Mendeleev Commun., 2012, 22, 284–286
Table 1 Parameters of intramolecular hydrogen bonds in the molecules
O(1)
C(6)
C(5)
C(22)
of compounds 4b,d.
C(21)
C(20)
C(2)
C(23)
C(24)
C(3)
N(1)–H(1)···O(3)
N(4)–H(4)···O(4)
C(4)
O(3)
O(2)
C(25)
N(4)
C(19)
C(1)
C(7)
Parameter
N(3)
S(1)
C(32)
C(31)
4b
4d
4b
4d
C(18)
N(1)
C(8)
O(6)
N(2)
C(26)
C(27)
C(15)
C(17)
d(N–H)/Å
d(H···O)/Å
ÐNHO/°
0.93(2)
1.89(9)
131.3(5)
2.61(0)
0.84(6)
1.99(2)
132.6(9)
2.63(9)
0.85(1)
1.97(4)
133.6(1)
2.63(4)
0.86(8)
1.96(9)
136.4(0)
2.66(6)
C(9)
C(30)
O(5)
C(13)
C(14)
C(16)
O(4)
C(29)
C(28)
C(10)
C(11)
C(12)
d(N–O)/Å
Figure 1 X-ray structure of 4b (thermal ellipsoids at 50% probability
level, ORTEP drawing).
F(8)
C(30)
F(7)
C(10)
C(9)
(see Online Supplementary Materials). X-ray study for products
4b,d was carried out.
F(6)
O(5)
F(5)
C(11)
C(13)
C(29)
C(15)
S(1)
C(12)
C(7)
N(1)
C(6)
C(27)
C(26)
O(6)
C(8)
In contrast to the previously obtained podand13 4a, compound
4b‡ has two independent coordination centres of b-amino enone
type, which are connected via central thiophene cycle and located
in the trans-position with respect to each other. The deviation
of C(9)C(11)C(13) plane of one phenylene fragment from the
C(18)N(3)C(22) plane containing thiophene cycle and another
phenylene is 24.8°, that makes the molecule non-planar. In crystal
compound 4b is s-trans,s-cis-conformer of EE-isomer of bis(amino
enone) tautomer (Figure 1).
C(16)
C(32)
C(34)
O(4)
C(25)
C(14)
N(2)
C(17)
N(4)
N(3)
C(19)
C(20)
C(18)
O(2)
C(24)
C(2)
O(3)
C(3)
C(31)
F(2)
C(23)
C(22)
C(21)
F(1)
C(4)
C(33)
C(1)
O(1)
C(5)
F(3)
F(4)
Figure 3 X-ray structure of 4d (thermal ellipsoids at 50% probability
level, ORTEP drawing)
There are two intramolecular hydrogen bonds (IMHB) in the
molecule with the participation of two NH groups of phenylene-
diamine moiety and two oxygen atoms of acetyl groups: N(1)–
H(1)···O(3) and N(4)–H(4)···O(4) (Table 1). Note that carbonyl
groups of acetyl fragments take part in the formation of IMHB
rather than ethoxycarbonyl groups as in the case of compound 4a.
The molecular packing (Figure 2) in the unit cell of compound
4b is organized by the two types of intermolecular hydrogen
bonding. The first type includes the interactions between atoms
O(4) and H(29A) of acetyl groups [2.66(7) Å] and the second type
is realized through the interaction of atoms O(1) and H(31B) of
ethoxycarbonyl groups of the adjacent molecules [2.89(9) Å].
To determine the influence of fluoroalkyl substituents on the
spatial structure of the molecule the X-ray analysis of 4d‡ was
carried out. Similarly to 4b, diethyl 2,2'-[2,5-thienylbis(amino-
methylidene-2-iminophenylene)]bis(3-oxo-4,4,5,5-tetrafluoro-
pentanoate) 4d in crystal is s-trans,s-cis-conformer of EE-iso-
mer of bis(amino enone) tautomer (Figure 3) and also has two
independent coordination centres. Acceptor properties of the fluoro-
alkyl group lead to the intramolecular H-bonding between NH
groupsofphenylenediaminemoietyandoxygenatoms of fluoroacyl
fragment: N(1)–H(1)···O(3) and N(4)–H(4)···O(4) (Table 1).
The presence of the polyfluoroalkyl groups in the molecule
changes the crystal packing so that the orientation of polyfluoro-
alkyl and hydrocarbon chains as a result of the intermolecular
interactions H···F [2.86(1) Å] becomes determinative (Figure 4).18
Unlike bis-azomethine 4b, where the intermolecular hydrogen
bonding makes the groups naturally equal, in the compound 4d
the interactions between fluorinated ethyl substituent and non-
fluorinated one take place. This reason accounts for the different
molecule packing.
H
H
2.89(9) Å
2.89(9) Å
O
O
2.66(7) Å
O
H
H
O
O
2.66(7) Å
O
2.89(9) Å
2.89(9) Å
H
H
Figure 2 The molecular packing of 4b (along the c axis).
‡
Crystallographic data for 4b: C32H32N4O6S, M = 600.68, monoclinic,
space group C2/c, a = 35.621(4), b = 10.5006(13) and c = 17.9570(9) Å,
b = 116.539(8)°, V = 6008.9(10) Å3, Z = 8, dcalc = 1.328 g cm–3, m(MoKa) =
= 0.159 cm–1, F(000) = 2528. A total number of 14194 reflections were
measured on an Xcalibur 3 diffractometer at 295(2) K [w/2q-scanning
technique, MoKa radiation (l = 0.71073 Å), graphite monochromator,
CCD detector], 5698 independent reflections (Rint = 0.0501), 2149 reflec-
tions with F0 > 4s(F0). The structure was solved by direct methods and
refined by the least-squares method with the use of SHELXL-9719
program package to R1 = 0.0416, wR2 = 0.0498 and GOOF = 0.998 [based
on reflections with I > 2s(I)].
Crystallographic data for 4d: C34H28F8N4O6S, M = 772.66, monoclinic,
space group C2/c, a = 65.3010(17), b = 5.4738(4) and c = 19.2195(13) Å,
b = 99.368(5)°, V = 6778.3(7) Å3, Z = 8, dcalc = 1.514 g cm–3, m(MoKa) =
= 0.192 cm–1, F(000) = 3168. A total number of 13122 reflections were
measured on an Xcalibur 3 diffractometer at 293(2) K [w/2q-scanning
technique, MoKa radiation (l = 0.71073 Å), graphite monochromator,
CCD detector], 6707 independent reflections (Rint = 0.0394), 3747
reflections with F0 > 4s(F0). The structure was solved by direct methods
and refined by the least-squares method with the use of SHELXL-9719
program package to R1 = 0.0561, wR2 = 0.1434 and GOOF = 1.004 [based
on reflections with I > 2s(I)].
H
2.84(8) Å
F
F
H
2.84(8) Å
2.84(8) Å
F
H
H
F
CCDC 848029 and 800075 contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The Cambridge
For details, see ‘Notice to Authors’, Mendeleev Commun., Issue 1, 2012.
2.84(8) Å
Figure 4 The molecular packing of 4d (along the c axis).
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