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).     

Bis(tetraphenylantimony) succinate,malate, and tartrate: Syntheses and structures

The reactions of pentaphenylantimony with succinic, malic, and tartaric acids (mole ratio 2: 1) in toluene afford bis(tetraphenylantimony) succinate (I), malate (II), and tartrate (III) in yields of 98, 92, and 94%, respectively. According to the X_ray diffraction analysis results, molecules I and II are centrosymmetric. In compound II, the hydroxy group in the acid residue is disordered over two positions. Crystal III includes two types of crystallographically independent molecules (a and b). The antimony atoms in compounds I, II, IIIa, and IIIb have distorted trigonal bipyramidal coordination modes. The axial angles C_axSbO_ax are 166.80(8)° (I); 174.8(2)° (II); 176.4(4)°, 177.4(3)° (IIIa); and 173.3(4)°, 172.7(4)° (IIIb). The equatorial angles C_eqSbC_eq vary in the ranges 99.3(1)°–154.5(1)° (I); 115.2(2)°–123.3(2)° (II); 115.7(4)°–123.3(4)° 115.2(5)°–125.6(5)° (IIIa); and 107.9(4)°-129.1(4)°, 113.7(4)°-124.8(5)° (IIIb). The Sb-C and Sb-O bonds are 2.138(3)-2.176(3), 2.319(2) Å (I); 2.111(6)–2.163(5), 2.243(4) Å (II); 2.072(13)–2.169(11), 2.252(7), 2.284(7) Å (IIIa); and 2.047(11)–2.190(11), 2.224(7), 2.256(7) Å (IIIb). The intramolecular distances Sb…O=C are 2.528(3) (I); 3.267(7) (II); 3.381(7), 3.436(7) (IIIa); and 3.351(7), 3.162(7) Å (IIIb). For structures I, II, and III, the CIF files are CCDC 929151, 941542, and 941543, respectively.     

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).     

Tri- and tetraphenylantimony propiolates: Syntheses and structures

The reaction of triphenylantimony with propiolic acid in the presence of hydrogen peroxide (molar ratios 1 : 2 : 1 and 1 : 1 : 1) in diethyl ether affords triphenylantimony dipropiolate Ph₃Sb[OC(O)C≡CH]₂ (I) and μ₂-oxobis[(propiolato)triphenylantimony] [Ph₃SbOC(O)C≡CH]₂O (II). Tetraphenylantimony propiolate Ph₄SbOC(O)C≡CH (III) is synthesized from pentaphenylantimony and propiolic or acetylenedicarboxylic acid in toluene. According to the X-ray diffraction data, the crystals of compounds I and III include two types of crystallographically independent molecules (a and b). The antimony atoms in molecules Ia, Ib, II, IIIa, and IIIb have the trigonal-bipyramidal coordination mode with different degrees of distortion. The OSbO and OSbC axial angles are 176.8(2)° (Ia, Ib), 170.17(15)°, 178.78(14)° (II), and 173.2(5)°, 174.4(5)° (IIIa, IIIb). The CSbC equatorial angles lie in the ranges 108.2(3)°–143.1(3)° (I), 109.0(2)°–131.0(2)° (II), and 113.1(4)°–125.4(4)° (III). The SbOSb angle in II is 141.55(19)°. The Sb-C bond lengths are 2.103(8)–2.141(5) (I), 2.105(5)–2.119(5) (II), and 2.076(12)–2.166(13) Å (III). The Sb-O distances increase in a series of I, II, and III: 2.139(6)–2.156(7) (Ia, Ib); 2.206(4), 2.218(3) (II); and 2.338(10), 2.340(10) Å (III).     

Crystal and molecular structures of ZnPhen(C2H5OCS2)2 and Zn(2,2′-Bipy)(n-C4H9OCS2)2 mixed-ligand coordination compounds

ZnPhen(EtOCS₂)₂ (I) and Zn(2,2′-Bipy)(n-BuOCS₂)₂ (II) mixed-ligand complexes have been synthesized. The structures were solved from X-ray diffraction data (CAD-4 and X8-APEX diffractometers, MoK _α radiation, 1879 and 3637 F _hkl , R = 0.0374 and 0.0315). Crystals I are monoclinic with parameters a = 11.678(3) Å, b = 19.215(3) Å, c = 9.655(1) Å; β = 101.23(1)°; V = 2125.0(7) ų; Z = 4, space group P2₁/c; crystals II are triclinic with parameters a = 8.7875(3) Å, b = 11.833(1) Å, c = 13.3454(6) Å; α = 112.154(2)°, β = 108.503(1)°, γ = 92.787(2)°; V = 1196.2(1) ų; Z = 2, space group 1 $P\bar 1$ . The structures are composed of discrete mononuclear molecules. The polyhedra of the Zn atoms are distorted trigonal bipyramids N₂S₃ formed by coordination of the N atoms of Phen or 2,2′-Bipy molecules and sulfur atoms of the monodentate and cyclic bidentate xanthogenate ligand. In structures I and II, dimer assemblies are formed by π-π interactions of Phen or 2,2′-Bipy molecules.     

Synthesis and structure of palladium complexes [Ph3PhCH2P]+[PdCl3(DMSO)]− · DMSO, [Ph4P]+[PdCl3(DMSO)]−, and [Ph4Sb(DMSO)]+[PdCl3(DMSO)]−

[Ph₃PhCH₂P]⁺[PdCl₃(DMSO)]^? · DMSO (I), [Ph₄P]⁺[PdCl₃(DMSO)]^? (II), and [Ph₄Sb(DMSO)]⁺[PdCl₃(DMSO)]^? (III) complexes have been synthesized via the reaction of palladium chloride with equimolar amounts of triphenylbenzylphosphonium chloride, tetraphenylphosphonium chloride, and tetraphenylstibonium chloride, respectively. According to X-ray diffraction data, the cations of complexes I (CPC = 104.90(8)°–111.61(9)°) and II (CPC = 105.12(10)°–111.46(10)°) have slightly distorted tetrahedral structures with P-C bond lengths of 1.786(2)–1.809(2) and 1.791(2)–1.799(2) Å, respectively. The antimony atom in the [Ph₄Sb(DMSO)]⁺ cation has a trigonal bipyramidal surrounding with the dimethyl sulfoxide (DMSO) oxygen atom in an axial position (Sb...O 2.567(2) Å). The palladium atoms in the square mononuclear anions of complexes I, II, and III are tetracoordinate, and Pd-Cl distances are 2.3101(5)–2.3104(5) Å, 2.2950(7)–2.2038(7) Å, and 2.2986(9)–2.3073(9) Å, respectively. The DMSO ligands are coordinated to the palladium atom through the sulfur atom (Pd-S, 2.2318(5) (I), 2.2383(6) (II), and 2.2410(9) Å (III)).     

Synthesis and structure of Bis(tetraphenylantimony) 1,2-diphenylethanedione dioximate toluene solvate Ph4SbONC(Ph)C(Ph)ONSbPh4 · 2PhCH3 and tetraphenylantimony 2-hydroxy-1,2-diphenylethanone oximate Ph4SbONC(Ph)CH(Ph)OH

Bis(tetraphenylantimony) 1,2-diphenylethanedione dioximate toluene solvate Ph₄SbONC(Ph)C(Ph)NOSbPh₄ · 2 PhCH₃ (I) and tetraphenylantimony 2-hydroxy-1,2-diphenyl(ethanone oximate Ph₄SbONC(Ph)CH(Ph)OH (II) have been synthesized by the reaction of pentaphenylantimony with 1,2-diphenylethane dioxime and 2-hydroxy-1,2-diphenylethanone oxime in toluene. A molecule of compound I is centrosymmetric with an inversion center at the midpoint of the C-C bond in the ethane moiety. A crystal of compound II contains two types of crystallographically independent molecules A and B. Antimony atoms in compounds I and II have a distorted tetragonal bipyramidal surrounding: equatorial CSbC and axial CSbO angles are 114.95(10)°–126.82(11)° and 173.24(9)° (I), 117.2(2)°–122.9(2)° and 178.15(18)° (IIA), and 112.3(2)°–127.7(2)° and 175.09(18)° (IIB), respectively. The Sb-C and Sb-O bond lengths are 2.106(3)–2.182(3) and 2.1344(17) ÅI), 2.118(5)–2.4199(5) and 2.153(4)Å(IIA), and 2.106(5)–2.200(5) and 2.120(4) Å (IIB), respectively. A molecule of compounds I, IIA, and IIB has been found to contain Sb...N intramolecular contacts (2.838(3), 2.867(5), and 2.889(5)Å, respectively). Molecules of compounds IIA and IIB contain O-H...N hydrogen bonds (H...N, 1.91(9) and 2.06(8) Å, respectively).     

Synthesis and study of tetraamminecobalt hydrogen hexamolybdometalates(III)

Tetraamminecobalt hydrogen hexamolybdoferrate [Co(NH₃)₄] · H[FeMo₆O₁₈(OH)₆] · 6H₂O (I) and tetraamminecobalt hydrogen hexamolybdogallate(III) [Co(NH₃)₄] · H[GaMo₆O₁₈(OH)₆] · 6H₂O (II) were synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, and X-ray diffraction. Crystals of I and II are monoclinic; a = 16.21 Å, b = 5.43 Å, c = 12.32 Å, β = 119.63°, V = 1092.11 ų, ρ_calcd = 2.21 g/cm³, and Z = 1 for I; a = 16.24 Å, b = 5.59 Å, c = 12.29 Å, β = 119.79°, V = 1064.05 ų, ρ_calcd = 2.15 g/cm³, and Z = 1 for II. Compounds I and II were used as catalysts for soft oxidation of natural gas.     

Synthesis and structure of platinum complexes [Ph4P]+[PtCl3(DMSO)]− and [Ph4P]+[PtCl5(DMSO)]−

The reaction of tetraphenylphosphonium chloride with an equimolar amount of potassium tetrachloroplatinate or hexachloroplatinic acid in dimethyl sulfoxide gave the complexes [Ph₄P]⁺[PtCl₃(DMSO)]^? (I) and [Ph₄P]⁺[PtCl₅(DMSO)]^? (II), respectively. The phosphorus atoms in the cations have tetrahedral environment, the CPC angles and P-C distances 105.63(13)°–112.13(14)°, 1.795(3)–1.797(3) Å I) and 105.7(3)°–112.9(3)°, 1.783(7)–1.791(6) Å II). The platinum coordination polyhedra in the anions [PtCl₃(DMSO)]^? and [PtCl₅(DMSO)]^? are distorted square (Pt-S, 2.1937(8); Pt-Cl, 2.2894(10)–2.3024(10) Å; trans-angles: SPtCl, 177.38(4)°; ClPtCl, 175.40(4)°) and octahedron (Pt-S 2.291(2) Å; Pt-Cl, 2.312(2)–2.334(2) Å, trans-angles: SPtCl, 178.28(9)°; ClPtCl, 178.80(9)° and 178.88(8)°).     

Hydrothermal synthesis, crystal structure, and photoluminescence of Pb(II) and Mn(II) coordination polymers based on imidazo[4,5-f][1,10]phenanthroline

Two new coordination polymers, [Pb(IDPT)₂(NO₃)₂] (I) and [Mn(IDPT)(SO₄)(H₂O)₂] (II) (IDPT = imidazo[4,5-f][1,10]phenanthroline), were synthesized by hydrothermal method and characterized by elemental analysis and single-crystal X-ray diffraction technique. The results reveal that the complex I belongs to monoclinic crystal system, space group C2/c and complex II belongs to monoclinic crystal system, P2₁/c space group. The cell parameters are: a = 19.1970(13), b = 7.3875(5), c = 17.3825(12) Å, β = 100.47(10)°, V = 2424.0(3) ų, Z = 4, F(000) = 1488 for I; a = 10.9135(6), b = 7.0230(4), c = 19.7034(10) Å, β = 99.32(10)°, V = 1490.25(14) ų, Z = 4, F(000) = 828 for II. In the structure of complex I, the metal center Pb(II) is six-coordinated, displays an octahedral geometry. Each molecule is further connected with neighboring one via π-π interactions into 1D chain. In complex II, Mn(II) is six-coordinated to form a distorted octahedral geometry. Compound II displays 1D supramolecular chain formed through hydrogen bonds. Additionally, the fluorescent properties for the complexes were investigated. Complexes I and II exhibit strong photoluminescence with emission maximum at 583 and 529 nm at room temperature.     

Synthesis and structure of lithium and rubidium compounds with 2-(diphenylacetyl)-1,3-indanedione

Complexes RbL (I) and [Li₂(C₂H₅OH)L₂] (II) (L = C₂₃H₁₅O₃) have been synthesized and their crystal structures have been studied. Both compounds have monoclinic crystals with space group P2₁/c and Z = 4; I: a = 11.632(2) Å, b = 15.154(3) Å, c = 11.457(2) Å, β = 104.34(3)°; II: a = 12.982(3)Å, b = 12.083(2) Å, c = 25.317(5) Å β = 100.11(3)°. In the structure of I, dimeric groups [Rb₂O₆] with a shared edge are linked by the ligands to give infinite layers perpendicular to the x axis and cavities that form oblong channels. In the structure of II, Li₂O₇ dimers are formed by vertex sharing. The coordination of one of the lithium atoms (Li(1)) is completed to tetrahedral by the oxygen atom of the ethanol molecule. The structure of II, like that of I, is layered.     

Crystalline modifications of tetra-(p-tolyl)antimony benzene sulfonate

Two structural isomers (I and II) have been obtained via the crystallization of tetra-(p-tolyl)antimony benzene sulfonate from toluene or water. The antimony atom in compound I has a distorted trigonal bipyramidal coordination to the carbon and oxygen atoms in axial positions (Sb-C, 2.097(11) (eq.), 2.103(10) (eq.), 2.111(10) (eq.), 2.139(10) (ax.) Å; Sb-O, 2.400(7) Å; OSbC, 176.9(3)°, C_eqSbC_eq, 115.3(4)°, 118.7(4)°, 119.1(4)°). A crystal of compound II is built of tetrahedral tetra-(p-tolyl)stibonium cations (Sb-C, 2.097(2), 2.097(2), 2.105(2), 2.106(3) Å; CSbC, 104.68(9)°-117.25(9)°) and benzene sulfonate anions (S-O, 1.439(2), 1.451(2), 1.454(2) Å; OSO, 112.82(15)°-113.70(16)°; OSC, 104.74(13)°-105.78(12)°).     

Chlorine reaction with platinum triamine [Pt(N,N-DimeTm)PyCl3]Cl (N,N-DimeTm = (CH3)2N(CH2)3NH2). Crystal structure of [Pt(N,N-DimeTm)Cl2], [Pt(N,N-DimeTm(Py)Cl3]Cl · H2O and [Pt{(CH3)2N(CH2)2C(O)NH}(Py)Cl3]

Treatment of platinum(II) diamine [Pt(N,N-DimeTm)Cl₂] (I) with pyridine gave tetramine [Pt(N,N-DimeTm)Py₂]Cl₂ (II); by oxidation with chlorine this was converted to Pt(IV) triamine, [Pt“(N,N-DimeTm(Py)Cl₃]Cl (III) with a six-membered chelate ring. According to X-ray diffraction data, the reaction of complex II with chlorine is accompanied by removal of the pyridine molecule from the trans-position to the NH₂ group of N,N-dimethyltrimethylenediamine. The reaction of complex III with chlorine at 20°C afforded a mixture of compounds (IV) and the complex [Pt“(CH₃)₂N(CH₂)₂C(O)NH”(Py)Cl₃] (V) with an amidate six-membered metal ring, dimethylpropioamide, which was also isolated upon refluxing a mixture of IV in an aqueous solution. The UV/Vis and IR spectra of the obtained complexes were studied, and X-ray diffraction analysis of I, III, and V was performed. The crystals of I are triclinic, space group P $ \bar 1 $ ; a = 7.6526(4) Å, b = 11.5571(6) Å, c = 12.4432(7) Å, α = 113.85(1)°, β = 96.54(2)°, γ = 106.78(2)°; Z = 4; R _hkl = 0.051. The crystals of III are monoclinic, space group C2/c; a = 36.715(2) Å, b = 7.8179(4) Å, c = 29.721(16) Å, β = 127.80(1)°; Z = 16; R _hkl = 0.036. The crystals of V are monoclinic, space group P2₁/n; a = 7.0398(6) Å, b = 27.458(2) Å, c = 7.687(6) Å, β = 106.270(1)°; Z = 4; R _hkl = 0.052.     

New fluorochromatouranylates of alkali metals: Synthesis and structure

Four new fluorochromatouranylates, namely, K[UO₂(CrO₄)F] · 1.5H₂O (I), Rb[UO₂(CrO₄)F] · 1.5H₂O (II), Rb[UO₂(CrO₄)F] · 0.5H₂O (III), and Cs[UO₂(CrO₄)F] · 0.5H₂O (IV), have been synthesized, and their crystallographic characteristics have been determined. All the compounds crystallize in monoclinic system, space group P2₁/c, with the unit cell parameters a = 13.1744(5) Å, b = 9.4598(3) Å, c = 13.0710(4) Å, β = 103.746(1)°, Z = 4, R = 0.0235 (I); a = 13.5902(7) Å, b = 9.5022(4) Å, c = 13.2271(6) Å, β = 102.914(2)°, Z = 4, R = 0.0247 (II); a = 24.7724(8) Å, b = 12.6671(4) Å, c = 9.4464(3) Å, β = 97.661(1)°, Z = 8, R = 0.0448 (III); a = 25.725(1) Å, b = 12.8261(5) Å, c = 9.4929(4) β = 97.208(1)°, Z = 8 (IV). The pairs of compounds I and II and compounds III and IV are isostructural. Crystals of compounds I–III have been subjected to complete X-ray diffraction study. It has been established that the structures of compounds I–III are built of [UO₂(CrO₄)F] _n ^n? layers, which are parallel to the (100) plane and linked into a framework by alkali-metal cations located between layers, together with water molecules. The effect of topological and geometric isomerism on the structural features of 34 known uranyl compounds of the AT³M² crystallochemical group, to which the studied compounds I–III also belong, is discussed.     

Coordination compounds of cobalt(II) and cadmium(II) with 2-amino-4-methylpyrimidine: Synthesis, crystal structure, and luminescent properties

The coordination compounds [CoL₂Cl₂] (I) and [CdL₂(H₂O)₂(NO₃)₂] (II) have been synthesized by the reaction of CoCl₂ · 6H₂O and Cd(NO₃)₂ · 4H₂O with L = 2-amino-4-methylpyrimidine (Ampym, C₅H₇N₃), and their structures have been solved. The crystals of complex I are triclinic, space group $P\bar 1$ , a = 5.627(1) Å, b = 11.191(1) Å, c = 12.445(1) Å, α = 81.00(1)°, β = 77.21(1)°, γ = 76.18(1)°, V = 737.7(2) ų, ρ_calcd = 1.567 g/cm³, Z = 2. The crystals of complex II are monoclinic, space group P2₁/c, a = 10.390(1) Å, b = 11.982(1) Å, c = 7.624(1) Å, β = 102.61(1)°, V = 926.1(2) ų, ρ_calcd = 1.760 g/cm³, Z = 2. Discrete [CoL₂Cl₂] moieties are realized in the structure of complex I. The cobalt atom is tetrahedrally coordinated to the two nitrogen atoms of crystallographically nonequivalent ligands L and two chlorine atoms (Co(1)-N_avg, 2.051(4)Å; Co(1)-Cl(1), 2.241(1) Å; Co(1)-Cl(2), 2.263 Å; bond angles at the cobalt atom lie within a range of 102.1°–118.6°). The complexes are linked into supramolecular zigzag chains by N-H...N(Cl) hydrogen bonds. In the structure of complex II, the Cd²⁺ ion (at the inversion center) is coordinated in pairs to the nitrogen atoms of ligand L and the O(NO₃) and O(H₂O) oxygen atoms. The coordination of the Cd²⁺ ion is distorted octahedral (Cd(1)-N(1), 2.341Å; Cd(1)-O(1), 2.340(4) Å; Cd(1)-O(4), 2.327(3) Å; bond angles at the cadmium atom lie within a range of 79.1°–100.9°). N-H...N hydrogen bonds link the complexes into supramolecular chains. These chains are linked into a supramolecular framework by the O-H...O hydrogen bonds between water molecules and NO₃ groups.     

Structure and properties of tripyridine nitrosocomplexes of ruthenium: mer-[Ru(NO)Py3Cl(OH)]Cl·1.5H2O and mer-[Ru(NO)Py3Cl(H2O)]Cl2·2H2O·0.5HCl

The reaction of K₂[Ru(NO)Cl₅] with pyridine in aqueous ethanol at pH ～ 7–8 affords a nitrosoruthenium hydroxocomplex mer-[Ru(NO)Py₃Cl(OH)]Cl·1.5H₂O (I) (yield ～55%). Treatment of hydroxocomplex I with hydrochloric acid at room temperature gives the aqua complex mer-[Ru(NO)Py₃Cl(H₂O)]Cl₂·2H₂O·0.5HCl (II). The structures of the compounds are determined by X-ray crystallography: I, space group P2₁/n, a = 9.2292(4) Å, b = 11.7781(4) Å, c = 17.4915(7) Å, β = 90.9560(10)°, R = 4.84%; II, space group P-1, a = 7.3528(9) Å, b = 11.5793(11) Å, c = 13.6961(16) Å, α = 84.558(3)°, β = 87.668(4)°, γ = 74.146(4)°, R = 6.22%. Compounds I and II are characterized by powder XRD, ¹H and ¹³C NMR, and IR spectroscopy. The thermal decomposition of compound II in the inert atmosphere is examined by thermal analysis.     

Study of new molecular and crystal structures of 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecane-2,8-dione and its salts: Monochloride,mononitrate, and tetraiodotellurate

This is the first work to synthesize 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecane-2,8-dione monohydrate, monochloride, mononitrate, and teteraiodotellurate: C₁₁H₂₀N₄O₂·H₂O (I), C₁₁H₂₁N₄O ₂ ⁺ ·Cl^? (II), C₁₁H₂₁N₄O ₂ ⁺ ·NO ₃ ^? (III), and 2(C₁₁H₂₁N₄O ₂ ⁺ )·TeI ₄ ^2? ·C₃H₆O (IV) and determine their structures. Crystals of I are monoclinic: space group P2₁/c, at 298 K a = 5.7118(7) Å, b = 17.842(2) Å, and c = 13.5905(16) Å; β = 91.621(11)°; V = 1384.5(3) ų; d _x = 1.239 g/cm³, Z = 4. Crystals of II are tetragonal: space group P4₃, at 298 K a = 6.4134(3) Å and c = 34.292(2) Å; V = 1410.47(14) ų; d _x = 1.303 g/cm³; Z = 4. Crystals of III are triclinic: space group \(P\bar 1\) , at 298 K a = 8.7614(14) Å, b = 9.3904(18) Å, and c = 10.028(2) Å; α = 63.27(2)°, β = 78.591(16)°, and γ = 84.308(15)°; V = 722.3(2) ų; d _x = 1.40 g/cm³; Z = 2. Crystals of IV are triclinic: space group \(P\bar 1\) , at 100 K a = 10.4630(4) Å, b = 11.9372(6) Å, and c = 16.4118(5) Å; α = 72.058(3)°, β = 76.406(3)°, and γ = 87.029(3)°; V = 1895.04(12) ų; d _x = 2.06 g/cm³; Z = 2. The synthesis of s and p metals with spirocarbone in acetone medium is found to be impossible due to the protonation by the oxygen atom of the carbonyl group. The main crystalline product of the complexation reaction is a monosalt. Evidence is provided that the recrystallization and drying of the synthesized spirocarbone preparation yields monohydrate (I); its purity and monophasity is confirmed by a Rietveld refinement of the powder X-ray pattern. The lattice parameters at room temperature are: a = 5.6885(12) Å, b = 17.8496(12) Å, and c = 13.518(3) Å; β = 91.449(15)°; V = 1372.1(4) ų. The sample is monophasic.     

Isomorphous crystal structures of 4,7,13,16,21,24-hexaoxo-1,10-diaziniabicyclo[8.8.8]·hexacosane bis(tribromide) and bis(bromoiodide)

Two compounds, 7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane bis(tribromide) and bis(bromodiiodide) — [H₂(Crypt-222)]²⁺·2Br ₃ ^? (I) and [H₂(Crypt-222)]²⁺·1.45(BrI₂)^?·0.4(Br₂I)^?·0.15 I ₃ ^? (II) — are prepared and characterized by single crystal XRD; the refinement of the second compound was more accurate. Isomorphous monoclinic structures (I, space group C2/c, Z = 4, a = 12.090, b = 15.833 Å, c = 15.732 Å, β = 95.83°; II, a = 12.548 Å, b = 16.417 Å, c = 15.748 Å, β = 94.53°) are solved by a direct method and refined in the anisotropic full-matrix approximation to R = 0.057 (I) and 0.044 (II) using all 2635 (I) and 2852 (II) measured independent reflections (automated CAD-4 diffractometer, λMoK _α). In the structures of I and II one of the trihalide anions sits at the inversion center i(000), and the second trihalide anion and the dication [H₂(Crypt-222)]²⁺ are situated at crystallographic axis 2. In the structure of II iodine is located in the center of trihalide anions, while the terminal atoms are disordered and are represented by a statistical combination of iodine and bromine atoms.     

Synthesis and crystal structure of the Ag(I) complex with a cyclic β-diketone, 2-(diphenylacetyl)indan-1,3-dione (L), and the HL molecule

An Ag(I) complex with HL (I), AgL (AgC₂₃H₁₅O₃, II), has been synthesized. Compounds I and II have been studied by X-ray diffraction. The crystals are monoclinic, I: space group P2₁/n, a = 10.459(2) Å, b = 12.354(2) Å, c = 13.390(3) Å, β = 96.67(3)°, Z = 4; II: space group P2₁/c, a = 10.764(2) Å, b = 10.683(2) Å, c = 15.939(3) Å, β = 101.57(3)°, Z = 4. The structural units of the crystal of I are neutral molecules with intramolecular hydrogen bonds. In structure II, the Ag₂O₆ dimeric groups and the ligands form infinite openwork layers perpendicular to the x axis and containing cavities. The layers are penetrated by channels with an oblong cross section. In the crystal of II, all intermolecular distances exceed the sums of the van der Waals radii of the corresponding atoms.     

Copper(I) halide complexes with N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium (L2+). Synthesis and crystal structures of the complexes [L0.5CuCl2], [L0.5CuCl0.72Br1.28], and [L0.5CuBr2]

The Eschweiler-Clarke reaction of ethylenediamine with formaldehyde and formic acid yielded N,N,N′,N′-tetramethylethylenediamine, which was alkylated with allyl chloride or allyl bromide to give the corresponding N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium (L²⁺) dihalides. In methanolic solutions of copper(II) halide and an appropriate ligand, ac electrochemical synthesis with copper wire electrodes afforded single crystals of Cu(I) complexes with L²⁺: [L_0.5CuCl₂] (I), [L_0.5CuCl_0.72Br_1.28] (II), and [L_0.5CuBr₂] (III). The crystal structures of complexes I–III were determined by X-ray diffraction study. The isostructural crystals of I and II are monoclinic, space group P2₁/n, Z = 4. For I: a = 7.632(4) Å, b = 11.318(5) Å, c = 10.635(5) Å, β = 98.551(7)°, V = 908.4(7) ų. For II: a = 7.7415(7) Å, b = 11.4652(9) Å, c = 10.7267(10) Å, β = 98.351(4)°, V = 942.0(2) ų. The organic cation L²⁺ acts as a bridge linking a pair of separate cuprous halide fragments Cu₂X₄. Although being isostoichiometric with I and II, complex III has a different structure. The crystals of III are monoclinic, space group P2₁/c, a = 6.519(2) Å, b = 9.060(3) Å, c = 16.284(6) Å, β = 97.219(4)°, V = 954.2(6) ų, Z = 4. In structure III, the inorganic fragment forms infinite polymer chains (CuBr ₂ ^? ) _n . The organic and inorganic parts are held together only by electrostatic interactions. Structures I–III are stabilized by hydrogen bonds (C)H…X (2.6–2.9 Å).