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2,2′-Di­methyl-4,4′-(sulfonyldi-p-phenyl­ene)dibut-3-yn-2-ol dihydrate

aCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China
*Correspondence e-mail: gaosunday@yahoo.com.cn

(Received 13 December 2008; accepted 21 December 2008; online 8 January 2009)

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.

Related literature

For the properties and synthesis of thermosetting acetyl­ene-terminated resins, see: Lu & Hamerton (2002[Lu, S. Y. & Hamerton, I. (2002). Prog. Polym. Sci. 27, 1661-1712.]). For the applications of the title compound, see: Hanson & Millburn (1984[Hanson, H. T. & Millburn, N. J. (1984). US Patent 4 439 590.]); Poon et al. (2006[Poon, S. Y., Wong, W. Y., Cheah, K. W. & Shi, J. X. (2006). Chem. Eur. J. 12, 2550-2563.]).

[Scheme 1]

Experimental

Crystal data
  • C22H22O4S·2H2O

  • Mr = 418.50

  • Orthorhombic, A m m 2

  • a = 19.751 (3) Å

  • b = 10.904 (3) Å

  • c = 5.092 (2) Å

  • V = 1096.5 (7) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.18 mm−1

  • T = 292 (2) K

  • 0.46 × 0.20 × 0.16 mm

Data collection
  • Enraf–Nonius CAD-4 diffractometer

  • Absorption correction: spherical (WinGX; Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) Tmin = 0.921, Tmax = 0.972

  • 1211 measured reflections

  • 888 independent reflections

  • 756 reflections with I > 2σ(I)

  • Rint = 0.014

  • 3 standard reflections every 50 reflections intensity decay: 1.2%

Refinement
  • R[F2 > 2σ(F2)] = 0.053

  • wR(F2) = 0.142

  • S = 1.09

  • 888 reflections

  • 81 parameters

  • 3 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.52 e Å−3

  • Δρmin = −0.40 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]); 284 Friedel pairs

  • Flack parameter: −0.1 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O3W—H1W⋯O2i 0.78 2.07 2.800 (6) 157
Symmetry code: (i) -x, -y+1, z.

Data collection: DIFRAC (Gabe & White, 1993[Gabe, E. J. & White, P. S. (1993). DIFRAC. Am. Crystallogr. Assoc. Pittsburgh Meet. Abstract PA104.]); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989[Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384-387.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

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.

Related literature top

For the properties and synthesis of thermosetting acetylene-terminated resins, see: Lu & Hamerton (2002). For the applications of the title compound, see: Hanson & Millburn (1984); Poon et al. (2006).

Experimental top

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).

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level [symmetry codes: (i) = x, 1-y, z; (ii) = 1-x, 1-y, z; (iii) = 1-x, y, z].
2,2'-Dimethyl-4,4'-(sulfonyldi-p-phenylene)dibut-3-yn-2-ol dihydrate top
Crystal data top
C22H22O4S·2H2OF(000) = 444
Mr = 418.50Dx = 1.267 Mg m3
Orthorhombic, Amm2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: A 2 -2Cell parameters from 19 reflections
a = 19.751 (3) Åθ = 4.9–7.6°
b = 10.904 (3) ŵ = 0.18 mm1
c = 5.092 (2) ÅT = 292 K
V = 1096.5 (7) Å3Block, colourless
Z = 20.46 × 0.20 × 0.16 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
756 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.014
Graphite monochromatorθmax = 25.5°, θmin = 1.0°
ω/2θ scansh = 2323
Absorption correction: for a sphere
(WinGX; Farrugia, 1999)
k = 1313
Tmin = 0.921, Tmax = 0.972l = 63
1211 measured reflections3 standard reflections every 50 reflections
888 independent reflections intensity decay: 1.2%
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH 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 = 1.09Δρmax = 0.52 e Å3
888 reflectionsΔρmin = 0.40 e Å3
81 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
3 restraintsExtinction coefficient: 0.011 (3)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983); 284 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.1 (2)
Crystal data top
C22H22O4S·2H2OV = 1096.5 (7) Å3
Mr = 418.50Z = 2
Orthorhombic, Amm2Mo Kα radiation
a = 19.751 (3) ŵ = 0.18 mm1
b = 10.904 (3) ÅT = 292 K
c = 5.092 (2) Å0.46 × 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 = 0.9723 standard reflections every 50 reflections
1211 measured reflections intensity decay: 1.2%
888 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.053H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.142Δρmax = 0.52 e Å3
S = 1.09Δρmin = 0.40 e Å3
888 reflectionsAbsolute structure: Flack (1983); 284 Friedel pairs
81 parametersAbsolute structure 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
xyzUiso*/Ueq
S10.50000.50000.5447 (4)0.0400 (6)
O10.50000.6154 (4)0.6856 (9)0.0545 (12)
O20.0928 (2)0.50000.3050 (9)0.0541 (12)
H2O0.0592 (5)0.50000.398 (4)0.065 (8)*
C10.4296 (2)0.50000.3319 (11)0.0372 (13)
C20.40288 (19)0.3902 (3)0.2490 (10)0.0452 (10)
H20.42180.31670.30520.054*
C30.34760 (18)0.3895 (4)0.0814 (10)0.0501 (11)
H30.32900.31560.02550.060*
C40.3202 (2)0.50000.0022 (12)0.0426 (15)
C50.2615 (3)0.50000.1766 (12)0.0445 (14)
C60.2125 (2)0.50000.3109 (12)0.0401 (13)
C70.1511 (2)0.50000.4712 (13)0.0371 (12)
C80.1503 (2)0.3873 (3)0.6405 (8)0.0519 (11)
H8A0.13440.31880.53960.078*
H8B0.19530.37080.70240.078*
H8C0.12080.40030.78770.078*
O3W0.0000 (3)0.3082 (3)0.2418 (8)0.0559 (12)*
H1W0.03320.34670.24480.078 (16)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0347 (9)0.0578 (12)0.0276 (11)0.0000.0000.000
O10.053 (2)0.071 (3)0.040 (3)0.0000.0000.022 (2)
O20.0384 (18)0.080 (3)0.044 (3)0.0000.001 (2)0.000
C10.030 (2)0.052 (3)0.030 (3)0.0000.002 (2)0.000
C20.0437 (18)0.044 (2)0.048 (3)0.0055 (17)0.0050 (19)0.003 (2)
C30.0418 (19)0.055 (2)0.053 (3)0.0022 (16)0.010 (2)0.010 (2)
C40.029 (2)0.064 (3)0.035 (4)0.0000.004 (2)0.000
C50.040 (3)0.063 (3)0.031 (3)0.0000.003 (3)0.000
C60.034 (3)0.050 (3)0.037 (3)0.0000.004 (3)0.000
C70.037 (2)0.045 (3)0.029 (3)0.0000.002 (3)0.000
C80.066 (2)0.049 (2)0.041 (3)0.0030 (19)0.002 (2)0.000 (2)
Geometric parameters (Å, º) top
S1—O11.448 (4)C3—H30.9300
S1—O1i1.448 (4)C4—C3ii1.388 (5)
S1—C11.763 (5)C4—C51.461 (7)
S1—C1i1.763 (5)C5—C61.185 (7)
O2—C71.428 (7)C6—C71.462 (7)
O2—H2O0.817 (10)C7—C81.501 (5)
C1—C2ii1.375 (5)C7—C8ii1.501 (5)
C1—C21.375 (5)C8—H8A0.9600
C2—C31.386 (5)C8—H8B0.9600
C2—H20.9300C8—H8C0.9600
C3—C41.388 (5)O3W—H1W0.7779
O1—S1—O1i120.6 (4)C3ii—C4—C5119.7 (3)
O1—S1—C1107.72 (13)C3—C4—C5119.7 (3)
O1i—S1—C1107.72 (13)C6—C5—C4177.8 (6)
O1—S1—C1i107.72 (13)C5—C6—C7178.7 (6)
O1i—S1—C1i107.72 (13)O2—C7—C6109.7 (5)
C1—S1—C1i104.1 (4)O2—C7—C8109.4 (3)
C7—O2—H2O108.2 (13)C6—C7—C8109.2 (3)
C2ii—C1—C2121.1 (5)O2—C7—C8ii109.4 (3)
C2ii—C1—S1119.4 (3)C6—C7—C8ii109.2 (3)
C2—C1—S1119.4 (3)C8—C7—C8ii109.9 (5)
C1—C2—C3119.8 (4)C7—C8—H8A109.5
C1—C2—H2120.1C7—C8—H8B109.5
C3—C2—H2120.1H8A—C8—H8B109.5
C2—C3—C4119.4 (4)C7—C8—H8C109.5
C2—C3—H3120.3H8A—C8—H8C109.5
C4—C3—H3120.3H8B—C8—H8C109.5
C3ii—C4—C3120.5 (5)
O1—S1—C1—C2ii24.6 (5)C2—C3—C4—C3ii0.2 (9)
O1i—S1—C1—C2ii156.2 (4)C2—C3—C4—C5179.3 (5)
C1i—S1—C1—C2ii89.6 (4)C3ii—C4—C5—C689.5 (5)
O1—S1—C1—C2156.2 (4)C3—C4—C5—C689.5 (5)
O1i—S1—C1—C224.6 (5)C4—C5—C6—C70.00 (3)
C1i—S1—C1—C289.6 (4)C5—C6—C7—O20.00 (2)
C2ii—C1—C2—C30.7 (8)C5—C6—C7—C8119.9 (3)
S1—C1—C2—C3179.9 (4)C5—C6—C7—C8ii119.9 (3)
C1—C2—C3—C40.5 (7)
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3W—H1W···O2iii0.782.072.800 (6)157
Symmetry code: (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC22H22O4S·2H2O
Mr418.50
Crystal system, space groupOrthorhombic, Amm2
Temperature (K)292
a, b, c (Å)19.751 (3), 10.904 (3), 5.092 (2)
V3)1096.5 (7)
Z2
Radiation typeMo Kα
µ (mm1)0.18
Crystal size (mm)0.46 × 0.20 × 0.16
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionFor a sphere
(WinGX; Farrugia, 1999)
Tmin, Tmax0.921, 0.972
No. of measured, independent and
observed [I > 2σ(I)] reflections
1211, 888, 756
Rint0.014
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.142, 1.09
No. of reflections888
No. of parameters81
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.52, 0.40
Absolute structureFlack (1983); 284 Friedel pairs
Absolute structure parameter0.1 (2)

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3W—H1W···O2i0.782.072.800 (6)156.7
Symmetry code: (i) x, y+1, z.
 

Acknowledgements

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.

References

First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationGabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationGabe, E. J. & White, P. S. (1993). DIFRAC. Am. Crystallogr. Assoc. Pittsburgh Meet. Abstract PA104.  Google Scholar
First citationHanson, H. T. & Millburn, N. J. (1984). US Patent 4 439 590.  Google Scholar
First citationLu, S. Y. & Hamerton, I. (2002). Prog. Polym. Sci. 27, 1661–1712.  Web of Science CrossRef CAS Google Scholar
First citationPoon, S. Y., Wong, W. Y., Cheah, K. W. & Shi, J. X. (2006). Chem. Eur. J. 12, 2550–2563.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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