Startseite Crystal structure of 4,4′-bis(dibromomethyl)-1,1′-biphenyl, C14H10Br4
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Crystal structure of 4,4′-bis(dibromomethyl)-1,1′-biphenyl, C14H10Br4

  • Kai-Long Zhong ORCID logo EMAIL logo , Yue Zhou , Tian-Yu Zhang und Chao-Bo Yang
Veröffentlicht/Copyright: 19. November 2024

Abstract

C14H10Br4, tetragonal, P43212 (no. 96), a = 6.8288(8) Å, c = 31.988(6) Å, V = 1491.7(5) Å3, Z = 4, R gt(F) = 0.0540, wR ref(F 2) = 0.1479, T = 193 K.

CCDC no.: 2395524

The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal: Colourless block
Size: 0.40 × 0.32 × 0.25 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 10.8 mm−1
Diffractometer, scan mode: Bruker Apex-II, φ and ω
θ max, completeness: 27.5°, >99 %
N(hkl)measured, N(hkl)unique, R int: 7429, 1718, 0.062
Criterion for I obs, N(hkl)gt: I obs > 2σ(I obs), 1,426
N(param)refined: 83
Programs: Bruker, 1 Shelx 2 , 3
Table 2:

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

Atom x y z U iso*/U eq
Br1 1.27421 (17) 0.07779 (19) 0.44101 (4) 0.0437 (4)
Br2 0.9563 (2) 0.0867 (2) 0.36905 (4) 0.0595 (5)
C1 1.1005 (16) 0.2456 (16) 0.4080 (3) 0.036 (2)
H1A 1.1837 0.3384 0.3916 0.043*
C2 0.9693 (15) 0.3658 (14) 0.4368 (3) 0.033 (2)
C3 0.8069 (16) 0.2929 (16) 0.4564 (3) 0.035 (2)
H3A 0.7737 0.1591 0.4525 0.042*
C4 0.6902 (15) 0.4069 (17) 0.4814 (3) 0.035 (2)
H4A 0.5797 0.3507 0.4949 0.042*
C5 0.7334 (15) 0.6056 (15) 0.4872 (3) 0.031 (2)
C6 0.8961 (16) 0.6788 (16) 0.4667 (3) 0.039 (3)
H6A 0.9287 0.8131 0.4699 0.047*
C7 1.0119 (16) 0.5633 (14) 0.4417 (3) 0.039 (3)
H7A 1.1214 0.6186 0.4277 0.047*

1 Source of material

The chemical reagents 4,4′-dimethylbiphenyl, dibenzoyl peroxide and N-bromosuccinimide were purchased from Aladdin Biochemical Technology Co., Ltd without further purification. A mixture of 4,4′-dimethylbiphenyl (3.6 g, 20 mmol), N-bromosuccinimide (7.1 g 90 mmol), dibenzoyl peroxide (0.48 g, 2 mmol) and benzene (120 mL) was stirred at 80 °C for 30 min. After refluxing under nitrogen for 5 h, the solution was allowed to cool and was filtered. The organic phase was concentrated under reduced pressure, then the crude products were purified by flash column chromatography. Colorless crystals of the title compound were obtained by slow volatilization of a solution of ethanol/hexane at room temperature.

1 H NMR (500 MHz, Chloroform-d): δ 7.66 (d, J = 8.5 Hz, 4H), 7.58 (d, J = 8.5 Hz, 4H), 6.70 (s, 2H).

2 Experimental details

Crystallographic data collection was carried out on a Bruker Smart Apex CCD area detector diffractometer with graphite-monochromated Mo Kα radiation at 193 K. 1 The structure of the title compound was solved with the Shelxs-2014 2 software package and refined with the Shelxl-2018 3 program. Hydrogen atoms were placed in idealized positions and refined as riding atoms. The U iso values were constrained to be 1.2 U eq of the parent atoms. The structure was refined as an inversion twin (ratio= 0.76(7)/0.23(7)).

3 Comment

Bromine chemistry has received much attention in organic synthesis in the past decades. 4 , 5 , 6 Dibromomethyl aromatic derivatives are identified as being an important building block for the synthesis of aromatic imines, aromatic aldehydes, aromatic acetals and polymeric compounds. 7 , 8 , 9 , 10 In our research we focused on the synthesis of dibromomethyl aromatic derivatives, we have systhesized and characterized crystal structure of 1,3,5-tris(dibromomethyl)benzene in the previously work. 11

Single-crystal structure determination revealed that the title compound crystallizes in the tetragonal system with space group P43212. The asymmetric unit consists of half 4,4′-bis(dibromomethyl)-1,1′-biphenyl molecule. The C–Br bond lengths are in the range of 1.922(11)–1.959(10) Å and the Br–C–Br angle is 109.2(5)°, those are similar to that observed in previously reported dibromomethyl aromatic compounds, such as 1,2-bis(dibromomethyl)benzene, 12 1,3-bis(dibromomethyl)benzene, 12 1,4-bis(dibromomethyl)benzene 13 and 1,3,5-tris(dibromomethyl)benzene. 11 As shown in the figure, the 4,4′-bis(dibromomethyl)-1,1′-biphenyl molecule is located on a twofold axis, with dihedral angle between the two benzene rings of 27.72(4)°. The dihedral angles between the plane defined the terminal dibromomethyl group and the least-squares plane of the benzene ring are 80.99° (C1/Br1/Br2 and C2/C3/C4/C5/C6) and 63.68(6)° (C1/Br1/Br2 and C2 i /C3 i /C4 i /C5 i /C6 i ) [symmetry codes: (i) y, x, −z + 1]. The two appended dibromomethyl groups make dihedral angle of 73.52(1)°. In the solid state, the neighbor molecules are linked by weak C1–H1A…Br1 ii and C1–H1A…Br2 ii [symmetry codes: (ii) −x + 5/2, y + 1/2, −z + 3/4] hydrogen bonds.


Corresponding author: Kai-Long Zhong, School of Life and Health, Nanjing Polytechnic Institute, Nanjing, 210048, People’s Republic of China, E-mail:

Acknowledgments

We gratefully acknowledge financial support through grants from Scientific Research Foundation of Nanjing Polytechnic Institute (No. NJPI-2022–04).

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This work was financially supported by the Key Scientific Research Foundation of Nanjing Polytechnic Institute (No. NJPI-2022-04) and the Science and Technology Group Project of Nanjing Polytechnic Institute

  3. Conflict of interest: The authors declare no conflicts of interest regarding this article.

References

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Received: 2024-10-07
Accepted: 2024-11-04
Published Online: 2024-11-19
Published in Print: 2025-02-25

© 2024 the author(s), published by De Gruyter, Berlin/Boston

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

Artikel in diesem Heft

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  28. The crystal structure of (9H-thioxanthen-9- ylidene)hydrazine monohydrate, C13H11N2SO0.5
  29. The crystal structure of pyridinium diaqua-{1,2-phenylenebis((carboxylatocarbonyl)amido-κ4 N,N′,O,O′)manganese(III), C15H14MnN3O8
  30. Crystal structure of the hydrogen storage active high entropy phase Tb0.82Sm0.18Ni0.83Co0.17Mg
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