Bis­(tetra­butyl­ammonium) bis­(malonato)­oxovanadate(IV)

The synthesis, EPR (electron paramagnetic resonance) characterization, and crystal structure of (C₁₆H₃₆N)₂[VO(C₃H₂O₄)₂] are described. The V atom is pentacoordinated by an oxo and two bidentate malonate ligands. The geometry around the metal is square-pyramidal and the two bidentate malonate ligands form the base of the pyramid. The V=O bond length is 1.556 (3) Å and the range of V-O bond lengths is 1.960 (3)-1.968 (3) Å. The EPR spectrum (g_iso = 1.965 and A_iso = 0.00965 cm^-1) is typical of a V^IV system.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.068
• wR factor = 0.183
• Data-to-parameter ratio = 16.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



GOODF_01  Alert C The least squares goodness of fit parameter lies
          outside the range 0.80 <> 2.00
          Goodness of fit given =      0.760

REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.87
         From the CIF: _reflns_number_total               7920
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         8500
         Completeness (_total/calc)             93.18%
          Alert C: < 95% complete

RINTA_01  Alert C The value of Rint is greater than 0.10
          Rint given   0.127


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

S1. Comment

Soluble vanadium derivatives are known to be efficient reagents and catalysts in oxidations of various organic compounds (Sheldon & Kochi, 1981; Shul'pin, 1988; Butler et al., 1994; Yamanaka et al., 1998). During the course of our research investigation on the synthesis of oxovanadium complexes (Shul'pin et al., 2001), the reaction between tetrabutylammonium vanadate and malonic acid has been studied and can be denoted as follows: 12[VO₃]^- + 24CH₂(COOH)₂ → 2[VO(CH₂(COO)₂)₂]^- + [V₁₀O₂₆]^4- + 6H₂O + O₂ + 4CH₃COO^- + 16CH₃COOH + 20CO₂

Tetrabutylammonium vanadate reacts in refluxing acetonitrile with malonic acid to give the disubstituted vanadate derivative [VO(mal)₂]^2-, (1) [mal = CH₂(COO)₂], and the mixed valence compound [V₁₀O₂₆]^4-, (2). Anions (1) and (2) can be isolated as tetrabutylammonium salts in the form of blue (I) and green (II) crystals. The reduction of vanadium(V) to vanadium(IV) is coupled to the oxidation of malonic acid to acetic acid which has been detected in the product mixture by gas chromatography. Compound (II) is already known and well characterized (Baxter & Wolczanski, 1989), only the molecular structure and properties of (I), [NBu₄]₂[VO(mal)₂], are discussed and presented here.

The malonato ligands are bonded to the vanadium through two carboxylate O atoms. The molecular structure of anion (I) shows a square-pyramidal geometry around the vanadium (Fig. 1). The two bidentate malonate ligands form the base of the pyramid, the V atom is elevated from the equatorial plane by 0.575 (2) Å, with an average V—O distances of 1.964 Å. An oxo ligand occupies the fifth coordination site, with a V═O distance of 1.556 (3) Å. The two six-membered V-malonate rings have boat conformations. A search on the Cambridge Structural Database (Allen & Kennard, 1993) reveals three other anions containing two malonate and one oxo ligands coordinated to a vanadium metal, and they all possess octahedral geometry (Pajunen & Panjunen, 1980; Piro & Baran, 1997; Fillipova & Kiosse, 2000), the sixth coordinated site being filled with a water molecule. An intensive network of weak hydrogen bonds is observed between the O atoms of the vanadate and the tetrabutylammonium cations.

To confirm the oxidation state of the metal, EPR studies of (I) have been performed. A signal having an octuplet structure with g_iso = 1.965, and A_iso = 0.00965 cm^-1 appears in the EPR spectrum of a solution containing [NBu₄]₂[VO(mal)₂] in dichloromethane. These EPR parameters agree with the presence of a vanadium(IV), d¹ system. Both the ¹H and ¹³C NMR signals of [VO(mal)₂] are extremely broad, due to the paramagnetic metal centre of the complex.

S2. Experimental

All reactions were carried out in air. Acetonitrile (Fluka) was distilled over CaH₂; all other solvents were distilled over appropriate drying agents prior to use. Tetrabutylammonium vanadate was prepared according to the literature method of Day et al. (1990). Malonic acid (Fluka) was used without purification. IR spectra were recorded with a Perkin–Elmer 1720x FT—IR spectrometer. Microanalyses were carried out by the Mikroelementar-analytisches Laboratorium of the ETH Zürich, Switzerland. NBu₄VO₃ (868 mg, 2.54 mmol) was dissolved in 20 ml of acetonitrile. After complete dissolution, malonic acid was added (535 mg, 5.14 mmol), and the solution stirred under reflux for 5 h. After filtration and removal of the solvent, a green powder was obtained, being a mixture of [NBu₄]₂[VO(mal)₂] and [NBu₄]₄[V₁₀O₂₆]. The mixture was dissolved in a minimum of acetone and diethyl ether was added to precipitate [NBu₄]₄[V₁₀O₂₆]. After filtration the solution was stored at 277 K, and about a week later, blue crystals of [NBu₄]₂[VO(mal)₂] were obtained (21% yield, based on vanadium). IR (KBr, cm^-1): 1637 (COO), 972 (VO) Analysis calculated for C₃₈H₇₆N₂O₉V: C 60.38, N 3.71, H 10.13, found: C 60.41, N 3.64, H 9.95%.

Computing details

Data collection: EXPOSE (Stoe & Cie, 1997); cell refinement: CELL (Stoe & Cie, 1997); data reduction: INTEGRATE (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON/PLUTON (Spek, 1990); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of the anion of (I), showing the numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Bis(tetrabutylammonium) bis(malonato)oxovanadate(IV)

Crystal data

(C16H36N)2[VO(C3H2O4)2]	Z = 2
Mr = 755.95	F(000) = 826
Triclinic, P1	Dx = 1.144 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6847 (9) Å	Cell parameters from 8000 reflections
b = 13.3123 (13) Å	θ = 2.0–25.9°
c = 17.1221 (15) Å	µ = 0.28 mm^−1
α = 92.613 (11)°	T = 223 K
β = 90.303 (11)°	Block, blue
γ = 95.348 (11)°	0.40 × 0.30 × 0.20 mm
V = 2195.5 (4) Å^3

Data collection

Stoe Image Plate Diffraction System diffractometer	3112 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.127
Graphite monochromator	θmax = 25.9°, θmin = 2.0°
Detector resolution: 0.81Å pixels mm^-1	h = −11→11
ϕ oscillation scans	k = −16→16
17277 measured reflections	l = −20→20
7920 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.068	H-atom parameters constrained
wR(F^2) = 0.183	w = 1/[σ^2(Fo^2) + (0.0859P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.76	(Δ/σ)max < 0.001
7920 reflections	Δρmax = 0.43 e Å^−3
471 parameters	Δρmin = −0.56 e Å^−3
2 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0137 (17)

Special details

Experimental. The crystal did not diffract above ca 40° in 2θ and in one of the (n-Bu)₄N⁺ cations a methyl group is disordered.

Image plate distance 70 mm, ϕ oscillation scans 0 - 200°, step Δϕ = 1°, 2θ range 3.27–52.1°, dmax-dmin = 12.45–0.81 Å.

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	Occ. (<1)
V1	0.66564 (9)	0.73089 (5)	0.22316 (4)	0.0528 (3)
O1	0.5411 (4)	0.7001 (2)	0.16650 (16)	0.0682 (9)
O2	0.6560 (3)	0.6321 (2)	0.30517 (15)	0.0619 (9)
O3	0.8253 (3)	0.6651 (2)	0.18145 (16)	0.0647 (9)
O4	0.5983 (3)	0.8200 (2)	0.30620 (15)	0.0624 (9)
O5	0.7675 (3)	0.8517 (2)	0.18318 (15)	0.0612 (8)
O6	0.6694 (4)	0.4807 (2)	0.35079 (17)	0.0786 (11)
O7	0.9393 (4)	0.5329 (2)	0.14934 (18)	0.0790 (11)
O8	0.5078 (4)	0.9589 (2)	0.34882 (17)	0.0788 (11)
O9	0.7889 (5)	1.0116 (3)	0.1548 (2)	0.1104 (15)
C1	0.8402 (6)	0.5691 (4)	0.1802 (2)	0.0646 (14)
C2	0.7278 (6)	0.5027 (3)	0.2178 (2)	0.0674 (14)
H2A	0.7599	0.4355	0.2222	0.081*
H2B	0.6464	0.4954	0.1831	0.081*
C3	0.6834 (5)	0.5393 (3)	0.2977 (2)	0.0601 (13)
C4	0.5600 (5)	0.9092 (3)	0.2963 (2)	0.0626 (13)
C5	0.5822 (6)	0.9506 (4)	0.2164 (3)	0.0785 (16)
H5A	0.5667	1.0223	0.2195	0.094*
H5B	0.5123	0.9160	0.1805	0.094*
C6	0.7245 (6)	0.9401 (4)	0.1822 (2)	0.0705 (15)
N1	0.4968 (4)	0.7496 (2)	0.53261 (17)	0.0502 (9)
C11	0.4260 (5)	0.8458 (3)	0.5250 (2)	0.0547 (12)
H11A	0.4877	0.9025	0.5473	0.066*
H11B	0.4142	0.8569	0.4693	0.066*
C12	0.2859 (5)	0.8474 (3)	0.5639 (2)	0.0612 (13)
H12A	0.2973	0.8471	0.6208	0.073*
H12B	0.2256	0.7871	0.5467	0.073*
C13	0.2191 (6)	0.9429 (4)	0.5418 (3)	0.0744 (15)
H13A	0.2889	1.0011	0.5468	0.089*
H13B	0.1885	0.9352	0.4871	0.089*
C14	0.0972 (7)	0.9630 (5)	0.5925 (3)	0.0972 (19)
H14A	0.0310	0.9035	0.5910	0.146*
H14B	0.0532	1.0196	0.5732	0.146*
H14C	0.1289	0.9786	0.6459	0.146*
C15	0.5125 (5)	0.7253 (3)	0.6180 (2)	0.0577 (12)
H15A	0.5523	0.6604	0.6201	0.069*
H15B	0.4200	0.7169	0.6410	0.069*
C16	0.6024 (6)	0.8037 (4)	0.6683 (2)	0.0655 (13)
H16A	0.6977	0.8089	0.6489	0.079*
H16B	0.5667	0.8699	0.6652	0.079*
C17	0.6012 (8)	0.7729 (5)	0.7526 (3)	0.100 (2)
H17A	0.6802	0.8122	0.7788	0.120*	0.397 (12)
H17B	0.5175	0.7967	0.7761	0.120*	0.397 (12)
H17C	0.6555	0.7145	0.7548	0.120*	0.603 (12)
H17D	0.6524	0.8281	0.7835	0.120*	0.603 (12)
C18A	0.6057 (18)	0.6714 (11)	0.7746 (8)	0.105 (7)	0.397 (12)
H18A	0.5944	0.6682	0.8307	0.158*	0.397 (12)
H18B	0.6942	0.6480	0.7599	0.158*	0.397 (12)
H18C	0.5314	0.6288	0.7481	0.158*	0.397 (12)
C18B	0.4762 (10)	0.7481 (7)	0.7920 (4)	0.081 (4)	0.603 (12)
H18D	0.4271	0.6886	0.7664	0.122*	0.603 (12)
H18E	0.4191	0.8041	0.7909	0.122*	0.603 (12)
H18F	0.4964	0.7344	0.8458	0.122*	0.603 (12)
C19	0.4134 (5)	0.6597 (3)	0.4936 (2)	0.0524 (11)
H19A	0.4692	0.6020	0.4940	0.063*
H19B	0.3312	0.6431	0.5254	0.063*
C20	0.3658 (5)	0.6708 (3)	0.4109 (2)	0.0582 (12)
H20A	0.2944	0.7183	0.4108	0.070*
H20B	0.4442	0.6988	0.3803	0.070*
C21	0.3082 (6)	0.5714 (4)	0.3735 (3)	0.0720 (15)
H21A	0.3818	0.5256	0.3710	0.086*
H21B	0.2345	0.5416	0.4066	0.086*
C22	0.2510 (7)	0.5796 (5)	0.2928 (3)	0.109 (2)
H22A	0.1751	0.6222	0.2950	0.164*
H22B	0.2176	0.5129	0.2716	0.164*
H22C	0.3233	0.6089	0.2596	0.164*
C23	0.6381 (5)	0.7691 (3)	0.4937 (2)	0.0527 (11)
H23A	0.6229	0.7827	0.4387	0.063*
H23B	0.6870	0.8301	0.5186	0.063*
C24	0.7317 (5)	0.6830 (3)	0.4973 (2)	0.0624 (13)
H24A	0.7472	0.6671	0.5518	0.075*
H24B	0.6880	0.6223	0.4693	0.075*
C25	0.8697 (6)	0.7170 (4)	0.4593 (3)	0.0817 (16)
H25A	0.8523	0.7370	0.4060	0.098*
H25B	0.9140	0.7762	0.4890	0.098*
C26	0.9670 (7)	0.6340 (5)	0.4565 (4)	0.115 (2)
H26A	0.9846	0.6141	0.5092	0.172*
H26B	1.0539	0.6585	0.4330	0.172*
H26C	0.9249	0.5762	0.4256	0.172*
N2	1.0588 (4)	0.7571 (2)	−0.01126 (18)	0.0530 (10)
C31	0.9041 (5)	0.7429 (3)	0.0011 (2)	0.0520 (12)
H31A	0.8878	0.7230	0.0549	0.062*
H31B	0.8657	0.6865	−0.0337	0.062*
C32	0.8237 (6)	0.8333 (3)	−0.0127 (3)	0.0692 (15)
H32A	0.8480	0.8862	0.0280	0.083*
H32B	0.8490	0.8606	−0.0634	0.083*
C33	0.6697 (6)	0.8029 (4)	−0.0114 (3)	0.0687 (14)
H33A	0.6463	0.7725	0.0384	0.082*
H33B	0.6462	0.7514	−0.0533	0.082*
C34	0.5825 (6)	0.8904 (4)	−0.0216 (3)	0.0872 (17)
H34A	0.5981	0.9386	0.0225	0.131*
H34B	0.4852	0.8654	−0.0243	0.131*
H34C	0.6084	0.9233	−0.0695	0.131*
C35	1.1257 (5)	0.8400 (3)	0.0433 (2)	0.0609 (13)
H35A	1.0834	0.9024	0.0338	0.073*
H35B	1.2241	0.8512	0.0302	0.073*
C36	1.1145 (6)	0.8204 (4)	0.1303 (2)	0.0744 (15)
H36A	1.0186	0.7966	0.1424	0.089*
H36B	1.1736	0.7674	0.1429	0.089*
C37	1.1579 (7)	0.9143 (4)	0.1792 (3)	0.0940 (19)
H37A	1.0955	0.9659	0.1683	0.113*
H37B	1.2518	0.9401	0.1645	0.113*
C38	1.1560 (8)	0.8966 (6)	0.2670 (3)	0.126 (3)
H38A	1.0634	0.8706	0.2819	0.189*
H38B	1.1823	0.9598	0.2960	0.189*
H38C	1.2210	0.8480	0.2787	0.189*
C39	1.1139 (5)	0.6570 (3)	0.0027 (2)	0.0585 (12)
H39A	1.0875	0.6375	0.0555	0.070*
H39B	1.0677	0.6061	−0.0342	0.070*
C40	1.2683 (6)	0.6535 (5)	−0.0050 (3)	0.0916 (19)
H40A	1.3161	0.6997	0.0347	0.110*
H40B	1.2974	0.6763	−0.0566	0.110*
C41	1.3106 (7)	0.5460 (5)	0.0049 (3)	0.0931 (19)
H41A	1.2523	0.4986	−0.0296	0.112*
H41B	1.4070	0.5435	−0.0117	0.112*
C42	1.2974 (6)	0.5127 (4)	0.0866 (3)	0.0813 (16)
H42A	1.3557	0.5586	0.1210	0.122*
H42B	1.3263	0.4450	0.0891	0.122*
H42C	1.2016	0.5126	0.1028	0.122*
C43	1.0916 (5)	0.7886 (3)	−0.0944 (2)	0.0605 (13)
H43A	1.0638	0.8569	−0.0998	0.073*
H43B	1.1922	0.7918	−0.1014	0.073*
C44	1.0234 (5)	0.7210 (3)	−0.1592 (2)	0.0608 (13)
H44A	0.9224	0.7205	−0.1553	0.073*
H44B	1.0476	0.6518	−0.1537	0.073*
C45	1.0699 (6)	0.7575 (4)	−0.2387 (2)	0.0835 (17)
H45A	1.0429	0.8259	−0.2444	0.100*
H45B	1.1713	0.7607	−0.2413	0.100*
C46	1.0085 (7)	0.6899 (4)	−0.3057 (3)	0.0908 (18)
H46A	1.0486	0.6257	−0.3061	0.136*
H46B	1.0286	0.7219	−0.3546	0.136*
H46C	0.9089	0.6786	−0.2994	0.136*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0700 (6)	0.0447 (4)	0.0428 (4)	−0.0001 (4)	0.0215 (4)	0.0017 (3)
O1	0.073 (2)	0.069 (2)	0.0586 (18)	−0.0140 (17)	0.0076 (17)	0.0012 (15)
O2	0.093 (3)	0.0441 (17)	0.0495 (16)	0.0074 (16)	0.0318 (15)	0.0045 (13)
O3	0.085 (3)	0.0496 (19)	0.0599 (18)	0.0073 (16)	0.0361 (16)	0.0048 (14)
O4	0.095 (3)	0.0485 (18)	0.0454 (16)	0.0115 (17)	0.0270 (15)	0.0034 (13)
O5	0.073 (2)	0.054 (2)	0.0560 (17)	0.0006 (16)	0.0253 (15)	0.0053 (14)
O6	0.121 (3)	0.0517 (19)	0.065 (2)	0.0082 (19)	0.0328 (19)	0.0170 (16)
O7	0.098 (3)	0.063 (2)	0.080 (2)	0.024 (2)	0.044 (2)	0.0063 (17)
O8	0.115 (3)	0.061 (2)	0.0634 (19)	0.026 (2)	0.0292 (19)	−0.0040 (16)
O9	0.167 (5)	0.055 (2)	0.106 (3)	−0.019 (2)	0.053 (3)	0.019 (2)
C1	0.091 (4)	0.053 (3)	0.051 (3)	0.008 (3)	0.030 (3)	0.003 (2)
C2	0.089 (4)	0.054 (3)	0.059 (3)	0.004 (3)	0.032 (3)	0.000 (2)
C3	0.080 (4)	0.048 (3)	0.052 (3)	−0.002 (2)	0.022 (2)	0.005 (2)
C4	0.091 (4)	0.049 (3)	0.049 (2)	0.010 (3)	0.016 (2)	0.002 (2)
C5	0.120 (5)	0.064 (3)	0.056 (3)	0.029 (3)	0.019 (3)	0.012 (2)
C6	0.114 (5)	0.044 (3)	0.051 (3)	−0.006 (3)	0.017 (3)	0.004 (2)
N1	0.070 (3)	0.0409 (19)	0.0403 (17)	0.0070 (17)	0.0157 (17)	0.0032 (14)
C11	0.069 (4)	0.045 (3)	0.051 (2)	0.012 (2)	0.012 (2)	0.0056 (19)
C12	0.066 (4)	0.062 (3)	0.056 (3)	0.011 (3)	0.015 (2)	0.004 (2)
C13	0.084 (4)	0.070 (3)	0.073 (3)	0.028 (3)	0.008 (3)	0.004 (3)
C14	0.107 (5)	0.100 (4)	0.092 (4)	0.047 (4)	0.018 (3)	0.000 (3)
C15	0.077 (4)	0.050 (3)	0.048 (2)	0.013 (2)	0.017 (2)	0.011 (2)
C16	0.080 (4)	0.063 (3)	0.054 (3)	0.005 (3)	0.009 (2)	0.002 (2)
C17	0.141 (7)	0.098 (5)	0.056 (3)	−0.016 (4)	0.000 (4)	0.004 (3)
C18A	0.117 (15)	0.126 (15)	0.079 (10)	0.024 (11)	−0.013 (9)	0.043 (9)
C18B	0.086 (8)	0.107 (8)	0.045 (4)	−0.021 (6)	0.002 (4)	0.001 (4)
C19	0.056 (3)	0.046 (2)	0.054 (2)	−0.002 (2)	0.012 (2)	0.0034 (19)
C20	0.067 (4)	0.057 (3)	0.049 (2)	−0.001 (2)	0.017 (2)	−0.001 (2)
C21	0.079 (4)	0.061 (3)	0.073 (3)	−0.004 (3)	0.020 (3)	−0.014 (2)
C22	0.138 (6)	0.123 (5)	0.055 (3)	−0.038 (4)	0.011 (3)	−0.023 (3)
C23	0.054 (3)	0.051 (3)	0.053 (2)	0.003 (2)	0.015 (2)	0.0069 (19)
C24	0.067 (4)	0.067 (3)	0.054 (3)	0.011 (3)	0.013 (2)	−0.004 (2)
C25	0.062 (4)	0.095 (4)	0.087 (4)	0.010 (3)	0.010 (3)	−0.013 (3)
C26	0.080 (5)	0.139 (6)	0.128 (5)	0.038 (4)	0.011 (4)	−0.029 (4)
N2	0.063 (3)	0.049 (2)	0.0470 (19)	0.0023 (18)	0.0178 (17)	0.0106 (16)
C31	0.062 (4)	0.049 (3)	0.047 (2)	0.006 (2)	0.014 (2)	0.0100 (19)
C32	0.098 (5)	0.055 (3)	0.058 (3)	0.017 (3)	0.025 (3)	0.009 (2)
C33	0.070 (4)	0.083 (4)	0.055 (3)	0.019 (3)	0.012 (2)	0.001 (2)
C34	0.092 (5)	0.094 (4)	0.082 (3)	0.041 (4)	0.013 (3)	−0.001 (3)
C35	0.064 (4)	0.056 (3)	0.061 (3)	−0.002 (2)	0.014 (2)	0.003 (2)
C36	0.077 (4)	0.089 (4)	0.053 (3)	−0.008 (3)	0.009 (2)	−0.005 (3)
C37	0.109 (5)	0.105 (5)	0.065 (3)	0.001 (4)	0.003 (3)	−0.013 (3)
C38	0.132 (7)	0.169 (7)	0.073 (4)	0.001 (5)	0.006 (4)	−0.020 (4)
C39	0.070 (4)	0.056 (3)	0.052 (2)	0.016 (2)	0.014 (2)	0.014 (2)
C40	0.088 (5)	0.106 (5)	0.089 (4)	0.032 (4)	0.039 (3)	0.043 (3)
C41	0.101 (5)	0.119 (5)	0.066 (3)	0.049 (4)	0.014 (3)	−0.001 (3)
C42	0.092 (5)	0.074 (4)	0.079 (3)	0.010 (3)	0.003 (3)	0.000 (3)
C43	0.072 (4)	0.061 (3)	0.050 (2)	0.005 (2)	0.026 (2)	0.015 (2)
C44	0.077 (4)	0.060 (3)	0.046 (2)	0.008 (2)	0.022 (2)	0.006 (2)
C45	0.110 (5)	0.087 (4)	0.050 (3)	−0.011 (3)	0.020 (3)	0.008 (3)
C46	0.108 (5)	0.106 (4)	0.059 (3)	0.009 (4)	0.021 (3)	0.006 (3)

Geometric parameters (Å, º)

V1—O1	1.556 (3)	C16—C17	1.519 (6)
V1—O2	1.964 (3)	C17—C18B	1.408 (9)
V1—O3	1.968 (3)	C17—C18A	1.423 (13)
V1—O4	1.964 (3)	C19—C20	1.504 (5)
V1—O5	1.960 (3)	C20—C21	1.501 (6)
O2—C3	1.288 (5)	C21—C22	1.498 (7)
O3—C1	1.299 (5)	C23—C24	1.530 (6)
O4—C4	1.294 (5)	C24—C25	1.529 (7)
O5—C6	1.284 (5)	C25—C26	1.518 (8)
O6—C3	1.225 (5)	N2—C35	1.509 (5)
O7—C1	1.225 (5)	N2—C39	1.509 (5)
O8—C4	1.231 (5)	N2—C31	1.509 (5)
O9—C6	1.204 (5)	N2—C43	1.529 (5)
C1—C2	1.503 (6)	C31—C32	1.520 (6)
C2—C3	1.509 (5)	C32—C33	1.509 (7)
C4—C5	1.505 (6)	C33—C34	1.517 (7)
C5—C6	1.516 (7)	C35—C36	1.526 (6)
N1—C19	1.508 (5)	C36—C37	1.498 (7)
N1—C11	1.517 (5)	C37—C38	1.531 (7)
N1—C15	1.521 (5)	C39—C40	1.508 (7)
N1—C23	1.531 (5)	C40—C41	1.541 (8)
C11—C12	1.516 (6)	C41—C42	1.490 (7)
C12—C13	1.540 (6)	C43—C44	1.505 (6)
C13—C14	1.505 (7)	C44—C45	1.524 (6)
C15—C16	1.527 (6)	C45—C46	1.509 (7)
O1—V1—O5	107.29 (15)	C15—N1—C23	111.4 (3)
O1—V1—O4	106.85 (16)	C12—C11—N1	115.7 (3)
O5—V1—O4	86.95 (12)	C11—C12—C13	109.4 (4)
O1—V1—O2	106.86 (16)	C14—C13—C12	112.5 (4)
O5—V1—O2	145.85 (14)	N1—C15—C16	115.5 (4)
O4—V1—O2	83.42 (11)	C17—C16—C15	109.7 (4)
O1—V1—O3	107.11 (15)	C18B—C17—C18A	74.2 (8)
O5—V1—O3	82.72 (13)	C18B—C17—C16	121.6 (6)
O4—V1—O3	146.04 (14)	C18A—C17—C16	123.5 (8)
O2—V1—O3	87.22 (12)	C20—C19—N1	116.7 (3)
C3—O2—V1	126.7 (2)	C21—C20—C19	111.6 (4)
C1—O3—V1	126.3 (3)	C22—C21—C20	113.7 (4)
C4—O4—V1	125.0 (3)	C24—C23—N1	115.1 (4)
C6—O5—V1	126.1 (3)	C25—C24—C23	108.0 (4)
O7—C1—O3	122.5 (4)	C26—C25—C24	111.7 (5)
O7—C1—C2	120.8 (4)	C35—N2—C39	111.5 (3)
O3—C1—C2	116.7 (4)	C35—N2—C31	110.9 (3)
C1—C2—C3	115.7 (4)	C39—N2—C31	106.8 (3)
O6—C3—O2	123.1 (4)	C35—N2—C43	106.7 (3)
O6—C3—C2	120.1 (4)	C39—N2—C43	110.3 (3)
O2—C3—C2	116.8 (4)	C31—N2—C43	110.8 (3)
O8—C4—O4	122.5 (4)	N2—C31—C32	116.6 (4)
O8—C4—C5	120.7 (4)	C33—C32—C31	110.4 (4)
O4—C4—C5	116.7 (4)	C32—C33—C34	113.4 (5)
C4—C5—C6	115.1 (4)	N2—C35—C36	115.6 (4)
O9—C6—O5	123.9 (5)	C37—C36—C35	111.1 (4)
O9—C6—C5	120.1 (5)	C36—C37—C38	112.8 (5)
O5—C6—C5	116.0 (4)	C40—C39—N2	116.3 (4)
C19—N1—C11	111.6 (3)	C39—C40—C41	111.4 (5)
C19—N1—C15	106.2 (3)	C42—C41—C40	113.4 (4)
C11—N1—C15	111.1 (3)	C44—C43—N2	115.9 (4)
C19—N1—C23	110.9 (3)	C43—C44—C45	110.7 (4)
C11—N1—C23	105.7 (3)	C46—C45—C44	112.7 (4)
O1—V1—O2—C3	72.1 (4)	C19—N1—C15—C16	176.2 (4)
O5—V1—O2—C3	−107.6 (4)	C11—N1—C15—C16	−62.3 (5)
O4—V1—O2—C3	177.8 (4)	C23—N1—C15—C16	55.3 (5)
O3—V1—O2—C3	−34.9 (4)	N1—C15—C16—C17	176.4 (4)
O1—V1—O3—C1	−70.2 (4)	C15—C16—C17—C18B	−51.7 (8)
O5—V1—O3—C1	−176.1 (4)	C15—C16—C17—C18A	39.6 (12)
O4—V1—O3—C1	110.5 (4)	C11—N1—C19—C20	50.3 (5)
O2—V1—O3—C1	36.6 (4)	C15—N1—C19—C20	171.6 (4)
O1—V1—O4—C4	−66.6 (4)	C23—N1—C19—C20	−67.2 (5)
O5—V1—O4—C4	40.5 (4)	N1—C19—C20—C21	169.1 (4)
O2—V1—O4—C4	−172.3 (4)	C19—C20—C21—C22	176.3 (4)
O3—V1—O4—C4	112.7 (4)	C19—N1—C23—C24	−61.3 (4)
O1—V1—O5—C6	69.0 (4)	C11—N1—C23—C24	177.5 (3)
O4—V1—O5—C6	−37.7 (4)	C15—N1—C23—C24	56.8 (4)
O2—V1—O5—C6	−111.3 (4)	N1—C23—C24—C25	−177.4 (3)
O3—V1—O5—C6	174.7 (4)	C23—C24—C25—C26	−177.1 (4)
V1—O3—C1—O7	175.9 (4)	C35—N2—C31—C32	60.5 (4)
V1—O3—C1—C2	−3.3 (6)	C39—N2—C31—C32	−177.8 (3)
O7—C1—C2—C3	133.7 (5)	C43—N2—C31—C32	−57.8 (4)
O3—C1—C2—C3	−47.1 (6)	N2—C31—C32—C33	170.5 (3)
V1—O2—C3—O6	−176.8 (4)	C31—C32—C33—C34	177.7 (4)
V1—O2—C3—C2	0.2 (6)	C39—N2—C35—C36	−55.4 (5)
C1—C2—C3—O6	−134.0 (5)	C31—N2—C35—C36	63.4 (5)
C1—C2—C3—O2	48.9 (7)	C43—N2—C35—C36	−175.8 (4)
V1—O4—C4—O8	173.9 (4)	N2—C35—C36—C37	−168.5 (4)
V1—O4—C4—C5	−6.2 (7)	C35—C36—C37—C38	−176.8 (5)
O8—C4—C5—C6	132.8 (5)	C35—N2—C39—C40	−57.7 (5)
O4—C4—C5—C6	−47.1 (7)	C31—N2—C39—C40	−179.0 (4)
V1—O5—C6—O9	−177.6 (4)	C43—N2—C39—C40	60.6 (5)
V1—O5—C6—C5	0.9 (6)	N2—C39—C40—C41	−176.0 (4)
C4—C5—C6—O9	−131.4 (5)	C39—C40—C41—C42	−70.8 (7)
C4—C5—C6—O5	50.1 (6)	C35—N2—C43—C44	−174.5 (4)
C19—N1—C11—C12	62.8 (4)	C39—N2—C43—C44	64.2 (5)
C15—N1—C11—C12	−55.6 (5)	C31—N2—C43—C44	−53.7 (5)
C23—N1—C11—C12	−176.5 (3)	N2—C43—C44—C45	−177.1 (4)
N1—C11—C12—C13	−172.5 (4)	C43—C44—C45—C46	177.8 (5)
C11—C12—C13—C14	−166.3 (4)