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 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(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).     

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 tri-m-tolylbismuth dicarboxylates

Tri-m-tolylbismuth bis(2-methoxybenzoate) (I) (84%), tri-m-tolylbismuth dibenzoate (II) (91%), and tri-m-tolylbismuth bis(trichloroacetate) (III) (92%) have been synthesized via the reaction between tri-m-tolylbismuth, carboxylic acid, and hydrogen peroxide. According to X-ray diffraction data, a bismuth atom in compounds I–III have a distorted trigonal bipyramidal coordination (disregarding the additional coordination of carbonyl oxygen atoms) to m-tolyl ligands in equatorial positions. The Bi-C bonds in compounds I, II, and III range within 2.193(3)–2.228(5) Å, and the Bi-O and Bi…O(=C) distances are 2.267(3), 2.282(3) Å and 2.791(6), 2.895(6) Å in I; 2.293(2), 2.296(3) Å and 2.815, 2.905(5) Å in II; and 2.278(4), 2.300(4) Å and 3.008(9), 3.115(9) Å in III. The equatorial CBiC angles on the side of Bi…O(=C) contacts are considerably enlarged, thus decreasing the other two angles (150.6°, 104.7°, and 104.7° in I, 140.2°, 107.4°, and 112.3° in II, and 138.0°, 110.1°, and 111.0° in III).     

P-Analog of Carbamic Acid: Crystal Structure of (CO)5CRH2P-COOH and Ab Initio Calculations

Abstract

Phosphinoformic acid is unstable like the N-analogue carbamic acid. We found however that the acid can be stabilized by coordination via P to a (CO)₅Cr-moiety [1]. In accordance with the conclusions of Leiserowitz [2] about solid carboxylic acids the crystal formic acid consists of hydrogen of the Cr atom is a distorted bonds between 1.881 and 1.928 A bond of 2.335 Å. The angular distortion is small as shown by a maximum deviation of about 2.3° fiom the ideal geometry. At the P atom all bonding angles involving the Cr atom are widened to a maximum of 124° and the other ones are reduced to a minimum of 95°. In the crystal structure two symmetry-related molecules are connected to each other by means of two equivalent hydrogen bonds 06… 07′ and 07… 06′ of 2.660 ç length between the carboxylic groups. Because of a twofold disorder along the bond P-C6, proven by bond lengths of 1.269(2) Å for C6–06 and 1.264(2) Å for C6–07 as well as by the localization and refinement of two H atoms with an occupancy factor of 0.5 bonded to each of the O atoms, no distinction can be made between the C=O double and the C-O single bond.     

Crystal structure of 1:1 Complexes between urea and two crown ether derivatives of phthalic acid, 2,3,5,6,8,9,11,12,14,15-decahydrobenzo[1,4,7,10,13,16]hexaoxacyclo-octadecin-18,19-dicarboxylic acid (i) and 2,3,5,6,8,9,11,12-octahydro-benzo[1,4,7,10,13]pentaoxacyclopentadecin-15,16-dicarboxylic acid (II)

The crystal structures of the titlke compounds have been determined by X-ray diffraction. Urea, I crystallizes in the triclinic PI space group with cell dimensions a = 8.336(2), b = 11.009(2), c = 13.313(2) Å, α = 105.55(3), β = 103.62(3), γ = 104.63(3)° and Z = 2 final R value 0.072 for 2105 observations. Urea, II crystallizes in the orthorhombic P2₁2₁2₁ space group with cell dimensions a = 8.750(2), b = 10.844(3) and c = 21.215(3) Å and Z = 4, final R value 0.083 for 599 observations. All the hydrogen atoms were located in the complex urea, I ; urea molecules form hydrogen bonded dimers about centers of symmetry, these dimers are sandwiched between macrocyclic rings forming one simple and one bifurcated hydrogen bond from the “endo” hydrogen atoms to the ether oxygen atoms. These units are held by hydrogen bonding between the urea molecules and carboxylic acids in two other units; these hydrogen bonds are cyclic involving eight atoms -(N-H(exo)…O(keto)-C-O-H…O(urea)-C)-. Only one carboxylic acid group per molecule takes part in these hydrogen bonds, the other forms a short, 2.490(7) Å, internal bond to the acceptor keto oxygen atom. N(H)…O bonds range from 2.930(7) to 3.206(7) Å, O(H)…O is 2.475(6) Å. In the complex urea, II each urea is hydrogen bonded to three different host molecules and vice versa; the urea “endo” hydrogen atoms bond to the ether oxygen atoms, while both “exo” hydrogen atoms take part in cyclic hydrogen bonds to carboxylic acids. There is not internal hydrogen bond. N(H)…O bonds range from 2.83 to 3.26(2) A and the O-…O bonds are 2.55 and 2.56(2) Å.     

Synthesis and structure of tri-<Emphasis Type="Italic">m</Emphasis>-tolylantimony bis(1-adamantanecarboxylate)

Tri(m-tolyl)antimony bis(1-adamantanecarboxylate) (3-MeC₆H₄)₃Sb[OC(O)C₁₀H₁₅]₂ has been synthesized with a yield of 90.0% by the reaction of tri(m-tolyl)antimony with 1-adamantanecarboxylic acid in the presence of hydrogen peroxide in ether. According to X-ray diffraction analysis data, the antimony atom has a distorted trigonal-bipyramidal coordination with the axially positioned oxygen atoms of carboxyl groups. The axial OSbO angle is 173.1(2)°; the equatorial CSbC angles are 112.0(1)°, 112.0(1)°, and 136.0(3)°; the Sb-O distance is 2.109(3)Å; the Sb-C distances are 2.103(5), 2.103(5), and 2.121(7) Å; intramolecular Sb…O(=C) contacts are 3.069(5) Å.     

New preparation method of chlorotriphenylantimony aryloxides Ph3SbCl(OAr)

The reaction of bis(2,6-dichlorophenoxo)triphenylantimony with triphenylantimony dichloride gave chloro(2,6-dichlorophenoxo)triphenylantimony Ph₃SbCl(OC₆H₃Cl₂-2,6) (I). 2,6-Dichlorophenoxotetraphenylantimony Ph₄Sb(OC₆H₃Cl₂-2,6) (II) was prepared from pentaphenylantimony and bis(2,6- dichlorophenoxo)triphenylantimony. According to X-ray diffraction data, the antimony atoms in I and II have a distorted trigonal-bipyramidal coordination with the following axial: OSbCl, 179.59(5)° (I); CSbO, 178.20(14)° (II); the equatorial angles are 115.72(9)°–124.87(10)° (I) and 111.43(18)°–123.18(19)° (II); the equatorial bond lengths are Sb–C, 2.099(3)–2.111(2) Å (I), 2.111(4)–2.122(5) Å (II); and the axial bond lengths are Sb–Cl, 2.4740(7) Å; Sb–O, 2.0802(16) Å (I); Sb–O, 2.237(3) Å; and Sb–C, 2.167(4) Å (II) (CIF files CCDC no. 998625 for I and no. 1010553 for II).     

Cocrystals of 1,4‐diethynylbenzene with 1,3‐diacetylbenzene and benzene‐1,4‐dicarbaldehyde exhibiting strong nonconventional alkyne–carbonyl C—H…O hydrogen bonds between the components

Weak interactions between organic molecules are important in solid‐state structures where the sum of the weaker interactions support the overall three‐dimensional crystal structure. The sp‐C—H…N hydrogen‐bonding interaction is strong enough to promote the deliberate cocrystallization of a series of diynes with a series of dipyridines. It is also possible that a similar series of cocrystals could be formed between molecules containing a terminal alkyne and molecules which contain carbonyl O atoms as the potential hydrogen‐bond acceptor. I now report the crystal structure of two cocrystals that support this hypothesis. The 1:1 cocrystal of 1,4‐diethynylbenzene with 1,3‐diacetylbenzene, C₁₀H₆·C₁₀H₁₀O₂, (1), and the 1:1 cocrystal of 1,4‐diethynylbenzene with benzene‐1,4‐dicarbaldehyde, C₁₀H₆·C₈H₆O₂, (2), are presented. In both cocrystals, a strong nonconventional ethynyl–carbonyl sp‐C—H…O hydrogen bond is observed between the components. In cocrystal (1), the C—H…O hydrogen‐bond angle is 171.8 (16)° and the H…O and C…O hydrogen‐bond distances are 2.200 (19) and 3.139 (2) Å, respectively. In cocrystal (2), the C—H…O hydrogen‐bond angle is 172.5 (16)° and the H…O and C…O hydrogen‐bond distances are 2.25 (2) and 3.203 (2) Å, 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).     

Study of the molecular and crystal structure of a new coordination polymer of copper(II) nitrate with 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecane-2,8-dione

A coordination polymer {[Cu(C₁₁H₂₀N₄O₂)₂(H₂O)]²⁺·2(NO ₃ ^? )} _n (I) is synthesized and analyzed using single-crystal XRD. The crystals are monoclinic: space group P2/c, a = 12.5237(6) Å, b = 7.3310(3) Å, c = 16.8926(8) Å, β = 92.569(4)°, V = 1549.38(13) ų, ρ_calc = 1.47 g/cm³, and Z = 2. The copper atom is in a special position in the second-order axis. The coordination polyhedron of the metal is a trigonal bipyramid. In the axial direction, it is coordinated by two oxygen atoms O(1) of the organic ligand molecules connected by the symmetry operation [?x, y, 0.5-z]; the angle O(1)Cu(1)O(1) ⁱ is 175.16(15)°. In the equatorial direction, the copper atom is coordinated by oxygen atoms O(2) of two ligand molecules connected with the reference molecule by the symmetry operations [?x, y, 0.5-z] and [x, 1-y, ?0.5+z] and the water molecule O(6) in a special position on the twofold axis. The OCuO angles between the equatorial oxygen atoms are 96.80(16)–131.60(8)°, and those between the axial and equatorial atoms are 87.58(8)-91.60(10)°. It is noteworthy that the length of the Cu-O(1) bond (1.955(2) Å) with the axial carbonyl oxygen atom is somewhat shorter than the bond (2.060(3) Å) with the equatorial atom. Nitrate anions are outside the coordination sphere of the metal. The Cu…Cu distance in the polymer is 8.33 Å. To confirm the purity of the sample of I, the powder X-ray pattern is refined by the Rietveld method; the lattice parameters at room temperature are: a = 12.535(4) Å, b = 7.3161(13) Å, c = 16.841(5) Å, β = 92.11(2)°, and V = 1543.4(7) ų.     

SYNTHESIS AND CHARACTERIZATION OF DIAQUA(3-pTOLYLIMINO-2-BUTANONE OXIMATO)(3-p-TOLYLIMINO-2-BUTANONE OXIME)NICKEL(II) PERCHLORATE

Abstract

[Ni(L^?1)(HL)(H₂O)₂].ClO₄ with a Schiff base ligand L (HL = 3-p-tolylimino-2-butanone oxime) was prepared and structurally characterized by IR, cyclic voltammetry and X-ray diffraction methods. The nickel atom has distorted octahedral coordination consisting of four nitrogen atoms and two oxygen atoms. The equatorial plane is formed by two oxime nitrogen atoms and two imine nitrogen atoms of two Schiff base ligand (L^?1 and HL) with Ni‐ N bond distances between 2.01(1) and 2.11(1)Å. Water oxygen atoms occupy axial positions with Ni‐ O bond distances of 2.06(1) and 2.15(1) Å. The oxime groups in the Schiff base ligands are coordinated to Ni atom through their nitrogen atoms. One asymmetric intramolecular hydrogen bridge between the two oxime groups is found in the title complex.     

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).     

Bis(1-adamantanecarboxylato)triphenylantimony: Synthesis and structure

Bis(1-adamantanecarboxylato)triphenylantimony Ph₃Sb[OC(O)C₁₀H₁₅]₂ was synthesized in 92% yield by reacting triphenylantimony with 1-adamantanecarboxylic acid in the presence of hydrogen peroxide in diethyl ether. X-ray crystallography shows that the antimony atom has a distorted trigonal-pyramidal coordination with axially positioned oxygen atoms of carboxy groups. The axial angle OSbO and equatorial angles CSbC are 179.93(6)° and 99.90(5)°, 99.90(5)°, and 160.20(9)°, respectively; intramolecular contacts Sb···O(=C) are 2.613(1) Å. Structure data on structurally characterized triarylantimony dicarboxylates are systematized.     

The structure of the metallated iridium complex [(C8H12)Ir{P(OC6H3Me)(OC6H4Me)2} {P(OCH2)3CMe}]

The crystal structure of [(C₈H₁₂)$\text{Ir{P(OC}$₆H₃Me)(OC₆H₄Me)₂} {P(OCH₂)₃CMe}] has been determined. a 18.32, b 18.98, c 9.35 Å, U 3251 ų, Pn2_1^a, Z = 4, R = 0.048, 2541 observed data.The coordination about the iridium atom is distorted trigonal bipyramidal; the two phosphorus atoms are equatorial, the σ-bonded carbon is axial, and the bidentate cyclooctadiene is bonded axialequatorial. The IrC(axial) bonds are longer than the IrC(equatorial) bonds: 2.22, 2.26; 2.17, 2.19 Å. The IrC(σ) bond length is 2.19 Å, not significantly different from the formally π-bonded C to Ir distances. The IrP lengths of 2.201 and 2.240 Å and the PIrP angle of 108.7° are normal. The longer IrP bond is in the five-membered chelate ring. The inertness to substitution is discussed.     

Tetrapotassium dicarbonato­dioxo­peroxo­uranium(VI) 2.5‐hydrate,K4[U(CO3)2O2(O2)]·2.5H2O

The title compound was obtained by reacting UO₂ powder in 2 M K₂CO₃ with hydrogen peroxide. The compound contains individual [U(CO₃)₂O₂(O₂)]⁴⁻ ions, which are linked via an extended network of K atoms and hydrogen bonding. The U atom is coordinated to two trans‐axial O atoms and six O atoms in the equatorial plane, forming distorted hexagonal bipyramids. The carbonate ligands are bound to the U center in a bidentate manner, with U—O bond distances ranging from 2.438 (5) to 2.488 (5) Å. The peroxo group forms a three‐membered ring with the U atom, with U—O bond distances of 2.256 (6) and 2.240 (6) Å. The U=O bond distances of 1.806 (5) and 1.817 (5) Å, and an O—U—O angle of 175.3 (3)° are characteristic of the linear uranyl(VI) unit.     

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.     

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.     

Synthesis and crystal structure of KBi(C6H4O7) · 3.5H2O

A novel compound, KBi(C₆H₄O₇) · 3.5H₂O (I), has been synthesized in the Bi(NO₃)₂-K₃(HCit) system (HCit^3? is an anion of citric acid C₆H₈O₇) at a component ratio (n) of 8 in a water-glycerol mixture, and its crystal structure has been determined. The crystals are unstable in air. The crystals are triclinic: a = 7.462 Å, b = 10.064 Å, c = 17.582 Å, α = 100.27°, β = 99.31°, γ = 105.48°, V = 1221.2 ų, Z = 2, space group $P\bar 1$ . In the structure of I, asymmetric binuclear fragments [Bi₂(Cit^4?)₂(H₂O)₂]^2? are linked through inversion centers into polymeric chain anions. Ions K⁺ and crystal water molecules are arranged in channels between the chains. The Bi(1)...Bi(2) distances in the binuclear fragment are 4.62 Å, and the Bi(1)...Bi(1) and Bi(2)...Bi(2) distances between bismuth atoms in the chain are 5.83 and 5.95 Å, respectively. The chains are linked through bridging oxygen atoms of the ligands Cit to form layers. In the centrosymmetric four-membered chelate ring Bi₂O₂ formed through Bi-O(Cit) bonds, the distances Bi(1)-Bi(1) are equal to 4.55 Å, and Bi(1)-O are 2.66 and 2.84 Å. The Bi-O bond lengths in I are in the range 2.12–3.16 Å. The Cit ligands act as hexadentate chelating/bridging ligands.