Home Crystal structure of 5H-dibenzo[c,f][1,5]oxabismocin-12 (7H)-yl acetate, C16H15O3Bi
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Crystal structure of 5H-dibenzo[c,f][1,5]oxabismocin-12 (7H)-yl acetate, C16H15O3Bi

  • Nianyuan Tan ORCID logo EMAIL logo , Shuisheng Wu , Donghui Lan , Chak-Tong Au and Bing Yi EMAIL logo
Published/Copyright: January 8, 2020

Abstract

C16H15O3Bi, orthorhombic, Pna21 (no. 33), a = 17.277(3) Å, b = 4.7288(8) Å, c = 17.776(3) Å, V = 1452.3(4) Å3, Z = 4, Rgt(F) = 0.0292, wR(F2) = 0.0678, T = 296 K.

CCDC no.: 1886916

The molecular 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:Rodlike, colorless
Size:0.24 × 0.12 × 0.06 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:12.14 mm−1
Diffractometer, scan mode:Bruker APEX-II, φ and ω-scans
θmax, completeness:26.4°, >99%
N(hkl)measured, N(hkl)unique, Rint:13322, 2925, 0.041
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 2697
N(param)refined:182
Programs:Bruker programs [1], SHELX [2], [3]
Table 2:

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

AtomxyzUiso*/Ueq
Bi10.19495(2)0.84302(5)0.52398(4)0.03465(13)
O10.2919(4)0.8698(13)0.4138(5)0.0419(18)
O20.1217(4)0.5831(17)0.6013(4)0.0406(16)
O30.1697(6)0.8829(19)0.6841(5)0.067(2)
C10.3029(5)0.6053(18)0.5549(6)0.030(2)
C20.3087(5)0.412(2)0.6147(6)0.033(2)
H20.2647740.3650760.6422900.040*
C30.3789(6)0.291(2)0.6330(5)0.042(2)
H30.3817990.1583340.6715820.050*
C40.4455(7)0.3676(19)0.5935(6)0.046(3)
H40.4931710.2913070.6068910.056*
C50.4407(5)0.5556(19)0.5348(8)0.041(2)
H50.4854230.6029720.5085330.049*
C60.3711(5)0.6765(14)0.5139(7)0.035(3)
C70.3650(7)0.8847(19)0.4500(6)0.043(2)
H7A0.3728421.0745550.4692530.052*
H7B0.4055240.8461850.4136750.052*
C80.1573(6)0.5423(18)0.4330(5)0.032(2)
C90.0858(5)0.409(2)0.4351(5)0.0344(19)
H90.0536770.4355160.4764800.041*
C100.0612(6)0.237(2)0.3761(7)0.046(2)
H100.0133860.1475590.3784200.055*
C110.1078(7)0.202(2)0.3152(7)0.052(3)
H110.0914050.0867590.2760260.063*
C120.1779(7)0.3331(19)0.3104(6)0.045(3)
H120.2084350.3105230.2677210.054*
C130.2037(5)0.5025(18)0.3705(6)0.035(2)
C140.2840(7)0.626(2)0.3652(7)0.048(3)
H14A0.3216540.4833820.3796290.057*
H14B0.2944230.6803230.3136420.057*
C150.1267(6)0.685(2)0.6685(6)0.044(2)
C160.0783(8)0.543(4)0.7273(7)0.073(4)
H16A0.0255390.6034740.7225290.110*
H16B0.0973540.5922150.7763520.110*
H16C0.0811070.3414670.7208650.110*

Source of material

The compound O(CH2C6H4)2BiCl is prepared by a literature known synthesis [4]. To a solution of O(CH2C6H4)2BiCl (0.265 g, 0.6 mmol) in 20 mL CH2Cl2, a suspension of CH3CO2Ag (0.110 g, 0.66 mmol) in 10 mL distilled water was added. The reaction mixture was stirred in the dark at room temperature for 24 h and then filtered. The organic phase was separated, washed with water and dried over anhydrous Na2SO4. After filtered, removal of the organic solvent under vacuum gave the title compound O(CH2C6H4)2BiO2CCH3. Crystals were obtained by crystallization from CH2Cl2/n-hexane. 1H NMR (400 MHz, CDCl3, TMS): δ = 8.16 (4H, d, J = 7.2 Hz), 7.54 (4H, t, J = 7.6 Hz), 7.41 (4H, d, J = 7.6 Hz), 7.27 (4H, t, J = 7.2 Hz), 5.21 (4H, d, J = 13.6 Hz), 4.80 (4H, d, J = 13.6 Hz), 2.31 (3H, s) ppm; 13C NMR (CDCl3, 100 MHz, TMS): δ = 178.51, 145.15, 136.98, 131.34, 127.77, 127.25, 77.66, 22.79 ppm.

Experimental details

The methylene and aromatic H atoms were generated geometrically and refined using the riding model with Uiso(H) set to 1.2Ueq(C). The methyl H atoms were allowed, rotate with a fixed angle around the C—C bond to best fit the experimental electron density with Uiso(H) set to 1.5Ueq(C) and C—H = 0.96 Å.

Comment

Over recent years there has been an increasing interest in the chemistry of the hypervalent organobismuth compounds having intramolecular N, O, S→Bi coordination owing to their novel structure chemistry and use in areas such as organic synthesis, catalysis and medicine [5], [6], [7], [8], [9], [10], [4], [11], [12], [13]. To the best of our knowledge, only one hypervalent organobismuth acetate with intramolecular N, O, S→Bi interactions, i.e. [2,6-(Me2NCH2)C6H3]Bi(O2CCH3)2, has been reported so far [9].

The asymmetric unit of the title structure contains one complete molecule (cf. the figure). In the molecular structure of organobismuth acetate, O(CH2C6H4)2BiO2CCH3, the transannular interaction between the bismuth atom and the oxygen atom is observed, and the Bi1-O1 distance [2.581(8) Å] is longer than those of the organobismuth halide, nitrate and cation with the 5,6,7,12-tetrahydrodibenz[c,f][1,5]oxabismocine framework, i.e. O(CH2C6H4)2BiCl (2.543(6) Å) [10], [O(CH2C6H4)2Bi]NO3 (2.508(2) Å) [10], and [O(CH2C6H4)2Bi(OH2)]+[SO3CF3] (2.417(7) Å) [4], indicating that the O→Bi coordination of the latter is slightly stronger than that of the former, and shorter than those of the organobismuth carbonate with same framework, i.e. [O(CH2C6H4)2Bi]2CO3 [2.587(4) and 2.618(3) Å] [12], suggesting that the O→Bi intramolecular interaction of the latter is slightly weaker than that of the former. The acetate group in the organobismuth acetate, O(CH2C6H4)2BiO2CCH3 acts as an asymmetric bidentate ligand [Bi(1)-O(2) 2.237(8) Å; Bi(1)-O(2) 2.8857(9) Å].

Acknowledgements

The work was supported by the Open Fund Project of Hunan Provincial Key Laboratory of Environmental Catalysis & Waste Regeneration (Hunan Institute of Engineering) (2018KF08), and the Talent Research Startup Fund of Hunan Institute of Engineering (No. 14006).

References

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Received: 2019-11-11
Accepted: 2019-12-12
Published Online: 2020-01-08
Published in Print: 2020-04-28

©2020 Nianyuan Tan et al., published by De Gruyter, Berlin/Boston

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

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  73. The crystal structure of 3-bromoisonicotinic acid, C6H4BrNO2
  74. The crystal structure of 5-nitropicolinic acid monohydrate, C6H6N2O5
  75. The crystal structure of 3-(4-hydroxybenzyl)-1,5-dioxaspiro[5.5]undecane-2,4-dione, C16H18O5
  76. Crystal structure of [[Mo3Se7(S2CNEt2)3]2(μ-Se)] ⋅ 2(C6H4Cl2), C42H68Cl4Mo6N6S12Se15
  77. Crystal structure of (E)-4-hydroxy-3-((5-phenyl-1,3,4-oxadiazol-2-yl)thio)pent-3-en-2-one, C13H12N2O3S
  78. The crystal structure of (2,3-dioxo-5,6:13,14-dibenzo-9,10-benzo-1,4,8,11-7, 11-diene-κ4N,N′,N′′,N′′′)-nickel(II), Ni(C22H14N4O2)
  79. Crystal structure of 3-(1-benzyl-2-ethyl-4-nitro-1H-imidazol-5-ylthio)-propanoic acid, C15H17N3O4S
  80. The crystal structure of dichlorobis(2-(dicyclohexylphosphino)-2′,4′,6′-tri-i-propyl-1,1′-biphenyl) palladium(II)-dichloroform, C68H100Cl8P2Pd
  81. Crystal structure and antimicrobial properties of (1,4,7,10-tetraoxacyclododecane-κ4O,O′,O′′,O′′′)cesium(I) pentaiodide, C16H32CsI5O8
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