Supporting information for:
Anion Binding Behavior of Heterocycle-Strapped Calix[4]pyrroles
Dustin E. Gross, Dae-Wi Yoon, Vincent M. Lynch, Chang-Hee Lee, and Jonathan L. Sessler
Table of Contents
Figure 1. 1H NMR titration of pyrrole-strapped calix[4]pyrrole 3 with TBAF in DMSO-d6. --- 2
Figure 2. 1H NMR titration of pyrrole-strapped calix[4]pyrrole 3 with TBACl in DMSO-d6. --- 3
Figure 3. 1H NMR titration of pyrrole-strapped calix[4]pyrrole 3 with TBABr in DMSO-d6. --- 4
Figure 4. 1H NMR titration of pyrrole-strapped calix[4]pyrrole 3 with TBAOBz in DMSO-d6. --- 5
Figure 5. 1H NMR titration of furan-strapped calix[4]pyrrole 4 with TBAF in DMSO-d6. --- 6
Figure 6. 1H NMR titration of furan-strapped calix[4]pyrrole 4 with TBACl in DMSO-d6. --- 7
Figure 7. 1H NMR titration of furan-strapped calix[4]pyrrole 4 with TBABr in DMSO-d6. --- 8
Figure 8. 1H NMR titration curve of furan-strapped calix[4]pyrrole 4 with TBABr in DMSO-d6. --- 9
Figure 9. 1H NMR titration of furan-strapped calix[4]pyrrole 4 with TBAOBz in DMSO-d6. --- 10
Figure 10. 1H NMR titration curve for calix[4]pyrrole 4 with TBAOBz in DMSO-d6.--- 11
Figure 11.ITC titration of calix[4]pyrrole 1 with TBAOBz in acetonitrile--- 12
Figure 12.ITC titration of phenyl-strapped calix[4]pyrrole 2 with TBABrand TBAOBz in
acetonitrile--- 12
Figure 13.ITC titration of pyrrole-strapped calix[4]pyrrole 3 with TBABrand TBAOBz in
acetonitrile--- 13
Figure 14.ITC titration of furan-strapped calix[4]pyrrole 4 with TBABrand TBAOBz in
acetonitrile--- 13
Figure 15. View of the pyrrole-strapped calix[4]pyrrole 3·F-·2MeOH complex showing
a partial atom labeling scheme. --- 14
Table 1. Crystal data and structure refinement for complex 3·F. --- 15
Table 2. Atomic coordinates (x 104) and equivalent isotropic displacement
parameters (Å2x 103) for complex 3·F. --- 16
Table 3. Bond lengths [Å] and angles [°] for complex 3·F. --- 19
Table 4. Anisotropic displacement parameters (Å2x 103) for complex 3·F. --- 28
Table 5. Hydrogen coordinates (x 104) and isotropic displacement parameters
(Å2x 10 3) for complex 3·F. --- 30
Table 6. Torsion angles [°] for complex 3·F. --- 33
Table 7. Hydrogen bonds for complex 3·F [Å and °]. --- 37
Figure 1. 1H NMR titration of pyrrole-strapped calix[4]pyrrole 3 with TBAF in DMSO-d6.
Figure 2. 1H NMR titration of pyrrole-strapped calix[4]pyrrole 3 with TBACl in DMSO-d6.
Figure 3. 1H NMR titration of pyrrole-strapped calix[4]pyrrole 3 with TBABr in DMSO-d6.
Figure 4. 1H NMR titration of pyrrole-strapped calix[4]pyrrole 3 with TBAOBz in DMSO-d6.
(★= from benzoate)
Figure 5. 1H NMR titration of furan-strapped calix[4]pyrrole 4 with TBAF in DMSO-d6.
Figure 6. 1H NMR titration of Furan-strapped calix[4]pyrrole 4 with TBACl in DMSO-d6.
Figure 7. 1H NMR titration of furan-strapped calix[4]pyrrole 4 with TBABr in DMSO-d6.
Figure 8. 1H NMR titration curve of furan-strapped calix[4]pyrrole 4 with TBABr in DMSO-d6.
Figure 9. 1H NMR titration of furan-strapped calix[4]pyrrole 4 with TBAOBz in DMSO-d6.
(★= from benzoate)
Figure 10. 1H NMR titration curve of furan-strapped calix[4]pyrrole 4 with TBAOBz in DMSO-d6.
Figure 11. Syringe: TBAOBz [10.22 mM]; Cell:1 [1.01 mM]
Figure 12. Left: syringe: TBABr [17.08 mM], cell:2[1.06 mM];
Right: syringe: TBAOBz [10.22 mM], cell:2 [1.00 mM]
Figure 13. Left: syringe:3 [1.08 mM], cell: TBABr [0.094 mM];
Right: syringe: TBAOBz [10.22 mM], cell:3[1.00 mM]
Figure 14. Left: syringe: TBABr [2.21 mM], cell:4[0.166 mM];
Right: syringe:TBAOBz [4.26 mM], cell:4[0.233 mM]
Figure 15. View of the pyrrole-strapped calix[4]pyrrole 3·F-·2MeOH complex showing a partial atom labeling scheme. Displacement ellipsoids are scaled to the 50% probability level. Dashed lines are indicative of H-bonding interactions. The geometry of these interactions is listed in Table 7.
Table 1. Crystal data and structure refinement for complex 3•F.
Empirical formula C56 H89 F N6 O6
Formula weight 961.33
Temperature 153(2) K
Wavelength 0.71073 Å
Crystal system Orthorhombic
Space group Fdd2
Unit cell dimensionsa = 40.2400(2) Å= 90°.
b = 40.8940(6) Å= 90°.
c = 13.2060(6) Å = 90°.
Volume21731.5(10) Å3
Z16
Density (calculated)1.175 Mg/m3
Absorption coefficient0.078 mm-1
F(000)8384
Crystal size0.20 x 0.15 x 0.13 mm
Theta range for data collection2.21 to 27.10°.
Index ranges-51<=h<=51, -52<=k<=52, -16<=l<=16
Reflections collected11647
Independent reflections6233 [R(int) = 0.0442]
Completeness to theta = 27.10°99.6 %
Absorption correctionNone
Refinement methodFull-matrix least-squares on F2
Data / restraints / parameters6233 / 1 / 654
Goodness-of-fit on F21.088
Final R indices [I>2sigma(I)]R1 = 0.0502, wR2 = 0.0982
R indices (all data)R1 = 0.0929, wR2 = 0.1108
Absolute structure parameter-0.4(10)
Extinction coefficient7.7(19)x10-8
Largest diff. peak and hole0.339 and -0.168 e.Å-3
Table 2. Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(Å2 x 103) for complex 3•F. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
______
xyzU(eq)
______
F1 8577(1) 4580(1) 3427(1) 32(1)
O1 8339(1) 3862(1) 1663(2) 48(1)
O2 8496(1) 3387(1) 963(3) 70(1)
O3 9767(1) 4500(1) 862(3) 71(1)
O4 9290(1) 4735(1) 1370(2) 44(1)
N1 9188(1) 4548(1) 4467(2) 30(1)
N2 8603(1) 4003(1) 4620(2) 31(1)
N3 8038(1) 4609(1) 4751(2) 32(1)
N4 8627(1) 5148(1) 4598(2) 30(1)
N5 8950(1) 4142(1) 1101(2) 37(1)
C1 9345(1) 4825(1) 4817(2) 29(1)
C2 9597(1) 4720(1) 5432(2) 31(1)
C3 9594(1) 4372(1) 5434(3) 32(1)
C4 9336(1) 4271(1) 4835(2) 28(1)
C5 9225(1) 3932(1) 4526(2) 30(1)
C6 8883(1) 3847(1) 4949(2) 29(1)
C7 8785(1) 3620(1) 5640(3) 35(1)
C8 8433(1) 3642(1) 5730(3) 36(1)
C9 8325(1) 3879(1) 5086(3) 34(1)
C10 7978(1) 3992(1) 4804(3) 36(1)
C11 7905(1) 4334(1) 5203(3) 34(1)
C12 7697(1) 4446(1) 5948(3) 37(1)
C13 7706(1) 4794(1) 5941(3) 37(1)
C14 7919(1) 4890(1) 5188(3) 32(1)
C15 8008(1) 5227(1) 4791(3) 34(1)
C16 8365(1) 5319(1) 5020(3) 32(1)
C17 8501(1) 5569(1) 5574(3) 37(1)
C18 8850(1) 5548(1) 5503(3) 35(1)
C19 8928(1) 5286(1) 4893(2) 31(1)
C20 9254(1) 5166(1) 4460(3) 31(1)
C21 9477(1) 3678(1) 4904(3) 37(1)
C22 9217(1) 3915(1) 3358(3) 39(1)
C23 7723(1) 3756(1) 5267(3) 48(1)
C24 7775(1) 5481(1) 5270(3) 48(1)
C25 7958(1) 5237(1) 3631(3) 43(1)
C26 9530(1) 5402(1) 4783(3) 39(1)
C27 7943(1) 3999(1) 3636(3) 39(1)
C28 7997(1) 3675(1) 3086(3) 46(1)
C29 8019(1) 3716(1) 1956(3) 55(1)
C30 8553(1) 3662(1) 1172(3) 42(1)
C31 8871(1) 3819(1) 948(3) 39(1)
C32 9153(1) 3656(1) 634(3) 50(1)
C33 9412(1) 3885(1) 615(3) 51(1)
C34 9284(1) 4184(1) 906(3) 40(1)
C35 9474(1) 4487(1) 1030(3) 44(1)
C36 9463(1) 5043(1) 1554(3) 47(1)
C37 9533(1) 5087(1) 2684(3) 41(1)
C38 9220(1) 5170(1) 3280(3) 33(1)
N1A 8739(1) 4634(1) 7909(2) 30(1)
C1A 8985(1) 4827(1) 8537(3) 35(1)
C2A 9218(1) 5054(1) 7953(3) 39(1)
C3A 9477(1) 5189(1) 8682(3) 44(1)
C4A 9731(1) 5403(1) 8151(4) 54(1)
C5A 8911(1) 4411(1) 7148(3) 34(1)
C6A 9115(1) 4125(1) 7562(3) 36(1)
C7A 9450(1) 4195(1) 8037(3) 40(1)
C8A 9662(1) 3886(1) 8077(3) 46(1)
C9A 8539(1) 4431(1) 8653(3) 35(1)
C10A 8277(1) 4209(1) 8189(3) 40(1)
C11A 8143(1) 3974(1) 8982(3) 54(1)
C12A 7864(1) 3762(1) 8593(3) 55(1)
C13A 8517(1) 4862(1) 7289(3) 37(1)
C14A 8344(1) 5141(1) 7854(3) 38(1)
C15A 8038(1) 5070(1) 8483(3) 47(1)
C16A 7835(1) 5377(1) 8667(4) 58(1)
O1B 8689(1) 5205(1) 482(2) 65(1)
C2B 8565(1) 5496(1) 910(4) 84(2)
O1C 8482(1) 4658(1) 1559(2) 42(1)
C2C 8129(1) 4640(1) 1377(3) 50(1)
______
Table 3. Bond lengths [Å] and angles [°] for complex 3•F.
______
S1
O1-C30 1.352(4)
O1-C29 1.470(4)
O2-C30 1.183(4)
O3-C35 1.201(4)
O4-C35 1.335(4)
O4-C36 1.462(4)
N1-C4 1.371(4)
N1-C1 1.376(4)
N1-H1N 0.81(4)
N2-C6 1.367(4)
N2-C9 1.372(4)
N2-H2N 0.80(3)
N3-C14 1.373(4)
N3-C11 1.381(4)
N3-H3N 0.88(3)
N4-C16 1.383(4)
N4-C19 1.389(4)
N4-H4N 0.99(4)
N5-C31 1.373(4)
N5-C34 1.376(4)
N5-H5N 0.91(3)
C1-C2 1.368(4)
C1-C20 1.517(4)
C2-C3 1.424(4)
C2-H2 0.95
C3-C4 1.367(4)
C3-H3 0.95
C4-C5 1.514(4)
C5-C6 1.525(4)
C5-C21 1.534(4)
C5-C22 1.545(5)
C6-C7 1.362(4)
C7-C8 1.422(4)
C7-H7 0.95
C8-C9 1.362(4)
C8-H8 0.95
C9-C10 1.520(4)
C10-C11 1.523(4)
C10-C23 1.536(5)
C10-C27 1.549(5)
C11-C12 1.368(5)
C12-C13 1.425(4)
C12-H12 0.95
C13-C14 1.368(5)
C13-H13 0.95
C14-C15 1.521(4)
C15-C16 1.515(4)
C15-C24 1.533(5)
C15-C25 1.545(5)
C16-C17 1.371(5)
C17-C18 1.411(4)
C17-H17 0.95
C18-C19 1.375(4)
C18-H18 0.95
C19-C20 1.515(4)
C20-C26 1.530(4)
C20-C38 1.565(5)
C21-H21A 0.98
C21-H21B 0.98
C21-H21C 0.98
C22-H22A 0.98
C22-H22B 0.98
C22-H22C 0.98
C23-H23A 0.98
C23-H23B 0.98
C23-H23C 0.98
C24-H24A 0.98
C24-H24B 0.98
C24-H24C 0.98
C25-H25A 0.98
C25-H25B 0.98
C25-H25C 0.98
C26-H26A 0.98
C26-H26B 0.98
C26-H26C 0.98
C27-C28 1.529(5)
C27-H27A 0.99
C27-H27B 0.99
C28-C29 1.505(6)
C28-H28A 0.99
C28-H28B 0.99
C29-H29A 0.99
C29-H29B 0.99
C30-C31 1.461(5)
C31-C32 1.381(5)
C32-C33 1.402(5)
C32-H32 0.95
C33-C34 1.383(5)
C33-H33 0.95
C34-C35 1.464(5)
C36-C37 1.529(5)
C36-H36A 0.99
C36-H36B 0.99
C37-C38 1.525(5)
C37-H37A 0.99
C37-H37B 0.99
C38-H38A 0.99
C38-H38B 0.99
N1A-C1A 1.514(4)
N1A-C9A 1.518(4)
N1A-C5A 1.524(4)
N1A-C13A 1.530(4)
C1A-C2A 1.527(5)
C1A-H1A1 0.99
C1A-H1A2 0.99
C2A-C3A 1.522(5)
C2A-H2A1 0.99
C2A-H2A2 0.99
C3A-C4A 1.516(5)
C3A-H3A1 0.99
C3A-H3A2 0.99
C4A-H4A1 0.98
C4A-H4A2 0.98
C4A-H4A3 0.98
C5A-C6A 1.530(4)
C5A-H5A1 0.99
C5A-H5A2 0.99
C6A-C7A 1.514(5)
C6A-H6A1 0.99
C6A-H6A2 0.99
C7A-C8A 1.527(4)
C7A-H7A1 0.99
C7A-H7A2 0.99
C8A-H8A1 0.98
C8A-H8A2 0.98
C8A-H8A3 0.98
C9A-C10A 1.522(4)
C9A-H9A1 0.99
C9A-H9A2 0.99
C10A-C11A 1.520(5)
C10A-H10A 0.99
C10A-H10B 0.99
C11A-C12A 1.505(5)
C11A-H11A 0.99
C11A-H11B 0.99
C12A-H12A 0.98
C12A-H12B 0.98
C12A-H12C 0.98
C13A-C14A 1.530(4)
C13A-H13A 0.99
C13A-H13B 0.99
C14A-C15A 1.512(5)
C14A-H14A 0.99
C14A-H14B 0.99
C15A-C16A 1.518(5)
C15A-H15A 0.99
C15A-H15B 0.99
C16A-H16A 0.98
C16A-H16B 0.98
C16A-H16C 0.98
O1B-C2B 1.409(5)
O1B-H1BA 0.84
C2B-H2BC 0.96
C2B-H2BA 0.96
C2B-H2BB 0.96
O1C-C2C 1.439(4)
O1C-H1C 0.84
C2C-H2CC 0.96
C2C-H2CA 0.96
C2C-H2CB 0.96
S1
C30-O1-C29 116.0(3)
C35-O4-C36 116.5(3)
C4-N1-C1 111.1(3)
C4-N1-H1N 126(2)
C1-N1-H1N 123(2)
C6-N2-C9 110.9(3)
C6-N2-H2N 122(2)
C9-N2-H2N 127(2)
C14-N3-C11 111.2(3)
C14-N3-H3N 125.2(19)
C11-N3-H3N 123.6(19)
C16-N4-C19 110.3(3)
C16-N4-H4N 124(2)
C19-N4-H4N 125(2)
C31-N5-C34 108.7(3)
C31-N5-H5N 126(2)
C34-N5-H5N 125(2)
C2-C1-N1 106.5(3)
C2-C1-C20 130.7(3)
N1-C1-C20 122.6(3)
C1-C2-C3 107.9(3)
C1-C2-H2 126.1
C3-C2-H2 126.1
C4-C3-C2 107.9(3)
C4-C3-H3 126.0
C2-C3-H3 126.0
C3-C4-N1 106.6(3)
C3-C4-C5 131.0(3)
N1-C4-C5 122.3(3)
C4-C5-C6 112.0(2)
C4-C5-C21 109.7(2)
C6-C5-C21 108.9(3)
C4-C5-C22 108.4(3)
C6-C5-C22 109.7(3)
C21-C5-C22 108.0(3)
C7-C6-N2 107.0(3)
C7-C6-C5 131.5(3)
N2-C6-C5 121.5(3)
C6-C7-C8 107.6(3)
C6-C7-H7 126.2
C8-C7-H7 126.2
C9-C8-C7 108.1(3)
C9-C8-H8 126.0
C7-C8-H8 126.0
C8-C9-N2 106.5(3)
C8-C9-C10 131.5(3)
N2-C9-C10 121.8(3)
C9-C10-C11 111.8(3)
C9-C10-C23 109.1(3)
C11-C10-C23 108.1(3)
C9-C10-C27 109.4(3)
C11-C10-C27 108.1(3)
C23-C10-C27 110.4(3)
C12-C11-N3 106.1(3)
C12-C11-C10 132.3(3)
N3-C11-C10 121.4(3)
C11-C12-C13 108.3(3)
C11-C12-H12 125.9
C13-C12-H12 125.9
C14-C13-C12 107.8(3)
C14-C13-H13 126.1
C12-C13-H13 126.1
C13-C14-N3 106.6(3)
C13-C14-C15 131.1(3)
N3-C14-C15 122.1(3)
C16-C15-C14 112.3(2)
C16-C15-C24 109.3(3)
C14-C15-C24 109.0(3)
C16-C15-C25 108.4(3)
C14-C15-C25 109.5(3)
C24-C15-C25 108.3(3)
C17-C16-N4 106.6(3)
C17-C16-C15 132.1(3)
N4-C16-C15 121.3(3)
C16-C17-C18 108.5(3)
C16-C17-H17 125.8
C18-C17-H17 125.7
C19-C18-C17 108.2(3)
C19-C18-H18 125.9
C17-C18-H18 125.9
C18-C19-N4 106.4(3)
C18-C19-C20 132.0(3)
N4-C19-C20 121.2(3)
C19-C20-C1 113.0(3)
C19-C20-C26 108.6(3)
C1-C20-C26 108.5(2)
C19-C20-C38 107.2(3)
C1-C20-C38 110.0(3)
C26-C20-C38 109.6(3)
C5-C21-H21A 109.5
C5-C21-H21B 109.5
H21A-C21-H21B 109.5
C5-C21-H21C 109.5
H21A-C21-H21C 109.5
H21B-C21-H21C 109.5
C5-C22-H22A 109.5
C5-C22-H22B 109.5
H22A-C22-H22B 109.5
C5-C22-H22C 109.5
H22A-C22-H22C 109.5
H22B-C22-H22C 109.5
C10-C23-H23A 109.5
C10-C23-H23B 109.5
H23A-C23-H23B 109.5
C10-C23-H23C 109.5
H23A-C23-H23C 109.5
H23B-C23-H23C 109.5
C15-C24-H24A 109.5
C15-C24-H24B 109.5
H24A-C24-H24B 109.5
C15-C24-H24C 109.5
H24A-C24-H24C 109.5
H24B-C24-H24C 109.5
C15-C25-H25A 109.5
C15-C25-H25B 109.5
H25A-C25-H25B 109.5
C15-C25-H25C 109.5
H25A-C25-H25C 109.5
H25B-C25-H25C 109.5
C20-C26-H26A 109.5
C20-C26-H26B 109.5
H26A-C26-H26B 109.5
C20-C26-H26C 109.5
H26A-C26-H26C 109.5
H26B-C26-H26C 109.5
C28-C27-C10 116.3(3)
C28-C27-H27A 108.2
C10-C27-H27A 108.2
C28-C27-H27B 108.2
C10-C27-H27B 108.2
H27A-C27-H27B 107.4
C29-C28-C27 112.4(3)
C29-C28-H28A 109.1
C27-C28-H28A 109.1
C29-C28-H28B 109.1
C27-C28-H28B 109.1
H28A-C28-H28B 107.9
O1-C29-C28 111.0(3)
O1-C29-H29A 109.4
C28-C29-H29A 109.4
O1-C29-H29B 109.4
C28-C29-H29B 109.4
H29A-C29-H29B 108.0
O2-C30-O1 124.3(4)
O2-C30-C31 122.8(3)
O1-C30-C31 112.9(3)
N5-C31-C32 108.4(3)
N5-C31-C30 126.7(3)
C32-C31-C30 124.6(3)
C31-C32-C33 107.1(3)
C31-C32-H32 126.4
C33-C32-H32 126.4
C34-C33-C32 107.9(3)
C34-C33-H33 126.0
C32-C33-H33 126.0
N5-C34-C33 107.8(3)
N5-C34-C35 126.6(3)
C33-C34-C35 125.6(3)
O3-C35-O4 125.1(3)
O3-C35-C34 122.1(3)
O4-C35-C34 112.8(3)
O4-C36-C37 110.5(3)
O4-C36-H36A 109.6
C37-C36-H36A 109.6
O4-C36-H36B 109.6
C37-C36-H36B 109.6
H36A-C36-H36B 108.1
C38-C37-C36 112.2(3)
C38-C37-H37A 109.2
C36-C37-H37A 109.2
C38-C37-H37B 109.2
C36-C37-H37B 109.2
H37A-C37-H37B 107.9
C37-C38-C20 116.0(3)
C37-C38-H38A 108.3
C20-C38-H38A 108.3
C37-C38-H38B 108.3
C20-C38-H38B 108.3
H38A-C38-H38B 107.4
C1A-N1A-C9A 106.2(2)
C1A-N1A-C5A 112.1(2)
C9A-N1A-C5A 110.0(2)
C1A-N1A-C13A 111.0(2)
C9A-N1A-C13A 111.7(2)
C5A-N1A-C13A 106.1(2)
N1A-C1A-C2A 116.2(3)
N1A-C1A-H1A1 108.2
C2A-C1A-H1A1 108.2
N1A-C1A-H1A2 108.2
C2A-C1A-H1A2 108.2
H1A1-C1A-H1A2 107.4
C3A-C2A-C1A 108.7(3)
C3A-C2A-H2A1 110.0
C1A-C2A-H2A1 110.0
C3A-C2A-H2A2 110.0
C1A-C2A-H2A2 110.0
H2A1-C2A-H2A2 108.3
C4A-C3A-C2A 112.2(3)
C4A-C3A-H3A1 109.2
C2A-C3A-H3A1 109.2
C4A-C3A-H3A2 109.2
C2A-C3A-H3A2 109.2
H3A1-C3A-H3A2 107.9
C3A-C4A-H4A1 109.5
C3A-C4A-H4A2 109.5
H4A1-C4A-H4A2 109.5
C3A-C4A-H4A3 109.5
H4A1-C4A-H4A3 109.5
H4A2-C4A-H4A3 109.5
N1A-C5A-C6A 117.7(3)
N1A-C5A-H5A1 107.9
C6A-C5A-H5A1 107.9
N1A-C5A-H5A2 107.9
C6A-C5A-H5A2 107.9
H5A1-C5A-H5A2 107.2
C7A-C6A-C5A 118.8(3)
C7A-C6A-H6A1 107.6
C5A-C6A-H6A1 107.6
C7A-C6A-H6A2 107.6
C5A-C6A-H6A2 107.6
H6A1-C6A-H6A2 107.1
C6A-C7A-C8A 110.7(3)
C6A-C7A-H7A1 109.5
C8A-C7A-H7A1 109.5
C6A-C7A-H7A2 109.5
C8A-C7A-H7A2 109.5
H7A1-C7A-H7A2 108.1
C7A-C8A-H8A1 109.5
C7A-C8A-H8A2 109.5
H8A1-C8A-H8A2 109.5
C7A-C8A-H8A3 109.5
H8A1-C8A-H8A3 109.5
H8A2-C8A-H8A3 109.5
N1A-C9A-C10A 115.8(3)
N1A-C9A-H9A1 108.3
C10A-C9A-H9A1 108.3
N1A-C9A-H9A2 108.3
C10A-C9A-H9A2 108.3
H9A1-C9A-H9A2 107.4
C11A-C10A-C9A 110.3(3)
C11A-C10A-H10A 109.6
C9A-C10A-H10A 109.6
C11A-C10A-H10B 109.6
C9A-C10A-H10B 109.6
H10A-C10A-H10B 108.1
C12A-C11A-C10A 113.1(3)
C12A-C11A-H11A 109.0
C10A-C11A-H11A 109.0
C12A-C11A-H11B 109.0
C10A-C11A-H11B 109.0
H11A-C11A-H11B 107.8
C11A-C12A-H12A 109.5
C11A-C12A-H12B 109.5
H12A-C12A-H12B 109.5
C11A-C12A-H12C 109.5
H12A-C12A-H12C 109.5
H12B-C12A-H12C 109.5
C14A-C13A-N1A 117.3(3)
C14A-C13A-H13A 108.0
N1A-C13A-H13A 108.0
C14A-C13A-H13B 108.0
N1A-C13A-H13B 108.0
H13A-C13A-H13B 107.2
C15A-C14A-C13A 119.6(3)
C15A-C14A-H14A 107.4
C13A-C14A-H14A 107.4
C15A-C14A-H14B 107.4
C13A-C14A-H14B 107.4
H14A-C14A-H14B 106.9
C14A-C15A-C16A 111.6(3)
C14A-C15A-H15A 109.3
C16A-C15A-H15A 109.3
C14A-C15A-H15B 109.3
C16A-C15A-H15B 109.3
H15A-C15A-H15B 108.0
C15A-C16A-H16A 109.5
C15A-C16A-H16B 109.5
H16A-C16A-H16B 109.5
C15A-C16A-H16C 109.5
H16A-C16A-H16C 109.5
H16B-C16A-H16C 109.5
C2B-O1B-H1BA 111.9
O1B-C2B-H2BC 108.1
O1B-C2B-H2BA 111.8
H2BC-C2B-H2BA 108.0
O1B-C2B-H2BB 111.4
H2BC-C2B-H2BB 108.0
H2BA-C2B-H2BB 109.4
C2C-O1C-H1C 109.5
O1C-C2C-H2CC 110.3
O1C-C2C-H2CA 109.0
H2CC-C2C-H2CA 110.0
O1C-C2C-H2CB 109.5
H2CC-C2C-H2CB 109.9
H2CA-C2C-H2CB 108.1
S1
______
Table 4. Anisotropic displacement parameters (Å2 x 103) for complex 3•F. The
anisotropic displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ]
______
U11U22U33U23U13U12
______
F131(1) 34(1)31(1) 1(1)-2(1) -2(1)
O143(1) 51(1)51(2) -15(1)3(1) -6(1)
O265(2) 45(2)100(2) -16(2)4(2) -4(1)
O344(2) 66(2)102(3) -11(2)27(2) -4(1)
O439(1) 48(1)46(2) -5(1)4(1) -2(1)
N124(1) 32(1)34(2) 2(1)-7(1) -1(1)
N232(2) 29(1)32(2) 8(1)-2(1) 0(1)
N329(1) 38(2)30(2) 3(1)6(1) 1(1)
N431(1) 27(1)34(2) -2(1)-3(1) -2(1)
N541(2) 41(2)30(2) -1(1)0(1) 7(1)
C125(2) 30(2)31(2) 0(1)0(1) -2(1)
C227(2) 35(2)32(2) -1(2)-2(2) -4(1)
C326(2) 36(2)35(2) 8(2)0(2) 4(1)
C425(2) 31(2)28(2) 4(1)3(1) 2(1)
C533(2) 30(2)28(2) 0(1)-3(1) 3(1)
C632(2) 25(2)29(2) -2(1)-2(1) 1(1)
C743(2) 28(2)33(2) 2(1)-3(2) 2(1)
C840(2) 28(2)41(2) 6(2)4(2) -3(1)
C935(2) 28(2)38(2) -1(2)2(2) -6(1)
C1028(2) 34(2)45(2) -1(2)-1(2) -1(1)
C1127(2) 35(2)38(2) 3(2)-4(2) -2(1)
C1230(2) 44(2)37(2) 7(2)2(2) -4(2)
C1330(2) 42(2)38(2) -2(2)1(2) 4(1)
C1424(2) 35(2)38(2) -2(2)-4(1) 5(1)
C1529(2) 33(2)40(2) 2(2)1(2) 4(1)
C1631(2) 30(2)34(2) 5(2)1(2) 4(1)
C1747(2) 27(2)37(2) -1(2)3(2) 2(2)
C1835(2) 28(2)41(2) -1(2)-5(2) -7(1)
C1931(2) 27(2)34(2) 1(1)-3(2) -2(1)
C2027(2) 29(2)36(2) 2(1)-7(1) -1(1)
C2137(2) 35(2)40(2) 1(2)-2(2) 4(1)
C2246(2) 38(2)33(2) 1(2)3(2) 2(2)
C2338(2) 42(2)66(3) 5(2)5(2) -7(2)
C2438(2) 39(2)67(3) 3(2)3(2) 8(2)
C2539(2) 44(2)46(2) 8(2)-7(2) -1(2)
C2631(2) 35(2)50(2) 3(2)-7(2) -1(1)
C2733(2) 36(2)47(2) -1(2)-6(2) -2(1)
C2838(2) 39(2)61(3) -6(2)2(2) -10(2)
C2946(2) 59(2)59(3) -20(2)-3(2) -14(2)
C3050(2) 36(2)41(2) -3(2)-8(2) 3(2)
C3147(2) 39(2)30(2) -3(2)-1(2) 4(2)
C3260(2) 44(2)46(2) -4(2)-1(2) 5(2)
C3349(2) 57(2)47(2) 0(2)8(2) 13(2)
C3440(2) 46(2)35(2) 4(2)5(2) 3(2)
C3543(2) 53(2)36(2) 3(2)8(2) 4(2)
C3646(2) 46(2)49(2) 0(2)7(2) -8(2)
C3733(2) 42(2)47(2) 4(2)0(2) -4(2)
C3828(2) 27(2)43(2) 2(2)0(2) -4(1)
N1A28(1) 34(1)28(1) 1(1)2(1) -1(1)
C1A34(2) 39(2)33(2) -6(2)-2(2) 1(2)
C2A41(2) 36(2)41(2) -4(2)6(2) -6(2)
C3A37(2) 40(2)55(2) -5(2)1(2) -2(2)
C4A43(2) 46(2)72(3) -8(2)9(2) -5(2)
C5A34(2) 37(2)29(2) -4(2)1(1) 0(1)
C6A36(2) 31(2)41(2) -1(2)4(2) 0(2)
C7A43(2) 36(2)41(2) -1(2)-5(2) 2(2)
C8A41(2) 41(2)56(2) -3(2)-4(2) 8(2)
C9A32(2) 42(2)30(2) 4(2)2(1) -1(2)
C10A37(2) 44(2)38(2) 2(2)-1(2) -4(2)
C11A63(2) 56(2)43(2) 2(2)4(2) -22(2)
C12A54(2) 57(2)54(3) -1(2)4(2) -15(2)
C13A34(2) 43(2)34(2) 8(2)4(2) 3(2)
C14A36(2) 38(2)41(2) 4(2)4(2) 5(2)
C15A42(2) 47(2)53(2) 3(2)10(2) 5(2)
C16A51(2) 57(2)66(3) 0(2)24(2) 3(2)
O1B93(2) 47(2)56(2) 1(1)19(2) 12(1)
C2B104(4) 59(3)89(4) -21(3)-1(3) 22(3)
O1C42(1) 51(1)33(1) 3(1)-3(1) 4(1)
C2C44(2) 64(2)41(2) -1(2)-8(2) 4(2)
______
Table 5. Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2 x 103)for complex 3•F.
______
x y z U(eq)
______
H2 9748 4856 5794 37
H3 9744 4234 5788 39
H7 8925 3473 5996 42
H8 8297 3513 6163 43
H12 7569 4313 6393 44
H13 7586 4935 6381 44
H17 8381 5729 5944 44
H18 9005 5690 5822 41
H21A 9479 3677 5646 56
H21B 9699 3734 4651 56
H21C 9414 3461 4657 56
H22A 9147 3696 3145 59
H22B 9439 3961 3089 59
H22C 9059 4077 3098 59
H23A 7765 3534 5022 72
H23B 7498 3823 5068 72
H23C 7741 3761 6007 72
H24A 7806 5482 6006 72
H24B 7544 5424 5114 72
H24C 7825 5698 4997 72
H25A 8014 5455 3376 65
H25B 7726 5187 3471 65
H25C 8103 5074 3312 65
H26A 9482 5620 4515 58
H26B 9743 5325 4516 58
H26C 9540 5411 5524 58
H27A 7718 4080 3467 46
H27B 8105 4160 3366 46
H28A 8205 3573 3335 55
H28B 7812 3525 3247 55
H29A 7994 3501 1623 65
H29B 7836 3859 1722 65
H32 9168 3431 464 60
H33 9636 3842 433 61
H36A 9326 5227 1308 56
H36B 9675 5045 1175 56
H37A 9630 4882 2956 49
H37B 9698 5263 2776 49
H38A 9043 5013 3086 39
H38B 9144 5391 3072 39
H1A1 9123 4671 8927 42
H1A2 8859 4961 9031 42
H2A1 9329 4932 7401 47
H2A2 9090 5236 7648 47
H3A1 9364 5318 9214 53
H3A2 9593 5005 9016 53
H4A1 9851 5272 7649 80
H4A2 9887 5490 8650 80
H4A3 9617 5584 7811 80
H5A1 9060 4548 6728 40
H5A2 8739 4321 6691 40
H6A1 8978 4012 8076 43
H6A2 9151 3969 7000 43
H7A1 9418 4281 8731 48
H7A2 9567 4365 7636 48
H8A1 9544 3717 8462 69
H8A2 9874 3934 8408 69
H8A3 9703 3807 7387 69
H9A1 8427 4581 9132 42
H9A2 8695 4294 9049 42
H10A 8092 4342 7915 48
H10B 8375 4083 7622 48
H11A 8326 3831 9218 65
H11B 8062 4101 9570 65
H12A 7677 3901 8391 82
H12B 7793 3612 9127 82
H12C 7942 3637 8006 82
H13A 8654 4959 6744 44
H13B 8343 4727 6960 44
H14A 8511 5243 8307 46
H14B 8282 5308 7346 46
H15A 8107 4976 9142 57
H15B 7899 4906 8130 57
H16A 7965 5532 9068 88
H16B 7631 5320 9035 88
H16C 7776 5477 8016 88
H1BA 8627 5039 808 98
H2BC 8522 5647 370 126
H2BA 8723 5595 1361 126
H2BB 8360 5459 1264 126
H1C 8520 4622 2174 64
H2CC 8011 4624 2007 75
H2CA 8084 4452 965 75
H2CB 8058 4831 1014 75
H3N 8178(8) 4601(7) 4240(30) 24(8)
H2N 8609(7) 4138(8) 4180(30) 25(9)
H5N 8807(8) 4304(8) 1270(30) 35(9)
H1N 9026(8) 4555(7) 4110(30) 29(9)
H4N 8602(9) 4961(10) 4130(30) 59(11)
______
Table 6. Torsion angles [°] for complex 3•F.
______
C4-N1-C1-C2-0.8(4)
C4-N1-C1-C20174.5(3)
N1-C1-C2-C31.1(4)
C20-C1-C2-C3-173.6(3)
C1-C2-C3-C4-1.1(4)
C2-C3-C4-N10.6(4)
C2-C3-C4-C5176.9(3)
C1-N1-C4-C30.1(4)
C1-N1-C4-C5-176.6(3)
C3-C4-C5-C6114.9(4)
N1-C4-C5-C6-69.4(4)
C3-C4-C5-C21-6.2(5)
N1-C4-C5-C21169.5(3)
C3-C4-C5-C22-123.9(4)
N1-C4-C5-C2251.8(4)
C9-N2-C6-C70.0(3)
C9-N2-C6-C5178.2(3)
C4-C5-C6-C7-114.1(4)
C21-C5-C6-C77.4(5)
C22-C5-C6-C7125.4(4)
C4-C5-C6-N268.2(4)
C21-C5-C6-N2-170.3(3)
C22-C5-C6-N2-52.3(4)
N2-C6-C7-C8-0.4(3)
C5-C6-C7-C8-178.3(3)
C6-C7-C8-C90.6(4)
C7-C8-C9-N2-0.6(4)
C7-C8-C9-C10174.8(3)
C6-N2-C9-C80.4(4)
C6-N2-C9-C10-175.6(3)
C8-C9-C10-C11111.5(4)
N2-C9-C10-C11-73.7(4)
C8-C9-C10-C23-7.9(5)
N2-C9-C10-C23166.9(3)
C8-C9-C10-C27-128.8(4)
N2-C9-C10-C2746.0(4)
C14-N3-C11-C12-0.3(3)
C14-N3-C11-C10175.3(3)
C9-C10-C11-C12-110.2(4)
C23-C10-C11-C129.9(5)
C27-C10-C11-C12129.4(4)
C9-C10-C11-N375.5(4)
C23-C10-C11-N3-164.5(3)
C27-C10-C11-N3-45.0(4)
N3-C11-C12-C130.1(3)
C10-C11-C12-C13-174.9(3)
C11-C12-C13-C140.2(4)
C12-C13-C14-N3-0.4(3)
C12-C13-C14-C15175.6(3)
C11-N3-C14-C130.5(3)
C11-N3-C14-C15-176.0(3)
C13-C14-C15-C16112.7(4)
N3-C14-C15-C16-71.9(4)
C13-C14-C15-C24-8.7(5)
N3-C14-C15-C24166.8(3)
C13-C14-C15-C25-126.9(4)
N3-C14-C15-C2548.5(4)
C19-N4-C16-C170.8(3)
C19-N4-C16-C15177.8(3)
C14-C15-C16-C17-119.0(4)
C24-C15-C16-C172.1(5)
C25-C15-C16-C17119.9(4)
C14-C15-C16-N464.9(4)
C24-C15-C16-N4-174.0(3)
C25-C15-C16-N4-56.1(4)
N4-C16-C17-C18-0.9(4)
C15-C16-C17-C18-177.4(3)
C16-C17-C18-C190.7(4)
C17-C18-C19-N4-0.2(4)
C17-C18-C19-C20172.7(3)
C16-N4-C19-C18-0.4(3)
C16-N4-C19-C20-174.2(3)
C18-C19-C20-C1118.5(4)
N4-C19-C20-C1-69.4(4)
C18-C19-C20-C26-1.9(5)
N4-C19-C20-C26170.2(3)
C18-C19-C20-C38-120.2(4)
N4-C19-C20-C3851.9(4)
C2-C1-C20-C19-112.3(4)
N1-C1-C20-C1973.7(4)
C2-C1-C20-C268.2(5)
N1-C1-C20-C26-165.8(3)
C2-C1-C20-C38128.0(4)
N1-C1-C20-C38-46.0(4)
C9-C10-C27-C2859.8(4)
C11-C10-C27-C28-178.3(3)
C23-C10-C27-C28-60.3(4)
C10-C27-C28-C29-169.9(3)
C30-O1-C29-C28110.0(4)
C27-C28-C29-O174.0(4)
C29-O1-C30-O20.9(5)
C29-O1-C30-C31-177.3(3)
C34-N5-C31-C32-1.2(4)
C34-N5-C31-C30173.0(3)
O2-C30-C31-N5175.3(4)
O1-C30-C31-N5-6.4(5)
O2-C30-C31-C32-11.3(6)
O1-C30-C31-C32166.9(3)
N5-C31-C32-C331.1(4)
C30-C31-C32-C33-173.3(3)
C31-C32-C33-C34-0.6(4)
C31-N5-C34-C330.8(4)
C31-N5-C34-C35-176.4(3)
C32-C33-C34-N5-0.1(4)
C32-C33-C34-C35177.1(3)
C36-O4-C35-O3-0.4(6)
C36-O4-C35-C34177.7(3)
N5-C34-C35-O3178.3(4)
C33-C34-C35-O31.6(6)
N5-C34-C35-O40.1(5)
C33-C34-C35-O4-176.6(4)
C35-O4-C36-C37-100.9(4)
O4-C36-C37-C38-73.4(4)
C36-C37-C38-C20170.8(3)
C19-C20-C38-C37174.7(2)
C1-C20-C38-C37-62.1(3)
C26-C20-C38-C3757.0(4)
C9A-N1A-C1A-C2A-179.9(3)
C5A-N1A-C1A-C2A60.0(3)
C13A-N1A-C1A-C2A-58.3(3)
N1A-C1A-C2A-C3A-172.1(3)
C1A-C2A-C3A-C4A176.9(3)
C1A-N1A-C5A-C6A66.9(3)
C9A-N1A-C5A-C6A-51.0(3)
C13A-N1A-C5A-C6A-171.9(3)
N1A-C5A-C6A-C7A-74.7(4)
C5A-C6A-C7A-C8A-161.0(3)
C1A-N1A-C9A-C10A-178.8(3)
C5A-N1A-C9A-C10A-57.4(3)
C13A-N1A-C9A-C10A60.1(4)
N1A-C9A-C10A-C11A169.0(3)
C9A-C10A-C11A-C12A175.8(3)
C1A-N1A-C13A-C14A-50.9(3)
C9A-N1A-C13A-C14A67.4(3)
C5A-N1A-C13A-C14A-172.9(3)
N1A-C13A-C14A-C15A-77.9(4)
C13A-C14A-C15A-C16A-159.6(3)
______
Table 7. Hydrogen bond interactions for complex 3•F [Å and °].
______
D-H...Ad(D-H)d(H...A)d(D...A)<(DHA)
______
N1-H1N...F10.81(4)2.02(4)2.820(3)170(3)
N2-H2N...F10.80(3)2.07(3)2.838(3)161(3)
N3-H3N...F10.88(3)1.93(3)2.786(3)164(3)
N4-H4N...F10.99(4)1.81(4)2.800(3)171(4)
N5-H5N...O1C0.91(3)1.99(4)2.896(4)177(3)
O1C-H1C...F10.841.682.516(3)174.8
______
S1