Synthesis and Crystal Structure of Tetraphenylbismuth Benzenesulfonate Hydrate and Tetraphenylbismuth 3,4-Dimethylbenzenesulfonate

The reaction of pentaphenylbismuth with SO₃ or with triphenylbismuth bis(benzenesulfonate) in benzene gave tetraphenylbismuth benzenesulfonate monohydrate (I). Tetraphenylbismuth 3,4-dimethylbenzenesulfonate (II) was prepared from pentaphenylbismuth and triphenylbismuth bis(3,4-dimethylbenzenesulfonate) in benzene. The structures of compounds I and II were established by X-ray diffraction. The Bi atoms have a distorted trigonal-bipyramidal coordination where the arenesulfonate group occupies an axial position. The Bi–C(average) and Bi–O distances in molecules I and II are 2.204(2), 2.695(2) Å and 2.205(2), 2.728(2) Å, respectively.     

Phenylbismuth Bis(2,5-dimethylbenzenesulfonate): Structure and properties

Phenylbismuth bis(2,5-dimethylbenzenesulfonate) (I), a coordination polymer in which a bismuth atom has a distorted square pyramidal coordination to an axial carbon atom (Bi-C, 2.247(5) Å) and basal oxygen atoms (Bi-O, 2.390(9)–2.403(10) Å), has been synthesized by the reaction between triphenylbismuth and 2,5-dimethylbenzenesulfonic acid (1: 2 mol/mol) in toluene and structurally characterized. Pentaphenylbismuth and pentaphenylantimony phenylate compound I to triphenylbismuth.     

Reaction of Triphenylbismuth Bis(arenesulfonates) with Triphenylstibine

Tetraphenylantimony arenesulfonates and diphenylbismuth arenesulfonates were prepared by reaction of triphenylbismuth bis(arenesulfonates) with triphenylstibine in toluene at 25°C. The crystal and molecular structure of diphenylbismuth 2,4-dimethylbenzenesulfonate was studied by single crystal X-ray diffraction. The molecules of the compound in the crystal form chains of Ph₂BiOSO₂C₆H₃Me₂-2,4 fragments linked with oxygen atoms of the sulfo group of the bridging arenesulfonate ligand.     

Structures of triphenylbismuth dicarboxylates

Tripheylbismuth bis(trichloroacetate) (I), triphenylbismuth bis(chloroacetate) (II), and triphenylbismuth bis(bromoacetate) (III) were synthesized by the reaction of triphenylbismuth with carboxylic acid. The Bi atoms of the synthesized compounds have a distorted trigonal-bipyramidal coordination with phenyl ligands in equatorial positions. The Bi-C bond lengths lie within intervals 2.194(2)–2.201(2), 2.193(8)–2.223(7), 2.191(4)–2.220(3) Å, the distances Bi-O and Bi···O(=C) are equal 2.308(2), 2.315(2), and 2.896(2), 2.931(2); 2.289(6), 2.302(6), and 2.891(6), 2.910(6); 2.295(3), 2.312(3), and 2.893(3), 2.920(3) Å in I, II, and III, respectively. Molecules of triphenylbismuth dicarboxylates show linear dependence between the maximum equatorial angle CBiC (on the side of a contact) and intramolecular distance Bi···O(=C).     

Synthesis and Structure of Triphenylbismuth Bis(Fluorobenzoates)

The reaction between triphenylbismuth, hydrogen peroxide, and 3,4,5-trifluorobenzoic or pentafluorobenzoic acid (molar ratio 1 : 1 : 2, respectively) in ether gave triphenylbismuth bis(3,4,5-trifluorobenzoate) (I) and triphenylbismuth bis(pentafluorobenzoate) (II) in 74 and 89% yields, respectively. The structures of compounds I and II were established by X-ray diffraction. The Bi atoms have a distorted trigonal-bipyramidal coordination with acylate groups in the axial positions. The OBiO angles are 170.2(2)° and 171.5(2)° in I and II, respectively. The Bi–C(Ph)_eq bond lengths vary in the range of 2.187(6)–2.204(5) Å, the Bi–O(acyl) lengths are 2.256(5) Å in I, and 2.281(5) and 2.318(5) Å in II. In the crystals I and II, the Bi and carbonyl O atoms are involved in intramolecular interactions (Bi···O(=C) 2.926(5)–3.176(5) Å), which increase the equatorial CBiC angles on the side of these contacts to 136.2(3)° and 138.6(2)° in I and II, respectively.     

Triphenylbismuth bis(3,4-dimethylbenzenesulfonate): Synthesis and structure

Triphenylbismuth bis(3,4-dimethylbenzenesulfonate) Ph₃Bi(OSO₂C₆H₃Me_2-3,4)₂ (I) has been synthesized by the reaction between triphenylbismuth and 3,4-dimethylbenzenesulfonic acid in the presence of tert-butylhydroperoxide (1: 2: 1 mol) in ether. The bismuth atom in complex I has a trigonal bipyramidal coordination to arenesulfonates substituents in axial positions (axial OBiO angle, 173.99(8)°; equatorial CBiC angles, 106.94(11)°, 112.24(11)°, 140.77(11)°). The Bi?C distances are 2.189(3), 2.192(3), and 2.197(3) Å; the Bi?O distances are 2.284(2) and 2.301(2) Å. Some intramolecular contacts are observed between the central atom and the oxygen atoms of sulfonate groups at the maximum equatorial angle (Bi···O 3.122(3), 3.189(4) Å).     

Synthesis and structure of triphenylbismuth bis(phenylcarboranylcarboxylate)

Triphenylbismuth bis(phenylcarboranylcarboxylate) was synthesized by the reaction of triphenylbismuth with phenylcarboranylcarboxylic acid in the presence of hydrogen peroxide. The bismuth atom has a distorted trigonal-bipyramidal coordination with phenyl ligands in equatorial positions. Bond lengths: Bi-C 2.195(3), 2.196(3), 2.204(3) Å, Bi-O 2.266(2), 2.276 Å. In the molecule there are the donor-acceptor interaction of Bi...O(=C) 2.980(2) and 3.130(3) Å. The value of the equatorial angle CBiC from the side of the Bi...O(=C) contact is 141.4(1)°, the angle OBiO is 168.2(1).     

Synthesis and structures of organoantimony and organobismuth derivatives of 4-sulfophenol and 2,4-disulfophenol

Tetraphenylbismuth 4-hydroxybenzenesulfonate (I) and tetraphenylantimony 4-hydroxybenzenesulfonate (II) are synthesized in yields up to 80% by the reaction of pentaphenylbismuth and pentaphenylantimony, respectively, with 4-sulfophenol. Compounds I and II are also prepared by the ligand redistribution reaction from pentaphenyl compounds of bismuth and antimony and triphenylbismuth bis(4-hydroxybenzenesulfonate) and triphenylantimony bis(4-hydroxybenzenesulfonate), respectively, in yields up to 87%. The recrystallization of compounds I and II from water gives crystalline hydrates Ph₄BiOSO₂C₆H₄(OH-4) · H₂O (III) and Ph₄SbOSO₂C₆H₄(OH-4) · H₂O (IV). Pentaphenylbismuth and pentaphenylantimony react with 2,4-disulfophenol in acetone, regardless of the ratio of the starting reactants, to form bis(tetraphenylbismuth) 4-hydroxybenzene-1,3-disulfonate (V) and bis(tetraphenylantimony) 4-hydroxybenzene-1,3-disulfonate (VI) in yields up to 74%. According to X-ray diffraction data, coordination of the bismuth atoms in compound I is trigonal-bipyramidal with the axial oxygen atom of the 4-hydroxybenzenesulfonate group (Bi···O 2.764 Å). In compound II, coordination of the Sb atom is tetrahedral (CSbC angles 106.2°–112.3°). In crystal III, the distances between the central atom and the nearest oxygen atoms of the arenesulfonate group and the hydrate water molecule are 3.094 and 3.125 Å, respectively. Crystals V and VI consist of doubly charged anions of 2,4-disulfophenol and several distorted tetrahedral cations of tetraphenylbismuthonium (CBi(1)C, CBi(2)C angles and Bi(1)-C, Bi(2)-C bond lengths vary in the intervals 102.1°–122.7°, 105.4°–114.0° and 2.103–2.230, 2.187–2.209 Å, respectively) and tetraphenylantimonium (CSb(1)C, CSb(2)C angles and Sb(1)-C, Sb(2)-C bond lengths 106.3°–112.2°, 101.3°–122.4° and 2.095–2.110, 2.092–2.123 Å, respectively). The Bi(1) and Sb(2) atoms are coordinated by one of the oxygen atoms of the 2,4-disulfophenol anions (distances Bi(1)···O(3) 2.803, Sb(2)···O(1), 2.704 Å).     

Synthesis and structures of triphenylbismuth diaroxides Ph3Bi(OAr)2, Ar = C6H3(Br2-2,4), C6H2(Br2-2,6)(NO2-4), and C6H2[(NO2)3-2,4,6]

Triphenylbismuth diaroxides Ph₃Bi(OAr)₂ (Ar = C₆H₃(Br₂-2,4) (I), C₆H₂(Br₂-2,6)(NO₂-4) (II), and C₆H₂[(NO₂)₃-2,4,6] (III) are synthesized in yields up to 74% by the reaction of triphenylbismuth with phenols in the presence of hydrogen peroxide (taken at a molar ratio 1: 2: 1, respectively) in ether. According to X-ray diffraction data, the bismuth atoms in compounds I-III have distorted trigonal-bipyramidal coordination with the aroxyl substituents in the axial positions; the Bi-C, Bi-O bond lengths and the OBiO, CBiC angles vary in the intervals 2.162–2.204, 2.150–2.299 ? and 172.4°–176.1°, 109.6°–139.9°, respectively. Compound II exhibits intramolecular contacts between the central atom and ortho-Br atoms (3.924, 4.101 ?), and compound III has similar contacts of the Bi atom with the O atoms of the ortho-nitro groups (3.114, 3.313 ?). Original Russian Text ? V.V. Sharutin, I.V. Egorova, O.K. Sharutina, A.P. Pakusina, M.A. Pushilin, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 1, pp. 14–21.     

Tetraphenylbismuth aroxides: Synthesis and structure

Tetraphenylbismuth aroxides Ph4BiOAr (Ar = C₆H₃Cl₂-2,6, C₆H₂(Br₂-2,6)(t-Bu)-4, C₆H₂(Br₂-2,6)(NO₂)-4 · 1/2C₆H₆, C₆H₃(NO₂)₂-2,4, C₆H₂(NO₂)₃-2,4,6) were synthesized in the yield up to 90% by the reaction of pentaphenylbismuth with phenols and triphenylbismuth diaroxides and studied by X-ray diffraction. The Bi atoms of tetraphenylbismuth aroxides have a distorted trigonal-bipyramidal coordination with the axial O atom of the aroxide group. The axial angles CBiO vary from 171.7(2)° to 179.3(3)°. The distances Bi-O change in the interval 2.453(2)–2.925(7) Å depending on the nature of substituents in the aromatic ring of the phenol residue. The increasing distance Bi-O in the series of compounds under study correlates with the tendency of the BiC₄ fragment to form the tetrahedral configuration.     

Tetraphenylantimony(V) hexachloroplatinate, tetrachloroaurate, and hexachlorostannate [Ph4Sb] 2+ [PtCl6]2?, [Ph4Sb]+[AuCl4]?, and [Ph4Sb] 2+ [SnCl6]2?: Synthesis and crystal structures

The reactions of tetraphenylantimony with hexachloroplatinic and chloroauric acids in benzene afford bis(tetraphenylantimony) hexachloroplatinate (I) and tetraphenylantimony tetrachloroaurate (II), respectively. Compound II is also synthesized from tetraphenylantimony chloride and chloroauric acid in acetone. Bis(tetraphenylantimony) hexachlorostannate (III) is synthesized from tin dichloride and tetraphenylantimony chloride in acetone or from tin tetrachloride and tetraphenylantimony chloride in benzene. The crystal structures of compounds I–III are determined by X-ray diffraction analysis. The antimony atoms in the [Ph₄Sb]⁺ cations have a distorted tetrahedral coordination (CSbC bond angles range from 105.7(1)° to 118.5(1)° (I), from 106.2(3)° to 114.4(3)° (II), and from 106.0(1)° to 117.1(1)° (III)). The Sb-C bond lengths vary in intervals of 2.094(2)–2.098(2), 2.087(7)–2.111(7), and 2.093–2.100(3) ?, respectively. The coordination of the Pt and Sn atoms in complexes I and III is close to an ideal octahedral coordination with ClPtCl and ClSnCl bond angles of 88.68(2)°–91.32(3)° and 88.84(3)°–91.16(3)°, respectively. The square coordination of the Au atom in complex II is slightly distorted: the Au-Cl bond lengths are 2.266(2)–2.277(2) ?, the ClAuCl bond angles are equal to 89.7(1)°–90.5(1)°, the root-mean-square deviation of the atoms from the coordination plane being 0.004 ?. Original Russian Text ? V.V. Sharutin, V.S. Senchurin, O.A. Fastovets, A.P. Pakusina, O.K. Sharutina, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 5, pp. 373–379.     

Synthesis and structure of triphenylbismuth bis(1-adamantanecarboxylate)

Triphenylbismuth bis(1-adamantanecarboxylate) was synthesized by reacting triphenylbismuth with 1-adamantanecarboxylic acid in the presence of hydrogen peroxide. In the complex, the coordination sphere of a bismuth atom is a trigonal bipyramid with C(Ph) atoms in the equatorial plane and O atoms in the apical positions. The Bi-C bond lengths are 2.213(4) Å (two bonds) and 2.222(5) Å; two Bi-O bond lengths are 2.306(3) Å. The Bi…O(=C) donor-acceptor interactions (2.716(3) Å) occur in the molecule. The equatorial CBiC angle on the side of the Bi…O(=C) contact is 157.1(2)°.     

Tetraphenylbismuth 2,4-Dimethylbenzenesulfonate: Synthesis and Structure

Tetraphenylbismuth 2,4-dimethylbenzenesulfonate was synthesized by reacting pentaphenylbismuth or bromine with diphenylbismuth 2,4-dimethylbenzenesulfonate and its structure was established using X-ray diffraction analysis. The Bi atom has a distorted trigonal bipyramidal coordination. The Bi–C bond lengths are equal to 2.199(4)–2.227(4) Å the Bi–O distance and axial CBiO angle are equal to 2.665(3) Å and 174.2(1)°, respectively.     

Triphenylbismuth Bis(2,4,6-Tribromophenoxide): Synthesis and Structure

A reaction of triphenylbismuth with 2,4,6-tribromophenol and hydrogen peroxide (molar ratio 1 : 2 : 1) in ether affords triphenylbismuth bis(2,4,6-tribromophenoxide). The complex obtained was structurally characterized by X-ray diffraction analysis. The coordination polyhedron of the Bi atom is a trigonal bipyramid with axial aroxy groups. The Bi–C and Bi–O bond lengths are 2.202(4), 2.203(4), 2.212(4) and 2.241(3), 2.245(3) Å, respectively. The intramolecular Bi···Br(1,4) contacts are 3.629(1) and 4.077(1) Å, respectively.     

Synthesis and Structure of New Crystal Modification of Tetraphenylantimony 4-Methylbenzenesulfonate

Tetraphenylantimony arenesulfonates were synthesized by the reaction of pentaphenylantimony with arenesulfonyl chlorides in toluene taken in a molar ratio of 1 : 1 : 2 in air. The structure of tetraphenylantimony 4-methylbenzenesulfonate was determined by X-ray diffraction analysis. The Sb atom has a distorted trigonal-bipyramidal coordination with phenyl and arenesulfonate groups in the axial positions. The Sb–C(Ph)_eq bond lengths vary in the 2.099(2)–2.123(2) Å range, and the Sb–C(41) and Sb–O(1) distances are 2.136(2) and 2.499(1) Å, respectively. The O(1)SbC(4) axial angle is 175.77(5)°.     

Synthesis and structure of triphenylbismuth bis(2-phenylaminobenzoate)

Interaction of triphenylbismuth with phenylanthranilic acid in the presence of hydrogen peroxide yields triphenylbismuth bis(2-phenylaminobenzoate), in which bismuth atoms have a distorted trigonal bipyramidal coordination with phenyl ligands in equatorial positions. The bond lengths (Å) are as follows: Bi-C, 2.193(5), 2.200(4), and 2.200(4); Bi-O, 2.252(4) and 2.300(4). Intramolecular hydrogen bonds N-H?O(=C) (H?O, 1.91, 1.97 Å; N?O, 2.634(9), 2.667(9) Å) and donor-acceptor interactions Bi?O(=C) (2.790(5) and 2.838(5) Å) exist in the molecule.     

Synthesis and structure of triphenylbismuth bis(pentachlorobenzoate)

Triphenylbismuth bis(pentachlorobenzoate) has been synthesized by the reaction between triphenylbismuth and pentachlorobenzoic acid in the presence of hydrogen peroxide in ether. According to X-ray diffraction data, the bismuth atoms in two crystallographically independent molecules (A and B) have a distorted trigonal bipyramidal coordination. The OBiO and CBiC angles between axial and equatorial substituents are 171.7(3)°, 173.6(3)°, and 105.3(4)°–146.9(4)°. The Bi-O and Bi-C bond lengths are 2.291(8)–2.315(8) and 2.197(11)–2.204(10) Å, respectively. The Bi…O(=C) distances are 2.843(10)–2.857(11) Å.     

Synthesis and structure of bis(monohaloacetates) of tris(5-bromo-2-methoxyphenyl)antimony

Tris(5-bromo-2-methoxyphenyl)antimony bis(monohaloacetates) [(5-Br)(2-MeO)C₆H₃]₃Sb[OC(O)CH₂X]₂, X = Cl (I), Br (II), I (III) have been synthesized by the reaction of tris(5-bromo-2-methoxyphenyl)antimony with chloro-, bromo-, and iodoacetic acids in the presence of hydrogen peroxide. According to X-ray analysis the antimony atom in I–III has a distorted trigonal-bipyramidal coordination.     

Different coordination modes and supramolecular aggregations in copper(II) pentane-2,4-dionato compounds with 2-pyridone and 3-hydroxypyridine

Abstract  

Copper(II) bis(pentane-2,4-dionato-κ² O,O′) compounds with 2-pyridone (1) and 3-hydroxypyridine (2) were prepared by the reaction of bis(pentane-2,4-dionato-κ² O,O′)copper(II) with selected ligands. The coordination of Cu(II) in both compounds is square pyramidal with the fifth coordination site occupied by the carbonyl oxygen atom of the 2-pyridone ligand in 1 and by the nitrogen atom of 3-hydroxypyridine in 2. The X-ray crystallographic studies revealed different crystal aggregation influenced by the ability of the 2-pyridone ligand to act as a hydrogen bond donor and acceptor, and 3-hydroxypyridine acting only as a hydrogen bond donor. Intermolecular N–H···O hydrogen bonding forms dimers in 1 and infinite chains in 2. Three-dimensional aggregation is achieved by π–π interactions and C–H···π (arene) hydrogen bonding.     

系列Mn(II)配位超分子的合成、晶体结构和表面光电压研究

采用水热合成方法得到了三种Mn(II)配位超分子: Mn(2,5-dcp)₂(H₂O)₂ (1), Mn(INA)₂(H₂O)₄ (2)和Mn(phen)₂Cl₂ (3) (2,5-dcp＝pyridine-2,5-dicarboxylic acid, INA＝iso-nicotinic acid, phen＝1,10-phenanthroline). 通过X射线单晶衍射、红外光谱(IR)、紫外光谱(UV-Vis)及表面光电压光谱(SPS)等方法对化合物进行了表征. 三种化合物中均存在大量的氢键, 使化合物晶体构成了无限延伸的三维网络结构. 表面光电压谱显示了化合物1～3在300～600 nm范围内呈现出正的光伏响应带, 具有P-型半导体的特征. 讨论了氢键在超分子构建中的作用以及不同配位环境对于配合物表面光电压的影响.