The crystal structure of (E)-3-(2-chlorophenyl)-1-ferrocenylprop-2-en-1-one, C19H15ClFeO

Lilei Zhang; Mengru Xie

doi:10.1515/ncrs-2022-0042

Open Access Published by De Gruyter (O) April 12, 2022

The crystal structure of (E)-3-(2-chlorophenyl)-1-ferrocenylprop-2-en-1-one, C₁₉H₁₅ClFeO

Lilei Zhang and Mengru Xie

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2022-0042

Abstract

C₁₉H₁₅ClFeO, triclinic, P 1 ‾ (no. 2), a = 10.2693(5) Å, b = 11.2568(6) Å, c = 20.8930(10) Å, α = 80.350(2)°, β = 76.9640(10)°, γ = 86.921(2)°, V = 2319.4(2) Å³, Z = 6, R _gt(F) = 0.0534, wR _ref(F ²) = 0.0968, T = 170 K.

CCDC no.: 2065551

One of the three crystallographically independent molecules of the title crystal 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:	Red block
Size:	0.14 × 0.11 × 0.06 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	1.15 mm⁻¹
Diffractometer, scan mode:	D8 VENTURE, φ and ω
θ _max, completeness:	26.4°, >99%
N(hkl)_measured, N(hkl)_unique, R _int:	26,628, 9450, 0.075
Criterion for I _obs, N(hkl)_gt:	I _obs > 2 σ(I _obs), 5797
N(param)_refined:	596
Programs:	Bruker [1], Olex2 [2], SHELX [3, 4]

Table 2:

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

Atom	x	y	z	U _iso*/U _eq
C1	1.0155 (4)	0.4610 (4)	0.6198 (2)	0.0373 (11)
H1	0.960078	0.462717	0.588888	0.045*
C2	1.0073 (4)	0.5422 (4)	0.66520 (19)	0.0328 (10)
H2	0.945593	0.607692	0.670343	0.039*
C3	1.1095 (4)	0.5077 (4)	0.70243 (19)	0.0281 (9)
C4	1.1787 (4)	0.4048 (4)	0.67834 (19)	0.0311 (10)
H4	1.251413	0.362770	0.693579	0.037*
C5	1.1198 (4)	0.3768 (4)	0.6279 (2)	0.0377 (11)
H5	1.146038	0.312180	0.603505	0.045*
C6	0.7975 (4)	0.2952 (4)	0.7341 (2)	0.0452 (12)
H6	0.739908	0.302203	0.703906	0.054*
C7	0.7985 (4)	0.3716 (4)	0.7808 (2)	0.0405 (11)
H7	0.740970	0.439368	0.787733	0.049*
C8	0.8982 (4)	0.2058 (4)	0.7405 (2)	0.0408 (12)
H8	0.919446	0.141657	0.715442	0.049*
C9	0.8997 (4)	0.3306 (4)	0.81551 (19)	0.0347 (11)
H9	0.922170	0.365818	0.849766	0.042*
C10	0.9613 (4)	0.2281 (4)	0.7903 (2)	0.0359 (11)
H10	1.032992	0.182115	0.804459	0.043*
C11	1.1288 (4)	0.5564 (4)	0.7604 (2)	0.0313 (10)
C12	1.0310 (4)	0.6468 (4)	0.7865 (2)	0.0326 (10)
H12	0.961178	0.672929	0.764049	0.039*
C13	1.0368 (4)	0.6930 (4)	0.8400 (2)	0.0333 (10)
H13	1.102249	0.660014	0.863935	0.040*
C14	0.9513 (4)	0.7905 (4)	0.8655 (2)	0.0304 (10)
C15	0.9658 (4)	0.8380 (4)	0.92081 (19)	0.0326 (10)
C16	0.8944 (4)	0.9384 (4)	0.9400 (2)	0.0357 (11)
H16	0.907633	0.969031	0.977684	0.043*
C17	0.8042 (4)	0.9941 (4)	0.9046 (2)	0.0379 (11)
H17	0.755690	1.063612	0.917485	0.045*
C18	0.7845 (4)	0.9485 (4)	0.8502 (2)	0.0438 (12)
H18	0.721330	0.986000	0.825976	0.053*
C19	0.8561 (4)	0.8492 (4)	0.8313 (2)	0.0355 (11)
H19	0.841250	0.818792	0.793790	0.043*
Cl2	1.07745 (11)	0.77116 (11)	0.96854 (5)	0.0466 (3)
Fe1	0.97948 (6)	0.37285 (5)	0.71595 (3)	0.02744 (16)
O1	1.2249 (3)	0.5230 (3)	0.78557 (14)	0.0403 (8)
C20	0.9865 (4)	1.1423 (4)	0.54650 (19)	0.0285 (10)
C21	1.1182 (4)	1.1056 (4)	0.5347 (2)	0.0370 (11)
H21	1.183095	1.153643	0.502557	0.044*
C22	1.1568 (4)	0.9992 (4)	0.5695 (2)	0.0430 (12)
H22	1.247855	0.973656	0.561463	0.052*
C23	1.0610 (4)	0.9299 (4)	0.6164 (2)	0.0412 (12)
H23	1.086541	0.857123	0.641055	0.049*
C24	0.9295 (4)	0.9668 (4)	0.6270 (2)	0.0348 (10)
H24	0.864572	0.916814	0.657899	0.042*
C25	0.8876 (4)	1.0757 (4)	0.59371 (19)	0.0282 (10)
C26	0.7478 (4)	1.1173 (4)	0.60747 (19)	0.0302 (10)
H26	0.723246	1.182520	0.577036	0.036*
C27	0.6534 (4)	1.0723 (4)	0.65834 (19)	0.0312 (10)
H27	0.675838	1.008159	0.689980	0.037*
C28	0.5135 (4)	1.1179 (4)	0.66806 (19)	0.0277 (9)
C29	0.4128 (4)	1.0457 (3)	0.71899 (19)	0.0266 (9)
C30	0.2730 (4)	1.0696 (4)	0.73013 (19)	0.0302 (10)
H30	0.229766	1.132473	0.705908	0.036*
C31	0.2100 (4)	0.9835 (4)	0.7834 (2)	0.0414 (12)
H31	0.116440	0.978203	0.801212	0.050*
C32	0.4358 (4)	0.9435 (4)	0.76660 (19)	0.0334 (10)
H32	0.519906	0.907585	0.770895	0.040*
C33	0.3085 (4)	0.9064 (4)	0.8061 (2)	0.0449 (12)
H33	0.292546	0.840643	0.841696	0.054*
C34	0.3406 (7)	1.0847 (6)	0.9093 (3)	0.084 (2)
H34	0.330805	1.016347	0.943366	0.100*
C35	0.4615 (6)	1.1296 (8)	0.8686 (4)	0.099 (3)
H35	0.548392	1.097618	0.870448	0.118*
C36	0.4308 (6)	1.2304 (6)	0.8247 (3)	0.079 (2)
H36	0.493395	1.278366	0.791218	0.094*
C37	0.2935 (5)	1.2477 (4)	0.8386 (2)	0.0506 (13)
H37	0.245483	1.309811	0.816460	0.061*
C38	0.2378 (5)	1.1580 (4)	0.8908 (2)	0.0532 (14)
H38	0.145249	1.148599	0.910401	0.064*
Cl3	0.94509 (10)	1.27827 (10)	0.50079 (5)	0.0379 (3)
Fe3	0.34247 (6)	1.08104 (6)	0.81255 (3)	0.03316 (17)
O3	0.4824 (3)	1.2107 (3)	0.63423 (14)	0.0410 (8)
C39	0.5045 (5)	0.8046 (5)	0.5223 (3)	0.0551 (15)
H39	0.564827	0.822707	0.480342	0.066*
C40	0.5044 (5)	0.8554 (4)	0.5770 (3)	0.0540 (14)
H40	0.564738	0.914693	0.579522	0.065*
C41	0.4022 (5)	0.8065 (4)	0.6284 (2)	0.0503 (14)
H41	0.379970	0.826266	0.672050	0.060*
C42	0.3371 (4)	0.7224 (4)	0.6043 (3)	0.0509 (14)
H42	0.263011	0.674663	0.628543	0.061*
C43	0.4027 (5)	0.7225 (5)	0.5376 (3)	0.0522 (14)
H43	0.380916	0.674609	0.508220	0.063*
C44	0.6925 (4)	0.5675 (4)	0.5647 (2)	0.0432 (12)
H44	0.739090	0.568845	0.519796	0.052*
C45	0.5810 (5)	0.4954 (4)	0.5981 (2)	0.0422 (12)
H45	0.539773	0.440223	0.579333	0.051*
C46	0.7221 (4)	0.6369 (4)	0.60951 (19)	0.0351 (11)
H46	0.791959	0.693528	0.600000	0.042*
C47	0.6293 (4)	0.6075 (4)	0.67183 (19)	0.0268 (9)
C48	0.5417 (4)	0.5193 (4)	0.6639 (2)	0.0327 (10)
H48	0.469530	0.483114	0.697084	0.039*
C49	0.6258 (4)	0.6647 (4)	0.73057 (19)	0.0268 (9)
C50	0.5211 (4)	0.6247 (3)	0.79105 (19)	0.0269 (9)
H50	0.448838	0.579188	0.787123	0.032*
C51	0.5247 (4)	0.6498 (3)	0.85000 (19)	0.0299 (10)
H51	0.594528	0.700316	0.851886	0.036*
C52	0.4309 (4)	0.6072 (4)	0.91309 (19)	0.0288 (10)
C53	0.3495 (4)	0.5080 (4)	0.9195 (2)	0.0352 (11)
H53	0.352028	0.470118	0.881845	0.042*
C54	0.2655 (4)	0.4644 (4)	0.9796 (2)	0.0416 (12)
H54	0.210028	0.397868	0.982867	0.050*
C55	0.2622 (4)	0.5173 (4)	1.0349 (2)	0.0426 (12)
H55	0.205722	0.485907	1.076325	0.051*
C56	0.3398 (4)	0.6149 (4)	1.0305 (2)	0.0404 (11)
H56	0.336586	0.651961	1.068528	0.048*
C57	0.4229 (4)	0.6589 (4)	0.97017 (19)	0.0314 (10)
Cl1	0.51792 (13)	0.78416 (11)	0.96709 (6)	0.0520 (3)
Fe2	0.53173 (6)	0.67378 (5)	0.59881 (3)	0.02652 (15)
O2	0.7091 (3)	0.7394 (3)	0.73009 (13)	0.0400 (8)

Source of material

A mixed solvent system comprising acetylferrocene (10 mmol) and 2-(4-chlorophenyl)acetaldehyde (10 mmol) were added to a flask. Then ethanol (25 mL) was added and stirred at room temperature for 20 min until all the solids are dissolved. To this solution 10 mL KOH (20%) was added and continue stirring until all raw materials disappear (monitored by thin layer chromatography). The reaction products were translated into 50 mL water with some solids separated out. The solids were obtained by suction filtration and washed with 30% ethanol aqueous solution. The single crystal of the title compound was obtained within seven days at room temperature by recrystallization.

Experimental details

All hydrogen atoms were placed in theoretical positions and refined as riding atoms. Their U _iso values were set to 1.2U _eq of the parent atoms.

Comment

Ferrocene is known as a widely applicable organometallic framework structure for the development of various functional derivatives that are applicated in drug design, catalysis, material science, agriculture, and electrochemistry [5], [6], [7]. The wide application of ferrocene derivatives is attributable to the unique properties of ferrocene scaffold, such as native excellent air stability, solubility, thermal, and photochemical stability [8, 9]. Substituting the benzene ring of a bioactive molecule by ferrocene group will dramatically change hydrophobicity, lipophilicity, solubility, and stability [10]. Various ferrocene derivatives were designed to exhibit a wide range of biological properties, like anti-cancer [11], anti-oxidant [12], anti-HIV, analgesic, anti-infective [13], anti-viral [14], anti-microbial [15], anti-convulsant effects [5, 16]. Therefore, in this work, one ferrocene derivative, i.e., (E)-3-(2-chlorophenyl)-1-ferrocenylprop-2-en-1-one, was synthesized and crystallized.

As displayed in the figure, the title compound adopts the s-trans configuration in all three crystallographically independent molecules. The bulky substituent is incorporated at C3 position of ferrocene unit, which makes the bond distances of C2–C3 (1.442(7) Å) and C3–C4 (1.431(7) Å) more elongate. Other bond length in the ferrocenyl group ranges from 1.404(7) Å to 1.418(6) Å. Compared with 3-ferrocenylprop-2-enal, the introducing of 2-chlorophenyl leads to bond lengths of C–C and C=C closer, which are closer to the typical single and double bonds [17]. However, similar to 3-ferrocenylprop-2-enal, the crystal structure of the title compound is also stabilized mainly by intermolecular C–H···O interactions [17].

Corresponding author: Lilei Zhang, College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, China, E-mail: zhanglilei@outlook.com

Funding source: Key Scientific Research Projects of Colleges and Universities in Henan Province http://dx.doi.org/10.13039/501100013066

Award Identifier / Grant number: 22A430032

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: This work was financially supported by the Key Scientific Research Projects of Colleges and Universities in Henan Province (22A430032).
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2022-01-22

Accepted: 2022-03-31

Published Online: 2022-04-12

Published in Print: 2022-08-26

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