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-

Page |S2

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

Page |S3

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

Page |S4

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)

Page |S6

Page |S7

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.

Page |S8

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

Page |S9

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

Page |S10

Spectral data:

Figure S 15 1H-NMR of Compound 4

Figure S 16 Mass Spectra of Compound 4

Page |S11

Figure S 17 1H-NMR of Compound 5

Figure S 18 Mass Spectra of Compound 5

Page |S12

Figure S 19 1H-NMR of Compound 6

Figure S 20 Mass Spectra of Compound 6

Page |S13

Figure S 21 1H-NMR of Compound 7

Figure S 22 Mass Spectra of Compound 7

Page |S14

Figure S 23 1H-NMR of Compound 8

Figure S 24 Mass Spectra of Compound 8

Page |S15

Figure S 25 1H-NMR of Compound 9

Figure S 26 Mass Spectra of Compound 9

Page |S16

Figure S 27 1H-NMR of Compound 13

Figure S 28 13C-NMR of Compound 13

Page |S17

Figure S 29 Mass Spectra of Compound 13

Figure S 30 HRMS of Compound 13

Page |S18

Figure S 31 1H-NMR of Compound 14

Figure S 32 13C-NMR of Compound 14

Page |S19

Figure S 33 Mass Spectra of Compound 14

Figure S 34 HRMS of Compound 14

Page |S20

Figure S 35 1H-NMR of Compound 15

Figure S 36 13C-NMR of Compound 15

Page |S21

Figure S 37 Mass Spectra of Compound 15

Figure S 38 HRMS of Compound 15

Page |S22

Figure S 39 1H-NMR of Compound 16

Figure S 40 13C-NMR of Compound 16

Page |S23

Figure S 41 HRMS of Compound 16

Figure S 42 1H-NMR of Compound 17

Page |S24

Figure S 43 13C-NMR of Compound 17

Figure S 44 Mass Spectra of Compound 17

Page |S25

Figure S 45 HRMS of Compound 17

Figure S 46 1H-NMR of Compound 18

Page |S26

Figure S 47 13C-NMR of Compound 18

Figure S 48 Mass Spectra of Compound 18

Page |S27

Figure S 49 HRMS of Compound 18

Figure S 50 1H-NMR of Compound 19

Page |S28

Figure S 51 13C-NMR of Compound 19

Figure S 52 Mass Spectra of Compound 19

Page |S29

Figure S 53 1H-NMR of Compound 20

Figure S 54 13C-NMR of Compound 20

Page |S30

Figure S 55 HRMS of Compound 20

Figure S 56 1H-NMR of Compound 21

Page |S31

#

* **

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

Page |S32

Figure S 59 HRMS of Compound 21

Figure S 60 1H-NMR of Compound 22

Page |S33

Figure S 61 13C-NMR of Compound 22

Figure S 62 HRMS of Compound 22

Page |S34

Figure S 63 1H-NMR of Compound 23

Figure S 64 13C-NMR of Compound 23

Page |S35

Figure S 65 Mass Spectra of Compound 23

Figure S 66 HRMS of Compound 23

Page |S36

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

Page |S37

Figure S 69 HRMS of Compound 24

Figure S 70 1H-NMR of Compound 25

Page |S38

Figure S 71 13C-NMR of Compound 25

Figure S 72 HRMS of Compound 25

Page |S39

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.