Crystal structures of two deca-vanadates(V) with penta-aqua-manganese(II) pendant groups: (NMe4)2[V10O28{Mn(H2O)5}2]·5H2O and [NH3C(CH2OH)3]2[V10O28{Mn(H2O)5}2]·2H2O.

Two heterometallic deca-vanadate(V) compounds, bis-(tetra-methyl-ammonium) deca-aquadi-μ4-oxido-tetra-μ3-oxido-hexa-deca-μ2-oxido-hexa-oxidodimang-anese(II)-deca-vanadate(V) penta-hydrate, (Me4N)2[V10O28{Mn(H2O)5}2]·5H2O, A, and bis-{[tris-(hy-droxy-meth-yl)meth-yl]ammonium} deca-aquadi-μ4-oxido-tetra-μ3-oxido-hexa-deca-μ2-oxido-hexa-oxidodimanganese(II)deca-vanadate(V) dihydrate, [NH3C(CH2OH)3]2[V10O28{Mn(H2O)5}2]·2H2O, B, have been synthesized under mild reaction conditions in an aqueous medium. Both polyanions present two [Mn(OH2)5](2+) complex units bound to the deca-vanadate cluster through oxide bridges. In A, the deca-vanadate unit has 2/m symmetry, whereas in B it has twofold symmetry. Apart from this, the main differences between A and B rest on the organic cations, tetra-methyl-ammonium and [tris-(hy-droxy-meth-yl)meth-yl]ammonium, respectively, and on the number and arrangement of the water mol-ecules of crystallization. In both compounds, the H atoms from the coordinating water mol-ecules participate in extensive three-dimensional hydrogen-bonding networks, which link the cluster units both directly and through solvent mol-ecules and, in B, through the 'tris-' cation hydroxyl groups. The cation in B also participates in N-H⋯O hydrogen bonds. A number of C-H⋯O inter-actions are also observed in both structures.

Chemical context

Research on the electronic properties, catalytic activities and biological roles of polyoxidovanadates 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, [HnV10O28](6−, 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., 2008 ▸; Wang, Yan et al., 2008 ▸; Wang et al., 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., 2008 ▸; Wang et al., 2011 ▸; Klištincová et al., 2009 ▸, 2010 ▸; Pavliuk et al., 2014 ▸).

Polyoxidovanadates containing manganese cations have been synthesized as ionic pairs (Shan & Huang, 1999 ▸; Lin et al., 2011 ▸) or as heterometallic aggregates in which the oxidovanadate 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 polyoxidovanadates 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 polyoxidovanadate (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.

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) were isolated in 12% yield, as the only reaction product, after one week at room temperature. X-ray diffraction analyses revealed very similar structures for the heteropolyanions in A and B.

Structural commentary

The anionic heteropolyanions 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 heteropolyanion. The anion lies about a mirror plane which passes through the V2, V4 and 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 ▸.

Figure 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.]

The V10O28 moiety in the structure of 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 ▸).

Figure 2

The corresponding view for [NH3C(CH2OH)3]2[V10O28{Mn(H2O)5}2]·2H2O, B. [Symmetry code: (1) 1 − x, y,  − z.]

Figure 3

The anion of compound B viewed approximately down the a axis of the V10O28 moiety. [Symmetry code: (1) 1 − x, y,  − z.]

Figure 4

The anion of compound B viewed approximately down the b axis of the V10O28 moiety. [Symmetry code: (1) 1 − x, y,  − z.]

Figure 5

The anion of compound B viewed approximately down the c axis of the V10O28 moiety. [Symmetry code: (1) 1 − x, y,  − z.]

Bond angles and lengths determined for [V10O28{Mn(H2O)5}2]2– are in the ranges 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 heteropolyanions, 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.

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. Additional C—H⋯O interactions are observed in the structures of both compounds.

Table 1

Hydrogen-bond geometry (Å, °) for compound A

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O11i	0.76 (2)	1.97 (2)	2.7199 (14)	168 (2)
O2—H2A⋯O7i	0.72 (2)	2.04 (2)	2.7457 (15)	167 (2)
O2—H2B⋯O3ii	0.78 (2)	2.05 (2)	2.8295 (18)	178 (2)
O3—H3A⋯O6ii	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⋯O11iii	0.96	2.51	3.362 (2)	148
C10—H10B⋯O11iv	0.96	2.51	3.362 (2)	148
C10—H10C⋯O2v	0.96	2.58	3.370 (3)	139
C10—H10C⋯O2vi	0.96	2.57	3.370 (3)	141
C11—H11A⋯O8vii	0.96	2.48	3.384 (3)	156
C12—H12A⋯O12iii	0.96	2.60	3.474 (4)	152
C12—H12C⋯O12iv	0.96	2.59	3.474 (4)	153

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Table 2

Hydrogen-bond geometry (Å, °) for compound B

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O14i	0.70 (12)	2.01 (12)	2.703 (7)	167 (12)
O1W—H1B⋯O12ii	0.70 (7)	2.04 (8)	2.727 (8)	169 (8)
O2W—H2A⋯O5iii	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⋯O7iii	0.70 (9)	1.94 (9)	2.636 (7)	176 (10)
O3W—H3B⋯O11A iv	0.88 (8)	1.91 (8)	2.752 (8)	160 (7)
O4W—H4A⋯O6v	0.82 (11)	1.90 (11)	2.708 (6)	167 (10)
O4W—H4B⋯O2W v	0.76 (9)	2.12 (9)	2.871 (7)	169 (9)
O5W—H5A⋯O8v	0.55 (11)	2.18 (11)	2.725 (10)	170 (16)
O5W—H5B⋯O13A iv	0.83 (14)	2.12 (13)	2.699 (12)	127 (12)
O5W—H5B⋯O13B iv	0.83 (14)	1.95 (14)	2.77 (2)	168 (13)
N1—H1C⋯O3W v	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⋯O4v	0.89	1.91	2.787 (6)	166
C11—H11C⋯O11v	0.97	2.46	3.392 (9)	160
O11A—H11A⋯O6WA v	0.82	1.96	2.758 (12)	166
O12A—H12A⋯O3iii	0.82	1.94	2.756 (7)	174
C13—H13E⋯O2	0.97	2.40	3.280 (10)	151
O13B—H13B⋯O6WB vi	0.77	1.92	2.60 (2)	148
O6WA—H6A⋯O3	0.82 (2)	2.23 (9)	2.966 (9)	150 (15)
O6WA—H6B⋯O10vii	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⋯O10vii	0.82 (2)	1.93 (8)	2.720 (19)	161 (24)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Database survey

For structures with the [V10O28{Mn(H2O)5}2]2– heteropolyanion, see: Klištincová 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 ▸).

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 (NMe

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 one third 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 [NH

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.

Refinement details

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

Table 3

Experimental details

	Compound A	Compound B
Crystal data
Chemical formula	(C4H12N)2·[Mn2V10O28(H2O)10]·5H2O	(C4H12NO3)2[Mn2V10O28(H2O)10]·2H2O
M r	1485.81	1527.76
Crystal system, space group	Monoclinic, I2/m	Monoclinic, C2/c
Temperature (K)	292	295
a, b, c (Å)	13.2434 (7), 9.6402 (5), 17.7628 (13)	19.3147 (8), 9.7733 (4), 22.7952 (10)
β (°)	98.626 (2)	96.392 (1)
V (Å3)	2242.1 (2)	4276.3 (3)
Z	2	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	2.64	2.78
Crystal size (mm)	0.48 × 0.38 × 0.15	0.49 × 0.26 × 0.13
Data collection
Diffractometer	Bruker D8 Venture/Photon 100 CMOS	Bruker D8 Venture/Photon 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2012 ▸)	Multi-scan (SADABS; Bruker, 2012 ▸)
T min, T max	0.562, 0.746	0.542, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	81983, 2953, 2752	71752, 3936, 3280
R int	0.025	0.039
(sin θ/λ)max (Å−1)	0.668	0.605
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.020, 0.060, 1.09	0.052, 0.114, 1.12
No. of reflections	2953	3936
No. of parameters	194	385
No. of restraints	0	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ2(F o 2) + (0.0329P)2 + 2.2668P] where P = (F o 2 + 2F c 2)/3	w = 1/[σ2(F o 2) + (0.0062P)2 + 110.7865P] where P = (F o 2 + 2F c 2)/3
Δρmax, Δρmin (e Å−3)	0.58, −0.34	0.78, −1.11

Computer programs: APEX2 and SAINT (Bruker, 2010 ▸), SHELXS97, SHELXL97 (Sheldrick, 2008 ▸), SHELXL2013 and SHELXL2014 (Sheldrick, 2015 ▸), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ▸).

Hydrogen atoms on the cation 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].

Crystal structure: contains datablock(s) Compound-A, Compound-B, global. DOI: 10.1107/S2056989014028230/hb7337sup1.cif

Structure factors: contains datablock(s) mpf-A. DOI: 10.1107/S2056989014028230/hb7337mpf-Asup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989014028230/hb7337mpf-Asup4.cdx

Structure factors: contains datablock(s) mpf-B. DOI: 10.1107/S2056989014028230/hb7337mpf-Bsup3.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989014028230/hb7337mpf-Bsup5.cdx

CCDC references: 1041495, 1041494

Additional supporting information: crystallographic information; 3D view; checkCIF report

(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) Å3	Prism, yellow
Z = 2	0.48 × 0.38 × 0.15 mm

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 on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020	Hydrogen site location: mixed
wR(F2) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0329P)2 + 2.2668P] where P = (Fo2 + 2Fc2)/3
2953 reflections	(Δ/σ)max = 0.001
194 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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.

	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)

	U11	U22	U33	U12	U13	U23
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

Mn1—O1	2.1365 (18)	V5—O10	1.8264 (8)
Mn1—O4	2.1412 (14)	V5—O8iii	1.8322 (10)
Mn1—O2	2.1863 (12)	V5—O6i	1.9136 (10)
Mn1—O2i	2.1863 (12)	V5—O11	2.0579 (10)
Mn1—O3	2.2136 (12)	V5—O9	2.3326 (10)
Mn1—O3i	2.2136 (12)	V5—V5i	3.0543 (5)
V2—O4	1.6350 (14)	V5—V4iii	3.1068 (4)
V2—O6	1.7916 (10)	O1—H1A	0.76 (2)
V2—O6i	1.7916 (10)	O2—H2A	0.72 (2)
V2—O7i	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—V5i	1.9137 (10)
V2—V5	3.1152 (4)	O8—V5iii	1.8322 (10)
V2—V5i	3.1153 (4)	O9—V3iii	2.1041 (9)
V3—O11	1.6917 (10)	O9—V4iii	2.2840 (12)
V3—O11ii	1.6918 (10)	O9—V5i	2.3327 (10)
V3—O7	1.9205 (9)	O10—V5i	1.8264 (8)
V3—O7ii	1.9205 (9)	N1—C11i	1.481 (2)
V3—O9	2.1041 (9)	N1—C11	1.481 (2)
V3—O9iii	2.1041 (9)	N1—C12	1.486 (4)
V3—V5	3.0928 (3)	N1—C10	1.496 (3)
V3—V5ii	3.0928 (3)	C10—H10A	0.9600
V4—O5	1.6013 (15)	C10—H10B	0.9600
V4—O8i	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—O7i	1.9959 (10)	C11—H11C	0.9600
V4—O9iii	2.2840 (12)	C12—H12A	0.9600
V4—V5ii	3.1069 (4)	C12—H12B	0.9600
V4—V5iii	3.1069 (4)	C12—H12C	0.9600
V5—O12	1.6030 (11)
O1—Mn1—O4	169.83 (9)	O5—V4—V5iii	135.13 (5)
O1—Mn1—O2	86.07 (6)	O8i—V4—V5iii	82.35 (3)
O4—Mn1—O2	87.28 (4)	O8—V4—V5iii	32.02 (3)
O1—Mn1—O2i	86.07 (6)	O7—V4—V5iii	123.83 (3)
O4—Mn1—O2i	87.28 (4)	O7i—V4—V5iii	86.97 (3)
O2—Mn1—O2i	98.27 (7)	O9iii—V4—V5iii	48.37 (3)
O1—Mn1—O3	92.53 (6)	V2—V4—V5iii	119.596 (11)
O4—Mn1—O3	94.47 (4)	V5ii—V4—V5iii	58.884 (11)
O2—Mn1—O3	84.40 (5)	O12—V5—O10	104.13 (6)
O2i—Mn1—O3	176.89 (5)	O12—V5—O8iii	103.30 (6)
O1—Mn1—O3i	92.53 (6)	O10—V5—O8iii	92.80 (6)
O4—Mn1—O3i	94.47 (4)	O12—V5—O6i	101.58 (6)
O2—Mn1—O3i	176.88 (5)	O10—V5—O6i	90.67 (6)
O2i—Mn1—O3i	84.40 (5)	O8iii—V5—O6i	153.19 (5)
O3—Mn1—O3i	92.89 (7)	O12—V5—O11	99.90 (6)
O4—V2—O6	103.51 (5)	O10—V5—O11	155.80 (5)
O4—V2—O6i	103.51 (5)	O8iii—V5—O11	84.37 (4)
O6—V2—O6i	97.40 (7)	O6i—V5—O11	81.68 (4)
O4—V2—O7i	98.09 (5)	O12—V5—O9	173.12 (5)
O6—V2—O7i	89.49 (4)	O10—V5—O9	82.29 (4)
O6i—V2—O7i	155.03 (4)	O8iii—V5—O9	78.56 (4)
O4—V2—O7	98.09 (5)	O6i—V5—O9	75.59 (4)
O6—V2—O7	155.03 (4)	O11—V5—O9	73.59 (3)
O6i—V2—O7	89.49 (4)	O12—V5—V5i	137.39 (5)
O7i—V2—O7	75.07 (5)	O10—V5—V5i	33.27 (4)
O4—V2—O9	172.10 (7)	O8iii—V5—V5i	83.88 (3)
O6—V2—O9	81.57 (4)	O6i—V5—V5i	84.57 (3)
O6i—V2—O9	81.57 (4)	O11—V5—V5i	122.69 (3)
O7i—V2—O9	75.72 (4)	O9—V5—V5i	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)	O8iii—V5—V3	79.01 (3)
O6i—V2—V4	128.77 (3)	O6i—V5—V3	77.29 (3)
O7i—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)	V5i—V5—V3	91.929 (7)
O4—V2—V5	137.34 (4)	O12—V5—V4iii	135.29 (5)
O6—V2—V5	84.70 (3)	O10—V5—V4iii	83.26 (4)
O6i—V2—V5	34.01 (3)	O8iii—V5—V4iii	32.02 (3)
O7i—V2—V5	124.08 (3)	O6i—V5—V4iii	122.63 (3)
O7—V2—V5	87.88 (3)	O11—V5—V4iii	81.71 (3)
O9—V2—V5	48.39 (3)	O9—V5—V4iii	47.04 (3)
V4—V2—V5	119.816 (10)	V5i—V5—V4iii	60.558 (6)
O4—V2—V5i	137.34 (4)	V3—V5—V4iii	61.520 (9)
O6—V2—V5i	34.02 (3)	O12—V5—V2	133.04 (5)
O6i—V2—V5i	84.70 (3)	O10—V5—V2	80.75 (4)
O7i—V2—V5i	87.88 (3)	O8iii—V5—V2	123.30 (3)
O7—V2—V5i	124.08 (3)	O6i—V5—V2	31.58 (3)
O9—V2—V5i	48.39 (3)	O11—V5—V2	80.81 (3)
V4—V2—V5i	119.816 (10)	O9—V5—V2	44.75 (3)
V5—V2—V5i	58.710 (11)	V5i—V5—V2	60.645 (6)
O11—V3—O11ii	106.92 (7)	V3—V5—V2	61.274 (8)
O11—V3—O7	97.20 (4)	V4iii—V5—V2	91.545 (10)
O11ii—V3—O7	96.82 (4)	Mn1—O1—H1A	127.0 (17)
O11—V3—O7ii	96.82 (4)	Mn1—O2—H2A	123.2 (17)
O11ii—V3—O7ii	97.20 (4)	Mn1—O2—H2B	122.5 (15)
O7—V3—O7ii	156.35 (6)	H2A—O2—H2B	108 (2)
O11—V3—O9	87.37 (4)	Mn1—O3—H3A	108.1 (19)
O11ii—V3—O9	165.69 (5)	Mn1—O3—H3B	117 (2)
O7—V3—O9	80.27 (4)	H3A—O3—H3B	114 (3)
O7ii—V3—O9	81.45 (4)	V2—O4—Mn1	179.96 (10)
O11—V3—O9iii	165.69 (5)	V2—O6—V5i	114.40 (5)
O11ii—V3—O9iii	87.38 (4)	V3—O7—V4	108.10 (4)
O7—V3—O9iii	81.45 (4)	V3—O7—V2	106.33 (4)
O7ii—V3—O9iii	80.27 (4)	V4—O7—V2	100.60 (4)
O9—V3—O9iii	78.34 (6)	V5iii—O8—V4	115.96 (5)
O11—V3—V5	38.47 (3)	V3iii—O9—V3	101.66 (6)
O11ii—V3—V5	145.38 (4)	V3iii—O9—V2	94.70 (4)
O7—V3—V5	90.52 (3)	V3—O9—V2	94.70 (4)
O7ii—V3—V5	88.69 (3)	V3iii—O9—V4iii	92.45 (4)
O9—V3—V5	48.93 (3)	V3—O9—V4iii	92.45 (4)
O9iii—V3—V5	127.22 (3)	V2—O9—V4iii	168.68 (7)
O11—V3—V5ii	145.38 (4)	V3iii—O9—V5	169.81 (5)
O11ii—V3—V5ii	38.47 (3)	V3—O9—V5	88.231 (11)
O7—V3—V5ii	88.68 (3)	V2—O9—V5	86.86 (4)
O7ii—V3—V5ii	90.52 (3)	V4iii—O9—V5	84.59 (4)
O9—V3—V5ii	127.22 (3)	V3iii—O9—V5i	88.232 (11)
O9iii—V3—V5ii	48.93 (3)	V3—O9—V5i	169.81 (5)
V5—V3—V5ii	176.145 (13)	V2—O9—V5i	86.86 (4)
O5—V4—O8i	103.31 (5)	V4iii—O9—V5i	84.59 (4)
O5—V4—O8	103.30 (5)	V5—O9—V5i	81.79 (4)
O8i—V4—O8	93.26 (7)	V5i—O10—V5	113.47 (8)
O5—V4—O7	100.85 (6)	V3—O11—V5	110.76 (5)
O8i—V4—O7	89.92 (4)	C11i—N1—C11	110.3 (3)
O8—V4—O7	154.18 (4)	C11i—N1—C12	109.32 (18)
O5—V4—O7i	100.85 (6)	C11—N1—C12	109.32 (18)
O8i—V4—O7i	154.18 (4)	C11i—N1—C10	109.79 (14)
O8—V4—O7i	89.92 (4)	C11—N1—C10	109.79 (14)
O7—V4—O7i	76.64 (6)	C12—N1—C10	108.3 (2)
O5—V4—O9iii	175.24 (8)	N1—C10—H10A	109.5
O8i—V4—O9iii	79.88 (4)	N1—C10—H10B	109.5
O8—V4—O9iii	79.88 (4)	H10A—C10—H10B	109.5
O7—V4—O9iii	75.47 (4)	N1—C10—H10C	109.5
O7i—V4—O9iii	75.48 (4)	H10A—C10—H10C	109.5
O5—V4—V2	90.98 (7)	H10B—C10—H10C	109.5
O8i—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
O7i—V4—V2	40.12 (3)	N1—C11—H11C	109.5
O9iii—V4—V2	84.26 (3)	H11A—C11—H11C	109.5
O5—V4—V5ii	135.13 (5)	H11B—C11—H11C	109.5
O8i—V4—V5ii	32.02 (3)	N1—C12—H12A	109.5
O8—V4—V5ii	82.35 (3)	N1—C12—H12B	109.5
O7—V4—V5ii	86.97 (3)	H12A—C12—H12B	109.5
O7i—V4—V5ii	123.83 (3)	N1—C12—H12C	109.5
O9iii—V4—V5ii	48.37 (3)	H12A—C12—H12C	109.5
V2—V4—V5ii	119.596 (11)	H12B—C12—H12C	109.5
O4—V2—O6—V5i	−174.84 (6)	O12—V5—O10—V5i	−178.86 (8)
O6i—V2—O6—V5i	−68.97 (7)	O8iii—V5—O10—V5i	−74.39 (8)
O7i—V2—O6—V5i	86.96 (6)	O6i—V5—O10—V5i	79.02 (8)
O7—V2—O6—V5i	35.96 (13)	O11—V5—O10—V5i	8.1 (2)
O9—V2—O6—V5i	11.32 (5)	O9—V5—O10—V5i	3.67 (8)
V4—V2—O6—V5i	87.13 (6)	V3—V5—O10—V5i	4.14 (11)
V5—V2—O6—V5i	−37.34 (5)	V4iii—V5—O10—V5i	−43.77 (7)
O5—V4—O8—V5iii	174.45 (7)	V2—V5—O10—V5i	48.91 (7)
O8i—V4—O8—V5iii	69.96 (7)	O11ii—V3—O11—V5	−178.88 (6)
O7—V4—O8—V5iii	−26.63 (13)	O7—V3—O11—V5	81.71 (5)
O7i—V4—O8—V5iii	−84.41 (6)	O7ii—V3—O11—V5	−79.19 (5)
O9iii—V4—O8—V5iii	−9.15 (5)	O9—V3—O11—V5	1.87 (5)
V2—V4—O8—V5iii	−82.75 (6)	O9iii—V3—O11—V5	−1.9 (2)
V5ii—V4—O8—V5iii	39.78 (5)	V5ii—V3—O11—V5	179.893 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O11iv	0.76 (2)	1.97 (2)	2.7199 (14)	168 (2)
O2—H2A···O7iv	0.72 (2)	2.04 (2)	2.7457 (15)	167 (2)
O2—H2B···O3v	0.78 (2)	2.05 (2)	2.8295 (18)	178 (2)
O3—H3A···O6v	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···O11vi	0.96	2.51	3.362 (2)	148
C10—H10B···O11vii	0.96	2.51	3.362 (2)	148
C10—H10C···O2viii	0.96	2.58	3.370 (3)	139
C10—H10C···O2ix	0.96	2.57	3.370 (3)	141
C11—H11A···O8x	0.96	2.48	3.384 (3)	156
C12—H12A···O12vi	0.96	2.60	3.474 (4)	152
C12—H12C···O12vii	0.96	2.59	3.474 (4)	153

(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) Å3	Plate, yellow
Z = 4	0.49 × 0.26 × 0.13 mm

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 on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052	Hydrogen site location: mixed
wR(F2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.0062P)2 + 110.7865P] where P = (Fo2 + 2Fc2)/3
3936 reflections	(Δ/σ)max < 0.001
385 parameters	Δρmax = 0.78 e Å−3
6 restraints	Δρmin = −1.11 e Å−3

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.

	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)

	U11	U22	U33	U12	U13	U23
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)

Mn1—O1W	2.126 (5)	V7—O6	1.921 (4)
Mn1—O5W	2.139 (7)	V7—O6i	1.921 (4)
Mn1—O1	2.169 (4)	V7—O13	2.106 (4)
Mn1—O4W	2.204 (5)	V7—O13i	2.106 (4)
Mn1—O3W	2.209 (5)	V7—V5i	3.0900 (11)
Mn1—O2W	2.231 (5)	O7—V4i	1.884 (4)
V2—O1	1.634 (4)	O8—V5i	1.860 (4)
V2—O4	1.789 (4)	O13—V3i	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—O13i	2.267 (4)	N1—H1C	0.8900
V3—V5i	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—O7i	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—O8i	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—V3i	3.1025 (14)	C13—H13D	0.9700
V6—O12	1.694 (4)	C13—H13E	0.9700
V6—O12i	1.694 (4)	C13—H13F	0.9700
V6—O5	1.928 (4)	O13A—H13A	0.8200
V6—O5i	1.928 (4)	O13B—H13B	0.8 (4)
V6—O13i	2.097 (4)	O6WA—H6A	0.82 (2)
V6—O13	2.097 (4)	O6WA—H6B	0.82 (2)
V6—V4i	3.0786 (11)	O6WB—H6C	0.82 (2)
V7—O14	1.692 (4)	O6WB—H6D	0.82 (2)
V7—O14i	1.692 (4)
O1W—Mn1—O5W	92.8 (3)	O12—V6—O12i	105.8 (3)
O1W—Mn1—O1	177.2 (2)	O12—V6—O5	96.61 (19)
O5W—Mn1—O1	90.0 (3)	O12i—V6—O5	97.57 (19)
O1W—Mn1—O4W	88.0 (2)	O12—V6—O5i	97.57 (19)
O5W—Mn1—O4W	87.5 (3)	O12i—V6—O5i	96.61 (19)
O1—Mn1—O4W	91.99 (18)	O5—V6—O5i	156.4 (3)
O1W—Mn1—O3W	89.5 (2)	O12—V6—O13i	166.4 (2)
O5W—Mn1—O3W	90.9 (3)	O12i—V6—O13i	87.80 (18)
O1—Mn1—O3W	90.57 (17)	O5—V6—O13i	81.29 (16)
O4W—Mn1—O3W	177.02 (19)	O5i—V6—O13i	80.50 (16)
O1W—Mn1—O2W	87.9 (3)	O12—V6—O13	87.80 (18)
O5W—Mn1—O2W	179.3 (3)	O12i—V6—O13	166.4 (2)
O1—Mn1—O2W	89.35 (19)	O5—V6—O13	80.50 (16)
O4W—Mn1—O2W	92.61 (19)	O5i—V6—O13	81.28 (16)
O3W—Mn1—O2W	88.9 (2)	O13i—V6—O13	78.6 (2)
O1—V2—O4	102.5 (2)	O12—V6—V4	39.04 (15)
O1—V2—O3	103.9 (2)	O12i—V6—V4	144.81 (16)
O4—V2—O3	96.10 (18)	O5—V6—V4	89.45 (12)
O1—V2—O6	97.69 (18)	O5i—V6—V4	89.76 (12)
O4—V2—O6	90.65 (17)	O13i—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—V4i	144.81 (16)
O4—V2—O5	155.64 (17)	O12i—V6—V4i	39.04 (15)
O3—V2—O5	89.03 (18)	O5—V6—V4i	89.76 (12)
O6—V2—O5	75.72 (15)	O5i—V6—V4i	89.45 (12)
O1—V2—O13	172.67 (19)	O13i—V6—V4i	48.76 (10)
O4—V2—O13	81.85 (16)	O13—V6—V4i	127.39 (11)
O3—V2—O13	81.31 (16)	V4—V6—V4i	176.15 (6)
O6—V2—O13	76.23 (14)	O14—V7—O14i	107.0 (3)
O5—V2—O13	75.39 (15)	O14—V7—O6	96.90 (17)
O1—V2—V3	88.16 (15)	O14i—V7—O6	96.68 (17)
O4—V2—V3	130.47 (14)	O14—V7—O6i	96.68 (17)
O3—V2—V3	128.43 (14)	O14i—V7—O6i	96.90 (17)
O6—V2—V3	39.82 (11)	O6—V7—O6i	157.1 (2)
O5—V2—V3	39.40 (12)	O14—V7—O13	87.36 (17)
O13—V2—V3	84.54 (10)	O14i—V7—O13	165.61 (18)
O1—V2—V4	137.61 (16)	O6—V7—O13	80.91 (15)
O4—V2—V4	84.31 (13)	O6i—V7—O13	81.34 (15)
O3—V2—V4	33.93 (13)	O14—V7—O13i	165.61 (18)
O6—V2—V4	124.28 (11)	O14i—V7—O13i	87.36 (17)
O5—V2—V4	86.88 (11)	O6—V7—O13i	81.34 (15)
O13—V2—V4	48.09 (10)	O6i—V7—O13i	80.91 (15)
V3—V2—V4	119.20 (4)	O13—V7—O13i	78.3 (2)
O2—V3—O7	103.4 (2)	O14—V7—V5	38.37 (13)
O2—V3—O8	103.3 (2)	O14i—V7—V5	145.37 (15)
O7—V3—O8	95.17 (19)	O6—V7—V5	90.71 (12)
O2—V3—O5	99.42 (19)	O6i—V7—V5	88.54 (12)
O7—V3—O5	89.87 (18)	O13—V7—V5	49.01 (11)
O8—V3—O5	154.91 (18)	O13i—V7—V5	127.24 (12)
O2—V3—O6	100.03 (19)	O14—V7—V5i	145.37 (15)
O7—V3—O6	154.59 (17)	O14i—V7—V5i	38.37 (13)
O8—V3—O6	88.95 (18)	O6—V7—V5i	88.54 (12)
O5—V3—O6	76.57 (15)	O6i—V7—V5i	90.71 (12)
O2—V3—O13i	174.03 (19)	O13—V7—V5i	127.24 (12)
O7—V3—O13i	80.37 (16)	O13i—V7—V5i	49.01 (11)
O8—V3—O13i	80.84 (16)	V5—V7—V5i	176.25 (7)
O5—V3—O13i	75.79 (15)	V2—O1—Mn1	176.3 (3)
O6—V3—O13i	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)
O13i—V3—V2	84.45 (10)	V7—O6—V3	107.72 (18)
O2—V3—V5i	136.00 (16)	V2—O6—V3	100.38 (17)
O7—V3—V5i	83.42 (14)	V3—O7—V4i	114.8 (2)
O8—V3—V5i	32.94 (13)	V3—O8—V5i	114.9 (2)
O5—V3—V5i	124.28 (12)	V5—O10—V4	113.5 (2)
O6—V3—V5i	86.64 (11)	V6—O12—V4	109.8 (2)
O13i—V3—V5i	48.52 (10)	V6—O13—V7	101.55 (16)
V2—V3—V5i	119.30 (4)	V6—O13—V2	94.78 (15)
O9—V4—O10	103.9 (2)	V7—O13—V2	93.34 (14)
O9—V4—O7i	102.1 (2)	V6—O13—V3i	92.73 (14)
O10—V4—O7i	91.83 (19)	V7—O13—V3i	93.04 (14)
O9—V4—O3	102.0 (2)	V2—O13—V3i	168.98 (19)
O10—V4—O3	91.66 (19)	V6—O13—V4	88.32 (14)
O7i—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)	V3i—O13—V4	85.80 (13)
O7i—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)	V3i—O13—V5	84.79 (13)
O7i—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)
O7i—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)
O7i—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
O7i—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—O8i	102.2 (2)	C12—C10—C11	110.4 (6)
O10—V5—O8i	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)
O8i—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
O8i—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
O8i—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
O8i—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
O8i—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—V3i	134.32 (17)	O13B—C13—H13F	109.1
O10—V5—V3i	82.75 (14)	C10—C13—H13F	109.1
O8i—V5—V3i	32.17 (13)	H13E—C13—H13F	107.8
O4—V5—V3i	122.87 (13)	C13—O13A—H13A	109.5
O14—V5—V3i	82.10 (11)	C13—O13B—H13B	109.5
O13—V5—V3i	46.69 (9)	H6A—O6WA—H6B	110 (4)
V4—V5—V3i	60.92 (3)	H6C—O6WB—H6D	110 (4)
V7—V5—V3i	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)	V3i—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)	O7i—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)
O7i—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)	O12i—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)	O5i—V6—O12—V4	−80.2 (2)
O3—V2—O4—V5	−70.4 (2)	O13i—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)	V4i—V6—O12—V4	179.93 (3)
O13—V2—O4—V5	9.9 (2)	O14i—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)	O6i—V7—O14—V5	79.1 (2)
O2—V3—O7—V4i	−174.8 (2)	O13—V7—O14—V5	−1.86 (18)
O8—V3—O7—V4i	−69.9 (2)	O13i—V7—O14—V5	−0.3 (8)
O5—V3—O7—V4i	85.5 (2)	V5i—V7—O14—V5	−179.85 (2)
O6—V3—O7—V4i	28.6 (6)	N1—C10—C11—O11A	54.2 (7)
O13i—V3—O7—V4i	9.9 (2)	C12—C10—C11—O11A	170.8 (6)
V2—V3—O7—V4i	84.1 (3)	C13—C10—C11—O11A	−63.0 (8)
V5i—V3—O7—V4i	−39.0 (2)	N1—C10—C12—O12A	−62.1 (8)
O2—V3—O8—V5i	174.5 (2)	C11—C10—C12—O12A	−179.3 (6)
O7—V3—O8—V5i	69.4 (2)	C13—C10—C12—O12A	54.4 (9)
O5—V3—O8—V5i	−31.4 (6)	N1—C10—C13—O13A	−175.5 (8)
O6—V3—O8—V5i	−85.5 (2)	C12—C10—C13—O13A	67.7 (10)
O13i—V3—O8—V5i	−9.9 (2)	C11—C10—C13—O13A	−57.5 (10)
V2—V3—O8—V5i	−85.1 (2)	N1—C10—C13—O13B	−102.3 (14)
O11—V5—O10—V4	179.6 (2)	C12—C10—C13—O13B	140.9 (14)
O8i—V5—O10—V4	76.2 (2)	C11—C10—C13—O13B	15.8 (15)
O4—V5—O10—V4	−77.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O14ii	0.70 (12)	2.01 (12)	2.703 (7)	167 (12)
O1W—H1B···O12iii	0.70 (7)	2.04 (8)	2.727 (8)	169 (8)
O2W—H2A···O5iv	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···O7iv	0.70 (9)	1.94 (9)	2.636 (7)	176 (10)
O3W—H3B···O11Av	0.88 (8)	1.91 (8)	2.752 (8)	160 (7)
O4W—H4A···O6vi	0.82 (11)	1.90 (11)	2.708 (6)	167 (10)
O4W—H4B···O2Wvi	0.76 (9)	2.12 (9)	2.871 (7)	169 (9)
O5W—H5A···O8vi	0.55 (11)	2.18 (11)	2.725 (10)	170 (16)
O5W—H5B···O13Av	0.83 (14)	2.12 (13)	2.699 (12)	127 (12)
O5W—H5B···O13Bv	0.83 (14)	1.95 (14)	2.77 (2)	168 (13)
N1—H1C···O3Wvi	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···O4vi	0.89	1.91	2.787 (6)	166
C11—H11C···O11vi	0.97	2.46	3.392 (9)	160
O11A—H11A···O6WAvi	0.82	1.96	2.758 (12)	166
O12A—H12A···O3iv	0.82	1.94	2.756 (7)	174
C13—H13E···O2	0.97	2.40	3.280 (10)	151
O13B—H13B···O6WBvii	0.77	1.92	2.60 (2)	148
O6WA—H6A···O3	0.82 (2)	2.23 (9)	2.966 (9)	150 (15)
O6WA—H6B···O10viii	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···O10viii	0.82 (2)	1.93 (8)	2.720 (19)	161 (24)