Bis{[amino­(iminium­yl)meth­yl]urea} tetra­kis­{2-[(di­methyl­amino)(iminium­yl)meth­yl]guanidine} di-μ6-oxido-tetra-μ3-oxido-tetra­deca-μ2-oxido-octa­oxidodeca­vanadium(V) tetra­hydrate

Pérez-Benítez, A.; Ariza-Ramírez, J.L.; Fortis-Valera, M.; Arroyo-Carmona, R.E.; Martínez de la Luz, M.I.; Ramírez-Contreras, D.; Bernès, S.

doi:10.1107/S2414314622006277

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 6| June 2022| x220627

https://doi.org/10.1107/S2414314622006277

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Bis{[amino(iminiumyl)methyl]urea} tetrakis{2-[(dimethylamino)(iminiumyl)methyl]guanidine} di-μ₆-oxido-tetra-μ₃-oxido-tetradeca-μ₂-oxido-octaoxidodecavanadium(V) tetrahydrate

Aarón Pérez-Benítez,^a Jorge Luis Ariza-Ramírez,^a Monserrat Fortis-Valera,^a Rosa Elena Arroyo-Carmona,^a María Isabel Martínez de la Luz,^a Diego Ramírez-Contreras ^a and Sylvain Bernès ^b ^*

^aFacultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 72570, Puebla, Mexico, and ^bInstituto de Física, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico
^*Correspondence e-mail: sylvain_bernes@hotmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 9 June 2022; accepted 14 June 2022; online 24 June 2022)

The title compound, (C₄H₁₂N₅)₄(C₂H₇N₄O)₂[V₁₀O₂₈]·4H₂O, is a by-product obtained by reacting ammonium metavanadate(V), metformin hydrochloride and acetic acid in the presence of sodium hypochlorite, at pH = 5. The crystal structure comprises a decavanadate(V) anion (V₁₀O₂₈)^6– lying on an inversion centre in space group P $[\overline{1}]$ , while cations and solvent water molecules are placed in general positions, surrounding the anion, and forming numerous N—H⋯O and O—H⋯O hydrogen bonds. Metforminium (C₄H₁₂N₅)⁺ and guanylurea (C₂H₇N₄O)⁺ cations display the expected shape. Interestingly, in physiology the latter cation is known to be the main metabolite of the former one. The reported structure thus supports the role of sodium hypochlorite as an oxidizing reagent being able to degrade metformin hydrochloride to form guanylurea.

Keywords: crystal structure; vanadium; decavanadate; metformin; hydrogen bond.

CCDC reference: 2179058

Structure description

Metformin hydrochloride (Metf·HCl: 1,1-dimethylbiguanide hydrochloride) is one of the most commonly prescribed medications for the treatment of type 2 diabetes (Maruthur et al., 2016 ). On the other hand, coordination compounds of vanadium, including polyoxidovanadates resulting from the condensation of the vanadate anion, likewise exhibit an antidiabetic effect, among other biological activities of interest in medicinal applications (Thompson et al., 2009 ; Rehder, 2020 ). We are involved in studies about the chemical crystallography of compounds including both types of antidiabetic species. In this context, we report here the crystal structure of a compound including a decavanadate(V) anion, metforminium cations, and a degradation product of the latter, guanylurea cation (1-carbamoylguanidinium).

The asymmetric unit of the title compound comprises one-half of the decavanadate(V) anion (V₁₀O₂₈)^6–, three cations and two water molecules of solvation. The chemical formula is thus (HMetf)₄(HGu)₂[V₁₀O₂₈]·4H₂O, where HMetf⁺ is the metforminium cation (C₄H₁₂N₅)⁺ and HGu⁺ is the guanylurea cation (C₂H₇N₄O)⁺. All hydrogen-atom positions in the cations were obtained from difference-Fourier maps, and their positions were refined, ensuring that the right tautomers are included in the structure model (Fig. 1). The decavanadate(V) anion is unprotonated, and displays its usual shape, with a point-group symmetry close to D_2h (real C_i). The twisted shape of both metforminium cations is also similar to that observed in other compounds (e.g. Sánchez-Lombardo et al., 2014 ; Farzanfar et al., 2015 ). For the first cation, the dihedral angle between C1/N1/N2/N3 and C2/C3/C4/N4/N5 mean planes is 60.39 (9)°, while the dihedral angle between the C5/N6/N7/N8 and C6/C7/C8/N9/N10 mean planes in the other metforminium cation is 58.26 (10)°. Regarding the guanylurea cation, it is nearly planar [maximum distance of 0.009 (4) Å for N12], as in a closely related salt, namely (HMetf)₂(HGu)₄[V₁₀O₂₈]·2H₂O (Chatkon et al., 2014 ). In the metforminium cations, the positive charges are not clearly localized, since all C—N bond lengths span a short range, here between 1.321 (3) and 1.355 (3) Å (N—CH₃ bonds are omitted). These cations are thus stabilized by resonance, with delocalized π-bonds, a common feature of guanidinium derivatives. In the case of the present guanylurea cation, one π-bond is probably delocalized over C9 N11 and C9 N12.

Figure 1
The structures of the molecular entities of the title compound, with displacement ellipsoids drawn at the 40% probability level. The centrosymmetric anion is shown, while the content for cations and water molecules is limited to the asymmetric unit.

The cation conformations, as well as their orientations with respect to the highly charged anion favour the formation of numerous hydrogen bonds, the NH₂ groups of HMetf⁺ and HGu⁺ being the main donors, and the O sites in the anion being the main acceptors (Table 1, Fig. 2). Empty channels oriented parallel to [100] are available in the crystal structure to accommodate water molecules (O16, O17). These molecules serve both as donor and acceptor groups for hydrogen bonding, and indeed form the strongest intermolecular contacts in the crystal structure, providing cohesion between the (001) layers in which anions and cations are located (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O7	0.89 (3)	1.99 (3)	2.876 (3)	170 (3)
N2—H2B⋯O12ⁱ	0.85 (3)	1.99 (3)	2.835 (3)	176 (3)
N4—H4A⋯O16ⁱⁱ	0.87 (3)	2.03 (3)	2.893 (3)	176 (3)
N4—H4B⋯O17	0.79 (3)	2.13 (3)	2.908 (3)	168 (3)
N6—H6A⋯O15ⁱⁱⁱ	0.91 (3)	2.08 (3)	2.984 (3)	171 (3)
N6—H6B⋯O9^iv	0.80 (3)	2.15 (3)	2.947 (3)	173 (3)
N7—H7A⋯O10^iv	0.75 (3)	2.64 (3)	3.362 (3)	161 (3)
N7—H7B⋯O13	0.81 (3)	2.23 (3)	3.031 (3)	169 (3)
N9—H9A⋯O17^v	0.84 (3)	2.06 (3)	2.886 (3)	170 (3)
N9—H9B⋯O16	0.81 (3)	2.10 (3)	2.889 (3)	165 (3)
N11—H11A⋯O11^vi	0.84 (3)	2.05 (3)	2.868 (2)	162 (3)
N11—H11B⋯O1	0.70 (3)	2.48 (3)	3.049 (2)	140 (3)
N11—H11B⋯O10	0.70 (3)	2.45 (3)	3.093 (2)	153 (3)
N13—H13⋯O6	0.82 (3)	2.11 (3)	2.926 (2)	175 (3)
N14—H14A⋯N8ⁱⁱⁱ	0.88 (4)	2.22 (4)	3.091 (3)	175 (3)
N14—H14B⋯O2^vii	0.74 (3)	2.44 (4)	3.055 (3)	140 (4)
N14—H14B⋯O4	0.74 (3)	2.53 (3)	3.156 (3)	143 (3)
O16—H16A⋯O8	0.80 (3)	1.97 (3)	2.770 (2)	178 (3)
O16—H16B⋯O3^v	0.71 (3)	2.23 (3)	2.929 (2)	171 (4)
O17—H17A⋯O8	0.75 (3)	2.12 (3)	2.861 (2)	170 (3)
O17—H17B⋯O5ⁱⁱ	0.78 (3)	2.13 (3)	2.866 (2)	159 (3)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) x+1, y, z; (v) ; (vi) ; (vii) .

Figure 2
Main interactions between the decavanadate(V) anion (polyhedral representation) and the first shell including six cations and four water molecules (ball-and-stick representation). Hydrogen bonds are represented by blue dashed lines, and the label associated to each hydrogen bond refers to its entry in Table 1

Figure 3
Part of the crystal structure, viewed down the a axis, emphasizing the positions of water molecules (space-fill representation).

Experimental conditions used for the synthesis of the title compound were very close to those used for the synthesis of (HMetf)₂(NH₄)₄[V₁₀O₂₈]·6H₂O, for which we previously reported the crystal structure (Polito-Lucas et al., 2021 ). The only difference is that sodium hypochlorite, NaOCl, was present in the reaction medium. At pH < 7, the hypochlorite anion OCl⁻ reacts with the metforminium cation, to form guanylurea (Armbruster et al., 2015 ). Aqueous NaOCl or solid NaOCl·5H₂O are commonly used in such oxidation processes in organic synthesis (Kirihara et al., 2017 ). On the other hand, in physiology guanylurea is known to be the main metabolite of metformin, through a biodegradation pathway (Tassoulas et al., 2021 ), and both molecules raise a serious problem of anthropogenic contamination, since high concentrations are found in waste water (Tisler & Zwiener, 2019 ; Poursat et al., 2019 ; Tucker & Wesolowski, 2020 ). The title compound highlights the fact that bleach, also present in waste water, has the ability to degrade metformin to guanylurea. However, the question as to whether the decavanadate(V) anion (or any other vanadium-containing species) promotes or inhibits metformin degradation remains open.

Synthesis and crystallization

Orange good-quality single crystals of the title compound were obtained during the reaction between ammonium metavanadate (NH₄VO₃, 1.50 g, 12.1 mmol) and metformin hydrochloride (Metf·HCl extracted from a commercial brand; 1.70 g, 10.2 mmol) in 50 ml of distilled water, 20 ml of 5% v/v acetic acid (commercial vinegar) and 2 ml of 5% v/v sodium hypochlorite (commercial bleach). In a typical procedure, NH₄VO₃ was dissolved by gently heating in a water bath followed by addition of Metf·HCl and stirring until dissolution. The water bath was removed, and once the mixture cooled down to room temperature, CH₃COOH and NaOCl solutions were added. A yellow–orange homogeneous solution was obtained, and pH = 5 was measured. The solution then was evaporated at ambient conditions and the two major products, (H₂Metf)₃[V₁₀O₂₈]·8H₂O (Sánchez-Lombardo et al., 2014) and (HMetf)₄(HGu)₂[V₁₀O₂₈]·4H₂O (estimated yields of ca 30 and 10%, respectively), were separated by fractional crystallization over the course of 5 to 10 d.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₅)₄(C₂H₇N₄O)₂[V₁₀O₂₈]·4H₂O
M_r	1756.44
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	263
a, b, c (Å)	8.9701 (3), 13.2202 (5), 14.0861 (5)
α, β, γ (°)	99.609 (3), 103.133 (3), 107.676 (3)
V (Å³)	1499.00 (10)
Z	1
Radiation type	Ag Kα, λ = 0.56083 Å
μ (mm⁻¹)	0.82
Crystal size (mm)	0.35 × 0.09 × 0.08

Data collection
Diffractometer	Stoe Stadivari
Absorption correction	Multi-scan (X-AREA; Stoe & Cie, 2019 )
T_min, T_max	0.471, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	66181, 11970, 7120
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.782

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.101, 0.83
No. of reflections	11970
No. of parameters	488
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.75
Computer programs: X-AREA (Stoe & Cie, 2019), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2179058

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622006277/wm4167sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622006277/wm4167Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2019); cell refinement: X-AREA (Stoe & Cie, 2019); data reduction: X-AREA (Stoe & Cie, 2019); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis{[amino(iminiumyl)methyl]urea} tetrakis{2-[(dimethylamino)(iminiumyl)methyl]guanidine} di-µ₆-oxido-tetra-µ₃-oxido-tetradeca-µ₂-oxido-octaoxidodecavanadium(V) tetrahydrate top

Crystal data top

(C₄H₁₂N₅)₄(C₂H₇N₄O)₂[V₁₀O₂₈]·4H₂O	Z = 1
M_r = 1756.44	F(000) = 888
Triclinic, P1	D_x = 1.946 Mg m⁻³
a = 8.9701 (3) Å	Ag Kα radiation, λ = 0.56083 Å
b = 13.2202 (5) Å	Cell parameters from 44097 reflections
c = 14.0861 (5) Å	θ = 2.2–30.9°
α = 99.609 (3)°	µ = 0.82 mm⁻¹
β = 103.133 (3)°	T = 263 K
γ = 107.676 (3)°	Prism, orange
V = 1499.00 (10) Å³	0.35 × 0.09 × 0.08 mm

Data collection top

Stoe Stadivari diffractometer	11970 independent reflections
Radiation source: Sealed X-ray tube, Axo Astix-f Microfocus source	7120 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.064
Detector resolution: 5.81 pixels mm^-1	θ_max = 26.0°, θ_min = 2.4°
ω scans	h = −12→14
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2019)	k = −20→20
T_min = 0.471, T_max = 1.000	l = −22→22
66181 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: mixed
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 0.83	w = 1/[σ²(F_o²) + (0.0523P)²] where P = (F_o² + 2F_c²)/3
11970 reflections	(Δ/σ)_max = 0.001
488 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.75 e Å⁻³
0 constraints

Special details top

Refinement. High-resolution data were collected (d_min = 0.64 Å), and all H atoms were discernible in difference-Fourier maps. Methyl H atoms were placed in calculated positions, with U_iso(H) = 1.5U_eq(carrier C). The positions for other H atoms were freely refined, and their isotropic displacements were calculated as U_iso(H) = 1.2U_eq(carrier N) and U_iso(H) = 1.5U_eq(carrier O).

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

	x	y	z	U_iso*/U_eq
V1	−0.18346 (3)	0.50285 (3)	0.48387 (2)	0.02031 (7)
V2	0.11454 (4)	0.67569 (3)	0.66199 (2)	0.02333 (7)
V3	0.29658 (4)	0.73708 (3)	0.50272 (3)	0.02746 (8)
V4	0.00747 (4)	0.56616 (3)	0.32784 (2)	0.02291 (7)
V5	−0.04938 (4)	0.74348 (3)	0.47654 (3)	0.02779 (8)
O1	−0.35393 (15)	0.39698 (12)	0.47679 (11)	0.0256 (3)
O2	0.14821 (19)	0.71282 (13)	0.78213 (11)	0.0346 (3)
O3	0.47419 (18)	0.82185 (14)	0.51151 (13)	0.0389 (4)
O4	−0.02963 (18)	0.52272 (14)	0.20790 (11)	0.0334 (3)
O5	−0.1391 (2)	0.83039 (14)	0.46158 (13)	0.0401 (4)
O6	−0.18582 (14)	0.45457 (11)	0.34529 (9)	0.0205 (3)
O7	−0.00402 (17)	0.75691 (12)	0.61355 (11)	0.0275 (3)
O8	0.16426 (17)	0.82016 (12)	0.48728 (11)	0.0293 (3)
O9	−0.08722 (16)	0.66811 (12)	0.34085 (11)	0.0266 (3)
O10	−0.24798 (15)	0.60808 (12)	0.46689 (11)	0.0257 (3)
O11	−0.09736 (14)	0.54661 (11)	0.62762 (10)	0.0209 (3)
O12	0.30173 (16)	0.75443 (12)	0.64019 (11)	0.0271 (3)
O13	0.21944 (16)	0.66484 (12)	0.36802 (11)	0.0270 (3)
O14	0.05231 (14)	0.60398 (11)	0.49536 (10)	0.0199 (2)
C1	−0.2523 (3)	0.8595 (2)	0.76688 (18)	0.0349 (5)
C2	0.0296 (3)	0.95180 (18)	0.81639 (17)	0.0315 (4)
C3	0.1549 (3)	0.8988 (2)	0.96161 (19)	0.0466 (6)
H3A	0.191943	0.952085	1.025219	0.070*
H3B	0.222871	0.854931	0.962427	0.070*
H3C	0.043527	0.852377	0.950131	0.070*
C4	0.3258 (3)	1.0073 (4)	0.8715 (3)	0.0729 (11)
H4C	0.344844	0.959712	0.819942	0.109*
H4D	0.407592	1.021958	0.934421	0.109*
H4E	0.331692	1.075066	0.853596	0.109*
N1	−0.2665 (3)	0.79810 (18)	0.67858 (16)	0.0376 (5)
H1A	−0.178 (3)	0.794 (2)	0.662 (2)	0.045*
H1B	−0.351 (3)	0.771 (2)	0.636 (2)	0.045*
N2	−0.3897 (3)	0.8602 (2)	0.7888 (2)	0.0537 (7)
H2A	−0.379 (4)	0.902 (3)	0.848 (3)	0.064*
H2B	−0.484 (4)	0.829 (3)	0.747 (3)	0.064*
N3	−0.1127 (2)	0.91530 (19)	0.83847 (15)	0.0404 (5)
N4	0.0405 (3)	0.99452 (18)	0.73832 (17)	0.0370 (4)
H4A	−0.045 (3)	1.001 (2)	0.700 (2)	0.044*
H4B	0.117 (3)	1.006 (2)	0.717 (2)	0.044*
N5	0.1645 (2)	0.95465 (18)	0.88149 (16)	0.0380 (4)
C5	0.5314 (2)	0.70581 (19)	0.20996 (16)	0.0304 (4)
C6	0.3190 (2)	0.77189 (18)	0.17505 (15)	0.0271 (4)
C7	0.0868 (3)	0.6332 (2)	0.04521 (17)	0.0366 (5)
H7C	0.083349	0.648205	−0.019487	0.055*
H7D	−0.022500	0.596148	0.046520	0.055*
H7E	0.150763	0.587596	0.057091	0.055*
C8	0.0538 (3)	0.7913 (2)	0.15167 (19)	0.0371 (5)
H8A	0.034360	0.776677	0.213139	0.056*
H8B	−0.048504	0.764710	0.099138	0.056*
H8C	0.104801	0.868982	0.161395	0.056*
N6	0.6537 (2)	0.6869 (2)	0.18114 (18)	0.0435 (5)
H6A	0.660 (3)	0.685 (2)	0.117 (2)	0.052*
H6B	0.720 (4)	0.676 (3)	0.222 (2)	0.052*
N7	0.5283 (3)	0.70352 (19)	0.30382 (16)	0.0378 (5)
H7A	0.595 (3)	0.695 (2)	0.341 (2)	0.045*
H7B	0.449 (3)	0.702 (2)	0.323 (2)	0.045*
N8	0.4152 (2)	0.72119 (17)	0.14230 (13)	0.0314 (4)
N9	0.3795 (2)	0.86178 (18)	0.25014 (16)	0.0355 (4)
H9A	0.479 (3)	0.886 (2)	0.283 (2)	0.043*
H9B	0.327 (3)	0.891 (2)	0.277 (2)	0.043*
N10	0.16091 (19)	0.73611 (15)	0.12336 (13)	0.0285 (4)
C9	−0.6276 (2)	0.42463 (19)	0.23836 (16)	0.0289 (4)
C10	−0.5215 (3)	0.3700 (2)	0.10014 (17)	0.0366 (5)
N11	−0.5989 (2)	0.4617 (2)	0.33434 (15)	0.0375 (5)
H11A	−0.674 (3)	0.468 (2)	0.358 (2)	0.045*
H11B	−0.522 (3)	0.477 (2)	0.370 (2)	0.045*
N12	−0.7731 (3)	0.4028 (3)	0.17683 (18)	0.0548 (7)
H12A	−0.785 (4)	0.375 (3)	0.117 (3)	0.066*
H12B	−0.846 (4)	0.412 (3)	0.200 (3)	0.066*
N13	−0.5049 (2)	0.41034 (18)	0.20225 (14)	0.0327 (4)
H13	−0.418 (3)	0.424 (2)	0.245 (2)	0.039*
N14	−0.3872 (3)	0.3626 (3)	0.08178 (18)	0.0559 (7)
H14A	−0.396 (4)	0.343 (3)	0.018 (3)	0.067*
H14B	−0.309 (4)	0.376 (3)	0.122 (3)	0.067*
O15	−0.6510 (2)	0.3447 (2)	0.03409 (13)	0.0559 (6)
O16	0.2449 (2)	0.97674 (15)	0.38087 (13)	0.0352 (4)
H16A	0.220 (4)	0.931 (3)	0.411 (2)	0.053*
H16B	0.312 (4)	1.023 (3)	0.412 (2)	0.053*
O17	0.2829 (2)	1.02959 (15)	0.62909 (14)	0.0364 (4)
H17A	0.247 (4)	0.972 (3)	0.597 (2)	0.055*
H17B	0.243 (4)	1.057 (3)	0.591 (2)	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.01787 (12)	0.02549 (16)	0.01941 (15)	0.01000 (12)	0.00608 (11)	0.00545 (12)
V2	0.02600 (14)	0.02310 (17)	0.01967 (16)	0.00949 (13)	0.00553 (12)	0.00253 (13)
V3	0.02363 (14)	0.02576 (18)	0.02969 (18)	0.00416 (13)	0.00690 (13)	0.00857 (14)
V4	0.02465 (14)	0.02587 (17)	0.01891 (15)	0.00888 (13)	0.00673 (12)	0.00732 (13)
V5	0.03017 (16)	0.02440 (17)	0.03055 (19)	0.01368 (14)	0.00625 (14)	0.00780 (14)
O1	0.0188 (5)	0.0315 (8)	0.0268 (7)	0.0086 (5)	0.0069 (5)	0.0084 (6)
O2	0.0442 (8)	0.0349 (9)	0.0224 (7)	0.0163 (7)	0.0071 (6)	0.0013 (6)
O3	0.0305 (7)	0.0358 (9)	0.0407 (9)	−0.0010 (7)	0.0081 (7)	0.0123 (7)
O4	0.0363 (7)	0.0405 (9)	0.0220 (7)	0.0115 (7)	0.0086 (6)	0.0084 (7)
O5	0.0462 (9)	0.0349 (9)	0.0428 (10)	0.0235 (8)	0.0069 (8)	0.0104 (8)
O6	0.0198 (5)	0.0232 (7)	0.0181 (6)	0.0078 (5)	0.0047 (5)	0.0049 (5)
O7	0.0328 (7)	0.0256 (7)	0.0254 (7)	0.0154 (6)	0.0061 (6)	0.0037 (6)
O8	0.0324 (7)	0.0210 (7)	0.0319 (8)	0.0073 (6)	0.0069 (6)	0.0084 (6)
O9	0.0290 (6)	0.0272 (7)	0.0251 (7)	0.0125 (6)	0.0051 (5)	0.0096 (6)
O10	0.0227 (6)	0.0292 (7)	0.0275 (7)	0.0138 (5)	0.0059 (5)	0.0065 (6)
O11	0.0208 (5)	0.0257 (7)	0.0184 (6)	0.0105 (5)	0.0075 (5)	0.0046 (5)
O12	0.0257 (6)	0.0245 (7)	0.0246 (7)	0.0041 (5)	0.0042 (5)	0.0030 (6)
O13	0.0246 (6)	0.0304 (8)	0.0261 (7)	0.0066 (6)	0.0095 (5)	0.0103 (6)
O14	0.0194 (5)	0.0210 (7)	0.0200 (6)	0.0084 (5)	0.0055 (5)	0.0055 (5)
C1	0.0335 (10)	0.0367 (12)	0.0359 (12)	0.0124 (9)	0.0124 (9)	0.0098 (10)
C2	0.0325 (9)	0.0275 (11)	0.0333 (11)	0.0109 (8)	0.0118 (9)	0.0012 (9)
C3	0.0523 (14)	0.0520 (16)	0.0332 (13)	0.0174 (13)	0.0097 (11)	0.0111 (12)
C4	0.0323 (12)	0.113 (3)	0.076 (2)	0.0184 (16)	0.0120 (14)	0.051 (2)
N1	0.0327 (9)	0.0389 (12)	0.0353 (11)	0.0124 (9)	0.0053 (8)	0.0012 (9)
N2	0.0298 (9)	0.0704 (18)	0.0462 (14)	0.0106 (11)	0.0101 (9)	−0.0085 (12)
N3	0.0301 (8)	0.0516 (13)	0.0327 (10)	0.0090 (9)	0.0103 (8)	0.0020 (9)
N4	0.0321 (9)	0.0411 (12)	0.0423 (12)	0.0162 (9)	0.0128 (9)	0.0141 (9)
N5	0.0317 (8)	0.0433 (12)	0.0386 (11)	0.0123 (8)	0.0100 (8)	0.0120 (9)
C5	0.0282 (9)	0.0331 (11)	0.0271 (10)	0.0095 (8)	0.0077 (8)	0.0038 (9)
C6	0.0273 (8)	0.0294 (10)	0.0243 (9)	0.0092 (8)	0.0083 (7)	0.0070 (8)
C7	0.0336 (10)	0.0374 (13)	0.0309 (12)	0.0082 (9)	0.0052 (9)	0.0025 (10)
C8	0.0314 (10)	0.0420 (14)	0.0408 (13)	0.0174 (10)	0.0118 (9)	0.0080 (11)
N6	0.0342 (9)	0.0738 (17)	0.0334 (11)	0.0310 (11)	0.0113 (8)	0.0181 (11)
N7	0.0344 (9)	0.0522 (13)	0.0315 (11)	0.0191 (9)	0.0107 (8)	0.0144 (9)
N8	0.0292 (8)	0.0433 (11)	0.0236 (8)	0.0179 (8)	0.0069 (7)	0.0051 (8)
N9	0.0273 (8)	0.0364 (11)	0.0363 (11)	0.0098 (8)	0.0077 (8)	−0.0022 (8)
N10	0.0250 (7)	0.0304 (9)	0.0276 (9)	0.0095 (7)	0.0060 (6)	0.0042 (7)
C9	0.0263 (8)	0.0365 (12)	0.0267 (10)	0.0142 (8)	0.0086 (8)	0.0084 (9)
C10	0.0320 (10)	0.0531 (15)	0.0264 (11)	0.0190 (10)	0.0085 (8)	0.0072 (10)
N11	0.0277 (8)	0.0597 (14)	0.0259 (10)	0.0196 (9)	0.0083 (7)	0.0051 (9)
N12	0.0317 (9)	0.103 (2)	0.0298 (11)	0.0350 (12)	0.0054 (9)	0.0002 (12)
N13	0.0239 (7)	0.0504 (12)	0.0242 (9)	0.0169 (8)	0.0060 (7)	0.0052 (8)
N14	0.0376 (10)	0.107 (2)	0.0276 (11)	0.0385 (13)	0.0090 (9)	0.0048 (13)
O15	0.0343 (8)	0.1055 (18)	0.0247 (8)	0.0323 (10)	0.0029 (7)	0.0022 (10)
O16	0.0415 (9)	0.0307 (9)	0.0326 (9)	0.0109 (7)	0.0097 (7)	0.0115 (7)
O17	0.0372 (8)	0.0302 (9)	0.0353 (9)	0.0093 (7)	0.0043 (7)	0.0050 (7)

Geometric parameters (Å, º) top

V1—O10	1.6925 (14)	C4—N5	1.454 (3)
V1—O1	1.7005 (13)	C4—H4C	0.9600
V1—O11	1.9126 (13)	C4—H4D	0.9600
V1—O6	1.9430 (13)	C4—H4E	0.9600
V1—O14	2.0836 (12)	N1—H1A	0.89 (3)
V1—O14ⁱ	2.1105 (13)	N1—H1B	0.79 (3)
V1—V5	3.0691 (5)	N2—H2A	0.89 (4)
V1—V3ⁱ	3.0755 (5)	N2—H2B	0.85 (3)
V2—O2	1.6113 (15)	N4—H4A	0.87 (3)
V2—O12	1.8102 (14)	N4—H4B	0.79 (3)
V2—O7	1.8324 (14)	C5—N6	1.329 (3)
V2—O6ⁱ	2.0062 (14)	C5—N8	1.334 (3)
V2—O11	2.0238 (13)	C5—N7	1.334 (3)
V2—O14	2.2495 (13)	C6—N9	1.324 (3)
V2—V4ⁱ	3.0888 (5)	C6—N10	1.331 (2)
V2—V5	3.1024 (5)	C6—N8	1.355 (3)
V3—O3	1.6091 (15)	C7—N10	1.457 (3)
V3—O13	1.8407 (15)	C7—H7C	0.9600
V3—O8	1.8484 (15)	C7—H7D	0.9600
V3—O12	1.8998 (15)	C7—H7E	0.9600
V3—O1ⁱ	2.0361 (15)	C8—N10	1.455 (3)
V3—O14	2.3243 (12)	C8—H8A	0.9600
V3—V5	3.0697 (5)	C8—H8B	0.9600
V3—V4	3.0951 (5)	C8—H8C	0.9600
V4—O4	1.6122 (15)	N6—H6A	0.91 (3)
V4—O9	1.8042 (15)	N6—H6B	0.80 (3)
V4—O13	1.8427 (13)	N7—H7A	0.75 (3)
V4—O6	2.0012 (13)	N7—H7B	0.81 (3)
V4—O11ⁱ	2.0196 (14)	N9—H9A	0.84 (3)
V4—O14	2.2434 (13)	N9—H9B	0.81 (3)
V4—V5	3.1169 (5)	C9—N11	1.296 (3)
V5—O5	1.6054 (16)	C9—N12	1.309 (3)
V5—O8	1.8331 (14)	C9—N13	1.361 (3)
V5—O7	1.8457 (15)	C10—O15	1.223 (3)
V5—O9	1.9040 (15)	C10—N14	1.316 (3)
V5—O10	2.0660 (14)	C10—N13	1.405 (3)
V5—O14	2.3191 (13)	N11—H11A	0.84 (3)
C1—N3	1.321 (3)	N11—H11B	0.70 (3)
C1—N1	1.323 (3)	N12—H12A	0.83 (3)
C1—N2	1.339 (3)	N12—H12B	0.82 (3)
C2—N4	1.327 (3)	N13—H13	0.82 (3)
C2—N5	1.328 (3)	N14—H14A	0.88 (4)
C2—N3	1.347 (3)	N14—H14B	0.74 (3)
C3—N5	1.453 (3)	O16—H16A	0.80 (3)
C3—H3A	0.9600	O16—H16B	0.71 (3)
C3—H3B	0.9600	O17—H17A	0.75 (3)
C3—H3C	0.9600	O17—H17B	0.78 (3)

O10—V1—O1	105.46 (7)	O10—V5—O14	74.12 (5)
O10—V1—O11	98.71 (6)	O5—V5—V1	131.07 (7)
O1—V1—O11	96.92 (6)	O8—V5—V1	125.08 (5)
O10—V1—O6	95.97 (6)	O7—V5—V1	78.36 (5)
O1—V1—O6	95.74 (6)	O9—V5—V1	78.38 (4)
O11—V1—O6	157.30 (5)	O10—V5—V1	31.41 (4)
O10—V1—O14	88.53 (6)	O14—V5—V1	42.73 (3)
O1—V1—O14	165.98 (6)	O5—V5—V3	137.49 (7)
O11—V1—O14	81.62 (5)	O8—V5—V3	33.66 (5)
O6—V1—O14	81.53 (5)	O7—V5—V3	85.71 (4)
O10—V1—O14ⁱ	167.14 (6)	O9—V5—V3	83.45 (4)
O1—V1—O14ⁱ	87.35 (6)	O10—V5—V3	122.77 (4)
O11—V1—O14ⁱ	80.52 (5)	O14—V5—V3	48.69 (3)
O6—V1—O14ⁱ	81.33 (5)	V1—V5—V3	91.420 (13)
O14—V1—O14ⁱ	78.65 (5)	O5—V5—V2	134.32 (7)
O10—V1—V5	39.51 (5)	O8—V5—V2	82.26 (5)
O1—V1—V5	144.96 (5)	O7—V5—V2	32.36 (4)
O11—V1—V5	89.98 (4)	O9—V5—V2	123.48 (4)
O6—V1—V5	90.41 (4)	O10—V5—V2	82.77 (4)
O14—V1—V5	49.05 (4)	O14—V5—V2	46.29 (3)
O14ⁱ—V1—V5	127.69 (3)	V1—V5—V2	61.613 (12)
O10—V1—V3ⁱ	143.79 (5)	V3—V5—V2	61.042 (11)
O1—V1—V3ⁱ	38.33 (5)	O5—V5—V4	133.62 (7)
O11—V1—V3ⁱ	88.31 (4)	O8—V5—V4	81.96 (5)
O6—V1—V3ⁱ	90.02 (4)	O7—V5—V4	123.82 (5)
O14—V1—V3ⁱ	127.68 (4)	O9—V5—V4	31.82 (4)
O14ⁱ—V1—V3ⁱ	49.04 (3)	O10—V5—V4	80.43 (4)
V5—V1—V3ⁱ	176.557 (14)	O14—V5—V4	45.90 (3)
O2—V2—O12	104.71 (7)	V1—V5—V4	61.206 (11)
O2—V2—O7	103.32 (7)	V3—V5—V4	60.033 (12)
O12—V2—O7	95.37 (7)	V2—V5—V4	91.958 (13)
O2—V2—O6ⁱ	99.03 (7)	V1—O1—V3ⁱ	110.47 (6)
O12—V2—O6ⁱ	89.97 (6)	V1—O6—V4	105.96 (6)
O7—V2—O6ⁱ	154.83 (6)	V1—O6—V2ⁱ	106.54 (6)
O2—V2—O11	98.92 (7)	V4—O6—V2ⁱ	100.85 (6)
O12—V2—O11	154.25 (6)	V2—O7—V5	115.02 (8)
O7—V2—O11	88.94 (6)	V5—O8—V3	112.99 (8)
O6ⁱ—V2—O11	76.20 (5)	V4—O9—V5	114.37 (7)
O2—V2—O14	173.33 (7)	V1—O10—V5	109.08 (6)
O12—V2—O14	80.50 (6)	V1—O11—V4ⁱ	108.12 (6)
O7—V2—O14	80.05 (6)	V1—O11—V2	106.80 (6)
O6ⁱ—V2—O14	76.60 (5)	V4ⁱ—O11—V2	99.62 (5)
O11—V2—O14	75.26 (5)	V2—O12—V3	115.31 (7)
O2—V2—V4ⁱ	88.84 (6)	V3—O13—V4	114.34 (7)
O12—V2—V4ⁱ	129.46 (5)	V1—O14—V1ⁱ	101.35 (5)
O7—V2—V4ⁱ	129.07 (5)	V1—O14—V4	93.34 (5)
O6ⁱ—V2—V4ⁱ	39.52 (4)	V1ⁱ—O14—V4	93.95 (5)
O11—V2—V4ⁱ	40.14 (4)	V1—O14—V2	93.60 (5)
O14—V2—V4ⁱ	84.60 (3)	V1ⁱ—O14—V2	93.05 (5)
O2—V2—V5	135.78 (6)	V4—O14—V2	168.99 (7)
O12—V2—V5	83.17 (5)	V1—O14—V5	88.22 (4)
O7—V2—V5	32.62 (5)	V1ⁱ—O14—V5	170.40 (6)
O6ⁱ—V2—V5	124.76 (4)	V4—O14—V5	86.16 (4)
O11—V2—V5	87.04 (4)	V2—O14—V5	85.53 (5)
O14—V2—V5	48.18 (3)	V1—O14—V3	170.95 (7)
V4ⁱ—V2—V5	119.903 (14)	V1ⁱ—O14—V3	87.68 (4)
O3—V3—O13	102.26 (8)	V4—O14—V3	85.29 (4)
O3—V3—O8	103.30 (8)	V2—O14—V3	86.51 (4)
O13—V3—O8	92.71 (7)	V5—O14—V3	82.77 (4)
O3—V3—O12	101.81 (7)	N3—C1—N1	125.0 (2)
O13—V3—O12	154.56 (6)	N3—C1—N2	116.8 (2)
O8—V3—O12	89.66 (7)	N1—C1—N2	118.1 (2)
O3—V3—O1ⁱ	100.28 (7)	N4—C2—N5	119.8 (2)
O13—V3—O1ⁱ	85.14 (6)	N4—C2—N3	122.1 (2)
O8—V3—O1ⁱ	156.22 (6)	N5—C2—N3	117.8 (2)
O12—V3—O1ⁱ	82.61 (6)	N5—C3—H3A	109.5
O3—V3—O14	174.67 (7)	N5—C3—H3B	109.5
O13—V3—O14	78.49 (5)	H3A—C3—H3B	109.5
O8—V3—O14	81.89 (5)	N5—C3—H3C	109.5
O12—V3—O14	76.79 (5)	H3A—C3—H3C	109.5
O1ⁱ—V3—O14	74.47 (5)	H3B—C3—H3C	109.5
O3—V3—V5	136.65 (7)	N5—C4—H4C	109.5
O13—V3—V5	85.37 (4)	N5—C4—H4D	109.5
O8—V3—V5	33.35 (4)	H4C—C4—H4D	109.5
O12—V3—V5	82.78 (4)	N5—C4—H4E	109.5
O1ⁱ—V3—V5	122.98 (4)	H4C—C4—H4E	109.5
O14—V3—V5	48.54 (3)	H4D—C4—H4E	109.5
O3—V3—V1ⁱ	131.48 (7)	C1—N1—H1A	120.9 (18)
O13—V3—V1ⁱ	79.52 (5)	C1—N1—H1B	121 (2)
O8—V3—V1ⁱ	125.17 (5)	H1A—N1—H1B	117 (3)
O12—V3—V1ⁱ	78.46 (5)	C1—N2—H2A	117 (2)
O1ⁱ—V3—V1ⁱ	31.20 (4)	C1—N2—H2B	123 (2)
O14—V3—V1ⁱ	43.29 (3)	H2A—N2—H2B	119 (3)
V5—V3—V1ⁱ	91.829 (13)	C1—N3—C2	121.3 (2)
O3—V3—V4	134.99 (6)	C2—N4—H4A	120.2 (18)
O13—V3—V4	32.85 (4)	C2—N4—H4B	125 (2)
O8—V3—V4	82.37 (5)	H4A—N4—H4B	114 (3)
O12—V3—V4	123.02 (4)	C2—N5—C3	120.9 (2)
O1ⁱ—V3—V4	83.12 (4)	C2—N5—C4	121.5 (2)
O14—V3—V4	46.25 (3)	C3—N5—C4	117.5 (2)
V5—V3—V4	60.738 (12)	N6—C5—N8	118.3 (2)
V1ⁱ—V3—V4	62.131 (11)	N6—C5—N7	117.9 (2)
O4—V4—O9	104.49 (7)	N8—C5—N7	123.7 (2)
O4—V4—O13	103.24 (7)	N9—C6—N10	119.0 (2)
O9—V4—O13	95.73 (7)	N9—C6—N8	122.24 (18)
O4—V4—O6	98.59 (7)	N10—C6—N8	118.44 (19)
O9—V4—O6	90.50 (6)	N10—C7—H7C	109.5
O13—V4—O6	154.96 (6)	N10—C7—H7D	109.5
O4—V4—O11ⁱ	98.58 (7)	H7C—C7—H7D	109.5
O9—V4—O11ⁱ	154.97 (6)	N10—C7—H7E	109.5
O13—V4—O11ⁱ	88.24 (6)	H7C—C7—H7E	109.5
O6—V4—O11ⁱ	76.41 (5)	H7D—C7—H7E	109.5
O4—V4—O14	172.62 (7)	N10—C8—H8A	109.5
O9—V4—O14	81.17 (6)	N10—C8—H8B	109.5
O13—V4—O14	80.64 (5)	H8A—C8—H8B	109.5
O6—V4—O14	76.39 (5)	N10—C8—H8C	109.5
O11ⁱ—V4—O14	75.10 (5)	H8A—C8—H8C	109.5
O4—V4—V2ⁱ	88.30 (6)	H8B—C8—H8C	109.5
O9—V4—V2ⁱ	130.12 (5)	C5—N6—H6A	121.6 (18)
O13—V4—V2ⁱ	128.48 (5)	C5—N6—H6B	116 (2)
O6—V4—V2ⁱ	39.63 (4)	H6A—N6—H6B	122 (3)
O11ⁱ—V4—V2ⁱ	40.24 (4)	C5—N7—H7A	122 (2)
O14—V4—V2ⁱ	84.39 (3)	C5—N7—H7B	123 (2)
O4—V4—V3	135.96 (6)	H7A—N7—H7B	115 (3)
O9—V4—V3	84.25 (5)	C5—N8—C6	118.98 (18)
O13—V4—V3	32.81 (5)	C6—N9—H9A	120 (2)
O6—V4—V3	124.78 (4)	C6—N9—H9B	126 (2)
O11ⁱ—V4—V3	85.92 (4)	H9A—N9—H9B	112 (3)
O14—V4—V3	48.45 (3)	C6—N10—C8	120.82 (19)
V2ⁱ—V4—V3	119.121 (14)	C6—N10—C7	120.68 (19)
O4—V4—V5	138.15 (6)	C8—N10—C7	118.08 (17)
O9—V4—V5	33.81 (5)	N11—C9—N12	119.9 (2)
O13—V4—V5	83.95 (5)	N11—C9—N13	119.58 (19)
O6—V4—V5	87.98 (4)	N12—C9—N13	120.6 (2)
O11ⁱ—V4—V5	123.03 (4)	O15—C10—N14	123.2 (2)
O14—V4—V5	47.94 (3)	O15—C10—N13	122.1 (2)
V2ⁱ—V4—V5	119.587 (14)	N14—C10—N13	114.7 (2)
V3—V4—V5	59.228 (12)	C9—N11—H11A	121.0 (19)
O5—V5—O8	103.84 (8)	C9—N11—H11B	124 (2)
O5—V5—O7	102.08 (8)	H11A—N11—H11B	116 (3)
O8—V5—O7	92.75 (7)	C9—N12—H12A	115 (2)
O5—V5—O9	101.85 (8)	C9—N12—H12B	119 (2)
O8—V5—O9	91.20 (7)	H12A—N12—H12B	126 (3)
O7—V5—O9	154.03 (7)	C9—N13—C10	124.73 (18)
O5—V5—O10	99.67 (7)	C9—N13—H13	115.2 (19)
O8—V5—O10	156.41 (6)	C10—N13—H13	120.0 (19)
O7—V5—O10	84.18 (6)	C10—N14—H14A	115 (2)
O9—V5—O10	82.01 (6)	C10—N14—H14B	123 (3)
O5—V5—O14	173.78 (7)	H14A—N14—H14B	122 (3)
O8—V5—O14	82.35 (5)	H16A—O16—H16B	111 (3)
O7—V5—O14	77.92 (5)	H17A—O17—H17B	99 (3)
O9—V5—O14	77.19 (5)

O10—V1—O1—V3ⁱ	−179.43 (7)	O7—V2—O12—V3	−70.42 (9)
O11—V1—O1—V3ⁱ	−78.38 (8)	O6ⁱ—V2—O12—V3	84.95 (8)
O6—V1—O1—V3ⁱ	82.74 (7)	O11—V2—O12—V3	28.32 (19)
O14—V1—O1—V3ⁱ	4.8 (3)	O14—V2—O12—V3	8.53 (7)
O14ⁱ—V1—O1—V3ⁱ	1.73 (7)	V4ⁱ—V2—O12—V3	83.39 (9)
V5—V1—O1—V3ⁱ	−178.31 (3)	V5—V2—O12—V3	−40.10 (7)
O2—V2—O7—V5	174.91 (8)	O3—V3—O12—V2	176.91 (9)
O12—V2—O7—V5	68.39 (9)	O13—V3—O12—V2	−22.2 (2)
O6ⁱ—V2—O7—V5	−33.07 (19)	O8—V3—O12—V2	73.38 (9)
O11—V2—O7—V5	−86.17 (8)	O1ⁱ—V3—O12—V2	−84.07 (8)
O14—V2—O7—V5	−10.96 (7)	O14—V3—O12—V2	−8.37 (7)
V4ⁱ—V2—O7—V5	−85.57 (8)	V5—V3—O12—V2	40.66 (7)
O5—V5—O7—V2	−175.65 (9)	V1ⁱ—V3—O12—V2	−52.71 (7)
O8—V5—O7—V2	−70.87 (9)	V4—V3—O12—V2	−7.28 (11)
O9—V5—O7—V2	27.55 (19)	O3—V3—O13—V4	−175.67 (9)
O10—V5—O7—V2	85.67 (8)	O8—V3—O13—V4	−71.43 (9)
O14—V5—O7—V2	10.70 (7)	O12—V3—O13—V4	23.5 (2)
V1—V5—O7—V2	54.41 (7)	O1ⁱ—V3—O13—V4	84.84 (8)
V3—V5—O7—V2	−37.93 (7)	O14—V3—O13—V4	9.73 (7)
V4—V5—O7—V2	11.29 (10)	V5—V3—O13—V4	−38.87 (7)
O5—V5—O8—V3	−178.80 (9)	V1ⁱ—V3—O13—V4	53.86 (7)
O7—V5—O8—V3	78.04 (9)	O4—V4—O13—V3	176.40 (9)
O9—V5—O8—V3	−76.28 (8)	O9—V4—O13—V3	70.03 (9)
O10—V5—O8—V3	−3.7 (2)	O6—V4—O13—V3	−33.6 (2)
O14—V5—O8—V3	0.62 (7)	O11ⁱ—V4—O13—V3	−85.20 (8)
V1—V5—O8—V3	0.33 (11)	O14—V4—O13—V3	−10.01 (7)
V2—V5—O8—V3	47.35 (7)	V2ⁱ—V4—O13—V3	−85.08 (9)
V4—V5—O8—V3	−45.74 (7)	V5—V4—O13—V3	38.28 (7)
O3—V3—O8—V5	−179.37 (9)	N1—C1—N3—C2	27.6 (4)
O13—V3—O8—V5	77.35 (8)	N2—C1—N3—C2	−156.9 (3)
O12—V3—O8—V5	−77.32 (8)	N4—C2—N3—C1	40.9 (4)
O1ⁱ—V3—O8—V5	−6.7 (2)	N5—C2—N3—C1	−146.1 (2)
O14—V3—O8—V5	−0.62 (7)	N4—C2—N5—C3	−173.7 (2)
V1ⁱ—V3—O8—V5	−1.73 (11)	N3—C2—N5—C3	13.1 (4)
V4—V3—O8—V5	46.10 (7)	N4—C2—N5—C4	2.3 (4)
O4—V4—O9—V5	−175.39 (8)	N3—C2—N5—C4	−170.9 (3)
O13—V4—O9—V5	−70.10 (8)	N6—C5—N8—C6	−160.5 (2)
O6—V4—O9—V5	85.61 (8)	N7—C5—N8—C6	22.6 (3)
O11ⁱ—V4—O9—V5	28.06 (18)	N9—C6—N8—C5	44.9 (3)
O14—V4—O9—V5	9.47 (7)	N10—C6—N8—C5	−141.8 (2)
V2ⁱ—V4—O9—V5	84.38 (8)	N9—C6—N10—C8	−3.0 (3)
V3—V4—O9—V5	−39.32 (6)	N8—C6—N10—C8	−176.5 (2)
O1—V1—O10—V5	178.99 (7)	N9—C6—N10—C7	−175.4 (2)
O11—V1—O10—V5	79.26 (7)	N8—C6—N10—C7	11.1 (3)
O6—V1—O10—V5	−83.36 (7)	N11—C9—N13—C10	179.5 (2)
O14—V1—O10—V5	−2.03 (7)	N12—C9—N13—C10	−1.6 (4)
O14ⁱ—V1—O10—V5	−6.3 (3)	O15—C10—N13—C9	0.5 (4)
V3ⁱ—V1—O10—V5	178.39 (3)	N14—C10—N13—C9	−179.9 (3)
O2—V2—O12—V3	−175.73 (8)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O7	0.89 (3)	1.99 (3)	2.876 (3)	170 (3)
N1—H1B···O3ⁱⁱ	0.79 (3)	2.40 (3)	3.041 (3)	140 (3)
N2—H2B···O12ⁱⁱ	0.85 (3)	1.99 (3)	2.835 (3)	176 (3)
N4—H4A···O16ⁱⁱⁱ	0.87 (3)	2.03 (3)	2.893 (3)	176 (3)
N4—H4B···O17	0.79 (3)	2.13 (3)	2.908 (3)	168 (3)
N6—H6A···O15^iv	0.91 (3)	2.08 (3)	2.984 (3)	171 (3)
N6—H6B···O9^v	0.80 (3)	2.15 (3)	2.947 (3)	173 (3)
N7—H7A···O5^v	0.75 (3)	2.51 (3)	3.059 (3)	131 (3)
N7—H7A···O10^v	0.75 (3)	2.64 (3)	3.362 (3)	161 (3)
N7—H7B···O13	0.81 (3)	2.23 (3)	3.031 (3)	169 (3)
N9—H9A···O17^vi	0.84 (3)	2.06 (3)	2.886 (3)	170 (3)
N9—H9B···O16	0.81 (3)	2.10 (3)	2.889 (3)	165 (3)
N11—H11A···O1^vii	0.84 (3)	2.59 (3)	3.175 (3)	128 (2)
N11—H11A···O11^vii	0.84 (3)	2.05 (3)	2.868 (2)	162 (3)
N11—H11B···O1	0.70 (3)	2.48 (3)	3.049 (2)	140 (3)
N11—H11B···O10	0.70 (3)	2.45 (3)	3.093 (2)	153 (3)
N12—H12A···O15	0.83 (3)	1.93 (3)	2.613 (3)	139 (3)
N12—H12B···O4ⁱⁱ	0.82 (3)	2.52 (4)	3.231 (3)	145 (3)
N12—H12B···O11^vii	0.82 (3)	2.60 (3)	3.271 (3)	140 (3)
N13—H13···O6	0.82 (3)	2.11 (3)	2.926 (2)	175 (3)
N14—H14A···N8^iv	0.88 (4)	2.22 (4)	3.091 (3)	175 (3)
N14—H14B···O2ⁱ	0.74 (3)	2.44 (4)	3.055 (3)	140 (4)
N14—H14B···O4	0.74 (3)	2.53 (3)	3.156 (3)	143 (3)
O16—H16A···O8	0.80 (3)	1.97 (3)	2.770 (2)	178 (3)
O16—H16B···O3^vi	0.71 (3)	2.23 (3)	2.929 (2)	171 (4)
O17—H17A···O8	0.75 (3)	2.12 (3)	2.861 (2)	170 (3)
O17—H17B···O5ⁱⁱⁱ	0.78 (3)	2.13 (3)	2.866 (2)	159 (3)

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

Funding information

Funding for this research was provided by: Consejo Nacional de Ciencia y Tecnología (grant No. 268178).

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