2-[7-(3,5-Dibromo-2-hy-droxy-phen-yl)-6-eth-oxy-carbonyl-2-oxo-5H-2,3,6,7-tetra-hydro-thio-pyrano[2,3-d][1,3]thia-zol-6-yl]acetic acid ethanol monosolvate.

The title compound, C(17)H(15)Br(2)NO(6)S(2)·C(2)H(5)OH, is the esterification reaction product of 2-(8,10-dibromo-2,6-dioxo-3,5,5a,11b-tetra-hydro-2H,6H-chromeno[4',3':4,5]thio-pyrano[2,3-d]thia-zol-5a-yl)acetic acid. Cleavage of the lactone ring and formation of eth-oxy-carbonyl and hy-droxy groups from its structural elements were observed. On the other hand, the carb-oxy-methyl group was not esterified. The H atom and carb-oxy-methyl group, both at stereogenic centres, show a cis conformation. The six-membered dihydro-thio-pyran ring adopts a half-chair conformation. All NH and OH groups participate in the three-dimensional hydrogen-bond network, which is additionally strengthened by C-H⋯O and C-H⋯S inter-actions. Intramolecular O-H⋯Br and C-H⋯O interactions also occur.

Related literature

For the biological activity of 4-thia­zolidinone and thio­pyrano[2,3-d]thia­zole-2-one derivatives, see: Lesyk & Zimenkovsky (2004 ▶); Lesyk et al. (2011 ▶); Kaminskyy et al. (2011 ▶); Matiychuk et al. (2008 ▶); Lesyk et al. (2006 ▶); Atamanyuk et al. (2008 ▶). For ring conformation analysis, see: Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C17H15Br2NO6S2·C2H6O

M = 599.31

Monoclinic,

a = 16.8176 (9) Å

b = 8.1654 (4) Å

c = 18.3841 (9) Å

β = 113.303 (6)°

V = 2318.6 (2) Å3

Z = 4

Mo Kα radiation

μ = 3.72 mm−1

T = 130 K

0.45 × 0.40 × 0.25 mm

Data collection

Oxford Diffraction Xcalibur Atlas diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.761, T max = 1.000

15312 measured reflections

5539 independent reflections

4500 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.073

S = 1.09

5539 reflections

298 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.08 e Å−3

Δρmin = −0.87 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812035325/bt5997sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035325/bt5997Isup2.hkl

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

C17H15Br2NO6S2·C2H6O	F(000) = 1200
Mr = 599.31	Dx = 1.717 Mg m−3
Monoclinic, P21/n	Melting point = 510–512 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 16.8176 (9) Å	Cell parameters from 6534 reflections
b = 8.1654 (4) Å	θ = 2.4–29.1°
c = 18.3841 (9) Å	µ = 3.72 mm−1
β = 113.303 (6)°	T = 130 K
V = 2318.6 (2) Å3	Block, colourless
Z = 4	0.45 × 0.40 × 0.25 mm

Oxford Diffraction Xcalibur Atlas diffractometer	5539 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4500 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 29.1°, θmin = 2.4°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −22→22
Tmin = 0.761, Tmax = 1.000	k = −10→11
15312 measured reflections	l = −24→24

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.044P)2] where P = (Fo2 + 2Fc2)/3
5539 reflections	(Δ/σ)max = 0.002
298 parameters	Δρmax = 1.08 e Å−3
0 restraints	Δρmin = −0.87 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	0.996319 (13)	0.62878 (3)	0.839566 (12)	0.03491 (8)
Br2	1.074501 (12)	0.35750 (3)	0.592151 (13)	0.02712 (7)
S1	0.75077 (3)	0.80961 (6)	0.48078 (3)	0.01618 (11)
C2	0.71841 (11)	0.8163 (2)	0.37660 (11)	0.0157 (4)
N3	0.69780 (10)	0.66259 (19)	0.34724 (9)	0.0148 (3)
H3	0.6864 (14)	0.639 (3)	0.2971 (14)	0.017 (6)*
C4	0.70683 (11)	0.5421 (2)	0.40400 (10)	0.0126 (4)
S5	0.68259 (3)	0.33898 (6)	0.37237 (3)	0.01932 (11)
C6	0.72417 (12)	0.2434 (2)	0.46983 (11)	0.0144 (4)
H6A	0.7010	0.1332	0.4647	0.017*
H6B	0.7866	0.2345	0.4884	0.017*
C7	0.70239 (11)	0.3352 (2)	0.53289 (10)	0.0115 (3)
C8	0.74732 (10)	0.5062 (2)	0.55304 (10)	0.0104 (3)
H8	0.7183	0.5682	0.5812	0.013*
C9	0.73311 (11)	0.5980 (2)	0.47848 (10)	0.0115 (4)
O10	0.71500 (8)	0.94164 (17)	0.33849 (8)	0.0213 (3)
C11	0.60359 (11)	0.3610 (2)	0.50519 (11)	0.0140 (4)
H11A	0.5927	0.4331	0.5422	0.017*
H11B	0.5816	0.4140	0.4538	0.017*
C12	0.55580 (11)	0.2028 (2)	0.49939 (11)	0.0156 (4)
O13	0.59224 (8)	0.07109 (16)	0.51734 (8)	0.0178 (3)
O14	0.47090 (8)	0.22172 (18)	0.47434 (9)	0.0224 (3)
H14	0.4454 (16)	0.132 (3)	0.4748 (16)	0.037 (8)*
C15	0.73196 (11)	0.2392 (2)	0.61104 (11)	0.0132 (4)
O16	0.70277 (8)	0.26568 (16)	0.66029 (7)	0.0182 (3)
O17	0.79311 (8)	0.12991 (15)	0.61807 (8)	0.0171 (3)
C18	0.82447 (13)	0.0290 (3)	0.69041 (12)	0.0246 (5)
H18A	0.8501	−0.0706	0.6807	0.030*
H18B	0.7759	−0.0016	0.7033	0.030*
C19	0.89052 (17)	0.1187 (3)	0.75959 (15)	0.0419 (7)
H19A	0.8633	0.2095	0.7738	0.063*
H19B	0.9361	0.1583	0.7452	0.063*
H19C	0.9143	0.0455	0.8038	0.063*
C20	0.84402 (11)	0.4998 (2)	0.60762 (10)	0.0112 (3)
C21	0.87065 (11)	0.5535 (2)	0.68594 (10)	0.0133 (4)
C22	0.95879 (12)	0.5481 (3)	0.73445 (10)	0.0186 (4)
C23	1.02008 (11)	0.4888 (3)	0.70848 (11)	0.0202 (4)
H23	1.0783	0.4837	0.7423	0.024*
C24	0.99208 (12)	0.4375 (2)	0.63082 (12)	0.0173 (4)
C25	0.90546 (11)	0.4444 (2)	0.58003 (11)	0.0143 (4)
H25	0.8883	0.4122	0.5275	0.017*
O26	0.80868 (9)	0.61034 (17)	0.70964 (8)	0.0207 (3)
H26	0.8325 (17)	0.644 (3)	0.7654 (17)	0.046 (8)*
O27	0.84716 (10)	1.0647 (2)	0.30489 (9)	0.0325 (4)
H27	0.8036 (16)	1.032 (3)	0.3155 (15)	0.041 (7)*
C28	0.91066 (14)	1.1225 (3)	0.37811 (13)	0.0307 (5)
H28A	0.9057	1.0634	0.4219	0.037*
H28B	0.9016	1.2380	0.3845	0.037*
C29	0.99888 (15)	1.0965 (3)	0.37809 (17)	0.0432 (7)
H29A	1.0085	0.9815	0.3744	0.065*
H29B	1.0419	1.1392	0.4262	0.065*
H29C	1.0027	1.1523	0.3336	0.065*

	U11	U22	U33	U12	U13	U23
Br1	0.01994 (11)	0.0685 (2)	0.01402 (10)	−0.00743 (10)	0.00428 (8)	−0.01027 (10)
Br2	0.01891 (11)	0.03218 (14)	0.03580 (13)	0.00589 (9)	0.01672 (9)	0.00288 (10)
S1	0.0194 (2)	0.0091 (2)	0.0160 (2)	−0.00223 (18)	0.00270 (18)	0.00152 (18)
C2	0.0100 (8)	0.0176 (10)	0.0185 (9)	0.0012 (7)	0.0047 (7)	0.0051 (8)
N3	0.0163 (8)	0.0157 (8)	0.0126 (7)	0.0013 (6)	0.0059 (6)	0.0032 (6)
C4	0.0135 (8)	0.0123 (9)	0.0132 (8)	0.0003 (7)	0.0064 (7)	0.0008 (7)
S5	0.0323 (3)	0.0126 (2)	0.0124 (2)	−0.0027 (2)	0.00818 (19)	−0.00275 (18)
C6	0.0185 (9)	0.0100 (9)	0.0158 (8)	−0.0028 (7)	0.0079 (7)	−0.0002 (7)
C7	0.0128 (8)	0.0092 (8)	0.0132 (8)	−0.0004 (7)	0.0057 (7)	0.0013 (7)
C8	0.0116 (8)	0.0093 (9)	0.0109 (8)	−0.0008 (7)	0.0051 (6)	−0.0008 (7)
C9	0.0108 (8)	0.0076 (8)	0.0153 (8)	−0.0006 (7)	0.0045 (7)	0.0007 (7)
O10	0.0198 (7)	0.0173 (7)	0.0241 (7)	−0.0006 (6)	0.0058 (6)	0.0102 (6)
C11	0.0137 (8)	0.0120 (9)	0.0165 (9)	−0.0002 (7)	0.0062 (7)	0.0002 (7)
C12	0.0138 (8)	0.0191 (10)	0.0140 (8)	−0.0025 (8)	0.0057 (7)	−0.0006 (8)
O13	0.0160 (6)	0.0110 (7)	0.0258 (7)	−0.0024 (5)	0.0076 (5)	0.0003 (6)
O14	0.0144 (7)	0.0158 (7)	0.0340 (8)	−0.0040 (6)	0.0064 (6)	0.0028 (6)
C15	0.0130 (8)	0.0094 (9)	0.0164 (8)	−0.0032 (7)	0.0050 (7)	0.0008 (7)
O16	0.0245 (7)	0.0170 (7)	0.0161 (6)	0.0012 (6)	0.0114 (6)	0.0035 (5)
O17	0.0189 (6)	0.0149 (7)	0.0186 (7)	0.0055 (5)	0.0087 (5)	0.0077 (5)
C18	0.0277 (11)	0.0191 (11)	0.0273 (11)	0.0066 (9)	0.0112 (9)	0.0122 (9)
C19	0.0368 (13)	0.0460 (16)	0.0305 (13)	0.0038 (11)	0.0001 (11)	0.0122 (11)
C20	0.0132 (8)	0.0084 (8)	0.0120 (8)	−0.0019 (7)	0.0051 (7)	0.0016 (7)
C21	0.0147 (8)	0.0132 (9)	0.0139 (8)	−0.0030 (7)	0.0075 (7)	0.0007 (7)
C22	0.0176 (9)	0.0250 (11)	0.0104 (8)	−0.0043 (8)	0.0024 (7)	−0.0002 (8)
C23	0.0123 (9)	0.0271 (11)	0.0183 (9)	−0.0019 (8)	0.0028 (7)	0.0053 (8)
C24	0.0141 (8)	0.0182 (10)	0.0227 (9)	0.0013 (8)	0.0106 (7)	0.0036 (8)
C25	0.0158 (9)	0.0120 (9)	0.0160 (8)	−0.0018 (7)	0.0072 (7)	0.0000 (7)
O26	0.0204 (7)	0.0289 (8)	0.0149 (7)	−0.0018 (6)	0.0091 (6)	−0.0064 (6)
O27	0.0262 (8)	0.0515 (11)	0.0188 (7)	−0.0123 (8)	0.0079 (6)	0.0049 (7)
C28	0.0312 (12)	0.0357 (14)	0.0252 (11)	−0.0081 (10)	0.0111 (9)	−0.0066 (10)
C29	0.0270 (12)	0.0459 (16)	0.0511 (16)	−0.0037 (11)	0.0094 (11)	0.0067 (13)

Br1—C22	1.8980 (18)	C15—O17	1.329 (2)
Br2—C24	1.9061 (19)	O17—C18	1.473 (2)
S1—C9	1.7510 (18)	C18—C19	1.507 (3)
S1—C2	1.773 (2)	C18—H18A	0.9700
C2—O10	1.229 (2)	C18—H18B	0.9700
C2—N3	1.356 (3)	C19—H19A	0.9600
N3—C4	1.398 (2)	C19—H19B	0.9600
N3—H3	0.88 (2)	C19—H19C	0.9600
C4—C9	1.342 (2)	C20—C25	1.394 (3)
C4—S5	1.7515 (19)	C20—C21	1.398 (2)
S5—C6	1.8212 (19)	C21—O26	1.361 (2)
C6—C7	1.541 (3)	C21—C22	1.396 (2)
C6—H6A	0.9700	C22—C23	1.383 (3)
C6—H6B	0.9700	C23—C24	1.380 (3)
C7—C15	1.536 (2)	C23—H23	0.9300
C7—C11	1.548 (2)	C24—C25	1.386 (2)
C7—C8	1.561 (2)	C25—H25	0.9300
C8—C9	1.496 (2)	O26—H26	0.98 (3)
C8—C20	1.537 (2)	O27—C28	1.427 (3)
C8—H8	0.9800	O27—H27	0.87 (3)
C11—C12	1.503 (3)	C28—C29	1.499 (3)
C11—H11A	0.9700	C28—H28A	0.9700
C11—H11B	0.9700	C28—H28B	0.9700
C12—O13	1.217 (2)	C29—H29A	0.9600
C12—O14	1.325 (2)	C29—H29B	0.9600
O14—H14	0.85 (3)	C29—H29C	0.9600
C15—O16	1.208 (2)
C9—S1—C2	91.59 (9)	C15—O17—C18	116.76 (15)
O10—C2—N3	126.65 (18)	O17—C18—C19	111.79 (18)
O10—C2—S1	124.54 (16)	O17—C18—H18A	109.3
N3—C2—S1	108.81 (14)	C19—C18—H18A	109.3
C2—N3—C4	114.77 (16)	O17—C18—H18B	109.3
C2—N3—H3	122.1 (14)	C19—C18—H18B	109.3
C4—N3—H3	122.6 (14)	H18A—C18—H18B	107.9
C9—C4—N3	114.66 (17)	C18—C19—H19A	109.5
C9—C4—S5	126.90 (15)	C18—C19—H19B	109.5
N3—C4—S5	118.44 (13)	H19A—C19—H19B	109.5
C4—S5—C6	97.51 (8)	C18—C19—H19C	109.5
C7—C6—S5	114.75 (12)	H19A—C19—H19C	109.5
C7—C6—H6A	108.6	H19B—C19—H19C	109.5
S5—C6—H6A	108.6	C25—C20—C21	119.64 (15)
C7—C6—H6B	108.6	C25—C20—C8	121.24 (15)
S5—C6—H6B	108.6	C21—C20—C8	119.12 (15)
H6A—C6—H6B	107.6	O26—C21—C22	124.10 (16)
C15—C7—C6	111.71 (14)	O26—C21—C20	117.57 (15)
C15—C7—C11	106.57 (14)	C22—C21—C20	118.33 (16)
C6—C7—C11	111.24 (14)	C23—C22—C21	122.58 (17)
C15—C7—C8	106.69 (13)	C23—C22—Br1	118.67 (13)
C6—C7—C8	112.13 (14)	C21—C22—Br1	118.74 (14)
C11—C7—C8	108.21 (14)	C24—C23—C22	117.86 (16)
C9—C8—C20	111.07 (14)	C24—C23—H23	121.1
C9—C8—C7	110.11 (14)	C22—C23—H23	121.1
C20—C8—C7	114.34 (13)	C23—C24—C25	121.48 (18)
C9—C8—H8	107.0	C23—C24—Br2	119.28 (14)
C20—C8—H8	107.0	C25—C24—Br2	119.23 (15)
C7—C8—H8	107.0	C24—C25—C20	120.06 (17)
C4—C9—C8	129.31 (16)	C24—C25—H25	120.0
C4—C9—S1	110.15 (14)	C20—C25—H25	120.0
C8—C9—S1	120.54 (13)	C21—O26—H26	112.4 (16)
C12—C11—C7	112.39 (15)	C28—O27—H27	105.8 (17)
C12—C11—H11A	109.1	O27—C28—C29	108.9 (2)
C7—C11—H11A	109.1	O27—C28—H28A	109.9
C12—C11—H11B	109.1	C29—C28—H28A	109.9
C7—C11—H11B	109.1	O27—C28—H28B	109.9
H11A—C11—H11B	107.9	C29—C28—H28B	109.9
O13—C12—O14	123.74 (17)	H28A—C28—H28B	108.3
O13—C12—C11	122.87 (16)	C28—C29—H29A	109.5
O14—C12—C11	113.39 (16)	C28—C29—H29B	109.5
C12—O14—H14	112.1 (17)	H29A—C29—H29B	109.5
O16—C15—O17	125.14 (17)	C28—C29—H29C	109.5
O16—C15—C7	122.17 (16)	H29A—C29—H29C	109.5
O17—C15—C7	112.67 (15)	H29B—C29—H29C	109.5
C9—S1—C2—O10	178.68 (17)	C7—C11—C12—O13	2.3 (3)
C9—S1—C2—N3	−0.71 (14)	C7—C11—C12—O14	−178.81 (15)
O10—C2—N3—C4	−179.39 (17)	C6—C7—C15—O16	−160.59 (16)
S1—C2—N3—C4	−0.01 (19)	C11—C7—C15—O16	−38.9 (2)
C2—N3—C4—C9	1.0 (2)	C8—C7—C15—O16	76.5 (2)
C2—N3—C4—S5	−179.55 (13)	C6—C7—C15—O17	20.9 (2)
C9—C4—S5—C6	−10.25 (18)	C11—C7—C15—O17	142.56 (15)
N3—C4—S5—C6	170.43 (14)	C8—C7—C15—O17	−102.00 (16)
C4—S5—C6—C7	41.76 (14)	O16—C15—O17—C18	2.8 (3)
S5—C6—C7—C15	174.57 (12)	C7—C15—O17—C18	−178.74 (15)
S5—C6—C7—C11	55.62 (17)	C15—O17—C18—C19	−81.1 (2)
S5—C6—C7—C8	−65.71 (16)	C9—C8—C20—C25	−52.6 (2)
C15—C7—C8—C9	171.17 (14)	C7—C8—C20—C25	72.8 (2)
C6—C7—C8—C9	48.57 (19)	C9—C8—C20—C21	126.18 (18)
C11—C7—C8—C9	−74.49 (18)	C7—C8—C20—C21	−108.48 (18)
C15—C7—C8—C20	45.32 (19)	C25—C20—C21—O26	178.33 (16)
C6—C7—C8—C20	−77.29 (18)	C8—C20—C21—O26	−0.5 (2)
C11—C7—C8—C20	159.65 (15)	C25—C20—C21—C22	−0.7 (3)
N3—C4—C9—C8	178.26 (16)	C8—C20—C21—C22	−179.45 (16)
S5—C4—C9—C8	−1.1 (3)	O26—C21—C22—C23	179.74 (18)
N3—C4—C9—S1	−1.5 (2)	C20—C21—C22—C23	−1.3 (3)
S5—C4—C9—S1	179.11 (11)	O26—C21—C22—Br1	−1.4 (3)
C20—C8—C9—C4	111.4 (2)	C20—C21—C22—Br1	177.50 (14)
C7—C8—C9—C4	−16.3 (3)	C21—C22—C23—C24	1.7 (3)
C20—C8—C9—S1	−68.83 (18)	Br1—C22—C23—C24	−177.11 (15)
C7—C8—C9—S1	163.48 (12)	C22—C23—C24—C25	−0.1 (3)
C2—S1—C9—C4	1.28 (14)	C22—C23—C24—Br2	179.24 (15)
C2—S1—C9—C8	−178.54 (14)	C23—C24—C25—C20	−1.8 (3)
C15—C7—C11—C12	−54.49 (19)	Br2—C24—C25—C20	178.81 (14)
C6—C7—C11—C12	67.49 (19)	C21—C20—C25—C24	2.2 (3)
C8—C7—C11—C12	−168.91 (14)	C8—C20—C25—C24	−179.02 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O26—H26···Br1	0.98 (3)	2.55 (3)	3.1181 (15)	117 (2)
C6—H6A···O13	0.97	2.44	3.033 (2)	119
N3—H3···O27i	0.89 (2)	1.83 (2)	2.713 (2)	171 (3)
O14—H14···O13ii	0.85 (3)	1.80 (3)	2.645 (2)	171 (3)
O26—H26···O16iii	0.98 (3)	1.96 (3)	2.7800 (19)	139 (2)
O27—H27···O10	0.87 (3)	1.86 (3)	2.724 (2)	174 (2)
C6—H6A···S1iv	0.97	2.75	3.5659 (17)	142
C23—H23···O10v	0.93	2.36	3.253 (2)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O26—H26⋯Br1	0.98 (3)	2.55 (3)	3.1181 (15)	117 (2)
C6—H6A⋯O13	0.97	2.44	3.033 (2)	119
N3—H3⋯O27i	0.89 (2)	1.83 (2)	2.713 (2)	171 (3)
O14—H14⋯O13ii	0.85 (3)	1.80 (3)	2.645 (2)	171 (3)
O26—H26⋯O16iii	0.98 (3)	1.96 (3)	2.7800 (19)	139 (2)
O27—H27⋯O10	0.87 (3)	1.86 (3)	2.724 (2)	174 (2)
C6—H6A⋯S1iv	0.97	2.75	3.5659 (17)	142
C23—H23⋯O10v	0.93	2.36	3.253 (2)	161

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .