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The title compound, C8H8Cl2N2OS, is an important inter­mediate for the synthesis of biologically active heterocyclic compounds. The planar hydrazide group is oriented with respect to the benzene ring at a dihedral angle of 88.93 (3)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022891/kp2105sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022891/kp2105Isup2.hkl
Contains datablock I

CCDC reference: 1302697

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.044
  • wR factor = 0.136
  • Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT417_ALERT_2_B Short Inter D-H..H-D H1B .. H2A .. 1.67 Ang.
Alert level C PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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).

Related literature top

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).

Experimental top

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.

Refinement top

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.

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with the 50% probability displacement ellipsoids (arbitrary spheres for H atoms).
[Figure 2] Fig. 2. The packing diagram of (I), viewed down the b axis.
[Figure 3] Fig. 3. Preparation of the title compound.
2-(2,4-Dichlorophenylsulfanyl)acetohydrazide top
Crystal data top
C8H8Cl2N2OSZ = 2
Mr = 251.13F(000) = 240
Triclinic, P1Dx = 1.657 Mg m3
Hall symbol: -P 1Melting point: 333(2) K
a = 7.350 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.133 (6) ÅCell parameters from 1520 reflections
c = 8.545 (6) Åθ = 2.7–24.9°
α = 94.802 (10)°µ = 0.82 mm1
β = 90.140 (9)°T = 293 K
γ = 98.492 (10)°Block, colourless
V = 503.4 (6) Å30.15 × 0.14 × 0.14 mm
Data collection top
Bruker SMART CCD
diffractometer
1644 independent reflections
Radiation source: rotating-anode generator1160 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
φω scansθmax = 25.0°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.882, Tmax = 0.892k = 99
3032 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H-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 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.12 e Å3
Crystal data top
C8H8Cl2N2OSγ = 98.492 (10)°
Mr = 251.13V = 503.4 (6) Å3
Triclinic, P1Z = 2
a = 7.350 (5) ÅMo Kα radiation
b = 8.133 (6) ŵ = 0.82 mm1
c = 8.545 (6) ÅT = 293 K
α = 94.802 (10)°0.15 × 0.14 × 0.14 mm
β = 90.140 (9)°
Data collection top
Bruker SMART CCD
diffractometer
1644 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1160 reflections with I > 2σ(I)
Tmin = 0.882, Tmax = 0.892Rint = 0.018
3032 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.136H-atom parameters constrained
S = 1.14Δρmax = 0.22 e Å3
1644 reflectionsΔρmin = 0.12 e Å3
127 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.26701 (14)1.01419 (12)0.39917 (10)0.0743 (4)
Cl20.29479 (11)0.81304 (11)0.18225 (9)0.0635 (3)
S10.0786 (2)0.6652 (3)0.1237 (2)0.0532 (6)
O10.4782 (3)0.4371 (3)0.2779 (3)0.0636 (7)
N10.2216 (3)0.4350 (3)0.5150 (3)0.0590 (7)
H1A0.32820.38040.53170.071*
H1B0.13470.44140.58380.071*
N20.1897 (3)0.5134 (3)0.3760 (3)0.0493 (6)
H2A0.08220.56740.36150.059*
C10.0239 (4)0.8374 (4)0.2621 (4)0.0553 (8)
H1C0.09010.84420.35360.066*
C20.1059 (4)0.7541 (4)0.1410 (4)0.0530 (8)
H2B0.22800.70420.15210.064*
C30.0111 (4)0.7427 (3)0.0025 (3)0.0420 (7)
C40.1726 (4)0.8207 (4)0.0105 (3)0.0440 (7)
C50.2569 (4)0.9021 (4)0.1106 (3)0.0500 (8)
H5A0.37960.95090.10150.060*
C60.1565 (4)0.9103 (4)0.2466 (4)0.0489 (7)
C70.2690 (3)0.5928 (4)0.1181 (4)0.0480 (8)
H7A0.29200.51220.02740.058*
H7B0.34500.67920.10760.058*
C80.3188 (4)0.5081 (4)0.2650 (4)0.0465 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0896 (7)0.0862 (7)0.0453 (5)0.0039 (5)0.0005 (4)0.0252 (5)
Cl20.0477 (5)0.0938 (7)0.0471 (5)0.0065 (4)0.0114 (3)0.0262 (4)
S10.0355 (11)0.0735 (14)0.0494 (13)0.0026 (9)0.0025 (9)0.0172 (11)
O10.0348 (11)0.0873 (17)0.0636 (15)0.0072 (11)0.0015 (10)0.0057 (12)
N10.0428 (14)0.085 (2)0.0482 (16)0.0029 (13)0.0014 (11)0.0211 (14)
N20.0376 (13)0.0612 (16)0.0485 (15)0.0014 (11)0.0028 (11)0.0158 (12)
C10.061 (2)0.067 (2)0.0393 (18)0.0140 (16)0.0130 (15)0.0063 (16)
C20.0393 (16)0.069 (2)0.050 (2)0.0043 (14)0.0081 (14)0.0072 (16)
C30.0410 (15)0.0484 (17)0.0376 (16)0.0080 (13)0.0005 (12)0.0075 (13)
C40.0432 (15)0.0502 (17)0.0382 (16)0.0057 (13)0.0063 (12)0.0033 (14)
C50.0521 (17)0.0557 (19)0.0398 (17)0.0019 (14)0.0020 (14)0.0080 (14)
C60.0595 (18)0.0514 (18)0.0356 (16)0.0073 (14)0.0010 (13)0.0043 (13)
C70.0322 (14)0.0607 (19)0.0501 (19)0.0027 (13)0.0025 (13)0.0057 (15)
C80.0359 (15)0.0531 (18)0.0493 (18)0.0052 (13)0.0026 (13)0.0006 (14)
Geometric parameters (Å, º) top
Cl1—C61.749 (3)C1—C21.376 (4)
Cl2—C41.729 (3)C1—H1C0.9300
S1—C31.353 (3)C2—C31.388 (4)
S1—C71.435 (3)C2—H2B0.9300
O1—C81.237 (3)C3—C41.405 (4)
N1—N21.399 (4)C4—C51.375 (4)
N1—H1A0.8600C5—C61.387 (4)
N1—H1B0.8600C5—H5A0.9300
N2—C81.334 (4)C7—C81.502 (4)
N2—H2A0.8600C7—H7A0.9700
C1—C61.371 (4)C7—H7B0.9700
C3—S1—C7117.5 (2)C5—C4—Cl2119.6 (2)
N2—N1—H1A120.0C3—C4—Cl2119.1 (2)
N2—N1—H1B120.0C4—C5—C6119.0 (3)
H1A—N1—H1B120.0C4—C5—H5A120.5
C8—N2—N1122.8 (2)C6—C5—H5A120.5
C8—N2—H2A118.6C1—C6—C5121.0 (3)
N1—N2—H2A118.6C1—C6—Cl1120.8 (2)
C6—C1—C2119.4 (3)C5—C6—Cl1118.2 (2)
C6—C1—H1C120.3S1—C7—C8110.3 (2)
C2—C1—H1C120.3S1—C7—H7A109.6
C1—C2—C3121.7 (3)C8—C7—H7A109.6
C1—C2—H2B119.2S1—C7—H7B109.6
C3—C2—H2B119.2C8—C7—H7B109.6
S1—C3—C2126.5 (3)H7A—C7—H7B108.1
S1—C3—C4116.0 (2)O1—C8—N2122.9 (3)
C2—C3—C4117.5 (3)O1—C8—C7118.5 (3)
C5—C4—C3121.3 (3)N2—C8—C7118.6 (2)

Experimental details

Crystal data
Chemical formulaC8H8Cl2N2OS
Mr251.13
Crystal system, space groupTriclinic, 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)
V3)503.4 (6)
Z2
Radiation typeMo Kα
µ (mm1)0.82
Crystal size (mm)0.15 × 0.14 × 0.14
Data collection
DiffractometerBruker SMART CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.882, 0.892
No. of measured, independent and
observed [I > 2σ(I)] reflections
3032, 1644, 1160
Rint0.018
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.136, 1.14
No. of reflections1644
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

 

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