metal-organic compounds
Bis(4-hydroxy-3-methoxybenzaldehyde 4-phenylthiosemicarbazonato-N1,S)nickel(II)
aDepartamento de Química, Universidade Federal de Sergipe, Av. Marechal Rondon s/n, Campus, 49100-000 São Cristóvão-SE, Brazil, and bInstitut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth Strasse 2, D-24118 Kiel, Germany
*Correspondence e-mail: adriano@daad-alumni.de
In the title compound, [Ni(C15H14N3O2S)2], the NiII atom lies on a center of symmetry. The deprotonated ligands act as N,S-donors, forming five-membered metalla-rings. The NiII atom is four-coordinated in a slightly distorted square-planar environment. In the crystal, the discrete complex molecules are linked by weak N—H⋯O hydrogen bonds, generating chains along [110]. The chains are further connected via weak O—H⋯N interactions into a layered network extending parallel to (001).
CCDC reference: 998671
Related literature
For the et al. (2013). For the of a similar complex, see: Akinchan & Abram (2000). For the coordination chemistry of thiosemicarbazone compounds, see: Lobana et al. (2009).
of the ligand, see: OliveiraExperimental
Crystal data
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Data collection: X-AREA (Stoe & Cie, 2008); cell X-AREA; data reduction: X-RED32 (Stoe & Cie, 2008); 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).
Supporting information
CCDC reference: 998671
10.1107/S1600536814009027/lr2126sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814009027/lr2126Isup2.hkl
Starting materials were commercially available and were used without further purification. 4-Hydroxy-3-methoxybenzaldehyde 4-phenylthiosemicarbazone was dissolved in THF (2 mmol/40 ml) with stirring maintained for 30 min, while the solution turns yellow. A solution of nickel acetate tetrahydrate (1 mmol/40 ml) in THF was added under continuous stirring. After 3 h the solvent was removed and the solid redissolved in methanol. Crystals suitable for X-ray diffraction were obtained by the slow evaporation of the solvent.
Crystal data, data collection and structure
details are summarized in Table 1. All non-hydrogen atoms were refined anisotropic. Most C—H atoms were positioned with idealized geometry (methyl and O—H atoms allowed to rotate but no to tip) and were refined isotropic with Uiso(H) = 1.2 Ueq(C, N) (1.5 for methyl and O—H atoms) using a riding model. The H atoms attached to N1 and C8 were refined with varying coordinates and varying isotropic displacement parameters.Thiosemicarbazone derivatives are N,S-donors with a wide range of coordination modes (Lobana et al., 2009). As part of our interest on the coordination chemistry of thiosemicarbazone ligands, we report herein the synthesis and the
of a new NiII complex with the 4-hydroxy-3-methoxybenzaldehyde 4-phenylthiosemicarbazone.The NiII atoms are four-coordinated in a slightly distorted planar environment by two bidentate deprotonated ligands forming discrete complexes. The
consists of one NiII cation that is located on a centre of inversion and one anionic ligand that occupies a general position (Fig. 1). During complex formation signficant structural changes of the N–N–C–S fragment are observed. For the uncoordinated 4-hydroxy-3-methoxybenzaldehyde 4-phenylthiosemicarbazone ligand the N–N, N–C and C–S bond distances amount to 1.3792 (17) Å, 1.3404 (19) Å and 1.6962 (15) Å. The distances indicate the double bond character for the N–N and C–S bonds, and the single bond character for the N–C bond (Oliveira et al., 2013).For the title compound, the acidic hydrogen of the hydrazine fragment is lost and the negative charge is delocalized over the N–N–C–S fragment. Therefore, for the coordinated ligand the N–N, N–C and C–S bond distances amount to 1.407 (4) Å, 1.306 (3) Å and 1.732 (4) Å. Similar values are found in the literature for the bis(4-hydroxy-3-methoxybenzaldehyde thiosemicarbazonato-N1,S)nickel(II) complex: 1.401 (3) Å, 1.317 (3) Å and 1.726 (3) Å (Akinchan & Abram, 2000). The N–C bond distances indicate a considerable double bond character, while the N–N and C–S bond distances are consistent with an increased single bond character.
The ligands are coordinated to the metal as N,S-donors (Fig. 1), building a slightly distorted planar environment, typical for low spin, strong field and d8
with Jahn-Teller effect. The maximal deviation from the least squares plane through all non-hydrogen atoms for the Ni1/C7/N2/N3/S1 ring amounts to 0.2373 (15) Å for N3. Additionally, the dihedral angle between the two aromatic rings of the ligands is 42.270 (68)°, showing that they are not planar (Fig. 1).The molecules are linked into chains along the a-b-direction forming a H-bonded coordination polymer (Fig. 2). The crystal packing is stabilized by intermolecular N—H···O and O—H···N hydrogen bonding (Table 1).
Data collection: X-AREA (Stoe & Cie, 2008); cell
X-AREA (Stoe & Cie, 2008); data reduction: X-RED32 (Stoe & Cie, 2008); 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).[Ni(C15H14N3O2S)2] | V = 712.47 (7) Å3 |
Mr = 659.41 | Z = 1 |
Triclinic, P1 | F(000) = 342 |
Hall symbol: -P 1 | Dx = 1.537 Mg m−3 |
a = 6.8080 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.5569 (4) Å | θ = 1.4–27.0° |
c = 14.3902 (8) Å | µ = 0.88 mm−1 |
α = 98.514 (4)° | T = 200 K |
β = 92.062 (5)° | Prism, red |
γ = 102.698 (5)° | 0.12 × 0.08 × 0.04 mm |
Stoe IPDS-1 diffractometer | 2539 independent reflections |
Radiation source: fine-focus sealed tube, Stoe IPDS-1 | 2539 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ scans | θmax = 27.0°, θmin = 1.4° |
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) | h = −8→8 |
Tmin = 0.800, Tmax = 0.936 | k = −9→9 |
3117 measured reflections | l = −18→16 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0482P)2 + 0.0121P] where P = (Fo2 + 2Fc2)/3 |
3117 reflections | (Δ/σ)max < 0.001 |
206 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
[Ni(C15H14N3O2S)2] | γ = 102.698 (5)° |
Mr = 659.41 | V = 712.47 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.8080 (4) Å | Mo Kα radiation |
b = 7.5569 (4) Å | µ = 0.88 mm−1 |
c = 14.3902 (8) Å | T = 200 K |
α = 98.514 (4)° | 0.12 × 0.08 × 0.04 mm |
β = 92.062 (5)° |
Stoe IPDS-1 diffractometer | 2539 independent reflections |
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) | 2539 reflections with I > 2σ(I) |
Tmin = 0.800, Tmax = 0.936 | Rint = 0.033 |
3117 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.33 e Å−3 |
3117 reflections | Δρmin = −0.19 e Å−3 |
206 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 | ||
Ni1 | 0.5000 | 1.0000 | 0.0000 | 0.02742 (11) | |
C1 | 0.1523 (3) | 0.8520 (2) | 0.32101 (13) | 0.0331 (4) | |
C2 | 0.3262 (3) | 0.8457 (3) | 0.37156 (15) | 0.0435 (5) | |
H2 | 0.4537 | 0.8789 | 0.3463 | 0.052* | |
C3 | 0.3138 (4) | 0.7905 (3) | 0.45971 (16) | 0.0516 (6) | |
H3 | 0.4338 | 0.7874 | 0.4946 | 0.062* | |
C4 | 0.1309 (5) | 0.7404 (4) | 0.49672 (18) | 0.0651 (7) | |
H4 | 0.1233 | 0.7025 | 0.5568 | 0.078* | |
C5 | −0.0420 (5) | 0.7461 (5) | 0.4453 (2) | 0.0808 (10) | |
H5 | −0.1697 | 0.7112 | 0.4701 | 0.097* | |
C6 | −0.0314 (4) | 0.8019 (4) | 0.35813 (18) | 0.0580 (6) | |
H6 | −0.1516 | 0.8058 | 0.3236 | 0.070* | |
N1 | 0.1511 (3) | 0.9162 (2) | 0.23399 (12) | 0.0329 (3) | |
H1N1 | 0.056 (4) | 0.957 (3) | 0.2191 (18) | 0.051 (7)* | |
C7 | 0.2813 (3) | 0.9123 (2) | 0.16455 (13) | 0.0281 (4) | |
S1 | 0.21900 (7) | 1.00329 (7) | 0.06685 (3) | 0.03549 (13) | |
N2 | 0.4377 (2) | 0.8401 (2) | 0.17166 (11) | 0.0312 (3) | |
N3 | 0.5427 (2) | 0.8441 (2) | 0.08926 (11) | 0.0300 (3) | |
C8 | 0.6613 (3) | 0.7309 (3) | 0.07729 (14) | 0.0337 (4) | |
H8 | 0.739 (3) | 0.737 (3) | 0.0244 (16) | 0.035 (5)* | |
C9 | 0.6955 (3) | 0.5875 (2) | 0.12971 (13) | 0.0317 (4) | |
C10 | 0.8662 (3) | 0.5206 (3) | 0.10650 (14) | 0.0364 (4) | |
H10 | 0.9538 | 0.5760 | 0.0637 | 0.044* | |
C11 | 0.9096 (3) | 0.3751 (3) | 0.14491 (14) | 0.0362 (4) | |
H11 | 1.0260 | 0.3307 | 0.1286 | 0.043* | |
C12 | 0.7829 (3) | 0.2951 (2) | 0.20690 (14) | 0.0322 (4) | |
C13 | 0.6150 (3) | 0.3636 (2) | 0.23340 (13) | 0.0302 (4) | |
C14 | 0.5702 (3) | 0.5083 (2) | 0.19495 (13) | 0.0315 (4) | |
H14 | 0.4552 | 0.5539 | 0.2126 | 0.038* | |
O1 | 0.8234 (2) | 0.14835 (19) | 0.24410 (11) | 0.0411 (3) | |
H1O1 | 0.7174 | 0.0896 | 0.2635 | 0.062* | |
O2 | 0.5064 (2) | 0.27403 (18) | 0.29749 (10) | 0.0392 (3) | |
C15 | 0.3366 (4) | 0.3391 (3) | 0.33051 (18) | 0.0478 (5) | |
H15A | 0.3816 | 0.4655 | 0.3637 | 0.072* | |
H15B | 0.2688 | 0.2604 | 0.3736 | 0.072* | |
H15C | 0.2423 | 0.3362 | 0.2769 | 0.072* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.03166 (19) | 0.03038 (17) | 0.02632 (18) | 0.01380 (13) | 0.00733 (13) | 0.01269 (13) |
C1 | 0.0424 (11) | 0.0294 (8) | 0.0300 (10) | 0.0098 (8) | 0.0091 (8) | 0.0086 (7) |
C2 | 0.0491 (12) | 0.0518 (12) | 0.0369 (11) | 0.0196 (10) | 0.0086 (9) | 0.0170 (9) |
C3 | 0.0757 (17) | 0.0529 (12) | 0.0328 (11) | 0.0258 (12) | 0.0006 (11) | 0.0125 (10) |
C4 | 0.094 (2) | 0.0699 (16) | 0.0338 (12) | 0.0125 (15) | 0.0135 (14) | 0.0237 (12) |
C5 | 0.073 (2) | 0.120 (3) | 0.0497 (16) | 0.0017 (18) | 0.0235 (15) | 0.0408 (17) |
C6 | 0.0508 (14) | 0.0816 (17) | 0.0419 (13) | 0.0049 (12) | 0.0113 (11) | 0.0246 (12) |
N1 | 0.0338 (8) | 0.0393 (8) | 0.0330 (8) | 0.0168 (7) | 0.0097 (7) | 0.0155 (7) |
C7 | 0.0309 (9) | 0.0265 (8) | 0.0288 (9) | 0.0073 (7) | 0.0057 (7) | 0.0092 (7) |
S1 | 0.0338 (3) | 0.0491 (3) | 0.0333 (3) | 0.0198 (2) | 0.0090 (2) | 0.0209 (2) |
N2 | 0.0375 (8) | 0.0353 (8) | 0.0285 (8) | 0.0173 (7) | 0.0103 (7) | 0.0140 (6) |
N3 | 0.0349 (8) | 0.0322 (7) | 0.0281 (8) | 0.0136 (6) | 0.0083 (6) | 0.0114 (6) |
C8 | 0.0405 (10) | 0.0369 (9) | 0.0320 (10) | 0.0188 (8) | 0.0123 (8) | 0.0149 (8) |
C9 | 0.0377 (10) | 0.0332 (9) | 0.0302 (9) | 0.0166 (8) | 0.0069 (8) | 0.0106 (7) |
C10 | 0.0432 (11) | 0.0371 (9) | 0.0360 (10) | 0.0180 (8) | 0.0142 (9) | 0.0127 (8) |
C11 | 0.0366 (10) | 0.0402 (10) | 0.0393 (11) | 0.0204 (8) | 0.0094 (8) | 0.0118 (8) |
C12 | 0.0360 (10) | 0.0306 (8) | 0.0347 (10) | 0.0137 (7) | 0.0011 (8) | 0.0114 (7) |
C13 | 0.0334 (9) | 0.0293 (8) | 0.0303 (9) | 0.0091 (7) | 0.0043 (8) | 0.0096 (7) |
C14 | 0.0343 (9) | 0.0308 (8) | 0.0351 (10) | 0.0152 (7) | 0.0067 (8) | 0.0112 (7) |
O1 | 0.0414 (8) | 0.0405 (7) | 0.0524 (9) | 0.0213 (6) | 0.0094 (7) | 0.0239 (6) |
O2 | 0.0418 (8) | 0.0387 (7) | 0.0475 (8) | 0.0176 (6) | 0.0163 (7) | 0.0240 (6) |
C15 | 0.0532 (13) | 0.0436 (11) | 0.0576 (14) | 0.0213 (10) | 0.0292 (11) | 0.0226 (10) |
Ni1—N3 | 1.9220 (15) | N2—N3 | 1.407 (2) |
Ni1—N3i | 1.9220 (15) | N3—C8 | 1.298 (2) |
Ni1—S1i | 2.1753 (5) | C8—C9 | 1.462 (2) |
Ni1—S1 | 2.1753 (5) | C8—H8 | 0.94 (2) |
C1—C6 | 1.376 (3) | C9—C10 | 1.398 (3) |
C1—C2 | 1.380 (3) | C9—C14 | 1.402 (3) |
C1—N1 | 1.409 (2) | C10—C11 | 1.383 (3) |
C2—C3 | 1.392 (3) | C10—H10 | 0.9500 |
C2—H2 | 0.9500 | C11—C12 | 1.375 (3) |
C3—C4 | 1.370 (4) | C11—H11 | 0.9500 |
C3—H3 | 0.9500 | C12—O1 | 1.375 (2) |
C4—C5 | 1.380 (5) | C12—C13 | 1.398 (3) |
C4—H4 | 0.9500 | C13—O2 | 1.367 (2) |
C5—C6 | 1.381 (4) | C13—C14 | 1.381 (2) |
C5—H5 | 0.9500 | C14—H14 | 0.9500 |
C6—H6 | 0.9500 | O1—H1O1 | 0.8400 |
N1—C7 | 1.361 (2) | O2—C15 | 1.423 (2) |
N1—H1N1 | 0.81 (3) | C15—H15A | 0.9800 |
C7—N2 | 1.306 (2) | C15—H15B | 0.9800 |
C7—S1 | 1.7322 (18) | C15—H15C | 0.9800 |
N3—Ni1—N3i | 180.00 (6) | C8—N3—N2 | 115.09 (15) |
N3—Ni1—S1i | 95.42 (5) | C8—N3—Ni1 | 123.66 (13) |
N3i—Ni1—S1i | 84.58 (5) | N2—N3—Ni1 | 121.20 (11) |
N3—Ni1—S1 | 84.58 (5) | N3—C8—C9 | 131.97 (17) |
N3i—Ni1—S1 | 95.42 (5) | N3—C8—H8 | 116.2 (13) |
S1i—Ni1—S1 | 180.00 (3) | C9—C8—H8 | 111.8 (13) |
C6—C1—C2 | 119.5 (2) | C10—C9—C14 | 119.10 (16) |
C6—C1—N1 | 116.8 (2) | C10—C9—C8 | 114.36 (17) |
C2—C1—N1 | 123.65 (18) | C14—C9—C8 | 126.46 (16) |
C1—C2—C3 | 119.7 (2) | C11—C10—C9 | 120.99 (18) |
C1—C2—H2 | 120.1 | C11—C10—H10 | 119.5 |
C3—C2—H2 | 120.1 | C9—C10—H10 | 119.5 |
C4—C3—C2 | 120.9 (2) | C12—C11—C10 | 119.49 (17) |
C4—C3—H3 | 119.6 | C12—C11—H11 | 120.3 |
C2—C3—H3 | 119.6 | C10—C11—H11 | 120.3 |
C3—C4—C5 | 118.9 (2) | C11—C12—O1 | 119.75 (16) |
C3—C4—H4 | 120.5 | C11—C12—C13 | 120.43 (16) |
C5—C4—H4 | 120.5 | O1—C12—C13 | 119.81 (17) |
C4—C5—C6 | 120.7 (3) | O2—C13—C14 | 125.69 (16) |
C4—C5—H5 | 119.6 | O2—C13—C12 | 113.95 (15) |
C6—C5—H5 | 119.6 | C14—C13—C12 | 120.35 (17) |
C1—C6—C5 | 120.3 (3) | C13—C14—C9 | 119.58 (16) |
C1—C6—H6 | 119.8 | C13—C14—H14 | 120.2 |
C5—C6—H6 | 119.8 | C9—C14—H14 | 120.2 |
C7—N1—C1 | 130.38 (17) | C12—O1—H1O1 | 109.5 |
C7—N1—H1N1 | 111.6 (19) | C13—O2—C15 | 117.54 (14) |
C1—N1—H1N1 | 117.9 (19) | O2—C15—H15A | 109.5 |
N2—C7—N1 | 121.37 (16) | O2—C15—H15B | 109.5 |
N2—C7—S1 | 123.56 (14) | H15A—C15—H15B | 109.5 |
N1—C7—S1 | 115.05 (13) | O2—C15—H15C | 109.5 |
C7—S1—Ni1 | 96.21 (6) | H15A—C15—H15C | 109.5 |
C7—N2—N3 | 110.66 (14) | H15B—C15—H15C | 109.5 |
Symmetry code: (i) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O1ii | 0.81 (3) | 2.37 (3) | 3.122 (2) | 154 (2) |
O1—H1O1···N2iii | 0.84 | 2.54 | 3.131 (2) | 129 |
Symmetry codes: (ii) x−1, y+1, z; (iii) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O1i | 0.81 (3) | 2.37 (3) | 3.122 (2) | 154 (2) |
O1—H1O1···N2ii | 0.84 | 2.54 | 3.131 (2) | 129 |
Symmetry codes: (i) x−1, y+1, z; (ii) x, y−1, z. |
Acknowledgements
We gratefully acknowledge financial support by the State of Schleswig–Holstein, Germany. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities. BRSF thanks CNPq/UFS for the award of a PIBIC scholarship and ABO acknowledges financial support through the FAPITEC/SE/FUNTEC/CNPq PPP 04/2011 program.
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