Startseite Naturwissenschaften Crystal structure of bis(μ-N-i-propyl-N-n-propyldithiocarbamato-κ3S,S′:S)bis(N-i-propyl-N-n-propyldithiocarbamato-κ2S,S′)dicadmium(II), C28H56Cd2N4S8
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Crystal structure of bis(μ-N-i-propyl-N-n-propyldithiocarbamato-κ3S,S′:S)bis(N-i-propyl-N-n-propyldithiocarbamato-κ2S,S′)dicadmium(II), C28H56Cd2N4S8

  • Yee Seng Tan und Edward R.T. Tiekink EMAIL logo
Veröffentlicht/Copyright: 30. März 2018

Abstract

C28H56Cd2N4S8, monoclinic, P21/n (no. 14), a = 9.9003(3) Å, b = 11.7373(3) Å, c = 17.4539(5) Å, β = 102.999(3)°, V = 1976.22(10) Å3, Z = 2, Rgt(F) = 0.0243, wRref(F2) = 0.0582, T = 100 K.

CCDC no.:: 1830038

Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Block, pale-yellow
Size:0.16 × 0.14 × 0.10 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:1.52 mm−1
Diffractometer, scan mode:XtaLAB Synergy, ω-scans
θmax, completeness:26.4°, >99%
N(hkl)measured, N(hkl)unique, Rint:26079, 4038, 0.065
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 3607
N(param)refined:196
Programs:CrysAlisPRO [1], SHELX [2, 3], WinXG and ORTEP [4]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
Cd0.02772(2)0.36417(2)0.06330(2)0.01411(6)
S10.27314(5)0.44245(4)0.10583(3)0.01487(12)
S20.03054(5)0.59879(5)0.08886(3)0.01340(11)
S3−0.15957(5)0.29769(4)0.13250(3)0.01586(12)
S40.03365(5)0.14132(5)0.07563(4)0.01705(12)
N10.29772(17)0.66637(15)0.12506(10)0.0121(4)
N2−0.18128(17)0.07113(15)0.13327(10)0.0122(4)
C10.2107(2)0.57904(18)0.10730(12)0.0116(4)
C20.2493(2)0.78571(18)0.13086(13)0.0147(4)
H20.14680.78730.10920.018*
C30.2764(3)0.8221(2)0.21631(14)0.0241(5)
H3A0.23220.76810.24580.036*
H3B0.23800.89840.21980.036*
H3C0.37650.82340.23860.036*
C40.3159(2)0.86568(18)0.08149(14)0.0189(5)
H4A0.41520.87240.10510.028*
H4B0.27240.94100.07950.028*
H4C0.30300.83520.02810.028*
C50.4488(2)0.64609(18)0.14605(13)0.0146(4)
H5A0.46740.57810.18030.017*
H5B0.49430.71200.17680.017*
C60.5139(2)0.62823(18)0.07590(13)0.0150(4)
H6A0.51520.70120.04770.018*
H6B0.45800.57300.03910.018*
C70.6613(2)0.5836(2)0.10356(14)0.0200(5)
H7A0.71590.63790.14070.030*
H7B0.70350.57450.05820.030*
H7C0.65940.50980.12950.030*
C8−0.1089(2)0.15970(18)0.11565(12)0.0128(4)
C9−0.1435(2)−0.04848(17)0.11873(13)0.0140(4)
H9−0.0692−0.04560.08830.017*
C10−0.2661(2)−0.11282(19)0.06898(15)0.0207(5)
H10A−0.3361−0.12560.09980.031*
H10B−0.2344−0.18630.05300.031*
H10C−0.3067−0.06790.02210.031*
C11−0.0847(3)−0.1106(2)0.19514(14)0.0225(5)
H11A−0.0052−0.06810.22540.034*
H11B−0.0549−0.18700.18360.034*
H11C−0.1561−0.11660.22580.034*
C12−0.2993(2)0.08886(18)0.17089(12)0.0133(4)
H12A−0.27480.15020.21050.016*
H12B−0.31360.01830.19910.016*
C13−0.4356(2)0.12018(18)0.11438(13)0.0159(5)
H13A−0.42160.18800.08330.019*
H13B−0.46620.05640.07740.019*
C14−0.5466(2)0.1453(2)0.15960(16)0.0259(6)
H14A−0.55780.07920.19190.039*
H14B−0.63460.16140.12250.039*
H14C−0.51900.21170.19360.039*

Source of material

The compound was obtained from reacting a 1:2 mixture of CdCl2 (Acros Organic) and Na[S2CN(i-Pr)n-Pr] [prepared from the 1:1:1 reaction of CS2 (Panreac), N(i-Pr)n-Pr (Alfa Aesar) and NaOH (Merck) in acetone solution] in water which resulted in a white precipitate. This was extracted with CH2Cl2 and filtered. The filtrate was allowed to stand for slow evaporation under ambient conditions. Colourless crystals formed after a few days. M.p.: 467.5−468.4 K. IR (cm−1): ν(C—S) 1188 (s, sh), 955 (s, br), ν(C—N) 1455 (s).

Experimental details

The C-bound H atoms were geometrically placed (C—H = 0.98−1.00 Å) and refined as riding with Uiso(H) =1.2–1.5Ueq(C).

Discussion

Until 2013, the structural chemistry of the binary cadmium dithiocarbamates, Cd(S2CNRR′)2, was dominated by a single structural motif comprising a binuclear complex with equal numbers of μ2-bridging and chelating dithiocarbamate ligands leading to five-coordinate cadmium centres [5, 6] . Very recently, a new motif was discovered featuring μ2-bridging dithiocarbamate ligands exclusively, resulting in linear coordination polymers and six-coordinate cadmium centres [7, 8] . It was during such crystal engineering studies that the title compound, {Cd[S2CN(i-Pr)n-Pr]2}2, with disparate R substituents, was characterised.

The molecular structure is shown in the figure (70% displacement ellipsoids) and the centrosymmetric binuclear complex features μ2-bridging and chelating dithiocarbamate ligands, as is normal for these compounds [5, 6] . Thus, one ligand chelates one cadmium atom and simultaneously bridges the second centrosymmetrically-related cadmium atom. The bridging S2 atom forms the longest of the Cd—S bond lengths in the structure at 2.6241(6) Å, for the bridging bond (symmetry operation: −x, 1 − y, −z), and 2.7888(6) Å. The shortest bond length of 2.5471(5) Å is found for the Cd—S1 bond. The other ligand is chelating with Cd—S bond lengths intermediate to those formed by the S1 and S2 atoms. The S5 donor set is highly distorted and based on the value of τ of 0.51, cf. the extreme values of 0.0 and 1.0 for ideal square-pyramidal and trigonal-bipyramidal geometries [9], respectively, the coordination geometry is intermediate between these extremes.

The aforementioned crystal chemistry studies on Cd[S2CN(iPr)CH2CH2OH]2 [6, 7] revealed the presence of supramolecular isomers for one-dimensional coordination polymers, i.e. {Cd[S2CN(iPr)CH2CH2OH]2⋅solvent}n for solvent = acetonitrile [6] and ethanol [7]. This came about as all dithiocarbamate ligands in the polymers are μ2-bridging. Solvent-mediated structural transformations were also observed between the polymers and the anticipated binuclear molecules, i.e. {Cd[S2CN(iPr)CH2CH2OH]2}2⋅solvent. The conclusion of these studies was that the polymers were kinetic outcomes of crystallisation and that the dimers were the thermodynamic products. The title structure is very similar to the zinc analogue, {Zn[S2CN(i-Pr)n-Pr]2}2 [10] except that the transannular interaction is not as significant so the coordination geometry for the zinc atom is best described as being distorted tetrahedral. This difference in structure relates to the different sizes of the zinc and cadmium atoms.

Acknowledgements

Sunway University is thanked for support of biological and crystal engineering studies of metal dithiocarbamates.

References

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Received: 2017-11-26
Accepted: 2018-3-15
Published Online: 2018-3-30
Published in Print: 2018-5-24

©2018 Yee Seng Tan et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.

Artikel in diesem Heft

  1. Cover and Frontmatter
  2. Bis(tetraethylammonium) carbonate – boric acid – water (1/2/5), C17H56B2N2O14
  3. Crystal structure of 4-methoxy-6-phenyl-2H-pyran-2-one, C12H10O3
  4. Crystal structure of tris{(3-((E)-(((E)-2-oxidobenzylidene)hydrazono)methyl)-2-oxo-2H-chromen-4-olato-κ3O,N:N′)}dicobalt(III)tris(dimethylformamide), C60H50Co2N9O15
  5. Crystal structure of poly[bis(1-methyl-[4,4′-bipyridin]-1-ium-κN)-tetrakis(μ3-sulfato-κ3O:O′:O′′)trizinc(II)], C22H22Zn3N4O16S4
  6. Crystal structure of (5Z,10Z)-3,13-dichloro-17,18-dioxo-5,11-diphenyl-8,9,17,18-tetrahydro-7H-dibenzo[e,n][1,4,8,12]tetraazacyclopentadecine-16,19-diido-κ4N,N′,N′′,N′′′)copper(II), C31H22N4O2Cl2Cu
  7. Crystal structure of bis{5-methoxy-2-(((2-oxo-2H-chromen-6-yl)imino)methyl)phenolato-κ2N,O}zinc(II), C34H24N2O8Zn
  8. Crystal structure of 2,2′-((((ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(azanylylidene))bis(methanylylidene))diphenolato-κ2N4O)nickel(II), C28H22N2O4Ni
  9. Crystal structure of 1,1′-((1E,1′E)-(((ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(azanylylidene))bis(methanylylidene))bis(naphthalen-2-olato)cobalt(II), C36H26N2O4Co
  10. Crystal structure of camptothecin, C20H16N2O4
  11. Crystal structure of (2-(chlorophenyl)-5-methyl-1,3-dioxane-5-carboxylato–κ2O,O′)(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N,N′,N′′,N′′′)nickel(II) perchlorate monohydrate, Ni(C16H36N4)(C12H12O4Cl)ClO4⋅H2O
  12. Crystal structure of 3-(2-chloro-6-methoxyquinolin-3-yl)-5-phenylisoxazole (C19H13ClN2O2)
  13. Crystal structure of tetrakis(μ2-acetato-κ2O:O′)-bis{[(E)-2,6-diisopropyl-N-(pyridin-3-ylmethylene)aniline]copper (II)}, C44H56Cu2N4O8
  14. Crystal structure of diethyl 2-(2-chlorophenyl)-1,3-dioxane-5,5-dicarboxylate, C16H19Cl1O6
  15. Crystal structure of (μ2-2,2′-bipyridine-3,3′-dicarboxylato)-bis(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)-di-nickel(II) perchlorate N,N′-dimethylformamide solvate, C50H92Cl2N12Ni2O14
  16. Crystal structure of catena-poly[triaqua(μ2-1,2-bis(4-pyridyl)ethane-κ2N:N′)-(1,2-bis(4-pyridyl)ethane-κN)nickel(II)] 2-aminonicotinate nitrate – 1,2-bis(4-pyridyl)ethane – water (2/1/8), C36H44N8NiO12
  17. Hydrothermal synthesis and crystal structure of poly[bis(μ2-3-(3,5-dicarboxyphenoxy)phthalato-κ3O,O′:O′′)-(μ2-1,2-di(pyridin-4-yl)ethane-κ2N:N′)copper(II)], C22H14CuNO9
  18. Crystal structure of catena-poly[aqua-(methanol-κO)-bis(μ2-4-(pyridin-4-yl)benzoato-κ2N:O)-bis(triphenylphospine-κP)disilver(I)], C61H52Ag2N2O6P2
  19. The crystal structure of 6-(4-bromobenzyl)-1,3,5-trimethyl-7-phenyl-1,5-dihydro-2H-pyrrolo[3,2-d]pyrimidine-2,4(3H)-dione, C22H20BrN3O2
  20. Synthesis and crystal structure of catena-poly[bis(2-(2-((2,6-dichlorophenyl)amino)phenyl)acetato-κO2O′,O′′)-(μ2-1,4-di(pyridin-4-yl)benzene-κ2N:N′)zinc(II)], C44H32N4ZnCl4O4
  21. Crystal structure of diaqua-bis[N-phenyl-2-(quinolin-8-yloxy)acetamide-κ3-N,O,O′]-nitrato(κ2O,O′)-cerium(III) dinitrate - acetone (1/2), C40H44N7O17Ce
  22. Crystal structure of the 2D coordination polymer poly[aqua(μ2-2,2′-(1,2-phenylene)diacetato-κ3O,O′:O′)-(μ2-4,4′-bis((1H-1,2,4-triazol-1-yl)methyl)-1,1′-biphenyl-κ2N:N′)cobalt(II)], C28H26CoN6O5
  23. Crystal structure of (dimethylformamide-κO)(perchlorato-κ2O,O′){μ2-6,6′-((1,2-phenylenebis(azanylylidene))bis(methanylylidene))bis(4-bromo-2-methoxyphenolate)-κ8N,N′,O:O,O′:O′,O′′,O′′′}sodium(I)nickel(II), C25H23Br2ClN3NaNiO9
  24. The crystal structure of catena-poly[bis((4-aminophenyl)sulfonyl)(pyrimidin-2-yl)amido-κ2N,N′)-bis(μ2-4,4′-bipyridine-N,N′2N:N′)zinc(II) – methanol (1/2), C32H34N10O6S2Zn
  25. Synthesis and crystal structure poly[aqua(μ3-2-(((7-hydroxy-3-(4-hydroxy-3-sulfonatophenyl)-4-oxo-4H-chromen-8-yl)methyl)ammonio)acetate-κ4O,O′:O′′:O′′′) sodium] monohydrate, C18H18NNaO11S
  26. Crystal structure of methyl 4′-amino-3′,5′-diisopropyl-[1,1′-biphenyl]-4-carboxylate, C20H25NO2
  27. Crystal structure of (η6-1-isopropyl-4-methyl benzene)-(N-(2,5-dichlorophenyl)-1-(pyridin-2-yl)methanimine-κ2N,N′)ruthenium(II) perchlorate, C22H22Cl4N2O4Ru
  28. Crystal structure of 2-(2-(1-Chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl)-1H-1,2,4-triazole-3(2H)-thione, C14H15Cl2N3OS
  29. Crystal structure of methyl 4′-amino-3′,5′-dimethyl-[1,1′-biphenyl]-4-carboxylate, C16H17NO2
  30. The crystal structure of 1-(5-ferrocenyl-3-(trifluoromethyl)-1H-pyrazol-1-yl)pentan-1-on, C19H19F3FeN2O
  31. The crystal structure of (3S,12R,20R,24S)-3,12-diacetyl-20,24-epoxy-dammarane-3,12,25-triol acetone solvate, C34H56O6
  32. Crystal structure of methyl 10-(pyridin-4-yl)-anthracene-9-carboxylate, C21H15NO2
  33. Crystal structure of catena-poly[diaqua-bis(di(N2,N6-dihydroxypyridine-2,6-dicarboxamide))potassium(I)]tetrahydrate, C14H25N6O14K
  34. Crystal structure of poly{[μ2-(E)-1,4-bis(1H-benzo[d]imidazol-1-yl)but-2-ene-κ2N:N′][μ3–cyclohexane-1,4-dicarboxylato-κ4O,O′:O′′:O′′′]cadmium(II)}, C26H26CdN4O4
  35. Crystal structure of poly[aqua(μ3-[2,2′-bipyridine]-3,3′-dicarboxylato-κ4N,N′:O:O′)zinc(II)] – dimethylformamide (1/1), C15H15N3O6Zn
  36. The crystal structure of poly[tetraaqua-tris(μ2-2,6-di(1H-imidazol-1-yl)naphthalene-κ2N:N′)-bis(thiophene-2,5-dicarboxylato-κ1O)]dicobalt(II), C30H24CoN6O6S
  37. Crystal structure of (S)-1-(5-(anthracen-9-yl)-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl)propan-1-one, C26H22N2O
  38. Crystal structure of 5-methyl-3,3-diphenyl-1-tosyl-1,2,3,4-tetrahydropyridine, C25H25NO2S
  39. Synthesis and crystal structure of μ-[1,1′-di(mesitylphosphanido)ferrocene]bis[η5-cyclopentadienylnickel(II)] tetrahydrofurane solvate, C42H48FeNi2OP2
  40. Synthesis and crystal structure of (E)-1-(4-(((E)-5-chloro-2-hydroxybenzylidene)amino)phenyl)ethan-1-one O-methyl oxime, C16H15ClN2O2
  41. Crystal structure of bis(1-(phenylsulfonyl)-2-(1-(pyrazin-2-yl)ethylidene)hydrazin-1-ido-κ3N,N′,O)nickel(II), C24H22N8O4S2Ni
  42. Crystal Structure of bis(1-(phenylsulfonyl)-2-(1-(pyrazin-2-yl)ethylidene)hydrazin-1-ido-κ3N,N′,O)copper(II), C24H22N8O4S2Cu
  43. Synthesis and crystal structure of poly[aqua{μ3-(1S,2S)-1-((7-hydroxy-3-(4-hydroxy-3-sulfonatophenyl)-4-oxo-4H-chromen-8-yl)methyl)pyrrolidin-1-ium-2-carboxylato-κ4O,O′:O′′:O′′′}sodium(I)] monohydrate, C21H22NNaO11S
  44. Halogen bonds in the crystal structure of 1,4-diiodotetrafluorobenzene–1,2-bis(4-pyridyl)propane (1/1), C19H14F4I2N2
  45. Crystal structure of bis(μ-N-i-propyl-N-n-propyldithiocarbamato-κ2S:S′) bis(N-i-propyl-N-n-propyldithiocarbamato-κ2S,S′)dizinc(II), C28H56N4S8Zn2
  46. Crystal structure of bis(μ-N-i-propyl-N-n-propyldithiocarbamato-κ3S,S′:S)bis(N-i-propyl-N-n-propyldithiocarbamato-κ2S,S′)dicadmium(II), C28H56Cd2N4S8
  47. Crystal structure of bis(μ2-di-n-butyldithiocarbamato-κ3S,S′:S3S:S:S′)-hexacarbonyl-di-rhenium(I), C24H36N2O6Re2
  48. Crystal structure of 7-(4-methylphenyl)imidazo[1,2-a][1,3,5]triazin-4-amine, C12H11N5
  49. Crystal structure of the co-crystal O-isopropyl phenylcarbamothioate – 4,4′-bipyridine (2/1), C15H17N2OS
  50. Crystal structure of the coordination polymer catena-poly[chlorido-{μ2-2-(((3,5-dimethyl-1H-pyrazol-1-yl)methyl)amino)-3-hydroxybutanoato-κ4N,N,O:O′}copper(II)], C11H16ClCuN2O3
  51. Synthesis and crystal structure of bis(μ2-acetato-κ2O:O′)-di(ethanol)-bis{μ2-5-(N,N′-diethylamine)-5′-methoxyl-2,2′-[ethylenediyldioxybis(nitrilomethylidyne)]diphenolato-κ6O:O,N,N,O′:O′}trinickel(II) – ethanol – acetonitrile (1/2/2), C58H86Ni3N8O18
  52. Crystal structure of the bis((E)-O-ethyl-N-phenylthiocarbamate) – 4,4′-bipyridine co-crystal (2/1), C28H30N4O2S2
  53. Crystal structure of the (E)-O-methyl-N-phenyl-thiocarbamate – 4,4′-bipyridine (1/1), C18H17N3OS
  54. Crystal structure of bis(μ2-diethyldithiocarbamato-κ3S,S′:S′)-bis(tricyclohexylphosphane-κP)dicopper(I), C46H86Cu2N2P2S4
  55. Crystal structure of N-(3-chlorophenyl)ethoxycarbothioamide, C9H10ClNOS
  56. Crystal structure of bis(μ2-pyrrolidine-1-carbodithioato-κ3S,S′:S;κ3S:S:S′)-bis(tricyclohexylphosphane-P)-di-copper(I), C46H82Cu2N2P2S4
  57. Crystal structure of N-(2-chlorophenyl)methoxycarbothioamide, C8H8ClNOS
  58. Crystal structure of chlorido-methanol-(N-(2-(oxy)-3-methoxybenzylidene)pyridine-4-carbohydrazonato-κ3O,N,O′)-(4-methylphenyl)methyl-tin(IV), C23H24ClN3O4Sn
  59. Crystal structure of N-(3-chlorophenyl)(propan-2-yloxy)carbothioamide, C10H12ClNOS
  60. Crystal structure of 1-[(Z)-[4-(4-methoxyphenyl)butan-2-ylidene]amino]-3-phenylurea, C18H21N3O2
  61. A triclinic polymorph of bis(μ-N,N-bis(2-hydroxyethyl)dithiocarbamato-κ3S,S′:S′) bis(N,N-bis(2-hydroxyethyl)dithiocarbamato-κ2S:S′)zinc(II), C20H40N4O8S8Zn2
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