Earth Alkaline Tetrathiosquarates: Syntheses and Crystal Structures of MgC4S4 · 6 H2O and CaC4S4 · 4 H2O

Concentrated aqueous solutions of magnesium chloride and calcium nitrate, respectively, allow on addition of the potassium salt of tetrathiosquarate, K₂C₄S₄ · H₂O, the isolation of the earth alkaline salts MgC₄S₄ · 6 H₂O ( 1 ) and CaC₄S₄ · 4 H₂O ( 2 ) as orange and red crystals. The crystal structure determinations ( 1 : monoclinic, C2/c, a = 17.2280(7), b = 5.9185(2), c = 13.1480(4) Å, β = 104.730(3)°, Z = 4; 2 : monoclinic, P2₁/m, a = 7.8515(3), b = 12.7705(5), c = 10.6010(4) Å, β = 93.228(2)°, Z = 4) show the presence of C₄S₄^2? ions with almost undistorted D_4h symmetry having average C–C and C–S bond lengths of 1.451Å and 1.659Å for 1 and 1.451Å and 1.655Å for 2 . The structure of 1 contains discrete, octahedral [Mg(H₂O)₆]²⁺ complexes. Several O–H····O and O–H····S bridges with H····O and H····S distances of less than 2.50Å connect cations and anions. The structure of 2 is built of concatenated, edge‐sharing Ca(H₂O)₆S₂ polyhedra. The Ca²⁺ ions have the coordination number eight, C₄S₄^2? act as a chelating ligands towards Ca²⁺ with Ca–S distances of 3.14Å. The infrared and Raman spectra show bands typical for the molecular building units of the two compounds.     

Synthesis,Crystal Structure,and Magnetic Properties of {[Cu(phen)]2(C4H2O4)2} · 4.5H2O with C4H4O4 = Maleic Acid

Reaction of CuCl₂ · 2H₂O, phenanthroline, maleic acid and NaOH in CH₃OH/H₂O (1:1 v/v) at pH = 7.0 yielded blue {[Cu(phen)]₂(C₄H₂O₄)₂} · 4.5H₂O, which crystallizes in the monoclinic space group C2/c (no. 15) with cell dimensions: a = 18.127(2)Å, b = 12.482(2)Å, c = 14.602(2)Å, β = 103.43(1)°, U = 3213.5(8)ų, Z = 4. The crystal structure consists of the centrosymmetric dinuclear {[Cu(phen)]₂(C₄H₂O₄)₂} complex molecules and hydrogen bonded H₂O molecules. The Cu atoms are each square‐pyramidally coordinated by two N atoms of one phen ligand and three carboxyl O atoms of two maleato ligands with one carboxyl O atom at the apical position (d(Cu‐N) = 2.008, 2.012Å, equatorial d(Cu‐O) = 1.933, 1.969Å, axial d(Cu‐O) = 2.306Å). Two square‐pyramids are condensed via two apical carboxyl O atoms with a relatively larger Cu···Cu separation of 3.346(1)Å. The dinuclear complex molecules are assembled via the intermolecular π—π stacking interactions into 1D ribbons. Crossover of the resulting ribbons via interribbon π—π stacking interactions forms a 3D network with the tunnels occupied by H₂O molecules. The title complex behaves paramagnetically between 5—300 K, following the Curie‐Weiss law _χm(T—θ) = 0.435 cm³ · mol^—1 · K with θ = 1.59 K.     

Earth Alkaline Tetrathiosquarates. II. – Syntheses and Crystal Structures of SrC4S4·4 H2O and Ba4K2(C4S4)5·16 H2O

Concentrated aqueous solutions of strontium chloride and barium chloride, respectively, allow on addition of the potassium salt of tetrathiosquarate, K₂C₄S₄·H₂O, the isolation of the earth alkaline salts SrC₄S₄·4 H₂O ( 1 ) and Ba₄K₂(C₄S₄)₅·16 H₂O ( 2 ), both as dark red crystals. The crystal structure determinations ( 1 : orthorhombic, Pnma, a = 8.149(1), b = 12.907(2), c = 10.790(2) Å, Z = 4; 2 : orthorhombic, Pbca, a = 15.875(3), b = 21.325(5), c = 16.119(1) Å, Z = 4) show the presence of C₄S₄²⁻ ions with only slightly distorted D_4h symmetry having average C–C and C–S bond lengths of 1.41Å and 1.681Å for 1 and 1.450Å and 1.657Å for 2 . The structure of 1 contains concatenated edge‐sharing Sr(H₂O)₆S₂ polyhedra. The Sr²⁺ ions are in eight‐fold coordination with Sr–O distances of 2.50–2.72Å and Sr–S distances of 3.21Å, (C₄S₄)²⁻ acts as a chelating ligand towards Sr²⁺. The structure is closely related to the previously reported Ca²⁺ containing analogue, which is of lower symmetry belonging to the monoclinic crystal system. A supergroup‐subgroup relation between the space groups of both structures is present. The structure of 2 is made up of Ba²⁺ and K⁺ ions in eight and nine‐fold coordination by H₂O molecules and (C₄S₄)²⁻ ions which act as chelating ligands towards one cation and bridging between two cations. The coordination polyhedra of the cations are connected by common edges and corners in two dimensions to layers which are connected by tetrathiosquarate ions to a three‐dimensional network. The infrared and Raman spectra show bands typical for the molecular building units of the two compounds.     

Charge‐assisted N—H·I and C—H·I hydrogen bonding in (1R,2S)‐1‐(ferrocenylmethyl)‐2‐(methoxymethyl)pyrrolidinium iodide

In the title compound, [Fe(C₅H₅)(C₁₂H₁₉NO)]I, the ferrocene moiety has an eclipsed conformation, with mean Fe—C bond lengths of 2.031 (4) and 2.020 (6) Å for the substituted and unsubstituted cyclo­penta­dienyl rings. The pyrrolidinium heterocycle adopts an envelope conformation and has its 1‐ and 2‐substituents in a relative trans disposition. Strong (+/−)‐charge‐assisted N—H·I and C—H·I hydrogen bonds are present. The crystal structure is also stabilized by weak C—H·O interactions.     

Cocrystals of 1,4‐diethynylbenzene with 1,3‐diacetylbenzene and benzene‐1,4‐dicarbaldehyde exhibiting strong nonconventional alkyne–carbonyl C—H…O hydrogen bonds between the components

Weak interactions between organic molecules are important in solid‐state structures where the sum of the weaker interactions support the overall three‐dimensional crystal structure. The sp‐C—H…N hydrogen‐bonding interaction is strong enough to promote the deliberate cocrystallization of a series of diynes with a series of dipyridines. It is also possible that a similar series of cocrystals could be formed between molecules containing a terminal alkyne and molecules which contain carbonyl O atoms as the potential hydrogen‐bond acceptor. I now report the crystal structure of two cocrystals that support this hypothesis. The 1:1 cocrystal of 1,4‐diethynylbenzene with 1,3‐diacetylbenzene, C₁₀H₆·C₁₀H₁₀O₂, (1), and the 1:1 cocrystal of 1,4‐diethynylbenzene with benzene‐1,4‐dicarbaldehyde, C₁₀H₆·C₈H₆O₂, (2), are presented. In both cocrystals, a strong nonconventional ethynyl–carbonyl sp‐C—H…O hydrogen bond is observed between the components. In cocrystal (1), the C—H…O hydrogen‐bond angle is 171.8 (16)° and the H…O and C…O hydrogen‐bond distances are 2.200 (19) and 3.139 (2) Å, respectively. In cocrystal (2), the C—H…O hydrogen‐bond angle is 172.5 (16)° and the H…O and C…O hydrogen‐bond distances are 2.25 (2) and 3.203 (2) Å, respectively.     

Zur Struktur eines ungewöhnlichen Tetramers des Lithiumphenolats: [C6H5OLi · C4H8O]4 · C6H5OH

The Structure of an unusual Tetramere of Lithium Phenoxide: [C₆H₅OLi · C₄H₈O]₄ · C₆H₅OH Single crystals of lithium phenoxide have been obtained from THF. In the structure (P 2₁/n, Z = 4, a = 11.69 Å, b = 21.15 Å, c = 18.55 Å, β = 91.11°) four lithium atoms and four phenoxide oxygen atoms are cubically arranged. Further, each lithium atom coordinates the oxygen atom of a tetrahydrofuran molecule. The ideal cubeform structure is disturbed by one phenol molecule which is coordinated in addition to four phenoxide and four THF molecules. Hence, one edge of the cube (Li4? O4) is substituted by the coordination of the phenol oxygen atom O5 with Li4 and hydrogen bonding between O4 and the hydroxy group of phenol. Van der Waals forces are the only interaction between these complexes.     

The O···H intramolecular hydrogen bond in 4‐X‐2‐hydroxybenzaldehydes: The relationships between geometrical parameters,estimated binding energies,and NMR data

The relationships among geometrical parameters, estimated binding energies, and nuclear magnetic resonance data in –C?O···H? O? intramolecular H‐bond of some substituted 2‐hydroxybenzaldehyde have theoretically been studied by B3LYP and MP2 methods with 6‐311++G** and AUG‐cc‐PVTZ basis sets. All substituents increase estimated hydrogen bond energies E_HBs (with the exception of NO₂ and C₂H₅), which are in good correlation with geometrical parameters, topological properties of electron density calculated at O···H bond critical points and ring critical points by using atoms in molecules method, the results of natural bond orbital analysis, and calculated nuclear magnetic resonance data. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Darstellung und Charakterisierung der Fulleren-Kokristallisate C60 · 12 C6H12, C70 · 12 C6H12, C60 · 12 CCl4, C60 · 2 CHBr3, C60 · 2 CHCl3, C60 · 2 H2CCl2

Synthesis and Characterization of the Fullerene Co-Crystals C₆₀ · 12 C₆H₁₂, C₇₀ · 12 C₆H₁₂, C₆₀ · 12 CCl₄, C₆₀ · 2CHBr₃, C₆₀ · 2CHCl₃, C₆₀ · 2H₂CCl₂ By crystallization of fullerenes from non-polar solvents (C₆H₁₂, CCl₄, CHBr₃, CHCl₃, H₂CCl₂) compounds of the following compositions were obtained: C₆₀ · 12C₆H₁₂, C₇₀ · 12C₆H₁₂, C₆₀ · 12CCl₄, C₆₀ · 2CHCl₃, C₆₀ · 2CHBr₃ and C₆₀ · 2H₂CCl₂. Lattice parameters have been determined by X-ray diffraction of powder samples; according to single-crystal examinations on C₆₀ · 12C₆H₁₂, C₆₀ · 12CCl₄ and C₆₀ · 2CHBr₃ the fullerene is orientationally disordered. C₆₀ · 12C₆H₁₂, cubic, a = 28.167(1) Å; C₇₀ · 12C₆H₁₂, cubic, a = 28.608(2) Å; C₆₀ · 12CCl₄, cubic, a = 27.42(1) Å; C₆₀ · 2CHBr₃, hexagonal, a = 10.212(1), c = 10.209(1) Å; C₆₀ · 2CHCl₃, hexagonal, a = 10.08(1), c = 10.11(2) Å; C₆₀ · 2H₂CCl₂, tetragonal, a = 16.400(1) Å, c = 11.645(7) Å.     

Fluorenyl Zinc Phosphonate Zn(H2O)PO3–C13H9·H2O: Hybrid Columnar Structure with Strong C–H···π Interactions

A new zinc phosphonate Zn(H₂O)PO₃–C₁₃H₉ · H₂O with a columnar structure was synthesized in hydrothermal conditions. This compound crystallizes in space group P2₁/c [a = 15.832(4) Å, b = 5.1915(10) Å, c = 17.519(4) Å and β = 114.479(6)°]. Its inorganic framework consists of isolated chains of corner‐sharing ZnO₃(H₂O) and PO₃C tetrahedra. These chains are linked to fluorene cycles, forming hybrid columns, interconnected through C–H ··· π bonds. The photoluminescence properties of this hybrid material show that its emission bands are red shifted with respect to those of the mother phosphonic acid. This effect is explained on the basis of the structural constraints imposed by the inorganic Zn‐phosphonate chains.     

A Sterically Hindered Phosphonic Acid with a Hydrogen‐Bonded Cage Structure: [4‐tert‐Bu‐2,6‐Mes2‐C6H2P(O)(OH)2·H2O]4

The synthesis and molecular structure of the novel phosphonic acid 4‐tert‐Bu‐2,6‐Mes₂‐C₆H₂P(O)(OH)₂ ( 1 ) is reported. Compound 1 crystallizes in form of its monohydrate as a hydrogen‐bonded cluster ( 1·H₂O )₄ comprizing four phosphonic acid molecules (O···O 2.383(3)‐3.006(4) Å). Additionally, sterically hindered terphenyl‐substituted phosphorus compounds of the type 4‐tert‐Bu‐2,6‐Mes₂‐C₆H₂PR(O)(OH) ( 5 , R = H; 7 , R = O₂CC₆H₄‐3‐Cl; 9 , R = OEt) were prepared, which all show dimeric hydrogen‐bonded structures with O···O distances in the range 2.489(2)–2.519(3) Å. Attempts at oxidizing 5 using H₂O₂, KMnO₄, O₃, or Me₃NO in order to give 1 failed. Crystallization of 5 in the presence of Me₃NO gave the novel hydrogen bonded aggregate 4‐tert‐Bu‐2,6‐Mes₂‐C₆H₂PH(O)(OH)·ONMe₃ ( 6 ) showing an O–H···O distance of 2.560(4) Å.     

1‐Benzoyl‐3‐[(2‐benzylsulfanyl)phenyl]thiourea

In the title compound, C₂₁H₁₈N₂OS₂, a strong intramolecular N—H...O hydrogen bond [N...O = 2.642 (3) Å] between the amide N atom and the benzoyl O atom forms an almost planar six‐membered ring in the central part of the molecule. In the crystal, molecules are packed through weak N—H...S interactions. Intra‐ and intermolecular hydrogen bonds and van der Waals interactions are the stabilizing forces for the crystal structure.     

meso‐5,5,7,12,12,14‐Hexamethyl‐1,4‐diaza‐8,11‐diazoniacyclotetradecane bis(2‐naphthoate) ethanol disolvate: centrosymmetric five‐component aggregates linked into sheets by C—H⃛π(arene) hydrogen bonding

The title compound is an ethanol‐solvated salt, C₁₆H₃₈N₄²⁺·2C₁₁H₇O₂⁻·2C₂H₆O, in which the cation lies across a centre of inversion in P2₁/c. The ions are linked by N—H⃛O hydrogen bonds [H⃛O = 1.70 and 2.30 Å, N⃛O = 2.624 (2) and 3.136 (2) Å, and N—H⃛O = 178 and 151°], and the ethanol mol­ecule is linked to the anion by an O—H⃛O hydrogen bond [H⃛O = 1.90 Å, O⃛O = 2.728 (2) Å and O—H⃛O = 171°], to form a centrosymmetric five‐component aggregate. C—H⃛O hydrogen bonds and aromatic π–π‐stacking interactions are absent, but the aggregates are linked into sheets by a single C—H⃛π(arene) hydrogen bond.     

trans‐Aquachloro[(1R,4R,8S,11S)‐6,13‐diammonio‐6,13‐dimethyl‐1,4,8,11‐tetra­azacyclo­tetra­decane‐κ4N1,4,8,11]nickel(II) trichloride trihydrate

The title compound, [NiCl(C₁₂H₃₂N₆)(H₂O)]Cl₃·3H₂O, has the bis­(diamine)‐substituted cyclic tetra­amine in a planar coordination to triplet ground‐state Ni^II [average Ni—N = 2.068 (3) Å], with a chloride ion [Ni—Cl = 2.4520 (5) Å] and a water mol­ecule [Ni—O = 2.177 (2) Å] coordinated in the axial sites. The amine substituents are protonated and equatorially oriented. The amine groups, ammonium groups, water molecules and chloride ions are linked by an extensive hydrogen‐bonding network.     

4‐Amino‐N‐isopropyl­benzamidinium chloride ethanol solvate

The title compound, C₁₀H₁₆N·Cl⁻·C₂H₆O, is an important intermediate in the convergent synthesis of amidine‐substituted polycyclic heterocycles, a class of compounds that shows significant anticancer activity. The molecule of (I) is not planar, having a dihedral angle of 25.00 (7)° between the aniline and amidine (–C—NH=C=NH₂) groups. The proton­ation of the amidine molecular fragment is accompanied by delocalized C—N bond distances of 1.320 (2) and 1.317 (2) Å. The cations and chloride anions are involved in a network of hydrogen bonds, resulting in the formation of infinite chains propagating along the b direction. The chains are further grouped within the ab plane, in such a way that the structure is segregated into layers dominated by hydro­phobic interactions involving N‐isopropyl residues and layers dominated by N—H⋯Cl [N⋯Cl = 3.275 (2)–3.596 (2) Å], O—H⋯Cl [O⋯Cl = 3.229 (3) Å] and N—H⋯O [N⋯O = 2.965 (3) Å] hydrogen bonds.     

Crystal Structure of the Mixed‐Valent Basic Mercury Nitrate HgI2(NO3)2·HgII(OH)(NO3)·HgII(NO3)2·4HgIIO [= Hg8O4(OH)(NO3)5]

Light‐yellow single crystals of the mixed‐valent mercury‐rich basic nitrate Hg₈O₄(OH)(NO₃)₅ were obtained as a by‐product at 85 °C from a melt consisting of stoichiometric amounts of (Hg^I₂)(NO₃)₂·2H₂O and Hg^II(OH)(NO₃). The title compound, represented by the more detailed formula Hg^I₂(NO₃)₂·Hg^II(OH)(NO₃)·Hg^II(NO₃)₂·4Hg^IIO, exhibits a new structure type (monoclinic, C2/c, Z = 4, a = 6.7708(7), b = 11.6692(11), c = 24.492(2) Å, β = 96.851(2)°, 2920 structure factors, 178 parameters, R1[F² > 2σ(F²)] = 0.0316) and is made up of almost linear [O‐Hg^II‐O] and [O‐Hg^I‐Hg^I‐O] building blocks with typical Hg^II‐O distances around 2.06Å and a Hg^I‐O distance of 2.13Å. The Hg₂²⁺ dumbbell exhibits a characteristic Hg‐Hg distance of 2.5079(7) Å. The different types of mercury‐oxygen units form a complex three‐dimensional network exhibiting large cavities which are occupied by the nitrate groups. The NO₃^? anions show only weak interactions between the nitrate oxygen atoms and the mercury atoms which are at distances > 2.6Å from one another. One of the three crystallographically independent nitrate groups is disordered.     

Die kristallstruktur des 2;1-Adduktes zwischen Antimontrichlorid und Diphenyl, 2SbCl3 · (C6H5)2

The Crystal Structure of the 2:1 Addition Compound between Antimony Trichloride and Diphenyl, 2SbCl₃ · (C₆H₅)₂ The 2:1 adduct of antimony trichloride with diphenyl, 2SbCl₃ · (C₆H₅)₂, crystallizes in the triclinic space group P1 with a = 13.498(5) Å, b = 7.884(2) Å, c = 9.341(3) Å, α = 86.40(2)°, β = 110.05(3)⁰, γ = 91.41(2)° and Z = 2. Each SbCl₃ molecule points to a phenyl ring of the diphenyl molecule. The distances from the two independent Sb atoms to the phenyl ring planes differ (3.26 and 3.08 Å). The torsion angle between the phenyl ring planes within the diphenyl molecule is 40.5°. The mean Sb? Cl bond distance is 2.39 Å. Longer Sb…Cl contacts of 3.44 to 3.46 Å and the π-donor-acceptor interactions complete the distorted octahedral coordination, and ψ-octahedral coordination respectively, of the Sb atoms.     

New coordination modes in potassium edta salts: K2[H2edta]·2H2O,K3[Hedta]·2H2O and K4[edta]·3.92H2O

Three potassium edta (edta is ethylenediaminetetraacetic acid, H₄Y) salts which have different degrees of ionization of the edta anion, namely dipotassium 2‐({2‐[bis(carboxylatomethyl)azaniumyl]ethyl}(carboxylatomethyl)azaniumyl)acetate dihydrate, 2K⁺·C₁₀H₁₄N₂O₈²⁻·2H₂O, (I), tripotassium 2,2′‐({2‐[bis(carboxylatomethyl)amino]ethyl}ammonio)diacetate dihydrate, 3K⁺·C₁₀H₁₃N₂O₈³⁻·2H₂O, (II), and tetrapotassium 2,2′,2′′,2′′′‐(ethane‐1,2‐diyldinitrilo)tetraacetate 3.92‐hydrate, 4K⁺·C₁₀H₁₂N₂O₈⁴⁻·3.92H₂O, (III), were obtained in crystalline form from water solutions after mixing edta with potassium hydroxide in different molar ratios. In (II), a new mode of coordination of the edta anion to the metal is observed. The HY³⁻ anion contains one deprotonated N atom coordinated to K⁺ and the second N atom is involved in intramolecular bifurcated N—H...O and N—H...N hydrogen bonds. The overall conformation of the HY³⁻ anions is very similar to that of the Y⁴⁻ anions in (III), although a slightly different spatial arrangement of the –CH₂COO⁻ groups in relation to (III) is observed, whereas the H₂Y²⁻ anions in (I) adopt a distinctly different geometry. The preferred synclinal conformation of the –NCH₂CH₂N– moiety was found for all edta anions. In all three crystals, the anions and water molecules are arranged in three‐dimensional networks linked via O—H...O and C—H...O [and N—H...O in (I) and (II)] hydrogen bonds. K...O interactions also contribute to the three‐dimensional polymeric architecture of the salts.     

catena‐Poly[[[tetrakis(1‐methylimidazole‐κN3)copper(II)]‐μ2‐sulfato‐κ2O:O′] acetonitrile hemisolvate sesquihydrate]

The title compound, [Cu(C₄H₈N₂)₄]SO₄·0.5CH₃CN·1.5H₂O, consists of a double chain wherein the Cu centres are octahedrally coordinated by four 1‐methyl­imidazole ligands in the equatorial plane and by two axial sulfate ions which act as bridges between the Cu centres. The Cu—N bond lengths lie between 1.9929 (14) and 2.0226 (14) Å, but the Cu—O bond distances are longer, with values between 2.3496 (13) and 2.8276 (14) Å. The water mol­ecules participate in the formation of a network of hydrogen bonds of significance in maintaining the connectivity of the structure.     

Tris(8‐quinolinolato‐N,O)­cobalt(III) ethanol solvate

In the crystal of the title complex, [Co(C₉H₆NO)₃]·C₂H₅OH, the central Co atom has a distorted octahedral coordination comprised of three N atoms and three O atoms from the three 8‐quinolinolato ligands. The three Co—O bond distances are in the range 1.887 (2)–1.910 (2) Å, while the three Co—N bond distances range from 1.919 (2) to 1.934 (2) Å. The solvent ethanol mol­ecule forms an intermolecular O—H?O hydrogen bonding with a quinolinolato ligand.     

Two Novel CuII Phenanthroline Adipato Complexes with π‐π Stacking Interactions: [Cu(phen)2(C6H8O4)] · 4.5 H2O and [(Cu2(phen)2Cl2)(C6H8O4)] · 4 H2O

The blue copper complex compounds [Cu(phen)₂(C₆H₈O₄)] · 4.5 H₂O ( 1 ) and [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)] · 4 H₂O ( 2 ) were synthesized from CuCl₂, 1,10‐phenanthroline (phen) and adipic acid in CH₃OH/H₂O solutions. [Cu(phen)₂‐ (C₆H₈O₄)] complexes and hydrogen bonded H₂O molecules form the crystal structure of ( 1 ) (P1 (no. 2), a = 10.086(2) Å, b = 11.470(2) Å, c = 16.523(3) Å, α = 99.80(1)°, β = 115.13(1)°, γ = 115.13(1)°, V = 1617.5(5) ų, Z = 2). The Cu atoms are square‐pyramidally coordinated by four N atoms of the phen ligands and one O atom of the adipate anion (d(Cu–O) = 1.989 Å, d(Cu–N) = 2.032–2.040 Å, axial d(Cu–N) = 2.235 Å). π‐π stacking interactions between phen ligands are responsible for the formation of supramolecular assemblies of [Cu(phen)₂(C₆H₈O₄)] complex molecules into 1 D chains along [111]. The crystal structure of ( 2 ) shows polymeric [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains (P1 (no. 2), a = 7.013(1) Å, b = 10.376(1) Å, c = 11.372(3) Å, α = 73.64(1)°, β = 78.15(2)°, γ = 81.44(1)°, V = 773.5(2) ų, Z = 1). The Cu atoms are fivefold coordinated by two Cl atoms, two N atoms of phen ligands and one O atom of the adipate anion, forming [CuCl₂N₂O] square pyramids with an axial Cl atom (d(Cu–O) = 1.958 Å, d(Cu–N) = 2.017–2.033 Å, d(Cu–Cl) = 2.281 Å; axial d(Cu–Cl) = 2.724 Å). Two square pyramids are condensed via the common Cl–Cl edge to centrosymmetric [Cu₂Cl₂N₄O₂] dimers, which are connected via the adipate anions to form the [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains. The supramolecular 3 D network results from π‐π stacking interactions between the chains. H₂O molecules are located in tunnels.