Bis(cyclohexylammonium) 2,2′-disulfanediyldibenzoate

Wei, X.; Li, J.; Yin, H.

doi:10.1107/S1600536810054012

organic compounds

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Volume 67| Part 2| February 2011| Page o319

doi:10.1107/S1600536810054012

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Bis(cyclohexylammonium) 2,2′-disulfanediyldibenzoate

Xinting Wei,^a Jing Li ^a and Handong Yin ^a ^*

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: handongyin@163.com

(Received 9 December 2010; accepted 24 December 2010; online 12 January 2011)

In the title molecular salt, 2C₆H₁₄N⁺·C₁₄H₈O₄S₂²⁻, the complete dianion is generated by crystallographic twofold symmetry and a twisted conformation is found [the C—S—S—C torsion angle is 87.13 (2)° and the dihedral angle between the rings is 83.4 (2)°]. In the crystal, intermolecular N—H⋯O hydrogen bonds link the cations and anions.

Related literature

For the design and synthesis of novel coordination architectures, see: Sato et al. (1996 ); Yaghi et al. (1998 ).

Experimental

Crystal data

2C₆H₁₄N⁺·C₁₄H₈O₄S₂²⁻
M_r = 504.69
Tetragonal, $[I \overline 4]$
a = 11.6411 (15) Å
c = 20.105 (3) Å
V = 2724.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 298 K
0.48 × 0.46 × 0.42 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.898, T_max = 0.910
5632 measured reflections
2394 independent reflections
1398 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.124
S = 1.05
2394 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 1153 Friedel pairs
Flack parameter: −0.07 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O1	0.89	1.91	2.785 (5)	167
N1—H1A⋯O1ⁱ	0.89	1.96	2.841 (5)	172
N1—H1B⋯O2ⁱⁱ	0.89	1.84	2.723 (5)	175
Symmetry codes: (i) y, -x+1, -z+2; (ii) -x+1, -y+1, z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810054012/bx2336sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810054012/bx2336Isup2.hkl

checkCIF report

Comment top

The design and synthesis of novel coordination architectures has resulted in a great number of research efforts, due not only to their intriguing structural topologies, but also to their unexpected properties as functional materials (Sato et al., 1996; Yaghi et al., 1998). The main strategy popularly used in this area is the building–block approach. 2,2'–Dithiodibenzoic acid is a good choice in the design of novel coordination architectures, since its four coordination sites are likely to engage in coordination to metal ions. We report here the crystal structure, of new salt of 2,2-dithiodisalicylate with cyclohexylammonium cation. The title compound, (I) is composed of 2,2-dithiodisalicylate and cyclohexylammonium ions, in a ratio of 1:2; the asymmetric unit consists of one-half molecule of the 2,2-dithiodisalicylate and one cyclohexylammonium cation. A twofold axis of symmetry passes through the centre of the S—S bond. A twisted conformation is found for the anion [the C—S—S—C torsion angle is 87.13 (2)° and the dihedral angle between the rings is 83.4 (2)°]. There are two N—H···O intermolecular and one intramolecular hydrogen bonds, (Fig. 2 and Table 2).

Related literature top

For the design and synthesis of novel coordination architectures, see: Sato et al. (1996); Yaghi et al. (1998).

Experimental top

The reaction was carried out under nitrogen atmosphere. 2,2'–Dithiodibenzoic acid (0.5 mmol) was dissolved in 10 ml methanol, and a solution of cyclohexylamine (1.0 mmol) in 20 ml toluene was added dropwise under intense agitation. The mixture was placed in air at room temperature. Suitable for X-ray analysis were obtained by slow evaporation of acetone solution over a period of two weeks. Analysis, calculated for [(C₁₄H₈O₄S₂)^2-.2(C₆H₁₄N)⁺ (Mr = 504.69): C 61.87, N 5.55, H 7.19%; found: C 61.82, N 5.50, H 7.15%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the compound, showing 50% probability displacement ellipsoids. H atoms have been omitted for clarity. (#1 - x + 1,-y + 2,z)
	Fig. 2. The crystal packing, linked by N—H···O hydrogen bonds. (#2 y,-x + 1,-z + 2 #3 - x + 1,-y + 1,z)

Bis(cyclohexylammonium) 2,2'-disulfanediyldibenzoate top

Crystal data top

2C₆H₁₄N⁺·C₁₄H₈O₄S₂²⁻	D_x = 1.230 Mg m⁻³
M_r = 504.69	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 1336 reflections
Hall symbol: I -4	θ = 3.2–18.6°
a = 11.6411 (15) Å	µ = 0.23 mm⁻¹
c = 20.105 (3) Å	T = 298 K
V = 2724.6 (6) Å³	Block, colourless
Z = 4	0.48 × 0.46 × 0.42 mm
F(000) = 1080

Data collection top

Bruker SMART diffractometer	2394 independent reflections
Radiation source: fine-focus sealed tube	1398 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
phi and ω scans	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→7
T_min = 0.898, T_max = 0.910	k = −12→13
5632 measured reflections	l = −23→22

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0468P)² + 1.0167P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2394 reflections	Δρ_max = 0.17 e Å⁻³
155 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1153 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.07 (12)

Crystal data top

2C₆H₁₄N⁺·C₁₄H₈O₄S₂²⁻	Z = 4
M_r = 504.69	Mo Kα radiation
Tetragonal, I4	µ = 0.23 mm⁻¹
a = 11.6411 (15) Å	T = 298 K
c = 20.105 (3) Å	0.48 × 0.46 × 0.42 mm
V = 2724.6 (6) Å³

Data collection top

Bruker SMART diffractometer	2394 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1398 reflections with I > 2σ(I)
T_min = 0.898, T_max = 0.910	R_int = 0.036
5632 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.124	Δρ_max = 0.17 e Å⁻³
S = 1.05	Δρ_min = −0.17 e Å⁻³
2394 reflections	Absolute structure: Flack (1983), 1153 Friedel pairs
155 parameters	Absolute structure parameter: −0.07 (12)
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.6618 (3)	0.6089 (3)	0.93400 (16)	0.0705 (10)
H1A	0.6773	0.5904	0.9760	0.106*
H1B	0.6574	0.5454	0.9096	0.106*
H1C	0.5951	0.6462	0.9322	0.106*
O1	0.4378 (3)	0.6925 (2)	0.92848 (17)	0.0819 (9)
O2	0.3371 (4)	0.5845 (3)	0.8579 (2)	0.1379 (17)
S1	0.48337 (10)	0.91347 (10)	0.91518 (6)	0.0769 (4)
C1	0.3688 (5)	0.6790 (4)	0.8808 (3)	0.0799 (14)
C2	0.3236 (3)	0.7842 (3)	0.8463 (2)	0.0575 (11)
C3	0.3708 (4)	0.8932 (3)	0.85641 (19)	0.0572 (10)
C4	0.3259 (4)	0.9841 (4)	0.8194 (2)	0.0729 (13)
H4	0.3587	1.0566	0.8235	0.088*
C5	0.2343 (5)	0.9691 (4)	0.7772 (2)	0.0786 (13)
H5	0.2045	1.0318	0.7543	0.094*
C6	0.1871 (4)	0.8638 (5)	0.7687 (2)	0.0757 (13)
H6	0.1244	0.8542	0.7406	0.091*
C7	0.2327 (4)	0.7705 (4)	0.8022 (2)	0.0691 (12)
H7	0.2022	0.6977	0.7950	0.083*
C8	0.7554 (4)	0.6845 (3)	0.9074 (2)	0.0643 (11)
H8	0.7267	0.7221	0.8671	0.077*
C9	0.7850 (4)	0.7765 (4)	0.9571 (2)	0.0739 (13)
H9A	0.8072	0.7412	0.9989	0.089*
H9B	0.7182	0.8242	0.9652	0.089*
C10	0.8830 (4)	0.8502 (4)	0.9313 (3)	0.0922 (16)
H10A	0.8579	0.8914	0.8919	0.111*
H10B	0.9040	0.9063	0.9648	0.111*
C11	0.9852 (4)	0.7788 (5)	0.9145 (3)	0.1032 (17)
H11A	1.0138	0.7418	0.9544	0.124*
H11B	1.0457	0.8275	0.8970	0.124*
C12	0.9542 (5)	0.6881 (5)	0.8633 (3)	0.110 (2)
H12A	1.0208	0.6405	0.8542	0.132*
H12B	0.9314	0.7250	0.8221	0.132*
C13	0.8565 (4)	0.6133 (5)	0.8887 (3)	0.0919 (16)
H13A	0.8344	0.5591	0.8544	0.110*
H13B	0.8823	0.5700	0.9271	0.110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.062 (2)	0.059 (2)	0.091 (3)	−0.0040 (17)	0.0074 (19)	−0.0104 (19)
O1	0.070 (2)	0.076 (2)	0.100 (2)	0.0034 (17)	0.002 (2)	0.0247 (19)
O2	0.186 (4)	0.051 (2)	0.177 (4)	−0.026 (3)	−0.053 (3)	0.031 (3)
S1	0.0775 (8)	0.0692 (8)	0.0839 (7)	−0.0112 (7)	−0.0063 (7)	0.0131 (7)
C1	0.075 (3)	0.055 (3)	0.110 (4)	−0.011 (3)	0.018 (3)	0.016 (3)
C2	0.056 (3)	0.049 (2)	0.067 (3)	−0.004 (2)	0.019 (2)	0.007 (2)
C3	0.057 (3)	0.052 (3)	0.062 (2)	0.000 (2)	0.016 (2)	0.005 (2)
C4	0.086 (3)	0.050 (3)	0.083 (3)	−0.005 (2)	0.008 (3)	0.010 (2)
C5	0.091 (4)	0.073 (4)	0.072 (3)	0.006 (3)	−0.005 (3)	0.007 (3)
C6	0.084 (4)	0.082 (4)	0.061 (3)	−0.008 (3)	0.005 (2)	−0.001 (3)
C7	0.071 (3)	0.066 (3)	0.070 (3)	−0.015 (2)	0.013 (3)	−0.005 (2)
C8	0.062 (3)	0.063 (3)	0.068 (3)	−0.005 (2)	0.000 (2)	−0.003 (2)
C9	0.059 (3)	0.063 (3)	0.099 (3)	0.003 (2)	0.006 (2)	−0.025 (3)
C10	0.088 (4)	0.073 (3)	0.115 (4)	−0.023 (3)	0.010 (3)	−0.014 (3)
C11	0.064 (3)	0.122 (5)	0.123 (4)	−0.025 (3)	0.012 (3)	−0.024 (4)
C12	0.078 (4)	0.131 (5)	0.121 (4)	−0.011 (4)	0.027 (3)	−0.034 (4)
C13	0.074 (3)	0.084 (3)	0.118 (4)	−0.003 (3)	0.019 (3)	−0.035 (3)

Geometric parameters (Å, º) top

N1—C8	1.499 (5)	C7—H7	0.9300
N1—H1A	0.8900	C8—C13	1.488 (6)
N1—H1B	0.8900	C8—C9	1.504 (6)
N1—H1C	0.8900	C8—H8	0.9800
O1—C1	1.260 (5)	C9—C10	1.520 (6)
O2—C1	1.248 (6)	C9—H9A	0.9700
S1—C3	1.780 (4)	C9—H9B	0.9700
S1—S1ⁱ	2.051 (2)	C10—C11	1.490 (7)
C1—C2	1.503 (6)	C10—H10A	0.9700
C2—C7	1.390 (6)	C10—H10B	0.9700
C2—C3	1.397 (5)	C11—C12	1.518 (7)
C3—C4	1.396 (5)	C11—H11A	0.9700
C4—C5	1.374 (6)	C11—H11B	0.9700
C4—H4	0.9300	C12—C13	1.521 (7)
C5—C6	1.355 (6)	C12—H12A	0.9700
C5—H5	0.9300	C12—H12B	0.9700
C6—C7	1.383 (6)	C13—H13A	0.9700
C6—H6	0.9300	C13—H13B	0.9700

C8—N1—H1A	109.5	N1—C8—H8	108.0
C8—N1—H1B	109.5	C9—C8—H8	108.0
H1A—N1—H1B	109.5	C8—C9—C10	110.3 (4)
C8—N1—H1C	109.5	C8—C9—H9A	109.6
H1A—N1—H1C	109.5	C10—C9—H9A	109.6
H1B—N1—H1C	109.5	C8—C9—H9B	109.6
C3—S1—S1ⁱ	105.63 (14)	C10—C9—H9B	109.6
O2—C1—O1	125.4 (5)	H9A—C9—H9B	108.1
O2—C1—C2	116.3 (5)	C11—C10—C9	111.2 (4)
O1—C1—C2	118.2 (4)	C11—C10—H10A	109.4
C7—C2—C3	119.8 (4)	C9—C10—H10A	109.4
C7—C2—C1	117.9 (4)	C11—C10—H10B	109.4
C3—C2—C1	122.3 (4)	C9—C10—H10B	109.4
C4—C3—C2	117.6 (4)	H10A—C10—H10B	108.0
C4—C3—S1	121.9 (3)	C10—C11—C12	110.6 (4)
C2—C3—S1	120.5 (3)	C10—C11—H11A	109.5
C5—C4—C3	121.6 (4)	C12—C11—H11A	109.5
C5—C4—H4	119.2	C10—C11—H11B	109.5
C3—C4—H4	119.2	C12—C11—H11B	109.5
C6—C5—C4	120.5 (5)	H11A—C11—H11B	108.1
C6—C5—H5	119.7	C11—C12—C13	110.4 (4)
C4—C5—H5	119.7	C11—C12—H12A	109.6
C5—C6—C7	119.6 (5)	C13—C12—H12A	109.6
C5—C6—H6	120.2	C11—C12—H12B	109.6
C7—C6—H6	120.2	C13—C12—H12B	109.6
C6—C7—C2	120.8 (4)	H12A—C12—H12B	108.1
C6—C7—H7	119.6	C8—C13—C12	111.0 (4)
C2—C7—H7	119.6	C8—C13—H13A	109.4
C13—C8—N1	109.8 (4)	C12—C13—H13A	109.4
C13—C8—C9	112.5 (4)	C8—C13—H13B	109.4
N1—C8—C9	110.3 (3)	C12—C13—H13B	109.4
C13—C8—H8	108.0	H13A—C13—H13B	108.0

O2—C1—C2—C7	13.8 (6)	C4—C5—C6—C7	−0.9 (7)
O1—C1—C2—C7	−168.7 (4)	C5—C6—C7—C2	2.4 (7)
O2—C1—C2—C3	−165.3 (5)	C3—C2—C7—C6	−0.9 (6)
O1—C1—C2—C3	12.3 (6)	C1—C2—C7—C6	180.0 (4)
C7—C2—C3—C4	−2.0 (6)	C13—C8—C9—C10	54.8 (6)
C1—C2—C3—C4	177.0 (4)	N1—C8—C9—C10	177.8 (4)
C7—C2—C3—S1	177.4 (3)	C8—C9—C10—C11	−55.9 (6)
C1—C2—C3—S1	−3.5 (5)	C9—C10—C11—C12	57.7 (6)
S1ⁱ—S1—C3—C4	2.2 (4)	C10—C11—C12—C13	−57.1 (7)
S1ⁱ—S1—C3—C2	−177.2 (3)	N1—C8—C13—C12	−178.4 (4)
C2—C3—C4—C5	3.6 (6)	C9—C8—C13—C12	−55.1 (6)
S1—C3—C4—C5	−175.9 (4)	C11—C12—C13—C8	55.5 (6)
C3—C4—C5—C6	−2.1 (7)

Symmetry code: (i) −x+1, −y+2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1	0.89	1.91	2.785 (5)	167
N1—H1A···O1ⁱⁱ	0.89	1.96	2.841 (5)	172
N1—H1B···O2ⁱⁱⁱ	0.89	1.84	2.723 (5)	175

Symmetry codes: (ii) y, −x+1, −z+2; (iii) −x+1, −y+1, z.

Experimental details

Crystal data
Chemical formula	2C₆H₁₄N⁺·C₁₄H₈O₄S₂²⁻
M_r	504.69
Crystal system, space group	Tetragonal, I4
Temperature (K)	298
a, c (Å)	11.6411 (15), 20.105 (3)
V (Å³)	2724.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.48 × 0.46 × 0.42

Data collection
Diffractometer	Bruker SMART diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.898, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	5632, 2394, 1398
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.124, 1.05
No. of reflections	2394
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.17
Absolute structure	Flack (1983), 1153 Friedel pairs
Absolute structure parameter	−0.07 (12)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1	0.89	1.91	2.785 (5)	167
N1—H1A···O1ⁱ	0.89	1.96	2.841 (5)	172
N1—H1B···O2ⁱⁱ	0.89	1.84	2.723 (5)	175

Symmetry codes: (i) y, −x+1, −z+2; (ii) −x+1, −y+1, z.

Acknowledgements

We acknowledge the National Natural Science Foundation of China (20771053), the National Basic Research Program (No. 2010CB234601) and the Natural Science Foundation of Shandong Province (Y2008B48) for financial support.

References

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