Cambridge Structural Data Research Articles

Реакции бромидов бутен[бис(трифенилфосфония)] и пентан[бис(трифенил-фосфония)] с аренсульфоновыми кислотами

The reaction of equimolar amounts of tetraorganylphosphonium bromides with arenesulfonic acids in water led to formation of ionic tetraorganylphosphonium arenesulfonates [Ph3PCH2CH=CHCH2PPh3][OSO2C9H3N(OH-4)(I-7)]2 ∙ 4H2O (1), [Ph3P(CH2)5PPh3][OSO2С6H4(COOH-2)][Br] (2), yielding up to 89 %. The structural features of complexes 1, 2 were established by X-ray diffraction. Crystals 1 [C58H54I2N2O12P2S2, M 1350.89; triclinic system, symmetry group P–1; cell parameters: a = 9.506(8), b = 11.323(12), c = 13.662(10) Å; a = 82.21(4)°, β = 89.26(2)°, g = 72.60(4)°, V = 1390(2) Å3, Z = 2; rcalc = 1.614 g/cm3], 2 [C48H45O5P2SBr, M 875.75; triclinic system, symmetry group P–1; cell parameters: a = 10.307(7), b = 14.226(9), c = 16.291(10) Å; a = 67.07(3)°, β = 83.74(3)°, g = 74.65(3)°, V = 2122(2) Å3, Z = 2; rcalc = 1.371 g/cm3] consist of tetraorganylphosphonium cations and arene-sulfonate anions with a tetrahedral sulfur atom. The crystal of complex 2 also contains [Br]- anions. The P–C bond lengths vary in the range 1.779(3)−1.815(4) Å. The CPC bond angles take values of 104.33(15)−112.00(10)°. The S–O distances vary within the range of 1.4397(18)−1.4576(19) Å. Complete tables of atomic coordinates, bond lengths and bond angles for structures have been deposited in the Cambridge Structural Data Bank (No. 2164291 (1), No. 2165072 (2), deposit@ccdc.cam.ac.uk; http://www.ccdc cam.ac.uk).

Синтез и строение бис[3,4-дифторбензоата] трис(2-метоксифенил)сурьмы [(2-MeO)C6H4]3Sb[OC(O)C6H3(F2-3,4)]2 и бис[бензолсульфоната] трис(2-метоксифенил)сурьмы [(2-MeO)C6H4]3Sb[OSO2C6H5

Tris(2-methoxyphenyl)antimony bis[3,4-difluorobenzoate] (1) and tris(2-methoxyphenyl)antimony bis[benzenesulfonate] (2) were obtained by oxidative addition reaction from triarylantimony and 3,4-difluorobenzoic/benzenesulfonic acid in the presence of tertiary bu-tyl hydroperoxide in ether. The structure of 1 and 2 was established with the use of IR spectrosco-py and X-ray diffraction analysis (XRD). Crystals 1 [C35H27O7F4Sb, M 757.32; triclinic syngony, symmetry group P–1; cell parameters: a = 9.219(4), b = 9.507(6), c = 20.240(11) Å; a = 99.43(3)°, β = 95.756(16)°, g = 107.90(3)°; V = 1643.6(16) Å3; Z = 2; rcalc = 1.530 g/cm3; 2q 6.68-54.98 de-grees; total reflections 31858; independent reflections 7153; number of specified parameters 427; Rint = 0.0429; GOOF 1.051; R1 = 0.0265, wR2 = 0.0551; residual electron density (max/min); 0.30/-0.44 e/Å3], 2 [C33H31O9S2Sb, M 757.46; monoclinic system, symmetry group C2/c; cell parame-ters: a = 21.157(9), b = 10.363(4), c = 18.285(7) Å; β = 126.590(13) deg., V = 3219(2) Å3, Z = 1; rcalk = 1.563 g/cm3; 2q 6.012-54.234 degrees; total reflections 32454; independent reflections 3541; number of specified parameters 231; Rint = 0.0283; GOOF 1.161; R1 = 0.0283, wR2 = 0.0659; residual electron density (max/min); 0.74/-0.83 e/Å3] consist of trigonal bipyramidal molecules with electronegative ligands in axial positions. The Sb–C bond lengths vary in the range 2.093(2)−2.125(3) Å, The OSbO bond angles take values 176.63(6)° and 174.52(10)°, respective-ly. The Sb–O distances in 1 (2.1106(17) and 2.1149(17) Å) are shorter than in 2 (2.128(2) and 2.128(2) Å). Intramolecular Sb∙∙∙O contacts in 1 (3.162(2) and 3.257(2) Å) are significantly smaller than in 2 (3.617(2) and 3.617(2) Å) and do not exceed the sum of their van der Waals radii (3.7 Å). Complete tables of atomic coordinates, bond lengths and bond angles for structures have been de-posited in the Cambridge Structural Data Bank (No. 2123247 (1), No. 2116583 (2), depos-it@ccdc.cam.ac.uk; http://www.ccdc cam.ac.uk).

SYNTHESIS AND FEATURES OF THE MOLECULAR AND CRYSTAL STRUCTURE OF THE Cp4Ru4(µ3-CO)4 CLUSTER

When preparing the ruthenium dimer [Ru(CO)2Cp]2 in the thermal reaction of cyclopentadiene with Ru3(CO)12, the tetranuclear cluster [Ru(μ3-CO)Cp]4 (I) was obtained as a minor product. Spectral (13C and 1H NMR, IR) and structural studies were carried out for cluster I. By crystallization under different conditions, two types of dark cherry crystals were obtained, cluster I itself (crystal 1) and its tetrahydrate (crystal 2), the structure of which was determined by X-ray diffraction. Structural data for 1 and 2 have been deposited in the Cambridge Structural Data Center (CCDC nos. 2241197 and 2241199, respectively; deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk). Based on a comparative analysis of cluster geometry, it is shown that the distortion of the Ru4(CO)4 framework in I from ideal Td symmetry in the structure of a pure compound is determined by the anisotropy of intermolecular contacts in the crystal. Features of chemical bonding in the [Ru(μ3-CO)Cp]4 cluster and its iron-containing analogue were studied using DFT calculations using topological analysis of electron density to compare energy characteristics and effective force constant bonding interactions. The necessity of using criteria for elastic deformations of interatomic interactions (force constants) for the correct description of structural and chemical phenomena, for example, such as the structural non-rigidity of the framework of transition metal clusters, has been demonstrated.

Синтез и строение комплексов сурьмы [n-C5H11PPh3]2[Sb2I8(acetone)2] и [Ph4P]3[Sb2I9]∙EtO(CH2)2OH

The interaction of antimony iodide with n-pentyltriphenylphosphonium iodide (1:1 mol.) in acetone and tetraphenylphosphonium iodide (3:2 mol.) in ethylene glycol monoethyl ether (ethyl cellosolve) has been used to synthesize ionic complexes [n-C5H11PPh3]2[Sb2I8(acetone)2] and [Ph4P]3[Sb2I9]∙EtO(CH2)2OH. According to the X-ray analysis data obtained on an automatic diffractometer D8 Quest Bruker (MoKa-radiation, λ = 0.71073 Å, graphite monochromator) at 293 K, of crystals 1 [C26H32OPI4Sb, M 1020.84, the triclinic syngony, the symmetry group Р-1; cell parameters: a = 10.573(4) Å, b = 13.303(5) Å, c = 13.569(5) Å, α = 117.749(16) degrees, β = 95.534(17) degrees, γ = 100.715(14) degrees; V = 1622.4(10) Å3; the crystal size is 0.32 × 0.22 × 0.13 mm; intervals of reflection indexes are -16 ≤ h ≤ 16, -20 ≤ k ≤ 20, -21 ≤ l ≤ 21; total reflections 98254; independent reflections 13003; Rint 0.0285; GOOF 1.037; R1 = 0.0438, wR2 = 0.0745; residual electron density 1.25/-2.06 e/Å3] and 2 [C76H70I9O2P3Sb2, M 2493.83, the triclinic syngony, the symmetry group Р–1; cell parameters: a = 10.881(7) Å, b = 16.549(7) Å, c = 25.287(12) Å, α = 109.03(2) degrees, β = 94.67(2) degrees, γ = 98.52(3) degrees; V = 4216(4) Å3; the crystal size is 0.37×0.11×0.07 mm; intervals of reflection indexes are -14 ≤ h ≤ 14, -22 ≤ k ≤ 22, -33 ≤ l ≤ 33; total reflections 146846; independent reflections 21003; Rint 0.0708; GOOF 1.014; R1 = 0.0763, wR2 = 0.0967; residual electron density 1.23/-1.06 e/Å3], the phosphorus atoms in cations have a slightly distorted tetrahedral coordination with the CPC bond angles 107.48(11)-111.52(11) and 106.5(3)-113.3(3) degrees and similar P–C bond lengths 1.795(3)–1.802(2) Å and 1.787(5)–1.809(6) Å in 1 and 2, respectively. In the centrosymmetric [Sb2I8(acetone)2]2– anion, the antimony atoms have a distorted octahedral coordination (trans-angles 171.476(9)–176.33(3) degrees, the acetone molecule occupies an axial position being coordinated by the oxygen atom (Sb∙∙∙O 2.820(10) Å). The Sb–Ib. bonds (3.0997(12) Å) are longer than Sb–Iterm: 2.7780(8)–2.9553(10) Å. In the [Sb2I9]3– anion trans-ISbI angles vary in the range 169.612(17)–173.426(19) degrees, Sb–Iterm. bonds 2.8613(13)–2.9609(12) Å are shorter than Sb–Ib: 3.0986(12)–3.2760(13) Å. Solvate ethyl cellosolve mole-cules form dimers via hydrogen bonds O(1)∙∙∙H(2A) 2.11 Å. Complete tables of coordinates of atoms, bond lengths and valence angles for structures 1 and 2 are deposited at the Cambridge Structural Data Bank (no. 1984511 (1), 2157456 (2); deposit@ccdc.cam.ac.uk; http: //www.ccdc.cam.ac.uk).

Синтез и кристаллическая структура бис(2-метилкарборанил-карбоксилата) трис(3-фторфенил)сурьмы

Oxidation of tris(3-fluorophenyl)antimony with hydrogen hydroperoxide in the presence of 2-methylcarboranylcarboxylic acid leads to the formation of tris(3-fluorophenyl)antimony bis(2-methylcarboranylcarboxylate) (1), the structural features of which have been established by X-ray diffraction analysis. According to X-ray diffraction analysis performed at 293 K on an automatic four-circle diffractometer D8 Quest Bruker (two-coordinate CCD detector, Mo Kα-radiation, λ = 0.71073 Å, graphite monochromator), the crystals are characterized by: C26H38B20F3O4Sb, M 809.52; monoclinic system, space group С2/c; cell parameters: a = 19.050(13), b = 14.441(9), c = 14.568(9) Å;  = 90, β = 98.51(2),  = 90; V = 3964(4) Å3; Z = 4; crystal size 0.8 × 0.55 × 0.29 mm; index ranges –25 ≤ h ≤ 25, –18 ≤ k ≤ 18, –18 ≤ l ≤ 19; total reflections 37401; independent reflections 4709; Rint 0.0545; GOOF 1.108; R1 = 0.0578, wR2 = 0.1482; residual electron density –0.59/1.09 e/Å3. According to X-ray diffraction analysis data, in the molecules of compound 1, the antimony atoms have a distorted trigonal-bipyramidal coordination with the oxygen atoms of the carboxylate ligands in the axial positions. The Sb–C bonds (2.104(4)–2.114(8) Å) are shorter than the Sb–O distances (2.113(3) Å), the OSbО axial angle is 178.48(15)°, the CSbC angles are 109.7(2)°, 118.4(2)°, 131.8(3)°, while a significant increase in one of the angles is associated with the cis-conformation of the carboxylate ligands relative to the equatorial plane. The conformation of aryl ligands with respect to the equatorial plane [C3] is propeller. Structure 1 contains intramolecular Sb•••O=С contacts between the antimony and oxygen atoms of the carbonyl groups of the carboxylate ligands, which are 3.089(3) Å. The formation of a spatial network in the crystal of compound 1 is due to the presence of weak hydrogen bonds with the participation of boron atoms of carboxylate ligands and fluorine of aryl ligands: B•••H (3.19 Å) and F•••B (3.45 Å). Complete tables of atomic coordinates, bond lengths, and bond angles are deposited at the Cambridge Structural Data Center (no. 2178731; deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk/data_request/ cif).

Синтез и строение продукта реакции пента-пара-толилсурьмы с гептафторпропил(t-бутил)дикетоном-1,3 p-Tol4Sb[t-BuC(O)СHС(О)С3F7

Penta(para-tolyl)antimony reacts with heptafluoropropyl(t-butyl)diketone-1,3 with the splitting out of toluene and formation of the substitution product p-Tol4Sb[t-BuC(O)СHС(О)С3F7] (1), yielding 82%. The compound was identified by IR spectroscopy and X-ray diffraction analysis. The X-ray analysis was performed on an automatic four-circle diffractometer D8 Quest Bruker (MoK radiation, λ = 0.71073 Å, graphite monochromator) at 293 K. Crystal size is 0.59 × 0.48 × 0.13 mm, P-1, a = 10.47(2), b = 10.94(2), c = 17.04 (3) Å, α = 73.12 (6), β = 88.94(8), γ = 89.94(8) deg., V = 1867 (7) Å3, Z = 2, ρ = 1.39 g/cm3, F(000) = 792.0, the 2θ interval is 3.89–56.999 deg., R1 = 0.2213, wR2 = 0.5429. According to the X-ray diffraction data, compound 1 is a molecular complex, in which the antimony atoms have an octahedral coordination with two oxygen atoms and two carbon atoms in the equatorial plane; the axial positions are occupied by the two remaining tolyl ligands. The CSbC axial angle is strongly distorted and is equal to 159.6 (8)°. The CSbO diagonal angles in the equatorial plane are 167.1(7)°, 166.9(7)°. The lengths of the Sb–C bonds are 2.11(2) and 2.19 (3) Å. The formation of the chain spatial structure of crystals is due to formation of bonds between the molecules involving fluorine (H∙∙∙F 2.64−2.83 Å) and carbon (C∙∙∙F 3.005 Å) atoms. Complete tables of atomic coordinates, bond lengths, and valence angles are deposited in the Cambridge Structural Data Bank (No. 2067768 (1); deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk/data_request/cif).

A novel сalcium trifluoroacetate structure

Objectives. The study was devoted to considering the features of the synthesis and crystal structure of calcium trifluoroacetate Ca2(CF3COO)4·8CF3COOH and investigating the products of its thermal behavior.Methods. The compositions of the proposed structural form were characterized by various physicochemical methods (X-ray diffraction, IR spectroscopy), and the products of thermal decomposition were determined under dynamic vacuum conditions.Results. The reaction between calcium carbonate and 99% trifluoroacetic acid yielded a new structural type of calcium trifluoroacetate Ca2(CF3COO)4·8CF3COOH (I) in the form of colorless prismatic crystals unstable air. X-ray diffraction results confirmed the composition I: space group P21, with unit cell parameters: a = 10.0193(5) Å, b = 15.2612(7) Å, c = 16.3342(8) Å, β = 106.106(2)°, V = 2399.6(2) Å3, Z = 2. The structure is molecular, constructed from Ca2(CF3COO)4·8CF3COOH dimers. The end molecules of the trifluoroacetic acid were involved in the formation of intramolecular hydrogen bonds with oxygen atoms of the bidentate bridging anions CF3COO−. There were strongly pronouncedsymmetric and asymmetric absorption bands of COO and CF3-groups in the IR spectrum of the resulting compound in the range of 1200–1800 cm−1. The definite peak of the oscillation of the OH-group at 3683 cm−1 corresponds to the trifluoroacetic acid molecules present in the structure. The broadpeak of the valence oscillations in the range of 3300–3500 cm−1 is caused by the presence of intramolecular hydrogen bonds. Decomposition began at 250°C and 10−2 mm Hg with calcium fluoride CaF2 as the final decomposition product.Conclusions. We obtained a previously undescribed calcium–trifluoroacetic acid complex whose composition can be represented by Ca2(CF3COO)4·8CF3COOH. The crystal island structure is a dimeric molecule where the calcium atoms are bound into dimers by four trifluoroacetate groups. The complex was deposited in the Cambridge Structural Data Bank with a deposit number CCDC 2081186. Although the compound has a molecular structure, thermal decomposition leads to the formation of calcium fluoride characterized by a small particle size, which may further determine its applications.

Реакция пентафенилфосфора с гексахлороплатиновой кислотой

Tetraphenylphosphonium hexachloroplatinate (1) was synthesized by the interaction of pentaphenylphosphorus with hexachloroplatinic acid in acetone. The recrystallization of complex 1 from dimethylsulfoxide gave tetraphenylphosphonium dimethylsulfoxidopentachloroplatinate (2). The compounds have been characterized by IR-spectroscopy and X-ray analysis. The absorption bands characterizing stretching vibrations of the phenyl groups are present in the IR spectra, recorded on a Shimadzu IRAffinity-1S Fourier spectrometer in the 4000–400 cm–1 area in KBr pellets. According to the X-ray analysis, the compound unit cell parameters are: triclinic syngony, space group (1, 2), а = 10.205(10), b = 10.970(15), c = 12.160(11) Å (1), а = 7.7667(4), b = 13.3069(7), c = 14.2562(7) Å (2), a = 73,65(4)°, β = 80.64(3)°, g = 77.48° (1), a = 80.972(4)°, β = 88.205(4)°, g = 89.199(4)° (2), V = 1272(2) Å3 (1), 1454.38(13) Å3 (2). The crystals of complexes 1 and 2 consist of the tetrahedral tetraphenylphosphonium cations and octahedral anions. In cations the phosphorus atoms have a slightly distorted tetrahedral environment (the CPC angles are 107.8(3)-113.2(3)° (1), 105.9(3)–112.9(3)° (2), the P-C distance is 1.785(6)-1.805(6) Å (1), 1.783(7)–1.791(6) Å (2). Platinum atoms in the anions of complexes 1 and 2 are hexacoordinated. In complex 2 the dimethyl sulfoxide ligand is coordinated with the Pt atom via the sulfur atom 2.290(2) Å. Complete tables of coordinates of atoms, bond lengths and valence angles are deposited at the Cambridge Structural Data (CCDC 1865783, 829586 http://www.ccdc.cam.ac.uk).

Синтез и строение бис(2,5-диметилбензолсульфоната) и бис(дибромфторацетата) трис(3-фторфенил)сурьмы

The interaction of tris(3-fluorophenyl)antimony with 2,5-dimethylbenzenesulfonic or dibromofluoroacetic acid in diethyl ether in the presence of tert-butyl hydroperoxide has synthe-sized tris(3-fluorophenyl)antimony bis(2,5-dimethylbenzenesulfonate) (1) and tris(3-fluorophenyl)antimony bis(dibromofluoroacetate) (2). The X-ray diffraction pattern has been obtained at 293 K on an automatic diffractometer D8 Quest Bruker (MoKα-radiation, λ = 0.71073 Å, graphite monochromator) for crystal 1 [C34H30F2O6S2Sb, M 777.45, the triclinic syngony, the symmetry group P–1; cell parameters: a 10.634(18) Å, b 11.38(2) Å, c 14.31(3) Å, α = 90.51(8) degrees, β = 90.35(11) degrees, γ = 112.79(5) degrees; V = 1596(5) Å3; the crystal size is 0.5×0.48×0.17 mm; intervals of reflection indexes are –15 ≤ h ≤ 14, –15 ≤ k ≤ 15, –19 ≤ l ≤ 19; total reflections 30473; independent reflections 8318; Rint 0.0920; GOOF 1.894; R1 = 0.1699, wR2 = 0.4237; residual electron density 6.78/–5.48 e/Å3] and crystal 2 [C22H12O4F7SbBr2, M 754.89, the triclinic syngony, the symmetry group P–1; cell parameters: a 8.98(3) Å, b 10.41(2) Å, c 14.92(3) Å, α = 90.77(7) degrees, β = 90.73(9) degrees, γ = 113.95(10) degrees; V = 1275(5) Å3; the crystal size is 0.65 × 0.32 × 0.14 mm; intervals of reflection indexes are –13 ≤ h ≤ 13, –15 ≤ k ≤ 14, –21 ≤ l ≤ 21; total reflections 61066; independent reflections 8511; Rint 0.0863; GOOF 1.983; R1 = 0.1529, wR2 = 0.4647; residual electron density 4.41/–3.48 e/Å3] the antimony atoms have a distorted trigonal-bipyramidal coordination. The axial OSbO angles are 178.2(3) (1) and 174.0(4) (2); the sum of the CSbC angles in the equatorial plane is 360. The Sb–O and Sb–C bond lengths are 2.108(9)–2.131(12) Å and 2.090(14)– 2.21(3) Å. The structural organization of crystals 1 and 2 is controlled by intermolecular bonds O···H 2.53–2.70 Å (1) and 2.57–2.60 Å (2), F•••H 2.46–2.59 Å (1) and Br•••H 3.02 Å (2). In 2 the short contacts C··· F have been observed between the aryl ligands of neighboring molecules 3.079 and 3.085 Å. Complete tables of coordinates of atoms, bond lengths and valence angles for structures 1 and 2 are deposited at the Cambridge Structural Data Bank (no. 2055553, 2055764; depos-it@ccdc.cam.ac.uk; http: //www.ccdc.cam.ac.uk).

Синтез и строение моно-, би- и трехъядерных органилсульфонатных производных триарилсурьмы

The interaction of triarylantimony (Ar = 4-FC6H4, 3-MeC6H4, 3-FC6H4) with tert-butyl hydroperoxide and 3,4-dimethylbenzenesulfonic acid, as well as 2,4-dinitrobenzenesulfonic and trifluoromethanesulfonic acids (1:2:1, 1:1:1, and 3:2:3 mol) in diethyl ether has led to synthesis of triarylantimony di- and oxo-sulfonates: tris(4-fluorophenyl)antimony bis(2,4-dimethylbenzenesulfonate) (4-FC6H4)3Sb(OSO2C6H3Me2-2,4)2 (1), tris-(3-methylphenyl) anti-mony µ-oxo-bis-(2,4-dinitrobenzenesulfonate) [(3-MeC6H4)3Sb(OSO2C6H3NO2-2,4)]2O (2), and a solvate of nona-(3-fluorophenyl)tristiboxane-1,5-diyl bis-(trifluoromethanesulfonate) with benzene CF3OSO2Sb(3-FC6H4)3OSb(3-FC6H4)3OSb(3-FC6H4)3OSO2CF3·PhH (3), which have been structurally characterized. The X-ray diffraction pattern has been obtained at 293 K on an auto-matic diffractometer D8 Quest Bruker (MoKα-radiation, λ = 0.71073 Å, graphite monochromator): crystals 1 [C34H30O6S2SbF3, M 777,45; the monoclinic syngony, the C2/c symmetry group; cell parameters: a = 18.980(10), b = 15.667(8), c = 12.271(7) Å; α = 90.00, β = 114.36(2), γ = 90.00; V = 3324(3) Å3; the crystal size is 0.51 × 0.32 × 0.82 mm; intervals of reflection in-dexes are –29 ≤ h ≤ 33, –27 ≤ k ≤ 27, –21 ≤ l ≤ 21; total reflections 63539; independent reflec-tions 9421; Rint 0.0468; GOOF 1.011; R1 = 0.0400, wR2 = 0.0801; residual electron density 0.88/0.92 e/Å3], 2 [C54H48N4O15S2Sb2, M 1300.58; the triclinic syngony, the P–1 symmetry group; cell parameters: a = 10.332(5), b = 12.312(5), c = 13.045(4) Å; α = 77.744(12), β = 84.85(2), γ = 74.25(2); V = 1559.8(11) Å3; the crystal size is 0.37 × 0.19 × 0.16 mm; inter-vals of reflection indexes are 15 ≤ h ≤ 15, 18 ≤ k ≤ 18, 19 ≤ l ≤ 19; total reflections 75043; independent reflections 11314; Rint 0.0372; GOOF 1.093; R1 = 0.0506, wR2 = 0.1511; residual electron density 2.75/0.59 e/Å3], and 3 [C62H42O8F15S2Sb3, M 1629.33; the monoclinic syngony, the P21/n symmetry group; cell parameters: a = 15.933(12), b = 16.759(12), c = 24.13(2) Å; α = 90.00, β = 91.51(3), γ = 91.51(3); V = 6441(9) Å3; the crystal size is 0.47 × 0.2 × 0.18 mm; intervals of reflection indexes are 20 ≤ h ≤ 20, 21 ≤ k ≤ 21, 31 ≤ l ≤ 31; total reflec-tions 139052; independent reflections 14671; Rint 0.0444; GOOF 1.134; R1 = 0.0435, wR2 = 0.0998; residual electron density 1.38/1.12 e/Å3], the antimony atoms have a distorted trigonal-bipyramidal coordination with the oxygen atoms in axial positions (trans-OSbO и cis-OSbС angles are 177.94(6)°, 85.02(6)–93.75(6)° (1), 175.52(6)°, 81.11(11)–94.47(9)° (2), and 175.09(14)178.32(13)°, 80.60(17)–96.79(17)° (3). The Sb–Osulf. bond lengths are 2.1212(17) Å (1), 2.289(2) Å (2), and 2.402(4), 2.430(4) Å (3), they are longer than those for Sb–Obridge 1.9340(7) (2) and 1.915(3)–2.039(3) Å (3). The SbC bond lengths in 1–3 change in a narrow range of values: 2.086(2)2.0946(19), 2.104(3)2.108(3), and 2.094(5)2.124(4) Å, respectively. The structural organization in crystals 1–3 is caused by the weak van-der-Waals interactions: S=О···Н–C 2.46–2.62 Å (1), S=О···Н–C 2.39–2.65 Å (2), and S=О···Н–C 2.46–2.65, C–F···Н–C 2.46–2.55 Å (3). Complete tables of coordinates of atoms, bond lengths and valence angles for structures 13 are deposited at the Cambridge Structural Data Bank (No. 1919945, 1898995 and 1575647; deposit@ccdc.cam.ac.uk; http: //www.ccdc.cam.ac.uk).

Дихлородицианоаураты органилтрифенилфосфония [Ph3PR][Au(CN)2Cl2] (R = n-Pr, i-Bu, n-Hp): синтез и строение

The interaction of potassium dichlorodicyanoaurate with n-propyl-, i-butyl- and n-heptyltriphenylphosphonium bromides in water followed by the recrystallization from acetoni-trile leads to the dichlorodicyanoaurate complexes [Ph3P(n-Pr)][Au(CN)2Cl2] (1), [Ph3P(i Bu)][Au(CN)2Cl2] (2), and [Ph3P(n-Hp)][Au(CN)2Cl2] (3). Compounds 1 and 2 have been identified by the IR spectroscopy; structure of compound 3 has been determined by the X-ray diffraction analysis. According to the X-ray data, complex 3 consists of n-heptyltriphenylphosphonium cation and two types of crystallographically independent centrosymmetric square-planar dichlorodicyanoaurate anions. The phosphorus atom in the cation has a slightly distorted tetrahedral coordination with the CPC bond angles within the interval 108.3(5)–110.5(5)°; the P–C distances are 1.801(10)–1.832(10) Å. The square-planar coordination of the gold atoms in centrosymmetric anions [Au(CN)2Cl2] is almost undistorted: the CAuC and ClAuCl trans-angles equal 180, the CAuCl cis-angles vary in a narrow range 74.5(9)–105.5(9). The Au–Cl bond lengths in anions do not exceed the sum of the covalent radii of the gold and chlorine atoms and equal 2.406(3), 2.388(3) Å; the Au–C bond lengths are 2.021(14), 2.037(13); they are close to the sum of the covalent radii of the gold and carbon atoms. The structural organization in crystals 3 is caused by the H∙∙∙N≡C (2.55–2.63 Å) and С–H∙∙∙Cl–Au (2.87 Å) hydrogen bonds. Moreover, the structure contains the additional С–H∙∙∙π(Ph) contacts with the distances from the hydrogen atom to the plane of the benzene ring that are equal to 2.80 Å. Complete tables of atomic coordinates, bond lengths, and valence angles are deposited in the Cambridge structural data Bank (No. 2094701 for 3; deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).

Синтез и строение хлорида циклопентадиенилдиферроценоилацетонатоциркония С5H5[С10H9FeC(O)CHC(O)CF3]2ZrCl

Interaction of zirconocene dichloride with ferrocenoyltrifluoroacetylacetone in benzene so-lution led to synthesis of a trans-isomer of cyclopentadienyl diferrocenoylacetonatozirconium chloride, the structure of which was proved by X-ray diffraction analysis. According to the X-ray analysis performed at 293 K on an automatic four-circle diffractometer D8 QuestBruker (MoCA radiation, λ = 0.71073 Å, graphite monochromator), the zirconium atoms in the trans-isomer of complex 1 have a distorted octahedral configuration [C33H25F6ClFe2ZrO4 (1), M 837.90; the crys-tal structure is triclinic, the symmetry group P ; crystal unit cell parameters: a = 10.16(3), b = 12.39(3), c = 13.44 (3) Å; α= 95.70(10)º, β = 102.62(14)º, γ = 93.77(2)° ; V = 1635 (6) Å3; crystal size 0.16 × 0.09 × 0.08 mm3; reflection index intervals –12 ≤ h ≤ 12, –15 ≤ k ≤ 15, –17 ≤ l ≤ 17; total reflections 23770; independent reflections 7090; Rint = 0.3164; GOOF = 1.054; R1 = 0.1601, wR2 = 0.3121; residual electron density 1.41/–1.80 e/Å3. In the IR spectrum of com-pound 1 the bands are observed at 808, 1007, 1055, 1409, 2855, 2926, 3099 cm–1, which can be attributed to fluctuations in the bonds of the ferrocene substituent. The intense vibration band at 1298 cm–1 corresponds to the vibrations of the CF3 groups. Valence vibrations of the Zr-O bonds appear in the IR spectrum as a series of bands in the region of 400–1000 cm–1. According to the X-ray diffraction analysis, the packing of complex 1 molecules into layers is possible due to short contacts С···С (3.323 Å). Each of the layers is formed by reference contacts Н···С (2.850 Å). Complete tables of atomic coordinates, bond lengths, and valence angles are deposited in the Cambridge structural data Bank (No. 1988379 for 1; deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).

Approaches for machine learning intermolecular interaction energies and application to energy components from symmetry adapted perturbation theory.

Accurate prediction of intermolecular interaction energies is a fundamental challenge in electronic structure theory due to their subtle character and small magnitudes relative to total molecular energies. Symmetry adapted perturbation theory (SAPT) provides rigorous quantum mechanical means for computing such quantities directly and accurately, but for a computational cost of at least O(N5), where N is the number of atoms. Here, we report machine learned models of SAPT components with a computational cost that scales asymptotically linearly, O(N). We use modified multi-target Behler-Parrinello neural networks and specialized intermolecular symmetry functions to address the idiosyncrasies of the intermolecular problem, achieving 1.2 kcal mol-1 mean absolute errors on a test set of hydrogen bound complexes including structural data extracted from the Cambridge Structural Database and Protein Data Bank, spanning an interaction energy range of 20 kcal mol-1. Additionally, we recover accurate predictions of the physically meaningful SAPT component energies, of which dispersion and induction/polarization were the easiest to predict and electrostatics and exchange-repulsion are the most difficult.

Синтез и строение гексабромоплатината циклопропилтрифенилфосфония

Using the interaction of potassium hexabromoplatinate with cyclopropyltriphenylphosphonium bromide in acetonitrile after crystallization from dimethyl sulfoxide, the [Ph 3 PC 3 H 5 ] 2 [PtBr 6 ] complex ( 1 ) has been obtained for the first time (red crystals, m.p. 235 °C). The compound 1 has been characterized by IR-spectroscopy and X-ray analysis. According to the data of X-ray analysis the unit cell crystallographic parameters of compound 1 are: orthorhombic syngony, the symmetry group Pna2 1 ; M 1281.22; cell parameters: a = 14.653(6), b = 18.874(8), c = 15.921(8) Å; a = 90.00 degrees, β = 90.00 degrees, g = 90.00 degrees; V = 4403(3) Å 3 ; ρ (calc.) = 1.933 g/cm 3 , Z = 8, the crystal size is 0.32×0.24×0.16 mm; intervals of reflection indexes –25 ≤ h ≤ 25, –17 ≤ k ≤ 19, –21 ≤ l ≤ 20; total reflections 66507; independent disclosures 10802; μ = 8.733 mm –1 ; R 1 = 0.0344; wR 2 = 0.0755 (all date), R 1 = 0.0484; wR 2 = 0.0807 ( F 2 > 2s( F 2 )); residual electron density 1,28/–2,05 e/Å 3 . In cations, the phosphorus atoms have a distorted tetrahedral coordination (the CPC angles equal 88.6(3)°-122.4(3)°, the P-C bond lengths are 1.541(5)-2.273(7) Å). The platinum atoms are coordinated by six bromine atoms in the anion (the BrPtBr trans -angles are close to 180°, the BrPtBr cis -angles have the values 89.17(4)-108.(3)°, the Pt-Br bond lengths are 2.1618(9)-2.9732(14) Å). Complete tables of coordinates of atoms, bond lengths and valence angles are deposited at the Cambridge Structural Data (№ 1969775; http://www.ccdc. cam.ac.uk).

Бис(бромдифторацетат) три-пара-толилвисмута. Синтез и особенности строения

The interaction of tri(para-tolyl)bismuth with tert-butyl hydroperoxide and bromodifluoroacetic acid in diethyl ether have synthesized tris(para-tolyl)bismuth bis(bromodifluoroacetate). The X-ray diffraction pattern for the crystal has been obtained at 293 K on an automatic diffractometer D8 Quest Bruker (MoKα-radiation, λ = 0.71073 Å, graphite monochromator), the results are [C25H21O4F4Br2Bi, M 830.22, the triclinic syngony, the symmetry group P–1; cell parameters: a = 10.292(8), b = 11.752(9), c = 12.693(9) Å, α = 89.42(2) degrees, β = 78.04(3) degrees, γ = 78.04(3) degrees; V = 1424.8(18) Å3; the crystal size is 0.73×0.57×0.41 mm; intervals of reflection indexes are –13 ≤ h ≤ 13, –15 ≤ k ≤ 15, –16 ≤ l ≤ 16; total reflections 45443; independent reflections 7096; Rint 0.1030; GOOF 1.049; R1 = 0.0739, wR2 = 0.1834; residual electron density 2.11/–2.78 e/Å3], the bismuth atom have a distorted trigonal-bipyramidal coordination. The OBiO axial angle is 172.2(3) degrees; the sum of the CBiC angles in the equatorial plane is 360.6. The Bi–O and Bi–C bond lengths are 2.275(8), 2.295(8) Å and 2.187(10)–2.212(13) Å. The Bi•••O=С distances are 3.127(10) and 3.159(10) Å, which is less than the sum of the van der Waals radii of bismuth and oxygen (3.59 Å). There are no intermolecular contacts H∙∙∙Hal in the crystal. Complete tables of coordinates of atoms, bond lengths and valence angles for the structure are deposited at the Cambridge Structural Data Bank (no. 1923097; deposit@ccdc.cam.ac.uk; http: //www.ccdc.cam.ac.uk).

Синтез и исследование структуры несимметричного двуядерного комплекса дифторида бора

A multi-ligand binuclear complex of boron difluoride was obtained in which two diketonate rings are connected by a sulfur atom through central carbon atoms (g). In the first cycle two methyl groups – the acetylacetonate fragment ( acac ) – are present as substituents; so are the methyl and phenyl groups – the benzoylacetonate fragment ( bzac ) – in the second cycle. The resulting complex has been characterized by IR and PMR spectroscopy and X-ray diffraction (XRD) methods. According to the X-ray diffraction data, the structure of the resulting complex follows the structure of aromatic sulfides. The interaction of substituents at β- and g-carbon atoms has been considered. 1 С 15 H 14 O 4 B 2 F 4 S, M 387.94, T 293(2) K, monoclinic, P 2 1 /c, a = 7.893(12), b = 23.41(4), c = 9.393(13) Å, a = 90°, b = 103.32(6)°, g = 90°, V = 1689(5) Å 3 , Z = 4, ρ = 1.525 g/сm 3 , µ = 0.252 mm –1 , F(000) = 792.0, crystal size 0.6×0.23×0.23 mm, 2q = 5.66-82.24°, index ranges –14 ≤ h ≤ 14, –36 ≤ k ≤ 36, –12 ≤ l ≤ 12, reflection collected 37642, independent reflections 6665, GOOD 1.320, parameters 238, R int = 0.0843, R 1 = 0.1198, wR 2 = 0.3542. Information on the structure of the obtained complex (tables of atom coordinates, bond lengths, and bond angles) was deposited at the Cambridge Structural Data Bank No. 1911543, deposit@ccdc.cam.ac.uk; http: //www.ccdc. cam.ac.uk).

Синтез и строение комплексов висмута [Ph4P]+2[Bi2I8(m2-Et2SO-O)]2– и [Ph4P]+2trans-[Bi2I8(dmso-O)2]2

The interaction of bismuth (III) iodide with tetraphenylphosphonium iodide in dimethylsulfoxide and diethylsolfoxide have synthesized bismuth complexes [Ph 4 P] + 2 [Bi 2 I 8 (m 2 -Et 2 SO- O )] 2– ( 1 ) и [Ph 4 P] + 2 trans -[Bi 2 I 8 (dmso- O ) 2 ] 2 - ( 2 ). They have been structurally characterized. The X-ray diffraction pattern has been obtained at 293 K on an automatic diffractometer D8 Quest Bruker (Mo K α -radiation, λ = 0.71073 Å, graphite monochromator) of crystals 1 [C 26 H 24 O 0.5 SI 4 BiP, M 1124.06, the monoclinic syngony, the symmetry group С2/с; cell parameters: а = 27.563(15) Å, b = 9.140(7) Å, с =28.978(17) Å; α = 90.00 degrees, β =119.069(17) degrees, γ = 90.00 degrees; V = 6381(7) Å 3 ; the crystal size 0.43×0.35×0.19 mm; intervals of reflection indexes are –41 ≤ h ≤ 41, –13 ≤ k ≤ 13, –43 ≤ l ≤ 42; total reflections 124163; independent reflections 11658; R int 0.0708; GOOF 1.025; R 1 = 0.0852, wR 2 = 0.1380; residual electron density –3.19/2.61 e/Å 3 ][C 28 H 32 O 2 PS 2 BiI 4 , M 1212.21; the triclinic syngony, the symmetry group Р-1; cell parameters: а = 9.409(10) Å, b = 14.149(16) Å, с =15.745(15) Å; α = 113.85 degrees, β =92.50(4) degrees, γ = 104.05 degrees; V = 1836(3) Å 3 ; the crystal size 0.64×0.43×0.4 mm; intervals of reflection indexes are –15 ≤ h ≤ 15, –23 ≤ k ≤ 24, –25 ≤ l ≤ 26; total reflections 117427; independent reflections 18300; R int 0.0927; GOOF 1.006; R 1 = 0.1366, wR 2 = 0.1369; residual electron density –2.99/2.59 e/Å 3 ] the phosphor atoms have a distorted tetrahedral coordination (the CPC angles are 107.7(3)–112.8(4)° ( 1 ), 107.2(3)–111.2(3)° ( 2 ); the Р–С bond lengths are 1.771(7)–1.823(8) Å ( 1 ), 1.786(6)–1.804(5) Å ( 2 )). The equatorial angles IBiI are 86.22(3)–92.87(3)° ( 1 ), 80.43(8)–95.86(8)° ( 2 ), the axial angles OBiI are 162.71(11)° ( 1 ), и 174.34(11)° ( 2 ); the equatorial Bi–I bond lengths are 2.8882(14)–3.2829(18) Å ( 1 ), 2.928(2)–3.364(3) Å ( 2 ), the axial Bi–I bond lengths are 2.9156(17) Å ( 1 ), 2.928(2) Å ( 2 ), the axial Bi–O bond lengths are 2.747(5)Å ( 1 ), 2.572(5) Å ( 2 ). Complete tables of coordinates of atoms, bond lengths and valence angles for structures 1 and 2 are deposited at the Cambridge Structural Data Bank (no. 1969793, 1969795; deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).

Синтез и строение 2-фенил-карборанилкарбоксилата дифенилвисмута

Diphenylbismuth 2-phenylcarboranylcarboxylate ( 1 ) has been obtained by the interaction between triphenylbismuth and 2-phenylcarboranylcarboxylic acid in benzene in 91% yield. The compound has been identified by IR spectroscopy and X-ray diffraction analysis. According to the X-ray diffraction analysis the target product 1 is a benzene solvate and has a polymer structure [C 48 H 56 O 4 B 20 Bi 2 , М = 1331.09; the triclinic system, space group Р ; a 10.602(7), b 13.211(10), c 20.07(2) Å; α 93.47(4), β 90.02(4), γ 90.01(3) degrees; V 2806(4) Å 3 ; Z 2; ρ calc 1.575 g/cm 3 ; µ 6.304 mm –1 ; F (000) 1284.0; crystal size 0.55×0.11×0.07 mm; 2θ for data collection 5.26–56.98 degrees; index ranges –13 ≤ h ≤ 13, –16 ≤ k ≤ 16, –25 ≤ l ≤ 25, total reflections 60631; independent reflections 11732; R int 0.0938; variables 727; GOOF 1.013; R 1 = 0.0338; wR 2 = 0.0628; residual electron density 1.50/–1.05 e/Å 3 ]. The crystal contains two types of crystallographically independent molecules ( a and b ), the crystallographic parameters of which are slightly different from each other. Bismuth atoms have a bisphenoid coordination with the apically located oxygen atoms of carboxylate substituents. Two phenyl ligands and an electron lone pair are in the equatorial plane. The OBiO axial angles are 159.62(12)° and 159.95(12)°. The CSbC equatorial angles are 103.4(2)° and 103.0(2)° in molecules a and b , respectively. The Bi–C bond lengths are 2.232(6), 2.303(7) Å ( a ) and 2.240(5), 2.300(7) Å ( b ); they are comparable with the similar distances for the previously structurally characterized diarylbismuth carboxylates. Through interactions of bismuth atoms with oxygen atoms, molecules of one layer in a crystal form the [···Bi(Ph) 2 –O–C(R)=O···] n polymer chains along the crystallographic axis a . Complete tables of coordinates of atoms, bond lengths and valence angles are deposited at the Cambridge Structural Data Bank (No. 1957181; deposit@ccdc.cam.ac.uk; http:// www.ccdc.cam.ac.uk/data_request/cif).

Синтез и строение комплексов циркония [Ph3PCH=CHMe]2[ZrCl6] и гафния [Ph3PCH2C(O)Me]2[HfCl6

The interaction of zirconium (IV) chloride and hafnium (IV) cloride with tetraorganylphosphonium chlorides in solutions of acetonitrile synthesized the following complexes: [Ph 3 PCH=CHCH 3 ][ZrCl 6 ] ( 1 ), [Ph 3 PCH 2 C(O)CH 3 ][HfCl 6 ] ( 2 ). The structures 1 and 2 were determined by XRDA and IR. The X-ray diffraction patterns of crystals 1 and 2 were obtained at 293 K on an automatic diffractometer D8 Quest Broker (MoK α radiation, λ = 0.71073 Å, graphite monochromator) the phosphorus atoms of complexes 1 and 2 have a distorted tetrahedral configuration in the cations. [C 42 H 40 P 2 Cl 6 Zr ( 1 ), M = 910.60; the triclinic syngony, the symmetry group P ; cell parameters: a = 10.189(8), b = 14.428(7), c = 15.229(8) Å; a = 83.31(2) degrees, β = 73.77(3) degrees, g = 87.75(3) degrees; V = 2135(2) Å 3 ; the crystal size is 0.72 × 0.36 × 0.3 mm; intervals of reflection indexes –12 ≤ h ≤ 12, –18 ≤ k ≤ 18, –19 ≤ l ≤ 19; total reflections 36133; independent disclosures 7367; R int = 0.0326; GOOF = 1.180; R 1 = 0.0907; w R 2 = 0.2675; residual electron density ­­–0.91/ 0.827 e/Å 3 , C 42 H 40 P 2 Cl 6 O 1 Hf ( 2 ), M = 1029.87; the triclinic syngony, the symmetry group P ; cell parameters: a = 10.323(3), b = 10.721(3), c = 11.122(3) Å; a = 67.634(13) degrees, β = 78.219(17) degrees, g = 73.041(14) degrees; V = 1082.7(5) Å 3 ; the crystal size is 0.57 × 0.39 × 0.22 mm; intervals of reflection indexes –19 ≤ h ≤ 19, –20 ≤ k ≤ 20, –21 ≤ l ≤ 21; total reflections 118390; independent disclosures 16166; R int = 0.0486; GOOF 1.009; R 1 = 0.0447; w R 2 = 0.0772; residual electron density ­–1,013/0,910 e/Å 3 ]. The СРС valence angles are 107.95(16)°–110.94(15)° and 106.72(17)°–113.51(17)° for 1 , 105.85(15)°–110.97(15)° for 2 , distance P-С 1.771(6)–1.801(6) Å и 1.781(6)–1.801(6) Å in 1 ; 1.790(2)–1.821(2) Å in 2 . In octahedral anions [ZrCl 6 ] 2− and [HfCl 6 ] 2– trans-angles ClZrCl and ClHfCl equal 180.0º, distance 2.462(3)–2.476(3) Å и 2.462(2)– 2.468(2) Å in a crystal solvate in 1 , 2.4513(10)–2.462(2) Å in 2 . Complete tables of coordinates of atoms, bond lengths and valence angles are deposited at the Cambridge Structural Data (No. 1913593 for 1 , 1919938 for 2 , deposit@ccdc.cam.ac.uk; http://www.ccdc. cam.ac.uk).

Минорный продукт [Ph3Sb(Cl)O]3C• PhH в реакции перераспределения лигандов арильных производных пятивалентной сурьмы

One of the reaction products of triphenylantimony dichloride and triphenylantimony bis (2,4-dibromophenoxide) (1:1 mol.) in benzene in air is the compound of three-coordinated carbon [Ph 3 Sb(Cl)O] 3 C × PhH ( 1 ). The compound has been identified by IR spectroscopy and X-ray diffraction analysis. According to the X-ray diffraction analysis the target product is a benzene solvate [С 61 H 51 Cl 3 O 3 Sb 3 , М = 1303.65; the monoclinic system, space group P2 1 /c; a 17.17(2), b 18.75(2); c 17.322(18) A; α 90.00, β 90.58(5), γ 90.00 град.; V 5576(11) A 3 ; Z 4; µ 1.630 mm –1 ; F (000) 2580.0; crystal size 0.28 × 0.22 × 0.11 mm; 2θ for data collection 6.4 - 36.8 degrees; index ranges −15 ≤ h ≤ 15, −16 ≤ k ≤ 16, −15 ≤ l ≤ 15; total reflections 24392; independent reflections 3981; R int 0.0516; variables 632, GOOF 1.141; R 1 = 0.0392; wR 2 = 0.0912; residual electron density 0.43/–0.35 e/A 3 ]. The COSb angles in the compound 1 vary in the interval 123.3(8)-127.1(8)°. The C–O shortened distances (1.365(15)–1.385(15) A) compared to the sum of the covalent radii of carbon and oxygen atoms (1.51 A) indicate an increase in the multiplicity of these bonds. The abnormal reduction of Sb–O distances (1.986(7), 2.001(7), 2.011(7) A) in the neutral molecule 1 compared to the sum of the covalent radii of antimony and oxygen atoms (2.14 A) implies delocalization of the electron density in the CO 3 Sb 3 core. The Sb – Cl distances are slightly longer than the sum of the covalent radii of antimony and chlorine atoms and are longer than ones in triphenylantimony dichloride. The antimony atoms have a distorted trigonal-bipyramidal coordination with heteroatoms in axial positions. The formation of the crystal structure is due to the formation of weak hydrogen bonds such as С···Н (2.72-2.90 A) and Сl···Н (2.94 A). Complete tables of coordinates of atoms, bond lengths and valence angles are deposited at the Cambridge Structural Data Bank (No. 1851485; deposit@ccdc.cam.ac.uk; http:// www.ccdc.cam.ac.uk/data_request/cif).