Photoreactions of 1-acetylisatin with alkynes: regioselectivity in oxetene formation and easy access to 3-alkylideneoxindoles and dispiro[oxindole[3,2']furan[3',3' ']oxindole]s

[reaction: see text] Photoinduced reactions of 1-acetylisatin (IS) with diphenylacetylenes 1a-c, 1-(p-methoxyphenyl)propyne 2, and 1,4-diphenyl-1,3-butadiyne 3 gave beta,beta-disubstituted 3-alkylidene oxindoles 6-12 respectively via [2+2] cycloaddition of 3IS* with the alkyne and subsequent oxetene ring opening. Photoreactions of IS with phenylacetylenes 4a-d and cyclopropylacetylene 5 furnished the dispiroindole[3,2']furan[3',3' ']indoles 13 and 14. Compounds 13 and 14 are formed in tandem reactions initiated by [2+2] cycloaddition of 3IS* with the alkynes to give spirooxetenes Va and Vb, which upon spontaneous ring opening gave the alpha,beta-unsaturated aldehydes IVa and IVb. It is proposed that hydrogen abstraction of 3IS* from the C(O)-H functionality in IV followed by dissociation of the triplet isatin ketyl (A)-aldehyde acyl (B) radical pair and an oxygenphilic attack of the acyl radical B at the C3 carbonyl oxygen atom of a neutral IS gave the 2:1 (IS:4) radical C, which took part in an intramolecular radical cyclization to give the dispiroindole[3,2']furan[3',3' ']indoles 13 and 14. The regioselectivity in the [2+2] photocycloadditions of IS with 4 to afford the oxetene Va depends on the intervening of the more stable 1,4-diradical intermediates VI, which have a linear alpha-phenyl-substituted vinyl radical where the phenyl provides spin delocalization of the radical center at the sp carbon atom.     

[Nd_2O(C_5H_5)_6](C_12H_9N_2)3Cl·mC_4H_8O的晶体结构

本文报告用单晶X-射线衍射法测定[Nd_2O(C-5H_5)_6](C_(12)H_9N_2)_3C1·mC_4H_5O的晶体结构。晶体属于单斜晶系,空间群为P2-1/c,晶胞参数为a=20.982(15),b=11.217(7),c=32.954(32),β=104.17(7)°;Z=4。Nd和C1原子坐标用直接法定出,其他原子坐标以差Fourier方法求得,经过最小二乘法修正,R因子为0.159。在分子中三个茂环皆通过η~5。键与Nd原子配位,两个Nd原子间存在桥氧原子,因而形成(Nd_2O(C_5H_5)_6)~(2-)阴离子,Nd-C键基本上属于离子键。三个邻菲罗啉基团通过氢键与C1原子连接形成大的阳离子[(C_(12)H_9N_2)3-C1]~(2+)。     

Chemical reduction of 2,4,6-tricyano-1,3,5-triazine and 1,3,5-tricyanobenzene. Formation of novel 4,4',6,6'-Tetracyano-2,2'-bitriazine and its radical anion

Chemical reduction of 2,4,6-tricyano-1,3,5-triazine, TCT, results in the formation of an unstable radical anion that undergoes immediate dimerization at a ring carbon to form [C(12)N(12)](2-), [TCT](2)(2-), characterized by a long 1.570 (4) A central C[bond]C. [TCT](2)(2-) can decompose into the radical anion of 4,4',6,6'-tetracyano-2,2'-bitriazine, [TCBT]*-, the one-electron reduced form of planar (D(2h)) TCBT, which is also structurally characterized as the [TMPD][TCBT] charge-transfer complex (TMPD = N,N,N',N'-tetramethyl-p-phenylenediamine) with a 1.492 (2) A central sp(2)[bond]sp(2) C[bond]C. Although crystals could not be obtained for the radical anion [TCBT]*-, the electrochemistry (E degrees = +0.03 V), EPR (g = 2.003, (2)A((14)N) = 3.347 G, and (4)A((14)N) = 0.765 G and a line width of 0.24 G), and theoretical calculations support the formation of [TCBT]*-. In addition, thermolysis of [TCT](2)(2-) yields [TCBT]*-. Chemical reduction of 2,4,6-tricyanobenzene, TCB, forms an unstable radical anion that immediately undergoes dimerization at a ring carbon to form [C(12)H(6)N(6)](2-), [TCB](2)(2-), which has a long 1.560 (5) A central C[bond]C. Reaction of TCT with tetrathiafulvalene (TTF) forms structurally characterized [TTF][TCT], and in the presence of water, TCT hydrolyzes to 2,4-dicyano-6-hydroxy-s-triazine, DCTOH. In contrast, the reaction of TCT with TMPD forms [TMPD][TCT], which in the presence of water forms structurally characterized [HTMPD](+)[DCTO](-).     

An unprecedented mode of ligation for a bridged amido-cyclopentadienide (constrained geometry) ligand; pi-olefinic interactions with gallium and indium

The surprising reaction of GaCl3 or InBr3 with the di-Grignard reagent [Me2Si(C5Me4)(N-t-Bu)](MgCl)2 x THF results in salts of the bimetallic anions of composition [X3M[C5Me4(N-t-Bu)]MX2]- (M = Ga, X = Cl; M = In; X = Br) in which the MX2 moiety undergoes an eta2-interaction with one of the double bonds of the localized cyclopentadienide ring.     

Synthesis and properties of highly fluorescent indolizino[3,4,5-ab]isoindoles

We report here the synthesis, X-ray structures, optical and electrochemical properties, fabrication of light-emitting devices, and density functional calculations for indolizino[3,4,5-ab]isoindole (INI) derivatives. Strongly luminescent heterocycles based on the INI unit were synthesized by 1,3-dipolar cycloaddition reactions between pyrido[2,1-a]isoindole (PIS) and acetylene or ethylene derivatives. They are indolizino[3,4,5-ab]isoindoles 2-9 and 14-15, benzo[1',2'-1,2]indolizino[3,4,5-ab]isoindoles 10, pyridazino[4',5':1,2]indolizino[3,4,5-ab]isoindoles 12-13, and 2,3-hydropyridazino[4',5':1,2]indolizino[3,4,5-ab]isoindole-1,4-dione 11. The relative luminescence quantum yield can be as high as 90%. Their reduction and oxidation potentials and high luminescence can make these heterocycles possible alternatives to tris(8-hydroxyquinolinato)aluminum (Alq(3)). The brightness of the light-emitting device reached as high as 10(4) cd/m(2) and indolizino[3,4,5-ab]isoindole 3 emits beautifully blue light. The X-ray crystal structures of INI derivatives were obtained for the first time. The geometries obtained from X-ray data and density functional theory calculations shed more light on an interesting formally antiaromatic 16pi system, which is divided into 10pi and 6pi aromatic systems. We also report a relatively easy protonation of INI, which occurs at a carbon, rather than nitrogen atom.     

Novel Ring Contraction Reaction for the Synthesis of Functionalized Tetrathiamacrocyclic Ligand Molecules

Chlorination of [14]aneS(4)-ol (1,4,8,11-tetrathiatetradecan-6-ol) and cis/trans-[14]aneS(4)-diol (cis/trans-1,4,8,11-tetrathiatetradecane-6,13-diol) yields the corresponding dichloro-substituted macrocycles [14]aneS(4)-Cl (1,4,8,11-tetrathiatetradecane 6-chloride) and cis/trans-[14]aneS(4)-Cl(2) (cis/trans-1,4,8,11-tetrathiatetradecane 6,13-dichloride) in good yield. Thiomethylation of the chlorides produces the ring-contracted pendent thioether macrocycles [13]aneS(4)-CH(2)SCH(3) (1,4,7,10-tetrathiatridecane-5-(methylthio)methane) and cis/trans-anti-[12]aneS(4)-(CH(2)SCH(3))(2) (1,4,7,10-tetrathiadodecane-5,11-bis((methylthio)methane)). The mechanism of the ring contraction reaction is discussed in terms of the reactivity of the monochlorinated macrocycle toward ring contraction and the stereochemistry of the chlorinated intermediates and the thiomethylated products, which are based on the X-ray crystal structure analyses of trans-[14]aneS(4)-Cl(2) and trans-anti-[12]aneS(4)-(CH(2)SCH(3))(2).     

A convenient approach to heterocyclic building blocks: synthesis of novel ring systems containing a [5,6]Pyrano[2,3-c]pyrazol-4(1H)-one moiety

Starting from commercially available educts, a straightforward synthetic route to new heterocyclic building blocks is exemplified with the one- or two-step synthesis of tri-, tetra-, or pentacyclic ring systems. Representatives of the following novel ring systems are prepared from 3-methyl-1-phenyl-2-pyrazolin-5-one and the corresponding o-halo-arenecarbonyl chloride using calcium hydroxide in refluxing 1,4-dioxane: pyrimidino[4',5':5,6]pyrano[2,3-c]pyrazol-4(1H)-one, thieno[3',2':5,6]pyrano[2,3c]pyrazol- 4-(1H)-one, thieno[3',4':5,6]pyrano[2,3-c]pyrazol-4(1H)-one, thieno[3',2':4',5']thieno[2',3':5,6]-pyrano[2,3-c]pyrazol-4(1H)-one, [1,3]dioxolo[5',6'][1]benzothieno[2',3':5,6]pyrano-[2,3-c]- pyrazol-4(1H)-one, pyridazino[4',3':5,6]pyrano[2,3-c]pyrazol-4(1H)-one and pyrazolo-[4',3':5',6']pyrido[3',4':5,6]pyrano[2,3-c]pyrazol-4(1H)-one. While the latter two ring systems are directly obtained due to a spontaneous intramolecular substitution reaction, in the other reactions uncyclised 4-aroylpyrazol-5-ols are produced, which are cyclised into the target heterocycles in a subsequent synthetic step (i.e. treatment with NaH in DMF). Detailed NMR spectroscopic investigations ((1)H-, (13)C-, (15)N-) with the obtained compounds were undertaken to unambiguously prove the new structures.     

Two new borates containing the first examples of large isolated polyborate anions: chain [B7O9(OH)5]2- and ring [B14O20(OH)6]4-

Two novel hydrated borates were synthesized under mild solvothermal conditions. One is hydrated rubidium borate, Rb2B7O9(OH)5, which contains the first example of the isolated chain heptaborate anion, [B7O9(OH)5]2-. The other is hydrated diethylenetriamine borate, [(C4H15N3)]2[B14O20(OH)6], which contains the first example of the largest isolated ring tetradecaborate anion, [B14O20(OH)6]4-.     

Reactions involving di-trans-[12]annulenes

The low temperature complete dehydrohalogenation of pentabromocyclododecene (C12H17Br5) with potassium tert-butoxide in THF followed by exposure to potassium metal leads to the formation of the anion radical of 1,5-di-trans-[12]annulene, which loses hydrogen and undergoes ring closure to form the anion radical of 11,12-dihydro-[8]annuleno-[6]annulene. This product can, in turn, be isolated as its neutral molecule via reoxidation with iodine. A [12]annulene obtained via the dimerization of 1,5-hexadiyne in the presence of 18-crown-6 and potassium tert-butoxide undergoes ring closure, with concomitant loss of hydrogen, to yield the heptalene anion radical. It follows that the heptalene anion radical precursor was the 1,7-di-trans isomer of [12]annulene.     

Pi-extended o-quinoidal tropone derivatives: experimental and theoretical studies of naphtho[2,3-c]tropone and anthro[2,3-c]tropone

pi-Extended o-quinoidal tropone derivatives, naphtho[2,3-c]tropone (3) and anthro[2,3-c]tropone (4), have been investigated theoretically as well as experimentally. The geometrical optimization of 3,4 and related compounds at the B3LYP level employing 6-31G* basis set as well as the GIAO calculations at the RHF level employing the 6-31+G* basis set have been performed to evaluate the contributions of the polarized resonance forms to these molecules. The GIAO calculated NICS(1) values indicate that the aromaticities of the tropone rings of o-quinoidal 3 and 4 are significantly increased as compared with that of parent tropone (1) at the expense of the fused benzenoid rings, consistent with the significant electronic polarization of these molecules in the ground state. On the other hand, the fusion of a benzene or naphthalene ring to the 2,3- or 4,5-position of tropone leads to diminution of aromaticity in the resulting tropone moiety. Experimentally, irradiation of 6,7-(2',3'-naphtho)bicyclo[3.2.0]hepta-3,6-dien-2-one (10) in a rigid glass at -196 degrees C leads to the formation of, which exhibits a characteristic UV-Vis absorption extending to 700 nm and undergoes rapid [pi 12 + pi 14] dimerization upon thawing the glass. In contrast, 6,7-(2',3'-anthro)bicyclo[3.2.0]hepta-3,6-dien-2-one (11) showed no sign of isomerization to 4 under the same reaction conditions.     

Examining the out-of-center distortion in the [NbOF5]2- anion

Out-of-center "primary" electronic distortions are inherent to the oxide fluoride anions of the early d0 transition metals. In the [NbOF5]2- anion, the Nb5+ moves from the center of the octahedron toward the oxide ligand to form a short Nb=O bond and long trans Nb-F bond. The combined results of single-crystal X-ray diffraction and electronic structure calculations indicate that the primary distortion of the [NbOF5]2- anion is affected by the coordination environment that is created by the three-dimensional extended structure. The formation of bonds between an M(L)4(2+) (M = Cd2+, Cu2+; L = 3-aminopyridine, 4-aminopyridine) cation and the oxide and/or trans-fluoride ligands of the [NbOF5]2- anion weakens the pi component of the Nb=O bond. At the same time, hydrogen bond interactions between the equatorial fluorides and the aminopyridine groups both lengthen the equatorial Nb-F bonds and can further reduce the symmetry of the [NbOF5]2- anion. These combined three-dimensional bond network interactions that serve to lengthen the Nb=O bond and thereby decrease the primary distortion of the [NbOF5]2- anion are illustrated in the structures of three new niobium oxide fluoride phases, [4-apyH]2[Cu(4-apy)4(NbOF5)2] (4-apy = 4-aminopyridine), Cd(3-apy)4NbOF5 (3-apy = 3-aminopyridine), and Cu(3-apy)4NbOF5, that were synthesized and characterized using X-ray diffraction. Crystal data for [4-apyH]2[Cu(4-apy)4(NbOF5)2]: tetragonal, space group /4(1)/ acd (No. 142), with a = 20.8745(8) A, c = 17.2929(9) A, and Z= 8. Cd(3-apy)4NbOF5: tetragonal, space group P4(3) (No. 78), with a = 8.4034(4) A, c = 34.933(3) A, and Z = 4. Cu(3-apy)4NbOF5: monoclinic, space group P2(1)/n (No. 14), with a = 8.822(1) A, b = 16.385(3) A, c = 8.902(1) A, beta = 109.270(3) degrees, and Z = 2.     

12]Annulene radical anions revisited: evaluation of structure assignments based on computed energetic and electron spin resonance data

We report density functional and coupled cluster calculations on numerous monocyclic and bicyclic (CH)12(*-) isomers. At the RCCSD(T)/cc-pVDZ//UB3LYP/6-31+G* level, a nearly planar, bond-equalized radical anion of 1,7-di-trans-[12]annulene (4a(*-)) is lowest in energy; several other isomers and conformations lie within 3 kcal/mol of 4a(*-). RCCSD(T)/AUG-cc-pVDZ//UB3LYP/6-31+G* results place the all-cis isomer 3(*-) slightly below 4a(*-) in energy. Validation studies on the heptalene radical anion, [16]annulene radical anion, and tri-trans-[12]annulene radical anion indicate that electron spin resonance (ESR) hyperfine coupling constants (aH values) computed at the BLYP/EPR-III level on DFT geometries give much better agreement with experimental values than those computed using B3LYP/6-31G*. We were unable to locate any C12H12(*-) isomer that could account for the ESR spectrum previously attributed to a highly twisted structure for the 1,7-di-trans-[12]annulene radical anion. Our computed energetic and ESR data for [12]annulene radical anions and their valence isomers suggest that 4a(*-) may have been made, yet its ESR spectrum was incorrectly assigned to the bicyclic isomer 6b(*-). Finally, the computed (1)H NMR shift values of the dianion of 4 reveal a distinct diatropic ring current that should aid in its characterization.     

A simple approach to coordination compounds of the pentacyanocyclopentadienide anion

Deprotonation of [Et(3)NH][C(5)(CN)(5)] with metal bases provides a very simple approach to coordination compounds containing the pentacyanocyclopentadienide anion [C(5)(CN)(5)](-) (1). The three-dimensional polymer [Na(thf)(1.5)(1)](∞) and the molecular dimer [{(tmeda)(2)Na(1)}(2)] are obtained by reaction of this precursor with NaH in the presence of thf or tmeda (Me(2)NCH(2)CH(2)NMe(2)). Their single-crystal X-ray structures both reveal σ-bonded C≡N-Na arrangements and π stacking between [C(5)(CN)(5)](-) ions. DFT calculations on the [C(5)(CN)(5)](-) ion have been used to investigate the structures and bonding in [Na(thf)(1.5)(1)](∞) and [{(tmeda)(2)Na(1)}(2)]. The absence of π bonding of the metal ions in both complexes is due to dispersion of the negative charge from the C(5) ring unit to the C[triple chemical bond]N groups in the [C(5)(CN)(5)](-) ion, making the coordination chemistry of this anion distinctly different from that of cyclopentadienide C(5)H(5)(-).     

A new tandem route to angular tetraquinanes. Synthesis of the Waihoensene ring system

[formula: see text] This paper describes a new tandem reaction sequence leading to angularly fused polyquinanes from squaric acid-derived bicyclo[6.3.0]-undecadienediones. Such compounds undergo a dual Michael addition. The enolate form in the first intermolecular addition undergoes the second intramolecular transannular addition to give the angular polyquinanes. A particularly interesting example is a catalytic transformation of cis-13-methylyricyclo[10.3.0.0]pentadeca-4(5),12(13)-diene-3 ,14-dione to (3R*,3aS*,5aR*,9aR*,11aR*)-3-methyl-1,2,3,5,5a,6 ,7,10,11,11a-decahydro-4H- pentaleno[6a,1-c]indene-2,10-dione, a compound having the tetracyclic ring system found in the natural product waihoensene. The mechanism and synthetic scope of these reactions are discussed.     

1,3-bicyclo[1.1.1]pentanediyl: the shortest rigid linear connector of phenylated photochromic units and a 1,5-dimethoxy-9,10-di(phenylethynyl)anthracene fluorophore

An excess of bis-1,3-(4-iodophenyl)bicyclo[1.1.1]pentane, prepared in 63 % yield by iodination of 1,3-diphenylbicyclo[1.1.1]pentane, was selectively mono-coupled with 9-ethynyl-1,5-dimethoxy-10-phenylethynylanthracene (26), and subsequently with the zinc derivatives of 1-(2-methyl/methoxy-4-methyl-5-phenylthiophen-3-yl)-2-(2-methyl/methoxy-4-methylthiophen-3-yl)perfluorocyclopentenes (38-H-41-H). Regioselective synthesis of the 2-unsubstituted thiophenes 38-H-41-H required intermediate preparation of 2-trimethylsilyl-3,5-dimethyl-4-bromothiophene (37) or 2-trimethylsilyl-5-methoxy-3-methyl-4-bromothiophene (40). Protection of the alpha-position of the thiophene ring with a 2-trimethylsilyl group blocks the rearrangement of the 4-lithio derivatives into the corresponding 2-lithiated thiophenes. With the bicyclo[1.1.1]pentane fragment linking the photochromic units 1-3 and 1,5-dimethoxy-9,10-di(phenylethynyl)anthracene as a fluorescent part, quantitative resonance energy transfer between the excited state of the fluorophore (donor) and the closed form of the photochromic units 1-3 (acceptors) was observed. The closed forms of the methoxy-substituted photochromic units 2 and 3 are less resistant to UV light (313 nm) than the closed form of 1.     

The chemical bond in polyphosphides: crystal structures, the electron localization function, and a new view of aromaticity in P4(2-) and P5(-)

The incongruent solvation of M(I)4P6 species (M(I) = K, Rb, Cs) in liquid ammonia leads to a broad variety of polyphosphides such as P7(3-), P11(3-), and the putatively aromatic P4(2-) and P5(-), which we investigated by using NMR spectroscopy and single-crystal X-ray structure analysis. The structures of Cs2P4 x 2 NH3, (K@[18]crown-6)3K3(P7)2 x 10 NH3, Rb3P7 x 7 NH3, and (Rb@[18]crown-6)3P7 x 6 NH3 are discussed and compared. The electron localization function ELF is used in a comparison of the chemical bonding of various phosphorus species. The variances of the basin populations provide a well-established measure for electron delocalization and therefore aromaticity. While comparable variance is calculated for P4(2-) and P5(-) it is observed in the lone pairs rather than in the basin populations of the bonds as in the prototypical aromatic hydrocarbons such as benzene or the cyclopentadienide anion. For this behavior, the term "lone pair aromaticity" is proposed.     

Condensation of [Si3O9]6- anions in the solid state to the dimeric cyclotrisilicate anion [Si6O17]10-

The structure of the silicate Rb10[Si6O17] containing a novel dimeric cyclotrisilicate anion is reported. The compound is formed by the reaction of a mixture of SiO2 and Rb at temperatures above 700 degrees C. Systematic investigations by means of differential thermal analysis and temperature-dependent powder X-ray diffraction experiments revealed that the new compound evolved from Rb6[Si3O9], which occurred as an intermediate product. Thus, the dimeric anion [Si6O17]10- is formed by condensation of the monomeric cyclotrisilicate [Si3O9]6-. For both silicates, [Si6O17]10- and [Si3O9]6-, the characteristic ring vibration modes were observed in the IR spectrum. The structure of Rb10[Si6O17] was solved and refined from single-crystal X-ray diffraction data in the orthorhombic space group Pbca (No. 61). Synthesis and structure determination of Rb10[Si6O17] bridge the gap to show that the recently reported structures of Rb14[Si4][Si6O17] and Rb14[Ge4][Si6O17] are indeed fascinating intergrowth structures of the stable oxide Rb10[Si6O17] and the Zintl phases RbSi (Rb4Si4) and RbGe (Rb4Ge4), respectively.     

An insight into the aromaticity of fullerene anions: experimental evidence for diamagnetic ring currents in the five-membered rings of C(60)(6-) and C(70)(6-)

Reduction of the two "closed" [6,6] methanofullerenes, [6,6]C(61)H(2) (1) and [6,6]C(71)H(2) (5), to the corresponding hexaanions with lithium metal causes the bridgehead-bridgehead bonds to open, at least partially, and this change gives rise to diamagnetic ring currents in the resulting homoconjugated six-membered rings (6-MRs). These new ring currents shield the overlying hydrogen atoms on the methylene bridge and induce upfield shifts of 1.60 and 0.11 ppm in their (1)H NMR resonances, respectively. Analogous reduction of the already "open" [5,6]methanofullerenes, [5,6]C(61)H(2) (2) and [5,6]C(71)H(2) (3 and 4), only slightly enhances the shielding of the hydrogen atoms over the homoconjugated 6-MRs (upfield shifts of 0.13, 0.68, and 0.14 ppm, respectively) but leads to exceptionally strong diamagnetic ring currents in the homoconjugated five- membered rings (5-MRs), as evidenced by dramatic shielding of the hydrogen atoms situated over them (upfield shift of 5.01, 6.78, and 1.63 ppm, respectively). The strongest shielding is seen for the hydrogen atom sitting over the 5-MR at the pole of C(71)H(2)(6)(-) (delta = -0.255 ppm) indicating that the excess charge density is concentrated at the poles.     

Chemistry related to cluster-borane analogues of the cyclopentadienide anion and ferrocene: New developments

A review on cluster-borane analogues of the cyclopentadienide anion (Cp) and ferrocene is presented. Analogues of Cp that have been so far isolated and characterised are the 11-vertex triheteroboranes of general structure [nido-E₃B₈H₈]⁻ (where E = CH or P and their combinations), the molecules of which contain an open pentagonal face. These anions were used as effective ligands for the preparation of “half- and full-sandwich” complexes [CpFeE₃B₈H₈] and [Fe(E₃B₈H₈)₂], respectively - analogues of ferrocene. Developments in this area of cluster-borane chemistry that include recent results in the synthesis and Fe-complexation reactions of 11-vertex tricarbaboranes (tricarbollides), phosphadicarbollides, and diphosphacarbollides are the subject of this work.     

Chlorine anion encapsulation by molecular capsules based on cucurbit[5]uril and decamethylcucurbit[5]uril

Three barrel-shaped artificial molecular capsules 1-3, based on normal cucurbit[5]uril (Q[5]) and decamethylcucurbit[5]uril (Me10Q[5]), were synthesized and structurally characterized by single-crystal X-ray diffraction. Encapsulation of a chlorine anion in the cavity of a Q[5] or Me10Q[5] to form closed a molecular capsule with the coordinated metal ions or coordinated metal ions and water molecules in the crystal structures of these compounds is common. The three complexes [Pr2(C30H30N20O10)Cl3(H2O)13]3+ 3 Cl- x 5 H2O (1), [Sr2(C40H50N20O10)(H2O)4Cl]3+ 3 Cl- x 2 (HCl) 19 H2O (2) and [K(C40H50N20O10)(H2O)Cl] x [Zn(H2O)2Cl2] x [ZnCl4]2- x 2 (H3O)+ x 8 H2O (3) all crystallize as isolated molecular capsules.