Aqua­[1,8-bis­(pyridin-2-yl)-3,6-dithia­octane-κ4 N,S,S′,N′]copper(II) dinitrate acetonitrile monosolvate

Mayra Manzanera-Estrada; Marcos Flores-Alamo; Jean-Michel Grevy M; Lena Ruiz-Azuara; Luis Ortiz-Frade

doi:10.1107/S1600536811056145

. 2012 Jan 11;68(Pt 2):m135–m136. doi: 10.1107/S1600536811056145

Aqua[1,8-bis(pyridin-2-yl)-3,6-dithiaoctane-κ⁴ N,S,S′,N′]copper(II) dinitrate acetonitrile monosolvate

Mayra Manzanera-Estrada ^a, Marcos Flores-Alamo ^b, Jean-Michel Grevy M ^c, Lena Ruiz-Azuara ^b, Luis Ortiz-Frade ^a,^*

PMCID: PMC3274872 PMID: 22346819

Abstract

In the title compound, [Cu(C₁₆H₂₀N₂S₂)(H₂O)](NO₃)₂·CH₃CN, the Cu^II atom displays a distorted square-pyramidal coordination, in which a water molecule occupies the apical position and the basal plane is formed by two N atoms and two S atoms of a 1,8-bis(pyridin-2-yl)-3,6-dithiaoctane ligand. The crystal packing is stabilized by O—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For a related compound, see: Rodríguez-Torres et al. (2009 ▶). For related structures of Cu(II) complexes with 1,8-bis(pyridin-2-yl)-3,6-dithiaoctane ligands, see: Brubaker et al. (1979 ▶); Humphery et al. (1988 ▶). For a description of the geometry of complexes with five-coordinate Cu^II ions, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[Cu(C₁₆H₂₀N₂S₂)(H₂O)](NO₃)₂·C₂H₃N
M _r = 551.09
Triclinic,
a = 8.8409 (5) Å
b = 10.8140 (5) Å
c = 13.5141 (6) Å
α = 79.895 (4)°
β = 71.500 (4)°
γ = 69.817 (4)°
V = 1146.86 (10) Å³
Z = 2
Mo Kα radiation
μ = 1.18 mm⁻¹
T = 138 K
0.59 × 0.30 × 0.08 mm

Data collection

Oxford Diffraction Gemini Atlas diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T _min = 0.624, T _max = 0.914
8086 measured reflections
4509 independent reflections
3744 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.076
S = 1.06
4509 reflections
305 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811056145/hy2502sup1.cif

e-68-0m135-sup1.cif^{(24KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811056145/hy2502Isup2.hkl

e-68-0m135-Isup2.hkl^{(216.4KB, 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
O1W—H1D⋯O5ⁱ	0.74 (3)	1.94 (3)	2.669 (2)	169 (3)
O1W—H1E⋯O1	0.77 (2)	2.00 (3)	2.754 (3)	166 (2)
C3—H3⋯O2ⁱⁱ	0.95	2.55	3.487 (3)	168
C8—H8A⋯O1ⁱⁱⁱ	0.99	2.54	3.447 (3)	152
C8—H8B⋯O4ⁱⁱⁱ	0.99	2.55	3.341 (3)	137
C10—H10A⋯O1ⁱⁱⁱ	0.99	2.43	3.228 (3)	137
C10—H10B⋯O5^iv	0.99	2.45	3.271 (3)	140
C13—H13⋯O6^iv	0.95	2.42	3.277 (3)	149
C14—H14⋯O2^v	0.95	2.56	3.220 (3)	127
C16—H16⋯O6^v	0.95	2.36	3.126 (3)	137
C17—H17A⋯O6	0.98	2.26	3.145 (3)	150

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

Acknowledgments

The authors thank CONACyT (130500) for financial support.

supplementary crystallographic information

Comment

Cu(II)–[1,8-bis(pyridin-2-yl)-3,6-dithiaoctane] complex has demonstrated biological activity against human tumor cervix line HeLa, which can be related to bio-mimetic Cu-SOD activity. Electrochemical studies indicate that the high flexibility of the 1,8-bis(pyridin-2-yl)-3,6-dithiaoctane ligand towards the preferential geometry of central atom could be an important factor in biological activity. However, the crystal structure of this compound was not obtained (Rodríguez-Torres et al., 2009).

The asymmetric unit of the title compound contains one complex cation [Cu(pdto)(H₂O)]²⁺ [pdto = 1,8-bis(pyridin-2-yl)-3,6-dithiaoctane], two nitrate anions and one acetonitrile solvent molecule (Fig. 1). The complex cation consists of a five-coordinated Cu^II ion in a distorted squared-pyramidal environment. The basal sites are occupied by N1, N2, S1 and S2 of the 1,8-bis(pyridin-2-yl)-3,6-dithiaoctane ligand (Humphery et al., 1988). The basal Cu—N/S bond lengths are in a range of 2.0169 (17)–2.3488 (6) Å. The aqua ligand in the apical position has a Cu1—O1W bond distance of 2.1342 (16) Å, 0.129 Å shorter than that of 2.263 Å observed in [Cu(pdto)(ClO₄)]ClO₄ (Brubaker et al., 1979). The basal CuN₂S₂ plane presents a slight distortion from planarity (τ = 0.1621) (Addison et al., 1984), as shown by the displacements of the atoms from a mean plane through them; the metal ion is situated 0.2260 (5) Å above the N1/N2/S1/S2 plane [least-squares plane: 7.663 (2)x + 1.291 (4)y + 9.420 (4)z = 14.302 (4)].

The nitrate anions and acetonitrile molecule are not involved in the coordination sphere of the Cu ion. In the crystal, O—H···O and weak C—H···O hydrogen bonds stabilize the crystal packing (Table 1). The water molecule (O1W) interacts with O1 and O5 acceptor atoms of the nitrate anions, forming a C₂²(5) motif.

Experimental

Cu(NO₃).2.5H₂O (0.129 g, 0.56 mmol) was dissolved in 20 ml of anhydrous acetonitrile, followed by slow addition of 1,8-bis(pyridin-2-yl)-3,6-dithiaoctane (0.1693 g, 0.56 mmol) contained in 5 ml of anhydrous acetonitrile. A deep blue solution was obtained, and by slow ether diffusion, crystals suitable for X-ray analysis were obtained after 3 days.