Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010601866X/ga3008sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010601866X/ga3008Isup2.hkl |
CCDC reference: 616275
Compound (Ib) was prepared from dimedone and sulfur chloride according to the procedure of Gompper or Gommper et al. (1964), and isolated through a silica gel column. Suitable crystals were obtained by evaporation of a benzene–methanol solution (m.p. 504–507 K).
All H atoms were located in a difference Fourier synthesis. C-bound H atoms were refined with restrained isotropic displacement parameters [Uiso(H) = 1.5Ueq(Cmethyl) or 1.2Ueq(Cmethylene)] using a riding model, with C—H distances of 0.96 (methyl) or 0.97 Å (methylene). The hydroxy H atom was refined isotropically with a fixed displacement parameter [Uiso(H) = 1.5Ueq(O)].
Data collection: MSC/AFC Diffractometer Control Software (Rigaku/MSC & Rigaku, 2001); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: CrystalStructure (Rigaku/MSC & Rigaku, 2001); program(s) used to solve structure: SIR97 (Altomare et al., 1999); 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.
C16H22O4S | Dx = 1.280 Mg m−3 |
Mr = 310.41 | Melting point = 504–507 K |
Tetragonal, P42bc | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P 4c -2ab | Cell parameters from 25 reflections |
a = 13.3426 (14) Å | θ = 13.6–14.9° |
c = 9.049 (2) Å | µ = 0.21 mm−1 |
V = 1610.9 (4) Å3 | T = 298 K |
Z = 4 | Rectangular, colorless |
F(000) = 664 | 1.00 × 0.40 × 0.20 mm |
Rigaku AFC-7S diffractometer | 1004 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 30.0°, θmin = 3.1° |
ω–2θ scans | h = 0→18 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = 0→13 |
Tmin = 0.815, Tmax = 0.959 | l = 0→12 |
1251 measured reflections | 3 standard reflections every 150 reflections |
1251 independent reflections | intensity decay: 0.4% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.034 | w = 1/[σ2(Fo2) + (0.0547P)2 + 0.1022P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.097 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.29 e Å−3 |
1251 reflections | Δρmin = −0.19 e Å−3 |
102 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.014 (2) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), ? Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.02 (17) |
C16H22O4S | Z = 4 |
Mr = 310.41 | Mo Kα radiation |
Tetragonal, P42bc | µ = 0.21 mm−1 |
a = 13.3426 (14) Å | T = 298 K |
c = 9.049 (2) Å | 1.00 × 0.40 × 0.20 mm |
V = 1610.9 (4) Å3 |
Rigaku AFC-7S diffractometer | 1004 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Rint = 0.000 |
Tmin = 0.815, Tmax = 0.959 | 3 standard reflections every 150 reflections |
1251 measured reflections | intensity decay: 0.4% |
1251 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | Δρmax = 0.29 e Å−3 |
S = 1.07 | Δρmin = −0.19 e Å−3 |
1251 reflections | Absolute structure: Flack (1983), ? Friedel pairs |
102 parameters | Absolute structure parameter: −0.02 (17) |
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 | 0.5000 | 0.0000 | 0.49915 (15) | 0.04238 (18) | |
O1 | 0.64894 (12) | −0.13934 (11) | 0.3584 (3) | 0.0615 (6) | |
O2 | 0.54750 (12) | 0.19631 (11) | 0.3452 (3) | 0.0527 (5) | |
C1 | 0.66713 (15) | −0.04862 (14) | 0.3349 (3) | 0.0427 (5) | |
C2 | 0.60061 (14) | 0.02907 (13) | 0.3803 (2) | 0.0349 (4) | |
C3 | 0.61346 (15) | 0.12553 (14) | 0.3283 (2) | 0.0380 (4) | |
C4 | 0.70493 (14) | 0.15521 (14) | 0.2436 (3) | 0.0421 (4) | |
C5 | 0.79513 (15) | 0.08584 (15) | 0.2671 (3) | 0.0417 (5) | |
C6 | 0.75876 (16) | −0.02253 (15) | 0.2466 (4) | 0.0474 (5) | |
C7 | 0.83915 (19) | 0.10036 (19) | 0.4220 (3) | 0.0543 (6) | |
C8 | 0.8748 (2) | 0.1106 (2) | 0.1517 (4) | 0.0638 (8) | |
H1 | 0.498 (3) | 0.181 (3) | 0.366 (5) | 0.079* | |
H2 | 0.7237 | 0.2227 | 0.2721 | 0.051* | |
H3 | 0.6886 | 0.1564 | 0.1391 | 0.051* | |
H4 | 0.7444 | −0.0334 | 0.1427 | 0.057* | |
H5 | 0.8125 | −0.0677 | 0.2743 | 0.057* | |
H6 | 0.8974 | 0.0587 | 0.4332 | 0.081* | |
H7 | 0.7900 | 0.0821 | 0.4948 | 0.081* | |
H8 | 0.8576 | 0.1693 | 0.4352 | 0.081* | |
H9 | 0.9313 | 0.0669 | 0.1644 | 0.096* | |
H10 | 0.8959 | 0.1789 | 0.1635 | 0.096* | |
H11 | 0.8473 | 0.1015 | 0.0545 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0457 (4) | 0.0454 (4) | 0.0361 (3) | −0.0045 (3) | 0.000 | 0.000 |
O1 | 0.0492 (8) | 0.0294 (6) | 0.1059 (16) | 0.0036 (6) | 0.0056 (11) | 0.0058 (10) |
O2 | 0.0438 (8) | 0.0309 (7) | 0.0835 (13) | 0.0040 (5) | −0.0009 (9) | −0.0017 (9) |
C1 | 0.0393 (9) | 0.0331 (8) | 0.0558 (12) | −0.0012 (8) | −0.0052 (10) | −0.0020 (9) |
C2 | 0.0348 (9) | 0.0303 (8) | 0.0397 (9) | −0.0010 (7) | −0.0036 (8) | −0.0011 (7) |
C3 | 0.0386 (9) | 0.0339 (9) | 0.0415 (10) | −0.0010 (6) | −0.0070 (9) | −0.0022 (8) |
C4 | 0.0416 (9) | 0.0365 (9) | 0.0483 (10) | −0.0025 (7) | −0.0027 (11) | 0.0050 (11) |
C5 | 0.0369 (9) | 0.0371 (9) | 0.0513 (12) | −0.0025 (7) | −0.0001 (10) | 0.0010 (10) |
C6 | 0.0405 (10) | 0.0390 (9) | 0.0629 (12) | 0.0005 (7) | 0.0036 (13) | −0.0086 (12) |
C7 | 0.0473 (13) | 0.0500 (12) | 0.0655 (16) | −0.0053 (10) | −0.0179 (12) | 0.0061 (12) |
C8 | 0.0474 (13) | 0.0707 (17) | 0.073 (2) | −0.0040 (12) | 0.0131 (13) | 0.0069 (15) |
S1—C2 | 1.763 (2) | C5—C8 | 1.526 (4) |
S1—C2i | 1.763 (2) | C5—C7 | 1.532 (4) |
O1—C1 | 1.253 (2) | C5—C6 | 1.537 (3) |
O2—C3 | 1.300 (2) | C6—H4 | 0.9700 |
O2—H1 | 0.72 (4) | C6—H5 | 0.9700 |
C1—C2 | 1.425 (3) | C7—H6 | 0.9600 |
C1—C6 | 1.502 (3) | C7—H7 | 0.9600 |
C2—C3 | 1.381 (3) | C7—H8 | 0.9600 |
C3—C4 | 1.495 (3) | C8—H9 | 0.9600 |
C4—C5 | 1.533 (3) | C8—H10 | 0.9600 |
C4—H2 | 0.9700 | C8—H11 | 0.9600 |
C4—H3 | 0.9700 | ||
C2—S1—C2i | 104.82 (15) | C7—C5—C6 | 110.5 (2) |
C3—O2—H1 | 116 (3) | C4—C5—C6 | 107.66 (16) |
O1—C1—C2 | 122.2 (2) | C1—C6—C5 | 114.27 (19) |
O1—C1—C6 | 118.2 (2) | C1—C6—H4 | 108.7 |
C2—C1—C6 | 119.46 (17) | C5—C6—H4 | 108.7 |
C3—C2—C1 | 120.16 (19) | C1—C6—H5 | 108.7 |
C3—C2—S1 | 120.48 (15) | C5—C6—H5 | 108.7 |
C1—C2—S1 | 119.33 (14) | H4—C6—H5 | 107.6 |
O2—C3—C2 | 123.6 (2) | C5—C7—H6 | 109.5 |
O2—C3—C4 | 114.88 (18) | C5—C7—H7 | 109.5 |
C2—C3—C4 | 121.53 (18) | H6—C7—H7 | 109.5 |
C3—C4—C5 | 114.21 (18) | C5—C7—H8 | 109.5 |
C3—C4—H2 | 108.7 | H6—C7—H8 | 109.5 |
C5—C4—H2 | 108.7 | H7—C7—H8 | 109.5 |
C3—C4—H3 | 108.7 | C5—C8—H9 | 109.5 |
C5—C4—H3 | 108.7 | C5—C8—H10 | 109.5 |
H2—C4—H3 | 107.6 | H9—C8—H10 | 109.5 |
C8—C5—C7 | 109.4 (2) | C5—C8—H11 | 109.5 |
C8—C5—C4 | 108.8 (2) | H9—C8—H11 | 109.5 |
C7—C5—C4 | 110.6 (2) | H10—C8—H11 | 109.5 |
C8—C5—C6 | 109.9 (2) | ||
O1—C1—C2—C3 | −167.6 (3) | O2—C3—C4—C5 | 160.8 (2) |
C6—C1—C2—C3 | 8.0 (3) | C2—C3—C4—C5 | −20.8 (3) |
O1—C1—C2—S1 | 10.6 (3) | C3—C4—C5—C8 | 168.1 (2) |
C6—C1—C2—S1 | −173.8 (2) | C3—C4—C5—C7 | −71.8 (2) |
C2i—S1—C2—C3 | 87.38 (17) | C3—C4—C5—C6 | 49.0 (3) |
C2i—S1—C2—C1 | −90.89 (17) | O1—C1—C6—C5 | −160.2 (2) |
C1—C2—C3—O2 | 168.6 (2) | C2—C1—C6—C5 | 24.1 (4) |
S1—C2—C3—O2 | −9.7 (3) | C8—C5—C6—C1 | −169.0 (2) |
C1—C2—C3—C4 | −9.7 (3) | C7—C5—C6—C1 | 70.2 (3) |
S1—C2—C3—C4 | 172.02 (17) | C4—C5—C6—C1 | −50.7 (3) |
Symmetry code: (i) −x+1, −y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O1i | 0.72 (4) | 2.04 (4) | 2.732 (2) | 163 (5) |
C4—H2···O1ii | 0.97 | 2.62 | 3.521 (3) | 154 |
C7—H8···O1ii | 0.96 | 2.65 | 3.524 (3) | 152 |
Symmetry codes: (i) −x+1, −y, z; (ii) −x+3/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C16H22O4S |
Mr | 310.41 |
Crystal system, space group | Tetragonal, P42bc |
Temperature (K) | 298 |
a, c (Å) | 13.3426 (14), 9.049 (2) |
V (Å3) | 1610.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 1.00 × 0.40 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC-7S diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.815, 0.959 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1251, 1251, 1004 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.097, 1.07 |
No. of reflections | 1251 |
No. of parameters | 102 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.19 |
Absolute structure | Flack (1983), ? Friedel pairs |
Absolute structure parameter | −0.02 (17) |
Computer programs: MSC/AFC Diffractometer Control Software (Rigaku/MSC & Rigaku, 2001), MSC/AFC Diffractometer Control Software, CrystalStructure (Rigaku/MSC & Rigaku, 2001), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
S1—C2 | 1.763 (2) | C1—C2 | 1.425 (3) |
O1—C1 | 1.253 (2) | C2—C3 | 1.381 (3) |
O2—C3 | 1.300 (2) | ||
O1—C1—C2—C3 | −167.6 (3) | C1—C2—C3—O2 | 168.6 (2) |
O1—C1—C2—S1 | 10.6 (3) | S1—C2—C3—O2 | −9.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O1i | 0.72 (4) | 2.04 (4) | 2.732 (2) | 163 (5) |
C4—H2···O1ii | 0.97 | 2.62 | 3.521 (3) | 153.9 |
C7—H8···O1ii | 0.96 | 2.65 | 3.524 (3) | 152.0 |
Symmetry codes: (i) −x+1, −y, z; (ii) −x+3/2, y+1/2, z. |
When two dimedone (5,5-dimethylcylohexane-1,3-dione) molecules are bridged at their 2-positions with X (where X = Se, S or CH2), they are bound with strong intramolecular O—H···O hydrogen bonds in enol forms, (Ia-)-(Ic). It is of interest to determine how their molecular structures and hydrogen bonds depend on the bridge X atoms.
The crystal structures of (Ia) (Kivekäs & Laitalainen, 1983) and (Ic) (Low et al., 2003; Bolte & Scholtyssik, 1997) are reported to be similar to each other, even though the space group for (Ia) is P42bc with Z = 4 and that for (Ic) is Pccn with Z = 8. The space group of the title compound, (Ib), is found to be P42bc with slightly smaller lattice constants a and c than those for (Ia). Although crystal structures of seven derivatives of structure (Ic) substituted at the methylene bridge with p-substituted phenyl groups have been determined by Bolte et al. (1997, 2001), their molecular structures are not further mentioned here to ensure focus on the structural differences due to unsubstituted bridge X atoms. The mean values for the structure and ring puckering parameters (Cremer & Pople, 1975; Taylor, 1980) of (Ic) are used here unless otherwise specified, since the structures of the two independent molecules in the crystal of (Ic) are similar to each other.
The C—X bond length decreases from 1.916 (10) Å for (Ia), to 1.763 (2) Å for (Ib), to 1.515 (1) Å for (Ic), while the C—X—C bond angle increases from 100.9 (4)° for (Ia), to 104.8 (2)° for (Ib) to 116.1 (1)° for (Ic). The C—X bond lengths are approximately correlated with the covalent radii of X [1.22, 1.02 and 0.68 Å for X = Se, S and CH2, respectively] (Cambridge Crystallographic Data Center, 2006). The intramolecular O···O hydrogen-bond distance of 2.732 (3) Å for (Ib) (Table 2) is also between the corresponding distances of 2.857 (12) Å for (Ia) and 2.641 (1) Å for (Ic).
The ring-puckering parameters of θ = 61.6 (3)° and ϕ2 = −2.4 (4)° for the C2—C1—C6—C5—C4—C3 sequence of the cyclohexen-1-one ring in (Ib) are indicative of conformations somewhere between half-boat and envelope for the cyclohexen-1-one ring as observed for (Ia) [θ = 60.9(1.7)° and ϕ2= −3.6(1.9)°] and (Ic) [θ = 59.0 (3)° and ϕ2= 178.5 (4)°; θ = 119.8 (3)° and ϕ2= 0.9 (6)°]. It is interesting that the total puckering amplitude Q decreases slightly but significantly from (Ia) to (Ic) [Q = 0.490 (15), 0.476 (2) and 0.458 (2) Å for (Ia)–(Ic), respectively. The average distance of O1 and O2 from the mean plane of the cyclohexen-1-one ring also decreases from 0.121 Å for (Ia), to 0.099 Å for (Ib) to 0.046 Å for (Ic). The observed dependence of Q on the bridge X atoms could therefore be ascribed to the intramolecular O—H···O hydrogen bonds, which bring about deformation of the cyclohexen-1-one ring by shrinking of the O1···O2' (and O2···O1') distances. The bond distances along the O1—C1—C2—C3—O2 sequence in (Ib) suggest some π conjugation as reported for (Ia) and (Ic), although the degrees of the bond alternation in (Ia)–(Ic) do not seem to be systematic.
In the crystals of (Ia)–(Ic), mirror-image molecules are stacked along the individual C2 axes passing through the bridge atoms, forming column structures. The C—X—C planes of the upper and lower molecules in these columns relate by ca 60° as displayed in Fig. 2 for (Ib). There are very weak intermolecular C—H···O hydrogen bonds (Desiraju & Steiner, 1999) between columns in the crystal of (Ib) (Fig. 2 and Table 2), forming layers of molecules normal to c. Similar weak intermolecular hydrogen bonds could also be identified in the crystals of (Ia) and (Ic), although Low et al. (2003) doubted their structural significance.