Supporting Information for Publication

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1 Supporting Information for Publication Structure-Spectra Correlations in Anilate Complexes with Picolines Katarzyna Łuczyńska,* ab Kacper Drużbicki, bc Krzysztof Lyczko a and Jan Cz. Dobrowolski ad. a Institute of Nuclear Chemistry and Technology, Dorodna 16, , Warsaw, Poland. k.luczynska@ichtj.waw.pl b Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, , Dubna, Russia. c Faculty of Physics, Adam Mickiewicz University, Umultowska 85, Poznan, Poland. d National Medicines Institute, 30/34 Chełmska Street, , Warsaw, Poland. Contents: Table S1. Crystallographic data and structure refinement parameters for the studied set of picoline-anilic acid complexes. Table S2. The most prominent interatomic distances (r) in ClA : 2-MP (1:1); BrA : 2-MP (1:1); ClA : 3-MP (1:1) and BrA : 3-MP (1:2) form II. The results are collected from X-Ray diffraction at 100K (XRD) and from Born-Oppenheimer NVT MD simulations (AIMD) at 75, 225 and 375K, respectively. Table S3. Collection of experimental ( 13 C CP/MAS NMR at 298K) and theoretical (PBE) chemical shifts (δ [ppm]) for ClA : 2- MP (1:1); BrA : 2-MP (1:1) ClA : 3-MP (1:1) and BrA : 3-MP (1:2), along with a detailed assignment. Table S4. The collection of the FT-IR, FT-RS and INS wavenumbers observed experimentally in the range above 120 cm -1 presented against the results of theoretical plane-wave DFT calculations (CASTEP PBE), performed under the experimental 293K cell-volume. The theoretical wavenumbers affected by the LO-TO splitting term are given in parentheses. The phonons symmetry defined by A u and A g species. Table S5. The collection of the FT-IR, FT-RS and INS wavenumbers observed experimentally in the range above 120 cm -1 presented against the results of theoretical plane-wave DFT calculations (CASTEP PBE), performed under the experimental 293K cell-volume. The theoretical wavenumbers affected by the LO-TO splitting term are given in parentheses. The phonons symmetry defined by A u and A g species. Table S6. The collection of the FT-IR, FT-RS and INS wavenumbers observed experimentally in the range above 120 cm -1 presented against the results of theoretical plane-wave DFT calculations (CASTEP PBE), performed under the experimental 293K cell-volume. The theoretical wavenumbers affected by the LO-TO splitting term are given in parentheses. The phonons symmetry defined by A u and A g species. Table S7. Collection of the thermal stability limits for each powder sample studied. Figure S1. Hirshfeld surface analysis of the intermolecular interactions in ClA : 2MP (1:1) and BrA : 2MP (1:1) complexes. Figure S2. Hirshfeld surface analysis of the intermolecular interactions in ClA : 3MP (1:1) and BrA : 3MP (1:2), Form II complexes. Figure S3. The fingerprint plots from Hirshfeld surface analysis of the intermolecular interactions in ClA : 2MP (1:1); BrA : 2MP (1:1); ClA : 3MP (1:1) and BrA : 3MP (1:2), Form II complexes. Figure S4. Percentage contributions from particular close contacts derived from Hirshfeld surface analysis of the intermolecular interactions in ClA : 2MP (1:1) and BrA : 2MP (1:1) complexes. 1

2 Figure S5. Percentage contributions from particular close contacts derived from Hirshfeld surface analysis of the intermolecular interactions in ClA : 3MP (1:1) and BrA : 3MP (1:2), Form II complexes. Figure S6. Room temperature FT-IR spectra of ClA : 2-MP (1:1); BrA : 2-MP (1:1) ClA : 3-MP (1:1) and BrA : 3-MP (1:2), presented along with theoretical spectra calculated with DFPT (fixed-cell PBE) as based on the crystallographic and hypothetical structures. The transverse-optical (TO) components are given as black lines, while longitudinal-optical (LO) spectra are given as red curves as averaged over multiple grain orientations. Please note that the highest-wavenumber range is supplemented with proton power spectra (NH and OH) from BOMD simulations. Figure S7. Room temperature FT-RS spectra of ClA : 2-MP (1:1); BrA : 2-MP (1:1) ClA : 3-MP (1:1) and BrA : 3-MP (1:2), presented along with theoretical quasi-harmonic spectra calculated with DFPT (transverse-optical components in fixed-cell PBE) as based on the crystallographic and hypothetical structures. Figure S8. Thermogravimetry (top) and differential scanning calorimetry (bottom) curves for 2-Methylpyridinium 2,5- dichloro-4-hydroxy-3,6-dioxocyclohexa-1,4-diene-1-olate (ClA : 2-MP 1:1) complex. Figure S9. Thermogravimetry (top) and differential scanning calorimetry (bottom) curves for 2-Methylpyridinium 2,5- dibromo-4-hydroxy-3,6-dioxocyclohexa-1,4-diene-1-olate (BrA : 2-MP 1:1) complex. Figure S10. Thermogravimetry (top) and differential scanning calorimetry (bottom) curves for 3-Methylpyridinium 2,5- dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-diolate 2,5-dichloro-3,6-dihydroxycyclohexa-2,5-diene-1,4-dione-1,4-diolate (ClA : 3-MP 1:1) complex. Figure S11. Thermogravimetry (top) and differential scanning calorimetry (bottom) curves for 3-Methylpyridinium 2,5- dibromo-3,6-dioxocyclohexa-1,4-diene-1,4-diolate (BrA : 3-MP 1:2) complex, polymorphic form I. Figure S12. Thermogravimetry (top) and differential scanning calorimetry (bottom) curves for 3-Methylpyridinium 2,5- dibromo-3,6-dioxocyclohexa-1,4-diene-1,4-diolate (BrA : 3-MP 1:2) complex, polymorphic form II. 2

3 Table S1. Crystallographic data and structure refinement parameters for the studied set of picoline-anilic acid complexes. Synthon :B:A: A: B: :B:A: A: B: :(B:A:B):A B:A:B B:A:B Molecular formula C 12H 9Cl 2NO 4 C 12H 9Br 2NO 4 C 24H 18Cl 4N 2O 8 C 18H 16Br 2N 2O 4 C 18H 16Br 2N 2O 4 Acronym ClA : 2-MP (1:1) BrA : 2-MP (1:1) ClA : 3-MP (1:1) BrA : 3-MP (1:2) I BrA : 3-MP (1:2) II Formula weight (g mol -1 ) T/K λ [CuKa] (Å) Crystal system triclinic triclinic triclinic monoclinic monoclinic Space group P -1 P -1 P -1 P2 1/c P2 1/c a (Å) (5) (6) (3) (3) (3) b (Å) (8) (7) (6) (3) (3) c (Å) (5) (7) (9) (4) (5) α ( ) (6) (6) (6) β ( ) (5) (7) (5) (4) (4) γ ( ) (6) (7) (5) Volume (Å) (7) (8) (6) (5) (6) Z Dc (g cm -3 ) μ (mm -1 ) F (000) Crystal size (mm) Ɵ range for data collection ( ) Reflections collected Independent reflections R int Absorption correction multi-scan multi-scan multi-scan multi-scan multi-scan Transmission, Tmin/Tmax / / / / / Data/restraints/parameters 2118/0/ /0/ /0/ /0/ /0/123 Goodness of fit on F Final R indices [I > 2s(I)] R indices (all data) R 1 = ; wr 2 = R 1 = ; wr 2 = R 1 = ; wr 2 = R 1 = ; wr 2 = R 1 = ; wr 2 = R 1 = ; wr 2 = R 1 = ; wr 2 = R 1 = ; wr 2 = R 1 = ; wr 2 = R 1 = ; wr 2 = Largest diff. peak/hole (e Å -3 ) / / / / /

4 Table S2. Most prominent interatomic distances (r) in ClA : 2-MP (1:1); BrA : 2-MP (1:1); ClA : 3-MP (1:1) and BrA : 3-MP (1:2) form II. The results are collected from X-Ray diffraction at 100K (XRD) and from Born-Oppenheimer NVT MD simulations (AIMD) at 75, 225 and 375K, respectively. Compound / Coordinate ClA : 2-MP (1:1) BrA : 2-MP (1:1) ClA : 3-MP (1:1) BrA : 3-MP (1:2) II XRD AIMD XRD AIMD XRD AIMD XRD AIMD 100K 75K 225K 375K 100K 75K 225K 375K 100K 75K 225K 375K 100K 75K 225K 375K r(oh) [Å] r(oh O) [Å] r(nh) [Å] r(nh O) [Å] r(ch O) [Å] C(6)H O(4) C(6)H O(2) C(12)H O(2) C(2)H O(3) C(5)H O(2) C(4)H O(4) H H [Å] - C(5)H C(6)H Table S3. Collection of experimental ( 13 C CP/MAS NMR at 298K) and theoretical (PBE) chemical shifts (δ [ppm]) for ClA : 2-MP (1:1); BrA : 2- MP (1:1) ClA : 3-MP (1:1) and BrA : 3-MP (1:2), along with a detailed assignment. ClA : 2-MP (1:1) BrA : 2-MP (1:1) Cla : 3-MP (1:1) Bra : 3-MP (1:2) [P2 1/c] 298K [P-1] 298K [P-1] Assignment 298K [P-1] [P1] Assignment 298K I II Assignment δ exp δ PBE δ exp δ PBE No. Unit δ exp δ PBE PBE No. Unit δ exp δ PBE δ PBE No. Unit C(11) 13 C=O /176.9 C(12) 13 C=O C8 13 C=O HN C(12) C=O HN /170.8 C(9) C=O HN C9 C=O HN C(8) C=O HO /164.9 C(8) C=O HO C(9) 13 C-OH O /158.2 C(11) C-OH O C(2) 13 C-CH /148.4 C(4) 13 C-H C4 13 C-H C(4) 13 C-H /142.6 C(2) N- 13 C-H O C2 N- 13 C-H O= C(6) N- 13 C-H O= /141.9 C(3) 13 C-CH C3 13 C-CH C(3) 13 C-H /135.3 C(6) N- 13 C-H O= C6 N- 13 C-H O= C(5) 13 C-H /128.3 C(5) 13 C-H C5 13 C-H C(10) 13 C-X /114.0 C(10) 13 C-X C(7) 13 C-X /112.1 C(7) 13 C-X C7 13 C-X C(1) 13 CH /19.7 C(1) 13 CH C1 δ ref ref δ ref δ ref a a a a CH 3 4

5 ClA : 2MP (1:1) a-axis b-axis c-axis BrA : 2MP (1:1) Figure S1. Hirshfeld surface analysis of the intermolecular interactions in ClA : 2MP (1:1) and BrA : 2MP (1:1) complexes. 5

6 ClA : 3MP (1:1) a-axis b-axis c-axis BrA : 2MP (1:1) Figure S2. Hirshfeld surface analysis of the intermolecular interactions in ClA : 3MP (1:1) and BrA : 3MP (1:2), Form II complexes. 6

7 ClA : 2MP (1:1) ClA : 3MP (1:1) ClA 2MP ClA 3MP BrA : 2MP (1:1) BrA : 3MP (1:2) ClA 2MP BrA 3MP Figure S3. The fingerprint plots from Hirshfeld surface analysis of the intermolecular interactions in ClA : 2MP (1:1); BrA : 2MP (1:1); ClA : 3MP (1:1) and BrA : 3MP (1:2), Form II complexes. 7

8 X-X X-O X-C X-H O-C O-H C-C C-H ClA:2MP (1:1) BrA:2MP (1:1) ClA:3MP (1:1) BrA:3MP (1:2) II BrA:3MP (1:2) II ClA:3MP (1:1) BrA:2MP (1:1) ClA:2MP (1:1) H-H Figure S4. Percentage contributions from particular close contacts derived from Hirshfeld surface analysis of the intermolecular interactions in ClA : 2MP (1:1) and BrA : 2MP (1:1) complexes ClA:2MP (1:1) BrA:2MP (1:1) ClA:3MP (1:1) BrA:3MP (1:2) II X-H O-C O-H C-C C-H H-H N-H BrA:3MP (1:2) II ClA:3MP (1:1) BrA:2MP (1:1) ClA:2MP (1:1) Figure S5. Percentage contributions from particular close contacts derived from Hirshfeld surface analysis of the intermolecular interactions in ClA : 3MP (1:1) and BrA : 3MP (1:2), Form II complexes. 8

9 Figure S6. Room temperature FT-IR spectra of ClA : 2-MP (1:1); BrA : 2-MP (1:1) ClA : 3-MP (1:1) and BrA : 3-MP (1:2), presented along with theoretical spectra calculated with DFPT (fixed-cell PBE) as based on the crystallographic and hypothetical structures. The transverse-optical (TO) components are given as black lines, while longitudinal-optical (LO) spectra are given as red curves as averaged over multiple grain orientations. Please note that the highest-wavenumber range is supplemented with proton power spectra (NH and OH) from BOMD simulations. 9

10 Figure S7. Room temperature FT-RS spectra of ClA : 2-MP (1:1); BrA : 2-MP (1:1) ClA : 3-MP (1:1) and BrA : 3-MP (1:2), presented along with theoretical quasi-harmonic spectra calculated with DFPT (transverse-optical components in fixed-cell PBE) as based on the crystallographic and hypothetical structures. 10

11 Table S4 The collection of the FT-IR, FT-RS and INS wavenumbers observed experimentally in the range above 120 cm -1 presented against the results of theoretical plane-wave DFT calculations (CASTEP PBE), performed under the experimental 293K cell-volume. The theoretical wavenumbers affected by the LO-TO splitting term are given in parentheses. The phonons symmetry defined by A u and A g species ClA : 2-MP (1:1) BrA : 2-MP (1:1) ClA : 3-MP (1:1) BrA : 3-MP (1:2) ra : -1 ] Tentative Band 298K PBE 298K PBE 298K PBE 298K PBE Assignment [Compound No.] IR RS IR RS IR RS IR RS [A [A [A u] [A u] [A g] [A g] [A u] [A u] [A g] [A g] [A u] [A u] [A u/b u g] [A g] [A u] [A g] ] g/b g] ν(oh)[1 2] ν(ch)[1 2] ν(ch)[3] / ν ass(ch 3)[4] ν ss(ch 3)[1-4] ν(nh)[1-4] ν(oh)[3] Difference Bands: ν(nh)[1,2,4] / ν(oh)[3] δ(nh O); ν(c=o)[1,2] / ν(c=o); δ(oh O)[3] / δ(nh O); ν(c=c) [MP] ; ν(c=o)[4] δ(nh O); ν(c=o); ν(c=c) [MP] [1,2,4] / δ(nh O); δ(oh O); ν(c=o); ν(c=c) [MP] [3] δ(oh O); ν(c=c) [XA] [1-3] / ν ss(c=c) [XA] [4] δ(nh O); ν(c=o); ν(c=c) [MP] [4] δ(nh O); ν(c=c) [XA] ; ν(c=c) [MP] ; β(ch)[1,2,4] / δ(nh O); δ(oh O); ν(c=c) [XA] ; ν(c=c) [MP] ; β(ch)[3] δ(nh O); δ(oh O); ν(c=c) [XA] ; β(ch)[1-4] β(ch); δ as(ch 3); β(nh)[1-2] δ as(ch 3); β(ch)[1-4] β(ch); δ as(ch 3)[1-2] δ ss(ch 3); ν(c=c) [XA] ; δ(oh O)[3] / δ ss(ch 3); β(ch); δ(nh O)[4] δ(oh O); ν(c=c) [XA] [1-2] / δ(nh O); ν(c=c) [XA] [4] ν(c=c) [XA] [1-2] / ν(c=c) [XA] ; δ ss(ch 3); δ(oh O)[3] δ ss(ch 3)[1-2] / δ ss(ch 3); ν(c=c) [MP] [3] δ(oh O); ν(c=c) [XA] ; β(ch); δ(nh O)[3] / ν(c=c) [XA] ; β(ch); δ(nh O)[4] δ(oh O); ν(c-o) [XA] [1-2] / δ(oh O); ν(c-o) [XA] ; ν(c=c) [XA] [3] δ(nh O); β(ch)[4] δ(oh O); ν(c=c) [XA] [3] / ν(c=c) [XA] ; β(ch)[4] δ(nh O); δ(oh O); β(ch); ν(c=c) [XA] [1,2,3] δ(nh O); β(ch); ν(c-o) [XA] ; ν(c=c) [XA] ; ν(c-x) [XA] [1-2] δ(nh O); δ(oh O); β(ch); ν(c=c) [XA] [1,2] δ(oh O); δ(nh O); β(ch); ν(c=c) [XA] ; ν(c-x) [XA] [3] / δ(nh O); β(ch); ν(c=c) [XA] ; ν(c-x) [XA] [4] ν(c-ch 3); β(ch)[4] δ(oh O); ν(c-ch 3); β(ch); ν(c=c) [XA] [1-3] δ(oh O); β(ch)[2-3] δ(oh O)[1,3] / δ(oh O); β(ch)[2] γ(nh O); β(ch)[4] β(ch)[1] δ(oh O); ν(c-x) [XA] [1-2] γ(nh O); γ(oh O); β(ch)[3] β(ch)[4] γ(nh O); β(ch)[1-2] γ(nh O)[1-2] / γ(nh O); γ(oh O)[3] γ(oh O); γ(nh O)[3] β [MP] [1-4] ρ(ch 3); γ(ch)[1-4] ρ(ch 3); γ(ch); β [MP] [1-4] ρ(ch 3); γ(ch); β [MP] [1-2] ρ(ch 3); γ(ch); β [MP] [1-2] / ρ(ch 3); β [MP] [3] / ρ(ch 3); γ(ch); β [MP] [4] β [XA] ; β(cco) [XA] [3] 11

12 Table S5. The collection of the FT-IR, FT-RS and INS wavenumbers observed experimentally in the range above 120 cm -1 presented against the results of theoretical plane-wave DFT calculations (CASTEP PBE), performed under the experimental 293K cell-volume. The theoretical wavenumbers affected by the LO-TO splitting term are given in parentheses. The phonons symmetry defined by A u and A g species ClA : 2-MP (1:1) BrA : 2-MP (1:1) ClA : 3-MP (1:1) BrA : 3-MP (1:2) ν [cm -1 ] Tentative Band 298K 10K DFPT 298K 10K DFPT 298K 10K DFPT 298K 10K DFPT Assignment [Compound No.] IR RS IR RS INS [A [A u] [A u] [A g] g] [A u] [A INS [Au] [Ag] IR RS IR RS [A INS [A g] [A u] [A u] [A g] INS u [A g g] [A u] [A g] /B u] /B g] γ(ch); ρ(ch ); β [XA] ; β(cco) [XA] [1] / β [XA] ; β(cco) [XA] [2] / ρ(ch 3); β [MP] [4] β [XA] ; β(cco) [XA] [1] / γ(ch); ρ(ch 3)[2] [u] [g] γ(ch); ρ(ch 3)[1,3,4] [u] 895 [u ] [g] 902 γ(oh O)[1,2] / γ(ch); ρ(ch 3)[3] [g] [g] γ(ch); ρ(ch 3)[1,2,4] / ν(c-x) [XA] [3] 843 [g] [g] γ(oh O)[1,2] / ν(c-x) [XA] [3] β [XA] Trigonal [1,3] [u] β [MP] Trigonal ; ν(c-ch 3)[1] / β [MP] Trigonal ; ν(c-ch 3); ν(c-x) [XA] [2] [u] β [MP] Trigonal ; ν(c-ch 3)[2] / β [MP] ; γ(ch)[3] [u] [u] β [MP] ; ν(c-ch 3); ν(c-x) [XA] [2] / β [MP] ; ν(c-ch 3)[4] / γ(ch); ρ(ch 3); β [XA] [3] β [XA] Trigonal [2] / β [MP] ; ν(c-ch 3)[4] [u] 788 γ [XA] [1,2] / γ(ch); ρ(ch 3)[4] β [XA] Twist [1] / γ [XA] [3] / β [XA] Trigonal [4] 762 [g] [g] γ(ch); ρ(ch 3)[1,2] / β [XA] Twist [3] / ν(c-x) [XA] [4] γ(ch)[1,2] γ [XA] [1,2] / β [XA] Twist [4] [u] [u] γ [MP] [1,2] [g] [u] γ(ch)[3,4] [u] [u] [u] [g] δ(cnc)[1-4] β [XA] Trigonal [1] [g] γ [XA] [1-4] β [XA] Quadratic [3-4] β [XA] Trigonal [3] [u] [g] [u] β [MP] Quadratic ; β [XA] Quadratic [1-3] β [XA] [2] [g] 527 γ [XA] [1-2] / β [XA] Quadratic ; γ [XA] [3] / β [MP] Quadratic [4] β [XA] [4] γ [XA] [3-4] [g] [g] [u] [u] γ [MP] [1-4] δ(cc=o)[3] 409 [u] 407 γ [MP] [3] β [XA] ; γ [MP] [1-3] 413 [u] 404 γ [MP] [4] [u ] γ [MP] ; δ(cc=o)[1,2,4] 398 [u] [u] γ [MP] [1] / β [XA] ; γ [MP] [2] / γ [MP] ; δ(cc=o)[4] γ [MP] ; δ(cc=o)[1] / β [XA] Quadratic [3] [g] [u] [u] δ(cc=o); δ(coh); Lib.(in-plane) [MP] ; δ(c-c-ch 381 3) [MP] [1-2] / δ(cc=o); δ(coh)[3] / β [XA] [4] [g] [u] 335 δ(coh); δ(c-c-ch 3) [MP] [1-2] / δ(cc=o); δ(c-c-ch 3) [MP] [3] / Lib.(in-plane) [MP] ; δ(c-c-ch 3) [MP] [4] γ [XA] [1] [g] [u] δ(cc=o); δ(cc-o)[1-2] / γ [XA] [3] / Lib. [XA] [4] [g] [g] 283 γ [XA] [2]; β [XA] Quadratic ; γ [XA] [3] [u] βtwist[xa] [1,3] / γ [MP] ; Lib.(out-of-plane) [MP] ; γ(c-ch 3) [MP] [2] / γ [XA] [4] 236 [g] [g] [u] 222 Lib.(out-of-plane) [MP] ; γ(c-ch 3) [MP] [1-4] [g] δ(cc-x) [XA] [1,3-4] γ [XA] [1,4] β [XA] Quadratic [2,4] [g] [u] [u] 183 γ [XA] [2] / δ(cc-x) [XA] [3] / γ [XA] ; τ(cccc) [MP] [4] δ(cc-x) [XA] ; τ(ch 3)[2] / τ(ch 3)[3] Lib.(out-of-plane) [MP] [2] 150 [u] [g] [u] τ(ch 3)[1] [g] τ(ch 3); Lib.(out-of-plane) [MP] [1,2,3] [u] [g] 130 τ(ch 3); ν(n O)[1,3] / τ(ch 3); Lib.(out-of-plane) [MP] [4] [u] 125 γ(c=o) [XA] ; Lib.(out-of-plane) [MP] [3,4] [u] [g] γ(c=o) [XA] ; Lib.(out-of-plane) [MP] [1] / ν(n O); τ(ch 122 3)[2,3] / γ(c=o) [XA] ; ν(n O); Lib.(out-of-plane) [MP] [4] ν(n O); Lib.(out-of-plane) [MP] ; Lib.(out-of-plane) [XA] [4] 12

13 Table S6. The collection of the FT-IR, FT-RS and INS wavenumbers observed experimentally in the range above 120 cm -1 presented against the results of theoretical plane-wave DFT calculations (CASTEP PBE), performed under the experimental 293K cell-volume. The theoretical wavenumbers affected by the LO-TO splitting term are given in parentheses. The phonons symmetry defined by A u and A g species. ClA : 2-MP (1:1) BrA : 2-MP (1:1) ClA : 3-MP (1:1) BrA : 3-MP (1:2) Form II P -1 P -1 P-1 P1 P2 1/c c11: -1 ] Tentative ν [cm -1 ] Tentative ν [cm -1 ] Tentative ν [cm -1 ] Tentative ν [cm -1 ] Tentative 298K 10K DFPT Band 298K 10K DFPT Band 298K 10K DFPT Band Band 298K 10K DFPT Band DFPT THz INS [A u/a g] Assignment THz INS [A u/a g] Assignment THz INS [A u/a g] Assignment Assignment THz INS [A u/a g] Assignment [Au] τ(n O)[τ(MP)] [Au] γ(c=o)[xa] ; Lib.(out-of-plane) [MP] γ(c=o) [XA] / ν(n O) [Au] τ(n O)[τ(MP)] / τ(ch 3) / Lib.(in-plane) [MP] / [Ag] Lib.(in-plane) [MP] [Au] γ(c=o)[xa] ; γ(xa); ; ν(o O); ν(o O) Lib.(in-plane) [MP] [Au] γ[xa] / τ(ch 3) / Lib.(in-plane) [MP] [Au] Lib.(out-ofplane) [XA] [Au] τ(n O)[τ(MP)] [Au] γ(c=o)[xa] ; γ(xa); ν(o O) Lib.(in-plane) [MP] Lib.(in-plane) [MP] [Au] γ(n O) / τ(ch ; τ(ch 3) / ν(o O) 3) [Au] Lib.(in-plane) [MP] [Au] Lib.(in-plane)[MP] [Au] ν(n O) / Transl. [MP] Lib.(out-of-plane) [XA] c-axis 89.2 / γ(xa XA) / Lib.(in-plane) [MP] [Au] γ(c=o) [XA] / γ(n O) / τ(ch 3) [Au] [Au] ν(o O) / Transl. [XA] Lib.(in-plane) [MP] / γ c-axis 79.6 [XA] [Au] γ(c=o) [XA] / τ(ch 3) γ(xa XA) [Au] γ(n O) / Lib.(in-plane) [MP] Transl. [MP] c-axis [Au] Lib.(out-of-plane) [MP] [Au] τ(n O) / τ(xa XA) [Au] τ(n O)[τ(MP)] / ν(n O) [Au] Lib.(in-plane) [MP] Lib.(out-ofplane) [XA] [Au] γ [XA] ; Lib.(in-plane) [MP] [Au] Transl.[XA] c-axis Lib.(in-plane) [XA] [Au] / Transl. [XA] [Au] b-axis / ν(o O) / ν(n O) / ν(o O) / ν(o O) [Au] [Ag] Lib.(out-ofplane) [MP] Lib.(in-plane) [MP] / τ(xa XA) [Au] Transl. [MP] c-axis [Au] Transl. [MP] c-axis [Au] γ(n O) / Lib.(in-plane) [MP] 65.0 Lib.(out-of-plane) [XA] / Lib.(in-plane) [MP] [Au] Transl. [XA] b-axis [Au] / ν(o O) τ(n O)[τ(MP)] / γ [XA] [Au] Lib.(in-plane) [XA] [Au] Lib.(in-plane) [MP] [Au] Lib.(in-plane) [MP] / ν(o O) 54.8 Lib.(in-plane) [MP] [Au] [Au] Lib.(in-plane) [MP] [Au] Lib.(in-plane) [XA] 27 Acoustic 23 Acoustic 24 Acoustic Acoustic 27 Acoustic NOTES Thermal Analysis Thermal stability of the powder samples was examined in argon atmosphere at the heating rate of 5 o C/min, using a TA SDT Q600 thermogravimetric analyzer. The calorimetric analysis was performed with a TA DSC Q2000 calorimeter, varying the temperature from 100K up to the decomposition point. Large sample along with the heating/cooling rate of 20K/min were used in search of weak second order phase transitions. No phase transitions were observed and these results are collected in the supplementary materials. Table S7. Collection of the thermal stability limits for each powder sample studied. Compound ClA : 2-MP (1:1) BrA : 2-MP (1:1) ClA : 3-MP (1:1) BrA : 3-MP (1:2) Form I BrA : 3-MP (1:2) Form II Decomposition Point 129 o C 125 o C 123 o C 49 o C 84 o C 13

14 Fig. S8. Thermogravimetry (top) and differential scanning calorimetry (bottom) curves for 2-Methylpyridinium 2,5-dichloro-4-hydroxy-3,6- dioxocyclohexa-1,4-diene-1-olate (ClA : 2-MP 1:1) complex. 14

15 Fig. S9. Thermogravimetry (top) and differential scanning calorimetry (bottom) curves for 2-Methylpyridinium 2,5-dibromo-4-hydroxy-3,6- dioxocyclohexa-1,4-diene-1-olate (BrA : 2-MP 1:1) complex. 15

16 Fig. S10. Thermogravimetry (top) and differential scanning calorimetry (bottom) curves for 3-Methylpyridinium 2,5-dichloro-3,6- dioxocyclohexa-1,4-diene-1,4-diolate 2,5-dichloro-3,6-dihydroxycyclohexa-2,5-diene-1,4-dione-1,4-diolate (ClA : 3-MP 1:1) complex. 16

17 Fig. S11. Thermogravimetry (top) and differential scanning calorimetry (bottom) curves for 3-Methylpyridinium 2,5-dibromo-3,6- dioxocyclohexa-1,4-diene-1,4-diolate (BrA : 3-MP 1:2) complex, polymorphic form I. 17

18 Fig. S12. Thermogravimetry (top) and differential scanning calorimetry (bottom) curves for 3-Methylpyridinium 2,5-dibromo-3,6- dioxocyclohexa-1,4-diene-1,4-diolate (BrA : 3-MP 1:2) complex, polymorphic form II. 18