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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 67| Part 1| January 2011| Pages o1-o5
doi:10.1107/S0108270110049371

The mixed diol–di­thiol 2,2-bis­­(sulfanylmeth­yl)propane-1,3-diol: characterization of key inter­mediates on a new synthetic pathway

CROSSMARK_Color_square_no_text.svg
Trevor R. Simmons,a Christopher J. Picketta and Joseph A. Wrighta*

aEnergy Materials Laboratory, School of Chemistry, University of East Anglia, Norwich NR4 7TJ, England
*Correspondence e-mail: joseph.wright@uea.ac.uk

(Received 27 September 2010; accepted 25 November 2010; online 8 December 2010)

A new synthetic route to 2,2-bis­(sulfanylmeth­yl)propane-1,3-diol, (II), is described starting from the commercially available 2,2-bis­(hydroxy­meth­yl)propane-1,3-diol. The structures of two inter­mediates on this route are described. 5,5-Dimethenyl-2,2-dimethyl-1,3-dioxane bis­(thio­cyanate) (systematic name: {[5-(cyano­sulfan­yl)-2,2-dimethyl-1,3-dioxan-5-yl]sulfan­yl}formo­nitrile), C10H14N2O2S2, (X)[link], crystallizes in the space group P21/c with no symmetry relationship between the two thio­cyanate groups. There is a short intra­molecular N⋯S contact for one thio­cyanate group, while the second group is positioned such that this type of inter­action is not possible. 1,3-(Hydroxy­meth­yl)propane-1,3-diyl bis­(thio­cyanate), C7H10N2O2S2, (XI)[link], also features a single short N⋯S contact in the solid state. Hydrogen bonding between two mol­ecules of compound (XI)[link] results in the formation of dimers in the crystal, which are then linked together by a second hydrogen-bond inter­action between the dimers. In addition, the structures of two inter­mediates from an unsuccessful alternative synthesis of (II) are reported. 2,2-Bis(chloro­meth­yl)propane-1,3-diol, C5H10Cl2O2, (VI)[link], crystallized as an inversion twin with a minor twin fraction of 0.43 (6). It forms a zigzag structure as a result of inter­molecular hydrogen bonding. The structure of 9,9-di­methyl-2,4,8,10-tetra­oxa-3λ4-thia­spiro­[5.5]undecan-3-one, C8H14O5S, (VII)[link], shows evidence for a weak S⋯O contact with a distance of 3.2529 (11) Å.

Comment

The structure of 2,2-bis­(hy­droxy­meth­yl)propane-1,3-diol [`penta­erythritol', (I), see Scheme 1[link]] was first reported by Llewellyn et al. (1937[Llewellyn, F. J., Cox, E. G. & Goodwin, T. H. (1937). J. Chem. Soc. pp. 883-894.]), and a search of the Cambridge Structural Database (CSD, Version 5.31; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) reveals an additional 12 structural reports to date. This is unsurprising as (I) is a cheap commercially available material and exhibits a large degree of hydrogen bonding in the solid state. In contrast, the mixed diol–dithiol 2,2-bis­(sulfanylmeth­yl)pro­pane-1,3-diol, (II) (see Scheme 2[link]), has received much less attention in the literature. The synthesis of (II) was first reported by Backer & Tamsma (1938[Backer, H. J. & Tamsma, A. F. (1938). Recl Trav. Chim. Pays-Bas, 57, 1183-1210.]), with further routes reported by Peppell & Signaigo (1946[Peppell, W. J. & Signaigo, F. K. (1946). US Patent 2 402 665.]), Bladon & Owen (1950[Bladon, P. & Owen, L. N. (1950). J. Chem. Soc. pp. 591-597.]) and Nygård (1967[Nygård, B. (1967). Ark. Kemi. 28, 89-97.]). Compound (II) has clear potential as a starting material for functionalized dithiol ligands, and it is therefore highly surprising that there have been no reports of (II) in the literature since Nygård's paper. None of the reported syntheses of (II) involves a direct route from (I) and, given the availability of the latter, this seemed to be an obvious avenue to explore in producing large amounts of (II) with minimal synthetic effort.

[Scheme 1]
[Scheme 2]

The first strategy examined for the synthesis of (II) is outlined in Scheme 1. Conversion of (I) first to the acetal, (III), and then to the dichloride, (IV), was expected to be readily achieved. From (IV), the next target would be the bis­(isothio­uronium) salt, (V), with the intention of one-pot conversion of (V) to (II) in analogy to the formation of ethane-1,2-dithiol (Speziale, 1963[Speziale, A. J. (1963). Org. Synth. Coll. Vol. 4, 401.]).

Formation of acetal (III) from (I) presented no difficulties. However, the reaction of (III) with thionyl chloride (SOCl2) was more challenging than initially anti­cipated. Reaction of (III) with SOCl2 in pyridine at room temperature led to the isolation of two distinct crystalline solids after column chromatography. Both materials appeared to give spectroscopic data which would be consistent with the desired material. However, examination by X-ray methods revealed that the two solids were in fact (VI)[link] and (VII)[link] (Scheme 1[link]). Presumably the formation of (VI)[link] was due to hydrolysis of the desired material, (IV), on standing for crystallization (which took place in the air). Compound (VI)[link] (Fig. 1[link]) crystallizes in the space group Cc and the chosen crystal was found to exhibit inversion twinning, with a final occupancy for the minor component of 0.43 (6). The hy­droxy groups in (VI)[link] lead to an extended two-dimensional hydrogen-bonding network (Fig. 2[link] and Table 1[link]), which links adjacent mol­ecules to form a layer structure perpendicular to the b axis. This comprises a zigzag arrangement of hydrogen bonds, which hold the alternating mol­ecules of (VI)[link] together. The location of the hydrogen-bonding framework at the centre of the layer leaves the Cl atoms on the `outside' of the layer.

The reaction to form a cyclic sulfur-containing ester, (VII)[link] (Fig. 3[link]), is similar to that reported by Rao et al. (2009[Rao, Z.-Y., Xiao, X., Zhang, Y.-Q., Xue, S.-F. & Tao, Z. (2009). Acta Cryst. E65, o36.]), who showed that the reaction of (II) directly with SOCl2 yields the bis­(ester), (VIII) (see below). The geometry of compound

[Scheme 3]
(VII)[link] is similar to that reported for (VIII) and is unremarkable. Both (VII)[link] and (VIII) show evidence of weak inter­molecular inter­actions. In (VII)[link], there is a close contact between symmetry-related S=O groups, with an S41⋯O41′ distance of 3.2529 (11) Å [symmetry code: (′) 2 − x, 1 − y, 2 − z], while in (VIII) there are a number of S⋯O distances in the range 3.308 (3)–3.315 (3) Å.

An alternative route to the desired chloride was explored by reacting (III) with 4-toluene­sulfonyl chloride in pyridine. This led to a crystalline material with spectroscopic data fully in agreement with the structure of (IV). While a diffraction study on this new material showed the correct connectivity for (IV), high residual values prevented a satisfactory completion of the refinement; application of a twin law failed to improve the residual values obtained.

With (IV) available, reaction to form the desired salt, (V), was attempted. Reaction under a range of conditions failed to yield any material with spectroscopic characteristics matching those expected for the desired material. Given this failure, an alternative route to (II) was devised via the isothio­cyanate compound, (XI)[link] (see Scheme 2[link]).

Starting from (III), the formation of (IX) by reaction with 4-toluene­sulfonyl chloride in the presence of pyridine pre­sented no significant difficulty. Compound (IX) could then be reacted with potassium thio­cyanate in dimethyl sulfoxide (DMSO) to yield (X)[link]. This reaction proceeded much more readily in dimethyl sulfoxide than in the commonly employed dimethyl­formamide (DMF), presumably because of the differing basicity of the two solvents. Compound (X)[link] could be crystallized as white needles from hexa­ne–ethyl acetate (Fig. 4[link]). Notably, compound (X)[link] crystallizes in the space group P21/c with no symmetry relationship between the two thio­cyanate groups. In contrast, the only other reported bis­(thio­cyanate) structure, for methyl­ene bis­(thio­cyanate), crystallizes in the space group I2/c and does exhibit a symmetry relationship between the two groups (Konnert & Britton, 1971[Konnert, J. H. & Britton, D. (1971). Acta Cryst. B27, 781-786.]). The latter structure exhibits a short inter­molecular N⋯S contact [3.17 (1) Å]. In (X), there is one intra­molecular contact [S4⋯N51 = 3.2377 (16) Å], while the locations of S5 and N41 preclude contacts for these atoms. The mol­ecular geometry of (X) is unremarkable.

Treatment with acid removed the acetal-protecting group from (X)[link] to yield (XI)[link] (Fig. 5). Compound (XI)[link] crystallizes in the space group Pbca and as in (X)[link] there is no symmetry relationship between the two thio­cyanate groups. The intramolecular contact distance S5⋯N41 of 3.264 (2) Å is similar to that in (X)[link] and again larger than in the previously reported methyl­ene bis­(thio­cyanate) (Konnert & Britton, 1971[Konnert, J. H. & Britton, D. (1971). Acta Cryst. B27, 781-786.]). Hydrogen bonding between mol­ecules of (XI)[link] occurs in two ways. Firstly, a pair of symmetry-related O—H⋯O hydrogen bonds create `dimers' of mol­ecules. These dimers are then linked in an extended ribbon parallel to the a axis by a second set of symmetry-related hydrogen bonds between a hydroxy group and atom N51 of the thio­cyanide group (Fig. 6 and Table 2). The ribbons are essentially flat without twists, and the ribbon plane lies parallel to (012).

Final reduction of (XI)[link] to (II) with lithium aluminium hydride proceeded cleanly, and (II) was crystallized from dichloro­methane–diethyl ether. The resulting material gave spectroscopic data consistent with the formulation as (II).

In summary, a new synthesis of (II) has been disclosed starting from the commercial tetraol, (I). The structures of a number of key inter­mediates on this pathway have been presented.

[Figure 1]
Figure 1
The structure of (VI)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2]
Figure 2
The two-dimensional hydrogen-bond network in (VI)[link]. H atoms, except for H2 and H3, have been omitted for clarity. The view is approximately along (100).
[Figure 3]
Figure 3
The structure of (VII)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4]
Figure 4
The structure of (X)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 5]
Figure 5
The structure of (XI)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 6]
Figure 6
The hydrogen-bond network in (XI)[link]. H atoms, except for H2 and H3, have been omitted for clarity. The view is approximately along (010).

Experimental

Compounds (VI)[link] and (VII)[link] were obtained by reaction of (III) with thionyl chloride in pyridine at 273 K. Column chromatography on silica (hexa­ne–ethyl acetate 4:1 v/v) yielded two fractions, one of which was initially an oil and the other of which was a solid. The oil crystallized after standing in the air for several days to yield yellow crystals of (VI)[link], while sublimation of the solid fraction at 1.3 Pa gave colourless crystals of (VII)[link]. Compound (X)[link] was formed by the reaction of (IX) with potassium thio­cyanate in dimethyl sulfoxide at 398 K. After aqueous work-up, column chromatography on silica (hexa­ne–ethyl acetate 1:2 v/v) gave a clear oil which crystallized after standing overnight. Reaction of compound (X)[link] with lithium alu­min­ium hydride in tetra­hydro­furan at 313 K followed by aqueous work-up gave (XI)[link] as an off-white solid. This was recrystallized from hot chloro­form. Full details of the syntheses of all the reported compounds and spectroscopic data are available in the archived CIF.

Compound (VI)[link]

Crystal data

  • C5H10Cl2O2

  • Mr = 173.03

  • Monoclinic, C c

  • a = 6.1635 (3) Å

  • b = 19.6495 (10) Å

  • c = 6.3889 (4) Å

  • β = 96.617 (5)°

  • V = 768.60 (7) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.77 mm−1

  • T = 140 K

  • 0.40 × 0.20 × 0.10 mm
Data collection

  • Oxford Diffraction Xcalibur 3/CCD diffractometer

  • Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis Pro. Version 1.171. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.776, Tmax = 1.000

  • 5628 measured reflections

  • 1707 independent reflections

  • 1609 reflections with I > 2σ(I)

  • Rint = 0.028
Refinement

  • R[F2 > 2σ(F2)] = 0.028

  • wR(F2) = 0.075

  • S = 1.08

  • 1707 reflections

  • 91 parameters

  • 2 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.46 e Å−3

  • Δρmin = −0.23 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 825 Friedel pairs

  • Flack parameter: 0.43 (6)

Table 1
Hydrogen-bond geometry (Å, °) for (VI)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O2—H2⋯O3i 0.77 (4) 1.91 (4) 2.653 (2) 165 (3)
O3—H3⋯O2ii 0.73 (3) 1.93 (3) 2.657 (2) 172 (3)
Symmetry codes: (i) x+1, y, z; (ii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].

Compound (VII)[link]

Crystal data

  • C8H14O5S

  • Mr = 222.25

  • Monoclinic, P 21 /c

  • a = 13.1287 (10) Å

  • b = 6.0588 (5) Å

  • c = 12.5024 (12) Å

  • β = 98.135 (8)°

  • V = 984.49 (15) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.32 mm−1

  • T = 140 K

  • 0.80 × 0.20 × 0.06 mm
Data collection

  • Oxford Diffraction Xcalibur 3/CCD diffractometer

  • Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis Pro. Version 1.171. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.771, Tmax = 1.000

  • 12831 measured reflections

  • 2222 independent reflections

  • 1805 reflections with I > 2σ(I)

  • Rint = 0.028
Refinement

  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.079

  • S = 1.06

  • 2222 reflections

  • 129 parameters

  • H-atom parameters constrained

  • Δρmax = 0.31 e Å−3

  • Δρmin = −0.39 e Å−3

Compound (X)[link]

Crystal data

  • C10H14N2O2S2

  • Mr = 258.35

  • Monoclinic, P 21 /c

  • a = 9.3934 (2) Å

  • b = 8.5696 (2) Å

  • c = 15.7918 (4) Å

  • β = 104.380 (2)°

  • V = 1231.38 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.42 mm−1

  • T = 140 K

  • 0.70 × 0.08 × 0.08 mm
Data collection

  • Oxford Diffraction Xcalibur 3/CCD diffractometer

  • Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis Pro. Version 1.171. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.840, Tmax = 1.000

  • 17624 measured reflections

  • 2791 independent reflections

  • 2222 reflections with I > 2σ(I)

  • Rint = 0.030
Refinement

  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.077

  • S = 1.01

  • 2791 reflections

  • 147 parameters

  • H-atom parameters constrained

  • Δρmax = 0.37 e Å−3

  • Δρmin = −0.25 e Å−3

Compound (XI)[link]

Crystal data

  • C7H10N2O2S2

  • Mr = 218.29

  • Orthorhombic, P b c a

  • a = 8.6971 (5) Å

  • b = 10.3972 (5) Å

  • c = 21.7280 (15) Å

  • V = 1964.8 (2) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.51 mm−1

  • T = 140 K

  • 0.39 × 0.13 × 0.01 mm
Data collection

  • Oxford Diffraction Xcalibur 3/CCD diffractometer

  • Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis Pro. Version 1.171. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.926, Tmax = 1.000

  • 25270 measured reflections

  • 2245 independent reflections

  • 1498 reflections with I > 2σ(I)

  • Rint = 0.082
Refinement

  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.069

  • S = 0.94

  • 2245 reflections

  • 124 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.31 e Å−3

  • Δρmin = −0.26 e Å−3

Table 2
Hydrogen-bond geometry (Å, °) for (XI)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O2—H2⋯O3i 0.78 (2) 1.97 (3) 2.744 (2) 170 (3)
O3—H3⋯N51ii 0.75 (2) 2.08 (2) 2.832 (2) 177 (3)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x+1, y, z.

All structure solutions and refinements were carried out from within the WinGX suite of programs (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]). All C-bound H atoms were refined using a riding model (SHELXL97; Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), and with Uiso(H) = 1.2Ueq(C) for CH and CH2 groups or 1.5Ueq(C) for methyl groups. Methyl groups were allowed additional rotational freedom. In structures (VII)[link] and (X)[link], the oxygen-bound H atoms were initially positioned using the CALC-OH program (Nardelli, 1999[Nardelli, M. (1999). J. Appl. Cryst. 32, 563-571.]), and both coordinates and Uiso values were freely refined. The chosen crystal of (VI)[link] was found to exhibit inversion twinning and the refinement of the absolute structure parameter yielded a value of 0.43 (6) for the minor twin component.

For all compounds, data collection: CrysAlis Pro (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis Pro. Version 1.171. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; program(s) used to solve structure: SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]). Software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004[Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335-338.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]) for (VI) and (VII); SHELXL97, enCIFer and PARST (Nardelli, 1995[Nardelli, M. (1995). J. Appl. Cryst. 28, 659.]) for (X) and (XI).

Supporting information

Crystal structure: contains datablocks XI, global, VI, VII, X. DOI: 10.1107/S0108270110049371/sk3390sup1.cif

Structure factors: contains datablock VI. DOI: 10.1107/S0108270110049371/sk3390VIsup2.hkl

Structure factors: contains datablock VII. DOI: 10.1107/S0108270110049371/sk3390VIIsup3.hkl

Structure factors: contains datablock X. DOI: 10.1107/S0108270110049371/sk3390Xsup4.hkl

Structure factors: contains datablock XI. DOI: 10.1107/S0108270110049371/sk3390XIsup5.hkl


Comment top

The structure of 2,2-bis(hydroxymethyl)propane-1,3-diol ['pentaerythritol', (I), Scheme 1] was first reported by Llewellyn et al. (1937), and a search of the Cambridge Structural Database (CSD, Version 5.31; Allen, 2002) reveals an additional 12 structural reports to date. This is unsurprising as (I) is a cheap, commercially available material and exhibits a large degree of hydrogen bonding in the solid state. In contrast, the mixed diol–dithiol 2,2-bis(sulfanylmethyl)propane-1,3-diol, (II) (Fig. 1) has received much less attention in the literature. The synthesis of (II) was first reported by Backer & Tamsma (1938), with further routes reported by Peppell & Signaigo (1946), Bladon & Owen (1950) and Nygård (1967). Compound (II) has clear potential as a starting material for functionalized dithiol ligands, and it is therefore highly surprising that there are no reports of (II) in the literature since Nygård's paper. None of the reported syntheses of (II) involves a direct route from (I), and given the availability of the latter this seemed to be an obvious avenue to explore in producing large amounts of (II) with minimal synthetic effort.

The first strategy examined for the synthesis of (II) is outlined in Scheme 1. Conversion of (I) first to the acetal, (III), and then to the dichloride, (IV), was expected to be readily achieved. From (IV), the next target would be the bis(isothiouronium) salt, (V), with the intention of one-pot conversion of (V) to (II) in analogy to the formation of ethane-1,2-dithiol (Speziale, 1963).

Formation of acetal, (III), from (I) presented no difficulities. However, the reaction of (III) with thionyl chloride (SOCl2) was more challenging than initially anticipated. Reaction of (III) with SOCl2 in pyridine at room temperature led to the isolation of two distinct crystalline solids after column chromatography. Both materials appeared to give spectroscopic data which would be consistent with the desired material. However, examination by X-ray methods revealed that the two solids were in fact (VI) and (VII) (Scheme 1). Presumably the formation of (VI) was due to hydrolysis of the desired material (IV) on standing for crystallization (which took place in the air). Compound (VI) (Fig. 2) crystallizes in space group Cc, and was found to be racemically twinned with a final occupancy for the minor component of 0.43 (6). The oxygen-bound hydrogen atoms were initially placed using the CALC-OH program (Nardelli, 1999) and were then refined freely. As anticipated, the hydroxy groups in (VI) lead to an extended two-dimensional hydrogen-bonding network (Fig. 3, Table 2), which links adjacent molecules to form a layer structure perpendicular to the b axis. This comprises a zigzag arrangement of hydrogen bonds, which hold the alternating molecules of (VI) together. The location of the hydrogen-bonding framework at the centre of the layer leaves the chlorine atoms on the 'outside' of the layer.

The reaction to form a cyclic sulfur-containing ester, (VII) (Fig. 4), is similar to that reported by Rao et al. (2009), who showed that the reaction of (II) directly with SOCl2 yields the bis(ester), (VIII) (Fig. 5). The geometry of compound (VII) (Table 4) is similar to that reported for (VIII), and is unremarkable. Both (VII) and (VIII) show evidence for [of?] weak intermolecular interactions. In (VII), there is a close contact between symmetry-related S═O groups, with an S41···O41' distance of 3.2529 (11) Å [symmetry code ('): 2 - x, 1 - y, 2 - z], while in (VIII), there are a number of S···O distances in the range 3.308 (3) to 3.315 (3) Å.

An alternative route to the desired chloride was explored by reacting (III) with 4-toluenesulfonyl chloride in pyridine. This led to a crystalline material with spectroscopic data fully in agreement with the structure of (IV). While a diffraction study on this new material showed the correct connectivity for (IV), high residual values prevented a satisfactory completion of the refinement; application of a twin law failed to improve the residual values obtained.

With (IV) available, reaction to form the desired salt (V) was attempted. Reaction under a range of conditions failed to yield any material with spectropscopic characteristics matching those expected for the desired material. Given this failure, an alternative route to (II) was devised via the isothiocynate compound (XI) (Scheme 2).

Starting from (III) the formation of (IX) by reaction with 4-toluenesulfonyl chloride in the presence of pyridine presented no significant difficulty. Compound (IX) could then be reacted with potassium thiocyanate in dimethylsulfoxide to yield (X). This reaction proceeded much more readily in dimethylsulfoxide than in the commonly employed dimethylformamide, presumably because of the differing basicity of the two solvents. Compound (X) could be crystallized as white needles from hexane–ethyl acetate (Fig. 6). Notably, compound (X) crystallizes in space group P21/c with no symmetry relationship between the two thiocyanate groups. In contrast, the only other reported bis(thiocyanate) structure, for methylene bis(thiocyanate), crystallizes in space group I2/c and does exhibit a symmetry relationship between the two groups (Konnert & Britton, 1971). The latter structure exhibits a short intermolecular N···S contact [3.17 (1) Å]. In (IX), there is one intramolecular contact: S4···N51 = 3.2377 (16) Å, while the locations of S5 and N41 preclude contacts for these atoms. The molecular geometry of (IX) is unremarkable (Table 5).

Treatment with acid removed the acetal-protecting group from (X) to yield (XI) (Fig. 7). The oxygen-bound hydrogen atoms in this structure were located using the the CALC-OH program (Nardelli, 1999) and were then refined freely. Compound (XI) crystallizes in space group Pbca and as in (X) there is no symmetry relationship between the two thiocyanate groups. The contact distance S4···N51, 3.264 (2) Å, is similar to that in (X) and again larger than the previously reported methylene bis(thiocyanate) (Konnert & Britton, 1971). Hydrogen bonding between molecules of (XI) occurs in two ways. Firstly, a pair of symmetry-related O—H···O hydrogen bonds create 'dimers' of molecules. These dimers are then linked in an infinite chain parallel to the a axis by a second set of symmetry-related hydrogen bonds between a hydroxyl group and nitrogen N51 of the thiocyanide group (Fig. 8, Table 7). The overall result is the formation of sheets of molecules, with a normal vector approximately parallel to the bisector of the angle between the b and c axes.

Final reduction of (XI) to (II) with lithium aluminium hydride proceeded cleanly, and (II) was crystallized from dichloromethane–diethyl ether. The resulting material gave spectroscopic data consistent with the formulation as (II).

In summary, a new synthesis of (II) has been disclosed starting from the commercial tetraol (I). The structures of a number of key intermediates on this pathway have been disclosed.

Related literature top

For related literature, see: Allen (2002); Backer & Tamsma (1938); Bladon & Owen (1950); Farrugia (1999); Konnert & Britton (1971); Llewellyn et al. (1937); Nardelli (1999); Nygård (1967); Peppell & Signaigo (1946); Rao et al. (2009); Sheldrick (2008); Speziale (1963).

Experimental top

Compounds (VI) and (VII) were obtained by reaction of (III) with thionyl chloride in pyridine at 273 K. Column chromatography on silica (hexane–ethyl acetate 4:1 v/v) yielded two fractions, one of which was initially an oil and one which was a solid. The oil crystallized after standing in the air for several days to yield yellow crystals of (VI), while sublimation of the solid fraction at 1.3 Pa gave colourless crystals of (VII). Compound (X) was formed by the reaction of (IX) with potassium thiocyanate in dimethyl sulfoxide at 398 K. After aqueous work-up, column chromatography on silica (hexane–ethyl acetate 1:2 v/v) gave a clear oil which crystallized after standing overnight. Reaction of compound (X) with lithium aluminium hydride in tetrahydrofuran at 313 K followed by aqueous work up gave (XI) as an off-white solid. This was recrystallized from hot chloroform. Full details for the synthesis of all compounds and spectroscopic data are available in the archived CIF.

Refinement top

All structure solutions and refinements were carried out from within the WinGX suite of programs (Farrugia, 1999). All C-bound H atoms were refined using a riding model (SHELXL97; Sheldrick, 2008), and with Uiso(H) = 1.2Ueq(C) for CH and CH2 groups or 1.5Ueq(C) for methyl groups. Methyl groups were allowed additional rotational freedom. In structures (VII) and (X) the oxygen-bound H atoms were initially positioned using the CALC-OH program (Nardelli, 1999), and both coordinates and Uiso values were freely refined. Structure (VI) was racemically twinned and was refined to a final occupancy of 0.43 (6) for the minor component.

Computing details top

For all compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997). Software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010) for (VI), (VII); SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and PARST (Nardelli, 1995) for (X), (XI).

Figures top
[Figure 1] Fig. 1. The structure of (VI), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The two-dimensional hydrogen-bond network in (VI). H atoms except for H3 and H3 have been omitted for clarity. The view is normal to (100).
[Figure 3] Fig. 3. The structure of (VII), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. The structure of (X), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 5] Fig. 5. The structure of (XI), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 6] Fig. 6. The hydrogen-bond network in (XI). H atoms except for H2 and H3 have been omitted for clarity. The view is normal to (010).
(VI) 2,2-bis(chloromethyl)propane-1,3-diol top
Crystal data top
C5H10Cl2O2F(000) = 360
Mr = 173.03Dx = 1.495 Mg m−3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 3911 reflections
a = 6.1635 (3) Åθ = 3.5–29.0°
b = 19.6495 (10) ŵ = 0.77 mm−1
c = 6.3889 (4) ÅT = 140 K
β = 96.617 (5)°Prism, colourless
V = 768.60 (7) Å30.40 × 0.20 × 0.10 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur 3/CCD
diffractometer		1707 independent reflections
Radiation source: Enhance (Mo) X-ray Source1609 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
Detector resolution: 16.0050 pixels mm-1θmax = 27.5°, θmin = 3.5°
ω scansh = −7→7
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		k = −25→25
Tmin = 0.776, Tmax = 1.000l = −7→8
5628 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075 w = 1/[σ2(Fo2) + (0.0513P)2 + 0.0128P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1707 reflectionsΔρmax = 0.46 e Å−3
91 parametersΔρmin = −0.23 e Å−3
2 restraintsAbsolute structure: Flack (1983), ???? Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.43 (6)
Crystal data top
C5H10Cl2O2V = 768.60 (7) Å3
Mr = 173.03Z = 4
Monoclinic, CcMo Kα radiation
a = 6.1635 (3) ŵ = 0.77 mm−1
b = 19.6495 (10) ÅT = 140 K
c = 6.3889 (4) Å0.40 × 0.20 × 0.10 mm
β = 96.617 (5)°
Data collection top
Oxford Diffraction Xcalibur 3/CCD
diffractometer		1707 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		1609 reflections with I > 2σ(I)
Tmin = 0.776, Tmax = 1.000Rint = 0.028
5628 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075Δρmax = 0.46 e Å−3
S = 1.08Δρmin = −0.23 e Å−3
1707 reflectionsAbsolute structure: Flack (1983), ???? Friedel pairs
91 parametersAbsolute structure parameter: 0.43 (6)
2 restraints
Special details top

Experimental. Syntheses were performed under nitrogen using standard Schlenk line techniques. Chemicals were obtained from Aldrich, Alfa Aesar or Fisher Scientific, and were used as received unless stated otherwise. Solvents were purged with nitrogen gas for several minutes and passed through activated silica columns (M. Braun solvent purifier). NMR spectra were recorded using a Bruker DPX-300 spectrometer with a 5 mm BBO probe. Chemical shifts are reported in p.p.m. and referenced to residual solvent resonances.

[5-(Hydroxymethyl)-2,2-dimethyl-1,3-dioxan-5- yl]methanol, (III): 2,2-Bis(hydroxymethyl)propane-1,3-diol, (I) (136 g, 1.00 mol), and 4-toluenesulfonoic acid (2.0 g, 10 mmol) were dissolved in DMF [dimethylformamide?] (700 cm3) and heated with stirring until solids were fully dissolved (381 K). The solution was then cooled to 313 K in a water bath, yielding a cloudy white solution. Neat 2,2-dimethoxypropane (123 cm3, 1.00 mol) was added and the reaction stirred for 60 h. After this time, Na2CO3 (2.0 g, 20 mmol) was added and the mixture stirred for a further 30 min. The solid was filtered off and the volume of the filtrate was reduced to 50 cm3 at reduced pressure. Water (1000 cm3) was added to the residue to give a clear solution and white solid. The solid was removed by filtration and the filtrate evaporated under reduced pressure to give white powder. The crude product was extracted with diethyl ether in a Soxhlet apparatus to give white crystalline solid (78.9 g, 45%). 1H NMR (DMSO-d6, 293 K, 300 MHz) δ 1.28 (s, 6H, Me), 3.33 (s, 4H), 3.57 (s, 4H).

5,5-Bis(chloromethyl)-2,2-dimethyl-1,3-dioxane, (IV): Compound (III) (2.07 g, 11 mmol) and 4-toluenesulfonyl chloride (4.45 g, 23 mmol) were dissolved in pyridine (10 cm3) and the solution heated to reflux for 20 h. After cooling to room temperature the solvent was removed under reduced pressure to give a brown solid. This was redissolved in ethyl acetate (100 cm3) and washed with HCl (1 M, 3 × 50 cm3), aqueous NaHCO3 (3 × 50 cm3) and aqueous NaCl (3 × 50 cm3). The solution was dried over MgSO4, filtered and the solvent removed under reduced pressure. Purification by column chromatography on silica (hexane–ethyl acetate 4: 1) gave an oily solid. Sublimation under reduced pressure (1.3 Pa) gave white crystalline solid (0.23 g, 18%). 1H NMR (CDCl3, 293 K, 300 MHz) δ 1.45 (s, 6H, Me), 3.73 (s, 4H, CH2Cl), 3.82 (s, 4H, CH2O).

2,2-Bis(chloromethyl)propane-1,3-diol, (VI), and 9,9-dimethyl-2,4,8,10-tetraoxa-3λ4– thiaspiro[5.5]undecan-3-one, (VII). Compound (III) (3.60 g, 20 mmol) was dissolved in pyridine (50 cm3) under nitrogen and cooled to 273 K. Thionyl chloride (3.72 cm3, 51 mmol) was added dropwise to give a yellowish solution. After 10 min the solution turned a dark orange with a white precipitate. The solution was heated to reflux for 1 h then cooled to room temperature to give a dark oily solution. Water (300 cm3) was added and aqueous phase was extracted with ethyl acetate (3 × 100 cm3). The combined organic fractions were washed with HCl (1 M, 3 × 50 cm3), aqueous NaHCO3 (3 × 50 cm3) and aqueous NaCl (3 × 50 cm3). The solution was dried over MgSO4, filtered and evaporated at reduced pressure to give an orange oil. Purification by column chromatography on silica (hexane–ethyl acetate 4: 1) gave a a yellow oil and a yellow solid. The yellow oil was left in air for several days giving colourless crystals of (VI). The yellow solid was sublimed under reduced pressure (1.3 Pa) to give colourless crystals of (VII). 1H NMR (CDCl3, 293 K, 300 MHz) δ 1.45 (s, 6H, Me), 3.53 (s, 2H), 3.93 (t, 1H, J = 1.1 Hz), 4.11 (s, 2H), 3.97 (t, 1H, J = 1.1 Hz), 4.64 (t, 1H, J = 1.1 Hz), 4.67 (t, 1H, J = 1.1 Hz).

5,5-Dimethenyl-2,2-dimethyl-1,3-dioxane bis(4-toluenesulfonate), (IX). 4-Toluenesulfonyl chloride (4.45 g, 23 mmol) was dissolved in pyridine (30 cm3) and added dropwise to a solution of (III) (1.76 g, 10 mol) in pyridine (30 cm3) at 273 K. The solution was allowed to warm to room temperature and stirred for 16 h. It was then poured into iced water (300 cm3) and HCl (6M, 5 cm3). The resulting precipitate was recovered by filtration, redissolved in ethyl acetate (200 cm3) and washed with HCl (1M, 3 × 50 cm3), aqueous NaHCO3 (3 × 50 cm3) and aqueous NaCl (3 × 50 cm3). The solution was dried over MgSO4, filtered and evaporated at reduced pressure to give a white solid (1.84 g, 60%) 1H NMR (CDCl3, 293 K, 300 MHz) δ 1.28 (s, 6H, Me2C), 2.49 (s, 6H, MeCAr), 3.63 (s, 4H), 3.99 (s, 4H), 7.41 (d, 4H, J = 8.7 Hz, aromatic), 7.79 (d, 4H, J = 9.1 Hz, aromatic)

5,5-Dimethenyl-2,2-dimethyl-1,3-dioxane bis(thiocyanate), (X). Compound (IX) (21.10 g, 44 mmol) and KSCN (41.92 g, 431 mmol) were dissolved in DMSO [dimethylsulfoxide?] (100 cm3). The solution was heated to 398 K and stirred for 40 min to give a caramel-coloured solution. The solution was cooled to room temperature and water (400 cm3) [added?] to give cloudy yellow solution. The solution was extracted with dichloromethane (3 × 100 cm3) and washed with HCl (1 M, 3 × 50 ml), aqueous NaHCO3 (3 × 50 cm3) and aqueous NaCl (3 × 50 cm3). The solution was dried over MgSO4, filtered and evaporated at reduced pressure. The resulting oil was purified via column chromatography (hexane–ethyl acetate 1: 2) to give a clear oil that when left in the air overnight yielded clear crystals (4.98 g, 45%) 1H NMR (CDCl3, 293 K, 300 MHz) δ 1.41 (s, 6H, Me), 3.29 (s, 4H), 3.85 (s, 4H).

1,3,-(Hydroxymethyl)propan-1,3-diyl bis(thiocyanate), (XI). Compound (X) (1.20 g, 4.0 mmol) was dissolved in THF [tetrahydrofuran?] (30 cm3) and HCl (6 M, 5 cm3) and heated to reflux for 90 min. After cooling to room temperature, the solvent was removed under reduced pressure to give an oil. Purified by column chromatography (hexane–ethyl acetate 1: 2) it gave an off-white oil, which crystallized on standing in air (0.65 g, 75%). 1H NMR (CDCl3, 293 K, 300 MHz) δ 3.24 (s, 4H), 3.68 (s, 4H).

2,2-Bis(sulfanylmethyl)propane-1,3-diol, (II). Compound (XI) (0.313 g, 1.0 mmol) was dissolved in dry THF (20 cm3) under nitrogen and added slowly via cannula to a cooled (273 K) suspension of LiAlH4 (1.21 g, 31 mmol) in dry THF (40 cm3). On completion of addition the solution was heated to 313 K and stirred for 48 h. The solution was then cooled to 273 K and quenched by dropwise addition of aqueous NH4Cl (25 cm3). The residue was extracted with ethyl acetate (3 × 25 ml) and dried over MgSO4. After filtration, removal of the solvent under reduced pressure gave a pungent off-white solid. This was recrystallized in hot chloroform to give the pure product (0.15 g, 64%). 1H NMR (CDCl3, 293 K, 300 MHz) δ 1.33 (t, 2H, J = 8.7 Hz, SH), 2.69 (d, 4H, J= 8.7 Hz, CH2S), 3.73 (s, 4H, CH2OH).

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

Refinement. The crystal was racemically twinned, and was refined using a twin matrix (-1 0 0 0 - 1 0 0 0 - 1). At the completion of refinement the component given here has occupancy of 0.43 (6).

The hydrogen atoms H(2) and H(3) were located using the CALC-OH program and were refined freely.

Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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) top
xyzUiso*/Ueq
C10.7909 (3)0.13770 (10)0.5028 (3)0.0197 (4)
C20.9249 (3)0.20254 (11)0.5065 (3)0.0275 (4)
H2A0.82640.24180.47310.033*
H2B1.00210.20940.64960.033*
C30.6142 (3)0.14634 (11)0.6516 (3)0.0280 (4)
H3A0.52870.10380.65470.034*
H3B0.68390.15560.79620.034*
C40.9320 (3)0.07572 (11)0.5656 (4)0.0288 (4)
H4A1.03760.06920.46170.035*
H4B0.83780.03480.56170.035*
C50.6855 (4)0.12745 (11)0.2759 (3)0.0296 (4)
H5A0.80210.12090.18340.035*
H5B0.60390.16910.22880.035*
O21.0828 (2)0.19936 (9)0.3555 (2)0.0318 (4)
O30.4718 (2)0.20143 (9)0.5815 (3)0.0313 (3)
Cl41.07971 (8)0.08378 (3)0.82505 (8)0.03635 (16)
Cl50.50322 (9)0.05610 (3)0.24649 (9)0.04208 (18)
H21.202 (6)0.1957 (16)0.404 (6)0.045 (8)*
H30.501 (5)0.2310 (14)0.648 (5)0.041 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0210 (8)0.0181 (9)0.0198 (9)0.0009 (7)0.0013 (6)−0.0004 (7)
C20.0250 (9)0.0252 (10)0.0322 (10)0.0003 (8)0.0028 (8)0.0028 (8)
C30.0248 (9)0.0331 (10)0.0262 (10)0.0019 (8)0.0038 (7)−0.0004 (8)
C40.0274 (10)0.0277 (11)0.0309 (10)0.0045 (8)0.0017 (8)0.0022 (9)
C50.0323 (11)0.0319 (10)0.0237 (10)0.0029 (9)−0.0001 (8)−0.0016 (8)
O20.0194 (7)0.0400 (9)0.0358 (9)−0.0019 (7)0.0025 (7)0.0163 (7)
O30.0212 (7)0.0334 (8)0.0380 (8)0.0067 (6)−0.0019 (6)−0.0129 (7)
Cl40.0293 (2)0.0435 (3)0.0342 (3)0.0032 (2)−0.00512 (19)0.0152 (2)
Cl50.0386 (3)0.0383 (3)0.0456 (4)−0.0059 (3)−0.0110 (3)−0.0130 (2)
Geometric parameters (Å, º) top
C1—C21.517 (3)C3—H3B0.9900
C1—C41.524 (3)C4—Cl41.804 (2)
C1—C51.532 (3)C4—H4A0.9900
C1—C31.535 (3)C4—H4B0.9900
C2—O21.449 (2)C5—Cl51.793 (2)
C2—H2A0.9900C5—H5A0.9900
C2—H2B0.9900C5—H5B0.9900
C3—O31.433 (3)O2—H20.77 (4)
C3—H3A0.9900O3—H30.73 (3)
C2—C1—C4111.96 (16)C1—C3—H3B109.7
C2—C1—C5107.21 (16)H3A—C3—H3B108.2
C4—C1—C5108.12 (16)C1—C4—Cl4112.59 (14)
C2—C1—C3108.74 (16)C1—C4—H4A109.1
C4—C1—C3110.46 (16)Cl4—C4—H4A109.1
C5—C1—C3110.30 (16)C1—C4—H4B109.1
O2—C2—C1111.09 (17)Cl4—C4—H4B109.1
O2—C2—H2A109.4H4A—C4—H4B107.8
C1—C2—H2A109.4C1—C5—Cl5113.23 (14)
O2—C2—H2B109.4C1—C5—H5A108.9
C1—C2—H2B109.4Cl5—C5—H5A108.9
H2A—C2—H2B108.0C1—C5—H5B108.9
O3—C3—C1110.03 (16)Cl5—C5—H5B108.9
O3—C3—H3A109.7H5A—C5—H5B107.7
C1—C3—H3A109.7C2—O2—H2115 (3)
O3—C3—H3B109.7C3—O3—H3109 (2)
C4—C1—C2—O262.4 (2)C2—C1—C4—Cl458.46 (19)
C5—C1—C2—O2−56.0 (2)C5—C1—C4—Cl4176.34 (14)
C3—C1—C2—O2−175.26 (17)C3—C1—C4—Cl4−62.88 (19)
C2—C1—C3—O361.3 (2)C2—C1—C5—Cl5−175.51 (13)
C4—C1—C3—O3−175.44 (16)C4—C1—C5—Cl563.61 (18)
C5—C1—C3—O3−56.0 (2)C3—C1—C5—Cl5−57.26 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.77 (4)1.91 (4)2.653 (2)165 (3)
O3—H3···O2ii0.73 (3)1.93 (3)2.657 (2)172 (3)
Symmetry codes: (i) x+1, y, z; (ii) x−1/2, −y+1/2, z+1/2.
(VII) 9,9-dimethyl-2,4,8,10-tetraoxa-3λ4-thiaspiro[5.5]undecan-3-one top
Crystal data top
C8H14O5SF(000) = 472
Mr = 222.25Dx = 1.499 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5825 reflections
a = 13.1287 (10) Åθ = 3.4–29.0°
b = 6.0588 (5) ŵ = 0.32 mm−1
c = 12.5024 (12) ÅT = 140 K
β = 98.135 (8)°Prism, colourless
V = 984.49 (15) Å30.80 × 0.20 × 0.06 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur 3/CCD
diffractometer		2222 independent reflections
Radiation source: Enhance (Mo) X-ray Source1805 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
Detector resolution: 16.0050 pixels mm-1θmax = 27.5°, θmin = 3.4°
ω scansh = −16→17
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		k = −7→7
Tmin = 0.771, Tmax = 1.000l = −16→16
12831 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0492P)2]
where P = (Fo2 + 2Fc2)/3
2222 reflections(Δ/σ)max = 0.001
129 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.39 e Å−3
Crystal data top
C8H14O5SV = 984.49 (15) Å3
Mr = 222.25Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.1287 (10) ŵ = 0.32 mm−1
b = 6.0588 (5) ÅT = 140 K
c = 12.5024 (12) Å0.80 × 0.20 × 0.06 mm
β = 98.135 (8)°
Data collection top
Oxford Diffraction Xcalibur 3/CCD
diffractometer		2222 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		1805 reflections with I > 2σ(I)
Tmin = 0.771, Tmax = 1.000Rint = 0.028
12831 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.079H-atom parameters constrained
S = 1.06Δρmax = 0.31 e Å−3
2222 reflectionsΔρmin = −0.39 e Å−3
129 parameters
Special details top

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

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 > 2σ(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) top
xyzUiso*/Ueq
C10.78608 (9)0.0967 (2)0.72178 (10)0.0142 (3)
C20.70686 (10)0.1782 (2)0.62931 (11)0.0181 (3)
H2A0.69400.33750.63880.022*
H2B0.73390.15870.55990.022*
C30.79634 (9)−0.1541 (2)0.70963 (11)0.0173 (3)
H3A0.8284−0.18700.64440.021*
H3B0.8415−0.21400.77310.021*
C40.74842 (10)0.1541 (2)0.82781 (11)0.0186 (3)
H4A0.73180.31350.82870.022*
H4B0.68480.07030.83400.022*
C50.88798 (10)0.2127 (2)0.71495 (11)0.0187 (3)
H5A0.91540.16340.64910.022*
H5B0.87640.37400.70930.022*
C210.62398 (10)−0.1749 (2)0.61483 (11)0.0170 (3)
C220.65135 (11)−0.2343 (2)0.50460 (11)0.0232 (3)
H22A0.7183−0.17010.49630.035*
H22B0.5987−0.17600.44830.035*
H22C0.6547−0.39520.49790.035*
C230.52239 (11)−0.2737 (2)0.63305 (13)0.0261 (3)
H23A0.5264−0.43500.62910.039*
H23B0.4679−0.22010.57740.039*
H23C0.5069−0.23030.70450.039*
O20.61281 (6)0.05888 (14)0.62652 (7)0.0176 (2)
O30.69761 (7)−0.25739 (14)0.70084 (8)0.0178 (2)
O40.82622 (7)0.10215 (16)0.91939 (7)0.0214 (2)
O50.96301 (7)0.16491 (16)0.80975 (8)0.0219 (2)
O410.90322 (8)0.47225 (17)0.91447 (8)0.0288 (3)
S410.93149 (2)0.24070 (6)0.92378 (3)0.02050 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0125 (6)0.0142 (6)0.0160 (6)−0.0011 (5)0.0028 (5)0.0001 (5)
C20.0197 (7)0.0131 (6)0.0205 (7)−0.0019 (5)−0.0003 (5)0.0019 (5)
C30.0143 (6)0.0151 (6)0.0215 (7)0.0012 (5)−0.0004 (5)−0.0015 (5)
C40.0137 (6)0.0236 (7)0.0187 (7)0.0002 (5)0.0024 (5)−0.0031 (6)
C50.0167 (6)0.0224 (7)0.0168 (7)−0.0051 (5)0.0024 (5)−0.0005 (5)
C210.0171 (7)0.0131 (6)0.0197 (7)0.0010 (5)−0.0015 (5)−0.0006 (5)
C220.0278 (7)0.0196 (7)0.0212 (7)0.0018 (6)−0.0003 (6)−0.0039 (6)
C230.0198 (7)0.0252 (8)0.0323 (8)−0.0066 (6)0.0003 (6)−0.0004 (6)
O20.0140 (5)0.0140 (5)0.0240 (5)0.0005 (3)−0.0001 (4)−0.0017 (4)
O30.0181 (5)0.0132 (5)0.0207 (5)−0.0023 (4)−0.0019 (4)0.0026 (4)
O40.0202 (5)0.0276 (5)0.0163 (5)−0.0040 (4)0.0024 (4)−0.0004 (4)
O50.0128 (5)0.0277 (5)0.0248 (5)−0.0016 (4)0.0016 (4)−0.0021 (4)
O410.0328 (6)0.0200 (5)0.0307 (6)−0.0004 (4)−0.0053 (5)−0.0058 (4)
S410.01916 (18)0.0206 (2)0.02027 (19)−0.00169 (14)−0.00235 (13)−0.00212 (14)
Geometric parameters (Å, º) top
C1—C41.5194 (18)C5—H5B0.9900
C1—C21.5239 (17)C21—O21.4338 (16)
C1—C51.5243 (17)C21—O31.4304 (15)
C1—C31.5347 (18)C21—C231.5084 (19)
C2—O21.4270 (15)C21—C221.5158 (19)
C2—H2A0.9900C22—H22A0.9800
C2—H2B0.9900C22—H22B0.9800
C3—O31.4295 (15)C22—H22C0.9800
C3—H3A0.9900C23—H23A0.9800
C3—H3B0.9900C23—H23B0.9800
C4—O41.4569 (16)C23—H23C0.9800
C4—H4A0.9900O4—S411.6113 (9)
C4—H4B0.9900O5—S411.6067 (10)
C5—O51.4590 (16)O41—S411.4516 (11)
C5—H5A0.9900
C4—C1—C2108.43 (11)C1—C5—H5B109.4
C4—C1—C5109.86 (11)H5A—C5—H5B108.0
C2—C1—C5108.55 (10)O3—C21—O2109.66 (10)
C4—C1—C3110.93 (11)O3—C21—C23105.41 (11)
C2—C1—C3107.81 (10)O2—C21—C23105.74 (10)
C5—C1—C3111.16 (10)O3—C21—C22112.25 (11)
O2—C2—C1110.46 (10)O2—C21—C22111.59 (11)
O2—C2—H2A109.6C23—C21—C22111.81 (11)
C1—C2—H2A109.6C21—C22—H22A109.5
O2—C2—H2B109.6C21—C22—H22B109.5
C1—C2—H2B109.6H22A—C22—H22B109.5
H2A—C2—H2B108.1C21—C22—H22C109.5
O3—C3—C1110.47 (10)H22A—C22—H22C109.5
O3—C3—H3A109.6H22B—C22—H22C109.5
C1—C3—H3A109.6C21—C23—H23A109.5
O3—C3—H3B109.6C21—C23—H23B109.5
C1—C3—H3B109.6H23A—C23—H23B109.5
H3A—C3—H3B108.1C21—C23—H23C109.5
O4—C4—C1110.95 (10)H23A—C23—H23C109.5
O4—C4—H4A109.4H23B—C23—H23C109.5
C1—C4—H4A109.4C2—O2—C21113.73 (9)
O4—C4—H4B109.4C3—O3—C21114.45 (10)
C1—C4—H4B109.4C4—O4—S41114.63 (8)
H4A—C4—H4B108.0C5—O5—S41115.79 (8)
O5—C5—C1111.10 (10)O41—S41—O5107.46 (6)
O5—C5—H5A109.4O41—S41—O4107.00 (6)
C1—C5—H5A109.4O5—S41—O498.53 (5)
O5—C5—H5B109.4
C4—C1—C2—O2−66.08 (13)O3—C21—O2—C257.19 (13)
C5—C1—C2—O2174.61 (10)C23—C21—O2—C2170.39 (11)
C3—C1—C2—O254.09 (14)C22—C21—O2—C2−67.83 (13)
C4—C1—C3—O365.64 (13)C1—C3—O3—C2156.11 (14)
C2—C1—C3—O3−52.94 (13)O2—C21—O3—C3−56.36 (13)
C5—C1—C3—O3−171.81 (10)C23—C21—O3—C3−169.77 (10)
C2—C1—C4—O4−173.71 (10)C22—C21—O3—C368.28 (14)
C5—C1—C4—O4−55.22 (14)C1—C4—O4—S4163.15 (13)
C3—C1—C4—O468.08 (13)C1—C5—O5—S41−60.57 (12)
C4—C1—C5—O553.66 (14)C5—O5—S41—O41−52.49 (10)
C2—C1—C5—O5172.07 (10)C5—O5—S41—O458.44 (9)
C3—C1—C5—O5−69.50 (13)C4—O4—S41—O4151.88 (10)
C1—C2—O2—C21−58.17 (14)C4—O4—S41—O5−59.42 (9)
(X) {[5-(cyanosulfanyl)-2,2-dimethyl-1,3-dioxan-5-yl]sulfanyl}formonitrile top
Crystal data top
C10H14N2O2S2F(000) = 544
Mr = 258.35Dx = 1.394 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9242 reflections
a = 9.3934 (2) Åθ = 3.6–29.2°
b = 8.5696 (2) ŵ = 0.42 mm−1
c = 15.7918 (4) ÅT = 140 K
β = 104.380 (2)°Rod, colourless
V = 1231.38 (5) Å30.70 × 0.08 × 0.08 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur 3/CCD
diffractometer		2791 independent reflections
Radiation source: Enhance (Mo) X-ray Source2222 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 16.0050 pixels mm-1θmax = 27.5°, θmin = 3.6°
ω scansh = −11→12
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		k = −10→11
Tmin = 0.840, Tmax = 1.000l = −20→20
17624 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0461P)2 + 0.1274P]
where P = (Fo2 + 2Fc2)/3
2791 reflections(Δ/σ)max = 0.001
147 parametersΔρmax = 0.37 e Å−3
0 restraintsΔρmin = −0.25 e Å−3
Crystal data top
C10H14N2O2S2V = 1231.38 (5) Å3
Mr = 258.35Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.3934 (2) ŵ = 0.42 mm−1
b = 8.5696 (2) ÅT = 140 K
c = 15.7918 (4) Å0.70 × 0.08 × 0.08 mm
β = 104.380 (2)°
Data collection top
Oxford Diffraction Xcalibur 3/CCD
diffractometer		2791 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		2222 reflections with I > 2σ(I)
Tmin = 0.840, Tmax = 1.000Rint = 0.030
17624 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.077H-atom parameters constrained
S = 1.01Δρmax = 0.37 e Å−3
2791 reflectionsΔρmin = −0.25 e Å−3
147 parameters
Special details top

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

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 > 2σ(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) top
xyzUiso*/Ueq
C10.23419 (15)0.29960 (17)0.41616 (9)0.0157 (3)
C20.16860 (15)0.30614 (18)0.31726 (9)0.0173 (3)
H2A0.14130.19970.29470.021*
H2B0.07860.37100.30440.021*
C30.27972 (17)0.46689 (17)0.44542 (9)0.0187 (3)
H3A0.19090.53280.43790.022*
H3B0.33160.46700.50820.022*
C40.11384 (16)0.23829 (18)0.45777 (9)0.0180 (3)
H4A0.07150.14260.42630.022*
H4B0.03450.31710.44890.022*
C50.37293 (16)0.19820 (17)0.43745 (10)0.0199 (3)
H5A0.40960.19200.50180.024*
H5B0.44940.25100.41460.024*
C210.31579 (16)0.52664 (17)0.30263 (9)0.0193 (3)
C220.44327 (18)0.5646 (2)0.26389 (11)0.0300 (4)
H22A0.51990.48510.28180.045*
H22B0.48330.66710.28470.045*
H22C0.40940.56610.20000.045*
C230.18848 (19)0.63992 (19)0.27201 (11)0.0264 (4)
H23A0.14630.62620.20920.040*
H23B0.22420.74720.28350.040*
H23C0.11300.61920.30370.040*
C410.15757 (17)0.3720 (2)0.61684 (10)0.0220 (3)
C510.27835 (18)−0.09155 (19)0.46874 (11)0.0257 (4)
N410.14691 (17)0.49023 (17)0.64877 (9)0.0329 (4)
N510.23023 (17)−0.15987 (17)0.51814 (10)0.0340 (4)
O20.27293 (11)0.37083 (12)0.27511 (6)0.0186 (2)
O30.37399 (11)0.53071 (12)0.39539 (6)0.0199 (2)
S40.17291 (4)0.19309 (5)0.57492 (2)0.02240 (11)
S50.35019 (5)−0.00049 (5)0.39382 (3)0.02761 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0154 (7)0.0195 (7)0.0119 (7)0.0010 (6)0.0031 (5)0.0003 (6)
C20.0172 (7)0.0218 (7)0.0128 (7)−0.0017 (6)0.0035 (6)0.0004 (6)
C30.0210 (8)0.0235 (8)0.0122 (7)−0.0010 (6)0.0052 (6)0.0000 (6)
C40.0178 (7)0.0239 (8)0.0119 (7)0.0015 (6)0.0028 (6)0.0033 (6)
C50.0191 (7)0.0213 (8)0.0193 (7)0.0015 (6)0.0049 (6)0.0023 (6)
C210.0219 (8)0.0213 (8)0.0144 (7)−0.0030 (6)0.0038 (6)0.0007 (6)
C220.0274 (9)0.0408 (10)0.0241 (9)−0.0086 (8)0.0109 (7)0.0022 (8)
C230.0321 (9)0.0233 (8)0.0225 (8)0.0020 (7)0.0040 (7)0.0055 (7)
C410.0209 (8)0.0314 (9)0.0151 (7)0.0060 (7)0.0070 (6)0.0043 (6)
C510.0250 (8)0.0231 (8)0.0287 (9)0.0047 (7)0.0060 (7)−0.0016 (7)
N410.0397 (9)0.0362 (9)0.0247 (8)0.0109 (7)0.0116 (7)0.0016 (7)
N510.0367 (9)0.0267 (8)0.0427 (9)−0.0025 (7)0.0172 (7)0.0010 (7)
O20.0212 (5)0.0225 (6)0.0135 (5)−0.0018 (4)0.0070 (4)−0.0001 (4)
O30.0191 (5)0.0262 (6)0.0140 (5)−0.0064 (4)0.0033 (4)0.0003 (4)
S40.0295 (2)0.0247 (2)0.01401 (18)0.00366 (17)0.00732 (15)0.00370 (15)
S50.0367 (2)0.0232 (2)0.0259 (2)0.00683 (18)0.01329 (18)0.00175 (17)
Geometric parameters (Å, º) top
C1—C21.5310 (19)C5—H5B0.9900
C1—C51.533 (2)C21—O21.4307 (17)
C1—C31.534 (2)C21—O31.4312 (17)
C1—C41.5346 (19)C21—C221.509 (2)
C2—O21.4265 (16)C21—C231.523 (2)
C2—H2A0.9900C22—H22A0.9800
C2—H2B0.9900C22—H22B0.9800
C3—O31.4334 (17)C22—H22C0.9800
C3—H3A0.9900C23—H23A0.9800
C3—H3B0.9900C23—H23B0.9800
C4—S41.8359 (14)C23—H23C0.9800
C4—H4A0.9900C41—N411.147 (2)
C4—H4B0.9900C41—S41.6903 (17)
C5—S51.8293 (16)C51—N511.154 (2)
C5—H5A0.9900C51—S51.6914 (17)
C2—C1—C5110.45 (11)C1—C5—H5B108.4
C2—C1—C3106.53 (12)S5—C5—H5B108.4
C5—C1—C3107.79 (12)H5A—C5—H5B107.4
C2—C1—C4107.26 (11)O2—C21—O3109.92 (11)
C5—C1—C4112.87 (12)O2—C21—C22105.64 (12)
C3—C1—C4111.77 (12)O3—C21—C22105.66 (12)
O2—C2—C1109.95 (11)O2—C21—C23111.03 (12)
O2—C2—H2A109.7O3—C21—C23112.31 (12)
C1—C2—H2A109.7C22—C21—C23111.94 (13)
O2—C2—H2B109.7C21—C22—H22A109.5
C1—C2—H2B109.7C21—C22—H22B109.5
H2A—C2—H2B108.2H22A—C22—H22B109.5
O3—C3—C1110.78 (11)C21—C22—H22C109.5
O3—C3—H3A109.5H22A—C22—H22C109.5
C1—C3—H3A109.5H22B—C22—H22C109.5
O3—C3—H3B109.5C21—C23—H23A109.5
C1—C3—H3B109.5C21—C23—H23B109.5
H3A—C3—H3B108.1H23A—C23—H23B109.5
C1—C4—S4115.68 (10)C21—C23—H23C109.5
C1—C4—H4A108.4H23A—C23—H23C109.5
S4—C4—H4A108.4H23B—C23—H23C109.5
C1—C4—H4B108.4N41—C41—S4176.90 (14)
S4—C4—H4B108.4N51—C51—S5176.96 (15)
H4A—C4—H4B107.4C2—O2—C21113.27 (11)
C1—C5—S5115.58 (10)C21—O3—C3115.06 (11)
C1—C5—H5A108.4C41—S4—C499.75 (7)
S5—C5—H5A108.4C51—S5—C5101.27 (7)
C5—C1—C2—O2−59.90 (15)C4—C1—C5—S564.74 (14)
C3—C1—C2—O256.90 (15)C1—C2—O2—C21−60.74 (15)
C4—C1—C2—O2176.72 (12)O3—C21—O2—C256.97 (15)
C2—C1—C3—O3−53.76 (15)C22—C21—O2—C2170.52 (12)
C5—C1—C3—O364.79 (14)C23—C21—O2—C2−67.92 (15)
C4—C1—C3—O3−170.62 (11)O2—C21—O3—C3−54.15 (15)
C2—C1—C4—S4171.61 (10)C22—C21—O3—C3−167.69 (12)
C5—C1—C4—S449.72 (15)C23—C21—O3—C370.00 (16)
C3—C1—C4—S4−71.98 (14)C1—C3—O3—C2154.79 (16)
C2—C1—C5—S5−55.33 (14)C1—C4—S4—C4185.30 (12)
C3—C1—C5—S5−171.34 (9)C1—C5—S5—C51−81.25 (12)
(XI) 1,3-bis(hydroxymethyl)propane-1,3-diyl bis(thiocyanate) top
Crystal data top
C7H10N2O2S2F(000) = 912
Mr = 218.29Dx = 1.476 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 4578 reflections
a = 8.6971 (5) Åθ = 3.4–29.0°
b = 10.3972 (5) ŵ = 0.51 mm−1
c = 21.7280 (15) ÅT = 140 K
V = 1964.8 (2) Å3Plate, colourless
Z = 80.39 × 0.13 × 0.01 mm
Data collection top
Oxford Diffraction Xcalibur 3/CCD
diffractometer		2245 independent reflections
Radiation source: Enhance (Mo) X-ray Source1498 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.082
Detector resolution: 16.0050 pixels mm-1θmax = 27.5°, θmin = 3.6°
ω scansh = −11→11
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		k = −13→13
Tmin = 0.926, Tmax = 1.000l = −27→27
25270 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069H atoms treated by a mixture of independent and constrained refinement
S = 0.94 w = 1/[σ2(Fo2) + (0.0294P)2]
where P = (Fo2 + 2Fc2)/3
2245 reflections(Δ/σ)max < 0.001
124 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.26 e Å−3
Crystal data top
C7H10N2O2S2V = 1964.8 (2) Å3
Mr = 218.29Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 8.6971 (5) ŵ = 0.51 mm−1
b = 10.3972 (5) ÅT = 140 K
c = 21.7280 (15) Å0.39 × 0.13 × 0.01 mm
Data collection top
Oxford Diffraction Xcalibur 3/CCD
diffractometer		2245 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		1498 reflections with I > 2σ(I)
Tmin = 0.926, Tmax = 1.000Rint = 0.082
25270 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.069H atoms treated by a mixture of independent and constrained refinement
S = 0.94Δρmax = 0.31 e Å−3
2245 reflectionsΔρmin = −0.26 e Å−3
124 parameters
Special details top

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

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 > 2σ(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.

The hydrogen atoms H(2) and H(3) were located using the CALC-OH program and were refined freely.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.4382 (2)0.69644 (19)0.89947 (9)0.0153 (5)
C20.3385 (2)0.68139 (19)0.95708 (10)0.0221 (5)
H2A0.40490.68450.99410.027*
H2B0.26510.75400.95950.027*
C30.5592 (2)0.5890 (2)0.89718 (10)0.0203 (5)
H3A0.50680.50450.89750.024*
H3B0.61810.59580.85830.024*
C40.5134 (2)0.82949 (19)0.90412 (10)0.0190 (5)
H4A0.57210.83370.94310.023*
H4B0.43120.89510.90630.023*
C50.3414 (2)0.67802 (18)0.84118 (9)0.0165 (5)
H5A0.29370.59160.84280.020*
H5B0.41110.67950.80520.020*
C410.5150 (3)0.9422 (2)0.79284 (11)0.0234 (5)
C510.0414 (3)0.7313 (2)0.86863 (11)0.0224 (5)
N410.4303 (2)0.98918 (19)0.75948 (9)0.0334 (5)
N51−0.0646 (2)0.69421 (19)0.89432 (9)0.0308 (5)
O20.25537 (18)0.56341 (16)0.95658 (8)0.0315 (4)
H20.289 (3)0.521 (2)0.9834 (12)0.047*
O30.66311 (16)0.59600 (14)0.94819 (7)0.0230 (4)
H30.737 (3)0.621 (3)0.9350 (11)0.035*
S40.64290 (6)0.87148 (5)0.84069 (3)0.02555 (16)
S50.18900 (6)0.79671 (5)0.82848 (3)0.02175 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0130 (11)0.0172 (11)0.0156 (11)−0.0016 (10)0.0002 (9)−0.0002 (10)
C20.0214 (12)0.0261 (12)0.0187 (12)−0.0011 (10)0.0009 (10)0.0018 (9)
C30.0172 (11)0.0185 (12)0.0252 (13)−0.0003 (10)−0.0047 (10)−0.0013 (10)
C40.0192 (12)0.0194 (12)0.0183 (12)−0.0008 (9)−0.0011 (10)−0.0002 (9)
C50.0124 (10)0.0163 (10)0.0207 (12)0.0021 (8)0.0015 (9)−0.0016 (9)
C410.0265 (13)0.0191 (13)0.0246 (14)−0.0006 (11)0.0110 (12)0.0022 (10)
C510.0178 (12)0.0213 (13)0.0281 (14)0.0047 (11)−0.0070 (11)−0.0035 (10)
N410.0344 (12)0.0369 (12)0.0289 (13)0.0066 (10)0.0060 (10)0.0055 (10)
N510.0201 (11)0.0332 (12)0.0393 (13)−0.0016 (10)0.0030 (10)−0.0018 (10)
O20.0272 (9)0.0368 (10)0.0305 (10)−0.0126 (8)−0.0071 (8)0.0170 (8)
O30.0146 (8)0.0295 (9)0.0250 (9)−0.0037 (7)−0.0055 (7)0.0078 (7)
S40.0179 (3)0.0251 (3)0.0336 (4)−0.0030 (3)0.0025 (3)0.0074 (3)
S50.0165 (3)0.0210 (3)0.0278 (3)0.0028 (2)−0.0015 (3)0.0053 (3)
Geometric parameters (Å, º) top
C1—C21.531 (3)C4—H4A0.9900
C1—C51.533 (3)C4—H4B0.9900
C1—C41.534 (3)C5—S51.8316 (19)
C1—C31.536 (3)C5—H5A0.9900
C2—O21.424 (2)C5—H5B0.9900
C2—H2A0.9900C41—N411.143 (3)
C2—H2B0.9900C41—S41.691 (3)
C3—O31.432 (2)C51—N511.144 (3)
C3—H3A0.9900C51—S51.695 (2)
C3—H3B0.9900O2—H20.78 (2)
C4—S41.833 (2)O3—H30.75 (2)
C2—C1—C5110.61 (16)C1—C4—S4115.31 (15)
C2—C1—C4106.26 (16)C1—C4—H4A108.4
C5—C1—C4113.68 (17)S4—C4—H4A108.4
C2—C1—C3109.89 (17)C1—C4—H4B108.4
C5—C1—C3105.00 (16)S4—C4—H4B108.4
C4—C1—C3111.44 (16)H4A—C4—H4B107.5
O2—C2—C1111.67 (17)C1—C5—S5115.95 (13)
O2—C2—H2A109.3C1—C5—H5A108.3
C1—C2—H2A109.3S5—C5—H5A108.3
O2—C2—H2B109.3C1—C5—H5B108.3
C1—C2—H2B109.3S5—C5—H5B108.3
H2A—C2—H2B107.9H5A—C5—H5B107.4
O3—C3—C1111.76 (17)N41—C41—S4178.6 (2)
O3—C3—H3A109.3N51—C51—S5175.1 (2)
C1—C3—H3A109.3C2—O2—H2106.8 (19)
O3—C3—H3B109.3C3—O3—H3105.3 (19)
C1—C3—H3B109.3C41—S4—C499.33 (10)
H3A—C3—H3B107.9C51—S5—C5101.53 (10)
C5—C1—C2—O253.0 (2)C5—C1—C4—S4−59.0 (2)
C4—C1—C2—O2176.88 (16)C3—C1—C4—S459.4 (2)
C3—C1—C2—O2−62.4 (2)C2—C1—C5—S563.80 (19)
C2—C1—C3—O3−63.0 (2)C4—C1—C5—S5−55.6 (2)
C5—C1—C3—O3178.02 (16)C3—C1—C5—S5−177.70 (14)
C4—C1—C3—O354.5 (2)C1—C4—S4—C4190.10 (17)
C2—C1—C4—S4179.08 (14)C1—C5—S5—C51−86.97 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.78 (2)1.97 (3)2.744 (2)170 (3)
O3—H3···N51ii0.75 (2)2.08 (2)2.832 (2)177 (3)
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x+1, y, z.

Experimental details

(VI)(VII)(X)(XI)
Crystal data
Chemical formulaC5H10Cl2O2C8H14O5SC10H14N2O2S2C7H10N2O2S2
Mr173.03222.25258.35218.29
Crystal system, space groupMonoclinic, CcMonoclinic, P21/cMonoclinic, P21/cOrthorhombic, Pbca
Temperature (K)140140140140
a, b, c (Å)6.1635 (3), 19.6495 (10), 6.3889 (4)13.1287 (10), 6.0588 (5), 12.5024 (12)9.3934 (2), 8.5696 (2), 15.7918 (4)8.6971 (5), 10.3972 (5), 21.7280 (15)
α, β, γ (°)90, 96.617 (5), 9090, 98.135 (8), 9090, 104.380 (2), 9090, 90, 90
V (Å3)768.60 (7)984.49 (15)1231.38 (5)1964.8 (2)
Z4448
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm−1)0.770.320.420.51
Crystal size (mm)0.40 × 0.20 × 0.100.80 × 0.20 × 0.060.70 × 0.08 × 0.080.39 × 0.13 × 0.01
Data collection
DiffractometerOxford Diffraction Xcalibur 3/CCD
diffractometer		Oxford Diffraction Xcalibur 3/CCD
diffractometer		Oxford Diffraction Xcalibur 3/CCD
diffractometer		Oxford Diffraction Xcalibur 3/CCD
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.776, 1.0000.771, 1.0000.840, 1.0000.926, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		5628, 1707, 1609 12831, 2222, 1805 17624, 2791, 2222 25270, 2245, 1498
Rint0.0280.0280.0300.082
(sin θ/λ)max (Å−1)0.6490.6500.6500.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.075, 1.08 0.029, 0.079, 1.06 0.029, 0.077, 1.01 0.040, 0.069, 0.94
No. of reflections1707222227912245
No. of parameters91129147124
No. of restraints2000
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrainedH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.46, −0.230.31, −0.390.37, −0.250.31, −0.26
Absolute structureFlack (1983), ???? Friedel pairs???
Absolute structure parameter0.43 (6)???

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SIR92 (Altomare et al., 1993), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010), SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and PARST (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) for (VI) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.77 (4)1.91 (4)2.653 (2)165 (3)
O3—H3···O2ii0.73 (3)1.93 (3)2.657 (2)172 (3)
Symmetry codes: (i) x+1, y, z; (ii) x−1/2, −y+1/2, z+1/2.
Selected geometric parameters (Å, º) for (VII) top
C3—O31.4295 (15)C21—O31.4304 (15)
C4—O41.4569 (16)O4—S411.6113 (9)
C5—O51.4590 (16)O5—S411.6067 (10)
C21—O21.4338 (16)O41—S411.4516 (11)
O41—S41—O5107.46 (6)O5—S41—O498.53 (5)
O41—S41—O4107.00 (6)
Selected bond lengths (Å) for (XI) top
C2—O21.424 (2)C41—S41.691 (3)
C3—O31.432 (2)C51—N511.144 (3)
C41—N411.143 (3)C51—S51.695 (2)
Hydrogen-bond geometry (Å, º) for (XI) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.78 (2)1.97 (3)2.744 (2)170 (3)
O3—H3···N51ii0.75 (2)2.08 (2)2.832 (2)177 (3)
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x+1, y, z.
 

Acknowledgements

The authors thank the BBSRC and the EPSRC for funding.

References

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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 67| Part 1| January 2011| Pages o1-o5
doi:10.1107/S0108270110049371
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