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Metal−organic layers (MOLs), with well-defined, abundant active sites and good electron transport capabilities, are ideal platforms for studying the photoreduction of CO2 to value-added chemicals feedstocks in 2D/2D assembled materials.

The exploitation of highly stable and active catalysts for the conversion of CO2 into valuable fuels is desirable but is a great challenge. Herein, we report that the incorporation of chromophores into metal-organic frameworks (MOFs) could afford robust catalysts for efficient CO2 conversion. Specifically, a porous Nd(III) MOF (Nd-TTCA; TTCA3- = triphenylene-2,6,10-tricarboxylate) was constructed by incorporating one-dimensional Nd(CO2)n chains and TTCA3- ligands, which exhibits a very high stability, retaining its framework not only in the air at 300 °C for 2 h but also in boiling aqueous solutions at pH 1-12 for 7 days. More importantly, Nd-TTCA has achieved a 5-fold improvement in photocatalytic activity for reducing CO2 to HCOOH and a 10-fold improvement in catalytic activity for the cycloaddition of CO2 into cyclic carbonate in comparison to those of H3TTCA itself. This work gives a new strategy to design efficient artificial crystalline catalysts for CO2 conversion.

Collective weakness makes strength: A case of multiple π-π stacking interactions stabilizing a porous supramolecular framework., Revealing the contribution of π-π stacking interactions in supramolecular assembly is important for understanding the intrinsic nature of molecular assembly fundamentally. However, because they are much weaker than covalent bonds, π-π stacking interactions are usually ignored in the construction of porous materials. Obtaining stable porous materials that are only dependent on π-π stacking interactions, despite being very challenging, could address this concern. Here, we present a porous supramolecular framework (π-1) stabilized only by intermolecular π-π stacking interactions. π-1 shows good thermal and chemical stability not only in various organic solvents but also in aqueous solution in a broad pH range. Furthermore, featuring one-dimensional channels with dangling thiolate groups, π-1 exhibits excellent Hg2+ removal performance, with adsorption capacity as high as 786.67 mg g−1 and an adsorption ratio as high as 99.998%. In addition, π-1 also shows high adsorption selectivity to Hg2+ in the presence of a series of interfering ions.

Presented in this article are the anion-tuning formation, crystal structures and luminescent properties of four coordination polymers of N,N′-di(3-pyridine) oxamide (DPOM), including two one-dimensional (1D) chain/ladder polymers, [Ni(DPOM)(H2O)4]SO4·2H2O (1) and [Cd4(DPOM)6(NO3)8] (2), as well as two 3D coordination polymers, [Zn2(DPOM)(H2O)4(SO4)2] (3) and [Cd2(DPOM)(H2O)4(SO4)2] (4). The results of single crystal X–ray diffraction analyses indicate that in these coordination polymers, DPOM ligand serves as a bridge, connecting metal ions by both terminal pyridine N atoms. 1 is a 1D chain structure formed by the bridge of DPOM. 2 is a 1D ladder-like structure featuring Cd(NO3)2 structural units bridged by DPOM ligands. Both 3 and 4 are 3D pillar-layer structures with the 2D inorganic layer ZnSO4/CdSO4 pillared by DPOM ligands. The results of photoluminescent measurements illustrate that upon excitation, 2–4 can emit fluorescence in 408, 416, and 422 nm in the solid state, respectively.

Three supramolecular compounds based on 1,4-benzeneditetrazole (H2BDT), (NH4)2(BDT) (1), [Mg(H2O)6](HBDT)2·2H2O (2), and [Mg(CH3OH)4(H2O)2](HBDT)2·2CH3OH (3) have been solvothermally synthesized and structurally characterized by single-crystal/powder X-ray diffraction. Structural analyses indicated that these compounds are 3D supramolecular structures stabilized by electrostatic interactions and intermolecular hydrogen bonds. The crystal to crystal transformation between 2 and 3 were investigated. The result showed that 2 is readily transform to 3 after immersed in methanol solution, while 3 can not be converted to 2 after immersed in distilled water solution.

The production of two-dimensional (2D) ultrathin metal-organic framework (MOF) nanosheets with functionalized surfaces is significant for extending their applications. To date, no protocol has been developed yet to solve this problem. Herein, we report a facile, mild, and efficient method to produce 2D monolayer MOF nanosheets with hydrophobic surfaces from layer-pillared 3D MOFs. This approach is based on the replacement of weaker coordinating pillar ligands with stronger coordinating capping ligands with the assistance of a high concentration gradient of the latter. Utilizing this method, the replacement of the 4,4'-bipyridine (bpy) pillars in two cadmium-based layer-pillared MOFs with alkylpyridine derivatives has been achieved, producing 2D MOF nanosheets with monolayer thickness and double-sided hydrophobic surfaces. The resulting hydrophobic 2D MOF nanosheets exhibit good performance for the separation of oil and water.

Five three-dimensional (3D) coordination polymers, {(NiL)[(NiL)(V16O42)]}n·2nH2O (1), [(NiL)3(VO3)6]n·5nH2O (2), [(NiL)3(V6O18)]n·7nH2O (3), [(NiL)3(V8O23)]n (4), and [(NiL)4(V10O29)]n (5), have been obtained by the reaction of the macrocyclic nickel complex [NiL](ClO4)2 (L = 1,4,8,11-tetraazacyclotetradecane) with NH4VO3 under different conditions. Single-crystal X-ray diffraction analyses revealed that the [VO3]– anion assumes diverse species and structures in these five coordination polymers, including the [V16O42]n4n– sheet, [V6O18]6– ring, [VO3]nn– chain, [VO3]nn– sheet, and [V10O29]n8n– chain. The [V16O42]n4n– sheets, [V6O18]6– rings, [VO3]nn– chains, [VO3]nn– sheets, and [V10O29]n8n– chains are linked together through [NiL]2+ bridges to form the 3D frameworks of 1–5. The single-crystal to single-crystal transformation between 2 and desolvated 2 was successfully realized. Electrochemical measurements indicate that 2 and 4 are potential catalysts for water splitting.

The development of porous metal-organic frameworks that can retain structural integrity under harsh physical and chemical conditions is essential from the perspective of their use in adsorption, catalysis, and sensors. Herein, a lanthanum carboxylate framework was found to exhibit exceptional stability, not only robust in boiling aqueous solutions at pH 2-12 and in boiling common organic solvents over 24 h but also stable upon ball milling for 1 h. Furthermore, this framework displayed highly selective separation for CO2 over N2 ( Sads = 940), as well as size-dependent selective adsorption behavior of water and alcohols.

Two highly stable dynamic metal–organic frameworks exhibit photochromism, tunable photoluminescence, and selective detection of oxygen, which can be recognised by the naked eye through color changes. Furthermore, they also display selective recognition of benzyl alcohol and halogenated solvents, respectively.

Solvothermal reaction of Co(II)/Zn(II) salt with 1,2,4,5-benzene tetracarboxylic dianhydride (BTD) leads to the formation of two coordination polymers based on benzene-1,2,4,5-tetracarboxylic acid (H4BTC), [Co2(BTC)(DMA)(H2O)]n (1) (DMA = N,N′-dimethylacetamide) and [Zn4(BTC)2(H2O)6]n·3nH2O (2). Both 1 and 2 have been characterized by infrared spectra (IR), elemental analyses (EA), thermogravimetric analyses (TG) and single-crystal/powder X-ray diffraction (XRD). The results of the single-crystal X-ray diffraction analyses reveal that both compounds are 3D coordination polymers. In 1, 1D Co(II)-carboxylate chains are linked together by the organic moiety of BTC4− ligands, forming a 3D coordination polymer. In 2, 1D Zn-BTC4− ribbons are connected together by [Zn2(H2O)3] building units, generating a 3D porous framework with 1D rectangular channels. Gas sorption measurements reveal that the two compounds can not adsorb N2. Photoluminescent study indicates that 2 exhibits luminescent properties with an emission peak at 527 nm.

By a pH value controlled synthesis strategy, hydrothermal reactions of Cd(NO3)2·4H2O with mixed-ligands of 5-amino-tetrazole (Hatz) and 1,2,4,5-benzenetetracarboxylic acid (H4btec) yielded two 3D cadmium(II) coordination polymers (CPs) of {K[Cd2(atz)(btec)(H2O)2]}n (1) and [Cd3(OH)(atz)(btec)(H2O)2]n·nH2O (2). Their structures were determined by elemental analysis (EA), infrared spectra (IR), thermogravimetric analysis (TGA) and single-crystal/powder X-ray diffraction. The results reveal that both 1 and 2 are 3D architectures. In 1, the Cd(II) ions are connected together by μ2-atz and μ6-btec4−, generating a rare (4,6)-connected anion framework. The anti-cation K+ ions locate the micropores and weakly interact with the carboxyl oxygen of the μ6-btec4− ligands. In 2, six Cd(II) ions are linked together through two μ3-OH− and two μ3-atz− to form a [Cd6(μ3-OH)2(μ3-atz)2]8+ unit, which is further connected with other equivalent units by μ9-btec4− spacers, resulting in a rare (5,10)-connected porous framework. The photoluminescent investigation illustrates that 1 and 2 show strong emissions at 470 and 457 nm upon excitation at 350 and 370 nm, respectively.

A rare (3,4,5)-connected self-interpenetrated metal-organic framework with an O-atom lined pore surface has been constructed from Zn(II) and H4L (H4L = 5,5'-(1,3,6,8-tetraoxobenzo[lmn][3,8]phenanthroline-2,7(1H,3H,6H,8H)diyl)-diisophthalic acid), which features an unprecedented 1D + 2D → 3D self-interpenetrated array and shows good controlled drug release properties.

Presented in this communication are four metal complexes based on 2-propyl-4,5-dicarboxylate-imidazole (H3PIDC), including two Co(II) coordination compounds, [Co(H2PIDC)2(H2O)2] · 4H2O (1) and 2[Co(H2PIDC)2(H2O)2] · 5H2O (2), as well as two Zn(II) coordination compounds, [Zn(H2PIDC)2(H2O)2] · 4H2O (3) and 2[Zn(H2PIDC)2(H2O)2] · 7H2O (4). They contain the same coordinated unit of [M(H2PIDC)2(H2O)2] (M = Zn or Co). Interestingly, among these four complexes, 1 and 2, or 3 and 4 crystallized in different space group, which may be related with the number of the crystallized H2O molecules.

Supramolecular isomerism for coordination networks refers to the existence of different architectures having the same building blocks and identical stoichiometries. For a given building block, different arrangements can lead to the formation of a series of supramolecular isomers. Two one-dimensional CoIIcoordination polymers based onN,N′-bis(pyridin-3-yl)oxalamide (BPO), bothcatena-poly[[[dichloridocobalt(II)]-bis[μ-N,N′-bis(pyridin-3-yl)oxalamide-κ2N:N′]] dimethylformamide disolvate], {[CoCl2(C12H10N4O2)2]·2C3H7NO}n, have been assembled by the solvothermal method. Single-crystal X-ray diffraction analyses reveal that the two compounds are supramolecular isomers, the isomerism being induced by the orientation of the dimethylformamide (DMF) molecules in the crystal lattice.

Six cadmium(II) coordination compounds with 2-propyl-imidazole-4,5-dicarboxylate (H3PIDC), including two mononuclear complexes, [Cd(H2PIDC)2(H2O)2]·4H2O (1) and [Cd2(H2PIDC)4(H2O)4]·7H2O (2), two square tetranuclear complexes, [Cd4(HPIDC)4(H2O)8]·2H2O (3) and [Cd4(HPIDC)4(py)8]·10H2O (py = pyridine, 4), one one-dimensional chain polymer, [Cd2(H2PIDC)4(H2O)2]n·2nH2O (5), as well as one two-dimensional layer polymer, [Cd(H2PIDC)2]n (6), have been prepared using solvent evaporation method and hydrothermal method. The results of single-crystal X-ray diffraction analyses indicate that, besides the common supramolecular interactions such as hydrogen bond and π···π stacking, the hydrophobic interaction among the propyl groups in the H3PIDC ligands also contributes to the stabilities of 1–6. The study of substance transformation for 3 reveals that the coordinated H2O molecules in 3 can be well replaced by pyridine molecules, indirectly leading to the formation of 4. The results of photoluminescent measurements il...

A novel 3D layer-pillared metal-organic framework of [Cd3(IDC)(BDC)1.5(H2O)]n (1), (H3IDC = imidazole-4,5-dicarboxylic acid, H2BDC = 1,4-benzenedicarboxylic acid) was obtained by hydrothermal reaction, which contains rare planar hexnuclear Cd(II) cluster structural units and represents an unprecedented trinodal (4,5,14)-connected topology network. Furthermore, the thermal stability and luminescent property of 1 have also been examined.

Two cadmium(II) metal–organic frameworks based on two mixed ligands of HBTA and H2BDC, [Cd5(BTA)6(BDC)2(DMF)4(H2O)2]n·n(2DMF·H2O) (1) and [Cd7(BTA)2(BDC)6(DMF)8]n·2nDMF (2) (HBTA = 1,2,3-benzenetriazole; H2BDC = 1,4-benzenedicarboxylic acid), have been prepared through methods of liquid to liquid diffusion and solvothermal reaction, respectively. The results of single-crystal X-ray diffraction analyses indicate that both MOFs are constructed from cadmium clusters. In 1, six BTA– anions connect five Cd(II) ions to generate a tetrahedral Cd5 cluster, which further links with four equivalent Cd5 clusters through four BDC2– bridges, forming a (4,4)-connected two–dimensional (2D) layer structure. In 2, each BTA– anion connects three Cd(II) ions to generate a triangular Cd3 cluster, which further links with four Cd3 clusters and two 3-connected BDC2– anions, forming a (3,6)-connected three-dimensional (3D) framework. The results of photoluminescent measurements illustrate that in the solid state, both 1 and 2 c...

A 3D metal-organic framework {[Cd2(TZ)3(BDC)0.5]·5H2O}n (1·5nH2O) (HTZ = 1H-tetrazole, H2BDC = 1,4-benzenedicarboxylic acid), has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The phase purity was confirmed by powder X-ray diffraction (PXRD), and the stability was identified by thermal gravimetric analysis (TG) and variable-temperature powder X-ray diffraction (VT-PXRD). The result of the single-crystal X-ray diffraction analysis indicates that 1 is a novel 3D microporous metal-organic framework constructed from Cd(II) metal centers and mixed linkers of TZ− anions and BDC2− anions. Photoluminescent measurement elucidates that 1 displays a strong and broad emission peak at 423 nm, which suggests that 1 may be a potential purple-light material.

1,4-benzeneditetrazolate [H2BDT] ( 1 ) and its 3D coordination polymer [Zn(BDT)]n ( 2 ), have been synthesized and structurally characterized by infrared spectroscopy (IR), thermal gravimetric analysis (TG), and single-crystal/powder X-ray diffraction. The result of the single-crystal X-ray diffraction analysis indicates that 1 is a 3D supramolecular structure stabilized by intermolecular hydrogen bonds and π…π stacking interactions. 2 is a 3D (4,4)-connected coordination polymer with the central metal Zn(II) ions linked together by BDT2− anions. Photoluminescent measurement for 2 in the solid state elucidates that 2 displays a strong photoluminescence at 469 nm, which suggests that 2 may be a potential blue-light material.

Single-crystal X-ray diffraction analysis of poly[bis(μ2-5-carboxy-2-propyl-1H-imidazole-4-carboxylato-κ3N3,O4:O5)copper(II)], [Cu(C8H9N2O4)2)]n, indicates that one carboxylic acid group of the 2-propyl-1H-imidazole-4,5-dicarboxylic acid (H3PDI) ligand is deprotonated. The resulting H2PDI−anion, acting as a bridge, connects the CuIIcations to form a two-dimensional (4,4)-connected layer. Adjacent layers are further linked through interlayer hydrogen-bond interactions, resulting in a three-dimensional supramolecular structure.

A new mixed-valence copper(I, II) coordination polymer, { [ Cu 2 I Cu 2 II I 2 L 4 ] · 4DMF } n 1 (HL = N′-(2-methylene pyridine)isonicotinohydrazide), was synthesized by N′-((N-oxide- pyridin-2-yl)methylene)isonicotinohydrazide and cuprous iodide. Complex 1 exhibit a one-dimensional structure built up from mixed valence units of Cu 2 I Cu 2 II L 4 linked by iodide anions. The coordinated environments of Cu(II) and Cu(I) are distorted octahedron and tetrahedron, respectively.

An extremely stable hydrogen-bonded organic framework, HOF-8, was fabricated. HOF-8 is not only thermally stable but also stable in water and common organic solvents. More interestingly, desolvated HOF-8 exhibits high CO2 adsorption as well as highly selective CO2 and C6H6 adsorption at ambient temperature.

In the title compound, [Co(C(9)H(8)NO(3))(C(12)H(8)N(2))(2)(H(2)O)]NO(3)·H(2)O, the Co(II) atom is six-coordinated by a carboxylate O atom of the hippurate (Hc) anion, a water O atom and four N atoms from two 1,10-phenanthroline ligands in a distorted octa-hedral geometry. The uncoordinated O atom of the hippuric acid anion is involved in an intra-molecular hydrogen bond to the coordinated water mol-ecule. The crystal packing is stabilized by inter-molecular O-H⋯O hydrogen bonds involving the Hc anions, the coordinated water mol-ecule, the nitrate anion and the uncoordinated water mol-ecule.

The title mononuclear copper(II) complex, [Cu(C(7)H(6)ClN(4)O(2))(2)(H(2)O)(2)]·2H(2)O, based on 8-chloro-theophylline (HCt), has the Cu atom at a center of symmetry in a slightly distorted trans square-planar geometry coordinated by two N atoms of two deprotonated HCt ligands and two O atoms of water mol-ecules. The crystal packing is stabilized by hydrogen bonds involving deprotonated HCt ligands, coordinated water mol-ecules and uncoordinated solvent water mol-ecules.

In the title compound, [Co(C(7)H(5)O(2))(2)(C(5)H(6)N(2))(2)], the Co(II) atom is hexa-coordinated by four O atoms from two benzoate anions, and two N atoms from two 2-amino-pyridine mol-ecules, resulting in a distorted octa-hedral geometry. Both benzoate anions act as bidentate ligands and both 2-amino-pyridine mol-ecules are coordinated to the metal through their pyridyl N atoms. The crystal packing is stabilized by inter-molecular N-H⋯O hydrogen bonds, C-H⋯π, and π-π stacking inter-actions involving benzoate anions and 2-amino-pyridine mol-ecules.

In the title dinuclear Cd(II) complex, [Cd(2)(C(2)N(4)O(2))(2)(C(10)H(8)N(2))(2)(H(2)O)(2)], each Cd atom is in a slightly distorted octa-hedral coordination by two N atoms and one O atom of two 1H-tetra-zole-5-carboxyl-ate (TZC) ligands, two N atoms of a 2,2'-bipyridyl ligand and one water O atom. The TZC ligand acts in a tridentate N,O-chelating N-bridging mode to two symmetry-equivalent Cd(II) atoms. The complex reveals mol-ecular C(i) symmetry. Extensive O-H⋯O hydrogen bonding plays an important role in the crystal packing.

The title mononuclear copper(II) complex, [Cu(C7H6ClN4O2)2(H2O)2]·2H2O, based on 8-chlorotheophylline (HCt), has the Cu atom at a center of symmetry in a slightly distorted trans square-planar geometry coordinated by two N atoms of two deprotonated HCt ligands and two O atoms of water molecules. The crystal packing is stabilized by hydrogen bonds involving deprotonated HCt ligands, coordinated water molecules and uncoordinated solvent water molecules.

In the title compound, [Co(C7H5O2)2(C5H6N2)2], the CoII atom is hexa­coordinated by four O atoms from two benzoate anions, and two N atoms from two 2-amino­pyridine mol­ecules, resulting in a distorted octa­hedral geometry. Both benzoate anions act as bidentate ligands and both 2-amino­pyridine mol­ecules are coordinated to the metal through their pyridyl N atoms. The crystal packing is stabilized by inter­molecular N—H⋯O hydrogen bonds, C—H⋯π, and π–π stacking inter­actions involving benzoate anions and 2-amino­pyridine mol­ecules.

In the title compound, [Cd(C7H5O2)2(C5H6N2)2], the CdII atom is hexa­coordinated by four O atoms from two crystallographically independent benzoate anions, and two pyridine N atoms from two crystallographically independent 2-amino­pyridine mol­ecules in a distorted octa­hedral geometry. In the crystal structure, the metal complexes are connected by N—H⋯O hydrogen bonding between the carboxylate O atoms of the benzoate anions and the amino H atoms of the 2-amino­pyridine ligands. The benzoate and the amino­pyridine rings are stacked in the direction of the crystallographic a axis, indicating π–π stacking inter­actions are present [centroid-centroid distance = 3.6790 (15) A].

The Zn atom of the title complex, [Zn(NCS)2(C7H8N4O)2(H2O)2] or [Zn(SCN)2(H-Pysc)2(H2O)2] [H-Pysc = N-aminocarbonyl-N′-(3-pyridylmethylene)hydrazine], derived from the condensation of pyridine-3-carbaldehyde and semicarbazone, is located at a crystallographic centre of inversion and is octahedrally coordinated by two thiocyanate anions, two aqua molecules and two molecules of the neutral Schiff base ligand H-Pysc. The Schiff base molecules act as monodentate ligands coordinating the metal through the pyridyl N atom, whereas the amide O and imine N atoms remain uncoordinated. The crystal packing is stabilized by intermolecular hydrogen bonds involving H-Pysc ligands, thiocyanate anions and water molecules.

The Cd atom in the title complex, [Cd(C2H3O2)(NCS)(C7H8N4O)(H2O)]·H2O, is coordinated by one neutral Schiff base ligand, one acetate anion, one thio­cyanate anion and one water mol­ecule, forming a distorted penta­gonal–bipyramidal geometry. The thio­cyanate S atom and the coordinated water ligand occupy the apical positions of the coordination polyhedron. The acetate acts as a bidentate ligand through the carboxylate O atoms. The Schiff base, derived from the condensation of pyridine-2-carbaldehyde and semicarbazone, acts as a tridentate ligand, coordinating the metal through the amide, imine and pyridyl N atoms in a meridional fashion. The crystal packing is stabilized by π–π stacking inter­actions between the neighboring pyridine rings and hydrogen bonds involving the Schiff base, thio­cyanate, water mol­ecules and uncoordinated solvent water mol­ecules.

In the title compound, [Pb(C7H4O3)]n, the PbII atom is coordinated by five O atoms from four salicylic acid ligands with Pb—O distances of 2.318 (16)–2.605 (15) A. Each ligand acts in a penta­dentate mode that leads to the formation of a two-dimensional polymeric network.

A three-dimensional tetrazole-based Cd(II) metal–organic framework containing rare large Cd8 and Cd23 secondary building units has been hydrothermally prepared through in situ metal/ligand reaction, which shows an unprecedented (4,10)-connected topology net.

In the crystal structure of the title compound, [Mg(CHN(4))(2)(H(2)O)(4)], the Mg(II) atom is six-coordinated by two N atoms from two tetra-zolide anions and four O atoms from four coordinated water mol-ecules in a slightly distorted octa-hedral geometry. The Mg atom is located on centres of inversion whereas the tetra-zolide anion and the water mol-ecules occupy general positions. The crystal packing is stabilized by intermolecular O-H⋯N hydrogen bonding between the tetra-zolide anions and the coordinated water mol-ecules.

The title compound, [Ni(2)(C(7)H(5)O(2))(4)(C(7)H(6)O(2))(2)], is composed of two Ni(II) ions, four bridging benzoate anions and two η(1)-benzoic acid mol-ecules. The [Ni(2)(PhCOO)(4)] unit adopts a typical paddle-wheel conformation. The center between the two Ni(II) atoms represents a crystallographic center of inversion. In addition, each Ni(II) ion also coordinates to one O atom from a benzoic acid mol-ecule. The crystal packing is realised by inter-molecular hydrogen-bonding inter-actions and π-π stacking inter-actions, with a centroid-centroid distance of 3.921 (1) Å.

The title compound, C(14)H(6)O(7)·C(10)H(8)N(2), has been hydro-thermally synthesized. Structural ananlysis indicates that the crystals are produced by cocrystallization of naphthalene-1,4,5,8-tetra-carboxylic acid 1,8-anhydride and 4,4'-bipyridine (bpy) mol-ecules. The crystal packing is stabilized by inter-molecular O-H⋯N and C-H⋯O hydrogen bonds and π-π stacking inter-actions [centroid-centroid distances = 3.5846 (9) Å].

In the crystal structure of the title compound, C(14)H(10)F(2)O, the dihedral angles between the benzene rings in the two crystallographically independent mol-ecules are 46.9 (2) and 47.6 (2)°. The mol-ecules are linked into dimers by C-H⋯F inter-actions and these dimers are further stacked into columns along the b axis by π-π inter-actions between the benzene rings [centroid-centroid distance = 3.8221 Å; the dihedral angle between the planes of these rings is 4.87 (2)°]. In addition, C-F⋯π interactions also contribute to the crystal packing (C⋯centroid distance = 3.5919 Å).

In the title complex, [Mn(SCN)2(H-Pysc)2(H2O)2] {H-Pysc = 3-[2-(amino­carbon­yl)hydrazonometh­yl]pyridine, C7H8N4O}, MnII, located at an inversion centre, is coordinated by two thio­cyanate anions, two water mol­ecules and two mol­ecules of the neutral Schiff base ligand H-Pysc, forming an octa­hedral configuration. The Schiff base acts as a monodentate ligand, coordinating to the metal through the pyridyl N atom, whereas the amide O and imine N atoms remain uncoordinated. The complex mol­ecules are held together by inter­molecular hydrogen bonds into a three-dimensional supra­molecular network.