Bis[2-(2-hydroxy­ethyl)pyridinium] μ-deca­vanadato-bis­[penta­aqua­manganate(II)] tetra­hydrate

The structure of the title compound, (C₇H₁₀NO)₂[Mn₂V₁₀O₂₈(H₂O)₁₀]·4H₂O or (C₅H₄NHCH₂CH₂OH)₂[{Mn(H₂O)₅}₂V₁₀O₂₈]·4H₂O, at 293 (2) K has triclinic (P) symmetry. The asymmetric unit consists of one half of a deca­vanadate anion of C_i symmetry, one [Mn(H₂O)₅]²⁺ group, one 2-(2-hydroxy­ethyl)pyridinium cation and two solvent water mol­ecules. The deca­vanadate ion bridges between two [Mn(H₂O)₅]²⁺ groups, thus forming a dodeca­nuclear complex unit. Complex units are connected via a hydrogen-bonding network, forming supra­molecular layers lying in the (001) plane. Cations and solvent water mol­ecules are located between these layers.

S1. Comment

Over the past few years, the role of vanadium compounds in living organisms has been intensively studied (Rehder, 2008). The biological activitiy of decavanadate, for example, in the modulation of ionic channels, calcium homeostasis and insulin mimetics, has been described by Aureliano & Madeira (1998).

Decavanadate ions serve as building blocks for supramolecular assemblies (da Silva et al., 2003) but their role as ligands coordinated to metal centres has only very recently been reported. As donor atoms [they?] can serve either terminal or bridging oxygen atoms (Fig. 1). In the title compound, (I) (Fig. 2), the bridging doubly monodentate V₁₀O₂₈^6– anion of C_i symmetry (although its symmetry is very close to the D_2h point group) is coordinated via centrosymmetrically arranged `out-of-the-main-plane' [plane in the V<sub>10</sub>O<sub>28</sub><sup>6–</sup> anion formed by V1, V2, V3, V1<sup>i</sup>, V2<sup>i</sup>, V3<sup>i</sup> atoms; symmetry code: (i) 1 – x, 2 – y, 1 – z] terminal O atoms O1 (F) to the [Mn(H<sub>2</sub>O)<sub>5</sub>]<sup>2+</sup> units, thus completing the octahedral coordination geometry of the Mn<sup>II</sup> atoms. This is similar to the coordination of V<sub>10</sub>O<sub>28</sub><sup>6–</sup> in [Zn(H<sub>2</sub>O)<sub>6</sub>][Zn<sub>2</sub>(H<sub>2</sub>O)<sub>10</sub>V<sub>10</sub>O<sub>28</sub>].6 H<sub>2</sub>O (Graia et al., 2008). There is also the possibility of coordination via `in-the-main-plane' lying terminal O atoms (G) (Klištincová et al., 2008) and `out-of-the-main-plane' lying µ-OV₂ bridging O atoms (C) (Li et al., 2007).

The coordination possibilities of the bridging O atoms of the B, D or E type are evidently restricted for sterical reasons.

The distance d(V5—O1) = 1.6350 (11) Å, which corresponds to the bond valence sum s = 1.59 (Brown, 1992), is slightly elongated in comparison with other V—O_t (O_t, terminal O atom) bond lengths which lie in the extremely narrow range 1.5951 (12)–1.5971 (12) Å. This elongation is somewhat larger in comparison with those [the bond lengths?] in (NH₄)₂[Cu₂(NH₃CH₂CH₂COO)₄(V₁₀O₂₈)].10H₂O (s = 1.68) (Klištincová et al., 2008) and [Zn(H₂O)₆][Zn₂(H₂O)₁₀V₁₀O₂₈].6H₂O (s = 1.63). The averaged bond lengths of the V—O_b (O_b, bridging O atom) bonds are 1.85 (11), 1.98 (4) and 2.23 (10) Å for bridging O atoms with coordination numbers two, three and six, respectively.

Mn^II has an octahedral coordination which is slightly shortened in the axial direction. The equatorial plane of the MnO₆ octahedron, given by the atoms Mn1 and O1M, O3M– O5M, is nearly parallel with the main plane of the V₁₀O₂₈^6– anion: the corresponding least-square planes form an angle 1.83 (3)°. The Mn—O distances in the equatorial plane are in the range 2.1902 (12)–2.2103 (12) Å (s = 0.32–0.34). The distance d(Mn1—O1) = 2.1630 (11) Å (s = 0.36) belongs to the bonding to the decavanadate anion and the shortest distance is d(Mn1—O2M) = 2.1420 (13) Å which corresponds to s = 0.39.

The dodecanuclear [{Mn(H₂O)₅}₂V₁₀O₂₈]^2– units are connected via a hydrogen-bonding network (Table 1) forming anionic supramolecular layers lying in the (001) plane (Fig. 3). In these layers, Mn-coordinated H₂O molecules acts as hydrogen-bond donors/acceptors and vanadate O atoms act as hydrogen-bond acceptors, forming interesting folded rings with graph set R₄⁶(16) (Etter et al., 1990; Bernstein et al., 1995) (Fig. 4) enforced by O2M—H21M···O7ⁱ and O2M—H22M···O6ⁱⁱ hydrogen bonds [symmetry codes: (i) 1 – x, 1 – y, 1 – z; (ii) 2 – x, 1 – y, 1 – z]. The negative charge of the layers is neutralized by the 2-hydroxyethylpyridinium cations lying between these layers. Cations and solvent water molecules are also involved in the extensive hydrogen-bonding network.

To evaluate the parallel-displaced π–π interaction between the pyridine rings, neighbouring least-squares planes defined by C1–C5 and N1 atoms with symmetry codes x, y, z and 2 – x, 1 – y, 2 – z were calculated. The interplanar distance R is equal to 3.47 Å and the centroid–centroid distance of the aromatic rings R_ct is 4.04 Å.

Related literature

For related literature, see: Aureliano & Madeira (1998); Bernstein et al. (1995); Brown (1992); Etter et al. (1990); Graia et al. (2008); Klištincová et al. (2008); Li et al. (2007); Nardelli (1999); Rehder (2008); da Silva et al. (2003).

S2. Experimental

To a solution of Mn(CH₃COO)₂ (0.346 g, 2 mmol) in water (20 ml), 2-hydroxyethylpyridine (0.45 ml, 4 mmol) was added. The opaque solution was stirred for 15 min and an aqueous solution of NH₄VO₃ (0.468 g, 4 mmol in 40 ml of water) was then added under [with?] immediate formation of a precipitate. The solution with the precipitate was stirred for a further 15 min and filtered. The pH of the filtrate was adjusted to 5.0 with diluted HCl; a yellow solution was obtained, to which ethanol (10 ml) was added. Orange crystals were isolated after standing for 7 d at room temperature. The compound is stable at room temperature.

The IR spectrum in KBr pellets was recorded on a FTIR Nicolet Magna 750 spectrometer. Vanadium was determined by titration with an aqueous solution of FeSO₄. C, H, N were estimated on a CHN analyser (Carlo Erba). The IR spectrum exhibits characteristic bands assigned to the organic cation (1640 m, 1620 m, 1560 m, 1540 m, 1505 m, 1050 m) and decavanadate group (970 vs, 827 s, 725 vs, 590 m). Analysis: calculated for C₁₄H₄₈N₂O₄₄Mn₂V₁₀ (found): C, 10.8 (10.6); H, 2.6 (3.1); N, 1.8 (1.7); V 32.7 (32.2).

S3. Refinement

H atoms of the cations were placed in geometrically idealized positions (C—H = 0.93 Å, N—H = 0.86 Å and O—H = 0.82 Å) and constrained to ride on their parent atoms [U_iso(H) = 1.2U_eq(C, N) and 1.5U_eq(O)]. H atoms of the water molecules were located in a difference map and refined with O—H interatomic distances restrained to 0.82 Å and H—H to 1.324 Å to obtain reasonable geometry (Nardelli, 1999), with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction Ltd, 2008); cell refinement: CrysAlis PRO (Oxford Diffraction Ltd, 2008); data reduction: CrysAlis PRO (Oxford Diffraction Ltd, 2008); program(s) used to solve structure: DIRDIF2008 (Beurskens et al., 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008) and PLATON (Spek, 2003); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures

	Fig. 1. The scheme of the decavanadate anion with idealized D2h point group geometry. A–G denote crystallographically non-equivalent O atoms, circles denote V atoms (according to da Silva et al., 2003).
	Fig. 2. The structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. The symmetry operation relating labelled atoms to unlabelled atoms is (1- x, 2 - y, 1 - z).
	Fig. 3. A view of the anionic layers packing along the a axis.
	Fig. 4. A detail of the R4^6(16) rings in the anionic chain. [Symmetry codes: (i) x, y - 1, z; (ii) 1 - x, 1 - y, 1 - z; (iii) 1 - x, 2 - y, 1 - z.]

Bis[2-(2-hydroxyethyl)pyridinium] µ-decavanadato-bis[pentaaquamanganate(II)] tetrahydrate

Crystal data

(C7H10NO)2[Mn2V10O28(H2O)10]·4H2O	Z = 1
Mr = 1567.82	F(000) = 778
Triclinic, P1	Dx = 2.267 Mg m^−3
a = 9.58016 (9) Å	Mo Kα radiation, λ = 0.7107 Å
b = 11.33329 (13) Å	Cell parameters from 16843 reflections
c = 12.07540 (17) Å	θ = 3.2–28.3°
α = 78.3429 (11)°	µ = 2.56 mm^−1
β = 74.6559 (11)°	T = 293 K
γ = 66.0748 (10)°	Prism, orange
V = 1149.02 (2) Å^3	0.28 × 0.25 × 0.15 mm

Data collection

Goniometer Xcalibur, detector: Ruby (Gemini R) diffractometer	5256 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4821 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
Detector resolution: 10.4340 pixels mm^-1	θmax = 28.3°, θmin = 3.2°
ω and π scans	h = −12→12
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction Ltd, 2008). Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995).	k = −14→14
Tmin = 0.597, Tmax = 0.739	l = −15→16
23048 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)] = 0.019	Hydrogen site location: difference Fourier map
wR(F^2) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0295P)^2 + 0.5514P] where P = (Fo^2 + 2Fc^2)/3
5256 reflections	(Δ/σ)max = 0.002
368 parameters	Δρmax = 0.35 e Å^−3
21 restraints	Δρmin = −0.35 e Å^−3

Special details

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 > 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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.79297 (3)	0.39482 (2)	0.53420 (2)	0.02206 (6)
O1M	0.90350 (14)	0.41783 (12)	0.66309 (11)	0.0263 (2)
O2M	0.87580 (16)	0.19011 (13)	0.58621 (17)	0.0491 (4)
O3M	0.68751 (14)	0.36128 (11)	0.40717 (11)	0.0256 (2)
O4M	1.01393 (13)	0.36637 (12)	0.40996 (12)	0.0284 (3)
O5M	0.57003 (14)	0.41958 (12)	0.65518 (12)	0.0284 (3)
H11M	0.9877 (19)	0.3594 (19)	0.6631 (19)	0.043*
H12M	0.851 (2)	0.412 (2)	0.7279 (15)	0.043*
H21M	0.826 (2)	0.147 (2)	0.594 (2)	0.043*
H22M	0.9641 (18)	0.144 (2)	0.586 (2)	0.043*
H31M	0.644 (2)	0.314 (2)	0.4311 (18)	0.043*
H32M	0.754 (2)	0.333 (2)	0.3493 (16)	0.043*
H41M	1.090 (2)	0.3037 (16)	0.418 (2)	0.043*
H42M	1.038 (2)	0.4287 (16)	0.3851 (19)	0.043*
H51M	0.543 (3)	0.3613 (16)	0.666 (2)	0.043*
H52M	0.498 (2)	0.4863 (16)	0.640 (2)	0.043*
V1	0.47782 (3)	0.93164 (3)	0.24082 (2)	0.02121 (7)
V2	0.66577 (3)	1.00391 (2)	0.50678 (2)	0.01531 (6)
V3	0.78612 (3)	0.94100 (3)	0.25379 (2)	0.02065 (7)
V4	0.52189 (3)	0.81964 (2)	0.68737 (2)	0.01805 (6)
V5	0.65040 (3)	0.75597 (2)	0.43420 (2)	0.01689 (6)
O1	0.71143 (13)	0.60131 (10)	0.48058 (10)	0.0234 (2)
O2	0.58036 (15)	0.66822 (11)	0.73126 (11)	0.0293 (3)
O3	0.95253 (14)	0.91909 (12)	0.17062 (11)	0.0321 (3)
O4	0.40717 (15)	0.90217 (13)	0.14834 (11)	0.0342 (3)
O5	0.67347 (13)	0.91537 (11)	0.16730 (9)	0.0235 (2)
O6	0.82584 (12)	0.97905 (10)	0.39929 (9)	0.0205 (2)
O7	0.29016 (12)	0.96465 (10)	0.37850 (9)	0.0204 (2)
O8	0.54748 (12)	0.76628 (10)	0.32609 (9)	0.0208 (2)
O9	0.82005 (12)	0.77401 (10)	0.33628 (9)	0.0207 (2)
O10	0.40917 (12)	1.11376 (10)	0.22206 (9)	0.0214 (2)
O11	0.68224 (12)	1.12077 (10)	0.23374 (9)	0.0211 (2)
O12	0.69776 (11)	0.82438 (9)	0.55668 (9)	0.0167 (2)
O13	0.44653 (11)	0.81802 (9)	0.54714 (9)	0.0166 (2)
O14	0.55658 (11)	0.97094 (9)	0.39193 (9)	0.0161 (2)
N1	0.73209 (18)	0.73192 (16)	0.95533 (14)	0.0379 (4)
H1	0.6892	0.7838	0.9007	0.057*
C5	0.6774 (3)	0.6392 (2)	1.0093 (2)	0.0541 (6)
H2	0.5955	0.6318	0.9873	0.065*
C4	0.7420 (3)	0.5559 (2)	1.0963 (2)	0.0577 (6)
H3	0.7045	0.4914	1.1347	0.069*
C3	0.8626 (3)	0.5682 (2)	1.12640 (19)	0.0557 (7)
H4	0.9078	0.5119	1.1858	0.067*
C2	0.9176 (3)	0.6637 (2)	1.06912 (18)	0.0439 (5)
H5	1.0006	0.6713	1.0893	0.053*
C1	0.8495 (2)	0.74829 (18)	0.98159 (15)	0.0317 (4)
C6	0.8953 (2)	0.85679 (18)	0.91466 (17)	0.0366 (4)
H7A	0.9641	0.8705	0.9527	0.044*
H7B	0.8027	0.9355	0.9149	0.044*
C7	0.9769 (2)	0.83289 (19)	0.79046 (16)	0.0349 (4)
H8A	0.9193	0.8009	0.7568	0.042*
H8B	0.9783	0.9141	0.7461	0.042*
O20	1.13282 (15)	0.74093 (13)	0.78403 (12)	0.0372 (3)
H20	1.1890	0.7769	0.7902	0.056*
O1W	0.6998 (4)	0.2075 (2)	0.99708 (16)	0.0828 (7)
H11W	0.696 (5)	0.175 (3)	1.0649 (12)	0.124*
H12W	0.699 (5)	0.155 (3)	0.960 (3)	0.124*
O2W	0.7058 (2)	0.4247 (2)	0.86556 (17)	0.0742 (6)
H21W	0.632 (3)	0.457 (3)	0.832 (3)	0.111*
H22W	0.716 (4)	0.3468 (14)	0.885 (3)	0.111*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01998 (12)	0.01629 (11)	0.03081 (13)	−0.00660 (9)	−0.00869 (10)	−0.00015 (9)
O1M	0.0215 (6)	0.0237 (6)	0.0315 (6)	−0.0053 (5)	−0.0081 (5)	−0.0012 (5)
O2M	0.0283 (7)	0.0193 (6)	0.1052 (14)	−0.0106 (5)	−0.0331 (8)	0.0112 (7)
O3M	0.0256 (6)	0.0238 (6)	0.0316 (6)	−0.0132 (5)	−0.0047 (5)	−0.0048 (5)
O4M	0.0212 (6)	0.0224 (6)	0.0400 (7)	−0.0070 (5)	−0.0063 (5)	−0.0021 (5)
O5M	0.0247 (6)	0.0217 (6)	0.0400 (7)	−0.0108 (5)	−0.0065 (5)	−0.0014 (5)
V1	0.02410 (13)	0.01993 (13)	0.02154 (13)	−0.00696 (10)	−0.00891 (10)	−0.00344 (10)
V2	0.01348 (11)	0.01252 (12)	0.02075 (13)	−0.00452 (9)	−0.00535 (9)	−0.00177 (9)
V3	0.01931 (13)	0.01897 (13)	0.02142 (13)	−0.00647 (10)	−0.00120 (10)	−0.00267 (10)
V4	0.02039 (12)	0.01307 (12)	0.01949 (13)	−0.00495 (9)	−0.00601 (10)	0.00067 (9)
V5	0.01743 (12)	0.01089 (12)	0.02153 (13)	−0.00361 (9)	−0.00493 (9)	−0.00228 (9)
O1	0.0258 (6)	0.0123 (5)	0.0303 (6)	−0.0044 (4)	−0.0079 (5)	−0.0014 (4)
O2	0.0363 (6)	0.0162 (5)	0.0322 (6)	−0.0070 (5)	−0.0115 (5)	0.0040 (5)
O3	0.0259 (6)	0.0336 (7)	0.0323 (6)	−0.0112 (5)	0.0038 (5)	−0.0066 (5)
O4	0.0410 (7)	0.0329 (7)	0.0345 (7)	−0.0105 (6)	−0.0194 (6)	−0.0077 (5)
O5	0.0270 (6)	0.0212 (5)	0.0203 (5)	−0.0065 (4)	−0.0042 (4)	−0.0040 (4)
O6	0.0156 (5)	0.0193 (5)	0.0257 (5)	−0.0061 (4)	−0.0043 (4)	−0.0014 (4)
O7	0.0201 (5)	0.0189 (5)	0.0252 (5)	−0.0078 (4)	−0.0091 (4)	−0.0020 (4)
O8	0.0236 (5)	0.0155 (5)	0.0252 (5)	−0.0068 (4)	−0.0078 (4)	−0.0040 (4)
O9	0.0175 (5)	0.0160 (5)	0.0252 (5)	−0.0028 (4)	−0.0035 (4)	−0.0036 (4)
O10	0.0244 (5)	0.0189 (5)	0.0210 (5)	−0.0062 (4)	−0.0100 (4)	0.0004 (4)
O11	0.0218 (5)	0.0189 (5)	0.0213 (5)	−0.0086 (4)	−0.0029 (4)	0.0007 (4)
O12	0.0152 (5)	0.0128 (5)	0.0220 (5)	−0.0037 (4)	−0.0067 (4)	−0.0008 (4)
O13	0.0168 (5)	0.0119 (5)	0.0218 (5)	−0.0058 (4)	−0.0052 (4)	−0.0002 (4)
O14	0.0157 (5)	0.0129 (5)	0.0198 (5)	−0.0047 (4)	−0.0052 (4)	−0.0012 (4)
N1	0.0318 (8)	0.0386 (9)	0.0352 (8)	−0.0090 (7)	−0.0101 (7)	0.0087 (7)
C5	0.0408 (11)	0.0516 (13)	0.0622 (15)	−0.0191 (10)	−0.0112 (11)	0.0157 (11)
C4	0.0573 (14)	0.0431 (13)	0.0492 (13)	−0.0111 (11)	0.0004 (11)	0.0139 (10)
C3	0.0715 (16)	0.0389 (12)	0.0305 (10)	0.0054 (11)	−0.0142 (10)	0.0016 (9)
C2	0.0472 (11)	0.0383 (11)	0.0360 (10)	0.0043 (9)	−0.0193 (9)	−0.0111 (9)
C1	0.0304 (9)	0.0301 (9)	0.0257 (8)	−0.0004 (7)	−0.0038 (7)	−0.0095 (7)
C6	0.0360 (10)	0.0312 (9)	0.0409 (10)	−0.0072 (8)	−0.0081 (8)	−0.0115 (8)
C7	0.0390 (10)	0.0362 (10)	0.0336 (9)	−0.0183 (8)	−0.0111 (8)	0.0018 (8)
O20	0.0357 (7)	0.0365 (7)	0.0432 (7)	−0.0180 (6)	−0.0016 (6)	−0.0115 (6)
O1W	0.155 (2)	0.0668 (13)	0.0394 (9)	−0.0552 (14)	−0.0224 (12)	−0.0004 (9)
O2W	0.0735 (13)	0.0630 (12)	0.0467 (10)	0.0013 (10)	−0.0042 (9)	0.0108 (9)

Geometric parameters (Å, º)

Mn1—O2M	2.1420 (13)	V4—O10^i	1.8227 (11)
Mn1—O1	2.1630 (11)	V4—O11^i	1.8414 (11)
Mn1—O4M	2.1902 (12)	V4—O12	1.9911 (11)
Mn1—O5M	2.1915 (12)	V4—O13	2.0147 (10)
Mn1—O1M	2.2073 (12)	V4—O14^i	2.2650 (10)
Mn1—O3M	2.2103 (12)	V5—O1	1.6350 (11)
O1M—H11M	0.810 (15)	V5—O8	1.7933 (11)
O1M—H12M	0.818 (15)	V5—O9	1.7990 (11)
O2M—H21M	0.793 (15)	V5—O13	2.0083 (10)
O2M—H22M	0.795 (15)	V5—O12	2.0244 (10)
O3M—H31M	0.779 (15)	V5—O14	2.2290 (10)
O3M—H32M	0.827 (15)	N1—C1	1.335 (2)
O4M—H41M	0.797 (15)	N1—C5	1.339 (3)
O4M—H42M	0.809 (15)	N1—H1	0.8600
O5M—H51M	0.779 (15)	C5—C4	1.359 (3)
O5M—H52M	0.819 (15)	C5—H2	0.9300
V1—O4	1.5971 (12)	C4—C3	1.364 (4)
V1—O5	1.8002 (11)	C4—H3	0.9300
V1—O10	1.8796 (11)	C3—C2	1.376 (4)
V1—O8	1.8940 (11)	C3—H4	0.9300
V1—O7	2.0640 (11)	C2—C1	1.382 (3)
V1—O14	2.3296 (10)	C2—H5	0.9300
V2—O7^i	1.6898 (10)	C1—C6	1.485 (3)
V2—O6	1.6910 (11)	C6—C7	1.518 (3)
V2—O12	1.9219 (10)	C6—H7A	0.9700
V2—O13^i	1.9321 (10)	C6—H7B	0.9700
V2—O14^i	2.0939 (10)	C7—O20	1.425 (2)
V2—O14	2.1099 (10)	C7—H8A	0.9700
V3—O3	1.5951 (12)	C7—H8B	0.9700
V3—O5	1.8202 (11)	O20—H20	0.8200
V3—O11	1.8664 (11)	O1W—H11W	0.826 (10)
V3—O9	1.8947 (11)	O1W—H12W	0.821 (10)
V3—O6	2.0521 (11)	O2W—H21W	0.821 (10)
V3—O14	2.3272 (10)	O2W—H22W	0.839 (10)
V4—O2	1.5967 (12)
O2M—Mn1—O1	179.46 (6)	O12—V4—O13	76.15 (4)
O2M—Mn1—O4M	88.91 (6)	O2—V4—O14^i	174.56 (5)
O1—Mn1—O4M	90.55 (5)	O10^i—V4—O14^i	80.99 (4)
O2M—Mn1—O5M	90.32 (6)	O11^i—V4—O14^i	80.27 (4)
O1—Mn1—O5M	90.22 (5)	O12—V4—O14^i	75.92 (4)
O4M—Mn1—O5M	178.09 (5)	O13—V4—O14^i	75.50 (4)
O2M—Mn1—O1M	88.71 (5)	O1—V5—O8	102.94 (5)
O1—Mn1—O1M	91.24 (4)	O1—V5—O9	103.32 (5)
O4M—Mn1—O1M	87.88 (5)	O8—V5—O9	96.67 (5)
O5M—Mn1—O1M	93.86 (5)	O1—V5—O13	99.42 (5)
O2M—Mn1—O3M	88.48 (5)	O8—V5—O13	89.69 (5)
O1—Mn1—O3M	91.57 (4)	O9—V5—O13	154.31 (4)
O4M—Mn1—O3M	91.80 (5)	O1—V5—O12	99.46 (5)
O5M—Mn1—O3M	86.43 (5)	O8—V5—O12	154.92 (4)
O1M—Mn1—O3M	177.17 (5)	O9—V5—O12	88.96 (5)
Mn1—O1M—H11M	109.9 (16)	O13—V5—O12	75.55 (4)
Mn1—O1M—H12M	109.9 (16)	O1—V5—O14	173.50 (5)
H11M—O1M—H12M	106.4 (19)	O8—V5—O14	81.23 (4)
Mn1—O2M—H21M	123.8 (16)	O9—V5—O14	80.95 (4)
Mn1—O2M—H22M	126.0 (16)	O13—V5—O14	75.45 (4)
H21M—O2M—H22M	109 (2)	O12—V5—O14	75.54 (4)
Mn1—O3M—H31M	114.3 (17)	V5—O1—Mn1	177.41 (7)
Mn1—O3M—H32M	111.3 (16)	V1—O5—V3	114.44 (6)
H31M—O3M—H32M	107.9 (19)	V2—O6—V3	110.66 (5)
Mn1—O4M—H41M	120.9 (16)	V2^i—O7—V1	110.70 (5)
Mn1—O4M—H42M	118.2 (16)	V5—O8—V1	114.73 (5)
H41M—O4M—H42M	109.4 (19)	V5—O9—V3	114.93 (5)
Mn1—O5M—H51M	115.5 (17)	V4^i—O10—V1	114.47 (5)
Mn1—O5M—H52M	114.2 (16)	V4^i—O11—V3	114.71 (6)
H51M—O5M—H52M	108.7 (19)	V2—O12—V4	107.20 (5)
O4—V1—O5	104.34 (6)	V2—O12—V5	107.14 (5)
O4—V1—O10	103.18 (6)	V4—O12—V5	100.72 (4)
O5—V1—O10	91.93 (5)	V2^i—O13—V5	107.07 (5)
O4—V1—O8	101.05 (6)	V2^i—O13—V4	107.61 (5)
O5—V1—O8	92.36 (5)	V5—O13—V4	100.46 (4)
O10—V1—O8	153.49 (5)	V2^i—O14—V2	101.73 (4)
O4—V1—O7	100.26 (6)	V2^i—O14—V5	94.25 (4)
O5—V1—O7	155.39 (5)	V2—O14—V5	94.06 (4)
O10—V1—O7	83.07 (5)	V2^i—O14—V4^i	92.45 (4)
O8—V1—O7	82.20 (5)	V2—O14—V4^i	93.39 (4)
O4—V1—O14	173.27 (6)	V5—O14—V4^i	168.77 (5)
O5—V1—O14	82.13 (4)	V2^i—O14—V3	170.22 (5)
O10—V1—O14	78.13 (4)	V2—O14—V3	87.97 (3)
O8—V1—O14	76.58 (4)	V5—O14—V3	86.22 (3)
O7—V1—O14	73.26 (4)	V4^i—O14—V3	85.66 (3)
O7^i—V2—O6	106.95 (5)	V2^i—O14—V1	88.65 (3)
O7^i—V2—O12	97.28 (5)	V2—O14—V1	169.59 (5)
O6—V2—O12	97.08 (5)	V5—O14—V1	85.86 (3)
O7^i—V2—O13^i	96.97 (5)	V4^i—O14—V1	85.30 (3)
O6—V2—O13^i	96.72 (5)	V3—O14—V1	81.63 (3)
O12—V2—O13^i	156.33 (4)	C1—N1—C5	123.61 (18)
O7^i—V2—O14^i	87.39 (5)	C1—N1—H1	118.2
O6—V2—O14^i	165.64 (5)	C5—N1—H1	118.2
O12—V2—O14^i	81.59 (4)	N1—C5—C4	119.8 (2)
O13^i—V2—O14^i	80.28 (4)	N1—C5—H2	120.1
O7^i—V2—O14	165.65 (5)	C4—C5—H2	120.1
O6—V2—O14	87.40 (5)	C5—C4—C3	119.0 (2)
O12—V2—O14	80.54 (4)	C5—C4—H3	120.5
O13^i—V2—O14	80.97 (4)	C3—C4—H3	120.5
O14^i—V2—O14	78.27 (4)	C4—C3—C2	120.2 (2)
O3—V3—O5	104.38 (6)	C4—C3—H4	119.9
O3—V3—O11	103.02 (6)	C2—C3—H4	119.9
O5—V3—O11	91.87 (5)	C3—C2—C1	120.0 (2)
O3—V3—O9	101.46 (6)	C3—C2—H5	120.0
O5—V3—O9	91.41 (5)	C1—C2—H5	120.0
O11—V3—O9	153.63 (5)	N1—C1—C2	117.44 (19)
O3—V3—O6	99.85 (6)	N1—C1—C6	117.14 (16)
O5—V3—O6	155.75 (5)	C2—C1—C6	125.41 (19)
O11—V3—O6	83.55 (5)	C1—C6—C7	113.35 (15)
O9—V3—O6	82.77 (5)	C1—C6—H7A	108.9
O3—V3—O14	173.61 (6)	C7—C6—H7A	108.9
O5—V3—O14	81.79 (4)	C1—C6—H7B	108.9
O11—V3—O14	78.12 (4)	C7—C6—H7B	108.9
O9—V3—O14	76.47 (4)	H7A—C6—H7B	107.7
O6—V3—O14	73.96 (4)	O20—C7—C6	111.21 (15)
O2—V4—O10^i	103.46 (6)	O20—C7—H8A	109.4
O2—V4—O11^i	102.30 (6)	C6—C7—H8A	109.4
O10^i—V4—O11^i	94.49 (5)	O20—C7—H8B	109.4
O2—V4—O12	100.69 (6)	C6—C7—H8B	109.4
O10^i—V4—O12	90.94 (5)	H8A—C7—H8B	108.0
O11^i—V4—O12	154.42 (5)	C7—O20—H20	109.5
O2—V4—O13	99.65 (5)	H11W—O1W—H12W	107.3 (17)
O10^i—V4—O13	155.28 (5)	H21W—O2W—H22W	105.4 (16)
O11^i—V4—O13	89.03 (5)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1M—H11M···O9^ii	0.81 (2)	1.85 (2)	2.6599 (16)	180 (3)
O1M—H12M···O2W	0.82 (2)	1.85 (2)	2.661 (2)	170 (2)
O2M—H21M···O7^iii	0.79 (2)	1.93 (2)	2.7179 (17)	177 (2)
O2M—H22M···O6^ii	0.80 (2)	1.96 (2)	2.7497 (17)	174 (2)
O3M—H31M···O13^iii	0.78 (2)	1.95 (2)	2.7150 (15)	166 (2)
O3M—H32M···O20^ii	0.83 (2)	1.83 (2)	2.6450 (18)	167 (2)
O4M—H41M···O12^ii	0.80 (2)	2.02 (2)	2.8033 (15)	166 (2)
O4M—H42M···O1M^ii	0.81 (2)	1.97 (2)	2.7773 (18)	176 (2)
O5M—H51M···O8^iii	0.78 (2)	1.94 (2)	2.7113 (16)	170 (2)
O5M—H52M···O3M^iii	0.82 (2)	2.03 (2)	2.8425 (18)	173 (2)
O1W—H11W···O11^iv	0.83 (1)	1.99 (1)	2.812 (2)	172 (3)
O1W—H12W···O4^iii	0.82 (1)	2.17 (2)	2.924 (2)	152 (4)
O2W—H21W···O2	0.82 (1)	2.38 (3)	2.868 (2)	119 (3)
O2W—H21W···O5M	0.82 (1)	2.52 (3)	3.165 (3)	136 (3)
O2W—H22W···O1W	0.84 (1)	1.89 (2)	2.659 (3)	152 (4)
N1—H1···O10^i	0.86	1.90	2.7531 (19)	175
O20—H20···O11^v	0.82	1.95	2.7490 (17)	166

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