1-Benzoyl-3-methyl-3-pentyl­thio­urea

Gunasekaran, N.; Jerome, P.; Karvembu, R.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536811013365

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1149

doi:10.1107/S1600536811013365

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1-Benzoyl-3-methyl-3-pentylthiourea

N. Gunasekaran,^a P. Jerome,^a R. Karvembu,^a ‡ Seik Weng Ng ^b and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, National Institute of Technology, Tiruchirappalli 620 015, India, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 5 April 2011; accepted 9 April 2011; online 16 April 2011)

Two independent molecules comprise the asymmetric unit of the title compound, C₁₄H₂₀N₂OS. These differ in the relative orientations of the pentyl chains [C—C—C—C torsion angles = −176.7 (3) and 176.4 (3)°]. Significant twists are evident in each molecule, the dihedral angles formed between the thiourea and amide residues being 53.47 (17) and 55.81 (17)°. In the crystal, each molecule self-associates via a centrosymmetric eight-membered {⋯HNC=S}₂ synthon, and these are connected into a supramolecular chain along [110] via C—H⋯O contacts. Disorder is noted for one of the independent molecules in that two orientations (50:50) were resolved for its benzene ring.

Related literature

For the coordination potental of thiourea derivatives, see: Pisiewicz et al. (2010 ). For pharmaceutical applications of thioruea deriavives, see: Venkatachalam et al. (2004 ); Bruce et al. (2007 ). For applications of thiourea derivatives in catalysis, see: Gunasekaran et al. (2010 , 2011 ). For closely related structures, see: Gunasekaran et al. (2010a ,b ,c ).

Experimental

Crystal data

C₁₄H₂₀N₂OS
M_r = 264.38
Triclinic, $[P \overline 1]$
a = 9.0992 (6) Å
b = 10.5297 (6) Å
c = 16.4038 (8) Å
α = 75.784 (5)°
β = 77.831 (5)°
γ = 82.877 (5)°
V = 1484.98 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 295 K
0.25 × 0.20 × 0.15 mm

Data collection

Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.853, T_max = 1.000
11884 measured reflections
6585 independent reflections
3555 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.184
S = 1.03
6585 reflections
321 parameters
37 restraints
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.88	2.87	3.604 (2)	143
N3—H3⋯S2ⁱⁱ	0.88	2.72	3.449 (2)	141
C10—H10b⋯O2ⁱⁱⁱ	0.97	2.55	3.397 (4)	146
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+2, -z+2; (iii) -x+2, -y+2, -z+1.

Data collection: CrysAlis PRO (Agilent, 2010); 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/S1600536811013365/hb5837sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811013365/hb5837Isup2.hkl

checkCIF report

Comment top

Thiourea derivatives exhibit remarkable coordination versatility towards metal cations (Pisiewicz et al., 2010). In continuation of structural studies of thiourea derivatives (Gunasekaran et al., 2010a; Gunasekaran et al., 2010b; Gunasekaran et al., 2010c), which have applications in the field of pharmaceuticals (Venkatachalam et al., 2004; Bruce et al., 2007) and catalysis (Gunasekaran et al., 2010; Gunasekaran et al., 2011), the crystal structure of the title compound, (I), was investigated.

Two independent molecules, Figs 1 and 2, comprise the asymmetric unit of (I). While similar, the molecules differ in the relative orientations of the pentyl groups, Fig. 3, as quantified in the values of the C10—C11—C12—C13 and C24—C25—C26—C27 torsion angles of -176.7 (3) and 176.4 (3) °, respectively, which indicate opposite orientations with respect to the remaining part of the respective molecules. While 50:50 disorder was found in the orientation of the phenyl ring in the second independent molecule, it is noted that the disordered rings are co-planar; dihedral angle = 6.9 (3) °. Significant twists are evident in each molecule with the dihedral angle formed between the thiourea and amide residues being 53.47 (17) ° [for S1,N1,N2,C7/O1,N1,C7,C7] and 55.81 (17) ° [for S2,N3,N4,C22/O2,N3,C21,C22]. Similarly, the terminal benzene ring is twisted out of the least-squares plane through the amide forming a C1—C6—C7—O1 torsion angle of -27.5 (4) °. For the second molecule, with disorder in the benzene ring, the C19—C20—C21—O2 and C19'—C20'—C21—O2 torsion angles are 154.8 (5) and 141.8 (6) °, respectively.

In the crystal packing, each independent molecule self-associates via a centrosymmetric eight-membered {···HNC═S}₂ synthon. The carbonyl-O2 atom forms an intermolecular C—H···O interaction that serves to link the centrosymmetric dimers into a linear supramolecular chain along [110], Fig. 4; the carbonyl-O1 atom is engaged in an intramolecular C—H···O contact.

Related literature top

For the coordination potental of thiourea derivatives, see: Pisiewicz et al. (2010). For pharmaceutical applications of thioruea deriavives, see: Venkatachalam et al. (2004); Bruce et al. (2007). For applications of thiourea derivatives in catalysis, see: Gunasekaran et al. (2010, 2011). For closely related structures, see: Gunasekaran et al. (2010a,b,c).

Experimental top

A solution of benzoyl chloride (0.7029 g, 5 mmol) in acetone (50 ml) was added drop-wise to a suspension of potassium thiocyanate (0.4859 g, 5 mmol) in anhydrous acetone (50 ml). The reaction mixture was heated under reflux for 45 min. and then cooled to room temperature. A solution of n-methylpentylamine (0.5060 g, 5 mmol) in acetone (30 ml) was added and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 ml) was added and the resulting white solid was filtered, washed with water and dried in vacuo. Crystals were grown at room temperature from its acetone solution. M.pt. 332–334 K; Yield 70%. FT—IR (KBr) ν(N—H) 3172, ν(C═O) 1685, ν(C═S) 1245 cm^-1.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 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), 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 first independent molecule of (I) showing displacement ellipsoids at the 35% probability level.
	Fig. 2. The molecular structure of the second independent molecule of (I) showing displacement ellipsoids at the 35% probability level.
	Fig. 3. Overlay diagram showing the superimposition of the S1-containing molecule (red) with the S2-containing molecule (blue).
	Fig. 4. Supramolecular chain in (I) mediated by N—H···S hydrogen bonding and C—H···O contacts shown as orange and blue dashed lines, respectively.

1-Benzoyl-3-methyl-3-pentylthiourea top

Crystal data top

C₁₄H₂₀N₂OS	Z = 4
M_r = 264.38	F(000) = 568
Triclinic, P1	D_x = 1.183 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0992 (6) Å	Cell parameters from 2904 reflections
b = 10.5297 (6) Å	θ = 2.3–29.3°
c = 16.4038 (8) Å	µ = 0.21 mm⁻¹
α = 75.784 (5)°	T = 295 K
β = 77.831 (5)°	Block, colourless
γ = 82.877 (5)°	0.25 × 0.20 × 0.15 mm
V = 1484.98 (15) Å³

Data collection top

Agilent Supernova Dual diffractometer with an Atlas detector	6585 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3555 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.034
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.3°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −13→13
T_min = 0.853, T_max = 1.000	l = −21→17
11884 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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.184	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.071P)² + 0.1338P] where P = (F_o² + 2F_c²)/3
6585 reflections	(Δ/σ)_max = 0.001
321 parameters	Δρ_max = 0.33 e Å⁻³
37 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₄H₂₀N₂OS	γ = 82.877 (5)°
M_r = 264.38	V = 1484.98 (15) Å³
Triclinic, P1	Z = 4
a = 9.0992 (6) Å	Mo Kα radiation
b = 10.5297 (6) Å	µ = 0.21 mm⁻¹
c = 16.4038 (8) Å	T = 295 K
α = 75.784 (5)°	0.25 × 0.20 × 0.15 mm
β = 77.831 (5)°

Data collection top

Agilent Supernova Dual diffractometer with an Atlas detector	6585 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	3555 reflections with I > 2σ(I)
T_min = 0.853, T_max = 1.000	R_int = 0.034
11884 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	37 restraints
wR(F²) = 0.184	H-atom parameters constrained
S = 1.03	Δρ_max = 0.33 e Å⁻³
6585 reflections	Δρ_min = −0.27 e Å⁻³
321 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	Occ. (<1)
S1	0.61942 (10)	0.45168 (7)	0.37694 (5)	0.0643 (3)
S2	0.53313 (10)	1.00478 (8)	0.86780 (5)	0.0709 (3)
O1	0.9407 (2)	0.6383 (2)	0.43989 (13)	0.0707 (6)
O2	0.9060 (2)	1.1826 (2)	0.88476 (13)	0.0753 (6)
N1	0.6894 (3)	0.6324 (2)	0.44660 (14)	0.0531 (6)
H1	0.5983	0.6498	0.4746	0.064*
N2	0.7833 (3)	0.6553 (2)	0.30138 (13)	0.0522 (6)
N3	0.6572 (3)	1.1566 (2)	0.93652 (13)	0.0548 (6)
H3	0.5849	1.1562	0.9816	0.066*
N4	0.6452 (2)	1.2346 (2)	0.79196 (13)	0.0504 (5)
C1	0.8832 (4)	0.6575 (3)	0.61411 (19)	0.0687 (9)
H1A	0.9727	0.6093	0.5978	0.082*
C2	0.8564 (5)	0.6965 (3)	0.6908 (2)	0.0818 (10)
H2	0.9271	0.6727	0.7265	0.098*
C3	0.7272 (5)	0.7696 (3)	0.7145 (2)	0.0810 (11)
H3A	0.7106	0.7961	0.7660	0.097*
C4	0.6215 (4)	0.8042 (3)	0.6629 (2)	0.0735 (9)
H4A	0.5337	0.8548	0.6789	0.088*
C5	0.6465 (4)	0.7633 (3)	0.58688 (18)	0.0616 (8)
H5	0.5743	0.7854	0.5522	0.074*
C6	0.7779 (3)	0.6897 (3)	0.56196 (17)	0.0531 (7)
C7	0.8127 (3)	0.6516 (3)	0.47817 (17)	0.0537 (7)
C8	0.7042 (3)	0.5864 (2)	0.37203 (16)	0.0492 (6)
C9	0.8225 (4)	0.7902 (3)	0.29168 (19)	0.0658 (8)
H9A	0.7595	0.8278	0.3359	0.099*
H9B	0.8073	0.8420	0.2367	0.099*
H9C	0.9263	0.7888	0.2960	0.099*
C10	0.8343 (3)	0.6011 (3)	0.22507 (17)	0.0571 (7)
H10A	0.8415	0.5060	0.2427	0.069*
H10B	0.9346	0.6280	0.1982	0.069*
C11	0.7337 (3)	0.6426 (3)	0.16005 (17)	0.0624 (8)
H11A	0.7196	0.7377	0.1454	0.075*
H11B	0.6357	0.6088	0.1848	0.075*
C12	0.7986 (4)	0.5931 (3)	0.07880 (18)	0.0645 (8)
H12A	0.8938	0.6311	0.0524	0.077*
H12B	0.8189	0.4985	0.0942	0.077*
C13	0.6965 (4)	0.6257 (4)	0.0148 (2)	0.0817 (10)
H13A	0.6789	0.7204	−0.0020	0.098*
H13B	0.6002	0.5900	0.0417	0.098*
C14	0.7584 (5)	0.5731 (4)	−0.0640 (2)	0.1030 (14)
H14A	0.6881	0.5970	−0.1024	0.154*
H14B	0.7741	0.4792	−0.0480	0.154*
H14C	0.8526	0.6097	−0.0918	0.154*
C15	0.9809 (9)	1.1289 (13)	1.0465 (5)	0.0735 (18)	0.50
H15	1.0559	1.1012	1.0051	0.088*	0.50
C16	1.0117 (6)	1.1274 (10)	1.1263 (5)	0.089 (2)	0.50
H16	1.1074	1.0987	1.1382	0.107*	0.50
C17	0.8995 (7)	1.1687 (8)	1.1882 (3)	0.087 (3)	0.50
H17	0.9202	1.1677	1.2415	0.104*	0.50
C18	0.7565 (6)	1.2116 (8)	1.1703 (4)	0.082 (2)	0.50
H18	0.6815	1.2393	1.2117	0.099*	0.50
C19	0.7257 (8)	1.2131 (11)	1.0906 (5)	0.0648 (19)	0.50
H19	0.6300	1.2418	1.0787	0.078*	0.50
C20	0.8379 (10)	1.1718 (14)	1.0287 (4)	0.0552 (16)	0.50
C15'	0.9290 (9)	1.1414 (12)	1.0646 (5)	0.0735 (18)	0.50
H15'	1.0083	1.1017	1.0314	0.088*	0.50
C16'	0.9421 (7)	1.1526 (10)	1.1454 (5)	0.089 (2)	0.50
H16'	1.0301	1.1204	1.1662	0.107*	0.50
C17'	0.8235 (8)	1.2120 (8)	1.1952 (3)	0.087 (3)	0.50
H17'	0.8323	1.2195	1.2492	0.104*	0.50
C18'	0.6918 (7)	1.2602 (8)	1.1641 (4)	0.082 (2)	0.50
H18'	0.6125	1.2999	1.1973	0.099*	0.50
C19'	0.6788 (8)	1.2490 (11)	1.0833 (5)	0.0648 (19)	0.50
H19'	0.5907	1.2812	1.0625	0.078*	0.50
C20'	0.7973 (11)	1.1896 (13)	1.0335 (4)	0.0552 (16)	0.50
C21	0.8010 (4)	1.1734 (3)	0.94459 (18)	0.0573 (7)
C22	0.6179 (3)	1.1403 (3)	0.86181 (16)	0.0498 (6)
C23	0.7007 (4)	1.3610 (3)	0.78851 (19)	0.0654 (8)
H23A	0.6846	1.3758	0.8453	0.098*
H23B	0.6474	1.4302	0.7534	0.098*
H23C	0.8065	1.3599	0.7645	0.098*
C24	0.6123 (3)	1.2216 (3)	0.71090 (17)	0.0564 (7)
H24A	0.5828	1.3080	0.6787	0.068*
H24B	0.5274	1.1682	0.7230	0.068*
C25	0.7425 (3)	1.1613 (3)	0.65679 (17)	0.0612 (8)
H25A	0.7716	1.0741	0.6880	0.073*
H25B	0.8280	1.2142	0.6442	0.073*
C26	0.7007 (4)	1.1520 (3)	0.57313 (18)	0.0655 (8)
H26A	0.6110	1.1041	0.5864	0.079*
H26B	0.6764	1.2399	0.5412	0.079*
C27	0.8234 (4)	1.0852 (3)	0.51769 (19)	0.0768 (9)
H27A	0.8489	0.9977	0.5499	0.092*
H27B	0.9126	1.1339	0.5036	0.092*
C28	0.7804 (5)	1.0744 (4)	0.4357 (2)	0.0996 (13)
H28A	0.8630	1.0315	0.4031	0.149*
H28B	0.7569	1.1607	0.4029	0.149*
H28C	0.6938	1.0242	0.4491	0.149*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0813 (6)	0.0575 (4)	0.0548 (5)	−0.0222 (4)	−0.0078 (4)	−0.0099 (3)
S2	0.0970 (7)	0.0662 (5)	0.0537 (5)	−0.0357 (5)	−0.0040 (4)	−0.0159 (4)
O1	0.0542 (14)	0.1030 (16)	0.0591 (13)	−0.0065 (12)	−0.0091 (11)	−0.0271 (12)
O2	0.0600 (14)	0.1055 (17)	0.0560 (13)	−0.0133 (12)	−0.0061 (11)	−0.0105 (12)
N1	0.0473 (14)	0.0685 (14)	0.0470 (13)	−0.0106 (11)	−0.0049 (10)	−0.0201 (11)
N2	0.0558 (14)	0.0595 (13)	0.0433 (12)	−0.0143 (11)	−0.0056 (10)	−0.0136 (11)
N3	0.0578 (15)	0.0684 (14)	0.0399 (12)	−0.0169 (12)	−0.0009 (10)	−0.0165 (11)
N4	0.0537 (14)	0.0545 (13)	0.0438 (12)	−0.0105 (11)	−0.0081 (10)	−0.0103 (10)
C1	0.079 (2)	0.0736 (19)	0.0589 (19)	−0.0030 (17)	−0.0228 (17)	−0.0192 (16)
C2	0.115 (3)	0.081 (2)	0.059 (2)	−0.011 (2)	−0.036 (2)	−0.0166 (18)
C3	0.120 (3)	0.072 (2)	0.0526 (19)	−0.020 (2)	−0.006 (2)	−0.0202 (17)
C4	0.082 (2)	0.068 (2)	0.067 (2)	−0.0166 (18)	0.0057 (19)	−0.0202 (17)
C5	0.067 (2)	0.0676 (18)	0.0528 (17)	−0.0205 (16)	−0.0036 (15)	−0.0167 (14)
C6	0.0601 (19)	0.0543 (15)	0.0464 (15)	−0.0152 (14)	−0.0063 (14)	−0.0120 (13)
C7	0.0560 (19)	0.0601 (17)	0.0463 (15)	−0.0085 (14)	−0.0105 (14)	−0.0116 (13)
C8	0.0487 (16)	0.0552 (15)	0.0455 (15)	−0.0074 (13)	−0.0100 (12)	−0.0115 (12)
C9	0.074 (2)	0.0660 (18)	0.0574 (18)	−0.0282 (16)	−0.0030 (15)	−0.0107 (15)
C10	0.0505 (17)	0.0713 (18)	0.0497 (16)	−0.0064 (14)	−0.0026 (13)	−0.0190 (14)
C11	0.062 (2)	0.0771 (19)	0.0505 (17)	−0.0022 (16)	−0.0114 (14)	−0.0184 (15)
C12	0.075 (2)	0.0686 (18)	0.0514 (17)	−0.0088 (16)	−0.0110 (15)	−0.0160 (14)
C13	0.095 (3)	0.094 (2)	0.062 (2)	0.000 (2)	−0.0252 (19)	−0.0226 (18)
C14	0.157 (4)	0.100 (3)	0.062 (2)	−0.013 (3)	−0.034 (2)	−0.025 (2)
C15	0.085 (6)	0.069 (3)	0.074 (3)	−0.011 (4)	−0.028 (4)	−0.016 (3)
C16	0.110 (6)	0.086 (4)	0.084 (4)	−0.017 (4)	−0.049 (5)	−0.011 (3)
C17	0.108 (7)	0.101 (5)	0.061 (3)	−0.042 (5)	−0.030 (4)	−0.008 (3)
C18	0.096 (6)	0.097 (6)	0.060 (3)	−0.043 (4)	0.000 (3)	−0.023 (3)
C19	0.066 (5)	0.077 (5)	0.053 (2)	−0.026 (4)	−0.007 (2)	−0.012 (3)
C20	0.059 (5)	0.055 (3)	0.0513 (19)	−0.017 (3)	−0.014 (2)	−0.0020 (16)
C15'	0.085 (6)	0.069 (3)	0.074 (3)	−0.011 (4)	−0.028 (4)	−0.016 (3)
C16'	0.110 (6)	0.086 (4)	0.084 (4)	−0.017 (4)	−0.049 (5)	−0.011 (3)
C17'	0.108 (7)	0.101 (5)	0.061 (3)	−0.042 (5)	−0.030 (4)	−0.008 (3)
C18'	0.096 (6)	0.097 (6)	0.060 (3)	−0.043 (4)	0.000 (3)	−0.023 (3)
C19'	0.066 (5)	0.077 (5)	0.053 (2)	−0.026 (4)	−0.007 (2)	−0.012 (3)
C20'	0.059 (5)	0.055 (3)	0.0513 (19)	−0.017 (3)	−0.014 (2)	−0.0020 (16)
C21	0.069 (2)	0.0562 (16)	0.0464 (16)	−0.0165 (15)	−0.0122 (15)	−0.0049 (13)
C22	0.0520 (17)	0.0552 (15)	0.0444 (15)	−0.0106 (13)	−0.0048 (12)	−0.0158 (13)
C23	0.077 (2)	0.0569 (16)	0.0643 (19)	−0.0220 (15)	−0.0176 (16)	−0.0047 (15)
C24	0.0570 (18)	0.0629 (17)	0.0504 (16)	−0.0062 (14)	−0.0157 (14)	−0.0096 (13)
C25	0.0575 (19)	0.0749 (19)	0.0518 (17)	−0.0068 (15)	−0.0125 (14)	−0.0126 (15)
C26	0.072 (2)	0.0721 (19)	0.0501 (17)	−0.0020 (16)	−0.0134 (15)	−0.0093 (15)
C27	0.083 (2)	0.088 (2)	0.0565 (19)	−0.0053 (19)	−0.0004 (17)	−0.0212 (17)
C28	0.142 (4)	0.101 (3)	0.053 (2)	0.013 (3)	−0.015 (2)	−0.0249 (19)

Geometric parameters (Å, º) top

S1—C8	1.674 (3)	C14—H14B	0.9600
S2—C22	1.677 (3)	C14—H14C	0.9600
O1—C7	1.210 (3)	C15—C16	1.3900
O2—C21	1.211 (3)	C15—C20	1.3900
N1—C7	1.387 (3)	C15—H15	0.9300
N1—C8	1.398 (3)	C16—C17	1.3900
N1—H1	0.8800	C16—H16	0.9300
N2—C8	1.324 (3)	C17—C18	1.3900
N2—C10	1.466 (3)	C17—H17	0.9300
N2—C9	1.470 (3)	C18—C19	1.3900
N3—C21	1.379 (4)	C18—H18	0.9300
N3—C22	1.401 (3)	C19—C20	1.3900
N3—H3	0.8800	C19—H19	0.9300
N4—C22	1.320 (3)	C20—C21	1.483 (5)
N4—C24	1.464 (3)	C15'—C16'	1.3900
N4—C23	1.466 (3)	C15'—C20'	1.3900
C1—C6	1.374 (4)	C15'—H15'	0.9300
C1—C2	1.383 (4)	C16'—C17'	1.3900
C1—H1A	0.9300	C16'—H16'	0.9300
C2—C3	1.362 (5)	C17'—C18'	1.3900
C2—H2	0.9300	C17'—H17'	0.9300
C3—C4	1.371 (5)	C18'—C19'	1.3900
C3—H3A	0.9300	C18'—H18'	0.9300
C4—C5	1.383 (4)	C19'—C20'	1.3900
C4—H4A	0.9300	C19'—H19'	0.9300
C5—C6	1.385 (4)	C20'—C21	1.503 (5)
C5—H5	0.9300	C23—H23A	0.9600
C6—C7	1.485 (4)	C23—H23B	0.9600
C9—H9A	0.9600	C23—H23C	0.9600
C9—H9B	0.9600	C24—C25	1.498 (4)
C9—H9C	0.9600	C24—H24A	0.9700
C10—C11	1.500 (4)	C24—H24B	0.9700
C10—H10A	0.9700	C25—C26	1.528 (4)
C10—H10B	0.9700	C25—H25A	0.9700
C11—C12	1.526 (4)	C25—H25B	0.9700
C11—H11A	0.9700	C26—C27	1.503 (4)
C11—H11B	0.9700	C26—H26A	0.9700
C12—C13	1.495 (4)	C26—H26B	0.9700
C12—H12A	0.9700	C27—C28	1.511 (5)
C12—H12B	0.9700	C27—H27A	0.9700
C13—C14	1.503 (4)	C27—H27B	0.9700
C13—H13A	0.9700	C28—H28A	0.9600
C13—H13B	0.9700	C28—H28B	0.9600
C14—H14A	0.9600	C28—H28C	0.9600

C7—N1—C8	122.5 (2)	C15—C16—H16	120.0
C7—N1—H1	118.8	C16—C17—C18	120.0
C8—N1—H1	118.8	C16—C17—H17	120.0
C8—N2—C10	121.0 (2)	C18—C17—H17	120.0
C8—N2—C9	123.9 (2)	C17—C18—C19	120.0
C10—N2—C9	115.1 (2)	C17—C18—H18	120.0
C21—N3—C22	124.8 (2)	C19—C18—H18	120.0
C21—N3—H3	117.6	C20—C19—C18	120.0
C22—N3—H3	117.6	C20—C19—H19	120.0
C22—N4—C24	120.8 (2)	C18—C19—H19	120.0
C22—N4—C23	124.7 (2)	C19—C20—C15	120.0
C24—N4—C23	114.4 (2)	C19—C20—C21	118.7 (5)
C6—C1—C2	120.2 (3)	C15—C20—C21	121.3 (5)
C6—C1—H1A	119.9	C16'—C15'—C20'	120.0
C2—C1—H1A	119.9	C16'—C15'—H15'	120.0
C3—C2—C1	120.4 (3)	C20'—C15'—H15'	120.0
C3—C2—H2	119.8	C15'—C16'—C17'	120.0
C1—C2—H2	119.8	C15'—C16'—H16'	120.0
C2—C3—C4	120.4 (3)	C17'—C16'—H16'	120.0
C2—C3—H3A	119.8	C18'—C17'—C16'	120.0
C4—C3—H3A	119.8	C18'—C17'—H17'	120.0
C3—C4—C5	119.4 (3)	C16'—C17'—H17'	120.0
C3—C4—H4A	120.3	C19'—C18'—C17'	120.0
C5—C4—H4A	120.3	C19'—C18'—H18'	120.0
C6—C5—C4	120.7 (3)	C17'—C18'—H18'	120.0
C6—C5—H5	119.7	C18'—C19'—C20'	120.0
C4—C5—H5	119.7	C18'—C19'—H19'	120.0
C1—C6—C5	119.0 (3)	C20'—C19'—H19'	120.0
C1—C6—C7	118.9 (3)	C19'—C20'—C15'	120.0
C5—C6—C7	122.0 (3)	C19'—C20'—C21	126.0 (6)
O1—C7—N1	122.1 (3)	C15'—C20'—C21	114.0 (6)
O1—C7—C6	122.1 (3)	O2—C21—N3	122.2 (3)
N1—C7—C6	115.8 (3)	O2—C21—C20	116.0 (5)
N2—C8—N1	116.8 (2)	N3—C21—C20	121.6 (5)
N2—C8—S1	124.5 (2)	O2—C21—C20'	128.5 (5)
N1—C8—S1	118.72 (19)	N3—C21—C20'	109.1 (5)
N2—C9—H9A	109.5	C20—C21—C20'	15.2 (6)
N2—C9—H9B	109.5	N4—C22—N3	117.9 (2)
H9A—C9—H9B	109.5	N4—C22—S2	124.2 (2)
N2—C9—H9C	109.5	N3—C22—S2	117.86 (19)
H9A—C9—H9C	109.5	N4—C23—H23A	109.5
H9B—C9—H9C	109.5	N4—C23—H23B	109.5
N2—C10—C11	114.3 (2)	H23A—C23—H23B	109.5
N2—C10—H10A	108.7	N4—C23—H23C	109.5
C11—C10—H10A	108.7	H23A—C23—H23C	109.5
N2—C10—H10B	108.7	H23B—C23—H23C	109.5
C11—C10—H10B	108.7	N4—C24—C25	113.6 (2)
H10A—C10—H10B	107.6	N4—C24—H24A	108.9
C10—C11—C12	112.1 (2)	C25—C24—H24A	108.9
C10—C11—H11A	109.2	N4—C24—H24B	108.9
C12—C11—H11A	109.2	C25—C24—H24B	108.9
C10—C11—H11B	109.2	H24A—C24—H24B	107.7
C12—C11—H11B	109.2	C24—C25—C26	110.7 (2)
H11A—C11—H11B	107.9	C24—C25—H25A	109.5
C13—C12—C11	113.5 (3)	C26—C25—H25A	109.5
C13—C12—H12A	108.9	C24—C25—H25B	109.5
C11—C12—H12A	108.9	C26—C25—H25B	109.5
C13—C12—H12B	108.9	H25A—C25—H25B	108.1
C11—C12—H12B	108.9	C27—C26—C25	113.6 (3)
H12A—C12—H12B	107.7	C27—C26—H26A	108.8
C12—C13—C14	113.4 (3)	C25—C26—H26A	108.8
C12—C13—H13A	108.9	C27—C26—H26B	108.8
C14—C13—H13A	108.9	C25—C26—H26B	108.8
C12—C13—H13B	108.9	H26A—C26—H26B	107.7
C14—C13—H13B	108.9	C26—C27—C28	113.3 (3)
H13A—C13—H13B	107.7	C26—C27—H27A	108.9
C13—C14—H14A	109.5	C28—C27—H27A	108.9
C13—C14—H14B	109.5	C26—C27—H27B	108.9
H14A—C14—H14B	109.5	C28—C27—H27B	108.9
C13—C14—H14C	109.5	H27A—C27—H27B	107.7
H14A—C14—H14C	109.5	C27—C28—H28A	109.5
H14B—C14—H14C	109.5	C27—C28—H28B	109.5
C16—C15—C20	120.0	H28A—C28—H28B	109.5
C16—C15—H15	120.0	C27—C28—H28C	109.5
C20—C15—H15	120.0	H28A—C28—H28C	109.5
C17—C16—C15	120.0	H28B—C28—H28C	109.5
C17—C16—H16	120.0

C6—C1—C2—C3	−1.4 (5)	C15'—C16'—C17'—C18'	0.0
C1—C2—C3—C4	0.6 (5)	C16'—C17'—C18'—C19'	0.0
C2—C3—C4—C5	0.6 (5)	C17'—C18'—C19'—C20'	0.0
C3—C4—C5—C6	−1.0 (5)	C18'—C19'—C20'—C15'	0.0
C2—C1—C6—C5	1.0 (4)	C18'—C19'—C20'—C21	−178.4 (12)
C2—C1—C6—C7	177.3 (3)	C16'—C15'—C20'—C19'	0.0
C4—C5—C6—C1	0.2 (4)	C16'—C15'—C20'—C21	178.6 (10)
C4—C5—C6—C7	−175.9 (3)	C22—N3—C21—O2	4.2 (4)
C8—N1—C7—O1	5.1 (4)	C22—N3—C21—C20	−171.5 (6)
C8—N1—C7—C6	−174.9 (2)	C22—N3—C21—C20'	179.1 (6)
C1—C6—C7—O1	−27.5 (4)	C19—C20—C21—O2	154.8 (5)
C5—C6—C7—O1	148.7 (3)	C15—C20—C21—O2	−25.8 (9)
C1—C6—C7—N1	152.6 (3)	C19—C20—C21—N3	−29.3 (10)
C5—C6—C7—N1	−31.3 (4)	C15—C20—C21—N3	150.1 (5)
C10—N2—C8—N1	166.1 (2)	C19—C20—C21—C20'	7 (4)
C9—N2—C8—N1	−15.9 (4)	C15—C20—C21—C20'	−174 (5)
C10—N2—C8—S1	−15.1 (4)	C19'—C20'—C21—O2	141.8 (6)
C9—N2—C8—S1	162.9 (2)	C15'—C20'—C21—O2	−36.7 (9)
C7—N1—C8—N2	−56.8 (3)	C19'—C20'—C21—N3	−32.8 (10)
C7—N1—C8—S1	124.4 (2)	C15'—C20'—C21—N3	148.7 (5)
C8—N2—C10—C11	96.6 (3)	C19'—C20'—C21—C20	179 (5)
C9—N2—C10—C11	−81.5 (3)	C15'—C20'—C21—C20	1 (4)
N2—C10—C11—C12	175.1 (2)	C24—N4—C22—N3	177.6 (2)
C10—C11—C12—C13	176.4 (3)	C23—N4—C22—N3	−6.0 (4)
C11—C12—C13—C14	−178.2 (3)	C24—N4—C22—S2	−4.8 (4)
C20—C15—C16—C17	0.0	C23—N4—C22—S2	171.5 (2)
C15—C16—C17—C18	0.0	C21—N3—C22—N4	−59.2 (4)
C16—C17—C18—C19	0.0	C21—N3—C22—S2	123.0 (3)
C17—C18—C19—C20	0.0	C22—N4—C24—C25	−91.2 (3)
C18—C19—C20—C15	0.0	C23—N4—C24—C25	92.1 (3)
C18—C19—C20—C21	179.4 (11)	N4—C24—C25—C26	−179.5 (2)
C16—C15—C20—C19	0.0	C24—C25—C26—C27	−176.7 (3)
C16—C15—C20—C21	−179.4 (11)	C25—C26—C27—C28	179.1 (3)
C20'—C15'—C16'—C17'	0.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.88	2.87	3.604 (2)	143
N3—H3···S2ⁱⁱ	0.88	2.72	3.449 (2)	141
C10—H10b···O2ⁱⁱⁱ	0.97	2.55	3.397 (4)	146

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

Experimental details

Crystal data
Chemical formula	C₁₄H₂₀N₂OS
M_r	264.38
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	9.0992 (6), 10.5297 (6), 16.4038 (8)
α, β, γ (°)	75.784 (5), 77.831 (5), 82.877 (5)
V (Å³)	1484.98 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.853, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11884, 6585, 3555
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.184, 1.03
No. of reflections	6585
No. of parameters	321
No. of restraints	37
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.27

Computer programs: CrysAlis PRO (Agilent, 2010), 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

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.88	2.87	3.604 (2)	143
N3—H3···S2ⁱⁱ	0.88	2.72	3.449 (2)	141
C10—H10b···O2ⁱⁱⁱ	0.97	2.55	3.397 (4)	146

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

Footnotes

‡Additional correspondence author, e-mail: kar@nitt.edu.

Acknowledgements

NG thanks the NITT for a Fellowship. The authors also thank the University of Malaya for supporting this study.

References

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