031.832.857 (2)176.5
O42—H42A···O49ix0.801.962.748 (2)166.2
O42—H42B···O25x0.842.012.842 (2)171.3
O43—H43A···O17xi0.921.882.762 (2)160.0
O43—H43B···O18x0.871.982.775 (2)151.6
O43—H43B···O200.872.533.045 (2)118.3
O44—H44A···O51xi0.782.042.728 (2)146.5
O44—H44B···O260.991.992.956 (2)166.0
O44—H44B···O24ii0.992.413.000 (2)117.6
O44—H44B···O19ii0.992.573.150 (2)117.4
O45—H45A···O7xi0.821.972.743 (2)155.5
O45—H45B···O500.732.002.732 (2)176.9
O46—H46A···O22xi0.931.882.796 (2)168.5
O46—H46B···O4xi0.762.313.054 (2)164.9
O47—H47A···O56B0.801.922.705 (5)168.4
O47—H47A···O56A0.801.972.747 (3)162.2
O47—H47B···O24ii0.832.102.916 (2)171.1
O48—H48A···O56B0.881.862.730 (5)168.2
O48—H48A···O56A0.881.902.731 (3)156.2
O48—H48B···O150.832.022.812 (2)157.6
O49—H49A···O11v0.802.333.047 (2)149.7
O49—H49A···O10v0.802.533.185 (2)139.7
O49—H49B···O470.911.832.717 (2)165.2
O50—H50A···O3xi0.842.212.949 (2)147.2
O50—H50B···O480.911.832.716 (2)165.4
O51—H51A···O540.871.962.830 (2)170.8
O51—H51B···O220.912.072.867 (2)146.5
O52—H52A···O2v0.852.353.054 (2)140.5
O52—H52B···O8xi0.712.413.075 (2)155.3
O52—H52B···O9xi0.712.523.096 (2)138.7
O53—H53A···O21iii0.922.032.878 (2)153.1
O53—H53B···O21viii1.121.862.969 (2)170.4
O54—H54A···O52vii0.871.952.805 (2)166.0
O54—H54B···O40.882.393.207 (2)155.3
O54—H54B···O150.882.513.008 (2)116.3
O55A—H55A···O120.821.982.780 (3)163.1
O55A—H55B···O3xi0.802.473.245 (3)163.1
O56A—H56A···O520.852.042.760 (3)141.4
O56A—H56B···O340.872.042.802 (3)146.3
O56A—H56B···O2v0.872.503.097 (3)126.4
Symmetry codes: (ii) x+1, y+1, z+1; (iii) x, y+1, z; (iv) x, y+1, z; (v) x+1, y+1, z; (vi) x+1, y+1, z; (vii) x1, y, z; (viii) x, y+1, z+1; (ix) x, y1, z; (x) x+1, y, z+1; (xi) x+1, y, z.
Coordination geometries of the water molecules around the Mg2+ cations. top
MgOε(a)Classification(b)
Compound I
MgO1519.0Class 1, Type D
O160.0Class 1, Type D
O1736.5Class 2, Type H
O188.6Class 1, Type D
O1940.1Class 2, Type H
O2017.2Class 1, Type D
Compound II
Mg1O2918.9Class 1, Type D
O3040.7Class 1", Type J
O318.3Class 1, Type D
O3234.0Class 2, Type H
O337.0Class 1, Type D
O3460.0Class 2, Type H
Mg2O3539.2Class 2, Type H
O3626.3Class 1, Type D
O376.0Class 1, Type D
O388.9Class 1, Type D
O3933.0Class 2, Type H
O4013.4Class 1, Type D
Mg3O4125.1Class 1, Type D
O4212.6Class 1, Type D
O4318.6Class 1, Type D
O4427.5Class 1, Type D
O450.0Class 1, Type D
O4636.6Class 1", Type J
(a) Angle between the Mg—O bond and the plane defined by the water molecule. (b) Classification defined by Ferraris and Franchini-Angela (1972).
 

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