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Crystallization of the title compound, C18H20OS, from cyclo­hexane gives the unsolvated crystal structure. Linear strands of mol­ecules are formed by S—H...O hydrogen bonds, with edge-to-face π–π inter­actions connecting neighboring strands.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038184/bt2464sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038184/bt2464Isup2.hkl
Contains datablock I

CCDC reference: 660231

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.083
  • wR factor = 0.202
  • Data-to-parameter ratio = 17.5

checkCIF/PLATON results

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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

Comment top

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).

Related literature top

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).

Experimental top

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.

Refinement top

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.

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. Infinite chains of hydrogen-bonded molecules extend along [010], with two neighboring chains forming edge-to-face π-π interactions to assemble a double strand. Each colour here represents one of these double strands.
[Figure 3] Fig. 3. The intermolecular hydrogen bonding and the π-π interactions are shown as red dashed lines.
(S)-4-(4-Mercaptophenyl)-2,2,4-trimethylchroman top
Crystal data top
C18H20OSF(000) = 608
Mr = 284.40Dx = 1.287 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3826 reflections
a = 10.4001 (17) Åθ = 2.5–28.0°
b = 10.5186 (17) ŵ = 0.21 mm1
c = 13.415 (2) ÅT = 100 K
V = 1467.5 (4) Å3Rectangular block, colourless
Z = 40.34 × 0.22 × 0.09 mm
Data collection top
Bruker APEX CCD area-detector
diffractometer
2993 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.085
Graphite monochromatorθmax = 27.1°, θmin = 2.5°
ω scansh = 1312
9049 measured reflectionsk = 1311
3229 independent reflectionsl = 1517
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)] = 0.083H-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 reflectionsΔρmax = 0.95 e Å3
185 parametersΔρmin = 0.82 e Å3
0 restraintsAbsolute structure: Flack (1983), 1373 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.08 (16)
Crystal data top
C18H20OSV = 1467.5 (4) Å3
Mr = 284.40Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 10.4001 (17) ŵ = 0.21 mm1
b = 10.5186 (17) ÅT = 100 K
c = 13.415 (2) Å0.34 × 0.22 × 0.09 mm
Data collection top
Bruker APEX CCD area-detector
diffractometer
2993 reflections with I > 2σ(I)
9049 measured reflectionsRint = 0.085
3229 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.083H-atom parameters constrained
wR(F2) = 0.202Δρmax = 0.95 e Å3
S = 1.13Δρmin = 0.82 e Å3
3229 reflectionsAbsolute structure: Flack (1983), 1373 Friedel pairs
185 parametersAbsolute structure parameter: 0.08 (16)
0 restraints
Special details top

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

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.2990 (2)0.3661 (2)0.40764 (19)0.0204 (6)
C20.3537 (3)0.4103 (4)0.5025 (2)0.0189 (7)
C30.3591 (3)0.5545 (3)0.5013 (2)0.0176 (7)
H3A0.42140.58100.44950.021*
H3B0.39310.58360.56630.021*
C40.2305 (3)0.6243 (3)0.4816 (2)0.0161 (7)
C50.1486 (3)0.5440 (3)0.4105 (3)0.0153 (7)
C60.0307 (3)0.5912 (4)0.3745 (3)0.0196 (7)
H60.00230.67260.39590.023*
C70.0447 (3)0.5230 (4)0.3091 (3)0.0224 (8)
H70.12440.55650.28670.027*
C80.0031 (3)0.4045 (4)0.2762 (3)0.0217 (7)
H80.05350.35760.23000.026*
C90.1109 (4)0.3555 (4)0.3105 (2)0.0201 (7)
H90.13870.27420.28830.024*
C100.1862 (3)0.4240 (3)0.3777 (3)0.0166 (7)
C110.2756 (4)0.3518 (4)0.5873 (3)0.0241 (8)
H11A0.18520.37690.58060.036*
H11B0.30900.38210.65130.036*
H11C0.28230.25900.58440.036*
C120.4894 (4)0.3556 (4)0.5036 (3)0.0266 (8)
H12A0.48510.26270.49940.040*
H12B0.53260.38020.56560.040*
H12C0.53780.38880.44660.040*
C130.1558 (4)0.6458 (4)0.5788 (3)0.0203 (7)
H13A0.07890.69680.56500.030*
H13B0.21060.69080.62660.030*
H13C0.13020.56360.60680.030*
C140.2636 (3)0.7516 (3)0.4314 (3)0.0159 (7)
C150.2511 (3)0.8686 (3)0.4769 (3)0.0193 (7)
H150.21370.87320.54140.023*
C160.2916 (4)0.9798 (4)0.4310 (3)0.0224 (8)
H160.28341.05910.46430.027*
C170.3444 (4)0.9742 (4)0.3354 (3)0.0234 (8)
C180.3545 (3)0.8584 (4)0.2882 (3)0.0230 (8)
H180.38930.85400.22280.028*
C190.3149 (3)0.7495 (4)0.3348 (3)0.0205 (7)
H190.32240.67060.30080.025*
S200.40742 (10)1.10569 (9)0.27025 (8)0.0319 (3)
H200.37921.20190.31310.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0182 (12)0.0245 (13)0.0185 (12)0.0082 (10)0.0025 (10)0.0046 (11)
C20.0143 (15)0.0305 (19)0.0118 (15)0.0046 (14)0.0008 (12)0.0034 (14)
C30.0148 (15)0.0269 (17)0.0111 (15)0.0027 (14)0.0027 (12)0.0023 (14)
C40.0123 (14)0.0224 (17)0.0137 (15)0.0011 (12)0.0007 (12)0.0026 (13)
C50.0106 (14)0.0225 (17)0.0128 (15)0.0009 (13)0.0024 (12)0.0014 (13)
C60.0128 (15)0.0200 (17)0.0259 (18)0.0005 (14)0.0014 (13)0.0010 (15)
C70.0117 (16)0.0288 (19)0.0267 (19)0.0021 (13)0.0040 (13)0.0023 (16)
C80.0204 (17)0.0285 (18)0.0161 (16)0.0090 (14)0.0020 (13)0.0013 (16)
C90.0247 (18)0.0228 (16)0.0127 (14)0.0004 (14)0.0017 (13)0.0038 (13)
C100.0132 (15)0.0222 (17)0.0144 (15)0.0013 (12)0.0005 (12)0.0030 (13)
C110.0245 (18)0.0270 (19)0.0207 (17)0.0022 (15)0.0034 (15)0.0056 (16)
C120.0231 (19)0.036 (2)0.0204 (17)0.0066 (16)0.0012 (15)0.0038 (17)
C130.0199 (17)0.0269 (18)0.0141 (16)0.0018 (14)0.0068 (13)0.0004 (14)
C140.0107 (14)0.0230 (17)0.0141 (16)0.0015 (13)0.0024 (12)0.0001 (13)
C150.0145 (16)0.0232 (17)0.0202 (17)0.0020 (13)0.0041 (13)0.0022 (14)
C160.0165 (17)0.0230 (18)0.028 (2)0.0019 (13)0.0006 (14)0.0009 (15)
C170.0111 (16)0.0297 (19)0.029 (2)0.0073 (14)0.0075 (14)0.0137 (16)
C180.0147 (15)0.039 (2)0.0154 (16)0.0090 (15)0.0049 (13)0.0029 (15)
C190.0164 (16)0.0294 (19)0.0158 (17)0.0014 (14)0.0032 (13)0.0010 (15)
S200.0311 (6)0.0228 (5)0.0419 (6)0.0045 (4)0.0043 (5)0.0083 (4)
Geometric parameters (Å, º) top
O1—C101.381 (4)C11—H11A0.9800
O1—C21.469 (4)C11—H11B0.9800
C2—C31.518 (5)C11—H11C0.9800
C2—C121.524 (5)C12—H12A0.9800
C2—C111.528 (5)C12—H12B0.9800
C3—C41.549 (5)C12—H12C0.9800
C3—H3A0.9900C13—H13A0.9800
C3—H3B0.9900C13—H13B0.9800
C4—C131.533 (4)C13—H13C0.9800
C4—C51.533 (4)C14—C151.381 (5)
C4—C141.538 (5)C14—C191.402 (5)
C5—C101.393 (5)C15—C161.387 (5)
C5—C61.409 (5)C15—H150.9500
C6—C71.378 (5)C16—C171.397 (6)
C6—H60.9500C16—H160.9500
C7—C81.391 (6)C17—C181.377 (6)
C7—H70.9500C17—S201.762 (4)
C8—C91.372 (5)C18—C191.368 (5)
C8—H80.9500C18—H180.9500
C9—C101.395 (5)C19—H190.9500
C9—H90.9500S20—H201.2000
C10—O1—C2116.2 (3)C2—C11—H11A109.5
O1—C2—C3108.7 (3)C2—C11—H11B109.5
O1—C2—C12104.4 (3)H11A—C11—H11B109.5
C3—C2—C12110.1 (3)C2—C11—H11C109.5
O1—C2—C11108.2 (3)H11A—C11—H11C109.5
C3—C2—C11115.4 (3)H11B—C11—H11C109.5
C12—C2—C11109.5 (3)C2—C12—H12A109.5
C2—C3—C4116.3 (3)C2—C12—H12B109.5
C2—C3—H3A108.2H12A—C12—H12B109.5
C4—C3—H3A108.2C2—C12—H12C109.5
C2—C3—H3B108.2H12A—C12—H12C109.5
C4—C3—H3B108.2H12B—C12—H12C109.5
H3A—C3—H3B107.4C4—C13—H13A109.5
C13—C4—C5109.2 (3)C4—C13—H13B109.5
C13—C4—C14111.0 (3)H13A—C13—H13B109.5
C5—C4—C14109.3 (3)C4—C13—H13C109.5
C13—C4—C3111.3 (3)H13A—C13—H13C109.5
C5—C4—C3108.9 (3)H13B—C13—H13C109.5
C14—C4—C3107.1 (3)C15—C14—C19117.3 (3)
C10—C5—C6117.1 (3)C15—C14—C4124.2 (3)
C10—C5—C4122.7 (3)C19—C14—C4118.5 (3)
C6—C5—C4120.2 (3)C14—C15—C16121.8 (3)
C7—C6—C5122.0 (3)C14—C15—H15119.1
C7—C6—H6119.0C16—C15—H15119.1
C5—C6—H6119.0C15—C16—C17119.5 (4)
C6—C7—C8119.4 (3)C15—C16—H16120.3
C6—C7—H7120.3C17—C16—H16120.3
C8—C7—H7120.3C18—C17—C16119.3 (3)
C9—C8—C7120.0 (3)C18—C17—S20116.0 (3)
C9—C8—H8120.0C16—C17—S20124.7 (3)
C7—C8—H8120.0C19—C18—C17120.5 (3)
C8—C9—C10120.5 (3)C19—C18—H18119.7
C8—C9—H9119.7C17—C18—H18119.7
C10—C9—H9119.7C18—C19—C14121.6 (4)
O1—C10—C5123.1 (3)C18—C19—H19119.2
O1—C10—C9116.0 (3)C14—C19—H19119.2
C5—C10—C9121.0 (3)C17—S20—H20109.5
C10—O1—C2—C349.3 (4)C6—C5—C10—O1179.6 (3)
C10—O1—C2—C12166.8 (3)C4—C5—C10—O11.2 (5)
C10—O1—C2—C1176.7 (4)C6—C5—C10—C91.2 (5)
O1—C2—C3—C456.0 (4)C4—C5—C10—C9178.0 (3)
C12—C2—C3—C4169.8 (3)C8—C9—C10—O1180.0 (3)
C11—C2—C3—C465.7 (4)C8—C9—C10—C50.8 (5)
C2—C3—C4—C1387.2 (4)C13—C4—C14—C1512.1 (4)
C2—C3—C4—C533.3 (4)C5—C4—C14—C15132.6 (3)
C2—C3—C4—C14151.4 (3)C3—C4—C14—C15109.5 (4)
C13—C4—C5—C10117.5 (4)C13—C4—C14—C19170.8 (3)
C14—C4—C5—C10120.9 (3)C5—C4—C14—C1950.2 (4)
C3—C4—C5—C104.2 (4)C3—C4—C14—C1967.6 (4)
C13—C4—C5—C663.3 (4)C19—C14—C15—C162.2 (5)
C14—C4—C5—C658.3 (4)C4—C14—C15—C16175.0 (3)
C3—C4—C5—C6175.0 (3)C14—C15—C16—C171.1 (6)
C10—C5—C6—C70.4 (5)C15—C16—C17—C180.4 (5)
C4—C5—C6—C7178.9 (3)C15—C16—C17—S20176.6 (3)
C5—C6—C7—C80.9 (6)C16—C17—C18—C190.9 (5)
C6—C7—C8—C91.4 (6)S20—C17—C18—C19176.4 (3)
C7—C8—C9—C100.5 (5)C17—C18—C19—C140.2 (5)
C2—O1—C10—C522.9 (5)C15—C14—C19—C181.8 (5)
C2—O1—C10—C9157.9 (3)C4—C14—C19—C18175.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
S20—H20···O1i1.202.303.488 (4)171
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC18H20OS
Mr284.40
Crystal system, space groupOrthorhombic, P212121
Temperature (K)100
a, b, c (Å)10.4001 (17), 10.5186 (17), 13.415 (2)
V3)1467.5 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.21
Crystal size (mm)0.34 × 0.22 × 0.09
Data collection
DiffractometerBruker APEX CCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
9049, 3229, 2993
Rint0.085
(sin θ/λ)max1)0.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.083, 0.202, 1.13
No. of reflections3229
No. of parameters185
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.95, 0.82
Absolute structureFlack (1983), 1373 Friedel pairs
Absolute structure parameter0.08 (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.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
S20—H20···O1i1.202.303.488 (4)171.0
Symmetry code: (i) x, y+1, z.
 

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