Crystal structure of (μ-hydrogen di­sulfato)-μ-oxido-bis­[(4,4′-di-tert-butyl-2,2′-bi­pyridine)­oxidovanadium(IV/V)] aceto­nitrile monosolvate

Kodama, S.; Hashiguchi, T.; Nomoto, A.

doi:10.1107/S2056989023009040

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ISSN: 2056-9890

Volume 79| Part 11| November 2023| Pages 1055-1058

https://doi.org/10.1107/S2056989023009040

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Crystal structure of (μ-hydrogen disulfato)-μ-oxido-bis[(4,4′-di-tert-butyl-2,2′-bipyridine)oxidovanadium(IV/V)] acetonitrile monosolvate

Shintaro Kodama,^a ^* Terushi Hashiguchi ^b and Akihiro Nomoto ^a

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka, Metropolitan University, 1-1 Gakuen-cho, Nakaku, Sakai, Osaka 599-8531, Japan, and ^bDepartment of Applied Chemistry, Graduate School of Engineering, Osaka, Prefecture University, 1-1 Gakuen-cho, Nakaku, Sakai, Osaka 599-8531, Japan
^*Correspondence e-mail: skodama@omu.ac.jp

Edited by X. Hao, Institute of Chemistry, Chinese Academy of Sciences (Received 10 October 2023; accepted 15 October 2023; online 19 October 2023)

The dinuclear oxidovanadium(IV/V) complex, [V₂(HS₂O₈)O₃(C₁₈H₂₄N₂)₂]·CH₃CN or [V₂O₂(μ-O)(μ-H(SO₄)₂)(4,4′-^tBubpy)₂]·CH₃CN (4,4′-^tBubpy = 4,4′-di-tert-butyl-2,2′-bipyridine), has crystallographic C₂ symmetry and exhibits a distorted octahedral geometry around the vanadium center, where the two 4,4′-^tBubpy ligands are nearly orthogonal to each other. The two vanadium ions are linked by an oxo anion and a unique protonated sulfate anion [H(SO₄)₂³⁻]. In the crystal, intermolecular C—H⋯π and π–π interactions between the 4,4′-^tBubpy ligands are present, leading to a three-dimensional network.

Keywords: crystal structure; vanadium; bipyridine; sulfate.

CCDC reference: 2301351

1. Chemical context

The sulfate anion (SO₄^2–) plays an important role as a ligand for transition-metal compounds, including polyoxometalates (Walsh et al., 2016 ), metal sulfates (Natarajan & Mandal, 2008 ), and polynuclear complexes with organic ligands (Papatriantafyllopoulou et al., 2009 ). Based on these compounds, a variety of catalysts (Wang et al., 2021 ), magnetic materials (Gómez-García et al., 2016 ), and metal–organic frameworks (Mi et al., 2022 ) have been developed in recent years. A hydrogensulfate anion (HSO₄⁻) is also found in transition-metal compounds, and HSO₄⁻ more often acts as a counter-anion than as a ligand (Díaz-Torres & Alvarez, 2011 ). Thus, transition-metal complexes having an HSO₄⁻ ligand are still limited in number. In sulfated metal oxide catalysts (e.g., V₂O₅-based catalysts), however, a surface-protonated sulfate group is often proposed as a Brønsted acid site and affects the catalytic activity (Xie et al., 2021 ). Hence, a transition-metal complex having a protonated sulfate anion as the ligand is expected to be an appropriate model compound to understand the active site of sulfated solid catalysts at the molecular level. Herein, we report the crystal structure of a dinuclear oxidovanadium(IV/V) complex with 4,4′-di-tert-butyl-2,2′-bipyridine (4,4′-^tBubpy) ligands, the two vanadium ions of which are linked by an oxo anion and a unique protonated sulfate anion [H(SO₄)₂³⁻].

2. Structural commentary

A single-crystal X-ray structure analysis revealed a novel dinuclear oxidovanadium(IV/V) complex [V₂O₂(μ-O)(μ-H(SO₄)₂)(4,4′-^tBubpy)₂] (V₂) with crystallographic C₂ symmetry (Fig. 1). Complex V₂ exhibits a distorted octahedral geometry around the vanadium centre, where the two 4,4′-^tBubpy ligands are nearly orthogonal to each other [the dihedral angle between the coordination planes of N1–V1–N2 and N1ⁱ–V1ⁱ–N2ⁱ is 86.48 (8)°]. The two vanadium ions are linked by bridging O^2– and H(SO₄)₂^3– ions. The lengths of the V=O_terminal [V1—O1; 1.5932 (14) Å], V—O_bridging [1.8268 (7)–2.2827 (12) Å], and V—N [2.1077 (14)–2.1399 (14) Å] bonds are within the expected values reported in the literature (Triantafillou et al., 2004 ; Inoue et al., 2018 ). For the S—O distances in the H(SO₄)₂^3– ion, the distances between S1 and O atoms (O3 and O5) attached to V atom are in the range of 1.4654 (13) to 1.5098 (12) Å, whereas the S=O_terminal [S1—O4; 1.4391 (13) Å] bond is substantially shorter. Although, like the O4 atom, the O6 atom is not attached to the V atom, the S1—O6 distance [1.5066 (13) Å] is comparable in length to the S1—O3 distance. Therefore, the S1—O6 distance can be attributed to the S—OH bond (Leszczyński et al., 2012 ). The hydrogen atom of the H(SO₄)₂^3– ligand is located with 0.5 occupancy at two positions (H6 and H6ⁱ) (Schindler & Wickleder, 2017 ) related by the C₂ axis passing through the midpoint of O6⋯O6ⁱ and the O2 atom. In addition, the O6⋯O6ⁱ distance (2.48 Å) reflects the strong intramolecular hydrogen-bond interaction in the H(SO₄)₂^3– ligand (Cleland et al., 1998 ).

Figure 1
Crystal structure of [V₂O₂(μ-O)(μ-H(SO₄)₂)(4,4′-^tBubpy)₂] (V₂) with numbered atoms. Ellipsoids are shown at the 50% probability level. Side view (top) and front view (bottom). The hydrogen atoms of 4,4′-^tBubpy ligands are omitted for clarity. Symmetry code: (i) −x + $[{5\over 4}]$ , y, −z + $[{5\over 4}]$ . The hydrogen atom of H(SO₄)₂^3– ligand is located at two positions (H6 and H6ⁱ) with 0.5 occupancy. Selected interatomic distances (Å): V1—O1 1.5932 (14), V1—O2 1.8268 (7), V1—O3 1.9692 (12), V1—O5ⁱ 2.2827 (12), V1—N1 2.1077 (14), V1—N2 2.1399 (14), S1—O3 1.5098 (12), S1—O4 1.4391 (13), S1—O5 1.4654 (13), S1—O6 1.5066 (13), O6⋯O6ⁱ 2.480 (2).

Bond-valence-sum calculations of complex V₂ (Table 1) suggest that the two V atoms (V1 and V1ⁱ) are in a mixed-valence state of V⁴⁺ and V⁵⁺. In addition, the UV-vis spectrum of V₂ in CH₃CN shows two weak absorption bands at 553 nm (ɛ = 82 M⁻¹ cm⁻¹) and 669 nm (ɛ = 29 M⁻¹ cm⁻¹), which are considered to be the d–d bands of V⁴⁺ (Ballhausen & Gray, 1962 ; Waidmann et al., 2009 ). To the best of our knowledge, the dinuclear structure of V₂ bearing the bridging H(SO₄)₂^3– ligand is unprecedented, although there are a few examples of vanadium complexes having the protonated sulfate anion (e.g., HSO₄⁻) as the ligand (Nilsson et al. 2009 ; Datta et al. 2015 ).

Table 1
BVS calculations for vanadium atoms of [V₂O₂(μ-O)(μ-H(SO₄)₂)(4,4′-^tBubpy)₂] (V₂)

BVS calculations were conducted using X-ray data of [V₂O₂(μ-O)(μ-H(SO₄)₂)(4,4′-^tBubpy)₂]. Bond-valence parameters: V^IV—O (1.784 Å), V^V—O (1.803 Å), and V—N (1.86 Å) (Brese & O'Keeffe, 1991 ).

[V₂O₂(μ-O)(μ-H(SO₄)₂)(4,4′-^tBubpy)₂]	V1
V(IV)	4.41
V(V)	4.59

3. Supramolecular features

In the crystal of V₂, intermolecular C—H⋯π interactions (Karle et al., 2007 ) between the H14A atom and the pyridine ring of the 4,4′-^tBubpy ligand (Table 2), along with intermolecular π–π interactions (Janiak, 2000 ) between the pyridine rings of the 4,4′-^tBubpy ligands [Cg1⋯Cg1ⁱ = 3.7222 (13) Å, interplanar distance = 3.6034 (16) Å, slippage = 0.933 Å. Cg1 is the centroid of the N1/C1–C5 ring; symmetry code: (i) −x + $[{5\over 4}]$ , −y + $[{5\over 4}]$ , z], are present (Fig. 2), forming a three-dimensional network (Fig. 3).

Table 2
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the N2/C6–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14A⋯Cg2ⁱ	0.98	2.78	3.431 (2)	124
Symmetry code: (i) .

Figure 2
Details of the C—H⋯π interactions and the π–π interactions between the 4,4′-^tBubpy ligands of V₂. Cg1 and Cg2 are the centroids of the N1/C1–C5 ring and the N2/C6–C10 ring, respectively. The hydrogen atoms of 4,4′-^tBubpy ligands except for H14A, H14B, and H14C are omitted for clarity.

Figure 3
Crystal packing view of V₂·CH₃CN along the a axis.

4. Synthesis and crystallization

To a solution of 4,4′-di-tert-butyl-2,2′-bipyridyl (4,4′-^tBubpy) (269.0 mg, 1.0 mmol) in EtOH (10 mL) was added a solution of VOSO₄·5H₂O (126.8 mg, 0.5 mmol) in EtOH (5.5 mL). After stirring for 2.5 h at 313 K, the solution was concentrated under reduced pressure, and the green precipitate was filtered using Et₂O and dried to afford a green powder. Then, the powder was suspended in water, and an aqueous solution of sodium lauryl sulfate was added. After the mixture had been stirred overnight at ambient temperature, the supernatant liquid was separated from a dark-green oily precipitate by decantation, and the precipitate was washed with water. The precipitate was dissolved in an EtOH–Et₂O mixed solvent. After the color of the solution turned from green to orange, it was evaporated, and the precipitate was filtered using Et₂O and dried to afford a yellowish brown solid, which was recrystallized from CH₃CN and Et₂O to give V₂ (30.8 mg, 13% based on V) as dark-brown crystals. Analysis calculated for C₃₆H₄₉N₄O₁₁S₂V₂·3H₂O: C, 46.30; H, 5.94; N, 6.00. Found: C, 45.95; H, 5.82; N, 6.05.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were positioned geometrically (C—H = 0.95–0.98 Å) and refined as riding with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_methyl).

Table 3
Experimental details

Crystal data
Chemical formula	[V₂(HS₂O₈)O₃(C₁₈H₂₄N₂)₂]·C₂H₃N
M_r	920.84
Crystal system, space group	Orthorhombic, Fddd
Temperature (K)	110
a, b, c (Å)	13.0134 (2), 34.9495 (5), 39.4864 (6)
V (Å³)	17958.9 (5)
Z	16
Radiation type	Mo Kα
μ (mm⁻¹)	0.57
Crystal size (mm)	0.16 × 0.11 × 0.06

Data collection
Diffractometer	Rigaku Saturn724+ (2×2 bin mode)
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.815, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	51528, 6582, 5675
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.110, 1.12
No. of reflections	6582
No. of parameters	287
No. of restraints	27
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.34
Computer programs: CrystalClear-SM Expert (Rigaku, 2011 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), OLEX2.solve (Bourhis et al., 2015 ), SHELXL2018/3 (Sheldrick, 2015 ), and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2301351

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023009040/nx2001sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023009040/nx2001Isup2.hkl

checkCIF report

Computing details top

Data collection: CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011); cell refinement: CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011); data reduction: CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011); program(s) used to solve structure: olex2.solve 1.5 (Bourhis et al., 2015); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: Olex2 1.5 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

(µ-Hydrogen disulfato)-µ-oxido-bis[(4,4'-di-tert-butyl-2,2'-bipyridine)oxidovanadium(IV/V)] acetonitrile monosolvate top

Crystal data top

[V₂(HS₂O₈)O₃(C₁₈H₂₄N₂)₂]·C₂H₃N	D_x = 1.362 Mg m⁻³
M_r = 920.84	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fddd	Cell parameters from 30626 reflections
a = 13.0134 (2) Å	θ = 1.9–30.6°
b = 34.9495 (5) Å	µ = 0.57 mm⁻¹
c = 39.4864 (6) Å	T = 110 K
V = 17958.9 (5) Å³	Block, clear dark brown
Z = 16	0.16 × 0.11 × 0.06 mm
F(000) = 7696

Data collection top

Rigaku Saturn724+ (2x2 bin mode) diffractometer	6582 independent reflections
Radiation source: Rotating Anode	5675 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm^-1	R_int = 0.049
profile data from ω–scans	θ_max = 30.5°, θ_min = 2.1°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −18→18
T_min = 0.815, T_max = 1.000	k = −49→50
51528 measured reflections	l = −55→54

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0469P)² + 46.648P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max = 0.003
6582 reflections	Δρ_max = 0.50 e Å⁻³
287 parameters	Δρ_min = −0.33 e Å⁻³
27 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	Occ. (<1)
V1	0.70713 (2)	0.54069 (2)	0.59096 (2)	0.02335 (8)
S1	0.75306 (3)	0.47690 (2)	0.64590 (2)	0.02120 (10)
O5	0.66572 (10)	0.49435 (3)	0.66352 (3)	0.0235 (2)
O3	0.78535 (10)	0.50242 (4)	0.61695 (3)	0.0255 (3)
O6	0.71873 (10)	0.43950 (3)	0.63066 (3)	0.0258 (3)
O4	0.84010 (10)	0.46966 (4)	0.66746 (3)	0.0299 (3)
O1	0.79258 (12)	0.57322 (4)	0.58859 (3)	0.0369 (3)
O2	0.625000	0.55852 (5)	0.625000	0.0394 (5)
N2	0.75091 (11)	0.51363 (4)	0.54454 (3)	0.0216 (3)
N1	0.60817 (12)	0.56465 (4)	0.55441 (3)	0.0224 (3)
C3	0.48418 (13)	0.59696 (5)	0.50377 (4)	0.0225 (3)
C6	0.69971 (13)	0.52426 (5)	0.51604 (4)	0.0202 (3)
C7	0.72724 (13)	0.51037 (5)	0.48439 (4)	0.0223 (3)
H7	0.688735	0.517593	0.464972	0.027*
C8	0.81169 (13)	0.48568 (5)	0.48092 (4)	0.0252 (3)
C11	0.41640 (14)	0.61383 (5)	0.47598 (5)	0.0260 (3)
C4	0.55602 (13)	0.56814 (4)	0.49641 (4)	0.0210 (3)
H4	0.562535	0.558953	0.473872	0.025*
C5	0.61741 (13)	0.55301 (4)	0.52172 (4)	0.0200 (3)
C2	0.47668 (14)	0.60821 (5)	0.53749 (5)	0.0265 (3)
H2	0.428897	0.627475	0.543821	0.032*
C10	0.83025 (13)	0.48947 (5)	0.54148 (4)	0.0259 (3)
H10	0.865230	0.481514	0.561393	0.031*
C9	0.86340 (14)	0.47561 (5)	0.51049 (5)	0.0283 (4)
H9	0.921500	0.459194	0.509397	0.034*
C1	0.53844 (15)	0.59148 (5)	0.56180 (4)	0.0266 (3)
H1	0.531067	0.599365	0.584695	0.032*
C15	0.84388 (15)	0.47210 (6)	0.44572 (5)	0.0329 (4)
C12	0.48286 (15)	0.62876 (5)	0.44658 (5)	0.0310 (4)
H12A	0.524627	0.607783	0.437528	0.047*
H12B	0.527993	0.649180	0.454815	0.047*
H12C	0.438268	0.638807	0.428664	0.047*
C13	0.34999 (16)	0.64692 (6)	0.48896 (6)	0.0375 (5)
H13A	0.394311	0.666815	0.498583	0.056*
H13B	0.302988	0.637465	0.506451	0.056*
H13C	0.310203	0.657649	0.470150	0.056*
C14	0.34585 (16)	0.58193 (6)	0.46305 (5)	0.0346 (4)
H14A	0.299790	0.573763	0.481303	0.052*
H14B	0.387562	0.560154	0.455598	0.052*
H14C	0.305067	0.591466	0.443967	0.052*
C18	0.93513 (18)	0.44437 (7)	0.44714 (6)	0.0434 (5)
H18A	0.915526	0.421472	0.459928	0.065*
H18B	0.993353	0.456879	0.458329	0.065*
H18C	0.954806	0.437044	0.424081	0.065*
C17	0.87660 (19)	0.50771 (7)	0.42503 (5)	0.0437 (5)
H17A	0.929138	0.521948	0.437572	0.065*
H17B	0.816724	0.524171	0.421258	0.065*
H17C	0.904661	0.499545	0.403158	0.065*
C16	0.75339 (19)	0.45218 (7)	0.42815 (6)	0.0467 (6)
H16A	0.695186	0.469893	0.426686	0.070*
H16B	0.733200	0.429568	0.441237	0.070*
H16C	0.773966	0.444343	0.405306	0.070*
N3	0.6842 (6)	0.5900 (2)	0.3294 (2)	0.102 (2)	0.5
C19	0.5721 (5)	0.64049 (17)	0.36076 (15)	0.0605 (14)	0.5
H19A	0.549690	0.660308	0.344825	0.091*	0.5
H19B	0.611988	0.652277	0.379037	0.091*	0.5
H19C	0.511740	0.627648	0.370330	0.091*	0.5
C20	0.6367 (5)	0.61212 (17)	0.34275 (17)	0.0616 (15)	0.5
H6	0.659 (3)	0.4376 (11)	0.6263 (12)	0.022 (11)*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.03845 (17)	0.01764 (13)	0.01395 (13)	−0.00275 (11)	−0.00195 (11)	0.00237 (10)
S1	0.0276 (2)	0.01950 (18)	0.01648 (18)	−0.00117 (15)	−0.00710 (15)	0.00280 (14)
O5	0.0351 (6)	0.0179 (5)	0.0175 (5)	0.0015 (5)	−0.0031 (5)	0.0012 (4)
O3	0.0312 (6)	0.0263 (6)	0.0188 (6)	−0.0014 (5)	−0.0056 (5)	0.0055 (5)
O6	0.0299 (7)	0.0197 (5)	0.0278 (6)	0.0026 (5)	−0.0082 (5)	−0.0035 (5)
O4	0.0337 (7)	0.0335 (7)	0.0225 (6)	−0.0012 (5)	−0.0126 (5)	0.0061 (5)
O1	0.0574 (9)	0.0273 (6)	0.0260 (7)	−0.0137 (6)	−0.0164 (6)	0.0075 (5)
O2	0.0866 (16)	0.0163 (8)	0.0154 (8)	0.000	−0.0162 (9)	0.000
N2	0.0258 (7)	0.0224 (6)	0.0165 (6)	−0.0021 (5)	−0.0045 (5)	0.0027 (5)
N1	0.0361 (8)	0.0169 (6)	0.0142 (6)	−0.0020 (5)	0.0000 (5)	−0.0007 (5)
C3	0.0267 (8)	0.0173 (7)	0.0236 (8)	−0.0009 (6)	−0.0029 (6)	−0.0032 (6)
C6	0.0248 (7)	0.0199 (7)	0.0160 (7)	−0.0009 (6)	−0.0030 (6)	0.0017 (6)
C7	0.0259 (8)	0.0238 (7)	0.0171 (7)	0.0025 (6)	−0.0047 (6)	−0.0001 (6)
C8	0.0259 (8)	0.0288 (8)	0.0207 (8)	0.0024 (7)	−0.0022 (6)	−0.0010 (6)
C11	0.0290 (8)	0.0202 (7)	0.0289 (8)	0.0042 (6)	−0.0069 (7)	−0.0053 (6)
C4	0.0267 (8)	0.0196 (7)	0.0167 (7)	0.0002 (6)	−0.0016 (6)	−0.0022 (6)
C5	0.0280 (8)	0.0163 (6)	0.0157 (7)	−0.0014 (6)	−0.0010 (6)	−0.0007 (5)
C2	0.0331 (9)	0.0202 (7)	0.0260 (8)	0.0017 (6)	0.0018 (7)	−0.0064 (6)
C10	0.0255 (8)	0.0306 (8)	0.0216 (8)	0.0004 (7)	−0.0069 (6)	0.0034 (7)
C9	0.0252 (8)	0.0342 (9)	0.0257 (8)	0.0061 (7)	−0.0041 (7)	0.0014 (7)
C1	0.0418 (10)	0.0195 (7)	0.0185 (7)	−0.0011 (7)	0.0019 (7)	−0.0046 (6)
C15	0.0333 (9)	0.0419 (10)	0.0234 (8)	0.0141 (8)	−0.0034 (7)	−0.0064 (8)
C12	0.0378 (10)	0.0261 (8)	0.0292 (9)	0.0026 (7)	−0.0079 (7)	0.0021 (7)
C13	0.0373 (10)	0.0317 (10)	0.0436 (11)	0.0128 (8)	−0.0062 (9)	−0.0083 (8)
C14	0.0348 (10)	0.0284 (9)	0.0407 (11)	−0.0005 (7)	−0.0120 (8)	−0.0066 (8)
C18	0.0416 (11)	0.0547 (13)	0.0337 (11)	0.0206 (10)	−0.0025 (9)	−0.0081 (10)
C17	0.0523 (13)	0.0544 (13)	0.0243 (9)	0.0141 (11)	0.0077 (9)	0.0033 (9)
C16	0.0444 (12)	0.0551 (14)	0.0404 (12)	0.0158 (10)	−0.0109 (10)	−0.0243 (11)
N3	0.088 (4)	0.100 (4)	0.117 (5)	−0.037 (3)	0.042 (4)	−0.029 (4)
C19	0.073 (3)	0.063 (3)	0.045 (3)	−0.037 (3)	0.003 (3)	−0.007 (2)
C20	0.053 (3)	0.065 (3)	0.067 (3)	−0.022 (3)	0.008 (3)	0.001 (2)

Geometric parameters (Å, º) top

V1—O5ⁱ	2.2827 (12)	C10—H10	0.9500
V1—O3	1.9692 (12)	C10—C9	1.385 (3)
V1—O1	1.5932 (14)	C9—H9	0.9500
V1—O2	1.8268 (7)	C1—H1	0.9500
V1—N2	2.1399 (14)	C15—C18	1.534 (3)
V1—N1	2.1077 (14)	C15—C17	1.549 (3)
S1—O5	1.4654 (13)	C15—C16	1.534 (3)
S1—O3	1.5098 (12)	C12—H12A	0.9800
S1—O6	1.5066 (13)	C12—H12B	0.9800
S1—O4	1.4391 (13)	C12—H12C	0.9800
O6—H6	0.80 (4)	C13—H13A	0.9800
N2—C6	1.360 (2)	C13—H13B	0.9800
N2—C10	1.339 (2)	C13—H13C	0.9800
N1—C5	1.359 (2)	C14—H14A	0.9800
N1—C1	1.337 (2)	C14—H14B	0.9800
C3—C11	1.526 (2)	C14—H14C	0.9800
C3—C4	1.405 (2)	C18—H18A	0.9800
C3—C2	1.392 (2)	C18—H18B	0.9800
C6—C7	1.388 (2)	C18—H18C	0.9800
C6—C5	1.486 (2)	C17—H17A	0.9800
C7—H7	0.9500	C17—H17B	0.9800
C7—C8	1.404 (2)	C17—H17C	0.9800
C8—C9	1.393 (2)	C16—H16A	0.9800
C8—C15	1.527 (2)	C16—H16B	0.9800
C11—C12	1.539 (3)	C16—H16C	0.9800
C11—C13	1.532 (2)	N3—C20	1.120 (9)
C11—C14	1.532 (2)	C19—H19A	0.9800
C4—H4	0.9500	C19—H19B	0.9800
C4—C5	1.384 (2)	C19—H19C	0.9800
C2—H2	0.9500	C19—C20	1.482 (8)
C2—C1	1.382 (3)

O3—V1—O5ⁱ	85.44 (5)	N2—C10—H10	118.7
O3—V1—N2	90.49 (5)	N2—C10—C9	122.69 (15)
O3—V1—N1	160.47 (5)	C9—C10—H10	118.7
O1—V1—O5ⁱ	172.18 (6)	C8—C9—H9	119.9
O1—V1—O3	98.89 (7)	C10—C9—C8	120.11 (16)
O1—V1—O2	102.02 (7)	C10—C9—H9	119.9
O1—V1—N2	94.54 (7)	N1—C1—C2	122.68 (16)
O1—V1—N1	95.89 (6)	N1—C1—H1	118.7
O2—V1—O5ⁱ	83.64 (5)	C2—C1—H1	118.7
O2—V1—O3	98.66 (5)	C8—C15—C18	112.05 (16)
O2—V1—N2	159.52 (5)	C8—C15—C17	107.79 (16)
O2—V1—N1	90.62 (5)	C8—C15—C16	110.01 (17)
N2—V1—O5ⁱ	78.84 (5)	C18—C15—C17	108.31 (18)
N1—V1—O5ⁱ	78.52 (5)	C18—C15—C16	108.92 (18)
N1—V1—N2	75.63 (5)	C16—C15—C17	109.72 (18)
O5—S1—O3	109.23 (7)	C11—C12—H12A	109.5
O5—S1—O6	108.70 (8)	C11—C12—H12B	109.5
O6—S1—O3	107.02 (7)	C11—C12—H12C	109.5
O4—S1—O5	113.76 (8)	H12A—C12—H12B	109.5
O4—S1—O3	109.43 (8)	H12A—C12—H12C	109.5
O4—S1—O6	108.49 (8)	H12B—C12—H12C	109.5
S1—O5—V1ⁱ	143.30 (7)	C11—C13—H13A	109.5
S1—O3—V1	130.69 (8)	C11—C13—H13B	109.5
S1—O6—H6	117 (3)	C11—C13—H13C	109.5
V1—O2—V1ⁱ	140.11 (10)	H13A—C13—H13B	109.5
C6—N2—V1	117.24 (11)	H13A—C13—H13C	109.5
C10—N2—V1	124.13 (11)	H13B—C13—H13C	109.5
C10—N2—C6	118.41 (14)	C11—C14—H14A	109.5
C5—N1—V1	118.52 (11)	C11—C14—H14B	109.5
C1—N1—V1	122.95 (11)	C11—C14—H14C	109.5
C1—N1—C5	118.51 (15)	H14A—C14—H14B	109.5
C4—C3—C11	120.86 (15)	H14A—C14—H14C	109.5
C2—C3—C11	122.56 (15)	H14B—C14—H14C	109.5
C2—C3—C4	116.56 (15)	C15—C18—H18A	109.5
N2—C6—C7	121.55 (15)	C15—C18—H18B	109.5
N2—C6—C5	114.41 (14)	C15—C18—H18C	109.5
C7—C6—C5	123.97 (14)	H18A—C18—H18B	109.5
C6—C7—H7	119.8	H18A—C18—H18C	109.5
C6—C7—C8	120.33 (15)	H18B—C18—H18C	109.5
C8—C7—H7	119.8	C15—C17—H17A	109.5
C7—C8—C15	119.64 (15)	C15—C17—H17B	109.5
C9—C8—C7	116.86 (16)	C15—C17—H17C	109.5
C9—C8—C15	123.49 (16)	H17A—C17—H17B	109.5
C3—C11—C12	110.40 (15)	H17A—C17—H17C	109.5
C3—C11—C13	112.15 (15)	H17B—C17—H17C	109.5
C3—C11—C14	107.75 (14)	C15—C16—H16A	109.5
C13—C11—C12	108.28 (16)	C15—C16—H16B	109.5
C14—C11—C12	109.39 (15)	C15—C16—H16C	109.5
C14—C11—C13	108.84 (16)	H16A—C16—H16B	109.5
C3—C4—H4	119.7	H16A—C16—H16C	109.5
C5—C4—C3	120.58 (15)	H16B—C16—H16C	109.5
C5—C4—H4	119.7	H19A—C19—H19B	109.5
N1—C5—C6	114.19 (14)	H19A—C19—H19C	109.5
N1—C5—C4	121.35 (15)	H19B—C19—H19C	109.5
C4—C5—C6	124.43 (14)	C20—C19—H19A	109.5
C3—C2—H2	119.9	C20—C19—H19B	109.5
C1—C2—C3	120.28 (16)	C20—C19—H19C	109.5
C1—C2—H2	119.9	N3—C20—C19	178.4 (7)

V1—N2—C6—C7	175.43 (12)	C7—C6—C5—N1	−175.49 (16)
V1—N2—C6—C5	−1.51 (18)	C7—C6—C5—C4	2.7 (3)
V1—N2—C10—C9	−172.91 (14)	C7—C8—C9—C10	0.7 (3)
V1—N1—C5—C6	−0.61 (18)	C7—C8—C15—C18	−178.11 (18)
V1—N1—C5—C4	−178.82 (12)	C7—C8—C15—C17	62.8 (2)
V1—N1—C1—C2	177.27 (13)	C7—C8—C15—C16	−56.8 (2)
O5ⁱ—V1—O2—V1ⁱ	36.88 (3)	C11—C3—C4—C5	179.87 (15)
O5—S1—O3—V1	−24.59 (12)	C11—C3—C2—C1	178.68 (16)
O3—V1—O2—V1ⁱ	−47.50 (4)	C4—C3—C11—C12	−54.6 (2)
O3—S1—O5—V1ⁱ	14.21 (15)	C4—C3—C11—C13	−175.46 (16)
O6—S1—O5—V1ⁱ	−102.23 (13)	C4—C3—C11—C14	64.8 (2)
O6—S1—O3—V1	92.92 (11)	C4—C3—C2—C1	0.4 (3)
O4—S1—O5—V1ⁱ	136.79 (12)	C5—N1—C1—C2	−1.0 (3)
O4—S1—O3—V1	−149.72 (10)	C5—C6—C7—C8	174.54 (16)
O1—V1—O2—V1ⁱ	−148.59 (5)	C2—C3—C11—C12	127.22 (18)
N2—V1—O2—V1ⁱ	68.14 (17)	C2—C3—C11—C13	6.4 (2)
N2—C6—C7—C8	−2.1 (3)	C2—C3—C11—C14	−113.38 (19)
N2—C6—C5—N1	1.4 (2)	C2—C3—C4—C5	−1.9 (2)
N2—C6—C5—C4	179.52 (15)	C10—N2—C6—C7	0.7 (2)
N2—C10—C9—C8	−2.1 (3)	C10—N2—C6—C5	−176.23 (15)
N1—V1—O2—V1ⁱ	115.25 (4)	C9—C8—C15—C18	3.4 (3)
C3—C4—C5—N1	1.9 (2)	C9—C8—C15—C17	−115.7 (2)
C3—C4—C5—C6	−176.08 (15)	C9—C8—C15—C16	124.7 (2)
C3—C2—C1—N1	1.0 (3)	C1—N1—C5—C6	177.74 (15)
C6—N2—C10—C9	1.4 (3)	C1—N1—C5—C4	−0.5 (2)
C6—C7—C8—C9	1.3 (3)	C15—C8—C9—C10	179.22 (18)
C6—C7—C8—C15	−177.25 (17)

Symmetry code: (i) −x+5/4, y, −z+5/4.

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the N2/C6–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···Cg2ⁱⁱ	0.98	2.78	3.431 (2)	124

Symmetry code: (ii) −x+1, −y+1, −z+1.

BVS calculations for vanadium atoms of [V₂O₂(µ-O)(µ-H(SO₄)₂)(4,4'-^tBubpy)₂] (V₂) top

BVS calculations were conducted using X-ray data of [V₂O₂(µ-O)(µ-H(SO₄)₂)(4,4'-^tBubpy)₂]. Bond-valence parameters: V^IV—O (1.784 Å), V^V—O (1.803 Å), and V—N (1.86 Å) (Brese et al., 1991).

[V₂O₂(µ-O)(µ-H(SO₄)₂)(4,4'-^tBubpy)₂]	V1
V(IV)	4.41
V(V)	4.59

Acknowledgements

The authors thank Dr Rika Tanaka, Dr Tamaki Nagasawa, Dr Matsumi Doe, Professor Ikuko Miyahara, and Professor Tetsuro Shinada (Osaka Metropolitan University) for the single-crystal X-ray analysis and elemental analysis measurements.

Funding information

Funding for this research was provided by: Japan Society for the Promotion of Science (grant No. JP21H01977).

References

Ballhausen, C. J. & Gray, H. B. (1962). Inorg. Chem. 1, 111–122. Web of Science CrossRef CAS Google Scholar
Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59–75. Web of Science CrossRef IUCr Journals Google Scholar
Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192–197. CrossRef CAS Web of Science IUCr Journals Google Scholar
Cleland, W. W., Frey, P. A. & Gerlt, J. A. (1998). J. Biol. Chem. 273, 25529–25532. Web of Science CrossRef CAS PubMed Google Scholar
Datta, C., Das, D., Mondal, P., Chakraborty, B., Sengupta, M. & Bhattacharjee, C. R. (2015). Eur. J. Med. Chem. 97, 214–224. CrossRef CAS PubMed Google Scholar
Díaz-Torres, R. & Alvarez, S. (2011). Dalton Trans. 40, 10742–10750. PubMed Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gómez-García, C. J., Escrivà, E., Benmansour, S., Borràs-Almenar, J. J., Folgado, J.-V. & Ramírez de Arellano, C. (2016). Inorg. Chem. 55, 2664–2671. PubMed Google Scholar
Inoue, Y., Kodama, S., Taya, N., Sato, H., Oh-ishi, K. & Ishii, Y. (2018). Inorg. Chem. 57, 7491–7494. CSD CrossRef CAS PubMed Google Scholar
Janiak, C. (2000). J. Chem. Soc. Dalton Trans. pp. 3885–3896. Web of Science CrossRef Google Scholar
Karle, I. L., Butcher, R. J., Wolak, M. A., da Silva Filho, D. A., Uchida, M., Brédas, J.-L. & Kafafi, Z. H. (2007). J. Phys. Chem. C, 111, 9543–9547. Web of Science CSD CrossRef CAS Google Scholar
Leszczyński, P. J., Budzianowski, A., Dobrzycki, Ł., Cyrański, M. K., Derzsi, M. & Grochala, W. (2012). Dalton Trans. 41, 396–402. PubMed Google Scholar
Mi, F.-Q., Ma, F.-X., Zou, S.-X., Zhan, D.-S. & Zhang, T. (2022). Dalton Trans. 51, 1313–1317. CSD CrossRef CAS PubMed Google Scholar
Natarajan, S. & Mandal, S. (2008). Angew. Chem. Int. Ed. 47, 4798–4828. Web of Science CrossRef CAS Google Scholar
Nilsson, J., Degerman, E., Haukka, M., Lisensky, G. C., Garribba, E., Yoshikawa, Y., Sakurai, H., Enydy, E. A., Kiss, T., Esbak, H., Rehder, D. & Norlander, E. (2009). Dalton Trans. 7902–7911. Google Scholar
Papatriantafyllopoulou, C., Manessi-Zoupa, E., Escuer, A. & Perlepes, S. P. (2009). Inorg. Chim. Acta, 362, 634–650. Web of Science CrossRef CAS Google Scholar
Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Schindler, L. V. & Wickleder, M. S. (2017). Z. Naturforsch. B, 72, 63–68. CrossRef ICSD CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Triantafillou, G. D., Tolis, E. I., Terzis, A., Deligiannakis, Y., Raptopoulou, C. P., Sigalas, M. P. & Kabanos, T. A. (2004). Inorg. Chem. 43, 79–91. Web of Science CSD CrossRef PubMed CAS Google Scholar
Waidmann, C. R., Zhou, X., Tsai, E. A., Kaminsky, W., Hrovat, D. A., Borden, W. T. & Mayer, J. M. (2009). J. Am. Chem. Soc. 131, 4729–4743. CSD CrossRef PubMed CAS Google Scholar
Walsh, J. J., Bond, A. M., Forster, R. J. & Keyes, T. E. (2016). Coord. Chem. Rev. 306, 217–234. Web of Science CrossRef CAS Google Scholar
Wang, X., Brunson, K., Xie, H., Colliard, I., Wasson, M. C., Gong, X., Ma, K., Wu, Y., Son, F. A., Idrees, K. B., Zhang, X., Notestein, J. M., Nyman, M. & Farha, O. K. (2021). J. Am. Chem. Soc. 143, 21056–21065. CSD CrossRef CAS PubMed Google Scholar
Xie, R., Ma, L., Li, Z., Qu, Z., Yan, N. & Li, J. (2021). ACS Catal. 11, 13119–13139. CrossRef CAS Google Scholar

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