The N atoms of the title compound, C 18 H 16 N 2 O 4 S 2 , are not preorganized for metal cation binding. The N—H groups form hydrogen bonds with symmetry-equivalent sulfonamide groups.

The crystal structure of hexaaquazinc triflate is reported. The zinc center is surrounded by an octahedral environment of aqua ligands. The triflate anions occupy the second coordination sphere forming O–H⋅⋅⋅O hydrogen bonds with the aqua ligands. Thermogravimetric analysis is consistent with six water molecules binding to the cation.

Bis-cage-annulated 18-crown-6 and 20-crown-6 macrocyclic ethers (i.e., 1 and 2 , respectively) have been synthesized, and their alkali metal picrate extraction profiles have been determined. Host system 1 proved to be a significantly more avid alkali metal cation complexant than 2 and somewhat more avid than 18-crown-6. Both 1 and 18-crown-6 display modest selectivity toward K + and Rb + . A stable host–guest complex was prepared by slow evaporation of a CH 2 Cl 2 –hexane solution of an equimolar mixture of 2 and potassium picrate. The X-ray crystal structure of this complex reveals that picrate anion functions as a bidentate ligand therein. The gas-phase interaction energy between the 2 ⋅ K + complex and picrate anion was calculated to be ca. −64.9 kcal mol −1 , thereby indicating that participation of picrate anion as an additional bidentate ligand results in significant stabilization of complex 10 .

The podand, bis(2-methoxyphenoxy)m-xylene (1), was designed and synthesized as a potential host for the cesium ion. Its structure was determined by single crystal X-ray diffraction. It crystallizes in P21/c with cell dimensions: a = 8.5723(7) Å, b = 8.3931(14) Å, c = 25.2879(26) Å, β = 96.224(9)○, and V = 1808.7(4) Å3. A crown derivative, tribenzo-21-crown-6 (2), was also prepared and structurally characterized. It also crystallizes in P21/c with cell dimensions: a = 15.5825(13) Å, b = 15.8648(16) Å, c = 8.8266(7) Å, β = 95.247(6)○, and V = 2172.9(3) Å3. The structures exhibit hydrogen bonding, and are evaluated in terms of complementarity and preorganization for cesium binding.

Reactions of W(CO)3(phen)(EtCN) with butane thiols, thiophenol, 1,2-benzenedithiol, and 3,4-toluenedithiol have been investigated. Reaction of butanethiol results in simple ligand exchange to form the thiol complex W(CO)3(phen)(nortBuSH). Reaction with thiophenol results in oxidative addition to form the W(II) thiolate hydride complex W (CO)3(phen)(SPh)(H). The lower reducing power of Mo compared to W is demonstrated in that simple ligand binding of PhSH to Mo(0) occurs forming Mo(CO)3(phen)(PhSH). Reactions of arene dithiols with W(CO)3(phen)(EtCN) were found to proceed with initial oxidative addition of one S–H bond of the chelating dithiols to form W(CO)3(phen)(H)[S–arene(SH)]. These complexes slowly eliminate H2 and CO to form W(CO)2(phen)(arenedithiolate) complexes. The same complexes can be formed by thiol/thiolate exchange reactions: W(CO)2(phen)(SR)2 (R=tBu, Ph) react quantitatively with arene dithiol to yield W(CO)2(phen)(arenedithiolate). The crystal structure of W(CO)2(phen)(3,4-toluenedithiolate) has been determined and is trigonal prismatic rather than octahedral. Values for ΔH° (thiol/thiolate exchange) have been measured by solution calorimetry relative to W(CO)2(phen)(StBu)2=0.0 kcal mol−1; (CO)2(phen)(SPh)2=−7.2±0.4 kcal mol−1 and W(CO)2(phen)(3,4-toluenedithiolate)=−12.5±0.6 kcal mol−1.

The crown ether portion of the title complex, C 50 H 66 O 6 ·C 3 H 7 NO, is not pre-organized for metal binding to the four calix­[4]­arene O atoms. N,N -Di­methyl­form­amide forms a hydrogen-bond bridge between two calix­[4]­arene–crown mol­ecules.

anti -25,27-Bis- n -octyloxycalix[4]arene, the paco -isomer of25,27-bis- n -octyloxycalix[4]arene crown-6 ether, and the paco - and1,3- alt isomers of 25,27-bis- n -octyloxycalix[4]arene t -butylbenzocrown-6 ether were prepared. The crystal structures of anti -25,27-bis- n -octyloxycalix[4]arene, paco -25,27-bis- n -octyloxycalix[4]arene crown-6, and 1,3- alt -25,27-bis- n -octyloxycalix[4]arene crown-6 were determined and thesolution structure of anti -25,27-bis- n -octyloxycalix[4]arene was studied by 2D- and VT-NMR. The extraction of alkali metal nitrates by the paco -25,27-bis- n -octyloxycalix[4]arene crown-6 and t -butylbenzocrown-6 ethers in 1,2-dichloroethane was compared to that of the corresponding 1,3- alt isomers.

Three 25,27-dihydrocalix[4]arene derivatives, bearing benzonitrile and acetone groups on the oxygens, were prepared and structurally characterized. All three structures crystallize in \(P\bar 1\), with cell dimensions: bis(benzonitrile)calix[4]arene·toluene, a = 11.530(2) Å, b = 12.013(2) Å, c = 14.089(4) Å, α = 103.555(18)°, β = 94.341(18)°, γ = 104.704(16)°, and V = 1815.9(7) Å3; anti-bis-acetone-calix[4]arene, a = 7.5847(8) Å, b = 12.0948(17) Å, c = 15.3375(16) Å, α = 78.982(10)°, β = 76.932(9)°, γ = 73.129(10)°, and V = 1299.6(3) Å3; syn-bis-acetone-calix[4]arene, a = 9.080(3) Å, b = 10.391(3) Å, c = 14.816(3) Å, α = 96.998(19)°, β = 100.02(2)°, γ = 103.93(3)°, and V = 1299.6(3) Å3.

The crown ether portion of the title complex, C50H66O6·C3H7NO, is not pre-organized for metal binding to the four calix­[4]­arene O atoms. N,N-Di­methyl­form­amide forms a hydrogen-bond bridge between two calix­[4]­arene–crown mol­ecules.

The structure of N , N ′-diphenyl-1,3-benzenedisulfonamide ( 1 ) was determined by single crystal X-ray diffraction. It crystallizes in P 2 1 / n with cell dimensions: a = 11.8390(6) Å, b = 12.3950(10) Å, c = 12.1184(10) Å, β = 94.388(6)°, and V = 1773.1(2) Å 3 . Its di- t -butyl derivative, N , N ′-bis(4- t -butylphenyl)-1,3-benzenedisulfonamide ( 2 ), was prepared and structurally characterized as two solvated structures. Both crystallize in P 1 with cell dimensions: 2 ⋅ CF 3 CH 2 OH, a = 9.469(2) Å, b = 10.0039(18) Å, c = 16.385(3) Å, α = 85.561(16)°, β = 83.035(18)°, γ = 72.459(16), and V = 1467.7(5) Å 3 ; 2 ⋅ ClCH 2 CH 2 Cl, a = 9.559(2) Å, b = 9.8125(12) Å, c = 17.100(6) Å, α = 82.495(19)°, β = 83.47(2)°, γ = 70.100(15), and V = 1491.1(6) Å 3 . The structures exhibit hydrogen-bonding, and are evaluated in terms of preorganization for anion binding.

Single crystal X-ray diffraction analyses of calix[4]arene-bis-crown-6 ( 1 ) and calix[4]arene-bis-benzocrown-6⋯1,2-dichloroethane ( 2 ) are reported. Thesestructures offer an opportunity to study the conformation of calix[4]arene-bis-crown-6 molecules in the absence of solvent, and when very weakly solvated. These structures exhibit different conformations of the crown ring, and limited flexibility of the calix[4]arene,but do not show solvent or crown inclusion in the calix[4]arene cavity. Comparisons to similar structures are made, and the implications for cesium binding are discussed.

The structure of the title compound, C 40 H 44 O 8 , differs from previously determined structures of triptyceno–crown ether mol­ecules as its longer crown ether chain does not congest a triptycene cavity.

Two Tc-containing products were isolated from the reaction between CS 2 and the electron-deficient complex TcCl(dppe) 2 . The title dithioformate complex, [Tc(S 2 CH)(dppe) 2 ]·3C 6 H 6 , where dppe is 1,2-bis(diphenylphosphino)ethane (C 26 H 24 P 2 ), exhibits Tc—P bond lengths ranging from 2.3566 (14) to 2.3884 (14) Å, which are little shorter than normally found. The other product is [TcCl(CS)(dppe) 2 ], and is the first reported Tc–thiocarbonyl complex.

Compound 5, a cage-annulated monoaza-18-crown-6 macrocyclic polyether, has been synthesized, and its alkali metal picrate extraction capabilities have been assessed relative to those of the parent monoaza-18-crown-6 host system. It was observed that both 5 and monoaza-18-crown-6 are selective K+ picrate extractants; however, 5 appears generally to be a somewhat more efficient alkali metal picrate extractant than monoaza-18-crown-6. Interestingly, both the avidity and selectivity of 5 toward extraction of alkali metal picrates from aqueous solution into CHCl3 appears to be pH dependent. In addition, the X-ray crystal structure of an unusual hydronium ion complex of 5 [i.e., 5(HCl)(H2O)-(CHCl3)2] has been determined. The X-ray structure thus determined is compared with the corresponding structure of 5(HCl)(H2O) that has been calculated via application of B3LYP Density Functional Theory.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Tribenzo-18-crown-6 binds two aceto­nitrile ligands, i.e. C 24 H 24 O 6 ·2C 2 H 3 N, one to each face of the crown ring. The crown conformation is relatively low in energy, but does not appear optimized for cation binding. Few significant intermolecular interactions are observed.

Two Tc-containing products were isolated from the reaction between CS 2 and the electron-deficient complex TcCl(dppe) 2 . The title di­thio­formate complex, [Tc(S 2 CH)(dppe) 2 ]·3C 6 H 6 , where dppe is 1,2-bis­(di­phenyl­phosphino)­ethane (C 26 H 24 P 2 ), exhibits Tc—P bond lengths ranging from 2.3566 (14) to 2.3884 (14) Å, which are little shorter than normally found. The other product is [TcCl(CS)(dppe) 2 ], and is the first reported Tc–thio­carbonyl complex.