Bis(cyclohexylammonium) 2,2′-disulfanediyldibenzoate

Abstract

In the title molecular salt, 2C₆H₁₄N⁺·C₁₄H₈O₄S₂ ²⁻, 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⁺·C₁₄H₈O₄S₂ ²⁻

• M _r = 504.69

• Tetragonal,

• a = 11.6411 (15) Å

• c = 20.105 (3) Å

• V = 2724.6 (6) ų

• 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[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 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)

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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%.

Refinement

The H atoms were positioned geometrically with aromatic C—H distances of 0.93 Å, and refined as riding on their parent atoms, with U_iso(H) = 1.2 U_eq(C). The H atoms were positioned geometrically with cyclohexylamine C—H distances of 0.97 Å and refined as riding on their parent atoms, with U_iso(H) = 1.5 U_eq(C). The N—H distance is 0.89 Å with U_iso(H) = 1.2 U_eq(N).

Figures

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)

Crystal data

2C6H14N+·C14H8O4S22−	Dx = 1.230 Mg m−3
Mr = 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

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

Refinement

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(Fo2) + (0.0468P)2 + 1.0167P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
2394 reflections	Δρmax = 0.17 e Å−3
155 parameters	Δρmin = −0.17 e Å−3
0 restraints	Absolute structure: Flack (1983), 1153 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.07 (12)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y+2, z.

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···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.