SUPPORTING INFORMATION TO. On Two Alizarin Polymorphs

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1 SUPPORTING INFORMATION TO On Two Alizarin Polymorphs by Michał K. Cyrański, a Michał H. Jamróz, b Anna Rygula, c Jan Cz. Dobrowolski, b,d Łukasz Dobrzycki *,a, and Malgorzata Baranska*,c,e a FACULTY OF CHEMISTRY,UNIVERSITY OF WARSAW,PASTEURA 1, WARSAW, POLAND b SPECTROSCOPY AND MOLECULAR MODELING GROUP, INDUSTRIAL CHEMISTRY RESEARCH INSTITUTE, 8 RYDYGIERA STREET, WARSAW, POLAND c FACULTY OF CHEMISTRY, JAGIELLONIAN UNIVERSITY,INGARDENA 3, CRACOW, POLAND d LABORATORY FOR THEORETICAL METHODS AND CALCULATIONS,NATIONAL MEDICINES INSTITUTE, 30/34 CHEŁMSKA STREET, WARSAW, POLAND e JAGIELLONIAN CENTER FOR EXPERIMENTAL THERAPEUTICS (JCET), JAGIELLONIAN UNIVERSITY, 14 BOBRZYNSKIEGO STR., KRAKOW, POLAND

2 Juxtaposition of the theoretical and experimental PXRD patterns Figure 1SI. Comparison of PXRD patterns of polymorph I (dashed blue line) and of polymorph II (dashed red line).

3 Figure 2SI. PXRD pattern (dashed line) and theoretically calculated pattern (solid line) of polymorph I. Note that the unit cell parameters slightly differ in 295K. They are a=20.188å, b=3.639å, c=21.149å, = Fig. 3SI. PXRD pattern (dashed line) and theoretically calculated pattern (solid line) of polymorph II. Note that the unit cell parameters slightly differ in 295K. They are a=8.265å, b=3.783å, c=17.014å, =100.43

4 Fig. 4SI. The Raman spectra of the alizarin form I (olive) and form II (red) crystals in the range cm -1.

5 Figure 5SI. The Raman spectra of the alizarin form I (olive) and form II (red) crystals in the range cm Figure 6SI. The IR spectra of the alizarin form I (red) and form II (dark blue) crystals in the range cm -1.

6 Fig. 7SI. Comparison of the Raman theoretical B3LYP/6-31++G** spectra of alizarin monomer (top) and dimer (bottom)

7 Fig. 8SI. Comparison of the IR theoretical B3LYP/6-31++G** spectra of alizarin monomer (top) and dimer (bottom)

8 Fig. 9SI. The ν(oh) and ν(ch) region of the experimental IR (red) and Raman (blue) spectra.

9 Figure 10SI. Comparison of the Raman experimental digitized (top) and theoretical (bottom) spectra of alizarin.

10 Figure 11SI. Comparison of the IR experimental digitized (top) and theoretical (bottom) spectra of alizarin.

11 Fig. 12SI. Comparison of the IR theoretical harmonic (top, red) and anharmonic (bottom, blue) B3LYP/aug cc-pvdz spectra of the alizarin molecule. Observe that in the anharmonic spectrum different bands are shifted by different factors.

12 Table 1SI. The B3LYP/aug-cc-pVDZ calculated fundamental frequencies of the alizarin molecule ν har ν anh I IR A R A R(ANHAR) Symm. PED (cm -1 ) (cm -1 ) (km/mol) (A 4 /amu) (%) (%) A' ν(o2-h) A' 85 ν s (CH_R1); 14 ν s (CH_R2) A' 83 ν s (CH_R2); 14 ν s (CH_R1) A' 99 ν a 1(CH_R2) A' 96 ν a 1(O1-H&CH_R1) A' 96 ν a 2(O1-H&CH_R1) A' 97 ν a 2(CH_R2) A' 98 ν a 3(CH_R2) A' 80 ν(c=04) A' 67 ν(c=03) A' 60 ν 1 (CC) A' 50 ν 2 (CC); 17 β(o1-h) A' 62 ν 3 (CC) A' 67 ν 4 (CC) A' 54 ν 5 (CC); 12 β 4 (CH) A' 41 β 1 (CH_R2); 20 ν 11 (CC) A' 54 ν 6 (CC); 19 β(o1-h) A' 39 ν 7 (CC); 22 β 2 (CH); 12 β 6 (CH) A' 42 ν 8 (CC); 38 β(o2-h) A' 24 β(o1-h); 13 ν 6 (CC); 13 ν 9 (CC); 11 ν 12 (CC); 10 β 8 (CCC) A' 68 ν 9 (CC) A' 44 ν(c-o1); 10 β 2 (CH) A' 56 ν(c-o2); 10 ν 10 (CC) A' 39 ν 70 (CC); 17 β 4 (CH); 12 β(o2-h) A' 46 β 2 (CH); 39 ν 10 (CC); 16 ν 7 (CC) A' 14 ν 8 (CC); 19 β(o2-h) A' 46 β 3 (CH) A' 34 β 4 (CH); 11 ν 1 (CC) A' 81 β 5 (CH_R2); 14 ν 13 (CC) A' 48 β 6 (CH) A' 55 β 1 (CCC) A' 56 ν 11 (CC); 21 β 1 (CH_R2) A' 45 ν 12 (CC); 13 β 1 (CCC) A'' 87 τ 1 (CH_R2) A' 53 ν 13 (CC) A" 86 τ 2 (CH) A" 87 τ 3 (CH_R1) A" 69 τ 4 (CH_R2); 18 τ(c=o3) A' 63 β 2 (CCC) A'' 36 τ(c=o3); 25 τ(o1-h); 12 τ 4 (CH_R2) A" 64 τ 5 (CH_R1&O1-H); 11 τ(c=o3&c=o4) A'' 56 τ(o1-h); 16 τ(c=o3) A' 59 ν 14 (CC) A'' 36 τ(c=o3&c=o4); 34 τ 6 (CH_R2)

13 A'' 75 τ 1 (CCCC) A' 68 β 3 (CCC) A'' 57 τ 6 (CH_R2); 30 τ(c=o3&c=o4) A'' 79 τ 2 (CCCC) A' 79 β 4 (CCC) A' 71 β 5 (CCC) A' 61 β 6 (CCC) A" 83 τ 3 (CCCC) A' 56 β 7 (CCC) A'' 51 τ 4 (CCCC); 36 τ(o2-h) A" 59 τ(o2-h); 29 τ 4 (CCCC) A' 63 β 1 (CCO) A' 68 ν(quinone) A" 80 τ 5 (CCCC) A" 83 τ 6 (CCCC) A' 62 β 8 (CCC) A' 60 β 9 (CCC); 11 ν 10 (CC) A' 81 β 2 (CCO) A'' 91 τ 7 (CCCC) A' 79 ν(accordion) A' 81 β 10 (CCC) A'' 88 τ 8 (CCCC) A' 74 β 11 (CCC) A'' 83 τ 9 (CCCC) A" 87 τ 10 (CCCC) A" 82 τ 11 (CCCC) A" 86 τ 12 (CCCC) A" 90 τ(butterfly)

14 Table 2SI. The parameters of experimental FT-IR and FT-Raman spectra of alizarin in polycrystalline powder IR Raman Calculations Freq I INT (%) I max (%) FWHM Freq I INT (%) I max (%) FWHM Freq I REL,anh I anh INT (%) (%) a sh ??? sh sh

15 τ τ

16 Table 3SI. Definitions of the local coordinates for PED analysis of alizarin calculated at the B3LYP/aug-cc-pVDZ level. coor. coef. inter mode type Atom frag ment Geom. value Freq 1 Freq 2 No1 No2 No3 No4 PED % s STRE OH f s STRE 3 21 CH f CH s STRE 5 23 CH f CH CH CH s STRE 5 23 CH f CH CH s STRE 3 21 CH f CH OH s STRE 3 21 CH f CH OH s STRE 5 23 CH f CH CH CH s STRE 6 24 CH f CH s STRE OC f s STRE 17 9 OC f s STRE 2 3 CC f CC CC OC OC OC s STRE 1 2 CC f CC CC f f f Freq 3 Notati ν(o2-h ν s (CH_R ν s (CH_R ν a 1(CH_ ν a 1(O1- H&CH_R ν a 2(O1- H&CH_R ν a 2(CH_ ν a 3(CH_ ν(c=04 ν(c=03 ν 1 (CC) ν 2 (CC)

17 CC CC OC s STRE 2 3 CC f CC CC CC OC s STRE 4 14 CC f CC CC CC OC OC s STRE 2 3 CC f CC CC CC OC s BEND HCC f HCC HCC HCC s STRE 1 13 CC f CC CC CC OC OC s STRE 5 6 CC f CC CC CC CC s STRE 1 2 CC f CC CC CC CC s BEND HOC f s BEND HOC f s STRE 5 6 CC f CC CC f f f f f f f f f ν 3 (CC) ν 4 (CC) ν 5 (CC) β 1 (CH_R ν 6 (CC) ν 7 (CC) ν 8 (CC) β(o2-h β(o1-h ν 9 (CC)

18 CC CC CC s STRE 15 1 OC f s STRE 16 2 OC f s STRE CC f CC s BEND HOC f HCC HCC HCC s BEND HOC f HCC HCC HCC HCC s BEND HOC f HCC HCC HCC s BEND HCC f HCC HCC HCC HCC HCC HCC HCC s BEND HCC f HCC HCC HCC s BEND CCC f CCC s STRE 1 2 CC f CC CC CC CC CC CC CC CC CC f f f f f f f f f ν(c-o1 ν(c-o2 ν 10 (CC) β 2 (CH) β 3 (CH) β 4 (CH) β 5 (CH_R β 6 (CH) β 1 (CCC) ν 11 (CC)

19 OC s STRE 3 4 CC f CC CC CC CC OC s TORS HCCC 0.00 f HCCH 0.00 s STRE 4 14 CC f CC CC CC CC CC CC CC OC s TORS HCCH 0.00 f HCCH HCCC HCCC HCCC s TORS HCCH 0.00 f HCCC HCCC 0.00 s TORS HCCC 0.00 f HCCC HCCC HCCC 0.00 s BEND CCC f CCC CCC CCC CCC CCO s OUT OCCC 0.00 f s TORS HOCC f HOCC HCCO HCCC s TORS HOCC f s STRE 1 2 CC f f f f f f f ν 12 (CC) τ 1 (CH_R ν 13 (CC) τ 2 (CH) τ 3 (CH_R τ 4 (CH_R β 2 (CCC) τ(c=o3 τ 5 (CH_R H) τ(o1-h ν 14 (CC)

20 CC CC CC CC CC CC CC OC OC s OUT OCCC 0.00 f OCCC 0.00 s OUT CCCC 0.00 f TORS CCCC CCCC CCCC CCCC CCCC OUT OCCC OCCC 0.00 s BEND CCC f CCC CCC CCO CCC CCO s TORS HCCC f HCCC HCCC HCCC s TORS CCCC 0.00 f CCCC OUT OCCC OCCC OCCC 0.00 s BEND CCC f CCC CCC CCO CCO s BEND CCC f CCC s BEND CCC f CCO CCC CCC CCC f f f τ(c=o3 τ 1 (CCCC β 3 (CCC) τ 6 (CH_R τ 2 (CCCC β 4 (CCC) β 5 (CCC) β 6 (CCC)

21 s TORS CCCC 0.00 f CCCC CCCC CCCO CCCO OUT OCCC 0.00 s BEND CCC f CCC CCC CCC CCC CCC CCO CCC s TORS CCCC 0.00 f CCCC CCCC CCCO CCCO s TORS HOCC 0.00 f s BEND CCO f CCC CCC CCO s STRE 1 4 CC f CC CC s TORS CCCC 0.00 f CCCC CCCC CCCO CCCO CCCO s TORS CCCC 0.00 f CCCC 0.00 s BEND CCC f CCC CCC CCC CCO CCO CCO s BEND CCO f f f f τ 3 (CCCC β 7 (CCC) τ 4 (CCCC τ(o2-h β 1 (CCO) ν(quin τ 5 (CCCC τ 6 (CCCC β 8 (CCC) O1H... breaki β 9 (CCC)

22 CCC CCC CCC CCC CCC CCC CCO CCO s BEND CCO f CCO CCO s OUT CCCC 0.00 f TORS CCCC CCCC CCCO CCCO CCCO CCCC CCCO CCCO OUT OCCC 0.00 s STRE 2 13 CC f CC CC CC CC CC s BEND CCO f CCC CCC CCC CCC CCC CCO CCO s TORS CCCC 0.00 f CCCC CCCC CCCC CCCO s BEND CCC f CCC CCC s TORS CCCC f CCCC CCCO CCCO β 2 (CCO) τ 7 (CCCC ν(acco β 10 (CCC τ 8 (CCCC β 11 (CCC τ 9 (CCCC

23 s TORS CCCO 0.00 f CCCC CCCC CCCO CCCC CCCO s TORS CCCC 0.00 f CCCC CCCC CCCC CCCC CCCO CCCO s TORS CCCC 0.00 f CCCC CCCC CCCC CCCO CCCC 0.00 s TORS CCCC f CCCC CCCC CCCO CCCC 0.00 τ 10 (CCC τ 11 (CCC ( f ( g τ 12 (CCC τ(butt