catena-Poly[hemi{bis­[4′-(3-pyrid­yl)-2,2′:6′,2′′-terpyridine-κ3 N 1,N 1′,N 1′′]copper(II)} [cuprate(I)-di-μ2-thio­cyanato-κ2 N:S;κ2 S:N]]

Wen-Juan Shi

doi:10.1107/S1600536809023356

. 2009 Jun 24;65(Pt 7):m814. doi: 10.1107/S1600536809023356

catena-Poly[hemi{bis[4′-(3-pyridyl)-2,2′:6′,2′′-terpyridine-κ³ N ¹,N ^1′,N ^1′′]copper(II)} [cuprate(I)-di-μ₂-thiocyanato-κ² N:S;κ² S:N]]

Wen-Juan Shi ^a,^*

PMCID: PMC2969290 PMID: 21582737

Abstract

The title compound, {[Cu(C₂₀H₁₄N₄)₂][Cu₂(NCS)₄]}_n, was obtained by reacting copper acetate hydrate, ammonium thiocyanate and 4′-(3-pyridyl)-2,2′:6′,2′′-terpyridine (3-pytpy) under solvothermal conditions. The polymeric complex is isostructural with the 4′-phenyl-2,2′:6′,2′′-terpyridine (phtpy) analogue. All intramolecular distances and angles are very similar for the two structures. Substitution of a phenyl group with a pyridyl group has no significant effect on the crystal packing which is accomplished by C—H⋯N and C—H⋯S hydrogen-bonding interactions.

Related literature

For background to 2,2′:6′,2′′-terpyridine derivatives and their complexes, see: Andres & Schubert (2004 ▶); Constable (1986 ▶); Hofmeier & Schubert (2004 ▶). For the isostructural 4′-phenyl-2,2′:6′,2′′-terpyridine (phtpy) analogue, see: Shi (2009 ▶).

Experimental

Crystal data

[Cu(C₂₀H₁₄N₄)₂][Cu₂(NCS)₄]
M _r = 1043.64
Triclinic,
a = 10.0031 (6) Å
b = 10.2202 (6) Å
c = 21.2612 (12) Å
α = 82.607 (1)°
β = 87.732 (1)°
γ = 80.132 (1)°
V = 2123.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.74 mm⁻¹
T = 295 K
0.16 × 0.13 × 0.11 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.769, T _max = 0.832
16747 measured reflections
8252 independent reflections
6751 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.103
S = 1.03
8252 reflections
568 parameters
H-atom parameters constrained
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); 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/S1600536809023356/zl2221sup1.cif

e-65-0m814-sup1.cif^{(35.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023356/zl2221Isup2.hkl

e-65-0m814-Isup2.hkl^{(403.6KB, 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
C4—H4⋯S4ⁱ	0.93	2.87	3.756 (3)	160
C15—H15⋯S2ⁱⁱ	0.93	2.83	3.676 (4)	151
C17—H17⋯S4ⁱ	0.93	2.80	3.650 (3)	152
C21—H21⋯S4ⁱⁱⁱ	0.93	2.79	3.627 (3)	150
C29—H29⋯S2^iv	0.93	2.78	3.654 (3)	156
C35—H35⋯N4^v	0.93	2.47	3.217 (4)	137

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

Acknowledgments

The author thanks Jiangxi Science and Technology Normal University for supporting this study.

supplementary crystallographic information

Comment

2,2':6',2''-Terpyridine and its derivatives have been intensively explored because of the interesting electronic, photonic, magnetic, reactive and structural properties shown by the transition metal complexes of these ligands (Andres & Schubert, 2004; Constable, 1986; Hofmeier & Schubert, 2004). We report here the synthesis and structure of the Cu^II complex based on the 4'-(3-pyridyl)-2,2':6',2''-terpyridine (3-pytpy) ligand.

Fig. 1 illustrates the essential structural features of the title complex which consists of a packing of one [Cu(3-pytpy)₂]²⁺ cation with two independent crystallographically centrosymmetric polymeric [Cu(SCN)₂]^- anions. The central Cu^II ion in the cation is coordinated by two tridentate chelating units of the two 3-pytpy ligands to form an octahedral coordination geometry. Each Cu^I ion in the anion exhibits a distorted tetrahedral geometry and is coordinated by two S atoms and two N atoms from four thiocyanate ligands. Each thiocyanate ligand acts as a 1,3-µ₂ bridge to link two Cu^I ions to generate two isostructural [Cu(SCN)₂]_n^n- anionic chains. The terpyridyl units of the 3-pytpy ligands are approximately planar [interannular torsion angles: 3.7 (1) °, 10.3 (2) °; 7.9 (3) °, 8.6 (2) °], the dihedral angles between the pendant and central pyridine ring are 18.4 (1) ° and 38.1 (2) °, respectively.

In the crystal packing, the neighbouring cationic units are packed by intermolecular C–H···N hydrogen bonds, and the [Cu(SCN)₂]_n^n- anionic chains are involved in intermolecular C–H···S hydrogen bonding interactions with the –CH groups of the 3-pytpy ligands, resulting in a three-dimensional supramolecular structure (Fig. 2).

Experimental

A mixture of copper acetate hydrate (40.1 mg, 0.20 mmol), 3-pytpy (31.0 mg, 0.10 mmol) and ammonium thiocyanate (15.3 mg, 0.20 mmol) in ethanol (10 ml) was sealed in a 15 ml Teflon-lined reactor, heated to 418 K for 72 h, and then cooled to room temperature at a rate of 6 K/h to give black crystals of the title compound. Yield: 9 mg (17%).