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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2335.
Published online 2010 August 18. doi:  10.1107/S1600536810032216
PMCID: PMC3008095

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

Abstract

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 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2335-scheme1.jpg

Experimental

Crystal data

  • C14H18N3S2 +·ClO4
  • M r = 391.88
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2335-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.071
  • wR(F 2) = 0.214
  • S = 1.11
  • 1736 reflections
  • 120 parameters
  • 9 restraints
  • H-atom parameters constrained
  • Δρmax = 0.41 e Å−3
  • Δρmin = −0.66 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032216/bh2303Isup2.hkl

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

Acknowledgments

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.

supplementary crystallographic information

Comment

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).

Experimental

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%.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.97 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2 times Ueq(C). The ammonium H-atom was similarly positioned [N—H 0.86 Å] and its temperature factor tied by a factor of 1.2.

The perchlorate ion is disordered about the twofold rotation axis with respect to one O atom; two O atoms were assigned half-occupancy. The Cl—O distances were restrained to within 0.005 Å of each other, as were the O···O separations.

Figures

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.

Crystal data

C14H18N3S2+·ClO4F(000) = 408
Mr = 391.88Dx = 1.460 Mg m3
Monoclinic, P2/nCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yacCell parameters from 1783 reflections
a = 8.1265 (6) Åθ = 3.7–72.5°
b = 9.2291 (7) ŵ = 4.31 mm1
c = 11.9872 (9) ÅT = 293 K
β = 97.534 (7)°Prism, yellow
V = 891.28 (12) Å30.15 × 0.15 × 0.10 mm
Z = 2

Data collection

Oxford Xcalibur Sapphire-3 diffractometer1736 independent reflections
Radiation source: fine-focus sealed tube1427 reflections with I > 2σ(I)
graphiteRint = 0.020
Detector resolution: 16.0855 pixels mm-1θmax = 72.7°, θmin = 4.8°
ω scansh = −6→9
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)k = −11→10
Tmin = 0.345, Tmax = 1.000l = −14→14
3124 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.071H-atom parameters constrained
wR(F2) = 0.214w = 1/[σ2(Fo2) + (0.1333P)2 + 0.2886P] where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
1736 reflectionsΔρmax = 0.41 e Å3
120 parametersΔρmin = −0.66 e Å3
9 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraintsExtinction coefficient: 0.077 (7)
Primary atom site location: structure-invariant direct methods

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

xyzUiso*/UeqOcc. (<1)
Cl10.7500−0.07951 (11)0.75000.0585 (5)
S10.15849 (15)0.6905 (2)0.51373 (9)0.1143 (7)
O10.7006 (6)−0.1628 (4)0.8355 (3)0.1259 (15)
O20.6180 (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
N10.4045 (4)0.6093 (3)0.6688 (2)0.0637 (8)
N20.25000.8558 (5)0.75000.0789 (13)
H20.33450.80070.74630.095*
C10.2997 (4)0.5641 (5)0.5824 (3)0.0703 (10)
C20.2947 (7)0.4216 (6)0.5433 (4)0.0947 (16)
H2A0.21970.39380.48170.114*
C30.4023 (10)0.3248 (6)0.5977 (6)0.108 (2)
H30.40220.22900.57360.130*
C40.5080 (8)0.3672 (5)0.6857 (5)0.1001 (16)
H40.58150.30160.72440.120*
C50.5067 (6)0.5111 (5)0.7187 (3)0.0844 (12)
H50.58230.54010.77960.101*
C60.2658 (7)0.8617 (6)0.5449 (5)0.115 (2)
H6A0.38430.84320.55660.137*
H6B0.24330.92420.47960.137*
C70.2201 (7)0.9415 (5)0.6454 (6)0.114 (2)
H7A0.28411.03040.65510.137*
H7B0.10360.96770.63180.137*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0546 (7)0.0504 (6)0.0705 (7)0.0000.0085 (4)0.000
S10.0748 (8)0.1960 (17)0.0662 (7)0.0179 (8)−0.0137 (5)0.0078 (7)
O10.178 (4)0.106 (2)0.101 (3)0.005 (3)0.046 (3)0.039 (2)
O20.107 (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)
N10.0638 (17)0.0756 (18)0.0492 (14)−0.0023 (13)−0.0020 (12)−0.0074 (12)
N20.077 (3)0.061 (2)0.103 (4)0.0000.030 (3)0.000
C10.0612 (19)0.104 (3)0.0463 (16)−0.0205 (18)0.0108 (13)−0.0068 (17)
C20.100 (3)0.119 (4)0.069 (2)−0.050 (3)0.025 (2)−0.036 (3)
C30.155 (5)0.076 (3)0.108 (4)−0.032 (3)0.071 (4)−0.020 (3)
C40.143 (5)0.076 (3)0.089 (3)0.022 (3)0.043 (3)0.008 (2)
C50.098 (3)0.090 (3)0.062 (2)0.016 (2)−0.0026 (19)−0.005 (2)
C60.100 (3)0.137 (4)0.113 (4)0.027 (3)0.037 (3)0.071 (4)
C70.095 (3)0.082 (3)0.174 (5)0.024 (3)0.052 (4)0.054 (3)

Geometric parameters (Å, °)

Cl1—O2'1.381 (4)C2—C31.357 (8)
Cl1—O1i1.383 (3)C2—H2A0.9300
Cl1—O11.383 (3)C3—C41.329 (10)
Cl1—O21.391 (4)C3—H30.9300
S1—C11.763 (4)C4—C51.387 (7)
S1—C61.820 (7)C4—H40.9300
N1—C11.319 (4)C5—H50.9300
N1—C51.319 (5)C6—C71.500 (9)
N2—C71.475 (6)C6—H6A0.9700
N2—C7ii1.475 (6)C6—H6B0.9700
N2—H20.8600C7—H7A0.9700
C1—C21.395 (7)C7—H7B0.9700
O2'—Cl1—O1i104.9 (8)C2—C3—H3120.1
O2'—Cl1—O1113.1 (4)C3—C4—C5118.7 (5)
O1i—Cl1—O1112.4 (3)C3—C4—H4120.6
O2'—Cl1—O2111.9 (4)C5—C4—H4120.6
O1i—Cl1—O2102.5 (12)N1—C5—C4123.8 (5)
O1—Cl1—O2111.4 (4)N1—C5—H5118.1
O2i—Cl1—O2117 (2)C4—C5—H5118.1
C1—S1—C6102.3 (2)C7—C6—S1115.4 (3)
C1—N1—C5116.3 (4)C7—C6—H6A108.4
C7—N2—C7ii115.2 (6)S1—C6—H6A108.4
C7—N2—H2108.5C7—C6—H6B108.4
C7ii—N2—H2108.5S1—C6—H6B108.4
N1—C1—C2123.3 (4)H6A—C6—H6B107.5
N1—C1—S1118.1 (3)N2—C7—C6112.9 (4)
C2—C1—S1118.6 (3)N2—C7—H7A109.0
C3—C2—C1118.1 (4)C6—C7—H7A109.0
C3—C2—H2A121.0N2—C7—H7B109.0
C1—C2—H2A121.0C6—C7—H7B109.0
C4—C3—C2119.8 (5)H7A—C7—H7B107.8
C4—C3—H3120.1
C5—N1—C1—C2−0.5 (5)C2—C3—C4—C5−0.9 (8)
C5—N1—C1—S1179.2 (3)C1—N1—C5—C4−0.3 (6)
C6—S1—C1—N125.3 (3)C3—C4—C5—N11.0 (8)
C6—S1—C1—C2−155.0 (3)C1—S1—C6—C7−94.7 (4)
N1—C1—C2—C30.6 (6)C7ii—N2—C7—C6154.1 (5)
S1—C1—C2—C3−179.1 (3)S1—C6—C7—N258.4 (5)
C1—C2—C3—C40.1 (7)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···N10.862.112.832 (5)141

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2303).

References

  • An, Y., Li, X.-F., Chen, H.-G. & Dong, L.-H. (2010). Acta Cryst. E66, o101.
  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography