7‐Vinyl‐8‐aza‐7‐de­aza‐2′‐deoxy­adenosine monohydrate

In the title compound, 4‐amino‐1‐(2‐deoxy‐β‐d ‐eythro‐pento­furan­osyl)‐3‐vinyl‐1H‐pyrazolo­[3,4‐d]­pyrimidine monohydrate, C₁₂H₁₅N₅O₃·H₂O, the conformation of the gly­cosyl bond is anti. The furan­ose moiety is in an S conformation with an unsymmetrical twist, and the conformation at the exocyclic C—C(OH) bond is +sc (gauche, gauche). The vinyl side chain is bent out of the heterocyclic ring plane by 147.5 (5)°. The three‐dimensional packing is stabilized by O—H·O, O—H·N and N—H·O hydrogen bonds.     

N‐(Ferrocenecarbonyl)‐N′‐(quinolin‐8‐yl)thio­urea

In the title compound, [Fe(C₅H₅)(C₁₆H₁₂N₃OS)], the 8‐am­inoquinoline and acyl­thio­urea moieties are almost planar. There are two perpendicular arrangements of the mol­ecules in the crystal with slightly different conformations. The two cyclo­penta­dienyl rings in each mol­ecule are parallel and eclipsed.     

7‐Iodo‐8‐aza‐7‐deaza‐2′‐deoxy­adenosine and 7‐bromo‐8‐aza‐7‐deaza‐2′‐deoxyadenosine

The isomorphous structures of the title molecules, 4‐amino‐1‐(2‐deoxy‐β‐d ‐erythro‐pento­furan­osyl)‐3‐iodo‐1H‐pyrazolo‐[3,4‐d]pyrimidine, (I), C₁₀H₁₂IN₅O₃, and 4‐amino‐3‐bromo‐1‐(2‐deoxy‐β‐d ‐erythro‐pento­furan­osyl)‐1H‐pyrazolo[3,4‐d]­pyrimidine, (II), C₁₀H₁₂BrN₅O₃, have been determined. The sugar puckering of both compounds is C1′‐endo (^1′E). The N‐­glycosidic bond torsion angle χ¹ is in the high‐anti range [?73.2 (4)° for (I) and ?74.1 (4)° for (II)] and the crystal structure is stabilized by hydrogen bonds.     

catena‐Poly[[[diaqua[3‐(pyridin‐4‐yl)benzoato‐κ2O,O′]terbium(III)]‐bis[μ‐3‐(pyridin‐4‐yl)benzoato‐κ2O:O′]] monohydrate]

In the title compound, {[Tb(C₁₂H₈NO₂)₃(H₂O)₂]·H₂O}_n, the Tb^III cation is in an eight‐coordinate environment, ligated by six carboxylate O atoms from five 3‐(pyridin‐4‐yl)benzoate (L) ligands and by two O atoms from water molecules. The cations are bridged by the carboxylate O atoms of the L ligands to form a two‐stranded polymeric chain which is assembled into a three‐dimensional supramolecular network through regular interchain O—H...N hydrogen bonding. On excitation at 320 nm, the title compound displays a series of emissions, which were assigned to the characteristic electronic transitions of Tb^III.     

N,N′‐Bis(2‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide and N,N′‐bis­(3‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide

The mol­ecules of N,N′‐bis­(2‐pyridylmeth­yl)ferrocene‐1,1′‐diyl­dicarboxamide, [Fe(C₁₂H₁₁N₂O)₂], contain intra­molecular N—H⋯N hydrogen bonds and are linked into sheets by three independent C—H⋯O hydrogen bonds. The mol­ecules of the isomeric compound N,N′‐bis­(3‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide lie across inversion centres, and the mol­ecules are linked into sheets by a combination of N—H⋯N hydrogen bonds and π–π stacking inter­actions between pyridyl groups.     

Dichloro­[(1E,1′E)‐1,1′‐(pyridine‐2,6‐di­yl)diethanone bis­(O‐methyloxime)‐κ3N1,N2,N6]cobalt(II)

In the title compound, [CoCl₂(C₁₁H₁₅N₃O₂)], the Co^II ion is five‐coordinated in a strongly distorted square‐pyramidal arrangement, with one of the two Cl atoms located in the apical position, and the other Cl atom and the three N‐donor atoms of the tridentate methyloxime ligand located in the basal plane. The non‐H atoms, except for the Cl atoms, lie on a mirror plane. The two equatorial Co—N_oxime distances are almost equal (mean 2.253 Å) and are substanti­ally longer than the equatorial Co—N_pyridine bond [2.0390 (19) Å]. The structure is stabilized by intra‐ and inter­molecular C—H⋯Cl contacts, which involve one of the methyl C atoms belonging to the methyloxime groups.     

Semisynthesis of 3′(2′)‐O‐(Aminoacyl)‐tRNA Derivatives as Ribosomal Substrate

An efficient synthesis of (3′‐terminally) 3′(2′)‐O‐aminoacylated pCpA derivatives is described, which could lead to the production of (aminoacyl)‐tRNAs following T4 RNA ligase mediated ligation. The tetrahydrofuranyl (thf) group was used as a permanent protective group for the 2′‐OH of the cytidine moiety which can be removed during the purification of the 3′(2′)‐O‐aminoacylated‐pCpA. This approach allowed for a general synthesis of (3′‐terminally) 3′(2′)‐O‐aminoacylated oligonucleotides. The fully protected pCpA 14 was synthesized by phosphoramidite chemistry and treated with NH₃ solution to remove the 2‐cyanoethyl and benzoyl groups (→ 15 ; Schemes 1 and 2). The 2′‐O‐thf‐protected‐pCpA 15 was coupled with α‐amino acid cyanomethyl esters, and the products 20a – c were deprotected and purified with AcOH buffer to afford 3′(2′)‐O‐aminoacylated pCpA 21a – c in high yields. The 3′(2′)‐O‐aminoacylated pCpA were efficiently ligated with tRNA(? CA) to yield (aminoacyl)‐tRNA which was an active substrate for the ribosome.     

8‐Aza‐7‐deaza‐2′‐de­oxy‐2‐(methyl­sulfan­yl)adenosine

In the title compound, 4‐amino‐1‐(2‐de­oxy‐β‐d ‐erythro‐pentofuranos­yl)‐6‐methyl­sulfanyl‐1H‐pyrazolo[3,4‐d]pyrimidine, C₁₁H₁₆N₅O₃S, the conformation of the glycosidic bond is between anti and high anti. The 2′‐deoxy­ribofuranosyl moiety adopts the C3′‐exo–C4′‐endo conformation (₃T⁴, S‐type sugar pucker), and the conformation at the exocyclic C—C bond is +sc (+gauche). The exocyclic 6‐amine group and the 2‐methyl­sulfanyl group lie on different sides of the heterocyclic ring system. The mol­ecules form a three‐dimensional hydrogen‐bonded network that is stabilized by O—H⋯N, N—H⋯O and C—H⋯O hydrogen bonds.     

Synthesis and Structure Elucidation of (R)‐3‐(2′‐hydroxyprop‐1‐yl) adenine

(R)‐3‐(2′‐hydroxyprop‐1‐yl) adenine 4 was obtained by alkylation of adenine 1 with R‐propylene carbonate 2 in the presence of pulverized sodium hydroxide in the synthetic process of tenofovir. The elucidation of the structure of 4 was confirmed by single crystal X‐ray diffraction and NMR experiments such as 1D ¹H, ¹³C, and DEPT, as well as 2D COSY, HSQC, and HMBC spectra.     

Synthesis of 2‐(sulfamoylphenyl)‐4′‐(iminoaryl/hetroaryl)‐4‐(4′′‐hydroxyphenyl)‐thiazoles and their O‐glucosides

In continuation of our work, we synthesized 2‐(sulfamoylphenyl)‐4′‐amino‐4‐(4″‐hydroxyphenyl)‐thiazole ( 3a ), which were reacted with various (aryl/hetroaryl) aldehyde to form 2‐(sulfamoylphenyl)‐4′‐(iminoaryl/hetroaryl)‐4‐(4″‐hydroxyphenyl)‐thiazoles ( 4a , 4b , 4c , 4d , 4e , 4f ). Glucosylation of compounds ( 4a , 4b , 4c , 4d , 4e , 4f ) have been done by using acetobromoglucose as a glucosyl donor to afford 2‐(sulfamoylphenyl)‐4′‐(iminoaryl/hetroaryl)‐4‐(2,3,4,6‐tetra‐O‐acetyl‐4″‐O‐β‐D ‐glucosidoxyphenyl)‐thiazoles ( 5a , 5b , 5c , 5d , 5e , 5f ), further on deacetylation to produce 2‐(sulfamoylphenyl)‐4′‐(iminoaryl/hetroaryl)‐4‐(4″‐O‐β‐D ‐glucosidoxyphenyl)‐thiazoles ( 6a , 6b , 6c , 6d , 6e , 6f ). The compounds are confirmed by FTIR, ¹H‐NMR, ¹³C‐NMR, and ES‐Mass spectral analysis. J. Heterocyclic Chem., (2011).     

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.     

N‐(2‐Amino­benz­yl)‐N,N‐bis­(quinolin‐2‐ylmeth­yl)amine

The title new diquinaldine derivative, C₂₇H₂₄N₄, forms mol­ecular assemblies organized by inter­molecular quinoline π–π stacking [3.356 (3) and 3.440 (3) Å] and both inter‐ and intra­molecular N—H⋯N hydrogen bonds [3.039 (3)–3.104 (3) Å and 129 (2)–172 (2)°]. The combination of such inter­actions provides readily definable contacts that propagate along each crystallographic axis.     

Chlorido[N,N′‐dibenzyl‐N′′‐(trichloroacetyl)phosphoramidato‐κ2O,O′](1,10‐phenanthroline‐κ2N,N′)copper(II)

In the title complex, [Cu(C₁₆H₁₆Cl₃N₃O₂P)Cl(C₁₂H₈N₂)], the Cu^II cation presents a square‐pyramidal environment, where the CuO₂N₂ base is formed by two O atoms from carbonyl and phosphoryl groups, and by two N atoms from a 1,10‐phenanthroline molecule. A coordinated Cl atom occupies the apex. N—H...Cl hydrogen bonds link the molecules into one‐dimensional chains. The trichloromethyl group is rotationally disordered over two positions, with occupancies of 0.747 (7) and 0.253 (7).     

Bromidobis[2‐(pyridin‐2‐yl)methanol‐κ2N,O]copper(II) bromide monohydrate

The title compound, [CuBr(C₆H₇NO)₂]Br·H₂O, is an ionic mononuclear complex in which the [CuBr(C₆H₇NO)₂]⁺ cation possesses distorted square‐pyramidal geometry. The Cu^II centre is coordinated by two neutral 2‐(pyridin‐2‐yl)methanol (2‐pyMeOH) ligands and a terminal bromide ligand. The 2‐pyMeOH ligands are coordinated in a bidentate chelating manner through the pyridine N and hydroxy O atoms, forming a five‐membered chelate ring with the Cu^II centre. The planes of the pyridine rings are twisted by 58.71 (14)° with respect to each other. The charge is balanced by a noncoordinating bromide anion which, together with a solvent water molecule, links the components through hydrogen bonds into infinite chains propagating along the a axis. The mononuclear cations appear to associate in pairs through weak interactions between the metal atom of one cation and the halogen atom of an adjacent cation.     

A capped trigonal prismatic cadmium complex with tetra‐ and tridentate ligands: bis­(tri­ethanol­amine)‐κ3N,O,O′;κ4N,O,O′,O′′‐cadmium(II) squarate monohydrate

In the crystal structure of the title compound, [Cd(C₆H₁₅NO₃)₂](C₄O₄)·H₂O, a supramolecular structure is observed. The asymmetric unit consists of one unit of the cationic Cd complex, one water mol­ecule and two half‐squarate anions, each sitting on a crystallographic inversion center. The different coordinations of the two triethanolamine (TEA) ligands results in an unusual example of coordination number seven for the Cd^II ion. Both TEA ligands coordinate to the Cd^II ion, forming a distorted monocapped trigonal prismatic geometry with approximate C_2v symmetry. One of the TEA ligands acts as an N,O,O′‐tridentate ligand, whereas the other behaves as an N,O,O′,O′′‐tetradentate donor. The anions and cations are linked to one another by hydrogen bonds between hydroxy H atoms of the TEA ligands and squarate O atoms. The crystal structure is stabilized by O—H⋯O hydrogen bonds between the unligated water mol­ecule and a squarate O atom, together with a weak π–ring interaction between the ethyl­ene group of a TEA ligand and a squarate anion.     

Aqua­(2,2′‐diamino‐4,4′‐bi‐1,3‐thia­zole‐κ2N,N′)(oxydiacetato‐κ3O,O′,O′′)cobalt(II) trihydrate

The title compound, [Co(C₄H₄O₅)(C₆H₆N₄S₂)(H₂O)]·3H₂O, displays a distorted octa­hedral coordination geometry. The tridentate oxydiacetate dianion chelates the Cu^II atom in the meridional mode. In the crystal packing, hydro­philic and hydro­phobic layers are arranged in an alternating manner. In addition, a three‐dimensional hydrogen‐bonding framework and π–π stacking are present.     

Poly[[[aqua­(2,2′‐bipyridine‐κ2N,N′)manganese(II)]‐μ3‐acetyl­enedicarboxylato‐κ3O:O′:O′′] monohydrate]

In the title complex, {[Mn(C₄O₄)(C₁₀H₈N₂)(H₂O)]·H₂O}_n, each Mn^II ion has a distorted octa­hedral coordination formed by two N atoms of a 2,2′‐bipyridine ligand, three carboxyl O atoms of three different acetyl­ene­dicarboxyl­ate ligands and one coordinated water mol­ecule. The acetyl­ene­dicarboxyl­ate ligands act in a tridentate mode connecting adjacent Mn^II ions and constructing a two‐dimensional structure which can be regarded as an unusual plywood‐like stacked network.     

Polymorphism in bipodal O,O′‐dimeth­yl N,N′‐(m‐phenyl­ene­di­carbonyl)bis(thio­carbamate)

The title compound, C₁₂H₁₂N₂O₄S₂, crystallizes in white and yellow polymeric forms as a result of inter­esting anti–anti and syn–anti conformational isomerism of the thio­carbon­yl and carbon­yl moieties relative to one another. This work is the first reported X‐ray crystallographic structure determination of isomers of this class of bipodal ligand. The white form, anti–anti, (I), crystallizes with the benzene ring lying about a twofold rotation axis, resulting in both of the thio­carbon­yl and carbon­yl moieties being anti relative to each other. The yellow modification crystallizes as syn–anti, (II), with one thio­carbon­yl moiety syn and the other anti relative to the respective carbon­yl groups. The individual mol­ecules of both (I) and (II) are extensively linked through inter­molecular hydrogen bonds. Inter­molecular hydrogen bonding in (II) includes a network of bifurcated N—H⋯O and N—H⋯S hydrogen bonds, while mol­ecules of (I) include bifurcated C—H⋯O hydrogen bonds.     

Synthesis of 9‐Halogenated 9‐Deazaguanine N7‐(2′‐Deoxyribonucleosides)

The syntheses of N⁷‐glycosylated 9‐deazaguanine 1a as well as of its 9‐bromo and 9‐iodo derivatives 1b , c are described. The regioselective 9‐halogenation with N‐bromosuccinimide (NBS) and N‐iodosuccinimide (NIS) was accomplished at the protected nucleobase 4a (2‐{[(dimethylamino)methylidene]amino}‐3,5‐dihydro‐3‐[(pivaloyloxy)methyl]‐4H‐pyrrolo[3,2‐d]pyrimidin‐4‐one). Nucleobase‐anion glycosylation of 4a – c with 2‐deoxy‐3,5‐di‐O‐(p‐toluoyl)‐α‐D ‐erythro‐pentofuranosyl chloride ( 5 ) furnished the fully protected intermediates 6a – c (Scheme 2). They were deprotected with 0.01M NaOMe yielding the sugar‐deprotected derivatives 8a – c (Scheme 3). At higher concentrations (0.1M NaOMe), also the pivaloyloxymethyl group was removed to give 7a – c , while conc. aq. NH₃ solution furnished the nucleosides 1a – c . In D₂O, the sugar conformation was always biased towards S (67–61%).     

Poly[(N,N‐dimethylformamide‐κO)(μ3‐4,4′‐ethylenedibenzoato‐κ5O,O′:O′:O′′,O′′′)(pyrazino[2,3‐f][1,10]phenanthroline‐κ2N8,N9)lead(II)]

In the title Pb^II coordination polymer, [Pb(C₁₆H₁₀O₄)(C₁₄H₈N₄)(C₃H₇NO)]_n, each Pb^II atom is eight‐coordinated by two chelating N atoms from one pyrazino[2,3‐f][1,10]phenanthroline (L) ligand, one dimethylformamide (DMF) O atom and five carboxylate O atoms from three different 4,4′‐ethylenedibenzoate (eedb) ligands. The eedb dianions bridge neighbouring Pb^II centres through four typical Pb—O bonds and one longer Pb—O interaction to form a two‐dimensional structure. The C atoms from the L and eedb ligands form C—H...O hydrogen bonds with the O atoms of eedb and DMF ligands, which further stabilize the structure. The title compound is the first Pb^II coordination polymer incorporating the L ligand.