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Acta Cryst. (2007). E63, m2391    [ doi:10.1107/S1600536807038275 ]

Dioxido{1-[(phenyl)(2-pyridyl)methylene]-4-(p-tolyl)thiosemicarbazonato}vanadium(V) dimethyl sulfoxide solvate

I. C. Mendes, N. L. Speziali and H. Beraldo

Abstract top

In the title compound, [V(C20H17N4S)O2]·C2H6OS, the organic ligand coordinates the metal atom in a tridentate manner via its azomethine nitrogen, thiolate sulfur and pyridyl (py) nitrogen atoms, resulting in two five-membered chelate rings. To match the steric requirements of coordination through the Npy-N-S chelating system, the 1-[(2-pyridyl)(phenyl)methylene]-4-(p-tolyl)thiosemicarbazonate ligand adopts a configuration different to that of the parent thiosemicarbazone. The V atom shows a distorted trigonal-bipyramidal coordination geometry.

Comment top

Thiosemicarbazones and their metal complexes are an important class of compounds with a wide range of pharmacological applications (Beraldo & Gambino, 2004). Vanadium complexes were found to present antimicrobial, antitumor and insulin-enhancing effects (Baran, 2000; Ahmad et al., 2006). Here we report the crystal strucuture of dioxovanadium(V) complex with 2-benzoylpyridine N(4)-(p-tolyl)thiosemicarbazone, [VO2(2Bz4pT)]·DMSO. 2-Benzoylpyridine N(4)-(p-tolyl)thiosemicarbazone (H2Bz4pT), crystallizes as the ZE isomer, where Z and E refer to the configuration around C7=N2 and C8—N3 bonds, respectively (Mendes et al., 2006). In the title complex, to match the steric requirements of coordination through the Npy—N—S chelating system, the deprotonated ligand adopts the EZ configuration (Fig. 1). The C8—N3 bond length changes from 1.361 (3) Å in the free base to 1.322 (5) Å in the complex due to deprotonation of N3 and formation of a new predominantly double bond. In turn, the C8—S1 bond changes from 1.653 (3) Å in H2Bz4pT to 1.738 (4) Å in the complex, in agreement with deprotonation at N3 and formation of a thiolate bond. Deprotonation of the ligand and subsequent coordination to the metal center influences also bond angles. Hence, the N2—N3—C8 bond angle changes from 120.5 (2)° in the free base to 112.1 (3)° in the complex, and N3—C8—S angle changes from 117.9 (2)° in the ligand to 125.0 (3)° in the complex. The atomic arrangement around the vanadium ion has a distorted trigonal bipyramidal geometry (Fig. 2): the interatomic angles in the equatorial plane are in the 111.1 (3)–127.1 (2)° range and the axial angle N1—V—S1 is 151.2 (1)°. The V=O bond distances of 1.606 (4)Å and 1.599 (4)Å are shorter than in the other 2-pyridine thiosemicarbazones vanadium complexes recently published (1.623–1.608 Å; Philip et al., 2005; Sreekanth et al., 2003). A single hydrogen bond was observed between N4—H4B and the oxygen atom from the DMSO molecule. The antifungal activities of the free base and the vanadium complex were evalueted against Candida albicans. The thiosemicarbazone proved to be better as antifungal agent than its vanadium complex, probably due to the bulkiness of the complex which does not facilitate its binding to the cell membrane.

Related literature top

For related literature, see: Ahmad et al. (2006); Baran (2000); Beraldo & Gambino (2004); Mendes et al. (2006); Philip et al. (2005); Sreekanth et al. (2003).

Experimental top

Synthesis of 2-benzoylpyridine N(4)-(p-tolyl) thiosemicarbazone has been reported recently (Mendes et al., 2006). The dioxovanadium(V) complex was obtained by mixing equimolar amounts (3 mmol) of the thiosemicarbazone with [VO(acac)2] (acac= acetylacetonate) in ethanol under reflux and stirring for 24 h. The obtained solid was washed with ethanol and ethyl ether and dried in vacuum·Yield 73%. Single crystals of the complex were growth from 1:9 DMSO/acetone solution.

Refinement top

All H atoms were located in a diffrence map. Nevertheless, their positions were calculated and refined using a riding model approximation, with distance restraints N—H = 0.86 Å, C—H = 0.93–0.96 Å, Uiso(H) = 1.5Ueq(C) for the methyl groups and Uiso(H) = 1.2Ueq(N,C) for the remaining H atoms.

Computing details top

Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The ZE and EZ configurational isomers of H2Bz4pT.
[Figure 2] Fig. 2. Molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Dioxido{1-[(phenyl)(2-pyridyl)methylene]-4-(p-\ tolyl)thiosemicarbazonato}vanadium(V) dimethyl sulfoxide solvate top
Crystal data top
[V(C20H17N4S)O2]·C2H6OSF000 = 2096
Mr = 506.5Dx = 1.418 Mg m−3
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 33 reflections
a = 13.9269 (13) Åθ = 6.4–11.4º
b = 15.399 (2) ŵ = 0.63 mm−1
c = 22.133 (4) ÅT = 298 (2) K
V = 4746.4 (12) Å3Prismatic, orange
Z = 80.2 × 0.2 × 0.2 mm
Data collection top
Siemens P4
diffractometer		Rint = 0.031
Radiation source: fine-focus sealed tubeθmax = 25.5º
Monochromator: graphiteθmin = 2.2º
T = 298(2) Kh = −13→16
ω/2θ scansk = −14→18
Absorption correction: nonel = −21→26
6630 measured reflections3 standard reflections
4420 independent reflections every 247 reflections
2706 reflections with I > 2σ(I) intensity decay: 4%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.165  w = 1/[σ2(Fo2) + (0.0577P)2 + 7.659P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
4420 reflectionsΔρmax = 0.85 e Å−3
289 parametersΔρmin = −0.59 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[V(C20H17N4S)O2]·C2H6OSV = 4746.4 (12) Å3
Mr = 506.5Z = 8
Orthorhombic, PbcaMo Kα
a = 13.9269 (13) ŵ = 0.63 mm−1
b = 15.399 (2) ÅT = 298 (2) K
c = 22.133 (4) Å0.2 × 0.2 × 0.2 mm
Data collection top
Siemens P4
diffractometer		Rint = 0.031
Absorption correction: none3 standard reflections
6630 measured reflections every 247 reflections
4420 independent reflections intensity decay: 4%
2706 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.059289 parameters
wR(F2) = 0.165H-atom parameters constrained
S = 1.02Δρmax = 0.85 e Å−3
4420 reflectionsΔρmin = −0.59 e Å−3
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 > 2sigma(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*/Ueq
S10.34368 (9)0.09146 (9)0.65651 (5)0.0561 (4)
V0.50439 (6)0.13499 (6)0.67446 (3)0.0491 (3)
O10.4814 (3)0.2109 (3)0.72207 (18)0.0966 (16)
O20.5450 (3)0.0505 (3)0.70781 (19)0.0936 (14)
N10.6366 (3)0.1836 (2)0.64408 (16)0.0479 (9)
C20.6489 (3)0.1988 (3)0.58420 (19)0.0435 (10)
C30.7355 (3)0.2282 (3)0.5620 (2)0.0529 (12)
H30.74290.23950.52100.064*
C40.8112 (4)0.2408 (4)0.6015 (2)0.0629 (14)
H40.87040.25960.58710.075*
C50.7987 (4)0.2256 (4)0.6614 (3)0.0682 (15)
H50.84920.23360.68830.082*
C60.7108 (4)0.1982 (4)0.6816 (2)0.0640 (15)
H60.70210.18950.72280.077*
C70.5650 (3)0.1763 (3)0.54705 (18)0.0364 (9)
N20.4935 (2)0.1421 (2)0.57668 (14)0.0362 (8)
N30.4155 (2)0.1158 (2)0.54342 (14)0.0374 (8)
C80.3450 (3)0.0871 (3)0.57804 (17)0.0364 (9)
N40.2660 (2)0.0531 (2)0.55245 (14)0.0400 (8)
H4B0.22200.03760.57760.048*
C90.2431 (3)0.0384 (3)0.49082 (18)0.0374 (9)
C100.1491 (3)0.0141 (3)0.4783 (2)0.0459 (11)
H100.10560.00740.50990.055*
C110.1198 (3)0.0000 (3)0.4202 (2)0.0528 (12)
H110.0566−0.01680.41310.063*
C120.1814 (4)0.0100 (3)0.3717 (2)0.0546 (13)
C130.2758 (3)0.0301 (3)0.3852 (2)0.0564 (13)
H130.31980.03410.35370.068*
C140.3074 (3)0.0445 (3)0.44336 (19)0.0475 (11)
H140.37140.05810.45060.057*
C150.1458 (4)−0.0011 (5)0.3077 (2)0.0866 (19)
H15A0.0786−0.01490.30820.130*
H15B0.1805−0.04720.28840.130*
H15C0.15560.05190.28570.130*
C160.5663 (3)0.1908 (3)0.48091 (18)0.0361 (9)
C170.5761 (3)0.2748 (3)0.4579 (2)0.0539 (12)
H170.58290.32130.48440.065*
C180.5759 (3)0.2896 (4)0.3967 (2)0.0612 (14)
H180.58290.34580.38190.073*
C190.5654 (3)0.2216 (4)0.3572 (2)0.0605 (14)
H190.56470.23170.31580.073*
C200.5559 (3)0.1383 (3)0.3789 (2)0.0527 (12)
H200.54920.09230.35200.063*
C210.5564 (3)0.1225 (3)0.44055 (18)0.0414 (10)
H210.55010.06600.45490.050*
S2A0.90467 (10)0.09940 (10)0.35510 (7)0.0709 (4)
O1A0.8871 (2)0.0091 (2)0.37672 (15)0.0626 (9)
C1A0.8368 (5)0.1666 (4)0.4021 (3)0.102 (2)
H1AA0.86610.16920.44140.152*
H1AB0.77290.14370.40580.152*
H1AC0.83400.22390.38510.152*
C2A0.8358 (7)0.1097 (5)0.2909 (3)0.127 (3)
H2AA0.86270.07470.25930.191*
H2AB0.83490.16940.27840.191*
H2AC0.77150.09080.29920.191*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0483 (7)0.0871 (10)0.0330 (6)−0.0164 (7)0.0038 (5)0.0001 (6)
V0.0433 (4)0.0734 (6)0.0307 (4)−0.0005 (4)−0.0021 (3)−0.0039 (4)
O10.064 (3)0.147 (4)0.079 (3)−0.018 (3)0.008 (2)−0.067 (3)
O20.058 (2)0.139 (4)0.084 (3)0.005 (3)0.002 (2)0.055 (3)
N10.046 (2)0.059 (2)0.038 (2)−0.0004 (19)−0.0084 (17)−0.0110 (18)
C20.042 (3)0.045 (3)0.043 (2)−0.002 (2)−0.005 (2)−0.009 (2)
C30.042 (3)0.063 (3)0.054 (3)−0.009 (2)−0.002 (2)−0.006 (2)
C40.043 (3)0.073 (4)0.073 (4)−0.012 (3)−0.006 (3)−0.010 (3)
C50.048 (3)0.087 (4)0.070 (4)−0.007 (3)−0.016 (3)−0.021 (3)
C60.061 (3)0.088 (4)0.044 (3)−0.003 (3)−0.012 (2)−0.015 (3)
C70.036 (2)0.032 (2)0.041 (2)−0.0014 (18)−0.0018 (19)−0.0046 (18)
N20.0353 (18)0.0397 (19)0.0336 (17)−0.0065 (16)−0.0016 (15)−0.0045 (15)
N30.0336 (19)0.049 (2)0.0294 (17)−0.0089 (16)−0.0014 (15)−0.0025 (15)
C80.040 (2)0.037 (2)0.032 (2)−0.0009 (19)0.0031 (19)0.0002 (18)
N40.0331 (19)0.053 (2)0.0337 (18)−0.0111 (17)0.0018 (15)0.0016 (16)
C90.040 (2)0.033 (2)0.039 (2)−0.0012 (19)−0.0027 (19)−0.0002 (18)
C100.036 (2)0.054 (3)0.047 (2)−0.007 (2)0.001 (2)0.000 (2)
C110.041 (3)0.067 (3)0.051 (3)−0.006 (2)−0.014 (2)−0.009 (2)
C120.061 (3)0.061 (3)0.042 (3)0.000 (3)−0.012 (2)−0.005 (2)
C130.050 (3)0.078 (4)0.041 (3)−0.007 (3)0.004 (2)−0.008 (2)
C140.035 (2)0.065 (3)0.043 (2)−0.008 (2)−0.001 (2)−0.006 (2)
C150.082 (4)0.130 (5)0.048 (3)−0.010 (4)−0.015 (3)−0.016 (3)
C160.028 (2)0.039 (2)0.041 (2)−0.0061 (18)−0.0005 (17)0.0006 (19)
C170.053 (3)0.045 (3)0.063 (3)−0.011 (2)0.000 (2)0.003 (2)
C180.052 (3)0.060 (3)0.072 (4)−0.007 (3)−0.002 (3)0.028 (3)
C190.048 (3)0.092 (4)0.041 (3)−0.006 (3)0.000 (2)0.020 (3)
C200.049 (3)0.070 (3)0.039 (2)−0.005 (3)0.001 (2)−0.007 (2)
C210.040 (2)0.045 (3)0.040 (2)−0.005 (2)0.0011 (19)0.001 (2)
S2A0.0606 (9)0.0785 (10)0.0736 (9)−0.0067 (8)0.0075 (7)0.0188 (8)
O1A0.054 (2)0.062 (2)0.072 (2)−0.0053 (17)0.0155 (17)0.0183 (18)
C1A0.125 (6)0.063 (4)0.116 (6)−0.003 (4)0.021 (5)−0.018 (4)
C2A0.175 (9)0.114 (6)0.093 (5)−0.011 (6)−0.041 (6)0.014 (5)
Geometric parameters (Å, °) top
S1—C81.738 (4)C11—H110.9300
S1—V2.3699 (14)C12—C131.383 (7)
V—O21.599 (4)C12—C151.512 (6)
V—O11.606 (4)C13—C141.379 (6)
V—N12.099 (4)C13—H130.9300
V—N22.172 (3)C14—H140.9300
N1—C61.344 (6)C15—H15A0.9600
N1—C21.357 (5)C15—H15B0.9600
C2—C31.379 (6)C15—H15C0.9600
C2—C71.469 (6)C16—C211.387 (6)
C3—C41.384 (6)C16—C171.397 (6)
C3—H30.9300C17—C181.375 (7)
C4—C51.357 (7)C17—H170.9300
C4—H40.9300C18—C191.372 (7)
C5—C61.370 (7)C18—H180.9300
C5—H50.9300C19—C201.375 (7)
C6—H60.9300C19—H190.9300
C7—N21.304 (5)C20—C211.386 (6)
C7—C161.481 (6)C20—H200.9300
N2—N31.374 (4)C21—H210.9300
N3—C81.322 (5)S2A—O1A1.491 (4)
C8—N41.344 (5)S2A—C2A1.722 (7)
N4—C91.418 (5)S2A—C1A1.746 (6)
N4—H4B0.8600C1A—H1AA0.9600
C9—C141.383 (6)C1A—H1AB0.9600
C9—C101.390 (6)C1A—H1AC0.9600
C10—C111.367 (6)C2A—H2AA0.9600
C10—H100.9300C2A—H2AB0.9600
C11—C121.384 (7)C2A—H2AC0.9600
C8—S1—V99.71 (15)C12—C11—H11119.1
O2—V—O1111.1 (3)C13—C12—C11116.6 (4)
O2—V—N197.32 (18)C13—C12—C15122.7 (5)
O1—V—N197.21 (18)C11—C12—C15120.8 (5)
O2—V—N2121.7 (2)C14—C13—C12122.7 (4)
O1—V—N2127.1 (2)C14—C13—H13118.6
N1—V—N273.97 (13)C12—C13—H13118.6
O2—V—S1100.46 (16)C13—C14—C9119.5 (4)
O1—V—S197.33 (14)C13—C14—H14120.3
N1—V—S1151.15 (10)C9—C14—H14120.3
N2—V—S177.38 (9)C12—C15—H15A109.5
C6—N1—C2118.5 (4)C12—C15—H15B109.5
C6—N1—V122.4 (3)H15A—C15—H15B109.5
C2—N1—V119.0 (3)C12—C15—H15C109.5
N1—C2—C3121.0 (4)H15A—C15—H15C109.5
N1—C2—C7114.0 (4)H15B—C15—H15C109.5
C3—C2—C7125.0 (4)C21—C16—C17118.5 (4)
C2—C3—C4119.2 (5)C21—C16—C7121.4 (4)
C2—C3—H3120.4C17—C16—C7120.1 (4)
C4—C3—H3120.4C18—C17—C16120.8 (5)
C5—C4—C3119.6 (5)C18—C17—H17119.6
C5—C4—H4120.2C16—C17—H17119.6
C3—C4—H4120.2C19—C18—C17120.1 (5)
C4—C5—C6119.1 (5)C19—C18—H18120.0
C4—C5—H5120.4C17—C18—H18120.0
C6—C5—H5120.4C18—C19—C20120.0 (4)
N1—C6—C5122.5 (5)C18—C19—H19120.0
N1—C6—H6118.8C20—C19—H19120.0
C5—C6—H6118.8C19—C20—C21120.5 (5)
N2—C7—C2114.9 (4)C19—C20—H20119.8
N2—C7—C16124.5 (3)C21—C20—H20119.8
C2—C7—C16120.6 (4)C20—C21—C16120.0 (4)
C7—N2—N3117.0 (3)C20—C21—H21120.0
C7—N2—V117.9 (3)C16—C21—H21120.0
N3—N2—V125.0 (2)O1A—S2A—C2A105.0 (3)
C8—N3—N2112.1 (3)O1A—S2A—C1A105.8 (3)
N3—C8—N4119.6 (3)C2A—S2A—C1A97.8 (4)
N3—C8—S1125.0 (3)S2A—C1A—H1AA109.5
N4—C8—S1115.3 (3)S2A—C1A—H1AB109.5
C8—N4—C9130.6 (3)H1AA—C1A—H1AB109.5
C8—N4—H4B114.7S2A—C1A—H1AC109.5
C9—N4—H4B114.7H1AA—C1A—H1AC109.5
C14—C9—C10118.5 (4)H1AB—C1A—H1AC109.5
C14—C9—N4125.1 (4)S2A—C2A—H2AA109.5
C10—C9—N4116.4 (4)S2A—C2A—H2AB109.5
C11—C10—C9120.7 (4)H2AA—C2A—H2AB109.5
C11—C10—H10119.6S2A—C2A—H2AC109.5
C9—C10—H10119.6H2AA—C2A—H2AC109.5
C10—C11—C12121.8 (4)H2AB—C2A—H2AC109.5
C10—C11—H11119.1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4B···O1Ai0.861.962.814 (4)170
Symmetry codes: (i) −x+1, −y, −z+1.
Selected geometric parameters (Å, °) top
S1—C81.738 (4)V—N12.099 (4)
S1—V2.3699 (14)V—N22.172 (3)
V—O21.599 (4)N3—C81.322 (5)
V—O11.606 (4)
O2—V—O1111.1 (3)N1—V—S1151.15 (10)
O2—V—N2121.7 (2)C8—N3—N2112.1 (3)
O1—V—N2127.1 (2)N3—C8—S1125.0 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4B···O1Ai0.861.962.814 (4)170
Symmetry codes: (i) −x+1, −y, −z+1.
Acknowledgements top

This work was partially supported by the Brazilian agencies CNPq and Instituto do Milênio-Inovação e Desenvolvimento de Novos Fármacos e Medicamentos (IM-INOFAR).

references
References top

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