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Acta Crystallogr Sect E Struct Rep Online. 2010 March 1; 66(Pt 3): o568.
Published online 2010 February 10. doi:  10.1107/S1600536810004472
PMCID: PMC2983563

2-Amino-4-tert-butyl-5-(2,4-dichloro­benz­yl)thia­zol-3-ium bromide

Abstract

The asymmetric unit of the title compound, C14H17Cl2N2S+·Br, contains one cation and two Br ions with site symmetry An external file that holds a picture, illustration, etc.
Object name is e-66-0o568-efi1.jpg. The dihedral angle between the planes of the thia­zol and the dichloro­phenyl rings is 77.8 (6)°. In the crystal, the ions are connected by N–H(...)Br hydrogen bonds.

Related literature

For background information and related structures, see: Cao et al. (2007 [triangle]); Hu et al. (2008 [triangle]); Marcantonio et al. (2002 [triangle]); Xu et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o568-scheme1.jpg

Experimental

Crystal data

  • C14H17Cl2N2S+·Br
  • M r = 396.17
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o568-efi2.jpg
  • a = 8.7797 (5) Å
  • b = 9.3898 (5) Å
  • c = 11.8430 (7) Å
  • α = 103.960 (1)°
  • β = 91.102 (1)°
  • γ = 116.648 (1)°
  • V = 837.66 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.89 mm−1
  • T = 173 K
  • 0.43 × 0.31 × 0.22 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004 [triangle]) T min = 0.370, T max = 0.569
  • 6572 measured reflections
  • 3255 independent reflections
  • 2726 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.099
  • S = 1.08
  • 3255 reflections
  • 187 parameters
  • H-atom parameters constrained
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.33 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT-Plus (Bruker, 2003 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810004472/bt5190sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004472/bt5190Isup2.hkl

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

Acknowledgments

This work was funded by the SIT program of Hunan University.

supplementary crystallographic information

Comment

Thiazol compounds have a wide range of biological activity. The title compund was obtained by the reaction of thiurea and 2-bromo-1-(2,4-dichlorophenyl)-4,4-dimethyl-3-pentanone.

Experimental

A solution with 0.05 mol of thiurea and 0.05 mol of 2-bromo-1-(2,4-dichlorophenyl)-4,4-dimethyl-3-pentanone in 100 ml of ethanol was refluxed, monitoring by TLC (yield 99.5 %; m.p. 507.6–508.5 K). Crystals were obtained by slow evaporation of an ethanol solution at room temperature.

Refinement

All H atoms were refined using a riding model, with N—H distances of 0.88 and C—H distances ranging from 0.95 to 0.98 Å, and with Uiso(H) = 1.2Ueq(C,N) or Uiso(H) = 1.5Ueq(Cmethyl).

Figures

Fig. 1.
The asymmetric unit of the title compound with atom labels and 50% probability displacement ellipsiods (arbitrary spheres for H atoms).

Crystal data

C14H17Cl2N2S+·BrZ = 2
Mr = 396.17F(000) = 400
Triclinic, P1Dx = 1.571 Mg m3
Hall symbol: -P 1Melting point: 508 K
a = 8.7797 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.3898 (5) ÅCell parameters from 3934 reflections
c = 11.8430 (7) Åθ = 2.5–27.0°
α = 103.960 (1)°µ = 2.89 mm1
β = 91.102 (1)°T = 173 K
γ = 116.648 (1)°Block, colorless
V = 837.66 (8) Å30.43 × 0.31 × 0.22 mm

Data collection

Bruker SMART 1000 CCD diffractometer3255 independent reflections
Radiation source: fine-focus sealed tube2726 reflections with I > 2σ(I)
graphiteRint = 0.021
ω scansθmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)h = −10→10
Tmin = 0.370, Tmax = 0.569k = −11→11
6572 measured reflectionsl = −14→14

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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0512P)2 + 0.723P] where P = (Fo2 + 2Fc2)/3
3255 reflections(Δ/σ)max < 0.001
187 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = −0.33 e Å3

Special details

Experimental. 1H NMR (CDCl3,400 MHz) of 4-tert-butyl-5-(2,4-dichlorobenzyl)thiazol-2-amine: δ (p.p.m.) 1.30(s, 9H, 3×CH3), 4.15(s, 2H, CH2),4.83(br, 2H, NH2),7.08(d, J = 11.2 Hz, 1H, C6H3 6-H),7.18(d, J = 11.2 Hz, 1H, C6H3 5-H),7.38(s, 1H, C6H3 3-H).
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Br10.50000.00000.50000.05632 (19)
Br20.00000.50000.00000.03684 (15)
Cl10.23215 (12)0.02866 (10)0.20559 (7)0.0408 (2)
Cl20.08968 (10)−0.20337 (10)−0.26428 (7)0.0404 (2)
S10.32616 (9)0.42272 (8)0.15292 (6)0.02508 (17)
C10.3491 (3)0.5970 (3)0.2559 (2)0.0225 (6)
C20.5883 (3)0.5746 (3)0.3167 (2)0.0211 (5)
C30.5156 (3)0.4406 (3)0.2230 (2)0.0219 (5)
C40.7575 (4)0.6530 (3)0.3986 (2)0.0265 (6)
C50.8920 (5)0.7846 (6)0.3502 (4)0.0696 (14)
H5A0.90560.73240.27150.084*
H5B1.00230.83890.40230.084*
H5C0.85480.86740.34560.084*
C60.7388 (5)0.7336 (6)0.5218 (3)0.0563 (11)
H6A0.70590.81970.51900.084*
H6B0.84870.78360.57360.084*
H6C0.64970.64920.55210.084*
C70.8196 (5)0.5284 (5)0.4073 (4)0.0635 (13)
H7A0.72970.43740.43180.095*
H7B0.92410.58320.46540.095*
H7C0.84510.48410.33040.095*
C80.5707 (4)0.3106 (3)0.1692 (3)0.0276 (6)
H8A0.57960.25650.22930.033*
H8B0.68660.36640.14680.033*
C90.4488 (3)0.1782 (3)0.0618 (2)0.0230 (6)
C100.2912 (4)0.0491 (3)0.0691 (2)0.0245 (6)
C110.1777 (4)−0.0692 (3)−0.0297 (3)0.0272 (6)
H110.0703−0.1556−0.02290.033*
C120.2274 (4)−0.0561 (3)−0.1384 (2)0.0255 (6)
C130.3842 (4)0.0667 (4)−0.1501 (3)0.0266 (6)
H130.41700.0712−0.22570.032*
C140.4927 (4)0.1830 (3)−0.0495 (3)0.0271 (6)
H140.60030.2686−0.05700.033*
N10.4907 (3)0.6601 (3)0.33357 (19)0.0215 (5)
H10.52110.75030.39200.026*
N20.2419 (3)0.6618 (3)0.2595 (2)0.0304 (6)
H2A0.26260.75180.31550.037*
H2B0.15010.61480.20580.037*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0824 (4)0.0488 (3)0.0407 (3)0.0505 (3)−0.0187 (3)−0.0205 (2)
Br20.0325 (2)0.0267 (2)0.0393 (3)0.00678 (19)−0.01243 (18)0.00437 (18)
Cl10.0576 (5)0.0352 (4)0.0299 (4)0.0215 (4)0.0178 (4)0.0092 (3)
Cl20.0381 (4)0.0391 (4)0.0337 (4)0.0203 (4)−0.0137 (3)−0.0106 (3)
S10.0235 (3)0.0200 (3)0.0266 (4)0.0115 (3)−0.0062 (3)−0.0042 (3)
C10.0233 (13)0.0222 (13)0.0209 (13)0.0118 (11)0.0017 (10)0.0022 (11)
C20.0217 (13)0.0184 (13)0.0209 (13)0.0094 (11)0.0019 (10)0.0018 (10)
C30.0195 (13)0.0192 (13)0.0236 (13)0.0087 (11)0.0002 (10)0.0009 (11)
C40.0242 (14)0.0234 (14)0.0251 (14)0.0111 (12)−0.0050 (11)−0.0043 (11)
C50.0270 (19)0.079 (3)0.074 (3)−0.003 (2)−0.0070 (19)0.030 (3)
C60.051 (2)0.077 (3)0.0328 (18)0.040 (2)−0.0144 (16)−0.0150 (18)
C70.057 (3)0.049 (2)0.074 (3)0.035 (2)−0.035 (2)−0.017 (2)
C80.0285 (15)0.0226 (14)0.0292 (15)0.0157 (12)−0.0023 (12)−0.0041 (12)
C90.0257 (14)0.0197 (13)0.0266 (14)0.0162 (12)−0.0010 (11)0.0006 (11)
C100.0295 (15)0.0241 (14)0.0229 (13)0.0172 (12)0.0055 (11)0.0020 (11)
C110.0248 (14)0.0201 (13)0.0349 (16)0.0114 (12)0.0033 (12)0.0029 (12)
C120.0278 (14)0.0213 (14)0.0262 (14)0.0158 (12)−0.0055 (11)−0.0035 (11)
C130.0348 (16)0.0282 (15)0.0239 (14)0.0201 (13)0.0045 (12)0.0080 (12)
C140.0259 (15)0.0211 (14)0.0327 (15)0.0112 (12)0.0056 (12)0.0043 (12)
N10.0241 (11)0.0183 (11)0.0201 (11)0.0115 (10)−0.0016 (9)−0.0011 (9)
N20.0290 (13)0.0294 (13)0.0322 (13)0.0193 (11)−0.0043 (10)−0.0034 (11)

Geometric parameters (Å, °)

Cl1—C101.736 (3)C7—H7A0.9800
Cl2—C121.742 (3)C7—H7B0.9800
S1—C11.714 (3)C7—H7C0.9800
S1—C31.764 (3)C8—C91.516 (4)
C1—N21.328 (4)C8—H8A0.9900
C1—N11.332 (3)C8—H8B0.9900
C2—C31.342 (4)C9—C141.386 (4)
C2—N11.402 (3)C9—C101.394 (4)
C2—C41.519 (4)C10—C111.389 (4)
C3—C81.515 (4)C11—C121.383 (4)
C4—C71.519 (5)C11—H110.9500
C4—C51.519 (5)C12—C131.380 (4)
C4—C61.522 (4)C13—C141.384 (4)
C5—H5A0.9800C13—H130.9500
C5—H5B0.9800C14—H140.9500
C5—H5C0.9800N1—H10.8800
C6—H6A0.9800N2—H2A0.8800
C6—H6B0.9800N2—H2B0.8800
C6—H6C0.9800
C1—S1—C390.62 (13)H7A—C7—H7C109.5
N2—C1—N1123.9 (2)H7B—C7—H7C109.5
N2—C1—S1125.4 (2)C3—C8—C9113.8 (2)
N1—C1—S1110.71 (19)C3—C8—H8A108.8
C3—C2—N1111.2 (2)C9—C8—H8A108.8
C3—C2—C4132.1 (2)C3—C8—H8B108.8
N1—C2—C4116.6 (2)C9—C8—H8B108.8
C2—C3—C8131.2 (3)H8A—C8—H8B107.7
C2—C3—S1111.4 (2)C14—C9—C10117.3 (2)
C8—C3—S1117.33 (19)C14—C9—C8119.8 (3)
C7—C4—C2112.7 (2)C10—C9—C8122.9 (3)
C7—C4—C5108.5 (3)C11—C10—C9122.7 (3)
C2—C4—C5107.7 (3)C11—C10—Cl1117.3 (2)
C7—C4—C6108.1 (3)C9—C10—Cl1120.0 (2)
C2—C4—C6110.3 (2)C12—C11—C10117.3 (3)
C5—C4—C6109.5 (3)C12—C11—H11121.3
C4—C5—H5A109.5C10—C11—H11121.3
C4—C5—H5B109.5C13—C12—C11122.2 (3)
H5A—C5—H5B109.5C13—C12—Cl2119.1 (2)
C4—C5—H5C109.5C11—C12—Cl2118.7 (2)
H5A—C5—H5C109.5C12—C13—C14118.6 (3)
H5B—C5—H5C109.5C12—C13—H13120.7
C4—C6—H6A109.5C14—C13—H13120.7
C4—C6—H6B109.5C13—C14—C9121.9 (3)
H6A—C6—H6B109.5C13—C14—H14119.1
C4—C6—H6C109.5C9—C14—H14119.1
H6A—C6—H6C109.5C1—N1—C2116.1 (2)
H6B—C6—H6C109.5C1—N1—H1122.0
C4—C7—H7A109.5C2—N1—H1122.0
C4—C7—H7B109.5C1—N2—H2A120.0
H7A—C7—H7B109.5C1—N2—H2B120.0
C4—C7—H7C109.5H2A—N2—H2B120.0
C3—S1—C1—N2−179.0 (3)C14—C9—C10—C11−1.8 (4)
C3—S1—C1—N10.8 (2)C8—C9—C10—C11178.1 (2)
N1—C2—C3—C8179.8 (3)C14—C9—C10—Cl1176.7 (2)
C4—C2—C3—C84.9 (5)C8—C9—C10—Cl1−3.4 (4)
N1—C2—C3—S11.3 (3)C9—C10—C11—C120.7 (4)
C4—C2—C3—S1−173.7 (2)Cl1—C10—C11—C12−177.9 (2)
C1—S1—C3—C2−1.2 (2)C10—C11—C12—C131.2 (4)
C1—S1—C3—C8180.0 (2)C10—C11—C12—Cl2179.3 (2)
C3—C2—C4—C7−27.2 (5)C11—C12—C13—C14−1.9 (4)
N1—C2—C4—C7158.0 (3)Cl2—C12—C13—C14−179.9 (2)
C3—C2—C4—C592.4 (4)C12—C13—C14—C90.7 (4)
N1—C2—C4—C5−82.3 (3)C10—C9—C14—C131.1 (4)
C3—C2—C4—C6−148.1 (3)C8—C9—C14—C13−178.8 (3)
N1—C2—C4—C637.1 (4)N2—C1—N1—C2179.6 (3)
C2—C3—C8—C9180.0 (3)S1—C1—N1—C2−0.3 (3)
S1—C3—C8—C9−1.5 (3)C3—C2—N1—C1−0.6 (3)
C3—C8—C9—C14103.4 (3)C4—C2—N1—C1175.2 (2)
C3—C8—C9—C10−76.5 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2B···Br20.882.483.296 (2)154
N1—H1···Br1i0.882.473.286 (2)153.7

Symmetry codes: (i) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5190).

References

  • Bruker (2001). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2003). SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cao, G., Hu, A.-X., Xu, J.-J. & Xia, L. (2007). Acta Cryst. E63, o2534.
  • Hu, A. X., Cao, G., Ma, Y. Q., Zhang, J. Y. & Ou, X. M. (2008). Chinese J. Struct. Chem.27, 1235–1239.
  • Marcantonio, K. M., Frey, L. F., Murry, J. A. & Chen, C. Y. (2002). Tetrahedron Lett.43, 8845–8848.
  • Sheldrick, G. M. (2004). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Xu, J.-J., Hu, A.-X. & Cao, G. (2007). Acta Cryst. E63, o533–o534.

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