A second polymorph of catena-poly[[(1,10-phenanthroline-κ2 N,N′)copper(II)]-di-μ-thio­cyanato-κ2 N:S;κ2 S:N]

Shi-Shen Zhang; Li-Jiang Chen; Yi-Feng Han

doi:10.1107/S1600536811001759

. 2011 Mar 5;67(Pt 4):m398. doi: 10.1107/S1600536811001759

A second polymorph of catena-poly[[(1,10-phenanthroline-κ² N,N′)copper(II)]-di-μ-thiocyanato-κ² N:S;κ² S:N]

Shi-Shen Zhang ^a,^*, Li-Jiang Chen ^a, Yi-Feng Han ^a

PMCID: PMC3099897 PMID: 21753934

Abstract

In the title coordination polymer, [Cu(NCS)₂(C₁₂H₈N₂)]_n, the Cu^II atom is situated on a twofold rotation axis and is coordinated by two N atoms from the bidentate 1,10-phenanthroline ligand and four thiocyanate groups to confer a CuN₄S₂ octahedral geometry and resulting in a layer structure extending parallel to (100).

Related literature

For the first polymorph of this composition, see: Breneman & Parker (1993 ▶). For related structures, see: Kulkarni et al. (2002 ▶); Morpurgo et al. (1984 ▶).

Experimental

Crystal data

[Cu(NCS)₂(C₁₂H₈N₂)]
M _r = 359.90
Monoclinic,
a = 14.0353 (13) Å
b = 10.3081 (9) Å
c = 10.2670 (9) Å
β = 111.034 (2)°
V = 1386.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.87 mm⁻¹
T = 294 K
0.25 × 0.22 × 0.15 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.633, T _max = 0.755
3938 measured reflections
1362 independent reflections
1254 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.076
S = 1.08
1362 reflections
97 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); 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 I, global. DOI: 10.1107/S1600536811001759/ng5084sup1.cif

e-67-0m398-sup1.cif^{(13.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811001759/ng5084Isup2.hkl

e-67-0m398-Isup2.hkl^{(67.3KB, hkl)}

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

Acknowledgments

This work was supported by the Qianjiang Talents Project of the Technology Office of Zhejiang Province (grant No. 2009R10029), the National Natural Science Foundation of China (grant No. 20803067) and the Zhejiang Provincial Top Academic Discipline of Applied Chemistry and Eco-Dyeing & Finishing Engineering (grant No. ZYG2010019).

supplementary crystallographic information

Comment

Phenanthroline and its derivatives have been achieving rapidly increasing attention not only for their potential application as functional materials, but aslo from their intriguing variety of architectures and topologies. 1, 10-Phenanthroline, as one kind of those ligand, has usually been used to construct a great variety of structurally interesting entities, such as monomers(Breneman et al. 1993), ploymers(Kulkarni et al. 2002; Morpurgo et al. 1984).

The structure of the title compound (I) is illustrated in Fig. 1. the Cu^II atom is coordinated by two N atoms from1, 10-Phenanthroline ligand, as well as by the two N atoms and two S atoms from four thiocyanate groups to confer a distorted octahedral coordination at the metal centre. Two S atoms occupy the axial position, showing weak interaction of Cu1—S1 bond [2.952 (3)], which give rise to one-dimensional chain along (100), the crystal packing is stabilized by the intermolecular π-π stacking interaction(Fig. 2).

In contrast to the first polymorph of this composition in which the distance of Cu—S bonds are longer [3.163 (2) Å], and the S—Cu—S' angles are nearly linear [170.86 (6)°]. The S—Cu—N angles in reported complex vary from 73.8 (1) to 99.1 (1)°, which make the octahedral geometry of this compound more disordered than the title compoud.

Experimental

The mixture of CuSCN (0.0244 g, 0.2 mmol), 1, 10-Phenanthroline (0.0132 g, 0.1 mmol), were placed and sealed in a 10 ml Teflon-lined stainless steel reactor and heated to 160 °C for 72 h, then cooled down to room temperature at a rate of 5 °C/ 60 min. Single crystals suitable for X-ray diffraction were obtained in the form of black bars in ca 35% yield.

The web of checkcif show one Alert level B(Hirshfeld Test Diff S1 – C7..8.52 su), we think this is the result of the sightly distorted S atom of the thiocyanate group for his weak interaction to the Cu atom.