5-(4-Eth­oxy­phen­yl)-3-(pyridin-2-yl)-4,5-dihydro-1H-pyrazole-1-carbothio­amide

Chantrapromma, S.; Nonthason, P.; Suwunwong, T.; Fun, H.-K.

doi:10.1107/S1600536812006642

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages o830-o831

doi:10.1107/S1600536812006642

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5-(4-Ethoxyphenyl)-3-(pyridin-2-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide

Suchada Chantrapromma,^a ^*‡ Phonpawee Nonthason,^a Thitipone Suwunwong ^a and Hoong-Kun Fun ^b §

^aCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: suchada.c@psu.ac.th

(Received 5 February 2012; accepted 14 February 2012; online 24 February 2012)

In the title compound, C₁₇H₁₈N₄OS, a pyrazoline derivative, the pyrazoline ring adopts an envelope conformation with the C atom bonded to the benzene ring as the flap atom. The dihedral angle between the pyridine and benzene rings is 80.50 (6)°. The ethoxyphenyl group is approximately planar, with an r.m.s. deviation of 0.0238 (1) Å for the nine non-H atoms. In the crystal, molecules are linked by N—H⋯O and N—H⋯S hydrogen bonds into a tape along the b axis. Weak C—H⋯N and C—H⋯π interactions are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ). For related literature on ring conformations, see: Cremer & Pople (1975 ). For related structures, see: Fun et al. (2012 ); Nonthason et al. (2011 ). For background to and applications of pyrazoline derivatives, see: Amir et al. (2008 ); Gong et al. (2011 ); Husain et al. (2008 ); Manna & Agrawal (2009 ); Özdemir et al. (2007 ); Sarkar et al. (2010 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₇H₁₈N₄OS
M_r = 326.42
Monoclinic, P 2₁ /c
a = 13.4622 (1) Å
b = 9.4175 (1) Å
c = 13.3002 (2) Å
β = 103.146 (1)°
V = 1642.01 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.34 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.934, T_max = 0.960
23465 measured reflections
4784 independent reflections
3970 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.097
S = 1.03
4784 reflections
217 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C5/N3 and C9–C14 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯S1ⁱ	0.925 (19)	2.472 (19)	3.3803 (12)	167.3 (15)
N4—H2N4⋯O1ⁱⁱ	0.825 (18)	2.296 (18)	3.0604 (15)	154.2 (17)
C3—H3A⋯N3ⁱⁱⁱ	0.95	2.51	3.4053 (18)	156
C2—H2A⋯Cg2ⁱⁱⁱ	0.95	2.67	3.4401 (14)	138
C7—H7A⋯Cg1^iv	0.99	2.69	3.4841 (13)	138
Symmetry codes: (i) -x+1, -y+2, -z+2; (ii) x, y+1, z; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x+2, -y+2, -z+2.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812006642/is5069sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812006642/is5069Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812006642/is5069Isup3.cml

checkCIF report

Comment top

Pyrazoline derivatives are of interest in many fields, such as in medicinal chemistry due to their various bioactivities i.e. antidepressant and anticonvulsant (Özdemir et al., 2007), antimicrobial (Manna & Agrawal, 2009), antiamoebic (Husain et al., 2008), analgesic and anti-inflammatory (Amir et al., 2008) properties, as well as being used as fluorescent sensors (Gong et al., 2011) and fluorescent probes (Sarkar et al., 2010). The title pyrazoline derivative (I) was synthesized because we want to modify the structure of heteroaryl chalcone derivative in order to enhance its fluorescence property, by cyclization with thiosemicarbazide. (I) possess fluorescent property as expected which will be reported elsewhere with its closely related compound (Nonthason et al., 2011).

In the molecule of the title pyrazoline derivative (Fig. 1), C₁₇H₁₈N₄OS, the pyrazoline ring adopts envelope conformation with the puckered C8 atom having the maximum deviation of 0.1408 (13) Å, and the puckering parameter Q = 0.2236 (13) Å and ϕ = 77.6 (3)° (Cremer & Pople, 1975). The dihedral angle between the pyridine and benzene ring is 80.50 (6)°. The conformation of the carbothioamide unit with respect to the pyrazoline ring can be indicated by the torsion angles N1–N2–C15–N4 = 1.90 (17)° and N1–N2–C15–S1 = -177.84 (8)°. The ethoxy group is co-planar with its attached benzene ring with the torsion angle C16–O1–C12–C11 = -0.39 (17)° and C12–O1–C16–C17 = 177.61 (11)°, and an r.m.s. deviation of 0.0238 (1) Å for the nine non H atoms (C9–C14/O1/C16/C17). Bond distances of (I) are in normal range (Allen et al., 1987) and comparable with the related structures (Fun et al., 2012; Nonthason et al., 2011)

In the crystal packing (Fig. 2), the molecules are linked by N—H···O, and N—H···S hydrogen bonds into a tape along the b axis. Weak C—H···N and C—H···π interactions are also present (Table 1).

Related literature top

For bond-length data, see: Allen et al. (1987). For related literature on ring conformations, see: Cremer & Pople (1975). For related structures, see: Fun et al. (2012); Nonthason et al. (2011). For background to and applications of pyrazoline derivatives, see: Amir et al. (2008); Gong et al. (2011); Husain et al. (2008); Manna & Agrawal (2009); Özdemir et al. (2007); Sarkar et al. (2010). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

The title compound was synthesized by cyclization reaction of E-3-(4-ethoxyphenyl)-1-(pyridin-2-yl)prop-2-en-1-one (0.25 g, 1 mmol) with excess thiosemicarbazide (0.18 g, 2 mmol) in a solution of KOH (0.11 g, 2 mmol) in ethanol (10 ml). The reaction mixture was vigorously stirred and refluxed for 5 h. The pale-yellow solid of the title compound obtained after cooling of the reaction was then filtered off under vacuum. Pale yellow block-shaped single crystals of the title compound suitable for X-ray structure determination were recrystallized from ethanol by slow evaporation of the solvent at room temperature after several days (m.p. 480–481 K).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 60% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. A packing diagram of the title compound viewed along the c axis. For the sake of clarity, only H atoms involved in the hydrogen bonds were shown. The hydrogen bonds were drawn as dashed lines.

5-(4-Ethoxyphenyl)-3-(pyridin-2-yl)-4,5-dihydro-1H-pyrazole-1- carbothioamide top

Crystal data top

C₁₇H₁₈N₄OS	F(000) = 688
M_r = 326.42	D_x = 1.320 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 480–481 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.4622 (1) Å	Cell parameters from 4784 reflections
b = 9.4175 (1) Å	θ = 1.6–30.0°
c = 13.3002 (2) Å	µ = 0.21 mm⁻¹
β = 103.146 (1)°	T = 100 K
V = 1642.01 (3) Å³	Block, pale yellow
Z = 4	0.34 × 0.22 × 0.20 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	4784 independent reflections
Radiation source: sealed tube	3970 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 30.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −18→18
T_min = 0.934, T_max = 0.960	k = −13→11
23465 measured reflections	l = −18→13

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) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0417P)² + 0.7316P] where P = (F_o² + 2F_c²)/3
4784 reflections	(Δ/σ)_max = 0.001
217 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₇H₁₈N₄OS	V = 1642.01 (3) Å³
M_r = 326.42	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.4622 (1) Å	µ = 0.21 mm⁻¹
b = 9.4175 (1) Å	T = 100 K
c = 13.3002 (2) Å	0.34 × 0.22 × 0.20 mm
β = 103.146 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4784 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3970 reflections with I > 2σ(I)
T_min = 0.934, T_max = 0.960	R_int = 0.028
23465 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.45 e Å⁻³
4784 reflections	Δρ_min = −0.26 e Å⁻³
217 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 120.0 (1) K.

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 > 2sigma(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	0.59440 (2)	0.80604 (3)	1.06339 (3)	0.01960 (9)
O1	0.68026 (7)	0.21264 (9)	0.77613 (7)	0.01893 (19)
N1	0.79666 (8)	0.91705 (11)	0.90593 (8)	0.0162 (2)
N2	0.74574 (8)	0.84262 (11)	0.96929 (8)	0.0159 (2)
N3	1.05784 (8)	0.87566 (12)	0.89934 (8)	0.0186 (2)
N4	0.61973 (9)	1.00933 (12)	0.93150 (9)	0.0214 (2)
H1N4	0.5594 (14)	1.0488 (19)	0.9404 (13)	0.033 (5)*
H2N4	0.6522 (13)	1.0458 (19)	0.8925 (14)	0.032 (5)*
C1	1.12851 (10)	0.92690 (15)	0.85186 (10)	0.0216 (3)
H1A	1.1969	0.8950	0.8749	0.026*
C2	1.10730 (10)	1.02328 (15)	0.77156 (10)	0.0228 (3)
H2A	1.1596	1.0559	0.7399	0.027*
C3	1.00762 (10)	1.07148 (15)	0.73821 (10)	0.0211 (3)
H3A	0.9908	1.1381	0.6833	0.025*
C4	0.93292 (9)	1.02150 (14)	0.78583 (10)	0.0187 (2)
H4A	0.8643	1.0528	0.7644	0.022*
C5	0.96155 (9)	0.92381 (13)	0.86619 (9)	0.0159 (2)
C6	0.88757 (9)	0.86558 (13)	0.92109 (9)	0.0153 (2)
C7	0.90988 (9)	0.75117 (13)	1.00217 (9)	0.0162 (2)
H7A	0.9520	0.7875	1.0681	0.019*
H7B	0.9445	0.6689	0.9789	0.019*
C8	0.80072 (9)	0.71273 (13)	1.01217 (9)	0.0147 (2)
H8A	0.7983	0.6995	1.0862	0.018*
C9	0.76061 (9)	0.58201 (13)	0.94880 (9)	0.0142 (2)
C10	0.68335 (9)	0.58700 (13)	0.85977 (9)	0.0167 (2)
H10A	0.6505	0.6749	0.8388	0.020*
C11	0.65281 (9)	0.46572 (13)	0.80034 (10)	0.0179 (2)
H11A	0.5992	0.4710	0.7401	0.022*
C12	0.70147 (9)	0.33741 (13)	0.83010 (9)	0.0159 (2)
C13	0.77894 (10)	0.32974 (13)	0.91996 (10)	0.0184 (2)
H13A	0.8118	0.2418	0.9409	0.022*
C14	0.80746 (9)	0.45060 (13)	0.97800 (9)	0.0180 (2)
H14A	0.8600	0.4447	1.0391	0.022*
C15	0.65479 (9)	0.89184 (13)	0.98368 (9)	0.0159 (2)
C16	0.60157 (10)	0.21507 (15)	0.68243 (11)	0.0246 (3)
H16A	0.6181	0.2859	0.6337	0.029*
H16B	0.5352	0.2406	0.6977	0.029*
C17	0.59640 (12)	0.06844 (16)	0.63618 (12)	0.0306 (3)
H17A	0.5425	0.0655	0.5728	0.046*
H17B	0.5814	−0.0008	0.6857	0.046*
H17C	0.6620	0.0453	0.6200	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02002 (15)	0.01758 (16)	0.02402 (17)	0.00250 (12)	0.01091 (12)	0.00250 (12)
O1	0.0221 (4)	0.0132 (4)	0.0194 (4)	−0.0009 (3)	0.0005 (3)	−0.0023 (3)
N1	0.0165 (5)	0.0138 (5)	0.0194 (5)	−0.0013 (4)	0.0066 (4)	0.0001 (4)
N2	0.0172 (5)	0.0121 (5)	0.0197 (5)	0.0011 (4)	0.0070 (4)	0.0016 (4)
N3	0.0160 (5)	0.0194 (6)	0.0208 (5)	0.0001 (4)	0.0048 (4)	0.0000 (4)
N4	0.0191 (5)	0.0181 (6)	0.0301 (6)	0.0044 (4)	0.0119 (5)	0.0068 (5)
C1	0.0161 (6)	0.0240 (7)	0.0258 (7)	0.0004 (5)	0.0072 (5)	−0.0014 (5)
C2	0.0230 (6)	0.0245 (7)	0.0236 (6)	−0.0037 (5)	0.0114 (5)	−0.0013 (5)
C3	0.0248 (6)	0.0207 (6)	0.0180 (6)	−0.0025 (5)	0.0054 (5)	0.0018 (5)
C4	0.0179 (6)	0.0186 (6)	0.0193 (6)	−0.0007 (5)	0.0032 (4)	0.0007 (5)
C5	0.0165 (5)	0.0145 (6)	0.0171 (5)	−0.0017 (4)	0.0046 (4)	−0.0023 (4)
C6	0.0158 (5)	0.0136 (6)	0.0165 (5)	−0.0012 (4)	0.0036 (4)	−0.0016 (4)
C7	0.0158 (5)	0.0145 (6)	0.0179 (6)	0.0005 (4)	0.0032 (4)	0.0004 (5)
C8	0.0159 (5)	0.0125 (6)	0.0162 (5)	0.0012 (4)	0.0044 (4)	0.0006 (4)
C9	0.0143 (5)	0.0130 (6)	0.0163 (5)	−0.0002 (4)	0.0055 (4)	0.0007 (4)
C10	0.0152 (5)	0.0139 (6)	0.0206 (6)	0.0023 (4)	0.0033 (4)	0.0012 (5)
C11	0.0158 (5)	0.0168 (6)	0.0193 (6)	0.0013 (5)	0.0001 (4)	−0.0005 (5)
C12	0.0165 (5)	0.0141 (6)	0.0181 (6)	−0.0021 (4)	0.0059 (4)	−0.0010 (5)
C13	0.0209 (6)	0.0129 (6)	0.0204 (6)	0.0020 (5)	0.0026 (5)	0.0025 (5)
C14	0.0207 (6)	0.0161 (6)	0.0154 (5)	0.0008 (5)	0.0005 (4)	0.0022 (5)
C15	0.0161 (5)	0.0129 (6)	0.0188 (6)	−0.0004 (4)	0.0043 (4)	−0.0032 (4)
C16	0.0219 (6)	0.0227 (7)	0.0254 (7)	−0.0008 (5)	−0.0027 (5)	−0.0057 (5)
C17	0.0315 (7)	0.0262 (8)	0.0311 (8)	−0.0015 (6)	0.0010 (6)	−0.0125 (6)

Geometric parameters (Å, º) top

S1—C15	1.6822 (13)	C7—C8	1.5483 (16)
O1—C12	1.3726 (15)	C7—H7A	0.9900
O1—C16	1.4406 (15)	C7—H7B	0.9900
N1—C6	1.2889 (15)	C8—C9	1.5201 (17)
N1—N2	1.3906 (14)	C8—H8A	1.0000
N2—C15	1.3628 (15)	C9—C10	1.3878 (16)
N2—C8	1.4756 (15)	C9—C14	1.4032 (17)
N3—C1	1.3454 (16)	C10—C11	1.3966 (17)
N3—C5	1.3492 (16)	C10—H10A	0.9500
N4—C15	1.3341 (17)	C11—C12	1.3885 (17)
N4—H1N4	0.925 (18)	C11—H11A	0.9500
N4—H2N4	0.825 (18)	C12—C13	1.3979 (17)
C1—C2	1.3810 (19)	C13—C14	1.3799 (18)
C1—H1A	0.9500	C13—H13A	0.9500
C2—C3	1.3902 (19)	C14—H14A	0.9500
C2—H2A	0.9500	C16—C17	1.5069 (19)
C3—C4	1.3871 (17)	C16—H16A	0.9900
C3—H3A	0.9500	C16—H16B	0.9900
C4—C5	1.3964 (18)	C17—H17A	0.9800
C4—H4A	0.9500	C17—H17B	0.9800
C5—C6	1.4685 (16)	C17—H17C	0.9800
C6—C7	1.5056 (17)

C12—O1—C16	117.61 (10)	N2—C8—H8A	111.0
C6—N1—N2	107.28 (10)	C9—C8—H8A	111.0
C15—N2—N1	119.74 (10)	C7—C8—H8A	111.0
C15—N2—C8	127.98 (10)	C10—C9—C14	117.94 (11)
N1—N2—C8	112.27 (9)	C10—C9—C8	123.27 (11)
C1—N3—C5	117.10 (11)	C14—C9—C8	118.69 (10)
C15—N4—H1N4	118.9 (11)	C9—C10—C11	121.48 (11)
C15—N4—H2N4	119.8 (12)	C9—C10—H10A	119.3
H1N4—N4—H2N4	121.3 (16)	C11—C10—H10A	119.3
N3—C1—C2	123.70 (12)	C12—C11—C10	119.43 (11)
N3—C1—H1A	118.2	C12—C11—H11A	120.3
C2—C1—H1A	118.2	C10—C11—H11A	120.3
C1—C2—C3	118.44 (12)	O1—C12—C11	124.56 (11)
C1—C2—H2A	120.8	O1—C12—C13	115.40 (11)
C3—C2—H2A	120.8	C11—C12—C13	120.03 (11)
C4—C3—C2	119.40 (12)	C14—C13—C12	119.62 (11)
C4—C3—H3A	120.3	C14—C13—H13A	120.2
C2—C3—H3A	120.3	C12—C13—H13A	120.2
C3—C4—C5	118.07 (12)	C13—C14—C9	121.48 (11)
C3—C4—H4A	121.0	C13—C14—H14A	119.3
C5—C4—H4A	121.0	C9—C14—H14A	119.3
N3—C5—C4	123.29 (11)	N4—C15—N2	115.59 (11)
N3—C5—C6	114.95 (11)	N4—C15—S1	124.18 (9)
C4—C5—C6	121.75 (11)	N2—C15—S1	120.24 (9)
N1—C6—C5	120.60 (11)	O1—C16—C17	107.17 (11)
N1—C6—C7	114.13 (10)	O1—C16—H16A	110.3
C5—C6—C7	125.17 (10)	C17—C16—H16A	110.3
C6—C7—C8	100.97 (9)	O1—C16—H16B	110.3
C6—C7—H7A	111.6	C17—C16—H16B	110.3
C8—C7—H7A	111.6	H16A—C16—H16B	108.5
C6—C7—H7B	111.6	C16—C17—H17A	109.5
C8—C7—H7B	111.6	C16—C17—H17B	109.5
H7A—C7—H7B	109.4	H17A—C17—H17B	109.5
N2—C8—C9	111.92 (10)	C16—C17—H17C	109.5
N2—C8—C7	100.10 (9)	H17A—C17—H17C	109.5
C9—C8—C7	111.48 (10)	H17B—C17—H17C	109.5

C6—N1—N2—C15	167.71 (11)	C6—C7—C8—C9	97.86 (11)
C6—N1—N2—C8	−13.34 (13)	N2—C8—C9—C10	1.69 (16)
C5—N3—C1—C2	−0.8 (2)	C7—C8—C9—C10	−109.50 (13)
N3—C1—C2—C3	0.6 (2)	N2—C8—C9—C14	178.00 (10)
C1—C2—C3—C4	−0.2 (2)	C7—C8—C9—C14	66.81 (14)
C2—C3—C4—C5	0.03 (19)	C14—C9—C10—C11	−0.20 (18)
C1—N3—C5—C4	0.56 (19)	C8—C9—C10—C11	176.13 (11)
C1—N3—C5—C6	−179.50 (11)	C9—C10—C11—C12	−0.76 (18)
C3—C4—C5—N3	−0.21 (19)	C16—O1—C12—C11	−0.39 (17)
C3—C4—C5—C6	179.86 (11)	C16—O1—C12—C13	−179.50 (11)
N2—N1—C6—C5	−179.01 (10)	C10—C11—C12—O1	−177.82 (11)
N2—N1—C6—C7	−2.46 (14)	C10—C11—C12—C13	1.26 (18)
N3—C5—C6—N1	170.77 (11)	O1—C12—C13—C14	178.37 (11)
C4—C5—C6—N1	−9.29 (18)	C11—C12—C13—C14	−0.79 (18)
N3—C5—C6—C7	−5.37 (17)	C12—C13—C14—C9	−0.19 (19)
C4—C5—C6—C7	174.57 (12)	C10—C9—C14—C13	0.68 (18)
N1—C6—C7—C8	15.72 (14)	C8—C9—C14—C13	−175.83 (11)
C5—C6—C7—C8	−167.92 (11)	N1—N2—C15—N4	1.90 (17)
C15—N2—C8—C9	82.65 (15)	C8—N2—C15—N4	−176.86 (11)
N1—N2—C8—C9	−96.19 (11)	N1—N2—C15—S1	−177.84 (8)
C15—N2—C8—C7	−159.15 (12)	C8—N2—C15—S1	3.40 (17)
N1—N2—C8—C7	22.01 (12)	C12—O1—C16—C17	177.61 (11)
C6—C7—C8—N2	−20.67 (11)

Hydrogen-bond geometry (Å, º) top

Cg₁ and Cg₂ are the centroids of the C1–C5/N1 and C9–C14 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···S1ⁱ	0.925 (19)	2.472 (19)	3.3803 (12)	167.3 (15)
N4—H2N4···O1ⁱⁱ	0.825 (18)	2.296 (18)	3.0604 (15)	154.2 (17)
C3—H3A···N3ⁱⁱⁱ	0.95	2.51	3.4053 (18)	156
C2—H2A···Cg2ⁱⁱⁱ	0.95	2.67	3.4401 (14)	138
C7—H7A···Cg1^iv	0.99	2.69	3.4841 (13)	138

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

Experimental details

Crystal data
Chemical formula	C₁₇H₁₈N₄OS
M_r	326.42
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.4622 (1), 9.4175 (1), 13.3002 (2)
β (°)	103.146 (1)
V (Å³)	1642.01 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.34 × 0.22 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.934, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	23465, 4784, 3970
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.097, 1.03
No. of reflections	4784
No. of parameters	217
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.26

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg₁ and Cg₂ are the centroids of the C1–C5/N1 and C9–C14 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···S1ⁱ	0.925 (19)	2.472 (19)	3.3803 (12)	167.3 (15)
N4—H2N4···O1ⁱⁱ	0.825 (18)	2.296 (18)	3.0604 (15)	154.2 (17)
C3—H3A···N3ⁱⁱⁱ	0.95	2.51	3.4053 (18)	156
C2—H2A···Cg2ⁱⁱⁱ	0.95	2.67	3.4401 (14)	138
C7—H7A···Cg1^iv	0.99	2.69	3.4841 (13)	138

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

Footnotes

‡Thomson Reuters ResearcherID: A-5085-2009.

§Thomson Reuters ResearcherID: A-3561-2009. Additional correspondence author, e-mail: hkfun@usm.my.

Acknowledgements

The authors thank the Prince of Songkla Univeristy for financial support through the Crystal Materials Research Unit and the Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160. PN thanks the Development and Promotion of Science and Technology Talents Project for a fellowship.

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