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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): i46–i47.
Published online 2009 May 23. doi:  10.1107/S1600536809019126
PMCID: PMC2969795

Sr5(VIVOF5)3F(H2O)3 refined from a non-merohedrally twinned crystal

Abstract

The title compound, penta­strontium tris­[penta­fluorido­oxido­vanadate(IV)] fluoride trihydrate, was obtained under hydro­thermal conditions. Its crystal structure has been refined from intensity data of a non-merohedrally twinned crystal. Two domains in almost equal proportions are related by a −180° rotation along the reciprocal [101]* vector. The structure may be considered as a derivative of the fluorite structure type, adopted here by SrF2. In the title compound, fluorite-like large rods are recognized, built up from a group of 16 Sr atoms of which 6 are substituted by V atoms, leading to [Sr10V6] units. These rods extend infinitely along the b axis and are inter­connected by the three water mol­ecules. Each of the water mol­ecules is shared by two different Sr atoms belonging to two different rods. The rods are also inter­connected by an ‘independent’ F atom in a distorted triangular [FSr3] coordination and by hydrogen-bonding inter­actions via donor water mol­ecules. The acceptors are either F atoms or the O atoms of the vanadyl ion, VO2+, that is part of the [VOF5] isolated octa­hedron.

Related literature

For VIV in [VOF5] coordination, see: Crosnier-Lopez et al. (1994 [triangle]). Sr2V2 IIIF10·H2O which was also synthesized during this study is isostructural with Sr2Fe2F10·H2O (Le Meins et al., 1997 [triangle]). For a description of similar ’independent’ F atoms in the crystal structure of Sr5Zr3F22, see: Le Bail (1996 [triangle]). For bond-valence analysis, see: Brown & Altermatt (1985 [triangle]); Brese & O’Keeffe (1991 [triangle]).

Experimental

Crystal data

  • Sr5(VOF5)3F(H2O)3
  • M r = 996.97
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-00i46-efi1.jpg
  • a = 11.217 (2) Å
  • b = 8.1775 (15) Å
  • c = 19.887 (4) Å
  • β = 105.999 (4)°
  • V = 1753.5 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 16.79 mm−1
  • T = 298 K
  • 0.36 × 0.08 × 0.04 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (TWINABS; Bruker, 2003 [triangle]) T min = 0.065, T max = 0.553 (expected range = 0.060–0.511)
  • 6596 measured reflections
  • 6596 independent reflections
  • 4299 reflections with I > 2σ(I)

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.083
  • S = 0.93
  • 6596 reflections
  • 290 parameters
  • 9 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 1.28 e Å−3
  • Δρmin = −1.11 e Å−3

Data collection: SMART (Bruker, 2003 [triangle]); cell refinement: SAINT (Bruker, 2003 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 1999 [triangle]) and ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)
Table 2
Valence-bond analysis of Sr5(VIVOF5)3F(H2O)3

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019126/wm2236sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019126/wm2236Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The title compound is the first hydrated strontium vanadium oxy-fluoride characterized crystallographically. It is built up from a network of SrOxFy polyhedra (x + y = 9 — 12), connected by faces, edges and vertices. Isolated (VIVOF5)3- octahedra with a short VIV═O bond (1.596 (4)—1.691 (4) Å) characteristic of a vanadyl ion, VO2+, (Crosnier-Lopez et al., 1994) are inserted into this network (Fig. 1). One of the fluorine atoms (F1) is shared exclusively by three strontium atoms (Sr1, Sr2, Sr3) in a triangular [FSr3] coordination, and will be named 'independent' according to previous descriptions (such a structure unit is also present in Sr5Zr3F22 (Le Bail, 1996); it shows the same A5B3X22 formula as the title compound). The three water molecules coordinate to these three (Sr1, Sr2, Sr3) strontium atoms, all of which have an overall ninefold coordination (Fig. 2), that is best described by a distorted tri-capped trigonal prism. The two remaining strontium atoms are exclusively coordinated by F atoms. The distorted [Sr(5)F12] cuboctahedron is connected to the [Sr(4)F11] polyhedra (best described as a defect cuboctahedron, lacking one vertex) by a square face (Fig. 3).

Any strong relation with the fluorite structure (adopted by SrF2) seems to be ruled out by the absence of F atoms in tetrahedral coordination [FSr4]. However, most F atoms are forming [FSr3V] distorted tetrahedra. One may consider that four strontium atoms (two Sr(4)F11 and two Sr(5)12 polyhedra sharing faces) represent a small fluorite structure relic around which half of the expected 12 Sr atoms are replaced by V atoms (forming [Sr10V6] blocks), which leads to the [FSr3V] distorted tetrahedra. Indeed, these blocks form infinite rods along the b axis, with formulation [Sr5V3]. The oxygen atoms of the six [VOF5] octahedra are part of the vanadyl VIV═O double bond and are all directed externally to these rods. This is well seen on the crystal structure projection (Fig. 4) where the water molecules are also placed in the rod interstices together with the F1 atom. Both types of ligands play a role in the interconnections between the rods. The relation of Sr5(VIVOF5)3F(H2O)3 with the SrF2 fluorite structure is provided in Fig. 5.

The hydrogen bonding involves both O and F atoms through Ow—H···O/F interactions (Table 1), participating in the interconnection of the [Sr10V6] rods. One of these hydrogen bonds is clearly bifurcated (O1—H11···O4/O5). The distinction between F and O atoms was evident from the valence bond analysis (Table 2) according to the empirical expression given by Brown & Altermatt (1985), using parameters from Brese & O'Keeffe (1991). The valence bond analysis allows also to recognize the water molecules. The short vanadium-oxygen bond is characteristic of a vanadyl VIV═O double bond.

Thermal analysis (TGA) measurement from selected crystals shows a mass loss starting close to 573 K, without any clear stop for the expected 3H2O release; the corresponding 5.42% mass loss is attained at 693 K, then the mass loss accelerates and attains 17% up to 873 K. The X-ray powder diffraction pattern of the final product is similar to fluorite-type SrF2, but the real composition is more probably corresponding to a fluorite solid solution with formula close to Sr5V3IIIO3F13, i.e. (Sr/V)(O/F)2 which may be topotactically rebuilt from the title compound arrangement by re-aligning the fluorite-like [Sr10V6] rods.

Experimental

Hydrothermal growth at 493 K from (SrF2/VF3) in HF 5M or 1M solutions produced mixtures of pale-blue-green needle-like crystals (dominant in 5M solution), accompanied with polycrystalline Sr2V2IIIF10.H2O (dominant in 1M solution). The latter compound is orthorhombic, with cell parameters a = 7.8653 (4) Å, b = 19.9298 (7) Å, c = 10.7322 (6) Å (from X-ray powder data), space group Cmca, and is isostructural with Sr2Fe2F10.H2O (Le Meins et al., 1997). All crystals of the title compound were found to be systematically affected by non-merohedral twinning (see Refinement section).

Refinement

From a first data collection on a conventional four-circle diffractometer, the structure could be solved in spite of the twinning, removing a lot of reflections that belong to two domains, or that were partly overlapping. However, the final data/parameter ratio was so poor that a second data collection was performed (years later), using a Bruker SMART APEX system.

24642 single reflections were attributed to domain 1 (4436 unique), 24601 to domain 2 (4416 unique), and there were 11156 overlapping reflections attributed to both domains.

The reflections were integrated and processed into a HKLF5 file used for the refinement. The final refinement was based on the data set of domain 1. The SHELXL BASF parameter refined to 0.511. A view of the reflection spots of domains 1 and 2 is shown in Fig. 6.

The H atoms were located in Fourier difference maps and their positions could be refined freely. Because of the large spread of O—H and H—H distances, they were finally refined applying soft constraints (0.90 (2) Å for O—H). Their thermal parameters were fixed at 1.2 times that of the corresponding water oxygen atom.

The distinction between F and O atoms was clear from the valence bond analysis, allowing also to recognize the water molecules. The short vanadium-oxygen bond is characteristic of a vanadyl VIV=O double bond.

In the final Fourier map the highest peak is 0.85 Å from atom Sr1 and the deepest hole is 0.82 Å from atom Sr2.

Figures

Fig. 1.
ORTEP-3 view of the [VIVOF5]3- octahedra showing the off-centered V position with short V=O distances (1.596–1.691 Å) and long opposite V—F distances (2.056–2.105 Å). Displacement ellipsoids are drawn at the 50% ...
Fig. 2.
ORTEP-3 view of the three SrX9 (X = F,O,H2O) tri-capped trigonal prisms, sharing the F1 atom and two of the three water molecules. This shows how three different fluorite-like [Sr10V6] infinite rods are mainly interconnected. Displacement ellipsoids are ...
Fig. 3.
ORTEP-3 view of the Sr(5)F12 cuboctahedron and Sr(4)F11 truncated cuboctahedron associated by a face. This situation is like in the fluorite-type structure of SrF2. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 4.
Crystal packing with view along [010] showing the isolated [VOF5] octahedra inside of fluorite-related [Sr10V6]∞ rods running along the b axis and delimited by the oxygen atoms of the vanadyl group, F1 atoms and the water molecules. Hydrogen bonds ...
Fig. 5.
Comparison between the [Sr10V6]∞ rods in the title compound (bottom) and the corresponding Sr16 block in the SrF2 fluorite-type structure (top), obtained by doubling its c axis and reversely replacing V by Sr atoms. The heights of the z coordinates ...
Fig. 6.
The two lattices of the two component crystal are visible. The SHELXL BASF parameter refines to 0.511 for this non-merohedral twin. The two domains are related by a rotation of -180° along the reciprocal [1 0 1]* vector.

Crystal data

Sr5(VOF5)3F(H2O)3F(000) = 1828
Mr = 996.97Dx = 3.776 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 323 reflections
a = 11.217 (2) Åθ = 2.0–30.0°
b = 8.1775 (15) ŵ = 16.79 mm1
c = 19.887 (4) ÅT = 298 K
β = 105.999 (4)°Needle, pale blue-green
V = 1753.5 (6) Å30.36 × 0.08 × 0.04 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer6596 independent reflections
Radiation source: normal-focus sealed tube4299 reflections with I > 2σ(I)
graphiteRint = 0.0000
Detector resolution: 8.366 pixels mm-1θmax = 30.0°, θmin = 1.9°
ω scansh = −15→15
Absorption correction: multi-scan (TWINABS; Bruker, 2003)k = 0→11
Tmin = 0.065, Tmax = 0.553l = 0→27
6596 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: difference Fourier map
wR(F2) = 0.083H atoms treated by a mixture of independent and constrained refinement
S = 0.93w = 1/[σ2(Fo2) + (0.0355P)2] where P = (Fo2 + 2Fc2)/3
6596 reflections(Δ/σ)max = 0.008
290 parametersΔρmax = 1.28 e Å3
9 restraintsΔρmin = −1.11 e Å3
0 constraints

Special details

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)

xyzUiso*/Ueq
Sr10.49725 (5)0.91553 (6)0.14704 (3)0.01037 (10)
Sr20.13869 (5)0.91614 (7)0.14686 (3)0.01133 (11)
Sr30.25819 (5)0.58877 (7)0.01760 (3)0.01119 (11)
Sr40.83170 (5)1.15579 (6)0.17512 (3)0.01218 (12)
Sr50.66417 (5)1.16611 (6)0.32847 (3)0.01202 (12)
V10.57273 (8)0.41800 (11)0.17307 (5)0.00985 (18)
V20.08398 (9)0.41537 (12)0.15922 (5)0.01143 (19)
V30.75847 (9)0.92212 (12)0.02341 (5)0.0121 (2)
F10.3050 (3)0.7747 (4)0.11547 (16)0.0152 (7)
F20.6850 (3)0.9235 (4)0.10740 (17)0.0184 (7)
F30.6078 (3)0.6508 (3)0.18699 (18)0.0162 (7)
F40.0792 (3)0.6462 (4)0.18369 (17)0.0151 (7)
F50.9049 (3)0.8968 (4)0.10573 (16)0.0148 (7)
F60.7705 (3)1.1521 (4)0.04540 (16)0.0171 (8)
F70.7368 (3)0.6882 (4)0.03245 (17)0.0199 (8)
F80.6052 (3)0.1825 (3)0.18916 (18)0.0176 (7)
F90.6924 (3)0.4171 (4)0.11824 (18)0.0201 (7)
F100.7406 (3)0.4169 (4)0.25298 (19)0.0279 (8)
F110.5154 (3)0.4220 (4)0.25564 (17)0.0219 (8)
F12−0.0364 (3)0.4062 (4)0.22370 (17)0.0157 (7)
F13−0.0774 (3)0.4719 (4)0.09201 (17)0.0186 (8)
F140.0383 (3)0.1884 (4)0.14929 (17)0.0169 (8)
F150.2141 (3)0.3756 (4)0.23846 (18)0.0249 (9)
F160.5983 (3)0.9396 (4)−0.03641 (17)0.0211 (8)
O10.3311 (4)1.1241 (5)0.1708 (2)0.0156 (9)
H110.314 (5)1.207 (5)0.1416 (19)0.019*
H120.339 (6)1.144 (6)0.2154 (11)0.019*
O20.4763 (4)0.7121 (5)0.0279 (2)0.0202 (9)
H210.482 (5)0.790 (5)−0.003 (2)0.024*
H220.547 (3)0.650 (6)0.038 (3)0.024*
O30.0503 (4)0.7198 (5)0.0304 (2)0.0201 (10)
H31−0.002 (4)0.653 (6)0.044 (3)0.024*
H320.012 (4)0.782 (6)−0.006 (2)0.024*
O40.4460 (4)0.4223 (5)0.1120 (2)0.0182 (9)
O50.1632 (4)0.4248 (5)0.0991 (2)0.0163 (9)
O60.8434 (4)0.9263 (5)−0.03483 (19)0.0145 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Sr10.0106 (3)0.0085 (2)0.0121 (3)−0.0001 (2)0.00308 (19)−0.0003 (2)
Sr20.0092 (3)0.0090 (2)0.0150 (3)0.0001 (2)0.0020 (2)0.0004 (2)
Sr30.0125 (3)0.0076 (2)0.0129 (3)−0.0005 (2)0.0026 (2)−0.0011 (2)
Sr40.0118 (3)0.0119 (3)0.0125 (3)−0.0007 (2)0.0029 (2)0.0001 (2)
Sr50.0119 (3)0.0112 (3)0.0129 (3)−0.0004 (2)0.0032 (2)−0.0001 (2)
V10.0104 (5)0.0067 (4)0.0117 (5)0.0003 (4)0.0019 (4)0.0005 (4)
V20.0095 (5)0.0078 (4)0.0166 (5)0.0005 (4)0.0030 (4)−0.0012 (4)
V30.0165 (5)0.0084 (4)0.0101 (5)0.0001 (4)0.0017 (4)0.0012 (4)
F10.0122 (17)0.0094 (17)0.0229 (18)−0.0031 (13)0.0030 (14)−0.0049 (14)
F20.0170 (19)0.0228 (18)0.0194 (18)−0.0064 (16)0.0119 (15)−0.0065 (16)
F30.0176 (19)0.0070 (14)0.023 (2)−0.0006 (13)0.0046 (15)−0.0006 (14)
F40.0139 (19)0.0122 (16)0.0189 (19)−0.0032 (14)0.0037 (15)−0.0027 (14)
F50.0097 (17)0.0175 (17)0.0132 (16)−0.0003 (14)−0.0037 (13)0.0020 (14)
F60.031 (2)0.0050 (15)0.0157 (18)0.0005 (15)0.0078 (16)0.0026 (13)
F70.028 (2)0.0085 (16)0.0213 (19)0.0012 (14)0.0038 (16)0.0002 (14)
F80.018 (2)0.0066 (15)0.026 (2)0.0014 (13)0.0024 (15)−0.0005 (14)
F90.0153 (18)0.0225 (18)0.0255 (19)−0.0043 (16)0.0105 (15)−0.0083 (17)
F100.0141 (19)0.037 (2)0.024 (2)0.0041 (18)−0.0099 (15)−0.0102 (18)
F110.026 (2)0.0264 (19)0.0156 (18)−0.0051 (17)0.0094 (15)−0.0014 (16)
F120.0193 (19)0.0149 (16)0.0160 (17)−0.0017 (15)0.0100 (14)0.0001 (15)
F130.0116 (19)0.0253 (19)0.0156 (18)0.0044 (15)−0.0017 (15)−0.0046 (15)
F140.017 (2)0.0093 (16)0.027 (2)−0.0020 (14)0.0101 (16)−0.0010 (14)
F150.025 (2)0.025 (2)0.020 (2)0.0053 (16)−0.0027 (17)−0.0023 (15)
F160.021 (2)0.021 (2)0.0180 (18)−0.0017 (15)0.0009 (15)0.0003 (15)
O10.017 (2)0.016 (2)0.013 (2)−0.0004 (17)0.0042 (18)0.0000 (16)
O20.014 (2)0.022 (2)0.023 (2)−0.0010 (18)0.0036 (19)0.0018 (19)
O30.017 (2)0.019 (3)0.023 (2)0.0015 (18)0.0039 (19)0.0065 (19)
O40.016 (2)0.017 (2)0.018 (2)0.0031 (19)−0.0015 (17)0.0026 (18)
O50.016 (2)0.013 (2)0.022 (2)−0.0003 (18)0.0098 (18)0.0031 (18)
O60.019 (2)0.013 (2)0.014 (2)0.0074 (18)0.0085 (17)0.0023 (17)

Geometric parameters (Å, °)

V1—O41.596 (4)Sr2—O32.768 (4)
V1—F111.921 (3)Sr2—F11ii2.932 (3)
V1—F91.949 (3)Sr3—F12.411 (3)
V1—F31.948 (3)Sr3—F6i2.438 (3)
V1—F81.970 (3)Sr3—F7vi2.481 (3)
V1—F102.103 (3)Sr3—O52.552 (4)
V2—O51.676 (4)Sr3—F13vii2.583 (3)
V2—F151.858 (4)Sr3—O22.602 (4)
V2—F141.921 (3)Sr3—O32.642 (4)
V2—F41.954 (3)Sr3—O42.763 (4)
V2—F131.986 (3)Sr3—F9vi2.904 (3)
V2—F122.105 (3)Sr4—F62.480 (3)
V3—O61.691 (4)Sr4—F14viii2.522 (3)
V3—F161.867 (4)Sr4—F12viii2.554 (3)
V3—F61.927 (3)Sr4—F22.629 (3)
V3—F71.943 (3)Sr4—F3iv2.637 (3)
V3—F51.985 (3)Sr4—F8iii2.640 (3)
V3—F22.056 (3)Sr4—F10iv2.676 (4)
Sr1—F12.372 (3)Sr4—F11iv2.681 (3)
Sr1—F22.444 (3)Sr4—F9iii2.704 (4)
Sr1—F16i2.468 (3)Sr4—F52.773 (3)
Sr1—F12ii2.487 (3)Sr4—F10iii2.978 (4)
Sr1—F32.513 (3)Sr5—F5iv2.536 (3)
Sr1—F8iii2.525 (3)Sr5—F13ii2.611 (3)
Sr1—O12.663 (4)Sr5—F12ii2.613 (3)
Sr1—O22.851 (4)Sr5—F9iv2.630 (3)
Sr1—F10iv3.062 (3)Sr5—F3iv2.662 (3)
Sr2—F12.418 (3)Sr5—F8iii2.668 (4)
Sr2—F15ii2.441 (3)Sr5—F4ii2.678 (3)
Sr2—F42.475 (3)Sr5—F7iv2.688 (3)
Sr2—F14iii2.501 (3)Sr5—F2iv2.780 (4)
Sr2—F5v2.527 (3)Sr5—F10iii2.811 (4)
Sr2—O6i2.629 (4)Sr5—F11iii2.816 (4)
Sr2—O12.685 (4)Sr5—F10iv2.978 (4)
O4—V1—F11102.29 (18)F4—V2—F1381.95 (14)
O4—V1—F9100.39 (18)O5—V2—F12172.52 (17)
F11—V1—F9157.28 (15)F15—V2—F1287.89 (15)
O4—V1—F3100.91 (18)F14—V2—F1280.22 (13)
F11—V1—F387.93 (15)F4—V2—F1279.42 (13)
F9—V1—F386.56 (15)F13—V2—F1278.43 (13)
O4—V1—F8103.38 (18)O6—V3—F16100.78 (18)
F11—V1—F888.19 (15)O6—V3—F696.80 (17)
F9—V1—F887.82 (15)F16—V3—F693.72 (15)
F3—V1—F8155.68 (13)O6—V3—F7101.05 (17)
O4—V1—F10178.88 (19)F16—V3—F790.65 (15)
F11—V1—F1078.18 (15)F6—V3—F7160.49 (14)
F9—V1—F1079.12 (15)O6—V3—F594.15 (16)
F3—V1—F1078.06 (14)F16—V3—F5165.02 (15)
F8—V1—F1077.64 (14)F6—V3—F585.67 (14)
O5—V2—F1599.56 (18)F7—V3—F585.24 (14)
O5—V2—F1498.63 (17)O6—V3—F2169.75 (17)
F15—V2—F1492.46 (15)F16—V3—F289.22 (15)
O5—V2—F4100.93 (17)F6—V3—F280.15 (14)
F15—V2—F491.55 (15)F7—V3—F280.90 (14)
F14—V2—F4159.08 (14)F5—V3—F275.92 (14)
O5—V2—F1394.19 (17)H11—O1—H12118 (3)
F15—V2—F13165.70 (15)H21—O2—H22109 (3)
F14—V2—F1389.31 (15)H31—O3—H32113 (3)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H11···O4iii0.88 (4)2.48 (5)3.131 (6)132 (5)
O1—H11···O5iii0.88 (4)2.44 (4)3.185 (6)143 (5)
O1—H12···F4ii0.88 (2)1.96 (3)2.796 (5)157 (5)
O2—H21···F160.90 (4)2.03 (4)2.817 (5)146 (5)
O2—H22···F70.92 (4)2.18 (4)2.905 (5)135 (4)
O3—H31···F130.90 (5)2.07 (5)2.937 (5)164 (5)
O3—H32···O6v0.89 (4)2.17 (4)2.873 (5)135 (5)

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

Table 2 Valence-bond analysis of Sr5(VIVOF5)3F(H2O)3

V1V2V3Sr1Sr2Sr3Sr4Sr5ΣΣexpected
F10.380.340.351.071
F20.380.320.190.131.021
F30.510.260.190.181.141
F40.500.290.170.961
F50.460.250.130.251.091
F60.540.320.291.151
F70.520.290.160.971
F80.480.250.190.171.091
F90.510.090.160.190.951
F100.340.060.17;0.070.12;0.070.831
F110.550.080.170.120.921
F120.340.280.230.201.051
F130.460.220.200.881
F140.550.270.261.081
F150.650.320.971
F160.640.300.941
O10.220.212.03*2
O20.140.272.01*2
O30.170.242.01*2
O41.660.171.832
O51.340.311.652
O61.290.251.542
Σ4.053.843.832.212.182.262.051.94
Σexpected44422222

Note: (*) adding a bond valence of 1.6 units, corresponding to the two H atoms linked to O1, O2 and O3, forming water molecules. The valence deficit observed on O4, O5 and O6, as well as on F4, F7, F13 and F16, is expected to be compensated by hydrogen bonding, since they behave as acceptors.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2236).

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