Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105030337/ga1108sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105030337/ga1108Isup2.hkl |
CCDC reference: 290563
The di-2-pyridyl ketone N4,N4-(butane-1,4-diyl)thiosemicarbazone ligand was prepared as described by Usman et al. (2002). A solution of the ligand (5 mmol) dissolved in dichloromethane (20 ml) was mixed with an equimolar amount of vanadyl(IV) acetylacetonate dissolved in the same solvent (10 ml). The mixture was stirred for 24 h and the resulting solution was allowed to stand at room temperature. After slow evaporation, orange–red crystals of the complex separated out; these were collected by filtration, washed with ether and dried over P4O10 in vacuo. Single crystals suitable for X-ray diffraction were collected by slow evaporation of a solution in a 1:1 mixture of methanol and dichloromethane. Elemental analysis found: C 48.9, H 4.16, N 17.77%; calculated: C 48.86, H 4.10, N 17.80%.
The H atoms were positioned geometrically and treated as riding on the parent C atoms, with C—H = 0.93–0.97 Å.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); 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(C16H16N5S)O2] | F(000) = 808 |
Mr = 393.34 | Dx = 1.511 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 545 reflections |
a = 11.718 (5) Å | θ = 2.4–28.1° |
b = 10.794 (5) Å | µ = 0.72 mm−1 |
c = 13.868 (6) Å | T = 293 K |
β = 99.727 (8)° | Rectangular, orange–red |
V = 1728.9 (14) Å3 | 0.40 × 0.25 × 0.22 mm |
Z = 4 |
Bruker SMART APEX CCD diffractometer | 4189 independent reflections |
Radiation source: fine-focus sealed tube | 3223 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 0.2 pixels mm-1 | θmax = 28.1°, θmin = 2.4° |
ω scans | h = −15→14 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −14→14 |
Tmin = 0.763, Tmax = 0.859 | l = −17→18 |
15040 measured reflections |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0682P)2 + 0.1736P] where P = (Fo2 + 2Fc2)/3 |
4134 reflections | (Δ/σ)max < 0.001 |
226 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
[V(C16H16N5S)O2] | V = 1728.9 (14) Å3 |
Mr = 393.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.718 (5) Å | µ = 0.72 mm−1 |
b = 10.794 (5) Å | T = 293 K |
c = 13.868 (6) Å | 0.40 × 0.25 × 0.22 mm |
β = 99.727 (8)° |
Bruker SMART APEX CCD diffractometer | 4189 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3223 reflections with I > 2σ(I) |
Tmin = 0.763, Tmax = 0.859 | Rint = 0.021 |
15040 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.35 e Å−3 |
4134 reflections | Δρmin = −0.20 e Å−3 |
226 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 | ||
V1 | 0.20125 (3) | 0.36596 (3) | 0.62136 (2) | 0.04135 (12) | |
S1 | 0.33418 (5) | 0.28681 (4) | 0.52658 (4) | 0.05365 (16) | |
O1 | 0.27554 (16) | 0.37173 (14) | 0.72992 (11) | 0.0638 (4) | |
O2 | 0.11705 (15) | 0.24632 (13) | 0.61271 (12) | 0.0620 (4) | |
N1 | 0.07509 (14) | 0.49376 (13) | 0.64234 (11) | 0.0419 (4) | |
N2 | 0.18169 (19) | 0.84121 (15) | 0.55871 (14) | 0.0583 (5) | |
N3 | 0.21935 (13) | 0.52135 (12) | 0.52509 (11) | 0.0372 (3) | |
N4 | 0.29862 (14) | 0.52556 (13) | 0.46407 (12) | 0.0414 (3) | |
N5 | 0.41885 (15) | 0.40797 (14) | 0.39043 (13) | 0.0469 (4) | |
C1 | −0.00246 (19) | 0.4676 (2) | 0.70046 (15) | 0.0514 (5) | |
H1 | −0.0005 | 0.3898 | 0.7294 | 0.062* | |
C2 | −0.0838 (2) | 0.5505 (2) | 0.71870 (16) | 0.0552 (5) | |
H2 | −0.1350 | 0.5304 | 0.7608 | 0.066* | |
C3 | −0.08895 (19) | 0.66459 (19) | 0.67357 (16) | 0.0512 (5) | |
H3 | −0.1453 | 0.7217 | 0.6833 | 0.061* | |
C4 | −0.00923 (18) | 0.69349 (17) | 0.61351 (14) | 0.0466 (4) | |
H4 | −0.0117 | 0.7701 | 0.5825 | 0.056* | |
C5 | 0.07417 (17) | 0.60672 (15) | 0.60032 (13) | 0.0388 (4) | |
C6 | 0.16241 (17) | 0.62297 (14) | 0.53789 (13) | 0.0378 (4) | |
C7 | 0.18407 (17) | 0.74662 (16) | 0.49651 (14) | 0.0420 (4) | |
C8 | 0.20532 (18) | 0.76257 (17) | 0.40239 (15) | 0.0464 (4) | |
H8 | 0.2068 | 0.6949 | 0.3611 | 0.056* | |
C9 | 0.2243 (2) | 0.88087 (19) | 0.37077 (18) | 0.0572 (6) | |
H9 | 0.2381 | 0.8943 | 0.3075 | 0.069* | |
C10 | 0.2224 (2) | 0.9781 (2) | 0.4338 (2) | 0.0713 (7) | |
H10 | 0.2353 | 1.0587 | 0.4144 | 0.086* | |
C11 | 0.2013 (3) | 0.95401 (19) | 0.5255 (2) | 0.0760 (8) | |
H11 | 0.2005 | 1.0206 | 0.5680 | 0.091* | |
C12 | 0.35070 (16) | 0.41729 (16) | 0.45730 (14) | 0.0405 (4) | |
C13 | 0.4849 (2) | 0.29667 (19) | 0.37340 (18) | 0.0563 (5) | |
H13A | 0.4338 | 0.2270 | 0.3542 | 0.068* | |
H13B | 0.5395 | 0.2745 | 0.4315 | 0.068* | |
C14 | 0.5474 (3) | 0.3354 (2) | 0.2907 (2) | 0.0708 (7) | |
H14A | 0.6246 | 0.3652 | 0.3163 | 0.085* | |
H14B | 0.5533 | 0.2663 | 0.2471 | 0.085* | |
C15 | 0.4745 (3) | 0.4371 (3) | 0.2381 (2) | 0.0741 (7) | |
H15A | 0.4118 | 0.4032 | 0.1908 | 0.089* | |
H15B | 0.5209 | 0.4914 | 0.2045 | 0.089* | |
C16 | 0.4284 (2) | 0.50519 (19) | 0.31792 (17) | 0.0536 (5) | |
H16A | 0.4814 | 0.5699 | 0.3457 | 0.064* | |
H16B | 0.3535 | 0.5418 | 0.2936 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V1 | 0.0580 (2) | 0.02954 (16) | 0.03669 (19) | −0.00026 (12) | 0.00859 (14) | 0.00275 (11) |
S1 | 0.0722 (4) | 0.0327 (2) | 0.0596 (3) | 0.0069 (2) | 0.0214 (3) | 0.0041 (2) |
O1 | 0.0807 (11) | 0.0651 (9) | 0.0422 (9) | 0.0205 (8) | 0.0007 (8) | −0.0021 (7) |
O2 | 0.0885 (12) | 0.0391 (7) | 0.0636 (10) | −0.0142 (7) | 0.0280 (9) | −0.0012 (6) |
N1 | 0.0498 (9) | 0.0374 (7) | 0.0392 (8) | −0.0030 (6) | 0.0096 (7) | 0.0032 (6) |
N2 | 0.0915 (14) | 0.0337 (8) | 0.0530 (11) | −0.0071 (8) | 0.0216 (10) | −0.0035 (7) |
N3 | 0.0471 (8) | 0.0302 (6) | 0.0348 (7) | −0.0014 (6) | 0.0079 (6) | −0.0004 (5) |
N4 | 0.0500 (9) | 0.0344 (7) | 0.0418 (8) | −0.0018 (6) | 0.0137 (7) | 0.0009 (6) |
N5 | 0.0521 (10) | 0.0396 (8) | 0.0511 (10) | −0.0006 (7) | 0.0151 (8) | −0.0046 (7) |
C1 | 0.0580 (13) | 0.0503 (11) | 0.0473 (11) | −0.0070 (9) | 0.0128 (10) | 0.0066 (8) |
C2 | 0.0550 (13) | 0.0692 (13) | 0.0442 (12) | −0.0098 (10) | 0.0160 (10) | −0.0062 (10) |
C3 | 0.0513 (12) | 0.0541 (11) | 0.0487 (12) | 0.0025 (9) | 0.0102 (9) | −0.0136 (9) |
C4 | 0.0569 (12) | 0.0398 (9) | 0.0434 (11) | 0.0022 (8) | 0.0090 (9) | −0.0043 (7) |
C5 | 0.0480 (10) | 0.0345 (8) | 0.0337 (9) | −0.0040 (7) | 0.0062 (8) | −0.0034 (7) |
C6 | 0.0493 (10) | 0.0297 (7) | 0.0344 (9) | −0.0031 (7) | 0.0072 (8) | −0.0004 (6) |
C7 | 0.0504 (11) | 0.0301 (8) | 0.0456 (10) | −0.0002 (7) | 0.0082 (8) | 0.0029 (7) |
C8 | 0.0583 (12) | 0.0366 (9) | 0.0453 (11) | 0.0020 (8) | 0.0114 (9) | 0.0027 (7) |
C9 | 0.0731 (15) | 0.0464 (11) | 0.0547 (13) | 0.0023 (10) | 0.0183 (11) | 0.0143 (9) |
C10 | 0.103 (2) | 0.0349 (10) | 0.0792 (17) | −0.0079 (11) | 0.0252 (15) | 0.0098 (10) |
C11 | 0.127 (2) | 0.0314 (10) | 0.0746 (17) | −0.0102 (12) | 0.0323 (16) | −0.0065 (10) |
C12 | 0.0449 (10) | 0.0342 (8) | 0.0417 (10) | −0.0033 (7) | 0.0053 (8) | −0.0033 (7) |
C13 | 0.0574 (13) | 0.0457 (11) | 0.0682 (15) | 0.0013 (9) | 0.0176 (11) | −0.0118 (10) |
C14 | 0.0781 (17) | 0.0721 (15) | 0.0683 (17) | 0.0028 (13) | 0.0302 (14) | −0.0186 (13) |
C15 | 0.0884 (19) | 0.0792 (17) | 0.0603 (15) | −0.0043 (14) | 0.0287 (14) | −0.0106 (13) |
C16 | 0.0597 (13) | 0.0508 (11) | 0.0535 (12) | −0.0069 (9) | 0.0187 (10) | −0.0009 (9) |
V1—O1 | 1.6080 (17) | C4—H4 | 0.9300 |
V1—O2 | 1.6174 (16) | C5—C6 | 1.467 (3) |
V1—N1 | 2.0781 (17) | C6—C7 | 1.491 (2) |
V1—N3 | 2.1763 (16) | C7—C8 | 1.380 (3) |
V1—S1 | 2.3613 (9) | C8—C9 | 1.380 (3) |
S1—C12 | 1.734 (2) | C8—H8 | 0.9300 |
N1—C1 | 1.343 (3) | C9—C10 | 1.368 (3) |
N1—C5 | 1.351 (2) | C9—H9 | 0.9300 |
N2—C11 | 1.335 (3) | C10—C11 | 1.362 (4) |
N2—C7 | 1.340 (2) | C10—H10 | 0.9300 |
N3—C6 | 1.311 (2) | C11—H11 | 0.9300 |
N3—N4 | 1.359 (2) | C13—C14 | 1.520 (3) |
N4—C12 | 1.329 (2) | C13—H13A | 0.9700 |
N5—C12 | 1.326 (3) | C13—H13B | 0.9700 |
N5—C13 | 1.470 (3) | C14—C15 | 1.502 (4) |
N5—C16 | 1.471 (3) | C14—H14A | 0.9700 |
C1—C2 | 1.362 (3) | C14—H14B | 0.9700 |
C1—H1 | 0.9300 | C15—C16 | 1.503 (3) |
C2—C3 | 1.378 (3) | C15—H15A | 0.9700 |
C2—H2 | 0.9300 | C15—H15B | 0.9700 |
C3—C4 | 1.388 (3) | C16—H16A | 0.9700 |
C3—H3 | 0.9300 | C16—H16B | 0.9700 |
C4—C5 | 1.388 (3) | ||
O1—V1—O2 | 109.11 (9) | N2—C7—C6 | 114.25 (17) |
O1—V1—N1 | 97.39 (8) | C8—C7—C6 | 123.03 (16) |
O2—V1—N1 | 95.79 (8) | C7—C8—C9 | 118.70 (19) |
O1—V1—N3 | 116.82 (8) | C7—C8—H8 | 120.7 |
O2—V1—N3 | 133.74 (8) | C9—C8—H8 | 120.7 |
N1—V1—N3 | 73.72 (6) | C10—C9—C8 | 119.1 (2) |
O1—V1—S1 | 103.39 (7) | C10—C9—H9 | 120.5 |
O2—V1—S1 | 96.97 (6) | C8—C9—H9 | 120.5 |
N1—V1—S1 | 150.45 (5) | C11—C10—C9 | 118.4 (2) |
N3—V1—S1 | 78.20 (5) | C11—C10—H10 | 120.8 |
C12—S1—V1 | 99.23 (7) | C9—C10—H10 | 120.8 |
C1—N1—C5 | 119.46 (17) | N2—C11—C10 | 124.4 (2) |
C1—N1—V1 | 120.95 (13) | N2—C11—H11 | 117.8 |
C5—N1—V1 | 119.53 (13) | C10—C11—H11 | 117.8 |
C11—N2—C7 | 116.7 (2) | N5—C12—N4 | 117.01 (16) |
C6—N3—N4 | 118.24 (14) | N5—C12—S1 | 117.56 (14) |
C6—N3—V1 | 117.20 (12) | N4—C12—S1 | 125.41 (15) |
N4—N3—V1 | 123.74 (11) | N5—C13—C14 | 103.33 (18) |
C12—N4—N3 | 112.64 (14) | N5—C13—H13A | 111.1 |
C12—N5—C13 | 124.77 (17) | C14—C13—H13A | 111.1 |
C12—N5—C16 | 123.28 (16) | N5—C13—H13B | 111.1 |
C13—N5—C16 | 111.73 (16) | C14—C13—H13B | 111.1 |
N1—C1—C2 | 122.7 (2) | H13A—C13—H13B | 109.1 |
N1—C1—H1 | 118.7 | C15—C14—C13 | 105.1 (2) |
C2—C1—H1 | 118.7 | C15—C14—H14A | 110.7 |
C1—C2—C3 | 118.7 (2) | C13—C14—H14A | 110.7 |
C1—C2—H2 | 120.6 | C15—C14—H14B | 110.7 |
C3—C2—H2 | 120.6 | C13—C14—H14B | 110.7 |
C2—C3—C4 | 119.4 (2) | H14A—C14—H14B | 108.8 |
C2—C3—H3 | 120.3 | C14—C15—C16 | 104.2 (2) |
C4—C3—H3 | 120.3 | C14—C15—H15A | 110.9 |
C5—C4—C3 | 119.18 (18) | C16—C15—H15A | 110.9 |
C5—C4—H4 | 120.4 | C14—C15—H15B | 110.9 |
C3—C4—H4 | 120.4 | C16—C15—H15B | 110.9 |
N1—C5—C4 | 120.45 (18) | H15A—C15—H15B | 108.9 |
N1—C5—C6 | 114.05 (16) | N5—C16—C15 | 103.47 (18) |
C4—C5—C6 | 125.40 (16) | N5—C16—H16A | 111.1 |
N3—C6—C5 | 113.91 (15) | C15—C16—H16A | 111.1 |
N3—C6—C7 | 124.95 (17) | N5—C16—H16B | 111.1 |
C5—C6—C7 | 121.12 (15) | C15—C16—H16B | 111.1 |
N2—C7—C8 | 122.72 (17) | H16A—C16—H16B | 109.0 |
O1—V1—S1—C12 | −111.81 (9) | V1—N3—C6—C5 | −13.4 (2) |
O2—V1—S1—C12 | 136.59 (9) | N4—N3—C6—C7 | −5.0 (3) |
N1—V1—S1—C12 | 21.65 (12) | V1—N3—C6—C7 | 165.09 (14) |
N3—V1—S1—C12 | 3.28 (7) | N1—C5—C6—N3 | 6.8 (2) |
O1—V1—N1—C1 | −68.93 (16) | C4—C5—C6—N3 | −169.71 (17) |
O2—V1—N1—C1 | 41.25 (16) | N1—C5—C6—C7 | −171.81 (16) |
N3—V1—N1—C1 | 175.22 (16) | C4—C5—C6—C7 | 11.7 (3) |
S1—V1—N1—C1 | 156.48 (12) | C11—N2—C7—C8 | −0.1 (4) |
O1—V1—N1—C5 | 108.18 (15) | C11—N2—C7—C6 | 179.6 (2) |
O2—V1—N1—C5 | −141.64 (14) | N3—C6—C7—N2 | −138.0 (2) |
N3—V1—N1—C5 | −7.67 (13) | C5—C6—C7—N2 | 40.4 (3) |
S1—V1—N1—C5 | −26.4 (2) | N3—C6—C7—C8 | 41.7 (3) |
O1—V1—N3—C6 | −78.52 (15) | C5—C6—C7—C8 | −139.9 (2) |
O2—V1—N3—C6 | 93.93 (16) | N2—C7—C8—C9 | −0.4 (3) |
N1—V1—N3—C6 | 11.62 (13) | C6—C7—C8—C9 | 179.9 (2) |
S1—V1—N3—C6 | −177.69 (14) | C7—C8—C9—C10 | 0.6 (4) |
O1—V1—N3—N4 | 90.95 (15) | C8—C9—C10—C11 | −0.3 (4) |
O2—V1—N3—N4 | −96.61 (16) | C7—N2—C11—C10 | 0.4 (5) |
N1—V1—N3—N4 | −178.91 (15) | C9—C10—C11—N2 | −0.2 (5) |
S1—V1—N3—N4 | −8.23 (12) | C13—N5—C12—N4 | 178.94 (18) |
C6—N3—N4—C12 | 179.83 (16) | C16—N5—C12—N4 | −7.1 (3) |
V1—N3—N4—C12 | 10.5 (2) | C13—N5—C12—S1 | −2.5 (3) |
C5—N1—C1—C2 | 0.6 (3) | C16—N5—C12—S1 | 171.50 (15) |
V1—N1—C1—C2 | 177.67 (16) | N3—N4—C12—N5 | 171.87 (15) |
N1—C1—C2—C3 | 1.8 (3) | N3—N4—C12—S1 | −6.6 (2) |
C1—C2—C3—C4 | −2.0 (3) | V1—S1—C12—N5 | −177.88 (14) |
C2—C3—C4—C5 | −0.1 (3) | V1—S1—C12—N4 | 0.55 (17) |
C1—N1—C5—C4 | −2.8 (3) | C12—N5—C13—C14 | −179.81 (19) |
V1—N1—C5—C4 | −179.91 (14) | C16—N5—C13—C14 | 5.6 (2) |
C1—N1—C5—C6 | −179.43 (16) | N5—C13—C14—C15 | −25.0 (3) |
V1—N1—C5—C6 | 3.4 (2) | C13—C14—C15—C16 | 35.3 (3) |
C3—C4—C5—N1 | 2.5 (3) | C12—N5—C16—C15 | −158.8 (2) |
C3—C4—C5—C6 | 178.79 (18) | C13—N5—C16—C15 | 15.9 (2) |
N4—N3—C6—C5 | 176.52 (15) | C14—C15—C16—N5 | −31.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13A···O1i | 0.97 | 2.54 | 3.411 (3) | 149 |
C3—H3···O1ii | 0.93 | 2.65 | 3.544 (3) | 162 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [V(C16H16N5S)O2] |
Mr | 393.34 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.718 (5), 10.794 (5), 13.868 (6) |
β (°) | 99.727 (8) |
V (Å3) | 1728.9 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.40 × 0.25 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.763, 0.859 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15040, 4189, 3223 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.112, 1.03 |
No. of reflections | 4134 |
No. of parameters | 226 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.20 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
V1—O1 | 1.6080 (17) | S1—C12 | 1.734 (2) |
V1—O2 | 1.6174 (16) | N3—C6 | 1.311 (2) |
V1—N1 | 2.0781 (17) | N3—N4 | 1.359 (2) |
V1—N3 | 2.1763 (16) | N4—C12 | 1.329 (2) |
V1—S1 | 2.3613 (9) | N5—C12 | 1.326 (3) |
O1—V1—O2 | 109.11 (9) | O2—V1—S1 | 96.97 (6) |
O1—V1—N1 | 97.39 (8) | N1—V1—S1 | 150.45 (5) |
O2—V1—N1 | 95.79 (8) | N3—V1—S1 | 78.20 (5) |
O1—V1—N3 | 116.82 (8) | C12—S1—V1 | 99.23 (7) |
O2—V1—N3 | 133.74 (8) | C6—N3—N4 | 118.24 (14) |
N1—V1—N3 | 73.72 (6) | N3—C6—C5 | 113.91 (15) |
O1—V1—S1 | 103.39 (7) | N3—C6—C7 | 124.95 (17) |
N1—C5—C6—N3 | 6.8 (2) | N3—C6—C7—N2 | −138.0 (2) |
C4—C5—C6—N3 | −169.71 (17) | N3—C6—C7—C8 | 41.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13A···O1i | 0.97 | 2.54 | 3.411 (3) | 148.9 |
C3—H3···O1ii | 0.93 | 2.65 | 3.544 (3) | 161.6 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y+1/2, −z+3/2. |
Thiosemicarbazones possessing N,N,S, N,N,O and O,N,S donor sites have emerged as an important class of biologically active ligands in the past few decades. The biological activity of thiosemicarbazones is related to their chelating ability with transition metal ions, bonding through S and N atoms (Klayman et al., 1984) and also on the parent aldehyde or ketone (Padhye & Kauffman, 1985; Lukevics et al., 1995). Among thousands of screened compounds (Klayman et al., 1979), 2-acetylpyridine thiosemicarbazones having the N4 atom disubstituted or as a part of the ring system possess the highest activity as antimalarial agents. Compared with the extensive studies on 2-acetylpyridine thiosemicarbazones (Garg et al., 1988), there are few reports on the metal complexes of thiosemicarbazones derived from di-2-pyridyl ketone (Duan et al., 1996; Philip et al., 2004). Vanadium coordination is seen in a variety of chemical and biological systems, thereby extending the inorganic pharmacology of thiosemicarbazones. Much of the biochemistry of vanadium is centered around the ability of vanadate ions, [H2VVO4]−, to adopt either a four-coordinate tetrahedral geometry or a five-coordinate trigonal-bipyramidal geometry (Crans, 1994). The establishment of the presence of a vanadium(IV)/vanadium(V) equilibrium in the reducing environment of living cells (Degani et al., 1981; Li et al., 1996), and the range of biological activities from antitumour, fungicide, bactericide, anti-inflammatory and antiviral activities of thiosemicarbazones (Sreekanth & Kurup, 2003), prompted us to undertake the crystal structure of the title compound, (I).
Recently, di-2-pyridyl ketone 4-methyl thiosemicarbazone acting as a pentadentate ligand towards rhenium carbonyls (Pereiras-Gabian et al., 2005) has been reported. We have reported the crystal structure of the present ligand, di-2-pyridyl ketone N4,N4-(butane-1,4-diyl)thiosemicarbazone (Usman et al., 2002; hereafter NBT), di-2-pyridyl ketone 4-methyl-4-phenyl-thiosemicarbazone (Philip et al., 2004) and the transition metal complexes of these ligands (Philip et al., 2004, 2005). We report here the first vanadium complex of the ligand di-2-pyridyl ketone N4,N4-(butane-1,4-diyl)thiosemicarbazone with the ligand in the tridentate form.
In the formation of (I), the NBT loses one H atom from its tautomeric thiol form and coordinates to vanadium through atoms N1, N3 and S1, which together with the oxo ligand O2 form the basal plane of a highly distorted square pyramid (Fig. 1 and Table 1). The atoms defining the basal plane have an average deviation of 0.191 Å from the plane; the second oxo ligand, O1, fills the apical position, with atoms V1 and O1 lying 0.539 (1) and 2.132 (2) Å from this plane. The O2—V1—N3 and O1—V1—N3 angles of 133.74 (8) and 116.82 (8)° are consistent with this description. The increase in C—S bond length from 1.671 (4) to 1.734 (2) Å together with a decrease in N4—C12 bond length from 1.374 (4) to 1.329 (2) Å in compound (I) compared with NBT confirms the coordination in the thiolate form. The E configuration about the C6—N3 and C12—N4 bonds relative to the N3—N4 bond of the thiosemicarbazone group is retained in (I).
Typically, vanadium(V) forms square-pyramidal five-coordinate complexes or octahedral six-coordinate complexes, except when significant steric constraints, such as those provided by a protein, are present (Mokry & Carrano, 1993). In (I), the τ value for the complex is 0.279, indicating a significant distortion towards the trigonal-bipyramidal form (Addison et al., 1984; Cornman et al., 1997). This configuration is in agreement with the values found in the dioxovanadium(V) complex of N,N'-dimethylethylenediamine (salicylaldehyde) (Xie et al., 2004). The formation of (I) in a highly distorted square-pyramidal rather than trigonal-bipyramidal geometry may be attributed to the electronic and/or steric requirements.
The V1—O1 distance is 0.009 (2) Å shorter than the V1—O2 distance, in agreement with values in similar dioxovanadium complexes (Sreekanth et al., 2003; Xie et al., 2004), but in contrast to another dioxovanadium complex (Maurya et al., 2002), where the two V—O distances are equal. The O—V—O angle is similar to those reported previously for the cis-VO2 moiety in other complexes (Xie et al., 2004; Sreekanth et al., 2003; Melchior et al., 1999; Asgedom et al., 1996; Lightenbarg et al., 1999; Maurya et al., 2002). The V1—N1 bond is 0.098 (2) Å shorter than the V1—N3 bond, thus confirming the strength of the pyridyl N coordination; this situation is also found in the dioxovanadium complex of 2-acetylpyridine morpholyl-3-thiosemicarbazone (Sreekanth et al., 2003) and the dioxovanadium complex of the ligand derived from 2-acetylpyridine and S-benzyldithiocarbazate (Maurya et al., 2002). The thiosemicarbazone moiety comprising atoms C6, N3, N4, C12, S1 and N5 shows a slight deviation from planarity after coordination, the maximum out of plane deviation at atom N4 changing from 0.0140 (1) Å for NBT to −0.0667 (3) Å in (I).
Ring-puckering analyses (Cremer & Pople, 1975) reveal that the pyrrolidine ring (Cg3), comprising atoms N5, C13, C14, C15 and C16, is closest to a twist form on atoms C14 and C15, with puckering parameters q2 = 0.337 (3) Å and ϕ = 278.1 (4)°, in contrast to the approximate envelope conformation in NBT. On complex formation, the thiosemicarbazone group forms two new five-membered rings, viz Cg1 [comprising atoms N3, N4, C12, S1 and V1, with a maximum out-of-plane deviation of 0.057 (2) Å for atom N3] and Cg2 [comprising atoms N1, C5, C6, N3 and V1, with a maximum deviation of 0.085 (2) Å for atom N3]. The other two rings, Cg4 (N1/C1–C5) and Cg5 (N2/C7–C11) are planar pyridyl rings; the Cg4 ring is close to coplanar with the thiosemicarbazone moiety, with a dihedral angle of 9.48 (1)° between their planes. The coordination of the azomethine N atom to the VV atom results in a slight redistribution of electron density along the thiosemicarbazone chain. This leads to a barely significant increase in length of 0.014 (4) Å for the azomethine bond C6—N3, a decrease in length of 0.045 (4) Å for the N4—C12 bond and an insignificant decrease of 0.002 (4) Å in the N3—N4 bond length in the complex compared with NBT.
In the crystal packing, each molecule is linked principally through one normal and one weak intermolecular C—H···O hydrogen bonds utilizing the oxo atoms O1 (Fig. 2 and Table 2). These V═O···H—C interactions are in agreement with previous reports (Mokry & Carrano, 1993). The crystal structure cohesion may also be reinforced by weak aromatic π–π stacking interactions and a weak V1— O2···π interaction with pyridyl ring Cg5 [symmetry code: −x, 1 − y, 1 − z; at 3.899 (3) Å distance and an angle subtended at O2 of 143.46 (8)°]. The latter type of interaction has not been observed before for similar systems.