Poly[[{μ3-tris­[2-(4-phenyl-1,2,3-triazol-1-yl)eth­yl]amine}silver(I)] hexa­fluorido­phosphate]

Hiromi Ohi; Mayumi Shimizu; Makoto Obata; Takuzo Funabiki; Shigenobu Yano

doi:10.1107/S1600536808028298

. 2008 Sep 13;64(Pt 10):m1256–m1257. doi: 10.1107/S1600536808028298

Poly[[{μ₃-tris[2-(4-phenyl-1,2,3-triazol-1-yl)ethyl]amine}silver(I)] hexafluoridophosphate]

Hiromi Ohi ^a, Mayumi Shimizu ^b, Makoto Obata ^b, Takuzo Funabiki ^c, Shigenobu Yano ^a,^*

PMCID: PMC2959415 PMID: 21201012

Abstract

The title compound, {[Ag(L)]PF₆)_n {L is tris[2-(4-phenyl-1,2,3-triazol-1-yl)ethyl]amine, C₃₀H₃₀N₁₀}, consists of alternating two-dimensional cationic layers of [Ag(L)]⁺ and anionic PF₆ ⁻ layers. Each Ag^I atom is three coordinated in a T-shaped geometry by three N atoms from three ligands. Each ligand links three Ag^I atoms, generating a two-dimensional network structure with two different metallacycles, A and B. In A, eight coordination units from four ligands connect four Ag^I atoms, forming a 48-membered ring. In B, four coordination units from two ligands link two Ag^I atoms, forming a 24-membered ring. Each B ring is surrounded by four A rings, and each A ring has four A and four B rings as neighbours. This cationic layer thus generates a 4.8² topology network, with each Ag^I centre and ligand acting as a three-connected topological node.

Related literature

For related literature, see: Newkome et al. (1999 ▶); Robin & Fromm (2006 ▶); Ohi et al. (2004 ▶, 2005 ▶); Obata et al. (2008 ▶).

Experimental

Crystal data

[Ag(C₃₀H₃₀N₁₀)]PF₆
M _r = 783.47
Monoclinic,
a = 14.893 (3) Å
b = 14.935 (3) Å
c = 15.735 (3) Å
β = 112.646 (5)°
V = 3230.2 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 193.1 K
0.30 × 0.15 × 0.05 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (Jacobson, 1998 ▶) T _min = 0.776, T _max = 0.963
31971 measured reflections
7326 independent reflections
4647 reflections with F ² > 2σ(F ²)
R _int = 0.075

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.055
S = 1.03
7326 reflections
463 parameters
All H-atom parameters refined
Δρ_max = 3.48 e Å⁻³
Δρ_min = −2.33 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC & Rigaku, 2006 ▶); cell refinement: CrystalClear; data reduction: CrystalStructure; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: CrystalStructure (Rigaku/MSC & Rigaku, 2006 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028298/bt2780sup1.cif

e-64-m1256-sup1.cif^{(39.3KB, cif)}

Structure factors: contains datablocks I, I. DOI: 10.1107/S1600536808028298/bt2780Isup2.hkl

e-64-m1256-Isup2.hkl^{(445.2KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Ag1—N4	2.208 (2)
Ag1—N7ⁱ	2.210 (3)
Ag1—N10ⁱⁱ	2.268 (2)

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N4—Ag1—N7ⁱ	132.43 (10)
N4—Ag1—N10ⁱⁱ	114.02 (10)
N7ⁱ—Ag1—N10ⁱⁱ	113.51 (10)

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

Acknowledgments

This work was financially supported in part by Grants-in-Aid for Scientific Research (Nos. 19350031 and 19614009) from the Ministry of Education, Culture, Sport, Science and Technology (MEXT) of the Japanese Government, the Japan–German exchange program supported by the Japan Society for the Promotion of Science (JSPS), Nara Women’s University Intramural Grant for Project Research, and grants from Osaka Gas, San-EiGen, and REI Medical Foundation for Chemical Research. The authors thank Professors Yuji Mikata, Takanori Nishioka, Akio Toshimitsu, Isamu Kinoshita and Michael Gottschaldt for valuable contributions.

supplementary crystallographic information

Comment

Coordination polymer complexes have attracted much attention due to their various intriguing framework topologies and their unique properties such as magnetism, physical gas adsorption, ion-exchange, heterogeneous catalysis, and so on (Newkome et al., 1999; Robin et al., 2006). We have recently demonstrated that a C₃ symmetric tripodal tripyridine ligand consisting of a 1,3,5-triethylbenzene spacer can be adopted in coordination polymer chemistry to give one- and/or two-dimensional coordination polymer complexes with a variety of network topology (Ohi et al., 2004, 2005). In this study, we synthesized a new C₃ symmetric lingad (L) consisting of triethylamine as the spacer and three 1,2,3-triazole groups as the metal binding site by using Huisgen reaction and used this ligand to synthesize a new Ag^I complex, [[Ag^I(L)](PF₆)]_n (I). We report here the crystal structure of Ag^I complex.

In the title compound (I), the asymmetric unit contained one ligand molecular, one Ag^I ion, and one PF₆^- counterion. No solvent molecules were incorporated in the structure. As shown in Fig. 1, each Ag^I ion features a T-shaped coordination geometry, being coordinated by three nitrogen atoms from three ligands [Ag—N: 2.208 (2)–2.268 (2) Å; N—Ag—N: 113.51 (10)–132.43 (10)°], and each ligand links three Ag^I atoms to generate a two-dimensional network structure with two different metallacycles A and B. In A, eight coordination moieties from four ligands connected four Ag^I atoms to form a 48-membered ring. In B, four coordination moieties from two ligands link two Ag^I atoms to form 24-membered ring. Each B ring is surrounded by four A rings, and each A ring neighbors upon four A and four B rings. Thus, this sheet generates a rare 4.8² topology network with each Ag^I center and lingad acting as a three-connected topological node (Fig. 2a). The two-dimensional polymer sheets are stacked alternate arranging cationic two-dimensional layers of [Ag^I(L)]⁺ and anionic (PF₆^-) layers to form laminated structure (Fig. 2b), where no specific interaction is probably between the sheets.

Experimental

The ligand tris((4-phenyl-1,2,3-triazole-1-yl)ethyl)amine) (L) was synthesized by using Huisgen reaction, which is known as cycloaddition of azide and acetylene derivatives to give 1,2,3-triazole unit (Obata et al., 2008). The title coordination complex, (I), was synthesized according to the following method. An acetone/CHCl₃ (v/v = 1/1, 5 ml) solution of Ag^IPF₆ (50.6 mg, 2.0 x 10 ^-4 mol) was added slowly to an acetone/CHCl₃ (v/v = 1/1, 45 ml) solution of L (104.6 mg, 2.0 x 10 ^-4 mol). After the mixture was stirred for 1 day under dark, the precipitate was collected by filtration to give white powder. This powder was dissolved in CH₃CN and insoluble materials were removed by filtration. The filtrate was concentrated under reduced pressure to give white powder (98.6 mg, yield 64%). Single crystals suitable for X-ray crystallographic analysis were obtained by recrystallization from CH₃CN/CHCl₃ (v/v = 2/1)/Et₂O. Anal. Calcd. for C₃₀H₃₀AgF₆N₁₀P: C 45.99, H 3.86, N 17.88. Found: C 46.17, H 4.00, N 17.80.