Different supra-molecular assemblies in two 1:1 proton-transfer compounds of sulfobenzoic acids with aromatic amines

Article abstract of DOI:10.1107/S0108270107033008

Two 1:1 proton-transfer complexes of sulfobenzoic acids with aromatic amines, namely 4-[2-(4-pyrid-yl)ethen-yl]pyridinium 2-carboxy-benzene-sulfonate, C12H11N2 ⁺·C7H5O5S^-, (I), and 1,10-phenanthrolin- 1-ium 4-carboxy-benzene-sulfonate dihydrate, C12H9N2 ⁺· C7H5O5S^-·2H2O, (II), have very different hydrogen-bonding patterns compared with reported organic sulfobenzoic acid complexes. In (I), two cations and two anions form a four-mol-ecule loop, in which π-π inter-actions occur. In (II), the anions and water mol-ecules form a three-dimensional hydrogen-bonding network, while the cations only act as pendant components. The water mol-ecules play a central role in the formation of the abundant hydrogen-bonding architecture in (II). The relative poorness and richness of hydrogen bonds in (I) and (II), respectively, give rise to novel hydrogen-bonding patterns. International Union of Crystallography 2007.

Full text of DOI:10.1107/S0108270107033008

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
benzoate trihydrate (Zhang & Zhu, 2006), tetraphenyl-
phosphonium 2-sulfobenzoic acid (Ferrer et al., 2002) and
dicyclohexylammonium 2-carboxybenzenesulfonate dihydrate
(Ng, 1995). Sulfobenzoic acid has ®ve potential sites for
hydrogen bonds: (i) two carboxyl O atoms and (ii) three
sulfonate O atoms. Therefore, further exploration of the
sulfobenzoic acid organic systems will provide abundant
supramolecular architectures. We report here two novel
sulfobenzoic acid organic complexes, (I) and (II), which are,
respectively, poor and rich in hydrogen bonds.
ISSN 0108-2701
Different supramolecular assemblies
in two 1:1 proton-transfer compounds
of sulfobenzoic acids with aromatic
amines
Jing Zhang and Long-Guan Zhu*
Department of Chemistry, Zhejiang University, Hangzhou 310027, People's
Republic of China
Correspondence e-mail: chezlg@zju.edu.cn
Received 16 June 2007
Accepted 5 July 2007
Online 26 July 2007
Two 1:1 proton-transfer complexes of sulfobenzoic acids with
aromatic amines, namely 4-[2-(4-pyridyl)ethenyl]pyridinium
+
2-carboxybenzenesulfonate, C12H11N2 ÁC7H5O5S , (I), and
Both (I) and (II) are 1:1 proton-transfer organic complexes
and each contains one protonated amine cation and one
deprotonated acid anion. Complex (I) is an anhydrous species,
while complex (II) contains two water molecules. As expected,
the sulfonic acid H atoms from 2-sulfobenzoic acid or
4-sulfobenzoic acid are transferred to the protonation sites on
the N atoms of 1,2-di-4-pyridylethylene or 1,10-phenanthro-
line in (I) and (II), respectively (Figs. 1 and 2). The protona-
tions at the N atoms in both structures are further con®rmed
by the CÐN bond distances and CÐNÐC bond angles in the
amine cations. According to an investigation of the CSD by
Athimoolam & Natarajan (2007), the protonation of the
amine N atom generally results in a slight deformation of the
ring and consequently a slightly larger CÐNÐC bond angle
(>120ꢀ); this phenomenon can also be observed in the title
structures, in that both the C17ÐN2ÐC19 angle in (I) and the
C8ÐN1ÐC18 angle in (II) are larger than 120ꢀ (Tables 1 and
3). The carboxyl group in (I) forms an interplanar angle of
74.0 (1)ꢀ with its attached benzene ring owing to the neigh-
boring steric effect of the sulfonate group, while in (II), the
carboxyl group is nearly coplanar with the benzene ring
[3.8 (1)ꢀ].
1,10-phenanthrolin-1-ium 4-carboxybenzenesulfonate dihy-
+
drate, C12H9N2 ÁC7H5O5S Á2H2O, (II), have very different
hydrogen-bonding patterns compared with reported organic
sulfobenzoic acid complexes. In (I), two cations and two
anions form a four-molecule loop, in which ꢀ±ꢀ interactions
occur. In (II), the anions and water molecules form a three-
dimensional hydrogen-bonding network, while the cations
only act as pendant components. The water molecules play a
central role in the formation of the abundant hydrogen-
bonding architecture in (II). The relative poorness and
richness of hydrogen bonds in (I) and (II), respectively, give
rise to novel hydrogen-bonding patterns.
Comment
Intermolecular interactions such as hydrogen bonds and ꢀ±ꢀ
stacking play an essential role in the formation of supra-
molecular organic complexes (Lehn, 2007; Egli & Sarkhel,
2007). In the supramolecular systems constructed by organic
synthons, carboxylic acids and protonated amines are
commonly used as donors or acceptors for hydrogen bonds
(Raj et al., 2003). Recently, 5-sulfosalicylic acid supra-
molecular systems containing both sulfonate and carboxylate
groups have been extensively explored (Smith, 2005; Smith et
al., 2005, 2006a,b,c; Fan et al., 2005), while investigations of
sulfobenzoic acid organic complexes are sparse. A search of
the Cambridge Structural Database (CSD; January 2007
update; Allen, 2002) gave only six sulfobenzoic organic
complexes, viz. two guanidinium complexes (guanidinium
4-carboxybenzenesulfonate and guanidinium 3-carboxy-
benzenesulfonate; Videnova-Adrabinska et al., 2001), 4,40-
bipyridinium bis(2-carboxybenzenesulfonate) dihydrate (Li et
al., 2004), bis{4-[(4-pyridyl)ethenyl]pyridinium} 4-sulfonato-
Figure 1
The molecular structure of (I), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level and
hydrogen bonds are shown as dashed lines.
o484 # 2007 International Union of Crystallography
DOI: 10.1107/S0108270107033008
Acta Cryst. (2007). C63, o484±o486

organic compounds
Three anhydrous 1:1 sulfonatobenzoic acid complexes have
been reported, and their structures are zero-dimensional
species without extended hydrogen bonding (Ferrer et al.,
2002) or three-dimensional networks (Videnova-Adrabinska
et al., 2001). Complex (I) forms a four-molecule loop (Fig. 3)
via NÁ Á ÁHÐO and OÐHÁ Á ÁN hydrogen bonds (Table 2). Only
one sulfonate O atom and one carboxyl O atom are involved
in the hydrogen bonds. In this loop, there is a ꢀ±ꢀ stacking
effect between two protonated 1,2-di-4-pyridylethylene mol-
ecules, with a Cg1Á Á ÁCg2(1
x, y, 1
z) separation of
ꢀ
Ê
3.9739 (15) A and a dihedral angle of 23.8 (1) (where Cg1 and
Cg2 are the centroids of the N1/C8±C12 and N2/C15±C19
Figure 4
The three-dimensional hydrogen-bonding network of (II). Hydrogen
bonds are shown as dashed lines. Bonds of the cations are shown as open
bonds and the N, O and S atoms are shown with octant shading.
rings). Moreover, signi®cant ꢀ±ꢀ interactions exist between
Ê
z) = 3.6914 (16) A]. This
loops [Cg1Á Á ÁCg1(2
x, y, 1
hydrogen-bonding loop is the ®rst such unit reported in
sulfobenzoic organic systems.
water molecules forms three hydrogen bonds with carboxyl
and sulfonate groups and another water molecule, resulting in
the hydrogen bonding extending in three directions. There are
also strong ꢀ±ꢀ stacking interactions involving protonated
1,10-phenanthroline and 4-sulfonatobenzoic acid units. The
centroid-to-centroid distances are 3.7109 (13), 3.6668 (13) and
The hydrogen-bonding pattern in complex (II) is also novel
and very different from those of reported sulfobenzoic acid
organic complexes, in which hydrogen-bonding networks are
formed by both cations and anions. In (II), the anions and
water molecules form a three-dimensional hydrogen-bonding
network with large cavities (Fig. 4 and Table 4), in which the
cations are hydrogen bonded as pendant components and
occupy the cavities of the networks. Compared with the more
limited hydrogen-bonding characteristic in complex (I),
abundant hydrogen bonding is observed in complex (II). All
®ve O atoms of the 4-sulfobenzoic acid unit are involved in the
formation of hydrogen bonds. It is obvious that water mol-
ecules also play a crucial role in the formation of the three-
dimensional hydrogen-bonded network. Each of the two
Ê
3.7976 (13) A for Cg1Á Á ÁCg2(x, 1 + y,z), Cg2Á Á ÁCg3(x, 1 + y,z)
and Cg2Á Á ÁCg3(1 + x, 1 + y, z), respectively (Cg1, Cg2 and
Cg3 are the centroids of the N1/C8±C11/C18, C2±C7 and C11±
C14/C18/C19 rings).
In conclusion, these two organic complexes have hydrogen-
bonding, ꢀ±ꢀ stacking and charge-transfer interactions,
assembling the molecular structures into supramolecular
architectures, and both hydrogen-bonding patterns in (I) and
(II) are novel and very different from those reported for
sulfobenzoic organic systems.
Experimental
A mixture of 2-sulfobenzoic acid (0.051 g, 0.25 mmol), 1,2-di-4-
pyridylethylene (0.046 g, 029 mmol) and water (10 ml) was re¯uxed
for 5 h. After cooling to room temperature, pale-yellow brick-shaped
crystals of (I) were obtained by ®ltration. A mixture of SnSO4
(0.086 g, 0.40 mmol), potassium hydrogen 4-sulfobenzoate (0.096 g,
0.40 mmol), 1,10-phenanthroline monohydrate (0.079 g, 0.40 mmol),
12 M HNO3 (0.1 ml) and water (15 ml) was sealed in a 30 ml Te¯on-
lined stainless steel autoclave and heated at 433 K for 72 h. After
cooling to room temperature, the colorless solid was ®ltered off and
washed with water. Crystals were obtained by recrystallization from
water. The synthetic procedure without SnSO4 did not lead to the
formation of complex (II). Thermogravimetric analysis revealed that
a weight loss in the temperature range 298±375 K corresponds to the
release of two water molecules (calculated 8.61%, found 8.80%).
Figure 2
The molecular structure of (II), showing the atom-labeling scheme.
Displacement ellipsoids are drawn at the 30% probability level and
hydrogen bonds are shown as dashed lines.
Compound (I)
Crystal data
+
C12H11N2 ÁC7H5O5S
ꢃ = 104.047 (2)ꢀ
3
Ê
Mr = 384.40
Triclinic, P1
V = 874.82 (19) A
Z = 2
Ê
a = 8.7451 (11) A
b = 10.0346 (13) A
Mo Kꢁ radiation
ꢄ = 0.22 mm
T = 295 (2) K
0.31 Â 0.24 Â 0.22 mm
1
Ê
Ê
c = 10.7877 (14) A
Figure 3
The hydrogen-bonding loop of (I). Hydrogen bonds are shown as dashed
lines.
ꢁ = 95.377 (1)ꢀ
ꢂ = 104.954 (1)ꢀ
+
+
ꢁ
Acta Cryst. (2007). C63, o484±o486
Zhang and Zhu
C12H11N2 ÁC7H5O5S and C12H9N2 ÁC7H5O5S Á2H2O o485

organic compounds
Data collection
Table 4
Hydrogen-bond geometry (A, ) for (II).
ꢀ
Ê
Bruker SMART CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
Tmin = 0.935, Tmax = 0.953
4632 measured re¯ections
3095 independent re¯ections
2534 re¯ections with I > 2ꢅ(I)
Rint = 0.015
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O6ÐH6BÁ Á ÁO1
O6ÐH6AÁ Á ÁO3i
O7ÐH7BÁ Á ÁO6
O7ÐH7AÁ Á ÁO5ii
N1ÐH1AÁ Á ÁO4
O2ÐH2AÁ Á ÁO7iii
0.844 (10)
0.851 (10)
0.85 (3)
0.848 (10)
0.825 (10)
0.86 (3)
1.956 (12)
1.957 (12)
1.83 (3)
1.915 (15)
2.13 (2)
1.737 (11)
2.783 (3)
2.786 (3)
2.674 (3)
2.731 (3)
2.805 (2)
2.588 (2)
166 (3)
164 (3)
170 (4)
161 (3)
139 (3)
171 (3)
Re®nement
R[F2 > 2ꢅ(F2)] = 0.039
wR(F2) = 0.111
S = 0.86
3095 re¯ections
250 parameters
2 restraints
H atoms treated by a mixture of
independent and constrained
re®nement
Symmetry codes: (i) y; x ‡ 1; z 14; (ii) y; x ‡ 2; z 41; (iii) x ‡ 1; y; z.
3
Ê
Áꢆmax = 0.18 e A
3
Ê
0.35 e A
Áꢆmin
=
H atoms on C atoms were placed in idealized positions and re®ned
Ê
as riding atoms [CÐH = 0.93 A and Uiso(H) = 1.2Ueq(C)]. H atoms
Table 1
Selected geometric parameters (A, ) for (I).
ꢀ
Ê
involved in hydrogen-bonding interactions (pyridinium, carboxyl and
water) were located from difference Fourier maps and re®ned with
N1ÐC12
N1ÐC8
1.328 (3)
1.329 (3)
N2ÐC17
N2ÐC19
1.331 (3)
1.335 (3)
Ê
distance restraints [OÐH = 0.85 (1) A and NÐH = 0.82 (1) A] and
Ê
2
®xed isotropic displacement parameters [Uiso(H) = 0.08 A ].
Ê
For both compounds, data collection: SMART (Bruker, 2002); cell
re®nement: SAINT (Bruker, 2002); data reduction: SAINT;
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); soft-
ware used to prepare material for publication: WinGX (Farrugia,
1999).
C12ÐN1ÐC8
117.2 (2)
C17ÐN2ÐC19
121.94 (18)
Table 2
Hydrogen-bond geometry (A, ) for (I).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N2ÐH2AÁ Á ÁO3
0.83 (3)
0.86 (3)
2.004 (14)
1.76 (3)
2.798 (2)
2.617 (2)
160 (3)
175 (3)
The authors thank the National Natural Science Foundation
of China (grant No. 50073019).
O1ÐH1AÁ Á ÁN1i
Symmetry code: (i) x ‡ 1; y; z ‡ 1.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SQ3086). Services for accessing these data are
described at the back of the journal.
Compound (II)
Crystal data
+
C12H9N2 ÁC7H5O5S Á2H2O
Z = 4
Mo Kꢁ radiation
ꢄ = 0.22 mm
T = 295 (2) K
Mr = 418.41
Tetragonal, P41
References
1
Ê
Ê
a = 7.1807 (6) A
Allen, F. H. (2002). Acta Cryst. B58, 380±388.
c = 36.171 (3) A
Ê
V = 1865.1 (3) A
0.33 Â 0.31 Â 0.25 mm
Athimoolam, S. & Natarajan, S. (2007). Acta Cryst. C63, o263±o266.
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Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
3
Data collection
Bruker SMART CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
Tmin = 0.931, Tmax = 0.947
11629 measured re¯ections
4269 independent re¯ections
3975 re¯ections with I > 2ꢅ(I)
Rint = 0.021
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837±838.
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70±76.
R[F2 > 2ꢅ(F2)] = 0.036
wR(F2) = 0.099
S = 0.80
4269 re¯ections
280 parameters
9 restraints
H atoms treated by a mixture of
independent and constrained
re®nement
3
Ê
Áꢆmax = 0.16 e A
3
Ê
0.29 e A
Áꢆmin
=
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Table 3
Selected geometric parameters (A, ) for (II).
ꢀ
Ê
N1ÐC8
N1ÐC18
1.332 (3)
1.356 (3)
N2ÐC17
N2ÐC19
1.319 (3)
1.345 (3)
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59, 320±328.
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C8ÐN1ÐC18
122.93 (19)
C17ÐN2ÐC19
117.0 (2)
+
+
ꢁ
o486 Zhang and Zhu C12H11N2 ÁC7H5O5S and C12H9N2 ÁC7H5O5S Á2H2O
Acta Cryst. (2007). C63, o484±o486