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In the structure of the title compound, C12H14Cl2N2OS, the plane of the thio­amide and amide groups forms a dihedral angle of 59.4 (1)° with the aromatic plane. The crystal packing shows inter­molecular N—H...S and C—H...O hydrogen bonds, resulting in chains along [001].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055808/fj2064sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055808/fj2064Isup2.hkl
Contains datablock I

CCDC reference: 672875

Key indicators

  • Single-crystal X-ray study
  • T = 153 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.031
  • wR factor = 0.089
  • Data-to-parameter ratio = 20.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 400 Deg. PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - C6 .. 6.64 su
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 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
checkCIF publication errors
Alert level G PUBL013_ALERT_1_G The _publ_section_comment (discussion of study) is missing. This is required for a full paper submission (but is optional for an electronic paper).
0 ALERT level A = Data missing that is essential or data in wrong format 1 ALERT level G = General alerts. Data that may be required is missing

Related literature top

For related literature, see: Saeed & Flörke (2006); Saeed & Flörke (2007).

Experimental top

A freshly distilled solution of pivaloyl chloride (1.20 g, 10 mmol) in acetone (50 ml) was added dropwise to a suspension of potassium thiocyanate (0.97 g, 10 mmol) in acetone (30 ml) and the reaction mixture was refluxed for 30 min. After cooling to room temperature, a solution of 2,4-dichloroaniline (10 mmol) in acetone (10 ml) was added and the resulting mixture refluxed for 2.0 h. The reaction mixture was poured into cold water when the thiourea was precipitated as a solid. Recrystallized from aqueous ethanol as colourless crystals (2.47 g, 81.0 mmol, 81%). IR (KBr) cm-1: 3351 (free NH), 3200 (assoc. NH), 1667 (CO), 1610, 1529, 1325 II, 1160 III, 744, 762; 1H NMR (CDCl3) 1,27 (9H, s, pivaloyl), 7.31–7.75 (aromatic), 9.19 (1H, s, broad, NH); 12.76 (1H, s, broad, NH); EIMS m/e: 281, 283, 149, 119, 91, 64.9; Analysis calculated for C12H14Cl2N2OS C, 47.22; H, 4.62; N, 9.18; S, 10.51 found C, 47.03; H, 4.21; N, 9.03; S, 10.59

Refinement top

Hydrogen atoms were located in difference syntheses, refined at idealized positions riding on the C/N (C/N—H = 0.88–0.98 Å) atoms with isotropic displacement parameters Uiso(H) = 1.2U(C/Neq) and 1.5(methyl-C). Methyl H atoms were refined on the basis of rigid groups allowed to rotate but not tip.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL (Bruker, 2002); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL (Bruker, 2002).

Figures top
[Figure 1] Fig. 1. Molecular structure of I. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Crystal packing of I viewed along [100] with hydrogen bond indicated as dashed lines. H-atoms not involved are omitted.
1-(2,4-Dichlorophenyl)-3-pivaloylthiourea top
Crystal data top
C12H14Cl2N2OSZ = 2
Mr = 305.21F(000) = 316
Triclinic, P1Dx = 1.438 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.7613 (13) ÅCell parameters from 831 reflections
b = 10.672 (2) Åθ = 2.6–28.3°
c = 11.687 (3) ŵ = 0.60 mm1
α = 89.971 (4)°T = 153 K
β = 87.442 (4)°Prism, colourless
γ = 79.142 (4)°0.50 × 0.35 × 0.20 mm
V = 705.0 (3) Å3
Data collection top
Bruker SMART APEX
diffractometer
3335 independent reflections
Radiation source: sealed tube3067 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
ϕ and ω scansθmax = 27.9°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 77
Tmin = 0.754, Tmax = 0.890k = 1413
6176 measured reflectionsl = 1515
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)] = 0.031Hydrogen site location: difference Fourier map
wR(F2) = 0.089H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0459P)2 + 0.2299P]
where P = (Fo2 + 2Fc2)/3
3335 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C12H14Cl2N2OSγ = 79.142 (4)°
Mr = 305.21V = 705.0 (3) Å3
Triclinic, P1Z = 2
a = 5.7613 (13) ÅMo Kα radiation
b = 10.672 (2) ŵ = 0.60 mm1
c = 11.687 (3) ÅT = 153 K
α = 89.971 (4)°0.50 × 0.35 × 0.20 mm
β = 87.442 (4)°
Data collection top
Bruker SMART APEX
diffractometer
3335 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
3067 reflections with I > 2σ(I)
Tmin = 0.754, Tmax = 0.890Rint = 0.018
6176 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.089H-atom parameters constrained
S = 1.11Δρmax = 0.43 e Å3
3335 reflectionsΔρmin = 0.22 e Å3
163 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
Cl10.30159 (7)0.38856 (4)0.00947 (3)0.02712 (11)
Cl20.31541 (7)0.07079 (4)0.07202 (3)0.02971 (11)
S10.26725 (6)0.38832 (3)0.43598 (3)0.02211 (10)
O10.1561 (2)0.72933 (11)0.19875 (10)0.0315 (3)
N10.2906 (2)0.61858 (11)0.35704 (10)0.0207 (2)
H1A0.37110.62270.41870.025*
N20.1156 (2)0.49459 (12)0.23844 (10)0.0230 (3)
H2A0.10670.56000.19190.028*
C10.2497 (2)0.72796 (14)0.29081 (12)0.0206 (3)
C20.3301 (3)0.84537 (13)0.33826 (12)0.0205 (3)
C30.2641 (3)0.86311 (15)0.46723 (13)0.0257 (3)
H3A0.09190.87570.47940.039*
H3B0.32040.93780.49590.039*
H3C0.33820.78700.50840.039*
C40.2103 (3)0.96304 (15)0.27303 (14)0.0288 (3)
H4A0.03860.97560.28730.043*
H4B0.24840.95020.19080.043*
H4C0.26751.03850.29940.043*
C50.6003 (3)0.82520 (16)0.31594 (14)0.0285 (3)
H5A0.63820.81390.23360.043*
H5B0.67610.74910.35650.043*
H5C0.65840.89980.34350.043*
C60.2191 (2)0.50284 (13)0.33738 (12)0.0192 (3)
C70.0187 (3)0.38919 (14)0.20202 (12)0.0203 (3)
C80.0899 (2)0.33226 (13)0.09547 (12)0.0194 (3)
C90.0097 (3)0.23329 (13)0.05465 (12)0.0206 (3)
H9A0.04110.19410.01740.025*
C100.1855 (3)0.19333 (13)0.12204 (12)0.0211 (3)
C110.2635 (3)0.24941 (15)0.22733 (13)0.0239 (3)
H11A0.38550.22100.27170.029*
C120.1605 (3)0.34757 (15)0.26677 (13)0.0241 (3)
H12A0.21270.38680.33870.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.02866 (19)0.0297 (2)0.02442 (19)0.00995 (15)0.00276 (14)0.00234 (14)
Cl20.0356 (2)0.0256 (2)0.0317 (2)0.01407 (16)0.00617 (15)0.00329 (15)
S10.02430 (18)0.01953 (18)0.02304 (18)0.00448 (13)0.00539 (13)0.00337 (13)
O10.0466 (7)0.0285 (6)0.0238 (5)0.0152 (5)0.0138 (5)0.0067 (4)
N10.0249 (6)0.0192 (6)0.0192 (5)0.0062 (5)0.0066 (4)0.0005 (4)
N20.0314 (7)0.0212 (6)0.0187 (6)0.0096 (5)0.0056 (5)0.0013 (5)
C10.0208 (6)0.0214 (7)0.0205 (6)0.0061 (5)0.0012 (5)0.0005 (5)
C20.0213 (6)0.0190 (7)0.0220 (7)0.0058 (5)0.0032 (5)0.0002 (5)
C30.0317 (8)0.0206 (7)0.0236 (7)0.0016 (6)0.0016 (6)0.0032 (5)
C40.0343 (8)0.0213 (7)0.0316 (8)0.0064 (6)0.0074 (6)0.0057 (6)
C50.0232 (7)0.0315 (8)0.0323 (8)0.0090 (6)0.0003 (6)0.0008 (6)
C60.0189 (6)0.0191 (6)0.0194 (6)0.0035 (5)0.0000 (5)0.0023 (5)
C70.0232 (7)0.0193 (6)0.0191 (6)0.0050 (5)0.0055 (5)0.0006 (5)
C80.0207 (6)0.0195 (6)0.0181 (6)0.0035 (5)0.0025 (5)0.0035 (5)
C90.0253 (7)0.0185 (7)0.0175 (6)0.0020 (5)0.0039 (5)0.0006 (5)
C100.0241 (7)0.0174 (6)0.0230 (7)0.0059 (5)0.0074 (5)0.0001 (5)
C110.0248 (7)0.0268 (7)0.0216 (7)0.0084 (6)0.0015 (5)0.0013 (6)
C120.0262 (7)0.0276 (7)0.0193 (7)0.0069 (6)0.0005 (5)0.0026 (6)
Geometric parameters (Å, º) top
Cl1—C81.7390 (14)C3—H3C0.9800
Cl2—C101.7382 (15)C4—H4A0.9800
S1—C61.6728 (15)C4—H4B0.9800
O1—C11.2237 (18)C4—H4C0.9800
N1—C11.3890 (18)C5—H5A0.9800
N1—C61.3959 (18)C5—H5B0.9800
N1—H1A0.8800C5—H5C0.9800
N2—C61.3348 (19)C7—C121.392 (2)
N2—C71.4202 (19)C7—C81.396 (2)
N2—H2A0.8800C8—C91.388 (2)
C1—C21.528 (2)C9—C101.385 (2)
C2—C41.534 (2)C9—H9A0.9500
C2—C31.541 (2)C10—C111.387 (2)
C2—C51.541 (2)C11—C121.386 (2)
C3—H3A0.9800C11—H11A0.9500
C3—H3B0.9800C12—H12A0.9500
C1—N1—C6127.71 (12)C2—C5—H5A109.5
C1—N1—H1A116.1C2—C5—H5B109.5
C6—N1—H1A116.1H5A—C5—H5B109.5
C6—N2—C7125.49 (12)C2—C5—H5C109.5
C6—N2—H2A117.3H5A—C5—H5C109.5
C7—N2—H2A117.3H5B—C5—H5C109.5
O1—C1—N1121.45 (13)N2—C6—N1115.21 (12)
O1—C1—C2121.99 (13)N2—C6—S1125.67 (11)
N1—C1—C2116.55 (12)N1—C6—S1119.12 (11)
C1—C2—C4108.52 (12)C12—C7—C8118.96 (13)
C1—C2—C3111.07 (12)C12—C7—N2121.05 (13)
C4—C2—C3109.68 (12)C8—C7—N2119.79 (13)
C1—C2—C5106.99 (12)C9—C8—C7121.34 (13)
C4—C2—C5109.64 (12)C9—C8—Cl1118.80 (11)
C3—C2—C5110.87 (13)C7—C8—Cl1119.83 (11)
C2—C3—H3A109.5C10—C9—C8118.08 (13)
C2—C3—H3B109.5C10—C9—H9A121.0
H3A—C3—H3B109.5C8—C9—H9A121.0
C2—C3—H3C109.5C9—C10—C11122.05 (13)
H3A—C3—H3C109.5C9—C10—Cl2118.93 (11)
H3B—C3—H3C109.5C11—C10—Cl2119.02 (11)
C2—C4—H4A109.5C12—C11—C10118.92 (13)
C2—C4—H4B109.5C12—C11—H11A120.5
H4A—C4—H4B109.5C10—C11—H11A120.5
C2—C4—H4C109.5C11—C12—C7120.63 (14)
H4A—C4—H4C109.5C11—C12—H12A119.7
H4B—C4—H4C109.5C7—C12—H12A119.7
C6—N1—C1—O15.8 (2)C12—C7—C8—C91.7 (2)
C6—N1—C1—C2174.84 (13)N2—C7—C8—C9176.72 (13)
O1—C1—C2—C416.44 (19)C12—C7—C8—Cl1176.39 (11)
N1—C1—C2—C4164.22 (13)N2—C7—C8—Cl11.40 (19)
O1—C1—C2—C3137.09 (15)C7—C8—C9—C100.9 (2)
N1—C1—C2—C343.57 (17)Cl1—C8—C9—C10177.21 (11)
O1—C1—C2—C5101.78 (16)C8—C9—C10—C110.3 (2)
N1—C1—C2—C577.55 (15)C8—C9—C10—Cl2179.26 (11)
C7—N2—C6—N1176.92 (13)C9—C10—C11—C120.7 (2)
C7—N2—C6—S13.0 (2)Cl2—C10—C11—C12179.65 (12)
C1—N1—C6—N25.6 (2)C10—C11—C12—C70.1 (2)
C1—N1—C6—S1174.33 (11)C8—C7—C12—C111.3 (2)
C6—N2—C7—C1258.5 (2)N2—C7—C12—C11176.24 (14)
C6—N2—C7—C8126.57 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.881.882.5990 (17)137
N1—H1A···S1i0.882.733.5814 (14)163
C9—H9A···O1ii0.952.513.1203 (19)122
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC12H14Cl2N2OS
Mr305.21
Crystal system, space groupTriclinic, P1
Temperature (K)153
a, b, c (Å)5.7613 (13), 10.672 (2), 11.687 (3)
α, β, γ (°)89.971 (4), 87.442 (4), 79.142 (4)
V3)705.0 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.60
Crystal size (mm)0.50 × 0.35 × 0.20
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.754, 0.890
No. of measured, independent and
observed [I > 2σ(I)] reflections
6176, 3335, 3067
Rint0.018
(sin θ/λ)max1)0.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.089, 1.11
No. of reflections3335
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.43, 0.22

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Bruker, 2002).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.881.882.5990 (17)137
N1—H1A···S1i0.882.733.5814 (14)163
C9—H9A···O1ii0.952.513.1203 (19)122
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z.
 

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