An open-framework cobalt molybdate possessing {Mo2O7} building block: hydrothermal synthesis and structural characterization of [CoMo2O7(4,4′-bipy)1.5]

The hydrothermal reaction of Co(COO)₂?·?4H₂O, MoO₃, H₃PO₄ and 4,4′-bipyridine yields bipyridine-ligated cobalt dimolybdate [CoMo₂O₇(4,4′-bipy)_1.5] (1) (4,4′-bipy?=?4,4′-bipyridine) in the triclinic system with space group of P 1 and cell parameters of a?=?7.1951(8)?Å, b?=?11.1708(17)?Å, c?=?11.4514(11)?Å, α?=?98.545(7)°, β?=?90.315(2)°, γ?=?105.777(5)°, V?=?874.88(19)?ų, and Z?=?2. Its structure consists of Co/Mo/O bimetal oxide layers with {Mo₂O₇} building blocks, linked by the coordination of 4,4′-bipy ligand with Co and Mo atoms, into a 3D porous hybrid framework.     

Synthesis and crystal structures of 3D supramolecular compounds: [ M (4,4′-bipy)2(H2O)4] · (4,4′-bipy)2 · (3,5-daba)2 · 8H2O ( M =Zn,Mn)

Two new supramolecular compounds [M(4,4′-bipy)₂ (H₂O)₄] ·?(4,4′-bipy)₂ ·?(3,5-daba)₂ ·?8H₂O (M=Zn(1) or Mn(2), 4,4′-bipy =?4,4′-bipyridine, 3,5-daba =?3,5-diaminobenzoic acid anion) were synthesized and characterized by elemental analysis and X-ray crystal diffraction. In [M(4,4′-bipy)₂(H₂O)₄]²⁺, the M(II) is coordinated by two nitrogen atoms from two 4,4′-bipy molecules and four oxygen atoms from four waters to form an octahedral configuration. There exist uncoordinated 4,4′-bipy molecules, 3,5-diaminobenzolate counterions and water guests in the compounds. The 3D structures of the title supramolecular compounds are constructed by rich hydrogen bonds among [M(4,4′-bipy)₂(H₂O)₄]²⁺, uncoordinated 4,4′-bipy molecules, water molecules and 3,5-daba, containing a diverting hexa-member water ring.     

A 3D interpenetrating supramolecular compound based on Cu ··· N weak coordination: synthesis,crystal structure and DFT investigation

A metal-organic hybrid compound, Cu[(pyc)₂(4,4′-bipy)] ·?H₂O (pyc =?pyridine-2-carboxylate, 4,4′-bipy =?4,4′-bipyridine), has been hydrothermally synthesized and characterized by X-ray determination, IR and elemental analysis. The compound crystallizes in tetragonal, space group I4₁/acd with a =?24.797(2) Å, b =?24.797(2) Å, c =?14.811(2) Å, β =?90°, V =?9106.7(18) ų, C₂₂ H₁₈N₄O₅Cu, Mr =?481.94, Dc =?1.406 g cm^?3, μ(Mo-Kα) =?0.999 mm^?3, F(000) =?3952, Z =?16, the final R =?0.0712 and wR =?0.1886 for 21727 observed reflections (I >?2σ). Compound 1 exhibits a three-dimensional interpenetrating network induced by weak Cu ··· N noncovalent interaction, C–H ··· π?and π–π interactions. Based on crystal data, quantum chemistry calculation at the DFT/B3LPY level was used to reveal the electronic structure of 1.     

Rheological phase synthesis,characterization and magnetic property of a cobalt(II)diphosphonate

A new Co(II) diphosphonate compound, [Co(HEDPH₂)₂] (4,4′-bipyH₂)?·?H₂O (1) has been successfully obtained by a rheological phase reaction at 80°C. Single-crystal diffraction analysis shows a 1-D chain structure and the 1-D chains are assembled via hydrogen bonds into a 3-D supramolecular structure with channels. The protonated 4,4′-bipy molecules are encapsulated in the channels. Magnetic study shows 1 to exhibit antiferromagnetic interaction in the 1D Co--O--P--O--Co chain. Crystal data for 1: monoclinic, space group Cc, a?=?15.754(6)?Å, b?=?14.457(5)?Å, c?=?10.020(4)?Å, β?=?92.024(6)°, V?=?2280.7(14)?ų, Z?=?4.     

Two New Dinuclear MnII Cluster-based Metal-organic Frameworks: Syntheses,Crystal Structures,and Magnetic Properties

Two new dinuclear Mn^II cluster-based metal-organic frameworks, namely [Mn₂(L)(DMPU)₃]_n ( 1 ) and [Mn(L)_0.5(4,4'-bipy)_0.5(H₂O)]_n ( 2 ) (H₄L = biphenyl-3,3',5,5'-tetracarboxylic acid, DMPU = 1,3-dimethyltetrahydropyrimidin-2(1H)-one, 4,4'-bipy = 4,4'-bipyridine), were solvothermally synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and magnetic studies. Compound 1 crystallizes in the monoclinic P2₁/n space group and displays a 3D framework with 4-connected crb/BCT -type topology, and compound 2 crystallizes in the monoclinic C2/c space group and displays a 3D framework with (4,6)-connected sqc422 -type topology. The magnetic studies of compounds 1 and 2 show the presence of weak antiferromagnetic interactions within the dinuclear Mn^II units.     

SYNTHESIS OF ONE-AND TWO-DIMENSIONAL ZINC AND CADMIUM COMPLEXES WITH 4, 4′-BIPY

Abstract

The zinc(II) and cadmium(II) complexes [Zn(4, 4′-bipy)(SCN)₂]_∞ 1 and [Cd(4, 4′-bipy)-(SCN)₂]_n 2 have been synthesized and their crystal structures determined by X-ray crystallography. Complex 1 is monoclinic, space group C2/c, with a = 18.076(5), b = 5.190(1), c = 17.315(4)Å; β = 115.54(2), V = 1465.8(8)ų, calculated density 1.530gcm^?3, Z = 4. In this compound, the rod-like ligand 4, 4′-bipy bridges Zn(II) centres, and the NCS groups are terminally coordinated. (N-Zn-N) is 108.5°, resulting in the formation of a zigzag Zn-bipy-Zn chain. These chains are arranged in parallel fashion. The 4, 4′-bipy ligands of adjacent layers are separated by 3.95 (Å). Complex 2 is monoclinic, space group C2/c, a = 11.902(2), b = 11.745(2), c = 10.500(2)Å; β = 109.71(3), V = 1381.8(4)ų calculated density 1.849gcm^?3, Z = 4. In this structure, the cadmium(II) ion is slightly distorted octahedral and the SCN groups act as doubly bridging ligands connecting cadmium atoms to form zigzag chains, separated by 4, 4′-bipy to create two-dimensional planes.     

The construction of two lanthanide coordination polymers based on 5-hydroxyisophthalate and bipyridine

Two lanthanide coordination polymers, [Tm₂·(5-IPA)₄·(2,2′-Hbipy)₂]·3H₂O (1, 5-H₂IPA?=?5-hydroxyisophthalic acid, 2,2′-bipy?=?2,2′-bipyridine) and [Er·(5-HIPA)₃·(4,4′-bipy)₃·(H₂O)₂]·3H₂O (2, 4,4′-bipy?=?4,4′-bipyridine), have formed by hydrothermal synthesis. Complex 1 exhibits a 2-D coordination network containing parallelepiped-shaped voids occupied by guest 2′2-bipy molecules. Complex 2 possesses a 1-D linear chain structure. The 1-D chains are linked by 4,4′-bipy molecules to form a 3-D supramolecular framework. IR spectroscopy, elemental analysis, and thermogravimetric analysis were also investigated.     

SYNTHESIS,CHARACTERIZATION AND CRYSTAL STRUCTURE OF DIAQUADI(2,2′'-BIPYRIDINE)DI(DICHLOROACETATO)LANTHANIDE(III) MONODICHLOROACETATO

Abstract

The title complexes, diaquadi(2,2″-bipyridine)di(dichloroacetato)lanthanide(III) monodichloroacetato [Ln(CHCl₂COO)₂(2,2′-bipy)₂(H₂O)₂]⁺(CHCl₂COO)^?(Ln = Dy, Ho, Tm, Er, Yb], were obtained and characterized. [Er(CHCl₂COO)₂(2,2′-bipy)₂(H₂O)₂]⁺(CHCl₂COO)^? crystallizes in the mooclinic space group P2₁/n with Z = 4. Cell dimensions are a = 15.886(9), b = 13.758(2), c = 16.343(4)Å, β = 113.31(3)°, and the structure was refined to an R of 0.049 for 3415 observed reflections. The Er(III) ion exhibits a distorted, square antiprismatic configuration. Four N atoms of 2,2′-bipy and four O atoms from two dichloroacetato and two water ligands are coordinated. One dichloroacetato group lies outside the polyhedron and is connected with water ligands by hydrogen bonds.     

Syntheses,crystal structures and fluorescent properties of two 4,4′-dipyridylsulfide based zinc(II) and cadmium(II) helical complexes

Two allomeric helical coordination polymers, {[Zn(4,4′-dps)₂(HSSA)(H₂O)₂] · 3(H₂O)} _n (1) and {[Cd(4,4′-dps)₂(HSSA)(H₂O)₂] · 3(H₂O)} _n (2) (4,4′-dps = 4,4′-dipyridylsulfide, H₃SSA = 5-sulfosalicylic acid), have been synthesized by similar experimental methods and characterized by elemental analysis, single-crystal X-ray diffraction, and fluorescence spectra. Both crystallize in monoclinic system, space group P₂1/n, with a = 11.7947(13) Å, b = 13.7475(15) Å, c = 20.183(2) Å, and Z = 4 for 1 and a = 11.940(7) Å, b = 14.068(8) Å, c = 20.323(12) Å, and Z = 4 for 2. In both complexes, the metal (Zn^II for 1 and Cd^II for 2) are six-coordinate with a N₃O₃ donor set in a distorted octahedron. Half of the 4,4′-dps are μ ₂-bridging, linking adjacent metal centers and forming P₂1/n dimensional helical structures along the b-axis. Fluorescence measurements show that 1 and 2 have medium fluorescent emission at 402 and 405 nm, respectively.     

Hydrothermal synthesis,crystal structure and fluorescence of a cyclic dimer copper compound constructed by 2-nitrobenzenedicarboxylate

The reaction of 2-nitro-1,4-benzenedicarboxylic acid (H₂nbdc) and 2,2′-bipyridine (2,2′-bipy) with CuCl₂ under hydrothermal conditions gives rise to a cyclic dimer [Cu(nbdc)(2,2′-bipy)(H₂O)]₂ · 2H₂O (1). X-ray structural analysis revealed that 1 crystallizes in a monoclinic space group P2₁/c with a = 7.3801(13) Å, b = 15.305(3) Å, c = 16.333(3) Å, β = 92.951(4)°, V = 1842.5(6) ų, and Z = 2. Compound 1 represents the first cyclic dimeric example with 1,4-benzenedicarboxylate or its derivatives, in which two carboxylates of the nbdc are nearly perpendicular due to the steric effect by the nitro group. Compound 1 also displays strong fluorescent emission in the solid state.     

Formation of [FeW12O40]5− under hydrothermal conditions: syntheses,crystal structures,and characterization of [Fe(2,2′-bipy)3]2[HFeW12O40] · 5H2O and (4,4′-H2bipy)6(Hpy)2(H3O)[FeW12O40]3 · 11H2O

Two supramolecular compounds based on tungstoferrate [FeW₁₂O₄₀]^5?, [Fe^II(2,2′-bipy)₃]₂[HFeW₁₂O₄₀] · 5H₂O (1), and [Hpy]₂[4,4′-H₂bipy]₆(H₃O)[FeW₁₂O₄₀]₃ · 11H₂O (2) (py = pyridine, bipy = bipyridine) were synthesized hydrothermally and characterized structurally. The hydrogen bonds between polyoxoanions and water and the edge-to-face π–π interaction between [Fe^II(2,2′-bipy)₃]²⁺ with a shortest C–C distance of 3.513 Å are the main forces to construct the 3-D architecture of 1. In 2, a 3-D supramolecular architecture is assembled by the tungstoferrate anions, protonated 4,4′-bipy cations, and water through hydrogen bonding. The variable-temperature magnetic susceptibilities indicate that 1 is paramagnetic with μ _eff corresponding to one Fe(III) with spin-only contribution, showing that Fe in the coordination cations has a +II oxidation number and low spin state.     

Syntheses,structures, and properties of four coordination compounds constructed from asymmetric semi-rigid V-shaped multicarboxylate ligand

Four new compounds, [Mn(HL)(phen)₂(H₂O)] (1), [Ni(HL)(phen)₂(H₂O)] (2), [Zn(HL)(4,4′-bipy)_1.5(H₂O)] _n ?·?2nH₂O (3) and [Zn₂(HL)₂(H₂O)₆] (4), have been synthesized from an asymmetric semi-rigid V-shaped multicarboxylate 4-(4-carboxy-phenoxy)-phthalic acid (H₃L) with 1,10-phenanthroline (phen), or 4,4′-bipyridine (4,4′-bipy) as auxiliary ligands. Single-crystal X-ray diffraction analysis reveals that 1, 2 and 4 have 0-D structures with 3-D supramolecular frameworks formed by intermolecular hydrogen bonds. Compound 3 shows a 1-D infinite ribbon bridged by 4,4′-bipy, which further forms a 3-D supramolecular architecture by π–π stacking interactions and hydrogen bonds. Thermal stabilities of 1–4 and luminescence properties of 3 and 4 have also been investigated.     

A 2D Zn(II) metal-organic framework constructed from 4,4′-(perfluoropropane-2,2-diyl)dibenzoic acid,synthesis, structure and photoluminescence

A Zn(II) metal-organic framework (MOF) [Zn₂(FPDB)₂(pyridine)₂] · 5H₂O (1) was synthesized solvothermally via reaction of Zn(ClO₄)₂ · 6H₂O and 4,4′-(perfluoropropane-2,2-diyl)dibenzoic acid (H₂FPDB). The X-ray single crystal diffraction analysis reveals that 1 crystallizes in monoclinic C2/c space group with a = 23.279(5) Å, b = 7.837(5) Å, c = 26.776(5) Å, β = 106.7(6)° and Z = 4. In 1, two adjacent zinc ions are bridged to form a dinuclear paddle-wheel SBU, and four neighboring SBUs are linked by FPDB ligands to construct a chair-type grid. Distorted grids extended along a and b axes to complete a double-sheet 2D layer and these layers stack with van der Waal's interactions to build the final structure. Compound 1 shows strong luminescence at room temperature in the solid state, suggesting that 1 may be an excellent fluorescent material.     

Crystal structures of two new dinuclear Ag(I) complexes constructed from 4,4′-biphenyldicarboxylic acid and N-containing ligands

The reaction of silver 4,4′-biphenyldicarboxylate with 1,3-diaminopropane (DAP) and 2-amino-5-methylpyridine (AMP) respectively results in the formation of two dinuclear silver(I) complexes: [Ag₂(DAP)₂](BPC)·2H₂O (1) and [Ag₂(BPC)(AMP)₄]·2H₂O (2), where BPC is 4,4′-biphenyldicarboxylate. The complexes are characterized by elemental analysis and X-ray crystallography. Complex 1 crystallizes in the triclinic system, P-1 space group, a = 8.585(2) Å, b = 8.849(2) Å, c = 9.890(3) Å, α = 107.893(3)°, β = 94.139(3)°, γ = 113.202(3)°, V = 640.9(3) ų, Z = 1. Complex 2 crystallizes in the triclinic system, P-1 space group, a = 11.818(3) Å, b = 13.132(4) Å, c = 13.281(4) Å, α = 92.571(4)°, β = 96.425(3)°, γ = 102.142(4)°, V = 1997.5(10) ų, Z = 2. Complex 1 consists of a macrocyclic dinuclear silver(I) dication, a 4,4′-biphenyldicarboxylate anion, and two water molecules of crystallization. Each Ag atom is in a linear coordination. Complex 2 consists of a dinuclear silver(I) complex molecule and two water molecules of crystallization. Each Ag atom is in a T-shaped coordination. The Ag...Ag separations are 5.127(2) Å in 1 and 3.172(2) Å in 2.     

Metal–organic Coordination Polymers Assembled from Divalent Transition Salts with a Flexible Spacer Ligand: Hydrothermal Syntheses,Crystal Structures,and Luminescent and Magnetic Properties

Seven new metal-organic coordination polymers, [M(tzda)(H₂O)₄] _n [M = Co(1), Ni (2) and Zn(3)], [Zn(tzda)(4,4′-bipy)] _n (4), [Cd(tzda)(4,4′-bipy)_0.5(H₂O)] _n (5) and [M(tzda)(4,4′-bipy)(H₂O)] _n [M = Co(6), Ni(7)] [H₂tzda = (1,3,4-thiadiazole-2,5-diyldithio)diacetic acid, 4,4′-bipy = 4,4′-bipyridine] have been hydrothermally synthesized and structurally characterized by X-ray single crystal diffraction. Compounds 1–3 display similar 1D zigzag chain structure. Compound 4 possesses a 2D-layered architecture generated from [Zn(tzda)] _n moiety with double-chain structure cross-linking 4,4′-bipy spacers, while compound 5 consists of –Cd–OCO–Cd–OCO– chains cross-linked through –CH₂SC₂N₂SSCH₂– spacers of tzda anions and 4,4′-bipy, also showing a 2D-layered structure. The structures of 6 and 7 seem more complicated, in which the [M(tzda)] _n layered subunits are extended to unique 3D framework by the bridging 4,4′-bipy ligand. Photoluminescence investigations reveal that 4 and 5 both display strong blue emissions in the solid state at room temperature, which could be significant in the field of luminescent materials. The magnetic studies of 6 and 7 show both display the characteristics of a weak antiferromagnetic coupling between metal ions in the system mediated by carboxylate bridges.     

Synthesis and structures of three triphosphonate compounds containing d10 transition metal ions

Three new triphosphonate compounds, [Zn(APTPH₄)(2,2′-bipy)(H₂O)]?·?2H₂O (1), [Cd(APTPH₄)(2,2′-bipy)(H₂O)]?·?2H₂O (2), and [Zn(APTPH₄)(phen)₂]?·?phen?·?4H₂O (3) (APTPH₆?=?1-aminopropane-1,1,3-triphosphonic acid, 2,2′-bipy?=?2,2′-bipyridine, phen?=?1,10-phenanthroline), are synthesized by a low-temperature hydrothermal method. Compounds 1 and 2 are isomorphous, both one-dimensional (1D) coordination polymers expanded into three-dimensional (3D) supramolecular structures by hydrogen bonds and π–π stacking interactions. Compound 3 is a molecular complex and forms a 3D network through an S-shaped water hexamer. Crystal data for 1: Triclinic, space group P 1, a?=?6.6814(5)?Å, b?=?10.0929(7)?Å, c?=?15.438(2)?Å, α?=?81.544(2)°, β?=?79.066(2)°, γ?=?82.278(2)°, Z?=?2; for 2: Triclinic, space group P 1, a?=?6.9380(8)?Å, b?= 10.043(2)?Å, c?=?15.681(2)?Å, α?=?81.357(2)°, β?=?78.510(2)°, γ?=?81.902(2)°, Z?=?2; Crystal data for 3: Triclinic, space group P 1, a?=?12.540(2)?Å, b?=?12.596(2)?Å, c?=?14.997(2)?Å, α?=?100.795(2)°, β?=?113.328(2)°, γ?=?101.358(2)°, Z?=?2.     

Synthesis, characterization, solvatochromic behavior and crystal structures of complexes [CoIII(salophen)(thioacetamide)2]ClO4 and [CoIII(salophen)(thiobenzamide)2]ClO4

Two new cobalt(III) complexes of the Schiff base N,N′-disalicylidene-1,2-phenylendiimine dianion (salophen), trans- [Co^III(salophen)(ta)₂]ClO₄, (ta = thioacetamide) (1) and trans-[Co^III(salophen)(tb)₂]ClO₄, (tb = thiobenzamide) (2) were synthesized and characterized using single-crystal X-ray diffraction and spectroscopic techniques. Both complexes show solvatochromism in a variety of solvents. Complex (1) crystallized from CHCl₃ as a solvate of orthorhombic symmetry, space group Pca2₁ with a = 17.3480(10) Å, b = 18.7522(10) Å, c = 18.8128(11) Å, α = β = γ = 90°, and Z = 8. The cobalt(III) center lies in a distorted octahedral environment. The crystal structure of (1) consists of two independent [Co^III(salophen)(ta)₂]⁺ cations and ClO₄ ^- anions held together essentially via hydrogen bonds and π-π stacking interactions. Complex (2), forming also a CHCl₃ solvate, crystallized in the monoclinic space group P2₁/n with a = 14.710(3) Å, b = 13.506(3) Å, c = 18.595(4) Å, β = 100.295(4)°, and Z = 4. The geometry around cobalt(III) center is a distorted octahedron. The crystal structure of (2) contains a [Co^III(salophen)(tb)₂]⁺ complex with a remarkably twisted salophen ligand. Both complexes, (1) and (2), contain approximately one disordered CHCl₃ molecule per Co in the solid state.     

New nano-particle La(III) supramolecular compound as a precursor for preparation of lanthanum oxybromide-, hydroxide-, and oxide-nanostructures

Nano-particles of a new La(III) supramolecular compound [La(4,4′-bipy)(H₂O)₂(NO₃)_3.75Br_0.25] · (4,4′-Hbipy) (1), have been synthesized from reaction of 4,4′-bipy with La(NO₃)₃ and NaBr by the sonochemical method. For the first time LaOBr, La(OH)₃ and La₂O₃ nano-structures were prepared from [La(4,4′-bipy)(H₂O)₂(NO₃)_3.75Br_0.25] · (4,4′-Hbipy) (1) by calcination at 400, 500, and 700°C, respectively. The structure of 1 was determined by X-ray crystallography and the nano-structures were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Thermal stabilities of nano and crystal samples of 1 were studied and compared with each other.     

A series of new oxo-vanadium(IV) complexes with octahedral coordinated vanadium centers

A series of new oxo-vanadium(IV) complexes, [VOCl0.69(OH)0.31 (2,2′-bipy)2]Cl·2H2O (1, 2,2′-bipy?=?2,2′-bipyridine) [(VO)₂Cl₄(4,4'-bipy)₃ (H₂O)₂] (2, 4,4'-bipy?=?4,4'-bipyridine), [VO(ida)(H₂O)]_n (3, H₂ida?=?iminodiacetic acid), and [(VO)₂(oa)₄]_n·4n(H₃O)·n(H₂O) (4, H₂oa?=?oxalic acid), have been synthesized and structurally characterized. 1 contains a [VOCl_0.69(OH)_0.31(2,2′-bipy)₂]⁺ cation, Cl ^– anion and two free H₂O molecules. 2 exhibits a binuclear centrosymmetric moiety built up from two [VOCl₂(4,4'-bipy)(H₂O)] units and one bridging 4,4'-bipy ligand, which provides a rare example of a 4,4'-bipy molecule acting as monodentate ligand. 3 displays a neutral chain [VO(ida)(H₂O)]_n constructed by the linkages of [VO(H₂O)]²⁺ units and ida^2? bridging ligands, while 4 offers the only example of three kinds of oa^2- ligands coexisting within the same anionic chain [(VO)₂(oa)₄^4-]_n. Their spectroscopic properties were investigated, and the magnetic susceptibility of 4 shows antiferromagnetic behavior.     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.