Synthesis and Crystal Structure of a Two-dimensional Silver（Ⅰ）-Iron（Ⅲ） Heteronuclear Coordination Polymer： {[Ag4Fe2（SCN）12（H2O）2] [（inaH）2（H2O）2]}n

The 2‐D heteronuclear coordination polymer {[Ag₄Fe2(SCN)₁₂(H₂O)₂] (inaH)₂(H₂O)₂}_n (1) (inaH is the abbreviation of protonated isonicotinic acid) with chemical formula C₂₄Ag₄Fe₂N₁₄O₈S₁₂ has been synthesized and characterized by single crystal X‐ray diffraction, elemental analysis and IR spectroscopy. The Ag₂S₂ rings connect two kinds of octahedral geometries of Fe(III) ions, [Fe(NCS)₆]^3– and Fe(H₂O)₂(NCS)₄]^? units with bridging thiocyanate ions leading to 2‐D [Ag₄Fe₂(SCN)₁₂(H₂O)₂^2– anion framework. Four kinds of rings including the unprecedented thirty‐two membered Ag₄Fe₄(SCN)₈ rings share comers or edges in the 2‐D anion layer structure. All thiocyanates coordinate to the metal ions according to the HSAB principle with N atoms binding to the Fe(III) ions and with S atoms binding to Ag(I) ions. Pronoated ina cations stabilize the layer structure as counter ions and hydrogen bonds were formed within the pronoated in a cations dimer and between the dimers and the lattice waters. Crystal data: M_r= 1560.44, triclinic, P1, a=0.76082(1) nm, b=0.9234 nm, c= 1.85611(4) nm, a= 103.0170(10)°, β=93.7780(10)°, y=97.4080(10)°, V= 1.25385(3) nm³, Z=1, μ(Mo Kα)=2.650 mm^?1, D_c,=2.067 g · cm^?3, F(000)=758, R₁=0.0412. wR₂=0.1003.     

Poly­[[bis­[aqua(1,10‐phenanthroline)­lanthanum(III)]‐μ‐aqua‐di‐μ‐5‐sulfonatoisophthalato] monohydrate] and poly­[[[tri­aqua­lanthanum(III)]‐μ‐5‐sulfonatoisophthalato] monohydrate]

In the two related polymeric title compounds, {[La₂(sip)₂(phen)₂(H₂O)₃]·H₂O}_n [sip is the 5‐sulfonatoisophthalate trianion (C₈H₃O₇S³⁻) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)], (I), and {[La(sip)(H₂O)₃]·H₂O}_n, (II), the lanthanum(III) ions are nine‐coordinate, with similar distorted monocapped square‐antiprism coordination geometry. The two crystal structures are very different. In (I), the sip anion acts as a pentadentate ligand, one of the coordinated water mol­ecules lies on a twofold axis and further inversion, n‐glide and translation operations generate a two‐dimensional framework. In (II), the sip anion functions as a hexadentate ligand and a three‐dimensional network with trinuclear 24‐membered rings is developed via inversion, n‐glide, twofold‐screw and translation operations. Both structures also have extensive O—H⋯O hydrogen‐bonded networks and π–π interactions.     

Poly[(acetone)tetraaqua[μ6‐ethyl (dichloromethylene)diphosphonato][μ5‐ethyl (dichloromethylene)diphosphonato]tribarium(II)]

The novel title compound, [Ba₃(C₃H₅Cl₂O₆P₂)₂(C₃H₆O)(H₂O)₄]_n, has a polymeric two‐dimensional network structure which lies parallel to the (10) plane. The asymmetric unit consists of three independent Ba²⁺ ions, two of them eight‐coordinated and the third nine‐coordinated, and two independent ethyl (dichloromethylene)diphosphonate(3−) ligands, one acetone ligand and four aqua ligands. The coordination environments around the BaO₈ polyhedra are best described as bicapped trigonal prismatic, while the BaO₉ polyhedron is in a distorted tricapped trigonal prismatic geometry. The two diphosphonate ligands adopt different coordination modes. Both ligands chelate three metal cations, but one is coordinated to six metal cations in total and forms two six‐membered and one four‐membered chelate ring, while the other is coordinated to five metal cations in total and forms one six‐membered and two four‐membered chelate rings, the fifth unsubstituted O atom remaining uncoordinated.     

3D coordination polymers with vanadyl fragments and alkaline earth metal ions

The reactions of vanadyl sulfate VOSO₄·3H₂O with barium or strontium cyclopropane-1,1-dicarboxylate (MCpdc, M = Ba, Sr, H₂Cpdc = C₃H₄(COOH)₂) afforded the polymeric heterometallic complexes {[(H₂O)₈Ba₂(VO)₂(Cpdc)₄]·2H₂O}n (1) and {[(H₂O)₆Sr(VO)(Cpdc)₂]}n (2), respectively. These complexes differ in the binding mode of mononuclear vanadyl fragments with alkaline earth metal ions. Coordination polymers 1 and 2 were characterized by ESR spectroscopy.     

Mixed cobalt(III) complexes with aromatic amino acids and di­amines. III.

The title compound, [Co(C₉H₁₀NO₃)₂(C₂H₈N₂)]Cl·4H₂O, is one of six possible diastereomers of the (1,2‐di­amino­ethane)­bis(S‐tyrosinato)­cobalt(III) complex. The cobalt(III) ion has an octahedral coordination, with three five‐membered chelate rings which have deformed coordination angles and coordinated O atoms in trans positions. In comparison with the previously reported crystal structure of the Δ‐C₁‐cis(O) diastereomer [Miodragovi?et al. (2001). Enantiomer, 6 , 299–308], the compound presented in this paper has more planar five‐membered amino­carboxyl­ate rings. Complex cations, chloride anions and water mol­ecules of crystallization are linked together by a network of hydrogen bonds. The chloride anions lie approximately between two Co atoms and form hydrogen bonds with all coordinated NH₂ groups. In the crystal structure, there is a weak intermolecular π?π interaction between the phenyl rings.     

(Ni3–xMgx)[B3P3O12(OH)6] · 6 H2O (x ≈ 1.5): A Novel BorophosphateHydrate Containing Isolated Six‐Membered Rings of Tetrahedra

A novel borophosphate‐hydrate, (Ni_3–xMg_x)[B₃P₃O₁₂(OH)₆] · 6 H₂O (x ≈ 1.5), has been prepared by hydrothermal synthesis (T = 170 °C) from a mixture of NiCl₂ · 6 H₂O, Mg(OH)₂, B₂O₃ and H₃PO₄. The crystal structure was determined at 293 K from single‐crystal X‐ray diffraction data (trigonal, R3c (no. 167), a = 14.957(10) Å, c = 13.812(6) Å, V = 2676(2) ų, Z = 6, R₁ = 0.0276, wR₂ = 0.0714 for 779 observed reflections with I > 2σ(I)). The crystal structure contains unbranched six‐membered rings [B₃P₃O₁₂(OH)₆]^6– of alternating corner linked borate and phosphate tetrahedra, which are stacked along [001] and connected via M^IIO₂(OH)₂(H₂O)₂ coordination polyhedra. Hydrogen bonding between the tetrahedral six‐membered rings and M^IIO₂(OH)₂(H₂O)₂ octahedra leads to a further cross‐linking. With respect to the arrangement of isolated six‐membered tetrahedral rings the crystal structure of this borophosphate‐hydrate is closely related to the cyclo‐hexasilicate dioptase, Cu₆[Si₆O₁₈] · 6 H₂O.     

Poly[[tetraaquatris(μ3‐2,2‐dimethylmalonato)dilanthanum(III)] monohydrate]

In the title complex, {[La₂(C₅H₆O₄)₃(H₂O)₄]·H₂O}_n, the La atoms are connected by bridging O atoms from carboxylate groups to build, through centres of inversion, two‐dimensional layers parallel to the ac plane containing decanuclear 20‐membered rings. The coordinated water molecules are involved in intralayer hydrogen‐bond interactions. Adjacent layers are linked via hydrogen bonding to the solvent water molecules. This work represents the first example of a new substituted malonate–lanthanide complex.     

A Three-dimensional Heteronuclear Polymer of [Ag2Fe（SCN）5（DMF）]n Containing Channels and One-dimensional Ag2S2-S-Ag2S2 Chains with Ag…Ag Interaction

Introduction So far, considerable attention has been paid to mag-netic interaction between two different metal ions.1-3 As a potential bridging ligand, thiocyanate can coordinate to a harder metal center with N atom and softer ones with S atom at the same time, resulting in the formation of small ferromagnetic coupling.2 On the other hand, the Fe(III) atom is a good candidate as a hard acid and Ag(I) is a good candidate as a soft acid, so that the Fe(III) centers could be expected to conn…     

Novel Lanthanide Complexes of Ciprofloxacin: Synthesis,Characterization, Crystal Structure and in vitro Antibacterial Activity Studies

Novel lanthanide coordination compounds with ciprofloxacin (CPFX), including eleven complexes Ln(CPFX)₂Cl(H₂O), (Ln=Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb; n = 7, 8, 9) and crystalline [Ce(CPFX)₂ (H₂O)₄] Cl (H₂O)_3.25 (C₂H₅‐OH)_0.25, were synthesized. The crystal is of triclinic space group Pi with a= 1.3865(2) nm, b = 1.3899(3) nm, c = 1.6505(2) nm, a = 92.73(1)°, β= 114.39(1)°, γ=115.55 (1)°, Z = 2 and R = 0.0449. FT‐IR, electronic spectroscopy and X‐ray diffraction were employed to show that the lanthanide ion, which displays an eight‐coordinate structure, is chelated by 3‐carboxyl and 4‐keto oxygen donors of CPFX and two six‐membered chelate rings are formed. Test of in vitro antibacterial activity against E. coli, P. aeruginosa and S. aureus indicated that the in vitro antibacterial activity of the ligand can be improved by complexation with Ce(III).     

Crystal engineering with heteroboranes. II. 1,2‐Di­carboxy‐1,2‐dicarba‐closo‐dodecaborane(12) ethanol hemisolvate

The title compound, 1,2‐(COOH)₂‐1,2‐closo‐C₂B₁₀H₁₀·0.5C₂H₆O or C₄H₁₂B₁₀O₄·0.5C₂H₆O, forms a tetramer by incorporating ethanol (solvent) mol­ecules through hydrogen bonding. Two eight‐membered rings [graph set R(8)] are formed by hydrogen bonding between two carboxyl­ic acid groups, whereas two ten‐membered rings [R(10)] are formed by hydrogen bonding between two carboxyl­ic acid groups and the OH group of an ethanol mol­ecule (solvent). Two crystallographically independent tetramers are present in the crystal structure.     

Investigation of commercial sodium cacodylate trihydrate: penta‐μ‐aqua‐disodium(I) bis(dimethylarsenate) and di‐μ‐aqua‐bis[triaquasodium(I)] bis(dimethylarsenate)

Crystals from commercial samples of sodium cacodylate trihydrate, NaO₂As(CH₃)₂·3H₂O, were analyzed by single‐crystal X‐ray diffraction and two phases were identified, viz. penta‐μ‐aqua‐disodium(I) bis(dimethylarsenate), {[Na₂(H₂O)₅](C₂H₆AsO₂)₂}_n, (I), and di‐μ‐aqua‐bis[triaquasodium(I)] bis(dimethylarsenate), [Na₂(H₂O)₈](C₂H₆AsO₂)₂, (II). Both (I) and (II) form layered structures in which hydrated Na⁺ ions form layers in the ab plane, the cacodylate ions being located in between the layers. In (I), the two non‐equivalent Na⁺ ions (located at twofold axes) and the three non‐equivalent aqua ligands (one of which also lies on a twofold axis) form infinite polymeric layers, but in (II), layers of discrete centrosymmetric [Na₂(H₂O)₈]²⁺ ions are present. One of the commercial samples analyzed contained almost exclusively crystals of the tetrahydrate (II), while another sample consisted of a mixture of the two phases.     

Synthesis,Crystal Structure,Vibrational Spectroscopy and Thermal Behavior of the First Alkali Metal Hydrated Hexaborate： K2[B6O9（OH）2]

New hydrated potassium hexaborate K2[B6O9（OH）2] has been synthesized under mild solvothermal conditions. The structure was determined by single-crystal X-ray diffraction and further characterized by FT-IR, Rarnan spectra and DTA-TG. It crystallizes in the monoclinic system with space group P21/n, a=0.9036（2） nm, b=0.66052（18） nm, c=1.5997（4） nm, β=91.862（4）°, V=0.9543（4） nm^3 and Z=4. Its crystal structure consists of K-O polyhedra and 1-D stepped polyborate chains constructed by new [B6O9（OH）2]2- fundamental building blocks. 1-D polyborate chains contain 3,8-membered boron rings. Adjacent chains are further linked via H-bonding interactions into 2-D layers. The K^＋ cations reside not only between the layers but also in the 8-membered boron rings of the chains, compensating the negative charges of the borate chains and holding the layers together into the 3-D structure through bonding with oxygen atoms of the chains.     

[2+4] and [2+2] Cycloaddition Reactions of N‐Sulfinyl Carboxylic Acid Amides with (CF3)2BNMe2. Crystal Structure of cyclo‐(CF3)2B‐NMe2‐S(=O)‐N=C(p‐CH3C6H4)‐O

N‐sulfinylacylamides R‐C(=O)‐N=S=O react with (CF₃)₂BNMe₂ ( 1 ) to form, by [2+4] cycloaddition, six‐membered rings cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(R)‐O for R = Me ( 2 ), t‐Bu ( 3 ), C₆H₅ ( 4 ), and p‐CH₃C₆H₄ ( 5 ) while N‐sulfinylcarbamic acid esters R‐O‐C(=O)‐N=S=O react with 1 to yield mixtures of six‐membered (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(OR)‐O) and four‐membered rings (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N(C=O)OR) for R = Me ( 6 and 9 ), Et ( 7 and 10 ), and C₆H₅ ( 8 and 11 ). The structure of 5 has been determined by X‐ray diffraction.     

Diamond‐ and Graphite‐Like Octacyanometalate‐Based Polymers Induced by Metal Ions

By using cyclohexane‐1,2‐diamine (chxn), Ni(ClO₄)₂ ? 6H₂O and Na₃[Mo(CN)₈] ? 4H₂O, a 3D diamond‐like polymer {[Ni^II(chxn)₂]₂[Mo^IV(CN)₈] ? 8H₂O}_n ( 1 ) was synthesised, whereas the reaction of chxn and Cu(ClO₄)₂ ? 6H₂O with Na₃[M^V(CN)₈] ? 4H₂O (M=Mo, W) afforded two isomorphous graphite‐like complexes {[Cu^II(chxn)₂]₃[Mo^V(CN)₈]₂ ? 2H₂O}_n ( 2 ) and {[Cu^II(chxn)₂]₃[W^V(CN)₈]₂ ? 2H₂O}_n ( 3 ). When the same synthetic procedure was employed, but replacing Na₃[Mo(CN)₈] ? 4H₂O by (Bu₃NH)₃[Mo(CN)₈] ? 4H₂O (Bu₃N=tributylamine), {[Cu^II(chxn)₂Mo^IV(CN)₈][Cu^II(chxn)₂] ? 2H₂O}_n ( 4 ) was obtained. Single‐crystal X‐ray diffraction analyses showed that the framework of 4 is similar to 2 and 3 , except that a discrete [Cu(chxn)₂]²⁺ moiety in 4 possesses large channels of parallel adjacent layers. The experimental results showed that in this system, the diamond‐ or graphite‐like framework was strongly influenced by the inducement of metal ions. The magnetic properties illustrate that the diamagnetic [Mo^IV(CN)₈] bridges mediate very weak antiferromagnetic coupling between the Ni^II ions in 1 , but lead to the paramagnetic behaviour in 4 because [Mo^IV(CN)₈] weakly coordinates to the Cu^II ions. The magnetic investigations of 2 and 3 indicate the presence of ferromagnetic coupling between the Cu^II and W^V/Mo^V ions, and the more diffuse 5d orbitals lead to a stronger magnetic coupling interaction between the W^V and Cu^II ions than between the Mo^V and Cu^II ions.     

A bis‐copper(II)–[d‐βVal3,7]ascidiacyclamide complex enveloping two square pyramids and sharing an apex atom from a carbonate anion

The four azole rings place structural restrictions on ascidiacyclamide (ASC). As a result, the structure of ASC exists in an equilibrium between two major forms (i.e. folded and square). [d ‐βVal^3,7]Ascidiacyclamide (βASC) was synthesized by replacing two d ‐Val‐Thz (Val is valine and Thz is thiazole) blocks with d ‐β‐Valine (D‐βVal‐Thz). This modification expands the peptide ring; the original 24‐membered macrocycle of ASC becomes a 26‐membered ring. Circular dichroism (CD) spectra showed that, in solution, the structural equilibrium is maintained with βASC, but the folded form is dominant. A copper complex was prepared, namely [[d ‐βVal^3,7]ascidiacyclamide(2?)]aqua‐μ‐carbonato‐dicopper(II) monohydrate, [Cu₂(C₃₈H₅₄N₈O₆S₂)(CO₃)(H₂O)]·H₂O, to determine the effect of the change in ring size on the coordinated structure. The obtained bis‐Cu^II–βASC complex contains two water molecules and a carbonate anion. Two Cu^II ions are chelated by three N‐donor atoms of two Thz–Ile–Oxz (Ile is isoleucine and Oxz is oxazoline) units. An O atom of the carbonate anion bridges two Cu^II ions, forming two square pyramids. These features are similar to the previously reported structure of the Cu^II–ASC complex, but the two pyramids are enveloped inside the peptide and share one apex. In the Cu^II–ASC complex, the apex of each square pyramid is an O atom of a water molecule, and the two pyramids are oriented toward the outside of the peptide. The incorporated β‐amino acids of βASC make the space inside the peptide large enough to envelop the two square pyramids. The observed structural changes in the bis‐Cu^II–βASC complex arising from ring expansion are particularly interesting in the context of the previously reported structure of the Cu^II–ASC complex.     

A Zeolite‐Like Zinc Phosphonocarboxylate Framework and Its Transformation into Two‐ and Three‐Dimensional Structures

Three zinc phosphonocarboxylates, Zn₂(pbc)₂?Hdma?H₃O?2H₂O ( 1 ), Zn(pbc)?Hdma ( 2 ), and Zn_4.5(pbc)₃(OH)(H₂O)_0.5?Hdma ( 3 ) (H₃pbc=4‐phosphonobenzoic acid, dma=dimethylamine) were synthesized by the mixed solvothermal reaction of Zn(Ac)₂?2H₂O and 4‐phosphonobenzoic acid in N,N‐dimethylformamide (DMF) and water. The zigzag and ladderlike chains completely constructed by triply fused 4‐membered rings (denoted SBU‐1) are linked by the organic moieties to form the 3D zeolite‐like structure 1 and the layered structure 2 , respectively. As for structure 3 , a new second building unit (SBU‐2) formed by the inset of the [Zn₃O₁₂] trimer into the 4‐membered ring as well as SBU‐1 is observed. The connections between the two types of SBUs lead to a “zinc phosphate” layer, which is linked by the organic groups to generate a 3D pillar‐layered structure. Both solution‐mediated and solid‐state transformations of 1 to 2 and 3 were observed. A possible mechanism for the transformation is proposed. Gas sorption studies show that 1 has accessible pores for methanol and water and exhibits size selectivity for alcohols.     

catena‐Poly­[[[bis(N,N′‐di­phenyl­thio­urea)­cadmium(II)]‐di‐μ‐thio­cyanato] dihydrate]

Bridging by the two thio­cyanato groups in centrosymmetric six‐coordinate bis­(thio­cyanato)­bis­(di­phenyl­thio­urea)­cad­mium(II) dihydrate leads tothe formation of eight‐membered [Cd—SCN→Cd—SCN→] rings that are linked at the metal atom to furnish chains running parallel to the a axis, i.e {[Cd(NCS)₂(C₁₃H₁₂N₂S)₂]·2H₂O}_n.     

Cyanide-bridged [Fe8M6] clusters displaying single-molecule magnetism (M=Ni) and electron-transfer-coupled spin transitions (M=Co)

Cyanide‐bridged metal complexes of [Fe₈M₆(μ‐CN)₁₄(CN)₁₀ (tp)₈(HL)₁₀(CH₃CN)₂][PF₆]₄?n CH₃CN?m H₂O (HL=3‐(2‐pyridyl)‐5‐[4‐(diphenylamino)phenyl]‐1H‐pyrazole), tp^?=hydrotris(pyrazolylborate), 1 : M=Ni with n=11 and m=7, and 2 : M=Co with n=14 and m=5) were prepared. Complexes 1 and 2 are isomorphous, and crystallized in the monoclinic space group P2₁/n. They have tetradecanuclear cores composed of eight low‐spin (LS) Fe^III and six high‐spin (HS) M^II ions (M=Ni and Co), all of which are bridged by cyanide ions, to form a crown‐like core structure. Magnetic susceptibility measurements revealed that intramolecular ferro‐ and antiferromagnetic interactions are operative in 1 and in a fresh sample of 2 , respectively. Ac magnetic susceptibility measurements of 1 showed frequency‐dependent in‐ and out‐of‐phase signals, characteristic of single‐molecule magnetism (SMM), while desolvated samples of 2 showed thermal‐ and photoinduced intramolecular electron‐transfer‐coupled spin transition (ETCST) between the [(LS‐Fe^II)₃(LS‐Fe^III)₅(HS‐Co^II)₃(LS‐Co^III)₃] and the [(LS‐Fe^III)₈(HS‐Co^II)₆] states.     

Assemblies of 1D and 2D Copper(II) Chiral Coordination Polymers by Salicylaldehyde Schiff Bases: Synthesis,Crystal Structures,and Magnetic Properties

Reaction of CuCl₂ · 2H₂O with chiral Schiff bases and sodium dicyanamide led to the formation of two chiral copper(II) coordination polymers, namely [Cu₄(L¹)₂(dca)₄]_n ( 1 ) and [Cu₂(L²)(μ‐Cl)(dca)(H₂O)]_n · nH₂O ( 2 ) {H₂L¹ = (1R, 3S)‐N′,N′′‐bis[salicylidene]‐1,3‐diamino‐ 1,2,2‐trimethylcyclopentane, H₂L² = (1R, 3S)‐N′,N′′‐bis[3‐ethoxysalicylidene]‐1,3‐diamino‐ 1,2,2‐trimethylcyclopentane, dca = dicyanamide}. Both complexes were structurally characterized by elemental analyses, IR spectroscopy and single‐crystal X‐ray diffraction. Complex 1 exhibits a two‐dimensional polymeric structure formed by single dca bridging tetranuclear Cu₄ units. Complex 2 displays a left‐handed helical chain structure constructed from Cu₂ dimers with single dca bridges. The chirality of 1 and 2 was confirmed by circular dichroism (CD) measurements in solution. Both complexes exhibit strong antiferromagnetic couplings with J = –308(4) cm^–1 for 1 and J = –123(1) cm^–1 for 2 in 2–300 K.     

Sodium hydrogen nitrilo­tri­acetate dihydrate

In the title compound, Na⁺·C₆H₈NO₆^?·2H₂O, the sodium ion is coordinated in a distorted octahedral manner by two carboxyl­ate O atoms and two water O atoms. Each of these water mol­ecules bridges two adjacent Na ions, resulting in two four‐membered rings of the type Na–O–Na–O.