A non-oxo methano­late-bridged divanadium(IV) complex with tris(2-sulfanidylphenyl)phosphane ligands: synthesis, structural characterization and magnetic investigation

Vanadium chemistry is of interest due its biological relevance and medical applications. In particular, the inter­actions of high-valent vanadium ions with sulfur-containing biologically important mol­ecules, such as cysteine and gluta­thione, might be related to the redox conversion of vanadium in ascidians, the function of amavadin (a vanadium-containing anion) and the anti­diabetic behaviour of vanadium compounds. A mechanistic understanding of these aspects is important. In an effort to investigate high-valent vanadium-sulfur chemistry, we have synthesized and characterized the non-oxo divanadium(IV) complex salt tetra­phenyl­phospho­nium tri-[mu]-methano­l­ato-[kappa]⁶O:O-bis­({tris[2-sul­fani­dyl-3-(trimethylsilyl)phenyl]phosphane-[kappa]⁴P,S,S',S''}vanadium(IV)) methanol disolvate, (C₂₄H₂₀P)[V^IV₂([mu]-OCH₃)₃(C₂₇H₃₆PS₃)₂]·2CH₃OH. Two V^IV metal centres are bridged by three methano­late ligands, giving a C2-symmetric V₂([mu]-OMe)₃ core structure. Each V^IV centre adopts a monocapped trigonal anti­­prismatic geometry, with the P atom situated in the capping position and the three S atoms and three O atoms forming two triangular faces of the trigonal anti­prism. The magnetic data indicate a paramagnetic nature of the salt, with an S = 1 spin state.

S1. Introduction

Vanadium chemistry has attracted much attention due its biological relevance and medical applications (Crans et al., 2004). In particular, the inter­actions of high-valent vanadium ions with the S-atom donors of biologically important molecules, such as cysteine and gluta­thione, might be related to the redox conversion of vanadium in ascidians (Michibata et al., 2003), the function of amavadin (a vanadium-containing anion) isolated from Amanita mushrooms (Garner et al., 2000) and the anti­diabetic behaviour of vanadium compounds (Rehder, 2003). To provide a mechanistic understanding for these aspects, the fundamental study of high-valent vanadium sulfur chemistry has been emphasized (Chang et al., 2011; Crans et al., 2010). High-valent vanadium ions are oxophilic and thus reported V^IV and V^V complexes mostly contain VO³⁺ and VO²⁺ units. In comparison, non-oxide high-valent vanadium complexes are relatively scarce (Hsu et al., 2006). The chemistry of non-oxide high-valent vanadium complexes has been of inter­est and has been investigated in our laboratory. We have utilized a tris­(2-sulfanidyl­phenyl)­phosphane ligand system to obtain a class of non-oxide divanadium complexes containing chalcogenide bridges (Wu et al., 2015). In a continuation of this research, a non-oxide divanadium(IV) complex with methano­late bridges has been synthesized and characterized at this work, namely tetra­phenyl­phospho­nium tri-µ-methano­lato-bis­({tris­[2-sulfanidyl-3-(tri­methyl­silyl)phenyl]­phosphane}vanadium(IV)) methanol disolvate, (Ph₄P)[V₂(MeO)₃(PS3'')₂].2MeOH, (I). To the best of our knowledge, several examples of divanadium(IV) and divanadium(V) complexes with bis­(alkoxide) bridges have been reported (Westrup et al., 2011; Scales et al., 2010; Romero-Fernandez et al., 2010; Nishina et al., 2010; Arbaoui et al., 2009; Zhang & Nomura, 2008; Lorber et al., 2008; Homden et al., 2008; Nunes et al., 2005; Preuss, Vogel et al., 2001; Preuss, Fischbeck et al., 2001; Lutz et al., 1999; Castellano et al., 1999; Kempe & Spannenberg, 1997; Devore et al., 1987), but a tris­(alkoxide) divanadium core structure is unprecedented in the literature.

S2. Experimental

S2.1. General considerations

All operations were carried out under an N₂ atmosphere using standard Schlenk and glove-box techniques. Solvents were dried and distilled under N₂ prior to use. The basic synthetic procedure was carried out according to our previous work. The PS3'' ligand, i.e. [P(C₆H₃-3-Me₃Si-2-S)₃]^3- (Block et al., 1989), and VO(i-PrO)₃ (Cornman et al., 1998) were synthesized according to literature methods. Electronic spectra were recorded at the range 300–1100 nm on a Hewlett Packard 8453 spectrophotometer. Elemental analyses were performed at the National Cheng Kung University with an Elemetar vario EL III. The electrospray ionization (ESI) mass spectrum was recorded at the Instrument Development Center of the National Cheng Kung University with a LTQ Orbitrap XL Thermo Fisher spectrometer. The NMR spectrum was recorded on a Bruker AMX400. The magnetization data was recorded on a SQUID magnetometer (Quantum Design MPMS SQUID VSM System) with an external 1 Tesla magnetic field for complex (I) over the temperature range 1.8 to 300 K.

S2.2. Synthesis and crystallization

H₃PS3'' (0.100 g, 0.174 mmol) and NaOCH₃ (0.029 g, 0.537 mmol) were dissolved in methanol. The solution was added to an iso­propanol solution of VO(i-PrO)₃ (0.043 g, 0.174 mmol). The resulting green solution was layered with (PPh₄)Br (0.073 g, 0.174 mmol) in methanol to give a green crystalline solid of (I) after one week [yield 0.044 g, 0.026 mmol, ca 30.0% based on VO(i-PrO)₃]. Calculated for C₈₁H₁₀₁O₃P₃S₆Si₆V₂: C 57.96, H 6.07, S 11.46%; found: C 57.44, H 5.97, S 11.31%. ¹H NMR: δ 7.96, 7.74, 7.50 (PPh₄⁺); 3.32 (µ-OCH₃); -0.43, -0.58 [P(C₆H₃-3-Me₃Si-2-S)₃]; -18.16, 9.6 [P(C₆H₃-3-Me₃Si-2-S]₃. UV–Vis–NIR [CH₂Cl₂, λ_max (ε, M^-1 cm^-1)]: 598 (5.2 × 10³), 846 (3.2 × 10³), 997(2.7 × 10³). Molecular mass (m/z) calculated: 1337.15; found: 1337.13 [M]^-1. (Fig. 1).

S2.3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. A green needle-shape crystal of (I) was mounted under liquid-nitro­gen vapour on a fine glass fibre with glue. All H atoms are included using the riding model. All other H atoms were placed in ideal positions, with C—H = 0.95 Å for aromatic groups or 0.98 Å for methyl groups, and refined using a riding model, with U_iso(H) = 1.2 or 1.5U_eq(C), respectively. Atoms S3, C9 and C29 are highly distorted and partial occupancies were used for their refinement; the assigned occupancies for S3/S3', C9/C9' and C29/C29' were 0.574 (6):0.426 (6), 0.574 (6):0.426 (6) and 0.5:0.5, respectively.

S3. Results and discussion

The anion of (I) consists of dinuclear V^IV centres bridging by three methano­late groups (Fig. 2). The crystallographic C₂ axis sits on one of bridging the O atoms (O2). Each V^IV centre adopts a distorted monocapped trigonal anti­prismatic geometry, where three S-atom donors of the PS3'' ligand and three bridging methano­late ligands form two triangular faces. The P atom of the PS3'' ligand is located on top of the triangular face formed by three S atoms. The average twist angle (φ) of two triangular faces is 54.13° (Fig. 3) (trigonal prism = 0°; trigonal anti­prism and o­cta­hedron = 60°) (Muetterties & Guggenberger, 1974; Karpishin et al., 1993). The S1—V1—O1, S2—V1—O2 and S3—V1—O1 angles (Table 2) are much smaller from those in an ideal o­cta­hedron (the axis angle is 180°), but closer to those in a trigonal anti­prism (Notni et al., 2009). The bond lengths of compound (I) are very similar to those in previously reported non-oxide divanadium complexes, [V₂(µ-E)(µ-η²:η²-E₂)(PS3)₂]ⁿ (E = S or Se, n = 0 or 2-, and PS3 indicates a PS3'' derivative) (Wu et al., 2015). The V···V separation in (I) is 2.899 (2) Å, which is similar to the values seen in [V₂(µ-E)(µ-η²:η²-E₂)(PS3)₂]ⁿ complexes (2.90–3.08 Å). The average V—S bond length in (I) is 2.426 Å, which is also close to those of [V₂(µ-E)(µ-η²:η²-E₂)(PS3)₂]ⁿ complexes. The three V—OCH₃ bond lengths are in the range 1.999 (4)–2.027 (4) Å (Table 2).

Complex (I) is not stable under aerobic conditions. It decomposes immediately in solution under exposure to the air. When dissolved in di­chloro­methane, the complex produced a green solution. The UV–Vis–NIR spectrum (NIR is near infrared) displays three intense peaks at 598 (ε = 5.2 × 10³ M^-1 cm^-1), 846 (ε = 3.2 × 10³ M^-1 cm^-1) and 997 nm (ε = 2.7 × 10³ M^-1 cm^-1) (see Fig. S1 in the Supporting information). The absorption bands with the high molar extinction coefficients are likely associated with strong ligand-to-metal charge transfer bands (LMCT) that mask d–d transitions. The ¹H NMR spectrum of (I) in DMSO-d₆ exhibits resonances between 9.5 and -18.16 p.p.m., indicating a paramagnetic character of the divanadium(IV) centres (see Fig. S2 in the Supporting information). The SQUID data for (I) shows the nature of paramagnetism (Fig. 4). The spin-only effective magnetic moment is 2.51 µ_B at 2 K and 2.80 µ_B per dimer at 300 K, which are consistent with the spin-only value (2.83 µ_B) for an S = 1 (triplet) system. The nature of the paramagnetism between two V^IV centres is also seen in two non-oxide divanadium(IV) complexes, [(µ-O)₂V₂{N(SiMe₃)₂}₄] (Duan et al., 1996) and [{(C₆F₅NCH₂CH₂)₂N(CH₂CH₂NHC₆F₅)}V(O)]₂ [these seem to contain oxide?] (Rosenberger et al., 1997), that both contain V₂O₂ cores. The V···V separations for these two V₂O₂ complexes are 2.612 and 3.100 Å, respectively. A theoretical method is needed to elucidate the magnetic properties resulting from the orbital inter­action in (I).

In summary, a non-oxide divanadium(IV) complex supported by a tris­[2-sulfanidyl-3-(tri­methyl­silyl)phenyl]­phosphane ligand has been synthesized and structurally characterized. Two V^IV centres are bridged by three methano­late groups, forming a [V^IV₂(µ-OMe)₃] core motif that is unprecedented in the literature. Each V^IV centre adopts a monocapped trigonal anti­prismatic geometry. Inter­estingly, complex (I) shows a paramagnetic nature and the magnetic data are consistent with an S = 1 system. The details of this chemistry and theoretical work is currently under investigation at our laboratory.

Structure description

Vanadium chemistry has attracted much attention due its biological relevance and medical applications (Crans et al., 2004). In particular, the inter­actions of high-valent vanadium ions with the S-atom donors of biologically important molecules, such as cysteine and gluta­thione, might be related to the redox conversion of vanadium in ascidians (Michibata et al., 2003), the function of amavadin (a vanadium-containing anion) isolated from Amanita mushrooms (Garner et al., 2000) and the anti­diabetic behaviour of vanadium compounds (Rehder, 2003). To provide a mechanistic understanding for these aspects, the fundamental study of high-valent vanadium sulfur chemistry has been emphasized (Chang et al., 2011; Crans et al., 2010). High-valent vanadium ions are oxophilic and thus reported V^IV and V^V complexes mostly contain VO³⁺ and VO²⁺ units. In comparison, non-oxide high-valent vanadium complexes are relatively scarce (Hsu et al., 2006). The chemistry of non-oxide high-valent vanadium complexes has been of inter­est and has been investigated in our laboratory. We have utilized a tris­(2-sulfanidyl­phenyl)­phosphane ligand system to obtain a class of non-oxide divanadium complexes containing chalcogenide bridges (Wu et al., 2015). In a continuation of this research, a non-oxide divanadium(IV) complex with methano­late bridges has been synthesized and characterized at this work, namely tetra­phenyl­phospho­nium tri-µ-methano­lato-bis­({tris­[2-sulfanidyl-3-(tri­methyl­silyl)phenyl]­phosphane}vanadium(IV)) methanol disolvate, (Ph₄P)[V₂(MeO)₃(PS3'')₂].2MeOH, (I). To the best of our knowledge, several examples of divanadium(IV) and divanadium(V) complexes with bis­(alkoxide) bridges have been reported (Westrup et al., 2011; Scales et al., 2010; Romero-Fernandez et al., 2010; Nishina et al., 2010; Arbaoui et al., 2009; Zhang & Nomura, 2008; Lorber et al., 2008; Homden et al., 2008; Nunes et al., 2005; Preuss, Vogel et al., 2001; Preuss, Fischbeck et al., 2001; Lutz et al., 1999; Castellano et al., 1999; Kempe & Spannenberg, 1997; Devore et al., 1987), but a tris­(alkoxide) divanadium core structure is unprecedented in the literature.

All operations were carried out under an N₂ atmosphere using standard Schlenk and glove-box techniques. Solvents were dried and distilled under N₂ prior to use. The basic synthetic procedure was carried out according to our previous work. The PS3'' ligand, i.e. [P(C₆H₃-3-Me₃Si-2-S)₃]^3- (Block et al., 1989), and VO(i-PrO)₃ (Cornman et al., 1998) were synthesized according to literature methods. Electronic spectra were recorded at the range 300–1100 nm on a Hewlett Packard 8453 spectrophotometer. Elemental analyses were performed at the National Cheng Kung University with an Elemetar vario EL III. The electrospray ionization (ESI) mass spectrum was recorded at the Instrument Development Center of the National Cheng Kung University with a LTQ Orbitrap XL Thermo Fisher spectrometer. The NMR spectrum was recorded on a Bruker AMX400. The magnetization data was recorded on a SQUID magnetometer (Quantum Design MPMS SQUID VSM System) with an external 1 Tesla magnetic field for complex (I) over the temperature range 1.8 to 300 K.

The anion of (I) consists of dinuclear V^IV centres bridging by three methano­late groups (Fig. 2). The crystallographic C₂ axis sits on one of bridging the O atoms (O2). Each V^IV centre adopts a distorted monocapped trigonal anti­prismatic geometry, where three S-atom donors of the PS3'' ligand and three bridging methano­late ligands form two triangular faces. The P atom of the PS3'' ligand is located on top of the triangular face formed by three S atoms. The average twist angle (φ) of two triangular faces is 54.13° (Fig. 3) (trigonal prism = 0°; trigonal anti­prism and o­cta­hedron = 60°) (Muetterties & Guggenberger, 1974; Karpishin et al., 1993). The S1—V1—O1, S2—V1—O2 and S3—V1—O1 angles (Table 2) are much smaller from those in an ideal o­cta­hedron (the axis angle is 180°), but closer to those in a trigonal anti­prism (Notni et al., 2009). The bond lengths of compound (I) are very similar to those in previously reported non-oxide divanadium complexes, [V₂(µ-E)(µ-η²:η²-E₂)(PS3)₂]ⁿ (E = S or Se, n = 0 or 2-, and PS3 indicates a PS3'' derivative) (Wu et al., 2015). The V···V separation in (I) is 2.899 (2) Å, which is similar to the values seen in [V₂(µ-E)(µ-η²:η²-E₂)(PS3)₂]ⁿ complexes (2.90–3.08 Å). The average V—S bond length in (I) is 2.426 Å, which is also close to those of [V₂(µ-E)(µ-η²:η²-E₂)(PS3)₂]ⁿ complexes. The three V—OCH₃ bond lengths are in the range 1.999 (4)–2.027 (4) Å (Table 2).

Complex (I) is not stable under aerobic conditions. It decomposes immediately in solution under exposure to the air. When dissolved in di­chloro­methane, the complex produced a green solution. The UV–Vis–NIR spectrum (NIR is near infrared) displays three intense peaks at 598 (ε = 5.2 × 10³ M^-1 cm^-1), 846 (ε = 3.2 × 10³ M^-1 cm^-1) and 997 nm (ε = 2.7 × 10³ M^-1 cm^-1) (see Fig. S1 in the Supporting information). The absorption bands with the high molar extinction coefficients are likely associated with strong ligand-to-metal charge transfer bands (LMCT) that mask d–d transitions. The ¹H NMR spectrum of (I) in DMSO-d₆ exhibits resonances between 9.5 and -18.16 p.p.m., indicating a paramagnetic character of the divanadium(IV) centres (see Fig. S2 in the Supporting information). The SQUID data for (I) shows the nature of paramagnetism (Fig. 4). The spin-only effective magnetic moment is 2.51 µ_B at 2 K and 2.80 µ_B per dimer at 300 K, which are consistent with the spin-only value (2.83 µ_B) for an S = 1 (triplet) system. The nature of the paramagnetism between two V^IV centres is also seen in two non-oxide divanadium(IV) complexes, [(µ-O)₂V₂{N(SiMe₃)₂}₄] (Duan et al., 1996) and [{(C₆F₅NCH₂CH₂)₂N(CH₂CH₂NHC₆F₅)}V(O)]₂ [these seem to contain oxide?] (Rosenberger et al., 1997), that both contain V₂O₂ cores. The V···V separations for these two V₂O₂ complexes are 2.612 and 3.100 Å, respectively. A theoretical method is needed to elucidate the magnetic properties resulting from the orbital inter­action in (I).

In summary, a non-oxide divanadium(IV) complex supported by a tris­[2-sulfanidyl-3-(tri­methyl­silyl)phenyl]­phosphane ligand has been synthesized and structurally characterized. Two V^IV centres are bridged by three methano­late groups, forming a [V^IV₂(µ-OMe)₃] core motif that is unprecedented in the literature. Each V^IV centre adopts a monocapped trigonal anti­prismatic geometry. Inter­estingly, complex (I) shows a paramagnetic nature and the magnetic data are consistent with an S = 1 system. The details of this chemistry and theoretical work is currently under investigation at our laboratory.

Synthesis and crystallization

H₃PS3'' (0.100 g, 0.174 mmol) and NaOCH₃ (0.029 g, 0.537 mmol) were dissolved in methanol. The solution was added to an iso­propanol solution of VO(i-PrO)₃ (0.043 g, 0.174 mmol). The resulting green solution was layered with (PPh₄)Br (0.073 g, 0.174 mmol) in methanol to give a green crystalline solid of (I) after one week [yield 0.044 g, 0.026 mmol, ca 30.0% based on VO(i-PrO)₃]. Calculated for C₈₁H₁₀₁O₃P₃S₆Si₆V₂: C 57.96, H 6.07, S 11.46%; found: C 57.44, H 5.97, S 11.31%. ¹H NMR: δ 7.96, 7.74, 7.50 (PPh₄⁺); 3.32 (µ-OCH₃); -0.43, -0.58 [P(C₆H₃-3-Me₃Si-2-S)₃]; -18.16, 9.6 [P(C₆H₃-3-Me₃Si-2-S]₃. UV–Vis–NIR [CH₂Cl₂, λ_max (ε, M^-1 cm^-1)]: 598 (5.2 × 10³), 846 (3.2 × 10³), 997(2.7 × 10³). Molecular mass (m/z) calculated: 1337.15; found: 1337.13 [M]^-1. (Fig. 1).

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. A green needle-shape crystal of (I) was mounted under liquid-nitro­gen vapour on a fine glass fibre with glue. All H atoms are included using the riding model. All other H atoms were placed in ideal positions, with C—H = 0.95 Å for aromatic groups or 0.98 Å for methyl groups, and refined using a riding model, with U_iso(H) = 1.2 or 1.5U_eq(C), respectively. Atoms S3, C9 and C29 are highly distorted and partial occupancies were used for their refinement; the assigned occupancies for S3/S3', C9/C9' and C29/C29' were 0.574 (6):0.426 (6), 0.574 (6):0.426 (6) and 0.5:0.5, respectively.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The ESI–MS diagram of the [V^IV2(µ-OMe)3(PS3'')2]^- anion. The molecular ion peaks display isotopic distribution at 1337.13 m/z (top), consistent with the calculated pattern of C57H81O3P2S6Si6V2 formulation (bottom).
	Fig. 2. The molecular structure of the [V^IV2(µ-OMe)3(PS3'')2]^- anion shown with 35% probability displacement ellipsoids. The H atoms and tetraphenylphosphonium cation have been omitted for clarity. Only the major-occupied sites of the disordered S3, C29 and C9 atoms are shown (see Section 2.3 for details). [Please provide a plot with the asymmetric unit fully labelled]
	Fig. 3. Definition of the trigonal twist angle (φ) and the twist angle in (I). [Please provide a revised plot with the labels not overlapping atoms or bonds]
	Fig. 4. The temperature dependence of the magnetic susceptibility of (I) at 1 Tesla, in the forms of χM (black dot) and µeff (blue dot).

Tetraphenylphosphonium tri-µ-methanolato-κ⁶O:O-bis({tris[2-sulfanidyl-3-(trimethylsilyl)phenyl]phosphane-κ⁴P,S,S',S''}vanadium(IV)) methanol disolvate

Crystal data

(C24H20P)[V2(CH3O)3(C27H36PS3)2]·2CH4O	F(000) = 3672
Mr = 1742.39	Dx = 1.290 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1430 reflections
a = 18.4740 (12) Å	θ = 2.2–18.6°
b = 25.4633 (18) Å	µ = 0.53 mm^−1
c = 19.3663 (13) Å	T = 150 K
β = 100.036 (2)°	Needle, dark-green
V = 8970.7 (11) Å^3	0.55 × 0.07 × 0.05 mm
Z = 4

Data collection

BRUKER SMART APEXCCD area detector diffractometer	7880 independent reflections
Radiation source: fine-focus sealed tube	5218 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.100
ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −19→21
Tmin = 0.760, Tmax = 0.974	k = −30→30
20475 measured reflections	l = −21→23

Refinement

Refinement on F^2	8 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.088	H-atom parameters constrained
wR(F^2) = 0.191	w = 1/[σ^2(Fo^2) + (0.0653P)^2 + 20.3783P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
7880 reflections	Δρmax = 0.81 e Å^−3
494 parameters	Δρmin = −0.47 e Å^−3

Special details

Experimental. A green needle-shape crystal of (I) was mounted under liquid-nitrogen vapor on a fine glass fiber with glue. Data were collected at 150 (2) K by a Nonius Kappa diffractometer equipped with a CCD detector. Least-squares refinement of the positional and anisotropic thermal parameters for the contribution of all non-hydrogen atoms and fixed hydrogen atoms was based on F². A SADABS absorption correction was made. The SHELXTL structural refinement program was employed. All the non-hydrogen atoms were refined with anisotropic displacement factors.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
V1	0.51582 (6)	0.28696 (4)	0.17927 (5)	0.0268 (3)
S1	0.41938 (10)	0.33631 (6)	0.10672 (9)	0.0349 (4)
S2	0.51154 (10)	0.19719 (6)	0.13735 (10)	0.0371 (5)
S3	0.6450 (3)	0.3206 (2)	0.1860 (3)	0.0303 (9)	0.547 (5)
S3'	0.6224 (4)	0.3396 (2)	0.1889 (3)	0.0303 (9)	0.453 (5)
P1	0.54546 (8)	0.28845 (6)	0.06435 (8)	0.0209 (4)
Si1	0.26051 (11)	0.36565 (8)	−0.01132 (13)	0.0480 (6)
Si2	0.58025 (10)	0.07536 (7)	0.11356 (11)	0.0351 (5)
Si3	0.76105 (11)	0.42678 (8)	0.18738 (11)	0.0422 (5)
O1	0.4351 (2)	0.25952 (15)	0.2283 (2)	0.0301 (10)
O2	0.5000	0.3411 (2)	0.2500	0.0320 (15)
C1	0.4076 (3)	0.3172 (2)	0.0179 (3)	0.0262 (14)
C2	0.4648 (3)	0.2896 (2)	−0.0030 (3)	0.0218 (13)
C3	0.4583 (3)	0.2679 (2)	−0.0697 (3)	0.0263 (14)
H3	0.4977	0.2485	−0.0827	0.032*
C4	0.3933 (3)	0.2749 (2)	−0.1167 (3)	0.0300 (15)
H4	0.3871	0.2593	−0.1619	0.036*
C5	0.3371 (3)	0.3050 (2)	−0.0971 (3)	0.0314 (15)
H5	0.2936	0.3107	−0.1305	0.038*
C6	0.3421 (3)	0.3271 (2)	−0.0307 (4)	0.0328 (16)
C7	0.2129 (5)	0.3917 (3)	−0.0988 (5)	0.068 (3)
H7A	0.1763	0.4180	−0.0914	0.102*
H7B	0.1884	0.3627	−0.1270	0.102*
H7C	0.2492	0.4079	−0.1235	0.102*
C8	0.2847 (4)	0.4245 (3)	0.0445 (4)	0.055 (2)
H8A	0.3037	0.4135	0.0928	0.082*
H8B	0.2408	0.4463	0.0438	0.082*
H8C	0.3224	0.4449	0.0265	0.082*
C9	0.1923 (17)	0.3197 (13)	0.0138 (12)	0.069 (7)	0.547 (5)
H9A	0.1829	0.2914	−0.0208	0.104*	0.547 (5)
H9B	0.1464	0.3386	0.0155	0.104*	0.547 (5)
H9C	0.2113	0.3049	0.0601	0.104*	0.547 (5)
C9'	0.210 (2)	0.3246 (16)	0.0476 (16)	0.069 (7)	0.453 (5)
H9'A	0.2405	0.3211	0.0940	0.104*	0.453 (5)
H9'B	0.1994	0.2897	0.0268	0.104*	0.453 (5)
H9'C	0.1636	0.3420	0.0521	0.104*	0.453 (5)
C10	0.5769 (3)	0.1872 (2)	0.0819 (3)	0.0243 (14)
C11	0.5984 (3)	0.2316 (2)	0.0483 (3)	0.0233 (14)
C12	0.6503 (3)	0.2287 (2)	0.0056 (3)	0.0255 (14)
H12	0.6641	0.2592	−0.0172	0.031*
C13	0.6821 (3)	0.1805 (2)	−0.0038 (3)	0.0283 (15)
H13	0.7188	0.1777	−0.0325	0.034*
C14	0.6601 (3)	0.1369 (2)	0.0288 (3)	0.0287 (15)
H14	0.6822	0.1042	0.0212	0.034*
C15	0.6074 (3)	0.1377 (2)	0.0723 (3)	0.0234 (13)
C16	0.6377 (4)	0.0210 (3)	0.0881 (4)	0.051 (2)
H16A	0.6894	0.0273	0.1083	0.077*
H16B	0.6321	0.0195	0.0369	0.077*
H16C	0.6219	−0.0124	0.1058	0.077*
C17	0.4823 (4)	0.0607 (3)	0.0785 (5)	0.068 (3)
H17A	0.4780	0.0460	0.0311	0.102*
H17B	0.4534	0.0930	0.0767	0.102*
H17C	0.4638	0.0351	0.1090	0.102*
C18	0.5958 (5)	0.0790 (3)	0.2109 (4)	0.067 (3)
H18A	0.5714	0.0492	0.2294	0.101*
H18B	0.5754	0.1119	0.2254	0.101*
H18C	0.6486	0.0777	0.2292	0.101*
C19	0.6456 (3)	0.3606 (2)	0.1092 (3)	0.0289 (15)
C20	0.5995 (3)	0.3443 (2)	0.0483 (3)	0.0227 (14)
C21	0.6019 (3)	0.3680 (2)	−0.0157 (3)	0.0300 (15)
H21	0.5708	0.3562	−0.0571	0.036*
C22	0.6508 (3)	0.4093 (2)	−0.0183 (4)	0.0315 (16)
H22	0.6521	0.4268	−0.0613	0.038*
C23	0.6973 (3)	0.4245 (2)	0.0420 (4)	0.0313 (16)
H23	0.7314	0.4519	0.0388	0.038*
C24	0.6968 (3)	0.4018 (2)	0.1073 (3)	0.0282 (15)
C25	0.8353 (5)	0.4642 (3)	0.1554 (5)	0.071 (3)
H25A	0.8765	0.4694	0.1941	0.106*
H25B	0.8163	0.4985	0.1375	0.106*
H25C	0.8522	0.4445	0.1177	0.106*
C26	0.8076 (5)	0.3746 (3)	0.2441 (5)	0.081 (3)
H26A	0.8287	0.3489	0.2154	0.121*
H26B	0.7720	0.3570	0.2683	0.121*
H26C	0.8469	0.3899	0.2787	0.121*
C27	0.7078 (5)	0.4706 (3)	0.2377 (4)	0.063 (2)
H27A	0.6694	0.4501	0.2545	0.094*
H27B	0.6851	0.4989	0.2072	0.094*
H27C	0.7409	0.4856	0.2779	0.094*
C28	0.3697 (4)	0.2325 (3)	0.2063 (4)	0.057 (2)
H28A	0.3765	0.1954	0.2192	0.085*
H28B	0.3556	0.2355	0.1552	0.085*
H28C	0.3309	0.2475	0.2288	0.085*
C29	0.5217 (9)	0.3949 (4)	0.2462 (13)	0.043 (5)	0.5
H29A	0.4806	0.4178	0.2522	0.065*	0.5
H29B	0.5355	0.4017	0.2004	0.065*	0.5
H29C	0.5637	0.4021	0.2834	0.065*	0.5
P2	0.5000	0.60856 (8)	0.2500	0.0234 (5)
C30	0.5154 (3)	0.5667 (2)	0.1800 (3)	0.0263 (14)
C31	0.4792 (4)	0.5194 (2)	0.1685 (3)	0.0380 (17)
H31	0.4434	0.5102	0.1962	0.046*
C32	0.4942 (4)	0.4850 (3)	0.1171 (3)	0.0449 (19)
H32	0.4698	0.4520	0.1104	0.054*
C33	0.5448 (4)	0.4992 (3)	0.0759 (4)	0.0436 (18)
H33	0.5572	0.4752	0.0422	0.052*
C34	0.5773 (4)	0.5477 (3)	0.0833 (4)	0.0415 (18)
H34	0.6099	0.5579	0.0529	0.050*
C35	0.5631 (4)	0.5820 (2)	0.1347 (3)	0.0349 (16)
H35	0.5856	0.6156	0.1394	0.042*
C36	0.4190 (3)	0.6479 (2)	0.2217 (3)	0.0236 (13)
C37	0.3502 (4)	0.6261 (3)	0.2203 (4)	0.0444 (18)
H37	0.3461	0.5909	0.2355	0.053*
C38	0.2879 (4)	0.6545 (3)	0.1973 (4)	0.056 (2)
H38	0.2410	0.6394	0.1980	0.067*
C39	0.2930 (4)	0.7040 (3)	0.1737 (4)	0.0473 (19)
H39	0.2496	0.7236	0.1575	0.057*
C40	0.3610 (4)	0.7265 (3)	0.1727 (3)	0.0407 (18)
H40	0.3641	0.7613	0.1558	0.049*
C41	0.4239 (4)	0.6985 (2)	0.1962 (3)	0.0295 (15)
H41	0.4706	0.7137	0.1950	0.035*
O3	0.5023 (14)	0.1534 (10)	0.8367 (13)	0.161 (6)*	0.453 (5)
C42	0.4962 (12)	0.1871 (8)	0.7827 (10)	0.073 (4)*	0.453 (5)
O4	0.5417 (11)	0.1588 (8)	0.8615 (11)	0.161 (6)*	0.547 (5)
C43	0.4884 (9)	0.1293 (7)	0.8889 (9)	0.073 (4)*	0.547 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0404 (7)	0.0204 (5)	0.0246 (6)	−0.0050 (5)	0.0197 (5)	−0.0023 (5)
S1	0.0386 (11)	0.0346 (9)	0.0354 (10)	0.0123 (8)	0.0171 (8)	−0.0029 (8)
S2	0.0518 (12)	0.0194 (8)	0.0508 (11)	−0.0047 (7)	0.0387 (9)	−0.0051 (7)
S3	0.035 (3)	0.036 (3)	0.0225 (11)	−0.0083 (17)	0.0140 (16)	−0.0017 (19)
S3'	0.035 (3)	0.036 (3)	0.0225 (11)	−0.0083 (17)	0.0140 (16)	−0.0017 (19)
P1	0.0226 (9)	0.0207 (8)	0.0221 (8)	0.0015 (7)	0.0112 (6)	0.0010 (7)
Si1	0.0299 (12)	0.0359 (11)	0.0826 (17)	0.0071 (9)	0.0225 (11)	0.0086 (11)
Si2	0.0371 (12)	0.0203 (9)	0.0517 (13)	0.0006 (8)	0.0181 (9)	−0.0009 (8)
Si3	0.0423 (13)	0.0401 (11)	0.0465 (13)	−0.0153 (9)	0.0145 (10)	−0.0083 (10)
O1	0.034 (3)	0.028 (2)	0.034 (3)	−0.003 (2)	0.021 (2)	−0.0008 (19)
O2	0.054 (4)	0.018 (3)	0.027 (3)	0.000	0.015 (3)	0.000
C1	0.031 (4)	0.019 (3)	0.032 (4)	0.003 (3)	0.012 (3)	0.007 (3)
C2	0.020 (3)	0.022 (3)	0.025 (3)	0.003 (3)	0.009 (3)	0.005 (3)
C3	0.035 (4)	0.024 (3)	0.022 (3)	−0.002 (3)	0.014 (3)	0.001 (3)
C4	0.030 (4)	0.031 (4)	0.031 (4)	−0.005 (3)	0.011 (3)	0.000 (3)
C5	0.020 (4)	0.033 (4)	0.039 (4)	−0.005 (3)	−0.002 (3)	0.015 (3)
C6	0.028 (4)	0.026 (3)	0.047 (4)	−0.002 (3)	0.014 (3)	0.007 (3)
C7	0.052 (6)	0.045 (5)	0.100 (7)	0.007 (4)	−0.003 (5)	0.007 (5)
C8	0.060 (6)	0.053 (5)	0.058 (5)	0.015 (4)	0.028 (4)	0.000 (4)
C9	0.050 (13)	0.064 (8)	0.106 (18)	0.006 (8)	0.051 (14)	0.020 (14)
C9'	0.050 (13)	0.064 (8)	0.106 (18)	0.006 (8)	0.051 (14)	0.020 (14)
C10	0.030 (4)	0.023 (3)	0.022 (3)	−0.006 (3)	0.009 (3)	−0.004 (3)
C11	0.023 (4)	0.022 (3)	0.026 (3)	0.005 (2)	0.006 (3)	0.000 (3)
C12	0.016 (3)	0.035 (4)	0.026 (3)	0.002 (3)	0.007 (3)	0.001 (3)
C13	0.022 (4)	0.029 (3)	0.038 (4)	0.008 (3)	0.015 (3)	0.000 (3)
C14	0.021 (4)	0.029 (3)	0.037 (4)	0.000 (3)	0.009 (3)	−0.009 (3)
C15	0.018 (3)	0.024 (3)	0.028 (3)	0.004 (3)	0.005 (3)	0.001 (3)
C16	0.053 (5)	0.028 (4)	0.079 (6)	0.014 (3)	0.028 (4)	0.007 (4)
C17	0.042 (5)	0.036 (4)	0.130 (9)	−0.010 (4)	0.026 (5)	−0.006 (5)
C18	0.123 (8)	0.038 (5)	0.050 (5)	0.005 (5)	0.039 (5)	0.015 (4)
C19	0.031 (4)	0.030 (3)	0.029 (4)	−0.010 (3)	0.014 (3)	−0.003 (3)
C20	0.020 (3)	0.022 (3)	0.030 (4)	−0.001 (2)	0.015 (3)	0.000 (3)
C21	0.034 (4)	0.023 (3)	0.036 (4)	0.005 (3)	0.013 (3)	0.003 (3)
C22	0.032 (4)	0.028 (3)	0.039 (4)	0.007 (3)	0.021 (3)	0.013 (3)
C23	0.033 (4)	0.018 (3)	0.050 (4)	0.000 (3)	0.026 (3)	0.001 (3)
C24	0.029 (4)	0.027 (3)	0.034 (4)	−0.001 (3)	0.020 (3)	−0.006 (3)
C25	0.071 (6)	0.064 (6)	0.080 (7)	−0.033 (5)	0.023 (5)	−0.012 (5)
C26	0.047 (6)	0.078 (7)	0.104 (8)	−0.010 (5)	−0.024 (5)	0.002 (6)
C27	0.072 (6)	0.068 (6)	0.048 (5)	−0.001 (5)	0.008 (4)	−0.023 (4)
C28	0.054 (5)	0.054 (5)	0.071 (6)	−0.021 (4)	0.036 (5)	−0.019 (4)
C29	0.066 (17)	0.011 (5)	0.058 (10)	−0.002 (6)	0.023 (12)	−0.008 (7)
P2	0.0311 (14)	0.0195 (11)	0.0208 (12)	0.000	0.0074 (10)	0.000
C30	0.026 (4)	0.028 (3)	0.025 (3)	0.006 (3)	0.003 (3)	0.001 (3)
C31	0.057 (5)	0.034 (4)	0.026 (4)	−0.010 (3)	0.016 (3)	0.004 (3)
C32	0.072 (6)	0.031 (4)	0.029 (4)	−0.004 (4)	0.003 (4)	−0.006 (3)
C33	0.046 (5)	0.048 (5)	0.034 (4)	0.015 (4)	−0.001 (3)	−0.010 (3)
C34	0.032 (4)	0.058 (5)	0.037 (4)	−0.002 (4)	0.016 (3)	−0.013 (4)
C35	0.036 (4)	0.029 (4)	0.043 (4)	0.002 (3)	0.018 (3)	0.001 (3)
C36	0.024 (4)	0.026 (3)	0.021 (3)	0.002 (3)	0.006 (3)	−0.002 (3)
C37	0.038 (5)	0.037 (4)	0.054 (5)	−0.003 (3)	−0.005 (4)	0.004 (3)
C38	0.025 (4)	0.070 (6)	0.068 (6)	−0.002 (4)	−0.004 (4)	0.006 (5)
C39	0.038 (5)	0.066 (5)	0.036 (4)	0.017 (4)	0.003 (3)	0.006 (4)
C40	0.062 (5)	0.035 (4)	0.024 (4)	0.018 (4)	0.006 (3)	0.003 (3)
C41	0.034 (4)	0.034 (4)	0.025 (3)	0.007 (3)	0.018 (3)	0.003 (3)

Geometric parameters (Å, º)

V1—O1^i	1.988 (4)	C2—C3	1.391 (8)
V1—O2	2.000 (4)	C3—C4	1.386 (9)
V1—O1	2.027 (4)	C4—C5	1.396 (8)
V1—S3'	2.363 (7)	C5—C6	1.392 (9)
V1—P1	2.3831 (17)	C10—C11	1.396 (8)
V1—S1	2.420 (2)	C10—C15	1.408 (8)
V1—S2	2.4224 (18)	C11—C12	1.373 (8)
V1—S3	2.517 (5)	C12—C13	1.386 (8)
V1—V1^i	2.8990 (19)	C13—C14	1.374 (8)
S1—C1	1.764 (6)	C14—C15	1.394 (8)
S2—C10	1.768 (6)	C19—C20	1.392 (8)
S3—C19	1.804 (8)	C19—C24	1.417 (8)
S3'—C19	1.756 (8)	C20—C21	1.386 (8)
P1—C20	1.795 (6)	C21—C22	1.393 (8)
P1—C2	1.802 (6)	C22—C23	1.379 (9)
P1—C11	1.804 (6)	C23—C24	1.393 (8)
Si1—C9	1.85 (3)	P2—C30	1.786 (6)
Si1—C8	1.857 (8)	P2—C30^i	1.786 (6)
Si1—C7	1.888 (9)	P2—C36^i	1.804 (6)
Si1—C6	1.890 (7)	P2—C36	1.804 (6)
Si1—C9'	1.91 (4)	C30—C31	1.377 (8)
Si2—C17	1.857 (8)	C30—C35	1.402 (8)
Si2—C18	1.859 (8)	C31—C32	1.390 (9)
Si2—C16	1.862 (6)	C32—C33	1.379 (10)
Si2—C15	1.883 (6)	C33—C34	1.370 (9)
Si3—C26	1.840 (9)	C34—C35	1.383 (9)
Si3—C25	1.863 (8)	C36—C37	1.383 (9)
Si3—C27	1.870 (7)	C36—C41	1.389 (8)
Si3—C24	1.891 (7)	C37—C38	1.366 (10)
O1—C28	1.391 (8)	C38—C39	1.350 (10)
O1—V1^i	1.988 (4)	C39—C40	1.383 (10)
O2—C29	1.434 (12)	C40—C41	1.371 (9)
O2—V1^i	2.000 (4)	O3—C42	1.343 (17)
C1—C2	1.387 (8)	O4—C43	1.414 (16)
C1—C6	1.420 (9)
O1^i—V1—O2	73.95 (14)	C28—O1—V1^i	133.3 (4)
O1^i—V1—O1	73.4 (2)	C28—O1—V1	134.3 (4)
O2—V1—O1	73.13 (14)	V1^i—O1—V1	92.45 (18)
O1^i—V1—S3'	83.4 (2)	C29—O2—V1^i	140.3 (10)
O2—V1—S3'	76.96 (16)	C29—O2—V1	123.2 (7)
O1—V1—S3'	146.12 (19)	V1^i—O2—V1	92.9 (2)
O1^i—V1—P1	134.74 (13)	C2—C1—C6	120.1 (6)
O2—V1—P1	135.50 (13)	C2—C1—S1	116.9 (5)
O1—V1—P1	138.62 (14)	C6—C1—S1	123.0 (5)
S3'—V1—P1	74.96 (15)	C1—C2—C3	121.7 (6)
O1^i—V1—S1	151.63 (12)	C1—C2—P1	111.9 (4)
O2—V1—S1	81.90 (8)	C3—C2—P1	126.3 (4)
O1—V1—S1	85.59 (13)	C4—C3—C2	118.9 (6)
S3'—V1—S1	105.70 (17)	C3—C4—C5	119.5 (6)
P1—V1—S1	73.45 (6)	C6—C5—C4	122.7 (6)
O1^i—V1—S2	87.33 (13)	C5—C6—C1	116.9 (6)
O2—V1—S2	151.60 (12)	C5—C6—Si1	117.8 (5)
O1—V1—S2	81.25 (12)	C1—C6—Si1	125.2 (5)
S3'—V1—S2	122.66 (15)	C11—C10—C15	120.8 (5)
P1—V1—S2	72.63 (6)	C11—C10—S2	116.6 (4)
S1—V1—S2	108.53 (8)	C15—C10—S2	122.7 (4)
O1^i—V1—S3	78.08 (17)	C12—C11—C10	121.5 (5)
O2—V1—S3	88.88 (13)	C12—C11—P1	127.1 (5)
O1—V1—S3	149.52 (17)	C10—C11—P1	111.2 (4)
P1—V1—S3	70.89 (12)	C11—C12—C13	118.9 (6)
S1—V1—S3	116.65 (13)	C14—C13—C12	119.3 (5)
S2—V1—S3	108.29 (13)	C13—C14—C15	124.1 (6)
O1^i—V1—V1^i	44.30 (11)	C14—C15—C10	115.5 (5)
O2—V1—V1^i	43.56 (11)	C14—C15—Si2	120.7 (4)
O1—V1—V1^i	43.25 (12)	C10—C15—Si2	123.9 (4)
S3'—V1—V1^i	103.19 (15)	C20—C19—C24	120.8 (6)
P1—V1—V1^i	178.14 (7)	C20—C19—S3'	116.6 (5)
S1—V1—V1^i	107.42 (6)	C24—C19—S3'	120.9 (5)
S2—V1—V1^i	108.45 (4)	C20—C19—S3	116.1 (5)
S3—V1—V1^i	107.26 (12)	C24—C19—S3	122.6 (5)
C1—S1—V1	112.1 (2)	C21—C20—C19	121.2 (5)
C10—S2—V1	110.68 (19)	C21—C20—P1	127.2 (5)
C19—S3—V1	107.0 (3)	C19—C20—P1	111.5 (4)
C19—S3'—V1	115.5 (4)	C20—C21—C22	118.9 (6)
C20—P1—C2	106.1 (3)	C23—C22—C21	119.6 (6)
C20—P1—C11	105.7 (3)	C22—C23—C24	123.4 (6)
C2—P1—C11	107.1 (3)	C23—C24—C19	116.1 (6)
C20—P1—V1	113.5 (2)	C23—C24—Si3	120.2 (5)
C2—P1—V1	112.36 (18)	C19—C24—Si3	123.7 (5)
C11—P1—V1	111.6 (2)	C30—P2—C30^i	106.7 (4)
C9—Si1—C8	117.6 (9)	C30—P2—C36^i	109.2 (3)
C9—Si1—C7	103.1 (8)	C30^i—P2—C36^i	109.5 (3)
C8—Si1—C7	105.5 (4)	C30—P2—C36	109.5 (3)
C9—Si1—C6	109.2 (10)	C30^i—P2—C36	109.2 (3)
C8—Si1—C6	114.5 (3)	C36^i—P2—C36	112.6 (4)
C7—Si1—C6	105.5 (4)	C31—C30—C35	118.9 (6)
C8—Si1—C9'	100.8 (11)	C31—C30—P2	120.5 (5)
C7—Si1—C9'	121.9 (11)	C35—C30—P2	120.6 (5)
C6—Si1—C9'	109.0 (12)	C30—C31—C32	121.0 (6)
C17—Si2—C18	110.5 (4)	C33—C32—C31	119.3 (7)
C17—Si2—C16	108.5 (4)	C34—C33—C32	120.3 (6)
C18—Si2—C16	108.1 (4)	C33—C34—C35	120.7 (6)
C17—Si2—C15	109.2 (3)	C34—C35—C30	119.6 (6)
C18—Si2—C15	112.5 (3)	C37—C36—C41	118.8 (6)
C16—Si2—C15	107.9 (3)	C37—C36—P2	119.6 (5)
C26—Si3—C25	105.9 (4)	C41—C36—P2	121.4 (5)
C26—Si3—C27	110.7 (4)	C38—C37—C36	120.9 (7)
C25—Si3—C27	110.7 (4)	C39—C38—C37	120.0 (7)
C26—Si3—C24	114.0 (3)	C38—C39—C40	120.5 (7)
C25—Si3—C24	107.0 (3)	C41—C40—C39	120.0 (7)
C27—Si3—C24	108.4 (3)	C40—C41—C36	119.8 (6)

Symmetry code: (i) −x+1, y, −z+1/2.