Structure and properties of two new heteroleptic bismuth(III) dithiocabamates of the general composition Bi(S2CNH2)2X (X = Cl, SCN)

2022 ◽  
Vol 0 (0) ◽  
Christoph Ludwig Teske ◽  
Huayna Terraschke ◽  
Sebastian Mangelsen ◽  
Wolfgang Bensch

Abstract The title compounds were prepared by precipitation from acidic solutions of the reactants in acetone/water. Bi(S2CNH2)2Cl (1) crystallizes in the non-centrosymmetric trigonal space group P32 with a = 8.6121(3) and c = 11.1554(4) Å, Z = 3; Bi(S2NH2)2SCN (2) in P21/c (monoclinic) with a = 5.5600(2), b = 14.3679(5), c = 12.8665(4) Å, and β = 90.37(3)°. In the crystal structure of 1 Bi3+ is in a sevenfold coordination of two bidentate and one monodentate S2CHNH2 − anions with an asymmetric coordination pattern of five Bi–S and two Bi–Cl− bonds. The linkage of these polyhedra via common Cl–S edges leads to a 1D polymeric structure with undulated chains propagating in the direction [001]. These chains are linked by strong and medium strong hydrogen bonds forming the 3D crystal structure. In the crystal structure of 2 the Bi3+ cation is in an eightfold coordination. The polyhedron can be described as a significantly distorted tetragonal anti-prism, capped by an additional S atom. Two of these prisms share a common quadrilateral face to form a “prism-double” (Bi2S10N2). These building units are linked by common edges, and the resulting 1D infinite angulated chains propagate along [100]. By contrast to organo-dithiocarbamate compounds, where C–H···X bridges are dominant, the interchain connections in the crystal structures of 1 and 2 are formed exclusively via N–H···S, N–H···Cl, and N–H···N interactions, generating the 3D networks. A significant eccentricity of the Bi3+ cation in the crystal structures of both complexes is observed. Both compounds emit light in the orange range of the electromagnetic spectrum.

1989 ◽  
Vol 44 (1) ◽  
pp. 41-55 ◽  
Jutta Hartmann ◽  
Shi-Qi Dou ◽  
Alarich Weiss

Abstract The 79Br and 127I NQR spectra were investigated for 1,2-diammoniumethane dibromide, -diiodide, 1,3-diammoniumpropane dibromide, -diiodide, piperazinium dibromide monohydrate, and piperazinium monoiodide in the temperature range 77 ≦ T/K ≦ 420. Phase transitions could be observed for the three iodides. The temperatures for the phase transitions are: 400 K and 404 K for 1,2-diammoniumethane diiodide, 366 K for 1,3-diammoniumpropane diiodide, and 196 K for piperazinium monoiodide.The crystal structures were determined for the piperazinium compounds. Piperazinium dibromide monohydrate crystallizes monoclinic, space group C2/c, with a= 1148.7 pm, 0 = 590.5 pm, c= 1501.6pm, β = 118.18°, and Z = 4. For piperazinium monoiodide the orthorhombic space group Pmn 21 was found with a = 958.1 pm, b = 776.9 pm, c = 989.3 pm, Z = 4. Hydrogen bonds N - H ... X with X = Br, I were compared with literature data.

2006 ◽  
Vol 62 (4) ◽  
pp. m827-m829 ◽  
David A. Grossie ◽  
William A. Feld ◽  
Lawrence Scanlon ◽  
Giselle Sandi ◽  
Zdzislaw Wawrzak

The crystals of the title compound, [Li2(C3H6O)4(H2O)2][Li2(C3H6O)2(H2O)4] [Li(C32H16N8)]4, were obtained by a recrystallization of dilithium phthalocyanine from an acetone/water/toluene solution. The title structure consists of two independent Li–phthalocyanine complexes along with acetone-bridged lithium dimers. The lithium dimers are located on inversion centers. The crystal structure is stabilized by a network of hydrogen bonds.

1990 ◽  
Vol 68 (1) ◽  
pp. 193-201 ◽  
Pascal Dufour ◽  
Yves Dartiguenave ◽  
Michèle Dartiguenave ◽  
Nathalie Dufour ◽  
Anne-Marie Lebuis ◽  

Crystals of 7-azaindole ([Formula: see text], a = 11.312(4), b = 14.960(6), c = 15.509(5) Å, α = 102.86(3), β = 108.78(3), γ = 90.71(3)°, Z = 16, R = 0.052) contain tetrameric units of approximate S4 symmetry, in which the molecules are associated by means of four complementary N—H … N hydrogen bonds. [CH3Hg(7-azaindole)]NO3 ([Formula: see text], a = 7.818(3), b = 7.884(3), c = 9.135(4) Å, α = 97.89(3), β = 109.13(3), γ = 103.28(3)°, Z = 2, R = 0.039) contains well-separated nitrate ions and complex cations in which the methylmercury group is linearly bonded to the pyridine nitrogen atom, whereas the five-membered ring remains protonated. In the neutral [CH3Hg(azaindolate)] complex ([Formula: see text], a = 10.926(10), b = 11.333(8), c = 11.647(10) Å, α = 92.13(8), β = 104.83(9), γ = 111.86(7)°, Z = 6, R = 0.048), methylmercury groups have substituted the N—H proton in the five-membered ring for the three symmetry-independent molecules. Intermolecular secondary Hg … N bonds are found with pyridine nitrogens. Keywords: azaindole, methylmercury, crystal structure.

2007 ◽  
Vol 62 (7-8) ◽  
pp. 417-424
Basavalinganadoddy Thimme Gowda ◽  
Sabine Foro ◽  
Jozef Kožíšek ◽  
Hartmut Fuess ◽  

The effect of ring substitution and N-chlorination on the molecular geometry of arylsulphonamides and N-chloro-arylsulphonamides have been studied by determining the crystal structures of 2-methyl- 4-chloro-benzenesulphonamide (2M4CBSA) and the sodium salt of N-chloro-2-methyl-4-chlorobenzenesulphonamide (NaNC2M4CBSA). The results are analyzed along with the crystal structures of benzenesulphonamide, 4-methyl-benzenesulphonamide and 4-chloro-benzenesulphonamide. The crystal structure of NaNC2M4CBSA has also been compared and correlated with the crystal structures of the above compounds and those of the sodium salts of N-chloro-benzenesulphonamide, Nchloro- 4-methyl-benzenesulphonamide, N-chloro-4-chloro-benzenesulphonamide and N-chloro-2,4- dichloro-benzenesulphonamide. The crystal system, space group, formula units and lattice constants in Å of the new structures are: 2M4CBSA: triclinic, P1, Z = 4, a = 7.9030(10), b = 8.6890(10), c = 13.272(2), α = 100.680(10)°, β = 98.500(10)°, γ = 90.050(10)°; NaNC2M4CBSA: monoclinic, C2/c, Z =4, a = 10.9690(10), b = 6.7384(6), c = 30.438(2), β = 98.442(7)°. The structure of 2M4CBSA is quite complex with four molecules in its asymmetric unit. The S-N bond length slightly decreases with substitution of electron-withdrawing groups, while the effect is more pronounced with disubstitution. The structure of NaNC2M4CBSA confirms that there is no interaction between nitrogen and sodium, and Na+ is attached to one of the sulphonyl oxygen atoms. The Na+ coordination sphere involves oxygen atoms from water moleculess of crystallization and neighbouring molecules. The S-N distance of 1.586 Å for the compound is consistent with a S-N double bond. The molecules are held together by hydrogen bonds with distances varying from 2.12 to 2.85 Å.

2021 ◽  
Vol 77 (3) ◽  
pp. 144-151
Matthias Weil ◽  
Uwe Kolitsch

The crystal structure of the mineral kröhnkite, Na2Cu(SO4)2(H2O)2, contains infinite chains composed of [CuO4(OH2)2] octahedra corner-linked with SO4 tetrahedra. Such or similar tetrahedral–octahedral `kröhnkite-type' chains are present in the crystal structures of numerous compounds with the composition AnM(XO4)2(H2O)2. The title compounds, (NH4)Mg(HSO4)(SO4)(H2O)2, ammonium magnesium hydrogen sulfate sulfate dihydrate, and NaSc(CrO4)2(H2O)2, sodium scandium bis(chromate) dihydrate, are members of the large family with such kröhnkite-type chains. At 100 K, (NH4)Mg(HSO4)(SO4)(H2O)2 has an unprecedented triclinic crystal structure and contains [MgO4(OH2)2] octahedra linked by SO3(OH) and SO4 tetrahedra into chains extending parallel to [\overline{1}10]. Adjacent chains are linked by very strong hydrogen bonds between SO3(OH) and SO4 tetrahedra into layers parallel to (111). Ammonium cations and water molecules connect adjacent layers through hydrogen-bonding interactions of medium-to-weak strength into a three-dimensional network. (NH4)Mg(HSO4)(SO4)(H2O)2 shows a reversible phase transition and crystallizes at room temperature in structure type E in the classification scheme for structures with kröhnkite-type chains, with half of the unit-cell volume for the resulting triclinic cell, and with disordered H atoms of the ammonium tetrahedron and the H atom between two symmetry-related sulfate groups. IR spectroscopic room-temperature data for the latter phase are provided. Monoclinic NaSc(CrO4)2(H2O)2 adopts structure type F1 in the classification scheme for structures with kröhnkite-type chains. Here, [ScO4(OH2)2] octahedra (point group symmetry \overline{1}) are linked by CrO4 tetrahedra into chains parallel to [010]. The Na+ cations (site symmetry 2) have a [6 + 2] coordination and connect adjacent chains into a three-dimensional framework that is consolidated by medium–strong hydrogen bonds involving the water molecules. Quantitative structural comparisons are made between NaSc(CrO4)2(H2O)2 and its isotypic NaM(CrO4)2(H2O)2 (M = Al and Fe) analogues.

2010 ◽  
Vol 65 (7) ◽  
pp. 907-916 ◽  
Ioannis Tiritiris ◽  
Falk Lissner ◽  
Thomas Schleid ◽  
Willi Kantlehner

Dicationic N,N´,N´,N´´,N´´-pentasubstituted guanidinium dichlorides 4a, b are obtained from the chloroformamidinium salt 2 and diamines 3a, b. N-[2-(Dimethylammonio)ethyl]-N´,N´,N´´,N´´-tetramethylguanidinium chloride tetraphenylborate (5a) and N-[3-(dimethylammonio)propyl]-N´,N´,N´´,N´´-tetramethylguanidinium chloride tetraphenylborate (5b) were synthesized from 4a, b by anion metathesis with one equivalent of sodium tetraphenylborate. The thermal properties of the salts 5a, b were studied by means of DSC methods, and their crystal structures were determined by single-crystal X-ray diffraction analysis. For 5a a solid-solid phase transition is observed at −156 ◦C to a low-temperature structure. The room-temperature modification (α-5a) crystallizes in the centrosymmetric orthorhombic space group Pbca (a = 13.1844(4), b = 13.8007(4), c = 34.7537(11) A° ).The guanidinium ions are interconnected via chloride ions through bridging N-H· · ·Cl hydrogen bonds, providing isolated units. The tetraphenylborate ions show some dynamic disordering in the crystal structure. The low-temperature modification (β -5a) also crystallizes orthorhombically, but in the non-centrosymmetric space group Pna21 (a = 13.1099(4), b = 69.1810(11), c = 13.5847(5) A° ) and consists of four crystallographically independent cations and anions in the unit cell. Compared with the room-temperature structure, a similar N-H· · ·Cl hydrogen bond pattern is observed in the β -phase, but the tetraphenylborate ions are now completely ordered. 5b crystallizes in the monoclinic space group P21/c (a = 10.8010(3), b = 14.1502(5), c = 20.9867(9) A° , β = 94.322(1)◦). In the crystal structure the guanidinium ions are linked via chloride ions through N-H· · ·Cl hydrogen bonds, but in contrast to 5a two infinite strands are formed along the a axis with the tetraphenylborate ions interspersed between them for charge compensation.

CrystEngComm ◽  
2014 ◽  
Vol 16 (14) ◽  
pp. 3040-3046 ◽  
Xiao-Peng Xuan ◽  
Liang-Liang Chang ◽  
Heng Zhang ◽  
Na Wang ◽  
Yang Zhao

Hydrogen bonds such as the classic O–H⋯X (halide ion) hydrogen bond and the carboxyl group dimer were observed in the crystal structures of hydrophilic and hydrophobic COOH-functionalized imidazolium ionic liquids, respectively.

Gerhard Laus ◽  
Volker Kahlenberg ◽  
Thomas Gelbrich ◽  
Sven Nerdinger ◽  
Herwig Schottenberger

Mutual carboxyl–carboxyl O—H...O hydrogen bonds link the molecules of the title compound, C7H5BrO3, into centrosymmetric dimers which display a centralR22(8) ring motif. In addition, there is an intramolecular hydroxyl–carboxyl O—H...O interaction present. A comparison with the crystal structures of 59 other substituted derivatives of salicylic acid shows that both the centrosymmetric carboxyl–carboxyl O—H...O dimer and the stacking mode of molecules along the shortaaxis observed in the title structure are frequent packing motifs in this set.

2014 ◽  
Vol 7 (1) ◽  
pp. 15-19 ◽  
Danica Čechová ◽  
Alena Martišková ◽  
Jan Moncol

Abstract The crystal structures of the title compounds, [Mn(phen)2Cl2] (I) and [Mn(bipy)2Cl2] (II), have been determined at 150 K. The manganese atoms in both compounds are coordinated by four pyridine nitrogen atoms from two 1,10-phenanthroline or 4,4´-bipyridine ligands and two chloride anions, resulting in a distorted cis-MnN4Cl2 octahedral geometry. Both complexes are connected through C-H・・・Cl hydrogen bonds into frameworks. The π-π stacking interactions are observed in crystal structure of both ones.

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