Two novel silver(I) coordination polymers: poly[(μ2‐2‐aminopyrimidine‐κ2N1:N3)bis(μ3‐thiocyanato‐κ3S:S:S)disilver(I)] and poly[(2‐amino‐4,6‐dimethylpyrimidine‐κN)(μ3‐thiocyanato‐κ3N:S:S)silver(I)]

2‐Aminopyrimidine (L1) and 2‐amino‐4,6‐dimethylpyrimidine (L2) have been used to create the two novel title complexes, [Ag₂(NCS)₂(C₄H₅N₃)]_n, (I), and [Ag(NCS)(C₆H₉N₃)]_n, (II). The structures of complexes (I) and (II) are mainly directed by the steric properties of the ligands. In (I), the L1 ligand is bisected by a twofold rotation axis running through the amine N atom and opposite C atoms of the pyrimidine ring. The thiocyanate anion adopts the rare μ₃‐κ³S coordination mode to link three tetrahedrally coordinated Ag^I ions into a two‐dimensional honeycomb‐like 6³ net. The L1 ligands further extend the two‐dimensional sheet to form a three‐dimensional framework by bridging Ag^I ions in adjacent layers. In (II), with three formula units in the asymmetric unit, the L2 ligand bonds to a single Ag^I ion in a monodentate fashion, while the thiocyanate anions adopt a μ₃‐κ¹N,κ²S coordination mode to link the AgL2 subunits to form two‐dimensional sheets. These layers are linked by N—H...N hydrogen bonds between the noncoordinated amino H atoms and both thiocyanate and pyrimidine N atoms.     

A cyclic tetramer of [Ag(1,4,7‐trithiacyclononane)]+, cyclo‐tetrakis(μ‐1,4,7‐trithiacyclononane‐κ3S1,S4,S7:κS1)tetrasilver(I) tetrakis(trifluoromethanesulfonate) nitromethane disolvate

(1,4,7‐Tri­thia­cyclo­nonane)silver tri­fluoro­methane­sulfonate crystallizes in a tetrameric form from nitro­methane, to give the title compound, [Ag₄(C₆H₁₂S₃)₄](CF₃SO₃)₄·2CH₃NO₂. The complex cation consists of four [AgL]⁺ units (L is 1,4,7‐tri­thia­cyclo­nonane), with four Ag—S—Ag bridges forming a cyclic tetramer. The almost planar Ag₄S₄ ring takes an octagonal form.     

A polymorph of tetrakis(acetonitrile‐κN)copper(I) tetrafluoridoborate

A P2₁2₁2₁ polymorph of the title compound, [Cu(CH₃CN)₄]BF₄, is reported. The crystal structure is very similar to the structure of the Pna2₁ polymorph reported by Jones & Crespo [Acta Cryst. (1998), C 54 , 18–20]. The anions and one of the three independent cations occupy similar positions in both polymorphs. Two of the four symmetry‐related positions of the other two cations are also identical in the two polymorphs, and the other two positions are related by mirror symmetry. The crystal used for the structure determination contained a volume fraction of 0.088 (7) of the Pna2₁ polymorph.     

A two‐dimensional silver(I) coordination polymer constructed from 4‐aminophenylarsonate and triphenylphosphane: poly[[(μ3‐4‐aminophenylarsonato‐κ3N:O:O)(triphenylphosphane‐κP)silver(I)] monohydrate]

The title compound, {[Ag(C₆H₇AsNO₃)(C₁₈H₁₅P)]·H₂O}_n, has been synthesized from the reaction of 4‐aminophenylarsonic acid with silver nitrate, in aqueous ammonia, with the addition of triphenylphosphane (PPh₃). The Ag^I centre is four‐coordinated by one amino N atom, one PPh₃ P atom and two arsonate O atoms, forming a severely distorted [AgNPO₂] tetrahedron. Two Ag^I‐centred tetrahedra are held together to produce a dinuclear [Ag₂O₂N₂P₂] unit by sharing an O–O edge. 4‐Aminophenylarsonate (Hapa⁻) adopts a μ₃‐κ³N:O:O‐tridentate coordination mode connecting two dinuclear units, resulting in a neutral [Ag(Hapa)(PPh₃)]_n layer lying parallel to the (10) plane. The PPh₃ ligands are suspended on both sides of the [Ag(Hapa)(PPh₃)]_n layer, displaying up and down orientations. There is an R₂²(8) hydrogen‐bonded dimer involving two arsonate groups from two Hapa⁻ ligands related by a centre of inversion. Additionally, there are hydrogen‐bonding interactions involving the solvent water molecules and the arsonate and amine groups of the Hapa⁻ ligands, and weak π–π stacking interactions within the [Ag(Hapa)(PPh₃)]_n layer. These two‐dimensional layers are further assembled by weak van der Waals interactions to form the final architecture.     

Monoclinic and triclinic concomitant polymorphs of di‐μ‐pyridazine‐1κ2N:2κ2N′‐bis­[(saccharinato)silver(I)]

Crystallization of the title compound, di‐μ‐pyridazine‐1κ²N:2κ²N′‐bis­[(2,3‐dihydro‐3‐oxobenzisosulfonazolato‐κN)silver(I)], [Ag₂(C₇H₄NO₃S)₂(C₄H₄N₂)₂], from acetonitrile yields both monoclinic, (I), and triclinic, (II), polymorphs. In both forms, the silver(I) ions have a slightly distorted trigonal AgN₃ coordination geometry and are doubly bridged by two neutral pyridazine (pydz) ligands, generating a centrosymmetric dimeric structure. The saccharinate (sac) ligands are N‐coordinated. The dihedral angles between the sac and pydz rings are 8.43 (7) and 7.94 (8)° in (I) and (II), respectively, suggesting that the dimeric mol­ecule is nearly flat. The bond geometry is similar in both polymorphs. In (I), the dimers inter­act with each other via aromatic π_sac–π_pydz stacking inter­actions, forming two‐dimensional layers, which are further crosslinked by weak C—H⋯O inter­actions. Compound (II) exhibits similar C—H⋯O and π–π inter­actions, but additional C—H⋯π and π⋯Ag inter­actions help to stabilize the packing of the dimers.     

Bis(μ‐N,N‐dimethyldithiocarbamato‐κ3S,S′:S′)bis[(dimethoxyphenylphosphane‐κP)(N,N‐dimethyldithiocarbamato‐κ2S,S′)cobalt(III)] bis(hexafluorophosphate)

Purple prismatic crystals of the title compound, [Co₂(C₃H₆NS₂)₄(C₈H₁₁O₂P)₂](PF₆)₂, were obtained by repeated recrystallization of trans‐[Co(C₃H₆NS₂)₂‐(C₈H₁₁O₂P)₂]PF₆ from CH₃CN/Et₂O and then from MeOH/CH₂Cl₂; during recrystallization one of the P(OMe)₂Ph ligands was dissociated from the Co^III center and the resulting Co^III complex fragment underwent dimerization. The complex cation has a dinuclear structure bridged by one S atom of each of two of the N,N‐di­methyl­di­thio­carbamate ligands, and has crystallographically imposed C₂ symmetry. Two P(OMe)₂Ph ligands are coordinated at the transoid positions of the Co₂(μ‐C₃H₆NS₂)₂(C₃H₆NS₂)₂ moiety, with Co—P bond lengths of 2.1921 (11) Å.     

A new polymorph of (O‐ethyl dithio­carbonato‐κ2S,S′)­bis­(tri­phenylphosphine‐κP)silver(I)

A new triclinic polymorphic modification of the title compound, [Ag(C₃H₅OS₂)(C₁₈H₁₅P)₂], has been found and compared with the previously known orthorhombic modification [Tiekink (1988). Coord. Chem. 17 , 239–243]. The two polymorphs have the same molecular shape, viz. a distorted tetrahedral geometry, with a chelating di­thio­carbonate (xanthate) and two PPh₃ ligands bonded to the Ag atom. However, in this new polymorph, the xanthate ligand is bonded asymmetrically to the Ag atom, with Ag—S distances of 2.5489 (6) and 2.8055 (7) Å, while for the orthorhombic polymorph these distances are 2.686 (4) and 2.601 (4) Å. The Ag—P distances are similar in both structures.     

Bis(tetra‐n‐butylammonium) bis(μ‐1,2‐dicyanoethene‐1,2‐dithiolato‐κ3S,S′:S′)bis[(1,2‐dicyanoethene‐1,2‐dithiolato‐κ2S,S′)cobalt(III)]

In the title compound, (C₁₆H₃₆N)₂[Co(C₄N₂S₂)₂]₂, pairs of [Co(C₄N₂S₂)₂]^? anions combine to form discrete crystallographically centrosymmetric dimers, which stack along the c axis, surrounded by the counter‐cations. The metal atom in the anion has a five‐coordinate distorted square‐pyramidal geometry.     

Poly[(μ3‐1,1‐dioxo‐1,2‐benzoisothiazole‐3‐thiolato‐κ3N:S3:S3)silver(I)]

The centrosymmetric title compound, [Ag(C₇H₄NO₂S₂)]_n, consists of dinuclear units in which two thiosaccharinate anions each bridge two Ag atoms via an endocyclic N atom and an exocyclic S atom across a crystallographic centre of inversion midway between the Ag atoms. The dimeric units are connected via Ag—S_exo interactions to create two‐dimensional networks. The thiosaccharinate anions bridge in a μ₃‐S:S:N manner. The Ag...Ag distance can be considered a strong argentophilic interaction.     

Tetrakis(μ‐triisopropylsilanethiolato)‐1:2κ4S:S;2:3κ4S:S‐bis(triisopropylsilanethiolato)‐1κS,3κS‐trizinc(II)

The title compound, [Zn₃(C₉H₂₁SiS)₆] or [(ⁱPr₃SiS)Zn(μ‐SSiⁱPr₃)₂Zn(μ‐SSiⁱPr₃)₂Zn(SSiⁱPr₃)], is the first structurally characterized homoleptic silanethiolate complex of zinc. A near‐linear arrangement of three Zn^II ions is observed, the metals at the ends being three‐coordinate with one terminally bound silanethiolate ligand. The central Zn^II ion is four‐coordinate and tetrahedral, with two bridging silanethiolate ligands joining it to each of the two peripheral Zn^II ions. The nonbonding intermetallic distances are 3.1344 (11) and 3.2288 (12) Å, while the Zn...Zn...Zn angle is 172.34 (2)°. A trimetallic silanethiolate species of this type has not been previously identified by X‐ray crystallography for any element.     

Bis(μ‐4‐chloro­benzoato‐κ2O:O)bis[(2‐aminopyridine‐κN)silver(I)]

The title compound, [Ag₂(C₇H₄ClO₂)₂(C₅H₆N₂)₂], lies about an inversion centre and the Ag atom is three‐coordinated by two O atoms and one N atom from three different ligands. The 4‐chloro­benzoate anion acts as a monodonor ligand, bridging two inversion‐related Ag atoms of the compound into a dimer. There are weak intermolecular N—H⋯O hydrogen bonds in the structure.     

Poly[μ2‐chloro‐μ2‐1,4‐oxathiane‐κ2S:S‐copper(I)]

The title complex, [CuCl(C₄H₈OS)]_n, contains infinite spiral (CuS)_n chains linked by bridging Cl atoms into layers. The Cl atoms do not form polymeric fragments with Cu^I, but combine into isolated centrosymmetric Cu₂Cl₂ units. The compound is non‐isomorphous with the Br‐containing analogue, which contains Cu₈S₈ rings linked by Br atoms into chains. The O atom of the 1,4‐oxathiane mol­ecule does not realize its coordination abilities in the known copper(I)–halide complexes, while in copper(II)–halide complexes, oxathiane is coordinated via the S and O atoms. This falls into a pattern of the preferred inter­actions, viz. weak acid (Cu^I atom) with weak base (S atom) and harder acid (Cu^II atom) with harder base (O atom).     

Bis(2‐amino‐2‐thiazolinium) tetra‐μ‐formato‐κ8O:O′‐bis[(formato‐κO)copper(II)]

In the title dimeric compound, (C₃H₇N₂S)₂[Cu₂(CHO₂)₆], each Cu^II atom has a square‐pyramidal coordination, with the nonbridging formate ion at the apical position. The complex anion is located on a crystallographic inversion centre, with a Cu...Cu separation of 2.6566 (4) Å. 2‐Amino‐2‐thiazolinium cations connect complex anions via hydrogen bonds to form a ribbon running along the a axis.     

Hexa‐μ2‐chloro‐μ4‐oxo‐tetrakis[(2‐ethyl­tetrazole‐κN4)copper(II)]

In the title molecular complex, [Cu₄Cl₆O(2‐EtTz)₄], where 2‐EtTz is 2‐ethyl­tetrazole (C₃H₆N₄), the central O atom is located on the symmetry site and is tetrahedrally coordinated to four Cu atoms, with Cu—O distances of 1.8966 (4) Å. A very slight distortion of Cu₄O from a regular tetrahedron is observed [two Cu—O—Cu angles are 108.76 (3)° and four others are 109.828 (13)°]. Each Cu atom is connected to three others via the Cl atoms, forming a slightly distorted Cl octahedron around the O atom, with O⋯Cl distances of 2.9265 (7) Å for Cl atoms lying on the twofold axis and 2.9441 (13) Å for those in general positions. The Cu atom has a distorted trigonal–bipyramidal environment, with three Cl atoms in the equatorial plane, and with the N atom of the 2‐ethyl­tetrazole ligand and the μ₄‐O atom in axial positions. The Cu atom is displaced out of the equatorial plane by ca 0.91 Å towards the coordinated N atom of the 2‐­ethyl­tetrazole ligand.     

catena‐Poly[[[μ‐1,3‐bis(diphenylphosphanyl)propane‐κ2P:P′][O‐ethyl (4‐methoxyphenyl)phosphonodithioato‐κ2S,S′]silver(I)] chloroform monosolvate]

Reaction of a mixture of AgOAc, Lawesson's reagent [2,4‐bis(4‐methoxyphenyl)‐1,3‐dithiadiphosphetane‐2,4‐disulfide] and 1,3‐bis(diphenylphosphanyl)propane (dppp) under ultrasonic treatment gave the title compound, {[Ag(C₉H₁₂O₂PS₂)(C₂₇H₂₆P₂)]·CHCl₃}_n, a novel one‐dimensional chain based on the in situ‐generated bipodal ligand [ArP(OEt)S₂]⁻ (Ar = 4‐methoxyphenyl). The compound consists of bidentate bridging 1,3‐bis(diphenylphosphanyl)propane (dppp) and in situ‐generated bidentate chelating [ArP(OEt)S₂]⁻ ligands. The dppp ligand links the [Ag{ArP(OEt)S₂}] subunit to form an achiral one‐dimensional infinite chain. These achiral chains are packed into chiral crystals by virtue of van der Waals interactions. No π–π interactions are observed in the crystal structure.     

Poly[[[tri(urea‐κO)manganese(II)]‐μ‐thiocyanato‐κ2N:S‐mercury(II)]‐tri‐μ‐tetrathiocyanato]

The title complex, [MnHg(SCN)₄(CH₄N₂O)₃]_n, consists of slightly distorted octahedral MnN₃O₃ and tetrahedral HgS₄ units. The Mn^II atom is coordinated by the O atoms of three urea mol­ecules and by the N atoms of three SCN^? ions; Hg^II is coordinated by four S atoms from SCN^? ions. Each pair of Mn^II and Hg^II atoms is connected by an –SCN– bridge, forming infinite two‐dimensional –Mn—NCS—Hg– networks.     

catena‐Poly­[[tetrakis(2‐allyl­tetrazole‐κN4)‐tetra‐μ‐chloro‐tricopper(II)]‐di‐μ‐chloro]

In the crystal structure of the title compound, [Cu₃Cl₆(C₄H₆N₄)₄]_n, there are three Cu atoms, six Cl atoms and four 2‐allyl­tetrazole ligands in the asymmetric unit. The polyhedron of one Cu atom adopts a flattened octahedral geometry, with two 2‐allyl­tetrazole ligands in the axial positions [Cu—N4 = 1.990 (2) and 1.991 (2) Å] and four Cl atoms in the equatorial positions [Cu—Cl = 2.4331 (9)–2.5426 (9) Å]. The polyhedra of the other two Cu atoms have a square‐pyramidal geometry, with three basal sites occupied by Cl atoms [Cu—Cl = 2.2487 (9)–2.3163 (8) and 2.2569 (9)–2.3034 (9) Å] and one basal site occupied by a 2‐allyl­tetrazole ligand [Cu—N4 = 2.028 (2) and 2.013 (2) Å]. A Cl atom lies in the apical position of either pyramid [Cu—Cl = 2.8360 (10) and 2.8046 (9) Å]. The possibility of including the tetrazole N3 atoms in the coordination sphere of the two Cu atoms is discussed. Neighbouring copper polyhedra share their edges with Cl atoms to form one‐dimensional polymeric chains running along the a axis.     

The coordination polymer poly[(μ3‐3‐aminocarbonylpyrazine‐2‐carboxylato‐κ3N1:O2:O2′)silver(I)]

The title compound, [Ag(C₆H₄N₃O₃)]_n or [Ag(pyzca)]_n (where pyzca is 3‐aminocarbonylpyrazine‐2‐carboxylate), (I), was obtained by silver‐catalysed partial hydrolysis of pyrazine‐2,3‐dicarbonitrile in aqueous solution. The compound has a distorted trigonal–planar coordination geometry around the Ag^I ion, with each ligand bridging three Ag^I ions to form a one‐dimensional strand of molecules parallel to the b axis. An extensive hydrogen‐bond pattern connects these strands to form a three‐dimensional network of mog topology.