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

  • Christoph Ludwig Teske EMAIL logo , Huayna Terraschke , Sebastian Mangelsen and Wolfgang Bensch
Published/Copyright: January 10, 2022
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 77 Issue 4-5

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.

Keywords: bismuth; crystal structure; dithiocarbamates; luminescence; synthesis; X-ray investigation

1 Introduction

Bismuth dithiocarbamates of the general formula Bi(S2CNR2)3 (R ≠ H) have been studied with increasing interest during the last decades mainly for their utility as, for example, biocides, antitumor agents, lubricants [1], [2], [3], [4], [5], [6], [7], and precursors for mono-dispersed nanoparticle-sized Bi2S3 [8]. Besides numerous reports on crystal structure investigations, a large variety of chemical and physical information about these compounds is available [9], [10], [11], [12], [13], [14], [15], [16], [17]. A frequent characteristic feature of the crystal structures is the edge (or face)-linked coordination polyhedron around Bi3+, which leads to the formation of so-called secondary Bi–S interactions. While the shape of the coordination polyhedra can vary quite appreciably, the assembly of the structure is obviously also subject to the influence of the organic moiety R, which can often take up a considerable amount of additional space. The question of the “prevalence of secondary Bi–S interactions, operating in the crystal structures” of dithiocarbamates of the general formula Bi(S2CNR2)3, is discussed in detail e.g., by Lai and Tiekink [12]. Comparatively little information is available for Bi-dithiocarbamates with R = H. We already published the crystal structures and properties of NH4Bi(S2CNH2)4·H2O and Bi(S2CNH2)3 [18]. Here we report the preparation, crystal structure, and some properties of the new heteroleptic Bi(III) dithiocarbamates Bi(S2CNH 2)2Cl (1) and Bi(S2NH 2)2SCN (2), where an additional structural influence of the halide and pseudohalide anions present in the coordination sphere of Bi3+ can be observed. The optical properties of the compounds were also investigated.

2 Experimental section

2.1 Synthesis

The title compounds were prepared by precipitation from acidic solutions of the reactants in acetone/water.

a) Bi(S2CNH2)2Cl (1): Solution (i): BiCl3 (1.26 g ≈ 0.004 mol) was dissolved in 100 mL H2O + 50 mL acetone + 5.5 mL conc. HCl (pH ≈ 1). After heating up to approx. 55 °C, while stirring continuously, a clear solution was formed after several minutes, and was now allowed to cool to 30–40 °C. Solution (ii): 0.88 g (ca. 0.008 mol) of colorless NH4S2CNH2 [19] in 20 mL H2O was added dropwise to solution (i). A dense, yellow precipitate formed temporarily at the point of entry, but quickly dissipated resulting in a clear, light-yellow solution. Already during cooling of the reaction mixture, small yellow needles started to precipitate. Further precipitation of the yellow translucent crystal needles (see ESI, Fig. S1) was achieved as the acetone slowly evaporated over 2–3 days at room temperature. After suction through a Büchner funnel, the precipitate was washed with 3 × 10 mL EtOH and afterwards dried in the desiccator above P2O5.

b) Bi(S2CNH2)2SCN (2): About 1 g of NH4SCN (ca. 0.013 mol) was dissolved in 50 mL formic acid/acetone (2/3 by volume) and 1.94 g Bi(NO3)3·5H2O (0.004 mol) was added resulting in a clear orange yellow solution (The hydrolysis [20, 21] of bismuth salts is depressed by the help of formic acid [22, 23]). 20 mL of solution (ii) (vide supra) was then added, followed by 30 mL H2O, giving rise to an orange precipitate. At the following day the translucent orange crystals (see ESI, Fig. S2) were sucked off using a Büchner funnel, rinsed with water and afterwards dried in the desiccator above P2O5.

2.2 Elemental analysis

The percent composition data (C, N, H, S; standard deviation in brackets) was determined by combustion analysis on a CHNS-Rapid-Element-Analyzer (Heraeus GmbH) using sulfanilamide as standard. Chloride was titrated potentiometric on a 736 GP-Titrino instrument (Metrohm AG) using AgNO3-solution (c = 0.01 mol L−1): Bi(S2CNH2)2Cl (428.76 g mol−1): C 5.62(5) (calcd. 5.60); H 0.99(9) (calcd. 0.94); N 6.57(4) (calcd. 6.53); S 28.96(16) (calcd. 29.92); Cl 7.8 (2) (calc. 8.27)%. Bi(S2CNH2)2SCN (451.35 g mol−1): C 8.04(4) (calcd. 7.98); H 1.03(2) (calcd. 0.89); N 9.27(2) (calcd. 9.31); S 36.16(16) (calcd. 35.52)%.

2.3 X-ray powder diffraction (XRPD)

X-ray powder diffraction (XRPD) experiments were performed using a STOE STADI P powder diffractometer (CuKα1 radiation; λ = 1.54056 Å, primary Ge(111) Johansson-type monochromator) at room temperature, equipped with a MYTHEN 1 K detector from DECTRIS. The samples were measured in transmission geometry as flat plates at room temperature. Rietveld refinements [24] were carried out with the Topas Academic [25] Version 6.0. Preferred orientation effects were accounted for by application of the March-Dollase function with one direction. The structure data from single crystal X-ray diffraction were used. After refinement of the lattice parameters, zero-point error and coefficient for the effect of preferred orientation, the refinement showed only a small residual. No additional Bragg reflections were observed proving the phase purity of the powdered samples (see ESI, Figs. S3 and S4 for difference plots).

2.4 Single crystal X-ray investigation

The single-crystal X-ray diffraction data was collected on a STOE Imaging Plate Diffraction System (IPDS-1) with graphite monochromatized MoKα radiation (λ = 0.7107 Å) at 200(2) K. The absorption correction was applied using X-Red [26] and X-Shape [27], after the correction of the raw data for Lorentz and polarization effects. The Shelxl-2014 program package [28] was used to solve the crystal structure by Direct Methods, and the refinement was performed against F 2. All atomic positions, except those of H atoms, were refined with anisotropic displacement parameters. The location of the hydrogen positions was achieved by means of difference Fourier maps. The hydrogen atoms were positioned geometrically, and were refined with isotropic displacement parameters applying a riding model, with a distance of N···H = 0.88 Å and U iso(H) = 1.5Ueq (N). Technical details of the data acquisition and selected refinement results are summarized in Table 1. The final atomic coordinates as well as the equivalent isotropic displacement parameters are listed in Table S1. Tables S2a and S2b (see ESI) show the lists of the shortest interatomic distances, selected bond angles, and geometric parameters of possible hydrogen-bonding interactions. Graphical representations of the structure were produced with the program Diamond [29].

Table 1:

Crystal data and structure refinement for 1 [Bi(S2CNH2)Cl] and 2 [Bi(S2NH2)2SCN].

1

2
Formula weight 428.74 451.37
Temperature/K 200(2) 200(2)
Wavelength/Å 0.71073 0.71073
Crystal system Trigonal Monoclinic
Space group P32 P21/c
a/Å 8.6121(3) 5.5600(2)
b/Å 8.6121(3) 14.3679(5)
c/Å 11.1554(4) 12.8665(4)
β/° 90 90.37(3)
Volume/Å3 716.53(6) 1027.83(6)
Z 3 4
Density (calculated) g/m3 2.98 2.92
μ/mm−1 19.5 18.1
F(000) 582 824
Crystal size/mm3 0.12 × 0.083 × 0.069 0.124 × 0.099 × 0.091
θ Range for data collection/° 2.731–28.267 2.125–28.281
Index ranges −11 ≤ h ≤ 10 −7 ≤ h ≤ 7
−11 ≤ k ≤ 11 −19 ≤ k ≤ 19
−14 ≤ l ≤ 14 −17 ≤ l ≤ 17
Reflections collected 9909 15,098
Independent reflections 2373 2551
R (int) 0.037 0.053
Completeness/% 100.0 100.0
Absorption correction Numerical Numerical
Max./min. transmission 0.140/0.066 0.115/0.064
Refinement method Full-matrix least-squares on F 2
Data/restraints/parameters 2373/1/94 2551/0/110
Goof (F 2) 1.097 1.013
R 1 [I > 2sigma(I)] 0.0269 0.0287
wR 2 0.0655 0.0746
R indices (all data) 0.0277 0.0331
wR 2 0.0657 0.0767
Absolute structure parameter −0.028(4)
Extinction coefficient 0.0047(6) 0.0033(3)
∆ρ/e Å−3 (max./min.) 1.07/−0.85 1.10/−0.76

Crystallographic data (including structure factors) for the structures in this paper have been deposited at the Cambridge Crystallographic Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies of the data can be obtained free of charge on quoting the depository number CCDC-2125912 for Bi(S2CNH2)2Cl and CCDC-2125913 for Bi(S2CNH2)2SCN (Fax: +44-1223-336-033; , http://www.ccdc.cam.ac.uk).

3 Further characterizations

3.1 Thermal stability

Differential thermal analysis and thermogravimetric (DTA-TG) investigations were carried out in a nitrogen atmosphere using an STA-429 instrument from Netzsch. These experiments showed that the thermal decomposition of 1 and 2 starts at relatively low temperatures between 440 and 450 K. XRPD patterns of the residues revealed the formation of mixtures containing Bi2S3 and elemental Bi, in accordance with results reported earlier for other halo-dithiocarbamates [30]. This seems to be an important difference to the corresponding tris(dithiocarbamates), where the final residues contain only MxSy (e.g., Bi2S3, [17]). Here we have found that the ratio (Bi2S3/Bi) is fluctuating, depending first and foremost on the applied experimental parameters, e.g., heating rate and final maximum temperature. Therefore, in the present study, no further thermoanalytic experiments were undertaken.

3.2 UV–VIS spectroscopy

For the collection of the reflectance spectra a UV–VIS-NIR-two-channel spectrometer Cary 5000 Instrument Version 1.12(Varian Techtron Pty., Darmstadt) was employed. The spectra were transformed into absorption spectra through the Kubelka-Munk function α/S = (1 − R)2/2R (α = absorption coefficient, R = reflectance with given wave length, and S = scattering coefficient) [31]. The optical band gap was estimated from the intersection point between the abscissa and the tangent to the linear part of the absorption edge in the plot α/S = f(E g) (see ESI, Figs. S5 and S6). BaSO4 powder was used as white standard.

3.3 Luminescence measurements

Luminescence measurements were carried out with a FL322 Fluorolog-3 fluorescence spectrometer (HORIBA Jobin Yvon GmbH) containing a 450 W xenon lamp, a R928P photomultiplier, an iHR-320-FA triple grating imaging spectrograph, and a Syncerity CCD detector. The solid Bi(S2CNH2)2Cl and Bi(S2CNH2)2SCN samples were measured at room temperature in Suprasil® silica glass ampoules. The color coordinates were calculated from the measured luminescence spectra, applying the Software Origin® [32].

4 Results and discussion

4.1 Crystal structure

4.1.1 Bi(S2CNH2)2Cl (1)

The compound crystallizes in the non-centrosymmetric trigonal space group P32 (No. 145) with Z = 3 formula units per unit cell (Table 1). The Bi3+ cation is surrounded by one S, S′-aniso-bidentate dithiocarbamate ligand with two significantly different Bi–S bonds (2.662(3) and 3.002(3) Å), and a second bidentate ligand with two very similar Bi–S bonds (2.642(3) and 2.690(3) Å). Two Cl− and one additional sulfur atom of a neighboring polyhedron complete the coordination environment (Bi···Cl = 2.842(3) and 3.294(3) Å, Bi···S = 3.095(3) Å) (Figure 1 and see ESI, Table S2a). The mean Bi–S distance (2.664(3) Å) to the three nearest sulfur atoms corresponds roughly to the sum of the ionic radii Σ r = 2.87 Å (with rBi3+ = 1.03 Å and rS2− = 1.84 Å, referring to CN = 6 [33]), and the short distance Bi···Cl = 2.842 Å matches Σ r = 2.84 Å (with rCl− = 1.81 Å [33]). The three longer distances Bi···S(1)/Cl (3.002–3.294(3) Å) (see ESI, Table S2a) can be assigned to so-called secondary Bi–S/Cl interactions [12, 13]. Similar bond length distributions are common for Bi3+ dithiocarbamates, such as in Bi{S2CN(iBu2)}3, Bi{S2CN(CH2)4}3, Bi{S2CN(CH2)6}3·CHCl3 and Bi{S2CN(Me)Ph}3·0.5CH3CN [12] (with distances Bi···S in the range from 2.5716(18) to 3.7582(16) Å). Furthermore, in NH4Bi(S2CNH2)4·H2O, Bi(CS2NH2)3 [18] (Bi···S from 2.6532(19) to 3.648(2) Å), and in Bi{S2CN(C3H7)2}2Cl, [34] (Bi···S from 2.6180(10) to 2.82290(10) Å) and (Bi···Cl from 2.9010(9) to 3.1276(10) Å), and in Bi{S2CN(CH2)4}2Cl·CHCl3 [35], the two different secondary Bi–S interactions (Bi···S = 2.99 and 3.10 Å) and the Bi···Cl = 2.9466(9) values are similar. To a first approximation, the coordination sphere around Bi3+ resembles a distorted trigonal mono-capped prism (Figure 1(b)).

Figure 1: Coordination of Bi3+ in crystals of compound 1. (a) The displacement ellipsoids are drawn at the 50% probability level. (b) Polyhedron around Bi3+ with open faces to illustrate the distorted capped trigonal prismatic shape (the C–NH2-groups are omitted, cen = centroid, see text).
Figure 1:

Coordination of Bi3+ in crystals of compound 1. (a) The displacement ellipsoids are drawn at the 50% probability level.

(b) Polyhedron around Bi3+ with open faces to illustrate the distorted capped trigonal prismatic shape (the C–NH2-groups are omitted, cen = centroid, see text).

There is a significant eccentricity of the Bi3+ cation that can be expressed as the distance between the positions of Bi3+ and the centroid cen, Figure 1(b), where cen is defined as the point for which the variance of squares of distances to the ligands is at the minimum [36]. In the present structure the Bi···cen distance amounts to 0.382 Å (see ESI, Table S2a,), as calculated by applying the procedure reported in reference [37]. The linkage of Bi-polyhedra via common Cl–S edges leads to a 1D polymeric structure with undulated chains propagating in the direction [001] (Figure 2). Strong and medium strong N–H···Cl and N–H···S hydrogen bonds (Figure 2, and ESI, Table S2a) lead to the formation of the 3D arrangement of the constituents.

Figure 2: View of the zig-zag chains of edge-linked Bi-centered polyhedra in the structure of 1. The chains are interconnected by hydrogen bonds (red, dashed lines).
Figure 2:

View of the zig-zag chains of edge-linked Bi-centered polyhedra in the structure of 1. The chains are interconnected by hydrogen bonds (red, dashed lines).

4.1.2 Bi(S2CNH2)2SCN (2)

The compound crystallizes in the centrosymmetric monoclinic space group P21/c (No. 14) with Z = 4 formula units per unit cell (Table 1). In the crystal structure the Bi–S separations are scattered over a large range from 2.6027(15) to 3.8822(16) Å (see ESI, Table S2b). Two thiocarbamate anions act as bidentate ligands with two shorter Bi···S bond lengths (2.6027(15) and 2.6693(14) Å) and two longer bonds (2.7892(17) and 2.8072(14) Å). This bonding pattern is not unusual and was also observed for several Bi3+-centered dithiocarbamate complexes [38], [39], [40]. These references contain many examples. Two monodentately acting dithiocarbamate anions are located at distances Bi···S = 3.5287(15) Å and 3.3474(14) Å, respectively. Following the discussion presented in reference [12] the long distances indicate so-called secondary interactions. One SCN− ligand is N-bonded with a Bi···N distance of 2.809(5) Å, which is rather long compared to Bi(SCN)x moieties reported in literature [41], [42], [43], [44], [45]. This may be due to the fact that this SCN− anion is also S-bonded to a neighboring polyhedron. The Bi3+ cation is further surrounded by two S-bonded SCN− ligands. One of the Bi···S contacts (3.2444(16) Å) is clearly within the range of the sum of the van der Waals radii, while the other one (Bi···S = 3.8822(16) Å) is a borderline case. Considering all Bi–S/N separations as strongly to weakly bonding contacts, the coordination polyhedron around Bi3+ can be described as a strongly distorted tetragonal anti-prism, capped by an additional sulfur atom (S2−). The Bi3+ cation is significantly displaced from the center of the polyhedron with the distance Bi···cen of 0.636 Å (Figure 3(b)).

Figure 3: Coordination polyhedra of Bi3+ in compound 2. (a) The displacement ellipsoids are drawn at the 50% probability level (hydrogens omitted for more clarity). The dashed lines indicate Bi···S distances >3.2 Å (see ESI, Table S2b). (b) Other representation of the BiS8N polyhedron illustrating the distorted antiprismatic character (Bi pink, S yellow, N blue). The quadrilateral faces are outlined in red, cen = centroid (see text).
Figure 3:

Coordination polyhedra of Bi3+ in compound 2. (a) The displacement ellipsoids are drawn at the 50% probability level (hydrogens omitted for more clarity). The dashed lines indicate Bi···S distances >3.2 Å (see ESI, Table S2b). (b) Other representation of the BiS8N polyhedron illustrating the distorted antiprismatic character (Bi pink, S yellow, N blue). The quadrilateral faces are outlined in red, cen = centroid (see text).

Two prisms of this type are linked, on the one hand, by the common quadrilateral face (S1, S5, S1, S5, Figure 3(b), red lines) situated opposite to S(2), Figure 4(a), resulting in a “prism-double”(Bi2S10N2) with a Bi3+···Bi3+ distance of 4.5318(7) Å. On the other hand, these “prism-doubles” are joined by common edges (S–S) (Figure 4(b), blue) and by a SCN-bridge (green).

Figure 4: Linkingage of the polyhedra in compound 2. (a) Two BiS8N-polyhedra (of 2) linked by the common quadrilateral face (red lines, C–NH2-groups are omitted). (b) Linkage of the “prism-doubles” by common edges (S–S) (blew) and by a SCN− bridge (green).
Figure 4:

Linkingage of the polyhedra in compound 2. (a) Two BiS8N-polyhedra (of 2) linked by the common quadrilateral face (red lines, C–NH2-groups are omitted). (b) Linkage of the “prism-doubles” by common edges (S–S) (blew) and by a SCN− bridge (green).

This mode of linkage leads to zig-zag chains propagating in the direction [100]. The chains are connected exclusively via N–H···S or N–H···N hydrogen bonding interactions forming the 3D network (see Figure 5). This connectivity pattern is different from that in organo-dithiocarbamate compounds, which also exhibit C–H···X bridges.

Figure 5: Infinite, angled chains (in crystals of compound 2) propagating in the direction [100] (H-bridges dashed lines, red).
Figure 5:

Infinite, angled chains (in crystals of compound 2) propagating in the direction [100] (H-bridges dashed lines, red).

A typical feature of the compounds investigated here, is the pronounced eccentricity of the Bi3+ cations in its coordination polyhedra. In a broader sense, the discussion in the literature of the stereochemistry of e.g., discrete octa-coordination (“dodecahedron and the square antiprism as coordination polyhedra”) [46] might also be interesting in this context. The following four points are important: “(1) direct interaction of the central atom with its ligands, (2) mutual repulsions of the ligands, (3) the perturbation introduced when non-bonding electrons are present in the valence shell of the central atom, and (4) the constraints imposed when other than monodentate ligands are employed”. Contemplating especially the crystal structure of Bi(S2CNH2)2SCN (distance Bi3+···cen = 0.636 Å, vide supra), at first glance, this might suggest that the lone electron pair (LEP) 6s 2 is stereochemically active (point 3). For a LEP to become stereo-chemically active, s–p mixing of the 6s–6p orbitals is a prerequisite. However, the heavier elements of the sixth period show a relativistic stabilization of the 6s shell [47]. Therefore, because of the large energy separation between the two orbitals and the very different spatial distribution of the 6s/6p wavefunctions of the Bi3+ cation [48] this mixing seems questionable. It was shown that in Bi complexes the interatomic distances for these additional interactions cover a quite large range. The character of normal covalent bonds (“bond lengths close to the sum of the covalent radii for the two elements involved”) and so-called secondary bonds (“interactions with interatomic distances significantly longer than a covalent bond but shorter than the sum of the van der Waals radii for the two elements concerned”) is discussed in detail in reference [49]. Furthermore, bidentate ligands and moreover, in addition to sulfur (S2−), chloride (Cl−), and nitrogen (N3−), are also involved in the coordination sphere of (Bi3+) (point 4). Anyhow, we note: the polarization of the 6s 2 electrons by this bonding situation cannot be totally excluded, but this would probably not be an active part. The nature of the lone electron pair of Bi3+, in dependence on coordination environment (and pressure), was investigated in detail by a density functional theory (DFT) study [50].

4.2 Optical properties

Figure 6 shows the emission (blue curve, λ ex = 375 nm) and excitation (green curve, λ em = 575 nm) spectra of Bi(S2CNH2)2Cl and Bi(S2CNH2)2SCN in the solid state. The emission spectra of these compounds are characterized by a broad band with maxima at 575 nm for 1 and 593 nm for 2. The difference between the emission spectra is expected due to the sensitivity of the optical properties of Bi3+ to the coordination environment, caused by the nephelauxetic effect and by the crystal field splitting [51]. For instance, the redshift of the emission spectrum of 2 is expected by the larger coordination number of Bi3+ and increasing covalence of the bonds in comparison to the situation in 1. It is important to notice that both compounds present a low luminescence intensity, assigned to the strong self-quenching effect caused by the overlap between the emission and absorption bands. The values for the optical band gaps, estimated from reflectance spectra (see ESI, Figs. S5 and S6), are 2.37 eV for 1 and 2.15 eV for 2. In addition, the same effect can be seen at the color coordinates of the emission plotted in the CIE (Commission internationale de l’éclairage) 1931 diagram for these compounds (Table 2, Figure 7). In this case, the color coordinates of 1 are shifted from (0.4430, 0.4901) to (0.4821, 0.4833) for 2.

Figure 6: Emission (blue curve, λ ex = 375 nm) and excitation (green curve, λ em = 575 nm) spectra of (a) Bi(S2CNH2)2Cl and (b) Bi(S2CNH2)2SCN in the solid state.
Figure 6:

Emission (blue curve, λ ex = 375 nm) and excitation (green curve, λ em = 575 nm) spectra of (a) Bi(S2CNH2)2Cl and (b) Bi(S2CNH2)2SCN in the solid state.

Table 2:

CIE 1931 color coordinates for Bi(S2CNH2)2Cl and Bi(S2CNH2)2SCN.

Bi(S2CNH2)2Cl Bi(S2CNH2)2SCN
CIE 1931 coordinate x 0.4430 0.4821
CIE 1931 coordinate y 0.4901 0.4833
Figure 7: Color coordinates of light emitted by Bi(S2CNH2)2Cl () and Bi(S2CNH2)2SCN () as solids plotted in the CIE 1931 diagram.
Figure 7:

Color coordinates of light emitted by Bi(S2CNH2)2Cl () and Bi(S2CNH2)2SCN () as solids plotted in the CIE 1931 diagram.

5 Conclusions

The above investigation has shown that the heteroleptic bismuth(III) dithiocabamates Bi(S2CNH2)2Cl (1) and Bi(S2CNH2)2SCN (2) can be precipitated from acidic solutions (acetone/water) of the reactants under the special conditions, as described (vide supra). Based on single crystal X-ray diffraction studies, the coordination sphere of the Bi3+ cations can be classified into the already known structural patterns of other Bi dithiocarbamates. In 1 there is a distorted mono-capped trigonal prismatic arrangement around Bi3+. This coordination geometry is found, for example, in Bi(S2CNH2)3 [18], Bi2S3, Cu4BiS10 [50], and [{Bi(pcdt)3}2]-EtOH [52] (pcdt = ammonium 1-pyrrolidinecarbodithioate), and seems to be a common asymmetric coordination environment of Bi3+. However, in the structure of 1 there are two Cl anions which are involved in the formation of Bi–Cl–Bi bridges with different bond lengths (Bi···Cl = 2.842(3) and 3.294(3) Å). A similar bonding situation was found e.g., in Bi[S2CN(C3H7)2]Cl with Bi···Cl = 2.9010(9) and 3.1276(10) Å [34]. In compound 2 the polyhedron around Bi3+ can be described as a strongly distorted tetragonal anti-prism. Two mono-capped anti-prisms form prism-doubles via a common quadrilateral face. Considering this structural feature, the formula Bi2[(S2CNH2)2SCN]2 may be closer to the real crystallographic situation. Such prism-doubles occur less frequently, and have been described in e.g., reference [16] (with intercationic distances (Bi···Bi) of 3.824(8), 3.725(9), 3.839(9), and 3.768(5) Å), and in Bi2[S2CN(C2H5OH)2]6 [53]. The latter has intercationic distances (Bi···Bi) of 3.893(4) and 3.807(4) Å, which are shorter than the distance observed here (4.5318(7) Å). The polyhedra in compounds 1 and 2 are linked by common edges to form chains. These chains are connected exclusively via N–H···S, N–H···Cl and or N–H···N bridges forming the 3D network. This is a special difference to the organo-dithiocarbamate compounds, where C–H···X interactions are dominant. Both compounds emit light in the orange range, however, strongly quenched due to the overlap between their emission and absorption ranges. The band in the emission spectrum of Bi(S2CNH2)2SCN is redshifted in comparison to the one of Bi(S2CNH2)2Cl, because of the influence of the nephelauxetic effect of the crystal field splitting on the optical properties of Bi3+.

Dedicated to Professor Christian Näther on the occasion of his 60th birthday.

Corresponding author: Christoph Ludwig Teske, Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, D-24118 Kiel, Germany, E-mail:

Funding source: Deutsche Forschungsgemeinschaft

Award Identifier / Grant number: TE 1147/1–1

Acknowledgments

We thank Inke Jeß for the measurements of the single-crystal data. One of the authors thanks Prof. Dr. M. Behrens, for allowing him to do this research in his laboratory. The authors thank the institutions: German Research Foundation (DFG), German Federal Ministry of Education and Research (BMBF) and Bavarian State Ministry of Science, Research and the Arts (StMWFK), for funding establishment at the time and further development and provisioning of the Electronic Journals Library and the electronic databases (EZB).

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Supplementary Material

The online version of this article offers supplementary material (ESI) (https://doi.org/10.1515/znb-2021-0176).

Received: 2021-12-05
Accepted: 2021-12-22
Published Online: 2022-01-10
Published in Print: 2022-05-25

© 2021 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Laudatio/Preface
  4. Christian Näther zum 60. Geburtstag gewidmet
  5. Research Articles
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  7. Crystal structure of phenanthrenide salts stabilized by 15-crown-5 and 18-crown-6
  8. Structure and properties of two new heteroleptic bismuth(III) dithiocabamates of the general composition Bi(S2CNH2)2X (X = Cl, SCN)
  9. Synthesis and structural characterization of three new mixed ligand alkaline-earth metal picrates
  10. Dimorphism of MnHAsO4(H2O): natural monoclinic krautite and its synthetic triclinic modification
  11. Synthesis, crystal structure, and topology of a polycatenated bismuth coordination polymer
  12. The unexpected crystal structure of thallium(I) tricyanomethanide Tl[C(CN)3]
  13. Synthesis, structure characterization and properties of a new oxidovanadium(IV) coordination polymer incorporating bridging (MoO4)2– and (Mo8O26)4– ligands
  14. Crystal structure of Dy11Ge4.33In5.67 and Tm11Ge4In6 from X-ray single-crystal and powder data
  15. Crystallisation of phosphates revisited: a multi-step formation process for SrHPO4
  16. Oxygen evolving reactions catalyzed by different manganese oxides: the role of oxidation state and specific surface area
  17. Synthesis and structural characterization of a new heterometallicmolybdate coordination polymer based on a µ3-bridging amino alcohol
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https://doi.org/10.1515/znb-2021-0176
Keywords for this article
bismuth; crystal structure; dithiocarbamates; luminescence; synthesis; X-ray investigation

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Laudatio/Preface
  4. Christian Näther zum 60. Geburtstag gewidmet
  5. Research Articles
  6. Bismuth-rich bimetallic clusters (CuBi8)3+ and [MBi10]4+ (M = Pd, Pt) from ionothermal synthesis
  7. Crystal structure of phenanthrenide salts stabilized by 15-crown-5 and 18-crown-6
  8. Structure and properties of two new heteroleptic bismuth(III) dithiocabamates of the general composition Bi(S2CNH2)2X (X = Cl, SCN)
  9. Synthesis and structural characterization of three new mixed ligand alkaline-earth metal picrates
  10. Dimorphism of MnHAsO4(H2O): natural monoclinic krautite and its synthetic triclinic modification
  11. Synthesis, crystal structure, and topology of a polycatenated bismuth coordination polymer
  12. The unexpected crystal structure of thallium(I) tricyanomethanide Tl[C(CN)3]
  13. Synthesis, structure characterization and properties of a new oxidovanadium(IV) coordination polymer incorporating bridging (MoO4)2– and (Mo8O26)4– ligands
  14. Crystal structure of Dy11Ge4.33In5.67 and Tm11Ge4In6 from X-ray single-crystal and powder data
  15. Crystallisation of phosphates revisited: a multi-step formation process for SrHPO4
  16. Oxygen evolving reactions catalyzed by different manganese oxides: the role of oxidation state and specific surface area
  17. Synthesis and structural characterization of a new heterometallicmolybdate coordination polymer based on a µ3-bridging amino alcohol
  18. Chemically and Light-Driven Coordination-Induced Spin State Switching (CISSS) of a nonheme-iron complex
  19. Extracting information from X-ray diffraction patterns containing Laue oscillations
  20. Gadolinium trisilicide − a paramagnetic representative of the YbSi3 type series
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