2,2,6,6-Tetra­methyl­piperidinium penta­chloro­benzene­thiol­ate

Baranowska, K.; Piwowarska, N.

doi:10.1107/S1600536808025877

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1781

doi:10.1107/S1600536808025877

Open

access

2,2,6,6-Tetramethylpiperidinium pentachlorobenzenethiolate

Katarzyna Baranowska ^a ^* and Natalia Piwowarska ^a

^aDepartment of Inorganic Chemistry, Faculty of Chemistry, Gdańsk University of Technology, 11/12 G. Narutowicz Street, 80952-PL Gdańsk, Poland
^*Correspondence e-mail: kasiab29@wp.pl

(Received 4 July 2008; accepted 11 August 2008; online 20 August 2008)

In the crystal structure of the title compound, C₉H₂₀N⁺·C₆Cl₅S⁻, two cation–anion pairs are linked by N—H⋯S hydrogen bonds to produce a cyclic aggregate of R₄²(8) type. The dimers are interconnected via π–π stacking [centroid–centroid distance = 3.851(2) Å] and weak C—H⋯Cl hydrogen-bonding interactions.

Related literature

For the structures of similar salts and comparison of bond distances, see: Baranowska et al. (2008 ); Dołęga et al. (2008 ); Baranowska (2007 ); Pladzyk & Baranowska (2007 ); Baranowska, Chojnacki, Konitz et al. (2006 ); Baranowska, Chojnacki, Gosiewska & Wojnowski (2006 ); Baranowska et al. (2003 ). For the graph-set description of hydrogen-bonding patterns, see: Bernstein et al. (1995 ); Etter (1990 ). For synthesis techniques, see: Perrin & Armarego (1988 ).

Experimental

Crystal data

C₉H₂₀N⁺·C₆Cl₅S⁻
M_r = 423.63
Triclinic, $[P \overline 1]$
a = 8.4230 (5) Å
b = 10.5081 (4) Å
c = 11.6142 (6) Å
α = 110.946 (4)°
β = 102.614 (4)°
γ = 95.286 (4)°
V = 920.39 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 120 (2) K
0.21 × 0.14 × 0.09 mm

Data collection

Oxford Diffraction KM4 CCD diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.779, T_max = 0.866
5583 measured reflections
3161 independent reflections
2930 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.097
S = 1.21
3161 reflections
279 parameters
All H-atom parameters refined
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯S1ⁱ	0.87 (2)	2.44 (2)	3.301 (2)	170 (2)
N1—H1A⋯S1	0.90 (2)	2.39 (2)	3.226 (2)	157 (2)
C14—H14C⋯Cl1ⁱⁱ	0.91 (3)	3.02 (2)	3.803 (2)	145 (2)
C15—H15B⋯Cl1	0.93 (2)	2.88 (2)	3.748 (2)	156 (2)
C13—H13B⋯Cl3ⁱⁱⁱ	0.98 (2)	3.02 (2)	3.905 (2)	151 (2)
C13—H13C⋯Cl4^iv	0.98 (2)	3.08 (2)	3.782 (2)	129 (2)
C9—H9B⋯Cl4^iv	0.95 (2)	2.92 (2)	3.708 (2)	141 (2)
C15—H15C⋯Cl4^v	0.94 (2)	2.94 (2)	3.646 (2)	133 (2)
C8—H8B⋯Cl5^vi	0.89 (3)	2.87 (3)	3.748 (2)	169 (2)
C10—H10A⋯Cl5ⁱ	0.97 (2)	3.02 (2)	3.966 (2)	167 (2)
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+2, -y, -z+1; (iii) -x+1, -y, -z; (iv) x, y, z+1; (v) x+1, y, z+1; (vi) -x+1, -y+1, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808025877/im2076sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025877/im2076Isup2.hkl

checkCIF report

Comment top

The crystal structure of the title compound shows an asymmetric unit consisting of one pentachlorobenzenethiolate anion and one 2,2,6,6-tetramethylpiperidinium cation. The ammonium thiolate forms a dimer [C₆Cl₅S^(-) H₂N⁽⁺⁾C₅H₆Me₄]₂(Fig. 1) in which four charge-assisted ⁽⁺⁾N—H···S^(-) hydrogen bonds form a stable core. This pattern of an eight-membered ring system with four donors and two acceptors is known as R₄²(8), using Etter's graph set analysis (Etter, 1990; Bernstein et al., 1995). In the crystal the dimers pack as seperate units bound together by van der Waals forces and weak C—H···Cl hydrogen bonds (Fig. 2). Similar (thiol-amine)₂ ring formation has been observed in other ammonium salts (Baranowska et al., 2008; Baranowska, 2007; Baranowska, Chojnacki, Konitz et al., 2006; Baranowska, Chojnacki, Gosiewska & Wojnowski, 2006). The dimers are interconnected via π–π stacking interactions between Cg1 and Cg2, where Cg1 is the centroid of the C1–C6 ring and Cg2 is the centroid of the C1–C6 ring at (1-x, -y, -z). The centroid-to-centroid (CC) distance is 3.851 (2) Å and the angle subtended by the plane normal to CC is 25.03°. Interactions of the C—H···Cl type are weak with the shortest H···Cl distance measuring to 2.86 Å.

The N···S distances lie in the range 3.226 (2)–3.301 (2) Å and are therefore comparable with values observed in zinc and cobalt silanethiolates complexes (Dołęga et al., 2008; Pladzyk & Baranowska, 2007) or aromatic thiolates (Baranowska, 2007; Baranowska et al. 2003).

Related literature top

For the structures of similar salts and comparison of bond distances, see: Baranowska et al. (2008); Dołęga et al. (2008); Baranowska (2007); Pladzyk & Baranowska (2007); Baranowska, Chojnacki, Konitz et al. (2006); Baranowska, Chojnacki, Gosiewska & Wojnowski (2006); Baranowska et al. (2003). For the graph-set description of hydrogen-bonding patterns, see: Bernstein et al. (1995); Etter (1990). For synthesis techniques, see: Perrin & Armarego (1988).

Experimental top

All manipulations were carried out under an atmosphere of nitrogen using standard Schlenk techniques. The solvents were purified and dried by standard methods (Perrin & Armarego, 1988).

C₆Cl₅SH (0.570 g, 2 mmol) was dissolved in tetrahydrofurane (ca 10 ml). Traces of impurities were removed by filtration under an argon atmosphere. Next, a portion of 2,2,6,6-tetramethylpiperidine (0338 ml, 2 mmol) was added at room temperature. The color of the mixture changed to dark red. Slow crystallization from THF at 5° C yielded yellow crystals suitable for X-ray diffraction.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Structure of [C₆Cl₅S^(-)H₂N⁽⁺⁾C₅H₆Me₄]₂, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. C-bound H atoms have been omitted for clarity.
	Fig. 2. The crystal packing of (I), viewed approximately down the a axis.

2,2,6,6-Tetramethylpiperidinium pentachlorobenzenethiolate top

Crystal data top

C₉H₂₀N⁺·C₆Cl₅S⁻	Z = 2
M_r = 423.63	F(000) = 436
Triclinic, P1	D_x = 1.529 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4230 (5) Å	Cell parameters from 6782 reflections
b = 10.5081 (4) Å	θ = 2.0–32.2°
c = 11.6142 (6) Å	µ = 0.90 mm⁻¹
α = 110.946 (4)°	T = 120 K
β = 102.614 (4)°	Prism, yellow
γ = 95.286 (4)°	0.21 × 0.14 × 0.09 mm
V = 920.39 (8) Å³

Data collection top

Oxford Diffraction KM4 CCD diffractometer	3161 independent reflections
Graphite monochromator	2930 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm^-1	R_int = 0.019
0.75° wide ω scans	θ_max = 25.1°, θ_min = 2.0°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)	h = −10→10
T_min = 0.779, T_max = 0.866	k = −12→12
5583 measured reflections	l = −13→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	All H-atom parameters refined
S = 1.21	w = 1/[σ²(F_o²) + (0.0605P)² + 0.2069P] where P = (F_o² + 2F_c²)/3
3161 reflections	(Δ/σ)_max < 0.001
279 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₉H₂₀N⁺·C₆Cl₅S⁻	γ = 95.286 (4)°
M_r = 423.63	V = 920.39 (8) Å³
Triclinic, P1	Z = 2
a = 8.4230 (5) Å	Mo Kα radiation
b = 10.5081 (4) Å	µ = 0.90 mm⁻¹
c = 11.6142 (6) Å	T = 120 K
α = 110.946 (4)°	0.21 × 0.14 × 0.09 mm
β = 102.614 (4)°

Data collection top

Oxford Diffraction KM4 CCD diffractometer	3161 independent reflections
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)	2930 reflections with I > 2σ(I)
T_min = 0.779, T_max = 0.866	R_int = 0.019
5583 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.097	All H-atom parameters refined
S = 1.21	Δρ_max = 0.67 e Å⁻³
3161 reflections	Δρ_min = −0.44 e Å⁻³
279 parameters

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
Cl1	0.93273 (6)	0.07455 (4)	0.24695 (4)	0.02718 (15)
Cl2	0.82093 (6)	−0.14335 (4)	−0.03115 (4)	0.02729 (15)
Cl3	0.58390 (6)	−0.08459 (5)	−0.24491 (4)	0.03127 (16)
Cl4	0.44756 (6)	0.19129 (5)	−0.17487 (4)	0.02934 (15)
Cl5	0.57116 (6)	0.41671 (5)	0.09814 (4)	0.02804 (15)
S1	0.80012 (6)	0.36293 (4)	0.32284 (4)	0.02321 (15)
C1	0.7446 (2)	0.23869 (17)	0.16726 (15)	0.0186 (4)
C2	0.7987 (2)	0.11030 (17)	0.13157 (16)	0.0191 (4)
C3	0.7504 (2)	0.01128 (17)	0.00666 (17)	0.0203 (4)
C4	0.6429 (2)	0.03617 (18)	−0.08959 (15)	0.0211 (4)
C5	0.5855 (2)	0.16113 (18)	−0.05775 (16)	0.0207 (4)
C6	0.6375 (2)	0.26039 (18)	0.06694 (17)	0.0197 (4)
N1	0.89358 (18)	0.38134 (15)	0.61365 (13)	0.0176 (3)
C7	0.7556 (2)	0.43976 (19)	0.66962 (16)	0.0238 (4)
C8	0.8123 (3)	0.4751 (2)	0.81401 (17)	0.0300 (4)
C9	0.8679 (2)	0.3550 (2)	0.84610 (18)	0.0309 (4)
C10	1.0115 (2)	0.31139 (19)	0.79179 (17)	0.0246 (4)
C11	0.9685 (2)	0.26709 (17)	0.64589 (16)	0.0208 (4)
C12	0.7388 (3)	0.5705 (2)	0.64296 (19)	0.0299 (4)
C13	0.5913 (2)	0.3374 (2)	0.60334 (19)	0.0309 (4)
C14	0.8482 (3)	0.12818 (19)	0.57438 (19)	0.0281 (4)
C15	1.1256 (2)	0.25939 (19)	0.60015 (18)	0.0252 (4)
H14B	0.758 (3)	0.125 (2)	0.611 (2)	0.030 (5)*
H13B	0.566 (3)	0.305 (2)	0.510 (2)	0.029 (5)*
H15C	1.177 (2)	0.190 (2)	0.6161 (19)	0.025 (5)*
H13A	0.511 (3)	0.388 (3)	0.627 (2)	0.039 (6)*
H13C	0.586 (3)	0.253 (3)	0.622 (2)	0.036 (6)*
H14A	0.802 (3)	0.112 (2)	0.486 (2)	0.026 (5)*
H15A	1.208 (3)	0.347 (2)	0.6435 (19)	0.022 (5)*
H15B	1.102 (3)	0.235 (2)	0.513 (2)	0.037 (6)*
H14C	0.908 (3)	0.061 (2)	0.580 (2)	0.034 (6)*
H12B	0.838 (3)	0.636 (3)	0.679 (3)	0.049 (7)*
H10B	1.046 (3)	0.235 (2)	0.808 (2)	0.031 (5)*
H10A	1.105 (3)	0.388 (2)	0.8295 (19)	0.026 (5)*
H12C	0.703 (3)	0.549 (2)	0.552 (2)	0.029 (5)*
H9B	0.780 (3)	0.277 (2)	0.810 (2)	0.035 (6)*
H1B	0.974 (3)	0.452 (2)	0.640 (2)	0.024 (5)*
H12A	0.661 (3)	0.616 (2)	0.682 (2)	0.032 (6)*
H1A	0.860 (3)	0.349 (2)	0.528 (2)	0.024 (5)*
H9A	0.896 (3)	0.382 (2)	0.935 (2)	0.032 (5)*
H8A	0.906 (3)	0.553 (2)	0.851 (2)	0.025 (5)*
H8B	0.728 (3)	0.501 (2)	0.846 (2)	0.040 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0345 (3)	0.0226 (2)	0.0221 (2)	0.00649 (19)	−0.00126 (19)	0.01083 (18)
Cl2	0.0355 (3)	0.0198 (2)	0.0260 (3)	0.00788 (19)	0.0098 (2)	0.0066 (2)
Cl3	0.0350 (3)	0.0329 (3)	0.0166 (2)	0.0010 (2)	0.00332 (19)	0.00236 (19)
Cl4	0.0234 (3)	0.0430 (3)	0.0236 (2)	0.0058 (2)	0.00059 (19)	0.0187 (2)
Cl5	0.0284 (3)	0.0250 (3)	0.0323 (3)	0.01072 (19)	0.0055 (2)	0.0130 (2)
S1	0.0333 (3)	0.0174 (2)	0.0158 (2)	0.00052 (18)	0.00399 (19)	0.00531 (18)
C1	0.0201 (8)	0.0188 (8)	0.0169 (8)	−0.0004 (6)	0.0056 (7)	0.0075 (7)
C2	0.0193 (8)	0.0206 (8)	0.0187 (8)	0.0019 (7)	0.0038 (7)	0.0105 (7)
C3	0.0212 (9)	0.0178 (8)	0.0223 (9)	0.0012 (7)	0.0072 (7)	0.0081 (7)
C4	0.0215 (9)	0.0241 (9)	0.0144 (8)	−0.0020 (7)	0.0050 (7)	0.0052 (7)
C5	0.0156 (8)	0.0294 (9)	0.0195 (8)	0.0016 (7)	0.0032 (7)	0.0139 (7)
C6	0.0184 (8)	0.0200 (8)	0.0227 (8)	0.0023 (6)	0.0066 (7)	0.0104 (7)
N1	0.0209 (8)	0.0174 (7)	0.0148 (7)	0.0040 (6)	0.0035 (6)	0.0072 (6)
C7	0.0224 (9)	0.0317 (9)	0.0188 (8)	0.0106 (7)	0.0067 (7)	0.0094 (7)
C8	0.0248 (10)	0.0456 (12)	0.0189 (9)	0.0122 (9)	0.0069 (8)	0.0097 (8)
C9	0.0293 (10)	0.0452 (12)	0.0177 (9)	0.0010 (9)	0.0032 (8)	0.0150 (8)
C10	0.0260 (10)	0.0246 (9)	0.0227 (9)	0.0028 (8)	0.0004 (7)	0.0126 (7)
C11	0.0239 (9)	0.0182 (8)	0.0209 (8)	0.0057 (7)	0.0025 (7)	0.0100 (7)
C12	0.0333 (11)	0.0302 (10)	0.0270 (10)	0.0163 (9)	0.0078 (9)	0.0098 (8)
C13	0.0206 (10)	0.0465 (12)	0.0268 (10)	0.0061 (9)	0.0032 (8)	0.0175 (9)
C14	0.0321 (11)	0.0211 (9)	0.0284 (10)	0.0008 (8)	0.0012 (8)	0.0117 (8)
C15	0.0267 (10)	0.0222 (9)	0.0243 (10)	0.0086 (8)	0.0036 (8)	0.0073 (8)

Geometric parameters (Å, º) top

Cl1—C2	1.7286 (16)	C8—H8B	0.89 (3)
Cl2—C3	1.7228 (18)	C9—C10	1.516 (3)
Cl3—C4	1.7225 (16)	C9—H9B	0.95 (2)
Cl4—C5	1.7283 (16)	C9—H9A	0.94 (2)
Cl5—C6	1.7246 (18)	C10—C11	1.535 (2)
S1—C1	1.7377 (16)	C10—H10B	0.94 (2)
C1—C6	1.411 (2)	C10—H10A	0.97 (2)
C1—C2	1.413 (2)	C11—C15	1.528 (3)
C2—C3	1.392 (2)	C11—C14	1.530 (2)
C3—C4	1.396 (3)	C12—H12B	0.94 (3)
C4—C5	1.394 (3)	C12—H12C	0.96 (2)
C5—C6	1.391 (2)	C12—H12A	0.95 (3)
N1—C7	1.525 (2)	C13—H13B	0.98 (2)
N1—C11	1.529 (2)	C13—H13A	0.92 (3)
N1—H1B	0.87 (2)	C13—H13C	0.98 (2)
N1—H1A	0.90 (2)	C14—H14B	0.95 (2)
C7—C12	1.524 (3)	C14—H14A	0.96 (2)
C7—C13	1.528 (3)	C14—H14C	0.91 (3)
C7—C8	1.533 (2)	C15—H15C	0.94 (2)
C8—C9	1.524 (3)	C15—H15A	0.99 (2)
C8—H8A	0.98 (2)	C15—H15B	0.93 (2)

C6—C1—C2	115.27 (15)	C10—C9—H9A	111.4 (14)
C6—C1—S1	120.91 (13)	C8—C9—H9A	108.9 (13)
C2—C1—S1	123.81 (13)	H9B—C9—H9A	108.0 (19)
C3—C2—C1	122.83 (15)	C9—C10—C11	112.65 (15)
C3—C2—Cl1	118.24 (13)	C9—C10—H10B	112.4 (14)
C1—C2—Cl1	118.93 (13)	C11—C10—H10B	105.7 (13)
C2—C3—C4	120.12 (16)	C9—C10—H10A	109.9 (12)
C2—C3—Cl2	120.71 (13)	C11—C10—H10A	107.8 (12)
C4—C3—Cl2	119.16 (14)	H10B—C10—H10A	108.1 (18)
C5—C4—C3	118.69 (16)	C15—C11—N1	105.70 (13)
C5—C4—Cl3	120.68 (13)	C15—C11—C14	109.75 (15)
C3—C4—Cl3	120.62 (14)	N1—C11—C14	110.28 (14)
C6—C5—C4	120.59 (16)	C15—C11—C10	110.55 (14)
C6—C5—Cl4	120.17 (14)	N1—C11—C10	107.83 (13)
C4—C5—Cl4	119.24 (13)	C14—C11—C10	112.49 (15)
C5—C6—C1	122.46 (16)	C7—C12—H12B	112.2 (16)
C5—C6—Cl5	118.30 (13)	C7—C12—H12C	111.0 (13)
C1—C6—Cl5	119.22 (13)	H12B—C12—H12C	109 (2)
C7—N1—C11	120.66 (13)	C7—C12—H12A	110.5 (14)
C7—N1—H1B	104.8 (14)	H12B—C12—H12A	105 (2)
C11—N1—H1B	106.9 (14)	H12C—C12—H12A	108.8 (19)
C7—N1—H1A	109.8 (13)	C7—C13—H13B	111.6 (12)
C11—N1—H1A	106.0 (13)	C7—C13—H13A	105.4 (15)
H1B—N1—H1A	108.1 (18)	H13B—C13—H13A	106 (2)
C12—C7—N1	106.27 (15)	C7—C13—H13C	114.9 (13)
C12—C7—C13	108.56 (16)	H13B—C13—H13C	105.8 (18)
N1—C7—C13	110.89 (15)	H13A—C13—H13C	113 (2)
C12—C7—C8	110.81 (16)	C11—C14—H14B	111.3 (13)
N1—C7—C8	106.89 (14)	C11—C14—H14A	111.4 (12)
C13—C7—C8	113.20 (16)	H14B—C14—H14A	107.1 (18)
C9—C8—C7	113.09 (16)	C11—C14—H14C	106.6 (14)
C9—C8—H8A	108.4 (12)	H14B—C14—H14C	111 (2)
C7—C8—H8A	107.6 (12)	H14A—C14—H14C	109.9 (19)
C9—C8—H8B	110.8 (15)	C11—C15—H15C	110.0 (12)
C7—C8—H8B	107.1 (15)	C11—C15—H15A	113.3 (12)
H8A—C8—H8B	110 (2)	H15C—C15—H15A	107.1 (17)
C10—C9—C8	110.57 (16)	C11—C15—H15B	111.8 (14)
C10—C9—H9B	107.8 (14)	H15C—C15—H15B	105.8 (19)
C8—C9—H9B	110.1 (14)	H15A—C15—H15B	108.5 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···S1ⁱ	0.87 (2)	2.44 (2)	3.301 (2)	170 (2)
N1—H1A···S1	0.90 (2)	2.39 (2)	3.226 (2)	157 (2)
C14—H14C···Cl1ⁱⁱ	0.91 (3)	3.02 (2)	3.803 (2)	145 (2)
C15—H15B···Cl1	0.93 (2)	2.88 (2)	3.748 (2)	156 (2)
C13—H13B···Cl3ⁱⁱⁱ	0.98 (2)	3.02 (2)	3.905 (2)	151 (2)
C13—H13C···Cl4^iv	0.98 (2)	3.08 (2)	3.782 (2)	129 (2)
C9—H9B···Cl4^iv	0.95 (2)	2.92 (2)	3.708 (2)	141 (2)
C15—H15C···Cl4^v	0.94 (2)	2.94 (2)	3.646 (2)	133 (2)
C8—H8B···Cl5^vi	0.89 (3)	2.87 (3)	3.748 (2)	169 (2)
C10—H10A···Cl5ⁱ	0.97 (2)	3.02 (2)	3.966 (2)	167 (2)

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

Experimental details

Crystal data
Chemical formula	C₉H₂₀N⁺·C₆Cl₅S⁻
M_r	423.63
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	8.4230 (5), 10.5081 (4), 11.6142 (6)
α, β, γ (°)	110.946 (4), 102.614 (4), 95.286 (4)
V (Å³)	920.39 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.21 × 0.14 × 0.09

Data collection
Diffractometer	Oxford Diffraction KM4 CCD diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.779, 0.866
No. of measured, independent and observed [I > 2σ(I)] reflections	5583, 3161, 2930
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.097, 1.21
No. of reflections	3161
No. of parameters	279
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.44

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···S1ⁱ	0.87 (2)	2.44 (2)	3.301 (2)	170 (2)
N1—H1A···S1	0.90 (2)	2.39 (2)	3.226 (2)	157 (2)
C14—H14C···Cl1ⁱⁱ	0.91 (3)	3.02 (2)	3.803 (2)	145 (2)
C15—H15B···Cl1	0.93 (2)	2.88 (2)	3.748 (2)	156 (2)
C13—H13B···Cl3ⁱⁱⁱ	0.98 (2)	3.02 (2)	3.905 (2)	151 (2)
C13—H13C···Cl4^iv	0.98 (2)	3.08 (2)	3.782 (2)	129 (2)
C9—H9B···Cl4^iv	0.95 (2)	2.92 (2)	3.708 (2)	141 (2)
C15—H15C···Cl4^v	0.94 (2)	2.94 (2)	3.646 (2)	133 (2)
C8—H8B···Cl5^vi	0.89 (3)	2.87 (3)	3.748 (2)	169 (2)
C10—H10A···Cl5ⁱ	0.97 (2)	3.02 (2)	3.966 (2)	167 (2)

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

Acknowledgements

The authors thank Dr Anna Dołęga and Dr Jarosław Chojnacki for helpful discussions during the preparation of the manuscript.

References

Baranowska, K. (2007). Acta Cryst. E63, o2653–o2655. Web of Science CSD CrossRef IUCr Journals Google Scholar
Baranowska, K., Chojnacki, J., Becker, B. & Wojnowski, W. (2003). Acta Cryst. E59, o765–o766. Web of Science CSD CrossRef IUCr Journals Google Scholar
Baranowska, K., Chojnacki, J., Gosiewska, M. & Wojnowski, W. (2006). Z. Anorg. Allg. Chem. 632, 1086–1090. Web of Science CSD CrossRef CAS Google Scholar
Baranowska, K., Chojnacki, J., Konitz, A., Wojnowski, W. & Becker, B. (2006). Polyhedron, 25, 1555–1560. Web of Science CSD CrossRef CAS Google Scholar
Baranowska, K., Liadis, K. & Wojnowski, W. (2008). Acta Cryst. E64, o1329. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Dołęga, A., Pladzyk, A., Baranowska, K. & Wieczerzak, M. (2008). Inorg. Chem. Commun. 11, 847–850. Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. Google Scholar
Perrin, D. D. & Armarego, W. L. F. (1988). Purification of Laboratory Chemicals. Oxford: Pergamon Press. Google Scholar
Pladzyk, A. & Baranowska, K. (2007). Acta Cryst. E63, m1594. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar