Based on the mixed-ligand system, five new entangled coordination polymers have been synthesized, namely, [Co1.5(1,3-bdc)1.5(tib)(H2O)] (1), [Ni(1,3-bdc)(tib)(H2O)2]·0.5H2O (2), [Cu(Hbtc)(Htpim)] (3), [Co(bpndc)(pytpy)(H2O)]·0.5H2O (4), and [Ni(bpndc)(pytpy)(H2O)]·0.5H2O (5), (1,3-bdc = 1,3-benzenedicarboxylate, btc = 1,3,5-benzenetricarboxylate, bpndc = 4,4′-benzophenone dicarboxylate, tib = 1,3,5-tris(1-imidazolyl)benzene, Htpim = 2,4,5-tri(4-pyridyl)-imidazole, pytpy = 2,4,6-tris(4-pyridyl)pyridine). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy and TG analyses. Compound 1 exhibits a new trinodal (3,4,4)-connected 3D self-penetrating framework with (83)2(63.82.9)2(84.9.10) topology. Compound 2 displays an interesting 2D → 3D polythreading framework constructed from sidearm-containing 2D 63-hcb nets. Compound 3 exhibits an unusual (2D → 3D) entangled array with the coexistence of polythreading and interdigitation self-assembled from sidearm-containing 2D double-edged nets. Compounds 4 and 5 both show an intriguing 3-fold interpenetrated PtS-type (4,4)-connected 3D framework containing meso-helices. In addition, the magnetic properties of compounds 1–5 have been investigated in the temperature range 2–300 K.

•Compounds 1–6 display different 2D → 3D interdigitated structures.•In 1 and 2, the 2D layers contain single-stranded meso-helical chains.•In 3, there are large rhombic cavities in the 2D sheet.•In 4, the 2D layer is built from rod-shaped SBUs.•In 5 and 6, the 2D layers exhibit highly undulating 44-sql networks.Six new coordination polymers, namely [Co2(1,2-bdc)2(bibp)2]·H2O (1), [Zn2(1,2-bdc)2(bibp)2]·H2O (2), [Ni2(1,2-bdc)2(bibp)3]·7H2O (3), [Cd(1,2-bdc)(bibp)0.5] (4), [Co(Hbtc)(bibp)] (5), [Cd(Hbtc)(bibp)] (6) (bibp = 1,4-bis(4-(imidazole-1-yl)benzyl)piperazine, 1,2-bdc = 1,2-benzenedicarboxylate, btc = 1,3,5-benzenetricarboxylate), have been synthesized under hydrothermal conditions. Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra and TG analyses. Compounds 1–6 display different 2D → 3D interdigitated structures due to their different 2D layers. In 1 and 2, the 2D layers contain single-stranded meso-helical chains. In 3, there are large rhombic cavities in the 2D sheet. In 4, the 2D layer is built from rod-shaped SBUs. In 5 and 6, the 2D layers exhibit highly undulating 44-sql networks. In addition, the magnetic properties for compounds 1, 3 and 5, and the photoluminescence properties for compounds 2, 4 and 6 have also been investigated.Six new coordination polymers have been synthesized by self-assembly of transition metal salts with a long flexible N-donor ligand (bibp, 1,4-bis(4-(imidazole-1-yl)benzyl)piperazine) and two aromatic polycarboxylates, which present different 2D → 3D interdigitated structures.

•Pillared-layer molybdenum-oxide-based inorganic–organic hybrid compounds.•8-Connected net with tetranuclear metal clusters as building blocks.•Nonoxygen-bound ligand coordinate directly to Mo and metal ion simultaneously.•The first 3D bimetallic pillar-layer hybrid contain A- and B-type Mo4O132− subunits.Three novel pillared-layer molybdenum-oxide-based inorganic–organic hybrids, namely, [Zn2(tyty)(μ3-OH)(MoO4)(H2O)] (1), [Co2(tyty)(μ3-OH)(MoO4)(H2O)] (2) and [Co(pytpy)2(Mo4O13)] (3) (Htyty = 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene, pytpy = 4′-(4-pyridyl)-4,2′:6′,4″-terpyridine), have been synthesized and characterized by elemental analyses, IR spectra, TG analyses and single-crystal X-ray diffraction. Compounds 1 and 2 are isostructural and display 3D pillared-layer frameworks based on bimetal-oxide layers pillared by the tyty ligands. Compound 3 shows a 3D pillared-layer framework constructed by pytpy coordinating directly to a molybdenum atom and Co atom simultaneously. Furthermore, the photoluminescence property of compound 1 and the magnetic properties of compounds 2 and 3 are discussed.Three pillared-layer molybdenum-oxide-based inorganic–organic hybrids have been prepared by self-assemblies of rigid/triangular N-containing ligands and bimetallic salts.

•1 is a (2D → 3D) interdigitated architecture assembled by bilayer motifs.•2 and 3 exhibit (2D → 3D) entangled frameworks with coexistence of polycatenation and interdigitation.•1–3 are (2D → 3D) entangled networks based on bifunctional Hppmba ligand.Self-assembly of transition metal salts with long bifunctional ligand affords three entangled coordination frameworks, namely, [Co(ppmba)2] (1), [Zn(ppmba)2]·0.5H2O (2) and [Cd(ppmba)2]·0.25H2O (3) (Hppmba = 4-((3-(pyridin-4-yl)-1H-pyrazol-1-yl)methyl)benzoic acid). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by element analyses, IR spectra, X-ray powder diffraction, and TG analyses. Compound 1 is a peculiar (2D → 3D) interdigitated architecture that is assembled from bilayer motifs. Compounds 2 and 3 exhibit fascinating (2D → 3D) entangled frameworks constructed from undulating 44-sql layers, which have both polycatenane and interdigitation characters. In addition, the magnetic properties of compound 1 and the photoluminescence properties of compounds 2 and 3 were studied.Three novel entangled metal–organic complexes, which show unusual interdigitated and polycatenated architectures, are reported.

•Two rare 3D porous metal-organic frameworks based on rigid trigonal N-donor ligand•1D metal-organic nanotubes generated from helical chains•Tetranodal (3,4,4,6)-connected network with an unprecedented topologyTwo isostructural 3D porous metal-organic frameworks (MOFs), namely [Co2(Htpim)2(odpa)]·8H2O (1) and [Ni2(Htpim)2(odpa)]·8H2O (2) (Htpim = 2,4,5-tri(4-pyridyl)-imidazole, odpa = 4,4′-oxydiphthalate), were prepared and characterized by elemental analyses, single crystal X-ray diffraction, powder X-ray diffraction, IR spectra and thermal analyses. The 3D architectures of compounds 1 and 2 are built from 1D metal-organic nanotubes (MONTs) which connect with each other by bridging ligands, and every 1D MONT is generated by linking the vertexes of helical chain with metal-organic fragments. In addition, the magnetic properties of 1 and 2 have also been studied.Two fascinating 3D porous coordination networks, containing helix-based metal-organic nanotubes, are reported, which add new members to the family of nanotubular metal-organic frameworks.

•Microporous interpenetrated frameworks based on polyoxometalates.•3D nets constructed from metal–organic layers pillared by the [Mo2O7]2 − anions.•The first POM-based hybrid materials featuring twofold interpenetrated hms net.Two novel polyoxometalate (POM)-based organic–inorganic hybrids, namely, [(CH3)2NH2][Co(tpba)(Mo2O7)]·2H2O (1) and [(CH3)2NH2][Ni(tpba)(Mo2O7)]·2H2O (2) (tpba = 4-([4,2′:6′,4′′-terpyridin]-4′-yl)benzoic acid), have been synthesized and characterized by elemental analyses, IR spectra, TG analyses and single-crystal X-ray diffraction. Compounds 1 and 2 are isostructural and feature microporous interpenetrated frameworks, which are constructed from metal–organic layers pillared by the [Mo2O7]2 − anions. Topologically, the overall structures of 1 and 2 can be classified as a rare (3,5)-connected twofold interpenetrated hms net, which has never been observed in POM-based hybrid materials prior to this work. Furthermore, the magnetic property of compound 1 are discussed.Compounds 1 and 2 exhibit 3D microporous interpenetrated frameworks, which are constructed from metal–organic layers pillared by the [Mo2O7]2 − anions.

•Compound 1 is an 8-fold [4+4] interpenetrated dia network.•Compound 1 contains unique quadruple-stranded intertwined homo-axis helices.•Compound 1 contains an inextricable octuple-stranded braid.•Compounds 2–4 display 5-fold interpenetrated dia networks.•Compounds 2–4 incorporate exceptional quintuple-stranded molecular braid.Four novel interpenetrated diamondoid (dia) networks, namely [Zn(1,4-bdc)(bibp)] (1), [Mn(bqdc)(bibp)] (2), [Cd(bqdc)(bibp)] (3), [Co4(bqdc)4(bibp)4] (4). (bibp = 1,4-bis(4-(imidazole-1-yl)benzyl)piperazine, 1,4-bdc = 1,4-benzenedicarboxylate, bqdc = 2,2′-biquinoline-4,4′-dicarboxylate), have been synthesized by using mixed spacer ligands with significantly different lengths. Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra and TG analyses. Compound 1 is an unusual 8-fold [4+4] interpenetrated dia network containing the unique quadruple-stranded braid (i.e. quadruple-stranded homo-axis helices), which is further entangled by another quadruple-stranded braid to produce an unprecedented octuple-stranded braid derived from eight individual dia nets. Compounds 2 and 3 are isostructural, while compound 4 is isoreticular to them. They all exhibit 5-fold interpenetrating dia networks containing an exceptional quintuple-stranded molecular braid. In addition, the photoluminescence properties of compounds 1 and 3, and the magnetic property of compound 4 were studied.Four novel interpenetrated diamondoid (dia) networks obtained by self-assembly of a new long linear N-donor ligand and transition metal salts in the presence of short ditopic carboxylate ligands, provide an 8-fold [4+4] interpenetrated dia network containing the unique quadruple-stranded braid as well as an unprecedented octuple-stranded braid, and three 5-fold interpenetrating dia networks containing an exceptional quintuple-stranded molecular braid.

•Compounds 1–4 display different interpenetrating networks based on the bibp ligand.•Compound 1 shows a 2-fold interpenetrating 3D framework with CdSO4 topology.•Compounds 2 and 3 exhibit 2-fold interpenetrating pcu frameworks.•Compound 4 is a 2D → 3D interdigitated network formed from 2D → 2D threefold interpenetrating motifs.Four novel interpenetrating coordination polymers have been hydrothermally synthesized based on a long flexible N-donor ligand (bibp) and different polycarboxylates, namely [Ni(1,3-bdc)(bibp)(H2O)]·0.5H2O (1), [Ni(btec)0.5(bibp)1.5]·H2O (2), [Co(btec)0.5(bibp)1.5]·H2O (3) and [Co(oba)(bibp)]·2H2O (4) (bibp = 1,4-bis(4-(imidazole-1-yl)benzyl)piperazine, 1,3-bdc = 1,3-benzenedicarboxylate, btec = 1,2,4,5-benzenetetracarboxylate, oba = 4,4′-oxybisbenzoate). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra and TG analyses. Compound 1 shows a 2-fold interpenetrating 3D framework with CdSO4 topology. Compounds 2 and 3 exhibit 2-fold interpenetrating pcu frameworks. Compound 4 is a 2D → 3D interdigitated network formed from 2D → 2D threefold interpenetrating motifs. In addition, the magnetic properties of compounds 1–4 have also been investigated in the temperature range 2–300 K.Four novel coordination polymers have been synthesized by self-assembly of nickel/cobalt acetates with a long flexible linear N-donor ligand (bibp, 1,4-bis(4-(imidazole-1-yl)benzyl)piperazine) and varied polycarboxylates, which present different interpenetrating networks.

•1 is a (3,6)-connected 3D self-penetrating net with an unprecedented topology.•2 is the first (2D → 3D) parallel polycatenation of 44-sql net with double edges.•The photoluminescence properties of compounds 1 and 2 were studied.Self-assembly of d10 metal salts with a semi-rigid V-shaped N-containing ligand affords two entangled coordination frameworks, namely [Zn2(bdc)1.5(tbpp)] (1) and [Cd(tbpp)2(H2O)]·H2O (2) (Htbpp = 4-(1-(4-(2H-tetrazol-5-yl)benzyl)-1H-pyrazol-3-yl)pyridine, H2bdc = 1,4-benzenedicarboxylate acid). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, X-ray powder diffraction and TG analyses. Compound 1 is a (3,6)-connected 3D self-penetrating network with an unprecedented (4.62)(43.67.74.8) topology. Compound 2 is the first example of (2D → 3D) parallel polycatenation of 44-sql net with double edges. Additionally, the photoluminescence properties of compounds 1 and 2 were studied.Two novel entangled coordination polymers are reported: compound 1 shows a 3D self-penetrating structure and represents a new topology, while compound 2 represents the first example of (2D → 3D) polycatenated network assembled from the 2D 44-sql layers with double edge.

•Polythreaded nets composed of 2D layers with dangling arms protruding from one side.•2D → 3D polythreaded net constructed from 2D layers with two types of lateral arms.•Polythreaded net assembled from 1D MONTs with lateral arms protruding from one side.Five new polythreaded coordination networks, [Co2(L)(bpp)(H2O)]·0.25H2O (1), [Co2(L)(bim)] (2), [Co2(L)(btb)] (3), [Co3(HL)2(phen)3] (4) and [Ni2(L)(bpp)2(H2O)2]·2H2O (5) (H4L = 5,5′-(1,3-phenylenebis(methyleneoxy)diisophthalic) acid, bpp = 1,3-di(4-pyridyl)propane, bim = 1,4-bis(imidazol-1-yl)butane, btb = 1,4-bis(1,2,4-triazol-1-yl)butane, phen = 1,10-phenanthroline), have been synthesized by self-assembly of transition-metal salts with a long flexible tetracarboxylate ligand and N-containing ligands. Their structures were characterized by single crystal X-ray diffraction, elemental analyses, X-ray powder diffraction, IR spectra and TG analyses. Compounds 1–3 exhibit unusual (2D → 2D) polythreaded frameworks that are built from 2D layers with dangling arms protruding from one side of the layers. Compound 4 displays a unique (2D → 3D) polythreaded framework constructed from 2D layers with two types of lateral arms. Compound 5 is an uncommon (1D → 1D) polythreaded framework that is first assembled from 1D metal–organic nanotubes (MONTs) with lateral arms protruding from one side of the 1D MONTs. In addition, the magnetic properties of them were also studied.Five new polythreaded coordination networks have been obtained by self-assembly of transition-metal salts with a long flexible tetracarboxylate ligand and N-containing ligands.

•Compounds 1 and 2 exhibit the novel 3D self-threading framework.•1 and 2 can be simplified to a CdSO4 net, which is really rare in self-threading system.•Entangled coordination networks constructed from H3L ligand remain largely unexplored.Two new isostructural metal-organic frameworks, namely [Co(HL)(bpp)] · 0.5H2O (1) and [Zn(HL)(bpp)] · 3H2O (2) (H3L = 5-(2′-carboxy-biphenyl-4-ylmethoxy)-isophthalic acid, bpp = 1,3-bis(4-pyridyl)propane), have been hydrothermally synthesized and further characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, IR spectra and TG analyses. Compounds 1 and 2 exhibit interesting 3D frameworks of (65.8)-CdSO4 topology with dangling arm (i.e. the uncoordinated 2′-carboxy-biphenyl-4-ylmethoxy group of HL ligand). The remarkable feature of these two compounds is that each dangling arm threads into two 6-membered rings belonging to the 3D net itself, displaying the self-threading character. The magnetic properties of 1 and photoluminescence of 2 have also been investigated.Two novel 3D self-threading metal-organic frameworks with CdSO4 topology, which add new members to the newborn self-threading family, are reported.

•1 is the first 3D alkaline-earth metal aldarate based on inorganic helical chains.•1 represents the first metal saccharate containing multidirectional helical chains.•1 is the first chiral MOF constructed from the D-saccharate ligands and barium ions.Self-assembly of the D-saccharate (D-sacc) ligand and barium salt under hydrothermal conditions yields an unprecedented homochiral three-dimensional (3D) metal saccharate, namely, [Ba(D-sacc)]n (1), which is based on inorganic helical chains as infinite rod-shaped secondary building units (SBUs). The structure of compound 1 was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analyses, IR spectrum, and thermogravimetric analysis. Compound 1 exhibits a novel 3D chiral architecture containing multidirectional helical chains, which is still rare in metal–organic complexes, especially in metal aldarates. To the best of our knowledge, compound 1 represents the first example of alkaline-earth metal aldarates featuring chiral and helical structures. Furthermore, the photoluminescent property of compound 1 was investigated in the solid state at room temperature.An unprecedented homochiral 3D metal saccharate, based on inorganic helical chains as infinite rod-shaped secondary building units, is reported, which represents the first example of homochiral alkaline-earth metal aldarates containing multidirectional helical chains.

•1 represents the first 2D nanoscaled quadruple-layer metal–organic framework based on octanuclear Co(II) clusters.•1 is the first (2D → 3D) interdigitated network assembled from sidearm-containing quadruple-layer motifs.•The centrosymmetric octanuclear Co(II) clusters observed in 1 is still highly rare up to now.Self-assembly of a flexible tricarboxylate ligand (H3L) and cobalt salt under hydrothermal conditions yields an unprecedented two-dimensional (2D) nanoscaled quadruple-layer networks [Co4(HL)3(μ3-OH)2(H2O)2]·5H2O (1) (H3L = (3,5-dicarboxyl-phenyl)-(4-(2′-carboxyl-phenyl)-benzyl)ether). The structure of compound 1 was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analyses, IR spectrum, and thermogravimetric analysis. Compound 1 represents the first 2D nanoscaled multiple-layer architecture constructed from octanuclear cobalt cluster building blocks. Furthermore, the adjacent sidearm-containing 2D quadruple-layer motifs are interdigitated in a mutual relationship to form a 3D supramolecular framework. In addition, the magnetic properties of compound 1 have been studied by measuring its magnetic susceptibility in the temperature range of 2–300 K, indicating the existence of antiferromagnetic coupling within the octanuclear cobalt cluster.An unprecedented 2D nanoscaled quadruple-layer metal–organic framework, based on centrosymmetric octanuclear Co(II) clusters as secondary building units, is reported, which represents the first example of (2D → 3D) interdigitated network self-assembled from 2D sidearm-containing quadruple-layer motifs.

•Non-coordinating octamolybdate-templated inorganic–organic hybrid compounds.•2D → 3D interdigitated architectures with 1D channels accommodating octamolybdates.•The first double-edged 2D net in the domain of POM-templated coordination polymers.Three non-coordinating octamolybdate-templated inorganic–organic hybrid compounds, namely, [Co2(timb)2(Htimb)(H2O)2(β-Mo8O26)0.5] (1), [Zn2(timb)2(Htimb)(H2O)2(β-Mo8O26)0.5] (2) and [Ag4(tyty)2(H2O)(β-Mo8O26)0.5] (3) (Htimb = 1-tetrazole-4-imidazole-benzene, Htyty = 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene), have been synthesized and characterized by elemental analyses, IR spectra, TG analyses and single-crystal X-ray diffraction. All compounds are based on the non-coordinating octamolybdate polyanions as templates. Compounds 1 and 2 are isostructural and display 2D → 3D interdigitated architectures with 1D channels accommodating octamolybdate anions. Compound 3 can be simplified to a double-edged 44-sql net with large pores, in which non-coordinating octamolybdate anions as guests are encapsulated. Furthermore, the magnetic property of compound 1 and the photoluminescence properties of compounds 2 and 3 are discussed.Graphical abstractThree non-coordinating octamolybdate-templated inorganic–organic hybrid compounds have been prepared by self-assemblies of two similar rigid N-containing ligands and metal salts in the presence of octamolybdates.

•Compound 1 is the first interdigitated metal–cfH framework assembled from 2D (6,3) nets.•Compound 2 is the first (2D → 3D) interdigitated metal–ppaH architecture.•Compound 3 defines the first example of 1D double-chain metal–levofH complex.•Compound 3 represents the first example of interdigitated metal–levofH complex.•Compounds 1–3 are three entangled metal–quinolone complexes.Three interdigitated metal–quinolone complexes, [Cd2(cfH)2(btec)(H2O)2]·6H2O (1), [Cd2(ppaH)2(1,3-bdc)2]·4.25H2O (2) and [Cd2(LevofH)(1,3-bdc)2(H2O)2] (3) (cfH = ciprofloxacin, ppaH = pipemidic acid, LevofH = levofloxacin, btec = 1,2,4,5-benzenetetracarboxylate, 1,3-bdc = 1,3-benzenedicarboxylate) have been synthesized and characterized by elemental analyses, IR spectra, X-ray powder diffractions, TG analyses and single crystal X-ray diffraction. Compound 1 exhibits a (2D → 3D) interdigitated architecture that is first assembled from 2D wavelike (6,3) nets with side arms. Compound 2 is the first example of (2D → 3D) interdigitated metal–ppaH complex, which is constructed from sidearm-containing 2D layers of (4,4) topology. Compound 3 is built from 1D double chains with dangling levofloxacin ligands protruding from one side of the chain, and each pair of these double chains are interdigitated with each other to generate a perfect molecular zipper. By inspection of the structures of 1–3, it is believed that the short aromatic polycarboxylate ligands are important for the construction of interdigitated metal–quinolone complexes. The photoluminescent properties of compounds 1–3 have also been investigated.Graphical abstractThree interdigitated metal–quinolone complexes, which are self-assembled from the quinolones and cadmium salts in the presence of short aromatic polycarboxylates, are reported.

An 8-connected entangled metal–organic framework has been synthesized and characterized, which not only represents the first entangled framework with coexistence of self-threading, polythreading and interpenetration, but also represents the highest connected topology presently known for self-threading and polythreading systems.

•1 is first polythreaded network assembled from 2D layers with two types of arms.•Up to now, the 2D motif decorated with distinct kinds of arms is highly rare.•So far, only a few coordination compounds containing Htpba ligand have been reported.Self-assembly of the trigonal 1,3,5-benzenetricarboxylate (H3btc) and copper salt in the presence of large trigonal N-containing ligand yields a fascinating entangled network, [Cu(Hbtc)(Htpba)]·1.5H2O (1) (Htpba = 4-([4,2′:6′,4″-terpyridin]-4′-yl) benzoic acid). Compound 1 exhibits a novel (2D → 3D) polythreaded network that is first assembled from 2D layers with two types of lateral arms. By inspection of the structure of 1, it is believed that the trigonal ligands with uncoordinated groups acting as dangling lateral arms play an important role in the formation of polythreaded network. The magnetic properties of compound 1 have been studied in the temperature range 2–300 K.The title compound exhibits an interesting (2D → 3D) polythreaded network that is first assembled from 2D layers with two distinct lateral arms.

Two novel NCN-pincer complex precursors bearing frameworks of 2,6-bis(oxazol-4-yl)benzene (A) and 2-(thiazol-4-yl)-6-(oxazol-4-yl)benzene (B) were synthesized. Palladations of A and B afforded two new bis(azole) pincer complexes, [(A-κ3NCN)PdBr] (1) and [(B-κ3NCN)PdBr] (2). Both complexes were fully characterized by NMR, MS, DSC-TGA and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in a noncentrosymmetric orthorhombic space group Cmc21 (No. 36, Z = 4). Complex 2 crystallizes in a centrosymmetric monoclinic space groupP21/n (No. 14, Z = 4). Despite the similarity in their chemical formulas, the structures of the two complexes are subtly different: they are built up of two-dimensional supramolecular layers with identical topology, but stacked in different sequences, i.e., the layers in complex 1 are stacked in an AAAA-type fashion, while those in complex 2 are stacked in an alternating AA−1AA−1 sequence (A denotes a layer; A−1 stands for A's inversion symmetry equivalent). In addition, the complexes showed good catalytic activity toward Mizoroki–Heck reactions.

Two novel NCN-pincer complex precursors bearing frameworks of 2,6-bis(oxazol-4-yl)benzene (A) and 2-(thiazol-4-yl)-6-(oxazol-4-yl)benzene (B) were synthesized. Palladations of A and B afforded two new bis(azole) pincer complexes, [(A-κ3NCN)PdBr] (1) and [(B-κ3NCN)PdBr] (2). Both complexes were fully characterized by NMR, MS, DSC-TGA and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in a noncentrosymmetric orthorhombic space group Cmc21 (No. 36, Z = 4). Complex 2 crystallizes in a centrosymmetric monoclinic space groupP21/n (No. 14, Z = 4). Despite the similarity in their chemical formulas, the structures of the two complexes are subtly different: they are built up of two-dimensional supramolecular layers with identical topology, but stacked in different sequences, i.e., the layers in complex 1 are stacked in an AAAA-type fashion, while those in complex 2 are stacked in an alternating AA−1AA−1 sequence (A denotes a layer; A−1 stands for A's inversion symmetry equivalent). In addition, the complexes showed good catalytic activity toward Mizoroki–Heck reactions.