Poly[bis(μ2‐2‐aminopyrazine‐κ2N1:N4)(μ2‐nitrato‐κ2O:O)(nitrato‐κ2O,O′)disilver(I)]: an achiral two‐dimensional coordination polymer forming chiral crystals

The solution reaction of AgNO₃ and 2‐aminopyrazine (apyz) in a 1:1 ratio gives rise to the title compound, [Ag₂(NO₃)₂(C₄H₅N₃)₂]_n, (I), which possesses a chiral crystal structure. In (I), both of the crystallographically independent Ag^I cations are coordinated in tetrahedral geometries by two N atoms from two apyz ligands and two O atoms from nitrate anions; however, the Ag^I centers show two different coordination environments in which one is coordinated by two O atoms from two different symmetry‐related nitrate anions and the second is coordinated by two O atoms from a single nitrate anion. The crystal structure consists of one‐dimensional Ag^I–apyz chains, which are further extended by μ₂‐κ²O:O nitrate anions into a two‐dimensional (4,4) sheet. N—H...O and C_apyz—H...O hydrogen bonds connect neighboring sheets to form a three‐dimensional supramolecular framework.     

Silver(I) sulfate coordination polymers with 4,4′‐bipyridazine and pyridazino[4,5‐d]pyridazine

Poly[[μ₄‐4,4′‐bipyridazine‐μ₅‐sulfato‐disilver(I)] monohydrate], {[Ag₂(SO₄)(C₈H₆N₄)]·H₂O}_n, (I), and poly[[aqua‐μ₄‐pyridazino[4,5‐d]pyridazine‐μ₃‐sulfato‐disilver(I)] monohydrate], {[Ag₂(SO₄)(C₆H₄N₄)(H₂O)]·H₂O}_n, (II), possess three‐ and two‐dimensional polymeric structures, respectively, supported by N‐tetradentate coordination of the organic ligands [Ag—N = 2.208 (3)–2.384 (3) Å] and O‐pentadentate coordination of the sulfate anions [Ag—O = 2.284 (3)–2.700 (2) Å]. Compound (I) is the first structurally examined complex of the new ligand 4,4′‐bipyridazine; it is based upon unprecedented centrosymmetric silver–pyridazine tetramers with tetrahedral AgN₂O₂ and trigonal–bipyramidal AgN₂O₃ coordination of two independent Ag^I ions. Compound (II) adopts a typical dimeric silver–pyridazine motif incorporating two kinds of square‐pyramidal AgN₂O₃ Ag^I ions. The structure exhibits short anion–π interactions involving noncoordinated sulfate O atoms [O...π = 3.041 (3) Å].     

A novel three‐dimensional coordination polymer constructed from pyrazine and copper(I): poly[[copper(I)‐di‐μ2‐pyrazine‐κ4N:N′] 3,5‐dicarboxybenzenesulfonate monohydrate]

In the title metal–organic framework complex, {[Cu(C₄H₄N₂)₂](C₈H₅O₇S)·H₂O}_n or {[Cu^I(pyz)₂](H₂SIP)·H₂O}_n (pyz is pyrazine and H₃SIP is 5‐sulfoisophthalic acid or 3,5‐dicarboxybenzenesulfonic acid), the asymmetric unit is composed of one copper(I) center, one whole pyrazine ligand, two half pyrazine ligands lying about inversion centres, one H₂SIP⁻ anion and one lattice water molecule, wherein each Cu^I atom is in a slightly distorted tetrahedral coordination environment completed by four pyrazine N atoms, with the Cu—N bond lengths in the range 2.017 (3)–2.061 (3) Å. The structure features a three‐dimensional diamondoid network with one‐dimensional channels occupied by H₂SIP⁻ anions and lattice water molecules. Interestingly, the guest–water hydrogen‐bonded network is also a diamondoid network, which interpenetrates the metal–pyrazine network.     

catena‐Poly[tris(ethylenediamine‐κ2N,N′)nickel(II) [[trithiocyanato‐κ3N‐sodium(I)]‐μ‐aqua‐κ2O:O]]

The title complex, {[Ni(C₂H₈N₂)₃][Na(NCS)₃(H₂O)]}_n, con­sists of discrete [Ni(en)₃]²⁺ dications (en is ethyl­enedi­amine) and polymeric [(H₂O)_0.5Na(NCS)₃(H₂O)_0.5]_n^2n? anions. The compound crystallizes in space group Pc1. The Ni^II atom lies on a threefold axis and has a distorted octahedral coordination geometry. The Na⁺ cation also lies on a site with imposed crystallographic threefold symmetry and is coordinated by the thio­cyanate N atoms (the thio­cyanates are in general posi­tions), by one water mol­ecule with crystallographically imposed 32 symmetry and by a second water mol­ecule with crystallographically imposed symmetry. The unique Na atom thus has trigonal–bipyramidal coordination. The O atoms of the water mol­ecules bridge the Na⁺ cations to form one‐dimensional polymeric chains in the crystal structure. The [Ni(en)₃]²⁺ dications are distributed around and between the chains and are linked to them via N—H?S hydrogen bonds.     

Poly[tetra‐μ2‐l‐lactato‐indium(III)sodium(I)]

The asymmetric unit of the title compound, [InNa(C₃H₅O₃)₄]_n, consists of one In^III ion, one Na^I ion and four crystallographically independent l ‐lactate monoanions. The coordination of the In^III ion is composed of five carboxylate O and two hydroxy O atoms in a distorted pentagonal–bipyramidal coordination geometry. The Na^I ion is six‐coordinated by four carboxylate O atoms and two hydroxy O atoms from four l ‐lactate ligands in a distorted octahedral geometry. Each In^III ion is coordinated by four surrounding l ‐lactate ligands to form an [In(l ‐lactate)₄]⁻ unit, which is further linked by Na^I ions through Na—O bonds to give a two‐dimensional layered structure. Hydrogen bonds between the hydroxy groups and carboxylate O atoms are observed between neighbouring layers.     

Rb6LiPr11Cl16[SeO3]12: Ein chloridisch derivatisiertes Rubidium‐Lithium‐Praseodym(III)‐Oxoselenat(IV)

Rb₆LiPr₁₁Cl₁₆[SeO₃]₁₂: A Chloride‐Derivatized Rubidium Lithium Praseodymium(III) Oxoselenate(IV) Transparent green square platelets with often truncated edges and corners of Rb₆LiPr₁₁Cl₁₆[SeO₃]₁₂ were obtained by the reaction of elemental praseodymium, praseodymium(III,IV) oxide and selenium dioxide with an eutectic LiCl–RbCl flux at 500 °C in evacuated silica ampoules. A single crystal of the moisture and air insensitive compound was characterized by X‐ray diffraction single‐crystal structure analysis. Rb₆LiPr₁₁Cl₁₆[SeO₃]₁₂ crystallizes tetragonally in the space group I4/mcm (no. 140; a = 1590.58(6) pm, c = 2478.97(9) pm, c/a = 1.559; Z = 4). The crystal structure is characterized by two types of layers parallel to the (001) plane following the sequence 121′2′1. Cl^? anions form cubes around the Rb⁺ cations (Rb1 and Rb2; CN = 8; d(Rb⁺?Cl^?) = 331 – 366 pm) within the first layer. One quarter of the possible places for Rb⁺ cations within this CsCl‐type kind of arrangement is not occupied, however the Cl^? anions of these vacancies are connected to Pr³⁺ cations (Pr4) above and below instead, forming square antiprisms of [(Pr4)O₄Cl₄]^9? units (d(Pr4?O) = 247–249 pm; d(Pr4?Cl) = 284–297 pm) that work as links between layer 1 and 2. Central cations of the second layer consist of Li⁺ and Pr³⁺. While the Li⁺ cations are surrounded by eight O^2? anions (d(Li?O5) = 251 pm) in the shape of cubes again, the Pr³⁺ cations are likewisely coordinated by eight O^2? anions as square antiprisms (for Pr1, d(Pr1?O2) = 242 pm) and by ten O^2? anions (for Pr2 and Pr3), respectively. The latter form tetracapped trigonal antiprisms (Pr2, d(Pr2?O) = 251–253 pm and 4 × 262 pm) or bicapped distorted cubes (Pr3, d(Pr3?O) = 245–259 pm and 2 × 279 pm). The non‐binding electron pairs (“lone pairs”) at the two crystallographically different Ψ¹‐tetrahedral [SeO₃]^2? anions (d(Se⁴⁺?O^2?) = 169–173 pm) are directing towards the empty cavities between the layer‐connecting [(Pr4)O₄Cl₄]^9? units.     

La3OCl[AsO3]2: Ein Lanthan‐Oxidchlorid‐Oxoarsenat(III) mit “lone‐pair”‐Kanalstruktur

La₃OCl[AsO₃]₂: A Lanthanum Oxide Chloride Oxoarsenate(III) with a “Lone‐Pair” Channel Structure La₃OCl[AsO₃]₂ was prepared by the solid‐state reaction between La₂O₃ and As₂O₃ using LaCl₃ and CsCl as fluxing agents in evacuated silica ampoules at 850 °C. The colourless crystals with pillar‐shaped habit crystallize tetragonally (a = 1299.96(9), c = 558.37(5) pm, c/a = 0.430) in the space group P4₂/mnm (no. 136) with four formula units per unit cell. The crystal structure contains two crystallographically different La³⁺ cations. (La1)³⁺ is coordinated by six oxygen atoms and two chloride anions in the shape of a bicapped trigonal prism (CN = 8), whereas (La2)³⁺ carries eight oxygen atoms and one Cl^? anion arranged in the shape of tricapped trigonal prism (CN = 9). The isolated pyramidal [AsO₃]^3? anions (d(As–O) = 175–179 pm) consist of three oxygen atoms (O2 and two O3), which surround the As³⁺ cations together with the free, non‐binding electron pair (lone pair) Ψ¹‐tetrahedrally (?(O–As–O) = 95°, 3×). One of the three crystallographically independent oxygen atoms (O1), however, is exclusively coordinated by four (La2)³⁺ cations in the shape of a real tetrahedron (d(O–La) = 236 pm, 4×). These [(O1)(La2)₄]¹⁰⁺ tetrahedra form endless chains in the direction of the c axis through trans‐edge condensation. Empty channels, constituted by the lone‐pair electrons of the Cl^? anions and the As³⁺ cations in the Ψ¹‐tetrahedral oxoarsenate(III) anions [AsO₃]^3?, run parallel to [001] as well.     

Quaternäre Caesium‐Kupfer(I)‐Lanthanoid(III)‐Selenide vom Typ CsCu3M2Se5 (M = Sm,Gd — Lu)

Quaternary Cesium Copper(I) Lanthanoid(III) Selenides of the Type CsCu₃M₂Se₅ (M = Sm, Gd — Lu) By oxidation of mixtures of copper and lanthanoid metal with elemental selenium in molar ratios of 1 : 1 : 2 and in addition of CsCl quaternary cesium copper(I) lanthanoid(III) selenides with the formula CsCu₃M₂Se₅ (M = Sm, Gd — Lu) were obtained at 750 °C within a week from torch‐sealed evacuated silica tubes. An excess of CsCl as flux helps to crystallize golden yellow or red, needle‐shaped, water‐resistant single crystals. The crystal structure of CsCu₃M₂Se₅ (M = Sm, Gd — Lu) (orthorhombic, Cmcm, Z = 4; e. g. CsCu₃Sm₂Se₅: a = 417.84(3), b = 1470.91(8), c = 1764.78(9) pm and CsCu₃Lu₂Se₅: a = 407.63(3), b = 1464.86(8), c = 1707.21(9) pm, respectively) contains [MSe₆]^9— octahedra which share edges to form double chains running along [100]. Those are further connected by vertices to generate a two‐dimensional layer parallel to (010). By edge‐ and vertex‐linking of [CuSe₄]^7— tetrahedra two crystallographically different Cu⁺ cations build up two‐dimensional puckered layers parallel to (010) as well. These sheet‐like structure interconnects the equation/tex2gif-stack-3.gif{[M₂Se₅]^4—} layers to create a three‐dimensional network according to equation/tex2gif-stack-4.gif{[Cu₃M₂Se₅]^—}. Thus empty channels along [100] form, apt to take up the Cs⁺ cations. These are surrounded by eight plus one Se^2— anions in the shape of (2+1)‐fold capped trigonal prisms with Cs—Se distances between 348 and 368 pm (8×) and 437 (for M = Sm) or 440 pm (for M = Lu), respectively, for the ninth ligand.     

Na3F[WO4]: A Sodium Fluoride Ortho‐Oxotungstate(VI) with Strands of Face‐Shared Fluoride‐Centred Sodium Octahedra According to $^{1}_{\infty}\rm \{[FNa_{6/2}]^{2+}\}$

During the reaction of Na₂[WO₄] with YF₃ purposed to yield fluoride‐derivatized yttrium oxotungstates(VI), colourless platelet‐shaped single crystals of Na₃F[WO₄] emerged as main product. The title compound crystallizes orthorhombically in the space group Pnma (a = 559.59(5), b = 751.02(7), c = 1285.98(9) pm) with four formula units per unit cell. Besides isolated ortho‐oxotungstate units [WO₄]^2? (d(W–O) = 176–178 pm) the crystal structure contains two crystallographically independent Na⁺ cations which are both octahedrally coordinated by four oxygen atoms and two fluoride anions. The F^? anions are surrounded by six sodium cations (d(F–Na) = 224–242 pm) also in an octahedral fashion. These octahedra built up chains along [100] by sharing trans‐oriented faces according to , which are stacked according to a hexagonal closest rod‐packing. The cationic strands are surrounded, interconnected and charge‐balanced by isolated [WO₄]^2? tetrahedra with almost ideal shape and every O^2? ligand is terminally coordinated by three Na⁺ cations.     

Tris(1,9‐diethyl­adeninium) triiodide diiodide

X‐ray analysis of the title compound reveals three crystallographically distinct cations of 1,9‐diethyl­adeninium, two iodide anions and one triiodide anion in the asymmetric unit, giving six residues and the formula 3C₉H₁₄N₅⁺·I₃⁻·2I⁻. Standard purine nomenclature is used to identify the atoms of each adenine moiety. Hydrogen bonding is observed between atoms N6 and N7 of a pair of cations [N⋯N = 2.885 (4)/2.902 (3) and 2.854 (3)/2.854 (3) Å], with additional hydrogen bonding to I⁻ anions via the other N6 H atom [N⋯I = 3.708 (3), 3.738 (3) and 3.638 (3) Å]. The triiodide anion is not involved in hydrogen bonding. The bond lengths and angles of the 1,9‐diethyl­adeninium cations are compared with literature values and confirm the formation of the imine tautomer.     

A novel three‐dimensional heterometallic coordination polymer: poly[[diaquadi‐μ3‐chlorido‐μ2‐chlorido‐tri‐μ3‐nicotinato‐tricopper(I)gadolinium(III)] hemihydrate]

In the title polymeric heterometallic compound, {[Cu₃Gd(C₆H₄NO₂)₃Cl₃(H₂O)₂]·0.5H₂O}_n, comprising copper(I) and gadolinium(III) cations bridged by nicotinate (nic) ligands and chloride anions, the Gd^III centers display a bicapped trigonal prismatic geometry, defined by six carboxylate O atoms and two water molecules. For copper(I), one Cu center is three‐coordinated by three chloride ions and displays a trigonal–planar geometry; the other two Cu centers are four‐coordinated and display a very distorted tetrahedral geometry. The chloride anions act in μ₂‐ and μ₃‐bridging modes, linking the Cu^I ions into an infinite chain. The nic ligand exhibits a tridentate coordination mode, with the carboxylate O atoms linking to two Gd^III ions and the N atom linking to one Cu^I ion. Thus, a novel three‐dimensional heterometallic coordination polymer is constructed from Gd–carboxylate subunits and Cu—Cl chains. In addition, intra‐ and intermolecular O—H...O and O—H...Cl hydrogen bonds are also observed within the three‐dimensional structure. Topologically, the framework represents an unusual 3,6‐connected (4.8²)₃(4¹⁰.6⁵) net.     

Einkristalle des Cer(IV)–Oxotellurats(IV) CeTe2O6

Single Crystals of the Cerium(IV) Oxotellurate(IV) CeTe₂O₆ Orange‐red, coffin‐shaped single crystals of CeTe₂O₆ (monoclinic, P2₁/n; a = 703.71(5), b = 1106.32(8), c = 735.24(5) pm, β = 108.066(6)°; Z = 4) were obtained by the reaction of admixtures of cerium dioxide and tellurium dioxide (CeO₂, TeO₂; molar ratio 1 : 2) in the presence of fluxing CsCl (750 °C, 4 d) in evacuated silica tubes. The crystal structure contains eightfold coordinated Ce⁴⁺ cations, which are surrounded by irregular trigonal dodecahedra of oxygen atoms. The interconnection of these [CeO₈] polyhedra occurs via two edges (O2–O2′ and O3–O3′) with equatorial orientation relative to each other forming zigzag chains {[CeO_4/1O_4/2]^8–} which run parallel to [100] and arrange as a hexagonal packing of rods. Both crystallographically different Te⁴⁺ cations exhibit trigonal non‐planar coordination figures (ψ¹ tetrahedra) with three oxygen atoms each as a result of the stereochemical activity of the non‐binding electron pairs (“lone pairs”). They also are responsible for the necessary cross‐linkage of the anionic {[CeO₆]^8–} chains. The isotypical relationship with Ce(SeO₃)₂ therefore justifies the formulation Ce(TeO₃)₂ for CeTe₂O₆.     

A new three‐dimensional silver(I) coordination framework with a diamondoid topology constructed from 2‐(pyridin‐4‐yl)‐1H‐imidazole‐4,5‐dicarboxylic acid

The title compound, poly[[μ₄‐5‐carboxy‐4‐carboxylato‐2‐(pyridin‐4‐yl)‐1H‐imidazol‐1‐ido]disilver(I)], [Ag₂(C₁₀H₅N₃O₄)]_n, was synthesized by reacting silver nitrate with 2‐(pyridin‐4‐yl)‐1H‐imidazole‐4,5‐dicarboxylic acid (H₃PyIDC) under hydrothermal conditions. The asymmetric unit contains two crystallographically independent Ag^I cations and one unique HPyIDC²⁻ anion. Both Ag^I cations are three‐coordinated in distorted T‐shaped coordination geometries. One Ag^I cation is coordinated by one N and two O atoms from two HPyIDC²⁻ anions, while the other is bonded to one O and two N atoms from two HPyIDC²⁻ anions. It is interesting to note that the HPyIDC²⁻ group acts as a μ₄‐bridging ligand to link the Ag^I cations into a three‐dimensional framework, which can be simplified as a diamondoid topology. The thermal stability and photoluminescent properties of the title compound have also been studied.     

Das neue Neodym(III)‐Oxidchlorid‐Oxoselenat(IV) Nd7O5Cl3[SeO3]4

Pale violet, needle‐shaped single crystals of the new neodymium(III) oxide chloride oxoselenate(IV) Nd₇O₅Cl₃[SeO₃]₄ were obtained by the reaction of Nd₂O₃ and NdCl₃ with SeO₂ (molar ratio: 3:1:4) in evacuated silica ampoules within seven days at 775 °C, if an excess of CsCl worked as fluxing agent. Nd₇O₅Cl₃[SeO₃]₄ crystallizes in the triclinic space group P with the lattice parameters a = 694.46(4), b = 944.53(5), c = 1567.92(9) pm, α = 87.821(3), β = 81.849(3), γ = 84.852(3)° and Z = 2. Its structure exhibits seven crystallographically different Nd³⁺ cations, of which (Nd1)³⁺ – (Nd4)³⁺ are coordinated by O^2– anions forming distorted square prisms. The polyhedra of (Nd1)³⁺ and (Nd2)³⁺ receive additional caps by one Cl^– anion each, and (Nd5)³⁺ – (Nd7)³⁺ show mixed square antiprismatic environments of O^2– and Cl^– anions too. However, the polyhedra of (Nd5)³⁺ and (Nd6)³⁺ include two, the polyhedron about (Nd7)³⁺ even three Cl^– anions. Two‐dimensional layers of edge‐ and vertex‐linked [ONd₄]¹⁰⁺ tetrahedra are built up by (O1)^2– – (O5)^2– together with all Nd³⁺ cations. All the other oxygen atoms belong to four crystallographically different Se⁴⁺ cations erecting ψ¹‐tetrahedral oxoselenate(IV) units [SeO₃]^2– with stereochemically active non‐bonding electron pairs (“lone pairs”) pointing into the free space between the layers. Three independent Cl^– anions in threefold coordination of Nd³⁺ cations interconnect the layers to form a three‐dimensional network, thereby achieving the charge balance.     

catena‐Poly[[silver(I)‐μ‐1,3‐bis(4‐pyridyl)propane] hemi(naphthalene‐1,5‐disulfonate) dihydrate]: a three‐dimensional metallo‐supramolecular sandwich lamellar network

The title compound, {[Ag(C₁₃H₁₄N₂)](C₁₀H₆O₆S₂)_0.5·2H₂O}_n, (I), features a three‐dimensional supramolecular sandwich architecture that consists of two‐dimensional cationic layers composed of polymeric chains of silver(I) ions and 1,3‐bis(4‐pyridyl)propane (bpp) ligands, linked by Ag...Ag and π–π interactions, alternating with anionic layers in which uncoordinated naphthalene‐1,5‐disulfonate (nds²⁻) anions and solvent water molecules form a hydrogen‐bonded network. The asymmetric unit consists of one Ag^I cation linearly coordinated by N atoms from two bpp ligands, one bpp ligand, one half of an nds²⁻ anion lying on a centre of inversion and two solvent water molecules. The two‐dimensional {[Ag(bpp)]⁺}_n cationic and {[(nds)·2H₂O]²⁻}_n anionic layers are assembled into a three‐dimensional supramolecular framework through long secondary coordination Ag...O interactions between the sulfonate O atoms and Ag^I centres and through nonclassical C—H...O hydrogen bonds.     

Chiral one‐ and two‐dimensional silver(I)–biotin coordination polymers

Reaction of biotin {C₁₀H₁₆N₂O₃S, HL; systematic name: 5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoic acid} with silver acetate and a few drops of aqueous ammonia leads to the deprotonation of the carboxylic acid group and the formation of a neutral chiral two‐dimensional polymer network, poly[[{μ₃‐5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}silver(I)] trihydrate], {[Ag(C₁₀H₁₅N₂O₃S)]·3H₂O}_n or {[Ag(L)]·3H₂O}_n, (I). Here, the Ag^I cations are pentacoordinate, coordinated by four biotin anions via two S atoms and a ureido O atom, and by two carboxylate O atoms of the same molecule. The reaction of biotin with silver salts of potentially coordinating anions, viz. nitrate and perchlorate, leads to the formation of the chiral one‐dimensional coordination polymers catena‐poly[[bis[nitratosilver(I)]‐bis{μ₃‐5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}] monohydrate], {[Ag₂(NO₃)₂(C₁₀H₁₆N₂O₃S)₂]·H₂O}_n or {[Ag₂(NO₃)₂(HL)₂]·H₂O}_n, (II), and catena‐poly[bis[perchloratosilver(I)]‐bis{μ₃‐5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}], [Ag₂(ClO₄)₂(C₁₀H₁₆N₂O₃S)₂]_n or [Ag₂(ClO₄)₂(HL)₂]_n, (III), respectively. In (II), the Ag^I cations are again pentacoordinated by three biotin molecules via two S atoms and a ureido O atom, and by two O atoms of a nitrate anion. In (I), (II) and (III), the Ag^I cations are bridged by an S atom and are coordinated by the ureido O atom and the O atoms of the anions. The reaction of biotin with silver salts of noncoordinating anions, viz. hexafluoridophosphate (PF₆⁻) and hexafluoridoantimonate (SbF₆⁻), gave the chiral double‐stranded helical structures catena‐poly[[silver(I)‐bis{μ₂‐5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}] hexafluoridophosphate], {[Ag(C₁₀H₁₆N₂O₃S)₂](PF₆)}_n or {[Ag(HL)₂](PF₆)}_n, (IV), and catena‐poly[[[{5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}silver(I)]‐μ₂‐{5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}] hexafluoridoantimonate], {[Ag(C₁₀H₁₆N₂O₃S)₂](SbF₆)}_n or {[Ag(HL)₂](SbF₆)}_n, (V), respectively. In (IV), the Ag^I cations have a tetrahedral coordination environment, coordinated by four biotin molecules via two S atoms, and by two carboxy O atoms of two different molecules. In (V), however, the Ag^I cations have a trigonal coordination environment, coordinated by three biotin molecules via two S atoms and one carboxy O atom. In (IV) and (V), neither the ureido O atom nor the F atoms of the anion are involved in coordination. Hence, the coordination environment of the Ag^I cations varies from AgS₂O trigonal to AgS₂O₂ tetrahedral to AgS₂O₃ square‐pyramidal. The conformation of the valeric acid side chain varies from extended to twisted and this, together with the various anions present, has an influence on the solid‐state structures of the resulting compounds. The various O—H...O and N—H...O hydrogen bonds present result in the formation of chiral two‐ and three‐dimensional networks, which are further stabilized by C—H...X (X = O, F, S) interactions, and by N—H...F interactions for (IV) and (V). Biotin itself has a twisted valeric acid side chain which is involved in an intramolecular C—H...S hydrogen bond. The tetrahydrothiophene ring has an envelope conformation with the S atom as the flap. It is displaced from the mean plane of the four C atoms (plane B) by 0.8789 (6) Å, towards the ureido ring (plane A). Planes A and B are inclined to one another by 58.89 (14)°. In the crystal, molecules are linked via O—H...O and N—H...O hydrogen bonds, enclosing R₂²(8) loops, forming zigzag chains propagating along [001]. These chains are linked via N—H...O hydrogen bonds, and C—H...S and C—H...O interactions forming a three‐dimensional network. The absolute configurations of biotin and complexes (I), (II), (IV) and (V) were confirmed crystallographically by resonant scattering.     

CsSc3F6[SeO3]2: A New Rare‐Earth Metal(III) Fluoride Oxoselenate(IV) With Sections Of The ReO3‐Type Structure

A new representative of rare‐earth metal(III) fluoride oxoselenates(IV) derivatized with alkali metals could be synthesized via solid‐state reactions. Colorless single crystals of CsSc₃F₆[SeO₃]₂ were obtained through the reaction of Sc₂O₃, ScF₃, and SeO₂ (molar ratio 1:1:3) with CsBr as reactant and fluxing agent. For this purpose, corundum crucibles embedded as liners into evacuated silica ampoules were applied as containers for these reactions at 700 °C for seven days. The new quintenary compound crystallizes in the trigonal space group P3m1 with a = 565.34(4) and c = 1069.87(8) pm (c/a = 1.892) for Z = 1. The crystal structure of CsSc₃F₆[SeO₃]₂ contains two crystallographically different Sc³⁺ cations. Each (Sc1)³⁺ is surrounded by six fluoride anions as octahedron, while the octahedra about (Sc2)³⁺ are formed by three fluoride anions and three oxygen atoms from three terminal [SeO₃]^2– anions. The [(Sc1)F₆]^3– octahedra link via common F^– vertices to six fac‐[(Sc2)F₃O₃]^6– octahedra forming ²_∞{[Sc₃F₆O₆]^9–} layers parallel to (001). These layers are separated by oxygen‐coordinated Cs⁺ cations (C.N. = 12), arranging for the charge compensation, while Se⁴⁺ cations within the layers surrounded by three oxygen atoms as ψ¹‐tetrahedral [SeO₃]^2– units complete the structure. EDX measurements confirmed the composition of the title compound and single‐crystal Raman studies showed the typical vibrational modes of isolated [SeO₃]^2– anions with ideal C_3v symmetry.     

Single Crystals of the Dodecaiodo‐closo‐dodecaborate Cs2[B12I12] · 2 CH3CN (≡ {Cs(NCCH3)}2[B12I12]) from Acetonitrile

Colourless, lath‐shaped single crystals of Cs₂[B₁₂I₁₂] · 2 CH₃CN (monoclinic, C2/m; a = 1550.3(2), b = 1273.2(1), c = 1051.5(1) pm, β = 120.97(1)°; Z = 2) are obtained by the reaction of Cs₂[B₁₂H₁₂] with an excess of I₂ and ICl (molar ratio: 1 : 2) in methylene iodide (CH₂I₂) at 180 °C (8 h) and recrystallization of the crude product from acetonitrile (CH₃CN). The crystal structure contains quasi‐icosahedral [B₁₂I₁₂]^2– anions (d(B–B) = 176–182 pm, d(B–I) = 211–218 pm) which arrange in a cubic closest‐packed fashion. All octahedral interstices are filled with centrosymmetric dimer‐cations {[Cs(N≡C–CH₃)]₂}²⁺ containing a diamond‐shaped four‐membered (Cs–N–Cs–N) ring of Cs⁺ cations and nitrogen atoms of the solvating acetonitrile molecules (d(Cs–N) = 321 pm, 2 ×). The cesium cations themselves actually reside in the distorted tetrahedral voids of the cubic [B₁₂I₁₂]^2– packing (d(Cs–I) = 402–461 pm, 10 ×) if one ignores the solvent particles.     

[μ‐4,5‐Bis(diphenylphosphino)‐9,9‐dimethylxanthene]bis[(trifluoroacetato)gold(I)] and its dichloromethane 0.58‐solvate

The dinuclear Au^I complex containing the 4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene (xantphos) ligand and trifluoroacetate anions exists in a solvent‐free form, [μ‐4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene]bis[(trifluoroacetato)gold(I)], [Au₂(C₂F₃O₂)₂(C₃₉H₃₂OP₂)], (I), and as a dichloromethane solvate, [Au₂(C₂F₃O₂)₂(C₃₉H₃₂OP₂)]·0.58CH₂Cl₂, (II). The trifluoroacetate anions are coordinated to the Au^I centres bridged by the xantphos ligand in both compounds. The Au^I atoms are in distorted linear coordination environments in both compounds. The phosphine substituents are in a syn arrangement in the xantphos ligand, which facilitates the formation of short aurophilic Au...Au interactions of 2.8966 (8) Å in (I) and 2.9439 (6) Å in (II).     

Anion‐directed Silver(I) Coordination Assemblies Based on 1‐(2‐Pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazolewith Diverse Supramolecular Networks and Dichromate Removal Capabilities

A series of silver(I) supramolecular complexes, namely, {[Ag(L²⁴)](NO₃)}_n ( 1 ), [Ag₂(L²⁴)(NO₂)₂]_n ( 2 ), and {[Ag_1.25(L²⁴)(DMF)](PF₆)_1.25}_n ( 3 ) were prepared by the reactions of 1‐(2‐pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazole (L²⁴) and silver(I) salts with different anions (AgNO₃, AgNO₂, AgPF₆). Single‐crystal X‐ray diffraction indicates that 1 – 3 display diverse supramolecular networks. The structure of dinuclear complex 1 is composed of a six‐membered Ag₂N₄ ring with the Ag ··· Ag distance of 4.4137(3) Å. In complex 2 , the adjacent Ag^I centers are interlinked by L²⁴ ligands into a 1D chain, the adjacent of which are further extended by the bridged nitrites to construct a 2D coordination architecture. Complex 3 shows a 3D (3,4)‐connected framework, which is generated by the linkage of L²⁴ ligands. All complexes were characterized by IR spectra, elemental analysis, and powder X‐ray diffraction. Notably, a structural comparison of the complexes demonstrates that their structures are predominated by the nature of anions. Additionally, 1 and 2 show efficient dichromate (Cr₂O₇^2–) capture in water system, which can be ascribed to the anion‐exchange.