Crystal structure of bis-(ammonium) bis-[penta-aqua-(di-methyl-formamide)-zinc(II)] deca-vanadate tetra-hydrate.

The crystalline product (NH4)2[Zn(C3H7NO)(H2O)5]2[V10O28]·4H2O was success-fully 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 deca-vanadate 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. © Ebrahimi et al. 2022.

Chemical context

Decavanadate anions, H V10O28 (6–, 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] [{Na2(H2O)6(μH2O)4Zn(H2O)2}V10O28] ·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]}·H2 ppz (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} (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.

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 2) 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 μ 3–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.

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.

Figure 2

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

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) ; (ii) ; (iii) .

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] [{Na2(H2O)6(μ-H2O)4Zn(H2O)2}V10O28] ·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.

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.

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[F 2 > 2σ(F 2)], wR(F 2), 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
Δρmax, Δρmin (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 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022003449/yz2017sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022003449/yz2017Isup2.hkl

CCDC reference: 2156016

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

(NH4)2[Zn(C3H7NO)(H2O)5]2[V10O28]·4H2O	F(000) = 1512
Mr = 1522.64	Dx = 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

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

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(Fo2) + (0.0284P)2 + 1.1852P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.002
4901 reflections	Δρmax = 0.36 e Å−3
372 parameters	Δρmin = −0.62 e Å−3
6 restraints

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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···O9iv	0.76 (3)	2.10 (3)	2.842 (2)	164 (3)
O6—H6O···O7iv	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)