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.     

N‐(3H‐Thia­zol‐2‐yl­idene)­nitr­amine and N‐methyl‐N‐(thia­zol‐2‐yl)­nitr­amine

The geometries of the thia­zole ring and the nitr­amino groups in N‐(3H‐thia­zol‐2‐yl­idene)­nitr­amine, C₃H₃N₃O₂S, (I), and N‐­methyl‐N‐(thia­zol‐2‐yl)­nitr­amine, C₄H₅N₃O₂S, (II), are very similar. The nitr­amine group in (II) is planar and twisted along the C—N bond with respect to the thia­zole ring. In both structures, the asymmetric unit includes two practically equal mol­ecules. In (I), the mol­ecules are arranged in layers connected to each other by N—H⋯N and much weaker C—H⋯O hydrogen bonds. In the crystal structure of (II), the mol­ecules are arranged in layers bound to each other by both weak C—H⋯O hydrogen bonds and S⋯O dipolar interactions.     

2,3‐Dihydro‐3‐methyl‐2‐nitrimino‐1,3‐thiazole

The title compound {alternatively, 3‐methyl‐2‐[oxido(oxo)hydrazono]‐2,3‐dihydro‐1,3‐thiazole}, C₄H₅N₃O₂S, was obtained by methyl­ation of N‐(2‐thia­zolyl)­nitr­amine. The molecule lies on a mirror plane and the thia­zole ring is planar, regular in shape and aromatic. The S atom participates in the aromatic sextet via an electron pair on the 3p_z orbital. In the crystal, the mol­ecules are arranged in parallel layers, bound to each other by weak C—H?O and C—H?N hydrogen bonds and by S?O dipolar interactions, with an interlayer separation of 3.23 Å.     

Tetrakis(μ‐benzothiazole‐2‐thiolato)‐1:2κ4N:S2;1:2κ4S2:N‐dichloro‐1κCl,2κCl‐dirhenium(III)(Re—Re) dichloromethane solvate: a bridged complex with a long Re—Re quadruple bond

The title compound, [Re₂(C₇H₄NS₂)₄Cl₂]·CH₂Cl₂, consists of dirhenium mol­ecules with bridging N,S‐benzo­thia­zole‐2‐thiol­ate ligands, axial Cl^? ligands and intramolecular hydrogen bonding. These mol­ecules adopt somewhat staggered conformations, with a long Re—Re quadruple bond distance of 2.2716 (3) Å.     

2,2′‐[2,3‐Di­hydro‐2‐(prop‐2‐enyl)‐1H‐isoindole‐1,3‐diyl­idene]bis(propane­di­nitrile)–tetra­thia­fulvalene (1/1), TCPI–TTF

The title complex, C₁₇H₉N₅·C₆H₄S₄, contains π‐deficient bis(di­nitrile) and TTF mol­ecules stacked alternately in columns along the a‐axis direction; the interplanar angle between the TTF molecule and the isoindolinyl C₄N[C(CN)₂]₂ moiety is 1.21 (4)°. The N‐allyl moiety in the TCPI mol­ecule is oriented at an angle of 87.10 (10)° with respect to the five‐membered C₄N ring, and the four C[triple‐bond]N bond lengths range from 1.134 (3) to 1.142 (3) Å, with C—C[triple‐bond]N angles in the range 174.3 (3)–176.9 (2)°. In the TTF system, the S—C bond lengths are 1.726 (3)–1.740 (3) and 1.751 (2)–1.763 (2) Å for the external S—C(H) and internal S—C(S) bonds, respectively.     

6‐(3,4‐Di­fluoro­benzoyl)‐3‐[2‐(4‐pyridyl)­ethyl]‐1,3‐benzo­thia­zol‐2(3H)‐one

A new type of benzo­thia­zolinone derivative with potential pharmacological activity, viz. 6‐(3,4‐di­fluoro­benzoyl)‐3‐[2‐(4‐pyridyl)­ethyl]‐1,3‐benzo­thia­zol‐2(3H)‐one, C₂₁H₁₄F₂N₂O₂S, has been prepared and studied by NMR, IR and single‐crystal X‐ray diffraction techniques. The mol­ecule is not planar, the pyridine and di­fluoro­benzene moieties being located above and below the benzo­thia­zole ring system. The carbonyl O atoms are involved in an intramolecular hydrogen‐bond‐type interaction.     

(2,2′‐Di­amino‐4,4′‐bi‐1,3‐thia­zole‐κ2N3,N3′)(oxy­diacetato‐κ3O,O′,O′′)­copper(II) monohydrate

The title compound, [Cu(C₄H₄O₅)(C₆H₆N₄S₂)]·H₂O, displays a square‐pyramidal coordination geometry. The tridentate oxy­di­acetate dianion chelates the Cu^II atom in the facial mode. The large difference [0.487 (4) Å] between the longest Cu—O distance in the basal plane and that in the apical direction correlates with the small displacement of the Cu^II atom [0.0576 (13) Å] from the basal plane towards the apex of the square pyramid. The intermolecular hydrogen‐bonding network results in a closely overlapped arrangement of the coordination basal plane and the thia­zole ring of a neighboring mol­ecule.     

4,7‐Bis(4‐pyridyl­ethynyl)‐2,1,3‐benzo­thia­diazo­le and its dipyridinium diperchlorate

The title compound, C₂₀H₁₀N₄S, and its dipyridinium salt, 4,4′‐(2,1,3‐benzo­diazol‐4,7‐diyl­diethynyl)­dipyridinium diperchlorate, C₂₀H₁₂N₄S²⁺·2ClO₄^?, display bond alternation in the 2,1,3‐benzo­thia­diazo­le rings, which suggests their quinonoid character. The dipyridinium dication mol­ecules stack along the a axis and form a dimer with short S?N interheteroatom contacts [3.146 (4) Å] between the two 1,2,5‐thia­diazo­le rings. The dimer is surrounded by the perchlorate anions with which it forms a large number of intermolecular N—H?O and C—H?O hydrogen bonds.     

4‐Fluoro‐2‐(phospho­no­methyl)­benzene­sulfonic acid monohydrate

The title compound, C₇H₈FO₆PS·H₂O, contains both phospho­nic and sulfonic acid functionalities. An extensive network of O—H?O hydrogen bonds is present in the crystal structure. The three acidic protons are associated with the phospho­nate group. Two protons experience typical hydrogen‐bond contacts with the sulfonate‐O atoms, while the third has a longer covalent bond of 1.05 (3) Å to the phospho­nate‐O atom and a short hydrogen‐bond contact of 1.38 (3) Å to the water O atom (all O—H?O angles are in the range 162–175°). The sulfonate group is positioned so that one S—O bond is nearly coplanar with the phenyl ring [torsion angle O—S—C—C ?8.6 (2)°]. The phospho­nate group is oriented approximately perpendicular to the ring [torsion angle P—C—C—C 99.2 (2)°] with one P—O bond anti to the benzyl C—C bond. The mol­ecules pack in layers in the b–c plane with the water mol­ecules in between adjacent pairs of inverted layers.     

4‐(4‐Chloro­phen­yl)‐3‐(4‐phenyl­pent‐4‐en­yloxy)‐1,3‐thia­zole‐2(3H)‐thione

The title compound, C₂₀H₁₈ClNOS₂, is a thia­zole‐derived thio­hydroxamic acid O‐ester. The value of Z′ is 3 and the asymmetric unit comprises three mol­ecules of identical helicity along the N—O bond. Two of these show an anti and the third a syn arrangement of substituents attached in positions 3 and 4 to the 1,3‐thia­zole nucleus.     

2‐[2‐Methyl‐5‐nitro‐4‐(phenyl­sulfonyl­methyl)­imidazol‐1‐yl]­ethanol and 2‐methyl‐5‐nitro‐4‐phenyl­sulfonyl­methyl‐1,3‐thia­zole

The title compounds, C₁₃H₁₅N₃O₅S and C₁₁H₁₀N₂O₄S₂, respectively, both contain a phenyl­sulfonyl group connected, through a methyl­ene bridge, to either a substituted nitro­imidazole or nitro‐1,3‐thia­zole ring. In the imidazole‐containing mol­ecule, the nitro and sulfonyl groups are trans relative to the sulfonyl–methyl bond, while in the thia­zole‐containing mol­ecule, these substituents are cis. The stabilizing interactions within the crystals are also different between the two compounds.     

Novel heterocyclic inhibitors of matrix metalloproteinases: three 6H‐1,3,4‐thiadiazines

The title compounds, (2S)‐N‐[5‐(4‐chloro­phenyl)‐2,3‐di­hydro‐6H‐1,3,4‐thia­diazin‐2‐yl­idene]‐2‐[(phenyl­sulfonyl)­amino]­pro­pan­amide, C₁₈H₁₇ClN₄O₃S₂, (I), (2R)‐N‐[5‐(4‐fluoro­phenyl)‐6H‐1,3,4‐thia­diazin‐2‐yl]‐2‐[(phenyl­sulfonyl)amino]­propan­amide, C₁₈H₁₇FN₄O₃S₂, (II), and (2S)‐N‐[5‐(5‐chloro‐2‐thienyl)‐6H‐1,3,4‐thia­diazin‐2‐yl]‐2‐[(phenyl­sulfonyl)­amino]­propan­amide, C₁₆H₁₅ClN₄O₃S₃, (III), are potent inhibitors of matrix metalloproteinases. In all three compounds, the thia­diazine ring adopts a screw‐boat conformation. The mol­ecules of compound (I) show a short intramolecular N_Ala—H?N_exo hydrogen bond [N?N 2.661 (3) Å] and are linked into a chain along the c axis by N_endo—H?S_endo and N_endo—H?O_Ala hydrogen bonds [N?S 3.236 (3) and N?O 3.375 (3) Å] between neighbouring mol­ecules. In compound (II), the mol­ecules are connected antiparallel into a chain along the a axis by N_exo—H?O_Ala and N_Ala—H?N_endo hydrogen bonds [N?O 2.907 (6) and N?N 2.911 (6) Å]. The mol­ecules of compound (III) are dimerized antiparallel through N_exo—H?N_endo hydrogen bonds [N?N 2.956 (7) and 2.983 (7) Å]. The different hydrogen‐bonding patterns can be explained by an amido–imino tautomerism (prototropic shift) shown by different bond lengths within the 6H‐1,3,4‐thia­diazine moiety.     

On the short carbonyl bond in bis[μ‐1,2‐benzisothiazol‐3(2H)‐one 1,1‐dioxido‐κ2N:O]bis{[1,2‐benzisothiazol‐3(2H)‐one 1,1‐dioxido‐κN]bis(imidazole)copper(II)}

The short carbonyl bond in the title compound, [Cu₂(C₇H₄­NO₃S)₄(C₃H₄N₂)₄] [Liu, Huang, Li & Lin (1991). Acta Cryst. C 47 , 41–43], is an artifact of disorder in the iso­thia­zol‐3(2H)‐one 1,1‐dioxide part of the 1,2‐benziso­thia­zol‐3(2H)‐one entity. In the present redetermination, all bond dimensions in the centrosymmetric dinuclear mol­ecule are normal. The five‐coordinate Cu atom shows trigonal–bipyramidal coordination. Hydro­gen bonds from the imidazole donor ligand link adjacent mol­ecules into a two‐dimensional layer structure.     

Dichloro(2,2′‐diamino‐4,4′‐bi‐1,3‐thiazole‐N3,N3′)copper(II)

The title complex, [CuCl₂(C₆H₆N₄S₂)], has a flattened tetrahedral coordination. The Cu^II atom is located on a twofold rotation axis and is coordinated by two N atoms from a chelating 2,2′‐di­amino‐4,4′‐bi‐1,3‐thia­zole ligand and by two Cl atoms. Intramolecular hydrogen bonding exists between the amino groups of the 2,2′‐di­amino‐4,4′‐bi‐1,3‐thia­zole ligand and the Cl atoms. The intermolecular separation of 3.425 (1) Å between parallel bi­thia­zole rings suggests there is a π–π interaction between them.     

2,2′‐(1,2‐Ethanediyldithio)bis(1,3‐benzothiazole)

In the title compound, C₁₆H₁₂N₂S₄, which is the result of the S‐alkyl­ation reaction of 2‐mercapto­benzo­thia­zole with ethyl­ene dibromide, the planes of the two benzo­thia­zole moieties form a dihedral angle of 3.84 (14)°. The bridging chain moiety, –SCH₂CH₂S–, adopts an antiperiplanar conformation. There are intermolecular S⃛S non‐bonded contacts of 3.6471 (9) Å, which stabilize the crystal packing.     

mer‐Tri­chloro­tris(1,3‐thia­zole‐N)­ruthenium(III)

The potentially cytostatic title compound, mer‐[RuCl₃(C₃H₃NS)₃], is the first Ru^III–thz (thz is 1,3‐thia­zole) complex characterized via X‐ray diffraction and consists of discrete complex mol­ecules with an octahedral coordination sphere in which the metal centre is linked to three chloride ions and to three thz ligands through the N atoms. The Ru—Cl and Ru—N bond distances average 2.3462 (6) and 2.0851 (19) Å, respectively.     

Conformational preferences in 2‐­nitrophenylthiolates: S‐(2‐nitro­phenyl) 4‐toluenethiosulfonate

In the title compound, C₁₃H₁₁NO₄S₂, the nitro group is rotated by 44.1 (1)° out of the plane of the adjacent aryl ring and the toluene­thio­sulfonate group is almost orthogonal to the plane of the nitrated aryl ring. There are three types of C—H?O hydrogen bond in the structure [C?O range 3.324 (3)–3.503 (3) Å; C—H?O range 160–173°] and these link the mol­ecules into a three‐dimensional framework.     

Precursor of a β‐lactamase inhibitor: allyl (4S,8S,9R)‐10‐[(E)‐ethyl­idene]‐4‐methoxy‐11‐oxo‐1‐aza­tri­cyclo­[7.2.0.03,8]­undec‐2‐ene‐2‐carboxyl­ate

The molecular structure of the title tricyclic compound, C₁₇H₂₁NO₄, which is the immediate precursor of a potent synthetic inhibitor {Lek157: sodium (8S,9R)‐10‐[(E)‐ethyl­idene]‐4‐methoxy‐11‐oxo‐1‐aza­tri­cyclo­[7.2.0.0^3,8]­undec‐2‐ene‐2‐carboxyl­ate} with remarkable potency, provides experimental evidence for the previously modelled relative position of the fused cyclo­hexyl ring and the carbonyl group of the β‐lactam ring, which takes part in the formation of the initial tetrahedral acyl–enzyme complex. In this hydro­phobic mol­ecule, the overall geometry is influenced by C—H?O intramolecular hydrogen bonds [3.046 (4) and 3.538 (6) Å, with corresponding normalized H?O distances of 2.30 and 2.46 Å], whereas the mol­ecules are interconnected through intermolecular C—H?O hydrogen bonds [3.335 (4)–3.575 (5) Å].     

4‐Methyl‐2‐[N‐(3,4‐methyl­ene­dioxy­benzyl­idene)hydrazino]­thia­zole and its reduction product, 4‐methyl‐2‐[N‐(3,4‐methyl­ene­dioxybenzyl­idene)hydrazono]‐4,5‐di­hydro­thia­zole

The crystal structures of 4‐methyl‐2‐[N‐(3,4‐methyl­ene­dioxybenzyl­idene)hydrazino]­thia­zole, C₁₂H₁₁N₃O₂S, and its reduction product 4‐methyl‐2‐[N‐(3,4‐methyl­ene­dioxybenzyl­idene)hydrazono]‐4,5‐di­hydro­thia­zole, C₁₂H₁₃N₃O₂S, have been determined and compared. In the reduction product, the tautomer observed bears an H atom on the exocyclic N atom. Both compounds form hydrogen‐bonded dimers over centers of inversion.     

Poly[tetrasodium(I)‐tetra‐μ2‐bis(butane‐1,4‐diyldioxy)borato‐μ2‐1,4‐butane­diol]

In the title compound, [Na₄(C₈H₁₆BO₄)₄(C₄H₁₀O₂)]_n, there are two coordination types for the four independent Na⁺ cations: two Na⁺ cations bond to six diolate O atoms [Na—O = 2.305 (2)–2.609 (2) Å], while the other two are five‐coordinate via one 1,4‐butane­diol [2.289 (2) and 2.349 (3) Å] and four diolate O atoms [2.295 (2)–2.408 (2) Å]. Corresponding to this, there are three‐ and four‐coordinate diolate O atoms, the latter bridging Na atoms. The 1,4‐butane­diol mol­ecules lie on inversion centres. The boron stereochemistry shows minor local perturbations from its usual tetrahedral state [B—O = 1.457 (4)–1.503 (4) Å]. The resulting polymer packs as sheets parallel to the (10) plane crosslinked by the butane­diol mol­ecules. The structure was solved using data from a multiple crystal.