1-Benzyl-3,5-bis­[(E)-3-thienyl­methyl­idene]piperidin-4-one

Gayathri, P.; Thiruvalluvar, A.; Rajeswari, K.; Pandiarajan, K.; Butcher, R.J.

doi:10.1107/S1600536811003758

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o571

doi:10.1107/S1600536811003758

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1-Benzyl-3,5-bis[(E)-3-thienylmethylidene]piperidin-4-one

P. Gayathri,^a A. Thiruvalluvar,^a ^* K. Rajeswari,^b K. Pandiarajan ^b and R. J. Butcher ^c

^aPG Research Department of Physics, Rajah Serfoji Government College (Autonomous), Thanjavur 613 005, Tamilnadu, India, ^bDepartment of Chemistry, Annamalai University, Annamalai Nagar 608 002, Tamilnadu, India, and ^cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: thiruvalluvar.a@gmail.com

(Received 17 January 2011; accepted 29 January 2011; online 5 February 2011)

In the title molecule, C₂₂H₁₉NOS₂, the piperidine ring adopts an envelope conformation with the benzyl substituent in an equatorial position. Each of the olefinic double bonds has an E configuration. The dihedral angle between the two thiophene rings is 1.55 (18)°. The thiophene rings form angles of 72.21 (14) and 73.43 (14)° with the phenyl ring. Both thiophene rings are disordered over two orientations [occupancy ratios of 0.799 (1):0.201 (1)] at 180° from one another. In the crystal, weak intermolecular C—H⋯O hydrogen bonds and C—H⋯π interactions help to stabilize the packing.

Related literature

For a related structure and applications of piperidone derivatives, see: Rajeswari et al. (2009 ).

Experimental

Crystal data

C₂₂H₁₉NOS₂
M_r = 377.52
Triclinic, $[P \overline 1]$
a = 6.1809 (3) Å
b = 12.7391 (9) Å
c = 12.9251 (7) Å
α = 112.657 (6)°
β = 95.845 (5)°
γ = 98.512 (5)°
V = 914.65 (11) Å³
Z = 2
Cu Kα radiation
μ = 2.71 mm⁻¹
T = 123 K
0.44 × 0.31 × 0.23 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.587, T_max = 1.000
6091 measured reflections
3615 independent reflections
3114 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.110
S = 1.03
3615 reflections
276 parameters
72 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg6 is the centroid of the C17–C22 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13A—H13A⋯O1ⁱ	0.95	2.39	3.177 (4)	140
C16—H16A⋯Cg6ⁱⁱ	0.99	2.68	3.6017 (19)	156
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x, -y+1, -z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811003758/jj2073sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003758/jj2073Isup2.hkl

checkCIF report

Comment top

As part of our research (Rajeswari et al., 2009), we have synthesized the title compound (I) and report its crystal structure here.

The molecular structure of the title compound (I) is shown in Fig. 1. The piperidine ring adopts an envelope conformation with the benzyl substituent in an equatorial position. The sum of the bond angles around N1 [328.38 (13)°] indicates a pyramidal geometry. The N1 atom deviates by 0.715 (2) Å from the least-squares plane passing through atoms C1—C5. Each of the olefinic double bonds has an E configuration. The dihedral angle between the two thiophene rings is 1.55 (18)°. The thiophene rings form angles of 72.21 (14) and 73.43 (14)° with the phenyl ring. Both thiophene rings are disordered over two orientations [occupancies of 0.799 (1)/0.201 (1)] at 180° from one another. In the crystal, weak intermolecular C13A—H13A···O1 hydrogen bonds and C16—H16A···π interactions involving the phenyl ring (C17—C22) help to stabilize the packing (Table 1, Fig. 2).

Related literature top

For a related structure and applications of piperidone derivatives, see: Rajeswari et al. (2009).

Experimental top

The mixture of 1-benzylpiperidin-4-one (1.9 ml, 0.01 mol) and thiophene-3-aldehyde (1.8 ml, 0.02 mol) in ethanol (95%, 10 ml), was added with 5 ml of 20% sodium hydroxide followed by the heating on a waterbath for 30 minutes. The solid separated was filtered and recrystallized by slow evaporation from 95% ethanol. The yield was (3.0 g, 80%).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radius. Both thiophene rings are disordered over two orientations (0.799 (1)/0.201 (1)).
	Fig. 2. The packing of the title compound, viewed down the a axis. Dashed lines indicate weak hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted.

1-Benzyl-3,5-bis[(E)-3-thienylmethylidene]piperidin-4-one top

Crystal data top

C₂₂H₁₉NOS₂	Z = 2
M_r = 377.52	F(000) = 396
Triclinic, P1	D_x = 1.371 Mg m⁻³
Hall symbol: -P 1	Melting point: 429 K
a = 6.1809 (3) Å	Cu Kα radiation, λ = 1.54184 Å
b = 12.7391 (9) Å	Cell parameters from 3996 reflections
c = 12.9251 (7) Å	θ = 6.4–74.0°
α = 112.657 (6)°	µ = 2.71 mm⁻¹
β = 95.845 (5)°	T = 123 K
γ = 98.512 (5)°	Chunk, colourless
V = 914.65 (11) Å³	0.44 × 0.31 × 0.23 mm

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	3615 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3114 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 10.5081 pixels mm^-1	θ_max = 74.2°, θ_min = 6.4°
ω scans	h = −6→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −14→15
T_min = 0.587, T_max = 1.000	l = −16→12
6091 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0635P)² + 0.4312P] where P = (F_o² + 2F_c²)/3
3615 reflections	(Δ/σ)_max = 0.001
276 parameters	Δρ_max = 0.37 e Å⁻³
72 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₂₂H₁₉NOS₂	γ = 98.512 (5)°
M_r = 377.52	V = 914.65 (11) Å³
Triclinic, P1	Z = 2
a = 6.1809 (3) Å	Cu Kα radiation
b = 12.7391 (9) Å	µ = 2.71 mm⁻¹
c = 12.9251 (7) Å	T = 123 K
α = 112.657 (6)°	0.44 × 0.31 × 0.23 mm
β = 95.845 (5)°

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	3615 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	3114 reflections with I > 2σ(I)
T_min = 0.587, T_max = 1.000	R_int = 0.026
6091 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	72 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.37 e Å⁻³
3615 reflections	Δρ_min = −0.27 e Å⁻³
276 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 > 2σ(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	Occ. (<1)
S1A	0.18315 (9)	1.03620 (4)	0.61944 (5)	0.0240 (2)	0.799 (1)
S2A	0.73267 (10)	0.08626 (5)	0.16709 (6)	0.0279 (2)	0.799 (1)
O1	0.8340 (2)	0.63874 (10)	0.50798 (10)	0.0306 (3)
N1	0.3176 (2)	0.57437 (11)	0.26094 (11)	0.0217 (4)
C1	0.3584 (3)	0.46955 (14)	0.27383 (14)	0.0246 (4)
C2	0.5717 (3)	0.49305 (13)	0.35403 (13)	0.0214 (4)
C3	0.6540 (3)	0.61272 (14)	0.44395 (13)	0.0220 (4)
C4	0.5080 (3)	0.69853 (13)	0.45572 (13)	0.0201 (4)
C5	0.2948 (3)	0.66158 (13)	0.37148 (13)	0.0212 (4)
C6	0.5750 (3)	0.80356 (12)	0.54314 (13)	0.0210 (4)
C7A	0.4685 (3)	0.90348 (14)	0.5796 (3)	0.0183 (5)	0.799 (1)
C8A	0.2461 (4)	0.90208 (14)	0.5516 (3)	0.0207 (6)	0.799 (1)
C9A	0.4535 (3)	1.0966 (3)	0.6871 (4)	0.0329 (4)	0.799 (1)
C10A	0.5831 (4)	1.0177 (2)	0.6602 (3)	0.0234 (6)	0.799 (1)
C11	0.6925 (3)	0.41222 (11)	0.34934 (12)	0.0223 (4)
C12A	0.6495 (7)	0.28977 (15)	0.2719 (3)	0.0228 (5)	0.799 (1)
C13A	0.8188 (6)	0.22914 (15)	0.2613 (3)	0.0238 (7)	0.799 (1)
C14A	0.4666 (3)	0.1060 (3)	0.1415 (4)	0.0310 (5)	0.799 (1)
C15A	0.4455 (6)	0.2152 (2)	0.2014 (4)	0.0263 (6)	0.799 (1)
C16	0.1124 (3)	0.54282 (14)	0.17762 (14)	0.0250 (4)
C17	0.0842 (3)	0.63387 (14)	0.13266 (13)	0.0231 (4)
C18	0.2395 (3)	0.66337 (15)	0.07197 (14)	0.0276 (5)
C19	0.2113 (3)	0.74264 (16)	0.02500 (15)	0.0310 (5)
C20	0.0256 (3)	0.79278 (16)	0.03671 (15)	0.0320 (5)
C21	−0.1304 (3)	0.76399 (16)	0.09586 (15)	0.0325 (5)
C22	−0.1007 (3)	0.68515 (15)	0.14398 (14)	0.0278 (5)
C8B	0.5804 (14)	1.0004 (7)	0.6512 (15)	0.0207 (6)	0.201 (1)
C9B	0.1915 (10)	1.0076 (7)	0.6059 (10)	0.0240 (2)	0.201 (1)
S1B	0.4253 (4)	1.1062 (3)	0.6913 (4)	0.0329 (4)	0.201 (1)
S2B	0.4472 (4)	0.0861 (3)	0.1254 (4)	0.0310 (5)	0.201 (1)
C13B	0.438 (2)	0.2290 (5)	0.2021 (17)	0.0238 (7)	0.201 (1)
C14B	0.7253 (7)	0.1115 (10)	0.1784 (12)	0.0279 (2)	0.201 (1)
C7B	0.4467 (8)	0.8937 (4)	0.5864 (15)	0.0183 (5)	0.201 (1)
C12B	0.640 (3)	0.2900 (3)	0.2707 (10)	0.0228 (5)	0.201 (1)
C10B	0.221 (2)	0.9007 (8)	0.5623 (14)	0.0234 (6)	0.201 (1)
C15B	0.800 (3)	0.2159 (10)	0.2558 (16)	0.0263 (6)	0.201 (1)
H1B	0.36535	0.40961	0.19840	0.0296*
H5A	0.25596	0.73017	0.36152	0.0255*
H5B	0.17305	0.62863	0.40123	0.0255*
H1A	0.23312	0.43872	0.30305	0.0296*
H16A	0.11277	0.46894	0.11292	0.0300*
H16B	−0.01661	0.52956	0.21384	0.0300*
H18	0.36607	0.62866	0.06278	0.0331*
H19	0.31915	0.76265	−0.01525	0.0372*
H20	0.00581	0.84676	0.00415	0.0383*
H21	−0.25789	0.79798	0.10372	0.0390*
H22	−0.20800	0.66618	0.18501	0.0333*
H6	0.713 (3)	0.8169 (16)	0.5895 (17)	0.026 (5)*
H8A	0.14054	0.83497	0.50085	0.0249*	0.799 (1)
H9A	0.50486	1.17598	0.73726	0.0395*	0.799 (1)
H10A	0.73660	1.03548	0.69141	0.0281*	0.799 (1)
H11	0.823 (3)	0.4373 (16)	0.4015 (17)	0.026 (5)*
H13A	0.96646	0.26254	0.30162	0.0286*	0.799 (1)
H14A	0.34781	0.04620	0.09052	0.0372*	0.799 (1)
H15A	0.30930	0.24073	0.19759	0.0316*	0.799 (1)
H8B	0.73734	1.01388	0.67126	0.0249*	0.201 (1)
H9B	0.05409	1.02885	0.59182	0.0288*	0.201 (1)
H10B	0.10440	0.83526	0.51955	0.0281*	0.201 (1)
H13B	0.31035	0.26169	0.19782	0.0286*	0.201 (1)
H14B	0.81485	0.05504	0.15365	0.0335*	0.201 (1)
H15B	0.94614	0.24115	0.29862	0.0316*	0.201 (1)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.0245 (2)	0.0238 (3)	0.0207 (3)	0.0093 (2)	0.0021 (2)	0.0046 (2)
S2A	0.0394 (3)	0.0223 (3)	0.0221 (3)	0.0103 (2)	0.0069 (2)	0.0073 (2)
O1	0.0245 (6)	0.0280 (6)	0.0298 (6)	0.0071 (5)	−0.0056 (5)	0.0036 (5)
N1	0.0241 (7)	0.0213 (6)	0.0165 (6)	0.0037 (5)	−0.0021 (5)	0.0060 (5)
C1	0.0267 (8)	0.0213 (7)	0.0214 (8)	0.0028 (6)	−0.0019 (6)	0.0061 (6)
C2	0.0223 (7)	0.0236 (8)	0.0174 (7)	0.0032 (6)	0.0026 (6)	0.0081 (6)
C3	0.0215 (8)	0.0249 (8)	0.0182 (7)	0.0035 (6)	0.0017 (6)	0.0083 (6)
C4	0.0206 (7)	0.0233 (7)	0.0170 (7)	0.0039 (6)	0.0028 (6)	0.0092 (6)
C5	0.0208 (7)	0.0231 (7)	0.0182 (7)	0.0044 (6)	0.0010 (6)	0.0074 (6)
C6	0.0193 (7)	0.0258 (8)	0.0178 (7)	0.0036 (6)	0.0016 (6)	0.0094 (6)
C7A	0.0202 (8)	0.0218 (8)	0.0143 (8)	0.0006 (6)	0.0049 (7)	0.0098 (7)
C8A	0.0215 (11)	0.0253 (10)	0.0147 (11)	0.0062 (8)	0.0045 (8)	0.0066 (8)
C9A	0.0376 (8)	0.0298 (7)	0.0286 (6)	0.0031 (6)	0.0043 (7)	0.0106 (5)
C10A	0.0225 (10)	0.0219 (11)	0.0185 (12)	−0.0006 (9)	0.0023 (8)	0.0025 (10)
C11	0.0221 (8)	0.0246 (8)	0.0185 (7)	0.0025 (6)	0.0017 (6)	0.0081 (6)
C12A	0.0290 (9)	0.0229 (8)	0.0173 (7)	0.0048 (6)	0.0044 (6)	0.0090 (6)
C13A	0.0308 (13)	0.0199 (11)	0.0208 (10)	0.0054 (10)	0.0040 (9)	0.0083 (9)
C14A	0.0412 (7)	0.0237 (9)	0.0216 (10)	0.0030 (6)	0.0020 (5)	0.0046 (7)
C15A	0.0285 (11)	0.0264 (11)	0.0248 (10)	0.0041 (10)	0.0016 (9)	0.0125 (11)
C16	0.0254 (8)	0.0253 (8)	0.0193 (7)	0.0011 (6)	−0.0047 (6)	0.0072 (6)
C17	0.0258 (8)	0.0224 (7)	0.0147 (7)	0.0009 (6)	−0.0047 (6)	0.0043 (6)
C18	0.0234 (8)	0.0327 (9)	0.0225 (8)	0.0031 (7)	−0.0017 (6)	0.0091 (7)
C19	0.0292 (9)	0.0368 (9)	0.0244 (8)	−0.0019 (7)	−0.0007 (7)	0.0141 (7)
C20	0.0406 (10)	0.0284 (8)	0.0251 (8)	0.0025 (7)	−0.0032 (7)	0.0127 (7)
C21	0.0360 (10)	0.0328 (9)	0.0286 (9)	0.0132 (8)	0.0037 (7)	0.0106 (7)
C22	0.0295 (9)	0.0327 (9)	0.0219 (8)	0.0076 (7)	0.0054 (7)	0.0113 (7)
C8B	0.0215 (11)	0.0253 (10)	0.0147 (11)	0.0062 (8)	0.0045 (8)	0.0066 (8)
C9B	0.0245 (2)	0.0238 (3)	0.0207 (3)	0.0093 (2)	0.0021 (2)	0.0046 (2)
S1B	0.0376 (8)	0.0298 (7)	0.0286 (6)	0.0031 (6)	0.0043 (7)	0.0106 (5)
S2B	0.0412 (7)	0.0237 (9)	0.0216 (10)	0.0030 (6)	0.0020 (5)	0.0046 (7)
C13B	0.0308 (13)	0.0199 (11)	0.0208 (10)	0.0054 (10)	0.0040 (9)	0.0083 (9)
C14B	0.0394 (3)	0.0223 (3)	0.0221 (3)	0.0103 (2)	0.0069 (2)	0.0073 (2)
C7B	0.0202 (8)	0.0218 (8)	0.0143 (8)	0.0006 (6)	0.0049 (7)	0.0098 (7)
C12B	0.0290 (9)	0.0229 (8)	0.0173 (7)	0.0048 (6)	0.0044 (6)	0.0090 (6)
C10B	0.0225 (10)	0.0219 (11)	0.0185 (12)	−0.0006 (9)	0.0023 (8)	0.0025 (10)
C15B	0.0285 (11)	0.0264 (11)	0.0248 (10)	0.0041 (10)	0.0016 (9)	0.0125 (11)

Geometric parameters (Å, º) top

S1A—C8A	1.718 (3)	C14B—C15B	1.30 (2)
S1A—C9A	1.718 (3)	C16—C17	1.507 (3)
S1B—C9B	1.719 (10)	C17—C18	1.397 (3)
S1B—C8B	1.718 (12)	C17—C22	1.391 (3)
S2A—C13A	1.718 (3)	C18—C19	1.386 (3)
S2A—C14A	1.718 (2)	C19—C20	1.388 (3)
S2B—C13B	1.718 (15)	C20—C21	1.382 (3)
S2B—C14B	1.719 (8)	C21—C22	1.394 (3)
O1—C3	1.235 (2)	C1—H1A	0.9900
N1—C5	1.470 (2)	C1—H1B	0.9900
N1—C16	1.472 (2)	C5—H5A	0.9900
N1—C1	1.462 (2)	C5—H5B	0.9900
C1—C2	1.506 (3)	C6—H6	0.943 (19)
C2—C3	1.490 (2)	C8A—H8A	0.9500
C2—C11	1.345 (2)	C8B—H8B	0.9500
C3—C4	1.491 (3)	C9A—H9A	0.9500
C4—C6	1.347 (2)	C9B—H9B	0.9500
C4—C5	1.508 (2)	C10A—H10A	0.9500
C6—C7A	1.458 (3)	C10B—H10B	0.9500
C6—C7B	1.458 (9)	C11—H11	0.92 (2)
C7A—C8A	1.381 (3)	C13A—H13A	0.9500
C7A—C10A	1.443 (4)	C13B—H13B	0.9500
C7B—C8B	1.372 (18)	C14A—H14A	0.9500
C7B—C10B	1.422 (14)	C14B—H14B	0.9500
C9A—C10A	1.341 (4)	C15A—H15A	0.9500
C9B—C10B	1.307 (17)	C15B—H15B	0.9500
C11—C12A	1.458 (3)	C16—H16A	0.9900
C11—C12B	1.458 (9)	C16—H16B	0.9900
C12A—C15A	1.438 (6)	C18—H18	0.9500
C12A—C13A	1.377 (5)	C19—H19	0.9500
C12B—C13B	1.38 (2)	C20—H20	0.9500
C12B—C15B	1.44 (2)	C21—H21	0.9500
C14A—C15A	1.340 (6)	C22—H22	0.9500

S1A···C8Aⁱ	3.648 (3)	C9A···H5Aⁱⁱⁱ	2.9400
S1A···S1Aⁱ	3.3576 (9)	C9A···H21ⁱ	2.9900
S1A···S2Aⁱⁱ	3.6853 (9)	C9B···H9Bⁱ	2.6700
S1A···C21ⁱ	3.6606 (19)	C9B···H8B^v	3.0200
S1B···C21ⁱ	3.469 (4)	C10B···H9Bⁱ	2.9700
S1B···C6ⁱⁱⁱ	3.631 (5)	C10B···H5A	2.7200
S1B···C18ⁱⁱⁱ	3.502 (5)	C12A···H1B	2.8100
S1B···C5ⁱⁱⁱ	3.609 (5)	C12B···H1B	2.7600
S1B···C4ⁱⁱⁱ	3.670 (5)	C13B···H19^vi	3.0000
S2A···C9Aⁱⁱ	3.651 (4)	C13B···H1B	2.4300
S2A···S1Aⁱⁱ	3.6853 (9)	C13B···H1A	3.0200
S2A···C10Aⁱⁱ	3.598 (3)	C14A···H19^vi	3.0200
S2A···C8Aⁱⁱ	3.569 (3)	C15A···H1B	2.6100
S2A···C7Aⁱⁱ	3.582 (3)	C15A···H19^vi	3.0200
S2B···C14B^iv	3.692 (15)	C17···H5A	2.7500
S2B···C8Bⁱⁱ	3.475 (16)	C17···H16A^ix	2.9700
S2B···S2B^iv	3.335 (6)	C17···H9Aⁱⁱⁱ	3.0500
S2B···C7Bⁱⁱ	3.618 (17)	C18···H16A^ix	2.8400
S1A···H10A^v	3.0000	C18···H9Aⁱⁱⁱ	2.6700
S1B···H21ⁱ	2.8300	C19···H16A^ix	2.9000
S1B···H5Aⁱⁱⁱ	2.9700	C19···H9Aⁱⁱⁱ	3.0800
S2A···H20^vi	3.1600	C20···H16A^ix	3.0700
S2A···H14A^iv	3.0400	H1A···H13A^v	2.5700
S2B···H19^vi	3.0900	H1A···H16B	2.5000
O1···C15B^vii	3.296 (19)	H1A···C13B	3.0200
O1···C13A^vii	3.177 (4)	H1A···H5B	2.3700
O1···H10B^viii	2.7400	H1A···H15A	2.5000
O1···H11^vii	2.79 (2)	H1A···H13B	2.2900
O1···H13A^vii	2.3900	H1B···C15A	2.6100
O1···H6	2.38 (2)	H1B···H15A	2.1200
O1···H11	2.39 (2)	H1B···C13B	2.4300
O1···H5B^viii	2.6200	H1B···H13B	1.8600
O1···H15B^vii	2.4900	H1B···C12A	2.8100
N1···H18	2.9300	H1B···C12B	2.7600
C1···C15A	3.154 (4)	H1B···H16A	2.2100
C1···C13B	2.974 (12)	H5A···C10B	2.7200
C4···C11ⁱⁱ	3.568 (2)	H5A···C7B	2.8400
C4···S1Bⁱⁱⁱ	3.670 (5)	H5A···C7A	2.8500
C5···C10B	3.228 (15)	H5A···C8A	2.6000
C5···S1Bⁱⁱⁱ	3.609 (5)	H5A···C17	2.7500
C5···C8A	3.133 (3)	H5A···H8A	2.0600
C6···C15Aⁱⁱ	3.415 (5)	H5A···C9Aⁱⁱⁱ	2.9400
C6···C12Bⁱⁱ	3.372 (12)	H5A···S1Bⁱⁱⁱ	2.9700
C6···S1Bⁱⁱⁱ	3.631 (5)	H5A···H10B	2.3400
C6···C13Bⁱⁱ	3.481 (18)	H5A···H9Aⁱⁱⁱ	2.5100
C6···C12Aⁱⁱ	3.381 (4)	H5B···H1A	2.3700
C7A···C13Aⁱⁱ	3.573 (4)	H5B···H8A	2.4900
C7A···C9Aⁱⁱⁱ	3.529 (6)	H5B···O1^v	2.6200
C7A···S2Aⁱⁱ	3.582 (3)	H5B···H16B	2.3400
C7B···S2Bⁱⁱ	3.618 (17)	H6···O1	2.38 (2)
C7B···C15Bⁱⁱ	3.26 (2)	H6···H10A	2.5500
C7B···C14Bⁱⁱ	3.34 (2)	H6···H8B	2.2900
C7B···C12Bⁱⁱ	3.512 (14)	H8A···H5B	2.4900
C8A···S2Aⁱⁱ	3.569 (3)	H8A···H5A	2.0600
C8A···C5	3.133 (3)	H8A···C4	3.0300
C8A···C13Aⁱⁱ	3.452 (4)	H8A···C5	2.5900
C8A···C10Aⁱⁱⁱ	3.475 (4)	H8B···C9B^viii	3.0200
C8A···S1Aⁱ	3.648 (3)	H8B···H6	2.2900
C8B···S2Bⁱⁱ	3.475 (16)	H8B···H9B^viii	2.3200
C8B···C14Bⁱⁱ	3.595 (18)	H9A···C17ⁱⁱⁱ	3.0500
C9A···C18ⁱⁱⁱ	3.520 (5)	H9A···H5Aⁱⁱⁱ	2.5100
C9A···S2Aⁱⁱ	3.651 (4)	H9A···C19ⁱⁱⁱ	3.0800
C9A···C7Aⁱⁱⁱ	3.529 (6)	H9A···C18ⁱⁱⁱ	2.6700
C9B···C9Bⁱ	3.357 (14)	H9B···H9Bⁱ	2.1900
C10A···C14Aⁱⁱ	3.504 (6)	H9B···H8B^v	2.3200
C10A···C8Aⁱⁱⁱ	3.475 (4)	H9B···C10Bⁱ	2.9700
C10A···S2Aⁱⁱ	3.598 (3)	H9B···C9Bⁱ	2.6700
C10B···C15Bⁱⁱ	3.23 (2)	H10A···H6	2.5500
C10B···C14Bⁱⁱ	3.40 (2)	H10A···S1A^viii	3.0000
C10B···C5	3.228 (15)	H10B···H5A	2.3400
C11···C4ⁱⁱ	3.568 (2)	H10B···C5	2.8100
C12A···C6ⁱⁱ	3.381 (4)	H10B···O1^v	2.7400
C12B···C6ⁱⁱ	3.372 (12)	H11···O1^vii	2.79 (2)
C12B···C7Bⁱⁱ	3.512 (14)	H11···O1	2.39 (2)
C13A···C8Aⁱⁱ	3.452 (4)	H11···H13A	2.4500
C13A···O1^vii	3.177 (4)	H13A···O1^vii	2.3900
C13A···C7Aⁱⁱ	3.573 (4)	H13A···H1A^viii	2.5700
C13B···C6ⁱⁱ	3.481 (18)	H13A···H11	2.4500
C13B···C1	2.974 (12)	H13B···H1B	1.8600
C14A···C10Aⁱⁱ	3.504 (6)	H13B···C2	2.9500
C14B···C7Bⁱⁱ	3.34 (2)	H13B···H1A	2.2900
C14B···C10Bⁱⁱ	3.40 (2)	H13B···C1	2.4000
C14B···C8Bⁱⁱ	3.595 (18)	H14A···S2A^iv	3.0400
C14B···S2B^iv	3.692 (15)	H15A···C1	2.6500
C15A···C6ⁱⁱ	3.415 (5)	H15A···H1B	2.1200
C15A···C1	3.154 (4)	H15A···H1A	2.5000
C15B···C10Bⁱⁱ	3.23 (2)	H15B···O1^vii	2.4900
C15B···O1^vii	3.296 (19)	H16A···C17^ix	2.9700
C15B···C7Bⁱⁱ	3.26 (2)	H16A···H1B	2.2100
C16···C18^ix	3.520 (2)	H16A···C20^ix	3.0700
C18···C16^ix	3.520 (2)	H16A···C18^ix	2.8400
C18···S1Bⁱⁱⁱ	3.502 (5)	H16A···C19^ix	2.9000
C18···C9Aⁱⁱⁱ	3.520 (5)	H16B···H22	2.3600
C21···S1Bⁱ	3.469 (4)	H16B···H1A	2.5000
C21···S1Aⁱ	3.6606 (19)	H16B···H5B	2.3400
C1···H13B	2.4000	H18···N1	2.9300
C1···H15A	2.6500	H19···S2B^vi	3.0900
C2···H13B	2.9500	H19···C14A^vi	3.0200
C4···H8A	3.0300	H19···C15A^vi	3.0200
C5···H10B	2.8100	H19···C13B^vi	3.0000
C5···H8A	2.5900	H20···S2A^vi	3.1600
C7A···H5A	2.8500	H21···S1Bⁱ	2.8300
C7B···H5A	2.8400	H21···C9Aⁱ	2.9900
C8A···H5A	2.6000	H22···H16B	2.3600

C8A—S1A—C9A	92.00 (17)	N1—C1—H1A	109.00
C8B—S1B—C9B	90.4 (6)	N1—C1—H1B	109.00
C13A—S2A—C14A	91.2 (2)	C2—C1—H1A	109.00
C13B—S2B—C14B	91.2 (7)	C2—C1—H1B	109.00
C1—N1—C5	109.61 (13)	H1A—C1—H1B	108.00
C5—N1—C16	110.43 (13)	N1—C5—H5A	109.00
C1—N1—C16	108.34 (14)	N1—C5—H5B	109.00
N1—C1—C2	111.86 (15)	C4—C5—H5A	109.00
C1—C2—C3	118.18 (16)	C4—C5—H5B	109.00
C1—C2—C11	123.85 (15)	H5A—C5—H5B	108.00
C3—C2—C11	117.97 (15)	C4—C6—H6	116.8 (13)
O1—C3—C2	121.03 (17)	C7A—C6—H6	112.8 (13)
C2—C3—C4	117.50 (15)	C7B—C6—H6	114.6 (14)
O1—C3—C4	121.44 (16)	S1A—C8A—H8A	124.00
C5—C4—C6	124.57 (17)	C7A—C8A—H8A	124.00
C3—C4—C6	117.12 (16)	C7B—C8B—H8B	125.00
C3—C4—C5	118.29 (14)	S1B—C8B—H8B	125.00
N1—C5—C4	110.75 (14)	C10A—C9A—H9A	124.00
C4—C6—C7A	130.47 (19)	S1A—C9A—H9A	124.00
C4—C6—C7B	127.9 (5)	C10B—C9B—H9B	123.00
C6—C7A—C8A	126.3 (2)	S1B—C9B—H9B	123.00
C8A—C7A—C10A	110.5 (2)	C9A—C10A—H10A	123.00
C6—C7A—C10A	123.0 (2)	C7A—C10A—H10A	123.00
C6—C7B—C10B	134.6 (12)	C9B—C10B—H10B	124.00
C6—C7B—C8B	112.0 (6)	C7B—C10B—H10B	124.00
C8B—C7B—C10B	112.4 (9)	C12A—C11—H11	114.6 (13)
S1A—C8A—C7A	111.9 (2)	C2—C11—H11	116.2 (13)
S1B—C8B—C7B	110.7 (7)	C12B—C11—H11	116.8 (15)
S1A—C9A—C10A	111.6 (3)	C12A—C13A—H13A	124.00
S1B—C9B—C10B	113.6 (8)	S2A—C13A—H13A	124.00
C7A—C10A—C9A	114.0 (3)	S2B—C13B—H13B	124.00
C7B—C10B—C9B	112.2 (11)	C12B—C13B—H13B	125.00
C2—C11—C12A	129.3 (2)	S2A—C14A—H14A	124.00
C2—C11—C12B	127.0 (7)	C15A—C14A—H14A	124.00
C11—C12A—C13A	119.8 (3)	S2B—C14B—H14B	124.00
C11—C12A—C15A	129.5 (3)	C15B—C14B—H14B	124.00
C13A—C12A—C15A	110.7 (3)	C12A—C15A—H15A	123.00
C13B—C12B—C15B	110.8 (11)	C14A—C15A—H15A	123.00
C11—C12B—C13B	126.5 (13)	C12B—C15B—H15B	123.00
C11—C12B—C15B	122.8 (14)	C14B—C15B—H15B	123.00
S2A—C13A—C12A	112.4 (3)	H16A—C16—H16B	108.00
S2B—C13B—C12B	111.1 (9)	N1—C16—H16B	109.00
S2A—C14A—C15A	112.4 (3)	C17—C16—H16A	109.00
S2B—C14B—C15B	112.9 (10)	N1—C16—H16A	109.00
C12A—C15A—C14A	113.3 (3)	C17—C16—H16B	109.00
C12B—C15B—C14B	113.7 (14)	C17—C18—H18	120.00
N1—C16—C17	113.51 (15)	C19—C18—H18	120.00
C18—C17—C22	118.42 (17)	C18—C19—H19	120.00
C16—C17—C18	119.81 (17)	C20—C19—H19	120.00
C16—C17—C22	121.66 (16)	C19—C20—H20	120.00
C17—C18—C19	120.85 (17)	C21—C20—H20	120.00
C18—C19—C20	120.05 (18)	C20—C21—H21	120.00
C19—C20—C21	119.84 (19)	C22—C21—H21	120.00
C20—C21—C22	120.03 (18)	C21—C22—H22	120.00
C17—C22—C21	120.80 (17)	C17—C22—H22	120.00

C9A—S1A—C8A—C7A	−0.2 (3)	C6—C4—C5—N1	151.56 (17)
C8A—S1A—C9A—C10A	−0.9 (3)	C4—C6—C7A—C8A	19.5 (4)
C14A—S2A—C13A—C12A	−0.4 (3)	C4—C6—C7A—C10A	−166.4 (3)
C13A—S2A—C14A—C15A	0.0 (4)	C10A—C7A—C8A—S1A	1.2 (3)
C5—N1—C1—C2	−62.00 (18)	C6—C7A—C8A—S1A	175.9 (2)
C16—N1—C1—C2	177.45 (13)	C6—C7A—C10A—C9A	−176.8 (3)
C16—N1—C5—C4	−177.33 (14)	C8A—C7A—C10A—C9A	−1.9 (4)
C1—N1—C16—C17	−164.29 (14)	S1A—C9A—C10A—C7A	1.7 (4)
C5—N1—C16—C17	75.66 (18)	C2—C11—C12A—C15A	−18.5 (5)
C1—N1—C5—C4	63.39 (18)	C2—C11—C12A—C13A	163.1 (2)
N1—C1—C2—C11	−153.36 (16)	C15A—C12A—C13A—S2A	0.7 (4)
N1—C1—C2—C3	26.7 (2)	C11—C12A—C13A—S2A	179.4 (2)
C11—C2—C3—C4	−174.12 (16)	C11—C12A—C15A—C14A	−179.2 (3)
C3—C2—C11—C12A	179.2 (2)	C13A—C12A—C15A—C14A	−0.7 (5)
C11—C2—C3—O1	4.2 (3)	S2A—C14A—C15A—C12A	0.4 (5)
C1—C2—C11—C12A	−0.8 (3)	N1—C16—C17—C18	62.1 (2)
C1—C2—C3—C4	5.8 (2)	N1—C16—C17—C22	−121.80 (17)
C1—C2—C3—O1	−175.89 (16)	C16—C17—C18—C19	176.81 (16)
O1—C3—C4—C5	177.70 (16)	C22—C17—C18—C19	0.6 (3)
O1—C3—C4—C6	−3.6 (3)	C16—C17—C22—C21	−176.10 (16)
C2—C3—C4—C5	−4.0 (2)	C18—C17—C22—C21	0.1 (3)
C2—C3—C4—C6	174.63 (16)	C17—C18—C19—C20	−0.8 (3)
C3—C4—C5—N1	−29.9 (2)	C18—C19—C20—C21	0.4 (3)
C3—C4—C6—C7A	−177.8 (2)	C19—C20—C21—C22	0.3 (3)
C5—C4—C6—C7A	0.7 (3)	C20—C21—C22—C17	−0.5 (3)

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

Hydrogen-bond geometry (Å, º) top

Cg6 is the centroid of the C17–C22 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13A—H13A···O1^vii	0.95	2.39	3.177 (4)	140
C16—H16A···Cg6^ix	0.99	2.68	3.6017 (19)	156

Symmetry codes: (vii) −x+2, −y+1, −z+1; (ix) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₂₂H₁₉NOS₂
M_r	377.52
Crystal system, space group	Triclinic, P1
Temperature (K)	123
a, b, c (Å)	6.1809 (3), 12.7391 (9), 12.9251 (7)
α, β, γ (°)	112.657 (6), 95.845 (5), 98.512 (5)
V (Å³)	914.65 (11)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	2.71
Crystal size (mm)	0.44 × 0.31 × 0.23

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.587, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6091, 3615, 3114
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.03
No. of reflections	3615
No. of parameters	276
No. of restraints	72
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.27

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg6 is the centroid of the C17–C22 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13A—H13A···O1ⁱ	0.95	2.39	3.177 (4)	140
C16—H16A···Cg6ⁱⁱ	0.99	2.68	3.6017 (19)	156

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

Acknowledgements

RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Rajeswari, K., Pandiarajan, K., Gayathri, P. & Thiruvalluvar, A. (2009). Acta Cryst. E65, o885. 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
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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