X-ray and DFT-calculated structures of a vanadyl Schiff base complex: (methanol-[kappa]O)[2-meth­oxy-6-({2-[(2-oxido-3-meth­oxy­benzyl­idene)­amino]­benzyl}­imino­methyl)­phenol­ato-[kappa]⁴O¹,N,N,O^1']oxido­vanadium(IV) mono­hydrate

The central V^V atom in the title mononuclear oxovanadium complex, [VO(C₂₃H₂₀N₂O₄)(CH₃OH)]·H₂O, has a distorted octa­hedral coordination. Two N atoms and two O atoms of the Schiff base define the base of the bipyramid and two O atoms are in the apical positions, one from vanadyl and the second from methanol. Density functional theory (DFT) calculations were performed for the title complex and its ligand to compare their geometry in the solid and gas phases. Additional analyses were made of the changes in the geometry of the ligand during complex formation. The HOMA (harmonic oscillator model of aromaticity) descriptor of [pi]-electron delocalization was calculated to estimate the aromaticity of the benzene rings in the title complex and its ligand.

S1. Comment

Schiff bases and their complexes with various metal ions are a very interesting class of compounds, covering coordination chemistry, chemical biology and medical science. Oxovanadium(IV) complexes of Schiff bases are now established as an important class of drugs because of their medical importance due to their insulin-like effect (Thompson et al., 1999). Additionally, these complexes are used in some chemical processes (Ben Zid et al., 2010) as catalysts, and also as biological models in understanding the structure of biomolecular and biological processes (Meshkini & Yazdanparast, 2010). Furthermore, vanadium compounds are interesting because of their adverse effect on the hydroprocessing catalysts used in refining crude oil (Bu et al., 1996).

We have recently described the crystal structure of the oxovanadium(IV) complex of a tetradentate Schiff base, [VO(acetph)], where H₂acetph is N,N'-bis(salicylidene)-1,2-phenylenediamine (Kurzak et al., 2011). Oxovanadium(IV) compounds with this ligand are essentially five-coordinated and form monomeric green crystals containing square-pyramidal coordination structures (Abe et al., 2006; Homden et al., 2008). However, orange polynuclear linear chain structures (V═O···V═O···) have been observed in the solid state for Schiff base oxovanadium(IV) complexes (Nakajima et al., 1996; Tsuchimoto et al., 2000; Fairhurst et al., 1995). Additionally, there is a rare group of oxovanadium(IV) complexes with a weak coordination of solvent molecules. Among these are complexes where the solvent is coordinated in equatorial (Fairhurst et al., 1995; Rayati et al., 2008) or axial positions (Jing et al., 2005; Uemura et al., 2000; Xie et al., 2007). In this article, the title oxovanadium(IV) complex with both a Schiff base and a coordinated methanol molecule (at the 6-position trans to the vanadyl O atom), (I), has been structurally characterized.

The molecular structure of (I) in the solid state and of its ligand [N,N'-bis(3-methoxysalicylidene)-2-aminobenzamine (H₂L); Dey et al., 2001] are presented in Figs. 1(a) and 1(b). In order to extend the structural studies, the molecular geometries of (I) and H₂L were optimized using quantum-mechanical density functional theory (DFT) calculations. The DFT-calculated molecular structures of (I) and H₂L are presented in Figs. 1(c) and 1(d). Selected interatomic distances and bond and torsion angles for the studied compounds, obtained by X-ray diffraction analysis and calculated by DFT, are given in Table 1. Some geometric parameters of H₂L (Dey et al., 2001) are presented for comparison.

In the solid state, (I) contains a distorted octahedral VO⁺² species, with the terminal oxide (atom O3) and the coordinated methanol molecule (atom O4) occupying the axial positions. The bond angles around the V^V centre formed by the N₂O₂ donor atoms from the Schiff base are almost 90°, so its deviation from strict planarity is quite small. The V^V cation is 0.322 (1) Å above the average plane defined by the N₂O₂ donor atoms and shifted towards vanadyl atom O3. In similar complexes found in the Cambridge Structural Database (CSD; CONQUEST, Version 1.13; Allen, 2002), the mean value of this displacement is 0.3 Å, and the value in (I) is about half that observed in unambiguously five-coordinate species such as [VO(acteph)] [0.6328 (7) Å; Kurzak et al., 2011].

The V═O bond distance and the in-plane V—O distances are comparable with those found in analogous six-coordinated derivatives (Allen, 2002), whereas in the case of the five-coordinated complex [VO(salen)], namely [N,N'-bis(salicylidene)ethane-1,2-diaminato]oxovanadium(IV), the corresponding distances are shorter (Riley et al., 1986).

The axial V1—O4(methanol) distance is similar to the average literature value of 2.3 Å for oxovanadium(IV) complexes with coordinated solvent molecules (Jing et al., 2005; Uemura et al., 2000; Xie et al., 2007).

Comparison of the V—N bond lengths in (I) with the corresponding values reported for six-coordinated complexes, where the solvent molecule occupies the axial position, shows that they are in the same range.

The axis of the V═O bond is tilted by 3.7 (1)° from the normal to the plane defined by the N₂O₂ donor atoms; in analogous six-coordinated oxovanadium(IV) complexes this parameter is in the range 2.3–6.7° (Allen, 2002).

The axis of the V1—O4 bond is tilted by only 0.2 (1)°. In this case, the average value in similar structures is 1.77° (Allen, 2002). In the DFT-calculated structure of (I) this angle increases to 4.5°; the value of the V1—O4 bond distance is longer than 3 Å and the displacement of the V atom from the N₂O₂ plane increases by more than 0.2 Å. In consequence, the V atom in the DFT-calculated structure of (I) adopts the features of five-coordination.

In the DFT structure of (I) there is an O4—H4···O7 hydrogen bond between the solvent molecules (MeOH and H₂O). This interaction in the solid-state structure of (I) concerns a water molecule bonded to a neighbouring complex molecule [O4—H4···O7ⁱ; symmetry code: (i) x+1, y, z], in view of the shorter distance between the atoms constituting this interaction. Otherwise, there are no significant differences between the values of the bond lengths and angles of (I) in the solid-state and calculated structures; the differences do not exceed 0.05 Å for bond distances and 3° for bond angles. However, the formation of the complex results in changes in the geometry of the ligand molecule, and there are three places in the structure where the differences in the torsion angles are particularly marked, i.e. rotation around the N1—C8, C8—C9 and C14—N2 bonds.

Three planar fragments may be distinguished in (I): plane A, formed by atoms C1–C6 (the benzene ring connected to atom O1), plane B, formed by atoms C9–C14 (the benzene ring connected to the atom N2), and plane C, formed by atoms C16–C21 (the benzene ring connected to atom O2). The values of the A/B, A/C and B/C angles are collected in Table 1. Based on these data, it can be concluded that the ligand molecule adopts a more coplanar conformation in the solid state than in the gas phase, as well as during complex formation.

The molecular structure of H₂L is partly stabilized by intramolecular O—H···N hydrogen bonds (Table 2), forming five-membered quasi-rings. An extra quasi-ring can be considered as a quasi-aromatic ring, which contains an H atom in the ligand or a metal ion in the complex. The resulting rings can be investigated as molecular patterns of intramolecular resonance-assisted hydrogen bonds. The position of the extra ring formed by the substituent interacting through the hydrogen bond is found to influence both the strength of that hydrogen bond and the local aromaticity of the polycyclic aromatic hydrocarbon (PAH) skeleton. Relatively speaking, a greater loss of aromaticity of the ipso-ring (benzene ring) can be observed for these kinked structures because of the greater participation of ipso-ring π-electrons in the formation of the quasi-ring (Krygowski et al., 2010; Palusiak et al., 2009).

The harmonic oscillator model of aromaticity (HOMA; Kruszewski & Krygowski, 1973; Krygowski, 1993) is a leading method for the quantitative determination of cyclic π-electron delocalization (aromaticity) in chemical compounds. It is based on the geometric criterion of aromaticity, which stipulates that bond lengths in aromatic systems are between the values typical for single and double bonds. The HOMA values calculated for (I) and H₂L are collected in Table 3. It can be seen that π-electronic effects play an important role in the stabilization of the molecular structures of these chemical species and, additionally, that the hydrogen-bonded quasi-ring can partially adopt the role of a typical aromatic ring. The aromatic characters of benzene rings A and C in the ligand molecule are almost identical and slightly smaller than in ring B. This loss of aromaticity of the ipso-rings (benzene rings A and C) is a result of the participation of π-electrons from the respective rings in the quasi-rings formed by the intramolecular O—H···N hydrogen bonds. The formation of the complex leads to a subsequent loss of aromaticity for rings A and B due to more effective π-electron communication with the quasi-rings. Due to the isolation of ring B by sp³ atom C8, its π-electrons have limited access to the quasi-ring.

A crystal packing diagram for (I) is shown in Fig. 2. Due to the additional O atom of the water molecule, the hydrogen-bond network is enriched in the solid-state structure of (I). The parameters of these interactions are given in Table 4. The two strong intermolecular hydrogen bonds O4—H4A···O7ⁱ and C12—H12···O2ⁱⁱ [symmetry code: (ii) -x + 2, -y + 1, -z + 1] form chains along the a axis. The V···V distance between neighbouring molecules in the crystal structure is 6.9808 (7) Å.

Related literature

For related literature, see: Abe et al. (2006); Allen (2002); Becke (1988, 1993); Ben Zid, Khedher & Ghorbel (2010); Boghaei & Mohebi (2002); Bu et al. (1996); Dey et al. (2001); Fairhurst et al. (1995); Frisch (2010); Homden et al. (2008); Jing et al. (2005); Kruszewski & Krygowski (1973); Krygowski (1993); Krygowski et al. (2010); Kurzak et al. (2011); Lee et al. (1988); Meshkini & Yazdanparast (2010); Nakajima et al. (1996); Palusiak et al. (2009); Rayati et al. (2008); Riley et al. (1986); Thompson et al. (1999); Tsuchimoto et al. (2000); Uemura et al. (2000); Xie et al. (2007).

S2. Experimental

Compound (I) was prepared according to the literature procedure of Boghaei & Mohebi (2002) under ambient conditions. To a hot solution of H₂L (7.7 mmol) with triethylamine (10 drops) in methanol (200 ml), a hot solution of oxovanadium(IV) sulfate (7.7 mmol) in methanol (120 ml) was added. The mixture was heated on a hotplate. The resulting red precipitate was collected by filtration, washed with methanol and dried in a vacuum (yield 64%, m.p. 461–462 K). Analysis, found: C 56.68, H 5.44, N 5.47%; C₂₄H₂₆N₂O₇V requires: C 57.03, H 5.18, N 5.54%. IR (Medium?, ν, cm^-1): 3428 (NH), 1320 (CO), 1613 (C═N), 481 (V—N), 348 (V—O) and 861 (V═O).

S3. Refinement

Based on the solid-state geometry, the molecular structures of H₂L and (I) were optimized using the B3LYP hybrid function (Becke, 1988, 1993; Lee et al., 1988) at the 6-311+G(d,p) level of theory. All species correspond to minima at the B3LYP/6-311+G(d,p) level with no imaginary frequencies. All calculations were performed using the GAUSSIAN09 program package (Frisch et al., 2010).

All H atoms were generated in idealized positions, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, C—H = 0.98 Å and U_iso(H) = 1.2U_eq(C) for C(sp⁴)-H [?], C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methylene H atoms and C—H = 0.96Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms, and their parameters were not refined. For O—H groups, O—H = 0.82 Å and U_iso(H) = 1.5U_eq(O) and all parameters were refined.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure in the solid state of (a) (I), (b) H2L (Dey et al., 2001), (c) DFT-calculated (I) and (d) DFT-calculated H2L. The solid-state (X-ray) structures are shown with 50% probability displacement ellipsoids. Dashed lines indicate intramolecular hydrogen bonds.
	Fig. 2. A packing diagram for (I), with the O4—H4···O7^i and C12—H12···O2^ii hydrogen bonds shown as dashed lines. [Symmetry codes: (i) x + 1, y, z; (ii) -x + 2, -y + 1, -z + 1.]

(methanol-κO)[2-methoxy-6-({2-[(2-oxido-3- methoxybenzylidene)amino]benzyl}iminomethyl)phenolato- κ⁴O¹,N,N,O^1']oxidovanadium(IV) monohydrate

Crystal data

[V(C23H20N2O4)O(CH4O)]·H2O	F(000) = 1052
Mr = 505.41	Dx = 1.437 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3633 reflections
a = 6.9808 (2) Å	θ = 2.9–25.0°
b = 34.6243 (12) Å	µ = 0.47 mm^−1
c = 9.6740 (4) Å	T = 290 K
β = 92.774 (4)°	Prism, red
V = 2335.52 (14) Å^3	0.35 × 0.17 × 0.15 mm
Z = 4

Data collection

Oxford Xcalibur diffractometer	3635 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
Graphite monochromator	θmax = 25.0°, θmin = 2.9°
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	h = −5→8
ω scans	k = −41→41
14484 measured reflections	l = −11→11
4113 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ^2(Fo^2) + (0.0276P)^2 + 1.8956P] where P = (Fo^2 + 2Fc^2)/3
4113 reflections	(Δ/σ)max = 0.001
319 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
V1	0.97255 (6)	0.387804 (12)	0.48332 (4)	0.02581 (13)
O1	0.8415 (2)	0.33856 (5)	0.43211 (18)	0.0347 (4)
O2	0.8394 (2)	0.38952 (5)	0.65745 (16)	0.0309 (4)
O3	0.8531 (2)	0.41606 (5)	0.38142 (18)	0.0364 (4)
O4	1.1675 (3)	0.34808 (6)	0.6282 (2)	0.0438 (5)
H4A	1.282 (5)	0.3436 (10)	0.622 (3)	0.059 (11)*
O5	0.5681 (3)	0.28915 (6)	0.3721 (2)	0.0511 (5)
O6	0.6404 (3)	0.37030 (7)	0.8650 (2)	0.0591 (6)
N1	1.1898 (3)	0.37296 (6)	0.3514 (2)	0.0309 (5)
N2	1.1545 (3)	0.43249 (6)	0.5625 (2)	0.0290 (5)
C1	0.8540 (4)	0.31939 (7)	0.3157 (3)	0.0321 (6)
C2	0.7092 (4)	0.29164 (8)	0.2791 (3)	0.0392 (7)
C3	0.7171 (5)	0.26968 (9)	0.1613 (3)	0.0548 (9)
H3	0.6228	0.2513	0.1409	0.066*
C4	0.8658 (6)	0.27485 (10)	0.0721 (4)	0.0652 (10)
H4	0.8687	0.2605	−0.0089	0.078*
C5	1.0066 (5)	0.30089 (9)	0.1035 (3)	0.0562 (9)
H5	1.1061	0.3039	0.0439	0.067*
C6	1.0049 (4)	0.32343 (8)	0.2249 (3)	0.0388 (6)
C7	1.1682 (4)	0.34804 (8)	0.2542 (3)	0.0386 (7)
H7	1.2696	0.3455	0.1959	0.046*
C8	1.3765 (4)	0.39329 (8)	0.3678 (3)	0.0368 (6)
H8A	1.4588	0.3851	0.2953	0.044*
H8B	1.4389	0.3864	0.4561	0.044*
C9	1.3501 (3)	0.43633 (7)	0.3608 (3)	0.0320 (6)
C10	1.4272 (4)	0.45807 (8)	0.2570 (3)	0.0402 (7)
H10	1.4931	0.4458	0.1882	0.048*
C11	1.4078 (4)	0.49788 (9)	0.2538 (3)	0.0454 (8)
H11	1.4543	0.5120	0.1808	0.054*
C12	1.3193 (4)	0.51644 (8)	0.3592 (3)	0.0445 (7)
H12	1.3135	0.5433	0.3605	0.053*
C13	1.2388 (4)	0.49533 (8)	0.4633 (3)	0.0377 (6)
H13	1.1770	0.5079	0.5334	0.045*
C14	1.2507 (3)	0.45532 (7)	0.4626 (3)	0.0297 (6)
C15	1.1606 (4)	0.44426 (8)	0.6887 (3)	0.0386 (6)
H15	1.2444	0.4645	0.7101	0.046*
C16	1.0530 (4)	0.42972 (8)	0.8002 (3)	0.0385 (6)
C17	1.0969 (5)	0.44444 (11)	0.9340 (3)	0.0562 (9)
H17	1.1983	0.4617	0.9472	0.067*
C18	0.9944 (5)	0.43402 (11)	1.0441 (3)	0.0582 (9)
H18	1.0270	0.4437	1.1318	0.070*
C19	0.8411 (4)	0.40888 (9)	1.0245 (3)	0.0483 (8)
H19	0.7709	0.4017	1.0996	0.058*
C20	0.7916 (4)	0.39445 (8)	0.8957 (3)	0.0382 (6)
C21	0.8971 (4)	0.40403 (7)	0.7784 (2)	0.0306 (6)
C22	1.0899 (5)	0.31710 (10)	0.7033 (4)	0.0625 (10)
H22A	1.1910	0.3043	0.7562	0.094*
H22B	1.0288	0.2991	0.6399	0.094*
H22C	0.9973	0.3269	0.7645	0.094*
C23	0.4237 (5)	0.26023 (10)	0.3509 (4)	0.0650 (10)
H23A	0.3347	0.2618	0.4233	0.097*
H23B	0.4825	0.2352	0.3522	0.097*
H23C	0.3568	0.2643	0.2631	0.097*
C24	0.5148 (5)	0.36129 (12)	0.9703 (4)	0.0717 (11)
H24A	0.4164	0.3442	0.9343	0.107*
H24B	0.4573	0.3846	1.0026	0.107*
H24C	0.5854	0.3490	1.0457	0.107*
O7	0.5371 (3)	0.32793 (8)	0.6284 (3)	0.0480 (6)
H7A	0.588 (6)	0.3436 (13)	0.674 (5)	0.090 (17)*
H7B	0.582 (6)	0.3239 (12)	0.561 (5)	0.080 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0255 (2)	0.0267 (2)	0.0254 (2)	−0.00361 (18)	0.00338 (15)	−0.00116 (18)
O1	0.0381 (10)	0.0331 (10)	0.0332 (10)	−0.0124 (8)	0.0062 (8)	−0.0075 (8)
O2	0.0316 (9)	0.0351 (9)	0.0261 (9)	−0.0046 (8)	0.0044 (7)	−0.0021 (8)
O3	0.0349 (10)	0.0401 (10)	0.0340 (10)	0.0002 (8)	−0.0009 (8)	0.0018 (8)
O4	0.0306 (11)	0.0472 (12)	0.0541 (13)	0.0031 (9)	0.0062 (9)	0.0151 (10)
O5	0.0521 (13)	0.0449 (12)	0.0559 (13)	−0.0227 (10)	−0.0026 (10)	−0.0053 (10)
O6	0.0647 (14)	0.0747 (15)	0.0400 (12)	−0.0282 (12)	0.0253 (11)	−0.0080 (11)
N1	0.0323 (12)	0.0266 (11)	0.0344 (12)	−0.0037 (9)	0.0088 (9)	−0.0016 (9)
N2	0.0256 (11)	0.0310 (11)	0.0307 (11)	−0.0054 (9)	0.0032 (9)	−0.0022 (9)
C1	0.0428 (15)	0.0235 (13)	0.0294 (14)	−0.0047 (11)	−0.0039 (11)	−0.0002 (11)
C2	0.0498 (17)	0.0302 (14)	0.0367 (15)	−0.0053 (12)	−0.0071 (13)	0.0020 (12)
C3	0.070 (2)	0.0401 (17)	0.053 (2)	−0.0132 (16)	−0.0145 (17)	−0.0107 (15)
C4	0.091 (3)	0.057 (2)	0.048 (2)	−0.009 (2)	−0.0003 (19)	−0.0250 (17)
C5	0.078 (2)	0.0506 (19)	0.0408 (17)	−0.0060 (18)	0.0141 (16)	−0.0136 (15)
C6	0.0535 (18)	0.0302 (14)	0.0328 (15)	−0.0025 (13)	0.0031 (13)	−0.0046 (11)
C7	0.0482 (17)	0.0346 (15)	0.0345 (15)	−0.0005 (12)	0.0169 (13)	−0.0012 (12)
C8	0.0303 (14)	0.0362 (15)	0.0451 (16)	−0.0017 (11)	0.0133 (12)	−0.0012 (12)
C9	0.0241 (13)	0.0363 (14)	0.0354 (14)	−0.0063 (11)	−0.0007 (11)	0.0014 (11)
C10	0.0355 (15)	0.0495 (17)	0.0358 (15)	−0.0119 (13)	0.0045 (12)	0.0018 (13)
C11	0.0364 (17)	0.0511 (18)	0.0478 (18)	−0.0158 (13)	−0.0069 (14)	0.0198 (14)
C12	0.0322 (15)	0.0344 (15)	0.066 (2)	−0.0067 (12)	−0.0066 (14)	0.0117 (14)
C13	0.0269 (14)	0.0343 (15)	0.0515 (17)	−0.0027 (11)	−0.0025 (12)	−0.0019 (13)
C14	0.0232 (12)	0.0327 (14)	0.0329 (14)	−0.0074 (10)	−0.0008 (10)	0.0001 (11)
C15	0.0325 (14)	0.0448 (16)	0.0385 (16)	−0.0134 (12)	0.0007 (12)	−0.0087 (13)
C16	0.0360 (15)	0.0495 (17)	0.0300 (14)	−0.0055 (13)	0.0006 (11)	−0.0046 (12)
C17	0.0526 (19)	0.078 (2)	0.0375 (17)	−0.0177 (17)	−0.0008 (14)	−0.0149 (16)
C18	0.059 (2)	0.088 (3)	0.0272 (15)	−0.0067 (19)	0.0002 (14)	−0.0120 (16)
C19	0.0542 (19)	0.064 (2)	0.0275 (14)	0.0019 (16)	0.0108 (13)	0.0021 (14)
C20	0.0401 (15)	0.0424 (16)	0.0326 (14)	−0.0014 (13)	0.0084 (12)	−0.0002 (12)
C21	0.0314 (14)	0.0345 (14)	0.0259 (13)	0.0039 (11)	0.0018 (11)	0.0002 (11)
C22	0.0482 (19)	0.058 (2)	0.081 (3)	0.0003 (16)	0.0042 (18)	0.0316 (19)
C23	0.058 (2)	0.056 (2)	0.079 (3)	−0.0291 (17)	−0.0130 (19)	0.0020 (18)
C24	0.076 (3)	0.086 (3)	0.056 (2)	−0.028 (2)	0.0360 (19)	−0.0046 (19)
O7	0.0355 (12)	0.0557 (15)	0.0531 (15)	−0.0024 (10)	0.0070 (11)	−0.0058 (12)

Geometric parameters (Å, º)

V1—O3	1.5951 (18)	C9—C10	1.385 (4)
V1—O2	1.9640 (16)	C9—C14	1.396 (4)
V1—O1	1.9865 (17)	C10—C11	1.385 (4)
V1—N1	2.092 (2)	C10—H10	0.9300
V1—N2	2.121 (2)	C11—C12	1.376 (4)
V1—O4	2.350 (2)	C11—H11	0.9300
O1—C1	1.314 (3)	C12—C13	1.385 (4)
O2—C21	1.318 (3)	C12—H12	0.9300
O4—C22	1.418 (4)	C13—C14	1.388 (4)
O4—H4A	0.82 (3)	C13—H13	0.9300
O5—C2	1.369 (3)	C15—C16	1.435 (4)
O5—C23	1.429 (3)	C15—H15	0.9300
O6—C20	1.368 (3)	C16—C17	1.411 (4)
O6—C24	1.411 (3)	C16—C21	1.414 (4)
N1—C7	1.280 (3)	C17—C18	1.360 (4)
N1—C8	1.483 (3)	C17—H17	0.9300
N2—C15	1.285 (3)	C18—C19	1.386 (4)
N2—C14	1.440 (3)	C18—H18	0.9300
C1—C6	1.411 (4)	C19—C20	1.371 (4)
C1—C2	1.427 (4)	C19—H19	0.9300
C2—C3	1.373 (4)	C20—C21	1.422 (4)
C3—C4	1.393 (5)	C22—H22A	0.9600
C3—H3	0.9300	C22—H22B	0.9600
C4—C5	1.357 (5)	C22—H22C	0.9600
C4—H4	0.9300	C23—H23A	0.9600
C5—C6	1.410 (4)	C23—H23B	0.9600
C5—H5	0.9300	C23—H23C	0.9600
C6—C7	1.441 (4)	C24—H24A	0.9600
C7—H7	0.9300	C24—H24B	0.9600
C8—C9	1.503 (4)	C24—H24C	0.9600
C8—H8A	0.9700	O7—H7A	0.78 (5)
C8—H8B	0.9700	O7—H7B	0.75 (4)
O3—V1—O2	104.86 (8)	C14—C9—C8	120.0 (2)
O3—V1—O1	98.73 (9)	C9—C10—C11	121.1 (3)
O2—V1—O1	90.49 (7)	C9—C10—H10	119.5
O3—V1—N1	98.42 (9)	C11—C10—H10	119.5
O2—V1—N1	156.56 (8)	C12—C11—C10	119.7 (3)
O1—V1—N1	88.61 (8)	C12—C11—H11	120.2
O3—V1—N2	93.54 (9)	C10—C11—H11	120.2
O2—V1—N2	88.17 (7)	C11—C12—C13	120.3 (3)
O1—V1—N2	167.58 (8)	C11—C12—H12	119.9
N1—V1—N2	87.73 (8)	C13—C12—H12	119.9
O3—V1—O4	176.12 (8)	C12—C13—C14	119.8 (3)
O2—V1—O4	77.93 (7)	C12—C13—H13	120.1
O1—V1—O4	83.85 (7)	C14—C13—H13	120.1
N1—V1—O4	78.69 (8)	C13—C14—C9	120.4 (2)
N2—V1—O4	83.80 (8)	C13—C14—N2	121.0 (2)
C1—O1—V1	126.76 (16)	C9—C14—N2	118.6 (2)
C21—O2—V1	129.47 (15)	N2—C15—C16	127.4 (2)
C22—O4—V1	121.57 (18)	N2—C15—H15	116.3
C22—O4—H4A	107 (2)	C16—C15—H15	116.3
V1—O4—H4A	127 (2)	C17—C16—C21	119.7 (3)
C2—O5—C23	118.4 (2)	C17—C16—C15	117.7 (3)
C20—O6—C24	118.6 (2)	C21—C16—C15	122.4 (2)
C7—N1—C8	118.0 (2)	C18—C17—C16	121.6 (3)
C7—N1—V1	123.43 (18)	C18—C17—H17	119.2
C8—N1—V1	118.53 (16)	C16—C17—H17	119.2
C15—N2—C14	117.9 (2)	C17—C18—C19	119.4 (3)
C15—N2—V1	124.47 (18)	C17—C18—H18	120.3
C14—N2—V1	116.65 (15)	C19—C18—H18	120.3
O1—C1—C6	124.5 (2)	C20—C19—C18	120.8 (3)
O1—C1—C2	118.5 (2)	C20—C19—H19	119.6
C6—C1—C2	116.9 (2)	C18—C19—H19	119.6
O5—C2—C3	124.7 (3)	O6—C20—C19	125.3 (3)
O5—C2—C1	113.8 (2)	O6—C20—C21	113.2 (2)
C3—C2—C1	121.5 (3)	C19—C20—C21	121.5 (3)
C2—C3—C4	120.2 (3)	O2—C21—C16	124.9 (2)
C2—C3—H3	119.9	O2—C21—C20	118.1 (2)
C4—C3—H3	119.9	C16—C21—C20	116.9 (2)
C5—C4—C3	120.0 (3)	O4—C22—H22A	109.5
C5—C4—H4	120.0	O4—C22—H22B	109.5
C3—C4—H4	120.0	H22A—C22—H22B	109.5
C4—C5—C6	121.3 (3)	O4—C22—H22C	109.5
C4—C5—H5	119.4	H22A—C22—H22C	109.5
C6—C5—H5	119.4	H22B—C22—H22C	109.5
C5—C6—C1	120.0 (3)	O5—C23—H23A	109.5
C5—C6—C7	116.9 (3)	O5—C23—H23B	109.5
C1—C6—C7	122.9 (2)	H23A—C23—H23B	109.5
N1—C7—C6	127.4 (2)	O5—C23—H23C	109.5
N1—C7—H7	116.3	H23A—C23—H23C	109.5
C6—C7—H7	116.3	H23B—C23—H23C	109.5
N1—C8—C9	111.1 (2)	O6—C24—H24A	109.5
N1—C8—H8A	109.4	O6—C24—H24B	109.5
C9—C8—H8A	109.4	H24A—C24—H24B	109.5
N1—C8—H8B	109.4	O6—C24—H24C	109.5
C9—C8—H8B	109.4	H24A—C24—H24C	109.5
H8A—C8—H8B	108.0	H24B—C24—H24C	109.5
C10—C9—C14	118.6 (2)	H7A—O7—H7B	115 (4)
C10—C9—C8	121.4 (2)
O3—V1—O1—C1	71.1 (2)	C2—C1—C6—C5	0.7 (4)
O2—V1—O1—C1	176.2 (2)	O1—C1—C6—C7	3.2 (4)
N1—V1—O1—C1	−27.2 (2)	C2—C1—C6—C7	−174.9 (3)
N2—V1—O1—C1	−100.1 (4)	C8—N1—C7—C6	175.9 (3)
O4—V1—O1—C1	−106.0 (2)	V1—N1—C7—C6	−6.3 (4)
O3—V1—O2—C21	−112.0 (2)	C5—C6—C7—N1	174.0 (3)
O1—V1—O2—C21	148.8 (2)	C1—C6—C7—N1	−10.3 (5)
N1—V1—O2—C21	61.2 (3)	C7—N1—C8—C9	123.6 (3)
N2—V1—O2—C21	−18.9 (2)	V1—N1—C8—C9	−54.2 (3)
O4—V1—O2—C21	65.2 (2)	N1—C8—C9—C10	−117.2 (3)
O2—V1—O4—C22	51.8 (2)	N1—C8—C9—C14	64.7 (3)
O1—V1—O4—C22	−40.0 (2)	C14—C9—C10—C11	0.3 (4)
N1—V1—O4—C22	−129.9 (3)	C8—C9—C10—C11	−177.8 (3)
N2—V1—O4—C22	141.2 (2)	C9—C10—C11—C12	3.4 (4)
O3—V1—N1—C7	−78.8 (2)	C10—C11—C12—C13	−4.2 (4)
O2—V1—N1—C7	107.9 (3)	C11—C12—C13—C14	1.2 (4)
O1—V1—N1—C7	19.8 (2)	C12—C13—C14—C9	2.6 (4)
N2—V1—N1—C7	−172.0 (2)	C12—C13—C14—N2	−174.6 (2)
O4—V1—N1—C7	103.8 (2)	C10—C9—C14—C13	−3.4 (4)
O3—V1—N1—C8	98.95 (19)	C8—C9—C14—C13	174.8 (2)
O2—V1—N1—C8	−74.4 (3)	C10—C9—C14—N2	174.0 (2)
O1—V1—N1—C8	−162.43 (18)	C8—C9—C14—N2	−7.9 (3)
N2—V1—N1—C8	5.71 (18)	C15—N2—C14—C13	−42.0 (3)
O4—V1—N1—C8	−78.43 (18)	V1—N2—C14—C13	127.3 (2)
O3—V1—N2—C15	115.2 (2)	C15—N2—C14—C9	140.7 (3)
O2—V1—N2—C15	10.4 (2)	V1—N2—C14—C9	−50.0 (3)
O1—V1—N2—C15	−73.6 (4)	C14—N2—C15—C16	169.9 (3)
N1—V1—N2—C15	−146.5 (2)	V1—N2—C15—C16	1.5 (4)
O4—V1—N2—C15	−67.7 (2)	N2—C15—C16—C17	173.7 (3)
O3—V1—N2—C14	−53.36 (18)	N2—C15—C16—C21	−11.6 (5)
O2—V1—N2—C14	−158.14 (17)	C21—C16—C17—C18	1.1 (5)
O1—V1—N2—C14	117.9 (3)	C15—C16—C17—C18	176.0 (3)
N1—V1—N2—C14	44.94 (17)	C16—C17—C18—C19	−1.1 (6)
O4—V1—N2—C14	123.81 (17)	C17—C18—C19—C20	−0.1 (5)
V1—O1—C1—C6	20.7 (4)	C24—O6—C20—C19	4.9 (5)
V1—O1—C1—C2	−161.21 (18)	C24—O6—C20—C21	−174.7 (3)
C23—O5—C2—C3	3.9 (4)	C18—C19—C20—O6	−178.3 (3)
C23—O5—C2—C1	−175.3 (3)	C18—C19—C20—C21	1.3 (5)
O1—C1—C2—O5	1.5 (3)	V1—O2—C21—C16	15.6 (4)
C6—C1—C2—O5	179.7 (2)	V1—O2—C21—C20	−166.85 (18)
O1—C1—C2—C3	−177.8 (3)	C17—C16—C21—O2	177.7 (3)
C6—C1—C2—C3	0.5 (4)	C15—C16—C21—O2	3.1 (4)
O5—C2—C3—C4	179.1 (3)	C17—C16—C21—C20	0.1 (4)
C1—C2—C3—C4	−1.7 (5)	C15—C16—C21—C20	−174.5 (3)
C2—C3—C4—C5	1.9 (5)	O6—C20—C21—O2	0.6 (4)
C3—C4—C5—C6	−0.7 (6)	C19—C20—C21—O2	−179.0 (3)
C4—C5—C6—C1	−0.5 (5)	O6—C20—C21—C16	178.4 (2)
C4—C5—C6—C7	175.3 (3)	C19—C20—C21—C16	−1.2 (4)
O1—C1—C6—C5	178.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O7^i	0.82 (3)	1.86 (4)	2.672 (3)	171 (3)
O7—H7B···O1	0.75 (4)	2.31 (4)	2.941 (3)	143 (4)
O7—H7B···O5	0.75 (4)	2.19 (4)	2.838 (4)	146 (4)
O7—H7A···O2	0.78 (5)	2.38 (4)	3.004 (3)	138 (4)
O7—H7A···O6	0.78 (5)	2.08 (5)	2.783 (4)	151 (4)
C12—H12···O2^ii	0.93	2.56	3.440 (3)	158

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