New ferrocene containing 3-(arylthio)propan-1-ones: Synthesis, spectral characterization and crystal structure of 3-[(4-chlorophenyl)thio]-1- ferrocenylpropan-1-one, 3-[(4-chlorophenyl)thio]-1-ferrocenyl-3-phenylpropan-1- one and 3-[(4-chlorophenyl)thio]-3-ferrocenyl-1-phenylpropan-1-one

Article abstract of DOI:10.1016/j.poly.2013.12.012

Three series of ferrocene containing 3-(arylthio)propan-1-ones (each of eight examples) have been synthesized by thia-Michael addition of the corresponding thiophenols to acryloylferrocene, 1-ferrocenyl-3-phenylprop-2-en- 1-one and 3-ferrocenyl-1-phenylprop-2-en-1-one promoted by the catalyst generated from a sacrificial zirconium anode. All the newly synthesized compounds (16 in total) were characterized by spectral data, whereas single crystal X-ray structure analysis was performed for 3-[(4-chlorophenyl)thio]-1- ferrocenylpropan-1-one (1h), 3-[(4-chlorophenyl)thio]-1-ferrocenyl-3- phenylpropan-1-one (2h) and 3-[(4-chlorophenyl)thio]-3-ferrocenyl-1- phenylpropan-1-one (3h). Molecular geometry and structural characteristics of three thiaketones (1h, 2h and 3h) were analysed and compared in detail. It was found that all three molecules do not form classical H-bonds and π?π interactions (regardless of the presence of 3 or 4 aromatic rings per a molecule). However, all three crystal structures abound in intermolecular C-H?π interactions while 2h and 3h in addition form intramolecular C-H?π as only evident interaction within the molecules.

Full text of DOI:10.1016/j.poly.2013.12.012

Polyhedron xxx (2014) xxx–xxx
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
New ferrocene containing 3-(arylthio)propan-1-ones: Synthesis, spectral
characterization and crystal structure of 3-[(4-chlorophenyl)thio]
-1-ferrocenylpropan-1-one, 3-[(4-chlorophenyl)thio]-1-ferrocenyl
-3-phenylpropan-1-one and 3-[(4-chlorophenyl)thio]-3-ferrocenyl-
1-phenylpropan-1-one
a
b,
a,
⇑
⇑
´
´
´
´
Dragana Stevanovic , Goran A. Bogdanovic , Rastko D. Vukicevic
a Department of Chemistry, Faculty of Science, University of Kragujevac, R. Domanovi´ca 12, 34000 Kragujevac, Serbia
Vinca Institute of Nuclear Sciences, Laboratory of Theoretical Physics and Condensed Matter Physics, University of Belgrade, PO Box 522, 11001 Belgrade, Serbia
b
ˇ
a r t i c l e i n f o
a b s t r a c t
Article history:
Three series of ferrocene containing 3-(arylthio)propan-1-ones (each of eight examples) have been syn-
thesized by thia-Michael addition of the corresponding thiophenols to acryloylferrocene, 1-ferrocenyl-3-
phenylprop-2-en-1-one and 3-ferrocenyl-1-phenylprop-2-en-1-one promoted by the catalyst generated
from a sacrificial zirconium anode. All the newly synthesized compounds (16 in total) were characterized
by spectral data, whereas single crystal X-ray structure analysis was performed for 3-[(4-chloro-
phenyl)thio]-1-ferrocenylpropan-1-one (1h), 3-[(4-chlorophenyl)thio]-1-ferrocenyl-3-phenylpropan-1-
one (2h) and 3-[(4-chlorophenyl)thio]-3-ferrocenyl-1-phenylpropan-1-one (3h). Molecular geometry
and structural characteristics of three thiaketones (1h, 2h and 3h) were analysed and compared in detail.
Received 8 November 2013
Accepted 13 December 2013
Available online xxxx
Dedicated to Professor Vukadin Leovac,
good colleague, dear friend and exceptional
scientist, on the happy occasion of his 70th
birthday.
It was found that all three molecules do not form classical H-bonds and
the presence of 3 or 4 aromatic rings per a molecule). However, all three crystal structures abound in
intermolecular C–Hꢀ ꢀ ꢀ interactions while 2h and 3h in addition form intramolecular C–Hꢀ ꢀ ꢀ as only
evident interaction within the molecules.
p
ꢀ ꢀ ꢀ
p interactions (regardless of
Keywords:
Ferrocene
3-(Arylthio)propan-1-ones
Crystal structure
Zirconium catalyst
Anodic dissolution
p
p
Ó 2013 Elsevier Ltd. All rights reserved.
1. Introduction
reported on the suitable and simple application of anodic dissolu-
tion of a zirconium electrode for the generation of a catalyst pro-
moting successful Ferrier rearrangement, as well as thia- and
aza-Michael reactions (addition of amines and thiols to conjugated
carbonyls, respectively) [19]. In continuation of our permanent
interest in synthetic applications of sacrificial anode [19,20], as
well as in synthesis of sulfur containing ferrocene derivatives
[21–25], in this paper we describe the synthesis and spectral char-
acterisation of three classes of ferrocene containing b-(aryl-
thio)propan-1-ones 1–3 (Fig. 1) utilising electrochemical
generated zirconium catalyst to promote addition of thiophenols
to the corresponding conjugated enones.
The synthesized compounds are surely of interest to the broad
auditorium of synthetics working in ferrocene chemistry, particu-
larly to those occupied with the synthesis of derivatives of this met-
alocene bearing two electron-donating groups (bidentate ligands).
Since b-(arylthio)propan-1-ones already contain a sulfur atom, the
additional electron-donating group can be designed by diverse
transformations of the carbonyl group, utilising the classical
synthetic methods, such as reduction to the corresponding alcohol
and successive substation of the hydroxyl group with nucleophiles,
Several important properties of zirconium compounds caused
their widespread use as catalysts of many synthetic important
reactions [1–3]. First of all, metal zirconium and both classes of zir-
conium compounds, Zr(IV) and ZrO(II), as well as zirconium oxide,
are commercially available and relatively inexpensive chemicals.
Zirconium compounds are relatively insensitive to moisture, easily
handled, of low toxicity and with high catalytic activity in many
reactions, such as Friedel–Crafts acylations [4], Fries rearrange-
ments [5], sodium borohydride reductions [6,7], multicomponent
condensations affording dihydropyrimidinones [8] and b-aryl-b-
mercaptoketones [9], esterifications of long chain aliphatic carbox-
ylic acids and alcohols [10], Pechmann reactions [11], etc. [1–3].
The particular attention synthetics paid to application of zirconium
compounds as catalysts of Michael reaction [12–18]. Recently, we
⇑
Corresponding authors. Tel.: +381 62211579 (G.A. Bogdanovic´), +381 34300268
(R.D. Vukic´evic´).
E-mail addresses: goranb@vin.bg.ac.rs (G.A. Bogdanovic´), vuk@kg.ac.rs
(R.D. Vukic´evic´).
0277-5387/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2013.12.012
Please cite this article in press as: D. Stevanovic´ et al., Polyhedron (2014), http://dx.doi.org/10.1016/j.poly.2013.12.012

´
2
D. Stevanovic et al. / Polyhedron xxx (2014) xxx–xxx
Fig. 1. Synthesized b-(arylthio)propan-1-ones with the assignation of C atoms for 1H NMR and 13C NMR spectra description.
condensations with amines, hydroxylamine(s), hydrazine(s), etc.,
and further transformations of such obtained products.
4.47 (pseudo t, J = 2.0 Hz, 2H, 2 ꢂ CH, Cp), 4.14 (s, 5H, 5 ꢂ CH,
Cp), 3.17 (A2B2, 4H, 2 ꢂ CH2), 2.37 (s, 3H, CH3); 13C NMR
(50 MHz, CDCl3): d = 201.7, 137.4, 135.2, 130.1, 127.4, 126.4,
125.6, 78.4, 72.2, 69.7, 69.1, 38.7, 26.7, 20.2; IR: 3098, 2923, 1666.
2. Experimental
2.2.2. 1-Ferrocenyl-3-[(4-tert-butylphenyl)thio]propan-1-one (1e)
m.p. 96 °C; 1H NMR (200 MHz, CDCl3): d = 7.41–7.03 (m, 4H, Ar),
4.74 (pseudo t, J = 2.2 Hz, 2H, 2 ꢂ CH, Cp), 4.15 (pseudo t, J = 2.0 Hz,
2H, 2 ꢂ CH, Cp), 4.15 (s, 5H, 5 ꢂ CH, Cp), 3.20 (A2B2, 4H, 2 ꢂ CH2);
13C NMR (50 MHz, CDCl3): d = 201.3, 135.5, 133.1, 129.6, 127.8,
127.0, 126.3, 78.2, 72.3, 69.7, 69.0, 38.2, 26.2; IR: 3101, 2926, 1663.
2.1. Materials and instruments
All chemicals were commercially available and used as re-
ceived, except that the solvents were purified by distillation. The
starting enones were prepared as described elsewhere in the liter-
ature [26,27]. Electrolyses were carried out in an udivided cell
using an Autolab potentiostat and a Uniwatt, Beha Labor-Netzgerät
(NG 394). A glass vessel provided with a spiral Zr-anode (/
= 15 mm, made from a / = 2 mm wire) and a spiral Pt-cathode
(/ = 8 mm, made from a / = 1 mm wire) was used as the electro-
lytic cell. A cylindrical platinum foil (2.5 cm diameter) and a plat-
inum spiral (1 cm diameter) were used as the working and the
counter electrode, respectively. Ultrasonic cleaner Elmasonic S
10, 30 W was used for the ultrasonically supported electrolysis.
Chromatographic separations were carried out using silica gel 60
(Merck, 230–400 mesh ASTM), whereas silica gel 60 on Al plates,
layer thickness 0.2 mm (Merck) was used for TLC. Melting points
(uncorrected) were determined on a Mel-Temp capillary melting
points apparatus, model 1001. The 1H and 13C NMR spectra of the
samples in CDCl3 were recorded on a Varian Gemini (200 MHz)
spectrometer. Chemical shifts are expressed in d (ppm), relative to
the residual solvent protons or 13CDCl3 as internal standards (CHCl3:
7.26 ppm for 1H and 77 ppm for 13C). IR measurements were carried
out with a Perkin-Elmer FTIR 31725-X spectrophotometer.
2.2.3. 3-[(2-Chlorophenyl)thio]-1-ferrocenylpropan-1-one (1f)
m.p. 96 °C; 1H NMR (200 MHz, CDCl3): d = 7.41–7.03 (m, 4H, Ar),
4.74 (pseudo t, J = 2.2 Hz, 2H, 2 ꢂ CH, Cp), 4.15 (pseudo t, J = 2.0 Hz,
2H, 2 ꢂ CH, Cp), 4.15 (s, 5H, 5 ꢂ CH, Cp), 3.20 (A2B2, 4H, 2 ꢂ CH2);
13C NMR (50 MHz, CDCl3): d = 201.3, 135.5, 133.1, 129.6, 127.8,
127.0, 126.3, 78.2, 72.3, 69.7, 69.0, 38.2, 26.2; IR: 3101, 2926, 1663.
2.2.4. 1-Ferrocenyl-3-phenyl-3-(o-tolylthio)propan-1-one (2b)
m.p. 91 °C; 1H NMR (200 MHz, CDCl3): d = 7.53–7.04 (m, 9H, Ar),
4.95 (dd, J = 8.8, 5.2 Hz, 1H, CH), 4.74–4.68 (m, 2H, 2 ꢂ CH, Cp),
4.46–4.43 (m, 2H, 2 ꢂ CH, Cp), 3.96 (s, 5H, 5 ꢂ CH, Cp), 3.42 (dd,
J = 17.3, 8.8 Hz, 1H, CHaHb), 3.25 (dd, J = 17.3, 5.2 Hz, 1H, CHaHb),
2.37 (s, 3H, CH3); 13C NMR (50 MHz, CDCl3): d = 200.5, 141.6, 139.8,
133.9, 132.3, 130.2, 128.4, 127.9, 127.4, 127.2, 126.3, 78.6, 72.3,
72.2, 69.7, 69.2, 69.0, 46.9, 46.1, 20.6; IR: 3112, 2923, 2852, 1659.
2.2.5. 1-Ferrocenyl-3-phenyl-3-(m-tolylthio)propan-1-one (2c)
m.p. 72 °C; 1H NMR (200 MHz, CDCl3): d = 7.45–6.97 (m, 9H, Ar),
4.99 (dd, J = 9.0, 5.0 Hz, 1H, CH), 4.69 (brd, J = 6.4 Hz, 2H, 2 ꢂ CH,
Cp), 4.44 (pseudo t, J = 1.8 Hz, 2H, 2 ꢂ CH, Cp), 3.94 (s, 5H,
5 ꢂ CH, Cp), 3.40 (dd, J = 17.3, 9.0 Hz, 1H, CHaHb), 3.22 (dd,
J = 17.3, 5.0 Hz, 1H, CHaHb), 2.26 (s, 3H, CH3); 13C NMR (50 MHz,
CDCl3): d = 200.6, 141.6, 138.5, 134.4, 132.7, 129.0, 128.6, 128.4,
128.1, 128.0, 127.4, 78.7, 72.3, 72.2, 69.6, 69.2, 69.0, 47.5, 46.2,
21.2; IR: 3114, 2922, 2852, 1658.
2.2. Synthetic procedure
The electrolytic cell was filled with 10 mL of an acetonitrile
solution of LiClO4 (0.1 M), 1 mmol of enone 4–6 and 2 mmol of
the corresponding nuclephile 7a–h. The cell was placed in the
ultrasound bath (at a frequency of 37 kHz, with an effective ultra-
sonic power of 30 W and a peak of 240 W) and the constant current
electrolysis (20 mA) was run 32 min (0.4 F molꢁ1) at room temper-
ature. After the electrolysis was finished, the reaction mixture was
left 30 min in the same bath and the solvent evaporated. The resi-
due was diluted with 20 mL of water, the obtained mixture ex-
tracted with three 20 mL portions of ethyl acetate and collected
organic layers dried overnight (anhydrous sodium sulfate). After
evaporation of the solvent the crude reaction product was purified
by column chromatography to give the products of the reaction.
The spectral data of known compounds were in complete agree-
ment with those published elsewhere (1a [28], 1c [29], 1d [29],
1g [29], 1h [29], 2a [30], 2h [30], and 3a [30]), whereas the data
confirming structures of newly synthesized ones follow.
2.2.6. 1-Ferrocenyl-3-phenyl-3-(p-tolylthio)propan-1-one (2d)
m.p. 80 °C; 1H NMR (200 MHz, CDCl3): d = 7.44–7.39 (m, 2H, Ar),
7.33–7.13 (m, 5H, Ar), 7.06–7.02 (m, 2H, Ar), 4.92 (dd, J = 9.0,
5.1 Hz, 1H, CH), 4.73–4.65 (m, 2H, 2 ꢂ CH, Cp), 4.44 (pseudo t,
J = 1.8 Hz, 2H, 2 ꢂ CH, Cp), 3.94 (s, 5H, 5 ꢂ CH, Cp), 3.39 (dd,
J = 17.2, 9.0 Hz, 1H, CHaHb), 3.20 (dd, J = 17.2, 5.1 Hz, 1H, CHaHb),
2.27 (s, 3H, CH3); 13C NMR (50 MHz, CDCl3): d = 200.6, 141.7,
137.5, 132.8, 130.9, 129.6, 128.4, 128.0, 127.4, 78.7, 72.3, 72.2,
69.6, 69.2, 69.0, 48.1, 46.1, 21.0; IR: 3110, 2921, 1660.
2.2.7. 3-[(4-tert-Butylphenyl)thio]-1-ferrocenyl-3-phenylpropan-1-
one (2e)
m.p. 143 °C; 1H NMR (200 MHz, CDCl3): d = 7.47–7.41 (m, 2H,
Ar), 7.37–7.19 (m, 7H, Ar), 4.95 (dd, J = 9.2, 4.9 Hz, 1H, CH), 4.73–
4.64 (m, 2H, 2 ꢂ CH, Cp), 4.44 (pseudo t, J = 1.9 Hz, 2H, 2 ꢂ CH,
Cp), 3.92 (s, 5H, 5 ꢂ CH, Cp), 3.40 (dd, J = 17.3, 9.2 Hz, 1H, CHaHb),
2.2.1. 1-Ferrocenyl-3-(o-tolylthio)propan-1-one (1b)
m.p. 62 °C; 1H NMR (200 MHz, CDCl3): d = 7.35–7.29 (m, 1H, Ar),
7.24–7.03 (m, 3H, Ar), 4.73 (pseudo t, J = 2.0 Hz, 2H, 2 ꢂ CH, Cp),
Please cite this article in press as: D. Stevanovic´ et al., Polyhedron (2014), http://dx.doi.org/10.1016/j.poly.2013.12.012

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D. Stevanovic et al. / Polyhedron xxx (2014) xxx–xxx
3.22 (dd, J = 17.3, 4.9 Hz, 1H, CHaHb), 1.26 (s, 9H, 3 ꢂ CH3); 13C NMR
2.2.14. 3-[(2-Chlorophenyl)thio]-3-ferrocenyl-1-phenylpropan-1-one
(3f)
(50 MHz, CDCl3): d = 200.7, 150.6, 141.6, 132.2, 131.2, 128.5, 128.0,
127.4, 125.9, 78.7, 72.3, 72.2, 69.7, 69.2, 69.1, 47.9, 46.3, 34.5, 31.2;
IR: 3111, 2955, 1657.
m.p. 94 °C; 1H NMR (200 MHz, CDCl3): d = 7.95–7.87 (m, 2H, Ar),
7.60–7.30 (m, 5H, Ar), 7.17–7.08 (m, 2H, Ar), 4.99 (dd, J = 6.5,
6.2 Hz, 1H, CH), 4.23–4.06 (m, 9H, 9 ꢂ CH, Cp), 3.69 (dd, J = 17.2,
6.5 Hz, 1H, CHaHb), 3.51 (dd, J = 17.2, 6.2 Hz, 1H, CHaHb); 13C
NMR (50 MHz, CDCl3): d = 197.3, 136.7, 136.6, 134.0, 133.6,
133.2, 129.8, 128.6, 128.2, 128.0, 127.0, 89.1, 68.8, 67.9, 67.8,
67.6, 67.3, 45.2, 42.6; IR: 3087, 3059, 2898, 1682.
2.2.8. 3-[(2-Chlorophenyl)thio]-1-ferrocenyl-3-phenylpropan-1-one
(2f)
m.p. 133 °C; 1H NMR (200 MHz, CDCl3): d = 7.57–7.45 (m, 2H,
Ar), 7.40–7.03 (m, 7H, Ar), 5.15 (dd, J = 9.3, 4.6 Hz, 1H, CH), 4.73–
4.68 (m, 2H, 2 ꢂ CH, Cp), 4.46 (pseudo t, J = 1.8 Hz, 2H, 2 ꢂ CH,
Cp), 3.94 (s, 5H, 5 ꢂ CH, Cp), 3.47 (dd, J = 17.3, 9.3 Hz, 1H, CHaHb),
3.24 (dd, J = 17.3, 4.6 Hz, 1H, CHaHb); 13C NMR (50 MHz, CDCl3):
d = 200.2, 140.8, 135.2, 134.3, 131.6, 129.7, 128.6, 128.0, 127.7,
127.6, 127.1, 78.5, 72.4, 72.3, 69.7, 69.2, 69.0, 46.2, 46.0; IR:
3119, 2923, 1659.
2.2.15. 3-[(3-Chlorophenyl)thio]-3-ferrocenyl-1-phenylpropan-1-one
(3g)
Viscous oil; 1H NMR (200 MHz, CDCl3): d = 7.98–7.88 (m, 2H,
Ar), 7.61–7.04 (m, 7H, Ar), 4.85 (dd, J = 7.2, 5.8 Hz, 1H, CH), 4.18–
4.02 (m, 9H, 9 ꢂ CH, Cp), 3.61 (dd, J = 17.1, 5.8 Hz, 1H, CHaHb),
3.21 (dd, J = 17.1, 7.2 Hz, 1H, CHaHb); 13C NMR (50 MHz, CDCl3):
d = 197.1, 136.7, 136.2, 134.0, 133.1, 132.6, 130.9, 129.6, 128.5,
127.9, 127.4, 89.4, 68.7, 67.9, 67.7, 67.6, 66.7, 44.2, 43.9; IR:
3087, 3059, 2896, 1682.
2.2.9. 3-[(3-Chlorophenyl)thio]-1-ferrocenyl-3-phenylpropan-1-one
(2g)
m.p. 108 °C; 1H NMR (200 MHz, CDCl3): d = 7.46–7.43 (m, 2H,
Ar), 7.34–7.14 (m, 7H, Ar), 5.03 (dd, J = 8.6, 5.4 Hz, 1H, CH), 4.74–
4.71 (m, 2H, 2 ꢂ CH, Cp), 4.48 (pseudo t, J = 1.8 Hz, 2H, 2 ꢂ CH,
Cp), 3.98 (s, 5H, 5 ꢂ CH, Cp), 3.41 (dd, J = 17.2, 8.6 Hz, 1H, CHaHb),
3.26 (dd, J = 17.2, 5.4 Hz, 1H, CHaHb); 13C NMR (50 MHz, CDCl3):
d = 200.2, 141.1, 136.8, 134.4, 131.4, 129.8, 129.6, 128.6, 128.0,
127.6, 127.2, 78.5, 72.4, 72.3, 69.7, 69.2, 69.0, 47.5, 46.1; IR:
3115, 2923, 1656.
2.2.16. 3-[(4-chlorophenyl)thio]-3-ferrocenyl-1-phenylpropan-1-one
(3h)
m.p. 137 °C; 1H NMR (200 MHz, CDCl3): d = 8.00–7.89 (m, 2H,
Ar), 7.64–7.41 (m, 3H, Ar), 7.26–7.13 (m, 4H, Ar), 4.79 (dd, J = 7.3,
5.7 Hz, 1H, CH), 4.13–4.09 (m, 7H, 7 ꢂ CH, Cp), 4.07–4.02 (m, 2H,
2 ꢂ CH, Cp), 3.60 (dd, J = 17.3, 5.7 Hz, 1H, CHaHb), 3.51 (dd,
J = 17.3, 7.3 Hz, 1H, CHaHb); 13C NMR (50 MHz, CDCl3): d = 197.3,
136.8, 135.0, 133.8, 133.2, 132.5, 128.8, 128.6, 128.0, 89.7, 68.8,
68.0, 67.9, 67.8, 66.7, 44.2, 44.1; IR: 3152, 2924, 2852, 1668.
2.2.10. 3-Ferrocenyl-1-phenyl-3-(o-tolylthio)propan-1-one (3b)
m.p. 83 °C; 1H NMR (200 MHz, CDCl3): d = 8.02–7.79 (m, 2H, Ar),
7.61–7.32 (m, 4H, Ar), 7.22–6.99 (m, 3H, Ar), 4.77 (dd, J = 6.9,
5.8 Hz, 1H, CH), 4.20–3.98 (m, 8H, 8 ꢂ CH, Cp), 3.96–3.88 (m, 1H,
1 ꢂ CH, Cp), 3.61 (dd, J = 17.1, 5.8 Hz, 1H, CHaHb), 3.51 (dd,
J = 17.1, 6.9 Hz, 1H, CHaHb), 2.29 (s, 3H, CH3); 13C NMR (50 MHz,
CDCl3): d = 197.4, 141.0, 136.9, 134.1, 133.7, 133.1, 130.2, 128.5,
128.0, 127.7, 126.2, 90.0, 68.7, 67.8, 67.7, 67.6, 66.6, 44.6, 43.4,
20.8; IR: 3087, 3058, 2919, 2898, 1682.
2.3. X-ray data collection and structure refinement for compounds 1h,
2h and 3h
Crystal data and experimental details for all three compounds
are summarized in Table 1. Single-crystal diffraction data were col-
lected at room temperature on an Agilent Gemini S diffractometer.
Data collection for 2 and 3 h was performed using Mo K
(0.71073 Å) radiation while the diffraction data for 1h were col-
lected using Cu K radiation (k = 1.5418 Å). Data integration and
a
2.2.11. 3-Ferrocenyl-1-phenyl-3-(m-tolylthio)propan-1-one (3c)
m.p. 93 °C; 1H NMR (200 MHz, CDCl3): d = 7.96–7.88 (m, 2H, Ar),
7.62–7.38 (m, 3H, Ar), 7.22–6.97 (m, 4H, Ar), 4.82 (pseudo t,
J = 6.5 Hz, 1H, CH), 4.18–4.06 (m, 9H, 9 ꢂ CH, Cp), 3.54 (pseudo d,
J = 6.5 Hz, 2H, CH2), 2.24 (s, 3H, CH3); 13C NMR (50 MHz, CDCl3):
d = 197.6, 138.4, 136.9, 134.1, 133.8, 133.1, 130.3, 128.6, 128.5,
128.3, 128.1, 90.0, 68.7, 67.8, 67.7, 67.6, 66.9, 44.5. 43.8, 21.1; IR:
3086, 3056, 2920, 2895, 1682.
a
scaling of the reflections were performed with the CRYSALIS software
[31]. Numerical absorption correction based on Gaussian integra-
tion over a multifaceted crystal model was performed. The crystal
structures of 1h, 2h and 3h were solved by direct methods, using
SIR2002 [32] and refined using SHELXL97 [33] program both incorpo-
rated in WINGX [34] program package.
All non-H atoms were refined anisotropically to convergence.
All H atoms were placed at geometrically calculated positions with
the C–H distances fixed to 0.93 from Csp2 and 0.97 and 0.98 Å from
methylene and methine Csp3, respectively. The corresponding iso-
tropic displacement parameters of the hydrogen atoms were equal
to 1.2 Ueq and 1.5 Ueq of the parent Csp2 and Csp3, respectively. Fig-
ures were produced using ORTEP-3 [35] and MERCURY, Version 2.4 [36].
The software used for the preparation of the materials for publica-
tion: WINGX [34], PLATON [37], PARST [38].
2.2.12. 3-Ferrocenyl-1-phenyl-3-(p-tolylthio)propan-1-one (3d)
m.p. 139 °C; 1H NMR (200 MHz, CDCl3): d = 7.97–7.88 (m, 2H,
Ar), 7.60–7.38 (m, 3H, Ar), 7.27–7.16 (m, 2H, Ar), 7.04–7.00 (m,
2H, Ar), 4.76 (pseudo t, J = 6.5 Hz, 1H, CH), 4.17–4.02 (m, 9H,
9 ꢂ CH, Cp), 3.53 (pseudo d, J = 6.5 Hz, 2H, CH2), 2.28 (s, 3H,
CH3); 13C NMR (50 MHz, CDCl3): d = 197.6, 137.6, 136.9, 134.0,
133.1, 130.3, 129.4, 128.5, 128.1, 90.0, 68.7, 67.8, 67.7, 67.5, 66.8,
44.3, 44.2, 21.1; IR: 3089, 2917, 2855, 1673.
3. Results and discussion
2.2.13. 3-[(4-tert-Butylphenyl)thio]-3-ferrocenyl-1-phenylpropan-1-
one (3e)
3.1. Synthesis
m.p. 118 °C; 1H NMR (200 MHz, CDCl3): d = 7.94–7.85 (m, 2H,
Ar), 7.56–7.15 (m, 7H, Ar), 4.81 (pseudo t, J = 6.5 Hz, 1H, CH),
4.17–4.03 (m, 9H, 9 ꢂ CH, Cp), 3.55 (pseudo d, J = 6.5 Hz, 2H,
CH2), 1.26 (s, 3H, 3 ꢂ CH3); 13C NMR (50 MHz, CDCl3): d = 197.5,
150.6, 136.9, 133.2, 133.0, 130.6, 128.4, 128.0, 125.6, 89.9, 68.7,
67.7, 67.6, 67.5, 66.9, 44.6, 43.9, 34.4, 31.1; IR: 3081, 2965, 2884,
1683.
Three series of ferrocene containing 3-(arylthio)propan-1-ones
were synthesized by thia-Michael addition of eight thiophenols
(7a–h) to the conjugated enones acryloylferrocene (4), 1-ferrocenyl-
3-phenylprop-2-en-1-one (5) and 3-ferrocenyl-1-phenylprop-2-en-
1-one (6) in the presence electrochemically generation zirconium
catalyst (Scheme 1).
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4
Table 1
Crystallographic data for the crystal structures of 1h, 2h and 3h.
1h
19H17ClFeOS
2h
3h
Empirical formula
Formula weight
Color, crystal shape
Crystal size (mm3)
T (K)
C
C25H21ClFeOS
460.78
orange, prism
0.36 ꢂ 0.19 ꢂ 0.03
293(2)
C25H21ClFeOS
460.78
orange, prism
0.50 ꢂ 0.36 ꢂ 0.31
293(2)
384.69
orange, prism
0.27 ꢂ 0.18 ꢂ 0.06
293(2)
Wavelength (Å)
Crystal system
Space group
Unit cell dimensions
a (Å)
1.5418
triclinic
0.71073
monoclinic
P21/n
0.71073
monoclinic
P21/n
ꢀ
P1
7.3519(5)
10.7781(10)
11.9790(8)
101.690(7)
104.013(6)
107.115(7)
840.91(11)
2
13.9615(5)
5.7503(2)
26.3696(12)
90
96.526(4)
90
2103.31(14)
4
1.455
5.92510(10)
12.0161(2)
28.9044(5)
90
91.7450(10)
90
2056.94(6)
4
1.488
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalc (Mg/m3)
1.519
9.807
l
(mmꢁ1
)
0.957
0.979
h Range for data collection (°)
Reflections collected
3.98 to 72.42
5180
3.16 to 28.95
16259
3.29 to 29.04
28507
Independent reflections, Rint
Data/restraints/parameters
Goodness-of-fit (GOF) on F2
3222, 0.0279
3222/0/209
1.019
4984, 0.0289
4984/0/262
1.034
5071, 0.0213
5071/0/262
1.029
Final R1/wR2 indices (I > 2rI
)
0.0355/0.0881
0.0442/0.0924
0.414/ꢁ0.244
0.0401/0.0793
0.0628/0.0877
0.250/ꢁ0.216
0.0268/0.0660
0.0326/0.0689
0.250/ꢁ0.270
Final R1/wR2 indices (all data)
Largest diff. peak and hole (e Åꢁ3
)
The reaction was performed by simple constant current elec-
trolysis (20 mA) of an acetonitrile solution of lithium perchlorate
containing substrates – the corresponding enones and thiophenols
(in a ratio 1:2), using a zirconium and platinum spirals as the an-
ode and cathode, respectively [20]. Since zirconium is the most
oxidizable component of the system, after establishing of an elec-
trical circuit the oxidative dissolution of the Zr-anode took place
and the formation of insoluble species was observed. Most proba-
bly these are the acting catalyst of the addition of thiophenols to
The addition of thiophenols 7a–h to 1-ferrocenyl-3-phenyl-
prop-2-en-1-one (5) proceeded in a similar manner (see Table 3).
The only remarkable discrepancy was occurred in the case of
o-thiocresol (7b), which gave the corresponding saturated ketone
2b in lower yield (50%).
However, the addition of thiophenols 7a–h to 3-ferrocenyl-1-
phenylprop-2-en-1-one (6) was considerably different regarding
the yields of the saturated ketones 3a–h (see Table 4). Although
the addition of three chlorothiophenols (7f–h) was as successful
as in the case of enones 4 and 5, yields obtained by reacting 6 with
thiophenol (7a) and three thiocresols (7b–d) were remarkable
lower (38–58%). It is not easy to rationale this phenomenon. Steric
effects should be rejected, since thiophenol 7e (containing a
voluminous tert-buthyl group) gave under the same conditions
the corresponding product 3e in the considerable higher yield
(91%) than p-thiocresol (58%).
the
p-electronic system of the conjugated enones. The isolation
and characterization of the catalyst is in progress and the results
will be reported elsewhere. Reactions were performed in a 1 mmol
scale and the electrolyses were carried out with 0.4 F/mol charge
consumption in order to generate 0.1 mmol of zirconium(IV) spe-
cies into the solution (since zirconium exchanges four electrons
with the anode), i.e. to provide 10 mol% of some Zr(IV) or ZrO(II)
species. In order to avoid coating of the insoluble catalyst at the an-
ode, the electrolysis was performed placing the electrolytic cell
into an ultrasound bath, providing, thus, an instantaneous removal
of the coated species from the electrode surface.
3.2. Spectral characterisation
Acryloylferrocene (4) was the first substrate we submitted to
the described reaction conditions and results obtained are summa-
rised in Table 2. As data listed therein show, the desired 3-(aryl-
thio)-1-ferrocenylpropan-1-ones (1a–h) were obtained in high
yields (76–91%).
All synthesized ferrocene-containing b-(arylthio)propanones
were characterized by IR, 1H and 13C NMR spectral data. In IR spec-
tra of the synthesized compounds the most recognizable band
appears in the carbonyl group region 1660–1666, 1656–1663 and
1668–1683 cmꢁ1 (for 1a–h, 2a–h and 3a–h, respectively).
Scheme 1. Synthesis ferrocene containing 3-(arylthio)propan-1-ones.
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D. Stevanovic et al. / Polyhedron xxx (2014) xxx–xxx
Table 2
Synthesis of 3-(arylthio)-1-ferrocenylpropan-1-ones 1a–h.
Entry
1
Thiophenol 7
Product 1
Yielda (%)
82
7a
1a
1b
7b
78
2
1c
7c
84
90
3
4
7d
1d
5
7e
1e
86
6
7
7f
1f
76
91
7g
1g
8
7h
1h
78
a
Isolated yields based on the starting enone 4.
Three sets of signals could be recognized in 1H NMR spectra of
(C600–1000, Fig. 1) appear as singlets at 3.92–4.17, as it could be
expected for acylferrocenes. However, chemical shifts, and partic-
ularly the shape of signals, of substituted ring’s protons are differ-
ent from each other. Signals of both kinds of the substituted ring’s
protons of compounds 1a–h (at C300/C400 and C200/C500, respectively,
Fig. 1) appear as pseudo-triplets, at 4.44–4.50 and 4.70–4.75 ppm.
The substituted ring’s protons of compound 2a–h have chemical
shifts very similar to those of 1a–h, but protons of C20/C50 (Fig. 1)
have the signals in the shape of multiplets. The signals of both
kinds of protons of compounds 3a–h (C300/C400 and C200/C500,
Fig. 1) represent complex multiplets at 3.91–4.23 ppm.
Signals of the aromatic ring’s protons are located in expected
region of 1H NMR spectra, and the only fact worth of comment is
the shape of the signal of these protons in 1e. Namely, only one
singlet for aromatic protons of this compound appears in the
corresponding region, apparently due to these protons are acciden-
tally isochronous.
each of three series of b-(arylthio)propanones: the first belonging
to protons of aliphatic parts of these molecules, the second to pro-
tons of ferrocene units and the third one to aromatic protons. The
chemical shifts and shapes of signals corresponding to the given pro-
tons in spectra of three series are, however, different. Thus, signals of
all four methylene protons of compounds 1a–h (–COCH2– and –
CH2S–) appear at similar chemical shifts (at 2.98–3.07 and 3.25–
3.32 ppm) as broad triplets (1a and 1e) or A2B2 multiplets (1b–d
and 1f–h). Signals of –COCH2– protons of compounds 2a–h and
3a–h are of the similar chemical shift as those of 1a–h, whereas their
shapes are different. Due to germinal couplings, these protons exhi-
bit doublets of doublets (2a–h, 3a,b,f–h) and pseudo-doublets (3c–
e) in their spectra. Protons from methine groups in these compounds
(–CHPh–S– and –CHFc–S–, where Fc = ferrocenyl) differ dramati-
cally. Their signals appear as doublets of doublets (2a–h, 3a,b,f–h)
and pseudo-triplets (3c–e) at 4.76–5.15 ppm. However, the methine
protons next to phenyl groups in the series 2a–h had values of their
chemical shifts shifted downfield by a relatively constant value of
0.14–0.18 ppm when compared to the corresponding protons in
compounds 3a–h. This could be interpreted as the result of the dif-
fering diamagnetic ring currents of the phenyl and ferrocenyl
groups. Such a trend is in general agreement with the difference in
chemical shifts of the methyl groups in toluene and methylferrocene
(ca. 0.3 ppm in CDCl3).
Signals belonging to the corresponding carbon atoms of the
synthesized compounds appear in the expected regions of their
13C NMR spectra.
3.3. Crystal structure discussion of 1h, 2h and 3h
Three compounds are characterized by single-crystal X-ray
structure analysis. Two of them, 2h and 3h, crystallize in the same
P21/n space group while 1h crystallizes in triclinic crystal system
Signals of the unsubstituted ring’s protons from the ferrocene
unit of compounds 1a–h, 2a–h (C60–100, Fig. 1) and 3a–h
ꢀ
(P1). All three molecules contain as a common structural part the
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D. Stevanovic et al. / Polyhedron xxx (2014) xxx–xxx
6
Table 3
Synthesis of 3-(arylthio)-1-ferrocenyl-3-phenylpropan-1-ones 2a–h.
Entry
1
Thiophenol 7
Product 2
Yielda (%)
86
7a
7b
2a
2b
2
50
2c
72
80
3
4
7c
7d
2d
5
6
7e
7f
2e
2f
88
93
7
8
7g
7h
2g
2h
98
97
a
Isolated yields based on the starting enone 5.
O1–C11–C12–C13–S1 aliphatic fragment and the C14–C19 phenyl
ring with Cl1 chlorine atom substituted in para position. In Fig. 2
the molecules of 1h, 2h and 3h are placed approximately in the
same projection regarding the above common fragment (the posi-
tion of O1–C11–C12 is used as a primary criterion for the orienta-
tion of molecules).
The O1–C11–C12–C13–S1 chain adopts different conformation
in crystal structure of 1h, 2h and 3h. Thus in 1h all non-hydrogen
atoms in this aliphatic fragment are practically coplanar (root-
mean-square deviation from a mean plane of fitted atoms is only
0.044 Å). For 2h and 3h rms deviation is 0.128 and 0.299 Å respec-
tively. However the difference in the conformation of the O1–C11–
C12–C13–S1 fragment could be illustrated in the best way by com-
parison of the O1–C11–C12–C13 torsion angle [3.4(4), 22.5(3) and
37.8(2)° in 1h, 2h and 3h respectively]. The C11–C12–C13–S1 tor-
sion angle also displays the largest deviation from coplanar posi-
tion for 3h structure [172.9(2), ꢁ171.8(2) and ꢁ146.1(1)° in 1h,
2h and 3h respectively]. Obviously the O1–C11–C12–C13–S1 chain
is the most puckered in the crystal structure of 3h. Bond lengths in
the chain are very similar (Table 5) with an exception for the value
of C13–S1 bond which is for about 0.04 Å shorter in 1h than in 2h
and 3h. Of course an explanation for this structural difference
could be found in the fact that the C13 bind different number of
hydrogen atoms in 1h versus 2h and 3h. Another structural differ-
ence can be found for the C13–S1–C14 angle which is for about 4°
smaller in 2h than in 1h and 3h (Table 5). The S1–C14–C15 and
S1–C14–C15 bond angles are very similar in 2h but significantly
different in 1h and 3h (Table 5). Geometrical parameters within
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D. Stevanovic et al. / Polyhedron xxx (2014) xxx–xxx
Table 4
Synthesis of 3-(arylthio)-3-ferrocenyl-1-phenylpropan-1-ones 3a–h.
Entry
1
Thiophenol 6
Product 3
Yielda (%)
50
7a
3a
2
7b
3b
38
3
4
7c
3c
45
58
7d
3d
5
7e
3e
91
6
7f
3f
79
7g
7h
3g
3h
97
98
7
8
a
Isolated yields based on the starting enone 6.
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´
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D. Stevanovic et al. / Polyhedron xxx (2014) xxx–xxx
Table 5
Selected bond lengths (Å) and bond angles (°) in crystal structures of 1h, 2h and 3h.
1h
2h
3h
Cl1ꢁC17
S1ꢁC14
1.743(3)
1.766(3)
1.801(2)
1.214(3)
1.513(3)
1.515(4)
1.384(3)
1.392(4)
1.380(4)
1.375(4)
1.369(4)
1.381(4)
1.737(2)
1.770(2)
1.842(2)
1.214(2)
1.518(3)
1.523(3)
1.387(3)
1.382(3)
1.377(3)
1.376(3)
1.372(4)
1.378(3)
1.7467(15)
1.7668(15)
1.8369(13)
1.2152(18)
1.515(2)
1.5336(19)
1.396(2)
1.387(2)
1.377(2)
1.375(2)
1.374(2)
1.385(2)
S1ꢁC13
O1ꢁC11
C11ꢁC12
C12ꢁC13
C14ꢁC15
C14ꢁC19
C15ꢁC16
C16ꢁC17
C17ꢁC18
C18ꢁC19
C14ꢁS1ꢁC13
O1ꢁC11ꢁC1
O1ꢁC11ꢁC12
C15ꢁC14ꢁS1
C19ꢁC14ꢁS1
C18ꢁC17ꢁCl1
C16ꢁC17ꢁCl1
104.2(1)
121.9(2)
122.0(2)
124.9(2)
116.3(2)
118.9(2)
120.2(2)
100.76(9)
121.76(18)
121.62(18)
121.69(17)
119.77(18)
119.45(19)
119.6(2)
104.75(7)
120.09(13)
119.96(13)
116.41(11)
125.10(11)
119.41(13)
119.62(12)
slightly longer than for corresponding C1–C11 bond in 1h
[1.471(4) Å] and 2h [1.465(3) Å].
There is no any classical H-bond in all three crystal structures.
Reason could be found in the fact that the molecules of 1h, 2h
and 3h do not possess any significant H-bond donor as O–H, N–H
or similar donor group. The C11–O1 carbonyl group may be ac-
cepted as the best H-bond acceptor in all three compounds but
in 1h the O1 atom does not form any C–Hꢀ ꢀ ꢀO weak hydrogen bond
with Hꢀ ꢀ ꢀO distance shorter than 2.60 Å. However, there are three
C–Hꢀ ꢀ ꢀO1 interactions in 1h with Hꢀ ꢀ ꢀO distances between 2.63
and 2.70 Å and the C–Hꢀ ꢀ ꢀO1 angles larger than 150° (Table 6).
Although weak, these intermolecular C–Hꢀ ꢀ ꢀO interactions proba-
bly stabilize the crystal packing of 1h. Using the C25–Hꢀ ꢀ ꢀO1 weak
H-bond (Table 6) the molecules in crystal structure of 2h form a
chain along the b unit cell axis (for illustration see Supplementary
material file, Fig. S1) while the molecules of 3h form a chain along
the a axis (Fig. S2) but using the C2–Hꢀ ꢀ ꢀO1 hydrogen bond
(Table 6).
The Cl1 atom in all there crystal structures does not form any C–
Hꢀ ꢀ ꢀCl interaction with Hꢀ ꢀ ꢀCl distance shorter than 2.90 Å. In 1h
and 2h there are two intermolecular contacts with Hꢀ ꢀ ꢀCl distances
of 2.95 and 2.94 Å but could not be taken as important since that
corresponding bond angles [C5–H5ꢀ ꢀ ꢀCl1i and C23–H23ꢀ ꢀ ꢀCl1ii for
1h and 2h respectively; symmetry codes: (i) x ꢁ 1,y,z ꢁ 1, (ii)
x + 1,y,z] are rather small (105° and 128°). It is known from the
charge density studies [39,40] that sulfur atom is able to act as a
good acceptor of C–H groups even at the Hꢀ ꢀ ꢀS distance of 3.10 Å.
In 1h and 3h there are two C–Hꢀ ꢀ ꢀS intermolecular interactions,
the C16–Hꢀ ꢀ ꢀS1 and C10–Hꢀ ꢀ ꢀS1 in 1h and 3h respectively
(Table 6).
Fig. 2. Crystal structure and atom-numbering scheme of compounds 1h (a), 2h (b)
and 3h (c). Displacement ellipsoids are drawn at the 40% probability level. H atoms
have been omitted for clarity.
the C14–C19 phenyl ring as well as the Cl1–C17 and S1–C14 bond
lengths are very similar for all three crystal structures.
The structures of 1h, 2h and 3h comprise a ferrocenyl group
substituted on one cyclopentadiene (Cp) ring. In 1h and 2h the
Cp rings adopt nearly eclipsed geometry. The C1–Cg1–Cg2–C10
torsion angle is ꢁ6.19° and 6.09° in 1h and 2h respectively (Cg1
and Cg2 are centroids of the corresponding Cp rings). In 3h the
Cp rings are somewhat less eclipsed with the C1–Cg1–Cg2–C10
torsion angle of ꢁ17.19°. As expected, in all three structures the
Cp rings are almost ideally parallel with a dihedral angle of
0.73(16)°, 1.17(10)° and 3.30(9)° for 1h, 2h and 3h respectively.
Also a distance of the Fe1 atom from a mean plane of the substi-
tuted Cp ring is somewhat shorter than a distance to the unsubsti-
tuted ring (1.645/1.652, 1.649/1.655 and 1.648/1.656 Å for 1h, 2h
and 3h respectively). In 1h and 2h the ferrocene unit (Fc) is con-
nected to the O1–C11–C12–C13–S1 aliphatic fragment via the
same C1–C11 bond but spatial directionality of the Fc and the
C14–C19 phenyl ring relating to the fragment is completely differ-
ent (Fig. 2). In molecule 3h the Fc unit is connected to the O1–S1
fragment via the C1–C13 bond with bond distance [1.5033(18) Å]
Regardless of the lack of classical H-bonds the present crystal
structures form numerous C–Hꢀ ꢀ ꢀ
tems, Cp and phenyl rings, act as
form a chain along the a unit cell axis using the C12–Hꢀ ꢀ ꢀ
molecular interaction (Table 6) with system from unsubstituted
p
p
interactions where all
acceptors. In 1h the molecules
inter-
p sys-
p
p
Cp ring. Formation of this chain is supplemented by above men-
tioned the C16–Hꢀ ꢀ ꢀS1 interaction (Fig. S3). In 2h the C14–C19 phe-
nyl ring participates in C4–Hꢀ ꢀ ꢀ
p interactions (Table 6, Fig. S4)
while in crystal structures of 3h both Cp rings and both phenyl
rings act as , C12–Hꢀ ꢀ ꢀ , C16–Hꢀ ꢀ ꢀ
acceptors in the C9–Hꢀ ꢀ ꢀ
and C23–Hꢀ ꢀ ꢀ intermolecular interactions (Table 6, Fig. S5). The
most interesting is that the C–Hꢀ ꢀ ꢀ interactions form only evident
intramolecular interactions in crystal structures of 2h and 3h
p
p
p
p
p
p
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D. Stevanovic et al. / Polyhedron xxx (2014) xxx–xxx
Table 6
Geometrical parameters for intra- and intermolecular CꢁHꢀ ꢀ ꢀO, CꢁHꢀ ꢀ ꢀS and CꢁHꢀ ꢀ ꢀ
p interactions in crystal structures of 1h, 2h and 3h. (Cg1, Cg2, Cg3 and Cg4 are midpoints of
the C6ꢁC10, C14ꢁC19, C20ꢁC25 and C1ꢁC5 rings respectively). Criteria for CꢁHꢀ ꢀ ꢀO interactions: the Hꢀ ꢀ ꢀO distance shorter than 2.65 Å and the CꢁHꢀ ꢀ ꢀO angle larger than 130°.
Criteria for CꢁHꢀ ꢀ ꢀp interactions: perpendicular distance of H atom on the corresponding ring shorter than 3.0 Å and the CꢁHꢀ ꢀ ꢀCg angle larger than 130°.
DꢁHꢀ ꢀ ꢀA
DꢁH (Å)
Hꢀ ꢀ ꢀA (Å)
Dꢀ ꢀ ꢀA (Å)
DꢁHꢀ ꢀ ꢀA (°)
Symmetry codes:
1h
C15ꢁH15ꢀ ꢀ ꢀO1
0.93
0.93
0.97
2.63
3.08
2.85
3.574(4)
3.859(7)
3.594(3)
167.3
157.6
133.7
ꢁx + 1,y ꢁ 2,ꢁz + 1
x ꢁ 1,y,z
C16–H16ꢀ ꢀ ꢀS1
C12–H12bꢀ ꢀ ꢀCg1
x ꢁ 1,y,z
2h
C25–H25ꢀ ꢀ ꢀO1
C4–H4ꢀ ꢀ ꢀCg2
C6–H6ꢀ ꢀ ꢀCg3
0.93
0.93
0.93
2.55
3.09
3.04
3.478(3)
3.994(2)
3.890(3)
172.0
165.4
152.6
x,y + 1,z
ꢁx,ꢁy,ꢁz + 1
x,y,z
3h
C2–H2ꢀ ꢀ ꢀO1
C10–H10ꢀ ꢀ ꢀS1
C7–H7ꢀ ꢀ ꢀCg3
C9–H9ꢀ ꢀ ꢀCg4
C12–H12aꢀ ꢀ ꢀCg3
C23–H23ꢀ ꢀ ꢀCg2
0.93
0.93
0.93
0.93
0.97
0.93
2.50
2.99
3.03
2.92
3.07
2.85
3.428(2)
3.804(2)
3.819(2)
3.591(2)
4.150(7)
3.635(2)
173.9
146.6
143.5
130.6
139.3
143.2
x ꢁ 1,y,z
ꢁx + 1.5,y + 0.5,ꢁz + 1.5
x,y,z
ꢁx + 0.5,y + 0.5,ꢁz + 1.5
ꢁx + 1,ꢁy,ꢁz + 1
ꢁx + 1,ꢁy,ꢁz + 1
(Fig. S6) and in that way it play certain influence to the present
conformation of the molecules. Namely in both molecules the
unsubstituted Cp ring act as C–H donor while the C20–C25 phenyl
Appendix A. Supplementary data
CCDC 970342, 970343 and 970344 contain the supplementary
crystallographic data for compounds 1h, 2h and 3h respectively.
These data can be obtained free of charge via http://www.ccdc.ca-
m.ac.uk/conts/retrieving.html, or from the Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK;
fax: +44 1223 336 033; or e-mail: deposit@ccdc.cam.ac.uk. Addi-
tional data concerning single crystal X-ray structural analysis
(Figs. S1–S6) are available in the Supplementary material file.
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.poly.2013.12.012.
ring participate as
p
acceptor (Table 6, C6–Hꢀ ꢀ ꢀ
p
and C7–Hꢀ ꢀ ꢀ
p for
2h and 3h respectively). Moreover these two rings (Cp and phenyl)
form almost ideally the most favorable orthogonal orientation
(dihedral angle between mean planes of the C6–C10 and C20–
C25 rings is 86.86(9)° and 82.79(5)° for 2h and 3h respectively).
It is worth mentioning that regardless of this conformational
similarity in two molecules, the C20–C25 ring has very different
orientation relating to other C14–C19 phenyl ring (dihedral angle
between two phenyl rings is 5.47 (11) and 69.10(4)° for 2h and
3h respectively).
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