catena-Poly[[copper(I)-μ-2,6-bis­[4-(pyridin-2-yl)thia­zol-2-yl]pyridine] hexa­fluoridophosphate acetonitrile monosolvate] from single-crystal synchrotron data

Linda Xiao; Mohan Bhadbhade; Anthony T Baker

doi:10.1107/S1600536813006831

. 2013 Mar 28;69(Pt 4):m231. doi: 10.1107/S1600536813006831

catena-Poly[[copper(I)-μ-2,6-bis[4-(pyridin-2-yl)thiazol-2-yl]pyridine] hexafluoridophosphate acetonitrile monosolvate] from single-crystal synchrotron data

Linda Xiao ^a, Mohan Bhadbhade ^b, Anthony T Baker ^a,^*

PMCID: PMC3629503 PMID: 23634021

Abstract

The title complex, {[Cu(C₂₁H₁₃N₅S₂)]PF₆·CH₃CN}_n, was formed immediately on adding together a methanol solution containing copper(I) ions and a methanol solution of 2,6-bis[4-(pyridin-2-yl)thiazol-2-yl]pyridine. Crystallographic studies of the complex reveal a coordination polymer with the ligand acting as a bis(bidentate) ligand with the pyridine N atom not coordinating a metal centre. The Cu^I atom is four-coordinate with approximately tetrahedral stereochemistry: the N₄ donor set is provided by bipyridine-like moieties of the two heterocyclic ligands. Parallel chains of the coordination polymer run along the b-axis direction with the disordered (0.50:0.50 occupancy ratio) PF₆ ⁻ anions and acetonitrile solvent molecules located between the chains.

Related literature

For a related complex, see: Baker & Matthews (1999 ▶). graphic file with name e-69-0m231-scheme1.jpg

Experimental

Crystal data

[Cu(C₂₁H₁₃N₅S₂)]PF₆·C₂H₃N
M _r = 649.05
Monoclinic,
a = 12.525 (3) Å
b = 13.950 (3) Å
c = 14.626 (3) Å
β = 97.72 (3)°
V = 2532.4 (9) Å³
Z = 4
Synchrotron radiation
λ = 0.71073 Å
μ = 1.16 mm⁻¹
T = 100 K
0.03 × 0.02 × 0.01 mm

Data collection

3-BM1 Australian Synchrotron diffractometer
28022 measured reflections
3890 independent reflections
3641 reflections with I > 2σ(I)
R _int = 0.024
θ_max = 23.8°

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.078
S = 1.08
3890 reflections
389 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: BLU-ICE (McPhillips et al., 2002 ▶); cell refinement: XDS (Kabsch, 1993 ▶); data reduction: XDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(34.8KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813006831/vm2190sup1.cif

e-69-0m231-sup1.cif^{(34.8KB, cif)}

Click here for additional data file.^{(190.7KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813006831/vm2190Isup2.hkl

e-69-0m231-Isup2.hkl^{(190.7KB, hkl)}

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

Acknowledgments

The authors thank the Australian Synchrotron Facility, Melbourne, for the X-ray data.

supplementary crystallographic information

Comment

We have prepared and studied many analogues of 2,2'-bipyridine and 2,2':6',2"-terpyridine (Baker and Matthews, 1999 and references therein) and have extended this work to the preparation of ligands analogous to quinquepyridine. For metal complexes of these quinquepyridine analogues, a number of features have been observed. The interpolation of a five-membered heterocycle appears to reduce the capacity of the ligands to employ all five donor atoms and we have seen several examples where the ligands act in a bis(bidentate) mode [2 + 2]. In such cases the ligands bridge between metal centres in binuclear complexes. Herein we report a coordination polymer shown in Scheme 1, again where the ligand binds in [2 + 2] mode. A thermal ellipsoid plot is shown in Fig. 1. Each copper centre has approximately tetrahedral stereochemistry as shown in Fig. 1. The principal cause of distortion being the bite angles of the bidentate ligand N2B—Cu1—N1B (82.47 (8)°) and N2Aⁱ—Cu1—N1Aⁱ (82.95 (8)°) (symmetry code: (i) -x + 1, y + 1/2, -z + 1/2) are considerably less than the ideal tetrahedral angle. Two 'thiazolylpyridine' moieties coordinate each copper(I) centre with the relevant bond lengths being Cu—N1Aⁱ 2.098 (2) Å, Cu—N1B 2.050 (2) Å, Cu—N2A 1.992 (2) Å and Cu—N2B 2.024 (2) Å. The Cu—N bond lengths are similar but the Cu—N_pyridinyl bonds are slightly shorter than the Cu—N_thiazolyl bonds. This indicates a slightly stronger interaction of the metal atom with the pyridinyl moiety, in line with base strength. A single chain of the coordination polymer, thus created, is depicted in Fig. 2 and packing of these chains that include PF₆^- anions and solvent molecules of acetonitriles are shown in Fig. 3.

Experimental

The quinquedentate ligand 2,6-bis(4-(pyridin-2-yl)thiazol-2-yl)pyridine was prepared by adding a solution of 2-(bromoacetyl)pyridinium hydrobromide (5.6 g, 20 mmol) in hot ethanol (50 ml) to a solution of 2,6-di(thioamido)pyridine (2.0 g, 10 mmol) in hot ethanol (50 ml). The solution was heated for 5 min, a yellow precipitate of 2,6-bis(4-(pyridin-2-yl)thiazol-2-yl)pyridinium hydrobromide separated soon. The mixture was allowed to stand for 30 min s and the yellow precipitate was filtered and washed with sodium bicarbonate (5%) until effervescence ceased. Yield: 75%. The complex was prepared as follows: Tetrakis(acetonitrile)copper(I) hexafluorophosphate (200 mg, 0.54 mmol) in hot methanol (20 ml) was added to a solution of the ligand (214 mg, 0.54 mmol) in hot methanol (20 ml). The reaction mixture was heated on the water bath for 1 h. An orange solid formed during this time and once cooled the solid was collected, washed with cooled methanol and stored over silica gel (yield 164 mg, 50%). Crystals were grown by vapour diffusion of diethyl ether into a concentrated acetonitrile solution of the complex.