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ISSN: 2053-2296

Virtual issue on Coordination polymers (July 2014)

Introduced by Len Barbour

The past two decades have witnessed a veritable explosion of reports detailing the solid-state structures of coordination compounds consisting of conceptually infinite one-dimensional chains, two-dimensional nets and three-dimensional frame­works. The concepts involved are relatively simple; crystalline coordination polymers are most often formed from solutions containing metal ions and bridging ligands. The seemingly unlimited opportunities for preparing novel coordination polymers arise not only from obvious choices that influence structural topology (i.e. bridging ligand geometry and metal ion coordination mode) but also from a range of other factors, some of which can be quite subtle. The collection of articles selected for this virtual issue of Acta Crystallographica Section C: Structural Chemistry serves to showcase the amazing diversity of the field.

The issue collects together a series of articles originally published in the journal between January 2012 and December 2013.

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Cover illustration: A layer of edge-shared Ca penta­gonal–bipyramidal polyhedra forming six-membered rings, viewed along the c axis, with succinate ligands shown in ball-and-stick representation. See Mazaj et al. [Acta Cryst. (2012), C68, m4-m6].

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Acta Crystallographica Section C: Structural Chemistry is pleased to announce a virtual issue presenting articles based on the structures of Coordination polymers. This special issue collects together a series of articles originally published in the journal between January 2012 and Decemeber 2013.

one-dimensional coordination polymers


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Colourless crystals of the title compound, [Cd2(C7H4IO2)4(C12H10N2)(H2O)2]n, were obtained by the self-assembly of Cd(NO3)2·4H2O, 1,2-bis­(pyridin-4-yl)ethene (bpe) and 4-iodo­benzoic acid (4-IBA). Each CdII atom is seven-coordinated in a penta­gonal-bipyramidal coordination environment by four carboxyl­ate O atoms from two different 4-IBA ligands, two O atoms from two water mol­ecules and one N atom from a bpe ligand. The CdII centres are bridged by the aqua mol­ecules and bpe ligands, which lie across centres of inversion, to give a two-dimensional net. Topologically, taking the CdII atoms as nodes and the [mu]-aqua and [mu]-bpe ligands as linkers, the two-dimensional structure can be simplified as a (6,3) network.

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The asymmetric unit of the title compound, {[La(C4H5O2)3(H2O)2]·C5H5N5·H2O}n, consists of an LaIII cation, three crotonate (but-2-enoate) anions and two coordinated water mol­ecules forming the neutral complex, completed by an external adenine mol­ecule and one hydration water mol­ecule. The LaO10 coordination polyhedra, connected through the sharing of a single edge, form isolated chains running along the [100] direction. These one-dimensional structures are characterized by two different centrosymmetric La2O2 loops, with La...La distances of 4.5394 (6) and 4.5036 (6) Å. The unbound adenine and water solvent mol­ecules form a highly planar hydrogen-bonded array parallel to (110) (r.m.s. deviation from the mean plane < 0.10 Å) which inter­sects the isolated La-crotonate chains in a slanted fashion to form an extremely connected hydrogen-bonded three-dimensional structure.

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The asymmetric unit of the title compound, poly[(dimethylamine-[kappa]N)[[mu]3-(E)-2,6-dimethyl-4-styryl­pyridine-3,5-dicar­boxyl­ato-[kappa]3O3:O3':O5]zinc(II)], [Zn(C17H13NO4)(C2H7N)]n, con­sists of one crystallographically independent distorted tetrahedral ZnII cation, one (E)-2,6-dimethyl-4-styryl­pyridine-3,5-dicarboxyl­ate (mspda2-) ligand and one coordinated dimethyl­amine mol­ecule. Two S- and R-type chiral units are generated from the axially prochiral mspda2- ligand through C-H...O hydrogen bonds. The R-type chiral units assemble a left-handed (M) Zn-mspda helical chain, while the right-handed (P) Zn-mspda helical chain is constructed from neighbouring S-type chiral units. The P- and M-type helical chains are inter­linked by carboxyl­ate O atoms to form a one-dimensional ladder. Inter­chain N-H...O hydrogen bonds extend these one-dimensional ladders into a two-dimensional supra­molecular architecture. The title compound exhibits luminescence at [lambda]max = 432 nm upon excitation at 365 nm.

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A novel one-dimensional CuII coordination polymer, catena-poly[bis­([mu]4-3-{[2-(3-hydroxy-2-oxido­benzyl­idene)­hydrazinylidene]­methyl}­benzene-1,2-diolato)­dimethanol­tricopper(II)], [Cu3(C14H10N2O4)2(CH3OH)2]n, (I), was constructed with a di-Schiff base supported centrosymmetric trinuclear CuII subunit. In the subunit, two peripheral symmetry-related CuII cations have square-pyramidal CuNO4 geometry and the central third CuII cation lies on an inversion centre with octahedral CuN2O4 geometry. In (I), each partially deproton­ated di-Schiff base 3-{[2-(3-hydroxy-2-oxido­benzyl­idene)­hy­dra­zinyl­idene]­methyl}­benzene-1,2-diolate ligand (Hbcaz3-) acts as a hepta­dentate ligand to bind the CuII centres into chains along the a axis. A centrosymmetric Cu2O2 unit containing an asymmetrically bridging O atom, being axial at one Cu atom and equatorial at the other Cu atom, links the trinuclear CuII subunit into a one-dimensional chain, which is reinforced by intra­molecular phenol-methanol O-H...O and methanol-phenolate O-H...O hydrogen bonds. Interchain [pi]-[pi] stacking interactions between pyrocatechol units, with a distance of 3.5251 (18) Å, contribute to the stability of the crystal packing.

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The structure of the title compound, [Cd2(C8H4O4)Cl2(C6H15NO3)]n, consists of one-dimensional chains in which each centrosymmetric tetra­nuclear Cd4Cl4O2 cluster is terminated by two chelating triethanol­amine (teaH3) ligands but linked to two adjacent clusters through four bridging benzene-1,4-dicarboxyl­ate (bdc) ligands. The tetra­nuclear Cd4Cl4O2 clusters are held together via bridging Cl and O atoms. Three directional hydrogen bonds from the multi-podal hy­droxy groups of the teaH3 ligand stabilize and extend the one-dimensional chains into a three-dimensional framework. All three hy­droxy groups of the teaH3 ligand form hydrogen bonds, illustrating the fact that the teaH3 ligand can serve as an excellent hydrogen-bond donor.

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In the title complex, [Ag(NO3)(C9H7N3OS)]n, [eta]1:[eta]1:[eta]1:[mu]2-bridging 2-(pyridin-4-ylsulfin­yl)pyrimidine (pypmSO) ligands with opposite chiralities are alternately arranged to link the AgI cations through two N atoms and one sulfinyl O atom of each ligand, leading to an extended zigzag coordination chain structure along the [\overline{2}01] direction. An FT-IR spectroscopic study shows a decreased stretching frequency for the [eta]1-O-bonded S=O group compared with that of the free ligand. The parallel chains are arranged and inter­connected via O(S=O)...[pi](pyridine/pyrimidine) and C-H(pyridine)...O(NO3-) inter­actions to furnish a layer almost parallel to the ac plane. Along the b axis, the layers are stacked and stabilized through anion(NO3-)...[pi](pyrimidine) inter­actions to form a three-dimensional supra­molecular framework. The ligand behaviour of the new diheterocyclic sulfoxide and the unconventional O(S=O)...[pi](pyridine/pyrimidine) and anion(NO3-)...[pi](pyrimidine) inter­actions in the supra­molecular assembly of the title complex are presented.

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The crystal structure of the title compound, {[Cu(C4H4O6)(C2H6N4O2)]·4H2O}n, contains the central CuII cation in a distorted octa­hedral coordination, symmetrically chelated by the two imine N atoms of a neutral oxamide dioxime (H2oxado) ligand [Cu-N = 1.9829 (16) Å] and unsymmetrically bis-chelated by two halves of the L-(+)-tartrate(2-) (tart) ligands, each half being linked to the CuII cation via the deprotonated carboxyl­ate group and protonated hy­droxy group [Cu-O = 1.9356 (14) and 2.4674 (13) Å, respectively]. The extended asymmetric unit is defined by twofold axes, one passing through the CuII cation and the centre of the oxamide dioxime (H2oxado) ligand and the another two (symmetry related) bisecting the central C-C bonds of the tartrate ions. The structure is chiral, consisting of enantio­meric linear-chain polymers oriented along [001], with virtual monomeric {Cu(tart0.5)2(H2oxado)} repeat units and with the chains inter­leaved face-to-face into `twin pillars'. Nanochannels exist, running parallel to the c axis and bisecting a and b, which host `double strings' of solvent water mol­ecules. Extensive hydrogen bonding (O-H...O and N-H...O) between the chains and solvent water mol­ecules, together with extended [pi]-[sigma] inter­actions, consolidate the bulk crystal structure.

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The new 4-amino-1,2,4-triazole asymmetric bridging ligand 4-amino-5-(pyridin-3-yl)-3-[4-(pyridin-4-yl)phen­yl]-4H-1,2,4-triazole (L) has been used to generate three novel isomorphic one-dimensional coordination polymers, viz. catena-poly[[tris­[dichloridomercury(II)]-bis­{[mu]3-4-amino-5-(pyridin-3-yl)-3-[4-(pyridin-4-yl)phen­yl]-4H-1,2,4-triazole}] aceto­nitrile monosolvate], {[Hg3Cl6(C18H14N6)2]·CH3CN}n, (I), and the bromido, {[Hg3Br6(C18H14N6)2]·CH3CN}n, (II), and iodido, {[Hg3I6(C18H14N6)2]·CH3CN}n, (III), analogs. The asymmetric ligand acts as a tridentate ligand to coordinate the three different HgII centers (two of which are symmetry-related). Two ligands and two symmetry-related HgII centers form centrosymmetric rectangular units which are linked into one-dimensional chains via the other unique Hg atoms, which sit on mirror planes. The chains are elaborated into a three-dimensional structure via inter­chain hydrogen bonds. The acetonitrile solvent mol­ecules are located in ellipsoidal cavities. The luminescent character of these three coordination complexes was investigated in the solid state.

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The mol­ecule of 3,5-bis­{4-[(benzimidazol-1-yl)methyl]phenyl}-4H-1,2,4-triazol-4-amine (L), C30H24N8, has an antiperiplanar conformation of the two terminal benzimidazole groups and forms two-dimensional networks along the crystallographic b axis via two types of inter­molecular hy­drogen bonds. However, in catena-poly[[[dichloridomercury(II)]-[mu]-3,5-bis­{4-[(benzimidazol-1-yl)methyl]phenyl}-4H-1,2,4-triazol-4-amine] dichloro­methane hemisolvate], {[HgCl2(C30H24N8)]·0.5CH2Cl2}n, synthesized by the combination of L with HgCl2, the L ligand adopts a synperiplanar conformation. The HgII cation lies in a distorted tetra­hedral environment, which is defined by two N atoms and two Cl atoms to form a one-dimensional zigzag chain. These zigzag chains stack via hydrogen bonds which expand the dimensionality of the structure from one to two.

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catena-Poly[benzyl­decyl­dimethyl­ammonium [plumbate(II)-tri-[mu]-bromido]], {(C19H34N)[PbBr3]}n, crystallizes as an inorganic-organic hybrid following monoclinic space-group symmetry P21/c. The structure consists of extended chains running along the [001] direction and built of [PbBr3]- units. These inorganic chains are separated by inter­digitated ammonium cations which form hydro­philic layers through weak C-H...Br inter­actions. The architecture is essentialy the same as found for n-alkyl­benzyl­dimethyl­ammonium bromides.

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Solvothermal reactions of Cu2(OH)2CO3 with 1,3-bis­(pyridin-4-yl)propane (bpp) in the presence of aqueous ammonia in 4-iodo­toluene/CH3CN or 1,4-diiodo­benzene/CH3CN afforded two [Cu2I2]-based coordination polymers, namely catena-poly[[[di-[mu]-iodido-dicopper(I)]-bis­[[mu]-1,3-bis­(pyridin-4-yl)propane-[kappa]2N:N']] p-toluidine tetra­solvate], {[Cu2I2(C13H14N2)2]·4C7H9N}n, (I), and the analogous 1,4-diiodo­benzene monosolvate, {[Cu2I2(C13H14N2)2]·C6H4I2}n, (II). The [Cu2I2] unit of (I) lies on a centre of symmetry at the mid-point of the two I atoms, while that of (II) has a twofold axis running through the I...I line. In (I) and (II), each Cu centre is tetra­hedrally coordinated by two [mu]-I and two N atoms from two different bpp ligands. Each rhomboid [Cu2I2] unit can be considered as a four-connecting node linked to the symmetry-related [Cu2I2] units via two pairs of bpp ligands to form a one-dimensional double chain along the c axis. The dimensions of the [Cu2I2(bpp)2]2 rings in (I) and (II) are different, which may be due to the presence of different guest solvent mol­ecules in the structures. In (I), one p-toluidine mol­ecule, derived from an Ullmann coupling reaction of 4-iodo­toluene with ammonia, inter­acts with the [Cu2I2] cluster fragment through N-H...I hydrogen bonds, while the two p-toluidine molecules interact via N-H...N hydrogen bonds. In (II), two I atoms of each 1,4-diiodo­benzene mol­ecule are linked to the I atoms of the [Cu2I2] fragments from a neighbouring chain via I...I secondary inter­actions.

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The structure of the title compound, poly[(dihydrogen­phosphato-[kappa]O)([mu]3-hydrogenphosphato)di-[mu]-oxido-(1,10-phenanthroline)copper(II)vanadium(V)], [CuV(HPO4)(H2PO4)O2(C12H8N2)]n, is defined by [(phen)Cu-[mu]-([kappa]2O:O'-VP2O10H3)2-Cu(phen)] units (phen is 1,10-phenanthroline), which are connected to neighbouring units through vanadyl bridges. Neighbouring chains have no covalent bonds between them, although they inter­digitate through the phen groups via [pi]-[pi] inter­actions.

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The title compound, [CuNa(C4H3O7S)(C10H8N2)(H2O)3]n, consists of one CuII cation, one NaI cation, one 2-sulfonato­butane­dioate trianion (SSC3-), one 2,2'-bipyridyl (bpy) ligand and three coordinated water mol­ecules as the building unit. The coordination of the CuII cation is composed of two pyridyl N atoms, one water O atom and two carboxyl­ate O atoms in a distorted square-pyramidal coordination geometry with an axial elongation. The NaI cation is six-coordinated by three water mol­ecules and three carboxyl­ate O atoms from three SSC3- ligands in a distorted octa­hedral geometry. Two SSC3- ligands link two CuII cations to form a Cu2(SSC)2(bpy)2 macrocyclic unit lying across an inversion centre, which is further linked by NaI cations via Na-O bonds to give a one-dimensional chain. Inter­chain hydrogen bonds link these chains to form a two-dimensional layer, which is further extended into a three-dimensional supra­molecular framework through [pi]-[pi] stacking inter­actions. The thermal stability of the title compound has also been investigated.

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The structures of the Mg, Ca, Sr and Ba salts of 1-naphthoic acid are examined and compared with analogous structures of salts of benzoate derivatives. It is shown that catena-poly[[[diaqua­bis­(1-naphtho­ato-[kappa]O)magnesium(II)]-[mu]-aqua] dihydrate], {[Mg(C11H7O2)2(H2O)3]·2H2O}n, exists as a one-dimensional coordination polymer that propagates only through Mg-OH2-Mg inter­actions along the crystallographic b direction. In contrast with related benzoate salts, the naphthalene systems are large enough to prevent inorganic chain-to-chain inter­actions, and thus species with inorganic channels rather than layers are formed. The Ca, Sr and Ba salts all have metal centres that lie on a twofold axis (Z' = 1 \over 2) and all have the common name catena-poly[[diaqua­metal(II)]-bis­([mu]-1-naphtho­ato)-[kappa]3O,O':O;[kappa]3O:O,O'], [M(C11H7O2)2(H2O)2]n, where M = Ca, Sr or Ba. The Ca and Sr salts are essentially isostructural, and all three species form one-dimensional coordination polymers through a carboxyl­ate group that forms three M-O bonds. The polymeric chains propagate via c-glide planes and through MOMO four-membered rings. Again, inorganic channel structures are formed rather than layered structures, and the three structures are similar to those found for Ca and Sr salicylates and other substituted benzoates.

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A novel infinite one-dimensional silver cylinder, namely poly[[mu]-ethyl­enedi­am­ine-[mu]5-(2-sulfanidylbenzoato)-[mu]4-(2-sul­fanidylbenzoato)-tetra­silver(I)], [Ag4(C7H4O2S)2(C2H8N2)]n, has been synthesized by one-pot reaction of equivalent molar silver nitrate and 2-mercaptobenzoic acid (H2mba) in the presence of ethyl­enediamine (eda). One Ag atom is located in an AgS2NO four-coordinated tetra­hedral geometry, two other Ag atoms are in an AgS2O three-coordinated T-shaped geometry and the fourth Ag atom is in an AgSNO coordination environment. The two mba ligands show two different binding modes. The [mu]2-N:N'-eda ligand, acting as a bridge, combines with mba ligands to extend the AgI ions into a one-dimensional silver cylinder incorporating abundant Ag...Ag inter­actions ranging from 2.9298 (11) to 3.2165 (13) Å. Inter­chain N-H...O hydrogen bonds extend the one-dimensional cylinder into an undulating two-dimensional sheet, which is further packed into a three-dimensional supra­molecular framework by van der Waals inter­actions; no [pi]-[pi] inter­actions were observed in the crystal structure.

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The title compound, {[Co(H2O)6][Co(SO4)(C10H8N2)(H2O)3][Co(SO4)2(C10H8N2)(H2O)2]}n, contains three crystallographically unique CoII centres, all of which are in six-coordinated environments. One CoII centre is coordinated by two bridging 4,4'-bipyridine (4,4'-bipy) ligands, one sulfate ion and three aqua ligands. The second CoII centre is surrounded by two N atoms of two 4,4'-bipy ligands and four O atoms, i.e. two O atoms from two monodentate sulfate ions and two from water mol­ecules. The third CoII centre forms part of a hexaaquacobalt(II) ion. In the crystal structure, there are two different one-dimensional chains, one being anionic and the other neutral, and adjacent chains are arranged in a cross-like fashion around the mid-point of the 4,4'-bipy ligands. The structure features O-H...O hydrogen-bonding inter­actions between sulfate anions and water mol­ecules, resulting in a three-dimensional supra­molecular network.

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Yellow needle-shaped crystals of the title compound, {[Ag(C30H22N4)][Ag(NO3)2]}n, were obtained by the reaction of AgNO3 and 9,10-bis­(benzimidazol-1-ylmethyl)anthracene (L) in a 2:1 ratio. The asymmetric unit consists of two AgI cations, one half L ligand and one nitrate anion. One AgI cation occupies a crystallographic inversion centre and links two N-atom donors of two distinct L ligands to form an infinite one-dimensional coordination polymer. The second AgI cation lies on a crystallographic twofold axis and is coordinated by two O-atom donors of two nitrate anions to form an [Ag(NO3)2]- counter-ion. The polymeric chains are linked into a supra­molecular framework via weak Ag...O [3.124 (5) Å] and Ag...[pi] (2.982 Å) inter­actions ([pi] is the centroid of an outer anthracene benzene ring). The [pi] inter­actions contain two short Ag...C contacts [2.727 (6) and 2.765 (6) Å], which can be considered to define Ag-[eta]2-anthracene bonding inter­actions. In comparison with a previously reported binuclear AgI complex [Du, Hu, Zhang, Zeng & Bu (2008). CrystEngComm, 10, 1866-1874], this new one-dimensional coordination polymer was obtained by changing the metal-ligand ratio during the synthesis.

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5-[4-(1,2,4-Triazol-4-yl)phen­yl]-1H-tetra­zole, C9H7N7, (I), an asymmetric heterobifunctional organic ligand containing triazole (tr) and tetra­zole (tz) termini linked directly through a 1,4-phenyl­ene spacer, crystallizes in the polar space group Pc. The heterocyclic functions, serving as single hydrogen-bond donor (tz) or acceptor (tr) units, afford hydrogen-bonded zigzag chains with no crystallographic centre of inversion. In the structure of catena-poly[[di­aqua­cad­mium(II)]bis{[mu]2-5-[4-(1,2,4-triazol-4-yl)phenyl]tetra­zol-1-ido-[kappa]2N1:N1'}], [Cd(C9H6N7)2(H2O)2]n, (II), the CdII dication resides on a centre of in­version in an octa­hedral {N4O2} environment. In the equatorial plane, the CdII polyhedron is built up from four N atoms of two kinds, namely of trans-coordinating tr and tz fragments [Cd-N = 2.2926 (17) and 2.3603 (18) Å], and the coordinating aqua ligands occupy the two apical sites. The metal centres are separated at a distance of 11.1006 (7) Å by means of the double-bridging tetra­zolate anion, L-, forming a chain structure. The water ligands and tz fragments inter­act with one another, like a double hydrogen-bond donor-acceptor synthon, leading to a hydrogen-bonded three-dimensional array.

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In the title compound, {[Tb(C12H8NO2)3(H2O)2]·H2O}n, the TbIII cation is in an eight-coordinate environment, ligated by six carboxyl­ate O atoms from five 3-(pyridin-4-yl)benzoate (L) ligands and by two O atoms from water mol­ecules. The cations are bridged by the carboxyl­ate O atoms of the L ligands to form a two-stranded polymeric chain which is assembled into a three-dimensional supra­molecular network through regular inter­chain O-H...N hydrogen bonding. On excitation at 320 nm, the title compound displays a series of emissions, which were assigned to the characteristic electronic transitions of TbIII.

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A one-dimensional coordination polymer, namely catena-poly[[aqua­pyridine­cadmium(II)]-[mu]3-{4,4'-[(2,4,6-trimethyl-1,3-phenyl­ene)bis­(methyl­ene)]dibenzoato}], [Cd(C25H22O4)(C5H5N)(H2O)]n, has been synthesized by a biphasic solvo­thermal reaction. The CdII cation is located in a CdO5N six-coordinated environment. The trans 4,4'-[(2,4,6-trimethyl-1,3-phenyl­ene)bis­(methyl­ene)]dibenzoate ligand connects the CdII cations to form a one-dimensional ribbon incorporating centrosymmetric [Cd2(COO)2] secondary building units. Inter-­ribbon O-H...O hydrogen bonds extend the one-dimensional ribbons into a two-dimensional sheet. No [pi]-[pi] inter­actions are observed. Comparing products synthesized using a different method, it was found that biphasic solvothermal conditions play a crucial role in obtaining large well-shaped single crystals; only intractable precipitates were obtained by the traditional single-phase solvothermal method.

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The title compound, {[Ni(C9H4O6)(C14H14N4)]·0.41H2O}n, exhibits a three-dimensional hydrogen-bonded supra­mole­cular framework. The NiII cation is six-coordinated in a distorted triangular prism defined by two N atoms from two 1,3-bis­(imidazol-l-ylmethyl)benzene (bix) ligands and four O atoms from two 5-carb­oxy­benzene-1,3-dicarboxyl­ate (HBTC) dianions. The bix molecules and HBTC dianions both act as bidentate ligands, linking the NiII cations to form a one-dimensional coordination polymer. A two-dimensional wave-like net is constructed by O-H...O hydrogen bonds linking adjacent chains. Partially occupied solvent water mol­ecules fill the cavities and link these layers to form a three-dimensional supra­molecular structure via O-H...O hydrogen bonds. The title compound was also characterized by powder X-ray diffraction and thermogravimetric analysis.

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In the title compound, {[Zn(C19H17N5O2)2(H2O)2](NO3)2}n, the ZnII cation is located at an inversion centre within a slightly distorted octa­hedron, ligated by four N atoms from four N2,N6-bis­[(pyridin-3-yl)methyl]pyridine-2,6-dicarboxam­ide (L) ligands occupying a plane about the ZnII atom with the two water O atoms perpendicular to that. In the complex mol­ecule, the bidentate bridging L ligands display helical R and S conformers, and link the ZnII cations into a one-dimensional centrosymmetric double-chain structure con­taining 32-membered rings. The nitrate anions reside in these rings and are involved in multiple N-H...O hydrogen-bond inter­actions. On excitation at 390 nm, the title compound displays a strong blue emission centred at 449 nm. Investigation of the thermal stability shows that the network structure is stable up to 420 K.

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The structure of the title compound, {(C5H5ClN)2[Hg3Cl8]}n, consists of 4-chloro­pyridinium cations and one-dimensional [Hg3Cl8]2- anion chains. There are two coordination environments for HgII in the inorganic chain. The first is a distorted tetra­hedral geometry made up of an HgCl2 unit with two Cl- anion bridges, while the second is an octa­hedral coordination geometry consisting of an HgCl2 unit and four chloride-anion bridges. This gives rise to a novel three-layer centrosymmetric polymer. Finally, the three-dimensional network comes about through the many C-H...Cl and N-H...Cl hydrogen bonds that link the organic and inorganic layers.

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A new one-dimensional platinum mixed-valence complex with nonhalogen bridging ligands, namely catena-poly[[[bis­(ethane-1,2-diamine-[kappa]2N,N')platinum(II)]-[mu]-thio­cyanato-[kappa]2S:S-[bis(ethane-1,2-diamine-[kappa]2N,N')platinum(IV)]-[mu]-thio­cyanato-[kappa]2S:S] tetra­kis­(perchlorate)], {[Pt2(SCN)2(C2H8N2)4](ClO4)4}n, has been isolated. The PtII and PtIV atoms are located on centres of inversion and are stacked alternately, linked by the S atoms of the thio­cyanate ligands, forming an infinite one-dimensional chain. The PtIV-S and PtII...S distances are 2.3933 (10) and 3.4705 (10) Å, respectively, and the PtIV-S...PtII angle is 171.97 (4)°. The introduction of nonhalogen atoms as bridging ligands in this complex extends the chemical modifications possible for controlling the amplitude of the charge-density wave (CDW) state in one-dimensional mixed-valence complexes. The structure of a discrete PtIV thio­cyan­ate compound, bis­(ethane-1,2-diamine-[kappa]2N,N')bis­(thio­cyanato-[kappa]S)platinum(IV) bis­(perchlorate) 1.5-hydrate, [Pt(SCN)2(C4H8N2)2](ClO4)2·1.5H2O, has monoclinic (C2) sym­metry. Two S-bound thio­cyanate ligands are located in trans positions, with an S-Pt-S angle of 177.56 (3)°.

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Poly[[tetraaquadi-[mu]4-citrato-tetrakis(2,6-diaminopurine)tetra­cobalt(II)] 6.35-hydrate], {[Co4(C6H4O7)2(C5H6N6)4(H2O)4]·6.35H2O}n, presents three different types of CoII cations in the asymmetric unit, two of them lying on symmetry elements (one on an inversion centre and the other on a twofold axis). The main fragment is further composed of one fully deprotonated citrate (cit) tetraanion, two 2,6-diamino­purine (dap) mol­ecules and two aqua ligands. The structure is completed by a mixture of fully occupied and disordered solvent water mol­ecules. The two independent dap ligands are neutral and the cit tetra­anion provides for charge balance, compensating the 4+ cationic charge. There are two well defined coordination geometries in the structure. The simplest is mononuclear, with the CoII cation arranged in a regular centrosymmetric octa­hedral array, coordinated by two aqua ligands, two dap ligands and two O atoms from the [beta]-carboxyl­ate groups of the bridging cit tetra­anions. The second, more complex, group is trinuclear, bis­ected by a twofold axis, with the metal centres coordinated by two cit tetra­anions through their [alpha]- and [beta]-carboxyl­ate and [alpha]-hy­droxy groups, and by two dap ligands bridging through one of their pyridine and one of their imidazole N atoms. The resulting coordination geometry around each metal centre is distorted octa­hedral. Both groups are linked alternately to each other, defining parallel chains along [201], laterally inter­leaved and well connected via hydrogen bonding to form a strongly coupled three-dimensional network. The compound presents a novel [mu]4-[kappa]5O:O,O':O',O'',O''':O'''' mode of coordination of the cit tetraanion.

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In the structure of the novel zinc complex catena-poly[[diaqua­(4-hy­droxy­benzo­hydrazide)­zinc(II)]-[mu]-sulfato], [Zn(SO4)(C7H8N2O2)(H2O)2]n, the complex cations are linked by sulfate­ counter-ions into helical polymeric chains extending along the b axis. Each helix is stabilized by six intrachain hydrogen bonds involving stronger O-H...O (1.83-2.06 Å) and weaker N-H...O (2.20-2.49 Å) interactions. The ZnII atom displays a distorted octahedral geometry formed by the 4-hy­droxy­benzo­hydrazide ligand, two water molecules and two SO42- ions, which is very similar to the metal-atom environment in a previously reported CoII complex [Zaslona, Drozdzewski & Kubiak (2010). J. Mol. Struct. 982, 1-8], especially the Zn-O and Zn-N bond lengths of 2.0453 (12)-2.1602 (9) and 2.1118 (12) Å, respectively.

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The title compound, {[Cd3(C6H13N2)2Cl8]·2H2O}n, consists of pendant proton­ated cationic diamine ligands bonded to an anionic one-dimensional coordination polymer chlorido­cadmate scaffold. Each coordination chain features two kinds of CdII centre, each with distorted octa­hedral coordination geometry. One CdII cation lies on a centre of inversion and is coordinated by six bridging chloride ligands, while the other is coordinated by four bridging chloride ligands, one terminal chloride ligand and a 1-aza-4-azonia­bicyclo­[2.2.2]octane aza N atom. This gives a reversible corner-sharing half-cubic linear polymer that lies along the crystallographic a direction. The chains inter­act through hydrogen bonding with solvent water, with each water mol­ecule accepting one N-H...O inter­action from a cation and donating to two O-H...Cl inter­actions with anionic chains, thus linking three separate chains and completing the packing structure.

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In the title mixed-ligand metal-organic polymeric compound, {[Cd(C14H8O6S)(C16H16N2)]·3H2O}n, the asymmetric unit contains a crystallographically unique CdII atom, one doubly deprotonated 4,4'-sulfonyl­dibenzoic acid (H2SDBA) ligand, one 3,4,7,8-tetra­methyl-1,10-phenanthroline (TMPHEN) mol­ecule and three solvent water mol­ecules. Each CdII centre is six-coordinated by two O atoms from a chelating carboxyl­ate group of a SDBA2- ligand, two O atoms from monodentate carboxyl­ate groups of two different SDBA2- ligands and two N atoms from a chelating TMPHEN ligand. There are two coordination patterns for the carboxyl­ate groups of the SDBA2- ligand, with one in a [mu]1-[eta]1:[eta]1 chelating mode and the other in a [mu]2-[eta]1:[eta]1 bis-monodentate mode. Single-crystal X-ray diffraction analysis revealed that the title compound is a one-dimensional double-chain polymer containing 28-membered rings based on the [Cd2(CO2)2] rhomboid subunit. More inter­estingly, a chair-shaped water hexa­mer cluster is observed in the compound.

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In the title mixed-ligand metal-organic polymeric complex [Cd(C14H8O6S)(C16H16N2)(H2O)]n, the asymmetric unit con­tains a crystallographically unique CdII atom, one doubly deprotonated 4,4'-sulfonyl­dibenzoic acid ligand (H2SDBA), one 3,4,7,8-tetra­methyl-1,10-phenanthroline (TMPHEN) mol­ecule and one water mol­ecule. Each CdII centre is coordinated by two N atoms from the chelating TMPHEN ligand, three O atoms from monodentate carboxyl­ate groups of three different SDBA2- ligands and one O atom from a coordinated water mol­ecule, giving a distorted CdN2O4 octa­hedral geom­etry. Single-crystal X-ray diffraction analysis reveals that the compound is a one-dimensional double-chain polymer con­taining 28-membered rings based on Cd2O2 clusters, with a Cd...Cd separation of 3.6889 (4) Å. These chains are linked by O-H...O and C-H...O hydrogen bonds to form a three-dimensional supra­molecular framework. The framework is reinforced by [pi]-[pi] and C-O...[pi] inter­actions.

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5-[(Imidazol-1-yl)methyl]benzene-1,3-dicarb­oxy­lic acid (H2L) was synthesized and the dimethyl­formamide- and dimethyl­acetamide-solvated structures of its adducts with CuII, namely catena-poly[[copper(II)-bis­[[mu]-3-carb­oxy-5-[(imidazol-1-yl)methyl]benzoato]] di­methyl­form­amide disolvate], {[Cu(C12H9N2O4)2]·2C3H7NO}n, (I), and catena-poly[[copper(II)-bis­[[mu]-3-carb­oxy-5-[(imid­azol-1-yl)methyl]benzoato]] dimethyl­acet­amide disolvate], {[Cu(C12H9N2O4)2]·2C4H9NO}n, (II), the formation of which are associated with mono-deprotonation of H2L. The two structures are isomorphous and isometric. They consist of one-dimensional coordination polymers of the organic ligand with CuII in a 2:1 ratio, [Cu([mu]-HL)2]n, crystallizing as the dimethyl­formamide (DMF) or dimethyl­acetamide (DMA) disolvates. The CuII cations are characterized by a coordination number of six, being located on centres of crystallographic inversion. In the polymeric chains, each CuII cation is linked to four neighbouring HL- ligands, and the organic ligand is coordinated via Cu-O and Cu-N bonds to two CuII cations. In the corresponding crystal structures of (I) and (II), the coordination chains, aligned parallel to the c axis, are further inter­linked by strong hydrogen bonds between the noncoordinated carb­oxy groups in one array and the coordinated carboxyl­ate groups of neighbouring chains. Mol­ecules of DMF and DMA (disordered) are accommodated at the inter­face between adjacent polymeric assemblies. This report provides the first structural evidence for the formation of coordination polymers with H2L via multiple metal-ligand bonds through both carboxyl­ate and imidazole groups.

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A one-dimensional AgI coordination complex, catena-poly[[silver(I)-[mu]-{2-[2-(pyridin-4-yl)-1H-benzimidazol-1-ylmethyl]phenol-[kappa]2N2:N3}] perchlorate monohydrate], {[Ag(C19H15N3O)]ClO4·H2O}n, was synthesized by the reaction of 2-[2-(pyridin-4-yl)-1H-benzimidazol-1-ylmethyl]phenol (L) with silver perchlorate. In the complex, the L ligands are arranged alternately and link AgI cations through one benzimidazole N atom and the N atom of the pyridine ring, leading to an extended zigzag chain structure. In addition, the one-dimensional chains are extended into a three-dimensional supra­molecular architecture via O-H...O hydrogen-bond inter­actions and [pi]-[pi] stacking inter­actions. The complex exhibits photoluminescence in acetonitrile solution, with an emission maximum at 390 nm, and investigation of the thermal stability reveals that the network structure is stable up to 650 K.

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The title compound, {(C6H14N2O2)[Cu2Cl6(H2O)]}n, consists of 1,4-dihy­droxy-1,4-diazo­niabicyclo­[2.2.2]octane dications and one-dimensional inorganic anionic {[Cu2Cl6(H2O)]2-}n chains in which both five-coordinate [CuCl3(H2O)]- and five-coordinate [CuCl3]- units exist. These two distinct type of unit are linked together by one chloride ion and are bridged across centres of inversion to further units of their own type through two chloride ions, giving rise to novel polymeric zigzag chains parallel to the c axis. The chains are connected by O-H...Cl hydrogen bonds to produce R24(16) ring motifs, resulting in two-dimensional layers parallel to the ac plane. These layers are linked into a three-dimensional framework with the organic cations via O-H...Cl hydrogen bonds. Hydrogen bonding between the chains, and between the chains and the organic cations, provides stability to the crystal structure.

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3,4-Dimeth­oxy-trans-cinnamic acid (Dmca) reacts with zinc sulfate in the presence of 4-(1H-pyrazol-3-yl)pyridine (L1) or 4,4'-bipyridine (L2) under hydro­thermal conditions to afford two mixed-ligand coordination complexes, namely tetra­kis­([mu]-3,4-dimeth­oxy-trans-cinnamato-[kappa]2O:O')bis­[[4-(1H-pyrazol-3-yl)pyridine]­zinc(II)] hepta­hydrate, [Zn2(C11H11O4)4(C8H7N3)2]·7H2O or [Zn2(Dmca)4(L1)2]·7H2O, (I), and catena-poly[[bis­(3,4-dimeth­oxy-trans-cinnamato-[kappa]O)zinc(II)]-[mu]-4,4'-bipyridine-[kappa]2N:N'], [Zn(C11H11O4)2(C10H8N2)]n or [Zn(Dmca)2(L2)]n, (II). The ZnII centres in the two compounds display different coordination polyhedra. In complex (I), the ZnII cation is five-coordinated with a pseudo-square-pyramidal geometry, while in complex (II) the ZnII cation sits on a twofold axis and adopts a distorted tetra­hedral coordination environment. Complex (I) features a centrosymmetric binuclear paddle-wheel-like structure, while complex (II) shows a chain structure. This study emphasizes the significant effect of the coordination mode of both carboxyl­ate-group and N-donor coligands on the formation of complex structures.

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The novel asymmetric bridging ligand 1-[(pyridin-3-yl)methyl]-2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole (L) has been used to construct the coordination polymers catena-poly[[[dibromidocadmium(II)]-[mu]3-1-[(pyridin-3-yl)methyl]-2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole] monohydrate], {[CdBr2(C24H18N4)]·H2O}n, (I), and catena-poly[[diiodidocadmium(II)]-[mu]3-1-[(pyridin-3-yl)methyl]-2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole], [CdI2(C24H18N4)]n, (II). Com­pounds (I) and (II) are closely related one-dimensional polymers based on 16- and 20-membered macrocycles along the chains, but they are not isomorphous. The chains are crosslinked into a two-dimensional network via hydrogen bonds and [pi]-[pi] inter­actions in (I), and into a three-dimensional framework through [pi]-[pi] inter­actions in (II). One well-ordered solvent water mol­ecule per asymmetric unit is included in (I) and forms O...Br hydrogen bonds.

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In the title compound, catena-poly[[[N,N'-bis­(pyridin-3-ylmeth­yl)-[1,1'-biphen­yl]-4,4'-dicarboxamide]­chlorido­zinc(II)]-[mu]-[1,1'-biphen­yl]-4,4'-dicarboxyl­ato-[[N,N'-bis­(pyridin-3-ylmeth­yl)-[1,1'-biphen­yl]-4,4'-dicarboxamide]­chloridozinc(II)]-[mu]-[N,N'-bis­(pyridin-3-ylmeth­yl)-[1,1'-biphen­yl]-4,4'-dicarboxamide]], [Zn2(C14H8O4)Cl2(C26H22N4O2)3]n, the ZnII centre is four-coordinate and approximately tetra­hedral, bonding to one carboxyl­ate O atom from a bidentate bridging dianionic [1,1'-biphen­yl]-4,4'-dicarboxyl­ate ligand, to two pyridine N atoms from two N,N'-bis­(pyridin-3-ylmeth­yl)-[1,1'-biphen­yl]-4,4'-dicarboxamide ligands and to one chloride ligand. The pyridyl ligands exhibit bidentate bridging and monodentate terminal coordination modes. The bidentate bridging pyridyl ligand and the bridging [1,1'-biphen­yl]-4,4'-dicarboxyl­ate ligand both lie on special positions, with inversion centres at the mid-points of their central C-C bonds. These bridging groups link the ZnII centres into a one-dimensional tape structure that propagates along the crystallographic b direction. The tapes are inter­linked into a two-dimensional layer in the ab plane through N-H...O hydrogen bonds between the monodentate ligands. In addition, the thermal stability and solid-state photoluminescence properties of the title compound are reported.

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The crystal structure of the title novel one-dimensional ABX3-type organic-inorganic hybrid complex {(C10H16N)[CdCl3]}n, (I), consists of benzyl­tri­methyl­ammonium (Me3BzN+) cations and one-dimensional anionic {[Cd([mu]-Cl)3]-}[infinity] chains. Each CdII centre is hexacoordinated by bridging chloride ligands, giving a slightly distorted octa­hedral Cd([mu]-Cl)6 arrangement. The octa­hedra are linked by two opposite shared faces, giving rise to an almost perfectly linear anionic {[Cd([mu]-Cl)3]-}[infinity] chain in the a-axis direction. Me3BzN+ cations located in the inter-chain spaces balance the charge. Noncovalent static attracting forces (Coulombic and van der Waals forces) and nonclassical C-H...Cl hydrogen-bond inter­actions stabilize the crystal structure.

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The asymmetric unit of the title compound, [Pb2(C8H3IO4)2(CH4O)]n, contains two PbII atoms, two 5-iodo­isophthalate (5-IIP2-) ligands and one coordinated methanol mol­ecule. One Pb atom is eight-coordinated, surrounded by seven carboxyl­ate O atoms from five 5-IIP2- ligands and one O atom from the terminal methanol ligand. The other Pb atom is seven-coordinated in a hemidirected geometry, surrounded by seven carboxyl­ate O atoms from five 5-IIP2- ligands. Both Pb atoms are connected by carboxyl­ate groups to form a one-di­men­sional infinite rod along the a axis; neighbouring rods are further linked by the aromatic rings of 5-IIP2- to generate the final three-dimensional structure with channels in the a direction. An O-H...O hydrogen bond between the methanol ligand and one of the carboxyl­ate groups of a 5-IIP2- ligand stablizes the three-dimensional framework. Inter­estingly, a centrosymmetric rhombus-shaped I4 unit is formed by four 5-IIP2- ligands, with I...I distances of 3.8841 (8) and 3.9204 (8) Å.

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The title complex, [NaNi(C5H7O2)3]n, contains an anionic tris­(acetyl­acetonato)nickelate(II) unit, [Ni(acac)3]- (acac is acetyl­acetonate), with a highly regular octa­hedral coordination geometry. The NiII cation lies on a Wyckoff a site, resulting in D3 symmetry of the anion. Charge balance is provided by sodium cations, which occupy Wyckoff type b sites. Each sodium cation is surrounded by two [Ni(acac)3]- anions, each of which is connected to the alkali metal through three O atoms, in a fac configuration. This arrangement leads to the formation of linear [Na{Ni(acac)3}]n chains along the c axis. The Ni...Na distance is 2.9211 (10) Å. The title complex is one of the few examples of heterometallic systems based on alkali and transition metal cations bridged by acetyl­acetonate ligands.

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In the title compound, {[Cu(C15H11ClN2O3)(C4H9NO)]n, the CuII cation has square-pyramidal geometry. The morpholine ligand serves as a bridge to link two symmetry-related metal atoms, resulting in an infinite chain structure along the a axis. Adjacent chains are extended into a two-dimensional layered structure via hydrogen bonds formed between morpholine and amide N atoms [N-H...N = 2.971 (3) Å].

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A new 3d-4f heterometallic polymer, poly[[aqua-[mu]3-chlorido-[[mu]3-4-(pyridin-4-yl)benzoato]tris­[[mu]2-4-(pyridin-4-yl)benzoato]dicopper(I)erbium(III)] dihydrate], {[Cu2Er(C12H8NO2)4Cl(H2O)]·2H2O}n, was synthesized by the hydro­thermal reaction of Er2O3, CuCl2·2H2O and 4-(pyridin-4-yl)benzoic acid in the presence of HClO4. The asymmetric unit contains one Er3+ cation, two Cu+ cations, one Cl- anion, four deprotonated 4-(pyridin-4-yl)benzoate ligands, one coordinated aqua ligand and two solvent water mol­ecules. This tubular one-dimensional polymer is constructed from alternating clusters of europium(III)-water and copper(I) chloride bridged by 4-(pyridin-4-yl)benzoate ligands. Extensive hydrogen-bonding inter­actions involving both the coordinated and the solvent water mol­ecules provide further stabilization to the structure.

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A novel supra­molecular framework, catena-poly[[[aqua(2-phenyl­quinoline-4-carboxyl­ato-[kappa]O)silver(I)]-[mu]-4,4'-bipyridine-[kappa]2N:N'] dihydrate], {[Ag(C16H10NO2)(C10H8N2)(H2O)]·2H2O}n, has been synthesized and structurally characterized. The AgI centres are four-coordinated and bridged by 4,4'-bi­pyridine (4,4'-bipy) ligands to form a one-dimensional Ag-bipy chain. The Ag-bipy chains are further linked together by inter­molecular O-H...O and O-H...N hydrogen-bonding inter­actions between adjacent chains, resulting in a three-dimensional framework.

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The solvothermal reactions of 2,6-bis­(1H-benzimidazol-2-yl)pyridine (H2bpp) and hydrated ZnCl2 in the presence of pyridine-2,4-di­carb­oxy­lic acid (2,4-pdcH2) or pyridine-2,5-di­carb­oxy­lic acid (2,5-pdcH2) afforded the title one-dimensional linear compounds, [Zn(C7H3NO4)(C19H13N5)]n or [Zn(2,4-pdc)(H2bpp)]n, (I), and [Zn(C7H3NO4)(C19H13N5)]n or [Zn(2,5-pdc)(H2bpp)]n, (II), respectively. The ZnII cations in these compounds have closely comparable geometries and both are octa­hedrally coordinated by N4O2 donor sets. The thermal stabilities have been investigated by thermogravimetric analysis (TGA) on the crystalline samples and their solid-state photoluminescence properties have been investigated at room temperature.

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The title structure con­tains two kinds of independent one-dimensional chain, viz. {[Cd(C8H15N2O2)Cl2]+}n and {[CdCl3(H2O)]-}n, and uncoordinated water mol­ecules. Each CdII cation in the former chain is octa­hedrally coordinated by two pairs of bridging chloride ligands and two O atoms from different bridging carboxyl­ate groups, while CdII cations in the latter chain are octa­hedrally surrounded by four bridging chloride ligands, one terminal chloride ligand and one coordinated water mol­ecule.

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The structural unit consists of one C2-symmetric [NbOF4]- anion, where the NbV centre is five-coordinated by four F atoms and one O atom in the first coordination shell, forming a square-pyramidal coordination geometry, and of one centrosymmetric coordinated [Cu2(obpy)2]+ cation (obpy is 2,2'-bipyridin-6-olate), in which the oxidation state of each Cu site is disordered, which is confirmed by XPS results.

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Single-crystal structural analysis reveals that the title complex is a one-dimensional polymeric chain, which is further extended to a three-dimensional supra­molecular network via a combination of hydrogen-bonding and aromatic stacking inter­actions.

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In CuI and AgI ladder-like coordination polymers, two metal ions are linked by two 2-ethyl-1-(pyridin-3-ylmeth­yl)-1H-benzimidazole ligands (bep) to form a centrosymmetric 18-membered M2(bep)2 metallacycle, while adjacent M2(bep)2 metallacycles are further inter­linked by another two bep ligands resulting in a ladder-like array.

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The structure of a nickel compound with a three-dimensional polycatenation framework formed by intermolecular hydrogen bonds and interlocking interactions is reported.

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The structure of a title novel one-dimensional ABX3-type organic-inorganic hybrid complex consists of benzyl­tri­ethyl­ammonium cations and one-dimensional anionic {[CdCl3]-}n chains, in which the CdII centres are in an unusual two-layer five-coordinated arrangement.

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A one-dimensional polymeric structure of CoII with sulfadiazine and 1,3-bis­(pyridin-4-yl)propane is further stabilized by inter­molecular hydrogen bonding. The structure is of inter­est with respect to its electrochemical properties in the reduction reaction of H2O2 to H2O. Investigation of the thermal stability shows that the complex is stable up to 543 K.

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In a polymer of 2,5-bis­[4-methyl-3-(pyridin-3-yl)phen­yl]-1,3,4-oxa­diazole (L) with ZnCl2, one-dimensional P (plus) and M (minus) helical chains are formed, where the ligand has different directions of twist. The helical chains stack together via inter­chain [pi]-[pi] and C-H...[pi] inter­actions.

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A one-dimensional coordination polymer with a twofold symmetric repeat unit containing three MnII centres. Two different coordination geometries are observed for the two independent MnII metal centres, viz. a distorted penta­gonal bipyramid and a distorted octa­hedron.

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The title compound comprises one-dimensional zigzag polymers of MgII cations bridged by isobutyrate groups. The crystal structure is characterized by stacks of hydro­phobic (isobutyrate) and hydro­philic (H2O) groups that alternate along the a axis.

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