Hydrogen-bonded chains in 2,2,2-trichloro-N,N′-bis(4-methoxyphenyl)- ethane-1,1-diamine and a three-dimensional hydrogen-bonded framework in 2,2,2-trichloro-N,N′-bis(4-chlorophenyl)-ethane-1,1-diamine

Article abstract of DOI:10.1107/S0108270107041546

In 2,2,2-trichloro-N,N′-bis-(4-methoxy-phenyl)-ethane-1,1-di-amine, C16H17Cl3N2O2, mol-ecules are linked into helical chains by N - H...O hydrogen bonds. Mol-ecules of 2,2,2-trichloro-N,N′-bis-(4-chloro-phenyl)- ethane-1,1-diamine, C14H11-Cl5N2, are conne

Full text of DOI:10.1107/S0108270107041546

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
formed by a combination of two independent CÐHÁ Á ÁCl
hydrogen bonds and one ClÁ Á ÁCl interaction.
In compounds (I) and (II), the trichloroethane-1,1-diamine
fragments adopt a gauche conformation with respect to the
C1ÐC2 bonds, similar to the situation in (III) and (IV). In
(II), the dihedral angle between the planes of the two aromatic
rings is 88.01 (2)ꢀ, indicating that these benzene rings are
perpendicular to one another. The orientation of the two rings
is marginally different from that in (I), where the dihedral
angle is 76.37 (3)ꢀ. Selected geometric parameters for (I) and
(II) are listed in Tables 1 and 3, respectively. The C2ÐCl1
bond in (I) is longer than the other CÐCl bonds in compounds
(I)±(IV), probably due to the presence of an intramolecular
N2ÐH2DÁ Á ÁCl1 hydrogen bond (Table 2). The same variation
of ca 9ꢀ occurs within each pair of exocyclic CÐCÐO valence
ISSN 0108-2701
Hydrogen-bonded chains in 2,2,2-
trichloro-N,N0-bis(4-methoxyphenyl)-
ethane-1,1-diamine and a three-
dimensional hydrogen-bonded frame-
work in 2,2,2-trichloro-N,N0-bis(4-
chlorophenyl)ethane-1,1-diamine
Zhen-Feng Zhang,a* Jian-Hua Qin,b Si-Qian Wangc and
Gui-Rong Qua
aCollege of Chemistry and Environmental Science, Henan Normal University,
Xinxiang 453007, People's Republic of China, bCollege of Chemistry, Luoyang
Normal University, Xinxiang 453007, People's Republic of China, and cInstitute of
Chemistry, Chinese Academy of Sciences, Beijing 100080, People's Republic of
China
Correspondence e-mail: zzf5188@sohu.com
Received 7 August 2007
Accepted 23 August 2007
Online 13 October 2007
In 2,2,2-trichloro-N,N0-bis(4-methoxyphenyl)ethane-1,1-di-
amine, C16H17Cl3N2O2, molecules are linked into helical
chains by NÐHÁ Á ÁO hydrogen bonds. Molecules of 2,2,2-tri-
chloro-N,N0-bis(4-chlorophenyl)ethane-1,1-diamine, C14H11-
Cl5N2, are connected into a three-dimensional framework by
two independent ClÁ Á ÁCl interactions and one CÐHÁ Á ÁCl
hydrogen bond.
Figure 1
The molecule of (I), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 50% probability level and H atoms are shown
as small spheres of arbitrary radii.
Comment
As a continuation of our structural studies of bis(aryl-
amino)trichloromethylmethanes (Zhang et al., 2007), we
report here the molecular and supramolecular structures of
2,2,2-trichloro-N,N0-bis(4-methoxyphenyl)ethane-1,1-diamine,
(I) (Fig. 1), and 2,2,2-trichloro-N,N0-bis(4-chlorophenyl)-
ethane-1,1-diamine, (II) (Fig. 2), where the supramolecular
aggregations prove to be different from those in 2,2,2-
trichloro-N,N0-diphenylethane-1,1-diamine, (III), and 2,2,2-
trichloro-N,N0-bis(4-methylphenyl)ethane-1,1-diamine, (IV),
which we reported recently (Zhang et al., 2007). In (III), the
two-dimensional supramolecular structure is built from CÐ
HÁ Á ÁCl and CÐHÁ Á Áꢀ(arene) contacts, while the crystal
structure of (IV) exhibits one-dimensional double columns
Figure 2
The molecular structure of (II), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level and H
atoms are shown as small spheres of arbitrary radii.
o622 # 2007 International Union of Crystallography
DOI: 10.1107/S0108270107041546
Acta Cryst. (2007). C63, o622±o625

organic compounds
angles in (I), as is well established for 4-methoxyphenyl units
(Seip & Seip, 1973). These deviations suggest the presence of
repulsive interactions between O2ÐCH3 and atom H14 (the
cating that atom C1 lies near the N1/C9±C14 plane. However,
Ê
atom C1 in (I) is displaced by 0.249 (3) and 0.265 (4) A from
the N2/C3±C8 and N1/C10±C15 planes, respectively.
The two NH H atoms in each molecule have very similar
chemical shifts and coupling constants with the adjacent CH
hydrogen [J = 8.8 Hz in (I) and 8.4 Hz in (II)], suggesting that,
in solution at room temperature, on the NMR timescale, the
molecules relax to a conformation where the two HÐNÐCÐ
H torsion angles have similar average magnitudes, though the
two HÐNÐCÐH torsion angles in each molecule in the solid
state are different [ 169 and 128ꢀ for H1DÐN1ÐC1ÐH1
and H2DÐN2ÐC1ÐH1, respectively, in (I), and 155 and
128ꢀ for H2DÐN2ÐCÐH1 and H1DÐN1ÐC1ÐH1,
respectively, in (II)].
Ê
distance between the methyl C atom and H14 is 2.61 A) or
O1ÐCH3 and H7 (the distance between the methyl C atom
Ê
and H7 is 2.55 A). The methoxy group on C6 is effectively
coplanar with the C3±C8 ring, as shown by the C7ÐC6ÐO1Ð
C9 torsion angle of 4.3 (4)ꢀ. The situation is, however,
different for the methoxy group on C13, where the torsion
angle is 21.3 (5)ꢀ and the methyl C atom is displaced from
Ê
the plane of the C10±C15 aryl ring by 0.408 (4) A. In
compound (II), the C1ÐN1ÐC9ÐC14 and C1ÐN2ÐC3ÐC4
torsion angles are 2.1 (3) and 9.5 (3)ꢀ, respectively, indi-
In compound (I), the molecules are linked into helical
chains by a single NÐHÁ Á ÁO hydrogen bond (Table 2). Atom
N1 in the molecule at (x, y, z) acts as a hydrogen-bond donor
1
to methoxy atom O1 in the molecule at (
x, y
12, z).
then generates a
2
1
Propagation by an a-glide plane at x =
C(9) (Bernstein et al., 1995) chain running parallel to the [010]
direction (Fig. 3). Eight chains of this type pass through each
4
Figure 5
Part of the crystal structure of (II), showing the formation of a C(9) chain
1
4
parallel to the [1, y, ] direction. Atoms marked with an asterisk (*) or
ampersand (&) are at the symmetry positions (x + 1, y 1, z) and (x 1,
y + 1, z), respectively.
Figure 3
Part of the crystal structure of (I), showing the formation of a C(9) helical
chain parallel to the [010] direction. For the sake of clarity, H atoms not
involved in the motif shown have been omitted. Atoms marked with an
1
2
1
asterisk (*) or ampersand (&) are at the symmetry positions (
1
x, y
,
2
z) and (
x, 12 + y, z), respectively.
2
Figure 4
Figure 6
Part of the crystal structure of (II), showing the formation of a C(5) chain
Part of the crystal structure of (II), showing the formation of a C(9) chain
parallel to the [110] direction. Atoms marked with an asterisk (*) or
ampersand (&) are at the symmetry positions (x 1, y 1, z) and (x + 1,
y + 1, z), respectively.
of rings along the [010] direction. Atoms marked with an asterisk (*) or
1
1
2
ampersand (&) are at the symmetry positions (2 x, + y,
1
z) and
2
(2 x,
+ y, 12 z), respectively.
2
ꢁ
Acta Cryst. (2007). C63, o622±o625
Zhang et al.
C16H17Cl3N2O2 and C14H11Cl5N2 o623

organic compounds
3
8
3
8
unit cell; four of these, running along the ( 14, y, ), (43, y, ),
Data collection
7
7
(
14, y, ) and (34, y, ) directions, are related to each other by
translational symmetry operations, and they are related by an
Nonius KappaCCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.822, Tmax = 0.876
23826 measured re¯ections
3233 independent re¯ections
2571 re¯ections with I > 2ꢄ(I)
Rint = 0.066
8 8
a-glide plane to the other four chains running along the
14, y, 18), (34, y, 18), ( 41, y, 85) and (43, y, 58) directions. There are no
(
direction-speci®c interactions between adjacent chains.
There are no aromatic ꢀ±ꢀ stacking interactions in the
structure of (II); instead, the molecules are linked into a
complex three-dimensional framework by a combination of
two independent ClÁ Á ÁCl interactions and one CÐHÁ Á ÁCl
hydrogen bond (Table 4). However, the structure of (II) can
be easily analyzed in terms of three one-dimensional
substrutures. In the ®rst substructure, atom Cl5 in the mol-
ecule at (x, y, z) forms an intermolecular interaction with
Re®nement
R[F2 > 2ꢄ(F2)] = 0.046
wR(F2) = 0.109
S = 1.05
210 parameters
H-atom parameters constrained
3
Ê
Áꢅmax = 0.36 e A
3
Ê
0.39 e A
3233 re¯ections
Áꢅmin
=
Table 1
Selected geometric parameters (A, ) for (I).
ꢀ
Ê
Ê
trichloromethyl atom Cl3 [Cl5Á Á ÁCl3 = 3.343 (2) A] in the
Cl1ÐC2
1.790 (3)
O2ÐC16
1.396 (4)
molecule at (x + 1, y, z). Propagation by translation then
generates a C(9) chain running along the [110] direction
(Fig. 4). In the same way, the second substructure is
constructed by way of a ClÁ Á ÁCl interaction: atom Cl4 in the
molecule at (x, y, z) forms another independent inter-
molecular interaction with trichloromethyl atom Cl2
C10ÐN1ÐC1
C3ÐN2ÐC1
N1ÐC1ÐC2
C8ÐC3ÐN2
O1ÐC6ÐC5
125.2 (2)
121.8 (2)
111.4 (2)
123.6 (2)
115.8 (2)
O1ÐC6ÐC7
125.1 (2)
125.2 (2)
117.6 (2)
125.1 (3)
116.1 (3)
C15ÐC10ÐN1
C11ÐC10ÐN1
C14ÐC13ÐO2
O2ÐC13ÐC12
Ê
[Cl4Á Á ÁCl2 = 3.469 (2) A] in the molecule at (x + 1, y 1, z), so
C3ÐN2ÐC1ÐN1
Cl3ÐC2ÐC1ÐN2
Cl2ÐC2ÐC1ÐN1
C1ÐN2ÐC3ÐC8
N2ÐC3ÐC4ÐC5
67.7 (3)
177.96 (18)
174.51 (18)
13.1 (4)
C9ÐO1ÐC6ÐC7
4.3 (4)
13.6 (4)
179.6 (3)
179.6 (3)
C1ÐN1ÐC10ÐC15
N1ÐC10ÐC11ÐC12
C11ÐC12ÐC13ÐO2
forming by translation a C(9) chain parallel to the [110]
direction (Fig. 5). In the third substructure, atom H8 in the
molecule at (x, y, z) acts as a hydrogen-bond donor to atom
Cl4 in the molecule at ( x + 2, y + 12, z + 21), thus generating a
178.9 (2)
1
4
C(5) chain along the (1, y, ) direction and generated by a 21
1
screw axis along (1, y, ) (Fig. 6). The combination of these
three chain motifs links molecules of (II) into a three-
dimensional framework.
4
Table 2
Hydrogen-bond and short-contact geometry (A, ) for (I).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N2ÐH2DÁ Á ÁCl1
0.86
0.86
2.67
2.54
3.030 (3)
3.150 (3)
107
128
N1ÐH1DÁ Á ÁO1i
Symmetry code: (i)
Experimental
x
12; y 12; z.
For the synthesis of (I), chloral hydrate (16.5 g, 0.1 mol) and
4-methoxyaniline (0.2 mol) were mixed in ethyl acetate (25±30 ml)
and heated until dissolution of the solid occurred. Cooling of the hot
solution, followed by slow evaporation of the solvent at room
temperature, yielded the crude product (yield 86%). Single crystals of
(I) were obtained by recrystallization from CH2Cl2. 1H NMR
(DMSO, 400 MHz): ꢁ 6.71 (m, 8H, 2Ar), 5.63 (d, J = 8.8 Hz, 2H,
2NH), 5.42 (t, J = 8.7 Hz, 1H, CH), 3.59 (s, 6H, 2CH3). Compound (II)
was synthesized by heating with stirring a mixture of chloral hydrate
(16.5 g, 0.1 mol), freshly distilled 4-chloroaniline (0.2 mol) and ethyl
acetate (25±30 ml) until dissolution of the solid occurred. Cooling of
the hot solution and slow evaporation of the solvent at room
temperature yielded a crystalline product (yield 82%). Single crystals
of (II) were obtained by recrystallization from hot dimethyl sulfoxide.
1H NMR (DMSO, 400 MHz): ꢁ 6.93 (m, 8H, 2Ar), 6.32 (d, J = 8.4 Hz,
2H, 2NH), 5.73 (t, J = 8.4 Hz, 1H, CH).
Compound (II)
Crystal data
3
Ê
C14H11Cl5N2
Mr = 384.50
V = 1605.3 (3) A
Z = 4
Orthorhombic, P212121
Ê
Mo Kꢂ radiation
1
a = 6.0186 (6) A
Ê
ꢃ = 0.90 mm
T = 291 (2) K
b = 8.0624 (8) A
Ê
c = 33.082 (3) A
0.42 Â 0.31 Â 0.28 mm
Data collection
Nonius KappaCCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.706, Tmax = 0.791
11400 measured re¯ections
2990 independent re¯ections
2898 re¯ections with I > 2ꢄ(I)
Rint = 0.016
Compound (I)
Crystal data
Re®nement
R[F2 > 2ꢄ(F2)] = 0.024
wR(F2) = 0.063
S = 1.03
2990 re¯ections
190 parameters
H-atom parameters constrained
Áꢅmax = 0.18 e A
3
3
Ê
Ê
C16H17Cl3N2O2
Mr = 375.67
Orthorhombic, Pbca
V = 3470.3 (14) A
Z = 8
3
Ê
0.23 e A
Áꢅmin
=
Mo Kꢂ radiation
Absolute structure: Flack (1983),
with 607 Friedel pairs
Flack parameter: 0.02 (5)
1
Ê
a = 9.717 (2) A
b = 10.575 (3) A
ꢃ = 0.54 mm
T = 291 (2) K
Ê
Ê
c = 33.772 (8) A
0.38 Â 0.29 Â 0.25 mm
ꢁ
o624 Zhang et al. C16H17Cl3N2O2 and C14H11Cl5N2
Acta Cryst. (2007). C63, o622±o625

organic compounds
Table 3
Selected geometric parameters (A, ) for (II).
program(s) used to solve structure: SHELXS97 (Sheldrick, 1997);
program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997);
molecular graphics: SHELXTL (Bruker, 1997); software used to
prepare material for publication: SHELXTL.
ꢀ
Ê
C9ÐC10
1.404 (3)
C3ÐN2ÐC1
N2ÐC3ÐC4
126.37 (16)
123.51 (17)
N1ÐC9ÐC14
123.45 (18)
The authors are grateful to the Physiochemical Analysis
Measurement Institute of Chemistry, Luoyang Normal
University. We also acknowledge the Initial Fund for Scienti®c
Research of Henan Normal University.
C3ÐN2ÐC1ÐN1
C1ÐN2ÐC3ÐC4
N2ÐC3ÐC4ÐC5
144.05 (18)
9.5 (3)
177.69 (19)
C1ÐN1ÐC9ÐC14
N1ÐC9ÐC14ÐC13
2.1 (3)
179.2 (2)
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: BM3036). Services for accessing these data are
described at the back of the journal.
Table 4
Hydrogen-bond and short-contact geometry (A, ) for (II).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
References
N1ÐH1DÁ Á ÁCl2
0.86
0.93
2.69
2.89
3.049 (2)
3.774 (3)
106
160
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
Bruker (1997). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison,
Wisconsin, USA.
Flack, H. D. (1983). Acta Cryst. A39, 876±881.
C8ÐH8Á Á ÁCl4i
Symmetry code: (i) x ‡ 2; y ‡ 12; z ‡ 21.
H atoms were placed in idealized positions and allowed to ride on
Ê
their respective parent atoms, with CÐH = 0.98 A and NÐH =
Ê
0.86 A, and with Uiso(H) = 1.2Ueq(carrier atom).
Seip, H. M. & Seip, R. (1973). Acta Chem. Scand. 27, 4024±4027.
È
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany.
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È
Gottingen, Germany.
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o524±o527.
For both compounds, data collection: SMART (Bruker, 1997); cell
re®nement: SMART; data reduction: SAINT (Bruker, 1997);
ꢁ
Acta Cryst. (2007). C63, o622±o625
Zhang et al.
C16H17Cl3N2O2 and C14H11Cl5N2 o625