Supporting Information Encapsulation of Vitamin B 1 and its Phosphate Derivatives by Cucurbit[7]uril: Tunability of the Binding Site and Affinity by the Presence of Phosphate Groups Shengke Li, Hang Yin, Ian W. Wyman, Qingwen Zhang, Donal H. Macartney,, and Ruibing Wang, State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Taipa, Macau, China Department of Chemistry, Queen s University, Kingston, ON, K7L 3N6, Canada Contents Theoretical calculations of C(2)-H/D exchange kinetics Figure S1. Electrospray mass spectrum for {1 CB[7]} + in water. Figure S2. Electrospray mass spectrum for {2 CB[7]} + in water. Figure S3. Electrospray mass spectrum for {3 CB[7]} + in water. Figure S4. The 1 H NMR spectra of free thiamine diphosphate (lower spectrum) and after the addition of 1.1 equivalents of CB[7] (upper spectrum) Figure S5. Job s plot for thiamine with CB[7] measured at 268 nm Figure S6. Job s plot for thiamine monophosphate with CB[7] measured at 250 nm Figure S7. Job s plot for thiamine diphosphate with CB[7] measured at 220 nm Figure S8. UV spectra of the thiamine 3 guests and its CB[7] host-guest complex Figure S9 Kinetic plots for the C(2)-H/D exchange reaction of 1 as a function of pd at 298K Figure S10. Kinetic plots for the C(2)-H/D exchange reaction of 1 CB[7] as a function of pd at 298K Figure S11. Kinetic plots for the C(2)-H/D exchange reaction of 2 as a function of pd at 298K Figure S12. Kinetic plots for the C(2)-H/D exchange reaction of 2 CB[7] as a function of pd at 298K Figure S13. Kinetic plots for the C(2)-H/D exchange reaction of 3 as a function of pd at 298K Figure S14. Kinetic plots for the C(2)-H/D exchange reaction of 3 CB[7] as a function of pd at 298K Figure S15. Energy minimized structure for {1 CB[7]} + with atom labeled with center numbers Table S1. Atomic coordinates for {1 CB[7]} + from energy-minimization calculations Figure S16. Energy minimized structure for {2 CB[7]} with atom labeled with center numbers Table S2. Atomic coordinates for {2 CB[7]} from energy-minimization calculations Figure S17. Energy minimized structure for {3 CB[7]} - with atom labeled with Page S3 S4 S4 S5 S6 S7 S7 S8 S9 S10 S10 S11 S11 S12 S12 S13 S13 S17 S17 S1
center numbers Table S3. Atomic coordinates for {3 CB[7]} - from energy-minimization calculations Full citation for reference 17 in paper S21 S21 S25 S2
Kinetics of C(2)-H/D exchange monitored by 1 H NMR Spectroscopy Determination of the first-order rate constants by semilogarithmic plots The proton/deuterium exchange was monitored via 1 H NMR spectroscopy as described above. Values describing the reaction progress, R, can be calculated from the integrations of the of C(2)-proton resonances [(I 2H ) t ] at time t, with an internal reference [(I 2H ) 0 ], at the beginning of the experiment (or at t = 0), according to equation (1). R = (I 2H ) t /(I 2H ) 0 (1) lnr = -k ex t (2) From equation (2), the first-order rate constant k ex can be determined from the slope of the linear semilogarithmic plot of the reaction progress versus the reaction time. Therefore, the first-order rate constant k ex values, in the presence and in the absence of CB[7], at various pd conditions can be determined. 1,2 Determination of the second-order rate constants The second-order rate constant, k DO, is calculated from the y-axis intercept of the linear fit with a fixed slope of one by plotting logk ex (first-order rate constants) against the pd values according to the equation (3). 1 log k ex = log (k DO K W /γ OL ) + pd (3) The value of pk W = 14.87 (for deuterated water). Under our experimental conditions the activity coefficient for deuterium oxide is γ OL = 0.83, as estimated from the solvent conditions and the ionic strength. 1 The pk a values of the thiamines in the absence and in the presence of CB[7] were estimated based on the second-order rate constants k DO and with k DO /k HO = 2.4, K W (H 2 O) = 1.00 x 10 14, and k HOH = 1 x 10 11 s -1 for the reverse protonation of the carbene by solvent water. 1 References (1) Amyes, T. L.; Diver, S. T.; Richard, J. P.; Rivas, F. M.; Toth, K. J. Am. Chem. Soc. 2004, 126, 4366. (2) Handy, S. T.; Okello, M. J. Org. Chem. 2005, 70, 1915. S3
Figure S1. Electrospray mass spectrum for {1 CB[7]} in water. Figure S2. Electrospray mass spectrum for {2 CB[7]} in water. S4
Figure S3. Electrospray mass spectrum for {ThDP CB[7]} - (m/z 1588.45 for [M+2H] + and 1610.45 for [M+H+Na] + ) in water. S5
1 6 5 N N 3 7 O 2 S N NH 2 4 -O P O P O -O O OH Figure S4. 1 H NMR spectra of free thiamine diphosphate (2 mm) (lower spectrum) and after the addition of 1.1 equivalents of CB[7] (upper spectrum) S6
0.10 0.08 Absorbance change 0.06 0.04 0.02 0.00 0.0 0.2 0.4 0.6 0.8 1.0 [CB[7]]/([CB[7]] + [Th]) Figure S5. Job s plot for thiamine with CB[7] measured at 268 nm 0.07 0.06 Absorbance change 0.05 0.04 0.03 0.02 0.01 0.00 0.0 0.2 0.4 0.6 0.8 1.0 [CB[7]]/([CB[7]] + [ThMP]) Figure S6. Job s plot for 2 with CB[7] measured at 250 nm. S7
0.030 0.025 Absorbance change 0.020 0.015 0.010 0.005 0.000 0.0 0.2 0.4 0.6 0.8 1.0 [CB[7]]/([CB[7]] + [ThDP]) Figure S7. Job s plot for 3 with CB[7] measured at 220 nm. S8
Figure S8. UV spectra of the thiamine 3 guests (0.1 mm) and its CB[7] (10 equiv.) host-guest complex in aqueous solution. S9
0.0-0.5-1.0 -ln(r) -1.5-2.0-2.5-3.0 0 1000 2000 3000 4000 5000 6000 Time, s Figure S9. Kinetic plots for the C(2)-H/D exchange reaction of thiamine as a function of pd at 298K: pd = 4.12 ( ), 4.36 ( ), 4.52 ( ), and 4.66 ( ). 0.0-0.2-0.4 -ln(r) -0.6-0.8-1.0-1.2 0 2000 4000 6000 8000 10000 Time, s Figure S10. Kinetic plots for the C(2)-H/D exchange reaction of {Th CB[7]} + as a function of pd at 298K: pd = 4.98 ( ), 4.93 ( ), 4.80 ( ), and 4.70 ( ). S10
0.0-0.2-0.4-0.6 -ln(r) -0.8-1.0-1.2-1.4-1.6-1.8 0 2000 4000 6000 8000 10000 12000 Time, s Figure S11. Kinetic plots for the C(2)-H/D exchange reaction of ThMP as a function of pd at 298K: pd = 3.45 ( ), 4.27 ( ), 4.66 ( ), and 4.84 ( ). 0.0-0.2-0.4 -ln(r) -0.6-0.8-1.0-1.2 0 2000 4000 6000 8000 10000 Time, s Figure S12. Kinetic plots for the C(2)-H/D exchange reaction of {ThMP CB[7]} as a function of pd at 298K: pd = 4.96 ( ), 4.79 ( ), 4.66 ( ), and 4.32 ( ). S11
0.0-0.5-1.0 -ln(r) -1.5-2.0-2.5-3.0-3.5 0 5000 10000 15000 20000 25000 30000 Time, s Figure S13. Kinetic plots for the C(2)-H/D exchange reaction of ThDP - as a function of pd at 298K: pd = 3.21 ( ), 4.20 ( ), 4.56 ( ), and 5.79 ( ). 0.0-0.2-0.4-0.6 -ln(r) -0.8-1.0-1.2-1.4-1.6 0 2000 4000 6000 8000 10000 Time, s Figure S14. Kinetic plots for the C(2)-H/D exchange reaction of {ThDP CB[7]} - as a function of pd at 298K: pd = 5.08( ), 4.93 ( ), 4.74( ), and 4.64 ( ). S12
Figure S15. Energy minimized structure for {1 CB[7]} + with atom labeled with center numbers (see table below) Table S1. Atomic coordinates for {1 CB[7]} from energy-minimization calculations (total energy = -5372.4927) Standard orientation: --------------------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Type X Y Z --------------------------------------------------------------------- 1 C 4.603089-3.918994-0.057086 2 C 5.497791-2.632779 0.080317 3 N 4.864557-1.921248 1.187108 4 C 3.887710-2.678866 1.817686 5 N 3.763087-3.867205 1.123200 6 N 3.924849-3.711411-1.327355 7 C 4.462565-2.641866-2.042254 8 N 5.387833-2.009403-1.214939 9 O 3.264721-2.351983 2.814712 10 O 4.187403-2.327282-3.180124 11 C 5.943942 1.013880 0.011650 12 C 5.454026 2.484970-0.175585 13 N 4.641515 2.710994 1.003248 14 C 4.310095 1.532694 1.637623 15 N 5.071508 0.519033 1.083834 16 N 5.732149 0.424952-1.281226 17 C 4.954859 1.230450-2.113198 18 N 4.715453 2.423419-1.422975 S13
19 O 3.491042 1.404340 2.550867 20 O 4.583133 0.963960-3.233739 21 C 5.359064-0.715963 1.806671 22 C 6.180428-0.893559-1.689554 23 C 2.926379 5.096214-0.520307 24 C 1.457379 5.647459-0.585495 25 N 0.959527 5.403696 0.758520 26 C 1.853902 4.719127 1.548438 27 N 3.003716 4.522901 0.818451 28 N 2.980070 4.147131-1.603316 29 C 1.764860 4.027033-2.274111 30 N 0.843346 4.861211-1.636950 31 O 1.671640 4.371653 2.711286 32 O 1.555251 3.345661-3.255809 33 C -2.178845 5.293663-0.457526 34 C -3.498937 4.477581-0.291712 35 N -3.179735 3.593478 0.834419 36 C -1.978915 3.921815 1.430185 37 N -1.455113 5.007733 0.764019 38 N -1.600997 4.724143-1.658284 39 C -2.538663 3.978720-2.384899 40 N -0.566013 1.117796 5.240485 41 C -1.309336 0.135145 5.786132 42 N -1.490460-1.068960 5.223491 43 C -0.889140-1.304448 4.061669 44 C -0.085677-0.352836 3.398451 45 C 0.010946 0.855297 4.083604 46 N 0.759333 2.019430 3.562274 47 H 1.660958 1.817058 3.087991 48 H 0.974098 2.631872 4.356502 49 H 0.146899 2.606848 2.953321 50 C -1.964785 0.396938 7.106067 51 C 0.668005-0.725633 2.149331 52 N 0.054968-0.247505 0.869385 53 C -1.164688 0.266931 0.766518 54 S -1.591154 0.623362-0.842521 55 C -0.029356 0.071434-1.414091 56 C 0.723972-0.365375-0.359784 57 C 2.092183-0.948170-0.426120 58 C 0.359430 0.159186-2.863571 59 C -0.753667-0.311014-3.800219 60 O -1.891433 0.472030-3.469844 61 H -2.707162 0.066493-3.802286 62 H -0.944572-1.380566-3.671556 63 H -0.435520-0.136883-4.836141 64 H 1.257486-0.436720-3.044310 65 H 0.602105 1.202353-3.099224 66 H 2.466141-0.894911-1.447212 67 H 2.082847-2.000724-0.129781 68 H 2.797840-0.419833 0.217099 69 H -1.584410-0.306256 7.853955 70 H -3.041313 0.219494 7.025785 71 H -1.779886 1.417967 7.438602 72 H -1.831928 0.377958 1.614508 73 H 0.739800-1.814688 2.100145 74 H 1.690386-0.344443 2.182206 75 H -1.033648-2.291179 3.626266 S14
76 N -3.662160 3.830835-1.564618 77 O -1.480496 3.354992 2.404503 78 O -2.414086 3.574523-3.516511 79 C -0.339883 5.788072 1.255019 80 C -0.402548 5.231220-2.295809 81 C 4.203161 4.016417 1.445360 82 C 4.206892 3.583289-2.133903 83 C -5.596435 1.545260-0.169251 84 C -5.930952 0.014279-0.230692 85 N -5.291416-0.515022 0.957573 86 C -4.475959 0.406126 1.574270 87 N -4.597560 1.612144 0.893168 88 N -5.116715 1.844866-1.497213 89 C -5.005335 0.707368-2.288560 90 N -5.356811-0.387885-1.503491 91 O -3.768422 0.216587 2.554151 92 O -4.692987 0.675830-3.463102 93 C -4.754622-3.499459-0.479871 94 C -3.580103-4.528642-0.591252 95 N -2.952870-4.462047 0.708624 96 C -3.448866-3.431263 1.491633 97 N -4.459245-2.806524 0.766205 98 N -4.624380-2.716942-1.683896 99 C -3.447167-2.983343-2.371121 100 N -2.788221-4.007676-1.695898 101 O -3.093519-3.146877 2.619873 102 O -3.082009-2.440503-3.397192 103 C -5.369293-1.889370 1.416905 104 C -5.551039-1.693914-2.114074 105 C -4.196925 2.839724 1.542011 106 C -4.873544 3.177189-2.023169 107 C -1.737191-4.769304-2.345984 108 C -1.998018-5.417423 1.225140 109 C 3.148468-4.720826-2.032143 110 C 2.843401-4.899856 1.550259 111 C 1.383216-5.622950-0.423573 112 C -0.174138-5.703306-0.554589 113 N -0.638118-5.277821 0.747680 114 N 1.573788-4.931757 0.845455 115 N 1.780617-4.878012-1.590300 116 C 0.696745-4.344142-2.283099 117 N -0.464599-4.789058-1.647052 118 C 0.376432-4.767906 1.537718 119 O 0.750128-3.645837-3.275276 120 O 0.255392-4.280229 2.649548 121 H 5.182383-4.851687-0.070216 122 H 6.546609-2.853846 0.318881 123 H 6.994620 0.932466 0.317748 124 H 6.267151 3.221073-0.221251 125 H 6.447655-0.787277 1.939013 126 H 4.877122-0.647144 2.783745 127 H 6.132792-0.914644-2.780212 128 H 7.217213-1.027552-1.360376 129 H 3.691897 5.874008-0.641730 130 H 1.402362 6.718930-0.818010 131 H -2.336708 6.376128-0.555753 132 H -4.372909 5.095146-0.045418 S15
133 H -0.529805 6.836449 0.999034 134 H -0.300215 5.684105 2.340220 135 H -0.385045 4.804146-3.301558 136 H -0.447396 6.328018-2.363772 137 H 3.994172 3.961952 2.514543 138 H 5.029745 4.716411 1.273835 139 H 3.999724 3.250678-3.153822 140 H 4.971704 4.372355-2.150990 141 H -6.462866 2.171370 0.083919 142 H -7.007551-0.199750-0.205509 143 H -5.746194-3.969046-0.431802 144 H -3.915393-5.553035-0.803683 145 H -6.402196-2.233677 1.284157 146 H -5.114341-1.890582 2.478455 147 H -5.415765-1.556647-3.188677 148 H -6.571204-2.044978-1.915331 149 H -5.077987 3.484203 1.678422 150 H -3.788217 2.569534 2.517357 151 H -4.786029 3.072873-3.106901 152 H -5.732081 3.815951-1.780659 153 H -1.563831-4.308640-3.320789 154 H -2.080742-5.805390-2.487423 155 H -1.971494-5.286213 2.308382 156 H -2.346720-6.428986 0.982982 157 H 3.118361-4.407907-3.078151 158 H 3.653164-5.692813-1.951611 159 H 2.617260-4.712620 2.601722 160 H 3.340949-5.872565 1.445183 161 H 1.873215-6.605670-0.402351 162 H -0.543966-6.712344-0.781624 S16
Figure S16. Energy minimized structure for {2 CB[7]} with atom labeled with center numbers (see table below) Table S2. Atomic coordinates for {2 CB[7]} from energy-minimization calculations (total energy = -5877.0788 au) Standard orientation: --------------------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Type X Y Z --------------------------------------------------------------------- 1 C -4.536178 0.987220 2.772997 2 C -4.488511 2.516738 2.381306 3 N -4.283834 2.450245 0.944324 4 C -4.328154 1.180948 0.443080 5 N -4.556683 0.320989 1.484914 6 N -3.324590 0.827708 3.545187 7 C -2.691001 2.028163 3.812767 8 N -3.390114 3.020496 3.160191 9 O -4.235916 0.873933-0.735837 10 O -1.761847 2.187961 4.562792 11 C -2.567199 5.375618 1.018751 12 C -1.224243 5.940655 0.397709 13 N -1.042183 5.103926-0.770176 14 C -1.985829 4.123385-0.885568 15 N -2.913017 4.303759 0.104818 16 N -2.162902 4.976026 2.339987 17 C -0.827498 5.208090 2.602763 18 N -0.274311 5.758341 1.466127 19 O -2.051146 3.297426-1.778631 20 O -0.274114 5.051971 3.662426 21 C -4.182905 3.606728 0.079746 S17
22 C -3.036724 4.417895 3.349456 23 C 2.192739 5.695060-0.784159 24 C 3.547950 4.945750-1.089902 25 N 3.202666 4.098831-2.206212 26 C 1.851104 4.037839-2.431986 27 N 1.255711 4.977048-1.625752 28 N 2.030731 5.513954 0.632368 29 C 2.945212 4.628727 1.169052 30 N 3.812942 4.266807 0.158028 31 O 1.287310 3.352635-3.261390 32 O 3.031036 4.313156 2.330196 33 C 5.750093 2.143994-1.525832 34 C 6.173600 0.620666-1.566506 35 N 5.200875 0.059129-2.485197 36 C 4.371134 0.997157-3.037604 37 N 4.748746 2.223279-2.564951 38 N 5.271816 2.300306-0.170896 39 C 5.465851 1.170178 0.605820 40 C -2.762658-1.448319-3.820922 41 C -2.153941-0.289085-3.523191 42 N -0.894526-0.509475-2.939283 43 C -0.561549-1.774583-2.855549 44 S -1.763652-2.793771-3.416193 45 C -0.019349 0.594916-2.366193 46 C 0.581432 0.172940-1.054487 47 C 1.938635-0.025854-0.937486 48 N 2.556649-0.280374 0.213552 49 C 1.792668-0.341171 1.315540 50 N 0.470589-0.239442 1.280825 51 C -0.155915 0.014737 0.129227 52 C 2.455966-0.499597 2.653287 53 N -1.499143 0.088461 0.202532 54 H -1.890944-0.044284 1.101544 55 H -2.107091 0.189293-0.568271 56 C -2.681556 1.101186-3.740109 57 C -4.193227-1.630083-4.255877 58 C -5.093085-1.553606-3.007698 59 O -6.458287-1.689840-3.476850 60 P -7.826479-1.456456-2.610086 61 O -8.623482-2.498777-3.551184 62 O -7.917208 0.121055-2.952834 63 H -7.288680 0.435803-3.584494 64 O -7.056052-1.876157-1.202985 65 H -7.657258-1.922938-0.479717 66 H -4.953838-0.614088-2.498534 67 H -4.853695-2.337412-2.315815 68 H -4.337307-2.585946-4.736976 69 H -4.480433-0.864617-4.959466 70 H -1.928029 1.726896-4.196371 71 H -2.980517 1.555420-2.811235 72 H -3.530446 1.055959-4.404138 73 H 1.702609-0.615817 3.413365 74 H 3.060941 0.377885 2.837775 75 H 3.127707-1.342019 2.664533 76 H 2.526534 0.016096-1.822894 77 H -0.654141 1.455834-2.252924 78 H 0.749930 0.824701-3.084948 S18
79 H 0.378837-2.116692-2.487534 80 N 6.058441 0.215954-0.193886 81 O 3.491182 0.778313-3.849679 82 O 5.291536 1.094690 1.797526 83 C 4.152204 3.437727-3.076230 84 C 5.053266 3.582378 0.475124 85 C -0.113867 5.375504-1.849327 86 C 1.096800 6.238926 1.471322 87 C 5.647420-2.934028-1.034842 88 C 4.814868-4.199100-0.571270 89 N 3.584095-4.053349-1.319429 90 C 3.538982-2.910158-2.074908 91 N 4.773081-2.319794-2.011507 92 N 5.831252-2.209276 0.198142 93 C 5.260453-2.824360 1.284990 94 N 4.704349-4.008306 0.850784 95 O 2.600276-2.546399-2.760441 96 O 5.320267-2.452217 2.433704 97 C 1.796083-5.684002 0.951769 98 C 0.370140-5.518045 1.622247 99 N -0.430992-4.966578 0.544218 100 C 0.303161-4.695864-0.575933 101 N 1.586264-5.102745-0.359596 102 N 2.661984-4.956195 1.840041 103 C 1.984740-4.328284 2.862403 104 N 0.648149-4.638907 2.729051 105 O -0.128366-4.259150-1.630062 106 O 2.481616-3.704521 3.768351 107 C 2.564213-5.072089-1.427243 108 C 4.114548-4.940576 1.789260 109 C 5.184708-1.306231-2.962575 110 C 6.612516-0.998262 0.367716 111 C -0.287775-4.287857 3.778074 112 C -1.878255-4.859828 0.541967 113 C -3.004776-0.331499 4.357694 114 C -4.877050-1.084828 1.290636 115 C -3.440649-2.407995 2.942376 116 C -2.531951-3.676725 2.712756 117 N -2.443390-3.739856 1.268108 118 N -3.815650-2.026282 1.597841 119 N -2.555391-1.502461 3.632650 120 C -1.320125-2.058546 3.917603 121 N -1.323018-3.342406 3.413904 122 C -3.187397-2.776254 0.631975 123 O -0.455750-1.560589 4.595833 124 O -3.339174-2.672370-0.568609 125 H -5.407174 0.715578 3.350065 126 H -5.398327 3.051549 2.605513 127 H -3.364472 6.101808 1.059025 128 H -1.286532 6.978364 0.106850 129 H -4.958155 4.311128 0.349849 130 H -4.340058 3.253783-0.924356 131 H -2.498743 4.482712 4.280695 132 H -3.948395 4.997530 3.396317 133 H 2.207883 6.743897-1.040343 134 H 4.359704 5.607074-1.354167 135 H 6.563166 2.824463-1.730293 S19
136 H 7.176517 0.459618-1.932417 137 H 4.942748 4.138375-3.308160 138 H 3.619446 3.162246-3.970723 139 H 5.036449 3.396375 1.536687 140 H 5.882017 4.236915 0.224930 141 H -0.455962 4.823755-2.708415 142 H -0.141335 6.439290-2.052147 143 H 1.441786 6.138948 2.487449 144 H 1.105655 7.278419 1.169503 145 H 6.596211-3.180825-1.485990 146 H 5.287843-5.140928-0.802780 147 H 2.113663-6.711278 0.859073 148 H -0.057714-6.449030 1.962498 149 H 3.052390-6.036284-1.477416 150 H 2.016960-4.885653-2.335110 151 H 4.451645-4.638994 2.767145 152 H 4.461110-5.938792 1.558170 153 H 6.174908-1.567583-3.314046 154 H 4.482213-1.326746-3.778879 155 H 6.690269-0.845881 1.431619 156 H 7.593119-1.152527-0.064520 157 H 0.295274-3.830055 4.560507 158 H -0.763582-5.191060 4.141048 159 H -2.186711-4.748991-0.483349 160 H -2.280868-5.776536 0.954531 161 H -2.197000-0.035650 5.007406 162 H -3.877681-0.599812 4.943880 163 H -5.164549-1.227906 0.262764 164 H -5.718532-1.314276 1.932031 165 H -4.321427-2.610866 3.534027 166 H -2.959208-4.589510 3.101539 167 H -8.103038-2.864961-4.251220 S20
Figure S17. Energy minimized structure for {3 CB[7]} with atom labeled with center numbers (see table below) Table S3. Atomic coordinates for {3 CB[7]} from energy-minimization calculations (total energy = -6440.9440 au Standard orientation: --------------------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Type X Y Z --------------------------------------------------------------------- 1 O 2.743913-5.284300 1.230861 2 O 4.068651-4.939859 0.431700 3 N 4.744264-4.014596 1.301324 4 O 4.018513-3.703894 2.430235 5 N 2.848071-4.431008 2.385493 6 N 1.696942-4.958919 0.277153 7 O 2.185513-4.413907-0.877231 8 N 3.546254-4.394560-0.805311 9 O 4.383809-3.002638 3.341923 10 O 1.528715-4.093132-1.853561 11 O 6.261775-2.460358-1.213260 12 O 6.578572-0.967566-1.636415 13 N 6.632565-0.285682-0.366880 14 O 6.415046-1.111929 0.707955 15 N 6.244901-2.391398 0.223679 16 N 4.979726-2.696979-1.843476 17 O 4.486927-1.600271-2.502512 S21
18 N 5.458785-0.636013-2.491708 19 O 6.464512-0.800254 1.874828 20 O 3.417152-1.539428-3.082130 21 O 6.097971-3.514317 1.126202 22 O 4.343347-3.990713-1.945431 23 O 5.844235 2.578616-1.920734 24 O 4.947009 3.866818-1.726615 25 N 4.586203 3.791028-0.329079 26 O 5.215818 2.753309 0.337086 27 N 6.004658 2.091110-0.579824 28 N 5.027174 1.768787-2.804655 29 O 3.880800 2.396763-3.211734 30 N 3.874628 3.652411-2.671484 31 O 5.196195 2.564677 1.529028 32 O 3.047436 1.933329-3.968401 33 O 2.002122 5.743209-0.889832 34 O 0.515470 5.972757-0.413682 35 N 0.579329 5.710765 0.997783 36 O 1.785654 5.162626 1.386810 37 N 2.607338 5.141044 0.276788 38 N 1.843610 4.877915-2.033189 39 O 0.578005 4.358345-2.135264 40 O -2.089603-2.289523-3.572753 41 O -1.894756-1.005065-3.230056 42 N -0.570130-0.790726-2.808533 43 O 0.189138-1.857128-2.871191 44 S -0.644317-3.210306-3.395748 45 O -0.055006 0.525426-2.243205 46 O 0.775215 0.280674-1.013625 47 O 2.131381 0.516845-1.028391 48 N 2.915589 0.421401 0.043145 49 O 2.328776 0.072125 1.198427 50 N 1.043557-0.243785 1.286400 51 O 0.250454-0.147831 0.215860 52 O 3.147134 0.067890 2.457524 53 N -1.034510-0.501273 0.413494 54 H -1.736939-0.508066-0.279167 55 H -1.268767-0.781446 1.333170 56 O -2.899067 0.113131-3.264909 57 O -3.413818-2.937338-3.872593 58 O -4.062917-3.347134-2.533171 59 O -5.512419-3.566141-2.761186 60 P -6.486073-2.355335-2.598445 61 O -6.633726-2.182973-1.046095 62 O -7.848578-2.896360-3.162740 63 H -8.091993-3.799828-3.065467 64 O -6.062105-1.115443-3.262857 65 P -7.991272 1.136535-1.942377 66 O -8.680119 1.681731-0.597998 67 O -6.606600 0.563001-1.258542 68 H -5.991216 0.252748-1.917829 69 O -8.798503-0.273764-2.029654 70 H -8.983730-0.654822-2.870124 71 H -3.936551-2.573512-1.797307 72 H -3.671738-4.266314-2.146201 73 H -3.301881-3.798856-4.513367 74 H -4.068019-2.235763-4.360596 S22
75 H -3.855431-0.260915-3.589347 76 H -2.566877 0.884561-3.948190 77 H -3.032461 0.558566-2.294281 78 H 3.467494 1.081485 2.657322 79 H 4.044344-0.518253 2.344924 80 H 2.553433-0.316019 3.269133 81 H 2.581370 0.779181-1.955989 82 H -0.919231 1.127987-2.030470 83 H 0.525764 1.015626-3.006636 84 H 1.228642-1.861523-2.631669 85 N -0.206629 4.997326-1.207654 86 O 2.098356 4.856725 2.511070 87 O 0.193620 3.552970-2.959346 88 O 4.029553 4.896276 0.431710 89 O 2.858258 4.617220-3.031434 90 O 6.981446 1.107951-0.160892 91 O 5.416201 0.503548-3.387130 92 O -2.632853 5.020975 1.091091 93 O -3.642033 4.028975 1.799833 94 N -2.975604 3.733798 3.041723 95 O -1.776631 4.398658 3.197325 96 N -1.572014 5.148294 2.058616 97 N -2.303170 4.311253-0.127611 98 O -2.892456 3.079636-0.212225 99 N -3.733458 2.934451 0.855168 100 O -1.086978 4.400294 4.186705 101 O -2.763038 2.293041-1.133190 102 O -4.348144 0.630107 3.105960 103 O -3.844239-0.841590 3.371481 104 N -2.560556-0.622314 3.997310 105 O -2.322009 0.708977 4.292310 106 N -3.380859 1.438777 3.798694 107 N -4.330359 0.700122 1.654504 108 O -4.027748-0.484757 1.054181 109 N -3.807734-1.414666 2.040484 110 O -1.408178 1.135104 4.951763 111 O -4.004056-0.709919-0.148691 112 O -3.487795 2.863076 4.076381 113 O -4.726291 1.878899 0.907810 114 O -0.444113 6.058039 1.965157 115 O -1.646598 4.902761-1.275236 116 O -3.669360-2.831218 1.754231 117 O -1.787116-1.642857 4.677545 118 O 0.299525-5.332971 0.399927 119 O 1.965880-4.461113 3.533478 120 O -0.455931-4.559610 2.716785 121 O -1.693075-3.679006 3.142548 122 N -1.073465-2.566489 3.818778 123 N 0.651075-3.886796 3.335589 124 N -0.518019-4.507443 1.268317 125 O -1.616829-3.833766 0.794750 126 N -2.331352-3.381515 1.878214 127 O 0.298159-2.698363 3.940664 128 O -1.956518-3.747512-0.370313 129 O 1.028749-1.977820 4.574922 130 H 2.671659-6.322367 1.518725 131 H 4.687228-5.800648 0.228803 S23
132 H 6.990662-3.176062-1.560888 133 H 7.506243-0.857558-2.176753 134 H 6.723208-4.326686 0.781194 135 H 6.423352-3.169791 2.093812 136 H 3.673596-3.954836-2.787162 137 H 5.111153-4.734629-2.111147 138 H 6.803035 2.782907-2.373166 139 H 5.463610 4.789991-1.942907 140 H 2.513836 6.651757-1.170670 141 H 0.145687 6.968975-0.605369 142 H 4.567374 5.799843 0.162867 143 H 4.187746 4.668199 1.473214 144 H 2.354403 4.219564-3.896199 145 H 3.342360 5.553426-3.273765 146 H 7.108718 1.224201 0.902816 147 H 7.910413 1.314601-0.677292 148 H 4.683140 0.288739-4.146550 149 H 6.397429 0.608008-3.832682 150 H -3.063643 5.983118 0.858900 151 H -4.618226 4.454228 1.973376 152 H -5.343681 0.821867 3.474783 153 H -4.498653-1.415480 4.010369 154 H -4.527313 3.095925 4.262150 155 H -2.893686 3.058496 4.953730 156 H -4.965895 1.562581-0.088541 157 H -5.619427 2.287181 1.360166 158 H -0.810514 7.048727 1.729123 159 H 0.023898 6.050874 2.935904 160 H -1.871878 4.283109-2.126523 161 H -2.056273 5.895729-1.417735 162 H -3.990007-2.985404 0.739529 163 H -4.320310-3.371753 2.428450 164 H -1.045937-1.125430 5.264961 165 H -2.448032-2.210708 5.324466 166 H -0.133736-5.268434-0.583313 167 H 0.258568-6.354551 0.757513 168 H 2.451018-3.880310 4.300965 169 H 1.844004-5.487932 3.856983 170 H -0.518890-5.583602 3.055166 171 H -2.381996-4.192580 3.797299 172 H -6.723586-1.278308-0.758766 173 H -8.979480 1.039446 0.025663 S24
Full Citation for Reference 17 (17) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A. Jr.; Vreven, T.; Kudin, N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision C.02, Gaussian, Pittsburgh, PA 2004. S25