4-Oxo-1,4-dihydro-benzo[h][1,3]thia-zeto[3,2-a]quinoline-1,3-dicarb-oxy-lic acid.

In the title mol-ecule, C(16)H(9)NO(5)S, there is an intra-molecular O-H⋯O hydrogen bond involving the quinolone carbonyl O atom and a carboxyl OH group. In the crystal, inter-molecular O-H⋯O hydrogen bonds between the carbonyl group of the quinolone carboxyl group, and a second carboxyl group on the thia-zeto moiety lead to the formation of chains propagating along [201] and perpendicular to the π-stacks of mol-ecules.

Related literature

For background to the biological importance of thia­zetoquinoline anti­biotics, see: Ozaki et al. (1991 ▶). For similar work using different procedures, see: Ito et al. (1992 ▶, 1994 ▶); Matsuoka et al. (1999 ▶).

Experimental

Crystal data

C16H9NO5S

M = 327.31

Monoclinic,

a = 7.237 (2) Å

b = 16.171 (5) Å

c = 11.929 (4) Å

β = 106.081 (8)°

V = 1341.5 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.27 mm−1

T = 153 K

0.18 × 0.04 × 0.04 mm

Data collection

Rigaku Saturn diffractometer

Absorption correction: numerical (ABSCOR; Higashi, 1999 ▶) T min = 0.974, T max = 0.996

17300 measured reflections

2769 independent reflections

2614 reflections with I > 2σ(I)

R int = 0.074

Refinement

R[F 2 > 2σ(F 2)] = 0.088

wR(F 2) = 0.164

S = 1.30

2769 reflections

214 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.31 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003333/su2249sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811003333/su2249Isup2.hkl

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

C16H9NO5S	F(000) = 672
Mr = 327.31	Dx = 1.621 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 4915 reflections
a = 7.237 (2) Å	θ = 2.2–30.6°
b = 16.171 (5) Å	µ = 0.27 mm−1
c = 11.929 (4) Å	T = 153 K
β = 106.081 (8)°	Needle, colourless
V = 1341.5 (7) Å3	0.18 × 0.04 × 0.04 mm
Z = 4

Rigaku Saturn diffractometer	2769 independent reflections
Radiation source: fine-focus sealed tube	2614 reflections with I > 2σ(I)
graphite - Rigaku SHINE	Rint = 0.074
Detector resolution: 14.63 pixels mm-1	θmax = 26.5°, θmin = 2.5°
ω scans	h = −9→9
Absorption correction: numerical (ABSCOR; Higashi, 1999)	k = −20→20
Tmin = 0.974, Tmax = 0.996	l = −14→14
17300 measured reflections

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)] = 0.088	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.30	w = 1/[σ2(Fo2) + (0.0366P)2 + 2.1946P] where P = (Fo2 + 2Fc2)/3
2769 reflections	(Δ/σ)max < 0.001
214 parameters	Δρmax = 0.31 e Å−3
2 restraints	Δρmin = −0.31 e Å−3

Experimental. Spectroscopic data:1H-NMR: (500 MHz, DMSO-d6): δ= 8.27(1H, d, J=8.8), 8.25(1H, d, J=8.4), 8.17(1H, d, J=7.5), 8.02(1H, d, J=8.80), 7.83(1H, dd, J=11.0, 4.0), 7.81–7.76(1H, m), 7.73(1H, s)}. 13C-NMR: (500 MHz, DMSO-d6): δ= 175.76, 165.64, 165.25, 164.26, 136.09, 135.26, 129.58, 128.97, 127.58, 126.05, 122.67, 122.33, 121.53, 121.15, 103.64, 70.43.

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
S1	0.60834 (14)	0.26465 (6)	0.14885 (8)	0.0347 (3)
O1	0.5029 (4)	−0.01520 (17)	0.3384 (2)	0.0387 (7)
O2	0.2537 (4)	0.33079 (19)	−0.0999 (3)	0.0512 (8)
O3	0.1270 (4)	0.25356 (17)	0.0178 (2)	0.0370 (6)
O4	0.7870 (4)	0.20609 (17)	0.3966 (2)	0.0379 (7)
O5	0.7226 (4)	0.08587 (19)	0.4695 (2)	0.0439 (7)
N1	0.4277 (4)	0.14703 (17)	0.0711 (2)	0.0257 (6)
C1	0.5397 (5)	0.1656 (2)	0.1790 (3)	0.0274 (7)
C2	0.5731 (5)	0.1139 (2)	0.2722 (3)	0.0289 (8)
C3	0.4829 (5)	0.0354 (2)	0.2544 (3)	0.0303 (8)
C4	0.3696 (5)	0.0139 (2)	0.1369 (3)	0.0277 (8)
C5	0.2892 (5)	−0.0668 (2)	0.1153 (3)	0.0318 (8)
H5	0.3105	−0.1057	0.1774	0.038*
C6	0.1828 (5)	−0.0887 (2)	0.0074 (3)	0.0317 (8)
H6	0.1297	−0.1428	−0.0048	0.038*
C7	0.1484 (5)	−0.0329 (2)	−0.0882 (3)	0.0281 (8)
C8	0.0343 (5)	−0.0566 (2)	−0.2002 (3)	0.0327 (8)
H8	−0.0180	−0.1108	−0.2118	0.039*
C9	−0.0019 (5)	−0.0027 (3)	−0.2920 (3)	0.0364 (9)
H9	−0.0819	−0.0190	−0.3661	0.044*
C10	0.0790 (6)	0.0762 (2)	−0.2765 (3)	0.0359 (9)
H10	0.0552	0.1130	−0.3410	0.043*
C11	0.1927 (5)	0.1015 (2)	−0.1696 (3)	0.0324 (8)
H11	0.2475	0.1553	−0.1611	0.039*
C12	0.2288 (5)	0.0480 (2)	−0.0719 (3)	0.0275 (8)
C13	0.3401 (5)	0.0702 (2)	0.0439 (3)	0.0254 (7)
C14	0.4427 (5)	0.2249 (2)	0.0104 (3)	0.0298 (8)
H14	0.5090	0.2174	−0.0521	0.036*
C15	0.2618 (5)	0.2759 (2)	−0.0304 (3)	0.0327 (8)
C16	0.7025 (5)	0.1379 (2)	0.3852 (3)	0.0332 (9)
H5A	0.649 (6)	0.039 (2)	0.432 (4)	0.052*
H3	0.008 (4)	0.277 (2)	−0.029 (3)	0.044*

	U11	U22	U33	U12	U13	U23
S1	0.0343 (5)	0.0303 (5)	0.0351 (5)	−0.0046 (4)	0.0023 (4)	−0.0016 (4)
O1	0.0403 (16)	0.0408 (16)	0.0313 (14)	0.0000 (12)	0.0036 (12)	0.0104 (12)
O2	0.0460 (17)	0.0450 (17)	0.062 (2)	0.0053 (14)	0.0138 (15)	0.0244 (16)
O3	0.0304 (14)	0.0391 (15)	0.0396 (15)	0.0034 (12)	0.0065 (12)	0.0059 (12)
O4	0.0335 (14)	0.0420 (16)	0.0337 (14)	−0.0013 (13)	0.0022 (11)	−0.0073 (12)
O5	0.0438 (17)	0.0558 (19)	0.0260 (14)	−0.0055 (14)	−0.0006 (12)	0.0038 (13)
N1	0.0257 (15)	0.0240 (15)	0.0263 (15)	−0.0017 (12)	0.0053 (12)	0.0024 (12)
C1	0.0220 (17)	0.0300 (18)	0.0289 (18)	−0.0005 (14)	0.0051 (14)	−0.0049 (15)
C2	0.0265 (18)	0.033 (2)	0.0273 (18)	−0.0005 (15)	0.0080 (14)	−0.0024 (15)
C3	0.0285 (18)	0.036 (2)	0.0268 (18)	0.0060 (16)	0.0076 (14)	0.0044 (15)
C4	0.0243 (17)	0.0300 (19)	0.0294 (18)	0.0035 (15)	0.0087 (14)	0.0009 (15)
C5	0.0285 (19)	0.0283 (19)	0.040 (2)	0.0039 (15)	0.0111 (16)	0.0066 (16)
C6	0.0278 (18)	0.0252 (19)	0.042 (2)	0.0007 (15)	0.0092 (16)	0.0008 (16)
C7	0.0237 (17)	0.0275 (18)	0.0326 (19)	0.0035 (14)	0.0072 (14)	−0.0029 (15)
C8	0.0259 (18)	0.033 (2)	0.039 (2)	−0.0002 (15)	0.0076 (16)	−0.0087 (17)
C9	0.0282 (19)	0.045 (2)	0.031 (2)	0.0022 (17)	0.0004 (15)	−0.0106 (17)
C10	0.039 (2)	0.038 (2)	0.0280 (19)	0.0004 (18)	0.0058 (16)	0.0025 (17)
C11	0.034 (2)	0.0300 (19)	0.0323 (19)	−0.0032 (16)	0.0082 (16)	−0.0041 (16)
C12	0.0220 (17)	0.0298 (19)	0.0303 (18)	0.0010 (14)	0.0065 (14)	−0.0007 (15)
C13	0.0224 (16)	0.0250 (17)	0.0302 (18)	0.0013 (14)	0.0094 (14)	0.0003 (15)
C14	0.0265 (18)	0.0290 (19)	0.0329 (19)	0.0002 (15)	0.0065 (15)	0.0027 (15)
C15	0.035 (2)	0.0271 (19)	0.0325 (19)	−0.0016 (16)	0.0029 (16)	−0.0013 (16)
C16	0.0300 (19)	0.044 (2)	0.0267 (19)	0.0051 (17)	0.0093 (15)	−0.0021 (17)

S1—C1	1.744 (4)	C5—C6	1.351 (5)
S1—C14	1.866 (4)	C5—H5	0.9500
O1—C3	1.271 (4)	C6—C7	1.421 (5)
O2—C15	1.205 (4)	C6—H6	0.9500
O3—C15	1.314 (5)	C7—C8	1.416 (5)
O3—H3	0.963 (19)	C7—C12	1.423 (5)
O4—C16	1.250 (5)	C8—C9	1.366 (5)
O5—C16	1.288 (5)	C8—H8	0.9500
O5—H5A	0.965 (19)	C9—C10	1.394 (6)
N1—C1	1.350 (4)	C9—H9	0.9500
N1—C13	1.392 (4)	C10—C11	1.375 (5)
N1—C14	1.472 (4)	C10—H10	0.9500
C1—C2	1.358 (5)	C11—C12	1.416 (5)
C2—C3	1.416 (5)	C11—H11	0.9500
C2—C16	1.464 (5)	C12—C13	1.438 (5)
C3—C4	1.456 (5)	C14—C15	1.509 (5)
C4—C13	1.406 (5)	C14—H14	1.0000
C4—C5	1.423 (5)
C1—S1—C14	73.49 (16)	C7—C8—H8	119.5
C15—O3—H3	107 (3)	C8—C9—C10	119.8 (3)
C16—O5—H5A	103 (3)	C8—C9—H9	120.1
C1—N1—C13	122.3 (3)	C10—C9—H9	120.1
C1—N1—C14	99.9 (3)	C11—C10—C9	121.1 (4)
C13—N1—C14	137.7 (3)	C11—C10—H10	119.5
N1—C1—C2	124.6 (3)	C9—C10—H10	119.5
N1—C1—S1	97.9 (2)	C10—C11—C12	120.5 (3)
C2—C1—S1	137.5 (3)	C10—C11—H11	119.7
C1—C2—C3	117.2 (3)	C12—C11—H11	119.7
C1—C2—C16	121.0 (3)	C11—C12—C7	118.3 (3)
C3—C2—C16	121.8 (3)	C11—C12—C13	124.3 (3)
O1—C3—C2	120.8 (3)	C7—C12—C13	117.3 (3)
O1—C3—C4	121.0 (3)	N1—C13—C4	115.7 (3)
C2—C3—C4	118.2 (3)	N1—C13—C12	123.0 (3)
C13—C4—C5	119.1 (3)	C4—C13—C12	121.3 (3)
C13—C4—C3	121.8 (3)	N1—C14—C15	116.8 (3)
C5—C4—C3	119.1 (3)	N1—C14—S1	88.6 (2)
C6—C5—C4	120.6 (3)	C15—C14—S1	112.6 (3)
C6—C5—H5	119.7	N1—C14—H14	112.3
C4—C5—H5	119.7	C15—C14—H14	112.3
C5—C6—C7	121.7 (3)	S1—C14—H14	112.3
C5—C6—H6	119.2	O2—C15—O3	127.1 (4)
C7—C6—H6	119.2	O2—C15—C14	119.8 (4)
C8—C7—C6	120.8 (3)	O3—C15—C14	113.1 (3)
C8—C7—C12	119.2 (3)	O4—C16—O5	123.0 (3)
C6—C7—C12	120.0 (3)	O4—C16—C2	120.2 (3)
C9—C8—C7	121.0 (4)	O5—C16—C2	116.8 (4)
C9—C8—H8	119.5

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O1	0.96 (4)	1.57 (4)	2.504 (4)	161 (4)
O3—H3···O4i	0.97 (3)	1.62 (3)	2.569 (4)	166 (3)

π···π	Distance	Angle of Elevation
Cg1···Cg2i	3.560 (2)	19.56
Cg3···Cg2i	3.644 (2)	22.75
Cg3···Cg3i	3.688 (2)	24.39

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O1	0.96 (4)	1.57 (4)	2.504 (4)	161 (4)
O3—H3⋯O4i	0.97 (3)	1.62 (3)	2.569 (4)	166 (3)

Symmetry code: (i) .

Table 2

π⋯π inter­actions (Å, °)

Angle of elevation defined as the angle of the Cg(I)→Cg(J) vector and the normal to plane J. Cg1, Cg2 and Cg3 are the centroids of the C7–C12, N1/C1–C4/C13 and C4–C7/C12/C13 rings, respectively.

π⋯π	Distance	Angle of Elevation
Cg1⋯Cg2i	3.560 (2)	19.56
Cg3⋯Cg2i	3.644 (2)	22.75
Cg3⋯Cg3i	3.688 (2)	24.39

Symmetry code: (i) −x + 1, −y, −z.