N-Carbamothioyl-amino-7-oxabicyclo-[2.2.1]hept-5-ene-2,3-dicarboximide.

The title compound, C(9)H(9)N(3)O(3)S, comprises a racemic mixture of chiral mol-ecules containing four stereogenic centres. The cyclo-hexane ring tends towards a boat conformation, while the tetra-hydro-furan ring and the dihydro-furan ring adopt envelope conformations. The dihedral angle between the thio-semicarbazide fragment and the fused-ring system is 77.20 (10)°. The crystal structure is stabilized by two inter-molecular N-H⋯O hydrogen bonds.

Related literature

For the use of 7-oxa-bicyclo­[2,2,1]hept-5-ene-2,3-dicarb­oxy­lic anhydride in clinical practice, see: Deng & Hu (2007 ▶). For the pharmacological activity of its derivatives, see: Hart et al. (2004 ▶). For bond lengths and angles in related structures, see: Goh et al. (2008 ▶).

Experimental

Crystal data

C9H9N3O3S

M = 239.25

Orthorhombic,

a = 8.3978 (8) Å

b = 8.9032 (9) Å

c = 13.5930 (14) Å

V = 1016.31 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 298 K

0.45 × 0.43 × 0.40 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.872, T max = 0.885

5015 measured reflections

1791 independent reflections

1632 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.071

S = 1.07

1791 reflections

145 parameters

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.16 e Å−3

Absolute structure: Flack (1983 ▶), 728 Friedel pairs

Flack parameter: 0.01 (9)

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 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681004835X/bx2331sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681004835X/bx2331Isup2.hkl

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

C9H9N3O3S	F(000) = 496
Mr = 239.25	Dx = 1.564 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2624 reflections
a = 8.3978 (8) Å	θ = 2.7–26.3°
b = 8.9032 (9) Å	µ = 0.31 mm−1
c = 13.5930 (14) Å	T = 298 K
V = 1016.31 (18) Å3	Block, light yellow
Z = 4	0.45 × 0.43 × 0.40 mm

Bruker SMART CCD area-detector diffractometer	1791 independent reflections
Radiation source: fine-focus sealed tube	1632 reflections with I > 2σ(I)
graphite	Rint = 0.023
phi and ω scans	θmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→9
Tmin = 0.872, Tmax = 0.885	k = −10→10
5015 measured reflections	l = −16→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H-atom parameters constrained
wR(F2) = 0.071	w = 1/[σ2(Fo2) + (0.0346P)2 + 0.1693P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
1791 reflections	Δρmax = 0.14 e Å−3
145 parameters	Δρmin = −0.16 e Å−3
0 restraints	Absolute structure: Flack (1983), 728 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (9)

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	0.97059 (7)	0.24096 (7)	0.78384 (4)	0.04347 (17)
N1	0.5849 (2)	0.39754 (19)	0.65892 (11)	0.0314 (4)
N2	0.7287 (2)	0.3264 (2)	0.67804 (13)	0.0407 (5)
H2	0.7712	0.2722	0.6327	0.049*
N3	0.7384 (2)	0.4298 (2)	0.83195 (13)	0.0447 (5)
H3A	0.6516	0.4766	0.8184	0.054*
H3B	0.7826	0.4413	0.8885	0.054*
O1	0.68615 (19)	0.5596 (2)	0.54443 (11)	0.0466 (4)
O2	0.4254 (2)	0.22814 (19)	0.73858 (12)	0.0529 (5)
O3	0.32651 (18)	0.33700 (17)	0.48808 (10)	0.0362 (4)
C1	0.5731 (3)	0.5099 (2)	0.58861 (14)	0.0321 (5)
C2	0.4001 (2)	0.5466 (2)	0.57606 (14)	0.0306 (5)
H2A	0.3754	0.6517	0.5911	0.037*
C3	0.3110 (2)	0.4351 (2)	0.64312 (15)	0.0322 (5)
H3	0.2452	0.4855	0.6927	0.039*
C4	0.4385 (3)	0.3383 (2)	0.68800 (14)	0.0334 (5)
C5	0.8043 (3)	0.3395 (2)	0.76542 (14)	0.0298 (5)
C6	0.3396 (3)	0.4970 (3)	0.47264 (15)	0.0357 (5)
H6	0.4065	0.5276	0.4171	0.043*
C7	0.1677 (3)	0.5434 (3)	0.46640 (18)	0.0457 (6)
H7	0.1252	0.6207	0.4287	0.055*
C8	0.0896 (3)	0.4521 (3)	0.52523 (17)	0.0450 (6)
H8	−0.0191	0.4531	0.5382	0.054*
C9	0.2106 (3)	0.3459 (3)	0.56743 (15)	0.0368 (5)
H9	0.1687	0.2495	0.5906	0.044*

	U11	U22	U33	U12	U13	U23
S1	0.0357 (3)	0.0469 (3)	0.0479 (3)	0.0058 (3)	−0.0064 (3)	0.0046 (3)
N1	0.0315 (9)	0.0367 (10)	0.0261 (8)	0.0045 (8)	−0.0032 (8)	−0.0030 (8)
N2	0.0382 (10)	0.0540 (12)	0.0299 (10)	0.0176 (9)	−0.0048 (8)	−0.0105 (8)
N3	0.0447 (11)	0.0553 (12)	0.0342 (10)	0.0059 (10)	−0.0116 (9)	−0.0121 (9)
O1	0.0357 (9)	0.0642 (12)	0.0399 (9)	−0.0093 (8)	0.0035 (8)	0.0077 (8)
O2	0.0607 (10)	0.0508 (10)	0.0472 (9)	−0.0104 (9)	−0.0100 (8)	0.0191 (9)
O3	0.0405 (8)	0.0351 (8)	0.0330 (8)	0.0003 (7)	−0.0017 (7)	−0.0079 (7)
C1	0.0368 (12)	0.0350 (11)	0.0245 (10)	−0.0046 (10)	−0.0007 (9)	−0.0048 (9)
C2	0.0333 (11)	0.0257 (11)	0.0329 (11)	0.0010 (9)	−0.0030 (10)	−0.0008 (9)
C3	0.0324 (11)	0.0354 (12)	0.0287 (10)	0.0009 (9)	0.0042 (9)	−0.0030 (9)
C4	0.0411 (13)	0.0348 (12)	0.0243 (10)	−0.0023 (10)	−0.0010 (9)	−0.0046 (9)
C5	0.0330 (11)	0.0283 (10)	0.0282 (11)	−0.0068 (9)	0.0014 (9)	0.0015 (9)
C6	0.0360 (11)	0.0411 (13)	0.0300 (11)	−0.0061 (11)	−0.0019 (9)	0.0050 (10)
C7	0.0449 (14)	0.0464 (15)	0.0459 (13)	0.0038 (12)	−0.0185 (12)	0.0023 (11)
C8	0.0292 (11)	0.0590 (17)	0.0469 (13)	−0.0001 (11)	−0.0064 (11)	−0.0078 (12)
C9	0.0352 (12)	0.0405 (12)	0.0345 (12)	−0.0095 (10)	0.0001 (10)	0.0027 (10)

S1—C5	1.668 (2)	C2—C3	1.542 (3)
N1—C1	1.387 (3)	C2—C6	1.558 (3)
N1—N2	1.388 (2)	C2—H2A	0.9800
N1—C4	1.395 (3)	C3—C4	1.504 (3)
N2—C5	1.352 (3)	C3—C9	1.549 (3)
N2—H2	0.8600	C3—H3	0.9800
N3—C5	1.331 (3)	C6—C7	1.505 (3)
N3—H3A	0.8600	C6—H6	0.9800
N3—H3B	0.8600	C7—C8	1.315 (3)
O1—C1	1.207 (2)	C7—H7	0.9300
O2—C4	1.203 (2)	C8—C9	1.502 (3)
O3—C6	1.444 (3)	C8—H8	0.9300
O3—C9	1.455 (3)	C9—H9	0.9800
C1—C2	1.499 (3)
C1—N1—N2	121.34 (18)	O2—C4—N1	123.4 (2)
C1—N1—C4	113.89 (17)	O2—C4—C3	129.3 (2)
N2—N1—C4	122.77 (17)	N1—C4—C3	107.21 (16)
C5—N2—N1	122.28 (18)	N3—C5—N2	116.96 (19)
C5—N2—H2	118.9	N3—C5—S1	124.34 (16)
N1—N2—H2	118.9	N2—C5—S1	118.69 (16)
C5—N3—H3A	120.0	O3—C6—C7	101.85 (18)
C5—N3—H3B	120.0	O3—C6—C2	99.98 (16)
H3A—N3—H3B	120.0	C7—C6—C2	106.61 (17)
C6—O3—C9	96.03 (15)	O3—C6—H6	115.5
O1—C1—N1	123.4 (2)	C7—C6—H6	115.5
O1—C1—C2	128.8 (2)	C2—C6—H6	115.5
N1—C1—C2	107.75 (17)	C8—C7—C6	105.9 (2)
C1—C2—C3	105.23 (17)	C8—C7—H7	127.0
C1—C2—C6	110.89 (17)	C6—C7—H7	127.0
C3—C2—C6	101.12 (16)	C7—C8—C9	106.5 (2)
C1—C2—H2A	112.9	C7—C8—H8	126.7
C3—C2—H2A	112.9	C9—C8—H8	126.7
C6—C2—H2A	112.9	O3—C9—C8	101.75 (17)
C4—C3—C2	105.28 (17)	O3—C9—C3	99.01 (15)
C4—C3—C9	111.29 (18)	C8—C9—C3	107.42 (18)
C2—C3—C9	101.62 (16)	O3—C9—H9	115.5
C4—C3—H3	112.6	C8—C9—H9	115.5
C2—C3—H3	112.6	C3—C9—H9	115.5
C9—C3—H3	112.6
C1—N1—N2—C5	114.5 (2)	C9—C3—C4—N1	115.12 (18)
C4—N1—N2—C5	−82.6 (3)	N1—N2—C5—N3	−3.0 (3)
N2—N1—C1—O1	−4.8 (3)	N1—N2—C5—S1	176.11 (16)
C4—N1—C1—O1	−169.10 (19)	C9—O3—C6—C7	−49.14 (18)
N2—N1—C1—C2	171.97 (16)	C9—O3—C6—C2	60.34 (17)
C4—N1—C1—C2	7.6 (2)	C1—C2—C6—O3	76.2 (2)
O1—C1—C2—C3	173.2 (2)	C3—C2—C6—O3	−34.98 (19)
N1—C1—C2—C3	−3.4 (2)	C1—C2—C6—C7	−178.11 (19)
O1—C1—C2—C6	64.6 (3)	C3—C2—C6—C7	70.7 (2)
N1—C1—C2—C6	−111.89 (18)	O3—C6—C7—C8	32.6 (2)
C1—C2—C3—C4	−1.5 (2)	C2—C6—C7—C8	−71.7 (2)
C6—C2—C3—C4	113.97 (17)	C6—C7—C8—C9	−1.1 (2)
C1—C2—C3—C9	−117.64 (18)	C6—O3—C9—C8	48.43 (18)
C6—C2—C3—C9	−2.2 (2)	C6—O3—C9—C3	−61.60 (17)
C1—N1—C4—O2	170.38 (19)	C7—C8—C9—O3	−30.6 (2)
N2—N1—C4—O2	6.3 (3)	C7—C8—C9—C3	72.9 (2)
C1—N1—C4—C3	−8.6 (2)	C4—C3—C9—O3	−73.4 (2)
N2—N1—C4—C3	−172.69 (17)	C2—C3—C9—O3	38.29 (19)
C2—C3—C4—O2	−173.1 (2)	C4—C3—C9—C8	−178.77 (18)
C9—C3—C4—O2	−63.8 (3)	C2—C3—C9—C8	−67.1 (2)
C2—C3—C4—N1	5.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3i	0.86	1.96	2.809 (2)	167
N3—H3B···O1ii	0.86	2.14	2.958 (2)	160
N3—H3A···N1	0.86	2.35	2.697 (2)	105

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3i	0.86	1.96	2.809 (2)	167
N3—H3B⋯O1ii	0.86	2.14	2.958 (2)	160

Symmetry codes: (i) ; (ii) .