Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022891/kp2105sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022891/kp2105Isup2.hkl |
CCDC reference: 1302697
A mixture of methyl-2-(2,4-dichlorophenylthio)acetate (2.51 g, 10 mmol) and hydrazine hydrate (15 ml, 80%) in absolute ethanol (50 ml) was refluxed for 5 h at 413–423 K. The excess solvent was removed by distillation. The solid residue was filtered off, washed with water and recrystallized from ethanol (30%) to give the title compound (yield, 2.28 g; 91%, m.p. 333–335 K). Colourless single crystals of (I) were obtained by slow evaporation of an ethanol solution at room temperature.
H atoms were positioned geometrically, with N—H = 0.86 Å (for NH and NH2) and C—H = 0.93 and 0.96 Å for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.2 for all other H atoms.
Aromatic hydrazides are important intermediates in heterocyclic chemistry and have been used for the synthesis of various biologically active five- membered heterocycles such as 2,5-disubstituted-1,3,4-oxadiazoles (Zheng et al., 2003; Al-Talib et al., 1990) and 5-substituted-2-mercapto-1,3,4- oxadiazoles (Yousif et al., 1986; Ahmad et al., 2001; Al-Soud et al., 2004; El-Emam et al., 2004). In view of the versatility of these compounds, we have synthesized the title compound, (I), and reported its crystal structure (Fig. 1). Bond distances and angles are within expected ranges (Allen et al., 1987). The dihedral angle between the planar hydrazidic group (C8/O1/N1/N2) and benzene ring (C1—C6) is 91.07 (3)°. The two centrosymmetrically related N1—H1A···O1 (N1···O1, 3.078 Å, H1A···O1, 2.666 Å, N1—H1A···O1, 110.8 °) hydrogen bonds form a dimer (Fig. 3).
For related literature, see: Ahmad et al. (2001); Al-Soud et al. (2004); Al-Talib et al. (1990); Allen et al. (1987); El-Emam et al. (2004); Yousif et al. (1986); Zheng et al. (2003); Furniss et al. (1978).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
C8H8Cl2N2OS | Z = 2 |
Mr = 251.13 | F(000) = 240 |
Triclinic, P1 | Dx = 1.657 Mg m−3 |
Hall symbol: -P 1 | Melting point: 333(2) K |
a = 7.350 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.133 (6) Å | Cell parameters from 1520 reflections |
c = 8.545 (6) Å | θ = 2.7–24.9° |
α = 94.802 (10)° | µ = 0.82 mm−1 |
β = 90.140 (9)° | T = 293 K |
γ = 98.492 (10)° | Block, colourless |
V = 503.4 (6) Å3 | 0.15 × 0.14 × 0.14 mm |
Bruker SMART CCD diffractometer | 1644 independent reflections |
Radiation source: rotating-anode generator | 1160 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
φ–ω scans | θmax = 25.0°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.882, Tmax = 0.892 | k = −9→9 |
3032 measured reflections | l = −10→10 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0784P)2] where P = (Fo2 + 2Fc2)/3 |
1644 reflections | (Δ/σ)max < 0.001 |
127 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.12 e Å−3 |
C8H8Cl2N2OS | γ = 98.492 (10)° |
Mr = 251.13 | V = 503.4 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.350 (5) Å | Mo Kα radiation |
b = 8.133 (6) Å | µ = 0.82 mm−1 |
c = 8.545 (6) Å | T = 293 K |
α = 94.802 (10)° | 0.15 × 0.14 × 0.14 mm |
β = 90.140 (9)° |
Bruker SMART CCD diffractometer | 1644 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1160 reflections with I > 2σ(I) |
Tmin = 0.882, Tmax = 0.892 | Rint = 0.018 |
3032 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.22 e Å−3 |
1644 reflections | Δρmin = −0.12 e Å−3 |
127 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.26701 (14) | 1.01419 (12) | −0.39917 (10) | 0.0743 (4) | |
Cl2 | 0.29479 (11) | 0.81304 (11) | 0.18225 (9) | 0.0635 (3) | |
S1 | −0.0786 (2) | 0.6652 (3) | 0.1237 (2) | 0.0532 (6) | |
O1 | −0.4782 (3) | 0.4371 (3) | 0.2779 (3) | 0.0636 (7) | |
N1 | −0.2216 (3) | 0.4350 (3) | 0.5150 (3) | 0.0590 (7) | |
H1A | −0.3282 | 0.3804 | 0.5317 | 0.071* | |
H1B | −0.1347 | 0.4414 | 0.5838 | 0.071* | |
N2 | −0.1897 (3) | 0.5134 (3) | 0.3760 (3) | 0.0493 (6) | |
H2A | −0.0822 | 0.5674 | 0.3615 | 0.059* | |
C1 | −0.0239 (4) | 0.8374 (4) | −0.2621 (4) | 0.0553 (8) | |
H1C | −0.0901 | 0.8442 | −0.3536 | 0.066* | |
C2 | −0.1059 (4) | 0.7541 (4) | −0.1410 (4) | 0.0530 (8) | |
H2B | −0.2280 | 0.7042 | −0.1521 | 0.064* | |
C3 | −0.0111 (4) | 0.7427 (3) | −0.0025 (3) | 0.0420 (7) | |
C4 | 0.1726 (4) | 0.8207 (4) | 0.0105 (3) | 0.0440 (7) | |
C5 | 0.2569 (4) | 0.9021 (4) | −0.1106 (3) | 0.0500 (8) | |
H5A | 0.3796 | 0.9509 | −0.1015 | 0.060* | |
C6 | 0.1565 (4) | 0.9103 (4) | −0.2466 (4) | 0.0489 (7) | |
C7 | −0.2690 (3) | 0.5928 (4) | 0.1181 (4) | 0.0480 (8) | |
H7A | −0.2920 | 0.5122 | 0.0274 | 0.058* | |
H7B | −0.3450 | 0.6792 | 0.1076 | 0.058* | |
C8 | −0.3188 (4) | 0.5081 (4) | 0.2650 (4) | 0.0465 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0896 (7) | 0.0862 (7) | 0.0453 (5) | −0.0039 (5) | 0.0005 (4) | 0.0252 (5) |
Cl2 | 0.0477 (5) | 0.0938 (7) | 0.0471 (5) | −0.0065 (4) | −0.0114 (3) | 0.0262 (4) |
S1 | 0.0355 (11) | 0.0735 (14) | 0.0494 (13) | −0.0026 (9) | −0.0025 (9) | 0.0172 (11) |
O1 | 0.0348 (11) | 0.0873 (17) | 0.0636 (15) | −0.0072 (11) | 0.0015 (10) | 0.0057 (12) |
N1 | 0.0428 (14) | 0.085 (2) | 0.0482 (16) | −0.0029 (13) | −0.0014 (11) | 0.0211 (14) |
N2 | 0.0376 (13) | 0.0612 (16) | 0.0485 (15) | −0.0014 (11) | 0.0028 (11) | 0.0158 (12) |
C1 | 0.061 (2) | 0.067 (2) | 0.0393 (18) | 0.0140 (16) | −0.0130 (15) | 0.0063 (16) |
C2 | 0.0393 (16) | 0.069 (2) | 0.050 (2) | 0.0043 (14) | −0.0081 (14) | 0.0072 (16) |
C3 | 0.0410 (15) | 0.0484 (17) | 0.0376 (16) | 0.0080 (13) | 0.0005 (12) | 0.0075 (13) |
C4 | 0.0432 (15) | 0.0502 (17) | 0.0382 (16) | 0.0057 (13) | −0.0063 (12) | 0.0033 (14) |
C5 | 0.0521 (17) | 0.0557 (19) | 0.0398 (17) | −0.0019 (14) | −0.0020 (14) | 0.0080 (14) |
C6 | 0.0595 (18) | 0.0514 (18) | 0.0356 (16) | 0.0073 (14) | −0.0010 (13) | 0.0043 (13) |
C7 | 0.0322 (14) | 0.0607 (19) | 0.0501 (19) | 0.0027 (13) | −0.0025 (13) | 0.0057 (15) |
C8 | 0.0359 (15) | 0.0531 (18) | 0.0493 (18) | 0.0052 (13) | 0.0026 (13) | −0.0006 (14) |
Cl1—C6 | 1.749 (3) | C1—C2 | 1.376 (4) |
Cl2—C4 | 1.729 (3) | C1—H1C | 0.9300 |
S1—C3 | 1.353 (3) | C2—C3 | 1.388 (4) |
S1—C7 | 1.435 (3) | C2—H2B | 0.9300 |
O1—C8 | 1.237 (3) | C3—C4 | 1.405 (4) |
N1—N2 | 1.399 (4) | C4—C5 | 1.375 (4) |
N1—H1A | 0.8600 | C5—C6 | 1.387 (4) |
N1—H1B | 0.8600 | C5—H5A | 0.9300 |
N2—C8 | 1.334 (4) | C7—C8 | 1.502 (4) |
N2—H2A | 0.8600 | C7—H7A | 0.9700 |
C1—C6 | 1.371 (4) | C7—H7B | 0.9700 |
C3—S1—C7 | 117.5 (2) | C5—C4—Cl2 | 119.6 (2) |
N2—N1—H1A | 120.0 | C3—C4—Cl2 | 119.1 (2) |
N2—N1—H1B | 120.0 | C4—C5—C6 | 119.0 (3) |
H1A—N1—H1B | 120.0 | C4—C5—H5A | 120.5 |
C8—N2—N1 | 122.8 (2) | C6—C5—H5A | 120.5 |
C8—N2—H2A | 118.6 | C1—C6—C5 | 121.0 (3) |
N1—N2—H2A | 118.6 | C1—C6—Cl1 | 120.8 (2) |
C6—C1—C2 | 119.4 (3) | C5—C6—Cl1 | 118.2 (2) |
C6—C1—H1C | 120.3 | S1—C7—C8 | 110.3 (2) |
C2—C1—H1C | 120.3 | S1—C7—H7A | 109.6 |
C1—C2—C3 | 121.7 (3) | C8—C7—H7A | 109.6 |
C1—C2—H2B | 119.2 | S1—C7—H7B | 109.6 |
C3—C2—H2B | 119.2 | C8—C7—H7B | 109.6 |
S1—C3—C2 | 126.5 (3) | H7A—C7—H7B | 108.1 |
S1—C3—C4 | 116.0 (2) | O1—C8—N2 | 122.9 (3) |
C2—C3—C4 | 117.5 (3) | O1—C8—C7 | 118.5 (3) |
C5—C4—C3 | 121.3 (3) | N2—C8—C7 | 118.6 (2) |
Experimental details
Crystal data | |
Chemical formula | C8H8Cl2N2OS |
Mr | 251.13 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.350 (5), 8.133 (6), 8.545 (6) |
α, β, γ (°) | 94.802 (10), 90.140 (9), 98.492 (10) |
V (Å3) | 503.4 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.82 |
Crystal size (mm) | 0.15 × 0.14 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.882, 0.892 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3032, 1644, 1160 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.136, 1.14 |
No. of reflections | 1644 |
No. of parameters | 127 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.12 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
Aromatic hydrazides are important intermediates in heterocyclic chemistry and have been used for the synthesis of various biologically active five- membered heterocycles such as 2,5-disubstituted-1,3,4-oxadiazoles (Zheng et al., 2003; Al-Talib et al., 1990) and 5-substituted-2-mercapto-1,3,4- oxadiazoles (Yousif et al., 1986; Ahmad et al., 2001; Al-Soud et al., 2004; El-Emam et al., 2004). In view of the versatility of these compounds, we have synthesized the title compound, (I), and reported its crystal structure (Fig. 1). Bond distances and angles are within expected ranges (Allen et al., 1987). The dihedral angle between the planar hydrazidic group (C8/O1/N1/N2) and benzene ring (C1—C6) is 91.07 (3)°. The two centrosymmetrically related N1—H1A···O1 (N1···O1, 3.078 Å, H1A···O1, 2.666 Å, N1—H1A···O1, 110.8 °) hydrogen bonds form a dimer (Fig. 3).