Patrycja Miszczyk, Dorota Wieczorek, Joanna Gałęzowska, Błażej Dziuk, Joanna Wietrzyk and Ewa Chmielewska. 1. Spectroscopic Data.

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; doi:10.3390/molecules22020254 S1 of S23 Supplementary Materials: Reaction of 3-Amino-1,2,4-Triazole with Diethyl Phosphite and Triethyl Orthoformate: Acid-Base Properties and Antiosteoporotic Activities of the Products Patrycja Miszczyk, Dorota Wieczorek, Joanna Gałęzowska, Błażej Dziuk, Joanna Wietrzyk and Ewa Chmielewska 1. Spectroscopic Data N HN N NH PO 3 H 2 Compound 1 H 2 O 3 P 4.05 4.00 3.95 3.90 3.85 3.80 f1 (ppm) 3.75 3.70 3.65 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 f1 (ppm) 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 Figure S1. 1 H-NMR spectrum of compound 1.

S2 of S23 100 95 90 85 80 75 70 65 60 55 50 f1 (ppm) 45 40 35 30 25 20 15 10 5 0-5 Figure S2. 31 P-NMR spectrum of compound 1. 57 56 55 54 53 52 51 f1 (ppm) 50 49 48 180 170 160 150 140 130 120 110 100 90 f1 (ppm) 80 70 60 50 40 30 20 10 0 Figure S3. 13 C-NMR spectrum of compound 1.

S3 of S23 Figure S4. HRMS spectrum of compound 1. Figure S5. IR spectrum of compound 1.

Molecules 2017, 22, 254 Figure S6. MS spectrum with fragmentation, for compound 1 (method of ionization ( )). Figure S7. MS spectrum with fragmentation, for compound 1 (method of ionization (+)). S4 of S23

S5 of S23 Compound 2: N N N N H PO 3 H 2 PO 3 H 2 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 f1 (ppm) 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 Figure S8. 1 H-NMR spectrum of compound 2. 15.8233 Figure S9. 31 P-NMR spectrum of compound 2..

S6 of S23 57 56 55 54 f1 (ppm) 53 52 51 190 180 170 160 150 140 130 120 110 100 90 f1 (ppm) 80 70 60 50 40 30 20 10 0 Figure S10. 13 C-NMR spectrum of compound 2. Figure S11. HRMS spectrum of compound 2.

Molecules 2017, 22, 254 S7 of S23 Figure S12. IR spectrum of compound 2. Figure S13. MS spectrum with fragmentation, for compound 2 (method of ionization ( )).

S8 of S23 Figure S14. MS spectrum with fragmentation, for compound 2 (method of ionization (+)). D H N N N NH PO 3 H 2 Compound 2 after prolonged (several days) storage in D2O/NaOD solution: H 2 O 3 P 3.64 3.60 3.56 f1 (ppm) 3.52 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 f1 (ppm) 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0-0.5-1.0 Figure S15. 1 H-NMR spectrum of compound 2 after prolonged (several days) storage in D2O/NaOD solution.

S9 of S23 1.00 19.08 2.19 2.95 1.00 2.61 1.18 3.40 1.00 19.08 2.19 2.95 1.00 21.7335 21.5473 17.5800 16.7838 15.8957 14.1132 13.9269 21.7335 21.5473 17.5800 16.7838 15.8957 14.1132 13.9269 10.0314 6.3779 4.2104 Figure S16. 31 P-NMR spectrum of a representative example of crude reaction mixture. 0.07 0.02 0.03 0.54 1.00 0.08 0.15 0.42 0.20 0.57 0.36 0.68 1.74 0.42 0.58 0.94 0.40 0.69 0.49 0.43 8.2701 7.7908 7.7316 7.4702 7.4193 7.3491 7.2434 4.0625 4.0438 4.0256 4.0071 3.9600 3.9140 3.8674 3.8586 3.8407 3.8225 3.8044 3.7912 3.7702 3.7519 3.7194 3.6993 3.6911 3.6703 3.6514 3.6333 3.6239 3.5841 3.5348 3.4968 3.4855 3.4745 3.4566 3.1535 3.1353 3.1172 3.0992 1.3602 1.3420 1.3238 1.2528 1.2346 1.2210 1.2029 1.1943 1.1759 1.1579 1.0928 1.0747 1.0566 1.0125 0.9948 0.9770 0.7871 0.7695 0.7518 Figure S17. 1 H-NMR spectrum of a representative example of crude reaction mixture.

S10 of S23 0.07 0.02 0.03 0.54 1.00 0.08 0.15 8.2701 7.7908 7.7316 7.4702 7.4193 7.3491 7.2434 Figure S18. 1 H-NMR spectrum of a representative example of crude reaction mixture (aromatic range). 0.42 0.20 0.57 0.36 0.68 1.74 0.42 4.0625 4.0438 4.0256 4.0071 3.9600 3.9140 3.8674 3.8586 3.8407 3.8225 3.8044 3.7912 3.7702 3.7519 3.7194 3.6993 3.6911 3.6703 3.6514 3.6333 3.6239 3.5841 3.5348 3.4968 3.4855 3.4745 3.4566 3.1535 3.1353 3.1172 3.0992 Figure S19. 1 H-NMR spectrum of a representative example of crude reaction mixture (aliphatic (ethyl) range).

S11 of S23 0.58 0.94 0.40 0.69 0.49 0.43 1.3602 1.3420 1.3238 1.2528 1.2346 1.2210 1.2029 1.1943 1.1759 1.1579 1.0928 1.0747 1.0566 1.0125 0.9948 0.9770 0.7871 0.7695 0.7518 Figure S20. 1 H-NMR spectrum of a representative example of crude reaction mixture (aliphatic (methyl) range). H-P correletion {7.2379,3.6996} {5.8180,3.7032} 2 4 6 {3.9446,9.5243} {3.8588,9.5288} 8 10 {3.7771,13.4717} {3.6849,13.4064} 12 {3.6910,15.4195} {3.5689,17.0738} {2.9658,16.2325} 14 16 {3.4747,17.0684} 18 {3.7730,21.1697} {3.6864,21.1823} {1.0208,20.1103} 20 22 24 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 f2 (ppm) 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 Figure S21. H-P correlation spectrum of a representative example of crude reaction mixture.

S12 of S23 Figure S22. HRMS spectrum of a representative example of crude reaction mixture. 2. Spectroscopic Titrations Compound 1 Compound 2 1.0 ph range: 1.57-11.75 increases with ph increase 1.0 ph range 2.04-11.18 0.8 decreases with ph increase 0.8 (A) Absorbance 0.6 0.4 increases with ph increase Absorbance 0.6 0.4 increases with ph increase shifts with ph increase 0.2 0.2 0.0 210 220 230 240 250 260 270 Wavelength [nm] 0.0 210 220 230 240 250 260 270 Wavelength [nm] (B) Molar Absorbance 20000 15000 10000 5000 L HL H 2 L H 3 L H 4 L H 5 L not detected Molar Absorbance 10000 8000 6000 4000 2000 L not detected HL H 2 L H 3 L H 4 L H 5 L not detected 0 210 220 230 240 250 260 270 Wavelength [nm] 0 210 220 230 240 250 260 270 Wavelength [nm] Figure S23. (A) Absorption spectrophotometric titration vs. ph of free compounds plotted in chosen ph values; (B) electronic spectra of species calculated in HypSpec.

S13 of S23 shift 31 P [ppm] 17 16 15 14 13 12 shift 1 H [ppm] 8.50 8.25 8.00 7.75 7.50 7.25 2 4 6 8 10 12 14 2 4 6 8 10 12 14 ph * ph * (A) (B) Figure S24. 31 P (A) and 1 Haromatic (B) NMR titration curves as a function of ph performed for compound 1. Concentration of the compound: [L] = 4 10 2. * not corrected for D2O. 3. Relevant Crystallographic Data for the Molecules and the Full Geometrical Information Table S1. Crystal data and structure refinement for compound 2. Identification Code 121_a Empirical formula C10 H30 Ca N8 O16 P4 Formula weight 682.38 Temperature 100.0 (1) K Wavelength 0.71073 A Crystal system, space group Triclinic, P-1 a = 10.6815 (4) A, α = 60.518 (5)deg Unit cell dimensions b = 12.5015 (6) A, β = 66.986 (4)deg c = 12.6155 (5) A, γ = 69.072 (4)deg Volume 1320.90 (12) A 3 Z, Calculated density 2, 1.716 Mg/m 3 Absorption coefficient 0.566 mm 1 F(000) 708 Crystal size 0.2 0.1 0.1 mm Theta range for data collection 3.132 25.999 Limiting indices 13 h 13, 12 k 15, 15 l 15 Reflections collected/unique 8995/5080 [R(int) = 0.0797] Completeness to θ = 25.242 98.40% Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters 5080/64/420 Goodness-of-fit on F 2 1.033 Final R indices [I > 2σ(I)] R1 = 0.0790, wr2 = 0.1307 R indices (all data) R1 = 0.1673, wr2 = 0.1644 Extinction coefficient n/a Largest diff. peak and hole 0.656 and 0.766 e A 3

S14 of S23 Table S2. Atomic coordinates ( 10 4 ) and equivalent isotropic displacement parameters (A^2 10^3) for 121_a (compound 2). X Y Z U(eq) Ca(1) 12,706(1) 4111(1) 5360(1) 18(1) P(10A) 10,846(2) 5748(2) 2879(2) 15(1) P(10B) 15,703(2) 2146(2) 6301(2) 20(1) P(14A) 11,386(2) 2806(2) 4194(2) 17(1) P(14B) 16,320(2) 4155(2) 3564(2) 17(1) N(1A) 11,402(6) 3004(5) 96(5) 19(1) N(2A) 11,718(6) 3357(5) 830(5) 19(1) N(4A) 9396(6) 3685(5) 1169(5) 17(1) N(8A) 10,205(6) 4285(5) 2266(5) 18(1) N(1B) 19,244(6) 71(5) 2852(5) 22(1) N(2B) 18,126(6) 787(5) 3410(5) 21(1) N(4B) 20,151(6) 848(5) 3515(5) 17(1) N(8B) 18,069(5) 1971(5) 4441(5) 18(1) O(11A) 9320(5) 6216(4) 3109(4) 19(1) O(12A) 11,548(5) 6653(5) 1518(4) 27(1) O(13A) 11,477(5) 5609(4) 3841(4) 20(1) O(15A) 11,735(5) 1713(4) 3864(5) 24(1) O(16A) 12,406(5) 2785(4) 4751(4) 21(1) O(17A) 9844(4) 2821(4) 5084(4) 18(1) O(11B) 16,299(5) 777(5) 7072(4) 31(1) O(12B) 14,188(5) 2466(4) 6465(4) 22(1) O(13B) 16,216(5) 2902(5) 6688(5) 30(1) O(15B) 16,744(5) 4191(5) 2223(4) 23(1) O(16B) 14,783(5) 4729(4) 3883(4) 20(1) O(17B) 17,268(5) 4704(4) 3690(4) 20(1) O(18) 15,481(9) 772(7) 7014(8) 92(3) O(19) 13,343(10) 7763(9) 1028(10) 102(3) O(20) 4590(18) 5097(18) 985(13) 81(5) O(21) 4970(30) 3290(30) 1580(30) 68(7) O(22) 4508(8) 2924(8) 794(9) 54(2) O(23) 4198(16) 466(11) 5186(13) 61(4) C(3A) 10,463(7) 3773(6) 1447(6) 18(2) C(5A) 10,062(8) 3200(6) 309(6) 22(2) C(6A) 12,529(8) 2531(6) -809(6) 24(2) C(7A) 13,346(8) 1271(7) -157(7) 38(2) C(9A) 11,267(7) 4244(6) 2756(6) 15(2) C(3B) 18,736(7) 1228(6) 3807(6) 19(2) C(5B) 20,413(8) 104(6) 2920(6) 22(2) C(6B) 18,979(9) 595(7) 2293(7) 36(2) C(7B) 18,382(9) 295(8) 1193(8) 44(2) C(9B) 16,581(7) 2479(6) 4633(6) 17(2) U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

S15 of S23 Table S3. Bond lengths [A] and angles [deg] for 121_a (compound 2). Symmetry transformations used to generate equivalent atoms: #1 x + 2, y + 1, z + 1; #2 x + 3, y + 1, z + 1; #3 x + 1, y, z + 1. Atoms Distance Ca(1)-O(11A) #1 2.273(5) Ca(1)-O(12B) 2.292(5) Ca(1)-O(16A) 2.295(5) Ca(1)-O(17B) #2 2.331(5) Ca(1)-O(16B) 2.359(5) Ca(1)-O(13A) 2.363(5) Ca(1)-P(10B) 3.489(2) Ca(1)-P(14A) 3.528(2) Ca(1)-P(10A) #1 3.561(2) P(10A)-O(11A) 1.483(5) P(10A)-O(13A) 1.518(5) P(10A)-O(12A) 1.574(5) P(10A)-C(9A) 1.841(6) P(10A)-Ca(1) #1 3.561(2) P(10B)-O(12B) 1.476(5) P(10B)-O(11B) 1.533(5) P(10B)-O(13B) 1.571(5) P(10B)-C(9B) 1.832(6) P(14A)-O(16A) 1.498(5) P(14A)-O(15A) 1.501(5) P(14A)-O(17A) 1.589(5) P(14A)-C(9A) 1.830(6) P(14B)-O(17B) 1.502(5) P(14B)-O(16B) 1.516(5) P(14B)-O(15B) 1.552(4) P(14B)-C(9B) 1.839(7) N(1A)-C(5A) 1.302(9) N(1A)-N(2A) 1.385(7) N(1A)-C(6A) 1.478(8) N(2A)-C(3A) 1.326(8) N(4A)-C(5A) 1.337(8) N(4A)-C(3A) 1.368(8) N(8A)-C(3A) 1.362(8) N(8A)-C(9A) 1.465(8) N(8A)-H(8AA) 0.8600 N(1B)-C(5B) 1.301(9) N(1B)-N(2B) 1.386(7) N(1B)-C(6B) 1.474(9) N(2B)-C(3B) 1.327(8) N(4B)-C(5B) 1.358(8) N(4B)-C(3B) 1.368(8) N(8B)-C(3B) 1.351(8) N(8B)-C(9B) 1.456(8) N(8B)-H(8BA) 0.8600 O(11A)-Ca(1) #1 2.273(5) O(12A)-H(12A) 0.837(10) O(15A)-H(15A) 0.841(10) O(17A)-H(17A) 0.840(10) O(11B)-H(11B) 1.03(9)

S16 of S23 O(13B)-H(13B) 0.88(8) O(15B)-H(15B) 0.82(7) O(17B)-Ca(1) #2 2.331(5) O(18)-H(18A) 0.843(10) O(18)-H(18B) 0.841(10) O(19)-H(19A) 0.848(10) O(19)-H(19B) 0.854(10) O(20)-H(20A) 0.839(10) O(20)-H(20B) 0.840(10) O(20)-H(21D) 1.23(18) O(21)-O(22) 1.56(3) O(21)-H(21C) 0.839(11) O(21)-H(21D) 0.840(10) O(22)-H(22A) 0.841(10) O(22)-H(22B) 0.844(10) O(23)-O(23) #3 1.73(3) O(23)-H(23A) 0.840(10) O(23)-H(23B) 0.842(10) C(5A)-H(5AB) 0.93 C(6A)-C(7A) 1.491(9) C(6A)-H(6AA) 0.9700 C(6A)-H(6AB) 0.9700 C(7A)-H(7AA) 0.9600 C(7A)-H(7AB) 0.9600 C(7A)-H(7AC) 0.9600 C(9A)-H(9AA) 0.9800 C(5B)-H(5BA) 0.9300 C(6B)-C(7B) 1.496(10) C(6B)-H(6BA) 0.9700 C(6B)-H(6BB) 0.9700 C(7B)-H(7BA) 0.9600 C(7B)-H(7BB) 0.9600 C(7B)-H(7BC) 0.9600 C(9B)-H(9BA) 0.9800 O(11A) #1-Ca(1)-O(12B) 98.32(16) O(11A) #1-Ca(1)-O(16A) 87.76(16) O(12B)-Ca(1)-O(16A) 88.68(16) O(11A) #1-Ca(1)-O(17B) #2 82.68(16) O(12B)-Ca(1)-O(17B) #2 89.53(16) O(16A)-Ca(1)-O(17B) #2 169.92(17) O(11A) #1-Ca(1)-O(16B) 169.68(16) O(12B)-Ca(1)-O(16B) 83.59(16) O(16A)-Ca(1)-O(16B) 102.44(17) O(17B) #2-Ca(1)-O(16B) 87.20(16) O(11A) #1-Ca(1)-O(13A) 90.91(16) O(12B)-Ca(1)-O(13A) 165.95(16) O(16A)-Ca(1)-O(13A) 81.08(16) O(17B) #2-Ca(1)-O(13A) 102.20(16) O(16B)-Ca(1)-O(13A) 89.22(16) O(11A) #1-Ca(1)-P(10B) 115.07(12) O(12B)-Ca(1)-P(10B) 17.58(12) O(16A)-Ca(1)-P(10B) 94.50(12)

S17 of S23 O(17B) #2-Ca(1)-P(10B) 86.69(12) O(16B)-Ca(1)-P(10B) 66.14(11) O(13A)-Ca(1)-P(10B) 153.56(12) O(11A) #1-Ca(1)-P(14A) 80.88(12) O(12B)-Ca(1)-P(14A) 105.20(12) O(16A)-Ca(1)-P(14A) 17.19(11) O(17B) #2-Ca(1)-P(14A) 159.30(12) O(16B)-Ca(1)-P(14A) 108.50(12) O(13A)-Ca(1)-P(14A) 65.68(12) P(10B)-Ca(1)-P(14A) 111.69(5) O(11A) #1-Ca(1)-P(10A) #1 14.86(12) O(12B)-Ca(1)-P(10A) #1 113.13(12) O(16A)-Ca(1)-P(10A) #1 87.00(12) O(17B) #2-Ca(1)-P(10A) #1 84.59(12) O(16B)-Ca(1)-P(10A) #1 161.24(12) O(13A)-Ca(1)-P(10A) #1 76.12(12) P(10B)-Ca(1)-P(10A) #1 129.94(6) P(14A)-Ca(1)-P(10A) #1 76.34(5) O(11A)-P(10A)-O(13A) 115.8(3) O(11A)-P(10A)-O(12A) 107.8(3) O(13A)-P(10A)-O(12A) 110.2(3) O(11A)-P(10A)-C(9A) 108.2(3) O(13A)-P(10A)-C(9A) 110.5(3) O(12A)-P(10A)-C(9A) 103.7(3) O(11A)-P(10A)-Ca(1) #1 23.15(18) O(13A)-P(10A)-Ca(1) #1 99.72(18) O(12A)-P(10A)-Ca(1) #1 130.8(2) C(9A)-P(10A)-Ca(1) #1 101.0(2) O(12B)-P(10B)-O(11B) 115.7(3) O(12B)-P(10B)-O(13B) 114.2(3) O(11B)-P(10B)-O(13B) 103.0(3) O(12B)-P(10B)-C(9B) 108.5(3) O(11B)-P(10B)-C(9B) 107.3(3) O(13B)-P(10B)-C(9B) 107.7(3) O(12B)-P(10B)-Ca(1) 27.97(18) O(11B)-P(10B)-Ca(1) 142.1(2) O(13B)-P(10B)-Ca(1) 105.2(2) C(9B)-P(10B)-Ca(1) 87.5(2) O(16A)-P(14A)-O(15A) 114.4(3) O(16A)-P(14A)-O(17A) 113.9(3) O(15A)-P(14A)-O(17A) 105.3(3) O(16A)-P(14A)-C(9A) 109.7(3) O(15A)-P(14A)-C(9A) 107.8(3) O(17A)-P(14A)-C(9A) 105.2(3) O(16A)-P(14A)-Ca(1) 26.93(17) O(15A)-P(14A)-Ca(1) 141.2(2) O(17A)-P(14A)-Ca(1) 100.34(17) C(9A)-P(14A)-Ca(1) 92.8(2) O(17B)-P(14B)-O(16B) 116.1(3) O(17B)-P(14B)-O(15B) 111.7(3) O(16B)-P(14B)-O(15B) 108.2(3) O(17B)-P(14B)-C(9B) 106.6(3)

S18 of S23 O(16B)-P(14B)-C(9B) 108.4(3) O(15B)-P(14B)-C(9B) 105.3(3) C(5A)-N(1A)-N(2A) 110.6(5) C(5A)-N(1A)-C(6A) 129.2(6) N(2A)-N(1A)-C(6A) 120.1(6) C(3A)-N(2A)-N(1A) 101.7(5) C(5A)-N(4A)-C(3A) 102.8(6) C(3A)-N(8A)-C(9A) 124.1(6) C(3A)-N(8A)-H(8AA) 117.9 C(9A)-N(8A)-H(8AA) 117.9 C(5B)-N(1B)-N(2B) 111.3(5) C(5B)-N(1B)-C(6B) 129.8(6) N(2B)-N(1B)-C(6B) 118.9(6) C(3B)-N(2B)-N(1B) 102.5(5) C(5B)-N(4B)-C(3B) 104.1(6) C(3B)-N(8B)-C(9B) 121.3(6) C(3B)-N(8B)-H(8BA) 119.4 C(9B)-N(8B)-H(8BA) 119.4 P(10A)-O(11A)-Ca(1) #1 142.0(3) P(10A)-O(12A)-H(12A) 109.5 P(10A)-O(13A)-Ca(1) 142.6(3) P(14A)-O(15A)-H(15A) 109.5 P(14A)-O(16A)-Ca(1) 135.9(3) P(14A)-O(17A)-H(17A) 109.5 P(10B)-O(11B)-H(11B) 109.5 P(10B)-O(12B)-Ca(1) 134.4(3) P(10B)-O(13B)-H(13B) 109.5 P(14B)-O(15B)-H(15B) 109.5 P(14B)-O(16B)-Ca(1) 138.6(3) P(14B)-O(17B)-Ca(1) #2 142.5(3) H(18A)-O(18)-H(18B) 105(3) H(19A)-O(19)-H(19B) 103(3) H(20A)-O(20)-H(20B) 106(3) H(20A)-O(20)-H(21D) 157(10) H(20B)-O(20)-H(21D) 51(10) O(22)-O(21)-H(21C) 109(10) O(22)-O(21)-H(21D) 120(10) H(21C)-O(21)-H(21D) 106(3) O(21)-O(22)-H(22A) 117(9) O(21)-O(22)-H(22B) 106(8) H(22A)-O(22)-H(22B) 105(3) O(23) #3-O(23)-H(23A) 117(10) O(23) #3-O(23)-H(23B) 64(10) H(23A)-O(23)-H(23B) 105(3) N(2A)-C(3A)-N(8A) 124.8(7) N(2A)-C(3A)-N(4A) 114.2(6) N(8A)-C(3A)-N(4A) 120.9(6) N(1A)-C(5A)-N(4A) 110.7(6) N(1A)-C(5A)-H(5AB) 124.7 N(4A)-C(5A)-H(5AB) 124.7 N(1A)-C(6A)-C(7A) 112.0(6) N(1A)-C(6A)-H(6AA) 109.2

S19 of S23 C(7A)-C(6A)-H(6AA) 109.2 N(1A)-C(6A)-H(6AB) 109.2 C(7A)-C(6A)-H(6AB) 109.2 H(6AA)-C(6A)-H(6AB) 107.9 C(6A)-C(7A)-H(7AA) 109.5 C(6A)-C(7A)-H(7AB) 109.5 H(7AA)-C(7A)-H(7AB) 109.5 C(6A)-C(7A)-H(7AC) 109.5 H(7AA)-C(7A)-H(7AC) 109.5 H(7AB)-C(7A)-H(7AC) 109.5 N(8A)-C(9A)-P(14A) 108.9(4) N(8A)-C(9A)-P(10A) 107.0(4) P(14A)-C(9A)-P(10A) 117.4(3) N(8A)-C(9A)-H(9AA) 107.7 P(14A)-C(9A)-H(9AA) 107.7 P(10A)-C(9A)-H(9AA) 107.7 N(2B)-C(3B)-N(8B) 125.3(6) N(2B)-C(3B)-N(4B) 113.1(6) N(8B)-C(3B)-N(4B) 121.7(6) N(1B)-C(5B)-N(4B) 109.0(6) N(1B)-C(5B)-H(5BA) 125.5 N(4B)-C(5B)-H(5BA) 125.5 N(1B)-C(6B)-C(7B) 111.9(6) N(1B)-C(6B)-H(6BA) 109.2 C(7B)-C(6B)-H(6BA) 109.2 N(1B)-C(6B)-H(6BB) 109.2 C(7B)-C(6B)-H(6BB) 109.2 H(6BA)-C(6B)-H(6BB) 107.9 C(6B)-C(7B)-H(7BA) 109.5 C(6B)-C(7B)-H(7BB) 109.5 H(7BA)-C(7B)-H(7BB) 109.5 C(6B)-C(7B)-H(7BC) 109.5 H(7BA)-C(7B)-H(7BC) 109.5 H(7BB)-C(7B)-H(7BC) 109.5 N(8B)-C(9B)-P(10B) 111.3(5) N(8B)-C(9B)-P(14B) 108.2(4) P(10B)-C(9B)-P(14B) 114.5(3) N(8B)-C(9B)-H(9BA) 107.5 P(10B)-C(9B)-H(9BA) 107.5 P(14B)-C(9B)-H(9BA) 107.5 Table S4. Anisotropic displacement parameters (A 2 10 3 ) for 121_a (compound 2). U11 U22 U33 U23 U13 U12 Ca(1) 16(1) 16(1) 18(1) 9(1) 3(1) 1(1) P(10A) 17(1) 14(1) 13(1) 6(1) 2(1) 2(1) P(10B) 22(1) 21(1) 13(1) 5(1) 4(1) 3(1) P(14A) 17(1) 14(1) 19(1) 10(1) 3(1) 3(1) P(14B) 19(1) 15(1) 11(1) 6(1) 3(1) 1(1) N(1A) 28(4) 11(3) 10(3) 4(2) 1(3) 1(3) N(2A) 21(3) 15(3) 12(3) 5(2) 0(3) 0(3) N(4A) 28(3) 12(3) 8(3) 3(2) 2(3) 6(3) N(8A) 17(3) 18(3) 15(3) 10(3) 1(3) 1(3)

S20 of S23 N(1B) 37(4) 4(3) 16(3) 3(2) 5(3) 1(3) N(2B) 30(4) 11(3) 14(3) 4(3) 2(3) 2(3) N(4B) 16(3) 11(3) 10(3) 1(2) 2(2) 3(2) N(8B) 13(3) 20(3) 22(3) 15(3) 6(3) 5(2) O(11A) 19(3) 16(2) 22(3) 10(2) 5(2) 1(2) O(12A) 33(3) 29(3) 17(3) 8(2) 2(2) 15(3) O(13A) 20(3) 16(3) 21(3) 10(2) 4(2) 1(2) O(15A) 22(3) 25(3) 28(3) 15(2) 9(2) 0(2) O(16A) 23(3) 16(3) 19(3) 9(2) 7(2) 4(2) O(17A) 23(3) 15(3) 18(3) 12(2) 3(2) 4(2) O(11B) 29(3) 28(3) 20(3) 6(2) 4(2) 4(2) O(12B) 22(3) 18(3) 16(3) 3(2) 1(2) 3(2) O(13B) 40(3) 27(3) 24(3) 11(3) 6(3) 9(3) O(15B) 25(3) 25(3) 10(3) 2(2) 1(2) 5(2) O(16B) 22(3) 16(3) 12(2) 2(2) 1(2) 1(2) O(17B) 19(3) 19(3) 19(3) 8(2) 2(2) 1(2) O(18) 146(8) 39(4) 108(7) 10(4) 72(6) 27(5) O(19) 115(7) 99(6) 106(7) 34(6) 35(6) 44(6) O(20) 80(11) 134(12) 43(8) 23(9) 11(7) 61(9) O(21) 78(15) 77(15) 63(14) 35(12) 5(11) 34(12) O(22) 43(5) 56(6) 57(6) 18(5) 10(4) 14(4) O(23) 69(10) 36(8) 84(10) 37(7) 33(9) 15(7) C(3A) 24(4) 12(4) 11(4) 2(3) 3(3) 4(3) C(5A) 33(5) 16(4) 15(4) 5(3) 7(3) 5(3) C(6A) 35(5) 18(4) 13(4) 10(3) 1(3) 3(3) C(7A) 38(5) 27(5) 21(4) 7(4) 7(4) 4(4) C(9A) 19(4) 11(3) 13(4) 5(3) 5(3) 1(3) C(3B) 29(4) 8(3) 13(4) 4(3) 6(3) 7(3) C(5B) 24(4) 13(4) 18(4) 7(3) 4(3) 7(3) C(6B) 56(6) 26(4) 26(5) 17(4) 2(4) 9(4) C(7B) 54(6) 41(5) 36(5) 22(4) 9(5) 4(5) C(9B) 16(4) 13(3) 18(4) 8(3) 4(3) 5(3) The anisotropic displacement factor exponent takes the form: 2 pi 2 [ h 2 a* 2 U11 +... + 2 h k a* b* U12 ]. Table S5. Hydrogen coordinates ( 10 4 ) and isotropic displacement parameters (A 2 10 3 ) for 121_a (compound 2). X Y Z U(eq) H(8AA) 9367 4655 2511 21 H(8BA) 18,533 2148 4738 21 H(12A) 12,250(50) 6790(60) 1534(16) 40 H(15A) 11,020(20) 1640(40) 3800(70) 36 H(17A) 9680(20) 3250(50) 5480(50) 26 H(11B) 15,940(70) 190(50) 6950(60) 47 H(13B) 15,800(70) 3700(70) 6390(70) 45 H(15B) 17,590(80) 4080(70) 1950(40) 35 H(18A) 14,700(60) 450(80) 7380(100) 110 H(18B) 15,510(100) 1551(17) 7400(90) 110 H(19A) 13,770(100) 8270(70) 950(110) 122 H(19B) 13,750(110) 7050(40) 1480(110) 122 H(20A) 4500(200) 5870(30) 540(150) 97 H(20B) 5250(150) 4760(150) 530(140) 97 H(21C) 5700(200) 2740(180) 1800(300) 82

S21 of S23 H(21D) 5200(300) 3990(110) 1300(400) 82 H(22A) 3840(70) 2550(80) 1170(90) 65 H(22B) 4220(100) 3610(60) 230(80) 65 H(23A) 4200(190) 1150(80) 5160(130) 73 H(23B) 4500(200) 550(140) 4430(50) 73 H(5AB) 9628 3027 84 26 H(6AA) 13,147 3119 1339 29 H(6AB) 12,132 2478 1349 29 H(7AA) 13,731 1317 388 58 H(7AB) 14,084 1008 773 58 H(7AC) 12,747 676 336 58 H(9AA) 12,162 4200 2125 18 H(5BA) 21,287 315 2611 26 H(6BA) 18,339 1139 2930 43 H(6BB) 19,843 1118 2019 43 H(7BA) 19,010 838 562 66 H(7BB) 17,506 789 1468 66 H(7BC) 18,245 171 842 66 H(9BA) 16,208 2056 4377 21 Table S6. Torsion angles ( ) for 121_a (compound 2). Symmetry transformations used to generate equivalent atoms: #1 x + 2, y + 1, z + 1; #2 x + 3, y + 1, z + 1; #3 x + 1, y, z + 1. C(5A)-N(1A)-N(2A)-C(3A) 0.7(7) C(6A)-N(1A)-N(2A)-C(3A) 177.0(5) C(5B)-N(1B)-N(2B)-C(3B) 0.3(7) C(6B)-N(1B)-N(2B)-C(3B) 179.5(6) O(13A)-P(10A)-O(11A)-Ca(1) #1 49.4(5) O(12A)-P(10A)-O(11A)-Ca(1) #1 173.2(4) C(9A)-P(10A)-O(11A)-Ca(1) # 175.2(5) O(11A)-P(10A)-O(13A)-Ca(1) 117.8(4) O(12A)-P(10A)-O(13A)-Ca(1) 119.6(4) C(9A)-P(10A)-O(13A)-Ca(1) 5.6(5) Ca(1)#1-P(10A)-O(13A)-Ca(1) 100.2(4) O(15A)-P(14A)-O(16A)-Ca(1) 175.0(3) O(17A)-P(14A)-O(16A)-Ca(1) 63.9(4) C(9A)-P(14A)-O(16A)-Ca(1) 53.8(5) O(11B)-P(10B)-O(12B)-Ca(1) 164.0(3) O(13B)-P(10B)-O(12B)-Ca(1) 76.7(4) C(9B)-P(10B)-O(12B)-Ca(1) 43.4(5) O(17B)-P(14B)-O(16B)-Ca(1) 117.4(4) O(15B)-P(14B)-O(16B)-Ca(1) 116.2(4) C(9B)-P(14B)-O(16B)-Ca(1) 2.4(5) O(16B)-P(14B)-O(17B)-Ca(1) #2 19.5(5) O(15B)-P(14B)-O(17B)-Ca(1) #2 144.2(4) C(9B)-P(14B)-O(17B)-Ca(1) #2 101.3(4) N(1A)-N(2A)-C(3A)-N(8A) 177.1(6) N(1A)-N(2A)-C(3A)-N(4A) 1.0(7) C(9A)-N(8A)-C(3A)-N(2A) 11.5(10) C(9A)-N(8A)-C(3A)-N(4A) 170.6(6) C(5A)-N(4A)-C(3A)-N(2A) 1.0(7) C(5A)-N(4A)-C(3A)-N(8A) 177.2(6) N(2A)-N(1A)-C(5A)-N(4A) 0.1(7) C(6A)-N(1A)-C(5A)-N(4A) 177.3(6) C(3A)-N(4A)-C(5A)-N(1A) 0.5(7)

S22 of S23 C(5A)-N(1A)-C(6A)-C(7A) 113.2(8) N(2A)-N(1A)-C(6A)-C(7A) 69.5(8) C(3A)-N(8A)-C(9A)-P(14A) 88.7(6) C(3A)-N(8A)-C(9A)-P(10A) 143.5(5) O(16A)-P(14A)-C(9A)-N(8A) 176.6(4) O(15A)-P(14A)-C(9A)-N(8A) 58.3(5) O(17A)-P(14A)-C(9A)-N(8A) 53.7(5) Ca(1)-P(14A)-C(9A)-N(8A) 155.2(4) O(16A)-P(14A)-C(9A)-P(10A) 54.9(4) O(15A)-P(14A)-C(9A)-P(10A) 180.0(3) O(17A)-P(14A)-C(9A)-P(10A) 68.1(4) Ca(1)-P(14A)-C(9A)-P(10A) 33.4(4) O(11A)-P(10A)-C(9A)-N(8A) 29.1(5) O(13A)-P(10A)-C(9A)-N(8A) 156.7(4) O(12A)-P(10A)-C(9A)-N(8A) 85.3(5) Ca(1)#1-P(10A)-C(9A)-N(8A) 51.8(4) O(11A)-P(10A)-C(9A)-P(14A) 93.7(4) O(13A)-P(10A)-C(9A)-P(14A) 34.0(5) O(12A)-P(10A)-C(9A)-P(14A) 152.0(4) Ca(1)#1-P(10A)-C(9A)-P(14A) 70.9(4) N(1B)-N(2B)-C(3B)-N(8B) 178.8(6) N(1B)-N(2B)-C(3B)-N(4B) 0.9(7) C(9B)-N(8B)-C(3B)-N(2B) 6.8(10) C(9B)-N(8B)-C(3B)-N(4B) 173.5(6) C(5B)-N(4B)-C(3B)-N(2B) 1.3(7) C(5B)-N(4B)-C(3B)-N(8B) 178.5(6) N(2B)-N(1B)-C(5B)-N(4B) 0.5(7) C(6B)-N(1B)-C(5B)-N(4B) 179.7(6) C(3B)-N(4B)-C(5B)-N(1B) 1.0(7) C(5B)-N(1B)-C(6B)-C(7B) 115.6(8) N(2B)-N(1B)-C(6B)-C(7B) 64.6(8) C(3B)-N(8B)-C(9B)-P(10B) 128.0(5) C(3B)-N(8B)-C(9B)-P(14B) 105.4(6) O(12B)-P(10B)-C(9B)-N(8B) 169.4(4) O(11B)-P(10B)-C(9B)-N(8B) 43.7(6) O(13B)-P(10B)-C(9B)-N(8B) 66.6(5) Ca(1)-P(10B)-C(9B)-N(8B) 171.8(4) O(12B)-P(10B)-C(9B)-P(14B) 67.6(4) O(11B)-P(10B)-C(9B)-P(14B) 166.8(4) O(13B)-P(10B)-C(9B)-P(14B) 56.5(5) Ca(1)-P(10B)-C(9B)-P(14B) 48.7(3) O(17B)-P(14B)-C(9B)-N(8B) 46.7(5) O(16B)-P(14B)-C(9B)-N(8B) 172.3(4) O(15B)-P(14B)-C(9B)-N(8B) 72.1(5) O(17B)-P(14B)-C(9B)-P(10B) 78.0(4) O(16B)-P(14B)-C(9B)-P(10B) 47.6(5) O(15B)-P(14B)-C(9B)-P(10B) 163.2(4)

S23 of S23 Table S7. Hydrogen bonds for 121_a (compound 2) [Å]. Symmetry transformations used to generate equivalent atoms: #1 x + 2, y + 1, z + 1; #2 x + 3, y + 1, z + 1; #3 x + 1, y, z + 1. D-H A D(D-H) D(H A) D(D A) <(DHA) N(8A)-H(8AA) O(11A) 0.86 2.39 2.822(7) 111.3 O(17A)-H(17A) O(13A) #1 0.84 1.84 2.613(6) 151.8 O(20)-H(20A) O(21) #4 0.839(10) 2.25(17) 2.80(4) 124(16) O(20)-H(20A) O(22) #4 0.839(10) 1.89(14) 2.575(18) 138(19) O(20)-H(20B) O(20) #4 0.840(10) 1.78(15) 2.40(3) 129(18) O(20)-H(20B) O(21) 0.840(10) 1.71(18) 1.94(4) 92(13) O(20)-H(20B) O(22) 0.840(10) 2.5(2) 2.88(2) 106(16) O(21)-H(21D) O(20) 0.840(10) 1.23(18) 1.94(4) 137(29) O(22)-H(22A) N(2A) #5 0.841(10) 2.25(8) 2.818(10) 125(8) O(22)-H(22B) O(20) #4 0.844(10) 2.02(8) 2.575(18) 123(8) O(23)-H(23A) O(16A) #5 0.840(10) 2.25(16) 2.768(13) 120(16) C(5A)-H(5AB) O(12A) #6 0.93 2.39 3.280(9) 160

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