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The title complex crystallizes as a tetraethanol solvate, [Ni(C9H10N3O2S)2]·4C2H6O, with the metal on a centre of inversion. Two singly deprotonated ligands coordinate the metal atom in a planar fashion. The metal complexes are organized into layers by an extended network of hydrogen bonds involving the NH2 groups, the phenolic OH groups and the solvent mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100001657/os1098sup1.cif
Contains datablocks I, default

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100001657/os1098Isup2.hkl
Contains datablock I

CCDC reference: 145524

Comment top

Transition metal complexes with thiosemicarbazones possess important biological activities. Antimalarial, antiviral and antibacterial activities have been proved for various representatives of this class of compounds (West et al., 1991). Nevertheless, structural studies are comparatively rare and predominantly deal with complexes having tridentate thiosemicarbazones. To our knowledge, there is only one report on a transition metal complex with the fairly hydrophilic, bidentate 4-hydroxy-3-methoxybenzaldehyde thiosemicarbazone (vanilline thiosemicarbazone, Hvtsc) (Ortner & Abram, 1998), whereas the coordination chemistry of the isomeric, but potentially tridentate, ligand 2-hydroxy-3-methoxybenzaldehyde thiosemicarbazone is better known (Cui & Hu, 1994a,b; Agarwala & Hingorani, 1997; Offiong et al., 1996). Here we describe the structure of the neutral nickel(II) complex, [Ni(vtsc)2], (I), which contains two chelate-bonded vanilline thiosemicarbazonato ligands. \sch

The structure consists of [Ni(vtsc)2] molecules (Fig. 1) with the metal on a centre of inversion and hydrogen-bonded molecules of solvent ethanol. The organic ligands are deprotonated at the azomethine position and bonded to the metal via the sulfur and N3 atoms forming five-membered chelate rings. This results in an almost planar coordination with maximum deviation of 0.161 (1) Å from a least-square plane formed by the atoms Ni, S, C1, N2 and N3 (r.m.s. 0.1189 Å). The hydroxyl group remains protonated and does not contribute to the coordination of the metal. A comparison of the bond lengths found for [Ni(vtsc)2] with those in the [Au(Hdamp)Cl(vtsc)]+ cation [Hdamp is 2-(dimethylammoniummethyl)phenyl], (Ortner & Abram, 1998) indicates a considerably higher degree of delocalization of electron density inside the chelate rings of the nickel compound under study. This is reflected by the C1—S bond length of 1.726 (3) Å (Table 1) which lies between the values of isolated C—S single and double bonds, whereas a C—S bond of 1.76 Å with almost single bond character has been found for the gold compound. The same is true for the C,N-skeletons of the thiosemicarbazone moieties which show nearly equal bonds for [Ni(vtsc)2], whereas alternating short and long values are observed for the gold complex. An unusually short C—C bond length is observed in one of the solvent molecules which is probably due to thermal motion and/or disorder.

The triclinic unit cell contains four molecules of the solvate ethanol. Hydrogen bridges between the complex molecules and two symmetry-related ethanol molecules form a two-dimensional arrangement. These layers are interconnected by additional hydrogen bonds between H30 and the nitrogen atoms of the thiosemicarbazone backbone of a complex molecule of the neigbouring layer. The hydrogen-bonding parameters are summarized in Table 2.

Experimental top

[Ni(vtsc)2] was prepared as previously reported (Akinchan et al., 1992). Brown, column-shaped single crystals of the sparingly soluble complex have been obtained from slow cooling of a concentrated ethanol solution.

Refinement top

Scattering factors, dispersion corrections and absorption coefficients were taken from International Tables for Crystallography, Vol. C. (1992).

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: SET4 in SDP (Frenz, 1983); data reduction: SDP; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. : Ellipsoid diagram (Zsolnai, 1997) of the molecular structure of [Ni(vtsc)2] showing 50% probability displacement ellipsoids. Symmetry operation: (i) -x, -y, -z.
'Bis(vanillin thiosemicarbazonato)nickel(II) ethanol solvate' top
Crystal data top
[Ni(C9H10N3O2S)2]·4C2H6OZ = 1
Mr = 691.50F(000) = 366
Triclinic, P1Dx = 1.396 Mg m3
a = 6.894 (1) ÅCu Kα radiation, λ = 1.54184 Å
b = 10.675 (1) ÅCell parameters from 25 reflections
c = 11.878 (2) Åθ = 18.2–26.7°
α = 73.19 (1)°µ = 2.50 mm1
β = 79.75 (1)°T = 203 K
γ = 84.91 (1)°Column, brown
V = 822.8 (2) Å30.30 × 0.25 × 0.25 mm
Data collection top
Enraf Nonius CAD4
diffractometer
2695 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.019
Graphite monochromatorθmax = 64.9°, θmin = 6.5°
ω scansh = 18
Absorption correction: ψ scans
SDP (Frenz, 1983)
k = 1212
Tmin = 0.503, Tmax = 0.536l = 1313
3560 measured reflections3 standard reflections every 200 reflections
2792 independent reflections intensity decay: 1.0%
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)] = 0.052H-atom parameters constrained
wR(F2) = 0.152Calculated w = 1/[σ2(Fo2) + (0.094P)2 + 0.5715P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
2792 reflectionsΔρmax = 0.65 e Å3
197 parametersΔρmin = 0.59 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0154 (19)
Crystal data top
[Ni(C9H10N3O2S)2]·4C2H6Oγ = 84.91 (1)°
Mr = 691.50V = 822.8 (2) Å3
Triclinic, P1Z = 1
a = 6.894 (1) ÅCu Kα radiation
b = 10.675 (1) ŵ = 2.50 mm1
c = 11.878 (2) ÅT = 203 K
α = 73.19 (1)°0.30 × 0.25 × 0.25 mm
β = 79.75 (1)°
Data collection top
Enraf Nonius CAD4
diffractometer
2695 reflections with I > 2σ(I)
Absorption correction: ψ scans
SDP (Frenz, 1983)
Rint = 0.019
Tmin = 0.503, Tmax = 0.5363 standard reflections every 200 reflections
3560 measured reflections intensity decay: 1.0%
2792 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.152H-atom parameters constrained
S = 1.09Δρmax = 0.65 e Å3
2792 reflectionsΔρmin = 0.59 e Å3
197 parameters
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
Ni0.00000.00000.00000.0358 (3)
S0.28664 (9)0.10377 (6)0.00553 (7)0.0456 (3)
N10.3298 (4)0.3510 (2)0.0016 (2)0.0499 (6)
H1A0.29420.42110.01460.060*
H1B0.44180.35130.02260.060*
N20.0440 (3)0.2462 (2)0.0556 (2)0.0408 (5)
N30.0624 (3)0.1260 (2)0.07254 (19)0.0384 (5)
C10.2123 (4)0.2426 (3)0.0189 (2)0.0400 (6)
C20.1939 (4)0.1084 (3)0.1424 (2)0.0410 (6)
H20.27220.03100.14700.049*
C110.2413 (4)0.1870 (3)0.2145 (2)0.0424 (6)
C120.1361 (5)0.2972 (3)0.2372 (3)0.0566 (8)
H120.02520.33090.20050.068*
C130.1953 (5)0.3568 (3)0.3142 (3)0.0614 (9)
H130.12210.43010.33010.074*
C140.3580 (5)0.3114 (3)0.3675 (3)0.0514 (7)
C150.4665 (4)0.2024 (3)0.3456 (2)0.0449 (6)
C160.4074 (4)0.1404 (3)0.2710 (2)0.0436 (6)
H160.47930.06560.25760.052*
C170.7436 (5)0.0548 (4)0.3817 (3)0.0606 (8)
H17A0.85090.03740.42780.091*
H17B0.79720.07410.29760.091*
H17C0.66340.02140.40470.091*
O10.6250 (3)0.1645 (2)0.4040 (2)0.0585 (6)
O20.4162 (3)0.3694 (2)0.4439 (2)0.0629 (6)
H2A0.33910.43200.45070.094*
O200.2447 (4)0.5963 (3)0.4781 (2)0.0767 (8)
H200.34380.63490.47860.115*
C210.1401 (9)0.6738 (5)0.3870 (6)0.1128 (19)
H21A0.21100.66700.30970.135*
H21B0.00980.63770.39860.135*
C220.1159 (10)0.8033 (5)0.3840 (5)0.1125 (18)
H22A0.04480.84980.31970.169*
H22B0.24410.84040.37110.169*
H22C0.04160.81140.45920.169*
O300.2661 (3)0.4154 (2)0.9294 (2)0.0552 (5)
H300.17660.36730.97100.083*
C310.2732 (7)0.4209 (4)0.8080 (3)0.0802 (12)
H31A0.37710.47970.75980.096*
H31B0.14750.45920.78350.096*
C320.3105 (8)0.2937 (5)0.7814 (4)0.0883 (13)
H32A0.31360.30620.69690.132*
H32B0.20620.23540.82650.132*
H32C0.43630.25570.80340.132*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.0362 (4)0.0333 (4)0.0422 (4)0.0023 (2)0.0098 (3)0.0163 (3)
S0.0386 (4)0.0415 (4)0.0666 (5)0.0051 (3)0.0156 (3)0.0282 (3)
N10.0463 (13)0.0379 (12)0.0737 (16)0.0073 (10)0.0243 (12)0.0221 (11)
N20.0429 (12)0.0341 (11)0.0502 (13)0.0057 (9)0.0151 (10)0.0169 (9)
N30.0394 (11)0.0341 (11)0.0430 (11)0.0034 (8)0.0094 (9)0.0128 (9)
C10.0405 (14)0.0383 (13)0.0442 (14)0.0018 (10)0.0094 (11)0.0156 (11)
C20.0415 (14)0.0385 (13)0.0474 (14)0.0050 (11)0.0122 (11)0.0177 (11)
C110.0433 (14)0.0449 (14)0.0455 (14)0.0042 (11)0.0134 (11)0.0206 (12)
C120.0562 (18)0.0600 (19)0.071 (2)0.0170 (15)0.0307 (15)0.0391 (16)
C130.0616 (19)0.064 (2)0.079 (2)0.0217 (16)0.0314 (17)0.0466 (18)
C140.0552 (17)0.0591 (18)0.0506 (16)0.0022 (14)0.0151 (13)0.0290 (14)
C150.0416 (14)0.0541 (16)0.0427 (14)0.0027 (12)0.0121 (11)0.0174 (12)
C160.0429 (14)0.0450 (14)0.0462 (14)0.0048 (11)0.0123 (11)0.0168 (12)
C170.0528 (18)0.074 (2)0.0621 (19)0.0166 (16)0.0220 (15)0.0275 (16)
O10.0510 (12)0.0744 (15)0.0633 (13)0.0143 (10)0.0273 (10)0.0340 (11)
O20.0634 (13)0.0742 (15)0.0730 (15)0.0133 (11)0.0290 (11)0.0487 (12)
O200.0734 (16)0.0777 (17)0.0888 (18)0.0213 (13)0.0353 (14)0.0321 (14)
C210.107 (4)0.087 (3)0.157 (5)0.016 (3)0.066 (4)0.031 (3)
C220.144 (5)0.082 (3)0.119 (4)0.009 (3)0.045 (4)0.024 (3)
O300.0544 (12)0.0465 (11)0.0676 (13)0.0068 (9)0.0144 (10)0.0159 (10)
C310.110 (3)0.062 (2)0.065 (2)0.002 (2)0.027 (2)0.0051 (18)
C320.106 (3)0.098 (3)0.061 (2)0.014 (3)0.012 (2)0.028 (2)
Geometric parameters (Å, º) top
Ni—N3i1.908 (2)C12—C131.387 (4)
Ni—N31.908 (2)C13—C141.368 (4)
Ni—Si2.1799 (7)C14—O21.367 (3)
Ni—S2.1799 (7)C14—C151.390 (4)
S—C11.726 (3)C15—O11.367 (3)
N1—C11.340 (3)C15—C161.380 (4)
N2—C11.317 (3)C17—O11.429 (4)
N2—N31.401 (3)O20—C211.425 (5)
N3—C21.301 (3)C21—C221.369 (7)
C2—C111.452 (4)O30—C311.419 (4)
C11—C121.394 (4)C31—C321.472 (6)
C11—C161.410 (4)
N3i—Ni—N3180.0C12—C11—C16118.0 (2)
N3i—Ni—Si85.42 (7)C12—C11—C2127.2 (2)
N3—Ni—Si94.58 (7)C16—C11—C2114.7 (2)
N3i—Ni—S94.58 (7)C13—C12—C11119.9 (3)
N3—Ni—S85.42 (7)C14—C13—C12121.5 (3)
Si—Ni—S180.0O2—C14—C13121.7 (3)
C1—S—Ni95.44 (9)O2—C14—C15118.5 (3)
C1—N2—N3112.2 (2)C13—C14—C15119.9 (3)
C2—N3—N2115.3 (2)O1—C15—C16125.4 (3)
C2—N3—Ni125.24 (18)O1—C15—C14115.2 (3)
N2—N3—Ni119.40 (16)C16—C15—C14119.4 (3)
N2—C1—N1118.1 (2)C15—C16—C11121.3 (3)
N2—C1—S122.6 (2)C15—O1—C17117.0 (2)
N1—C1—S119.4 (2)C22—C21—O20114.1 (5)
N3—C2—C11131.6 (2)O30—C31—C32114.8 (3)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O30ii0.872.072.930 (3)168
O20—H20···O2iii0.832.022.753 (3)146
O2—H2A···O200.831.912.705 (3)160
N1—H1B···O30iv0.872.193.023 (3)161
O30—H30···N2v0.832.012.838 (3)174
O30—H30···N3v0.832.633.360 (3)147
Symmetry codes: (ii) x, y+1, z+1; (iii) x+1, y+1, z+1; (iv) x1, y, z1; (v) x, y, z+1.

Experimental details

Crystal data
Chemical formula[Ni(C9H10N3O2S)2]·4C2H6O
Mr691.50
Crystal system, space groupTriclinic, P1
Temperature (K)203
a, b, c (Å)6.894 (1), 10.675 (1), 11.878 (2)
α, β, γ (°)73.19 (1), 79.75 (1), 84.91 (1)
V3)822.8 (2)
Z1
Radiation typeCu Kα
µ (mm1)2.50
Crystal size (mm)0.30 × 0.25 × 0.25
Data collection
DiffractometerEnraf Nonius CAD4
diffractometer
Absorption correctionψ scans
SDP (Frenz, 1983)
Tmin, Tmax0.503, 0.536
No. of measured, independent and
observed [I > 2σ(I)] reflections
3560, 2792, 2695
Rint0.019
(sin θ/λ)max1)0.587
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.152, 1.09
No. of reflections2792
No. of parameters197
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.65, 0.59

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), SET4 in SDP (Frenz, 1983), SDP, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
Ni—N31.908 (2)N2—N31.401 (3)
Ni—S2.1799 (7)N3—C21.301 (3)
S—C11.726 (3)C2—C111.452 (4)
N2—C11.317 (3)
N3—Ni—S85.42 (7)N2—N3—Ni119.40 (16)
C1—S—Ni95.44 (9)N2—C1—S122.6 (2)
C1—N2—N3112.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O30i0.872.072.930 (3)167.7
O20—H20···O2ii0.832.022.753 (3)146.3
O2—H2A···O200.831.912.705 (3)159.5
N1—H1B···O30iii0.872.193.023 (3)160.8
O30—H30···N2iv0.832.012.838 (3)173.9
O30—H30···N3iv0.832.633.360 (3)146.9
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z+1; (iii) x1, y, z1; (iv) x, y, z+1.
 

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