Crystal structures of two deca­vanadates(V) with penta­aqua­manganese(II) pendant groups: (NMe₄)₂[V₁₀O₂₈{Mn(H₂O)₅}₂]·5H₂O and [NH₃C(CH₂OH)₃]₂[V₁₀O₂₈{Mn(H₂O)₅}₂]·2H₂O

Two heterometallic deca­vanadate(V) hydrated salts with tetra­methyl­ammonium and [tris­(hy­droxy­meth­yl)meth­yl]ammonium counter-cations have been synthesized under mild reaction conditions in an aqueous medium. Both polyanions present two [Mn(OH₂)₅]²⁺ complex units bound to the deca­vanadate cluster through oxide bridges.

Key indicators

Structure: Compound-A

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](N-C) = 0.004 Å
• H-atom completeness 89%
• Disorder in solvent or counterion
• R factor = 0.020
• wR factor = 0.060
• Data-to-parameter ratio = 15.2

Structure: Compound-B

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.010 Å
• Disorder in solvent or counterion
• R factor = 0.052
• wR factor = 0.114
• Data-to-parameter ratio = 10.2

checkCIF/PLATON results

No syntax errors found



Datablock: Compound-A



Alert level A
PLAT900_ALERT_1_A No Matching Reflection File (FCF) Found ........    Please Check

Alert level B
PLAT306_ALERT_2_B Isolated Oxygen Atom (H-atoms Missing ?) .......        O13 Check
PLAT430_ALERT_2_B Short Inter D...A Contact  O13    ..  O13     ..       2.76 Ang.

Alert level C
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ     Please Check
PLAT043_ALERT_1_C Calculated and Reported Mol. Weight Differ by ..      10.08 Check
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...     Please Check
PLAT220_ALERT_2_C Large Non-Solvent  O     Ueq(max)/Ueq(min) Range        3.1 Ratio
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of          N1 Check
PLAT430_ALERT_2_C Short Inter D...A Contact  O10    ..  O14B    ..       2.85 Ang.

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C8 H54 Mn2 N2 O43 V10
            Atom count from the _atom_site data:  C8 H48 Mn2 N2 O43 V10
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    2
           From the CIF: _chemical_formula_sum  C8 H54 Mn2 N2 O43 V10
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         16.00     16.00    0.00
           H        108.00     96.00   12.00
           Mn         4.00      4.00    0.00
           N          4.00      4.00    0.00
           O         86.00     86.00    0.00
           V         20.00     20.00    0.00
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT302_ALERT_4_G Anion/Solvent Disorder ............ Percentage =          4 Note
PLAT311_ALERT_2_G Isolated Disordered Oxygen Atom (No H's ?) .....       O14A Check
PLAT311_ALERT_2_G Isolated Disordered Oxygen Atom (No H's ?) .....       O14B Check
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.44 Ratio

   1 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check




Datablock: Compound-B



Alert level A
PLAT222_ALERT_3_A Large Non-Solvent    H    Uiso(max)/Uiso(min) ..       10.0 Ratio
PLAT900_ALERT_1_A No Matching Reflection File (FCF) Found ........    Please Check

Alert level B
PLAT354_ALERT_3_B Short   O-H (X0.82,N0.98A) O2W    -   H2A    ...       0.59 Ang.
PLAT354_ALERT_3_B Short   O-H (X0.82,N0.98A) O5W    -   H5A    ...       0.54 Ang.
PLAT417_ALERT_2_B Short Inter D-H..H-D       H5B    ..  H13B    ..       1.80 Ang.

Alert level C
PLAT213_ALERT_2_C Atom O1W             has ADP max/min Ratio .....        3.3 prolat
PLAT214_ALERT_2_C Atom O13B    (Anion/Solvent) ADP max/min Ratio          4.3 prolat
PLAT220_ALERT_2_C Large Non-Solvent  O     Ueq(max)/Ueq(min) Range        3.8 Ratio
PLAT223_ALERT_4_C Large Solvent/Anion  H     Ueq(max)/Ueq(min) ...        3.8 Ratio
PLAT245_ALERT_2_C U(iso) H1B     Smaller than U(eq) O1W     by ...      0.041 AngSq
PLAT245_ALERT_2_C U(iso) H2A     Smaller than U(eq) O2W     by ...      0.018 AngSq
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0103 Ang.
PLAT354_ALERT_3_C Short   O-H (X0.82,N0.98A) O1W    -   H1A    ...       0.70 Ang.
PLAT354_ALERT_3_C Short   O-H (X0.82,N0.98A) O1W    -   H1B    ...       0.69 Ang.
PLAT354_ALERT_3_C Short   O-H (X0.82,N0.98A) O3W    -   H3A    ...       0.70 Ang.
PLAT924_ALERT_1_C The Reported and Calculated Rho(min) Differ by .       1.11 eA-3

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          6 Note
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          6 Report
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.     110.79 Why ?
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT173_ALERT_4_G The CIF-Embedded .res File Contains DANG Records          1 Report
PLAT302_ALERT_4_G Anion/Solvent Disorder ............ Percentage =         22 Note
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2 Note
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.24 Ratio
PLAT794_ALERT_5_G Tentative Bond Valency for Mn1     (IX)    .....       0.36 Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          6 Note

   2 ALERT level A = Most likely a serious problem - resolve or explain
   3 ALERT level B = A potentially serious problem, consider carefully
  11 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  11 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   8 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

---

S1. Chemical context

Research on the electronic properties, catalytic activities and biological roles of polyoxovanadates has advanced enormously during the last few decades (Bošnjaković-Pavlović et al., 2009; Liu & Zhou, 2010). Among these aggregates, the decavanadate(V) anion is the most intensively studied because of its biological effect on the activities of several enzymes (Aureliano & Ohlin, 2014) and its insulin-mimetic action (Chatkon et al., 2013; Aureliano, 2014). The first functionalization of decavanadate anions, [H_nV₁₀O₂₈]^(6-n)-, with transition metal complexes was reported in 2007 (Li et al., 2007). Since then, structures involving different binding modes with non-equivalent terminal and bridging oxido ligands have been described (Wang, Sun et al. OK?, 2008, 2011; Long et al., 2010; Xu et al., 2012) and examples with first-row, d-block metal ions include complexation with copper(II), manganese(II) and zinc(II) (Wang, Sun et al. OK?, 2008; Klištincová et al., 2009, 2010; Pavliuk et al., 2014).

Polyoxovanadates containing manganese cations have been synthesized as ionic pairs (Shan & Huang, 1999; Lin et al., 2011) or as heterometallic aggregates in which the oxovanadate cluster acts as a metalloligand to the manganese complex (Inami et al., 2009; Klištincová et al., 2009). Recent inter­est in this kind of compound lies in a possible synergistic effect (involving the two metal elements) for the enhancement of the catalytic activity towards oxidation of organic substrates, such as in the photocatalytic degradation of dyes (Wu et al., 2012).

While the synthesis of decavanadates with different organic cations as building blocks for supra­molecular assemblies is largely explored (da Silva et al., 2003), a systematic procedure for their functionalization with transition metal complexes has not been well established. Our research group is currently involved in the synthesis of heterometallic polyoxovanadates containing manganese(II) because of their potential activity as catalysts of olefin epoxidation. In this context, the reaction between NH₄VO₃ and mannitol to give A was carried out in aqueous solution in the presence of tetra­methyl­ammonium chloride (molar proportion 2:1:2), following a procedure described earlier by our group to produce the mixed-valence polyoxovanadate (Me₄N)₆[V₁₅O₃₆(Cl)] (Nunes et al., 2012). The dark-green solution obtained after reflux for 24 h received one molar equivalent of Mn(OAc)₂·4H₂O and was kept under reflux for 24 more hours. A mixture of dark-green crystals of (Me₄N)₆[V₁₅O₃₆(Cl)] and yellow prisms of (NMe₄)₂[V₁₀O₂₈{Mn(H₂O)₅}₂]·5H₂O (A) was isolated after four weeks at room temperature, the latter in 9% yield. Product A contains two tetra­methyl­ammonium cations and the [V₁₀O₂₈]^6– unit is covalently bound to two [Mn(OH₂)₅]²⁺ complexes by terminal oxido bridges (Scheme 1).

The rational synthesis of the heteropolyanion [V₁₀O₂₈{Mn(H₂O)₅}₂]^2–, in its turn, was achieved by reaction of NH₄VO₃ with tris­(hy­droxy­methyl)­methyl­amine ('tris­') and manganese(II) chloride at pH 3 in a 5:3:1 molar proportion. Yellow crystals of [(NH₃C(CH₂OH)₃]₂[V₁₀O₂₈{Mn(H₂O)₅}₂]·2H₂O (B, Scheme 2) were isolated in 12% yield, as the only reaction product, after one week at room temperature. X-ray diffraction analyses revealed the same molecular structure for the heteropolyanion in A and B.

S2. Structural commentary

The anionic clusters are essentially identical in the two complexes. However, in A, the molecule lies about the centre of the cell which is a point of 2/m symmetry, so that the unique part of the anionic cluster is one quarter of that cluster. The anion lies about a mirror plane which passes through V2 and V4 and the manganese atoms, and there is a twofold symmetry axis which is perpendicular to the mirror plane and passes through V3 and the centre of the cell, Fig. 1.

The V₁₀O₂₈ cluster in compound B lies about a twofold symmetry axis which passes through the vanadium atoms V6 and V7, Fig. 2. This is the only crystallographic symmetry in this ion which, nevertheless, shows a very similar structure to that found in the ion in compound A; views showing this pseudo-symmetry are presented in Figs. 3, 4 and 5. The unique part here is one half of the anion. The previously reported analysis of this anion [with a 2-(2-hy­droxy­ethyl)­pyridinium cation] showed the cluster to be lying about an inversion centre (Klištincová et al., 2009).

Bond angles and distances determined for [V₁₀O₂₈{Mn(H₂O)₅}₂]^2– are in the range reported in the literature (Klištincová et al., 2009). In both our compounds, there is a wide range of V—O bond lengths. The vanadium atoms on the outer shell of the clusters, e.g. V4 and V5 in A, and V2–V5 in B, are five-coordinate with a square-pyramidal pattern; there is a sixth oxygen atom in the direction of an o­cta­hedral site but, at ca 2.3 Å from the vanadium atom, rather longer than the normal coordination distance. Of the five bonded oxygen atoms, the apical site (opposite the distant, sixth, site) has the shortest V—O distance, ca 1.6 Å, corresponding to a vanadyl group. The more `inter­nal' vanadium atoms in each structure, viz V3 in A, and V6 and V7 in B, have more uniform V—O distances in more regular o­cta­hedral patterns.

S3. Supra­molecular features

In both compounds, O—H···O hydrogen bonds from all the coordinating water molecules link the anions with neighbouring anions, either directly, through both the cluster O atoms and the coordinating water molecules, or indirectly through the solvent water molecules (Tables 1 and 2). In compound B, additional hydroxyl groups are available in the 'tris­' cation, and these add further links in the extensive hydrogen bonding scheme.

S4. Database survey

For structures with the [V₁₀O₂₈{Mn(H₂O)₅}₂]^2– heteropolyanion, see: Klištincová et al. (2009) and Inami et al. (2009). For structures with manganese(II) coordination complexes as counter-ions for [V₁₀O₂₈]^6–, see: Klištincová et al. (2010); Shan & Huang (1999); Lin et al. (2011) and Mestiri et al. (2013).

S5. Synthesis and crystallization

General

All reactions were performed in air with purified (Milli-Q^®) water. Commercial reagents were used without purification. The starting materials NH₄VO₃, MnCl₂·4H₂O and Mn(OAc)₂·4H₂O were supplied by Aldrich, while mannitol (C₆H₈(OH)₆) and (Me₄N)Cl were purchased from USB and Merck, respectively. Infrared (FTIR) spectra were recorded on a BIORAD FTS-3500GX spectrophotometer from KBr pellets in the 400–4000 cm^-1 region.

Synthesis of (NMe₄)₂[V₁₀O₂₈{Mn(H₂O)₅}₂]·5H₂O (A)

Solid NH₄VO₃ (0.500 g, 4.27 mmol) and [(CH₃)₄N]Cl (0.468 g, 4.27 mmol) were added to a solution of mannitol (0.366 g, 2.13 mmol) in 60 ml of water to produce a suspension that turned into a deep blue–greenish solution after one hour under reflux. After 24 more hours, a solution of Mn(OAc)₂·4H₂O (1.04 g, 4.27 mmol) in 10 ml of water was added to this reaction mixture, which remained under reflux for one more day. The solution was concentrated to 1/3 of its initial volume and, after four weeks at room temperature, a mixture of deep-green crystals of (Me₄N)₆[V₁₅O₃₆(Cl)] (Nunes et al., 2012) and yellow prisms of A was obtained, the latter in 9% yield based on vanadium (56 mg). The FTIR spectrum recorded for A shows the characteristic bands of the Me₄N⁺ cation at 3031, 1639, 1485 and 1263 cm^-1 and of the inorganic anion at 966, 833, 744, 584 and 455 cm^-1.

Synthesis of [NH₃C(CH₂OH)₃]₂[V₁₀O₂₈{Mn(H₂O)₅}₂]·2H₂O (B)

A solution containing tris­(hy­droxy­methyl)­methyl­amine (0.720 g, 6.0 mmol) in 20 mL of water was added to a solution of NH₄VO₃ (1.17 g, 10.0 mmol) in the same volume of solvent. This reaction mixture was then refluxed until it became a clear solution, after which its pH was adjusted to 3 with aqueous HCl. A solution of MnCl₂·4H₂O (0.394 g, 2.0 mmol) in 10 mL of water was then added as a layer on top of the reaction mixture and, after two weeks at room temperature, yellow crystals of B were obtained (180 mg) in 12% yield based on vanadium. The FTIR spectrum of B shows characteristic bands of the tris­H⁺ cation at 3188, 2927, 2856, 1743, 1637, 1417, 1161 and 1112 cm^-1 and of the inorganic anion at 941, 842 and 684 cm^-1.

S6. Refinement details

Crystal data, data collection and structure refinement details for the two structures are summarized in Table 3.

Hydrogen atoms on the cation atoms were included in idealized positions (with methyl and methyl­ene group C—H distances set at 0.96 and 0.97 Å, N—H at 0.89 Å and O—H at 0.82 Å) and their U_iso values were set to ride on the U_eq values of the parent atoms. Hydrogen atoms in the anions (on coordinating water molecules) were located in difference maps and were refined freely.

There are two independent solvent water molecules, one of which is disordered over two sites close to a centre of symmetry, in compound A. No hydrogen atoms were identified in these water molecules.

In B, there is one solvent water molecule which is disordered over two sites; the hydrogen atoms here were located in difference maps and were refined with distance restraints [O—H = 0.82 (2) Å].

Related literature

For related literature, see: Aureliano (2014); Aureliano & Ohlin (2014); Bošnjaković-Pavlović, Spasojevic-de Bire, Tomaz, Bouhmaida, Avecilla, Mioc, Pessoa & Ghermani (2009); Inami et al. (2009); Klištincová et al. (2009, 2010); Li et al. (2007); Lin et al. (2011); Liu & Zhou (2010); Long et al. (2010); Mestiri et al. (2013); Nunes et al. (2012); Pavliuk et al. (2014); Shan & Huang (1999); Silva et al. (2003); Wang et al. (2011); Wang, Sun, Liu, Gao, Gu & Liu (2008); Wang, Yan, Du & Niu (2008); Wu et al. (2012); Xu et al. (2012).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for Compound-A; SHELXS97 (Sheldrick 2008) for Compound-B. Program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015) for Compound-A; SHELXL2014 (Sheldrick, 2015) for Compound-B. For both compounds, molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 2012).

Figures

	Fig. 1. View of the components of (NMe4)2[V10O28{Mn(H2O)5}2]·5H2O, A, indicating the atom-numbering scheme. No H atoms were identified on the disordered solvent water molecules. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (1) 1 - x, y, 1 - z; (2) 1 - x, 1 - y, 1 - z; (3) x, 1 - y, z; (4) 1 - x, -y, -z; (5) 1 - x, y, -z.]
	Fig. 2. The corresponding view for [NH3C(CH2OH)3]2[V10O28{Mn(H2O)5}2]·2H2O, B. [Symmetry code: (1) 1 - x, y, 1/2 - z.]
	Fig. 3. The anion of compound B viewed approximately down the a axis of the V10O28 cluster. [Symmetry code: (1) 1 - x, y, 1/2 - z.]
	Fig. 4. The anion of compound B viewed approximately down the b axis of the V10O28 cluster. [Symmetry code: (1) 1 - x, y, 1/2 - z.]
	Fig. 5. The anion of compound B viewed approximately down the c axis of the V10O28 cluster. [Symmetry code: (1) 1 - x, y, 1/2 - z.]

(Compound-A) Bis(tetramethylammonium) decaaquadi-µ₄oxido-tetra-µ₃-oxido-hexadeca-µ₂-oxido-hexaoxidodimanganesedecavanadate pentahydrate

Crystal data

(C4H12N)2·[Mn2V10O28(H2O)10]·5H2O	F(000) = 1480
Mr = 1485.81	Dx = 2.201 Mg m^−3
Monoclinic, I2/m	Mo Kα radiation, λ = 0.71073 Å
a = 13.2434 (7) Å	Cell parameters from 9256 reflections
b = 9.6402 (5) Å	θ = 3.1–28.3°
c = 17.7628 (13) Å	µ = 2.64 mm^−1
β = 98.626 (2)°	T = 292 K
V = 2242.1 (2) Å^3	Prism, yellow
Z = 2	0.48 × 0.38 × 0.15 mm

Data collection

Bruker D8 Venture/Photon 100 CMOS diffractometer	2953 independent reflections
Radiation source: fine-focus sealed tube	2752 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 10.4167 pixels mm^-1	θmax = 28.4°, θmin = 3.1°
ϕ and ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −12→12
Tmin = 0.562, Tmax = 0.746	l = −23→23
81983 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.020	Hydrogen site location: mixed
wR(F^2) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0329P)^2 + 2.2668P] where P = (Fo^2 + 2Fc^2)/3
2953 reflections	(Δ/σ)max = 0.001
194 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.23106 (3)	0.5000	0.18528 (2)	0.02403 (8)
V2	0.32741 (2)	0.5000	0.39643 (2)	0.01725 (8)
V3	0.5000	0.66921 (3)	0.5000	0.01425 (8)
V4	0.54714 (3)	0.5000	0.35620 (2)	0.01948 (8)
V5	0.28084 (2)	0.65841 (2)	0.54017 (2)	0.02209 (7)
O1	0.15020 (19)	0.5000	0.07177 (11)	0.0480 (6)
O2	0.13101 (10)	0.32849 (12)	0.20645 (7)	0.0293 (2)
O3	0.33574 (10)	0.33360 (12)	0.15931 (7)	0.0310 (3)
O4	0.28574 (12)	0.5000	0.30500 (8)	0.0253 (3)
O5	0.50366 (14)	0.5000	0.26708 (8)	0.0328 (4)
O6	0.25845 (7)	0.36038 (10)	0.43170 (6)	0.0223 (2)
O7	0.44883 (7)	0.62838 (10)	0.39540 (5)	0.01665 (18)
O8	0.64321 (8)	0.36184 (11)	0.36540 (5)	0.0230 (2)
O9	0.40458 (10)	0.5000	0.51485 (7)	0.0153 (2)
O10	0.20825 (11)	0.5000	0.54989 (9)	0.0257 (3)
O11	0.40317 (7)	0.77369 (10)	0.51675 (5)	0.02001 (19)
O12	0.20299 (9)	0.78080 (13)	0.55243 (7)	0.0365 (3)
H1A	0.1272 (17)	0.437 (2)	0.0491 (13)	0.053 (7)*
H2A	0.1052 (16)	0.285 (2)	0.1767 (12)	0.038 (6)*
H2B	0.1397 (15)	0.285 (2)	0.2440 (13)	0.038 (6)*
H3A	0.3060 (19)	0.283 (3)	0.1339 (14)	0.053 (7)*
H3B	0.392 (2)	0.359 (3)	0.1441 (17)	0.087 (10)*
N1	0.85954 (17)	0.5000	0.23196 (11)	0.0348 (4)
C10	0.9084 (2)	0.5000	0.16133 (14)	0.0373 (5)
H10A	0.8883	0.4181	0.1321	0.056*	0.5
H10B	0.8870	0.5807	0.1315	0.056*	0.5
H10C	0.9813	0.5011	0.1750	0.056*
C11	0.8902 (2)	0.3739 (2)	0.27733 (14)	0.0706 (8)
H11A	0.8699	0.2930	0.2473	0.106*
H11B	0.9630	0.3735	0.2920	0.106*
H11C	0.8577	0.3735	0.3221	0.106*
C12	0.7469 (3)	0.5000	0.2091 (2)	0.0895 (16)
H12A	0.7269	0.4184	0.1797	0.134*	0.5
H12B	0.7142	0.5007	0.2539	0.134*
H12C	0.7270	0.5810	0.1791	0.134*	0.5
O13	0.5022 (2)	0.3567 (5)	0.0856 (2)	0.1752 (17)
O14A	0.5000	0.0973 (14)	0.0000	0.143 (14)	0.280 (18)
O14B	0.4760 (18)	0.0000	0.0562 (15)	0.158 (18)	0.220 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.03393 (17)	0.01631 (15)	0.01903 (15)	0.000	−0.00521 (12)	0.000
V2	0.01907 (15)	0.01704 (15)	0.01409 (15)	0.000	−0.00259 (11)	0.000
V3	0.01883 (15)	0.01043 (13)	0.01303 (14)	0.000	0.00088 (10)	0.000
V4	0.02432 (16)	0.02264 (17)	0.01183 (14)	0.000	0.00388 (11)	0.000
V5	0.02267 (12)	0.01995 (13)	0.02474 (13)	0.00444 (9)	0.00709 (9)	−0.00058 (9)
O1	0.0908 (17)	0.0167 (8)	0.0266 (9)	0.000	−0.0232 (9)	0.000
O2	0.0407 (6)	0.0190 (5)	0.0250 (6)	−0.0052 (4)	−0.0054 (5)	−0.0005 (4)
O3	0.0325 (6)	0.0240 (5)	0.0345 (6)	−0.0022 (5)	−0.0016 (5)	−0.0062 (5)
O4	0.0290 (7)	0.0270 (8)	0.0168 (6)	0.000	−0.0066 (5)	0.000
O5	0.0423 (9)	0.0413 (9)	0.0144 (7)	0.000	0.0030 (6)	0.000
O6	0.0219 (5)	0.0214 (5)	0.0223 (5)	−0.0047 (4)	−0.0010 (4)	−0.0013 (4)
O7	0.0214 (4)	0.0149 (4)	0.0128 (4)	0.0009 (3)	−0.0001 (3)	0.0016 (3)
O8	0.0285 (5)	0.0222 (5)	0.0195 (4)	0.0022 (4)	0.0078 (4)	−0.0029 (4)
O9	0.0191 (6)	0.0138 (6)	0.0128 (6)	0.000	0.0011 (5)	0.000
O10	0.0216 (7)	0.0268 (7)	0.0301 (8)	0.000	0.0082 (6)	0.000
O11	0.0256 (5)	0.0141 (4)	0.0202 (4)	0.0030 (4)	0.0031 (4)	−0.0001 (3)
O12	0.0341 (6)	0.0312 (6)	0.0458 (7)	0.0121 (5)	0.0113 (5)	−0.0029 (5)
N1	0.0484 (12)	0.0300 (10)	0.0304 (10)	0.000	0.0201 (9)	0.000
C10	0.0470 (14)	0.0381 (13)	0.0311 (12)	0.000	0.0204 (10)	0.000
C11	0.128 (2)	0.0406 (12)	0.0531 (13)	0.0137 (13)	0.0449 (15)	0.0168 (10)
C12	0.051 (2)	0.153 (5)	0.071 (3)	0.000	0.0329 (19)	0.000
O13	0.0805 (18)	0.238 (4)	0.220 (4)	0.022 (2)	0.064 (2)	0.065 (3)
O14A	0.027 (5)	0.059 (8)	0.33 (4)	0.000	−0.022 (10)	0.000
O14B	0.101 (15)	0.21 (4)	0.135 (19)	0.000	−0.077 (14)	0.000

Geometric parameters (Å, º)

Mn1—O1	2.1365 (18)	V5—O10	1.8264 (8)
Mn1—O4	2.1412 (14)	V5—O8^iii	1.8322 (10)
Mn1—O2	2.1863 (12)	V5—O6^i	1.9136 (10)
Mn1—O2^i	2.1863 (12)	V5—O11	2.0579 (10)
Mn1—O3	2.2136 (12)	V5—O9	2.3326 (10)
Mn1—O3^i	2.2136 (12)	V5—V5^i	3.0543 (5)
V2—O4	1.6350 (14)	V5—V4^iii	3.1068 (4)
V2—O6	1.7916 (10)	O1—H1A	0.76 (2)
V2—O6^i	1.7916 (10)	O2—H2A	0.72 (2)
V2—O7^i	2.0314 (10)	O2—H2B	0.78 (2)
V2—O7	2.0314 (10)	O3—H3A	0.74 (3)
V2—O9	2.1964 (12)	O3—H3B	0.87 (3)
V2—V4	3.0988 (5)	O6—V5^i	1.9137 (10)
V2—V5	3.1152 (4)	O8—V5^iii	1.8322 (10)
V2—V5^i	3.1153 (4)	O9—V3^iii	2.1041 (9)
V3—O11	1.6917 (10)	O9—V4^iii	2.2840 (12)
V3—O11^ii	1.6918 (10)	O9—V5^i	2.3327 (10)
V3—O7	1.9205 (9)	O10—V5^i	1.8264 (8)
V3—O7^ii	1.9205 (9)	N1—C11^i	1.481 (2)
V3—O9	2.1041 (9)	N1—C11	1.481 (2)
V3—O9^iii	2.1041 (9)	N1—C12	1.486 (4)
V3—V5	3.0928 (3)	N1—C10	1.496 (3)
V3—V5^ii	3.0928 (3)	C10—H10A	0.9600
V4—O5	1.6013 (15)	C10—H10B	0.9600
V4—O8^i	1.8322 (10)	C10—H10C	0.9600
V4—O8	1.8322 (10)	C11—H11A	0.9600
V4—O7	1.9959 (10)	C11—H11B	0.9600
V4—O7^i	1.9959 (10)	C11—H11C	0.9600
V4—O9^iii	2.2840 (12)	C12—H12A	0.9600
V4—V5^ii	3.1069 (4)	C12—H12B	0.9600
V4—V5^iii	3.1069 (4)	C12—H12C	0.9600
V5—O12	1.6030 (11)
O1—Mn1—O4	169.83 (9)	O5—V4—V5^iii	135.13 (5)
O1—Mn1—O2	86.07 (6)	O8^i—V4—V5^iii	82.35 (3)
O4—Mn1—O2	87.28 (4)	O8—V4—V5^iii	32.02 (3)
O1—Mn1—O2^i	86.07 (6)	O7—V4—V5^iii	123.83 (3)
O4—Mn1—O2^i	87.28 (4)	O7^i—V4—V5^iii	86.97 (3)
O2—Mn1—O2^i	98.27 (7)	O9^iii—V4—V5^iii	48.37 (3)
O1—Mn1—O3	92.53 (6)	V2—V4—V5^iii	119.596 (11)
O4—Mn1—O3	94.47 (4)	V5^ii—V4—V5^iii	58.884 (11)
O2—Mn1—O3	84.40 (5)	O12—V5—O10	104.13 (6)
O2^i—Mn1—O3	176.89 (5)	O12—V5—O8^iii	103.30 (6)
O1—Mn1—O3^i	92.53 (6)	O10—V5—O8^iii	92.80 (6)
O4—Mn1—O3^i	94.47 (4)	O12—V5—O6^i	101.58 (6)
O2—Mn1—O3^i	176.88 (5)	O10—V5—O6^i	90.67 (6)
O2^i—Mn1—O3^i	84.40 (5)	O8^iii—V5—O6^i	153.19 (5)
O3—Mn1—O3^i	92.89 (7)	O12—V5—O11	99.90 (6)
O4—V2—O6	103.51 (5)	O10—V5—O11	155.80 (5)
O4—V2—O6^i	103.51 (5)	O8^iii—V5—O11	84.37 (4)
O6—V2—O6^i	97.40 (7)	O6^i—V5—O11	81.68 (4)
O4—V2—O7^i	98.09 (5)	O12—V5—O9	173.12 (5)
O6—V2—O7^i	89.49 (4)	O10—V5—O9	82.29 (4)
O6^i—V2—O7^i	155.03 (4)	O8^iii—V5—O9	78.56 (4)
O4—V2—O7	98.09 (5)	O6^i—V5—O9	75.59 (4)
O6—V2—O7	155.03 (4)	O11—V5—O9	73.59 (3)
O6^i—V2—O7	89.49 (4)	O12—V5—V5^i	137.39 (5)
O7^i—V2—O7	75.07 (5)	O10—V5—V5^i	33.27 (4)
O4—V2—O9	172.10 (7)	O8^iii—V5—V5^i	83.88 (3)
O6—V2—O9	81.57 (4)	O6^i—V5—V5^i	84.57 (3)
O6^i—V2—O9	81.57 (4)	O11—V5—V5^i	122.69 (3)
O7^i—V2—O9	75.72 (4)	O9—V5—V5^i	49.10 (2)
O7—V2—O9	75.72 (4)	O12—V5—V3	130.66 (5)
O4—V2—V4	87.69 (6)	O10—V5—V3	125.13 (4)
O6—V2—V4	128.77 (3)	O8^iii—V5—V3	79.01 (3)
O6^i—V2—V4	128.77 (3)	O6^i—V5—V3	77.29 (3)
O7^i—V2—V4	39.28 (3)	O11—V5—V3	30.76 (3)
O7—V2—V4	39.28 (3)	O9—V5—V3	42.84 (2)
O9—V2—V4	84.41 (4)	V5^i—V5—V3	91.929 (7)
O4—V2—V5	137.34 (4)	O12—V5—V4^iii	135.29 (5)
O6—V2—V5	84.70 (3)	O10—V5—V4^iii	83.26 (4)
O6^i—V2—V5	34.01 (3)	O8^iii—V5—V4^iii	32.02 (3)
O7^i—V2—V5	124.08 (3)	O6^i—V5—V4^iii	122.63 (3)
O7—V2—V5	87.88 (3)	O11—V5—V4^iii	81.71 (3)
O9—V2—V5	48.39 (3)	O9—V5—V4^iii	47.04 (3)
V4—V2—V5	119.816 (10)	V5^i—V5—V4^iii	60.558 (6)
O4—V2—V5^i	137.34 (4)	V3—V5—V4^iii	61.520 (9)
O6—V2—V5^i	34.02 (3)	O12—V5—V2	133.04 (5)
O6^i—V2—V5^i	84.70 (3)	O10—V5—V2	80.75 (4)
O7^i—V2—V5^i	87.88 (3)	O8^iii—V5—V2	123.30 (3)
O7—V2—V5^i	124.08 (3)	O6^i—V5—V2	31.58 (3)
O9—V2—V5^i	48.39 (3)	O11—V5—V2	80.81 (3)
V4—V2—V5^i	119.816 (10)	O9—V5—V2	44.75 (3)
V5—V2—V5^i	58.710 (11)	V5^i—V5—V2	60.645 (6)
O11—V3—O11^ii	106.92 (7)	V3—V5—V2	61.274 (8)
O11—V3—O7	97.20 (4)	V4^iii—V5—V2	91.545 (10)
O11^ii—V3—O7	96.82 (4)	Mn1—O1—H1A	127.0 (17)
O11—V3—O7^ii	96.82 (4)	Mn1—O2—H2A	123.2 (17)
O11^ii—V3—O7^ii	97.20 (4)	Mn1—O2—H2B	122.5 (15)
O7—V3—O7^ii	156.35 (6)	H2A—O2—H2B	108 (2)
O11—V3—O9	87.37 (4)	Mn1—O3—H3A	108.1 (19)
O11^ii—V3—O9	165.69 (5)	Mn1—O3—H3B	117 (2)
O7—V3—O9	80.27 (4)	H3A—O3—H3B	114 (3)
O7^ii—V3—O9	81.45 (4)	V2—O4—Mn1	179.96 (10)
O11—V3—O9^iii	165.69 (5)	V2—O6—V5^i	114.40 (5)
O11^ii—V3—O9^iii	87.38 (4)	V3—O7—V4	108.10 (4)
O7—V3—O9^iii	81.45 (4)	V3—O7—V2	106.33 (4)
O7^ii—V3—O9^iii	80.27 (4)	V4—O7—V2	100.60 (4)
O9—V3—O9^iii	78.34 (6)	V5^iii—O8—V4	115.96 (5)
O11—V3—V5	38.47 (3)	V3^iii—O9—V3	101.66 (6)
O11^ii—V3—V5	145.38 (4)	V3^iii—O9—V2	94.70 (4)
O7—V3—V5	90.52 (3)	V3—O9—V2	94.70 (4)
O7^ii—V3—V5	88.69 (3)	V3^iii—O9—V4^iii	92.45 (4)
O9—V3—V5	48.93 (3)	V3—O9—V4^iii	92.45 (4)
O9^iii—V3—V5	127.22 (3)	V2—O9—V4^iii	168.68 (7)
O11—V3—V5^ii	145.38 (4)	V3^iii—O9—V5	169.81 (5)
O11^ii—V3—V5^ii	38.47 (3)	V3—O9—V5	88.231 (11)
O7—V3—V5^ii	88.68 (3)	V2—O9—V5	86.86 (4)
O7^ii—V3—V5^ii	90.52 (3)	V4^iii—O9—V5	84.59 (4)
O9—V3—V5^ii	127.22 (3)	V3^iii—O9—V5^i	88.232 (11)
O9^iii—V3—V5^ii	48.93 (3)	V3—O9—V5^i	169.81 (5)
V5—V3—V5^ii	176.145 (13)	V2—O9—V5^i	86.86 (4)
O5—V4—O8^i	103.31 (5)	V4^iii—O9—V5^i	84.59 (4)
O5—V4—O8	103.30 (5)	V5—O9—V5^i	81.79 (4)
O8^i—V4—O8	93.26 (7)	V5^i—O10—V5	113.47 (8)
O5—V4—O7	100.85 (6)	V3—O11—V5	110.76 (5)
O8^i—V4—O7	89.92 (4)	C11^i—N1—C11	110.3 (3)
O8—V4—O7	154.18 (4)	C11^i—N1—C12	109.32 (18)
O5—V4—O7^i	100.85 (6)	C11—N1—C12	109.32 (18)
O8^i—V4—O7^i	154.18 (4)	C11^i—N1—C10	109.79 (14)
O8—V4—O7^i	89.92 (4)	C11—N1—C10	109.79 (14)
O7—V4—O7^i	76.64 (6)	C12—N1—C10	108.3 (2)
O5—V4—O9^iii	175.24 (8)	N1—C10—H10A	109.5
O8^i—V4—O9^iii	79.88 (4)	N1—C10—H10B	109.5
O8—V4—O9^iii	79.88 (4)	H10A—C10—H10B	109.5
O7—V4—O9^iii	75.47 (4)	N1—C10—H10C	109.5
O7^i—V4—O9^iii	75.48 (4)	H10A—C10—H10C	109.5
O5—V4—V2	90.98 (7)	H10B—C10—H10C	109.5
O8^i—V4—V2	130.01 (3)	N1—C11—H11A	109.5
O8—V4—V2	130.01 (3)	N1—C11—H11B	109.5
O7—V4—V2	40.12 (3)	H11A—C11—H11B	109.5
O7^i—V4—V2	40.12 (3)	N1—C11—H11C	109.5
O9^iii—V4—V2	84.26 (3)	H11A—C11—H11C	109.5
O5—V4—V5^ii	135.13 (5)	H11B—C11—H11C	109.5
O8^i—V4—V5^ii	32.02 (3)	N1—C12—H12A	109.5
O8—V4—V5^ii	82.35 (3)	N1—C12—H12B	109.5
O7—V4—V5^ii	86.97 (3)	H12A—C12—H12B	109.5
O7^i—V4—V5^ii	123.83 (3)	N1—C12—H12C	109.5
O9^iii—V4—V5^ii	48.37 (3)	H12A—C12—H12C	109.5
V2—V4—V5^ii	119.596 (11)	H12B—C12—H12C	109.5
O4—V2—O6—V5^i	−174.84 (6)	O12—V5—O10—V5^i	−178.86 (8)
O6^i—V2—O6—V5^i	−68.97 (7)	O8^iii—V5—O10—V5^i	−74.39 (8)
O7^i—V2—O6—V5^i	86.96 (6)	O6^i—V5—O10—V5^i	79.02 (8)
O7—V2—O6—V5^i	35.96 (13)	O11—V5—O10—V5^i	8.1 (2)
O9—V2—O6—V5^i	11.32 (5)	O9—V5—O10—V5^i	3.67 (8)
V4—V2—O6—V5^i	87.13 (6)	V3—V5—O10—V5^i	4.14 (11)
V5—V2—O6—V5^i	−37.34 (5)	V4^iii—V5—O10—V5^i	−43.77 (7)
O5—V4—O8—V5^iii	174.45 (7)	V2—V5—O10—V5^i	48.91 (7)
O8^i—V4—O8—V5^iii	69.96 (7)	O11^ii—V3—O11—V5	−178.88 (6)
O7—V4—O8—V5^iii	−26.63 (13)	O7—V3—O11—V5	81.71 (5)
O7^i—V4—O8—V5^iii	−84.41 (6)	O7^ii—V3—O11—V5	−79.19 (5)
O9^iii—V4—O8—V5^iii	−9.15 (5)	O9—V3—O11—V5	1.87 (5)
V2—V4—O8—V5^iii	−82.75 (6)	O9^iii—V3—O11—V5	−1.9 (2)
V5^ii—V4—O8—V5^iii	39.78 (5)	V5^ii—V3—O11—V5	179.893 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O11^iv	0.76 (2)	1.97 (2)	2.7199 (14)	168 (2)
O2—H2A···O7^iv	0.72 (2)	2.04 (2)	2.7457 (15)	167 (2)
O2—H2B···O3^v	0.78 (2)	2.05 (2)	2.8295 (18)	178 (2)
O3—H3A···O6^v	0.74 (3)	1.92 (3)	2.6573 (16)	174 (3)
O3—H3B···O13	0.87 (3)	1.91 (3)	2.737 (3)	158 (3)
C10—H10A···O11^vi	0.96	2.51	3.362 (2)	148
C10—H10B···O11^vii	0.96	2.51	3.362 (2)	148
C10—H10C···O2^viii	0.96	2.58	3.370 (3)	139
C10—H10C···O2^ix	0.96	2.57	3.370 (3)	141
C11—H11A···O8^x	0.96	2.48	3.384 (3)	156
C12—H12A···O12^vi	0.96	2.60	3.474 (4)	152
C12—H12C···O12^vii	0.96	2.59	3.474 (4)	153

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

(Compound-B) Bis{[tris(hydroxymethyl)methyl]ammonium} decaaquadi-µ₄oxido-tetra-µ₃-oxido-hexadeca-µ₂-oxido-hexaoxidodimanganesedecavanadate dihydrate

Crystal data

(C4H12NO3)2[Mn2V10O28(H2O)10]·2H2O	F(000) = 3032
Mr = 1527.76	Dx = 2.373 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.3147 (8) Å	Cell parameters from 38099 reflections
b = 9.7733 (4) Å	θ = 3.0–25.4°
c = 22.7952 (10) Å	µ = 2.78 mm^−1
β = 96.392 (1)°	T = 295 K
V = 4276.3 (3) Å^3	Plate, yellow
Z = 4	0.49 × 0.26 × 0.13 mm

Data collection

Bruker D8 Venture/Photon 100 CMOS diffractometer	3936 independent reflections
Radiation source: fine-focus sealed tube	3280 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 10.4167 pixels mm^-1	θmax = 25.5°, θmin = 2.9°
ϕ and ω scans	h = −23→23
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −11→11
Tmin = 0.542, Tmax = 0.745	l = −27→27
71752 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: mixed
wR(F^2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0062P)^2 + 110.7865P] where P = (Fo^2 + 2Fc^2)/3
3936 reflections	(Δ/σ)max < 0.001
385 parameters	Δρmax = 0.78 e Å^−3
6 restraints	Δρmin = −1.11 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.80093 (5)	0.43409 (10)	0.18078 (4)	0.0239 (2)
V2	0.60396 (5)	0.43006 (10)	0.17920 (4)	0.0172 (2)
V3	0.62652 (5)	0.43454 (11)	0.31542 (4)	0.0182 (2)
V4	0.47896 (5)	0.58914 (11)	0.11421 (5)	0.0226 (3)
V5	0.47615 (5)	0.27690 (11)	0.11376 (5)	0.0222 (2)
V6	0.5000	0.59971 (13)	0.2500	0.0165 (3)
V7	0.5000	0.26656 (14)	0.2500	0.0153 (3)
O1	0.6885 (2)	0.4257 (4)	0.17944 (18)	0.0228 (9)
O2	0.7094 (2)	0.4358 (5)	0.31283 (18)	0.0239 (9)
O3	0.5769 (2)	0.5689 (4)	0.12912 (18)	0.0223 (9)
O4	0.5757 (2)	0.2948 (4)	0.12929 (18)	0.0195 (9)
O5	0.59743 (19)	0.5594 (4)	0.24810 (17)	0.0185 (8)
O6	0.59724 (18)	0.3057 (4)	0.24851 (17)	0.0148 (8)
O7	0.6131 (2)	0.5718 (4)	0.36695 (18)	0.0234 (9)
O8	0.6144 (2)	0.2967 (4)	0.36707 (18)	0.0220 (9)
O9	0.4718 (3)	0.7085 (5)	0.0667 (2)	0.0362 (12)
O10	0.4714 (2)	0.4332 (5)	0.06979 (18)	0.0255 (9)
O11	0.4680 (2)	0.1569 (5)	0.0664 (2)	0.0324 (11)
O12	0.4913 (2)	0.7043 (4)	0.19037 (19)	0.0251 (10)
O13	0.49147 (19)	0.4337 (4)	0.19135 (17)	0.0157 (8)
O14	0.4907 (2)	0.1636 (4)	0.18997 (18)	0.0186 (9)
O1W	0.9115 (3)	0.4350 (7)	0.1854 (4)	0.056 (2)
O2W	0.8106 (3)	0.2701 (6)	0.2493 (2)	0.0282 (12)
O3W	0.7972 (3)	0.2741 (5)	0.1120 (2)	0.0260 (10)
O4W	0.8094 (3)	0.5982 (5)	0.2475 (2)	0.0255 (10)
O5W	0.7904 (4)	0.5909 (8)	0.1149 (3)	0.0463 (17)
H1A	0.929 (6)	0.497 (12)	0.182 (5)	0.08 (4)*
H1B	0.936 (4)	0.383 (8)	0.187 (3)	0.015 (19)*
H2A	0.832 (4)	0.227 (8)	0.248 (3)	0.01 (2)*
H2B	0.820 (5)	0.297 (10)	0.286 (4)	0.06 (3)*
H3A	0.820 (5)	0.220 (10)	0.119 (4)	0.05 (3)*
H3B	0.799 (4)	0.295 (8)	0.075 (4)	0.03 (2)*
H4A	0.841 (6)	0.653 (11)	0.245 (4)	0.08 (4)*
H4B	0.775 (5)	0.636 (9)	0.245 (4)	0.04 (3)*
H5A	0.812 (6)	0.626 (12)	0.119 (5)	0.06 (5)*
H5B	0.774 (7)	0.564 (14)	0.082 (6)	0.11 (5)*
N1	0.8230 (3)	0.5979 (5)	0.3845 (2)	0.0246 (12)
H1C	0.7881	0.6509	0.3932	0.029*
H1D	0.8090	0.5474	0.3529	0.029*
H1E	0.8588	0.6500	0.3770	0.029*
C10	0.8451 (3)	0.5061 (7)	0.4357 (3)	0.0275 (14)
C11	0.8775 (4)	0.5944 (7)	0.4861 (3)	0.0341 (16)
H11B	0.8885	0.5386	0.5211	0.041*
H11C	0.9205	0.6343	0.4758	0.041*
O11A	0.8302 (3)	0.7007 (6)	0.4981 (3)	0.0517 (15)
H11A	0.8462	0.7751	0.4899	0.078*
C12	0.8985 (4)	0.4081 (8)	0.4159 (4)	0.047 (2)
H12B	0.9374	0.4588	0.4034	0.056*
H12C	0.9159	0.3489	0.4484	0.056*
O12A	0.8665 (4)	0.3279 (6)	0.3681 (3)	0.0591 (18)
H12A	0.8860	0.2534	0.3679	0.089*
C13	0.7796 (5)	0.4328 (9)	0.4506 (4)	0.050 (2)
H13C	0.7442	0.4997	0.4573	0.061*	0.694 (13)
H13D	0.7615	0.3755	0.4177	0.061*	0.694 (13)
H13E	0.7442	0.4383	0.4170	0.061*	0.306 (13)
H13F	0.7902	0.3369	0.4580	0.061*	0.306 (13)
O13A	0.7939 (7)	0.3553 (10)	0.4991 (4)	0.073 (4)	0.694 (13)
H13A	0.8064	0.2791	0.4896	0.110*	0.694 (13)
O13B	0.7539 (9)	0.487 (3)	0.4988 (9)	0.062 (8)	0.306 (13)
H13B	0.73 (2)	0.44 (3)	0.510 (12)	0.093*	0.306 (13)
O6WA	0.6367 (5)	0.4696 (11)	0.0226 (4)	0.051 (3)	0.694 (13)
H6A	0.617 (6)	0.465 (16)	0.053 (3)	0.077*	0.694 (13)
H6B	0.612 (6)	0.509 (16)	−0.003 (4)	0.077*	0.694 (13)
O6WB	0.6316 (9)	0.596 (3)	0.0209 (8)	0.046 (6)	0.306 (13)
H6C	0.627 (13)	0.58 (4)	0.055 (4)	0.069*	0.306 (13)
H6D	0.595 (8)	0.58 (3)	0.000 (8)	0.069*	0.306 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0168 (4)	0.0170 (5)	0.0383 (6)	−0.0012 (4)	0.0049 (4)	−0.0002 (4)
V2	0.0119 (4)	0.0152 (5)	0.0248 (5)	0.0002 (4)	0.0037 (4)	0.0007 (4)
V3	0.0119 (4)	0.0167 (5)	0.0258 (5)	−0.0004 (4)	0.0012 (4)	−0.0009 (4)
V4	0.0206 (5)	0.0193 (6)	0.0279 (6)	0.0007 (4)	0.0024 (4)	0.0071 (4)
V5	0.0191 (5)	0.0225 (6)	0.0252 (6)	−0.0010 (4)	0.0029 (4)	−0.0040 (4)
V6	0.0137 (7)	0.0058 (6)	0.0301 (8)	0.000	0.0025 (6)	0.000
V7	0.0103 (6)	0.0120 (7)	0.0240 (7)	0.000	0.0029 (5)	0.000
O1	0.0148 (19)	0.022 (2)	0.032 (2)	0.0009 (18)	0.0057 (17)	0.0007 (19)
O2	0.0143 (19)	0.027 (2)	0.030 (2)	0.0033 (19)	0.0016 (17)	−0.0001 (19)
O3	0.020 (2)	0.021 (2)	0.027 (2)	−0.0017 (19)	0.0046 (17)	0.0027 (19)
O4	0.017 (2)	0.016 (2)	0.026 (2)	0.0000 (17)	0.0064 (17)	−0.0027 (18)
O5	0.0172 (19)	0.014 (2)	0.024 (2)	0.0007 (17)	0.0026 (16)	−0.0001 (17)
O6	0.0073 (17)	0.0087 (19)	0.029 (2)	0.0015 (15)	0.0031 (15)	0.0002 (16)
O7	0.020 (2)	0.021 (2)	0.028 (2)	−0.0034 (19)	0.0000 (17)	−0.0054 (19)
O8	0.016 (2)	0.020 (2)	0.029 (2)	0.0006 (17)	0.0030 (17)	0.0019 (18)
O9	0.035 (3)	0.032 (3)	0.041 (3)	0.000 (2)	0.002 (2)	0.019 (2)
O10	0.022 (2)	0.031 (2)	0.023 (2)	0.000 (2)	0.0011 (17)	0.005 (2)
O11	0.027 (2)	0.036 (3)	0.034 (3)	−0.004 (2)	0.002 (2)	−0.009 (2)
O12	0.022 (2)	0.019 (2)	0.034 (3)	0.0004 (19)	0.0054 (18)	0.0065 (19)
O13	0.0134 (18)	0.0105 (18)	0.023 (2)	0.0000 (17)	0.0030 (15)	0.0035 (16)
O14	0.0148 (19)	0.0076 (18)	0.034 (2)	−0.0003 (16)	0.0046 (17)	−0.0011 (17)
O1W	0.016 (3)	0.014 (3)	0.139 (7)	0.002 (3)	0.013 (3)	0.002 (3)
O2W	0.031 (3)	0.021 (3)	0.033 (3)	0.010 (2)	0.005 (2)	0.000 (2)
O3W	0.026 (3)	0.017 (2)	0.035 (3)	0.002 (2)	0.004 (2)	0.001 (2)
O4W	0.015 (2)	0.018 (2)	0.045 (3)	−0.003 (2)	0.007 (2)	−0.004 (2)
O5W	0.055 (4)	0.038 (4)	0.046 (4)	−0.014 (3)	0.003 (3)	0.007 (3)
N1	0.024 (3)	0.015 (3)	0.035 (3)	−0.004 (2)	0.002 (2)	−0.001 (2)
C10	0.032 (4)	0.020 (3)	0.030 (3)	0.001 (3)	0.001 (3)	0.002 (3)
C11	0.037 (4)	0.034 (4)	0.031 (4)	−0.002 (3)	0.003 (3)	−0.004 (3)
O11A	0.082 (4)	0.033 (3)	0.039 (3)	0.010 (3)	0.002 (3)	−0.013 (3)
C12	0.049 (5)	0.041 (5)	0.046 (5)	0.018 (4)	−0.012 (4)	−0.008 (4)
O12A	0.082 (5)	0.043 (3)	0.046 (3)	0.038 (3)	−0.020 (3)	−0.021 (3)
C13	0.069 (6)	0.040 (5)	0.045 (5)	−0.030 (5)	0.020 (4)	−0.005 (4)
O13A	0.122 (10)	0.053 (6)	0.041 (5)	−0.038 (7)	−0.005 (5)	0.013 (4)
O13B	0.010 (8)	0.13 (2)	0.049 (11)	−0.012 (10)	0.010 (7)	−0.020 (13)
O6WA	0.059 (6)	0.061 (7)	0.035 (5)	0.007 (5)	0.009 (4)	0.002 (4)
O6WB	0.024 (9)	0.081 (18)	0.034 (10)	−0.008 (10)	0.007 (7)	0.001 (10)

Geometric parameters (Å, º)

Mn1—O1W	2.126 (5)	V7—O6	1.921 (4)
Mn1—O5W	2.139 (7)	V7—O6^i	1.921 (4)
Mn1—O1	2.169 (4)	V7—O13	2.106 (4)
Mn1—O4W	2.204 (5)	V7—O13^i	2.106 (4)
Mn1—O3W	2.209 (5)	V7—V5^i	3.0900 (11)
Mn1—O2W	2.231 (5)	O7—V4^i	1.884 (4)
V2—O1	1.634 (4)	O8—V5^i	1.860 (4)
V2—O4	1.789 (4)	O13—V3^i	2.267 (4)
V2—O3	1.812 (4)	O1W—H1A	0.70 (12)
V2—O6	2.009 (4)	O1W—H1B	0.70 (7)
V2—O5	2.031 (4)	O2W—H2A	0.60 (7)
V2—O13	2.221 (4)	O2W—H2B	0.87 (10)
V2—V3	3.0875 (14)	O3W—H3A	0.70 (9)
V2—V4	3.1056 (14)	O3W—H3B	0.88 (8)
V3—O2	1.609 (4)	O4W—H4A	0.82 (11)
V3—O7	1.821 (4)	O4W—H4B	0.76 (9)
V3—O8	1.821 (4)	O5W—H5A	0.55 (11)
V3—O5	1.992 (4)	O5W—H5B	0.83 (14)
V3—O6	2.010 (4)	N1—C10	1.496 (8)
V3—O13^i	2.267 (4)	N1—H1C	0.8900
V3—V5^i	3.1025 (14)	N1—H1D	0.8900
V4—O9	1.587 (5)	N1—H1E	0.8900
V4—O10	1.826 (5)	C10—C12	1.513 (10)
V4—O7^i	1.884 (4)	C10—C11	1.517 (9)
V4—O3	1.895 (4)	C10—C13	1.525 (10)
V4—O12	2.061 (5)	C11—O11A	1.431 (9)
V4—O13	2.316 (4)	C11—H11B	0.9700
V4—V5	3.0521 (15)	C11—H11C	0.9700
V4—V6	3.0786 (11)	O11A—H11A	0.8200
V5—O11	1.590 (5)	C12—O12A	1.426 (9)
V5—O10	1.824 (5)	C12—H12B	0.9700
V5—O8^i	1.860 (4)	C12—H12C	0.9700
V5—O4	1.925 (4)	O12A—H12A	0.8200
V5—O14	2.053 (4)	C13—O13A	1.343 (12)
V5—O13	2.334 (4)	C13—O13B	1.36 (2)
V5—V7	3.0900 (11)	C13—H13C	0.9700
V5—V3^i	3.1025 (14)	C13—H13D	0.9700
V6—O12	1.694 (4)	C13—H13E	0.9700
V6—O12^i	1.694 (4)	C13—H13F	0.9700
V6—O5	1.928 (4)	O13A—H13A	0.8200
V6—O5^i	1.928 (4)	O13B—H13B	0.8 (4)
V6—O13^i	2.097 (4)	O6WA—H6A	0.82 (2)
V6—O13	2.097 (4)	O6WA—H6B	0.82 (2)
V6—V4^i	3.0786 (11)	O6WB—H6C	0.82 (2)
V7—O14	1.692 (4)	O6WB—H6D	0.82 (2)
V7—O14^i	1.692 (4)
O1W—Mn1—O5W	92.8 (3)	O12—V6—O12^i	105.8 (3)
O1W—Mn1—O1	177.2 (2)	O12—V6—O5	96.61 (19)
O5W—Mn1—O1	90.0 (3)	O12^i—V6—O5	97.57 (19)
O1W—Mn1—O4W	88.0 (2)	O12—V6—O5^i	97.57 (19)
O5W—Mn1—O4W	87.5 (3)	O12^i—V6—O5^i	96.61 (19)
O1—Mn1—O4W	91.99 (18)	O5—V6—O5^i	156.4 (3)
O1W—Mn1—O3W	89.5 (2)	O12—V6—O13^i	166.4 (2)
O5W—Mn1—O3W	90.9 (3)	O12^i—V6—O13^i	87.80 (18)
O1—Mn1—O3W	90.57 (17)	O5—V6—O13^i	81.29 (16)
O4W—Mn1—O3W	177.02 (19)	O5^i—V6—O13^i	80.50 (16)
O1W—Mn1—O2W	87.9 (3)	O12—V6—O13	87.80 (18)
O5W—Mn1—O2W	179.3 (3)	O12^i—V6—O13	166.4 (2)
O1—Mn1—O2W	89.35 (19)	O5—V6—O13	80.50 (16)
O4W—Mn1—O2W	92.61 (19)	O5^i—V6—O13	81.28 (16)
O3W—Mn1—O2W	88.9 (2)	O13^i—V6—O13	78.6 (2)
O1—V2—O4	102.5 (2)	O12—V6—V4	39.04 (15)
O1—V2—O3	103.9 (2)	O12^i—V6—V4	144.81 (16)
O4—V2—O3	96.10 (18)	O5—V6—V4	89.45 (12)
O1—V2—O6	97.69 (18)	O5^i—V6—V4	89.76 (12)
O4—V2—O6	90.65 (17)	O13^i—V6—V4	127.39 (11)
O3—V2—O6	155.37 (17)	O13—V6—V4	48.76 (10)
O1—V2—O5	99.30 (19)	O12—V6—V4^i	144.81 (16)
O4—V2—O5	155.64 (17)	O12^i—V6—V4^i	39.04 (15)
O3—V2—O5	89.03 (18)	O5—V6—V4^i	89.76 (12)
O6—V2—O5	75.72 (15)	O5^i—V6—V4^i	89.45 (12)
O1—V2—O13	172.67 (19)	O13^i—V6—V4^i	48.76 (10)
O4—V2—O13	81.85 (16)	O13—V6—V4^i	127.39 (11)
O3—V2—O13	81.31 (16)	V4—V6—V4^i	176.15 (6)
O6—V2—O13	76.23 (14)	O14—V7—O14^i	107.0 (3)
O5—V2—O13	75.39 (15)	O14—V7—O6	96.90 (17)
O1—V2—V3	88.16 (15)	O14^i—V7—O6	96.68 (17)
O4—V2—V3	130.47 (14)	O14—V7—O6^i	96.68 (17)
O3—V2—V3	128.43 (14)	O14^i—V7—O6^i	96.90 (17)
O6—V2—V3	39.82 (11)	O6—V7—O6^i	157.1 (2)
O5—V2—V3	39.40 (12)	O14—V7—O13	87.36 (17)
O13—V2—V3	84.54 (10)	O14^i—V7—O13	165.61 (18)
O1—V2—V4	137.61 (16)	O6—V7—O13	80.91 (15)
O4—V2—V4	84.31 (13)	O6^i—V7—O13	81.34 (15)
O3—V2—V4	33.93 (13)	O14—V7—O13^i	165.61 (18)
O6—V2—V4	124.28 (11)	O14^i—V7—O13^i	87.36 (17)
O5—V2—V4	86.88 (11)	O6—V7—O13^i	81.34 (15)
O13—V2—V4	48.09 (10)	O6^i—V7—O13^i	80.91 (15)
V3—V2—V4	119.20 (4)	O13—V7—O13^i	78.3 (2)
O2—V3—O7	103.4 (2)	O14—V7—V5	38.37 (13)
O2—V3—O8	103.3 (2)	O14^i—V7—V5	145.37 (15)
O7—V3—O8	95.17 (19)	O6—V7—V5	90.71 (12)
O2—V3—O5	99.42 (19)	O6^i—V7—V5	88.54 (12)
O7—V3—O5	89.87 (18)	O13—V7—V5	49.01 (11)
O8—V3—O5	154.91 (18)	O13^i—V7—V5	127.24 (12)
O2—V3—O6	100.03 (19)	O14—V7—V5^i	145.37 (15)
O7—V3—O6	154.59 (17)	O14^i—V7—V5^i	38.37 (13)
O8—V3—O6	88.95 (18)	O6—V7—V5^i	88.54 (12)
O5—V3—O6	76.57 (15)	O6^i—V7—V5^i	90.71 (12)
O2—V3—O13^i	174.03 (19)	O13—V7—V5^i	127.24 (12)
O7—V3—O13^i	80.37 (16)	O13^i—V7—V5^i	49.01 (11)
O8—V3—O13^i	80.84 (16)	V5—V7—V5^i	176.25 (7)
O5—V3—O13^i	75.79 (15)	V2—O1—Mn1	176.3 (3)
O6—V3—O13^i	75.54 (14)	V2—O3—V4	113.8 (2)
O2—V3—V2	89.59 (15)	V2—O4—V5	114.3 (2)
O7—V3—V2	130.18 (15)	V6—O5—V3	107.48 (19)
O8—V3—V2	128.75 (14)	V6—O5—V2	106.83 (18)
O5—V3—V2	40.33 (12)	V3—O5—V2	100.27 (18)
O6—V3—V2	39.80 (11)	V7—O6—V2	106.44 (18)
O13^i—V3—V2	84.45 (10)	V7—O6—V3	107.72 (18)
O2—V3—V5^i	136.00 (16)	V2—O6—V3	100.38 (17)
O7—V3—V5^i	83.42 (14)	V3—O7—V4^i	114.8 (2)
O8—V3—V5^i	32.94 (13)	V3—O8—V5^i	114.9 (2)
O5—V3—V5^i	124.28 (12)	V5—O10—V4	113.5 (2)
O6—V3—V5^i	86.64 (11)	V6—O12—V4	109.8 (2)
O13^i—V3—V5^i	48.52 (10)	V6—O13—V7	101.55 (16)
V2—V3—V5^i	119.30 (4)	V6—O13—V2	94.78 (15)
O9—V4—O10	103.9 (2)	V7—O13—V2	93.34 (14)
O9—V4—O7^i	102.1 (2)	V6—O13—V3^i	92.73 (14)
O10—V4—O7^i	91.83 (19)	V7—O13—V3^i	93.04 (14)
O9—V4—O3	102.0 (2)	V2—O13—V3^i	168.98 (19)
O10—V4—O3	91.66 (19)	V6—O13—V4	88.32 (14)
O7^i—V4—O3	154.04 (18)	V7—O13—V4	170.1 (2)
O9—V4—O12	99.6 (2)	V2—O13—V4	86.37 (13)
O10—V4—O12	156.56 (19)	V3^i—O13—V4	85.80 (13)
O7^i—V4—O12	83.15 (18)	V6—O13—V5	170.2 (2)
O3—V4—O12	83.47 (18)	V7—O13—V5	88.06 (14)
O9—V4—O13	173.7 (2)	V2—O13—V5	86.46 (13)
O10—V4—O13	82.46 (17)	V3^i—O13—V5	84.79 (13)
O7^i—V4—O13	77.84 (16)	V4—O13—V5	82.05 (13)
O3—V4—O13	77.14 (16)	V7—O14—V5	110.9 (2)
O12—V4—O13	74.10 (15)	Mn1—O1W—H1A	120 (9)
O9—V4—V5	137.1 (2)	Mn1—O1W—H1B	132 (6)
O10—V4—V5	33.24 (13)	H1A—O1W—H1B	107 (10)
O7^i—V4—V5	83.91 (14)	Mn1—O2W—H2A	119 (7)
O3—V4—V5	85.01 (14)	Mn1—O2W—H2B	116 (6)
O12—V4—V5	123.32 (13)	H2A—O2W—H2B	101 (9)
O13—V4—V5	49.23 (10)	Mn1—O3W—H3A	115 (8)
O9—V4—V6	130.8 (2)	Mn1—O3W—H3B	121 (5)
O10—V4—V6	125.37 (14)	H3A—O3W—H3B	107 (9)
O7^i—V4—V6	78.24 (13)	Mn1—O4W—H4A	115 (7)
O3—V4—V6	78.80 (13)	Mn1—O4W—H4B	108 (6)
O12—V4—V6	31.19 (12)	H4A—O4W—H4B	109 (9)
O13—V4—V6	42.92 (10)	Mn1—O5W—H5A	108 (10)
V5—V4—V6	92.13 (4)	Mn1—O5W—H5B	114 (9)
O9—V4—V2	134.20 (18)	H5A—O5W—H5B	126 (10)
O10—V4—V2	81.76 (13)	C10—N1—H1C	109.5
O7^i—V4—V2	123.37 (13)	C10—N1—H1D	109.5
O3—V4—V2	32.27 (13)	H1C—N1—H1D	109.5
O12—V4—V2	81.98 (12)	C10—N1—H1E	109.5
O13—V4—V2	45.54 (9)	H1C—N1—H1E	109.5
V5—V4—V2	60.90 (3)	H1D—N1—H1E	109.5
V6—V4—V2	61.87 (3)	N1—C10—C12	107.0 (6)
O11—V5—O10	104.4 (2)	N1—C10—C11	107.9 (5)
O11—V5—O8^i	102.2 (2)	C12—C10—C11	110.4 (6)
O10—V5—O8^i	92.89 (19)	N1—C10—C13	106.5 (6)
O11—V5—O4	102.3 (2)	C12—C10—C13	112.3 (7)
O10—V5—O4	90.75 (18)	C11—C10—C13	112.4 (6)
O8^i—V5—O4	153.41 (18)	O11A—C11—C10	109.8 (6)
O11—V5—O14	99.8 (2)	O11A—C11—H11B	109.7
O10—V5—O14	155.59 (19)	C10—C11—H11B	109.7
O8^i—V5—O14	84.32 (17)	O11A—C11—H11C	109.7
O4—V5—O14	81.60 (17)	C10—C11—H11C	109.7
O11—V5—O13	173.5 (2)	H11B—C11—H11C	108.2
O10—V5—O13	82.00 (17)	C11—O11A—H11A	109.5
O8^i—V5—O13	78.27 (16)	O12A—C12—C10	108.9 (6)
O4—V5—O13	76.18 (15)	O12A—C12—H12B	109.9
O14—V5—O13	73.68 (14)	C10—C12—H12B	109.9
O11—V5—V4	137.74 (19)	O12A—C12—H12C	109.9
O10—V5—V4	33.29 (14)	C10—C12—H12C	109.9
O8^i—V5—V4	84.94 (14)	H12B—C12—H12C	108.3
O4—V5—V4	83.76 (13)	C12—O12A—H12A	109.5
O14—V5—V4	122.39 (12)	O13A—C13—C10	110.4 (9)
O13—V5—V4	48.72 (10)	O13B—C13—C10	112.4 (11)
O11—V5—V7	130.60 (19)	O13A—C13—H13C	109.6
O10—V5—V7	124.92 (15)	C10—C13—H13C	109.6
O8^i—V5—V7	78.82 (13)	O13A—C13—H13D	109.6
O4—V5—V7	77.53 (12)	C10—C13—H13D	109.6
O14—V5—V7	30.77 (11)	H13C—C13—H13D	108.1
O13—V5—V7	42.93 (10)	O13B—C13—H13E	109.1
V4—V5—V7	91.65 (4)	C10—C13—H13E	109.1
O11—V5—V3^i	134.32 (17)	O13B—C13—H13F	109.1
O10—V5—V3^i	82.75 (14)	C10—C13—H13F	109.1
O8^i—V5—V3^i	32.17 (13)	H13E—C13—H13F	107.8
O4—V5—V3^i	122.87 (13)	C13—O13A—H13A	109.5
O14—V5—V3^i	82.10 (11)	C13—O13B—H13B	109.5
O13—V5—V3^i	46.69 (9)	H6A—O6WA—H6B	110 (4)
V4—V5—V3^i	60.92 (3)	H6C—O6WB—H6D	110 (4)
V7—V5—V3^i	61.69 (3)
O1—V2—O3—V4	174.8 (2)	O14—V5—O10—V4	−6.4 (6)
O4—V2—O3—V4	70.3 (2)	O13—V5—O10—V4	−1.5 (2)
O6—V2—O3—V4	−34.8 (6)	V7—V5—O10—V4	−2.1 (3)
O5—V2—O3—V4	−85.9 (2)	V3^i—V5—O10—V4	45.64 (19)
O13—V2—O3—V4	−10.5 (2)	O9—V4—O10—V5	−178.9 (3)
V3—V2—O3—V4	−86.4 (2)	O7^i—V4—O10—V5	−76.0 (2)
O9—V4—O3—V2	−176.2 (3)	O3—V4—O10—V5	78.3 (2)
O10—V4—O3—V2	−71.7 (2)	O12—V4—O10—V5	1.0 (6)
O7^i—V4—O3—V2	25.9 (6)	O13—V4—O10—V5	1.5 (2)
O12—V4—O3—V2	85.3 (2)	V6—V4—O10—V5	0.9 (3)
O13—V4—O3—V2	10.2 (2)	V2—V4—O10—V5	47.49 (19)
V5—V4—O3—V2	−39.1 (2)	O12^i—V6—O12—V4	−179.3 (3)
V6—V4—O3—V2	54.1 (2)	O5—V6—O12—V4	80.9 (2)
O1—V2—O4—V5	−176.1 (2)	O5^i—V6—O12—V4	−80.2 (2)
O3—V2—O4—V5	−70.4 (2)	O13^i—V6—O12—V4	0.7 (9)
O6—V2—O4—V5	85.9 (2)	O13—V6—O12—V4	0.73 (19)
O5—V2—O4—V5	30.8 (6)	V4^i—V6—O12—V4	179.93 (3)
O13—V2—O4—V5	9.9 (2)	O14^i—V7—O14—V5	178.4 (3)
V3—V2—O4—V5	85.5 (2)	O6—V7—O14—V5	−82.4 (2)
V4—V2—O4—V5	−38.54 (19)	O6^i—V7—O14—V5	79.1 (2)
O2—V3—O7—V4^i	−174.8 (2)	O13—V7—O14—V5	−1.86 (18)
O8—V3—O7—V4^i	−69.9 (2)	O13^i—V7—O14—V5	−0.3 (8)
O5—V3—O7—V4^i	85.5 (2)	V5^i—V7—O14—V5	−179.85 (2)
O6—V3—O7—V4^i	28.6 (6)	N1—C10—C11—O11A	54.2 (7)
O13^i—V3—O7—V4^i	9.9 (2)	C12—C10—C11—O11A	170.8 (6)
V2—V3—O7—V4^i	84.1 (3)	C13—C10—C11—O11A	−63.0 (8)
V5^i—V3—O7—V4^i	−39.0 (2)	N1—C10—C12—O12A	−62.1 (8)
O2—V3—O8—V5^i	174.5 (2)	C11—C10—C12—O12A	−179.3 (6)
O7—V3—O8—V5^i	69.4 (2)	C13—C10—C12—O12A	54.4 (9)
O5—V3—O8—V5^i	−31.4 (6)	N1—C10—C13—O13A	−175.5 (8)
O6—V3—O8—V5^i	−85.5 (2)	C12—C10—C13—O13A	67.7 (10)
O13^i—V3—O8—V5^i	−9.9 (2)	C11—C10—C13—O13A	−57.5 (10)
V2—V3—O8—V5^i	−85.1 (2)	N1—C10—C13—O13B	−102.3 (14)
O11—V5—O10—V4	179.6 (2)	C12—C10—C13—O13B	140.9 (14)
O8^i—V5—O10—V4	76.2 (2)	C11—C10—C13—O13B	15.8 (15)
O4—V5—O10—V4	−77.4 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O14^ii	0.70 (12)	2.01 (12)	2.703 (7)	167 (12)
O1W—H1B···O12^iii	0.70 (7)	2.04 (8)	2.727 (8)	169 (8)
O2W—H2A···O5^iv	0.60 (7)	2.12 (7)	2.716 (7)	172 (9)
O2W—H2B···O12A	0.87 (10)	2.01 (10)	2.858 (8)	164 (8)
O3W—H3A···O7^iv	0.70 (9)	1.94 (9)	2.636 (7)	176 (10)
O3W—H3B···O11A^v	0.88 (8)	1.91 (8)	2.752 (8)	160 (7)
O4W—H4A···O6^vi	0.82 (11)	1.90 (11)	2.708 (6)	167 (10)
O4W—H4B···O2W^vi	0.76 (9)	2.12 (9)	2.871 (7)	169 (9)
O5W—H5A···O8^vi	0.55 (11)	2.18 (11)	2.725 (10)	170 (16)
O5W—H5B···O13A^v	0.83 (14)	2.12 (13)	2.699 (12)	127 (12)
O5W—H5B···O13B^v	0.83 (14)	1.95 (14)	2.77 (2)	168 (13)
N1—H1C···O3W^vi	0.89	2.03	2.898 (7)	164
N1—H1D···O2	0.89	2.31	3.032 (7)	138
N1—H1D···O4W	0.89	2.45	3.105 (7)	130
N1—H1E···O4^vi	0.89	1.91	2.787 (6)	166
C11—H11C···O11^vi	0.97	2.46	3.392 (9)	160
O11A—H11A···O6WA^vi	0.82	1.96	2.758 (12)	166
O12A—H12A···O3^iv	0.82	1.94	2.756 (7)	174
C13—H13E···O2	0.97	2.40	3.280 (10)	151
O13B—H13B···O6WB^vii	0.77	1.92	2.60 (2)	148
O6WA—H6A···O3	0.82 (2)	2.23 (9)	2.966 (9)	150 (15)
O6WA—H6B···O10^viii	0.82 (2)	2.16 (5)	2.952 (10)	165 (17)
O6WB—H6C···O3	0.82 (2)	2.03 (13)	2.802 (17)	156 (29)
O6WB—H6D···O10^viii	0.82 (2)	1.93 (8)	2.720 (19)	161 (24)

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