Hydrogen bonding in meso-4,5-diphenyl-3,6-diazaoctane-1,8-diol: The formation of one-dimensional linear chains of edge-fused rings

Article abstract of DOI:10.1107/S0108270106001053

The molecule of the title compound, C₁₈H₂₄N ₂O₂, resides on a crystallographic inversion centre. The molecule adopts a transoid conformation with respect to the central C - C single bond and is in the meso form.

Full text of DOI:10.1107/S0108270106001053

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Calhorda, 2000). The title compound, (I), is the intermediate
product obtained during the synthesis of macromolecular
metal complexes, which is an ongoing project in our labora-
tory. We present here the complete geometric characterization
of (I) in the solid state, together with an analysis of the
intermolecular interactions in the crystal structure.
ISSN 0108-2701
Hydrogen bonding in meso-4,5-di-
phenyl-3,6-diazaoctane-1,8-diol: the
formation of one-dimensional linear
chains of edge-fused rings
a
a
b
È
Muharrem DincËer, Namõk Ozdemir, * Sinan Saydam,
c
a
È
Ozer BekarogÆlu and Orhan Buyukgungor
È
È È
È
The structure of (I), together with the atom-labelling
scheme, is shown in Fig. 1. Both phenyl and 2-hydroxyethyl-
amino moieties adopt a transoid con®guration with respect to
the C7ÐC7i bond [symmetry code: (i) x + 21, y + 12, z],
which minimizes the steric hinderance in the molecule. The
compound crystallizes in space group C2/c and the molecules
reside on inversion centres located at the mid-point of the
C7ÐC7i bond. Selected bond lengths and angles are listed in
Table 1. The N1ÐC7 and N1ÐC8 imine bond lengths are
aDepartment of Physics, Arts and Sciences Faculty, Ondokuz Mayis University,
55139 Samsun, Turkey, bDepartment of Chemistry, Arts and Sciences Faculty, Fõrat
University, 23119 Elazõg, Turkey, and cDepartment of Chemistry, Arts and Sciences
Æ
Faculty, Istanbul Technical University, 34469 Maslak-Istanbul, Turkey
Correspondence e-mail: namiko@omu.edu.tr
Received 25 November 2005
Accepted 10 January 2006
Online 21 January 2006
Ê
1.478 (2) and 1.473 (2) A, respectively, and are in the accepted
The molecule of the title compound, C18H24N2O2, resides on a
crystallographic inversion centre. The molecule adopts a
transoid conformation with respect to the central CÐC single
bond and is in the meso form. A polarimetric study of the
compound did not show any optical activity, indicating that the
compound is a racemic mixture entirely consistent with the
centrosymmetric C2=c space group. In the molecule, there is
one intramolecular NÐHÁ Á ÁO interaction, resulting in the
formation of a ®ve-membered ring. In the crystal structure,
intermolecular OÐHÁ Á ÁN and CÐHÁ Á ÁO interactions are also
observed. These interactions form an R22(9) ring and one-
dimensional linear chains of edge-fused rings running parallel
to the [010] direction, which stabilize the crystal packing.
range for covalent single bonds (Allen et al., 1987). The ÈNC
torsion angle (C7ÐN1ÐC8ÐC9) is 171.2 (2)ꢀ, which shows
that the conformation about the N1ÐC8 bond is (+)anti-
periplanar. However, the ÈCC torsion angle (N1ÐC8ÐC9Ð
O1) is 54.5 (2)ꢀ, indicating that the conformation about the
C8ÐC9 bond is ( )synclinal. As can be seen from these
torsion angles, the C7ÐN1ÐC8ÐC9 backbone is in a zigzag
chain form. However, the hydroxy O atom does not lie in the
plane of this chain and is oriented towards the imine N atom.
This orientation leads to an intramolecular NÐHÁ Á ÁO
hydrogen bond, resulting in the formation of a ®ve-membered
ring.
Comment
The generation of different types of packing motifs in crys-
talline lattices has been illustrated in detail in the literature.
Hydrogen-bonding motifs play an important role in the
interaction, recognition and conformation of both small and
large molecules, e.g. in biologically active molecules (Watson
& Crick, 1953; Zeng et al., 2000). These motifs have frequently
been used as supramolecular synthons to direct solid-state
È
structures (crystal engineering; Steiner, 2002; Aakeroy &
Seddon, 1993) and for the synthesis of complex supramole-
cules. Molecular assembly in a crystal is predominantly
governed by intermolecular forces, conventionally described
by strong and directional NÐHÁ Á ÁO, OÐHÁ Á ÁO and OÐ
HÁ Á ÁN hydrogen bonds (Desiraju, 2002). In molecules lacking
these hydrogen-bond donors and acceptors, other types of
weak and less directional forces, such as CÐHÁ Á ÁO, CÐHÁ Á Áꢀ
and ꢀ±ꢀ interactions, become important in generating supra-
molecular architectures (Desiraju & Steiner, 1999; Hunder &
Sanders, 1990; Nishio et al., 1998; Umezawa et al., 1998;
Figure 1
The molecule of (I), showing the atom-labelling scheme and 50%
probability displacement ellipsoids. The intramolecular NÐHÁ Á ÁO
hydrogen bonds are represented by dashed lines. [Symmetry code: (i)
x + 12, y + 12, z.]
Acta Cryst. (2006). C62, o89±o91
DOI: 10.1107/S0108270106001053
# 2006 International Union of Crystallography o89

organic compounds
In the crystal lattice of (I), the 1,2-diphenylethane part of
the molecule resides along the a axis of the unit cell, while two
symmetry-related 2-(methylamino)ethanol parts of the mol-
ecule lie along the c axis of the unit cell. In this arrangement,
the molecules are connected to each other by means of
hydrogen bonds between 2-hydroxyethylamino tails. There
are no intermolecular interactions between molecules in the a
or c direction. In the construction of this connection, two
2-hydroxyethylamino tails of the 21 screw symmetry-related
molecules, which interdigitate with the 2-hydroxyethylamino
tails of two neighbouring molecules translated linearly along
the b axis of the unit cell, play an active role, in which each tail
is connected to neighbouring tails by means of one OÐHÁ Á ÁN
hydrogen bond and one leading CÐHÁ Á ÁO hydrogen bond
(Taylor & Kennard, 1982; Steiner & Desiraju, 1998), so the
hydroxy O atom acts as both donor and acceptor in two
other signi®cant interactions, such as ꢀ±ꢀ and CÐHÁ Á Áꢀ
interactions, in the crystal structure of (I).
Experimental
The synthesis of the title compound was performed with minor
modi®cations of the literature method of KocËak (2000). Benzalde-
hyde (10.6 g, 0.1 mol) and 2-aminoethanol (6.1 g, 0.1 mol) were
mixed and heated in a water bath for 1 h. The mixture was then
cooled to room temperature and a mixture of aluminium amalgam
(7.0 g) in ether (400 ml) and distilled water (7.5 ml) was added slowly.
The reaction mixture was kept at room temperature for 24 h with
stirring and the precipitate which formed was removed by suction
®ltration. The compound was extracted from the precipitate with
benzene by the use of a Soxhlet extractor. The white crystalline
compound which formed was removed by ®ltration and recrystallized
from ethanol [yield: 6.90 g, 46%; m.p. 362 K, literature value 363 K
(Jeyaprabha et al., 2005)]. 1H NMR (DMSO-d6): ꢁ 7.16 (m, 10H, Ar-
H), 4.19 (t, 2H, OH, D2O exchangeable), 3.77 (s, 2H, >CHÐ), 3.31 (t,
4H, OÐCH2Ð), 2.31 (t, 4H, NÐCH2), 1.92 (s, 2H, ÐNHÐ, D2O
exchangeable); characteristic IR bands (cm 1) are: 3410 [ꢂ(OÐH)],
2800±3000 [aliphatic ꢂ(CÐH)], 3000±3100 [aromatic ꢂ(CÐH)], 3292
[ꢂ(NÐH)], 1619 [ꢂ(C N)]. The compound is soluble in common
organic solvents such as benzene, toluene, ethanol and methanol.
different hydrogen bonds. Atom O1 acts as a hydrogen-bond
,
1
2
donor, via atom H1O, to atom N1 at ( x + 32, y
z + 32),
while atom C8 acts as a hydrogen-bond donor, via atom H8B,
to atom O1 at ( x + 32, y
,
z + 32), so generating a
1
2
centrosymmetric R22(9) ring (Bernstein et al., 1995). The
geometric parameters of the CÐHÁ Á ÁO bonds are well within
the accepted ranges (Desiraju, 1991, 1996) and the CÐHÁ Á ÁO
angle is close to the optimally observed value of 160ꢀ. A
similiar type of graph set produced by intermolecular inter-
actions of these types is also observed in the literature (Howie
et al., 2003). Propagation of this hydrogen-bonding motif
generates one-dimensional linear chains of edge-fused rings
running parallel to the [010] direction (Fig. 2). In addition, as
can be seen in Fig. 2, this arrangement forms another one-
dimensional linear chain of edge-fused rings running parallel
to the [010] direction between two chains of fused R22(9) rings
[graph set R44(16)]. The detailed geometry of the intra- and
intermolecular interactions is given in Table 2. There are no
Crystal data
3
C18H24N2O2
Mr = 300.39
Monoclinic, C2=c
Dx = 1.217 Mg m
Mo Kꢄ radiation
Cell parameters from 4012
re¯ections
Ê
a = 17.585 (2) A
ꢅ = 2.4±27.9ꢀ
ꢆ = 0.08 mm
T = 296 K
Ê
b = 6.8615 (5) A
1
Ê
c = 13.9453 (16) A
ꢃ = 103.035 (10)ꢀ
3
Ê
V = 1639.3 (3) A
Z = 4
Prism, colourless
0.57 Â 0.51 Â 0.44 mm
Data collection
Stoe IPDS-2 diffractometer
! scans
4103 measured re¯ections
1597 independent re¯ections
1388 re¯ections with I > 2ꢇ(I)
Rint = 0.096
ꢅmax = 26.0ꢀ
h = 16 ! 21
k = 8 ! 8
l = 17 ! 17
Re®nement
Re®nement on F2
R[F2 > 2ꢇ(F2)] = 0.053
wR(F2) = 0.148
w = 1/[ꢇ2(Fo2) + (0.0838P)2
+ 0.3333P]
2
where P = (Fo + 2Fc2)/3
S = 1.09
1597 re¯ections
148 parameters
All H-atom parameters re®ned
(Á/ꢇ)max < 0.001
3
Ê
Áꢈmax = 0.31 e A
3
Ê
0.20 e A
Áꢈmin
=
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
O1ÐC9
N1ÐC8
N1ÐC7
1.408 (2)
1.4732 (16)
1.4781 (16)
C1ÐC7
C7ÐC7i
C8ÐC9
1.512 (2)
1.541 (2)
1.512 (2)
C8ÐN1ÐC7
C6ÐC1ÐC7
C2ÐC1ÐC7
N1ÐC7ÐC1
111.95 (10)
120.45 (14)
121.35 (13)
109.75 (10)
N1ÐC7ÐC7i
C1ÐC7ÐC7i
N1ÐC8ÐC9
O1ÐC9ÐC8
109.20 (13)
112.29 (13)
110.78 (12)
113.23 (12)
Symmetry code: (i) x ‡ 32; y ‡ 21; z ‡ 1.
The H atoms were located in a difference map and re®ned
Figure 2
Part of the crystal structure of (I), showing the formation of one-
dimensional linear chains of edge-fused rings along [010].
Ê
Ê
isotropically, with CÐH = 0.93 (3)±1.036 (16) A, OÐH = 0.91 (3) A
Ê
and NÐH = 0.922 (16) A.
ꢁ
o90 DinËcer et al.
C18H24N2O2
Acta Cryst. (2006). C62, o89±o91

organic compounds
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
Table 2
Hydrogen-bond geometry (A, ).
ꢀ
Ê
Calhorda, M. J. (2000). Chem. Commun. pp. 801±810.
Desiraju, G. R. (1991). Acc. Chem. Res. 24, 290±296.
Desiraju, G. R. (1996). Acc. Chem. Res. 29, 441±449.
Desiraju, G. R. (2002). Acc. Chem. Res. 35, 565±573.
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural
Chemistry and Biology. New York: Oxford University Press Inc.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837±838.
Howie, R. A., Jabbar, A., Lewis, J. R., Nizami, S. S. & Ritchie, C. F. (2003). Acta
Cryst. C59, o516±o519.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N1ÐH1Á Á ÁO1
0.92 (2)
0.91 (3)
0.99 (2)
2.48 (2)
1.95 (3)
2.60 (2)
2.901 (2)
2.859 (2)
3.548 (2)
107.8 (11)
175 (2)
161 (2)
O1ÐH1OÁ Á ÁN1ii
C8ÐH8BÁ Á ÁO1ii
Symmetry code: (ii) x ‡ 32; y
;
z ‡ 32.
1
2
Data collection: X-AREA (Stoe & Cie, 2002); cell re®nement:
X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s)
used to solve structure: SHELXS97 (Sheldrick, 1997); program(s)
used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular
graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to
prepare material for publication: WinGX (Farrugia, 1999) and
PLATON (Spek, 2003).
Hunder, C. A. & Sanders, J. K. M. (1990). J. Am. Chem. Soc. 112, 5525±5534.
Jeyaprabha, C., Sathiyanarayanan, S. & Venkatachari, G. (2005). Appl. Surf.
Sci. 246, 108±116.
KocËak, M. (2000). Transition Met. Chem. 25, 231±233.
Nishio, M., Hirota, M. & Umezawa, Y. (1998). In The CÐHÁ Á Áꢀ Interaction:
Evidence, Nature and Consequences. New York: Wiley±VCH.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
È
Gottingen, Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
Steiner, T. (2002). Angew. Chem. Int. Ed. 41, 48±76.
Steiner, T. & Desiraju, G. R. (1998). J. Chem. Soc. Chem. Commun. pp. 891±
892.
Stoe & Cie (2002). X-AREA (Version 1.18) and X-RED32 (Version 1.04). Stoe
& Cie, Darmstadt, Germany.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GZ1025). Services for accessing these data are
described at the back of the journal.
Taylor, R. & Kennard, O. (1982). J. Am. Chem. Soc. 104, 5063±5070.
Umezawa, Y., Tsuboyama, S., Honda, K., Uzawa, J. & Nishio, M. (1998). Bull.
Chem. Soc. Jpn, 71, 1207±1213.
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ꢁ
Acta Cryst. (2006). C62, o89±o91
DinËcer et al. C18H24N2O2 o91