N-(2-Furo­yl)-N′-(2-pyrid­yl)thio­urea

Estévez-Hernández, O.; Duque, J.; Pérez, H.; Santos Jr, S.; Mascarenhas, Y.

doi:10.1107/S1600536809011301

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Pages o929-o930

doi:10.1107/S1600536809011301

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N-(2-Furoyl)-N′-(2-pyridyl)thiourea

O. Estévez-Hernández,^a ^* J. Duque,^a H. Pérez,^b S. Santos Jr ^c and Y. Mascarenhas ^d

^aLaboratory of Molecular Engineering, Institute of Materials (IMRE), University of Havana, Cuba, ^bDepartamento de Química Inorgánica, Facultad de Química, Universidad de La Habana, Cuba, ^cLaboratório de Física, Universidade Federal do Tocantins, Palmas, Tocantins, Brazil, and ^dInstituto de Física de São Carlos, Universidade de São Paulo, São Carlos, Brazil
^*Correspondence e-mail: osvaldo@imre.oc.uh.cu

(Received 16 March 2009; accepted 26 March 2009; online 31 March 2009)

The title compound, C₁₁H₉N₃O₂S, crystallizes with two independent molecules in the asymmetric unit. The central thiourea core makes dihedral angles of −3.3 (3) and 0.6 (3)° with the furan carbonyl groups in each molecule, whereas the pyridine ring is inclined by 4.63 (2) and 11.28 (7)°, respectively. The trans–cis geometry of the thiourea fragment is stabilized by an intramolecular N—H⋯N hydrogen bond between the H atom of the cis-thioamide group and the pyridine N atom. In the crystal structure, intermolecular bifurcated N—H⋯S and N—H⋯O hydrogen bonds form centrosymmetric tetramers extending along the b axis.

Related literature

For general background, see: Aly et al. (2007 ); Su et al. (2006 ). For related structures, see: Duque et al. (2008 ); Corrêa et al. (2008 ); Theodoro et al. (2008 ); Valdés-Martínez et al. (2002 ); Koch (2001 ); Pérez et al. (2008 ). For the synthesis, see: Otazo-Sánchez et al. (2001 ).

Experimental

Crystal data

C₁₁H₉N₃O₂S
M_r = 247.27
Monoclinic, P 2₁ /c
a = 6.9510 (1) Å
b = 15.7000 (4) Å
c = 20.2700 (6) Å
β = 90.284 (2)°
V = 2212.05 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 150 K
0.12 × 0.08 × 0.06 mm

Data collection

Enraf–Nonius KappaCCD diffractometer
Absorption correction: none
22281 measured reflections
4337 independent reflections
3574 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.122
S = 1.10
4337 reflections
323 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.89 (2)	2.23 (2)	2.653 (2)	109.3 (18)
N1—H1⋯N3	0.89 (2)	1.84 (2)	2.612 (2)	145 (2)
N1A—H1A⋯O2A	0.87 (2)	2.22 (2)	2.661 (2)	111.6 (18)
N1A—H1A⋯N3A	0.87 (2)	1.90 (2)	2.632 (2)	141 (2)
N2—H2⋯O1Aⁱ	0.84 (3)	2.13 (2)	2.940 (2)	162 (2)
N2A—H2A⋯S1Aⁱ	0.86 (2)	2.51 (2)	3.3530 (15)	170 (2)
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; 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, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809011301/ng2563sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011301/ng2563Isup2.hkl

checkCIF report

Comment top

The importance of aroylthioureas is found largely in heterocyclic syntheses and many of these substrates have interesting biological activities (Aly et al., 2007). Aroylthioureas have also attracted much attention because of their unique properties, such as the strong coordination ability (Su et al., 2006). The title compound (I), Fig. 1, was synthesized from furoyl isothiocyanate and 2-aminopyridine in dry acetone. Studies of a number of substituted thioureas, including N-furoylthioureas, show intramolecular hydrogen bonding between N'H and the furoyl oxygen (Duque et al., 2008; Theodoro et al., 2008; Corrêa et al., 2008). There is also an intermolecular NH hydrogen bond with a sulfur of a neighboring molecule to form a two-dimensional network in these latter thioureas. The molecule structure of the title compound is shown in Figure 1. This thiourea derivative, like other pyridyl thioureas, is found in a conformation resulting from intramolecular hydrogen bonding of N2H(N'H) to the pyridine nitrogen, N3, and cis-cis like N-phenyl- N'-(2-pyridyl)thiourea derivatives (Valdés-Martínez et al., 2002). The title compound crystallizes in the thioamide form with two independent molecules in the asymmetric unit. The main bond lengths are within the ranges obtained for similar compounds (Koch et al., 2001 and Pérez et al. 2008). The C2—S1 and C1—O1 bonds (Table 1) both show the expected double-bond character. The short values of the C2—N1, C2—N2 and C1—N2 bonds indicate partial double bond character. These results can be explained by the existence of resonance in this part of the molecule. The C=S distance for compound I (two unique molecules) averages 1.667 (2) Å. The furan carbonyl (O1—C1—C3—O2 and O1a—C1a—C3a—O2a, two unique molecules) groups are inclined at an angle of -3.3 (3) ° and 0.6 (3) ° with respect to the plane formed by the thiourea moiety, whereas the 2-pyridyl (C7—C8—C9—C10—C11 and C7a—C8a—C9a—C10a—C11a, two unique molecules) rings are inclined at an angle of -3.3 (3) ° and 0.6 (3) °, respectively. In addition, the dihedral angles of two independent molecules between the furoyl groups and pyridine ring planes are 85.1 (2)° and 82.96 (8) °, respectively. The trans-cis geometry in the thiourea moiety is stabilized by the N1—H1···N3 intramolecular hydrogen bond. Another weaker bifurcated intramolecular hydrogen interaction between the furan oxygen atom O2 and the N1—H1 hydrogen atom is observed. The crystal structure is very interesting, stabilized by intermolecular bifurcated N—H···S (non bonding distance of 3.353 (2) Å and bond angle of 170 (2)°) and N—H···O (non bonding distance of 2.940 (2) Å and bond angle of 162 (2)°) hydrogen bonds forming centrosymmetric tetramers extending along the b axis.

Related literature top

For general background, see: Aly et al. (2007); Su et al. (2006). For related structures, see: Duque et al. (2008); Corrêa et al. (2008); Theodoro et al. (2008); Valdés-Martínez et al. (2002); Koch et al. (2001); Pérez et al. (2008). For the synthesis, see: Otazo-Sánchez et al. (2001).

Experimental top

The title compound (I) was synthesized according to a previous report (Otazo-Sánchez et al., 2001), by converting furoyl chloride into furoyl isothiocyanate and then condensing with 2-aminopyridine. The resulting solid product was crystallized from ethanol yielding X-ray quality single crystals (m.p 150–151 °C). Elemental analysis (%) for C₁₁H₉N₃O₂S calculated: C 53.44, H 3.64, N 17.00, S 12.96; found: C 53.50, H 3.46, N 16.99, S 12.58.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. The intramolecular N—H···O hydrogen bond is shown as a dashed line.
	Fig. 2. View of the crystal packing of the title compound. Intermolecular hydrogen bonds are shown as dashed lines.

N-(2-Furoyl)-N'-(2-pyridyl)thiourea top

Crystal data top

C₁₁H₉N₃O₂S	F(000) = 1024
M_r = 247.27	D_x = 1.485 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 13181 reflections
a = 6.9510 (1) Å	θ = 2.9–26.0°
b = 15.7000 (4) Å	µ = 0.29 mm⁻¹
c = 20.2700 (6) Å	T = 150 K
β = 90.284 (2)°	Block, colorless
V = 2212.05 (9) Å³	0.12 × 0.08 × 0.06 mm
Z = 8

Data collection top

Enraf–Nonius KappaCCD diffractometer	3574 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube Enraf Nonius FR590	R_int = 0.060
Horizontally mounted graphite crystal monochromator	θ_max = 26.0°, θ_min = 2.9°
ϕ scans and ω scans with κ offsets	h = −8→8
22281 measured reflections	k = −19→18
4337 independent reflections	l = −24→24

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F_o²) + (0.0699P)² + 0.3338P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.122	(Δ/σ)_max = 0.001
S = 1.10	Δρ_max = 0.45 e Å⁻³
4337 reflections	Δρ_min = −0.46 e Å⁻³
323 parameters

Crystal data top

C₁₁H₉N₃O₂S	V = 2212.05 (9) Å³
M_r = 247.27	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.9510 (1) Å	µ = 0.29 mm⁻¹
b = 15.7000 (4) Å	T = 150 K
c = 20.2700 (6) Å	0.12 × 0.08 × 0.06 mm
β = 90.284 (2)°

Data collection top

Enraf–Nonius KappaCCD diffractometer	3574 reflections with I > 2σ(I)
22281 measured reflections	R_int = 0.060
4337 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.45 e Å⁻³
4337 reflections	Δρ_min = −0.46 e Å⁻³
323 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.

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

	x	y	z	U_iso*/U_eq
S1A	0.26900 (7)	0.58701 (3)	−0.01361 (2)	0.03185 (16)
S1	0.86024 (7)	0.20621 (3)	−0.13099 (2)	0.03742 (17)
N1A	0.0427 (2)	0.55696 (11)	0.09207 (8)	0.0285 (4)
O1A	−0.12681 (18)	0.64878 (9)	0.02319 (7)	0.0327 (3)
O2	0.7008 (2)	−0.07818 (9)	0.00044 (7)	0.0379 (4)
N3	0.8621 (2)	0.08935 (10)	0.07607 (8)	0.0313 (4)
N2A	0.3235 (2)	0.48042 (10)	0.08445 (8)	0.0292 (4)
N1	0.7790 (2)	0.07419 (10)	−0.04921 (9)	0.0297 (4)
O2A	−0.23343 (19)	0.56744 (9)	0.18216 (7)	0.0370 (3)
N2	0.8903 (2)	0.19839 (11)	−0.00248 (8)	0.0278 (4)
C3	0.6597 (3)	−0.06607 (12)	−0.06512 (10)	0.0311 (4)
C2A	0.2051 (2)	0.53986 (12)	0.05684 (9)	0.0268 (4)
C1	0.6980 (3)	0.01830 (13)	−0.09411 (10)	0.0330 (4)
C11	0.8702 (3)	0.06331 (14)	0.13915 (10)	0.0370 (5)
H11	0.8452	0.0063	0.1483	0.044*
N3A	0.1495 (2)	0.44154 (11)	0.17897 (8)	0.0316 (4)
C1A	−0.1108 (3)	0.60931 (12)	0.07437 (9)	0.0277 (4)
C11A	0.1415 (3)	0.40025 (13)	0.23715 (10)	0.0358 (5)
H11A	0.0287	0.4035	0.2615	0.043*
C7A	0.3113 (3)	0.43617 (12)	0.14412 (10)	0.0294 (4)
C7	0.8961 (2)	0.17098 (12)	0.06335 (9)	0.0270 (4)
O1	0.6582 (3)	0.03377 (10)	−0.15091 (8)	0.0527 (4)
C8	0.9405 (3)	0.23029 (14)	0.11254 (10)	0.0340 (4)
H8	0.9641	0.2871	0.1022	0.041*
C3A	−0.2598 (3)	0.61301 (12)	0.12527 (9)	0.0290 (4)
C6A	−0.3910 (3)	0.58333 (14)	0.22036 (11)	0.0404 (5)
H6A	−0.4116	0.5604	0.262	0.048*
C10A	0.2925 (3)	0.35352 (14)	0.26215 (11)	0.0411 (5)
H10A	0.2823	0.3257	0.3025	0.049*
C4A	−0.4268 (3)	0.65642 (12)	0.12727 (10)	0.0312 (4)
H4A	−0.4767	0.6921	0.0948	0.037*
C6	0.6596 (3)	−0.16117 (14)	0.01396 (12)	0.0418 (5)
H6	0.6744	−0.1867	0.0551	0.05*
C9	0.9482 (3)	0.20191 (14)	0.17660 (11)	0.0401 (5)
H9	0.9766	0.2398	0.2105	0.048*
C2	0.8401 (2)	0.15650 (12)	−0.05889 (9)	0.0275 (4)
C5A	−0.5112 (3)	0.63660 (14)	0.18931 (11)	0.0368 (5)
H5A	−0.6279	0.6569	0.2052	0.044*
C10	0.9135 (3)	0.11655 (15)	0.19077 (10)	0.0389 (5)
H10	0.9195	0.0963	0.2338	0.047*
C9A	0.4598 (3)	0.34887 (15)	0.22583 (11)	0.0448 (5)
H9A	0.5645	0.3182	0.2418	0.054*
C4	0.5942 (3)	−0.13956 (14)	−0.09150 (12)	0.0410 (5)
H4	0.5561	−0.1485	−0.135	0.049*
C8A	0.4710 (3)	0.38987 (14)	0.16572 (10)	0.0379 (5)
H8A	0.5818	0.3867	0.1403	0.045*
C5	0.5951 (3)	−0.20049 (14)	−0.03991 (12)	0.0410 (5)
H5	0.5577	−0.2572	−0.0431	0.049*
H2A	0.425 (3)	0.4683 (14)	0.0623 (11)	0.037 (6)*
H2	0.934 (3)	0.2477 (17)	−0.0082 (12)	0.044 (7)*
H1A	0.024 (3)	0.5257 (16)	0.1268 (12)	0.043 (6)*
H1	0.796 (3)	0.0567 (15)	−0.0081 (12)	0.041 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.0344 (3)	0.0315 (3)	0.0297 (3)	0.00331 (19)	0.00427 (19)	0.0052 (2)
S1	0.0482 (3)	0.0361 (3)	0.0280 (3)	−0.0017 (2)	0.0017 (2)	0.0040 (2)
N1A	0.0284 (8)	0.0290 (9)	0.0281 (9)	0.0000 (6)	0.0010 (6)	0.0050 (7)
O1A	0.0311 (7)	0.0331 (7)	0.0338 (8)	−0.0008 (6)	−0.0009 (5)	0.0078 (6)
O2	0.0430 (8)	0.0330 (8)	0.0377 (9)	−0.0026 (6)	0.0002 (6)	0.0033 (6)
N3	0.0331 (8)	0.0301 (9)	0.0308 (9)	−0.0014 (7)	−0.0010 (6)	0.0036 (7)
N2A	0.0291 (8)	0.0297 (9)	0.0287 (9)	0.0039 (7)	0.0026 (6)	0.0016 (7)
N1	0.0338 (9)	0.0277 (9)	0.0277 (9)	0.0000 (6)	−0.0026 (7)	0.0006 (7)
O2A	0.0383 (8)	0.0430 (9)	0.0298 (8)	0.0064 (6)	0.0011 (6)	0.0052 (6)
N2	0.0289 (8)	0.0251 (9)	0.0294 (9)	−0.0025 (7)	0.0005 (6)	0.0012 (7)
C3	0.0282 (9)	0.0312 (10)	0.0340 (11)	0.0029 (8)	−0.0028 (7)	−0.0032 (8)
C2A	0.0285 (9)	0.0236 (10)	0.0282 (10)	−0.0023 (7)	−0.0014 (7)	−0.0019 (7)
C1	0.0354 (10)	0.0309 (11)	0.0327 (12)	0.0022 (8)	−0.0039 (8)	−0.0034 (8)
C11	0.0377 (11)	0.0383 (12)	0.0351 (12)	0.0001 (9)	−0.0003 (8)	0.0087 (9)
N3A	0.0361 (9)	0.0301 (9)	0.0285 (9)	−0.0011 (7)	0.0021 (6)	0.0014 (7)
C1A	0.0275 (9)	0.0254 (10)	0.0302 (11)	−0.0045 (7)	−0.0026 (7)	0.0012 (8)
C11A	0.0466 (12)	0.0326 (11)	0.0283 (11)	−0.0042 (9)	0.0026 (8)	0.0012 (8)
C7A	0.0359 (10)	0.0242 (9)	0.0280 (10)	−0.0011 (8)	−0.0016 (8)	0.0002 (8)
C7	0.0216 (8)	0.0302 (10)	0.0293 (10)	0.0009 (7)	0.0011 (7)	0.0023 (8)
O1	0.0830 (12)	0.0382 (9)	0.0368 (9)	−0.0051 (8)	−0.0204 (8)	−0.0002 (7)
C8	0.0349 (10)	0.0325 (11)	0.0344 (11)	−0.0032 (8)	−0.0006 (8)	−0.0009 (9)
C3A	0.0313 (10)	0.0280 (10)	0.0277 (10)	−0.0029 (8)	−0.0026 (7)	0.0016 (8)
C6A	0.0450 (12)	0.0450 (13)	0.0312 (12)	−0.0007 (9)	0.0083 (9)	−0.0009 (9)
C10A	0.0553 (13)	0.0387 (12)	0.0294 (11)	0.0014 (10)	−0.0013 (9)	0.0083 (9)
C4A	0.0301 (10)	0.0285 (10)	0.0349 (11)	−0.0014 (8)	−0.0021 (7)	0.0028 (8)
C6	0.0418 (12)	0.0326 (12)	0.0510 (14)	−0.0034 (9)	0.0031 (9)	0.0079 (10)
C9	0.0415 (11)	0.0460 (13)	0.0326 (12)	0.0006 (9)	−0.0045 (8)	−0.0061 (10)
C2	0.0238 (8)	0.0273 (10)	0.0314 (11)	0.0044 (7)	0.0018 (7)	−0.0007 (8)
C5A	0.0322 (10)	0.0382 (12)	0.0401 (12)	−0.0015 (9)	0.0065 (8)	−0.0052 (9)
C10	0.0368 (11)	0.0523 (14)	0.0276 (11)	0.0016 (9)	−0.0003 (8)	0.0046 (10)
C9A	0.0500 (13)	0.0462 (13)	0.0383 (13)	0.0116 (10)	−0.0053 (10)	0.0099 (10)
C4	0.0341 (11)	0.0399 (12)	0.0489 (14)	0.0018 (9)	−0.0076 (9)	−0.0103 (10)
C8A	0.0394 (11)	0.0395 (12)	0.0348 (12)	0.0068 (9)	0.0004 (8)	0.0040 (9)
C5	0.0323 (11)	0.0302 (11)	0.0604 (15)	−0.0014 (8)	−0.0008 (9)	0.0028 (10)

Geometric parameters (Å, º) top

S1A—C2A	1.6705 (19)	N3A—C11A	1.347 (3)
S1—C2	1.6633 (19)	C1A—C3A	1.467 (3)
N1A—C2A	1.365 (2)	C11A—C10A	1.375 (3)
N1A—C1A	1.393 (2)	C11A—H11A	0.93
N1A—H1A	0.87 (2)	C7A—C8A	1.395 (3)
O1A—C1A	1.213 (2)	C7—C8	1.398 (3)
O2—C6	1.362 (3)	C8—C9	1.373 (3)
O2—C3	1.371 (2)	C8—H8	0.93
N3—C7	1.329 (2)	C3A—C4A	1.346 (3)
N3—C11	1.343 (3)	C6A—C5A	1.338 (3)
N2A—C2A	1.363 (2)	C6A—H6A	0.93
N2A—C7A	1.398 (3)	C10A—C9A	1.381 (3)
N2A—H2A	0.86 (2)	C10A—H10A	0.93
N1—C2	1.375 (3)	C4A—C5A	1.425 (3)
N1—C1	1.382 (2)	C4A—H4A	0.93
N1—H1	0.89 (2)	C6—C5	1.330 (3)
O2A—C6A	1.367 (3)	C6—H6	0.93
O2A—C3A	1.369 (2)	C9—C10	1.392 (3)
N2—C2	1.363 (2)	C9—H9	0.93
N2—C7	1.402 (2)	C5A—H5A	0.93
N2—H2	0.84 (3)	C10—H10	0.93
C3—C4	1.350 (3)	C9A—C8A	1.381 (3)
C3—C1	1.474 (3)	C9A—H9A	0.93
C1—O1	1.207 (2)	C4—C5	1.417 (3)
C11—C10	1.371 (3)	C4—H4	0.93
C11—H11	0.93	C8A—H8A	0.93
N3A—C7A	1.334 (2)	C5—H5	0.93

C2A—N1A—C1A	128.01 (17)	C9—C8—H8	121.1
C2A—N1A—H1A	116.0 (15)	C7—C8—H8	121.1
C1A—N1A—H1A	115.3 (15)	C4A—C3A—O2A	110.57 (17)
C6—O2—C3	106.52 (16)	C4A—C3A—C1A	130.76 (18)
C7—N3—C11	118.14 (18)	O2A—C3A—C1A	118.66 (16)
C2A—N2A—C7A	131.03 (17)	C5A—C6A—O2A	110.37 (19)
C2A—N2A—H2A	115.6 (15)	C5A—C6A—H6A	124.8
C7A—N2A—H2A	113.4 (15)	O2A—C6A—H6A	124.8
C2—N1—C1	128.90 (18)	C11A—C10A—C9A	118.3 (2)
C2—N1—H1	112.8 (15)	C11A—C10A—H10A	120.8
C1—N1—H1	118.3 (15)	C9A—C10A—H10A	120.8
C6A—O2A—C3A	106.10 (15)	C3A—C4A—C5A	105.96 (18)
C2—N2—C7	131.01 (17)	C3A—C4A—H4A	127
C2—N2—H2	114.8 (16)	C5A—C4A—H4A	127
C7—N2—H2	114.0 (16)	C5—C6—O2	110.4 (2)
C4—C3—O2	109.50 (18)	C5—C6—H6	124.8
C4—C3—C1	132.2 (2)	O2—C6—H6	124.8
O2—C3—C1	118.28 (17)	C8—C9—C10	120.1 (2)
N2A—C2A—N1A	114.79 (17)	C8—C9—H9	119.9
N2A—C2A—S1A	119.45 (14)	C10—C9—H9	119.9
N1A—C2A—S1A	125.73 (14)	N2—C2—N1	114.32 (17)
O1—C1—N1	126.22 (19)	N2—C2—S1	119.24 (15)
O1—C1—C3	121.33 (18)	N1—C2—S1	126.44 (15)
N1—C1—C3	112.44 (17)	C6A—C5A—C4A	107.00 (18)
N3—C11—C10	123.3 (2)	C6A—C5A—H5A	126.5
N3—C11—H11	118.4	C4A—C5A—H5A	126.5
C10—C11—H11	118.4	C11—C10—C9	117.83 (19)
C7A—N3A—C11A	118.13 (17)	C11—C10—H10	121.1
O1A—C1A—N1A	126.07 (17)	C9—C10—H10	121.1
O1A—C1A—C3A	121.29 (17)	C10A—C9A—C8A	119.8 (2)
N1A—C1A—C3A	112.65 (16)	C10A—C9A—H9A	120.1
N3A—C11A—C10A	123.00 (19)	C8A—C9A—H9A	120.1
N3A—C11A—H11A	118.5	C3—C4—C5	106.5 (2)
C10A—C11A—H11A	118.5	C3—C4—H4	126.7
N3A—C7A—C8A	122.58 (18)	C5—C4—H4	126.7
N3A—C7A—N2A	118.80 (17)	C9A—C8A—C7A	118.12 (19)
C8A—C7A—N2A	118.60 (17)	C9A—C8A—H8A	120.9
N3—C7—C8	122.89 (18)	C7A—C8A—H8A	120.9
N3—C7—N2	118.45 (17)	C6—C5—C4	107.01 (19)
C8—C7—N2	118.65 (17)	C6—C5—H5	126.5
C9—C8—C7	117.75 (19)	C4—C5—H5	126.5

C6—O2—C3—C4	0.1 (2)	C6A—O2A—C3A—C1A	179.28 (17)
C6—O2—C3—C1	−177.81 (17)	O1A—C1A—C3A—C4A	−0.9 (3)
C7A—N2A—C2A—N1A	−2.9 (3)	N1A—C1A—C3A—C4A	179.17 (19)
C7A—N2A—C2A—S1A	175.31 (16)	O1A—C1A—C3A—O2A	−179.68 (17)
C1A—N1A—C2A—N2A	−174.81 (17)	N1A—C1A—C3A—O2A	0.4 (2)
C1A—N1A—C2A—S1A	7.1 (3)	C3A—O2A—C6A—C5A	−0.2 (2)
C2—N1—C1—O1	−3.4 (3)	N3A—C11A—C10A—C9A	0.0 (3)
C2—N1—C1—C3	177.41 (17)	O2A—C3A—C4A—C5A	−0.3 (2)
C4—C3—C1—O1	5.4 (3)	C1A—C3A—C4A—C5A	−179.11 (19)
O2—C3—C1—O1	−177.24 (19)	C3—O2—C6—C5	−0.1 (2)
C4—C3—C1—N1	−175.4 (2)	C7—C8—C9—C10	0.4 (3)
O2—C3—C1—N1	2.0 (2)	C7—N2—C2—N1	2.3 (3)
C7—N3—C11—C10	−0.6 (3)	C7—N2—C2—S1	−176.68 (14)
C2A—N1A—C1A—O1A	0.7 (3)	C1—N1—C2—N2	171.78 (17)
C2A—N1A—C1A—C3A	−179.38 (17)	C1—N1—C2—S1	−9.3 (3)
C7A—N3A—C11A—C10A	0.4 (3)	O2A—C6A—C5A—C4A	0.0 (2)
C11A—N3A—C7A—C8A	−0.1 (3)	C3A—C4A—C5A—C6A	0.1 (2)
C11A—N3A—C7A—N2A	−178.41 (17)	N3—C11—C10—C9	0.8 (3)
C2A—N2A—C7A—N3A	9.8 (3)	C8—C9—C10—C11	−0.7 (3)
C2A—N2A—C7A—C8A	−168.59 (19)	C11A—C10A—C9A—C8A	−0.7 (4)
C11—N3—C7—C8	0.3 (3)	O2—C3—C4—C5	−0.2 (2)
C11—N3—C7—N2	179.18 (16)	C1—C3—C4—C5	177.4 (2)
C2—N2—C7—N3	5.8 (3)	C10A—C9A—C8A—C7A	0.9 (3)
C2—N2—C7—C8	−175.35 (17)	N3A—C7A—C8A—C9A	−0.5 (3)
N3—C7—C8—C9	−0.2 (3)	N2A—C7A—C8A—C9A	177.75 (19)
N2—C7—C8—C9	−179.06 (16)	O2—C6—C5—C4	0.0 (2)
C6A—O2A—C3A—C4A	0.3 (2)	C3—C4—C5—C6	0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.89 (2)	2.23 (2)	2.653 (2)	109.3 (18)
N1—H1···N3	0.89 (2)	1.84 (2)	2.612 (2)	145 (2)
N1A—H1A···O2A	0.87 (2)	2.22 (2)	2.661 (2)	111.6 (18)
N1A—H1A···N3A	0.87 (2)	1.90 (2)	2.632 (2)	141 (2)
N2—H2···O1Aⁱ	0.84 (3)	2.13 (2)	2.940 (2)	162 (2)
N2A—H2A···S1Aⁱ	0.86 (2)	2.51 (2)	3.3530 (15)	170 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₉N₃O₂S
M_r	247.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	6.9510 (1), 15.7000 (4), 20.2700 (6)
β (°)	90.284 (2)
V (Å³)	2212.05 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.12 × 0.08 × 0.06

Data collection
Diffractometer	Enraf–Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	22281, 4337, 3574
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.122, 1.10
No. of reflections	4337
No. of parameters	323
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.46

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Bruno et al., 2002), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.89 (2)	2.23 (2)	2.653 (2)	109.3 (18)
N1—H1···N3	0.89 (2)	1.84 (2)	2.612 (2)	145 (2)
N1A—H1A···O2A	0.87 (2)	2.22 (2)	2.661 (2)	111.6 (18)
N1A—H1A···N3A	0.87 (2)	1.90 (2)	2.632 (2)	141 (2)
N2—H2···O1Aⁱ	0.84 (3)	2.13 (2)	2.940 (2)	162 (2)
N2A—H2A···S1Aⁱ	0.86 (2)	2.51 (2)	3.3530 (15)	170 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

The authors acknowledge financial support from the Brazilian agency CNPq. OE-H thanks CONACyT of Mexico for research grant No. 61541.

References

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