Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680001878X/cf6006sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680001878X/cf6006Isup2.hkl |
CCDC reference: 155881
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.034
- wR factor = 0.087
- Data-to-parameter ratio = 9.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
ABSMU_01 Alert C The ratio of given/expected absorption coefficient lies outside the range 0.99 <> 1.01 Calculated value of mu = 0.263 Value of mu given = 0.260 General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.00 From the CIF: _reflns_number_total 1272 Count of symmetry unique reflns 1275 Completeness (_total/calc) 99.76% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
In a 50 ml round-bottomed flask fitted with a Dean–Stark apparatus, benzene (30 ml), N,N'-dibenzyl-(R)-cystinol (392 mg, 1 mmol), paraformaldehyde (90 mg, 3 mmol) and p-toluenesulfonic acid (10 mg) were added. The mixture was heated at reflux for 5 h and cooled to room temperature. The benzene was removed under vacuum and the residue dissolved in CH2Cl2 (30 ml), washed with 0.5 N NaOH aqueous solution, dried with MgSO4, filtered, and the solvent removed under vacuum to afford 353 mg (yield 87%) of the title compound. A crystal suitable for X-ray analysis was grown by slow evaporation of a dichloromethane solution (m.p. 320–321 K). Elemental analysis for C22H28N2O2S2, calculated: C 63.43, H 6.77, N 6.72%; found C 63.20, H 7.26, N 7.10%. [α]D20 = +14.8 (c 1.96, CHCl3). 1H NMR (200 MHz, CDCl3, Bruker): δ 2.47 (dd, 2H, J = 8.4 Hz, J = 13.2 Hz), 2.76 (dd, 2H, J = 5.8 Hz, J = 13.2 Hz), 3.21–3.36 (m, 2H), 3.48 (dd, 2H, J = 5.0 Hz, J = 8.4 Hz), 3.70–3.76 (m, 4H), 4.04 (dd, 2H, J = 7.0 Hz, J = 8.4 Hz), 4.29 (s, 4H), 7.19–7.34 (m, 10H). 13C NMR (50 MHz, CDCl3): δ 41.08, 58.92, 62.06, 69.06, 85.98, 127.97, 128.24, 128.60.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1992); cell refinement: CAD-4 EXPRESS; data reduction: HELENA (Spek, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of (I) with 50% probability ellipsoids. H atoms have been omitted for clarity. The C atoms of the phenyl ring are numbered consecutively. |
C11H14NOS | F(000) = 444 |
Mr = 208.29 | Dx = 1.265 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
a = 20.281 (3) Å | Cell parameters from 25 reflections |
b = 8.925 (2) Å | θ = 10.5–14.3° |
c = 6.053 (1) Å | µ = 0.26 mm−1 |
β = 93.112 (12)° | T = 293 K |
V = 1094.1 (3) Å3 | Plate, yellow |
Z = 4 | 0.2 × 0.2 × 0.1 mm |
CAD-4 diffractometer | 996 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 27.0°, θmin = 2.5° |
ω/2θ scans | h = 0→25 |
Absorption correction: ψ scan (North et al., 1968) | k = −11→0 |
Tmin = 0.949, Tmax = 0.974 | l = −7→7 |
1307 measured reflections | 3 standard reflections every 200 reflections |
1272 independent reflections | intensity decay: 4.3% |
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)] = 0.034 | H-atom parameters not refined |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0379P)2 + 0.1198P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.001 |
1272 reflections | Δρmax = 0.18 e Å−3 |
136 parameters | Δρmin = −0.20 e Å−3 |
1 restraint | Absolute structure: Flack (1983), no Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.1 (3) |
C11H14NOS | V = 1094.1 (3) Å3 |
Mr = 208.29 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 20.281 (3) Å | µ = 0.26 mm−1 |
b = 8.925 (2) Å | T = 293 K |
c = 6.053 (1) Å | 0.2 × 0.2 × 0.1 mm |
β = 93.112 (12)° |
CAD-4 diffractometer | 996 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.025 |
Tmin = 0.949, Tmax = 0.974 | 3 standard reflections every 200 reflections |
1307 measured reflections | intensity decay: 4.3% |
1272 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters not refined |
wR(F2) = 0.087 | Δρmax = 0.18 e Å−3 |
S = 1.10 | Δρmin = −0.20 e Å−3 |
1272 reflections | Absolute structure: Flack (1983), no Friedel pairs |
136 parameters | Absolute structure parameter: 0.1 (3) |
1 restraint |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.50087 (3) | 0.53766 (15) | 0.66834 (13) | 0.0510 (2) | |
C1 | 0.56305 (13) | 0.3979 (4) | 0.7434 (5) | 0.0435 (7) | |
H1A | 0.5598 | 0.3714 | 0.8979 | 0.052* | |
H1B | 0.5543 | 0.3083 | 0.6559 | 0.052* | |
C2 | 0.63272 (14) | 0.4520 (4) | 0.7074 (5) | 0.0452 (7) | |
H2 | 0.6365 | 0.4809 | 0.5524 | 0.054* | |
N3 | 0.68072 (11) | 0.3317 (3) | 0.7682 (4) | 0.0461 (6) | |
C4 | 0.73203 (16) | 0.4033 (5) | 0.9075 (6) | 0.0608 (9) | |
H4A | 0.7529 | 0.3316 | 1.0095 | 0.073* | |
H4B | 0.7655 | 0.4466 | 0.8184 | 0.073* | |
O5 | 0.69972 (12) | 0.5151 (4) | 1.0224 (4) | 0.0733 (8) | |
C6 | 0.6552 (2) | 0.5801 (4) | 0.8590 (7) | 0.0746 (13) | |
H6A | 0.6772 | 0.6569 | 0.7766 | 0.090* | |
H6B | 0.6177 | 0.6249 | 0.9274 | 0.090* | |
C7 | 0.70738 (16) | 0.2514 (5) | 0.5825 (6) | 0.0550 (9) | |
H7A | 0.7464 (18) | 0.184 (5) | 0.648 (5) | 0.068 (11)* | |
H7B | 0.7223 (15) | 0.318 (4) | 0.472 (6) | 0.058 (10)* | |
C11 | 0.65849 (14) | 0.1447 (4) | 0.4731 (5) | 0.0468 (7) | |
C12 | 0.63029 (16) | 0.1704 (5) | 0.2645 (5) | 0.0546 (9) | |
H12 | 0.6413 | 0.2570 | 0.1892 | 0.066* | |
C13 | 0.58643 (19) | 0.0713 (5) | 0.1657 (6) | 0.0676 (12) | |
H13 | 0.5680 | 0.0913 | 0.0247 | 0.081* | |
C14 | 0.5694 (2) | −0.0573 (5) | 0.2731 (8) | 0.0760 (12) | |
H14 | 0.5403 | −0.1257 | 0.2048 | 0.091* | |
C15 | 0.5962 (2) | −0.0836 (5) | 0.4837 (7) | 0.0765 (12) | |
H15 | 0.5839 | −0.1687 | 0.5602 | 0.092* | |
C16 | 0.64076 (17) | 0.0152 (5) | 0.5811 (6) | 0.0626 (10) | |
H16 | 0.6593 | −0.0051 | 0.7217 | 0.075* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0418 (4) | 0.0495 (4) | 0.0606 (5) | 0.0064 (5) | −0.0073 (3) | −0.0063 (5) |
C1 | 0.0350 (13) | 0.0422 (16) | 0.0525 (17) | 0.0012 (13) | −0.0032 (12) | 0.0057 (14) |
C2 | 0.0366 (15) | 0.0467 (17) | 0.0510 (17) | −0.0041 (14) | −0.0080 (13) | 0.0115 (15) |
N3 | 0.0354 (12) | 0.0534 (16) | 0.0481 (14) | 0.0002 (12) | −0.0086 (11) | 0.0109 (13) |
C4 | 0.0440 (17) | 0.077 (3) | 0.0595 (19) | −0.0090 (19) | −0.0152 (14) | 0.005 (2) |
O5 | 0.0687 (14) | 0.073 (2) | 0.0745 (15) | −0.0062 (17) | −0.0276 (12) | −0.0053 (16) |
C6 | 0.063 (2) | 0.057 (3) | 0.100 (3) | −0.0080 (18) | −0.033 (2) | −0.001 (2) |
C7 | 0.0410 (17) | 0.068 (2) | 0.056 (2) | 0.0025 (18) | 0.0040 (15) | 0.0097 (19) |
C11 | 0.0399 (15) | 0.0497 (19) | 0.0514 (17) | 0.0082 (15) | 0.0073 (13) | 0.0081 (16) |
C12 | 0.0539 (18) | 0.058 (2) | 0.0522 (18) | 0.0004 (17) | 0.0032 (15) | 0.0156 (18) |
C13 | 0.067 (2) | 0.070 (3) | 0.065 (2) | 0.0010 (19) | −0.0102 (18) | 0.0026 (19) |
C14 | 0.075 (3) | 0.059 (3) | 0.093 (3) | −0.014 (2) | −0.007 (2) | 0.001 (2) |
C15 | 0.083 (3) | 0.053 (3) | 0.093 (3) | −0.010 (2) | 0.002 (2) | 0.025 (2) |
C16 | 0.0609 (19) | 0.065 (3) | 0.0612 (19) | 0.006 (2) | −0.0027 (16) | 0.025 (2) |
S1—C1 | 1.814 (3) | O5—C6 | 1.427 (4) |
S1—S1i | 2.0363 (16) | C7—C11 | 1.502 (5) |
C1—C2 | 1.520 (4) | C11—C12 | 1.377 (4) |
C2—N3 | 1.482 (4) | C11—C16 | 1.385 (5) |
C2—C6 | 1.520 (5) | C12—C13 | 1.369 (5) |
N3—C4 | 1.452 (4) | C13—C14 | 1.373 (6) |
N3—C7 | 1.462 (4) | C14—C15 | 1.378 (6) |
C4—O5 | 1.399 (5) | C15—C16 | 1.373 (5) |
C1—S1—S1i | 102.98 (11) | O5—C6—C2 | 105.7 (3) |
C2—C1—S1 | 112.6 (2) | N3—C7—C11 | 112.8 (3) |
N3—C2—C6 | 103.0 (2) | C12—C11—C16 | 117.8 (3) |
N3—C2—C1 | 109.7 (2) | C12—C11—C7 | 122.0 (3) |
C6—C2—C1 | 113.8 (3) | C16—C11—C7 | 120.2 (3) |
C4—N3—C7 | 112.3 (2) | C13—C12—C11 | 121.4 (3) |
C4—N3—C2 | 105.4 (3) | C12—C13—C14 | 120.5 (4) |
C7—N3—C2 | 115.5 (2) | C13—C14—C15 | 119.0 (4) |
O5—C4—N3 | 105.2 (3) | C16—C15—C14 | 120.3 (4) |
C4—O5—C6 | 104.0 (3) | C15—C16—C11 | 121.0 (3) |
S1i—S1—C1—C2 | 72.9 (2) | C4—N3—C7—C11 | 164.8 (3) |
S1—C1—C2—N3 | −179.02 (19) | C2—N3—C7—C11 | −74.3 (4) |
S1—C1—C2—C6 | 66.3 (3) | N3—C7—C11—C12 | 109.9 (3) |
C6—C2—N3—C4 | −10.8 (3) | N3—C7—C11—C16 | −70.6 (4) |
C1—C2—N3—C4 | −132.2 (3) | C16—C11—C12—C13 | −0.4 (5) |
C6—C2—N3—C7 | −135.3 (3) | C7—C11—C12—C13 | 179.2 (3) |
C1—C2—N3—C7 | 103.3 (3) | C11—C12—C13—C14 | −0.1 (6) |
C7—N3—C4—O5 | 159.3 (3) | C12—C13—C14—C15 | 1.3 (6) |
C2—N3—C4—O5 | 32.8 (3) | C13—C14—C15—C16 | −2.1 (7) |
N3—C4—O5—C6 | −42.1 (3) | C14—C15—C16—C11 | 1.7 (6) |
C4—O5—C6—C2 | 34.7 (4) | C12—C11—C16—C15 | −0.4 (5) |
N3—C2—C6—O5 | −14.1 (4) | C7—C11—C16—C15 | 180.0 (3) |
C1—C2—C6—O5 | 104.5 (3) | C1—S1—S1i—C1i | 90.2 (2) |
Symmetry code: (i) −x+1, y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C11H14NOS |
Mr | 208.29 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 293 |
a, b, c (Å) | 20.281 (3), 8.925 (2), 6.053 (1) |
β (°) | 93.112 (12) |
V (Å3) | 1094.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.2 × 0.2 × 0.1 |
Data collection | |
Diffractometer | CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.949, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1307, 1272, 996 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.087, 1.10 |
No. of reflections | 1272 |
No. of parameters | 136 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.18, −0.20 |
Absolute structure | Flack (1983), no Friedel pairs |
Absolute structure parameter | 0.1 (3) |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1992), CAD-4 EXPRESS, HELENA (Spek, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
S1—C1 | 1.814 (3) | N3—C4 | 1.452 (4) |
S1—S1i | 2.0363 (16) | N3—C7 | 1.462 (4) |
C1—C2 | 1.520 (4) | C4—O5 | 1.399 (5) |
C2—N3 | 1.482 (4) | O5—C6 | 1.427 (4) |
C2—C6 | 1.520 (5) | C7—C11 | 1.502 (5) |
C1—S1—S1i | 102.98 (11) | C4—N3—C2 | 105.4 (3) |
C2—C1—S1 | 112.6 (2) | C7—N3—C2 | 115.5 (2) |
N3—C2—C6 | 103.0 (2) | O5—C4—N3 | 105.2 (3) |
N3—C2—C1 | 109.7 (2) | C4—O5—C6 | 104.0 (3) |
C6—C2—C1 | 113.8 (3) | O5—C6—C2 | 105.7 (3) |
C4—N3—C7 | 112.3 (2) | N3—C7—C11 | 112.8 (3) |
Symmetry code: (i) −x+1, y, −z+1. |
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The title compound [alternatively called 3,3'-dibenzyl-4,4'-dithiodi(oxazolane)], (I), a chiral disulfide, was prepared from L-cysteine in a short synthetic sequence and applied successfully as a highly efficient catalyst (Braga et al., 1999).
The asymmetric unit contains a half molecule of the disulfide. The complete molecule is generated by a twofold axis parallel to b, bisecting the S—S bond.
All bond distances and angles are normal. The torsion angle C1—-S1–S1i—C1i [symmetry code: (i) 1 - x, y, 1 - z] of 90.4 (2)° is close to the average found for similar compounds in the Cambridge Structural Database (Allen & Kennard, 1983) (86.29°). No close intermolecular contacts are seen, though the S—S bonds are almost aligned along the z axis and the intermolecular S···S distance is 4.0177 (17) Å.
The Cremer & Pople (1975) puckering parameters for the five-membered ring C2—N3—C4—O5—C6 were calculated by PLATON (Spek, 1995) to be Q2 = 0.373 Å and ϕ2 = 14.92°, corresponding to a twist conformation with the axis through C2.