Bis(thio­semicarbazide)nickel(II) bis­[2-(thio­semicarbazonometh­yl)benzene­sulfonate] dihydrate

Wei Zhang; Yuan-Tao Chen

doi:10.1107/S1600536809022144

. 2009 Jun 13;65(Pt 7):m774. doi: 10.1107/S1600536809022144

Bis(thiosemicarbazide)nickel(II) bis[2-(thiosemicarbazonomethyl)benzenesulfonate] dihydrate

Wei Zhang ^a, Yuan-Tao Chen ^a,^*

PMCID: PMC2969405 PMID: 21582704

Abstract

In the title compound, [Ni(CH₅N₃S)₂](C₈H₈N₃O₃S₂)₂·2H₂O, the Ni^II atom lies on a inversion centre and is four-coordinated by two N and two S atoms of two thiosemicarbazide ligands in an almost square-planar coordination. In the crystal structure, the molecules are linked into a three-dimensional network via C—H⋯O, C—H⋯N, N—H⋯O, N—H⋯S and O—H⋯O hydrogen bonds.

Related literature

For the design and synthesis of organic–inorganic hybrid materials and their potential practical applications, see: Hagrman et al. (1998 ▶); Ranford et al. (1998 ▶).

Experimental

Crystal data

[Ni(CH₅N₃S)₂](C₈H₈N₃O₃S₂)₂·2H₂O
M _r = 793.61
Triclinic,
a = 7.3853 (8) Å
b = 9.9043 (11) Å
c = 11.3140 (18) Å
α = 86.670 (2)°
β = 77.611 (1)°
γ = 75.177 (1)°
V = 781.40 (17) Å³
Z = 1
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 298 K
0.33 × 0.21 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.716, T _max = 0.872
4091 measured reflections
2717 independent reflections
2268 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.078
S = 1.03
2717 reflections
205 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022144/at2808sup1.cif

e-65-0m774-sup1.cif^{(19KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022144/at2808Isup2.hkl

e-65-0m774-Isup2.hkl^{(133.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Ni1—N5	1.903 (2)
Ni1—S3	2.1788 (7)

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N5ⁱ—Ni1—N5	180
N5ⁱ—Ni1—S3	91.59 (6)
N5—Ni1—S3	88.41 (6)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S2ⁱⁱ	0.86	2.73	3.475 (2)	147
N3—H3A⋯N2	0.86	2.29	2.643 (3)	105
N3—H3A⋯O4ⁱⁱⁱ	0.86	2.58	3.224 (3)	132
N4—H4⋯O4ⁱⁱⁱ	0.86	1.97	2.794 (3)	160
O4—H4C⋯O2	0.85	1.97	2.819 (3)	172
O4—H4D⋯O3^iv	0.85	2.19	3.036 (3)	172
O4—H4D⋯O4^v	0.85	2.58	2.903 (3)	104
N5—H5A⋯O2^vi	0.90	1.97	2.837 (3)	163
N5—H5B⋯O1ⁱⁱⁱ	0.90	2.23	2.893 (3)	130
N6—H6A⋯O3^vii	0.86	2.03	2.866 (3)	165
N6—H6B⋯S2^viii	0.86	2.50	3.298 (2)	156
C2—H2⋯O1	0.93	2.50	3.066 (3)	119
C5—H5⋯O2	0.93	2.38	2.811 (3)	108
C8—H8⋯N2	0.93	2.48	2.790 (4)	100

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Symmetry codes: (ii) Inline graphic ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Acknowledgments

The authors thank the Program for New Century Excellent Talents in Universities for a research grant.

supplementary crystallographic information

Comment

The design and synthesis of organic/inorganic hybrid materials have attracted intense attention in recent years owing to their potential practical applications, such as antitumor, antidiabetic, antitubercular activities, magnetism and catalysis (Ranford, et al., 1998; Hagrman, et al., 1998). In order to achieve supramolecular transition metal complexes by self-assembly, and to explore the relationship between the structure and the biological properties, as one part of our systematic work, in this paper, we report on the synthesis and crystal structure of the title compound, (I).

As shown in Fig. 1, the Ni^II atom lies on a inversion centre and it is four-coordinate with two N donors and two S donors of two thiosemicarbazide ligands, and adopts distorted square coordination. The bond distances of Ni1—N5 (N5A) [1.903 (2) Å], Ni1—S3 (S3A) [2.1788 (7)Å] are consistent with the bond lengths reported previously. The bond distances of Ni1—N5 (N5A) are shorter than the Ni1—S3 (S3A), showing that the strength of Ni1—N5 (N5A) are stronger than the Ni1—S3(S3A) (Table 1). In the crystal packing, the molecules form a one-dimensional chain structure by the C—H···O, N—H···O, N—H···S and O—H···O hydrogen bonds (Table 2).

Experimental

The solution of 1.0 mmol 2-formyl-benzenesulfonate-thiosemicarbazide was added to a solution of 0.5 mmol Ni(NCS)₂.4H₂O in 5 ml ethanol at room temperature. The mixture was refluxed for 4 h with stirring, then the resulting precipitate was filtered, washed, and dried in vacuo over P₄O₁₀ for 48 h. Single crystals suitable for X-ray structural analysis was obtained by slowly evaporating from methanol at room temperature.