catena-Poly[[[diaqua­copper(II)]-bis­(μ2-di-4-pyridyl disulfide-κ2 N:N′)] bis­(hydrogen phthalate) monohydrate]

Hong-Lin Zhu; Jie Zhang; Jian-Li Lin

doi:10.1107/S1600536810001716

. 2010 Jan 20;66(Pt 2):m185. doi: 10.1107/S1600536810001716

catena-Poly[[[diaquacopper(II)]-bis(μ₂-di-4-pyridyl disulfide-κ² N:N′)] bis(hydrogen phthalate) monohydrate]

Hong-Lin Zhu ^a, Jie Zhang ^a, Jian-Li Lin ^a,^*

PMCID: PMC2979707 PMID: 21579653

Abstract

The asymmetric unit of the title compound, {[Cu(C₁₀H₈N₂S₂)₂(H₂O)₂](C₈H₅O₄)₂·H₂O}_n, contains one Cu^II ion, two bridging di-4-pyridyl disulfide (4-DPDS) ligands of the same chirality, two coordinating water molecules, two hydrogen phthalate anions and one uncoordinated water molecule. The polymeric structure consists of two types of polymeric chains, each composed from repeated chiral rhomboids. The Cu^II ions adopt a distorted octahedral coordination geometry and are coordinated by four pyridine N atoms and two water O atoms. The coordinated water molecules and hydrogen phthalate anions are located between the repeated rhomboidal chains, and form hydrogen bonds with the coordinated water molecules.

Related literature

For general background to 4,4′-dipyridyldisulfide, see Horikoshi & Mochida (2006 ▶). For coordination complexes with the title ligand, see: Manna et al. (2005 ▶, 2007 ▶); Luo et al. (2003 ▶).

Experimental

Crystal data

[Cu(C₁₀H₈N₂S₂)₂(H₂O)₂](C₈H₅O₄)₂·H₂O
M _r = 888.44
Orthorhombic,
a = 20.253 (4) Å
b = 10.732 (2) Å
c = 17.228 (3) Å
V = 3744.6 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 295 K
0.40 × 0.13 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.870, T _max = 0.901
34124 measured reflections
8513 independent reflections
5968 reflections with I > 2σ(I)
R _int = 0.077

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.081
S = 1.02
8513 reflections
506 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ▶), 4088 Friedel pairs
Flack parameter: 0.00 (7)

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810001716/cv2686sup1.cif

e-66-0m185-sup1.cif^{(27.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810001716/cv2686Isup2.hkl

e-66-0m185-Isup2.hkl^{(416.5KB, 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
O1—HW1⋯O7	0.81	2.51	3.118 (6)	133
O1—HW2⋯O3ⁱ	0.81	1.92	2.658 (4)	153
O2—H2C⋯O7ⁱⁱ	0.75	2.13	2.878 (4)	174
O2—H2D⋯O9	0.80	2.05	2.841 (4)	171
O3—H3C⋯O4ⁱⁱ	0.81	2.02	2.800 (4)	163
O3—H3D⋯O11	0.76	2.03	2.784 (5)	172
O5—H5C⋯O6	0.85	1.51	2.358 (5)	178
O8—H8C⋯O11	0.87	1.50	2.367 (4)	178

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

Acknowledgments

This project was supported by the National Natural Science Foundation of China (grant No. 20072022), the Science and Technology Department of Zhejiang Province (grant No. 2006 C21105) and the Education Department of Zhejiang Province. Grateful thanks are also extended to the K. C. Wong Magna Fund in Ningbo University.

supplementary crystallographic information

Comment

Over past few years, the 4,4'-dipyridyldisulfide has received considerable attention due to both its conformational flexibility and axial chirality (Horikoshi & Mochida, 2006). A large number of metal coordination networks have been reported by using these ligands only or in combination with suitable anions (Manna et al., 2005, 2007; Luo et al., 2003). In this contribution, we report the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound, {[Cu(4-DPDS)₂(H₂O)₂].2(C₈H₅O₄)^-.H₂O}_n (4-DPDS = 4,4'-dipyridinedisulfide),contains one Cu^II ion, two bridging 4-DPDS ligands of the same chirality, two coordinating water molecules, two hydrogen phthalate anions and one lattice water molecule (Fig. 1). The copper atoms are each coordinated by four pyridine nitrogen atoms and two aqua ligands to complete an elongated octahedral CuN₄O₂ chromophore of "4 + 2" coordination type due to Jahn-Teller effect. The equatorial positions are occupied by four N toms of four 4-DPDS ligands, and the axial ones by two aqua O atoms. The Cu—O distances of 2.513 (3) Å and 2.438 (3) Å are significantly larger than those to the nitrogen atoms (Cu—N = 2.031 (3)–2.054 (3) Å), indicating a weak coordination capability of the aqua ligand. The cis and trans N—Cu—N angles fall in the regions 88.97 (9)–90.99 (9)° and 173.34 (13)–176.78 (12)°, respectively, exhibiting small deviation from the corresponding values for a regular geometry. The bond lengths (with the Cu atoms) are all within the normal ranges (Manna et al., 2007).

The Cu atoms are bridged by four 4-DPDS ligands to form one-dimensional double–stranded chains extending in the [010] direction. The one-dimensional chains with respect to the neighbour are close-packed in ···ABAB··· sequence (Fig. 2). Despite the Cu—Cu distance spanned by the two 4-DPDS are 10.732 (2) Å, but no similar mesoporous structure form, because the HL^- anions and lattice H₂O molecule reside in cavities in the one-dimensional chain metallacycle. The HL^- anions play a role in balancing in charge, the carboxylic –COOH groups favor formation of strong intramolecular hydrogen bond to carboxylate O6 atom and O11 atom, and the lattice H₂O molecule form hydrogen bonds to two HL^- ainions. The distance of S—S between adjacent chains is 5.17 (1) Å, which is much greater than van der waals distance (3.7 Å), shows that there is no S—S weak interaction.The chains are linked via those interchain hydrogen bonds between the aqua ligand and the carboxylate atoms (Table 1) into two-dimensional layers (Fig. 3).

Experimental

Dropwise addition of 0.5 ml 1.0 M NaOH to a aqueous solution of Cu(NO₃)₂.3H₂O (0.0603 g, 0.25 mmol) in 4 ml H₂O produced the blue precipitate, which was then centrifuged and washed with double-distilled water four times. The precipitate was subsequently moved to a stirred suspension of phthalic acid (0.0510 g, 0.25 mmol) and DPDS (4,4'-dipyridinedisulfide) (0.0575 g, 0.25 mmol) in 30 ml hot water. The mixture was further stirred for 30 min and the insoluble solid was filtere off. The colourless filtrate was allowed to stand at the room temperature. Slow evaporation for about a month afforded a small amount of blue block crystals.