Bis[2-(2-pyridyl­sulfan­yl)eth­yl]ammonium perchlorate

Wang, G.-Q.; Ma, C.-H.; Li, X.-F.; Li, W.-G.; Ng, S.W.

doi:10.1107/S1600536810032216

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2335

https://doi.org/10.1107/S1600536810032216

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Bis[2-(2-pyridylsulfanyl)ethyl]ammonium perchlorate

Guo-Qing Wang,^a Cong-Hui Ma,^b Xiao-Feng Li,^c Wen-Ge Li ^c and Seik Weng Ng ^d ^*

^aShanghai Sunvea Chemical Materials Science and Technology Co. Ltd, Shanghai 201611, People's Republic of China, ^bQingdao University of Science and Technology, Qingdao 266042, People's Republic of China, ^cInstitute of Marine Materials Science and Engineering, Shanghai Maritime University, Shanghai 201306, People's Republic of China, and ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 21 July 2010; accepted 10 August 2010; online 18 August 2010)

The cation and anion of the title salt, C₁₄H₁₈N₃S₂⁺·ClO₄⁻, lie on a twofold rotation axis. The cation is a W-shaped entity with the aromatic rings at the ends; the ammonium NH₂⁺ group is a hydrogen-bond donor to the pyridyl N atoms. The perchlorate ion has one O atom disordered over two sites in a 0.50:0.50 ratio.

Related literature

For the structure of tris[2-(2-pyridylsulfanyl)ethyl]ammonium perchlorate, see: An et al. (2010 ).

Experimental

Crystal data

C₁₄H₁₈N₃S₂⁺·ClO₄⁻
M_r = 391.88
Monoclinic, P 2/n
a = 8.1265 (6) Å
b = 9.2291 (7) Å
c = 11.9872 (9) Å
β = 97.534 (7)°
V = 891.28 (12) Å³
Z = 2
Cu Kα radiation
μ = 4.31 mm⁻¹
T = 293 K
0.15 × 0.15 × 0.10 mm

Data collection

Oxford Xcalibur Sapphire-3 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.345, T_max = 1.000
3124 measured reflections
1736 independent reflections
1427 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.214
S = 1.11
1736 reflections
120 parameters
9 restraints
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1	0.86	2.11	2.832 (5)	141

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810032216/bh2303sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032216/bh2303Isup2.hkl

checkCIF report

Comment top

We are engaged in the study of metal complexes of di- and tri-(pyridylsulfanyl)alkylamines as such compounds owing to their flexible nature. We reported earlier the synthesis of tris[2-(2-pyridylsulfanyl)ethyl]amine, whose reaction with copper perchlorate gave instead tris[2-(2-pyridylsulfanyl)ethyl]ammonium perchlorate (An et al., 2010). The two-legged bis[2-(2-pyridylsulfanyl)ethyl]amine, in the present study, reacted with copper perchlorate to afford the corresponding ammonium perchlorate (Scheme and Fig. 1).

Related literature top

For the structure of tris[2-(2-pyridylsulfanyl)ethyl]ammonium perchlorate, see: An et al. (2010).

Experimental top

Bis(2-chloroethyl)ammonium hydrochloride (8.92 g, 0.05 mol) in ethanol (100 ml) was added to a solution (353 K) of 2-mercaptopyridine (12.23 g, 0.11 mol) and potassium hydroxide (6.17 g, 0.11 mol) in ethanol (200 ml). The mixture was heated at 353 K for 8 h. The solvent was removed to yield a yellow oil; this was column chromatographed with ethly acetate/petroleum ether (3/5 v/v) as eluent; yield 65%. ¹H NMR (CDCl₃, 400 MHz, p.p.m.): 3.316–3.349 (t, 4H), 2.959–2.992 (t, 4H), 6.924–6.960 (m, 2H), 7.154–7.173 (m, 2H), 7.416–7.459 (m, 2H), 8.382–8.393 (m, 2H).

The title salt was obtained from the reaction of bis[2-(2-pyridylsulfanyl)ethyl]amine (0.5 mmol, 0.146 g) and copper perchlorate (0.5 mmol, 0.132 g) in ethanol. Colorless crystals were separated from the blue solution after three days. CH&N elemental analysis, calculated for C₁₄H₁₈O₄N₃S₂Cl: C 42.91, H 4.63, N 10.72%; Found: C 42.73, H 4.35, N 11.02%.

Structure description top

For the structure of tris[2-(2-pyridylsulfanyl)ethyl]ammonium perchlorate, see: An et al. (2010).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [C₁₄H₁₈N₃S₂]⁺[ClO₄]^- at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. For the cation, the unlabeled atoms are related to the labeled ones by symmetry 1/2-x, y, 3/2-z.

Bis[2-(2-pyridylsulfanyl)ethyl]ammonium perchlorate top

Crystal data top

C₁₄H₁₈N₃S₂⁺·ClO₄⁻	F(000) = 408
M_r = 391.88	D_x = 1.460 Mg m⁻³
Monoclinic, P2/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yac	Cell parameters from 1783 reflections
a = 8.1265 (6) Å	θ = 3.7–72.5°
b = 9.2291 (7) Å	µ = 4.31 mm⁻¹
c = 11.9872 (9) Å	T = 293 K
β = 97.534 (7)°	Prism, yellow
V = 891.28 (12) Å³	0.15 × 0.15 × 0.10 mm
Z = 2

Data collection top

Oxford Xcalibur Sapphire-3 diffractometer	1736 independent reflections
Radiation source: fine-focus sealed tube	1427 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 16.0855 pixels mm^-1	θ_max = 72.7°, θ_min = 4.8°
ω scans	h = −6→9
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −11→10
T_min = 0.345, T_max = 1.000	l = −14→14
3124 measured reflections

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)] = 0.071	H-atom parameters constrained
wR(F²) = 0.214	w = 1/[σ²(F_o²) + (0.1333P)² + 0.2886P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
1736 reflections	Δρ_max = 0.41 e Å⁻³
120 parameters	Δρ_min = −0.66 e Å⁻³
9 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.077 (7)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₄H₁₈N₃S₂⁺·ClO₄⁻	V = 891.28 (12) Å³
M_r = 391.88	Z = 2
Monoclinic, P2/n	Cu Kα radiation
a = 8.1265 (6) Å	µ = 4.31 mm⁻¹
b = 9.2291 (7) Å	T = 293 K
c = 11.9872 (9) Å	0.15 × 0.15 × 0.10 mm
β = 97.534 (7)°

Data collection top

Oxford Xcalibur Sapphire-3 diffractometer	1736 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1427 reflections with I > 2σ(I)
T_min = 0.345, T_max = 1.000	R_int = 0.020
3124 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	9 restraints
wR(F²) = 0.214	H-atom parameters constrained
S = 1.11	Δρ_max = 0.41 e Å⁻³
1736 reflections	Δρ_min = −0.66 e Å⁻³
120 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.7500	−0.07951 (11)	0.7500	0.0585 (5)
S1	0.15849 (15)	0.6905 (2)	0.51373 (9)	0.1143 (7)
O1	0.7006 (6)	−0.1628 (4)	0.8355 (3)	0.1259 (15)
O2	0.6180 (11)	−0.001 (2)	0.6944 (18)	0.231 (14)	0.50
O2'	0.8847 (16)	0.0079 (15)	0.7855 (10)	0.184 (11)	0.50
N1	0.4045 (4)	0.6093 (3)	0.6688 (2)	0.0637 (8)
N2	0.2500	0.8558 (5)	0.7500	0.0789 (13)
H2	0.3345	0.8007	0.7463	0.095*
C1	0.2997 (4)	0.5641 (5)	0.5824 (3)	0.0703 (10)
C2	0.2947 (7)	0.4216 (6)	0.5433 (4)	0.0947 (16)
H2A	0.2197	0.3938	0.4817	0.114*
C3	0.4023 (10)	0.3248 (6)	0.5977 (6)	0.108 (2)
H3	0.4022	0.2290	0.5736	0.130*
C4	0.5080 (8)	0.3672 (5)	0.6857 (5)	0.1001 (16)
H4	0.5815	0.3016	0.7244	0.120*
C5	0.5067 (6)	0.5111 (5)	0.7187 (3)	0.0844 (12)
H5	0.5823	0.5401	0.7796	0.101*
C6	0.2658 (7)	0.8617 (6)	0.5449 (5)	0.115 (2)
H6A	0.3843	0.8432	0.5566	0.137*
H6B	0.2433	0.9242	0.4796	0.137*
C7	0.2201 (7)	0.9415 (5)	0.6454 (6)	0.114 (2)
H7A	0.2841	1.0304	0.6551	0.137*
H7B	0.1036	0.9677	0.6318	0.137*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0546 (7)	0.0504 (6)	0.0705 (7)	0.000	0.0085 (4)	0.000
S1	0.0748 (8)	0.1960 (17)	0.0662 (7)	0.0179 (8)	−0.0137 (5)	0.0078 (7)
O1	0.178 (4)	0.106 (2)	0.101 (3)	0.005 (3)	0.046 (3)	0.039 (2)
O2	0.107 (12)	0.31 (3)	0.29 (2)	0.088 (14)	0.074 (13)	0.21 (2)
O2'	0.185 (18)	0.188 (15)	0.198 (14)	−0.139 (14)	0.098 (13)	−0.118 (12)
N1	0.0638 (17)	0.0756 (18)	0.0492 (14)	−0.0023 (13)	−0.0020 (12)	−0.0074 (12)
N2	0.077 (3)	0.061 (2)	0.103 (4)	0.000	0.030 (3)	0.000
C1	0.0612 (19)	0.104 (3)	0.0463 (16)	−0.0205 (18)	0.0108 (13)	−0.0068 (17)
C2	0.100 (3)	0.119 (4)	0.069 (2)	−0.050 (3)	0.025 (2)	−0.036 (3)
C3	0.155 (5)	0.076 (3)	0.108 (4)	−0.032 (3)	0.071 (4)	−0.020 (3)
C4	0.143 (5)	0.076 (3)	0.089 (3)	0.022 (3)	0.043 (3)	0.008 (2)
C5	0.098 (3)	0.090 (3)	0.062 (2)	0.016 (2)	−0.0026 (19)	−0.005 (2)
C6	0.100 (3)	0.137 (4)	0.113 (4)	0.027 (3)	0.037 (3)	0.071 (4)
C7	0.095 (3)	0.082 (3)	0.174 (5)	0.024 (3)	0.052 (4)	0.054 (3)

Geometric parameters (Å, º) top

Cl1—O2'	1.381 (4)	C2—C3	1.357 (8)
Cl1—O1ⁱ	1.383 (3)	C2—H2A	0.9300
Cl1—O1	1.383 (3)	C3—C4	1.329 (10)
Cl1—O2	1.391 (4)	C3—H3	0.9300
S1—C1	1.763 (4)	C4—C5	1.387 (7)
S1—C6	1.820 (7)	C4—H4	0.9300
N1—C1	1.319 (4)	C5—H5	0.9300
N1—C5	1.319 (5)	C6—C7	1.500 (9)
N2—C7	1.475 (6)	C6—H6A	0.9700
N2—C7ⁱⁱ	1.475 (6)	C6—H6B	0.9700
N2—H2	0.8600	C7—H7A	0.9700
C1—C2	1.395 (7)	C7—H7B	0.9700

O2'—Cl1—O1ⁱ	104.9 (8)	C2—C3—H3	120.1
O2'—Cl1—O1	113.1 (4)	C3—C4—C5	118.7 (5)
O1ⁱ—Cl1—O1	112.4 (3)	C3—C4—H4	120.6
O2'—Cl1—O2	111.9 (4)	C5—C4—H4	120.6
O1ⁱ—Cl1—O2	102.5 (12)	N1—C5—C4	123.8 (5)
O1—Cl1—O2	111.4 (4)	N1—C5—H5	118.1
O2ⁱ—Cl1—O2	117 (2)	C4—C5—H5	118.1
C1—S1—C6	102.3 (2)	C7—C6—S1	115.4 (3)
C1—N1—C5	116.3 (4)	C7—C6—H6A	108.4
C7—N2—C7ⁱⁱ	115.2 (6)	S1—C6—H6A	108.4
C7—N2—H2	108.5	C7—C6—H6B	108.4
C7ⁱⁱ—N2—H2	108.5	S1—C6—H6B	108.4
N1—C1—C2	123.3 (4)	H6A—C6—H6B	107.5
N1—C1—S1	118.1 (3)	N2—C7—C6	112.9 (4)
C2—C1—S1	118.6 (3)	N2—C7—H7A	109.0
C3—C2—C1	118.1 (4)	C6—C7—H7A	109.0
C3—C2—H2A	121.0	N2—C7—H7B	109.0
C1—C2—H2A	121.0	C6—C7—H7B	109.0
C4—C3—C2	119.8 (5)	H7A—C7—H7B	107.8
C4—C3—H3	120.1

C5—N1—C1—C2	−0.5 (5)	C2—C3—C4—C5	−0.9 (8)
C5—N1—C1—S1	179.2 (3)	C1—N1—C5—C4	−0.3 (6)
C6—S1—C1—N1	25.3 (3)	C3—C4—C5—N1	1.0 (8)
C6—S1—C1—C2	−155.0 (3)	C1—S1—C6—C7	−94.7 (4)
N1—C1—C2—C3	0.6 (6)	C7ⁱⁱ—N2—C7—C6	154.1 (5)
S1—C1—C2—C3	−179.1 (3)	S1—C6—C7—N2	58.4 (5)
C1—C2—C3—C4	0.1 (7)

Symmetry codes: (i) −x+3/2, y, −z+3/2; (ii) −x+1/2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.86	2.11	2.832 (5)	141

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈N₃S₂⁺·ClO₄⁻
M_r	391.88
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	293
a, b, c (Å)	8.1265 (6), 9.2291 (7), 11.9872 (9)
β (°)	97.534 (7)
V (Å³)	891.28 (12)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	4.31
Crystal size (mm)	0.15 × 0.15 × 0.10

Data collection
Diffractometer	Oxford Xcalibur Sapphire-3
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.345, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3124, 1736, 1427
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.214, 1.11
No. of reflections	1736
No. of parameters	120
No. of restraints	9
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.66

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.86	2.11	2.832 (5)	141

Acknowledgements

The authors thank the Special Foundation for Nanotechnology of the Shanghai Committee for Science and Technology (grant No. 1052nm00600), the Foundation of the Science and Technology Programme of Shanghai Maritime University (grant No. 20100128), the State Key Laboratory of Pollution Control and Resource Reuse Foundation (grant No. PCRRF09001) and the University of Malaya for supporting this study.

References

An, Y., Li, X.-F., Chen, H.-G. & Dong, L.-H. (2010). Acta Cryst. E66, o101. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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