Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038184/bt2464sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038184/bt2464Isup2.hkl |
CCDC reference: 660231
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.005 Å
- R factor = 0.083
- wR factor = 0.202
- Data-to-parameter ratio = 17.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.10 From the CIF: _reflns_number_total 3229 Count of symmetry unique reflns 1856 Completeness (_total/calc) 173.98% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1373 Fraction of Friedel pairs measured 0.740 Are heavy atom types Z>Si present yes PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4 = . S
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Dianin's compound was synthesized according to the literature method (Brienne & Jacques, 1975) and the chirally pure (S)-enantiomer was sequentially converted to the thiol derivative (Hardy et al., 1977). Single crystals suitable for X-ray analysis were then obtained by slow evaporation of a solution of (S)-4-p-mercaptophenyl-2,2,4-trimethylchroman in cyclohexane.
All H atoms were positioned geometrically and constrained to ride on their parent atoms; Uiso(H) values were set at 1.2 times Ueq(C, S) for CH2, aromatic C and S—H groups and 1.5 times Ueq(C) for CH3 groups.
In conjunction with our investigation on the formation of clathrates (Esterhuysen et al., 2005; Lloyd & Bredenkamp, 2005; Lloyd et al., 2005) we have synthesized an enantiomerically pure form of 4-p-mercaptophenyl-2,2,4-trimethylchroman, (I), the thiol derivative of Dianin's compound.
It is well known that a racemic mixture of (I) packs in such a way that six thiol molecules are linked to each other by a network of S—H···S hydrogen bonds such that the S atoms form a near-planar hexagon (Hardy et al., 1977). Thus three molecules having identical chirality point upwards and three molecules of opposing chirality point downwards (Finocchearo & Failla, 1996).
Herein we report the crystal structure which reveals that the packing of the chirally pure compound (Fig 1) is very different from that of its racemate. The packing can be described as sheets of hydrogen–bonded molecules forming infinite chains, parallel to the b axis (Fig 2). Two adjacent chains are held together by edge-to-face π-π interactions forming double strands (C—H to centroid distance of 3.897 Å) (Fig 3). This packing is very similar to the close packed (S)-Dianin's structure (Lloyd & Bredenkamp, 2005).
For related literature, see: Brienne & Jacques (1975); Esterhuysen et al. (2005); Finocchearo & Failla (1996); Hardy et al. (1977); Jacobs et al. (2006); Lloyd & Bredenkamp (2005); Lloyd et al. (2005).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001; Atwood & Barbour, 2003); software used to prepare material for publication: X-SEED.
C18H20OS | F(000) = 608 |
Mr = 284.40 | Dx = 1.287 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3826 reflections |
a = 10.4001 (17) Å | θ = 2.5–28.0° |
b = 10.5186 (17) Å | µ = 0.21 mm−1 |
c = 13.415 (2) Å | T = 100 K |
V = 1467.5 (4) Å3 | Rectangular block, colourless |
Z = 4 | 0.34 × 0.22 × 0.09 mm |
Bruker APEX CCD area-detector diffractometer | 2993 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.085 |
Graphite monochromator | θmax = 27.1°, θmin = 2.5° |
ω scans | h = −13→12 |
9049 measured reflections | k = −13→11 |
3229 independent reflections | l = −15→17 |
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)] = 0.083 | H-atom parameters constrained |
wR(F2) = 0.202 | w = 1/[σ2(Fo2) + (0.1287P)2 + 1.5786P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max < 0.001 |
3229 reflections | Δρmax = 0.95 e Å−3 |
185 parameters | Δρmin = −0.82 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1373 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.08 (16) |
C18H20OS | V = 1467.5 (4) Å3 |
Mr = 284.40 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.4001 (17) Å | µ = 0.21 mm−1 |
b = 10.5186 (17) Å | T = 100 K |
c = 13.415 (2) Å | 0.34 × 0.22 × 0.09 mm |
Bruker APEX CCD area-detector diffractometer | 2993 reflections with I > 2σ(I) |
9049 measured reflections | Rint = 0.085 |
3229 independent reflections |
R[F2 > 2σ(F2)] = 0.083 | H-atom parameters constrained |
wR(F2) = 0.202 | Δρmax = 0.95 e Å−3 |
S = 1.13 | Δρmin = −0.82 e Å−3 |
3229 reflections | Absolute structure: Flack (1983), 1373 Friedel pairs |
185 parameters | Absolute structure parameter: 0.08 (16) |
0 restraints |
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 | ||
O1 | 0.2990 (2) | 0.3661 (2) | 0.40764 (19) | 0.0204 (6) | |
C2 | 0.3537 (3) | 0.4103 (4) | 0.5025 (2) | 0.0189 (7) | |
C3 | 0.3591 (3) | 0.5545 (3) | 0.5013 (2) | 0.0176 (7) | |
H3A | 0.4214 | 0.5810 | 0.4495 | 0.021* | |
H3B | 0.3931 | 0.5836 | 0.5663 | 0.021* | |
C4 | 0.2305 (3) | 0.6243 (3) | 0.4816 (2) | 0.0161 (7) | |
C5 | 0.1486 (3) | 0.5440 (3) | 0.4105 (3) | 0.0153 (7) | |
C6 | 0.0307 (3) | 0.5912 (4) | 0.3745 (3) | 0.0196 (7) | |
H6 | 0.0023 | 0.6726 | 0.3959 | 0.023* | |
C7 | −0.0447 (3) | 0.5230 (4) | 0.3091 (3) | 0.0224 (8) | |
H7 | −0.1244 | 0.5565 | 0.2867 | 0.027* | |
C8 | −0.0031 (3) | 0.4045 (4) | 0.2762 (3) | 0.0217 (7) | |
H8 | −0.0535 | 0.3576 | 0.2300 | 0.026* | |
C9 | 0.1109 (4) | 0.3555 (4) | 0.3105 (2) | 0.0201 (7) | |
H9 | 0.1387 | 0.2742 | 0.2883 | 0.024* | |
C10 | 0.1862 (3) | 0.4240 (3) | 0.3777 (3) | 0.0166 (7) | |
C11 | 0.2756 (4) | 0.3518 (4) | 0.5873 (3) | 0.0241 (8) | |
H11A | 0.1852 | 0.3769 | 0.5806 | 0.036* | |
H11B | 0.3090 | 0.3821 | 0.6513 | 0.036* | |
H11C | 0.2823 | 0.2590 | 0.5844 | 0.036* | |
C12 | 0.4894 (4) | 0.3556 (4) | 0.5036 (3) | 0.0266 (8) | |
H12A | 0.4851 | 0.2627 | 0.4994 | 0.040* | |
H12B | 0.5326 | 0.3802 | 0.5656 | 0.040* | |
H12C | 0.5378 | 0.3888 | 0.4466 | 0.040* | |
C13 | 0.1558 (4) | 0.6458 (4) | 0.5788 (3) | 0.0203 (7) | |
H13A | 0.0789 | 0.6968 | 0.5650 | 0.030* | |
H13B | 0.2106 | 0.6908 | 0.6266 | 0.030* | |
H13C | 0.1302 | 0.5636 | 0.6068 | 0.030* | |
C14 | 0.2636 (3) | 0.7516 (3) | 0.4314 (3) | 0.0159 (7) | |
C15 | 0.2511 (3) | 0.8686 (3) | 0.4769 (3) | 0.0193 (7) | |
H15 | 0.2137 | 0.8732 | 0.5414 | 0.023* | |
C16 | 0.2916 (4) | 0.9798 (4) | 0.4310 (3) | 0.0224 (8) | |
H16 | 0.2834 | 1.0591 | 0.4643 | 0.027* | |
C17 | 0.3444 (4) | 0.9742 (4) | 0.3354 (3) | 0.0234 (8) | |
C18 | 0.3545 (3) | 0.8584 (4) | 0.2882 (3) | 0.0230 (8) | |
H18 | 0.3893 | 0.8540 | 0.2228 | 0.028* | |
C19 | 0.3149 (3) | 0.7495 (4) | 0.3348 (3) | 0.0205 (7) | |
H19 | 0.3224 | 0.6706 | 0.3008 | 0.025* | |
S20 | 0.40742 (10) | 1.10569 (9) | 0.27025 (8) | 0.0319 (3) | |
H20 | 0.3792 | 1.2019 | 0.3131 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0182 (12) | 0.0245 (13) | 0.0185 (12) | 0.0082 (10) | −0.0025 (10) | −0.0046 (11) |
C2 | 0.0143 (15) | 0.0305 (19) | 0.0118 (15) | 0.0046 (14) | 0.0008 (12) | 0.0034 (14) |
C3 | 0.0148 (15) | 0.0269 (17) | 0.0111 (15) | −0.0027 (14) | −0.0027 (12) | 0.0023 (14) |
C4 | 0.0123 (14) | 0.0224 (17) | 0.0137 (15) | −0.0011 (12) | 0.0007 (12) | −0.0026 (13) |
C5 | 0.0106 (14) | 0.0225 (17) | 0.0128 (15) | −0.0009 (13) | 0.0024 (12) | 0.0014 (13) |
C6 | 0.0128 (15) | 0.0200 (17) | 0.0259 (18) | 0.0005 (14) | −0.0014 (13) | −0.0010 (15) |
C7 | 0.0117 (16) | 0.0288 (19) | 0.0267 (19) | −0.0021 (13) | −0.0040 (13) | 0.0023 (16) |
C8 | 0.0204 (17) | 0.0285 (18) | 0.0161 (16) | −0.0090 (14) | −0.0020 (13) | 0.0013 (16) |
C9 | 0.0247 (18) | 0.0228 (16) | 0.0127 (14) | −0.0004 (14) | 0.0017 (13) | −0.0038 (13) |
C10 | 0.0132 (15) | 0.0222 (17) | 0.0144 (15) | −0.0013 (12) | −0.0005 (12) | 0.0030 (13) |
C11 | 0.0245 (18) | 0.0270 (19) | 0.0207 (17) | −0.0022 (15) | 0.0034 (15) | 0.0056 (16) |
C12 | 0.0231 (19) | 0.036 (2) | 0.0204 (17) | 0.0066 (16) | −0.0012 (15) | 0.0038 (17) |
C13 | 0.0199 (17) | 0.0269 (18) | 0.0141 (16) | −0.0018 (14) | 0.0068 (13) | −0.0004 (14) |
C14 | 0.0107 (14) | 0.0230 (17) | 0.0141 (16) | −0.0015 (13) | −0.0024 (12) | 0.0001 (13) |
C15 | 0.0145 (16) | 0.0232 (17) | 0.0202 (17) | −0.0020 (13) | 0.0041 (13) | 0.0022 (14) |
C16 | 0.0165 (17) | 0.0230 (18) | 0.028 (2) | −0.0019 (13) | 0.0006 (14) | −0.0009 (15) |
C17 | 0.0111 (16) | 0.0297 (19) | 0.029 (2) | −0.0073 (14) | −0.0075 (14) | 0.0137 (16) |
C18 | 0.0147 (15) | 0.039 (2) | 0.0154 (16) | −0.0090 (15) | −0.0049 (13) | 0.0029 (15) |
C19 | 0.0164 (16) | 0.0294 (19) | 0.0158 (17) | 0.0014 (14) | −0.0032 (13) | −0.0010 (15) |
S20 | 0.0311 (6) | 0.0228 (5) | 0.0419 (6) | −0.0045 (4) | −0.0043 (5) | 0.0083 (4) |
O1—C10 | 1.381 (4) | C11—H11A | 0.9800 |
O1—C2 | 1.469 (4) | C11—H11B | 0.9800 |
C2—C3 | 1.518 (5) | C11—H11C | 0.9800 |
C2—C12 | 1.524 (5) | C12—H12A | 0.9800 |
C2—C11 | 1.528 (5) | C12—H12B | 0.9800 |
C3—C4 | 1.549 (5) | C12—H12C | 0.9800 |
C3—H3A | 0.9900 | C13—H13A | 0.9800 |
C3—H3B | 0.9900 | C13—H13B | 0.9800 |
C4—C13 | 1.533 (4) | C13—H13C | 0.9800 |
C4—C5 | 1.533 (4) | C14—C15 | 1.381 (5) |
C4—C14 | 1.538 (5) | C14—C19 | 1.402 (5) |
C5—C10 | 1.393 (5) | C15—C16 | 1.387 (5) |
C5—C6 | 1.409 (5) | C15—H15 | 0.9500 |
C6—C7 | 1.378 (5) | C16—C17 | 1.397 (6) |
C6—H6 | 0.9500 | C16—H16 | 0.9500 |
C7—C8 | 1.391 (6) | C17—C18 | 1.377 (6) |
C7—H7 | 0.9500 | C17—S20 | 1.762 (4) |
C8—C9 | 1.372 (5) | C18—C19 | 1.368 (5) |
C8—H8 | 0.9500 | C18—H18 | 0.9500 |
C9—C10 | 1.395 (5) | C19—H19 | 0.9500 |
C9—H9 | 0.9500 | S20—H20 | 1.2000 |
C10—O1—C2 | 116.2 (3) | C2—C11—H11A | 109.5 |
O1—C2—C3 | 108.7 (3) | C2—C11—H11B | 109.5 |
O1—C2—C12 | 104.4 (3) | H11A—C11—H11B | 109.5 |
C3—C2—C12 | 110.1 (3) | C2—C11—H11C | 109.5 |
O1—C2—C11 | 108.2 (3) | H11A—C11—H11C | 109.5 |
C3—C2—C11 | 115.4 (3) | H11B—C11—H11C | 109.5 |
C12—C2—C11 | 109.5 (3) | C2—C12—H12A | 109.5 |
C2—C3—C4 | 116.3 (3) | C2—C12—H12B | 109.5 |
C2—C3—H3A | 108.2 | H12A—C12—H12B | 109.5 |
C4—C3—H3A | 108.2 | C2—C12—H12C | 109.5 |
C2—C3—H3B | 108.2 | H12A—C12—H12C | 109.5 |
C4—C3—H3B | 108.2 | H12B—C12—H12C | 109.5 |
H3A—C3—H3B | 107.4 | C4—C13—H13A | 109.5 |
C13—C4—C5 | 109.2 (3) | C4—C13—H13B | 109.5 |
C13—C4—C14 | 111.0 (3) | H13A—C13—H13B | 109.5 |
C5—C4—C14 | 109.3 (3) | C4—C13—H13C | 109.5 |
C13—C4—C3 | 111.3 (3) | H13A—C13—H13C | 109.5 |
C5—C4—C3 | 108.9 (3) | H13B—C13—H13C | 109.5 |
C14—C4—C3 | 107.1 (3) | C15—C14—C19 | 117.3 (3) |
C10—C5—C6 | 117.1 (3) | C15—C14—C4 | 124.2 (3) |
C10—C5—C4 | 122.7 (3) | C19—C14—C4 | 118.5 (3) |
C6—C5—C4 | 120.2 (3) | C14—C15—C16 | 121.8 (3) |
C7—C6—C5 | 122.0 (3) | C14—C15—H15 | 119.1 |
C7—C6—H6 | 119.0 | C16—C15—H15 | 119.1 |
C5—C6—H6 | 119.0 | C15—C16—C17 | 119.5 (4) |
C6—C7—C8 | 119.4 (3) | C15—C16—H16 | 120.3 |
C6—C7—H7 | 120.3 | C17—C16—H16 | 120.3 |
C8—C7—H7 | 120.3 | C18—C17—C16 | 119.3 (3) |
C9—C8—C7 | 120.0 (3) | C18—C17—S20 | 116.0 (3) |
C9—C8—H8 | 120.0 | C16—C17—S20 | 124.7 (3) |
C7—C8—H8 | 120.0 | C19—C18—C17 | 120.5 (3) |
C8—C9—C10 | 120.5 (3) | C19—C18—H18 | 119.7 |
C8—C9—H9 | 119.7 | C17—C18—H18 | 119.7 |
C10—C9—H9 | 119.7 | C18—C19—C14 | 121.6 (4) |
O1—C10—C5 | 123.1 (3) | C18—C19—H19 | 119.2 |
O1—C10—C9 | 116.0 (3) | C14—C19—H19 | 119.2 |
C5—C10—C9 | 121.0 (3) | C17—S20—H20 | 109.5 |
C10—O1—C2—C3 | −49.3 (4) | C6—C5—C10—O1 | −179.6 (3) |
C10—O1—C2—C12 | −166.8 (3) | C4—C5—C10—O1 | 1.2 (5) |
C10—O1—C2—C11 | 76.7 (4) | C6—C5—C10—C9 | 1.2 (5) |
O1—C2—C3—C4 | 56.0 (4) | C4—C5—C10—C9 | −178.0 (3) |
C12—C2—C3—C4 | 169.8 (3) | C8—C9—C10—O1 | 180.0 (3) |
C11—C2—C3—C4 | −65.7 (4) | C8—C9—C10—C5 | −0.8 (5) |
C2—C3—C4—C13 | 87.2 (4) | C13—C4—C14—C15 | 12.1 (4) |
C2—C3—C4—C5 | −33.3 (4) | C5—C4—C14—C15 | 132.6 (3) |
C2—C3—C4—C14 | −151.4 (3) | C3—C4—C14—C15 | −109.5 (4) |
C13—C4—C5—C10 | −117.5 (4) | C13—C4—C14—C19 | −170.8 (3) |
C14—C4—C5—C10 | 120.9 (3) | C5—C4—C14—C19 | −50.2 (4) |
C3—C4—C5—C10 | 4.2 (4) | C3—C4—C14—C19 | 67.6 (4) |
C13—C4—C5—C6 | 63.3 (4) | C19—C14—C15—C16 | −2.2 (5) |
C14—C4—C5—C6 | −58.3 (4) | C4—C14—C15—C16 | 175.0 (3) |
C3—C4—C5—C6 | −175.0 (3) | C14—C15—C16—C17 | 1.1 (6) |
C10—C5—C6—C7 | −0.4 (5) | C15—C16—C17—C18 | 0.4 (5) |
C4—C5—C6—C7 | 178.9 (3) | C15—C16—C17—S20 | −176.6 (3) |
C5—C6—C7—C8 | −0.9 (6) | C16—C17—C18—C19 | −0.9 (5) |
C6—C7—C8—C9 | 1.4 (6) | S20—C17—C18—C19 | 176.4 (3) |
C7—C8—C9—C10 | −0.5 (5) | C17—C18—C19—C14 | −0.2 (5) |
C2—O1—C10—C5 | 22.9 (5) | C15—C14—C19—C18 | 1.8 (5) |
C2—O1—C10—C9 | −157.9 (3) | C4—C14—C19—C18 | −175.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
S20—H20···O1i | 1.20 | 2.30 | 3.488 (4) | 171 |
Symmetry code: (i) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C18H20OS |
Mr | 284.40 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 10.4001 (17), 10.5186 (17), 13.415 (2) |
V (Å3) | 1467.5 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.34 × 0.22 × 0.09 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9049, 3229, 2993 |
Rint | 0.085 |
(sin θ/λ)max (Å−1) | 0.641 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.083, 0.202, 1.13 |
No. of reflections | 3229 |
No. of parameters | 185 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.95, −0.82 |
Absolute structure | Flack (1983), 1373 Friedel pairs |
Absolute structure parameter | 0.08 (16) |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001; Atwood & Barbour, 2003), X-SEED.
D—H···A | D—H | H···A | D···A | D—H···A |
S20—H20···O1i | 1.20 | 2.30 | 3.488 (4) | 171.0 |
Symmetry code: (i) x, y+1, z. |
In conjunction with our investigation on the formation of clathrates (Esterhuysen et al., 2005; Lloyd & Bredenkamp, 2005; Lloyd et al., 2005) we have synthesized an enantiomerically pure form of 4-p-mercaptophenyl-2,2,4-trimethylchroman, (I), the thiol derivative of Dianin's compound.
It is well known that a racemic mixture of (I) packs in such a way that six thiol molecules are linked to each other by a network of S—H···S hydrogen bonds such that the S atoms form a near-planar hexagon (Hardy et al., 1977). Thus three molecules having identical chirality point upwards and three molecules of opposing chirality point downwards (Finocchearo & Failla, 1996).
Herein we report the crystal structure which reveals that the packing of the chirally pure compound (Fig 1) is very different from that of its racemate. The packing can be described as sheets of hydrogen–bonded molecules forming infinite chains, parallel to the b axis (Fig 2). Two adjacent chains are held together by edge-to-face π-π interactions forming double strands (C—H to centroid distance of 3.897 Å) (Fig 3). This packing is very similar to the close packed (S)-Dianin's structure (Lloyd & Bredenkamp, 2005).