Br···HN, N···HC, Br···HC, and Br···Br intermolecular interactions as supramolecular synthons: Synthesis and crystal structure of bis(2-amino-5-methylpyridinium) tetrabromomercurate(II)

The bis(2-amino-5-methylpyridinium) tetrabromomercurate(II) (C₆H₉N₂)₂[HgBr₄] salt is triclinic, P1, with the following cell parameters: a=8.060(8) ?, b=9.035(9) ?, c=14.964(10) ?, α=96.032(19)°, β=90.317(15)°, γ=113.32(2)°, V=993.8(15) ?³, with Z=2 formula units. The crystal structure consists of alternating stacks of inorganic HgBr₄ ²⁻ anions and organic layers of 2-amino-5-methylpyridinium cations parallel to c-axis. The cohesion forces that connect molecules in the organic layers are N···HC hydrogen bonding and π–π stacking. The HgBr₄ ²⁻ units in the inorganic stacks are attracted via Br···Br intermolecular interactions.Supplementary material CCDC 270395 contains the supplementary crystallographic data. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by e-mailing at data_request@ccdc.cam.ac.uk, or by contacting the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: + 44(0)1223-336033.     

Selinidin: Crystal structure generated by C–H···O, C–H···π and π-π interactions

The title compound, 9,10-dihydro-8,8-dimethyl-2-oxo-2H,8H-benzo[1,2-b:3,4-b']dipyran-9-yl-2-methyl-2-butenoate, C₁₉H₂₀O₅, was isolated from the roots of Selinum vaginatum. The compound crystallizes into monoclinic space group P2 ₁ with unit cell parameters: a = 12.830(2) Å, b = 9.041(1) Å, c = 14.983(1) Å, β = 95.09(1)°, Z = 4. The crystal structure has been determined using direct methods and refined by full-matrix least-squares to a final R value of 0.0529 for 3142 observed reflections. There are two independent molecules, A and B, per asymmetric unit. In both the molecules, the coumarin nucleus is planar. However pronounced differences are observed in the conformation of dihydropyran ring which has a half-chair conformation with an 8β-9α orientation in molecule A and is intermediate between half-chair and sofa in molecule B. Differences also occur in the conformation of the 2-methylbutenoyloxy side chain at C9 due to the different geometry of C–H···π interactions in molecules A and B. Molecules A and B are connected by π–π interactions between their coumarin fragments forming dimers. The dimers interact through C–H···O and C–H···πhydrogen bonds.     

Synthesis and crystal structure of 5,7-diallyloxy-4-methylcoumarin

The title compound, 5,7-diallyloxy-4-methyl-2H-[1]-benzopyran-2-one, (C₁₆H₁₆O₄), was prepared by condensation of ethyl acetoacetate with phloroglucinol followed by allylation of the 5,7-dihydroxy-4-methylcoumarin thus obtained. The compound crystallizes into monoclinic space group P2₁/c with unit cell parameters a = 7.531(1) Å, b = 22.596(4) Å, c = 8.090(1) Å, β = 92.74(2)°, Z = 4. The crystal structure was solved by direct methods using single crystal X-ray diffraction data and refined to R = 0.0596 for 2166 observed reflections. The coumarin moiety is perfectly planar, with dihedral angle between the two fused rings of 0.46(5)°. The two allyloxy groups have different behaviour, one of them being disordered. Molecules form chains of weak C–HO and C–Hπ hydrogen bonds.     

π–π Interactions in diimine Pt(II) complexes with thiacrown ligands: The crystal structure of (1,4,7-trithiacyclononane)(3,4,7,8-tetramethyl-1, 10-phenanthroline)platinum(II) hexafluorophosphate

We wish to report the crystal structure for the heteroleptic platinum(II) complex with the crown thioether 1,4,7-trithiacyclononane (9S3) and the diimine ligand 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen), [Pt(9S3)(tmphen)](PF₆)₂ (1). The Pt(II) center is surrounded by a cis-S₂N₂ ligand environment formed by the bidentate diimine and two of the three sulfur atoms from the 9S3 ligand. These two sulfurs are positioned 2.2665(10) and 2.2612(11) Å from the Pt(II), but the third sulfur shows a long distance interaction at 2.8849(13) Å to form an elongated square pyramidal structure. An examination of the structure reveals π–π-intermolecular stacking of the phen groups with alternating distances of 3.53 and 3.62 Å between the planes of the phen ligands. A detailed survey of 12 other divalent Pt(II) and Pd(II) diimine complexes of 9S3 reveals three different stacking motifs involving π–π interactions in the solid state. Crystal Data for (1): P-1, a = 10.868(2) Å, b = 11.292(2) Å, c = 11.513(2) Å, α = 93.76(3)°, β = 90.82(3)°, γ = 92.28(3)°, V = 1408.5(5) Å³, Z = 2.

A supramolecular structure of bis(1,3-diphenyl-1,3-propanedionato-O,O′) (1,10-phenanthroline-N,N′)cobalt(II) based on C–H…O, C–H…π and π…π interactions

The compound bis(1,3-diphenyl-1,3-propanedionato-O,O′) (1,10-phenanthroline-N, N′)cobalt(II) (Co(DBM)₂(1,10-phe)) was investigated as a potential host component for functional inclusion materials. The molecules of the complex in the crystal (a=21.015(5) ?, b=17.456(5) ?, c=9.503(3) ?, β=107.04(2)°, s.g. C 2/c) are centrosymmetric and assemble by way of C–H···O and C–H···π hydrogen bonds as well as π···π stacking interactions to provide a supramolecular ladder-like motif that is accompanied by a variant of the six phenyl-embrace synthon.     

Crystal structure of cis-[Rh(biq)2Cl2]Cl·3H2O: Solid-state characterization and crystal packing analysis

The title compound, cis-[Rh(biq)₂Cl₂]Cl·3H₂O (biq = 2,2′-biquinoline) crystallized in the monoclinic space group P2 ₁ /n with a = 11.231(2) Å, b = 20.895(4) Å, c = 14.081(3) Å, β = 94.76(3)°, V = 3293.0(11) ų, D _c = 1.565 g cm⁻³, μ = 0.806 mm⁻¹, F(000) = 1576 and Z = 4. It contains a monomeric [Rh(biq)₂Cl₂]⁺ cation, a chloride ion and three molecules of H₂O. The rhodium(III) ion is hexa coordinated forming a distorted octahedral arrangement. The mean Rh(III)–N distance for the four Rh(III)–N bonds is 2.0625 Å. The two chloride atoms are bonded in a cis configuration [Rh(III)–Cl bond distances are 2.329(3) and 2.341(4) Å]. The structure shows a curling stacks of cationic complexes interacting via offset-face-to-face (OFF) π–π aryl interaction motif. Water molecules and chloride ions are hydrogen bonded (H₂O···H–OH and Cl···H–OH) and links the curling stacks by hydrogen bonding via Rh–Cl···H–OH interactions.     

Syntheses and Crystal Structures of Two Apigenin Alkylation Derivatives

Abstract Two apigenin alkylation derivatives, 4′,7-dimethoxyl-5-hydroxyflavone (I) and 4′,7-diethoxyl-5-hydroxyflavone (II), have been synthesized and their crystal structures were determined by ¹H NMR and single crystal X-ray diffraction study. (I) is triclinic, space group P−1 with a = 7.120(5) ?, b = 7.297(5) ?, c = 13.559(10) ?, α = 89.313(12)°, β = 86.298(12)°, γ = 83.999(13)° and Z = 2. (II) is monoclinic, space group P 2₁ /c with a = 16. 309(4) ?, b = 7.303(2) ?, c = 15.185(4) ?, α = 90.00°, β = 115.70(2)°, γ = 90.00° and Z = 4. They have the same flavone skeleton which is composed of a benzopyranone moiety and a phenyl moiety. Molecules of (I) are linked into a two-dimensional network by a combination of C–H···O hydrogen bond and π–π stacking interactions. (II) shows some discrepancies with (I) and the molecules are linked into a column by π–π stacking interaction. Graphical Abstract Two apigenin alkylation derivatives, 4′,7-dimethoxyl-5-hydroxyflavone (I) and 4′,7-diethoxyl-5-hydroxyflavone (II) were synthesized and their crystal structures were determined by single-crystal X-ray diffraction. Hydrogen bonding and π–π stacking interactions assemble (I) into a two-dimensional network, and in the crystal structure of (II), π–π stacking interaction leads to the formation of a column.      

Supramolecular Network via Hydrogen Bonding and π–π Stacking in 4,4′-Bipyridin-1-ium Perchlorate Dihydrate

Abstract The crystal structure of 4,4′-bipyridin-1-ium perchlorate dihydrate, [C₁₀H₉N₂](ClO₄) · 2H₂O, is determined by room temperature X-ray diffraction. The compound crystallizes in the triclinic space group P-1 with a = 8.122(3) ?, b = 9.726(3) ?, c = 17.648(6) ?, α = 78.181(4)°, β = 82.797(5)°, γ = 67.439(4)°, Z = 2, V = 1258.4(7) ?³. In the compound, monoprotonated 4,4′-bipyridin-1-ium cations are self-assembled into supramolecular chains along the a-axis through N–H···N hydrogen bonds in a head-to-tail fashion. The chains are stacked via π–π stacking interactions to create two-dimensional sheets. The interlayer space is occupied by the hydrogen-bonded water chains that are linked to the organic sheets via C–H···O interactions and the perchlorate anions that are linked to the water chains and the organic sheets via O–H···O and C–H···O hydrogen bonds, respectively, thus generating a three-dimensional supramolecular architecture. Index Abstract Supramolecular Network via Hydrogen Bonding and π–π Stacking in 4,4′-Bipyridin-1-ium perchlorate dihydrate Jian-Yong Zhang, Ai-Ling Cheng and En-Qing Gao* Monoprotonated 4,4′-bipyridin-1-ium cations are self-assembled into supramolecular chains along the a-axis through N–H···N hydrogen bonds, and these chains are stacked via π–π stacking and hydrogen bond interactions involving water molecules and perchlorate anions.      

Intermolecular interactions involved in the crystal structure of 2-amino-5-methylpyridinium hexabromostannate (IV), (C<Subscript>6</Subscript>H<Subscript>9</Subscript>N<Subscript>2</Subscript>)<Subscript>2</Subscript>[SnBr<Subscript>6</Subscript>]

The salt bis(2-amino-5-methylpyridinium) hexabromostannate(IV) (C₆H₉N₂)₂[SnBr₆] is monoclinic, P2 ₁ /c, with the following cell parameters: a=9.1636(18) ?, b=28.767(7) ?, c=16.956(17) ?, β=101.008(5)°, V=4387.5(17) ?³, Z=8, formula units. X-ray crystallography revealed that the structure can be regarded as a semi-regular three-dimensional array of anions, with pairs of cations forming layers perpendicular to b axis in the cavities between the anions. The cohesion forces that connects molecules in the organic layers are hydrophilic N⋯HCH₂ and HN⋯HN hydrogen bonding as well as hydrophobic π-π stacking and CH₃⋯π interactions. Cations and anions are connected via strong Br⋯H hydrogen bonding. Supplementary material CCDC 276493 contains the supplementary crystallographic data. These data can be obtained free of charge via www.ccdc. cam.ac.uk/data_request/cif, by e-mailing data_ request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033.     

Synthesis,spectroscopic and structural studies of <Emphasis Type="Italic">N</Emphasis>-(1<Emphasis Type="Italic">H</Emphasis>-benzimidazol-2-yl)-<Emphasis Type="Italic">N</Emphasis>′-benzyl propionamidine

N-(1H-Benzimidazol-2-yl) propionimidic acid ethyl ester (1) reacts with benzylamine to yield the corresponding N-(1H-Benzimidazol-2-yl)-N′-benzyl proponamidine (2). The structure and conformation of the amidine 2 were determined by ¹H and ¹³C NMR and X-ray diffraction. The product crystallizes in monoclinic system with space group P2₁/c, a = 10.7913 ?, b = 15.5164 ?, c = 9.1130 ?, β = 108.378° and Z = 4. In the crystal there are two N–HN hydrogen bonds, the first is intramolecular H-Bond links H4 to N1; the second one is intermolecular and it links H2 to N3 of a second molecule leading to inversion-related dimers. The X-ray results were compared with those obtained by semi-empirical and ab-initio calculations.     

Structures of two N-methylated tricyclic quinolones with antimalarial activity

The crystal structures of two N-methylated tricyclic quinolones were determined. 3-amino-6-methoxy-9-methyl-(1H)pyrazolo[3,4-b]-4-quinolone hydrate, C₁₂H₁₂N₄O₂ · H₂O (1) crystallizes in P-1 with a=11.5078(18) ?, b=13.0614(19) ?, c=9.0860(15) ?, α=106.229(4)°, β=108.378(3)°, γ=71.118(3)° and Z=4, while 2,4-diamino-10-methyl-9-methoxypyrimido[4,5-b]-5-quinolone, C₁₃H₁₃N₅O₂ (2) crystallizes in P2₁/n with a=10.6643(17) ?, b=10.1114(17) ?, c=11.3185(18) ?, β=99.351(4)° and Z=4. Both molecules are essentially planar, including the exocyclic groups. 1 and 2 have moderate antimalarial activity which seems to be related to the formation of intramolecular N – H · · · O=C hydrogen bonds; 1 does not form these bonds and has approximately twice the activity of 2. In both crystal structures there are extensive networks of N–H · · · O and N–H · · · N hydrogen bonds, and in 1 the water molecules of solvation form N–H · · · Ow, Ow–H · · · O=C and Ow–H · · · Ow bonds.     

Synthesis and crystal structure of cyanohydrin trimethylsilyl ether of o-chlorobenzoylferrocene

The cyanohydrin trimethylsilyl ether of o-chlorobenzoylferrocene has been synthesized by the addition of trimethylsilyl cyanide (TMSCN) in methylene chloride in the presence of zinc iodide. Its structure was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic, space group P2₁/n with the following crystallographic parameters: a = 9.480(3) ?, b = 22.319(6) ?, c = 9.783(3) ?, β = 101.197(4)°, μ = 0.943 mm^− 1, V=2030.5(10) ?³, Z=4, F(0 0 0) = 880, D _calc=1.386 mg/m³, T=293(2) K, 1.82° ≤ θ ≤ 26.40°, the final R factor: R ₁=0.0366, wR ₂=0.0802.     

The Synthesis and Structure of Two Novel <Emphasis Type="Italic">N</Emphasis>-(Benzothiazol-2-yl)benzamides

Abstract  Two novel benzothiazoles 2-chloro-N-(benzothiazol-2-yl)benzamide (1) and 2-chloro-N-(6-cyanobenzothiazol-2-yl)benzamide (2) were obtained in multistep synthesis. They were characterised by means of IR, ¹H- and ¹³C-NMR spectroscopy and also by single-crystal X-ray diffraction. The compound 1 crystallises with triclinic space group P , a = 9.5923(8) ?, b = 9.8583(8) ?, c = 13.8962(10) ?, α = 89.162(6)°, β = 77.741(7)°, γ = 80.064(7)°, V = 1264.5(2) ?³, Z = 4 and compound 2 crystallises as methanol solvate with monoclinic space group P 2₁/n, a = 7.5093(9) ?, b = 13.0211(14) ?, c = 16.032(2) ?, β = 92.717(10)°, V = 1565.9(3) ?³, Z = 4. Both crystal structures consist of discrete dimers connected into a three-dimensional network by intermolecular C–H···O and C–H···X (X = Cl or S) hydrogen bonds and by face-to-face π–π stacking interactions. Index Abstract  The synthesis and structure of two novel N-(benzothiazol-2-yl)benzamides. Irena Ćaleta, Dominik Cinčić, GraceKarminski-Zamola and Branko Kaitner. Hydrogen bonds and π–π interactions in N-(benzothiazol-2-yl)benzamides N-(benzothiazol-2-yl)benzamides.      

Variable Ag—O bonding patterns in silver cyclic amide tri-aryl-phosphine complexes

The solid-state structures of five new tri-arylphosphine silver cyclic amide complexes having a systematic variation in the ring structures have been resolved. Normal Ag—N bonding and variable, weaker Ag—O bonding interactions, which can be attributed to the ring modifications, form the basis of the bonding patterns. Reported here are the solid-state structures of silver complexes of tri-arylphosphine derivatives of silver 1(2H)-phthalazinone, silver phthalimide, silver 1,2,3-benzotriazin-4(3H)-one, silver 2H-1,3-benzoxazine-2,4(3H)-dione and silver 2,3-dihydro-1,4-phthalazine- dione. The unit cell parameters are: P-1, a = 11.179(2) ?, b = 15.508(3) ?, c = 22.636(5) ?, α = 104.30(3)°, β = 95.39(3)°, γ = 94.62(3)°; C2/c, a = 17.3600(8) ?, b = 15.4930(8) ?, c = 15.0760(7) ?, β = 113.911(2)°; P-1, a = 11.0656(2) ?, b = 11.9447(2) ?, c = 17.4764(3) ?, α = 79.5254(9)°, β = 80.2877(9)°, γ = 68.9136(7)°; P-1, a = 10.5743(4) ?, b = 11.8439(4) ?, c = 19.0110(8) ?, α = 102.4280(13)°, β = 104.0330(12)°, γ = 100.2520(18)°, P-1, a = 13.6908(3) ?, b = 16.2230(4) ?, c = 18.3678(7) ?, α = 86.8920(10)°, β = 69.5290(10)°, γ = 70.7840(10)°, respectively. Four of the complexes include ligand chelation by Ag—O bonding to the adjacent carbonyl in addition to the main Ag—N connection.     

Synthesis and Crystal Structure of a New Schiff Base 4-[(2-hydroxy-benzylidene)-amino]-<Emphasis Type="Italic">N</Emphasis>-(5-methyl-isoxazol-3-yl)-benzenesulfonamide

Abstract  The structure of the title compound (C₁₇H₁₅N₃O₄S)₂ the schiff base, bis(N-(5-methyl-3-isoxazolyl)-4-[(2-hydroxy benzylidene)-amino]) benzene sulfonamide was elucidated by H¹, C¹³ NMR, UV–VIS and IR spectroscopic techniques. The X-ray structure was determined in order to establish the conformation of the molecule. The compound crystallizes in the triclinic space group P-1, with a = 11.419(1), b = 11.426(0), c = 13.316(1) ?, α = 71.94(2), β = 89.79(1), γ = 89.14(2)° and Z = 4. Two benzene rings and azomethine group are practically coplanar, as a result of intramolecular hydrogen bonds involving the hydroxy O atom and azomethine N atom. The component species further interact via N–H···N and C–H···O hydrogen bonds and π–π stacking interactions. Index Abstract  The title compound (C₁₇H₁₅N₃O₄S)₂, Schiff base, bis(N-(5-methyl-3-isoxazolyl)-4-[(2-hydroxy benzylidene)-amino]) benzene sulfonamide was synthesized by the condensation of 4-amino-N-(5-methyl-3-isoxazolyl) benzene sulfonamide (SMZ) and 2-hydroxy benzaldehyde (SA). Its structure was confirmed by single crystal X-ray diffraction analysis. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis,Characterization, and Crystal Structure of <Emphasis Type="Italic">N</Emphasis>-<Emphasis Type="Italic">p</Emphasis>-Bromophenyl-<Emphasis Type="Italic">N</Emphasis>′-Phenylacetylthiourea

Abstract   N-p-bromophenyl-N′-phenylacetylthiourea was characterized by elemental analysis, IR and ¹H NMR etc. Single crystal structure of the title compound was determined on X-ray diffraction instrument. The title compound crystallizes in monoclinic space group c2/c, with a = 21.442(5) ?, b = 12.208(2) ?, c = 11.955(2) ?, β = 109.375(4)°, and D _calc = 1.571 g/cm³ for Z = 8. An intermolecular hydrogen bond N–H···S which links two thiourea molecules as a dimer and an offset face-to-face π–π stacking interaction were observed in the title compound. The strong non-covalent interaction influences the conformation and property of thiourea derivatives. Index Abstract  The title compound, N-p-bromophenyl-N′-phenylacetylthiourea, was synthesized by the treatment of phenylacetyl chloride with 4-bromoaniline and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that hydrogen bonds and face-to-face π–π stacking interactions have strong influence on the conformation and molecular stacking of the title compound.      

A crystallographic study of 2-hydroxyacetophenone N(4)-cyclohexyl thiosemicarbazone

The crystal structure of 2-hydroxyacetophenone N(4)-cyclohexyl thiosemicarbazone is described. The compound crystallizes in the triclinic crystal system, space group , Z = 4, V = 1569.6(3) ?³ with unit cell parameters a = 6.9436(8) ?, b = 12.4762(15) ?, c = 18.588(2) ?, α = 100.187(2)°, β = 97.069(2)° and γ = 92.340(2)°. There are two independent molecules in the asymmetric unit. The crystal structure reveals that the compound exists in the thione form and S1 and N1 are at E configuration to each other with respect to N2-C8 bond. Similarly, S2 and N4 are trans to each other with respect to N5-C23 bond in the second molecule of the asymmetric unit. The packing of the molecules in the crystal lattice is stabilized by intermolecular hydrogen bonds.     

Conformational diversity: Six conformers side-by-side in the crystal cell of 2,2′,7,7′-tetramethoxy-9,9′-spiro-9-silabifluorene

X-ray crystal structure analysis of a sublimation-grown spiro silabifluorene, that is highly fluorescent in the violet-blue, established that there are six cocrystallized ordered conformers in the asymmetric unit. Crystals were grown by a vapor transport method under argon gas flow at temperatures between 255–280°C. As expected, there are no cocrystallized solvent molecules. There is no π-stacking of the aryl groups. There is no possibility for normal hydrogen bond formation; however, several CH⋯π bonds occur. The packing is efficient with a density of 1.24 g/cc. Each conformer deviates from tetrahedral geometry around the Si atom. Cell data are: C₂₈H₂₄O₄Si×12, sp. gr. P, a=16.2750(5) ?, b=20.6613(5) ?, c=23.8289(5) ?, α=102.025(2)°, β=94.252(2)°, and γ=109.916(2)°, V=7275(1) ?³.     

Crystal and Molecular Structure of <Emphasis Type="Italic">trans</Emphasis>-1,2-bis(2-benzothiazolyl)ethene

Abstract The crystal and molecular structure of trans-1,2-bis(2-benzothiazolyl)ethene is reported. Crystal data for 1: monoclinic, space group C 2/c, a = 24.926(3) ?, b = 4.843(1) ?, c = 11.164(1) ?, β = 105.274(5) °, V = 1300.0(3) ?³, and D _c = 1.50 g/cm³ for Z = 4 and R = 0.028. The molecule crystallizes in the form of a colorless plate and forms one-dimensional slipped π-stacks. Graphical Abstract The title compound crystallizes to form 1D slipped π-stacks in the solid state. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.