CRYSTAL STRUCTURE OF (2,2’-DIPYRIDYLAMINE)-μ3-(1,3-BENZENEDICARBOXYLATO)ZINC(II)

Abstract

Designing of mixed Zn(II) complexes with benzenedicarboxylato and amine ligands attracts much attention because of the amazing chain, layer or 3D framework structures that arise [1]. Besides the variety of topologies, these compounds can potentially be applied in catalysis, nonlinear optics and absorption [2]. Due to all the above, and also in accordance with our previous research [3], a new chain Zn(II) complex with dianion of isophthalic acid (ipht) and 2,2’-dipyridylamine (dipya) has been synthesized. In the title complex, [Zn(dipya)(ipht)], ipht acts as bridging ligand with one monodentate and another chelate COO group (Fig. 1). Zn(II) atom is surrounded by two N atoms from chelately coordinated dipya and three O atoms from two ipht ligands, making a deformed square pyramidal environment. Bond distances and angles are in the range of 1.955(2) – 2.322(3) Å and 58.94(9) – 143.81(9) º, respectively. Each ipht ligand links two Zn(II) atoms making chains along the c-axis (Fig. 2). Aromatic rings of ipht and dipya are almost perpendicular with dihedral angles of 89.18(6) and 90.82(6) º. By intermolecular hydrogen bonds [d = 2.06(3) Å] between the amine H atom from dipya and uncoordinated O atom from monodentate COO group of ipht, the chains are packed in the layers nearly parallel to the ac-plane. Crystal data: C18H13N3O4Zn, Mr = 400.68, monoclinic system, space group P21/n, a = 11.3220(6), b = 8.8510(5), c = 17.6750(8) Å, β = 102.323(5) o, V = 1730.42(16) Å3, Z = 4, F(000) = 816, ρx = 1.538 g cm–3, μ (Mo Kα) = 1.448 mm–1. The refinement on F 2 (239 parameters) yielded R1 = 0.0514, wR2 = 0.0883, S = 1.045 for all data, and R1 = 0.0377 for 2694 observed reflections with I ≥ 2σ(I). Fig. 1. The asymmetric unit of [Zn(dipya)(ipht)]

Dizajniranje mešovitih Zn(II)-kompleksa sa dikarboksilatima benzena i aminskim ligandima privlači veliku pažnju zbog fascinantnih lančastih, slojevitih i 3D struktura koje pri tom nastaju [1]. Pored različitih topologija, ova jedinjenja se potencijalno mogu primeniti u katalizi, nelinearnoj optici i apsorpciji [2]. Zbog svega navedenog, a u skladu sa našim prethodnim istraživanjima [3], sintetisan je novi lančasti Zn(II)-kompleks sa anjonom izoftalne kiseline (ipht) i 2,2’-dipiridilaminom (dipya). U navedenom komleksu, [Zn(dipya)(ipht)], ipht je mostovni ligand sa jednom monodentatnom i drugom helatnom COO-grupom (sl. 1). Zn(II)-atom okružen je sa dva atoma azota iz helatno koordiniranog dipya i tri atoma kiseonika iz dva ipht liganda, čineći okruženje u obliku deformisane kvadratne piramide. Dužine veza i uglovi nalaze se redom u opsegu 1,955(2) – 2,322(3) Å i 58,94(9) – 143,81(9) º. Svaki ipht ligand povezuje dva Zn(II)-atoma formirajući lanac duž c-ose (sl. 2). Aromatični prstenovi ipht i dipya su približno normalni sa diedarskim uglovima od 89,18(6) i 90,82(6) º. Intermolekulskim vodoničnim vezama [d = 2,06(3) Å] između aminskog H-atoma iz dipya i nekoordiniranog O-atoma iz monodentatne COO-grupe, lanci su povezani u slojeve približno paralelne ac-ravni. Sl. 2. Lanci [Zn(dipya)(ipht)] duž c-ose Strukturni podaci: C18H13N3O4Zn, Mr = 400,68, monokliničan sistem, prostorna grupa P21/n, a = 11,3220(6), b = 8,8510(5), c = 17,6750(8) Å, β = 102,323(5) º, V = 1730,42(16) Å3, Z = 4, F(000) = 816, ρx = 1,538 g cm–3, μ (Mo Kα) = 1,448 mm–1. Utačnjavanje sa F 2 (239 parametara) dalo je R1 = 0,0514, wR2 = 0,0883, S = 1,045 za sve podatke, i R1 = 0,0377 za 2694 refleksija sa I ≥ 2σ(I).