Supplementary Information s48

Supplementary Information

Solid-State Photodimerization in an Organic Salt of 1,2-Bis(4-pyridyl)ethylene and Trifluoromethanesulphonic Acid via Pedal-like Motion ABDUL MALIK P. PEEDIKAKKAL Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia Email: [email protected] Tel: +966 3860 7552

Table of Contents Page 1 Figure S1. H NMR spectrum of 1 before UV irradiation in d6-DMSO. The inset shows the structure of S3 protonated bpe. 1 Figure S2. H NMR spectrum of 1 after UV irradiation in D2O. The inset shows the structure of S4 protonated rctt-tpcb. Scheme S1. The protonated rctt-tpcb (2), rtct-tpcb (3) and rcct-tpcb (4) isomers. S4 1 Figure S3. H NMR spectrum of 2 in d6-DMSO after 3 days. The peaks correspond to all the three S5 isomers [1]. Condition: 10 mg of 2 dissolved in d6-DMSO (0.5 mL) at room temperature and monitored over period of time using 1H NMR spectroscopy. 1 Figure S4. Figure S4. H NMR spectrum of 2 in d6-DMSO after refluxing for 30 min at 100°C shows S6 100% rtct-tpcb [1]. Condition: 10 mg of 2 dissolved in d6-DMSO (0.5 mL) and refluxed in heating oven at at 100°C for 30 min. 1 Figure S5. H NMR spectrum of 1 crystals in d6-DMSO before UV irradiation in the solution-state. The S7 peak at 2.49 and 3.50 ppm indicate DMSO and H2O in DMSO respectively. The rest of the peaks are for protonated bpe. 1 Figure S6. H NMR spectrum of 1 crystals in d6-DMSO after UV irradiation in the solution-state for 24 h. S8 The peak at 2.49 and 3.50 ppm indicate DMSO and H2O in DMSO respectively. The solution irradiation of 1 indicates the formation of mixture of products including isomerized [bpeH]+ and dimerized [bpeH]+ as observed peaks with relatively high percentage of unreacted [bpeH]+. Figure S7. TGA-DTA analysis of 1. Compound 1 is stable up to ~ 260°C. S9 Figure S8. Microscopic image of single crystals of 1. S10 Table S1. Crystallographic Data for 1. S11 Figure S9. A view of the infinite 1D hydrogen bonded assembly of [bpe-H]+ cations in the bc-plane. The S12 C-H hydrogen atoms are omitted for clarity. Table S2. Atomic coordinates and equivalent isotropic displacement parameters for 1. S13 Table S3. Bond lengths [Å] and angles [°] for 1. S15 Table S4. Anisotropic displacement parameters for 1. S19 4 S21 Table S5. Hydrogen coordinates ( x 10 ) and isotropic displacement parameters for 1. Table S6. Hydrogen bonds for 1. S22

S1 NMR spectra

S2 1 Figure S1. H NMR spectrum of 1 before UV irradiation in d6-DMSO. The inset shows the structure of protonated bpe.

H H Ha N N Hb Hc

1 Figure S2. H NMR spectrum of 1 after UV irradiation in D2O. The inset shows the structure of protonated rctt-tpcb.

S3 Scheme S1. The protonated rctt-tpcb (2), rtct-tpcb (3) and rcct-tpcb (4) isomers

1 Figure S3. H NMR spectrum of 2 in d6-DMSO after 3 days. The peaks correspond to all

the three isomers [1]. Condition: 10 mg of 2 dissolved in d6-DMSO (0.5 mL) at room temperature and monitored over period of time using 1H NMR spectroscopy.

S4 1 Figure S4. H NMR spectrum of 2 in d6-DMSO after refluxing for 30 min at 100°C shows

100% rtct-tpcb [1]. Condition: 10 mg of 2 dissolved in d6-DMSO (0.5 mL) and refluxed in heating oven at at 100°C for 30 min.

S5 S6 1 Figure S5. H NMR spectrum of 1 crystals in d6-DMSO before UV irradiation in the solution-state. The peak at 2.49 and 3.50 ppm

indicate DMSO and H2O in DMSO respectively. The rest of the peaks are for protonated bpe.

S7 1 Figure S6. H NMR spectrum of 1 crystals in d6-DMSO after UV irradiation in the solution-state for 24 h. The peak at 2.49 and 3.50 ppm

indicate DMSO and H2O in DMSO respectively. The solution irradiation of 1 indicates the formation of mixture of products including isomerized [bpeH]+ and dimerized [bpeH]+ as observed peaks with relatively high percentage of unreacted [bpeH]+.

S8 S9 TGA Analysis

Sample: AM437 File: C:\TA\Data\TGA\Abdul\NEW\AM437\AM437.001 Size: 9.5977 mg TGA-DTA Operator: Abdul Run Date: 14-Jan-09 16:13 Comment: Ramp 10°c/min to 600°c in N2 Instrument: 2960 SDT V3.0F 120 0.010 ) C °

100 / g

0.005 m / C ° (

242.86°C c n

80 e r ) 67.29°C e f % f ( i

30.34°C D

h 0.000 e g i r e u t a W r

60 e 348.81°C p m e T

-0.005 r e

20 -0.010 0 100 200 300 400 500 600 Exo Up Temperature (°C) Universal V3.9A TA Instruments

Figure S7. TGA-DTA analysis of 1. Compound 1 is stable up to ~ 260°C.

S10 Single Crystal X-ray Crystallographic Analysis Intensity data for 1 were collected on a Bruker APEX diffractometer attached with a CCD detector and graphite-monochromated MoK (λ = 0.71073 Å) radiation using a sealed tube (2.4 kW). Absorption corrections were made using the program SADABS1 and the crystallographic package SHELXTL2 was used for all calculations. Crystal data as well as details of data collection and refinement of 1 are summarized in Table S1.

Figure S8. Microscopic image of single crystals of 1.

S11 Table S1. Crystallographic Data for 1.

Compound 1

Formula C26H22F6N4O6S2 Formula weight 664.60 T/K 100(2) Cryst. Syst. Triclinic space group P a/Å 8.2801(7) b/Å 12.0613(10) c/Å 13.7409(11) /o 89.283(2) /o 76.992(2) /o 89.378(2) vol/Å 3 / Z 1336.92(19) / 2 ρ, Mg.cm–3 1.651  /mm-1 0.293 Reflns col. 16507

Ind. Reflns/ Rint / GooF 6145/ 0.0358/1.045

Final R[I>2], R1/ wR2 0.0520/ 0.1290

R indices (all data), R1/ wR2 0.0730/ 0.1408 Largest diff. peak and hole / e.Å-3 0.703 and -0.351

Figure S9. A view of the infinite 1D hydrogen bonded assembly of [bpe-H]+ cations in

S12 the bc-plane. The C-H hydrogen atoms are omitted for clarity.

Table S2. Atomic coordinates and equivalent isotropic displacement parameters for 1. U(eq) is ij defined as one third of the trace of the orthogonalized U tensor. ______x y z U(eq) ______N(1) 8992(2) 12434(1) 6576(1) 18(1) N(2) 8836(2) 4681(1) 6650(1) 18(1) N(3) 1154(2) 5395(1) 8382(1) 21(1) N(4) 1272(2) -2354(1) 8309(1) 20(1)

S13 C(1) 10340(3) 11939(2) 6025(2) 18(1) C(2) 10488(2) 10807(2) 5985(2) 18(1) C(3) 9204(3) 10146(2) 6514(2) 17(1) C(4) 7817(3) 10682(2) 7089(2) 20(1) C(5) 7740(3) 11825(2) 7105(2) 21(1) C(6) 9415(2) 8938(2) 6449(2) 18(1) C(7) 8262(2) 8197(2) 6833(2) 19(1) C(8) 10058(3) 5343(2) 6160(2) 19(1) C(9) 9942(3) 6483(2) 6194(2) 19(1) C(10) 8502(3) 6992(2) 6753(2) 17(1) C(11) 7255(3) 6296(2) 7264(2) 20(1) C(12) 7464(3) 5163(2) 7198(2) 20(1) C(13) 2453(3) 4789(2) 7908(2) 27(1) C(14) 2363(3) 3645(2) 7933(2) 30(1) C(15) 926(3) 3126(2) 8469(2) 26(1) C(16) -367(3) 3793(2) 8941(2) 27(1) C(17) -241(3) 4919(2) 8884(2) 22(1) C(20) 2557(3) -1824(2) 7743(2) 25(1) C(21) 2687(3) -691(2) 7694(2) 30(1) C(22) 1451(3) -44(2) 8262(2) 28(1) C(23) 84(3) -589(2) 8850(2) 28(1) C(24) 45(3) -1740(2) 8855(2) 22(1) S(1) 5085(1) 6843(1) 10060(1) 20(1) O(1) 6849(2) 6648(1) 9787(1) 27(1) O(2) 4159(2) 6450(1) 9366(1) 30(1) O(3) 4324(2) 6665(1) 11102(1) 28(1) C(25) 4932(3) 8349(2) 9936(2) 22(1) F(1) 5661(2) 8699(1) 9017(1) 35(1) F(2) 5649(2) 8874(1) 10570(1) 39(1) F(3) 3350(2) 8694(1) 10114(1) 32(1) S(2) 5242(1) 1833(1) 5144(1) 17(1) O(4) 6884(6) 1440(4) 4890(5) 31(1) O(5) 4311(13) 1444(7) 4439(6) 24(1) O(6) 4443(6) 1441(3) 6110(3) 30(1) C(26) 5133(7) 3373(7) 5052(4) 65(3) F(4) 5839(5) 3751(3) 4133(3) 27(1)

S14 F(5) 5832(4) 3749(4) 5779(3) 49(1) F(6) 3512(5) 3612(3) 5320(3) 33(1) S(2A) 5073(2) 3368(2) 5070(1) 13(1) O(4A) 6028(12) 3518(9) 4064(5) 31(1) O(5A) 6154(9) 3792(7) 5660(6) 24(1) O(6A) 3483(8) 3861(7) 5198(7) 30(1) C(26A) 5198(9) 1826(8) 5141(6) 65(3) F(4A) 6853(8) 1689(7) 4902(7) 27(1) F(5A) 4390(20) 1475(12) 4457(11) 49(1) F(6A) 4404(9) 1732(5) 6109(5) 33(1) C(18A) 624(3) 1920(2) 8593(2) 17(1) C(19A) 1734(3) 1164(2) 8160(2) 17(1) C(19B) 644(13) 1186(9) 8560(8) 17(1) C(18B) 1708(13) 1939(9) 8175(8) 17(1)

S15 ______Table S3. Bond lengths [Å] and angles [°] for 1. ______N(1)-C(1) 1.339(3) N(1)-C(5) 1.344(3) N(2)-C(12) 1.344(3) N(2)-C(8) 1.346(3) N(3)-C(17) 1.336(3) N(3)-C(13) 1.341(3) N(4)-C(20) 1.333(3) N(4)-C(24) 1.341(3) C(1)-C(2) 1.371(3) C(2)-C(3) 1.396(3) C(3)-C(4) 1.396(3) C(3)-C(6) 1.467(3) C(4)-C(5) 1.380(3) C(6)-C(7) 1.330(3) C(7)-C(10) 1.467(3) C(8)-C(9) 1.377(3) C(9)-C(10) 1.404(3) C(10)-C(11) 1.394(3) C(11)-C(12) 1.376(3) C(13)-C(14) 1.382(3) C(14)-C(15) 1.400(3) C(15)-C(16) 1.377(3) C(15)-C(18A) 1.480(3) C(15)-C(18B) 1.583(11) C(16)-C(17) 1.364(3) C(20)-C(21) 1.371(3) C(21)-C(22) 1.380(3) C(22)-C(23) 1.399(3) C(22)-C(19A) 1.478(3) C(22)-C(19B) 1.638(11) C(23)-C(24) 1.389(3) S(1)-O(2) 1.4392(16) S(1)-O(1) 1.4416(15)

S16 S(1)-O(3) 1.4421(16) S(1)-C(25) 1.827(2) C(25)-F(2) 1.329(2) C(25)-F(1) 1.337(2) C(25)-F(3) 1.340(2) S(2)-O(4) 1.405(4) S(2)-O(6) 1.420(3) S(2)-O(5) 1.453(4) S(2)-C(26) 1.863(8) C(26)-F(6) 1.339(5) C(26)-F(4) 1.342(5) C(26)-F(5) 1.348(5) S(2A)-O(6A) 1.413(4) S(2A)-O(5A) 1.437(4) S(2A)-O(4A) 1.441(5) S(2A)-C(26A) 1.864(8) C(26A)-F(4A) 1.344(5) C(26A)-F(5A) 1.346(5) C(26A)-F(6A) 1.349(5) C(18A)-C(19A) 1.334(4) C(19B)-C(18B) 1.296(16)

C(1)-N(1)-C(5) 120.40(17) C(12)-N(2)-C(8) 118.02(17) C(17)-N(3)-C(13) 121.45(19) C(20)-N(4)-C(24) 117.82(18) N(1)-C(1)-C(2) 121.36(19) C(1)-C(2)-C(3) 119.93(19) C(4)-C(3)-C(2) 117.60(18) C(4)-C(3)-C(6) 124.32(19) C(2)-C(3)-C(6) 118.07(18) C(5)-C(4)-C(3) 119.94(19) N(1)-C(5)-C(4) 120.76(19) C(7)-C(6)-C(3) 125.51(19) C(6)-C(7)-C(10) 124.42(19) N(2)-C(8)-C(9) 122.52(19)

S17 C(8)-C(9)-C(10) 119.82(19) C(11)-C(10)-C(9) 116.97(18) C(11)-C(10)-C(7) 119.21(18) C(9)-C(10)-C(7) 123.82(19) C(12)-C(11)-C(10) 119.93(19) N(2)-C(12)-C(11) 122.74(19) N(3)-C(13)-C(14) 119.8(2) C(13)-C(14)-C(15) 119.8(2) C(16)-C(15)-C(14) 117.7(2) C(16)-C(15)-C(18A) 115.1(2) C(14)-C(15)-C(18A) 127.2(2) C(16)-C(15)-C(18B) 151.0(4) C(14)-C(15)-C(18B) 91.2(4) C(18A)-C(15)-C(18B) 36.0(4) C(17)-C(16)-C(15) 120.7(2) N(3)-C(17)-C(16) 120.5(2) N(4)-C(20)-C(21) 123.5(2) C(20)-C(21)-C(22) 119.6(2) C(21)-C(22)-C(23) 117.5(2) C(21)-C(22)-C(19A) 115.0(2) C(23)-C(22)-C(19A) 127.6(2) C(21)-C(22)-C(19B) 149.4(4) C(23)-C(22)-C(19B) 92.9(4) C(19A)-C(22)-C(19B) 34.8(4) C(24)-C(23)-C(22) 119.3(2) N(4)-C(24)-C(23) 122.3(2) O(2)-S(1)-O(1) 115.64(9) O(2)-S(1)-O(3) 115.44(10) O(1)-S(1)-O(3) 115.31(10) O(2)-S(1)-C(25) 102.76(10) O(1)-S(1)-C(25) 102.59(10) O(3)-S(1)-C(25) 102.09(10) F(2)-C(25)-F(1) 107.12(18) F(2)-C(25)-F(3) 107.11(17) F(1)-C(25)-F(3) 107.08(17) F(2)-C(25)-S(1) 111.95(15)

S18 F(1)-C(25)-S(1) 111.66(14) F(3)-C(25)-S(1) 111.63(15) O(4)-S(2)-O(6) 110.3(3) O(4)-S(2)-O(5) 110.6(6) O(6)-S(2)-O(5) 107.9(4) O(4)-S(2)-C(26) 111.7(3) O(6)-S(2)-C(26) 111.7(2) O(5)-S(2)-C(26) 104.4(4) F(6)-C(26)-F(4) 112.8(5) F(6)-C(26)-F(5) 107.1(5) F(4)-C(26)-F(5) 114.3(6) F(6)-C(26)-S(2) 104.4(4) F(4)-C(26)-S(2) 112.2(5) F(5)-C(26)-S(2) 105.3(5) O(6A)-S(2A)-O(5A) 117.3(6) O(6A)-S(2A)-O(4A) 111.4(5) O(5A)-S(2A)-O(4A) 102.7(7) O(6A)-S(2A)-C(26A) 117.7(5) O(5A)-S(2A)-C(26A) 106.8(5) O(4A)-S(2A)-C(26A) 98.3(5) F(4A)-C(26A)-F(5A) 115.6(11) F(4A)-C(26A)-F(6A) 118.4(8) F(5A)-C(26A)-F(6A) 117.0(11) F(4A)-C(26A)-S(2A) 99.6(6) F(5A)-C(26A)-S(2A) 104.4(9) F(6A)-C(26A)-S(2A) 96.2(6) C(19A)-C(18A)-C(15) 122.5(2) C(18A)-C(19A)-C(22) 123.5(2) C(18B)-C(19B)-C(22) 109.4(9) C(19B)-C(18B)-C(15) 109.3(9) ______

S19 Table S4. Anisotropic displacement parameters for 1. The anisotropic displacement factor 2 2 2 11 12 exponent takes the form: -2 [ h a* U + ... + 2 h k a* b* U ] ______U11 U22 U33 U23 U13 U12 ______N(1) 22(1) 13(1) 21(1) -1(1) -8(1) 1(1) N(2) 25(1) 12(1) 20(1) 0(1) -7(1) 0(1) N(3) 29(1) 11(1) 26(1) -2(1) -11(1) 0(1) N(4) 28(1) 12(1) 21(1) 0(1) -10(1) 0(1) C(1) 21(1) 18(1) 16(1) 2(1) -5(1) -2(1) C(2) 18(1) 20(1) 17(1) -2(1) -4(1) 2(1) C(3) 22(1) 15(1) 16(1) -1(1) -8(1) 1(1) C(4) 20(1) 17(1) 22(1) 2(1) -4(1) -3(1) C(5) 20(1) 19(1) 23(1) -3(1) -5(1) 3(1) C(6) 20(1) 17(1) 18(1) -1(1) -5(1) 3(1) C(7) 20(1) 18(1) 19(1) -2(1) -4(1) 4(1) C(8) 20(1) 18(1) 19(1) -1(1) -5(1) 3(1) C(9) 20(1) 17(1) 20(1) 1(1) -5(1) -2(1) C(10) 24(1) 15(1) 16(1) 0(1) -9(1) -1(1) C(11) 21(1) 19(1) 20(1) -2(1) -4(1) 3(1) C(12) 23(1) 16(1) 20(1) 2(1) -4(1) -3(1) C(13) 21(1) 30(1) 30(1) 4(1) -3(1) -2(1) C(14) 33(1) 30(1) 28(1) -8(1) -9(1) 18(1) C(15) 43(1) 16(1) 26(1) -1(1) -23(1) -1(1) C(16) 27(1) 29(1) 28(1) 8(1) -12(1) -10(1) C(17) 21(1) 25(1) 19(1) -1(1) -5(1) 7(1) C(20) 27(1) 25(1) 24(1) -1(1) -8(1) 2(1) C(21) 38(1) 26(1) 27(1) 8(1) -13(1) -14(1) C(22) 53(2) 14(1) 25(1) 3(1) -25(1) -2(1) C(23) 39(1) 26(1) 21(1) -8(1) -15(1) 13(1) C(24) 25(1) 24(1) 18(1) 2(1) -6(1) -1(1) S(1) 17(1) 20(1) 21(1) 0(1) 1(1) 1(1) O(1) 18(1) 26(1) 33(1) 0(1) 1(1) 5(1) O(2) 27(1) 32(1) 30(1) -6(1) -4(1) -3(1) O(3) 29(1) 28(1) 23(1) 5(1) 4(1) 4(1)

S20 C(25) 18(1) 25(1) 22(1) 2(1) -2(1) 2(1) F(1) 34(1) 32(1) 32(1) 11(1) 7(1) 4(1) F(2) 46(1) 25(1) 50(1) -6(1) -23(1) -1(1) F(3) 19(1) 30(1) 45(1) 4(1) 0(1) 10(1) S(2) 11(1) 20(1) 16(1) 1(1) 2(1) -2(1) O(4) 42(2) 14(3) 33(2) -1(2) 2(1) 20(2) O(5) 28(2) 22(2) 26(2) 3(1) -12(1) -5(1) O(6) 25(2) 13(2) 40(2) 20(1) 16(1) 10(1) C(26) 63(4) 69(4) 62(4) -5(3) -15(3) -1(3) F(4) 25(2) 14(2) 35(2) 6(1) 6(1) 8(1) F(5) 31(2) 52(2) 66(3) -24(2) -14(2) -5(2) F(6) 41(2) 11(2) 44(2) 12(1) -3(1) 14(1) S(2A) 8(1) 12(1) 16(1) 0(1) 0(1) -2(1) O(4A) 42(2) 14(3) 33(2) -1(2) 2(1) 20(2) O(5A) 28(2) 22(2) 26(2) 3(1) -12(1) -5(1) O(6A) 25(2) 13(2) 40(2) 20(1) 16(1) 10(1) C(26A) 63(4) 69(4) 62(4) -5(3) -15(3) -1(3) F(4A) 25(2) 14(2) 35(2) 6(1) 6(1) 8(1) F(5A) 31(2) 52(2) 66(3) -24(2) -14(2) -5(2) F(6A) 41(2) 11(2) 44(2) 12(1) -3(1) 14(1) C(18A) 18(1) 15(1) 17(1) 1(1) -4(1) -2(1) C(19A) 18(1) 15(1) 17(1) 1(1) -4(1) -2(1) C(19B) 18(1) 15(1) 17(1) 1(1) -4(1) -2(1) C(18B) 18(1) 15(1) 17(1) 1(1) -4(1) -2(1)

S21 ______Table S5. 4 Hydrogen coordinates ( x 10 ) and isotropic displacement parameters for 1. ______x y z U(eq) ______

H(1N) 8900(40) 13320(30) 6550(20) 71(10) H(3N) 1280(40) 6270(30) 8360(20) 62(10) H(1) 11213 12382 5654 22 H(2) 11462 10472 5598 22 H(4) 6927 10260 7468 24 H(5) 6791 12186 7495 25 H(6) 10463 8662 6102 21 H(7) 7212 8466 7184 22 H(8) 11038 5012 5776 23 H(9) 10833 6922 5841 23 H(11) 6263 6602 7657 24 H(12) 6602 4703 7556 24 H(13) 3433 5144 7555 32 H(14) 3273 3212 7588 36 H(16) -1358 3464 9311 32 H(17) -1151 5369 9203 26 H(20) 3430 -2253 7353 30 H(21) 3624 -354 7271 35 H(23) -808 -176 9242 33 H(24) -884 -2105 9259 26 H(18A) -399 1675 8997 20 H(19A) 2760 1415 7765 20 H(19B) -436 1324 8955 20 H(18B) 2787 1802 7778 20

S22 ______Table S6. Hydrogen bonds for 1 ______D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ______N(1)-H(1N)...N(2)#1 1.07(3) 1.65(3) 2.714(2) 172(3) N(3)-H(3N)...N(4)#1 1.06(3) 1.67(3) 2.718(2) 174(3) ______Symmetry transformations used to generate equivalent atoms: #1 x,y+1,z

S23 References: 1) Peedikakkal A M P, Peh C S Y, Koh L L, Vittal J J 2010 Inorg. Chem. 49 6775 2) Sheldrick, G. M. SADABS, version 2.05, University of Göttingen, Göttingen, Germany. 3) Sheldrick, G M 1997 SHELXS-97, Program for X-ray Crystal Structure Determination, (University of Göttingen, Germany); Sheldrick G M 1997 SHELXL-97, Program for X-ray Crystal Structure Refinement (University of Göttingen, Germany).