Polymorphism in ammonium 2,4,6-trimethyl­benzene­sulfonate

Aucott, S.M.; Dale, S.H.; Elsegood, M.R.J.; Holmes, K.E.; Gilby, L.M.; Kelly, P.F.

doi:10.1107/S0108270104034274

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 3| March 2005| Pages o134-o137

doi:10.1107/S0108270104034274

Polymorphism in ammonium 2,4,6-trimethylbenzenesulfonate

Stephen M. Aucott,^a Sophie H. Dale,^a Mark R. J. Elsegood,^a Kathryn E. Holmes,^a Liam M. Gilby ^a and Paul F. Kelly ^a ^*

^aChemistry Department, Loughborough University, Loughborough, Leicestershire LE11 3TU, England
^*Correspondence e-mail: p.f.kelly@lboro.ac.uk

(Received 9 November 2004; accepted 23 December 2004; online 12 February 2005)

During investigations into sulfide- and selenide-amination reactions using the aminating agent o-mesitylsulfonylhydroxylamine, the monoclinic, (I), and orthorhombic, (II), polymorphs of ammonium 2,4,6-trimethylbenzenesulfonate, NH₄⁺·C₉H₁₁O₃S⁻, have been crystallized. Investigation of the hydrogen-bonding motifs within the two polymorphs shows that both contain N⁺—H⋯O⁻ hydrogen bonds between the ammonium cations and the 2,4,6-trimethylbenzenesulfonate anions. Polymorph (I) contains $[R_{4}^{4}]$ (12) and $[R_{4}^{2}]$ (8) graph-set ring motifs, while polymorph (II) contains the same $[R_{4}^{4}]$ (12) ring motif in combination with an $[R_{4}^{3}]$ (10) motif. The two hydrogen-bonding patterns result in slightly different packing structures for the two polymorphs, but both are based on a thick-sheet arrangement, in which the NH₄⁺ cations are enveloped between two layers of 2,4,6-trimethylbenzenesulfonate anions. In (I), the aromatic rings of the anions are approximately coplanar, giving parallel sheets, whereas in (II) the sheets are antiparallel and the anions pack in a herring-bone manner within the sheets, with angles of 78.76 (8)° between the planes of the aromatic rings.

Keywords: .

Comment

Sulfonate anions have been used in the formation of hydrogen-bonding arrays (Haynes et al., 2004 ; Russell & Ward, 1997 ), in particular in co-crystallization studies with the guanidinium cation, [C(NH₂)₃]⁺. We present here the monoclinic, (I), and orthorhombic, (II), polymorphs of ammonium 2,4,6-trimethylbenzenesulfonate.

The polymorphs crystallize simultaneously as colourless columns and needles, respectively, upon slow diffusion of diethyl ether vapour into methanolic solutions of the crude mixtures resulting from two reactions utilizing the aminating agent o-mesitylsulfonylhydroxylamine (MSH). Preliminary evidence (mass spectrometry and ⁷⁷Se NMR spectroscopy) indicates that the first reaction, of Ph₂Se with MSH, results in the formation of Ph₂SeNH₂⁺·2,4,6-Me₃C₆H₂SO₃⁻. Attempts to crystallize the compound have failed due to its high sensitivity to water, resulting in the hydrolysis of the cation to yield the title compound and, presumably, Ph₂Se=O. In the second reaction, amination of the thio crown ether [9]aneS₃(1,4,7-trithiacyclononane) leads to the formation of the [9]aneS(NH₂)S₂(μ-N)}²⁺ cation (in which an N atom bridges two of the S atoms), rather than the expected trisulfimidium cation, {[9-ane][S(NH₂)]₃}³⁺, with the formation of the title compound as a stable by-product (Elsegood et al., 2002 ).

Both polymorphs crystallize with one formula unit in the asymmetric unit (Figs. 1 and 2). The geometry of the 2,4,6-trimethylbenzenesulfonate anion in (I) (Table 1) and (II) (Table 3) shows good agreement with that previously determined (for example, Russell & Ward, 1997, and references therein). In both polymorphs, the methyl group showing the greatest deviation from the least-squares plane of the aromatic ring in the anion is that para to the sulfonate group (C8), with values of 0.139 (2) Å in (I) and 0.096 (6) Å in (II). Atom S1 deviates from the plane of the aromatic ring by 0.2339 (17) Å in (I) and by 0.190 (5) Å in (II).

In both polymorphs, each NH₄⁺ cation forms hydrogen bonds to four symmetry-related 2,4,6-trimethylbenzenesulfonate anions through N⁺—H⋯O⁻ hydrogen bonds, using each of the N—H groups once. The geometries of the hydrogen bonds in polymorphs (I) and (II) are similar (Tables 2 and 4) and in both cases hydrogen bonds link the cations and anions into two-dimensional sheets.

The reason for the polymorphism observed in (I) and (II) is clearly seen in the hydrogen-bonding motifs within the structures. In the monoclinic polymorph, (I), two types of graph-set ring motif (Etter, 1990 ; Etter et al., 1990 ; Bernstein et al., 1995 ) are observed (Fig. 3). In the larger of the two ring motifs, two sulfonate groups and two NH₄⁺ cations hydrogen bond together through N⁺—H⋯O⁻ hydrogen bonds, using two acceptor O atoms from each sulfonate group and two N—H donor groups from each NH₄⁺ cation, creating an $[R_{4}^{4}]$ (12) motif. A smaller $[R_{4}^{2}]$ (8) motif results from the hydrogen bonding of two sulfonate groups and two NH₄⁺ cations, using two N—H groups from each cation and only one O-atom acceptor from each sulfonate group.

Polymorph (II) (Fig. 4) exhibits the same $[R_{4}^{4}]$ (12) motif as observed for (I), but in place of the second, motif seen in (I), viz. $[R_{4}^{2}]$ (8), there is an $[R_{4}^{3}]$ (10) motif, in which two NH₄⁺ cations each donate two N—H groups, while one sulfonate group utilizes two acceptor O atoms and a second utilizes only one acceptor O atom in the hydrogen-bonding motif.

A recent study of supramolecular synthons in organic sulfonate structures in the Cambridge Structural Database (Haynes et al., 2004) has highlighted the three hydrogen-bonded ring motifs seen in (I) and (II) as three of the most common ring motifs in sulfonate compounds containing NH donors. The $[R_{4}^{2}]$ (8), $[R_{4}^{3}]$ (10) and $[R_{4}^{4}]$ (12) motifs occur in 13.47, 13.64 and 17.85%, respectively, of all sulfonate/NH-donor crystal structures. The study also highlights an R₆⁶(18) ring motif built from three sulfonate groups providing two O donor atoms each, and three NH_x donors providing two NH donors each. This motif occurs in 12.29% of all sulfonate/NH-donor crystal structures and is observed in both polymorphs (I) and (II) as a combination of two smaller rings.

The differences in the hydrogen-bonding motifs observed in (I) and (II) result in differences in the packing of the two-dimensional sheets. Both contain the same two-dimensional sheet arrangement, in which, within the sheets, two layers of 2,4,6-trimethylbenzenesulfonate anions sandwich one layer of NH₄⁺ cations, the charged NH₄⁺ cations and SO₃⁻ groups of the anions being enveloped between layers of relatively hydrophobic aromatic rings. In the case of (I), the sheets are parallel and extend in the crystallographic ac plane, whereas in (II), the sheets are antiparallel and extend in the crystallographic bc plane. Figs. 5 and 6 show the result of the different hydrogen-bonding motifs in (I) and (II), in that the polymorphs pack with different alignments of the aromatic rings of the 2,4,6-trimethylbenzenesulfonate anions. In (I) (Fig. 5), all of the aromatic groups are approximately coplanar, with maximum angles of 5.74 (7)° between the least-squares planes of symmetry-related anions. In contrast, while the close-packed aromatic groups of adjacent sheets are approximately coplanar in (II), with maximum angles of 1.77 (19)° between the least-squares planes of symmetry-related anions (Fig. 6), the least-squares planes of the aromatic rings in the two different layers within each thick sheet are aligned at angles of 78.76 (8)° to each other, in a herring-bone manner.

In conclusion, small differences in the hydrogen-bonding motifs have led to the crystallization of two polymorphs of the title compound. In consideration of the frequency of the use of MSH as an aminating agent, we hope that the presentation of these results will aid researchers in the identification of crystals of their desired novel aminated compounds, rather than of the ammonium 2,4,6-trimethylbenzenesulfonate by-product. Indeed, in addition to the two aforementioned specific examples, we have noted the compound forming as a by-product in variable yield in other thio ether and mixed sulfide ligand amination reactions. This highlights the ubiquitous nature of the product in MSH amination reactions and thus serves to emphasize the need for its effective identification.

Figure 1
A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.

Figure 2
A view of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.

Figure 3
A view of the hydrogen-bonding array in (I). H atoms (except those bound to N atoms) and all C atoms (except C1) have been removed for clarity. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z; (ii) 1 − x, −y, 1 − z; (iii) 1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z.]

Figure 4
A view of the hydrogen-bonding array in (II). H atoms (except those bound to N atoms) and all C atoms (except C1) have been removed for clarity. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) −x, y − $[{1\over 2}]$ , $[{1\over 2}]$ − z; (ii) $[{1\over 2}]$ + x, y, $[{1\over 2}]$ − z; (iii) $[{1\over 2}]$ − x, y − $[{1\over 2}]$ , z.]

Figure 5
A packing plot of (I), viewed along the crystallographic b axis. H atoms not involved in hydrogen bonding have been omitted for clarity and hydrogen bonds are shown as dashed lines.

Figure 6
A packing plot of (II), viewed along the crystallographic a axis. H atoms not involved in hydrogen bonding have been omitted for clarity and hydrogen bonds are shown as dashed lines.

Experimental

Colourless columnar crystals of (I) and colourless needles of (II) crystallized simultaneously upon slow diffusion of diethyl ether vapour into a methanolic solution of a crude reaction mixture containing the title compound as either a by-product or a hydrolysis product (see Comment for further details).

Compound (I)

Crystal data

NH₄⁺·C₉H₁₁O₃S⁻
M_r = 217.28
Monoclinic, P2₁/c
a = 13.7562 (15) Å
b = 8.4253 (9) Å
c = 9.4761 (10) Å
β = 97.368 (2)°
V = 1089.2 (2) Å³
Z = 4
D_x = 1.325 Mg m⁻³
Mo Kα radiation
Cell parameters from 5637 reflections
θ = 2.8–28.4°
μ = 0.28 mm⁻¹
T = 150 (2) K
Column, colourless
0.76 × 0.19 × 0.13 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
ω rotation scans with narrow frame
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.816, T_max = 0.965
8693 measured reflections
2510 independent reflections
2202 reflections with I > 2σ(I)
R_int = 0.037
θ_max = 28.5°
h = −17 → 17
k = −10 → 11
l = −12 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.094
S = 1.04
2510 reflections
142 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0544P)² + 0.3258P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected bond lengths (Å) for (I)

S1—O1	1.4632 (10)
S1—O2	1.4584 (10)
S1—O3	1.4557 (10)

Table 2
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.83 (2)	1.98 (2)	2.8124 (17)	171.5 (18)
N1—H1B⋯O1ⁱ	0.92 (2)	1.91 (2)	2.8261 (17)	175.0 (17)
N1—H1C⋯O3ⁱⁱ	0.87 (2)	1.96 (2)	2.8253 (16)	172.8 (18)
N1—H1D⋯O1ⁱⁱⁱ	0.83 (2)	2.18 (2)	2.9846 (16)	162.7 (18)
Symmetry codes: (i) $[x, {\script{1\over 2}}-y, z+{\script{1\over 2}}]$ ; (ii) 1-x, -y, 1-z; (iii) $[1-x, y+{\script{1\over 2}}, {\script{1\over 2}}-z]$ .

Compound (II)

Crystal data

NH₄⁺·C₉H₁₁O₃S⁻
M_r = 217.29
Orthorhombic, Pbca
a = 8.4792 (13) Å
b = 9.6152 (15) Å
c = 26.864 (4) Å
V = 2190.2 (6) Å³
Z = 8
D_x = 1.318 Mg m⁻³
Mo Kα radiation
Cell parameters from 2914 reflections
θ = 2.8–26.7°
μ = 0.28 mm⁻¹
T = 150 (2) K
Needle, colourless
0.45 × 0.04 × 0.02 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
ω rotation scans with narrow frame
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)T_min = 0.885, T_max = 0.995
14 511 measured reflections
1929 independent reflections
1328 reflections with I > 2σ(I)
R_int = 0.047
θ_max = 25.0°
h = −10 → 10
k = −11 → 11
l = −31 → 31

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.199
S = 1.15
1929 reflections
142 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.105P)² + 1.889P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 3
Selected bond lengths (Å) for (II)

S1—O1	1.438 (3)
S1—O2	1.450 (3)
S1—O3	1.456 (3)
S1—C1	1.780 (4)

Table 4
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.90 (2)	1.86 (2)	2.755 (4)	173 (3)
N1—H1B⋯O3ⁱ	0.93 (2)	1.84 (2)	2.734 (4)	160 (3)
N1—H1C⋯O2ⁱⁱ	0.89 (2)	1.96 (2)	2.828 (4)	165 (3)
N1—H1D⋯O3ⁱⁱⁱ	0.92 (2)	1.95 (2)	2.861 (4)	167 (3)
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, {\script{1\over 2}}-z]$ ; (ii) $[x+{\script{1\over 2}}, y, {\script{1\over 2}}-z]$ ; (iii) $[{\script{1\over 2}}-x, y-{\script{1\over 2}}, z]$ .

Aromatic (C—H = 0.95 Å) and methyl (C—H = 0.98 Å) H atoms were placed in geometrically calculated positions and refined using a riding model. In (I), N-bound H atoms were located in a difference Fourier map and their coordinates refined freely. In (II), the N-bound H atoms were refined using restraints on the N—H bond length [target value = 0.90 (3) Å] and on the H—N—H angle (restrained to give similar 1,3-distances). In both structures, U_iso(H) values were set at 1.2U_eq(C) for aryl H, and at 1.5U_eq(N,C) for NH and methyl H atoms. Data for (II) were truncated at 2θ = 50° as only statistically insignificant data were present above this limit.

For both compounds, data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepar material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S0108270104034274/bm1599sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104034274/bm1599Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270104034274/bm1599IIsup3.hkl

Comment top

Sulfonate anions have been used in the formation of hydrogen-bonding arrays (Haynes et al., 2004; Russell & Ward, 1997), in particular in co-crystallization studies with the guanidinium cation, [C(NH₂)₃]⁺. Here, we present the monoclinic, (I), and orthorhombic, (II), polymorphs of ammonium 2,4,6-trimethylbenzenesulfonate.

The polymorphs crystallize simultaneously as colourless columns and needles, respectively, upon slow diffusion of diethyl ether vapour into methanolic solutions of the crude mixtures resulting from two reactions utilizing the aminating agent o-mesitylsulfonylhydroxylamine (MSH). Preliminary evidence (mass spectrometry, ⁷⁷Se NMR spectroscopy) indicates that the first reaction, of Ph₂Se with MSH, results in the formation of Ph₂SeNH₂⁺.2,4,6-Me₃C₆H₂SO₃⁻. Attempts to crystallize the compound have failed, due to its high sensitivity to water, resulting in the hydrolysis of the cation to yield the title compound and, presumably, Ph₂Se═O. In the second reaction, amination of the thio crown ether [9]aneS₃ leads to the formation of the {[9-ane]S(NH₂)S₂(µ-N)}²⁺ cation (in which an N atom bridges two of the S atoms), rather than the expected trisulfimidium cation, {[9-ane][S(NH₂)]₃}³⁺, with the formation of the title compound as a stable by-product (Elsegood et al., 2002).

Both polymorphs crystallize with one formula unit in the asymmetric unit (Figs. 1 and 2). The geometry of the 2,4,6-trimethylbenzenesulfonate anion in (I) (Table 1) and (II) (Table 3) shows good agreement with that previously determined (for example, Russell & Ward, 1997). In both polymorphs, the methyl group showing the greatest deviation from the least-squares plane of the aromatic ring in the anion is that para to the sulfonate group (C8), with values of 0.149 (2) Å [From the Co-Editor: please check value of 0.149 - I get 0.139] in (I) and 0.096 (6) Å in (II). Atom S1 deviates from the plane of the aromatic ring by 0.2339 (17) Å in (I) and by 0.190 (5) Å in (II).

In both polymorphs, each NH₄⁺ cation forms hydrogen bonds to four symmetry-related 2,4,6-trimethylbenzenesulfonate anions through N⁺—H···O⁻ hydrogen bonds, using each of the N—H groups once. The geometries of the hydrogen bonds in polymorphs (I) and (II) are similar (Tables 2 and 4), and in both cases hydrogen bonds link the cations and anions into two-dimensional sheets.

The reason for the polymorphism observed in (I) and (II) is clearly seen in the hydrogen-bonding motifs within the structures. In the monoclinic polymorph, (I), two types of graph-set ring motif (Etter, 1990; Etter et al., 1990; Bernstein et al., 1995) are observed (Fig. 3). In the larger of the two ring motifs, two sulfonate groups and two NH₄⁺ cations hydrogen bond together through N⁺—H···O⁻ hydrogen bonds, using two acceptor O atoms from each sulfonate group and two N—H donor groups from each NH₄⁺ cation, creating an R₄⁴(12) motif. A smaller R₄²(8) motif results from the hydrogen bonding of two sulfonate groups and two NH₄⁺ cations, using two N—H groups from each cation and only one O acceptor from each sulfonate group.

Polymorph (II) (Fig. 4) exhibits the same R₄⁴(12) motif as observed for (I), but in place of the second, R₄²(8), motif seen in (I), there is an R₄³(10) motif, in which two NH₄⁺ cations each donate two N—H groups, while one sulfonate group utilizes two acceptor O atoms and a second utilizes only one acceptor O atom in the hydrogen-bonding motif.

A recent study of supramolecular synthons in organic sulfonate structures in the Cambridge Structural Database (Haynes et al., 2004) has highlighted the three hydrogen-bonded ring motifs seen in (I) and (II) as three of the most common ring motifs in sulfonate compounds containing NH donors. The R₄²(8), R₄³(10) and R₄⁴(12) motifs occur in 13.47, 13.64 and 17.85%, respectively, of all sulfonate/NH-donor crystal structures. The study also highlights an R₆⁶(18) ring motif built from three sulfonate groups providing two O donor atoms each, and three NHx donors providing two NH donors each. This motif occurs in 12.29% of all sulfonate/NH-donor crystal structures, and is observed in both polymorphs (I) and (II) as a combination of two smaller rings.

The differences in the hydrogen-bonding motifs observed in (I) and (II) result in differences in the packing of the two-dimensional sheets. Both contain the same two-dimensional sheet arrangement, in which, within the sheets, two layers of 2,4,6-trimethylbenzenesulfonate anions sandwich one layer of NH₄⁺ cations, the charged NH₄⁺ cations and SO₃⁻ groups of the anions being enveloped between layers of relatively hydrophobic aromatic rings. In the case of (I), the sheets are parallel and extend in the crystallographic ac plane, whereas in (II), the sheets are anti-parallel and extend in the crystallographic bc plane. Figs. 5 and 6 show the result of the different hydrogen-bonding motifs in (I) and (II), in that the polymorphs pack with different alignments of the aromatic rings of the 2,4,6-trimethylbenzenesulfonate anions. In (I) (Fig. 5), all of the aromatic groups are approximately coplanar, with maximum angles of 5.74 (7)° between the least-squares planes of symmetry-related anions. In contrast, while the close-packed aromatic groups of adjacent sheets are approximately coplanar in (II), with maximum angles of 1.77 (19)° between the least-squares planes of symmetry-related anions (Fig. 6), the least-squares planes of the aromatic rings in the two different layers within each thick sheet are aligned at angles of 78.76 (8)° to each other, in a herringbone manner.

In conclusion, small differences in the hydrogen-bonding motifs have led to the crystallization of two polymorphs of the title compound. In consideration of the frequency of the use of MSH as an aminating agent, we hope that the presentation of these results will aid researchers in the identification of crystals of their desired novel aminated compounds, rather than of the ammonium 2,4,6-trimethylbenzenesulfonate by-product. Indeed, in addition to the two aforementioned specific examples, we have noted the compound forming as a by-product in variable yield in other thio ether and mixed sulfide ligand amination reactions. This highlights the ubiquitous nature of the product in MSH amination reactions, and thus serves to emphasize the need for its effective identification.

Experimental top

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures top

	Fig. 1. A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 2. A view of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 3. A view of the hydrogen-bonding array in (I). H atoms except those bound to N atoms, and all C atoms except C1, have been removed for clarity. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x, 1/2 − y, 1/2 + z; (ii) 1 − x, −y, 1 − z; (iii) 1 − x, 1/2 + y, 1/2 − z.]
	Fig. 4. A view of the hydrogen-bonding array in (II). H atoms except those bound to N atoms, and all C atoms except C1, have been removed for clarity. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) −x, y − 1/2, 1/2 − z; (ii) 1/2 + x, y, 1/2 − z; (iii) 1/2 − x, y − 1/2, z.]
	Fig. 5. A packing plot of (I), viewed along the crystallographic b axis. H atoms not involved in hydrogen bonding have been omitted for clarity and hydrogen bonds are shown as dashed lines.
	Fig. 6. A packing plot of (II), viewed along the crystallographic a axis. H atoms not involved in hydrogen bonding have been omitted for clarity and hydrogen bonds are shown as dashed lines.

(I) Ammonium 2,4,6-trimethylbenzenesulfonate top

Crystal data top

NH₄⁺·C₉H₁₁O₃S⁻	F(000) = 464
M_r = 217.28	D_x = 1.325 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5637 reflections
a = 13.7562 (15) Å	θ = 2.8–28.4°
b = 8.4253 (9) Å	µ = 0.28 mm⁻¹
c = 9.4761 (10) Å	T = 150 K
β = 97.368 (2)°	Column, colourless
V = 1089.2 (2) Å³	0.76 × 0.19 × 0.13 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2510 independent reflections
Radiation source: sealed tube	2202 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω rotation with narrow frame scans	θ_max = 28.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −17→17
T_min = 0.816, T_max = 0.965	k = −10→11
8693 measured reflections	l = −12→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: geom, except NH coords freely refined
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0544P)² + 0.3258P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2510 reflections	Δρ_max = 0.32 e Å⁻³
142 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints

Crystal data top

NH₄⁺·C₉H₁₁O₃S⁻	V = 1089.2 (2) Å³
M_r = 217.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.7562 (15) Å	µ = 0.28 mm⁻¹
b = 8.4253 (9) Å	T = 150 K
c = 9.4761 (10) Å	0.76 × 0.19 × 0.13 mm
β = 97.368 (2)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2510 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2202 reflections with I > 2σ(I)
T_min = 0.816, T_max = 0.965	R_int = 0.037
8693 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.32 e Å⁻³
2510 reflections	Δρ_min = −0.36 e Å⁻³
142 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.64160 (2)	0.00789 (4)	0.27714 (3)	0.02395 (12)
O1	0.63608 (7)	0.05481 (12)	0.12765 (10)	0.0319 (2)
O2	0.55555 (7)	0.05991 (13)	0.33985 (11)	0.0352 (2)
O3	0.65527 (8)	−0.16295 (11)	0.29157 (10)	0.0338 (2)
C1	0.74346 (9)	0.10754 (15)	0.37443 (13)	0.0233 (2)
C2	0.81442 (10)	0.02519 (17)	0.46791 (14)	0.0295 (3)
C3	0.88446 (10)	0.11580 (19)	0.55276 (15)	0.0343 (3)
H3	0.9331	0.0622	0.6153	0.041*
C4	0.88601 (10)	0.27970 (19)	0.54963 (14)	0.0328 (3)
C5	0.81765 (10)	0.35636 (17)	0.45313 (14)	0.0299 (3)
H5	0.8198	0.4688	0.4470	0.036*
C6	0.74563 (9)	0.27438 (15)	0.36442 (13)	0.0250 (3)
C7	0.82054 (13)	−0.1534 (2)	0.4874 (2)	0.0493 (4)
H7A	0.7656	−0.1898	0.5353	0.074*
H7B	0.8825	−0.1809	0.5453	0.074*
H7C	0.8175	−0.2048	0.3941	0.074*
C8	0.95741 (12)	0.3727 (2)	0.65283 (17)	0.0463 (4)
H8A	0.9378	0.3656	0.7485	0.069*
H8B	0.9573	0.4842	0.6231	0.069*
H8C	1.0234	0.3287	0.6537	0.069*
C9	0.67356 (10)	0.37130 (16)	0.26617 (16)	0.0326 (3)
H9A	0.6856	0.4845	0.2846	0.049*
H9B	0.6066	0.3449	0.2830	0.049*
H9C	0.6817	0.3474	0.1671	0.049*
N1	0.46762 (10)	0.27413 (15)	0.51265 (13)	0.0291 (2)
H1A	0.4879 (14)	0.207 (2)	0.459 (2)	0.044*
H1B	0.5235 (14)	0.325 (2)	0.554 (2)	0.044*
H1C	0.4341 (14)	0.235 (2)	0.576 (2)	0.044*
H1D	0.4309 (15)	0.337 (2)	0.465 (2)	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02388 (18)	0.02563 (19)	0.02225 (18)	−0.00339 (11)	0.00263 (12)	−0.00235 (10)
O1	0.0344 (5)	0.0372 (5)	0.0229 (5)	−0.0062 (4)	−0.0006 (4)	0.0002 (4)
O2	0.0249 (5)	0.0426 (6)	0.0391 (6)	−0.0061 (4)	0.0076 (4)	−0.0106 (4)
O3	0.0411 (6)	0.0250 (5)	0.0351 (5)	−0.0044 (4)	0.0033 (4)	−0.0020 (4)
C1	0.0209 (5)	0.0277 (6)	0.0212 (5)	−0.0016 (4)	0.0023 (4)	−0.0018 (4)
C2	0.0268 (6)	0.0337 (7)	0.0276 (6)	0.0024 (5)	0.0015 (5)	0.0024 (5)
C3	0.0265 (6)	0.0481 (8)	0.0267 (6)	0.0002 (6)	−0.0023 (5)	0.0035 (6)
C4	0.0241 (6)	0.0491 (8)	0.0255 (6)	−0.0083 (6)	0.0041 (5)	−0.0078 (6)
C5	0.0276 (6)	0.0307 (7)	0.0322 (7)	−0.0055 (5)	0.0067 (5)	−0.0066 (5)
C6	0.0225 (6)	0.0283 (6)	0.0247 (6)	−0.0015 (5)	0.0047 (4)	−0.0018 (5)
C7	0.0451 (9)	0.0374 (8)	0.0606 (10)	0.0077 (7)	−0.0113 (8)	0.0112 (8)
C8	0.0354 (8)	0.0674 (11)	0.0350 (8)	−0.0157 (8)	−0.0002 (6)	−0.0142 (7)
C9	0.0311 (7)	0.0257 (6)	0.0398 (7)	−0.0002 (5)	0.0004 (5)	0.0035 (5)
N1	0.0350 (6)	0.0279 (6)	0.0235 (5)	−0.0006 (5)	0.0010 (5)	0.0052 (4)

Geometric parameters (Å, º) top

S1—O1	1.4632 (10)	C6—C9	1.5099 (18)
S1—O2	1.4584 (10)	C7—H7A	0.9800
S1—O3	1.4557 (10)	C7—H7B	0.9800
S1—C1	1.7852 (12)	C7—H7C	0.9800
C1—C6	1.4094 (18)	C8—H8A	0.9800
C1—C2	1.4132 (18)	C8—H8B	0.9800
C2—C3	1.400 (2)	C8—H8C	0.9800
C2—C7	1.517 (2)	C9—H9A	0.9800
C3—C4	1.381 (2)	C9—H9B	0.9800
C3—H3	0.9500	C9—H9C	0.9800
C4—C5	1.385 (2)	N1—H1A	0.83 (2)
C4—C8	1.5130 (19)	N1—H1B	0.92 (2)
C5—C6	1.3970 (17)	N1—H1C	0.87 (2)
C5—H5	0.9500	N1—H1D	0.83 (2)

O1—S1—O2	111.66 (6)	C2—C7—H7A	109.5
O1—S1—O3	110.37 (6)	C2—C7—H7B	109.5
O2—S1—O3	111.14 (6)	H7A—C7—H7B	109.5
O1—S1—C1	108.23 (6)	C2—C7—H7C	109.5
O2—S1—C1	105.81 (6)	H7A—C7—H7C	109.5
O3—S1—C1	109.46 (6)	H7B—C7—H7C	109.5
C6—C1—C2	120.86 (11)	C4—C8—H8A	109.5
C6—C1—S1	117.15 (9)	C4—C8—H8B	109.5
C2—C1—S1	121.74 (10)	H8A—C8—H8B	109.5
C3—C2—C1	117.49 (13)	C4—C8—H8C	109.5
C3—C2—C7	116.60 (13)	H8A—C8—H8C	109.5
C1—C2—C7	125.90 (13)	H8B—C8—H8C	109.5
C4—C3—C2	122.98 (13)	C6—C9—H9A	109.5
C4—C3—H3	118.5	C6—C9—H9B	109.5
C2—C3—H3	118.5	H9A—C9—H9B	109.5
C3—C4—C5	117.99 (12)	C6—C9—H9C	109.5
C3—C4—C8	120.97 (14)	H9A—C9—H9C	109.5
C5—C4—C8	120.98 (15)	H9B—C9—H9C	109.5
C4—C5—C6	122.40 (13)	H1A—N1—H1B	104.6 (17)
C4—C5—H5	118.8	H1A—N1—H1C	114.4 (19)
C6—C5—H5	118.8	H1B—N1—H1C	111.8 (17)
C5—C6—C1	118.17 (12)	H1A—N1—H1D	109.2 (18)
C5—C6—C9	117.55 (12)	H1B—N1—H1D	110.5 (18)
C1—C6—C9	124.26 (11)	H1C—N1—H1D	106.5 (18)

O3—S1—C1—C6	175.86 (9)	C7—C2—C3—C4	−177.98 (14)
O2—S1—C1—C6	−64.29 (11)	C2—C3—C4—C5	−3.1 (2)
O1—S1—C1—C6	55.53 (11)	C2—C3—C4—C8	174.37 (13)
O3—S1—C1—C2	−9.81 (12)	C3—C4—C5—C6	2.7 (2)
O2—S1—C1—C2	110.03 (11)	C8—C4—C5—C6	−174.68 (13)
O1—S1—C1—C2	−130.15 (11)	C4—C5—C6—C1	−0.14 (19)
C6—C1—C2—C3	1.99 (19)	C4—C5—C6—C9	178.49 (12)
S1—C1—C2—C3	−172.12 (10)	C2—C1—C6—C5	−2.28 (18)
C6—C1—C2—C7	−179.42 (14)	S1—C1—C6—C5	172.10 (9)
S1—C1—C2—C7	6.5 (2)	C2—C1—C6—C9	179.19 (12)
C1—C2—C3—C4	0.7 (2)	S1—C1—C6—C9	−6.44 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.83 (2)	1.98 (2)	2.8124 (17)	171.5 (18)
N1—H1B···O1ⁱ	0.92 (2)	1.91 (2)	2.8261 (17)	175.0 (17)
N1—H1C···O3ⁱⁱ	0.87 (2)	1.96 (2)	2.8253 (16)	172.8 (18)
N1—H1D···O1ⁱⁱⁱ	0.83 (2)	2.18 (2)	2.9846 (16)	162.7 (18)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) −x+1, y+1/2, −z+1/2.

(II) Ammonium 2,4,6-trimethylbenzenesulfonate top

Crystal data top

NH₄⁺·C₉H₁₁O₃S⁻	F(000) = 928
M_r = 217.29	D_x = 1.318 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2914 reflections
a = 8.4792 (13) Å	θ = 2.8–26.7°
b = 9.6152 (15) Å	µ = 0.28 mm⁻¹
c = 26.864 (4) Å	T = 150 K
V = 2190.2 (6) Å³	Needle, colourless
Z = 8	0.45 × 0.04 × 0.02 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1929 independent reflections
Radiation source: sealed tube	1328 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ω rotation with narrow frame scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→10
T_min = 0.885, T_max = 0.995	k = −11→11
14511 measured reflections	l = −31→31

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: geom, except NH coords refined with restraints
R[F² > 2σ(F²)] = 0.066	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.199	w = 1/[σ²(F_o²) + (0.105P)² + 1.889P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max = 0.001
1929 reflections	Δρ_max = 0.78 e Å⁻³
142 parameters	Δρ_min = −0.27 e Å⁻³
19 restraints

Crystal data top

NH₄⁺·C₉H₁₁O₃S⁻	V = 2190.2 (6) Å³
M_r = 217.29	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.4792 (13) Å	µ = 0.28 mm⁻¹
b = 9.6152 (15) Å	T = 150 K
c = 26.864 (4) Å	0.45 × 0.04 × 0.02 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1929 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1328 reflections with I > 2σ(I)
T_min = 0.885, T_max = 0.995	R_int = 0.047
14511 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	19 restraints
wR(F²) = 0.199	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	Δρ_max = 0.78 e Å⁻³
1929 reflections	Δρ_min = −0.27 e Å⁻³
142 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.03991 (11)	0.32818 (9)	0.17594 (3)	0.0389 (4)
O1	0.1481 (4)	0.2483 (3)	0.20563 (12)	0.0668 (9)
O2	−0.0804 (4)	0.2418 (3)	0.15329 (10)	0.0594 (8)
O3	−0.0293 (3)	0.4403 (3)	0.20508 (10)	0.0498 (7)
C1	0.1445 (4)	0.4138 (3)	0.12734 (12)	0.0375 (8)
C2	0.0551 (5)	0.4918 (4)	0.09317 (13)	0.0419 (9)
C3	0.1362 (6)	0.5705 (4)	0.05764 (15)	0.0525 (11)
H3	0.0772	0.6222	0.0340	0.063*
C4	0.2987 (6)	0.5759 (4)	0.05566 (15)	0.0518 (11)
C5	0.3816 (5)	0.4953 (4)	0.08895 (14)	0.0507 (11)
H5	0.4934	0.4959	0.0870	0.061*
C6	0.3113 (5)	0.4129 (4)	0.12527 (13)	0.0426 (9)
C7	−0.1230 (5)	0.4999 (5)	0.09263 (15)	0.0599 (12)
H7A	−0.1671	0.4057	0.0933	0.090*
H7B	−0.1579	0.5476	0.0623	0.090*
H7C	−0.1595	0.5516	0.1219	0.090*
C8	0.3831 (7)	0.6691 (5)	0.01907 (18)	0.0741 (16)
H8A	0.4962	0.6482	0.0196	0.111*
H8B	0.3665	0.7666	0.0284	0.111*
H8C	0.3414	0.6530	−0.0145	0.111*
C9	0.4187 (5)	0.3305 (5)	0.15908 (17)	0.0578 (12)
H9A	0.5285	0.3445	0.1489	0.087*
H9B	0.3922	0.2315	0.1568	0.087*
H9C	0.4050	0.3620	0.1935	0.087*
N1	0.3041 (4)	0.0706 (3)	0.26924 (11)	0.0397 (8)
H1C	0.345 (4)	0.110 (3)	0.2963 (10)	0.059*
H1B	0.225 (3)	0.009 (3)	0.2791 (12)	0.059*
H1A	0.261 (4)	0.133 (3)	0.2482 (11)	0.059*
H1D	0.380 (3)	0.020 (3)	0.2526 (12)	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0416 (6)	0.0406 (6)	0.0346 (6)	−0.0004 (4)	0.0017 (4)	0.0036 (4)
O1	0.0603 (18)	0.076 (2)	0.0640 (19)	0.0160 (16)	0.0086 (16)	0.0338 (17)
O2	0.0701 (19)	0.0580 (18)	0.0501 (17)	−0.0251 (15)	−0.0001 (15)	−0.0014 (14)
O3	0.0513 (16)	0.0557 (16)	0.0425 (14)	−0.0010 (13)	0.0098 (13)	−0.0035 (13)
C1	0.048 (2)	0.0340 (18)	0.0301 (18)	−0.0003 (16)	0.0053 (16)	−0.0052 (14)
C2	0.055 (2)	0.0362 (19)	0.0343 (19)	0.0100 (17)	0.0062 (17)	0.0000 (15)
C3	0.076 (3)	0.039 (2)	0.043 (2)	0.011 (2)	0.011 (2)	0.0034 (17)
C4	0.078 (3)	0.034 (2)	0.043 (2)	−0.009 (2)	0.020 (2)	−0.0068 (17)
C5	0.051 (2)	0.050 (2)	0.051 (2)	−0.012 (2)	0.014 (2)	−0.016 (2)
C6	0.047 (2)	0.044 (2)	0.0363 (19)	−0.0030 (17)	0.0027 (17)	−0.0113 (16)
C7	0.056 (3)	0.075 (3)	0.049 (2)	0.020 (2)	0.003 (2)	0.013 (2)
C8	0.110 (4)	0.050 (3)	0.062 (3)	−0.021 (3)	0.037 (3)	−0.006 (2)
C9	0.043 (2)	0.081 (3)	0.050 (2)	0.003 (2)	−0.002 (2)	−0.008 (2)
N1	0.0417 (17)	0.0382 (16)	0.0390 (17)	−0.0066 (14)	−0.0044 (14)	0.0003 (14)

Geometric parameters (Å, º) top

S1—O1	1.438 (3)	C6—C9	1.511 (6)
S1—O2	1.450 (3)	C7—H7A	0.9800
S1—O3	1.456 (3)	C7—H7B	0.9800
S1—C1	1.780 (4)	C7—H7C	0.9800
C1—C2	1.407 (5)	C8—H8A	0.9800
C1—C6	1.415 (5)	C8—H8B	0.9800
C2—C3	1.399 (5)	C8—H8C	0.9800
C2—C7	1.512 (6)	C9—H9A	0.9800
C3—C4	1.380 (7)	C9—H9B	0.9800
C3—H3	0.9500	C9—H9C	0.9800
C4—C5	1.376 (6)	N1—H1C	0.89 (2)
C4—C8	1.510 (5)	N1—H1B	0.93 (2)
C5—C6	1.391 (5)	N1—H1A	0.90 (2)
C5—H5	0.9500	N1—H1D	0.92 (2)

O1—S1—O2	112.09 (19)	C2—C7—H7A	109.5
O1—S1—O3	110.76 (19)	C2—C7—H7B	109.5
O1—S1—C1	109.62 (17)	H7A—C7—H7B	109.5
O2—S1—O3	111.48 (18)	C2—C7—H7C	109.5
O2—S1—C1	107.93 (16)	H7A—C7—H7C	109.5
O3—S1—C1	104.64 (16)	H7B—C7—H7C	109.5
C2—C1—C6	121.1 (3)	C4—C8—H8A	109.5
C2—C1—S1	117.2 (3)	C4—C8—H8B	109.5
C6—C1—S1	121.6 (3)	H8A—C8—H8B	109.5
C3—C2—C1	117.9 (4)	C4—C8—H8C	109.5
C3—C2—C7	117.2 (3)	H8A—C8—H8C	109.5
C1—C2—C7	124.9 (3)	H8B—C8—H8C	109.5
C4—C3—C2	122.5 (4)	C6—C9—H9A	109.5
C4—C3—H3	118.7	C6—C9—H9B	109.5
C2—C3—H3	118.7	H9A—C9—H9B	109.5
C5—C4—C3	117.6 (4)	C6—C9—H9C	109.5
C5—C4—C8	121.0 (4)	H9A—C9—H9C	109.5
C3—C4—C8	121.4 (4)	H9B—C9—H9C	109.5
C4—C5—C6	123.9 (4)	H1C—N1—H1B	108 (2)
C4—C5—H5	118.0	H1C—N1—H1A	113 (2)
C6—C5—H5	118.0	H1B—N1—H1A	108 (2)
C5—C6—C1	116.9 (4)	H1C—N1—H1D	111 (2)
C5—C6—C9	117.5 (4)	H1B—N1—H1D	107 (2)
C1—C6—C9	125.6 (4)	H1A—N1—H1D	109 (2)

O1—S1—C1—C2	177.1 (3)	C7—C2—C3—C4	177.4 (4)
O2—S1—C1—C2	54.8 (3)	C2—C3—C4—C5	2.8 (6)
O3—S1—C1—C2	−64.1 (3)	C2—C3—C4—C8	−175.9 (3)
O1—S1—C1—C6	−7.7 (4)	C3—C4—C5—C6	−2.2 (6)
O2—S1—C1—C6	−130.1 (3)	C8—C4—C5—C6	176.5 (3)
O3—S1—C1—C6	111.1 (3)	C4—C5—C6—C1	0.0 (5)
C6—C1—C2—C3	−1.2 (5)	C4—C5—C6—C9	−179.9 (4)
S1—C1—C2—C3	174.0 (3)	C2—C1—C6—C5	1.7 (5)
C6—C1—C2—C7	−179.7 (4)	S1—C1—C6—C5	−173.2 (3)
S1—C1—C2—C7	−4.5 (5)	C2—C1—C6—C9	−178.4 (3)
C1—C2—C3—C4	−1.2 (6)	S1—C1—C6—C9	6.7 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.90 (2)	1.86 (2)	2.755 (4)	173 (3)
N1—H1B···O3ⁱ	0.93 (2)	1.84 (2)	2.734 (4)	160 (3)
N1—H1C···O2ⁱⁱ	0.89 (2)	1.96 (2)	2.828 (4)	165 (3)
N1—H1D···O3ⁱⁱⁱ	0.92 (2)	1.95 (2)	2.861 (4)	167 (3)

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x+1/2, y, −z+1/2; (iii) −x+1/2, y−1/2, z.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	NH₄⁺·C₉H₁₁O₃S⁻	NH₄⁺·C₉H₁₁O₃S⁻
M_r	217.28	217.29
Crystal system, space group	Monoclinic, P2₁/c	Orthorhombic, Pbca
Temperature (K)	150	150
a, b, c (Å)	13.7562 (15), 8.4253 (9), 9.4761 (10)	8.4792 (13), 9.6152 (15), 26.864 (4)
α, β, γ (°)	90, 97.368 (2), 90	90, 90, 90
V (Å³)	1089.2 (2)	2190.2 (6)
Z	4	8
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.28	0.28
Crystal size (mm)	0.76 × 0.19 × 0.13	0.45 × 0.04 × 0.02

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.816, 0.965	0.885, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	8693, 2510, 2202	14511, 1929, 1328
R_int	0.037	0.047
(sin θ/λ)_max (Å⁻¹)	0.672	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.094, 1.04	0.066, 0.199, 1.15
No. of reflections	2510	1929
No. of parameters	142	142
No. of restraints	0	19
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.36	0.78, −0.27

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Bruker, 2000), SHELXTL and local programs.

Selected bond lengths (Å) for (I) top

S1—O1	1.4632 (10)	S1—O3	1.4557 (10)
S1—O2	1.4584 (10)

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.83 (2)	1.98 (2)	2.8124 (17)	171.5 (18)
N1—H1B···O1ⁱ	0.92 (2)	1.91 (2)	2.8261 (17)	175.0 (17)
N1—H1C···O3ⁱⁱ	0.87 (2)	1.96 (2)	2.8253 (16)	172.8 (18)
N1—H1D···O1ⁱⁱⁱ	0.83 (2)	2.18 (2)	2.9846 (16)	162.7 (18)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) −x+1, y+1/2, −z+1/2.

Selected bond lengths (Å) for (II) top

S1—O1	1.438 (3)	S1—O3	1.456 (3)
S1—O2	1.450 (3)	S1—C1	1.780 (4)

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.90 (2)	1.86 (2)	2.755 (4)	173 (3)
N1—H1B···O3ⁱ	0.93 (2)	1.84 (2)	2.734 (4)	160 (3)
N1—H1C···O2ⁱⁱ	0.89 (2)	1.96 (2)	2.828 (4)	165 (3)
N1—H1D···O3ⁱⁱⁱ	0.92 (2)	1.95 (2)	2.861 (4)	167 (3)

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x+1/2, y, −z+1/2; (iii) −x+1/2, y−1/2, z.

Acknowledgements

The authors acknowledge the EPSRC for Postdoctoral Research Assistant support (LMG and SMA).

References

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ISSN: 2053-2296

Volume 61| Part 3| March 2005| Pages o134-o137

doi:10.1107/S0108270104034274