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

Du, J.; Peng, J.-M.; Li, L.; Cai, S.-H.; Hu, A.-X.

doi:10.1107/S1600536810004472

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o568

doi:10.1107/S1600536810004472

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

Jie Du,^a Jun-Mei Peng,^a Ling Li,^a Shi-Hong Cai ^a and Ai-Xi Hu ^a ^*

^aCollege of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China
^*Correspondence e-mail: axhu0731@yahoo.com.cn

(Received 3 February 2010; accepted 4 February 2010; online 10 February 2010)

The asymmetric unit of the title compound, C₁₄H₁₇Cl₂N₂S⁺·Br⁻, contains one cation and two Br⁻ ions with site symmetry $[\overline1]$ . 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 ); Hu et al. (2008 ); Marcantonio et al. (2002 ); Xu et al. (2007 ).

Experimental

Crystal data

C₁₄H₁₇Cl₂N₂S⁺·Br⁻
M_r = 396.17
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.029
wR(F²) = 0.099
S = 1.08
3255 reflections
187 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯Br2	0.88	2.48	3.296 (2)	154
N1—H1⋯Br1ⁱ	0.88	2.47	3.286 (2)	153.7
Symmetry code: (i) x, y+1, z.

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

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

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

Crystal data top

C₁₄H₁₇Cl₂N₂S⁺·Br⁻	Z = 2
M_r = 396.17	F(000) = 400
Triclinic, P1	D_x = 1.571 Mg m⁻³
Hall symbol: -P 1	Melting point: 508 K
a = 8.7797 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3898 (5) Å	Cell parameters from 3934 reflections
c = 11.8430 (7) Å	θ = 2.5–27.0°
α = 103.960 (1)°	µ = 2.89 mm⁻¹
β = 91.102 (1)°	T = 173 K
γ = 116.648 (1)°	Block, colorless
V = 837.66 (8) Å³	0.43 × 0.31 × 0.22 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	3255 independent reflections
Radiation source: fine-focus sealed tube	2726 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→10
T_min = 0.370, T_max = 0.569	k = −11→11
6572 measured reflections	l = −14→14

Refinement top

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0512P)² + 0.723P] where P = (F_o² + 2F_c²)/3
3255 reflections	(Δ/σ)_max < 0.001
187 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₄H₁₇Cl₂N₂S⁺·Br⁻	γ = 116.648 (1)°
M_r = 396.17	V = 837.66 (8) Å³
Triclinic, P1	Z = 2
a = 8.7797 (5) Å	Mo Kα radiation
b = 9.3898 (5) Å	µ = 2.89 mm⁻¹
c = 11.8430 (7) Å	T = 173 K
α = 103.960 (1)°	0.43 × 0.31 × 0.22 mm
β = 91.102 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	3255 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2726 reflections with I > 2σ(I)
T_min = 0.370, T_max = 0.569	R_int = 0.021
6572 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.08	Δρ_max = 0.37 e Å⁻³
3255 reflections	Δρ_min = −0.33 e Å⁻³
187 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br1	0.5000	0.0000	0.5000	0.05632 (19)
Br2	0.0000	0.5000	0.0000	0.03684 (15)
Cl1	0.23215 (12)	0.02866 (10)	0.20559 (7)	0.0408 (2)
Cl2	0.08968 (10)	−0.20337 (10)	−0.26428 (7)	0.0404 (2)
S1	0.32616 (9)	0.42272 (8)	0.15292 (6)	0.02508 (17)
C1	0.3491 (3)	0.5970 (3)	0.2559 (2)	0.0225 (6)
C2	0.5883 (3)	0.5746 (3)	0.3167 (2)	0.0211 (5)
C3	0.5156 (3)	0.4406 (3)	0.2230 (2)	0.0219 (5)
C4	0.7575 (4)	0.6530 (3)	0.3986 (2)	0.0265 (6)
C5	0.8920 (5)	0.7846 (6)	0.3502 (4)	0.0696 (14)
H5A	0.9056	0.7324	0.2715	0.084*
H5B	1.0023	0.8389	0.4023	0.084*
H5C	0.8548	0.8674	0.3456	0.084*
C6	0.7388 (5)	0.7336 (6)	0.5218 (3)	0.0563 (11)
H6A	0.7059	0.8197	0.5190	0.084*
H6B	0.8487	0.7836	0.5736	0.084*
H6C	0.6497	0.6492	0.5521	0.084*
C7	0.8196 (5)	0.5284 (5)	0.4073 (4)	0.0635 (13)
H7A	0.7297	0.4374	0.4318	0.095*
H7B	0.9241	0.5832	0.4654	0.095*
H7C	0.8451	0.4841	0.3304	0.095*
C8	0.5707 (4)	0.3106 (3)	0.1692 (3)	0.0276 (6)
H8A	0.5796	0.2565	0.2293	0.033*
H8B	0.6866	0.3664	0.1468	0.033*
C9	0.4488 (3)	0.1782 (3)	0.0618 (2)	0.0230 (6)
C10	0.2912 (4)	0.0491 (3)	0.0691 (2)	0.0245 (6)
C11	0.1777 (4)	−0.0692 (3)	−0.0297 (3)	0.0272 (6)
H11	0.0703	−0.1556	−0.0229	0.033*
C12	0.2274 (4)	−0.0561 (3)	−0.1384 (2)	0.0255 (6)
C13	0.3842 (4)	0.0667 (4)	−0.1501 (3)	0.0266 (6)
H13	0.4170	0.0712	−0.2257	0.032*
C14	0.4927 (4)	0.1830 (3)	−0.0495 (3)	0.0271 (6)
H14	0.6003	0.2686	−0.0570	0.033*
N1	0.4907 (3)	0.6601 (3)	0.33357 (19)	0.0215 (5)
H1	0.5211	0.7503	0.3920	0.026*
N2	0.2419 (3)	0.6618 (3)	0.2595 (2)	0.0304 (6)
H2A	0.2626	0.7518	0.3155	0.037*
H2B	0.1501	0.6148	0.2058	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0824 (4)	0.0488 (3)	0.0407 (3)	0.0505 (3)	−0.0187 (3)	−0.0205 (2)
Br2	0.0325 (2)	0.0267 (2)	0.0393 (3)	0.00678 (19)	−0.01243 (18)	0.00437 (18)
Cl1	0.0576 (5)	0.0352 (4)	0.0299 (4)	0.0215 (4)	0.0178 (4)	0.0092 (3)
Cl2	0.0381 (4)	0.0391 (4)	0.0337 (4)	0.0203 (4)	−0.0137 (3)	−0.0106 (3)
S1	0.0235 (3)	0.0200 (3)	0.0266 (4)	0.0115 (3)	−0.0062 (3)	−0.0042 (3)
C1	0.0233 (13)	0.0222 (13)	0.0209 (13)	0.0118 (11)	0.0017 (10)	0.0022 (11)
C2	0.0217 (13)	0.0184 (13)	0.0209 (13)	0.0094 (11)	0.0019 (10)	0.0018 (10)
C3	0.0195 (13)	0.0192 (13)	0.0236 (13)	0.0087 (11)	0.0002 (10)	0.0009 (11)
C4	0.0242 (14)	0.0234 (14)	0.0251 (14)	0.0111 (12)	−0.0050 (11)	−0.0043 (11)
C5	0.0270 (19)	0.079 (3)	0.074 (3)	−0.003 (2)	−0.0070 (19)	0.030 (3)
C6	0.051 (2)	0.077 (3)	0.0328 (18)	0.040 (2)	−0.0144 (16)	−0.0150 (18)
C7	0.057 (3)	0.049 (2)	0.074 (3)	0.035 (2)	−0.035 (2)	−0.017 (2)
C8	0.0285 (15)	0.0226 (14)	0.0292 (15)	0.0157 (12)	−0.0023 (12)	−0.0041 (12)
C9	0.0257 (14)	0.0197 (13)	0.0266 (14)	0.0162 (12)	−0.0010 (11)	0.0006 (11)
C10	0.0295 (15)	0.0241 (14)	0.0229 (13)	0.0172 (12)	0.0055 (11)	0.0020 (11)
C11	0.0248 (14)	0.0201 (13)	0.0349 (16)	0.0114 (12)	0.0033 (12)	0.0029 (12)
C12	0.0278 (14)	0.0213 (14)	0.0262 (14)	0.0158 (12)	−0.0055 (11)	−0.0035 (11)
C13	0.0348 (16)	0.0282 (15)	0.0239 (14)	0.0201 (13)	0.0045 (12)	0.0080 (12)
C14	0.0259 (15)	0.0211 (14)	0.0327 (15)	0.0112 (12)	0.0056 (12)	0.0043 (12)
N1	0.0241 (11)	0.0183 (11)	0.0201 (11)	0.0115 (10)	−0.0016 (9)	−0.0011 (9)
N2	0.0290 (13)	0.0294 (13)	0.0322 (13)	0.0193 (11)	−0.0043 (10)	−0.0034 (11)

Geometric parameters (Å, º) top

Cl1—C10	1.736 (3)	C7—H7A	0.9800
Cl2—C12	1.742 (3)	C7—H7B	0.9800
S1—C1	1.714 (3)	C7—H7C	0.9800
S1—C3	1.764 (3)	C8—C9	1.516 (4)
C1—N2	1.328 (4)	C8—H8A	0.9900
C1—N1	1.332 (3)	C8—H8B	0.9900
C2—C3	1.342 (4)	C9—C14	1.386 (4)
C2—N1	1.402 (3)	C9—C10	1.394 (4)
C2—C4	1.519 (4)	C10—C11	1.389 (4)
C3—C8	1.515 (4)	C11—C12	1.383 (4)
C4—C7	1.519 (5)	C11—H11	0.9500
C4—C5	1.519 (5)	C12—C13	1.380 (4)
C4—C6	1.522 (4)	C13—C14	1.384 (4)
C5—H5A	0.9800	C13—H13	0.9500
C5—H5B	0.9800	C14—H14	0.9500
C5—H5C	0.9800	N1—H1	0.8800
C6—H6A	0.9800	N2—H2A	0.8800
C6—H6B	0.9800	N2—H2B	0.8800
C6—H6C	0.9800

C1—S1—C3	90.62 (13)	H7A—C7—H7C	109.5
N2—C1—N1	123.9 (2)	H7B—C7—H7C	109.5
N2—C1—S1	125.4 (2)	C3—C8—C9	113.8 (2)
N1—C1—S1	110.71 (19)	C3—C8—H8A	108.8
C3—C2—N1	111.2 (2)	C9—C8—H8A	108.8
C3—C2—C4	132.1 (2)	C3—C8—H8B	108.8
N1—C2—C4	116.6 (2)	C9—C8—H8B	108.8
C2—C3—C8	131.2 (3)	H8A—C8—H8B	107.7
C2—C3—S1	111.4 (2)	C14—C9—C10	117.3 (2)
C8—C3—S1	117.33 (19)	C14—C9—C8	119.8 (3)
C7—C4—C2	112.7 (2)	C10—C9—C8	122.9 (3)
C7—C4—C5	108.5 (3)	C11—C10—C9	122.7 (3)
C2—C4—C5	107.7 (3)	C11—C10—Cl1	117.3 (2)
C7—C4—C6	108.1 (3)	C9—C10—Cl1	120.0 (2)
C2—C4—C6	110.3 (2)	C12—C11—C10	117.3 (3)
C5—C4—C6	109.5 (3)	C12—C11—H11	121.3
C4—C5—H5A	109.5	C10—C11—H11	121.3
C4—C5—H5B	109.5	C13—C12—C11	122.2 (3)
H5A—C5—H5B	109.5	C13—C12—Cl2	119.1 (2)
C4—C5—H5C	109.5	C11—C12—Cl2	118.7 (2)
H5A—C5—H5C	109.5	C12—C13—C14	118.6 (3)
H5B—C5—H5C	109.5	C12—C13—H13	120.7
C4—C6—H6A	109.5	C14—C13—H13	120.7
C4—C6—H6B	109.5	C13—C14—C9	121.9 (3)
H6A—C6—H6B	109.5	C13—C14—H14	119.1
C4—C6—H6C	109.5	C9—C14—H14	119.1
H6A—C6—H6C	109.5	C1—N1—C2	116.1 (2)
H6B—C6—H6C	109.5	C1—N1—H1	122.0
C4—C7—H7A	109.5	C2—N1—H1	122.0
C4—C7—H7B	109.5	C1—N2—H2A	120.0
H7A—C7—H7B	109.5	C1—N2—H2B	120.0
C4—C7—H7C	109.5	H2A—N2—H2B	120.0

C3—S1—C1—N2	−179.0 (3)	C14—C9—C10—C11	−1.8 (4)
C3—S1—C1—N1	0.8 (2)	C8—C9—C10—C11	178.1 (2)
N1—C2—C3—C8	179.8 (3)	C14—C9—C10—Cl1	176.7 (2)
C4—C2—C3—C8	4.9 (5)	C8—C9—C10—Cl1	−3.4 (4)
N1—C2—C3—S1	1.3 (3)	C9—C10—C11—C12	0.7 (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—C13	1.2 (4)
C1—S1—C3—C8	180.0 (2)	C10—C11—C12—Cl2	179.3 (2)
C3—C2—C4—C7	−27.2 (5)	C11—C12—C13—C14	−1.9 (4)
N1—C2—C4—C7	158.0 (3)	Cl2—C12—C13—C14	−179.9 (2)
C3—C2—C4—C5	92.4 (4)	C12—C13—C14—C9	0.7 (4)
N1—C2—C4—C5	−82.3 (3)	C10—C9—C14—C13	1.1 (4)
C3—C2—C4—C6	−148.1 (3)	C8—C9—C14—C13	−178.8 (3)
N1—C2—C4—C6	37.1 (4)	N2—C1—N1—C2	179.6 (3)
C2—C3—C8—C9	180.0 (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—C14	103.4 (3)	C4—C2—N1—C1	175.2 (2)
C3—C8—C9—C10	−76.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···Br2	0.88	2.48	3.296 (2)	154
N1—H1···Br1ⁱ	0.88	2.47	3.286 (2)	153.7

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₇Cl₂N₂S⁺·Br⁻
M_r	396.17
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	8.7797 (5), 9.3898 (5), 11.8430 (7)
α, β, γ (°)	103.960 (1), 91.102 (1), 116.648 (1)
V (Å³)	837.66 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.89
Crystal size (mm)	0.43 × 0.31 × 0.22

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.370, 0.569
No. of measured, independent and observed [I > 2σ(I)] reflections	6572, 3255, 2726
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.099, 1.08
No. of reflections	3255
No. of parameters	187
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.33

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···Br2	0.88	2.48	3.296 (2)	153.6
N1—H1···Br1ⁱ	0.88	2.47	3.286 (2)	153.7

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

Acknowledgements

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

References

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