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The title mononuclear oxovanadium(IV) complex, [VO(C36H38N2O2)], has a distorted square-pyramidal coordination. The complex was shown to be the exo isomer.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004534/qa0262sup1.cif
Contains datablocks vo3tb, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004534/qa0262Isup2.hkl
Contains datablock I

CCDC reference: 145635

Comment top

The crystal structure and the thermal isomerization of [VO(3-EtO-sal-meso-stien)] have been investigated by the authors (Hoshina et al., 1999), together with the thermal dehydrogenation in the solid state (Hoshina et al., 1998, 2000).

In the crystals of [VO(3-tBu,5-Me-salen)], (I), the complex has an asymmetric distortion with a tBu—C···C—tBu torsion angle of 25.1° (Cornman et al., 1997). Distortion of the title compound in the crystal is moderate and the C9—C8···C37—C38 torsion angle is 10.1 (3)°°.

Experimental top

To a hot methanol solution (50 ml) of vanadium(IV) oxide sulfate (0.25 g, 1 mmol) were added H2(3-tBu-sal-meso-stien) (0.53 g, 1 mmol) and pyridine (2 ml), and the mixture was stirred for 1 h at 333 K. The resulting green precipitate was collected by filtration and washed with ether (yield 80%). Found: C 72.34, H 6.52, N 4.72%; calculated for C36H38N2O3V: C 72.35, H 6.41, N 4.69%. An analysis of the product by high-performance liquid reverse-phase chromatography suggested that only one of two possible geometrical isomers had been obtained. Crystals of the title compound, exo-[VO(3-tBu-sal-meso-stien)], were grown from an acetonitrile solution.

Refinement top

All H-atom positional parameters were calculated geometrically, and fixed with Uiso(H) = 1.2Ueq(parent atom).

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN.

(I) top
Crystal data top
[VO(C36H38N2O2)]Dx = 1.268 Mg m3
Mr = 597.65Mo Kα radiation, λ = 0.71073 Å
Monoclinic, C2/cCell parameters from 25 reflections
a = 32.529 (4) Åθ = 14.8–15.0°
b = 11.877 (5) ŵ = 0.35 mm1
c = 18.909 (7) ÅT = 297 K
β = 121.01 (1)°Prismatic, green
V = 6261 (3) Å30.5 × 0.3 × 0.1 mm
Z = 8
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.045
θ–2θ scansθmax = 27.5°
Absorption correction: integration
(Coppens et al., 1965)
h = 4242
Tmin = 0.866, Tmax = 0.979k = 015
7427 measured reflectionsl = 250
7203 independent reflections3 standard reflections every 150 reflections
3823 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2H-atom parameters not refined
R[F2 > 2σ(F2)] = 0.061 w = 1/[σ2(Fo2) + (0.1616P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.219(Δ/σ)max = 0.0001
S = 1.18Δρmax = 0.81 e Å3
7203 reflectionsΔρmin = 0.73 e Å3
379 parameters
Crystal data top
[VO(C36H38N2O2)]V = 6261 (3) Å3
Mr = 597.65Z = 8
Monoclinic, C2/cMo Kα radiation
a = 32.529 (4) ŵ = 0.35 mm1
b = 11.877 (5) ÅT = 297 K
c = 18.909 (7) Å0.5 × 0.3 × 0.1 mm
β = 121.01 (1)°
Data collection top
Rigaku AFC-7R
diffractometer
3823 reflections with I > 2σ(I)
Absorption correction: integration
(Coppens et al., 1965)
Rint = 0.045
Tmin = 0.866, Tmax = 0.9793 standard reflections every 150 reflections
7427 measured reflections intensity decay: none
7203 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.061379 parameters
wR(F2) = 0.219H-atom parameters not refined
S = 1.18Δρmax = 0.81 e Å3
7203 reflectionsΔρmin = 0.73 e Å3
Special details top

Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
V10.21722 (2)0.13575 (6)0.69752 (4)0.0278 (2)
O20.2192 (1)0.0058 (3)0.7218 (2)0.0431 (8)
O30.1792 (1)0.1420 (3)0.5794 (2)0.0360 (7)
O40.1653 (1)0.2075 (3)0.7006 (2)0.0374 (7)
N50.2750 (1)0.1740 (3)0.6837 (2)0.0324 (8)
N60.2623 (1)0.2212 (3)0.8053 (2)0.0307 (8)
C70.1902 (2)0.1033 (4)0.5255 (3)0.0328 (9)
C80.1539 (2)0.0567 (4)0.4502 (3)0.0336 (10)
C90.1023 (2)0.0449 (4)0.4313 (3)0.038 (1)
C100.1023 (2)0.0336 (5)0.4959 (4)0.060 (2)
C110.0683 (2)0.0068 (5)0.3465 (3)0.058 (1)
C120.0829 (2)0.1609 (5)0.4333 (4)0.062 (2)
C130.1673 (2)0.0197 (4)0.3946 (3)0.043 (1)
C140.2140 (2)0.0315 (5)0.4097 (3)0.050 (1)
C150.2487 (2)0.0779 (5)0.4819 (3)0.045 (1)
C160.2381 (2)0.1124 (4)0.5421 (3)0.036 (1)
C170.2755 (2)0.1593 (4)0.6165 (3)0.039 (1)
C180.3156 (2)0.2385 (3)0.7512 (3)0.0326 (9)
C190.3649 (1)0.2139 (4)0.7657 (3)0.0354 (10)
C200.3795 (2)0.1071 (4)0.7592 (3)0.046 (1)
C210.4268 (2)0.0896 (5)0.7788 (4)0.063 (2)
C220.4594 (2)0.1775 (6)0.8074 (4)0.074 (2)
C230.4452 (2)0.2824 (6)0.8158 (4)0.072 (2)
C240.3979 (2)0.3008 (4)0.7933 (4)0.055 (1)
C250.3137 (2)0.2259 (3)0.8319 (3)0.0339 (9)
C260.3430 (1)0.1313 (4)0.8904 (3)0.0298 (9)
C270.3249 (2)0.0250 (4)0.8886 (3)0.041 (1)
C280.3528 (2)0.0566 (4)0.9459 (3)0.045 (1)
C290.3987 (2)0.0329 (5)1.0044 (3)0.049 (1)
C300.4184 (2)0.0708 (5)1.0072 (3)0.054 (1)
C310.3904 (2)0.1525 (4)0.9506 (3)0.043 (1)
C320.2494 (2)0.2722 (4)0.8513 (3)0.036 (1)
C330.2018 (2)0.2803 (4)0.8372 (3)0.0370 (10)
C340.1967 (2)0.3265 (5)0.9012 (3)0.050 (1)
C350.1533 (2)0.3366 (5)0.8929 (3)0.053 (1)
C360.1124 (2)0.3030 (4)0.8179 (3)0.044 (1)
C370.1145 (2)0.2602 (4)0.7517 (3)0.0324 (9)
C380.0690 (2)0.2289 (4)0.6702 (3)0.0353 (10)
C390.0700 (2)0.1052 (4)0.6490 (3)0.046 (1)
C400.0233 (2)0.2471 (5)0.6740 (3)0.048 (1)
C410.0646 (2)0.3041 (5)0.6004 (3)0.050 (1)
C420.1613 (2)0.2476 (4)0.7622 (3)0.0334 (10)
H10A0.11470.10740.49450.0693*
H10B0.07120.04440.48820.0693*
H10C0.12300.00510.55130.0693*
H11A0.07970.08150.34350.0657*
H11B0.06800.03780.30440.0657*
H11C0.03660.01470.33570.0657*
H12A0.10150.19580.48600.0672*
H12B0.05000.15560.42240.0672*
H12C0.08200.20850.39230.0672*
H130.14430.01420.34470.0596*
H140.22290.00770.37160.0618*
H150.28080.08480.49310.0540*
H170.30280.18400.61640.0479*
H180.30920.31490.73600.0423*
H200.35650.04540.73920.0585*
H210.43700.01900.77530.0830*
H220.49140.16620.82010.0914*
H230.46690.34360.83690.0840*
H240.38760.37450.79770.0675*
H250.32640.29290.86200.0427*
H270.29230.00860.84920.0542*
H280.34040.12940.94240.0535*
H290.41730.08781.04520.0569*
H300.45040.08521.04850.0641*
H310.40330.22470.95380.0508*
H320.27400.30970.89860.0464*
H340.22600.35090.95230.0579*
H350.15090.36960.93660.0672*
H360.08350.31340.81610.0570*
H39A0.09800.08860.64370.0568*
H39B0.07250.05520.69080.0568*
H39C0.04250.08200.59720.0568*
H40A0.00600.22850.62150.0631*
H40B0.01950.32540.68430.0631*
H40C0.02290.20280.71530.0631*
H41A0.06130.38210.60970.0599*
H41B0.09160.29650.59370.0599*
H41C0.03620.28480.54710.0599*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V10.0286 (4)0.0281 (4)0.0294 (4)0.0022 (3)0.0168 (3)0.0044 (3)
O20.056 (2)0.029 (2)0.044 (2)0.005 (1)0.026 (2)0.001 (1)
O30.030 (1)0.047 (2)0.033 (2)0.002 (1)0.018 (1)0.007 (1)
O40.034 (2)0.048 (2)0.036 (2)0.003 (1)0.023 (1)0.007 (1)
N50.032 (2)0.030 (2)0.036 (2)0.001 (1)0.018 (2)0.001 (2)
N60.032 (2)0.028 (2)0.031 (2)0.002 (1)0.015 (2)0.003 (2)
C70.040 (2)0.029 (2)0.034 (2)0.005 (2)0.023 (2)0.000 (2)
C80.043 (2)0.028 (2)0.031 (2)0.003 (2)0.020 (2)0.001 (2)
C90.031 (2)0.043 (3)0.035 (2)0.001 (2)0.012 (2)0.008 (2)
C100.058 (3)0.072 (4)0.054 (3)0.019 (3)0.031 (3)0.003 (3)
C110.051 (3)0.066 (4)0.042 (3)0.009 (3)0.013 (3)0.019 (3)
C120.037 (3)0.062 (4)0.065 (4)0.011 (2)0.010 (3)0.015 (3)
C130.048 (3)0.046 (3)0.031 (2)0.000 (2)0.017 (2)0.007 (2)
C140.062 (3)0.058 (3)0.041 (3)0.009 (3)0.034 (3)0.003 (2)
C150.041 (3)0.062 (3)0.044 (3)0.011 (2)0.029 (2)0.007 (2)
C160.042 (2)0.037 (3)0.036 (2)0.004 (2)0.025 (2)0.000 (2)
C170.040 (2)0.040 (3)0.049 (3)0.000 (2)0.032 (2)0.004 (2)
C180.032 (2)0.026 (2)0.039 (2)0.005 (2)0.018 (2)0.001 (2)
C190.025 (2)0.041 (3)0.038 (2)0.006 (2)0.015 (2)0.004 (2)
C200.038 (3)0.041 (3)0.063 (3)0.002 (2)0.028 (2)0.003 (2)
C210.051 (3)0.062 (4)0.083 (4)0.013 (3)0.040 (3)0.005 (3)
C220.020 (2)0.096 (5)0.101 (5)0.000 (3)0.028 (3)0.014 (4)
C230.034 (3)0.066 (4)0.103 (5)0.008 (3)0.025 (3)0.019 (4)
C240.034 (3)0.042 (3)0.079 (4)0.009 (2)0.023 (3)0.005 (3)
C250.032 (2)0.026 (2)0.040 (2)0.005 (2)0.016 (2)0.008 (2)
C260.026 (2)0.033 (2)0.032 (2)0.004 (2)0.016 (2)0.002 (2)
C270.030 (2)0.041 (3)0.052 (3)0.000 (2)0.021 (2)0.000 (2)
C280.042 (3)0.031 (2)0.062 (3)0.005 (2)0.026 (3)0.005 (2)
C290.055 (3)0.048 (3)0.042 (3)0.017 (2)0.024 (3)0.005 (2)
C300.047 (3)0.056 (3)0.038 (3)0.004 (2)0.007 (2)0.009 (2)
C310.035 (2)0.038 (3)0.044 (3)0.001 (2)0.012 (2)0.004 (2)
C320.035 (2)0.034 (2)0.037 (2)0.001 (2)0.017 (2)0.009 (2)
C330.043 (3)0.034 (2)0.038 (2)0.003 (2)0.024 (2)0.005 (2)
C340.054 (3)0.055 (3)0.041 (3)0.005 (2)0.024 (2)0.013 (2)
C350.061 (3)0.060 (4)0.050 (3)0.006 (3)0.038 (3)0.011 (3)
C360.050 (3)0.043 (3)0.056 (3)0.012 (2)0.038 (3)0.005 (2)
C370.039 (2)0.029 (2)0.039 (2)0.005 (2)0.027 (2)0.005 (2)
C380.030 (2)0.039 (2)0.041 (2)0.006 (2)0.021 (2)0.008 (2)
C390.045 (3)0.044 (3)0.050 (3)0.003 (2)0.025 (2)0.004 (2)
C400.033 (2)0.062 (3)0.060 (3)0.009 (2)0.032 (2)0.016 (3)
C410.046 (3)0.063 (3)0.043 (3)0.003 (2)0.024 (2)0.019 (3)
C420.042 (2)0.029 (2)0.040 (2)0.007 (2)0.029 (2)0.001 (2)
Geometric parameters (Å, º) top
V1—O21.601 (3)C21—H210.918
V1—O31.917 (3)C22—C231.37 (1)
V1—O41.918 (4)C22—H220.949
V1—N52.077 (5)C23—C241.387 (9)
V1—N62.063 (3)C23—H230.946
O3—C71.325 (7)C24—H240.956
O4—C421.326 (7)C25—C261.519 (6)
N5—C171.291 (8)C25—H250.942
N5—C181.491 (5)C26—C271.386 (7)
N6—C251.480 (6)C26—C311.388 (5)
N6—C321.294 (7)C27—C281.388 (6)
C7—C81.412 (5)C27—H270.949
C7—C161.428 (8)C28—C291.351 (6)
C8—C91.533 (8)C28—H280.943
C8—C131.400 (9)C29—C301.376 (8)
C9—C101.536 (9)C29—H290.952
C9—C111.531 (7)C30—C311.383 (7)
C9—C121.525 (8)C30—H300.942
C10—H10A0.972C31—H310.944
C10—H10B0.953C32—C331.433 (8)
C10—H10C0.969C32—H320.948
C11—H11A0.975C33—C341.415 (9)
C11—H11B0.953C33—C421.405 (5)
C11—H11C0.946C34—C351.342 (10)
C12—H12A0.954C34—H340.989
C12—H12B0.980C35—C361.413 (6)
C12—H12C0.948C35—H350.953
C13—C141.401 (9)C36—C371.384 (9)
C13—H130.940C36—H360.932
C14—C151.361 (6)C37—C381.533 (5)
C14—H140.947C37—C421.438 (8)
C15—C161.411 (9)C38—C391.529 (7)
C15—H150.953C38—C401.542 (8)
C16—C171.416 (6)C38—C411.538 (8)
C17—H170.937C39—H39A0.987
C18—C191.510 (7)C39—H39B0.958
C18—C251.564 (8)C39—H39C0.967
C18—H180.942C40—H40A0.983
C19—C201.383 (7)C40—H40B0.971
C19—C241.384 (7)C40—H40C0.946
C20—C211.398 (9)C41—H41A0.959
C20—H200.975C41—H41B0.956
C21—C221.385 (9)C41—H41C0.980
O2—V1—O3106.1 (1)C21—C22—C23119.7 (6)
O2—V1—O4109.0 (2)C21—C22—H22120.8
O2—V1—N5109.9 (2)C23—C22—H22119.4
O2—V1—N6106.7 (1)C22—C23—C24119.7 (5)
O3—V1—O488.2 (1)C22—C23—H23121.8
O3—V1—N585.9 (1)C24—C23—H23118.5
O3—V1—N6146.6 (1)C19—C24—C23121.4 (5)
O4—V1—N5140.7 (1)C19—C24—H24118.4
O4—V1—N686.6 (1)C23—C24—H24120.1
N5—V1—N677.8 (2)N6—C25—C18106.1 (3)
V1—O3—C7127.9 (2)N6—C25—C26113.2 (4)
V1—O4—C42132.3 (2)N6—C25—H25107.7
V1—N5—C17124.4 (3)C18—C25—C26117.2 (4)
V1—N5—C18117.6 (4)C18—C25—H25106.5
C17—N5—C18117.3 (4)C26—C25—H25105.6
V1—N6—C25117.3 (3)C25—C26—C27123.9 (3)
V1—N6—C32125.6 (3)C25—C26—C31118.5 (4)
C25—N6—C32117.1 (3)C27—C26—C31117.6 (4)
O3—C7—C8119.8 (5)C26—C27—C28121.2 (4)
O3—C7—C16120.1 (3)C26—C27—H27119.6
C8—C7—C16120.1 (5)C28—C27—H27119.1
C7—C8—C9121.1 (5)C27—C28—C29119.7 (5)
C7—C8—C13117.3 (5)C27—C28—H28120.0
C9—C8—C13121.6 (4)C29—C28—H28120.1
C8—C9—C10108.6 (4)C28—C29—C30120.9 (4)
C8—C9—C11113.2 (5)C28—C29—H29119.6
C8—C9—C12109.2 (4)C30—C29—H29119.5
C10—C9—C11107.1 (4)C29—C30—C31119.3 (4)
C10—C9—C12111.0 (6)C29—C30—H30119.4
C11—C9—C12107.6 (4)C31—C30—H30121.3
C9—C10—H10A110.8C26—C31—C30121.2 (5)
C9—C10—H10B113.3C26—C31—H31119.2
C9—C10—H10C111.3C30—C31—H31119.6
H10A—C10—H10B107.4N6—C32—C33126.8 (4)
H10A—C10—H10C106.1N6—C32—H32116.5
H10B—C10—H10C107.7C33—C32—H32116.6
C9—C11—H11A109.6C32—C33—C34117.3 (4)
C9—C11—H11B110.1C32—C33—C42122.1 (5)
C9—C11—H11C112.6C34—C33—C42120.6 (5)
H11A—C11—H11B107.2C33—C34—C35121.0 (4)
H11A—C11—H11C107.7C33—C34—H34117.9
H11B—C11—H11C109.5C35—C34—H34121.0
C9—C12—H12A111.7C34—C35—C36118.7 (6)
C9—C12—H12B110.9C34—C35—H35119.1
C9—C12—H12C110.9C36—C35—H35122.1
H12A—C12—H12B106.6C35—C36—C37123.6 (6)
H12A—C12—H12C109.3C35—C36—H36114.1
H12B—C12—H12C107.2C37—C36—H36122.3
C8—C13—C14122.6 (4)C36—C37—C38121.8 (5)
C8—C13—H13119.4C36—C37—C42117.1 (4)
C14—C13—H13117.9C38—C37—C42121.2 (5)
C13—C14—C15119.9 (6)C37—C38—C39110.9 (3)
C13—C14—H14122.6C37—C38—C40112.0 (5)
C15—C14—H14117.6C37—C38—C41109.7 (4)
C14—C15—C16120.3 (6)C39—C38—C40107.3 (4)
C14—C15—H15120.4C39—C38—C41109.8 (5)
C16—C15—H15119.2C40—C38—C41107.0 (4)
C7—C16—C15119.6 (4)C38—C39—H39A111.4
C7—C16—C17122.0 (5)C38—C39—H39B112.6
C15—C16—C17118.3 (5)C38—C39—H39C114.0
N5—C17—C16126.3 (5)H39A—C39—H39B105.8
N5—C17—H17116.9H39A—C39—H39C105.2
C16—C17—H17116.8H39B—C39—H39C107.4
N5—C18—C19116.4 (4)C38—C40—H40A112.1
N5—C18—C25108.9 (4)C38—C40—H40B111.6
N5—C18—H18106.0C38—C40—H40C112.5
C19—C18—C25112.0 (3)H40A—C40—H40B105.1
C19—C18—H18106.7H40A—C40—H40C107.1
C25—C18—H18106.1H40B—C40—H40C108.0
C18—C19—C20123.0 (4)C38—C41—H41A111.8
C18—C19—C24118.0 (4)C38—C41—H41B111.9
C20—C19—C24118.8 (5)C38—C41—H41C111.7
C19—C20—C21119.6 (5)H41A—C41—H41B108.2
C19—C20—H20119.5H41A—C41—H41C106.3
C21—C20—H20120.8H41B—C41—H41C106.5
C20—C21—C22120.6 (6)O4—C42—C33121.4 (5)
C20—C21—H21120.5O4—C42—C37119.6 (3)
C22—C21—H21118.8C33—C42—C37119.1 (5)

Experimental details

Crystal data
Chemical formula[VO(C36H38N2O2)]
Mr597.65
Crystal system, space groupMonoclinic, C2/c
Temperature (K)297
a, b, c (Å)32.529 (4), 11.877 (5), 18.909 (7)
β (°) 121.01 (1)
V3)6261 (3)
Z8
Radiation typeMo Kα
µ (mm1)0.35
Crystal size (mm)0.5 × 0.3 × 0.1
Data collection
DiffractometerRigaku AFC-7R
diffractometer
Absorption correctionIntegration
(Coppens et al., 1965)
Tmin, Tmax0.866, 0.979
No. of measured, independent and
observed [I > 2σ(I)] reflections
7427, 7203, 3823
Rint0.045
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.219, 1.18
No. of reflections7203
No. of parameters379
No. of restraints?
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.81, 0.73

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), TEXSAN.

Selected bond lengths (Å) top
V1—O21.601 (3)V1—N52.077 (5)
V1—O31.917 (3)V1—N62.063 (3)
V1—O41.918 (4)
 

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