Two N‐substituted 3,5‐diphenyl‐2‐pyrazoline‐1‐thiocarboxamides

The structures of N‐ethyl‐3‐(4‐fluoro­phen­yl)‐5‐(4‐methoxy­phen­yl)‐2‐pyrazoline‐1‐thio­carboxamide, C₁₉H₂₀FN₃OS, (I), and 3‐(4‐fluoro­phen­yl)‐N‐methyl‐5‐(4‐methyl­phen­yl)‐2‐pyrazoline‐1‐thio­carboxamide, C₁₈H₁₈FN₃S, (II), have similar geometric parameters. The meth­oxy/methyl‐substituted phenyl groups are almost perpendicular to the pyrazoline (pyraz) ring [inter­planar angles of 89.29 (8) and 80.39 (10)° for (I) and (II), respectively], which is coplanar with the fluoro­phenyl ring [inter­planar angles of 5.72 (9) and 10.48 (10)°]. The pyrazoline ring approximates an envelope conformation in both structures, with the two‐coordinate N atom involved in an intra­molecular N—H⋯N_pyraz inter­action. In (I), N—H⋯O and C—H⋯S inter­molecular hydrogen bonds are the primary inter­actions, whereas in (II), there are no intermolecular hydrogen bonds.     

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.     

Tetra­kis(μ2‐1,8‐naphthyridine)‐1:2κ4N:N′;3:4κ4N:N′‐bis­(μ2‐salicylato)‐1:4κ2O:O′;2:3κ2O:O′‐tetrakis­(salicylic acid)‐1κO,2κO,3κO,4κO‐tetra­silver(I)(4 Ag—Ag)

The title complex, [Ag₄(C₇H₅O₃)₂(C₈H₆N₂)₄(C₇H₆O₃)₄], lies about an inversion centre and has a unique tetra­nuclear structure consisting of four Ag^I atoms bridged by four N atoms from two 1,8‐naphthyridine (napy) ligands to form an N:N′‐bridge and four O atoms from two salicylate (SA) ligands to form an O:O′‐bridge. The Ag atoms have distorted octa­hedral coordination geometry. The centrosymmetric Ag₄ ring has Ag—Ag separations of 2.772 (2) and 3.127 (2) Å, and Ag—Ag—Ag angles of 107.70 (4) and 72.30 (4)°. All SA hydroxy groups take part in intra­molecular O—H⋯O hydrogen bonding. In the crystal packing, the napy rings are oriented parallel and overlap one another. These π–π inter­actions, together with weak inter­molecular C—H⋯O contacts, stabilize the crystal structure.     

Azin­yl sulfides. LXXXI. 14‐Phen­yl‐7‐thia­pyrano[2,3‐c;6,5‐c′]diquinoline‐14‐carbonitrile

The mol­ecules of the title compound, C₂₆H₁₅N₃S, have a penta­cyclic ring system which is almost planar, with the central ring in a flattened boat conformation. The folding angle between the two quinoline rings is 6.75 (7)°. The 14‐phen­yl substituent is in a quasi‐axial conformation, while the 14‐cyano substituent is in a quasi‐equatorial conformation with respect to the thio­pyran ring. The S⋯C—C_phen­yl and S⋯C—C_CN angles are 116.8 (2) and 129.3 (2)°, respectively. The plane of the phen­yl group is nearly coplanar with the plane bis­ecting the dihedral angle of the penta­cyclic ring system.     

2‐Amino­pyridinium–fumarate–fumaric acid (2/1/1)

The title complex, 2C₅H₇N₂⁺·C₄H₂O₄²⁻·C₄H₄O₄, contains cyclic eight‐membered hydrogen‐bonded rings involving 2‐­aminopyridinium and fumarate ions. The fumaric acid mol­ecules and fumarate ions lie on inversion centers and are linked into zigzag chains by O—H⋯O hydrogen bonds. The dihedral angle between the pyridinium ring and the hydrogen‐bonded fumarate ion is 7.60 (4)°. The fumarate anion is linked to the pyridinium cations by intermolecular N—H⋯O hydrogen bonds. The heterocycle is fully protonated, thus enabling amine–imine tautomerization.     

Diacetatobis(2‐amino­benzothia­zole‐κN)cobalt(II)

The title complex, [Co(C₂H₃O₂)₂(C₇H₆N₂S)₂], contains a Co centre with a slightly distorted tetra­hedral coordination geometry, involving two acetate ligands and two N atoms from the thia­zole moiety [Co—O = 2.0025 (14) and 1.9953 (16) Å, and Co—N = 2.0524 (18) and 2.0568 (18) Å]. The inter­planar angle between the two benzothia­zole moieties is 77.86 (3)°. The amine groups, acting as donors, participate in intra‐ and inter­molecular N—H⋯O hydrogen bonds, with N⋯O distances in the range 2.806 (2)–2.857 (2) Å.     

(Glycylglycinato‐κ3O,N,N′)(2‐methyl‐1H‐benzimidazole‐κN3)copper(II) trihydrate

In the title compound, [Cu(C₄H₆N₂O₃)(C₈H₈N₂)]·3H₂O, the Cu^II atom is coordinated in a square‐planar manner by one O atom and three N atoms from glycylglycinate and 2‐methyl­benzimidazole ligands. The ternary complexes assemble into one‐dimensional chains through C—H⋯π inter­actions and direct N—H⋯O hydrogen bonding, as well as into hydrogen‐bonded water helices with branches which also link the complex chains into a three‐dimensional supra­molecular structure.     

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.     

Two derivatives of 5‐amino­tetrazole: 5‐amino‐1‐phenyl­tetrazole and 5‐amino‐1‐(1‐naphthyl)­tetrazole

In the mol­ecules of 5‐amino‐1‐phenyl­tetrazole, C₇H₇N₅, (I), and 5‐amino‐1‐(1‐naphthyl)­tetrazole, C₁₁H₉N₅, (II), the tetrazole rings and aryl fragments are not coplanar; corresponding dihedral angles are 50.58 (5) and 45.19 (7)° for the two independent mol­ecules of (I), and 64.14 (5)° for (II). Intermolecular N—H⋯N hydrogen bonds between the amino groups and tetrazole N atoms are primarily responsible for formation of two‐dimensional networks extending parallel to the bc plane in both compounds. The presence of the amino group has a distinct effect on the geometry of the tetrazole rings in each case.     

catena‐Poly­[[(di‐2‐pyridyl­amine)­silver(I)]‐μ‐nicotinato] and catena‐poly­[[(di‐2‐pyridyl­amine)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato]

In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐nico­tinato‐κ²N:O], [Ag(C₆H₄NO₂)(C₁₀H₉N₃)]_n, the Ag^I atom is tetracoordinated by two N atoms from the di‐2‐pyridyl­amine (BPA) ligand [Ag—N = 2.3785 (18) and 2.3298 (18) Å] and by one N atom and one carboxyl­ate O atom from nicotinate ligands [Ag—N = 2.2827 (15) Å and Ag—O = 2.3636 (14) Å]. Bridging by nicotinate N and O atoms generates a polymeric chain structure, which extends along [100]. The carboxyl O atom not bonded to the Ag atom takes part in an intrachain C—H⋯O hydrogen bond, further stabilizing the chain. Pairs of chains are linked by N—H⋯O hydrogen bonds to generate ribbons. There are no π–π interactions in this complex. In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato‐κ²O¹:O²], [Ag(C₇H₅O₄)(C₁₀H₉N₃)]_n, the Ag^I atom has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand [Ag—N = 2.286 (5) and 2.320 (5) Å] and to one carboxyl­ate O atom from the 2,6‐di­hydroxy­benzoate ligand [Ag—O = 2.222 (4) Å]; the fourth, weaker, Ag‐atom coordination is to one of the phenol O atoms [Ag⋯O = 2.703 (4) Å] of an adjacent moiety, and this interaction generates a polymeric chain along [100]. Pairs of chains are linked about inversion centers by N—H⋯O hydrogen bonds to form ribbons, within which there are π–π interactions. The ribbons are linked about inversion centers by pairs of C—H⋯O hydrogen bonds and additional π–π interactions between inversion‐related pairs of 2,6‐di­hydroxy­benzoate ligands to generate a three‐dimensional network.     

4‐[N,N‐Bis(2‐hydroxy­imino‐2‐phenyl­ethyl)­amino]‐1,5‐di­methyl‐2‐phenyl‐2,3‐di­hydro‐1H‐pyrazol‐3‐one monohydrate

The title compound, C₂₇H₂₇N₅O₃·H₂O, is built up from pyrazolinone, phenyl and aceto­phenone oxime moieties. The 2‐­phenyl substituent is nearly perpendicular to the pyrazo­linone ring, with a dihedral angle of 87.66 (1)°. The aceto­phenone oxime moieties are twisted out of the pyrazolinone‐ring plane by 47.04 (1)°. The mol­ecules in the crystal pack in an antiparallel fashion and are held together by hydrogen‐bonded water mol­ecules and intermolecular O—H⋯O and O—H⋯N hydrogen bonds.     

A bicapped trigonal–prismatic lead complex: catena‐poly[[[aqua­bis(1,10‐phenanthroline‐κ2N,N′)lead(II)]‐μ‐squarato‐κO1:κ2O2,O3] dihydrate]

The asymmetric unit of the title compound, {[Pb(C₄O₄)(C₁₂H₈N₂)₂(H₂O)]·2H₂O}_n, contains one squarate dianion, two phenanthroline (phen) ligands and one aqua ligand all coordinated to Pb, and two solvent water mol­ecules. The eight‐coordinate Pb metal ion displays a distorted bicapped trigonal–prismatic coordination environment, defined by three squarate O atoms, four N atoms from two chelating phen ligands and one O atom from the coordinated water mol­ecule. The crystal structure contains chains of squarate‐1,2,3‐bridged Pb^II ions running in the [010] direction. These polymeric chains are linked to one another via offset face‐to‐face π–π inter­actions between the phen ligands, which lead to a two‐dimensional network extending along the (001) plane. The crystal structure is also stabilized by O—H⋯O inter­molecular hydrogen‐bond inter­actions, forming a three‐dimensional network.     

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.     

1,3‐Bis(4‐methyl­phen­yl)triazene, 1‐(4‐chloro­phen­yl)‐3‐(4‐fluoro­phen­yl)triazene and 1‐(4‐fluoro­phen­yl)‐3‐(4‐methyl­phen­yl)triazene

The title 4,4′‐disubstituted diphen­yl‐1,3‐triazines, C₁₄H₁₅N₃, (I), C₁₂H₉ClFN₃, (II), and C₁₃H₁₂FN₃, (III), each contain a triazene group (–N=N—NH–) having an extended conformation. The dihedral angles between the two benzene rings in (I), (II) and (III) are 4.3, 3.4 and 6.5°, respectively. The mol­ecules are almost entirely planar, with maximum deviations from the mean planes of 0.1087 (2), −0.1072 (7) and 0.1401 (3) Å, respectively. In each compound, the molecules are linked by N—H⋯N hydrogen bonds to form chains and pack similarly in the crystal structures.     

Di­aza­bi­cyclo­[2.2.2]­octane‐1,4‐diium dichromate

The title compound, (C₆H₁₄N₂)[Cr₂O₇], consists of a di­aza­bi­cyclo­[2.2.2]­octane‐1,4‐diium cation and a discrete dichromate anion, which are linked in the crystal by N—H⋯O hydrogen bonds. The cation is ordered and distorted, owing to the confinement and twist of the hydrogen bonds involved. Two CrO₄ tetrahedra are joined through a shared O atom to form the dichromate anion. Chiral supramolecular chains of the title compound are built up via N—H⋯O hydrogen bonds, and C—H⋯O interactions play subordinate roles in forming the structure.     

Monoclinic and triclinic concomitant polymorphs of di‐μ‐pyridazine‐1κ2N:2κ2N′‐bis­[(saccharinato)silver(I)]

Crystallization of the title compound, di‐μ‐pyridazine‐1κ²N:2κ²N′‐bis­[(2,3‐dihydro‐3‐oxobenzisosulfonazolato‐κN)silver(I)], [Ag₂(C₇H₄NO₃S)₂(C₄H₄N₂)₂], from acetonitrile yields both monoclinic, (I), and triclinic, (II), polymorphs. In both forms, the silver(I) ions have a slightly distorted trigonal AgN₃ coordination geometry and are doubly bridged by two neutral pyridazine (pydz) ligands, generating a centrosymmetric dimeric structure. The saccharinate (sac) ligands are N‐coordinated. The dihedral angles between the sac and pydz rings are 8.43 (7) and 7.94 (8)° in (I) and (II), respectively, suggesting that the dimeric mol­ecule is nearly flat. The bond geometry is similar in both polymorphs. In (I), the dimers inter­act with each other via aromatic π_sac–π_pydz stacking inter­actions, forming two‐dimensional layers, which are further crosslinked by weak C—H⋯O inter­actions. Compound (II) exhibits similar C—H⋯O and π–π inter­actions, but additional C—H⋯π and π⋯Ag inter­actions help to stabilize the packing of the dimers.     

Bis­(saccharinato‐κN)zinc(II) com­plexes with N,N′‐bidentate 2‐amino­methyl­pyridine and 2‐amino­ethylpyridine

The structures of trans‐bis[2‐(amino­methyl)­pyridine‐κ²N,N′]­bis­(saccharinato‐κN)­zinc(II), [Zn(C₇H₄NO₃S)₂(C₆H₈N₂)₂], (I), and [2‐(amino­ethyl)­pyridine‐κ²N,N′]bis­(saccharinato‐κN)­zinc(II), [Zn(C₇H₄NO₃S)₂(C₇H₁₀N₂)], (II), exhibit octa‐ and tetrahedrally coordinated Zn^II atoms, respectively. The di­amine ligands behave as N,N′‐bidentate ligands, while saccharinate (sac) is coordinated through the N atom. In (I), the complex lies about an inversion centre with the Zn atom disordered and displaced by 0.256 (2) Å from a centre of symmetry towards a sac N atom. The crystal structure of (I) is stabilized by N—H⋯O hydrogen bonds and the crystal packing of (II) is determined by hydrogen bonding as well as weak π–π stacking interactions between the sac ligands.     

(4,6‐Dimercapto‐1,3,5‐triazine‐2‐thiol­ato‐S2)­tris­(tri­phenyl­phosphine‐P)gold(I) di­methyl­form­amide solvate

In the title compound, [Au(C₃H₂N₃S₃)(C₁₈H₁₅P)₃]·C₃H₇NO, the Au^I atom has a distorted tetrahedral geometry consisting of one uncoordinated di­methyl­form­amide mol­ecule, one tri­thio­cyanurate ligand and three PPh₃ ligands. The S—Au distance is 2.909 (2) Å, and the P—Au distances fall in the range 2.400 (14)–2.4074 (13) Å. The S—Au—P angles are 92.81 (6), 99.17 (6) and 104.21 (5)°, and the P—Au—P angles are 114.46 (5), 119.04 (5) and 119.66 (5)°.     

(R)‐1‐Phenyl­ethyl­ammonium 6‐amino‐5‐nitro­pyrimidine‐2,4(1H,3H)‐dionate (R)‐1‐phenyl­ethyl­amine hemisolvate: hydrogen‐bonded sheets of ions with pendent solvent mol­ecules

In the title compound, 2C₈H₁₂N⁺·2C₄H₃N₄O₄⁻·C₈H₁₁N, the anions are linked by paired N—H⋯N hydrogen bonds [H⋯N = 2.07 and 2.11 Å, N⋯N = 2.942 (3) and 2.978 (3) Å and N—H⋯N = 173 and 170°] and by paired N—H⋯O hydrogen bonds [H⋯O = 1.98 and 2.05 Å, N⋯O = 2.855 (3) and 2.917 (3) Å, and N—H⋯O = 173 and 167°] into chains of rings. These chains are linked into sheets by further N—H⋯O hydrogen bonds in which all of the donors are provided by the cations [H⋯O = 1.83–2.17 Å, N⋯O = 2.747 (3)–2.965 (3) Å and N—H⋯O = 141–168°]. The neutral amine molecule is pendent from the sheet and is linked to it by a single N—H⋯N hydrogen bond [H⋯N = 2.00 Å, N⋯N = 2.901 (3) Å and N—H⋯N = 175°].     

Tolterodinium (+)‐(2R,3R)‐hydrogen tartrate

In the crystal structure of (R)‐N,N‐diisopropyl‐3‐(2‐hydroxy‐5‐methyl­phenyl)‐3‐phenyl­propyl­aminium (2R,3R)‐hydrogen tartrate, C₂₂H₃₂NO⁺·C₄H₅O₆⁻, the hydrogen tartrate anions are linked by O—H⋯O hydrogen bonds to form helical chains built from (9) rings. These chains are linked by the tolterodine molecules via N—H⋯O and O—H⋯O hydrogen bonds to form separate sheets parallel to the (101) plane.