Two rhod­amine derivatives: 9‐[2‐(ethoxycarbonyl)phenyl]‐3,6‐bis(ethyl­amino)‐2,7‐di­methyl­xanthyl­ium chloride monohydrate and 3,6‐di­amino‐9‐[2‐(methoxy­carbonyl)­phenyl]xanthyl­ium chloride trihydrate

The title compounds, C₂₈H₃₁N₂O₃⁺·Cl^?·H₂O (common name rhod­amine‐6g), (I), and C₂₁H₁₇N₂O₃⁺·Cl^?·3H₂O (common name rhod­amine‐123), (II), both have planar xanthene skeletons with a formal +1 charge on the amino N atoms delocalized through the π‐electron system so that the N—Csp² bond distances indicate significant double‐bond character. The substituted planar phenyl groups make angles of 63.29 (8) and 87.96 (11)° with the xanthene planes in (I) and (II), respectively. In both mol­ecules, the carbonyl bond vectors point toward the xanthene rings. The ethyl­amine groups in (I) are oriented similarly with their CH₂–CH₃ bond vectors pointing nearly perpendicular to the xanthene plane. The chloride ions and water mol­ecules are disordered in both structures. In (I), the chloride ion and water mol­ecule are disordered between two sites. One water and chloride alternately occupy the same site with occupancy factors of 0.5. The other 0.5‐chloride and 0.5‐water occupy two distinct positions separated by 0.747 (8) Å. In (II), the chloride ion is disordered between three sites and one of the waters is disordered about two other sites. Both crystal structures are stabilized by hydrogen bonds involving the chloride ions, amino groups and water mol­ecules, as well as by π–π stacking between xanthene planes.     

3,3′‐[o‐Phenyl­enebis­(methyl­eneoxy)]­bis(6‐chloro­flavone) and 3,3′‐propyl­ene­dioxy­bis­[6‐chloro‐2‐(2‐furyl)‐4H‐1‐benzopyran‐4‐one]

The title compound 3,3′‐[o‐phenyl­enebis­(methyl­eneoxy)]­bis(6‐chloro­flavone), C₃₈H₂₄Cl₂O₆, (I), crystallizes in the monoclinic space group C2/c, with the molecules lying across twofold rotation axes so that there is half a mol­ecule in the asymmetric unit, while the other title compound, 3,3′‐propyl­ene­dioxy­bis­[6‐chloro‐2‐(2‐furyl)‐4H‐1‐benzopyran‐4‐one], C₂₉H₁₈Cl₂O₈, (II), crystallizes in monoclinic space group P2₁/n with one mol­ecule in the asymmetric unit. In both compounds, the benzopyran moiety is nearly planar, with dihedral angles between the two fused rings of 1.43 (8)° in (I), and 2.54 (7) and 3.00 (6)° with respect to the benzopyran moieties in the two halves of (II). The furan rings are twisted by 8.3 (1) and 8.4 (1)° in the two halves of (II). In both compounds, the molecular structure is stabilized by intramolecular C—H⃛O hydrogen bonds, while the crystal packing is stabilized by C—H⃛Cl and C—H⃛O intermolecular hydrogen bonds in (I) and (II), respectively.     

Mononuclear nickel(II) and zinc(II) complexes with deprotonated forms of the tripodal hexadentate ligand 1,3‐bis(2‐hydroxybenzylidene)‐2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methylpropane‐1,3‐diamine

In the crystal structures of both title compounds, [1,3‐bis(2‐hydroxybenzylidene)‐2‐methyl‐2‐(2‐oxidobenzylideneaminomethyl)propane‐1,3‐diamine]nickel(II) [2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methyl‐1,3‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine]nickel(II) chloride methanol disolvate, [Ni(C₂₆H_25.5N₃O₃)]₂Cl·2CH₄O, and [1,3‐bis(2‐hydroxybenzylidene)‐2‐methyl‐2‐(2‐oxidobenzylideneaminomethyl)propane‐1,3‐diamine]zinc(II) perchlorate [2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methyl‐1,3‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine]zinc(II) methanol trisolvate, [Zn(C₂₆H₂₅N₃O₃)]ClO₄·[Zn(C₂₆H₂₆N₃O₃)]·3CH₄O, the 3d metal ion is in an approximately octahedral environment composed of three facially coordinated imine N atoms and three phenol O atoms. The two mononuclear units are linked by three phenol–phenolate O—H...O hydrogen bonds to form a dimeric structure. In the Ni compound, the asymmetric unit consists of one mononuclear unit, one‐half of a chloride anion and a methanol solvent molecule. In the O—H...O hydrogen bonds, two H atoms are located near the centre of O...O and one H atom is disordered over two positions. The Ni^II compound is thus formulated as [Ni(H_1.5L)]₂Cl·2CH₃OH [H₃L is 1,3‐bis(2‐hydroxybenzylidene)‐2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methylpropane‐1,3‐diamine]. In the analogous Zn^II compound, the asymmetric unit consists of two crystallographically independent mononuclear units, one perchlorate anion and three methanol solvent molecules. The mode of hydrogen bonding connecting the two mononuclear units is slightly different, and the formula can be written as [Zn(H₂L)]ClO₄·[Zn(HL)]·3CH₃OH. In both compounds, each mononuclear unit is chiral with either a Δ or a Λ configuration because of the screw coordination arrangement of the achiral tripodal ligand around the 3d metal ion. In the dimeric structure, molecules with Δ–Δ and Λ–Λ pairs co‐exist in the crystal structure to form a racemic crystal. A notable difference is observed between the M—O(phenol) and M—O(phenolate) bond lengths, the former being longer than the latter. In addition, as the ionic radius of the metal ion decreases, the M—O and M—N bond distances decrease.     

The supramolecular architecture of tris(naphthalene‐1,5‐diaminium) bis(5‐aminonaphthalen‐1‐aminium) octakis[hydrogen (5‐carboxypyridin‐3‐yl)phosphonate]

The asymmetric unit of the title compound, 3C₁₀H₁₂N₂²⁺·2C₁₀H₁₁N₂⁺·8C₆H₅NO₅P⁻, contains one and a half naphthalene‐1,5‐diaminium cations, in which the half‐molecule has inversion symmetry, one 5‐aminonaphthalen‐1‐aminium cation and four hydrogen (5‐carboxypyridin‐3‐yl)phosphonate anions. The crystal structure is layered and consists of hydrogen‐bonded anionic monolayers between which the cations are arranged. The acid monoanions are organized into one‐dimensional chains along the [101] direction via hydrogen bonds established between the phosphonate sites. (C)O—H...N_py hydrogen bonds (py is pyridine) crosslink the chains to form an undulating (010) monolayer. The cations serve both to balance the charge of the anionic network and to connect neighbouring layers via multiple hydrogen bonds to form a three‐dimensional supramolecular architecture.     

A synchrotron study of (2R,5′S)‐5′‐benzyl‐5‐bromo‐6‐methoxyspiro[indane‐2,2′‐piperazine]‐3′,6′‐dione dimethylformamide solvate

Synchrotron radiation was used to study the structure of the title compound, C₂₀H₁₉BrN₂O₃·C₃H₇NO, which was obtained as fine fragile needle‐shaped crystals by recrystallization from dimethylformamide (DMF), one molecule of which is incorporated per asymmetric unit into the crystal. The compound adopts a compact closed conformation with the orientation of the benzyl group such that the aryl ring is positioned over the piperazinedione ring, resulting in a C_spiro...C_trans—C—C_Ph pseudo‐torsion angle of −3.3 (3)°. The five‐membered ring is present in an expected envelope conformation and the six‐membered piperazinedione ring adopts a less puckered boat‐like conformation. Reciprocal amide‐to‐amide hydrogen bonding between adjacent piperazinedione rings and C—H...O interactions involving DMF molecules propagate in the crystal as a thick ribbon in the a‐axis direction.     

4,17,25,26‐Tetraaza‐6,9,12,15‐tetra­oxa‐2,19,21,24‐tetrathiatricyclo[18.4.11,4.117,20]hexacosa‐1(25),20(26)‐diene‐3,5,16,18‐tetraone

The title compound, C₁₄H₁₆N₄O₈S₄, has crystallographic C₂ symmetry with half a molecule in the asymmetric unit and a dihedral angle of 58.7 (1)° between the two planar 1,3,4‐thiadiazole five‐membered rings of the macrocyclic, giving the molecule a twisted conformation.     

Bromo­di­methyl(N‐methyl­pyrrolidin‐2‐one‐O)­tin(IV)‐di‐μ‐bromo‐bromo­di­methyl­tin(IV)

The preparation and X‐ray analysis of the title compound, [Sn₂Br₄(CH₃)₄(C₅H₉NO)], are described. The compound contains two Sn atoms in the asymmetric unit, that complexed by N‐methyl­pyrrolidin‐2‐one being hexacoordinated (a), the other exhibiting pentacoordination (b). The most important features are three different Sn—Br bond lengths at both Sn atoms with the following values: (a) 2.5060 (9), 2.7152 (10) and 3.7118 (10) Å; (b) 2.5084 (10), 2.5279 (9) and 3.5841 (10) Å.     

1‐Methyl‐5,6‐di­phenyl­pyrazine‐2(1H)‐thione

The title compound, C₁₇H₁₄N₂S, crystallizes in a triclinic unit cell, with two crystallographically independent mol­ecules in the asymmetric unit. The two independent mol­ecules pack in the same sense and form segregated layers along the c axis. The crystal is light‐stable and no dimers are formed under irradiation. The intermolecular distances between the potential reactive centers (the C‐3 and C‐5 ring positions) are 4.093 (4) and 5.643 (4) Å for mol­ecule A, and 4.081 (4) and 5.614 (4) Å for mol­ecule B.     

5‐[4‐(Diethoxyphosphoryl)‐2,3,5,6‐tetrafluorophenyl]‐10,15,20‐tris(pentafluorophenyl)porphyrin

The title compound, C₄₈H₂₀F₁₉N₄O₃P, prepared by the nucleophilic attack of triethyl phosphite on one of the 4‐fluoro atoms of 5,10,15,20‐tetrakis(pentafluorophenyl)porphyrin, contains a single molecule in the asymmetric unit. The porphyrin unit is almost planar [largest non‐H atom deviation = 0.174 (6) Å], and has the planes of the neighbouring benzene rings oriented at angles ranging from 64.3 (2) to 89.6 (3)° relative to the porphyrin core. The P=O group is almost coplanar with the attached benzene ring, subtending an angle of 4.0 (3)°. Several weak supramolecular interactions, namely C—H...π, C—F...π, P=O...π, C—H...(O,F) and F...F contacts, contribute to the crystal packing.     

1,2‐Bis­(methylsulfanyl)‐1,2‐dicarba‐closo‐dodecaborane(12)

In the title compound, 1,2‐(SCH₃)₂‐1,2‐closo‐C₂B₁₀H₁₀ or C₄H₁₆B₁₀S₂, the methylsulfanyl groups are bonded to the C atoms of the 1,2‐dicarba‐closo‐dodecaborane cage. The C_cage—C_cage distance is 1.8033 (18) Å and the S—C_cage—C_cage—S torsion angle is 1.07 (13)°. The C_cage—C_cage distance is compared with those in other 1,2‐dicarba‐closo‐dodecaborane derivatives.     

Decamethyl­ferrocenium bis­(2‐oxo‐1,3‐dithiole‐4,5‐dithiolato‐κ2S4,S5)nickelate(III) tetra­hydro­furan solvate

The title compound, [Fe(C₁₀H₁₅)₂][Ni(C₃OS₄)₂]·C₄H₈O or [Fe(Cp*)₂][Ni(dmio)₂]·THF, where [Fe(Cp*)₂]⁺ is the deca­methyl­ferrocenium cation, dmio is the 2‐oxo‐1,3‐dithiole‐4,5‐dithiol­ate dianion and THF is tetra­hydro­furan, crystallizes with two independent half‐anion units [one Ni atom is at the centre of symmetry (, , 0) and the other is at the centre of symmetry (, 0, )], one cation unit (located in a general position) and one THF solvent mol­ecule in the asymmetric unit. The crystal structure consists of two‐dimensional layers composed of parallel mixed chains, where pairs of cations alternate with single anions. These layers are separated by sheets of anions and THF mol­ecules.     

Influence of 1,4‐dioxane solvent inclusion on the crystal structure of 5,5′‐diphenyl‐2,2′‐(p‐phenylene)di‐1,3‐oxazole (POPOP)

Crystallization of 5,5′‐diphenyl‐2,2′‐(p‐phenylene)di‐1,3‐oxazole (POPOP), C₂₄H₁₆N₂O₂, from chloroform or 1,4‐dioxane yielded crystals in pure and solvated forms, respectively. The solvated crystals of POPOP were found to contain 1,4‐dioxane in a strict 1:2 compound–solvent stoichiometry, C₂₄H₁₆N₂O₂·C₄H₈O₂, thus being a defined solvent‐inclusion compound. The crystal system is monoclinic in both cases and the asymmetric unit of the cell contains only half of the molecule (plus one dioxane molecule in the case of the solvated structure), owing to the centrosymmetry of the di‐1,3‐oxazole molecule.     

μ‐4,4′‐Bipyridine‐κ2N:N′‐bis[triaqua(4,4′‐bipyridine‐κN)cadmium(II)] bis(3‐aminobenzoate) bis(perchlorate) dihydrate: a novel supramolecular system constructed by π–π and hydrogen‐bonding interactions

The title dicadmium compound, [Cd₂(C₁₀H₈N₂)₅(H₂O)₆](C₇H₆NO₂)₂(ClO₄)₂·2H₂O, is located around an inversion centre. Each Cd^II centre is coordinated by three N atoms from three different 4,4′‐bipyridine ligands and three O atoms from three coordinating water molecules in a distorted octahedral coordination environment. In the dicadmium cation unit, one 4,4′‐bipyridine (4,4′‐bipy) molecule acts as a bidentate bridging ligand between two Cd metal ions, while the other four 4,4′‐bipy molecules act only as monodentate terminal ligands, resulting in a rare `H‐type' [Cd₂(C₁₀H₈N₂)₅(H₂O)₆] host unit. These host units are connected to each other viaπ–π stacking interactions, giving rise to a three‐dimensional supramolecular grid network with large cavities. The 3‐aminobenzoate anions, perchlorate anions and water molecules are encapsulated in the cavities by numerous hydrogen‐bonding interactions. To the best of our knowledge, this is the first example of a coordination compound based on both 4,4′‐bipyridine ligands together with discrete 3‐aminobenzoate anions.     

catena‐Poly[[[(benzene‐1,3,5‐tricarboxylic acid)(1,10‐phenanthroline)cadmium(II)]‐μ‐oxalato] 1H‐benzotriazole solvate monohydrate]

In the title compound, [Cd(C₂O₄)(C₁₂H₈N₂)(C₉H₆O₆)]·C₆H₅N₃·H₂O, the Cd^II atom has a distorted pentagonal–bipyramidal geometry, defined by two N atoms and five O atoms from bidentate 1,10‐phenanthroline ligands, oxalate ligands and benzene‐1,3,5‐tricarboxylic acid ligands. The oxalate ligands in the asymmetric unit possess inversion symmetry. The triazole molecule is not coordinated to the Cd atom. The structure of the title compound features a one‐dimensional chain running along the crystallographic a axis, and a three‐dimensional supramolecular network is formed via aromatic π–π interactions and hydrogen‐bonding interactions.     

Tetra­allyl (2,2′‐bipyridyl)‐rac‐3,3,7,7‐tetra­methyl‐trans‐5‐palladatricyclo[4.1.0.02,4]­heptane‐1,2,4,6‐tetra­carboxyl­ate above and below the phase‐transition temperature of 194 K

The crystal structure of the title compound, (2,2′‐bipyridyl‐κ²N,N′)(tetra­allyl 3,3,3′,3′‐tetra­methyl‐1,1′‐bi­cyclo­propane‐1,1′,2,2′‐tetra­carboxyl­ato‐κ²C²,C^2′)­palladium(II), [Pd(C₂₆H₃₂­O₈)(C₁₀­H₈­N₂)], is disordered above 194 K. A doubling of the unit cell is observed on cooling. The structure at 143 K contains two ordered mol­ecules related by a pseudo‐translation vector of approximately (0.44,0.00,0.50) or a pseudo‐inversion center at approximately (0.22,0.00,0.25). Weak intermolecular C—H?O interactions are enhanced in the low‐temperature structure.     

(E)‐(4‐Hydroxyphenyl)(4‐nitrophenyl)diazene, (E)‐(4‐methoxyphenyl)(4‐nitrophenyl)diazene and (E)‐[4‐(6‐bromohexyloxy)phenyl](4‐cyanophenyl)diazene

Syntheses and X‐ray structural investigations have been carried out for (E)‐(4‐hydroxy­phenyl)(4‐nitro­phenyl)­diazene, C₁₂H₉N₃O₃, (Ia), (E)‐(4‐methoxy­phenyl)(4‐nitro­phenyl)­diazene, C₁₃H₁₁N₃O₃, (IIIa), and (E)‐[4‐(6‐bromo­hexyl­oxy)­phenyl](4‐cyano­phenyl)­diazene, C₁₉H₂₀BrN₃O, (IIIc). In all of these compounds, the mol­ecules are almost planar and the azo­benzene core has a trans geometry. Compound (Ia) contains four and compound (IIIc) contains two independent mol­ecules in the asymmetric unit, both in space group P (No. 2). In compound (Ia), the independent mol­ecules are almost identical, whereas in crystal (IIIc), the two independent mol­ecules differ significantly due to different conformations of the alkyl tails. In the crystals of (Ia) and (IIIa), the mol­ecules are arranged in almost planar sheets. In the crystal of (IIIc), the mol­ecules are packed with a marked separation of the azo­benzene cores and alkyl tails, which is common for the solid crystalline precursors of mesogens.     

1,4‐Phenylenebis(methylene) bis(9H‐carbazole‐9‐carbodithioate)

The molecules of the title compound, C₃₄H₂₄N₂S₄, lie across centres of inversion in the space group P2₁/n. The spacer unit linking the benzene rings and carbazole units is effectively planar, while the carbazole unit itself is slightly folded. Molecules are linked into sheets by a single C—H...π(arene) hydrogen bond and the hydrogen‐bonded sheets are themselves linked into a three‐dimensional framework structure by a single π–π stacking interaction.     

(2,2′‐Bi­pyridine‐κ2N)­bis­[N‐(2‐pyridyl‐κN)‐p‐toluene­sulfon­amido‐κN]zinc(II)

The structure of the title compound, [Zn(C₁₂­H₁₁­N₂­O₂S)₂(C₁₀H₈N₂)], consists of monomeric mol­ecules in which the central ZnN₂N′N′′ unit has a distorted tetrahedral geometry, with bond lengths ranging from 2.020 (3) to 2.109 (3) Å. The anionic ligands are potential bidentate donors and thus there are two secondary Zn—N interactions. The shorter of these is 2.317 (3) Å and completes at the Zn atom an irregular five‐coordinated geometry, which can be described as a square pyramid showing 30% distortion towards the trigonal bipyramid; the other Zn—N contact is much longer at 2.549 (3) Å.     

(4‐Aminopyridine‐κN1)(phthalocyaninato‐κ4N)zinc(II) tetrahydrofuran disolvate

The title compound, [Zn(C₃₂H₁₆N₈)(C₅H₆N₂)]·2C₄H₈O, consists of one (phthalocyaninato)zinc (ZnPc) unit, a coordinated 4‐aminopyridine (4‐ap) molecule and two tetrahydrofuran (THF) solvent molecules. The central Zn atom is (4+1)‐coordinated by four isoindole N atoms of the Pc core and by the pyridine N atom of 4‐aminopyridine. The Zn atom is displaced by 0.4464 (8) Å from the isoindole N₄ plane towards the pyridine N atom. The crystal structure is stabilized by intermolecular amine–phthalocyaninate N—H...N hydrogen bonds and π–π interactions between the aggregated Pc rings, which form molecular layers, and by weak van der Waals interactions between the layers. As well as hindering the aggregation of ZnPc molecules by occupying an axial position, the amino group will add new interactions which will favor applications of ZnPc, for example, as a sensitizer of photodynamic therapy.     

3,5‐Di­amino‐6‐(2‐fluoro­phenyl)‐1,2,4‐triazine–di­methyl­form­amide (1/1)

The title compound, C₉H₈FN₅·C₃H₇NO, contains two independent complexes in the asymmetric unit, each consisting of one 3,5‐di­amino‐6‐(2‐fluoro­phenyl)‐1,2,4‐triazine mol­ecule and one di­methyl­form­amide solvent mol­ecule. One triazine mol­ecule is disordered over two conformations within the crystal, the occupancies being 62 (1) and 38 (1)%. The phenyl ring of this mol­ecule resolves into two conformations rotated by almost 180° about the bridging bond between the two rings, while the triazine rings approximately superimpose on each other. The triazine mol­ecules of the asymmetric unit differ in the dihedral angles between their respective phenyl and triazine ring planes, these being 57.6 (2)° for the fully occupied, and 76.9 (6) and 106.8 (8)° for the partially occupied mol­ecules. An extensive network of hydrogen bonds maintains the crystal structure.