Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020237/na6016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020237/na6016Isup2.hkl |
CCDC reference: 155903
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (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
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.
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).
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.
Fig. 1. The molecular structure of the title compound with 30% probability ellipsoids. | |
Fig. 2. The unit cell of the title compound. |
C10H9ClN4S | F(000) = 520 |
Mr = 252.72 | Dx = 1.451 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.492 (2) Å | Cell parameters from 4658 reflections |
b = 7.797 (2) Å | θ = 2.1–25.0° |
c = 19.877 (5) Å | µ = 0.49 mm−1 |
β = 94.962 (5)° | T = 298 K |
V = 1156.8 (5) Å3 | Block, colorless |
Z = 4 | 0.30 × 0.25 × 0.20 mm |
Bruker SMART 1000 diffractometer | 1730 reflections with I > 2σ(I) |
ω scans | Rint = 0.018 |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | θmax = 25.0° |
Tmin = 0.868, Tmax = 0.909 | h = −8→8 |
4658 measured reflections | k = −9→8 |
2037 independent reflections | l = −18→23 |
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) = 0.096 | Δρmax = 0.20 e Å−3 |
S = 1.04 | Δρmin = −0.22 e Å−3 |
2037 reflections | Extinction correction: SHELXL97 |
145 parameters | Extinction coefficient: none |
H-atom parameters constrained |
C10H9ClN4S | V = 1156.8 (5) Å3 |
Mr = 252.72 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.492 (2) Å | µ = 0.49 mm−1 |
b = 7.797 (2) Å | T = 298 K |
c = 19.877 (5) Å | 0.30 × 0.25 × 0.20 mm |
β = 94.962 (5)° |
Bruker SMART 1000 diffractometer | 2037 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | 1730 reflections with I > 2σ(I) |
Tmin = 0.868, Tmax = 0.909 | Rint = 0.018 |
4658 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 145 parameters |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.20 e Å−3 |
2037 reflections | Δρmin = −0.22 e Å−3 |
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 |
x | y | z | Uiso*/Ueq | ||
S1 | 0.34824 (7) | −0.15592 (6) | 0.09071 (2) | 0.05693 (19) | |
C1 | 0.3898 (3) | −0.2988 (3) | 0.02298 (11) | 0.0635 (5) | |
C2 | 0.2507 (2) | 0.0204 (2) | 0.04756 (8) | 0.0418 (4) | |
C3 | 0.1417 (2) | 0.1572 (2) | −0.04489 (8) | 0.0466 (4) | |
C4 | 0.1329 (2) | 0.2832 (2) | 0.05641 (7) | 0.0380 (3) | |
C5 | 0.1306 (2) | 0.4513 (2) | 0.16120 (8) | 0.0433 (4) | |
C6 | 0.0012 (3) | 0.5099 (2) | 0.20206 (10) | 0.0539 (5) | |
C7 | 0.0492 (4) | 0.5548 (3) | 0.26927 (11) | 0.0761 (7) | |
C8 | 0.2250 (5) | 0.5400 (3) | 0.29508 (11) | 0.0826 (8) | |
C9 | 0.3523 (4) | 0.4809 (3) | 0.25546 (11) | 0.0748 (7) | |
C10 | 0.3057 (3) | 0.4358 (3) | 0.18929 (9) | 0.0566 (5) | |
Cl1 | −0.22025 (8) | 0.52618 (9) | 0.16925 (3) | 0.0813 (2) | |
N1 | 0.21284 (18) | 0.14894 (17) | 0.08828 (7) | 0.0416 (3) | |
N2 | 0.2191 (2) | 0.01494 (18) | −0.01963 (7) | 0.0469 (4) | |
N3 | 0.09564 (18) | 0.29457 (18) | −0.01172 (6) | 0.0434 (3) | |
N4 | 0.08359 (19) | 0.41910 (18) | 0.09176 (6) | 0.0439 (3) | |
H1A | 0.4445 | −0.4021 | 0.0412 | 0.095* | |
H1B | 0.4686 | −0.2444 | −0.0061 | 0.095* | |
H1C | 0.2786 | −0.3263 | −0.0024 | 0.095* | |
H3A | 0.1171 | 0.1602 | −0.0915 | 0.056* | |
H4A | 0.0168 | 0.4941 | 0.0702 | 0.053* | |
H7A | −0.0371 | 0.5944 | 0.2964 | 0.091* | |
H8A | 0.2575 | 0.5705 | 0.3397 | 0.099* | |
H9A | 0.4707 | 0.4710 | 0.2733 | 0.090* | |
H10A | 0.3932 | 0.3944 | 0.1630 | 0.068* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0653 (3) | 0.0443 (3) | 0.0590 (3) | 0.0078 (2) | −0.0076 (2) | −0.0001 (2) |
C1 | 0.0589 (11) | 0.0478 (11) | 0.0836 (15) | 0.0051 (9) | 0.0056 (10) | −0.0100 (10) |
C2 | 0.0403 (8) | 0.0402 (9) | 0.0449 (9) | −0.0046 (7) | 0.0034 (7) | −0.0007 (7) |
C3 | 0.0570 (10) | 0.0485 (10) | 0.0342 (8) | −0.0057 (8) | 0.0041 (7) | −0.0017 (7) |
C4 | 0.0382 (8) | 0.0409 (8) | 0.0347 (8) | −0.0041 (7) | 0.0025 (6) | 0.0007 (7) |
C5 | 0.0588 (10) | 0.0364 (8) | 0.0352 (8) | −0.0006 (7) | 0.0067 (7) | 0.0017 (7) |
C6 | 0.0760 (13) | 0.0401 (9) | 0.0483 (10) | 0.0035 (9) | 0.0208 (9) | 0.0044 (8) |
C7 | 0.133 (2) | 0.0481 (11) | 0.0527 (13) | 0.0023 (13) | 0.0399 (14) | −0.0029 (9) |
C8 | 0.142 (3) | 0.0666 (15) | 0.0374 (11) | −0.0171 (15) | −0.0019 (14) | −0.0017 (10) |
C9 | 0.0989 (17) | 0.0779 (15) | 0.0442 (11) | −0.0145 (13) | −0.0127 (11) | 0.0031 (10) |
C10 | 0.0655 (12) | 0.0606 (12) | 0.0431 (10) | −0.0022 (9) | 0.0007 (8) | 0.0033 (9) |
Cl1 | 0.0679 (4) | 0.0861 (4) | 0.0944 (5) | 0.0178 (3) | 0.0335 (3) | 0.0153 (3) |
N1 | 0.0468 (8) | 0.0405 (8) | 0.0372 (7) | −0.0001 (6) | 0.0015 (6) | 0.0009 (6) |
N2 | 0.0553 (9) | 0.0437 (8) | 0.0419 (8) | −0.0031 (7) | 0.0064 (6) | −0.0040 (6) |
N3 | 0.0504 (8) | 0.0447 (8) | 0.0345 (7) | −0.0007 (6) | 0.0007 (6) | −0.0007 (6) |
N4 | 0.0521 (8) | 0.0445 (8) | 0.0346 (7) | 0.0098 (6) | 0.0012 (6) | −0.0003 (6) |
S1—C2 | 1.7469 (17) | N4—C4 | 1.341 (2) |
S1—C1 | 1.795 (2) | N4—C5 | 1.417 (2) |
Cl1—C6 | 1.734 (2) | C5—C10 | 1.386 (3) |
N1—C2 | 1.334 (2) | C5—C6 | 1.394 (2) |
N1—C4 | 1.338 (2) | C6—C7 | 1.398 (3) |
N2—C3 | 1.330 (2) | C7—C8 | 1.376 (4) |
N2—C2 | 1.337 (2) | C8—C9 | 1.368 (4) |
N3—C3 | 1.319 (2) | C9—C10 | 1.377 (3) |
N3—C4 | 1.362 (2) | ||
C2—S1—C1 | 102.28 (10) | N4—C4—N3 | 115.34 (14) |
C2—N1—C4 | 114.23 (14) | C10—C5—C6 | 118.38 (17) |
C3—N2—C2 | 112.60 (14) | C10—C5—N4 | 121.60 (15) |
C3—N3—C4 | 113.85 (14) | C6—C5—N4 | 119.90 (16) |
C4—N4—C5 | 126.43 (14) | C5—C6—C7 | 120.3 (2) |
N1—C2—N2 | 126.99 (15) | C5—C6—Cl1 | 119.71 (15) |
N1—C2—S1 | 113.28 (12) | C7—C6—Cl1 | 119.99 (17) |
N2—C2—S1 | 119.72 (13) | C8—C7—C6 | 119.6 (2) |
N3—C3—N2 | 127.80 (15) | C9—C8—C7 | 120.4 (2) |
N1—C4—N4 | 120.16 (14) | C8—C9—C10 | 120.3 (2) |
N1—C4—N3 | 124.50 (15) | C9—C10—C5 | 121.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4a···N3i | 0.86 | 2.15 | 2.991 (2) | 168 |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C10H9ClN4S |
Mr | 252.72 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 7.492 (2), 7.797 (2), 19.877 (5) |
β (°) | 94.962 (5) |
V (Å3) | 1156.8 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.49 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART 1000 diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.868, 0.909 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4658, 2037, 1730 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.096, 1.04 |
No. of reflections | 2037 |
No. of parameters | 145 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.22 |
Computer programs: SMART1000 Software (Bruker, 1998), SAINT in SMART1000 Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXL97.
S1—C2 | 1.7469 (17) | N2—C2 | 1.337 (2) |
S1—C1 | 1.795 (2) | N3—C3 | 1.319 (2) |
N1—C2 | 1.334 (2) | N3—C4 | 1.362 (2) |
N1—C4 | 1.338 (2) | N4—C4 | 1.341 (2) |
N2—C3 | 1.330 (2) | N4—C5 | 1.417 (2) |
C2—S1—C1 | 102.28 (10) | N2—C2—S1 | 119.72 (13) |
C2—N1—C4 | 114.23 (14) | N3—C3—N2 | 127.80 (15) |
C3—N2—C2 | 112.60 (14) | N1—C4—N4 | 120.16 (14) |
C3—N3—C4 | 113.85 (14) | N1—C4—N3 | 124.50 (15) |
C4—N4—C5 | 126.43 (14) | N4—C4—N3 | 115.34 (14) |
N1—C2—N2 | 126.99 (15) | C10—C5—N4 | 121.60 (15) |
N1—C2—S1 | 113.28 (12) | C6—C5—N4 | 119.90 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4a···N3i | 0.86 | 2.15 | 2.991 (2) | 168 |
Symmetry code: (i) −x, −y+1, −z. |
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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 C═N 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).