Syntheses and structures of adducts of stoichiometry MX:dpex (2:1)(n), M = Cu, Ag, X = (pseudo-) halogen, dppx = Ph2E(CH2)xEPh2, E = P, As

Single crystal X-ray studies have defined the structures of a number of adducts of the form MX:dpex (2:1), M = univalent coinage metal (Cu, Ag), X = (pseudo-)halide, dpex = bis(diphenylpnicogeno)alkane, Ph₂E(CH₂)_xEPh₂, E = P, As, of diverse types, some novel. The adducts of AgCl,Br:dppm and AgNCO:dpem (x = 1) are tetranuclear as is the AgNO₃:dppp (x = 3) array, all derivative of the familiar ‘step’ structure while the combination CuCN:dppm yields a two-dimensional web of twenty-membered macro/metallacycles. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solution (¹H, ¹³C, ³¹P NMR, ESI MS) and in the solid state (IR).     

The structural definition of adducts of stoichiometry MX:dpex (2:3)(∞), M = Cu, Ag, X = simple anion, dpex = Ph2E(CH2)xEPh2, E = P, As

Single crystal X-ray structural characterizations are recorded for a number of adducts of MX:dpex (2:3) stoichiometry (MX = simple univalent copper or silver salt; dpex = Ph₂E(CH₂)_xEPh₂ (E = P, As)). CuX:dppe (2:3) (X = Cl, Br, I, CN) are binuclear [(dppe-P,P′)CuX(P-dppe-P′)CuX(P,P′-dppe)], all centrosymmetric. AgX:dpex (2:3) (dpex = ‘dpae’ (Ph₂As(CH₂)₂AsPh₂), X = Br, F₃CCO₂ (= ‘tfa’), F₃CSO₃ (≡ ‘tfs’); dpex = ‘dpape’ (Ph₂As(CH₂)₂PPh₂), X = CN, SCN, OClO₃) are one-dimensional polymers ?-E′)₁AgX(E-dpex-E′)₂-AgX(E-dpex-E′)₁AgX?, P, As sites scrambled in the latter. AgNO₃:dpam (2:3) is also a one-dimensional polymer, ?AgO·NO·OAg(As-dpam-As)AgO·NO·OAg? (‘dpam’ ≡ Ph₂As(CH₂)₂AsPh₂). AgX:dpae (2:3) (X = I, CN, ClO₄, NO₃) and AgX:dpape (2:3) (X = Br, I, NO₃) are two-dimensional polymers with large 30-membered macrocyclic rings; similar webs are found for dppx ligands in AgOH:dppb (2:3) and AgNCO, Agtfa:dpph (2:3) with 42- and 54-membered rings. Complexes AgX:dpape (1:3) (X = Cl, Br) are defined as mono-nuclear [XAg(Ph₂P(CH₂)₂AsPh₂)₃] arrays, the unidentate ligands predominantly P-bound. Synthetic procedures for the adducts are reported, selected compounds being characterized both in solution (¹H, ³¹P NMR, ESI MS) and in the solid state (IR).     

New oligo-/poly-meric forms for MX:dpex (1:1) complexes (M = Cu, Ag; X = (pseudo-)halide; dpex = Ph2E(CH2)xEPh2, E = (P), As; x = 1, 2)

Single-crystal X-ray structural characterizations of MX:dpam (1:1) (‘dpam’ = Ph₂AsCH₂AsPh₂) are reported for MX = AgCl, Br; CuI, CN/Cl (all isomorphous) and AgI, AgSCN, CuSCN arrays, all being of the novel form [(μ-X){M(μ-X)(As-dpam-As′)₂M′}]_∞, essentially the familiar M(E-dpem-E′)₂M′ binuclear array with both ‘bridging’ and (linking) ‘terminal’ (pseudo-)halides involved in the polymer. A different arrangement of bridging and linking entities is found with AgX:dpae (1:1)_2(∞|∞), X = Br, NCO, ‘dpae’ = Ph₂As(CH₂)₂AsPh₂, now comprising [M(μ-X)₂(As-dpae-As)M] kernels linked by As-dpae-As′, while in the thiocyanate analogue units are linked by the dpae ligands into a two-dimensional web. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solution (¹H, ¹³C, ³¹P NMR, ESI MS) and in the solid state (IR).     

The structural definition of adducts of stoichiometry AgX:dppf (1:1)(n), X = simple anion, dppf = bis(diphenylphosphino)ferrocene

Single crystal X-ray structural characterizations are recorded for an array of adducts of the form AgX:dppf (1:1)_(n), X = simple (pseudo-)halide or oxy-anion, ‘dppf’ = bis(diphenyl phosphino)ferrocene, for adducts X = Cl (new phase), Br, I, SCN, OCN, CN, NO₃ (new phase), O₂CCH₃, n = 2, the form being dimeric [(dppf-P,P′)Ag(μ-X)₂Ag(P,P′-dppf)], for X = I, SCN, [Ag(μ-X)₂(P-dppf-P′)₂Ag′]; for X = O₂CCF₃, n = ∞, the form is an extended polymer: ?Ag(O · CO · CF₃)(P-dppf-P′)Ag′(O?. A dichloromethane solvate phase of CuI:dppf (1:1)₂ (also centrosymmetric) is also recorded. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solution (¹H, ¹³C, ³¹P NMR, ESI MS) and in the solid state (IR). The topology of the structures in the solid state was found to depend on the nature of the counterion.     

Transition metal halide salts of 8-methylquinolinium: Synthesis and structures of (8-methylquinolinium)2 MX4·nH2O (M = Cu, Co, Zn; X = Cl, Br; n = 0, 1)

The reactions of metal(II) chlorides and bromides with 8-methylquinoline (8-mequin) in neutral and acidic solutions were investigated. The reaction with ZnCl₂, ZnBr₂, CoCl₂, CoBr₂, CuCl₂ or CuBr₂ with the appropriate HX in water or aqueous ethanol gave complexes of the formula (8-mequin)₂MX₄ (1, M = Cu, X = Cl; 2, M = Cu, X = Br; 3, M = Co, X = Cl; 4, M = Co, X = Br) or (8-mequin)₂ZnX₄·nH₂O (5, X = Cl, n = 0; 6, X = Br, n = 0; 7, X = Cl, n = 1; 8, X = Br, n = 1). Crystals of 1, 2 and 4-8 suitable for single crystal X-ray diffraction were obtained and the structures reported. Compounds 1 and 2 crystallize in the monoclinic space group C2/c, while 4-8 crystallize in the triclinic space group, . Variable temperature magnetic susceptibility data indicate very weak interactions for the copper compounds 1 and 2, while the magnetic behavior of 3 and 4 is dominated by single ion anisotropy, with weaker antiferromagnetic interactions.     

Synthesis, spectroscopic and structural characterization of adducts of stoichiometry CuX:dppe (1:2) (X = I, ClO4, BH4, O3SCF3, SCN, dppe = Ph2P(CH2)2PPh2)

Syntheses and spectroscopic features (IR, NMR and ESI MS) are reported for five 1:2 adducts of CuX with dppe (X = I, ClO₄, NCS, O₃SCF₃ (tfs) BH₄; dppe = Ph₂P(CH₂)₂PPh₂). ESI MS and ³¹P NMR spectroscopy indicate that these species dissociate in solution yielding free diphosphine and 3:2 species. A single crystal X-ray structure determination has been carried out on Cu(dppe)₂NCS defining a four-coordinate complex of the form [(P,P′-dpex)M(P-dpex)X] for M = Cu, the thiocyanate being N-bound; the ionic [Cu(P,P′-dppe)₂]tfs has also been structurally characterized.     

Hydrothermal syntheses and structures of a novel zincophosphite, [C6N2H18] · [Zn3(HPO3)4]

A novel three-dimensional organically templated zincophosphite, [C₆N₂H₁₈] · [Zn₃(HPO₃)₄], was synthesized under milder hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction, differential thermal-thermogravimetric analysis, powder X-ray diffraction, ³¹P MAS NMR spectrum, and IR spectroscopy. It crystallizes in the monoclinic system, space group C2/c with cell parameters: a = 8.7820(4) Å, b = 14.9417(7) Å, c = 15.4943(5) Å, β = 92.940(2)°, and Z = 4. The structure consists of a network of strictly alternating ZnO₄ tetrahedra and pseudo-pyramid, forming 4-membered ring chains. The structure has a 4.8.16-net and 8- and 16-membered ring channels where completely protonated N,N,N′,N′-tetramethylenediamine cations are encapsulated. The structure is stabilized by template-to-framework hydrogen bonding. In phosphites system, this compound possesses extra-large-pores.     

The structural definition of adducts of stoichiometry MX:dppx (1:1) M = Cu, Ag, X = simple anion, dppx=Ph2P(CH2)xPPh2, x = 3-6

Single crystal X-ray structural characterizations are recorded for a wide range of adducts of the form MX:dppx (1:1)_(n), M = silver(I) (predominantly), copper(I), X = simple (pseudo-) halide or oxy-anion (the latter spanning, where accessible, perchlorate, nitrate, carboxylate - a range of increasing basicity), dppx=bis(diphenylphosphino)alkane, Ph₂P(CH₂)_xPPh₂, x = 3-6. Adducts are defined of two binuclear forms: (i) [LM(μ-X)₂L], with each ligand chelating a single metal atom, and (ii) [M(μ-X)₂(μ-(P-L-P′))₂M′] where both ligands L and halides bridge the two metal atoms; a few adducts are defined as polymers, the ligands connecting M(μ-X)₂M′ kernels, this motif persisting in all forms. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solution (¹H, ¹³C, ³¹P NMR, ESI MS) and in the solid state (IR).     

Synthesis and characterization of Fe(III)(3-CH3O-qsal)2PF6 · nH2O (n = 0, 2)

Compounds Fe^III(3-CH₃O-qsal)₂PF₆ · nH₂O (n = 0, 2) (1, 1 · 2H₂O) were synthesized and characterized: the structure of 1 and the magnetic properties of both compounds were determined. Compound 1 · 2H₂O presents properties characteristic of high-spin Fe(III), while 1 presents properties of low-spin Fe(III) with an onset of a gradual spin crossover at ca. 300 K.     

BEDT-TTF salts of the unsymmetrical [M(tfadt)2] dithiolene complexes (M = Ni, Au; tfadt = S2C2(CN)(CF3))

Two closely related 1:1 salts are obtained upon electrocrystallization of BEDT-TTF (BEDT-TTF: bis(ethylenedithio)tetrathiafulvalene) in the presence of the isosteric [M(tfadt)₂]⁻ dithiolene complexes (tfadt: 1-trifluoromethyl-2-cyano-1,2-dithiolato), which essentially differ by their spin state, S = 0 in [Au(tfadt)₂]⁻, S = 1/2 in [Ni(tfadt)₂]⁻. In both [BEDT-TTF][M(tfadt)₂] salts, the BEDT-TTF radical cations form chains with a strong lateral overlap and strong antiferromagnetic interactions while the paramagnetic anions in the nickel-containing salt [BEDT-TTF][Ni(tfadt)₂] are essentially non-interacting. The structural differences between the nickel and gold complexes are analyzed and discussed.     

Syntheses, spectroscopic and structural characterization of some (solvated) binuclear adducts of the form Ag(oxyanion):dpem(:S) (1:1(:x))2 (oxyanion = ClO4, F3CCO2, F3CSO3; dpem = Ph2E(CH2)EPh2 (E = P, As))

Syntheses, spectroscopic (IR, NMR and ESI MS) and single crystal X-ray structural characterizations are reported for a wide variety of adducts of Ag(oxyanion):dpem(:S) (1:1(:n))₂ (oxyanion = ClO₄, F₃CCO₂ (tfa) F₃CSO₃ (tfs); dpem = Ph₂E(CH₂)EPh₂) stoichiometry among which the basic Ag(Ph₂E(CH₂)EPh₂)₂Ag core is diversely perturbed by interactions with anions and solvent molecules. ESI MS and ³¹P NMR spectroscopy indicated that dinuclear species also exist in solution.     

Hydrothermal synthesis and structure of a Cu(I) bromide coordination polymer, [(tpyprz)3Cu10Br10] (tpyprz = tetra-2-pyridylpyrazine)

The hydrothermal reaction of CuBr₂ and tpyprz in the presence of NH₄VO₃ and HF for 72 h at 170 °C provided [(tpyprz)₃Cu₁₀Br₁₀] (1) in 20% yield. The two-dimensional structure of 1 may be described as Cu(I)-tpyprz chains, linked through {Cu₄Br₅}⁻ clusters in the ac-plane and decorated with {Cu₃Br₅}²⁻ clusters projecting from one face of the layer in the b-direction. The Cu(I) sites exhibit distorted trigonal coordination {CuBr₃} and distorted tetrahedral geometries, {CuBr₂N₂} and {CuN₄}. Crystal data for 1: monoclinic space group C2, a = 12.7561(8) Å, b = 19.359(1) Å, c = 15.860(1) Å, β = 97.178(1)°, V = 3885.8(4) Å³, Z = 2, D_calc = 2.222 g cm⁻³, μ(Mo Kα) = 78.75 cm⁻¹.     

Synthesis and structural characterization of adducts of silver(I) carboxylate salts AgX (X = CF3COO, CH3COO) with ER3 (E = P, As; R = Ph, cy, o-tolyl) and oligodentate aromatic bases derivative of 2,2′-bipyridyl, L, AgX:PR3:L (1:1:1)

Twenty-one adducts of the form AgX:ER₃:L (1:1:1) (X = CF₃COO (‘tfa’), CH₃COO (‘ac’), E = P, As; R = Ph, cy, o-tolyl; L = 2,2′-bipyridyl (‘bpy’)-based ligand) have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, ¹H, ¹⁹F and ³¹P NMR) and single crystal X-ray diffraction studies. The resulting complexes are predominantly of the form [(R₃E)AgL]⁺X⁻, with a trigonal EAgN₂ coordination environment, the planarity of which may be perturbed by the approach of anion or solvent. The carboxylate anions have been found to be uni-, or semi-bidentate, or also completely ionic, as in the complexes [Ag(PPh₃)(bpy)(H₂O)](tfa) and [Ag(PPh₃)(dpk · H₂O)](tfa) (‘dpk · H₂O’ = bis(2-pyridyl)ketone (hydrated)). The complexes Agac:PPh₃:dpa (1:1:1) and Agac:P(o-tol)₃:dpa:MeCN (1:1:1:1) are dinuclear, with bridging unidentate acetate and terminal unidentate dpa (‘dpa’ = bis(2-pyridyl)amine).     

Hydrothermal synthesis and characterization of a new inorganic-organic hybrid compound AMP[ZnCl3] (AMP = 2-aminomethylpyridinium)

A novel organic-inorganic hybrid complex [(2-NH₂CH₂C₅H₄N)ZnCl₃] has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, thermal analysis and spectroscopic studies. The compound crystallizes in the triclinic system, space group , a = 7.5339(9), b = 7.589(2), c = 9.365(2) Å, α = 104.55(2)°, β = 97.22(1)°, γ = 87.88(2)°, V = 513.6(2), Z = 2. In the title compound the 2-aminomethylpyridine acts as a ligand covalently linked to Zn(II) cation to form a slightly distorted ZnCl₃N tetrahedral environment. Each [Zn(C₆H₈N₂)Cl₃] unit is connected to one neighbor by a pair of hydrogen bonds between the apical chlorides and amine hydrogen atoms and to the other by a couple of π-π stacking interactions between the aromatic rings of the coordinated ligands forming a novel one-dimensional chain-like arrangement. The title complex is the first one that contains both coordinated and hydrogen bonded 2-aminomethylpyridine. Solid state ¹³C and ¹⁵N CP-MAS-NMR spectroscopies are in agreement with the X-ray structure. Ab initio calculations allow the attribution of carbons and nitrogen to the independent crystallographic sites. The Raman spectroscopy confirmed the presence of Zn-Cl and Zn-N bonds.     

Heterobimetallic Fe-Pd and Fe-Pt NCN pincer complexes (NCN = [C6H2(CH2NMe2)2-2,6])

The meta-diaminoaryl ferrocenes Fc-NCN-H (3) and Fc-CC-NCN-H (5) (Fc = (η⁵-C₅H₅)(η⁵-C₅H₄)Fe, NCN-H = C₆H₃(CH₂NMe₂)₂-3,5) can be used as precursors in the preparation of heterobimetallic transition metal complexes of structural type Fc-NCN-MX (NCN = [C₆H₂(CH₂NMe₂)₂-2,6]⁻; MX = PdCl (7), PtCl (8), PtI (9)) and Fc-CC-NCN-MX (MX = PdCl (11), PdI (12), PtCl (13)), respectively. They are accessible by applying different synthesis procedures, including oxidative addition and metallation-transmetallation processes.Cyclovoltammetric studies show that the ferrocene moieties in 3, 5, 7-9 and 11-13 can reversibly be oxidised. The potential of the Fe(II)/Fe(III) redox couple decreases with increasing electron density at the NCN pincer unit. The use of 8 as a possible (electro)chemical sensor in the detection of SO₂ is discussed as well.The solid-state structures of 8 and 13 are reported. The crystals of 8 contain two molecules of 8 in the asymmetric unit. The plane of the C₆H₂ moiety is with 27.2(3)° and 38.2(3)° tilted towards the C₅H₄ entity, while in 13 an angle of 45.9(3)° can be found. The d⁸-electron configured platinum atoms possess a somewhat distorted square-planar surrounding, setup by two Me₂NCH₂ortho-substituents, the NCN C_ipso carbon atom and the chloride ligand.     

Preparation, crystal structures and spectroscopic properties of novel [MCl3 − n(P)3 + n] (M = Co, Rh; n = 0, 1, 2 or 3) series of complexes containing tripodal tridentate phosphine, 1,1,1-tris(dimethylphosphinomethyl)ethane

Cobalt(III) and rhodium(III) complexes of the series of [M^IIICl_3 − n(P)_3 + n]ⁿ⁺ (M = Co or Rh; n = 0, 1, 2 or 3) have been prepared with the use of 1,1,1-tris(dimethylphosphinomethyl)ethane (tdmme) and mono- or didentate phosphines. The single-crystal X-ray analyses of both series of complexes revealed that the M-P and M-Cl bond lengths were dependent primarily on the strong trans influence of the phosphines, and secondarily on the steric congestion around the metal center resulting from the coordination of several phosphine groups. In fact, the M-P(tdmme) bonds became longer in the order of [MCl₃(tdmme)] < [MCl₂(tdmme)(PMe₃)]⁺ < [MCl(tdmme)(dmpe)]²⁺ (dmpe = 1,2-bis(dimethylphosphino)ethane) < [M(tdmme)₂]³⁺ for both Co^III and Rh^III series of complexes, while the M-Cl bond lengths were shortened in this order (except for [M(tdmme)₂]³⁺). Such a steric congestion around the metal center can also account for the structural and spectroscopic characteristics of the series of complexes, [MCl(tdmme)(dmpm, dmpe or dmpp)]²⁺ (dmpm = bis(dimethylphosphino)methane, dmpp = 1,3-bis(dimethylphosphino)propane). The X-ray analysis for [CoCl(tdmme)(dmpm or dmpe)](BF₄)₂ showed that all Co-P bonds in the dmpm complex were shorter by 0.03-0.04 Å than those in the dmpe complex. Furthermore, the first d-d transition energy of the Co^III complexes and the ¹J_Rh-P(tdmme) coupling constants observed for the Rh^III complexes indicated an unusual order in the coordination bond strengths of the didentate diphosphines, i.e., dmpm > dmpe > dmpp.     

Meso-[{Ru(phen)2}2(μ-bpm)]: A high-affinity DNA bulge probe {bpm = 2,2′-bipyrimidine; phen = 1,10-phenanthroline}

The binding of the stereoisomers of [{Ru(Me₂bpy)₂}₂(μ-bpm)]⁴⁺, [{Ru(phen)₂}₂(μ-bpm)]⁴⁺ and [{Ru(Me₂phen)₂}₂(μ-bpm)]⁴⁺ (Me₂bpy = 4,4′-dimethyl-2,2′-bipyridine; bpm = 2,2′-bipyrimidine; phen = 1,10-phenanthroline; Me₂phen = 4,7-dimethyl-1,10-phenanthroline) to a tridecanucleotide d(CCGAGAATTCCGG)₂ which contains a single adenine bulge site, and four control dodecanucleotides, have been studied using a fluorescence intercalator displacement (FID) assay. The meso isomer of [{Ru(phen)₂}₂(μ-bpm)]⁴⁺ showed the strongest binding to the bulge-containing tridecanucleotide. In order to gain a greater understanding of the basis of the higher affinity exhibited by the meso isomer towards the bulge sequence, a ¹H NMR study of the binding of the two enantiomers (ΔΔ and ΛΛ) of rac-[{Ru(phen)₂}₂(μ-bpm)]⁴⁺, and the, meso (ΔΛ) diastereoisomer, to the tridecanucleotide d(CCGAGAATTCCGG)₂ was carried out. The NMR results suggest that the meso isomer binds selectively at the bulge site in the tridecanucleotide minor groove, but closer to the 3′-direction and with less structural perturbations of the groove than the ΔΔ and ΛΛ isomers. The results of this study confirm that dinuclear ruthenium complexes have excellent potential as DNA bulge probes, and meso-[{Ru(phen)₂}₂(μ-bpm)]⁴⁺ in particular has a high affinity (1 × 10⁶ M⁻¹) and selectivity for a single adenine bulge site.     

Nature of the Ln-Co magnetic interactions in compounds [Ln2Co3(C5H4NPO3)6] · 4H2O with open-framework structures

The reactions of Ln(NO₃)₃ · xH₂O, CoSO₄ · 7H₂O or ZnSO₄ · 6H₂O and 2-pyridylphosphonic acid under hydrothermal conditions result in heterometallic phosphonate compounds with formula [Ln₂M₃(C₅H₄NPO₃)₆] · 4H₂O (Ln₂M₃; M = Co^II or Zn^II; Ln = La^III, Ce^III, Pr^III, Nd^III, Sm^III, Eu^III, Gd^III, Tb^III, Dy^III). These compounds are isostructural and crystallize in a chiral cubic space group I2₁3. Each structure contains the {LnO₉} polyhedra and {MN₂O₄} octahedra which are connected by edge-sharing to form an inorganic open-framework structure with a 3-connected 10-gon (10, 3) topology. The nature of Ln^III-Co^II magnetic interactions in Ln₂Co₃ is investigated by a comparison with their Ln^III-Zn^II analogues. It is found that the Ln^III-Co^II interaction is weak antiferromagnetic for Ln = Ce and ferromagnetic for Ln = Sm, Gd, Tb and Dy. In the cases of Ln = Pr, Nd and Eu, no significant magnetic interaction is observed.     

Homogeneous oxidative coupling catalysts. Mechanism of catalysts formation by oxidation of [(Pip)nCuX]4 (n = 1 or 2, Pip = piperidine, X = Cl, Br or I) by dioxygen in aprotic media

This paper reports the mechanism of formation of oxidative coupling catalysts [(Pip)_nCuX]₄O₂, n = 1 or 2 and X = Cl, Br or I, which represent half of the catalytical cycle, Scheme 1. The mechanism has been described as a pre-equilibrium between [(Pip)_nCuX]₄ and O₂. K values are very sensitive to how strong the hydrogen-bonding between copper (I) tetranuclear and incoming dioxygen is, such association is also sensitive to the variation of X. The pronounced pre-equilibrium is the reason behind the oxidation of [(Pip)_nCuI]₄, which is not the case for pyridine type of ligands. The pre-equilibrium followed by rate determining step k₂, which is responsible to the formation of the oxidative coupling catalysts [(Pip)_nCuX]₄O₂. The overall reaction is a second-order process, first order in each [[(Pip)_nCuX]₄] and [O₂], with rate constant k_on (k_on = Kk₂) and exothermic ΔH^≠ varying from −3 to −12 kcal mol⁻¹ and ΔS^≠ varying from −87 to −65 cal deg⁻¹ mol⁻¹. k_on were found to be very sensitive to n value 1 or 2 and to the type of X (Cl, Br or I).     

Spin crossover in a mononuclear compound [Fe(EPPA)(bpym)](ClO4)2 (EPPA = N-(2-aminoethyl)-N-(3-aminopropyl)-2-(aminomethyl)pyridine, bpym = 2,2′-bipyrimidine): Synthesis, structure, and magnetic properties

The synthesis, magnetic properties and single crystal study of a new spin crossover compound [Fe(EPPA)(bpym)](ClO₄)₂ with EPPA = N-(2-aminoethyl)-N-(3-aminopropyl)-2-(aminomethyl)pyridine, bpym = 2,2′-bipyrimidine are reported. Variable-temperature magnetic susceptibility data collected in the temperature range 10-294 K reveal the occurrence of a relatively cooperative spin transition with T_1/2 = 108 K. The crystal structure of [Fe(EPPA)(bpym)](ClO₄)₂ was determined by single-crystal X-ray diffraction method. The structure of the complex consists of mononuclear [Fe(EPPA)(bpym)](ClO₄)₂ units. The potentially bis-bidentate bpym ligand acting as a bidentate one, is coordinated to iron(II) in cis-position by two nitrogen atoms. The four remaining positions in the pseudooctahedral [FeN₆] core are occupied by one pyridinic and three aliphatic nitrogens of the EPPA ligand. The network of cooperative links in the crystal lattice is represented by H-bonding and π stacking interactions.