Synthesis and crystal structure of di-μ-methoxo-bis­(oxido{N′-[3-(oxido­imino)­butan-2-yl­idene]benzo­hydrazonato-κ3O,N,O′}vanadium(V))

Saladi, N.; Srivastava, A.K.

doi:10.1107/S2056989022010775

research communications

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ISSN: 2056-9890

Volume 78| Part 12| December 2022| Pages 1213-1216

https://doi.org/10.1107/S2056989022010775

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Synthesis and crystal structure of di-μ-methoxo-bis(oxido{N′-[3-(oxidoimino)butan-2-ylidene]benzohydrazonato-κ³O,N,O′}vanadium(V))

Nirupama Saladi ^a ^* and Ankit Kumar Srivastava ^a

^aSchool of Chemistry, University of Hyderabad, Hyderabad 500 046, India
^*Correspondence e-mail: 19chph09@uohyd.ac.in

Edited by S. Parkin, University of Kentucky, USA (Received 10 October 2022; accepted 10 November 2022; online 15 November 2022)

The structure of the dimeric oxomethoxovanadium(V) complex, [V₂(CH₃O)₂(C₁₁H₁₁N₃O₃)₂] or [VO(μ-OMe)(L)]₂ (1), with N′-[3-(hydroxyimino)-butan-2-ylidene]benzohydrazide (H₂L, where 2 Hs represent the dissociable oxime and amide protons) is reported. The oximate functionality can coordinate through either the O or the N atom. In the present complex, it is coordinated through the O atom. Here, methoxo groups bridge the two V^V centers with a V⋯V separation of 3.3275 (10) Å. Within the centrosymmetric edge-shared dioctahedral structure, each metal center is in a distorted octahedral NO₅ environment, assembled by the O,N,O-donor L^2– ligand, bridging OMe⁻ groups and the oxo group. The complex is diamagnetic in nature and brown in color. Solution electrical conductivity measurements confirmed its electrically non-conducting behavior.

Keywords: crystal structure; oxomethoxovanadium(V); Schiff base; dinuclear complex.

CCDC reference: 2218751

1. Chemical context

Interest in the coordination complexes of vanadium is primarily due to their variety of roles in biological processes such as nitrogen fixation, haloperoxidation, phosphorylation, insulin mimicking, anti-microbial and anti-fungal activities, and for their possible use as efficient catalysts in various organic reactions (Noblía et al., 2004 ; Plass et al., 2007 ; Zabin & Abdelbaset, 2016 ; Tsave et al., 2016 ; Tanabe & Nishibayashi, 2019 ; Assey & Mgohamwende, 2020 ). Oxovanadium(V) (VO³⁺) and dioxovanadium(V) (VO₂⁺) catalyzed reactions include C—C bond formation, hydrogenation, dehydrogenation, sulfide oxidation, C—C/C—O bond cleavage, alcohol/aldehyde/ketone oxidation, deoxydehydration (Langeslay et al., 2019 ). Oxovanadium(IV/V) materials have also found several industrial applications such as gas sensors, electrochemical and optical switching devices, and reversible cathode materials for Li batteries (Guerrero-Pérez, 2017 ).

Our research group has previously reported some pentavalent vanadium complexes with aroylhydrazine-based Schiff bases (Srivastava et al., 2020 ). Herein we report a dinuclear centrosymmetric complex [VO(μ-OMe)(L)]₂, where we have used an ambidentate oxime containing N′-[3-(hydroxyimino)butan-2-ylidene]benzohydrazide (H₂L).

2. Structural commentary

The dimeric complex [VO(μ-OMe)(L)]₂ (1) crystallizes in the triclinic P $[\overline{1}]$ space group. Here the asymmetric unit contains half of the formula unit and the two halves of the dimeric molecule are related by an inversion center. A displacement ellipsoid plot of 1 is illustrated in Fig. 1. The meridionally spanning L^2– coordinates to the metal center via the oximate-O, the imine-N and the amidate-O atoms (O1, N2 and O2, respectively) and forms fused five- and six-membered chelate rings. The methoxo-O atom (O3) completes an NO₃ square plane (r.m.s. deviation = 0.02 Å) and the oxo group (O4) occupies the apical position to complete a square-pyramidal NO₄ coordination environment around the metal center. As generally observed in a square-pyramidal geometry, here the vanadium atom is also shifted towards the apical oxo group by 0.34 Å. The dimeric structure is formed by two such inversion-symmetry-related square-pyramidal units, in which the methoxo-O atoms act as equatorial–axial bridging atoms. As a result, a divanadium(V) core, [OV(μ-OMe)₂VO]⁴⁺, is formed at the center of 1 and each metal center in it resides in a distorted octahedral NO₅ coordination sphere. Overall, two O,N,O-donor L^2–, two methoxo-O atoms, and the two oxo-O atoms constitute an edge-shared dioctahedral geometry [O₃NVO₂VNO₃] (Fig. 1). The central V₂(μ-OMe)₂ moiety has a pair of short [1.8351 (14) Å] and a pair of long [2.3240 (14) Å] V—O bonds (Table 1). The longer pair of bonds is trans to the corresponding oxo groups. The V⋯V distance is 3.3275 (10) Å. In general, the V=O, V—N, and V—O bond lengths in 1 are comparable with the corresponding bond lengths in other pentavalent vanadium complexes with analogous ligands (Dash et al., 2012 ; Sutradhar et al., 2013 ; Srivastava et al., 2018 ; Srivastava et al., 2020).

Table 1
Selected geometric parameters (Å, °)

V1—O4	1.5795 (16)	V1—O2	1.9469 (14)
V1—O1	1.8200 (16)	V1—N2	2.1013 (16)
V1—O3	1.8351 (14)	V1—O3ⁱ	2.3240 (14)

O4—V1—O1	100.13 (9)	O2—V1—N2	74.61 (6)
O4—V1—O3	103.30 (7)	O4—V1—O3ⁱ	177.40 (7)
O1—V1—O3	107.22 (7)	O1—V1—O3ⁱ	79.72 (7)
O4—V1—O2	100.48 (8)	O3—V1—O3ⁱ	74.33 (6)
O1—V1—O2	149.15 (7)	O2—V1—O3ⁱ	80.69 (6)
O3—V1—O2	90.01 (6)	N2—V1—O3ⁱ	87.30 (5)
O4—V1—N2	95.24 (7)	C12—O3—V1ⁱ	124.22 (14)
O1—V1—N2	80.87 (6)	V1—O3—V1ⁱ	105.67 (6)
O3—V1—N2	157.85 (6)
Symmetry code: (i) .

Figure 1
The molecular structure of [VO(μ-OMe)(L)]₂ (1). The non-hydrogen atoms are displayed as 30% probability ellipsoids. Unlabeled non-hydrogen atoms are related to the labeled non-hydrogen atoms by an inversion center (symmetry operator: −x, −y + 1, −z).

3. Supramolecular features

We have investigated the self-assembly pattern of complex 1 via intermolecular hydrogen-bonding interactions having an H⋯A distance of up to 3 Å. Only non-classical C—H⋯A (A = O and N) interactions have been found (Table 2). These are: one bifurcated C—H⋯O/N, two C—H⋯O and one C—H⋯N interactions involving the methyl C—H (C1—H1A and C4—H4A) and methoxo C—H groups (C12—H12B and C12—H12C) as donors, and iminolate-O (O2), oxo-O (O4), oximate-N (N1), and imine-N (N3) atoms as acceptors. The C—H⋯O (C12—H12B⋯O2 and C12—H12C⋯O4) interactions link the complex molecules and form linear chains parallel to each other. The bifurcated C—H⋯O/N (C1—H1A⋯O4/N1) hydrogen bonds connect the parallel linear chains and a di-periodic layered structure is formed. The C—H⋯N (C4—H4A⋯N3) interactions provide the links between the layers, assembling a three-dimensional network structure (Fig. 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O4ⁱⁱ	0.96	2.98	3.583 (3)	122
C1—H1A⋯N1ⁱⁱⁱ	0.96	3.02	3.508 (3)	113
C4—H4A⋯N3^iv	0.96	2.81	3.663 (3)	149
C12—H12B⋯O2^v	0.96	2.96	3.531 (3)	119
C12—H12C⋯O4^v	0.96	2.81	3.629 (3)	144
Symmetry codes: (ii) ; (iii) ; (iv) ; (v) .

Figure 2
Three-dimensional network of 1 viewed down the b-axis. Green dashed lines indicate non-classical hydrogen bonds listed in Table 2

. Hydrogen atoms not involved in these interactions are omitted for clarity.

4. Database survey

Five more structures of analogous dinuclear dimethoxo bridged oxovanadium(V) complexes are reported in the literature and deposited in the Cambridge Structure Database (CSD v5.43; Groom et al., 2016 ). These are [VO(μ-OMe)(L¹)]₂ (CSD refcode XIVJUH) with H₂L¹ = benzoylhydrazone of 2-hydroxy-5-methoxybenzaldehyde (Sangeetha et al., 2000 ), [VO(μ-OMe)(L²)]₂ (CSD: GAVROL) with H₂L² = diacetyl monoxime (4-methoxybenzoyl)hydrazone (Deng et al., 2005 ), [VO(μ-OMe)(L³)]₂ (CSD: KUBSUW) with H₂L³ = benzoic acid (1-methyl-3-oxo-butylidene)hydrazide, [VO(μ-OMe)(L⁴)]₂ (CSD: KUBTAD) with H₂L⁴ = 4-Cl-benzoic acid (1-methyl-3-oxo-butylidene)hydrazide (Sarkar & Pal, 2009 ), and [VO(μ-OMe)(HL⁵)]₂ (CSD: FUDTUW) with H₃L⁵ = diacetylmonoxime salicyloylhydrazone (Srivastava et al., 2020).

5. Synthesis and crystallization

The Schiff base (H₂L) was prepared in ∼72% yield by a condensation reaction with equimolar amounts of diacetyl-monoxime and benzohydrazide in methanol, following a reported procedure (Naskar et al., 2007 ).

A methanol solution (10 ml) of [VO(acac)₂] (80 mg, 0.3 mmol) was added to a methanol solution (10 ml) of H₂L (65 mg, 0.3 mmol) and the mixture was stirred under aerobic conditions for 6 h at room temperature. The resulting brown solution was kept for slow evaporation at room temperature in air. The dark-brown crystalline material was obtained in about a week. It was filtered, washed with cold methanol, and dried in air. A single crystal suitable for X-ray structure determination was selected from the crystals thus obtained. Yield: 47 mg (50%). HRMS in acetonitrile m/z found (calculated) for ([M + Li]⁺): 637.3059 (637.1008).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All non-hydrogen atoms were refined anisotropically. A riding model was used to include all hydrogen atoms at idealized positions with C—H distances of 0.93 Å (C_ar—H) and 0.96 Å (C_Me—H) and U_iso = 1.2 or 1.5 U_eq of the attached carbon atom.

Table 3
Experimental details

Crystal data
Chemical formula	[V₂(CH₃O)₂(C₁₁H₁₁N₃O₃)₂]
M_r	630.40
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	298
a, b, c (Å)	7.3050 (16), 9.825 (2), 11.121 (3)
α, β, γ (°)	105.586 (8), 107.226 (8), 101.610 (9)
V (Å³)	699.3 (3)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.73
Crystal size (mm)	0.23 × 0.22 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.851, 0.863
No. of measured, independent and observed [I > 2σ(I)] reflections	26928, 2849, 2495
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.085, 1.05
No. of reflections	2849
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.29
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXS97 (Sheldrick 2008 ), SHELXL2014/7 (Sheldrick 2015 ), Mercury (Macrae et al., 2020 ), and WinGX publication routines (Farrugia, 2012 ).

Supporting information

CCDC reference: 2218751

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022010775/pk2672sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022010775/pk2672Isup3.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick 2015); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).

Di-µ-methoxo-bis(oxido{N'-[3-(oxidoimino)butan-2-ylidene]benzohydrazonato-κ³O,N,O'}vanadium(V)) top

Crystal data top

[V₂(CH₃O)₂(C₁₁H₁₁N₃O₃)₂]	Z = 1
M_r = 630.40	F(000) = 324
Triclinic, P1	D_x = 1.497 Mg m⁻³
a = 7.3050 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.825 (2) Å	Cell parameters from 9603 reflections
c = 11.121 (3) Å	θ = 3.0–26.3°
α = 105.586 (8)°	µ = 0.73 mm⁻¹
β = 107.226 (8)°	T = 298 K
γ = 101.610 (9)°	Block, brown
V = 699.3 (3) Å³	0.23 × 0.22 × 0.21 mm

Data collection top

Bruker APEXII CCD diffractometer	2495 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.046
φ and ω scans	θ_max = 26.4°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −9→9
T_min = 0.851, T_max = 0.863	k = −12→12
26928 measured reflections	l = −13→13
2849 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0355P)² + 0.3713P] where P = (F_o² + 2F_c²)/3
2849 reflections	(Δ/σ)_max < 0.001
184 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The structure was solved by direct methods and refined on F² using full-matrix least-squares procedures.

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

	x	y	z	U_iso*/U_eq
V1	−0.08607 (5)	0.44936 (3)	0.10918 (3)	0.03903 (12)
O1	0.1665 (2)	0.50789 (16)	0.23557 (15)	0.0541 (4)
O2	−0.29767 (19)	0.30059 (14)	−0.05246 (14)	0.0404 (3)
O3	−0.0981 (2)	0.58907 (14)	0.02824 (14)	0.0409 (3)
O4	−0.2093 (3)	0.48301 (18)	0.20281 (16)	0.0578 (4)
N1	0.2299 (3)	0.4859 (2)	0.35485 (19)	0.0553 (5)
N2	−0.0753 (2)	0.24395 (17)	0.12871 (16)	0.0359 (3)
N3	−0.2005 (2)	0.11897 (17)	0.01885 (15)	0.0369 (4)
C1	0.2508 (4)	0.3332 (3)	0.4857 (2)	0.0611 (6)
H1A	0.316716	0.428766	0.555551	0.092*
H1B	0.345953	0.279053	0.482381	0.092*
H1C	0.143345	0.279288	0.503827	0.092*
C2	0.1669 (3)	0.3528 (2)	0.3532 (2)	0.0454 (5)
C3	0.0332 (3)	0.2233 (2)	0.23344 (19)	0.0380 (4)
C4	0.0235 (3)	0.0707 (2)	0.2350 (2)	0.0484 (5)
H4A	0.011744	0.007875	0.148658	0.073*
H4B	−0.091311	0.031769	0.254590	0.073*
H4C	0.143812	0.074359	0.302670	0.073*
C5	−0.3129 (3)	0.1622 (2)	−0.06967 (19)	0.0355 (4)
C6	−0.4598 (3)	0.0488 (2)	−0.19731 (19)	0.0369 (4)
C7	−0.5068 (3)	−0.1011 (2)	−0.2135 (2)	0.0457 (5)
H7	−0.452941	−0.130314	−0.141287	0.055*
C8	−0.6331 (3)	−0.2060 (2)	−0.3364 (2)	0.0551 (6)
H8	−0.662785	−0.306194	−0.347149	0.066*
C9	−0.7154 (4)	−0.1640 (3)	−0.4428 (2)	0.0618 (6)
H9	−0.799625	−0.235320	−0.525864	0.074*
C10	−0.6730 (4)	−0.0165 (3)	−0.4264 (2)	0.0681 (7)
H10	−0.730846	0.012005	−0.498326	0.082*
C11	−0.5455 (4)	0.0906 (3)	−0.3042 (2)	0.0534 (6)
H11	−0.517565	0.190539	−0.294152	0.064*
C12	−0.2584 (4)	0.6538 (3)	0.0049 (3)	0.0625 (7)
H12A	−0.215116	0.743512	−0.011824	0.094*
H12B	−0.294736	0.676184	0.082561	0.094*
H12C	−0.372897	0.585240	−0.071673	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.0405 (2)	0.03042 (18)	0.0430 (2)	0.00729 (14)	0.01466 (15)	0.01163 (14)
O1	0.0502 (9)	0.0411 (8)	0.0513 (9)	−0.0025 (7)	0.0044 (7)	0.0144 (7)
O2	0.0355 (7)	0.0337 (7)	0.0459 (8)	0.0062 (6)	0.0091 (6)	0.0146 (6)
O3	0.0379 (7)	0.0321 (7)	0.0557 (8)	0.0134 (6)	0.0187 (6)	0.0166 (6)
O4	0.0737 (11)	0.0503 (9)	0.0594 (10)	0.0227 (8)	0.0364 (9)	0.0188 (8)
N1	0.0509 (11)	0.0482 (11)	0.0458 (10)	0.0052 (9)	0.0016 (8)	0.0096 (8)
N2	0.0333 (8)	0.0333 (8)	0.0376 (8)	0.0067 (6)	0.0127 (7)	0.0102 (7)
N3	0.0358 (8)	0.0347 (8)	0.0356 (8)	0.0075 (7)	0.0113 (7)	0.0101 (7)
C1	0.0609 (15)	0.0654 (15)	0.0410 (12)	0.0124 (12)	0.0056 (11)	0.0138 (11)
C2	0.0405 (11)	0.0473 (12)	0.0406 (11)	0.0116 (9)	0.0098 (9)	0.0106 (9)
C3	0.0345 (10)	0.0413 (10)	0.0383 (10)	0.0114 (8)	0.0146 (8)	0.0130 (8)
C4	0.0535 (13)	0.0465 (12)	0.0470 (12)	0.0206 (10)	0.0148 (10)	0.0191 (10)
C5	0.0316 (9)	0.0366 (10)	0.0396 (10)	0.0067 (8)	0.0177 (8)	0.0131 (8)
C6	0.0316 (9)	0.0378 (10)	0.0391 (10)	0.0058 (8)	0.0153 (8)	0.0113 (8)
C7	0.0422 (11)	0.0410 (11)	0.0504 (12)	0.0095 (9)	0.0157 (9)	0.0146 (9)
C8	0.0523 (13)	0.0381 (11)	0.0623 (14)	0.0043 (10)	0.0213 (11)	0.0053 (10)
C9	0.0574 (14)	0.0589 (15)	0.0445 (13)	0.0026 (12)	0.0132 (11)	−0.0016 (11)
C10	0.0775 (18)	0.0694 (17)	0.0404 (12)	0.0095 (14)	0.0067 (12)	0.0199 (12)
C11	0.0619 (14)	0.0455 (12)	0.0437 (12)	0.0054 (10)	0.012 (1)	0.0183 (10)
C12	0.0553 (14)	0.0576 (14)	0.098 (2)	0.0325 (12)	0.0389 (14)	0.0391 (14)

Geometric parameters (Å, º) top

V1—O4	1.5795 (16)	C4—H4A	0.9600
V1—O1	1.8200 (16)	C4—H4B	0.9600
V1—O3	1.8351 (14)	C4—H4C	0.9600
V1—O2	1.9469 (14)	C5—C6	1.475 (3)
V1—N2	2.1013 (16)	C6—C11	1.378 (3)
V1—O3ⁱ	2.3240 (14)	C6—C7	1.392 (3)
O1—N1	1.361 (2)	C7—C8	1.377 (3)
O2—C5	1.298 (2)	C7—H7	0.9300
O3—C12	1.433 (3)	C8—C9	1.369 (4)
N1—C2	1.289 (3)	C8—H8	0.9300
N2—C3	1.293 (2)	C9—C10	1.369 (4)
N2—N3	1.385 (2)	C9—H9	0.9300
N3—C5	1.308 (2)	C10—C11	1.382 (3)
C1—C2	1.499 (3)	C10—H10	0.9300
C1—H1A	0.9600	C11—H11	0.9300
C1—H1B	0.9600	C12—H12A	0.9600
C1—H1C	0.9600	C12—H12B	0.9600
C2—C3	1.472 (3)	C12—H12C	0.9600
C3—C4	1.491 (3)

O4—V1—O1	100.13 (9)	N2—C3—C4	121.05 (18)
O4—V1—O3	103.30 (7)	C2—C3—C4	119.71 (18)
O1—V1—O3	107.22 (7)	C3—C4—H4A	109.5
O4—V1—O2	100.48 (8)	C3—C4—H4B	109.5
O1—V1—O2	149.15 (7)	H4A—C4—H4B	109.5
O3—V1—O2	90.01 (6)	C3—C4—H4C	109.5
O4—V1—N2	95.24 (7)	H4A—C4—H4C	109.5
O1—V1—N2	80.87 (6)	H4B—C4—H4C	109.5
O3—V1—N2	157.85 (6)	O2—C5—N3	123.23 (17)
O2—V1—N2	74.61 (6)	O2—C5—C6	118.16 (17)
O4—V1—O3ⁱ	177.40 (7)	N3—C5—C6	118.58 (17)
O1—V1—O3ⁱ	79.72 (7)	C11—C6—C7	119.27 (19)
O3—V1—O3ⁱ	74.33 (6)	C11—C6—C5	119.82 (18)
O2—V1—O3ⁱ	80.69 (6)	C7—C6—C5	120.85 (18)
N2—V1—O3ⁱ	87.30 (5)	C8—C7—C6	120.0 (2)
N1—O1—V1	129.68 (13)	C8—C7—H7	120.0
C5—O2—V1	117.55 (12)	C6—C7—H7	120.0
C12—O3—V1	124.15 (13)	C9—C8—C7	120.4 (2)
C12—O3—V1ⁱ	124.22 (14)	C9—C8—H8	119.8
V1—O3—V1ⁱ	105.67 (6)	C7—C8—H8	119.8
C2—N1—O1	116.97 (17)	C10—C9—C8	119.7 (2)
C3—N2—N3	117.28 (16)	C10—C9—H9	120.2
C3—N2—V1	126.48 (13)	C8—C9—H9	120.2
N3—N2—V1	116.22 (11)	C9—C10—C11	120.8 (2)
C5—N3—N2	107.95 (15)	C9—C10—H10	119.6
C2—C1—H1A	109.5	C11—C10—H10	119.6
C2—C1—H1B	109.5	C6—C11—C10	119.8 (2)
H1A—C1—H1B	109.5	C6—C11—H11	120.1
C2—C1—H1C	109.5	C10—C11—H11	120.1
H1A—C1—H1C	109.5	O3—C12—H12A	109.5
H1B—C1—H1C	109.5	O3—C12—H12B	109.5
N1—C2—C3	125.5 (2)	H12A—C12—H12B	109.5
N1—C2—C1	114.69 (19)	O3—C12—H12C	109.5
C3—C2—C1	119.7 (2)	H12A—C12—H12C	109.5
N2—C3—C2	119.24 (18)	H12B—C12—H12C	109.5

O4—V1—O1—N1	41.62 (19)	N3—N2—C3—C4	0.1 (3)
O3—V1—O1—N1	149.08 (17)	V1—N2—C3—C4	178.75 (14)
O2—V1—O1—N1	−89.6 (2)	N1—C2—C3—N2	−20.0 (3)
N2—V1—O1—N1	−52.12 (18)	C1—C2—C3—N2	163.8 (2)
O3ⁱ—V1—O1—N1	−141.01 (18)	N1—C2—C3—C4	160.6 (2)
O4—V1—O3—C12	−27.48 (19)	C1—C2—C3—C4	−15.7 (3)
O1—V1—O3—C12	−132.69 (18)	V1—O2—C5—N3	3.6 (2)
O2—V1—O3—C12	73.30 (18)	V1—O2—C5—C6	−174.43 (12)
N2—V1—O3—C12	118.6 (2)	N2—N3—C5—O2	1.7 (2)
O3ⁱ—V1—O3—C12	153.6 (2)	N2—N3—C5—C6	179.71 (15)
O4—V1—O3—V1ⁱ	178.90 (8)	O2—C5—C6—C11	13.4 (3)
O1—V1—O3—V1ⁱ	73.68 (8)	N3—C5—C6—C11	−164.71 (19)
O2—V1—O3—V1ⁱ	−80.33 (7)	O2—C5—C6—C7	−169.48 (17)
N2—V1—O3—V1ⁱ	−35.03 (18)	N3—C5—C6—C7	12.4 (3)
O3ⁱ—V1—O3—V1ⁱ	−0.001 (1)	C11—C6—C7—C8	1.9 (3)
V1—O1—N1—C2	48.4 (3)	C5—C6—C7—C8	−175.28 (19)
C3—N2—N3—C5	172.97 (16)	C6—C7—C8—C9	−0.9 (3)
V1—N2—N3—C5	−5.80 (18)	C7—C8—C9—C10	−0.6 (4)
O1—N1—C2—C3	0.3 (3)	C8—C9—C10—C11	1.1 (4)
O1—N1—C2—C1	176.7 (2)	C7—C6—C11—C10	−1.4 (3)
N3—N2—C3—C2	−179.30 (16)	C5—C6—C11—C10	175.8 (2)
V1—N2—C3—C2	−0.7 (3)	C9—C10—C11—C6	−0.1 (4)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4ⁱⁱ	0.96	2.98	3.583 (3)	122
C1—H1A···N1ⁱⁱⁱ	0.96	3.02	3.508 (3)	113
C4—H4A···N3^iv	0.96	2.81	3.663 (3)	149
C12—H12B···O2^v	0.96	2.96	3.531 (3)	119
C12—H12C···O4^v	0.96	2.81	3.629 (3)	144

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

Acknowledgements

We thank Professor S. Pal, School of Chemistry, University of Hyderabad, for his constant support and helpful discussions throughout this work.

Funding information

Funding for this research was provided by: The Ministry of Education, Government of India [grant No. F11/9/2019-102U3(A) to the Univesity of Hyderabad, Institution of Eminence].

References

Assey, G. E. & Mgohamwende, R. (2020). Pharm. & Pharmacol. Int. J. 8, 136–146. CrossRef Google Scholar
Bruker (2014). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dash, S. P., Pasayat, S., Saswati, Dash, H. R., Das, S., Butcher, R. J. & Dinda, R. (2012). Polyhedron, 31, 524–529. CrossRef CAS Google Scholar
Deng, Z.-P., Gao, S., Huo, L.-H. & Zhao, H. (2005). Acta Cryst. E61, m2214–m2216. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Guerrero-Pérez, M. O. (2017). Catal. Today, 285, 226–233. Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Langeslay, R. R., Kaphan, D. M., Marshall, C. L., Stair, P. C., Sattelberger, A. P. & Delferro, M. (2019). Chem. Rev. 119, 2128–2191. Web of Science CrossRef CAS PubMed Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Naskar, S., Mishra, D., Butcher, R. J. & Chattopadhyay, S. K. (2007). Polyhedron, 26, 3703–3714. CrossRef CAS Google Scholar
Noblía, P., Baran, E. J., Otero, L., Draper, P., Cerecetto, H., González, M., Piro, O. E., Castellano, E. E., Inohara, T., Adachi, Y., Sakurai, H. & Gambino, D. (2004). Eur. J. Inorg. Chem. pp. 322–328. Google Scholar
Plass, W., Bangesh, M., Nica, S. & Buchholz, A. (2007). Model Studies of Vanadium-Dependent Haloperoxidation: Structural and Functional Lessons, ACS Symposium Series, Vol. 974, pp. 163–177. Washington: American Chemical Society. Google Scholar
Sangeetha, N. R., Kavita, V., Wocadlo, S., Powell, A. K. & Pal, S. (2000). J. Coord. Chem. 51, 55–66. CrossRef CAS Google Scholar
Sarkar, A. & Pal, S. (2009). Inorg. Chim. Acta, 362, 3807–3812. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Srivastava, A. K., Ghosh, S., Jana, S. & Pal, S. (2018). Inorg. Chim. Acta, 483, 329–336. CrossRef CAS Google Scholar
Srivastava, A. K., Ghosh, S. & Pal, S. (2020). Inorg. Chim. Acta, 502, 119344. CrossRef Google Scholar
Sutradhar, M., Roy Barman, T., Ghosh, S. & Drew, M. G. B. (2013). J. Mol. Struct. 1037, 276–282. CrossRef CAS Google Scholar
Tanabe, Y. & Nishibayashi, Y. (2019). Coord. Chem. Rev. 381, 135–150. Web of Science CrossRef CAS Google Scholar
Tsave, O., Petanidis, S., Kioseoglou, E., Yavropoulou, M. P., Yovos, J. G., Anestakis, D. & Salifoglou, A. (2016). Oxidative Med. Cell. Longev. Article ID 4013639. https://doi.org/10.1155/2016/4013639 Google Scholar
Zabin, S. A. & Abdelbaset, M. (2016). Eur. J. Chem. 7, 322–328. CrossRef CAS Google Scholar

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