Hydrogen bonding in two ammonium salts of 5-sulfosalicylic acid: Ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate and triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate

Article abstract of DOI:10.1107/S0108270113008846

The structures of two ammonium salts of 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid, 5-SSA) have been determined at 200 K. In the 1:1 hydrated salt, ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate, NH ₄⁺·C₇H₅O₆S ^-·H₂O, (I), the 5-SSA^- monoanions give two types of head-to-tail laterally linked cyclic hydrogen-bonding associations, both with graph-set R₄⁴(20). The first involves both carboxylic acid O - H···O_water and water O - H···O_sulfonate hydrogen bonds at one end, and ammonium N - H···O_sulfonate and N - H···O_carboxy hydrogen bonds at the other. The second association is centrosymmetric, with end linkages through water O - H···O_sulfonate hydrogen bonds. These conjoined units form stacks down c and are extended into a three-dimensional framework structure through N - H···O and water O - H···O hydrogen bonds to sulfonate O-atom acceptors. Anhydrous triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4- hydroxybenzenesulfonate, 3NH₄⁺·C₇H ₄O₆S^2-·C₇H₅O ₆S^-, (II), is unusual, having both dianionic 5-SSA ^2- and monoanionic 5-SSA^- species. These are linked by a carboxylic acid O - H···O hydrogen bond and, together with the three ammonium cations (two on general sites and the third comprising two independent half-cations lying on crystallographic twofold rotation axes), give a pseudo-centrosymmetric asymmetric unit. Cation-anion hydrogen bonding within this layered unit involves a cyclic R₃ ³(8) association which, together with extensive peripheral N - H···O hydrogen bonding involving both sulfonate and carboxy/carboxylate acceptors, gives a three-dimensional framework structure. This work further demonstrates the utility of the 5-SSA^- monoanion for the generation of stable hydrogen-bonded crystalline materials, and provides the structure of a dianionic 5-SSA^2- species of which there are only a few examples in the crystallographic literature.

Full text of DOI:10.1107/S0108270113008846

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Comment
3-Carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic
acid, 5-SSA) is a very strong acid which is capable of
protonating water, and the structures of a number of
pseudopolymorphic hydrates are known, namely the dihy-
drate and trihydrate (Mootz & Fayos, 1970; Attig & Mootz,
1977), and the pentahydrate (Merschenz-Quack & Mootz,
1990). Protonated polyaqua species have been found in these
structures, e.g. H7O3+ in the trihydrate (Mootz & Fayos, 1970).
5-SSA has proved to be a useful acid for the formation of
ISSN 0108-2701
Hydrogen bonding in two ammonium
salts of 5-sulfosalicylic acid:
ammonium 3-carboxy-4-hydroxy-
benzenesulfonate monohydrate and
triammonium 3-carboxy-4-hydroxy-
benzenesulfonate 3-carboxylato-
4-hydroxybenzenesulfonate
Graham Smith* and Urs D. Wermuth
Science and Engineering Faculty, Queensland University of Technology,
GPO Box 2434, Brisbane, Queensland 4001, Australia
Correspondence e-mail: g.smith@qut.edu.au
Received 19 March 2013
Accepted 1 April 2013
The structures of two ammonium salts of 3-carboxy-4-
hydroxybenzenesulfonic acid (5-sulfosalicylic acid, 5-SSA)
have been determined at 200 K. In the 1:1 hydrated salt,
ammonium 3-carboxy-4-hydroxybenzenesulfonate mono-
+
hydrate, NH4 ꢀC7H5O6SꢁꢀH2O, (I), the 5-SSAꢁ monoanions
give two types of head-to-tail laterally linked cyclic hydrogen-
bonding associations, both with graph-set R44(20). The first
involves both carboxylic acid O—Hꢀ ꢀ ꢀOwater and water O—
Hꢀ ꢀ ꢀOsulfonate hydrogen bonds at one end, and ammonium N—
Hꢀ ꢀ ꢀOsulfonate and N—Hꢀ ꢀ ꢀOcarboxy hydrogen bonds at the
other. The second association is centrosymmetric, with end
linkages through water O—Hꢀ ꢀ ꢀOsulfonate hydrogen bonds.
These conjoined units form stacks down c and are extended
into a three-dimensional framework structure through N—
Hꢀ ꢀ ꢀO and water O—Hꢀ ꢀ ꢀO hydrogen bonds to sulfonate
O-atom acceptors. Anhydrous triammonium 3-carboxy-4-
hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzene-
stable crystalline salts with Lewis bases (Bakasova et al., 1991;
Raj et al., 2003; Smith et al., 2005, 2006, 2011; Smith &
Wermuth, 2008, 2009; Smith, Wermuth & Healy, 2004; Smith,
Wermuth & White, 2004). Because no structures of ammo-
nium salts of 5-SSA have been reported, we attempted to
prepare 1:1 and 1:2 salts for crystallographic analysis. Both 1:1
and 1:0.5 reactions with ammonium carbonate gave the
+
monohydrated 1:1 salt NH4 ꢀ5-SSAꢁꢀH2O, (I), but a suitable
+
sulfonate, 3NH4 ꢀC7H4O6S2ꢁꢀC7H5O6Sꢁ, (II), is unusual,
having both dianionic 5-SSA2ꢁ and monoanionic 5-SSAꢁ
species. These are linked by a carboxylic acid O—Hꢀ ꢀ ꢀO
hydrogen bond and, together with the three ammonium cations
(two on general sites and the third comprising two independent
half-cations lying on crystallographic twofold rotation axes),
give a pseudo-centrosymmetric asymmetric unit. Cation–anion
hydrogen bonding within this layered unit involves a cyclic
R33(8) association which, together with extensive peripheral
N—Hꢀ ꢀ ꢀO hydrogen bonding involving both sulfonate and
carboxy/carboxylate acceptors, gives a three-dimensional
framework structure. This work further demonstrates the
utility of the 5-SSAꢁ monoanion for the generation of stable
hydrogen-bonded crystalline materials, and provides the
structure of a dianionic 5-SSA2ꢁ species of which there are
only a few examples in the crystallographic literature.
Figure 1
The molecular conformation and atom-numbering scheme for the
5-SSAꢁ monoanion, the ammonium cation and the solvent water
molecule in (I). Inter-species hydrogen bonds are shown as dashed lines
and displacement ellipsoids are drawn at the 50% probability level.
534 # 2013 International Union of Crystallography
doi:10.1107/S0108270113008846
Acta Cryst. (2013). C69, 534–537

organic compounds
In (I), the 1:1 hydrated ammonium salt of 5-SSA (Fig. 1),
the 5-SSAꢁ monoanion is involved in six intermolecular
hydrogen-bonding associations, four with the ammonium
cation and two with the water molecule, which acts both as a
bridge between sulfonate O-atom acceptors and as an
acceptor in the carboxylic acid O—Hꢀ ꢀ ꢀO hydrogen bond
(Table 1). The 5-SSAꢁ monoanions give two types of head-to-
tail lateral cyclic hydrogen-bonding dimeric associations,
through both carboxylic acid O—Hꢀ ꢀ ꢀOwater and water O—
Hꢀ ꢀ ꢀOsulfonate hydrogen bonds at one end, and through N—
Hꢀ ꢀ ꢀOsulfonate and N—Hꢀ ꢀ ꢀOcarboxy hydrogen bonds at the
other. Both of these conjoined units have graph-set R44(20)
(Etter et al., 1990; Bernstein et al., 1995) and form stacks down
c, and they are extended into a three-dimensional framework
structure through N—Hꢀ ꢀ ꢀO and water O—Hꢀ ꢀ ꢀO hydrogen
bonds to sulfonate O-atom acceptors (Fig. 3). Among these
are examples of R44(12) and R34(10) cyclic associations.
In salt (II), the asymmetric unit (Fig. 2) contains a 5-SSA2ꢁ
dianion (A), a 5-SSAꢁ monoanion (B) and three ammonium
cations. Two of these (centred at N1 and N2) occupy general
positions, while the third comprises two independent half-
cations (N3 and N4) lying on crystallographic twofold rotation
axes. The anions are close to being coplanar [dihedral angle
between the A and B benzene rings = 8.04 (10)ꢂ] and associate
Figure 2
The molecular conformation and atom-numbering scheme for the
5-SSA2ꢁ dianion (A), the 5-SSAꢁ monoanion (B), the two ammonium
cations on general sites (centred at N1 and N2) and the two ammonium
cations (N3 and N4) lying on twofold rotation axes in the asymmetric unit
of (II). Inter-species hydrogen bonds are shown as dashed lines and
displacement ellipsoids are drawn at the 50% probability level.
crystalline 1:2 salt could not be obtained, even with ammonia.
However, the 1:1 stoichiometric reaction of 5-SSA with
piperidine-4-carboxamide (isonipecotamide) did not give the
expected proton-transfer salt of that Lewis base but instead
head-to-head through a strong carboxylic acid O—
Hꢀ ꢀ ꢀOcarboxylate hydrogen bond. The hydrogen-bonded cation–
anion asymmetric unit is pseudo-centrosymmetric and
features an inter-anion cyclic hydrogen-bonding association
involving atom N1 [graph set R23(8); Table 2]. A related
conjoined association involving atom N2 [N2—H22ꢀ ꢀ ꢀO11B:
+
gave the unusual ammonium salt of 5-SSA, 3NH4 ꢀ5-SSA2ꢁꢀ-
5-SSAꢁ, (II), the ammonium ion presumably being derived
from the hydrolysis of the amide by 5-SSA. The structures of
both (I) and (II) (Figs. 1 and 2) are reported here.
ꢂ
˚
Nꢀ ꢀ ꢀO = 2.909 (3) A and N—Hꢀ ꢀ ꢀO = 108 ] is also present.
Extensive peripheral hydrogen bonding and N—Hꢀ ꢀ ꢀO
Figure 3
A perspective view of the three-dimensional hydrogen-bonded framework structure of (I). Hydrogen-bonding associations are shown as dashed lines
and non-associative H atoms have been omitted. For symmetry codes, see Table 1.
NH4 ꢀC7H5O6SꢁꢀH2O and 3NH4 ꢀC7H4O6S2ꢁꢀC7H5O6Sꢁ 535
+
+
ꢃ
Smith and Wermuth
Acta Cryst. (2013). C69, 534–537

organic compounds
Figure 4
The three-dimensional hydrogen-bonded framework structure of (II) in a perspective view down the b-axial direction of the unit cell. Hydrogen-bonding
associations are shown as dashed lines and non-associative H atoms have been omitted. For symmetry codes, see Table 2.
interactions involving the ammonium anions and both sulfo-
nate and carboxy/carboxylate O-atom acceptors gives a three-
dimensional framework structure (Fig. 4).
Experimental
Compound (I) was synthesized by heating together 3-carboxy-4-hy-
droxybenzenesulfonic acid (5-sulfosalicylic acid, 1 mmol) and
(NH4)2CO3 (either 0.5 mmol or 1 mmol) in water (30 ml) for 10 min.
Colourless flat prisms were obtained after total room-temperature
evaporation of the solvent over a period of several months.
Compound (II) was obtained as the product from the attempted
preparation of a salt of 5-sulfosalicylic acid with the Lewis base
4-carbamoylpiperidine (isonipecotamide). Isonipecotamide (1 mmol)
and 5-sulfosalicylic acid (1 mmol) in methanol (50 ml) were heated
under reflux for 10 min and, after concentration to ca 30 ml, total
room-temperature evaporation of the hot-filtered solution gave a
viscous product containing a small quantity of colourless crystals of (II),
from which a specimen was cleaved for the X-ray analysis.
The 5-SSAꢁ monoanions and 5-SSA2ꢁ dianions in (I) and
(II) have features which are commonly found in other struc-
tures of both the parent acid and its anions (Attig & Mootz,
1977; Smith, Wermuth & White, 2004). In these, the carboxylic
acid group is essentially coplanar with the benzene ring, due
largely to the cyclic (S6) motif generated by the short intra-
molecular phenolic O—Hꢀ ꢀ ꢀOcarboxy hydrogen bond. In (I),
the C2—C1—C11—O11 torsion angle is ꢁ175.28 (13)ꢂ, and in
(II) the corresponding angles are ꢁ178.22 (19) (A) and
ꢁ177.44 (19)ꢂ (B). A second feature common to most 5-SSA
structures is the relatively short intramolecular aromatic C—
Hꢀ ꢀ ꢀO interaction with one O atom of the sulfonate group,
resulting in its lying close to the plane of the benzene ring
[Cꢀ ꢀ ꢀO contacts and C—C—S—O torsion angles of
Hydrated salt (I)
Crystal data
+
2.9242 (19) A and ꢁ13.37 (14)ꢂ, respectively, in (I),
˚
NH4 ꢀC7H5O6SꢁꢀH2O
3
˚
V = 1011.94 (5) A
Z = 4
Mo Kꢁ radiation
ꢂ = 0.34 mmꢁ1
T = 200 K
ꢂ
˚
˚
2.930 (3) A and 20.9 (2) , respectively, in anion A of (II), and
ꢂ
Mr = 253.23
Monoclinic, P21=c
2.910 (3) A and ꢁ23.3 (2) , respectively, in anion B of (II)].
˚
a = 11.8476 (3) A
These values compare with values of, for example,
ꢂ
˚
b = 7.2879 (2) A
ꢂ
˚
˚
2.9480 (18) A and ꢁ14.41 (14) , and 2.884 (3) A and ꢁ6.0 (2)
˚
c = 12.1343 (3) A
0.30 ꢄ 0.22 ꢄ 0.12 mm
ꢀ = 105.018 (3)ꢂ
in the hydroxylamine and morpholine (monohydrate) salts,
respectively (Smith et al., 2011).
The work presented here further demonstrates the utility of
the 5-SSAꢁ monoanion, in particular for the generation of
stable hydrogen-bonded crystalline materials, as well as
providing an example of a structure having a dianionic
5-SSA2ꢁ species, of which there are few occurrences in the
crystallographic literature.
Data collection
Oxford Gemini-S CCD area-
detector diffractometer
Absorption correction: multi-scan
(CrysAlis PRO; Oxford
Diffraction, 2010)
6550 measured reflections
1986 independent reflections
1681 reflections with I > 2ꢃ(I)
Rint = 0.022
Tmin = 0.970, Tmax = 0.980
NH4 ꢀC7H5O6SꢁꢀH2O and 3NH4 ꢀC7H4O6S2ꢁꢀC7H5O6Sꢁ
Acta Cryst. (2013). C69, 534–537
+
+
ꢃ
536 Smith and Wermuth

organic compounds
Table 1
Geometry of hydrogen-bonds and other interactions (A, ) for (I).
Refinement
ꢂ
˚
R[F2 > 2ꢃ(F2)] = 0.029
wR(F2) = 0.064
S = 0.96
3804 reflections
293 parameters
1 restraint
H atoms treated by a mixture of
independent and constrained
refinement
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
ꢁ3
˚
Áꢄmax = 0.21 e A
N1—H1Aꢀ ꢀ ꢀO53i
N1—H1Bꢀ ꢀ ꢀO12ii
N1—H1Cꢀ ꢀ ꢀO52iii
N1—H1Cꢀ ꢀ ꢀO53iv
N1—H1Dꢀ ꢀ ꢀO52
O2—H2ꢀ ꢀ ꢀO12
0.94 (2)
0.92 (2)
0.86 (2)
0.86 (2)
0.92 (2)
0.99 (3)
0.89 (2)
0.76 (2)
0.83 (2)
1.96 (2)
1.99 (2)
2.40 (2)
2.25 (2)
1.98 (2)
1.67 (3)
1.78 (2)
2.04 (2)
2.26 (2)
2.8881 (18)
2.861 (2)
173 (2)
ꢁ3
˚
Áꢄmin = ꢁ0.22 e A
156.2 (19)
129.3 (18)
140.7 (19)
169 (2)
158 (3)
177 (2)
Absolute structure: Flack (1983),
1668 Friedel pairs
Flack parameter: 0.47 (5)
3.0230 (19)
2.9703 (19)
2.8825 (19)
2.6092 (17)
2.6706 (18)
2.7985 (18)
3.0591 (18)
O11—H11ꢀ ꢀ ꢀO1W
O1W—H11Wꢀ ꢀ ꢀO51v
O1W—H12Wꢀ ꢀ ꢀO53vi
177 (3)
160 (2)
H atoms involved in hydrogen-bonding interactions were located
by difference methods and their positional and isotropic displace-
ment parameters were refined. However, in the final stages of the
refinement of (II), all ammonium H atoms were allowed to ride on
their parent atoms, with Uiso(H) = 1.2Ueq(N). Other H atoms were
1
1
2
Symmetry codes: (i) ꢁx þ 1; ꢁy; ꢁz þ 1; (ii) x þ 1; ꢁy þ ; z þ ; (iii) ꢁx þ 1,
2
1
3
1
2
1
2
1
1
2
y ꢁ ; ꢁz þ ; (iv) x; ꢁy þ ; z þ ; (v) ꢁx; ꢁy; ꢁz þ 1; (vi) ꢁx; y ꢁ ; ꢁz þ .
2
2
2
˚
included in the refinement at calculated positions (C—H = 0.93 A)
Table 2
Geometry of hydrogen-bonds and other interactions (A, ) for (II).
ꢂ
˚
and were also allowed to ride, with Uiso(H) = 1.2Ueq(C). For (II), the
absolute structure parameter (Flack, 1983) was refined as the relative
population of an inversion twin domain, with a resulting value of
0.47 (5) (1668 Friedel pairs), thus indicating an inversion twin with
approximately equal domain populations.
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
O2A—H2Aꢀ ꢀ ꢀO12A
O2B—H2Bꢀ ꢀ ꢀO12B
O11B—H11Bꢀ ꢀ ꢀO11A
N1—H11ꢀ ꢀ ꢀO53Ai
N1—H12ꢀ ꢀ ꢀO51Bii
N1—H13ꢀ ꢀ ꢀO11A
N1—H14ꢀ ꢀ ꢀO12B
N1—H14ꢀ ꢀ ꢀO52Biii
N2—H21ꢀ ꢀ ꢀO51Biv
N2—H22ꢀ ꢀ ꢀO11B
N2—H22ꢀ ꢀ ꢀO12Ai
N2—H23ꢀ ꢀ ꢀO12A
N2—H24ꢀ ꢀ ꢀO53Av
N3—H31ꢀ ꢀ ꢀO2A
0.80 (3)
0.87 (3)
0.92 (3)
0.91
0.90
0.96
0.84
0.84
0.96
0.97
0.97
0.86
0.96
0.88
0.98
0.98
0.85
0.81
1.79 (2)
1.78 (3)
1.65 (3)
1.95
1.94
2.01
2.19
2.31
1.90
2.45
2.52
1.93
2.43
2.23
1.93
2.47
2.10
2.15
2.536 (2)
2.554 (2)
2.564 (2)
2.841 (2)
2.823 (3)
2.917 (2)
2.831 (2)
2.773 (2)
2.846 (3)
2.909 (2)
3.418 (2)
2.794 (2)
2.810 (2)
2.9753 (18)
2.848 (3)
2.9901 (16)
2.906 (2)
2.891 (2)
155 (2)
146 (3)
175 (3)
168
168
156
133
115
171
108
153
177
103
143
155
113
156
152
For both compounds, data collection: CrysAlis PRO (Oxford
Diffraction, 2010); cell refinement: CrysAlis PRO; data reduction:
CrysAlis PRO; program(s) used to solve structure: SHELXS97
(Sheldrick, 2008); program(s) used to refine structure: SHELXL97
(Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics:
PLATON (Spek, 2009); software used to prepare material for
publication: PLATON.
The authors acknowledge financial support from the
Australian Research Council and the Faculty of Science and
Technology, Queensland University of Technology.
N3—H32ꢀ ꢀ ꢀO51Avi
N3—H32ꢀ ꢀ ꢀO52Avii
N4—H41ꢀ ꢀ ꢀO2B
N4—H42ꢀ ꢀ ꢀO52Bviii
1
2
3
2
1
1
Symmetry codes: (i) x; y þ 1; z; (ii) x þ ; y ꢁ ; z; (iii) x þ ; y ꢁ ; z; (iv) x; y ꢁ 1; z; (v)
2
2
1
1
3
2
1
2
3
2
1
3
2
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FG3289). Services for accessing these data are
described at the back of the journal.
x ꢁ ; y þ ; z; (vi) ꢁx þ ; y ꢁ ; ꢁz þ 1; (vii) ꢁx þ ; y þ ; ꢁz þ 1; (viii) ꢁx þ ,
2
2
2
1
y þ ; ꢁz þ 2.
2
Refinement
References
R[F2 > 2ꢃ(F2)] = 0.029
wR(F2) = 0.080
S = 1.10
1986 reflections
177 parameters
H atoms treated by a mixture of
independent and constrained
refinement
Attig, R. & Mootz, D. (1977). Acta Cryst. B33, 2422–2427.
Bakasova, Z. B., Abdybaliev, D. A., Sharipov, Kh. T., Akbaev, A. A.,
Ibragimov, R. T., Talipov, S. A. & Ismankulov, A. I. (1991). Uzb. Khim. Zh.
pp. 22–25.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
ꢁ3
˚
Áꢄmax = 0.32 e A
ꢁ3
˚
Áꢄmin = ꢁ0.41 e A
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Salt (II)
Merschenz-Quack, A. & Mootz, D. (1990). Acta Cryst. C46, 1478–1480.
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Oxfordshire, England.
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G., Cantoni, A., Rychlewska, U. & Warzajtis, B. (2003). CrystEngComm, 5,
70–76.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
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849.
Crystal data
3NH4 ꢀC7H4O6S2ꢁꢀC7H5O6Sꢁ
+
3
˚
V = 1948.20 (15) A
Z = 4
Mo Kꢁ radiation
ꢂ = 0.35 mmꢁ1
T = 200 K
Mr = 487.48
Monoclinic, C2
˚
a = 18.7682 (8) A
˚
b = 5.0027 (2) A
˚
c = 21.2122 (10) A
0.35 ꢄ 0.20 ꢄ 0.15 mm
ꢀ = 101.990 (4)ꢂ
Data collection
Oxford Gemini-S CCD area-
detector diffractometer
Absorption correction: multi-scan
(CrysAlis PRO; Oxford
Diffraction, 2010)
6235 measured reflections
3804 independent reflections
3399 reflections with I > 2ꢃ(I)
Rint = 0.018
Smith, G., Wermuth, U. D. & Sagatys, D. S. (2011). J. Chem. Crystallogr. 41,
17–25.
Smith, G., Wermuth, U. D. & White, J. M. (2004). Acta Cryst. C60, o575–o581.
Smith, G., Wermuth, U. D. & White, J. M. (2005). Acta Cryst. C61, o105–o109.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Tmin = 0.970, Tmax = 0.980
NH4 ꢀC7H5O6SꢁꢀH2O and 3NH4 ꢀC7H4O6S2ꢁꢀC7H5O6Sꢁ 537
+
+
ꢃ
Smith and Wermuth
Acta Cryst. (2013). C69, 534–537

supplementary materials
supplementary materials
Acta Cryst. (2013). C69, 534-537 [doi:10.1107/S0108270113008846]
Hydrogen bonding in two ammonium salts of 5-sulfosalicylic acid: ammonium
3-carboxy-4-hydroxybenzenesulfonate monohydrate and triammonium 3-carb-
oxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate
Graham Smith and Urs D. Wermuth
(I) Ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate
Crystal data
NH4+·C7H5O6S−·H2O
Mr = 253.23
F(000) = 528
Dx = 1.662 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 4154 reflections
θ = 3.3–28.8°
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 11.8476 (3) Å
b = 7.2879 (2) Å
c = 12.1343 (3) Å
β = 105.018 (3)°
V = 1011.94 (5) Å3
Z = 4
µ = 0.34 mm−1
T = 200 K
Plate, colourless
0.30 × 0.22 × 0.12 mm
Data collection
Oxford Gemini-S CCD area-detector
diffractometer
Radiation source: Enhance (Mo) X-ray source
Graphite monochromator
Detector resolution: 16.077 pixels mm-1
ω scans
6550 measured reflections
1986 independent reflections
1681 reflections with I > 2σ(I)
Rint = 0.022
θmax = 26.0°, θmin = 3.3°
h = −14→14
k = −8→8
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
l = −14→14
T
min = 0.970, Tmax = 0.980
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.029
wR(F2) = 0.080
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.10
1986 reflections
177 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0488P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.002
Δρmax = 0.32 e Å−3
Δρmin = −0.41 e Å−3
Acta Cryst. (2013). C69, 534-537
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supplementary materials
Special details
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are
estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the
estimation of distances, angles and torsion angles
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
S5
0.37799 (3)
−0.03102 (11)
−0.07816 (10)
−0.16178 (10)
0.34009 (10)
0.45827 (9)
0.42377 (10)
0.04430 (13)
0.05972 (14)
0.17155 (14)
0.26804 (14)
0.25331 (13)
0.14291 (13)
−0.07415 (13)
0.58883 (13)
−0.29627 (11)
−0.096 (3)
0.25408 (5)
0.74348 (15)
0.17557 (16)
0.45066 (16)
0.06649 (14)
0.32167 (15)
0.27654 (15)
0.4338 (2)
0.6246 (2)
0.6994 (2)
0.5877 (2)
0.3955 (2)
0.3203 (2)
0.3551 (2)
0.0734 (2)
0.04628 (19)
0.655 (4)
0.47006 (3)
0.35866 (10)
0.35930 (9)
0.31543 (10)
0.48037 (9)
0.57398 (9)
0.36926 (9)
0.38498 (12)
0.38732 (12)
0.42016 (13)
0.44817 (13)
0.44433 (12)
0.41430 (12)
0.35021 (12)
0.74498 (13)
0.31417 (12)
0.337 (2)
0.0153 (1)
0.0237 (3)
0.0222 (3)
0.0237 (4)
0.0218 (3)
0.0220 (3)
0.0204 (3)
0.0158 (4)
0.0176 (4)
0.0180 (5)
0.0180 (4)
0.0159 (4)
0.0166 (4)
0.0173 (5)
0.0197 (4)
0.0282 (4)
0.081 (9)*
0.0220*
O2
O11
O12
O51
O52
O53
C1
C2
C3
C4
C5
C6
C11
N1
O1W
H2
H3
0.18100
0.82620
0.42320
H4
0.34260
0.63830
0.46950
0.0220*
H6
0.13380
0.19350
0.41350
0.0200*
H11
H1A
H1B
H1C
H1D
H11W
H12W
−0.152 (2)
0.136 (3)
0.344 (2)
0.063 (8)*
0.061 (7)*
0.031 (5)*
0.038 (6)*
0.044 (6)*
0.042 (7)*
0.055 (8)*
0.583 (2)
−0.044 (3)
0.097 (3)
0.713 (2)
0.6668 (19)
0.5567 (18)
0.555 (2)
0.7774 (15)
0.8010 (18)
0.6940 (19)
0.371 (2)
0.071 (3)
0.163 (3)
−0.306 (2)
0.016 (3)
−0.314 (2)
−0.039 (3)
0.267 (2)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
S5
0.0142 (2)
0.0202 (6)
0.0173 (6)
0.0162 (6)
0.0224 (6)
0.0180 (6)
0.0219 (6)
0.0158 (2)
0.0203 (6)
0.0220 (6)
0.0271 (7)
0.0167 (6)
0.0238 (6)
0.0204 (6)
0.0163 (2)
0.0293 (6)
0.0269 (6)
0.0264 (6)
0.0275 (6)
0.0209 (6)
0.0223 (6)
−0.0009 (2)
0.0053 (5)
−0.0055 (5)
−0.0006 (5)
−0.0015 (5)
0.0010 (5)
−0.0010 (5)
0.0047 (2)
0.0043 (5)
0.0048 (5)
0.0028 (5)
0.0086 (5)
−0.0011 (5)
0.0120 (5)
0.0002 (2)
0.0033 (5)
−0.0014 (5)
−0.0007 (5)
0.0022 (5)
−0.0018 (5)
0.0000 (4)
O2
O11
O12
O51
O52
O53
Acta Cryst. (2013). C69, 534-537
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supplementary materials
C1
0.0158 (8)
0.0213 (8)
0.0222 (8)
0.0182 (8)
0.0165 (8)
0.0180 (8)
0.0177 (8)
0.0173 (8)
0.0304 (7)
0.0191 (8)
0.0193 (8)
0.0148 (8)
0.0202 (8)
0.0183 (8)
0.0164 (8)
0.0231 (9)
0.0218 (8)
0.0332 (8)
0.0132 (7)
0.0130 (7)
0.0175 (8)
0.0164 (7)
0.0135 (7)
0.0160 (7)
0.0116 (7)
0.0203 (7)
0.0222 (7)
−0.0004 (7)
0.0025 (7)
−0.0017 (7)
−0.0054 (7)
0.0009 (6)
−0.0023 (7)
−0.0014 (7)
0.0014 (6)
−0.0139 (6)
0.0053 (6)
0.0061 (6)
0.0061 (6)
0.0059 (6)
0.0051 (6)
0.0054 (6)
0.0045 (6)
0.0055 (6)
0.0089 (6)
−0.0001 (6)
0.0018 (6)
0.0006 (6)
0.0004 (6)
0.0004 (6)
−0.0011 (6)
−0.0013 (6)
0.0002 (6)
−0.0017 (6)
C2
C3
C4
C5
C6
C11
N1
O1W
Geometric parameters (Å, º)
S5—O51
1.4545 (11)
N1—H1A
0.94 (2)
S5—O52
1.4546 (11)
1.4700 (12)
1.7615 (16)
1.354 (2)
1.3149 (19)
1.2304 (19)
0.99 (3)
N1—H1C
C1—C11
C1—C6
C1—C2
C2—C3
C3—C4
C4—C5
C5—C6
C3—H3
C4—H4
C6—H6
0.86 (2)
1.473 (2)
1.400 (2)
1.402 (2)
1.392 (2)
1.373 (2)
1.411 (2)
1.377 (2)
0.9300
S5—O53
S5—C5
O2—C2
O11—C11
O12—C11
O2—H2
O11—H11
O1W—H12W
O1W—H11W
N1—H1B
N1—H1D
0.89 (2)
0.83 (2)
0.76 (2)
0.9300
0.92 (2)
0.9300
0.92 (2)
O51—S5—O52
O51—S5—O53
O51—S5—C5
113.01 (6)
111.40 (7)
107.57 (7)
112.60 (7)
106.59 (7)
105.11 (7)
99.4 (19)
111.0 (14)
110 (2)
O2—C2—C3
O2—C2—C1
C1—C2—C3
C2—C3—C4
C3—C4—C5
S5—C5—C6
C4—C5—C6
S5—C5—C4
C1—C6—C5
O11—C11—C1
O12—C11—C1
O11—C11—O12
C2—C3—H3
C4—C3—H3
C3—C4—H4
C5—C4—H4
C1—C6—H6
C5—C6—H6
117.15 (13)
122.61 (15)
120.24 (14)
120.57 (14)
119.52 (15)
120.62 (11)
120.31 (14)
118.96 (12)
120.32 (14)
114.58 (13)
122.31 (14)
123.12 (14)
120.00
O52—S5—O53
O52—S5—C5
O53—S5—C5
C2—O2—H2
C11—O11—H11
H11W—O1W—H12W
H1A—N1—H1C
H1A—N1—H1D
H1B—N1—H1D
H1C—N1—H1D
H1B—N1—H1C
H1A—N1—H1B
C6—C1—C11
108 (2)
114 (2)
112 (2)
110 (2)
105.4 (19)
108 (2)
120.00
120.00
120.87 (13)
120.10 (14)
119.02 (14)
120.00
C2—C1—C11
120.00
C2—C1—C6
120.00
O51—S5—C5—C4
O51—S5—C5—C6
O52—S5—C5—C4
O52—S5—C5—C6
O53—S5—C5—C4
170.43 (11)
−13.37 (14)
48.96 (13)
C2—C1—C11—O11
C2—C1—C11—O12
C6—C1—C11—O11
C6—C1—C11—O12
O2—C2—C3—C4
−175.28 (13)
4.8 (2)
5.8 (2)
−134.84 (12)
−70.76 (13)
−174.16 (14)
−178.65 (14)
Acta Cryst. (2013). C69, 534-537
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supplementary materials
O53—S5—C5—C6
C6—C1—C2—O2
C6—C1—C2—C3
C11—C1—C2—O2
C11—C1—C2—C3
C2—C1—C6—C5
C11—C1—C6—C5
105.45 (13)
179.07 (13)
−1.0 (2)
C1—C2—C3—C4
C2—C3—C4—C5
C3—C4—C5—S5
C3—C4—C5—C6
S5—C5—C6—C1
C4—C5—C6—C1
1.5 (2)
−0.5 (2)
175.28 (12)
−0.9 (2)
0.1 (2)
179.98 (14)
−0.4 (2)
−174.81 (11)
1.3 (2)
178.61 (13)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H1A···O53i
N1—H1B···O12ii
N1—H1C···O52iii
N1—H1C···O53iv
N1—H1D···O52
O2—H2···O12
0.94 (2)
0.92 (2)
0.86 (2)
0.86 (2)
0.92 (2)
0.99 (3)
0.89 (2)
0.76 (2)
0.83 (2)
0.93
1.96 (2)
1.99 (2)
2.40 (2)
2.25 (2)
1.98 (2)
1.67 (3)
1.78 (2)
2.04 (2)
2.26 (2)
2.53
2.8881 (18)
2.861 (2)
173 (2)
156.2 (19)
129.3 (18)
140.7 (19)
169 (2)
158 (3)
177 (2)
177 (3)
160 (2)
140
3.0230 (19)
2.9703 (19)
2.8825 (19)
2.6092 (17)
2.6706 (18)
2.7985 (18)
3.0591 (18)
3.3049 (19)
3.387 (2)
O11—H11···O1W
O1W—H11W···O51v
O1W—H12W···O53vi
C3—H3···O51vii
C4—H4···O52viii
C6—H6···O11
0.93
2.56
148
0.93
2.43
2.741 (2)
100
C6—H6···O51
0.93
2.54
2.9242 (19)
105
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+3/2; (iv) x, −y+1/2, z+1/2; (v) −x, −y, −z+1; (vi) −x, y−1/2, −z+1/2; (vii)
x, y+1, z; (viii) −x+1, −y+1, −z+1.
(II) Triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate
Crystal data
3NH4+·C7H4O6S2−·C7H5O6S−
Mr = 487.48
F(000) = 1016
Dx = 1.662 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 4309 reflections
θ = 3.3–28.6°
Monoclinic, C2
Hall symbol: C 2y
a = 18.7682 (8) Å
b = 5.0027 (2) Å
c = 21.2122 (10) Å
β = 101.990 (4)°
V = 1948.20 (15) Å3
Z = 4
µ = 0.35 mm−1
T = 200 K
Prism, colourless
0.35 × 0.20 × 0.15 mm
Data collection
Oxford Gemini-S CCD area-detector
diffractometer
Radiation source: Enhance (Mo) X-ray source
Graphite monochromator
Detector resolution: 16.077 pixels mm-1
ω scans
6235 measured reflections
3804 independent reflections
3399 reflections with I > 2σ(I)
Rint = 0.018
θmax = 26.0°, θmin = 3.3°
h = −20→22
k = −6→6
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
l = −26→22
T
min = 0.970, Tmax = 0.980
Acta Cryst. (2013). C69, 534-537
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supplementary materials
Refinement
Refinement on F2
Hydrogen site location: inferred from
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.029
wR(F2) = 0.064
S = 0.96
3804 reflections
293 parameters
1 restraint
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
neighbouring sites
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0372P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.21 e Å−3
Δρmin = −0.22 e Å−3
Absolute structure: Flack (1983), 1668 Friedel
pairs
Flack parameter: 0.47 (5)
Special details
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are
estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the
estimation of distances, angles and torsion angles
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
S5B
0.57238 (3)
0.88602 (8)
0.73560 (8)
0.85187 (8)
0.55039 (9)
0.53507 (9)
0.56776 (10)
0.76141 (12)
0.81332 (12)
0.79130 (12)
0.71836 (12)
0.66613 (12)
0.68730 (11)
0.78613 (11)
0.95259 (3)
0.63906 (8)
0.78318 (8)
0.66852 (8)
0.98105 (9)
0.95508 (8)
0.98664 (8)
0.76202 (11)
0.71172 (11)
0.73507 (12)
0.80832 (12)
0.85320 (10)
0.6623 (4)
0.1825 (3)
0.2752 (3)
1.0130 (4)
0.6018 (4)
0.9980 (5)
0.5330 (4)
0.6960 (4)
0.8985 (4)
0.9423 (5)
0.7820 (4)
0.5788 (4)
0.3196 (4)
−0.89285 (10)
−0.6322 (4)
−0.2015 (3)
−0.2910 (3)
−0.7701 (3)
−1.1831 (3)
−0.7920 (3)
−0.5447 (4)
−0.6871 (4)
−0.8908 (5)
−0.9517 (4)
0.88754 (3)
0.90275 (9)
0.78231 (8)
0.82377 (8)
0.82910 (9)
0.88215 (10)
0.94496 (9)
0.85860 (11)
0.89824 (10)
0.93500 (11)
0.93189 (11)
0.89291 (10)
0.85716 (10)
0.81982 (10)
0.62625 (3)
0.58388 (8)
0.72237 (7)
0.67398 (8)
0.57438 (8)
0.62381 (7)
0.68988 (8)
0.64253 (11)
0.59609 (10)
0.56095 (11)
0.57040 (11)
0.0237 (2)
0.0307 (6)
0.0241 (5)
0.0296 (6)
0.0412 (6)
0.0499 (7)
0.0510 (7)
0.0197 (7)
0.0209 (7)
0.0247 (7)
0.0242 (7)
0.0195 (7)
0.0205 (7)
0.0199 (7)
0.0186 (2)
0.0289 (5)
0.0228 (5)
0.0301 (6)
0.0326 (6)
0.0256 (5)
0.0281 (5)
0.0180 (6)
0.0196 (7)
0.0238 (7)
0.0207 (7)
O2B
O11B
O12B
O51B
O52B
O53B
C1B
C2B
C3B
C4B
C5B
C6B
C11B
S5A
O2A
O11A
O12A
O51A
O52A
O53A
C1A
C2A
C3A
C4A
Acta Cryst. (2013). C69, 534-537
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supplementary materials
C5A
C6A
C11A
N1
0.85886 (11)
0.83560 (11)
0.73660 (12)
0.93692 (10)
0.58715 (9)
0.50000
−0.8110 (4)
−0.6089 (4)
−0.3307 (4)
−0.1249 (4)
0.1316 (4)
−0.8115 (5)
0.9029 (6)
0.536 (6)
1.00390
0.61511 (10)
0.65088 (10)
0.68218 (10)
0.78033 (9)
0.70855 (9)
0.50000
0.0181 (7)
0.0178 (6)
0.0195 (7)
0.0309 (6)
0.0243 (6)
0.0225 (8)
0.0312 (9)
0.050 (9)*
0.0300*
N2
N3
N4
1.00000
1.00000
H2B
H3B
H4B
H6B
H11B
H2A
H3A
H4A
H6A
H11
H12
H13
H14
H21
H22
H23
H24
H31
H32
H41
H42
0.8928 (15)
0.82590
0.8762 (14)
0.96160
0.70370
1.07950
0.95590
0.0290*
0.65230
0.47090
0.83190
0.0250*
0.7513 (16)
0.6370 (13)
0.70140
0.049 (7)
−0.506 (5)
−0.98650
−1.08800
−0.51500
−0.01030
−0.25720
−0.20350
−0.03740
0.07340
0.7586 (16)
0.6065 (12)
0.53100
0.078 (12)*
0.030 (8)*
0.0290*
0.82380
0.54660
0.0250*
0.86960
0.68090
0.0210*
0.95760
0.75620
0.0370*
0.96770
0.79650
0.0370*
0.89030
0.76240
0.0370*
0.93010
0.81210
0.0370*
0.57660
0.74860
0.0290*
0.61630
0.29430
0.71460
0.0290*
0.61260
0.00450
0.69680
0.0290*
0.54010
0.14480
0.68010
0.0290*
0.53500
−0.69410
−0.92950
0.81290
0.51290
0.0270*
0.50980
0.46590
0.0270*
0.96300
0.98120
0.0380*
0.98700
1.00450
1.02500
0.0380*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
S5B
0.0234 (3)
0.0188 (8)
0.0209 (8)
0.0182 (9)
0.0356 (10)
0.0290 (9)
0.0407 (11)
0.0235 (12)
0.0179 (12)
0.0288 (13)
0.0346 (13)
0.0239 (12)
0.0188 (11)
0.0180 (12)
0.0177 (3)
0.0172 (8)
0.0222 (8)
0.0180 (9)
0.0249 (3)
0.0242 (3)
0.0317 (10)
0.0290 (10)
0.0381 (11)
0.0334 (11)
0.0894 (16)
0.0327 (11)
0.0170 (12)
0.0202 (12)
0.0198 (12)
0.0205 (13)
0.0173 (12)
0.0214 (12)
0.0230 (12)
0.0234 (3)
0.0345 (10)
0.0243 (9)
0.0371 (11)
0.0085 (2)
0.0003 (7)
0.0040 (6)
0.0068 (7)
0.0220 (8)
−0.0010 (9)
0.0227 (10)
0.0034 (8)
0.0009 (9)
−0.0050 (9)
0.0024 (9)
0.0024 (9)
0.0007 (9)
0.0021 (9)
0.0021 (2)
0.0036 (7)
0.0030 (6)
0.0082 (7)
0.0083 (2)
0.0054 (7)
0.0055 (7)
0.0063 (7)
0.0106 (8)
0.0165 (9)
0.0120 (9)
0.0052 (9)
0.0067 (10)
0.0024 (9)
0.0083 (10)
0.0058 (9)
0.0031 (9)
0.0062 (9)
0.0084 (2)
0.0013 (7)
0.0059 (7)
0.0064 (8)
−0.0002 (2)
−0.0052 (8)
−0.0070 (7)
−0.0075 (7)
0.0178 (9)
O2B
0.0416 (11)
0.0224 (9)
0.0327 (10)
0.0560 (12)
0.0331 (9)
0.0816 (14)
0.0189 (12)
0.0257 (11)
0.0244 (13)
0.0186 (11)
0.0180 (12)
0.0208 (11)
0.0195 (11)
0.0164 (2)
0.0331 (10)
0.0224 (8)
0.0354 (9)
O11B
O12B
O51B
O52B
O53B
C1B
0.0103 (11)
−0.0196 (10)
0.0024 (8)
0.0050 (9)
C2B
C3B
−0.0033 (9)
−0.0007 (9)
0.0001 (9)
C4B
C5B
C6B
−0.0011 (9)
0.0025 (10)
0.0012 (2)
−0.0084 (9)
−0.0071 (7)
−0.0104 (8)
C11B
S5A
O2A
O11A
O12A
Acta Cryst. (2013). C69, 534-537
sup-6

supplementary materials
O51A
O52A
O53A
C1A
C2A
C3A
C4A
C5A
C6A
C11A
N1
0.0340 (10)
0.0232 (8)
0.0197 (8)
0.0188 (11)
0.0181 (11)
0.0282 (12)
0.0288 (13)
0.0190 (12)
0.0178 (10)
0.0230 (12)
0.0260 (10)
0.0189 (9)
0.0258 (15)
0.0114 (13)
0.0300 (9)
0.0189 (7)
0.0349 (9)
0.0158 (10)
0.0193 (11)
0.0201 (11)
0.0168 (12)
0.0178 (11)
0.0167 (11)
0.0174 (11)
0.0400 (12)
0.0225 (10)
0.0197 (13)
0.062 (2)
0.0412 (11)
0.0340 (10)
0.0286 (10)
0.0205 (12)
0.0208 (12)
0.0206 (12)
0.0164 (12)
0.0186 (12)
0.0187 (11)
0.0190 (12)
0.0290 (11)
0.0324 (11)
0.0237 (15)
0.0207 (15)
0.0080 (7)
0.0045 (7)
−0.0009 (7)
0.0019 (9)
0.0007 (9)
0.0014 (10)
0.0030 (8)
0.0037 (8)
−0.0007 (8)
0.0016 (8)
0.0131 (9)
0.0049 (8)
0.0000
0.0250 (8)
0.0044 (7)
0.0023 (7)
0.0069 (9)
0.0024 (9)
−0.0006 (9)
0.0045 (10)
0.0068 (9)
0.0031 (9)
0.0063 (9)
0.0107 (8)
0.0071 (8)
0.0094 (12)
0.0044 (11)
0.0084 (8)
0.0013 (7)
−0.0060 (7)
0.0017 (9)
0.0054 (9)
−0.0017 (10)
−0.0015 (8)
0.0027 (9)
−0.0015 (9)
0.0026 (9)
0.0062 (10)
−0.0028 (9)
0.0000
N2
N3
N4
0.0000
0.0000
Geometric parameters (Å, º)
S5B—O51B
S5B—O52B
S5B—O53B
S5B—C5B
S5A—O51A
S5A—O52A
S5A—O53A
S5A—C5A
O2B—C2B
O11B—C11B
O12B—C11B
O2B—H2B
O11B—H11B
O2A—C2A
O11A—C11A
O12A—C11A
O2A—H2A
N1—H13
1.461 (2)
N3—H32
0.9800
1.432 (2)
1.435 (2)
1.776 (2)
1.4551 (18)
1.4541 (16)
1.4582 (17)
1.774 (2)
1.358 (3)
1.300 (3)
1.239 (3)
0.87 (3)
0.92 (3)
1.362 (3)
1.265 (3)
1.269 (3)
0.80 (3)
0.9600
N3—H31
0.8800
N4—H41
0.8500
N4—H42
0.8100
N4—H41ii
N4—H42ii
C1B—C11B
C1B—C6B
C1B—C2B
C2B—C3B
C3B—C4B
C4B—C5B
C5B—C6B
C3B—H3B
C4B—H4B
C6B—H6B
C1A—C11A
C1A—C6A
C1A—C2A
C2A—C3A
C3A—C4A
C4A—C5A
C5A—C6A
C3A—H3A
C4A—H4A
C6A—H6A
0.8500
0.8100
1.480 (3)
1.404 (3)
1.407 (3)
1.393 (3)
1.374 (3)
1.397 (3)
1.375 (3)
0.9300
0.9300
0.9300
1.499 (3)
1.393 (3)
1.408 (3)
1.386 (3)
1.382 (3)
1.386 (3)
1.388 (3)
0.9300
N1—H14
0.8400
N1—H12
0.9000
N1—H11
0.9100
N2—H22
0.9700
N2—H23
0.8600
N2—H24
0.9600
N2—H21
0.9600
0.9300
N3—H32i
0.9800
0.9300
N3—H31i
0.8800
O51B—S5B—O52B
O51B—S5B—O53B
O51B—S5B—C5B
O52B—S5B—O53B
O52B—S5B—C5B
111.44 (12)
112.82 (12)
105.41 (10)
113.34 (13)
106.89 (10)
S5B—C5B—C6B
C4B—C5B—C6B
S5B—C5B—C4B
C1B—C6B—C5B
O11B—C11B—C1B
120.59 (16)
120.2 (2)
119.15 (16)
120.5 (2)
116.60 (19)
Acta Cryst. (2013). C69, 534-537
sup-7

supplementary materials
O53B—S5B—C5B
O51A—S5A—C5A
O51A—S5A—O52A
O51A—S5A—O53A
O53A—S5A—C5A
O52A—S5A—O53A
O52A—S5A—C5A
C2B—O2B—H2B
C11B—O11B—H11B
C2A—O2A—H2A
H11—N1—H12
106.30 (11)
108.15 (10)
112.02 (9)
113.25 (10)
105.98 (10)
111.55 (9)
105.32 (9)
108.9 (19)
116 (2)
O11B—C11B—O12B
122.44 (19)
120.96 (19)
120.00
O12B—C11B—C1B
C2B—C3B—H3B
C4B—C3B—H3B
H41—N4—H42ii
H41—N4—H42
120.00
111.00
108.00
H41ii—N4—H42
111.00
H41—N4—H41ii
H41ii—N4—H42ii
H42—N4—H42ii
C5B—C4B—H4B
C3B—C4B—H4B
C5B—C6B—H6B
C1B—C6B—H6B
C2A—C1A—C11A
C6A—C1A—C11A
C2A—C1A—C6A
C1A—C2A—C3A
O2A—C2A—C1A
O2A—C2A—C3A
C2A—C3A—C4A
C3A—C4A—C5A
S5A—C5A—C4A
S5A—C5A—C6A
C4A—C5A—C6A
C1A—C6A—C5A
O11A—C11A—O12A
O12A—C11A—C1A
O11A—C11A—C1A
C4A—C3A—H3A
C2A—C3A—H3A
C3A—C4A—H4A
C5A—C4A—H4A
C5A—C6A—H6A
C1A—C6A—H6A
116.00
108.00
102.5 (18)
111.00
102.00
120.00
H12—N1—H13
108.00
120.00
H12—N1—H14
106.00
120.00
H11—N1—H13
120.00
120.00
H11—N1—H14
106.00
120.56 (19)
121.06 (19)
118.37 (19)
120.5 (2)
122.02 (19)
117.50 (19)
120.0 (2)
120.4 (2)
119.53 (16)
120.75 (16)
119.7 (2)
120.97 (19)
123.22 (19)
117.62 (19)
119.2 (2)
120.00
H13—N1—H14
105.00
H22—N2—H24
116.00
H23—N2—H24
111.00
H21—N2—H22
111.00
H22—N2—H23
109.00
H21—N2—H24
104.00
H21—N2—H23
105.00
H32—N3—H32i
H31—N3—H32i
H31i—N3—H32
H31—N3—H32
106.00
114.00
114.00
113.00
H31—N3—H31i
H31i—N3—H32i
C2B—C1B—C11B
C2B—C1B—C6B
C6B—C1B—C11B
O2B—C2B—C3B
C1B—C2B—C3B
O2B—C2B—C1B
C2B—C3B—C4B
C3B—C4B—C5B
96.00
113.00
119.5 (2)
118.57 (19)
121.96 (19)
117.5 (2)
120.5 (2)
122.05 (19)
119.8 (2)
120.4 (2)
120.00
120.00
120.00
120.00
119.00
O51B—S5B—C5B—C4B
O51B—S5B—C5B—C6B
O52B—S5B—C5B—C4B
O52B—S5B—C5B—C6B
O53B—S5B—C5B—C4B
O53B—S5B—C5B—C6B
O53A—S5A—C5A—C6A
O52A—S5A—C5A—C4A
O51A—S5A—C5A—C4A
O51A—S5A—C5A—C6A
O52A—S5A—C5A—C6A
O53A—S5A—C5A—C4A
96.72 (19)
−80.60 (19)
−144.60 (19)
38.1 (2)
C1B—C2B—C3B—C4B
C2B—C3B—C4B—C5B
C3B—C4B—C5B—S5B
C3B—C4B—C5B—C6B
C4B—C5B—C6B—C1B
S5B—C5B—C6B—C1B
C6A—C1A—C2A—O2A
C6A—C1A—C2A—C3A
C11A—C1A—C2A—O2A
C11A—C1A—C2A—C3A
C2A—C1A—C6A—C5A
C11A—C1A—C6A—C5A
−1.0 (3)
1.1 (3)
−177.43 (18)
−0.1 (3)
−23.3 (2)
−1.1 (3)
159.43 (19)
20.9 (2)
176.24 (16)
−178.38 (19)
1.7 (3)
−40.39 (19)
79.54 (19)
−100.82 (18)
139.26 (17)
−158.72 (17)
2.0 (3)
−177.9 (2)
−1.0 (3)
178.59 (19)
Acta Cryst. (2013). C69, 534-537
sup-8

supplementary materials
C6B—C1B—C2B—C3B
C6B—C1B—C2B—O2B
C6B—C1B—C11B—O11B
C6B—C1B—C11B—O12B
C11B—C1B—C2B—O2B
C11B—C1B—C2B—C3B
C2B—C1B—C6B—C5B
C11B—C1B—C6B—C5B
C2B—C1B—C11B—O11B
C2B—C1B—C11B—O12B
O2B—C2B—C3B—C4B
−0.2 (3)
C2A—C1A—C11A—O11A
−178.22 (19)
2.6 (3)
179.3 (2)
2.5 (3)
C2A—C1A—C11A—O12A
C6A—C1A—C11A—O11A
C6A—C1A—C11A—O12A
O2A—C2A—C3A—C4A
C1A—C2A—C3A—C4A
C2A—C3A—C4A—C5A
C3A—C4A—C5A—S5A
C3A—C4A—C5A—C6A
S5A—C5A—C6A—C1A
C4A—C5A—C6A—C1A
2.2 (3)
−177.0 (2)
−0.7 (3)
−176.95 (19)
178.7 (2)
−1.4 (3)
179.81 (19)
1.2 (3)
0.3 (3)
−178.8 (2)
−177.44 (19)
3.0 (3)
−179.92 (18)
0.4 (3)
−179.69 (16)
−0.1 (3)
179.6 (2)
Symmetry codes: (i) −x+1, y, −z+1; (ii) −x+2, y, −z+2.
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O2A—H2A···O12A
O2B—H2B···O12B
O11B—H11B···O11A
N1—H11···O53Aiii
N1—H12···O51Biv
N1—H13···O11A
N1—H14···O12B
N1—H14···O52Bv
N2—H21···O51Bvi
N2—H22···O11B
N2—H22···O12Aiii
N2—H23···O12A
N2—H24···O53Avii
N3—H31···O2A
N3—H32···O51Aviii
N3—H32···O52Aix
N4—H41···O2B
N4—H42···O52Bx
C4B—H4B···O53B
C6A—H6A···O53A
0.80 (3)
0.87 (3)
0.92 (3)
0.91
1.79 (2)
1.78 (3)
1.65 (3)
1.95
2.536 (2)
2.554 (2)
2.564 (2)
2.841 (2)
2.823 (3)
2.917 (2)
2.831 (2)
2.773 (2)
2.846 (3)
2.909 (2)
3.418 (2)
2.794 (2)
2.810 (2)
2.9753 (18)
2.848 (3)
2.9901 (16)
2.906 (2)
2.891 (2)
2.910 (3)
2.930 (3)
155 (2)
146 (3)
175 (3)
168
0.90
1.94
168
0.96
2.01
156
0.84
2.19
133
0.84
2.31
115
0.96
1.90
171
0.97
2.45
108
0.97
2.52
153
0.86
1.93
177
0.96
2.43
103
0.88
2.23
143
0.98
1.93
155
0.98
2.47
113
0.85
2.10
156
0.81
2.15
152
0.93
2.55
104
0.93
2.57
103
Symmetry codes: (iii) x, y+1, z; (iv) x+1/2, y−3/2, z; (v) x+1/2, y−1/2, z; (vi) x, y−1, z; (vii) x−1/2, y+1/2, z; (viii) −x+3/2, y−1/2, −z+1; (ix) −x+3/2, y+1/2,
−z+1; (x) −x+3/2, y+1/2, −z+2.
Acta Cryst. (2013). C69, 534-537
sup-9