Three N2‐benzoyl­oxybenz­amidines: sheet structures built from hard and soft hydrogen bonds and aromatic π–π stacking interactions

Molecules of the title compounds N²‐(benzoyl­oxy)­benz­ami­dine, C₁₄H₁₂N₂O₂, (I), N²‐(2‐hydroxy­benzoyl­oxy)­benz­ami­dine, C₁₄H₁₂N₂O₃, (II), and N²‐benzoyloxy‐2‐hydroxybenzamidine, C₁₄H₁₂N₂O₃, (III), all have extended chain conformations, with the aryl groups remote from one another. In (I), the mol­ecules are linked into chains by a single N—H⋯N hydrogen bond [H⋯N = 2.15 Å, N⋯N = 3.029 (2) Å and N—H⋯N = 153°] and these chains are linked into sheets by means of aromatic π–π stacking interactions. There is one intramolecular O—H⋯O hydrogen bond in (II), and a combination of one three‐centre N—H⋯(N,O) hydrogen bond [H⋯N = 2.46 Å, H⋯O = 2.31 Å, N⋯N = 3.190 (2) Å, N⋯O = 3.146 (2) Å, N—H⋯N = 138° and N—H⋯O = 154°] and one two‐centre C—H⋯O hydrogen bond [H⋯O = 2.46 Å, C⋯O = 3.405 (2) Å and C—H⋯O = 173°] links the mol­ecules into sheets. In (III), an intramolecular O—H⋯N hydrogen bond and two N—H⋯O hydrogen bonds [H⋯O = 2.26 and 2.10 Å, N⋯O = 2.975 (2) and 2.954 (2) Å, and N—H⋯O = 138 and 163°] link the molecules into sheets.     

Adducts of 1,1,1‐tris(4‐hydroxyphenyl)ethane with diamines: three‐dimensional hydrogen‐bonded frameworks formed with 1,6‐diaminohexane and 2,2′‐bipyridyl

The adduct 1,6‐di­amino­hexane–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2) is a salt {hexane‐1,6‐diyldiammonium–4‐[1,1‐bis(4‐hydroxyphenyl)ethyl]phenolate (1/2)}, C₆H₁₈N₂²⁺·2C₂₀H₁₇O₃^?, in which the cation lies across a centre of inversion in space group P. The anions are linked by two short O—H?O hydrogen bonds [H?O 1.74 and 1.76 Å, O?O 2.5702 (12) and 2.5855 (12) Å, and O—H?O 168 and 169°] into a chain containing two types of R(24) ring. Each cation is linked to four different anion chains by three N—H?O hydrogen bonds [H?O 1.76–2.06 Å, N?O 2.6749 (14)–2.9159 (14) Å and N—H?O 156–172°]. In the adduct 2,2′‐bipyridyl–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2), C₁₀H₈N₂·2C₂₀H₁₈O₃, the neutral di­amine lies across a centre of inversion in space group P2₁/n. The tris­(phenol) mol­ecules are linked by two O—H?O hydrogen bonds [H?O both 1.90 Å, O?O 2.7303 (14) and 2.7415 (15) Å, and O—H?O 173 and 176°] into sheets built from R(38) rings. Pairs of tris­(phenol) sheets are linked via the di­amine by means of a single O—H?N hydrogen bond [H?N 1.97 Å, O?N 2.7833 (16) Å and O—H?N 163°].     

Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): monomeric and polymeric adducts with 1,2‐bis(4‐pyridyl)­ethene and 1,6‐di­amino­hexane

In the adduct ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–1,2‐bis(4‐pyridyl)­ethene (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₂H₁₀N₂, there is an intramolecular O—H?O hydrogen bond in the ferro­cene­diol component and a single O—H?N hydrogen bond linking the diol to the di­amine, which is disordered over two sets of sites, so forming a finite monomeric adduct. In the adduct ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–1,6‐di­amino­hexane (2/1), 2[Fe(C₁₈H₁₅O)₂]·C₆H₁₆N₂, the amine lies across a centre of inversion in space group P. There is an intramolecular O—H?O hydrogen bond in the ferrocenediol, and the molecular components are linked by O—H?N and N—H?O hydrogen bonds, one of each type, into a C(13)[R(12)] chain of rings.     

5‐Chloro‐N‐(2‐hydroxy‐5‐methyl­phenyl)­salicyl­ald­imine

The title compound, N‐(5‐chloro‐2‐oxido­benzyl­idene)‐2‐hydroxy‐5‐methyl­anilinium, C₁₄H₁₂ClNO₂, is a tridentate Schiff base with almost planar molecules. Each mol­ecule contains a strong intramolecular N—H?O hydrogen bond [2.576 (2) Å]. There is also an intermolecular O—H?O hydrogen bond [2.695 (2) Å] linking neighbouring mol­ecules into infinite chains along the [101] direction.     

3‐[(2‐Oxo‐1‐naphthylidene)methyl­amino]­benzoic acid

The title compound, C₁₈H₁₃NO₃, exists as a keto­amino tautomer implying a fairly short N—H?O intramolecular hydrogen bond between the 2‐naphthalenone and amino moieties [N?O 2.531 (3) Å] which is enhanced by the π‐electron delocalization effect. The naphthald­imine and 3‐carboxy­phenyl fragments are inclined at an angle of 4.41 (7)°, so the mol­ecule is almost planar. The mol­ecules are connected by intermolecular O—H?O hydrogen bonds between the carboxy and keto O atoms, forming infinite chains around the twofold screw axes parallel to b .     

2‐Amino‐4‐(4‐pyridyl)­pyrimidine and the 1:1 adduct with 4‐amino­benzoic acid

The structure of the title compound, C₉H₈N₄, comprises non‐planar mol­ecules that associate via pyrimidine N—H?N dimer R(8) hydrogen‐bonding associations [N?N 3.1870 (17) Å] and form linear hydrogen‐bonded chains via a pyrimidine N—H?N(pyridyl) interaction [N?N 3.0295 (19) Å]. The dihedral angle between the two rings is 24.57 (5)°. The structure of the 1:1 adduct with 4‐amino­benzoic acid, C₉H₈N₄·C₇H₇NO₂, exhibits a hydrogen‐bond­ing network involving COOH?N(pyridyl) [O?N 2.6406 (17) Å], pyrimidine N—H?N [N?N 3.0737 (19) and 3.1755 (18) Å] and acid N—H?O interactions [N?O 3.0609 (17) and 2.981 (2) Å]. The dihedral angle between the two linked rings of the base is 38.49 (6)° and the carboxyl­ic acid group binds to the stronger base group in contrast to the (less basic) complementary hydrogen‐bonding site.     

Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): monomeric and dimeric 1:1 adducts with 1,2‐bis(4‐pyridyl)­ethane and 1,2‐­diamino­ethane

In ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–4,4′‐ethyl­enedi­pyridine (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₂H₁₂N₂, there is an intra­molecular O—H?O hydrogen bond in the ferrocenediol component and a single O—H?N hydrogen bond linking the two components into a finite monomeric adduct. Ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–ethyl­enedi­amine (1/1), [Fe(C₁₈H₁₅O)₂]·C₂H₈N₂, crystallizes with Z′ = 2 in space group P, and there are two independent four‐component aggregates in the structure, both of which are centrosymmetric. In the first type of aggregate, the molecular components are linked by O—H?N and N—H?O hydrogen bonds, in which both di­amine N atoms participate; in the second type of aggregate, the di­amine component is disordered over two sets of sites, but only one N atom is involved in the hydrogen bonding.     

Chains of fused rings in the hydrogen‐bonded structure of meso‐­6,13‐di­amino‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane–2,2′‐biphenol (1/2)

The title compound is a salt, [C₁₂H₃₂N₆]²⁺·2[HOC₆H₄C₆H₄O]^?. The centrosymmetric cation contains two intramolecular N—H?N hydrogen bonds with an N?N distance of 2.8290 (13) Å, and the pendent amino groups are in axial sites; the anion contains an intramolecular O—H?O hydrogen bond with an O?O distance of 2.4656 (11) Å. The ions are linked into continuous chains by means of four types of N—H?O hydrogen bonds with N?O distances ranging from 2.7238 (12) Å to 3.3091 (13) Å, associated with N—H?O angles in the range 148–160°.     

π‐Stacked hydrogen‐bonded dimers in 2‐(2‐nitro­phenyl­amino­carbonyl)­benzoic acid,and hydrogen‐bonded sheets in orthorhombic and monoclinic polymorphs of 2‐(4‐nitro­phenyl­amino­carbonyl)­benzoic acid

Molecules of 2‐(2‐nitrophenylaminocarbonyl)benzoic acid, C₁₄H₁₀N₂O₅, are linked into centrosymmetric R(8) dimers by a single O—H⋯O hydrogen bond [H⋯O = 1.78 Å, O⋯O = 2.623 (2) Å and O—H⋯O = 178°] and these dimers are linked into sheets by a single aromatic π–π stacking interaction. The isomeric compound 2‐(4‐nitrophenylaminocarbonyl)benzoic acid crystallizes in two polymorphic forms. In the orthorhombic form (space group P2₁2₁2₁ with Z′ = 1, crystallized from ethanol), the mol­ecules are linked into sheets of R(22) rings by a combination of one N—H⋯O hydrogen bond [H⋯O = 1.96 Å, N⋯O = 2.833 (3) Å and N—H⋯O = 171°] and one O—H⋯O hydrogen bond [H⋯O = 1.78 Å, O⋯O = 2.614 (3) Å and O—H⋯O = 173°]. In the monoclinic form (space group P2₁/n with Z′ = 2, crystallized from acetone), the mol­ecules are linked by a combination of two N—H⋯O hydrogen bonds [H⋯O = 2.09 and 2.16 Å, N⋯O = 2.873 (4) and 2.902 (3) Å, and N—H⋯O = 147 and 141°] and two O—H⋯O hydrogen bonds [H⋯O = 1.84 and 1.83 Å, O⋯O = 2.664 (3) and 2.666 (3) Å, and O—H⋯O = 166 and 174°] into sheets of some complexity. These sheets are linked into a three‐dimensional framework by a single C—H⋯O hydrogen bond [H⋯O = 2.45 Å, C⋯O = 3.355 (4) Å and C—­H⋯O = 160°].     

Phthal­imide at 120 K: perforated molecular ribbons containing three different ring motifs

Molecules of phthal­imide [1H‐iso­indole‐1,3(2H)‐dione], C₈H₅NO₂, are linked by N—H?O hydrogen bonds [H?O 2.02 Å, N?O 2.8781 (16) Å and N—H?O 167°] and by C—H?O hydrogen bonds [H?O 2.54 and 2.56 Å, C?O 3.3874 (18) and 3.4628 (19) Å, and C—H?O 149 and 159°] into molecular ribbons, which are pierced by three different ring motifs; there are two centrosymmetric R(8) rings, each containing a single hydrogen bond, N—H?O in one case and C—H?O in the other, and R(9) rings containing all three hydrogen bonds.     

6‐Amino‐3‐methyl‐5‐nitro­so­pyrimi­dine‐2,4(1H,3H)‐dione forms a three‐dimensional hydrogen‐bonded framework structure

Molecules of the title compound, C₅H₆N₄O₃, are linked into a single three‐dimensional framework by a two‐centre N—H⃛O hydrogen bond [H⃛O = 1.92 Å, N⃛O = 2.785 (2) Å and N—H⃛O = 168°], a two‐centre N—H⃛H hydrogen bond [H⃛N = 2.19 Å, N⃛N = 3.017 (2) Å and N—H⃛N = 157°] and the intermolecular component of an effectively planar three‐centre N—H⃛(O)₂ hydrogen bond [H⃛O = 2.03 and 2.31 Å, N⃛O = 2.645 (2) and 2.957 (2) Å, N—H⃛O = 126 and 130°, and O⃛H⃛O = 101°].     

Hydro­gen bonding in substituted nitro­anilines: isolated nets in 1,3‐­diamino‐4‐nitrobenzene and continuously interwoven nets in 3,5‐­dinitro­aniline

Molecules of 1,3‐diamino‐4‐nitrobenzene, C₆H₇N₃O₂, are linked by N—H?O hydrogen bonds [N?O 2.964 (2) and 3.021 (2) Å; N—H?O 155 and 149°] into (4,4) nets. In 3,5‐di­nitro­aniline, C₆H₅N₃O₄, where Z′ = 2, the mol­ecules are linked by three N—H?O hydrogen bonds [N?O 3.344 (2)–3.433 (2) Å and N—H?O 150–167°] into deeply puckered nets, each of which is interwoven with its two immediate neighbours.     

Bis(4‐hydroxy­benzoato‐O)(1,4,8,11‐tetra­aza­cyclo­tetra­decane‐κ4N)nickel(II): a three‐dimensional framework built from O—H⋯O and N—H⋯O hydrogen bonds

The title compound, [Ni(C₇H₅O₃)₂(C₁₀H₂₄N₄)], contains octahedral Ni^II in a centrosymmetric trans configuration with Ni—N distances of 2.0637 (17) and 2.0699 (16) Å and an Ni—O distance of 2.1100 (14) Å. The mol­ecules are linked by a single type of O—H?O hydrogen bond [O?O 2.618 (2) Å and O—H?O 161°] into two‐dimensional sheets; a singletype of N—H?O hydrogen bond [N?O 2.991 (2) Å and N—H?O 139°] links these sheets into a three‐dimensional framework.     

3‐(p‐Chloro­phenyl)‐4‐phenyl‐4,5‐di­hydro­isoxazole‐5‐spiro‐2′‐1′,2′,3′,4′‐tetra­hydro­naphthalen‐1′‐one

In the title compound, C₂₄H₁₈ClNO₂, the phenyl ring and the tetralone moiety are approximately orthogonal to the isoxazoline ring. The isoxazoline ring adopts an envelope conformation, while the cyclo­hexenone ring of the tetralone moiety has an intermediate sofa/half‐chair conformation. In this structure, one C—H?N intermolecular and two C—H?O intramolecular hydrogen bonds occur; the H?A distances are 2.60, and 2.35 and 2.57 Å, respectively. The mol­ecules are held together by an intermolecular C—H?N hydrogen bond, forming a one‐dimensional chain along the [100] direction.     

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.     

Hydro­gen‐bond networks in tris(4‐hydroxy­phenyl)­methane and its 1:1 molecular complex with 4,4′‐bi­pyridine

In tris(4‐hydroxy­phenyl)­methane (or 4,4′,4′′‐methane­triyl­tri­phenol), C₁₉H₁₆O₃, mol­ecules are connected by O—H⃛O hydrogen bonds [O⃛O = 2.662 (2) and 2.648 (2) Å] into two‐dimensional square networks that are twofold interpenetrated. In tris(4‐hydroxy­phenyl)­methane–4,4′‐bi­pyridine (1/1), C₁₉H₁₆O₃·C₁₀H₈N₂, trisphenol mol­ecules form rectangular networks via O—H⃛O [O⃛O = 2.694 (3) Å] and C—H⃛O [C⃛O = 3.384 (3) Å] hydrogen bonds. Bi­pyridine mol­ecules hydrogen bonded to phenol moieties [O⃛N = 2.622 (3) and 2.764 (3) Å] fill the voids to complete the structure.     

Ferrocene compounds. XXXIV. 1′‐(tert‐Butoxycarbonylamino)ferrocene‐1‐carboxylic acid

Heteroannularly substituted ferrocene derivatives can act as model systems for various hydrogen‐bonded assemblies of biomol­ecules formed, for instance, by means of O—H⋯O and N—H⋯O hydrogen bonding. The crystal structure analysis of 1′‐(tert‐butoxy­carbonyl­amino)­ferrocene‐1‐carbox­ylic acid, [Fe(C₁₀H₁₄NO₂)(C₆H₅O₂)] or (C₅H₄COOH)Fe(C₅­H₄NHCOOC(CH₃)₃, reveals two independent mol­ecules within the asymmetric unit, and these are joined into discrete dimers by two types of intermolecular hydrogen bonds, viz. O—H⋯O and N—H⋯O. The –COOH and –NHCOOR groups are archetypes for dimer formation via two eight‐membered rings. The O—H⋯O hydrogen bonds [2.656 (3) and 2.663 (3) Å] form a cyclic carboxylic acid dimer motif. Another eight‐membered ring is formed by N—H⋯O hydrogen bonds [2.827 (3) and 2.854 (3) Å] between the N—H group and an O atom of another carbamoyl moiety. The dimers are assembled in a herring‐bone fashion in the bc plane.     

2‐Amino‐7‐chloro‐2′‐deoxy­tubercidin

In 4‐chloro‐7‐(2‐de­oxy‐β‐d ‐erythro‐pento­furanos­yl)‐7H‐pyr­rolo­[2,3‐d]­pyrimidine‐2,4‐diamine, C₁₁H₁₄ClN₅O₃, the conformation of the N‐glycosylic bond is between anti and high‐anti [χ = −102.5 (6)°]. The 2′‐deoxy­ribofuranosyl unit adopts the C3′‐endo‐C4′‐exo (³T₄) sugar pucker (N‐type) with P = 19.6° and τ_m = 32.9° [terminology: Saenger (1989). Landolt‐Börnstein New Series, Vol. 1, Nucleic Acids, Subvol. a, edited by O. Madelung, pp. 1–21. Berlin: Springer‐Verlag]. The orientation of the exocyclic C4′—C5′ bond is +ap (trans) with a torsion angle γ = 171.5 (4)°. The compound forms a three‐dimensional network that is stabilized by four inter­molecular hydrogen bonds (N—H⋯O and O—H⋯N) and one intra­molecular hydrogen bond (N—H⋯Cl).     

2′‐De­oxy‐2‐fluoro­tubercidin

In the title compound [systematic name: 7‐(2‐de­oxy‐β‐d ‐erythro‐pentofuranos­yl)‐2‐fluoro‐7H‐pyrrolo[2,3‐d]pyrimidin‐2‐amine], C₁₁H₁₃FN₄O₃, the conformation of the N‐glycosylic bond is between anti and high‐anti [χ = −110.2 (3)°]. The 2′‐deoxy­ribofuranosyl unit adopts the N‐type sugar pucker (₄T³), with P = 40.3° and τ_m = 39.2°. The orientation of the exocyclic C4′—C5′ bond is −ap (trans), with a torsion angle γ = −168.39 (18)°. The nucleobases are arranged head‐to‐head. The crystal structure is stabilized by four inter­molecular hydrogen bonds of types N—H⋯N, N—H⋯O and O—H⋯O.     

2‐[(2‐Hydro­xy‐4‐nitro­phenyl)­amino­methyl­ene]­cyclo­hexa‐3,5‐dien‐1(2H)‐one

The title compound, C₁₃H₁₀N₂O₄, adopts the keto–amine tautomeric form and displays an intramolecular N—H⋯O [N⋯O = 2.579 (2) Å] and three intermolecular O—H⋯O [O⋯O = 2.561 (2) Å] and C—H⋯O [C⋯O = 3.274 (2) and 3.318 (2) Å] hydrogen bonds. The keto–amine structure is favoured by through‐mol­ecule conjugation between the hydroxy O atom and imine N atom. The dihedral angle between the planes of the two aromatic rings is 10.79 (4)°.