Über bismut-haltige heterocyclen: I. Methylierte und phenylierte bismocane,intra- und intermolekulare koordinationserhöhung an bismut(III)

Methyl and phenyl oxadithia and trithiabismocanes have been synthesized from methyl or phenyl diethoxybismutane and the respective dithiol. The light-sensitive compounds have been investigated by mass, vibrational and ¹³C NMR spectra: ν(BiMe) 470–460, ν(BiS₂) 300–240 cm^?1; δ(¹³Me) ?12 ppm. The crystal structure of 5-phenyl-1,4,6,5-oxadithiabismocane has been determined (R = 0.056). The eight-membered ring has the chair-chair conformation. Besides three direct bonds (BiPh 225(2), BiS 256.0(2) and 260.2(3) pm) there are one transannular (Bi?O 297(1) and two intermolecular contacts (Bi ?S 344.0(3) and 350.9(3) pm) to bismuth in resulting a ψ-monocapped octahedral sphere of coordination. These polyhedra are connected in sharing two different edges, and the crystal structure exhibits double chains of molecules.     

Crystal and molecular structure and vibrational spectra of 2,6-bis(diphenylphosphorylmethyl)-4-methylphenol and its complex with cerium(III) nitrate

The structure of 2,6-bis(diphenylphosphorylmethyl)-4-methylphenol 2,6-[Ph₂P(O)CH₂]₂-4-MeC₆H₂OH(L¹) and its 1: 1 complex with cerium(III) nitrate were studied by X-ray diffraction. A rather strong intramolecular hydrogen bond P=O…H-O (O…O, 2.646(1) Å) exists in the L¹ molecules. In the crystal, the molecules are combined into centrosymmetric dimers through the stacking interaction between the central phenol rings; the distance between the ring planes is 3.39 Å. In the complex molecule, [Ce(L¹)(NO₃)₃ · Me₂C(O)], the neutral ligand L¹ is tridentate and the three nitrate ions are bidentate, and the tenth coordination site is occupied by acetone oxygen. No intramolecular H-bonds are present. In the crystal, the complex molecules are combined into centrosymmetric dimers through intermolecular hydrogen bonds O-H…O-NO₂ (O…O, 2.713(8) Å). The vibrational (IR, Raman) spectra of the ligand and the complex were studied and the principal bands were assigned. According to IR spectroscopy, the P=O…H-O intramolecular hydrogen bond is retained in both the ligand and the complex molecules.     

Synthesis and crystal structure of 2-{5-[2-(2,6-dichlorophenylamino)benzyl]-4-p-tolyl-4H-1,2,4-triazol-3-ylthio}acetate

The compound 2-{5-[2-(2,6-dichlorophenylamino)benzyl]-4-p-tolyl-4H-1,2,4-triazol-3-ylthio}acetate has been prepared and characterized by IR, ¹H NMR, ¹³C NMR and mass spectra. The crystal and molecular structure were further confirmed using single crystal X-ray diffraction. The crystal structure has been found to be stabilized by intermolecular C–H···O interaction generating bifurcated hydrogen bonds whereas the C–H···N interactions generate chain of molecules. The intramolecular N–H···N hydrogen bond forms a ring with S(7) graph-set motif.     

Crystal structure of calcium dihydroethylenediaminetetraacetate(2-) dihydrate Ca(H2Edta)·2H2O

The crystals of Ca(H₂Edta)·2H₂O (orthorhombic system, a = 8.5919(7) Å, b = 17.807(2) Å, c = 18.941(2) Å; Z = 8, space group Pbca) precipitate from solutions of Na₂H₂Edta·2H₂O and CaCl₂. The Ca atom is surrounded by the oxygen atoms of the water molecule and the carboxyl groups of the five neighboring H₂Edta^2? anions with protonated nitrogen atoms (distorted octahedron). As a result, a three-dimensional framework of [Ca(H₂O)H₂Edta)] with built-in crystal water molecules is formed.     

[La2Cl3(OAc)2(H2O)7]Cl: Das erste Lanthanid-Acetat-Halogenid-Hydrat mit Chlorid in innerer Koordinationssphäre

[La₂Cl₃(OAc)₂(H₂O)₇]Cl: The First Lanthanide-Acetate-Halide-Hydrate with Chloride in Inner-Sphere Coordination [La₂Cl₃(OAc)₂(H₂O)₇]Cl has been obtained as single crystals through the reaction of LaCl₃ · 7H₂O with diluted acetic acid or from La₂O₃ with acetyl chloride. In the crystal structure (triclinic, Z = 2, P1 (no. 2), a = 919.6(2), b = 950.7(2), c = 1178.9(2) pm, α = 82.52(1), β = 84.14(1), γ = 64.69(1)°, R = 0.021, R_w = 0.020), La³⁺ is surrounded by nine ligands (O, Cl). La1 has two chloride and seven oxygen ligands whereas La2 has one chloride and eight oxygen atoms as nearest neighbours. Four of the oxygen ligands of each lanthanum cation originate from a ?tetradentate”? acetate anion, the others from crystal water molecules. The ?tetradentate”? acetate groups are coordinated not only to one central La³⁺ as chelate ligands, but also to the ?left”? and ?right”? La³⁺ neighbours. Thereby, a one-dimensional infinite cationic chain, [La₂Cl₃(OAc)₂(H₂O)₇]⁺, is formed that runs in the [011] direction. These chains are held together by ?lonesome”? chloride ions which are surrounded by (4 + 1) water molecules and connected to the chains via hydrogen bonds.     

Nitrosolates and related compounds—IX: Coordination compounds of divalent copper,nickel and cobalt with nitroacetate(2−) ions as chelating ligands. Crystal and molecular structure of potassium bis[nitroacetato(2−)]cuprate(II)-water (1/1)

The syntheses of K₂[Cu(nac)₂]·H₂O (4), [Cu(nac)(N-N)(H₂O)]·H₂O (N-N = bpy, phen; 5,6) and [M(nac)(N-N)₂]·xH₂O (M = Ni, Co; 7–10) with nitroacetate(2?) ions (nac^2?) as chelating ligands are described.The structure of 4 has been determined by single crystal X-ray diffraction and contains square planar [Cu(nac)₂]^2? units in which the nitro and carboxyl groups of the two chelate ligands are in cis positions. Two of the units form a centrosymmetric dimer with a four-membered CuOCu“O”-ring, the dimers being connected by exo-oxygens of the ligands into two-dimensional layers. The water molecules and the potassium ions are arranged between the layers; there are two kinds of potassium ions with distorted (1+4+1) and (2+4+3) coordinations respectively.     

Structure of a new trinuclear nickel(II) complex with a salen-type bisoxime ligand

A new trinuclear Ni(II) complex {[NiL(DMF)]₂(OAc)₂Ni}·2DMF (H₂L = 4,4′-dichloro-2,2′-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol) is synthesized and characterized by elemental analyses, IR spectra, UV-Vis spectra and X-ray crystallography. The results show that the Ni(II) complex consists of three Ni(II) ions, two tetradentate (μ-L)^2? units, two coordinated μ-acetate ions, two coordinated DMF molecules, and two crystallization DMF molecules. All hexacoordinated Ni(II) ions of the complex have a slightly distorted octahedral geometry. The crystal packing of the Ni(II) complex reveals a notable feature of this structure: the formation of an infinite supramolecular 2D layered structure by virtue of intermolecular C-H…O hydrogen bonding.     

Template synthesis and structures of bis-ferrocenylboronate macrobicyclic iron(ii) tris-dioximates

A series of ferrocenylboron-capped tris-dioximate iron(ii) clathrochelates was synthesized by the template condensation of three molecules of dimethylglyoxime (H₂Dm), cyclohexanedione 1,2-dioxime (H₂Nx), or cyclooctanedione 1,2-dioxime (H₂Ox) and two molecules of ferrocenylboronic acid (FcB(OH)₂) on the Fe²⁺ ion matrix. The yields of the clathrochelate derivatives of alicyclic dioximes were substantially higher than that of their acyclic analog, because the molecules of alicyclic H₂Nx and H₂Ox α-dioximes have the s-cis-configuration suitable for complex formation, whereas the H₂Dm molecules in solution have the s-trans-configuration. The synthesized compounds were characterized using elemental analysis, IR and UV-Vis spectroscopies, MALDI-TOF mass spectrometry, ¹H and ¹³C{¹H} NMR and ⁵⁷Fe Mössbauer spectroscopies, and X-ray diffraction analysis. The crystal of FeDm₃(BFc)₂·CHCl₃ contains two types of crystallographically nonequivalent clathrochelate molecules. The intermolecular contacts C-H?Cp formed by the ferrocenyl fragments and cyclooctane carbocycles and the interactions Cp-H?O were observed in the crystal of FeOx₃(BFc)₂. The structural lability of the cyclooctane substituents allows the FeOx₃(BFc)₂ molecules to arrange by the “bump-into-hollow” mode because of attractive H?H interactions between the ribbed substituents of the neighboring molecules. The geometry of the ferrocenylborate iron(ii) clathrochelates is intermediate between a trigonal prism and a trigonal antiprism.     

Metal-organic frameworks from chiral square-pyramidal copper(II) complexes: Enantiospecific inclusion and perfectly polar alignment of guest and host molecules

The physical properties of [CuL¹₂(H₂O)] (1) and [CuL²₂(H₂O)] (2) and preparation and crystal structures of the inclusion compounds 1·(P)-C₂H₄Br₂, 2·(M)-C₂H₄Br₂, 1·CH₃CN and 2·CH₃CN are described. HL¹ and HL² (H represents the dissociable phenolic proton) are the N,O-donor chiral reduced Schiff bases N-(2-hydroxy-5-nitrobenzyl)-(R)-α-methyl-benzylamine and N-(2-hydroxy-5-nitrobenzyl)-(S)-α-methylbenzylamine, respectively. All the compounds crystallize in the non-centrosymmetric space group C2. In the crystal lattice, the host [CuLⁿ₂(H₂O)] (1 and 2) molecules connected by O−H?O and C−H?O interactions form perfectly polar two-dimensional networks. In these chiral and polar host frameworks, enantiospecific inclusion with polar ordering of the right-handed (P) and the left-handed (M) gauche form of 1,2-dibromoethane as well as polar alignment of acetonitrile molecules are observed. The host and guest molecules are linked by C−H?O interactions. The O-atoms of the nitro substituent on the ligands of 1 and 2 act as the acceptors in all these intermolecular O−H?O and C−H?O interactions. The structures reported in this work provide rare examples of enantiospecific trapping of the chiral rotamers of 1,2-dibromoethane as well as perfectly polar alignment of both guest and host molecules.     

Self‐Assembly of Polyoxometalate‐Supported Ln‐H nydroxo/Oxo Clusters with 1D Extended Structure: [LnIII(H2O)7Cr(OH)6Mo6O18]n·4nH2O (Ln = Ce,Sm, Eu)

Three novel polyoxometalate compounds consisting of Anderson‐type anions and trivalent lanthanide cations, [Ln(H₂O)₇Cr(OH)₆Mo₆O₁₈]_n·4nH₂O (Ln = Ce 1 ; Sm 2 ; Eu 3 ), have been synthesized in aqueous solution and characterized by single crystal X‐ray diffraction, elemental analyses, IR spectra, and TG analyses. Single crystal X‐ray diffractions reveal that the structures of the 1:1 composite compound formed by the heteropolyanion [Cr(OH)₆Mo₆O₁₈]^3? as the building unit and the [Ln(H₂O)₇]³⁺ complex fragment as the linker, which exhibit a type of zig‐zag chain with alternating cations and anions through the Mo‐Ot′‐Ln‐Ot′‐Mo linkage in the crystal. The magnetic properties of 1 ? 3 have been studied by measuring their magnetic susceptibility over the temperature range of 2‐300 K. The UV‐vis spectra of 1 give the Mo‐O and Cr^III‐O charge transfer transitions at 203 and 543 nm, respectively. In addition, the fluorescent characteristic transition of the Eu³⁺ ions in compound 3 is reported.     

Coordination polymer of uranyl nitrate with 4,4,10,10-Tetramethyl-1,3,7,9-Tetraazaspiro[5.5]undecane-2,8-dione (Spirocarbone, Sk): Synthesis and study of molecular and crystal structures

The coordination polymer {[UO₂(NO₃)₂(C₁₁H₂₀N₄O₂)] · 2H₂O} _n (I) was obtained and examined by X-ray diffraction. The crystals are monoclinic, space group C2/c; a = 23.1386(13), b = 5.41575(15), c = 19.7769(11) Å, β = 125.285(8)°, V = 2023.01(17) ų, ρ_calcd = 2.20 g/cm³, Z = 4. The U atom occupies a special position in the center of inversion. Its coordination polyhedron is a distorted hexagonal bipyramid with axial oxo ligands. In the equatorial plane, the U(1) atom is coordinated by four O atoms of two bidentate nitrate anions and two O atoms of two carbonyl groups of organic spirocarbone (Sk) molecules, which are related by the symmetry operation (0.5 ? x, 0.5 ? y, ?z). In the crystal, polymer chains are parallel to the direction (101). Water molecules are hydrogen-bonded to the N(1) atom of ligand Sk; in addition, they are linked together by the intermolecular hydrogen bonds O(6)-H(6d)…O(6)ⁱ(ⁱ1/2 ? x, ?1/2 + y, 1/2 ? z); H…O 2.11 Å angle O-H…O 160°) and to the nitrate anions by the hydrogen bonds O(6)-H(6e)…O(3)ⁱ; H…O 2.29 Å; the angle O-H…O 149°). In the crystal, hydrogen-bonded water molecules form chains along the axis y that are perpendicular to the coordination polymers. To verify the purity of complex I, the Rietveld refinement of its X-ray powder diffraction pattern was performed. At room temperature, the unit cell parameters are a = 23.2965(6), b = 5.51225(15), c = 19.8588(6) Å, β = 125.6063(17)°, V = 2073.40(10) ų.     

Conformational stability and force field of chloromonophosphazenes: MNDO calculations,vibrational spectra and normal coordinate analyses of Cl3PNP(X)Cl2 (X = O,S) and [Cl3PNPCl3][Y] (Y = Cl,PCl6)

The potential energy around the PN bonds for the Cl₃PNP(X)Cl₂ (X = O, S) molecules and [Cl₃PNPCl₃]⁺ cation have been derived from MNDO (modified neglect of diatomic overlap) calculations. The most stable conformations are two s-trans isomers in nearly eclipsed forms. The calculated structural parameters agree well with the X-ray experimental data. Barriers of 6 and 1.5 kJ/mol for the rotations of the POCl₂ and PCl₃ groups are predicted. In addition, the Raman spectra and the qualitative depolarization measurements for these molecules in the liquid phase have been obtained. All the data indicate that the molecules exist as a mixture of two rotamers in the molten phase. These two conformers are stabilized in the crystal packing of Cl₃PNP(O)Cl₂. The observed frequencies are in good agreement with the calculated values obtained by normal coordinate analysis. The MNDO calculation of the harmonic force field is in reasonable agreement with the experimental values. The force-constant values assigned to the torsional modes around the PN bonds correspond to low barriers for the internal rotations. These easy internal rotations around the PN and PN bonds can explain the flexibility of the phosphazene backbone and the elastomeric properties of the polyphosphazene polymers.     

Transition metal complexes with squarate anion and the pyridyl-donor ligand 1,3-bis(4-pyridyl)propane (BPP): Synthesis,crystal structure and spectroscopic investigation

Synthesis, crystal structure and the vibrational spectra of coordination polymers with 1,3-bis(4-pyridyl)propane (BPP) and squarate ion ligands and transition metal ions (M = Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺) are described. All compounds are isostructural, and the BPP is not coordinated to metal site since it is in cationic form due to protonation of N atoms from pyridyl rings. The metal is coordinated to two squarate ions and two water molecules in an octahedral distorted geometry. The two water molecules are involved in medium hydrogen bonds with squarate ligands and the average of O?O distance is 2.679(3) Å. Squarate ions adopt the 1,3-bis(monodentate) coordination mode bridging two metal centers giving rise to a 2D arrangement with (4,4) topology. The four-member ring is slightly distorted and the M–M distances are respectively 8.024 and 8.111 Å. The cationic form of BPP molecules are located inside of four-member ring cavity, presenting two different orientations, in which one molecule is inverted comparing to another. Vibrational spectra of all compounds are very similar, in agreement to crystal data. In all infrared spectra of the compounds a medium band at 1640 cm⁻¹ is observed, assigned to the in plane deformation mode of NH bond, indicative of the formation of cationic BPP. In the Raman spectra of the investigated compounds is observed a weak band around 1800 cm⁻¹, assigned to the stretching mode of free CO bond, whereas the medium band observed around 1600 cm⁻¹ is tentatively assigned to coordinated CO stretching mode. At last, a very important achievement of this investigation refers to the coordination geometries of all the investigated compounds, which are governed only by the ligands, independently of the different electronic properties of the metal ions.     

Experimental and theoretical study of N-(2-hydroxyethyl)morpholine betaine

N-(2-hydroxyethyl)morpholine betaine (HEMB) has been characterized by a single crystal X-ray analysis, FTIR spectroscopy and DFT calculations. The crystals are monoclinic, space group P2₁/c with a=10.273(2), b=9.360(2), c=9.447(2) Å and β=104.72(3)Å. Two molecules of HEMB form a centrosymmetric dimer (X2) connected by a pair of hydrogen bonds between the CH₂CH₂OH and COO⁻ groups, with the O?O distance of 2.672(2) Å. The morpholine ring adopts a chair conformation with the CH₂CH₂OH group in the axial and the CH₂COO⁻ group in the equatorial position. The structures of the dimer, B2, and two monomers, B1a and B1b, have been optimized by the B3LYP approach using the 6-31G(d,p) basis set. The computed structure of B2, agrees well with the experimental X2. From two stable monomeric conformers the more favored is B1a, with the intramolecular hydrogen bond with the O-H?O distance of 2.566 Å. The effects of hydrogen bonding and electrostatic interactions on the conformation of the molecules investigated have been discussed. The FTIR spectrum shows a broad absorption in the 3300-2600 cm⁻¹ region, typical of moderate O-H?O hydrogen bonds.     

Crystal structure,infrared and raman spectra of tripotassium trisaccha-rinate dihydrate,K<Subscript>3</Subscript>(C<Subscript>7</Subscript>H<Subscript>4</Subscript>NO<Subscript>3</Subscript>S)<Subscript>3</Subscript>·2H<Subscript>2</Subscript>O

The crystal structure of tripotassium trisaccharinate dihydrate, K₃(C₇H₄NO₃S)₃·2H₂O, is triclic, space group\(P \bar 1, Z = 2\). It consists of three crystallographically independent potassium and saccharinato ions as well as two structurally different water molecules. Potassium coordination polyhedra are irregular, with K1 and K3 six-coordinated and the third one K2 seven-coordinated. The K?O distances range from 2.652(9) to 3.100(2) Å(mean: 2.790 Å) whereas the K?N distance is 3.025(3) Å. The water molecules W2 is disordered over three positions with occupancies of approximately 0.6, 0.2 and 0.2. The hydrogen atom (H1W1) of the ordered water molecule (O1W) is hydrogen bonded to the sulfonyl oxygen atom (O11) (R(O...O)=2.976(3) Å), whereas the other hydrogen atom (H2W1) is bifurcated to the carbonyl oxygen atom (O13) (R(O...O)=2.851(3) Å) and the disordered water molecules (O23W) (R(O...O)=3.067(12) Å). The carbonyl oxygens (O13, O23 and O33) and one of the disordered water molecules (O22W) are involved in C?H...O hydrogen bonds (R(C?H...O)=3.027(4)–3.304(9) Å). Structural characteristics of the studied compound are compared with the analogous trisodium trisaccharinate dihydrate and dipotassium sodium trisaccharinate monohydrate. Infrared and Raman spectra of the title compound have been analyzed in relation to the structure, and compared with the spectra of trisodium trisaccharinate dihydrate.     

Crystal structure of thallium(I) 2-thiobarbiturate

The crystal and molecular structures of thallium(I) thiobarbiturate C₄H₃N₂O₂STl (C₄H₄N₂O₂S is 2-thiobarbituric acid, Н₂ТВА) have been determined. Crystallographic data for Tl(НТВА) are a = 11.2414(7) Å, b = 3.8444(3) Å, с = 14.8381(9) Å, β = 99.452(2)°, V = 649.00(7) ų, space group P2/с, Z = 4. Each of the two independent thallium ions is bonded to four oxygen and two sulfur atoms to form a distorted tetrahedron. N?H…O and C?H…S hydrogen bonds form a branched three-dimensional network. The structure is also stabilized by π?π interaction between heterocyclic НТВА^- ions. The IR spectra of Tl(НТВА) agree with X-ray powder diffraction data. The compound is also stable below 280°C, and Tl₂SO₄ is one of the thermolysis products in an oxidative medium in the region of 500?650°C.     

Binding of fluorine containing anions by new cationic Co(III) complex: Competitive interaction of chloride and hexafluorophosphate with [Co(phen)(H2biim)2]

A new mixed ligand cobalt(III) complex salt [Co(phen)(H₂biim)₂]Cl₃ (1) (where phen = 1,10-phenanthroline, H₂biim = 2,2′-biimidazole) has been synthesized for the first time. In an effort to explore this new cationic complex [Co(phen)(H₂biim)₂]³⁺ as binding agent for fluoroanions, complex salt [Co(phen)(H₂biim)₂](PF₆)₂Cl·2H₂O(2) has been synthesized and characterized. Single crystal X-ray structure determination has revealed that complex salt 2 crystallizes in monoclinic crystal system with space group P2₁/c and consist of one complex cation, one chloride, two hexafluorophosphate anions and two water molecules of crystallization. The packing analyses revealed that the complex cations are arranged in such a way that N-H groups of biimidazole moiety are involved in N-H?Cl interaction with chloride ion while C-H groups of phen/H₂biim are involved in C-H?F interaction with hexafluorophosphate to keep these groups in close proximity. A strong network of hydrogen bond interactions C-H?F, N-H?O, N-H?Cl, C-H?O (water) and O-H?O (water) are responsible for the stabilization of 3D supramolecular architecture. To the best of our knowledge, this is the first crystal structure of any salt containing the cation [Co(phen)(H₂biim)₂]³⁺.     

Solution and single crystal raman spectra of potassium hexacyanochromate(III)

Some inconsistency has existed in the assignment of the vibrational spectra of the Cr(CN)₆^3? ion, and the crystal structure of K₃Cr(CN)₆ has been described both as monoclinic C_2h⁵ and as orthorhombic D_2h¹⁴. The solution and single crystal Raman spectra were recorded at room temperature. On the basis of these data a new assignment was made and the crystal structure was determined to be orthorhombic.     

[Mo4O4(μ-S)4(μ-OH)2(μ-H2O)(H2O)2(pba)]2−: An Original Coordination Mode for the Ligand 1,3-Propylenebis(Oxamate)

The novel polyoxothioanion [Mo₄S₄O₄(OH)₂(OH₂)₃pba]^2? where pba^4? ligand is the 1,3-propylenebis(oxamate), was prepared by reacting Mo₁₂S₁₂O₁₂(OH)₁₂(OH₂)₆ ring with [Cu-pba]^2? in aqueous medium. NaK[Mo₄O₄(μ-S)₄(μ-OH)₂(μ-H₂O)(H₂O)₂(pba)] ·7H₂O was isolated in the solid state and fully characterized by X-ray diffraction study (tetragonal, P4(2)/m [a=20.4962(4) Å; b=20.4962(4) Å; c=14.7013(5) Å). The molecular structure consists of an arc cycle shape tetranuclear enchainment {Mo₄S₄O₄(OH)₂ (OH₂)₃} closed by a pba^4? ligand. The 3-D packing, resulting from the connection between K⁺ and Na⁺ and the coordination complex {Mo₄-pba]^2? is described. The ¹H-NMR characterization of the complex in aqueous solution is given. The ¹H-NMR spectrum exhibits four signals assigned to four enantiotopic protons of the alkyl chain of the pba^4? ligand and is in agreement with crystal structure of the complex [Mo₄-pba]^2?. The compound was also characterized by infrared spectroscopy.     

Three New Thioantimonates(V): Solvothermal Syntheses and Crystal Structures of [M(chxn)3]3(SbS4)2·4H2O (M = Ni,Co) and [Co(dien)2][Co(tren)SbS4]2·4H2O

The three new thioantimonates(V) [Ni(chxn)₃]₃(SbS₄)₂·4H₂O ( I ), [Co(chxn)₃]₃(SbS₄)₂·4H₂O ( II ) (chxn is trans‐1,2‐diaminocyclohexane) and [Co(dien)₂][Co(tren)SbS₄]₂·4H₂O ( III ) (dien is diethylenetriamine and tren is tris(2‐aminoethyl)amine) were synthesized under solvothermal conditions. Compounds I and II are isostructural crystallizing in space group C2/c. The structures are composed of isolated [M(chxn)₃]²⁺ complexes (M = Ni, Co), [SbS₄]^3? anions and crystal water molecules. Short S···N/S···O/O···O separations indicate hydrogen bonding interactions between the different constituents. Compound III crystallizes in space group and is composed of [Co(dien)₂]²⁺ and [Co(tren)SbS₄]^? anions and crystal water molecules. In the cationic complex the Co²⁺ ion is in an octahedral environment of two dien ligands whereas in [Co(tren)SbS₄]^? the Co²⁺ ion is in a trigonal bipyramidal coordination of four N atoms of tren and one S atom of the [SbS₄]^3? anion, i.e., two different coordination polyhedra around Co²⁺ coexist in this compound. Like in the former compounds an extended hydrogen bonding network connects the complexes and the water molecules into a three‐dimensional network.