1-[4-(Di­methyl­amino)­benzyl­idene]-4-o-tolyl­thio­semicarbazide

Huang, R.-Y.; Xu, Q.-J.; Lin, L.-R.

doi:10.1107/S1600536813012890

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 6| June 2013| Pages o906-o907

doi:10.1107/S1600536813012890

Open

access

ADDENDA AND ERRATA

A correction has been published for this article. To view the correction, click here.

1-[4-(Dimethylamino)benzylidene]-4-o-tolylthiosemicarbazide

Rui-Yun Huang,^a Qin-Juan Xu ^a and Li-Rong Lin ^a ^*

^aDepartment of Chemistry, Xiamen University, Xiamen 361005, People's Republic of China
^*Correspondence e-mail: linlr@xmu.edu.cn

(Received 21 April 2013; accepted 10 May 2013; online 18 May 2013)

The asymmetric unit of the title compound, C₁₇H₂₀N₄S, contains two independent molecules, the main difference between them being the dihedral angles between the benzene rings [19.99 (17) and 9.72 (17)°]. The molecules both have a trans conformation about the C=N double bond and intramolecular C—H⋯S and N—H⋯N hydrogen bonds are observed in both molecules. In the crystal, molecules are linked by weak N—H⋯S hydrogen bonds with graph-set motif R₂²(8). In each molecule, all but one of the N atoms and both the S atoms are involved in hydrogen bonding.

Related literature

For details of anion recognition, see: Sessler et al. (2006 ); Amendola et al. (2006 ); Fahlbusch et al. (2006 ); Gale & Quesada (2006 ); Perez & Riera (2008 ); Willans et al. (2009 ); Amendola & Fabbrizzi (2009 ); Haridas et al. (2012 ). For applications of thiosemicarbazides, see: Basuli et al. (1998 ); Pandeya et al. (1999 ); Kowol et al. (2010 ). For thiosemicarbazones acting as anion acceptors, see: Chikate et al. (2005 ); Krisitin (2005 ). For details of the synthesis of the Schiff base ligand, see: Pouralimardan et al. (2007 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₇H₂₀N₄S
M_r = 312.43
Triclinic, $[P \overline 1]$
a = 9.172 (3) Å
b = 12.224 (4) Å
c = 15.563 (5) Å
α = 86.933 (6)°
β = 86.990 (7)°
γ = 70.382 (6)°
V = 1640.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 173 K
0.20 × 0.15 × 0.03 mm

Data collection

Brucker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick,2008 ) T_min = 0.961, T_max = 0.994
7929 measured reflections
5640 independent reflections
3127 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.155
S = 0.95
5640 reflections
419 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4N⋯N2	0.95 (3)	2.05 (3)	2.587 (3)	114 (3)
C12—H12A⋯S1	0.93	2.64	3.239 (4)	123
C29—H29A⋯S2	0.93	2.57	3.257 (4)	131
N7—H7N⋯S1ⁱ	0.86	2.61	3.458 (3)	170
N3—H3N⋯S2ⁱⁱ	0.86	2.59	3.439 (3)	171
N8—H8N⋯N6	0.97 (3)	2.01 (3)	2.587 (4)	116 (2)
Symmetry codes: (i) x, y, z+1; (ii) x, y, z-1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; 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, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813012890/bx2440sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813012890/bx2440Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813012890/bx2440Isup3.mol

Supporting information file. DOI: 10.1107/S1600536813012890/bx2440Isup4.cml

checkCIF report

Comment top

Recently, anions recognition and sensing has attracted growing attentions due to their important roles in the fields of environmental science, biology, catalysis and medicine (Sessler et al. 2006). Substantial progress has been made in the development of anion receptors (Amendola et al. 2006, Gale et al. 2006, Perez & Riera 2008, Amendola et al. 2009, Kowol et al. 2010, Haridas et al. 2012). Thiosemicarbazide has been widely used in catalysis, drug, bacterialcide, flotation agent, (Pouralimardan et al. 2007). Some thiosemicarbazide derivatives show interesting biological effects, such as anticancer and anti-HIV properties (Pandeya et al. 1999; Fahlbusch et al. 2006). There are also a few reports of thiosemicarbazide acting as anion acceptors (Chikate et al. 2005). The introduction of a strong electron-donating group such as the N,N-dimethylanilino group through a double bond imparts new properties that are not commonly observed for the parent thiourea. As part of our work in this area, we report here the synthesis and structure of the title compound.The asymmetric unit of the title compound, C₁₇H₂₀N₄S, consists of two crystallographically independent molecules. The main differences of both molecules are the dihedral angles between the benzene rings, 19.99 (17)° and 9.72 (17)°. In the crystal, molecules are linked by weak intermolecular N—H···S hydrogen bonds with set graph-motif R²₂(8) (Bernstein et al., 1995). Intramolecular C—H···S and N—H···N hydrogen bonds are observe. In both molecules, all of the N atoms and two of the S atoms are involved in hydrogen bonding, with an average H···S distance of 2.61Å and N— H···S angles in the range 170–171°. The molecules have a trans configuration about the C=N double bond.

Related literature top

For details of anion recognition, see: Sessler et al. (2006); Amendola et al. (2006); Fahlbusch et al. (2006); Gale & Quesada (2006); Perez & Riera (2008); Willans et al. (2009); Amendola & Fabbrizzi (2009); Haridas et al. (2012). For applications of thiosemicarbazides, see: Basuli et al. (1998); Pandeya et al. (1999); Kowol et al. (2010). For thiosemicarbazones acting as anion acceptors, see: Chikate et al. (2005); Krisitin (2005). For details of the synthesis of the Schiff base ligand, see: Pouralimardan et al. (2007). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

The title compound was synthesized by refluxing an ethanol solution (20 ml) of 4-(dimethylamino) benzaldehyde (10 mmol) and 4-(4-methylphenyl)-3-thiosemicarbazide (10 mmol) for 3 h. The resulting yellow and clear solution was then cooled to room temperature. Light-yellow crystals were obtained, filtered and washed with cold ethanol. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of an acetonitrile and dichromethane mixed solution. M.P. 179~180 °C, MS (APCI) m/z (%): M⁺ 311.4, ¹H-NMR (CDCl₃), δ (p.p.m.): 9.53 (s,NH), 9.00 (s, NH), 7.84 (s, CH=N), 7.77 (dd, 1H, J = 4 Hz, ArH), 7.63 (d, 2H, J = 12 Hz, ArH), 7.32~7.30 (m, 1H, ArH), 7.25~7.23 (m, 2H, ArH), 7.02~6.99 (m, 2H, ArH), 3.10 (s, 6H, CH₃), 2.39 (s, 3H, CH₃).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. ORTEP plot of the title compound. The thermal ellipsoids are drawn at 30% probability level.

1-[4-(Dimethylamino)benzylidene]-4-o-tolylthiosemicarbazide top

Crystal data top

C₁₇H₂₀N₄S	Z = 4
M_r = 312.43	F(000) = 664
Triclinic, P1	D_x = 1.265 Mg m⁻³
Hall symbol: -P 1	Melting point: 452 K
a = 9.172 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.224 (4) Å	Cell parameters from 9709 reflections
c = 15.563 (5) Å	θ = 1.8–25.0°
α = 86.933 (6)°	µ = 0.20 mm⁻¹
β = 86.990 (7)°	T = 173 K
γ = 70.382 (6)°	Block, yellow
V = 1640.3 (9) Å³	0.20 × 0.15 × 0.03 mm

Data collection top

Brucker SMART APEX diffractometer	5640 independent reflections
Radiation source: fine-focus sealed tube	3127 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scan	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick,2008)	h = −9→10
T_min = 0.961, T_max = 0.994	k = −14→14
7929 measured reflections	l = −18→15

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ²(F_o²) + (0.0697P)²] where P = (F_o² + 2F_c²)/3
5640 reflections	(Δ/σ)_max = 0.001
419 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³
0 constraints

Crystal data top

C₁₇H₂₀N₄S	γ = 70.382 (6)°
M_r = 312.43	V = 1640.3 (9) Å³
Triclinic, P1	Z = 4
a = 9.172 (3) Å	Mo Kα radiation
b = 12.224 (4) Å	µ = 0.20 mm⁻¹
c = 15.563 (5) Å	T = 173 K
α = 86.933 (6)°	0.20 × 0.15 × 0.03 mm
β = 86.990 (7)°

Data collection top

Brucker SMART APEX diffractometer	5640 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick,2008)	3127 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.994	R_int = 0.027
7929 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.29 e Å⁻³
5640 reflections	Δρ_min = −0.17 e Å⁻³
419 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
H4N	0.578 (4)	0.812 (3)	0.419 (2)	0.090 (12)*
S2	1.04941 (11)	0.49993 (7)	1.21135 (6)	0.0688 (3)
S1	0.71619 (13)	0.85281 (7)	0.21044 (6)	0.0790 (3)
N8	0.9444 (3)	0.4024 (2)	1.08541 (17)	0.0587 (7)
N6	0.7262 (3)	0.5924 (2)	1.04273 (16)	0.0592 (7)
N7	0.8225 (3)	0.5919 (2)	1.10796 (16)	0.0617 (7)
H7N	0.8092	0.6550	1.1341	0.074*
N3	0.7612 (3)	0.6926 (2)	0.33190 (16)	0.0667 (8)
H3N	0.8358	0.6518	0.2990	0.080*
N2	0.7239 (3)	0.6441 (2)	0.40899 (16)	0.0622 (7)
C3	0.7517 (4)	0.3395 (3)	0.6503 (2)	0.0591 (8)
C27	0.9379 (4)	0.4935 (3)	1.13162 (18)	0.0526 (8)
N4	0.5776 (3)	0.8602 (2)	0.36927 (18)	0.0651 (8)
C20	0.3119 (3)	0.7492 (3)	0.8192 (2)	0.0540 (8)
C8	0.7901 (4)	0.4768 (2)	0.50474 (19)	0.0548 (8)
C25	0.5234 (3)	0.7076 (2)	0.95183 (19)	0.0530 (8)
C23	0.3245 (4)	0.8396 (3)	0.8656 (2)	0.0591 (8)
H23A	0.2616	0.9154	0.8530	0.071*
C28	1.0406 (4)	0.2847 (3)	1.0853 (2)	0.0544 (8)
C10	0.6811 (4)	0.8030 (3)	0.3086 (2)	0.0600 (8)
C21	0.4065 (4)	0.6374 (3)	0.8423 (2)	0.0639 (9)
H21A	0.4001	0.5748	0.8132	0.077*
N5	0.2121 (3)	0.7702 (2)	0.75317 (19)	0.0726 (8)
C24	0.4275 (4)	0.8183 (2)	0.9290 (2)	0.0580 (8)
H24A	0.4340	0.8808	0.9583	0.070*
C9	0.8135 (4)	0.5414 (3)	0.4282 (2)	0.0614 (9)
C7	0.8969 (4)	0.3691 (3)	0.5240 (2)	0.0648 (9)
H7B	0.9836	0.3406	0.4874	0.078*
C26	0.6322 (4)	0.6915 (3)	1.0191 (2)	0.0576 (8)
C11	0.4741 (4)	0.9757 (3)	0.37105 (19)	0.0559 (8)
C22	0.5090 (4)	0.6176 (2)	0.9070 (2)	0.0619 (9)
H22A	0.5704	0.5418	0.9210	0.074*
C33	1.0155 (4)	0.2181 (3)	1.0214 (2)	0.0612 (9)
C6	0.8797 (4)	0.3028 (3)	0.5947 (2)	0.0635 (9)
H6B	0.9557	0.2315	0.6057	0.076*
N1	0.7278 (3)	0.2725 (2)	0.71832 (18)	0.0754 (8)
C16	0.3454 (4)	0.9972 (3)	0.42636 (19)	0.0617 (9)
C5	0.6640 (4)	0.5151 (3)	0.5611 (2)	0.0727 (10)
H5A	0.5900	0.5876	0.5505	0.087*
C4	0.6443 (4)	0.4499 (3)	0.6320 (2)	0.0758 (10)
H4B	0.5582	0.4793	0.6688	0.091*
C29	1.1542 (4)	0.2360 (3)	1.1439 (2)	0.0695 (9)
H29A	1.1705	0.2813	1.1861	0.083*
C14	0.2744 (4)	1.1999 (3)	0.3839 (2)	0.0814 (11)
H14A	0.2066	1.2757	0.3886	0.098*
C30	1.2434 (4)	0.1207 (3)	1.1403 (2)	0.0768 (10)
H30A	1.3192	0.0875	1.1803	0.092*
C15	0.2464 (4)	1.1115 (3)	0.4309 (2)	0.0777 (10)
H15A	0.1585	1.1280	0.4672	0.093*
C32	1.1080 (5)	0.1035 (3)	1.0189 (2)	0.0777 (11)
H32A	1.0941	0.0577	0.9763	0.093*
C31	1.2200 (5)	0.0552 (3)	1.0775 (3)	0.0832 (12)
H31A	1.2805	−0.0228	1.0746	0.100*
C13	0.4014 (4)	1.1774 (3)	0.3301 (2)	0.0771 (10)
H13A	0.4204	1.2373	0.2972	0.092*
C12	0.5015 (4)	1.0657 (3)	0.3246 (2)	0.0731 (10)
H12A	0.5897	1.0506	0.2886	0.088*
C2	0.8405 (4)	0.1598 (3)	0.7369 (2)	0.0862 (12)
H2B	0.8578	0.1132	0.6872	0.129*
H2C	0.8027	0.1222	0.7844	0.129*
H2D	0.9361	0.1689	0.7515	0.129*
C34	0.8908 (4)	0.2672 (3)	0.9584 (2)	0.0783 (10)
H34A	0.7927	0.2977	0.9888	0.117*
H34B	0.8883	0.2071	0.9218	0.117*
H34C	0.9111	0.3284	0.9240	0.117*
C19	0.1023 (4)	0.8841 (3)	0.7355 (2)	0.0801 (11)
H19A	0.0530	0.9171	0.7885	0.120*
H19B	0.0255	0.8780	0.6982	0.120*
H19C	0.1552	0.9330	0.7081	0.120*
C17	0.3151 (5)	0.9008 (3)	0.4802 (2)	0.0911 (12)
H17A	0.3184	0.8389	0.4439	0.137*
H17B	0.2147	0.9297	0.5085	0.137*
H17C	0.3927	0.8722	0.5225	0.137*
C18	0.2157 (4)	0.6813 (3)	0.6966 (2)	0.0889 (12)
H18A	0.3104	0.6605	0.6623	0.133*
H18B	0.1293	0.7093	0.6596	0.133*
H18C	0.2097	0.6143	0.7297	0.133*
C1	0.6037 (4)	0.3152 (3)	0.7806 (2)	0.0912 (12)
H1A	0.5071	0.3430	0.7521	0.137*
H1B	0.6180	0.3776	0.8101	0.137*
H1C	0.6029	0.2536	0.8214	0.137*
H8N	0.864 (3)	0.425 (2)	1.0437 (18)	0.062 (9)*
H9A	0.903 (3)	0.512 (2)	0.3926 (16)	0.041 (8)*
H26A	0.635 (4)	0.761 (3)	1.045 (2)	0.082 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2	0.0767 (6)	0.0649 (5)	0.0642 (6)	−0.0209 (5)	−0.0089 (4)	−0.0088 (4)
S1	0.1248 (9)	0.0507 (5)	0.0585 (6)	−0.0272 (5)	0.0087 (5)	−0.0021 (4)
N8	0.0627 (19)	0.0517 (16)	0.0603 (17)	−0.0157 (14)	−0.0058 (15)	−0.0080 (14)
N6	0.0618 (18)	0.0560 (17)	0.0585 (17)	−0.0181 (14)	−0.0022 (14)	−0.0015 (13)
N7	0.0688 (19)	0.0515 (16)	0.0644 (17)	−0.0178 (14)	−0.0060 (15)	−0.0105 (13)
N3	0.089 (2)	0.0469 (15)	0.0544 (16)	−0.0118 (14)	0.0088 (15)	0.0007 (13)
N2	0.078 (2)	0.0491 (16)	0.0560 (17)	−0.0172 (15)	−0.0005 (14)	0.0036 (13)
C3	0.074 (2)	0.0452 (18)	0.055 (2)	−0.0161 (17)	−0.0033 (18)	−0.0022 (15)
C27	0.056 (2)	0.0499 (18)	0.0516 (18)	−0.0180 (16)	0.0068 (15)	−0.0011 (15)
N4	0.078 (2)	0.0502 (16)	0.0579 (18)	−0.0105 (15)	0.0004 (15)	0.0052 (14)
C20	0.050 (2)	0.0517 (19)	0.058 (2)	−0.0142 (16)	0.0050 (16)	−0.0031 (15)
C8	0.066 (2)	0.0457 (17)	0.0501 (18)	−0.0146 (16)	−0.0012 (16)	−0.0036 (15)
C25	0.058 (2)	0.0464 (18)	0.0518 (19)	−0.0145 (16)	0.0065 (16)	−0.0031 (14)
C23	0.059 (2)	0.0453 (18)	0.063 (2)	−0.0063 (16)	0.0053 (17)	0.0054 (16)
C28	0.056 (2)	0.0527 (19)	0.0555 (19)	−0.0210 (17)	0.0090 (16)	0.0005 (16)
C10	0.075 (2)	0.0449 (18)	0.061 (2)	−0.0197 (17)	−0.0036 (18)	−0.0047 (16)
C21	0.071 (2)	0.0473 (19)	0.071 (2)	−0.0149 (17)	−0.0082 (19)	−0.0087 (16)
N5	0.070 (2)	0.0604 (18)	0.077 (2)	−0.0055 (15)	−0.0151 (16)	−0.0037 (15)
C24	0.064 (2)	0.0441 (18)	0.063 (2)	−0.0155 (16)	0.0108 (17)	−0.0079 (15)
C9	0.075 (3)	0.051 (2)	0.056 (2)	−0.0177 (19)	0.0027 (19)	−0.0048 (17)
C7	0.070 (2)	0.053 (2)	0.058 (2)	−0.0039 (18)	0.0071 (17)	−0.0050 (16)
C26	0.064 (2)	0.050 (2)	0.060 (2)	−0.0201 (18)	0.0066 (17)	−0.0069 (17)
C11	0.060 (2)	0.0527 (19)	0.0515 (19)	−0.0145 (17)	−0.0028 (16)	−0.0019 (15)
C22	0.062 (2)	0.0412 (17)	0.075 (2)	−0.0084 (16)	0.0012 (18)	−0.0022 (16)
C33	0.074 (2)	0.060 (2)	0.054 (2)	−0.0301 (19)	0.0160 (17)	−0.0107 (16)
C6	0.068 (2)	0.0466 (18)	0.060 (2)	0.0018 (16)	0.0001 (17)	−0.0012 (16)
N1	0.089 (2)	0.0561 (17)	0.0674 (19)	−0.0107 (16)	0.0108 (17)	0.0104 (14)
C16	0.073 (2)	0.064 (2)	0.0496 (19)	−0.0246 (19)	−0.0016 (17)	−0.0051 (16)
C5	0.076 (3)	0.0494 (19)	0.074 (2)	0.0017 (18)	0.001 (2)	0.0050 (18)
C4	0.073 (2)	0.061 (2)	0.072 (2)	0.0006 (19)	0.0183 (19)	0.0071 (18)
C29	0.072 (2)	0.058 (2)	0.076 (2)	−0.0192 (19)	0.001 (2)	−0.0033 (18)
C14	0.084 (3)	0.061 (2)	0.083 (3)	−0.003 (2)	0.008 (2)	−0.006 (2)
C30	0.071 (3)	0.066 (2)	0.083 (3)	−0.011 (2)	0.007 (2)	0.005 (2)
C15	0.070 (3)	0.076 (3)	0.076 (3)	−0.012 (2)	0.0144 (19)	−0.013 (2)
C32	0.101 (3)	0.066 (2)	0.067 (2)	−0.030 (2)	0.022 (2)	−0.0169 (19)
C31	0.101 (3)	0.055 (2)	0.086 (3)	−0.020 (2)	0.033 (3)	−0.009 (2)
C13	0.086 (3)	0.057 (2)	0.080 (3)	−0.016 (2)	0.012 (2)	−0.0020 (18)
C12	0.072 (2)	0.059 (2)	0.078 (2)	−0.0108 (19)	0.0117 (19)	0.0023 (18)
C2	0.119 (3)	0.063 (2)	0.061 (2)	−0.012 (2)	−0.003 (2)	0.0100 (18)
C34	0.101 (3)	0.086 (2)	0.062 (2)	−0.050 (2)	0.003 (2)	−0.0141 (19)
C19	0.066 (2)	0.074 (2)	0.092 (3)	−0.012 (2)	−0.014 (2)	0.010 (2)
C17	0.103 (3)	0.092 (3)	0.083 (3)	−0.041 (2)	0.019 (2)	−0.005 (2)
C18	0.090 (3)	0.086 (3)	0.089 (3)	−0.023 (2)	−0.024 (2)	−0.007 (2)
C1	0.089 (3)	0.095 (3)	0.079 (3)	−0.021 (2)	0.009 (2)	0.015 (2)

Geometric parameters (Å, º) top

S2—C27	1.670 (3)	C22—H22A	0.9300
S1—C10	1.670 (3)	C33—C32	1.374 (4)
N8—C27	1.340 (4)	C33—C34	1.491 (4)
N8—C28	1.413 (4)	C6—H6B	0.9300
N8—H8N	0.97 (3)	N1—C1	1.430 (4)
N6—C26	1.277 (4)	N1—C2	1.443 (4)
N6—N7	1.379 (3)	C16—C15	1.391 (4)
N7—C27	1.357 (4)	C16—C17	1.503 (4)
N7—H7N	0.8600	C5—C4	1.367 (4)
N3—C10	1.343 (3)	C5—H5A	0.9300
N3—N2	1.388 (3)	C4—H4B	0.9300
N3—H3N	0.8600	C29—C30	1.375 (4)
N2—C9	1.279 (4)	C29—H29A	0.9300
C3—N1	1.358 (4)	C14—C13	1.357 (5)
C3—C6	1.382 (4)	C14—C15	1.361 (4)
C3—C4	1.402 (4)	C14—H14A	0.9300
N4—C10	1.347 (4)	C30—C31	1.365 (5)
N4—C11	1.414 (4)	C30—H30A	0.9300
N4—H4N	0.94 (3)	C15—H15A	0.9300
C20—N5	1.369 (4)	C32—C31	1.367 (5)
C20—C21	1.391 (4)	C32—H32A	0.9300
C20—C23	1.391 (4)	C31—H31A	0.9300
C8—C5	1.378 (4)	C13—C12	1.371 (4)
C8—C7	1.381 (4)	C13—H13A	0.9300
C8—C9	1.440 (4)	C12—H12A	0.9300
C25—C22	1.379 (4)	C2—H2B	0.9600
C25—C24	1.383 (4)	C2—H2C	0.9600
C25—C26	1.445 (4)	C2—H2D	0.9600
C23—C24	1.356 (4)	C34—H34A	0.9600
C23—H23A	0.9300	C34—H34B	0.9600
C28—C29	1.378 (4)	C34—H34C	0.9600
C28—C33	1.393 (4)	C19—H19A	0.9600
C21—C22	1.370 (4)	C19—H19B	0.9600
C21—H21A	0.9300	C19—H19C	0.9600
N5—C18	1.426 (4)	C17—H17A	0.9600
N5—C19	1.440 (4)	C17—H17B	0.9600
C24—H24A	0.9300	C17—H17C	0.9600
C9—H9A	0.94 (2)	C18—H18A	0.9600
C7—C6	1.366 (4)	C18—H18B	0.9600
C7—H7B	0.9300	C18—H18C	0.9600
C26—H26A	0.97 (3)	C1—H1A	0.9600
C11—C12	1.370 (4)	C1—H1B	0.9600
C11—C16	1.383 (4)	C1—H1C	0.9600

C27—N8—C28	134.1 (3)	C1—N1—C2	116.9 (3)
C27—N8—H8N	110.5 (17)	C11—C16—C15	117.4 (3)
C28—N8—H8N	115.4 (17)	C11—C16—C17	121.2 (3)
C26—N6—N7	116.2 (3)	C15—C16—C17	121.4 (3)
C27—N7—N6	121.1 (3)	C4—C5—C8	122.0 (3)
C27—N7—H7N	119.5	C4—C5—H5A	119.0
N6—N7—H7N	119.5	C8—C5—H5A	119.0
C10—N3—N2	120.1 (3)	C5—C4—C3	121.2 (3)
C10—N3—H3N	120.0	C5—C4—H4B	119.4
N2—N3—H3N	120.0	C3—C4—H4B	119.4
C9—N2—N3	115.3 (3)	C30—C29—C28	120.2 (3)
N1—C3—C6	122.5 (3)	C30—C29—H29A	119.9
N1—C3—C4	121.1 (3)	C28—C29—H29A	119.9
C6—C3—C4	116.5 (3)	C13—C14—C15	119.9 (3)
N8—C27—N7	112.7 (3)	C13—C14—H14A	120.1
N8—C27—S2	129.1 (3)	C15—C14—H14A	120.1
N7—C27—S2	118.2 (2)	C31—C30—C29	119.6 (4)
C10—N4—C11	131.7 (3)	C31—C30—H30A	120.2
C10—N4—H4N	111 (2)	C29—C30—H30A	120.2
C11—N4—H4N	117 (2)	C14—C15—C16	121.9 (3)
N5—C20—C21	121.8 (3)	C14—C15—H15A	119.0
N5—C20—C23	121.2 (3)	C16—C15—H15A	119.0
C21—C20—C23	117.0 (3)	C31—C32—C33	121.6 (4)
C5—C8—C7	116.5 (3)	C31—C32—H32A	119.2
C5—C8—C9	123.9 (3)	C33—C32—H32A	119.2
C7—C8—C9	119.6 (3)	C30—C31—C32	120.4 (3)
C22—C25—C24	116.6 (3)	C30—C31—H31A	119.8
C22—C25—C26	123.6 (3)	C32—C31—H31A	119.8
C24—C25—C26	119.7 (3)	C14—C13—C12	119.5 (3)
C24—C23—C20	120.8 (3)	C14—C13—H13A	120.3
C24—C23—H23A	119.6	C12—C13—H13A	120.3
C20—C23—H23A	119.6	C11—C12—C13	121.2 (3)
C29—C28—C33	120.5 (3)	C11—C12—H12A	119.4
C29—C28—N8	123.2 (3)	C13—C12—H12A	119.4
C33—C28—N8	116.3 (3)	N1—C2—H2B	109.5
N3—C10—N4	113.9 (3)	N1—C2—H2C	109.5
N3—C10—S1	118.4 (2)	H2B—C2—H2C	109.5
N4—C10—S1	127.7 (2)	N1—C2—H2D	109.5
C22—C21—C20	121.4 (3)	H2B—C2—H2D	109.5
C22—C21—H21A	119.3	H2C—C2—H2D	109.5
C20—C21—H21A	119.3	C33—C34—H34A	109.5
C20—N5—C18	121.6 (3)	C33—C34—H34B	109.5
C20—N5—C19	121.7 (3)	H34A—C34—H34B	109.5
C18—N5—C19	116.7 (3)	C33—C34—H34C	109.5
C23—C24—C25	122.7 (3)	H34A—C34—H34C	109.5
C23—C24—H24A	118.7	H34B—C34—H34C	109.5
C25—C24—H24A	118.7	N5—C19—H19A	109.5
N2—C9—C8	122.8 (3)	N5—C19—H19B	109.5
N2—C9—H9A	116.4 (15)	H19A—C19—H19B	109.5
C8—C9—H9A	120.4 (15)	N5—C19—H19C	109.5
C6—C7—C8	122.3 (3)	H19A—C19—H19C	109.5
C6—C7—H7B	118.8	H19B—C19—H19C	109.5
C8—C7—H7B	118.8	C16—C17—H17A	109.5
N6—C26—C25	123.4 (3)	C16—C17—H17B	109.5
N6—C26—H26A	119.9 (19)	H17A—C17—H17B	109.5
C25—C26—H26A	116.6 (18)	C16—C17—H17C	109.5
C12—C11—C16	120.0 (3)	H17A—C17—H17C	109.5
C12—C11—N4	122.7 (3)	H17B—C17—H17C	109.5
C16—C11—N4	117.2 (3)	N5—C18—H18A	109.5
C21—C22—C25	121.5 (3)	N5—C18—H18B	109.5
C21—C22—H22A	119.2	H18A—C18—H18B	109.5
C25—C22—H22A	119.2	N5—C18—H18C	109.5
C32—C33—C28	117.8 (3)	H18A—C18—H18C	109.5
C32—C33—C34	120.3 (3)	H18B—C18—H18C	109.5
C28—C33—C34	121.9 (3)	N1—C1—H1A	109.5
C7—C6—C3	121.4 (3)	N1—C1—H1B	109.5
C7—C6—H6B	119.3	H1A—C1—H1B	109.5
C3—C6—H6B	119.3	N1—C1—H1C	109.5
C3—N1—C1	122.2 (3)	H1A—C1—H1C	109.5
C3—N1—C2	120.3 (3)	H1B—C1—H1C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···N2	0.95 (3)	2.05 (3)	2.587 (3)	114 (3)
C12—H12A···S1	0.93	2.64	3.239 (4)	123
C29—H29A···S2	0.93	2.57	3.257 (4)	131
N7—H7N···S1ⁱ	0.86	2.61	3.458 (3)	170
N3—H3N···S2ⁱⁱ	0.86	2.59	3.439 (3)	171
N8—H8N···N6	0.97 (3)	2.01 (3)	2.587 (4)	116 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₇H₂₀N₄S
M_r	312.43
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	9.172 (3), 12.224 (4), 15.563 (5)
α, β, γ (°)	86.933 (6), 86.990 (7), 70.382 (6)
V (Å³)	1640.3 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.20 × 0.15 × 0.03

Data collection
Diffractometer	Brucker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick,2008)
T_min, T_max	0.961, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	7929, 5640, 3127
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.155, 0.95
No. of reflections	5640
No. of parameters	419
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.17

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···N2	0.95 (3)	2.05 (3)	2.587 (3)	114 (3)
C12—H12A···S1	0.93	2.64	3.239 (4)	123
C29—H29A···S2	0.93	2.57	3.257 (4)	131
N7—H7N···S1ⁱ	0.86	2.61	3.458 (3)	169.7
N3—H3N···S2ⁱⁱ	0.86	2.59	3.439 (3)	170.5
N8—H8N···N6	0.97 (3)	2.01 (3)	2.587 (4)	116 (2)

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

Acknowledgements

This work was supported financially by the National Natural Science Foundation of China (No. 21271150) and the Natural Science Foundation of Fujian Province (No. 2010 J01048).

References

Amendola, V., Bonizzoni, M., Esteban-Gomez, D., Fabbrizzi, L., Licchelli, M., Sancenn, F. & Taglietti, A. (2006). Coord. Chem. Rev. 250, 1451–1470. Web of Science CrossRef CAS Google Scholar
Amendola, V. & Fabbrizzi, L. (2009). Chem. Commun. pp. 513–531. Web of Science CrossRef Google Scholar
Basuli, F., Ruf, M., Pierpont, C. G. & Bhattacharya, S. (1998). Inorg. Chem. 37, 6113–6116. Web of Science CSD CrossRef PubMed CAS 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
Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chikate, R. C., Belapure, A. R. & Padhye, S. B. (2005). Polyhedron, 24, 889–899. Web of Science CrossRef CAS Google Scholar
Fahlbusch, T., Frank, M., Schatz, J. & Schmaderer, H. (2006). Eur. J. Org. Chem. pp. 1899–1903. Web of Science CrossRef Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gale, P. A. & Quesada, R. (2006). Coord. Chem. Rev. 250, 3219–3244. Web of Science CrossRef CAS Google Scholar
Haridas, V., Sahu, S., Praveen Kumar P. P. & Sapala, A. R. (2012). RSC Adv. 2, 12594–12605. Google Scholar
Kowol, C. R., Trondl, R., Arion, V. B., Jakupec, M. A., Lichtscheidl, I. & Keppler, B. K. (2010). Dalton Trans. 39, 704–706. Web of Science CSD CrossRef CAS PubMed Google Scholar
Krisitin, B. J. (2005). Acc. Chem. Res. 38, 671–678. Web of Science CrossRef PubMed Google Scholar
Pandeya, S. N., Sriram, D., Nath, G. & DeClercq, E. (1999). Eur. J. Pharm. Sci. 9, 25–31. Web of Science CrossRef PubMed CAS Google Scholar
Perez, J. & Riera, L. (2008). Chem. Soc. Rev. 37, 2658–2667. Web of Science PubMed CAS Google Scholar
Pouralimardan, O., Chamayou, A.-C., Janiak, C. & Hosseini-Monfared, H. (2007). Inorg. Chim. Acta, 360, 1599–1608. Web of Science CSD CrossRef CAS Google Scholar
Sessler, J. L., Gale, P. A. & Cho, W. S. (2006). In Anion Receptor Chemistry. Cambridge: RSC Publishing. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Willans, C. E., Anderson, K. M., Potts, L. C. & Steed, J. W. (2009). Org. Biomol. Chem. 7, 2756–2759. Web of Science CSD CrossRef PubMed CAS Google Scholar