mer-(3,5-Dichloro-2-oxidobenzaldehyde thio­semicarbazonato-κ3 S,N 1,O)(methanol-κO)(1,10-phenanthroline-κ2 N,N′)nickel(II)

J Y Gao; Z Liu; Y Wang

doi:10.1107/S1600536809013208

. 2009 Apr 18;65(Pt 5):m523–m524. doi: 10.1107/S1600536809013208

mer-(3,5-Dichloro-2-oxidobenzaldehyde thiosemicarbazonato-κ³ S,N ¹,O)(methanol-κO)(1,10-phenanthroline-κ² N,N′)nickel(II)

J Y Gao ^a, Z Liu ^a,^*, Y Wang ^a

PMCID: PMC2977580 PMID: 21583766

Abstract

In the title compound, [Ni(C₈H₅Cl₂N₃OS)(C₁₂H₈N₂)(CH₃OH)], the Ni^II atom is octahedrally coordinated by one N, one O and one S atom from a 3,5-dichloro-2-oxidobenzaldehyde thiosemicarbazonate ligand, another O atom from methanol and another two N atoms from 1,10-phenanthroline. The crystal structure is constructed by N—H⋯Cl, N—H⋯N, C—H⋯S and O—H⋯S hydrogen bonds.

Related literature

For nickel complexes with salicylic aldehyde thiosemicarbazone ligands, see: Dapporto et al. (1984 ▶); Schulte et al. (1991 ▶); García-Reynaldos et al. (2007 ▶); Kolotilov et al. (2007 ▶); Qiu & Wu (2004 ▶). For related Cu(II) compounds with a distorted octahedral coordination as a result of the Jahn–Teller effect, see: García-Orozco et al. (2002 ▶). For bond-length data, see: Orpen et al. (1989 ▶). For related structures, see: Seena & Kurup (2007 ▶); Wang et al. (2008 ▶); Zhang et al. (2007 ▶).

Experimental

Crystal data

[Ni(C₈H₅Cl₂N₃OS)(C₁₂H₈N₂)(CH₄O)]
M _r = 533.07
Monoclinic,
a = 12.058 (1) Å
b = 12.946 (1) Å
c = 14.973 (2) Å
β = 105.918 (1)°
V = 2247.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.22 mm⁻¹
T = 298 K
0.30 × 0.28 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.710, T _max = 0.857
10910 measured reflections
3951 independent reflections
2708 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.119
S = 1.06
3951 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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/S1600536809013208/im2109sup1.cif

e-65-0m523-sup1.cif^{(24.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809013208/im2109Isup2.hkl

e-65-0m523-Isup2.hkl^{(193.7KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯S1ⁱ	0.82	2.49	3.310 (3)	174
N3—H3A⋯N2ⁱⁱ	0.86	2.24	3.087 (4)	170
N3—H3B⋯Cl1ⁱⁱⁱ	0.86	2.86	3.573 (2)	142
C11—H11⋯S1^iv	0.93	2.81	3.593 (5)	142

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

We acknowledge financial support by the Key Laboratory of Non-ferrous Metal Materials and New Processing Technology, Ministry of Education, P. R. China.

supplementary crystallographic information

Comment

As a special kind of Schiff bases, thiosemicarbazones and their metal complexes have become the subjects of intensive study because of their wide ranging biological activities, analytical applications and interesting chemical and structural properties. By now there are not many nickel complexes with salicylic aldehyde thiosemicarbazone ligands [Dapporto et al. (1984); Schulte et al. (1991); García-Reynaldos et al. (2007); Kolotilov et al. (2007); Qiu et al. (2004)]. The additional use of 1,10-phenanthroline as the third ligand depicts another structural type.

In (I), the Ni^II atom is coordinated by one N, one O and one S atom from the tridentate dianionic 3,5-dichlorosalicylaldehyde thiosemicarbazonato ligand, one O atom from methanol and two N atoms from phen. The six atoms form a distorted octahedral coordination sphere around the metal because of Jahn-Teller effect (García-Orozco et al., 2002). The Ni—S bond length is 2.358 (1) Å, which is very close to 2.295Å (Orpen et al. 1989). The three-dimensional network of (I) is established by N–H···Cl, N–H···N, C–H···S and O–H···S hydrogen bonds (Fig.2).

Experimental

A solution of 3,5-dichlorosalicylaldehyde (10 mmol) in EtOH (30 ml) was added dropwise to an aqueous solution (25 ml) of thiosemicarbazide (10 mmol) and 1.5 ml acetic anhydride with stirring at ca 70° C for 4.5 h. The light brown precipitate was removed by filtration and recrystallized from 1:1 (v/v) MeOH/EtOH. Then a mixture of the ligand (1 mmol) and nickel nitrate (1 mmol) in MeOH (35 ml) was stirred at ca 65° C for 2 h. After 1,10-phenanthroline (1 mmol) was added to the mixture heating was continued for another 2 h. The Ni complex was dissolved in DMF and the resulting red solution was filtrated. After 4 days, red block crystals were obtained by slow evaporation of the solvent from the filtrate.