research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 6| June 2015| Pages 621-623

Crystal structure of (2-chloro­eth­yl)[2-(methyl­sulfan­yl)benz­yl]ammonium chloride

aDepartment of Chemistry, UCS, Tumkur University, Tumkur 572 103, Karnataka, India, bDepartment of Chemistry, Indian Institute of Technology, Delhi, New Delhi 110 016, India, and cDepartment of Studies and Research in Physics, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India
*Correspondence e-mail: raghukp1@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 31 January 2015; accepted 26 April 2015; online 13 May 2015)

In the title mol­ecular salt, C10H15ClNS+·Cl, the cation is [RR"NH2]+, where R′ is 2-MeS-C6H4CH2– and R" is –CH2CH2Cl, and the anion is Cl. In the cation, the N atom is protonated with sp3-hybridization and with a tetra­hedral geometry. In the crystal, the anions are connected to the cations through two pairs of N—H⋯Cl hydrogen bonds, generating a four-centred inversion dimer with an R42(8) ring motif.

1. Chemical context

Chloro­ethyl-functionalized derivatives containing S- and N-donor sites are used for the preparation of (S, N, S/Se/Te/P/As/Sb)-type tridentate hybrid ligands by nucleophilic substitution of the chloro (Cl) group by RS, ArSe, ArTe, Ph2P, Ar2As (Kumar et al., 2008a[Kumar, P. R., Upreti, S. & Singh, A. K. (2008a). Inorg. Chim. Acta, 361, 1426-1436.]; Singh et al., 1999[Singh, A. K., Amburose, C. V., Kraemer, T. S. & Jasinski, J. P. (1999). J. Organomet. Chem. 592, 251-257.]; Singh & Singh, 2010[Singh, P. & Singh, A. K. (2010). Eur. J. Inorg. Chem. pp. 4187-4195.], 2012[Singh, P. & Singh, A. K. (2012). Inorg. Chim. Acta, 387, 441-445.]; Kumar et al., 2008b[Kumar, P. R., Upreti, S. & Singh, A. K. (2008b). Polyhedron, 27, 1610-1622.]). Metal complexes of this type of hybrid ligand are important and have found applications as catalysts in organic synthesis (Singh et al., 2013[Singh, P., Das, D., Prakash, O. & Singh, A. K. (2013). Inorg. Chim. Acta, 394, 77-84.]). Keeping this in mind, it was thought worthwhile to synthesise and characterise the title mol­ecular salt. We report herein on its synthesis, by chlorination of 2-(2-methyl­thio)­benzyl­amino)­ethanol using thionyl chloride, and on its crystal structure.

[Scheme 1]

2. Structural commentary

In the cation of the title mol­ecular salt (Fig. 1[link]), the –CH2–N+H2–CH2–CH2–Cl substituent has an extended conformation with all of the non-H atoms lying in a plane [maximum deviation = 0.032 (4) Å for atom C8]. The N1 atom is protonated with sp3-hybridization and has a tetra­hedral geometry. The S1 atom lies in the plane of the benzene ring to which it is attached while the methyl C10 atom is displaced from the plane of the benzene ring by 1.773 (5) Å.

[Figure 1]
Figure 1
The mol­ecular structure of the title mol­ecular salt, showing the atom labelling. The displacement ellipsoids are drawn at the 50% probability level.

The title mol­ecular salt was also characterised by NMR and FT–IR spectroscopy. In the proton NMR spectrum, the signals for the NCH2 and CH2Cl protons gave two triplets at 3.25 and 3.9 p.p.m., respectively. The [C10H15ClSN]+ cation is a secondary ammonium ion in which the N atom is protonated and hence undergoes sp3 hybridization, resulting in a tetra­hedral geometry around the N atom. This was confirmed by NMR as the 〉NH2+ protons are highly deshielded and are observed as a broad singlet at 10.03 p.p.m. In the FT–IR spectrum of title salt, the N–H stretching band was observed at 1569 cm−1.

3. Supra­molecular features

In the crystal, the cation and anion are connected through two pairs of N—H⋯Cl hydrogen bonds. These hydrogen bonds result in the formation of four-centred inversion dimers with an [R_{4}^{2}](8) ring motif (Table 1[link] and Fig. 2[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1B⋯Cl2 0.89 2.21 3.090 (3) 169
N1—H1A⋯Cl2i 0.89 2.32 3.163 (3) 158
Symmetry code: (i) -x+1, -y, -z.
[Figure 2]
Figure 2
The crystal packing of the title mol­ecular salt, viewed along the a axis. The N—H⋯Cl hydrogen bonds are shown as dashed lines (see Table 1[link] for details).

4. Database survey

A search of the Cambridge Structural Database (Version 5.36; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) found no hits for similar compounds. However, tridentate (S, N, S/Se/Te)-type ligands containing the cationic part of the title salt and their PdII and RuII complexes have been synthesised and structurally characterized (Kumar et al., 2008a[Kumar, P. R., Upreti, S. & Singh, A. K. (2008a). Inorg. Chim. Acta, 361, 1426-1436.]; Singh & Singh, 2012[Singh, P. & Singh, A. K. (2012). Inorg. Chim. Acta, 387, 441-445.]; Singh et al., 2012[Singh, P., Das, D., Kumar, A. & Singh, A. K. (2012). Inorg. Chem. Commun. 15, 163-166.]).

5. Synthesis and crystallization

The synthesis of the title compound is illustrated in Fig. 3[link]. 2-(2-Methyl­thio)­benzyl­amino)­ethanol (2 g, 10 mmol) was dissolved in 20 ml of dry chloro­form and the solution was cooled in an ice bath. Freshly distilled SOCl2 (3 ml, 40 mmol) dissolved in 20 ml of dry chloro­form was added to it dropwise over a period of 15 min. When the addition was complete, the temperature of the reaction mixture was increased slowly and the mixture was stirred under reflux for 6 h. Thereafter, the reaction mixture was cooled and concentrated to 10 ml on a rotary evaporator, giving a light-brown solid. The solid was dissolved in 10 ml of methanol, boiled with a pinch of activated charcoal and filtered. The filtrate was treated with 20 ml of diethyl ether. It gave a white crystalline product (caution: eye and skin irritant), which was filtered, washed with diethyl ether (10 ml × 4) and dried between the folds of filter paper. Colourless prisms of the title compound were grown in ethanol by slow evaporation of the solvent (yield: 70%; m.p.: 413 K; ΛM = 3.0 cm2 mol−1 ohm−1. Elemental analysis, found (calc.): C, 47.87 (47.68), H, 5.95 (5.99), N, 5.68 (5.55) %; 1H NMR (CDCl3, 298 K): δ (vs TMS): 2.55 (s, 3H, SCH3), 3.25 (t, J = 6.09 Hz, 2H, H1), 3.9 (t, J = 6,6 Hz, 2H, H2), 4.94 (s, 2H, H3), 7.26 (t, J = 6.96 Hz, 1H, H8), 7.34–7.46 (m, 2H, H6,7), 7.72–7.74 (d, J = 7.5 Hz, 1H, H9), 10.03 (bs, 2H, NH2+). 13C{1H} NMR (CDCl3, 298 K): δ (vs TMS): 16.85 (SCH3), 48.17 (C2), 49.27 (C1), 57.12 (C3), 126.26 (C6), 127.89 (C7) , 128.87 (C4), 130.25 (C8), 131.50 (C9), 138.95 (C5). FT–IR (KBr, cm−1): 3415 (s), 1569 (b) (N–H), 1590 (C–N), 763 (C–S).

[Figure 3]
Figure 3
The synthesis of the title mol­ecular salt.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. The hydrogen atoms attached to atom N1 were located in a difference Fourier map. In the final cycles of refinement they were included in calculated positions, as were the C-bound H atoms, and treated as riding atoms: N—H = 0.89 Å, C—H = 0.93–0.97 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(N,C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula C10H15ClNS+·Cl
Mr 252.19
Crystal system, space group Monoclinic, P21/n
Temperature (K) 298
a, b, c (Å) 6.5717 (10), 11.8058 (17), 16.201 (2)
β (°) 97.374 (3)
V3) 1246.5 (3)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.65
Crystal size (mm) 0.28 × 0.24 × 0.20
 
Data collection
Diffractometer Bruker APEXII CCD
Absorption correction Multi-scan (SADABS; Bruker, 2013[Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.839, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections 9002, 2255, 1584
Rint 0.100
(sin θ/λ)max−1) 0.600
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.158, 1.04
No. of reflections 2255
No. of parameters 128
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.50, −0.23
Computer programs: APEX2 and SAINT (Bruker, 2013[Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Chemical context top

Chloro­ethyl-functionalized derivatives containing S- and N-donor sites are used for the preparation of (S, N, S/Se/Te/P/As/Sb)-type tridentate hybrid ligands by nucleophilic substitution of the chloro (Cl-) group by RS-, ArSe-, ArTe- , Ph2P-, Ar2As- (Kumar et al., 2008a; Singh et al., 1999; Singh & Singh, 2010, 2012; Kumar et al., 2008b). Metal complexes of this type of hybrid ligand are important and have found applications as catalysts in organic synthesis (Singh et al., 2013). Keeping this in mind, it was thought worthwhile to synthesise and characterise the title molecular salt. We report herein on its synthesis, by chlorination of 2-(2-methyl­thio)­benzyl­amino)­ethanol using thio­nyl chloride, and on its crystal structure.

Structural commentary top

In the cation of the title molecular salt, the –CH2–N+H2–CH2–CH2–Cl substituent has an extended conformation with all of the non-H atoms lying in a plane [maximum deviation = 0.032 (4) Å for atom C8]. The N1 atom is protonated with sp3-hybridization and has a tetra­hedral geometry. The S1 atom lies in the plane of the benzene ring to which it is attached while the methyl C10 atom is displaced from the plane of the benzene ring by 1.773 (5) Å.

The title molecular salt was also characterised by NMR and FT–IR spectroscopy. In the proton NMR spectrum, the signals for the NCH2 and CH2Cl protons gave two triplets at 3.25 and 3.9 p.p.m., respectively. The [C10H15ClSN]+ cation is a secondary ammonium ion in which the N atom is protonated and hence undergoes sp3 hybridization, resulting in a tetra­hedral geometry around the N atom. This was confirmed by NMR as the NH2+ protons are highly deshielded and are observed as a broad singlet at 10.03 p.p.m. In the FT–IR spectrum of title salt, the N–H stretching band was observed at 1569 cm-1.

Supra­molecular features top

In the crystal, the cation and anion are connected through two pairs of N—H···Cl hydrogen bonds. These hydrogen bonds result in the formation of four-centred inversion dimers with an R42(8) ring motif (Table 1 and Fig. 2).

Database survey top

A search of the Cambridge Structural Database (Version 5.36; Groom & Allen, 2014) found no hits for similar compounds. However, tridentate (S, N, S/Se/Te)-type ligands containing the cationic part of the title salt and their PdII and RuII complexes have been synthesised and structurally characterized (Kumar et al., 2008a; Singh & Singh, 2012; Singh et al., 2012).

Synthesis and crystallization top

The synthesis of the title compound is illustrated in Fig. 3. 2-(2-Methyl­thio)­benzyl­amino)­ethanol (2 g, 10 mmol) was dissolved in 20 ml of dry chloro­form and the solution was cooled in an ice bath. Freshly distilled SOCl2 (3 ml, 40 mmol) dissolved in 20 ml of dry chloro­form was added to it dropwise over a period of 15 min. When the addition was complete, the temperature of reaction mixture was increased slowly and the mixture was stirred under reflux for 6 h. Thereafter, the reaction mixture was cooled and concentrated to 10 ml on a rotary evaporator, giving a light-brown solid. The solid was dissolved in 10 ml of methanol, boiled with a pinch of activated charcoal and filtered. The filtrate was treated with 20 ml of di­ethyl ether. It gave a white crystalline product (caution: eye and skin irritant), which was filtered, washed with di­ethyl ether (10 ml × 4) and dried between the folds of filter paper. Colourless prisms of the title compound were grown in ethanol by slow evaporation of the solvent (yield: 70%; m.p.: 413 K; ΛM = 3.0 cm2 mol-1 ohm-1. Elemental analysis, found (calc.): C, 47.87 (47.68), H, 5.95 (5.99), N, 5.68 (5.55) %; 1H NMR (CDCl3, 298 K): δ (vs TMS): 2.55 (s, 3H, SCH3), 3.25 (t, J = 6.09 Hz, 2H, H1), 3.9 (t, J = 6,6 Hz, 2H, H2), 4.94 (s, 2H, H3), 7.26 (t, J = 6.96 Hz, 1H, H8), 7.34–7.46 (m, 2H, H6,7), 7.72–7.74 (d, J = 7.5 Hz, 1H, H9), 10.03 (bs, 2H, NH2+). 13C{1H} NMR (CDCl3, 298 K): δ (vs TMS): 16.85 (SCH3), 48.17 (C2), 49.27 (C1), 57.12 (C3), 126.26 (C6), 127.89 (C7 ), 128.87 (C4), 130.25 (C8), 131.50 (C9), 138.95 (C5). FT–IR (KBr, cm-1): 3415 (s), 1569 (b) (N–H), 1590 (C–N), 763 (C–S).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydrogen atoms attached to atom N1 were located in a difference Fourier map. In the final cycles of refinement they were included in calculated positions, as were the C-bound H atoms, and treated as riding atoms: N—H = 0.89 Å, C—H = 0.93–0.97 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(N,C) for other H atoms.

Related literature top

For related literature, see: Groom & Allen (2014); Kumar et al. (2008a, 2008b); Singh & Singh (2010, 2012); Singh et al. (1999, 2013); Singh, Das, Kumar & Singh (2012).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecular salt, showing the atom labelling. The displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The crystal packing of the title molecular salt, viewed along the a axis. The N—H···Cl hydrogen bonds are shown as dashed lines (see Table 1 for details).
[Figure 3] Fig. 3. The synthesis of the title molecular salt.
(2-Chloroethyl)[2-(methylsulfanyl)benzyl]ammonium chloride top
Crystal data top
C10H15ClNS+·ClF(000) = 528
Mr = 252.19Dx = 1.344 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.5717 (10) Åθ = 2.1–25.0°
b = 11.8058 (17) ŵ = 0.65 mm1
c = 16.201 (2) ÅT = 298 K
β = 97.374 (3)°Prism, colourless
V = 1246.5 (3) Å30.28 × 0.24 × 0.20 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer
1584 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.100
phi and ω scansθmax = 25.3°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
h = 77
Tmin = 0.839, Tmax = 0.881k = 1414
9002 measured reflectionsl = 1919
2255 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.065H-atom parameters constrained
wR(F2) = 0.158 w = 1/[σ2(Fo2) + (0.0727P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2255 reflectionsΔρmax = 0.50 e Å3
128 parametersΔρmin = 0.23 e Å3
Crystal data top
C10H15ClNS+·ClV = 1246.5 (3) Å3
Mr = 252.19Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.5717 (10) ŵ = 0.65 mm1
b = 11.8058 (17) ÅT = 298 K
c = 16.201 (2) Å0.28 × 0.24 × 0.20 mm
β = 97.374 (3)°
Data collection top
Bruker APEXII CCD
diffractometer
2255 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
1584 reflections with I > 2σ(I)
Tmin = 0.839, Tmax = 0.881Rint = 0.100
9002 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0650 restraints
wR(F2) = 0.158H-atom parameters constrained
S = 1.04Δρmax = 0.50 e Å3
2255 reflectionsΔρmin = 0.23 e Å3
128 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.73384 (17)0.10230 (10)0.26820 (8)0.0632 (4)
Cl10.2925 (2)0.37387 (9)0.02280 (9)0.0769 (4)
N10.3518 (5)0.0518 (2)0.10476 (19)0.0437 (8)
H1A0.27510.02080.06130.052*
H1B0.48270.04110.09800.052*
C10.3504 (6)0.1317 (3)0.1757 (2)0.0442 (9)
C20.5336 (6)0.1815 (3)0.2109 (2)0.0443 (9)
C40.4120 (7)0.3622 (4)0.1571 (3)0.0615 (12)
H40.43400.43930.15030.074*
C30.5612 (7)0.2969 (3)0.2011 (3)0.0557 (11)
H30.68280.33070.22470.067*
C50.2319 (8)0.3142 (4)0.1233 (3)0.0675 (13)
H50.13010.35840.09400.081*
C60.2013 (7)0.1992 (4)0.1330 (3)0.0612 (12)
H60.07770.16690.11020.073*
C80.3102 (6)0.1754 (3)0.1051 (3)0.0497 (10)
H8A0.40130.21130.14930.060*
H8B0.17010.18840.11570.060*
C70.3103 (6)0.0073 (3)0.1812 (2)0.0489 (10)
H7A0.16830.00470.18960.059*
H7B0.39680.02410.22870.059*
C90.3421 (8)0.2266 (3)0.0230 (3)0.0657 (13)
H9A0.25110.19060.02120.079*
H9B0.48220.21360.01250.079*
C100.6669 (8)0.1210 (4)0.3711 (3)0.0762 (15)
H10A0.53360.08920.37410.114*
H10B0.76620.08340.41040.114*
H10C0.66510.20030.38400.114*
Cl20.80532 (15)0.04958 (9)0.07270 (6)0.0537 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0557 (7)0.0679 (8)0.0632 (8)0.0149 (6)0.0034 (6)0.0005 (6)
Cl10.0879 (9)0.0413 (7)0.1012 (10)0.0074 (6)0.0111 (7)0.0136 (6)
N10.0465 (19)0.0362 (18)0.0467 (19)0.0002 (14)0.0010 (15)0.0050 (15)
C10.053 (2)0.038 (2)0.042 (2)0.0005 (19)0.0068 (19)0.0023 (17)
C20.050 (2)0.041 (2)0.040 (2)0.0010 (18)0.0013 (18)0.0014 (18)
C40.088 (4)0.035 (2)0.060 (3)0.005 (2)0.005 (3)0.005 (2)
C30.064 (3)0.042 (2)0.058 (3)0.011 (2)0.003 (2)0.004 (2)
C50.088 (4)0.050 (3)0.058 (3)0.018 (3)0.011 (3)0.001 (2)
C60.054 (3)0.058 (3)0.066 (3)0.005 (2)0.013 (2)0.005 (2)
C80.049 (2)0.032 (2)0.067 (3)0.0023 (18)0.006 (2)0.001 (2)
C70.056 (2)0.043 (2)0.048 (2)0.0082 (19)0.007 (2)0.0038 (18)
C90.085 (3)0.037 (2)0.071 (3)0.002 (2)0.003 (3)0.004 (2)
C100.084 (4)0.084 (4)0.058 (3)0.020 (3)0.001 (3)0.014 (3)
Cl20.0499 (6)0.0577 (7)0.0524 (6)0.0044 (5)0.0020 (5)0.0074 (5)
Geometric parameters (Å, º) top
S1—C21.776 (4)C3—H30.9300
S1—C101.792 (5)C5—C61.384 (6)
Cl1—C91.768 (4)C5—H50.9300
N1—C71.477 (5)C6—H60.9300
N1—C81.485 (5)C8—C91.501 (6)
N1—H1A0.8900C8—H8A0.9700
N1—H1B0.8900C8—H8B0.9700
C1—C61.378 (5)C7—H7A0.9700
C1—C21.394 (5)C7—H7B0.9700
C1—C71.496 (5)C9—H9A0.9700
C2—C31.386 (5)C9—H9B0.9700
C4—C51.362 (6)C10—H10A0.9600
C4—C31.373 (6)C10—H10B0.9600
C4—H40.9300C10—H10C0.9600
C2—S1—C1099.7 (2)N1—C8—C9110.2 (3)
C7—N1—C8114.0 (3)N1—C8—H8A109.6
C7—N1—H1A108.8C9—C8—H8A109.6
C8—N1—H1A108.8N1—C8—H8B109.6
C7—N1—H1B108.8C9—C8—H8B109.6
C8—N1—H1B108.8H8A—C8—H8B108.1
H1A—N1—H1B107.6N1—C7—C1111.1 (3)
C6—C1—C2118.8 (4)N1—C7—H7A109.4
C6—C1—C7118.6 (4)C1—C7—H7A109.4
C2—C1—C7122.6 (3)N1—C7—H7B109.4
C3—C2—C1119.1 (4)C1—C7—H7B109.4
C3—C2—S1118.6 (3)H7A—C7—H7B108.0
C1—C2—S1122.3 (3)C8—C9—Cl1110.5 (3)
C5—C4—C3120.1 (4)C8—C9—H9A109.5
C5—C4—H4120.0Cl1—C9—H9A109.5
C3—C4—H4120.0C8—C9—H9B109.5
C4—C3—C2121.1 (4)Cl1—C9—H9B109.5
C4—C3—H3119.5H9A—C9—H9B108.1
C2—C3—H3119.5S1—C10—H10A109.5
C4—C5—C6119.6 (4)S1—C10—H10B109.5
C4—C5—H5120.2H10A—C10—H10B109.5
C6—C5—H5120.2S1—C10—H10C109.5
C1—C6—C5121.3 (4)H10A—C10—H10C109.5
C1—C6—H6119.3H10B—C10—H10C109.5
C5—C6—H6119.3
C6—C1—C2—C30.7 (6)C3—C4—C5—C60.6 (7)
C7—C1—C2—C3178.2 (4)C2—C1—C6—C51.2 (6)
C6—C1—C2—S1179.2 (3)C7—C1—C6—C5177.8 (4)
C7—C1—C2—S11.9 (5)C4—C5—C6—C10.5 (7)
C10—S1—C2—C387.1 (4)C7—N1—C8—C9175.9 (3)
C10—S1—C2—C192.8 (4)C8—N1—C7—C1178.6 (3)
C5—C4—C3—C21.1 (7)C6—C1—C7—N181.3 (5)
C1—C2—C3—C40.4 (6)C2—C1—C7—N197.7 (4)
S1—C2—C3—C4179.7 (3)N1—C8—C9—Cl1179.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Cl20.892.213.090 (3)169
N1—H1A···Cl2i0.892.323.163 (3)158
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Cl20.892.213.090 (3)169
N1—H1A···Cl2i0.892.323.163 (3)158
Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC10H15ClNS+·Cl
Mr252.19
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)6.5717 (10), 11.8058 (17), 16.201 (2)
β (°) 97.374 (3)
V3)1246.5 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.65
Crystal size (mm)0.28 × 0.24 × 0.20
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2013)
Tmin, Tmax0.839, 0.881
No. of measured, independent and
observed [I > 2σ(I)] reflections
9002, 2255, 1584
Rint0.100
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.158, 1.04
No. of reflections2255
No. of parameters128
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.23

Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

 

Acknowledgements

PRK thanks Professor Ajai K. Singh of IIT Delhi, India, for his valuable guidance during his PhD studies. BSP thanks Dr H. C. Devarajegowda, Department of Physics, Yuvarajas College (constituent), University of Mysore, for his support.

References

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Volume 71| Part 6| June 2015| Pages 621-623
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