Startseite Crystal structure of (μ2-N,N′-bis((pyridin-4-yl)methyl)ethanediamide-κ2N:N′)-tetrakis(diethylcarbamodithioato-κ2S,S′)dizinc(II), C34H54N8O2S8Zn2
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Crystal structure of (μ2-N,N′-bis((pyridin-4-yl)methyl)ethanediamide-κ2N:N′)-tetrakis(diethylcarbamodithioato-κ2S,S′)dizinc(II), C34H54N8O2S8Zn2

  • Hadi D. Arman , Pavel Poplaukhin und Edward R.T. Tiekink EMAIL logo
Veröffentlicht/Copyright: 21. November 2017

Abstract

C34H54N8O2S8Zn2, monoclinic, C2/c (no. 15), a = 20.192(7) Å, b = 16.448(5) Å, c = 14.150(5) Å, β = 102.368(8)°, V = 4590(3) Å3, Z = 4, Rgt(F) = 0.052, wRref(F2) = 0.123, T = 98 K.

CCDC no.: 1583785

The molecular structure of the title compound is shown in the figure. Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Colourless prism
Size:0.30 × 0.17 × 0.08 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:14.5 cm−1
Diffractometer, scan mode:AFC12K/SATURN724, ω scans
2θmax, completeness:55°, >99%
N(hkl)measured, N(hkl)unique, Rint:16452, 5264, 0.062
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 4749
N(param)refined:251
Programs:Rigaku programs [1, 2] , SHELX [3, 4] , ORTEP [5]
Table 2:

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

AtomxyzUiso*/Ueq
Zn0.21031(2)0.20249(2)0.73375(3)0.01958(11)
O10.52122(12)0.43816(14)0.91005(18)0.0298(5)
S10.28223(4)0.08693(5)0.73415(6)0.02308(18)
S20.22879(5)0.14223(5)0.90076(6)0.02747(19)
S30.09406(4)0.24463(5)0.70649(6)0.02297(17)
S40.16676(4)0.20584(5)0.55226(6)0.02545(19)
N10.30869(13)0.01153(15)0.90478(19)0.0208(5)
N20.03936(13)0.26094(15)0.51813(19)0.0210(5)
N30.27190(13)0.30336(15)0.75524(19)0.0191(5)
N40.43457(14)0.52858(16)0.8992(2)0.0236(6)
H4N0.4174(18)0.5658(17)0.931(2)0.028*
C10.27747(16)0.07369(18)0.8533(2)0.0215(6)
C20.30565(17)−0.00001(19)1.0066(2)0.0247(7)
H2A0.3110−0.05861.02270.030*
H2B0.26050.01721.01580.030*
C30.3597(2)0.0473(2)1.0755(3)0.0343(8)
H3A0.40460.03041.06700.051*
H3B0.35580.03671.14220.051*
H3C0.35360.10561.06170.051*
C40.34887(17)−0.04722(19)0.8627(3)0.0255(7)
H4A0.3256−0.05800.79490.031*
H4B0.3508−0.09910.89880.031*
C50.42110(18)−0.0190(2)0.8643(3)0.0327(8)
H5A0.41990.03500.83470.049*
H5B0.4430−0.05760.82790.049*
H5C0.4468−0.01630.93140.049*
C60.09407(16)0.23985(17)0.5843(2)0.0205(6)
C7−0.02380(17)0.2883(2)0.5439(3)0.0273(7)
H7A−0.04660.32840.49560.033*
H7B−0.01300.31550.60780.033*
C8−0.0714(2)0.2176(2)0.5477(3)0.0378(9)
H8A−0.07820.18700.48690.057*
H8B−0.11510.23830.55670.057*
H8C−0.05170.18180.60180.057*
C90.03756(17)0.2543(2)0.4136(2)0.0257(7)
H9A−0.00960.24410.37850.031*
H9B0.06560.20750.40210.031*
C100.0637(2)0.3312(2)0.3743(3)0.0338(8)
H10A0.03660.37780.38690.051*
H10B0.06020.32550.30450.051*
H10C0.11130.33970.40640.051*
C110.28589(16)0.34213(19)0.8404(2)0.0225(6)
H110.26600.32290.89130.027*
C120.32830(16)0.40935(19)0.8573(2)0.0220(6)
H120.33640.43570.91840.026*
C130.35884(15)0.43817(18)0.7848(2)0.0203(6)
C140.34439(17)0.39753(19)0.6969(2)0.0233(6)
H140.36400.41530.64510.028*
C150.30149(17)0.3313(2)0.6848(2)0.0244(7)
H150.29240.30410.62410.029*
C160.40502(17)0.51158(18)0.7985(2)0.0238(6)
H16A0.44190.50250.76350.029*
H16B0.37890.55960.76940.029*
C170.48952(16)0.48855(18)0.9465(2)0.0221(6)

Source of materials

The compound was isolated from the 2:1 reaction of Zn(S2CNEt2)2 and (4-NC5H4)CH2N(H)C(=O)—C(=O)N(H)CH2-(C5H4N-4) following standard procedures [6, 7] . Colourless crystals were obtained by the diffusion of ethyl ether into a dimethylformamide solution of the compound. M.p.: >553 K but, turns opaque at 513 K. IR (cm−1): ν(C–S) 1065 (s, sh), ν(C–N) 1484 (s).

Experimental details

The C-bound H atoms were geometrically placed (C—H = 0.95 − 0.99 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C). The N-bound H-atoms were located in difference Fourier maps, and refined with a distance restraint of N—H = 0.88(1) Å, and with Uiso(H) set to 1.2Ueq(N). Owing to poor agreement, two low order reflections, i.e. (2 0 0) and (−1 1 1), were omitted from the final cycles of refinement. The maximum and minimum residual electron density peaks of 0.48 and 1.02 e Å−3, respectively, were located 1.37 and 0.81 Å from the Zn atom.

Comment

The isomeric molecules of general formula (n-NC5H4)CH2N(H)C(=O)—C(=O)N(H)CH2-(C5H4N-n), for n = 2, 3 and 4, abbreviated as nLH2, are bifunctional in the sense that they contain a central di-amide moiety as well as pyridyl-N donors. With metals, the situation may be envisaged whereby the pyridyl-N atoms bridge metal centres and the diamide forms supramolecular tapes via amide-N—H⋯O(amide) hydrogen bonding. As a continuation of investigations coordinating nLH2 with zinc dithiocarbamates, i.e. Zn(S2CNRR′)2 for R, R′ = alkyl [6, 7] , the title compound, [Zn[S2CNEt2]2}24LH2, was studied.

The binuclear complex is disposed about a centre of inversion with the unlabelled atoms in the Figure related by the symmetry operation 1 − x, 1 − y, 2 − z. The Zn atom is coordinated by two dithiocarbamate ligands forming Zn–S bonds that span the relatively narrow range 2.3913(10) to 2.5306(12) Å, and the pyridyl-N atom. The resulting NS4 coordination approximates a square pyramid, with the N atom in the apical position, as judged by the value of τ = 0.20, cf. τ = 0.0 for an ideal square pyramid and 1.0 for an ideal trigonal bipyramid [8]. In these respects, the structure resembles literature precedents [6, 7] . Interestingly, the molecular packing does not feature conventional hydrogen bonding interactions. Instead, the three-dimensional architecture features methylene-C—H⋯O(amide) and pyridyl-C–H⋯S interactions. This observation contradicts binuclear {Zn[S2CN(Me)CH2CH2OH]2}23LH2 [6], where supramolecular chains were formed as a result of hydroxy-O—H⋯(hydroxy) hydrogen bonding. The diamide fuctionality come into play to connect centrosymmetrically related chains into double chains via hydroxy-O—H⋯O (amide) hydrogen bonding. The situation changed somewhat when the dithiocarbamate ligand carry residues incapable of forming hydrogen bonding interactions. Thus, in binuclear {Zn[S2CN(n-Pr)2]2}23LH2 the diamide groups form amide-N—H⋯O(amide) hydrogen bonds to form supramolecular tapes [7].

Acknowledgements

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

References

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Received: 2017-10-4
Accepted: 2017-11-3
Published Online: 2017-11-21
Published in Print: 2018-1-26

©2018 Hadi D. Arman 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. Editorial 2018
  3. Crystal structure of dimethanol-bis{3-(((2-oxidonaphthalen-1-yl)methylene)amino)-2-oxo-2H-chromen-4-olato-κ3O,N:O′}dizinc(II), C42H30Zn2N2O10
  4. Crystal structure of aqua-bis{[2,6-dimethyl-N-(pyridin-2-ylmethylene)aniline-κ2N,N′]}zinc(II) triflate monohydrate [ZnC29H31N4O]CF3SO3⋅H2O
  5. Crystal structure of (E)-1-(4-{[(E)-4-Diethylamino-2-hydroxybenzene methylene]amino}phenyl)ethanone methoxy oxime, C20H27ClN3O3
  6. Crystal structure of (E)-1-(4-(((E)-4-(diethylamino)-2-hydroxybenzylidene)amino)phenyl)ethan-1-one oxime, C19H23N3O2
  7. Crystal structure of poly[(μ2-1,4-bis((2-ethyl-1H-benzo[d]imidazol-1-yl)methyl)benzene-κ2N:N′)-(μ2-4,4′-sulfonyldibenzoato-κ2O:O′)zinc(II)], C40H34N4O6SZn
  8. Crystal structure of catena-poly[diaqua(μ3-pyrazine-2,3-dicarboxylato-κ4O,N:O′:O′′)zinc(II)] 1.25 hydrate, C6H8.5N2O7.25Zn
  9. Crystal structure of fac-(acetylacetonato-κ2O,O′)tricarbonyl(tri-m-tolyl phosphane-κP)rhenium(I), C29H28O5PRe
  10. Crystal structure of bis(μ2-methanolato-κ2O:O)-bis(methanol-κ1O)-bis{3-((4-methoxy-2-oxidobenzylidene)amino)-2-oxo-2H-chromen-4-olato-κ3O,O′,N}dichromium(III), C38H36Cr2N2O14
  11. Crystal structure of poly[aqua-(μ3-pyridine-3,5-dicarboxylato-κ5O,O′:O′′,O′′′,N)zinc(II)], C7H7NO6Zn
  12. Crystal structure of bis((1-(((4-(((benzyloxy)imino)methyl)phenyl)imino)methyl)naphthalen-2-yl)oxy-κ2O,N)copper(II), C52H42CuN4O4
  13. Crystal structure of bis{5-(diethylamino)-2-(((2-oxo-2H-chromen-6-yl)imino)methyl)phenolato-κ2O,N}cobalt(II), C40H38CoN4O6
  14. Crystal structure of diaqua-bis(N,N-dimethylformamide-κ1O)-bis{3-((5-chloro-2-oxidobenzylidene)amino)-2-oxo-2H-chromen-4-olato-κ4N,O,O′:O′}dinickel(II), C38H34Ni2Cl2N4O12
  15. Crystal structure of tetrakis(methanol-κO)bis{3-((4-methoxy-2-oxidobenzylidene)amino)-2-oxo-2H-chromen-4-olato-κ3O,N,O′}bicobalt(II), C38H38Co2N2O14
  16. Crystal structure of (S)-tert-butyl-(1-hydroxypropan-2-yl)carbamate, C8H17NO3
  17. Crystal structure of 4-(4′-(pyridin-4-yl)-[1,1′-biphenyl]-4-yl)pyridin-1-ium catena-poly[{5-carboxy-4′-methyl-[1,1′-biphenyl]-3-carboxylato-κ2O,O′}-(μ2-4′-methyl-[1,1′-biphenyl]-3,5-dicarboxylato-κ4O,O′:O′′,O′′′)lead(II)], C52H40N2O9Pb
  18. Crystal structure of catena-poly[diaqua-(μ2-5-methylisophthalato-κ2O:O′)(μ2-1,4-bis((1H-1,2,4-triazol-1-yl)methyl)benzene-κ2N:N′)], NiC21H22O6N6
  19. Crystal structure of the salt tris(guanidinium) tris(tetrapropylammonium) bis(pyridine-2,4,6-tricarboxylate) – water (1/10), C55H126N14O22
  20. Crystal structure of 5-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-3,7,8-trimethoxy-4H-chromen-4-one, C19H18O8
  21. Crystal structure of poly{[μ2-1,1′-(sulfonylbis(4,1-phenylene))bis(2-methyl-1H-imidazole)-κ2N:N′][μ2-4,4′-oxydibenzoato-κ2O:O′]cobalt(II)} hemihydrate, C34H27N4O7.5SCo
  22. The crystal structure of 25,27-(2,2′-[(2-thioxo-1,3-dithiole-4,5-diyl)disulfanediyl]diethanolate)-26,28-dihydroxycalix[4]arene — dichloromethane (1/1), C36H32Cl2O4S5
  23. The crystal structure of 1,2-bis(3-(pyridin-3-yl)-1,2,4-oxadiazol-5-yl)ethane, C16H12N6O2
  24. Crystal structure of 1-benzyl-3-((4-bromophenyl)amino)-4-(4-methoxyphenyl)-1H-pyrrole-2,5-dione, C24H19BrN2O3
  25. Crystal structure of bis(2-((allylcarbamothioyl)imino)-4-methylthiazol-3-ido-κ2N,S)palladium(II), C16H20N6PdS4
  26. Crystal structure of pyrimidine-2,5-dicarboxylic acid 1.5 hydrate, C12H14N4O11
  27. Crystal structure of trans-diaqua-bis(1H-pyrazole-3-carboxylato-κ2N,O)manganese(II), C8H10N4O6Mn
  28. Crystal structure of catena-(μ3-5-bromoisophthatato-κO,O′: O′′,O′′′′)-(1,2-bis(imidazol-1-yl)ethane-κN:N′)cobalt(II), C16H13CoN4O4Br
  29. Investigation of the compound La5Zn2−xPb1 + x (x = 0.20–0.32)
  30. Crystal structure of (OC-6-13)-diaqua-bis(3,5-di(pyridin-3-yl)-4H-1,2,4-triazol-4-amine-κ1N)-bis(dicyanamido-κ1N)zinc(II) tetrahydrate, ZnC28H32N18O6
  31. Crystal structure of Ga0.62(3)Sb0.38(3)Pd3
  32. Crystal structure of Ga0.47(1)Sb0.53(1)Pd2
  33. A derivative of the Corey lactone – crystal structure of (3aR,4S,5R,6aS)-4-(((tert-butyldimethylsilyl)oxy)methyl)-2-oxohexahydro-2H-cyclopenta[b]furan-5-yl benzoate, C21H30O5Si
  34. A Corey lactone: crystal structure of (3aR,4R,5R,6aS)-5-benzoyloxy-4(hydroxymethyl)hexahydro-2H-cyclopenta[b]furan-2-one, C15H16O5
  35. Hydrothermal synthesis and crystal structure of poly[aqua-(μ2-1,3-bis(4-pyridyl)propane-κ2N:N′)-(μ2-1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylato-κ2O:O′)manganese(II) hydrate, C22H20Cl6N2O6Mn
  36. Crystal structure of 2-acetylpyrrole S-methylthiosemicarbazonium hydroiodide, C8H13IN4S
  37. Crystal structure of [N,N-bis((pyrrol-2-yl)ethylidene)butane-1,4-diamine-κ4N,N′,N′′,N′′′]-nickel(II), C16H20N4Ni
  38. Crystal structure of poly[aqua-(μ5-2,5-dicarboxybenzoato-κ5O:O:O′:O′′:O′′′)sodium(I)], C9H7NaO7
  39. Crystal structure of bis(N′-((1H-pyrrol-2-yl)methylene)-1-methylthio-methanethiohydrazido-κ2S,N)nickel(II), C14H16N6NiS4
  40. Crystal structure of 1-(4-((benzo[d][1,3]dioxol-5-yloxy)methyl)phenethyl)-4-(3-chlorophenyl) piperazin-1-ium chloride, C26H28Cl2N2O3
  41. Crystal structure of 2-(4-(2-(4-(2-fluorophenyl)piperazin-1-yl)ethyl)benzyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide, C26H26FN3O3S – a saccharin dervative
  42. Crystal structure of 3-(2-dimethylaminoethyl)-2,3-dihydro-2-thioxoquinazolin-4(1H)-one, C12H15N3OS
  43. Crystal structure of 3-(3-dimethylaminopropyl)-2,3-dihydro-2-thioxoquinazolin-4(1H)-one, C13H17N3OS
  44. The crystal structure of trans-tetraaqua-bis(p-tolylsulfinato-κO)calcium(II)), C14H22O8S2Ca
  45. The crystal structure of (E)-N′-(pyridin-2-ylmethylene)pyrazine-2-carbohydrazide, C11H9N5O
  46. Crystal structure of (E)-3-(pyren-1-yl)-1-(pyridin-4-yl)prop-2-en-1-one, C24H15NO
  47. Crystal structure of catena-poly[diaqua-(μ2-tartrato-κ4O,O′:O′′,O′′′)cobalt(II)], C4H8CoO8
  48. Crystal structure of 4-chloro-2-methyl-6-(4-(trifluoromethoxy)phenyl)pyrimidine, C12H8ClF3N2O
  49. Crystal structure of 1-(4-fluorophenyl)-N-(5-((triphenylstannyl)thio)thiophen-2-yl)methanimine, C27H20FN3S2Sn
  50. Crystal structure of methyl (Z)-2-(5-fluoro-2-oxoindolin-3-ylidene)hydrazine-1-carbodithioate, C10H8FN3OS2
  51. Crystal structure of tert-butyl (Z)-4-(2-(5-methoxy-3-(2-((methylthio)carbonothioyl)hydrazono)-2-oxoindolin-1-yl)ethyl)piperazine-1-carboxylate, C22H31N5O4S2
  52. The crystal structure of (E)-2-((2-(o-tolylcarbamothioyl)hydrazono)methyl)benzoic acid, C16H15N3O2S
  53. Crystal structure of 2-chloro-1,3-di-tert-pentyl-4,4-diphenyl-1,3,2λ3,4-diazaphosphasiletidine, C22H32ClN2PSi
  54. Crystal structure of tetramethyl 5,5′-(buta-1,3-diyne-1,4-diyl)diisophthalate, C24H18O8
  55. Crystal structural of 2-amino-4-(4-methoxyphenyl)-3-cyano-7,7-dimethyl-5-oxo-4H-5,6,7,8-tetrahydrobenzo[b]pyran, C19H20N2O3
  56. Crystal structure of 1,3,5-tris((trimethylsilyl)methyl)-1,3,5-triazinane-2,4,6-trione, C15H33N3O3Si3
  57. The crystal structure of bis(2-benzoyl-5-hydroxylphenolato-κ2O,O′)copper(II), C26H18CuO6
  58. Crystal structure of 2,6-bis(3-(pyrazin-2-yl)-1H-1,2,4-triazol-5-yl)pyridine – 1-ethyl-3-methyl-1H-imidazol-3-ium bromide (1/1), C23H22N13Br
  59. The crystal structure of (E)-N-benzyl-N′-benzylidene-4-methylbenzenesulfonohydrazide, C21H20N2O2S
  60. Crystal structure of ethyl (E)-5-((2-(3-hydroxybenzoyl)hydrazono)methyl)-3,4-dimethyl-1H-pyrrole-2-carboxylate – water – ethanol (1/1/1), C19H27N3O6
  61. The crystal structure of (E)-4-(3-ethoxy-2-hydroxybenzylideneamino)benzoic acid, C16H15NO4
  62. Crystal structure of (μ2-N,N′-bis((pyridin-4-yl)methyl)ethanediamide-κ2N:N′)-tetrakis(diethylcarbamodithioato-κ2S,S′)dizinc(II), C34H54N8O2S8Zn2
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