Kristallstruktur von Tetraphenylphosphonium-Monothiocyanatohydro-closo-Decaborat, [P(C6H5)4]2[2-(SCN)B10H9] · CH3CN

Crystal Structure of Tetraphenylphosphonium Monothiocyanatohydro-closo-Decaborate, [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN The X-ray structure determination of [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN (monoclinic, space group P2₁/n, a = 10.6040(10), b = 13.8880(9), c = 33.888(3) Å, β = 94.095(8)°, Z = 4) reveals the S coordination of the SCN substituent with a B? S distance of 1.913(6) Å and a B? S? C angle of 105.3(3)°. The SCN group is nearly linear (178.2(7)°).     

Darstellung und Kristallstrukturen von [P(C6H5)4][1-(NH3)B10H9] und Cs[(NH3)B12H11] · 2CH3OH

Synthesis and Crystal Structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH The reduction of [1-(NO₂)B₁₀H₉]^2? with aluminum in alkaline solution yields [1-(NH₃)B₁₀H₉]^? and by treatment of [B₁₂H₁₂]^2? with hydroxylamine-O-sulfonic acid [(NH₃)B₁₂H₁₁]^? is formed. The crystal structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] (triclinic, space group P1 , a = 7.491(2), b = 13.341(2), c = 14.235(1) Å, α = 68.127(9), β = 81.85(2), γ = 86.860(3)°, Z = 2) and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH (monoclinic, space group P2₁/n, a = 14.570(2), b = 7.796(1), c = 15.076(2) Å, β = 111.801(8)°, Z = 4) reveal for both compounds the bonding of an ammine substituent to the cluster anion.     

Reaktionen von 1,1,3,3‐Tetrakis(dimethylamino)‐1 λ5, 3 λ5‐diphosphet mit 5‐Cyano‐1‐pentin und mit 2‐(Cyanmethyl)‐1‐methylpyrrol

Diphosphabenzenes. VII. Reactions of 1,1,3,3‐Tetrakis(dimethylamino)‐1 λ⁵, 3 λ⁵‐diphosphete with 5‐Cyano‐1‐pentine and 2‐(Cyanomethyl)‐1‐methylpyrrol 5‐Cyano‐1‐pentine reacts with the equimolar amount of the λ⁵‐diphosphete 1 to give the λ⁵‐diphosphinine (λ⁵‐diphosphabenzene) ( 3 ), while reaction with the double equimolar amount of 1 yields the λ⁵‐diphosphinine ( 4 ). The acyclic compount 6 is the main product of the reaction between 1 and 2‐(cyanomethyl)‐1‐methylpyrrol, 5 . Melting points of 4 · CH₃CN and 6 , and mass, nmr and ir spectra of 3 , 4 , and 6 are reported. The crystal structure of 4 · CH₃CN shows an open‐chain ylidic CPCP‐sequence, which is linked to a λ⁵‐diphosphinine via an ethylene bridge. The X‐ray structure analysis of 6 confirms the existence as an acyclic conjugated double ylid.     

Reaktionen von [B12H12–n(OH)n]2–, n = 1, 2 mit Säuredichloriden und Kristallstruktur von Cs2[1,2-B12H10(ox)] · CH3OH

Reactions of [B₁₂H_12–n(OH)_n]^2–, n = 1, 2 with Acid Dichlorides and Crystal Structure of Cs₂[1,2-B₁₂H₁₀(ox)] · CH₃OH By treatment of [B₁₂H₁₁(OH)]^2– with organic and inorganic acid dichlorides in acetonitrile the bridged dicluster compounds [B₁₂H₁₁(ox)B₁₂H₁₁)]^4– ( 1 ), [B₁₂H₁₁(p-OOCC₆H₄COO)B₁₂H₁₁]^4– ( 2 ), [B₁₂H₁₁(m-OOCC₆H₄COO)B₁₂H₁₁]^4– ( 3 ), [B₁₂H₁₁(SO₃)B₁₂H₁₁]^4– ( 4 ), [B₁₂H₁₁(SO₄)B₁₂H₁₁]^4– ( 5 ) are obtained in good yields. The dihydroxododecaborates [1,2-B₁₂H₁₀(OH)₂]^2– and [1,7-B₁₂H₁₀(OH)₂]^2– afford clusters with an anellated ring: [1,2-B₁₂H₁₀(ox)]^2– ( 6 ), [1,2-B₁₂H₁₀(SO₄)]^2– ( 7 ) and [1,7-B₁₂H₁₀(OOC(CH₂)₈COO)]^2– ( 8 ). Isomerically pure [1,7-B₁₂H₁₀(OH)₂]^2– ( 9 ) is formed by reaction of (H₃O)₂[B₁₂H₁₂] with ethylene glycol. All new compounds are characterized by vibrational, ¹¹B, ¹³C and ¹H NMR spectra. The crystal structure of Cs₂[1,2-B₁₂H₁₀(ox)] · CH₃OH (monoclinic, space group P 2₁/c, a = 9.616(2), b = 10.817(1), c = 15.875(6) Å, β = 95.84(8)°, Z = 4) reveals a distortion of the B₁₂ icosahedron caused by the anellated six-membered heteroring.     

Reaktionen des [η2-{P–PtBu2}Pt(PPh3)2] und [η2-{P–PtBu2}Pt(dppe)] mit Metallcarbonylen. Bildung von [η2-{(CO)5M · PPtBu2}Pt(PPh3)2] (M = Cr,W) und [η2-{(CO)5Cr · PPtBu2}Pt(dppe)]

Coordination Chemistry of P-rich Phosphanes and Silylphosphanes. XVI [1] Reactions of [g²-{P–P^tBu₂}Pt(PPh₃)₂] and [g²-{P–P^tBu₂}Pt(dppe)] with Metal Carbonyls. Formation of [g²-{(CO)₅M · PP^tBu₂}Pt(PPh₃)₂] (M = Cr, W) and [g²-{(CO)₅Cr · PP^tBu₂}Pt(dppe)] [η²-{P–P^tBu₂}Pt(PPh₃)₂] 4 reacts with M(CO)₅ · THF (M = Cr, W) by adding the M(CO)₅ group to the phosphinophosphinidene ligand yielding [η²-{(CO)₅Cr · PP^tBu₂}Pt(PPh₃)₂] 1 , or [η²-{(CO)₅W · PP^tBu₂}Pt(PPh₃)₂] 2 , respectively. Similarly, [η²-{P–P^tBu₂}Pt(dppe)] 5 yields [η²-{(CO)₅Cr · PP^tBu₂}Pt(dppe)] 3 . Compounds 1 , 2 and 3 are characterized by their ¹H- and ³¹P-NMR spectra, for 2 and 3 also crystal structure determinations were performed. 2 crystallizes in the monoclinic space group P2₁/n (no. 14) with a = 1422.7(1) pm, b = 1509.3(1) pm, c = 2262.4(2) pm, β = 103.669(9)°. 3 crystallizes in the triclinic space group P1 (no. 2) with a = 1064.55(9) pm, b = 1149.9(1) pm, c = 1693.2(1) pm, α = 88.020(8)°, β = 72.524(7)°, γ = 85.850(8)°.     

Palladium(II)‐Komplexe des 1,1,3,3,5,5‐Hexakis(dimethylamino)‐λ5‐[1,3,5]triphosphinins

Palladium(II) Complexes of 1,1,3,3,5,5‐Hexakis(dimethylamino)‐λ⁵‐[1,3,5]triphosphinine 1,1,3,3,5,5‐Hexakis(dimethylamino)‐1λ⁵‐3λ⁵‐5λ⁵‐[1,3,5]triphosphinine ( 5 ) reacts with (benzonitrile)₂PdCl₂ to give the chelate complex dichloro(dodeca‐N‐methyl‐1λ⁵,3λ⁵,5λ⁵‐1,3,5‐triphosphinine‐1,1,3,3,5,5‐hexaamin‐C²,C⁴)palladium ( 6 ). In a pyridine‐d₅ solution of 6 the complex dichloro(dodeca‐N‐methyl‐1λ⁵,3λ⁵,5λ⁵‐1,3,5‐triphosphinine‐1,1,3,3,5,5‐hexaamin‐C²)((²H₅)pyridine‐N)palladium ( 7 ) is formed. The solute 7 could not be isolated as a solid, because elimination of the solvent regenerates 6 quantitatively. Properties, nmr and ir spectra of 6 and 7 are reported. 6 is characterized by the results of an X‐ray structural analysis.     

Das Tris(cyclopentadienyl)methylsilan-Trianion – ein neues Ligandensystem und Komplexbildung mit Rhodium

The Tris(cyclopentadienyl)methylsilane Trianion – a New Ligand System and Complex Formation with Rhodium Starting from MeSiCl₃ the title compound was synthesized by two steps as the virtually insoluble trithallium salt ( 1 ). Reaction of 1 with [(C₂H₄)₂RhCl]₂ in pentane gives {MeSi[C₅H₄Rh(C₂H₄)₂]₃} ( 2 ). Under UV irradiation of 2 in pentane in the presence of benzene only two [C₅H₄Rh(C₂H₄)₂] units of 2 react with loss of ethene and formation of the μ-η³ : η³ benzene compound {MeSi[(C₅H₄Rh)₂(C₆H₆)][C₅H₄Rh(C₂H₄)₂]} ( 3 ). The novel complexes 2 and 3 were characterized spectroscopically and by X-ray structure analysis.     

Azametalla-closo-dodecaboranes

The azaborate K₂[nido-NB₁₀H₁₁] is gained from nido-NB₁₀H₁₃ and K[BHEt₃] in a 1:2 ratio. The anion [NB₁₀H₁₁]^2?, which is isoelectronic with [C₂B₉H₁₁]^2?, reacts with [{η⁶-(C₆R₆) · RuCl₂}₂] (R = H, Me), [{η⁵-(C₅Me₅)RhCl₂}₂], or [Ni(PPh₃)₂Cl₂] to give the azametalla-closo-dodecaboranes MNB₁₀H₁₁ with M = (C₆Me₆)Ru ( 2 ), (C₆H₆)Ru ( 3 ), (C₅Me₅)Rh ( 4 ), and (Ph₃P)₂Ni ( 5 ), respectively. The azametallaborane K[Co(NB₁₀H₁₁)₂] ( 6 ), which contains a sandwich-type coordinated Co atom, is formed from K₂[NB₁₀H₁₁] and CoCl₂. The structure of 2 · CH₂Cl₂ was determined by X-ray diffraction. The products 2 – 6 can be derived from the icosahedral anion [B₁₂H₁₂]^2? on replacing a BH^2? moiety by the isoelectronic nitrene NH and a BH moiety by the isolobal metal-complex fragment M. The N atom is six-coordinated in the cluster skeletons 2 – 6 .     

Crystallographic report: The [bis(η5‐methylcyclopentadienyl)titanium(IV)‐bis(N‐methylglycine)] dichloride

The crystal network of [Cp′₂Ti(N?CH₃? Gly)₂]²⁺[Cl^?]₂ (Cp′ = (CH₃)C₅H₄) complex, which crystallizes as a solvate with CH₃OH, is built up with discrete cationic units connected through intermolecular H· · ·Cl bonds. The α‐amino acid ligands are attached through an intramolecular H· · ·O bond within one cationic unit. Copyright © 2004 John Wiley & Sons, Ltd.     

Three zinc(II) and cadmium(II) complexes containing 4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole and polynitrile ligands: synthesis,molecular and supramolecular structures,and photoluminescence properties

Three photoluminescent complexes containing either Zn^II or Cd^II have been synthesized and their structures determined. Bis[4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole‐κ²N ¹,N ⁵]bis(dicyanamido‐κN ¹)zinc(II), [Zn(C₁₂H₁₀N₆)₂(C₂N₃)₂], (I), bis[4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole‐κ²N ¹,N ⁵]bis(dicyanamido‐κN ¹)cadmium(II), [Cd(C₁₂H₁₀N₆)₂(C₂N₃)₂], (II), and bis[4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole‐κ²N ¹,N ⁵]bis(tricyanomethanido‐κN ¹)cadmium(II), [Cd(C₁₂H₁₀N₆)₂(C₄N₃)₂], (III), all crystallize in the space group P , with the metal centres lying on centres of inversion, but neither analogues (I) and (II) nor Cd^II complexes (II) and (III) are isomorphous. A combination of N—H…N and C—H…N hydrogen bonds and π–π stacking interactions generates three‐dimensional framework structures in (I) and (II), and a sheet structure in (III). The photoluminescence spectra of (I)–(III) indicate that the energies of the π–π* transitions in the coordinated triazole ligand are modified by minor changes of the ligand geometry associated with coordination to the metal centres.     

The Reaction of Molybdenum with 2,3-Dihydroxynaphthalene

[H2N（CH2）3NH312[MoO2（C10H6O2）2] （1） was synthesized by the 2,3-dihydroxynaphthalene in the mixed solvent of CH3OH, CH3CN reaction of （n-Bu4N）4[Mo8O26] with and 1,3-propanediarnine. （C5HllN2）2- [HeN（CH2）3NH2][MoO2（CloH6O2）2] （2） was obtained by the reaction of Na2MoO4.2H20 with 2,3-dihydroxynaphthalene in the same solvent above. Both of the complexes possess complex anion [Mo（VI）O2（OC10H6O）2]^2- which shows pseudo-octahedrally coordinated fashion, while the counterions are two protonated 1,3-propanediamine in complex 1 and （CsH11N2）^＋ in complex 2. （C5H11N2）＋ is the byproduct of reaction 2, which results from combination of acetonitrile with 1,3-propanediamine. Packing diagrams of the two complexes are also different. There is anti-parallel-aligned-double-meso-bilayer unit in complex 1. However there are four chiral anions arranged in anticlockwise orientation in complex 2.     

Chloridobis[2‐(diphenylphosphanyl)ethanamine‐κ2P,N](triphenylphosphane‐κP)ruthenium(II) chloride toluene monosolvate

The aminophosphane ligand 1‐amino‐2‐(diphenylphosphanyl)ethane [Ph₂P(CH₂)₂NH₂] reacts with dichloridotris(triphenylphosphane)ruthenium(II), [RuCl₂(PPh₃)₃], to form chloridobis[2‐(diphenylphosphanyl)ethanamine‐κ²P,N](triphenylphosphane‐κP)ruthenium(II) chloride toluene monosolvate, [RuCl(C₁₈H₁₅P)(C₁₄H₁₆NP)₂]Cl·C₇H₈ or [RuCl(PPh₃){Ph₂P(CH₂)₂NH₂}₂]Cl·C₇H₈. The asymmetric unit of the monoclinic unit cell contains two molecules of the Ru^II cation, two chloride anions and two toluene molecules. The Ru^II cation is octahedrally coordinated by two chelating Ph₂P(CH₂)₂NH₂ ligands, a triphenylphosphane (PPh₃) ligand and a chloride ligand. The three P atoms are meridionally coordinated, with the Ph₂P– groups from the ligands being trans. The two –NH₂ groups are cis, as are the chloride and PPh₃ ligands. This chiral stereochemistry of the [RuCl(PPh₃){Ph₂P(CH₂)₂NH₂}₂]⁺ cation is unique in ruthenium–aminophosphane chemistry.     

Synthesis,crystal structures and luminescence properties of seven mononuclear zinc(II), cadmium(II), cobalt(II) and nickel(II) complexes with 5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole

Due to their versatile coordination modes and metal‐binding conformations, triazolyl ligands can provide a wide range of possibilities for the construction of supramolecular structures. Seven mononuclear transition metal complexes with different structural forms, namely aquabis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ²N ¹,N ⁵]zinc(II), [Zn(C₁₄H₁₁N₄)₂(H₂O)], (I), bis[5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole‐κ²N ³,N ⁴]bis(nitrato‐κO )zinc(II), [Zn(NO₃)₂(C₁₄H₁₂N₄)₂], (II), bis(methanol‐κO )bis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ²N ¹,N ⁵]zinc(II), [Zn(C₁₄H₁₁N₄)₂(CH₄O)₂], (III), diiodidobis[5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole‐κ²N ³,N ⁴]cadmium(II), [CdI₂(C₁₄H₁₂N₄)₂], (IV), bis[5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole‐κ²N ³,N ⁴]bis(nitrato‐κO )cadmium(II), [Cd(NO₃)₂(C₁₄H₁₂N₄)₂], (V), aquabis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ²N ¹,N ⁵]cobalt(II), [Co(C₁₄H₁₁N₄)₂(H₂O)], (VI), and diaquabis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ²N ¹,N ⁵]nickel(II), [Ni(C₁₄H₁₁N₄)₂(H₂O)₂], (VII), have been prepared by the reaction of transition metal salts (Zn^II, Cd^II, Co^II and Ni^II) with 3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole (pymphtzH) under either ambient or hydrothermal conditions. These compounds have been characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction. All the complexes form three‐dimensional supramolecular structures through hydrogen bonds or through π–π stacking interactions between the centroids of the pyridyl or arene rings. The pymphtzH and pymphtz⁻ entities act as bidentate coordinating ligands in each structure. Moreover, all the pyridyl N atoms are coordinated to metal atoms (Zn, Cd, Co or Ni). The N atom in the 4‐position of the triazole group is coordinated to the Zn and Cd atoms in the crystal structures of (II), (IV) and (V), while the N atom in the 1‐position of the triazolate group is coordinated to the Zn, Co and Ni atoms in (I), (III), (VI) and (VII).     

Two New Modifications of [P(C6H5)4]2[Cu2I4]

Single crystals of two new modifications of [P(C₆H₅)₄]₂[Cu₂I₄] were obtained by reaction of granulated copper with iodine and [P(C₆H₅)₄]I in dry acetone under nitrogen atmosphere. They crystallise monoclinically, space group P2₁/n (No. 14), a = 11.550(6), b = 7.236(2), c = 27.232(13) Å, β = 98.13(3)°, V = 2253(2) ų, and Z = 2 ([P(C₆H₅)₄]₂[Cu₂I₄]-C), and space group Cc (No. 9), a = 17.133(5), b = 15.941(5), c = 18.762 (6) Å, β = 114.02(1)°, V = 4681(3) ų, and Z = 4 ([P(C₆H₅)₄]₂[Cu₂I₄]-D), respectively. In these compounds the [CuI₂]^? anions form dimers di-μ-iodo-diiodocuprate(I), which are either planar ( C ) or folded ( D ).     

Synthesis and Crystal Structure of Two CuII‐benzene‐1,2,4,5‐tetracarboxylates with Three‐Dimensional Open Frameworks

Two new three‐dimensional frameworks with zeolite‐like channels were prepared in the presence of 1,6‐diaminohexane. Cu_1.5(H₃N–(CH₂)₆–NH₃)_0.5[C₆H₂(COO)₄] · 5H₂O ( 1 ) crystallizes in the triclinic space group P$\bar{1}$ with a = 772.56(7), b = 1110.36(7), c = 1111.98(8) pm, α = 98.720(7)°, β = 108.246(9)°, and γ = 95.559(7)°. Cu₂(H₃N–(CH₂)₆–NH₃)_0.5(OH)[C₆H₂(COO)₄] · 3H₂O ( 2 ) crystallizes in the monoclinic space group P2/c with a = 1159.34(11), b = 1059.44(7), c = 1582.2(2) pm, and β = 106.130(11)°. The Cu²⁺ coordination polyhedra are connected by [C₆H₂(COO)₄]^4– anions to yield three‐dimensional frameworks with wide centrosymmetric channel‐like voids. Complex 1 reveals voids extending along [100] with diagonals of 900 pm and 300 pm, whereas in complex 2 the diagonal of the nearly rectangular crossection of the channels extending parallel to [001] is 900 pm. The negative excess charges of the frameworks are compensated by [H₃N–(CH₂)₆–NH₃]²⁺ cations, which occupy the voids along with water molecules. The [H₃N–(CH₂)₆–NH₃]²⁺ cations are not connected to Cu²⁺ and have served as templates.     

(Bzl4P)2[Bi2I8] – ein Iodobismutat mit fünffach koordiniertem Bi3+‐Ion

(Bzl₄P)₂[Bi₂I₈] – an Iodobismuthate with Penta‐coordinated Bi³⁺ Ions (Bzl₄P)₂[Bi₂I₈] ( 1 , Bzl = –CH₂–C₆H₅) is the first iodobismuthate showing square pyramidal coordination of the Bi³⁺ ion. The anion structure of 1 is compared with that of (Ph₄P)₂[Bi₂I₈(thf)₂] ( 2 ), in which the vacant coordination sites in 1 are occupied by THF ligands. (Bzl₄P)₂[Bi₂I₈] ( 1 ): Space group P1 (No. 2), a = 1300.6(6), b = 1316.8(6), c = 2157.0(9) pm, α = 78.66(3), β = 87.17(3), γ = 60.62(3)°, V = 3151(2)_.10⁶ pm³; (Ph₄P)₂[Bi₂I₈(thf)₂] ( 2 ): Space group P1 (No. 2), a = 1146.5(1), b = 1181.2(1), c = 1249.2(1) pm, α = 92.28(1), β = 105.71(1), γ = 95.67(1)°, V = 1616.6(2)_.10⁶ pm³.     

P,P′-(2,5-Dihydroxy-3,6-dimethyl-2,5-dioxo-2λ5,5λ5-[1,4,2,5]-dioxadiphosphinan-2,5-diyl)-bis-phosphonsäure

P,P′-(2,5-Dihydroxy-3,6-dimethyl-2,5-dioxo-2λ⁵,5λ⁵-[1,4,2,5]dioxadiphosphinane-2,5-diyl)-bis-phosphonic Acid The tetrahydrate 1 of the title compound crystallizes in the monoclinic space group P2₁/c with a = 845.8, b = 1 098, c = 981.7 pm, β = 113.02° and Z = 2. The anions of the oxonium compound (H₃O⁺ · H₂O)₂(C₄H₁₀O₁₂P₄^2?) are layered by hydrogen bridges. The ¹H, ¹³C and ³¹P NMR spectra (4 and 5 spin systems) are discussed.     

Kristallstruktur von Dipyridiniomethan-Monohalogenohydro-closo-Decaboraten(2–), [(C5H5N)2CH2][2-XB10H9]; X  Cl,Br, I

Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Decaborates(2–), [(C₅H₅N)₂CH₂][2-XB₁₀H₉]; X = Cl, Br, I [B₁₀H₁₀]^2? reacts with chlorine, bromine and iodine or with N-halogenosuccinimide, yielding the monohalogenodecaborates [2-XB₁₀H₉]^2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of the isotypic chloro and bromo compounds [(C₅H₅N)₂CH₂][2-XB₁₀H₉] (monoclinic, space group C2/c, Z = 8; for X ? Cl: a = 33.174(5), b = 7.2809(4), c = 16.2232(7) Å, β = 113.307(7)°; for X = Br: a = 33.525(11), b = 7.281(2), c = 16.297(4) Å, β = 113.62(2)°) and of the iodo compound [(C₅H₅N)₂CH₂][2-IB₁₀H₉] (monoclinic, space group P2₁, Z = 2, a = 7.143(3), b = 13.568(4), c = 9.479(7) Å, β = 97.57(5)°) show columns of substituted boron clusters [2-XB₁₀H₉]^2?, X = Cl, Br, I and bent dications [(C₅H₅N)₂CH₂]²⁺ along the shortest axis wich are assembled to alternating layers in the crystal lattice.     

Controlled Aggregation of Multiple Guanidinium Ions through a Hydrogen‐Bonded Network Assembly with Deprotonated Forms of Kemp’s Triacid

A series of five complexes that incorporate the guanidinium ion and various deprotonated forms of Kemp’s triacid (H₃KTA) have been synthesized and characterized by single‐crystal X‐ray analysis. The complex [C(NH₂)₃⁺] ? [H₂KTA^?] ( 1 ) exhibits a sinusoidal layer structure with a centrosymmetric pseudo‐rosette motif composed of two ion pairs. The fully deprotonated Kemp’s triacid moiety in 3 [C(NH₂)₃⁺] ? [KTA^3?] ( 2 ) forms a record number of eighteen acceptor hydrogen bonds, thus leading to a closely knit three‐dimensional network. The KTA^3? anion adopts an uncommon twist conformation in [(CH₃)₄N⁺] ? 2 [C(NH₂)₃⁺] ? [KTA^3?] ? 2 H₂O ( 3 ). The crystal structure of [(nC₃H₇)₄N⁺] ? 2 [C(NH₂)₃⁺] ? [KTA^3?] ( 4 ) features a tetrahedral aggregate of four guanidinium ions stabilized by an outer shell that comprises six equatorial carboxylate groups that belong to separate [KTA^3?] anions. In 3 [(C₂H₅)₄N⁺] ? 20 [C(NH₂)₃⁺] ? 11 [HKTA^2?] ? [H₂KTA^?] ? 17 H₂O ( 5 ), an even larger centrosymmetric inner core composed of eight guanidinium ions and six bridging water molecules is enclosed by a crust composed of eighteen axial carboxyl/carboxylate groups from six HKTA^2? anions.     

Syntheses and structures of three macrocyclic supramolecular complexes and one ZnII‐containing coordination polymer generated from a semi‐rigid multidentate N‐containing ligand

Semirigid organic ligands can adopt different conformations to construct coordination polymers with more diverse structures when compared to those constructed from rigid ligands. A new asymmetric semirigid organic ligand, 4‐{2‐[(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine ( L ), has been prepared and used to synthesize three bimetallic macrocyclic complexes and one coordination polymer, namely, bis(μ‐4‐{2‐[(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine)bis[dichloridozinc(II)] dichloromethane disolvate, [Zn₂Cl₄(C₁₂H₁₀N₆)₂]·2CH₂Cl₂, ( I ), the analogous chloroform monosolvate, [Zn₂Cl₄(C₁₂H₁₀N₆)₂]·CHCl₃, ( II ), bis(μ‐4‐{2‐[(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine)bis[diiodidozinc(II)] dichloromethane disolvate, [Zn₂I₄(C₁₂H₁₀N₆)₂]·2CH₂Cl₂, ( III ), and catena‐poly[[[diiodidozinc(II)]‐μ‐4‐{2‐[(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine] chloroform monosolvate], {[ZnI₂(C₁₂H₁₀N₆)]·CHCl₃}_n, ( IV ), by solution reaction with ZnX₂ (X = Cl and I) in a CH₂Cl₂/CH₃OH or CHCl₃/CH₃OH mixed solvent system at room temperature. Complex ( I ) is isomorphic with complex ( III ) and has a bimetallic ring possessing similar coordination environments for both of the Zn^II cations. Although complex ( II ) also contains a bimetallic ring, the two Zn^II cations have different coordination environments. Under the influence of the I^? anion and guest CHCl₃ molecule, complex ( IV ) displays a significantly different structure with respect to complexes ( I )–( III ). C—H…Cl and C—H…N hydrogen bonds, and π–π stacking or C—Cl…π interactions exist in complexes ( I )–( IV ), and these weak interactions play an important role in the three‐dimensional structures of ( I )–( IV ) in the solid state. In addition, the fluorescence properties of L and complexes ( I )–( IV ) were investigated.