Benzyl N,N-bis-[2-(pentafluoroanilino)-ethyl]-carbamate

Article abstract of DOI:10.1107/S0108270107057939

The title compound, C24H17F10N3O2, exhibits intra-molecular N - H...O hydrogen bonding, as well as intra-molecular Ar...Ar^F face-to-face inter-actions. The mol-ecules are linked together by N - H...F - C hydrogen bonds, forming chains parallel to the a axis. Adjacent symmetry-related chains are combined in double zipper-like ribbons by parallel Ar^F...Ar^F offset π-stacking inter-actions. International Union of Crystallography 2007.

Full text of DOI:10.1107/S0108270107057939

organic compounds
Acta Crystallographica Section C
Crystal Structure
As expected for carbamate derivatives, the C11ÐN1 and
C11ÐO2 bond lengths of (I) are almost equal [1.356 (2) and
Ê
1.351 (2) A, respectively] due to strong conjugation effects
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ISSN 0108-2701
(Fig. 1). This causes the central carbamate group (N1/O1/O2/
C11), together with the adjacent ꢁ-C atoms (C12/C21/C31), to
Ê
be planar within 0.110 (1) A. Compound (I) contains three
Benzyl N,N-bis[2-(pentafluoro-
anilino)ethyl]carbamate
outward aryl substituents. One of them, ¯uorinated ring C23±
C28, is linked to the carbamate fragment by an NÐHÁ Á ÁO
Ê
hydrogen bond [2.07 (2) A]. To the best of our knowledge,
similar hydrogen bonding has been observed only once before,
in the structure of 2-(penta¯uorophenylamino)-pent-2-en-4-
one, C6F5NHC(Me) CHCOMe (Gordon et al., 2002). The
rotation of the C23±C28 aryl ring around the N2ÐC23 bond
seems to be restricted due to noticeable conjugation with
neighbouring amine atom N2. This is con®rmed by the C24Ð
C23ÐN2ÐH2 torsion angle [ 5.6 (17)ꢀ] and by suf®cient
Andrei V. Churakov,a* Sergey S. Karlov,b Elmira Kh.
Lermontova,a Galina S. Zaitsevab and Judith A. K.
Howardc
aN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of
Sciences, 31 Leninskii prospect, Moscow 119991, Russian Federation, bDepartment
of Chemistry, Moscow State University, Leninskie Gory, Moscow 119992, Russian
Federation, and cDepartment of Chemistry, University of Durham, Science
Laboratories, South Road, Durham DH1 3LE, England
Ê
shortening of the N2ÐC23 bond distance [1.375 (2) A]. The
other two aryl groups, C13±C18 and C33±C38, are nearly
parallel [dihedral angle = 11.56 (6)ꢀ] and are bonded by the
well known ArÁ Á ÁArF face-to-face interaction (Dunitz, 2004),
Correspondence e-mail: churakov@igic.ras.ru
Received 22 September 2007
Accepted 11 November 2007
Online 30 November 2007
Ê
with a centroid-to-centroid separation of 3.749 A and a
displacement angle (Janiak, 2000) of 15.0ꢀ. Thus, the confor-
mation of the molecule of (I) is completely predetermined by
the aforementioned intramolecular interactions.
The title compound, C24H17F10N3O2, exhibits intramolecular
NÐHÁ Á ÁO hydrogen bonding, as well as intramolecular
ArÁ Á ÁArF face-to-face interactions. The molecules are linked
together by NÐHÁ Á ÁFÐC hydrogen bonds, forming chains
parallel to the a axis. Adjacent symmetry-related chains are
combined in double zipper-like ribbons by parallel ArFÁ Á ÁArF
offset ꢀ-stacking interactions.
In the crystal structure of (I), translationally related mol-
ecules are linked together by NÐHÁ Á ÁFÐC hydrogen bonds
Ê
[2.17 (2) A], forming chains parallel to the a axis (Fig. 2). The
low propensity of organic ¯uorine to participate in hydrogen
bonding has been the subject of several reports (Howard et al.,
Comment
Interest in tris-amine derivatives, RN(CH2CH2NHR0)2, has
grown steadily over the past two decades. These ligands are
widely used to stabilize unusual metal oxidation states and
Â
coordination geometry around various metal centres (Faure et
al., 1999; Ward et al., 2002; Gade & Mountford, 2001). Their
complexes were applied in several catalytic processes (Gade &
Mountford, 2001; Schrodi et al., 2001). Particular attention has
been paid to the complexes of ¯uorinated tris-amine ligands
Figure 1
The structure of (I), showing the atom-numbering scheme. Displacement
ellipsoids are drawn at the 50% probability level and H atoms are shown
as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds
and the ArÁ Á ÁArF face-to-face interaction.
due to the electron-withdrawing properties of the C6F5 group
and additional secondary ArÐFÁ Á ÁM interactions (Schrock et
al., 1998; Cochran et al., 2000). We report here the structure of
the title mixed aryl/penta¯uoroaryl substituted bis(amino-
ethyl)carbamate, (I).
Figure 2
The hydrogen-bonded (dashed lines) chains in (I) parallel to the a axis. H
atoms not involved in hydrogen bonds have been omitted.
Acta Cryst. (2007). C63, o761±o762
DOI: 10.1107/S0108270107057939
# 2007 International Union of Crystallography o761

organic compounds
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
N1ÐC11
N2ÐC23
N3ÐC33
1.355 (2)
1.375 (2)
1.379 (2)
O1ÐC11
O2ÐC11
1.224 (2)
1.351 (2)
C11ÐN1ÐC31
C11ÐN1ÐC21
C31ÐN1ÐC21
C23ÐN2ÐC22
C33ÐN3ÐC32
124.19 (15)
117.67 (15)
118.13 (14)
121.97 (16)
125.41 (16)
C11ÐO2ÐC12
O1ÐC11ÐO2
O1ÐC11ÐN1
O2ÐC11ÐN1
113.69 (14)
123.02 (16)
124.25 (17)
112.72 (15)
C24ÐC23ÐN2ÐH2
5.6 (17)
Table 2
Hydrogen-bond geometry (A, ).
ꢀ
Ê
Figure 3
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Double zipper-like chains parallel to the a axis. Dashed lines indicate
hydrogen bonds and ArFÁ Á ÁArF offset ꢀ-stacking interactions. H atoms
not involved in hydrogen bonds have been omitted.
N2ÐH2Á Á ÁO1
0.86 (2)
0.86 (2)
2.07 (2)
2.17 (2)
2.886 (2)
2.9282 (19)
157 (2)
147 (2)
N3ÐH3Á Á ÁF37i
Symmetry code: (i) x 1; y; z.
1996; Dunitz & Taylor, 1997). However, in this case, this
unusual hydrogen bonding may result from the high acidity of
atom H3 caused by the neighbouring highly electron-with-
drawing C6F5 group. Adjacent symmetry-related chains are
combined in double zipper-like ribbons by parallel ArFÁ Á ÁArF
offset ꢀ-stacking interactions (Fig. 3). The interplanar
H atoms were located in a difference Fourier map and re®ned
freely.
Data collection: SMART (Bruker, 2003); cell re®nement: SAINT
(Bruker, 2003); data reduction: SAINT; program(s) used to solve
structure: SHELXTL (Bruker, 2003); program(s) used to re®ne
structure: SHELXTL; molecular graphics: SHELXTL; software used
to prepare material for publication: SHELXTL.
F
F
Ê
Ar Á Á ÁAr distance is 3.8191 (4) A, the centroid-to-centroid
ꢀ
Ê
separation is 3.902 A and the displacement angle is 25.0 .
Finally, these chains are linked by intermolecular ArÁ Á ÁArF
interactions, forming a complex three-dimensional network.
In conclusion, the molecular geometry and crystal packing
of (I) are determined by the different types of secondary
bonding formed by the pena¯uoroanilino groups.
AVC thanks the Royal Society of Chemistry, UK, for an
International Travel Grant. The authors are grateful to the
RFBR (grant No. 06-03-33032a) for ®nancial support.
Experimental
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SF3060). Services for accessing these data are
described at the back of the journal.
The title compound was obtained as a side product from an alkylation
reaction of HN(CH2CH2NHC6F5)2 with benzyl chloride in the
presence of K2CO3, according to the general method described by
Cochran et al. (2000). Crystals were obtained by recrystallization
from toluene.
References
Crystal data
Bruker (2003). SADABS, SAINT, SHELXTL and SMART. Bruker AXS Inc.,
Madison, Wisconsin, USA.
Cochran, F. V., Bonitatebus, P. J. Jr & Schrock, R. R. (2000). Organometallics,
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3
Ê
C24H17F10N3O2
Mr = 569.41
Orthorhombic, Pbca
a = 7.6382 (7) A
b = 14.9272 (15) A
Ê
c = 40.857 (4) A
Data collection
V = 4658.4 (8) A
Z = 8
Mo Kꢁ radiation
1
Ê
ꢂ = 0.16 mm
T = 120 (2) K
Ê
Â
Â
Faure, J.-L., Gornitzka, H., Reau, R., Stalke, D. & Bertrand, G. (1999). Eur. J.
Inorg. Chem. pp. 2295±2299.
0.30 Â 0.20 Â 0.20 mm
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Bruker SMART 1K diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
Tmin = 0.925, Tmax = 1.000
(expected range = 0.896±0.969)
25323 measured re¯ections
5603 independent re¯ections
4174 re¯ections with I > 2ꢃ(I)
Rint = 0.048
Re®nement
R[F2 > 2ꢃ(F2)] = 0.048
wR(F2) = 0.102
S = 1.04
420 parameters
All H-atom parameters re®ned
3
Ê
Áꢄmax = 0.25 e A
Ward, B. D., Dubberley, S. R., Maisse-FrancËois, A., Gade, L. H. & Mountford,
P. (2002). J. Chem. Soc. Dalton Trans. pp. 4649±4657.
3
Ê
0.27 e A
5603 re¯ections
Áꢄmin
=
ꢁ
o762 Churakov et al. C24H17F10N3O2
Acta Cryst. (2007). C63, o761±o762