Poly[aqua(μ2‐benzene‐1,4‐dicarboxylato)(μ2‐4,4′‐bipyridine N,N′‐dioxide)cadmium(II)], a threefold interpenetrating diamond net

In the title compound, [Cd(C₈H₄O₄)(C₁₀H₈N₂O₂)(H₂O)]_n, (I), each Cd^II atom is seven‐coordinated in a distorted monocapped trigonal prismatic coordination geometry, surrounded by four carboxylate O atoms from two different benzene‐1,4‐dicarboxylate (1,4‐bdc) anions, two O atoms from two distinct 4,4′‐bipyridine N,N′‐dioxide (bpdo) ligands and one water O atom. The Cd^II atom and the water O atom are on a twofold rotation axis. The bpdo and 1,4‐bdc ligands are on centers of inversion. Each crystallographically unique Cd^II center is bridged by the 1,4‐bdc dianions and bpdo ligands to give a three‐dimensional diamond framework containing large adamantanoid cages. Three identical such nets are interlocked with each other, thus directly leading to the formation of a threefold interpenetrated three‐dimensional diamond architecture. To the best of our knowledge, (I) is the first example of a threefold interpenetrating diamond net based on both bpdo and carboxylate ligands. There are strong linear O—H...O hydrogen bonds between the water molecules and carboxylate O atoms within different diamond nets. Each diamond net is hydrogen bonded to its two neighbors through these hydrogen bonds, which further consolidates the threefold interpenetrating diamond framework.     

Poly[propane‐1,3‐diammonium [tetra‐μ3‐oxo‐hexaoxotrimolybdenum(VI)] dihydrate]

The crystal structure of the title compound, {(C₃H₁₂N₂)[Mo₃O₁₀]·2H₂O}_n, is composed of [Mo₃O₁₀]²⁻ anionic chains, propane‐1,3‐diammonium cations and solvent water molecules. The [Mo₃O₁₀]²⁻ chain is constructed from edge‐sharing MoO₆ octahedra. The protonated propane‐1,3‐diamine cations and solvent water molecules are located between the chains and are linked to the O atoms of the inorganic chains by hydrogen bonds.     

Bis[tris(2,2′‐bipyridyl‐κ2N,N′)cobalt(II)] cyclo‐tetravanadate undecahydrate

The title compound, [Co(C₁₀H₈N₂)₃]₂[V₄O₁₂]·11H₂O, is composed of two symmetry‐related cations containing octahedrally coordinated Co^II ions, a centrosymmetric [V₄O₁₂]⁴⁻ anion with an eight‐membered ring structure made up of four VO₄ tetrahedra, and 11 solvent water molecules. The Co^II cations and vanadate anions are isolated and build cation and anion layers, respectively. In addition, the title compound exhibits a three‐dimensional network through intra‐ and intermolecular hydrogen‐bond interactions between water molecules and O atoms of the anions, and the crystal structure is stabilized mainly by hydrogen bonds.     

trans‐Di­aqua­bis(5‐carboxy‐1H‐imidazole‐4‐carboxyl­ato‐κ2N3,O4)­cobalt(II) 4,4′‐bi­pyridine solvate

In the title compound, [Co(C₅H₃N₂O₄)₂(H₂O)₂]·C₁₀H₈N₂, the Co atom is trans‐coordinated by two pairs of N and O atoms from two monoanionic 4,5‐di­carboxy­imidazole ligands, and by two O atoms from two coordinated water mol­ecules, in a distorted octahedral geometry. The 4,4′‐bi­pyridine solvent molecule is not involved in coordination but is linked by an N—H⋯N hydrogen bond to the neutral [Co(C₅H₃N₂O₄)₂(H₂O)₂] mol­ecule. Both mol­ecules are located on inversion centers. The crystal packing is stabilized by N—H⋯N and O—H⋯O hydrogen bonds, which produce a three‐dimensional hydrogen‐bonded network. Offset π–π stacking interactions between the pyridine rings of adjacent 4,4′‐bi­pyridine molecules were observed, with a face‐to‐face distance of 3.345 (1) Å.     

A novel one‐dimensional coordination polymer,catena‐poly[[diaquacobalt(II)]‐μ‐(2,2′‐bipyridyl‐3,3′‐dicarboxylato‐κ4N,N′:O,O′)]

The title compound, [Co(C₁₂H₆N₂O₄)(H₂O)₂]_n, has been hydro­thermally synthesized and structurally characterized. It consists of polymeric chains of [Co{μ‐(2,2′‐bipyridyl‐3,3′‐di­carboxyl­ato‐κ⁴N,N′:O,O′)}(H₂O)₂] units, in which each Co^II cation is octahedrally coordinated by two chelating pyridyl N atoms, two chelating carboxyl O atoms from different carboxylate groups of another bipyridyl ligand, and two water mol­ecules as terminal ligands. A crystallographic twofold axis parallel to the chain axis, passes through the Co atom.     

catena‐Poly[[[pentaaquathulium(III)]‐μ‐5‐sulfonatobenzene‐1,3‐dicarboxylato] 4,4′‐bipyridyl 1.5‐solvate hemihydrate]

The crystal structure of the title compound, {[Tm(C₈H₃O₇S)(H₂O)₅]·1.5C₁₀H₈N₂·0.5H₂O}_n, is built up from two [Tm(SIP)(H₂O)₅] molecules (SIP³⁻ is 5‐sulfonatobenzene‐1,3‐dicarboxylate), three 4,4′‐bipyridyl (bpy) molecules and one solvent water molecule. One of the bpy molecules and the solvent water molecule are located on an inversion centre and a twofold rotation axis, respectively. The Tm^III ion coordination is composed of four carboxylate O atoms from two trianionic SIP³⁻ ligands and five coordinated water molecules. The Tm³⁺ ions are linked by the SIP³⁻ ligands to form a one‐dimensional zigzag chain propagating along the c axis. The chains are linked by interchain O—H...O hydrogen bonds to generate a two‐dimensional layered structure. The bpy molecules are not involved in coordination but are linked by O—H...N hydrogen bonds to form two‐dimensional layers. The two‐dimensional layers are further bridged by the bpy molecules as pillars and the solvent water molecules through hydrogen bonds, giving a three‐dimensional supramolecular structure. π–π stacking interactions between the parallel aromatic rings, arranged in an offset fashion with a face‐to‐face distance of 3.566 (1) Å, are observed in the crystal packing.     

A three‐dimensional framework in 2,2′‐biimidazolium bis(2,2′‐biimidazole‐κ2N,N′)bis(biphenyl‐2,4′‐dicarboxylato‐κO)manganese(II) hexahydrate

In the title salt, (C₆H₈N₄)[Mn(C₁₄H₈O₄)₂(C₆H₆N₄)₂]·6H₂O, the Mn^II atom lies on an inversion centre and is coordinated by four N atoms from two 2,2′‐biimidazole (biim) ligands and two O atoms from two biphenyl‐2,4′‐dicarboxylate (bpdc) anions to give a slightly distorted octahedral coordination, while the cation lies about another inversion centre. Adjacent [Mn(bpdc)₂(biim)₂]²⁻ anions are linked via two pairs of N—H...O hydrogen bonds, leading to an infinite chain along the [100] direction. The protonated [H₂biim]²⁺ moiety acts as a charge‐compensating cation and space‐filling structural subunit. It bridges two [Mn(bpdc)₂(biim)₂]²⁻ anions through two pairs of N—H...O hydrogen bonds, constructing two R₂²(9) rings, leading to a zigzag chain in the [2] direction, which gives rise to a ruffled set of [H₂biim]²⁺[Mn(bpdc)₂(biim)₂]²⁻ moieties in the [01] plane. The water molecules give rise to a chain structure in which O—H...O hydrogen bonds generate a chain of alternating four‐ and six‐membered water–oxygen R₄²(8) and R₆⁶(12) rings, each lying about independent inversion centres giving rise to a chain along the [100] direction. Within the water chain, the (H₂O)₆ water rings are hydrogen bonded to two O atoms from two [Mn(bpdc)₂(biim)₂]²⁻ anions, giving rise to a three‐dimensional framework.     

Crystal‐to‐crystal transformation upon dehydration of a copper(II) 2,2′:6′,2′′‐terpyridine complex

The reaction of 2,2′:6′,2′′‐terpyridine (terpy) with CuCl₂ in the presence of sodium sulfite led to the synthesis of the ionic complex aquachlorido(2,2′:6′,2′′‐terpyridyl‐κ³N,N′,N′′)copper(II) chlorido(dithionato‐κO)(2,2′:6′,2′′‐terpyridyl‐κ³N,N′,N′′)cuprate(II) dihydrate, [CuCl(C₁₅H₁₁N₃)(H₂O)][CuCl(S₂O₆)(C₁₅H₁₁N₃)]·2H₂O, (I), and the in situ synthesis of the S₂O₆²⁻ dianion. Compound (I) is composed of a [CuCl(terpy)(H₂O)]⁺ cation, a [Cu(S₂O₆)(terpy)]⁻ anion and two solvent water molecules. Thermogravimetric analysis indicated the loss of two water molecules at ca 363 K, and at 433 K the weight loss indicated a total loss of 2.5 water molecules. The crystal structure analysis of the resulting pale‐green dried crystals, μ‐dithionato‐κ²O:O′‐bis[chlorido(2,2′:6′,2′′‐terpyridyl‐κ³N,N′,N′′)copper(II)] monohydrate, [Cu₂Cl₂(S₂O₆)(C₁₅H₁₁N₃)₂]·H₂O, (II), revealed a net loss of 1.5 water molecules and the formation of a binuclear complex with two [CuCl(terpy)]⁺ cations bridged by a dithionate dianion. The crystal‐to‐crystal transformation involved an effective reduction in the unit‐cell volume of ca 7.6%. In (I), the ions are linked by O—H...O hydrogen bonds involving the coordinated and solvent water molecules and O atoms of the dithionate unit, to form ribbon‐like polymer chains propagating in [100]. These chains are linked by Cu...Cl interactions [3.2626 (7) Å in the cation and 3.3492 (7) Å in the anion] centred about inversion centres, to form two‐dimensional networks lying in and parallel to (01). In (II), symmetry‐related molecules are linked by O—H...O hydrogen bonds involving the partially occupied disordered water molecule and an O atom of the bridging thiosulfite anion, to form ribbon‐like polymer chains propagating in [100]. These chains are also linked by Cu...Cl interactions [3.3765 (12) Å] centred about inversion centres to form similar two‐dimensional networks to (I) lying in and parallel to (02), crosslinked into three dimensions by C—H...O=S and C—H...O(water) interactions.     

catena‐Poly[[diaquazinc(II)]‐μ‐4,4′‐sulfonyldibenzoato‐κ2O:O′]

The title compound, [Zn(C₁₄H₈O₆S)(H₂O)₂]_n, is the first reported metal complex of the 4,4′‐sulfonyldibenzoate anion. The structure comprises zigzag chains of alternating [Zn(H₂O)₂]²⁺ and sulfonyldibenzoate units, the central Zn and S atoms of which lie on crystallographic twofold axes. The Zn^II centre occupies a strongly distorted tetrahedral environment [O—Zn—O = 83.30 (7)–136.19 (8)°], coordinated by the two water O atoms [Zn—O = 1.986 (2) Å] and one O atom from each of two carboxylate groups [Zn—O = 1.9942 (19) Å], with much longer contacts to the other O atoms of these carboxylates [Zn—O = 2.528 (2) Å]. Hydrogen bonds between carboxylate O atoms and coordinated water molecules in adjacent chains lead to the formation of a three‐dimensional network structure.     

Cobalt(II) and cadmium(II) square grids supported with 4,4′‐bipyrazole and accommodating 3‐carboxyadamantane‐1‐carboxylate

In poly[[bis(μ‐4,4′‐bi‐1H‐pyrazole‐κ²N²:N^2′)bis(3‐carboxyadamantane‐1‐carboxylato‐κO¹)cobalt(II)] dihydrate], {[Co(C₁₂H₁₅O₄)₂(C₆H₆N₄)₂]·2H₂O}_n, (I), the Co²⁺ cation lies on an inversion centre and the 4,4′‐bipyrazole (4,4′‐bpz) ligands are also situated across centres of inversion. In its non‐isomorphous cadmium analogue, {[Cd(C₁₂H₁₅O₄)₂(C₆H₆N₄)₂]·2H₂O}_n, (II), the Cd²⁺ cation lies on a twofold axis. In both compounds, the metal cations adopt an octahedral coordination, with four pyrazole N atoms in the equatorial plane [Co—N = 2.156 (2) and 2.162 (2) Å; Cd—N = 2.298 (2) and 2.321 (2) Å] and two axial carboxylate O atoms [Co—O = 2.1547 (18) Å and Cd—O = 2.347 (2) Å]. In both structures, interligand hydrogen bonding [N...O = 2.682 (3)–2.819 (3) Å] is essential for stabilization of the MN₄O₂ environment with its unusually high (for bulky adamantanecarboxylates) number of coordinated N‐donor co‐ligands. The compounds adopt two‐dimensional coordination connectivities and exist as square‐grid [M(4,4′‐bpz)₂]_n networks accommodating monodentate carboxylate ligands. The interlayer linkage is provided by hydrogen bonds from the carboxylic acid groups via the solvent water molecules [O...O = 2.565 (3) and 2.616 (3) Å] to the carboxylate groups in the next layer [O...O = 2.717 (3)–2.841 (3) Å], thereby extending the structures in the third dimension.     

Bis(2,2′‐bi­pyridine‐κ2N,N′)(oxalato‐κ2O,O′)­cobalt(II) pentahydrate

The synthesis and crystal structure of the mononuclear title compound, [Co(C₂O₄)(C₁₀H₈N₂)₂]·5H₂O, is reported. The Co atom is six‐coordinated by two O atoms of a bidentate oxalate group and by four N atoms of two bi­pyridine ligands. The neutral [Co(C₂O₄)(C₁₀H₈N₂)₂] entities are connected by π–π stacking interactions of the aromatic systems into a two‐dimensional layer, interconnected through a ladder‐like hydrogen‐bonding pattern of solvate water mol­ecules.     

Poly[[aqua(μ7‐ethylenediaminetetraacetato)dicadmium(II)] monohydrate]

The title compound, {[Cd₂(C₁₀H₁₂N₂O₈)(H₂O)]·H₂O}_n, consists of two crystallographically independent Cd^II cations, one ethylenediaminetetraacetate (edta) tetraanion, one coordinated water molecule and one solvent water molecule. The coordination of one of the Cd atoms, Cd1, is composed of five O atoms and two N atoms from two tetraanionic edta ligands in a distorted pentagonal–bipyramidal coordination geometry. The other Cd atom, Cd2, is six‐coordinated by five carboxylate O atoms from five edta ligands and one water molecule in a distorted octahedral geometry. Two neighbouring Cd1 atoms are bridged by a pair of carboxylate O atoms to form a centrosymmetric [Cd₂(edta)₂]⁴⁻ unit located on the inversion centre, which is further extended into a two‐dimensional layered structure through Cd2—O bonds. There are hydrogen bonds between the coordinated water molecules and carboxylate O atoms within the layer. The solvent water molecules occupy the space between the layers and interact with the host layers through O—H...O and C—H...O interactions.     

New organic–inorganic frameworks incorporating iso‐ and heteropolymolybdate units and a 3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium multiple hydrogen‐bond donor

Poly[bis(3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium) γ‐octamolybdate(VI) dihydrate], {(C₁₀H₁₆N₄)₂[Mo₈O₂₆]·2H₂O}_n, (I), and bis(3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium) α‐dodecamolybdo(VI)silicate tetrahydrate, (C₁₀H₁₆N₄)₂[SiMo₁₂O₄₀]·4H₂O, (II), display intense hydrogen bonding between the cationic pyrazolium species and the metal oxide anions. In (I), the asymmetric unit contains half a centrosymmetric γ‐type [Mo₈O₂₆]⁴⁻ anion, which produces a one‐dimensional polymeric chain by corner‐sharing, one cation and one water molecule. Three‐centre bonding with 3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium, denoted [H₂Me₄bpz]²⁺ [N...O = 2.770 (4)–3.146 (4) Å], generates two‐dimensional layers that are further linked by hydrogen bonds involving water molecules [O...O = 2.902 (4) and 3.010 (4) Å]. In (II), each of the four independent [H₂Me₄bpz]²⁺ cations lies across a twofold axis. They link layers of [SiMo₁₂O₄₀]⁴⁻ anions into a three‐dimensional framework, and the preferred sites for pyrazolium/anion hydrogen bonding are the terminal oxide atoms [N...O = 2.866 (6)–2.999 (6) Å], while anion/aqua interactions occur preferentially viaμ₂‐O sites [O...O = 2.910 (6)–3.151 (6) Å].     

The structure of {[Co(pht)(bpy)(H2O)]·3H2O}n (pht is phthalate and bpy is 4,4′‐bipyridine) and the role of solvent water clusters in structure stability

The Co^II cation in poly[[aqua(μ‐benzene‐1,2‐dicarboxylato‐κ³O¹,O²:O¹)(μ‐4,4′‐bipyridine‐κ²N:N′)cobalt(II)] trihydrate], {[Co(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)]·3H₂O}_n, is octahedrally coordinated by two N atoms of two 4,4′‐bipyridine ligands, three O atoms from phthalate anions and a fourth O atom from a coordinated water molecule. The packing consists of planes of coordination polymers linked by hydrogen bonds mediated by three solvent water molecules; the linkage is achieved by the water molecules forming intricate oligomeric clusters which also involve the O atoms of the phthalate ligands.     

Diaquabis(2,5‐dihydroxybenzoato‐κO)bis(1,10‐phenanthroline‐κ2N,N′)strontium(II) bis(1,10‐phenanthroline) tetrahydrate

The title compound, [Sr(C₇H₅O₄)₂(C₁₂H₈N₂)₂(H₂O)₂]·2C₁₂H₈N₂·4H₂O, consists of an Sr^II complex, uncoordinated phenanthroline (phen) molecules and solvent water molecules. The Sr^II ion is located on a twofold axis and is coordinated by two phen ligands, two dihydroxybenzoate anions and two water molecules in a distorted tetragonal antiprismatic geometry. Partially overlapped arrangements exist between parallel coordinated and parallel uncoordinated phen rings; the face‐to‐face separations between the former (coordinated) and the latter (uncoordinated) rings are 3.436 (13) and 3.550 (14) Å, respectively. This difference suggests the effect of metal coordination on π–π stacking between phen rings.     

Triaqua(μ‐7‐iodo‐8‐oxidoquinoline‐5‐sulfonato‐κ2N,O8)dioxidouranium(VI) dihydrate

In the title compound, [U(C₉H₄INO₄S)O₂(H₂O)₃]·2H₂O, the asymmetric unit contains a UO₂²⁺ ion coordinated by the N and O atoms of a 7‐iodo‐8‐oxidoquinoline‐5‐sulfonate dianion (ferron anion) and three coordinated water molecules, and two uncoordinated water molecules. The UO₂²⁺ ion exhibits a seven‐coordinate pentagonal bipyramidal geometry. The usual sulfonate oxygen coordination is absent but the sulfonate O atoms, along with the coordinated and lattice water molecules, play a vital role in assembling the three‐dimensional structure via an extensive network of intermolecular O—H...O hydrogen bonds and π–π stacking interactions.     

Di­aqua­bis(1,10‐phenanthroline‐κ2N,N′)­manganese(II) thiodiglycolate bis(1,10‐phenanthroline‐κ2N,N′)(thiodiglycolato‐κ2O,O′)­manganese(II) tridecahydrate

The title compound, [Mn(C₁₂H₈N₂)₂(H₂O)₂](C₄H₄O₄S)·[Mn(C₄H₄O₄S)(C₁₂H₈N₂)₂]·13H₂O, contains one dianion of thio­diglycolic acid (tdga²⁻) and two independent man­ganese(II) moieties, viz. [Mn(phen)₂(H₂O)₂]²⁺ and [Mn(tdga)(phen)₂], where phen is 1,10‐phenanthroline. The Mn^II atoms are octahedrally coordinated by four N atoms of two bidentate phen ligands [Mn—N = 2.240 (2)–2.3222 (19) Å] and either two water O atoms or two tdga carboxyl O atoms [Mn—O = 2.1214 (17)–2.1512 (17) Å]. The tdga ligand chelates as an O,O′‐bidentate ligand, forming an eight‐membered ring with one Mn atom. The free tdga²⁻ dianion is hydrogen bonded to an [Mn(phen)₂(H₂O)₂]²⁺ ion, with O⋯O distances of 2.606 (2) and 2.649 (2) Å. The crystal structure is further stabilized by an extensive network of hydrogen bonds involving 13 water mol­ecules.     

Two two‐dimensional hydrogen‐bonded coordination networks: bis(3‐carboxybenzoato‐κO)bis(4‐methyl‐1H‐imidazole‐κN3)copper(II) and bis(3‐methylbenzoato‐κN)bis(4‐methyl‐1H‐imidazole‐κN3)copper(II) monohydrate

The title two‐dimensional hydrogen‐bonded coordination compounds, [Cu(C₈H₅O₄)₂(C₄H₆N₂)₂], (I), and [Cu(C₈H₇O₂)₂(C₄H₆N₂)₂]·H₂O, (II), have been synthesized and structurally characterized. The molecule of complex (I) lies across an inversion centre, and the Cu²⁺ ion is coordinated by two N atoms from two 4‐methyl‐1H‐imidazole (4‐MeIM) molecules and two O atoms from two 3‐carboxybenzoate (HBDC⁻) anions in a square‐planar geometry. Adjacent molecules are linked through intermolecular N—H...O and O—H...O hydrogen bonds into a two‐dimensional sheet with (4,4) topology. In the asymmetric part of the unit cell of (II) there are two symmetry‐independent molecules, in which each Cu²⁺ ion is also coordinated by two N atoms from two 4‐MeIM molecules and two O atoms from two 3‐methylbenzoate (3‐MeBC⁻) anions in a square‐planar coordination. Two neutral complex molecules are held together via N—H...O(carboxylate) hydrogen bonds to generate a dimeric pair, which is further linked via discrete water molecules into a two‐dimensional network with the Schläfli symbol (4³)₂(4⁶,6⁶,8³). In both compounds, as well as the strong intermolecular hydrogen bonds, π–π interactions also stabilize the crystal stacking.     

Diaquabis(quinoxaline‐2‐carboxylato‐κ2N1,O)copper(II)

In the title compound, [Cu(C₉H₅N₂O₂)₂(H₂O)₂], the Cu^II ion lies on an inversion centre and has an elongated centrosymmetric octahedral environment, equatorially trans‐coordinated by two N,O‐bidentate quinoxaline‐2‐carboxylate ligands and axially coordinated by two water O atoms. Symmetry‐related molecules are linked by strong O—H...O hydrogen bonds, involving the uncoordinated carboxyl O atom of the carboxylate group and the coordinated water molecules, to form a two‐dimensional network. Weak intermolecular C—H...N interactions also stabilize the crystal structure.     

Tetraaqua(4,4′‐dimethyl‐2,2′‐bipyridine‐κ2N,N′)nickel(II) sulfate monohydrate: a simple molecule with an extremely complex hydrogen‐bonding scheme

The title ionic compound, [Ni(C₁₂H₁₂N₂)(H₂O)₄]SO₄·H₂O, is composed of an Ni^II cation coordinated by a chelating 4,4′‐dimethyl‐2,2′‐bipyridine ligand via its two N atoms [mean Ni—N = 2.056 (2) Å] and by four aqua ligands [mean Ni—O = 2.073 (9) Å], the net charge being balanced by an external sulfate anion. The whole structure is stabilized by a solvent water molecule. Even though the individual constituents are rather featureless, they generate an extremely complex supramolecular structure consisting of a central hydrogen‐bonded two‐dimensional hydrophilic nucleus made up of complex cations, sulfate anions and coordinated and solvent water molecules, with pendant hydrophobic 4,4′‐dimethyl‐2,2′‐bipyridine ligands which interact laterally with their neighbours viaπ–π interactions. The structure is compared with closely related analogues in the literature.