Benzothia-zol-2-amine-3-meth-oxy-carbonyl-7-oxabicyclo-[2.2.1]hept-5-ene-2-carb-oxy-lic acid (1/1).

In the title 1:1 adduct, C(7)H(6)N(2)S·C(9)H(10)O(5), all non-H atoms of the benzothia-zol-2-amine mol-ecule are essentially coplanar, with a maximum deviation of 0.0286 (9) Å for the S atom. In the crystal, inter-molecular N-H⋯O and O-H⋯N hydrogen bonds connect two mol-ecules of each type into centrosymmetric four-component clusters.

Related literature

For applications of 3-(meth­oxy­carbon­yl)-7-oxa-bicyclo­[2.2.1]hept-5-ene-2-carb­oxy­lic acid and its derivatives, see: Deng & Hu (2007 ▶). For a related structure, see: Wang et al. (2008 ▶).

Experimental

Crystal data

C7H6N2S·C9H10O5

M = 348.37

Monoclinic,

a = 10.2737 (10) Å

b = 10.4325 (11) Å

c = 15.0308 (17) Å

β = 93.646 (1)°

V = 1607.7 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 298 K

0.44 × 0.42 × 0.35 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.905, T max = 0.924

7888 measured reflections

2849 independent reflections

1679 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.123

S = 1.03

2849 reflections

218 parameters

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.28 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810052542/lh5186sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810052542/lh5186Isup2.hkl

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

C7H6N2S·C9H10O5	F(000) = 728
Mr = 348.37	Dx = 1.439 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1736 reflections
a = 10.2737 (10) Å	θ = 2.3–22.2°
b = 10.4325 (11) Å	µ = 0.23 mm−1
c = 15.0308 (17) Å	T = 298 K
β = 93.646 (1)°	Block, light yellow
V = 1607.7 (3) Å3	0.44 × 0.42 × 0.35 mm
Z = 4

Bruker SMART CCD diffractometer	2849 independent reflections
Radiation source: fine-focus sealed tube	1679 reflections with I > 2σ(I)
graphite	Rint = 0.044
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −12→12
Tmin = 0.905, Tmax = 0.924	k = −12→11
7888 measured reflections	l = −17→15

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0403P)2 + 0.9023P] where P = (Fo2 + 2Fc2)/3
2849 reflections	(Δ/σ)max < 0.001
218 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.28 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
N1	0.4153 (2)	0.6895 (2)	0.77925 (16)	0.0453 (7)
N2	0.5207 (3)	0.5250 (3)	0.85991 (17)	0.0582 (8)
H2A	0.5263	0.5700	0.9079	0.070*
H2B	0.5514	0.4483	0.8601	0.070*
O1	0.3673 (2)	0.2580 (2)	0.52228 (13)	0.0535 (6)
O2	0.3477 (3)	0.1157 (3)	0.41181 (16)	0.0818 (9)
O3	0.0688 (2)	0.1771 (2)	0.49890 (13)	0.0617 (7)
O4	0.0927 (2)	0.3513 (2)	0.58303 (13)	0.0582 (6)
H4	0.0728	0.3016	0.6222	0.087*
O5	0.0846 (2)	0.2395 (2)	0.30892 (13)	0.0513 (6)
S1	0.45412 (9)	0.48354 (8)	0.68714 (6)	0.0561 (3)
C1	0.3281 (3)	0.2196 (3)	0.4405 (2)	0.0465 (8)
C2	0.0935 (3)	0.2904 (3)	0.5075 (2)	0.0420 (8)
C3	0.2594 (3)	0.3276 (3)	0.39140 (18)	0.0389 (7)
H3	0.3188	0.4010	0.3896	0.047*
C4	0.1297 (3)	0.3720 (3)	0.43033 (18)	0.0393 (7)
H4A	0.1347	0.4625	0.4476	0.047*
C5	0.0336 (3)	0.3534 (3)	0.3470 (2)	0.0471 (8)
H5	−0.0588	0.3494	0.3594	0.057*
C6	0.0675 (3)	0.4538 (3)	0.2804 (2)	0.0525 (9)
H6	0.0209	0.5280	0.2656	0.063*
C7	0.1755 (3)	0.4154 (3)	0.2479 (2)	0.0510 (9)
H7	0.2214	0.4562	0.2046	0.061*
C8	0.2104 (3)	0.2917 (3)	0.29452 (19)	0.0477 (8)
H8	0.2683	0.2352	0.2631	0.057*
C9	0.4275 (4)	0.1628 (3)	0.5812 (2)	0.0713 (11)
H9A	0.3621	0.1046	0.5998	0.107*
H9B	0.4689	0.2043	0.6325	0.107*
H9C	0.4915	0.1162	0.5504	0.107*
C10	0.4647 (3)	0.5736 (3)	0.7857 (2)	0.0460 (8)
C11	0.3640 (3)	0.7130 (3)	0.6929 (2)	0.0446 (8)
C12	0.3787 (3)	0.6131 (3)	0.6332 (2)	0.0470 (8)
C13	0.3350 (3)	0.6251 (4)	0.5446 (2)	0.0638 (10)
H13	0.3454	0.5582	0.5048	0.077*
C14	0.2767 (4)	0.7362 (4)	0.5167 (2)	0.0722 (12)
H14	0.2479	0.7453	0.4571	0.087*
C15	0.2594 (3)	0.8357 (4)	0.5750 (2)	0.0652 (10)
H15	0.2179	0.9102	0.5544	0.078*
C16	0.3029 (3)	0.8262 (3)	0.6639 (2)	0.0547 (9)
H16	0.2917	0.8936	0.7032	0.066*

	U11	U22	U33	U12	U13	U23
N1	0.0546 (16)	0.0395 (17)	0.0419 (16)	0.0030 (13)	0.0026 (13)	−0.0020 (12)
N2	0.085 (2)	0.0442 (18)	0.0454 (17)	0.0167 (16)	0.0036 (15)	−0.0005 (14)
O1	0.0663 (15)	0.0479 (15)	0.0437 (13)	0.0040 (11)	−0.0162 (11)	−0.0004 (11)
O2	0.122 (2)	0.0556 (17)	0.0649 (17)	0.0284 (16)	−0.0192 (15)	−0.0140 (14)
O3	0.0928 (18)	0.0521 (16)	0.0407 (13)	−0.0243 (14)	0.0078 (12)	−0.0001 (11)
O4	0.0928 (18)	0.0474 (14)	0.0354 (13)	−0.0022 (13)	0.0114 (12)	−0.0016 (11)
O5	0.0674 (15)	0.0475 (14)	0.0376 (12)	−0.0173 (12)	−0.0078 (11)	0.0021 (11)
S1	0.0723 (6)	0.0454 (6)	0.0512 (5)	−0.0042 (5)	0.0095 (4)	−0.0105 (4)
C1	0.049 (2)	0.049 (2)	0.0406 (19)	−0.0010 (17)	−0.0008 (15)	0.0009 (17)
C2	0.0448 (18)	0.045 (2)	0.0358 (19)	−0.0019 (16)	0.0019 (14)	0.0015 (16)
C3	0.0438 (18)	0.0360 (18)	0.0364 (17)	−0.0060 (14)	−0.0007 (14)	−0.0001 (14)
C4	0.0461 (18)	0.0365 (18)	0.0349 (16)	−0.0033 (15)	−0.0011 (14)	−0.0007 (14)
C5	0.0470 (19)	0.051 (2)	0.0426 (19)	−0.0059 (16)	−0.0058 (15)	0.0068 (17)
C6	0.060 (2)	0.051 (2)	0.0444 (19)	−0.0001 (18)	−0.0153 (17)	0.0096 (17)
C7	0.068 (2)	0.050 (2)	0.0335 (18)	−0.0141 (19)	−0.0058 (17)	0.0080 (16)
C8	0.061 (2)	0.049 (2)	0.0333 (17)	−0.0028 (17)	0.0037 (15)	0.0004 (15)
C9	0.085 (3)	0.065 (3)	0.060 (2)	0.011 (2)	−0.021 (2)	0.015 (2)
C10	0.0497 (19)	0.044 (2)	0.0450 (19)	−0.0030 (16)	0.0108 (15)	−0.0010 (16)
C11	0.0409 (18)	0.047 (2)	0.0455 (19)	−0.0080 (16)	0.0020 (15)	0.0001 (16)
C12	0.0486 (19)	0.052 (2)	0.0399 (19)	−0.0135 (16)	0.0028 (15)	−0.0056 (16)
C13	0.069 (2)	0.071 (3)	0.051 (2)	−0.018 (2)	−0.0037 (19)	−0.014 (2)
C14	0.071 (3)	0.093 (3)	0.050 (2)	−0.018 (2)	−0.0163 (19)	0.005 (2)
C15	0.056 (2)	0.073 (3)	0.065 (3)	−0.007 (2)	−0.0136 (19)	0.013 (2)
C16	0.054 (2)	0.053 (2)	0.056 (2)	−0.0020 (18)	−0.0012 (17)	0.0009 (18)

N1—C10	1.312 (4)	C4—H4A	0.9800
N1—C11	1.391 (4)	C5—C6	1.504 (4)
N2—C10	1.323 (4)	C5—H5	0.9800
N2—H2A	0.8600	C6—C7	1.304 (4)
N2—H2B	0.8600	C6—H6	0.9300
O1—C1	1.330 (3)	C7—C8	1.501 (4)
O1—C9	1.443 (3)	C7—H7	0.9300
O2—C1	1.188 (4)	C8—H8	0.9800
O3—C2	1.214 (4)	C9—H9A	0.9600
O4—C2	1.302 (3)	C9—H9B	0.9600
O4—H4	0.8200	C9—H9C	0.9600
O5—C8	1.432 (4)	C11—C12	1.390 (4)
O5—C5	1.432 (4)	C11—C16	1.395 (4)
S1—C12	1.733 (3)	C12—C13	1.384 (4)
S1—C10	1.752 (3)	C13—C14	1.359 (5)
C1—C3	1.499 (4)	C13—H13	0.9300
C2—C4	1.504 (4)	C14—C15	1.377 (5)
C3—C8	1.556 (4)	C14—H14	0.9300
C3—C4	1.560 (4)	C15—C16	1.385 (4)
C3—H3	0.9800	C15—H15	0.9300
C4—C5	1.557 (4)	C16—H16	0.9300
C10—N1—C11	110.7 (3)	C6—C7—H7	127.1
C10—N2—H2A	120.0	C8—C7—H7	127.1
C10—N2—H2B	120.0	O5—C8—C7	101.9 (3)
H2A—N2—H2B	120.0	O5—C8—C3	101.0 (2)
C1—O1—C9	116.9 (3)	C7—C8—C3	106.5 (3)
C2—O4—H4	109.5	O5—C8—H8	115.2
C8—O5—C5	95.9 (2)	C7—C8—H8	115.2
C12—S1—C10	88.80 (16)	C3—C8—H8	115.2
O2—C1—O1	124.2 (3)	O1—C9—H9A	109.5
O2—C1—C3	126.3 (3)	O1—C9—H9B	109.5
O1—C1—C3	109.5 (3)	H9A—C9—H9B	109.5
O3—C2—O4	123.7 (3)	O1—C9—H9C	109.5
O3—C2—C4	121.9 (3)	H9A—C9—H9C	109.5
O4—C2—C4	114.3 (3)	H9B—C9—H9C	109.5
C1—C3—C8	113.2 (3)	N1—C10—N2	124.2 (3)
C1—C3—C4	115.1 (2)	N1—C10—S1	115.4 (2)
C8—C3—C4	100.9 (2)	N2—C10—S1	120.5 (3)
C1—C3—H3	109.1	C12—C11—N1	114.8 (3)
C8—C3—H3	109.1	C12—C11—C16	119.9 (3)
C4—C3—H3	109.1	N1—C11—C16	125.3 (3)
C2—C4—C5	112.0 (2)	C13—C12—C11	120.8 (3)
C2—C4—C3	112.4 (2)	C13—C12—S1	128.9 (3)
C5—C4—C3	100.0 (2)	C11—C12—S1	110.3 (2)
C2—C4—H4A	110.7	C14—C13—C12	118.9 (4)
C5—C4—H4A	110.7	C14—C13—H13	120.5
C3—C4—H4A	110.7	C12—C13—H13	120.5
O5—C5—C6	101.9 (3)	C13—C14—C15	121.2 (3)
O5—C5—C4	101.3 (2)	C13—C14—H14	119.4
C6—C5—C4	106.6 (2)	C15—C14—H14	119.4
O5—C5—H5	115.1	C14—C15—C16	120.9 (4)
C6—C5—H5	115.1	C14—C15—H15	119.5
C4—C5—H5	115.1	C16—C15—H15	119.5
C7—C6—C5	105.9 (3)	C15—C16—C11	118.2 (3)
C7—C6—H6	127.0	C15—C16—H16	120.9
C5—C6—H6	127.0	C11—C16—H16	120.9
C6—C7—C8	105.8 (3)
C9—O1—C1—O2	−5.4 (5)	C6—C7—C8—O5	32.5 (3)
C9—O1—C1—C3	175.8 (3)	C6—C7—C8—C3	−73.0 (3)
O2—C1—C3—C8	1.0 (5)	C1—C3—C8—O5	87.8 (3)
O1—C1—C3—C8	179.7 (2)	C4—C3—C8—O5	−35.8 (3)
O2—C1—C3—C4	116.3 (4)	C1—C3—C8—C7	−166.1 (3)
O1—C1—C3—C4	−64.9 (3)	C4—C3—C8—C7	70.3 (3)
O3—C2—C4—C5	48.4 (4)	C11—N1—C10—N2	179.8 (3)
O4—C2—C4—C5	−132.4 (3)	C11—N1—C10—S1	0.4 (3)
O3—C2—C4—C3	−63.3 (4)	C12—S1—C10—N1	0.6 (2)
O4—C2—C4—C3	115.9 (3)	C12—S1—C10—N2	−178.8 (3)
C1—C3—C4—C2	−3.9 (3)	C10—N1—C11—C12	−1.6 (4)
C8—C3—C4—C2	118.4 (3)	C10—N1—C11—C16	179.2 (3)
C1—C3—C4—C5	−122.8 (3)	N1—C11—C12—C13	−178.4 (3)
C8—C3—C4—C5	−0.6 (3)	C16—C11—C12—C13	0.9 (5)
C8—O5—C5—C6	49.2 (2)	N1—C11—C12—S1	2.1 (3)
C8—O5—C5—C4	−60.7 (2)	C16—C11—C12—S1	−178.7 (2)
C2—C4—C5—O5	−82.4 (3)	C10—S1—C12—C13	179.0 (3)
C3—C4—C5—O5	36.8 (3)	C10—S1—C12—C11	−1.5 (2)
C2—C4—C5—C6	171.4 (3)	C11—C12—C13—C14	−0.3 (5)
C3—C4—C5—C6	−69.4 (3)	S1—C12—C13—C14	179.2 (3)
O5—C5—C6—C7	−31.4 (3)	C12—C13—C14—C15	−0.7 (6)
C4—C5—C6—C7	74.3 (3)	C13—C14—C15—C16	1.0 (6)
C5—C6—C7—C8	−0.6 (3)	C14—C15—C16—C11	−0.4 (5)
C5—O5—C8—C7	−49.7 (3)	C12—C11—C16—C15	−0.5 (5)
C5—O5—C8—C3	60.0 (2)	N1—C11—C16—C15	178.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3i	0.86	2.08	2.849 (3)	148
N2—H2B···O3ii	0.86	2.46	2.987 (4)	120
N2—H2B···O5ii	0.86	2.14	2.949 (4)	157
O4—H4···N1iii	0.82	1.89	2.676 (3)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3i	0.86	2.08	2.849 (3)	148
N2—H2B⋯O3ii	0.86	2.46	2.987 (4)	120
N2—H2B⋯O5ii	0.86	2.14	2.949 (4)	157
O4—H4⋯N1iii	0.82	1.89	2.676 (3)	162

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