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

Franco, M.P.; Rüdiger, A.L.; Soares, J.F.; Nunes, G.G.; Hughes, D.L.

doi:10.1107/S2056989014028230

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 2| February 2015| Pages 146-150

doi:10.1107/S2056989014028230

Open

access

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

Maurício P. Franco,^a André Luis Rüdiger,^a Jaísa F. Soares,^a Giovana G. Nunes ^a and David L. Hughes ^b ^*

^aDepartamento de Química, Universidade Federal do Paraná, Centro Politécnico, Jardim das Américas, 81530-900 Curitiba, PR, Brazil, and ^bSchool of Chemistry, University of East Anglia, Norwich NR4 7TJ, England
^*Correspondence e-mail: d.l.hughes@uea.ac.uk

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 7 December 2014; accepted 29 December 2014; online 10 January 2015)

Two heterometallic decavanadate(V) compounds, bis(tetramethylammonium) decaaquadi-μ₄-oxido-tetra-μ₃-oxido-hexadeca-μ₂-oxido-hexaoxidodimanganese(II)decavanadate(V) pentahydrate, (Me₄N)₂[V₁₀O₂₈{Mn(H₂O)₅}₂]·5H₂O, A, and bis{[tris(hydroxymethyl)methyl]ammonium} decaaquadi-μ₄-oxido-tetra-μ₃-oxido-hexadeca-μ₂-oxido-hexaoxidodimanganese(II)decavanadate(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 decavanadate cluster through oxide bridges. In A, the decavanadate 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, tetramethylammonium and [tris(hydroxymethyl)methyl]ammonium, respectively, and on the number and arrangement of the water molecules of crystallization. In both compounds, the H atoms from the coordinating water molecules participate in extensive three-dimensional hydrogen-bonding networks, which link the cluster units both directly and through solvent molecules 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 interactions are also observed in both structures.

Keywords: crystal structure; decavanadate; heteropolyanion; manganese(II); organic cations.

CCDC references: 1041495; 1041494

1. 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, [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., 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.

2. 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, $[{1\over 2}]$ − z.]

Figure 3
The anion of compound B viewed approximately down the a axis of the V₁₀O₂₈ moiety. [Symmetry code: (1) 1 − x, y, $[{1\over 2}]$ − z.]

Figure 4
The anion of compound B viewed approximately down the b axis of the V₁₀O₂₈ moiety. [Symmetry code: (1) 1 − x, y, $[{1\over 2}]$ − z.]

Figure 5
The anion of compound B viewed approximately down the c axis of the V₁₀O₂₈ moiety. [Symmetry code: (1) 1 − x, y, $[{1\over 2}]$ − 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.

3. 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⋯O11^iv	0.96	2.51	3.362 (2)	148
C10—H10C⋯O2^v	0.96	2.58	3.370 (3)	139
C10—H10C⋯O2^vi	0.96	2.57	3.370 (3)	141
C11—H11A⋯O8^vii	0.96	2.48	3.384 (3)	156
C12—H12A⋯O12ⁱⁱⁱ	0.96	2.60	3.474 (4)	152
C12—H12C⋯O12^iv	0.96	2.59	3.474 (4)	153
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) x+1, y, z; (vi) x+1, -y+1, z; (vii) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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⋯O6^v	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⋯O8^v	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⋯O4^v	0.89	1.91	2.787 (6)	166
C11—H11C⋯O11^v	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⋯O10^vii	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^vii	0.82 (2)	1.93 (8)	2.720 (19)	161 (24)
Symmetry codes: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+1, z-{\script{1\over 2}}]$ ; (v) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[x, -y+1, z+{\script{1\over 2}}]$ ; (vii) -x+1, -y+1, -z.

4. 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 ).

5. 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 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 [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.

6. 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[F² > 2σ(F²)], wR(F²), 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_o²) + (0.0329P)² + 2.2668P] where P = (F_o² + 2F_c²)/3	w = 1/[σ²(F_o²) + (0.0062P)² + 110.7865P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (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].

Supporting information

CCDC references: 1041495; 1041494

Crystal structure: contains datablocks Compound-A, Compound-B, global. DOI: 10.1107/S2056989014028230/hb7337sup1.cif

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

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

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

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

checkCIF report

Chemical context top

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.

Structural commentary top

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.

Supramolecular features top

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.

Database survey top

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).

Synthesis and crystallization top

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.

Refinement details top

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 top

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 top

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 top

	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 top

Crystal data top

(C₄H₁₂N)₂·[Mn₂V₁₀O₂₈(H₂O)₁₀]·5H₂O	F(000) = 1480
M_r = 1485.81	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0329P)² + 2.2668P] where P = (F_o² + 2F_c²)/3
2953 reflections	(Δ/σ)_max = 0.001
194 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

(C₄H₁₂N)₂·[Mn₂V₁₀O₂₈(H₂O)₁₀]·5H₂O	V = 2242.1 (2) Å³
M_r = 1485.81	Z = 2
Monoclinic, I2/m	Mo Kα radiation
a = 13.2434 (7) Å	µ = 2.64 mm⁻¹
b = 9.6402 (5) Å	T = 292 K
c = 17.7628 (13) Å	0.48 × 0.38 × 0.15 mm
β = 98.626 (2)°

Data collection top

Bruker D8 Venture/Photon 100 CMOS diffractometer	2953 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	2752 reflections with I > 2σ(I)
T_min = 0.562, T_max = 0.746	R_int = 0.025
81983 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.58 e Å⁻³
2953 reflections	Δρ_min = −0.34 e Å⁻³
194 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	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

Geometric parameters (Å, º) top

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)

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) top

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 top

Crystal data top

(C₄H₁₂NO₃)₂[Mn₂V₁₀O₂₈(H₂O)₁₀]·2H₂O	F(000) = 3032
M_r = 1527.76	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0062P)² + 110.7865P] where P = (F_o² + 2F_c²)/3
3936 reflections	(Δ/σ)_max < 0.001
385 parameters	Δρ_max = 0.78 e Å⁻³
6 restraints	Δρ_min = −1.11 e Å⁻³

Crystal data top

(C₄H₁₂NO₃)₂[Mn₂V₁₀O₂₈(H₂O)₁₀]·2H₂O	V = 4276.3 (3) Å³
M_r = 1527.76	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 19.3147 (8) Å	µ = 2.78 mm⁻¹
b = 9.7733 (4) Å	T = 295 K
c = 22.7952 (10) Å	0.49 × 0.26 × 0.13 mm
β = 96.392 (1)°

Data collection top

Bruker D8 Venture/Photon 100 CMOS diffractometer	3936 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	3280 reflections with I > 2σ(I)
T_min = 0.542, T_max = 0.745	R_int = 0.039
71752 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	6 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0062P)² + 110.7865P] where P = (F_o² + 2F_c²)/3
3936 reflections	Δρ_max = 0.78 e Å⁻³
385 parameters	Δρ_min = −1.11 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

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···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.

Hydrogen-bond geometry (Å, º) for (Compound-A) top

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···O11^iv	0.96	2.51	3.362 (2)	148
C10—H10C···O2^v	0.96	2.58	3.370 (3)	139
C10—H10C···O2^vi	0.96	2.57	3.370 (3)	141
C11—H11A···O8^vii	0.96	2.48	3.384 (3)	156
C12—H12A···O12ⁱⁱⁱ	0.96	2.60	3.474 (4)	152
C12—H12C···O12^iv	0.96	2.59	3.474 (4)	153

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

Hydrogen-bond geometry (Å, º) for (Compound-B) top

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···O6^v	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···O8^v	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···O4^v	0.89	1.91	2.787 (6)	166
C11—H11C···O11^v	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···O10^vii	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^vii	0.82 (2)	1.93 (8)	2.720 (19)	161 (24)

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

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 diffractometer	Bruker D8 Venture/Photon 100 CMOS diffractometer
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[F² > 2σ(F²)], wR(F²), 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_o²) + (0.0329P)² + 2.2668P] where P = (F_o² + 2F_c²)/3	w = 1/[σ²(F_o²) + (0.0062P)² + 110.7865P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.34	0.78, −1.11

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

Acknowledgements

Financial support from the Brazilian agencies CNPq (grant No. 307592/2012–0) and CAPES (grant PVE A099/2013) is gratefully acknowledged. The authors also thank CNPq, CAPES and Fundação Araucária (Brazil) for fellowships.

References

Aureliano, M. (2014). Inorg. Chim. Acta, 420, 4–7. Google Scholar
Aureliano, M. & Ohlin, C. A. (2014). J. Inorg. Biochem. 137, 123–130. Google Scholar
Bošnjaković-Pavlović, N., Spasojević-de Biré, A., Tomaz, I., Bouhmaida, N., Avecilla, F., Mioč, U. B., Pessoa, J. C. & Ghermani, N. E. (2009). Inorg. Chem. 48, 9742–9753. Google Scholar
Bruker (2010). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2012). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chatkon, A., Chatterjee, P. B., Sedgwick, M. A., Haller, K. J., Crans, D. C. (2013). Eur. J. Inorg. Chem. pp. 1859–1868. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Inami, S., Nishio, M., Hayashi, Y., Isobe, K., Kameda, H. & Shimoda, T. (2009). Eur. J. Inorg. Chem. pp. 5253–5258. Google Scholar
Klištincová, L., Rakovský, E. & Schwendt, P. (2009). Acta Cryst. C65, m97–m99. Web of Science CSD CrossRef IUCr Journals Google Scholar
Klištincová, L., Rakovský, E. & Schwendt, P. (2010). Transition Met. Chem. 35, 229–236. Google Scholar
Li, T. H., Lu, J., Gao, S. Y., Li, F. & Cao, R. (2007). Chem. Lett. 36, 356–357. Google Scholar
Lin, S. W., Wu, Q., Tan, H. Q. & Wang, E. B. (2011). J. Coord. Chem. 64, 3661–3669. Google Scholar
Liu, J. L. & Zhou, Y. Z. (2010). Prog. Chem. 22, 51–57. Google Scholar
Long, D. L., Tsunashima, R. & Cronin, L. (2010). Angew. Chem. Int. Ed. 49, 1736–1758. Google Scholar
Mestiri, I., Ayed, B. & Haddad, A. (2013). J. Cluster Sci. 24, 85–96. Google Scholar
Nunes, G. G., Bonatto, A. C., de Albuquerque, C. G., Barison, A., Ribeiro, R. R., Back, D. F., Andrade, A. V. C., de Sá, E. L., Pedrosa, F. de O., Soares, J. F. & de Souza, E. M. (2012). J. Inorg. Biochem. 108, 36–46. Google Scholar
Pavliuk, M. V., Makhankova, V. G., Khavryuchenko, O. V., Kokozay, V. N., Omelchenko, I. V., Shishkin, O. V. & Jezierska, J. (2014). Polyhedron, 81, 597–606. Google Scholar
Shan, Y. K. & Huang, S. D. (1999). J. Chem. Crystallogr. 29, 93–97. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Silva, J. L. F. da, da Piedade, M. F. M. & Duarte, M. T. (2003). Inorg. Chim. Acta, 356, 222–242. Google Scholar
Wang, L., Li, Y., Wang, Y. Y., Liang, Z. Q., Yu, J. H. & Xu, R. R. (2011). Inorg. Chem. Commun. 14, 1640–1643. Google Scholar
Wang, L., Sun, X. P., Liu, M. L., Gao, Y. Q., Gu, W. & Liu, X. (2008). J. Cluster Sci. 19, 531–542. Google Scholar
Wang, J. P., Yan, Q. X., Du, X. D. & Niu, J. Y. (2008). J. Clust Sci. 19, 491–498. Google Scholar
Wu, Q., Hao, X. L., Feng, X. J., Wang, Y. H., Li, Y. G., Wang, E. B., Zhu, X. Q. & Pan, X. H. (2012). Inorg. Chem. Commun. 22, 137–140. Google Scholar
Xu, W. T., Jiang, F. L., Zhou, Y. F., Xiong, K. C., Chen, L., Yang, M., Feng, R. & Hong, M. C. (2012). Dalton Trans. 41, 7737–7745. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 2| February 2015| Pages 146-150

doi:10.1107/S2056989014028230

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)