Crystal structure of bis­(ammonium) bis­[penta­aqua­(di­methyl­formamide)­zinc(II)] deca­vanadate tetra­hydrate

Ebrahimi, A.; Gyepes, R.; Bujdoš, M.; Krivosudský, L.

doi:10.1107/S2056989022003449

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ISSN: 2056-9890

Volume 78| Part 5| May 2022| Pages 481-484

https://doi.org/10.1107/S2056989022003449

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Crystal structure of bis(ammonium) bis[pentaaqua(dimethylformamide)zinc(II)] decavanadate tetrahydrate

Arash Ebrahimi,^a Róbert Gyepes,^b Marek Bujdoš ^c and Lukáš Krivosudský ^a ^*

^aComenius University in Bratislava, Faculty of Natural Sciences, Department of Inorganic Chemistry, Mlynská dolina, Ilkovičova 6, 842 15 Bratislava, Slovakia, ^bCharles University, Department of Inorganic Chemistry, Hlavova 2030, Prague, 128 00, Czech Republic, and ^cComenius University in Bratislava, Faculty of Natural Sciences, Institute of Laboratory Research on Geomaterials, Mlynská dolina, Ilkovičova 6, 842 15 Bratislava, Slovakia
^*Correspondence e-mail: lukas.krivosudsky@uniba.sk

Edited by C. Schulzke, Universität Greifswald, Germany (Received 3 March 2022; accepted 27 March 2022; online 5 April 2022)

The crystalline product (NH₄)₂[Zn(C₃H₇NO)(H₂O)₅]₂[V₁₀O₂₈]·4H₂O was successfully isolated from an H₂O/DMF solvent combination by evaporation at ambient temperature. The salt crystallizes in the P2₁/n space group. Imidazole, initially used in the synthesis but not present in the product, and DMF solvent appear to affect the synthesis and crystallization as structural-directing agents. In the title compound, the complex cation [Zn(H₂O)₅(DMF)]²⁺ acts as a counter-ion without being directly coordinated to the decavanadate anion. An extensive framework of hydrogen bonds integrates the whole architecture as evidenced by X-ray crystallography. The polyoxometalate [V₁₀O₂₈]^6– lies on a center of symmetry while the complex cation [Zn(H₂O)₅(DMF)]²⁺ links three adjacent anions through a set of 2 + 2 + 3 hydrogen bonds.

Keywords: crystal structure; decavanadate; zinc complexes; polyoxometalate; hydrogen bonds.

CCDC reference: 2156016

1. Chemical context

Decavanadate anions, H_xV₁₀O₂₈^(6–x)–, are the major species in equilibrated aqueous vanadate solutions (Rehder, 2015 ; Gorzsás et al., 2009 ) at vanadium(V) concentrations above 1 mM in the pH range of ≃2–6 (Schmidt et al., 2001 ; Pettersson et al., 1985 ), and are also stabilized in some organic solvents (Slebodnick & Pecoraro, 1998 ). There are altogether 54 compounds in the CSD (WebCSD, accessed January 2022; Groom et al., 2016 ) that contain a decavanadate anion and a transition-metal complex cation, either coordinated or as a free counter-ion. Both groups are evenly abundant (27 structures). In our search for conditions under which the decavanadate acts as a ligand we focused on Zn²⁺ complexes that have already shown the ability to act as a counter-ion: (NH₄)₂[Zn (H₂O)₆]₂[V₁₀O₂₈]·4H₂O (Udomvech et al., 2012 ), [Zn(H₂O)₆]_n[{Na₂(H₂O)₆(μ₂-H₂O)₄Zn(H₂O)₂}V₁₀O₂₈]_n·4nH₂O (Yerra & Das, 2017 ), [Zn₃(Htrz)₆(H₂O)₆][V₁₀O₂₈]·10H₂O·Htrz (Xu et al., 2012 ), (C₄H₁₄N₂)₂]·[Zn(H₂O)₆][V₁₀O₂₈]·6H₂O (Jin et al., 2018 ), (NH₄)₂[Zn(H₂O)₅(NH₃CH₂CH₂COO)]₂[V₁₀O₂₈]·nH₂O (Klištincová et al., 2010 ); as well as being directly coordinated to decavanadate: {[Zn₂(H₂O)₁₄[V₁₀O₂₈]}·H₂ppz (Wang et al., 2008 ), {[Zn(en)₂]₃[V₁₀O₂₈]}·5H₂O (Pang et al., 2012 ), {[Zn(im)₂(DMF)₂]₂[H₂V₁₀O₂₈]·im·DMF (Xu et al., 2012), {[Zn₃(trz)₃(H₂O)₄(DMF)]₂[V₁₀O₂₈]·4H₂O}_n (Xu et al., 2012), [(CH₃)₄N]₂[Zn(H₂O)₅]₂[V₁₀O₂₈]}·5H₂O (Huang et al., 2021 ) and {[Zn(H₂O)₆][Zn₂[V₁₀O₂₈](H₂O)₁₀]}·6H₂O (Graia et al., 2008 ) (im = imidazole, Htrz = 1,2,4-triazole, DMF = N,N′-dimethylformamide, en = ethane-1,2-diamine, ppz = piperazine). Employing zinc(II) centers as part of linker moieties for the construction of polyoxometalate-based metal organic frameworks (POMOFs) comes with an advantage over traditionally used rare metals regarding costs, and sometimes even efficiency. Important applications of POMOFs in materials chemistry include, for instance, photovoltaics (Luo et al., 2012 ) and hydrogen evolution (Nohra et al., 2011 ). Despite extensive experimental work with an inexpensive multicomponent system H₂O/DMF/imidazole/Zn²⁺/V⁵⁺, we were not able to isolate from the various preparations any crystalline product other than (NH₄)₂[Zn(H₂O)₅(DMF)]₂[V₁₀O₂₈]·4H₂O (1). Its crystal structure is presented here.

2. Structural commentary

Compound 1 crystallizes from a bicomponent solvent H₂O/DMF at room temperature in the form of orange block-shaped crystals in monoclinic symmetry [P2₁/n; β = 108.628 (1)°]. Although imidazole is not present in the crystal structure, neither as a free molecule or cation nor as a ligand, its presence was necessary for crystallization to take place. In the absence of imidazole we observed the formation of oily solutions without crystalline product or the slow reduction of vanadium accompanied by a change in color of the solution from orange to greenish. The asymmetric unit of (NH₄)₂[Zn(H₂O)₅(DMF)]₂[V₁₀O₂₈]·4H₂O (Fig. 1) comprises one half of the [V₁₀O₂₈]^6– polyoxometalate, one [Zn(H₂O)₅(DMF)]²⁺ complex cation, one NH₄⁺ and two molecules of water of crystallization. The H atoms of the ammonium cation and water molecules were found in the difference map and refined freely except for three water molecules where restraints on the O—H distances were applied. The H atoms bound to the C atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms. The Zn²⁺ center in [Zn(H₂O)₅(DMF)]²⁺ is coordinated by five aqua ligands with Zn—O bond lengths in the range 2.0482 (16)–2.1273 (16) Å and one N,N′-dimethylformamide ligand coordinated through the oxygen atom with a Zn—O bond length of 2.0926 (14) Å, forming an irregular octahedron. The decavanadate anion [V₁₀O₂₈]^6– is present in a fully deprotonated form, as further confirmed by elemental analysis and charge balance. It resides in a special position on the center of symmetry, as observed many times before (Rakovský & Krivosudský, 2014 ). The anion adopts C_i symmetry (idealized D_2h) and is composed of ten edge-sharing heavily distorted octahedra. The terminal vanadium–oxygen bond lengths (V=O groups) are in the range 1.5929 (14)–1.6210 (14) Å, with an average value of 1.6083 Å. The bond lengths of the bridging μ–O atoms are in the range 1.6890 (13)–2.0696 (14) Å, with an average value of 1.853 Å. The bond lengths of the bridging μ₃–O atoms with coordination numbers of three are in the range 1.8700 (14)–2.0208 (14) Å, with an average value of 1.9725 Å. Bond lengths of the hexacoordinated oxygen atom trapped inside the decavanadate (O16) are in the range 2.1033 (13)–2.3337 (13) Å, with an average value of 2.2222 Å. All metrical parameters fall in their typical ranges.

Figure 1
The molecular structure of 1 showing 50% displacement ellipsoids illustrated with DIAMOND (Brandenburg & Putz, 2005

). The half of the decavanadate anion that is not part of the asymmetric unit is displayed as faded.

3. Supramolecular features

The supramolecular structure of 1 is stabilized by a rich network of hydrogen bonds that involves all components of the compound. The strongest hydrogen bonds are formed by the complex cation (Fig. 2, Table 1), which serves as a linker for decavanadate anions in its vicinity. More specifically, [Zn(H₂O)₅(DMF)]²⁺ forms 2 + 2 + 3 hydrogen bonds through its aqua ligands (as donors) to three different [V₁₀O₂₈]⁶⁻ anions (as acceptors). The structural parameters of the hydrogen bonds are summarized in Table 1. Based on the D⋯A distances ranging from 2.659 (2) to 2.892 (2) Å and the angles D—H⋯A falling into the range 164 (3)–177 (3)°, the hydrogen bonds may be considered relatively strong examples.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O15ⁱ	0.75 (3)	1.98 (3)	2.722 (2)	167 (3)
O3—H3P⋯O18	0.83 (3)	2.07 (3)	2.892 (2)	173 (3)
O4—H4O⋯O17ⁱⁱ	0.74 (3)	1.97 (3)	2.710 (2)	177 (3)
O5—H5O⋯O19	0.85 (3)	1.82 (3)	2.659 (2)	169 (3)
O5—H5P⋯O9ⁱⁱⁱ	0.76 (3)	2.10 (3)	2.842 (2)	164 (3)
O6—H6O⋯O7ⁱⁱⁱ	0.82 (3)	1.95 (3)	2.771 (2)	173 (3)
O6—H6P⋯O11ⁱⁱ	0.78 (2)	2.00 (2)	2.769 (2)	170 (3)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
Relative positions of the three adjacent decavanadate anions (orange polyhedra) linked by a single [Zn(H₂O)₅(DMF)]²⁺ cation.

4. Database survey

In a search of the Cambridge Structural Database (WebCSD, accessed January 2022; Groom et al., 2016) for closely related decavanadates bearing mononuclear zinc(II) complex cations which are not coordinated to the decavanadate anion, six entries were found: (NH₄)₂[Zn(H₂O)₆]₂[V₁₀O₂₈]·4H₂O ICSD Entry: 422816 (Udomvech et al., 2012), [Zn(H₂O)₆]_n[{Na₂(H₂O)₆(μ-H₂O)₄Zn(H₂O)₂}V₁₀O₂₈]_n·4nH₂O ICSD Entry: 427974 (Yerra & Das, 2017), (C₄H₁₄N₂)₂]·[Zn(H₂O)₆][V₁₀O₂₈]·6H₂O YEYYEJ (Jin et al., 2018), (NH₄)₂[Zn(H₂O)₅(NH₃CH₂CH₂COO)]₂[V₁₀O₂₈]·nH₂O XABQIC (Klištincová et al., 2010), [Zn(3-Hdpye)(H₂O)₅]₂[V₁₀O₂₈]·4H₂O OXUYUD (Wang et al., 2016 ), and [Zn(H₂O)₆][Na₃(H₂O)₁₄][HV₁₀O₂₈]·4H₂O SUDGUW (Amanchi & Das, 2018 ). The overall compositions (cations, decavanadate anion, water) are in all cases similar to that of the title compound.

5. Synthesis and crystallization

NH₄VO₃ (0.464 g, 4 mmol) was dissolved in 20 ml of water and stirred upon heating. After being cooled down to ambient temperature, decavanadate was prepared in situ by adjusting the pH to 4 with 2 M HCl until the color of the solution changed from bright yellow to orange. Under continuous stirring, imidazole (0.136 g, 2 mmol) was poured into the mixture and the pH was adjusted to 4 by adding 2 M HCl again. Finally, first ZnSO₄·7H₂O (0.287 g, 1 mmol) and secondly 20 mL of DMF were added to the clear solution. The mixture was filtered, and the clear orange filtrate was left to crystallize at RT. The orange crystals were isolated a few days later. The vanadium content was determined using an ICP MS Thermo Scientific iCap-Q; the zinc content was determined using an AAS Perkin-Elmer Model 1100. An infrared spectrum was recorded on a Nicolet FTIR 6700 spectrometer in Nujol mull. Analytical data for C₆H₅₀N₄O₄₄V₁₀Zn₂: theoretical V 33.5%, Zn 8.6%; found V 32.4%, Zn 8.40%. Characteristic bands in the FTIR spectrum (in cm⁻¹): V₁₀O₂₈ 964, 951, 938, 805, 596; NH₄⁺ 1416; DMF 1658, 1382, 1118.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were refined isotropically and those on carbon atoms were placed in geometrically idealized positions (C—H = 0.93 Å) and constrained to ride on their parent atoms with U_iso(H) = 1.2 U_eq(C). Hydrogen atoms of the water molecules and the ammonium cation were found in the difference-Fourier map. For the two lattice water molecules and one coordinated water, the O—H distances were restrained with DFIX while orientation and displacement parameters were refined freely. All other water hydrogen atoms and the ammonium cation hydrogen atoms were refined freely.

Table 2
Experimental details

Crystal data
Chemical formula	(NH₄)₂[Zn(C₃H₇NO)(H₂O)₅]₂[V₁₀O₂₈]·4H₂O
M_r	1522.64
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	15.5436 (6), 8.6538 (4), 16.7362 (7)
β (°)	108.628 (1)
V (Å³)	2133.27 (16)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	3.31
Crystal size (mm)	0.49 × 0.23 × 0.10

Data collection
Diffractometer	Nonius KappaCCD with Buker APEXII detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.57, 0.73
No. of measured, independent and observed [I > 2σ(I)] reflections	29908, 4901, 4354
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.056, 1.06
No. of reflections	4901
No. of parameters	372
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.62
Computer programs: Instrument Service (Bruker, 2021 ), SAINT (Bruker, 2021 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and DIAMOND (Brandenburg & Putz, 2005 ).

Supporting information

CCDC reference: 2156016

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022003449/yz2017sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022003449/yz2017Isup2.hkl

checkCIF report

Computing details top

Data collection: Instrument Service (Bruker, 2021); cell refinement: SAINT (Bruker, 2019); data reduction: SAINT (Bruker, 2019); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: DIAMOND (Brandenburg & Putz, 2005).

Bis(ammonium) bis[pentaaqua(dimethylformamide)zinc(II)] decavanadate tetrahydrate top

Crystal data top

(NH₄)₂[Zn(C₃H₇NO)(H₂O)₅]₂[V₁₀O₂₈]·4H₂O	F(000) = 1512
M_r = 1522.64	D_x = 2.370 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.5436 (6) Å	Cell parameters from 9949 reflections
b = 8.6538 (4) Å	θ = 2.6–27.5°
c = 16.7362 (7) Å	µ = 3.31 mm⁻¹
β = 108.628 (1)°	T = 120 K
V = 2133.27 (16) Å³	Prism, orange
Z = 2	0.49 × 0.23 × 0.10 mm

Data collection top

Nonius KappaCCD with Buker APEXII detector diffractometer	4354 reflections with I > 2σ(I)
data from phi and ω scans	R_int = 0.033
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 27.5°, θ_min = 2.2°
T_min = 0.57, T_max = 0.73	h = −20→19
29908 measured reflections	k = −11→11
4901 independent reflections	l = −21→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.056	w = 1/[σ²(F_o²) + (0.0284P)² + 1.1852P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
4901 reflections	Δρ_max = 0.36 e Å⁻³
372 parameters	Δρ_min = −0.62 e Å⁻³
6 restraints

Special details top

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

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

	x	y	z	U_iso*/U_eq
Zn1	0.31800 (2)	0.46454 (3)	0.54363 (2)	0.00759 (6)
O1	0.36049 (10)	0.62987 (16)	0.47301 (9)	0.0114 (3)
O2	0.31034 (13)	0.30400 (19)	0.45168 (11)	0.0159 (3)
H2O	0.276 (2)	0.240 (3)	0.4386 (19)	0.027 (9)*
H2P	0.350 (2)	0.281 (4)	0.439 (2)	0.043 (11)*
O3	0.44977 (11)	0.3899 (2)	0.60794 (10)	0.0125 (3)
H3O	0.4493 (17)	0.310 (3)	0.6204 (16)	0.012 (7)*
H3P	0.478 (2)	0.433 (3)	0.653 (2)	0.027 (8)*
O4	0.27068 (12)	0.31855 (17)	0.62168 (10)	0.0107 (3)
H4O	0.2351 (18)	0.260 (3)	0.6034 (16)	0.012 (7)*
H4P	0.311 (2)	0.274 (3)	0.6540 (19)	0.026 (8)*
O5	0.32040 (12)	0.64584 (19)	0.62565 (10)	0.0147 (3)
H5O	0.338 (2)	0.648 (4)	0.679 (2)	0.037 (9)*
H5P	0.309 (2)	0.728 (4)	0.609 (2)	0.041 (10)*
O6	0.17863 (11)	0.51996 (18)	0.48529 (10)	0.0107 (3)
H6O	0.1613 (18)	0.600 (3)	0.4584 (16)	0.025 (8)*
H6P	0.1389 (16)	0.463 (3)	0.4648 (17)	0.018 (7)*
C1	0.31089 (15)	0.6545 (2)	0.39870 (13)	0.0127 (4)
H1	0.267624	0.577353	0.372375	0.015*
N1	0.31404 (12)	0.7783 (2)	0.35441 (11)	0.0126 (4)
C2	0.37449 (17)	0.9071 (3)	0.38953 (16)	0.0207 (5)
H2A	0.339767	0.991473	0.403582	0.031*
H2B	0.402328	0.943400	0.348019	0.031*
H2C	0.422078	0.873260	0.440631	0.031*
C3	0.24580 (16)	0.8028 (3)	0.27197 (15)	0.0230 (5)
H3A	0.208105	0.710072	0.255621	0.035*
H3B	0.276127	0.823842	0.229986	0.035*
H3C	0.207451	0.891060	0.275052	0.035*
V1	0.66396 (2)	0.54542 (4)	0.97966 (2)	0.00519 (8)
V2	0.48442 (2)	0.68753 (4)	0.99591 (2)	0.00468 (8)
V3	0.54965 (2)	0.33633 (4)	0.83349 (2)	0.00615 (8)
V4	0.37025 (2)	0.46974 (4)	0.84932 (2)	0.00550 (8)
V5	0.51936 (2)	0.68687 (4)	0.82367 (2)	0.00627 (8)
O7	0.63516 (9)	0.70057 (15)	0.90117 (8)	0.0068 (3)
O8	0.48640 (9)	0.80713 (15)	0.91677 (8)	0.0066 (3)
O9	0.76998 (9)	0.57672 (15)	1.03142 (9)	0.0079 (3)
O10	0.60927 (9)	0.67399 (15)	1.05199 (8)	0.0057 (3)
O11	0.45500 (9)	0.79640 (15)	1.06789 (8)	0.0066 (3)
O12	0.57404 (10)	0.20530 (16)	0.77742 (9)	0.0102 (3)
O13	0.42410 (9)	0.32537 (15)	0.79962 (8)	0.0067 (3)
O14	0.26409 (10)	0.43520 (16)	0.80457 (9)	0.0096 (3)
O15	0.66637 (9)	0.39324 (15)	0.90763 (8)	0.0068 (3)
O16	0.51531 (9)	0.50621 (14)	0.92593 (8)	0.0055 (3)
O17	0.36261 (9)	0.60759 (15)	0.94154 (8)	0.0061 (3)
O18	0.54495 (10)	0.51674 (15)	0.77235 (9)	0.0072 (3)
O19	0.39504 (9)	0.63135 (15)	0.79227 (8)	0.0070 (3)
O20	0.51633 (10)	0.82531 (16)	0.75840 (9)	0.0107 (3)
N2	0.13802 (14)	0.5436 (2)	0.65462 (12)	0.0091 (4)
H2R	0.0918 (19)	0.476 (3)	0.6319 (17)	0.017 (7)*
H2S	0.176 (2)	0.502 (3)	0.691 (2)	0.024 (8)*
H2T	0.1165 (18)	0.620 (3)	0.6764 (16)	0.019 (7)*
H2Q	0.165 (2)	0.572 (3)	0.618 (2)	0.031 (8)*
O21	0.41424 (12)	0.08923 (19)	0.64987 (12)	0.0191 (4)
H21A	0.446 (2)	0.032 (3)	0.6837 (18)	0.036 (9)*
H21B	0.3783 (19)	0.042 (3)	0.6175 (18)	0.037 (10)*
O22	0.46542 (13)	0.2601 (2)	0.41289 (12)	0.0260 (4)
H22A	0.472 (2)	0.250 (4)	0.3693 (16)	0.040 (10)*
H22B	0.5092 (18)	0.296 (4)	0.4460 (18)	0.039 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.00799 (12)	0.00689 (11)	0.00765 (11)	−0.00058 (9)	0.00214 (9)	−0.00008 (9)
O1	0.0120 (8)	0.0121 (7)	0.0107 (7)	−0.0031 (6)	0.0046 (6)	0.0005 (6)
O2	0.0122 (9)	0.0163 (8)	0.0222 (9)	−0.0065 (7)	0.0099 (7)	−0.0108 (7)
O3	0.0122 (8)	0.0103 (8)	0.0122 (8)	0.0005 (7)	0.0001 (6)	0.0005 (7)
O4	0.0087 (8)	0.0085 (7)	0.0129 (8)	−0.0020 (7)	0.0006 (7)	0.0017 (6)
O5	0.0246 (9)	0.0090 (8)	0.0068 (8)	0.0014 (7)	−0.0002 (7)	−0.0004 (6)
O6	0.0079 (8)	0.0077 (7)	0.0133 (8)	−0.0006 (6)	−0.0009 (6)	0.0015 (6)
C1	0.0122 (11)	0.0143 (10)	0.0135 (10)	0.0001 (9)	0.0069 (9)	−0.0010 (8)
N1	0.0106 (9)	0.0150 (9)	0.0142 (9)	0.0021 (7)	0.0069 (8)	0.0037 (7)
C2	0.0288 (14)	0.0143 (11)	0.0244 (12)	−0.0034 (10)	0.0162 (11)	0.0011 (9)
C3	0.0163 (12)	0.0374 (14)	0.0168 (12)	0.0070 (11)	0.0073 (10)	0.0110 (11)
V1	0.00446 (17)	0.00613 (15)	0.00523 (15)	0.00007 (12)	0.00188 (13)	−0.00022 (12)
V2	0.00508 (17)	0.00396 (15)	0.00497 (15)	0.00072 (12)	0.00156 (13)	0.00013 (12)
V3	0.00678 (17)	0.00668 (16)	0.00561 (16)	0.00051 (13)	0.00282 (13)	−0.00102 (12)
V4	0.00511 (17)	0.00675 (15)	0.00438 (15)	0.00021 (12)	0.00115 (13)	−0.00009 (12)
V5	0.00768 (18)	0.00618 (16)	0.00514 (16)	0.00000 (13)	0.00230 (13)	0.00097 (12)
O7	0.0071 (7)	0.0072 (6)	0.0068 (6)	−0.0008 (5)	0.0032 (6)	−0.0003 (5)
O8	0.0068 (7)	0.0058 (6)	0.0074 (7)	0.0003 (5)	0.0024 (6)	0.0003 (5)
O9	0.0070 (7)	0.0088 (6)	0.0081 (7)	0.0001 (6)	0.0027 (6)	0.0000 (5)
O10	0.0057 (7)	0.0055 (6)	0.0056 (6)	−0.0004 (5)	0.0011 (5)	−0.0006 (5)
O11	0.0068 (7)	0.0061 (6)	0.0072 (7)	0.0007 (5)	0.0027 (6)	0.0000 (5)
O12	0.0104 (8)	0.0113 (7)	0.0097 (7)	0.0000 (6)	0.0045 (6)	−0.0033 (6)
O13	0.0066 (7)	0.0076 (6)	0.0061 (6)	0.0000 (5)	0.0023 (6)	−0.0003 (5)
O14	0.0078 (7)	0.0121 (7)	0.0081 (7)	−0.0005 (6)	0.0014 (6)	0.0002 (6)
O15	0.0060 (7)	0.0077 (6)	0.0075 (7)	0.0001 (5)	0.0033 (6)	0.0000 (5)
O16	0.0045 (7)	0.0057 (6)	0.0063 (6)	0.0001 (5)	0.0019 (6)	0.0004 (5)
O17	0.0045 (7)	0.0062 (6)	0.0075 (6)	0.0009 (5)	0.0019 (5)	0.0002 (5)
O18	0.0071 (7)	0.0084 (6)	0.0064 (6)	−0.0006 (5)	0.0029 (6)	−0.0002 (5)
O19	0.0074 (7)	0.0079 (6)	0.0055 (6)	0.0012 (5)	0.0017 (6)	0.0014 (5)
O20	0.0117 (8)	0.0109 (7)	0.0095 (7)	−0.0005 (6)	0.0033 (6)	0.0018 (6)
N2	0.0090 (9)	0.0078 (8)	0.0095 (9)	0.0005 (8)	0.0014 (8)	0.0011 (7)
O21	0.0162 (9)	0.0113 (8)	0.0217 (9)	−0.0007 (7)	−0.0056 (8)	−0.0002 (7)
O22	0.0184 (10)	0.0405 (11)	0.0223 (10)	−0.0112 (8)	0.0110 (9)	−0.0143 (9)

Geometric parameters (Å, º) top

Zn1—O2	2.0482 (16)	V2—O11	1.7029 (14)
Zn1—O5	2.0772 (16)	V2—O10	1.8700 (14)
Zn1—O3	2.0886 (16)	V2—O17	1.9470 (14)
Zn1—O1	2.0926 (14)	V2—O16	2.1033 (13)
Zn1—O4	2.1113 (16)	V2—O16ⁱ	2.1256 (13)
Zn1—O6	2.1273 (16)	V2—V3ⁱ	3.0726 (5)
O1—C1	1.255 (3)	V2—V5	3.0993 (5)
O2—H2O	0.75 (3)	V3—O12	1.5929 (14)
O2—H2P	0.74 (3)	V3—O13	1.8525 (14)
O3—H3O	0.73 (3)	V3—O18	1.8552 (14)
O3—H3P	0.83 (3)	V3—O15	1.9067 (14)
O4—H4O	0.74 (3)	V3—O11ⁱ	2.0310 (14)
O4—H4P	0.79 (3)	V3—O16	2.3168 (14)
O5—H5O	0.84 (3)	V3—V5	3.0662 (5)
O5—H5P	0.76 (3)	V3—V4	3.1066 (5)
O6—H6O	0.82 (2)	V4—O14	1.6074 (15)
O6—H6P	0.78 (2)	V4—O19	1.8031 (14)
C1—N1	1.313 (3)	V4—O13	1.8434 (14)
C1—H1	0.9500	V4—O17	1.9841 (14)
N1—C2	1.455 (3)	V4—O10ⁱ	2.0101 (14)
N1—C3	1.463 (3)	V4—O16	2.2317 (14)
C2—H2A	0.9800	V4—V5	3.1181 (5)
C2—H2B	0.9800	V5—O20	1.6118 (14)
C2—H2C	0.9800	V5—O18	1.8115 (14)
C3—H3A	0.9800	V5—O7	1.8559 (14)
C3—H3B	0.9800	V5—O19	1.8954 (14)
C3—H3C	0.9800	V5—O8	2.0696 (14)
V1—O9	1.6210 (14)	V5—O16	2.3337 (13)
V1—O15	1.7939 (14)	N2—H2R	0.91 (3)
V1—O7	1.8312 (14)	N2—H2S	0.79 (3)
V1—O17ⁱ	2.0027 (14)	N2—H2T	0.87 (3)
V1—O10	2.0208 (14)	N2—H2Q	0.88 (3)
V1—O16	2.2215 (14)	O21—H21A	0.79 (2)
V1—V4ⁱ	3.0765 (5)	O21—H21B	0.76 (2)
V1—V5	3.1011 (5)	O22—H22A	0.78 (2)
V1—V3	3.1047 (5)	O22—H22B	0.79 (2)
V2—O8	1.6890 (13)

O2—Zn1—O5	173.36 (7)	O11ⁱ—V3—V2ⁱ	31.29 (4)
O2—Zn1—O3	89.40 (7)	O16—V3—V2ⁱ	43.72 (3)
O5—Zn1—O3	94.90 (7)	V5—V3—V2ⁱ	92.705 (12)
O2—Zn1—O1	89.57 (7)	O12—V3—V1	134.03 (5)
O5—Zn1—O1	85.10 (6)	O13—V3—V1	123.55 (4)
O3—Zn1—O1	93.90 (6)	O18—V3—V1	81.71 (4)
O2—Zn1—O4	96.37 (7)	O15—V3—V1	31.85 (4)
O5—Zn1—O4	88.82 (6)	O11ⁱ—V3—V1	81.33 (4)
O3—Zn1—O4	88.52 (7)	O16—V3—V1	45.57 (3)
O1—Zn1—O4	173.62 (6)	V5—V3—V1	60.334 (11)
O2—Zn1—O6	90.11 (7)	V2ⁱ—V3—V1	62.101 (11)
O5—Zn1—O6	86.20 (6)	O12—V3—V4	134.74 (5)
O3—Zn1—O6	173.47 (6)	O13—V3—V4	32.71 (4)
O1—Zn1—O6	92.61 (6)	O18—V3—V4	81.72 (4)
O4—Zn1—O6	85.06 (6)	O15—V3—V4	122.81 (4)
C1—O1—Zn1	118.11 (14)	O11ⁱ—V3—V4	82.82 (4)
Zn1—O2—H2O	126 (2)	O16—V3—V4	45.79 (3)
Zn1—O2—H2P	123 (3)	V5—V3—V4	60.676 (11)
H2O—O2—H2P	107 (3)	V2ⁱ—V3—V4	61.307 (10)
Zn1—O3—H3O	110 (2)	V1—V3—V4	91.121 (12)
Zn1—O3—H3P	118 (2)	O14—V4—O19	104.99 (7)
H3O—O3—H3P	103 (3)	O14—V4—O13	102.14 (7)
Zn1—O4—H4O	121 (2)	O19—V4—O13	94.71 (6)
Zn1—O4—H4P	111 (2)	O14—V4—O17	99.59 (6)
H4O—O4—H4P	107 (3)	O19—V4—O17	91.24 (6)
Zn1—O5—H5O	130 (2)	O13—V4—O17	155.11 (6)
Zn1—O5—H5P	121 (2)	O14—V4—O10ⁱ	97.90 (7)
H5O—O5—H5P	108 (3)	O19—V4—O10ⁱ	155.58 (6)
Zn1—O6—H6O	123.2 (19)	O13—V4—O10ⁱ	88.61 (6)
Zn1—O6—H6P	127.5 (19)	O17—V4—O10ⁱ	76.46 (5)
H6O—O6—H6P	102 (3)	O14—V4—O16	172.94 (6)
O1—C1—N1	125.2 (2)	O19—V4—O16	81.20 (6)
O1—C1—H1	117.4	O13—V4—O16	80.45 (6)
N1—C1—H1	117.4	O17—V4—O16	76.62 (5)
C1—N1—C2	122.21 (19)	O10ⁱ—V4—O16	75.50 (5)
C1—N1—C3	120.29 (19)	O14—V4—V1ⁱ	88.21 (5)
C2—N1—C3	116.75 (19)	O19—V4—V1ⁱ	130.95 (4)
N1—C2—H2A	109.5	O13—V4—V1ⁱ	128.99 (4)
N1—C2—H2B	109.5	O17—V4—V1ⁱ	39.72 (4)
H2A—C2—H2B	109.5	O10ⁱ—V4—V1ⁱ	40.38 (4)
N1—C2—H2C	109.5	O16—V4—V1ⁱ	85.11 (4)
H2A—C2—H2C	109.5	O14—V4—V3	134.99 (5)
H2B—C2—H2C	109.5	O19—V4—V3	83.90 (4)
N1—C3—H3A	109.5	O13—V4—V3	32.89 (4)
N1—C3—H3B	109.5	O17—V4—V3	124.63 (4)
H3A—C3—H3B	109.5	O10ⁱ—V4—V3	85.94 (4)
N1—C3—H3C	109.5	O16—V4—V3	48.08 (3)
H3A—C3—H3C	109.5	V1ⁱ—V4—V3	119.349 (14)
H3B—C3—H3C	109.5	O14—V4—V5	138.20 (5)
O9—V1—O15	104.24 (7)	O19—V4—V5	33.46 (4)
O9—V1—O7	103.57 (7)	O13—V4—V5	83.20 (4)
O15—V1—O7	96.26 (6)	O17—V4—V5	88.66 (4)
O9—V1—O17ⁱ	98.45 (6)	O10ⁱ—V4—V5	123.81 (4)
O15—V1—O17ⁱ	90.58 (6)	O16—V4—V5	48.31 (3)
O7—V1—O17ⁱ	154.50 (6)	V1ⁱ—V4—V5	120.716 (13)
O9—V1—O10	97.95 (6)	V3—V4—V5	59.021 (11)
O15—V1—O10	155.49 (6)	O20—V5—O18	104.25 (7)
O7—V1—O10	88.44 (6)	O20—V5—O7	103.77 (7)
O17ⁱ—V1—O10	75.81 (5)	O18—V5—O7	94.15 (6)
O9—V1—O16	171.99 (6)	O20—V5—O19	101.19 (7)
O15—V1—O16	81.84 (6)	O18—V5—O19	91.23 (6)
O7—V1—O16	80.63 (6)	O7—V5—O19	152.28 (6)
O17ⁱ—V1—O16	76.05 (5)	O20—V5—O8	100.13 (6)
O10—V1—O16	75.19 (5)	O18—V5—O8	155.54 (6)
O9—V1—V4ⁱ	87.61 (5)	O7—V5—O8	81.94 (6)
O15—V1—V4ⁱ	129.85 (4)	O19—V5—O8	81.98 (6)
O7—V1—V4ⁱ	128.56 (4)	O20—V5—O16	173.31 (6)
O17ⁱ—V1—V4ⁱ	39.28 (4)	O18—V5—O16	82.22 (5)
O10—V1—V4ⁱ	40.12 (4)	O7—V5—O16	77.15 (5)
O16—V1—V4ⁱ	84.47 (4)	O19—V5—O16	76.68 (5)
O9—V1—V5	136.35 (5)	O8—V5—O16	73.35 (5)
O15—V1—V5	83.63 (5)	O20—V5—V3	137.94 (5)
O7—V1—V5	32.99 (4)	O18—V5—V3	33.71 (4)
O17ⁱ—V1—V5	124.67 (4)	O7—V5—V3	85.86 (4)
O10—V1—V5	87.51 (4)	O19—V5—V3	83.66 (4)
O16—V1—V5	48.63 (3)	O8—V5—V3	121.86 (4)
V4ⁱ—V1—V5	120.389 (14)	O16—V5—V3	48.51 (3)
O9—V1—V3	138.31 (5)	O20—V5—V2	130.78 (5)
O15—V1—V3	34.12 (4)	O18—V5—V2	124.94 (5)
O7—V1—V3	85.11 (4)	O7—V5—V2	76.63 (4)
O17ⁱ—V1—V3	86.96 (4)	O19—V5—V2	78.01 (4)
O10—V1—V3	123.27 (4)	O8—V5—V2	30.65 (4)
O16—V1—V3	48.13 (4)	O16—V5—V2	42.72 (3)
V4ⁱ—V1—V3	118.865 (14)	V3—V5—V2	91.233 (12)
V5—V1—V3	59.218 (11)	O20—V5—V1	136.08 (5)
O8—V2—O11	106.98 (7)	O18—V5—V1	82.44 (5)
O8—V2—O10	98.98 (6)	O7—V5—V1	32.50 (4)
O11—V2—O10	98.61 (6)	O19—V5—V1	122.27 (4)
O8—V2—O17	96.31 (6)	O8—V5—V1	81.48 (4)
O11—V2—O17	94.96 (6)	O16—V5—V1	45.59 (3)
O10—V2—O17	155.59 (6)	V3—V5—V1	60.448 (11)
O8—V2—O16	87.47 (6)	V2—V5—V1	60.851 (11)
O11—V2—O16	165.32 (6)	O20—V5—V4	132.78 (5)
O10—V2—O16	81.25 (6)	O18—V5—V4	82.01 (5)
O17—V2—O16	80.53 (5)	O7—V5—V4	122.67 (4)
O8—V2—O16ⁱ	165.68 (6)	O19—V5—V4	31.63 (4)
O11—V2—O16ⁱ	87.09 (6)	O8—V5—V4	79.96 (4)
O10—V2—O16ⁱ	81.02 (6)	O16—V5—V4	45.57 (3)
O17—V2—O16ⁱ	79.50 (5)	V3—V5—V4	60.303 (11)
O16—V2—O16ⁱ	78.36 (6)	V2—V5—V4	60.938 (10)
O8—V2—V3ⁱ	145.25 (5)	V1—V5—V4	90.971 (12)
O11—V2—V3ⁱ	38.27 (5)	V1—O7—V5	114.51 (7)
O10—V2—V3ⁱ	89.35 (4)	V2—O8—V5	110.69 (7)
O17—V2—V3ⁱ	88.85 (4)	V2—O10—V4ⁱ	108.53 (6)
O16—V2—V3ⁱ	127.24 (4)	V2—O10—V1	107.55 (6)
O16ⁱ—V2—V3ⁱ	48.87 (4)	V4ⁱ—O10—V1	99.50 (6)
O8—V2—V5	38.66 (5)	V2—O11—V3ⁱ	110.45 (7)
O11—V2—V5	145.64 (5)	V4—O13—V3	114.40 (7)
O10—V2—V5	90.27 (4)	V1—O15—V3	114.03 (7)
O17—V2—V5	89.87 (4)	V2—O16—V2ⁱ	101.64 (6)
O16—V2—V5	48.82 (4)	V2—O16—V1	93.07 (5)
O16ⁱ—V2—V5	127.18 (4)	V2ⁱ—O16—V1	94.24 (5)
V3ⁱ—V2—V5	176.038 (14)	V2—O16—V4	93.27 (5)
O12—V3—O13	102.07 (7)	V2ⁱ—O16—V4	92.58 (5)
O12—V3—O18	104.42 (7)	V1—O16—V4	169.57 (7)
O13—V3—O18	91.28 (6)	V2—O16—V3	170.95 (7)
O12—V3—O15	102.19 (7)	V2ⁱ—O16—V3	87.41 (5)
O13—V3—O15	154.51 (6)	V1—O16—V3	86.30 (5)
O18—V3—O15	90.18 (6)	V4—O16—V3	86.13 (5)
O12—V3—O11ⁱ	98.81 (6)	V2—O16—V5	88.46 (5)
O13—V3—O11ⁱ	84.97 (6)	V2ⁱ—O16—V5	169.89 (7)
O18—V3—O11ⁱ	156.74 (6)	V1—O16—V5	85.77 (5)
O15—V3—O11ⁱ	83.72 (6)	V4—O16—V5	86.12 (5)
O12—V3—O16	173.76 (6)	V3—O16—V5	82.50 (4)
O13—V3—O16	77.99 (5)	V2—O17—V4	106.64 (6)
O18—V3—O16	81.80 (5)	V2—O17—V1ⁱ	107.55 (6)
O15—V3—O16	77.04 (5)	V4—O17—V1ⁱ	101.01 (6)
O11ⁱ—V3—O16	74.96 (5)	V5—O18—V3	113.48 (7)
O12—V3—V5	137.23 (5)	V4—O19—V5	114.91 (7)
O13—V3—V5	84.58 (4)	H2R—N2—H2S	110 (3)
O18—V3—V5	32.81 (4)	H2R—N2—H2T	108 (2)
O15—V3—V5	82.95 (4)	H2S—N2—H2T	109 (3)
O11ⁱ—V3—V5	123.94 (4)	H2R—N2—H2Q	112 (3)
O16—V3—V5	48.99 (3)	H2S—N2—H2Q	104 (3)
O12—V3—V2ⁱ	130.07 (5)	H2T—N2—H2Q	114 (2)
O13—V3—V2ⁱ	78.67 (4)	H21A—O21—H21B	109 (3)
O18—V3—V2ⁱ	125.52 (4)	H22A—O22—H22B	111 (3)
O15—V3—V2ⁱ	79.82 (4)

Zn1—O1—C1—N1	160.84 (16)	V1ⁱ—V4—O13—V3	−84.80 (8)
O1—C1—N1—C2	−3.0 (3)	V5—V4—O13—V3	39.62 (6)
O1—C1—N1—C3	−172.8 (2)	O12—V3—O13—V4	−177.51 (8)
O9—V1—O7—V5	174.37 (7)	O18—V3—O13—V4	−72.47 (8)
O15—V1—O7—V5	68.06 (8)	O15—V3—O13—V4	20.64 (18)
O17ⁱ—V1—O7—V5	−36.62 (17)	O11ⁱ—V3—O13—V4	84.54 (7)
O10—V1—O7—V5	−87.82 (7)	O16—V3—O13—V4	8.87 (7)
O16—V1—O7—V5	−12.58 (7)	V5—V3—O13—V4	−40.31 (6)
V4ⁱ—V1—O7—V5	−87.71 (8)	V2ⁱ—V3—O13—V4	53.56 (6)
V3—V1—O7—V5	35.75 (6)	V1—V3—O13—V4	8.43 (9)
O20—V5—O7—V1	−174.70 (8)	O9—V1—O15—V3	−177.41 (7)
O18—V5—O7—V1	−68.93 (8)	O7—V1—O15—V3	−71.66 (8)
O19—V5—O7—V1	31.69 (17)	O17ⁱ—V1—O15—V3	83.73 (7)
O8—V5—O7—V1	86.78 (7)	O10—V1—O15—V3	28.39 (18)
O16—V5—O7—V1	12.11 (7)	O16—V1—O15—V3	7.90 (7)
V3—V5—O7—V1	−36.23 (6)	V4ⁱ—V1—O15—V3	83.63 (8)
V2—V5—O7—V1	56.03 (6)	V5—V1—O15—V3	−41.12 (6)
V4—V5—O7—V1	14.23 (9)	O20—V5—O18—V3	−178.51 (8)
O11—V2—O8—V5	−179.02 (6)	O7—V5—O18—V3	76.15 (8)
O10—V2—O8—V5	79.05 (7)	O19—V5—O18—V3	−76.64 (8)
O17—V2—O8—V5	−81.86 (7)	O8—V5—O18—V3	−3.5 (2)
O16—V2—O8—V5	−1.67 (7)	O16—V5—O18—V3	−0.26 (7)
O16ⁱ—V2—O8—V5	−9.8 (3)	V2—V5—O18—V3	−0.44 (10)
V3ⁱ—V2—O8—V5	−178.97 (3)	V1—V5—O18—V3	45.77 (6)
O8—V2—O10—V4ⁱ	−178.45 (6)	V4—V5—O18—V3	−46.29 (6)
O11—V2—O10—V4ⁱ	72.71 (7)	O12—V3—O18—V5	−179.26 (8)
O17—V2—O10—V4ⁱ	−50.33 (16)	O13—V3—O18—V5	77.94 (8)
O16—V2—O10—V4ⁱ	−92.44 (6)	O15—V3—O18—V5	−76.62 (8)
O16ⁱ—V2—O10—V4ⁱ	−12.94 (6)	O11ⁱ—V3—O18—V5	−2.3 (2)
V3ⁱ—V2—O10—V4ⁱ	35.44 (5)	O16—V3—O18—V5	0.27 (7)
V5—V2—O10—V4ⁱ	−140.62 (5)	V2ⁱ—V3—O18—V5	0.97 (10)
O8—V2—O10—V1	−71.68 (7)	V1—V3—O18—V5	−45.80 (6)
O11—V2—O10—V1	179.48 (6)	V4—V3—O18—V5	46.56 (6)
O17—V2—O10—V1	56.44 (16)	O14—V4—O19—V5	−174.03 (7)
O16—V2—O10—V1	14.33 (6)	O13—V4—O19—V5	−70.12 (8)
O16ⁱ—V2—O10—V1	93.83 (6)	O17—V4—O19—V5	85.69 (8)
V3ⁱ—V2—O10—V1	142.21 (5)	O10ⁱ—V4—O19—V5	26.93 (18)
V5—V2—O10—V1	−33.84 (5)	O16—V4—O19—V5	9.44 (7)
O8—V2—O11—V3ⁱ	179.95 (7)	V1ⁱ—V4—O19—V5	85.04 (8)
O10—V2—O11—V3ⁱ	−77.85 (7)	V3—V4—O19—V5	−39.01 (6)
O17—V2—O11—V3ⁱ	81.80 (7)	O20—V5—O19—V4	177.33 (8)
O16—V2—O11—V3ⁱ	10.5 (3)	O18—V5—O19—V4	72.55 (8)
O16ⁱ—V2—O11—V3ⁱ	2.61 (7)	O7—V5—O19—V4	−28.78 (17)
V5—V2—O11—V3ⁱ	178.87 (3)	O8—V5—O19—V4	−83.86 (8)
O14—V4—O13—V3	177.55 (8)	O16—V5—O19—V4	−9.16 (7)
O19—V4—O13—V3	71.10 (8)	V3—V5—O19—V4	39.64 (6)
O17—V4—O13—V3	−32.15 (18)	V2—V5—O19—V4	−52.98 (6)
O10ⁱ—V4—O13—V3	−84.67 (8)	V1—V5—O19—V4	−9.28 (9)
O16—V4—O13—V3	−9.14 (7)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O15ⁱⁱ	0.75 (3)	1.98 (3)	2.722 (2)	167 (3)
O3—H3P···O18	0.83 (3)	2.07 (3)	2.892 (2)	173 (3)
O4—H4O···O17ⁱⁱⁱ	0.74 (3)	1.97 (3)	2.710 (2)	177 (3)
O5—H5O···O19	0.85 (3)	1.82 (3)	2.659 (2)	169 (3)
O5—H5P···O9^iv	0.76 (3)	2.10 (3)	2.842 (2)	164 (3)
O6—H6O···O7^iv	0.82 (3)	1.95 (3)	2.771 (2)	173 (3)
O6—H6P···O11ⁱⁱⁱ	0.78 (2)	2.00 (2)	2.769 (2)	170 (3)

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

Funding information

The authors are grateful for support from the Scientific Grant Agency of the Ministry of Education of Slovak Republic and Slovak Academy of Sciences VEGA, Project No. 1/0669/22.

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