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.     

Synthesis and crystal structure of Mn(II) and Zn(II) complexes with 1,3,5-tris(carboxymethoxyl)benzene ligand

Two complexes (H₂bipy)[M₂(TB)₂(H₂O)₈]·5H₂O (M = Mn 1, Zn 2) (bipy = 4,4′-bipyridine, H₃TB = 1,3,5-tris(carboxymethoxyl)benzene) were synthesized by the reaction of the corresponding metal salt with ligand H₃TB and 4,4′-bipy in an aqueous methanol solution at room temperature, respectively. Their structures were determined by single crystal X-ray diffraction analysis. Both complexes 1 and 2 crystallize in the triclinic space group with the crystal parameters of 1: a = 9.725(12) ?, b = 10.651(13) ?, c = 10.882(13) ?, α = 91.72(2)°, β = 96.41(2)°, γ = 97.72(2)°, V = 1109(2) ?³, Z = 1 and 2: a = 9.610(10) ?, b = 10.55(2) ?, c = 10.83(2) ?, α = 91.60(4)°, β = 95.32(2)°, γ = 97.73(4)°, V = 1082(3) ?³, Z = 1. Complexes 1 and 2 have the same dinuclear structure, in which each metal atom is six coordinated with distorted octahedral geometry by two oxygen atoms from two different TB³⁻ ligands and four ones from four coordinated water molecules. The dinuclear units are further linked by hydrogen bonding and π–π interactions to form the three-dimensional framework structure.     

Hydrogen bonds and π–π stacking interaction in 4′, 7-dimethoxylisoflavone and 4′,7-diacetyl-O-isoflavone

4′,7-dimethoxylisoflavone, C₁₇H₁₄O₄, (I), is linked into a supramolecular structure by a variety of weak but direction-specific intermolecular forces, the molecules are linked into chains through C–H⋅sO hydrogen bonds, these chains are further linked by face-to-face (F-tape) π–π stacking into a one-dimensional bi-chain, another type π–π stacking, edge-to-face (T-tape), assemble the bi-chain into framework together with C–H⋅sO hydrogen bonds. 4′,7-diacetyl-O-isoflavone, C₁₉H₁₅O₆, (II), shows some discrepancies with I and the molecules are assembled into framework all by C–H⋅sO hydrogen bonds. The molecules are linked into centrosymmetric dimers built from classic R₂² (8) rings by pairs of C–H⋅sO hydrogen bonds, the dimers are linked into (011) sheets by combination of the R₂² (8) ring and C–H⋅sO hydrogen bonds, another C–H⋅sO hydrogen bond assemble the sheets into three-dimensional network.     

C–H...O,C–H...π and π–π stacking interactions in 3-(2,4-dimethylphenyloxymethyl)-3,4-dihydroisocoumarin

3-(2,4-Dimethylphenyloxymethyl)-3,4-dihydroisocoumarin (C₁₈H₁₈O₃) was prepared by the alkylation of o-lithio N-methyl benzamide with 2-(2,4-dimethylphenoxy)methyl oxirane, followed by alkaline hydrolysis. The compound crystallizes in the orthorhombic space group Pbca with unit cell parameters : a = 8.239(2) Å, b = 14.918(5) Å, c = 24.831(9) Å, Z = 8. The crystal structure was solved by direct methods and refined to R = 0.0514 for 1564 observed reflections. The heterocyclic ring adopts a distorted half-chair conformation. Molecules are connected by π–π interactions between phenyl rings of the isocoumarin nucleus forming dimers. Dimers are connected via C–H...O hydrogen bonds forming chains. Further intermolecular C–H...π hydrogen bonds link the dimer chains to form supramolecular structure.     

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.     

Synthesis and characterization of a lead(II) complex [Pb(phen)(H<Subscript>2</Subscript>O)(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>] (phen = 1,10-phenanthroline)

The monomeric lead(II) complex, [Pb(phen)(H₂O)(NO₃)₂] was prepared by a hydrothermal reaction of Pb(NO₃)₂, nitrilotriacetic acid, NaOH, 1,10-phenanthroline, and H₂O. The structure was determined by X-ray crystallography. It crystallizes in monoclinic P2(1)/n space group with the crystal cell parameters of a = 6.3568(6), b = 20.2345(19), c = 11.2722(9) Å, β = 98.337(4)^°, V = 1434.6(2) ų, and Z = 4. The crystal X-ray analysis shows that the lead atom is six-coordinated by two N atoms of phen ligand, three oxygen atoms of nitrate anions and one water molecule. Owing to the presence of a lone pair of electrons of lead atom, a significant gap occurs in the coordination geometry around Pb ion. A 3D architecture is formed through the strong hydrogen bonding and π–π stacking interactions.     

3-Methyl-3a,4-Dihydro-3H-Thiochromeno[4,3-c]isoxazol

Abstract  The crystal structure of the title compound, C₁₁H₁₁NOS, was determined by an X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P2₁/c with cell parameters a = 10.533(2) ?, b = 12.7826(19) ?, c = 7.6491(17) ?, β = 107.997(17)^°, V = 979.5(3) ?³ and Z = 4. The S containing heterocycle adopts a sofa conformation, whereas the 5-membered ring adopts an envelope conformation. The crystal packing is characterized by weak C–H···N contacts and π-stacking interactions. Graphical Abstract  The title compound, 3-methyl-3a,4-dihydro-3H-thiochromeno[4,3-c]isoxazol was synthesized by an 1,3 dipolar cycloaddition reaction and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that the aromatic 6-membered ring is planar, whereas the ring containing the S atom adopts a sofa conformation and the 5-membered ring an envelope conformation. The methyl group is in an equatorial position.      

Synthesis and Crystal Structure of 5,7,12,13b,13c,14-Hexahydro-1,4,-dibromo-8,11-dimethoxy-13b,13c-bis(ethoxycarbonyl)-6H,13H-5a,6a,12a,13a-tetra azbenz[5,6]azuleno[2,1,8-ija]benz[f]azulene-6,13-dione

The title compound has been synthesized by the reaction of 4 with 1,4-dimethoxybenzene. The yielded product 5 was investigated with X-ray crystallographic, NMR, EI-MS, and IR techniques. The crystal belongs to a monoclinic system, space group P2₁/c with unit cell parameters a = 12.7790(17) Å, b = 21.565(3) Å, c = 12.2544(16) Å, α = 90°, β = 107.014(2)°, γ = 90°, V = 3229.3(7) Å³, Z = 4, D_c = 1.661, M_r = 807.32, μ = 2.732 mm^?1, F(000) = 1632, R₁ = 0.0540 and wR₂ = 0.0989.     

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-[2-(6-bromonaphthalenyloxymethyl)]-3-(4-morpholinomethyl)-1,3,4-oxadiazole-2(3<Emphasis Type="Italic">H</Emphasis>)-thione

Abstract  The title compound, C₁₈H₁₈BrN₃O₃S, a derivative of 1,3,4-oxadiazole, crystallizes in the triclinic space group P-1 with unit cell parameters a = 6.8731(3), b = 8.9994(4), c = 15.7099(6) ?, α = 92.779(3)°, β = 130.575(3)°, γ = 107.868(4)°, Z = 2. The dihedral angle between the mean planes of the planar naphthyl and morpholine (chair) rings with the planar oxadiazol ring is 50.1(8) and 76.8(6)°, respectively. The planar naphthyl ring is twisted 52.2(5)° with the mean plane of the morpholine ring. A group of four intermolecular close contacts are observed between a bromine atom and hydrogen atoms from the closely packed naphthyl, morpholine and oxy–methyl groups in the unit cell. These molecular interactions in concert with an additional series of π–π stacking interactions that occur between the center of gravity of the two 6-membered rings of the naphthalene group influence the twist angles of each of these three groups. A MOPAC AM1 calculation of the conformation energy of the crystal structure [226.0128(9) kcal] compared to that of the minimum energy structure after geometry optimization [29.9744(1) kcal] reveals a significantly reduced value. The twist angles of the three groups above also change after the AM1 calculation giving support to the influence of both intermolecular C–H···Br short-range interactions and Cg π–π stacking interactions on these angles which therefore play a role in stabilizing crystal packing. Graphical Abstract  Crystal structure of 5-{[(6-bromonaphthalen-2-yl)oxy]methyl}-3-(morpholin-4-ylmethyl)-1,3,4-oxadiazole-2(3H)-thione, C₁₈H₁₈BrN₃O₃S, is reported and its geometric and packing parameters described and compared to a MOPAC computational calculation. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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.     

The co-crystal of iron(II) complex hydrate with hydroxybenzoic acid: [Fe(Phen)<Subscript>3</Subscript>]Cl(p-hydroxybenzoate).2(p-hydroxybenzoic acid).7H<Subscript>2</Subscript>O

Crystal of [Fe(Phen)₃]Cl(PHB).2(PHBH).7H₂O (1) is triclinic, space group P-1 with a = 12.0388(11) ?, b = 15.5286(14) ?, c = 15.7794(14) ?, α = 89.759(2)°, β = 75.818(2)°, γ = 71.900(2)° and Z = 2, (phen = phenanthroline, PHBH = p-hydroxybenzoic acid, PHB = p-hydroxybenzoate anion). The phen in adjacent Fe(phen)₃ ²⁺ cations are π–π interacted forming offset face to face (OFF) motifs. Juxtaposition of four phen ligands from two cations encapsulate an R₂ ²(8) dimeric unit of H-bonded PHBH molecules within a centrosymmetric box froming a filled aryl box motif (FAB). Alternation of OFF and FAB motifs form {OFF⋯FAB}∞ strands. The Fe(phen)₃ ²⁺ cation engages its phen ligands in π–π and/or CH–π interactions with two crystalographically different PHBH molecules and one PHB anion. Seven water molecules and a chloride anion per iron(II) trisphenanthroline cation fill empty spaces in the structure forming a hydrophilic cluster. Extensive intermolecular H-bond interactions occur between water molecules, chloride anions, PHBH molecules, and PHB anions. Thermal analysis of (1) was done under N_2(g). The TG, and dTG curves revealed the expected mass losses. All associated processes are endothermic as shown in the DSC curve.     

A structural study of copper(II) carboxylates: Crystal structure and physical characterisation of [Cu2(2-bromopropanoato)4(caffeine)2]

Based on the bond-valence sum model the continual transition between the bidentate and monodentate bonding mode of carboxylato group and minimum of Cu–O bond lengths were estimated. The dependence of Cu⋯Cu separation on Cu–N bond length in binuclear Cu(II) carboxylates with caffeine were derived and fitted to the observed data. The crystal structure of [Cu₂(2-bromopropanoato)₄(caffeine)₂] has been determined by X-ray crystallography. The structure consists of centrosymmetric binuclear units where the two Cu atoms are coordinated by four disordered bridging 2-bromopropionates and two caffeine ligands at the apices of a bicapped square prism. Both 2-bromopropionates show disorder of their –Br and –CH₃ substituents. Stacking π·π interactions between the adjacent caffeine molecules link the complex units in 1-D networks. The binuclear structure of the studied compound is consistent with magnetic data and EPR spectrum.     

Synthesis and crystal structure of a new two-dimensional chromium(III) network through hydrogen bonds

A new chromium(III) complex, [Cr(ox)(bdmpza)(H₂O)], (ox = oxalate dianion and bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate, respectively), has been synthesized and characterized by X-ray crystallography. This compound crystallizes in the monoclinic space group P2₁/c, with a = 7.008(3) Å, b = 14.229(5) Å, c = 16.497(7) Å, = 101.588(7)°, V = 1611.5(11) ų, Z = 4. The chromium atom has a distorted octahedral environment with different coordination atoms. Bis(3,5-dimethylpyrazol-1-yl)acetate anion is a tridentate ligand, and the oxalate group acts as a chelating bidentate ligand. This compound also forms an infinite two-dimensional network through O–H O hydrogen bonds. The lengths of the hydrogen bonds are 2.765(5) and 2.733(5) Å, respectively.     

Crystal structure of irisolidone from the flowers of Pueraia lobata

Irisolidone (5,7-dihydroxy-6,4′-dimethoxyisoflavone) was isolated from the flowers of Pueraia lobata and its crystal structure was examined by X-ray single crystal diffraction. The crystal structure of irisolidone is monoclinic, space group P2₁/c with a = 15.491(9) ?, b = 7.895(4) ?, c = 13.321(7) ?, β = 110.546(9)° and Z = 4. Hydrogen bonding and aromatic π–π stacking assemble the title compound into a three-dimensional networking structure.     

Structures and Non-linear Optical Properties of Multi-Sulfur π-Conjugated Compounds 4,5-Vinylenedithio-1,3-dithiole-2-thione (C5H2S5) and 4,5-Vinylenedithio-1,3-dithiole-2-one (C5H2OS4)

Abstract Both the title multi-sulfur molecules C₅H₂S₅ (1) and C₅H₂OS₄ (2) have a chair conformation, while molecule 1 has a higher degree of π-conjugation. Both the crystals are characterized by short S···S intermolecular contacts and by face-to-face column-like packing style, but crystal 1 has been more stabilized which may be the result of its stronger π–π intermolecular interactions. Compound 1 crystallizes in non-centrosymmetric polar space group Pmn2₁ with a = 10.6826(17), b = 9.3633(11), c = 4.0764(6) ?, V = 407.74(10) ?³, and Z = 2. The molecular dipole moment of 1 is ±62.5(1)° away from the macro-polarization direction along the c-axis. Consequently, the crystalline powder of crystal 1 exhibit a second harmonic generating (SHG) intensity 0.5 time strong as that of urea standard powder crystals when irradiated by a 1,080 nm of Nd:YAP laser beam. Compound 2 shows no SHG effect because it crystallizes in centrosymmtric space group Pbca with a = 11.4208(8), b = 7.8843(9), c = 33.587(3) ?, V = 3024.3(5) ?³, and Z = 16. Index Abstract Structures and Non-linear Optical Properties of Multi-Sulfur π-Conjugated Compounds 4,5-Vinylenedithio-1,3-dithiole-2-thione (C₅H₂S₅) and 4,5-Vinylenedithio-1,3-dithiole-2-one (C₅H₂OS₄) Gang Xue, Qi Fang,* Wen-Tao Yu, Xia Chen, and Hong Lei Compound C₅H₂S₅ crystallizes in the polar space group Pmn2₁ and its crystalline powder exhibits a second harmonic generating (SHG) intensity 0.5 times that of urea standard (1080 nm → 540 nm), while the similar compound C₅H₂OS₄ has no SHG effect because of its centrosymmetric space group Pbca.      

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.     

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.      

The crystal structure of a bis(2,6-pyridinedicarboxylato)chromate(III) anion with an elaborate network of hydrogen bonding and π stacking

The synthesis, X-ray crystallography, spectroscopic, and electrochemical properties of the title compound, [Hdpa][Cr(dipic)₂]·3H₂O, 1, are reported. Compound 1 crystallized in the triclinic space group P-1 with a = 7.1057(11) ?, b = 12.965(2) ?, c = 14.269(2) ?, α = 80.306(3)°, β = 82.101(2)°, γ = 83.799(2)°, and V = 1278.6(4) ?³ with Z = 2. The distorted octahedral chromium anions are part of an elaborate network of hydrogen bonding formed by the waters of solvation, the anion, and cation as well as π-stacking interactions.     

Synthesis and Crystal Structure of 4-Methyl-6H-pyrido[3,2,1-<Emphasis Type="Italic">jk</Emphasis>]carbazol-6-one

Abstract  The synthesis, NMR and X-ray structure of 4-methyl-6H-pyrido[3,2,1-jk]carbazol-6-one—a potential DNA intercalator are reported. The compound crystallizes in the orthorhombic Pbca space group with unit cell parameters: a = 7.775(8), b = 15.113(7), c = 19.849(7) ?, V = 2332.8(3) ?³, Mr = 233.26 and Z = 8. In the three-dimensional arrangement of the molecules no classical hydrogen bonds were found; weak π···π and C–H···O interactions are responsible for the packing of the molecules in the crystal structure. Index Abstract  In the three-dimensional arrangement of the title compound no classical hydrogen bonds were found; weak π···π and C–H···O interactions are responsible for the packing of the molecules in the crystal structure.