Inorganica Chimica Acta, 45 (1980) L65-L67 L65

@Elsevier Sequoia S.A., Lausanne - Printed in Switzerland

Classification and Nomenclature of Coronands, Cryp- open-chain polyethers various glyme notations
tands, Podands, and of Their Complexes independent of the above ones have been employed
[8, 91. Since these notations are often incomplete
[3, 5, 6, IO] and difficult to be compared with one
EDWIN WEBER and FRITZ VijCTLE another [4, 7, Ill, it is desirable to unite them in a
Institut fir Organ&he Chemie und Biochemie der Universi- common nomenclature, to precisely define them and
tcjt,Gerhard-Domagk-Str.I, D-5300 Bonn I, F.R.G. enlarge their scope without losing their practicability
Received March 2 1,198O ]121*
Table I shows a classification of the various
organic neutral ligand systems, which is first of all
essential: Multidentate monocyclic ligands with any
The common notations in use nowadays for crown type of donor atoms are called coronands [ 131
ethers and cryptands like ‘[ 181 crown6 [I] and (‘crown compounds’), while the term crown ether
‘[2.2.2] cryptand’ [2] have been extended in various is reserved for cyclic oligoethers containing oxygen
ways during recent years to neutral ligands, which only. Moreover, a subdivision of the coronands,
contain heteroatoms other than 0 and N, aromatic crypfunds [2] and podands [ 141 according to the
nuclei and chains other than -CH2XH2- [Z&7]. For number of arms or bridges is demonstrated, whilst

TABLE I. Topology and Classification of Organic Neutral L&and? (D = Donor Atom, A = Anchor Group,“= Chain Segment
without Donor Atom, B = Bridgehead Atom).

Podandsb (openchain) Coronandsc’d (cyclic) Cryptand$ (spherical)

D
wD
(1) Coronand’ (Monocoronand)

(2) Podand (Dipodand) (2) Coronand (Dicoronand) (3) Cryptand (Tricryptand)g

(3) Podand (Tripodand) (3) Coronand (Tricoronand) (4) Cryptand (Tetracryptand)’

aFor mixed openchain/cyclic ligand systems lying between these topologies we suggest notations like ‘podandocoronand’ or
‘coronandocryptand’ under consideration of the follobwmf order of priority: podand < coronand < cryptand; the class naye is
derived from the topologicaIly higher ligand unit. n-O--. ‘n = 1 _ _. dD = 0 (crown ether). en= 1 ___ For
simplificity the numbers in the braces may be omitted. gDifferent topologies apart from those shown exist.
L66 Inorganica ChimicaActa Letters

the minimum number of donor atoms, chain seg- 2: 12((2,6)Thiopheno,Ss-1.2s A-coronand-4)

ments and anchor groups are stated. Names are p: 18((2,6)Pyridinoecoronandd)
also derived from these structural elements.
Substituents and functional groups in the basic
skeleton (class name) are denoted by prefmes and
Coronand Nomenclature suffvres (camp. 2 and 2).

A few samples of crown compound names are Heteroatom and Bridge Sequence, Numbering
given below: The sequence of donor sites in the ligand skeleton
is given by hetero elemental symbols arranged in the
order or priority laid down by the IUPAC rules
[0 precedes S and N (camp. 4J, lowest locants for the
second heteroatom (camp. z> or for substituents and
functional groups (camp. 2)] . Heterocycles with
donor sites are treated as &gle atoms (camp. Hz).
The sequence for the chain segments without donor
1: 18(0eCoronandd); short name: 18C6 atoms corresponds to that of the heteroatoms, begin-
2: 9-Methyl-l8(0eeoronand6)2-en ning from the donor atom of highest priority. The
3: 22(0e-1.2.3a.2.5Coronand-6) numbering is principally carried out according to
f: I-Methyl-14(OSNO-2.3.2.3coronand-4) IUPAC rules (this is also valid for the cryptands but
does not apply in case of the podands; see below).

Punctuation and Symbolism

In the braces {) one obtains information about Cryptand Nomenclature
the topologv of the ligand (camp. Table I), whereby
(1)may be omitted. The number following the It is developed using the same symbolism in
braces or preceding the angular brackets 0 give the principle (see _p-13). In the angular brackets the
ring size, e.g. ‘18’ for J and 2. In presence of aromatic bridgehead atom cfhighest priority is named, and in
and heteroaromatic units in the ring the shortest way the square brackets follows the sequence of the
to the next donor atom is considered (camp. _e=). individual bridges, starting from the preceding bridge-
The angular bmckets 0 contain in the following head. The bridge with the highest number of donor
order: a) donor hetero atoms expressed by the ele- atoms has priority; with equal numbers of donor
mental symbols 0, S, etc. ; b) bridges, i.e. C-C chains atoms in the bridges, the priority is determined by
between the donor hetero atom, denoted by numbers that of the heteroatoms and in second instance by
which correspond to the bridging C-atoms, bridge that of substitution, Following the notations of the
units like aromatic nuclei or more complex groups bridges are the symbol of the second bridgehead
(their positions are marked in round brackets). The atom, the class name and finally the whole number of
designation ‘2’ for ethano, the most common bridge, donor heteroatoms. Further bridges are specified
is omitted when only this bridge is present or when before the class name by square brackets with super-
such a procedure does not curtail the clarity of the scripts indicating their locations (camp. L?, ii).
structure (camp. 1 and 2). With heteroaromatics the
direct annexation-of nuclei is to be regarded as a
normal case and as such is not be considered separa-
tely (e.g. denoted by ‘0’ in i). c) Also included in
the angular brackets are the class mrme (e.g.
coronand) and d) the total number of donor hetero-
atoms. Examples for aromatic unit- and hetero-
aromatic unitcontaining coronands are: z: n = 1, rg: n = 2 LA 12
== ;;

2: (N[Os] [O] sNCryptand6)

LCJ:(N[Oz] sNCryptand-8)
11i’CN[O(2,6)Pyridino‘O-2.12.21[02]sN-cryptand-8)
f?: {3)(N[ONSNO][Or]sNC[S] 7q13Cryptand-12)6,14dion
i$: {3)(N[ONO]~[0]N([O]7’19Cryptand-10)
8
=
Podand Nomenclature
5 5: 17-Chloro-l5(0s-(1,2)benzeno.24coronand-5)
E: 18(05 (2,6)Pyridino+l,2)benzeno.22 .(1,2)ben- The sequence and numbering begin with the donor
zeno.1 Jcoronandd) atom of highest priority at one end of the chain; the
Inorganica Chimica Acta Letters L67

numbering thus differs from that of IUPAC, in this Acknowledgement

case only. Ends without donor aoms (e.g. methyl
in M) are treated as substituents which prefix the
We are greatful to Dr. P. Koo Tze Mew and Miss
name; otherwise the rules, which have been devel-
B. Jendmy.
loped for coronands, are also valid for the mono-
podands. In the case of oligopodands (camp. ig) the
chain with the highest number of donor atoms is
first named. Additional arms are then denoted in
decreasing order of priority and with superscripts
to their location, whereby the following sequence C. J. Pedersen and H. K. Frensdorff, Angew. Chem., 84,
applies: number of donor atoms, type (priority) 16(1972);Angew. Chem., Int. Ed. Engl., 11, 16 (1972).
B. Dietrich, J. M. Lehn and J. P. Sauvage, Chem. unserer
of the donor atoms, priority of end groups (the
Zeit, 7, 120(1973).
latter based on IUPAC rules (C-14.1 .)). N. F. Curtis, Coord. Chem. Rev., 3, 3 (1968).
Examples are: V. L. Goedken, P. H. Merrell and D. H. Busch, J. Am.
Chem. Sot., 94, 3397 (1972); J. C. Dabrowiak, P. H.
MerreB and D. H. Busch, Inorg. Chem., II, 1979
(1972).
5 J. S. Bradshaw, J. Y. Hui, Y. Chan, B. L. Haymore, R.
M. Izatt and J. J. Christensen, J. Heterocycl. Chem., 11,
14 1; A9 45 (1974).
==
6 L. A. Ochrymowicz, ChingPong Mak and J. D. Michna,
A:: 1 ,lODimethyl(04podand4) J. Org. Chem., 39, 2079 (1974).
AZ: ((I)Quinolino,Os(8)quinolinopodand-7) 7 G. A. Melson, ‘Coordination Chemistry of Macrocyclic
Compounds’, Plenum Press, New York (1979), p. 6ff.
ri: 16-Methyl-l ,lPdipheny1{3}(0zNOzN(S(‘)-podand-7)
8 J. Smid, Angew. them., 84, 127 (1972); Angew. Chem.,
Int. Ed. Engl., 11, 112 (1972).
For the designation of Coronand-, Czyptand-, 9 F. Viigtle and E. Weber, Kontakte (Merck), 2177, 16.
Podandcomplexes, we use the common rules for 10 P. A. S. Smith, Aldrichimica Acta, 10 (2), 30 (1977).
cationic complex units in coordination chemistry, 11 Cf. ‘Oxo-crowns’: G. D. Beresford and J. F. Stoddart,
Tetrahedron Lett., 867 (1980); ‘Spherands’: D. J. Cram,
e.g. 1 8(06-Coronand-6)potassium thiocyanate for the T. Kaneda, G. M. Lein and R. C. Helgeson, J. Chem. Sot.
A-potassium thiocyanate complex and <N[O,] sN- Chem. Commun.. 948 (1979).
Cryptand-8)barium iodide for il-BaIs, etc. 12 Cf: the somewhat similar situation in phane chemistry:
The nomenclature described here allows an essen- F. Vogtle and P. Neumann, Tetrahedron, 26, 5847
tially easier recognition of the compound group and (1970).
13 F. Vijgtle and E. Weber, Angew. Chem., 86, 896
other important characteristics such as topology and (1974);Angew. Chem., Int. Ed. Engl., 13, 814 (1974).
donor centers. Details and borderline cases will be 14 F. Vijgtle and E. Weber, Angew. Chem., 91, 813
discussed in a full paper. (1979); Angew. Chem., Int. Ed. Engl., 18, 753 (1979).