organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Polymorphism in ammonium 2,4,6-tri­methyl­benzene­sulfonate

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[Haynes, D. A., Chisholm, J. A., Jones, W. & Motherwell, W. D. S. (2004). CrystEngComm, 6, 584-588.]; Russell & Ward, 1997[Russell, V. A. & Ward, M. D. (1997). J. Mater. Chem. 7, 1123-1133.]), 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[Elsegood, M. R. J., Holmes, K. E., Gilby, L. M. & Kelly, P. F. (2002). Can. J. Chem. 18, 1410-1414.]).

[Scheme 1]

Both polymorphs crystallize with one formula unit in the asymmetric unit (Figs. 1[link] and 2[link]). The geometry of the 2,4,6-trimethyl­benzene­sulfonate anion in (I) (Table 1[link]) and (II) (Table 3[link]) shows good agreement with that previously determined (for example, Russell & Ward, 1997[Russell, V. A. & Ward, M. D. (1997). J. Mater. Chem. 7, 1123-1133.], 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[link] and 4[link]) 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, M. C. (1990). Acc. Chem. Res. 23, 120-126.]; Etter et al., 1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]; Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) are observed (Fig. 3[link]). 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[link]) 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[Haynes, D. A., Chisholm, J. A., Jones, W. & Motherwell, W. D. S. (2004). CrystEngComm, 6, 584-588.]) 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 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 antiparallel and extend in the crystallographic bc plane. Figs. 5[link] and 6[link] 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[link]), 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[link]), 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]
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]
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]
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]
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]
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]
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

  • Mr = 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

  • Dx = 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[Sheldrick, G. M. (2003). SADABS. Version 2.08. University of Göttingen, Germany.])Tmin = 0.816, Tmax = 0.965

  • 8693 measured reflections

  • 2510 independent reflections

  • 2202 reflections with I > 2σ(I)

  • Rint = 0.037

  • θmax = 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(Fo2) + (0.0544P)2 + 0.3258P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.32 e Å−3

  • Δρmin = −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 DA 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

  • Mr = 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

  • Dx = 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[Sheldrick, G. M. (2003). SADABS. Version 2.08. University of Göttingen, Germany.])Tmin = 0.885, Tmax = 0.995

  • 14 511 measured reflections

  • 1929 independent reflections

  • 1328 reflections with I > 2σ(I)

  • Rint = 0.047

  • θmax = 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(Fo2) + (0.105P)2 + 1.889P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.78 e Å−3

  • Δρmin = −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 DA 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, Uiso(H) values were set at 1.2Ueq(C) for aryl H, and at 1.5Ueq(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[Bruker (2001). SMART (Version 5.611) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART (Version 5.611) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000[Bruker (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepar material for publication: SHELXTL and local programs.

Supporting information


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, Ph2SeO. 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

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).

Refinement top

Aromatic H (C—H = 0.95 Å) and methyl H (C—H = 0.98 Å) atoms were placed in geometrically calculated positions and refined using a riding model. N-bound H atoms were located in the difference Fourier map, and refined in (II) 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). Treatment in (I)? Uiso(H) values were set at 1.2Ueq(C) for aryl H, and 1.5Ueq(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.

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
[Figure 1] 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.
[Figure 2] 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.
[Figure 3] 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.]
[Figure 4] 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.]
[Figure 5] 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.
[Figure 6] 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+·C9H11O3SF(000) = 464
Mr = 217.28Dx = 1.325 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5637 reflections
a = 13.7562 (15) Åθ = 2.8–28.4°
b = 8.4253 (9) ŵ = 0.28 mm1
c = 9.4761 (10) ÅT = 150 K
β = 97.368 (2)°Column, colourless
V = 1089.2 (2) Å30.76 × 0.19 × 0.13 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
2510 independent reflections
Radiation source: sealed tube2202 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ω rotation with narrow frame scansθmax = 28.5°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1717
Tmin = 0.816, Tmax = 0.965k = 1011
8693 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: geom, except NH coords freely refined
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.094 w = 1/[σ2(Fo2) + (0.0544P)2 + 0.3258P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2510 reflectionsΔρmax = 0.32 e Å3
142 parametersΔρmin = 0.36 e Å3
0 restraints
Crystal data top
NH4+·C9H11O3SV = 1089.2 (2) Å3
Mr = 217.28Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.7562 (15) ŵ = 0.28 mm1
b = 8.4253 (9) ÅT = 150 K
c = 9.4761 (10) Å0.76 × 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)
Tmin = 0.816, Tmax = 0.965Rint = 0.037
8693 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.094H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.32 e Å3
2510 reflectionsΔρmin = 0.36 e Å3
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
xyzUiso*/Ueq
S10.64160 (2)0.00789 (4)0.27714 (3)0.02395 (12)
O10.63608 (7)0.05481 (12)0.12765 (10)0.0319 (2)
O20.55555 (7)0.05991 (13)0.33985 (11)0.0352 (2)
O30.65527 (8)0.16295 (11)0.29157 (10)0.0338 (2)
C10.74346 (9)0.10754 (15)0.37443 (13)0.0233 (2)
C20.81442 (10)0.02519 (17)0.46791 (14)0.0295 (3)
C30.88446 (10)0.11580 (19)0.55276 (15)0.0343 (3)
H30.93310.06220.61530.041*
C40.88601 (10)0.27970 (19)0.54963 (14)0.0328 (3)
C50.81765 (10)0.35636 (17)0.45313 (14)0.0299 (3)
H50.81980.46880.44700.036*
C60.74563 (9)0.27438 (15)0.36442 (13)0.0250 (3)
C70.82054 (13)0.1534 (2)0.4874 (2)0.0493 (4)
H7A0.76560.18980.53530.074*
H7B0.88250.18090.54530.074*
H7C0.81750.20480.39410.074*
C80.95741 (12)0.3727 (2)0.65283 (17)0.0463 (4)
H8A0.93780.36560.74850.069*
H8B0.95730.48420.62310.069*
H8C1.02340.32870.65370.069*
C90.67356 (10)0.37130 (16)0.26617 (16)0.0326 (3)
H9A0.68560.48450.28460.049*
H9B0.60660.34490.28300.049*
H9C0.68170.34740.16710.049*
N10.46762 (10)0.27413 (15)0.51265 (13)0.0291 (2)
H1A0.4879 (14)0.207 (2)0.459 (2)0.044*
H1B0.5235 (14)0.325 (2)0.554 (2)0.044*
H1C0.4341 (14)0.235 (2)0.576 (2)0.044*
H1D0.4309 (15)0.337 (2)0.465 (2)0.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.02388 (18)0.02563 (19)0.02225 (18)0.00339 (11)0.00263 (12)0.00235 (10)
O10.0344 (5)0.0372 (5)0.0229 (5)0.0062 (4)0.0006 (4)0.0002 (4)
O20.0249 (5)0.0426 (6)0.0391 (6)0.0061 (4)0.0076 (4)0.0106 (4)
O30.0411 (6)0.0250 (5)0.0351 (5)0.0044 (4)0.0033 (4)0.0020 (4)
C10.0209 (5)0.0277 (6)0.0212 (5)0.0016 (4)0.0023 (4)0.0018 (4)
C20.0268 (6)0.0337 (7)0.0276 (6)0.0024 (5)0.0015 (5)0.0024 (5)
C30.0265 (6)0.0481 (8)0.0267 (6)0.0002 (6)0.0023 (5)0.0035 (6)
C40.0241 (6)0.0491 (8)0.0255 (6)0.0083 (6)0.0041 (5)0.0078 (6)
C50.0276 (6)0.0307 (7)0.0322 (7)0.0055 (5)0.0067 (5)0.0066 (5)
C60.0225 (6)0.0283 (6)0.0247 (6)0.0015 (5)0.0047 (4)0.0018 (5)
C70.0451 (9)0.0374 (8)0.0606 (10)0.0077 (7)0.0113 (8)0.0112 (8)
C80.0354 (8)0.0674 (11)0.0350 (8)0.0157 (8)0.0002 (6)0.0142 (7)
C90.0311 (7)0.0257 (6)0.0398 (7)0.0002 (5)0.0004 (5)0.0035 (5)
N10.0350 (6)0.0279 (6)0.0235 (5)0.0006 (5)0.0010 (5)0.0052 (4)
Geometric parameters (Å, º) top
S1—O11.4632 (10)C6—C91.5099 (18)
S1—O21.4584 (10)C7—H7A0.9800
S1—O31.4557 (10)C7—H7B0.9800
S1—C11.7852 (12)C7—H7C0.9800
C1—C61.4094 (18)C8—H8A0.9800
C1—C21.4132 (18)C8—H8B0.9800
C2—C31.400 (2)C8—H8C0.9800
C2—C71.517 (2)C9—H9A0.9800
C3—C41.381 (2)C9—H9B0.9800
C3—H30.9500C9—H9C0.9800
C4—C51.385 (2)N1—H1A0.83 (2)
C4—C81.5130 (19)N1—H1B0.92 (2)
C5—C61.3970 (17)N1—H1C0.87 (2)
C5—H50.9500N1—H1D0.83 (2)
O1—S1—O2111.66 (6)C2—C7—H7A109.5
O1—S1—O3110.37 (6)C2—C7—H7B109.5
O2—S1—O3111.14 (6)H7A—C7—H7B109.5
O1—S1—C1108.23 (6)C2—C7—H7C109.5
O2—S1—C1105.81 (6)H7A—C7—H7C109.5
O3—S1—C1109.46 (6)H7B—C7—H7C109.5
C6—C1—C2120.86 (11)C4—C8—H8A109.5
C6—C1—S1117.15 (9)C4—C8—H8B109.5
C2—C1—S1121.74 (10)H8A—C8—H8B109.5
C3—C2—C1117.49 (13)C4—C8—H8C109.5
C3—C2—C7116.60 (13)H8A—C8—H8C109.5
C1—C2—C7125.90 (13)H8B—C8—H8C109.5
C4—C3—C2122.98 (13)C6—C9—H9A109.5
C4—C3—H3118.5C6—C9—H9B109.5
C2—C3—H3118.5H9A—C9—H9B109.5
C3—C4—C5117.99 (12)C6—C9—H9C109.5
C3—C4—C8120.97 (14)H9A—C9—H9C109.5
C5—C4—C8120.98 (15)H9B—C9—H9C109.5
C4—C5—C6122.40 (13)H1A—N1—H1B104.6 (17)
C4—C5—H5118.8H1A—N1—H1C114.4 (19)
C6—C5—H5118.8H1B—N1—H1C111.8 (17)
C5—C6—C1118.17 (12)H1A—N1—H1D109.2 (18)
C5—C6—C9117.55 (12)H1B—N1—H1D110.5 (18)
C1—C6—C9124.26 (11)H1C—N1—H1D106.5 (18)
O3—S1—C1—C6175.86 (9)C7—C2—C3—C4177.98 (14)
O2—S1—C1—C664.29 (11)C2—C3—C4—C53.1 (2)
O1—S1—C1—C655.53 (11)C2—C3—C4—C8174.37 (13)
O3—S1—C1—C29.81 (12)C3—C4—C5—C62.7 (2)
O2—S1—C1—C2110.03 (11)C8—C4—C5—C6174.68 (13)
O1—S1—C1—C2130.15 (11)C4—C5—C6—C10.14 (19)
C6—C1—C2—C31.99 (19)C4—C5—C6—C9178.49 (12)
S1—C1—C2—C3172.12 (10)C2—C1—C6—C52.28 (18)
C6—C1—C2—C7179.42 (14)S1—C1—C6—C5172.10 (9)
S1—C1—C2—C76.5 (2)C2—C1—C6—C9179.19 (12)
C1—C2—C3—C40.7 (2)S1—C1—C6—C96.44 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.83 (2)1.98 (2)2.8124 (17)171.5 (18)
N1—H1B···O1i0.92 (2)1.91 (2)2.8261 (17)175.0 (17)
N1—H1C···O3ii0.87 (2)1.96 (2)2.8253 (16)172.8 (18)
N1—H1D···O1iii0.83 (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+·C9H11O3SF(000) = 928
Mr = 217.29Dx = 1.318 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2914 reflections
a = 8.4792 (13) Åθ = 2.8–26.7°
b = 9.6152 (15) ŵ = 0.28 mm1
c = 26.864 (4) ÅT = 150 K
V = 2190.2 (6) Å3Needle, colourless
Z = 80.45 × 0.04 × 0.02 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
1929 independent reflections
Radiation source: sealed tube1328 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
ω rotation with narrow frame scansθmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1010
Tmin = 0.885, Tmax = 0.995k = 1111
14511 measured reflectionsl = 3131
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: geom, except NH coords refined with restraints
R[F2 > 2σ(F2)] = 0.066H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.199 w = 1/[σ2(Fo2) + (0.105P)2 + 1.889P]
where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max = 0.001
1929 reflectionsΔρmax = 0.78 e Å3
142 parametersΔρmin = 0.27 e Å3
19 restraints
Crystal data top
NH4+·C9H11O3SV = 2190.2 (6) Å3
Mr = 217.29Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 8.4792 (13) ŵ = 0.28 mm1
b = 9.6152 (15) ÅT = 150 K
c = 26.864 (4) Å0.45 × 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)
Tmin = 0.885, Tmax = 0.995Rint = 0.047
14511 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06619 restraints
wR(F2) = 0.199H atoms treated by a mixture of independent and constrained refinement
S = 1.15Δρmax = 0.78 e Å3
1929 reflectionsΔρmin = 0.27 e Å3
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
xyzUiso*/Ueq
S10.03991 (11)0.32818 (9)0.17594 (3)0.0389 (4)
O10.1481 (4)0.2483 (3)0.20563 (12)0.0668 (9)
O20.0804 (4)0.2418 (3)0.15329 (10)0.0594 (8)
O30.0293 (3)0.4403 (3)0.20508 (10)0.0498 (7)
C10.1445 (4)0.4138 (3)0.12734 (12)0.0375 (8)
C20.0551 (5)0.4918 (4)0.09317 (13)0.0419 (9)
C30.1362 (6)0.5705 (4)0.05764 (15)0.0525 (11)
H30.07720.62220.03400.063*
C40.2987 (6)0.5759 (4)0.05566 (15)0.0518 (11)
C50.3816 (5)0.4953 (4)0.08895 (14)0.0507 (11)
H50.49340.49590.08700.061*
C60.3113 (5)0.4129 (4)0.12527 (13)0.0426 (9)
C70.1230 (5)0.4999 (5)0.09263 (15)0.0599 (12)
H7A0.16710.40570.09330.090*
H7B0.15790.54760.06230.090*
H7C0.15950.55160.12190.090*
C80.3831 (7)0.6691 (5)0.01907 (18)0.0741 (16)
H8A0.49620.64820.01960.111*
H8B0.36650.76660.02840.111*
H8C0.34140.65300.01450.111*
C90.4187 (5)0.3305 (5)0.15908 (17)0.0578 (12)
H9A0.52850.34450.14890.087*
H9B0.39220.23150.15680.087*
H9C0.40500.36200.19350.087*
N10.3041 (4)0.0706 (3)0.26924 (11)0.0397 (8)
H1C0.345 (4)0.110 (3)0.2963 (10)0.059*
H1B0.225 (3)0.009 (3)0.2791 (12)0.059*
H1A0.261 (4)0.133 (3)0.2482 (11)0.059*
H1D0.380 (3)0.020 (3)0.2526 (12)0.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0416 (6)0.0406 (6)0.0346 (6)0.0004 (4)0.0017 (4)0.0036 (4)
O10.0603 (18)0.076 (2)0.0640 (19)0.0160 (16)0.0086 (16)0.0338 (17)
O20.0701 (19)0.0580 (18)0.0501 (17)0.0251 (15)0.0001 (15)0.0014 (14)
O30.0513 (16)0.0557 (16)0.0425 (14)0.0010 (13)0.0098 (13)0.0035 (13)
C10.048 (2)0.0340 (18)0.0301 (18)0.0003 (16)0.0053 (16)0.0052 (14)
C20.055 (2)0.0362 (19)0.0343 (19)0.0100 (17)0.0062 (17)0.0000 (15)
C30.076 (3)0.039 (2)0.043 (2)0.011 (2)0.011 (2)0.0034 (17)
C40.078 (3)0.034 (2)0.043 (2)0.009 (2)0.020 (2)0.0068 (17)
C50.051 (2)0.050 (2)0.051 (2)0.012 (2)0.014 (2)0.016 (2)
C60.047 (2)0.044 (2)0.0363 (19)0.0030 (17)0.0027 (17)0.0113 (16)
C70.056 (3)0.075 (3)0.049 (2)0.020 (2)0.003 (2)0.013 (2)
C80.110 (4)0.050 (3)0.062 (3)0.021 (3)0.037 (3)0.006 (2)
C90.043 (2)0.081 (3)0.050 (2)0.003 (2)0.002 (2)0.008 (2)
N10.0417 (17)0.0382 (16)0.0390 (17)0.0066 (14)0.0044 (14)0.0003 (14)
Geometric parameters (Å, º) top
S1—O11.438 (3)C6—C91.511 (6)
S1—O21.450 (3)C7—H7A0.9800
S1—O31.456 (3)C7—H7B0.9800
S1—C11.780 (4)C7—H7C0.9800
C1—C21.407 (5)C8—H8A0.9800
C1—C61.415 (5)C8—H8B0.9800
C2—C31.399 (5)C8—H8C0.9800
C2—C71.512 (6)C9—H9A0.9800
C3—C41.380 (7)C9—H9B0.9800
C3—H30.9500C9—H9C0.9800
C4—C51.376 (6)N1—H1C0.89 (2)
C4—C81.510 (5)N1—H1B0.93 (2)
C5—C61.391 (5)N1—H1A0.90 (2)
C5—H50.9500N1—H1D0.92 (2)
O1—S1—O2112.09 (19)C2—C7—H7A109.5
O1—S1—O3110.76 (19)C2—C7—H7B109.5
O1—S1—C1109.62 (17)H7A—C7—H7B109.5
O2—S1—O3111.48 (18)C2—C7—H7C109.5
O2—S1—C1107.93 (16)H7A—C7—H7C109.5
O3—S1—C1104.64 (16)H7B—C7—H7C109.5
C2—C1—C6121.1 (3)C4—C8—H8A109.5
C2—C1—S1117.2 (3)C4—C8—H8B109.5
C6—C1—S1121.6 (3)H8A—C8—H8B109.5
C3—C2—C1117.9 (4)C4—C8—H8C109.5
C3—C2—C7117.2 (3)H8A—C8—H8C109.5
C1—C2—C7124.9 (3)H8B—C8—H8C109.5
C4—C3—C2122.5 (4)C6—C9—H9A109.5
C4—C3—H3118.7C6—C9—H9B109.5
C2—C3—H3118.7H9A—C9—H9B109.5
C5—C4—C3117.6 (4)C6—C9—H9C109.5
C5—C4—C8121.0 (4)H9A—C9—H9C109.5
C3—C4—C8121.4 (4)H9B—C9—H9C109.5
C4—C5—C6123.9 (4)H1C—N1—H1B108 (2)
C4—C5—H5118.0H1C—N1—H1A113 (2)
C6—C5—H5118.0H1B—N1—H1A108 (2)
C5—C6—C1116.9 (4)H1C—N1—H1D111 (2)
C5—C6—C9117.5 (4)H1B—N1—H1D107 (2)
C1—C6—C9125.6 (4)H1A—N1—H1D109 (2)
O1—S1—C1—C2177.1 (3)C7—C2—C3—C4177.4 (4)
O2—S1—C1—C254.8 (3)C2—C3—C4—C52.8 (6)
O3—S1—C1—C264.1 (3)C2—C3—C4—C8175.9 (3)
O1—S1—C1—C67.7 (4)C3—C4—C5—C62.2 (6)
O2—S1—C1—C6130.1 (3)C8—C4—C5—C6176.5 (3)
O3—S1—C1—C6111.1 (3)C4—C5—C6—C10.0 (5)
C6—C1—C2—C31.2 (5)C4—C5—C6—C9179.9 (4)
S1—C1—C2—C3174.0 (3)C2—C1—C6—C51.7 (5)
C6—C1—C2—C7179.7 (4)S1—C1—C6—C5173.2 (3)
S1—C1—C2—C74.5 (5)C2—C1—C6—C9178.4 (3)
C1—C2—C3—C41.2 (6)S1—C1—C6—C96.7 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.90 (2)1.86 (2)2.755 (4)173 (3)
N1—H1B···O3i0.93 (2)1.84 (2)2.734 (4)160 (3)
N1—H1C···O2ii0.89 (2)1.96 (2)2.828 (4)165 (3)
N1—H1D···O3iii0.92 (2)1.95 (2)2.861 (4)167 (3)
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x+1/2, y, z+1/2; (iii) x+1/2, y1/2, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaNH4+·C9H11O3SNH4+·C9H11O3S
Mr217.28217.29
Crystal system, space groupMonoclinic, P21/cOrthorhombic, Pbca
Temperature (K)150150
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), 9090, 90, 90
V3)1089.2 (2)2190.2 (6)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.280.28
Crystal size (mm)0.76 × 0.19 × 0.130.45 × 0.04 × 0.02
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
diffractometer
Bruker SMART 1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.816, 0.9650.885, 0.995
No. of measured, independent and
observed [I > 2σ(I)] reflections
8693, 2510, 2202 14511, 1929, 1328
Rint0.0370.047
(sin θ/λ)max1)0.6720.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.094, 1.04 0.066, 0.199, 1.15
No. of reflections25101929
No. of parameters142142
No. of restraints019
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.360.78, 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—O11.4632 (10)S1—O31.4557 (10)
S1—O21.4584 (10)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.83 (2)1.98 (2)2.8124 (17)171.5 (18)
N1—H1B···O1i0.92 (2)1.91 (2)2.8261 (17)175.0 (17)
N1—H1C···O3ii0.87 (2)1.96 (2)2.8253 (16)172.8 (18)
N1—H1D···O1iii0.83 (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—O11.438 (3)S1—O31.456 (3)
S1—O21.450 (3)S1—C11.780 (4)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.90 (2)1.86 (2)2.755 (4)173 (3)
N1—H1B···O3i0.93 (2)1.84 (2)2.734 (4)160 (3)
N1—H1C···O2ii0.89 (2)1.96 (2)2.828 (4)165 (3)
N1—H1D···O3iii0.92 (2)1.95 (2)2.861 (4)167 (3)
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x+1/2, y, z+1/2; (iii) x+1/2, y1/2, z.
 

Acknowledgements

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

References

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