Hydrogen bonding in proton-transfer compounds of 5-sulfosalicylic acid with a series of aliphatic nitrogen Lewis bases

Article abstract of DOI:10.1007/s10870-010-9826-3

The crystal structures of the proton-transfer compounds of 5-sulfosalicylic acid (3-carboxy-4-hydroxybenzenesulfonic acid) with the aliphatic nitrogen Lewis bases, hydroxylamine, triethylamine, pyrrolidine,morpholine, N-methylmorpholine and piperazine, viz. hydroxyammonium 3-carboxy-4- hydroxybenzenesulfonate (1), triethylaminium 3-carboxy-4-hydroxybenzenesulfonate (2), pyrrolidinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate (3), morpholinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate (4), N-methylmorpholinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate (5) and piperazine-1,4-diium bis(3-carboxy-4-hydroxybenzenesulfonate) hexahydrate (6) have been determined and their comparative structural features and hydrogen-bonding patterns described. Crystals of 4 are triclinic, space group P-1 while the remainder are monoclinic with space group either P2_1/c (1-3) or P2_1/n (5, 6). Unit cell dimensions and contents are: for 1, a = 5.0156(3), b = 10.5738(6), c = 18.4785(9) A, β = 96.412(5)°, Z = 4; for 2, a = 8.4998(4), b = 12.3832(6), c = 15.4875(9) A, β = 102.411(5)°, Z = 4; for 3, a = 6.8755(2), b = 15.5217(4), c = 12.8335(3) A, β = 92.074(2)°, Z = 4; for 4, a = 6.8397(2), b = 12.9756(5), c = 15.8216(6) A, α = 90.833(3), β = 95.949(3), γ = 92.505(3)°, Z = 4; for 5, a = 7.0529(3), b = 13.8487(7), c = 15.6448(6) A, β = 90.190(6)°, Z = 4; for 6, a = 7.0561(2), b = 15.9311(4), c = 12.2102(3) A, β = 100.858(3)°, Z = 2. The hydrogen bonding generates structures which are either two-dimensional (2 and 5) or three-dimensional (1, 3, 4 and 6). Compound 6 represents the third reported structure of a salt of 5-sulfosalicylic acid having a dicationic piperazine species. Springer Science+Business Media, LLC 2010.

Full text of DOI:10.1007/s10870-010-9826-3

J Chem Crystallogr (2011) 41:17–25
DOI 10.1007/s10870-010-9826-3
ORIGINAL PAPER
Hydrogen Bonding in Proton-Transfer Compounds
of 5-Sulfosalicylic Acid with a Series of Aliphatic
Nitrogen Lewis Bases
•
Graham Smith Urs D. Wermuth Dalius S. Sagatys
•
Received: 7 October 2009 / Accepted: 27 May 2010 / Published online: 13 June 2010
Ó Springer Science+Business Media, LLC 2010
Abstract The crystal structures of the proton-transfer
compounds of 5-sulfosalicylic acid (3-carboxy-4-hydro-
xybenzenesulfonic acid) with the aliphatic nitrogen Lewis
bases, hydroxylamine, triethylamine, pyrrolidine, morpholine,
N-methylmorpholine and piperazine, viz. hydroxyammonium
3-carboxy-4-hydroxybenzenesulfonate (1), triethylaminium
3-carboxy-4-hydroxybenzenesulfonate (2), pyrrolidinium
3-carboxy-4-hydroxybenzenesulfonate monohydrate (3),
morpholinium 3-carboxy-4-hydroxybenzenesulfonate mono-
hydrate (4), N-methylmorpholinium 3-carboxy-4-hydroxy-
benzenesulfonate monohydrate (5) and piperazine-1,4-diium
bis(3-carboxy-4-hydroxybenzenesulfonate) hexahydrate (6)
have been determined and their comparative structural features
and hydrogen-bonding patterns described. Crystals of 4 are
triclinic, space group P-1 while the remainder are monoclinic
with space group either P21/c (1–3) or P21/n (5, 6). Unit cell
dimensions and contents are: for 1, a = 5.0156(3),
represents the third reported structure of a salt of 5-sulfosali-
cylic acid having a dicationic piperazine species.
Keywords 5-Sulfosalicylic acid ꢀ Proton-transfer
compounds ꢀ Aliphatic nitrogen Lewis bases ꢀ
Hydrogen bonding
Introduction, Results and Discussion
The utility of 3-carboxy-4-hydroxybenzenesulfonic acid
(5-sulfosalicylic acid, 5-SSA) for the formation of stable
crystalline salts with nitrogen Lewis bases has been rec-
ognized for some time particularly those of the aromatic
amines, making it a useful synthon for crystal engineering
purposes [1–4]. In addition a number of the compounds of
5-SSA possess unusual conductivity properties [4] shared
by the acid itself, which is sufficiently strong to protonate
water [5, 6]. The potential of 5-SSA as an anion or dianion
in self-assembly processes can be attributed largely to the
presence of the interactive sulfonate, carboxylic acid and
phenolic functional groups which are capable of acting both
as proton donors and acceptors in hydrogen-bonding
interactions. We have prepared and crystallographically
characterized a series of structures of these aromatic Lewis
base salts, including those with the 4-X-substituted anilines
(X = F, Cl, Br [7], CO2H [8]), 3-aminobenzoic acid [9],
3-methoxyaniline [10], benzylamine [11], the 2-X-substi-
tuted pyridines (X = NH2, OH) [12] and pyrimidine
(X = NH2) [12], the aromatic polyamines (2,6-diamino-
pyridine and 1,4-phenylenediamine) [13] and bicyclic
heteroaromatic amines (quinoline, 8-aminoquinoline,
8-hydroxyquinoline and quinaldic acid) [3]. There have also
been a large number of additional structures of aromatic
amine salts of 5-SSA reported up until the present time,
o
˚
b = 10.5738(6), c = 18.4785(9) A, b = 96.412(5) , Z = 4;
˚
for 2, a = 8.4998(4), b = 12.3832(6), c = 15.4875(9) A,
b = 102.411(5)o, Z = 4; for 3, a = 6.8755(2), b =
o
˚
15.5217(4), c = 12.8335(3) A, b = 92.074(2) , Z = 4; for 4,
˚
a = 6.8397(2), b = 12.9756(5), c = 15.8216(6) A, a =
90.833(3), b = 95.949(3), c = 92.505(3)o, Z = 4; for 5,
˚
a = 7.0529(3), b = 13.8487(7), c = 15.6448(6) A, b =
90.190(6)o, Z = 4; for 6, a = 7.0561(2), b = 15.9311(4),
o
˚
c = 12.2102(3) A, b = 100.858(3) , Z = 2. The hydrogen
bonding generates structures which are either two-dimensional
(2 and 5) or three-dimensional (1, 3, 4 and 6). Compound 6
G. Smith (&) ꢀ U. D. Wermuth ꢀ D. S. Sagatys
School of Physical and Chemical Sciences,
Queensland University of Technology,
G.P.O. Box 2434, Brisbane, QLD 4001, Australia
e-mail: g.smith@qut.edu.au
123

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J Chem Crystallogr (2011) 41:17–25
including those of simple monocyclic heteroaromatic
amines [14–24], polycyclic heteroaromatic amines [25–28]
and complex amines [29–31]. With these compounds, water
molecules of solvation are commonly present and are
involved in the molecular assembly processes, giving
mostly three-dimensional framework structures in which
there is a high probability of formation of water
O–HꢀꢀꢀOsulfonate hydrogen bonds [32]. The aromatic and
heteroaromatic Lewis base salts have additional potential
for structure stabilization through cation–anion aromatic
p–p ring interactions, although the incidence of this is
limited to the structures of the salts of 5-SSA largely, but
not exclusively with the heteroaromatic amines, e.g., the
2-X-substituted pyridines [12], pyridine-2,6-diamine [13] and
quinoline-2-carboxylic acid [3]. However, in the crystallo-
graphic literature there are fewer structures of the aliphatic
Lewis base salts of 5-SSA. Examples are guanidinium
3-carboxy-4-hydroxybenzenesulfonate [33], bis(guanidinium)
3-carboxylato-4-hydroxybenzenesulfonate monohydrate [34],
ethylenediaminium bis(3-carboxy-4-hydroxybenzenesul-
fonate) tetrahydrate [35] and the heteroaliphatic examples
piperidinium 3-carboxy-4-hydroxybenzenesulfonate mono-
hydrate [36], piperazine-1,4-diium bis(3-carboxy-4-hydro-
xybenzenesulfonate) dihydrate [37] and the second piper-
azine compound piperazine-1,4-diium bis(piperazine-1-
ium) bis(3-carboxylato-4-hydroxybenzenesulfonate) dihy-
drate [38], in which there are both mono- and dicationic
species. The dianionic 5-SSA2- species has a relatively low
incidence among the known structures of salts of this acid,
being limited to the piperazine example just considered
[38], one of the guanidine salts [34], the benzylamine salt
[11], the 1,4-phenylenediamine salt [13], the 2-aminopyri-
dine salt [14], a 5-methyimidazolium salt [21] (both anionic
and dianionic 5-SSA salts are reported here), the 2-amino-
4,6-dimethylpyrimidine salt [23] and the quinacrinium salt
[31].
Et
Et
Et
N
OH
H2N
N
H
HO3S
TEA
PYRR
HYD
H
N
OH
O
O
CO2H
N
N
H
N
5-SSA
Me
H
PIPZ
MMORPH
MORPH
Scheme 1 Compound codes for 5-sulfosalicylic acid and Lewis
bases
[37]) and the third compound variant of the piperazinium
salt with 5-SSA. The structures 1–6 are reported here and
their hydrogen-bonding patterns described.
General Structure Comparison
The structure determinations of compounds 1–6 all show
two and three-dimensional hydrogen-bonded network and
framework structures. Figures 1, 2, 3, 4, 5 and 6 show the
molecular configuration and atom naming schemes used
for the individual 5-SSA anion species, the protonated
cation species in compounds 1–6 and in 3–6, the water
molecules of solvation. Non-hydrogen atoms are shown as
40% probability displacement ellipsoids with the exception
of 1 (50%) [39]. Inter-species hydrogen bonds are shown as
dashed lines.
In all six compounds, protonation by the sulfonate group
of 5-SSA of the amine nitrogen of the Lewis base occurs
(two in the case of the dianion piperazine), with a sub-
sequent strong primary hydrogen-bonding interaction
We therefore synthesized a series of compounds of 5-SSA
with a number of aliphatic amines in aqueous alcoholic
(ethanol or 2-propanol) solutions. The compounds giving
products suitable for crystallographic characterization were
those with hydroxylamine (HYD), triethylamine (TEA) and
the cyclic amines pyrrolidine (PYRR), morpholine
(MORPH), N-methylmorpholine (MMORPH) and pipera-
zine (PIPZ) (Scheme 1), the compounds. hydroxyammonium
3-carboxy-4-hydroxybenzenesulfonate (1), triethylaminium
3-carboxy-4-hydroxybenzenesulfonate (2), pyrrolidinium
3-carboxy-4-hydroxybenzenesulfonate monohydrate (3),
morpholinium 3-carboxy-4-hydroxybenzenesulfonate monohy-
drate (4), N-methylmorpholinium 5-sulfosalicylate monohy-
drate (5) and piperazine-1,4-diium bis(3-carboxy-4-hydro-
xybenzenesulfonate) hexahydrate (6), respectively. Compound
6 therefore represents a second hydrate pseudopolymorphic
form of a piperazinium salt of 5-SSA (the other is the dihydrate
Fig. 1 The 5-SSA anion and the oxammmonium cation in 1. Inter-
species hydrogen bonds in the R22(7) association are shown as dashed
lines. Non-hydrogen atoms are shown as 50% probability ellipsoids
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J Chem Crystallogr (2011) 41:17–25
19
Fig. 5 The 5-SSA anion, the N-methylmorpholinium cation and the
water molecule in 5 (40% probability)
Fig. 2 The 5-SSA anion and the triethylaminium cation in 2 (40%
probability)
Fig. 6 The 5-SSA anion, the pipazinium dication and the three water
molecules in 6 (40% probability). The dication molecule lies on a
crystallographic inversion centre with atoms N11vii, C21vii and C61vii
related to N11, C21 and C61 by the symmetry operation (vii) -x ? 2,
-y, -z
Fig. 3 The 5-SSA anion, the pyrrolidinium cation and the water
molecule of solvation in 3, showing the R22(7) hydrogen-bonding
association (40% probability)
between this group and at least one oxygen acceptor from
the 5-SSA sulfonate group, with the exception of 6 where
only N–HꢀꢀꢀOwater or ꢀꢀꢀOphenol interactions are found. With
6 and the other hydrated examples 3–5, this common water
O–HꢀꢀꢀOsulfonate interaction is present, often bridging sul-
fonate groups (4–6) giving structure extension. In all six
structures, a strong 5-SSA carboxylic acidꢀꢀꢀO interaction is
˚
present, usually with water when present [2.568(2) A (3);
˚
2.6316(18) and 2.5930(17) A (4); 2.557(2) A (5)], the
˚
unusual exception being with 6 where the interaction is
˚
with a sulfonate-O acceptor [2.614(2) A]. This is also the
case with anhydrous 1 and 2 [2.5930(16) (1) and
˚
2.6134(19) A (2)]. Additional secondary hydrogen-bonding
interactions give structure extension into the two and three-
dimensional structures. With the 5-SSA anion species, the
usual short intramolecular phenolic O–HꢀꢀꢀOcarboxyl
˚
hydrogen bond is found [range 2.5911(17) A (4B)–
˚
2.6413(17) A (6)]. This association is consistent with the
essential coplanarity of the carboxyl group and the parent
benzene ring [torsion angle range for C2–C1–C7–O71:
-176.07(16)° (2) to 179.86(14)° (5).
Fig. 4 The two 5-SSA anions (A and B), the two morpholinium
cations (C and D) and the two water molecules of solvation (O1W,
O2W) in the asymmetric unit of 4 (40% probability)
123

20
J Chem Crystallogr (2011) 41:17–25
˚
The Individual Structures
[(HYD)? (5-SSA)-] (1)
Table 1 Hydrogen-bonding interactions (A/°) for 1–6
D–HꢀꢀꢀA
D–H
HꢀꢀꢀA
DꢀꢀꢀA
\DHꢀꢀꢀA
(a) Compound 1a
O2–H2ꢀꢀꢀO72
0.94(3) 1.75(3) 2.5930(16)
0.94(3) 2.46(3) 2.8436(15)
0.81(3) 1.88(3) 2.6818(16)
0.78(2) 2.29(2) 2.8337(19)
0.78(2) 2.14(2) 2.8284(19)
148(2)
104(2)
170(3)
127(2)
148(2)
The structure of the anhydrous compound 1 with hydroxyl-
amine shows a primary cyclic but somewhat twisted R22 (7)
hydrogen-bonding interaction between both the protonated
N?–H and O–H donors of the hydroxyammonium cation and
two of the sulfonate-O acceptors of the 5-SSA anion (Fig. 1).
This interaction is symmetric [N11–HꢀꢀꢀO51, 2.8318(19);
O2–H2ꢀꢀꢀO72i
O71–H71ꢀꢀꢀO53ii
O21–H21ꢀꢀꢀO51iii
O21–H21ꢀꢀꢀO52
N11–H11AꢀꢀꢀO51
N11–H11BꢀꢀꢀO2iv
N11–H11BꢀꢀꢀO72v
N11–H11CꢀꢀꢀO52vi
(b) Compound 2b
O2–H2ꢀꢀꢀO72
0.94(2) 1.92(2) 2.8318(19) 163.5(18)
˚
O21–HꢀꢀꢀO52, 2.8284(19) A]. Hydrogen-bonding extension
0.89(2) 2.11(2)
0.89(2) 2.31(2)
2.897(2)
2.925(2)
146.9(18)
126.6(17)
occurs through the second and third aminium protons as well
as the carboxylic acid protons to sulfonate-O acceptors
(Table 1a) resulting in the three-dimensional framework
structure (Fig. 7). The intramolecular phenolic-carboxylate
0.90(2) 1.96(2) 2.8483(19) 170.0(19)
0.84(3) 1.85(3) 2.6134(19)
0.84(3) 2.56(3) 3.0652(19)
0.75(3) 1.88(3) 2.6297(19)
152(2)
121(2)
174(4)
176(2)
˚
O21–H2ꢀꢀꢀO51i
O–HꢀꢀꢀO hydrogen bond is 2.5930(16) A.
O71–H71ꢀꢀꢀO53ii
N11–H11ꢀꢀꢀO52
[(TEA)? (5-SSA)-] (2)
0.87(3) 1.90(3)
2.767(2)
(c) Compound 3c
O2–H2ꢀꢀꢀO72
The structure of anhydrous 2 with triethylamine shows a
direct strong N?–HꢀꢀꢀOsulfonate hydrogen-bonding interac-
0.89(3) 1.71(4)
0.87(3) 1.69(3)
0.80(4) 2.47(3)
0.80(4) 2.20(4)
0.90(3) 2.19(2)
0.90(3) 2.48(2)
0.88(3) 1.84(3)
0.89(4) 1.82(4)
2.594(2)
2.568(2)
3.014(3)
2.878(3)
2.993(3)
3.063(3)
2.713(2)
2.713(2)
179(3)
179(4)
O71–H71ꢀꢀꢀO1Wi
N11–H11AꢀꢀꢀO72ii
N11–H11AꢀꢀꢀO51iii
N11–H11BꢀꢀꢀO1Wii
N11–H11BꢀꢀꢀO52
O1W–H11WꢀꢀꢀO53iv
O1W–H12WꢀꢀꢀO51
(d) Compound 4d
O2A–H2AꢀꢀꢀO72A
O2B–H2BꢀꢀꢀO72B
O71A–H71AꢀꢀꢀO1Wi
O71B–H71BꢀꢀꢀO2Wii
N1C–H11CꢀꢀꢀO2Wiii
N1C–H12CꢀꢀꢀO53B
N1C–H12CꢀꢀꢀO72Biv
N1D–H11DꢀꢀꢀO51A
N1D–H12DꢀꢀꢀO1W
N1D–H12DꢀꢀꢀO71Ai
O1W–H11WꢀꢀꢀO52B
˚
tion [N11–HꢀꢀꢀO52, 2.767(2) A] linking the TEA cation
127(3)
and the 5-SSA anion species (Fig. 2). Head-to-tail car-
boxylic acid O–HꢀꢀꢀOsulfonate interactions give chains which
extend along the a cell direction while the phenolic proton
associates with the third sulfonate-O acceptor giving
peripheral extension (Table 1b), resulting in the two-
dimensional network structure (Fig. 8). The intramolecular
143(3)
147.7(19)
123.3(17)
179(4)
177(3)
˚
O–HꢀꢀꢀO hydrogen bond is 2.6134(19) A.
0.84(3) 1.80(3) 2.5933(17)
0.79(2) 1.86(2) 2.5911(17)
0.86(2) 1.77(2) 2.6316(18)
0.85(3) 1.74(3) 2.5920(17)
156(2)
155(2)
180(3)
177(2)
[(PYRR)? (5-SSA)-ꢀH2O] (3)
In the structure of the monohydrate compound 3 with pyr-
rolidine, the water molecule closes two conjoint cyclic
associations with the 5-SSA anion: the first: graph set R22(6),
betweenasingle N?-H donor of the cation and two sulfonate-
O acceptors of the 5-SSA anion (O51, O52) (see Fig. 3); the
second: graph set R23(8) between both aminium protons and
the carboxylic acid of the anion (Fig. 9). This second inter-
action is asymmetric with the carboxylic acid hydrogen bond
0.84(4) 2.26(2) 3.0004(18) 147.0(19)
0.96(2) 1.91(2) 2.8255(18) 157.7(17)
0.96(2) 2.51(2) 2.9626(17) 108.4(14)
0.93(2) 1.94(2) 2.8480(19) 165.3(18)
0.90(2) 2.05(3) 2.9280(19)
165(2)
0.90(2) 2.51(2) 2.8784(18) 105.0(19)
0.80(3) 2.08(3) 2.8772(19)
170(2)
173(2)
177(2)
179(2)
O1W–H12WꢀꢀꢀO53Bv 0.80(3) 1.96(2) 2.7517(18)
˚
to the water molecule quite short [O–HꢀꢀꢀO, 2.568(2) A].
O2W–H21WꢀꢀꢀO52A
0.81(2) 1.95(2) 2.7626(17)
O2W–H22WꢀꢀꢀO51Avi 0.87(2) 1.88(2) 2.7497(17)
Further structure extension occurs through the water mole-
cule and the third sulfonate oxygen (Table 1c) resulting in
the three-dimensional framework structure (Fig. 9). The
(e) Compound 5e
˚
O2–H2ꢀꢀꢀO72
0.84(3) 1.86(3)
0.89(3) 1.66(2)
0.82(2) 1.92(2)
0.81(3) 2.01(3)
0.81(3) 1.92(3)
2.606(2)
2.557(2)
2.724(2)
2.797(3)
2.723(3)
147(2)
180(3)
164(2)
165(3)
174(3)
intramolecular O–HꢀꢀꢀO hydrogen bond is 2.594(2) A.
O71–H71ꢀꢀꢀO1W
N11–H11ꢀꢀꢀO51
O1W–H11WꢀꢀꢀO53i
O1W–H12WꢀꢀꢀO52ii
(f) Compound 6f
O2–H2ꢀꢀꢀO72
[(MORPH)? (5-SSA)-ꢀH2O] (4)
The asymmetric unit of the compound 4 with morpholine
contains two morpholinium cations (C and D), two 5-SSA
anions (A and B) and two water molecules of solvation
(Fig. 4). Although the mutual inter-species hydrogen-
bonding interactions (cation C with anion B and cation D
0.82(2) 1.91(2) 2.6413(17)
0.82(2) 2.57(2) 3.011(2)
148(2)
O2–H2ꢀꢀꢀO2Wi
114.7(18)
123

J Chem Crystallogr (2011) 41:17–25
21
Table 1 continued
D–HꢀꢀꢀA
D–H
HꢀꢀꢀA
DꢀꢀꢀA
\DHꢀꢀꢀA
O71–H71ꢀꢀꢀO52ii
N11–H11AꢀꢀꢀO2iii
N11–H11AꢀꢀꢀO2Wiv
N11–H11BꢀꢀꢀO1W
O1W–H11WꢀꢀꢀO3W
O1W–H12WꢀꢀꢀO71iv
O2W–H21WꢀꢀꢀO51
O2W–H22WꢀꢀꢀO52v
O3W–H31WꢀꢀꢀO72vi
O3W–H32WꢀꢀꢀO53
a
0.86(2) 1.74(2) 2.5810(18)
167(2)
0.95(2) 2.58(2) 2.9855(19) 106.4(18)
0.95(2) 1.85(2)
0.91(3) 1.90(2)
0.78(3) 1.89(3)
0.84(3) 2.17(3)
0.84(3) 2.03(3)
0.86(3) 1.99(3)
0.78(3) 2.18(3)
0.84(3) 1.98(3)
2.781(2)
2.792(3)
2.658(3)
2.992(2)
2.859(2)
2.848(2)
2.946(2)
2.812(2)
167(2)
167.1(18)
170(3)
167(3)
172(3)
179(3)
168(3)
175(4)
Symmetry codes: (i) -x ? 2, -y ? 1, -z ? 1; (ii) -x ? 2, y ? ‘,
-z ? ‘; (iii) x - 1, y, z; (iv) -x ? 1, y ? ‘, -z ? ‘; (v) x - 1,
-y ? 1‘, z - ‘; (vi) -x, -y ? 1, -z
Fig. 8 The one-dimensional sheet structure of 2 in a view down the
c cell direction. (for symmetry codes, see Table 1b)
b
Symmetry codes: (i) x - 1, y, z; (ii) -x - 1, y ? ‘, -z ? ‘
c
Symmetry codes: (i) -x ? 1, y - ‘, -z ? ‘; (ii) -x ? 1, y ? ‘,
-z ? ‘; (iii) x, -y ? ‘, z ? ‘; (iv) x - 1, y, z
d
Symmetry codes: (i) -x ? 1, -y ? 1, -z ? 1; (ii) -x ? 2,
-y ? 1, -z; (iii) x, y - 1, z; (iv) -x ? 2, -y, -z; (v) x - 1, y, z; (vi)
x ? 1, y, z
e
Symmetry codes: (i) x - ‘, -y ? 1‘, z ? ‘; (ii) x ? ‘,
-y ? 1‘, z ? ‘
f
Symmetry codes: (i) -x ? 1, -y, -z ? 1; (ii) -x ? 1‘, y - ‘,
-z ? ‘; (iii) x, y, z ? 1; (iv) -x ? 1, -y, -z; (v) x - 1, y, z;
(vi) -x ? 1‘, y ? 1‘, -z ? ‘
Fig. 9 The three-dimensional hydrogen-bonded structure of 3 in a
perspective view down the approximate a cell direction of the unit
cell (for symmetry codes, see Table 1c)
aminium proton of the cation as well as the carboxylic acid
of the anion and the water protons, with largely sulfonate-O
acceptors (Table 1d) resulting in the three-dimensional
framework structure (Fig. 10). The interactions include
similar cyclic R22(6) associations (anion A, cation D and
O1W) as well as R23(8) associations (anion B, cation C and
O2W), as found in compound 3. The water molecules also
form bridges between sulfonate groups forming links
which extend down the b axial direction in the unit cell.
The intramolecular O–HꢀꢀꢀO hydrogen bonds are
Fig. 7 A perspective view of the three-dimensional hydrogen-bonded
structure of 1 in the unit cell looking down the approximate a cell
direction (for symmetry codes, see Table 1a). Hydrogen-bonding
associations are shown as broken lines
˚
˚
2.5933(17) A (A) and 2.5911(17) A (B).
[(MMOPPH)? (5-SSA)-ꢀH2O] (5)
with anion A) are geometrically and dimensionally similar,
no higher symmetry could be identified in the triclinic cell.
Hydrogen-bonding extension occurs through the second
In the structure of the monohydrated salt 5, the N?-H group
of the protonated N-methylmorpholine molecule gives a
123

22
J Chem Crystallogr (2011) 41:17–25
piperazine-1,4-diium dication lying across a crystallo-
graphic inversion centre (symmetry code: (vii) -x ? 2,
-y, -z), a 5-SSA monoanion and three water molecules of
solvation (Fig. 6). Crystallographically imposed inversion
symmetry is also found in the other two known piparazi-
nium compounds [37, 38] in which one is dicationic with a
monoanionic 5-SSA anion [37], the other with both mono-
and dications and a 5-SSA dianion [38]. In the structure of
6, the H-donors of the protonated N centres of the piper-
azine dication give interactions with water-O acceptors
(O1W, O2W) while the carboxylic acid group is hydrogen-
bonded to a sulfonate oxygen rather than to a water mol-
ecule as is the more common case in aminium sulfonate
salts. Two of the water molecules (O2W, O3W) are
hydrogen-bonded to sulfonate oxygens with O2W bridging,
while O1W forms a bridge linking OW3 and the piperazine
dication. Other hydrogen-bonding associations (Table 1f)
complete the three-dimensional framework structure
(Fig. 12). The intramolecular O–HꢀꢀꢀO hydrogen bond is
Fig. 10 A perspective view of the three-dimensional hydrogen-
bonded structure of 4 down the approximate a cell direction in the
unit cell. (for symmetry codes, see Table 1d)
direct interaction with a sulfonate-O acceptor of the 5-SSA
anion (Fig. 5). The water molecule of solvation bridges
two sulfonate-O acceptors (O52, O53) forming hydrogen-
bonded chains which extend down the a direction of the
unit cell. As well it acts as an acceptor for the carboxylic
acid proton giving a strong hydrogen bond [O–HꢀꢀꢀO,
˚
somewhat longer [2.6413(17) A] than those usually found
in the 5-SSA structures, including those reported here
˚
˚
[range for 1–5: 2.5911(17) A (for 4) to 2.6134(10) A (for
3)].
˚
2.557(2) A] which links the chains peripherally, giving the
Conclusion
two-dimensional structure (Fig. 11; Table 1e). The intra-
˚
molecular O–HꢀꢀꢀO hydrogen bond is 2.606(2) A.
With the aliphatic amine salts of 5-sulfosalicylic acid
reported here, the dimensionality of the resultant hydrogen-
bonding structure is largely dependent on the degree of
substitution of the amine. Unlike the aromatic amines
where the nature of the aromatic rings influence stacking
effects (although the incidence of formal, though weak p–p
[(PIPY)2? 2(5-SSA)-ꢀ6H2O] (6)
In the structure of the hydrated compound 6 of piperazine
with 5-SSA, the asymmetric unit comprises a half
Fig. 12 The three dimensional hydrogen-bonded structure of 6 in the
unit cell viewed down the a cell direction (for symmetry codes: (viii),
x ? 1, y, z; (ix) -x ? 2, -y, -z ? 1. For other codes, see Table 1f)
Fig. 11 The two-dimensional hydrogen bonding in the structure of 5
viewed down the b cell direction. (for symmetry codes, see Table 1e)
123

J Chem Crystallogr (2011) 41:17–25
23
associations is low), with the aliphatic examples the degree
of association generally follows amine type: 1° [ 2° [ 3°.
The presence of the three interactive functional groups
on the 5-SSA molecule does, however, influence the
resultant primary interactions in the structures as does the
presence of water molecules of solvation when present.
Each of these factors contributes to the two-dimensional
structures of the salts with the tertiary amine compounds
(2, 5), where either water molecules extend the chains of
5-SSA anions (5), or the chain extension is homomolecular
(2) with the aminium cation peripherally bound. These two
structures are comparable except for the water molecule in
5 which may be present due to the lesser steric effects of
the N-methyl ring substituent cf. the triethyl groups in 2.
However, stabilization of the hydrated 5-SSA salt struc-
tures is generally the result of inter-sulfonate-group
hydrogen-bond bridging, as seen in 3–5. The small bifunc-
tional hydroxylammonium cation in 1 provides a particu-
larly interesting example largely because of the presence of
the stereochemically interactive a-hydroxy group which
gives, along with the expected three-dimensional structure,
unusual conjoint cyclic hydrogen-bonding associations.
acid) and the appropriate aliphatic Lewis base or base salt
[hydroxylamine hydrochloride (1), triethylamine (2), pyr-
rolidine (3), morpholine (4) and N-methylmorpholine (5) in
either 50 mL of 50% ethanol–water (1 and 5) or 50 mL of
50% 2-propanol–water (2, 3, 4). Compound 6 was prepared
using a similar procedure in 50% 2-propanol–water but
with piperazinium phosphate rather than piperazine. After
concentration to ca. 30 mL, partial room temperature
evaporation of the hot-filtered solutions gave in all cases
colourless crystal prisms or plates.
Crystallography
X-ray diffraction data for 1–6 were obtained either at
ambient temperature [297(2) K] (compounds 3–6) or at
173(2) K (1 and 2) on an Oxford Diffraction Gemini-S
Ultra CCD-detector diffractometer using graphite crystal
˚
monochromatized Mo Ka radiation (k = 0.71073 A). Data
collection and reduction was completed using CrysAlis
CCD and CrysAlis RED [40] with data corrected for
absorption (SADABS [41]). The structures were solved by
direct methods using SIR-92 [42] or SHELXS97 [43] and
refined with anisotropic thermal parameters for all non-
hydrogen atoms using SHELXL97 [43] operating within
WinGX [44]. Hydrogen atoms potentially involved in
hydrogen-bonding interactions were located by difference
methods and their positional and isotropic thermal dis-
placement parameters were refined. Others were included
in the refinement at calculated positions and treated as
riding models. General crystallographic details are given in
Table 2. The atom numbering scheme employed for the
Experimental
Preparation
The title compounds 1–5 were synthesized by heating
together under reflux for 10 min., 1 mmol quantities of 5-
sulfosalicylic acid (3-carboxy-4-hydroxybenzenesulfonic
Table 2 Crystal data for compounds 1–6
Compound
1
2
3
4
5
6
CCDC reference
Melting point (°C)
Molecular formula
Mr
734364
240
734369
140
734368
140
734366
734365
150
734367
108–110
C11H17NO8S
323.33
285
C7H9NO7S
251.22
C13H21NO6S
319.38
C11H17NO7S
307.32
C12H19NO8S
337.35
C18H34N2O18S2
630.62
Temperature (K)
Wavelength (k)
Crystal system
Space group
173(2)
173(2)
297(2)
297(2)
297(2)
297(2)
0.71073
Monoclinic
P21/c
0.71073
Monoclinic
P21/c
0.71073
Monoclinic
P21/c
0.71073
0.71073
Monoclinic
P21/n
0.71073
Monoclinic
P21/n
Triclinic
P-1
˚
a (A)
5.0156(3)
10.5738(6)
18.4785(9)
90
8.4998(4)
12.3832(6)
15.4875(9)
90
6.8755(2)
15.5217(4)
12.8335(3)
90
6.8397(2)
12.9756(5)
15.8216(6)
90.833(3)
95.949(3)
92.505(3)
1395.00(9)
7.0529(3)
13.8487(7)
15.6448(6)
90
7.0561(2)
15.9311(4)
12.2102(3)
90
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
96.412(5)
90
102.411(5)
90
92.074(2)
90
90.190(6)
90
100.858(3)
90
3
˚
V (A )
973.86(9)
1592.04(15)
1368.69(5)
1528.07(12)
1347.99(6)
123

24
J Chem Crystallogr (2011) 41:17–25
Table 2 continued
Compound
1
2
3
4
5
6
Z
4
4
4
4
4
2
Dc (g cm-3
)
1.713
0.355
520
1.332
0.228
680
1.491
0.268
648
1.625
0.272
680
1.466
0.252
712
1.554
0.284
664
l (mm-1
)
F(000)
Instrument
Oxford Diffraction Oxford Diffraction Oxford Diffraction Oxford Diffraction Oxford Diffraction Oxford
CCD
CCD
CCD
CCD
CCD
Diffraction
CCD
Reflections
total, hmax (°)
4,439, 25.0
9,216, 27.0
6,497, 25.0
16,005, 27.5
6,215, 25.0
8,314, 27.5
Crystal size
(mm)
0.30 9 0.25 9 0.25 0.60 9 0.15 9 0.15 0.50 9 0.45 9 0.40 0.40 9 0.25 9 0.08 0.30 9 0.25 9 0.25 0.35 9 0.25
9 0.25
Collection range
h
k
l
-5 to 5
-12 to 12
-21 to 21
1,679
-10 to 9
-15 to 13
-19 to 18
3,360
-8 to 8
-15 to 18
-15 to 14
2,398
-8 to 8
-16 to 16
-20 to 20
6,329
-8 to 8
-16 to 11
-18 to 17
2,646
-8 to 8
-20 to 19
-14 to 15
2,996
Reflections
(independent)
Reflections [F2 [ 2 1,473
2,821
1,844
4,710
2,072
2,282
r(F2)]
Rint
0.0149
0.0231
0.0397
0.1040
1.11
0.0227
0.0442
0.1257
1.07
0.0195
0.0333
0.0877
0.99
0.0168
0.0347
0.0907
1.00
0.0216
0.0348
0.0955
1.06
R1a [F2 [ 2r(F2)] 0.0268
wR2a (all data)
Sa
0.0799
1.16
np
169
205
205
427
219
221
Transmission
factors (max/min)
0.888/0.940
0.896/0.970
0.865/0.902
0.953/0.980
0.930/0.952
0.840/0.931
Residuals:
Dmax./min
0.285/-0.354
0.306/-0.294
0.409/-0.656
0.288/-0.366
0.213/-0.331
0.322/-
0.394
-3
˚
(e A
)
a
‘
‘
R1 = (R |Fo| - |Fc|)/R |Fo|); wR2 = {R [w(F2o - Fc2)2]/R [w(Fo2)2]} ; S = {R [w(Fo2 - F2c)2]/(n - p)}
References
5-SSA anion species in all compounds (Figs. 1, 2, 3, 4, 5
and 6) [39] follows the convention used in previous
structural studies by our group [3, 7–13, 30, 31].
1. Bakasova ZB, Abdybaliev DA, Sharipov KhT, Akbaev AA, Ibragi-
mov BT, Talipov SA, Ismankulov AI (1991) Uzb Khim Zh, p. 22
2. Raj SB, Sethuraman V, Francis S, Hemamalini M, Muthiah PT,
Bocelli G, Cantoni A, Rychlewska U, Warzajtis B (2003)
CrystEngComm 5:70
Supplementary Material
3. Smith G, Wermuth UD, White JM (2004) Acta Crystallogr
C60:o575
4. Madarasz J, Bombicz P, Jarmi K, Pokol G, Gal S (2002) J Therm
Anal Calorim 69:281
5. Mootz D, Fayos J (1970) Acta Crystallogr B26:2046
6. Marschenz-Quack A, Mootz D (1990) Acta Crystallogr C46:1471
7. Smith G, Wermuth UD, White JM (2005) Acta Crystallogr
C61:o105
CCDC 734364–CCDC 734369 contain the supplementary
crystallographic data for compounds 1–6 from this paper.
These data can be obtained free of charge via www.ccdc.cam.
ac.uk/datarequest/cif by e-mailing data_request@ccdc.cam.
ac.uk, or contacting The Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK.
8. Smith G, Wermuth UD, White JM (2005) Acta Crystallogr
E61:o313
9. Smith G (2005) Acta Crystallogr E61:o3398
10. Smith G, Wermuth UD, Healy PC (2006) Acta Crystallogr
E62:o2313
11. Smith G, Wermuth UD, Healy PC (2006) Acta Crystallogr
E62:o1863
Acknowledgments The authors acknowledge financial support
from the Australian Research Council, the School of Physical and
Chemical Sciences (Queensland University of Technology) and the
School of Biomolecular and Physical Sciences, Griffith University.
123

J Chem Crystallogr (2011) 41:17–25
25
12. Smith G, Wermuth UD, Healy PC (2006) J Chem Crystallogr
36:841
28. Peng Y-L, Jia L-H (2009) Acta Crystallogr E65:o365 [3,30-(4-
phenylenedimethylene)diimidazole]
13. Smith G, Wermuth UD, Healy PC (2005) Acta Crystallogr
C61:o555
29. Hemamalini M, Muthiah PJ, Sridhar B, Rajaram RK (2005) Acta
Crystallogr E61:o1480 (pyrimethamine)
14. Yang D-J, Qu S-H (2006) Acta Crystallogr E62:o5127 (2-
aminopyridine)
30. Smith G, Wermuth UD, Healy PC (2006) Aust J Chem 59:320
(brucine)
15. Meng X-G, Zhou C-S, Wang L, Liu C-L (2007) Acta Crystallogr
C63:o667 (3-aminopyridine)
31. Smith G, Wermuth UD (2008) Acta Crystallogr C64:o428
(quinacrine)
16. Su K-M, Li Z-H (2007) Acta Crystallogr E63:o4900 (2,6-
imethylpyridine)
32. Haynes DA, Chisholm JA, Jones W, Motherwell WDS (2004)
CrystEngComm 6:584
17. Wang Z, Yao K, Liu Z, Xu H (2008) Acta Crystallogr E64:o1192
(4-carboxypyridine)
33. Zhang X-L, Chen X-M, Ng SW (2004) Acta Crystallogr
E60:o453
18. Xie Z-Y (2007) Acta Crystallogr E63:o2956 [4-
(hydrazinocarbonyl)pyridine]
34. Smith G, Wermuth UD, Healy PC (2004) Acta Crystallogr
E60:o687
19. Yang D (2007) Acta Crystallogr E63:o4038 (imidazole)
20. Hou H-Y (2007) Acta Crystallogr E63:o3868 (2-
methylimidazole)
21. Meng X-G, Xiao Y-L, Wang Z-L, Liu C-L (2008) Acta Crys-
tallogr C64:o53 (5-methylimidazole)
22. Subashini A, Muthiah PT, Bocelli G, Cantoni A (2007) J Chem
Crystallogr 37:597 (2,6-diamino-4-oxopyrimidine)
23. Balasubramanian K, Muthiah PT, Lynch DE (2007) Chem Cent J
1:28 (2-amino-4,6-dimethylpyrimidine)
24. Wang J-R, Yang Z-H, Liu C-H, Li L-L (2008) Acta Crystallogr
E64:o1289 (pyrazine)
35. Gao S, Huo L-H, Ng SW (2004) Acta Crystallogr E60:o2197
36. Li Z, Cheng B, Kunmei S (2008) Acta Crystallogr E64:o1085
37. Li Z-H, Su K-M (2007) Acta Crystallogr E63:o4711
38. Su K-M, Li Z-H (2007) Acta Crystallogr E63:o4816
39. Spek AL (2009) Acta Crystallogr D65:48
40. Oxford Diffraction (2008) CrysAlis CCD and CrysAlis RED
(version 1.171.32.5) X-ray data acquisition programs. Oxford
Diffraction Ltd., Yarnton, England
41. Sheldrick GM (1996) SADABS: absorption correction program
¨
for area detectors. University of Gottingen, Germany
42. Altomare A, Cascarno G, Giocovasso C, Guagliardi A, Burla
MC, Polidori G, Camalli M (1994) J Appl Crystallogr 27:435
43. Sheldrick GM (2008) Acta Crystallogr A64:112
25. Wang Z-L, Wei L-H (2007) Acta Crystallogr E63:o1448
(benzimidazole)
26. Fan S-R, Xiao H-P, Zhu L-G (2005) Acta Crystallogr E61:o253
(1,10-phenanthroline)
44. Farrugia LJ (1999) J Appl Crystallogr 32:837
27. Muthiah PJ, Hemamalini M, Bocelli G, Cantoni A (2003) Acta
Crystallogr E59:o2015 (4,40-bipyridine)
123