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The crystal structure of the title compound, C10H9ClN4S, is reported. There is π-conjugation between triazine and the bridging N4 atom, where N atoms are sp2 hybridized. The plane of the triazine ring forms a dihedral angle of 54.35 (4)° with the phenyl plane. There exists an intermolecular N—H...N hydrogen bond to form a dimer with an N...N separation of 2.991 (2) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020237/na6016sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020237/na6016Isup2.hkl
Contains datablock I

CCDC reference: 155903

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.031
  • wR factor = 0.096
  • Data-to-parameter ratio = 14.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry




Comment top

Heterocycles are of very important consideration in a study on new pharmaceuticals and agrochemicals. In recent years, many new chemicals have been synthesized that have structures containing heterocyclic rings, such as triazine. In our study on this type of compounds, we have found that substituted triazine-2-amine exhibited good biological activity. Adenosine antagonistic effect on human A1 receptor has been reported (Kuefner-Mueal et al., 1999). Nitrification inhibitory effects have been studied (Koizumi et al., 1994) and pest control, fungicidal activity and herbicidal activity effects have also been observed (Schapter et al., 1999; Kubuyama et al., 1998; Riebel et al., 1998). Since knowledge of the stereochemistry is useful in the rational design of pharmaceuticals and agrochemicals, we herein report the synthesis and X-ray crystal structure of the title complex, (I).

In the title compound, the N4—C4 bond length is remarkably shorter than a single C—N bond (1.47 Å; Sasada, 1984) and close to the CN double-bond distance (1.28 Å; Wang et al., 1998), which is indicative of significant double-bond character. The N4 atom and the triazine ring form a π78 configuration in which the N4 atom is sp2 hybridized. The C1—S1 bond length is slightly longer than that of C2—S1, which may be due to the note that an sp2 C atom has a smaller covalent radius than an sp3 C atom. The lengths of N—C of triazine ring are in the range of 1.319 (2)–1.362 (2) Å, in which the N3—C4 bond length is slightly longer than that of N3—C3. Atoms C1–C4/N1–N4/S1 are nearly coplanar, with an average deviation of 0.016 (1) Å, and form a 54.35 (4)° dihedral angle with the phenyl plane. Molecules of (I) are linked into dimers by intermolecular N—H···N hydrogen bonds (see Table 2).

Experimental top

To a solution of 0.77 g (5 mmol) N-(2-chlorophenyl)methanimidamide in 15 ml anhydrous toluene and 15 ml dimethylacetamide, 0.30 g (10 mmol) 80% NaOH was added with stirring, then 0.73 g (5 mmol) N-cyanocarbonimidodithioic acid dimethyl ester dropwise. After stirring for 24 h, the mixture was poured into 50 ml ice water, then quenched carefully with 10% aqueous HCl. The solid was purified by silica-gel column chromatography to give the title compound, (I) (yield: 60%). FT–IR data (KBr pellet, cm-1): 3398, 1598, 1543, 1497. Analysis calculated for (I): C 47.53, H 3.59, N 22.17%; Found: C 47.43, H 3.73, N 22.10%. Crystals of (I) were obtained as blocks by recrystallization from a petroleum ether/ethyl acetate mixture.

Refinement top

All the H atoms were located geometrically and placed in calculated positions (C—H = 0.93 Å and N—H 0.86 Å) and Uiso(H) was assigned as 1.2Ueq(C/N). SHELXS97(Sheldrick, 1997), Molecular graphics: XP (Sheldrick, 1997).

Computing details top

Data collection: SMART1000 Software (Bruker, 1998); cell refinement: SMART1000 Software; data reduction: SAINT in SMART1000 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with 30% probability ellipsoids.
[Figure 2] Fig. 2. The unit cell of the title compound.
4-methylthio-N-(2-chlorophenyl)triazine-2-amine top
Crystal data top
C10H9ClN4SF(000) = 520
Mr = 252.72Dx = 1.451 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.492 (2) ÅCell parameters from 4658 reflections
b = 7.797 (2) Åθ = 2.1–25.0°
c = 19.877 (5) ŵ = 0.49 mm1
β = 94.962 (5)°T = 298 K
V = 1156.8 (5) Å3Block, colorless
Z = 40.30 × 0.25 × 0.20 mm
Data collection top
Bruker SMART 1000
diffractometer
1730 reflections with I > 2σ(I)
ω scansRint = 0.018
Absorption correction: multi-scan
(SADABS; Blessing, 1995)
θmax = 25.0°
Tmin = 0.868, Tmax = 0.909h = 88
4658 measured reflectionsk = 98
2037 independent reflectionsl = 1823
Refinement top
Refinement on F2 w = 1/[σ2(Fo2) + (0.0547P)2 + 0.2627P] P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.031(Δ/σ)max = 0.007
wR(F2) = 0.096Δρmax = 0.20 e Å3
S = 1.04Δρmin = 0.22 e Å3
2037 reflectionsExtinction correction: SHELXL97
145 parametersExtinction coefficient: none
H-atom parameters constrained
Crystal data top
C10H9ClN4SV = 1156.8 (5) Å3
Mr = 252.72Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.492 (2) ŵ = 0.49 mm1
b = 7.797 (2) ÅT = 298 K
c = 19.877 (5) Å0.30 × 0.25 × 0.20 mm
β = 94.962 (5)°
Data collection top
Bruker SMART 1000
diffractometer
2037 independent reflections
Absorption correction: multi-scan
(SADABS; Blessing, 1995)
1730 reflections with I > 2σ(I)
Tmin = 0.868, Tmax = 0.909Rint = 0.018
4658 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031145 parameters
wR(F2) = 0.096H-atom parameters constrained
S = 1.04Δρmax = 0.20 e Å3
2037 reflectionsΔρmin = 0.22 e Å3
Special details top

Experimental. Single crystal X-ray diffraction measurements were carried out with a BRUKER SMART 1000 CCD diffractometer. The structure was solved by direct and difference Fourier methods. The final refinement was performed by full-matrix least-squares methods with anisotropic thermal parameters for non-hydrogen atoms.

Refinement. Full-matrix

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.34824 (7)0.15592 (6)0.09071 (2)0.05693 (19)
C10.3898 (3)0.2988 (3)0.02298 (11)0.0635 (5)
C20.2507 (2)0.0204 (2)0.04756 (8)0.0418 (4)
C30.1417 (2)0.1572 (2)0.04489 (8)0.0466 (4)
C40.1329 (2)0.2832 (2)0.05641 (7)0.0380 (3)
C50.1306 (2)0.4513 (2)0.16120 (8)0.0433 (4)
C60.0012 (3)0.5099 (2)0.20206 (10)0.0539 (5)
C70.0492 (4)0.5548 (3)0.26927 (11)0.0761 (7)
C80.2250 (5)0.5400 (3)0.29508 (11)0.0826 (8)
C90.3523 (4)0.4809 (3)0.25546 (11)0.0748 (7)
C100.3057 (3)0.4358 (3)0.18929 (9)0.0566 (5)
Cl10.22025 (8)0.52618 (9)0.16925 (3)0.0813 (2)
N10.21284 (18)0.14894 (17)0.08828 (7)0.0416 (3)
N20.2191 (2)0.01494 (18)0.01963 (7)0.0469 (4)
N30.09564 (18)0.29457 (18)0.01172 (6)0.0434 (3)
N40.08359 (19)0.41910 (18)0.09176 (6)0.0439 (3)
H1A0.44450.40210.04120.095*
H1B0.46860.24440.00610.095*
H1C0.27860.32630.00240.095*
H3A0.11710.16020.09150.056*
H4A0.01680.49410.07020.053*
H7A0.03710.59440.29640.091*
H8A0.25750.57050.33970.099*
H9A0.47070.47100.27330.090*
H10A0.39320.39440.16300.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0653 (3)0.0443 (3)0.0590 (3)0.0078 (2)0.0076 (2)0.0001 (2)
C10.0589 (11)0.0478 (11)0.0836 (15)0.0051 (9)0.0056 (10)0.0100 (10)
C20.0403 (8)0.0402 (9)0.0449 (9)0.0046 (7)0.0034 (7)0.0007 (7)
C30.0570 (10)0.0485 (10)0.0342 (8)0.0057 (8)0.0041 (7)0.0017 (7)
C40.0382 (8)0.0409 (8)0.0347 (8)0.0041 (7)0.0025 (6)0.0007 (7)
C50.0588 (10)0.0364 (8)0.0352 (8)0.0006 (7)0.0067 (7)0.0017 (7)
C60.0760 (13)0.0401 (9)0.0483 (10)0.0035 (9)0.0208 (9)0.0044 (8)
C70.133 (2)0.0481 (11)0.0527 (13)0.0023 (13)0.0399 (14)0.0029 (9)
C80.142 (3)0.0666 (15)0.0374 (11)0.0171 (15)0.0019 (14)0.0017 (10)
C90.0989 (17)0.0779 (15)0.0442 (11)0.0145 (13)0.0127 (11)0.0031 (10)
C100.0655 (12)0.0606 (12)0.0431 (10)0.0022 (9)0.0007 (8)0.0033 (9)
Cl10.0679 (4)0.0861 (4)0.0944 (5)0.0178 (3)0.0335 (3)0.0153 (3)
N10.0468 (8)0.0405 (8)0.0372 (7)0.0001 (6)0.0015 (6)0.0009 (6)
N20.0553 (9)0.0437 (8)0.0419 (8)0.0031 (7)0.0064 (6)0.0040 (6)
N30.0504 (8)0.0447 (8)0.0345 (7)0.0007 (6)0.0007 (6)0.0007 (6)
N40.0521 (8)0.0445 (8)0.0346 (7)0.0098 (6)0.0012 (6)0.0003 (6)
Geometric parameters (Å, º) top
S1—C21.7469 (17)N4—C41.341 (2)
S1—C11.795 (2)N4—C51.417 (2)
Cl1—C61.734 (2)C5—C101.386 (3)
N1—C21.334 (2)C5—C61.394 (2)
N1—C41.338 (2)C6—C71.398 (3)
N2—C31.330 (2)C7—C81.376 (4)
N2—C21.337 (2)C8—C91.368 (4)
N3—C31.319 (2)C9—C101.377 (3)
N3—C41.362 (2)
C2—S1—C1102.28 (10)N4—C4—N3115.34 (14)
C2—N1—C4114.23 (14)C10—C5—C6118.38 (17)
C3—N2—C2112.60 (14)C10—C5—N4121.60 (15)
C3—N3—C4113.85 (14)C6—C5—N4119.90 (16)
C4—N4—C5126.43 (14)C5—C6—C7120.3 (2)
N1—C2—N2126.99 (15)C5—C6—Cl1119.71 (15)
N1—C2—S1113.28 (12)C7—C6—Cl1119.99 (17)
N2—C2—S1119.72 (13)C8—C7—C6119.6 (2)
N3—C3—N2127.80 (15)C9—C8—C7120.4 (2)
N1—C4—N4120.16 (14)C8—C9—C10120.3 (2)
N1—C4—N3124.50 (15)C9—C10—C5121.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4a···N3i0.862.152.991 (2)168
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC10H9ClN4S
Mr252.72
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)7.492 (2), 7.797 (2), 19.877 (5)
β (°) 94.962 (5)
V3)1156.8 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.49
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerBruker SMART 1000
diffractometer
Absorption correctionMulti-scan
(SADABS; Blessing, 1995)
Tmin, Tmax0.868, 0.909
No. of measured, independent and
observed [I > 2σ(I)] reflections
4658, 2037, 1730
Rint0.018
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.096, 1.04
No. of reflections2037
No. of parameters145
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.22

Computer programs: SMART1000 Software (Bruker, 1998), SAINT in SMART1000 Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXL97.

Selected geometric parameters (Å, º) top
S1—C21.7469 (17)N2—C21.337 (2)
S1—C11.795 (2)N3—C31.319 (2)
N1—C21.334 (2)N3—C41.362 (2)
N1—C41.338 (2)N4—C41.341 (2)
N2—C31.330 (2)N4—C51.417 (2)
C2—S1—C1102.28 (10)N2—C2—S1119.72 (13)
C2—N1—C4114.23 (14)N3—C3—N2127.80 (15)
C3—N2—C2112.60 (14)N1—C4—N4120.16 (14)
C3—N3—C4113.85 (14)N1—C4—N3124.50 (15)
C4—N4—C5126.43 (14)N4—C4—N3115.34 (14)
N1—C2—N2126.99 (15)C10—C5—N4121.60 (15)
N1—C2—S1113.28 (12)C6—C5—N4119.90 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4a···N3i0.862.152.991 (2)168
Symmetry code: (i) x, y+1, z.
 

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