supplementary materials


zl2486 scheme

Acta Cryst. (2012). E68, m1138    [ doi:10.1107/S1600536812028917 ]

[1-(5-Bromo-2-oxidobenzylidene)thiosemicarbazidato-[kappa]3O,N1,S](pyridine-[kappa]N)nickel(II)

F. R. S. Pederzolli, L. Bresolin, J. Beck, J. Daniels and A. B. de Oliveira

Abstract top

The reaction of 5-bromosalicylaldehyde thiosemicarbazone with nickel acetate tetrahydrate and pyridine yielded the title compound, [Ni(C8H6BrN3OS)(C5H5N)]. The NiII atom is four-coordinated in a square-planar environment by one deprotonated dianionic thiosemicarbazone ligand, acting in a tridentate chelating mode through N, O and S atoms forming two metalla-rings, and by one pyridine molecule. The complex molecules are linked into dimers by pairs of centrosymmetrical N-H...N interactions. In addition, molecules are connected through intermolecular Br...Br interactions [3.545 (1) Å], forming chains along the b-axis direction.

Comment top

Thiosemicarbazone derivatives have a wide range of applications in biological inorganic chemistry and a very interesting coordination chemistry (Lobana et al., 2009). For example, CuII and NiII complexes with 5-bromosalicylaldehyde thiosemicarbazone show antibacterial activity against Staphylococcus aureus and Escherichia coli (Joseph et al., 2010). As part of our study of thiosemicarbazone derivatives, we report herein the synthesis and the crystal structure of a new NiII complex with 5-bromosalicylaldehyde thiosemicarbazone. In the title compound, in which the molecular structure unit matches the asymmetric unit, the NiII ion is coordinated in a square planar environment by one deprotonated dianionic 5-bromosalicylaldehyde thiosemicarbazone and one pyridine ligand (Fig. 1). The selected bond angles formed between donor atoms trough the Ni atom are N1—Ni1—N4 = 177.00 (10)° and O1—Ni1—S1 = 176.46 (6)°, and show a slightly distorted coordination environment. The thiosemicarbazone ligand is coordinated to the NiII ion in a tridentate chelating mode, forming five- and six-membered rings, as a "NOS" donor with the O/S atoms trans to each other, while the N1 azomethine atom is trans to the N4 atom from the pyridine ligand.

The acidic hydrogen of the hydrazine fragment is lost by the reaction with KOH, which is in agreement with thiosemicarbazone derivatives prepared from aldehydes or ketones. The negative charge is delocalized over the C—N—N—C—S fragment as indicated by their intermediate bond distances. The imine and thioamide C—N distances indicate considerable double bond character, while the C—S distance is consistent with increased single bond character. These distances are C7—N1 = 1.295 (3) Å, N1—N2 = 1.403 (3) Å, N2—C8 = 1.289 (4) Å and C8—S1 = 1.735 (3) Å. The hydrogen of the hydroxyl group is also deprotonated with KOH, resulting in the dianionic form of the ligand.

The ligand shows a Z—E—E—Z conformation for the donor atoms about the C1—C7/C7—N1/N1—N2/N2—C8 bonds and the mean deviations from the least squares planes for the chelated fragments Ni1/N1/C7/C1/C2/O1 and Ni1/N1/N2/C8/S1 amount to 0.0286 (15) Å for N1 and 0.0170 (12) Å for N1, respectively, and the dihedral angle between the two planes is 2.97 (11)°. The Z—E—E—Z conformation is also observed for the free ligand (Kargar et al., 2010) as well as for a complex with similar coordination environment (Güveli et al., 2009).

Both ligands are almost planar (Fig. 1 and Fig. 2) and the maximum deviation from the least squares plane through all non-hydrogen atoms for the deprotonated thiosemicarbazone fragment C1/C2/C3/C4/C5/C6/C7/C8/Br1/N1/N2/N3/O1/S1 and for the pyridine molecule C9/C10/C11/C12/C13/N4 amount to 0.0668 (25) Å for C7 and 0.0059 (21) Å for C9, respectively, and the dihedral angle between the two planes is 61.15 (6)°.

The molecules are linked by pairs of centrosymmetrical N—H···N interactions (Fig. 2 and Table 1; N3—H5···N2i) forming a dimeric molecular structure, which stabilizes the crystal packing. Symmetry codes: (i) -x, -y + 1, -z.

The crystal structure shows that molecules are additionally connected through intermolecular Br···Br interactions into chains along the crystallographic b direction (Fig. 3). The Br···Br distances amount to 3.545 (1) Å, which are shorter than the sum of the van der Waals radii for Br atoms (3.70 Å).

Related literature top

For the synthesis of 5-bromosalicylaldehyde thiosemicarbazone and for the antibacterial activity of their complexes, see: Joseph et al. (2010). For the crystal structure of 5-bromosalicylaldehyde thiosemicarbazone, see: Kargar et al. (2010). For the crystal structure of an NiII complex with a similar coordination environment, see: Güveli et al. (2009). For the coordination chemistry of thiosemicarbazone derivatives, see: Lobana et al. (2009).

Experimental top

Starting materials were commercially available and were used without further purification. The synthesis of 5-bromosalicylaldehyde thiosemicarbazone was adapted from a procedure reported previously (Joseph et al., 2010). 5-Bromosalicylaldehyde thiosemicarbazone (0.5 mmol) was dissolved in tetrahydrofurane (50 ml) and treated with one KOH pellet. After 30 min stirring under slight warming to 333 K, the solution was filtered and added to a nickel acetate tetrahydrate (0.5 mmol) solution in pyridine (10 ml). The reaction mixture was refluxed for 4 h under continuous stirring and showed a brown-red colour. Brown-red crystals of the complex, suitable for X-ray analysis, were obtained after six weeks by adding a 3:1 mixture of dimethylformamide and toluene (80 ml) to the reaction solution.

Refinement top

H atoms attached to C atoms were positioned with idealized geometry and were refined isotropic with Ueq(H) set to 1.2 times of the Ueq(C) using a riding model with C—H = 0.93 Å. H atoms attached to N atoms atoms were positioned with idealized geometry and were refined isotropically with Ueq(H) set to 1.2 times of Ueq(N) using a riding model with N3—H1 = 0.7822 Å and N3—H2 = 0.8025 Å.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. : The molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 40% probability level.
[Figure 2] Fig. 2. : Molecules of the title compound connected through pairs of inversion symmetric N—H···N interactions. Hydrogen bonding is indicated by dashed lines. Symmetry code: (i) -x, -y + 1, -z.
[Figure 3] Fig. 3. : Molecules of the title compound connected through intermolecular Br···Br interactions into chains along the crystallographic b direction. The Br···Br distances amount to 3.545 (1) Å and the interactions are indicated by dashed lines.
[1-(5-Bromo-2-oxidobenzylidene)thiosemicarbazidato- κ3O,N1,S](pyridine-κN)nickel(II) top
Crystal data top
[Ni(C8H6BrN3OS)(C5H5N)]F(000) = 816
Mr = 409.94Dx = 1.881 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 17227 reflections
a = 12.2447 (4) Åθ = 2.9–27.5°
b = 4.1135 (1) ŵ = 4.25 mm1
c = 31.1380 (11) ÅT = 293 K
β = 112.646 (1)°Needle, red
V = 1447.46 (8) Å30.93 × 0.10 × 0.05 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
3224 independent reflections
Radiation source: fine-focus sealed tube, Bruker Kappa CCD2697 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
Detector resolution: 9 pixels mm-1θmax = 27.6°, θmin = 3.3°
CCD rotation images, thick slices scansh = 1515
Absorption correction: multi-scan
(Blessing, 1995)
k = 55
Tmin = 0.443, Tmax = 0.830l = 4040
13946 measured reflections
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0442P)2 + 0.6555P]
where P = (Fo2 + 2Fc2)/3
3224 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 0.61 e Å3
0 restraintsΔρmin = 0.66 e Å3
Crystal data top
[Ni(C8H6BrN3OS)(C5H5N)]V = 1447.46 (8) Å3
Mr = 409.94Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.2447 (4) ŵ = 4.25 mm1
b = 4.1135 (1) ÅT = 293 K
c = 31.1380 (11) Å0.93 × 0.10 × 0.05 mm
β = 112.646 (1)°
Data collection top
Nonius KappaCCD
diffractometer
3224 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
2697 reflections with I > 2σ(I)
Tmin = 0.443, Tmax = 0.830Rint = 0.051
13946 measured reflectionsθmax = 27.6°
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.083Δρmax = 0.61 e Å3
S = 1.05Δρmin = 0.66 e Å3
3224 reflectionsAbsolute structure: ?
190 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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*/Ueq
Br11.37247 (2)0.72025 (7)0.228104 (10)0.04622 (11)
Ni10.80812 (3)0.06339 (9)0.089703 (11)0.03527 (11)
S10.71884 (6)0.35252 (19)0.02859 (2)0.04380 (17)
O10.87955 (16)0.1736 (5)0.14418 (7)0.0419 (4)
N10.93997 (18)0.0757 (5)0.07408 (7)0.0339 (4)
N20.9399 (2)0.2507 (6)0.03540 (8)0.0403 (5)
N30.8245 (2)0.5541 (7)0.02746 (9)0.0519 (6)
H10.88310.60690.030.062*
H20.77690.69860.03340.062*
N40.67067 (19)0.0743 (6)0.10494 (8)0.0383 (5)
C11.0684 (2)0.2490 (6)0.13889 (9)0.0350 (5)
C20.9877 (2)0.2887 (6)0.16117 (9)0.0357 (5)
C31.0269 (2)0.4575 (7)0.20359 (10)0.0423 (6)
H30.97510.48580.21870.051*
C41.1399 (2)0.5829 (7)0.22359 (10)0.0428 (6)
H41.16420.69230.25190.051*
C51.2167 (2)0.5430 (6)0.20077 (9)0.0377 (5)
C61.1830 (2)0.3830 (7)0.15955 (10)0.0377 (5)
H61.23580.36160.14480.045*
C71.0394 (2)0.0704 (7)0.09658 (9)0.0380 (6)
H71.09710.05790.08410.046*
C80.8393 (2)0.3869 (7)0.01258 (9)0.0390 (6)
C90.5660 (2)0.0532 (7)0.07772 (10)0.0439 (6)
H90.5580.14370.04930.053*
C100.4699 (3)0.0547 (9)0.09040 (12)0.0553 (8)
H100.39860.14750.07110.066*
C110.4810 (3)0.0826 (9)0.13187 (12)0.0586 (8)
H110.41720.08450.14110.07*
C120.5869 (3)0.2171 (8)0.15973 (11)0.0569 (8)
H120.59550.31310.18790.068*
C130.6808 (3)0.2087 (8)0.14557 (10)0.0476 (7)
H130.75280.29850.16470.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.03290 (15)0.0510 (2)0.05011 (18)0.00359 (11)0.01082 (12)0.00312 (13)
Ni10.03052 (17)0.0412 (2)0.03447 (17)0.00019 (13)0.01296 (13)0.00106 (13)
S10.0378 (3)0.0507 (4)0.0424 (4)0.0046 (3)0.0148 (3)0.0052 (3)
O10.0321 (9)0.0540 (12)0.0406 (10)0.0025 (8)0.0151 (8)0.0049 (9)
N10.0352 (10)0.0337 (11)0.0336 (10)0.0034 (8)0.0141 (9)0.0010 (9)
N20.0419 (12)0.0419 (13)0.0399 (12)0.0010 (10)0.0189 (10)0.0039 (10)
N30.0488 (14)0.0583 (17)0.0502 (14)0.0046 (12)0.0210 (12)0.0152 (12)
N40.0346 (11)0.0443 (13)0.0356 (11)0.0030 (9)0.0130 (9)0.0002 (9)
C10.0327 (12)0.0355 (13)0.0367 (13)0.0030 (10)0.0132 (10)0.0025 (10)
C20.0297 (11)0.0387 (14)0.0389 (13)0.0030 (10)0.0134 (10)0.0046 (11)
C30.0359 (13)0.0526 (17)0.0410 (13)0.0018 (12)0.0179 (11)0.0023 (12)
C40.0387 (13)0.0475 (16)0.0393 (13)0.0025 (12)0.0118 (11)0.0041 (12)
C50.0289 (11)0.0358 (14)0.0438 (14)0.0008 (10)0.0089 (10)0.0030 (11)
C60.0311 (12)0.0391 (14)0.0443 (14)0.0020 (10)0.0159 (11)0.0018 (11)
C70.0348 (12)0.0405 (15)0.0426 (14)0.0023 (11)0.0191 (11)0.0007 (11)
C80.0431 (14)0.0363 (14)0.0376 (13)0.0049 (11)0.0157 (11)0.0021 (11)
C90.0365 (13)0.0535 (18)0.0393 (14)0.0004 (12)0.0120 (11)0.0060 (12)
C100.0349 (14)0.072 (2)0.0588 (18)0.0048 (14)0.0179 (13)0.0068 (16)
C110.0478 (17)0.076 (2)0.064 (2)0.0003 (16)0.0339 (16)0.0031 (17)
C120.062 (2)0.071 (2)0.0460 (17)0.0009 (17)0.0303 (16)0.0069 (16)
C130.0418 (14)0.0607 (19)0.0390 (14)0.0018 (13)0.0141 (12)0.0074 (13)
Geometric parameters (Å, º) top
Br1—C51.909 (3)C2—C31.403 (4)
Ni1—N11.858 (2)C3—C41.380 (4)
Ni1—O11.8576 (19)C3—H30.93
Ni1—N41.917 (2)C4—C51.390 (4)
Ni1—S12.1516 (8)C4—H40.93
S1—C81.735 (3)C5—C61.358 (4)
O1—C21.311 (3)C6—H60.93
N1—C71.295 (3)C7—H70.93
N1—N21.403 (3)C9—C101.378 (4)
N2—C81.289 (4)C9—H90.93
N3—C81.373 (4)C10—C111.367 (5)
N3—H10.7822C10—H100.93
N3—H20.8025C11—C121.369 (5)
N4—C91.341 (4)C11—H110.93
N4—C131.342 (4)C12—C131.381 (4)
C1—C61.411 (4)C12—H120.93
C1—C21.419 (3)C13—H130.93
C1—C71.429 (4)
N1—Ni1—O195.87 (9)C5—C4—H4120.5
N1—Ni1—N4177.00 (10)C6—C5—C4121.4 (2)
O1—Ni1—N486.32 (9)C6—C5—Br1119.63 (19)
N1—Ni1—S187.15 (7)C4—C5—Br1118.9 (2)
O1—Ni1—S1176.46 (6)C5—C6—C1120.5 (2)
N4—Ni1—S190.60 (7)C5—C6—H6119.8
C8—S1—Ni195.77 (10)C1—C6—H6119.8
C2—O1—Ni1127.26 (17)N1—C7—C1125.8 (2)
C7—N1—N2113.1 (2)N1—C7—H7117.1
C7—N1—Ni1125.23 (18)C1—C7—H7117.1
N2—N1—Ni1121.70 (16)N2—C8—N3118.8 (2)
C8—N2—N1112.4 (2)N2—C8—S1122.9 (2)
C8—N3—H1115.1N3—C8—S1118.2 (2)
C8—N3—H2114.2N4—C9—C10122.3 (3)
H1—N3—H2112.6N4—C9—H9118.8
C9—N4—C13118.4 (2)C10—C9—H9118.8
C9—N4—Ni1123.42 (18)C11—C10—C9118.9 (3)
C13—N4—Ni1118.17 (19)C11—C10—H10120.5
C6—C1—C2119.3 (2)C9—C10—H10120.5
C6—C1—C7118.2 (2)C10—C11—C12119.4 (3)
C2—C1—C7122.5 (2)C10—C11—H11120.3
O1—C2—C3119.0 (2)C12—C11—H11120.3
O1—C2—C1123.2 (2)C11—C12—C13119.3 (3)
C3—C2—C1117.8 (2)C11—C12—H12120.4
C4—C3—C2122.0 (2)C13—C12—H12120.4
C4—C3—H3119N4—C13—C12121.7 (3)
C2—C3—H3119N4—C13—H13119.2
C3—C4—C5118.9 (3)C12—C13—H13119.2
C3—C4—H4120.5
N1—Ni1—S1—C81.82 (11)C3—C4—C5—C60.3 (4)
N4—Ni1—S1—C8176.20 (12)C3—C4—C5—Br1179.4 (2)
N1—Ni1—O1—C21.9 (2)C4—C5—C6—C10.7 (4)
N4—Ni1—O1—C2179.8 (2)Br1—C5—C6—C1179.7 (2)
O1—Ni1—N1—C74.3 (2)C2—C1—C6—C51.3 (4)
S1—Ni1—N1—C7177.6 (2)C7—C1—C6—C5177.2 (2)
O1—Ni1—N1—N2175.74 (19)N2—N1—C7—C1175.7 (2)
S1—Ni1—N1—N22.40 (18)Ni1—N1—C7—C14.3 (4)
C7—N1—N2—C8178.1 (2)C6—C1—C7—N1177.7 (3)
Ni1—N1—N2—C81.9 (3)C2—C1—C7—N10.7 (4)
O1—Ni1—N4—C9119.2 (2)N1—N2—C8—N3177.0 (2)
S1—Ni1—N4—C962.5 (2)N1—N2—C8—S10.2 (3)
O1—Ni1—N4—C1358.9 (2)Ni1—S1—C8—N21.6 (3)
S1—Ni1—N4—C13119.3 (2)Ni1—S1—C8—N3178.4 (2)
Ni1—O1—C2—C3178.72 (19)C13—N4—C9—C101.0 (4)
Ni1—O1—C2—C10.8 (4)Ni1—N4—C9—C10177.1 (2)
C6—C1—C2—O1179.6 (2)N4—C9—C10—C110.9 (5)
C7—C1—C2—O12.0 (4)C9—C10—C11—C120.1 (5)
C6—C1—C2—C30.9 (4)C10—C11—C12—C130.6 (5)
C7—C1—C2—C3177.5 (2)C9—N4—C13—C120.2 (4)
O1—C2—C3—C4179.5 (3)Ni1—N4—C13—C12178.0 (2)
C1—C2—C3—C40.0 (4)C11—C12—C13—N40.6 (5)
C2—C3—C4—C50.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1···N2i0.782.313.095 (3)178
Symmetry code: (i) x+2, y1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1···N2i0.782.313.095 (3)178
Symmetry code: (i) x+2, y1, z.
Acknowledgements top

We gratefully acknowledge financial support through the DECIT/SCTIE-MS-CNPq-FAPERGS-Pronem-# 11/2029–1 and PRONEX-CNPq-FAPERGS projects.

references
References top

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