8-Bromo-3,4-dihydro-2H-1,3-thia­zino[2,3:2′,1′]imidazo[5′,4′-b]pyridine

Ghacham, H.B.; Rodi, Y.K.; Capet, F.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S1600536810012778

organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1079

https://doi.org/10.1107/S1600536810012778

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8-Bromo-3,4-dihydro-2H-1,3-thiazino[2,3:2′,1′]imidazo[5′,4′-b]pyridine

Hend Bel Ghacham,^a Youssef Kandri Rodi,^a Frédéric Capet,^b El Mokhtar Essassi ^c and Seik Weng Ng ^d ^*

^aLaboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques, Université Sidi Mohamed Ben Abdallah, Fés, Morocco, ^bUnité de Catalyse et de Chimie du Solide (UCCS), UMR 8181, Ecole Nationale Supérieure de Chimie de Lille, Lille, France, ^cLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, and ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 6 April 2010; accepted 6 April 2010; online 14 April 2010)

The imidazopyridine ring system in the title compound, C₉H₈BrN₃S, is almost planar [r.m.s. deviation of the C and N atoms = 0.007 (1) Å]. The S and methylene C atoms connected to the five-membered ring lie within this plane. The remaining two methylene groups of the thiazine ring are disordered over two sets of sites in a 0.817 (5):0.183 (5) ratio.

Related literature

The parent triclyclic condensed imidazole (without bromine) has been patented as a pharmaceutical; see: Hideg et al. (1975 , 1976 ). For other compounds synthesized from 6-bromo-1H-imidazo[4,5-b]pyridine-2(3H)-thione, see: Liszkiewicz et al. (2007 ); Prasad et al. (1986 ); Yutilov & Svertilova (1988 ).

Experimental

Crystal data

C₉H₈BrN₃S
M_r = 270.15
Monoclinic, C 2/c
a = 20.2738 (3) Å
b = 13.2786 (2) Å
c = 7.3169 (1) Å
β = 102.193 (1)°
V = 1925.33 (5) Å³
Z = 8
Mo Kα radiation
μ = 4.45 mm⁻¹
T = 100 K
0.46 × 0.14 × 0.12 mm

Data collection

Bruker X8 APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.234, T_max = 0.618
30460 measured reflections
3561 independent reflections
3003 reflections with I > 2σ(I)
R_int = 0.039
Standard reflections: 0

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.064
S = 0.99
3561 reflections
146 parameters
14 restraints
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810012778/bt5242sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012778/bt5242Isup2.hkl

checkCIF report

Comment top

Commerically-available 6-bromo-1H-imidazo[4,5-b]pyridine-2(3H)-thione has been used to react with a range of organic compounds to furnish chemicals having useful biological activities (Liszkiewicz et al., 2007; Prasad et al., 1986; Yutilov & Svertilova, 1988). The compound reacts with 1-chloropropanal under catalytic conditions to yield the title triclyclic condensed imidazole (Scheme I, Fig. 1). The imidazopyridine fused ring is planar. One ethylene fragment of the six-membered ring is twisted such that one atom lies above and the other below the plane. This fragment is disordered over two positions.

Related literature top

The parent triclyclic condensed imidazole (without bromine) has been patented as a pharmaceutical; see: Hideg et al. (1975, 1976). For other compounds synthesized from 6-bromo-1H-imidazo[4,5-b]pyridine-2(3H)-thione, see: Liszkiewicz et al. (2007); Prasad et al. (1986); Yutilov & Svertilova (1988).

Experimental top

6-Bromo-1H-imidazo[4,5-b]pyridine-2(3H)-thione (1 mmol), potassium carbonate (4 mmol), tetra-n-butylammonium bromide (0.1 mmol) and 1-chloro-propanol (1.5 mmol) in DMF (15 ml) were stirred for 72 h. After completion of reaction (as monitored by TLC), the salt was filtered and the solvent removed under reduced pressure. The resulting residue was purified by column chromatography on silica gel using chloroform/hexane (1/1) as eluent. Colorless crystals were isolated when the solvent was allowed to evaporate.

Structure description top

The parent triclyclic condensed imidazole (without bromine) has been patented as a pharmaceutical; see: Hideg et al. (1975, 1976). For other compounds synthesized from 6-bromo-1H-imidazo[4,5-b]pyridine-2(3H)-thione, see: Liszkiewicz et al. (2007); Prasad et al. (1986); Yutilov & Svertilova (1988).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₉H₈BrN₃O at the 70% probability level; H atoms are drawn as spheres of an arbitrary radius. The disorder is not shown.

8-Bromo-3,4-dihydro-2H1,3-thiazino[2,3:2',1']imidazo[5',4'- b]pyridine top

Crystal data top

C₉H₈BrN₃S	F(000) = 1072
M_r = 270.15	D_x = 1.864 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9070 reflections
a = 20.2738 (3) Å	θ = 2.8–32.5°
b = 13.2786 (2) Å	µ = 4.45 mm⁻¹
c = 7.3169 (1) Å	T = 100 K
β = 102.193 (1)°	Block, colourless
V = 1925.33 (5) Å³	0.46 × 0.14 × 0.12 mm
Z = 8

Data collection top

Bruker X8 APEXII diffractometer	3561 independent reflections
Radiation source: fine-focus sealed tube	3003 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
φ and ω scans	θ_max = 32.8°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −30→30
T_min = 0.234, T_max = 0.618	k = −20→20
30460 measured reflections	l = −11→11

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0351P)² + 1.6536P] where P = (F_o² + 2F_c²)/3
3561 reflections	(Δ/σ)_max = 0.001
146 parameters	Δρ_max = 0.49 e Å⁻³
14 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

C₉H₈BrN₃S	V = 1925.33 (5) Å³
M_r = 270.15	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 20.2738 (3) Å	µ = 4.45 mm⁻¹
b = 13.2786 (2) Å	T = 100 K
c = 7.3169 (1) Å	0.46 × 0.14 × 0.12 mm
β = 102.193 (1)°

Data collection top

Bruker X8 APEXII diffractometer	3561 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3003 reflections with I > 2σ(I)
T_min = 0.234, T_max = 0.618	R_int = 0.039
30460 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	14 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 0.99	Δρ_max = 0.49 e Å⁻³
3561 reflections	Δρ_min = −0.55 e Å⁻³
146 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.446434 (7)	0.655625 (11)	0.45346 (2)	0.02338 (5)
S1	0.082325 (17)	0.50817 (3)	0.60465 (5)	0.01612 (7)
N1	0.20317 (6)	0.43515 (8)	0.54957 (17)	0.0139 (2)
N2	0.19469 (6)	0.60483 (9)	0.56459 (18)	0.0162 (2)
N3	0.31734 (6)	0.42166 (9)	0.50005 (18)	0.0167 (2)
C1	0.07654 (9)	0.37320 (13)	0.6425 (4)	0.0175 (4)	0.817 (5)
H1A	0.0993	0.3568	0.7726	0.021*	0.817 (5)
H1B	0.0285	0.3537	0.6256	0.021*	0.817 (5)
C2	0.10897 (9)	0.31333 (13)	0.5076 (3)	0.0178 (4)	0.817 (5)
H2A	0.0888	0.3342	0.3780	0.021*	0.817 (5)
H2B	0.0991	0.2409	0.5196	0.021*	0.817 (5)
C1'	0.0642 (4)	0.3746 (5)	0.5409 (16)	0.0186 (18)	0.183 (5)
H1'A	0.0233	0.3527	0.5836	0.022*	0.183 (5)
H1'B	0.0556	0.3670	0.4033	0.022*	0.183 (5)
C2'	0.1237 (3)	0.3089 (6)	0.6309 (11)	0.0158 (18)	0.183 (5)
H2'A	0.1106	0.2371	0.6148	0.019*	0.183 (5)
H2'B	0.1360	0.3232	0.7667	0.019*	0.183 (5)
C3	0.18508 (7)	0.32823 (10)	0.5435 (2)	0.0179 (3)
H3A	0.2062	0.2962	0.6639	0.021*	0.817 (5)
H3B	0.2030	0.2947	0.4433	0.021*	0.817 (5)
H3C	0.2240	0.2887	0.6118	0.021*	0.183 (5)
H3D	0.1748	0.3051	0.4119	0.021*	0.183 (5)
C4	0.16459 (7)	0.51691 (10)	0.57248 (19)	0.0142 (2)
C5	0.26416 (7)	0.47390 (10)	0.52582 (19)	0.0140 (2)
C6	0.25763 (7)	0.57918 (10)	0.53377 (19)	0.0143 (2)
C7	0.31223 (7)	0.63821 (10)	0.5118 (2)	0.0166 (2)
H7	0.3111	0.7097	0.5143	0.020*
C8	0.36844 (7)	0.58455 (10)	0.4857 (2)	0.0158 (2)
C9	0.37001 (7)	0.47932 (11)	0.4812 (2)	0.0175 (3)
H9	0.4101	0.4471	0.4641	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01399 (7)	0.02031 (8)	0.03740 (10)	−0.00406 (5)	0.00897 (6)	0.00137 (6)
S1	0.01303 (14)	0.01364 (14)	0.02374 (16)	0.00071 (11)	0.00854 (12)	−0.00036 (12)
N1	0.0120 (5)	0.0103 (4)	0.0206 (5)	−0.0002 (4)	0.0058 (4)	−0.0006 (4)
N2	0.0136 (5)	0.0117 (5)	0.0246 (6)	0.0011 (4)	0.0068 (4)	0.0003 (4)
N3	0.0131 (5)	0.0136 (5)	0.0244 (6)	0.0008 (4)	0.0065 (4)	−0.0004 (4)
C1	0.0156 (8)	0.0145 (7)	0.0240 (11)	−0.0020 (6)	0.0079 (7)	0.0010 (7)
C2	0.0155 (7)	0.0133 (7)	0.0255 (11)	−0.0024 (6)	0.0066 (7)	−0.0022 (6)
C1'	0.020 (4)	0.015 (3)	0.023 (5)	−0.005 (3)	0.009 (3)	−0.001 (3)
C2'	0.016 (3)	0.013 (3)	0.020 (4)	−0.001 (2)	0.005 (3)	0.002 (3)
C3	0.0153 (6)	0.0099 (5)	0.0301 (7)	−0.0009 (4)	0.0088 (5)	−0.0011 (5)
C4	0.0128 (5)	0.0125 (5)	0.0183 (6)	0.0014 (4)	0.0054 (4)	−0.0002 (5)
C5	0.0123 (5)	0.0122 (5)	0.0179 (6)	−0.0001 (4)	0.0043 (4)	−0.0003 (4)
C6	0.0132 (5)	0.0114 (5)	0.0187 (6)	0.0005 (4)	0.0041 (5)	0.0006 (4)
C7	0.0144 (6)	0.0128 (5)	0.0230 (6)	−0.0008 (4)	0.0047 (5)	0.0008 (5)
C8	0.0119 (5)	0.0153 (6)	0.0208 (6)	−0.0022 (4)	0.0046 (5)	0.0011 (5)
C9	0.0128 (6)	0.0160 (6)	0.0250 (7)	0.0010 (5)	0.0067 (5)	0.0002 (5)

Geometric parameters (Å, º) top

Br1—C8	1.8986 (13)	C1'—C2'	1.521 (13)
S1—C4	1.7367 (14)	C1'—H1'A	0.9900
S1—C1	1.8211 (18)	C1'—H1'B	0.9900
S1—C1'	1.851 (6)	C2'—C3	1.536 (6)
N1—C4	1.3689 (17)	C2'—H2'A	0.9900
N1—C5	1.3836 (17)	C2'—H2'B	0.9900
N1—C3	1.4647 (17)	C3—H3A	0.9900
N2—C4	1.3243 (17)	C3—H3B	0.9900
N2—C6	1.3844 (17)	C3—H3C	0.9900
N3—C5	1.3286 (17)	C3—H3D	0.9900
N3—C9	1.3445 (18)	C5—C6	1.4067 (18)
C1—C2	1.521 (3)	C6—C7	1.3931 (19)
C1—H1A	0.9900	C7—C8	1.391 (2)
C1—H1B	0.9900	C7—H7	0.9500
C2—C3	1.522 (2)	C8—C9	1.3982 (19)
C2—H2A	0.9900	C9—H9	0.9500
C2—H2B	0.9900

C4—S1—C1	100.42 (7)	N1—C3—C2	111.68 (12)
C4—S1—C1'	100.1 (3)	N1—C3—C2'	111.7 (3)
C4—N1—C5	105.63 (11)	N1—C3—H3A	109.3
C4—N1—C3	128.79 (12)	C2—C3—H3A	109.3
C5—N1—C3	125.55 (11)	N1—C3—H3B	109.3
C4—N2—C6	103.85 (11)	C2—C3—H3B	109.3
C5—N3—C9	113.77 (12)	H3A—C3—H3B	107.9
C2—C1—S1	111.42 (14)	N1—C3—H3C	109.3
C2—C1—H1A	109.3	C2'—C3—H3C	109.3
S1—C1—H1A	109.3	N1—C3—H3D	109.3
C2—C1—H1B	109.3	C2'—C3—H3D	109.3
S1—C1—H1B	109.3	H3C—C3—H3D	107.9
H1A—C1—H1B	108.0	N2—C4—N1	114.41 (12)
C1—C2—C3	112.43 (15)	N2—C4—S1	121.96 (10)
C1—C2—H2A	109.1	N1—C4—S1	123.61 (10)
C3—C2—H2A	109.1	N3—C5—N1	126.67 (12)
C1—C2—H2B	109.1	N3—C5—C6	127.66 (13)
C3—C2—H2B	109.1	N1—C5—C6	105.67 (11)
H2A—C2—H2B	107.8	N2—C6—C7	131.50 (12)
C2'—C1'—S1	110.1 (6)	N2—C6—C5	110.44 (12)
C2'—C1'—H1'A	109.6	C7—C6—C5	118.06 (12)
S1—C1'—H1'A	109.6	C8—C7—C6	114.94 (12)
C2'—C1'—H1'B	109.6	C8—C7—H7	122.5
S1—C1'—H1'B	109.6	C6—C7—H7	122.5
H1'A—C1'—H1'B	108.2	C7—C8—C9	122.59 (13)
C1'—C2'—C3	111.2 (6)	C7—C8—Br1	119.37 (10)
C1'—C2'—H2'A	109.4	C9—C8—Br1	118.04 (10)
C3—C2'—H2'A	109.4	N3—C9—C8	122.97 (13)
C1'—C2'—H2'B	109.4	N3—C9—H9	118.5
C3—C2'—H2'B	109.4	C8—C9—H9	118.5
H2'A—C2'—H2'B	108.0

C4—S1—C1—C2	−42.19 (16)	C1—S1—C4—N1	10.57 (15)
C1'—S1—C1—C2	49.0 (7)	C1'—S1—C4—N1	−12.8 (4)
S1—C1—C2—C3	67.0 (2)	C9—N3—C5—N1	−179.92 (13)
C4—S1—C1'—C2'	44.5 (7)	C9—N3—C5—C6	0.4 (2)
C1—S1—C1'—C2'	−48.5 (7)	C4—N1—C5—N3	179.51 (14)
S1—C1'—C2'—C3	−69.0 (8)	C3—N1—C5—N3	−2.5 (2)
C4—N1—C3—C2	17.2 (2)	C4—N1—C5—C6	−0.78 (15)
C5—N1—C3—C2	−160.32 (14)	C3—N1—C5—C6	177.23 (13)
C4—N1—C3—C2'	−19.3 (4)	C4—N2—C6—C7	179.69 (15)
C5—N1—C3—C2'	163.2 (3)	C4—N2—C6—C5	−0.67 (16)
C1—C2—C3—N1	−52.1 (2)	N3—C5—C6—N2	−179.37 (14)
C1—C2—C3—C2'	44.8 (5)	N1—C5—C6—N2	0.92 (16)
C1'—C2'—C3—N1	54.3 (7)	N3—C5—C6—C7	0.3 (2)
C1'—C2'—C3—C2	−42.7 (5)	N1—C5—C6—C7	−179.37 (12)
C6—N2—C4—N1	0.15 (16)	N2—C6—C7—C8	178.98 (14)
C6—N2—C4—S1	−178.61 (10)	C5—C6—C7—C8	−0.6 (2)
C5—N1—C4—N2	0.41 (16)	C6—C7—C8—C9	0.3 (2)
C3—N1—C4—N2	−177.51 (14)	C6—C7—C8—Br1	179.90 (10)
C5—N1—C4—S1	179.16 (10)	C5—N3—C9—C8	−0.9 (2)
C3—N1—C4—S1	1.2 (2)	C7—C8—C9—N3	0.6 (2)
C1—S1—C4—N2	−170.77 (14)	Br1—C8—C9—N3	−179.09 (11)
C1'—S1—C4—N2	165.9 (4)

Experimental details

Crystal data
Chemical formula	C₉H₈BrN₃S
M_r	270.15
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	20.2738 (3), 13.2786 (2), 7.3169 (1)
β (°)	102.193 (1)
V (Å³)	1925.33 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.45
Crystal size (mm)	0.46 × 0.14 × 0.12

Data collection
Diffractometer	Bruker X8 APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.234, 0.618
No. of measured, independent and observed [I > 2σ(I)] reflections	30460, 3561, 3003
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.762

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.064, 0.99
No. of reflections	3561
No. of parameters	146
No. of restraints	14
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.55

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

The authors thank the University Sidi Mohammed Ben Abdallah, the Université Mohammed V-Agdal and the University of Malaya for supporting this study.

References

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