Supporting Information Copyright Wiley-VC Verlag Gmb & Co. KGaA, 69451 Weinheim, 2008
Copper Complexes of Mono- and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models. Dipl. Chem. Kai Ruth [a], Dipl. Chem. Sandor Tüllman [a], Dipl. Chem. annes Vitze [a], Dr. Michael Bolte [a], Dr. ans-wolfram Lerner [a], Prof. Dr. Max C. olthausen [a]*, and Prof. Dr. Matthias Wagner [a]* [a] Institut für Anorganische und Analytische Chemie, Johann Wolfgang Goethe-Universität Frankfurt am Main, Max-von-Laue-Straße 7, D-60438 Frankfurt, Germany.
Crystal Structure Determinations of 3 and 7 Single crystals of 3 and 7 were measured on a STOE IPDS-II diffractometer with graphitemonochromated MoK α radiation. Empirical absorption corrections with program PLATON [1] were performed. The structures were solved by direct methods [2] and refined with full-matrix least-squares on F 2 using the program SELXL97. [3] ydrogen atoms were placed on ideal positions and refined with fixed isotropic displacement parameters using a riding model. [1] A. L. Spek, J. Appl. Crytallogr. 2003, 36, 7-13. [2] G. M. Sheldrick, Acta Crystallogr. Sect. A. 1990, 46, 467-473. [3] G. M. Sheldrick, SELXL-97. A Program for the Refinement of Crystal Structures, Universität Göttingen, 1997. 2S
Figure 1aS: Molecular structure of 3 in the solid state; displacement ellipsoids at the 50 % probability level. Selected bond lengths (Å) and bond angles (deg): B(1)-C(1) 1.621(4), B(1)- C(11 # ) 1.637(4), B(1)-C(21) 1.639(4), B(1)-S(1) 2.029(3), S(1)-C(11) 1.809(3), S(1)-C(12) 1.807(3), S(2)-C(21) 1.820(3), S(2)-C(22) 1.814(3); C(11 # )-B(1)-S(1) 102.7(2), B(1)-C(11 # )- S(1 # ) 113.1(2), C(11)-S(1)-B(1) 105.2(1). Symmetry transformation used to generate equivalent atoms: #: -x+1,-y+1,-z+1. Figure 1bS: Molecular structure of 7 in the solid state; displacement ellipsoids at the 50 % probability level. Selected bond lengths (Å) and bond angles (deg): B(1)-C(1) 1.613(12), B(1)-C(11) 1.607(13), B(1)-Br(1) 2.097(8), B(1)-S(1 # ) 1.972(10), S(1)-C(1) 1.806(9), S(1)- C(2) 1.795(10); C(1)-B(1)-S(1 # ) 107.3(6), B(1)-C(1)-S(1) 114.5(6), C(1)-S(1)-B(1 # ) 105.8(4). Symmetry transformation used to generate equivalent atoms: #: -x+1,-y,-z. 3S
Table 1S. Crystallographic Data for 3 and 7. 3 7 formula C 20 30 B 2 S 4 C 22 36 B 2 Br 2 S 2 Si 2 fw 420.30 602.25 color, shape colorless, plate colorless, plate crystal size (mm) 0.23 0.18 0.09 0.26 0.24 0.13 temp (K) 173(2) 173(2) radiation Mo K α, 0.71073 Å Mo K α, 0.71073 Å crystal system monoclinic triclinic space group P2 1 /n P-1 a (Å) 9.4940(10) 6.8589(15) b (Å) 7.3513(6) 6.9110(15) c (Å) 16.0747(16) 14.975(3) α ( ) 90 89.832(18) β ( ) 93.977(8) 83.438(18) γ ( ) 90 89.579(17) V (Å 3 ) 1119.20(19) 705.2(3) Z 2 1 D calcd (g cm -3 ) 1.247 1.418 F(000) 448 308 µ(mm -1 ) 0.427 3.116 no. of reflns collected 9338 5294 no. of indep reflns (R int ) 2097 (0.0722) 2598 (0.1192) no. of reflns obsd (I>2σ(I)) 1629 1912 no. of data/restraints/params 2097/0/119 2598/0/137 GOOF on F 2 1.074 1.004 R1, wr2 (I>2σ(I)) 0.0491, 0.0949 0.0948, 0.2325 R1, wr2 (all data) 0.0713, 0.1016 0.1182, 0.2497 largest diff peak and hole (eå -3 ) 0.248/-0.299 1.314 /-1.494 4S
Polymeric Structure of K[5] Figure 1cS 5S
Cyclic Voltammograms of K[5] and K[11] Figure 2aS: Cyclic voltammogram of K[5] vs. Fc/Fc + ; C 2 Cl 2, [NBu 4 ][B(C 6 F 5 ) 4 ] as supporting electrolyte (0.05 M), scan rate 200 mvs -1. Figure 2bS: Cyclic voltammogram of K[11] vs. Fc/Fc + ; C 2 Cl 2, [NBu 4 ][B(C 6 F 5 ) 4 ] as supporting electrolyte (0.05 M), scan rate 200 mvs -1. 6S
Sterically indered Interconversion of [Cu I [N 4 ] tet ] - and Cu II [N 4 ] spl N N N N R'(R)B N N Cu N N B(R)R' areas where counterrotation of the red (left) and the black (right) fragment leads to steric congestion and thus to the existence of the distorted minimum structure Cu II [N 4 ] dspl Figure 3S 7S
Comparison of DFT Structures with X-ray Data: K[CuI[N2S2]tet] Table 2S: Comparison of computed and experimental (X-ray diffraction) geometries of K[11]. Numbering scheme: cf. caption of Figure 6. Level of theory employed: BP86/TZVP+ECP(Cu). Bond lengths in Å, bond angles and torsion angles in deg. Parameter Experiment Calculated Cu(1)-N(12) 2.054(7) 2.063 Cu(1)-N(42) 2.058(7) 2.063 Cu(1)-S(1) 2.251(2) 2.301 Cu(1)-S(2) 2.267(2) 2.301 K(1)-N(22) 2.851(7) 2.828 K(1)-N(52) 2.757(7) 2.828 K(1)-N(12) 3.072(7) 3.037 N(12)-Cu(1)-N(42) 108.5(3) 111.1 N(12)-Cu(1)-S(1) 102.2(2) 100.7 N(12)-Cu(1)-S(2) 104.5(2) 107.1 N(42)-Cu(1)-S(1) 111.5(2) 107.1 N(42)-Cu(1)-S(2) 101.3(2) 100.7 S(1)-Cu(1)-S(2) 127.7(1) 129.8 C(1)-S(1)-Cu(1) 104.0(3) 102.5 C(2)-S(2)-Cu(1) 101.9(3) 102.5 B(1)-Cu(1)-B(2) 140.9(2) 139.8 B(1)-N(11)-N(12)-Cu(1) -4.2(11) -11.1 B(1)-C(1)-S(1)-Cu(1) 48.2(6) 51.0 B(2)-N(41)-N(42)-Cu(1) 17.4(10) 11.1 B(2)-C(2)-S(2)-Cu(1) 54.9(7) 51.0 8S
CuII[N4S]spy Table 3S: Comparison of computed and experimental (X-ray diffraction) geometries of 12. Numbering scheme: cf. caption of Figure 7. Level of theory employed: BP86/TZVP+ECP(Cu). Bond lengths in Å, bond angles and torsion angles in deg. Parameter Experiment Calculated Cu(1)-N(12) 2.009(7) 2.028 Cu(1)-N(22) 1.999(6) 2.007 Cu(1)-N(42) 1.980(7) 2.022 Cu(1)-N(52) 1.986(6) 2.021 Cu(1)-S(1) 2.805(3) 2.728 N(12)-Cu(1)-N(22) 88.4(2) 87.9 N(12)-Cu(1)-N(42) 172.5(3) 173.7 N(12)-Cu(1)-N(52) 90.0(3) 91.7 N(42)-Cu(1)-N(52) 88.4(3) 88.2 N(12)-Cu(1)-S(1) 83.1(2) 81.3 N(22)-Cu(1)-S(1) 90.1(2) 92.3 C(1)-S(1)-Cu(1) 98.7(3) 100.7 B(1)-Cu(1)-B(2) 168.1(1) 170.5 B(1)-N(11)-N(12)-Cu(1) -1.5(9) -2.6 B(1)-N(21)-N(22)-Cu(1) -1.8(10) -2.9 B(1)-C(1)-S(1)-Cu(1) -15.7(8) -19.4 B(2)-N(41)-N(42)-Cu(1) -0.9(9) -7.0 B(2)-N(51)-N(52)-Cu(1) 5.6(9) 5.2 9S
BP86/TZVP+ECP(Cu)/RI-Optimized Structures, total energies (in a. u.) given refer to single-point calculations including the COSMO solvent model. K[Cu I [N 2 S 2 ] tet ] 74 E tot (BP86/TZVP+ECP(Cu)/RI+COSMO(C 2 Cl 2 )): -3168.75206 Cu -0.000004 1.338667-0.000340 B 3.325460 0.121683 0.122307 C 5.469851 0.491339-1.388485 C 6.803016 0.279654-1.751613 C 7.588195-0.628624-1.033230 C 7.022411-1.317205 0.042783 C 5.686009-1.095004 0.398044 C 4.871694-0.187408-0.304840 S 1.665998 2.314465 1.250673 S -1.666009 2.314059-1.251597 C 3.201028 1.737143 0.395551 C 1.795762 4.129678 0.972946 C 2.700303-1.192592-2.067696 N 2.383234-0.325563-1.069523 C 1.631832-1.266715-2.956826 N 1.118151 0.171938-1.282977 C 0.671668-0.388455-2.427584-0.315866-0.132932-2.804313 3.677642 0.596913 2.938222 3.669579-1.677794-2.079835 C 3.261272-0.375302 2.696966 N 2.933595-0.699595 1.415318 N 2.451796-1.981572 1.361936 C 2.477995-2.433909 2.631042 2.132131-3.441657 2.852568 3.121026-1.535911 4.589293 C 2.979870-1.463148 3.516169 4.875878 1.198302-1.975056 7.231188 0.824040-2.596515 8.630222-0.798213-1.311860 7.623042-2.032192 0.609839 5.268334-1.647067 1.242768 K -0.000016-2.343265 0.000403 C -1.795694 4.129357-0.974403-0.920074 4.595483-1.441907-2.707903 4.509896-1.452115 2.707986 4.510306 1.450565 0.920166 4.595992 1.440306 C -3.201030 1.737033-0.396243-3.248466 2.261102 0.569903-4.048985 2.089611-1.003031-3.677450 0.595821-2.938474 C -3.261187-0.376336-2.696802 B -3.325449 0.121680-0.122340 N -2.383223-0.325066 1.069676 N -2.933582-0.700129-1.415010-3.121024-1.537750-4.588642 N -1.118063 0.172391 1.282778 C -0.671593-0.387408 2.427685 0.315991-0.131797 2.804222-2.132381-3.442882-2.851099-1.570718-1.848195 3.870058 C -2.700357-1.191474 2.068365-3.669690-1.676551 2.080823 N -2.451937-1.982144-1.361082 10S
C -4.871682-0.187268 0.304917-4.876165 1.199617 1.974158 C -5.470007 0.492178 1.388030-7.231488 0.825540 2.595668 C -6.803173 0.280581 1.751209 C -7.588185-0.628301 1.033408-8.630214-0.797815 1.312075-7.622722-2.033066-0.608645 C -7.022230-1.317584-0.042065-5.268025-1.648065-1.241693 C -5.685825-1.095478-0.397374 C -2.979879-1.464553-3.515545 C -2.478135-2.435002-2.630003 C -1.631845-1.265241 2.957472 4.048977 2.089977 1.002199 3.248464 2.260813-0.570811 1.808897 4.357294-0.099879-1.808781 4.357285 0.098356 1.570688-1.850162-3.869096 [Cu I [N 2 S 2 ] tet ] - 73 E tot (BP86/TZVP+ECP(Cu)/RI+COSMO(C 2 Cl 2 )): -2568.80893 Cu 0.004935-0.053179-0.181348 B -3.679651-0.208139-0.019224 C -4.775017 2.037299-0.924640 C -5.815444 2.788680-1.482149 C -7.067363 2.201873-1.695333 C -7.260107 0.862139-1.342616 C -6.211360 0.122461-0.783971 C -4.941793 0.687121-0.555718 S -1.322350-1.617508-1.247943 S 1.276983 1.545504-1.258790 C -2.883317-0.631496-1.389193 C -0.926244-1.840459-3.033283 C -3.338787 1.383570 2.008606 N -2.815864 0.667059 0.978703 C -2.300819 1.963212 2.728214 N -1.444415 0.756315 1.013411 C -1.138275 1.539999 2.064883-0.095508 1.753165 2.282845-3.430247-3.128959-0.342912-4.411754 1.400037 2.161063 C -4.049879-2.797612 0.484247 N -4.201708-1.470478 0.763480 N -4.986630-1.301151 1.869103 C -5.313671-2.537065 2.275365-5.940582-2.661653 3.156085-4.834175-4.605173 1.515262 C -4.754143-3.525122 1.437499-3.806502 2.517356-0.757538-5.649736 3.836116-1.748446-7.884961 2.783972-2.127625-8.235072 0.392078-1.497515-6.386377-0.917797-0.499904 C 0.871659 1.743931-3.045069-0.124076 2.199770-3.109264 1.607726 2.403821-3.525108-1.689377-2.470907-3.510559 0.049854-2.337204-3.095319 C 2.881733 0.632286-1.399295 2.673622-0.279902-1.977722 11S
3.553198 1.262561-2.004916 3.331095 3.124429-0.298732 C 3.894960 2.794091 0.567600 B 3.672566 0.208640-0.026061 N 2.851803-0.779460 0.898601 N 4.068856 1.466522 0.831943 4.532941 4.602258 1.693854 N 1.482995-0.894938 0.951690 C 1.210226-1.759709 1.947109 0.175669-2.008760 2.166092 5.576750 2.658974 3.375578 2.495471-2.902160 3.385304 C 3.405789-1.558931 1.864319 4.481326-1.569673 1.996615 N 4.772541 1.297562 1.990983 C 5.016067-0.561956-0.560108 4.004192-2.422709-1.001809 C 4.951579-1.878800-1.059695 5.979004-3.544873-1.980977 C 6.066519-2.519853-1.610671 C 7.293382-1.851321-1.684137 8.168878-2.347035-2.110677 8.339527-0.010105-1.244940 C 7.385570-0.542410-1.199779 6.358405 1.103699-0.262633 C 6.262602 0.086713-0.649536 C 4.498369 3.522276 1.587157 C 5.025148 2.534063 2.445883 C 2.391986-2.209959 2.556533-3.573973-1.216636-2.018122-2.625828 0.283304-1.942759-0.878165-0.868808-3.540430 0.864446 0.768974-3.548145-2.376825 2.593413 3.607871 [Cu I [N 3 S] tet ] - 73 E tot (BP86/TZVP+ECP(Cu)/RI+COSMO(C 2 Cl 2 )): -2568.81306 Cu -0.212487-0.378125 0.059075 B 3.445501-0.206302 0.007600 C 2.701120-1.161775 1.113224 2.366340-0.527006 1.947224 3.440417-1.873039 1.516712 S 1.233440-2.147392 0.572458 B -3.533836 0.126651 0.036688 C -5.169898 0.068362 0.174515-5.600337 0.188966-0.832577-5.495603 0.942295 0.761414 S -5.959248-1.427196 0.934100 C 0.750735-2.931105 2.166189-0.119657-3.566980 1.961724 0.469794-2.168244 2.903720 1.575675-3.547349 2.550010 C -7.722763-0.928469 0.819031-8.325017-1.741475 1.246259-8.021697-0.774893-0.227679-7.910490-0.007491 1.389247 N 4.005093-1.042008-1.205649 N 4.699252-0.410426-2.198642 C 5.108837-1.380892-3.029697 5.684916-1.118282-3.914917 C 4.696008-2.654950-2.585101 12S
4.866453-3.623046-3.046575 C 3.993203-2.390215-1.414129 3.462589-3.056092-0.741021 N 2.520026 0.942716-0.564480 N 1.143662 0.965008-0.574182 C 0.783249 2.104222-1.196202-0.271594 2.337965-1.311099 C 1.914257 2.828675-1.605462 1.945270 3.776304-2.132565 C 2.990161 2.055494-1.188408 4.058691 2.196372-1.301716 C 4.683189 0.476924 0.837186 C 4.459800 1.540222 1.735712 3.458123 1.974078 1.805451 C 5.483412 2.070490 2.528576 5.272113 2.899967 3.208990 C 6.776980 1.543188 2.448166 7.581747 1.954772 3.062449 C 7.026964 0.485814 1.567361 8.034335 0.067701 1.488689 C 5.993621-0.034973 0.779433 6.212429-0.851084 0.086898 N -2.841226 0.045451 1.453712 N -1.479511 0.127845 1.580820 C -1.224694 0.239751 2.898054-0.196772 0.330498 3.237529 C -2.417883 0.233368 3.641491-2.538768 0.303602 4.717506 C -3.419753 0.109560 2.684270-4.496557 0.027483 2.790167 N -2.997932-1.034246-0.880746 N -1.663109-1.143986-1.170794 C -1.549473-2.117617-2.092397-0.564964-2.386290-2.464420 C -2.810762-2.646928-2.416942-3.043774-3.440598-3.119221 C -3.702542-1.930442-1.625180-4.778005-2.016865-1.509818 C -3.216276 1.574978-0.651359 C -3.067822 2.742119 0.123178-3.064457 2.660939 1.213757 C -2.901486 4.001930-0.462375-2.774946 4.884375 0.170166 C -2.883454 4.132000-1.855124-2.745961 5.112309-2.317337 C -3.028051 2.988986-2.648660-3.001145 3.073529-3.738114 C -3.192983 1.734669-2.050643-3.288405 0.852065-2.688903 [Cu I [N 4 ] tet ] - 73 E tot (BP86/TZVP+ECP(Cu)/RI+COSMO(C 2 Cl 2 )): -2568.81371 Cu 0.172089-0.426400-0.028260 N -1.106289 0.856987-0.899251 B -3.221418-0.170690 0.190840 N -2.471356 0.715557-0.883214 N -2.603879-1.641832 0.198998 N -1.260531-1.870902 0.325862 C -1.107411-3.199141 0.477591 13S
C -2.353627-3.849211 0.465804 C -3.276598-2.822742 0.290261 C -4.792128-0.314424-0.233538 C -5.848021 0.001738 0.641893 C -7.190631-0.167484 0.277280 C -7.519309-0.665552-0.986309 C -6.491608-0.991582-1.879341 C -5.156424-0.817378-1.502465 C -3.026539 1.611631-1.745316 C -2.008858 2.339123-2.351357 C -0.827644 1.827627-1.788861 N 1.429800-0.157638 1.529108 C 1.188645-0.255379 2.850058 C 2.391385-0.300043 3.576288 C 3.385496-0.230743 2.605999 N 2.793340-0.147780 1.382533 B 3.460074 0.043131-0.031556 C 2.789363-2.691186-2.551422 C 3.675288-1.957789-1.767867 C 1.518579-2.210650-2.186843 0.534559-2.506485-2.539332 N 1.621344-1.248964-1.252279 C 2.798185 2.614930 0.166559 C 2.590617 3.892531-0.364903 C 2.663969 4.100179-1.746187 C 2.938888 3.014404-2.585059 C 3.140682 1.741026-2.041123 C 3.076226 1.504492-0.653394 C 5.100696 0.053908 0.077642 S 5.988069-1.440211 0.726274 C 7.718236-0.838856 0.597346 C -2.925560 0.435808 1.686385 N 2.957014-1.098803-0.993190 5.393907 0.905750 0.712381 5.504337 0.257135-0.927293 8.375736-1.641759 0.957090 7.872767 0.054611 1.219103 7.977856-0.604894-0.445056 0.207895 2.100403-1.972169-2.111622 3.129560-3.087498-4.103015 1.674071-1.853809-0.106840-3.610414 0.578754-2.558985-4.910371 0.564521-4.358178-2.847024 0.222240-5.615171 0.413305 1.626756-7.982492 0.094519 0.984011-8.565051-0.798254-1.274682-6.732262-1.383493-2.871168-4.368512-1.083885-2.212171 3.032838-3.465867-3.271478 4.755460-2.010382-1.676261 0.162130-0.297630 3.202379 2.523152-0.382231 4.650264 4.466309-0.274970 2.692102 3.339153 0.902222-2.714632 2.987232 3.158849-3.667749 2.496153 5.094859-2.165828 2.359956 4.728153 0.300850 2.723928 2.471723 1.247674-3.376602-0.204878 2.463264-1.832967 0.431174 1.830764 S -3.494138 2.169134 1.950860 C -2.646259 2.541369 3.535821 14S
-2.898900 3.574765 3.810058-2.982721 1.867054 4.336674-1.556710 2.459009 3.419584 Cu II [N 4 S] spy 73 E tot (BP86/TZVP+ECP(Cu)/RI+COSMO(C 2 Cl 2 )): -2568.6702 Cu 0.072317-0.318771 0.027811 B -3.267599-0.439784 0.041561 C -3.037688-2.064082 0.063499-3.252564-2.468875-0.937646-3.720000-2.549598 0.776207 S -1.330727-2.607441 0.512592 B 3.278363 0.335536-0.020268 C 4.896279 0.546620-0.038702 5.163044 1.200746 0.807010 5.155762 1.103855-0.953202 S 5.996182-0.942274 0.038815 C -1.158309-4.151152-0.464332-0.141589-4.526563-0.294860-1.297637-3.956541-1.535521-1.882415-4.901881-0.123140 C 7.634317-0.116169-0.014365 8.396940-0.904287 0.025764 7.764587 0.552347 0.847354 7.756634 0.453572-0.945397 N -2.584273 0.257712 1.292247 N -1.228711 0.404601 1.404738 C -0.983919 1.011103 2.582166 0.036239 1.241896 2.867397 C -2.186718 1.250890 3.256772-2.324077 1.726278 4.221388 C -3.173296 0.756067 2.408273-4.251720 0.731472 2.512796 N -2.573879 0.185579-1.243409 N -1.218571 0.266497-1.393402 C -0.973452 0.805072-2.603758 0.048842 0.983682-2.917105 C -2.180258 1.060148-3.265348-2.319765 1.492386-4.249757 C -3.166880 0.652427-2.371954-4.247329 0.668448-2.453367 C -4.846992-0.037396 0.008159 C -5.878285-0.992113-0.064649-5.632173-2.055904-0.085807 C -7.229210-0.624458-0.112716-8.000530-1.395706-0.168597 C -7.589984 0.724383-0.088242-8.641623 1.015462-0.123482 C -6.588156 1.699033-0.019652-6.855189 2.757979-0.002076 C -5.244304 1.318477 0.025495-4.479972 2.098684 0.073721 N 2.777760-0.559059-1.223284 N 1.448412-0.833887-1.361486 C 1.307751-1.613220-2.451535 0.321270-1.952884-2.749182 C 2.557054-1.836980-3.043450 2.777805-2.418657-3.931359 C 3.460972-1.153400-2.231532 4.543133-1.077127-2.273597 N 2.786549-0.418056 1.276415 15S
N 1.460416-0.696401 1.447789 C 1.333135-1.358745 2.614433 0.354792-1.696504 2.940518 C 2.586943-1.498431 3.222430 2.817238-1.982032 4.165024 C 3.479468-0.891830 2.340480 4.560411-0.797236 2.371030 C 2.603393 1.814168-0.103825 C 2.376942 2.448371-1.341274 2.578934 1.901260-2.267000 C 1.906000 3.762834-1.422119 1.737907 4.223510-2.398291 C 1.650466 4.488242-0.254447 1.280841 5.513851-0.312175 C 1.876003 3.887719 0.987753 1.683995 4.446474 1.906587 C 2.347120 2.572385 1.055250 2.525641 2.124246 2.037155 Cu II [N 4 ] spl 73 E tot (BP86/TZVP+ECP(Cu)/RI+COSMO(C 2 Cl 2 )): -2568.66915 Cu -0.197144-0.682895 0.193326 N 1.054882 0.341331 1.309296 B 3.122426-0.163683-0.187571 N 2.412288 0.370646 1.131825 N 2.564099-1.633115-0.455304 N 1.228717-1.903104-0.511061 C 1.088702-3.199923-0.860757 C 2.347778-3.778269-1.055238 C 3.252687-2.751976-0.790077 C 4.720766-0.279822 0.064474 C 5.664328 0.270248-0.823504 C 7.042104 0.122109-0.621251 C 7.517785-0.587203 0.484353 C 6.604410-1.147518 1.384289 C 5.231445-0.993800 1.171305 C 2.957868 1.142852 2.101499 C 1.946267 1.607679 2.940144 C 0.770339 1.075847 2.406809 N -1.424487-0.837041-1.351245 C -1.167354-1.278035-2.602120 C -2.342561-1.281503-3.358186 C -3.327629-0.825693-2.482603 N -2.763759-0.567258-1.279114 B -3.406849 0.138958-0.015500 C -2.892104-1.809952 3.190325 C -3.738663-1.262826 2.227264 C -1.600365-1.556547 2.713581-0.634690-1.812626 3.138978 N -1.666192-0.889379 1.542499 C -2.387020 2.402580-0.969596 C -1.991627 3.739107-0.843127 C -2.030997 4.367967 0.404137 C -2.470642 3.648313 1.519791 C -2.862767 2.313282 1.381669 C -2.828872 1.653022 0.137000 C -5.028936 0.245111-0.153960 S -5.984425-1.324509-0.374318 C -7.686753-0.644109-0.467435 C 2.638770 0.749947-1.456880 N -2.985363-0.716953 1.242039 16S
-5.263525 0.905811-1.004003-5.415867 0.753732 0.743665-8.368683-1.493175-0.602528-7.790694 0.038030-1.321964-7.950277-0.116965 0.459365-0.259692 1.181713 2.729795 2.051436 2.251095 3.806073 4.027233 1.319661 2.114932 0.097698-3.635696-0.946302 2.573661-4.799373-1.341140 4.336174-2.736369-0.813946 5.317538 0.847754-1.682653 7.745482 0.566572-1.328766 8.591499-0.703111 0.645398 6.963200-1.705399 2.252166 4.536409-1.446605 1.884149-3.175446-2.325208 4.101104-4.821454-1.253005 2.152332-0.157986-1.565512-2.876303-2.466240-1.578532-4.393334-4.395702-0.696769-2.621290-3.205730 1.770061 2.267601-2.508048 4.129617 2.499791-1.720749 5.409513 0.506868-1.651684 4.291953-1.721723-2.349942 1.933880-1.956880 3.078348 0.366667-2.393290 1.541104 0.688710-1.561078 S 3.064246 2.529841-1.291319 C 2.235646 3.199901-2.783170 2.421932 4.281257-2.799366 2.647096 2.751211-3.697595 1.152802 3.022749-2.735907 Cu II [N 4 ] dspl 73 E tot (BP86/TZVP+ECP(Cu)/RI+COSMO(C 2 Cl 2 )): -2568.66525 Cu -0.197144-0.682895 0.193326 N 1.054882 0.341331 1.309296 B 3.122426-0.163683-0.187571 N 2.412288 0.370646 1.131825 N 2.564099-1.633115-0.455304 N 1.228717-1.903104-0.511061 C 1.088702-3.199923-0.860757 C 2.347778-3.778269-1.055238 C 3.252687-2.751976-0.790077 C 4.720766-0.279822 0.064474 C 5.664328 0.270248-0.823504 C 7.042104 0.122109-0.621251 C 7.517785-0.587203 0.484353 C 6.604410-1.147518 1.384289 C 5.231445-0.993800 1.171305 C 2.957868 1.142852 2.101499 C 1.946267 1.607679 2.940144 C 0.770339 1.075847 2.406809 N -1.424487-0.837041-1.351245 C -1.167354-1.278035-2.602120 C -2.342561-1.281503-3.358186 C -3.327629-0.825693-2.482603 N -2.763759-0.567258-1.279114 B -3.406849 0.138958-0.015500 C -2.892104-1.809952 3.190325 17S
C -3.738663-1.262826 2.227264 C -1.600365-1.556547 2.713581-0.634690-1.812626 3.138978 N -1.666192-0.889379 1.542499 C -2.387020 2.402580-0.969596 C -1.991627 3.739107-0.843127 C -2.030997 4.367967 0.404137 C -2.470642 3.648313 1.519791 C -2.862767 2.313282 1.381669 C -2.828872 1.653022 0.137000 C -5.028936 0.245111-0.153960 S -5.984425-1.324509-0.374318 C -7.686753-0.644109-0.467435 C 2.638770 0.749947-1.456880 N -2.985363-0.716953 1.242039-5.263525 0.905811-1.004003-5.415867 0.753732 0.743665-8.368683-1.493175-0.602528-7.790694 0.038030-1.321964-7.950277-0.116965 0.459365-0.259692 1.181713 2.729795 2.051436 2.251095 3.806073 4.027233 1.319661 2.114932 0.097698-3.635696-0.946302 2.573661-4.799373-1.341140 4.336174-2.736369-0.813946 5.317538 0.847754-1.682653 7.745482 0.566572-1.328766 8.591499-0.703111 0.645398 6.963200-1.705399 2.252166 4.536409-1.446605 1.884149-3.175446-2.325208 4.101104-4.821454-1.253005 2.152332-0.157986-1.565512-2.876303-2.466240-1.578532-4.393334-4.395702-0.696769-2.621290-3.205730 1.770061 2.267601-2.508048 4.129617 2.499791-1.720749 5.409513 0.506868-1.651684 4.291953-1.721723-2.349942 1.933880-1.956880 3.078348 0.366667-2.393290 1.541104 0.688710-1.561078 S 3.064246 2.529841-1.291319 C 2.235646 3.199901-2.783170 2.421932 4.281257-2.799366 2.647096 2.751211-3.697595 1.152802 3.022749-2.735907 18S