Dimethyl 2,2′-[ethane-1,2-diylbis(sulfanedi­yl)]dibenzoate

Hu, X.; Yu, J.; Yuan, L.

doi:10.1107/S1600536810022403

organic compounds

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Volume 66| Part 7| July 2010| Page o1675

doi:10.1107/S1600536810022403

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Dimethyl 2,2′-[ethane-1,2-diylbis(sulfanediyl)]dibenzoate

Xiaoming Hu,^a ^* Jianghua Yu ^b and Limin Yuan ^b

^aSchool of Chemistry and Chemical Engineering, Pingdingshan University, Pingdingshan 467002, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Yangzhou Universitry, Yangzhou 225002, People's Republic of China
^*Correspondence e-mail: xiaominghu10@163.com

(Received 10 June 2010; accepted 11 June 2010; online 16 June 2010)

The title compound, C₁₈H₁₈O₄S₂, was synthesized by the reaction of 1,2-dibromoethane with methyl thiosalicylate. The complete molecule is generated by crystallographic twofold symmetry: two methyl benzoate units are linked by an –S–(CH₂)₂–S– bridging chain with a gauche S—CH₂—CH₂—S torsion angle [72.88 (16)°]. The two aromatic rings form a dihedral angle of 79.99 (6)°. In the crystal, adjacent molecules are linked into a three-dimensional network by non-classical C—H⋯O hydrogen bonds.

Related literature

For the potential use of dithiodibenzoates in the construction of diverse frameworks with tailored properties and functions, see: Humphrey et al. (2004 ); Li et al. (2007 ); Murugavel et al. (2001 ); Wang et al. (2004 ); Zhou et al. (2009 ).

Experimental

Crystal data

C₁₈H₁₈O₄S₂
M_r = 362.44
Monoclinic, C 2
a = 15.077 (3) Å
b = 5.3913 (10) Å
c = 12.495 (2) Å
β = 120.662 (2)°
V = 873.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 296 K
0.52 × 0.32 × 0.22 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.850, T_max = 0.932
3836 measured reflections
1948 independent reflections
1864 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.082
S = 1.08
1948 reflections
110 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack (1983 ), 834 Friedel pairs
Flack parameter: −0.02 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O2ⁱ	0.93	2.51	3.435 (2)	171
Symmetry code: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2000 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810022403/jh2166sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810022403/jh2166Isup2.hkl

checkCIF report

Comment top

The flexibility and conformational freedom of the disulfide derivatives of the benzoate – dithiodibenzoates - provides a possibility for the construction of diverse frameworks with tailored properties and functions (Murugavel et al., 2001; Humphrey et al., 2004; Wang et al. 2004; Li et al., 2007; Zhou et al., 2009). The flexible bridging ligands adopt unusually twisted structures with different C—S—S—C torsion angles in constructing complexes.

The title compound described here is a longer analogue of 2,2'-dithiodibenzoate with the two methyl benzoate units interconnected by a flexible –S-(CH₂)₂-S– bridge (Fig. 1). The torsion angle S—CH₂—CH₂—S is 72.88 (16)°. The two aromatic rings form a dihedral angle of 79.99 (6)°. The C1(sp²)-S bond length [1.769 (2) Å] is significantly shorter than the C8(sp³)-S [1.814 (2) Å] bond length due to p-π conjugation. There are no significant S···S nor S···O contacts present in the structure and C—H···π (arene) hydrogen bonds and aromatic π···π stacking interactions are also absent. In the crystal, intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into a three-dimensional supramolecular structure (Fig. 2).

Related literature top

For complexes of 2,2'-dithiodibenzoic acid, see: Humphrey et al. (2004); Li et al. (2007); Murugavel et al. (2001); Wang et al. (2004); Zhou et al. (2009).

Experimental top

The title compound was synthesized as follows: a solution of 1,2-dibromoethane (0.94 g, 5 mmol) in methanol (10 ml) was added dropwise to a mixture of methyl thiosalicylate (1.85 g, 11 mmol), KOH (0.617 g, 11 mmol) and ethanol (10 ml). The reaction mixture was stirred and heated for 12 h. The precipitate was filtered off, washed with water.Yield 72%; Colourless block crystals suitable for single-crystals X-ray analysis were obtained by recrystallization from an acetonitrile solution.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids. Unlabeled atoms are related to labeled atoms by the symmetry code (-x, y, -z).
	Fig. 2. View of the connections inter- and intramolecules in (I) with the C—H···O interactions shown as orange dashed lines.

Dimethyl 2,2'-[ethane-1,2-diylbis(sulfanediyl)]dibenzoate top

Crystal data top

C₁₈H₁₈O₄S₂	F(000) = 380
M_r = 362.44	D_x = 1.378 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 2178 reflections
a = 15.077 (3) Å	θ = 2.7–27.4°
b = 5.3913 (10) Å	µ = 0.32 mm⁻¹
c = 12.495 (2) Å	T = 296 K
β = 120.662 (2)°	Block, colourless
V = 873.6 (3) Å³	0.52 × 0.32 × 0.22 mm
Z = 2

Data collection top

Bruker SMART APEXII diffractometer	1948 independent reflections
Radiation source: fine-focus sealed tube	1864 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −19→18
T_min = 0.850, T_max = 0.932	k = −6→6
3836 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0441P)² + 0.1272P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1948 reflections	Δρ_max = 0.23 e Å⁻³
110 parameters	Δρ_min = −0.15 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 834 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (7)

Crystal data top

C₁₈H₁₈O₄S₂	V = 873.6 (3) Å³
M_r = 362.44	Z = 2
Monoclinic, C2	Mo Kα radiation
a = 15.077 (3) Å	µ = 0.32 mm⁻¹
b = 5.3913 (10) Å	T = 296 K
c = 12.495 (2) Å	0.52 × 0.32 × 0.22 mm
β = 120.662 (2)°

Data collection top

Bruker SMART APEXII diffractometer	1948 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	1864 reflections with I > 2σ(I)
T_min = 0.850, T_max = 0.932	R_int = 0.023
3836 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.082	Δρ_max = 0.23 e Å⁻³
S = 1.08	Δρ_min = −0.15 e Å⁻³
1948 reflections	Absolute structure: Flack (1983), 834 Friedel pairs
110 parameters	Absolute structure parameter: −0.02 (7)
1 restraint

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	U_iso*/U_eq
C1	0.24609 (11)	0.0317 (4)	0.17607 (14)	0.0440 (3)
C2	0.31876 (12)	0.1986 (4)	0.26461 (15)	0.0455 (4)
C3	0.42223 (14)	0.1865 (5)	0.29514 (18)	0.0590 (5)
H3	0.4700	0.2970	0.3530	0.071*
C4	0.45387 (16)	0.0121 (6)	0.2402 (2)	0.0689 (7)
H4	0.5224	0.0062	0.2606	0.083*
C5	0.38363 (18)	−0.1516 (5)	0.1556 (2)	0.0694 (7)
H5	0.4051	−0.2695	0.1192	0.083*
C6	0.28109 (16)	−0.1440 (4)	0.12343 (19)	0.0577 (5)
H6	0.2348	−0.2574	0.0660	0.069*
C7	0.28831 (13)	0.3846 (4)	0.32683 (16)	0.0478 (4)
C8	0.05804 (14)	−0.2095 (4)	0.02558 (17)	0.0525 (4)
H8A	0.0717	−0.1916	−0.0420	0.063*
H8B	0.0879	−0.3649	0.0679	0.063*
C9	0.3458 (2)	0.6901 (7)	0.4813 (3)	0.0898 (8)
H9A	0.2859	0.7821	0.4230	0.135*
H9B	0.4035	0.8008	0.5233	0.135*
H9C	0.3330	0.6119	0.5411	0.135*
O1	0.36822 (11)	0.5052 (4)	0.41658 (15)	0.0793 (5)
O2	0.20111 (11)	0.4248 (3)	0.30111 (15)	0.0675 (4)
S1	0.11495 (3)	0.04719 (7)	0.13359 (4)	0.04790 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0394 (7)	0.0510 (9)	0.0398 (7)	0.0110 (9)	0.0188 (6)	0.0069 (9)
C2	0.0355 (8)	0.0578 (11)	0.0388 (8)	0.0087 (7)	0.0157 (7)	0.0098 (7)
C3	0.0380 (9)	0.0805 (14)	0.0535 (10)	0.0051 (9)	0.0198 (8)	0.0137 (10)
C4	0.0461 (10)	0.100 (2)	0.0675 (12)	0.0304 (14)	0.0340 (9)	0.0303 (14)
C5	0.0659 (14)	0.0845 (17)	0.0697 (14)	0.0365 (12)	0.0433 (12)	0.0199 (12)
C6	0.0567 (11)	0.0623 (12)	0.0551 (11)	0.0187 (10)	0.0292 (9)	0.0041 (9)
C7	0.0387 (9)	0.0555 (11)	0.0409 (8)	−0.0024 (8)	0.0143 (7)	0.0010 (8)
C8	0.0529 (10)	0.0413 (9)	0.0474 (10)	0.0051 (8)	0.0141 (8)	−0.0028 (7)
C9	0.0861 (18)	0.0898 (19)	0.0753 (16)	−0.0203 (16)	0.0279 (14)	−0.0349 (16)
O1	0.0477 (7)	0.1046 (15)	0.0671 (8)	−0.0113 (9)	0.0159 (6)	−0.0323 (10)
O2	0.0418 (7)	0.0789 (10)	0.0765 (9)	−0.0027 (7)	0.0264 (7)	−0.0284 (8)
S1	0.03542 (19)	0.0520 (2)	0.0488 (2)	0.0033 (2)	0.01601 (15)	−0.0082 (2)

Geometric parameters (Å, º) top

C1—C6	1.401 (3)	C6—H6	0.9300
C1—C2	1.413 (3)	C7—O2	1.203 (2)
C1—S1	1.7685 (15)	C7—O1	1.324 (2)
C2—C3	1.406 (2)	C8—C8ⁱ	1.527 (4)
C2—C7	1.478 (3)	C8—S1	1.8143 (19)
C3—C4	1.384 (4)	C8—H8A	0.9700
C3—H3	0.9300	C8—H8B	0.9700
C4—C5	1.370 (4)	C9—O1	1.429 (3)
C4—H4	0.9300	C9—H9A	0.9600
C5—C6	1.386 (3)	C9—H9B	0.9600
C5—H5	0.9300	C9—H9C	0.9600

C6—C1—C2	118.08 (15)	O2—C7—O1	122.42 (19)
C6—C1—S1	121.47 (16)	O2—C7—C2	124.88 (16)
C2—C1—S1	120.44 (14)	O1—C7—C2	112.71 (16)
C3—C2—C1	119.52 (18)	C8ⁱ—C8—S1	108.52 (12)
C3—C2—C7	119.22 (18)	C8ⁱ—C8—H8A	110.0
C1—C2—C7	121.26 (14)	S1—C8—H8A	110.0
C4—C3—C2	120.8 (2)	C8ⁱ—C8—H8B	110.0
C4—C3—H3	119.6	S1—C8—H8B	110.0
C2—C3—H3	119.6	H8A—C8—H8B	108.4
C5—C4—C3	119.61 (18)	O1—C9—H9A	109.5
C5—C4—H4	120.2	O1—C9—H9B	109.5
C3—C4—H4	120.2	H9A—C9—H9B	109.5
C4—C5—C6	120.9 (2)	O1—C9—H9C	109.5
C4—C5—H5	119.5	H9A—C9—H9C	109.5
C6—C5—H5	119.5	H9B—C9—H9C	109.5
C5—C6—C1	121.0 (2)	C7—O1—C9	116.51 (17)
C5—C6—H6	119.5	C1—S1—C8	102.68 (10)
C1—C6—H6	119.5

C6—C1—C2—C3	1.1 (3)	S1—C1—C6—C5	178.76 (16)
S1—C1—C2—C3	−178.69 (15)	C3—C2—C7—O2	173.83 (19)
C6—C1—C2—C7	−178.26 (18)	C1—C2—C7—O2	−6.8 (3)
S1—C1—C2—C7	1.9 (2)	C3—C2—C7—O1	−6.6 (3)
C1—C2—C3—C4	−0.4 (3)	C1—C2—C7—O1	172.80 (18)
C7—C2—C3—C4	178.97 (18)	O2—C7—O1—C9	−0.9 (3)
C2—C3—C4—C5	−0.4 (3)	C2—C7—O1—C9	179.6 (2)
C3—C4—C5—C6	0.5 (3)	C6—C1—S1—C8	2.60 (18)
C4—C5—C6—C1	0.3 (3)	C2—C1—S1—C8	−177.58 (15)
C2—C1—C6—C5	−1.1 (3)	C8ⁱ—C8—S1—C1	−176.60 (15)

Symmetry code: (i) −x, y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1	0.93	2.34	2.679 (3)	101
C4—H4···O2ⁱⁱ	0.93	2.51	3.435 (2)	171

Symmetry code: (ii) x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₈O₄S₂
M_r	362.44
Crystal system, space group	Monoclinic, C2
Temperature (K)	296
a, b, c (Å)	15.077 (3), 5.3913 (10), 12.495 (2)
β (°)	120.662 (2)
V (Å³)	873.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.52 × 0.32 × 0.22

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.850, 0.932
No. of measured, independent and observed [I > 2σ(I)] reflections	3836, 1948, 1864
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.082, 1.08
No. of reflections	1948
No. of parameters	110
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.15
Absolute structure	Flack (1983), 834 Friedel pairs
Absolute structure parameter	−0.02 (7)

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2000), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2ⁱ	0.93	2.51	3.435 (2)	171.2

Symmetry code: (i) x+1/2, y−1/2, z.

Acknowledgements

This work was supported by the Top-Class Foundation of Pingdingshan University (grant No. 2006047).

References

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