Crystal structures of inclusion compounds of 4-aminobenzenesulfamidine (sulfaguanidine) with two dicyclohexano-18-crown-6 isomers

The crystal structures of inclusion compounds of 4-aminobenzenesulfamidine (sulfaguanidine) (L) with two dicyclohexano-18-crown-6 (DCH-6) isomers A(cis-syn-cis) and B(cis-anti-cis) have been determined by X-ray methods. The complexes exhibit 1:2 host-guest ratios. In fact the complex of isomer A is formulated as [DCH-6^A·[L]H₂O]L (complexI), while that of isomerB is DCH-6 ^B L₂ (complex I1).In the crystals, host and guests are connected by O-H...0 and N-H...O bonds.     

Crystal structure of inclusion compounds: The complexes of thecis-syn-cis and thecis-anti-cis isomers of dicyclohexano-18-crown-6 with 4-methylbenzenesulfamide

The crystal structure of two complexes of the isomerscis-syn-cis (isomer A) andcis-anti-cis (isomer B) of dicyclohexano-18-crown-6 with 4-methylbenzenesulfamide have been determined by X-ray single crystal diffraction methods. The two structures have been solved by direct methods and refined to agreement values of 0.067 and 0.038 for isomers A and B respectively. The first isomer forms an inclusion compound with a host/guest ratio of 1 : I; the second one of I:2. The amino groups of the guest molecules are connected by N-H...O hydrogen bonds with oxygen atoms of the polyether molecules. The methyl groups of 4-methylbenzenesulfamide do not form hydrogen bonds.[/p]The host-guest interactions in the molecular complexes, the reciprocal influence of the two molecules on their conformation and the intermolecular contacts between the molecules in the crystal are discussed.     

On the solid-state conformations of 18-crown-6 complexes

A procedure for displaying macrocylic torsion angles as a map on polar coordinates is discussed with reference to the solid-state conformations of l8-crown-6 and its complexes. The maps aid in comparisons of related structures, in the perception of pseudo-symmetry elements, and in the classification of the conformations of 18-crown-6. Only four conformational groups are found in the 1 : 1 complexes of 18-crown-6 with sodium, potassium, rubidium, cesium, thallium(I), calcium and strontium cations. The relationship of donor number, mean cavity radius and effective ionic radius combined with skeletal drawings of the donors and the polar map of the torsion angles provide a composite picture of the structures and insight into the balance between cation-donor interaction energy and conformational energy.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Synthesis and Crystal Structure of 3,3＇-Dimethyl-dibenzo-18-crown-6

1 INTRODUCTION Since the report about unusual coordination num- bers and arrangements to metal ions of crown ether compounds by Pedersen[1], the crown ether compounds have attracted much attention. Due to their novel coordination modes, crown ethers have been widely used in catalyst, solvent extraction, iso- tope separation, bionics, material chemistry, host- guest chemistry and supramolecular chemistry[2~5]. So it is vital to study the synthesis of new crown ethers and their crystal stru…     

Synthesis and crystal structure of ammonium (picrate) (dibenzo-18-crown-6)

NH₄(Pic)(DB18C6) (Pic=picrate and DB18C6=dibenzo-18-crown-6), (C₂₆H₃₀N₄O₁₃) FW 606.56, arthorhombic,Pmn2₁,a=26.045(5),b=12.055(3),c=8.982(3) Å,V=2820(1) ų,Z=4,D _c =1.429 g/cm³, CuK, =1.54184 Å, (CuK)=9.5 cm^–1,F(000)=1272,T=298 K. The structure has been refined toR=0.0475 for 2617 unique observed reflections. In the lattice the 1:1 complex exists as a 2:2 dimer in which the crown are coupled through the Pic anions and NH₄ ⁺ cations. The asymmetric unit consists of two independent half crown ethers of which two opposite O atoms are on the mirror plane, two half ammonium cations of which the N and two H atoms are also on the mirror plane while the Pic anion is in a general position. Relative to each other, the corwn ethers are shifted by about 7.3 Å alongb and 1 Å alongc. The 1:1 sandwich of NH₄ with DB18C6 and Pic on dimerisation becomes a club pseudo-sandwich with three phenyl rings on either side of the mirror plane, thus forming a nearly parallel stack with a 3.6 Å inter-ring distance. The NH₄ ions hold the structure; two H atoms on the mirror plane are hydrogen-bonded to the opposite oxygens of the crown located on the purely aliphatic part of the ring (2.10(1), 2.06(3) and 2.26(3), 2.05(1) Å) for the two independent crowns, respectively, while the other two H atoms form mirror-related bifurcated hydrogen bonds with the phenoxide oxygen (1.99(1) and 2.01(1) Å) and theo-nitrogen oxygen (2.44(2) and 2.34(1) Å) of the picrates. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82037 (29 pages)     

二环己基并18冠6的制备方法

二苯并-18－冠-6;二环己基并18冠6的制备方法     

Host: Guest chemistry of diaza-18-crown-6: Selective precipitation from mixtures of oligohydroxy phenols and the structures of five host: Guest complexes

Diaza-18-crown-6 (1,4,10,13-tetraoxa-7,16-diaza-cyclo-octadecane) selectively precipitates as a 1,4-dihydroxybenzene-complex from a mixture of isomeric phenols and as a 2,6-dihydroxynapthalene-complex from mixtures of isomeric diols. These selective precipitations are discussed in terms of structure and solubility of the host-guest complexes and phenol acidity. The crystal structures of diaza-18-crown-6 with guestsp-nitrophenol (2: 1), 2,4-dinitroaniline (2: 1), 5,5-diethylbarbituric acid (2: 1), salicylaldoxime (2: 1) and 1,4-dihydroxybut-2-yne (1: 1) are reported. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82065 (74 pages).     

[{Pt4(en)4(NHCOtBu)4}{Tl(18-crown-6)}2](PF6)6的合成与晶体结构

The compound [{Pt₄(en)₄(NHCO^tBu)₄}{Tl(18-crown-6)}₂](PF₆)₆ has been synthesized by a simple one-pot multicomponent reaction. Its structure was determined by X-ray single crystal diffraction analysis. The cation of the compound consists of one linearly arranged [Pt₄(en)₄(NHCO^tBu)₄]⁴⁺ chain and two [Tl(18-crown-6)]⁺ ions located at the two ends of the platinum chain. The complex crystallizes in a triclinic P1 with a=1.060 5(1), b=1.252 3(1), c=2.015(2) nm, α=107.430(2)°, β=91.032(2)°, γ=101.910(2)°, V=2.489 6(4) nm³, Z=2, R₁=0.074 4, wR₂(I>2σ(I))=0.222 5, S=1.062. CCDC: 294083.     

Crystalline inclusion compounds of tetrabenzo-18-crown-6 with uncharged organic molecules. Solid-state structure of the nitroethane complex

Tetrabenzo-18-crown-6 (1) shows distinct solid-state inclusion properties towards a number of OH-acidic, CH-acidic and low-polar uncharged organic molecules. The single crystal X-ray analysis of the inclusion complex between1 and EtNO₂ (11) is reported. Crystals are monoclinic,P2₁/c, witha=12.887(1),b=19.365(2),c=10.776(1) Å, =96.33(2)^o,D _c=1.321g cm^–1,Z=4. The host macroring has a conformation similar to a dentist's-chair. The complex is stabilized mainly by C–H...O type interactions involving the methyl group of the EtNO₂ guest molecule which is highly disordered. The nitroethane guests are trapped in channels formed by the host macrocycles. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82150 (11 pages)     

一维链状冠醚配合物:[{Na(18-C-6)}2(H2O)]n[M(SCN)4]n(M=Pd、Pt)的合成与结构

The reactions of 18-crown-6 with Na₂[M(SCN)₄] (M= Pd,Pt) were studied and the complex 1 [{Na(18-C-6)}₂(H₂O)]_n[Pd(SCN)₄]_n and complex 2 [{Na(18-C-6)}₂(H₂O)]_n[Pt(SCN)₄]_n were characterized by ele-mental analysis, IR and X-ray diffraction analysis. The complexes belong to monoclinic, space group P2₁/n with cell dimensions, 1:a=1.05734(7),b=1.42250(10),c=1.47762(10) nm,β=107.5330(10)°,V=2.1192(2)nm³,Z=2,D_calcd=1.460g·cm^-3,F(000)=964,R₁=0.0406,wR₂=0.1264 and 2:a=1.05985(19),b=1.4237(3),c=1.4744(3) nm,β=107. 096(3)°, V=2.1264(7)nm³,Z=2,D_calcd=1.690g·cm^-3,F(000)=1028,R₁=0.0292,wR₂=0.0859. In the solid state, the complexes 1 and 2 show an one-dimensional chain of [{Na(18-C-6)}₂(H₂O)]²⁺ complex cations and [M(SCN)₄]^2- (M=Pd,Pt) complex anions bridged by Na-N in-teractions.     

Crystal structure of the 1 : 4 complex between 18-crown-6 and a polyfunctional guest: 2-hydroxymethyl-4-(1,1,3,3-tetramethylbutyl)phenol

Single crystal X-ray analysis of the 1 : 4 complex between 18-crown-6 and 2-hydroxymethyl-4-(1,1,3,3-tetramethylbutyl)phenol is reported. Crystals of the complex are triclinic witha = 11.929 (2),b = 18.655(2),c = 8.313(1)Å, = 93.14(1), = 94.02(1), = 100.89(1)^o, andD _c = 1.111 g cm^–3 forZ = 1. TheR index is 0.057 for 5935 reflections measured at 293 K. The complex lies on a center of symmetry, the macroring has the Ci symmetry (g ⁺ g ⁺ aag ^– aag ^– ag ^– g ^– aag ⁺ aag ⁺ a). The CH₂-OH group at theortho position to the phenolic OH lies near the benzene ring plane; this conformation differs from the one found for uncomplexed phenol-alcohol molecules. The packing is characterized by layers of hydrogen bonded entities parallel toac; alongb the layers are stabilized by van der Waals interactions.     

吖啶基功能化二苯并-18-冠-6的合成

通过改变离去基团的活性、亲核试剂、溶剂的极性、离子性及反应温度等,对传统的U llm ann合成法进行了优化,将二苯并-18-冠-6进一步功能化,合成了未见文献报道的N,N′-二-(9-吖啶基)-4,4′-二氨基二苯并-18-冠-6,收率在87%以上。其结构经1H NMR,IR及元素分析表征。     

Structure of 〔Na(DB18C6) (CH_3OH)〕_2W_6O_(19)·(DB18C6)·(CH_3OH)

1INrnODUCTIoNlnthepreviouspapers,wehavereportedthesynthesisandcrystalstructureofseveralcrownetherpolyoxometalates"-",nowwestudythestructureofthetitlecomplexandcompareitwithsomeothercrownetherpolyoxometalatecomplexes.2EXPERmENTALToal5OmLaqueoussolutioncontaining32g(1OOmol)Na,WO#.2H,Opre-justedtopH=3.5withchloricacid,14g(4Ommol)(n-Bu)'NBrwasadded,thenwhitepowderwasformed.ThewhiteprecipitateobtainedwithafiltrationwaskeptasthenewmaterialAinnextstep.AmixtureoflgAandO.3g(O.8mmol)DB18…     

Synthesis and Characterization of One-dimensional Dicyclohexyl-18-crown-6 Complexes with M2[Cd(mnt)2] (M = Na, K)

Two supramolecular crown ether complexes [Na(DC18C6-A)(H₂O)]{[Na(DC18C6-A)][Cd(mnt)₂]} (1) and [K(DC18C6-A)]₂[Cd(mnt)₂] (2) (DC18C6-A = cis-syn-cis-dicyclohexyl-18-crown-6, isomer A; mnt = maleonitriledithiolate) have been synthesized and characterized by elemental analysis, FT-IR spectroscopy and X-ray single crystal diffraction. Complex 1 is composed of one [Na(DC18C6-A)(H₂O)]⁺ complex cation and one {[Na(DC18C6-A)][Cd(mnt)₂]}⁻ complex anion and displays an infinite chain-like structure through N–Na–N interactions. In complex 2, [K(DC18C6-A)]⁺ complex cation and [Cd(mnt)₂]²⁻ complex anion afford a novel 1D ladder-like structure by N–K–N, N–K–S interactions.     

Crystal Structure of N,N'-Bis(dodecyl)diaza- 18-crown-6 Complexed Sodium Perchlorate

The crystal structure of a new complex of a diaza-crown ether having two side arms has been determined from X-ray diffraction data. The compound crystallizes in space group P1 with cell dimensions a = 9.982(1), b = 10.685(1), c = 20.376(2)Å, = 81.09(1), = 80.92(1), = 88.43(1)0, Z = 2. The structure has been solved by direct methods and refined to the final R value of 0.053 for 3458 observed reflections and 424 parameters. The diaza-18-crown-6 ligand adopts an approximate D3d conformation. The Na+ ion is held inside the molecular cavity of this macroring ligand and a ClO-4 oxygen coordinates with Na+. The average Na–-O (18-crown-6) and Na–-N bond lengths are 2.426(4) and 2.786(5)Å, respectively; the Na–-O (ClO-4) bond length is 2.472(4)Å. The mean cavity radius is 1.10 Å and the NN nonbonding distance is 4.605(6)Å.     

A europium(II) complex with bis-pyridino-18-crown-6

A new Eu(II) complex, bis(perchlorato)(bis-pyridino-18-crown)europium(II), has been obtained in the crystalline form by electrolytic reduction. The metal ion is 10-coordinated and its surrounding consists of four macrocycle O atoms, two N ones and four O atoms from perchlorate anions. The compound shows a very broad absorption band, starting gently from 600 nm towards the UV region, and two weak luminescence bands with maxima at 430 and 500 nm. The performed density functional theory (DFT) calculations have shown that the absorption results from mixed f–d, f–s and charge transfer transitions. The possible mechanism of luminescence is also discussed.     

Dibenzo-18-crown-6 modified with kojic acid fragments

Diazonium salts were prepared by diazotization of 4′-amino-, 4′,4″-, and 4′,5″-diaminodibenzo-18-crown-6. Their coupling products with kojic acid (5-hydroxy-2-hydroxymethyl-γ-pyrone) were synthesized for the first time: 4′-(6-aza-5-hydroxy-2-hydroxymethyl-γ-pyronyl)-, 4′,4″-di-(6-aza-5-hydroxy-2-hydroxymethyl-γ-pyronyl)-, and 4′,5″-di-(6-aza-5-hydroxy-2-hydroxymethyl-γ-pyronyl)-dibenzo-18-crown-6. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 415–416, September–October, 2006.     

微波辅助二苯并-18-冠-6的合成

以邻苯二酚与二甘醇二取代物为原料,氢氧化钾为碱和模板剂,在微波辅助下,采用“一锅煮”法合成二苯并-18-冠-6。 经单因素及正交实验考察了原料、溶剂、时间、温度和功率对反应收率的影响,获得了最佳的工艺条件：以邻苯二酚与二氯乙醚为原料,二甲亚砜为溶剂,反应温度70 ℃,时间60 min,功率500 W,收率可达46.3%。     

Second crystal modification of 1,10-diazonia-18-crown-6 dichloride

The second crystal modification (II) of 1,10-diazonia-18-crown-6 dichloride [H₂DA18C6]²⁺·2Cl^?, where [H₂DA18C6]²⁺ is the 1,10-diaza-18-crown-6 dication (DA18C6) with two protonated nitrogen atoms, was investigated by XRD. The monoclinic modification (II) (space group P2₁/n, a = 9.600 Å, b = 5.689 Å, c = 15.749 Å, β = 91.03°, Z = 2) was solved by direct methods and refined by full-matrix least squares analysis in an anisotropic approximation to R = 0.032 for all 2494 independent reflections collected (CAD-4 automatic diffractometer, λMoK _α). In modification II, the conformation of the DA18C6 dication and the ion packing differ from those in triclinic modification I investigated previously.     

New Derivatives of Dibenzo-18-crown-6 with Salsolidine and Salsoline Fragments

New derivatives of dibenzo-18-crown-6 were prepared by condensing 4,4(5)-dibenzo-18-crown-6-dicarboxylic acid dichloride with salsolidine and salsoline. The structures of these compounds were proved by PMR and IR spectral methods.