(–)‐Dioxosantadienic acid: hydrogen‐bonding patterns in a bicyclic sesquiterpenoid keto acid and its mono­hydrate

The an­hydrous form, (I), of the title compound, (?)‐2‐(1,2,3,4,4a,7‐hexa­hydro‐4a,8‐di­methyl‐1,7‐dioxo‐2‐naphthyl)­propionic acid, C₁₅H₁₈O₄, derived from a naturally occurring sesquiterpenoid, has two mol­ecules in the asymmetric unit, (I) and (I′), differing in the conformations of the saturated ring and the carboxyl group. The compound aggregates as carboxyl‐to‐ketone hydrogen‐bonding catemers [O?O = 2.776 (3) and 2.775 (3) Å]. Two crystallographically independent sets of single‐strand hydrogen‐bonding helices with opposite end‐to‐end orientation pass through the cell in the b direction, one consisting exclusively of mol­ecules of (I) and the other entirely of (I′). Three C—H?O=C close contacts are found in (I). The monohydrate, C₁₅H₁₈O₄·H₂O, (II), with two mol­ecules of (I) plus two water mol­ecules in its asymmetric unit, forms a complex three‐dimensional hydrogen‐bonding network including acid‐to‐water, water‐to‐acid, water‐to‐ketone, water‐to‐water and acid‐to‐acid hydrogen bonds, plus three C—H?O=C close contacts. In both (I) and (II), only the ketone remote from the acid is involved in hydrogen bonding.     

(–)‐Gibberic acid: hydrogen‐bonding pattern of the monohydrate of a non‐­racemic tetracyclic δ‐keto acid derivative of gibberellin A3

In the the title compound, 1,7‐di­methyl‐8‐oxo‐4bα,7α‐gibba‐1,3,4a(10a)‐triene‐10β‐carboxyl­ic acid monohydrate, C₁₈H₂₀O₃·H₂O, the water of hydration accepts a hydrogen bond from the carboxyl and donates hydrogen bonds to the carboxyl carbonyl and the ketone in two different screw‐related neighbors, which are mutually translational, yielding a complex three‐dimensional hydrogen‐bonding array.     

Phenyl‐ and mesitylglyoxylic acids: catemeric hydrogen bonding in two α‐keto acids

α‐Oxo­benzene­acetic (phenyl­glyoxy­lic) acid, C₈H₆O₃, adopts a transoid di­carbonyl conformation in the solid state, with the carboxyl group rotated 44.4 (1)° from the nearly planar benzoyl moiety. The heterochiral acid‐to‐ketone catemers [O?O = 2.686 (3) and H?O = 1.78 (4) Å] have a second, longer, intermolecular O—H?O contact to a carboxyl sp³ O atom [O?O = 3.274 (2) and H?O = 2.72 (4) Å], with each flat ribbon‐like chain lying in the bc plane and extending in the c direction. In α‐oxo‐2,4,6‐tri­methyl­benzene­acetic (mesityl­glyoxy­lic) acid, C₁₁H₁₂O₃, the ketone is rotated 49.1 (7)° from planarity with the aryl ring and the carboxyl group is rotated a further 31.2 (7)° from the ketone plane. The solid consists of chiral conformers of a single handedness, aggregating in hydrogen‐bonding chains whose units are related by a 3₁ screw axis, producing hydrogen‐bonding helices that extend in the c direction. The hydrogen bonding is of the acid‐to‐acid type [O?O = 2.709 (6) and H?O = 1.87 (5) Å] and does not formally involve the ketone; however, the ketone O atom in the acceptor mol­ecule has a close polar contact with the same donor carboxyl group [O?O = 3.005 (6) and H?O = 2.50 (5) Å]. This secondary hydrogen bond is probably a major factor in stabilizing the observed cisoid di­carbonyl conformation. Several intermolecular C—H?O close contacts were found for the latter compound.     

Two isomers of 2,4‐di­benzyl‐8‐azabicyclo­[3.2.1]­octan‐3‐ol

The crystal structures of the title compounds, 2α,4α‐di­benzyl‐3α‐tropanol (2α,4α‐di­benzyl‐8‐methyl‐8‐aza­bi­cyclo­[3.2.1]­octan‐3α‐ol), C₂₂H₂₇NO, (I), and 2α,4α‐di­benzyl‐3β‐tropanol (2α,4α‐di­benzyl‐8‐methyl‐8‐aza­bi­cyclo­[3.2.1]­octan‐3β‐ol), C₂₂H₂₇NO, (II), show that both compounds have a piperidine ring in a chair conformation and a pyrrolidine ring in an envelope conformation. Isomer (I) is asymmetric, the benzyl groups having different orientations, whereas isomer (II) is mirror symmetric, and the N and O atoms, the C atom attached to the hydroxy group, and the methyl C atom attached to the N atom lie on the mirror plane. In the crystal structures of both (I) and (II), the mol­ecules are linked together by intermolecular O—H⋯N hydrogen bonds to form chains that run parallel to the a direction in (I) and parallel to b in (II).     

The epimeric 9‐oxobicyclo[3.3.1]nonane‐3‐carboxylic acids: hydrogen‐bonding patterns of the endo acid and the lactol of the exo acid

The two δ‐keto carboxylic acids of the title, both C₁₀H₁₄O₃, are epimeric at the site of carboxyl attachment. The endo (3α) epimer, (I), has its keto‐acid ring in a boat conformation, with the tilt of the carboxyl group creating conformational chirality. The mol­ecules form hydrogen bonds by centrosymmetric pairing of carboxyl groups across the corners of the chosen cell [O⃛O = 2.671 (2) Å and O—H⃛O = 179 (2)°]. Two close intermolecular C—H⃛O contacts exist for the ketone. The exo (3β) epimer exists in the closed ring–chain tautomeric form as the lactol, 8‐hydroxy‐9‐oxatri­cyclo­[5.3.1.0^3,8]­undecan‐10‐one, (II). The mol­ecules have conformational chirality, and the hydrogen‐bonding scheme involves intermolecular hydroxyl‐to‐carbonyl chains of mol­ecules screw‐related in b [O⃛O = 2.741 (2) Å and O—H⃛O = 177 (2)°].     

16‐[3‐Methoxy‐4‐(2‐piperidin‐1‐yl­ethoxy)­benzyl­idene]‐17‐oxoandrost‐5‐en‐3β‐yl acetate monohydrate

The title compound, C₃₆H₄₉NO₅·H₂O, has the outer two six‐membered rings of the steroid nucleus in chair conformations. The central ring B of the steroid nucleus is in an 8β,9α‐half‐chair conformation, while ring D of the steroid adopts a slightly distorted 13β,14α‐half‐chair conformation. The piperidine ring is in a chair conformation. The methoxy­benzyl­idene moiety has an E configuration with respect to the carbonyl group at position 17. Intermolecular O—H?O and O—H?N hydrogen bonds link the steroid and water mol­ecules into chains which run parallel to the b axis.     

4‐Oxo­cyclo­hexane­carboxyl­ic acid: hydrogen bonding in the monohydrate of a δ‐keto acid

The title monohydrate, C₇H₁₀O₃·H₂O, aggregates as a complex hydrogen‐bonding network, in which the water mol­ecule accepts a hydrogen bond from the carboxyl group of one mol­ecule and donates hydrogen bonds to ketone and carboxyl Czdbnd;O functions in two additional mol­ecules, yielding a sheet‐like structure of parallel ribbons. The keto acid adopts a chiral conformation through rotation of the carboxyl group by 62.50 (15)° relative to the plane defined by its point of attachment and the ketone C and O atoms. Two C—H⋯O close contacts exist in the structure.     

The antifolate trimetrexate: ­observation of the enzyme‐binding conformation

The crystal structure of the title compound contains four 2,4‐di­amino‐5‐methyl‐6‐[(3,4,5‐tri­methoxy­anilino)­methyl]­quin­az­oline mol­ecules, two di­methyl sulfoxide mol­ecules and three water mol­ecules in the asymmetric unit, i.e. 4C₁₉H₂₃N₅O₃·2C₂H₆OS·3H₂O. All four quinazoline mol­ecules adopt trans,gauche conformations. An extensive hydrogen‐bond network involving N?N base‐pairing interactions, as well as the di­methyl sulfoxide and water mol­ecules, stabilizes the crystal structure.     

16‐(4‐Cyanobenzylidene)‐3β‐pyrrolidinoandrost‐5‐en‐17β‐ol monohydrate

In the title compound, C₃₁H₄₀N₂O·H₂O, the outer two six‐membered rings are in chair conformations, while the central ring is in an 8β,9α‐half‐chair conformation. The five‐membered ring adopts a 13β‐envelope conformation and the cyano­benzyl­idene moiety has an E configuration with respect to the hydroxyl group at position 17. The steroid nuclei are linked by intermolecular O—H?O and O—H?N hydrogen bonds to form a molecular network. The molecular packing has an interesting feature, with the steroids aligned parallel to the b axis, forming a closed loop through hydrogen bonds linked via water mol­ecules.     

(+)‐3‐Oxo‐4‐pregnene‐20β‐carboxyl­ic acid: catemeric hydrogen bonding in a steroidal keto acid

The title keto acid, (+)‐23,24‐dinor‐3‐oxo­chol‐4‐en‐22‐oic acid, C₂₂H₃₂O₃, forms carboxyl‐to‐ketone hydrogen‐bonding catemers [O?O = 2.699 (4) Å and O—H?O = 173°], linking mol­ecules screw‐related in b. The four mol­ecules in the cell form two parallel counter‐directional chains, screw‐related in a. Intermolecular C—H?O=C close contacts to different neighboring mol­ecules were found for the ketone and the acid.     

6‐Hydroxy‐2,2‐di­methyl‐3,4‐di­hydro‐2H‐benzo[b]pyran

The title compound, 2,2‐di­methyl­chroman‐6‐ol, C₁₁H₁₄O₂, has been identified as a side product from the condensation of hydro­quinone with 2‐methyl­but‐3‐en‐2‐ol. The pyran ring has a half‐chair conformation. The hydroxyl groups are involved in intermolecular hydrogen bonding which generates infinite spiral chains around the fourfold screw axes; the O?O hydrogen‐bonded distances are 2.661 (1) Å.     

4,5‐Di­azafluoren‐9‐one benzoyl­hydrazone monohydrate

The title compound, C₁₈H₁₂N₄O·H₂O, adopts the keto tautomeric form and the azomethine C=N double bond is in the E configuration. The dihedral angle between the planes of the di­aza­fluorene moiety and the phenyl ring is 11.3 (1)°. In the solid state, the mol­ecules form infinite chain‐like structures via O—H?N hydrogen bonds involving the water mol­ecules and di­aza­fluorene moieties.     

trans‐Diaquabis(1H‐imidazole‐4,5‐di­carboxyl­ate‐κ2N3,O4)­manganese(II)

In the title compound, [Mn(C₅H₃N₂O₄)₂(H₂O)₂], the Mn^II atom lies on an inversion centre, is trans‐coordinated by two N,O‐bidentate 1H‐imidazole‐4,5‐di­carboxyl­ate monoanionic ligands [Mn—O = 2.202 (3) Å and Mn—N = 2.201 (4) Å] and two water mol­ecules [Mn—O = 2.197 (4) Å], and exhibits a distorted octahedral geometry, with adjacent cis angles of 76.45 (13), 86.09 (13) and 89.20 (13)°. The complete solid‐state structure can be described as a three‐dimensional supramol­ecular framework, stabilized by extensive hydrogen‐bonding interactions involving the coordinated water mol­ecules, the carboxy O atoms and the protonated imidazole N atoms of the imidazole‐4,5‐di­carboxyl­ate ligands.     

Supramolecular structures of 5‐[3‐(4‐methyl­phenyl)‐ and 5‐[3‐(4‐chloro­phenyl)‐2‐propenyl­idene]‐2,2‐di­methyl‐1,3‐dioxane‐4,6‐dione

2,2‐Di­methyl‐5‐[3‐(4‐methyl­phenyl)‐2‐propenyl­idene]‐1,3‐di­ox­ane‐4,6‐dione, C₁₆H₁₆O₄, crystallizes in the triclinic space group , with two mol­ecules in the asymmetric unit. These mol­ecules and a centrosymmetrically related pair, linked together by weak C—H?O hydrogen bonds, form a tetramer. 5‐[3‐(4‐Chloro­phenyl)‐2‐propenyl­idene]‐2,2‐di­methyl‐1,3‐dioxane‐4,6‐dione, C₁₅H₁₃ClO₄, also crystallizes in the triclinic space group , with one mol­ecule in the asymmetric unit. Centrosymmetrically related mol­ecules are linked together by weak C—H?O hydrogen bonds to form dimers which are further linked by yet another pair of centrosymmetrically related C—H?O hydrogen bonds to form a tube which runs parallel to the a axis.     

9α‐Fluoro‐16α‐methyl‐3,11‐dioxoandrosta‐1,4‐diene‐17β‐carboxyl­ic acid: catemeric hydrogen bonding and acetic acid solvation in a steroidal keto acid related to dexamethasone

The title keto acid crystallizes as a solvate, C₂₁H₂₅FO₄·C₂H₄O₂, with two mol­ecules each of steroid and acetic acid per asymmetric unit. The former are approximately parallel, with opposite end‐to‐end orientation, and form translational carboxyl‐to‐ketone hydrogen‐bonding catemers [O⋯O = 2.679 (6) and 2.650 (5) Å, and O—H⋯O = 165 and 162°] that involve the 3‐ketone group and follow the a axis. The acetic acid mol­ecules are paired by hydrogen bonding, and neither they nor the F atom nor the 11‐ketone group play any overt role in the hydrogen‐bonding scheme of the steroid. Intermolecular C—H⋯O=C close contacts involving three different neighboring mol­ecules exist to the 11‐ketone group, the steroidal carboxyl group and one of the acetic acid molecules.     

Amino­pyrimidine–carboxyl­(ate) interactions in trimethoprim maleate,an antifolate drug

In the title cocrystal, trimethoprim maleate [2,4‐di­amino‐5‐(3,4,5‐tri­methoxy­benzyl)­pyrimidin‐1‐ium maleate], C₁₄H₁₉­N₄O₃⁺·­C₄H₃O₄^?, the trimethoprim mol­ecule is protonated at N1. The carboxyl group of the maleate ion makes a specific double hydrogen bond of type N—H?O with the 2‐amino group and the protonated N1 atom of the trimethoprim cation which is similar to the carboxyl­ate–trimethoprim cation interaction observed in the complex of di­hydro­folate reductase with trimethoprim. The pyrimidine moieties of trimethoprim cations are centrosymmetrically paired through a pair of N—H?N hydrogen bonds involving the 4‐amino group and the pyridinium N3 atom of a symmetry‐related molecule. One of the O atoms at the maleate carboxyl­ate group bridges the 2‐­amino and 4‐amino groups on either side of the paired trimethoprim cations. The other O atom of the carboxyl­ate group forms an intramolecular O—H?O hydrogen bond with the carboxyl group. These characteristic hydrogen bonds result in infinite two‐dimensional aggregation of rings into a supramolecular ladder, which is further crosslinked through weak C—H?O interactions with methoxy groups of neighbouring trimethoprim mol­ecules to form a layered structure.     

Piperazine‐1,4‐diium–2,4‐dinitrophenolate–water (1/2/2)

In the title 1/2/2 adduct, C₄H₁₂N₂²⁺·2C₆H₃N₂O₅^?·2H₂O, the dication lies on a crystallographic inversion centre and the asymmetric unit also has one anion and one water mol­ecule in general positions. The 2,4‐di­nitro­phenolate anions and the water mol­ecules are linked by two O—H?O and two C—H?O hydrogen bonds to form molecular ribbons, which extend along the b direction. The piperazine dication acts as a donor for bifurcated N—H?O hydrogen bonds with the phenolate O atom and with the O atom of the o‐nitro group. Six symmetry‐related molecular ribbons are linked to a piperazine dication by N—H?O and C—H?O hydrogen bonds.     

2,3,6,7‐Tetra­hydroxy‐9,10‐di­methyl‐9,10‐di­hydro‐9,10‐ethano­anthracene bis(1,4‐dioxane) solvate

2,3,6,7‐Tetra­hydroxy‐9,10‐di­methyl‐9,10‐di­hydro‐9,10‐ethano­anthracene crystallizes with 1,4‐dioxane to give a bis‐solvate, C₁₈H₁₈O₄·2C₄H₈O₂. The bis­(catechol) mol­ecule is located on a twofold axis and the two aromatic rings form a dihedral angle of 130.61 (4)°. Hydro­gen bonds are formed between the hydroxyl groups and either a neighbouring bis­(catechol) mol­ecule or the ether‐O atom of a dioxane mol­ecule.     

A structural hierarchy in the hydrogen‐bonded adduct ethane‐1,2‐di­phospho­nic acid–4,4′‐bipyridyl–water (1/1/2): an N‐component N‐­dimensional structure (N = 3) with substructures having N = 1 and 2

The title compound, 4,4′‐bipyridinium ethane‐1,2‐diyl‐1,2‐di­phospho­nate dihydrate, is a hydrated salt, C₁₀H₁₀N₂²⁺·­C₂H₆O₆P₂^2?·2H₂O, in which the components are linked by extensive hydrogen bonding. The cations and anions lie on inversion centres and with the water mol­ecules each form separate one‐component one‐dimensional chains along [100]: the anions and the water mol­ecules form a two‐component two‐dimensional substructure, (001) sheets, while the cations and anions form a second two‐component two‐dimensional substructure, (011) sheets. All three components combine to form a three‐dimensional framework.     

Self‐assembly of 2‐pivaloyl‐6‐chloro­pterin

In the title compound, N‐(6‐chloro‐4‐oxo‐3,4‐di­hydro­pteridin‐2‐yl)­‐2,2‐di­methyl­propan­amide, C₁₁H₁₂ClN₅O₂, the rings in the pterin moiety are planar. The amide carbonyl O atom is in syn‐periplanar conformation while the C—N—C—C propanamide linkage is antiperiplanar. The N—H?N and N—H?O intermolecular hydrogen bonds transform the mol­ecules into infinite chains.