Cocrystals of 6‐methyl‐2‐thiouracil: presence of the acceptor–donor–acceptor/donor–acceptor–donor synthon

The results of seven cocrystallization experiments of the antithyroid drug 6‐methyl‐2‐thiouracil (MTU), C₅H₆N₂OS, with 2,4‐diaminopyrimidine, 2,4,6‐triaminopyrimidine and 6‐amino‐3H‐isocytosine (viz. 2,6‐diamino‐3H‐pyrimidin‐4‐one) are reported. MTU features an ADA (A = acceptor and D = donor) hydrogen‐bonding site, while the three coformers show complementary DAD hydrogen‐bonding sites and therefore should be capable of forming an ADA/DAD N—H...O/N—H...N/N—H...S synthon with MTU. The experiments yielded one cocrystal and six cocrystal solvates, namely 6‐methyl‐2‐thiouracil–2,4‐diaminopyrimidine–1‐methylpyrrolidin‐2‐one (1/1/2), C₅H₆N₂OS·C₄H₆N₄·2C₅H₉NO, (I), 6‐methyl‐2‐thiouracil–2,4‐diaminopyrimidine (1/1), C₅H₆N₂OS·C₄H₆N₄, (II), 6‐methyl‐2‐thiouracil–2,4‐diaminopyrimidine–N,N‐dimethylacetamide (2/1/2), 2C₅H₆N₂OS·C₄H₆N₄·2C₄H₉NO, (III), 6‐methyl‐2‐thiouracil–2,4‐diaminopyrimidine–N,N‐dimethylformamide (2/1/2), C₅H₆N₂OS·0.5C₄H₆N₄·C₃H₇NO, (IV), 2,4,6‐triaminopyrimidinium 6‐methyl‐2‐thiouracilate–6‐methyl‐2‐thiouracil–N,N‐dimethylformamide (1/1/2), C₄H₈N₅⁺·C₅H₅N₂OS⁻·C₅H₆N₂OS·2C₃H₇NO, (V), 6‐methyl‐2‐thiouracil–6‐amino‐3H‐isocytosine–N,N‐dimethylformamide (1/1/1), C₅H₆N₂OS·C₄H₆N₄O·C₃H₇NO, (VI), and 6‐methyl‐2‐thiouracil–6‐amino‐3H‐isocytosine–dimethyl sulfoxide (1/1/1), C₅H₆N₂OS·C₄H₆N₄O·C₂H₆OS, (VII). Whereas in cocrystal (I) an R₂²(8) interaction similar to the Watson–Crick adenine/uracil base pair is formed and a two‐dimensional hydrogen‐bonding network is observed, the cocrystals (II)–(VII) contain the triply hydrogen‐bonded ADA/DAD N—H...O/N—H...N/N—H...S synthon and show a one‐dimensional hydrogen‐bonding network. Although 2,4‐diaminopyrimidine possesses only one DAD hydrogen‐bonding site, it is, due to orientational disorder, triply connected to two MTU molecules in (III) and (IV).     

Comparison of the hydrogen‐bond patterns in 2‐amino‐1,3,4‐thiadiazolium hydrogen oxalate, 2‐amino‐1,3,4‐thiadiazole–succinic acid (1/2), 2‐amino‐1,3,4‐thiadiazole–glutaric acid (1/1) and 2‐amino‐1,3,4‐thiadiazole–adipic acid (1/1)

The X‐ray single‐crystal structure determinations of the chemically related compounds 2‐amino‐1,3,4‐thiadiazolium hydrogen oxalate, C₂H₄N₃S⁺·C₂HO₄⁻, (I), 2‐amino‐1,3,4‐thiadiazole–succinic acid (1/2), C₂H₃N₃S·2C₄H₆O₄, (II), 2‐amino‐1,3,4‐thiadiazole–glutaric acid (1/1), C₂H₃N₃S·C₅H₈O₄, (III), and 2‐amino‐1,3,4‐thiadiazole–adipic acid (1/1), C₂H₃N₃S·C₆H₁₀O₄, (IV), are reported and their hydrogen‐bonding patterns are compared. The hydrogen bonds are of the types N—H...O or O—H...N and are of moderate strength. In some cases, weak C—H...O interactions are also present. Compound (II) differs from the others not only in the molar ratio of base and acid (1:2), but also in its hydrogen‐bonding pattern, which is based on chain motifs. In (I), (III) and (IV), the most prominent feature is the presence of an R₂²(8) graph‐set motif formed by N—H...O and O—H...N hydrogen bonds, which are present in all structures except for (I), where only a pair of N—H...O hydrogen bonds is present, in agreement with the greater acidity of oxalic acid. There are nonbonding S...O interactions present in all four structures. The difference electron‐density maps show a lack of electron density about the S atom along the S...O vector. In all four structures, the carboxylic acid H atoms are present in a rare configuration with a C—C—O—H torsion angle of ∼0°. In the structures of (II)–(IV), the C—C—O—H torsion angle of the second carboxylic acid group has the more common value of ∼|180|°. The dicarboxylic acid molecules are situated on crystallographic inversion centres in (II). The Raman and IR spectra of the title compounds are presented and analysed.     

trans‐Diaquabis(3‐hydroxybenzoato‐κO1)bis(nicotinamide‐κN1)copper(II)

The title compound, [Cu(C₇H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂], is a two‐dimensional hydrogen‐bonded supramolecular complex. The Cu^II ion resides on a centre of symmetry and is in an octahedral coordination environment comprising two pyridine N atoms, two carboxylate O atoms and two O atoms from water molecules. Intermolecular N—H...O and O—H...O hydrogen bonds produce R₂²(4), R₂²(8) and R₂²(15) rings which lead to one‐dimensional polymeric chains. An extensive two‐dimensional network of N—H...O and O—H...O hydrogen bonds and C—H...π interactions are responsible for crystal stabilization.     

Crystal structure of pharmaceutical cocrystals of 2,6‐diaminopyridine with piracetam and theophylline

Pharmaceutical cocrystals are crystalline solids formed by an active pharmaceutical ingredient and a cocrystal former. The cocrystals 2,6‐diaminopyridine (DAP)–piracetam [PIR; systematic name: 2‐(2‐oxopyrrolidin‐1‐yl)acetamide] (1/1), C₅H₇N₃·C₆H₁₀N₂O₂, (I), and 2,6‐diaminopyridine–theophylline (TEO; systematic name: 1,3‐dimethyl‐7H‐purine‐2,6‐dione) (1/1), C₅H₇N₃·C₇H₈N₄O₂, (II), were prepared by the solvent‐assisted grinding method and were characterized by IR spectroscopy and powder X‐ray diffraction. Cocrystal (I) crystallized in the orthorhombic space group Pbca and showed a 1:1 stoichiometry. The DAP and PIR molecules are linked by an N—H…O hydrogen‐bond interaction. Self‐assembly of PIR molecules forms a sheet of C (4) and C (7) chains. Cocrystal (II) crystallized in the monoclinic P 2₁/c space group and also showed a 1:1 stoichiometry. The DAP and TEO molecules are connected by N—H…N and N—H…O hydrogen bonds, forming an R ₂²(9) heterosynthon. A bidimensional supramolecular array is formed by interlinked DAP–TEO tetramers, producing a two‐dimensional sheet.     

Supramolecular architectures in cytosinium 6‐chloronicotinate monohydrate and 5‐bromo‐6‐methylisocytosinium hydrogen sulfate

Aminopyrimidine derivatives are biologically important as they are components of nucleic acids and drugs. The crystals of two new salts, namely cytosinium 6‐chloronicotinate monohydrate, C₄H₆N₃O⁺·C₆H₃ClNO₂⁻·H₂O, ( I ), and 5‐bromo‐6‐methylisocytosinium hydrogen sulfate (or 2‐amino‐5‐bromo‐4‐oxo‐6‐methylpyrimidinium hydrogen sulfate), C₅H₇BrN₃O⁺·HSO₄⁻, ( II ), have been prepared and characterized by single‐crystal X‐ray diffraction. The pyrimidine ring of both compounds is protonated at the imine N atom. In hydrated salt ( I ), the primary R₂²(8) ring motif (supramolecular heterosynthon) is formed via a pair of N—H…O(carboxylate) hydrogen bonds. The cations, anions and water molecule are hydrogen bonded through N—H…O, N—H…N, O—H…O and C—H…O hydrogen bonds, forming R₂²(8), R₃²(7) and R₅⁵(21) motifs, leading to a hydrogen‐bonded supramolecular sheet structure. The supramolecular double sheet structure is formed via water–carboxylate O—H…O hydrogen bonds and π–π interactions between the anions and the cations. In salt ( II ), the hydrogen sulfate ions are linked via O—H…O hydrogen bonds to generate zigzag chains. The aminopyrimidinium cations are embedded between these zigzag chains. Each hydrogen sulfate ion bridges two cations via pairs of N—H…O hydrogen bonds and vice versa, generating two R₂²(8) ring motifs (supramolecular heterosynthon). The cations also interact with one another via halogen–halogen (Br…Br) and halogen–oxygen (Br…O) interactions.     

3,3′,5,5′‐Tetramethyl‐4,4′‐bipyrazole–pentafluorophenol (2/3)

In the title compound, 2C₁₀H₁₄N₄·3C₆HF₅O, one of the pentafluorophenol molecules resides on a mirror plane bisecting the O...F axis. The components aggregate by N—H...N, N—H...O and O—H...N hydrogen bonds involving equal disordering of the H atoms into molecular ensembles based on a 2:1 pyrazole–phenol cyclic pattern [O...N = 2.7768 (16) Å and N...N = 2.859 (2) Å], crosslinked into one‐dimensional columns via hydrogen bonding between the outer pyrazole groups and additional pentafluorophenol molecules. The latter yields a 1:1 pyrazole–phenol catemer with alternating strong O—H...N [2.5975 (16) Å] and weaker N—H...O [2.8719 (17) Å] hydrogen bonds. This is the first reported molecular adduct of a pentafluorinated phenol and a nitrogen base, and suggests the utility of highly acidic phenols and pyrazoles for developing hydrogen‐bonded cocrystals.     

Diaquabis(4‐fluorobenzoato‐κO)bis(nicotinamide‐κN)cobalt(II)

The title compound, [Co(C₇H₄FO₂)₂(C₆H₆N₂O)₂(H₂O)₂], is a three‐dimensional hydrogen‐bonded supramolecular complex. The Co^II ion resides on a centre of symmetry and is in an octahedral coordination environment comprising two pyridyl N atoms, two carboxylate O atoms and two O atoms from water molecules. Intermolecular N—H...O and O—H...O hydrogen bonds produce R₃²(6), R₂²(12) and R₂²(16) rings, which lead to two‐dimensional chains. An extensive three‐dimensional network of C—H...F, N—H...O and O—H...O hydrogen bonds and π–π interactions are responsible for crystal stabilization.     

Crystal structures of the pyrazinamide–p‐aminobenzoic acid (1/1) cocrystal and the transamidation reaction product 4‐(pyrazine‐2‐carboxamido)benzoic acid in the molten state

The synthesis of pharmaceutical cocrystals is a strategy to enhance the performance of active pharmaceutical ingredients (APIs) without affecting their therapeutic efficiency. The 1:1 pharmaceutical cocrystal of the antituberculosis drug pyrazinamide (PZA) and the cocrystal former p‐aminobenzoic acid (p‐ABA), C₇H₇NO₂·C₅H₅N₃O, (1), was synthesized successfully and characterized by relevant solid‐state characterization methods. The cocrystal crystallizes in the monoclinic space group P2₁/n containing one molecule of each component. Both molecules associate via intermolecular O—H...O and N—H...O hydrogen bonds [O...O = 2.6102 (15) Å and O—H...O = 168.3 (19)°; N...O = 2.9259 (18) Å and N—H...O = 167.7 (16)°] to generate a dimeric acid–amide synthon. Neighbouring dimers are linked centrosymmetrically through N—H...O interactions [N...O = 3.1201 (18) Å and N—H...O = 136.9 (14)°] to form a tetrameric assembly supplemented by C—H...N interactions [C...N = 3.5277 (19) Å and C—H...N = 147°]. Linking of these tetrameric assemblies through N—H...O [N...O = 3.3026 (19) Å and N—H...O = 143.1 (17)°], N—H...N [N...N = 3.221 (2) Å and N—H...N = 177.9 (17)°] and C—H...O [C...O = 3.5354 (18) Å and C—H...O = 152°] interactions creates the two‐dimensional packing. Recrystallization of the cocrystals from the molten state revealed the formation of 4‐(pyrazine‐2‐carboxamido)benzoic acid, C₁₂H₉N₃O₃, (2), through a transamidation reaction between PZA and p‐ABA. Carboxamide (2) crystallizes in the triclinic space group P with one molecule in the asymmetric unit. Molecules of (2) form a centrosymmetric dimeric homosynthon through an acid–acid O—H...O hydrogen bond [O...O = 2.666 (3) Å and O—H...O = 178 (4)°]. Neighbouring assemblies are connected centrosymmetrically via a C—H...N interaction [C...N = 3.365 (3) Å and C—H...N = 142°] engaging the pyrazine groups to generate a linear chain. Adjacent chains are connected loosely via C—H...O interactions [C...O = 3.212 (3) Å and C—H...O = 149°] to generate a two‐dimensional sheet structure. Closely associated two‐dimensional sheets in both compounds are stacked via aromatic π‐stacking interactions engaging the pyrazine and benzene rings to create a three‐dimensional multi‐stack structure.     

mer‐Diaquabis(1H‐imidazole‐κN3)[orotato(2–)]cobalt(II)

In the title complex, mer‐diaqua[2,6‐dioxo‐1,2,3,6‐tetrahydropyrimidine‐4‐carboxylato(2−)]bis(1H‐imidazole‐κN³)cobalt(II), [Co(C₅H₂N₂O₄)(C₃H₄N₂)₂(H₂O)₂], the Co^II ion is coordinated by a deprotonated N atom and the carboxylate O atom of the orotate ligand, two imidazole N atoms and two aqua ligands in a distorted octahedral geometry. The title complex exists as discrete doubly hydrogen‐bonded dimers, and a three‐dimensional network of O—H...O and N—H...O hydrogen bonds and weak π–π interactions is responsible for crystal stabilization.     

(6‐Oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylato‐κ2O5,O6)bis[2‐(2‐pyridyl)‐1H‐benzimidazole‐κ2N2,N3]manganese(II) monohydrate

In the title compound, [Mn(C₅H₂N₂O₄)(C₁₂H₉N₃)₂]·H₂O, the Mn^II centre is surrounded by three bidentate chelating ligands, namely, one 6‐oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylate (or uracil‐5‐carboxylate, Huca²⁻) ligand [Mn—O = 2.136 (2) and 2.156 (3) Å] and two 2‐(2‐pyridyl)‐1H‐benzimidazole (Hpybim) ligands [Mn—N = 2.213 (3)–2.331 (3) Å], and it displays a severely distorted octahedral geometry, with cis angles ranging from 73.05 (10) to 105.77 (10)°. Intermolecular N—H...O hydrogen bonds both between the Hpybim and the Huca²⁻ ligands and between the Huca²⁻ ligands link the molecules into infinite chains. The lattice water molecule acts as a hydrogen‐bond donor to form double O...H—O—H...O hydrogen bonds with the Huca²⁻ O atoms, crosslinking the chains to afford an infinite two‐dimensional sheet; a third hydrogen bond (N—H...O) formed by the water molecule as a hydrogen‐bond acceptor and a Hpybim N atom further links these sheets to yield a three‐dimensional supramolecular framework. Possible partial π–π stacking interactions involving the Hpybim rings are also observed in the crystal structure.     

Hydrogen‐bonded zigzag chains in 2,2′‐dithiodibenzoic acid–1,3‐di‐4‐pyridylpropane (1/1)

The title 1:1 cocrystal, C₁₄H₁₀O₄S₂·C₁₃H₁₄N₂ or H₂L·bpp, has the two components connected by O—H...N hydrogen bonds to generate a one‐dimensional zigzag chain running along the crystallographic a direction. These chains are further stacked into a three‐dimensional supramolecular network by weak C—H...O and C—H...π contacts. Comparison of the structural differences with previous findings suggests that deprotonated forms, hydrogen‐bonding sites and flexible ligand conformations become significant factors that influence the topological arrangement and binding stoichiometry of the resulting cocrystals.     

trans‐Diaquabis(nicotinamide‐κN)bis(salicylato‐κO)cobalt(II)

The title compound, [Co(C₇H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂], forms a three‐dimensional hydrogen‐bonded supramolecular structure. The Co^II ion is in an octahedral coordination environment comprising two pyridyl N atoms, two carboxylate O atoms and two O atoms from water molecules. Intermolecular N—H...O and O—H...O hydrogen bonds produce R₂²(8), R₂²(12) and R₂²(14) rings, which lead to two‐dimensional chains. An extensive three‐dimensional supramolecular network of C—H...O, N—H...O and O—H...O hydrogen bonds and C—H...π interactions is responsible for crystal structure stabilization. This study is an example of the construction of a supramolecular assembly based on hydrogen bonds in mixed‐ligand metal complexes.     

A three‐dimensional hydrogen‐bonded framework in 2‐amino‐6‐(N‐methylanilino)pyrimidin‐4(3H)‐one and a ribbon of fused hydrogen‐bonded rings in 2‐amino‐6‐(N‐methylanilino)‐5‐nitropyrimidin‐4(3H)‐one

The molecular dimensions of both 2‐amino‐6‐(N‐methylanilino)pyrimidin‐4(3H)‐one, C₁₁H₁₂N₄O, (I), and 2‐amino‐6‐(N‐methylanilino)‐5‐nitropyrimidin‐4(3H)‐one, C₁₁H₁₁N₅O₃, (II), are consistent with considerable polarization of the molecular–electronic structures. The molecules of (I) are linked into a three‐dimensional framework by a combination of one N—H...N hydrogen bond, two independent N—H...O hydrogen bonds and one C—H...π(arene) hydrogen bond. The molecules of (II) are linked into ribbons containing three types of edge‐fused ring by the combination of two independent three‐centre N—H...(O)₂ hydrogen bonds.     

Cocrystals of 6‐propyl‐2‐thiouracil: N—H...O versus N—H...S hydrogen bonds

In order to investigate the relative stability of N—H...O and N—H...S hydrogen bonds, we cocrystallized the antithyroid drug 6‐propyl‐2‐thiouracil with two complementary heterocycles. In the cocrystal pyrimidin‐2‐amine–6‐propyl‐2‐thiouracil (1/2), C₄H₅N₃·2C₇H₁₀N₂OS, (I), the `base pair' is connected by one N—H...S and one N—H...N hydrogen bond. Homodimers of 6‐propyl‐2‐thiouracil linked by two N—H...S hydrogen bonds are observed in the cocrystal N‐(6‐acetamidopyridin‐2‐yl)acetamide–6‐propyl‐2‐thiouracil (1/2), C₉H₁₁N₃O₂·2C₇H₁₀N₂OS, (II). The crystal structure of 6‐propyl‐2‐thiouracil itself, C₇H₁₀N₂OS, (III), is stabilized by pairwise N—H...O and N—H...S hydrogen bonds. In all three structures, N—H...S hydrogen bonds occur only within R₂²(8) patterns, whereas N—H...O hydrogen bonds tend to connect the homo‐ and heterodimers into extended networks. In agreement with related structures, the hydrogen‐bonding capability of C=O and C=S groups seems to be comparable.     

Helical supramolecular assembly of N2,N2′‐bis[3‐(morpholin‐4‐yl)propyl]‐N1,N1′‐(1,2‐phenylene)dioxalamide dimethyl sulfoxide monosolvate

In the title compound, C₂₄H₃₆N₆O₆·C₂H₆OS, the carbonyl groups are in an antiperiplanar conformation, with O=C—C=O torsion angles of 178.59 (15) and −172.08 (16)°. An intramolecular hydrogen‐bonding pattern is depicted by four N—H...O interactions, which form two adjacent S(5)S(5) motifs, and an N—H...N interaction, which forms an S(6) ring motif. Intermolecular N—H...O hydrogen bonding and C—H...O soft interactions allow the formation of a meso‐helix. The title compound is the first example of a helical 1,2‐phenylenedioxalamide. The oxalamide traps one molecule of dimethyl sulfoxide through N—H...O hydrogen bonding. C—H...O soft interactions give rise to the two‐dimensional structure.     

2‐Ethyl‐1‐[5‐(4‐methylphenyl)pyrazol‐3‐yl]‐3‐(thiophene‐2‐carbonyl)isothiourea: molecular ribbons containing three types of hydrogen‐bonded ring

The title compound, C₁₈H₁₈N₄OS₂, was prepared by reaction of S,S‐diethyl 2‐thenoylimidodithiocarbonate with 5‐amino‐3‐(4‐methylphenyl)‐1H‐pyrazole using microwave irradiation under solvent‐free conditions. In the molecule, the thiophene unit is disordered over two sets of atomic sites, with occupancies of 0.814 (4) and 0.186 (4), and the bonded distances provide evidence for polarization in the acylthiourea fragment and for aromatic type delocalization in the pyrazole ring. An intramolecular N—H...O hydrogen bond is present, forming an S(6) motif, and molecules are linked by N—H...O and N—H...N hydrogen bonds to form a ribbon in which centrosymmetric R₂²(4) rings, built from N—H...O hydrogen bonds and flanked by inversion‐related pairs of S(6) rings, alternate with centrosymmetric R₂²(6) rings built from N—H...N hydrogen bonds.     

Three‐dimensional hydrogen‐bonded framework in bis(melamin‐1‐ium) naphthalene‐1,5‐disulfonate melamine pentahydrate

Crystals of the title compound, 2C₃H₇N₆⁺·C₁₀H₆O₆S₂²⁻·C₃H₆N₆·5H₂O, are built up of neutral 2,4,6‐triamino‐1,3,5‐triazine (melamine), singly protonated melaminium cations, naphthalene‐1,5‐disulfonate dianions and water molecules. Two independent anions lie across centres of inversion in the space group P. The melamine molecules are connected by N—H...N hydrogen bonds into two different one‐dimensional polymers almost parallel to the (010) plane, forming a stacking structure along the b axis. The centrosymmetric naphthalene‐1,5‐disulfonate anions interact with water molecules via O—H...O hydrogen bonds, forming layers parallel to the (001) plane. The cations and anions are connected by N—H...O and O—H...N hydrogen bonds to form a three‐dimensional supramolecular framework.     

The ternary complex 4‐(2‐pyridyl)pyridinium–3,5‐di­nitro­benzoate–3,5‐di­nitro­benzoic acid (1/1/1)

In the title ternary complex, C₁₀H₉N₂⁺·C₇H₃N₂O₆^?·C₇H₄N₂O₆, the pyridinium cation adopts the role of the donor in an intermolecular N—H?O hydrogen‐bonding interaction with the carboxyl­ate group of the 3,5‐di­nitro­benzoate anion. The mol­ecules of the ternary complex form molecular ribbons perpendicular to the b direction, which are stabilized by one N—H?O, one O—H?O and five C—H?O intermolecular hydrogen bonds. The ribbons are further interconnected by three intermolecular C—H?O hydrogen bonds into a three‐dimensional network.     

2‐Aminopyrimidine–3,3,3‐triphenylpropanoic acid (1/1)

The title bimolecular compound, C₄H₅N₃·C₂₁H₁₈O₂, constructed from 2‐aminopyrimidine and 3,3,3‐triphenylpropanoic acid, forms a tetramolecular hydrogen‐bonded motif via O—H...N, N—H...O and N—H...N contacts. This aggregate organizes to give crystal‐packing motifs with hydrophilic and hydrophobic regions.     

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.