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Halogen-Bonded [N–I–N]− Complexes wi h Symme ic o Asymme ic Th ee-
Cen e –Fou -Elec on Bonds
© Au ho s, 2023
Published e sion
Yu, Shilin; T uong, Khai-Nghi; Siepmann, Ma cel; Sii i, A o; Schumache ,
Ch is ian; Wa d, Jas S.; Rissanen, Ka i
Yu, S., T uong, K.-N., Siepmann, M., Sii i, A., Schumache , C., Wa d, J. S., & Rissanen, K. (2023).
Halogen-Bonded [N–I–N]− Complexes wi h Symme ic o Asymme ic Th ee-Cen e –Fou -
Elec on Bonds. C ys al G ow h and Design, 23(2), 662-669.
h ps://doi.o g/10.1021/acs.cgd.2c01162
2023
Halogen-Bonded [N−I−N]−Complexes wi h Symme ic o
Asymme ic Th ee-Cen e −Fou -Elec on Bonds
Published as pa o a C ys al G ow h and Design i ual special issue on Nonco alen In e ac ions: Celeb a ing
P o . Gu u Row
Shilin Yu,
⊥
Khai-Nghi T uong,
⊥
Ma cel Siepmann, A o Sii i, Ch is ian Schumache , Jas S. Wa d,
and Ka i Rissanen*
Ci e This: h ps://doi.o g/10.1021/acs.cgd.2c01162
Read Online
ACCESS Me ics & Mo e A icle Recommenda ions *
sı Suppo ing In o ma ion
ABSTRACT: A se ies o LH[Z−I−Z] halogen(I) complexes,
whe e Z= saccha ina o o ph halimido anions and LH =
py idinium, py azinium, e abu yl (TBA)- o e ame hylammo-
nium (TMA) ca ions, we e p epa ed, s uc u ally cha ac e ized,
and discussed as complexes consis ing o a [N−I−N]−anion wi h a
h ee-cen e − ou -elec on (3c-4e) halogen bond, and a hyd ogen-
bonding (py idinium o py azinium) o ine (TBA o TMA)
ca ion. The symme ic [N−I−N]−anion, eminiscen o he
iiodide [I−I−I]−anion, is ound o be s uc u ally equi alen o
i s ca ionic analogue [N−I−N]+wi h N−I bond leng hs o 2.26 Å.
In con as o he homolep ic [N−I−N]+complexes, asymme y o
he N−I bond leng hs (2.21 and 2.28 Å) was obse ed o hose
[N−I−N]−complexes which mani es ed a hyd ogen bond o only
one saccha ina o moie y, hus being s uc u ally analogous o he asymme ic he e olep ic [N−I−N]+complexes. The esul s show
ha he 3c-4e [N−I−N] halogen bond, being ei he posi i ely o nega i ely cha ged, can be asymme ized by an ex e nal hyd ogen
bond ([N−I−N]−) o by using wo di e en ligands (he e olep ic [N−I−N]+).
O e he las 20 yea s he s udy o he in e ac ions o
pola ized halogen a oms wi h nucleophilic coun e pa s,
i.e., halogen bonding
1−5
(XB) R−X···Nu (R = any a om, X =
halogen, and Nu = a nucleophile), has ma u ed o be an
impo an esea ch a ea in he domain o nonco alen
in e ac ions and has ecen ly been de ined o occu be ween
he elec ophilic egion o a halogen a om and neu al o
anionic nucleophiles.
6
The e has been a ecen boom o
halogen bonding and o he elec ophile−nucleophile in e -
ac ions, such as chalcogen
7
and pnic ogen
8
bonding, as
demons a ed by he apid inc ease o publica ions o e he
pas decade.
9−11
Halogen bonding has ound u ili y as a nonco alen
in e ac ion o cons uc sup amolecula sys ems, and due o
he simila i y o he bonding geome ies and di ec ionali y,
compa isons wi h hyd ogen bonding can be d awn. Halogen
bonding has been success ully applied o con ol he sel -
assembly o a mul i ude o hos −gues sys ems (ion-pai
ecogni ion, biomolecula /chemical sepa a ions), as well as he
syn hesis o ma e ials wi h e sa ile unc ionali ies such as
po osi y, magne ism, phospho escence, and liquid c ys allin-
i y.
1−5
C ys al enginee ing
1−4,12
has es ablished he di ec ion-
ali y and speci ici y o halogen bonding, esul ing in complex
s uc u es wi h appealing a chi ec u es, wi h hollow capsula
molecula assemblies solely based on classical halogen bonding
ha ing been epo ed ecen ly.
13,14
Due o i s elec onic o igin
as a σ-hole in e ac ion, halogen bonding is mo e di ec ional
han hyd ogen bonding,
15
hough he classical R−X···Nu
halogen bonding has been mo e di icul o s udy in solu ion
and has he e o e been s udied mos ly in he solid s a e.
16−19
A special niche o halogen-bonding esea ch has eme ged
om hose s udies whe e an elec on has been emo ed om
he halogen a om, esul ing in a posi i ely cha ged halenium
ion, X+(X = I, B , o Cl), ye mo e app op ia ely named as
halogen(I) ca ions. Acco ding o he de ini ion o he halogen
bond,
6
hese ca ions can be ega ded as e y s ong bis-
unc ional XB dono s; howe e , he ee halogen(I) ca ion is
highly eac i e and canno be isola ed o used as such.
Ne e heless, he halogen(I) ca ions can be s abilized by
Recei ed: Oc obe 14, 2022
Re ised: Janua y 19, 2023
Communica ionpubs.acs.o g/c ys al
© XXXX The Au ho s. Published by
Ame ican Chemical Socie y A
h ps://doi.o g/10.1021/acs.cgd.2c01162
C ys . G ow h Des. XXXX, XXX, XXX−XXX
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complexa ion wi h wo sui able Lewis bases (L), apping hem
as a [L−X−L]+complex exhibi ing a h ee-cen e − ou -
elec on (3c-4e) bond. Combining an iodine(I) ca ion wi h
wo py idine ligands leads o he bis(py idine)iodine(I) ca ion
wi h a [N−I−N]+3c-4e bond, epo ed al eady in he 1960s
by Hassel e al.,
20
C eigh on e al.,
21
and Haque e al.
22
Such
s abilized halogen(I) complexes ha e a ac ed a lo o
a en ion, especially wi hin he halogen bonding communi y,
and ha e ecen ly been e iewed.
23,24
The iconic example,
bis(py idine)iodine(I) e a luo obo a e (Ba luenga’s e-
agen ),
25
is a mild iodina ion eagen and an oxidan .
Ba luenga’s eagen is a ela i ely s able whi e solid and is
soluble in bo h o ganic and aqueous solu ions, and i s
applicabili y in o ganic syn hesis has been widely demon-
s a ed.
26
E delyi
27−32
has demons a ed wi h e y p ecise and
comp ehensi e s udies in solu ion, supplemen ed wi h
compu a ional calcula ions, ha he [N−I−N]+halogen
bond has a e y s ong in e ac ion a io RXB < 0.65 (RXB
de ined as he sum o he dW adii o he in e ac ing a oms
di ided by hei con ac dis ance), as well as being linea and
symme ic wi h he iodine a om loca ed in he cen e be ween
he N a oms wi h a e y small N−I dis ance a ia ion. O e he
las 5 yea s he ield o halogen(I) chemis y has expanded
g ea ly, wi h ecen de elopmen s including he i s iodine(I)-
based capsules,
33−36
helica es,
37
asymme ic complexes,
38,39
halogen-bonded o ganic amewo ks (XOF),
40
halogen-
bonded hie a chical ma e ials,
41
and solid-s a e nucleophilic
I+···Ag+in e ac ions.
42−44
In addi ion o he a o emen ioned posi i ely cha ged XB
complexes, he almos nea ly as s ong (RXB = 0.65−0.67) bu
neu al N−I···N and N−I···O−N XB complexes, which a e
easily p epa ed om sui able haloimides and halosul onimides
as he XB dono s and py idine de i a i es o py idine N-oxides
as he XB accep o s, ha e been ex ensi ely s udied by
Fou migue
45,46
and us.
17−19,47,48
Un il e y ecen ly i was
belie ed ha o he uncha ged XB complexes canno exhibi
halogen bonds (RXB < 0.65) simila ly s ong as hose o
a o emen ioned complexes, ye ou ecen wo k on s abilized
ca bonyl hypoiodi es
49−51
has shown ha RXB alues below
0.62 a e possible.
The composi ionally simila bu nega i ely cha ged [O−I−
O]
52,53
o [N−I−N]
54−57
sys ems ha e been much less
s udied, and no a all in he con ex o halogen bonding. The
ew X- ay s uc u es o he [N−I−N]−sys ems
54−57
as hei
e abu ylammonium (TBA) sal s (Figu e 1) mani es
s uc u es analogous o hei [N−I−N]+coun e pa s.
Co esponding [N−B −N]−X- ay s uc u es ha e been also
epo ed ( om ph halimide, CSD codes
58
JUBNEZ,
56
XITPEY,
56
and JEJZED
57
).
Based on he sca ci y o he [N−I−N]−sys ems, we became
in e es ed in sys ema ically s udying (Scheme 1) speci ic [N−
I−N]−sys ems in he con ex o halogen bonding and
compa ing hem o hei ca ionic [N−I−N]+coun e pa s, as
well as o he neu al haloimide and hypoiodi e XB sys ems.
Inspi ed by he p e ious wo k on halogen-bonded
complexes o haloimides and py idine-based ligands,
17−19,45−48
Figu e 1. X- ay s uc u es o [N···I···N]−complexes YUNPUV
54
and DIQWIM.
55
Scheme 1. Lis o Componen s Used in This Wo k: 1 and 4 as he XB Dono s and 3, 6 and L1−L8 as he XB Accep o s
Scheme 2. Syn hesis o 1L1 and he Se endipi ous Fo ma ion o L1H[3−I−3]
C ys al G ow h & Design pubs.acs.o g/c ys al Communica ion
h ps://doi.o g/10.1021/acs.cgd.2c01162
C ys . G ow h Des. XXXX, XXX, XXX−XXX
B
a cle -con aining dio hosubs i u ed py idine, 2,6-di olyl-4-
(dime hylamino)py idine (L1;Scheme 1) was syn hesized
h ough a known p ocedu e (see he Suppo ing In o ma ion)
o ob ain he expec ed halogen-bonded complex 1L1. The
complexa ion o 1(NISac) wi h L1 in CHCl3p oceeded
smoo hly, and he 1H NMR spec um (Figu e S3) indica ed
he o ma ion o he 1:1 halogen-bonded complex 1L1
(Scheme 2). The e idence ha only he halogen-bonded
complex 1L1 o ms in solu ion is clea ly isible in he 1H NMR
spec a (Figu e S3), whe e he g adual addi ion o he ligand
L1 (Figu e S2) in o he solu ion o N-iodosaccha in (1)
sa u a es wi h a 1:1 1:L1 a io, while L1H[3-I-3] would ha e
p esen ed i sel wi h a 0.5:1 a io.
Howe e , when he eac ion mix u e (1 equi . o L1 wi h a
sligh excess o 1) was le o slowly e apo a e, single c ys als o
he comple ely unp eceden ed anionic [N−I−N]−complex
L1H[3−I−3] we e ob ained (Scheme 2). The composi ion o
L1H[3−I−3] consis ed o he p o ona ed L1 ligand (L1H+)
and he in si u o med [3−I−3]−complex anion. The s uc u e
o he complex anion, which can be ega ded as wo nega i ely
cha ged saccha ina o anions and an iodine(I) ca ion o ming a
h ee-cen e − ou -elec on (3c-4e) halogen bond be ween he
saccha ina o anion ni ogen a oms and he iodine(I) ca ion,
was e ealed by SCXRD analysis. We pos ula e ha , upon
concen a ion o he eac ion mix u e, he p esence o small
amoun s o wa e in he CHCl3sol en likely led o he
eac ion whe e 1(N-iodosaccha in), halogen-bonded o he
s e ically demanding XB accep o L1, unde wen a e e sible
p o ona ion eac ion
59
o a o d 2(saccha in) and HOI
(hypoiodous acid), which is e y uns able and apidly
Scheme 3. O he Syn he ic Rou es o [N−I−N]−Complexes
Table 1. Geome ical Pa ame e s o he [N−I−N]−Complexes
complex N−I (Å) I−N (Å) N···N (Å) N−I−N (deg) C−N···N−C (deg) N···O�C (Å) N−H···O�C (deg)
L1H[3−I−3] 2.250(4) 2.250(4) 4.479(6) 180 180 2.854(6)
a
(×2) 141.8
a
(×2)
2.239(4) 2.239(4) 4.497(6) 180 180
L1H[3−I−3]H2O 2.265(4) 2.275(4) 4.541(7) 178.8(2) −128.9(2) 2.944(7)
a
157.0
a
2.910(7)
b
148.1
b
L2H[3−I−3] 2.250(5) 2.250(5) 4.500(8) 180 −180 2.708(8) (×2) 146.2 (×2)
2.261(5) 2.261(5) 4.521(8) 180 −180
L3H[3−I−3]
c
2.218(4) 2.293(4) 4.512(6) 179.5(2) 174.3(2) 2.733(6) 175.3
L3H[3−I−3] DFT (in DCM) 2.210 2.275 4.484 178.2 165.9 2.746 162.8
L4H[3−I−3] 2.252(8) 2.252(8) 4.502(14) 180 180 2.681(14) (×2) 162.0(×2)
2.262(9) 2.262(9) 4.526(15) 180 180
L5H[3−I−3]
c
2.225(5) 2.262(5) 4.487(7) 177.6(2) 31.8(2) 2.821(7) 163.8
L6H[3−I−3] (C-monoclinic) 2.247(5) 2.253(5) 4.499(9) 179.6(2) −176.8(2)
L6H[3−I−3] (P-monoclinic) 2.250(5) 2.250(5) 4.499(8) 180 180
2.240(6) 2.240(6) 4.446(8) 180 180
L7H[3−I−3]
c
2.217(5) 2.281(5) 4.496(8) 176.3(2) 150.0(2) 2.671(8) 141.8
L8H[3−I−3]
d
2.191(7) 2.299(6) 4.486(9) 174.8(2) ±72.2(2) 2.732(9) 178.1
TMA[6−I−6] 2.293(11) 2.293(11) 4.587(14) 180 0.5(4)
TMA[6−I−6] DFT (in DCM) 2.235 2.246 4.481 179.2 7.6
a e age (XRD) 2.255(6) 2.258(6) 4.505(9) 179.1(2)
a e age
c
(XRD) (asym) 2.214(5) 2.284(5) 4.495(8) 176.1(2)
DIQWIM
54
2.247 2.250 4.495 176.8 36.2
[N−I−N]+(CSD)
e
2.260 2.262 4.520 178.5 ca. −140 o +180
ca. 0
ca. +140 o +180
a
N−H···O�S.
b
HO-H···O�C.
c
Asymme ic [N−I−N], excluded om he a e age N−I calcula ion.
d
N−H···O hyd ogen bond be ween he
mo philinopy idinium moie ies.
e
The a e age bond geome ies om CSD. Da a analyzed om 58 (97 da a poin s) X- ay s uc u es con aining a
[N−I−N]+halogen bond o py idine-based ligands/bases as XB accep o s.
The o sion angles o m h ee g oups 1s −140 o −180°, 2nd +140
+180°and he 3 d a ound ze o. The la ge majo i y o he o sion angles a e close o ze o.
C ys al G ow h & Design pubs.acs.o g/c ys al Communica ion
h ps://doi.o g/10.1021/acs.cgd.2c01162
C ys . G ow h Des. XXXX, XXX, XXX−XXX
C
unde goes a disp opo iona ion eac ion o o m elemen al
iodine. This was also suppo ed by he obse a ion o a deep
pinkish colo . Saccha in 2can eac wi h L1, which ac s as a
s ong Lewis base, leading o o ma ion o L1H+and he
saccha ina o anion 3. The newly o med 3 hen coo dina es
wi h 1(N-iodosaccha in), a o ding he anionic [N−I−N]−
complex anion [3−I−3]−, which is mo e s able han a mix u e
o 1and 3(Scheme 3a).
The se endipi ous disco e y o he o ma ion o he
L1H[3−I−3] led us o de elop wo di e en syn he ic ou es
(Scheme 3) o ob ain simila complexes. The s a ing ma e ials
in ou e a) a e solids; hus, o es i mechanochemis y could
be used as well, he complex L3H[3−I−3] was p epa ed
mechanochemically unde sol en - ee condi ions (see sec ion
2.3 in he Suppo ing In o ma ion). Subsequen c ys alliza ion
o he complexes in a sui able sol en (dichlo ome hane, slow
e apo a ion, o apo di usion o n-pen ane o e hyl ace a e
in o a dichlo ome hane solu ion o he complex) o di ec ly
om he eac ion mix u e ( ou e b) led o he o ma ion o he
new [N−I−N]−complexes L1H[3−I−3]H2O, L2H[3−I−3],
L3H[3−I−3], L4H[3−I−3], L5H[3−I−3], L6H[3−I−3],
L7H[3−I−3], and L8H[3−I−3]. Besides he saccha ina o-
Figu e 2. X- ay s uc u es o he symme ic [N−I−N]−complexes L1H[3−I−3], L1H[3−I−3]·H2O, L2H[3−I−3], L4H[3−I−3] and L6H[3−
I−3] ( he mal displacemen pa ame e s a he 50% p obabili y le el). The as e isk e e s o ca ego y C, om he C-monoclinic polymo ph (Table
1).
Figu e 3. X- ay s uc u es o he asymme ic [N−I−N]−complexes L3H[3−I−3], L5H[3−I−3], L7H[3−I−3], and L8H[3−I−3] ( he mal
displacemen pa ame e s a he 50% p obabili y le el).
C ys al G ow h & Design pubs.acs.o g/c ys al Communica ion
h ps://doi.o g/10.1021/acs.cgd.2c01162
C ys . G ow h Des. XXXX, XXX, XXX−XXX
D

based [3−I−3]−anions, he e ame hylammonium (TMA)
sal o he ph halimido-based complex TMA[6−I−6] was also
p epa ed using ou e b) (Scheme 3) s a ing om TMA 6
( e ame hyl ph haloimida o sal ) and 4(N-iodoph halimide).
The complex TMA[6−I−6] was p epa ed o compa e he
e ec o a ca ion incapable o hyd ogen bonding (TMA) o he
hyd ogen-bond dona ing ca ions, L1H+−L8H+.
Based on geome ical pa ame e s (Table 1) om he single-
c ys al X- ay di ac ion (SCXRD) analysis, he p epa ed [N−
I−N]−complexes can be di ided in o h ee ca ego ies: (A)
symme ic, HB (L1H[3−I−3], L1H[3−I−3]H2O, L2H[3−I−
3], and L4H[3−I−3]), (B) asymme ic, HB (L3H[3−I−3],
L5H[3−I−3], L7H[3−I−3], and L8H[3−I−3]), and (C)
symme ic, non-HB (L6H[3−I−3] (C-monoclinic), L6H[3−
I−3] (P-monoclinic), and TMA[6−I−6]). As he e is a small
a ia ion o he N−I bond dis ances in he known [N−I−N]+
complexes, he de ini ion o asymme y o he [N−I−N]−
moie y is based on he s a is ically signi ican de ia ion om
he symme ic si ua ion. This has been done by aking in o
accoun he es ima ed s anda d de ia ions (esds) o he N−I
bond dis ances a he 3σle el. The N−I bond dis ance
a e ages (Table 1) in ca ego y A all wi h 99.5% p obabili y
be ween 2.237 and 2.273 Å and be ween 2.240 and 2.276 Å
and be ween 2.199 and 2.229 Å and be ween 2.267 and 2.299
Å in ca ego y B.
The non-HB ca ego y C has only wo examples, wi h he
ph halimida o anion [6−I−6]−exhibi ing clea ly longe ,
symme ic N−I bond dis ances [2.293(11) Å], while bo h
polymo phs o L6H[3−I−3] show N−I dis ances analogous o
hose o ca ego y A. Simila sys ema ic and s a is ically
signi ican di e ences ha e been obse ed only in he
he e olep ic [N−I−N]+complexes
60
bu ha e no been
obse ed o he homolep ic [N−I−N]+complexes,
23,24,58,59
whe e he a e age N−I bond leng h is 2.26 Å (Table 1). The
N−I bond leng hs o all he symme ic species (Figu e 2) a e
ema kably wi hin he excep ionally na ow ange o 2.239(4)
Å o L1H[3−I−3] and 2.262(9) Å o L4H[3−I−3], which
a e all c ys allog aphically indis inguishable om one ano he
wi h espec o hei esd alues, wi h he alues hemsel es all
lying wi hin he epo ed ange o he analogous [N−I−N]+
complexes.
58,59
The la ges a ia ion was obse ed o he asymme ic
(Figu e 3)L8H[3−I−3] wi h N−I bond leng hs o 2.191(7)
and 2.299(6) Å, wi h he o me bond leng h being sho e
han any epo ed o he analogous [N−I−N]+complexes.
The e a e only wo epo ed un es ained asymme ic [N−I−
N]+solid-s a e s uc u es, bo h by he au ho s,
38,60
which
possess he e olep ic ligands: [I(py idine)(DMAP)]PF6and
[I(m z)(DMAP)]PF6(DMAP = 4-dime hylaminopy idine;
m z = 1-me hyl-1,2,3- iazole). These complexes exhibi ed
N−I bond leng h di e ences o 0.020 and 0.148/0.177 Å (as
wo independen molecules we e p esen in he asymme ic
uni cell), espec i ely, which makes he N−I bond leng h
di e ence induced by hyd ogen bonding in L8H[3−I−3]
(0.108 Å) a iable s a egy owa d ins iga ing asymme y in 3c-
4e halogen-bonded complexes (whe he neu al o posi i ely/
nega i ely cha ged), and appa en ly one ha can quan i a i ely
i al he me hodology o u ilizing he e olep ic pai s o
nucleophiles which su e s om disad an ages like ligand
sc ambling.
38,44
The N−I−N angles (Table 1) a e p edominan ly symme y-
es ained and he e o e pe ec ly linea (180°), wi h only
mino de ia ions om linea i y obse ed o he asymme ic
complexes (maximum o 174.8(2)° o L8H[3−I−3]). As
no ed p e iously o [N−I−N]+and neu al O−I−N
complexes,
23,24,27−32,49−51
he N···N in amolecula dis ances
wi hin he complexes a e dic a ed by he elec onic
conside a ions o he iodine(I) ca ions which igh ly es ic s
his dis ance as i sa is ies i s own elec onic needs. This is
e lec ed in he negligible de ia ion om he a e age alues o
4.505(9) Å (symme ic) and 4.495(8) Å (asymme ic) o all
complexes (Table 1), which is a mos 0.049 Å o he
asymme ic complex L6H[3−I−3]. Howe e , his is no
including TMA[6−I−6] (Figu e 4) ha exhibi s a sligh ly
la ge de ia ion o 0.082 Å, which con ains a much mo e
s e ically bulky ca ion ha canno be di ec ly compa ed o he
o he examples.
Due o he known inaccu acy o he hyd ogen a om
posi ions (calcula ed o hei idealized posi ions and e ined
as iding a oms), he hea ie elemen (N and O) dis ances a e
ins ead gi en o he NH hyd ogen-bond dono s o he (C�)
O hyd ogen-bond accep o g oups. These in e molecula
dis ances ange om 2.67(1) o 2.94(1) Å (Table 1) and
can all be conside ed hyd ogen bond con ac s o easonable
s eng h.
To p o ide insigh in o whe he he packing in e ac ions in
he asymme ic complexes (ca ego y B) play a la ge ole han
he hyd ogen bonding, a DFT calcula ion in solu ion was
pe o med (SPARTAN20,
61
M06-2X/de 2-TZVP wi h C-
PCM DCM sol en model; see he Suppo ing In o ma ion
o de ails) o L3H[3−I−3]. The compu a ionally ob ained
geome y (Table 1 and Figu e 3) o L3H[3−I−3] ag ees
su p isingly well wi h he c ys allog aphically de e mined
s uc u e, wi h a de ia ions o only +0.008 and −0.018 Å o
he N−I bond dis ances, −0.028 Å o he N···N dis ances, and
−1.3° o he N−I−N angle. This clea ly indica es ha he
packing o ces in ca ego y B a e no he cause o he
asymme ic [N−I−N]−moie y bu ha i is caused by he
hyd ogen bonding om he HB-dono ca ion o only one o
he saccha ina o ligands (Figu e 3). In he DFT-calcula ed
Figu e 4. X- ay s uc u e o TMA[6−I−6] ( he mal displacemen pa ame e s a he 50% p obabili y le el; le ) and he DFT s uc u e (M06-2X/
de 2-TZVP wi h C-PCM DCM sol en model; igh ).
C ys al G ow h & Design pubs.acs.o g/c ys al Communica ion
h ps://doi.o g/10.1021/acs.cgd.2c01162
C ys . G ow h Des. XXXX, XXX, XXX−XXX
E
model o L3H[3−I−3] S�O···cen oid(py) is 2.969 Å wi h
an o hogonal o ien a ion ( o sion S−O−N−C = 89.4°,Figu e
3) owa d he S�O bond, indica ing a O···πin e ac ion. In he
X- ay s uc u e o L3H[3−I−3] he same o sion angle is
−8.6°(Figu e 3), no mani es ing he same py idinium ca ion
O···πin e ac ion due o he weak H-bonds o he S�O g oups
o he adjacen [3−I−3]−anions. As he ph halimida o-based
complex TMA[6−I−6] (Figu e 4) shows symme ic bu
longe N−I bond dis ances (Table 1), i s s uc u e was also
compu a ionally s udied as wi h L3H[3−I−3] (Figu e 4). The
compu ed geome y di e s in all geome ical pa ame e s om
he SCXRD-ob ained s uc u e, excep o he N−I−N angle
(Table 1). The DFT-ob ained N−I bond dis ances a e no
symme ical (2.235 s 2.246 Å) and de ia e −0.058 and
−0.047 Å om he SCXRD alues. The N···N leng h also
de ia es −0.106 Å om he SCXRD alue (Table 1). This
small, bu ma ked, de ia ion be ween he DFT and SCXRD
alues esul s om he packing in e ac ions be ween he TMA
ca ion and he [6−I−6]−anion, as hey o m a 1-D polyme ,
[···TMA+···[6−I−6]−···TMA+···[6−I−6]−···TMA+···[6−I−
6]−···]n, in he solid s a e (Figu e S6 in he Suppo ing
In o ma ion).
In conclusion, a se ies o anionic [N−I−N]−complexes
con aining hyd ogen-bond accep o s on he N-based ligands
we e syn hesized and cha ge-balanced wi h a a ie y o
di e en hyd ogen-bond dono s. The esul ing complexes
could be so ed in o h ee g oups based on SCXRD s udies:
symme ic HB (hyd ogen-bonded), asymme ic HB, and
asymme ic non-HB. The X- ay s udies e ealed wo impo an
ou comes; he anionic halogen-bonded [N−I−N]−complexes
we e s uc u ally simila o hei ca ionic [N−I−N]+analogues,
wi h a nea -iden ical ange o N−I bond leng hs being
obse ed, and asymme y in he N−I bond leng hs o he
[N−I−N]−complexes could be in oduced ia hyd ogen
bonding o one o hei ni ogen-based ligands, wi h me ics
compa able o o su passing hose o he asymme y esul ing
om he s a egy o c ea ing he e olep ic [N1−I−N2]+
sys ems, which su e om he disad an age o ligand
sc ambling, and which is no an issue o he homolep ic
complexes epo ed he ein.
■ASSOCIATED CONTENT
*
sı Suppo ing In o ma ion
The Suppo ing In o ma ion is a ailable ee o cha ge a
h ps://pubs.acs.o g/doi/10.1021/acs.cgd.2c01162.
Expe imen al de ails, syn hesis and single c ys al
p epa a ion, and single-c ys al di ac ion da a (PDF)
Accession Codes
CCDC 2212725−2212735 con ain he supplemen a y c ys-
allog aphic da a o his pape . These da a can be ob ained
ee o cha ge ia www.ccdc.cam.ac.uk/da a_ eques /ci , o by
emailing [email p o ec ed], o by con ac ing The
Camb idge C ys allog aphic Da a Cen e, 12 Union Road,
Camb idge CB2 1EZ, UK; ax: +44 1223 336033.
■AUTHOR INFORMATION
Co esponding Au ho
Ka i Rissanen −Uni e si y o Jy askyla, Depa men o
Chemis y, 40014 Jy äskylä, Finland; o cid.o g/0000-
0002-7282-8419; Email: [email p o ec ed]
Au ho s
Shilin Yu −Uni e si y o Jy askyla, Depa men o Chemis y,
40014 Jy äskylä, Finland
Khai-Nghi T uong −Uni e si y o Jy askyla, Depa men o
Chemis y, 40014 Jy äskylä, Finland
Ma cel Siepmann −Uni e si y o Jy askyla, Depa men o
Chemis y, 40014 Jy äskylä, Finland
A o Sii i −Uni e si y o Jy askyla, Depa men o Chemis y,
40014 Jy äskylä, Finland
Ch is ian Schumache −RWTH Aachen Uni e si y, Ins i u e
o O ganic Chemis y, 52074 Aachen, Ge many;
o cid.o g/0000-0003-3056-554X
Jas S. Wa d −Uni e si y o Jy askyla, Depa men o
Chemis y, 40014 Jy äskylä, Finland; o cid.o g/0000-
0001-9089-9643
Comple e con ac in o ma ion is a ailable a :
h ps://pubs.acs.o g/10.1021/acs.cgd.2c01162
Au ho Con ibu ions
⊥
S.Y. and K.-N.T. con ibu ed equally o he expe imen al
wo k. The manusc ip was w i en h ough con ibu ions o all
au ho s. All au ho s ha e gi en app o al o he inal e sion o
he manusc ip .
Funding
The Academy o Finland (K.R., g an no. 351121), he Magnus
Eh n oo h Founda ion (J.S.W.), and he Uni e si y o
Jy askyla. C.S. is g a e ul o a DAAD sho - e m g an o
doc o al s uden s and a Kekuleschola ship p o ided by he
Ve band de Chemischen Indus ie e.V.
No es
The au ho s decla e no compe ing inancial in e es .
■ACKNOWLEDGMENTS
We kindly acknowledge he inancial suppo om he
a o emen ioned unding sou ces.
■REFERENCES
(1) Ca allo, G.; Me angolo, P.; Milani, R.; Pila i, T.; P iimagi, A.;
Resna i, G.; Te aneo, G. The Halogen Bond. Chem. Re . 2016,116
(4), 2478−2601.
(2) Gilday, L. C.; Robinson, S. W.; Ba end , T. A.; Lang on, M. J.;
Mullaney, B. R.; Bee , P. D. Halogen Bonding in Sup amolecula
Chemis y. Chem. Re . 2015,115 (15), 7118−7195.
(3) Kolá , M. H.; Hobza, P. Compu e Modeling o Halogen Bonds
and O he σ-Hole In e ac ions. Chem. Re . 2016,116 (9), 5155−
5187.
(4) Wang, H.; Wang, W.; Jin, W. J. σ-Hole Bond s π-Hole Bond: A
Compa ison Based on Halogen Bond. Chem. Re . 2016,116 (9),
5072−5104.
(5) Pancholi, J.; Bee , P. D. Halogen Bonding Mo i s o Anion
Recogni ion. Coo d. Chem. Re . 2020,416, 213281.
(6) Desi aju, G. R.; Ho, P. S.; Kloo, L.; Legon, A. C.; Ma qua d , R.;
Me angolo, P.; Poli ze , P.; Resna i, G.; Rissanen, K. De ini ion o he
Halogen Bond (IUPAC Recommenda ions 2013). Pu e Appl. Chem.
2013,85 (8), 1711−1713.
(7) Aake oy, C. B.; B yce, D. L.; Desi aju, G. R.; F on e a, A.; Legon,
A. C.; Nico a, F.; Rissanen, K.; Scheine , S.; Te aneo, G.;
Me angolo, P.; Resna i, G. De ini ion o he Chalcogen Bond
(IUPAC Recommenda ions 2019). Pu e Appl. Chem. 2019,91, 1889−
1892.
(8) Va adwaj, A.; Va adwaj, P. R.; Ma ques, H. M.; Yamashi a, K.
De ini ion o he Pnic ogen Bond: A Pe spec i e. Ino ganics. 2022,10,
149.
C ys al G ow h & Design pubs.acs.o g/c ys al Communica ion
h ps://doi.o g/10.1021/acs.cgd.2c01162
C ys . G ow h Des. XXXX, XXX, XXX−XXX
F
(9) Robidas, R.; Reinha d, D. L.; Legaul , C. Y.; Hube , S. M.
Iodine(III)-Based Halogen Bond Dono s: P ope ies and Applica-
ions. Chem. Rec. 2021,21, 1912−1927.
(10) Szell, P. M. J.; Zablo ny, S.; B yce, D. L. Halogen Bonding as a
Sup amolecula Dynamics Ca alys . Na . Commun. 2019,10 (1), 916.
(11) Saccone, M.; Ca alano, L. Halogen Bonding beyond C ys als in
Ma e ials Science. J. Phys. Chem. B 2019,123 (44), 9281−9290.
(12) Rissanen, K. Halogen Bonded Sup amolecula Complexes and
Ne wo ks. C ys EngComm 2008,10 (9), 1107−1113.
(13) Dumele, O.; T app, N.; Diede ich, F. Halogen Bonding
Molecula Capsules. Angew. Chem., In . Ed. 2015,54 (42), 12339−
12344.
(14) Beyeh, N. K.; Pan, F.; Rissanen, K. A Halogen-Bonded Dime ic
Reso cina ene Capsule. Angew. Chem., In . Ed. 2015,54 (25), 7303−
7307.
(15) A unan, E.; Desi aju, G. R.; Klein, R. A.; Sadlej, J.; Scheine , S.;
Alko a, I.; Cla y, D. C.; C ab ee, R. H.; Dannenbe g, J. J.; Hobza, P.;
Kjae gaa d, H. G.; Legon, A. C.; Mennucci, B.; Nesbi , D. J. De ining
he Hyd ogen Bond: An Accoun (IUPAC Technical Repo ). Pu e
Appl. Chem. 2011,83 (8), 1619−1636.
(16) T o , R. W.; Mäkelä, T.; Topic, F.; Valkonen, A.; Raa ikainen,
K.; Rissanen, K. Al e na i e Mo i s o Halogen Bonding. Eu . J. O g.
Chem. 2013,2013, 1617−1637.
(17) Raa ikainen, K.; Rissanen, K. In e ac ion be ween Amines and
N-Haloimides: A New Mo i o Unp eceden edly Sho B ···N and
I···N Halogen Bonds. C ys EngComm 2011,13 (23), 6972−6977.
(18) Raa ikainen, K.; Rissanen, K. B ea hing Molecula C ys als:
Halogen- and Hyd ogen-Bonded Po ous Molecula C ys als wi h
Sol en Induced Adap a ion o he Nanosized Channels. Chem. Sci.
2012,3(4), 1235−1239.
(19) Pu eddy, R.; Ju cek, O.; Bhowmik, S.; Mäkelä, T.; Rissanen,
K. Ve y S ong −N−X+···−O−N+ Halogen Bonds. Chem. Commun.
2016,52 (11), 2338−2341.
(20) Hassel, O.; Hope, H.; Sö ensen, N. A.; Dam, H.; Sjöbe g, B.;
To , J. S uc u e o he Solid Compound Fo med by Addi ion o Two
Molecules o Iodine o One Molecule o Py idine. Ac a Chem. Scand.
1961,15, 407−416.
(21) C eigh on, J. A.; Haque, I.; Wood, J. L. The Iododipy idinium
Ion. Chem. Commun. 1966, No. 8, 229.
(22) Haque, I.; Wood, J. L. The Vib a ional Spec a and S uc u e o
he Bis(Py idine)Iodine(I), Bis(Py idine)B omine(I), Bis(γ-
Picoline)Iodine-(I) and Bis(γ-Picollne)B omine(I) Ca ions. J. Mol.
S uc . 1968,2(3), 217−238.
(23) Tu unen, L.; E délyi, M. Halogen Bonds o Halonium Ions.
Chem. Soc. Re . 2020,49 (9), 2688−2700.
(24) Hakke , S. B.; E délyi, M. Halogen Bond Symme y: The N−
X−N Bond. J. Phys. O g. Chem. 2015,28 (3), 226−233.
(25) Ba luenga, J.; T incado, M.; Rubio, E.; González, J. M.
IPy2BF4-P omo ed In amolecula Addi ion o Masked and Un-
masked Anilines o Alkynes: Di ec Assembly o 3-Iodoindole Co es.
Angew. Chem., In . Ed. 2003,42 (21), 2406−2409.
(26) Chalke , J. M.; Thompson, A. L.; Da is, B. G. Sa e and Scalable
P epa a ion o Ba luenga’s Reagen . O ganic Syn heses. 2011, No. 87,
288−298.
(27) on de Heiden, D.; Vande kooy, A.; E délyi, M. Halogen
Bonding in Solu ion: NMR Spec oscopic App oaches. Coo d. Chem.
Re . 2020,407, 213147.
(28) Lindblad, S.; Mehme i, K.; Veiga, A. X.; Nekoueishah aki, B.;
G ä ens ein, J.; E délyi, M. Halogen Bond Asymme y in Solu ion. J.
Am. Chem. Soc. 2018,140 (41), 13503−13513.
(29) Ka im, A.; Rei i, M.; Ca lsson, A.-C. C.; G ä ens ein, J.;
E délyi, M. The Na u e o [N−Cl−N]+ and [N−F−N]+ Halogen
Bonds in Solu ion. Chem. Sci. 2014,5(8), 3226−3233.
(30) Ca lsson, A.-C. C.; Uh bom, M.; Ka im, A.; B a h, U.;
G ä ens ein, J.; E délyi, M. Sol en E ec s on Halogen Bond
Symme y. C ys EngComm 2013,15 (16), 3087−3092.
(31) Ca lsson, A.-C. C.; G ä ens ein, J.; Budnjo, A.; Lau ila, J. L.;
Be gquis , J.; Ka im, A.; Kleinmaie , R.; B a h, U.; E délyi, M.
Symme ic Halogen Bonding Is P e e ed in Solu ion. J. Am. Chem.
Soc. 2012,134 (12), 5706−5715.
(32) Ca lsson, A.-C. C.; G ä ens ein, J.; Lau ila, J. L.; Be gquis , J.;
E délyi, M. Symme y o [N−X−N]+halogen Bonds in Solu ion.
Chem. Commun. 2012,48 (10), 1458−1460.
(33) Tu unen, L.; Wa zok, U.; Pu eddy, R.; Beyeh, N. K.; Schalley,
C. A.; Rissanen, K. [N···I+···N] Halogen-Bonded Dime ic Capsules
om Te akis(3-Py idyl)E hylene Ca i ands. Angew. Chem., In . Ed.
2016,55 (45), 14033−14036.
(34) Tu unen, L.; Peu onen, A.; Fo sblom, S.; Kalenius, E.;
Lah inen, M.; Rissanen, K. Te ame ic and Dime ic [N···I+···N]
Halogen-Bonded Sup amolecula Cages. Chem. - Eu . J. 2017,23
(48), 11714−11718.
(35) Tu unen, L.; Wa zok, U.; Schalley, C. A.; Rissanen, K. Nano-
Sized I12L6Molecula Capsules Based on he [N···I+···N] Halogen
Bond. Chem. 2017,3(5), 861−869.
(36) Taipale, E.; Wa d, J. S.; Fio ini, G.; S a es, D. L.; Schalley, C.
A.; Rissanen, K. Dime ic Iodine(i) and Sil e (i) Cages om T ipodal
N-Dono Ligands ia he [N−Ag−N]+ o [N−I−N]+ Ca ion
Exchange Reac ion. Ino g. Chem. F on . 2022,9(10), 2231−2239.
(37) Vande kooy, A.; Gup a, A. K.; Földes, T.; Lindblad, S.;
O habe , A.; Pápai, I.; E délyi, M. Halogen Bonding Helica es
Encompassing Iodonium Ca ions. Angew. Chem., In . Ed. 2019,58
(27), 9012−9016.
(38) Wa d, J. S.; Fio ini, G.; F on e a, A.; Rissanen, K. Asymme ic
[N−I−N]+ Halonium Complexes. Chem. Commun. 2020,56 (60),
8428−8431.
(39) Taipale, E.; Siepmann, M.; T uong, K.-N.; Rissanen, K.
Iodine(I) and Sil e (I) Complexes o Benzoimidazole and Py -
idylca bazole De i a i es. Chem. - Eu . J. 2021,27, 17412−17419.
(40) Gong, G.; L , S.; Han, J.; Xie, F.; Li, Q.; Xia, N.; Zeng, W.;
Chen, Y.; Wang, L.; Wang, J.; Chen, S. Halogen-Bonded O ganic
F amewo k (XOF) Based on Iodonium-B idged N···I+···N In e -
ac ions: A Type o Diphase Pe iodic O ganic Ne wo k. Angew. Chem.,
In . Ed. 2021,60 (27), 14831−14835.
(41) Wa d, J. S. The solid-s a e hie a chy and iodina ion po en ial o
[bis(3-ace aminopy idine)iodine(I)]PF6.C ys EngComm. 2022,24,
7029.
(42) Yu, S.; Kuma , P.; Wa d, J. S.; F on e a, A.; Rissanen, K. A
“Nucleophilic” Iodine in a Halogen-Bonded Iodonium Complex
Mani es s an Unp eceden ed I+···Ag+ In e ac ion. Chem. 2021,7(4),
948−958.
(43) Wa d, J. S.; F on e a, A.; Rissanen, K. U ili y o Th ee-
Coo dina e Sil e Complexes Towa d he Fo ma ion o Iodonium
Ions. Ino g. Chem. 2021,60 (7), 5383−5390.
(44) Wilcox, S.; Se hio, D.; Wa d, J. S.; F on e a, A.; Lindh, R.;
Rissanen, K.; E délyi, M. Do 2-Coo dina e Iodine(i) and Sil e (i)
Complexes Fo m Nucleophilic Iodonium In e ac ions (NIIs) in
Solu ion? Chem. Commun. 2022,58 (32), 4977−4980.
(45) Makho kina, O.; Lie ig, J.; Jeannin, O.; Fou migué, M.;
Aube , E.; Espinosa, E. Coc ys al o Sal : Solid S a e-Con olled
Iodine Shi in C ys alline Halogen-Bonded Sys ems. C ys . G ow h
Des. 2015,15 (7), 3464−3473.
(46) Aube , E.; Espinosa, E.; Nicolas, I.; Jeannin, O.; Fou migué, M.
Towa d a Re e se Hie a chy o Halogen Bonding be ween B omine
and Iodine. Fa aday Discuss. 2017,203, 389−406.
(47) Pu eddy, R.; Rau iainen, J. M.; Mäkelä, T.; Rissanen, K.
S ong N−X···O−N Halogen Bonds: A Comp ehensi e S udy on N-
Halosaccha in Py idine N-Oxide Complexes. Angew. Chem., In . Ed.
2019,58 (51), 18610−18618.
(48) Any an i, G.; Bauzá, A.; Gen iluomo, L.; Rod igues, J.;
Po alone, G.; F on e a, A.; Rissanen, K.; Pu eddy, R. Sho X···N
Halogen Bonds Wi h Hexame hylene e aamine as he Accep o .
F on . Chem. 2021,9, 623595.
(49) Yu, S.; Wa d, J. S.; T uong, K.-N.; Rissanen, K. Ca bonyl
Hypoiodi es as Ex emely S ong Halogen Bond Dono s. Angew.
Chem., In . Ed. 2021,60 (38), 20739−20743.
C ys al G ow h & Design pubs.acs.o g/c ys al Communica ion
h ps://doi.o g/10.1021/acs.cgd.2c01162
C ys . G ow h Des. XXXX, XXX, XXX−XXX
G
(50) K ame , E.; Yu, S.; Wa d, J. S.; Rissanen, K. Dihypoiodi es
S abilised by 4-E hylpy idine h ough O−I−N Halogen Bonds. Dal .
T ans. 2021,50 (42), 14990−14993.
(51) Wa d, J. S.; Ma ono a, J.; Wilson, L. M. E.; K ame , E.; Aa ,
R.; Rissanen, K. Ca bonyl Hypoiodi es om Pi alic and T imesic
Acid and Thei Sil e (i) In e media es. Dal . T ans. 2022,51 (38),
14646−14653.
(52) Muniz, K.; Ga cía, B.; Ma ínez, C.; Piccinelli, A. Dioxoiodane
Compounds as Ve sa ile Sou ces o Iodine(I) Chemis y. Chem. -
Eu . J. 2017,23 (7), 1539−1545.
(53) Kand nálo á, M.; Kokan, Z.; Ha el, V.; Necas, M.; Sindelá , V.
Hype alen Iodine Based Re e sible Co alen Bond in Ro axane
Syn hesis. Angew. Chem., In . Ed. 2019,58 (50), 18182−18185.
(54) Guzmán San iago, A. J.; B own, C. A.; Somme , R. D.; Ison, E.
A. Iden i ica ion o Key Func ionaliza ion Species in he Cp*I (Iii)-
Ca alyzed-O ho Halogena ion o Benzamides. Dal . T ans. 2020,49
(45), 16166−16174.
(55) Lucche i, N.; Tkache a, A.; Fan asia, S.; Muniz, K. Radical C−
H-Amina ion o He e oa enes Using Dual Ini ia ion by Visible Ligh
and Iodine. Ad . Syn h. Ca al. 2018,360 (20), 3889−3893.
(56) Be ges, J.; Ga cía, B.; Muniz, K. An Elec ophilic B omine
Redox Ca alysis o he Syn hesis o Indole Alkaloid Building Blocks
by Selec i e Alipha ic C−H Amina ion. Angew. Chem., In . Ed. 2018,
57 (48), 15891−15895.
(57) Elding, M.; La sson, A. K.; S ensson, G.; Albe sson, J.;
Ebe son, L. S uc u e o a ′hype alen ’ Linea Bis(Ph halimida o)-
B oma e(I) Complex. Ac a C ys allog . Sec . C C ys . S uc . Commun.
1992,48 (11), 2078−2080.
(58) G oom, C. R.; B uno, I. J.; Ligh oo , M. P.; Wa d, S. C.
CSD2022.2, The Camb idge S uc u al Da abase. Ac a C ys allog .
2016,B72, 171−179.
(59) Wa d, J. S.; T uong, K.-N.; E délyi, M.; Rissanen, Halogen-
Bonded Halogen(I) Ion Complexes, Comp ehensi e Ino ganic
Chemis y III; Else ie : 2023. DOI: 10.1016/B978-0-12-823144-
9.00043-1.
(60) Yu, S.; Wa d, J. S. Ligand Exchange among Iodine(i)
Complexes. Dal on T ans. 2022,51 (12), 4668−4674.
(61) SPARTAN20; Wa e unc ion Inc.: 2020.
C ys al G ow h & Design pubs.acs.o g/c ys al Communica ion
h ps://doi.o g/10.1021/acs.cgd.2c01162
C ys . G ow h Des. XXXX, XXX, XXX−XXX
H
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