Electronic Supplementary Data

Supramolecular interactions between a diamine-diamide ligand and anions,

trigonal planar NO3- and spherical Cl-: Multiple hydrogen bond cooperativity

through water molecules

Jyothi Sunkari, Shashank Kundha, Raghava Rao Gundapaneni, Anjali Reddy, Someshwar Pola, Sreedhar Kodumuru & Jagannatha Swamy Sreedasyam*

Department of Chemistry, Kakatiya University, Warangal 506 009, India

Email: sj_swamy@yahoo.com

No. Contents Pg No.

1 Table S1 − Atomic coordinates and equivalent isotropic displacement parameters for compound 1 (PBAB). U(eq) is defined as one third of the trace of the orthogonalized Uij tensor

2

2 Table S2 − Anisotropic displacement parameters (Å2× 103) for compound 1 (PBAB). The anisotropic displacement factor exponent takes the form: −2[h2a*2U11 + ... + 2 h k a* b* U12]

3

3 Table S3 − Bond lengths [Å] and angles [°] for compound 1 (PBAB) 4 4 Table S4 − Hydrogen bond parameters for compound 1 (PBAB) [Å and °] 6 5 Table S5 − Atomic coordinates (× 104) and equivalent isotropic displacement parameters (Å2×103) for

compound 2 [PBABH22+(NO3)2. 2H2O]. U(eq) is defined as one third of the trace of the

orthogonalized Uij tensor.

6

6 Table S6 − Bond lengths [Å] and angles [°] for compound 2 [PBABH22+(NO3)2. 2H2O] 7

7 Table S7 − Anisotropic displacement parameters (Å2 × 103) for compound 2 [PBABH22+(NO3)2. 2H2O].

The anisotropic displacement factor exponent takes the form: -2π2[ h2a*2U11 + ... + 2 h k a* b* U12 ] 8

8 Table S8 − Hydrogen coordinates (× 104) and isotropic displacement parameters (Å2 × 103) for compound 2 [PBABH2

2+(NO3)2. 2H2O]. 9

9 Table S9 − Hydrogen bonding parameters (Å, deg) of compound 2 [PBABH22+(NO3)2. 2H2O]. 9

10 Table S10 − Atomic coordinates (× 104) and equivalent isotropic displacement parameters (Å2 × 103) for compound 3 [PBABH2

2+(Cl)2. 2H2O]. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

10

11 Table S11 − Bond lengths [Å] and angles [°]compound 3 [PBABH22+(Cl)2. 2H2O] 11

12 Table S12 − Anisotropic displacement parameters (Å2 × 103) compound (3) [PBABH22+(Cl)2. 2H2O].

The anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11 + ... + 2 h k a* b* U12] 13

13 Table S13 − Hydrogen coordinates (× 104) and isotropic displacement parameters (Å2

× 103)

compound 3 [PBABH2

2+(Cl)2. 2H2O]

14

14 Table S14 − Hydrogen bonding parameters (Å, deg) of compound (3) [PBABH2

2+(Cl)2. 2H2O] 14

15 Fig. S1 − IR spectrum of PBAB 15 16 Fig. S2 − IR spectrum of PBABH2(NO3)2.2H2O 15 17 Fig. S3 − IR spectrum of PBABH2(Cl)2.2H2O 16 18 Fig. S4 − 1H NMR spectrum of PBAB 16

19 Fig. S5 − 1H NMR spectrum of PBABH2(NO3)2.2H2O 17

20 Fig. S6 − 1H NMR spectrum of PBABH2(Cl)2.2H2O 17

1

Table S1 − Atomic coordinates and equivalent isotropic displacement parameters for compound 1 (PBAB). U(eq) is defined as one third of the trace of the orthogonalized Uij tensor

Atom x y z U(eq) C1 1.9805(2) 6.5323(1) 3.7412(3) 324 C2 2.2717(2) 7.7043(1) 4.4356(3) 300 C3 1.4472(2) 8.1886(1) 5.4377(3) 294 C4 0.2823(2) 7.4793(1) 5.7516(3) 374 C5 0.0159(2) 6.3092(1) 5.1028(3) 340 C6 0.8252(2) 5.7831(1) 4.1008(3) 303 C7 4.5197(2) 6.6832(1) 0.9440(3) 306 C8 2.8556(2) 6.0643(1) 2.6431(1) 285 C9 5.4928(2) 8.3450(1) 2.3202(3) 253 C10 5.5112(2) 7.8260(1) 0.7987(3) 293 C11 5.1120(2) 8.0112(1) -3.7218(3) 281 C12 5.9876(2) 7.2751(1) -4.5387(3) 285 C13 5.6705(2) 6.9932(1) 5.8566(3) 330 C14 4.4810(2) 7.4527(1) 6.3845(3) 327 C15 3.6023(2) 8.1853(1) 5.5961(3) 319 C16 3.9044(2) 8.4732(1) 4.2706(3) 284 C17 6.5731(2) 7.5701(1) 0.2631(3) 289 N1 0.4941(2) 4.6167(1) 3.4919(3) 398 N2 2.9817(2) 9.1402(1) -3.4827(3) 317 N3 3.5419(2) 7.0183(1) 1.9886(3) 300 N4 6.0450(2) 7.3744(1) 1.5977(3) 437 O1 5.3062(2) 9.4901(1) -1.8446(3) 314 O2 2.9436(2) 4.8665(1) 2.3309(3) 275

2

Table S2 − Anisotropic displacement parameters (Å2 × 103) for Compound 1 (PBAB). The anisotropic displacement factor exponent takes the form: - 2[ h2a*2U11 + ... + 2 h k a* b* U12 ]

Atom U11 U22 U33 U23 U13 U12 C1 316 291 290 76 22 90 C2 334 272 290 68 3 43 C3 390 303 286 12 44 88 C4 456 410 311 104 61 185 C5 338 379 320 105 52 71 C6 311 329 279 88 48 49 C7 382 219 334 -2 99 83 C8 258 235 366 52 33 49 C9 249 236 284 22 39 68

C10 375 264 254 38 40 93 C11 270 235 322 67 38 -19 C12 301 207 340 21 69 9 C13 359 267 367 22 107 28 C14 355 320 286 19 23 15 C15 302 324 325 281 1 51 C16 301 213 341 31 57 0 C17 285 291 269 29 -2 52 N1 375 376 411 211 16 -58 N2 304 316 337 -12 19 102 N3 276 290 335 58 55 23 N4 297 234 306 20 72 65 O1 389 239 312 7 35 66 O2 496 212 632 422 39 40

3

Table S3 − Bond lengths [Å] and angles [°] for compound 1 (PBAB)

C(1)-C(3) 1.492(2) C(2)-C(8) 1.394 (2) C(2)- C(3) 1.401(2) C(3)-C(4) 1.391 (2) C(4)-C(10) 1.376(2) C(4)-H(4) 0.9300 C(5)-C(7) 1.372(2) C(5)-C(12) 1.392(2) C(5)-H(5) 0.9300 C(6)-O(3) 1.2306(18) C(6)-C(7) 1.480(2) C(7)-C(9) 1.406(2) C(8)-C(11) 1.368 (2) C(8)-H(8) 0.9300 C(9)-C(14) 1.401(2) C(10)-C(11) 1.375(3) C(10)-H(10) 0.9300 C(11)-H(11) 0.9300 C(12)-C(13) 0.9300 C(12)-H(12) 0.9300 C(13)-C(14) 1.357(3) C(13)-H(13) 0.9300 C(14)-H(14) 0.9300 C(15)-N(1) 1.4502(19) C(15)-C(16) 1.512(2) C(15)-H(15B) 0.9700 C(15)-H(15A) 0.9700 C(15)-H(16B) 0.9700 C(15)-H(16A) 0.9700 C(16)-H(16B) 0.9700 C(16)-H(16A) 0.9700 C(17)-N(2) 1.4548(19) C(17)-C(16) 1.507(2) C(17)-H(16B) 0.9700 C(17)-H(16A) N(1)-C(1) N(1)-H(2) N(2)- C(6) N(2)-H(1)

0.9700 1.3283(`18)

0.882(17) 1.3275(`19)

0.900(18) N(3)-C(9) 1.359(2) N(3)-H(3B) 0.79(3) N(3)- H(3A) 0.87(2) N(4)-C(2) 1.372(2) N(4)-H(4B) 0.82(2) N(4)- H(4A) 0.89(2) O(1)-C(1) 1.2351(17) O(3)-C(6) 1.2306(18) N(2)- C(17)-C(16) 110.24(13) N2- C17- H17A 109.6 C16 -C17 -H17A 109.6 N2 -C17 -H17B 109.6 C16- C17 -H17B 109.6 H17A- C17 -H17B 108.1 C9 -N3- H3B 118.3(18)

4

Table S3 − Bond lengths [Å] and angles [°] for compound 1 (PBAB)

C9- N3 -H3A 122.2(14) H3B- N3 -H3A 119(2) N1 -C15 -C16 114.52(12) N1 -C15- H15A 108.6 C16 -C15- H15A 108.6 N1- C15 -H15B 108.6 C16- C15-H15B 108.6 H15A- C15 -H15B 107.6 C17 -C16 -C15 113.67(12) C17 -C16 -H16A 108.8 C15- C16- H16A 108.8 C17 -C16- H16B 108.8 C15- C16- H16B 108.8 H16A- C16- H16B 107.7 C2 -N4 -H4B 116.9(15) C2- N4- H4A 116.2(13) H4B- N4 -H4A 123(2) C6 -N2- C17 122.79(13) C17- N2 -H1 119.2(11) C1- N1- C15 122.81(13) C1- N1- H2 119.3(11) O1- C1-N1 121.85(14) O1- C1 -C3 121.82(13) N1- C1- C3 116.33(12) N4- C2- C8 120.17(16) N4- C2 -C3 121.40(15) C4- C3 -C2 119.20(14) C4 -C3- C1 120.55(13) C10- C4 -C3 121.39(16) C10- C4-H4 119.3 C3 -C4 -H4 119.3 C12- C5- C7 121.85(16) C12- C5- H5 119.1 C7 -C5- H5 119.1 O3- C6- N2 120.76(15) O3- C6 -C7 121.93(14) N2 -C6- C7 117.30(13) C5- C7- C9 118.79(15) C5 -C7- C6 120.54(13) C9- C7- C6 120.67(14) C11 -C8 -C2 121.29(16) C11- C8- H8 119.4 C2 -C8 -H8 119.4 N3- C9- C14 120.07(17) N3- C9- C7 122.05(17) C14- C9- C7 117.85(16) C11- C10 -C4 119.17(16) C11- C10- H10 120.4 C4- C10- H10 120.4 C8- C11- C10 120.57(16) C8- C11- H11 119.7 C10- C11-- H11 119.7 C5- C12- C13 119.07(18) C5- C12 -H12 120.5

5

Table S3 − Bond lengths [Å] and angles [°] for compound 1 (PBAB)

C13- C12- H12 120.5 C14- C13 -C12 120.55(17) C14- C13- H13 119.7 C12- C13- H13 119.7 C13 -C14- C9 121.79(17) C13- C14- H14 119.1 C9 -C14 -H14 119.1

Table S4 − Hydrogen bond parameters for compound 1 (PBAB) [Å and °]

D-H...A D...H/ Å D...A/ Å H...A/ Å ∠D-H...Ao Symmetry N2−H2A ⋅⋅⋅O1 0.884 2.865(1) 2.223 129.19( 2) x,y,z N1 −H1A ⋅⋅⋅O2 0.8802 2.7221(1) 2.084 128.65(2) x,y,z N4 −H4 ⋅⋅⋅O2 0.880 2.785(1) 1.939 160.57(2) -x+2, -y+1,-z N1 −H1B ⋅⋅⋅O2 0.880 3.403(1) 2.900(1) 118.00(2) x-1,+y,+z C10 − H 10A⋅⋅⋅O1 0.990 3.130(1) 2.569(1) 115.88(2) x,y,z C12− H12 ⋅⋅⋅O2 0.950 3.415(1) 2.869(1) 117.63(1) -x+2,-y+1,-z C10 −H10B ⋅⋅⋅N2 0.990 3.572(1) 2.961(1) 120.91(2) -x+2,-y+2,-z C2 −H2 ⋅⋅⋅O1 0.950 3.359(1) 2.880(1) 112.44(2) -x+2,-y+2,-z C2 −H2 ⋅⋅⋅N2 0.950 3.827 (1) 2.894 167.51(1) -x+2,-y+2,-z C17 −H17A ⋅⋅⋅N3 0.990 3.489(1) 2.899(1) 119.06(2) x+1,+y,+z C12 −H12 ⋅⋅⋅N2 0.950 3.394(1) 2.913(1) 112.67(1) x+1,+y,+z C7 −H7B ⋅⋅⋅N1 0.990 3.655(1) 2.850(1) 139.04(1) x+1,+y,+z

Table S5 − Atomic coordinates (× 104) and equivalent isotropic displacement parameters (Å2 × 103) for compound 2 [PBABH22+(NO3)2. 2H2O]. U(eq) is defined as one third of the trace of the

orthogonalized Uij tensor. x y z U(eq)

C(1) 5966(2) 3165(2) 4861(1) 38(1) C(2) 6445(2) 4392(2) 4707(1) 49(1) C(3) 6883(2) 5242(2) 5201(1) 58(1) C(4) 6827(2) 4890(2) 5869(1) 62(1) C(5) 6346(2) 3701(2) 6041(1) 55(1) C(6) 5921(2) 2848(2) 5544(1) 42(1) C(7) 5491(2) 2234(2) 4320(1) 39(1) C(8) 5323(2) 1717(2) 3112(1) 48(1) C(9) 5000 2564(3) 2500 46(1) N(1) 5412(2) 1596(2) 5760(1) 50(1) N(2) 5721(2) 2525(2) 3686(1) 45(1) N(3) 3368(2) 2687(2) 6856(1) 54(1) O(1) 4898(1) 1248(1) 4463(1) 57(1) O(2) 3374(2) 3094(2) 6275(1) 94(1) O(3) 2897(2) 3339(2) 7297(1) 86(1) O(4) 3802(2) 1595(2) 6979(1) 83(1) O(5) 7165(2) 804(2) 6748(1) 60(1)

6

Table S6 − Bond lengths [Å] and angles [°] for compound 2 [PBABH22+(NO3)2·2H2O]

C(1)-C(6) 1.389(2) C(1)-C(2) 1.390(3) C(1)-C(7) 1.503(2) C(2)-C(3) 1.374(3) C(2)-H(2) 0.9300 C(3)-C(4) 1.372(3) C(3)-H(3A) 0.9300 C(4)-C(5) 1.365(3) C(4)-H(4) 0.9300 C(5)-C(6) 1.376(3) C(5)-H(5) 0.9300 C(6)-N(1) 1.458(3) C(7)-O(1) 1.234(2) C(7)-N(2) 1.322(2) C(8)-N(2) 1.451(2) C(8)-C(9) 1.512(2) C(8)-H(8A) 0.9700 C(8)-H(8B) 0.9700 C(9)-C(8)#1 1.512(2) C(9)-H(9A) 0.9700 C(9)-H(9B) 0.9700 N(1)-H(1A) 0.92(3) N(1)-H(2B) 0.90(3) N(1)-H(2C) 0.88(3) N(2)-H(2A) 0.80(2) N(3)-O(2) 1.220(2) N(3)-O(4) 1.226(2) N(3)-O(3) 1.228(2) O(5)-H(3X) 0.83(3) O(5)-H(5Y) 0.83(4) C(6)-C(1)-C(2) 116.82(16) C(6)-C(1)-C(7) 121.31(16) C(2)-C(1)-C(7) 121.85(16) C(3)-C(2)-C(1) 121.90(19) C(3)-C(2)-H(2) 119.0 C(1)-C(2)-H(2) 119.0 C(4)-C(3)-C(2) 119.5(2) C(4)-C(3)-H(3A) 120.2 C(2)-C(3)-H(3A) 120.2 C(5)-C(4)-C(3) 120.27(19) C(5)-C(4)-H(4) 119.9 C(3)-C(4)-H(4) 119.9 C(4)-C(5)-C(6) 119.95(19) C(4)-C(5)-H(5) 120.0 C(6)-C(5)-H(5) 120.0 C(5)-C(6)-C(1) 121.53(18) C(5)-C(6)-N(1) 117.35(17) C(1)-C(6)-N(1) 121.12(16) O(1)-C(7)-N(2) 121.65(17) O(1)-C(7)-C(1) 121.03(16) N(2)-C(7)-C(1) 117.31(16)

7

Table S6 − Bond lengths [Å] and angles [°] for compound 2 [PBABH22+(NO3)2·2H2O]

N(2)-C(8)-C(9) 111.03(17) N(2)-C(8)-H(8A) 109.4 C(9)-C(8)-H(8A) 109.4 N(2)-C(8)-H(8B) 109.4 C(9)-C(8)-H(8B) 109.4 H(8A)-C(8)-H(8B) 108.0 C(8)#1-C(9)-C(8) 110.9(2) C(8)#1-C(9)-H(9A) 109.5 C(8)-C(9)-H(9A) 109.5 C(8)#1-C(9)-H(9B) 109.5 C(8)-C(9)-H(9B) 109.5 H(9A)-C(9)-H(9B) 108.0 C(6)-N(1)-H(1A) 106.5(16) C(6)-N(1)-H(2B) 111.4(19) H(1A)-N(1)-H(2B) 114(2) C(6)-N(1)-H(2C) 108.4(17) H(1A)-N(1)-H(2C) 109(2) H(2B)-N(1)-H(2C) 108(2) C(7)-N(2)-C(8) 123.43(17) C(7)-N(2)-H(2A) 121.1(15) C(8)-N(2)-H(2A) 114.7(15) O(2)-N(3)-O(4) 118.2(2) O(2)-N(3)-O(3) 120.5(2) O(4)-N(3)-O(3) 121.3(2) H(3X)-O(5)-H(5Y) 108(3)

Symmetry transformations used to generate equivalent atoms: #1 -x+1,y,-z+1/2

Table S7 − Anisotropic displacement parameters (Å2 × 103) for compound 2 [PBABH22+(NO3)2. 2H2O]. The

anisotropic displacement factor exponent takes the form: -2π2[ h2a*2U11 + ... + 2 h k a* b*U12] U11 U22 U33 U23 U13 U12

C(1) 40(1) 39(1) 35(1) -2(1) -2(1) 4(1) C(2) 59(1) 42(1) 45(1) 0(1) 0(1) -1(1) C(3) 67(1) 41(1) 64(1) -4(1) -7(1) -7(1) C(4) 76(1) 51(1) 58(1) -16(1) -19(1) -2(1) C(5) 74(1) 53(1) 39(1) -6(1) -10(1) 4(1) C(6) 47(1) 40(1) 38(1) -2(1) -2(1) 3(1) C(7) 45(1) 38(1) 34(1) 1(1) 0(1) 1(1) C(8) 68(1) 45(1) 31(1) -1(1) -4(1) -7(1) C(9) 60(2) 44(2) 35(1) 0 -2(1) 0 N(1) 66(1) 50(1) 33(1) -1(1) 5(1) -5(1) N(2) 58(1) 46(1) 32(1) 2(1) -1(1) -12(1) N(3) 60(1) 53(1) 51(1) 2(1) 6(1) -1(1) O(1) 83(1) 52(1) 35(1) -1(1) 1(1) -23(1) O(2) 133(2) 90(1) 63(1) 24(1) 33(1) 20(1) O(3) 110(2) 90(1) 58(1) -5(1) 18(1) 30(1) O(4) 105(1) 62(1) 83(1) 6(1) -1(1) 22(1) O(5) 79(1) 50(1) 53(1) 2(1) 5(1) -1(1)

8

Table S8 − Hydrogen coordinates (× 104) and isotropic displacement parameters (Å2 × 103) for compound 2 [PBABH22+(NO3)2. 2H2O].

x y z U(eq)

H(2) 6470 4645 4255 58 H(3A) 7215 6050 5084 69 H(4) 7119 5463 6206 75 H(5) 6306 3468 6495 66 H(8A) 4623 1203 3229 58 H(8B) 5961 1107 3004 58 H(9A) 4320 3127 2596 55 H(9B) 5680 3127 2404 55 H(1A) 5180(20) 1140(30) 5371(13) 69(7) H(2A) 6190(20) 3100(20) 3600(11) 44(6) H(2B) 5930(30) 1150(30) 6035(15) 81(9) H(2C) 4760(30) 1760(30) 5984(14) 71(8) H(3X) 6920(30) 1160(30) 7094(17) 94(11) H(5Y) 7350(30) 30(40) 6847(16) 96(11)

Table S9 - Hydrogen bonding parameters (Å, deg) of compound 2 [PBABH22+(NO3)2. 2H2O].

D-H...A D...H/ Å D...A/ Å H...A/ Å ∠D-H...Ao Symmetry

1 N(1) --H(1A) ..O(1 0.884 2.865(1) 2.223 129.19( 2) x,y,z N1 −H1A ⋅⋅⋅O2 0.8802 2.7221(1) 2.084 128.65(2) x,y,z N4 −H4 ⋅⋅⋅O2 0.880 2.785(1) 1.939 160.57(2) -x+2, -y+1,-z N1 −H1B ⋅⋅⋅O2 0.880 3.403(1) 2.900(1) 118.00(2) x-1,+y,+z C10 − H 10A ⋅⋅⋅O1 0.990 3.130(1) 2.569(1) 115.88(2) x,y,z C12− H12 ⋅⋅⋅O2 0.950 3.415(1) 2.869(1) 117.63(1) -x+2,-y+1,-z C10 −H10B ⋅⋅⋅N2 0.990 3.572(1) 2.961(1) 120.91(2) -x+2,-y+2,-z C2 −H2 ⋅⋅⋅O1 0.950 3.359(1) 2.880(1) 112.44(2) -x+2,-y+2,-z C2 −H2 ⋅⋅⋅N2 0.950 3.827 (1) 2.894 167.51(1) -x+2,-y+2,-z C17 −H17A ⋅⋅⋅N3 0.990 3.489(1) 2.899(1) 119.06(2) x+1,+y,+z C12 −H12 ⋅⋅⋅N2 0.950 3.394(1) 2.913(1) 112.67(1) x+1,+y,+z C7 −H7B ⋅⋅⋅N1 0.990 3.655(1) 2.850(1) 139.04(1) x+1,+y,+z

Translation of ARU-code to Equivalent Position Code

[ 3655. ] = 1-x,-y,-z; [ 7555. ] = 1/2-x,1/2-y,-z [ 8554. ] = 1/2+x,1/2-y,-1/2+z; [ 6555. ] = 1/2-x,1/2+y,1/2-z

9

Table S10 − Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for compound 3 [PBABH22+(Cl)2. 2H2O]. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor

Atom x y z U(eq)

C1 8.3856(2) 4.517(2) 5.6739(11) 310 C2 8.790(2) 3.591(3) 6.1817(12) 425 C3 9.352(2) 2.393(3) 5.9758(13) 484 C4 9.509(2) 2.121(3) 5.2685(14) 475 C5 9.082(2) 3.035(2) 4.7607(12) 406 C6 8.5058(17) 4.256(2) 4.9511(10) 291 C7 8.0026(18) 5.240(2) 4.4025(11) 305 C8 7.760(2) 5.823(2) 3.1482(10) 416 C9 7.4604(18) 4.953(3) 2.5077(9) 394 C10 7.025(2) 5.834(3) 1.9015(11) 432 C11 6.9788(18) 5.206(2) 6.400(10) 297 C12 6.5226(17) 4.204(2) 0.872(10) 297 C13 5.982(2) 2.956(2) 2.688(12) 396 C14 5.565(2) 2.048(2) -2.403(14) 476 C15 5.709(2) 2.340(3) -9.492(13) 478 C16 6.253(2) 3.551(3) -1.1472(12) 419 C17 6.6396(18) 4.475(2) -6.377(11) 304 O1 7.3686(15) 6.2360(17) 4.5772(8) 469 O2 7.6651(16) 6.1609(17) 4.805(8) 490(6) O3 4.6004(16) 3.3128(19) 1.8438(9) 462(5) O4 1.054(2) 5.117(3) 1.7912(12) 630(8) N1 7.808(2) 5.782(2) 5.9304(10) 358(6) N2 8.2310(18) 4.974(2) 3.7299(9) 355(6) N3 6.6419(18) 4.987(2) 1.2986(9) 370(6) N4 7.203(2) 5.764(2) -8.865(11) 378(6) Cl1 2.633(5) 3.0234(6) 2.9863(3) 440(2) Cl2 5.8426(6) 4.103(7) 1.9162(3) 494(2)

10

Table S11 − Bond lengths [Å] and angles [°]compound (3) [PBABH22+(Cl)2. 2H2O].

C1-C6 1.392(3) C1-C2 1.382(3) C2-C3 1.375(4) C3-C4 1.371(4) C4-C5 1.383(3) C5-C6 1.393(3) C6-C7 1.509(3) C8-C9 1.505(3) C9-C10 1.502(3) C11-C12 1.507(3) C12-C13 1.392(3) C13-C14 1.378(3) C14-C15 1.376(4) C15-C16 1.372(4) C16-C17 1.377(3) C2-H2 0.9300 C3-H3 0.9300 C4-H4 0.9300 C5-H5 0.9300 C8- H8B 0.9700 C8- H8A 0.9700 C9-H8A 0.9700 C9- H9B 0.9700 C10- H10A 0.9700 C10-H10B 0.9700 C13-H13 0.9300 C14-H14 0.9300 C15-H15 0.9300 C16-H16 0.9300 O1-C7 1.244(3) O2-C11 1.242(3) O1- H3B 0.8500 O3- H3B 0.8500 O4- H3B 0.81(4) O4- H3B 0.73(3) N1-C1 1.466(3) N2-C8 1.466(3) N2-C7 1.321(3) N3-C11 1.318(3) N3-C10 1.460(3) N4-C17 1.474(3) N1-H3N1 1.04(3) N1- H1N1 0.94(3) N1- H1N1 0.84(3) N2- H2N2 0.78(3) N3- H3N3 0.78(2) N4- H3N4 0.98(3) N4- H1N4 0.95(3) N4- H2N4 0.87(2) H3A- O3-H3B 110.00 H4A-O4-H4B 105(3) C7-N2-C8 122.47(18) C10-N3-C11 123.79(19) H1N1-N1-H2N1 103(3)

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Table S11 − Bond lengths [Å] and angles [°]compound (3) [PBABH22+(Cl)2. 2H2O].

H1N1-N1-H3N1 115(3) C1-N1-H3N1 104.9(17) C1-N1-H2N1 108.5(17) H2N1-N1-H3N1 116(2) C1-N1-H1N1 110.1(18) C7-N2- H2N2 121(2) C8-N2-H2N2 115(2) C10-N3-H3N3 116.3(18) C11-N3-H3N3 118.9(18) C11-N3-H3N3 118.9(18) C17-N4-H2N4 108.7(17) C17-N4-H1N4 107.5(17) H3N4-N4-H2N4 104(3) H3N4-N4-H1N4 112(2) H2N4-N4-H1N4 116(2) C17-N4-H3N4 108.7(17) N1-C1-C6 121.34(18) C2-C1-C6 121.70(19) N1-C1-C2 116.95(19) C1-C2-C3 119.8(2) C2-C3-C4 119.9(2) C3-C4-C5 120.2(2) C4-C5-C6 121.3(2) C1-C6-C7 121.09(17) C5-C6-C7 121.86(18) C1-C6-C5 117.03(18) N2-C7-C6 117.33(18) O1-C7-N2 121.47(19) O1-C7-C6 121.16(18) N2-C8-C9 111.54(17) C8-C9-C10 111.4(2) N3 -C10-C9 111.6(2) N3-C11-C12 116.59(18) O2-C11-C12 121.16(17) O2-C11-N3 122.22(19) C11-C12-C13 122.07(18) C11-C12-C17 121.37(17) C13-C12-C17 116.56(18) C12-C13-C14 121.7(2) C13-C14-C15 120.2(2) C14-C15-C16 119.7(2) C15-C16-C17 120.0(2) N4-C17-C12 120.88(18) N4-C17-C16 117.25(19) C12-C17-C16 121.87(19) C3-C2-H2 120.00 C1-C2-H2 120.00 C2-C3-H3 120.00 C4-C3-H3 120.00 C5-C4-H4 120.00 C3-C4-H4 120.00 C4-C5-H5 119.00 C6-C5-H5 119.00 N2-C8-H8A 109.00

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Table S11 − Bond lengths [Å] and angles [°]compound (3) [PBABH22+(Cl)2. 2H2O].

C9-C8-H8B 109.00 H8A-C8-H8B 108.00 N2-C8-H8B 109.00 C9-C8-H8A 109.00 C10-C9-H9A 109.00 C8-C9-H9A 109.00 C8-C9-H9B 109.00 H9A-C9-H9B 108.00 C10-C9-H9B 109.00 N3-C10-H10B 109.00 C9-C10-H10A 109.00 H10A-C10-H10B 108.00 C9-C10-10B 109.00 N3-C10-H10A 109.00 C12-C13-H13 119.00 C14-C13-H13 119.00 C15-C14-H14 120.00 C13-C14-H14 120.00 C14-C15-H15 120.00 C16-C15-H15 120.00 C17-C16-H16 120.00 C15-C16-H16 120.00

Table S12 − Anisotropic displacement parameters (Å2 × 103) compound (3) [PBABH22+(Cl)2. 2H2O]. The anisotropic displacement factor exponent takes the form: -2π2[ h2a*2U11 + ... + 2 h k a* b* U12].

Atom U11 U22 U33 U23 U13 U12 C1 340 309 280 3 10 17 C2 528 451 294 66 62 10 C3 555 421 474 149 129 55 C4 530 364 531 40 25 102 C5 508 346 365 11 32 65 C6 321 296 255 9 9 23 C7 357 285 273 8 27 18 C8 621 389 237 24 42 32 C9 453 416 311 8 32 17 C10 626 431 238 8 49 17 C11 378 265 247 10 3 5 C12 318 275 297 7 20 10 C13 492 321 376 10 56 71 C14 558 297 573 36 54 111 C15 542 388 501 146 109 34 C16 512 417 328 36 62 29 C17 358 287 267 4 20 9 O1 709 416 283 9 10 209 O2 718 455 298 22 21 256 O3 547 419 421 39 64 43 O4 806 467 621 39 258 14 N1 458 370 246 25 22 21 N2 433 388 244 2 30 86 N3 438 403 270 1 25 110 N4 539 328 268 14 12 64 Cl1 492 455 375 32 62 54 Cl2 591 454 440 20 16 8

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Table S13 − Hydrogen coordinates (× 104) and isotropic displacement parameters

(Å2 × 103) compound (3) [PBABH22+(Cl)2. 2H2O]

x y z U(eq) H(2) 8683 3778 6661 50(9) H(3) 9625 1766 6315 58 H(3A) 4878 2532 1974 69 H(3B) 4423 3789 2207 69 H(4) 9903 1320 5129 57 H(4A) 770(2) 5790(3) 1844(14) 45(9) H(4B) 830(3) 4640(4) 2115(19) 92(13) H(5) 9180 2829 4282 48 H(8A) 7055 6303 3305 49 H(8B) 8340 6518 3019 49 H(9A) 6855 4283 2631 47 H(9B) 8156 4443 2361 47 H(10A) 6369 6400 2059 51 H(10B) 7653 6451 1752 51 H(13) 5900 2730 7459 47 H(14) 5184 1235 104 57 H(15) 5437 1719 1292 57 H(16) 6361 3747 1625 50 H1N1 7180(3) 5550(3) 6230(17) 72(10) H2N2 8280(2) 6200(3) 6207(13) 41(7) H3N1 7560(3) 6320(3) 5473(16) 74(9) H2N2 8720(2) 4450(3) 3623(14) 48(8) H3N3 6120(2) 4470(2) 1368(13) 39(7) H1N4 7470(2) 6260(3) 479(15) 59(8) H2N4 6710(2) 6200(3) 1162(13) 450(8) H3N4 7850(3) 5520(3) 1202(18) 80(10)

Table S14 − Hydrogen bonding parameters (Å, deg) of compound (3) [PBABH22+(Cl)2. 2H2O]

D-H...A D...H/ Å H...A/ Å D...A/ Å ∠D-H...Ao N4 --H3N4 ..O4 0.98 1.78(3) 2.753(3) 173( 3) N1 −H1N1 ⋅⋅⋅Cl2 0.94 2.20(3) 3.129(2) 169(3) N1 −H2N1 ⋅⋅⋅Cl1 0.84 2.35(1) 3.188 170(2) O3 −H3A ⋅⋅⋅Cl2 0.85 2.32 3.130(1) 160.00(2) O3 − H 3B ⋅⋅⋅Cl2 0.850 2.290(1) 3.131(2) 169.00 N4− H2N4 ⋅⋅⋅O3 0.87 2.01(2) 2.852(3) 164(3) O4 −H4A ⋅⋅⋅Cl1 0.73 2.47(3) 3.200(3) 178(3) O4 −H4B ⋅⋅⋅Cl1 0.81 2.36(4) 3.157(3) 173(4) N2 −H3N3 ⋅⋅⋅O3 0.78 2.24 (2) 3.006(3) 164(2) N2 −H2N2 ⋅⋅⋅Cl1 0.78 2.53(3) 3.292(2) 166(3) N4 −H1N4 ⋅⋅⋅O2 0.95 1.82(3) 2.650(3) 144(2) N4 −H1N4⋅⋅⋅O1 0.95 2.42(3) 3.022(3) 121(2) N4 −H3N1⋅⋅⋅O1 1.04 1.70(3) 2.629(2) 146(2) N4 −H1N4⋅⋅⋅O2 1.04 2.43(3) 3.066(3) 119(2) C3 −H3⋅⋅⋅O4 0.93 2.5800 3.442(4) 154.00 C5 −H5⋅⋅⋅Cl1 0.93 2.7500 3.612(2) 155.00 C5 −H5⋅⋅⋅N2 0.93 2.5500 2.854(3) 100.00 C8 −H8A⋅⋅⋅O1 0.97 2.4200 2.761(2) 100.00 C10 −H10B⋅⋅⋅O2 0.97 2.4100 2.797(3) 103.00 C15 −H15⋅⋅⋅Cl2 0.93 2.7700 3.653(3) 160.00

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Fig S1 − IR spectrum of PBAB.

Fig S2 - IR spectrum of PBABH2(NO3)2.2H2O.

15

Fig S3 − IR spectrum of PBABH2(Cl)2.2H2O.

Fig S4 − 1H NMR spectrum of PBAB.

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Fig S5 − 1H NMR spectrum of PBABH2(NO3)2.2H2O.

Fig S6 − 1H NMR spectrum of PBABH2(Cl)2.2H2O.

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