PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3327.
Published online 2010 November 27. doi:  10.1107/S160053681004835X
PMCID: PMC3011812

N-Carbamothioyl­amino-7-oxabicyclo­[2.2.1]hept-5-ene-2,3-dicarboximide

Abstract

The title compound, C9H9N3O3S, comprises a racemic mixture of chiral mol­ecules containing four stereogenic centres. The cyclo­hexane ring tends towards a boat conformation, while the tetra­hydro­furan ring and the dihydro­furan ring adopt envelope conformations. The dihedral angle between the thio­semicarbazide fragment and the fused-ring system is 77.20 (10)°. The crystal structure is stabilized by two inter­molecular 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 [triangle]). For the pharmacological activity of its derivatives, see: Hart et al. (2004 [triangle]). For bond lengths and angles in related structures, see: Goh et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3327-scheme1.jpg

Experimental

Crystal data

  • C9H9N3O3S
  • M r = 239.25
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3327-efi1.jpg
  • 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 [triangle]) 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 [triangle]), 728 Friedel pairs
  • Flack parameter: 0.01 (9)

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Acknowledgments

Shandong Provincial Natural Science Foundation, China, is thanked for support (ZR2009BL027).

supplementary crystallographic information

Comment

7-Oxa-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride has been widely employed in clinical practice, as it is less toxic and much easier to be synthesized [Deng et al., 2007]. Its derivatives are also pharmacologically active [Hart et al., 2004]. We report here the crystal structure of the title compound, (I) which comprises a racemic mixture of chiral molecules containing four stereogenic centres. The cyclohexane ring tends towards a boat conformation, the tetrahydrofuran ring and the dihydrofuran ring adopt envelope conformations (Fig. 1). The bond lengths and bond angles are normal range and comparable to those in the similar compound [Goh, et al., 2008] as representative example. The dihedral angle between the thiosemicarbazide fragment and fused-ring system is 77.20 (10)°. The crystal structure is stabilized by two intermolecular N—H···O and one intramolecular N—H···N hydrogen bonds (Table 1, Fig. 2).

Experimental

A mixture of exo-7-oxa-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride (0.332 g, 2 mmol) and thiocarbanide (0.182 g, 2 mmol) in methanol (5 ml) was stirred for 5 h at room temperature, and then refluxed for 1 h. After cooling the precipitate was filtered and dried, the title compound was obtained. The crude product of 20 mg was dissolved in methanol of 10 ml. The solution was filtered to remove impurities, and then the filtrate was left for crystallization at room temperature. The single-crystal suitable for X-ray determination was obtained by evaporation from the methanol solution after 5 d.

Refinement

H atoms were initially located from difference maps and then refined in a riding model with C—H = 0.93–0.96 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoide are drawn at 30% probability level.
Fig. 2.
The crystal packing of (I), viewed along b axis. Dashed lines indicate hydrogen bonds.

Crystal data

C9H9N3O3SF(000) = 496
Mr = 239.25Dx = 1.564 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2624 reflections
a = 8.3978 (8) Åθ = 2.7–26.3°
b = 8.9032 (9) ŵ = 0.31 mm1
c = 13.5930 (14) ÅT = 298 K
V = 1016.31 (18) Å3Block, light yellow
Z = 40.45 × 0.43 × 0.40 mm

Data collection

Bruker SMART CCD area-detector diffractometer1791 independent reflections
Radiation source: fine-focus sealed tube1632 reflections with I > 2σ(I)
graphiteRint = 0.023
phi and ω scansθmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 1997)h = −9→9
Tmin = 0.872, Tmax = 0.885k = −10→10
5015 measured reflectionsl = −16→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.071w = 1/[σ2(Fo2) + (0.0346P)2 + 0.1693P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1791 reflectionsΔρmax = 0.14 e Å3
145 parametersΔρmin = −0.16 e Å3
0 restraintsAbsolute structure: Flack (1983), 728 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.01 (9)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S10.97059 (7)0.24096 (7)0.78384 (4)0.04347 (17)
N10.5849 (2)0.39754 (19)0.65892 (11)0.0314 (4)
N20.7287 (2)0.3264 (2)0.67804 (13)0.0407 (5)
H20.77120.27220.63270.049*
N30.7384 (2)0.4298 (2)0.83195 (13)0.0447 (5)
H3A0.65160.47660.81840.054*
H3B0.78260.44130.88850.054*
O10.68615 (19)0.5596 (2)0.54443 (11)0.0466 (4)
O20.4254 (2)0.22814 (19)0.73858 (12)0.0529 (5)
O30.32651 (18)0.33700 (17)0.48808 (10)0.0362 (4)
C10.5731 (3)0.5099 (2)0.58861 (14)0.0321 (5)
C20.4001 (2)0.5466 (2)0.57606 (14)0.0306 (5)
H2A0.37540.65170.59110.037*
C30.3110 (2)0.4351 (2)0.64312 (15)0.0322 (5)
H30.24520.48550.69270.039*
C40.4385 (3)0.3383 (2)0.68800 (14)0.0334 (5)
C50.8043 (3)0.3395 (2)0.76542 (14)0.0298 (5)
C60.3396 (3)0.4970 (3)0.47264 (15)0.0357 (5)
H60.40650.52760.41710.043*
C70.1677 (3)0.5434 (3)0.46640 (18)0.0457 (6)
H70.12520.62070.42870.055*
C80.0896 (3)0.4521 (3)0.52523 (17)0.0450 (6)
H8−0.01910.45310.53820.054*
C90.2106 (3)0.3459 (3)0.56743 (15)0.0368 (5)
H90.16870.24950.59060.044*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0357 (3)0.0469 (3)0.0479 (3)0.0058 (3)−0.0064 (3)0.0046 (3)
N10.0315 (9)0.0367 (10)0.0261 (8)0.0045 (8)−0.0032 (8)−0.0030 (8)
N20.0382 (10)0.0540 (12)0.0299 (10)0.0176 (9)−0.0048 (8)−0.0105 (8)
N30.0447 (11)0.0553 (12)0.0342 (10)0.0059 (10)−0.0116 (9)−0.0121 (9)
O10.0357 (9)0.0642 (12)0.0399 (9)−0.0093 (8)0.0035 (8)0.0077 (8)
O20.0607 (10)0.0508 (10)0.0472 (9)−0.0104 (9)−0.0100 (8)0.0191 (9)
O30.0405 (8)0.0351 (8)0.0330 (8)0.0003 (7)−0.0017 (7)−0.0079 (7)
C10.0368 (12)0.0350 (11)0.0245 (10)−0.0046 (10)−0.0007 (9)−0.0048 (9)
C20.0333 (11)0.0257 (11)0.0329 (11)0.0010 (9)−0.0030 (10)−0.0008 (9)
C30.0324 (11)0.0354 (12)0.0287 (10)0.0009 (9)0.0042 (9)−0.0030 (9)
C40.0411 (13)0.0348 (12)0.0243 (10)−0.0023 (10)−0.0010 (9)−0.0046 (9)
C50.0330 (11)0.0283 (10)0.0282 (11)−0.0068 (9)0.0014 (9)0.0015 (9)
C60.0360 (11)0.0411 (13)0.0300 (11)−0.0061 (11)−0.0019 (9)0.0050 (10)
C70.0449 (14)0.0464 (15)0.0459 (13)0.0038 (12)−0.0185 (12)0.0023 (11)
C80.0292 (11)0.0590 (17)0.0469 (13)−0.0001 (11)−0.0064 (11)−0.0078 (12)
C90.0352 (12)0.0405 (12)0.0345 (12)−0.0095 (10)0.0001 (10)0.0027 (10)

Geometric parameters (Å, °)

S1—C51.668 (2)C2—C31.542 (3)
N1—C11.387 (3)C2—C61.558 (3)
N1—N21.388 (2)C2—H2A0.9800
N1—C41.395 (3)C3—C41.504 (3)
N2—C51.352 (3)C3—C91.549 (3)
N2—H20.8600C3—H30.9800
N3—C51.331 (3)C6—C71.505 (3)
N3—H3A0.8600C6—H60.9800
N3—H3B0.8600C7—C81.315 (3)
O1—C11.207 (2)C7—H70.9300
O2—C41.203 (2)C8—C91.502 (3)
O3—C61.444 (3)C8—H80.9300
O3—C91.455 (3)C9—H90.9800
C1—C21.499 (3)
C1—N1—N2121.34 (18)O2—C4—N1123.4 (2)
C1—N1—C4113.89 (17)O2—C4—C3129.3 (2)
N2—N1—C4122.77 (17)N1—C4—C3107.21 (16)
C5—N2—N1122.28 (18)N3—C5—N2116.96 (19)
C5—N2—H2118.9N3—C5—S1124.34 (16)
N1—N2—H2118.9N2—C5—S1118.69 (16)
C5—N3—H3A120.0O3—C6—C7101.85 (18)
C5—N3—H3B120.0O3—C6—C299.98 (16)
H3A—N3—H3B120.0C7—C6—C2106.61 (17)
C6—O3—C996.03 (15)O3—C6—H6115.5
O1—C1—N1123.4 (2)C7—C6—H6115.5
O1—C1—C2128.8 (2)C2—C6—H6115.5
N1—C1—C2107.75 (17)C8—C7—C6105.9 (2)
C1—C2—C3105.23 (17)C8—C7—H7127.0
C1—C2—C6110.89 (17)C6—C7—H7127.0
C3—C2—C6101.12 (16)C7—C8—C9106.5 (2)
C1—C2—H2A112.9C7—C8—H8126.7
C3—C2—H2A112.9C9—C8—H8126.7
C6—C2—H2A112.9O3—C9—C8101.75 (17)
C4—C3—C2105.28 (17)O3—C9—C399.01 (15)
C4—C3—C9111.29 (18)C8—C9—C3107.42 (18)
C2—C3—C9101.62 (16)O3—C9—H9115.5
C4—C3—H3112.6C8—C9—H9115.5
C2—C3—H3112.6C3—C9—H9115.5
C9—C3—H3112.6
C1—N1—N2—C5114.5 (2)C9—C3—C4—N1115.12 (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—S1176.11 (16)
C4—N1—C1—O1−169.10 (19)C9—O3—C6—C7−49.14 (18)
N2—N1—C1—C2171.97 (16)C9—O3—C6—C260.34 (17)
C4—N1—C1—C27.6 (2)C1—C2—C6—O376.2 (2)
O1—C1—C2—C3173.2 (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—C664.6 (3)C3—C2—C6—C770.7 (2)
N1—C1—C2—C6−111.89 (18)O3—C6—C7—C832.6 (2)
C1—C2—C3—C4−1.5 (2)C2—C6—C7—C8−71.7 (2)
C6—C2—C3—C4113.97 (17)C6—C7—C8—C9−1.1 (2)
C1—C2—C3—C9−117.64 (18)C6—O3—C9—C848.43 (18)
C6—C2—C3—C9−2.2 (2)C6—O3—C9—C3−61.60 (17)
C1—N1—C4—O2170.38 (19)C7—C8—C9—O3−30.6 (2)
N2—N1—C4—O26.3 (3)C7—C8—C9—C372.9 (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—O338.29 (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—N15.8 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O3i0.861.962.809 (2)167
N3—H3B···O1ii0.862.142.958 (2)160
N3—H3A···N10.862.352.697 (2)105

Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x+3/2, −y+1, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2331).

References

  • Bruker (1997). SADABS, SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Deng, L. P. & Hu, Y. Z. (2007). J. Heterocycl. Chem.44, 597–601.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Goh, Y. W., Pool, B. R. & White, J. M. (2008). J. Org. Chem.73, 151–156. [PubMed]
  • Hart, M. E., Chamberlin, A. R., Walkom, C., Sakoff, J. A. & McCluskey, A. (2004). Bioorg. Med. Chem. Lett.14, 1969–1973. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography