Halogen bonding in the crystal structures of 1,2-diiodo alkenes

12 Pages·2015·3.57 MB·English

by  Christina Hettstedt

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Halogen bonding in the crystal structures of
e.
c 1,2-diiodo alkenes†
n
e
M. Lic Citethis:NewJ.Chem.,2015,
0:43 Aported 39,8522 Christina Hettstedt, Peter Mayer and Konstantin Karaghiosoff*
3n
2:U
3 0 Received(inMontpellier,France) The crystal structures of 1,2-diiodoolefins are governed by extensive halogen bonding involving I(cid:2)(cid:2)(cid:2)I,
202n 3. 14thMay2015, I(cid:2)(cid:2)(cid:2)O and I(cid:2)(cid:2)(cid:2)C interactions. These interactions are discussed considering nine new crystal structures
1/25/butio Accepted4thAugust2015 determinedinourlaboratoryandseveraladditionalcrystalstructuresfromtheliteraturethatcomplement
ed on s Attri DOI:10.1039/c5nj00821b ourdata.
adon www.rsc.org/njc
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ugust 2015. Der a Creative IHnaltorgoendbuoncdtiinognis currently a widely discussed topic in the aAasntdytph1iec,2ah,l3ae,l4xo-agtmeetnrpalfbelouinosdrpor-d5oo,v6ni-ddoeridioadbnoydtbhteheneczoeon-tcher8eyrsotaarlss4t,o4hf0e-pbhaipceycnreaipdztiionnree.
0 Aund literature.Inthelast15yearsanincreasingnumberofreviews andtetraiodoethene.9Theotherpossiblecase–halogenbonds
n 2ed (approximately 50) have been published on this subject. This in crystals where the halogen bond donor and acceptor are
os
Published cle is licen ytcyeepanertsuorfi(efosinratgedorem1taboiulleetcdwualmasriencinvhetaesnrtiaigscmattioednaniwndadstehtdaeiisltcohonevloeyrrieyndothafbeholauasltotgtfweewno iignneccnlluubddoeensddsidtnrountchotuerrasenasmdofnecimtormooglpeeoncuu,nloedxys–gceisonn,mtaauihncahilnolggeesens.g.doiriosadcuipns-essyeasdst.ehmTahlaoiss-
s Article. This arti mbofoanctderyrisinatgallsseceeinegnriecnfe.e.e42r–Mi6n)ag.n3Hyaastlhowegoeernlletbaicosanildnisnsavyernestthirgeealteitcivoacnnhste5imnhiatsvhtereybfaieenelndd faucncDecptiiitooondrao(lIoi(cid:2)tl(cid:2)ie(cid:2)eIfs,inIi(cid:2)ne(cid:2)s(cid:2)tOhhe,aIov(cid:2)ri(cid:2)ng(cid:2)Nagn,iIac(cid:2)d(cid:2)fd(cid:2)rCait(mipo)e)n.waolrkhaplroogveindebgoonoddeaxcacmepptloesr
s
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c publishedandhalogenbondinghasprovedtobeimportantin forsuchstructures.Inthesecompoundshalogenbondingshould
c
A
n medicinal chemistry as well as in chemical biology.6 In 2013, playakeyroleindeterminingthefeaturesofthecrystalstructure.
e
Op theofficialIUPACdefinitionwasreleasedwhichstatesamongst In order to put light on the importance of halogen bonding as
others that typical halogen bonds R–X(cid:2)(cid:2)(cid:2)Y–Z are formed directinginteractionintheformationofthestructureinthesolid
betweenahalogenbonddonor(R–X,X=electrophilichalogen statewehavedeterminedandinvestigatedthecrystalstructures
atom, e.g. I , CH Br, halonium ion) and a halogen bond ofaseriesof1,2-diiodoolefines(Fig.1).Inthispaperouraimis
2 3
acceptor Y (Y = lone pair possessing atom, a p-system or an toinvestigateweakhalogenbondsofiodinewiththelessstrong
anion).7 Additionally, the contact distance of X(cid:2)(cid:2)(cid:2)Y has to be halogen bond acceptors oxygen, iodine itself and aromatic,
shorterthanthesumofthevanderWaalsradii,theR–Xbond aliphaticoracetylenicp-systems.Thesystemsweincludeinthis
length should be elongated and the contact angle R–X(cid:2)(cid:2)(cid:2)Y study consist of the new crystal structures of nine 1,2-diiodo-
shouldbenearto1801.7 olefinesdeterminedinour laboratoryandthe crystal structures
Generally,iodinecontainingmoleculesformstrongerhalo- ofseveral1,2-diiodolefinesfromtheliteraturethatcomplement
gen bonds than corresponding bromine, chlorine or fluorine ourdata.
containingderivatives.3cInmostcasesreportedintheliterature
structuresshowinghalogenbondingwereobtainedbyforming
co-crystalsbetweentwodifferentcompounds,oneofwhichacts
DepartmentofChemistry,Ludwig-MaximiliansUniversity(LMU),
Butenandtstr.5–13(HausD),81377Munich,Germany.
E-mail:[email protected];Fax:[phone];
Tel:[phone]
†Electronic supplementary information (ESI) available: Containing additional
analyticaldata,figuresofthedisorderanddataforthecrystalstructures.CCDC
988931,988932and1037178–1037184.ForESIandcrystallographicdatainCIFor Fig.1 Additional (E)-iodoolefines that have been synthesized from the
otherelectronicformatseeDOI:10.1039/c5nj00821b correspondingalkyne.
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Particular attention is directed towards how the molecules
are arranged in the crystal with respect to the optimal space
filling and at the same time optimal formation of weak inter-
actions. This is of course dependent on the substituents and
theiracceptorabilities,whichareconnectedtothedoublebond.
Wewouldliketofindakindof‘‘ranking’’oftheinteractionsin
terms of which interaction is responsible for the structural
arrangementintheseweaksystemsandwhichinteractionsare
e. subordinate. What is stronger in this case: hydrogen bonds
c
n (HBs)orhalogenbonds(XBs).Fromthissystematicconsidera-
e
M. Lic tion we try to find general trends that could be suitable for
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0:43 porte acrpypsltiaclaetinognisn.eeringofpurecompounds/crystalsconcerningfuture Fig.3 (Z)- and cyclic diiodo compounds from the literature with their
3n
2:U namesfromCSD.
3 0
202n 3. Results and discussion
ed on 1/25/s Attributio S1,y2n-Dthiieosdisoolefines1–8(Fig.1)wereallsynthesizedby1,2-addition
dn
wnloaommo pofroIc2edtourtehse.10coTrhreesupnosnydminmgeatrciectaylledniieosdoacocleofridniengesttoerslit5eraantdur6e
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ust 2015. Da Creative tahreeInnCeuawIllcaacntadasleywszeetrdheepprrtoreacpneadsreuidsroefmrpouemrbsltiswhheeercdeorborbyetsDapiuonanenddeinetxgaclae.lp(kFtyinfgoe.rs2t)vh.i1ae1
uger acetal 7, where a mixture of the cis (7a) and trans (7b) deriva-
Ad
0 un tiveswasformed.Fromthismixturethetwoisomerscouldbe
n 2ed separated by fractional crystallization and were structurally
os
Published cle is licen iGnevneesrtiaglarteemdavriakssicnognlceecrrnyisntgalthXe-racyrydstiffalrasctrtuiocntu.res
Article. This arti Swienrgeleocbrtyasitnaelds,sbuyitraebclreysftoarllXiz-aratiyodnifffrroamctioEnt,OoAfca.lFlicgo.m6poshuonwdss
ss their molecular structures. A feature of most structures is a
e
c
Ac disorderofthediiodoalkenemoleculesovertwopositions.Only
en the structures of compounds 7a, 7b and 5 show no disorder.
p
O Herewediscussthehigheroccupiedpositionsofthedisordered
atoms.Forthediphenyldiiodide1andthealcoholderivative4
the disorder concerns over 80% of the molecule. Hence the Fig.4 (E)-DiiodoolefinesfromtheliteraturewiththeirnamesfromCSD.
valuesoftheatomdistancesandhalogenbondsofthesemole-
culeshavetobetreatedcarefullyindiscussionandcomparison
TheazideWIFVAJ13depictedinthebottomofFig.4would
with other data. Nevertheless, we include these data in the
fit perfectly in the topic of this comparison but the quality of
comparisons here, because the detected values of compounds
the structural data is inadequate. That’s why we exclude this
1 and 4 lie in the medium range of all here discussed com-
datafromthisdiscussion.Wealsofoundthecrystalstructures
pounds. Figures showing the disorder of all compounds are
ofC H I 14andC H I 14inCSDwhichwouldalsofitverywell
contained in the ESI.† Of the literature compounds from CSD 2 4 2 2 2 2
in the discussion here. Unfortunately the structures are from
there is only one disordered (RIDTOO12). The structures of all
the year 193514 and thusthe cif filescontain not enoughdata
literaturecompoundsdiscussedhereandsomeadditionalones
forshowingthestructureswithmodernmethods.
for the statistics with their names from CSD are depicted in
Fig.3and4.
Crystalstructures
The crystal structure of 8 contains the second shortest CQO
bond (1.186(4) Å, Fig. 5) and the shortest C–I (trans) bond
(2.109(4)Å)ofourstructureswhichislocatedundertheshorter
C–I bonds in this discussion (Fig. 8). The carboxyl group is
stronglytwistedoutofthedoublebondplane(82.7(4)1forOMe
and(cid:3)104.7(5)1forCQO)comparedtodimethylfumarate,which
Fig.2 Syntheticpathwayofthenew1,2-diiodoolefinicesters5and6. iscompletelyplanar.15
Thisjournalis©TheRoyalSocietyofChemistryandtheCentreNationaldelaRechercheScientifique2015 NewJ.Chem.,2015,39,8522--8533 | 8523
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the molecules form layers parallel to the bc-plane that are
stackedalongthea-axis(Fig.7).
Lookingatthesmaller,oxygencontainingmoleculesfromthe
literature(RIDTOO,12GIWTEM,16GIWTIQ,16NIMGOF17),where
no large substituent or phenyl ring is attached to the double
bond,somecommonfeaturesandalsodifferencesinthecrystal
structurescomparedto8canbedetected.
RIDTOO12 is the only carboxylic acid containing molecule,
e. that does not form I(cid:2)(cid:2)(cid:2)O halogen bonds (the less occupied
c
n disordered part seems to form an I(cid:2)(cid:2)(cid:2)O halogen bond but its
e
M. Lic arrangement fits perfectly in the network built up by the I(cid:2)(cid:2)(cid:2)I
Ad
0:43 porte itnhtaetraccatuiosenst)h.eThmeosltercuuclteusretoisfodrommidniamteedrs.byThheysderodgiemnebrsonadres
3 2:30 Un Fdiigsc.u5sseSdtahtiesrteic,asledpiastrraitbeudtioinncoisf/ttrhaensCQandOliatetoramtudreistcaonmcepsouonfdaslladniidodoiudress. arranged in a way that a complex network is formed under
202n 3. Thetrendgoestolongerbondscomparedtotheliteraturevalueof1.19Å.22 assistance of I(cid:2)(cid:2)(cid:2)I halogen bonds that are the shortest here
ed on 1/25/s Attributio ThereferenceofAllenetal.21(1.199Å)ismoreappropriate. o((F1b0isg.e2.r(1v30e))1d.)Aw(dh3d.i8cit0hi1om(n1ao)lslytÅ,p)trhoienbmatebrolmyleiocnuledlcaicuralsatterrsutIch(cid:2)t(cid:2)ua(cid:2)trIethiasetoatmwlmisotdisnitsgptaloanfncaealsrl
adon The crystal structure is governed by the shortest I(cid:2)(cid:2)(cid:2)O othercarboxylgroupsisduetohalogenbonding.
om
nlm halogenbonds(3.005(3)Å)occurringinthiswork(Fig.9)with InGIWTIQ16thehydrogenatthedoublebondissubstituted
wo
ugust 2015. Doer a Creative C a(pd1nao1in7raos.l4mro.(2foT)sth1ht)ielstihnoianxetytaegirnreCadnc–itcaIi(cid:2)aso(cid:2)tnhe(cid:2)Osaislaaongngegeinnlneetebr(ar1oat7nec3ddt.i1oab(nc1yc)bb1e)eoptattwhonerdieoanadnidConQnteehaOeot(cid:2)foio(cid:2)tm(cid:2)hdIseian,lneaognnaldees btagolrysoaoaucpmdoiiemmsthpetwyrleslitsgeitnrleoytdeudrpoicff.uoTetnrhnoeifenscttsthecteedrrydisvcotiaauilnbhscltreyredubarcsootenguedornefp.tblhTaoehnnesedumsbb.yosTtl8ieht1cue.u2elc(ne9ats)r1blfeooaarnxdmydsl
0 Aund both carbonyl groups function as halogen bond acceptors, participates in I(cid:2)(cid:2)(cid:2)O halogen bonding (3.089(6) Å). The I(cid:2)(cid:2)(cid:2)O
n 2ed forcingthemoleculetoformfourhalogenbonds.Duetothis, halogen bond ranges among the shorter ones of the here
os
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Article. This arti
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Fig.6 Overview over the asymmetric units or molecular structures of our compounds 1–8 with the specific atom numbering. Symmetry codes:
1[(a)(1(cid:3)x,1(cid:3)y,2(cid:3)z)];3[(a)(1(cid:3)x,y,1.5(cid:3)z)];8[(a)(2(cid:3)x,(cid:3)y,1(cid:3)z)].DIAMONDrepresentation,thermalellipsoidsaredrawnat50%probabilitylevel.
8524 | NewJ.Chem.,2015,39,8522--8533 Thisjournalis©TheRoyalSocietyofChemistryandtheCentreNationaldelaRechercheScientifique2015
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Paper NJC
e.
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Ad Fig.9 Statistical distribution of the intermolecular I(cid:2)(cid:2)(cid:2)O halogen bond
0:43 porte lceonmgtphosuonfdaslalnddiiooduidrse.sThdeiscmuasxsiemduhmerdeis,tsaenpcaeraistethdeinsucmis/otrfatnhesavannddlieterrWatauarles
3n
2:U radiioftheinvolvedatoms(3.50Å).
3 0
1/25/202bution 3. (F(daig)).((2x7,(cid:3)0.Nx5,e(cid:3)(cid:3)twyyo,,r1(cid:3)k(cid:3)0in.5zt)h,+e(bzc)).r(yxDs,It0Aa.Ml5sOt(cid:3)rNuycD,tu0rr.e5ep+orefszte)h,ne(tcad)tii(eo2snt(cid:3),etrxh8,e.(cid:3)rSm0y.am5lme+lleyipt,rs0yo.ci5dos(cid:3)daezrse):,
ed on s Attri drawnat50%probabilitylevel.
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Published cle is licen lFeign.g1th0soSftaaltlisdtiiicoadliddeisstrdibisuctuiossnedofhethree,sinetpearrmatoeldecinulcairs/It(cid:2)r(cid:2)a(cid:2)nIshaanlodgleitnerbatounrde
Article. This arti craodmiipoofuthnedsinavnodlvoeudrsa.tTohmesm(3a.x9i6mÅu)m. distanceisthesumofthevanderWaals
s
s
e
c
c
A
n the I(cid:2)(cid:2)(cid:2)O halogen bond compared to the value found in the
e
Op crystalstructureofGIWTOQ.16Themoleculesformalsochains
interconnectedviatheI(cid:2)(cid:2)(cid:2)Ohalogenbondswhichresultsinthe
Fig.8 Statistical distribution of the C–I atom distances of all diiodides
formationoflayers.
discussedhere,separatedincis/transandliteraturecompoundsandours.
C I 18wasexcludedbecauseoftheveryshortC–Idistance(1.987(3)Å), If both substituents at the double bond of GIWTEM16 are
22
F CI19 and C I 20 are included in the literature trans category. cis Diido replaced by CH OH groups as it is the case for NIMGOF17 the
3 24 2
compounds, which are mostly cyclic, have shorter C–I atom distances moleculesformhydrogen-andI(cid:2)(cid:2)(cid:2)Ohalogenbonds(3.429(1)Å)
thanlinearonesandthosewithtransconfiguration.Theyareevenshorter asalreadydescribedintheoriginalliterature.17Themolecules
thantheliteraturevaluegivenfortheC –Idistance(2.095Å).21
Ar do not form dimers via hydrogen bonds and due to the high
flexibilityofthemoleculethereagainisthepossibilitytoform
detected distances (Fig. 9). Additionally, the molecules form I(cid:2)(cid:2)(cid:2)I halogen bonds (3.875(3) Å) which range like the I(cid:2)(cid:2)(cid:2)O
also long I(cid:2)(cid:2)(cid:2)I halogen bonds (3.938(9) Å, Fig. 10). All inter- intermoleculardistancesamongstthelongerones(Fig.10).All
molecular interactions lead to the formation of a complex intermolecularinteractionsformacomplexnetwork.
network. Substitution of one CH OH group by a phenyl ring leads
2
The bulkiness of the CH OMe group included in the mole- to compound 4. As observed for the carboxyl groups in the
2
culesofGIWTEM16insteadofHorMeseemstobehighenough previouslydiscussedcrystalstructures,herethephenylringis
to prevent the molecules from I(cid:2)(cid:2)(cid:2)I halogen bond formation. twistedoutofthedoublebondplane((cid:3)80.9(7)1).Thehydroxyl
Themoleculesformchainsviahydrogenbondsparalleltothe groups make hydrogen bonds (Fig. 11) forming right twisted
bc-plane.Againthecarboxylgroupistwistedoutofthedouble helical chains along the c-axis with four molecules forming a
bondplaneby80.3(9)1andtheCQObondformsI(cid:2)(cid:2)(cid:2)Ohalogen turn(Fig.12).
bonds (3.308(8) Å) which ranges amongst the longer here The distance between the turns d(O1(cid:2)(cid:2)(cid:2)O1f) is 7.532(3) Å.
detected intermolecular I(cid:2)(cid:2)(cid:2)O distances (Fig. 9). The steric Startingfromtheasymmetricunitthemoleculesinthecrystal
increase of the CH OMe substituent leads to an elongation of also form a helix interconnected by I1(cid:2)(cid:2)(cid:2)I2e halogen bonds
2
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0:43 Aported Fhiaglo.1g1enCbroynstdasl s(It2ructoturI1eg)ofin4c.luOdnesetthurreneotfutrhneshoeflixthfeorhmeelixdfboyrmtheedI(cid:2)v(cid:2)i(cid:2)aI
2:3Un hydrogenbonds(O1toO1j;O1jtoO1h;O1htoO1g)d(O–H)=0.84(2)Å,
2023 n 3.0 dre(Osid1(cid:2)u(cid:2)e(cid:2)sOa1rde)=om2.i6tt9e3d(3fo)rÅc,l+aritOy.1–SyHm1(cid:2)m(cid:2)(cid:2)eOtr1ydc=od16es9:.6(a(2))(1(cid:3).0So.2m5e+(xI),C1Q.25C((cid:3)I)Pyh, Fuingi.t.13All CAl–lHintheyrmdroolgeecnulaartoimntseraarcetioonmsitetemdanfoartincglarfirtyo.mSytmhemaestyrymcmoedterisc:
ded on 1/25/ns Attributio 0(rie).7p(15r.e5+s(cid:3)ezn)xt,,a(1tcio(cid:3))n(1y,.,2t1h5.e5(cid:3)r+mxza,)l,0e(.2jl)li5(pxs+,oyiy,d,1s0+a.2rze5),d(+kr)az(w)1,.n5(g(cid:3)a)t(xx5,,01y%,(cid:3)3pyr+,o2bz.5)a,b+(hilzi)t)y(.xDl,eIyvA,eM2l.O+NzD), (cid:3)p((adr1))o(b(+(cid:3)(cid:3)a00bz.i.)2l2.i5t5Dy+I+lAexMv,xe1O,l..21N5.2D(cid:3)5ry(cid:3)e,p(cid:3)ry0e,s.20e5n.7t+5atzi+o),n(ze,)),t(h1(ce.2)rm5(1(cid:3)a.2lx5e,l0l(cid:3)i.p2s5xo,+id0sy.2,a(cid:3)5re0+.7d5yra,+w0zn.)2,5a(ft)+(5x0,z%y),,
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ugust 2015. Doer a Creative C catholsemoRcpeoopofrulraienmcsdippnoog5nrtCdatiHhnnec2gOebsHitonrnubsdcyttauaabnriamgllilzeeidtsnhog(ymTltahiebnselateetssirtnrignugrcoEtiuunSrpIte†e,)ar.asacsitniiontndhsiecaccthaesadenbgoeyf
0 Aund completely. In the molecular structure of 5 the C1–I1 (2.118(1) Å)
n 2ed atomdistanceisalittleelongatedcomparedtotheC2–I2(2.109(1)Å)
Published ocle is licens bdtooisnotdaunrlecnoegt(ht1he.,r1w9sh7tri(c1uh)ctcÅuo)rmeospfa5(r6e,iss8wt)heblelutlotontihngeetsvhatelCumQeoeOfd8iub.TmohnedraCcnQogmeOpoaaftroaemldl
Article. This arti cstrryustcatulsretrsu(cFtiugr.e5t)haenpdhleonnyglerrintghaisnatlhsoetliwteisrtaetduroeuvtaolufeth.2e1dInoutbhlies
s bond plane (91.0(5)1), same observations can be made for the
s
ce carbonylgroup(51.0(6)1),butthisangleissmallerthanexpected
c
A
n andobservedfortheabovediscussedstructures.
Ope Fig.12 Helix along the c-axis in the crystal structure of 4. All C–H The crystal structure of 5 is governed by I(cid:2)(cid:2)(cid:2)O (3.143(1) Å)
hydrogenatomsareomittedforclarity.Symmetrycodes:(a)((cid:3)0.25+x,
and I(cid:2)(cid:2)(cid:2)C(p) (3.372(1) Å) halogen bonds (Fig. 15). The inter-
1.25(cid:3)y,0.75+z),(b)(1.5(cid:3)x,1(cid:3)y,(cid:3)0.5+z),(c)(1.25(cid:3)x,0.25+y,
0.25+z).DIAMONDrepresentation,thermalellipsoidsaredrawnat50% molecular I(cid:2)(cid:2)(cid:2)O distance ranges among the shorter ones com-
probabilitylevel. paredtoallstructureshereandisthesecondshortestinteraction
ofthiskindobservedforoursubstances(Fig.9).
TheintermolecularI2(cid:2)(cid:2)(cid:2)C7(p)distanceistheshortestofall
(3.927(3) Å) with I2 as the halogen bond donor and I1 as the substancesinthiscomparisonandhighlydirectional(Fig.14).
corresponding acceptor. The turns of this second helix are TheC2–I2bondpointsdirectlytowardstheC7–C8bondofthe
threetimesaslargeasthehelixformedbythehydrogenbonds phenylringoftheadjacentmolecule.Thetwokindsofhalogen
(d(O1(cid:2)(cid:2)(cid:2)O1g) = 22.597(2) Å) (Fig. 12). The molecules within the bondsmakethemoleculesformchainsalongtheb-axisinthe
helixformchainsalongthec-axisviaI1(cid:2)(cid:2)(cid:2)C7fcontacts(3.563(1)Å). crystalstructureof5(Fig.15)andinfactthereisnointeraction
In the crystal structure there are also I(cid:2)(cid:2)(cid:2)O1a (3.420(3) Å) betweenthechainsotherthanvanderWaalsinteractions.
contacts(Fig.13).TheI1(cid:2)(cid:2)(cid:2)I2einteractionisoneofthelongest, Changingtheesterfrommethyltoethylasinthecaseof6
here observed I(cid:2)(cid:2)(cid:2)I halogen bonds (3.927(3) Å, Fig. 10). The there again can be observed a different arrangement of the
I(cid:2)(cid:2)(cid:2)C(p) interaction is the atom distance concerning in the moleculesinthecrystal(Fig.16).
mediumrange(Fig.14).AlthoughthedirectionoftheC–Ibond TheC–Ibondsof6aremuchmoresimilarthanthoseofthe
andtheorientationofthephenylringindicatealmostnointer- methylester 5. The C1–I1 bond (2.116(5) Å) that is part of
action.TheI(cid:2)(cid:2)(cid:2)Ohalogenbondrangesamongthelongesthere I(cid:2)(cid:2)(cid:2)C(p)interactions(3.530(3) Å)isthelongerone.Thephenyl
detectedintermolecularI(cid:2)(cid:2)(cid:2)Ointeractions(Fig.9).Consequently substituentandtheestercarbonylgrouparetwistedoutofthe
themaininteractionsthatareresponsibleforthisarrangement double bond plane about 87.2(5)1 and 104.0(5)1, respectively.
ofthemoleculesinthecrystalarethehydrogenbonds.However, Thelattervalueiscomparablewiththevaluethatcanbefound
despite the quite long I(cid:2)(cid:2)(cid:2)I distances, I(cid:2)(cid:2)(cid:2)I halogen bonds are in the crystal structure of the diester 8. The I(cid:2)(cid:2)(cid:2)C(p) halogen
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Paper NJC
increase caused by the insertion of the CH group pushes the
2
molecules away from each other and the intermolecular inter-
actionsbecomeweaker.ThisresultsalsoinlongerI(cid:2)(cid:2)(cid:2)Ointer-
actions(3.326(2)Å,3.498(2)Å)comparedtothevaluesthatcan
bedetectedinthecrystalstructureof5.Comparedtoallvalues
for the I(cid:2)(cid:2)(cid:2)O interactions in this comparison, the data of 6
belongtothelongerones(Fig.9).
Changing the substituent from an ester to an ethyl acetal,
e. therearetwodifferentisomers.Forthe(Z)isomer(7a)thetwo
c
n C–I distances are clearly different; the longer C2–I2 distance
e
M. Lic (2.115(3)Å)isassociatedwiththephenylbondedcarbonatom
Ad
0:43 porte aCn1d–I1I2ddiosetasnncoet(f2o.r0m91a(3n)yÅh)alofogremnsboI1n(cid:2)d(cid:2)s(cid:2)O. I21bwhiathlotgheensbhoonrtdesr
3n
2023 2:n 3.0 U Fleign.g1th4soSftaaltlisdtiiicoadliddiesstrdibisuctuiosnseodfhtheerein,steerpmaroalteecdulinarcIi(cid:2)s(cid:2)/(cid:2)tCra(pn)shaanlodglietenrbatounrde h(3e.r3e30o(b2s)eÅrv)etdha(tFirga.n9g)e.TbhetiwseoebnsetrhveatlioonngiesruI(cid:2)n(cid:2)u(cid:2)Osuhaal,lobgeecnaubsoenfdosr
ed on 1/25/s Attributio craodmiipoofuthnedsinavnodlvoeudrsa.tTohmesm(3a.x6i5mÅu)m. distanceisthesumofthevanderWaals h2o.ua1ltoÅog)fe22nthwbeoodunoldduibnblgeeeabxospnleigdchteptdlae.2lno,7enT(g6ha5et.i2op(nh4e)o1n)fybtlhureitnCngo–iItsbtcholaentadrml(ytuytcpwhiicslatielkldey
adon inthestructuresdiscussedbefore.Themoleculesformzig-zag
om
nlm chains along the b-axis interconnected via the I(cid:2)(cid:2)(cid:2)O contacts.
wo
ugust 2015. Doer a Creative C TpHabahecierlkeirteeywdateroienhfnoatvorhmeefutchhrrteayhlsboetograerlidnnteotberrgolaiinvncdeteisoa,bnnwesthowbepeerteteiwnmaelsaestlnoesritpishcaethchecienhfndailirelnaiensnd,gcfweo(Fhraiinagcd.hli1tta7thrl)eee.
0 Aund geometricalflexibility.Sameobservationscanalsobemadein
n 2ed thecrystalstructureofMIQKUU,23theonlyacyclicciscompound
os
Article. Published This article is licen tSFhyigem.rmm15aeltreCyllhicpaosidonesidsas:lo(aanr)eg(xdt,hr1aew+bn-ya,axzti)s5,i(0nb%)th(pxe,ro(cid:3)cbr1yas+btailyilt,syztrl)eu.vDcetIuAl.rMeOofNtDheremperethsyelnetsatteiorn5., tcftorhooemtmThmphetleohe(Zlteeea)cllriiuyrstaleodenrmiaffgisteeeurmqrree7uen.ainttHettcheroeroimegfCindp–to.haIreahetado(lEmot)ogeditnshisoebtmao(nZnec)rdeisss7ocbiamnnietnhbree7ta(hoE.be)Isniecsrrocvyomesndteatrarlan7sidbst
s
s
e
c
c
A
n
e
p
O
Fig.16 Chainsalongtheb-axisinthecrystalstructureoftheethylester6.
Symmetrycodes:(a)(x,(cid:3)1+y,z),(b)(x,1+y,z),(c)(1(cid:3)x,2(cid:3)y,1(cid:3)z),
(d)(1(cid:3)x,1(cid:3)y,1(cid:3)z).DIAMONDrepresentation,thermalellipsoidsare
drawnat50%probabilitylevel.
Fig.17 ZigzagchainsgovernedbyshortintermolecularI(cid:2)(cid:2)(cid:2)Ocontactsin
bondlengthliesinthemediumrangeofallhalogenbondsofthis
b-direction, in the crystal structure of compound 7a. Symmetry codes:
sortheredetected(Fig.14)andisresponsiblefortheformationof (a)(0.5(cid:3)x,0.5+y,1.5(cid:3)z),(b)(0.5(cid:3)x,(cid:3)0.5+y,1.5(cid:3)z),(c)(x,(cid:3)1+y,z).
chains that are dominating the crystal structure of 6. The steric DIAMONDrepresentation,thermalellipsoidsaredrawnat50%probabilitylevel.
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Fig.18 Crystalstructureofcompound7b.Viewofthechainsalongthe Fig.20 I(cid:2)(cid:2)(cid:2)C(p)Halogenbondsinthecrystalstructureof4formingchains
ce. c-axisresultingfromintermolecularI(cid:2)(cid:2)(cid:2)C(p)interactions.Symmetrycodes: inb-direction.Symmetrycodes:(a)(x,1+y,z),(b)(x,(cid:3)1+y,z).DIAMOND
AM. d Licen (tah)e(rxm,0al.5e(cid:3)llipys,o(cid:3)id0s.5ar+ezd),ra(bw)n(xa,t05.50(cid:3)%yp,ro0b.5ab+ilzit)y.DleIvAeMl.ONDrepresentation, representation,thermalellipsoidsaredrawnat50%probabilitylevel.
0:43 porte In molecules 2 (containing I3) and 3 (containing I5) the
3n
2:U are with 2.124(5) Å (C1–I1) and 2.131(5) Å (C2–I2) longer. The phenyl rings are also twisted out of the double bond plane
3 0
202n 3. corresponding dihedral angle of the phenyl ring (73.4(6)1) is ((cid:3)86.6(8)1forM2and72.1(8)1forM3).Eachmoleculeformsa
ed on 1/25/s Attributio l(da3ir.s4gc4ue1rss(5eb)duÅtb)edtfoheresep.tiwTtehisitsiitnIs2g(cid:2)i(cid:2)an(cid:2)nCcg7lul(eps)iiosinnstmeirnaacllteIi(cid:2)or(cid:2)nt(cid:2)hCisa(pnth)ienhsaethlcooegnesdtnrsuhbcotourntredessst hIcnoenlbincoaetlchtcehhdaeilvniciaethsIa(cid:2)tth(cid:2)(cid:2)ceIaanhlatbeloerngceaontninvbegorntmeddoslien(cItu3o(cid:2)le(cid:2)es(cid:2)aIc6Mha1o3t.a8hn8ed4r(bM6y)2sÅya,mrIe4mi(cid:2)n(cid:2)e(cid:2)ttIer5yrc-.
dn observedinthiscomparison(Fig.14)andthecorrespondingC2–I2 3.885(5)Å,Fig.21)thatrangeinthemiddleofallheredetected
ao
om
nlm bondiselongatedcomparedtotheotherone.Theseinteractions I(cid:2)(cid:2)(cid:2)I interactions (Fig. 10). The helices itself are not connected
wo
oC resultintheformationofchainsalongthec-axis(Fig.18)ascould with each other. Looking at the angles of the halogen bonds,
ust 2015. Da Creative ablestoKweebeeepnionibogsdetihrnveeedpahniendnotyhxleysgucebrnysstaittraueleosntbrtsuaecsrtvuaerdce.oonfst5a.nNtoanidntcehraacntgioinngs taahrneedrnetehaaerroettohtwelirnotewadoriff(aIer3re(cid:2)e(cid:2)nn(cid:2)tIe6at–reCnt2od5reen1c5cti9ae.ns0g.(2uT)l1aw,roI(5I(cid:2)6o(cid:2)(cid:2)f(cid:2)(cid:2)I(cid:2)4tIh–3eC–C1f61o7u1r7931a..25n((g22l))e11s),
Augder theoxygencontainingsubstituentagainstaHleadsustocom- I4(cid:2)(cid:2)(cid:2)I5–C26 97.7(2)1). These values indicate that I4 and I6 act
0 un
n 2ed pound 3. In this crystal structure the C–I bond lengths are as halogen bond donors and I3 and I5 act as halogen bond
Published ocle is licens adprlieaffnetheree(n8dt0oa.m9n(id2n)at1hn).etHipnehtreeernmaylloslroeincIug(cid:2)l(cid:2)ai(cid:2)srCit(nwpt)ieshrtaeacdltoioogunentsowbfhotinhcdhesdra(o3nu.g5be7lse3u(b1no)dnÅedr) atlehcnecgedtphotosnroosrf.aRthteoemmaacsrck(eIap4bt/Iloe6r)iasatrotehmasstho(tIhr3te/eIrc5o)crobrmeescppaauornseedditnhtogetCohp–eIpCobs–oiIntebdoswnaodsf
s Article. This arti htfoharelmolgocenhngaebirnosonandlesosn(Fginitght.he1ia9s-)a.dxiHisscehureessaiwdoentoh(tFaaivigle.cao1nn4)n.eexTcahtmeedpmvleioalttehhcaeutlIes(cid:2)sh(cid:2)(cid:2)oCowf(ps3), ehaxnepldieccetthseeda,rcechoaanrirnsaisdnegirneidtnegrpcaotrhnaenlleeXclBtteoddtehvfiienaicteIi(cid:2)oll(cid:2)n(cid:2)eCdo(pgfe)tshinoetfeItrUhaPceAtiuConn2i.stTcaherleel
s
ce that a decrease in steric hindrance leads to a maximum of arrangedbetweentwohelixstrands(Fig.22).Theindependent
c
A intermolecularinteraction. occurrenceofI(cid:2)(cid:2)(cid:2)CandI(cid:2)(cid:2)(cid:2)Ihalogenbondsinthesamecrystal
n
pe The largest change in crystal packing is caused by the sub- structureletsusconclude,thatinthiscasetheenergyofboth
O
stitutionoftheHtomethyl.Theasymmetricunitofcompound interactions is very similar. This left twisted helical chain
2containsthreeindependentmolecules.Molecule1(containsI1) arrangementisverysimilartothecrystalstructureof4.
formsI(cid:2)(cid:2)(cid:2)C(p)halogenbonds(3.543(5)Å)whoselengthslieinthe Changingmethyltophenyl,asitisthecaseforcompound1
mediumrangeofallheredetectedI(cid:2)(cid:2)(cid:2)C(p)interactions(Fig.14). again I(cid:2)(cid:2)(cid:2)C(p) halogen bonds (3.543(3) Å) are the dominant
The phenyl ring of M1 is twistedout of the double bondplane
about (cid:3)79.0(1)1. These molecules form chains along the b-axis
viatheI(cid:2)(cid:2)(cid:2)C(p)interactions(Fig.20).
Fig.19 Crystal structure ofcompound 3. View of the chains along the Fig.21 Helicaldoublestrandchainsalongtheb-axisinthecrystalstruc-
a-axisresultingfromintermolecularI(cid:2)(cid:2)(cid:2)C(p)interactions.Symmetrycodes: tureof2,formedbyI(cid:2)(cid:2)(cid:2)Ihalogenbonds.Symmetrycodes:(a)(x,1+y,z),
(a)(1(cid:3)x,y,1.5(cid:3)z),(b)(0.5(cid:3)x,0.5(cid:3)y,2(cid:3)z),(c)(0.5+x,0.5(cid:3)y,(cid:3)0.5+z), (b)(x,(cid:3)1+y,z),(c)((cid:3)x,(cid:3)0.5+y,0.5(cid:3)z),(d)((cid:3)x,0.5+y,0.5(cid:3)z),(e)(1+x,
(d)(1.5(cid:3)x,0.5(cid:3)y,1(cid:3)z),(e)(1+x,y,(cid:3)1+z).DIAMONDrepresentation, y,(cid:3)1+z).DIAMONDrepresentation,thermalellipsoidsaredrawnat50%
thermalellipsoidsaredrawnat50%probabilitylevel. probabilitylevel.
8528 | NewJ.Chem.,2015,39,8522--8533 Thisjournalis©TheRoyalSocietyofChemistryandtheCentreNationaldelaRechercheScientifique2015
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Paper NJC
In the molecular structure of RUWRUX26 there are two
diiodoolefinicmoietiesnearbyandtwistedinawaythatmakes
conjugationofthedoublebondunlikely.Themoleculeitselfis
quiteflexibleandistwistedinawaythatamaximumhalogen
bondformationispossible.Theasymmetricunitpersistsoftwo
moleculeswithallinalleightiodineatoms.Sevenofthemform
halogenbonds.
e.
c
n Discussion and conclusion
e
M. Lic
Ad
0:43 porte Lstoroukcitnugresatofthtehesicmoimlapriotuiensdsthdaitsccuanssebdeafboouvned, aincothmepectriytsiotanl
3n
3 2:0 U betweentheformationofhydrogenbondsandtheformationof
202n 3. halogen bonds can be observed when both is possible. Also a
ed on 1/25/s Attributio Fthhiagelo.c2g-2eanxibTsohinnedhtsheealicrecersbysfeottawrlmesetqrnuucathdtuesrehstaropafend2d.ssTuohbfeuqnumiatsodlweschhuiaclpehesfdothrumantitsfsto.rraDmnIdAIsM(cid:2)(cid:2)aO(cid:2)lCoNn(pDg) ciasolwmparpyesesteisnteitoe.nmAlblteaotcwibdeeesnathntehdedadlocimoffheinorealsnnttfohirnamltoehgraeycndtriboonogennadnibndognaadlclscoewpthhtioecrrhss
adon representation,thermalellipsoidsaredrawnat50%probabilitylevel. subordinate themselves. When halogen bonds occur in the
om
nlm crystalstructure thenthe participatinghalogenbondacceptor
wo
ugust 2015. Doer a Creative C ioownfvaterearrrllalaancpinttieotodefnr.ta.hTcTethhiCeoisn1lis–anIto1tteeflrritmnhaeogisalweitcniytuphileastrhhtdeweiriasesdttaeojnadbccseeoenuristvtepinodhfte(hFtnheiygelm.sd1ueo4dbu)is.ubtiAmltelusreobanonttnhgidees letrihenkvaseeturCirsseOec2olcReapastoreilrmyiPslaahlnregconeotyrnlattihlaswcatatnwycssiosintwnegdadlrietroiasountntetrseoi.dfc.TtehhTffeihescidsthosouawbpbospleeuerlnbvdsoaintniidnodnupacllaeern.tasTenhugtoees
0 Aund plane ((cid:3)80.5(8)1) as observed for the phenyl substituents of all concludethattheenergyofthehalogenbondishigherthanthe
Published on 2cle is licensed saotctihttiIueonrenntchttohemiescprmreoypsuotllnaaedlccesusdtldreubsiscycftoauursrbmseiecodcyfhchlEaieciMnrlesUa.cZ(VtFIoiiWagn.e2th42ti3hws)e.hirneertaeerromentoweleopchmueloanrlyelicnsutuleebrs-- methnoeeUsrctgnlryyydshetthrayedlerxsmoctrglouuelcsneticuobunroleenofdfwostrihmnaesnavdtveiioarI(cid:2)yn(cid:2)t,sh(cid:2)Imaehgacaleollnonmegjrueoanglleabscttiuoaonltneed.mRsIaeDnreTtOrceoOlne1v2caewnrnhtiefnorger
Article. This arti ianrethtweisatseydmlmaregterliycouuntito.fBtohtehdsouubbslteitubeonntds polfanboetahltmhooulegchulneos tchoentIa(cid:2)i(cid:2)n(cid:2)Oinghfaulongcetinonbaolngdrofuoprminactliuodnedcainntbheemmaodleec.uIlseathnatoxcyoguelnd
ss I(cid:2)(cid:2)(cid:2)C(p)halogenbondsoccurinthiscrystalstructureduetothe act ashalogenbondacceptor,thenitfunctionsassuch.Inthe
e
c esteroracidgroupsoccurringhere,theincludedcarbonylgroup
Ac sterichindranceofthelargesubstituents.Onemoleculeofthe
en asymmetric unit forms I(cid:2)(cid:2)(cid:2)I halogen bonds (3.835(4) Å) and alwaysformsthehalogenbond.ThoseCQOfunctionsseemsto
Op chainsinterconnectedviathose.Theothermoleculeformsalso be the stronger halogen bond acceptor than the OH or OR
groups that are also present. Exceptions are small molecules
chains but those are interconnected by I(cid:2)(cid:2)(cid:2)O halogen bonds
likeRIDTOO12wherestrongerinteractionslikehydrogenbonds
(3.347(5)Å).
are possible. Also exceptions are rigid molecules with stericly
InthecrystalstructureofULEFUN25themoleculecontainstwo
demanding substituents in the cis configuration like 7a and
terminaldiiodoolefinicmoietiesandisgenerallyquiteflexible.The
MIQKUU,23 where very weak or even no halogen bonds under
moleculesarearrangedinawaythatleadstomaximumhalogen
participationoftheoxygenoccur.
bondformation,fouroutoffouriodineatomsformhalogenbonds,
Asonecanclearlyseeforthecrystalstructuresthatarebuilt
includingI(cid:2)(cid:2)(cid:2)I,I(cid:2)(cid:2)(cid:2)OandI(cid:2)(cid:2)(cid:2)C(p)interactions.
up by the molecules arranged in chains (7b, 1, 2, 3, 5) mostly
I(cid:2)(cid:2)(cid:2)C(p) interactions are responsible for the chains. In the
crystalstructureof5thechainsarebuiltupbyI(cid:2)(cid:2)(cid:2)Ointeractions
supportedbytheI(cid:2)(cid:2)(cid:2)C(p)halogenbonds,resultinginthestrongest
I(cid:2)(cid:2)(cid:2)C(p)andthesecondstrongestI(cid:2)(cid:2)(cid:2)Ointeractions.
When there are only iodine and a p-system present in a
moleculetoactashalogenbondacceptorasisthecasefor1,2,
3, C I and C I then, except for C I and parts of the crystal
2 2 2 4 2 4
structure of 2, the heteroatomic I(cid:2)(cid:2)(cid:2)C(p) interaction is always
preferredinthecrystalstructureinsteadofthehomoatomicI(cid:2)(cid:2)(cid:2)I
halogenbond.Inthisstudynoiodineinteractionswitholefinic
Fig.23 I(cid:2)(cid:2)(cid:2)C(p) Halogen bonds in the crystal structure of 1 forming
double bonds could be observed. The main interactions occur
chains.Symmetrycodes:(a)(1(cid:3)x,1(cid:3)y,2(cid:3)z),(b)((cid:3)x,1(cid:3)y,1(cid:3)z),(c)
((cid:3)1+x,y,(cid:3)1+z),(d)(1+x,y,1+z),(e)(2(cid:3)x,1(cid:3)y,3(cid:3)z).DIAMOND betweenaniodineatomandthep-systemofaphenylring.Inthe
representation,thermalellipsoidsaredrawnat50%probabilitylevel. crystalstructureofC2I2thehalogenbondacceptoristheCRC
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Chemical shifts are referred to Me Si (1H, 13C) as external
4
standards.Allspectraweremeasured,ifnotmentionedother-
wise, at 25 1C. The assignment of the signals in the 1H and
13CNMRspectraisbasedon2D(1H,1H-COSY45,1H,13C-HMQC
and1H,13C-HMBC)experiments.Massspectrometricdatawere
Fig.24 StructuresofKAFBOJandKAFBIDfromtheliterature.
obtainedwithaJEOLMstationJMS700spectrometerusingthe
directEImode.Themolecularstructuresinthecrystallinestate
triplebond.InthecrystalstructureofRETRIR27whereaphenyl were determined by single crystal X-ray diffraction. For data
e. ring and a triple bond are included in the same molecule, the collectionanXcalibur3diffractometerequippedwithaSpellman
c
n triplebondisthefavoredhalogenbondacceptor. generator (voltage 50 kV, current 40 mA) and a Kappa CCD
e
M. Lic FortheI(cid:2)(cid:2)(cid:2)Ihalogenbondformationitisnoticeablethatthey detector with an X-ray radiation wavelength of 0.71073 Å was
Ad
0:43 porte olickceuRrIeDitThOeOr,i1n2GcrIyWstTalIQst,1r6uNctIuMreGsOcFo,n17si2stainngdo4f.Tsmheasllteerrimcdoelemcualneds usosfetdw.aTrhe2e9daantdactohleledctaitoanrwedauscpteiornforwmitehdtwhiethCtrhyseAClirsysRAEliDsCsoCfDt-
3n
3 2:0 U of the substituents of those molecules is either small or the ware.30ThestructuresweresolvedwithSIR-92orwithSIR-2004,
202n 3. substituents cannot act as halogen bond acceptor or both. That refined with SHELXL-97 and finally checked using PLATON.31
ed on 1/25/s Attributio gOwiirvtehtshhetyihgeohceicorudiroindineintaehteocomcnrsytsettnhatel.sTpthrouescrsteiubtrihleiestyomtfoolalecrcogunelrveefslregaxeriebalanebdmleiontloteectruwalicestst. mTmheeetnhtasobdsa.on32rdpAtrlielofrniensleewmvaeenrnettdscoaartrareeacgntiedvdepnbayirnaSmCTeaAtbLelEres31oA.fBCthSCPeDAXCC-rK1a0ym3m7u1el7tai9ssuc(ar1en)-,
adon themselvesinawayofmaximumhalogenbondformationwhere 1037183 (2), 1037178 (3), 1037181 (4), 1037184 (5), 1037182 (6),
om
nlm also I(cid:2)(cid:2)(cid:2)I halogen bonds occur. Stating which intermolecular 988932(7a),988931(7b)and1037180(8).
wo
ugust 2015. Doer a Creative C citnwrytiessWtrtaaiinlcthtsgito:rtnu2hciitlssuefdrbteo,asmc4okifgnrircagoonhumttn)ipdnooufstuhntcedhhsesm2ismtaorinluleadccrtu4iutlryeiass(lrdiseaemrhsrpaaairrntdkegaleybtmhpleeoe,sncostoipbniplnseoi.dstiehtree- S(1yn(etEhq/.Ze,s)-e13s.,032-Dige,th4oxmy-1m,2o-ld)iioandod-13-p,3h-ednieytlhporxoyp-1e-nph(7ean,y7lb)p.rIoopdyinnee
0 Aund ing the diversity of interactions (O(cid:2)(cid:2)(cid:2)H, I(cid:2)(cid:2)(cid:2)O, I(cid:2)(cid:2)(cid:2)I, I(cid:2)(cid:2)(cid:2)C(p)) (817.04 mg, 4 mmol) were dissolved in CHCl3 (5 mL) and
n 2ed occurringinthecrystalstructureof4.Intherelevantpartofthe refluxedfor19hwhilestirring.Aftercoolingtoroomtemperature
Published ocle is licens twchriyetshletasfolsusbtrromutchotulcerrceyusoltefasl2isntthrauetrcueturanrrebesusatortleheledytoIum(cid:2)r(cid:2)n(cid:2)iInsahitnaeldtohgebeyncrhybseotlnaicldasslt.rcuNhceatvuienrres- tsThohedeirusemoalcuttthiiooinonsmuwlifaxasttuedr(re1ie0wdmawsLiq)thuaneNndacw2hSaeOsdh4weadintdhwitathh5ew%saot(levwre/(nv1)t0swmoalLus)teitovwanipcooef.-
s Article. This arti hhofyadl4orgoaegrneenbsombnoadnlsldeisrs.btThehrceaeeucstoiemrrteehsseparoesnltdahriegnegm.IhoneleltichxuelbecusryilasttraeulpcsotbrnuyncettuhctreeedIo(cid:2)f(cid:2)b(cid:2)2yI 4rsao5tl7eid.d9.2(4T450h%e[M,st8+e]4r,2efo.o5iu0snommd:ge4)r.5icH7.mR92Mix2tS5ur((E1e0Io)0:f%m7)/w.zacsalocbdtafoinre(dC1a3sHy1e6lIl2oOw2i)sh=
s
ce the asymmetric unit contains two independent molecules that 7a: d (270.17 MHz, CDCl ) 7.38–7.26 (5H, m, H ), 3.92
c H 3 Ar
A
n form helices that are symmetry generated and also twisted into (1H,s,CH),3.42,3.36(4H,AB-system,2JHH=9.4Hz,CH2),1.17
e
Op eachotherwithoutconnection.Forthestericdemandmethyland (6H,t,3JHH=7.1Hz,CH3).
CH2OHseemstobeequivalentinthiscase. dC (67.93 MHz, CDCl3) 143.8 (Ci), 128.9 (Cp), 128.5 (Cm),
Discussingthequestion,whetherthetwistingofthephenyl 127.8 (C ), 122.4 (QCI), 115.7 (Ph–CI), 99.1 (CH), 62.6 (CH ),
o 2
ringattheCQCdoublebondiscorrelatedduetotheformation 15.1(CH ).
3
of halogen bonding to iodine the two isomers KAFBOJ28 and 7b: d (270.17 MHz, CDCl ) 7.38–7.19 (5H, m, H ), 8.83
H 3 Ar
KAFBID28canbeconsidered(Fig.24).InthecaseofKAFBOJ28 (1H,s,CH),3.77,3.66(4H,AB-system,2J =9.5Hz,CH ),1.33
HH 2
clearhalogenbondingofiodinetothep-systemcanbeobserved (6H,t,3J =7.1Hz,CH ).
HH 3
inthecrystal.Ontheotherhand,inthecaseofKAFBID28only d (67.93MHz,CDCl )147.2(C),128.6(C ),128.5(C ),128.3
C 3 i m p
hydrogenbondingandnohalogenbondingisfound.Lookingat (C ),107.2(CH),106.5(QCI),96.8(Ph–CI),63.0(CH ),15.3(CH ).
o 2 3
the torsion angles, regarding the phenyl substituents the twist- (E)-Methyl 2,3-diiodo-3-phenylacrylate (5). Methyl 3-phenyl-
ing of the phenyl ring of KAFBOJ is with 74.4(7)1 much larger propiolate (0.44 mL, 3 mmol) was dissolved in MeCN (10 mL)
thanthetwistinginKAFBID(37.6(6)1).Thelargertwistinginthe and I (1 eq., 761.4 mg, 3 mmol) and CuI (5 mol%, 28.6 mg,
2
caseofKAFBOJismostprobablycausedbytheeffectofhalogen 0.15 mmol) were added in one portion. The reaction mixture
bonding,whichfitswelltotheobservationsmadeintherelated was refluxed for 20 h. After cooling to room temperature, the
diiodoolefins1–7. reaction mixture was quenched with a 5% (w/v) solution of
sodium thiosulfate (10 mL) and washed with water (10 mL)
Experimental section twice.ThesolutionwasdriedwithNa SO andthesolventwas
2 4
evaporated. Compound 7 was isolated as a colourless solid
Materialsandmethods
(94%,1.17g).
All chemicals were commercially available and were used as d (270.17MHz,CDCl)7.49–7.28(5H,m,H ),3.93(3H,s,CH).
H 3 Ar 3
received.NMRspectrawererecordedwithaJEOLEX400Eclipse d (67.93 MHz, CDCl )166.9(CQO),145.1 (C), 129.3(C ),
C 3 i Ar
instrumentoperatingat400.128MHz(1H)and100.626MHz(13C). 128.7(C ),128.0(C ),98.6(C–I),85.7(C–I),53.7(CH ).
Ar Ar 3
8530 | NewJ.Chem.,2015,39,8522--8533 Thisjournalis©TheRoyalSocietyofChemistryandtheCentreNationaldelaRechercheScientifique2015
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Paper NJC
8 CHIO6624395.91100(2)Colorlessblock0.200.20(cid:4)(cid:4)0.10MonoclinicP2/c18.6795(4)7.5937(2)8.5520(4)90108.798(5)90533.59(4)22.4645.8710.7106936010h10(cid:3)rr9k9(cid:3)rr10l10(cid:3)rr5167 10529230.029860 4.77–32.460.0174,0.0420 0.0211,0.04270.9690.499,0.671(cid:3)
(cid:4)
M. Licence. 7b CHIO131622458.06100(2)Colorlessplate0.3230.181(cid:4)0.021MonoclinicP2/c110.7818(7)10.2566(6)14.5072(9)90109.917(7)901508.32(16)42.0174.1590.7106986414h14(cid:3)rr13k13(cid:3)rr19l19(cid:3)rr13331 371929190.049166 4.3–28.30.0307,0.0656 0.0472,0.05931.0290.682,1.285(cid:3)
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1/25/2023 2:30:43 bution 3.0 Unporte 7a CHIO131622458.06100(2)Colorlessplate0.4170.176(cid:4)(cid:4)0.053MonoclinicP2/n111.3978(4)7.2145(2)18.1044(6)9098.253(3)901473.30(8)42.0654.2580.7106986415h15(cid:3)rr99k(cid:3)rr24l14(cid:3)rr24970 364732150.042166 4.2–28.30.0231,0.0566 0.0294,0.05311.0980.68,1.06(cid:3)
Access Article. Published on 20 August 2015. Downloaded on This article is licensed under a Creative Commons Attri 456 CHIOCHIOCHIO98210822111022385.95413.96427.99173(2)100(2)173(2)ColorlessplateColorlessblockColorlessblock0.350.100.40.150.200.15(cid:4)(cid:4)(cid:4)(cid:4)(cid:4)(cid:4)0.050.050.10TetragonalMonoclinicMonoclinicI4/aC2/cP2/n1123.9673(5)20.5998(15)12.8366(5)23.9673(5)7.1799(2)7.0467(2)7.5322(3)18.253(2)14.2790(6)90909090120.835(11)96.053(4)9090904326.7(2)2318.1(4)1284.41(9)16842.3702.3722.2135.7695.3994.8760.710690.710690.710692816152079228h2928h2817h18(cid:3)(cid:3)(cid:3)rrrrrr20k295k59k9(cid:3)(cid:3)(cid:3)rrrrrr7l931l3120l20(cid:3)(cid:3)(cid:3)rrrrrr108661330816765 2116287637601501226427470.03260.05960.0364161133156 4.32–33.584.18–32.504.26–32.350.0225,0.04120.0250,0.05310.0232,0.0424 0.0386,0.04320.0367,0.05470.0416,0.04490.8900.9400.9170.443,0.3040.758,1.3950.957,0.878(cid:3)(cid:3)(cid:3)
n
e
p
O 3 CHI862355.93100(2)Colorlessblock0.220.12(cid:4)(cid:4)0.05MonoclinicC2/c10.1365(4)15.9425(6)5.7295(2)9094.279(4)90923.31(6)42.5606.7390.7106964014h14(cid:3)rr22k22(cid:3)rr8l8(cid:3)rr9343 136111260.031175 4.17–30.090.0176,0.0404 0.0245,0.04151.0270.626,0.592(cid:3)
pounds1–8 2 CHI982369.95200(2)Colorlessblock0.300.15(cid:4)(cid:4)0.10MonoclinicP2/c118.9368(9)7.6070(3)22.9348(12)90109.349(6)903117.2(3)122.3655.9930.71069201623h22(cid:3)rr9k9(cid:3)rr19l28(cid:3)rr15609 609843520.0363319 4.17–26.00.0282,0.0525 0.0457,0.05520.8570.822,1.536(cid:3)
m
o
ucturedataofc 1 CHI14102432.02173(2)Colorlessplate0.400.25(cid:4)(cid:4)0.08Monoclinic/nP215.7078(3)17.4128(8)7.0077(4)90110.984(6)90650.30(6)22.2064.8060.710694007h7(cid:3)rr21k21(cid:3)rr8l8(cid:3)rr8934 126610990.030367 4.14–25.980.0162,0.0368 0.0210,0.03741.0580.462,0.339(cid:3)
str
Table1Crystal Compound FormulaMT,[K]Color,habitCryst.size,[mm]CrystalsystemSpacegroupa,[Å]b,[Å]c,[Å]1a,[]1b,[]1g,[]3]V,[ÅZ3(cid:3)r,[gcm]calcd1(cid:3)m],[mmIrradiation,[Å]F(000)Indexranges ReflnscollectedReflnsuniqueReflnsobsdRintParamsrefined1yrange,[],wRR124s[I2(I)],wRR12(alldata)GooFd,pmax3(cid:3)d,[enm]pmin
Thisjournalis©TheRoyalSocietyofChemistryandtheCentreNationaldelaRechercheScientifique2015 NewJ.Chem.,2015,39,8522--8533 | 8531