Supramolecular Assemblies of Mononuclear and Polymeric Nickel(II) Glutarato Complexes via π‐π Stacking Interactions and Hydrogen Bonds: [Ni(H2O)3(phen)(C5H6O4)] · H2O and [Ni(H2O)2(phen)(C5H6O4)]

Syntheses of the sky blue complex compounds [Ni(H₂O)₃(phen)(C₅H₆O₄)] · H₂O ( 1 ) and [Ni(H₂O)₂(phen)(C₅H₆O₄)] ( 2 ) were carried out by the reactions of 1,10‐phenanthroline monohydrate, glutaric acid, NiSO₄ · 6 H₂O and Na₂CO₃ in CH₃OH/H₂O at pH = 6.9 and 7.5, respectively. The crystal structure of 1 (P 1 (no. 2), a = 14.289 Å, b = 15.182 Å, c = 15.913 Å, α = 67.108°, β = 87.27°, γ = 68.216°, V = 2934.2 ų, Z = 2) consists of hydrogen bonded [Ni(H₂O)₃‐ (phen)(C₅H₆O₄)]₂ dimers and H₂O molecules. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, three water O atoms and one carboxyl O atom from one monodentate glutarato ligand (d(Ni–N) = 2.086, 2.090 Å; d(Ni–O) = 2.064–2.079 Å). Through the π‐π stacking interactions and intermolecular hydrogen bonds, the dimers are assembled to form 2 D layers parallel to (0 1 1). The crystal structure of 2 (P2₁/n (no. 14), a = 7.574 Å, b = 11.938 Å, c = 18.817 Å, β = 98.48°, V = 1682.8 ų, Z = 4) contains [Ni(H₂O)₂(phen)(C₅H₆O₄)_2/2] supramolecular chains extending along [010]. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, two water O atoms and two carboxyl O atoms from different bis‐monodentate glutarato ligands with d(Ni–N) = 2.082, 2.105 Å and d(Ni–O) = 2.059–2.087 Å. The supramolecular chains are assembled into a 3 D network by π‐π stacking interactions and interchain hydrogen bonds. A TG/DTA of 2 shows two endothermic effects at 132 °C and 390 °C corresponding to the complete dehydration and the lost of phen.     

Acetato(N‐phenylpyridine‐2‐carboxamidato‐κ2N,N)(N‐phenylpyridine‐2‐carboxamide‐κ2N1,O)copper(II)

The title complex, [Cu(C₁₂H₉N₂O)(C₂H₃O₂)(C₁₂H₁₀N₂O)], is a neutral Cu^II complex with a primary N₃O₂ coordination sphere. The Cu centre coordinates to both a deprotonated and a neutral molecule of N‐phenylpyridine‐2‐carboxamide and also to an acetate anion. The coordination around the metal centre is asymmetric, the deprotonated ligand providing two N donor atoms [Cu—N = 1.995 (2) and 2.013 (2) Å] and the neutral ligand providing one N and one O donor atom to the coordination environment [Cu—N = 2.042 (2) Å and Cu—O = 2.2557 (19) Å], the fifth donor being an O atom of the acetate ion [Cu—O = 1.9534 (19) Å]. The remaining O atom from the acetate ion can be considered as a weak donor atom [Cu—O = 2.789 (2) Å], conferring to the Cu complex an asymmetric octahedral geometry. The crystal structure is stabilized by intermolecular N—H...O, C—H...O and C—H...π interactions.     

Synthesis and Crystal Structure of [(1‐(Phenyltriazenido)‐2‐(phenyltriazeno)benzene)(nitrato)mercury(II)], {Hg[PhN3C6H4N3(H)Ph](NO3)}, a Complex with Weak Metal‐Arene π‐Interactions

The reaction of PhN₃(H)C₆H₄N₃(H)Ph with Hg(NO₃)₂ in THF in the presence of triethylamine yields {Hg[PhN₃C₆H₄N₃(H)Ph](NO₃)} as a yellow powder that can be recrystallized from THF/acetone. The crystals belong to the monoclinic system, space group P2₁ with the cell dimensions a = 9.639(2), b = 5.412(1), c = 19.675(4) Å, β= 97.47(3)°, V = 1017.7 (4) ų, Z = 2. The crystal structure determination (2668 unique reflections with [I>2σ(I)], 262 parameters, R₁ = 0.0393) shows that the structure consists of mononuclear complexes. Hg atoms are linearly coordinated by one N_α atom of the triazenide unit of the planar ligand [Hg‐N(1) = 2.101(8) Å] and an O atom of the NO₃^— ion [Hg‐O(1) = 2.11(1) Å]. Additional weak Hg‐N contacts [Hg‐N(4) = 2.662(9) and Hg‐N(3) = 2.851(9) Å] and an intramolecular hydrogen bond between the triazenide hydrogen and an O atom of the nitrate group are observed [N(6)‐H(6)···O(2) = 2.92(2) Å]. The complexes are stacked to infinite chains by metal‐arene π‐interactions. Each Hg atom is coordinated by the terminal phenyl rings of two neighboring complexes [Hg‐C from 3.40(1) to 4.10(1) Å] in a η² fashion.     

Bilayers in 4‐iodo‐N‐(2‐iodo‐4‐nitrophenyl)benzamide generated by a combination of an N—H⋯O=C hydrogen bond and two independent iodo–nitro interactions

Molecules of the title compound, C₁₃H₈I₂N₂O₃, are linked into C(4) chains by a single N—H⋯O=C hydrogen bond [H⋯O = 2.10 Å, N⋯O = 2.832 (5) Å and N—H⋯O = 140°]. Two independent two‐centre iodo–nitro interactions, both involving the same O atom but different I atoms [I⋯O = 3.205 (3) and 3.400 (3) Å, and C—I⋯O = 160.4 (2) and 155.7 (2)°], link the hydrogen‐bonded chains into bilayers.     

Three N2‐benzoyl­oxybenz­amidines: sheet structures built from hard and soft hydrogen bonds and aromatic π–π stacking interactions

Molecules of the title compounds N²‐(benzoyl­oxy)­benz­ami­dine, C₁₄H₁₂N₂O₂, (I), N²‐(2‐hydroxy­benzoyl­oxy)­benz­ami­dine, C₁₄H₁₂N₂O₃, (II), and N²‐benzoyloxy‐2‐hydroxybenzamidine, C₁₄H₁₂N₂O₃, (III), all have extended chain conformations, with the aryl groups remote from one another. In (I), the mol­ecules are linked into chains by a single N—H⋯N hydrogen bond [H⋯N = 2.15 Å, N⋯N = 3.029 (2) Å and N—H⋯N = 153°] and these chains are linked into sheets by means of aromatic π–π stacking interactions. There is one intramolecular O—H⋯O hydrogen bond in (II), and a combination of one three‐centre N—H⋯(N,O) hydrogen bond [H⋯N = 2.46 Å, H⋯O = 2.31 Å, N⋯N = 3.190 (2) Å, N⋯O = 3.146 (2) Å, N—H⋯N = 138° and N—H⋯O = 154°] and one two‐centre C—H⋯O hydrogen bond [H⋯O = 2.46 Å, C⋯O = 3.405 (2) Å and C—H⋯O = 173°] links the mol­ecules into sheets. In (III), an intramolecular O—H⋯N hydrogen bond and two N—H⋯O hydrogen bonds [H⋯O = 2.26 and 2.10 Å, N⋯O = 2.975 (2) and 2.954 (2) Å, and N—H⋯O = 138 and 163°] link the molecules into sheets.     

2‐Amino‐5‐nitro­thia­zole monoethanol solvate: triply‐interwoven hydrogen‐bonded sheets containing centrosymmetric R(8) and R(38) rings

2‐Amino‐5‐nitro­thia­zole crystallizes from solution in ethanol as a monosolvate, C₃H₃N₃O₂S·C₂H₆O, in which the thia­zole component has a strongly polarized molecular–electronic structure. The thia­zole mol­ecules are linked into centrosymmetric dimers by paired N—H⋯N hydrogen bonds [H⋯N = 2.09 Å, N⋯N = 2.960 (6) Å and N—H⋯N = 169°], and these dimers are linked by the ethanol mol­ecules, via a two‐centred N—H⋯O hydrogen bond [H⋯O = 1.98 Å, N⋯O = 2.838 (5) Å and N—H⋯O = 164°] and a planar asymmetric three‐centred O—H⋯(O)₂ hydrogen bond [H⋯O = 2.07 and 2.53 Å, O⋯O = 2.900 (5) and 3.188 (5) Å, O—H⋯O = 169 and 136°, and O⋯H⋯O = 55°], into sheets built from alternating (8) and (38) rings. These sheets are triply interwoven.     

2‐[(2‐Hydro­xy‐4‐nitro­phenyl)­amino­methyl­ene]­cyclo­hexa‐3,5‐dien‐1(2H)‐one

The title compound, C₁₃H₁₀N₂O₄, adopts the keto–amine tautomeric form and displays an intramolecular N—H⋯O [N⋯O = 2.579 (2) Å] and three intermolecular O—H⋯O [O⋯O = 2.561 (2) Å] and C—H⋯O [C⋯O = 3.274 (2) and 3.318 (2) Å] hydrogen bonds. The keto–amine structure is favoured by through‐mol­ecule conjugation between the hydroxy O atom and imine N atom. The dihedral angle between the planes of the two aromatic rings is 10.79 (4)°.     

A three‐dimensional supramolecular network built with the zigzag chain complex bis(5‐carboxy‐1H‐imidazole‐4‐carboxyl­ato)copper(II)

In the title complex, poly[copper(II)‐di‐μ‐5‐carboxy‐1H‐imidazole‐4‐carboxyl­ato], [Cu(C₅H₃N₂O₄)₂]_n or [Cu(H₂Imda)₂]_n, each imidazole moiety is bonded to the Cu atom via O and N atoms to give a square‐planar coordination [Cu—O = 2.014 (2) and 2.016 (2) Å, and Cu—N = 1.982 (3) and 1.992 (2) Å]. The distorted square‐pyramidal geometry at the Cu atom results from coordination to an adjacent O atom [Cu—O = 2.305 (2) Å], which generates zigzag chains. There is a sixth, weaker, octahedral coordination to the Cu atom from an inversion‐related O atom [Cu—O = 3.090 (2) Å], which links the chains into sheets in the (100) plane. Imidazole moieties in the sheets are linked in the [100] direction by pairs of N—H⋯O and C—H⋯O hydrogen bonds, thus generating a three‐dimensional network.     

Molecular and Low‐dimensional Coordination Compounds of Copper(II) and 3, 5‐Dimethylpyrazole — Synthesis,Crystal Structure,and Properties

Three 3, 5‐dimethylpyrazole (pz*) copper(II) complexes, [Cu(pz*)₄(H₂O)](ClO₄)₂ ( 1 ), [Cu(pz*)₂(NCS)₂]·H₂O ( 2 ), and [Cu(pz*)₂(OOCCH=CHCOO)(H₂O)]·1.5H₂O ( 3 ), have been synthesized and characterized with single crystal X‐ray structure analysis. 1 crystallizes in the tetragonal space group, 14/m, with a = 14.027 (3) Å, c = 16.301 (5) Å, and Z = 4. 2 crystallizes in the monoclinic space group, P2₁/c, with a = 8.008 (3) Å, b = 27.139 (9) Å, c = 8.934 (3) Å, β = 106.345 (6)°, and Z = 4. 3 crystallizes in the triclinic space group, P1¯, with a = 7.291 (9) Å, b = 10.891 (13) Å, c = 11.822 (14) Å, α = 80.90 (2)°, β = 79.73(2)°, γ = 70.60(2)°, and Z = 2. In 1 , one water molecule and four pz* ligands are coordinated to Cu^II. Two [Cu(pz*)₄(H₂O)]²⁺ units are connected to ClO₄^— via hydrogen bonds. One lattice water molecule is found in the unit cell of 2 , which forms an one‐dimensional chain via intermolecular hydrogen bonds with the N‐H atom of pz*. In 3 , the oxygen atom of the coordinated water molecule is connected with two C=O groups of two neighbouring maleic acid molecules to form a linear parallelogram structure. Another C=O group of maleic acid forms a hydrogen bond with the N‐H atom of pz* to create a two‐dimensional structure. The spectroscopic and bond properties are also discussed.     

6‐Amino‐3‐methyl‐5‐nitro­so­pyrimi­dine‐2,4(1H,3H)‐dione forms a three‐dimensional hydrogen‐bonded framework structure

Molecules of the title compound, C₅H₆N₄O₃, are linked into a single three‐dimensional framework by a two‐centre N—H⃛O hydrogen bond [H⃛O = 1.92 Å, N⃛O = 2.785 (2) Å and N—H⃛O = 168°], a two‐centre N—H⃛H hydrogen bond [H⃛N = 2.19 Å, N⃛N = 3.017 (2) Å and N—H⃛N = 157°] and the intermolecular component of an effectively planar three‐centre N—H⃛(O)₂ hydrogen bond [H⃛O = 2.03 and 2.31 Å, N⃛O = 2.645 (2) and 2.957 (2) Å, N—H⃛O = 126 and 130°, and O⃛H⃛O = 101°].     

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.     

4‐Iodo­anilinium 3‐nitro­phthalate(1–): tripartite sheets built from O—H...O and N—H...O hydrogen bonds

In the title compound, 4‐iodoanilinium 2‐carboxy‐6‐nitrobenzoate, C₆H₇IN⁺·C₈H₄NO₆⁻, the anions are linked by an O—H...O hydrogen bond [H...O = 1.78 Å, O...O = 2.614 (3) Å and O—H...O = 171°] into C(7) chains, and these chains are linked by two two‐centre N—H...O hydrogen bonds [H...O = 1.86 and 1.92 Å, N...O = 2.700 (3) and 2.786 (3) Å, and N—H...O = 153 and 158°] and one three‐centre N—H...(O)₂ hydrogen bond [H...O = 2.02 and 2.41 Å, N...O = 2.896 (3) and 2.789 (3) Å, N—H...O = 162 and 105°, and O...H...O = 92°], thus forming sheets con­taining R(6), R(8), R(13) and R(18) rings.     

catena‐Poly­[[(di‐2‐pyridyl­amine)­silver(I)]‐μ‐nicotinato] and catena‐poly­[[(di‐2‐pyridyl­amine)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato]

In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐nico­tinato‐κ²N:O], [Ag(C₆H₄NO₂)(C₁₀H₉N₃)]_n, the Ag^I atom is tetracoordinated by two N atoms from the di‐2‐pyridyl­amine (BPA) ligand [Ag—N = 2.3785 (18) and 2.3298 (18) Å] and by one N atom and one carboxyl­ate O atom from nicotinate ligands [Ag—N = 2.2827 (15) Å and Ag—O = 2.3636 (14) Å]. Bridging by nicotinate N and O atoms generates a polymeric chain structure, which extends along [100]. The carboxyl O atom not bonded to the Ag atom takes part in an intrachain C—H⋯O hydrogen bond, further stabilizing the chain. Pairs of chains are linked by N—H⋯O hydrogen bonds to generate ribbons. There are no π–π interactions in this complex. In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato‐κ²O¹:O²], [Ag(C₇H₅O₄)(C₁₀H₉N₃)]_n, the Ag^I atom has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand [Ag—N = 2.286 (5) and 2.320 (5) Å] and to one carboxyl­ate O atom from the 2,6‐di­hydroxy­benzoate ligand [Ag—O = 2.222 (4) Å]; the fourth, weaker, Ag‐atom coordination is to one of the phenol O atoms [Ag⋯O = 2.703 (4) Å] of an adjacent moiety, and this interaction generates a polymeric chain along [100]. Pairs of chains are linked about inversion centers by N—H⋯O hydrogen bonds to form ribbons, within which there are π–π interactions. The ribbons are linked about inversion centers by pairs of C—H⋯O hydrogen bonds and additional π–π interactions between inversion‐related pairs of 2,6‐di­hydroxy­benzoate ligands to generate a three‐dimensional network.     

Dichloro(isopropylamido)bis(iso­propylamine)(isopropylimido)­tantalum(V), a monomeric TaV compound with imido,amido and amino moieties

The title compound, [Ta(C₃H₇N)(C₃H₈N)Cl₂(C₃H₉N)₂], is the first monomeric example of a metal complex that features imido, amido and amino moieties in the same mol­ecule. The Ta atom has distorted octahedral coordination, with the imido moiety trans to chlorine and the pseudo‐axial ligands bent away from the imido moiety. Principal dimensions include Ta=N = 1.763 (8) Å, Ta—N(H) = 1.964 (7) Å, and Ta—N(H₂) = 2.247 (7) and 2.262 (7) Å.     

trans‐Bis(dimethyl sulfoxide‐κO)bis(3‐oxo‐3,4‐dihydroquinoxaline‐2‐carboxylato‐κ2N1,O2)copper(II)

The title compound, [Cu(C₉H₅N₂O₃)₂(C₂H₆OS)₂], consists of octahedrally coordinated Cu^II ions, with the 3‐oxo‐3,4‐dihydroquinoxaline‐2‐carboxylate ligands acting in a bidentate manner [Cu—O = 1.9116 (14) Å and Cu—N = 2.1191 (16) Å] and a dimethyl sulfoxide (DMSO) molecule coordinated axially via the O atom [Cu—O = 2.336 (5) and 2.418 (7) Å for the major and minor disorder components, respectively]. The whole DMSO molecule exhibits positional disorder [0.62 (1):0.38 (1)]. The octahedron around the Cu^II atom, which lies on an inversion centre, is elongated in the axial direction, exhibiting a Jahn–Teller effect. The ligand exhibits tautomerization by H‐atom transfer from the hydroxyl group at position 3 to the N atom at position 4 of the quinoxaline ring of the ligand. The complex molecules are linked through an intermolecular N—H...O hydrogen bond [N...O = 2.838 (2) Å] formed between the quinoxaline NH group and a carboxylate O atom, and by a weak intermolecular C—H...O hydrogen bond [3.392 (11) Å] formed between a carboxylate O atom and a methyl C atom of the DMSO ligand. There is a weak intramolecular C—H...O hydrogen bond [3.065 (3) Å] formed between a benzene CH group and a carboxylate O atom.     

Non‐Isomorphic Chlorine—Bromine Substitution in the Copper(I) Halide π‐Complexes with 1‐Allyl‐4‐aminopyridinium

By alternating‐current electrochemical synthesis crystals of {Cu[H₂NC₅H₄N(C₃H₅)]Br₂} ˙ H₂O ( I ), {Cu[H₂NC₅H₄N(C₃H₅)]Br_0.65Cl_1.35} ˙ H₂O ( II ) and {Cu[H₂NC₅H₄N(C₃H₅)]Cl₂} ( III ) π‐complexes have been obtained and structurally investigated. The I and II compounds are isostructural and crystallize in a monoclinic sp. gr. P2₁/c, I : a = 7.359(2)Å, b = 12.3880(6)Å, c = 13.637(3)Å, β = 107.03(1)°, V = 1188.7(4)ų, Z = 4 for C₈H₁₃N₂OBr₂Cu composition, R = 0.0293 for 2140 reflections. II : a = 7.2771(6)Å, b = 12.3338(3)Å, c = 13.4366(7)Å, β = 107.632(2)°, V = 1149.3(1)ų, Z = 4 for C₈H₁₃N₂Br_0.65Cl_1.35Cu composition, R = 0.0463 for 2185 reflections. Metal and halogen atoms form centrosymmetric Cu₂X₄ dimers. Each copper atom is surrounded by three halogen atoms and by a weakly bonded C=C‐group of the onium moiety. Isolated {Cu[H₂NC₅H₄N(C₃H₅)]}₂X₄ dimers are combined into a three‐dimensional network due to a bridging function of water molecules via a system of rather strong hydrogen bonds. Chlorine derivative III crystallizes in another structure type: sp. gr. C2/c, a = 21.568(7)Å, b = 7.260(2)Å, c = 13.331(3)Å, β = 95.65(2)°, V = 2077(2)ų, Z = 8 for C₈H₁₁N₂Cl₂Cu composition. Copper atom, included in CuCl₂^— isolated fragment, is coordinated to a C=C‐bond of ligand moiety. N‐H…Cl hydrogen bonds unite Cu[H₂NC₅H₄N(C₃H₅)]Cl₂ subunits into infinite ribbons. π‐Interaction in III appears to be more effective than in I and II .     

Di­chloro­(methanol‐κO)[(methoxy)tris(1‐methyl‐1H‐imidazol‐2‐yl)­methane‐κ2N3]­iron(II) (ca 153 K)

In the quasi‐trigonal–bipyramidal environment of the five‐coordinate Fe^II atom in the title compound, [FeCl₂(C₁₄H₁₈N₆O)(CH₄O)], the methanol and one of the N‐atom donors of the potentially tridentate ligand are disposed axially: Fe—N(axial) is 2.149 (2) Å, Fe—N(equatorial) is 2.108 (2) Å and N—Fe—O is 174.14 (7)°.     

Bis­(acetato‐O)­tetrakis­(imidazole‐N3)­nickel(II)

In the title compound, [Ni(C₂H₃O)₂(C₃H₄N₂)₄], the Ni atom is coordinated centrosymmetrically by four N and two O atoms in an octahedral coordination [Ni—N = 1.986 (3) and 2.054 (3) Å; Ni—O = 2.697 (3) Å]. The O atoms of the acetate anions form hydrogen bonds to adjacent imidazole moieties, with the free O atom forming a somewhat shorter bond [N?O = 2.679 (3) and 2.870 (4) Å]. The hydrogen bonds give rise to a two‐dimensional layer structure.     

4,4′‐Tri­methyl­enedipyridinium bis­[carboxy­methyl­phos­pho­nate(1–)]: a three‐dimensional framework structure built from O—H⃛O,N—H⃛O and C—H⃛O hydrogen bonds

In the title compound, C₁₃H₁₆N₂²⁺·2C₂H₄O₅P⁻, the cation lies across a twofold rotation axis in space group Fdd2. The anions are linked into molecular ladders by two O—H⃛O hydrogen bonds [H⃛O = 1.73 and 1.77 Å, O⃛O = 2.538 (2) and 2.598 (3) Å, and O—H⃛O = 160 and 170°], these ladders are linked into sheets by a single type of N—H⃛O hydrogen bond [H⃛O = 1.75 Å, N⃛O = 2.624 (3) Å and N—H⃛O = 171°] and the sheets are linked into a three‐dimensional framework by a single type of C—H⃛O hydrogen bond [H⃛O = 2.48 Å, C⃛O = 3.419 (4) Å and C—H⃛O = 167°].     

Bis­[bis­(pyrimidin‐2‐yl‐κN)­amine](dicyan­amido‐κN1)(tri­fluoro­methanesulfonato‐κO)copper(II) ethanol hemisolvate forms a hydrogen‐bonded chain

In the crystal structure of [Cu(CF₃SO₃)(C₂N₃)(C₈H₇N₅)₂]·0.5C₂H₆O, the Cu^II atom adopts a distorted octahedral geometry, with the basal plane formed by two N atoms of one dipyrimidinyl­amine ligand, one N atom of the second pyrimidine ligand and a nitrile N atom of the dicyan­amide anion [Cu—N = 1.972 (2)–2.021 (2) Å]. The apical positions are occupied by an N atom of the second ligand [Cu—N = 2.208 (2) Å], and an O atom of the tri­fluoro­methane­sulfonate anion [Cu—O = 2.747 (2) Å] at a semi‐coordination distance. Pairs of inversion‐related N—H⋯N hydrogen bonds of the so‐called Watson–Crick type, augmented by two C—H⋯N contacts, link adjacent complexes into an infinite one‐dimensional chain running in the [101] direction.