Carbaporphyrinoids containing a pyridine moiety: 3-aza-meta-benziporphyrin and 24-thia-3-aza-meta-benziporphyrin

Article abstract of DOI:10.1002/ejoc.200500496

6,11,16,21-Tetraaryl-3-aza-m-benziporphyrin, an analog of 5,10,15,20-tetraarylporphyrin with one of the pyrrole units replaced by a pyridine ring pointing outwards, linked at β,β′ positions, was formed by condensation of 3,5-bis[phenyl(2-pyrrolyl)methyl]p

Full text of DOI:10.1002/ejoc.200500496

FULL PAPER
DOI: 10.1002/ejoc.200500496
Carbaporphyrinoids Containing a Pyridine Moiety: 3-Aza-meta-benziporphyrin
and 24-Thia-3-aza-meta-benziporphyrin
Radomir Mys´liborski[a] and Lechosław Latos-Grazyn´ski*[a]
˙
Keywords: Porphyrin / Carbaporphyrinoid / Phlorin / Chlorin / Pyriporphyrin
6,11,16,21-Tetraaryl-3-aza-m-benziporphyrin, an analog of
5,10,15,20-tetraarylporphyrin with one of the pyrrole units
replaced by a pyridine ring pointing outwards, linked at β,βЈ
positions, was formed by condensation of 3,5-bis[phenyl(2-
phy. Both molecules show a similar degree of nonplanarity
with the pyridine ring sharply tipped out of the N(23)X(24)
N(25) plane, making room for the 6,21-phenyl groups which
are almost coplanar with the macrocycle. The protonation of
pyrrolyl)methyl]pyridine, pyrrole and p-tolualdehyde cata- 6,21-diphenyl-11,16-di-p-tolyl-3-aza-m-benziporphyrin with
lyzed by TFA. The [3+1] approach, which involved a conden- trifluoroacetic acid proceeds stepwise, subsequently yielding
sation of 3,5-bis[phenyl(2-pyrrolyl)methyl]pyridine with 2,5-
bis[hydroxy(p-tolyl)methyl]thiophene was applied to afford
6,11,16,21-tetraaryl-24-thia-3-aza-m-benziporphyrin. Intro-
duction of bulky substituents at ortho positions of meso-aryl
compounds, adjacent to the pyridine ring, resulted in an in-
two dicationic and one tricationic species. Protonated 6,21-
diphenyl-11,16-di-p-tolyl-24-thia-3-aza-m-benziporphyrin
reacts reversibly with water to give 6-hydroxy-6,21-di-
phenyl-11,16-di-p-tolyl-24-thia-3-aza-m-benziphlorin. The
protonation of 6,21-dimesityl-11,16-di-p-tolyl-24-thia-3-aza-
crease in the yield of condensation. 3-Aza-m-benziporphyr- m-benziporphyrin initiates an unprecedented process, which
ins and 24-thia-3-aza-m-benziporphyrins have the 1H NMR
spectroscopic features of non-aromatic molecules. Crystal
structures of 6,21-diphenyl-11,16-di-p-tolyl-3-aza-m-benzi-
porphyrin and 6,21-diphenyl-11,16-di-p-tolyl-24-thia-3-aza-
converts the non-aromatic carbaporphyrinoid reversibly into
the aromatic 2-hydroxy-6,21-dimesityl-11,16-di-p-tolyl-24-
thia-3-aza-m-benzichlorin.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
m-benziporphyrin were determined by X-ray crystallogra- Germany, 2005)
(pyrrole, furan, thiophene)[13–18] to yield N-, O- or S-con-
Introduction
fused porphyrins, respectively. In this way the electronic
structure of the porphyrin is profoundly altered leading to
reactivity patterns that are unknown to the parent porphy-
rins or heteroporphyrins.
Large families of expanded, contracted, and isomeric
porphyrins were brought into existence by changing the
number and sequence of the constituent pyrrole rings and
carbon linkages.[1,2] A group of modifications that we have
found particularly interesting involves the introduction of
C–H moieties into the coordination core of the porphyrin,
so as to replace one or more of the pyrrolic nitrogen atoms.
Such molecules, known as carbaporphyrinoids, offer the
possibility of stabilizing rare types of metal–carbon bonds
in a macrocyclic setting.[3–7] The inner C–H unit of a carba-
porphyrinoid is a part of carbocyclic or heterocyclic moie-
ties. In the first group of carbaporphyrinoids the inner
C–H bond belongs to a carbocyclic fragment,[5] as exem-
plified by benzene in benziporphyrins.[8–12] Actually, various
compounds of this type are known that incorporate dif-
ferent mono- and polycyclic moieties into their structures.
The choice of the carbocycle affects the degree of π-conju-
gation in the system, and consequently the macrocyclic aro-
maticity in some carbaporphyrinoids is attenuated or totally
absent. Alternatively, the CH fragment is provided by ap-
propriately oriented five-membered heterocyclopentadienes
Recently, we have synthesized 6,11,16,21-tetraphenyl-
benziporphyrin (1), which can be formally constructed by
replacement of one of the pyrrole rings of 5,10,15,20-
tetraphenylporphyrin (TPP)H2 with a meta-phenylene moi-
ety.[10] Benziporphyrins are versatile ligands, which offer a
means to study the metal–arene couple in a macrocyclic en-
vironment.[6,10–12,19–21] The coordination brings the metal
ion into the vicinity of the arene leading to activation of
C–H bonds followed by dissociation and coordination or
weak interactions, which can be spectroscopically observed.[12]
Here, in search of a route to control the properties of
benziporphyrins we have synthesized 6,11,16,21-tetraaryl-
3-aza-m-benziporphyrin (2). Formally this macrocycle has
been constructed by replacement of one of the pyrrole rings
of 5,10,15,20-tetraarylporphyrin with a pyridine moiety,
linked to the macrocycle by the 3,5-carbon atoms. Alterna-
tively, the molecule can be treated as a derivative of
6,11,16,21-tetraaryl-m-benziporphyrin (1) where the 3-CH
fragment has been exchanged with the nitrogen atom to
yield 6,11,16,21-tetraaryl-3-aza-m-benziporphyrin (2). As it
is readily seen, by analogy to a porphyrin/N-confused por-
[a] Department of Chemistry, University of Wrocław,
14 F. Joliot-Curie St., Wrocław 50383, Poland
E-mail: LLG@wchuwr.chem.uni.wroc.pl
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R. Mys´liborski, L. Latos-Grazyn´ski
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FULL PAPER
phyrin couple, the 3-aza-m-benziporphyrin can be related sation precursor, i.e. 3,5-bis[aryl(hydroxy)methyl]pyridine
to a regular pyriporphyrin 3 (22-aza-m-benziporphyrin) ap- (4) (Scheme 2), which is a suitable synthon for introducing
plying the N-confusion concept as shown in Scheme 1.
the N-confused pyridine ring into a porphyrin-like skeleton.
The lithiation of 3,5-dibromopyridine (5), with n-butyllith-
ium yielded the 3,5-dilithium derivative 6.[34] The lithiation
step has been followed by reaction with benz- or mesital-
dehydes, to convert 6 into the target molecules 4 or 4-M,
respectively (Scheme 2).
Scheme 2. Synthesis of 3,5-bis[aryl(hydroxy)methyl]pyridine 4.
Typically, the condensation of pyrrole, arenealdehyde,
1,3-bis(arylhydroxymethyl)heterocyclopentadiene or 1,3-bis-
[aryl(hydroxy)methyl]benzene in the presence of BF3·Et2O
or TFA, resulted in the synthesis of tetraarylheteroporphy-
rin or tetraaryl-m-benziporphyrin, respectively.[3,10,11] Con-
trary to our expectations the analogous procedure, using 4
as a substrate, has not produced any detectable amount of
the targeted carbaporphyrinoid 2. Presumably the substrate
4 has been deactivated by acidic catalysts as previously de-
tected in syntheses of porphyrins containing meso-2/3/4-py-
ridyl substituents.[35]
In order to overcome this problem the [3+1] strategy, fre-
quently applied in the synthesis of β-substituted porphy-
rins,[36] has been exploited. In such an approach 3,5-bis-
[aryl(2-pyrrolyl)methyl]pyridine (7) is the key compound
as the “3” component of the condensation reaction
(Scheme 3).
Scheme 1. m-Benziporphyrin and aza-m-benziporphyrins.
However, the regular pyriporphyrin (22-aza-m-benzipor-
phyrin) 3 has not been synthesized until now, although the
related, reduced macrocycle has been reported.[22] The re-
arrangement of the N-substituted porphyrins in the pres-
ence of nickel() acetate resulted in the formation of a
chlorin-like macrocycle, which contains a reduced pyridine
fragment.[23] The incorporation of 3-hydroxypyridine into
the porphyrinic macrocycle results in the formation of
2-oxypyriporphyrin by a keto/enol tautomerization, which
contains a pyridone moiety.[24–27] The [4+1] condensation
of tetrapyrrole and 3-hydroxypyridine-2,6-dicarboxalde-
hyde gave the sapphyrin derivative where the central pyrrole
ring was replaced by 3-hydroxypyridine.[28] The reaction of
2,6-dipyrrolylpyridine and benzaldehyde afforded dipyri-
hexaphyrin(1.0.0.1.0.0), containing two pyridine moieties,
which replaced two central pyrrole rings of hexaphyrin-
(1.0.0.1.0.0).[29,30] (Oxypyriporphyrin)nickel() was formed
in the cyclization of (vic-dihydroxyoctaethylchlorin)-
nickel() by secochlorin formation.[31,32] Reaction of dichlo-
rocarbene with meso-octamethylcalix[4]pyrrole caused pyr-
role ring expansion, affording chlorocalixpyridinopyrroles
and chlorocalixpyridines, which correspond to the porphy-
rinogen oxidation state.[33]
Scheme 3. Synthesis of 2,5-bis[aryl(2-pyrrolyl)methyl]pyridine 7.
Paradoxically, the carbaporphyrinoid 6,11,16,21-tetra-
aryl-3-aza-m-benziporphyrin 2 is the very first “true” pyri-
porphyrin containing an unperturbed pyridine ring in the
N-confused macrocyclic framework.
In a typical experiment, 4 is converted into 8, i.e. the
tosylate or mesylate derivatives of 7. Compound 8 was not
isolated but used directly in the next synthetic step. We
found that it is necessary to replace the OH group in 4 by
a better leaving group. The condensation of 4 with pyrrole
to obtain 7 was unsuccessful. Contrary, the 45–90% yield
of 7 or 7-M has been achieved using the mesylate derivative
8 depending on aryl substitution.
Results and Discussion
Synthesis
The key step in the synthesis of 6,11,16,21-tetraaryl-3-
A condensation of 3,5-bis[2-pyrrolyl(phenyl)methyl]pyri-
aza-m-benziporphyrin (2) is the construction of the conden- dine 7 with 1 equiv. of pyrrole and 6 equiv. of p-tolual-
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Carbaporphyrinoids Containing a Pyridine Moiety
FULL PAPER
dehyde in dichloromethane, catalyzed by TFA and followed
by oxidation with DDQ, resulted in 6,21-diphenyl-11,16-di-
p-tolyl-3-aza-m-benziporphyrin (2) (Scheme 4). After chro-
matographic workup and crystallization, 2 was obtained in
2.5% yield.
Figure 1. Electronic spectra of 2 (−) and 10 (···) in CH2Cl2.
Scheme 4. Synthesis of 2.
For topological reasons the molecules 2 and 10 cannot
retain the macrocyclic aromaticity typical of porphyrins.
Thus, the 1H NMR spectra of 2 and 10 show resonances at
positions consistent with non-aromatic structures (Fig-
ure 2).
The rigorous [3+1] approach was applied to afford 6,21-
diphenyl-11,16-di-p-tolyl-24-thia-3-aza-m-benziporphyrin
(10) (Scheme 5). The condensation of 3,5-bis[phenyl(2-
pyrrolyl)methyl]pyridine (7) with 2,5-bis[hydroxy(p-tolyl)-
methyl]thiophene (9) in dichloromethane, catalyzed by TFA
and followed by oxidation with DDQ, resulted in 10 in 3%
yield.
Scheme 5. Synthesis of 10.
Analogous condensations have been carried out using
3,5-bis[mesityl(2-pyrrolyl)methyl]pyridine (7-M). Introduc-
tion of bulky substituents at ortho positions of meso-aryl
groups, adjacent to the incorporated pyridine ring, in-
creased the stability of 7 toward acidolysis during the con-
densation. The scrambling effect has been minimized and
the unreacted compound 7-M was observed after 6 h of
condensation. Significantly, the rather modest structural
change of 7 resulted in a remarkable increase in the yield
of condensation [6,21-dimesityl-11,16-di-p-tolyl-3-aza-m-
benziporphyrin (2-M), 15%; 6,21-dimesityl-11,16-di-p-tolyl-
24-thia-3-aza-m-benziporphyrin (10-M), 18%].
1
Figure 2. H NMR spectra ([D2]dichloromethane, 298 K) of 2 (A)
and 10 (B). Resonance assignments (obtained from COSY and
NOESY experiments) follow the numbering scheme given in
Scheme 1.
The macrocyclic aromatic ring current is absent in 2,
clearly illustrated by the downfield shift of the NH(24) reso-
nance (δ = 10.25 ppm, [D2]dichloromethane, 298 K) (Fig-
ure 2, trace A) and the positions of pyrrole and pyridine
resonances, assigned by 2D experiments {δ = 7.24 H(8/19),
6.59 H(9/18), 6.75 H(13/14), 8.11 H(2/4), 7.72 H(22) ppm,
[D2]dichloromethane, 298 K}. Scalar coupling detected be-
tween the NH(24) and H(13/14) pyrrole protons is consis-
tent with the prevalence of the symmetrical tautomer 2. The
NMR spectroscopic features of 10 resemble those of 2 {δ =
Spectroscopic Studies
The electronic spectrum of 2 (Figure 1) demonstrates two 7.33 H(8/19), 6.69 H(9/18), 7.21 H(13/14), 8.19 H(2/4), 7.66
bands at 411 nm and 700–760 nm resembling the spectro- H(22) ppm, [D2]dichloromethane, 298 K}. The marked dif-
scopic features of non-aromatic 6,11,16,21-tetraphenyl- ference between the H(8/19) and H(9/18) chemical shifts
benziporphyrin (1).[10] The electronic spectrum of 10 re- (ca. 0.6 ppm) is caused by the peculiar orientation of meso
sembles that of 2 but with a distinctive hypochromic shift substituents as shown in the X-ray structures. Because of
of the low-energy band.
significant puckering of the macrocycle the 6/21-phenyl
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R. Mys´liborski, L. Latos-Grazyn´ski
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FULL PAPER
rings are nearly coplanar with the macrocycle, which results
in deshielding of the H(8/19) hydrogen atoms. An analo-
gous difference of chemical shifts was recently reported for
tetraaryl-m-benziporphyrin.[10] The 1H chemical shift values
for the thiophene and pyrrole hydrogen atoms of 2 and 10
are in the range determined for other non-aromatic fully
conjugated systems, which contain thiophene and pyrrole
moieties.[37] The pyridine moiety embedded in the macro-
cyclic structure shows similar chemical shifts to those seen
for 4 or 7.
The discussed 1H and 13C NMR spectra of 2 and 10
correspond to an effectively planar structure contrary to the
puckered structures observed in the solid state for free
bases. This leads to the suggestion that 3-aza-m-benzipor-
phyrin macrocycles, analogous with m- and p-benziporphy-
rins, are conformationally flexible in solution.[11,20] This is
a result of the loss of macrocyclic aromaticity combined
with the constraint generated by the introduction of pyri-
dine. However, it has been noticed that the H(22) reso-
nances of 2-M and 10-M are in unusually downfield posi-
tions {δH(22) = 8.81 2-M; 8.30 10-M ppm, [D]chloroform,
298 K}. Thus, the replacement of the 6,21-phenyl groups by
mesityl substituents results in a downfield relocation of the
H(22) resonances of 2-M and 10-M (1.0 and 0.6 ppm with
respect to 2 and 10, respectively). These changes are ac-
companied by a rather modest upfield relocation of the
H(8/19) resonances, which approach the position of the
H(9/18) counterparts, suggesting that these β-H hydrogen
atoms acquire a similar orientation with respect to the
Figure 3. Molecular structure of 2 (top: perspective view, bottom:
side view). Perimeter hydrogen atoms and meso-aryl groups omitted
for clarity. The hydrogen bond between the dichloromethane mole-
cule (the most abundant occupation) and the perimeter nitrogen
atom is shown in both projections. Thermal ellipsoids are at the
50% probability level.
shielding zones of the adjacent meso-aryl groups. The effec- completely blocks macrocyclic delocalization while retain-
tively orthogonal position of the meso-phenyl groups re- ing unperturbed pyridine aromaticity.
moves the source of shift difference for the H(8/19) and
Figure 4 shows the molecular structure of 10. The funda-
H(9/18) resonances seen for 2 and 10. Clearly, the detected mental structural features of 2 have been preserved in the
spectroscopic changes have been triggered by introduction structure of 10. In particular the macrocyclic ring is puck-
of the bulky mesityl substituents at the 6- and 21-positions, ered and the angle between the pyridine mean plane and
as they are primarily visible at the adjacent molecular frag- the plane of N(23)S(24)N(25) atoms equals 42.6(1)°. There
ments.
is an appreciable effect of the conjugation on the thiophene
fragment. The bond lengths within the thiophene ring are
altered. Thus, the Cα–Cβ bonds [1.447(3), 1.442(3) Å] are
longer than the Cβ–Cβ distances [1.347(3) Å] whereas the
reverse is true for thiophene[38] and tetrathiaporphy-
Structural Studies
X-ray analyses have been performed for compounds 2 rinogen.[39] The Cα–S bond lengths of 1.750(2) and
and 10. The molecular structure of 2 is visualized in Fig- 1.756(2) Å remain practically unchanged. The C(11)–C(12)
ure 3.
[1.378(3) Å] and C(15)–C(16) [1.382(3) Å] distances reflect
The pyridine ring is sharply tipped out of the N(23)N(24) some double-bond character in the bonds that link the thio-
N(25) plane, making room for the 6,21-phenyl groups, phene ring to the macrocyclic frame.
which are almost coplanar with the macrocycle. An angle
In the crystal lattice of 2 the pyridine nitrogen atom N(3)
between the pyridine mean plane and the plane of N(23) is adjacent to the molecule of dichloromethane, which
N(24)N(25) atoms equals 39.8(1)°. π-Bonds within the tri- forms a weak hydrogen bond C–H···N(3) for each of the
pyrrane subunit are largely localized in the manner indicated three disordered orientations. The C–H···N(3) distances
by the valence structure of 2. On the other hand, the bond equal 2.41 (156°), 2.52 (140°), 2.40 Å (124°), respectively
lengths in the six-membered ring are pyridine-like: C(1)– [the appropriate C–H···N(3) angle is given in parentheses].
C(2) 1.413(2), C(2)–N(3) 1.329(2), N(3)–C(4) 1.337(2), The analogous interaction has been observed in the crystal
C(4)–C(5) 1.403(2) (2), C(1)–C(22) 1.393(3), C(5)–C(22) of 10 where the C–H···N(3) distances equal 2.30 (149°), 2.69
1.393(3) Å. The C(21)–C(1) and C(5)–C(6) distances (155°), and 2.55 Å (168°). The C–H···N(3) structural char-
[1.459(2) Å and 1.465(2) Å] approach the single-bond limit acteristics in 2 and 10 are comparable to other cases of
for C(sp2)–C(sp2). These structural features confirm that C–H···N hydrogen bonds, where the pyridine nitrogen atom
the six-membered ring incorporated in the framework of 2 is involved.[40,41]
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Carbaporphyrinoids Containing a Pyridine Moiety
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Figure 4. Molecular structure of 10 (top: perspective view, bottom:
side view). Perimeter hydrogen atoms and meso-aryl groups omitted
for clarity. The hydrogen bond between the dichloromethane mole-
cule (the most abundant occupation) and the perimeter nitrogen
atom is shown in both projections. Thermal ellipsoids are at the
50% probability level.
Figure 5. 1H NMR spectra (downfield regions presented): (A) 2
(203 K), (B) 2Ј-H2 (203 K), (C) 2ЈЈ-H2 (203 K), (D) 2-H3 (183 K) as
obtained during the course of titration of 2 with TFA in [D2]-
dichloromethane. NH resonances are shown in the associated in-
sets. The inner NH resonances of 2-H3 at δ = 10.97 and 11.72 ppm,
overlapped with the COOH resonance of TFA, are not shown in
trace D. Resonance assignments follow the numbering given in
Scheme 1.
Titration of 2 with TFA
1
The H NMR spectroscopic titration of 2 with trifluoro-
acetic acid (TFA) has been carried out in [D2]dichlorometh-
ane at 203 K (Figure 5). The individual resonances of neu-
tral 2 and two dicationic species 2Ј-H2 and 2ЈЈ-H2
Thus, the monocation 2Ј-H is expected to demonstrate
(Scheme 6) have been identified one after the other during two NH resonances (intensity ratio 1:1). Alternatively, one
the 1H NMR titration. Eventually, at the highest concentra- NH resonance but with a relative intensity of two hydrogen
tion of TFA at 183 K the tricationic form 2-H3 has been atoms should be detected for 2ЈЈ-H. However, instead of a
detected. These observations have been attributed to a slow monocationic pattern the very first addition of TFA pro-
1
exchange among the detected ionic forms at 203 K. The un- vides the H NMR spectroscopic features readily assigned
ambiguous assignments of resonances have been obtained to a dication 2Ј-H2. This dication demonstrates two NH
1
by 2D H NMR COSY and NOESY spectroscopic experi- resonances of the predictable, because of symmetry, 2:1 in-
ments. The protonation mechanism was originally analyzed tensity ratio. The appropriate scalar couplings NH(23/25)–
based on the well-separated set of NH singlets in the δ = H(8/19), NH(23/25)–H(9/18) and NH(24)–H(12/13) have
9–18 ppm spectral region to be correlated with the spectro- been detected in the COSY spectra of 2Ј-H2, unambigu-
scopic pattern of pyridine and β-H resonances located at ously confirming the complete protonation of the pyrrole
the δ = 9–6 ppm region.
nitrogen atoms. The further stepwise addition of TFA re-
The general mechanism of protonation, which includes sults in the gradual increase of the 2ЈЈ-H2 concentration ac-
the considered tautomeric species, is presented in Scheme 6. companied by the parallel intensity loss of 2Ј-H2. In par-
The very first protonation step concerns the basic nitrogen ticular, the second set of two NH singlets has been detected
atoms of the macrocyclic core (see below). Thus, the at higher TFA concentrations. The spectral pattern (Fig-
number of resonances, contained in individual H(2/4), ure 5, trace C) corresponds to the dication (2ЈЈ-H2) because
H(22), β-H and NH sets indicate unambiguously the the protonation status of the inner nitrogen atoms remains
number of the species formed in the particular stage of the intact, considering the relative intensity of resonances (2:1)
titration. Their multiplicity and relative NH intensities and scalar couplings to the appropriate β-hydrogen atoms.
1
could be discussed in structural terms. We have already Thus, it is important to realize that the H NMR spectral
shown that the neutral form is protonated at the 24(NH) changes require at least two different dications in equilib-
position (δ = 10.07 ppm, 203 K). Hypothetically one can rium. Presumably, the process involves two tight ionic ag-
predict the formation of two tautomers at a monocationic gregates {[2-H2](CF3COO)}+ and {[2-H2](CF3COO)2}.
level (Scheme 6): [NH(23), N(24), NH(25)]; [NH(23),
The considerable difference of the NH shifts for two di-
NH(24), N(25)].
cations most probably results from the steric requirements
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R. Mys´liborski, L. Latos-Grazyn´ski
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Formation of 6-Hydroxy-3-aza-m-benziphlorin (11)
In contrast to 6,21-diphenyl-11,16-di-p-tolyl-3-aza-
m-benziporphyrin (2), where the protonations of basic ni-
trogen atoms have been solely detected, the reaction of 6,21-
diphenyl-11,16-di-p-tolyl-24-thia-3-aza-m-benziporphyrin
(10) with TFA includes a profound modification of the
macrocycle (Figure 6, Scheme 7).
1
Figure 6. H NMR spectrum of 11 ([D2]dichloromethane, 203 K).
Resonance assignments follow the numbering given in Scheme 1.
Scheme 6. Protonation of 2.
Scheme 7. Structure of 11.
imposed by monocoordinate (one TFA ligand bound above
Formally, the reaction can be classified as an addition of
the porphyrin plane) and dicoordinate arrangements (two water to 10 to produce 6-hydroxy-6,21-diphenyl-11,16-di-
TFA ligands on the opposite side of the porphyrin plane). p-tolyl-3-aza-m-benziphlorin (11), which structurally re-
The contribution of the NH hydrogen atom in the network sembles porphyrin-derived phlorins and is analogous to
of hydrogen bonds, which involve CF3COO– and alkyl-substituted benziphlorin and pyriphlorin.[8,22]
CF3COOH, offers the other factor, which substantially
Previously, we have also shown that the reaction of 1
changes the NH chemical shift. Actually, the dications of with water or methanol yields 6-hydroxy-6,11,16,21-tetra-
6,11,16,21-tetraaryl-3-aza-m-benziporphyrin 2-H2 behave phenylbenziphlorin and 6-methoxy-6,11,16,21-tetraphenyl-
as other polyprotonated macrocyclic cationic ligands,[42] in- benziphlorin.[10] This reactivity resembles the nucleophilic
cluding extended porphyrins,[1,43] which are known for their meso addition of hydride or hydroxide to (TPP)AuIIICl to
selective interactions with inorganic and organic anions. yield phlorin or hydroxyphlorin complexes.[46]
The coordination of TFA by the 2-methyl-5,10,15,20-tetra-
phenyl-2-aza-21-carbaporphyrin,[44] and 5,10,15,20-tetra- 6-position was observed. The H NMR spectrum reflects
arylporphyrin dications have been described previously.[45]
symmetry lowering of 11 in comparison to 2 (Figure 6). In
The reaction is regioselective since only saturation at the
1
The additional equilibria, which are reflected by the particular, the two pyrrolic (δ = 7.79/7.29 and 6.95/
smooth change of chemical shifts for 2ЈЈ-H2, also suggest 6.91 ppm) and one thiophenic (δ = 7.48/7.00 ppm) AB pat-
the independent interaction of this ionic aggregate with the terns have been identified ([D2]dichloromethane, 203 K).
bulk of TFA through a network of hydrogen bonds. The The C(6) carbon atom of 11 produces a resonance at δ =
last protonation step, set off by the large molar excess of 77.0 ppm, which is consistent with its tetrahedral geometry.
TFA, yielded the trication 2-H3. This protonation engages Analogously, the addition of ethanol to 10 yielded
the perimeter nitrogen atom of pyridine. Significantly, the 6-ethoxy-6,21-diphenyl-11,16-di-p-tolyl-3-aza-m-benziphlo-
pyridinium N(3)H resonance has been directly identified at rin (11-OEt). The diagnostic set of two complex multiplets
the unique position δ = 16.56 ppm (183 K). The detected at δ = 3.25 and 3.19 ppm ([D]chloroform, 298 K) has been
scalar couplings (COSY) N(3)H–H(2/4) confirmed the pro- assigned to the ethoxy methylene group. The difference in
tonation at this particular position.
the chemical shifts detected for the two methylene
5044
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2005, 5039–5048

Carbaporphyrinoids Containing a Pyridine Moiety
FULL PAPER
multiplets is due to the diastereotopic effect as the chirality
center is created at the tetrahedrally hybridized C(6) atom.
Addition of triethylamine to 11 resulted in the quantitative
recovery of 10. The easy accessibility of phlorin 11 is related
to the loss of aromaticity incurred by 10.
Formation of 2-Hydroxy-24-thia-3-aza-m-benzichlorin (12)
The titration of 6,21-dimesityl-11,16-di-p-tolyl-24-thia-
3-aza-m-benziporphyrin (10-M) (203 K, [D2]dichlorometh-
ane) with TFA reveals the changes in resonance positions,
which correspond to the regular nitrogen protonation of 24-
thia-3-aza-m-benziporphyrin. However, the severe broaden-
ing of all resonances assigned to protonated species, ob-
served even at 183 K, ruled out a detailed analysis of ionic
structures. The protonation initiates an addition of the
water molecule, which yields the aromatic 2-hydroxy-6,21-
dimesityl-11,16-di-p-tolyl-24-thia-3-aza-m-benzichlorin (12)
(Scheme 8). Actually, such a route is preferred at 298 K,
where 10-M converts into 12 after addition of TFA, dichlo-
roacetic acid or HCl(g). The large amount of triethylamine
enables the quantitative recovery of 12 into 10-M.
Figure 7. 1H NMR spectrum (selected downfield regions presented)
of 12 ([D]chloroform, HCl(g), 203 K).
Mechanistically, the formation of 12 can be considered
as an alternate route to an acid-initiated addition of water
to 24-thia-3-aza-m-benziporphyrins. The formation of phlo-
rin seems to be characteristic of 10. In spite of the obvious
structural similarities, the replacement of meso-phenyl
groups in 10 by meso-mesityl groups in 10-M redirects the
hydroxy anion addition to the pyridine moiety to form 12.
Clearly, the steric hindrance of mesityl groups limits the
access at the 6-position, which is preferable for 10. Thus,
10-M yielded the new aromatic macrocycle by initial pro-
tonation, followed by an addition of the hydroxy group at
C(2). In the course of this reversible process the trigonal to
tetrahedral rearrangements originate at the C(2) atom but
their consequences are extended to the whole structure al-
lowing the aromatic conjugation. The trapped carbapor-
phyrinoid 12 is structurally related to the hypothetical
12-H (Scheme 8) as both contain an identical macrocyclic
frame. In this same line, the macrocycles 10-M and 12-H
are mutually convertible by a hydrogenation/dehydrogena-
tion step presuming that the addition of two hydrogen
atoms is localized at the C(2) and one of the internal nitro-
gen atoms.
Scheme 8. Structure of 12.
The complete assignments of all 1H NMR resonances for
12 are shown in Figure 7. All pyrrole resonances δ = 8.22/
8.21 [AB, 3J(H,H) = 4.6 Hz], 8.02/7.97 [AB, 3J(H,H) =
4.8 Hz] and thiophene resonances δ = 9.23/9.20 ppm [AB,
3J(H,H) = 5 Hz] are shifted downfield ([D]chloroform,
298 K). The strongly upfield position of the H(22) signal
4
[δ = –3.36 ppm, J(H,H) = 1.8 Hz], scalar-coupled with the
downfield shifted H(4) signal (δ = 9.53 ppm) are readily ac-
counted for by the aromatic ring-current effect. The struc-
turally informative H(2) resonance was identified at δ =
6.74 ppm. The 13C chemical shift of C(2) (δ = 76.8 ppm)
is consistent with the tetrahedral hybridization. The fully
Conclusion
The targeted 6,11,16,21-tetraaryl-3-aza-m-benziporphy-
protonated 12 (solution saturated with HCl) demonstrated rin 2 and 6,11,16,21-tetraaryl-21-thia-3-aza-m-benziporphy-
three NH resonances at δ = 16.2, 1.75, and 1.80 ppm readily rin 10 contain a (CNNN) or (CNSN) coordination core of
assigned to the perimeter and inner core localizations.
carbaporphyrinoids. Significantly, the nitrogen atom at the
Addition of ethanol to 10-M in the presence of dichloro- macrocyclic perimeter provides some means to control
acetic acid afforded 2-ethoxy-6,21-dimesityl-11,16-di- overall macrocyclic properties by protonation or alkylation.
p-tolyl-24-thia-3-aza-m-benzichlorin (12-OEt). The diag- Potentially, an external N-coordination of pyridine offers a
nostic set of two complex multiplets at δ = 3.46 and route to construct polymetallic arrays where the pyridine
3.02 ppm have been assigned to the ethoxy methylene moiety will serve as a unique bridge, which links two metal
group. The strong difference in the chemical shifts detected ions involving a simultaneous coordination by C- and N-
for the two methylene multiplets is due to the diastereotopic ends. The flexibility of macrocyclic structures, discovered in
effect as the chirality center is created on the tetrahedrally the course of protonation studies, leads to alternative, non-
hybridized C(2) atom.
conventional routes to modify complex molecular arrays.
Eur. J. Org. Chem. 2005, 5039–5048
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5045

R. Mys´liborski, L. Latos-Grazyn´ski
˙
FULL PAPER
was removed in vacuo. The residue was dissolved in 5 mL of pyrrole
and the reaction mixture, protected from light, was stirred under
nitrogen for 3 d. The reaction was quenched by addition of CH2Cl2
(50 mL). The resulting solution was washed with 10% H2SO4
(6×10 mL) and water. The solution was neutralized by addition of
K2CO3 until the liberation of CO2 had ceased, extracted with
CH2Cl2 several times and dried with MgSO4, filtered, and the sol-
vent removed with a vacuum rotary evaporator. The excess of pyr-
role was removed in a vacuum line. The dark residue was chromato-
graphed on a grade II basic alumina column. The product was
eluted with CH2Cl2/CH3OH (99.8:0.2, v/v) and the solvent was
Experimental Section
Instrumentation: NMR spectra were recorded with a Bruker Avance
500 spectrometer (base frequencies: 500.13 MHz 1H, 125.77 MHz
13C). Spectra were referenced to the residual solvent signals. As-
signments of 1H NMR spectra were obtained from COSY and
NOESY maps, and 13C NMR spectra were based on 1H-13C
HMQC and HMBC experiments. Absorption spectra were re-
corded with a diode-array Hewlett Packard 8453 spectrometer.
Mass spectra were recorded with an AD-604 spectrometer using the
electron impact and liquid matrix secondary ion mass spectrometry
techniques.
1
evaporated. Yield: 350 mg (45%). H NMR (CDCl3, 298 K, mix-
ture of stereoisomers): δ = 8.30 (2 H, 2/6-pyridine), 7.79 (2 H, NH),
7.35 (1 H, 4-pyridine), 7.29–7.10 (10 H, Ph); pyrrole: δ = 6.68 (2
H), 6.11 (2 H), 5.71 (2 H), 5.40 (2 H, methine) ppm. 13C NMR
(CDCl3, 298 K): δ = 148.6 (2/6-pyridine), 142.0 (1-Ph), 138.5 (3/5-
pyridine), 136.8 (4-pyridine), 132.5 (2-pyrrole), 128.93, 128.87,
127.3 (2/3/4-Ph), 117.8 (5-pyrrole), 108.6 (4-pyrrole), 108.4 (3-pyr-
role), 48.3 (methine) ppm. MS (ESI): m/z = 377.
Materials: 3,5-Dibromopyridine, n-butyllithium, mesitaldehyde and
mesyl chloride (from Aldrich) were used as received. Chloroform
(stabilized with amylene) was received from AppliChem. Basic alu-
mina (Aldrich or Alfa-Aesar) was deactivated before chromatog-
raphy. 2,5-Bis[hydroxy(p-tolyl)methyl]thiophene (9) was obtained
as described in the literature.[47]
3,5-Bis[hydroxy(phenyl)methyl]pyridine (4; 4-M): nBuLi (15.9 mL of
1.6  solution in hexanes, 24.55 mmol) was added to a dry THF
solution of 3,5-dibromopyridine (3 g, 12.66 mmol, –100 °C). The
resulting mixture was stirred at –100 °C for 0.5 h. Benzaldehyde
(2.6 mL, distilled; or 3.75 mL of mesitaldehyde for 4-M) was then
added and the reaction mixture was left for several hours while the
cooling bath reached room temperature. The solvents were evapo-
rated under reduced pressure. In the case of 4 the foam that had
formed was dissolved in 20% H2SO4 (150 mL) and washed four
times with CH2Cl2 (25 mL). The acid layer was neutralized with
K2CO3, and the product was extracted several times with CH2Cl2
(25 mL). The combined solutions were dried with MgSO4 and fil-
tered. The solvents were evaporated under reduced pressure. The
residue was dissolved in CH2Cl2 and chromatographed on a grade
III basic alumina column. The fraction eluted with CH2Cl2/
CH3OH (85:15, v/v) was collected, and the solvent was removed
with a vacuum rotary evaporator to give 4 as the yellow foam. An
essential modification of the procedure was necessary to separate
4-M. The foam was dissolved in 20% H2SO4 (50 mL) and CH2Cl2
(50 mL). Both layers were transferred into a beaker and diluted
with water (400 mL). The solution was neutralized by addition of
K2CO3 (with vigorous stirring) and separated. The solution was
extracted several times with CH2Cl2 (25 mL), dried with MgSO4,
filtered, and the solvent removed with a vacuum rotary evaporator.
The residue was dissolved in CH2Cl2 and chromatographed on a
grade II basic alumina column and 4-M was eluted with CH2Cl2/
CH3OH (95:5, v/v). Yields: 4: 1.7 g (46%); 4-M: 950 mg (20%). 4:
7-M: The synthetic procedure followed that of 7 until the excess
pyrrole was removed. The black residue was dissolved in CH2Cl2
and n-hexane was added. The volume was reduced. The yellow
solution of 7-M was decanted. The procedure was repeated several
times. The solutions were combined and the solvent was removed
1
with a vacuum rotary evaporator. Yield: 852 mg (90%). H NMR
(CDCl3, 298 K, mixture of stereoisomers): δ = 8.33 (2 H, 2/6-pyri-
dine), 7.76 (2 H, NH), 7.36 (1 H, 4-pyridine), 6.80 (4 H, m-Mes);
pyrroles: δ = 6.80 (2 H), 6.62 (2 H), 6.10 (2 H), 5.52 (2 H, methine),
2.26 (6-H, Me-4Ј), 1.96 (12-H, Me-2Ј) ppm. 13C NMR (CDCl3,
298 K, mixture of stereoisomers): δ = 148.4 (2/6-pyridine), 136.2
(3/5-pyridine), 136.6 (4-pyridine), 137.6 (1-Mes), 136.9 (4-Mes),
134.4 (2-Mes), 132.0 (1-pyrrole), 130.6 (3-Mes), 116.9 (5-pyrrole),
108.5 (4-pyrrole), 107.3 (3-pyrrole), 42.6 (methine), 21.1 (Me-2Ј),
21.0 (Me-4Ј) ppm. MS (ESI): m/z = 474.
6,21-Diphenyl-11,16-di-p-tolyl-3-aza-m-benziporphyrin (2): 3,5-bis-
[phenyl(2-pyrrolyl)methyl]pyridine (7) (195 mg, 0.5 mmol), pyrrole
(35 µL, 0.5 mmol), and p-tolualdehyde (355 mL, 3 mmol) were
added to dry CH2Cl2 (500 mL) under nitrogen. TFA (300 µL,
3.9 mmol) was added and the reaction mixture was protected from
light and stirred for 1 h. The reaction mixture was neutralized with
560 µL (4 mmol) of triethylamine. DDQ (357 mg, 1.58 mmol) was
subsequently added and the mixture was stirred for several minutes,
and evaporated under reduced pressure. The residue is subjected
to chromatography (grade II basic alumina, CH2Cl2). The desired
product eluted as a green band following a trace of (TTP)H2.
Recrystallization from CH2Cl2/n-hexane yielded deep green crys-
tals. Yield: 8.1 mg (2.5%). 1H NMR (CDCl3, 298 K): δ = 10.36
4
1H NMR (CDCl3, 298 K): δ = 8.43 [d, J(H,H) = 2.2 Hz, 2 H, 2/
4
6-pyridine], 7.75 [t, J(H,H) = 2.2 Hz, 1 H, 4-pyridine], 7,35–7,25
(10 H, Ph), 5.85, 2.40 (s, CHOH, CHOH) ppm. 13C NMR (CDCl3,
298 K): δ = 147.1 (2/6-pyridine), 143.0 (1-Ph), 139.6 (3/5-pyridine),
132.8 (4-pyridine), 128.9, 128.1, 126.7 (2/3/4-Ph), 74,1 (methine)
ppm. MS (ESI): m/z = 291. 4-M: 1H NMR (CDCl3, 298 K, mixture
of stereoisomers): δ = 8.11 (2 H, 2/6-pyridine), 7.76 (1 H, 4-pyri-
dine), 6.79 (4 H, m-Mes), 6.26, (2 H, CHOH), 2.80 (2 H, CHOH),
2.24 (6 H, Me-4Ј), 2.15 (12 H, Me-2Ј) ppm. 13C NMR (CDCl3,
298 K, mixture of stereoisomers): δ = 145.5 (2/6-pyridine), 138.5
(3/5-pyridine), 137.8 (4-Mes), 136.9, 135.8 (1/2-Mes), 131.1 (4-pyri-
dine), 130.3 (3-Mes), 69.4 (methine), 21.7 (Me-2Ј), 21.0 (Me-4Ј)
ppm. MS (ESI): m/z = 390.
4
[s, 1 H, NH(24)], 8.12, 7.80 [A2B, (2 + 1) H, J (H,H) = 2.06 Hz,
H(2/4), H(22)], 7.41–7.47 (m, 10 H, Ph), 7.32, 7.23 [A2B2, (2×2)
H, 3J(H,H) = 8.02, o/m-Tol], 7.19 [AB, 2 H, 3J(H,H) = 4.81 Hz,
H(8/19)], 6.73 [s, 2 H, H(13/14)], 6.57 [AB, 2 H, 3J(H,H) = 4.81 Hz,
H(9/18)], 2.42 (s, 6 H, p-Tol) ppm. 13C NMR (CDCl3, 298 K): δ =
172.7 (10/17), 158.0 (7/20), 152.1 (2/4), 148.3 (12/15), 141.7, 140.8,
132.4 (4-Tol), 136.5 (8/19), 136.4, 133.2 (1-Tol) 133.1 (Ph), 132.1
(2-Tol), 131.4 (9/18), 130.2 (13/14), 128.74 (Ph), 128.67 (3-Tol),
127.6 (Ph), 115.6, 115.2 (22), 21.4 (p-Me) ppm. UV/Vis (CH2Cl2):
λmax (log ε) = 322 (4.48), 411 (4.75), 730 nm (very broad, 3.99).
HRMS (ESI): m/z = 655.2880 (655.2861 for [C47H34N4 + H]+).
3,5-Bis[phenyl(2-pyrrolyl)methyl]pyridine (7): Mesyl chloride
(325 µL, 2.1 equiv. in 500 mL of CHCl3) was added dropwise (2 h)
to the solution of 4 (582 mg, 2 mmol) and triethylamine (585 µL,
2.1 equiv.) in CHCl3 under nitrogen at 0 °C. Subsequently, the reac-
tion mixture was refrigerated for 3 d. After this time, the solvent
6,21-Dimesityl-11,16-di-p-tolyl-3-aza-m-benziporphyrin (2-M): 2-M
was obtained analogously to 2, with 7-M replacing 7. The conden-
sation reaction took 4 h. Yield after the CH2Cl2/CH3OH crystalli-
zation: 55.5 mg (15%). 1H NMR (CDCl3, 298 K): δ = 10.43 [s,
5046
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2005, 5039–5048

Carbaporphyrinoids Containing a Pyridine Moiety
FULL PAPER
1 H, NH(24)], 8.81, 8.30 [AB2, (2 + 1) H, 4J(H,H) = 2.06 Hz, H(2/
4), H(22)], 7.30, 7.21 [A2B2, (2×2) H, 3J(H,H) = 7.79 Hz, o/m-Tol],
6,21-Dimesityl-11,16-di-p-tolyl-24-thia-3-aza-m-benziporphyrin (10-
M): 10-M was obtained analogously to 2-M but in place of pyrrole
and aldehyde 2,5-bis[hydroxy(p-tolyl)methyl]thiophene (9) (162 mg,
0.5 mmol) was used. Yield: 68 mg (18%). 1H NMR (CDCl3,
3
6.92 (s, 4 H, m-Mes), 6.78 [AB, 2 H, J(H,H) = 4.81 Hz, H(8/19)],
6.67 [s, 2 H, H(13/14)], 6.57 (AB, 2 H, 3J(H,H) = 4.81 Hz, H(9/
18)], 2.42 (s, 6 H, p-Tol), 2.35 (s, 6 H, Me-4Ј), 1.99 (s, 12 H, Me-
4
298 K): δ = 8.35, 8.30 [A2B, (2 + 1) H, J(H,H) = 2.13 Hz, H(2/4),
2Ј) ppm. 13C NMR (CDCl3, 298 K): δ = 172.1 (10/17), 158.8 (7/ H(22)], 7.35, 7.21 [A2B2, (2×2) H, 3J(H,H) = 8.03 Hz, o/m-Tol],
20), 152.8 (2/4), 138.1 (1/5), 137.8 (4-Mes), 137.63 (2-Mes), 137.57
(1-Mes), 137.4 (4-Tol), 136.63 (9/18), 136.57 (1-Tol), 132.0 (2-Tol), H, J(H,H) = 4.72 Hz, H(9/18), H(8/19)], 2.42 (s, 6 H, p-Tol), 2.36
131.4 (8/19), 131.1 (6/21), 130.0 (13/14), 128.8 (3-Tol), 128.0 (3-
(s, 6 H, Me-4Ј), 1.99 (s, 12 H, Me-2Ј) ppm. 13C NMR (CDCl3,
7.21 [s, 2 H, H(13/14)], 6.93 (s, 4 H, m-Mes), 6.87, 6.61 [AB, (2×2)
3
Mes), 123.2 (22), 115.3 (11/16), 21.5, (p-Tol) 21.3 (Me-2Ј), 20,9 298 K): δ = 172.5 (10/17), 156.7 (7/20), 154.9 (12/15), 152.8 (2/4),
(Me-4Ј) ppm. UV/Vis (CH2Cl2): λmax (log ε) = 325 (4.60), 410 141.6 (6/21), 138.1 (4-Mes), 138.0 (Mes), 137.7 (4-Tol), 137.3 (2-
(4.68), 730 nm (very broad, 3.94).
Mes), 137.1 (8/19), 136.0 (13/14), 135.7 (1-Tol), 132.7 (1/5), 131.1
(2-Tol), 130.2 (9/18), 129.9 (11/16), 129.1 (3-Tol), 128.3 (3-Mes),
123.6 (22), 21.5 (p-Tol), 21.3 (Me-4Ј), 20.9 (Me-2Ј) ppm. UV/Vis
(CH2Cl2): λmax (log ε) = 323 (4.59), 412 (4.66), 655 nm (4.01).
HRMS (ESI): m/z = 756.3456 (756.3412 for [C53H45N3S + H]+).
6,21-Diphenyl-11,16-di-p-tolyl-24-thia-3-aza-m-benziporphyrin (10):
Compound 10 was obtained analogously to 2 but in place of pyr-
role and aldehyde, 2,5-bis[hydroxyl(p-tolyl)methyl]thiophene (9)
(162 mg, 0.5 mmol) was used. Yield: 10 mg (3%). 1H NMR
(CDCl3, 298 K): δ = 8.20, 7.70 [A2B, (2 + 1) H, 4J(H,H) = 2.06 Hz,
X-ray Data Collection and Refinement: Crystals of 2 and 10 were
H(2/4), H(22)], 7.47–7.38 (m, 10 H, Ph),7.33, 7.26 [A2B2, (2×2) H, prepared by diffusion of n-hexane into a CH2Cl2 solution con-
3
3J(H,H) = 8.02, o/m-Tol], 7.28 [AB, 2 H, J(H,H) = 4.58 Hz, H(8/
19)], 7.18 [s, 2 H, H(13/14)], 6.66 [AB, 2 H, 3J(H,H) = 4.58 Hz,
H(9/18)], 2.42 (s, 6 H, p-Tol). 13C NMR (CD2Cl2, 298 K): δ = 172.7
(10/17), 156.2 (7/20), 154.9 (12/15), 152.4 (2/4), 143.9 (6/21), 142.2
tained in a thin tube (4 °C). Data collection: The measurement of
2 was performed with an Oxford Diffraction KM4 Xcalibur PX κ-
geometry diffractometer using Mo-Kα radiation (λ = 0.71073 Å), T
= 100 K, in the ω-scan mode, 2θmax = 72.36°; the measurement of
(1-Ph), 138.2 (4-Tol), 136.9 (8/19), 136.1 (13/14), 135.8, 135.1, 133.0 10 was performed with an Oxford Diffraction KM4 CCD κ-geome-
(Ph), 131.3 (2-Tol), 130.7 (9/18), 130.1 (3-Tol), 129.4 (Ph), 129.3,
128.2 (Ph), 119.4 (22), 21.4 (Me) ppm. UV/Vis (CH2Cl2): λmax
(log ε) = 319 (4.37), 352 (4.34), 412 (4.65), 661 nm (3.98). HRMS
(ESI): m/z = 672.2496 (672.2473 for [C47H33N3S+H]+).
try diffractometer using Mo-Kα radiation (λ = 0.71073 Å), T =
100 K, in the ω-scan mode, 2θmax = 56.92°. The structures were
solved by using direct methods with SHELXS-97 and refined
against |F2| using SHELXL-97 (G. M. Sheldrick, University of
Table 1. Crystal data for 2 and 10 with refinement details.
Compound
2
10
Crystals grown by
slow diffusion of n-hexane
into CH2Cl2 solution
dark green plate
0.4×0.2×0.1
C47H34N4·CH2Cl2
739.71
slow diffusion of n-hexane
into CH2Cl2 solution
dark green plate
0.8×0.5×0.4
C47H33N3S·CH2Cl2
756.75
Crystal habit
Crystal size [mm]
Empirical formula
Formula mass
a [Å]
10.205(3)
10.311(3)
b [Å]
c [Å]
13.074(3)
14.236(3)
12.935(3)
14.395(3)
α [°]
β [°]
82.55(3)
84.24(3)
82.41(3)
88.03(3)
γ [°]
82.84(3)
1861.8(8)
82.84(3)
1887.9(8)
V [Å3]
Z
2
2
dcalcd [gcm–3]
Crystal system
Space group
µ [mm–1]
1.319
triclinic
P1
0.216
1.331
triclinic
P1
0.267
¯
¯
Absorption correction
T [K]
Radiation: Mo-Kα [Å]
θ range [°]
hkl range
not applied
100(2)
0.71073
4.68–36.18
–15 Յ h Յ 16
–21 Յ k Յ 21
–23 Յ l Յ 23
not applied
100(2)
0.71073
2.86–28.46
–13 Յ h Յ 13
–16 Յ k Յ 16
–18 Յ l Յ 19
Reflections:
Measured
42754
9826
543/1
1.133
0.0826
0.2363
20403
6493
539/1
1.087
0.0585
0.1599
Unique [I/2σ(I)]
Parameters/restraints
S
[a]
R1
wR2
[a] R1 = Σ||Fo – Fc||/Σ|Fo|, wR2 = {Σ[w(Fo – Fc ) ]/Σ[w(Fo2)2]}1/2
.
2
2 2
Eur. J. Org. Chem. 2005, 5039–5048
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5047

R. Mys´liborski, L. Latos-Grazyn´ski
˙
FULL PAPER
[19] M. Ste˛pien´, L. Latos-Grazyn´ski, T. D. Lash, L. Szterenberg,
˙
Göttingen, Germany, 1997). For 2 final R1/wR2 indices [for
I Ͼ 2σ(I)]: 0.0826/0.2363; max./min. residual electron density:
+0.42/–0.47 eÅ–3, H atoms except inner H(22) and H(24) were
fixed in idealized positions using the riding model constraints. For
10 final R1/wR2 indices [for I Ͼ 2σ(I)]: 0.0585/0.1599; max./min.
residual electron density: +0.50/–0.45 eÅ–3, H atoms except inner
H(22) were fixed in idealized positions using the riding model
constraints. A disordered molecule of dichloromethane is present
in both structures. Crystal data are compiled in Table 1. CCDC-
271579 and -271580 contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Inorg. Chem. 2001, 40, 6892.
[20] M. Ste˛pien´, L. Latos-Grazyn´ski, L. Szterenberg, Inorg. Chem.
˙
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