4,4,6-Trimethyl-1-(3-methyl­phen­yl)-3,4-dihydro­pyrimidine-2(1H)-thione

Saeed, A.; Khera, R.A.; Parvez, M.

doi:10.1107/S1600536810004708

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o635

doi:10.1107/S1600536810004708

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4,4,6-Trimethyl-1-(3-methylphenyl)-3,4-dihydropyrimidine-2(1H)-thione

Aamer Saeed,^a ^* Rasheed Ahmad Khera ^a and Masood Parvez ^b

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^bDepartment of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
^*Correspondence e-mail: aamersaeed@yahoo.com

(Received 31 January 2010; accepted 6 February 2010; online 13 February 2010)

The asymmetric unit of the title compound, C₁₄H₁₈N₂S, contains two independent and conformationally similar molecules, which form cyclic dimers via intermolecular hydrogen bonds of the type N—H⋯S [graph set R²₂(8)]. The structure is isomorphous with that of one of the polymorphs of 4,4,6-trimethyl-1-phenyl-3,4-dihydropyrimidine-2(1H)-thione [Yamin et al. (2005 ). Acta Cryst. E61, o55–o57].

Related literature

For the biological activity of pyrimidine-2-thiones, see: Alam et al. (2005 ); Sriram et al. (2006 ); Swamy et al. (2005 ). For related structures, see: Yamin et al. (2005); Ismail et al. (2007 ). For graph-set analysis, see Etter et al. (1990 ).

Experimental

Crystal data

C₁₄H₁₈N₂S
M_r = 246.36
Orthorhombic, P b c a
a = 10.5904 (3) Å
b = 16.9189 (5) Å
c = 30.5713 (10) Å
V = 5477.7 (3) Å³
Z = 16
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 173 K
0.14 × 0.12 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1997 ) T_min = 0.970, T_max = 0.983
19135 measured reflections
4830 independent reflections
3231 reflections with I > 2.0σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.115
S = 1.04
4830 reflections
315 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S2	0.88	2.62	3.419 (2)	151
N3—H3N⋯S1	0.88	2.60	3.447 (2)	163

Data collection: COLLECT (Hooft, 1998 ); cell refinement: HKL DENZO (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK (Otwinowski & Minor, 1997); 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: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks Global, I. DOI: 10.1107/S1600536810004708/zs2028sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810004708/zs2028Isup2.hkl

checkCIF report

Comment top

The title compound C₁₄H₁₈N₂S (I) belongs to a novel and rare class of dihydropyrimidine-2-thiones. Their synthesis has been attracting widespread attention because of their diverse pharmacological properties such as antibacterial (Alam et al., 2005), antitumour (Swamy et al., 2005) and antioxidative activities (Sriram et al., 2006). The crystal structure of a closely related compound, 4,4,6-trimethyl-1-phenyl-3,4-dihydropyrimidine-2(1H)-thione (Yamin et al., 2005) and its triclinic polymorph (Ismail et al., 2007) have been reported.

The asymmetric unit of the title compound is composed of two molecules (Fig. 1) exhibiting intermolecular hydrogen bonds of the type N—H···S (Table 1) forming cyclic dimers [graph set R²₂(8) (Etter et al., 1990)]. The two molecules are conformationally similar [e.g. the inter-ring torsion angle C1–N2–C8–C13 (molecule 1), -83.1 (3)° and C15–N4–C22–C27, -85.9 (3)° (molecule 2)] and are related by pseudo two-fold rotational symmetry. The title compound is isomorphous with one of the polymorphs of 4,4,6-trimethyl-1-phenyl-3,4-dihydropyrimidine-2(1H)-thione (Yamin et al., 2005). However, in the triclinic polymorph of this related compound (Ismail et al., 2007), which also forms a cyclic dimer, the two molecules have crystallographic inversion symmetry.

Related literature top

For the biological activity of pyrimidine-2-thiones, see: Alam et al. (2005); Sriram et al. (2006); Swamy et al. (2005). For related structures, see: Yamin et al. (2005); Ismail et al. (2007). For graph-set analysis, see Etter et al. (1990).

Experimental top

The title compound was prepared by the reaction of 3-methylaniline with 4-methylpent-3-en-2-one in the presence of potassium thiocyanate in acetone: details of the synthesis will be reported later. Recrystallization from methanol afforded the title compound as colourless crystals: Anal. calcd. for C₁₄H₁₈N₂S: C, 68.25; H, 7.36; N, 11.37; S, 13.01%; found: C, 68.09; H, 7.41; N, 11.51; S, 13.12.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: HKL DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. ORTEP-3 (Farrugia, 1997) drawing of the two molecules in the asymmetric unit of (I) with displacement ellipsoids plotted at 50% probability level. Hydrogen bonds have been drawn with dashed lines.

4,4,6-Trimethyl-1-(3-methylphenyl)-3,4-dihydropyrimidine-2(1H)-thione top

Crystal data top

C₁₄H₁₈N₂S	F(000) = 2112
M_r = 246.36	D_x = 1.195 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 8634 reflections
a = 10.5904 (3) Å	θ = 1.0–25.3°
b = 16.9189 (5) Å	µ = 0.22 mm⁻¹
c = 30.5713 (10) Å	T = 173 K
V = 5477.7 (3) Å³	Block, colorless
Z = 16	0.14 × 0.12 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	4830 independent reflections
Radiation source: fine-focus sealed tube	3231 reflections with I > 2.0σ(I)
Graphite monochromator	R_int = 0.041
ϕ & ω scans	θ_max = 25.3°, θ_min = 2.3°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −12→12
T_min = 0.970, T_max = 0.983	k = −20→20
19135 measured reflections	l = −36→36

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.038P)² + 3.05P] where P = (F_o² + 2F_c²)/3
4830 reflections	(Δ/σ)_max < 0.001
315 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₄H₁₈N₂S	V = 5477.7 (3) Å³
M_r = 246.36	Z = 16
Orthorhombic, Pbca	Mo Kα radiation
a = 10.5904 (3) Å	µ = 0.22 mm⁻¹
b = 16.9189 (5) Å	T = 173 K
c = 30.5713 (10) Å	0.14 × 0.12 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	4830 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	3231 reflections with I > 2.0σ(I)
T_min = 0.970, T_max = 0.983	R_int = 0.041
19135 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.04	Δρ_max = 0.25 e Å⁻³
4830 reflections	Δρ_min = −0.23 e Å⁻³
315 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
S1	0.85314 (7)	0.07897 (4)	0.325070 (19)	0.03644 (19)
S2	0.84290 (7)	0.24913 (4)	0.43316 (2)	0.03863 (19)
N1	0.75860 (19)	0.22309 (11)	0.32616 (6)	0.0343 (5)
H1N	0.7579	0.2164	0.3547	0.041*
N2	0.76802 (18)	0.16559 (11)	0.25790 (6)	0.0305 (5)
N3	0.7806 (2)	0.09853 (11)	0.43444 (6)	0.0376 (5)
H3N	0.7897	0.1032	0.4060	0.045*
N4	0.7743 (2)	0.16054 (12)	0.50157 (6)	0.0354 (5)
C1	0.7907 (2)	0.16081 (13)	0.30203 (7)	0.0285 (6)
C2	0.7240 (2)	0.30212 (14)	0.30983 (8)	0.0327 (6)
C3	0.6741 (2)	0.29264 (14)	0.26468 (8)	0.0365 (6)
H3	0.6220	0.3332	0.2530	0.044*
C4	0.6990 (2)	0.23009 (14)	0.23982 (8)	0.0325 (6)
C5	0.6260 (3)	0.33607 (17)	0.34098 (9)	0.0513 (8)
H5A	0.6052	0.3902	0.3321	0.062*
H5B	0.6601	0.3365	0.3708	0.062*
H5C	0.5496	0.3034	0.3401	0.062*
C6	0.8409 (3)	0.35435 (16)	0.31010 (10)	0.0476 (7)
H6A	0.8182	0.4077	0.3003	0.057*
H6B	0.9045	0.3321	0.2903	0.057*
H6C	0.8753	0.3569	0.3398	0.057*
C7	0.6571 (3)	0.22143 (16)	0.19344 (8)	0.0440 (7)
H7A	0.6124	0.2694	0.1843	0.053*
H7B	0.6003	0.1759	0.1909	0.053*
H7C	0.7309	0.2133	0.1746	0.053*
C8	0.8098 (2)	0.10194 (14)	0.23002 (7)	0.0293 (6)
C9	0.7269 (2)	0.04236 (14)	0.21939 (7)	0.0316 (6)
H9	0.6433	0.0432	0.2306	0.038*
C10	0.7653 (2)	−0.01925 (14)	0.19210 (8)	0.0346 (6)
C11	0.8885 (3)	−0.01932 (15)	0.17714 (8)	0.0380 (6)
H11	0.9167	−0.0617	0.1592	0.046*
C12	0.9715 (2)	0.04068 (16)	0.18757 (8)	0.0386 (6)
H12	1.0554	0.0397	0.1766	0.046*
C13	0.9320 (2)	0.10269 (15)	0.21418 (7)	0.0339 (6)
H13	0.9879	0.1447	0.2213	0.041*
C14	0.6721 (3)	−0.08216 (16)	0.17965 (9)	0.0494 (8)
H14A	0.7167	−0.1264	0.1658	0.059*
H14B	0.6104	−0.0602	0.1591	0.059*
H14C	0.6283	−0.1009	0.2059	0.059*
C15	0.7974 (2)	0.16412 (14)	0.45766 (8)	0.0325 (6)
C16	0.7484 (3)	0.01867 (14)	0.45061 (8)	0.0390 (7)
C17	0.7067 (3)	0.02656 (17)	0.49684 (9)	0.0549 (8)
H17	0.6667	−0.0176	0.5101	0.066*
C18	0.7217 (3)	0.09111 (15)	0.52074 (8)	0.0420 (7)
C19	0.8654 (3)	−0.03424 (16)	0.44798 (10)	0.0569 (8)
H19A	0.8435	−0.0878	0.4576	0.068*
H19B	0.9317	−0.0129	0.4670	0.068*
H19C	0.8959	−0.0359	0.4177	0.068*
C20	0.6454 (3)	−0.01520 (17)	0.42148 (10)	0.0532 (8)
H20A	0.6238	−0.0686	0.4314	0.064*
H20B	0.6756	−0.0174	0.3912	0.064*
H20C	0.5704	0.0186	0.4230	0.064*
C21	0.6857 (4)	0.09640 (19)	0.56755 (10)	0.0709 (10)
H21A	0.6561	0.0447	0.5777	0.085*
H21B	0.6180	0.1354	0.5710	0.085*
H21C	0.7591	0.1127	0.5849	0.085*
C22	0.8055 (2)	0.22713 (14)	0.52939 (8)	0.0331 (6)
C23	0.7123 (2)	0.27825 (15)	0.54251 (8)	0.0355 (6)
H23	0.6288	0.2718	0.5317	0.043*
C24	0.7391 (3)	0.33970 (15)	0.57156 (8)	0.0381 (6)
C25	0.8616 (3)	0.34748 (16)	0.58649 (8)	0.0425 (7)
H25	0.8815	0.3887	0.6064	0.051*
C26	0.9557 (3)	0.29648 (17)	0.57300 (8)	0.0464 (7)
H26	1.0396	0.3033	0.5833	0.056*
C27	0.9278 (3)	0.23536 (16)	0.54441 (8)	0.0403 (7)
H27	0.9918	0.1997	0.5353	0.048*
C28	0.6363 (3)	0.39498 (17)	0.58604 (10)	0.0541 (8)
H28A	0.6659	0.4260	0.6111	0.065*
H28B	0.5617	0.3644	0.5945	0.065*
H28C	0.6144	0.4306	0.5619	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0510 (4)	0.0257 (3)	0.0326 (3)	0.0049 (3)	−0.0024 (3)	0.0000 (3)
S2	0.0582 (5)	0.0254 (3)	0.0322 (3)	−0.0035 (3)	−0.0002 (3)	0.0002 (3)
N1	0.0497 (13)	0.0252 (11)	0.0281 (10)	0.0039 (10)	0.0008 (10)	−0.0014 (9)
N2	0.0352 (12)	0.0272 (11)	0.0292 (10)	0.0041 (10)	−0.0024 (10)	−0.0019 (9)
N3	0.0615 (15)	0.0240 (11)	0.0274 (11)	−0.0043 (11)	0.0009 (11)	−0.0011 (9)
N4	0.0493 (14)	0.0276 (11)	0.0291 (11)	−0.0034 (11)	0.0026 (10)	−0.0016 (9)
C1	0.0295 (13)	0.0243 (13)	0.0318 (13)	−0.0033 (11)	0.0000 (11)	−0.0012 (10)
C2	0.0375 (15)	0.0245 (13)	0.0362 (13)	0.0026 (12)	−0.0003 (12)	−0.0029 (11)
C3	0.0383 (15)	0.0272 (14)	0.0439 (15)	0.0046 (12)	−0.0074 (13)	0.0029 (12)
C4	0.0326 (14)	0.0304 (14)	0.0345 (14)	0.0000 (12)	−0.0033 (12)	0.0016 (11)
C5	0.0586 (19)	0.0457 (18)	0.0495 (16)	0.0192 (16)	0.0048 (15)	−0.0015 (14)
C6	0.0503 (18)	0.0360 (16)	0.0564 (17)	−0.0044 (14)	−0.0067 (15)	0.0013 (13)
C7	0.0522 (18)	0.0370 (16)	0.0427 (15)	0.0072 (14)	−0.0087 (14)	0.0001 (12)
C8	0.0337 (15)	0.0272 (13)	0.0270 (12)	0.0039 (12)	−0.0030 (11)	0.0003 (10)
C9	0.0310 (14)	0.0335 (14)	0.0304 (13)	0.0018 (12)	0.0000 (11)	0.0007 (11)
C10	0.0437 (16)	0.0299 (14)	0.0300 (13)	0.0001 (13)	−0.0069 (12)	0.0011 (11)
C11	0.0471 (17)	0.0375 (16)	0.0293 (13)	0.0127 (14)	−0.0058 (13)	−0.0053 (12)
C12	0.0360 (15)	0.0475 (17)	0.0324 (14)	0.0066 (14)	0.0006 (12)	−0.0001 (13)
C13	0.0338 (15)	0.0375 (15)	0.0305 (13)	−0.0008 (12)	−0.0011 (12)	−0.0006 (11)
C14	0.061 (2)	0.0392 (16)	0.0475 (16)	−0.0060 (15)	−0.0062 (15)	−0.0059 (13)
C15	0.0375 (15)	0.0285 (14)	0.0316 (13)	0.0011 (12)	−0.0027 (11)	−0.0003 (11)
C16	0.0558 (18)	0.0235 (14)	0.0378 (15)	−0.0044 (13)	0.0016 (14)	0.0008 (11)
C17	0.083 (2)	0.0356 (17)	0.0457 (17)	−0.0191 (17)	0.0134 (16)	0.0015 (13)
C18	0.0555 (18)	0.0337 (15)	0.0369 (14)	−0.0072 (14)	0.0043 (14)	0.0028 (12)
C19	0.067 (2)	0.0353 (17)	0.068 (2)	0.0020 (16)	−0.0107 (17)	0.0072 (15)
C20	0.060 (2)	0.0351 (16)	0.0645 (19)	−0.0108 (15)	−0.0136 (16)	0.0014 (14)
C21	0.114 (3)	0.054 (2)	0.0451 (17)	−0.026 (2)	0.0167 (19)	0.0044 (15)
C22	0.0427 (16)	0.0287 (14)	0.0278 (12)	−0.0003 (13)	0.0009 (12)	−0.0017 (10)
C23	0.0359 (15)	0.0386 (15)	0.0319 (13)	−0.0014 (13)	−0.0031 (12)	−0.0013 (12)
C24	0.0479 (17)	0.0339 (15)	0.0325 (13)	0.0029 (14)	0.0026 (13)	−0.0058 (12)
C25	0.0503 (18)	0.0429 (17)	0.0343 (14)	−0.0076 (15)	−0.0065 (14)	−0.0086 (12)
C26	0.0418 (17)	0.0542 (19)	0.0431 (16)	−0.0059 (16)	−0.0066 (14)	0.0004 (14)
C27	0.0400 (16)	0.0384 (16)	0.0425 (15)	0.0029 (13)	0.0002 (13)	−0.0008 (12)
C28	0.0571 (19)	0.0471 (18)	0.0580 (18)	0.0050 (16)	0.0054 (16)	−0.0155 (15)

Geometric parameters (Å, º) top

S1—C1	1.688 (2)	C11—H11	0.9500
S2—C15	1.692 (2)	C12—C13	1.392 (3)
N1—C1	1.331 (3)	C12—H12	0.9500
N1—C2	1.473 (3)	C13—H13	0.9500
N1—H1N	0.8800	C14—H14A	0.9800
N2—C1	1.373 (3)	C14—H14B	0.9800
N2—C4	1.425 (3)	C14—H14C	0.9800
N2—C8	1.443 (3)	C16—C17	1.487 (4)
N3—C15	1.329 (3)	C16—C20	1.520 (4)
N3—C16	1.478 (3)	C16—C19	1.531 (4)
N3—H3N	0.8800	C17—C18	1.324 (4)
N4—C15	1.366 (3)	C17—H17	0.9500
N4—C18	1.426 (3)	C18—C21	1.484 (4)
N4—C22	1.450 (3)	C19—H19A	0.9800
C2—C3	1.487 (3)	C19—H19B	0.9800
C2—C5	1.521 (3)	C19—H19C	0.9800
C2—C6	1.521 (3)	C20—H20A	0.9800
C3—C4	1.329 (3)	C20—H20B	0.9800
C3—H3	0.9500	C20—H20C	0.9800
C4—C7	1.493 (3)	C21—H21A	0.9800
C5—H5A	0.9800	C21—H21B	0.9800
C5—H5B	0.9800	C21—H21C	0.9800
C5—H5C	0.9800	C22—C23	1.372 (3)
C6—H6A	0.9800	C22—C27	1.381 (3)
C6—H6B	0.9800	C23—C24	1.396 (3)
C6—H6C	0.9800	C23—H23	0.9500
C7—H7A	0.9800	C24—C25	1.382 (4)
C7—H7B	0.9800	C24—C28	1.501 (4)
C7—H7C	0.9800	C25—C26	1.381 (4)
C8—C9	1.376 (3)	C25—H25	0.9500
C8—C13	1.381 (3)	C26—C27	1.386 (4)
C9—C10	1.396 (3)	C26—H26	0.9500
C9—H9	0.9500	C27—H27	0.9500
C10—C11	1.382 (4)	C28—H28A	0.9800
C10—C14	1.501 (3)	C28—H28B	0.9800
C11—C12	1.380 (3)	C28—H28C	0.9800

C1—N1—C2	126.47 (19)	C10—C14—H14A	109.5
C1—N1—H1N	116.8	C10—C14—H14B	109.5
C2—N1—H1N	116.8	H14A—C14—H14B	109.5
C1—N2—C4	121.07 (19)	C10—C14—H14C	109.5
C1—N2—C8	118.86 (19)	H14A—C14—H14C	109.5
C4—N2—C8	119.99 (18)	H14B—C14—H14C	109.5
C15—N3—C16	128.0 (2)	N3—C15—N4	117.6 (2)
C15—N3—H3N	116.0	N3—C15—S2	120.77 (18)
C16—N3—H3N	116.0	N4—C15—S2	121.60 (18)
C15—N4—C18	120.7 (2)	N3—C16—C17	107.7 (2)
C15—N4—C22	120.1 (2)	N3—C16—C20	108.3 (2)
C18—N4—C22	119.22 (19)	C17—C16—C20	112.2 (2)
N1—C1—N2	117.0 (2)	N3—C16—C19	109.3 (2)
N1—C1—S1	121.21 (17)	C17—C16—C19	110.0 (2)
N2—C1—S1	121.80 (17)	C20—C16—C19	109.3 (2)
N1—C2—C3	107.76 (19)	C18—C17—C16	124.3 (2)
N1—C2—C5	107.5 (2)	C18—C17—H17	117.9
C3—C2—C5	112.3 (2)	C16—C17—H17	117.9
N1—C2—C6	108.8 (2)	C17—C18—N4	120.0 (2)
C3—C2—C6	110.9 (2)	C17—C18—C21	123.5 (3)
C5—C2—C6	109.4 (2)	N4—C18—C21	116.6 (2)
C4—C3—C2	123.1 (2)	C16—C19—H19A	109.5
C4—C3—H3	118.4	C16—C19—H19B	109.5
C2—C3—H3	118.4	H19A—C19—H19B	109.5
C3—C4—N2	119.3 (2)	C16—C19—H19C	109.5
C3—C4—C7	124.2 (2)	H19A—C19—H19C	109.5
N2—C4—C7	116.5 (2)	H19B—C19—H19C	109.5
C2—C5—H5A	109.5	C16—C20—H20A	109.5
C2—C5—H5B	109.5	C16—C20—H20B	109.5
H5A—C5—H5B	109.5	H20A—C20—H20B	109.5
C2—C5—H5C	109.5	C16—C20—H20C	109.5
H5A—C5—H5C	109.5	H20A—C20—H20C	109.5
H5B—C5—H5C	109.5	H20B—C20—H20C	109.5
C2—C6—H6A	109.5	C18—C21—H21A	109.5
C2—C6—H6B	109.5	C18—C21—H21B	109.5
H6A—C6—H6B	109.5	H21A—C21—H21B	109.5
C2—C6—H6C	109.5	C18—C21—H21C	109.5
H6A—C6—H6C	109.5	H21A—C21—H21C	109.5
H6B—C6—H6C	109.5	H21B—C21—H21C	109.5
C4—C7—H7A	109.5	C23—C22—C27	120.9 (2)
C4—C7—H7B	109.5	C23—C22—N4	119.8 (2)
H7A—C7—H7B	109.5	C27—C22—N4	119.2 (2)
C4—C7—H7C	109.5	C22—C23—C24	120.6 (2)
H7A—C7—H7C	109.5	C22—C23—H23	119.7
H7B—C7—H7C	109.5	C24—C23—H23	119.7
C9—C8—C13	121.5 (2)	C25—C24—C23	118.1 (2)
C9—C8—N2	119.4 (2)	C25—C24—C28	121.6 (2)
C13—C8—N2	119.2 (2)	C23—C24—C28	120.3 (2)
C8—C9—C10	120.1 (2)	C26—C25—C24	121.3 (2)
C8—C9—H9	119.9	C26—C25—H25	119.3
C10—C9—H9	119.9	C24—C25—H25	119.3
C11—C10—C9	118.3 (2)	C25—C26—C27	120.0 (3)
C11—C10—C14	122.4 (2)	C25—C26—H26	120.0
C9—C10—C14	119.3 (2)	C27—C26—H26	120.0
C12—C11—C10	121.6 (2)	C22—C27—C26	119.0 (3)
C12—C11—H11	119.2	C22—C27—H27	120.5
C10—C11—H11	119.2	C26—C27—H27	120.5
C11—C12—C13	119.9 (2)	C24—C28—H28A	109.5
C11—C12—H12	120.1	C24—C28—H28B	109.5
C13—C12—H12	120.1	H28A—C28—H28B	109.5
C8—C13—C12	118.7 (2)	C24—C28—H28C	109.5
C8—C13—H13	120.7	H28A—C28—H28C	109.5
C12—C13—H13	120.7	H28B—C28—H28C	109.5

C2—N1—C1—N2	−12.6 (4)	C16—N3—C15—N4	−5.1 (4)
C2—N1—C1—S1	168.88 (18)	C16—N3—C15—S2	176.2 (2)
C4—N2—C1—N1	−7.6 (3)	C18—N4—C15—N3	−6.2 (4)
C8—N2—C1—N1	175.5 (2)	C22—N4—C15—N3	172.5 (2)
C4—N2—C1—S1	170.90 (17)	C18—N4—C15—S2	172.50 (19)
C8—N2—C1—S1	−6.0 (3)	C22—N4—C15—S2	−8.8 (3)
C1—N1—C2—C3	25.6 (3)	C15—N3—C16—C17	13.6 (4)
C1—N1—C2—C5	146.8 (2)	C15—N3—C16—C20	135.1 (3)
C1—N1—C2—C6	−94.7 (3)	C15—N3—C16—C19	−105.9 (3)
N1—C2—C3—C4	−21.0 (3)	N3—C16—C17—C18	−12.5 (4)
C5—C2—C3—C4	−139.2 (3)	C20—C16—C17—C18	−131.6 (3)
C6—C2—C3—C4	98.0 (3)	C19—C16—C17—C18	106.6 (3)
C2—C3—C4—N2	5.3 (4)	C16—C17—C18—N4	3.8 (5)
C2—C3—C4—C7	−175.9 (2)	C16—C17—C18—C21	−176.6 (3)
C1—N2—C4—C3	11.0 (3)	C15—N4—C18—C17	6.8 (4)
C8—N2—C4—C3	−172.1 (2)	C22—N4—C18—C17	−171.9 (3)
C1—N2—C4—C7	−167.8 (2)	C15—N4—C18—C21	−172.8 (3)
C8—N2—C4—C7	9.1 (3)	C22—N4—C18—C21	8.5 (4)
C1—N2—C8—C9	94.8 (3)	C15—N4—C22—C23	100.7 (3)
C4—N2—C8—C9	−82.2 (3)	C18—N4—C22—C23	−80.6 (3)
C1—N2—C8—C13	−85.9 (3)	C15—N4—C22—C27	−83.1 (3)
C4—N2—C8—C13	97.1 (3)	C18—N4—C22—C27	95.6 (3)
C13—C8—C9—C10	0.1 (4)	C27—C22—C23—C24	−0.2 (4)
N2—C8—C9—C10	179.3 (2)	N4—C22—C23—C24	175.8 (2)
C8—C9—C10—C11	1.4 (3)	C22—C23—C24—C25	0.2 (4)
C8—C9—C10—C14	−177.9 (2)	C22—C23—C24—C28	−179.5 (2)
C9—C10—C11—C12	−1.8 (4)	C23—C24—C25—C26	0.4 (4)
C14—C10—C11—C12	177.4 (2)	C28—C24—C25—C26	−179.9 (3)
C10—C11—C12—C13	0.8 (4)	C24—C25—C26—C27	−0.9 (4)
C9—C8—C13—C12	−1.2 (4)	C23—C22—C27—C26	−0.2 (4)
N2—C8—C13—C12	179.5 (2)	N4—C22—C27—C26	−176.4 (2)
C11—C12—C13—C8	0.8 (3)	C25—C26—C27—C22	0.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S2	0.88	2.62	3.419 (2)	151
N3—H3N···S1	0.88	2.60	3.447 (2)	163

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈N₂S
M_r	246.36
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	173
a, b, c (Å)	10.5904 (3), 16.9189 (5), 30.5713 (10)
V (Å³)	5477.7 (3)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.14 × 0.12 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1997)
T_min, T_max	0.970, 0.983
No. of measured, independent and observed [I > 2.0σ(I)] reflections	19135, 4830, 3231
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.115, 1.04
No. of reflections	4830
No. of parameters	315
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.23

Computer programs: COLLECT (Hooft, 1998), HKL DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S2	0.88	2.62	3.419 (2)	151
N3—H3N···S1	0.88	2.60	3.447 (2)	163

Acknowledgements

The authors gratefully acknowledge a research grant from the Higher Education Commission of Pakistan under project No. 20-Miscel/R&D/00/3834.

References

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