Supporting Information
Exo- and Endo-hedral Interactions of
Counteranions with Tetracationic M2L4
Metallosupramolecular Architectures.
James E. M. Lewisa and James D. Crowley*a
a
Department of Chemistry, University of Otago, PO Box 56, Dunedin,
New Zealand; Fax: +64 3 479 7906; Tel: +64 3 479 7731.
*jcrowley@chemistry.otago.ac.nz
S1
Contents
1
2
3
4
Experimental Procedures ................................................................................................................ 3
1.1
General.................................................................................................................................... 3
1.2
Synthesis of [Pd2L4](NO3)4 ....................................................................................................... 3
1.3
Synthesis of [Pd2L4](OTf)4 ........................................................................................................ 4
1.4
Synthesis of [Pd2L4](OMs)4 ...................................................................................................... 6
1.5
Synthesis of [Pd2L4](OTs)4 ....................................................................................................... 7
Additional 1H DOSY NMR Spectra ................................................................................................. 10
2.1
Bu4NOTs ................................................................................................................................ 10
2.2
Bu4NOMs ............................................................................................................................... 10
2.3
Ligand 1 ................................................................................................................................. 11
2.4
[Pd2L4](BF4)4 ........................................................................................................................... 11
Stacked 1H NMR Spectra ............................................................................................................... 12
3.1
Bu4NOMs and [Pd2L4](OMs)4 ................................................................................................. 12
3.2
Bu4NOTs and [Pd2L4](OTs)4.................................................................................................... 12
Stacked 19F NMR Spectra .............................................................................................................. 13
4.1
NaOTf and [Pd2L4](OTf)4 ........................................................................................................ 13
4.2
NaBF4 and [Pd2L4](BF4)4 ......................................................................................................... 13
5
UV-Vis Spectra............................................................................................................................... 14
6
X-ray Data...................................................................................................................................... 15
6.1
Experimental ......................................................................................................................... 15
6.2
[Pd2L4](BF4)4 ........................................................................................................................... 16
6.3
[Pd2L4](OTf)4 .......................................................................................................................... 18
6.4
[Pd2L4](OMs)4 ........................................................................................................................ 20
6.5
[Pd2L4](OTs)4 .......................................................................................................................... 22
7
Calculation of Cavity Volume ........................................................................................................ 24
8
SPARTAN Models of 2⊃X- ............................................................................................................. 25
9
References .................................................................................................................................... 29
S2
1
1.1
Experimental Procedures
General
Unless otherwise stated, all reagents were purchased from commercial sources and used without
further purification. Ligand 1[1] and complex 2(BF4)4[2] were synthesised according to literature
procedure. All solvents were laboratory reagent grade. 1H and 13C NMR spectra were recorded on
either a 400 MHz Varian 400 MR or Varian 500 MHz VNMRS spectrometer. Chemical shifts are
reported in parts per million and referenced to residual solvent peaks (d6-DMSO: 1H δ 2.50 ppm; 13C
δ 39.52 ppm). Coupling constants (J) are reported in Hertz (Hz). Standard abbreviations indicating
multiplicity were used as follows: m = multiplet, q = quartet, t = triplet, dt = double triplet, d =
doublet, dd = double doublet, s = singlet. IR spectra were recorded on a Bruker ALPHA FT-IR
spectrometer with an attached ALPHA-P measurement module. Microanalyses were performed at
the Campbell Microanalytical Laboratory at the University of Otago. Electrospray mass spectra
(ESMS) were collected on a Bruker micro-TOF-Q spectrometer. UV-visible absorption spectra were
acquired with a Jasco V550 UV/VIS spectrophotometer.
1.2
Synthesis of [Pd2L4](NO3)4
1 (0.05 g, 0.18 mmol, 2 eq.) and Pd(NO3)2(H2O)2 (0.02 g, 0.09 mmol, 1 eq.) were stirred in DMF (5 mL)
for one hour. After filtering through Celite the filtrate was left for vapour diffusion of diethyl ether to
precipitate the product as a tan solid. Yield 0.07 g (0.04 mmol, 94%). 1H NMR (d6-DMSO, 400 MHz) δ:
9.72 (s, 8H, Ha), 9.40 (d, J = 5.9 Hz, 8H, Hb), 8.32 (d, J = 8.0 Hz, 8H, Hd), 7.97 (t, J = 7.8 Hz, 4H, Hf), 7.84
(dd, J = 5.9, 7.9 Hz, 8H, Hc), 7.75 (d, J = 7.8 Hz, 8H, He). Diffusion coefficient (d6-DMSO, 298 K) D: 1.09
× 10-10 m2s-1. 13C NMR (d6-DMSO, 100 MHz) δ: 153.6 (Ca), 151.1 (Cb), 143.3 (Cd), 141.9, 138.0 (Cf),
128.6 (Ce), 127.3 (Cc), 121.6, 93.4, 83.3. IR (ATR): ν (cm-1) 3071, 1651, 1572, 1558, 1481, 1444, 1422,
1328, 1239, 1196, 1105, 1029, 984, 912, 693. HRESI-MS (DMSO/CH3CN): m/z = 304.0880 [LNa]+ calc.
3040845; 585.1807 [L2Na]+ calc. 585.1798; 866.2741 [L3Na]+ calc. 866.2751. UV-Vis (DMSO, ε [M-1cm1
]): λmax nm = 313 (1.11 × 105). Anal. calc. for 2(NO3)4·7H2O·Et2O: C, 53.79; H, 3.84; N, 12.55%. Found:
C, 53.76; H, 3.82; N, 12.38%.
Figure 1 1H NMR spectrum (400 MHz, d6-DMSO) of [Pd2L4](NO3)4.
S3
Figure 2 13C NMR spectrum (100 MHz, d6-DMSO) of [Pd2L4](NO3)4.
Figure 3 1H DOSY NMR spectrum (500 MHz, d6-DMSO) of [Pd2L4](NO3)4.
1.3
Synthesis of [Pd2L4](OTf)4
[Pd(CH3CN)4](BF4)2 (0.02 g, 0.09 mmol, 1 eq.) and silver triflate (0.05 g, 0.18 mmol, 2 eq.) were
stirred in acetonitrile (5 mL) for 30 minutes. After filtering through Celite, 1 (0.05 g, 0.18 mmol, 2
eq.) was added as a solid and stirred for a further 30 minutes. Diethyl ether was added to precipitate
the product as a tan solid that was washed with diethyl ether and dried in vacuo. Yield 0.07 g
(0.04 mmol, 86%). 1H NMR (d6-DMSO, 400 MHz) δ: 9.54 (d, J = 1.4 Hz, 8H, Ha), 9.38 (d, J = 5.1 Hz, 8H,
Hb), 8.35 (d, 8H, J = 8.0 Hz, Hd), 8.01 (t, J = 7.8 Hz, 4H, Hf), 7.86 (dd, J = 5.9, 7.9 Hz, 8H, Hc), 7.79 (d, J =
7.8 Hz, 8H, He). 19F NMR (d6-DMSO, 376 MHz) δ: -77.76. Diffusion coefficient (d6-DMSO, 298 K) D:
1.16 × 10-10 m2s-1. 13C NMR (d6-DMSO, 100 MHz) δ: 153.3 (Ca), 151.0 (Cb), 143.5 (Cd), 141.8, 138.3
(Cf), 128.6 (Ce), 127.3 (Cc), 121.5, 93.3, 83.6. IR (ATR): ν (cm-1) 3071, 1654, 1574, 1557, 1482, 1444,
1420, 1388, 1161, 1120, 1031, 1010, 810. HRESI-MS (CH3CN): m/z = 282.1230 [LH]+ calc. 282.1026;
334.0635 [PdL2]2+ calc. 334.0472; 334.0635 [Pd2L4]4+ calc. 334.0466; 457.0587 [Pd2L4Cl]3+ calc.
457.0526; 495.0546 [Pd2L4OTf]3+ calc. 495.0471; 817.0560 [Pd2L4(OTf)2]2+ calc. 817.0470. UV-Vis
(DMSO, ε [M-1cm-1]): λmax nm = 318 (1.16 × 105). Anal. calc. for 2(OTf)4·2CH3CN·11H2O: C, 45.56; H,
3.28; N, 8.85%. Found: C, 45.39; H, 3.14; N, 9.11%.
S4
Figure 4 1H NMR spectrum (400 MHz, d6-DMSO) of [Pd2L4](OTf)4.
Figure 5 13C NMR spectrum (100 MHz, d6-DMSO) of [Pd2L4](OTf)4.
Figure 6 19F NMR spectrum (376 MHz, d6-DMSO) of [Pd2L4](OTf)4.
Figure 7 1H DOSY NMR spectrum (500 MHz, d6-DMSO) of [Pd2L4](OTf)4.
S5
1.4
Synthesis of [Pd2L4](OMs)4
[Pd(CH3CN)2Cl2] (0.02 g, 0.09 mmol, 1 eq.) and silver mesylate (0.04 g, 0.18 mmol, 2 eq.) were stirred
in acetonitrile (5 mL) for 30 minutes. After filtering through Celite, 1 (0.05 g, 0.18 mmol, 2 eq.) was
added and the reaction mixture stirred for a further 30 minutes. The resulting tan precipitate was
isolated by filtration, washed with diethyl ether and dried in vacuo. Yield 0.06 g (0.04 mmol, 82%).
1
H NMR (d6-DMSO, 400 MHz) δ: 9.61 (s, br, 8H, Ha), 9.48 (d, J = 4.5 Hz, 8H, Hb), 8.34 (dt, J = 1.5, 8.1
Hz, 8H, Hd), 8.01 (dd, J = 7.5, 8.1 Hz, 4H, Hf), 7.85 (dd, J = 6.0, 8.0 Hz, 8H, Hc), 7.79 (d, J = 7.8 Hz, 8H,
He). Diffusion coefficient (d6-DMSO, 298 K) D: 1.09 × 10-10 m2s-1 (24+); 3.99 × 10-10 m2s-1 (OMs-).
13
C NMR (d6-DMSO, 100 MHz) δ: 153.5 (Ca), 151.3 (Cb), 143.3 (Cd), 141.9, 138.2 (Cf), 128.6 (Ce), 127.3
(Cc), 121.4, 93.3, 83.6, 30.7 (COMs). IR (ATR): ν (cm-1) 3074, 2967, 1575, 1557, 1481, 1443, 1415, 1160,
1039, 984, 951, 809, 771. HRESI-MS (DMSO/CH3CN): m/z = 282.1332 [LH]+ calc. 282.1026; 334.0629
[PdL2]2+ calc. 334.0472; 334.0629 [Pd2L4]4+ calc. 334.0466; 387.0100 [PdL]+ calc. 386.9990; 387.0100
[Pd2L2]2+ calc. 386.9984. UV-Vis (DMSO, ε [M-1cm-1]): λmax nm = 314 (1.03 × 105). Anal. calc. for
2(OMs)4·10H2O: C, 50.61; H, 3.91; N, 9.28%. Found: C, 50.50; H, 3.87; N, 9.29%.
Figure 8 1H NMR spectrum (500 MHz, d6-DMSO) of [Pd2L4](OMs)4.
S6
Figure 9 13C NMR spectrum (100 MHz, d6-DMSO) of [Pd2L4](OMs)4.
Figure 10 1H DOSY NMR spectrum (500 MHz, d6-DMSO) of [Pd2L4](OMs)4.
1.5
Synthesis of [Pd2L4](OTs)4
1 (0.05 g, 0.18 mmol, 2 eq.), Pd(CH3CN)2Cl2 (0.02 g, 0.09 mmol, 1 eq.) and silver tosylate (0.05 g,
0.18 mmol, 2 eq.) were stirred in DMF (3 mL) at 50 °C for 1 h. The cooled reaction mixture was
filtered through Celite and the product precipitated by vapour diffusion of diethyl ether. The
precipitate was isolated by filtration and washed with further diethyl ether before drying in vacuo.
Yield 0.07 g (0.03 mmol, 74%). 1H NMR (d6-DMSO, 400 MHz) δ: 9.57 (d, J = 1.1 Hz, 8H, Ha), 9.46 (d, J =
5.7 Hz, 8H, Hb), 8.34 (dt, J = 1.4, 8.1 Hz, 8H, Hd), 8.00 (dd, J = 7.5, 8.1 Hz, 4H, Hf), 7.83 (dd, J = 6.0, 7.9
Hz, 8H, Hc), 7.79 (d, J = 7.8 Hz, 8H, He), 7.54 (d, J = 8.0 Hz, 8H, HOTs), 7.13 (d, J = 7.8 Hz, 8H, HOTs), 2.28
(s, 12H, HOTs). Diffusion coefficient (d6-DMSO, 298 K) D: 1.06 × 10-10 m2s-1 (24+); 3.07 × 10-10 m2s-1
(OTs-). 13C NMR (d6-DMSO, 100 MHz) δ: 153.3 (Ca), 151.1 (Cb), 145.7, 143.5 (Cd), 141.8, 138.3 (Cf),
S7
137.7, 128.6 (Ce), 128.1, 127.3 (Cc), 125.5, 121.5, 93.3, 83.6, 20.8. IR (ATR): ν (cm-1) 3071, 1654, 1572,
1556, 1480, 1444, 1420, 1386, 1178, 1120, 1103, 1064, 1032, 1009, 983, 811. HRESI-MS
(DMSO/CH3CN): m/z = 282.1265 [LH]+ calc. 282.1026; 334.0672 [PdL2]2+ calc. 334.0472; 334.0672
[Pd2L4]4+ calc. 334.0466; 502.4174 [PdsL4OTs]3+ calc. 502.4004; 527.5611 [Pd2L3]2+ calc. 527.5460. UVVis (DMSO, ε [M-1cm-1]): λmax nm = 314 (9.66 × 104). Anal. calc. for 2(OTs)4·10H2O: C, 56.70; H, 4.21; N,
7.63%. Found: C, 56.67; H, 4.50; N, 8.05%.
Figure 11 1H NMR spectrum (400 MHz, d6-DMSO) of [Pd2L4](OTs)4.
Figure 12 13C NMR spectrum (100 MHz, d6-DMSO) of [Pd2L4](OTs)4.
S8
Figure 13 1H DOSY NMR spectrum (500 MHz, d6-DMSO) of [Pd2L4](OTs)4.
S9
2
2.1
Additional 1H DOSY NMR Spectra
Bu4NOTs
Figure 14 1H DOSY NMR spectrum (500 MHz, d6-DMSO) of Bu4NOTs.
2.2
Bu4NOMs
Figure 15 1H DOSY NMR spectrum (500 MHz, d6-DMSO) of Bu4NOMs.
S10
2.3
Ligand 1
Figure 16 1H DOSY NMR spectrum (500 MHz, d6-DMSO) of 1.
2.4
[Pd2L4](BF4)4
Figure 17 1H DOSY NMR spectrum (500 MHz, d6-DMSO) of [Pd2L4](BF4)4.
S11
3
3.1
Stacked 1H NMR Spectra
Bu4NOMs and [Pd2L4](OMs)4
Figure 18 Stacked 1H NMR spectra (500 MHz, d6-DMSO) of [Pd2L4](OMs)4 (top) and Bu4NOMs (bottom).
3.2
Bu4NOTs and [Pd2L4](OTs)4
Figure 19 Stacked 1H NMR spectra (500 MHz, d6-DMSO) of [Pd2L4](OTs)4 (top) and Bu4NOTs (bottom).
S12
4
4.1
Stacked 19F NMR Spectra
NaOTf and [Pd2L4](OTf)4
Figure 20 Stacked 19F NMR spectra (376 MHz, d6-DMSO) of [Pd2L4](OTf)4 (top) and NaOTf (bottom).
4.2
NaBF4 and [Pd2L4](BF4)4
Figure 21 Stacked 19F NMR spectra (376 MHz, d6-DMSO) of [Pd2L4](BF4)4 (top) and NaBF4 (bottom).
S13
5
UV-Vis Spectra
Figure 22 UV-Vis spectra of palladium(II) complexes in DMSO at 10-5 M.
S14
6
6.1
X-ray Data
Experimental
[Pd2L4](BF4)4 and [Pd2L4](OTf)4 structures were collected at 89 K on a Bruker Kappa Apex II area
detector diffractometer using monochromated Mo Kαradiation. The structure was solved by direct
methods and refined against F2 using anisotropic thermal displacement parameters for all nonhydrogen atoms using APEX II software. Hydrogen atoms were placed in calculated positions and
refined using a riding model.
[Pd2L4](OTs)4 and [Pd2L4](OMs)4 structures were collected at 100 K on an Agilent Technologies
SuperNova diffractometer with Atlas detector using Cu Kα radiation. The structure was solved by
SIR92[3] and refined against F2 using anisotropic thermal displacement parameters for all nonhydrogen atoms using SHELXTL 6.14 software. Hydrogen atoms were placed in calculated positions
and refined using a riding model.
Due to the extent of disordered anions and solvent molecules in the crystal lattices for each of these
structures, the SQUEEZE routine within PLATON was implemented. SQUEEZE details for each
structure are listed below.
S15
6.2
[Pd2L4](BF4)4
Empirical formula
C78H50B4F16N12OPd2S
Formula weight
1763.40
Temperature
89(2) K
Wavelength
0.71073 Å
Crystal system
Monoclinic
Space group
C2/m
Unit cell dimensions
a = 13.505(4) Å
= 90°.
b = 23.381(7) Å
= 93.130(17)°.
c = 14.131(4) Å
 = 90°.
Å3
Volume
4455(2)
Z
2
Density (calculated)
1.314 Mg/m3
Absorption coefficient
0.507 mm-1
F(000)
1764
Crystal size
0.40 x 0.16 x 0.12 mm3
Theta range for data collection
1.44 to 26.64°.
Index ranges
-16<=h<=16, -29<=k<=28, -17<=l<=17
Reflections collected
29352
Independent reflections
4705 [R(int) = 0.1465]
Completeness to theta = 26.64°
97.8 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
0.9416 and 0.8229
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
4705 / 0 / 205
Goodness-of-fit on F2
1.019
Final R indices [I>2sigma(I)]
R1 = 0.0739, wR2 = 0.1929
R indices (all data)
R1 = 0.1123, wR2 = 0.2140
Largest diff. peak and hole
1.297 and -0.830 e.Å-3
S16
Figure 23 Mercury ellipsoid plot of [Pd2L4]4+. Ellipsoids are shown at the 50% probability level.
Platon Squeeze Details
Platon squeeze void nr
Platon squeeze void average x
Platon squeeze void average y
Platon squeeze void average z
Platon squeeze void volume
Platon squeeze void count electrons
Platon squeeze void content
1
2
-0.085
-0.026
0.000
0.500
-0.084
0.059
884
884
212
212
There are two void spaces, each with an electron count of
212. This can be accounted for by four tetrafluoroborate
(BF4) anions (41 electrons each) and one solvent molecule of
DMSO (42 electrons) in each void space.
S17
6.3
[Pd2L4](OTf)4
Empirical formula
C99H91F12N19O21Pd2S4
Formula weight
2451.95
Temperature
93(2) K
Wavelength
0.71073 Å
Crystal system
Triclinic
Space group
P-1
Unit cell dimensions
a = 13.390(4) Å
= 67.802(11)°.
b = 14.621(3) Å
= 70.017(12)°.
c = 17.121(4) Å
 = 88.790(12)°.
Å3
Volume
2894.0(13)
Z
1
Density (calculated)
1.407 Mg/m3
Absorption coefficient
0.474 mm-1
F(000)
1250
Crystal size
0.32 x 0.17 x 0.09 mm3
Theta range for data collection
1.38 to 26.68°.
Index ranges
-16<=h<=16, -18<=k<=17, -21<=l<=21
Reflections collected
31315
Independent reflections
11932 [R(int) = 0.0549]
Completeness to theta = 26.68°
97.5 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
0.9586 and 0.8631
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
11932 / 0 / 681
Goodness-of-fit on F2
1.084
Final R indices [I>2sigma(I)]
R1 = 0.0835, wR2 = 0.2352
R indices (all data)
R1 = 0.1122, wR2 = 0.2583
Largest diff. peak and hole
1.482 and -1.029 e.Å-3
S18
Figure 24 Mercury ellipsoid plot of [Pd2L4](OTf)4. Ellipsoids are shown at the 50% probability level.
Platon Squeeze Details
Platon squeeze void nr
Platon squeeze void average x
Platon squeeze void average y
Platon squeeze void average z
Platon squeeze void volume
Platon squeeze void count electrons
Platon squeeze void content
1
0.000
-0.004
0.500
417
64
Void electron count of 64 can be accounted for by two
MeCN (44 electrons) and two water (20 electrons)
molecules (total 64 electrons).
S19
6.4
[Pd2L4](OMs)4
Empirical formula
C100H89N21.50O12Pd2S4
Formula weight
2124.97
Temperature
100(2) K
Wavelength
1.54184 Å
Crystal system
Triclinic
Space group
P-1
Unit cell dimensions
a = 13.9197(9) Å
= 61.790(9)°.
b = 14.8539(13) Å
= 73.019(7)°.
c = 15.6864(13) Å
 = 89.926(6)°.
Å3
Volume
2697.3(4)
Z
1
Density (calculated)
1.308 Mg/m3
Absorption coefficient
3.956 mm-1
F(000)
1092
Crystal size
0.24 x 0.16 x 0.07 mm3
Theta range for data collection
3.36 to 76.50°.
Index ranges
-10<=h<=17, -18<=k<=17, -19<=l<=19
Reflections collected
13748
Independent reflections
8785 [R(int) = 0.0500]
Completeness to theta = 76.50°
77.5 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
0.7692 and 0.4503
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
8785 / 0 / 560
Goodness-of-fit on F2
1.973
Final R indices [I>2sigma(I)]
R1 = 0.1041, wR2 = 0.2671
R indices (all data)
R1 = 0.1161, wR2 = 0.2771
Largest diff. peak and hole
2.827 and -2.559 e.Å-3
S20
Figure 25 Mercury ellipsoid plot of [Pd2L4](OMs)4. Ellipsoids are shown at the 50% probability level.
Platon Squeeze Details
Platon squeeze void nr
Platon squeeze void average x
Platon squeeze void average y
Platon squeeze void average z
Platon squeeze void volume
Platon squeeze void count electrons
Platon squeeze void content
1
2
3
0.000
0.362
0.638
0.5000
0.315
0.685
0.000
0.376
0.624
598
8
9
154
3
3
Void electron count of 154 can be accounted for by seven
molecules of acetonitrile (22 electrons each).
S21
6.5
[Pd2L4](OTs)4
Empirical formula
C116H70N12O11Pd2S4
Formula weight
2148.88
Temperature
100(2) K
Wavelength
1.54184 Å
Crystal system
Monoclinic
Space group
I2/m
Unit cell dimensions
a = 14.1685(9) Å
= 90°.
b = 28.8623(18) Å
= 92.038(5)°.
c = 15.1053(11) Å
 = 90°.
Å3
Volume
6173.2(7)
Z
2
Density (calculated)
1.156 Mg/m3
Absorption coefficient
3.440 mm-1
F(000)
2188
Crystal size
0.23 x 0.16 x 0.10 mm3
Theta range for data collection
3.06 to 75.20°.
Index ranges
-17<=h<=12, -35<=k<=29, -18<=l<=18
Reflections collected
13041
Independent reflections
6264 [R(int) = 0.0769]
Completeness to theta = 75.20°
96.1 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
0.7248 and 0.5051
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
6264 / 18 / 352
Goodness-of-fit on F2
1.333
Final R indices [I>2sigma(I)]
R1 = 0.1216, wR2 = 0.3179
R indices (all data)
R1 = 0.1334, wR2 = 0.3304
Largest diff. peak and hole
6.160 and -1.982 e.Å-3
S22
Figure 26 Mercury ellipsoid plot of [Pd2L4](OTs)4. Ellipsoids are shown at the 50% probability level.
Platon Squeeze Details
Platon squeeze void nr
Platon squeeze void average x
Platon squeeze void average y
Platon squeeze void average z
Platon squeeze void volume
Platon squeeze void count electrons
Platon squeeze void content
1
2
-0.009
-0.056
0.000
0.500
0.007
0.095
660
660
299
299
Two void spaces each of 299 electrons can be accounted for
by two tosylate anions (89 electrons each) and three DMF
molecules (39 electrons each) (total 295 electrons).
S23
7
Calculation of Cavity Volume
The structural dimensions of 2 were obtained from the X-ray crystal structure of 2(BF4)4. Utilising the
NPy···NPy and Ha···Ha internal distances, the void space was calculated as an ellipsoid.
𝑉=
4
𝜋𝑟 𝑟 𝑟
3 𝑎 𝑏𝑐
Van der Waals radius of H = 1.20 Å
Van der Waals radius of N = 1.55 Å
𝑟𝑎 =
8.23 − 2 × 1.20
= 3.52 Å
2
𝑟𝑏 = 𝑟𝑐 =
𝑉=
10.31 − 2 × 1.55
= 3.61 Å
2
4
× 𝜋 × 3.52 × 3.61 × 3.61 = 192 Å3
3
S24
8
SPARTAN Models of 2⊃X-
Figure 27 SPARTAN ’06 model of 2⊃SbF6.
Figure 28 SPARTAN ’06 model of 2⊃BF4.
S25
Figure 29 SPARTAN ’06 model of 2⊃NO3.
Figure 30 SPARTAN ’06 model of 2⊃OMs.
S26
Figure 31 SPARTAN ’06 model of 2⊃OTf.
Figure 32 SPARTAN ’06 model of 2⊃OTs.
S27
Figure 33 SPARTAN ’06 model of 2⊃OTs.
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9
[1]
[2]
[3]
References
K. J. Kilpin, M. L. Gower, S. G. Telfer, G. B. Jameson, J. D. Crowley, Inorg. Chem. 2011, 50,
1123.
J. E. M. Lewis, E. L. Gavey, S. A. Cameron, J. D. Crowley, Chem. Sci. 2012, 3, 778.
A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, M. C. Burla, G. Polidori, M. Camalli,
J. Appl. Crystallogr. 1994, 27, 435.
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