Two isostructural carboranes: 3‐phenyl‐1,2‐dicarba‐closo‐dodecaborane(12) and 1‐phenyl‐1,7‐dicarba‐closo‐dodecaborane(12)

Two phenyl‐substituted carboranes, 3‐phenyl‐1,2‐dicarba‐closo‐dodecaborane(12), C₈H₁₆B₁₀, (I), and 1‐phenyl‐1,7‐dicarba‐closo‐dodecaborane(12), C₈H₁₆B₁₀, (II), were found to be isostructural. Comparison of the bond angles at the ipso‐C atoms of the phenyl substituent for (I) and (II) [117.71 (3) and 118.45 (10)°, respectively] indicates that electron donation of the carborane cage for B‐ and C‐substituted carboranes is different.     

Two tetrahydrofuran solvates of HN(SePPh2)2

The X‐ray crystal structures of P,P′‐imino­bis­(di­phenyl­seleno­phosphine) tetra­hydro­furan solvate, C₂₄H₂₁NP₂Se₂·C₄H₈O, (I), and bis­(tetra­hydro­furan) solvate, C₂₄H₂₁NP₂Se₂·2C₄H₈O, (II), have been determined; (I) has twofold crystallographic symmetry. In each compound, the O atom of one mol­ecule of tetra­hydro­furan is hydrogen bonded to the amide‐H atom of HN(SePPh₂)₂. The conformation of the Se—P—N—P—Se chains in (I), (II), and the crystal structure of the unsolvated HN(SePPh₂)₂ are different.     

Dichloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane]zinc(II) and di‐μ‐chloro‐bis­{chloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane]cadmium(II)}

The Zn atom in dichloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)­methane]zinc(II), [ZnCl₂(C₁₁H₁₆N₄)], (I), is tetra­hedrally coordinated by two N atoms from one bis­(3,5‐dimethyl­pyrazol­yl)methane ligand and two terminal Cl atoms. The mol­ecule has no crystallographic symmetry. One H atom of the CH₂ group of the bis­(3,5‐dimethyl­pyrazol­yl)methane ligand inter­acts with a Cl atom of an adjacent mol­ecule to yield inter­molecular C—H⋯Cl contacts, thereby forming a one‐dimensional zigzag chain extending along the b axis. On the other hand, in di‐μ‐chloro‐bis­{chloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane]cadmium(II)}, [Cd₂Cl₄(C₁₁H₁₆N₄)₂], (II), each of the two crystallographically equivalent Cd atoms is penta­coordinated by two N atoms from one bis­(3,5‐dimethyl­pyrazol­yl)methane ligand, and by one terminal and two bridging Cl⁻ anions. The mol­ecule has a crystallographic centre of symmetry located at the mid‐point of the Cd⋯Cd line. One H atom of the CH₂ group of the bis­(3,5‐dimethyl­pyrazolyl)­methane ligand inter­acts with a Cl atom of an adjacent mol­ecule to produce pairwise inter­molecular C—H⋯Cl contacts, thereby affording chains of mol­ecules running along the c axis.     

Two novel bis­(2,9‐dimeth­yl‐1,10‐phenanthroline)copper(I) complexes: [Cu(dmp)2]2(PF6)2·0.5(bpmh)·CH3CN and [Cu(dmp)2][N(CN)2]

Two new salts of the cation [Cu^I(dmp)₂]⁺ (dmp is 2,9‐dimeth­yl‐1,10‐phenanthroline, C₁₄H₁₂N₂), namely bis­[bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ²N,N′)copper(I)] bis­(hexa­fluorophos­phate) hemi[bis­(4‐pyridylmethyl­idene)hydrazine] acetonitrile solvate, [Cu(C₁₄H₁₂N₂)₂]₂(PF₆)₂·0.5C₁₂H₁₀N₄·C₂H₃N or [Cu(dmp)₂]₂(PF₆)₂·0.5(bpmh)·CH₃CN [bpmh is bis­(4‐pyridylmethyl­idene)hydrazine, C₁₂H₁₀N₄], (I), and bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ²N,N′)copper(I) dicyanamide, [Cu(C₁₄H₁₂N₂)₂](C₂N₃) or [Cu(dmp)₂][N(CN)₂], (II), are reported. The Cu—N bond lengths and the distortion from idealized tetra­hedral geometry of the dmp ligands are discussed and compared with related compounds. The bpmh molecule in (I) is π–π stacked with a dmp ligand at a distance of 3.4 Å, rather than coordinated to the metal atom. The molecule lies across an inversion center in the crystal. In (II), the normally coordinated dicyanamide mol­ecule is present as an uncoordinated counter‐ion.     

New electron‐deficient chiral phosphines: (4R,5R)‐1,3‐bis(trifluoromethanesulfonyl)perhydro‐1,3,2‐benzodiazaphosphol‐2‐yl] substituted amines

Three chiral electron‐deficient phosphine ligands, [(4R,15R)‐,3‐bis­(tri­fluoro­methane­sulfonyl)­per­hydro‐1,3,2‐benzodiazaphosphol‐2‐yl]­diethyl­amine, C₁₂H₂₀F₆N₃O₄PS₂, (IIIa), [(4R,5R)‐1,3‐bis­(tri­fluoro­methane­sulfonyl)­per­hydro‐1,3,2‐benzodi­aza­phosphol‐2‐yl]­di­methyl­amine, C₁₀H₁₆F₆N₃O₄PS₂, (IIIb), and bis­[(4R,5R)‐1,3‐bis­(tri­fluoro­methane­sulfonyl)­per­hydro‐1,3,2‐benzodi­aza­phosphol‐2‐yl]­methyl­amine, (IV), as the chloroform solvate, C₁₇H₂₃F₁₂N₅O₈P₂S₄·0.98CHCl₃, have been prepared from (1R,2R)‐N,N′‐bis­(tri­fluoro­methane­sulfonyl)‐1,2‐cyclo­hexane­di­amine and diethyl phosphor­amido­us dichloride, dimethyl phosphoramidous dichloride or methyl imidodi­phosphorus tetrachloride. The π‐acceptor abilities of these new types of ligands have been evaluated by X‐ray determination of the P—N bond lengths; it has been found that the most promising ligand is the bis­(phosphine) (IV).     

1,2‐Bis­(methylsulfanyl)‐1,2‐dicarba‐closo‐dodecaborane(12)

In the title compound, 1,2‐(SCH₃)₂‐1,2‐closo‐C₂B₁₀H₁₀ or C₄H₁₆B₁₀S₂, the methylsulfanyl groups are bonded to the C atoms of the 1,2‐dicarba‐closo‐dodecaborane cage. The C_cage—C_cage distance is 1.8033 (18) Å and the S—C_cage—C_cage—S torsion angle is 1.07 (13)°. The C_cage—C_cage distance is compared with those in other 1,2‐dicarba‐closo‐dodecaborane derivatives.     

1,3‐Dibenzoylimidazolidine‐2‐thione and 1,3‐dibenzo­yl‐3,4,5,6‐tetra­hydro­pyrimidine‐2(1H)‐thione

The title compounds, 1,3‐dibenzo­ylimidazolidine‐2‐thione, C₁₇H₁₄N₂O₂S, (I), and 1,3‐dibenzo­yl‐3,4,5,6‐tetra­hydro­pyrimidine‐2(1H)‐thione, C₁₈H₁₆N₂O₂S, (II), were obtained from the reactions of imidazolidine‐2‐thione and 1,4,5,6‐tetra­hydro­pyrimidine‐2‐thiol, respectively, with benzoyl chloride. Compounds (I) and (II) contain, respectively, imidazolidinethione [C=S = 1.6509 (14) Å] and ­pyrimidinethione [C=S = 1.6918 (19) Å] moieties bonded to two benzoyl rings. The mol­ecules of (I) exhibit C₂ symmetry, the C=S bond lying along the twofold rotation axis, while the mol­ecules of (II) have mirror symmetry (C_s). The imida­zolidine ring in (I) is essentially planar, while the pyrimidine ring in (II) adopts a boat conformation. Mol­ecules of (I) are linked by weak inter­molecular C—H⋯O inter­actions, while mol­ecules of (II) are held together by van der Waals inter­actions.     

A bis­(acetyl­acetonato)­uranium(IV) complex of the Schiff base N,N′‐bis(3‐hydroxy­salicyl­idene)‐2‐methyl‐1,2‐propane­di­amine

The title complex, bis­(acetyl­acetonato‐κ²O,O′)[N,N′‐bis(3‐hydroxy‐2‐oxidobenzaldimino)‐2‐methyl‐1,2‐propane­di­amine‐κ⁴N,O,O′,N′]­uranium(IV) tetra­hydro­furan solvate, [U(C₁₈H₁₈N₂O₄)(C₅H₇O₂)₂]·C₄H₈O, is a rare example of a uranium(IV) complex with a compartmental Schiff base. The U atom is located in the N₂O₂ inner site of the hexadentate N,N′‐bis(3‐hydroxy‐2‐oxidobenzaldimino)‐2‐methyl‐1,2‐pro­pane­di­amine group and is bound also to the two O atoms of both acetyl­acetonate moieties, which results in a dodecahedral coordination environment. Centrosymmetric dimers are formed through intermolecular hydrogen bonds that link the terminal uncoordinated hydroxy groups to one another and to the O atoms of the acetyl­acetonate ligands.     

trans‐Di­chloro‐cis‐bis(3,6‐di­methyl­carbazolyl)‐cis‐bis­(tetra­hydro­furan)­zirconium(IV) benzene sesquisolvate

In the title compound, [ZrCl₂(C₁₄H₁₂N)₂(C₄H₈O)₂]·1.5C₆H₆, the Zr atom is pseudo‐octahedral, with two Cl atoms in trans positions and two tetra­hydro­furan mol­ecules in cis positions. The two 3,6‐di­methyl­carbazolyl ligands are in cis positions and are canted with respect to one another. The two Zr—N distances are 2.1148 (18) and 2.1236 (18) Å, and the N—Zr—N angle is 95.08 (7)°. The title compound crystallizes as the benzene solvate, with one of the benzene mol­ecules positioned on an inversion center.     

Facial π⋯Cl⋯π inter­actions as the directing motif of the supra­molecular structures of Mg2+ and Ca2+ bis[hydro­tris(pyrazol­yl)­borate] chloro­form disolvates

The isomorphous complexes bis­[hydro­tris(pyrazol­yl)­borato]­mag­nesium(II) chloro­form disolvate, [Mg(C₉H₁₀BN₆)₂]·2CHCl₃, and bis­[hydro­tris(pyrazol­yl)borato]calcium(II) chloro­form disolvate, [Ca(C₉H₁₀BN₆)₂]·2CHCl₃, crystallize in the cubic space group Pa with Z = 4. The metal atoms occupy sites of symmetry, and their coordination is very similar to that found for the unsolvated Mg[HB(Pz)₃]₂ and Ca[HB(Pz)₃]₂ complexes (Pz is pyrazole). The inclusion of chloro­form mol­ecules on threefold rotation axes not only leads to high‐symmetry crystal structures but also plays an important role in stabilizing the three‐dimensional supramolecular architecture through facial Pz⋯Cl⋯Pz inter­actions.     

(1S,2R,2′S)‐ and (1S,2S,2′S)‐1‐phenyl‐2‐phenyl­thio‐2‐(tetra­hydro­pyran‐2′‐yl­thio)­ethanol diastereoisomers at 193 K

In the synthesis of 1‐phenyl‐2‐phenyl­thio‐2‐(tetra­hydro­pyran‐2‐yl­thio)­ethanol, C₁₉H₂₂O₂S₂, four diastereoisomers are formed. Two non‐centrosymmetric enantiomeric forms which crystallize in space groups P2₁2₁2₁ and Pna2₁ are presented. The former has an intramolecular hydrogen bond between the hydroxyl group and the O atom of the tetra­hydro­pyran ring. In the latter isomer, the hydroxyl group forms an intermolecular hydrogen bond to the O atom of the tetra­hydro­pyran­yl group of a neighbouring mol­ecule, joining the mol­ecules into chains in the c‐axis direction; the O?O distances are 2.962 (4) and 2.764 (3) Å, respectively. The tetra­hydro­pyran rings are in chair conformations in both isomers and the S side chain has an equatorial orientation in the former, but an axial orientation in the latter mol­ecule.     

(μ‐Tri‐tert‐butoxysilanethiol­ato)­bis[(tetra­hydro­furan)lithium(I)] and catena‐poly[[bis­(μ‐tri‐tert‐butoxy­silanethiol­ato)dilithium(I)]‐μ‐dimethoxy­ethane]: solvent coordination as the structure‐forming factor

The title compounds, μ‐(tri‐tert‐butoxy­silanethiol­ato‐κ²S:S)‐bis[(tetra­hydro­furan‐κO)lithium(I)], [Li₂(C₁₂H₂₇O₃SSi)₂(C₄H₈O)₂], (I), and catena‐poly[[bis­(μ‐tri‐tert‐butoxysilanethiol­ato)‐1:2κ²S;1κS:2κS,O‐dilithium(I)]‐μ‐dimethoxy­ethane‐κ²O:O′], [Li₂(C₁₂H₂₇O₃SSi)₂(C₄H₁₀O₂)]_n, (II), were obtained by the reaction of tri‐tert‐butoxy­silanethiol with metallic lithium. The crude product, when recrystallized from tetra­hydro­furan (THF) yields (I), and when recrystallized from 1,2‐dimethoxy­ethane (DME) gives (II). Compound (I) forms centrosymmetric dimers in the solid state with an Li₂S₂ central core, whereas (II) forms infinitely long chains, in which the centrosymmetric dimeric units are linked together by the bidentate DME ligand (also residing on an inversion centre), thus forming a coordination polymer. The formation of a one‐dimensional structure in (II) is a consequence of replacement of a monodentate THF solvent mol­ecule with a bidentate DME mol­ecule.     

The dimeric mixed‐ligand titana­carborane sandwich [1‐(Cp)‐1‐Ti‐2‐(Me)‐3‐(SiMe3)‐2,3‐C2B4H4]2

The title dimer, bis­[1‐cyclo­penta­dienyl‐2‐methyl‐1‐titana‐3‐tri­methylsilyl‐2,3‐dicarba‐closo‐hexaborane(6)], [Ti(C₅H₅)(C₆­H₁₆­B₄Si)]₂, reveals that the centrosymmetric mol­ecule consists of two bent‐sandwich titanacarboranes bridged by the B—H—Ti bonds. The average bond distances are Ti—B 2.445 (3), Ti—C(cage) 2.334 (2) and Ti—C(Cp) 2.376 (3) Å, and the corresponding bond angles are Cp—Ti—Cp 163.2 (1) and Cp—Ti—Cb (Cb = C₂B₃ face) 139.9 (1)°; the Ti—H separations are 2.10 (2) and 2.19 (2) Å.     

Two furo­pyridine complexes of nickel(II) iso­thio­cyanate

Pyridine fused with a furan ring (fupy), and its di­methyl derivative, have been used for the first time as ligands to synthesize potentially new Werner clathrates. The extended aromatic system of pyridine‐like ligands influences considerably the molecular structure of prepared nickel complexes. The molecular structure of tetrakis­(furo­[3,2‐c]­pyridine)­bis(iso­thio­cyanato)­nickel(II) tetra­hydro­furan (THF) solvate, [Ni(NCS)₂(C₇H₅NO)₄]·C₄H₈O or [Ni(NCS)₂(fupy)₄]·THF, (I), reveals a `four‐blade propeller' arrangement of ligands, with the angles between the fupy planes and the basal octahedron plane spanning the range 38.7–55.3°. These angles are much larger (69.9–78.8°) in the centrosymmetric complex tetrakis(2,3‐di­methyl­furo­[3,2‐c]­pyridine)­bis­(iso­thio­cyanato)nickel(II) 6.6‐hydrate, [Ni(NCS)₂(C₉H₉NO)₄]·6.6H₂O or [Ni(NCS)₂(Me₂fupy)₄]·6.6H₂O, (II), in which crystallographically imposed inversion symmetry is present.     

(Z)‐2‐Methylbuten‐1‐yl(aryl)iodonium trifluoromethanesulfonates containing electron‐withdrawing groups on the aryl moiety

The crystal structures of [(Z)‐2‐methyl­but‐1‐en‐1‐yl]­[4‐(tri­fluoro­methyl)­phenyl]­iodo­nium tri­fluoro­methane­sulfonate, C₁₂H₁₃F₃I⁺·CF₃O₃S^?, (I), (3,5‐di­chloro­phenyl)­[(Z)‐2‐methyl­but‐1‐en‐1‐yl]­iodo­nium tri­fluoro­methane­sulfonate, C₁₁H₁₂­Cl₂I⁺·CF₃O₃S^?, (II), and bis{[3,5‐bis­(tri­fluoro­methyl)­phenyl][(Z)‐2‐methyl­but‐1‐en‐1‐yl]­iodo­nium} bis­(tri­fluoro­methane­sulfonate) di­chloro­methane solvate, 2C₁₃H₁₂F₆I⁺·­2CF₃­O₃S^?·CH₂Cl₂, (III), are described. Neither simple acyclic β,β‐di­alkyl‐substituted alkenyl­(aryl)­idonium salts nor a series containing electron‐deficient aryl rings have been described prior to this work. Compounds (I)–(III) were found to have distorted square‐planar geometries, with each I atom interacting with two tri­fluoro­methane­sulfonate counter‐ions.     

rac‐(Z)‐Ethyl 2‐bromo‐2‐[(3R,5R)‐3‐bromo‐5‐methyl­tetra­hydro­furan‐2‐yl­idene]acetate

In the title compound, C₉H₁₂Br₂O₃, a (tetra­hydro­furan‐2‐yl­idene)acetate, the double bond has the Z form. In the tetra­hydro­furan group, the relative configuration of the Br atom in the 3‐position and the methyl group in the 5‐position is anti. The compound crystallizes with two independent mol­ecules per asymmetric unit and, in the crystal structure, the individual mol­ecules are linked to their symmetry‐equivalent mol­ecules by C—H⋯O hydrogen bonds, so forming centrosymmetric hydrogen‐bonded dimers.     

A novel three‐dimensional copper(II) coordination polymer with 1,4‐bis(1,2,4‐triazol‐1‐ylmeth­yl)benzene and thio­cyanate

In the title complex, poly[copper(II)‐di‐μ₂‐thio­cyanato‐μ₂‐1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene], [Cu(NCS)₂(C₁₂H₁₂N₆)]_n, the Cu^II atom lies on an inversion centre in a tetra­gonally distorted octa­hedral environment. Four N atoms from thio­cyanate and 1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene (bbtz) ligands fill the equatorial positions, and S atoms from symmetry‐related thio­cyanate ligands fill the axial positions. The benzene ring of the bbtz ligand lies about an inversion centre. Single thio­cyanate bridges link the Cu^II atoms into two‐dimensional sheets containing an unprecedented 16‐membered [Cu₄(μ‐NCS‐N:S)₄] ring. The bbtz ligands further link the two‐dimensional sheets into a three‐dimensional network.     

Four bis(1‐chloro‐2,2,4,4‐tetramethyl‐3‐oxocyclobutan‐1‐yl)oligosulfanes

The four oligosulfanes, bis(1‐chloro‐2,2,4,4‐tetra­methyl‐3‐oxo­cyclo­butan‐1‐yl)­disulfane, C₁₆H₂₄Cl₂O₂S₂, (III), 1,3‐bis(1‐chloro‐2,2,4,4‐tetra­methyl‐3‐oxo­cyclo­butan‐1‐yl)­trisulfane, C₁₆H₂₄Cl₂O₂S₃, (V), 1,4‐bis(1‐chloro‐2,2,4,4‐tetra­methyl‐3‐oxo­cyclo­butan‐1‐yl)­tetrasulfane, C₁₆H₂₄Cl₂O₂S₄, (VII), and 1,6‐bis(1‐chloro‐2,2,4,4‐tetra­methyl‐3‐oxo­cyclo­butan‐1‐yl)­hexasul­fane, C₁₆H₂₄Cl₂O₂S₆, (VIII), all have similar geometric parameters, with the C—C bond lengths involving the chloro‐substituted cyclo­butanyl C atom being elongated to about 1.59 Å. There are two mol­ecules in the asymmetric units of the tri‐ and tetrasulfanes, and the mol­ecules in the latter compound have local C₂ symmetry. The mol­ecule of the hexasulfane has crystallographic C₂ symmetry. Most of the cyclo­butanyl rings are not perfectly planar and have slight but varying degrees of distortion towards a flattened tetrahedron. The polysulfane chain in each structure has a helical conformation, with each additional S atom in the chain adding approximately one quarter of a turn to the helix.     

Di‐μ‐phenyl­thio‐bis­[bis(η5‐methyl­cyclo­penta­dienyl)(tetra­hydro­furan)lanthanum(III)] bis­(tetra­hydro­furan) solvate

The title complex, [La₂(C₆H₇)₄(C₆H₅S)₂(C₄H₈O)₂]·2C₄H₈O, is a centrosymmetric dimer bridged through the S atoms of the benzene­thiolate ligands. The bridging La₂S₂ unit is completely planar, while the geometry around the nine‐coordinate La atom is that of a distorted trigonal bipyramid. The La—S—La and S—La—S angles are 117.51 (4) and 62.5 (1)°, respectively, and the average La—S bond length is 2.9759 Å. The crystals contain two tetra­hydro­furan solvate mol­ecules for every complex mol­ecule.     

(Aceto­nitrile)­[2,6‐bis­(pyrazol‐1‐yl)­pyridine](isonicotin­amide)copper(II)–tetra­fluoro­borate–aceto­nitrile (1/2/2)

Molecules of the title compound, [Cu(C₂H₃N)(C₁₁H₉N₅)(C₆H₆N₂O)](BF₄)₂·2C₂H₃N, comprise (aceto­nitrile)[2,6‐bis(pyrazol‐1‐yl)­pyridine](isonicotin­amide)copper(II) cations, tetra­fluoro­borate anions and lattice aceto­nitrile mol­ecules. The cations have distorted square‐pyramidal geometries in which the N₃‐donor, viz. 2,6‐bis­(pyrazol‐1‐yl)­pyridine, and the N‐donor, viz. the isonicotin­amide ligand, occupy the four basal positions, with the coordinated aceto­nitrile N‐donor atom occupying the apical position. Pairs of cations are linked by N—H?F hydrogen bonds through tetra­fluoro­borate anions, forming centrosymmetric dimers, which are further linked by C—H?O hydrogen bonds into two‐dimensional undulating sheets, three of which interpenetrate to generate a two‐dimensional network.