1-{(E)-[4-(4-Meth­oxy­phen­yl)butan-2-yl­idene]amino}-3-methyl­thio­urea

Tan, M.-Y.; Ravoof, T.B.S.A.; Tahir, M.I.M.; Crouse, K.A.; Tiekink, E.R.T.

doi:10.1107/S160053681201611X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages o1461-o1462

doi:10.1107/S160053681201611X

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1-{(E)-[4-(4-Methoxyphenyl)butan-2-ylidene]amino}-3-methylthiourea

Ming-Yueh Tan,^a Thahira Begum S. A. Ravoof,^a Mohamed Ibrahim Mohamed Tahir,^a Karen A. Crouse ^a ‡ and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, Universiti Putra Malaysia, 43400 Serdang, Malaysia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 12 April 2012; accepted 13 April 2012; online 21 April 2012)

Two independent molecules comprise the asymmetric unit of the title compound, C₁₃H₁₉N₃OS, which differ in the conformations of the residues linking the thiourea and the terminal benzene ring, as manifested in the C_m—C_m—C_a—C_a torsion angles [78.03 (16) and −93.64 (16)°, respectively; m = methylene and a = aromatic]. The dihedral angles [84.40 (4) and 88.28 (5)°] formed between the thiourea residue and the benzene ring indicate an almost orthogonal relationship. In each thiourea residue, the N—H hydrogen atoms are anti, and the terminal N—H hydrogen atom forms an intramolecular N—H⋯N hydrogen bond with the imine-N atom. In each case, the conformation about the imine C=N double bond [1.2812 (17) and 1.2801 (17) Å] is E. In the crystal, the molecules are connected by N—H⋯S hydrogen bonds and these are connected into four molecule aggregates via N—H⋯O hydrogen bonds, which are assembled into a two-dimensional array parallel to (011) via C—H⋯π and π–π interactions [ring centroid–centroid distance = 3.8344 (9) Å].

Related literature

For background to chalcone thiosemicarbazides, see: Zhang et al. (2011 ). For background to hydrazinecarbodithioates, see: Khoo et al. (2005 ); Chan et al. (2008 ); Ravoof et al. (2010 ). For related syntheses, see: Tian et al. (1997 ); Tarafder et al. (2002 ).

Experimental

Crystal data

C₁₃H₁₉N₃OS
M_r = 265.37
Triclinic, $[P \overline 1]$
a = 9.6344 (4) Å
b = 11.1759 (6) Å
c = 13.4619 (8) Å
α = 80.324 (5)°
β = 87.103 (4)°
γ = 76.360 (4)°
V = 1388.48 (13) Å³
Z = 4
Cu Kα radiation
μ = 2.01 mm⁻¹
T = 100 K
0.41 × 0.23 × 0.14 mm

Data collection

Oxford Diffraction Xcaliber Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.51, T_max = 0.75
18287 measured reflections
5312 independent reflections
4995 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.101
S = 1.01
5312 reflections
343 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯N3	0.87 (1)	2.15 (1)	2.5931 (16)	111 (1)
N4—H4n⋯N6	0.87 (1)	2.13 (1)	2.5818 (17)	112 (1)
N2—H2n⋯S2	0.87 (1)	2.70 (1)	3.5686 (11)	176 (1)
N5—H5n⋯S1	0.88 (1)	2.65 (1)	3.5276 (11)	178 (1)
N1—H1n⋯O2ⁱ	0.87 (1)	2.51 (2)	3.0979 (16)	125 (1)
C1—H1B⋯Cg1ⁱⁱ	0.98	2.94	3.5930 (17)	125
Symmetry codes: (i) x+1, y-1, z+1; (ii) x-1, y, z.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ), DIAMOND (Brandenburg, 2006 ) and Qmol (Gans & Shalloway, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681201611X/qm2063sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681201611X/qm2063Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681201611X/qm2063Isup3.cml

checkCIF report

Comment top

To initiate comparative studies between hydrazinecarbothioamide Schiff bases (Zhang et al., 2011) and hydrazinecarbodithioate derivatives synthesized in our laboratory in on-going investigations (Khoo et al. 2005; Chan et al. 2008; Ravoof et al., 2010), the title compound was synthesized and characterized crystallographically.

Two independent molecules comprise the asymmetric unit of (I), Fig. 1. As evidenced from the overlay diagram, Fig. 2, while the thiourea residues are super-imposable, minor conformational differences are seen in the links between these and the terminal benzene rings. Significant differences are noted between the chemically equivalent C5—C6—C7—C8 and C18—C19—C20—C21 torsion angles of 78.03 (16) and -93.64 (16)°, respectively. The dihedral angles formed between the thiourea residues (N1,C1,S1,N2 and N4,C15,S2,N5) and the benzene rings are 84.40 (4) and 88.28 (5)°, respectively. In each case, the methoxy group is co-planar with the benzene ring to which it is connected as seen in the values of the C13—O1—C10—C9 and C26—O2—C23—C22 torsion angles of 175.41 (12) and -5.62 (19)°, respectively. In each thiourea residue, the N—H hydrogen atoms are anti, and the terminal N—H hydrogen atom forms an intramolecular N—H···N hydrogen bond with the imine-N atom, Table 1. The conformation about the imine C═N double bond [N3═C3 = 1.2812 (17) Å and N6═C16 = 1.2801 (17) Å] is E in each case.

As indicated in Fig. 1, the independent molecules are connected by N—H···S hydrogen bonds leading to an eight-membered {···HNCS}₂ synthon, Table 1. These are connected into four molecule aggregates via N—H···O hydrogen bonds, Table 1. The four molecule aggregates are assembled into a two-dimensional array parallel to (011) via C—H···π, Table 1, and π–π interactions occurring between the benzene rings [ring centroid(C7–C12)···centroid(C20–C25)ⁱ distance = 3.8344 (9) Å with a tilt angle = 2.08 (7)° for symmetry operation i: 1 + x, -1 + y, 1 + z). Layers stack without significant intermolecular interactions between them, Fig. 4.

Related literature top

For background to chalcone thiosemicarbazides, see: Zhang et al. (2011). For background to hydrazinecarbodithioates, see: Khoo et al. (2005); Chan et al. (2008); Ravoof et al. (2010). For related syntheses, see: Tian et al. (1997); Tarafder et al. (2002).

Experimental top

The title compound was synthesized following established literature procedures (Tian et al. 1997; Tarafder et al. 2002). To 4-methyl-3-thiosemicarbazide (1.05 g, 10 mmol) dissolved in hot absolute ethanol (25 ml) was added an equimolar amount of 4-(4-methoxyphenyl)butan-2-one (1.70 ml) also in hot absolute ethanol (20 ml). The mixture was stirred for about half an hour at ~340 K and then cooled to room temperature. The Schiff base precipitated was filtered and dried in vacuo over anhydrous silica gel. Colourless crystals were obtained after one week from a 1:1 mixture of 2-propanol and absolute ethanol. Yield 76%, M.pt. 356 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997), DIAMOND (Brandenburg, 2006) and Qmol (Gans & Shalloway, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the two independent molecules in (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. Hydrogen bonds are shown as dashed lines.
	Fig. 2. An overlay diagram of two independent molecules in (I). The S1-containing molecule is illustrated in red and the S2-molecule in blue. Molecules have been aligned so that the N1,S1,N2 and N4,S2,N5 planes are overlapped.
	Fig. 3. A view of the supramolecular layer parallel to (011) in (I) mediated by N—H···S, N—H···O, C—H···π and π–π interactions shown as blue, orange, brown and purple dashed lines, respectively.
	Fig. 4. A view in projection down the a axis of the unit-cell contents for (I). The N—H···S, N—H···O, C—H···π and π–π interactions shown as blue, orange, brown and purple dashed lines, respectively.

1-{(E)-[4-(4-Methoxyphenyl)butan-2-ylidene]amino}-3-methylthiourea top

Crystal data top

C₁₃H₁₉N₃OS	Z = 4
M_r = 265.37	F(000) = 568
Triclinic, P1	D_x = 1.269 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54180 Å
a = 9.6344 (4) Å	Cell parameters from 10673 reflections
b = 11.1759 (6) Å	θ = 3–71°
c = 13.4619 (8) Å	µ = 2.01 mm⁻¹
α = 80.324 (5)°	T = 100 K
β = 87.103 (4)°	Prism, colourless
γ = 76.360 (4)°	0.41 × 0.23 × 0.14 mm
V = 1388.48 (13) Å³

Data collection top

Oxford Diffraction Xcaliber Eos Gemini diffractometer	5312 independent reflections
Radiation source: sealed X-ray tube	4995 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 16.1952 pixels mm^-1	θ_max = 71.6°, θ_min = 3.3°
ω/2θ scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→13
T_min = 0.51, T_max = 0.75	l = −16→16
18287 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.065P)² + 0.5168P] where P = (F_o² + 2F_c²)/3
5312 reflections	(Δ/σ)_max = 0.001
343 parameters	Δρ_max = 0.29 e Å⁻³
4 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₃H₁₉N₃OS	γ = 76.360 (4)°
M_r = 265.37	V = 1388.48 (13) Å³
Triclinic, P1	Z = 4
a = 9.6344 (4) Å	Cu Kα radiation
b = 11.1759 (6) Å	µ = 2.01 mm⁻¹
c = 13.4619 (8) Å	T = 100 K
α = 80.324 (5)°	0.41 × 0.23 × 0.14 mm
β = 87.103 (4)°

Data collection top

Oxford Diffraction Xcaliber Eos Gemini diffractometer	5312 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	4995 reflections with I > 2σ(I)
T_min = 0.51, T_max = 0.75	R_int = 0.022
18287 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	4 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.29 e Å⁻³
5312 reflections	Δρ_min = −0.41 e Å⁻³
343 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 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
S1	0.20415 (3)	0.32321 (3)	0.48243 (2)	0.01907 (11)
O1	1.27782 (10)	−0.24724 (9)	0.93804 (7)	0.0204 (2)
N1	0.34458 (12)	0.15989 (11)	0.63195 (9)	0.0183 (2)
H1N	0.4267 (12)	0.1245 (15)	0.6602 (12)	0.022*
N2	0.47979 (11)	0.26896 (10)	0.52508 (8)	0.0144 (2)
H2N	0.4854 (17)	0.3310 (12)	0.4776 (10)	0.017*
N3	0.59623 (11)	0.19555 (10)	0.57947 (8)	0.0145 (2)
C1	0.21511 (15)	0.11973 (14)	0.66758 (12)	0.0241 (3)
H1A	0.1413	0.1919	0.6817	0.036*
H1B	0.2356	0.0584	0.7293	0.036*
H1C	0.1813	0.0818	0.6157	0.036*
C2	0.34971 (14)	0.24605 (12)	0.55167 (10)	0.0147 (3)
C3	0.71806 (14)	0.22229 (12)	0.56058 (10)	0.0147 (3)
C4	0.74688 (14)	0.32895 (13)	0.48538 (10)	0.0182 (3)
H4A	0.7270	0.3172	0.4174	0.027*
H4B	0.8472	0.3322	0.4892	0.027*
H4C	0.6853	0.4072	0.5003	0.027*
C5	0.84347 (14)	0.13959 (13)	0.61947 (10)	0.0170 (3)
H5A	0.8808	0.1903	0.6607	0.020*
H5B	0.9199	0.1102	0.5713	0.020*
C6	0.81204 (14)	0.02645 (13)	0.68873 (11)	0.0206 (3)
H6A	0.7314	0.0545	0.7343	0.025*
H6B	0.7824	−0.0286	0.6476	0.025*
C7	0.93936 (14)	−0.04719 (13)	0.75113 (10)	0.0174 (3)
C8	0.97580 (14)	−0.00550 (13)	0.83614 (10)	0.0174 (3)
H8	0.9211	0.0709	0.8534	0.021*
C9	1.08986 (14)	−0.07296 (13)	0.89598 (10)	0.0165 (3)
H9	1.1128	−0.0427	0.9535	0.020*
C10	1.17070 (14)	−0.18502 (13)	0.87166 (10)	0.0164 (3)
C11	1.13875 (15)	−0.22751 (13)	0.78626 (11)	0.0206 (3)
H11	1.1945	−0.3033	0.7685	0.025*
C12	1.02383 (16)	−0.15758 (13)	0.72690 (11)	0.0209 (3)
H12	1.0028	−0.1864	0.6682	0.025*
C13	1.35572 (17)	−0.36669 (14)	0.91966 (12)	0.0280 (3)
H13A	1.2909	−0.4232	0.9244	0.042*
H13B	1.4311	−0.4003	0.9699	0.042*
H13C	1.3988	−0.3588	0.8521	0.042*
S2	0.50040 (3)	0.51322 (3)	0.32073 (2)	0.01570 (10)
O2	−0.50895 (10)	0.90797 (9)	−0.24093 (7)	0.0197 (2)
N4	0.35843 (12)	0.67030 (11)	0.16874 (9)	0.0175 (2)
H4N	0.2787 (13)	0.6966 (15)	0.1361 (12)	0.021*
N5	0.22689 (12)	0.55527 (10)	0.27342 (8)	0.0151 (2)
H5N	0.2193 (17)	0.4984 (13)	0.3255 (9)	0.018*
N6	0.11708 (12)	0.60815 (10)	0.20570 (8)	0.0156 (2)
C14	0.48459 (14)	0.71634 (14)	0.13471 (11)	0.0214 (3)
H14A	0.5147	0.7551	0.1875	0.032*
H14B	0.4623	0.7782	0.0735	0.032*
H14C	0.5618	0.6467	0.1202	0.032*
C15	0.35546 (14)	0.58411 (12)	0.24972 (10)	0.0140 (3)
C16	−0.00410 (14)	0.58042 (12)	0.22484 (10)	0.0152 (3)
C17	−0.04030 (15)	0.49618 (14)	0.31617 (11)	0.0209 (3)
H17A	0.0148	0.4107	0.3147	0.031*
H17B	−0.1426	0.4982	0.3166	0.031*
H17C	−0.0168	0.5244	0.3770	0.031*
C18	−0.11934 (14)	0.63481 (13)	0.14771 (10)	0.0181 (3)
H18A	−0.1999	0.6888	0.1793	0.022*
H18B	−0.1550	0.5657	0.1287	0.022*
C19	−0.07400 (15)	0.71084 (14)	0.05199 (11)	0.0225 (3)
H19A	−0.0429	0.7827	0.0700	0.027*
H19B	0.0088	0.6584	0.0212	0.027*
C20	−0.19197 (14)	0.75844 (13)	−0.02456 (10)	0.0189 (3)
C21	−0.20533 (16)	0.69260 (14)	−0.10058 (12)	0.0241 (3)
H21	−0.1412	0.6142	−0.1027	0.029*
C22	−0.31004 (16)	0.73782 (13)	−0.17421 (11)	0.0229 (3)
H22	−0.3162	0.6911	−0.2260	0.027*
C23	−0.40494 (14)	0.85161 (12)	−0.17094 (10)	0.0161 (3)
C24	−0.39597 (14)	0.91792 (13)	−0.09373 (10)	0.0166 (3)
H24	−0.4620	0.9952	−0.0905	0.020*
C25	−0.29074 (14)	0.87139 (13)	−0.02154 (10)	0.0183 (3)
H25	−0.2858	0.9173	0.0310	0.022*
C26	−0.50890 (16)	0.84812 (14)	−0.32718 (11)	0.0236 (3)
H26A	−0.4153	0.8393	−0.3609	0.035*
H26B	−0.5828	0.8987	−0.3740	0.035*
H26C	−0.5286	0.7655	−0.3056	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01121 (17)	0.02285 (19)	0.01953 (19)	−0.00212 (13)	−0.00427 (12)	0.00540 (14)
O1	0.0189 (5)	0.0203 (5)	0.0185 (5)	0.0022 (4)	−0.0064 (4)	−0.0012 (4)
N1	0.0115 (5)	0.0217 (6)	0.0190 (6)	−0.0038 (4)	−0.0029 (4)	0.0054 (5)
N2	0.0122 (5)	0.0158 (6)	0.0133 (5)	−0.0030 (4)	−0.0032 (4)	0.0036 (4)
N3	0.0124 (5)	0.0160 (5)	0.0134 (5)	−0.0012 (4)	−0.0033 (4)	0.0007 (4)
C1	0.0135 (6)	0.0271 (8)	0.0276 (8)	−0.0058 (6)	−0.0012 (6)	0.0089 (6)
C2	0.0122 (6)	0.0166 (6)	0.0147 (6)	−0.0021 (5)	−0.0018 (5)	−0.0020 (5)
C3	0.0131 (6)	0.0177 (6)	0.0130 (6)	−0.0036 (5)	−0.0012 (5)	−0.0010 (5)
C4	0.0138 (6)	0.0226 (7)	0.0164 (6)	−0.0055 (5)	−0.0020 (5)	0.0046 (5)
C5	0.0120 (6)	0.0200 (7)	0.0171 (6)	−0.0038 (5)	−0.0024 (5)	0.0032 (5)
C6	0.0152 (6)	0.0220 (7)	0.0224 (7)	−0.0057 (5)	−0.0056 (5)	0.0060 (6)
C7	0.0139 (6)	0.0188 (7)	0.0176 (6)	−0.0059 (5)	−0.0019 (5)	0.0056 (5)
C8	0.0151 (6)	0.0160 (6)	0.0187 (7)	−0.0024 (5)	0.0014 (5)	0.0019 (5)
C9	0.0165 (6)	0.0192 (7)	0.0136 (6)	−0.0055 (5)	−0.0002 (5)	0.0001 (5)
C10	0.0134 (6)	0.0197 (7)	0.0142 (6)	−0.0039 (5)	−0.0014 (5)	0.0031 (5)
C11	0.0221 (7)	0.0181 (7)	0.0192 (7)	−0.0007 (5)	−0.0024 (5)	−0.0017 (5)
C12	0.0253 (7)	0.0209 (7)	0.0166 (7)	−0.0060 (6)	−0.0059 (6)	−0.0003 (5)
C13	0.0268 (8)	0.0250 (8)	0.0263 (8)	0.0076 (6)	−0.0089 (6)	−0.0044 (6)
S2	0.01168 (16)	0.01806 (18)	0.01548 (17)	−0.00205 (12)	−0.00432 (12)	0.00184 (13)
O2	0.0198 (5)	0.0215 (5)	0.0161 (5)	0.0002 (4)	−0.0070 (4)	−0.0032 (4)
N4	0.0121 (5)	0.0198 (6)	0.0181 (6)	−0.0039 (4)	−0.0049 (4)	0.0057 (5)
N5	0.0121 (5)	0.0171 (6)	0.0139 (5)	−0.0029 (4)	−0.0038 (4)	0.0042 (4)
N6	0.0132 (5)	0.0169 (6)	0.0149 (5)	−0.0021 (4)	−0.0042 (4)	0.0014 (4)
C14	0.0158 (6)	0.0245 (7)	0.0231 (7)	−0.0090 (6)	−0.0034 (5)	0.0058 (6)
C15	0.0132 (6)	0.0136 (6)	0.0150 (6)	−0.0018 (5)	−0.0016 (5)	−0.0032 (5)
C16	0.0134 (6)	0.0162 (6)	0.0151 (6)	−0.0026 (5)	−0.0014 (5)	−0.0005 (5)
C17	0.0150 (6)	0.0270 (8)	0.0191 (7)	−0.0076 (6)	−0.0027 (5)	0.0051 (6)
C18	0.0138 (6)	0.0224 (7)	0.0176 (7)	−0.0067 (5)	−0.0030 (5)	0.0030 (5)
C19	0.0152 (6)	0.0299 (8)	0.0199 (7)	−0.0077 (6)	−0.0044 (5)	0.0077 (6)
C20	0.0147 (6)	0.0236 (7)	0.0165 (7)	−0.0073 (5)	−0.0010 (5)	0.0061 (5)
C21	0.0217 (7)	0.0197 (7)	0.0258 (7)	0.0027 (6)	−0.0046 (6)	0.0015 (6)
C22	0.0256 (7)	0.0211 (7)	0.0211 (7)	−0.0012 (6)	−0.0049 (6)	−0.0054 (6)
C23	0.0146 (6)	0.0181 (7)	0.0143 (6)	−0.0050 (5)	−0.0026 (5)	0.0031 (5)
C24	0.0153 (6)	0.0172 (7)	0.0157 (6)	−0.0027 (5)	0.0002 (5)	0.0005 (5)
C25	0.0186 (6)	0.0248 (7)	0.0129 (6)	−0.0095 (5)	−0.0007 (5)	−0.0009 (5)
C26	0.0269 (7)	0.0262 (8)	0.0181 (7)	−0.0043 (6)	−0.0084 (6)	−0.0045 (6)

Geometric parameters (Å, º) top

S1—C2	1.6943 (13)	S2—C15	1.6881 (13)
O1—C10	1.3759 (16)	O2—C23	1.3736 (16)
O1—C13	1.4236 (17)	O2—C26	1.4341 (16)
N1—C2	1.3284 (18)	N4—C15	1.3319 (18)
N1—C1	1.4556 (17)	N4—C14	1.4530 (17)
N1—H1N	0.871 (9)	N4—H4n	0.869 (9)
N2—C2	1.3563 (17)	N5—C15	1.3616 (17)
N2—N3	1.3837 (15)	N5—N6	1.3860 (15)
N2—H2N	0.870 (9)	N5—H5n	0.875 (9)
N3—C3	1.2812 (17)	N6—C16	1.2801 (17)
C1—H1A	0.9800	C14—H14A	0.9800
C1—H1B	0.9800	C14—H14B	0.9800
C1—H1C	0.9800	C14—H14C	0.9800
C3—C4	1.4983 (18)	C16—C17	1.4974 (19)
C3—C5	1.5054 (17)	C16—C18	1.5055 (17)
C4—H4A	0.9800	C17—H17A	0.9800
C4—H4B	0.9800	C17—H17B	0.9800
C4—H4C	0.9800	C17—H17C	0.9800
C5—C6	1.5217 (19)	C18—C19	1.5242 (19)
C5—H5A	0.9900	C18—H18A	0.9900
C5—H5B	0.9900	C18—H18B	0.9900
C6—C7	1.5110 (18)	C19—C20	1.5119 (18)
C6—H6A	0.9900	C19—H19A	0.9900
C6—H6B	0.9900	C19—H19B	0.9900
C7—C12	1.388 (2)	C20—C21	1.384 (2)
C7—C8	1.395 (2)	C20—C25	1.396 (2)
C8—C9	1.3855 (19)	C21—C22	1.396 (2)
C8—H8	0.9500	C21—H21	0.9500
C9—C10	1.3908 (19)	C22—C23	1.3863 (19)
C9—H9	0.9500	C22—H22	0.9500
C10—C11	1.3893 (19)	C23—C24	1.3911 (19)
C11—C12	1.3952 (19)	C24—C25	1.3870 (19)
C11—H11	0.9500	C24—H24	0.9500
C12—H12	0.9500	C25—H25	0.9500
C13—H13A	0.9800	C26—H26A	0.9800
C13—H13B	0.9800	C26—H26B	0.9800
C13—H13C	0.9800	C26—H26C	0.9800

C10—O1—C13	116.80 (11)	C23—O2—C26	116.28 (10)
C2—N1—C1	123.67 (11)	C15—N4—C14	123.68 (11)
C2—N1—H1N	114.8 (11)	C15—N4—H4N	114.8 (11)
C1—N1—H1N	121.4 (11)	C14—N4—H4N	121.5 (11)
C2—N2—N3	117.48 (11)	C15—N5—N6	117.04 (11)
C2—N2—H2N	119.0 (11)	C15—N5—H5N	119.8 (11)
N3—N2—H2N	123.5 (11)	N6—N5—H5N	122.7 (11)
C3—N3—N2	118.22 (11)	C16—N6—N5	118.43 (11)
N1—C1—H1A	109.5	N4—C14—H14A	109.5
N1—C1—H1B	109.5	N4—C14—H14B	109.5
H1A—C1—H1B	109.5	H14A—C14—H14B	109.5
N1—C1—H1C	109.5	N4—C14—H14C	109.5
H1A—C1—H1C	109.5	H14A—C14—H14C	109.5
H1B—C1—H1C	109.5	H14B—C14—H14C	109.5
N1—C2—N2	116.68 (11)	N4—C15—N5	116.10 (11)
N1—C2—S1	123.03 (10)	N4—C15—S2	123.13 (10)
N2—C2—S1	120.28 (10)	N5—C15—S2	120.77 (10)
N3—C3—C4	125.83 (12)	N6—C16—C17	125.70 (12)
N3—C3—C5	117.16 (11)	N6—C16—C18	117.21 (11)
C4—C3—C5	117.01 (11)	C17—C16—C18	117.07 (11)
C3—C4—H4A	109.5	C16—C17—H17A	109.5
C3—C4—H4B	109.5	C16—C17—H17B	109.5
H4A—C4—H4B	109.5	H17A—C17—H17B	109.5
C3—C4—H4C	109.5	C16—C17—H17C	109.5
H4A—C4—H4C	109.5	H17A—C17—H17C	109.5
H4B—C4—H4C	109.5	H17B—C17—H17C	109.5
C3—C5—C6	115.30 (11)	C16—C18—C19	115.25 (11)
C3—C5—H5A	108.4	C16—C18—H18A	108.5
C6—C5—H5A	108.4	C19—C18—H18A	108.5
C3—C5—H5B	108.4	C16—C18—H18B	108.5
C6—C5—H5B	108.4	C19—C18—H18B	108.5
H5A—C5—H5B	107.5	H18A—C18—H18B	107.5
C7—C6—C5	112.58 (11)	C20—C19—C18	112.97 (11)
C7—C6—H6A	109.1	C20—C19—H19A	109.0
C5—C6—H6A	109.1	C18—C19—H19A	109.0
C7—C6—H6B	109.1	C20—C19—H19B	109.0
C5—C6—H6B	109.1	C18—C19—H19B	109.0
H6A—C6—H6B	107.8	H19A—C19—H19B	107.8
C12—C7—C8	117.58 (12)	C21—C20—C25	117.58 (12)
C12—C7—C6	121.97 (12)	C21—C20—C19	121.45 (13)
C8—C7—C6	120.45 (12)	C25—C20—C19	120.97 (13)
C9—C8—C7	121.52 (12)	C20—C21—C22	122.09 (13)
C9—C8—H8	119.2	C20—C21—H21	119.0
C7—C8—H8	119.2	C22—C21—H21	119.0
C8—C9—C10	119.84 (12)	C23—C22—C21	119.25 (13)
C8—C9—H9	120.1	C23—C22—H22	120.4
C10—C9—H9	120.1	C21—C22—H22	120.4
O1—C10—C11	124.80 (12)	O2—C23—C22	124.70 (12)
O1—C10—C9	115.30 (12)	O2—C23—C24	115.59 (12)
C11—C10—C9	119.89 (12)	C22—C23—C24	119.69 (12)
C10—C11—C12	119.18 (13)	C25—C24—C23	120.07 (12)
C10—C11—H11	120.4	C25—C24—H24	120.0
C12—C11—H11	120.4	C23—C24—H24	120.0
C7—C12—C11	121.94 (13)	C24—C25—C20	121.28 (13)
C7—C12—H12	119.0	C24—C25—H25	119.4
C11—C12—H12	119.0	C20—C25—H25	119.4
O1—C13—H13A	109.5	O2—C26—H26A	109.5
O1—C13—H13B	109.5	O2—C26—H26B	109.5
H13A—C13—H13B	109.5	H26A—C26—H26B	109.5
O1—C13—H13C	109.5	O2—C26—H26C	109.5
H13A—C13—H13C	109.5	H26A—C26—H26C	109.5
H13B—C13—H13C	109.5	H26B—C26—H26C	109.5

C2—N2—N3—C3	−174.61 (11)	C15—N5—N6—C16	178.41 (11)
C1—N1—C2—N2	−176.85 (13)	C14—N4—C15—N5	177.38 (12)
C1—N1—C2—S1	1.81 (19)	C14—N4—C15—S2	−2.45 (19)
N3—N2—C2—N1	4.06 (17)	N6—N5—C15—N4	6.56 (17)
N3—N2—C2—S1	−174.64 (9)	N6—N5—C15—S2	−173.61 (9)
N2—N3—C3—C4	1.38 (19)	N5—N6—C16—C17	1.1 (2)
N2—N3—C3—C5	−178.93 (10)	N5—N6—C16—C18	−177.38 (11)
N3—C3—C5—C6	5.04 (18)	N6—C16—C18—C19	3.64 (18)
C4—C3—C5—C6	−175.24 (12)	C17—C16—C18—C19	−174.98 (12)
C3—C5—C6—C7	−175.80 (11)	C16—C18—C19—C20	177.51 (12)
C5—C6—C7—C12	−102.04 (15)	C18—C19—C20—C21	−93.64 (16)
C5—C6—C7—C8	78.03 (16)	C18—C19—C20—C25	87.00 (16)
C12—C7—C8—C9	−1.6 (2)	C25—C20—C21—C22	2.1 (2)
C6—C7—C8—C9	178.36 (12)	C19—C20—C21—C22	−177.31 (13)
C7—C8—C9—C10	−0.1 (2)	C20—C21—C22—C23	−0.7 (2)
C13—O1—C10—C11	−3.41 (19)	C26—O2—C23—C22	−5.62 (19)
C13—O1—C10—C9	175.41 (12)	C26—O2—C23—C24	172.95 (12)
C8—C9—C10—O1	−177.48 (11)	C21—C22—C23—O2	177.50 (13)
C8—C9—C10—C11	1.4 (2)	C21—C22—C23—C24	−1.0 (2)
O1—C10—C11—C12	177.71 (12)	O2—C23—C24—C25	−177.41 (11)
C9—C10—C11—C12	−1.1 (2)	C22—C23—C24—C25	1.2 (2)
C8—C7—C12—C11	1.9 (2)	C23—C24—C25—C20	0.2 (2)
C6—C7—C12—C11	−178.01 (13)	C21—C20—C25—C24	−1.8 (2)
C10—C11—C12—C7	−0.6 (2)	C19—C20—C25—C24	177.55 (12)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C7–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···N3	0.87 (1)	2.15 (1)	2.5931 (16)	111 (1)
N4—H4n···N6	0.87 (1)	2.13 (1)	2.5818 (17)	112 (1)
N2—H2n···S2	0.87 (1)	2.70 (1)	3.5686 (11)	176 (1)
N5—H5n···S1	0.88 (1)	2.65 (1)	3.5276 (11)	178 (1)
N1—H1n···O2ⁱ	0.87 (1)	2.51 (2)	3.0979 (16)	125 (1)
C1—H1B···Cg1ⁱⁱ	0.98	2.94	3.5930 (17)	125

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₉N₃OS
M_r	265.37
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.6344 (4), 11.1759 (6), 13.4619 (8)
α, β, γ (°)	80.324 (5), 87.103 (4), 76.360 (4)
V (Å³)	1388.48 (13)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.01
Crystal size (mm)	0.41 × 0.23 × 0.14

Data collection
Diffractometer	Oxford Diffraction Xcaliber Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.51, 0.75
No. of measured, independent and observed [I > 2σ(I)] reflections	18287, 5312, 4995
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.101, 1.01
No. of reflections	5312
No. of parameters	343
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.41

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), DIAMOND (Brandenburg, 2006) and Qmol (Gans & Shalloway, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C7–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···N3	0.871 (14)	2.150 (14)	2.5931 (16)	111.0 (13)
N4—H4n···N6	0.868 (14)	2.132 (14)	2.5818 (17)	111.6 (13)
N2—H2n···S2	0.870 (14)	2.700 (13)	3.5686 (11)	175.9 (13)
N5—H5n···S1	0.876 (13)	2.652 (13)	3.5276 (11)	178.4 (12)
N1—H1n···O2ⁱ	0.871 (14)	2.511 (16)	3.0979 (16)	125.4 (12)
C1—H1B···Cg1ⁱⁱ	0.98	2.94	3.5930 (17)	125

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

Footnotes

‡Additional correspondence author, e-mail: kacrouse@gmail.com.

Acknowledgements

Support for the project came from Universiti Putra Malaysia (UPM) under their research University Grant Scheme (RUGS Nos. 9199834 and 9174000) and from the Malaysian Ministry of Science, Technology and Innovation (grant No. 09–02-04–0752-EA001). MYT wishes to thank UPM for a Graduate Research Fellowship award. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

References

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Volume 68| Part 5| May 2012| Pages o1461-o1462

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