Startseite Crystal structure of (E)-2-(((6-bromopyridin-2-yl)methylene)amino)-3′,6′-bis(diethylamino)spiro[isoindoline-1,9′-xanthen]-3-one, C34H34N5O2Br
Artikel Open Access

Crystal structure of (E)-2-(((6-bromopyridin-2-yl)methylene)amino)-3′,6′-bis(diethylamino)spiro[isoindoline-1,9′-xanthen]-3-one, C34H34N5O2Br

  • Ai-Ping Xing , Dai Zeng und Xin-Ling Wang EMAIL logo
Veröffentlicht/Copyright: 15. Dezember 2018

Abstract

C34H34N5O2Br, orthorhombic Pca21 (no. 29), a = 21.3626(13) Å, b = 11.8358(8) Å, c = 12.0998(9) Å, Z = 4, V = 3059.38(4) Å3, Rgt(F) = 0.0507, wRref(F2) = 0.1401, T = 173 K.

CCDC no.: 1877002

The asymmetric unit of the title 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:Needle, clear colorless
Size:0.20 × 0.10 × 0.05 mm
Wavelength:Cu Kα radiation (1.54184Å)
μ:2.14 mm−1
Diffractometer, scan mode:SuperNova, ω-scans
θmax, completeness:70°, >99%
N(hkl)measured, N(hkl)unique, Rint:44776, 5403, 0.032
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 5322
N(param)refined:383
Programs:CrysAlisPRO [1], SHELX [2], [3] , OLEX2 [4]
Table 2:

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

AtomxyzUiso*/Ueq
Br10.71823(3)0.43127(7)0.52183(7)0.0704(3)
C10.6900(2)0.5235(5)0.4019(5)0.0488(13)
C20.7302(3)0.5440(6)0.3156(8)0.0650(19)
H20.77130.51320.31400.078*
C30.7083(4)0.6107(7)0.2324(9)0.078(2)
H30.73480.62890.17190.093*
C40.6474(3)0.6522(5)0.2354(6)0.0581(16)
H40.63180.69850.17750.070*
C50.6103(2)0.6242(4)0.3251(5)0.0389(11)
C60.5445(2)0.6589(4)0.3331(4)0.0362(10)
H60.51850.63150.39080.043*
C70.4425(2)0.8307(4)0.1764(4)0.0370(10)
C80.3745(2)0.8360(4)0.1875(4)0.0363(10)
C90.3310(3)0.8944(4)0.1232(5)0.0448(12)
H90.34400.93980.06270.054*
C100.2687(3)0.8844(5)0.1501(6)0.0553(15)
H100.23820.92340.10740.066*
C110.2495(3)0.8186(5)0.2381(6)0.0553(15)
H110.20620.81270.25470.066*
C120.2932(2)0.7602(4)0.3034(5)0.0461(13)
H120.28030.71650.36520.055*
C130.3557(2)0.7686(3)0.2750(4)0.0343(9)
C140.4111(2)0.7094(3)0.3288(4)0.0315(9)
C150.4065(2)0.5829(3)0.3154(4)0.0309(9)
C160.4107(3)0.5312(4)0.2116(4)0.0405(11)
H160.41870.57680.14860.049*
C170.4037(3)0.4168(4)0.1976(5)0.0444(12)
H170.40670.38550.12550.053*
C180.3923(3)0.3459(4)0.2870(5)0.0428(12)
C190.3873(2)0.3962(4)0.3923(5)0.0410(11)
H190.37830.35090.45510.049*
C200.3956(2)0.5117(4)0.4041(4)0.0341(9)
C210.40575(18)0.6615(3)0.5321(4)0.0318(9)
C220.4079(2)0.6897(4)0.6436(4)0.0360(10)
H220.39990.63330.69770.043*
C230.4218(2)0.8003(4)0.6773(4)0.0368(10)
C240.4358(3)0.8800(4)0.5937(4)0.0404(11)
H240.44710.95510.61330.048*
C250.4330(2)0.8490(4)0.4836(4)0.0362(10)
H250.44170.90450.42900.043*
C260.4180(2)0.7393(4)0.4488(4)0.0313(9)
C270.3775(4)0.1550(5)0.3666(7)0.074(2)
H27A0.40170.18330.43060.089*
H27B0.39350.07890.34770.089*
C280.3103(5)0.1461(10)0.3980(10)0.109(3)
H28A0.29510.22010.42240.163*
H28B0.30570.09130.45820.163*
H28C0.28590.12100.33400.163*
C290.3928(4)0.1801(5)0.1620(6)0.0635(17)
H29A0.40270.09870.16920.076*
H29B0.42810.21670.12270.076*
C300.3339(4)0.1933(5)0.0939(6)0.0643(17)
H30A0.29920.15420.13060.096*
H30B0.34050.16050.02040.096*
H30C0.32380.27370.08650.096*
C310.4401(3)0.9426(5)0.8228(5)0.0573(16)
H31A0.47490.97030.77610.069*
H31B0.45530.93870.90000.069*
C320.3859(5)1.0254(5)0.8163(7)0.080(3)
H32A0.37611.04070.73860.120*
H32B0.39761.09610.85310.120*
H32C0.34920.99290.85290.120*
C330.4063(3)0.7474(4)0.8729(4)0.0433(12)
H33A0.37230.69800.84530.052*
H33B0.39010.78860.93810.052*
C340.4597(3)0.6755(5)0.9082(6)0.0545(13)
H34A0.47640.63480.84400.082*
H34B0.44540.62100.96370.082*
H34C0.49260.72310.94000.082*
N10.6315(2)0.5602(4)0.4082(4)0.0428(10)
N20.52310(18)0.7272(3)0.2597(4)0.0366(8)
N30.46293(18)0.7576(3)0.2596(3)0.0335(8)
N40.3870(3)0.2300(4)0.2733(5)0.0601(14)
N50.4221(2)0.8298(3)0.7865(4)0.0444(10)
O10.39164(17)0.5499(2)0.5118(3)0.0406(7)
O20.47625(19)0.8795(3)0.1113(3)0.0473(9)

Source of materials

All starting materials are commercially available, and are used without further purification. The title compound was facilely synthesized from Rhodmine B by a two-step reaction.

The synthesis of the intermediate Rhodamine B hydrozone. Rhodamine B hydrozone is prepared according to the literature method [5]. To a 100 mL flask, Rhodamine B (2 mmol, 0.958 g) was dissolved in 30 mL ethanol. 3.0 mL (excess) hydrazine monohydrate (80%) was then added dropwise under vigorous stirring at room temperature. After the addition, the mixture was refluxed for 3 h. The solution changed from dark purple to light orange and became clear. Then the mixture was cooled and solvent was removed by reduced pressure. The resulting precipitate was filtered, washed 3 times with ethanol/water (1:1). Yield: ca. 70%.

The synthesis of the title compound. Rhodamine B hydrozone (1 mmol, 0.46 g) was dissolved in absolute ethanol, and ethanol solution of 6-bromo-2-pyridinecarbaldehyde (1 mmol, 0.186 g) was dropped to the solution under stirring. The mixture was refluxed for 5 h, and light purple precipitates appeared. The precipitate was filtered, washed 3 times with methanol/water (1:1). Yield: ca. 80%. The light purple product (0.05 mmol, 31.2 mg) was dissolved in ethanol/dichloromethane (1:1) (10 mL) to give a colorless solution to evaporate slowly at room temperature. After several days, colorless needle crystals appeared. Yield: ca. 70%.

Experimental details

The H atoms were added geometrically using riding models. Their Uiso values were set to 1.2Ueq of the parent C and N atoms, and 1.5Ueq of the parent O atoms. The classical Flack parameter was 0.00(3) [2].

Discussion

In recent years, there has been a great interest in the development of fluorescent chemosensors and fluorescent probes. Rhodamine B derivatives have attracted great attention of scientists by virtue of their long-wavelength emission and availability [5], [6], [7], [8], [9], [10].

In this paper, we report a rhodamine B pyridyl aroylhydrozone compound. The asymmetric unit contains a neutral molecule in a ring-closed form. The amide C = O bond distance is 1.214(6) Å, indicative of the keto form of the amide (cf. the figure). The dihedral angle between the least-square plane of the xanthenyl moiety and the pyridyl aroylhydrozone group is 84.69°. There are no obvious hydrogen bonding interactions or π–π interactions between adjacent molecules. Bond lengths and angles in the title molecule are in the expected ranges [11]. The title molecule may have some applications as the nitrogen atoms in pyridine ring and imine, oxygen atom in carbonyl group have strong coordination ability to transition metals and rare-earth metals [12].

Acknowledgements

This work was supported by the project of scientific and technological in Henan Province (Project No. 172102310433).

References

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Received: 2018-09-11
Accepted: 2018-11-04
Published Online: 2018-12-15
Published in Print: 2019-03-26

©2019 Ai-Ping Xing et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 Public License.

Artikel in diesem Heft

  1. Cover and Frontmatter
  2. Crystal structure of 1H-indole-5-carboxylic acid – 4,4′-bipyridine (2/1), C14H11N2O2
  3. Crystal structure of ethyl 2-amino-4-(4-ethoxyphenyl)-5-oxo-4H,5H-pyrano[3,2-c] chromene-3-carboxylate, C23H21NO6
  4. Crystal structure of ethyl 2-amino-4-(4-bromothiophen-2-yl)-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carboxylate, C16H16BrNO4S
  5. The crystal structure of 6-amino-2-methyl-8-(4-(methylthio)phenyl)-2,3,8,8a-tetrahydroisoquinoline-5,7,7(1H)-tricarbonitrile – ethanol (1/1), C20H19N5S
  6. Crystal structure of 6-amino-8-(4-isopropylphenyl)-2-methyl-2,3,8,8a-tetrahydroisoquinoline-5,7,7(1H)-tricarbonitrile-ethanol (1/1), C24H29N5O
  7. Crystal structure of 1,1′-(ethane-1,2-diyl)bis(3-ethyl-1H-imidazol-3-ium)bis(hexafluorido phosphate), C12H20F12N4P2
  8. Crystal structure of dimethyl (3aS,6R,6aS,7S)-2-pivaloyl-2,3-dihydro-1H,6H,7H-3a,6:7,9a-diepoxybenzo[de]isoquinoline-3a1,6a-dicarboxylate, C21H25NO8
  9. Crystal structure of methyl 4-(4-bromothiophen-2-yl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate, C18H20BrNO3S
  10. Hydrothermal synthesis and crystal structure of catena-poly[bis(4-((pyridin-4-ylmethyl)amino)benzoato-κ3N:O,O′)zinc(II) – 1,2-di(pyridin-4-yl)ethene – water (1/1/1), C38H34N6O5Zn
  11. The crystal structure of 1,2-dimethyl-3,4-dinitrobenzene, C8H8N2O4
  12. Synthesis and crystal structure of trans-tetraaqua-bis(3-(((7-hydroxy-3-(4-hydroxy-3-sulfonatophenyl)-4-oxo-4H-chromen-8-yl)methyl)ammonio)propanoato-κO)zinc(II) tetrahydrate, C38H48N2O26S2Zn
  13. Crystal structure of diaqua-bis(μ2-6-chloropyridin-2-olato-κ3N,O:O)-tetrakis(chloropyridin-2-olato-κ1O)-bis(penanthroline-κ2N,N′)diterbium(III), C54H38Cl6Tb2N10O8
  14. Crystal structure of oxidobis(piperidine-1-carbodithioato-κ2S,S′)vanadium(IV), C12H20N2OS4V
  15. Crystal structure of 2-((tert-butyldimethylsilyl)oxy)-5-methylisophthalaldehyde, C15H22O3Si
  16. Crystal structure of catena-poly[tetraiodido-(μ2-1,4-bis(2-methyl-1H-imidazol-1-yl)benzene-κ2N:N′)dimercury(II)], C14H14Hg2I4N4
  17. Crystal structure of tetrakis(n-butyl)-(μ2-1,2-bis(2-oxidobenzoyl)hydrazine-1,2-diido-κ6N,O,O′:N′,O′′,O′′′)ditin(IV), C30H44N2O4Sn2
  18. Crystal structure of ethyl 2-amino-4-(4-hydroxy-3-methoxyphenyl)-7-methyl-5-oxo-4H,5H-pyrano-[4,3-b]pyran-3-carboxylate, C19H19NO7
  19. Crystal structure of 3-aminopyrazine-2-carbohydrazide, C5H7N5O
  20. Crystal structure of ethanol-bis(N-((5-(ethoxycarbonyl)-3,4-dimethyl-1H-pyrrol-2-yl)methylene)benzohydrazonato-κ2N,O)copper(II), C36H42N6O7Cu
  21. Crystal structure of 3-methyl-2-oxo-2H-chromen-7-yl propionate, C13H12O4
  22. Crystal structure of 2-(dimethylamino)ethyl 4-aminobenzoate, C11H16N2O2
  23. Crystal structure of 3-(benzo[d]thiazol-2-ylamino)isobenzofuran-1(3H)-one, C15H10N2O2S
  24. Crystal structure of 3-((1H-benzo[d]imidazol-2-yl)amino)-2-(1H-benzo[d]imidazol-2-yl)isoindolin-1-one, C22H16N6O
  25. Crystal structure of (2,2′-bipyridine-κ2N,N′)bis(4-(dimethylamino)phenyldiphenylphosphane-κP)copper(I) tetrafluoroborate, C50H48BCuF4N4P2
  26. Crystal structure of citric acid–acetonitrile (1/1), C8H11NO7
  27. Crystal structure of diethyl 2-(4-methoxyphenyl)-1-phenyl-1,2-dihydropyridine-3,5-dicarboxylate, C24H25NO5
  28. The crystal structure of poly[triaqua-bis(μ3-2,5-dihydroxyterephthalato-κ4O,O′:O′′:O′′′)-(μ4-oxalato-κ4O,O′:O′′,O′′′)cerium(III)], C9H10CeO11
  29. Crystal structure of 1-(5-(anthracen-9-yl)-3-(4-hydroxyphenyl)-4,5-dihydro-1H-pyrazol-1-yl)propan-1-one, C26H22N2O2
  30. Synthesis and crystal structure of 5-(8-(((2-carboxyethyl)ammonio)methyl)-7-hydroxy-4-oxo-4H-chromen-3-yl)-2-hydroxybenzenesulfonate trihydrate, C19H23NO12S
  31. Crystal structure of rac-trans-6,6′-((cyclohexane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(2-bromophenolato-κ4N,N′,O,O′)-bis(methanol)cobalt(III) chloride, C22H25Br2Co8N2O4Cl
  32. Crystal structure of 1-((R)-(2′-(dimethylamino)-[1,1′-binaphthalen]-2-yl))-3-((S)-2-hydroxy-1-phenylethyl)thiourea, C31H29N3OS
  33. Crystal structure and photochemical property of 1,8-bis(p-tolylthio)pyrene, C30H22S2
  34. Crystal structure of 2-(2-(2-amino-6-chloro-9H-purin-9-yl)ethyl)propane-1,3-diyl diacetate, C14H18ClN5O4
  35. Crystal structure of ethyl 5-amino-1-(pyridin-2-yl)-1H-pyrazole-4-carboxylate, C11H12N4O2
  36. Crystal structure of trichloro-(4-chloro-2,6-bis(diphenylmethyl)-N-((pyridin-2-yl)methylene)aniline)-aluminum dichloromethane solvate, C39H31AlCl6N2
  37. Bis(ethanol-κO)-bis(6-aminopicolinato-κ2N,O)magnesium(II), C16H22O6N4Mg
  38. Crystal structure of catena-poly[aqua-(μ2-1,7-dicarba-closo-dodecaborane-1,7-dicarboxylato-κ2O:O′)-(1,10-phenanthrolin-κ2N,N′)copper(II)], C16H20B10CuN2O5
  39. Crystal structure of (1,2-dicarba-closo-dodecaborane-1,2-dithiolato κ2S,S′)-bis(1,10-phenanthroline κ2N,N′)zinc(II), C26H26B10Zn4S2
  40. Crystal structure of diaqua-bis(1,10-phenanthroline-κ2N,N′)-bis(1,7-dicarba-closo-dodecaborane-1,7-dicarboxylato-κ3O,O′:O′′) dicobalt(II) — ethanol (1/1), C34H46B20Co2N4O11
  41. Crystal structure of ((5,5′-dimethoxy-2,2′-(1,2-phenylenebis(nitrilomethylidyne)))diphenolato-κ4O,N,O′,N′)copper(II), C22H18N2CuO4
  42. Crystal structure of 1-(5-bromo-2-(4-methoxyphenyl)-1H-indol-7-yl)ethan-1-ol, C17H14BrNO2
  43. Crystal structure of (E)-2-(((6-bromopyridin-2-yl)methylene)amino)-3′,6′-bis(diethylamino)spiro[isoindoline-1,9′-xanthen]-3-one, C34H34N5O2Br
  44. Crystal structure of (Z)-2-((adamantan-1-ylimino)methyl)-5-methoxyphenol, C18H23NO2
  45. Crystal structure of bis((E)-2-ethoxy-6-(((2-hydroxyethyl)imino)methyl)phenolato-κ2N,O)copper(II), C22H28N2CuO6
  46. Crystal structure of 2,3-diphenyl-5,6-bis(4-methoxyphenyl)pyrazine, C30H24N2O2
  47. Crystal structure of dichlorido bis[1-((2,4-dimethyl-1H-imidazol-1-yl)methyl)-1H-benzo[d][1,2,3]triazole-κN]cadmium(II), Cd(C12H13N5)2Cl2
  48. The crystal structure of 1,5-di(naphthalen-2-yl)-3-(pyridin-2-yl)pentane-1,5-dione, C30H23NO2
  49. The crystal structure of 2-((3-methylthiophen-2-yl)methylene)malononitrile, C9H6N2S
  50. The crystal structure of 1,4-dinitroso-2,3,5,6-tetraacetoxy-piperazine, C12H16N4O10
  51. Crystal structure of bis(2,4,6-trichlorophenyl) malonate, C15H6Cl6O4
  52. The crystal structure of trans-dichlorido-bis(pyridine-2-carboxylato-κ2N,O)platinum(IV), C12H8Cl2N2O4Pt
  53. Crystal structure of 3-nitroquinoline 1-oxide, C9H6N2O3
  54. Crystal structure of 2-(piperidin-1-ium-4-yl)-1H-benzo[d]imidazol-3-ium dichloride dihydrate, C12H21Cl2N3O2
  55. Crystal structure of (4S,4aS,6aR,6bR,12aS,12bR,14aS,14bR)-3,3,6a,6b,9,9,12a-heptamethyloctadecahydro-1H,3H-4,14b-ethanophenanthro[1,2-h]isochromene, C30H50O
  56. Crystal structure of (E)-4-((2-fluoro-3-(trifluoromethyl)benzylidene)amino)-3-methyl-1H-1,2,4-triazole-5(4H)-thione, C11H8F4N4S
  57. Crystal structure of 5-(4-fluorophenyl)-4-methyl-2,4-dihydro-3H-1,2,4-triazole-3-thione, C9H8FN3S
  58. Crystal structure of catena-poly[(1-(4-fluorophenyl)-N–(5-((trimethylstannyl)thio)-1,3,4-thiadiazol-2-yl)methanimine], (C12H14FN3S2Sn)n
  59. The crystal structure of 4-(methoxycarbonyl)benzoic acid, C9H8O4
  60. The crystal structure of N,N′-(6-(thiophen-2-yl)-1,3,5-triazine-2,4-diyl)bis(2-methylpropane-2-sulfonamide) – ethyl acetate(2/1), C34H54N10O6S6
  61. Crystal structure of N′-(1-(2-hydroxyphenyl)ethylidene)-5-methyl-1-phenyl-1H-1,2,3-triazole-4-carbohydrazide, C18H17N5O2
  62. Crystal structure of 3-(4-methoxyphenyl)-1-phenylprop-2-yn-1-one, C16H12O2
  63. Crystal structure of N′-(1-(benzofuran-2-yl)ethylidene)-2-cyanoacetohydrazide, C13H11N3O2
  64. Crystal structure of hexa-μ2-chlorido-μ4-oxido-tetrakis(1-vinyl-1H-imidazole-κN)tetracopper(II), C20H24Cu4Cl6N8O
  65. Crystal structure of N′-((1E,2E)-4-(7-methoxy-2-oxo-2H-chromen-8-yl)-2-methylbut-2-en-1-ylidene)-4-methylbenzenesulfonohydrazide, C22H22O5N2S
  66. Crystal structure of 2-acetyl pyrene, C18H12O
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