Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038275/gk2096sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038275/gk2096Isup2.hkl |
CCDC reference: 660145
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.007 Å
- R factor = 0.059
- wR factor = 0.165
- Data-to-parameter ratio = 15.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for V PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for S2A PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C15 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 6
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for V (4) 4.94
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
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).
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.
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.
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.
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).
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).
[V(C20H17N4S)O2]·C2H6OS | F(000) = 2096 |
Mr = 506.5 | Dx = 1.418 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 33 reflections |
a = 13.9269 (13) Å | θ = 6.4–11.4° |
b = 15.399 (2) Å | µ = 0.63 mm−1 |
c = 22.133 (4) Å | T = 298 K |
V = 4746.4 (12) Å3 | Prismatic, orange |
Z = 8 | 0.2 × 0.2 × 0.2 mm |
Siemens P4 diffractometer | Rint = 0.031 |
Radiation source: fine-focus sealed tube | θmax = 25.5°, θmin = 2.2° |
Graphite monochromator | h = −13→16 |
ω/2θ scans | k = −14→18 |
6630 measured reflections | l = −21→26 |
4420 independent reflections | 3 standard reflections every 247 reflections |
2706 reflections with I > 2σ(I) | intensity decay: 4% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0577P)2 + 7.659P] where P = (Fo2 + 2Fc2)/3 |
4420 reflections | (Δ/σ)max = 0.001 |
289 parameters | Δρmax = 0.85 e Å−3 |
0 restraints | Δρmin = −0.59 e Å−3 |
[V(C20H17N4S)O2]·C2H6OS | V = 4746.4 (12) Å3 |
Mr = 506.5 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.9269 (13) Å | µ = 0.63 mm−1 |
b = 15.399 (2) Å | T = 298 K |
c = 22.133 (4) Å | 0.2 × 0.2 × 0.2 mm |
Siemens P4 diffractometer | Rint = 0.031 |
6630 measured reflections | 3 standard reflections every 247 reflections |
4420 independent reflections | intensity decay: 4% |
2706 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.85 e Å−3 |
4420 reflections | Δρmin = −0.59 e Å−3 |
289 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.34368 (9) | 0.09146 (9) | 0.65651 (5) | 0.0561 (4) | |
V | 0.50439 (6) | 0.13499 (6) | 0.67446 (3) | 0.0491 (3) | |
O1 | 0.4814 (3) | 0.2109 (3) | 0.72207 (18) | 0.0966 (16) | |
O2 | 0.5450 (3) | 0.0505 (3) | 0.70781 (19) | 0.0936 (14) | |
N1 | 0.6366 (3) | 0.1836 (2) | 0.64408 (16) | 0.0479 (9) | |
C2 | 0.6489 (3) | 0.1988 (3) | 0.58420 (19) | 0.0435 (10) | |
C3 | 0.7355 (3) | 0.2282 (3) | 0.5620 (2) | 0.0529 (12) | |
H3 | 0.7429 | 0.2395 | 0.5210 | 0.064* | |
C4 | 0.8112 (4) | 0.2408 (4) | 0.6015 (2) | 0.0629 (14) | |
H4 | 0.8704 | 0.2596 | 0.5871 | 0.075* | |
C5 | 0.7987 (4) | 0.2256 (4) | 0.6614 (3) | 0.0682 (15) | |
H5 | 0.8492 | 0.2336 | 0.6883 | 0.082* | |
C6 | 0.7108 (4) | 0.1982 (4) | 0.6816 (2) | 0.0640 (15) | |
H6 | 0.7021 | 0.1895 | 0.7228 | 0.077* | |
C7 | 0.5650 (3) | 0.1763 (3) | 0.54705 (18) | 0.0364 (9) | |
N2 | 0.4935 (2) | 0.1421 (2) | 0.57668 (14) | 0.0362 (8) | |
N3 | 0.4155 (2) | 0.1158 (2) | 0.54342 (14) | 0.0374 (8) | |
C8 | 0.3450 (3) | 0.0871 (3) | 0.57804 (17) | 0.0364 (9) | |
N4 | 0.2660 (2) | 0.0531 (2) | 0.55245 (14) | 0.0400 (8) | |
H4B | 0.2220 | 0.0376 | 0.5776 | 0.048* | |
C9 | 0.2431 (3) | 0.0384 (3) | 0.49082 (18) | 0.0374 (9) | |
C10 | 0.1491 (3) | 0.0141 (3) | 0.4783 (2) | 0.0459 (11) | |
H10 | 0.1056 | 0.0074 | 0.5099 | 0.055* | |
C11 | 0.1198 (3) | 0.0000 (3) | 0.4202 (2) | 0.0528 (12) | |
H11 | 0.0566 | −0.0168 | 0.4131 | 0.063* | |
C12 | 0.1814 (4) | 0.0100 (3) | 0.3717 (2) | 0.0546 (13) | |
C13 | 0.2758 (3) | 0.0301 (3) | 0.3852 (2) | 0.0564 (13) | |
H13 | 0.3198 | 0.0341 | 0.3537 | 0.068* | |
C14 | 0.3074 (3) | 0.0445 (3) | 0.44336 (19) | 0.0475 (11) | |
H14 | 0.3714 | 0.0581 | 0.4506 | 0.057* | |
C15 | 0.1458 (4) | −0.0011 (5) | 0.3077 (2) | 0.0866 (19) | |
H15A | 0.0786 | −0.0149 | 0.3082 | 0.130* | |
H15B | 0.1805 | −0.0472 | 0.2884 | 0.130* | |
H15C | 0.1556 | 0.0519 | 0.2857 | 0.130* | |
C16 | 0.5663 (3) | 0.1908 (3) | 0.48091 (18) | 0.0361 (9) | |
C17 | 0.5761 (3) | 0.2748 (3) | 0.4579 (2) | 0.0539 (12) | |
H17 | 0.5829 | 0.3213 | 0.4844 | 0.065* | |
C18 | 0.5759 (3) | 0.2896 (4) | 0.3967 (2) | 0.0612 (14) | |
H18 | 0.5829 | 0.3458 | 0.3819 | 0.073* | |
C19 | 0.5654 (3) | 0.2216 (4) | 0.3572 (2) | 0.0605 (14) | |
H19 | 0.5647 | 0.2317 | 0.3158 | 0.073* | |
C20 | 0.5559 (3) | 0.1383 (3) | 0.3789 (2) | 0.0527 (12) | |
H20 | 0.5492 | 0.0923 | 0.3520 | 0.063* | |
C21 | 0.5564 (3) | 0.1225 (3) | 0.44055 (18) | 0.0414 (10) | |
H21 | 0.5501 | 0.0660 | 0.4549 | 0.050* | |
S2A | 0.90467 (10) | 0.09940 (10) | 0.35510 (7) | 0.0709 (4) | |
O1A | 0.8871 (2) | 0.0091 (2) | 0.37672 (15) | 0.0626 (9) | |
C1A | 0.8368 (5) | 0.1666 (4) | 0.4021 (3) | 0.102 (2) | |
H1AA | 0.8661 | 0.1692 | 0.4414 | 0.152* | |
H1AB | 0.7729 | 0.1437 | 0.4058 | 0.152* | |
H1AC | 0.8340 | 0.2239 | 0.3851 | 0.152* | |
C2A | 0.8358 (7) | 0.1097 (5) | 0.2909 (3) | 0.127 (3) | |
H2AA | 0.8627 | 0.0747 | 0.2593 | 0.191* | |
H2AB | 0.8349 | 0.1694 | 0.2784 | 0.191* | |
H2AC | 0.7715 | 0.0908 | 0.2992 | 0.191* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0483 (7) | 0.0871 (10) | 0.0330 (6) | −0.0164 (7) | 0.0038 (5) | 0.0001 (6) |
V | 0.0433 (4) | 0.0734 (6) | 0.0307 (4) | −0.0005 (4) | −0.0021 (3) | −0.0039 (4) |
O1 | 0.064 (3) | 0.147 (4) | 0.079 (3) | −0.018 (3) | 0.008 (2) | −0.067 (3) |
O2 | 0.058 (2) | 0.139 (4) | 0.084 (3) | 0.005 (3) | 0.002 (2) | 0.055 (3) |
N1 | 0.046 (2) | 0.059 (2) | 0.038 (2) | −0.0004 (19) | −0.0084 (17) | −0.0110 (18) |
C2 | 0.042 (3) | 0.045 (3) | 0.043 (2) | −0.002 (2) | −0.005 (2) | −0.009 (2) |
C3 | 0.042 (3) | 0.063 (3) | 0.054 (3) | −0.009 (2) | −0.002 (2) | −0.006 (2) |
C4 | 0.043 (3) | 0.073 (4) | 0.073 (4) | −0.012 (3) | −0.006 (3) | −0.010 (3) |
C5 | 0.048 (3) | 0.087 (4) | 0.070 (4) | −0.007 (3) | −0.016 (3) | −0.021 (3) |
C6 | 0.061 (3) | 0.088 (4) | 0.044 (3) | −0.003 (3) | −0.012 (2) | −0.015 (3) |
C7 | 0.036 (2) | 0.032 (2) | 0.041 (2) | −0.0014 (18) | −0.0018 (19) | −0.0046 (18) |
N2 | 0.0353 (18) | 0.0397 (19) | 0.0336 (17) | −0.0065 (16) | −0.0016 (15) | −0.0045 (15) |
N3 | 0.0336 (19) | 0.049 (2) | 0.0294 (17) | −0.0089 (16) | −0.0014 (15) | −0.0025 (15) |
C8 | 0.040 (2) | 0.037 (2) | 0.032 (2) | −0.0009 (19) | 0.0031 (19) | 0.0002 (18) |
N4 | 0.0331 (19) | 0.053 (2) | 0.0337 (18) | −0.0111 (17) | 0.0018 (15) | 0.0016 (16) |
C9 | 0.040 (2) | 0.033 (2) | 0.039 (2) | −0.0012 (19) | −0.0027 (19) | −0.0002 (18) |
C10 | 0.036 (2) | 0.054 (3) | 0.047 (2) | −0.007 (2) | 0.001 (2) | 0.000 (2) |
C11 | 0.041 (3) | 0.067 (3) | 0.051 (3) | −0.006 (2) | −0.014 (2) | −0.009 (2) |
C12 | 0.061 (3) | 0.061 (3) | 0.042 (3) | 0.000 (3) | −0.012 (2) | −0.005 (2) |
C13 | 0.050 (3) | 0.078 (4) | 0.041 (3) | −0.007 (3) | 0.004 (2) | −0.008 (2) |
C14 | 0.035 (2) | 0.065 (3) | 0.043 (2) | −0.008 (2) | −0.001 (2) | −0.006 (2) |
C15 | 0.082 (4) | 0.130 (5) | 0.048 (3) | −0.010 (4) | −0.015 (3) | −0.016 (3) |
C16 | 0.028 (2) | 0.039 (2) | 0.041 (2) | −0.0061 (18) | −0.0005 (17) | 0.0006 (19) |
C17 | 0.053 (3) | 0.045 (3) | 0.063 (3) | −0.011 (2) | 0.000 (2) | 0.003 (2) |
C18 | 0.052 (3) | 0.060 (3) | 0.072 (4) | −0.007 (3) | −0.002 (3) | 0.028 (3) |
C19 | 0.048 (3) | 0.092 (4) | 0.041 (3) | −0.006 (3) | 0.000 (2) | 0.020 (3) |
C20 | 0.049 (3) | 0.070 (3) | 0.039 (2) | −0.005 (3) | 0.001 (2) | −0.007 (2) |
C21 | 0.040 (2) | 0.045 (3) | 0.040 (2) | −0.005 (2) | 0.0011 (19) | 0.001 (2) |
S2A | 0.0606 (9) | 0.0785 (10) | 0.0736 (9) | −0.0067 (8) | 0.0075 (7) | 0.0188 (8) |
O1A | 0.054 (2) | 0.062 (2) | 0.072 (2) | −0.0053 (17) | 0.0155 (17) | 0.0183 (18) |
C1A | 0.125 (6) | 0.063 (4) | 0.116 (6) | −0.003 (4) | 0.021 (5) | −0.018 (4) |
C2A | 0.175 (9) | 0.114 (6) | 0.093 (5) | −0.011 (6) | −0.041 (6) | 0.014 (5) |
S1—C8 | 1.738 (4) | C11—H11 | 0.9300 |
S1—V | 2.3699 (14) | C12—C13 | 1.383 (7) |
V—O2 | 1.599 (4) | C12—C15 | 1.512 (6) |
V—O1 | 1.606 (4) | C13—C14 | 1.379 (6) |
V—N1 | 2.099 (4) | C13—H13 | 0.9300 |
V—N2 | 2.172 (3) | C14—H14 | 0.9300 |
N1—C6 | 1.344 (6) | C15—H15A | 0.9600 |
N1—C2 | 1.357 (5) | C15—H15B | 0.9600 |
C2—C3 | 1.379 (6) | C15—H15C | 0.9600 |
C2—C7 | 1.469 (6) | C16—C21 | 1.387 (6) |
C3—C4 | 1.384 (6) | C16—C17 | 1.397 (6) |
C3—H3 | 0.9300 | C17—C18 | 1.375 (7) |
C4—C5 | 1.357 (7) | C17—H17 | 0.9300 |
C4—H4 | 0.9300 | C18—C19 | 1.372 (7) |
C5—C6 | 1.370 (7) | C18—H18 | 0.9300 |
C5—H5 | 0.9300 | C19—C20 | 1.375 (7) |
C6—H6 | 0.9300 | C19—H19 | 0.9300 |
C7—N2 | 1.304 (5) | C20—C21 | 1.386 (6) |
C7—C16 | 1.481 (6) | C20—H20 | 0.9300 |
N2—N3 | 1.374 (4) | C21—H21 | 0.9300 |
N3—C8 | 1.322 (5) | S2A—O1A | 1.491 (4) |
C8—N4 | 1.344 (5) | S2A—C2A | 1.722 (7) |
N4—C9 | 1.418 (5) | S2A—C1A | 1.746 (6) |
N4—H4B | 0.8600 | C1A—H1AA | 0.9600 |
C9—C14 | 1.383 (6) | C1A—H1AB | 0.9600 |
C9—C10 | 1.390 (6) | C1A—H1AC | 0.9600 |
C10—C11 | 1.367 (6) | C2A—H2AA | 0.9600 |
C10—H10 | 0.9300 | C2A—H2AB | 0.9600 |
C11—C12 | 1.384 (7) | C2A—H2AC | 0.9600 |
C8—S1—V | 99.71 (15) | C12—C11—H11 | 119.1 |
O2—V—O1 | 111.1 (3) | C13—C12—C11 | 116.6 (4) |
O2—V—N1 | 97.32 (18) | C13—C12—C15 | 122.7 (5) |
O1—V—N1 | 97.21 (18) | C11—C12—C15 | 120.8 (5) |
O2—V—N2 | 121.7 (2) | C14—C13—C12 | 122.7 (4) |
O1—V—N2 | 127.1 (2) | C14—C13—H13 | 118.6 |
N1—V—N2 | 73.97 (13) | C12—C13—H13 | 118.6 |
O2—V—S1 | 100.46 (16) | C13—C14—C9 | 119.5 (4) |
O1—V—S1 | 97.33 (14) | C13—C14—H14 | 120.3 |
N1—V—S1 | 151.15 (10) | C9—C14—H14 | 120.3 |
N2—V—S1 | 77.38 (9) | C12—C15—H15A | 109.5 |
C6—N1—C2 | 118.5 (4) | C12—C15—H15B | 109.5 |
C6—N1—V | 122.4 (3) | H15A—C15—H15B | 109.5 |
C2—N1—V | 119.0 (3) | C12—C15—H15C | 109.5 |
N1—C2—C3 | 121.0 (4) | H15A—C15—H15C | 109.5 |
N1—C2—C7 | 114.0 (4) | H15B—C15—H15C | 109.5 |
C3—C2—C7 | 125.0 (4) | C21—C16—C17 | 118.5 (4) |
C2—C3—C4 | 119.2 (5) | C21—C16—C7 | 121.4 (4) |
C2—C3—H3 | 120.4 | C17—C16—C7 | 120.1 (4) |
C4—C3—H3 | 120.4 | C18—C17—C16 | 120.8 (5) |
C5—C4—C3 | 119.6 (5) | C18—C17—H17 | 119.6 |
C5—C4—H4 | 120.2 | C16—C17—H17 | 119.6 |
C3—C4—H4 | 120.2 | C19—C18—C17 | 120.1 (5) |
C4—C5—C6 | 119.1 (5) | C19—C18—H18 | 120.0 |
C4—C5—H5 | 120.4 | C17—C18—H18 | 120.0 |
C6—C5—H5 | 120.4 | C18—C19—C20 | 120.0 (4) |
N1—C6—C5 | 122.5 (5) | C18—C19—H19 | 120.0 |
N1—C6—H6 | 118.8 | C20—C19—H19 | 120.0 |
C5—C6—H6 | 118.8 | C19—C20—C21 | 120.5 (5) |
N2—C7—C2 | 114.9 (4) | C19—C20—H20 | 119.8 |
N2—C7—C16 | 124.5 (3) | C21—C20—H20 | 119.8 |
C2—C7—C16 | 120.6 (4) | C20—C21—C16 | 120.0 (4) |
C7—N2—N3 | 117.0 (3) | C20—C21—H21 | 120.0 |
C7—N2—V | 117.9 (3) | C16—C21—H21 | 120.0 |
N3—N2—V | 125.0 (2) | O1A—S2A—C2A | 105.0 (3) |
C8—N3—N2 | 112.1 (3) | O1A—S2A—C1A | 105.8 (3) |
N3—C8—N4 | 119.6 (3) | C2A—S2A—C1A | 97.8 (4) |
N3—C8—S1 | 125.0 (3) | S2A—C1A—H1AA | 109.5 |
N4—C8—S1 | 115.3 (3) | S2A—C1A—H1AB | 109.5 |
C8—N4—C9 | 130.6 (3) | H1AA—C1A—H1AB | 109.5 |
C8—N4—H4B | 114.7 | S2A—C1A—H1AC | 109.5 |
C9—N4—H4B | 114.7 | H1AA—C1A—H1AC | 109.5 |
C14—C9—C10 | 118.5 (4) | H1AB—C1A—H1AC | 109.5 |
C14—C9—N4 | 125.1 (4) | S2A—C2A—H2AA | 109.5 |
C10—C9—N4 | 116.4 (4) | S2A—C2A—H2AB | 109.5 |
C11—C10—C9 | 120.7 (4) | H2AA—C2A—H2AB | 109.5 |
C11—C10—H10 | 119.6 | S2A—C2A—H2AC | 109.5 |
C9—C10—H10 | 119.6 | H2AA—C2A—H2AC | 109.5 |
C10—C11—C12 | 121.8 (4) | H2AB—C2A—H2AC | 109.5 |
C10—C11—H11 | 119.1 |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4B···O1Ai | 0.86 | 1.96 | 2.814 (4) | 170 |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [V(C20H17N4S)O2]·C2H6OS |
Mr | 506.5 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 298 |
a, b, c (Å) | 13.9269 (13), 15.399 (2), 22.133 (4) |
V (Å3) | 4746.4 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.63 |
Crystal size (mm) | 0.2 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Siemens P4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6630, 4420, 2706 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.165, 1.02 |
No. of reflections | 4420 |
No. of parameters | 289 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.85, −0.59 |
Computer programs: XSCANS (Siemens, 1991), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
S1—C8 | 1.738 (4) | V—N1 | 2.099 (4) |
S1—V | 2.3699 (14) | V—N2 | 2.172 (3) |
V—O2 | 1.599 (4) | N3—C8 | 1.322 (5) |
V—O1 | 1.606 (4) | ||
O2—V—O1 | 111.1 (3) | N1—V—S1 | 151.15 (10) |
O2—V—N2 | 121.7 (2) | C8—N3—N2 | 112.1 (3) |
O1—V—N2 | 127.1 (2) | N3—C8—S1 | 125.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4B···O1Ai | 0.86 | 1.96 | 2.814 (4) | 170 |
Symmetry code: (i) −x+1, −y, −z+1. |
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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.