Nonpreorganized neutral acyclic anion receptors: Structural investigations of N,N′-diphenyl-1,3-benzenedisulfonamide and N,N′ bis(4-t-butylphenyl)-1,3-benzenedisulfonamide

Article abstract of DOI:10.1023/A:1020283701925

The structure of N,N′-diphenyl-1,3-benzenedisulfonamide (1) was determined by single crystal X-ray diffraction. It crystallizes in P2 ₁/n with cell dimensions: a = 11.8390(6) A, b = 12.3950(10) A, c = 12.1184(10) A, β = 94.388(6)°, and V = 1773

Full text of DOI:10.1023/A:1020283701925

Journal of Chemical Crystallography, Vol. 32, No. 7, July 2002 (�C 2002)
Nonpreorganized neutral acyclic anion receptors:
0
Structural investigations of N,N -diphenyl-1,
0
3
3
-benzenedisulfonamide and N,N bis(4-t-butylphenyl)-1,
-benzenedisulfonamide1
(2)
(2)
(2) �
Cassandra T. Eagle, Konstantinos Kavallieratos, and Jeffrey C. Bryan
Received August 15, 2001
0
The structure of N,N -diphenyl-1,3-benzenedisulfonamide (1) was determined by single
˚
crystal X-ray diffraction. It crystallizes in P21/n with cell dimensions: a = 11.8390(6) A,
˚
˚
�
˚ 3
b = 12.3950(10) A, c = 12.1184(10) A, � = 94.388(6) , and V = 1773.1(2) A . Its di-
0
t-butyl derivative, N,N -bis(4-t-butylphenyl)-1,3-benzenedisulfonamide (2), was prepared
¯
and structurally characterized as two solvated structures. Both crystallize in P1 with cell
˚
˚
˚
dimensions: 2 � CF3CH2OH, a = 9.469(2) A, b = 10.0039(18) A, c = 16.385(3) A, � =
�
�
˚ 3
8
5.561(16) , � = 83.035(18) , � = 72.459(16), and V = 1467.7(5) A ; 2 � ClCH2CH2Cl,
˚
˚
˚
�
�
a = 9.559(2) A, b = 9.8125(12) A, c = 17.100(6) A, � = 82.495(19) , � = 83.47(2) ,
˚
3
�
= 70.100(15), and V = 1491.1(6) A . The structures exhibit hydrogen-bonding, and are
evaluated in terms of preorganization for anion binding.
KEY WORDS: anion; crystal structure; synthesis; conformation; dual-host; extraction.
Introduction
Despite its apparent simplicity and versatil-
combined with a calix[4]arene-crown ether cation
host, can significantly enhance extraction of the
2
CsNO ion pair. In fact, this dual-host system
3
2
ity, the use of dual-host systems for the extraction
of ion pairs remains a relatively unexplored area
gave the largest synergistic effects yet observed,
prompting us to further investigate the origins
of these effects. As part of these investigations,
1
,2
of separations research. We recently demon-
strated that simple disulfonamide molecules,
0
0
we report here the solid-state structures of N,N -
diphenyl-1,3-benzenedisulfonamide and N,N -
bis(4-t-butylphenyl)-1,3-benzenedisulfonamide.
The two N H bonds in these disulfonamide
molecules serve as potential sites for hydrogen
bonding interactions with anions. If they are
structurally predisposed to bind a single anion,
this chelation could explain the strong synergistic
effects observed in the ion pair extraction of
CsNO3.
(
1)
This paper has been authored by a contractor of the U.S. Gov-
ernment under contract No. DE-AC05-00OR22725. Accordingly,
the U.S. Government retains a nonexclusive, royalty-free license
to publish or reproduce the published form of this contribution, or
allow others to do so, for the U.S. Government purposes.
Chemical and Analytical Sciences Division, Oak Ridge National
Laboratory, Oak Ridge, Tennessee 37831-6119.
(2)
�
To whom correspondence should be addressed. E-mail: bryanjc@
ornl.gov.
165
1
074-1542/02/0700-0165/0 �C 2002 Plenum Publishing Corporation

1
66
Eagle, Kavallieratos, and Bryan
0
Experimental
N,N -Bis(4-t-butylphenyl)-1,3-benzenedisul-
fonamide (2). The compound was synthesized
as earlier with the exception that (2.22 g,
Syntheses
8
.1 mmol) of 1,3-benzenesulfonylchloride was
0
N,N -Bis-diphenyl
1,3-benzenedisulfona-
gradually added to a solution of 4-(t-Bu)-aniline
3
mide (1). The compound was synthesized
(6.02 g, 40.3 mmol) in 1,2-dichloroethane
by a modification of the previously published
(50 mL) and was allowed to react for 2 h. Yield:
4
1
�
method. 1,3-Benzenesulfonylchloride (2.00 g,
1.86 g (46%). H-NMR (CD Cl , 19.2 C): �
2 2
7
.3 mmol) was added gradually to a solution of
aniline (3.39 g, 36.3 mmol) in 1,2-dichloroethane
50 mL) and was allowed to react for 2 h.
The reaction mixture was washed with 1N
HCl (3 � 50 mL) to remove the excess ani-
line, and subsequently with saturated NaHCO3
(
ppm) 8.38 (s,-br, 1H, ar, H-2), 7.77 (dd, 2H, ar,
H-4), 7.43 (t, 1H, ar, H-5), 7.29 (d, 4H, Ph, H-2),
.96 (d, 4H, Ph, H-3), 6.78 (s, br, 2H, N-H), 1.25
s, 18H t-Bu).
(
6
(
Crystallography
(
2 � 50 mL), and water (2 � 50 mL). The organic
layer was dried by using a granular Na SO
A summary of crystallographic data is given
2
4
column, and reduced by rotary evaporation
to 10 mL. Slow addition of hexanes gave the
crystalline product that was dried in vacuo for 8 h
in Table 1, and selected bond lengths and angles
are given in Tables 2 and 3. Complete crystallo-
graphic data are available as supplementary mate-
rial. Intensity data were obtained using a Nonius
CAD4 diffractometer fitted with a 1.1 mm colli-
�
at 60 C. Yield: 2.59 g (91%). The product was
found to be spectroscopically identical to the one
4
˚
previously reported.
mator using Mo K� radiation (� = 0.71073 A)
Table 1. Crystal Data and Structure Refinement
Compound
CCDC deposit no.
Color/shape
Chemical formula
Formula weight
Temperature, K
Crystal system
Space group
1
2 �CF3CH2OH
CCDC-1003/6123
Colorless/fragment
C28H35F3N2O5S2
600.7
100(2)
Triclinic
¯
P1
2 � ClCH2CH2Cl
CCDC-1003/6124
Colorless/fragment
C28H36Cl2N2O4S2
599.6
100(2)
Triclinic
¯
P1
CCDC-1003/6122
Colorless/block
C18H16N2O4S2
388.47
100(2)
Monoclinic
P21/n
˚
˚
˚
Unit cell dimensions
a = 11.8390(6) A
a = 9.469(2) A
a = 9.559(2) A
˚
˚
˚
b = 12.3950(10) A
b = 10.0039(18) A
b = 9.8125(12) A
˚
˚
˚
c = 12.1184(10) A
c = 16.385(3) A
c = 17.100(6) A
�
�
�
�
�
= 85.561(16)
� = 82.495(19)
�
= 94.388(6)�
� = 83.035(18)
� = 83.47(2)
�
�
�
= 72.459(16)
� = 70.100(15)
Volume, A3
˚
1773.1(2)
4
1.45
1467.7(5)
2
1.36
1491.1(6)
2
1.34
Z
Dcalc,(g cm 3)
�
Absorption coefficient
0.327
2.3–27.5
7207
4062(Rint = 0.026)
4062/0/241
1.03
0.240
2.1–26.5
8867
6032(Rint = 0.026)
6032/0/392
1.06
0.393
2.2–24.0
6011
4646(Rint = 0.030)
4646/230/403
1.04
�
range, deg
Reflections measured
Independent reflections
Data/restraints/parameters
Goodness of fit on F2
R1 [I > 2�(I)]
0.034
0.050
0.066
wR2 (all data)
0.094
0.146
0.218

Nonpreorganized neutral acyclic anion receptors
167
Table 2. Selected Torsion Angles (deg)
1
2 �CF3CH2OH
2 � ClCH2CH2Cl
C(12) C(11) N(1) S(1)
C(11) N(1) S(1) C(1)
N(1) S(1) C(1) C(2)
C(2) C(3) S(2) N(2)
C(3) S(2) N(2) C(21)
S(2) N(2) C(21) C(22)
124.7(2)
� 53.1(1)
124.0(1)
127.8(1)
� 47.4(2)
125.8(2)
� 129.8(2)
54.3(2)
� 133.5(5)
57.4(4)
47.6(3)
48.5(3)
55.0(3)
40.4(5)
54.8(5)
55.7(5)
� 150.6(2)
� 147.3(5)
P
2
2
2 2
and an Oxford Cryosystems 600 series low tempe-
rature device. Calculations were carried out using
against |F| of the quantity w(F � F ) was
o
c
used to adjust the refined parameters.
5
6
0
XCAD4 (data reduction), SHELXTL (absor-
ption correction, structure solution/refinement,
N, N -Diphenyl-1, 3-benzenedisulfonamide
(1). The crystals were grown by slow evapo-
ration of a 1,1,1-trifluoroethanol solution. Cell
constants and an orientation matrix were ob-
tained from a crystal measuring 0.44 � 0.43 �
7
and molecular graphics), and PLATON (struc-
ture analysis). All non-hydrogen atoms were re-
fined anisotropically. Except as noted below, each
H atom was placed in a calculated position, refined
using a riding model, and given an isotropic dis-
3
0.30 mm , by least-squares refinement, using the
setting angles of 25 reflections in the range 10 <
� < 20 . The highest peak in the final difference
�
placement parameter equal to 1.2 (CH, CH ) or
2
�
3
˚
1
.5 (CH , NH, OH) times the equivalent isotropic
map measured 0.34 e � A .
3
0
displacement parameter of the atom to which it
is attached. When warranted, methyl H atomic
positions were allowed to rotate about the adja-
cent C C bond. H atoms attached to N or O were
located in a difference map, and their positional
parameters refined. Chemically equivalent N H
distances were restrained to be equal in the struc-
tures of 2. Full-matrix least squares refinement
N,N -Bis(4-t-butylphenyl)-1,3-benzenedisul-
fonamide � 1,1-trifluoroethanol, (2 � CF3CH2OH).
The crystals were grown by slow evaporation of
a 1,1,1-trifluoroethanol solution. Cell constants
and an orientation matrix were obtained from a
3
crystal measuring 0.57 � 0.39 � 0.13 mm , by
least squares refinement, using the setting angles
�
of 24 reflections in the range 10 < � < 16 . One
˚
a
Table 3. Hydrogen Bond Geometry (A, deg)
D ---- H ���A
H ���A
D ���A
6
D
---- H ���A
i
1
1
2
2
2
2
2
2
2
N1 ---- H1 ���O4
2.20(2)
2.07(2)
2.03(3)
2.07(3)
2.04(4)
3.28
2.06(5)
2.05(6)
2.50
3.059(2)
2.862(2)
2.845(3)
2.878(3)
2.810(3)
3.941(4)
2.886(6)
2.911(6)
3.213(9)
160(2)
167(2)
175(3)
175(4)
165(3)
126
158(5)
168(6)
129
ii
N2 ---- H2 ���O1
iii
� CF3CH2OH
� CF3CH2OH
� CF3CH2OH
� CF3CH2OH
� ClCH2CH2Cl
� ClCH2CH2Cl
� ClCH2CH2Cl
N1 ---- H1 ���O2
iv
N2 ---- H2 ���O3
v
O5 ---- H5 ���O4
vi
C7 ---- H7A ���Cg1
iii
N1 ---- H1 ���O2
vi
N2 ---- H2 ���O3
C7 ---- H7A ���O4
aNo su’s are given for some parameters because the positional parameters of those H atoms
involved were not refined. Cg1 refers to the calculated centroid of the arene ring C1-
6
1
. Symmetry codes: (i) 1/2 + x, 1/2 � y, 1/2 + z; (ii) 1/2 � x, 1/2 + y, 3/2 � z; (iii)
� x, � y, 1 � z; (iv) � x, � y, 1 � z; (v) � x, 1 � y, 1 � z; (vi) 1 � x, 1 � y, 1 � z.

1
68
Eagle, Kavallieratos, and Bryan
t-butyl group is disordered and is modeled over
two sites (52:48 for C18–C20). No restraints
were applied to the refinement of the disordered
atoms. The highest peak in the final difference
�
3
˚
map measured 0.54 e � A .
0
N,N -Bis(4-t-butylphenyl)-1,3-benzenedisul-
fonamide � 1,2-dichloroethane, (2 � ClCH CH
2
2
Cl). Suitable crystals were obtained from 1,2-
dichloroethane. Cell constants and an orientation
matrix were obtained from a crystal measuring
3
0
.44 � 0.24 � 0.11 mm , by least squares refine-
ment, using the setting angles of 25 reflections in
0
Fig. 1. Molecular structure of N,N -diphenyl-1,3-benzene-
�
the range 10 < � < 19 . Both t-butyl groups are
disulfonamide, (1), showing 50% probability displacement
ellipsoids. Most H atoms are omitted for clarity.
disordered, and are modeled as a twofold disorder
(68:32 for C17–C20 and 60:40 for C27–C30).
All chemically equivalent bond distances and
angles between and within the two disordered
groups are restrained to be roughly equal. Within
each disordered group, the Ui j components
benzenedisulfonamide structures (2 � CF CH OH
3
2
and 2 � ClCH CH Cl) adopt the same overall con-
2
2
formation, while 1 adopts a different conforma-
tion. The primary difference is in the C C S N
(rotation about the C S bond) torsion angles,
of bonded atoms or disordered atoms within
˚
�
0
.7 A of each other are restrained to be similar.
which are 124.0(1) and 127.8(1) in 1, and range
�
Despite these restraints the thermal ellipsoids
of some disordered atoms exhibit unusual elon-
gation, suggesting further, unresolved disorder.
The positional parameters for amide H atoms
were allowed to refine, although the two N H
distances were restrained to be approximately
equal. The highest peak in the final difference
from 40.4(5) to 54.8(5) in the structures of 2. Ba-
sically this places the central arene group between
the N H groups in 1, while these groups appear
to have mostly empty space between them in 2.
These relative orientations of the N H groups
have been termed “anti–anti” and “syn–syn,”
respectively.4 The syn–syn conformation, as
�
3
˚
map measured 0.90 e � A , and the lowest
�
3
˚
valley � 0.70 e � A .
Results and Discussion
The structures of 1, 2 � CF CH OH and
3
2
2
� ClCH CH Cl are illustrated in Figs. 1–3, re-
2
2
spectively. The configuration of each disulfon-
amide molecule can be expressed in terms of the
six torsion angles for the six single bonds that lie
between the three arene rings (Table 2). In terms
of orienting the N H groups for anion binding,
only rotation about the C S and S N bonds are
important, as rotation about the N C bonds only
determines the relative position of the outer arene
rings (C11–C16 and C21–C26). As can be seen in
0
Fig. 2. Molecular structure of N,N -bis(4-t-butylphenyl)-
1
,3-benzenedisulfonamide � 1,1,1-trifluoroethanol, (2 � CF
3
CH OH), showing 50% probability displacement ellipsoids.
2
Minor disorder components and most H atoms are omitted
for clarity.
0
Table 2, the two N,N -bis(4-t-butylphenyl)-1,3-

Nonpreorganized neutral acyclic anion receptors
169
groups of a single disulfonamide molecule bind
two separate disulfonamide molecules in this
manner, resulting in the formation of 1-D chains.
While the structure of 1 is not coordinated
to a solvent molecule, nor does it contain solvent
in the crystal lattice, both structures of 2 crystal-
lized with a solvent molecule acting as a hydro-
gen bond donor to a sulfonyl oxygen atom (see
Figs. 2 and 3 and Table 3). No other hydrogen
bonding to or from the solvent molecules is
observed. As would be expected, the hydrogen
bond formed by CF CH OH is apparently much
3
2
stronger than that formed by ClCH CH Cl, since
2
2
0
it has a much shorter H ���A separation (2.04(4)
Fig. 3. Molecular structure of N,N -bis(4-t-butylphenyl)-
˚
˚
1
,3-benzenedisulfonamide � 1,2-dichloroethane, (2 � ClCH
2
A versus 2.50 A) and much better directionality
�
8
CH Cl), showing 50% probability displacement ellipsoids.
2
6
(
D H ��� A = 165(3) and 129 ).
Minor disorder components and most H atoms are omitted
for clarity.
No �-stacking is observed in 1, but a cou-
ple of edge–face arene interactions are present.
Edges of both outer arene rings (C11–C16 and
C21–C26) interact with either face of the cen-
tral arene ring (C1–C6), forming an odd sand-
wich. �-Stacking of the central ring is observed
observed in the structures of 2, would appear to
be preferable for anion binding.
All three structures exhibit hydrogen bond-
ing between symmetry equivalent disulfonamide
molecules (Table 3). One amide hydrogen
atom binds to a sulfonyl oxygen atom of a
symmetry-related disulfonamide molecule while
the amide hydrogen atom on the symmetry-
equivalent molecule binds to the equivalent sul-
fonyl oxygen atom of the original molecule, form-
ing an eight-member ring (Fig. 4). The two N H
in the structures of 2, with interplanar distances of
˚
4
2
.041(2) and 3.900(3) A for 2 � CF CH OH and
3
2
� ClCH CH Cl, respectively. Edge–face inter-
2
2
actions like those seen in 1 are not observed in 2,
presumably because of the presence of the bulky
t-butyl group on the outer arene rings. However,
the central ring (C1–C6) interacts with one of the
outer rings (C11–C16), and the two outer rings
(
C11–C16 → C21–C26) interact with each other
in both structures of 2.
In conclusion, we have observed two confor-
mations for disulfonamide molecules which have
demonstrated strong synergistic effects observed
1
in the ion pair extraction of CsNO . The con-
3
formation observed for the t-butyl derivative ap-
pearstobemoreconducivetowardsanionbinding,
but intermolecular hydrogen bonding and arene–
arene interactions, observed in all three structures,
may play a role in stabilizing the observed confor-
mations. We are currently investigating the inter-
actions of disulfonamide molecules with anions,
through structural, theoretical, and liquid–liquid
extraction studies. The results of this work will be
reported shortly.
Fig. 4. Exampleofhydrogenbondingbetweendisulfonamide
molecules. For clarity, only fragments of the two molecules
are shown. Fragments shown are from 2 � CF
3 2
CH OH. Sym-
metry code (i) 1 � x, � y, 1 � z.

1
70
Acknowledgments
This research was sponsored by the Division of
Eagle, Kavallieratos, and Bryan
Danby, A.; Van Berkel, G.J.; Kelly, M.A.; Sachleben, R.A.;
Moyer, B.A.; Bowman-James, K. Anal. Chem. 2000, 72, 5258–
264; (c) Chrisstoffels, L.A.J.; de Jong, F.; Reinhoudt, D.N.;
Sivelli, S.; Gazzola, L.; Casnati, A.; Ungaro, R. J. Am. Chem.
Soc. 1999, 121, 10142–10151; (d) Murad, M.M.; Hayashita, T.;
Shigemori, K.; Nishizawa, S.; Teramae, N. Anal. Sci. 1999, 15,
185.
. Kavallieratos, K.; Moyer, B.A. Chem. Commun. 2001, 1620–
621.
. Autenrieth, W.; Hennings, R. Ber. 1902, 1388.
5
Chemical Sciences, Geosciences, and Biosciences, Of-
fice of Basic Energy Sciences, U.S. Department of En-
ergy, under contract DE-AC05-00OR22725 with Oak
Ridge National Laboratory, managed and operated by
UT-Battelle, LLC.
1
2
1
3
4. Kavallieratos, K.; Bertao, C.M.; Crabtree, R.H. J. Org. Chem.
999, 64, 1675–1683.
1
5
6
. Harms, K. XCAD4, Universit a¨ t Marburg, Germany, 1995.
. SHELXTL (Version 5.1, IRIX), Bruker AXS, Madison,
Wisconsin, 1997.
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. (a) Kavallieratos, K.; Sachleben, R.A.; Van Berkel, G.J.;
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