Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110049371/sk3390sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110049371/sk3390VIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110049371/sk3390VIIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110049371/sk3390Xsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110049371/sk3390XIsup5.hkl |
CCDC references: 813484; 813485; 813486; 813487
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.
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.
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).
C5H10Cl2O2 | F(000) = 360 |
Mr = 173.03 | Dx = 1.495 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 3911 reflections |
a = 6.1635 (3) Å | θ = 3.5–29.0° |
b = 19.6495 (10) Å | µ = 0.77 mm−1 |
c = 6.3889 (4) Å | T = 140 K |
β = 96.617 (5)° | Prism, colourless |
V = 768.60 (7) Å3 | 0.40 × 0.20 × 0.10 mm |
Z = 4 |
Oxford Diffraction Xcalibur 3/CCD diffractometer | 1707 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1609 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 16.0050 pixels mm-1 | θmax = 27.5°, θmin = 3.5° |
ω scans | h = −7→7 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −25→25 |
Tmin = 0.776, Tmax = 1.000 | l = −7→8 |
5628 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.028 | H 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 reflections | Δρmax = 0.46 e Å−3 |
91 parameters | Δρmin = −0.23 e Å−3 |
2 restraints | Absolute structure: Flack (1983), ???? Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.43 (6) |
C5H10Cl2O2 | V = 768.60 (7) Å3 |
Mr = 173.03 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 6.1635 (3) Å | µ = 0.77 mm−1 |
b = 19.6495 (10) Å | T = 140 K |
c = 6.3889 (4) Å | 0.40 × 0.20 × 0.10 mm |
β = 96.617 (5)° |
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 = 1.000 | Rint = 0.028 |
5628 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.075 | Δρmax = 0.46 e Å−3 |
S = 1.08 | Δρmin = −0.23 e Å−3 |
1707 reflections | Absolute structure: Flack (1983), ???? Friedel pairs |
91 parameters | Absolute structure parameter: 0.43 (6) |
2 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7909 (3) | 0.13770 (10) | 0.5028 (3) | 0.0197 (4) | |
C2 | 0.9249 (3) | 0.20254 (11) | 0.5065 (3) | 0.0275 (4) | |
H2A | 0.8264 | 0.2418 | 0.4731 | 0.033* | |
H2B | 1.0021 | 0.2094 | 0.6496 | 0.033* | |
C3 | 0.6142 (3) | 0.14634 (11) | 0.6516 (3) | 0.0280 (4) | |
H3A | 0.5287 | 0.1038 | 0.6547 | 0.034* | |
H3B | 0.6839 | 0.1556 | 0.7962 | 0.034* | |
C4 | 0.9320 (3) | 0.07572 (11) | 0.5656 (4) | 0.0288 (4) | |
H4A | 1.0376 | 0.0692 | 0.4617 | 0.035* | |
H4B | 0.8378 | 0.0348 | 0.5617 | 0.035* | |
C5 | 0.6855 (4) | 0.12745 (11) | 0.2759 (3) | 0.0296 (4) | |
H5A | 0.8021 | 0.1209 | 0.1834 | 0.035* | |
H5B | 0.6039 | 0.1691 | 0.2288 | 0.035* | |
O2 | 1.0828 (2) | 0.19936 (9) | 0.3555 (2) | 0.0318 (4) | |
O3 | 0.4718 (2) | 0.20143 (9) | 0.5815 (3) | 0.0313 (3) | |
Cl4 | 1.07971 (8) | 0.08378 (3) | 0.82505 (8) | 0.03635 (16) | |
Cl5 | 0.50322 (9) | 0.05610 (3) | 0.24649 (9) | 0.04208 (18) | |
H2 | 1.202 (6) | 0.1957 (16) | 0.404 (6) | 0.045 (8)* | |
H3 | 0.501 (5) | 0.2310 (14) | 0.648 (5) | 0.041 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0210 (8) | 0.0181 (9) | 0.0198 (9) | 0.0009 (7) | 0.0013 (6) | −0.0004 (7) |
C2 | 0.0250 (9) | 0.0252 (10) | 0.0322 (10) | 0.0003 (8) | 0.0028 (8) | 0.0028 (8) |
C3 | 0.0248 (9) | 0.0331 (10) | 0.0262 (10) | 0.0019 (8) | 0.0038 (7) | −0.0004 (8) |
C4 | 0.0274 (10) | 0.0277 (11) | 0.0309 (10) | 0.0045 (8) | 0.0017 (8) | 0.0022 (9) |
C5 | 0.0323 (11) | 0.0319 (10) | 0.0237 (10) | 0.0029 (9) | −0.0001 (8) | −0.0016 (8) |
O2 | 0.0194 (7) | 0.0400 (9) | 0.0358 (9) | −0.0019 (7) | 0.0025 (7) | 0.0163 (7) |
O3 | 0.0212 (7) | 0.0334 (8) | 0.0380 (8) | 0.0067 (6) | −0.0019 (6) | −0.0129 (7) |
Cl4 | 0.0293 (2) | 0.0435 (3) | 0.0342 (3) | 0.0032 (2) | −0.00512 (19) | 0.0152 (2) |
Cl5 | 0.0386 (3) | 0.0383 (3) | 0.0456 (4) | −0.0059 (3) | −0.0110 (3) | −0.0130 (2) |
C1—C2 | 1.517 (3) | C3—H3B | 0.9900 |
C1—C4 | 1.524 (3) | C4—Cl4 | 1.804 (2) |
C1—C5 | 1.532 (3) | C4—H4A | 0.9900 |
C1—C3 | 1.535 (3) | C4—H4B | 0.9900 |
C2—O2 | 1.449 (2) | C5—Cl5 | 1.793 (2) |
C2—H2A | 0.9900 | C5—H5A | 0.9900 |
C2—H2B | 0.9900 | C5—H5B | 0.9900 |
C3—O3 | 1.433 (3) | O2—H2 | 0.77 (4) |
C3—H3A | 0.9900 | O3—H3 | 0.73 (3) |
C2—C1—C4 | 111.96 (16) | C1—C3—H3B | 109.7 |
C2—C1—C5 | 107.21 (16) | H3A—C3—H3B | 108.2 |
C4—C1—C5 | 108.12 (16) | C1—C4—Cl4 | 112.59 (14) |
C2—C1—C3 | 108.74 (16) | C1—C4—H4A | 109.1 |
C4—C1—C3 | 110.46 (16) | Cl4—C4—H4A | 109.1 |
C5—C1—C3 | 110.30 (16) | C1—C4—H4B | 109.1 |
O2—C2—C1 | 111.09 (17) | Cl4—C4—H4B | 109.1 |
O2—C2—H2A | 109.4 | H4A—C4—H4B | 107.8 |
C1—C2—H2A | 109.4 | C1—C5—Cl5 | 113.23 (14) |
O2—C2—H2B | 109.4 | C1—C5—H5A | 108.9 |
C1—C2—H2B | 109.4 | Cl5—C5—H5A | 108.9 |
H2A—C2—H2B | 108.0 | C1—C5—H5B | 108.9 |
O3—C3—C1 | 110.03 (16) | Cl5—C5—H5B | 108.9 |
O3—C3—H3A | 109.7 | H5A—C5—H5B | 107.7 |
C1—C3—H3A | 109.7 | C2—O2—H2 | 115 (3) |
O3—C3—H3B | 109.7 | C3—O3—H3 | 109 (2) |
C4—C1—C2—O2 | 62.4 (2) | C2—C1—C4—Cl4 | 58.46 (19) |
C5—C1—C2—O2 | −56.0 (2) | C5—C1—C4—Cl4 | 176.34 (14) |
C3—C1—C2—O2 | −175.26 (17) | C3—C1—C4—Cl4 | −62.88 (19) |
C2—C1—C3—O3 | 61.3 (2) | C2—C1—C5—Cl5 | −175.51 (13) |
C4—C1—C3—O3 | −175.44 (16) | C4—C1—C5—Cl5 | 63.61 (18) |
C5—C1—C3—O3 | −56.0 (2) | C3—C1—C5—Cl5 | −57.26 (19) |
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−1/2, −y+1/2, z+1/2. |
C8H14O5S | F(000) = 472 |
Mr = 222.25 | Dx = 1.499 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5825 reflections |
a = 13.1287 (10) Å | θ = 3.4–29.0° |
b = 6.0588 (5) Å | µ = 0.32 mm−1 |
c = 12.5024 (12) Å | T = 140 K |
β = 98.135 (8)° | Prism, colourless |
V = 984.49 (15) Å3 | 0.80 × 0.20 × 0.06 mm |
Z = 4 |
Oxford Diffraction Xcalibur 3/CCD diffractometer | 2222 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1805 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 16.0050 pixels mm-1 | θmax = 27.5°, θmin = 3.4° |
ω scans | h = −16→17 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −7→7 |
Tmin = 0.771, Tmax = 1.000 | l = −16→16 |
12831 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-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 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
C8H14O5S | V = 984.49 (15) Å3 |
Mr = 222.25 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.1287 (10) Å | µ = 0.32 mm−1 |
b = 6.0588 (5) Å | T = 140 K |
c = 12.5024 (12) Å | 0.80 × 0.20 × 0.06 mm |
β = 98.135 (8)° |
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 = 1.000 | Rint = 0.028 |
12831 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.31 e Å−3 |
2222 reflections | Δρmin = −0.39 e Å−3 |
129 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.78608 (9) | 0.0967 (2) | 0.72178 (10) | 0.0142 (3) | |
C2 | 0.70686 (10) | 0.1782 (2) | 0.62931 (11) | 0.0181 (3) | |
H2A | 0.6940 | 0.3375 | 0.6388 | 0.022* | |
H2B | 0.7339 | 0.1587 | 0.5599 | 0.022* | |
C3 | 0.79634 (9) | −0.1541 (2) | 0.70963 (11) | 0.0173 (3) | |
H3A | 0.8284 | −0.1870 | 0.6444 | 0.021* | |
H3B | 0.8415 | −0.2140 | 0.7731 | 0.021* | |
C4 | 0.74842 (10) | 0.1541 (2) | 0.82781 (11) | 0.0186 (3) | |
H4A | 0.7318 | 0.3135 | 0.8287 | 0.022* | |
H4B | 0.6848 | 0.0703 | 0.8340 | 0.022* | |
C5 | 0.88798 (10) | 0.2127 (2) | 0.71495 (11) | 0.0187 (3) | |
H5A | 0.9154 | 0.1634 | 0.6491 | 0.022* | |
H5B | 0.8764 | 0.3740 | 0.7093 | 0.022* | |
C21 | 0.62398 (10) | −0.1749 (2) | 0.61483 (11) | 0.0170 (3) | |
C22 | 0.65135 (11) | −0.2343 (2) | 0.50460 (11) | 0.0232 (3) | |
H22A | 0.7183 | −0.1701 | 0.4963 | 0.035* | |
H22B | 0.5987 | −0.1760 | 0.4483 | 0.035* | |
H22C | 0.6547 | −0.3952 | 0.4979 | 0.035* | |
C23 | 0.52239 (11) | −0.2737 (2) | 0.63305 (13) | 0.0261 (3) | |
H23A | 0.5264 | −0.4350 | 0.6291 | 0.039* | |
H23B | 0.4679 | −0.2201 | 0.5774 | 0.039* | |
H23C | 0.5069 | −0.2303 | 0.7045 | 0.039* | |
O2 | 0.61281 (6) | 0.05888 (14) | 0.62652 (7) | 0.0176 (2) | |
O3 | 0.69761 (7) | −0.25739 (14) | 0.70084 (8) | 0.0178 (2) | |
O4 | 0.82622 (7) | 0.10215 (16) | 0.91939 (7) | 0.0214 (2) | |
O5 | 0.96301 (7) | 0.16491 (16) | 0.80975 (8) | 0.0219 (2) | |
O41 | 0.90322 (8) | 0.47225 (17) | 0.91447 (8) | 0.0288 (3) | |
S41 | 0.93149 (2) | 0.24070 (6) | 0.92378 (3) | 0.02050 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0125 (6) | 0.0142 (6) | 0.0160 (6) | −0.0011 (5) | 0.0028 (5) | 0.0001 (5) |
C2 | 0.0197 (7) | 0.0131 (6) | 0.0205 (7) | −0.0019 (5) | −0.0003 (5) | 0.0019 (5) |
C3 | 0.0143 (6) | 0.0151 (6) | 0.0215 (7) | 0.0012 (5) | −0.0004 (5) | −0.0015 (5) |
C4 | 0.0137 (6) | 0.0236 (7) | 0.0187 (7) | 0.0002 (5) | 0.0024 (5) | −0.0031 (6) |
C5 | 0.0167 (6) | 0.0224 (7) | 0.0168 (7) | −0.0051 (5) | 0.0024 (5) | −0.0005 (5) |
C21 | 0.0171 (7) | 0.0131 (6) | 0.0197 (7) | 0.0010 (5) | −0.0015 (5) | −0.0006 (5) |
C22 | 0.0278 (7) | 0.0196 (7) | 0.0212 (7) | 0.0018 (6) | −0.0003 (6) | −0.0039 (6) |
C23 | 0.0198 (7) | 0.0252 (8) | 0.0323 (8) | −0.0066 (6) | 0.0003 (6) | −0.0004 (6) |
O2 | 0.0140 (5) | 0.0140 (5) | 0.0240 (5) | 0.0005 (3) | −0.0001 (4) | −0.0017 (4) |
O3 | 0.0181 (5) | 0.0132 (5) | 0.0207 (5) | −0.0023 (4) | −0.0019 (4) | 0.0026 (4) |
O4 | 0.0202 (5) | 0.0276 (5) | 0.0163 (5) | −0.0040 (4) | 0.0024 (4) | −0.0004 (4) |
O5 | 0.0128 (5) | 0.0277 (5) | 0.0248 (5) | −0.0016 (4) | 0.0016 (4) | −0.0021 (4) |
O41 | 0.0328 (6) | 0.0200 (5) | 0.0307 (6) | −0.0004 (4) | −0.0053 (5) | −0.0058 (4) |
S41 | 0.01916 (18) | 0.0206 (2) | 0.02027 (19) | −0.00169 (14) | −0.00235 (13) | −0.00212 (14) |
C1—C4 | 1.5194 (18) | C5—H5B | 0.9900 |
C1—C2 | 1.5239 (17) | C21—O2 | 1.4338 (16) |
C1—C5 | 1.5243 (17) | C21—O3 | 1.4304 (15) |
C1—C3 | 1.5347 (18) | C21—C23 | 1.5084 (19) |
C2—O2 | 1.4270 (15) | C21—C22 | 1.5158 (19) |
C2—H2A | 0.9900 | C22—H22A | 0.9800 |
C2—H2B | 0.9900 | C22—H22B | 0.9800 |
C3—O3 | 1.4295 (15) | C22—H22C | 0.9800 |
C3—H3A | 0.9900 | C23—H23A | 0.9800 |
C3—H3B | 0.9900 | C23—H23B | 0.9800 |
C4—O4 | 1.4569 (16) | C23—H23C | 0.9800 |
C4—H4A | 0.9900 | O4—S41 | 1.6113 (9) |
C4—H4B | 0.9900 | O5—S41 | 1.6067 (10) |
C5—O5 | 1.4590 (16) | O41—S41 | 1.4516 (11) |
C5—H5A | 0.9900 | ||
C4—C1—C2 | 108.43 (11) | C1—C5—H5B | 109.4 |
C4—C1—C5 | 109.86 (11) | H5A—C5—H5B | 108.0 |
C2—C1—C5 | 108.55 (10) | O3—C21—O2 | 109.66 (10) |
C4—C1—C3 | 110.93 (11) | O3—C21—C23 | 105.41 (11) |
C2—C1—C3 | 107.81 (10) | O2—C21—C23 | 105.74 (10) |
C5—C1—C3 | 111.16 (10) | O3—C21—C22 | 112.25 (11) |
O2—C2—C1 | 110.46 (10) | O2—C21—C22 | 111.59 (11) |
O2—C2—H2A | 109.6 | C23—C21—C22 | 111.81 (11) |
C1—C2—H2A | 109.6 | C21—C22—H22A | 109.5 |
O2—C2—H2B | 109.6 | C21—C22—H22B | 109.5 |
C1—C2—H2B | 109.6 | H22A—C22—H22B | 109.5 |
H2A—C2—H2B | 108.1 | C21—C22—H22C | 109.5 |
O3—C3—C1 | 110.47 (10) | H22A—C22—H22C | 109.5 |
O3—C3—H3A | 109.6 | H22B—C22—H22C | 109.5 |
C1—C3—H3A | 109.6 | C21—C23—H23A | 109.5 |
O3—C3—H3B | 109.6 | C21—C23—H23B | 109.5 |
C1—C3—H3B | 109.6 | H23A—C23—H23B | 109.5 |
H3A—C3—H3B | 108.1 | C21—C23—H23C | 109.5 |
O4—C4—C1 | 110.95 (10) | H23A—C23—H23C | 109.5 |
O4—C4—H4A | 109.4 | H23B—C23—H23C | 109.5 |
C1—C4—H4A | 109.4 | C2—O2—C21 | 113.73 (9) |
O4—C4—H4B | 109.4 | C3—O3—C21 | 114.45 (10) |
C1—C4—H4B | 109.4 | C4—O4—S41 | 114.63 (8) |
H4A—C4—H4B | 108.0 | C5—O5—S41 | 115.79 (8) |
O5—C5—C1 | 111.10 (10) | O41—S41—O5 | 107.46 (6) |
O5—C5—H5A | 109.4 | O41—S41—O4 | 107.00 (6) |
C1—C5—H5A | 109.4 | O5—S41—O4 | 98.53 (5) |
O5—C5—H5B | 109.4 | ||
C4—C1—C2—O2 | −66.08 (13) | O3—C21—O2—C2 | 57.19 (13) |
C5—C1—C2—O2 | 174.61 (10) | C23—C21—O2—C2 | 170.39 (11) |
C3—C1—C2—O2 | 54.09 (14) | C22—C21—O2—C2 | −67.83 (13) |
C4—C1—C3—O3 | 65.64 (13) | C1—C3—O3—C21 | 56.11 (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—C3 | 68.28 (14) |
C5—C1—C4—O4 | −55.22 (14) | C1—C4—O4—S41 | 63.15 (13) |
C3—C1—C4—O4 | 68.08 (13) | C1—C5—O5—S41 | −60.57 (12) |
C4—C1—C5—O5 | 53.66 (14) | C5—O5—S41—O41 | −52.49 (10) |
C2—C1—C5—O5 | 172.07 (10) | C5—O5—S41—O4 | 58.44 (9) |
C3—C1—C5—O5 | −69.50 (13) | C4—O4—S41—O41 | 51.88 (10) |
C1—C2—O2—C21 | −58.17 (14) | C4—O4—S41—O5 | −59.42 (9) |
C10H14N2O2S2 | F(000) = 544 |
Mr = 258.35 | Dx = 1.394 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9242 reflections |
a = 9.3934 (2) Å | θ = 3.6–29.2° |
b = 8.5696 (2) Å | µ = 0.42 mm−1 |
c = 15.7918 (4) Å | T = 140 K |
β = 104.380 (2)° | Rod, colourless |
V = 1231.38 (5) Å3 | 0.70 × 0.08 × 0.08 mm |
Z = 4 |
Oxford Diffraction Xcalibur 3/CCD diffractometer | 2791 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2222 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 16.0050 pixels mm-1 | θmax = 27.5°, θmin = 3.6° |
ω scans | h = −11→12 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −10→11 |
Tmin = 0.840, Tmax = 1.000 | l = −20→20 |
17624 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-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 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C10H14N2O2S2 | V = 1231.38 (5) Å3 |
Mr = 258.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.3934 (2) Å | µ = 0.42 mm−1 |
b = 8.5696 (2) Å | T = 140 K |
c = 15.7918 (4) Å | 0.70 × 0.08 × 0.08 mm |
β = 104.380 (2)° |
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 = 1.000 | Rint = 0.030 |
17624 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.37 e Å−3 |
2791 reflections | Δρmin = −0.25 e Å−3 |
147 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.23419 (15) | 0.29960 (17) | 0.41616 (9) | 0.0157 (3) | |
C2 | 0.16860 (15) | 0.30614 (18) | 0.31726 (9) | 0.0173 (3) | |
H2A | 0.1413 | 0.1997 | 0.2947 | 0.021* | |
H2B | 0.0786 | 0.3710 | 0.3044 | 0.021* | |
C3 | 0.27972 (17) | 0.46689 (17) | 0.44542 (9) | 0.0187 (3) | |
H3A | 0.1909 | 0.5328 | 0.4379 | 0.022* | |
H3B | 0.3316 | 0.4670 | 0.5082 | 0.022* | |
C4 | 0.11384 (16) | 0.23829 (18) | 0.45777 (9) | 0.0180 (3) | |
H4A | 0.0715 | 0.1426 | 0.4263 | 0.022* | |
H4B | 0.0345 | 0.3171 | 0.4489 | 0.022* | |
C5 | 0.37293 (16) | 0.19820 (17) | 0.43745 (10) | 0.0199 (3) | |
H5A | 0.4096 | 0.1920 | 0.5018 | 0.024* | |
H5B | 0.4494 | 0.2510 | 0.4146 | 0.024* | |
C21 | 0.31579 (16) | 0.52664 (17) | 0.30263 (9) | 0.0193 (3) | |
C22 | 0.44327 (18) | 0.5646 (2) | 0.26389 (11) | 0.0300 (4) | |
H22A | 0.5199 | 0.4851 | 0.2818 | 0.045* | |
H22B | 0.4833 | 0.6671 | 0.2847 | 0.045* | |
H22C | 0.4094 | 0.5661 | 0.2000 | 0.045* | |
C23 | 0.18848 (19) | 0.63992 (19) | 0.27201 (11) | 0.0264 (4) | |
H23A | 0.1463 | 0.6262 | 0.2092 | 0.040* | |
H23B | 0.2242 | 0.7472 | 0.2835 | 0.040* | |
H23C | 0.1130 | 0.6192 | 0.3037 | 0.040* | |
C41 | 0.15757 (17) | 0.3720 (2) | 0.61684 (10) | 0.0220 (3) | |
C51 | 0.27835 (18) | −0.09155 (19) | 0.46874 (11) | 0.0257 (4) | |
N41 | 0.14691 (17) | 0.49023 (17) | 0.64877 (9) | 0.0329 (4) | |
N51 | 0.23023 (17) | −0.15987 (17) | 0.51814 (10) | 0.0340 (4) | |
O2 | 0.27293 (11) | 0.37083 (12) | 0.27511 (6) | 0.0186 (2) | |
O3 | 0.37399 (11) | 0.53071 (12) | 0.39539 (6) | 0.0199 (2) | |
S4 | 0.17291 (4) | 0.19309 (5) | 0.57492 (2) | 0.02240 (11) | |
S5 | 0.35019 (5) | −0.00049 (5) | 0.39382 (3) | 0.02761 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0154 (7) | 0.0195 (7) | 0.0119 (7) | 0.0010 (6) | 0.0031 (5) | 0.0003 (6) |
C2 | 0.0172 (7) | 0.0218 (7) | 0.0128 (7) | −0.0017 (6) | 0.0035 (6) | 0.0004 (6) |
C3 | 0.0210 (8) | 0.0235 (8) | 0.0122 (7) | −0.0010 (6) | 0.0052 (6) | 0.0000 (6) |
C4 | 0.0178 (7) | 0.0239 (8) | 0.0119 (7) | 0.0015 (6) | 0.0028 (6) | 0.0033 (6) |
C5 | 0.0191 (7) | 0.0213 (8) | 0.0193 (7) | 0.0015 (6) | 0.0049 (6) | 0.0023 (6) |
C21 | 0.0219 (8) | 0.0213 (8) | 0.0144 (7) | −0.0030 (6) | 0.0038 (6) | 0.0007 (6) |
C22 | 0.0274 (9) | 0.0408 (10) | 0.0241 (9) | −0.0086 (8) | 0.0109 (7) | 0.0022 (8) |
C23 | 0.0321 (9) | 0.0233 (8) | 0.0225 (8) | 0.0020 (7) | 0.0040 (7) | 0.0055 (7) |
C41 | 0.0209 (8) | 0.0314 (9) | 0.0151 (7) | 0.0060 (7) | 0.0070 (6) | 0.0043 (6) |
C51 | 0.0250 (8) | 0.0231 (8) | 0.0287 (9) | 0.0047 (7) | 0.0060 (7) | −0.0016 (7) |
N41 | 0.0397 (9) | 0.0362 (9) | 0.0247 (8) | 0.0109 (7) | 0.0116 (7) | 0.0016 (7) |
N51 | 0.0367 (9) | 0.0267 (8) | 0.0427 (9) | −0.0025 (7) | 0.0172 (7) | 0.0010 (7) |
O2 | 0.0212 (5) | 0.0225 (6) | 0.0135 (5) | −0.0018 (4) | 0.0070 (4) | −0.0001 (4) |
O3 | 0.0191 (5) | 0.0262 (6) | 0.0140 (5) | −0.0064 (4) | 0.0033 (4) | 0.0003 (4) |
S4 | 0.0295 (2) | 0.0247 (2) | 0.01401 (18) | 0.00366 (17) | 0.00732 (15) | 0.00370 (15) |
S5 | 0.0367 (2) | 0.0232 (2) | 0.0259 (2) | 0.00683 (18) | 0.01329 (18) | 0.00175 (17) |
C1—C2 | 1.5310 (19) | C5—H5B | 0.9900 |
C1—C5 | 1.533 (2) | C21—O2 | 1.4307 (17) |
C1—C3 | 1.534 (2) | C21—O3 | 1.4312 (17) |
C1—C4 | 1.5346 (19) | C21—C22 | 1.509 (2) |
C2—O2 | 1.4265 (16) | C21—C23 | 1.523 (2) |
C2—H2A | 0.9900 | C22—H22A | 0.9800 |
C2—H2B | 0.9900 | C22—H22B | 0.9800 |
C3—O3 | 1.4334 (17) | C22—H22C | 0.9800 |
C3—H3A | 0.9900 | C23—H23A | 0.9800 |
C3—H3B | 0.9900 | C23—H23B | 0.9800 |
C4—S4 | 1.8359 (14) | C23—H23C | 0.9800 |
C4—H4A | 0.9900 | C41—N41 | 1.147 (2) |
C4—H4B | 0.9900 | C41—S4 | 1.6903 (17) |
C5—S5 | 1.8293 (16) | C51—N51 | 1.154 (2) |
C5—H5A | 0.9900 | C51—S5 | 1.6914 (17) |
C2—C1—C5 | 110.45 (11) | C1—C5—H5B | 108.4 |
C2—C1—C3 | 106.53 (12) | S5—C5—H5B | 108.4 |
C5—C1—C3 | 107.79 (12) | H5A—C5—H5B | 107.4 |
C2—C1—C4 | 107.26 (11) | O2—C21—O3 | 109.92 (11) |
C5—C1—C4 | 112.87 (12) | O2—C21—C22 | 105.64 (12) |
C3—C1—C4 | 111.77 (12) | O3—C21—C22 | 105.66 (12) |
O2—C2—C1 | 109.95 (11) | O2—C21—C23 | 111.03 (12) |
O2—C2—H2A | 109.7 | O3—C21—C23 | 112.31 (12) |
C1—C2—H2A | 109.7 | C22—C21—C23 | 111.94 (13) |
O2—C2—H2B | 109.7 | C21—C22—H22A | 109.5 |
C1—C2—H2B | 109.7 | C21—C22—H22B | 109.5 |
H2A—C2—H2B | 108.2 | H22A—C22—H22B | 109.5 |
O3—C3—C1 | 110.78 (11) | C21—C22—H22C | 109.5 |
O3—C3—H3A | 109.5 | H22A—C22—H22C | 109.5 |
C1—C3—H3A | 109.5 | H22B—C22—H22C | 109.5 |
O3—C3—H3B | 109.5 | C21—C23—H23A | 109.5 |
C1—C3—H3B | 109.5 | C21—C23—H23B | 109.5 |
H3A—C3—H3B | 108.1 | H23A—C23—H23B | 109.5 |
C1—C4—S4 | 115.68 (10) | C21—C23—H23C | 109.5 |
C1—C4—H4A | 108.4 | H23A—C23—H23C | 109.5 |
S4—C4—H4A | 108.4 | H23B—C23—H23C | 109.5 |
C1—C4—H4B | 108.4 | N41—C41—S4 | 176.90 (14) |
S4—C4—H4B | 108.4 | N51—C51—S5 | 176.96 (15) |
H4A—C4—H4B | 107.4 | C2—O2—C21 | 113.27 (11) |
C1—C5—S5 | 115.58 (10) | C21—O3—C3 | 115.06 (11) |
C1—C5—H5A | 108.4 | C41—S4—C4 | 99.75 (7) |
S5—C5—H5A | 108.4 | C51—S5—C5 | 101.27 (7) |
C5—C1—C2—O2 | −59.90 (15) | C4—C1—C5—S5 | 64.74 (14) |
C3—C1—C2—O2 | 56.90 (15) | C1—C2—O2—C21 | −60.74 (15) |
C4—C1—C2—O2 | 176.72 (12) | O3—C21—O2—C2 | 56.97 (15) |
C2—C1—C3—O3 | −53.76 (15) | C22—C21—O2—C2 | 170.52 (12) |
C5—C1—C3—O3 | 64.79 (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—S4 | 171.61 (10) | C22—C21—O3—C3 | −167.69 (12) |
C5—C1—C4—S4 | 49.72 (15) | C23—C21—O3—C3 | 70.00 (16) |
C3—C1—C4—S4 | −71.98 (14) | C1—C3—O3—C21 | 54.79 (16) |
C2—C1—C5—S5 | −55.33 (14) | C1—C4—S4—C41 | 85.30 (12) |
C3—C1—C5—S5 | −171.34 (9) | C1—C5—S5—C51 | −81.25 (12) |
C7H10N2O2S2 | F(000) = 912 |
Mr = 218.29 | Dx = 1.476 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 4578 reflections |
a = 8.6971 (5) Å | θ = 3.4–29.0° |
b = 10.3972 (5) Å | µ = 0.51 mm−1 |
c = 21.7280 (15) Å | T = 140 K |
V = 1964.8 (2) Å3 | Plate, colourless |
Z = 8 | 0.39 × 0.13 × 0.01 mm |
Oxford Diffraction Xcalibur 3/CCD diffractometer | 2245 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1498 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.082 |
Detector resolution: 16.0050 pixels mm-1 | θmax = 27.5°, θmin = 3.6° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −13→13 |
Tmin = 0.926, Tmax = 1.000 | l = −27→27 |
25270 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H 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 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C7H10N2O2S2 | V = 1964.8 (2) Å3 |
Mr = 218.29 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.6971 (5) Å | µ = 0.51 mm−1 |
b = 10.3972 (5) Å | T = 140 K |
c = 21.7280 (15) Å | 0.39 × 0.13 × 0.01 mm |
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 = 1.000 | Rint = 0.082 |
25270 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.31 e Å−3 |
2245 reflections | Δρmin = −0.26 e Å−3 |
124 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.4382 (2) | 0.69644 (19) | 0.89947 (9) | 0.0153 (5) | |
C2 | 0.3385 (2) | 0.68139 (19) | 0.95708 (10) | 0.0221 (5) | |
H2A | 0.4049 | 0.6845 | 0.9941 | 0.027* | |
H2B | 0.2651 | 0.7540 | 0.9595 | 0.027* | |
C3 | 0.5592 (2) | 0.5890 (2) | 0.89718 (10) | 0.0203 (5) | |
H3A | 0.5068 | 0.5045 | 0.8975 | 0.024* | |
H3B | 0.6181 | 0.5958 | 0.8583 | 0.024* | |
C4 | 0.5134 (2) | 0.82949 (19) | 0.90412 (10) | 0.0190 (5) | |
H4A | 0.5721 | 0.8337 | 0.9431 | 0.023* | |
H4B | 0.4312 | 0.8951 | 0.9063 | 0.023* | |
C5 | 0.3414 (2) | 0.67802 (18) | 0.84118 (9) | 0.0165 (5) | |
H5A | 0.2937 | 0.5916 | 0.8428 | 0.020* | |
H5B | 0.4111 | 0.6795 | 0.8052 | 0.020* | |
C41 | 0.5150 (3) | 0.9422 (2) | 0.79284 (11) | 0.0234 (5) | |
C51 | 0.0414 (3) | 0.7313 (2) | 0.86863 (11) | 0.0224 (5) | |
N41 | 0.4303 (2) | 0.98918 (19) | 0.75948 (9) | 0.0334 (5) | |
N51 | −0.0646 (2) | 0.69421 (19) | 0.89432 (9) | 0.0308 (5) | |
O2 | 0.25537 (18) | 0.56341 (16) | 0.95658 (8) | 0.0315 (4) | |
H2 | 0.289 (3) | 0.521 (2) | 0.9834 (12) | 0.047* | |
O3 | 0.66311 (16) | 0.59600 (14) | 0.94819 (7) | 0.0230 (4) | |
H3 | 0.737 (3) | 0.621 (3) | 0.9350 (11) | 0.035* | |
S4 | 0.64290 (6) | 0.87148 (5) | 0.84069 (3) | 0.02555 (16) | |
S5 | 0.18900 (6) | 0.79671 (5) | 0.82848 (3) | 0.02175 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0130 (11) | 0.0172 (11) | 0.0156 (11) | −0.0016 (10) | 0.0002 (9) | −0.0002 (10) |
C2 | 0.0214 (12) | 0.0261 (12) | 0.0187 (12) | −0.0011 (10) | 0.0009 (10) | 0.0018 (9) |
C3 | 0.0172 (11) | 0.0185 (12) | 0.0252 (13) | −0.0003 (10) | −0.0047 (10) | −0.0013 (10) |
C4 | 0.0192 (12) | 0.0194 (12) | 0.0183 (12) | −0.0008 (9) | −0.0011 (10) | −0.0002 (9) |
C5 | 0.0124 (10) | 0.0163 (10) | 0.0207 (12) | 0.0021 (8) | 0.0015 (9) | −0.0016 (9) |
C41 | 0.0265 (13) | 0.0191 (13) | 0.0246 (14) | −0.0006 (11) | 0.0110 (12) | 0.0022 (10) |
C51 | 0.0178 (12) | 0.0213 (13) | 0.0281 (14) | 0.0047 (11) | −0.0070 (11) | −0.0035 (10) |
N41 | 0.0344 (12) | 0.0369 (12) | 0.0289 (13) | 0.0066 (10) | 0.0060 (10) | 0.0055 (10) |
N51 | 0.0201 (11) | 0.0332 (12) | 0.0393 (13) | −0.0016 (10) | 0.0030 (10) | −0.0018 (10) |
O2 | 0.0272 (9) | 0.0368 (10) | 0.0305 (10) | −0.0126 (8) | −0.0071 (8) | 0.0170 (8) |
O3 | 0.0146 (8) | 0.0295 (9) | 0.0250 (9) | −0.0037 (7) | −0.0055 (7) | 0.0078 (7) |
S4 | 0.0179 (3) | 0.0251 (3) | 0.0336 (4) | −0.0030 (3) | 0.0025 (3) | 0.0074 (3) |
S5 | 0.0165 (3) | 0.0210 (3) | 0.0278 (3) | 0.0028 (2) | −0.0015 (3) | 0.0053 (3) |
C1—C2 | 1.531 (3) | C4—H4A | 0.9900 |
C1—C5 | 1.533 (3) | C4—H4B | 0.9900 |
C1—C4 | 1.534 (3) | C5—S5 | 1.8316 (19) |
C1—C3 | 1.536 (3) | C5—H5A | 0.9900 |
C2—O2 | 1.424 (2) | C5—H5B | 0.9900 |
C2—H2A | 0.9900 | C41—N41 | 1.143 (3) |
C2—H2B | 0.9900 | C41—S4 | 1.691 (3) |
C3—O3 | 1.432 (2) | C51—N51 | 1.144 (3) |
C3—H3A | 0.9900 | C51—S5 | 1.695 (2) |
C3—H3B | 0.9900 | O2—H2 | 0.78 (2) |
C4—S4 | 1.833 (2) | O3—H3 | 0.75 (2) |
C2—C1—C5 | 110.61 (16) | C1—C4—S4 | 115.31 (15) |
C2—C1—C4 | 106.26 (16) | C1—C4—H4A | 108.4 |
C5—C1—C4 | 113.68 (17) | S4—C4—H4A | 108.4 |
C2—C1—C3 | 109.89 (17) | C1—C4—H4B | 108.4 |
C5—C1—C3 | 105.00 (16) | S4—C4—H4B | 108.4 |
C4—C1—C3 | 111.44 (16) | H4A—C4—H4B | 107.5 |
O2—C2—C1 | 111.67 (17) | C1—C5—S5 | 115.95 (13) |
O2—C2—H2A | 109.3 | C1—C5—H5A | 108.3 |
C1—C2—H2A | 109.3 | S5—C5—H5A | 108.3 |
O2—C2—H2B | 109.3 | C1—C5—H5B | 108.3 |
C1—C2—H2B | 109.3 | S5—C5—H5B | 108.3 |
H2A—C2—H2B | 107.9 | H5A—C5—H5B | 107.4 |
O3—C3—C1 | 111.76 (17) | N41—C41—S4 | 178.6 (2) |
O3—C3—H3A | 109.3 | N51—C51—S5 | 175.1 (2) |
C1—C3—H3A | 109.3 | C2—O2—H2 | 106.8 (19) |
O3—C3—H3B | 109.3 | C3—O3—H3 | 105.3 (19) |
C1—C3—H3B | 109.3 | C41—S4—C4 | 99.33 (10) |
H3A—C3—H3B | 107.9 | C51—S5—C5 | 101.53 (10) |
C5—C1—C2—O2 | 53.0 (2) | C5—C1—C4—S4 | −59.0 (2) |
C4—C1—C2—O2 | 176.88 (16) | C3—C1—C4—S4 | 59.4 (2) |
C3—C1—C2—O2 | −62.4 (2) | C2—C1—C5—S5 | 63.80 (19) |
C2—C1—C3—O3 | −63.0 (2) | C4—C1—C5—S5 | −55.6 (2) |
C5—C1—C3—O3 | 178.02 (16) | C3—C1—C5—S5 | −177.70 (14) |
C4—C1—C3—O3 | 54.5 (2) | C1—C4—S4—C41 | 90.10 (17) |
C2—C1—C4—S4 | 179.08 (14) | C1—C5—S5—C51 | −86.97 (16) |
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. |
Experimental details
(VI) | (VII) | (X) | (XI) | |
Crystal data | ||||
Chemical formula | C5H10Cl2O2 | C8H14O5S | C10H14N2O2S2 | C7H10N2O2S2 |
Mr | 173.03 | 222.25 | 258.35 | 218.29 |
Crystal system, space group | Monoclinic, Cc | Monoclinic, P21/c | Monoclinic, P21/c | Orthorhombic, Pbca |
Temperature (K) | 140 | 140 | 140 | 140 |
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), 90 | 90, 98.135 (8), 90 | 90, 104.380 (2), 90 | 90, 90, 90 |
V (Å3) | 768.60 (7) | 984.49 (15) | 1231.38 (5) | 1964.8 (2) |
Z | 4 | 4 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.77 | 0.32 | 0.42 | 0.51 |
Crystal size (mm) | 0.40 × 0.20 × 0.10 | 0.80 × 0.20 × 0.06 | 0.70 × 0.08 × 0.08 | 0.39 × 0.13 × 0.01 |
Data collection | ||||
Diffractometer | Oxford Diffraction Xcalibur 3/CCD diffractometer | Oxford Diffraction Xcalibur 3/CCD diffractometer | Oxford Diffraction Xcalibur 3/CCD diffractometer | Oxford Diffraction Xcalibur 3/CCD diffractometer |
Absorption correction | Multi-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, Tmax | 0.776, 1.000 | 0.771, 1.000 | 0.840, 1.000 | 0.926, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5628, 1707, 1609 | 12831, 2222, 1805 | 17624, 2791, 2222 | 25270, 2245, 1498 |
Rint | 0.028 | 0.028 | 0.030 | 0.082 |
(sin θ/λ)max (Å−1) | 0.649 | 0.650 | 0.650 | 0.649 |
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 reflections | 1707 | 2222 | 2791 | 2245 |
No. of parameters | 91 | 129 | 147 | 124 |
No. of restraints | 2 | 0 | 0 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.46, −0.23 | 0.31, −0.39 | 0.37, −0.25 | 0.31, −0.26 |
Absolute structure | Flack (1983), ???? Friedel pairs | ? | ? | ? |
Absolute structure parameter | 0.43 (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).
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−1/2, −y+1/2, z+1/2. |
C3—O3 | 1.4295 (15) | C21—O3 | 1.4304 (15) |
C4—O4 | 1.4569 (16) | O4—S41 | 1.6113 (9) |
C5—O5 | 1.4590 (16) | O5—S41 | 1.6067 (10) |
C21—O2 | 1.4338 (16) | O41—S41 | 1.4516 (11) |
O41—S41—O5 | 107.46 (6) | O5—S41—O4 | 98.53 (5) |
O41—S41—O4 | 107.00 (6) |
C2—O2 | 1.424 (2) | C41—S4 | 1.691 (3) |
C3—O3 | 1.432 (2) | C51—N51 | 1.144 (3) |
C41—N41 | 1.143 (3) | C51—S5 | 1.695 (2) |
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. |
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.