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

Wen-Juan Shi

doi:10.1107/S1600536809023009

. 2009 Jun 20;65(Pt 7):m801. doi: 10.1107/S1600536809023009

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

Wen-Juan Shi ^a,^*

PMCID: PMC2969286 PMID: 21582726

Abstract

Reaction of 4′-phenyl-2,2′:6′,2′′-terpyridine (phtpy), copper acetate hydrate and ammonium thiocyanate under solvothermal conditions led to the formation of the title compound, {[Cu(C₂₁H₁₅N₃)₂][Cu₂(NCS)₄]}_n. The structure is composed of discrete [Cu(phtpy)₂]²⁺ cations and polymeric anionic {[Cu(SCN)₂]⁻} chains propagating along [010]. The central Cu²⁺ ion in the cation is coordinated by two tridentate chelating phtpy ligands in a distorted octahedral geometry. In each of the two crystallographically independent centrosymmetric anions, the Cu^I atoms are bridged in a 1,3-μ₂-bridging mode by two S and two N atoms, resulting in a distorted tetrahedral CuN₂S₂ coordination. The [Cu(phtpy)₂]²⁺ cations are fixed between these polymers by intermolecular C—H⋯S hydrogen bonds.

Related literature

For related 2,2′:6′,2′′-terpyridine derivatives and their complexes, see: Heller & Schubert (2003 ▶); Hofmeier & Schubert (2004 ▶); Shi et al. (2007 ▶). For the isostructural 4′-(3-pyridyl)-2,2′:6′,2′′-terpyridine (3-pytpy) analogue, see: Shi (2009 ▶).

Experimental

Crystal data

[Cu(C₂₁H₁₅N₃)₂][Cu₂(NCS)₄]
M _r = 1041.66
Triclinic,
a = 10.1803 (6) Å
b = 10.1829 (6) Å
c = 21.3203 (12) Å
α = 83.571 (1)°
β = 89.566 (1)°
γ = 81.676 (1)°
V = 2173.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.70 mm⁻¹
T = 295 K
0.15 × 0.14 × 0.12 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.785, T _max = 0.823
17217 measured reflections
8453 independent reflections
5988 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.141
S = 1.03
8453 reflections
568 parameters
54 restraints
H-atom parameters constrained
Δρ_max = 1.53 e Å⁻³
Δρ_min = −0.89 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/S1600536809023009/at2820sup1.cif

e-65-0m801-sup1.cif^{(34.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023009/at2820Isup2.hkl

e-65-0m801-Isup2.hkl^{(413.5KB, 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
C28—H28⋯S3ⁱ	0.93	2.82	3.697 (5)	158
C36—H36⋯S1	0.93	2.81	3.657 (5)	152

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank Jiangxi Science and Technology Normal University for supporting this study.

supplementary crystallographic information

Comment

2,2':6',2''-Terpyridine and its derivatives have attracted considerable interest as ligands in metal complexes because of their versatility as building blocks for supramolecular assembles and polymers (Heller & Schubert, 2003; Hofmeier & Schubert, 2004). As a continuing effort of our research on complexes of terpyridine derivatives (Shi et al., 2007), we here report the title compound by using 4'-phenyl-2,2':6',2''-terpyridine (phtpy) as ligand, containing discrete cations [Cu(phtpy)₂]²⁺ and one-dimensional polymeric anionic chains [Cu(SCN)₂]_n^n-.

As shown in Fig. 1, the molecular structure of the title compound consists of three independent fragments. The central Cu²⁺ ion in the cation is coordinated by two tridentate chelating phtpy ligands to form a distorted octahedral geometry. The phtpy ligands are approximately orthogonal to one another, with a dihedral angle of 76.4 (2) ° between planes through the three six-membered rings of the two ligands. The pendent and central pyridine in one phtpy are almost coplanar with a dihedral angle of 1.4 (1) °, but in the other phtpy, a corresponding serious tilt of 35.3 (2) ° is formed. There exists two independent crystallographically centrosymmetric [Cu(SCN)₂]^- anions, in which each Cu⁺ centre is coordinated by two S atoms and two N atoms from four isothiocyanate ligands with a distorted tetrahedron geometry. Each isothiocyanate anion acts as a 1,3-µ₂ bridging ligand to bridge two Cu⁺ ions, resulting in the formation of polymeric [Cu(SCN)₂]_n^n- anionic chains. All the SCN^- groups are almost linear with the S–C–N bond angles in the range 176.3 (7) °–179.1 (4) °.

Two –CH groups in the [Cu(phtpy)₂]²⁺ cation interact with two S atoms form two polymeric [Cu(SCN)₂]_n^n- anionic chains through C–H···S hydrogen bonds [C···S = 3.697 (5) Å and 3.657 (5) Å, respectively] to form a two-dimensional supramolecular array (Fig.ure 2).

Experimental

A mixture of copper acetate hydrate (39.9 mg, 0.20 mmol), phtpy (30.9 mg, 0.10 mmol) and ammonium thiocyanate (15.2 mg, 0.20 mmol) in ethanol (12 ml) was sealed in a 15 ml Teflon-lined reactor, heated to 423 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: 12 mg (22%)].