(3,5-Dichloro­salicylaldehyde thio­semi­carbazonato-κ3 S,N 1,O)(N,N′-dimethyl­formamide-κO)copper(II) dimethyl­formamide solvate

Yuan Wang; Zheng Liu; Jiong-Yang Gao

doi:10.1107/S1600536808008982

. 2008 Apr 10;64(Pt 5):m633–m634. doi: 10.1107/S1600536808008982

(3,5-Dichlorosalicylaldehyde thiosemicarbazonato-κ³ S,N ¹,O)(N,N′-dimethylformamide-κO)copper(II) dimethylformamide solvate

Yuan Wang ^a, Zheng Liu ^a, Jiong-Yang Gao ^a,^*

PMCID: PMC2961129 PMID: 21202186

Abstract

In the title compound, [Cu(C₈H₅Cl₂N₃OS)(C₃H₇NO)]·C₃H₇NO, the Cu^II atom is coordinated in a slightly distorted square-planar geometry by an O, an S and an N atom from the tridentate ligand 3,5-dichlorosalicylaldehyde thiosemicarbazonate ligand and one O atom from dimethylformamide. At the same time, the Cu atom is in contact with S and Cl atoms from another two complexes [Cu⋯S and Cu⋯Cl = 2.9791 (2) and 3.3800 (3) Å, respectively], thereby forming a [4 + 2] coordination geometry. The crystal structure exhibits N—H⋯O and N—H⋯N hydrogen bonds.

Related literature

For studies of thiosemicarbazone complexes containing amino acids, see: Garcia-Orozco et al. (2002 ▶); Seena et al. (2007 ▶); Valdes-Martinez et al. (1995 ▶); Singh et al. (1997 ▶); Shen et al. (1997 ▶); Zimmer et al. (1991 ▶).

Experimental

Crystal data

[Cu(C₈H₅Cl₂N₃OS)(C₃H₇NO)]·C₃H₇NO
M _r = 471.84
Monoclinic,
a = 9.4979 (10) Å
b = 9.8057 (12) Å
c = 21.744 (2) Å
β = 94.263 (2)°
V = 2019.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.47 mm⁻¹
T = 298 (2) K
0.49 × 0.47 × 0.24 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.532, T _max = 0.719
9869 measured reflections
3558 independent reflections
2587 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.098
S = 1.06
3558 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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/S1600536808008982/om2219sup1.cif

e-64-0m633-sup1.cif^{(20.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808008982/om2219Isup2.hkl

e-64-0m633-Isup2.hkl^{(170.9KB, hkl)}

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

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

Cu1—O1	1.909 (2)
Cu1—N1	1.954 (3)
Cu1—O2	1.985 (2)
Cu1—S1	2.2567 (10)

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O1—Cu1—N1	93.55 (11)
O1—Cu1—O2	90.55 (11)
N1—Cu1—O2	172.04 (11)
O1—Cu1—S1	176.26 (8)
N1—Cu1—S1	86.04 (8)
O2—Cu1—S1	89.43 (8)
C4—O1—Cu1	127.5 (2)
C9—O2—Cu1	123.8 (3)
C1—S1—Cu1	94.29 (11)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2ⁱ	0.86	2.14	2.992 (4)	170
N3—H3B⋯O3ⁱⁱ	0.86	2.08	2.886 (4)	157

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

Acknowledgments

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

supplementary crystallographic information

Comment

As a special kind of Schiff base, 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 (Zimmer, et al., 1991). In addition, salicylaldehyde thiosemicarbazone and its substituent analogs as well as their copper complexes has been synthesized. The N—S donor also have theoretical interest, as they are capable of furnishing an environment of controlled geometry and ligand field strength.

In the title compound there is a DMF molecule coordinated through O, in addition to one N, one O and one S atom from the tridentate ligand 3,5-dichlorosalicylaldehyde thiosemicarbazone forming a slightly distorted planar square geometry (Fig. 1). In the unit cell, above and below the distorted square plane are Cl and S atoms at a long distance forming a "4 + 2" geometry. The weak interaction length of S–Cu is 2.9791 (2) Å. This bond distance are in the range of upper values for a long coordination distance (2.5–3.0 Å) in Cu(II) compounds. The length of Cl–Cu is 3.3800 (3) Å (Fig. 2). All of these facts can be seen as the result of the Jahn-Teller effect (Garcia-Orozco et al., 2002). A three-dimensional network is formed through these Cl–Cu, S–Cu contacts, N–H···N and N–H···O hydrogen bonds (Fig.3).

Experimental

An EtOH solution (15 ml) of 3,5-dichlorosalicylaldehyde (5 mmol) was added dropwise to the solution (15 ml) of thiosemicarbazide (5 mmol) and 0.75 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 solution. Then a mixture of the ligand (0.5 mmol) and copper nitrate (0.5 mmol) in EtOH (35 ml) was stirred at ca 65° C for 2 h to give the desired complex. The Cu complex was dissolved in DMF, and ether slowly diffused into the DMF solution to afford almost quantitatively green crystals of the mononuclear complex at ambient temperature after several days.