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Supporting Information for
Benzochalcogendiazole-based conjugated molecules:
Investigating the effects of substituents and heteroatom
juggling
Heta A. Patel[a] [+], Viraj J. Bhanvadia[a] [+], Hemant M. Mande[a], Sanjio S. Zade [b] and Arun L. Patel* [a]
[a] Department of Chemistry, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara-390002, India. E-mail: arunpatel_5376@yahoo.co.in
[b] Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER), Kolkata, Mohanpur-741246, India.[+] The authors Heta A. Patel and Viraj J. Bhanvadia contributed equally to this article.
Content Page no.XRD characterization data of catalyst S1
Spectroscopic data S1
Crystallographic sample preparation and measurement details S1
Thermal ellipsoid plots of synthesized compounds S2-S4
Crystallographic data and structures refinement parameters S5
Crystallographic torsional angles S5
Crystal packing and non-bonding interactions S6-S9
Spectral Data S10-S38
References S39
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2019
Page |S1
1. Powder XRD characterization of catalyst
Figure S 1 XRD of PANI and PANI-Pd1
2. Spectroscopic data
400 6000.0
0.1
0.2
0.3
0.4
0.5
Abso
rptio
n (a
.u.)
Wavelength (nm)
20 21 17 14 22 23 24 25
Figure S 2 Absorption spectra of compounds 14, 17, 20-25 in chloroform solution (10-5 M)
2. Crystallographic data
Crystallographic sample preparation and measurement details
The suitable single crystals of compounds 13-15, 18, 19, 21 and 23 were obtained by
slow evaporation of the saturated solution in petroleum ether/chloroform of
corresponding compounds. The preparation of co-crystal was conducted through
solution crystallization experiment, by mixing the corresponding reactants in 1:1 molar
ratio (Compound 19 and terephthalic acid) into a hot methanolic solution for 30 minutes.
The product was filtered and the suitable single crystal of co-crystal was obtained by
slow evaporation of the saturated dimethyl sulphoxide (DMSO) solution to get needle-
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like orange crystal. Diffraction data were collected by mounting suitable single crystal on
an Xcalibur, Eos, Gemini diffractometer using Cu Kα (λ = 1.54184) and/or Mo Kα (λ =
0.71073) radiation. Diffraction data of compounds 14, 15, 18 and 23 are collected at
lower temperatures using liquid nitrogen. The thermal ellipsoid plots (at 50% probability)
for each crystal structure are shown in Figure S 2-S 9. Crystallographic data and structure
refinement parameters are listed in Table S 1 and 2.
Figure S 3 Thermal ellipsoid plot of compound 13; ellipsoids are shown at 50% thermal probability
Figure S 4 Thermal ellipsoid plot of compound 14; ellipsoids are shown at 50% thermal probability
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Figure S 5 Thermal ellipsoid plot of compound 15; ellipsoids are shown at 50% thermal probability
Figure S 6 Thermal ellipsoid plot of compound 18; ellipsoids are shown at 50% thermal probability
Figure S 7 Thermal ellipsoid plot of compound 21; ellipsoids are shown at 50% thermal probability
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Figure S 8 Thermal ellipsoid plot of compound 23; ellipsoids are shown at 50% thermal probability
Figure S 9 Thermal ellipsoid plot of compound 19; ellipsoids are shown at 50% thermal probability
Figure S 10 Thermal ellipsoid plot of co-crystal; ellipsoids are shown at 50% thermal probability
Page |S5
Table S1. Crystallographic data and structures refinement parameters
Identification code Compound 13 Compound 14 Compound 15 Compound 18 Compound 21 Compound 23 Compound 19 Co-crystalEmpirical formula C22H16N2O C22H16N2S C22H16N2Se C72H60N6Se3 C24H16N2O4S C22H14F2N2S C40H30N8OS2 C28H24N4O5S0.25
Formula weight 322.35 342.44 387.33 1246.20 428.47 376.43 702.87 504.53Temperature/K 293(2) 199.94(12) 150.0 (10) 150.00(10) 293(2) 149.98(10) 293(2) 293(2)Crystal system monoclinic monoclinic monoclinic triclinic triclinic monoclinic triclinic monoclinicSpace group Pn P21/c P21/c P-1 P-1 P21/c P-1 P21/c
a/Å 8.7248(13) 9.6081(3) 9.6424(15) 11.8825(6) 8.8200(19) 9.5114(10) 9.4466(4) 13.0978(6)b/Å 8.5852(10) 15.1360(4) 15.1758(17) 12.7306(5) 10.9047(16) 15.6910(17) 9.9176(4) 8.4281(4)c/Å 11.5340(17) 11.7745(3) 11.7826(13) 20.6914(8) 10.9265(19) 11.5516(11) 19.5777(9) 21.7783(9)α/° 90.00 90.00 90 90.924(3) 76.670(14) 90 79.605(4) 90.00β/° 105.252 101.041(3) 101.61(17) 101.853(4) 67.630(18) 98.966(9) 86.538(4) 103.164(4)γ/° 90.00 90.00 90 111.378(4) 89.677(14) 90 70.028(4) 90.00
Volume/Å3 833.5 1680.64(8) 1688.9(4) 2838.3(2) 941.7(3) 1702.9(3) 1695.58(13) 2340.93(18)Z 2 4 4 2 2 4 2 4
ρcalcg/cm3 1.284 1.353 1.523 1.4581 1.5110 1.4681 1.3766 1.432Crystal size/mm3 .3 × .21 × .19 .34× .21 × .15 .35 × .32 × .16 .42 × .23 × .15 .42 × .23 × .15 .42×.23× .15 .09×.08× .05 .32 × .28 × .25
Radiation MoKα (λ = 0.71073)
CuKα (λ = 1.54184)
Mo Kα (λ = 0.71073)
Mo Kα (λ = 0.71073)
Mo Kα (λ = 0.71073)
Mo Kα (λ = 0.71073)
Cu Kα (λ = 1.54184)
CuKα (λ = 1.54184)
Reflections collected 9353 5794 7713 27620 20429 7888 10879 6730
Independent reflections
3741 [Rint = 0.0477, Rsigma =
0.0687]
3159 [Rint = 0.0161, Rsigma =
0.0260]
3808 [Rint = 0.0628, Rsigma
= 0.1267]
12985 [Rint = 0.0348, Rsigma
= 0.0624]
4611 [Rint = 0.2856, Rsigma
= 0.4136]
3893 [Rint = 0.0273, Rsigma
= 0.0414]
6471 [Rint = 0.0179, Rsigma
= 0.0298]
4452 [Rint = 0.0197, Rsigma =
0.0454]Data/restraints/para
meters 3741/2/227 3159/0/226 3808/0/227 12985/0/736 4611/0/280 3893/0/244 6471/0/468 4452/0/341
Goodness-of-fit on F2 1.012 1.021 1.067 1.021 0.933 1.066 1.046 1.054
Final R indexes [I>=2σ (I)]
R1 = 0.0620, wR2 = 0.1374
R1 = 0.0730, wR2 = 0.1773
R1 = 0.0961, wR2 = 0.1747
R1 = 0.0385, wR2 = 0.0720
R1 = 0.1132, wR2 = 0.2178
R1 = 0.1213, wR2 = 0.3057
R1 = 0.0633, wR2 = 0.1823
R1 = 0.0749, wR2 = 0.1957
Final R indexes [all data]
R1 = 0.1186, wR2 = 0.1707
R1 = 0.0829, wR2 = 0.1856
R1 = 0.1731, wR2 = 0.2183
R1 = 0.0669, wR2 = 0.0808
R1 = 0.3780, wR2 = 0.3364
R1 = 0.1595, wR2 = 0.3486
R1 = 0.0726, wR2 = 0.1941
R1 = 0.1047, wR2 = 0.2210
Largest diff. peak/hole/eÅ-3 0.73/-0.46 1.10/-0.86 3.29/-3.24 0.68/-0.78 1.91/-1.55 0.57/-1.05 1.60/-0.55 0.98/-0.30
CCDC Number 1876836 1850340 1850346 1850348 1876837 1850345 1850341 1850342
Table S2. Crystallographic torsional angles
Compound Torsional Angles13 -3.75o (C2−C1−C10−C11); -2.15o (C6−C7−C18−C19)14 -16.83o (C9−C1−C10−C11); -25.56o (C8−C7−C18−C19)15 -19.54o (C9−C1−C10−C11); -26.37o (C8−C7−C18−C19)18 13.04o (C9−C1−C10−C11); 12.53o (C6−C7−C19−C20)21 -15.12o (C2−C1−C10−C11); -7.57o (C8−C7−C21−C22)23 17.96o (C9−C1−C10−C11); 26.29o (C8−C7−C19−C20)19 -8.85o (C2−C1−C10−C11); 5.73o (C6−C7−C18−C19)
Co-crystal 5.13o (C2−C1−C10−C11); -1.39o (C6−C7−C18−C19)
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Figure S 11 (a) crystal packing of compound 13 along b-axis. (b) C-H···π interaction between the adjacent molecules of compound 14; (c) crystal packing of compound 14 with 2-D interlock pattern; (d) C-H···π interaction and Se···Se interaction between the adjacent molecules of compound 15; (e) crystal packing of compound 15 with 2-D interlock pattern; (f) Se···Se and Se···N interactions promoted crystal packing of compound 18 along b-axis.
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Figure S 12 (a) π-π stacking, C-H···π interaction and N-H hydrogen bonding promoted crystal packing of compound 21; (b) 2-D rectangular crystal packing of compound 21 along c-axis (c) crystal packing of compound 23 with 2-D interlock pattern along c-axis; (d) π-π stacking, C-H···π interaction, F-H hydrogen bonding and supramolecular S···F interaction promoted crystal packing of compound 23.
Figure S 13 Non-bonding N···O interactions and intermolecular hydrogen bonding (N-H and O-H) within the crystal structure of compound 19
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Figure S 14 (a) ORTEP diagram of the crystal structure of co-crystal; ellipsoids are at 50% thermal probability; (b) π-π stacking and non-bonding S···C interaction promoted crystal packing of co-crystal; (c) non-bonding N···O interactions and intermolecular hydrogen bonding (S-H and O-H) within the crystal structure of co-crystal
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Spectral data:
Figure S 15 1H-NMR of Compound 4
Figure S 16 Mass Spectra of Compound 4
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Figure S 17 1H-NMR of Compound 5
Figure S 18 Mass Spectra of Compound 5
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Figure S 19 1H-NMR of Compound 6
Figure S 20 Mass Spectra of Compound 6
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Figure S 21 1H-NMR of Compound 7
Figure S 22 Mass Spectra of Compound 7
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Figure S 23 1H-NMR of Compound 8
Figure S 24 Mass Spectra of Compound 8
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Figure S 25 1H-NMR of Compound 9
Figure S 26 Mass Spectra of Compound 9
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Figure S 27 1H-NMR of Compound 13
Figure S 28 13C-NMR of Compound 13
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Figure S 29 Mass Spectra of Compound 13
Figure S 30 HRMS of Compound 13
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Figure S 31 1H-NMR of Compound 14
Figure S 32 13C-NMR of Compound 14
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Figure S 33 Mass Spectra of Compound 14
Figure S 34 HRMS of Compound 14
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Figure S 35 1H-NMR of Compound 15
Figure S 36 13C-NMR of Compound 15
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Figure S 37 Mass Spectra of Compound 15
Figure S 38 HRMS of Compound 15
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Figure S 39 1H-NMR of Compound 16
Figure S 40 13C-NMR of Compound 16
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Figure S 41 HRMS of Compound 16
Figure S 42 1H-NMR of Compound 17
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Figure S 43 13C-NMR of Compound 17
Figure S 44 Mass Spectra of Compound 17
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Figure S 45 HRMS of Compound 17
Figure S 46 1H-NMR of Compound 18
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Figure S 47 13C-NMR of Compound 18
Figure S 48 Mass Spectra of Compound 18
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Figure S 49 HRMS of Compound 18
Figure S 50 1H-NMR of Compound 19
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Figure S 51 13C-NMR of Compound 19
Figure S 52 Mass Spectra of Compound 19
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Figure S 53 1H-NMR of Compound 20
Figure S 54 13C-NMR of Compound 20
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Figure S 55 HRMS of Compound 20
Figure S 56 1H-NMR of Compound 21
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#
* **
Figure S 57 13C-NMR of Compound 21; (# = signal from “grease” and * = signals from
“petroleum ether”)2
Figure S 58 Mass Spectra of Compound 21
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Figure S 59 HRMS of Compound 21
Figure S 60 1H-NMR of Compound 22
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Figure S 61 13C-NMR of Compound 22
Figure S 62 HRMS of Compound 22
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Figure S 63 1H-NMR of Compound 23
Figure S 64 13C-NMR of Compound 23
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Figure S 65 Mass Spectra of Compound 23
Figure S 66 HRMS of Compound 23
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Figure S 67 1H-NMR of Compound 24
#
* ***
Figure S 68 13C-NMR of Compound 24; (# = signal from “grease” and * = signals from
“petroleum ether”)2
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Figure S 69 HRMS of Compound 24
Figure S 70 1H-NMR of Compound 25
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Figure S 71 13C-NMR of Compound 25
Figure S 72 HRMS of Compound 25
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References1 H. A. Patel, A. L. Patel and A. V. Bedekar, Appl. Organometal. Chem, 2015, 29,
1–6.
2 H. E. Gottlieb, V. Kotlyar and A. Nudelman, J. Org. Chem., 1997, 62, 7512–7515.