Synthesis and structural features of tris(5-bromo-2-methoxyphenyl)antimony dicarboxylates

Tris(5-bromo-2-methoxyphenyl)antimony bis(4-nitrophenylacetate) (I), tris(5-bromo-2-methoxyphenyl)antimony bis(2-methoxybenzoate) (II), and tris(5-bromo-2-methoxyphenyl)antimony bis(phenylpropiolate) (III) have been synthesized via the reaction between tris(5-bromo-2-methoxyphenyl) antimony and 4-nitrophenylacetic acid, 2-methoxybenzoic acid, and phenylpropiolic acid, respectively, in the presence of hydrogen peroxide (molar ratio: 1: 2: 1). According to X-ray diffraction data, the antimony atom in molecules of complexes I–III has a distorted trigonal bipyramidal coordination. The OSbO axial angles and the CSbC bond angles in the equatorial plane are 173.27(15)°, 172.96(11)°, 172.99(10)°, and 115.5(2)°–123.3(2)°, 108.81(16)°–129.32(17)°, and 110.66(17)°–127.91(17)°, respectively. The Sb-O bond lengths are 2.092(4) and 2.115(4)Å in I, 2.088(3) and 2.097(2) Å in II, and 2.096(3) and 2.120(3) Å in III. The Sb-C bonds range within 2.095(6)–2.123(6) Å in I, 2.107(4)–2.117(4) Å in II, and 2.097(4)–2.116(4) Å in III. Complexes I, II, and III are observed to have intramolecular Sb…OCH₃ contacts (3.169–3.226, 3.134–3.174, and 3.147–3.196 Å, respectively) in addition to Sb…O=C interactions (3.121, 3.139Å; 2.944, 3.038 A0; 3.111, 3.120 Å).     

Tris(2-methoxy-5-bromophenyl)antimony bis(2-nitrobenzoate): Synthesis and specific features of the structure

Tris(5-bromo-2-methoxyphenyl)antimony bis(2-nitrobenzoate) (I) is synthesized by the reaction of tris(5-bromo-2-methoxyphenyl)antimony with 2-nitrobenzoic acid in the presence of hydrogen peroxide (mole ratio 1: 2: 1). According to the X-ray diffraction data, the antimony atom has distorted trigonal bipyramidal coordination. The axial angle OSbO is 177.92(11)°, equatorial bonds CSbC are 109.23(16)°–128.31(16)°, and the Sb-O and Sb-C bond lengths are 2.095(3)–2.125(3) and 2.098(4)–2.113(4) Å, respectively. A specific feature of the structure of complex I is the presence of intramolecular contacts Sb...O(CH₃) (2.992–3.175 Å along with the interactions Sb...O=C (3.039–3.117 Å). The structural organization in crystal is due to weak hydrogen bonds N-O...H-C, C=O...H-C, C-Br...H-C.     

Tris(5-bromo-2-methoxyphenyl)bismuth bisbenzenesulfonate solvate with toluene: Synthesis and structure

Tris(5-bromo-2-methoxyphenyl)bismuth bisbenzenesulfonate, which crystallizes from toluene in the solvate form (5-Br-2-MeOC₆H₃)₃Bi(OSO₂Ph)₂ ? TolH (I), has been synthesized by the reaction between tris(5-bromo-2-methoxyphenyl)bismuth and benzenesulfonic acid in the presence of hydrogen peroxide (1: 2: 1 mol/mol/mol) in ether. A crystal contains two types of crystallographically independent molecules (a and b), in which bismuth atoms have a trigonal bipyramidal coordination to benzenesulfonate substituents in axial positions. The axial OBiO angle is 175.4(3)° (Ia) and 175.5(3)° (Ib), and the equatorial CBiC angles are 111.2(3)°, 122.0(4)°, 126.7(4)° (Ia) and 111.3(4)°, 123.3(3)°, 125.2(4)° (Ib). The Bi–C distances are 2.189(9), 2.198(9), 2.200(10) Å (Ia) and 2.198(9), 2.202(9), 2.209(9) Å (Ib). The Bi–O bond lengths are 2.274(8), 2.306(8) Å (Ia) and 2.248(8), 2.303(8) Å (Ib). Intramolecular contacts between the bismuth atom and the oxygen atoms of methoxy and sulfonate groups take place in molecules.     

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.     

Tris(<Emphasis Type="Italic">para</Emphasis>-tolyl)- and tris(4-fluorophenyl)antimony diaroxides: syntheses and structures

Bis(4-bromophenoxy)tris(para-tolyl)antimony (I), bis(4-nitrophenoxy)tris(para-tolyl)antimony (II), bis(4-nitrophenoxy)tris(4-fluorophenyl)antimony (III), bis(2,3,4,5,6-pentafluorophenoxy)tris(4-fluorophenyl) antimony (IV), and bis(2,3,4,5,6-pentachlorophenoxy)tris(4-fluorophenyl)antimony (V) (CIF files CCDC 1470829 (I), 1474589 (II), 1062337 (III), 1470476 (IV), and 1472954 (V)) are synthesized in high yields by the reactions of tris(para-tolyl)- and tris(4-fluorophenyl)antimony with 4-bromo-, 4-nitro-, 2,3,4,5,6-pentafluoro-, and 2,3,4,5,6-pentachlorophenol, respectively, in diethyl ether in the presence of tert-butyl hydroperoxide. The Sb atoms in compounds I–V have a distorted trigonal bipyramidal coordination with the aroxy groups in the axial positions (angles OSbO 174.08(11)°–179.4(5)°). The average Sb–C bond lengths in compounds I–V are similar and independent of the nature of the para-substituent in the aryl rings. The Sb–O distances are close to the sum of covalent radii of Sb and O atoms. Hydrogen bonds H···F are involved in the formation of the crystal structures of compounds III–V.     

Tris(5-bromo-2-methoxyphenyl)bismuth dicarboxylates [(C<Subscript>6</Subscript>H<Subscript>3</Subscript>(Br-5)(MeO-2)]<Subscript>3</Subscript>Bi[OC(O)CHal<Subscript>3</Subscript>]<Subscript>2</Subscript> (Hal = F,Cl): synthesis and structure

Tris(5-bromo-2-methoxyphenyl)bismuth dicarboxylates [(C₆H₃(Br-5)(MeO-2)]₃Bi[OC(O)CHal₃]₂, Hal = F (II) and Cl (III), have been synthesized by the reaction between tris(5-bromo-2-methoxyphenyl)bismuth (I) and trifluoroacetic acid and thrichloroacetic acid, respectively, in the presence of hydrogen peroxide in ether. According to X-ray diffraction data, a crystal of complex I contains two types of crystallographically independent molecules (a and b) both with a trigonal pyramid configuration. The bismuth atoms in complexes II and III have a distorted trigonal bipyramidal coordination with carboxylate substituents in axial positions. Axial OBiO angles are 166.3(3)° (II) and 171.6(2)° (III); equatorial CBiC angles are 118.0(3)°–123.1(3)° (II) and 113.6(3)°–127.4(3)° (III). Bi–C bond lengths are 2.189(7)–2.200(8) Å (II) and 2.190(8)–2.219(7) Å (III), and Bi–О distances are 2.280(6), 2.459(16) Å (II) and 2.264(5), 2.266(5) Å (III). Intramolecular contacts between the central atom and the oxygen atoms of carbonyl groups (Bi···O 3.028(9), 3.162(9) Å (II); 3.117(9), 3.202(9) Å (III)) are observed at maximum equatorial angles. The oxygen atoms of methoxy groups are coordinated to the bismuth atom. The Bi···O distances in complexes II and III (3.028(16), 3.157(16), 3.162(16) and 3.17(16), 3.143(16), 3.202(16) Å, respectively) are slightly longer than in complex I (3.007(9)–3.136(4) Å).     

Synthesis and crystal structure of Fe(III) and Al(III) complexes with 2-diphenylacetyl-1,3-indandione

Iron(III) and aluminum(III) complexes with 2-diphenylacetyl-1,3-indandione (HL) have been synthesized. The structures of the obtained compounds FeL₃(I) and AlL₃(II) were studied. The isostructural crystals are monoclinic, I: Z = 8, space group P2_1/c, a = 16.061(3) Å, b = 16.658(3) Å, c = 22.015(4) Å, β = 111.41(3)°; II: Z = 8, space group P2_1/c, a = 16.115(14) Å, b = 16.476(8) Å, c = 21.949(20) Å, β = 111.04(11)°. The structural units of crystals I and II are neutral molecules in which each ligand is bidentately coordinated to a central metal atom through the oxygen atom of the acyl keto group and an oxygen atom of the indandione fragment to form a six-membered chelate ring. In the crystals, neutral molecules I and II form pseudodimers due to stacking of indandione moieties of two adjacent coordination spheres and additional C-H…O contacts. Each pseudodimer is in contact with six neighboring dimers also through hydrogen bonds C-H…O to form an infinite framework.     

Synthesis and structure of diethylenetriammonium tetrachloroaurates(III)

The (DienH₃)[AuCl₄]₃ · H₂O (I) and (DienH₃)₂[AuCl₄]Cl₅ (II) compounds were obtained by the reaction of HAuCl₄ with diethylenetriamine trihydrochloride (DienH₃Cl₃) in hydrochloric acid. The compounds were characterized by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. Crystals of I and II are monoclinic with space group P2₁/n. For I, a = 12.2314(3) Å, b = 14.6077(5) Å, c = 13.2680(5) Å, β = 106.7350(10)°, V = 2270.22(13) ų, Z = 8. For II, a = 6.62990(10) Å, b = 17.9026(5) Å, c = 10.3661(3) Å, β = 101.9230(10)°, V = 1203.83(5) ų, Z = 2. Both structures are ionic. The gold atoms in I and II have a 4 + 2 coordination environment. The Au-Cl bond lengths are within 2.276–2.294 Å, and the axial Au…Cl contacts are within 3.315–3.405 Å. The diethylenetriammonium cation in I and II has different conformations.     

Synthesis and structure of tris(4-<Emphasis Type="Italic">N,N</Emphasis>-dimethylaminophenyl) antimony(V) dicarboxylates and diaroxides

Tris(4-N,N-dimethylaminophenyl)antimony dicarboxylates (4-Me₂NC₆H₄)₃Sb[OC(O)R]₂ (R = C₆H₄Me-2 (I), C₆H₄Me-4 (II), CH=CHPh (III)), (4-Me₂NC₆H₄)₃Sb[OC(O)C(O)O] (IV), and (4-Me₂NC₆H₄)₃Sb[OC(O)C₆Cl₄C(O)O] (V)) and tris(4-N,N-dimethylaminophenyl)antimony diaroxides (4-Me₂NC₆H₄)₃Sb(OAr)₂ (Ar = Ph (VI), C₆H₂Br₃-2,4,6 (VII), and C₆H₃Me₂-2,6 (VIII)) have been synthesized by the reaction of tris(4-N,N-dimethylaminophenyl)antimony in ether with carboxylic acids or phenols in the presence of hydrogen peroxide. According to X-ray diffraction analysis data, the Sb atoms in compounds I and VII have a distorted trigonal-bipyramidal coordination, and the axial OSbO angles are 175.4(1)° and 177.9(3)°, respectively. The Sb-O bond lengths are 2.133(3) and 2.142(2) Å in compound I and 2.089(5) Å in compound VII.     

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).     

Syntheses and structures of tris(<Emphasis Type="Italic">para</Emphasis>-tolyl)-, tris(3-fluorophenyl)-, and tris(4-fluorophenyl)antimony dioximates

Tris(para-tolyl)antimony bis(2-oxybenzaldoximate) (I), tris(para-tolyl)antimony bis(2-nitrobenzaldoximate) (II), tris(para-tolyl)antimony bis(2-bromobenzaldoximate) (III), tris(3-fluorophenyl)antimony bis(2-oxybenzaldoximate) (IV), tris(4-fluorophenyl)antimony bis(2-bromobenzaldoximate) (V), and tris(4-fluorophenyl)antimony bis(2-nitrobenzaldoximate) (VI) are synthesized by the reactions of tris(paratolyl)-, tris(3-fluorophenyl)-, and tris(4-fluorophenyl)antimony with 2-oxy-, 2-nitro-, and 2-bromobenzaldoxime in diethyl ether in the presence of tert-butyl hydroperoxide. The Sb atoms in complexes I–VI have a distorted trigonal bipyramidal coordination mode with the oximate ligands in the axial positions. CIF files CCDC nos. 1062231 (I), 1059962 (II), 1465384 (III), 1465109 (IV), 1471948 (V), and 1060387 (VI).     

Tetraphenylantimony <Emphasis Type="Italic">N</Emphasis>-benzoylglycinate: synthesis and structure

Tetraphenylantimony N-benzoylglycinate (I) has been synthesized by the reaction between pentaphenylantimony and N-benzoylglycine in toluene. According to X-ray diffraction data, the antimony atom in a molecule of complex I has a trigonal bipyramidal coordination to the oxygen atom in axial position. The Sb?C_eq, Sb?C_ax, and Sb?O bond lengths are 2.116(6)?2.138(6), 2.183(6), and 2.200(4) Å, respectively. The intramolecular Sb?O=C distance between the carbonyl oxygen atom and the central antimony atom is 3.35(2) Å.     

2-(diphenylphosphinylmethoxy)aniline: Synthesis,vibrational spectra,and crystal structure

The synthesis, vibrational spectra, and X-ray diffraction analysis results for 2-(diphenylphosphinylmethoxy) aniline, 2-[(C₆H₅)₂P(O)OCH₂]C₆H₄NH₂(I), are described. The crystals are monoclinic: a = 18.4515(17) Å, b = 10.5421(12) Å, c = 17.897(2) Å, β = 104.479(8)°, V = 3370.7(6) ų, Z = 8, space group P2₁/c, R = 0.0546 for 1770 reflections with I > 2σ(I). The unit cell contains two crystallographically independent molecules Ia and Ib joined by an N-H …O hydrogen bond between a hydrogen atom of the amino group of aniline in molecule Ia (Ib) and the phosphoryl oxygen atom of molecule Ib (Ia) (O…H 2.18 and 2.19 Å, N…O, 2.979(5) and 3.000(5) Å; NHO angle, 154° and 157°).     

Synthesis and structural features of tris(5-bromo-2-methoxyphenyl)antimony bis (cyclopropanecarboxylate)

Reaction of tris(5-bromo-2-methoxyphenyl)antimony with cyclopropanecarboxylic acid in the presence of hydrogen peroxide (1:2:1 mol) results in tris(5-bromo-2-methoxyphenyl)antimony bis(cyclopropanecarboxylate) I. The structure of the resulting complex was proved by the XRD analysis.     

Tetraphenylantimony perrhenate and tetraphenylantimony chlorate: Syntheses and structures

The reaction of tetraphenylantimony chloride with sodium perrhenate or potassium chlorate yields tetraphenylantimony perrhenate (I) and tetraphenylantimony chlorate (II), respectively. Complex I was also synthesized from pentaphenylantimony and triphenylantimony diperrhenate in toluene. According to X-ray diffraction, crystals I and II consist of almost regular tetrahedral tetraphenylstibonium cations (CSbC, 109.4(2)°–109.5(7)° in I and 109.1(1)°–109.6(1)° in II) and [ReO₄]^? (OreO, 107.6(3)°–113.3(5)°) and [ClO₃]^? (OClO, 96.3(9)°, 116.4(5)°) anions, respectively. The average Sb-C bond lengths (2.094(3) Å in I, 2.097(2) Å in II) are close to the sum of the covalent radii of the Sb and C atoms. The average distances Re-O in complex I (1.672(4) Å) and Cl-O in complex II (1.315 Å) correspond to multiple bonds.     

Synthesis and study of hexaamminecadmium hydrogen hexamolybdocobaltate(III) and hexamolybdochromate(III)

Hexaamminecadmium hydrogen hexamolybdocobaltate(III) and hydrogen hexamolybdochromate(III) of compositions [Cd(NH₃)₆] · H[CoMo₆O₁₈(OH)₆] · 6H₂O (I) and [Cd(NH₃)₆] · H[CrMo₆O₁₈(OH)₆] · 6H₂O (II), respectively, were synthesized and studied by mass spectroscopy, thermo-gravimetry, X-ray powder diffraction, and IR spectroscopy. Crystals of I and II are monoclinic. For I: a = 10.79 Å, b = 3.70 Å, c = 11.95 Å, β = 91.05°, V = 470.12 ų, ρ_calc = 2.37 g/cm³, Z = 2; and for II: a = 10.80 Å, b = 3.68 Å, c = 11.97 Å, β = 91.07°, V = 468.98 ų, ρ_calc = 2.36 g/cm³, Z = 2.     

Crystal structure of adducts of copper(II) acetylacetonate and hexafluoroacetylacetonate with 4-aminopyridine

Single crystal X-ray diffraction is used to investigate two synthesized β-diketonate complexes of copper(II) with aminopyridine: Cu(4-NH₂Py)(aa)₂ (I) and Cu(4-NH₂Py)(hfa)₂ (II). The crystals of I and II have a monoclinic system; the unit cell parameters of I are: P2₁/n space group, a = 8.2921(3) Å, b = 14.7243(5) Å, c = 13.4970(4) Å, β = 102.426(1)°, V = 1609.32(9) ų, Z = 4; for II: C2/c space group, a = 23.5704(5) Å, b = 11.4977(2) Å, c = 16.0285(3) Å, β = 109.265(1)°, V = 4100.6(1) ų, Z = 8. The structures of I and II are molecular; they are composed of isolated molecules. The coordination polyhedron of the copper atom is formed by the O atoms of two acetylacetonate ligands (Cu-O 1.940(2)–2.171(2) I and the O atoms of two hexafluoroacetylacetonate ligands (Cu-O 1.940(2)–2.215(3) Å) in II. The molecules of 4-NH₂Py are bonded to the copper atom via the nitrogen atom of the aromatic ring (Cu-N 2.008(2) Å in I and Cu-N 1.978(3) Å in II). Noncoordinated amino groups join the molecules of the complexes together by means of N-H…O hydrogen bonds.     

Synthesis and structure of tris(4-<Emphasis Type="Italic">N,N</Emphasis>-dimethylaminophenyl)antimony bis(4-methyl benzoate)

The tris(4-N,N-dimethylaminophenyl)antimony bis(4-methyl benzoate) (I) was synthesized by the reaction of tris(4-N,N-dimethylaminophenyl)antimony with 4-methylbenzoic acid in ether in the presence of hydrogen peroxide. According to the X-ray diffraction data, in this molecule the antimony atom is in distorted trigonal-bipyramidal coordination (the axial angle OSbO is 176.15(4)°). The CSbC angles in the equatorial plane are 105.27(6)°, 108.01(6)°, 146.71(6)° (the sum is 359.99°). The Sb-O and Sb-C bond lengths are 2.131(1), 2.137(1) Å and 2.099(2), 2.100(1), 2.107(1) Å, respectively. The intramolecular contacts Sb...O=C are 2.826(1) and 2.928(1) Å.     

Hexa(isothiocyanato)chromates(III) of Some Yttrium Group Lanthanide(III) and Europium Complexes with Nicotinic Acid: Synthesis and Crystal Structures

Double ionic complexes [M(C₅H₅NCOO)₃(H₂O)₂][Cr(NCS)₆] · nH₂O, where M = Eu (I), n = 1.15; Dy (II), Er (III), n = 1.5; M = Yb (IV), n = 2, have been synthesized by the reaction between M(NO₃)₃, M = Eu, Dy, Er, Yb, K₃[Cr(NCS)₆], and nicotinic acid (C₅H₅NCOO) in an aqueous solution and studied by chemical analysis, IR spectroscopy, and X-ray diffraction. Crystals of complexes I–IV are monoclinic, space group P2₁/n, Z = 4; a = 9.5358(2) Å, b = 25.4871(5) Å, c = 15.4303(4) Å, β = 105.513(1)°, V = 3613.6(1) ų, ρ_calcd = 1.799 g/cm³ for I, a = 9.5901(5) Å, b = 25.8599(15) Å, c = 15.6316(9) Å, β = 106.829(2)°, V = 3710.6(4) ų, ρ_calcd = 1.782 g/cm³ for II, a = 9.5640(3) Å, b = 25.8936(11) Å, c = 15.6498(7) Å, β = 106.895(2)°, V = 3708.3(3) ų, ρ_calcd = 1.791 g/cm³ for III, and a = 9.5049(2) Å, b = 25.6378(4) Å, c = 15.5120(3) Å, β = 106.934(1)°, V = 3616.1(1) ų, ρ_calcd = 1.864 g/cm³ for IV.     

Synthesis and crystal structures of cobalt(III) and zinc(II) complexes derived from 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol with urease inhibitory activity

A new mononuclear cobalt(III) complex, [CoL₂(N₃)]₂ · CH₃OH (I), and a new mononuclear zinc(II) complex, [ZnLCl(CH₃OH)] (II) (HL = 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol), were prepared and structurally characterized by elemental analyses, infrared spectroscopy, and single- crystal X-ray diffraction. The crystal of I is monoclinic: space group P2₁/c, a = 18.742(2) Å, b = 15.197(2) Å, c = 25.646(2) Å, β = 125.996(3)°, V = 5909.8(11) ų, Z = 4. The crystal of II is monoclinic: space group P2₁/c, a = 7.257(1) Å, b = 24.707(2) Å, c = 9.637(1) Å, β = 101.557(2)°, V = 1692.9(3) ų, Z = 4. The Co atom in I is in an octahedral coordination, and the Zn atom in II is in a trigonal-bipyramidal coordination. The urease inhibitory test shows that complex I has strong urease inhibitory activity, while complex II has no activity.