4-Benzyl-N-methyl­piperazine-1-carbothio­amide

Alanazi, A.M.; El-Emam, A.A.; El-Brollosy, N.R.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536812005685

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages o712-o713

doi:10.1107/S1600536812005685

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4-Benzyl-N-methylpiperazine-1-carbothioamide

Amer M. Alanazi,^a ‡ Ali A. El-Emam,^a Nasser R. El-Brollosy,^a Seik Weng Ng ^b § and Edward R. T. Tiekink ^b ^*

^aDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 3 February 2012; accepted 8 February 2012; online 17 February 2012)

The asymmetric unit in the title thiourea derivative, C₁₃H₁₉N₃S, comprises three independent molecules (A, B and C). The thiourea groups are superimposable for the three molecules, but there are significant conformational differences. Molecules A and B are approximate mirror images of each other, and molecule C has an intermediate conformation. The dihedral angles between the thiourea groups and the phenyl rings are 52.10 (5), 63.29 (5) and 66.46 (6)° in molecules A, B and C, respectively. Each independent molecule self-associates into a supramolecular chain along [100] via N—H⋯S hydrogen bonds. Molecules of A and B assemble into layers four molecules thick in the ac plane via C—H⋯S and C—H⋯π interactions. Molecules of C self-assemble into layers in the ac plane via C—H⋯S interactions. The layers stack along the b axis with no specific interactions between them.

Related literature

For the various biological activities exhibited by 1,4-disubstituted piperazine derivatives, see: Kadi et al. (2010 ); Al Hussainy et al. (2011 ); Moussa et al. (2011 ); Kamiński et al. (2011 ); Sheng et al. (2011 ); Yang et al. (2011 ); Liu et al. (2011 ).

Experimental

Crystal data

C₁₃H₁₉N₃S
M_r = 249.37
Monoclinic, C c
a = 5.8472 (1) Å
b = 80.3936 (9) Å
c = 8.6219 (1) Å
β = 103.292 (1)°
V = 3944.39 (9) Å³
Z = 12
Cu Kα radiation
μ = 2.03 mm⁻¹
T = 100 K
0.40 × 0.30 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.497, T_max = 0.687
45632 measured reflections
7865 independent reflections
7864 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.087
S = 1.03
7865 reflections
475 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ), 3714 Friedel pairs
Flack parameter: 0.020 (8)

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C21–C26 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.87 (1)	2.59 (2)	3.387 (2)	153 (2)
N4—H4⋯S2ⁱ	0.88 (1)	2.64 (2)	3.367 (2)	140 (2)
N7—H7⋯S3ⁱⁱ	0.87 (1)	2.65 (2)	3.397 (2)	144 (2)
C3—H3b⋯S1ⁱⁱⁱ	0.99	2.83	3.8213 (17)	175
C22—H22⋯S2^iv	0.95	2.87	3.7867 (17)	163
C29—H29b⋯S3^v	0.99	2.86	3.8007 (17)	160
C10—H10⋯Cg1^vi	0.95	2.64	3.5665 (18)	164
Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x, y, z-1; (v) $[x, -y+2, z-{\script{1\over 2}}]$ ; (vi) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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: X-SEED (Barbour, 2001 ), 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/S1600536812005685/pk2388sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812005685/pk2388Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812005685/pk2388Isup3.cml

checkCIF report

Comment top

1,4-Disubstituted piperazine derivatives are known for their diverse biological activities such as a CNS stimulant (Al Hussainy et al., 2011; Moussa et al., 2011), anti-convulsant (Kamiński et al., 2011), anti-microbial (Sheng et al., 2011), anti-cancer (Yang et al. 2011) and histamine antagonist (Liu et al., 2011). In continuation of our interest in the chemical and pharmacological properties of 1,4-piperazine derivatives (Kadi et al., 2010), we synthesized the title compound, (I), as an intermediate for potential chemotherapeutic agents.

Three independent molecules comprise the asymmetric unit of (I), Fig. 1. There are significant differences in conformation between these as highlighted in Fig. 2. The independent molecules containing the S1 and S2 are approximately mirror images of each other and the conformation of the S3 containing molecule is intermediate between those of the others. The dihedral angles formed between the thiourea moiety and the phenyl rings are 52.10 (5), 63.29 (5) and 66.46 (6)°, respectively. Each piperazine ring has a chair conformation.

Each independent molecule self-associates into a supramolecular chain via N—H···S hydrogen bonds, Table 1. Chains are orientated along the a axis and an example is illustrated for the S1-containing molecule in Fig. 3. In the crystal packing, the S1- and S2-containing chains are connected into layers four molecules thick via C—H···S and C—H···π interactions. The S3-containing molecules are also connected into layers via C—H···S interactions. Globally, layers, which are formed in the ac plane, stack along the b axis, Fig. 4, with no specific interactions between them.

Related literature top

For the various biological activities exhibited by 1,4-disubstituted piperazine derivatives, see: Kadi et al. (2010); Al Hussainy et al. (2011); Moussa et al. (2011); Kamiński et al. (2011); Sheng et al. (2011); Yang et al. (2011); Liu et al. (2011).

Experimental top

Methyl isothiocyanate (3.66 g, 0.05 mol) was added to a solution of 1-benzylpiperazine (8.81 g, 0.05 mol) in ethanol (15 ml). The mixture was stirred for 5 min. at room temperature and allowed to stand for 1 h. The separated crude product was filtered, washed with cold ethanol, dried and crystallized from ethanol to yield 11.60 g (93%) of the title compound as colourless crystals. M.p.: 365–367 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: X-SEED (Barbour, 2001), DIAMOND (Brandenburg, 2006) and Qmol (Gans & Shalloway, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The three independent molecules of (I) showing displacement ellipsoids at the 70% probability level.
	Fig. 2. An overlay diagram of the three independent molecules in (I). The S1-, S2- and S3-containing molecules are shown as red, green and blue images, respectively. The diagram was drawn so that the thiourea SN₂ planes were superimposed.
	Fig. 3. A view of the linear supramolecular chain along [100] in (I) for the S1-containing molecule. The N—H···S hydrogen bonds are shown as orange dashed lines.
	Fig. 4. A view in projection down the a axis of the unit-cell contents for (I). The N—H···S, C—H···S and C—H···π interactions are shown as orange, blue and purple dashed lines, respectively.

4-Benzyl-N-methylpiperazine-1-carbothioamide top

Crystal data top

C₁₃H₁₉N₃S	F(000) = 1608
M_r = 249.37	D_x = 1.260 Mg m⁻³
Monoclinic, Cc	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: C -2yc	Cell parameters from 33030 reflections
a = 5.8472 (1) Å	θ = 3.3–76.0°
b = 80.3936 (9) Å	µ = 2.03 mm⁻¹
c = 8.6219 (1) Å	T = 100 K
β = 103.292 (1)°	Prism, colourless
V = 3944.39 (9) Å³	0.40 × 0.30 × 0.20 mm
Z = 12

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	7865 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	7864 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.023
Detector resolution: 10.4041 pixels mm^-1	θ_max = 76.2°, θ_min = 3.3°
ω scan	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −100→100
T_min = 0.497, T_max = 0.687	l = −10→9
45632 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0617P)² + 2.8424P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
7865 reflections	Δρ_max = 0.17 e Å⁻³
475 parameters	Δρ_min = −0.28 e Å⁻³
5 restraints	Absolute structure: Flack (1983), 3714 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.020 (8)

Crystal data top

C₁₃H₁₉N₃S	V = 3944.39 (9) Å³
M_r = 249.37	Z = 12
Monoclinic, Cc	Cu Kα radiation
a = 5.8472 (1) Å	µ = 2.03 mm⁻¹
b = 80.3936 (9) Å	T = 100 K
c = 8.6219 (1) Å	0.40 × 0.30 × 0.20 mm
β = 103.292 (1)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	7865 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	7864 reflections with I > 2σ(I)
T_min = 0.497, T_max = 0.687	R_int = 0.023
45632 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.087	Δρ_max = 0.17 e Å⁻³
S = 1.03	Δρ_min = −0.28 e Å⁻³
7865 reflections	Absolute structure: Flack (1983), 3714 Friedel pairs
475 parameters	Absolute structure parameter: 0.020 (8)
5 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.50009 (7)	0.777950 (5)	1.00020 (5)	0.01532 (9)
S2	0.87096 (7)	0.897767 (5)	0.78870 (6)	0.02086 (10)
S3	1.18962 (7)	0.971979 (5)	0.91464 (5)	0.01999 (10)
N1	0.0947 (3)	0.776304 (18)	1.08448 (19)	0.0173 (3)
N2	0.1815 (2)	0.753280 (17)	0.94877 (18)	0.0144 (3)
N3	0.2430 (2)	0.718795 (17)	1.03126 (17)	0.0140 (3)
N4	0.4150 (3)	0.90408 (2)	0.7317 (2)	0.0228 (3)
N5	0.5198 (3)	0.88474 (2)	0.5646 (2)	0.0240 (3)
N6	0.4284 (3)	0.869454 (18)	0.25554 (19)	0.0191 (3)
N7	1.6534 (3)	0.974994 (19)	1.0019 (2)	0.0197 (3)
N8	1.4576 (3)	0.999011 (19)	0.9073 (2)	0.0198 (3)
N9	1.4317 (3)	1.034283 (18)	0.94704 (19)	0.0173 (3)
C1	0.1387 (4)	0.79283 (2)	1.1550 (2)	0.0225 (4)
H1A	0.0044	0.7963	1.1975	0.034*
H1B	0.1608	0.8008	1.0734	0.034*
H1C	0.2806	0.7925	1.2415	0.034*
C2	0.2449 (3)	0.76844 (2)	1.0126 (2)	0.0137 (3)
C3	0.3403 (3)	0.74281 (2)	0.8827 (2)	0.0150 (3)
H3A	0.4718	0.7496	0.8629	0.018*
H3B	0.2548	0.7380	0.7799	0.018*
C4	0.4367 (3)	0.72882 (2)	0.9992 (2)	0.0141 (3)
H4A	0.5424	0.7217	0.9535	0.017*
H4B	0.5289	0.7336	1.1001	0.017*
C5	0.0859 (3)	0.72945 (2)	1.0969 (2)	0.0160 (3)
H5A	0.1731	0.7344	1.1986	0.019*
H5B	−0.0447	0.7227	1.1191	0.019*
C6	−0.0130 (3)	0.74327 (2)	0.9801 (2)	0.0162 (3)
H6A	−0.1043	0.7384	0.8793	0.019*
H6B	−0.1194	0.7504	1.0254	0.019*
C7	0.3317 (3)	0.70532 (2)	1.1436 (2)	0.0180 (3)
H7A	0.1977	0.7001	1.1777	0.022*
H7B	0.4381	0.7101	1.2394	0.022*
C8	0.4621 (3)	0.69206 (2)	1.0749 (2)	0.0156 (3)
C9	0.3552 (3)	0.68384 (2)	0.9342 (2)	0.0190 (3)
H9	0.1998	0.6867	0.8803	0.023*
C10	0.4738 (3)	0.67146 (2)	0.8724 (2)	0.0206 (4)
H10	0.3994	0.6660	0.7763	0.025*
C11	0.7005 (3)	0.66696 (2)	0.9502 (2)	0.0224 (4)
H11	0.7811	0.6585	0.9078	0.027*
C12	0.8083 (3)	0.67501 (3)	1.0903 (3)	0.0270 (4)
H12	0.9631	0.6720	1.1445	0.032*
C13	0.6897 (3)	0.68752 (2)	1.1513 (2)	0.0221 (4)
H13	0.7653	0.6930	1.2468	0.027*
C14	0.4563 (4)	0.91684 (3)	0.8541 (3)	0.0289 (4)
H14A	0.3138	0.9235	0.8450	0.043*
H14B	0.5859	0.9240	0.8406	0.043*
H14C	0.4972	0.9116	0.9594	0.043*
C15	0.5853 (3)	0.89524 (2)	0.6890 (2)	0.0183 (3)
C16	0.6725 (3)	0.87163 (2)	0.5276 (2)	0.0217 (4)
H16A	0.6189	0.8607	0.5584	0.026*
H16B	0.8353	0.8735	0.5897	0.026*
C17	0.6683 (3)	0.87160 (2)	0.3512 (2)	0.0197 (4)
H17A	0.7333	0.8822	0.3222	0.024*
H17B	0.7686	0.8625	0.3277	0.024*
C18	0.2841 (3)	0.88317 (2)	0.2911 (2)	0.0250 (4)
H18A	0.1219	0.8820	0.2258	0.030*
H18B	0.3480	0.8938	0.2622	0.030*
C19	0.2787 (3)	0.88349 (3)	0.4658 (3)	0.0288 (4)
H19A	0.1848	0.8931	0.4871	0.035*
H19B	0.2035	0.8732	0.4934	0.035*
C20	0.4227 (3)	0.86947 (2)	0.0847 (2)	0.0218 (4)
H20A	0.4999	0.8797	0.0582	0.026*
H20B	0.2571	0.8697	0.0238	0.026*
C21	0.5437 (3)	0.85450 (2)	0.0335 (2)	0.0174 (3)
C22	0.7283 (3)	0.85659 (2)	−0.0422 (2)	0.0218 (4)
H22	0.7796	0.8675	−0.0605	0.026*
C23	0.8382 (3)	0.84281 (3)	−0.0912 (2)	0.0261 (4)
H23	0.9624	0.8443	−0.1442	0.031*
C24	0.7663 (4)	0.82698 (3)	−0.0626 (2)	0.0273 (4)
H24	0.8430	0.8176	−0.0944	0.033*
C25	0.5821 (4)	0.82472 (2)	0.0124 (2)	0.0241 (4)
H25	0.5324	0.8138	0.0310	0.029*
C26	0.4710 (3)	0.83840 (2)	0.0601 (2)	0.0199 (4)
H26	0.3449	0.8368	0.1111	0.024*
C27	1.6719 (4)	0.95786 (2)	1.0581 (3)	0.0270 (4)
H27A	1.8369	0.9544	1.0814	0.040*
H27B	1.5792	0.9506	0.9756	0.040*
H27C	1.6122	0.9570	1.1551	0.040*
C28	1.4467 (3)	0.98267 (2)	0.9419 (2)	0.0173 (3)
C29	1.2526 (3)	1.00855 (2)	0.8240 (2)	0.0190 (4)
H29A	1.1104	1.0015	0.8082	0.023*
H29B	1.2740	1.0119	0.7179	0.023*
C30	1.2203 (3)	1.02388 (2)	0.9194 (2)	0.0185 (3)
H30A	1.0835	1.0303	0.8606	0.022*
H30B	1.1889	1.0205	1.0229	0.022*
C31	1.6314 (3)	1.02468 (2)	1.0357 (2)	0.0198 (3)
H31A	1.6020	1.0213	1.1399	0.024*
H31B	1.7745	1.0317	1.0561	0.024*
C32	1.6704 (3)	1.00929 (2)	0.9431 (3)	0.0224 (4)
H32A	1.7117	1.0126	0.8425	0.027*
H32B	1.8028	1.0027	1.0065	0.027*
C33	1.3987 (3)	1.04941 (2)	1.0354 (2)	0.0211 (4)
H33A	1.5498	1.0555	1.0657	0.025*
H33B	1.3520	1.0462	1.1347	0.025*
C34	1.2144 (3)	1.06078 (2)	0.9392 (2)	0.0191 (3)
C35	1.0308 (3)	1.06664 (2)	1.0025 (2)	0.0228 (4)
H35	1.0206	1.0633	1.1065	0.027*
C36	0.8622 (4)	1.07731 (3)	0.9142 (3)	0.0293 (4)
H36	0.7379	1.0813	0.9584	0.035*
C37	0.8752 (4)	1.08209 (2)	0.7633 (3)	0.0291 (5)
H37	0.7604	1.0894	0.7038	0.035*
C38	1.0559 (4)	1.07622 (2)	0.6975 (3)	0.0258 (4)
H38	1.0638	1.0794	0.5928	0.031*
C39	1.2246 (3)	1.06567 (2)	0.7857 (2)	0.0224 (4)
H39	1.3484	1.0617	0.7410	0.027*
H1	−0.051 (2)	0.7729 (3)	1.067 (3)	0.028 (6)*
H4	0.267 (2)	0.9013 (4)	0.694 (3)	0.042 (8)*
H7	1.782 (3)	0.9792 (3)	0.983 (3)	0.023 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01399 (17)	0.01385 (17)	0.0188 (2)	−0.00057 (13)	0.00511 (14)	0.00019 (14)
S2	0.01745 (19)	0.0237 (2)	0.0202 (2)	−0.00384 (15)	0.00181 (15)	−0.00261 (17)
S3	0.0180 (2)	0.01849 (19)	0.0244 (2)	−0.00296 (15)	0.00670 (16)	−0.00357 (16)
N1	0.0150 (7)	0.0164 (7)	0.0226 (8)	0.0012 (5)	0.0084 (6)	−0.0018 (6)
N2	0.0134 (6)	0.0152 (7)	0.0162 (7)	−0.0008 (5)	0.0063 (5)	−0.0001 (5)
N3	0.0135 (7)	0.0151 (6)	0.0143 (7)	0.0008 (5)	0.0050 (5)	0.0018 (5)
N4	0.0188 (7)	0.0241 (8)	0.0249 (9)	−0.0005 (6)	0.0039 (6)	−0.0082 (6)
N5	0.0162 (7)	0.0268 (8)	0.0273 (9)	0.0014 (6)	0.0016 (6)	−0.0106 (7)
N6	0.0176 (7)	0.0171 (7)	0.0220 (8)	0.0016 (6)	0.0032 (6)	−0.0040 (6)
N7	0.0180 (7)	0.0173 (7)	0.0256 (8)	−0.0002 (5)	0.0085 (6)	0.0028 (6)
N8	0.0135 (7)	0.0189 (7)	0.0268 (8)	0.0001 (5)	0.0041 (6)	0.0037 (6)
N9	0.0146 (7)	0.0184 (7)	0.0192 (7)	0.0010 (5)	0.0044 (5)	0.0015 (6)
C1	0.0272 (9)	0.0157 (8)	0.0284 (10)	0.0031 (7)	0.0143 (8)	−0.0031 (7)
C2	0.0158 (8)	0.0139 (7)	0.0107 (8)	0.0027 (6)	0.0015 (6)	0.0030 (6)
C3	0.0178 (8)	0.0160 (7)	0.0122 (8)	0.0000 (6)	0.0057 (6)	−0.0010 (6)
C4	0.0132 (7)	0.0157 (7)	0.0140 (8)	−0.0007 (6)	0.0043 (6)	−0.0009 (6)
C5	0.0153 (8)	0.0177 (8)	0.0162 (8)	−0.0010 (6)	0.0063 (6)	0.0015 (6)
C6	0.0126 (7)	0.0160 (7)	0.0203 (9)	0.0004 (6)	0.0045 (6)	0.0008 (6)
C7	0.0216 (8)	0.0180 (8)	0.0153 (8)	0.0014 (7)	0.0063 (6)	0.0033 (6)
C8	0.0185 (8)	0.0149 (7)	0.0137 (8)	−0.0006 (6)	0.0044 (6)	0.0027 (6)
C9	0.0187 (8)	0.0188 (8)	0.0174 (9)	0.0002 (6)	−0.0003 (7)	0.0023 (6)
C10	0.0266 (9)	0.0168 (8)	0.0158 (9)	−0.0019 (7)	−0.0004 (7)	0.0000 (6)
C11	0.0262 (9)	0.0181 (8)	0.0209 (10)	0.0047 (7)	0.0013 (7)	−0.0002 (7)
C12	0.0211 (9)	0.0299 (10)	0.0256 (10)	0.0090 (8)	−0.0038 (8)	−0.0047 (8)
C13	0.0202 (9)	0.0234 (8)	0.0194 (9)	0.0023 (7)	−0.0026 (7)	−0.0039 (7)
C14	0.0329 (11)	0.0267 (9)	0.0252 (11)	0.0062 (8)	0.0026 (8)	−0.0086 (8)
C15	0.0190 (8)	0.0166 (8)	0.0190 (9)	−0.0022 (6)	0.0039 (7)	0.0005 (6)
C16	0.0181 (8)	0.0208 (8)	0.0251 (10)	0.0007 (6)	0.0024 (7)	−0.0058 (7)
C17	0.0164 (8)	0.0146 (8)	0.0279 (10)	0.0006 (6)	0.0044 (7)	−0.0030 (6)
C18	0.0169 (8)	0.0250 (9)	0.0307 (11)	0.0042 (7)	0.0005 (8)	−0.0083 (8)
C19	0.0135 (8)	0.0385 (11)	0.0322 (11)	0.0017 (8)	0.0008 (8)	−0.0148 (9)
C20	0.0227 (9)	0.0188 (8)	0.0224 (9)	0.0038 (7)	0.0020 (7)	0.0012 (7)
C21	0.0177 (8)	0.0168 (8)	0.0153 (8)	0.0015 (6)	−0.0010 (6)	−0.0005 (6)
C22	0.0209 (8)	0.0234 (8)	0.0197 (9)	−0.0006 (7)	0.0016 (7)	0.0023 (7)
C23	0.0221 (9)	0.0395 (11)	0.0162 (9)	0.0040 (8)	0.0034 (7)	−0.0018 (8)
C24	0.0315 (10)	0.0285 (9)	0.0168 (9)	0.0118 (8)	−0.0052 (8)	−0.0084 (7)
C25	0.0284 (10)	0.0183 (8)	0.0202 (9)	−0.0012 (7)	−0.0053 (8)	−0.0031 (7)
C26	0.0209 (8)	0.0199 (8)	0.0174 (9)	−0.0016 (7)	0.0014 (7)	0.0003 (6)
C27	0.0230 (9)	0.0175 (9)	0.0388 (12)	0.0024 (7)	0.0038 (8)	0.0041 (7)
C28	0.0191 (8)	0.0192 (8)	0.0148 (8)	0.0000 (6)	0.0065 (6)	−0.0017 (6)
C29	0.0162 (8)	0.0195 (8)	0.0209 (9)	0.0017 (6)	0.0032 (7)	0.0030 (7)
C30	0.0144 (8)	0.0205 (8)	0.0206 (9)	0.0006 (6)	0.0041 (7)	0.0022 (7)
C31	0.0138 (8)	0.0222 (8)	0.0224 (9)	0.0001 (6)	0.0019 (7)	0.0040 (7)
C32	0.0155 (8)	0.0184 (8)	0.0338 (11)	0.0011 (6)	0.0062 (7)	0.0045 (7)
C33	0.0210 (9)	0.0215 (8)	0.0202 (9)	0.0005 (7)	0.0034 (7)	−0.0009 (7)
C34	0.0185 (8)	0.0156 (7)	0.0220 (9)	−0.0023 (6)	0.0026 (7)	−0.0023 (7)
C35	0.0204 (9)	0.0242 (8)	0.0238 (9)	−0.0008 (7)	0.0054 (7)	−0.0057 (7)
C36	0.0219 (9)	0.0279 (9)	0.0356 (12)	0.0042 (7)	0.0014 (8)	−0.0132 (8)
C37	0.0303 (10)	0.0178 (8)	0.0331 (12)	0.0042 (7)	−0.0054 (9)	−0.0054 (7)
C38	0.0310 (10)	0.0189 (8)	0.0241 (10)	−0.0033 (7)	−0.0006 (8)	0.0004 (7)
C39	0.0225 (9)	0.0197 (8)	0.0255 (10)	−0.0005 (7)	0.0063 (7)	−0.0004 (7)

Geometric parameters (Å, º) top

S1—C2	1.7021 (18)	C13—H13	0.9500
S2—C15	1.7058 (19)	C14—H14A	0.9800
S3—C28	1.7003 (19)	C14—H14B	0.9800
N1—C2	1.344 (2)	C14—H14C	0.9800
N1—C1	1.459 (2)	C16—C17	1.516 (3)
N1—H1	0.873 (10)	C16—H16A	0.9900
N2—C2	1.353 (2)	C16—H16B	0.9900
N2—C3	1.462 (2)	C17—H17A	0.9900
N2—C6	1.468 (2)	C17—H17B	0.9900
N3—C5	1.462 (2)	C18—C19	1.515 (3)
N3—C4	1.467 (2)	C18—H18A	0.9900
N3—C7	1.466 (2)	C18—H18B	0.9900
N4—C15	1.342 (2)	C19—H19A	0.9900
N4—C14	1.452 (2)	C19—H19B	0.9900
N4—H4	0.879 (10)	C20—C21	1.512 (2)
N5—C15	1.349 (2)	C20—H20A	0.9900
N5—C16	1.463 (2)	C20—H20B	0.9900
N5—C19	1.474 (2)	C21—C26	1.398 (2)
N6—C20	1.466 (3)	C21—C22	1.394 (3)
N6—C17	1.465 (2)	C22—C23	1.394 (3)
N6—C18	1.463 (2)	C22—H22	0.9500
N7—C28	1.350 (2)	C23—C24	1.380 (3)
N7—C27	1.456 (2)	C23—H23	0.9500
N7—H7	0.874 (10)	C24—C25	1.390 (3)
N8—C28	1.352 (2)	C24—H24	0.9500
N8—C29	1.464 (2)	C25—C26	1.387 (3)
N8—C32	1.466 (2)	C25—H25	0.9500
N9—C31	1.461 (2)	C26—H26	0.9500
N9—C30	1.465 (2)	C27—H27A	0.9800
N9—C33	1.471 (2)	C27—H27B	0.9800
C1—H1A	0.9800	C27—H27C	0.9800
C1—H1B	0.9800	C29—C30	1.518 (2)
C1—H1C	0.9800	C29—H29A	0.9900
C3—C4	1.527 (2)	C29—H29B	0.9900
C3—H3A	0.9900	C30—H30A	0.9900
C3—H3B	0.9900	C30—H30B	0.9900
C4—H4A	0.9900	C31—C32	1.518 (3)
C4—H4B	0.9900	C31—H31A	0.9900
C5—C6	1.521 (2)	C31—H31B	0.9900
C5—H5A	0.9900	C32—H32A	0.9900
C5—H5B	0.9900	C32—H32B	0.9900
C6—H6A	0.9900	C33—C34	1.508 (3)
C6—H6B	0.9900	C33—H33A	0.9900
C7—C8	1.509 (2)	C33—H33B	0.9900
C7—H7A	0.9900	C34—C35	1.393 (3)
C7—H7B	0.9900	C34—C39	1.395 (3)
C8—C13	1.391 (3)	C35—C36	1.394 (3)
C8—C9	1.397 (2)	C35—H35	0.9500
C9—C10	1.388 (3)	C36—C37	1.375 (3)
C9—H9	0.9500	C36—H36	0.9500
C10—C11	1.389 (3)	C37—C38	1.391 (3)
C10—H10	0.9500	C37—H37	0.9500
C11—C12	1.387 (3)	C38—C39	1.388 (3)
C11—H11	0.9500	C38—H38	0.9500
C12—C13	1.392 (3)	C39—H39	0.9500
C12—H12	0.9500

C2—N1—C1	123.32 (15)	N6—C17—C16	110.94 (15)
C2—N1—H1	119.3 (17)	N6—C17—H17A	109.5
C1—N1—H1	115.2 (18)	C16—C17—H17A	109.5
C2—N2—C3	122.50 (14)	N6—C17—H17B	109.5
C2—N2—C6	124.76 (15)	C16—C17—H17B	109.5
C3—N2—C6	110.14 (13)	H17A—C17—H17B	108.0
C5—N3—C4	109.39 (13)	N6—C18—C19	111.49 (17)
C5—N3—C7	109.60 (13)	N6—C18—H18A	109.3
C4—N3—C7	111.04 (13)	C19—C18—H18A	109.3
C15—N4—C14	124.31 (17)	N6—C18—H18B	109.3
C15—N4—H4	120 (2)	C19—C18—H18B	109.3
C14—N4—H4	115 (2)	H18A—C18—H18B	108.0
C15—N5—C16	123.23 (16)	N5—C19—C18	109.87 (16)
C15—N5—C19	124.14 (16)	N5—C19—H19A	109.7
C16—N5—C19	112.05 (15)	C18—C19—H19A	109.7
C20—N6—C17	111.29 (15)	N5—C19—H19B	109.7
C20—N6—C18	109.20 (15)	C18—C19—H19B	109.7
C17—N6—C18	108.50 (14)	H19A—C19—H19B	108.2
C28—N7—C27	123.50 (16)	N6—C20—C21	112.84 (15)
C28—N7—H7	119.0 (17)	N6—C20—H20A	109.0
C27—N7—H7	115.4 (17)	C21—C20—H20A	109.0
C28—N8—C29	122.84 (15)	N6—C20—H20B	109.0
C28—N8—C32	125.57 (16)	C21—C20—H20B	109.0
C29—N8—C32	111.57 (14)	H20A—C20—H20B	107.8
C31—N9—C30	109.05 (14)	C26—C21—C22	119.05 (17)
C31—N9—C33	110.49 (15)	C26—C21—C20	120.58 (17)
C30—N9—C33	110.48 (14)	C22—C21—C20	120.37 (16)
N1—C1—H1A	109.5	C23—C22—C21	120.49 (18)
N1—C1—H1B	109.5	C23—C22—H22	119.8
H1A—C1—H1B	109.5	C21—C22—H22	119.8
N1—C1—H1C	109.5	C24—C23—C22	119.85 (19)
H1A—C1—H1C	109.5	C24—C23—H23	120.1
H1B—C1—H1C	109.5	C22—C23—H23	120.1
N1—C2—N2	117.68 (15)	C23—C24—C25	120.29 (18)
N1—C2—S1	119.53 (13)	C23—C24—H24	119.9
N2—C2—S1	122.76 (13)	C25—C24—H24	119.9
N2—C3—C4	109.83 (14)	C26—C25—C24	120.01 (18)
N2—C3—H3A	109.7	C26—C25—H25	120.0
C4—C3—H3A	109.7	C24—C25—H25	120.0
N2—C3—H3B	109.7	C25—C26—C21	120.32 (18)
C4—C3—H3B	109.7	C25—C26—H26	119.8
H3A—C3—H3B	108.2	C21—C26—H26	119.8
N3—C4—C3	110.15 (13)	N7—C27—H27A	109.5
N3—C4—H4A	109.6	N7—C27—H27B	109.5
C3—C4—H4A	109.6	H27A—C27—H27B	109.5
N3—C4—H4B	109.6	N7—C27—H27C	109.5
C3—C4—H4B	109.6	H27A—C27—H27C	109.5
H4A—C4—H4B	108.1	H27B—C27—H27C	109.5
N3—C5—C6	110.40 (14)	N7—C28—N8	116.46 (16)
N3—C5—H5A	109.6	N7—C28—S3	120.46 (14)
C6—C5—H5A	109.6	N8—C28—S3	123.08 (14)
N3—C5—H5B	109.6	N8—C29—C30	110.46 (15)
C6—C5—H5B	109.6	N8—C29—H29A	109.6
H5A—C5—H5B	108.1	C30—C29—H29A	109.6
N2—C6—C5	109.26 (14)	N8—C29—H29B	109.6
N2—C6—H6A	109.8	C30—C29—H29B	109.6
C5—C6—H6A	109.8	H29A—C29—H29B	108.1
N2—C6—H6B	109.8	N9—C30—C29	110.24 (15)
C5—C6—H6B	109.8	N9—C30—H30A	109.6
H6A—C6—H6B	108.3	C29—C30—H30A	109.6
N3—C7—C8	113.36 (14)	N9—C30—H30B	109.6
N3—C7—H7A	108.9	C29—C30—H30B	109.6
C8—C7—H7A	108.9	H30A—C30—H30B	108.1
N3—C7—H7B	108.9	N9—C31—C32	110.76 (16)
C8—C7—H7B	108.9	N9—C31—H31A	109.5
H7A—C7—H7B	107.7	C32—C31—H31A	109.5
C13—C8—C9	118.39 (16)	N9—C31—H31B	109.5
C13—C8—C7	120.94 (16)	C32—C31—H31B	109.5
C9—C8—C7	120.66 (16)	H31A—C31—H31B	108.1
C10—C9—C8	120.64 (17)	N8—C32—C31	110.32 (15)
C10—C9—H9	119.7	N8—C32—H32A	109.6
C8—C9—H9	119.7	C31—C32—H32A	109.6
C9—C10—C11	120.47 (17)	N8—C32—H32B	109.6
C9—C10—H10	119.8	C31—C32—H32B	109.6
C11—C10—H10	119.8	H32A—C32—H32B	108.1
C12—C11—C10	119.41 (18)	N9—C33—C34	112.23 (15)
C12—C11—H11	120.3	N9—C33—H33A	109.2
C10—C11—H11	120.3	C34—C33—H33A	109.2
C11—C12—C13	120.02 (18)	N9—C33—H33B	109.2
C11—C12—H12	120.0	C34—C33—H33B	109.2
C13—C12—H12	120.0	H33A—C33—H33B	107.9
C8—C13—C12	121.07 (17)	C35—C34—C39	118.79 (18)
C8—C13—H13	119.5	C35—C34—C33	120.46 (18)
C12—C13—H13	119.5	C39—C34—C33	120.75 (17)
N4—C14—H14A	109.5	C34—C35—C36	120.4 (2)
N4—C14—H14B	109.5	C34—C35—H35	119.8
H14A—C14—H14B	109.5	C36—C35—H35	119.8
N4—C14—H14C	109.5	C37—C36—C35	120.2 (2)
H14A—C14—H14C	109.5	C37—C36—H36	119.9
H14B—C14—H14C	109.5	C35—C36—H36	119.9
N4—C15—N5	117.16 (16)	C36—C37—C38	120.24 (19)
N4—C15—S2	120.08 (14)	C36—C37—H37	119.9
N5—C15—S2	122.76 (15)	C38—C37—H37	119.9
N5—C16—C17	110.51 (16)	C39—C38—C37	119.6 (2)
N5—C16—H16A	109.5	C39—C38—H38	120.2
C17—C16—H16A	109.5	C37—C38—H38	120.2
N5—C16—H16B	109.5	C38—C39—C34	120.79 (19)
C17—C16—H16B	109.5	C38—C39—H39	119.6
H16A—C16—H16B	108.1	C34—C39—H39	119.6

C1—N1—C2—N2	−178.60 (16)	C16—N5—C19—C18	−54.2 (2)
C1—N1—C2—S1	−0.4 (2)	N6—C18—C19—N5	57.3 (2)
C3—N2—C2—N1	−173.39 (15)	C17—N6—C20—C21	67.05 (19)
C6—N2—C2—N1	−13.5 (2)	C18—N6—C20—C21	−173.20 (15)
C3—N2—C2—S1	8.5 (2)	N6—C20—C21—C26	57.5 (2)
C6—N2—C2—S1	168.43 (13)	N6—C20—C21—C22	−123.02 (18)
C2—N2—C3—C4	103.74 (18)	C26—C21—C22—C23	0.3 (3)
C6—N2—C3—C4	−58.78 (18)	C20—C21—C22—C23	−179.21 (17)
C5—N3—C4—C3	−58.61 (17)	C21—C22—C23—C24	−1.0 (3)
C7—N3—C4—C3	−179.71 (14)	C22—C23—C24—C25	1.1 (3)
N2—C3—C4—N3	58.52 (18)	C23—C24—C25—C26	−0.5 (3)
C4—N3—C5—C6	59.46 (17)	C24—C25—C26—C21	−0.2 (3)
C7—N3—C5—C6	−178.57 (14)	C22—C21—C26—C25	0.3 (3)
C2—N2—C6—C5	−102.90 (18)	C20—C21—C26—C25	179.78 (16)
C3—N2—C6—C5	59.14 (18)	C27—N7—C28—N8	174.58 (18)
N3—C5—C6—N2	−59.65 (18)	C27—N7—C28—S3	−4.9 (3)
C5—N3—C7—C8	170.23 (14)	C29—N8—C28—N7	172.40 (17)
C4—N3—C7—C8	−68.80 (18)	C32—N8—C28—N7	−6.1 (3)
N3—C7—C8—C13	125.55 (18)	C29—N8—C28—S3	−8.1 (3)
N3—C7—C8—C9	−55.6 (2)	C32—N8—C28—S3	173.38 (15)
C13—C8—C9—C10	−0.1 (3)	C28—N8—C29—C30	125.94 (18)
C7—C8—C9—C10	−178.96 (16)	C32—N8—C29—C30	−55.4 (2)
C8—C9—C10—C11	0.4 (3)	C31—N9—C30—C29	−60.03 (19)
C9—C10—C11—C12	−0.2 (3)	C33—N9—C30—C29	178.35 (14)
C10—C11—C12—C13	−0.3 (3)	N8—C29—C30—N9	57.94 (19)
C9—C8—C13—C12	−0.4 (3)	C30—N9—C31—C32	59.9 (2)
C7—C8—C13—C12	178.45 (18)	C33—N9—C31—C32	−178.47 (15)
C11—C12—C13—C8	0.6 (3)	C28—N8—C32—C31	−126.48 (19)
C14—N4—C15—N5	−174.97 (19)	C29—N8—C32—C31	54.9 (2)
C14—N4—C15—S2	4.0 (3)	N9—C31—C32—N8	−57.3 (2)
C16—N5—C15—N4	−165.25 (18)	C31—N9—C33—C34	172.72 (15)
C19—N5—C15—N4	5.4 (3)	C30—N9—C33—C34	−66.52 (19)
C16—N5—C15—S2	15.8 (3)	N9—C33—C34—C35	128.33 (18)
C19—N5—C15—S2	−173.59 (16)	N9—C33—C34—C39	−51.8 (2)
C15—N5—C16—C17	−133.87 (19)	C39—C34—C35—C36	−0.6 (3)
C19—N5—C16—C17	54.5 (2)	C33—C34—C35—C36	179.21 (17)
C20—N6—C17—C16	179.77 (15)	C34—C35—C36—C37	0.3 (3)
C18—N6—C17—C16	59.61 (19)	C35—C36—C37—C38	0.4 (3)
N5—C16—C17—N6	−57.42 (19)	C36—C37—C38—C39	−0.7 (3)
C20—N6—C18—C19	178.58 (15)	C37—C38—C39—C34	0.4 (3)
C17—N6—C18—C19	−60.0 (2)	C35—C34—C39—C38	0.3 (3)
C15—N5—C19—C18	134.3 (2)	C33—C34—C39—C38	−179.54 (17)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C21–C26 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.87 (1)	2.59 (2)	3.387 (2)	153 (2)
N4—H4···S2ⁱ	0.88 (1)	2.64 (2)	3.367 (2)	140 (2)
N7—H7···S3ⁱⁱ	0.87 (1)	2.65 (2)	3.397 (2)	144 (2)
C3—H3b···S1ⁱⁱⁱ	0.99	2.83	3.8213 (17)	175
C22—H22···S2^iv	0.95	2.87	3.7867 (17)	163
C29—H29b···S3^v	0.99	2.86	3.8007 (17)	160
C10—H10···Cg1^vi	0.95	2.64	3.5665 (18)	164

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₉N₃S
M_r	249.37
Crystal system, space group	Monoclinic, Cc
Temperature (K)	100
a, b, c (Å)	5.8472 (1), 80.3936 (9), 8.6219 (1)
β (°)	103.292 (1)
V (Å³)	3944.39 (9)
Z	12
Radiation type	Cu Kα
µ (mm⁻¹)	2.03
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.497, 0.687
No. of measured, independent and observed [I > 2σ(I)] reflections	45632, 7865, 7864
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.087, 1.03
No. of reflections	7865
No. of parameters	475
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.28
Absolute structure	Flack (1983), 3714 Friedel pairs
Absolute structure parameter	0.020 (8)

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C21–C26 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.87 (1)	2.59 (2)	3.387 (2)	153 (2)
N4—H4···S2ⁱ	0.88 (1)	2.64 (2)	3.367 (2)	140 (2)
N7—H7···S3ⁱⁱ	0.87 (1)	2.65 (2)	3.397 (2)	144 (2)
C3—H3b···S1ⁱⁱⁱ	0.99	2.83	3.8213 (17)	175
C22—H22···S2^iv	0.95	2.87	3.7867 (17)	163
C29—H29b···S3^v	0.99	2.86	3.8007 (17)	160
C10—H10···Cg1^vi	0.95	2.64	3.5665 (18)	164

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

Footnotes

‡Additional correspondence author, e-mail: elemam5@hotmail.com.

§Current address: Chemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia.

Acknowledgements

The financial support of the Deanship of Scientific Research and the Research Center of the College of Pharmacy, King Saud University, is greatly appreciated. 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).

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Volume 68| Part 3| March 2012| Pages o712-o713

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