4,4′ Di­thio­diphenol: a chain of rings generated by two pairs of O—H⋯O hydrogen bonds

organic papers

o2318

Structure Reports Online

ISSN 1600-5368

4,4

_{-Dithiodiphenol: a chain of rings generated}

by two pairs of OÐH

O hydrogen bonds

Qing-ling Ni, Xiu-Jian Wang,* Jian-Qiang Zeng and

Hong-Xia Jian

School of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin 541004, People's Republic of China

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.003 AÊ

Rfactor = 0.033

wRfactor = 0.094

Data-to-parameter ratio = 13.8

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

In the title compound, C12H10O2S2, molecules are linked into

chains by two pairs of OÐH O hydrogen bonds [H O =

1.99 (2) AÊ, O O = 2.759 (2) and 2.783 (2) AÊ and OÐH O = 162 and 165 (2)_{]. Four hydroxy groups are linked togethervia}

hydrogen bonds to form a four-membered ring, which acts as a supramolecular synthon in the construction of one-dimen-sional chains of rings.

Comment

Hydrogen bonding, which is a powerful organizing force in designing various supramolecules and solid-state architectures (Subramanian & Zaworotko, 1994), is extensively used not only for networking numerous organic and organometallic compounds (Desiraju, 2000), but also for generating inter-esting supramolecular properties, such as electrical, optical and magnetic (LeÂtard et al., 1998). The molecule of the title compound, 4,40_{-dithiodiphenol, (I), with hydroxy groups and a}

¯exible SÐS bond, easily affords hydrogen bonding (Sugiura

et al., 1992) in crystal engineering to generate a supramolec-ular synthon or spacer.

In a previous paper (Wanget al., 1999), the compound bis(2-hydroxyphenyl) disul®de or 2,20_{-dithiodiphenol, (II), which}

was oxidized from 2-mercaptophenol, acts as a spacer to link anions together to form one-dimensional chains through hydrogen bonding. In order to explore extensively the hydrogen-bond effect on the formation of three-dimensional networks in the solid state and the in¯uence of these on the properties of compounds, we prepared compound (I). As with compound (II), (I) was oxidized in air from 4-mercaptophenol, and was intended to act as a building block to construct a three-dimensional organic±inorganic hybrid supramolecule through hydrogen bonding. Unfortunately, only the organic species (I) crystallized from the methanol solution.

The structure of (I) (Fig. 1) is similar to that of (II) (Wanget

al., 1999). Selected bond lengths and angles are listed in

Table 1. The CÐS bonds [average 1.773 AÊ], the SÐSÐC

angles [average 104.5_{] and the torsion angle C1ÐS1ÐS2Ð}

C11 [82.5 (1)_{] in (I) are similar to corresponding values in}

(II). However, the SÐS bond length [2.0524 (11) AÊ] in (I) is signi®cantly longer than the average SÐS bond length value of 2.017 (6) AÊ in (II). According to Hordvik's (1996) obser-vation (Desiraju, 2000), a relationship exists between the SÐS bond length and the CÐSÐSÐC torsion angle in organic disul®des, probably caused by lone-pair repulsion which will

be minimized when the dihedral angle is 90_{. The greater}

deviation of this angle [82.5 (1)_{in (I) compared with 84.3in}

(II)] from the ideal value could be caused by the restriction of the rotation of the SÐS bond by the hydrogen bonds, which

cannot release the molecular strain. The two benzene rings in the title compound form a dihedral angle of 48.1 (2)_.

The hydroxy groups in the title compound form OÐH O

hydrogen bonds which link molecules head-to-tail, forming one-dimensional chains. In addition, adjacent one-dimen-sional chains are linked together through further hydrogen bonding to form a chain of rings (Fig. 2 and Table 2).

Experimental

To a solution (15 ml) of MeOH containing (Bu4N)4[Mo8O26] (0.55 g, 0.25 mmol), a solution of 4-mercaptophenol (0.252 g, 2.0 mmol) in 4 ml of MeOH was added with stirring at room temperature. The solution turned yellow immediately. After stirring for 4 h, the reac-tion solureac-tion was concentrated to 5 ml under reduced pressure. Addition of diethyl ether gave yellow crystals which were suitable for X-ray diffraction.

Crystal data

C12H10O2S2 Mr= 250.32

Monoclinic, C2=c a= 20.886 (4) AÊ

b= 10.959 (2) AÊ

c= 11.263 (2) AÊ

= 115.09 (3) V= 2334.7 (9) AÊ3 Z= 8

Dx= 1.424 Mg mÿ3

MoKradiation Cell parameters from 3841

re¯ections

= 2.2±27.0

= 0.44 mmÿ1 T= 293 (2) K Block, yellow 0.110.110.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer

!scans

Absorption correction: multi-scan (SADABS; Bruker, 1998)

Tmin= 0.953,Tmax= 0.966 6726 measured re¯ections

2547 independent re¯ections 2071 re¯ections withI> 2(I)

Rint= 0.015

max= 27.0 h=ÿ26!23

k=ÿ13!11

l=ÿ14!13

Refinement

Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.033} wR(F2_{) = 0.094} S= 1.05 2547 re¯ections 185 parameters

All H-atom parameters re®ned

w= 1/[2_(F

o2) + (0.0496P)2

+ 0.722P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.014

max= 0.24 e AÊÿ3

min=ÿ0.19 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

S1ÐC1 1.7787 (17) S1ÐS2 2.0524 (11) S2ÐC11 1.7672 (17)

O1ÐC4 1.3738 (19) O2ÐC8 1.377 (2) C1ÐS1ÐS2 103.77 (6)

C11ÐS2ÐS1 105.17 (6) C2ÐC1ÐS1 119.12 (14)

C6ÐC1ÐS1 121.49 (14) C5ÐC4ÐO1 118.08 (15) C9ÐC8ÐO2 121.94 (15)

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

O1ÐH1 O2i _{0.79 (2) 1.99 (2) 2.759 (2) 162 (2)}

O2ÐH11 O1ii _{0.81 (2) 1.99 (2) 2.7829 (19) 165 (2)}

Symmetry codes: (i)1

2ÿx;ÿ12ÿy;ÿz; (ii)xÿ12;yÿ12;z.

organic papers

Acta Cryst.(2004). E60, o2318±o2320 Ni, Wang, Zeng and Jian C₁₂H₁₀O₂S₂

o2319

Figure 1

A view of the structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 2

All H atoms were located in a difference Fourier map and re®ned independently with isotropic displacement parameters. The re®ned OÐH distances are 0.79 (2) and 0.81 (2) AÊ, while the CÐH distances are in the range 0.92 (2)±0.98 (2) AÊ.

Data collection:SMART(Bruker, 1998); cell re®nement:SAINT

(Bruker, 1998); data reduction: SAINT; program(s) used to solve structure:SHELXS97 (Sheldrick, 1997a); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997a); molecular graphics:

SHELXTL(Sheldrick, 1997b); software used to prepare material for publication:SHELXL97.

This work was sponsored by the Natural Science Founda-tion of Guangxi Province.

References

Bruker (1998).SMART,SAINTandSADABS.Bruker AXS Inc., Madison, Wisconsin, USA.

Desiraju, G. R. (2000).Stimulating Concepts in Chemistry, edited by F. VoÈgtle, J. F. Stoddart & M. Shibasaki, pp. 293±302. Weinheim: Wiley VCH. Hordvik, A. (1996).Acta Chem. Scand.20, 1885±1895.

LeÂtard, J. F., Guionneau, P., Rabardel, L., Howard, J. A. K., Goeta, A. E., Chasseau, D. & Kahn, O. (1998).Inorg. Chem.37, 4432±4441.

Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.

Sheldrick, G. M. (1997b).SHELXTL.Bruker AXS Inc., Madison, Wisconsin, USA.

Subramanian, S. & Zaworotko, M. J. (1994).Coord. Chem. Rev.137, 357±401. Sugiura, K., Toyoda, J., Okamoto, H., Okaniwa, K., Mitani, T., Kawamoto, A.,

Tanaka, J. & Nakasuji, K. (1992).Angew. Chem. Int. Engl.31, 852±854. Wang, X.-J., Chen, Z.-F., Kang, B.-S., Liang, H., Liu, H.-Q., Yu, K.-B., Su, C.-Y.

& Chen, Z.-N. (1999).Polyhedron,18, 647±655.

organic papers

supporting information

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Acta Cryst. (2004). E60, o2318–o2320

supporting information

Acta Cryst. (2004). E60, o2318–o2320 [https://doi.org/10.1107/S1600536804028636]

4,4

′

-Dithiodiphenol: a chain of rings generated by two pairs of O

—

H

···

O

hydrogen bonds

Qing-ling Ni, Xiu-Jian Wang, Jian-Qiang Zeng and Hong-Xia Jian

4,4′-Dithiodiphenol

Crystal data

C12H10O2S2

Mr = 250.32 Monoclinic, C2/c

Hall symbol: -C 2yc

a = 20.886 (4) Å

b = 10.959 (2) Å

c = 11.263 (2) Å

β = 115.09 (3)°

V = 2334.7 (9) Å3

Z = 8

F(000) = 1040

Dx = 1.424 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3841 reflections

θ = 2.2–27.0°

µ = 0.44 mm−1

T = 293 K Block, yellow

0.11 × 0.11 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: multi-scan (SADABS; Siemens, 1998)

Tmin = 0.953, Tmax = 0.966

6726 measured reflections 2547 independent reflections 2071 reflections with I > 2σ(I)

Rint = 0.015

θmax = 27.0°, θmin = 2.2°

h = −26→23

k = −13→11

l = −14→13

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.033}

wR(F2_{) = 0.094}

S = 1.05 2547 reflections 185 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

All H-atom parameters refined

w = 1/[σ2_(F

o2) + (0.0496P)2 + 0.722P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.014

Δρmax = 0.24 e Å−3

supporting information

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Acta Cryst. (2004). E60, o2318–o2320 Special details

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

S1 0.24192 (3) 0.11462 (5) 0.33220 (5) 0.06695 (17)

S2 0.14322 (2) 0.14461 (4) 0.18475 (5) 0.05762 (16)

O1 0.43270 (7) 0.05363 (14) 0.07053 (14) 0.0648 (4)

O2 0.01560 (7) −0.33155 (12) −0.03513 (14) 0.0641 (4)

C1 0.29650 (8) 0.09545 (16) 0.24787 (16) 0.0503 (4)

C2 0.33037 (10) −0.01454 (17) 0.25722 (18) 0.0591 (4)

C3 0.37673 (10) −0.02977 (17) 0.20021 (18) 0.0585 (4)

C4 0.38735 (8) 0.06480 (15) 0.12950 (16) 0.0481 (4)

C5 0.35261 (9) 0.17381 (16) 0.11703 (19) 0.0548 (4)

C6 0.30811 (9) 0.19026 (17) 0.17761 (19) 0.0560 (4)

C7 0.09625 (10) −0.17254 (17) −0.0154 (2) 0.0601 (5)

C8 0.04642 (8) −0.22269 (15) 0.02139 (16) 0.0480 (4)

C9 0.02876 (9) −0.16365 (17) 0.11104 (17) 0.0521 (4)

C10 0.06040 (8) −0.05426 (16) 0.16365 (16) 0.0513 (4)

C11 0.10938 (8) −0.00209 (14) 0.12630 (16) 0.0459 (4)

C12 0.12695 (9) −0.06259 (17) 0.03597 (19) 0.0574 (4)

H10 0.0489 (10) −0.0130 (17) 0.2281 (18) 0.065 (5)*

H5 0.3587 (10) 0.2384 (19) 0.0661 (19) 0.071 (6)*

H9 −0.0032 (10) −0.2011 (17) 0.1390 (18) 0.061 (5)*

H6 0.2853 (11) 0.2677 (19) 0.1695 (19) 0.069 (6)*

H7 0.1046 (11) −0.211 (2) −0.082 (2) 0.079 (6)*

H12 0.1590 (12) −0.028 (2) 0.012 (2) 0.082 (6)*

H3 0.4009 (10) −0.102 (2) 0.2084 (19) 0.067 (6)*

H2 0.3240 (11) −0.082 (2) 0.308 (2) 0.072 (6)*

H11 −0.0109 (13) −0.352 (2) −0.003 (2) 0.082 (7)*

H1 0.4426 (11) −0.016 (2) 0.069 (2) 0.074 (7)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

S1 0.0626 (3) 0.0916 (4) 0.0563 (3) −0.0140 (2) 0.0344 (2) −0.0141 (2)

S2 0.0589 (3) 0.0508 (3) 0.0772 (3) 0.00150 (18) 0.0424 (2) −0.0022 (2)

O1 0.0665 (8) 0.0606 (8) 0.0849 (10) 0.0014 (6) 0.0493 (7) −0.0020 (7)

O2 0.0636 (8) 0.0600 (8) 0.0835 (9) −0.0075 (6) 0.0454 (7) −0.0104 (6)

C1 0.0439 (8) 0.0591 (9) 0.0501 (9) −0.0084 (7) 0.0218 (7) −0.0062 (7)

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Acta Cryst. (2004). E60, o2318–o2320

C3 0.0641 (11) 0.0506 (10) 0.0653 (11) 0.0057 (8) 0.0317 (9) 0.0029 (8)

C4 0.0429 (8) 0.0536 (9) 0.0498 (8) −0.0053 (7) 0.0215 (7) −0.0057 (7)

C5 0.0544 (9) 0.0499 (9) 0.0667 (11) −0.0046 (7) 0.0321 (8) 0.0043 (8)

C6 0.0527 (9) 0.0503 (9) 0.0717 (11) 0.0007 (8) 0.0329 (9) −0.0006 (8)

C7 0.0700 (11) 0.0607 (11) 0.0715 (12) 0.0000 (9) 0.0513 (10) −0.0065 (9)

C8 0.0434 (8) 0.0513 (9) 0.0537 (9) 0.0048 (7) 0.0247 (7) 0.0038 (7)

C9 0.0456 (8) 0.0664 (11) 0.0546 (9) −0.0032 (7) 0.0310 (7) 0.0018 (8)

C10 0.0485 (9) 0.0653 (10) 0.0514 (9) 0.0009 (8) 0.0321 (7) −0.0030 (8)

C11 0.0425 (8) 0.0504 (9) 0.0513 (8) 0.0051 (6) 0.0262 (7) 0.0042 (7)

C12 0.0611 (10) 0.0615 (10) 0.0702 (11) −0.0026 (8) 0.0478 (9) −0.0003 (9)

Geometric parameters (Å, º)

S1—C1 1.7787 (17) C5—C6 1.378 (2)

S1—S2 2.0524 (11) C5—H5 0.95 (2)

S2—C11 1.7672 (17) C6—H6 0.96 (2)

O1—C4 1.3738 (19) C7—C12 1.372 (3)

O1—H1 0.79 (2) C7—C8 1.386 (2)

O2—C8 1.377 (2) C7—H7 0.94 (2)

O2—H11 0.81 (2) C8—C9 1.375 (2)

C1—C2 1.379 (3) C9—C10 1.376 (2)

C1—C6 1.388 (2) C9—H9 0.944 (19)

C2—C3 1.380 (3) C10—C11 1.384 (2)

C2—H2 0.98 (2) C10—H10 0.97 (2)

C3—C4 1.381 (2) C11—C12 1.388 (2)

C3—H3 0.92 (2) C12—H12 0.90 (2)

C4—C5 1.374 (2)

C1—S1—S2 103.77 (6) C5—C6—H6 118.7 (12)

C11—S2—S1 105.17 (6) C1—C6—H6 121.2 (12)

C4—O1—H1 109.7 (16) C12—C7—C8 119.86 (15)

C8—O2—H11 108.2 (17) C12—C7—H7 121.1 (13)

C2—C1—C6 119.33 (16) C8—C7—H7 118.7 (13)

C2—C1—S1 119.12 (14) C9—C8—O2 121.94 (15)

C6—C1—S1 121.49 (14) C9—C8—C7 120.13 (16)

C1—C2—C3 120.57 (17) O2—C8—C7 117.93 (15)

C1—C2—H2 120.8 (12) C8—C9—C10 119.81 (15)

C3—C2—H2 118.6 (12) C8—C9—H9 119.2 (12)

C2—C3—C4 119.56 (17) C10—C9—H9 120.9 (12)

C2—C3—H3 121.5 (13) C9—C10—C11 120.72 (15)

C4—C3—H3 119.0 (13) C9—C10—H10 120.2 (11)

C5—C4—O1 118.08 (15) C11—C10—H10 119.0 (11)

C5—C4—C3 120.31 (15) C10—C11—C12 119.01 (15)

O1—C4—C3 121.61 (16) C10—C11—S2 119.54 (12)

C4—C5—C6 120.06 (17) C12—C11—S2 121.29 (12)

C4—C5—H5 120.5 (12) C7—C12—C11 120.46 (15)

C6—C5—H5 119.5 (12) C7—C12—H12 120.9 (14)

supporting information

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Acta Cryst. (2004). E60, o2318–o2320 Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1—H1···O2i _{0.79 (2) 1.99 (2) 2.759 (2) 162 (2)}

O2—H11···O1ii _{0.81 (2) 1.99 (2) 2.7829 (19) 165 (2)}