2-(6-Bromo-benzo[d]thia-zol-2-yl)-5,5-di-methyl-thia-zol-4(5H)-one.

The title compound, C12H9BrN2OS2, was obtained by reacting 6-bromo-benzo[d]thia-zole-2-carbo-nitrile in iso-propanol with ethyl 2-mercapto-2-methyl-propano-ate at reflux temperature for several hours. The resulting di-methyl-oxyluciferin derivative shows partial double-bond character of the carbon-carbon bond between the two heterocyclic moieties [C-C = 1.461 (3) Å]. This double bond restricts rotation around this C-C axis, therefore leading to an almost planar mol-ecular structure [N-C-C-S torsion angle = 9.7 (3)°]. The five-membered thiazoline ring is not completely planar as a result of the bulky S atom [C-S-C-C torsion angle = 5.17 (12)°].

Related literature

For the chemi- and bioluminescence of firefly luciferin and related compounds, see: Jung et al. (1975 ▶); White et al. (1961 ▶, 1979 ▶); Branchini et al. (2002 ▶). For structural modifications of firefly luciferin, see: Meroni et al. (2009 ▶); McCutcheon et al. (2012 ▶); Branchini et al. (2012 ▶); Würfel (2012 ▶). Luciferin and related structures are widely used in clinical and biochemical applications, see: Schäffer (1987a ▶,b ▶); Kricka (1988 ▶); Josel et al. (1994a ▶,b ▶); Shinde et al. (2006 ▶). For details of the synthetic procedure, see: Armarego & Chai (2009 ▶); Bardsley et al. (2009a ▶,b ▶); Würfel et al. (2012 ▶).

Experimental

Crystal data

C12H9BrN2OS2

M = 341.24

Monoclinic,

a = 12.8246 (3) Å

b = 11.9115 (3) Å

c = 8.5375 (2) Å

β = 99.735 (1)°

V = 1285.41 (5) Å3

Z = 4

Mo Kα radiation

μ = 3.51 mm−1

T = 133 K

0.06 × 0.05 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer

7856 measured reflections

2927 independent reflections

2676 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.065

S = 1.02

2927 reflections

165 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.40 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor 1997 ▶); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813031334/im2444sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813031334/im2444Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813031334/im2444Isup3.cml

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

C12H9BrN2OS2	F(000) = 680
Mr = 341.24	Dx = 1.763 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7856 reflections
a = 12.8246 (3) Å	θ = 2.4–27.5°
b = 11.9115 (3) Å	µ = 3.51 mm−1
c = 8.5375 (2) Å	T = 133 K
β = 99.735 (1)°	Prism, colourless
V = 1285.41 (5) Å3	0.06 × 0.05 × 0.04 mm
Z = 4

Nonius KappaCCD diffractometer	2676 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
Graphite monochromator	θmax = 27.5°, θmin = 2.4°
phi– + ω–scan	h = −16→16
7856 measured reflections	k = −15→15
2927 independent reflections	l = −11→11

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.065	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0282P)2 + 1.1743P] where P = (Fo2 + 2Fc2)/3
2927 reflections	(Δ/σ)max = 0.001
165 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	0.858415 (15)	0.276647 (17)	−0.06700 (2)	0.02385 (8)
S1	0.46626 (4)	0.21606 (4)	0.14052 (6)	0.01968 (11)
S2	0.26944 (4)	0.47143 (4)	0.31410 (6)	0.02169 (12)
O1	0.11449 (13)	0.20363 (13)	0.3753 (2)	0.0295 (4)
N1	0.48242 (12)	0.42814 (14)	0.21789 (19)	0.0197 (3)
N2	0.26810 (13)	0.25109 (15)	0.2854 (2)	0.0206 (3)
C1	0.42214 (15)	0.34012 (16)	0.2154 (2)	0.0190 (4)
C2	0.57634 (15)	0.28879 (16)	0.1035 (2)	0.0180 (4)
C3	0.66043 (15)	0.24949 (16)	0.0334 (2)	0.0188 (4)
H3A	0.6623	0.1748	−0.0049	0.023*
C4	0.74046 (15)	0.32508 (17)	0.0230 (2)	0.0188 (4)
C5	0.73963 (15)	0.43642 (17)	0.0770 (2)	0.0202 (4)
H5A	0.7973	0.4850	0.0691	0.024*
C6	0.65474 (15)	0.47491 (17)	0.1416 (2)	0.0208 (4)
H6A	0.6525	0.5505	0.1765	0.025*
C7	0.57210 (15)	0.40109 (16)	0.1549 (2)	0.0188 (4)
C8	0.32045 (15)	0.34245 (16)	0.2709 (2)	0.0189 (4)
C9	0.17367 (16)	0.27547 (16)	0.3418 (2)	0.0211 (4)
C10	0.14997 (15)	0.40174 (16)	0.3551 (2)	0.0195 (4)
C11	0.05518 (16)	0.43242 (19)	0.2281 (2)	0.0250 (4)
H11B	−0.0072	0.3904	0.2471	0.037*
H11C	0.0708	0.4134	0.1228	0.037*
H11D	0.0412	0.5131	0.2330	0.037*
C12	0.13018 (16)	0.42953 (18)	0.5223 (2)	0.0231 (4)
H12B	0.0677	0.3886	0.5433	0.035*
H12C	0.1183	0.5104	0.5307	0.035*
H12D	0.1919	0.4073	0.6002	0.035*

	U11	U22	U33	U12	U13	U23
Br1	0.02181 (11)	0.02233 (12)	0.02884 (12)	0.00282 (7)	0.00841 (8)	−0.00194 (8)
S1	0.0206 (2)	0.0135 (2)	0.0256 (2)	−0.00276 (17)	0.00599 (19)	−0.00213 (18)
S2	0.0223 (2)	0.0131 (2)	0.0311 (3)	−0.00125 (17)	0.00843 (19)	−0.00089 (19)
O1	0.0320 (8)	0.0187 (7)	0.0420 (9)	−0.0057 (6)	0.0182 (7)	−0.0017 (7)
N1	0.0204 (8)	0.0157 (8)	0.0237 (8)	−0.0015 (6)	0.0059 (6)	−0.0001 (6)
N2	0.0204 (8)	0.0160 (8)	0.0263 (8)	−0.0018 (6)	0.0062 (7)	−0.0031 (7)
C1	0.0208 (9)	0.0163 (9)	0.0196 (9)	0.0010 (7)	0.0024 (7)	−0.0003 (7)
C2	0.0200 (9)	0.0158 (9)	0.0177 (9)	−0.0029 (7)	0.0019 (7)	0.0015 (7)
C3	0.0218 (9)	0.0138 (9)	0.0204 (9)	0.0018 (7)	0.0023 (7)	−0.0015 (8)
C4	0.0183 (8)	0.0198 (9)	0.0187 (9)	0.0023 (7)	0.0043 (7)	0.0016 (8)
C5	0.0212 (9)	0.0175 (9)	0.0220 (9)	−0.0030 (7)	0.0035 (7)	0.0009 (7)
C6	0.0224 (9)	0.0152 (9)	0.0258 (10)	−0.0004 (7)	0.0064 (8)	−0.0014 (8)
C7	0.0203 (9)	0.0157 (9)	0.0202 (9)	0.0006 (7)	0.0026 (7)	0.0007 (7)
C8	0.0216 (9)	0.0139 (9)	0.0209 (9)	0.0001 (7)	0.0024 (7)	−0.0003 (7)
C9	0.0231 (9)	0.0180 (10)	0.0229 (10)	−0.0001 (7)	0.0058 (8)	−0.0019 (8)
C10	0.0204 (9)	0.0158 (9)	0.0235 (9)	−0.0007 (7)	0.0067 (7)	−0.0001 (7)
C11	0.0232 (9)	0.0288 (11)	0.0226 (10)	0.0006 (8)	0.0031 (8)	0.0017 (8)
C12	0.0255 (10)	0.0225 (10)	0.0221 (10)	0.0031 (8)	0.0064 (8)	−0.0012 (8)

Br1—C4	1.8985 (19)	C3—H3A	0.9500
S1—C2	1.730 (2)	C4—C5	1.405 (3)
S1—C1	1.742 (2)	C5—C6	1.379 (3)
S1—S2	4.3686 (7)	C5—H5A	0.9500
S2—C8	1.734 (2)	C6—C7	1.396 (3)
S2—C10	1.8276 (19)	C6—H6A	0.9500
O1—C9	1.210 (3)	C9—C10	1.542 (3)
N1—C1	1.301 (3)	C10—C12	1.528 (3)
N1—C7	1.387 (2)	C10—C11	1.530 (3)
N2—C8	1.296 (3)	C11—H11B	0.9800
N2—C9	1.407 (3)	C11—H11C	0.9800
C1—C8	1.461 (3)	C11—H11D	0.9800
C2—C3	1.399 (3)	C12—H12B	0.9800
C2—C7	1.412 (3)	C12—H12C	0.9800
C3—C4	1.379 (3)	C12—H12D	0.9800
C2—S1—C1	88.17 (9)	N1—C7—C2	114.75 (17)
C2—S1—S2	104.45 (7)	C6—C7—C2	120.10 (18)
C1—S1—S2	16.82 (6)	N2—C8—C1	121.36 (18)
C8—S2—C10	89.82 (9)	N2—C8—S2	120.25 (15)
C8—S2—S1	18.27 (7)	C1—C8—S2	118.38 (15)
C10—S2—S1	107.45 (6)	O1—C9—N2	123.07 (18)
C1—N1—C7	109.63 (17)	O1—C9—C10	122.21 (19)
C8—N2—C9	110.44 (17)	N2—C9—C10	114.71 (17)
N1—C1—C8	122.68 (18)	C12—C10—C11	111.89 (16)
N1—C1—S1	117.44 (15)	C12—C10—C9	110.22 (17)
C8—C1—S1	119.88 (15)	C11—C10—C9	108.90 (17)
C3—C2—C7	121.53 (17)	C12—C10—S2	110.94 (14)
C3—C2—S1	128.47 (15)	C11—C10—S2	110.32 (14)
C7—C2—S1	109.99 (15)	C9—C10—S2	104.29 (13)
C4—C3—C2	116.41 (18)	C10—C11—H11B	109.5
C4—C3—H3A	121.8	C10—C11—H11C	109.5
C2—C3—H3A	121.8	H11B—C11—H11C	109.5
C3—C4—C5	123.22 (18)	C10—C11—H11D	109.5
C3—C4—Br1	118.70 (15)	H11B—C11—H11D	109.5
C5—C4—Br1	118.07 (15)	H11C—C11—H11D	109.5
C6—C5—C4	119.70 (18)	C10—C12—H12B	109.5
C6—C5—H5A	120.2	C10—C12—H12C	109.5
C4—C5—H5A	120.2	H12B—C12—H12C	109.5
C5—C6—C7	118.98 (18)	C10—C12—H12D	109.5
C5—C6—H6A	120.5	H12B—C12—H12D	109.5
C7—C6—H6A	120.5	H12C—C12—H12D	109.5
N1—C7—C6	125.15 (18)
C2—S1—S2—C8	−164.7 (2)	C3—C2—C7—C6	−2.3 (3)
C1—S1—S2—C8	−149.8 (3)	S1—C2—C7—C6	177.93 (15)
C2—S1—S2—C10	179.56 (9)	C9—N2—C8—C1	179.51 (17)
C1—S1—S2—C10	−165.6 (2)	C9—N2—C8—S2	−1.7 (2)
C7—N1—C1—C8	−178.67 (17)	N1—C1—C8—N2	−171.43 (19)
C7—N1—C1—S1	0.8 (2)	S1—C1—C8—N2	9.2 (3)
C2—S1—C1—N1	−1.39 (16)	N1—C1—C8—S2	9.7 (3)
S2—S1—C1—N1	−167.0 (3)	S1—C1—C8—S2	−169.70 (11)
C2—S1—C1—C8	178.06 (16)	C10—S2—C8—N2	−2.53 (17)
S2—S1—C1—C8	12.46 (13)	S1—S2—C8—N2	−167.5 (3)
C1—S1—C2—C3	−178.28 (19)	C10—S2—C8—C1	176.35 (16)
S2—S1—C2—C3	−174.01 (16)	S1—S2—C8—C1	11.38 (12)
C1—S1—C2—C7	1.52 (15)	C8—N2—C9—O1	−174.9 (2)
S2—S1—C2—C7	5.78 (14)	C8—N2—C9—C10	6.1 (2)
C7—C2—C3—C4	2.4 (3)	O1—C9—C10—C12	54.4 (3)
S1—C2—C3—C4	−177.87 (15)	N2—C9—C10—C12	−126.62 (18)
C2—C3—C4—C5	−0.7 (3)	O1—C9—C10—C11	−68.7 (3)
C2—C3—C4—Br1	178.80 (14)	N2—C9—C10—C11	110.29 (19)
C3—C4—C5—C6	−1.2 (3)	O1—C9—C10—S2	173.56 (18)
Br1—C4—C5—C6	179.35 (15)	N2—C9—C10—S2	−7.5 (2)
C4—C5—C6—C7	1.3 (3)	C8—S2—C10—C12	123.84 (15)
C1—N1—C7—C6	−178.89 (19)	S1—S2—C10—C12	128.72 (12)
C1—N1—C7—C2	0.5 (2)	C8—S2—C10—C11	−111.60 (15)
C5—C6—C7—N1	179.72 (18)	S1—S2—C10—C11	−106.71 (13)
C5—C6—C7—C2	0.3 (3)	C8—S2—C10—C9	5.19 (14)
C3—C2—C7—N1	178.30 (17)	S1—S2—C10—C9	10.08 (14)
S1—C2—C7—N1	−1.5 (2)