A new zinc complex [Zn(L1)Cl2]2?CH3OH?2H2O (complex 1), where L1 stands for 2,6-Bis{[(4-ethylphenyl)imino]ethyl}pyridine (L1) has been synthesized and characterized. The crystal structure of L1 and complex 1 have been determined by single-crystal X-ray diffraction. Both compounds crystallize in the monoclinic P21/c space group. For the ligand L1, the crystal parameters are a?=?16.7487(7) Å, b?=?5.8177(3) Å, c?=?21.8427(10) Å, β?=?104.1350(10)° and Z?=?4. For complex 1, the crystal parameters are a?=?8.0216(14) Å, b?=?13.433(2) Å, c?=?24.640(4) Å, β?=?90.223(3)° and Z?=?2. In the crystal structure of complex 1, L1 acts as a tridentate ligand and coordinated with Zn1 with three nitrogen atoms. Together with two chlorine atoms, Zn1 atom is five-coordinated in a trigonal bipyramidal geometry. Hydrogen bonds play great role in the crystal structure of complex 1 and form a two-dimensional network. Furthermore, the DNA-binding property of complex 1 with fish sperm DNA (FS-DNA) has been investigated by electronic absorption titration. The result suggests that complex 1 might interact with FS-DNA via groove binding mode.
Graphical abstractThe single crystals of 2,6-Bis{[(4-ethylphenyl)imino]ethyl}pyridine (L1) and it’s Zinc(II) complex [Zn(L1)Cl2]?CH3OH?H2O (1) were determined. In the crystal structure of complex 1, Zn1 atom is five-coordinated in a trigonal bipyramidal geometry. A two-dimensional network is formed by hydrogen bonds. DNA-binding study indicated that complex 1 interact with FS-DNA via groove binding mode.
The title compound, C33H50N2O2, is a side product in the reaction of all-trans-retinoic acid (atRA) with N-hydroxysuccinimide, in the presence of the coupling agent N,N′-dicyclohexylcarbodiimide, which produces the ‘active’ ester succinimidyl all-trans-retinoate as the product. It crystallizes in the orthorhombic Pbca space group. The compound was characterized by 1H-NMR, 13C-NMR, ESI–MS and IR spectroscopy and its structure was determined by single-crystal X-ray diffraction. For example in the 13C-NMR spectrum, diagnostic peaks are those of the two amide carbonyl C atoms at δ 169.5 and 154.2 ppm, the ten olefinic C atoms of the unsaturated chain of atRA moiety at δ 149.0, 139.3, 137.7, 137.3, 134.9, 130.2, 130.0, 129.4, 128.5 and 121.5 ppm and the two methine C atoms of the N,N′-dicyclohexylurea moiety at δ 57.9 and 49.5 ppm. Detailed analysis of its molecular and supramolecular structure showed that close-packing principles (elongated shape/large hydrophobic region of the molecule) together with chemical factors (N–H?O and C–H?O intermolecular interactions) direct the 3D self-assembly process in the crystalline state. Hirshfeld surface analysis was employed, a powerful approach to quickly and easily gain insight into molecular environments in the crystalline state.
Graphical AbstractThe synthesis and X-ray structure of 1-((2E, 4E, 6E, 8E)-3,7-dimethyl-9-(2,6,6-trimethylcyclohex-1-enyl)nona-2,4,6,8-tetraenoyl)-1,3-dicyclohexylurea, a side product in the synthesis of succinimidyl all-trans-retinoate, is reported; Hirshfeld surface analysis was employed to identify intermolecular interactions.
Twenty-four aryl benzyl sulfides, diaryl sulfides and dibenzyl sulfides were synthesized by four methods and characterized by 1H NMR, FT-IR and Gas chromatography. The reaction conditions of different synthesis methods were studied from the aspects of time, solvent, base and dispersant. The molecular structures of benzylphenyl sulfide (2S), (4-tert-butylbenzyl)(4-methylphenyl) sulfide (4S), (4-methylbenzyl)(4-methylphenyl) sulfide (9S), di(4-methylphenyl) sulfide (11S), (3,5-dimethylphenyl)(4-methyl phenyl) sulfide (15S), and dibenzyl sulfide (19S) [22] have been determined by single-crystal X-ray crystallography. Compounds 2S and 15S crystallize in the monoclinic space group P21/c, with a?=?12.278(3), b?=?15.894(3), c?=?5.6056(11) Å, β?=?94.532(2)°, and Z?=?4 for 2S, and a?=?9.800(9), b?=?7.950(7), c?=?16.690(15) Å, β?=?100.890(12)°, and Z?=?4 for 15S. The unit cell of 4S has a triclinic Pī symmetry with the cell parameters a?=?6.0436(10), b?=?8.7871(14), c?=?15.535(2) Å, α?=?81.921(2)°, β?=?81.977(2)°, γ?=?80.889(2)°, and Z?=?2. Compounds 9S and 11S both crystallize in the orthorhombic space group P212121, with a?=?6.188(3), b?=?8.041(4), c?=?26.005(14) Å, and Z?=?4 for 9S, and a?=?5.835(2), b?=?8.010(3), c?=?25.131(9) Å, and Z?=?4 for 11S.
Graphic AbstractTwenty-four aryl sulfide compounds with different substituents were synthesized and characterized, and the molecular structures of six different sulfide compounds have been determined by single-crystal X-ray crystallography.
Single crystal X-ray diffraction analysis of upper rim functionalized tetrabromo-resorcin[4]arenes are presented and their guest encapsulation abilities are discussed. The Br-atoms either attached directly to resorcinarene rim or extended by methylene group (CH2–Br). The substituents on the upper-rim plays an important role in the guest encapsulation characteristic of the resorcinarene cavity. In the crystal structure the host–guest supramolecular systems were stabilized by C–H?O, C–H?π and C?H···Br nonbonding interactions. The Hirshfeld surfaces analysis and the related 2D fingerprint plots provided qualitative and quantitative account of the various supramolecular non-bonding interactions present within the crystal.
Graphic AbstractGuest encapsulation characteristic of tetrabromo-functionalized resorcin[4]arenes.
Treatment of [Fe2(CO)6(μ-S2C3H6)] (1) with triphenylstibine in a 1:1 molar ratio at room temperature in presence of Me3NO resulted compound [Fe2(CO)5(SbPh3)(μ-S2C3H6)] (2) in 88% yield as red crystals. When the reaction was carried out under a 1:5 molar ratio in presence of Me3NO, it resulted a monosubstituted compound [Fe2(CO)5(SbPh3)(μ-S2C3H6)] (2) in 63% yield along with a disubstituted compound [Fe2(CO)4(SbPh3)2(μ-S2C3H6)] (3) in low yield (8%) as red crystals. Reaction of 2 with triphenylstibine in a 1:5 molar ratio under same condition resulted 3 in moderate yield (46%). Compounds 2 and 3 were characterized by elemental analyses, IR, 1H NMR and 13C NMR spectroscopic data. Crystal structures of the compounds were unambiguously determined by single crystal X-Ray diffraction studies. Compound 2 crystalized as monoclinic crystal system with the space group P21/c, a?=?9.464(4) Å, b?=?16.902(7) Å, c?=?17.081(7) Å, β?=?101.216(13)° and Z?=?4. Compound 3 was triclinic, space group P-1, a?=?9.552(3) Å, b?=?13.985(5) Å, c?=?16.487(6) Å, α?=?78.372(16)°, β?=?89.976(14)°, γ?=?71.638(11)° and Z?=?2.
Graphic AbstractTwo new diiron propane-1,3-dithiolate complexes, [Fe2(CO)5(SbPh3)(μ-S2C3H6)] (2) and [Fe2(CO)4(SbPh3)2(μ-S2C3H6)] (3), were synthesized by the displacement of carbonyl groups from [Fe2(CO)6(μ-S2C3H6)] (1) with triphenylstibine, and the resulting complexes were structurally characterized.
Solid state molecular structure of compound 2 (left) and compound 3 (right)
A co-crystal of cobalt(II) complexes, Co(AMTTO)2(CH3CN)2]2+(NO3)2. [Co(AMTTO)2(H2O)2]2+(NO3)2, compound (1) was isolated from the reaction of Co(NO3)2?6H2O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine (AMTTO) in acetonitrile as solvent. Isolated crystals were characterized by elemental analyses, IR spectroscopy as well as X-ray diffraction studies. Crystal data for 1 at 95 K revealed a monoclinic space group P21/n, a?=?11.7903(5), b?=?12.1279(5), c?=?14.1443(6) Å, β?=?99.244(4)°, Z?=?2, R1?=?0.0339. Compound 1 consists of two co-crystallized Co(II) complexes [Co(AMTTO)2(CH3CN)2]2+ and [Co(AMTTO)2(H2O)2]2+ and four nitrate counter anions In both complexes, cobalt(II) ions are in an octahedral arrangement. Two S, N bidentate AMTTO ligands are coordinated to both Co(II) ions. The coordination sphere of Co1 is completed by two acetonitrile molecules, and these positions are occupied by water molecules for Co2.
Graphic AbstractA co-crystal of cobalt(II) compound was isolated from the reaction of Co(NO3)2?6H2O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine in acetonitrile as solvent.
Lanthanide containing polymer chain of title compound {Na[Yb(L)4(iPrOH)]}n is formed by alternating complex anions and sodium cations. The anion is composed by four deprotonated bidentate chelate ligands of sulfonylamidophosphate type N-(bis(benzylamino)phosphoryl)-4-methylbenzenesulfonamide (L?) coordinated to the Yb(III) ion via O atoms belonging to the sulfonyl and phosphoryl groups. The coordination polyhedron of the ytterbium has a slightly distorted triangular dodecahedron conformation, TDD-8, D2d. The Na+ cation is coordinated by four sulfonyl O atoms, the NaO4 polyhedra shape is intermediate between axially vacant trigonal bipyramid C3v and tetrahedron Td. Single-crystal X-ray diffraction studies show that one 2-propanol molecule is hydrogen-bonded to the sulphonyl oxygen of one of the chelate ligands. Also the extensive network of hydrogen bonding interactions between the aromatic rings both in the structural unit and between the polymer chains were detected. They were investigated by the analysis of Hirshfeld surfaces and fingerprint plots. The correlations between structure parameters obtained and the physico-chemical properties of the {Na[Yb(L)4(iPrOH)]}n were investigated.
Graphic AbstractNew tetrakis-complex {Na[Yb(L)4(iPrOH)]}n was synthesized and characterized by X-ray crystallography. Structural packaging characteristics were investigated by the analysis of Hirshfeld surfaces.
Graphical Abstract
The synthesis and crystal structure of pyridine-3-carbaldehyde-N-ethylthiosemicarbazone (3-pytscH-NHEt) 1, and its CuI complex of stoichiometry, [CuCl(3-pytscH-NHEt)(PPh3)2] 2, studied using single crystal X-ray crystallography, are reported in this paper. Crystal data: 1, monoclinic, P21/n, a?=?6.6322(3), b?=?21.1200(8), c?=?7.2989(3) Å; β?=?91.883(4), T?=?173(2), R factor?=?0.0457; 2: triclinic, P-1, a?=?19.3600(5), b?=?20.6241(6), c?=?23.8015(6) Å,α?=?92.647(2), β?=?104.388(2), γ?=?114.377(3), R factor?=?0.0662. The thio-ligand, as a neutral entity, is coordinating to Cu through its S donor atom in complex 2. It has exhibited an unusual feature of forming four independent molecules (A, B, C, D) in the unit cell, with minor differences in the bond angles / distances / torsion angles. The geometry of each molecule of 2 is distorted tetrahedral. Crystal packing, as well as Infrared, electronic absorption and proton NMR spectroscopic studies, are also reported. Copper compound 2 represents the first example of a structurally studied copper coordination compound of 3-pyridyl based thiosemicarbazones.
Graphical AbstractCopper(I) chloride with pyridine-3-carbaldehyde-N-ethylthiosemicarbazone and PPh3 in CH3CN yielded a copper compound, 2 (Green-Cl, blue-N; aqua-Cu, orange-S, magneta-P).
A series of heterotrimetallic manganese-lanthanide-sodium dimer metallacrowns has been synthesized and characterized by single-crystal X-ray analysis: {LnNa[12-MCMn(III)N(shi)-4]}2(iph)4, where LnIII?=?La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Tm (12), Yb (13), Lu (14), and Y (15); MC is metallacrown; shi3? is salicylhydroximate; and iph2? is isophthalate. The manganese(III) ions and shi3? ligands generate the 12-MC-4 framework with one LnIII and Na+ ion bound to each [12-MCMn(III)N(shi)-4] on opposite sides of the central MC cavity. The carboxylate groups of the isophthalate ligands bridge between the central LnIII ion and each ring MnIII ion, and the meta-arrangement of the carboxylate groups joins two LnNa[12-MCMn(III)N(shi)-4] units together to form the dimer through the LnIII ions, which reside on the interior of the molecule. The identity of the central LnIII ion slightly impacts the size the [12-MCMn(III)N(shi)-4] framework. As the crystal radius of the LnIII ion increases from LuIII (1.02 Å) to LaIII (1.19 Å), the 12-MC-4 framework expands to accommodate the larger LnIII ion as the MC cavity increases in size (0.53 Å for LuIII to 0.58 Å for LaIII) and the average cross cavity MnIII-MnIII and oxime oxygen-oxime oxygen distances also increase (MnIII-MnIII distances: 6.48 Å for LuIII to 6.52 Å for LaIII; Ooxime-Ooxime distances: 3.66 Å for LuIII to 3.75 Å for LaIII). In addition, the larger LnIII ions reside further from the MC cavity as indicated by the LnIII-oxime oxygen mean plane (OoxMP) distance. The LnIII-OoxMP distance steadily decreases from LaIII (1.7527(12) Å) to LuIII (1.5575(15) Å).
Graphic AbstractThe complex {LaNa[12-MCMn(III)N(shi)-4]}2(iph)4(DMF)6(H2O)2 is a dimer of [12-MC-4] molecules linked by four isophthalate anions
Two Ag(I)-based coordination polymers, namely [Ag2(3,3′-tmbpt)(o-Hbdc)2]·H2O (1) and [Ag8(3,3′-tmbpt)4(1,2,4-Hbtc)4(H2O)] (2) (3,3′-tmbpt?=?1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, o-H2bdc?=?1,2-benzenedicarboxylic acid and 1,2,4-H3btc?=?1,2,4-benzenetricarboxylic acid), have been synthesized. Single-crystal X-ray diffraction analyses, elemental analyses, infrared spectra, powder X-ray diffraction analyses and thermogravimetric analyses have been carried out to characterize the structures of 1 and 2. Compound 1 shows a (3,4)-connected 2D layered structure with a Schläfli symbol of (42·6)(42·63·8). The intermolecular O–H···O hydrogen-bonding interactions extend the 2D layer into a 3D supramolecular architecture. Compound 2 exhibits a (3,3)-connected double-layered structure with a Schläfli symbol of (4·8·10)2(82·10)2. The intermolecular C–H···O hydrogen-bonding interactions link the double-layers to form a 3D supramolecular architecture. Moreover, there are intramolecular and intermolecular π–π interactions in 1 and 2, which stabilize the whole 3D supramolecular architectures. The band gaps of 1 and 2 are 3.19 and 3.09 eV, respectively, indicating the potential of 1 and 2 as semiconductive materials with wide band gaps. Moreover, 1 and 2 emit intense blue-green light, which may be potential photoactive materials.
Graphic AbstractTwo Ag(I)-based 3D supramolecular coordination polymers constructed from a multidentate N-donor ligand and two aromatic polycarboxylate anions via hydrogen-bonding and π–π interactions have been synthesized and characterized. The band gaps and photoluminescent properties of the compounds have been studied.
The title metallacrown (MC) complexes LnIII[15-MCFeIIIN(shi)-5](OAc)2Cl(C5H5N)6 (Ln1), where OAc– is acetate, shi3? is salicylhydroximate, and Ln?=?Gd and Dy, were synthesized via a self-assembly reaction in methanol and pyridine. Single crystals were grown using slow evaporation and characterized using X-ray diffraction. Seven-coordinate capped octahedron geometries were observed for the lanthanide ion in both complexes, which is uncommon for trivalent lanthanide species. The 15-MC-5 is a ruffled metallacrown archetype similar to previously reported mixed-valent manganese metallacrowns.
Graphic AbstractThe title metallacrown (MC) complexes LnIII[15-MCFeIIIN(shi)-5](OAc)2Cl(C5H5N)6 (Ln1), where OAc– is acetate, shi3? is salicylhydroximate, and Ln?=?Gd and Dy, contains seven-coordinate capped octahedron geometries for the lanthanide ion in both complexes, which is uncommon for trivalent lanthanide species.
Dysprosium oxychloride, DyOCl, was synthesized using a simple hydrolysis method with DyCl3·6H2O. X-ray powder diffraction (XRD) data was used to determine the crystal structure. The DyOCl compound is isostructural to the matlockite (PbFCl) crystal structure and crystallizes in the tetragonal P4/nmm (#129) space group. The crystal structure contains the alternating cationic layers of (DyO)n and anionic layers of nCl? along the c-axis. The structural data including unit cell, volume, and density of DyOCl were compared to other rare-earth oxychloride data from the Inorganic Crystal Structure Database (ICSD) and our previous study on TbOCl. Fourier-transform infrared spectroscopy was performed on DyOCl and peaks observed at 543 and 744 cm?1 were attributed to Dy–O and Dy–Cl. Scanning electron microscopy analysis showed irregularly shaped crystals. Hot-stage XRD, thermogravimetry, as well as differential scanning calorimetry coupled to a gas chromatograph and a mass spectrometer (evolved gas analysis) were performed on DyCl3·6H2O to understand the phase transformation to DyOCl (and Dy2O3) as a function of temperature and time at temperature.
Graphic AbstractDyOCl compound with the tetragonal P4/nmm space group is composed of the alternating layers of (DyO)n and nCl? along the c-axis.
Two mono-nuclear axially distorted octahedral copper(II) complexes have been prepared and characterized via FT-IR, UV–Visible, elctrochemical, electron spin resonance and powder and single crystal XRD techniques. The complexes consist of a phenanthroline and two carboxylate ligands each bonded in bidentate fashion. Carboxylates are ortho-nitro-2-phenyl acetate (L1) and para-chloro-2-phenyl acetate (L2). Structural study showed that both complexes possess Jahn–Teller distorted octahedral geometry. The bulk purity was assessed from the matching experimental and simulated powder XRD spectra. The results of spectroscopic techniques are consistent with each other. ESR data revealed single electron occupancy of dx2 ? y2 orbital with 2B1g as ground state typical of tetragonally distorted octahedral geometry. Electrochemical solution study showed diffusion controlled electron transfer processes with diffusion co-efficient values of 10.323?×?10–8 cm2s–1 and 0.972?×?10–8 cm2s–1 for 1 and 2. Complexes exhibited excellent DNA-binding activity studied via UV–Visible spectroscopy, cyclic voltammetry, florescence spectroscopy and viscometry yielding Kb values of 1.871?×?104 M–1 (1) and 1.577?×?104 M–1 (2), 0.38?×?104 M–1 (1) and 6.39?×?104 M–1 (2) and 2.1?×?106 M–1 (1) and 2.0?×?06 M–1 (2), respectively, for the first three techniques. Complexes possess good antifungal activity against three fungal strains.
Graphic AbstractThe 2:1 molar reaction of [Fe2(CO)6{(µ-SCH2)2CH2}] (1) and a bidentate diphosphine ligand, 1,6-bis(diphenylphosphino)hexane (dpph), in the presence of Me3NO resulted in the isolation of [Fe2(CO)5{Ph2P(CH2)3}{(µ-SCH2)2CH2}]2 (2) as red crystals in 71?% yield. The dpph ligand in compound 2, coordinates two Fe2S2 subunits as bridging mode and hence makes a linkage between two [Fe2(CO)5{(µ-SCH2)2CH2}] fragments. Each Fe2S2 butterfly of the complex consists of two fused Fe(S-C-C-C-S) six-membered rings, one of which attains a chair conformation, and the other is necessarily in a boat conformation. Compound 2 has unequivocally been characterized by elemental analysis, IR, 1H NMR and 31P NMR spectroscopy together with single crystal X-ray diffraction studies. Crystals of 2 are triclinic, space group P-1, a = 9.918(4) Å, b = 10.347(3) Å, c = 14.581(5) Å, α?=?72.239(12)º, β?=?80.342(12)º, γ?=?68.550(14)º and Z = 1.
Graphic AbstractA novel tetranuclear propane-1,3-dithiolate complex, [Fe2(CO)5{Ph2P(CH2)3}{(μ-SCH2)2CH2}]2 (2), bearing a bridging bis(diphenylphosphino)hexane (dpph) ligand, was synthesized from the Me3NO aided room temperature displacement of carbonyls from [Fe2(CO)6{(μ-SCH2)2CH2}] (1), and structurally characterized.
Synthesis and structural characterization of two heterodinuclear ZnII-LnIII complexes with the formula [ZnLn(HL)(µ-OAc)(NO3)2(H2O)x(MeOH)1-x]NO3 · n H2O · n MeOH [Ln?=?Pr (1), Nd (2)] and the crystal and molecular structure of [ZnNd(HL)(µ-OAc)(NO3)2(H2O)] [ZnNd(HL)(OAc)(NO3)2(H2O)](NO3)2 · n H2O · n MeOH (3) are reported. The asymmetrical compartmental ligand (E)-2-(1-(2-((2-hydroxy-3-methoxybenzylidene)amino)-ethyl)imidazolidin-2-yl)-6-methoxyphenol (H2L) is formed from N1,N3-bis(3-methoxysalicylidene)diethylenetriamine (H2valdien) through intramolecular aminal formation, resulting in a peripheral imidazoline ring. The structures of 1–3 were revealed by X-ray crystallography. The smaller ZnII ion occupies the inner N2O2 compartment of the ligand, whereas the larger and more oxophilic LnIII ions are found in the outer O2O2’ site.
Graphic AbstractSynthesis and structural characterization of two heterodinuclear ZnII-LnIII complexes (Ln?=?Pr, Nd) bearing an asymmetrical compartmental ligand formed in situ from N1,N3-bis(3-methoxysalicylidene)diethylenetriamine (H2valdien) through intramolecular aminal formation are reported.
Graphical Abstract
Two molecule of compound 5 crystallized in a non symmetrical manner with four co-crystallized water molecules which play an important role in the crystal packing as strong hydrogen-bond donors.The synthesis and crystal structures of 48 new rare-earth (RE?=?La3+—Y3+)-3,5-dihalogenated benzoic acid (3,5-dibromobenzoic acid [3,5-dBrBA] and 3-bromo-5-iodobenzoic acid [3,5-BrIBA])-terpyridine [TPY] complexes are reported. Ligand based supramolecular assembly drives the formation of five distinct structure types across the lanthanide series. Featured in these structures are multiple significant halogen bonding interactions occurring at the terminal halide substituents in the form of halogen–halogen, halogen–oxygen, and halogen–π interactions. This series complements previous efforts to synthesize and evaluate a catalogue of Ln-halobenzoic acid-TPY materials. With these data, a comparison of the influence of halogen interactions on supramolecular assembly is provided. As one might expect, the frequency with which halogen bonding occurs and the displacement of other assembly mechanisms, depends on the number and polarizability of the halogen species. Structures across these series fall into multiple distinct structure types, as defined by tecton geometry. Since these tectons are isostructural across each respective series, trends in halogen bond propensity can be derived. In this comparison, the likelihood of halogen bonding and disruption of π–π stacking is shown to increase as halogen size increases.
Graphic AbstractTwo new series of rare-earth (RE = La3+–Y3+)-3,5-dihalogenated benzoic acid (3,5-dibromobenzoic acid and 3-bromo-5-iodobenzoic acid)-terpyridine complexes are synthesized and compared, with respect to supramolecular assembly, to each other and previously reported RE-halogenated benzoic acid-terpyridine series in order to study the role of halogen bonding in this system.
The crystal and molecular structures of the fluorocymantrenes [(C5H4F)Mn(CO)3] and [(C5H5?nFn)Mn (CO)2(PPh3)] (n?=?1–3) have been studied. The influence of the phosphine for carbonyl substitution on the bond parameters is larger than the influence of the increasing fluorine content. In most cases the Mn?→?P vector is in a transoid position relative to the fluorine substituents, and therefore the conformational parameters of the PPh3 propeller are in these cases very similar. The crystal structures show many intermolecular C–H?O hydrogen bonds and only very few C–H?F hydrogen bonds.
Graphic AbstractThe influence of the phosphine for carbonyl substitution on the bond parameters of the fluorocymantrenes [(C5H4F)Mn(CO)3] and [(C5H5?nFn)Mn (CO)2(PPh3)] (n?=?1–3) is larger than the influence of the increasing fluorine content.