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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1735–o1736.
Published online 2009 July 1. doi:  10.1107/S1600536809024672
PMCID: PMC2977335

1-(2-Chloro-5-nitro­phen­yl)-3-(2,2-di­methyl­propion­yl)thio­urea

Abstract

With the exception of the C atoms of two of the methyl groups of the tert-butyl substituent, all of the non-H atoms of the title compound, C12H14ClN3O3S, lie on a mirror plane. The 2-chloro-5-nitro­phenyl and 2,2-dimethyl­propionyl substituents are, respectively, cis and trans relative to the thio­carbonyl S atom across the two C—N bonds. Intra­molecular N—H(...)O and C—H(...)S hydrogen bonds form S(6) ring motifs, also in the mirror plane. Despite the presence of two N—H subsituents, no inter­molecular hydrogen bonds are observed in the crystal structure. Weak π–π contacts [centroid–centroid distances of 4.2903 (17) Å] involving adjacent aromatic rings link the mol­ecules in a head-to-tail fashion above and below the mol­ecular plane.

Related literature

For the use of thio­urea derivatives in organic synthesis, see: Eynde & Watte (2003 [triangle]); Fu et al. (1999 [triangle]); Rashdan et al. (2006 [triangle]); Maryanoff et al. (1986 [triangle]); Wang et al. (2005 [triangle]); Saeed et al. (2008 [triangle]); and in analysis, see: Koch (2001 [triangle]). For their bioactivity and pharmaceutical applications, see: Upadhyaya & Srivastava (1982 [triangle]); Krishnamurthy et al. (1999 [triangle]); Blum & Hayes (1979 [triangle]); DeBeer et al. (1936 [triangle]). For related structures, see: Saeed & Flörke (2007a [triangle],b [triangle]); Yusof et al. (2006 [triangle], 2008 [triangle]). For reference structural data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1735-scheme1.jpg

Experimental

Crystal data

  • C12H14ClN3O3S
  • M r = 315.77
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1735-efi2.jpg
  • a = 9.529 (2) Å
  • b = 6.546 (2) Å
  • c = 22.166 (6) Å
  • V = 1382.7 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.44 mm−1
  • T = 89 K
  • 0.36 × 0.09 × 0.06 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2006 [triangle]) T min = 0.833, T max = 0.974
  • 12525 measured reflections
  • 1434 independent reflections
  • 1166 reflections with I > 2σ(I)
  • R int = 0.069

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.092
  • S = 1.09
  • 1434 reflections
  • 130 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.27 e Å−3
  • Δρmin = −0.43 e Å−3

Data collection: APEX2 (Bruker, 2006 [triangle]); cell refinement: APEX2 and SAINT (Bruker, 2006 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]) and TITAN2000 (Hunter & Simpson, 1999 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 [triangle]), PLATON (Spek, 2009 [triangle]) and publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024672/lh2851sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024672/lh2851Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the University of Otago for the purchase of the diffractometer.

supplementary crystallographic information

Comment

Substituted thioureas are versatile building blocks for the synthesis of a variety of heterocyclic compounds with a broad range of useful applications and exhibiting a wide range of bioactivity. Solid-phase Biginelli pyrimidine synthesis (Eynde & Watte, 2003) and synthesis of imidazoline derivatives (Fu et al., 1999) have been carried out using resin-bound thioureas. Pyridyl thioureas are switchable anion receptors (Rashdan et al., 2006); thioureas are also efficient guanylating agents (Maryanoff et al., 1986) while N,N-dialkyl-N-aroyl thioureas are efficient ligands for the separation of platinum group metals (Koch, 2001). Acyl thioureas are well known for their superior pesticidal, fungicidal, antiviral and plant-growth regulatory activities (Upadhyaya & Srivastava, 1982). 1,3-Dialkyl or diaryl thioureas show powerful antifungal activity against plant pathogens Pyricularia oryzae and Drechslera oryzae (Krishnamurthy et al., 1999). Substituted thioureas are potent enhancers of 30S dynein ATPase activity and inhibitors of 14S dynein ATPase activity (Blum & Hayes, 1979). Aryl and alkyl-aryl thioureas display strong hypnotic potency in mice (DeBeer et al., 1936). 1-Aroyl-3-arylthioureas are an exceptionally important group of thioureas which have attracted recent interest. They have been used in the synthesis of imidazole-2-thiones (Wang et al., 2005) and 2-(aroylimino)-3-aryl-4-phenyl-1,3-thiazolines (Saeed et al., 2008). We report here the structure of the title thiourea derivative (I), Fig. 1.

With the exception of the C12 atoms of two methyl groups of the t-butyl substituent all of the non-hydrogen atoms of the title compound, C13H15N2O3SCl lie on a mirror plane. Intramolecular N2—H2N···O1 and C9—H9···S1 hydrogen bonds each form a 6-membered ring, also in the mirror plane. Bond distances within the molecule are normal (Allen et al. 1987) and similar to those observed in comparable structures (Saeed & Flörke 2007a,b; Yusof et al. 2006, 2008). Despite the presence of both amide and thioamide groups in the molecule, no intermolecular hydrogen bonds are observed in the crystal structure. Weak π–π contacts between neighbouring C4···C9 rings, Fig 2, with centroid···centroid distances 4.2903 (17)Å and perpendicular distances between the molecular planes of 3.273Å link adjacent molecules above and below the molecular plane along b. These stacks of molecules form sheets parallel to the c axis, Fig. 3.

Experimental

A solution of pivaloyl chloride (10 mmol) in anhydrous acetone (50 ml) was added dropwise to a suspension of potassium thiocyanate (10 mmol) in acetone (30 ml) and the reaction mixture was refluxed for 30 min. After cooling to room temperature, a solution of 2-chloro-5-nitroaniline (1.28 g, 10 mmol) in acetone (10 ml) was added and the resulting mixture refluxed for 2 h. The reaction mixture was poured into cold water and the thiourea was precipitated as a white solid. Recrystallization from ethanol gave colorless crystals of (I) (8.6 mmol, 86%). IR (KBr) cm-1: 3351 (free NH), 3200 (assoc. NH), 1667 (CO), 1610 (arom.), 1529 (thioureido I) 1325 II, 1160 III, 744, 762.

Refinement

The H atoms bound to N1 and N2 and C11 were located in a difference Fourier map and their coordinates refined with Uiso= 1.2Ueq (N/C). All other H atoms were refined using a riding model with d(C—H) = 0.95 Å, for aromatic H atoms with Uiso= 1.2Ueq (C). For the remaining methyl groups d(C—H) = 0.98 Å, Uiso = 1.5Ueq (C).

Figures

Fig. 1.
The structure of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level. Intramolecular hydrogen bonds are drawn as dashed lines. The atom labeled C12A is related to the C12 atom by the symmetry operation x, -y ...
Fig. 2.
π–π interactions for (1).
Fig. 3.
Crystal packing for (I) viewed down the a axis.

Crystal data

C12H14ClN3O3SF(000) = 656
Mr = 315.77Dx = 1.517 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 2410 reflections
a = 9.529 (2) Åθ = 2.3–24.6°
b = 6.546 (2) ŵ = 0.44 mm1
c = 22.166 (6) ÅT = 89 K
V = 1382.7 (7) Å3Needle, colourless
Z = 40.36 × 0.09 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer1434 independent reflections
Radiation source: fine-focus sealed tube1166 reflections with I > 2σ(I)
graphiteRint = 0.069
ω scansθmax = 25.7°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2006)h = −11→11
Tmin = 0.833, Tmax = 0.974k = −6→8
12525 measured reflectionsl = −26→26

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 1.09w = 1/[σ2(Fo2) + (0.0461P)2 + 0.3426P] where P = (Fo2 + 2Fc2)/3
1434 reflections(Δ/σ)max < 0.001
130 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = −0.43 e Å3

Special details

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)

xyzUiso*/Ueq
C10.1946 (3)0.25000.36075 (12)0.0163 (6)
O10.3187 (2)0.25000.34713 (8)0.0217 (5)
N10.1523 (3)0.25000.42088 (10)0.0184 (5)
H1N0.070 (4)0.25000.4268 (16)0.037 (11)*
C20.2314 (3)0.25000.47417 (11)0.0143 (6)
S10.14289 (7)0.25000.53901 (3)0.0192 (2)
N20.3713 (2)0.25000.46466 (10)0.0143 (5)
H2N0.397 (3)0.25000.4222 (15)0.030 (9)*
C40.4846 (3)0.25000.50580 (12)0.0130 (6)
C50.6210 (3)0.25000.48174 (11)0.0147 (6)
Cl10.64439 (7)0.25000.40389 (3)0.0181 (2)
C60.7399 (3)0.25000.51801 (12)0.0168 (6)
H60.83050.25000.50020.020*
C70.7261 (3)0.25000.58025 (12)0.0183 (6)
H70.80600.25000.60590.022*
C80.5911 (3)0.25000.60368 (11)0.0167 (6)
N30.5743 (3)0.25000.67027 (10)0.0204 (5)
O20.6808 (2)0.25000.70124 (9)0.0286 (5)
O30.4544 (2)0.25000.69074 (9)0.0317 (6)
C90.4711 (3)0.25000.56877 (11)0.0147 (6)
H90.38100.25000.58710.018*
C100.0727 (3)0.25000.31561 (11)0.0170 (6)
C110.1330 (3)0.25000.25185 (13)0.0308 (8)
H11A0.059 (4)0.25000.2261 (16)0.037*
H11B0.188 (2)0.132 (3)0.2442 (10)0.037*
C12−0.0158 (2)0.0571 (3)0.32488 (9)0.0229 (5)
H12A−0.08970.05150.29420.034*
H12B−0.05850.06020.36510.034*
H12C0.0442−0.06380.32130.034*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0149 (14)0.0200 (15)0.0142 (14)0.000−0.0001 (11)0.000
O10.0135 (10)0.0360 (12)0.0155 (9)0.0000.0018 (8)0.000
N10.0109 (13)0.0317 (14)0.0125 (11)0.0000.0003 (10)0.000
C20.0129 (13)0.0185 (14)0.0113 (13)0.000−0.0021 (10)0.000
S10.0149 (4)0.0307 (4)0.0121 (3)0.0000.0020 (3)0.000
N20.0124 (12)0.0196 (12)0.0110 (11)0.000−0.0008 (9)0.000
C40.0134 (13)0.0108 (13)0.0146 (13)0.000−0.0025 (10)0.000
C50.0183 (14)0.0129 (13)0.0128 (13)0.000−0.0007 (11)0.000
Cl10.0149 (4)0.0262 (4)0.0132 (3)0.0000.0020 (2)0.000
C60.0128 (14)0.0169 (14)0.0209 (14)0.0000.0010 (11)0.000
C70.0190 (15)0.0148 (14)0.0210 (14)0.000−0.0057 (12)0.000
C80.0213 (15)0.0150 (14)0.0139 (13)0.000−0.0018 (11)0.000
N30.0258 (14)0.0213 (13)0.0142 (12)0.000−0.0011 (10)0.000
O20.0284 (12)0.0391 (13)0.0182 (10)0.000−0.0114 (9)0.000
O30.0266 (12)0.0527 (15)0.0157 (10)0.0000.0031 (9)0.000
C90.0165 (14)0.0122 (13)0.0154 (13)0.000−0.0002 (11)0.000
C100.0147 (14)0.0258 (15)0.0104 (13)0.000−0.0018 (11)0.000
C110.0193 (17)0.062 (2)0.0115 (14)0.000−0.0013 (13)0.000
C120.0222 (11)0.0220 (11)0.0245 (10)0.0000 (9)−0.0078 (8)−0.0021 (9)

Geometric parameters (Å, °)

C1—O11.221 (3)C7—C81.387 (4)
C1—N11.392 (3)C7—H70.9500
C1—C101.533 (4)C8—C91.380 (4)
N1—C21.401 (3)C8—N31.485 (3)
N1—H1N0.80 (4)N3—O21.226 (3)
C2—N21.349 (3)N3—O31.229 (3)
C2—S11.667 (3)C9—H90.9500
N2—C41.414 (3)C10—C111.526 (4)
N2—H2N0.97 (3)C10—C121.533 (3)
C4—C91.402 (3)C10—C12i1.533 (3)
C4—C51.405 (4)C11—H11A0.91 (4)
C5—C61.389 (4)C11—H11B0.95 (2)
C5—Cl11.740 (3)C12—H12A0.9800
C6—C71.386 (4)C12—H12B0.9800
C6—H60.9500C12—H12C0.9800
O1—C1—N1121.1 (2)C9—C8—C7123.9 (2)
O1—C1—C10124.9 (2)C9—C8—N3117.9 (2)
N1—C1—C10113.9 (2)C7—C8—N3118.2 (2)
C1—N1—C2130.6 (2)O2—N3—O3124.3 (2)
C1—N1—H1N116 (3)O2—N3—C8117.9 (2)
C2—N1—H1N113 (3)O3—N3—C8117.8 (2)
N2—C2—N1113.6 (2)C8—C9—C4118.8 (2)
N2—C2—S1129.4 (2)C8—C9—H9120.6
N1—C2—S1117.0 (2)C4—C9—H9120.6
C2—N2—C4130.8 (2)C11—C10—C12109.35 (14)
C2—N2—H2N113.7 (19)C11—C10—C12i109.35 (14)
C4—N2—H2N115.5 (19)C12—C10—C12i111.0 (2)
C9—C4—C5117.6 (2)C11—C10—C1108.6 (2)
C9—C4—N2124.9 (2)C12—C10—C1109.25 (14)
C5—C4—N2117.5 (2)C12i—C10—C1109.25 (14)
C6—C5—C4122.3 (2)C10—C11—H11A107 (2)
C6—C5—Cl1118.0 (2)C10—C11—H11B111.9 (14)
C4—C5—Cl1119.7 (2)H11A—C11—H11B108.5 (18)
C7—C6—C5119.9 (2)C10—C12—H12A109.5
C7—C6—H6120.0C10—C12—H12B109.5
C5—C6—H6120.0H12A—C12—H12B109.5
C6—C7—C8117.4 (2)C10—C12—H12C109.5
C6—C7—H7121.3H12A—C12—H12C109.5
C8—C7—H7121.3H12B—C12—H12C109.5
O1—C1—N1—C20.0C6—C7—C8—N3180.0
C10—C1—N1—C2180.0C9—C8—N3—O2180.0
C1—N1—C2—N20.0C7—C8—N3—O20.000 (1)
C1—N1—C2—S1180.0C9—C8—N3—O30.000 (1)
N1—C2—N2—C4180.0C7—C8—N3—O3180.0
S1—C2—N2—C40.000 (1)C7—C8—C9—C40.000 (1)
C2—N2—C4—C90.000 (1)N3—C8—C9—C4180.0
C2—N2—C4—C5180.0C5—C4—C9—C80.000 (1)
C9—C4—C5—C60.0N2—C4—C9—C8180.0
N2—C4—C5—C6180.0O1—C1—C10—C110.0
C9—C4—C5—Cl1180.0N1—C1—C10—C11180.0
N2—C4—C5—Cl10.0O1—C1—C10—C12119.21 (15)
C4—C5—C6—C70.000 (1)N1—C1—C10—C12−60.79 (15)
Cl1—C5—C6—C7180.0O1—C1—C10—C12i−119.21 (15)
C5—C6—C7—C80.000 (1)N1—C1—C10—C12i60.79 (15)
C6—C7—C8—C90.000 (1)

Symmetry codes: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9···S10.952.513.197 (3)130
N2—H2N···O10.97 (3)1.82 (3)2.653 (3)141 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2851).

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