Crystal structures of a series of bis­(acetyl­aceto­nato)oxovanadium(IV) complexes containing N-donor pyridyl ligands

Rood, J.A.; Reehl, S.R.; Jacoby, K.A.; Oliver, A.

doi:10.1107/S2056989020006246

research communications

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ISSN: 2056-9890

Volume 76| Part 6| June 2020| Pages 826-830

https://doi.org/10.1107/S2056989020006246

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Crystal structures of a series of bis(acetylacetonato)oxovanadium(IV) complexes containing N-donor pyridyl ligands

Jeffrey A. Rood,^a ^* Steven R. Reehl,^a Kaitlyn A. Jacoby ^a and Allen Oliver ^b

^aElizabethtown College, Department of Chemistry and Biochemistry, 1 Alpha Drive, Elizabethtown, PA 17022-2298, USA, and ^bUniversity of Notre Dame, Department of Chemistry and Biochemistry, Notre Dame, IN 46556-5670, USA
^*Correspondence e-mail: roodj@etown.edu

Edited by M. Zeller, Purdue University, USA (Received 1 May 2020; accepted 7 May 2020; online 15 May 2020)

Crystal structures for a series of bis(acetylacetonato)oxovanadium(IV) complexes containing N-donor pyridyl ligands are reported, namely, bis(acetylacetonato-κ²O,O′)oxido(pyridine-κN)vanadium(IV), [V(C₅H₇O₂)₂O(C₅H₅N)], 1, bis(acetylacetonato-κ²O,O′)oxido(pyridine-4-carbonitrile-κN)vanadium(IV), [V(C₅H₇O₂)₂O(C₆H₄N₂)], 2, and bis(acetylacetonato-κ²O,O′)(4-methoxypyridine-κN)oxidovanadium(IV), [V(C₅H₇O₂)₂O(C₆H₇NO)], 3, Compounds 1–3 have the formulae VO(C₅H₇O₂)₂L, where L = pyridine (1), 4-cyano-pyridine (2), and 4-methoxypyridine (3). Compound 1 was previously reported [Meicheng et al. (1984 ). Kexue Tongbao, 29, 759–764 and DaSilva, Spiazzi, Bortolotto & Burrow (2007). Acta Crystallogr., E63, m2422] and redetermined here at cryogenic temperatures. Compounds 1 and 2 as pyridine and 4-cyanopyridine adducts, respectively, crystallize as distorted octahedral structures with the oxo and pyridyl ligands trans to one another. A crystallographic twofold axis runs through the O—V—N bonds. Compound 3 containing a 4-methoxypyridine ligand crystallizes as a distorted octahedral structure with the oxo and pyridyl ligands cis to one other, removing the twofold symmetry seen in the other complexes.

Keywords: crystal structure; vanadium(IV); coordination compound; cis/trans isomers; bidentate ligands.

CCDC references: 2002530; 2002529; 2002528

1. Chemical context

Oxovanadium(IV) complexes have been cited as having numerous practical pharmacological applications ranging from anticancer agents to anti-fungal agents and, more recently, as an insulin mimetic (Singh et al., 2014 ; Abakumova et al., 2012 ; Amin et al., 2000 ). Currently investigations are underway to further understand how the oxovanadium complexes perform this wide array of tasks. As an insulin mimetic, it is postulated that oxovanadium complexes interact with multiple points of the cell signaling pathway associated with the insulin hormone (Amin et al., 2000; Srivastava & Mehdi, 2005 ). Alternatively, studies have shown that it interacts directly with glucose transporters found on the cellular surface (Hiromura et al. 2007 ; Makinen & Brady, 2002 ). Furthermore, vanadium has been found to have important interactions in DNA repair systems, which have made it a lucrative target for much oncological/pharmacological research (Abakumova et al., 2012; Kostova, 2009 ).

Oxovanadium complexes chelated by two acetylacetonate ligands form a five-coordinate bonding system that can act as a Lewis acid (Nenashev et al. 2015 ; Ugone et al., 2019 ; Costa Pessoa, 2015 ; Correia et al. 2017 ). This system can undergo a reaction with a Lewis base to increase its coordination bonding number to six. Of the extensive studies regarding the properties and applications of such complexes, relatively few single-crystal structures have been reported. For instance, five compounds containing N-donor ligands, a focus of this work, have been characterized by single-crystal diffraction (Meicheng et al., 1983 , 1984; Silva et al., 2013 ; Kadirova et al., 2009 ; da Silva et al. 2007 ; Caira et al., 1972 ). Given the structural dependence on functions and application, a deeper study of the molecular structure of such complexes is warranted. In this work, we describe the structures of VO(C₅H₇O₂)₂L, where L = pyridine (1), 4-cyano-pyridine (2), and 4-methoxypyridine (3), and the isolation of different isomeric forms. The complexes were synthesized rapidly in an Anton Paar Monowave 50 synthesis reactor in 5 minutes at 323 K and crystallized upon cooling the mother liquor.

2. Structural commentary

Figs. 1–3 illustrate the molecular structures of compounds 1–3. Compounds 1 and 2 crystallize in the monoclinic space group C2/c. In both complexes, a twofold axis runs along the O—V—N bonding axis, leading to an asymmetric unit that consists of half of the molecular structure. Upon symmetry expansion, both 1 and 2 adopt distorted octahedral geometries around the vanadium metal center with the oxo and pyridyl ligands trans to one another. Each acetylacetonate ligand chelates the vanadium center through two oxygen atoms to form a five-membered ring. In 1 and 2, the equatorial plane consisting of the vanadium center and four acetylacetonate oxygen atoms distorts away from the V=O double bond. In 1, the O_oxo—V—O_acac bond angles are 98.05 (3)° and 99.84 (3)° and in 2 are 98.42 (4)° and 98.91 (3)°.

Figure 1
A view of compound 1, showing the atom labeling. Displacement ellipsoids are at the 50% probability level and H atoms have been omitted for clarity. [Symmetry code (i) −x + 1, y, −z + $[{3\over 2}]$ ].

Figure 2
A view of compound 2, showing the atom labeling. Displacement ellipsoids are at the 50% probability level and H atoms have been omitted for clarity. [Symmetry code (i) −x + 1, y, −z + $[{3\over 2}]$ ].

Figure 3
A view of compound 3, showing the atom labeling. Displacement ellipsoids are at the 50% probability level and H atoms have been omitted for clarity.

Compound 3 exists as a different isomeric form, with the oxo and 4-methoxypyridine ligand being cis to one another. This removes the twofold symmetry seen in compounds 1 and 2 and compound 3 crystallizes in the space group P2₁/n. Similarly to 1 and 2, compound 3 adopts a distorted octahedral geometry upon chelation by two bidentate acetylacetonate ligands.

The V—O and V=O bond lengths for 1–3 are are similar to those observed in related complexes (Singh et al., 2014; Abakumova et al. 2012; Meicheng et al., 1983; Silva et al., 2013; Kadirova et al., 2009). Most notable are variances in the V—N bond lengths in the complexes. In 1 and 2, the V—N bond lengths are of similar nature at 2.3861 (16) and 2.4022 (15) Å, respectively. However in 3, the V—N bond length is much shorter at 2.1140 (12) Å, likely from a combination of the cis-isomeric structure in 3 and the electron-donating methoxy group of the 4-methoxypyridine ligand.

3. Supramolecular features

Several non-covalent interactions (Tables 1–3 ) exist in the supramolecular structures of compounds 1–3. Figs. 4–6 show the crystal packing diagrams for the compounds with the interactions shown as dashed orange lines. In 1, these interactions are centered around the oxo ligand, with methyl groups of the acetylacetonate ligands forming CH₂—H⋯Oⁱⁱ interactions at a distance of 2.575 (9) Å between O1ⁱⁱ and H5A and the aryl protons of the pyridine ligand forming Ar—H⋯Oⁱⁱⁱ interactions at a distance of 2.429 (9) Å between O1ⁱⁱⁱ and H7 [symmetry codes: (ii) −x + 1, −y + 1, −z + 1; (iii) x − $[{1\over 2}]$ , y − $[{1\over 2}]$ , z]. Similar interactions exist in 2 with CH₂—H⋯Oⁱⁱ interactions at a distance of 2.591 (9) Å between the oxo ligand, O1ⁱⁱ, and H4C of the methyl group of the acetylacetonate and Ar—H⋯Oⁱⁱⁱ interactions at a distance of 2.588 (9) Å between the 4-cyanopyridine proton H7 and O1ⁱⁱⁱ [symmetry codes: (ii) −x + 1, −y + 2, −z + 1; (iii) x − $[{1\over 2}]$ , y − $[{1\over 2}]$ , z]. Compound 2 also displays interactions between the methyl groups of the acetylacetonate and the π-bond within 4-cyanopyridine at a distance of 2.682 (9) Å from the proton to the center of the π-bond.

Table 1
Hydrogen-bond geometry (Å, °) for compound 1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O1ⁱⁱ	0.98	2.58	3.2589 (18)	127
C7—H7⋯O1ⁱⁱⁱ	0.95	2.43	3.2487 (17)	144
Symmetry codes: (ii) -x+1, -y+1, -z+1; (iii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Table 2
Hydrogen-bond geometry (Å, °) for compound 2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4C⋯O1ⁱⁱ	0.98	2.47	3.4249 (16)	164
C7—H7⋯O1ⁱⁱⁱ	0.95	2.59	3.4673 (14)	154
Symmetry codes: (ii) -x+1, -y+2, -z+1; (iii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Table 3
Hydrogen-bond geometry (Å, °) for compound 3

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.95	2.57	3.488 (2)	163
C12—H12⋯O2ⁱⁱ	0.95	2.37	3.2567 (18)	156
C14—H14⋯O4ⁱⁱⁱ	0.95	2.57	3.2462 (18)	129
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

Figure 4
Crystal packing diagram of compound 1 with non-covalent interactions shown with dotted orange lines.

Figure 5
Crystal packing diagram of compound 2 with non-covalent interactions shown with dotted orange lines.

Figure 6
Crystal packing diagram of compound 3 with non-covalent interactions shown with dotted orange lines.

Compared to 1 and 2, compound 3 displays different types of non-covalent interactions. The methine proton, H2, of the acetylacetonate interacts with the oxo ligand oxygen, O1ⁱ at a distance of 2.568 (8) Å and the aryl protons H12 and H14 interact with acetylacetonate oxygens atoms O2ⁱⁱ and O4ⁱⁱⁱ at distances of 2.366 (8) Å and 2.569 (8) Å, respectively [symmetry codes: (i) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (ii) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iii) −x + 1, −y + 1, −z + 1]. Additionally, there are weaker interactions between the π-system of the acetylacetonate and 4-methoxypyridine, evident by a 3.196 (9) Å distance from C3 to C14ⁱⁱⁱ.

4. Synthesis and crystallization

Bis(acetylacetonato)oxovanadium(IV) (VO(acac)₂) and the N-donor ligands pyridine, 4-cyanopyridine, and 4-methoxypyridine were purchased and used without further purification. To an Anton Paar Monowave synthesis reactor vial, a 1:1 molar ratio of VO(acac)₂ and an N-donor ligand (0.75 mmol scale) was added and dissolved into 5 mL of dichloromethane. Once dissolved completely, each solution was reacted in an Anton Paar Monowave 50 synthesis reactor at 323 K for 5 min. Following all of the reactions, a slight precipitate was filtered and the resulting filtrate was allowed to slowly evaporate to produce single crystals suitable for X-ray diffraction studies. In addition to characterization by single crystal X-ray diffraction, each complex was characterized by FTIR spectroscopy. Compound 1 IR (neat) ν (cm⁻¹): 3065(w), 2964(w), 1574(m), 1522(s), 1443(m), 1378(s) 1351(s), 1274(m), 1218(w), 1196(w), 1147(w), 1074(w), 1018(m), 964(s), 931(m), 890(w), 782(w), 763(m), 708(m), 676(m). Compound 2 IR (neat) ν(cm⁻¹): 3084(w), 3034(w), 1557(m), 1540(w), 1522(s), 1411(m), 1375(s), 1277(m), 1211(w), 1190(w), 1018(m), 960(s), 929(m), 850(m), 789(m), 737(w), 679(m), 667(m). Compound 3 IR (neat) ν(cm⁻¹): 3072(w), 3017(w), 1577(m), 1513(s), 1431(m), 1367(s), 1329(m), 1291(m), 1273(m), 1210(m), 1109(w), 1058(w), 1029(m), 948(s), 928(m), 836(m), 807(m), 780(m), 678(w), 658(m).

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. Single crystals were examined under Infineum V8512 oil. The datum crystal was affixed to a MiTeGen loop and transferred to the cold nitrogen stream of a Bruker APEXII diffractometer equipped with an Oxford Cryosystems 700 low-temperature apparatus. Unit-cell parameters were determined using reflections harvested from three sets of 12 0.5° ω scans scans. An optimal data-collection strategy was determined for an arbitrary hemisphere of data to 99.8% completeness to a resolution of 0.8 Å. (Bruker, 2015 ) Unit-cell parameters were refined using reflections harvested from the data collection with I ≥ 10σ(I). All data were corrected for Lorentz and polarization effects, and runs were scaled using SADABS (Krause et al., 2015 ). The structures were solved using the Autostructure option within APEX3. This option employs an iterative application of the direct methods, Patterson synthesis, and dual-space routines of SHELXT (Sheldrick, 2015a ). The models were refined routinely (SHELXL; Sheldrick, 2015b ). Hydrogen atoms were placed at calculated geometries and allowed to ride on the position of the parent atom. Methyl H atoms were allowed to rotate but not to tip to best fit the experimental electron density. Hydrogen displacement parameters were set to 1.5U_eq(C) for methyl and 1.2U_eq(C) for all other hydrogen atoms.

Table 4
Experimental details

	1	2	3
Crystal data
Chemical formula	[V(C₅H₇O₂)₂O(C₅H₅N)]	[V(C₅H₇O₂)₂O(C₆H₄N₂)]	[V(C₅H₇O₂)₂O(C₆H₇NO)]
M_r	344.25	369.26	374.28
Crystal system, space group	Monoclinic, C2/c	Monoclinic, C2/c	Monoclinic, P2₁/n
Temperature (K)	120	120	120
a, b, c (Å)	7.8820 (5), 15.2092 (11), 13.9871 (9)	9.1930 (9), 13.5080 (9), 13.3651 (9)	9.6619 (15), 11.9922 (19), 15.344 (2)
β (°)	103.367 (2)	99.030 (3)	94.651 (2)
V (Å³)	1631.33 (19)	1639.1 (2)	1772.0 (5)
Z	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	0.63	0.63	0.59
Crystal size (mm)	0.23 × 0.14 × 0.11	0.15 × 0.11 × 0.07	0.32 × 0.19 × 0.11

Data collection
Diffractometer	Bruker APEXII	Bruker APEXII	Bruker Kappa X8-APEXII
Absorption correction	Numerical (SADABS; Krause et al., 2015)	Numerical (SADABS; Krause et al., 2015)	Numerical (SADABS; Krause et al., 2015)
T_min, T_max	0.912, 0.966	0.927, 0.980	0.862, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	17837, 2037, 1882	21763, 2038, 1832	25688, 4413, 3730
R_int	0.025	0.032	0.033
(sin θ/λ)_max (Å⁻¹)	0.667	0.667	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.073, 1.06	0.027, 0.071, 1.08	0.030, 0.081, 1.05
No. of reflections	2037	2038	4413
No. of parameters	104	114	222
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.26	0.41, −0.40	0.33, −0.36
Computer programs: APEX3 and SAINT (Bruker, 2015), SHELXT2018/2 (Sheldrick, 2015a), SHELXL2018/3 (Sheldrick, 2015b), XP (Bruker, 2015), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2002530; 2002529; 2002528

Crystal structure: contains datablocks compound1, compound2, compound3, global. DOI: https://doi.org/10.1107/S2056989020006246/zl2781sup1.cif

Structure factors: contains datablock compound1. DOI: https://doi.org/10.1107/S2056989020006246/zl2781compound1sup2.hkl

Structure factors: contains datablock compound2. DOI: https://doi.org/10.1107/S2056989020006246/zl2781compound2sup3.hkl

Structure factors: contains datablock compound3. DOI: https://doi.org/10.1107/S2056989020006246/zl2781compound3sup4.hkl

checkCIF report

Computing details top

For all structures, data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: XP (Bruker, 2015) and Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(acetylacetonato-κ²O,O')oxido(pyridine-κN)vanadium(IV) (compound1) top

Crystal data top

[V(C₅H₇O₂)₂O(C₅H₅N)]	F(000) = 716
M_r = 344.25	D_x = 1.402 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.8820 (5) Å	Cell parameters from 8119 reflections
b = 15.2092 (11) Å	θ = 2.7–28.3°
c = 13.9871 (9) Å	µ = 0.63 mm⁻¹
β = 103.367 (2)°	T = 120 K
V = 1631.33 (19) Å³	Tablet, blue
Z = 4	0.23 × 0.14 × 0.11 mm

Data collection top

Bruker APEXII diffractometer	2037 independent reflections
Radiation source: fine-focus sealed tube	1882 reflections with I > 2σ(I)
Detector resolution: 8.33 pixels mm^-1	R_int = 0.025
combination of ω and φ–scans	θ_max = 28.3°, θ_min = 2.7°
Absorption correction: numerical (SADABS; Krause et al., 2015)	h = −10→10
T_min = 0.912, T_max = 0.966	k = −20→20
17837 measured reflections	l = −18→18

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0362P)² + 1.4639P] where P = (F_o² + 2F_c²)/3
2037 reflections	(Δ/σ)_max < 0.001
104 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.26 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.

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

	x	y	z	U_iso*/U_eq
V1	0.500000	0.41643 (2)	0.750000	0.01694 (10)
O1	0.500000	0.52179 (9)	0.750000	0.0239 (3)
O2	0.54371 (12)	0.39403 (6)	0.61740 (7)	0.0211 (2)
O3	0.24437 (11)	0.39799 (6)	0.69551 (7)	0.0212 (2)
N1	0.500000	0.25955 (10)	0.750000	0.0193 (3)
C1	0.43127 (17)	0.37920 (9)	0.53797 (9)	0.0209 (3)
C2	0.25102 (18)	0.37547 (10)	0.52875 (10)	0.0264 (3)
H2	0.179805	0.365061	0.465064	0.032*
C3	0.16766 (17)	0.38580 (8)	0.60560 (10)	0.0211 (3)
C4	−0.02841 (18)	0.38382 (11)	0.58352 (12)	0.0312 (3)
H4A	−0.066433	0.356674	0.638591	0.047*
H4B	−0.072855	0.349511	0.523659	0.047*
H4C	−0.073646	0.443987	0.573924	0.047*
C5	0.5033 (2)	0.36549 (12)	0.44857 (11)	0.0322 (3)
H5A	0.542558	0.421933	0.427631	0.048*
H5B	0.412268	0.340944	0.395398	0.048*
H5C	0.601990	0.324655	0.464361	0.048*
C6	0.37706 (16)	0.21376 (9)	0.78046 (9)	0.0224 (3)
H6	0.289206	0.245242	0.802491	0.027*
C7	0.37197 (19)	0.12280 (10)	0.78135 (10)	0.0274 (3)
H7	0.282169	0.092712	0.803098	0.033*
C8	0.500000	0.07661 (13)	0.750000	0.0293 (4)
H8	0.500002	0.014145	0.750000	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.01327 (15)	0.02129 (16)	0.01593 (15)	0.000	0.00271 (10)	0.000
O1	0.0223 (6)	0.0235 (7)	0.0260 (7)	0.000	0.0059 (5)	0.000
O2	0.0176 (4)	0.0282 (5)	0.0176 (4)	−0.0010 (3)	0.0040 (3)	0.0010 (3)
O3	0.0142 (4)	0.0279 (5)	0.0207 (4)	0.0012 (3)	0.0021 (3)	−0.0002 (4)
N1	0.0155 (7)	0.0221 (7)	0.0198 (7)	0.000	0.0033 (5)	0.000
C1	0.0230 (6)	0.0206 (6)	0.0185 (6)	0.0018 (5)	0.0037 (5)	0.0021 (5)
C2	0.0206 (6)	0.0354 (8)	0.0203 (6)	0.0013 (5)	−0.0014 (5)	−0.0029 (5)
C3	0.0170 (6)	0.0195 (6)	0.0249 (6)	0.0011 (4)	0.0004 (5)	0.0001 (5)
C4	0.0163 (6)	0.0408 (8)	0.0333 (8)	0.0005 (6)	−0.0004 (6)	−0.0075 (6)
C5	0.0312 (8)	0.0463 (9)	0.0195 (6)	0.0008 (7)	0.0069 (6)	−0.0013 (6)
C6	0.0170 (6)	0.0276 (7)	0.0227 (6)	−0.0019 (5)	0.0047 (5)	−0.0003 (5)
C7	0.0286 (7)	0.0284 (7)	0.0244 (7)	−0.0090 (5)	0.0043 (5)	0.0005 (5)
C8	0.0403 (12)	0.0217 (9)	0.0228 (9)	0.000	0.0013 (8)	0.000

Geometric parameters (Å, º) top

V1—O1	1.6024 (14)	C2—H2	0.9500
V1—O2	1.9925 (9)	C3—C4	1.5047 (18)
V1—O2ⁱ	1.9925 (9)	C4—H4A	0.9800
V1—O3ⁱ	2.0023 (9)	C4—H4B	0.9800
V1—O3	2.0023 (9)	C4—H4C	0.9800
V1—N1	2.3861 (16)	C5—H5A	0.9800
O2—C1	1.2710 (16)	C5—H5B	0.9800
O3—C3	1.2766 (16)	C5—H5C	0.9800
N1—C6	1.3402 (15)	C6—C7	1.384 (2)
N1—C6ⁱ	1.3402 (15)	C6—H6	0.9500
C1—C2	1.3977 (19)	C7—C8	1.3816 (18)
C1—C5	1.5025 (19)	C7—H7	0.9500
C2—C3	1.392 (2)	C8—H8	0.9500

O1—V1—O2	99.84 (3)	C1—C2—H2	117.4
O1—V1—O2ⁱ	99.85 (3)	O3—C3—C2	125.19 (12)
O2—V1—O2ⁱ	160.31 (6)	O3—C3—C4	115.80 (12)
O1—V1—O3ⁱ	98.05 (3)	C2—C3—C4	119.01 (12)
O2—V1—O3ⁱ	87.43 (4)	C3—C4—H4A	109.5
O2ⁱ—V1—O3ⁱ	89.83 (4)	C3—C4—H4B	109.5
O1—V1—O3	98.05 (3)	H4A—C4—H4B	109.5
O2—V1—O3	89.83 (4)	C3—C4—H4C	109.5
O2ⁱ—V1—O3	87.42 (4)	H4A—C4—H4C	109.5
O3ⁱ—V1—O3	163.90 (6)	H4B—C4—H4C	109.5
O1—V1—N1	180.0	C1—C5—H5A	109.5
O2—V1—N1	80.16 (3)	C1—C5—H5B	109.5
O2ⁱ—V1—N1	80.15 (3)	H5A—C5—H5B	109.5
O3ⁱ—V1—N1	81.95 (3)	C1—C5—H5C	109.5
O3—V1—N1	81.95 (3)	H5A—C5—H5C	109.5
C1—O2—V1	127.47 (9)	H5B—C5—H5C	109.5
C3—O3—V1	126.95 (9)	N1—C6—C7	123.15 (13)
C6—N1—C6ⁱ	117.39 (16)	N1—C6—H6	118.4
C6—N1—V1	121.31 (8)	C7—C6—H6	118.4
C6ⁱ—N1—V1	121.30 (8)	C8—C7—C6	118.72 (14)
O2—C1—C2	125.19 (12)	C8—C7—H7	120.6
O2—C1—C5	115.52 (12)	C6—C7—H7	120.6
C2—C1—C5	119.28 (12)	C7—C8—C7ⁱ	118.87 (19)
C3—C2—C1	125.12 (13)	C7—C8—H8	120.6
C3—C2—H2	117.4	C7ⁱ—C8—H8	120.6

V1—O2—C1—C2	−0.2 (2)	C1—C2—C3—O3	−1.8 (2)
V1—O2—C1—C5	179.40 (9)	C1—C2—C3—C4	177.47 (13)
O2—C1—C2—C3	−1.3 (2)	C6ⁱ—N1—C6—C7	−0.21 (9)
C5—C1—C2—C3	179.11 (14)	V1—N1—C6—C7	179.79 (9)
V1—O3—C3—C2	5.89 (19)	N1—C6—C7—C8	0.41 (18)
V1—O3—C3—C4	−173.40 (9)	C6—C7—C8—C7ⁱ	−0.19 (9)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O1ⁱⁱ	0.98	2.58	3.2589 (18)	127
C7—H7···O1ⁱⁱⁱ	0.95	2.43	3.2487 (17)	144

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

Bis(acetylacetonato-κ²O,O')oxido(pyridine-4-carbonitrile-κN)vanadium(IV) (compound2) top

Crystal data top

[V(C₅H₇O₂)₂O(C₆H₄N₂)]	F(000) = 764
M_r = 369.26	D_x = 1.496 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.1930 (9) Å	Cell parameters from 7973 reflections
b = 13.5080 (9) Å	θ = 2.7–28.1°
c = 13.3651 (9) Å	µ = 0.63 mm⁻¹
β = 99.030 (3)°	T = 120 K
V = 1639.1 (2) Å³	Block, green
Z = 4	0.15 × 0.11 × 0.07 mm

Data collection top

Bruker APEXII diffractometer	2038 independent reflections
Radiation source: fine-focus sealed tube	1832 reflections with I > 2σ(I)
Detector resolution: 8.33 pixels mm^-1	R_int = 0.032
combination of ω and φ–scans	θ_max = 28.3°, θ_min = 2.7°
Absorption correction: numerical (SADABS; Krause et al., 2015)	h = −12→12
T_min = 0.927, T_max = 0.980	k = −18→18
21763 measured reflections	l = −17→17

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0324P)² + 1.6979P] where P = (F_o² + 2F_c²)/3
2038 reflections	(Δ/σ)_max = 0.001
114 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
V1	0.500000	0.89112 (2)	0.750000	0.01271 (10)
O1	0.500000	1.00987 (10)	0.750000	0.0210 (3)
O2	0.60596 (10)	0.86813 (7)	0.63185 (7)	0.0166 (2)
O3	0.31046 (10)	0.86962 (7)	0.65896 (7)	0.0151 (2)
N1	0.500000	0.71328 (11)	0.750000	0.0130 (3)
N2	0.500000	0.31564 (14)	0.750000	0.0318 (4)
C1	0.54997 (15)	0.87153 (9)	0.53874 (10)	0.0157 (3)
C2	0.39870 (16)	0.87878 (10)	0.50203 (10)	0.0195 (3)
H2	0.369478	0.886023	0.431015	0.023*
C3	0.28850 (15)	0.87607 (9)	0.56257 (10)	0.0155 (3)
C4	0.65451 (16)	0.86478 (11)	0.46315 (11)	0.0214 (3)
H4A	0.653674	0.797228	0.436328	0.032*
H4B	0.754227	0.881506	0.496340	0.032*
H4C	0.623837	0.911208	0.407492	0.032*
C5	0.12947 (16)	0.88186 (11)	0.51467 (11)	0.0223 (3)
H5A	0.121409	0.870964	0.441516	0.033*
H5B	0.090305	0.947415	0.527156	0.033*
H5C	0.073029	0.830993	0.544114	0.033*
C6	0.37746 (14)	0.66216 (10)	0.75924 (9)	0.0148 (3)
H6	0.290548	0.697948	0.765924	0.018*
C7	0.37194 (14)	0.55958 (10)	0.75947 (10)	0.0164 (3)
H7	0.283303	0.525726	0.765917	0.020*
C8	0.500000	0.50744 (14)	0.750000	0.0161 (4)
C9	0.500000	0.40014 (15)	0.750000	0.0222 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.01153 (15)	0.01478 (16)	0.01141 (15)	0.000	0.00052 (11)	0.000
O1	0.0213 (7)	0.0169 (7)	0.0235 (7)	0.000	−0.0005 (6)	0.000
O2	0.0149 (4)	0.0214 (5)	0.0137 (4)	0.0006 (3)	0.0032 (4)	0.0027 (3)
O3	0.0127 (4)	0.0194 (5)	0.0126 (4)	0.0007 (3)	0.0002 (3)	0.0002 (3)
N1	0.0133 (7)	0.0150 (7)	0.0108 (7)	0.000	0.0026 (5)	0.000
N2	0.0394 (11)	0.0174 (9)	0.0429 (12)	0.000	0.0196 (9)	0.000
C1	0.0198 (6)	0.0124 (6)	0.0158 (6)	0.0018 (5)	0.0055 (5)	0.0022 (4)
C2	0.0215 (7)	0.0261 (7)	0.0108 (6)	0.0043 (5)	0.0016 (5)	0.0008 (5)
C3	0.0170 (6)	0.0136 (6)	0.0150 (6)	0.0023 (4)	−0.0009 (5)	−0.0013 (5)
C4	0.0248 (7)	0.0232 (7)	0.0179 (7)	0.0058 (5)	0.0092 (6)	0.0039 (5)
C5	0.0171 (6)	0.0310 (8)	0.0168 (7)	0.0039 (5)	−0.0031 (5)	−0.0014 (6)
C6	0.0134 (6)	0.0181 (6)	0.0135 (6)	0.0005 (5)	0.0035 (5)	0.0003 (5)
C7	0.0162 (6)	0.0186 (6)	0.0151 (6)	−0.0032 (5)	0.0044 (5)	0.0001 (5)
C8	0.0219 (9)	0.0148 (9)	0.0121 (8)	0.000	0.0042 (7)	0.000
C9	0.0257 (10)	0.0212 (10)	0.0218 (10)	0.000	0.0107 (8)	0.000

Geometric parameters (Å, º) top

V1—O1	1.6040 (14)	C2—H2	0.9500
V1—O3ⁱ	1.9838 (9)	C3—C5	1.5031 (18)
V1—O3	1.9838 (9)	C4—H4A	0.9800
V1—O2ⁱ	2.0055 (9)	C4—H4B	0.9800
V1—O2	2.0055 (9)	C4—H4C	0.9800
V1—N1	2.4022 (15)	C5—H5A	0.9800
O2—C1	1.2706 (17)	C5—H5B	0.9800
O3—C3	1.2752 (17)	C5—H5C	0.9800
N1—C6	1.3435 (15)	C6—C7	1.3866 (19)
N1—C6ⁱ	1.3435 (15)	C6—H6	0.9500
N2—C9	1.141 (3)	C7—C8	1.3946 (16)
C1—C2	1.4035 (19)	C7—H7	0.9500
C1—C4	1.5024 (18)	C8—C9	1.449 (3)
C2—C3	1.3928 (19)

O1—V1—O3ⁱ	98.42 (3)	O3—C3—C2	125.06 (13)
O1—V1—O3	98.42 (3)	O3—C3—C5	115.03 (12)
O3ⁱ—V1—O3	163.17 (6)	C2—C3—C5	119.91 (12)
O1—V1—O2ⁱ	98.91 (3)	C1—C4—H4A	109.5
O3ⁱ—V1—O2ⁱ	89.01 (4)	C1—C4—H4B	109.5
O3—V1—O2ⁱ	88.39 (4)	H4A—C4—H4B	109.5
O1—V1—O2	98.91 (3)	C1—C4—H4C	109.5
O3ⁱ—V1—O2	88.39 (4)	H4A—C4—H4C	109.5
O3—V1—O2	89.01 (4)	H4B—C4—H4C	109.5
O2ⁱ—V1—O2	162.19 (6)	C3—C5—H5A	109.5
O1—V1—N1	180.0	C3—C5—H5B	109.5
O3ⁱ—V1—N1	81.58 (3)	H5A—C5—H5B	109.5
O3—V1—N1	81.58 (3)	C3—C5—H5C	109.5
O2ⁱ—V1—N1	81.09 (3)	H5A—C5—H5C	109.5
O2—V1—N1	81.09 (3)	H5B—C5—H5C	109.5
C1—O2—V1	126.40 (9)	N1—C6—C7	123.05 (12)
C3—O3—V1	126.45 (9)	N1—C6—H6	118.5
C6—N1—C6ⁱ	118.13 (15)	C7—C6—H6	118.5
C6—N1—V1	120.93 (8)	C6—C7—C8	118.22 (12)
C6ⁱ—N1—V1	120.93 (8)	C6—C7—H7	120.9
O2—C1—C2	124.87 (12)	C8—C7—H7	120.9
O2—C1—C4	116.92 (12)	C7ⁱ—C8—C7	119.33 (17)
C2—C1—C4	118.19 (12)	C7ⁱ—C8—C9	120.33 (8)
C3—C2—C1	124.49 (13)	C7—C8—C9	120.33 (8)
C3—C2—H2	117.8	N2—C9—C8	180.0
C1—C2—H2	117.8

V1—O2—C1—C2	−9.23 (18)	C1—C2—C3—C5	−178.42 (13)
V1—O2—C1—C4	172.30 (9)	C6ⁱ—N1—C6—C7	−0.12 (9)
O2—C1—C2—C3	−4.8 (2)	V1—N1—C6—C7	179.88 (9)
C4—C1—C2—C3	173.61 (13)	N1—C6—C7—C8	0.22 (17)
V1—O3—C3—C2	14.38 (18)	C6—C7—C8—C7ⁱ	−0.11 (8)
V1—O3—C3—C5	−165.06 (9)	C6—C7—C8—C9	179.89 (8)
C1—C2—C3—O3	2.2 (2)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4C···O1ⁱⁱ	0.98	2.47	3.4249 (16)	164
C7—H7···O1ⁱⁱⁱ	0.95	2.59	3.4673 (14)	154

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

Bis(acetylacetonato-κ²O,O')(4-methoxypyridine-κN)oxidovanadium(IV) (compound3) top

Crystal data top

[V(C₅H₇O₂)₂O(C₆H₇NO)]	F(000) = 780
M_r = 374.28	D_x = 1.403 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.6619 (15) Å	Cell parameters from 9171 reflections
b = 11.9922 (19) Å	θ = 2.4–28.3°
c = 15.344 (2) Å	µ = 0.59 mm⁻¹
β = 94.651 (2)°	T = 120 K
V = 1772.0 (5) Å³	Block, blue
Z = 4	0.32 × 0.19 × 0.11 mm

Data collection top

Bruker Kappa X8-APEXII diffractometer	4413 independent reflections
Radiation source: fine-focus sealed tube	3730 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 8.33 pixels mm^-1	θ_max = 28.4°, θ_min = 2.2°
combination of ω and φ–scans	h = −12→12
Absorption correction: numerical (SADABS; Krause et al., 2015)	k = −16→16
T_min = 0.862, T_max = 0.983	l = −20→20
25688 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0348P)² + 1.1201P] where P = (F_o² + 2F_c²)/3
4413 reflections	(Δ/σ)_max < 0.001
222 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
V1	0.46984 (2)	0.46573 (2)	0.27536 (2)	0.01335 (7)
O1	0.53209 (11)	0.36808 (9)	0.21879 (7)	0.0206 (2)
O2	0.52992 (10)	0.59883 (9)	0.20819 (6)	0.0187 (2)
O3	0.63443 (10)	0.49106 (8)	0.36048 (7)	0.0167 (2)
O4	0.37408 (11)	0.59132 (8)	0.35341 (7)	0.0175 (2)
O5	0.28270 (11)	0.46703 (8)	0.20760 (6)	0.0173 (2)
O6	0.26958 (12)	0.12492 (9)	0.54929 (7)	0.0244 (2)
N1	0.39173 (13)	0.35591 (10)	0.37014 (8)	0.0153 (2)
C1	0.63492 (16)	0.66210 (12)	0.22605 (10)	0.0185 (3)
C2	0.73408 (16)	0.64880 (13)	0.29670 (10)	0.0198 (3)
H2	0.809349	0.699961	0.302343	0.024*
C3	0.72947 (15)	0.56495 (12)	0.35957 (9)	0.0161 (3)
C4	0.84276 (16)	0.55651 (13)	0.43262 (10)	0.0222 (3)
H4A	0.801910	0.538371	0.487292	0.033*
H4B	0.891915	0.627884	0.439042	0.033*
H4C	0.908201	0.497767	0.419094	0.033*
C5	0.6492 (2)	0.75837 (15)	0.16467 (12)	0.0334 (4)
H5A	0.656443	0.730050	0.105296	0.050*
H5B	0.732960	0.801013	0.183335	0.050*
H5C	0.567632	0.806796	0.165362	0.050*
C6	0.24885 (15)	0.62275 (12)	0.35059 (9)	0.0167 (3)
C7	0.14287 (16)	0.58216 (14)	0.29076 (10)	0.0215 (3)
H7	0.050317	0.605404	0.297396	0.026*
C8	0.16543 (16)	0.51020 (13)	0.22263 (10)	0.0193 (3)
C9	0.21222 (17)	0.71170 (13)	0.41458 (10)	0.0226 (3)
H9A	0.242406	0.687897	0.474206	0.034*
H9B	0.111497	0.723372	0.409565	0.034*
H9C	0.258989	0.781507	0.401452	0.034*
C10	0.04535 (18)	0.47785 (17)	0.15869 (12)	0.0320 (4)
H10A	0.069407	0.492688	0.098957	0.048*
H10B	−0.036755	0.521553	0.170540	0.048*
H10C	0.025355	0.398275	0.165035	0.048*
C11	0.28395 (15)	0.28757 (12)	0.34893 (9)	0.0177 (3)
H11	0.238256	0.293682	0.291934	0.021*
C12	0.23542 (15)	0.20886 (12)	0.40496 (10)	0.0184 (3)
H12	0.157914	0.163143	0.387202	0.022*
C13	0.30337 (15)	0.19861 (12)	0.48803 (9)	0.0171 (3)
C14	0.41468 (15)	0.26970 (12)	0.51178 (9)	0.0178 (3)
H14	0.462236	0.265216	0.568336	0.021*
C15	0.45407 (15)	0.34604 (12)	0.45204 (9)	0.0174 (3)
H15	0.529131	0.394613	0.469025	0.021*
C16	0.15152 (19)	0.05480 (15)	0.52768 (11)	0.0289 (4)
H16A	0.069247	0.101227	0.513676	0.043*
H16B	0.136044	0.006690	0.577595	0.043*
H16C	0.168604	0.008556	0.476993	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.01255 (12)	0.01250 (12)	0.01468 (12)	−0.00034 (9)	−0.00089 (8)	0.00034 (8)
O1	0.0192 (5)	0.0202 (5)	0.0224 (5)	0.0020 (4)	0.0010 (4)	−0.0016 (4)
O2	0.0180 (5)	0.0185 (5)	0.0191 (5)	−0.0031 (4)	−0.0018 (4)	0.0043 (4)
O3	0.0132 (5)	0.0166 (5)	0.0196 (5)	−0.0025 (4)	−0.0022 (4)	0.0028 (4)
O4	0.0155 (5)	0.0173 (5)	0.0190 (5)	0.0005 (4)	−0.0022 (4)	−0.0022 (4)
O5	0.0162 (5)	0.0176 (5)	0.0173 (5)	−0.0002 (4)	−0.0031 (4)	−0.0015 (4)
O6	0.0245 (6)	0.0265 (6)	0.0216 (5)	−0.0115 (5)	−0.0014 (4)	0.0063 (4)
N1	0.0151 (6)	0.0142 (5)	0.0163 (6)	−0.0009 (5)	−0.0007 (4)	0.0001 (4)
C1	0.0189 (7)	0.0172 (7)	0.0199 (7)	−0.0017 (6)	0.0035 (6)	0.0020 (5)
C2	0.0164 (7)	0.0199 (7)	0.0230 (7)	−0.0051 (6)	0.0019 (6)	0.0003 (6)
C3	0.0132 (6)	0.0170 (6)	0.0182 (7)	0.0004 (5)	0.0013 (5)	−0.0024 (5)
C4	0.0160 (7)	0.0246 (8)	0.0250 (8)	−0.0026 (6)	−0.0047 (6)	−0.0006 (6)
C5	0.0366 (10)	0.0311 (9)	0.0315 (9)	−0.0130 (8)	−0.0041 (7)	0.0151 (7)
C6	0.0172 (7)	0.0167 (7)	0.0162 (6)	0.0002 (5)	0.0022 (5)	0.0026 (5)
C7	0.0129 (7)	0.0282 (8)	0.0233 (7)	0.0017 (6)	−0.0003 (6)	−0.0023 (6)
C8	0.0147 (7)	0.0217 (7)	0.0207 (7)	−0.0014 (6)	−0.0029 (5)	0.0015 (6)
C9	0.0224 (8)	0.0238 (8)	0.0218 (7)	0.0028 (6)	0.0029 (6)	−0.0042 (6)
C10	0.0188 (8)	0.0435 (11)	0.0320 (9)	0.0003 (7)	−0.0087 (7)	−0.0111 (8)
C11	0.0186 (7)	0.0173 (7)	0.0165 (7)	−0.0031 (6)	−0.0035 (5)	−0.0013 (5)
C12	0.0169 (7)	0.0176 (7)	0.0201 (7)	−0.0046 (6)	−0.0011 (5)	−0.0022 (5)
C13	0.0174 (7)	0.0162 (6)	0.0178 (7)	−0.0015 (5)	0.0025 (5)	0.0007 (5)
C14	0.0166 (7)	0.0202 (7)	0.0160 (6)	−0.0022 (6)	−0.0020 (5)	0.0003 (5)
C15	0.0159 (7)	0.0180 (7)	0.0176 (7)	−0.0035 (6)	−0.0023 (5)	−0.0013 (5)
C16	0.0308 (9)	0.0289 (9)	0.0271 (8)	−0.0160 (7)	0.0030 (7)	0.0037 (7)

Geometric parameters (Å, º) top

V1—O1	1.6035 (11)	C5—H5C	0.9800
V1—O3	1.9975 (10)	C6—C7	1.406 (2)
V1—O2	2.0110 (11)	C6—C9	1.511 (2)
V1—O5	2.0115 (10)	C7—C8	1.386 (2)
V1—N1	2.1440 (12)	C7—H7	0.9500
V1—O4	2.1767 (11)	C8—C10	1.508 (2)
O2—C1	1.2786 (18)	C9—H9A	0.9800
O3—C3	1.2770 (17)	C9—H9B	0.9800
O4—C6	1.2647 (18)	C9—H9C	0.9800
O5—C8	1.2835 (18)	C10—H10A	0.9800
O6—C13	1.3494 (17)	C10—H10B	0.9800
O6—C16	1.4342 (19)	C10—H10C	0.9800
N1—C11	1.3442 (18)	C11—C12	1.384 (2)
N1—C15	1.3541 (18)	C11—H11	0.9500
C1—C2	1.396 (2)	C12—C13	1.391 (2)
C1—C5	1.503 (2)	C12—H12	0.9500
C2—C3	1.397 (2)	C13—C14	1.397 (2)
C2—H2	0.9500	C14—C15	1.371 (2)
C3—C4	1.505 (2)	C14—H14	0.9500
C4—H4A	0.9800	C15—H15	0.9500
C4—H4B	0.9800	C16—H16A	0.9800
C4—H4C	0.9800	C16—H16B	0.9800
C5—H5A	0.9800	C16—H16C	0.9800
C5—H5B	0.9800

O1—V1—O3	98.71 (5)	H5B—C5—H5C	109.5
O1—V1—O2	99.54 (5)	O4—C6—C7	124.29 (14)
O3—V1—O2	88.10 (4)	O4—C6—C9	117.52 (13)
O1—V1—O5	94.97 (5)	C7—C6—C9	118.18 (13)
O3—V1—O5	166.27 (4)	C8—C7—C6	123.87 (14)
O2—V1—O5	90.78 (4)	C8—C7—H7	118.1
O1—V1—N1	94.97 (5)	C6—C7—H7	118.1
O3—V1—N1	87.44 (4)	O5—C8—C7	125.57 (13)
O2—V1—N1	165.31 (5)	O5—C8—C10	115.03 (14)
O5—V1—N1	90.24 (5)	C7—C8—C10	119.40 (14)
O1—V1—O4	176.32 (5)	C6—C9—H9A	109.5
O3—V1—O4	83.48 (4)	C6—C9—H9B	109.5
O2—V1—O4	83.45 (4)	H9A—C9—H9B	109.5
O5—V1—O4	82.80 (4)	C6—C9—H9C	109.5
N1—V1—O4	82.13 (4)	H9A—C9—H9C	109.5
C1—O2—V1	128.18 (9)	H9B—C9—H9C	109.5
C3—O3—V1	129.31 (9)	C8—C10—H10A	109.5
C6—O4—V1	129.46 (9)	C8—C10—H10B	109.5
C8—O5—V1	132.83 (9)	H10A—C10—H10B	109.5
C13—O6—C16	117.11 (12)	C8—C10—H10C	109.5
C11—N1—C15	116.68 (12)	H10A—C10—H10C	109.5
C11—N1—V1	121.24 (10)	H10B—C10—H10C	109.5
C15—N1—V1	121.92 (10)	N1—C11—C12	124.07 (13)
O2—C1—C2	125.53 (13)	N1—C11—H11	118.0
O2—C1—C5	115.67 (13)	C12—C11—H11	118.0
C2—C1—C5	118.80 (14)	C11—C12—C13	118.10 (13)
C1—C2—C3	124.06 (14)	C11—C12—H12	121.0
C1—C2—H2	118.0	C13—C12—H12	121.0
C3—C2—H2	118.0	O6—C13—C12	124.98 (13)
O3—C3—C2	124.77 (13)	O6—C13—C14	116.26 (13)
O3—C3—C4	115.17 (13)	C12—C13—C14	118.76 (13)
C2—C3—C4	120.05 (13)	C15—C14—C13	118.85 (13)
C3—C4—H4A	109.5	C15—C14—H14	120.6
C3—C4—H4B	109.5	C13—C14—H14	120.6
H4A—C4—H4B	109.5	N1—C15—C14	123.52 (13)
C3—C4—H4C	109.5	N1—C15—H15	118.2
H4A—C4—H4C	109.5	C14—C15—H15	118.2
H4B—C4—H4C	109.5	O6—C16—H16A	109.5
C1—C5—H5A	109.5	O6—C16—H16B	109.5
C1—C5—H5B	109.5	H16A—C16—H16B	109.5
H5A—C5—H5B	109.5	O6—C16—H16C	109.5
C1—C5—H5C	109.5	H16A—C16—H16C	109.5
H5A—C5—H5C	109.5	H16B—C16—H16C	109.5

V1—O2—C1—C2	2.0 (2)	C6—C7—C8—O5	3.7 (3)
V1—O2—C1—C5	−177.67 (11)	C6—C7—C8—C10	−175.99 (16)
O2—C1—C2—C3	−1.8 (3)	C15—N1—C11—C12	−0.6 (2)
C5—C1—C2—C3	177.87 (15)	V1—N1—C11—C12	174.86 (11)
V1—O3—C3—C2	2.2 (2)	N1—C11—C12—C13	−0.9 (2)
V1—O3—C3—C4	−177.27 (10)	C16—O6—C13—C12	−2.3 (2)
C1—C2—C3—O3	−0.4 (2)	C16—O6—C13—C14	177.13 (14)
C1—C2—C3—C4	179.04 (14)	C11—C12—C13—O6	−179.03 (14)
V1—O4—C6—C7	−2.3 (2)	C11—C12—C13—C14	1.6 (2)
V1—O4—C6—C9	179.17 (9)	O6—C13—C14—C15	179.74 (13)
O4—C6—C7—C8	−6.1 (3)	C12—C13—C14—C15	−0.8 (2)
C9—C6—C7—C8	172.47 (15)	C11—N1—C15—C14	1.4 (2)
V1—O5—C8—C7	8.0 (2)	V1—N1—C15—C14	−173.97 (11)
V1—O5—C8—C10	−172.33 (11)	C13—C14—C15—N1	−0.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.95	2.57	3.488 (2)	163
C12—H12···O2ⁱⁱ	0.95	2.37	3.2567 (18)	156
C14—H14···O4ⁱⁱⁱ	0.95	2.57	3.2462 (18)	129

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

Acknowledgements

JR gratefully acknowledges Elizabethtown College and the Department of Chemistry and Biochemistry for funding and support.

Funding information

We also acknowledge the National Science Foundation (grant No. CHE-0958425) for instrument support.

References

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Volume 76| Part 6| June 2020| Pages 826-830

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of a series of bis­­(acetyl­aceto­nato)oxovanadium(IV) complexes containing N-donor pyridyl ligands

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Synthesis and crystallization

5. Refinement

Supporting information

Acknowledgements

Funding information

References

research communications

Crystal structures of a series of bis(acetylacetonato)oxovanadium(IV) complexes containing N-donor pyridyl ligands

3. Supramolecular features