Observed Diffractometer Data Research Articles

ChemInform Abstract: SYNTHETIC AND STRUCTURAL STUDIES OF TIN(IV) COMPLEXES OF CROWN ETHERS

AbstractDie Reaktion von Sn(IV)‐Halogeniden mit Crownethern in MeOH oder MeOH/ CHCI; liefert die Komplexe (Ia) und (Ib), Umkristallisation des Chloro‐Komplexes von I8‐Crown‐6 aus den gleichen Lösungsmitteln führt durch weitere Hydratation zu (Ic) bzw. (ll).

ChemInform Abstract: DONOR PROPERTIES OF ARYLPHOSPHINES TOWARDS SELENIUM: X‐RAY CRYSTAL STRUCTURE OF TRIS(M‐TRIFLUOROMETHYLPHENYL)PHOSPHINE SELENIDE

Crystals of the title compound are orthorhombic, space group Pbca, with a= 31.822(15), b= 11.047(6), c= 12.426(7)A, and Z= 8. The structure was solved using multisolution direct methods and refined by least squares to R 0.054 (R′ 0.059) for 1 964 observed diffractometer data. Phosphorus adopts a distorted tetrahedral geometry with mean Se–P–C and C–P–C angles of 113.1 and 105.6° respectively. The P–Se bond length [2.094(2)A] is the shortest reported for a tertiary phosphine selenide and is attributed to the electron-withdrawing properties of the (C6H4CF3-m) groups and the consequent increased s character of the phosphorus orbital involved in bonding with selenium.

Crystal Structure of 2-Thiopyrrole-1,2-dicarboximide-(bis-triphenylphosphine)copper(I)chloride, [(Ph3P)2Cu(Cl)C6H4N2OS

Crystals of the title compound are monoclinic, space group C2/c, a = 3858.0(7), b = 1013.8(2), c = 2982.1(6) pm, β = 139.76(3)° and Z = 8. The structure was refined to R = 0.063 for 2155 unique observed diffractometer data. The copper atom is coordinated tetrahedrally by 2P, CI and S, contrary to a previous spectroscopic assignment

Preparation and Structure of Tetraphenylphosphonium Aquotetrachlorothionitrosylosmium(II), [PPh4][(H2O)Os(NS)Cl4

Trithiazyltrichloride reacts with osmium trichloride to give a green product of composition Os(NS)Cl3 (1). Addition of [PPh4]Cl to 1 in aqueous solution yields [PPh4]2[Os(NS)Cl5] (2) which is converted to [PPh4][(H2O)Os(NS)CI4] (3) by recrystallisation from a 1:1 water/methanol mixture. Crystals of 3 are monoclinic, space group P21/c, with a = 1103.3(2), b = 1959.8(3), c = 1254.3(2) pm, β = 96.51(3)° and Z = 4. The structure was solved by automated Patterson interpretation and refined to R = 0.029 for 3177 unique observed diffractometer data. The osmium atom is octahedrally co-ordinated with H2O trans to the NS group. The Os-N-S unit is almost linear [174.9(3)°] with Os-N 173.1(4) and N-S 151.4(5) pm. The anions form dimeric units in the crystal, each held together by four O-H···Cl hydrogen bonds

Mercury(II) halide complexes of tertiary phosphines. Part VIII. Structural characterisation of the mixed cadmium-mercury complex I 2Cd(μ-I) 2Hg(PPr 3) 2

Reaction of equimolar amounts of Cd 2I 4(PPr 3) 2 and Hg 2I 4(PPr 3) 2 leads to formation of the complex CdHgI 4(PPr 3) 2. Phosphorus-31 and mercury-199 nmr studies show both phosphines to be co-ordinated to mercury in solution, and a single crystal X-ray analysis confirms the unsymmetrical nature of the complex in the solid state also: I 2Cd(μ-I) 2Hg(PPr 3) 2. The crystals of the complex are monoclinic, space group P2 1/c, with a = 10.694(6), b = 13.794(7), c = 22.415(9) Å, β = 96.25(5)°. The structure was solved via the heavy-atom method and refined to an R value of 0.048 for 3053 observed diffractometer data. The [CdI 2Hg] ring is almost planar and each metal atom is four co-ordinate. The coordination polyhedron about mercury is highly irregular and the large PHgP angle of 152.8(1)° is attributed both to the presence of two strong σ-donor phoshines and to the bridging nature of the halogen atoms attached to mercury. The far-i.r. spectrum of the complex is discussed.

Preparation and crystal structures of [As(CF3)2O(OH)]2, [As(CF3)-O(OH)Cl]2, and As4(CF3)6O6(OH)2; a novel cage structure containing four- and six-co-ordinated arsenic

The compounds [As(CF3)2O(OH)]2(1) and As4(CF3)6O6(OH)2(3) have been prepared by oxidative hydrolysis of As(CF3)3, and a mixture of As(CF3)l2 and As(CF3)2l, respectively; [As(CF3)O(OH)Cl]2(2) was isolated from the reaction of compound (3) with SiMe3Cl. Crystals of compound (1) are triclinic, space group P, a= 584.2(1), b= 703.7(1), c= 958.6(1) pm, α= 103.91(1), β= 103.10(1), γ= 107.90(1)°, and Z= 1. Crystals of compounds (2) and (3) are monoclinic, space group P21/n, with a= 554.3(1), b= 934.5(2), c= 1 149.6(2) pm, β= 92.70(1)°, and Z= 2 for (2), and a= 880.3(2), b= 1 011.4(2), c= 1 256.7(3) pm, β= 104.17(2)°, and Z= 2 for (3). The structures were refined to R= 0.036, 0.038, and 0.046 for 1 520, 749, and 1 328 unique observed diffractometer data for compounds (1), (2), and (3), respectively. All three molecules have centrosymmetric structures with four-membered (AsO)2 rings. In compounds (1) and (2) the rings bridge equatorial and axial positions of the trigonal-bipyramidal co-ordinated arsenic atoms; the equatorial ring As–O bonds are much shorter than the axial ring As–O bonds. The structures may be interpreted as intermediate stages in a dimerisation reaction pathway. Compound (3) possesses a novel cage structure involving octahedrally and tetrahedrally co-ordinated arsenic, and an (AsO)4 ring in which the AsIII–O bonds are much shorter than AsV–O bonds.

Reaction between magnesium chloride and iron(III) chloride in tetrahydrofuran. The crystal structure of Di-μ-chlorodichloroiron(II) tetrakis(tetrahydrofuran)magnesium(II)

The direct reaction between magnesium chloride and iron(III) chloride in tetrahydrofuran (THF) yields the [MgCl(THF) 5][FeCl 4] complex ( I). It is unstable and in reacting with THF undergoes reduction to produce the complex FeCl 2(μ-Cl) 2Mg(THF) 4 ( II). Crystals of ( II) are orthorhombic, space group Pbcn, with a = 9.18(1) b = 16.30(2) c = 15.85(1)Å. The structure was solved by the heavy atom method and refined by least squares to R = 0.053 for 1194 observed diffractometer data. The molecule is heterobimetallic with an Fe…Mg distance 3.455(3)Ǎ and the Fe and Mg atoms are bridged by two Cl atoms.

Synthetic and structural studies of tin(IV) complexes of crown ethers

Fourteen inorganic tin(IV) and organotin(IV) complexes of crown ethers (L), of general formulae SnX4·L·2H2O, SnCl4·L·4H2O·nCHCl3(n= 0 or 1), (SnR2X2)n·L·2H2O (n= 1 or 2), and (SnPh3X)2·L·2H2O, have been synthesised. The structure and bonding in these adducts are discussed in terms of their i.r. and 119Sn Mossbauer spectroscopic data. These suggest co-ordination to the tin either by one or more of the polyether O atoms, or by the water molecules of hydration (the crown ether acting as a second-sphere ligand). The latter structure is confirmed by a single-crystal X-ray determination of Sn(OH2)2Cl4·18-crown-6·2H2O·CHCl3. The crystals are monoclinic, space group P21/n, with a= 10.315(6), b= 13.630(8), c= 20.649(13)A, and β= 94.68(5)°. The structure was solved using multisolution direct methods and refined by least squares to R= 0.062 (R′= 0.068) for 3 142 observed diffractometer data. The water molecules within the octahedral Sn(OH2)2Cl4 units are found to be cis to each other and are involved in an extensive hydrogen-bonding scheme. The latter links together the 18-crown-6 molecules, unco-ordinated water molecules, and Sn(OH2)2Cl4 octahedra, to give hydrogen-bonded chains which run parallel to the b axis.

Donor properties of arylphosphines towards selenium: X-ray crystal structure of tris(m-trifluoromethylphenyl)phosphine selenide

Crystals of the title compound are orthorhombic, space group Pbca, with a= 31.822(15), b= 11.047(6), c= 12.426(7)A, and Z= 8. The structure was solved using multisolution direct methods and refined by least squares to R 0.054 (R′ 0.059) for 1 964 observed diffractometer data. Phosphorus adopts a distorted tetrahedral geometry with mean Se–P–C and C–P–C angles of 113.1 and 105.6° respectively. The P–Se bond length [2.094(2)A] is the shortest reported for a tertiary phosphine selenide and is attributed to the electron-withdrawing properties of the (C6H4CF3-m) groups and the consequent increased s character of the phosphorus orbital involved in bonding with selenium.

Mercury(II) halide complexes of tertiary phosphines. Part 9. Study of the tris(2-cyanoethyl)phosphine complexes [HgX2{P(CH2CH2CN)3}m](X = Cl, Br, or I; m= 1 or 2): crystal structures of [HgBr2{P(CH2CH2CN)3}2]· Me2CO and [{HgCl2[P(CH2CH2CN)3]}n

The complexes [HgX2{P(CH2CH2CN)3}m](X = Cl, Br, or I; m= 1 or 2) have been prepared and characterised by analytical and far-i.r. spectroscopic data. In addition, the X-ray crystal structures of [HgBr2{P(CH2CH2CN)3}2]·Me2CO (1) and [{HgCl2[P(CH2CH2CN)3]}n](2) have been determined. Crystals of (1) are monoclinic, space group P21/n, with a= 9.174(6), b= 15.795(9), c= 20.741 (11)A, β= 93.01 (5)°:, and Z= 4; those of (2) are orthorhombic, space group P212121, with a= 20.872(14), b= 7.854(8), c= 8.519(9)A, and Z= 4. Both structures were solved using the heavy-atom method and refined to final R values of 0.043 for (1) and 0.053 for (2) using 2 511 and 1 252 observed diffractometer data respectively. Complex (1) is found to be monomeric, while (2) adopts a polymeric structure in which almost linear Cl–Hg–P(CH2CH2CN)3 units are linked by chlorine atoms to give single chains. The geometry about mercury in the two complexes indicates tris(2-cyanoethyl)phosphine to be a strong σ-donor and comparable with triethylphosphine in its interactions with mercury(II) halides. This is confirmed by far-i.r. studies of the six complexes prepared.

ChemInform Abstract: SYNTHESES OF SOME ORGANOGOLDTRIOSMIUM CLUSTERS: X‐RAY CRYSTAL STRUCTURE OF (OS3(CO)8(PPH3)(AU(PPH3))(2‐NHC5H4N))

Abstract(CO)8(PPh3) Au(PPh3) (2‐NHC5H4N)].

ChemInform Abstract: PREPARATION AND SOME REACTIONS OF (OS5(CO)19): THE MOLECULAR STRUCTURES OF (OS5(CO)19) AND (OS5(CO)16(P(OME)3)3)

AbstractDie Reaktion des Os‐Clusters (I) mit CO bei 160°C und 90 at führt zur Bildung der Verbindung (II), in deren Metallatomgerüst zwei Os‐Dreiecke über eine gemeinsame Ecke verknüpft sind.

Synthesis of triosmium clusters containing amidine ligands: X-ray structural characterization of [Os3(µ-H)(CO)9{NPhC(Ph)NH}

Reactions of [Os3(CO)10(NCMe)2] with amidines have been used to synthesize the complexes [Os3(µ-H)(CO)10{NHC(Me)NH}](1) and [Os3(µ-H)(CO)10{NPhC(Ph)NH}](2); these amidine clusters have been thermally decarbonylated to the corresponding nonacarbonyl compounds of which [Os3(µ-H)(CO)9(MeCN2H2)](3), alone, exists as two tautomeric forms in CDCl3 solution at 20 °C. The structure of [Os3(µ-H)(CO)9{NPhC(Ph)NH}](4) was established by X-ray crystallography. The complex crystallises in the monoclinic space group P21/c with a= 20.002(10), b= 14.492(7), c= 17.999(6)Å, β= 102.80(3)°, and Z= 8. The structure was solved by a combination of direct methods and Fourier-difference techniques, and refined to R= 0.047 for 3 565 unique, observed diffractometer data. There are two independent but structurally similar molecules of (4) per asymmetric unit. In each molecule the Os atoms define an isosceles triangle one edge of which is bridged by the protonated nitrogen atom of the NPhC(Ph)NH ligand; the other N atom is terminally bound to the third Os atom in an axial site. In this way the amidine-ligand caps one triangular face of the metal framework and formally donates five electrons to the cluster.

Some reactions of [Os3(CO)10(NCMe)2] with arenes; the molecular structure of [Os3H2(CO)9(C6H4)

The cluster [Os3H2(CO)9(C6H4)] was obtained in good yield by the reaction of [Os3(CO)10(NCMe)2] with benzene under reflux. This benzyne cluster crystallises in space group P21/c with a= 17.391(5), b= 13.190(2), c= 16.512(3)A, β= 92.39(2)°, and Z= 8. The structure was solved by a combination of direct methods and Fourier difference techniques, and refined by blocked-cascade least squares to R= 0.079 for 3 438 observed diffractometer data. In each of the two independent molecules the three Os atoms define an irregular triangle the longest edge [mean 3.034(4)A] of which is bridged by the benzyne ligand which is co-ordinated to the third Os atom via a π bond. This long edge is also bridged by a hydride and the other hydride bridges one of the other Os–Os edges [mean 2.858(3)A]. The third Os–Os edge [mean 2.751(2)A] is unbridged. When the reaction is carried out in toluene or chlorobenzene rather than benzene the complexes [Os3H2(CO)9(C6H3Me)] and [Os3H2(CO)9(C6H3Cl)] are obtained. In each case two isomers have been identified by 1H n.m.r. spectroscopy. With trans-stilbene the only complex characterised has been formulated as [Os3H2(CO)9(C6H3CHCHC6H5)] in which one ring is co-ordinated to the cluster in a similar manner to that in [Os3H2(CO)9(C6H4)].

Crystal structure of the complex cis-oxobis[piperidine N-oxido(1–)-NO]thiomolybdenum(VI), containing a cis-MoOS2+group

The first example of a MoOS2+ complex, cis-[MoOS(C5H10NO)2][C5H10NO = piperidine N-oxido(1–)], prepared by reaction of the corresponding cis-MoO22+ complex with B2S3, has been crystallographically characterised. The title compound crystallises in the monoclinic space group P21/n, with a= 9.671(1), b= 22.401(2), c= 13.116(2)A, β= 95.51(1)°, and eight molecules, comprising two crystallographically distinct species, per unit cell. The structure has been determined from 4 033 unique observed diffractometer data and refined to R= 0.047. The two independent molecules are virtually identical, and possess Mo–O and Mo–S bonds of length 1.723(12) and 2.106(5)A respectively and an O–Mo–S interbond angle of 116.9(7)°. The dimensions and a selection of spectroscopic properties of the title complex are compared with those of the corresponding cis-[MoY2(C5H10NO)2](Y = O or S) complexes; cis-[MoS2(C5H10NO)2] may be prepared by treating the MoOS2+ complex with B2S3.

Syntheses of some organogoldtriosmium clusters; X-ray crystal structure of [Os3(CO)8(PPh3){Au(PPh3)}(2-NHC5H4N)

The clusters [Os3(CO)9{Au(PPh3)}(C2Ph)](1), [Os3(CO)10{Au(PPh3)}(OH)](2), [Os3(CO)10{Au(PPh3)}(NHSO2C6H4Me-p)](3), and [Os3(CO)8(Y){Au(PPh3)}(2-NHC5H4N)][Y = PPh3(4) or CO (5)] were prepared from the appropriate neutral osmium cluster and chloro(triphenylphosphine)gold(I). [Os3(CO)8(PPh3){Au(PPh3)}(2-NHC5H4N)](4) was shown by X-ray analysis to consist of an isosceles triangle of osmium atoms substituted by an equatorial phosphine ligand and eight carbonyls. A 2-pyridylamido ligand caps one side of the Os3 triangle and a (triphenylphosphine)aurio group bridges the longest Os–Os bond. The complex crystallises in space group P21/n with a= 14.567(5), b= 18.010(24), c= 18.456(7)Å, β= 92.22(3)°, and Z= 4. The structure was solved by a combination of direct methods and Fourier-difference techniques, and refined by blocked-cascade least-squares methods to R= 0.065 to 3 541 observed diffractometer data.

Reactions of tetrasulphur tetranitride with titanium and vanadium tetrachlorides; crystal structure of VCl2(S2N3)

Tetrasulphur tetranitride reacts with excess of VCl4 in CH2Cl2to form a mixture of VCl2(S2N3)(2) and S2N2·VCl4(3), whereas with excess of TiCl4 only S4N4·TiCl4(1) is formed. Crystals of (2) are triclinic, space group P, with a= 571.3(2), b= 695.7(3), c= 772.9(3) pm, α= 95.38(3), β= 99.62(3), γ= 97.58(3)°, and Z= 2. The structure was refined to R= 0.053 for 1 601 unique observed diffractometer data. It consists of chlorine-bridged dimers, linked by additional weak V–N interactions to form polymeric chains. The six-membered VNSNSN ring is effectively planar.

Reactions of [Ru5C(CO)15], involving bridging ligands : crystal and molecular structures of the complexes [Ru5(H)C(CO)14(SEt)], [Ru5(H)C(CO)13(PPh3)(SEt)], [Ru5(H)C(CO)12(PPh3)(SEt)], and [Ru5C(CO)13(PPh3){µ-Au(PPh3)}(µ-I)

The cluster [Ru5C(CO)15] reacts with H2S, H2Se, and HSR (R = Me or Et) to give [Ru5(H)C(CO)14(SH)], [Ru5(H)C(CO)14(SeH)], and [Ru5(H)C(CO)14(SR)], respectively. The complex [Ru5(H)C(CO)14(SEt)] crystallises in space group P21/n with a= 15.315(3), b= 16.739(4), c= 10.286(3)A, β= 89.31(2)°, and Z= 4. The structure was solved by a combination of direct methods and Fourier-difference techniques, and refined by blocked-cascade least squares to R= 0.032 for 4134 observed diffractometer data. The Ru5 metal arrangement is intermediate between a square-based pyramid and a bridged ‘butterfly’ with a carbido-carbon at the centre of the cluster. The sulphur atom of the SEt group bridges one edge of the square pyramid where the Ru ⋯ Ru separation is 3.410(1)A. In the reaction of [Ru5C(CO)15] with HSEt the postulated intermediate [Ru5(H)C(CO)15(SEt)] was not isolated. The first product was [Ru5(H)C(CO)14(SEt)](4). When (4) is heated to 81 °C a further molecule of CO is lost and the complex [Ru5(H)C(CO)13(SEt)] isolated. A phosphine derivative of this complex was also prepared and characterised crystallographically; [Ru5(H)C(CO)13(PPh3)(SEt)](6) crystallises in space group P21/c with a= 15.892(2), b= 11.474(1), c= 21.387(2)A, β= 92.50(1)°, and Z= 4. The structure was solved and refined using the same techniques as for (4) to R= 0.036 for 5 861 reflections. The structure resembles that of (4) with the SEt group bridging a long Ru ⋯ Ru edge [3.438(1)A] but with one of the carbonyl groups on a Ru atom associated with the SEt bridge replaced by a phosphine ligand. An analogous reaction occurs when [Ru5C(CO)14{µ-Au(PPh3)}(µ-I)] is heated in heptane to give [Ru5C(CO)13{µ-Au(PPh3)}(µ-I)]. This complex also readily takes up phosphine to give [Ru5C(CO)13(PPh3){µ-Au(PPh3)}(µ-I)](12), which has been characterised crystallographically, crystallising in space group P with a= 9.899(3), b= 14.628(6), c= 18.788(7)A, α= 100.29(3), β= 91.31(3), γ= 93.69(3)°, and Z= 2. The structure was solved and refined as described above to R= 0.042 for 6 075 reflections. The general geometry of the Ru5C core observed in (6) is retained and the iodine ligand bridges a long Ru ⋯ Ru edge [3.526(1)A], and the Au(PPh3) group replaces the bridging hydride. Further heating of the cluster (6) results in the loss of a further CO ligand to give [Ru5(H)C(CO)12(PPh3)(SEt)](7) which may exist in two isomeric forms. The structure of one of the isomers shows that Ru–Ru bond formation has occurred and the geometry of the Ru5C core may be described as a centred, square-based pyramid. The SEt group now bridges a basal Ru–Ru edge [2.698(1)A] and the phosphine ligand is co-ordinated to a basal Ru atom. The complex (7) crystallises in space group P with a= 10.162(2), b= 13.807(4), c= 14.660(4)A, α= 78.20(2), β= 74.12(2), γ= 87.38(2)°, and Z= 2. This converged to R = 0.041 for 4 050 reflections. The adducts [Ru5C(CO)15{µ-Au(PPh3)}X](X =Cl or Br) and their derivatives [Ru5C(CO)14{µ-Au(PPh3)}X] react with PPh3 to eliminate‘ Au(PPh3)X ’ and produce [Ru5C(CO)14(PPh3)].

Preparation and crystal and molecular structure of a polymeric bis(sulphinylnitrilo)sulphur complex of silver(I): [Ag4{S(NSO)2}9][AsF6]4·SO2

The title compound was isolated from the reaction of AgAsF6 with S(NSO)2 in liquid SO2. It crystallises in the rhombohedral space group R3c, with a=b= 18.249(5), c= 35.95(2)A, and Z= 6. The structure was refined to R= 0.070 for 1 653 unique observed diffractometer data. There are two crystallographically independent silver atoms. One lies on a three-fold axis and is octahedrally co-ordinated by the terminal oxygens of six S(NSO)2 ligands; the other occupies a general position and is unsymmetrically co-ordinated by the nitrogen atoms of three S(NSO)2 ligands. The ligands bridge the silver atoms to form a polymeric cationic network; the AsF6– anions and SO2 solvent molecule occupy holes in this network without themselves acting as ligands.

Preparation of trimeric and tetrameric bis(trifluoromethyl)arsazene; X-ray study of [(CF3)2AsN

Two new aminoarsines, (CF3)2AsN(SiMe3)2(1) and CF3As[N(SiMe3)2]2(2), are formed by reaction of (CF3)2AsCl and (CF3)AsCl2 with LiN(SiMe3)2. Chlorination of (1) yields [(CF3)2As(Cl)N(SiMe3)]2(3). On refluxing (3) in n-hexane or n-heptane, the synthesis of trimeric and tetrameric bis(trifluoromethyl)arsazenes, [(CF3)2AsN]3(4) and [(CF3)2AsN]4(5), is accomplished. Pyrolysis of (3) also produced (4) and (5). Crystals of (5) are triclinic, space group P, with a= 991.2(5), b= 1 012.9(6), c= 1 432.8(7) pm, α= 108.21(4), β= 96.03(4), γ= 109.44(4)°, and Z= 2. The structure was solved by direct methods and refined to R 0.069 for 2 183 unique observed diffractometer data. The molecular symmetry approximates to (S4), with a slight alternation in As–N distances [171.6(7) and 173.2(9) pm].