supplementary materials
2,2'-Dimethyl-4,4'-(sulfonyldi-p-phenylene)dibut-3-yn-2-ol dihydrate
The asymmetric unit of the title compound, C22H22O4S·2H2O, contains one quarter of the organic molecule and one half water molecule, the site symmetries of the S atom and the water O atom being mm2 and m, respectively. The dihedral angle between the benzene rings is 76.27 (11)°. In the crystal structure, intermolecular O-H
O hydrogen bonds link the molecules into chains running parallel to the a axis.
1,1'-Sulfonylbis(4-iodobenzene) (10.00 g, 21.28 mmol), triethylamine (100 ml),
PdCl2(PPh3)2 (0.02 g, 0.03 mmol), PPh3 (0.04 g, 0.15 mmol),
2-methylbut-3-yn-2-ol (4.29 g, 51.10 mmol) and CuI (0.04 g, 0.21 mmol) were
added to a 250 ml three-ecked flask, and the mixture heated to reflux for 10 h. After completion of the reaction, the mixture was filtered and the filtrate
was evaporated under reduced pressure.
Single crystals suitable for X-ray analysis were obtained by slow evaporation
of an ethanol/ water solution (10:1 v/v) (6.90 g, 85% yield; m.p. 435–437 K).
The hydroxy H atom was located in a difference Fourier map and refined
isotropically with the O—H distance restrained to 0.82Å. The water
H atom was located in a difference Fourier map and refined as riding.
All other H atoms were positioned geometrically and refined using a
riding model, with C—H = 0.93–0.96 Å and Uiso(H) =
1.2Ueq(C) or 1.5Ueq (C) for methyl H atoms.
Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
2,2'-Dimethyl-4,4'-(sulfonyldi-
p-phenylene)dibut-3-yn-2-ol dihydrate
top
Crystal data top
| C22H22O4S·2H2O | F(000) = 444 |
| Mr = 418.50 | Dx = 1.267 Mg m−3 |
| Orthorhombic, Amm2 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: A 2 -2 | Cell parameters from 19 reflections |
| a = 19.751 (3) Å | θ = 4.9–7.6° |
| b = 10.904 (3) Å | µ = 0.18 mm−1 |
| c = 5.092 (2) Å | T = 292 K |
| V = 1096.5 (7) Å3 | Block, colourless |
| Z = 2 | 0.46 × 0.20 × 0.16 mm |
Data collection top
Enraf–Nonius CAD-4
diffractometer | 756 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.014 |
| graphite | θmax = 25.5°, θmin = 1.0° |
| ω/2θ scans | h = −23→23 |
Absorption correction: for a sphere
(WinGX; Farrugia, 1999) | k = −13→13 |
| Tmin = 0.921, Tmax = 0.972 | l = −6→3 |
| 1211 measured reflections | 3 standard reflections every 50 reflections |
| 888 independent reflections | intensity decay: 1.2% |
Refinement top
| Refinement on F2 | Hydrogen site location: mixed |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.053 | w = 1/[σ2(Fo2) + (0.0747P)2 + 1.0802P]
where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.142 | (Δ/σ)max < 0.001 |
| S = 1.09 | Δρmax = 0.52 e Å−3 |
| 888 reflections | Δρmin = −0.40 e Å−3 |
| 81 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 3 restraints | Extinction coefficient: 0.011 (3) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983); 284 Friedel pairs |
| Secondary atom site location: difference Fourier map | Flack parameter: −0.1 (2) |
Crystal data top
| C22H22O4S·2H2O | V = 1096.5 (7) Å3 |
| Mr = 418.50 | Z = 2 |
| Orthorhombic, Amm2 | Mo Kα radiation |
| a = 19.751 (3) Å | µ = 0.18 mm−1 |
| b = 10.904 (3) Å | T = 292 K |
| c = 5.092 (2) Å | 0.46 × 0.20 × 0.16 mm |
Data collection top
Enraf–Nonius CAD-4
diffractometer | 756 reflections with I > 2σ(I) |
Absorption correction: for a sphere
(WinGX; Farrugia, 1999) | Rint = 0.014 |
| Tmin = 0.921, Tmax = 0.972 | θmax = 25.5° |
| 1211 measured reflections | 3 standard reflections every 50 reflections |
| 888 independent reflections | intensity decay: 1.2% |
Refinement top
| R[F2 > 2σ(F2)] = 0.053 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.142 | Δρmax = 0.52 e Å−3 |
| S = 1.09 | Δρmin = −0.40 e Å−3 |
| 888 reflections | Absolute structure: Flack (1983); 284 Friedel pairs |
| 81 parameters | Flack parameter: −0.1 (2) |
| 3 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| | x | y | z | Uiso*/Ueq | |
| S1 | 0.5000 | 0.5000 | 0.5447 (4) | 0.0400 (6) | |
| O1 | 0.5000 | 0.6154 (4) | 0.6856 (9) | 0.0545 (12) | |
| O2 | 0.0928 (2) | 0.5000 | −0.3050 (9) | 0.0541 (12) | |
| H2O | 0.0592 (5) | 0.5000 | −0.398 (4) | 0.065 (8)* | |
| C1 | 0.4296 (2) | 0.5000 | 0.3319 (11) | 0.0372 (13) | |
| C2 | 0.40288 (19) | 0.3902 (3) | 0.2490 (10) | 0.0452 (10) | |
| H2 | 0.4218 | 0.3167 | 0.3052 | 0.054* | |
| C3 | 0.34760 (18) | 0.3895 (4) | 0.0814 (10) | 0.0501 (11) | |
| H3 | 0.3290 | 0.3156 | 0.0255 | 0.060* | |
| C4 | 0.3202 (2) | 0.5000 | −0.0022 (12) | 0.0426 (15) | |
| C5 | 0.2615 (3) | 0.5000 | −0.1766 (12) | 0.0445 (14) | |
| C6 | 0.2125 (2) | 0.5000 | −0.3109 (12) | 0.0401 (13) | |
| C7 | 0.1511 (2) | 0.5000 | −0.4712 (13) | 0.0371 (12) | |
| C8 | 0.1503 (2) | 0.3873 (3) | −0.6405 (8) | 0.0519 (11) | |
| H8A | 0.1344 | 0.3188 | −0.5396 | 0.078* | |
| H8B | 0.1953 | 0.3708 | −0.7024 | 0.078* | |
| H8C | 0.1208 | 0.4003 | −0.7877 | 0.078* | |
| O3W | 0.0000 (3) | 0.3082 (3) | −0.2418 (8) | 0.0559 (12)* | |
| H1W | −0.0332 | 0.3467 | −0.2448 | 0.078 (16)* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| S1 | 0.0347 (9) | 0.0578 (12) | 0.0276 (11) | 0.000 | 0.000 | 0.000 |
| O1 | 0.053 (2) | 0.071 (3) | 0.040 (3) | 0.000 | 0.000 | −0.022 (2) |
| O2 | 0.0384 (18) | 0.080 (3) | 0.044 (3) | 0.000 | 0.001 (2) | 0.000 |
| C1 | 0.030 (2) | 0.052 (3) | 0.030 (3) | 0.000 | −0.002 (2) | 0.000 |
| C2 | 0.0437 (18) | 0.044 (2) | 0.048 (3) | 0.0055 (17) | −0.0050 (19) | 0.003 (2) |
| C3 | 0.0418 (19) | 0.055 (2) | 0.053 (3) | −0.0022 (16) | −0.010 (2) | −0.010 (2) |
| C4 | 0.029 (2) | 0.064 (3) | 0.035 (4) | 0.000 | 0.004 (2) | 0.000 |
| C5 | 0.040 (3) | 0.063 (3) | 0.031 (3) | 0.000 | 0.003 (3) | 0.000 |
| C6 | 0.034 (3) | 0.050 (3) | 0.037 (3) | 0.000 | 0.004 (3) | 0.000 |
| C7 | 0.037 (2) | 0.045 (3) | 0.029 (3) | 0.000 | −0.002 (3) | 0.000 |
| C8 | 0.066 (2) | 0.049 (2) | 0.041 (3) | −0.0030 (19) | −0.002 (2) | 0.000 (2) |
Geometric parameters (Å, °) top
| S1—O1 | 1.448 (4) | C3—H3 | 0.9300 |
| S1—O1i | 1.448 (4) | C4—C3ii | 1.388 (5) |
| S1—C1 | 1.763 (5) | C4—C5 | 1.461 (7) |
| S1—C1i | 1.763 (5) | C5—C6 | 1.185 (7) |
| O2—C7 | 1.428 (7) | C6—C7 | 1.462 (7) |
| O2—H2O | 0.817 (10) | C7—C8 | 1.501 (5) |
| C1—C2ii | 1.375 (5) | C7—C8ii | 1.501 (5) |
| C1—C2 | 1.375 (5) | C8—H8A | 0.9600 |
| C2—C3 | 1.386 (5) | C8—H8B | 0.9600 |
| C2—H2 | 0.9300 | C8—H8C | 0.9600 |
| C3—C4 | 1.388 (5) | O3W—H1W | 0.7779 |
| | | |
| O1—S1—O1i | 120.6 (4) | C3ii—C4—C5 | 119.7 (3) |
| O1—S1—C1 | 107.72 (13) | C3—C4—C5 | 119.7 (3) |
| O1i—S1—C1 | 107.72 (13) | C6—C5—C4 | 177.8 (6) |
| O1—S1—C1i | 107.72 (13) | C5—C6—C7 | 178.7 (6) |
| O1i—S1—C1i | 107.72 (13) | O2—C7—C6 | 109.7 (5) |
| C1—S1—C1i | 104.1 (4) | O2—C7—C8 | 109.4 (3) |
| C7—O2—H2O | 108.2 (13) | C6—C7—C8 | 109.2 (3) |
| C2ii—C1—C2 | 121.1 (5) | O2—C7—C8ii | 109.4 (3) |
| C2ii—C1—S1 | 119.4 (3) | C6—C7—C8ii | 109.2 (3) |
| C2—C1—S1 | 119.4 (3) | C8—C7—C8ii | 109.9 (5) |
| C1—C2—C3 | 119.8 (4) | C7—C8—H8A | 109.5 |
| C1—C2—H2 | 120.1 | C7—C8—H8B | 109.5 |
| C3—C2—H2 | 120.1 | H8A—C8—H8B | 109.5 |
| C2—C3—C4 | 119.4 (4) | C7—C8—H8C | 109.5 |
| C2—C3—H3 | 120.3 | H8A—C8—H8C | 109.5 |
| C4—C3—H3 | 120.3 | H8B—C8—H8C | 109.5 |
| C3ii—C4—C3 | 120.5 (5) | | |
| | | |
| O1—S1—C1—C2ii | 24.6 (5) | C2—C3—C4—C3ii | −0.2 (9) |
| O1i—S1—C1—C2ii | 156.2 (4) | C2—C3—C4—C5 | −179.3 (5) |
| C1i—S1—C1—C2ii | −89.6 (4) | C3ii—C4—C5—C6 | −89.5 (5) |
| O1—S1—C1—C2 | −156.2 (4) | C3—C4—C5—C6 | 89.5 (5) |
| O1i—S1—C1—C2 | −24.6 (5) | C4—C5—C6—C7 | 0.00 (3) |
| C1i—S1—C1—C2 | 89.6 (4) | C5—C6—C7—O2 | 0.00 (2) |
| C2ii—C1—C2—C3 | −0.7 (8) | C5—C6—C7—C8 | −119.9 (3) |
| S1—C1—C2—C3 | −179.9 (4) | C5—C6—C7—C8ii | 119.9 (3) |
| C1—C2—C3—C4 | 0.5 (7) | | |
| Symmetry codes: (i) −x+1, −y+1, z; (ii) x, −y+1, z. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3W—H1W···O2iii | 0.78 | 2.07 | 2.800 (6) | 157 |
| Symmetry codes: (iii) −x, −y+1, z. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3W—H1W···O2i | 0.78 | 2.07 | 2.800 (6) | 157 |
| Symmetry codes: (i) −x, −y+1, z. |
The authors are grateful to the Undergraduates' Innovative Experiment Project of
Sichuan University and the Experimental Technical Project of Sichuan
University (07–54) for financial support, and thank Mr Zhi-Hua Mao of Sichuan
University for the X-ray data collection.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387.
Gabe, E. J. & White, P. S. (1993). DIFRAC. Am. Crystallogr. Assoc. Pittsburgh Meet. Abstract PA104.
Hanson, H. T. & Millburn, N. J. (1984). US Patent 4 439 590.
Lu, S. Y. & Hamerton, I. (2002). Pro. Polym. Sci. 27, 1661–1712.
Poon, S. Y., Wong, W. Y., Cheah, K. W. & Shi, J. X. (2006). Chem. Eur. J. 12, 2550–2563.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./rz2282fig1thm.gif)
Acetylene-terminated resins are commercially employed in composite materials, in particular where high strength, light weight materials capable of withstanding high temperatures are required (Lu & Hamerton, 2002). The title compound is an important intermediate for the preparation of these acetylene-terminated compounds (Hanson & Millburn, 1984) and a series of luminescent and thermally stable materials (Poon et al., 2006). We report here the synthesis and crystal structure of the title compound (Fig. 1).
The asymmetric unit of the title compound contains one fourth of the organic molecule and one half water molecule, the site symmetries of the S1 sulphur atom and the O3W water oxygen atom being mm2 and m, respectively. The dihedral angles between the benzene rings is 103.73 (11)°. The displacement of the C7 atom of the 2-hydroxy-2-methyl-4-but-3-ynyl substituent from the plane of the aromatic ring is -0.1870 (14) Å. In the crystal structure, the water molecules and the hydroxy groups are involved in the formation of intermolecular O—H···O hydrogen bonds (Table 1) forming chains running parallel to the a axis.