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The crystal structure of the title complex, bis­(tetra-n-butyl­ammonium) bis(\mu-\alpha-hydroxy­benzene­acetato)-1κ2O1,O2:2κO2;1κO2:2κ2O1O2-bis­[oxo­(peroxo)­vanadium(V)] α-hydroxy­benzene­acetic acid solvate, (C16H36N)2­[V2O2(O2)2(C8H6O3)2]·C8H8O3, consists of dimeric anions with twofold rotation symmetry, cations and mol­ecules of mandelic acid. Deprotonated hydroxyl O atoms of the mandelate dianion ligands bridge the V atoms to give a non-planar V2O2 ring. Each V atom has distorted pentagonal pyramidal coordination geometry, with an oxo ligand in the axial position. The mandelic acid mol­ecule is disordered and coordinates weakly to the second axial site of each V atom through a carboxyl­ate O atom.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199013475/cf1306sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199013475/cf1306Isup2.hkl
Contains datablock I

CCDC reference: 142724

Comment top

Vanadium compounds are important in biochemistry and biology in many ways (Sigel & Sigel, 1995; Djordjevic et al., 1995). Peroxo complexes form a new category of compounds, with effective insulin-mimetic activity (Sigel & Sigel, 1995). Vanadium peroxo complexes are formed as intermediates in oxidation reactions catalysed by haloperoxidase, which contains V in the active site (Messerschmidt et al., 1997). This enzyme has been found in a variety of seaweeds (Wever et al., 1991). Anions of α-hydroxycarboxylic acids also represent an interesting class of biogenic ligands. Several dinuclear vanadium monoperoxo complexes with biogenic heteroligands such as citrate (Djordjevic et al., 1989), malate (Djordjevic et al., 1995), and tartrate ions (Schwendt et al., 1998) have been prepared recently. We report here a related complex with the mandelate dianion as ligand, bis(tetra-n-butylammonium) bis[(mandelato)oxo(peroxo)vanadate(V)] mandelic acid solvate, (I). \scheme

The crystal structure of (I) consists of dimeric anions with crystallographic twofold rotation symmetry (Fig. 1), unexceptional (Bu4N)+ cations and one molecule of neutral mandelic acid per dimeric anion. The component cations, anions and mandelic acid molecules are held together by electrostatic forces and hydrogen bonds.

The two V atoms in the anion are doubly bridged by the deprotonated hydroxyl O atoms of two mandelato ligands, O5 and O5i [symmetry code: (i) 1 − x, y, 1/2 − z], to give a central V2O2 ring. This ring is not planar, but has a dihedral angle of folding of 151.79 (8)° about the O5···O5i line. Each mandelato anion also coordinates terminally to one V atom through its carboxylate group to form five-membered chelate rings. The primary coordination of V is distorted pentagonal pyramidal by six O atoms. The equatorial plane involves the peroxo group [O2 and O3, with O—O = 1.432 (3) Å], the two bridging O atoms and the carboxylate atom O4, which have a maximum deviation of 0.10 (7) Å from this plane. The axial position is occupied by the doubly-bonded oxo ligand O1, 1.89 (7) Å out of the equatorial plane, with V—O1 = 1.578 (2) Å. The V atom is displaced 0.32 (1) Å out of the equatorial plane, towards the axial oxo ligand.

The neutral mandelic acid molecule is disordered about the twofold rotation axis in such a way that the O atoms coincide in the two orientations. One carboxylate O atom, on the twofold axis, is coordinated to the two V atoms in an axial position opposite the oxo ligand, the V—O8 distance being 2.550 (3) Å.

Experimental top

A solution of NH4VO3 (2.5 mmol) in water (10 ml) was mixed with a solution of mandelic acid (2.5 mmol) in water (5 ml). After cooling of the solution to 273 K, H2O2 (30%, 5 ml) and ethanol (2.5 mmol, 10 ml) were added with stirring. Russet (dark red below?) crystals were isolated after a few days at 278 K.

Refinement top

All C atoms of the neutral disordered mandelic acid molecule have a site occupation factor of 1/2, while O8 lies on the twofold rotation axis and O7 represents two different O atoms in the two disordered orientations. H atoms of the neutral disordered mandelic acid were set in an idealized positions and their parameters were calculated. Other H-atom parameters were refined independently.

Computing details top

Data collection: KM-4 Software (Galdecki et al., 1996); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Johnson & Burnett, 1996); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of the dimeric anion of (I), [V2O2(O2)2(C8H6O3)2]2−, with 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as spheres of arbitrary radii.
Bis(tetra-n-butylammonium) Bis[µ-2-hydroxy-2-phenyl- ethanoato(2-)]-bis[oxomonoperoxovanadate(V)] top
Crystal data top
(C16H36N)2[V2O2(O2)2(C8H6O3)2]·C8H8O3F(000) = 2432
Mr = 1135.20Dx = 1.272 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 41 reflections
a = 19.657 (12) Åθ = 1.6–25.1°
b = 17.066 (3) ŵ = 0.38 mm1
c = 17.670 (5) ÅT = 150 K
V = 5928 (4) Å3Prism, dark red
Z = 40.4 × 0.3 × 0.3 mm
Data collection top
4-circle κ-axis Kuma KM-4
diffractometer with Oxford Cryosytems Cryostream cooler
Rint = 0.023
Radiation source: fine-focus sealed tubeθmax = 25.1°, θmin = 1.6°
Graphite monochromatorh = 230
ω/2θ scansk = 193
5680 measured reflectionsl = 021
5210 independent reflections3 standard reflections every 300 reflections
3329 reflections with I > 2σ(I) intensity decay: 2.0%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0838P)2 + 5.65P]
where P = (Fo2 + 2Fc2)/3
5210 reflections(Δ/σ)max = 0.001
383 parametersΔρmax = 0.66 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
(C16H36N)2[V2O2(O2)2(C8H6O3)2]·C8H8O3V = 5928 (4) Å3
Mr = 1135.20Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 19.657 (12) ŵ = 0.38 mm1
b = 17.066 (3) ÅT = 150 K
c = 17.670 (5) Å0.4 × 0.3 × 0.3 mm
Data collection top
4-circle κ-axis Kuma KM-4
diffractometer with Oxford Cryosytems Cryostream cooler
Rint = 0.023
5680 measured reflections3 standard reflections every 300 reflections
5210 independent reflections intensity decay: 2.0%
3329 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.168H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.66 e Å3
5210 reflectionsΔρmin = 0.40 e Å3
383 parameters
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
V10.57814 (3)0.69623 (3)0.22800 (3)0.03233 (18)
O10.61333 (11)0.77895 (14)0.21963 (14)0.0415 (6)
N10.77877 (14)0.85962 (17)0.34708 (16)0.0378 (7)
C10.53831 (19)0.6788 (2)0.07320 (19)0.0407 (8)
O20.62799 (11)0.64963 (15)0.30686 (13)0.0420 (6)
C20.47521 (17)0.7142 (2)0.10889 (17)0.0362 (7)
H20.43580.67840.09970.043*
O30.64933 (11)0.62301 (14)0.23374 (13)0.0390 (5)
O40.58532 (12)0.66062 (15)0.12102 (13)0.0441 (6)
O50.48649 (11)0.71961 (13)0.18755 (11)0.0325 (5)
C50.45873 (16)0.7933 (2)0.07630 (19)0.0367 (8)
O60.54194 (15)0.66761 (17)0.00506 (14)0.0556 (7)
C60.47267 (18)0.8614 (2)0.1156 (2)0.0442 (8)
H60.49140.85870.16510.053*
C70.4594 (2)0.9332 (2)0.0833 (2)0.0545 (10)
H70.46870.97990.11070.065*
O70.41079 (14)0.4824 (2)0.2623 (2)0.0767 (11)
H7O0.398 (4)0.528 (5)0.278 (4)0.15 (3)*
C80.4327 (2)0.9378 (3)0.0113 (2)0.0568 (11)
H80.42400.98750.01090.068*
O80.50000.5791 (2)0.25000.0514 (10)
C90.4186 (2)0.8706 (3)0.0281 (2)0.0563 (10)
H90.40060.87370.07790.068*
C100.4304 (2)0.7987 (2)0.0040 (2)0.0503 (10)
H100.41930.75230.02300.060*
C110.5264 (3)0.5147 (4)0.2526 (5)0.0482 (19)0.50
C120.4826 (6)0.4549 (6)0.2915 (5)0.076 (3)0.50
H120.48580.46060.34770.091*0.50
C130.4975 (8)0.3697 (6)0.2677 (4)0.037 (4)0.50
C140.5005 (5)0.3119 (9)0.3216 (7)0.042 (4)0.50
H140.49890.32380.37410.050*0.50
C150.5062 (14)0.2333 (16)0.2955 (15)0.069 (8)0.50
H150.51000.19170.33090.083*0.50
C160.5063 (13)0.2180 (14)0.2221 (13)0.071 (11)0.50
H160.51370.16530.20680.086*0.50
C170.4967 (8)0.2723 (10)0.1675 (10)0.053 (4)0.50
H170.49090.25900.11570.064*0.50
C180.4960 (6)0.3492 (8)0.1932 (8)0.036 (3)0.50
H180.49440.39000.15670.043*0.50
C310.83151 (19)0.9095 (2)0.3872 (2)0.0461 (9)
H31A0.87150.87620.39830.055*
H31B0.84660.95100.35190.055*
C320.8094 (3)0.9481 (2)0.4600 (2)0.0624 (12)
H32A0.80220.90810.49980.075*
H32B0.76620.97680.45220.075*
C330.8663 (3)1.0058 (3)0.4843 (3)0.0884 (18)
H33A0.91060.97810.48420.106*
H33B0.86911.04920.44720.106*
C340.8533 (4)1.0384 (4)0.5607 (4)0.126 (3)
H34A0.88941.07560.57380.189*
H34B0.85260.99570.59790.189*
H34C0.80931.06530.56100.189*
C410.71599 (18)0.9076 (2)0.3270 (2)0.0435 (8)
H41A0.68470.87400.29740.052*
H41B0.69240.92200.37450.052*
C420.7292 (2)0.9821 (3)0.2821 (3)0.0661 (12)
H42A0.74840.96820.23200.079*
H42B0.76311.01450.30910.079*
C430.6643 (2)1.0294 (3)0.2709 (3)0.0671 (12)
H43A0.64131.03580.32030.081*
H43B0.67631.08230.25200.081*
C440.6163 (3)0.9918 (3)0.2166 (3)0.0921 (18)
H44A0.60050.94190.23740.138*
H44B0.63970.98240.16840.138*
H44C0.57731.02650.20810.138*
C510.81340 (17)0.8282 (2)0.27666 (19)0.0421 (8)
H51A0.82590.87300.24390.051*
H51B0.85610.80170.29190.051*
C520.77127 (18)0.7716 (3)0.2311 (2)0.0513 (10)
H52A0.75990.72560.26290.062*
H52B0.72810.79730.21630.062*
C530.8079 (2)0.7444 (3)0.1612 (2)0.0544 (10)
H53A0.85140.71940.17590.065*
H53B0.81850.79020.12890.065*
C540.7654 (2)0.6867 (3)0.1168 (2)0.0610 (12)
H54B0.75810.63940.14720.091*
H54A0.78910.67280.06990.091*
H54C0.72140.71040.10450.091*
C610.75488 (19)0.7932 (2)0.39740 (19)0.0416 (8)
H61A0.73050.81580.44130.050*
H61B0.72190.76100.36870.050*
C620.8101 (2)0.7405 (2)0.4264 (2)0.0526 (10)
H62A0.83990.77020.46130.063*
H62B0.83830.72200.38350.063*
C630.7804 (3)0.6709 (3)0.4672 (3)0.0642 (12)
H63A0.75730.63630.43030.077*
H63B0.74590.68930.50410.077*
C640.8348 (3)0.6252 (3)0.5082 (4)0.103 (2)
H64A0.81450.57920.53240.155*
H64B0.85590.65850.54690.155*
H64C0.86960.60820.47200.155*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V10.0297 (3)0.0336 (3)0.0337 (3)0.0011 (2)0.0004 (2)0.0004 (2)
O10.0365 (12)0.0364 (13)0.0517 (14)0.0064 (10)0.0022 (10)0.0036 (11)
N10.0406 (14)0.0392 (17)0.0336 (14)0.0022 (12)0.0016 (12)0.0026 (13)
C10.053 (2)0.035 (2)0.0334 (18)0.0023 (16)0.0016 (16)0.0028 (15)
O20.0375 (12)0.0493 (15)0.0393 (13)0.0053 (11)0.0024 (10)0.0027 (11)
C20.0428 (18)0.0383 (19)0.0276 (16)0.0008 (15)0.0022 (14)0.0006 (14)
O30.0356 (12)0.0419 (14)0.0394 (13)0.0047 (10)0.0023 (10)0.0058 (11)
O40.0429 (13)0.0509 (15)0.0385 (13)0.0107 (11)0.0010 (11)0.0047 (12)
O50.0337 (11)0.0356 (13)0.0281 (11)0.0032 (9)0.0021 (9)0.0001 (10)
C50.0346 (16)0.044 (2)0.0318 (16)0.0017 (15)0.0003 (13)0.0001 (15)
O60.0731 (18)0.0633 (18)0.0304 (13)0.0188 (15)0.0026 (12)0.0054 (12)
C60.052 (2)0.042 (2)0.0385 (19)0.0011 (17)0.0006 (16)0.0014 (16)
C70.065 (3)0.043 (2)0.055 (2)0.0013 (19)0.006 (2)0.0002 (19)
O70.0360 (14)0.083 (3)0.111 (3)0.0040 (15)0.0001 (16)0.031 (2)
C80.057 (2)0.054 (3)0.059 (2)0.011 (2)0.002 (2)0.019 (2)
O80.055 (2)0.037 (2)0.062 (2)0.0000.0204 (18)0.000
C90.059 (2)0.064 (3)0.046 (2)0.007 (2)0.0118 (19)0.013 (2)
C100.058 (2)0.054 (2)0.039 (2)0.0027 (19)0.0101 (17)0.0029 (18)
C110.035 (3)0.038 (4)0.072 (5)0.004 (3)0.009 (4)0.002 (4)
C120.122 (9)0.063 (6)0.043 (5)0.022 (6)0.004 (5)0.003 (4)
C130.059 (5)0.029 (4)0.022 (12)0.011 (4)0.014 (10)0.006 (4)
C140.037 (4)0.060 (14)0.027 (7)0.011 (9)0.001 (3)0.032 (10)
C150.068 (11)0.085 (18)0.055 (13)0.027 (11)0.006 (11)0.047 (10)
C160.049 (10)0.041 (6)0.12 (3)0.007 (8)0.011 (12)0.013 (9)
C170.053 (6)0.075 (13)0.032 (8)0.015 (8)0.010 (5)0.015 (8)
C180.040 (5)0.045 (9)0.022 (9)0.001 (6)0.006 (5)0.004 (6)
C310.053 (2)0.040 (2)0.044 (2)0.0088 (17)0.0102 (17)0.0015 (17)
C320.098 (3)0.043 (2)0.046 (2)0.001 (2)0.009 (2)0.0035 (19)
C330.120 (4)0.061 (3)0.085 (4)0.018 (3)0.052 (3)0.020 (3)
C340.194 (7)0.080 (4)0.104 (5)0.036 (5)0.076 (5)0.031 (4)
C410.0414 (18)0.044 (2)0.045 (2)0.0002 (16)0.0034 (15)0.0076 (17)
C420.070 (3)0.061 (3)0.068 (3)0.002 (2)0.002 (2)0.026 (2)
C430.071 (3)0.060 (3)0.071 (3)0.000 (2)0.007 (2)0.026 (2)
C440.122 (5)0.069 (4)0.085 (4)0.019 (3)0.032 (3)0.003 (3)
C510.0362 (17)0.053 (2)0.0367 (18)0.0030 (16)0.0037 (15)0.0004 (17)
C520.0383 (18)0.070 (3)0.046 (2)0.0120 (18)0.0031 (16)0.009 (2)
C530.050 (2)0.077 (3)0.036 (2)0.012 (2)0.0030 (16)0.004 (2)
C540.057 (2)0.092 (3)0.0346 (19)0.014 (2)0.0040 (17)0.010 (2)
C610.051 (2)0.038 (2)0.0359 (17)0.0039 (16)0.0065 (16)0.0026 (15)
C620.066 (2)0.041 (2)0.050 (2)0.0069 (19)0.0015 (19)0.0053 (18)
C630.091 (3)0.038 (2)0.064 (3)0.008 (2)0.006 (2)0.007 (2)
C640.120 (5)0.063 (3)0.128 (5)0.028 (3)0.004 (4)0.040 (4)
Geometric parameters (Å, º) top
V1—O11.579 (2)C31—C321.509 (6)
V1—O31.879 (2)C31—H31A0.9900
V1—O21.880 (2)C31—H31B0.9900
V1—O51.979 (2)C32—C331.550 (7)
V1—O41.991 (2)C32—H32A0.9900
V1—O5i2.000 (2)C32—H32B0.9900
N1—C611.516 (4)C33—C341.484 (8)
N1—C511.516 (4)C33—H33A0.9900
N1—C311.518 (4)C33—H33B0.9900
N1—C411.523 (4)C34—H34A0.9800
C1—O61.221 (4)C34—H34B0.9800
C1—O41.290 (4)C34—H34C0.9800
C1—C21.517 (5)C41—C421.521 (5)
O2—O31.432 (3)C41—H41A0.9900
C2—O51.410 (4)C41—H41B0.9900
C2—C51.502 (5)C42—C431.523 (6)
C2—H21.0000C42—H42A0.9900
O5—V1i2.000 (2)C42—H42B0.9900
C5—C61.382 (5)C43—C441.491 (7)
C5—C101.396 (5)C43—H43A0.9900
C6—C71.378 (5)C43—H43B0.9900
C6—H60.9500C44—H44A0.9800
C7—C81.378 (6)C44—H44B0.9800
C7—H70.9500C44—H44C0.9800
O7—C11i1.378 (8)C51—C521.505 (5)
O7—C121.576 (12)C51—H51A0.9900
O7—H7O0.86 (8)C51—H51B0.9900
C8—C91.371 (6)C52—C531.503 (5)
C8—H80.9500C52—H52A0.9900
O8—C11i1.216 (8)C52—H52B0.9900
O8—C111.216 (8)C53—C541.512 (6)
C9—C101.371 (6)C53—H53A0.9900
C9—H90.9500C53—H53B0.9900
C10—H100.9500C54—H54B0.9800
C11—O7i1.378 (8)C54—H54A0.9800
C11—C121.501 (12)C54—H54C0.9800
C12—C131.541 (15)C61—C621.501 (5)
C12—H121.0000C61—H61A0.9900
C13—C181.362 (16)C61—H61B0.9900
C13—C141.372 (14)C62—C631.507 (6)
C14—C151.42 (3)C62—H62A0.9900
C14—H140.9500C62—H62B0.9900
C15—C161.32 (3)C63—C641.510 (7)
C15—H150.9500C63—H63A0.9900
C16—C171.35 (4)C63—H63B0.9900
C16—H160.9500C64—H64A0.9800
C17—C181.390 (18)C64—H64B0.9800
C17—H170.9500C64—H64C0.9800
C18—H180.9500
O1—V1—O3105.87 (12)C31—C32—C33107.8 (4)
O1—V1—O2102.67 (12)C31—C32—H32A110.2
O3—V1—O244.80 (10)C33—C32—H32A110.2
O1—V1—O5100.65 (11)C31—C32—H32B110.2
O3—V1—O5146.27 (10)C33—C32—H32B110.2
O2—V1—O5145.84 (10)H32A—C32—H32B108.5
O1—V1—O498.80 (12)C34—C33—C32111.4 (6)
O3—V1—O478.20 (10)C34—C33—H33A109.3
O2—V1—O4122.53 (11)C32—C33—H33A109.3
O5—V1—O477.47 (9)C34—C33—H33B109.3
O1—V1—O5i99.78 (11)C32—C33—H33B109.3
O3—V1—O5i124.43 (10)H33A—C33—H33B108.0
O2—V1—O5i82.09 (10)C33—C34—H34A109.5
O5—V1—O5i69.57 (10)C33—C34—H34B109.5
O4—V1—O5i144.53 (10)H34A—C34—H34B109.5
C61—N1—C51110.8 (3)C33—C34—H34C109.5
C61—N1—C31110.9 (3)H34A—C34—H34C109.5
C51—N1—C31106.0 (3)H34B—C34—H34C109.5
C61—N1—C41106.7 (2)C42—C41—N1115.7 (3)
C51—N1—C41111.2 (3)C42—C41—H41A108.4
C31—N1—C41111.2 (3)N1—C41—H41A108.4
O6—C1—O4124.5 (3)C42—C41—H41B108.4
O6—C1—C2121.3 (3)N1—C41—H41B108.4
O4—C1—C2114.2 (3)H41A—C41—H41B107.4
O3—O2—V167.55 (13)C41—C42—C43111.6 (3)
O5—C2—C5110.7 (3)C41—C42—H42A109.3
O5—C2—C1107.9 (3)C43—C42—H42A109.3
C5—C2—C1112.0 (3)C41—C42—H42B109.3
O5—C2—H2108.7C43—C42—H42B109.3
C5—C2—H2108.7H42A—C42—H42B108.0
C1—C2—H2108.7C44—C43—C42112.6 (5)
O2—O3—V167.65 (13)C44—C43—H43A109.1
C1—O4—V1119.9 (2)C42—C43—H43A109.1
C2—O5—V1119.08 (19)C44—C43—H43B109.1
C2—O5—V1i128.5 (2)C42—C43—H43B109.1
V1—O5—V1i105.58 (10)H43A—C43—H43B107.8
C6—C5—C10118.9 (3)C43—C44—H44A109.5
C6—C5—C2121.3 (3)C43—C44—H44B109.5
C10—C5—C2119.7 (3)H44A—C44—H44B109.5
C7—C6—C5120.1 (3)C43—C44—H44C109.5
C7—C6—H6119.9H44A—C44—H44C109.5
C5—C6—H6119.9H44B—C44—H44C109.5
C6—C7—C8120.4 (4)C52—C51—N1114.7 (3)
C6—C7—H7119.8C52—C51—H51A108.6
C8—C7—H7119.8N1—C51—H51A108.6
C11i—O7—C1251.6 (5)C52—C51—H51B108.6
C11i—O7—H7O87 (5)N1—C51—H51B108.6
C12—O7—H7O115 (5)H51A—C51—H51B107.6
C9—C8—C7119.9 (4)C53—C52—C51112.0 (3)
C9—C8—H8120.1C53—C52—H52A109.2
C7—C8—H8120.1C51—C52—H52A109.2
C11i—O8—C1150.6 (7)C53—C52—H52B109.2
C8—C9—C10120.3 (4)C51—C52—H52B109.2
C8—C9—H9119.8H52A—C52—H52B107.9
C10—C9—H9119.8C52—C53—C54111.3 (3)
C9—C10—C5120.4 (4)C52—C53—H53A109.4
C9—C10—H10119.8C54—C53—H53A109.4
C5—C10—H10119.8C52—C53—H53B109.4
O8—C11—O7i137.4 (7)C54—C53—H53B109.4
O8—C11—C12112.9 (7)H53A—C53—H53B108.0
O7i—C11—C12109.2 (7)C53—C54—H54B109.5
C11—C12—C13114.1 (9)C53—C54—H54A109.5
C11—C12—O799.2 (7)H54B—C54—H54A109.5
C13—C12—O7111.2 (8)C53—C54—H54C109.5
C11—C12—H12110.6H54B—C54—H54C109.5
C13—C12—H12110.6H54A—C54—H54C109.5
O7—C12—H12110.6C62—C61—N1115.1 (3)
C18—C13—C14119.2 (12)C62—C61—H61A108.5
C18—C13—C12120.1 (10)N1—C61—H61A108.5
C14—C13—C12119.8 (8)C62—C61—H61B108.5
C13—C14—C15117.1 (11)N1—C61—H61B108.5
C13—C14—H14121.4H61A—C61—H61B107.5
C15—C14—H14121.4C61—C62—C63110.7 (4)
C16—C15—C14120 (2)C61—C62—H62A109.5
C16—C15—H15119.8C63—C62—H62A109.5
C14—C15—H15119.8C61—C62—H62B109.5
C15—C16—C17124 (3)C63—C62—H62B109.5
C15—C16—H16117.8H62A—C62—H62B108.1
C17—C16—H16117.8C62—C63—C64111.2 (4)
C16—C17—C18114.5 (19)C62—C63—H63A109.4
C16—C17—H17122.7C64—C63—H63A109.4
C18—C17—H17122.7C62—C63—H63B109.4
C13—C18—C17123.9 (17)C64—C63—H63B109.4
C13—C18—H18118.0H63A—C63—H63B108.0
C17—C18—H18118.0C63—C64—H64A109.5
C32—C31—N1116.5 (3)C63—C64—H64B109.5
C32—C31—H31A108.2H64A—C64—H64B109.5
N1—C31—H31A108.2C63—C64—H64C109.5
C32—C31—H31B108.2H64A—C64—H64C109.5
N1—C31—H31B108.2H64B—C64—H64C109.5
H31A—C31—H31B107.3
Symmetry code: (i) x+1, y, z+1/2.

Experimental details

Crystal data
Chemical formula(C16H36N)2[V2O2(O2)2(C8H6O3)2]·C8H8O3
Mr1135.20
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)150
a, b, c (Å)19.657 (12), 17.066 (3), 17.670 (5)
V3)5928 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.4 × 0.3 × 0.3
Data collection
Diffractometer4-circle κ-axis Kuma KM-4
diffractometer with Oxford Cryosytems Cryostream cooler
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5680, 5210, 3329
Rint0.023
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.168, 1.03
No. of reflections5210
No. of parameters383
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.66, 0.40

Computer programs: KM-4 Software (Galdecki et al., 1996), KM-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPIII (Johnson & Burnett, 1996), SHELXL97.

Selected geometric parameters (Å, º) top
V1—O11.579 (2)V1—O5i2.000 (2)
V1—O31.879 (2)C1—O41.290 (4)
V1—O21.880 (2)C1—C21.517 (5)
V1—O51.979 (2)O2—O31.432 (3)
V1—O41.991 (2)C2—O51.410 (4)
O1—V1—O3105.87 (12)O2—V1—O5i82.09 (10)
O1—V1—O2102.67 (12)O5—V1—O5i69.57 (10)
O3—V1—O244.80 (10)O4—V1—O5i144.53 (10)
O1—V1—O5100.65 (11)O4—C1—C2114.2 (3)
O3—V1—O5146.27 (10)O3—O2—V167.55 (13)
O2—V1—O5145.84 (10)C5—C2—C1112.0 (3)
O1—V1—O498.80 (12)O2—O3—V167.65 (13)
O3—V1—O478.20 (10)C1—O4—V1119.9 (2)
O2—V1—O4122.53 (11)C2—O5—V1119.08 (19)
O5—V1—O477.47 (9)C2—O5—V1i128.5 (2)
O1—V1—O5i99.78 (11)V1—O5—V1i105.58 (10)
O3—V1—O5i124.43 (10)
Symmetry code: (i) x+1, y, z+1/2.
 

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