1H and 13C NMR study of α-acetylenic PIII and PIV derivatives. Signs and magnitudes of J(P?C) and J(P?H)

All J(P? H) and J(P? C) values, including signs, have been obtained in acetylenic and propynylic phosphorus derivatives, R₂P(X)? C?C? H and R₂P(X)? C?C? CH₃ (X ? oxygen, lone pair and R ? C₆H₅, N(CH₃)₂, OC₂H₅, N(C₆H₅)₂, Cl) from ¹H and ¹³C NMR spectra. In P^IV derivatives the following signs are obtained: ¹J(P? C)+, ²J(P? C)+, ³J(P? C)+, ³J(P? H)+, ⁴J(P? H)? . Linear relations are observed between ¹J(P? C), ²J(P? C) and ³J(P? C) versus ³J(P? H), indicating that these coupling constants are mainly dependent on the Fermi contact term, though the other terms of the Ramsey theory do not seem to be negligible for ¹J(P? C) and ²J(P? C). In P^III derivatives these signs are: ¹J(P? C)- and +, ²J(P? C)+, ³J(P? C)-, ³J(P? H)-, ⁴J(P? H)+. Only ³J(P? C) and ³J(P? H) reflect a small contribution of the Fermi contact term while in ¹J(P? C) and ²J(P? C) this contribution seems to be negligible relative to the orbital and/or spin dipolar coupling mechanisms.     

Tetraarylester der μ-Imidodiphosphorsäure und ihre Thioderivate — Strukturuntersuchungen

Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by ¹H, ¹³C, and ³¹P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the ²J_{P? N? P} coupling constants were determined by ¹³C{¹H, ³¹P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group.     

Supramolecular interactions in salts/cocrystals involving pyrimidine derivatives of sulfonate/carboxylic acid

The crystal structures of three compounds involving aminopyrimidine derivatives are reported, namely, 5-fluorocytosinium sulfanilate–5-fluorocytosine–4-azaniumylbenzene-1-sulfonate (1/1/1), C₄H₅FN₃O⁺·C₆H₆NO₃S⁻·C₄H₄FN₃O·C₆H₇NO₃S, I , 5-fluorocytosine–indole-3-propionic acid (1/1), C₄H₄FN₃O·C₁₁H₁₁NO₂, II , and 2,4,6-triaminopyrimidinium 3-nitrobenzoate, C₄H₈N₅⁺·C₇H₄NO₄⁻, III , which have been synthesized and characterized by single-crystal X-ray diffraction. In I , there are two 5-fluorocytosine (5FC) molecules (5FC-A and 5FC-B) in the asymmetric unit, with one of the protons disordered between them. 5FC-A and 5FC-B are linked by triple hydrogen bonds, generating two fused rings [two R₂²(8) ring motifs]. The 5FC-A molecules form a self-complementary base pair [R₂²(8) ring motif] via a pair of N—H…O hydrogen bonds and the 5FC-B molecules form a similar complementary base pair [R₂²(8) ring motif]. The combination of these two types of pairing generates a supramolecular ribbon. The 5FC molecules are further hydrogen bonded to the sulfanilate anions and sulfanilic acid molecules via N—H…O hydrogen bonds, generating R₄⁴(22) and R⁶₆(36) ring motifs. In cocrystal II , two types of base pairs (homosynthons) are observed via a pair of N—H…O/N—H…N hydrogen bonds, generating R₂²(8) ring motifs. The first type of base pair is formed by the interaction of an N—H group and the carbonyl O atom of 5FC molecules through a couple of N—H…O hydrogen bonds. Another type of base pair is formed via the amino group and a pyrimidine ring N atom of the 5FC molecules through a pair of N—H…N hydrogen bonds. The base pairs (via N—H…N hydrogen bonds) are further bridged by the carboxyl OH group of indole-3-propionic acid and the O atom of 5FC through O—H…O hydrogen bonds on either side of the R₂²(8) motif. This leads to a DDAA array. In salt III , one of the N atoms of the pyrimidine ring is protonated and interacts with the carboxylate group of the anion through N—H…O hydrogen bonds, leading to the primary ring motif R₂²(8). Furthermore, the 2,4,6-triaminopyrimidinium (TAP) cations form base pairs [R₂²(8) homosynthon] via N—H…N hydrogen bonds. A carboxylate O atom of the 3-nitrobenzoate anion bridges two of the amino groups on either side of the paired TAP cations to form another ring [R₃²(8)]. This leads to the generation of a quadruple DADA array. The crystal structures are further stabilized by π–π stacking ( I and III ), C—H…π ( I and II ), C—F…π ( I ) and C—O…π ( II ) interactions.     

Dérivés Alléniques du Phosphore. Influence de l'État de Coordination du Phosphore et de la Nature des Radicaux Liés au Phosphore sur les Signes de J(P?H)

The signs of the phosphorus-proton coupling constants in various allenic organophosphorus compounds have been determined by either analysis of the AB₂X spectra or double resonance. Probable absolute signs have been obtained by taking ³J(P? H) as positive. In allenic phosphine oxides, the following signs are obtained: ²J(P? H) +ve, ³J(P? H) +ve, ⁴J(P? H) ?ve, ⁵J(P? H) +ve and the ⁴J(P? H) coupling constant varies mostly with the inductive effect of the substituents bound to the phosphorus atom. In allenic phosphines, these sings are: ²J(P? H) +ve, ³J(P? H) +ve, ⁴J(P? H) ?ve and +ve and the ⁴J(P? H) coupling constant varies with both the inductive and resonance effects to the substituents. This coupling constant is negative except when the phosphorus atom is bound to groups which are electron-donating by resonance effects. These results are discussed in relation to the pπ? dπ bonding in phosphine.     

The synergistic co‐operation of N—H…O=P hydrogen bonds and C—H…OX weak intermolecular interactions (X is =P or —C) in the (CH3O)2P(O)(NH–NHC6F5) amidophosphoester: a combined X‐ray crystallographic and theoretical study

The asymmetric unit of O,O′‐dimethyl [(2,3,4,5,6‐pentafluorophenyl)hydrazinyl]phosphonate, C₈H₈F₅N₂O₃P, is composed of two symmetry‐independent molecules with significant differences in the orientations of the C₆F₅ and OMe groups. In the crystal structure, a one‐dimensional assembly is mediated from classical N—H…O hydrogen bonds, which includes R₂²(8), D(2) and some higher‐order graph‐set motifs. By also considering weak C—H…O=P and C—H…O—C intermolecular interactions, a two‐dimensional network extends along the ab plane. The strengths of the hydrogen bonds were evaluated using quantum chemical calculations with the GAUSSIAN09 software package at the B3LYP/6‐311G(d,p) level of theory. The LP(O) to σ*(NH) and σ*(CH) charge‐transfer interactions were examined according to second‐order perturbation theory in natural bond orbital (NBO) methodology. The hydrogen‐bonded clusters of molecules, including N—H…O and C—H…O interactions, were constructed as input files for the calculations and the strengths of the hydrogen bonds are as follows: N—H…O [R₂²(8)] > N—H…O [D(2)] > C—H…O. The decomposed fingerprint plots show that the contribution portions of the F…H/H…F contacts in both molecules are the largest.     

2J(P,C) and 3J(P,C) Coupling Constants in Some New Phosphoramidates. Crystal Structures of CF3C(O)N(H)P(O)[N(CH3)(CH2C6H5)]2 and 4‐NO2‐C6H4N(H)P(O)[4‐CH3‐NC5H9]2

Some new phosphoramidates were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR spectroscopy and elemental analysis. The structures of CF₃C(O)N(H)P(O)[N(CH₃)(CH₂C₆H₅)]₂ ( 1 ) and 4‐NO₂‐C₆H₄N(H)P(O)[4‐CH₃‐NC₅H₉]₂ ( 6 ) were confirmed by X‐ray single crystal determination. Compound 1 forms a centrosymmetric dimer and compound 6 forms a polymeric zigzag chain, both via ‐N‐H…O=P‐ intermolecular hydrogen bonds. Also, weak C‐H…F and C‐H…O hydrogen bonds were observed in compounds 1 and 6 , respectively. ¹³C NMR spectra were used for study of ²J(P,C) and ³J(P,C) coupling constants that were showed in the molecules containing N(C₂H₅)₂ and N(C₂H₅)(CH₂C₆H₅) moieties, ²J(P,C)>³J(P,C). A contrast result was obtained for the compounds involving a five‐membered ring aliphatic amine group, NC₄H₈. ²J(P,C) for N(C₂H₅)₂ moiety and in NC₄H₈ are nearly the same, but ³J(P, C) values are larger than those in molecules with a pyrrolidinyl ring. This comparison was done for compounds with six and seven‐membered ring amine groups. In compounds with formula XP(O)[N(CH₂R)(CH₂C₆H₅)]₂, ²J(P,CH₂)_benzylic>²J(P,CH₂)_aliphatic, in an agreement with our previous study.     

H/D isotope effect on charge‐inverted hydrogen‐bonded systems: Systematic classification of three different types in H3XH…YH3 (X = C,Si, or Ge,and Y = B,Al, or Ga) with multicomponent calculation

Three different H/D isotope effect in nine H₃XH(D)^…YH₃ (X = C, Si, or Ge, and Y = B, Al, or Ga) hydrogen‐bonded (HB) systems are classified using MP2 level of multicomponent molecular orbital method, which can take account of the nuclear quantum nature of proton and deuteron. First, in the case of H₃CH(D)^…YH₃ (Y = B, Al, or Ge) HB systems, the deuterium (D) substitution induces the usual H/D geometrical isotope effect such as the contraction of covalent R(C? H(D)) bonds and the elongation of intermolecular R(H(D)^…Y) and R(C^…Y) distances. Second, in the case of H₃XH(D)^…YH₃ (X = Si or Ge, and Y = Al or Ge) HB systems, where H atom is negatively charged called as charge‐inverted hydrogen‐bonded (CIHB) systems, the D substitution leads to the contraction of intermolecular R(H(D)^…Y) and R(X^…Y) distances. Finally, in the case of H₃XH(D)^…BH₃ (X = Si or Ge) HB systems, these intermolecular R(H(D)^…Y) and R(X^…Y) distances also contract with the D substitution, in which the origin of the contraction is not the same as that in CIHB systems. The H/D isotope effect on interaction energies and spatial distribution of nuclear wavefunctions are also analyzed. © 2015 Wiley Periodicals, Inc.     

Synthesis,Interionic Structure,and Reactivity toward CO and p‐Methylstyrene of Palladacyclic Compounds Bearing α‐Diimine Ligands

Palladacyclic compounds [Pd(C₆H₄(C₆H₅C?O)C?N? R)(N? N)] [X] (R = Et, ⁱPr, 2,6‐ⁱPr₂C₆H₃; N? N = bpy = 2,2′‐bipyridine, or 1,4‐(o,o′‐dialkylaryl)‐1,4‐diazabuta‐1,3‐dienes; [X]^? = [BF₄]^? or [PF₆]^?) were synthesized from the dimers [{Pd(C₆H₄(C₆H₅C?O)C?N? R)(μ‐Cl)}₂] and N? N ligands. Their interionic structure in CD₂Cl₂ was determined by means of ¹⁹F,¹H‐HOESY experiments and compared with that in the solid state derived from X‐ray single‐crystal studies. [Pd(C₆H₄(C₆H₅C?O)C?N? R)(N? N)] [X] complexes were found to copolymerize CO and p‐methylstyrene affording syndiotactic or isotactic copolymers when bpy or 1,4‐(o,o′‐dimethylaryl)‐1,4‐diazabuta‐1,3‐dienes were used, respectively. The reactions with CO and p‐methylstyrene of the bpy derivatives were investigated. Two intermediates derived from a single and a double insertion of CO into the Pd? C bonds were isolated and completely characterized in solution.     

Inequivalence Magnetique Due a la Presence d'un Atome de Phosphore Asymetrique ou Pseudo-Asymetrique

In phosphinous esters of general formula R? PH(O)OR', the asymmetric phosphorus atom induces magnetic non-equivalence in geminal protons and methyl groups. When alkoxy groups also possess an asymmetric carbon, the presence of the two possible diastereoisomers in equal amounts is proven by ³¹P and ¹H NMR. ³¹P NMR reveals that the phosphorus atom in phosphonous esters R? P(O·C₄H₉-s)₂ of racemic sec. butyl alcohol, is a centre of pseudo-asymmetry.     

Weak hydrogen bonding and fluorous interactions in the chloride and bromide salts of 4‐[(2,2,3,3‐tetrafluoropropoxy)methyl]pyridinium

Neutralization of 4‐[(2,2,3,3‐tetrafluoropropoxy)methyl]pyridine with hydrohalo acids HX (X = Cl and Br) yielded the pyridinium salts 4‐[(2,2,3,3‐tetrafluoropropoxy)methyl]pyridinium chloride, C₉H₁₀F₄NO⁺·Cl⁻, (1), and 4‐[(2,2,3,3‐tetrafluoropropoxy)methyl]pyridinium bromide, C₉H₁₀F₄NO⁺·Br⁻, (2), both carrying a fluorous side chain at the para position of the pyridinium ring. Single‐crystal X‐ray diffraction techniques revealed that (1) and (2) are isomorphous. The halide anions accept four hydrogen bonds from N—H, ortho‐C—H and CF₂—H groups. Two cations and two anions form a centrosymmetric dimeric building block, utilizing complimentary N—H…X …H—Csp ³ connections. These dimers are further crosslinked, utilizing another complimentary Csp ²—H…X …H—Csp ² connection. The pyridinium rings are π‐stacked, forming columns running parallel to the a axis that make angles of ca 44–45° with the normal to the pyridinium plane. There are also supramolecular C—H…F—C interactions, namely bifurcated C—H…F and bifurcated C—F…H interactions; additionally, one type II C—F…F—C halogen bond has been observed.     

Reactions of phosphorus fluorides and ortho-carborane ditertiary aminophosphines

Fluorophosphine bidentate ligands containing o-carborane as backbone can be prepared by the reaction of the lithium-o-carboranes and PF₂X derivatives to give only two species: the unsymmetrical (C₆H₅)₂P[B₁₀H₁₀C₂]PF₂ and the cyclic FP[B₁₀H₁₀C₂]₂PF, both in low yield. However, exchange of F and NMe₂ groups by use of PF₅ or PF₃ provides a facile way to produce several new fluorophosphines.Phosphorus pentafluoride forms solid adducts with the o-phosphino derivatives (C₆H₅)₂P[B₁₀H₁₀C₂]P(NMe₂)₂, (Me₂N)₂P[B₁₀H₁₀C₂]P(NMe₂)₂ and (C₆H₅)₂P[B₁₀H₁₀C₂]H. All the adducts contain a phosphorus-phosphorus bond as evidenced from i.r., NMR and stoichiometry. The stability of the adducts reflects the strength of the PP bond formed upon complexation. When suspensions or solutions of the adducts are heated they exchange F and NMe₂ groups and no redox occurs. The products (C₆H₅)₂P[B₁₀H₁₀C₂]P(F)NMe₂(I) and Me₂N(F)P[B₁₀H₁₀C₂]P(F)NMe₂(II) react further with PF₅ giving (C₆H₅)₂P[B₁₀H₁₀C₂]PF₂(III) and F₂P[B₁₀H₁₀C₂]PF₂(IV).The precursors also react with phosphorus trifluoride to produce only (I) and (Me₂N)₂P[B₁₀H₁₀C₂]P(F)NMe₂(V) regardless of the reaction conditions. All the products I–V have been identified by ¹H, ¹⁹F, and ³¹P NMR and i.r. spectroscopy, mass spectrometry, and elemental analysis. The NMR spectra of the novel (IV) have been analysed as X₂AA¹X¹₂ spin system.     

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.     

Mono‐ and dinuclear CuII complexes of the benzyldipicolylamine (BDPA) ligand: crystal structure,synthesis and characterization

The crystal structures of mono‐ and dinuclear Cu^II trifluoromethanesulfonate (triflate) complexes with benzyldipicolylamine (BDPA) are described. From equimolar amounts of Cu(triflate)₂ and BDPA, a water‐bound Cu^II mononuclear complex, aqua(benzyldipicolylamine‐κ³N ,N′ ,N ′′)bis(trifluoromethanesulfonato‐κO )copper(II) tetrahydrofuran monosolvate, [Cu(CF₃SO₃)₂(C₁₉H₁₉N₃)(H₂O)]·C₄H₈O, (I), and a triflate‐bridged Cu^II dinuclear complex, bis(μ‐trifluoromethanesulfonato‐κ²O :O ′)bis[(benzyldipicolylamine‐κ³N ,N′ ,N ′′)(trifluoromethanesulfonato‐κO )copper(II)], [Cu₂(CF₃SO₃)₄(C₁₉H₁₉N₃)₂], were synthesized. The presence of residual moisture in the reaction medium afforded water‐bound complex (I), whereas dinuclear complex (II) was synthesized from an anhydrous reaction medium. Single‐crystal X‐ray structure analysis reveals that the Cu^II centres adopt slightly distorted octahedral geometries in both complexes. The metal‐bound water molecule in (I) is involved in intermolecular O—H…O hydrogen bonds with triflate ligands and tetrahydrofuran solvent molecules. In (II), weak intermolecular C—H…F(triflate) and C—H…O(triflate) hydrogen bonds stabilize the crystal lattice. Complexes (I) and (II) were also characterized fully using FT–IR and UV–Vis spectroscopy, cyclic voltammetry and elemental analysis.     

Structural characterization of silver dialkylphosphite salts using solid‐state 109Ag and 31P NMR spectroscopy,IR spectroscopy and DFT calculations

High‐resolution solid‐state ¹⁰⁹Ag and ³¹P NMR spectroscopy was used to investigate a series of silver dialkylphosphite salts, Ag(O)P(OR)₂ (R = CH₃, C₂H₅, C₄H₉ and C₈H₁₇), and determine whether they adopt keto, enol or dimer structures in the solid state. The silver chemical shift, CS, tensors and |J(¹⁰⁹Ag, ³¹P)| values for these salts were determined using ¹⁰⁹Ag (Ξ = 4.652%) NMR spectroscopy. The magnitudes of J(¹⁰⁹Ag, ³¹P) range from 1250 ± 10 to 1318 ± 10 Hz and are the largest reported so far. These values indicate that phosphorus is directly bonded to silver for all these salts and thus exclude the enol structure. All ³¹P NMR spectra exhibit splittings due to indirect spin–spin coupling to ¹⁰⁷Ag (I = 1/2, NA = 51.8%) and ¹⁰⁹Ag (I = 1/2, NA = 48.2%). The ¹J(¹⁰⁹Ag, ³¹P) values measured by both ¹⁰⁹Ag and ³¹P NMR spectroscopy agree within experimental error. Analysis of ³¹P NMR spectra of stationary samples for these salts allowed the determination of the phosphorus CS tensors. The absence of characteristic P?O stretching absorption bands near 1250 cm^?1 in the IR spectra for these salts exclude the simple keto tautomer. Thus, the combination of solid‐state NMR and IR results indicate that these silver dialkylphosphite salts probably have a dimer structure. Values of silver and phosphorus CS tensors as well as ¹J(¹⁰⁹Ag, ³¹P) values for a dimer model calculated using the density functional theory (DFT) method are in agreement with the experimental observations. Copyright © 2010 John Wiley & Sons, Ltd.     

Transition‐Metal‐Mediated Cleavage of Fluoro‐Silanes under Mild Conditions

Si?F bond cleavage of fluoro‐silanes was achieved by transition‐metal complexes under mild and neutral conditions. The Iridium‐hydride complex [Ir(H)(CO)(PPh₃)₃] was found to readily break the Si?F bond of the diphosphine‐ difluorosilane {(o‐Ph₂P)C₆H₄}₂Si(F)₂ to afford a silyl complex [{[o‐(iPh₂P)C₆H₄]₂(F)Si}Ir(CO)(PPh₃)] and HF. Density functional theory calculations disclose a reaction mechanism in which a hypervalent silicon species with a dative Ir→Si interaction plays a crucial role. The Ir→Si interaction changes the character of the H on the Ir from hydridic to protic, and makes the F on Si more anionic, leading to the formation of H^δ+???F^δ? interaction. Then the Si?F and Ir?H bonds are readily broken to afford the silyl complex and HF through σ‐bond metathesis. Furthermore, the analogous rhodium complex [Rh(H)(CO)(PPh₃)₃] was found to promote the cleavage of the Si?F bond of the triphosphine‐monofluorosilane {(o‐Ph₂P)C₆H₄}₃Si(F) even at ambient temperature.     

Reduced 3,4′‐bipyrazoles from a simple pyrazole precursor: synthetic sequence,molecular structures and supramolecular assembly

The reaction of 5‐chloro‐3‐methyl‐1‐phenyl‐1H‐pyrazole‐4‐carbaldehyde and N‐benzylmethylamine under microwave irradiation gives 5‐[benzyl(methyl)amino]‐3‐methyl‐1‐phenyl‐1H‐pyrazole‐4‐carbaldehyde, C₁₉H₁₉N₃O, (I). Subsequent reactions under basic conditions, between (I) and a range of acetophenones, yield the corresponding chalcones. These undergo cyclocondensation reactions with hydrazine to produce reduced bipyrazoles which can be N‐formylated with formic acid or N‐acetylated with acetic anhydride. The structures of (I) and of representative examples from this reaction sequence are reported, namely the chalcone (E )‐3‐{5‐[benzyl(methyl)amino]‐3‐methyl‐1‐phenyl‐1H‐pyrazol‐4‐yl}‐1‐(4‐bromophenyl)prop‐2‐en‐1‐one, C₂₇H₂₄BrN₃O, (II), the N‐formyl derivative (3RS )‐5′‐[benzyl(methyl)amino]‐3′‐methyl‐1′,5‐diphenyl‐3,4‐dihydro‐1′H ,2H‐[3,4′‐bipyrazole]‐2‐carbaldehyde, C₂₈H₂₇N₅O, (III), and the N‐acetyl derivative (3RS )‐2‐acetyl‐5′‐[benzyl(methyl)amino]‐5‐(4‐methoxyphenyl)‐3′‐methyl‐1′‐phenyl‐3,4‐dihydro‐1′H ,2H‐[3,4′‐bipyrazole], which crystallizes as the ethanol 0.945‐solvate, C₃₀H₃₁N₅O₂·0.945C₂H₆O, (IV). There is significant delocalization of charge from the benzyl(methyl)amino substituent onto the carbonyl group in (I), but not in (II). In each of (III) and (IV), the reduced pyrazole ring is modestly puckered into an envelope conformation. The molecules of (I) are linked by a combination of C—H…N and C—H…π(arene) hydrogen bonds to form a simple chain of rings; those of (III) are linked by a combination of C—H…O and C—H…N hydrogen bonds to form sheets of R ²₂(8) and R ⁶₆(42) rings, and those of (IV) are linked by a combination of O—H…N and C—H…O hydrogen bonds to form a ribbon of edge‐fused R ²₄(16) and R ⁴₄(24) rings.     

Conformational flexibility in amidophosphoesters: a CSD analysis completed with two new crystal structures of (C6H5O)2P(O)X [X = NHC7H13 and N(CH2C6H5)2]

The crystal structures of diphenyl (cycloheptylamido)phosphate, C₁₉H₂₄NO₃P or (C₆H₅O)₂P(O)(NHC₇H₁₃), ( I ), and diphenyl (dibenzylamido)phosphate, C₂₆H₂₄NO₃P or (C₆H₅O)₂P(O)[N(CH₂C₆H₅)₂], ( II ), are reported. The NHC₇H₁₃ group in ( I ) provides two significant hydrogen‐donor sites in N—H…O and C—H…O hydrogen bonds, needed for a one‐dimensional hydrogen‐bond pattern along [100] in the crystal, while ( II ), with a (C₆H₅CH₂)₂N moiety, lacks these hydrogen bonds, but its three‐dimensional supramolecular structure is mediated by C—H…π interactions. The conformational behaviour of the phenyl rings in ( I ), ( II ) and analogous structures from the Cambridge Structural Database (CSD) were studied in terms of flexibility, volume of the other group attached to phosphorus and packing forces. From this study, synclinal (±sc), anticlinal (±ac) and antiperiplanar (±ap) conformations were found to occur. In the structure of ( II ), there is an intramolecular C_ortho—H…O interaction that imposes a +sc conformation for the phenyl ring involved. For the structures from the CSD, the +sc and ±ap conformations appear to be mainly imposed by similar C_ortho—H…O intramolecular interactions. The large contribution of the C…H/H…C contacts (32.3%) in the two‐dimensional fingerprint plots of ( II ) is a result of the C—H…π interactions. The differential scanning calorimetry (DSC) analyses exhibit peak temperatures (T_m) at 109 and 81 °C for ( I ) and ( II ), respectively, which agree with the strengths of the intermolecular contacts and the melting points.     

Supramolecular architectures in the salt trimethoprimium ferrocene‐1‐carboxylate and the cocrystal 4‐amino‐5‐chloro‐2,6‐dimethylpyrimidine–ferrocene‐1‐carboxylic acid (1/1)

In the salt trimethoprimium ferrocenecarboxylate [systematic name: 2,4‐diamino‐5‐(3,4,5‐trimethoxybenzyl)pyrimidin‐1‐ium ferrocene‐1‐carboxylate], (C₁₄H₁₉N₄O₃)[Fe(C₅H₅)(C₆H₄O₂)], (I), of the antibacterial compound trimethoprim, the carboxylate group interacts with the protonated aminopyrimidine group of trimethoprim via two N—H…O hydrogen bonds, generating a robust R ₂²(8) ring motif (heterosynthon). However, in the cocrystal 4‐amino‐5‐chloro‐2,6‐dimethylpyrimidine–ferrocene‐1‐carboxylic acid (1/1), [Fe(C₅H₅)(C₆H₅O₂)]·C₆H₈ClN₃, (II), the carboxyl–aminopyrimidine interaction [R ₂²(8) motif] is absent. The carboxyl group interacts with the pyrimidine ring via a single O—H…N hydrogen bond. The pyrimidine rings, however, form base pairs via a pair of N—H…N hydrogen bonds, generating an R ₂²(8) supramolecular homosynthon. In salt (I), the unsubstituted cyclopentadienyl ring is disordered over two positions, with a refined site‐occupation ratio of 0.573 (10):0.427 (10). In this study, the two five‐membered cyclopentadienyl (Cp) rings of ferrocene are in a staggered conformation, as is evident from the C…Cg …Cg …C pseudo‐torsion angles, which are in the range 36.13–37.53° for (I) and 22.58–23.46° for (II). Regarding the Cp ring of the minor component in salt (I), the geometry of the ferrocene ring is in an eclipsed conformation, as is evident from the C…Cg …Cg …C pseudo‐torsion angles, which are in the range 79.26–80.94°. Both crystal structures are further stabilized by weak π–π interactions.     

cis‐Tetra­carbonyl­[(4‐fluoro­phenyl)di­phenyl­phosphine‐P](piperidine‐N)molybdenum(0)

The title mol­ecule, [Mo{P(C₆H₅)₂(C₆H₄F)}(HNC₅H₁₀)(CO)₄] or [Mo(C₁₈H₁₄FP)(C₅H₁₁N)(CO)₄], has irregular octahedral geometry about the Mo atom. The mol­ecules form a complicated hydrogen‐bonded network comprising C—H?O, C—H?F and C—H?π hydrogen bonds and π–π interactions. The C—H?π and π–π interactions form chains containing C—H?π/π–π dimers linked via C—H?π interactions and the chains are linked into a three‐dimensional network via C—H?O and C—H?F hydrogen bonds.     

Supramolecular interactions in carboxylate and sulfonate salts of 2,6‐diamino‐4‐chloropyrimidinium

Two new salts, namely 2,6‐diamino‐4‐chloropyrimidinium 2‐carboxy‐3‐nitrobenzoate, C₄H₆ClN₄⁺·C₈H₄NO₆⁻, (I), and 2,6‐diamino‐4‐chloropyrimidinium p‐toluenesulfonate monohydrate, C₄H₆ClN₄⁺·C₇H₇O₃S⁻·H₂O, (II), have been synthesized and characterized by single‐crystal X‐ray diffraction. In both crystal structures, the N atom in the 1‐position of the pyrimidine ring is protonated. In salt (I), the protonated N atom and the amino group of the pyrimidinium cation interact with the carboxylate group of the anion through N—H…O hydrogen bonds to form a heterosynthon with an R ₂²(8) ring motif. In hydrated salt (II), the presence of the water molecule prevents the formation of the familiar R ₂²(8) ring motif. Instead, an expanded ring [i.e. R ₃²(8)] is formed involving the sulfonate group, the pyrimidinium cation and the water molecule. Both salts form a supramolecular homosynthon [R ₂²(8) ring motif] through N—H…N hydrogen bonds. The molecular structures are further stabilized by π–π stacking, and C=O…π, C—H…O and C—H…Cl interactions.