butterfly. hydrogen-atom reduced analogue of the mn n ... · preparation of a “twisted basket”...

Supporting Information for

Preparation of a ldquoTwisted Basketrdquo Mn4N8 cluster a two-hydrogen-atom reduced analogue of the Mn4N8 pinned

butterflyMichael R Gau Clifton R Hamilton and Michael J Zdilla

Electronic Supplementary Material (ESI) for ChemCommThis journal is copy The Royal Society of Chemistry 2014

Contents

Experimentalhelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip3

Cyclic voltammetryhelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip 4

X-Ray tableshelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip 5

Experimental

All operations were carried out under rigorous dry anaerobic conditions using glovebox and Schlenk line techniques All reagents were purchased and used as obtained from commercial providers (Aldrich Fisher Strem) unless otherwise specified THF and pyridine were purified by distillation from sodium-benzophenone ketyl Aniline was distilled using CaH2 as a scavenger DCM pentane toluene and benzene were purified using a PureSolve solvent purification system Solvents were degassed and stored over 3 Aring molecular sieves for 12 hours before use Deuterated NMR solvents were purchased from Sigma-Aldrich or Cambridge Isotope Laboratories and stored over 3 Aring molecular sieves for 12 hours before use Visible absorption spectroscopy was performed on a Shimadzu 2550 spectrometer X-Ray crystal structure determinations were performed using a Bruker Kappa APEX II DUO diffractometer equipped with an Oxford Cryostream [MnII

2(μ-NHPh)2(NR2)2(THF)2] (1b) was prepared according to a previously described protocol24 Cyclic voltammagrams were obtained using a CHI-630D electrochemical analyzerworkstation with PIcoamp booster Electrochemical studies were performed under anaerobic conditions using 7 mg 3 in 5 mL of 11 acetonitrilepyridine solvent with tert-butyl ammonium perchlorate electrolyte (01 M) using a standard three-electrode assembly glassy carbon working Pt wire auxiliary and a AgAgClO4 (001 M) reference were employed Potentials were corrected to ferrocene which was used as an internal standard Microanalysis data were obtained from the CENTC Elemental Analysis Facility at the University of Rochester Samples were weighed with a PerkinElmer Model AD-6 Autobalance and their compositions were determined with a PerkinElmer 2400 Series II Analyzer Air-sensitive samples were handled in a VAC Atmospheres glovebox

[Mn4(μ-N2Ph2)2(μ-HNPh2)4(py)4]

Method 1 To a solution of [Mn[N(Si(CH3)3)2]2 (360 mg 09209 mmol) in 3 mL of pyridine was added a solution of aniline (HNPh) (90μL 09874 mmol) in 1 mL of pyridine The mixture was allowed to react for 10 minutes Then a solution of NN-diphenylhydrazine (75 mg 04076 mmol) in 3 mL of toluene and 10 mL of pentane was added This mixture was agitated for 30 seconds and placed in the freezer at -40deg C for 3 hours An orangered solid was formed and the solution was decanted The orange solid was dried in vacuo and dissolved in 3 mL of DCM and 3 mL of pyridine The solution was gently heated at 35deg C until all solid was dissolved and was placed in the freezer at -40deg C for 48 hours The solution was decanted and the red-orange crystals were washed 3-5 times with 3 mL aliquots of pentane and dried in vacuo The crystals were identified using X-ray crystallography Yield 222 mg (01543 mmols 758) Anal Calcd for C53H66Mn4N12 frac12 CH2Cl2 C 6273 H 500 N 1282 Found C 6255 H 491 N 1272 UV-Vis (dichloromethane) max [nm] ( x 10-5) 240(20) 286 (066) 332 (022)

Method 2 via Addition of Diphenylhydrazine and Heat To a solution of 2 (75 mg 00499 mmol) in 6 mL of DCM was added a solution of N Nrsquo-diphenylhydrazine (10 mg 005435 mmol) in 4 mL of DCM The mixture was stirred and heated at 45deg C for 2 hours in a pressure flask The solution was allowed to cool to 25deg C and then dried in

vacuo The solid was washed 3 times with 5 mL of pentane and extracted 3 times with 3 mL of toluene to remove unreacted 2 and hydrazine The resulting residue (crude 3) was dissolved in 1 mL of pyridine Red crystals were isolated through a pyridineether vapor diffusion in a double-vial apparatus The crystals were washed 3-5 times with 3 mL aliquots of pentane and dried in vacuo The crystals were isomorphic and identified by X-ray crystallography as the orthorhombic F tetrapyridine solvate polymorph a = 181979(16) Aring b = 22599(2) Aring c = 40496(5) Aring α = 90deg β = 90deg γ = 90deg Yield 10 mg 000782 mmol (158 yield)

Quantification of azobenzene 006165 mmol of azobenzene (slightly more than one equivalent per hydrazine added) was quantified in the pentane extract of the above reaction (method 2) using 1H-NMR The pentane extraction from above was dried in vacuo The solid was dissolved in C6D6 and analyzed with 2 μL of THF as an internal standard

Control experiment for the conversion of 2 to 3 with diphenylhydrazine 2 was heated at 45degC for 2 hours without the addition of hydrazine While some azobenzene was observed due to thermal decomposition the appearance of the final pyridine extract was different (dark reddish black) and crystals of 3 could not be obtained from this extract

Cyclic Voltammetry

-4-35-3-25-2-15-1-050051 Potential (V) vs FcFc+

Figure S1 Cyclic voltammagram of 3 vs ferrocene Scan rate 100 mVs OCP = -163 V

Crystal Structure Report for 3

Figure X1 Structure of 34 CH2Cl2 Ellipsoids set at 30 probability level C-H hydrogens omitted for clarity N-H hydrogens shown as open circles

A specimen of C73H69Mn4N13 approximate dimensions 0370 mm x 0420 mm x 0430 mm was used for the X-ray crystallographic analysis The X-ray intensity data were measured

The integration of the data using a monoclinic unit cell yielded a total of 62461 reflections to a maximum θ angle of 2799deg (076 Aring resolution) of which 15944 were independent (average redundancy 3918 completeness = 995 Rint = 329) and 13424 (8419) were greater than 2σ(F2) The final cell constants of a = 136312(10) Aring b = 181096(13) Aring c = 27002(2) Aring β = 935179(15)deg volume = 66530(8) Aring3 are based upon the refinement of the XYZ-centroids of reflections above 20 σ(I) The calculated minimum and maximum transmission coefficients (based on crystal size) are 06859 and 07456

The structure was solved and refined using the Bruker SHELXTL Software Package using the space group P 1 21c 1 with Z = 4 for the formula unit C73H69Mn4N13 The final anisotropic full-matrix least-squares refinement on F2 with 811 variables converged at R1 = 443 for the observed data and wR2 = 1027 for all data The goodness-of-fit was 1111 The largest peak in the final difference electron density synthesis was 0781 e-

Aring3 and the largest hole was -0443 e-Aring3 with an RMS deviation of 0061 e-Aring3 On the basis of the final model the calculated density was 1346 gcm3 and F(000) 2792 e-

Table X11 Sample and crystal data for 3 Chemical formula C73H69Mn4N13

Formula weight 134817Temperature 101(2) KWavelength 071073 AringCrystal size 0370 x 0420 x 0430 mmCrystal system monoclinicSpace group P 1 21c 1Unit cell dimensions a = 136312(10) Aring α = 90deg

b = 181096(13) Aring β = 935179(15)degc = 27002(2) Aring γ = 90deg

Volume 66530(8) Aring3

Z 4Density (calculated) 1346 gcm3

Absorption coefficient 0795 mm-1

F(000) 2792

Table X12 Data collection and structure refinement for 3 Theta range for data collection 136 to 2799deg

Index ranges -18lt=hlt=14 -19lt=klt=23 -35lt=llt=35Reflections collected 62461Independent reflections 15944 [R(int) = 00329]Max and min transmission 07456 and 06859Structure solution technique direct methodsStructure solution program SHELXS-97 (Sheldrick 2008)Refinement method Full-matrix least-squares on F2

Refinement program SHELXL-2013 (Sheldrick 2013)Function minimized Σ w(Fo

2 - Fc2)2

Data restraints parameters 15944 0 811Goodness-of-fit on F2 1111Δσmax 0001Final R indices 13424 data Igt2σ(I) R1 = 00443 wR2 = 00957

all data R1 = 00564 wR2 = 01027

Weighting scheme w=1[σ2(Fo2)+(00185P)2+96585P]

where P=(Fo2+2Fc

2)3Largest diff peak and hole 0781 and -0443 eAring-3

RMS deviation from mean 0061 eAring-3

Table X13 Atomic coordinates and equivalent isotropic atomic displacement parameters (Aring2) for 3 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor

xa yb zc U(eq)Mn1 021091(2) 016357(2) 020890(2) 002384(8)Mn2 026369(2) 018696(2) 008740(2) 002462(8)Mn3 007001(2) 028653(2) 012015(2) 002499(8)Mn4 028531(3) 033892(2) 018227(2) 002680(8)N10 024576(14) 008747(11) 027107(7) 00279(4)N3 010755(14) 019111(11) 007870(7) 00289(4)N1 022589(15) 027331(11) 023783(7) 00295(4)N4 031633(15) 014010(11) 015634(7) 00300(4)N2 017800(15) 037180(11) 012547(7) 00298(4)N5 006389(14) 016334(10) 018999(7) 00257(4)N8 035105(14) 027826(11) 008884(7) 00283(4)N6 002509(14) 023730(10) 018246(7) 00260(4)N7 038923(14) 030061(11) 013793(7) 00288(4)N30 094390(15) 033736(11) 007877(7) 00304(4)N40 033351(16) 044557(12) 021453(7) 00340(5)

xa yb zc U(eq)C51 000021(16) 010784(13) 017502(8) 00248(4)C61 096652(16) 026178(13) 021885(8) 00268(5)N20 030825(14) 011370(11) 002817(7) 00288(4)C22 00899(2) 046184(15) 017255(10) 00375(6)C21 014151(17) 044435(13) 013165(9) 00297(5)C23 00474(2) 053008(17) 017748(12) 00479(7)C26 01553(2) 050012(15) 009633(10) 00385(6)C24 00561(2) 058320(16) 014131(12) 00476(7)C25 01108(2) 056936(15) 010110(12) 00433(6)C66 092524(17) 033353(14) 021453(10) 00334(5)C65 086731(19) 036183(17) 025017(11) 00425(7)C64 08458(2) 03205(2) 029092(11) 00520(8)C62 094273(19) 021994(16) 026030(9) 00357(6)C63 08827(2) 02494(2) 029539(10) 00487(7)C86 031595(18) 031563(14) 000433(9) 00314(5)C81 035848(16) 033032(13) 005268(9) 00286(5)C85 03177(2) 036678(16) 096670(10) 00400(6)C82 04047(2) 039943(15) 005961(10) 00382(6)C83 04042(2) 045040(16) 002113(11) 00472(7)C84 03618(2) 043503(16) 097449(11) 00475(7)C71 048552(17) 028208(13) 014978(9) 00289(5)C72 052662(18) 030157(13) 019744(9) 00310(5)C76 054712(18) 024343(15) 011880(10) 00368(6)C73 062237(19) 028307(15) 021281(11) 00389(6)C74 068141(19) 024386(17) 018204(12) 00455(7)C75 06427(2) 022459(17) 013543(12) 00457(7)C202 039606(19) 012147(15) 000905(9) 00352(5)C206 025136(19) 005756(15) 001149(9) 00354(5)C204 03710(2) 001615(18) 095746(10) 00481(7)C205 02798(2) 000750(17) 097659(11) 00450(7)C203 04295(2) 007393(17) 097374(10) 00443(7)C31 006255(16) 018333(14) 003043(9) 00306(5)C34 09781(3) 01640(3) 093438(13) 00697(12)C36 00032(2) 012101(18) 001812(12) 00491(7)C33 00327(3) 02264(2) 094636(11) 00632(10)C32 00740(2) 023535(18) 099399(10) 00447(7)C35 09623(2) 01115(2) 096963(14) 00627(10)C304 07792(2) 039722(17) 002864(10) 00478(8)C302 09450(2) 040305(19) 005732(12) 00579(9)C305 07744(2) 03316(2) 005188(15) 00694(11)C303 08640(3) 043447(19) 003250(13) 00665(11)

xa yb zc U(eq)C306 08587(2) 030323(19) 007602(14) 00653(11)C52 003055(18) 003341(13) 018109(9) 00301(5)C56 090438(18) 011942(14) 015355(9) 00311(5)C55 08460(2) 006074(16) 013759(10) 00402(6)C53 09704(2) 097554(14) 016529(10) 00394(6)C54 08779(2) 098823(16) 014270(11) 00452(7)C41 034796(19) 006601(14) 014975(8) 00315(5)C46 02806(2) 001192(15) 013528(10) 00423(6)C42 04478(2) 00469(2) 015773(11) 00511(8)C44 04051(4) 09195(2) 013831(15) 00755(13)C43 04756(3) 09719(2) 015246(14) 00721(13)C45 03095(3) 093985(18) 012915(13) 00630(10)C402 02837(2) 048286(18) 024708(11) 00491(7)C403 02994(3) 05567(2) 025727(14) 00677(10)C406 04037(2) 048216(15) 019211(10) 00415(6)C405 04250(3) 055581(16) 020055(11) 00520(8)C11 027325(17) 027579(12) 028619(8) 00254(4)C16 036961(19) 025247(14) 029381(10) 00344(5)C14 03679(2) 027906(16) 038066(10) 00463(7)C15 04170(2) 025408(16) 034055(10) 00426(6)C12 02236(2) 030035(15) 032730(10) 00380(6)C13 02718(2) 030165(16) 037444(10) 00458(7)C102 01951(2) 009409(15) 031161(9) 00381(6)C104 02693(2) 098733(16) 034878(10) 00457(7)C106 03093(2) 003139(15) 026985(9) 00376(6)C105 03233(2) 098058(15) 030769(10) 00447(7)C103 02049(2) 004557(18) 035123(10) 00479(7)C4A 06788(2) 03145(2) 090743(14) 00563(8)N1A 06113(3) 02244(2) 098163(13) 00751(10)C5A 05969(2) 03327(2) 093096(14) 00616(10)C6A 05664(2) 02866(3) 096765(14) 00706(12)C2A 06926(4) 02092(2) 095850(17) 00834(14)C404 03716(3) 059346(18) 023370(13) 00625(9)C3A 07281(3) 02521(2) 092199(15) 00701(11)

Table X14 Bond lengths (Aring) for 3 Mn1-N5 20376(19) Mn1-N4 2124(2)Mn1-N1 2140(2) Mn1-N10 22013(19)Mn2-N8 2036(2) Mn2-N3 21283(19)Mn2-N4 2130(2) Mn2-N20 2192(2)

Mn3-N6 20315(19) Mn3-N2 2132(2)Mn3-N3 2138(2) Mn3-N30 21944(19)Mn4-N7 2032(2) Mn4-N1 2114(2)Mn4-N2 21381(19) Mn4-N40 2202(2)N10-C102 1335(3) N10-C106 1337(3)N3-C31 1413(3) N1-C11 1421(3)N4-C41 1424(3) N2-C21 1418(3)N5-C51 1373(3) N5-N6 1450(3)N8-C81 1366(3) N8-N7 1451(3)N6-C61 1377(3) N7-C71 1373(3)N30-C306 1314(4) N30-C302 1324(4)N40-C402 1327(4) N40-C406 1339(4)C51-C56 1412(3) C51-C52 1416(3)C61-C62 1406(3) C61-C66 1418(3)N20-C206 1340(3) N20-C202 1340(3)C22-C23 1374(4) C22-C21 1382(4)C21-C26 1409(4) C23-C24 1381(4)C26-C25 1402(4) C24-C25 1377(4)C66-C65 1381(4) C65-C64 1377(5)C64-C63 1384(5) C62-C63 1395(4)C86-C85 1376(4) C86-C81 1421(3)C81-C82 1408(3) C85-C84 1385(4)Table X14 (cont)C82-C83 1390(4) C83-C84 1381(4)C71-C76 1407(4) C71-C72 1416(3)C72-C73 1386(3) C76-C75 1394(4)C73-C74 1387(4) C74-C75 1380(4)C202-C203 1383(4) C206-C205 1380(4)C204-C203 1372(4) C204-C205 1384(4)C31-C32 1378(4) C31-C36 1416(4)C34-C35 1372(6) C34-C33 1380(6)C36-C35 1402(4) C33-C32 1382(4)C304-C303 1336(5) C304-C305 1348(5)C302-C303 1379(4) C305-C306 1384(4)C52-C53 1382(4) C56-C55 1381(4)C55-C54 1387(4) C53-C54 1386(4)C41-C46 1383(4) C41-C42 1409(4)C46-C45 1376(4) C42-C43 1420(5)C44-C45 1363(6) C44-C43 1386(6)C402-C403 1380(4) C403-C404 1375(5)C406-C405 1381(4) C405-C404 1370(5)C11-C16 1383(3) C11-C12 1407(3)

C16-C15 1382(4) C14-C13 1373(4)C14-C15 1383(4) C12-C13 1396(4)C102-C103 1385(4) C104-C105 1374(4)C104-C103 1377(4) C106-C105 1379(4)C4A-C5A 1359(5) C4A-C3A 1360(5)N1A-C6A 1325(6) N1A-C2A 1333(5)C5A-C6A 1380(6) C2A-C3A 1367(5)

Table X15 Bond angles (deg) for 3 N5-Mn1-N4 12184(8) N5-Mn1-N1 9943(8)N4-Mn1-N1 11211(8) N5-Mn1-N10 11066(7)N4-Mn1-N10 10513(8) N1-Mn1-N10 10696(7)N8-Mn2-N3 12358(8) N8-Mn2-N4 9814(8)N3-Mn2-N4 11305(8) N8-Mn2-N20 10851(8)N3-Mn2-N20 10512(7) N4-Mn2-N20 10763(7)N6-Mn3-N2 12027(8) N6-Mn3-N3 9995(8)N2-Mn3-N3 11574(8) N6-Mn3-N30 10983(8)N2-Mn3-N30 10427(8) N3-Mn3-N30 10612(7)N7-Mn4-N1 12252(8) N7-Mn4-N2 9824(8)N1-Mn4-N2 11299(8) N7-Mn4-N40 10931(8)N1-Mn4-N40 10928(8) N2-Mn4-N40 10235(8)C102-N10-C106 1172(2) C102-N10-Mn1 11809(17)C106-N10-Mn1 12453(17) C31-N3-Mn2 11822(15)C31-N3-Mn3 11734(15) Mn2-N3-Mn3 10392(8)C11-N1-Mn4 11752(15) C11-N1-Mn1 11310(14)Mn4-N1-Mn1 10715(8) C41-N4-Mn1 11965(15)C41-N4-Mn2 11077(14) Mn1-N4-Mn2 10738(9)C21-N2-Mn3 11567(15) C21-N2-Mn4 11376(15)Mn3-N2-Mn4 10660(9) C51-N5-N6 11462(17)C51-N5-Mn1 13205(15) N6-N5-Mn1 11220(13)C81-N8-N7 11497(19) C81-N8-Mn2 12801(15)N7-N8-Mn2 11486(14) C61-N6-N5 11484(18)C61-N6-Mn3 13185(16) N5-N6-Mn3 11330(13)C71-N7-N8 11538(19) C71-N7-Mn4 12956(16)N8-N7-Mn4 11417(13) C306-N30-C302 1156(2)C306-N30-Mn3 11958(18) C302-N30-Mn3 12477(19)C402-N40-C406 1171(2) C402-N40-Mn4 1238(2)C406-N40-Mn4 11734(17) N5-C51-C56 1244(2)N5-C51-C52 1192(2) C56-C51-C52 1164(2)N6-C61-C62 1245(2) N6-C61-C66 1187(2)C62-C61-C66 1167(2) C206-N20-C202 1176(2)C206-N20-Mn2 12160(16) C202-N20-Mn2 12076(17)C23-C22-C21 1214(3) C22-C21-C26 1182(2)C22-C21-N2 1204(2) C26-C21-N2 1215(2)C22-C23-C24 1202(3) C25-C26-C21 1202(2)Table X15 (cont)C25-C24-C23 1203(3) C24-C25-C26 1195(3)C65-C66-C61 1216(3) C64-C65-C66 1209(3)C65-C64-C63 1188(3) C63-C62-C61 1205(3)C64-C63-C62 1215(3) C85-C86-C81 1219(2)

N8-C81-C82 1248(2) N8-C81-C86 1189(2)C82-C81-C86 1163(2) C86-C85-C84 1210(3)C83-C82-C81 1206(3) C84-C83-C82 1220(3)C83-C84-C85 1181(3) N7-C71-C76 1254(2)N7-C71-C72 1180(2) C76-C71-C72 1165(2)C73-C72-C71 1216(2) C75-C76-C71 1207(3)C72-C73-C74 1210(3) C75-C74-C73 1182(2)C74-C75-C76 1220(3) N20-C202-C203 1227(3)N20-C206-C205 1232(2) C203-C204-C205 1190(3)C206-C205-C204 1185(3) C204-C203-C202 1191(3)C32-C31-N3 1219(2) C32-C31-C36 1177(3)N3-C31-C36 1204(2) C35-C34-C33 1207(3)C35-C36-C31 1204(3) C34-C33-C32 1198(4)C31-C32-C33 1218(3) C34-C35-C36 1194(3)C303-C304-C305 1184(3) N30-C302-C303 1236(3)C304-C305-C306 1189(3) C304-C303-C302 1195(3)N30-C306-C305 1239(3) C53-C52-C51 1215(2)C55-C56-C51 1210(2) C56-C55-C54 1218(2)C52-C53-C54 1211(2) C53-C54-C55 1182(2)C46-C41-C42 1192(3) C46-C41-N4 1201(2)C42-C41-N4 1207(3) C45-C46-C41 1210(3)C41-C42-C43 1188(4) C45-C44-C43 1203(3)C44-C43-C42 1198(3) C44-C45-C46 1208(4)N40-C402-C403 1231(3) C404-C403-C402 1189(3)N40-C406-C405 1235(3) C404-C405-C406 1182(3)C16-C11-C12 1185(2) C16-C11-N1 1200(2)C12-C11-N1 1214(2) C15-C16-C11 1210(3)C13-C14-C15 1203(3) C16-C15-C14 1200(3)C13-C12-C11 1201(3) C14-C13-C12 1199(3)N10-C102-C103 1231(3) C105-C104-C103 1188(3)N10-C106-C105 1233(3) C104-C105-C106 1189(3)C104-C103-C102 1187(3) C5A-C4A-C3A 1182(4)C6A-N1A-C2A 1151(4) C4A-C5A-C6A 1187(4)Table X15 (cont)N1A-C6A-C5A 1244(3) N1A-C2A-C3A 1242(4)C405-C404-C403 1191(3) C4A-C3A-C2A 1194(3)

Table X16 Torsion angles (deg) for 3 C51-N5-N6-C61 821(2) Mn1-N5-N6-C61 -10848(17)C51-N5-N6-Mn3 -9896(18) Mn1-N5-N6-Mn3 7044(15)C81-N8-N7-C71 -930(2) Mn2-N8-N7-C71 10235(19)

C81-N8-N7-Mn4 9679(19) Mn2-N8-N7-Mn4 -6789(17)N6-N5-C51-C56 04(3) Mn1-N5-C51-C56 -16630(17)N6-N5-C51-C52 -17950(19) Mn1-N5-C51-C52 138(3)N5-N6-C61-C62 -10(3) Mn3-N6-C61-C62 -17969(18)N5-N6-C61-C66 -17993(18) Mn3-N6-C61-C66 14(3)C23-C22-C21-C26 41(4) C23-C22-C21-N2 -1750(2)Mn3-N2-C21-C22 605(3) Mn4-N2-C21-C22 -634(3)Mn3-N2-C21-C26 -1185(2) Mn4-N2-C21-C26 1176(2)C21-C22-C23-C24 -03(5) C22-C21-C26-C25 -49(4)N2-C21-C26-C25 1742(2) C22-C23-C24-C25 -28(5)C23-C24-C25-C26 19(5) C21-C26-C25-C24 20(4)N6-C61-C66-C65 -1788(2) C62-C61-C66-C65 22(3)C61-C66-C65-C64 -14(4) C66-C65-C64-C63 -05(4)N6-C61-C62-C63 1799(2) C66-C61-C62-C63 -11(4)C65-C64-C63-C62 16(4) C61-C62-C63-C64 -07(4)N7-N8-C81-C82 40(3) Mn2-N8-C81-C82 16633(19)N7-N8-C81-C86 -17499(19) Mn2-N8-C81-C86 -127(3)C85-C86-C81-N8 1776(2) C85-C86-C81-C82 -15(3)C81-C86-C85-C84 04(4) N8-C81-C82-C83 -1767(2)C86-C81-C82-C83 23(4) C81-C82-C83-C84 -21(4)C82-C83-C84-C85 08(5) C86-C85-C84-C83 00(4)N8-N7-C71-C76 -08(3) Mn4-N7-C71-C76 16763(19)N8-N7-C71-C72 -17920(19) Mn4-N7-C71-C72 -108(3)N7-C71-C72-C73 1782(2) C76-C71-C72-C73 -04(3)N7-C71-C76-C75 -1771(2) C72-C71-C76-C75 13(4)C71-C72-C73-C74 -07(4) C72-C73-C74-C75 08(4)C73-C74-C75-C76 01(4) C71-C76-C75-C74 -12(4)C206-N20-C202-C203 -06(4) Mn2-N20-C202-C203 1762(2)Table X16 (cont)C202-N20-C206-C205 11(4) Mn2-N20-C206-C205 -1757(2)N20-C206-C205-C204 -08(4) C203-C204-C205-C206 -01(5)C205-C204-C203-C202 05(4) N20-C202-C203-C204 -01(4)Mn2-N3-C31-C32 -661(3) Mn3-N3-C31-C32 597(3)Mn2-N3-C31-C36 1142(2) Mn3-N3-C31-C36 -1200(2)C32-C31-C36-C35 33(4) N3-C31-C36-C35 -1770(3)C35-C34-C33-C32 15(5) N3-C31-C32-C33 1777(3)C36-C31-C32-C33 -25(4) C34-C33-C32-C31 02(5)C33-C34-C35-C36 -08(5) C31-C36-C35-C34 -16(5)C306-N30-C302-C303 -14(5) Mn3-N30-C302-C303 -1784(3)C303-C304-C305-C306 -41(6) C305-C304-C303-C302 39(6)N30-C302-C303-C304 -12(6) C302-N30-C306-C305 12(6)Mn3-N30-C306-C305 1784(3) C304-C305-C306-N30 16(7)

N5-C51-C52-C53 -1780(2) C56-C51-C52-C53 20(3)N5-C51-C56-C55 1774(2) C52-C51-C56-C55 -27(3)C51-C56-C55-C54 12(4) C51-C52-C53-C54 02(4)C52-C53-C54-C55 -18(4) C56-C55-C54-C53 11(4)Mn1-N4-C41-C46 594(3) Mn2-N4-C41-C46 -663(2)Mn1-N4-C41-C42 -1207(2) Mn2-N4-C41-C42 1136(2)C42-C41-C46-C45 08(4) N4-C41-C46-C45 -1794(2)C46-C41-C42-C43 -24(4) N4-C41-C42-C43 1778(2)C45-C44-C43-C42 04(5) C41-C42-C43-C44 18(5)C43-C44-C45-C46 -21(5) C41-C46-C45-C44 15(5)C406-N40-C402-C403 19(5) Mn4-N40-C402-C403 -1626(3)N40-C402-C403-C404 -17(6) C402-N40-C406-C405 -11(4)Mn4-N40-C406-C405 1644(2) N40-C406-C405-C404 00(5)Mn4-N1-C11-C16 -624(3) Mn1-N1-C11-C16 633(2)Mn4-N1-C11-C12 1189(2) Mn1-N1-C11-C12 -1154(2)C12-C11-C16-C15 -09(4) N1-C11-C16-C15 -1797(2)C11-C16-C15-C14 02(4) C13-C14-C15-C16 07(4)C16-C11-C12-C13 07(4) N1-C11-C12-C13 1795(2)C15-C14-C13-C12 -08(4) C11-C12-C13-C14 01(4)C106-N10-C102-C103 -08(4) Mn1-N10-C102-C103 1745(2)C102-N10-C106-C105 09(4) Mn1-N10-C106-C105 -1740(2)C103-C104-C105-C106 -15(4) N10-C106-C105-C104 02(5)C105-C104-C103-C102 16(5) N10-C102-C103-C104 -05(5)C3A-C4A-C5A-C6A -13(5) C2A-N1A-C6A-C5A 19(6)Table X16 (cont)C4A-C5A-C6A-N1A -06(5) C6A-N1A-C2A-C3A -16(7)C406-C405-C404-C403 02(5) C402-C403-C404-C405 05(6)C5A-C4A-C3A-C2A 17(6) N1A-C2A-C3A-C4A -02(7)

Crystal Structure Report for 3_DCM A specimen of C72H72Cl8Mn4N12 approximate dimensions 0080 mm x 0120 mm x 0140 mm was used for the X-ray crystallographic analysis The X-ray intensity data were measured

The integration of the data using a tetragonal unit cell yielded a total of 24305 reflections to a maximum θ angle of 2667deg (079 Aring resolution) of which 4129 were independent (average redundancy 5886 completeness = 990 Rint = 401) and 3268 (7915) were greater than 2σ(F2) The final cell constants of a = 18311(4) Aring b = 18311(4) Aring c = 47150(11) Aring volume = 15809(8) Aring3 are based upon the refinement of the XYZ-centroids of reflections above 20 σ(I) The calculated minimum and maximum transmission coefficients (based on crystal size) are 05503 and 07454

The structure was solved and refined using the Bruker SHELXTL Software Package using the space group I 41a c d with Z = 8 for the formula unit C72H72Cl8Mn4N12 The final anisotropic full-matrix least-squares refinement on F2 with 273 variables converged at R1 = 471 for the observed data and wR2 = 1310 for all data The goodness-of-fit was 1048 The largest peak in the final difference electron density synthesis was 0490 e-



Table X21 Sample and crystal data for 3_DCM Chemical formula C72H72Cl8Mn4N12

Formula weight 160877Temperature 100(2) KWavelength 071073 AringCrystal size 0080 x 0120 x 0140 mmCrystal system tetragonalSpace group I 41a c dUnit cell dimensions a = 18311(4) Aring α = 90deg

b = 18311(4) Aring β = 90degc = 47150(11) Aring γ = 90deg




F(000) 6592

Table X22 Data collection and structure refinement for 3_DCM Theta range for data collection 239 to 2667deg



2 - Fc2)2


all data R1 = 00647 wR2 = 01310


where P=(Fo2+2Fc



Table X23 Atomic coordinates and equivalent isotropic atomic displacement parameters (Aring2) for 3_DCM U(eq) is defined as one third of the trace of the orthogonalized Uij tensor

xa yb zc U(eq)Mn1 057842(2) 031514(2) 010082(2) 003475(14)N4 048160(12) 037446(12) 011207(5) 00365(5)N3 053947(11) 025237(13) 006853(4) 00381(5)C14 057289(14) 020631(15) 004971(5) 00372(6)N2 065675(13) 039595(13) 008525(6) 00473(6)C12 065052(15) 020737(16) 004788(6) 00404(6)C11 053627(17) 015742(16) 003161(6) 00459(7)C10 053578(16) 048625(16) 013000(6) 00472(7)C9 05753(2) 011051(19) 001399(7) 00580(8)C8 068750(17) 016083(17) 003010(6) 00486(7)C7 049143(14) 045110(14) 011084(6) 00385(6)C13 065055(19) 011127(18) 001313(7) 00564(8)C6 05125(3) 06017(2) 010850(12) 00984(17)C5 04580(2) 04925(2) 009002(10) 00835(13)C3 05460(2) 056103(19) 012898(9) 00657(9)

xa yb zc U(eq)C2 04692(3) 05682(2) 008924(14) 0126(2)C17 07468(4) 05091(3) 006920(13) 0113(2)C15 07777(5) 04421(6) 00787(2) 0080(3)C4 07271(4) 03907(4) 00872(2) 0055(2)C1 06320(7) 04573(6) 00700(3) 0063(3)C16 06744(10) 05126(7) 00622(3) 0077(4)C1A 06483(10) 04290(12) 00647(4) 0126(8)C16A 06948(15) 04877(15) 00554(4) 0182(12)C4A 07090(7) 04212(8) 01036(3) 0096(5)C15A 07510(7) 04805(8) 00965(3) 0108(6)Cl2 087224(14) 026260(11) 005310(3) 01673(10)C21 08945(8) 02889(4) 002102(16) 0107(4)Cl1 08552(6) 03724(7) 001301(13) 0217(3)C21A 0836(2) 0316(3) 00250(8) 019(3)Cl1A 08737(5) 03928(4) 001443(13) 0080(3)

Table X24 Bond lengths (Aring) for 3_DCM Mn1-N3 2037(2) Mn1-N4 2122(2)Mn1-N4 2146(2) Mn1-N2 2188(2)N4-C7 1416(3) N4-Mn1 2122(2)N3-C14 1369(3) N3-N3 1448(4)C14-C11 1407(4) C14-C12 1424(4)N2-C1A 1155(15) N2-C4 1295(8)N2-C4A 1371(11) N2-C1 1409(12)C12-C8 1374(4) C11-C9 1392(4)C10-C7 1375(4) C10-C3 1383(5)C9-C13 1379(5) C8-C13 1386(5)C7-C5 1384(4) C6-C2 1353(7)C6-C3 1364(6) C5-C2 1401(6)C17-C16A 122(2) C17-C16 137(2)C17-C15A 1394(12) C17-C15 1424(12)C15-C4 1379(10) C1-C16 133(2)C1A-C16A 144(2) C4A-C15A 1372(12)Cl2-C21 1639(7) Cl2-C21A 178(3)C21-Cl1 1731(11) C21A-Cl1A 165(2)

Table X25 Bond angles (deg) for 3_DCM N3-Mn1-N4 12186(9) N3-Mn1-N4 10044(8)N4-Mn1-N4 10917(7) N3-Mn1-N2 11113(9)N4-Mn1-N2 10679(9) N4-Mn1-N2 10639(9)C7-N4-Mn1 11860(17) C7-N4-Mn1 11274(17)Mn1-N4-Mn1 10963(9) C14-N3-N3 1142(2)C14-N3-Mn1 13252(17) N3-N3-Mn1 11254(14)N3-C14-C11 1249(2) N3-C14-C12 1185(2)C11-C14-C12 1166(3) C1A-N2-C4A 1167(8)C4-N2-C1 1145(7) C1A-N2-Mn1 1233(7)C4-N2-Mn1 1254(4) C4A-N2-Mn1 1182(4)C1-N2-Mn1 1200(6) C8-C12-C14 1214(3)C9-C11-C14 1207(3) C7-C10-C3 1214(3)C13-C9-C11 1216(3) C12-C8-C13 1212(3)C10-C7-C5 1181(3) C10-C7-N4 1208(2)C5-C7-N4 1211(3) C9-C13-C8 1185(3)C2-C6-C3 1194(4) C7-C5-C2 1197(4)C6-C3-C10 1203(4) C6-C2-C5 1211(4)C16A-C17-C15A 1145(8) C16-C17-C15 1202(7)C4-C15-C17 1143(8) N2-C4-C15 1268(8)C16-C1-N2 1242(13) C1-C16-C17 1176(12)N2-C1A-C16A 1245(14) C17-C16A-C1A 1228(13)N2-C4A-C15A 1202(8) C4A-C15A-C17 1195(9)Cl2-C21-Cl1 1110(6) Cl1A-C21A-Cl2 1224(13)

Table X26 Torsion angles (deg) for 3_DCM N3-N3-C14-C11 -03(4) Mn1-N3-C14-C11 1687(2)N3-N3-C14-C12 1794(2) Mn1-N3-C14-C12 -116(4)N3-C14-C12-C8 1778(3) C11-C14-C12-C8 -25(4)N3-C14-C11-C9 -1773(3) C12-C14-C11-C9 30(4)C14-C11-C9-C13 -15(5) C14-C12-C8-C13 03(4)C3-C10-C7-C5 11(5) C3-C10-C7-N4 1798(3)Mn1-N4-C7-C10 612(3) Mn1-N4-C7-C10 -688(3)Mn1-N4-C7-C5 -1201(3) Mn1-N4-C7-C5 1099(3)C11-C9-C13-C8 -07(5) C12-C8-C13-C9 13(5)C10-C7-C5-C2 -08(7) N4-C7-C5-C2 -1795(5)C2-C6-C3-C10 01(8) C7-C10-C3-C6 -08(6)C3-C6-C2-C5 02(10) C7-C5-C2-C6 01(10)C16A-C17-C15-C4 -408(15) C16-C17-C15-C4 -163(13)C15A-C17-C15-C4 714(9) C1A-N2-C4-C15 339(14)C4A-N2-C4-C15 -807(11) C1-N2-C4-C15 77(12)Mn1-N2-C4-C15 -1768(7) C17-C15-C4-N2 52(13)C1A-N2-C1-C16 -82(2) C4-N2-C1-C16 -112(14)C4A-N2-C1-C16 357(14) Mn1-N2-C1-C16 1731(9)N2-C1-C16-C17 07(17) C16A-C17-C16-C1 70(2)C15A-C17-C16-C1 -401(15) C15-C17-C16-C1 135(16)C4-N2-C1A-C16A -37(2) C4A-N2-C1A-C16A 9(3)C1-N2-C1A-C16A 81(3) Mn1-N2-C1A-C16A 1732(18)C16-C17-C16A-C1A -91(3) C15A-C17-C16A-C1A -10(3)C15-C17-C16A-C1A 42(3) N2-C1A-C16A-C17 -2(4)C1A-N2-C4A-C15A -4(2) C4-N2-C4A-C15A 783(14)C1-N2-C4A-C15A -304(16) Mn1-N2-C4A-C15A -1687(11)N2-C4A-C15A-C17 -8(2) C16A-C17-C15A-C4A 14(2)C16-C17-C15A-C4A 447(18) C15-C17-C15A-C4A -707(14)C21A-Cl2-C21-Cl1 291(15) C21-Cl2-C21A-Cl1A -65(3)

Crystal Structure Report for 3_Py4

Figure X3 Structure of 34 Py Left Ellipsoids set at 30 probability level C-H hydrogens omitted for clarity N-H hydrogens shown as open circles Right ball and stick view with atom labels


The integration of the data using an orthorhombic unit cell yielded a total of 11276 reflections to a maximum θ angle of 2082deg (100 Aring resolution) of which 3678 were independent (average redundancy 3066 completeness = 998 Rint = 246) and 3182 (8651) were greater than 2σ(F2) The final cell constants of a = 181979(16) Aring b = 22599(2) Aring c = 40496(5) Aring volume = 16654(3) Aring3 are based upon the refinement of the XYZ-centroids of reflections above 20 σ(I) The calculated minimum and maximum transmission coefficients (based on crystal size) are 06669 and 07446

The structure was solved and refined using the Bruker SHELXTL Software Package using the space group F d d 2 with Z = 8 for the formula unit C88H84Mn4N16 The final anisotropic full-matrix least-squares refinement on F2 with 594 variables converged at R1 = 379 for the observed data and wR2 = 1031 for all data The goodness-of-fit was 1052 The largest peak in the final difference electron density synthesis was 0210 e-Aring3 and the largest hole was -0154 e-Aring3 with an RMS deviation of 0035 e-Aring3 On the basis of the final model the calculated density was 1265 gcm3 and F(000) 6592 e-

Table X31 Sample and crystal data for 3_Py4 Chemical formula C88H84Mn4N16

Formula weight 158547Temperature 100(2) KWavelength 071073 AringCrystal size 0150 x 0250 x 0330 mmCrystal system orthorhombicSpace group F d d 2Unit cell dimensions a = 181979(16) Aring α = 90deg





F(000) 6592

Table X32 Data collection and structure refinement for 3_Py4 Theta range for data collection 152 to 2082degIndex ranges -18lt=hlt=18 -19lt=klt=22 -40lt=llt=33Reflections collected 11276Independent reflections 3678 [R(int) = 00246]Max and min transmission 07446 and 06669Structure solution technique direct methodsStructure solution program SHELXS-97 (Sheldrick 2008)Refinement method Full-matrix least-squares on F2


2 - Fc2)2

Data restraints parameters 3678 292 594Goodness-of-fit on F2 1052Final R indices 3182 data Igt2σ(I) R1 = 00379 wR2 = 00990

all data R1 = 00450 wR2 = 01031


where P=(Fo2+2Fc

2)3Absolute structure parameter 0030(14)Largest diff peak and hole 0210 and -0154 eAring-3

Table X33 Atomic coordinates and equivalent isotropic atomic displacement parameters (Aring2) for 3_Py4 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor

xa yb zc U(eq)N1 05111(3) 00309(2) 009333(17) 00628(15)N3 05157(5) 01000(3) 017488(18) 0094(2)N6 03719(4) 00157(3) 014581(18) 00746(17)C11 05726(4) 00427(3) 007479(19) 0065(2)C12 06024(5) 01006(3) 00759(2) 0076(2)C13 06668(6) 01140(4) 00595(3) 0102(3)C14 07035(6) 00730(5) 00406(3) 0113(3)C15 06733(6) 00170(4) 00380(2) 0094(3)C16 06111(5) 00025(3) 00544(2) 0074(2)N2 04141(7) 01555(5) 01078(4) 0064(4)C21 04315(7) 01656(5) 00756(3) 0069(3)C22 04118(7) 02169(5) 00601(4) 0097(4)C23 03720(8) 02595(7) 00787(5) 0095(4)C24 03528(10) 02489(10) 01094(6) 0109(6)C25 03745(7) 01949(6) 01246(4) 0095(5)Mn1 045956(6) 007410(4) 013104(10) 00662(4)N2A 0414(2) 01618(14) 01219(8) 0107(18)C21A 0386(2) 01692(12) 00917(8) 0091(15)C22A 0345(3) 02198(16) 00845(8) 0117(17)C23A 0335(3) 02631(15) 01086(8) 015(2)C24A 0365(3) 02543(14) 01398(7) 0156(18)C25A 0405(3) 02025(15) 01452(7) 0167(19)C41 04440(7) 00512(6) 02474(3) 0086(3)C42 04933(7) 00801(5) 02679(2) 0085(3)C43 04735(11) 01259(6) 02877(3) 0116(5)C44 04021(16) 01507(7) 02867(4) 0161(8)C45 03509(11) 01195(10) 02684(4) 0175(9)C46 03706(6) 00731(7) 02478(3) 0105(4)N4 04622(3) 00068(3) 022505(17) 00747(18)C41A 0434(4) 0054(3) 02451(15) 0080(18)C42A 0469(3) 0103(3) 02587(15) 0083(18)C43A 0435(3) 0136(3) 02834(15) 0080(18)C44A 0365(3) 0119(3) 02943(15) 0077(18)C45A 0330(3) 0070(3) 02808(16) 0076(18)C46A 0364(3) 0037(3) 02562(15) 0076(18)N5 0312(2) 0911(2) 02003(12) 014(2)C51 0307(3) 0895(2) 02319(11) 014(2)C52 0250(3) 0858(3) 02422(10) 014(2)C53 0198(2) 0840(2) 02193(12) 0143(19)C54 0204(2) 0857(2) 01865(12) 0145(19)C55 0263(2) 0894(2) 01778(11) 0139(19)

xa yb zc U(eq)Mn2 040739(6) 096622(5) 018739(10) 00731(4)N5A 03101(8) 09230(7) 02088(3) 0102(4)C51A 03187(10) 08737(7) 02273(3) 0106(5)C52A 02608(14) 08423(8) 02408(4) 0116(6)C53A 01926(12) 08666(11) 02383(4) 0145(7)C54A 01803(9) 09123(10) 02180(5) 0179(9)C55A 02402(9) 09417(7) 02046(4) 0122(5)C61 03035(5) 00427(3) 01461(2) 0069(2)C62 02890(6) 00860(5) 01698(3) 0107(3)C63 02203(8) 01125(5) 01720(4) 0132(4)C64 01640(10) 00977(7) 01501(4) 0145(5)C65 01796(7) 00586(9) 01262(4) 0162(7)C66 02487(6) 00287(5) 01238(2) 0106(3)C81 05090(8) 01657(8) 01782(5) 0083(6)C82 04687(10) 01970(7) 02015(4) 0082(5)C83 04718(11) 02565(10) 02047(5) 0107(6)C84 05217(13) 02869(10) 01860(6) 0116(7)C85 05653(14) 02562(10) 01623(7) 0137(8)C86 05571(10) 01944(10) 01596(5) 0099(6)C91 05635(18) 01546(9) 01752(5) 0097(6)C92 06257(15) 01626(9) 01525(4) 0106(6)C93 06667(15) 02126(9) 01535(5) 0123(6)C94 06540(17) 02569(10) 01743(6) 0135(7)C95 05942(18) 02509(10) 01965(6) 0132(7)C96 05533(16) 01994(8) 01970(5) 0115(6)

Table X34 Bond lengths (Aring) for 3_Py4 N1-C11 1375(9) N1-N1 1454(10)N1-Mn1 2040(6) N3-C91 151(2)N3-Mn2 2111(7) N3-Mn1 2131(6)N6-C61 1386(10) N6-Mn2 2122(6)N6-Mn1 2156(6) C11-C16 1414(11)C11-C12 1417(10) C12-C13 1380(12)C13-C14 1375(14) C14-C15 1383(14)C15-C16 1352(12) N2-C25 1331(18)N2-C21 1362(19) N2-Mn1 2226(12)C21-C22 1367(15) C22-C23 142(2)C23-C24 131(3) C24-C25 142(3)Mn1-N2A 218(3) N2A-C25A 1327(14)N2A-C21A 1340(14) C21A-C22A 1390(13)

C22A-C23A 1396(14) C23A-C24A 1395(14)C24A-C25A 1390(14) C41-C42 1387(15)C41-N4 1391(12) C41-C46 1426(15)C42-C43 1358(16) C43-C44 141(2)C44-C45 138(2) C45-C46 1387(19)N4-N4 1409(12) N4-C41A 143(5)N4-Mn2 2040(6) C41A-C42A 1388(15)C41A-C46A 141(4) C42A-C43A 1391(14)C43A-C44A 1390(14) C44A-C45A 1388(14)C45A-C46A 1392(14) N5-C51 1335(14)N5-C55 1336(14) N5-Mn2 220(3)C51-C52 1392(14) C52-C53 1393(14)C53-C54 1389(14) C54-C55 1390(14)Mn2-N3 2111(7) Mn2-N5A 2199(12)N5A-C51A 1352(17) N5A-C55A 1352(19)C51A-C52A 1383(19) C52A-C53A 136(3)C53A-C54A 134(2) C54A-C55A 1386(18)C61-C66 1382(12) C61-C62 1396(13)C62-C63 1389(15) C63-C64 1395(19)C64-C65 134(2) C65-C66 1431(18)C81-C86 132(3) C81-C82 139(2)C82-C83 135(2) C83-C84 137(3)C84-C85 143(3) C85-C86 141(3)Table X34 (cont)C91-C96 135(3) C91-C92 147(3)C92-C93 136(2) C93-C94 133(3)C94-C95 142(4) C95-C96 138(3)

Table X35 Bond angles (deg) for 3_Py4 C11-N1-N1 1143(6) C11-N1-Mn1 1337(5)N1-N1-Mn1 1094(4) C91-N3-Mn2 1013(13)C91-N3-Mn1 1206(8) Mn2-N3-Mn1 1088(3)C61-N6-Mn2 1199(5) C61-N6-Mn1 1134(5)Mn2-N6-Mn1 1085(3) N1-C11-C16 1267(7)N1-C11-C12 1183(7) C16-C11-C12 1150(7)C13-C12-C11 1207(8) C14-C13-C12 1222(9)C13-C14-C15 1177(9) C16-C15-C14 1212(9)C15-C16-C11 1230(8) C25-N2-C21 1203(12)C25-N2-Mn1 1225(11) C21-N2-Mn1 1171(8)N2-C21-C22 1213(13) C21-C22-C23 1178(14)C24-C23-C22 1209(17) C23-C24-C25 1195(17)

N2-C25-C24 1201(16) N1-Mn1-N3 1223(3)N1-Mn1-N6 1048(2) N3-Mn1-N6 1070(3)N1-Mn1-N2A 1189(10) N3-Mn1-N2A 941(8)N6-Mn1-N2A 1089(12) N1-Mn1-N2 1045(4)N3-Mn1-N2 1076(4) N6-Mn1-N2 1104(4)C25A-N2A-C21A 1207(18) C25A-N2A-Mn1 1241(18)C21A-N2A-Mn1 1144(19) N2A-C21A-C22A 1200(16)C21A-C22A-C23A 1202(17) C24A-C23A-C22A 1186(17)C25A-C24A-C23A 1178(17) N2A-C25A-C24A 1227(18)C42-C41-N4 1252(11) C42-C41-C46 1158(10)N4-C41-C46 1188(10) C43-C42-C41 1228(13)C42-C43-C44 1219(13) C45-C44-C43 1155(13)C44-C45-C46 1223(16) C45-C46-C41 1208(13)C41-N4-N4 1129(7) N4-N4-C41A 120(3)C41-N4-Mn2 1339(6) N4-N4-Mn2 1123(4)C41A-N4-Mn2 126(3) C42A-C41A-C46A 120(2)C42A-C41A-N4 131(4) C46A-C41A-N4 107(4)C41A-C42A-C43A 121(2) C44A-C43A-C42A 1191(18)Table X35 (cont)C45A-C44A-C43A 1208(19) C44A-C45A-C46A 121(2)C45A-C46A-C41A 119(2) C51-N5-C55 1222(19)C51-N5-Mn2 115(2) C55-N5-Mn2 122(2)N5-C51-C52 1198(18) C51-C52-C53 1191(18)C54-C53-C52 1197(18) C53-C54-C55 1184(17)N5-C55-C54 1208(18) N4-Mn2-N3 1000(3)N4-Mn2-N6 1204(2) N3-Mn2-N6 1127(3)N4-Mn2-N5A 1073(3) N3-Mn2-N5A 1083(5)N6-Mn2-N5A 1075(4) N4-Mn2-N5 1176(14)N3-Mn2-N5 1005(16) N6-Mn2-N5 1041(12)C51A-N5A-C55A 1158(12) C51A-N5A-Mn2 1194(12)C55A-N5A-Mn2 1247(10) N5A-C51A-C52A 1237(15)C53A-C52A-C51A 1173(16) C54A-C53A-C52A 1206(16)C53A-C54A-C55A 1186(17) N5A-C55A-C54A 1228(15)C66-C61-N6 1228(8) C66-C61-C62 1182(9)N6-C61-C62 1190(7) C63-C62-C61 1212(11)C62-C63-C64 1210(13) C65-C64-C63 1175(14)C64-C65-C66 1231(13) C61-C66-C65 1188(11)C86-C81-C82 1190(17) C83-C82-C81 1234(18)C82-C83-C84 1182(18) C83-C84-C85 120(2)C86-C85-C84 118(2) C81-C86-C85 121(2)C96-C91-C92 1149(19) C96-C91-N3 123(2)C92-C91-N3 1226(16) C93-C92-C91 121(2)

C94-C93-C92 123(2) C93-C94-C95 118(2)C96-C95-C94 120(2) C91-C96-C95 123(2)

Table X36 Torsion angles (deg) for 3_Py4 N1-N1-C11-C16 54(10) Mn1-N1-C11-C16 1648(6)N1-N1-C11-C12 -1740(6) Mn1-N1-C11-C12 -146(10)N1-C11-C12-C13 1758(8) C16-C11-C12-C13 -36(11)C11-C12-C13-C14 23(15) C12-C13-C14-C15 06(16)C13-C14-C15-C16 -19(16) C14-C15-C16-C11 04(14)N1-C11-C16-C15 -1770(8) C12-C11-C16-C15 24(11)C25-N2-C21-C22 3(2) Mn1-N2-C21-C22 -1739(9)N2-C21-C22-C23 0(2) C21-C22-C23-C24 -2(2)Table X36 (cont)C22-C23-C24-C25 2(3) C21-N2-C25-C24 -3(2)Mn1-N2-C25-C24 1739(11) C23-C24-C25-N2 0(2)C25A-N2A-C21A-C22A 00(5) Mn1-N2A-C21A-C22A 170(3)N2A-C21A-C22A-C23A 00(4) C21A-C22A-C23A-C24A -01(10)C22A-C23A-C24A-C25A 00(13) C21A-N2A-C25A-C24A 00(10)Mn1-N2A-C25A-C24A -170(3) C23A-C24A-C25A-N2A 00(13)N4-C41-C42-C43 1755(10) C46-C41-C42-C43 08(17)C41-C42-C43-C44 -52(19) C42-C43-C44-C45 10(2)C43-C44-C45-C46 -11(3) C44-C45-C46-C41 7(3)C42-C41-C46-C45 -15(19) N4-C41-C46-C45 -1766(12)C42-C41-N4-N4 -03(14) C46-C41-N4-N4 1743(11)C42-C41-N4-C41A -160(20) C46-C41-N4-C41A 20(20)C42-C41-N4-Mn2 -1685(8) C46-C41-N4-Mn2 61(17)C41-N4-C41A-C42A 45(17) N4-N4-C41A-C42A 22(6)Mn2-N4-C41A-C42A -144(4) C41-N4-C41A-C46A -120(20)N4-N4-C41A-C46A -145(3) Mn2-N4-C41A-C46A 49(4)C46A-C41A-C42A-C43A 00(4) N4-C41A-C42A-C43A -166(7)C41A-C42A-C43A-C44A 01(4) C42A-C43A-C44A-C45A -02(10)C43A-C44A-C45A-C46A 03(13) C44A-C45A-C46A-C41A -02(13)C42A-C41A-C46A-C45A 00(9) N4-C41A-C46A-C45A 169(6)C55-N5-C51-C52 00(5) Mn2-N5-C51-C52 -178(4)N5-C51-C52-C53 00(4) C51-C52-C53-C54 -01(10)C52-C53-C54-C55 02(13) C51-N5-C55-C54 01(10)Mn2-N5-C55-C54 178(4) C53-C54-C55-N5 -02(13)C55A-N5A-C51A-C52A 1(2) Mn2-N5A-C51A-C52A -1778(10)N5A-C51A-C52A-C53A -7(2) C51A-C52A-C53A-C54A 13(3)C52A-C53A-C54A-C55A -12(3) C51A-N5A-C55A-C54A -1(2)Mn2-N5A-C55A-C54A 1785(14) C53A-C54A-C55A-N5A 6(3)

Mn2-N6-C61-C66 -1185(7) Mn1-N6-C61-C66 1111(7)Mn2-N6-C61-C62 617(9) Mn1-N6-C61-C62 -686(8)C66-C61-C62-C63 31(14) N6-C61-C62-C63 -1772(9)C61-C62-C63-C64 -15(17) C62-C63-C64-C65 -2(2)C63-C64-C65-C66 5(2) N6-C61-C66-C65 1795(8)C62-C61-C66-C65 -08(12) C64-C65-C66-C61 -33(18)C86-C81-C82-C83 5(3) C81-C82-C83-C84 -6(3)C82-C83-C84-C85 4(3) C83-C84-C85-C86 -2(4)C82-C81-C86-C85 -3(3) C84-C85-C86-C81 1(3)Table X36 (cont)Mn2-N3-C91-C96 -116(2) Mn1-N3-C91-C96 124(2)Mn2-N3-C91-C92 63(2) Mn1-N3-C91-C92 -57(3)C96-C91-C92-C93 -2(4) N3-C91-C92-C93 179(2)C91-C92-C93-C94 0(4) C92-C93-C94-C95 0(4)C93-C94-C95-C96 3(4) C92-C91-C96-C95 5(4)N3-C91-C96-C95 -177(2) C94-C95-C96-C91 -5(4)

Contents

Experimentalhelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip3

Cyclic voltammetryhelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip 4

X-Ray tableshelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip 5

Experimental









Cyclic Voltammetry















F(000) 2792




2 - Fc2)2


all data R1 = 00564 wR2 = 01027


where P=(Fo2+2Fc


























F(000) 6592




2 - Fc2)2


all data R1 = 00647 wR2 = 01310


where P=(Fo2+2Fc




















F(000) 6592



2 - Fc2)2


all data R1 = 00450 wR2 = 01031


where P=(Fo2+2Fc









C94-C93-C92 123(2) C93-C94-C95 118(2)C96-C95-C94 120(2) C91-C96-C95 123(2)



Experimental









Cyclic Voltammetry















F(000) 2792




2 - Fc2)2


all data R1 = 00564 wR2 = 01027


where P=(Fo2+2Fc


























F(000) 6592




2 - Fc2)2


all data R1 = 00647 wR2 = 01310


where P=(Fo2+2Fc




















F(000) 6592



2 - Fc2)2


all data R1 = 00450 wR2 = 01031


where P=(Fo2+2Fc









C94-C93-C92 123(2) C93-C94-C95 118(2)C96-C95-C94 120(2) C91-C96-C95 123(2)






Cyclic Voltammetry















F(000) 2792




2 - Fc2)2


all data R1 = 00564 wR2 = 01027


where P=(Fo2+2Fc


























F(000) 6592




2 - Fc2)2


all data R1 = 00647 wR2 = 01310


where P=(Fo2+2Fc




















F(000) 6592



2 - Fc2)2


all data R1 = 00450 wR2 = 01031


where P=(Fo2+2Fc









C94-C93-C92 123(2) C93-C94-C95 118(2)C96-C95-C94 120(2) C91-C96-C95 123(2)















F(000) 2792




2 - Fc2)2


all data R1 = 00564 wR2 = 01027


where P=(Fo2+2Fc


























F(000) 6592




2 - Fc2)2


all data R1 = 00647 wR2 = 01310


where P=(Fo2+2Fc




















F(000) 6592



2 - Fc2)2


all data R1 = 00450 wR2 = 01031


where P=(Fo2+2Fc









C94-C93-C92 123(2) C93-C94-C95 118(2)C96-C95-C94 120(2) C91-C96-C95 123(2)






2 - Fc2)2


all data R1 = 00564 wR2 = 01027


where P=(Fo2+2Fc


























F(000) 6592




2 - Fc2)2


all data R1 = 00647 wR2 = 01310


where P=(Fo2+2Fc




















F(000) 6592



2 - Fc2)2


all data R1 = 00450 wR2 = 01031


where P=(Fo2+2Fc









C94-C93-C92 123(2) C93-C94-C95 118(2)C96-C95-C94 120(2) C91-C96-C95 123(2)
























F(000) 6592




2 - Fc2)2


all data R1 = 00647 wR2 = 01310


where P=(Fo2+2Fc




















F(000) 6592



2 - Fc2)2


all data R1 = 00450 wR2 = 01031


where P=(Fo2+2Fc









C94-C93-C92 123(2) C93-C94-C95 118(2)C96-C95-C94 120(2) C91-C96-C95 123(2)






2 - Fc2)2


all data R1 = 00647 wR2 = 01310


where P=(Fo2+2Fc




















F(000) 6592



2 - Fc2)2


all data R1 = 00450 wR2 = 01031


where P=(Fo2+2Fc









C94-C93-C92 123(2) C93-C94-C95 118(2)C96-C95-C94 120(2) C91-C96-C95 123(2)


















F(000) 6592



2 - Fc2)2


all data R1 = 00450 wR2 = 01031


where P=(Fo2+2Fc









C94-C93-C92 123(2) C93-C94-C95 118(2)C96-C95-C94 120(2) C91-C96-C95 123(2)









C94-C93-C92 123(2) C93-C94-C95 118(2)C96-C95-C94 120(2) C91-C96-C95 123(2)



butterfly. hydrogen-atom reduced analogue of the mn n ... · preparation of a “twisted basket”...

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