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BY 4.0 license Open Access Published by De Gruyter (O) April 20, 2022

The crystal structure of (4-fluorophenyl)(5-(hydroxymethyl)furan-2-yl)methanol, C12H11FO3

Yanrong Gao, Hui Ran and Wenqiang Tang ORCID logo

Abstract

C12H11FO3, monoclinic, P21/c (no. 14), a = 12.0648(9) Å, b = 8.3896(5) Å, c = 10.5727(9) Å, β = 104.204(8)°, V = 1037.44(14) Å3, Z = 4, R gt (F) = 0.0614, wR ref (F 2) = 0.1516, T = 293 K.

CCDC no.: 2164519

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: Colorless block
Size: 0.25 × 0.18 × 0.09 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 0.11 mm−1
Diffractometer, scan mode: Rigaku EOS, φ and ω-scans
θ max, completeness: 29.3°, >99%
N(hkl)measured, N(hkl)unique, R int: 4794, 2386, 0.029
Criterion for I obs, N(hkl)gt: I obs > 2 σ(I obs), 1831
N(param)refined: 147
Programs: CrysAlisPRO [1], OLEX2 [2], SHELX [3, 4]

Table 2:

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

x y z U iso*/U eq
C1 0.5807 (2) 1.1485 (3) 0.4555 (3) 0.0465 (6)
C2 0.5541 (2) 1.1186 (3) 0.3251 (3) 0.0553 (7)
H2 0.488307 1.161184 0.270524 0.066*
C3 0.6273 (2) 1.0232 (3) 0.2753 (3) 0.0477 (6)
H3 0.610352 1.001393 0.186385 0.057*
C4 0.7247 (2) 0.9603 (3) 0.3562 (2) 0.0365 (5)
C5 0.7490 (2) 0.9956 (3) 0.4879 (2) 0.0409 (6)
H5 0.815466 0.955703 0.543011 0.049*
C6 0.6763 (2) 1.0892 (3) 0.5394 (3) 0.0454 (6)
H6 0.692091 1.111043 0.628249 0.054*
C7 0.8018 (2) 0.8522 (3) 0.3006 (2) 0.0403 (6)
H7 0.772644 0.846663 0.205654 0.048*
C8 0.80144 (18) 0.6883 (3) 0.3564 (2) 0.0340 (5)
C9 0.7376 (2) 0.6190 (3) 0.4284 (2) 0.0393 (5)
H9 0.678465 0.665697 0.457347 0.047*
C10 0.7784 (2) 0.4594 (3) 0.4518 (3) 0.0427 (6)
H10 0.751049 0.382337 0.499653 0.051*
C11 0.86342 (19) 0.4413 (2) 0.3917 (2) 0.0344 (5)
C12 0.9415 (2) 0.3077 (3) 0.3858 (2) 0.0404 (6)
H12A 1.019196 0.347937 0.404234 0.048*
H12B 0.937413 0.231329 0.453436 0.048*
F1 0.50954 (15) 1.2440 (2) 0.5034 (2) 0.0749 (6)
O1 0.91720 (15) 0.90533 (19) 0.3301 (2) 0.0508 (5)
H1 0.920018 0.994687 0.299638 0.076*
O2 0.87890 (13) 0.58147 (17) 0.33035 (15) 0.0364 (4)
O3 0.91688 (15) 0.22764 (19) 0.26324 (17) 0.0437 (4)
H3A 0.955981 0.265661 0.217323 0.065*

Source of materials

An amount of 5 mmol 5-hydroxymethylfurfural (HMF) was dissolved in anhydrous tetrahydrofuran (THF). The fluoro-Grignard reagent (4-fluorophenyl magnesium bromide, 12.5 mL, 1 mol/L) was added to the solution slowly at ice-water bath conditions. The mixture was then stirred for 30 min at room temperature. Subsequently, 0.5 mL saturated ammonium chloride solution was added, and stirred for 30 min. The solution was later extracted three times with ethyl acetate, and the organic phases were combined. The product was further purified by column chromatography (1:1 petroleum ether/ethyl acetate). Upon slow evaporation at room temperature, crystals were acquired after one week.

Experimental details

All H atoms were refined as riding atoms in their geometrically idealized positions, with d(C–H) = 0.93 Å and U iso (H) = 1.2 U eq (C).

Comment

HMF (Hydroxymethylfurfural) is considered as an important building block platform, because it can be obtained from direct transformation of fructose, glucose, sucrose, cellulose, and inulin [5, 6]. The functional groups of HMF, including C=O, C–O, and furan ring, allows this compound some flexibility in its catalytic conversions of multifunctional substrates and in the future of value-added chemicals and fuel component [5, 7]. For example, the synthesis of 2,5-diformylfuran (DFF) from selective oxidation of HMF is commercially important, because DFF is a versatile precursor for the synthesis of fungicides, pharmaceuticals, and functional polymers [8], [9], [10], [11], [12]. Additionally, the oxidized derivative 2,5-furandicarboxylic acid (FDCA) was identified as one of the most valuable biomass-derived platform chemicals by U. S. Department of Energy [13, 14]. Therefore, a novel HMF analog, i.e., (4-fluorophenyl)(5-(hydroxymethyl)furan-2-yl)methanol, was synthesized and crystallized.

As displayed in figure, there is one molecule in the asymmetric unit of the title compound. The C–O bond lengths of 1.422(3) Å (C7–O1) and 1.425(3) Å (C12–O3) suggest the localized single bonds. The dihedral angle of the 4-fluorobenzene ring and furan ring is quite large (70.25°). The hydroxymethyl group donates its H atom to the O atom of the methanol group in the strong intermolecular hydrogen bond (O1–H1…O3, 1.9905(17) Å), and then contributes to the stable three-dimensional structures, which is like similar structures [15, 16]. Bond lengths and angles are as expected [1517].


Corresponding author: Wenqiang Tang, Collaborative Innovation Center of Green Manufacturing Technology for Traditional Chinese Medicine in Shaanxi province, School of Pharmacy, Shaanxi Institute of International Trade & Commerce, Xi’an, China, E-mail:

Funding source: Natural Science Foundation of Shaanxi Provincehttp://dx.doi.org/10.13039/501100007128

Award Identifier / Grant number: 2021JQ-883

Funding source: Key Breeding Program by the Collaborative Innovation Center of Green Manufacturing Technology for Traditional Chinese Medicine in Shaanxi provincehttp://dx.doi.org/10.13039/501100009103

Award Identifier / Grant number: 2019XT-1-02

Funding source: Effective Substances of Traditional Chinese Medicine Innovative Team in Shaanxi Institute of International Trade & Commercehttp://dx.doi.org/10.13039/501100009103

Award Identifier / Grant number: SSY18TD01

Funding source: Key Laboratory of Molecular Imaging and Drug Synthesis of Xianyang Cityhttp://dx.doi.org/10.13039/501100011710

Award Identifier / Grant number: 2021QXNL-PT-0008

  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 projects of the Natural Science Foundation of Shaanxi Province (2021JQ-883), Key Breeding Program by the Collaborative Innovation Center of Green Manufacturing Technology for Traditional Chinese Medicine in Shaanxi Province (2019XT-1-02), Effective Substances of Traditional Chinese Medicine Innovative Team in Shaanxi Institute of International Trade & Commerce (SSY18TD01), and Key Laboratory of Molecular Imaging and Drug Synthesis of Xianyang City (2021QXNL-PT-0008).

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

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Received: 2022-03-06
Accepted: 2022-04-05
Published Online: 2022-04-20
Published in Print: 2022-08-26

© 2022 Yanrong Gao et al., published by De Gruyter, Berlin/Boston

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

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