Home Synthesis and crystal structure of bis(μ2-acetato-κ2O:O′)-bis(μ2-1-(8-(2-oxidophenyl)-3,6-dioxa-2,7-diazaocta-1,7-dien-1-yl)naphthalen-2-olato-κ6O:O,N,N′,O′:O′)trizinc(II), C44H38Zn3N4O12
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Synthesis and crystal structure of bis(μ2-acetato-κ2O:O′)-bis(μ2-1-(8-(2-oxidophenyl)-3,6-dioxa-2,7-diazaocta-1,7-dien-1-yl)naphthalen-2-olato-κ6O:O,N,N′,O′:O′)trizinc(II), C44H38Zn3N4O12

  • Zong-Li Ren , Chang Liu , Lan Wang , Yun-Dong Peng and Wen-Kui Dong EMAIL logo
Published/Copyright: October 20, 2018

Abstract

C44H38Zn3N4O12, monoclinic, C2/c (no. 15), a = 16.2076(17) Å, b = 13.9361(19) Å, c = 19.029(3) Å, β = 107.635(14)°, V = 4096.1(10) Å3, Z = 4, Rgt(F) = 0.0760, wRref(F2) = 0.1768, T = 173 K.

CCDC no.: 1853674

The crystal structure is shown in the figure. 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:Yellow block
Size:0.20 × 0.20 × 0.20 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:0.5 mm−1
Diffractometer, scan mode:Bruker SMART, φ and ω-scans
θmax, completeness:50°, >99%
N(hkl)measured, N(hkl)unique, Rint:28278, 7220, 0.055
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 4975
N(param)refined:582
Programs:Bruker programs [1], SHELX [2]
Table 2:

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

AtomxyzUiso*/Ueq
Zn10.00000.55777(9)0.25000.0350(4)
Zn20.19058(5)0.54874(7)0.26763(5)0.0404(3)
O10.1077(3)0.6531(4)0.2863(3)0.0367(13)
O20.3745(3)0.5945(4)0.3520(3)0.0560(17)
O30.3491(4)0.4232(5)0.2622(4)0.070(2)
O40.1024(3)0.4596(4)0.2850(3)0.0432(14)
O50.1583(3)0.5779(4)0.1619(3)0.0506(16)
O60.0160(3)0.5655(4)0.1459(3)0.0404(14)
N10.2887(4)0.6336(5)0.3286(4)0.0476(19)
N20.2708(4)0.4244(5)0.2805(4)0.050(2)
C10.1219(5)0.7234(6)0.3330(4)0.0358(19)
C20.0512(5)0.7729(6)0.3447(4)0.040(2)
H2−0.00450.75310.31880.049*
C30.0606(5)0.8487(6)0.3924(4)0.042(2)
H30.01180.87970.39720.051*
C40.1437(5)0.8802(6)0.4341(4)0.043(2)
C50.1507(6)0.9552(7)0.4821(6)0.072(3)
H50.10040.98370.48600.087*
C60.2306(7)0.9906(7)0.5255(5)0.067(3)
H60.23471.04070.55870.080*
C70.3057(7)0.9457(7)0.5161(6)0.073(3)
H70.36050.96720.54300.087*
C80.2972(6)0.8694(7)0.4666(6)0.066(3)
H80.34710.84110.46150.080*
C90.2161(5)0.8336(6)0.4242(4)0.042(2)
C100.2065(5)0.7543(6)0.3746(4)0.038(2)
C110.2815(5)0.7040(6)0.3719(4)0.044(2)
H110.33310.72400.40570.053*
C120.4081(5)0.5827(7)0.2905(5)0.062(3)
H12A0.46840.56390.30970.074*
H12B0.40650.64470.26690.074*
C130.3630(6)0.5116(8)0.2325(6)0.068(3)
H13A0.30770.53790.20380.081*
H13B0.39750.50140.19950.081*
C140.2589(6)0.3438(7)0.3081(5)0.065(3)
H140.30050.29660.31200.079*
C150.1861(5)0.3202(6)0.3337(5)0.051(2)
C160.1915(6)0.2338(7)0.3711(6)0.082(4)
H160.24000.19520.37730.098*
C170.1276(7)0.2039(7)0.3991(6)0.074(3)
H170.13440.14810.42710.088*
C180.0525(6)0.2577(7)0.3854(5)0.061(3)
H180.00720.23610.40170.073*
C190.0449(6)0.3440(6)0.3473(5)0.048(2)
H19−0.00580.37960.33860.058*
C200.1116(5)0.3786(6)0.3216(4)0.041(2)
C210.0789(5)0.5836(6)0.1235(4)0.040(2)
C220.0607(5)0.6181(7)0.0470(5)0.063(3)
H22A0.03120.56880.01340.094*
H22B0.11420.63350.03760.094*
H22C0.02490.67430.04000.094*

Source of material

Synthesis of the ligand H2L: A solution of salicylaldehyde (305.3 mg, 2.5 mmol) in ethanol (50 mL) was added to a solution of 1,2-bis(aminooxy)ethane (460.5 mg, 5 mmol) in ethanol (100 mL) and the mixture was heated at 323–328 K for 6 h. The solution was concentrated in vacuo and the residue was purified by column chromatography (SiO2, chloroform/ethyl acetate 30:1) to afford a yellow oily product of 2-[O-(1-ethyloxyamide)]oxime-phenol. Yield 69.8%. Elemental analysis – Anal. Calcd. for C9H12N2O3: C, 55.09%; H, 6.16%; N, 14.28%. Found: C, 55.33%; H, 6.03%; N, 14.02%. Then, a solution of 2-[O-(1-ethyloxyamide)]oxime-phenol (294.3 mg, 1.5 mmol) in ethanol (10 mL) was added to a solution of 2-hydroxy-1-naphthaldehyde (258.3 mg, 1.5 mmol) in ethanol (20 mL) and the mixture was heated at 333 K for 2 h. After cooling to room temperature, white precipitates were collected. Yield 71.3%, m.p. 402–403 K. Elemental analysis – Anal. Calcd. for C20H18N2O4: C, 68.56%; H, 5.18%; N, 8.00%. Found: C, 68.83%; H, 4.98%; N, 7.83%.

Synthesis of the Zn(II) complex An ethanol solution (3.0 mL) of zinc(II) acetate tetrahydrate (7.7 mg, 0.03 mmol) was added to a acetonitrile solution (2.0 mL) of H2L (700.7 mg, 0.02 mmol) at room temperature, the color of the mixing solution turned light yellow immediately. After the mixture was stirred for 10 min and then the mixture was filtered. The resulting filtrate as left undisturbed for about two weeks to form clear light yellow block-like crystals. Yield: 63.3%. Elemental analysis – Anal. Calcd. for C44H38Zn3N4O12: C, 56.55%; H, 4.00%; N, 6.18%; Zn, 14.43%. Found: C, 56.73%; H, 4.21%; N, 6.01%, Zn, 14.22%.

Experimental details

Hydrogen atoms were placed in their geometrically idealized positions and constrained to ride on their parent atoms.

Discussion

Some salen-type ligands (R-CCH = N—C(CH2)2-CN = CH—CR) and their transition metal complexes have been extensively investigated for several decades [4], [5], [6], [7], which can be used in electrochemical and biological fields [9], magnetisms, luminescent materials and supramolecular architectures [10], [11], [12], [13]. It is important to introduce suitable functional groups into the organic ligands in order to improve or tune the properties of these metal complexes. When an O-alkyl oxime moiety (–CCH = N—CO—C(CH2)n-CO—CN = CH—C) instead of the imine moiety is used, the larger electronegativity of the oxygen atoms is expected to affect the electronic properties of the Salamo-type ligands, which leads to much more stable complexes [14].

The title compound is only built up by the C44H38Zn3N4O12 molecules, in which all bond lengths are within the normal ranges (cf. the figure). Because of the centrosymmetric trinuclear structure of the title Zn(II) complex, the two terminal Zn(II) atoms (Zn2 and Zn2′) are both in the cis-N2O2 coordination of the deprotonated (L)2− units. The carboxylate oxygen (O5) atom from the briding acetato ligand coordinates to Zn2 in axial positions. The coordination sphere of the central Zn1 atom is completed by four phenoxo oxygen (O1, O1′, O4 and O4′) atoms from two (L)2− moieties and two acetato oxygen (O6 and O6′) atoms. All of the six oxygen atoms coordinate to Zn1 constituting an octahedral geometry [15], [16].

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Received: 2018-07-12
Accepted: 2018-10-08
Published Online: 2018-10-20
Published in Print: 2018-12-19

©2018 Zong-Li Ren et al., published by De Gruyter, Berlin/Boston

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

Articles in the same Issue

  1. Cover and Frontmatter
  2. Crystal structure of bis(6,6′-((ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(2,4-diiodophenolato)-κ4N,N′,O,O′)cer(IV), C32H20CeI8N4O4
  3. Crystal structure of (6,6′-((ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(2-chlorophenolato-κ2N,O))copper(II), C16H12Cl2CuN2O2
  4. Crystal structure of poly[aqua-(μ3-4-(pyridin-4-yl)isophthalato-κ4O,O′:O′′:O′′′)-(μ2-5-carboxy-2-(pyridin-4-yl)benzoato-κ2O:O′)samarium(III)], C26H18N2O9Sm
  5. Crystal structure of 1-{4-[(2-hydroxy-5-nitrobenzylidene)amino]phenyl}ethanone O-methyl oxime, C16H15N3O4
  6. Synthesis and crystal structure of bis(μ2-acetato-κ2O:O′)-bis(μ2-1-(8-(2-oxidophenyl)-3,6-dioxa-2,7-diazaocta-1,7-dien-1-yl)naphthalen-2-olato-κ6O:O,N,N′,O′:O′)trizinc(II), C44H38Zn3N4O12
  7. Synthesis and crystal structure of bis(μ2-acetato-κ2O:O′)–bis(μ2–(8-(2-oxidophenyl)-3,6-dioxa-2,7-diazaocta-1,7-dien-1-yl)naphthalen-2-olato-κ6O:O,N,N′,O′:O′)tricobalt(II), C44H38Co3N4O12
  8. Crystal structure of poly[aqua(μ4-2,2′,2′′-nitrilotriacetato-κ6O1,O3,O5:O2:O4:O6)-yttrium(III)], C6H8NO7Y
  9. Crystal structure of catena-poly[bromido-(μ2-pyrazine-2-carboxylato-κ3N:N′,O)copper(II)], C10H6N4Cu2O4Br
  10. Crystal structure of poly[dodekais(μ2-2,6-difluorobenzoato-κ2O:O′)-bis((μ3-hexamethylenetetramine-κ3N:N′:N′′)hexacopper(II)], C48H30N4O12F12Cu3
  11. Crystal structure of methyl 4-(4-hydroxy-3-nitrophenyl)-2-methyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate, C18H18N2O6
  12. Crystal structure of N-phenyl-2-(propan-2-ylidene)hydrazine-1-carbothioamide, C10H13N3S
  13. Crystal structure of sodium caesium zinc phosphate, NaCsZnP2O7
  14. Crystal structure of methyl 4-(4-isopropylphenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydro-quinoline-3-carboxylate, C23H29NO3
  15. Crystal structure of catena-poly[bis(μ2-1,3-di(4H-1,2,4-triazol-4-yl)benzene-κ2N:N′)-bis(thiocyanato-κ1N)cobalt(II), C22H16CoN14S2
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  17. Crystal structure of bis(2,5-di(pyridin-2-yl)-1,3,4-thiadiazole-κ2N,N′)-bis(thiocyanato-κ1N)cobalt(II), C26H16CoN10S4
  18. Crystal structure of (bis((1H-benzo[d]imidazol2-yl)methyl)amine-κ3N,N′,N′′)-(pyridine-2,6-dicarboxylato-κ3N,O,O′)zinc(II) — methanol — water (1/2/1), C25H28N6O7Zn
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  23. Crystal structural of diethyl 4-(3,5-dibromo-4-hydroxyphenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate, C19H21Br2NO5
  24. Crystal structure of catena-poly[tetraaqua(μ2-4-(1H-imidazol-1-yl)pyridine-κ2N:N′))zinc(II)] thiophene-2,5-dicarboxylate, C14H17N3O8ZnS
  25. Crystal structure of (20S)-20-(dimethylamino)-3-(tigloylamino)-5α-pregn-2,16-dien-4-one, C28H42N2O2
  26. Crystal structure of rac-trans-N,N′-bis(3,5-diiodosalicylidene)-1,2-cyclohexanediamine, C20H18I4N2O2
  27. Crystal structure of 2-bromo-7-(4-(dimethylamino)phenyl)-10-methylacridin-9 (10H)-one, C22H19BrN2O
  28. Crystal structure of catena-poly[(μ2-pentane-1,5-dicarboxylato-κ2O:O′)-(μ2-2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κ2N:N′)zinc(II)] sesquihydrate, C17H21N4O5.5Zn
  29. Crystal structure of ethyl 2-amino-4-(3,4-difluorophenyl)-5-oxo-4H,5H-pyrano[3,2-c] chromene-3-carboxylate, C21H15F2NO5
  30. Crystal structure of 9-(5-methylthiophen-2-yl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione, C18H18O3S
  31. Crystal structure of [5,5′-((propane-1,3-diylbis(azanylylidene))bis(ethan-1-yl-2-ylidene))bis(3-(ethoxycarbonyl)-2,4-dimethylpyrrol-1-ido)-κ4N,N′,N′′,N′′′]nickel(II), C23H30N4O4Ni
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  37. Crystal structure of catena-poly[aqua-bis(formato-κ1O)-(μ2-1,1′-(oxybis(1,4-phenylene))-bis(1H-1,2,4-triazole)-κ2N:N′)copper(II)]hydrate, C18H16CuN6O6
  38. Crystal structure of 5-bromo-2-(naphthalen-6-yl)pyridine, C15H10BrN
  39. Crystal structure of N-(4-methoxybenzyl)pyridazin-3-amine- a rare Z′ = 4 structure, C12H13N3O
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  41. Crystal structure of methyl 4-methyl-2,5-di(pyridin-4-yl)-1H-pyrrole-3-carboxylate monohydrate C17H15N3O2⋅H2O
  42. Crystal structure of dimethyl 5-(10-(methoxycarbonyl)anthracen-9-yl) isophthalate,C26H20O6
  43. Crystal structure of tert-butyl (R)-(1-(benzylamino)-3-methoxy-1-oxopropan-2-yl)carbamate, C16H24N2O4
  44. Crystal structure of aqua-bis(1,5-dimethyl-2-phenyl-4-(((E)-4-pyridylmethylene)amino)pyrazolidin-3-one-κN)-(nitrato-κO)-(nitrato-κ2O,O′)zinc(II), C34H34N10O9Zn
  45. Crystal structure of catena-poly[dichlorido-(μ2-1,5-dimethyl-2-phenyl-4-((pyridin-4-ylmethylene)amino)-1,2-dihydro-3H-pyrazol-3-one-κ2N:O)cobalt(II)] – methanol (1/1), C18H20Cl2CoN4O2
  46. Crystal structure of poly[diaqua-bis(μ2-1-(4-(1H-imidazol-1-yl)benzyl)-1H-1,2,4-triazole-κ2N:N′)manganese(II)]bis(2-carboxybenzoate) dihydrate, MnC40H40N10O12
  47. The crystal structure of 4-((3,4-dichlorobenzylidene)amino)-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one, C18H15Cl2N3O
  48. Crystal structure of bis(2-methoxy-6-((2-(pyrimidin-2-yl)hydrazono)methyl)phenolato-κ3N,N′,O)iron(III) perchlorate, C24H22N8O8ClFe
  49. The crystal structure of 2-[4-hydroxy-3-methoxyphenyl]-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl, C14H19N2O4
  50. Crystal structure of diaqua-bis(3,3-dimethylacrylato-κ2O,O′)zinc(II), C10H18ZnO6
  51. Crystal structure of dichloro-tetrakis[(E)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol-κN]cadmium (II), C60H74CdCl6N12O4
  52. Crystal structure of (20R)-20,25-epoxy-dammaran-3,12-dione, C30H48O3
  53. Crystal structure of (E)-3′,6′-bis(ethylamino)-2′,7′-dimethyl-2-((pyridin-2-ylmethylene)amino)spiro[isoindoline-1,9′-xanthen]-3-one, C32H31N5O2
  54. The crystal structure of 2-(4-fluorophenyl)-1,3,4-oxadiazole, C8H5FN2O
  55. Crystal structure of (2,2′-bipyridine-κ2N,N′)bis(tri(p-tolyl)phosphine-κP)copper(I) tetrafluoroborate – 4,4′-bipyridine (2/1), C57H54BCuF4N3P2
  56. The crystal structure of 2,6-dimethyl-3,5-dinitrocyclohexa-2,5-diene-1,4-dione, C8H6N2O6
  57. The crystal structure of 2,3-dimethyl-1,4-dinitrobenzene – a Z′ = 4 structure, C8H8N2O4
  58. Crystal structure of [(1,2-η)-1,2,3,4,5-pentamethyl-cyclopenta-2,4-dien-1-yl] (1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-κ6N2,O4) rubidium (I), [Rb(diaza-18-crown-6)]Cp*, C22H41N2O4Rb
  59. Crystal structure of 2-(4-fluorophenyl)-N-phenyl-2-(phenylamino)ethanesulfonamide – toluene (1/0.5), C23.5H23FN2O2S
  60. Crystal structure of pyrene-4-aldehyde, C17H10O
  61. Crystal structure of 2-(furan-2-yl)-5-methyl-1,3-dioxane-5-carboxylic acid, C10H12O5
  62. Crystal structure of 2-(4-chlorophenyl)-3-phenyl-1,8-naphthyridine, C20H13N2Cl
  63. Crystal structure and photochromism of 1-(2-ethyl-5-formylthiophen-3yl)-2-(2-cyano-1,5-dimethyl-4-pyrrl)-3,3,4,4,5,5-hexafluorocyclopent-1-ene, C19H14F6N2OS
  64. Crystal structure of 2-(4-bromophenyl)-1,3-dimethyl-1H-perimidin-3-ium iodide, C19H16BrIN2
  65. Crystal structure of 2-(4-(dimethylamino)phenyl)-10-methylacridin-9(10H)-one, C22H20N2O
  66. Crystal structure of 4-(acetoxymethyl)-6-(3-acetyl-3-(4-fluorophenyl)thioureido)cyclohex-4-ene-1,2,3-triyl triacetate, C24H26FN2O9S
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