supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, o3878    [ doi:10.1107/S1600536807040962 ]

10,11-Dihydroxy-4-azatricyclo[5.2.2.02,6]undec-8-ene-3,5-dione

M. Krawiecka, I. Wawrzycka-Gorczyca, A. Galazka, J. Kossakowski and A. E. Koziol

Abstract top

The succinimide ring of the title compound, C10H11NO4, is endo-cis-substituted to the bicyclooctene system. The hydroxyl groups of the diol fragment are cis oriented, the O-C-C-O torsion angle being -20.7 (2)°. One of the OH groups is a double donor in two O-H...O hydrogen bonds to the second group, forming both a weak intramolecular hydrogen bond [S(5) motif] and a centrosymmetric intermolecular dimer; the H...O distances are 2.34 and 2.10 Å for the intra- and intermolecular bonds, respectively. Accompanying intermolecular O-H...Ocarbonyl, N-H...O and C-H...O hydrogen bonds link the molecules into tapes parallel to the b axis and layers perpendicular to the c axis.

Comment top

A search for known structures of simple succinimide derivatives with mono- or bicyclic hydrocarbon moieties revealed several molecules having hydrophobic substituents (refcodes: IHEPUG, PHYPHM, ODEMAL, YITBUY, QICWOO, PEMWOU, PEMWUA, PESVOZ) as well as sulfinyl (WEWCAC) and sulfonylamino (YEXTUQ) fragments (The Cambridge Structural Database, Ver. 5.28 and upgrades; Allen, 2002). Their preferred molecular association is a chain formed between imide groups through N—H···O═C hydrogen bonds.

Continuing our studies (Kossakowski & Krawiecka, 2000) we designed a synthesis for several new derivatives containing the title compound (I). Molecule (I) has a bicyclooctene nucleus. One of its rings shares two C atoms with the cis bonded succinimide moiety, while the second ring has two hydroxyl substituents (Fig. 1). In the bicyclic hydrocarbon fragment, the six-membered rings adopt a distorted boat conformation. The hydroxyl groups are cis oriented to each other and linked by the weak intra-molecular O11—H···O10 hydrogen bond (Table 1). The motif of this intra-molecular hydrogen bond is S(5) (Bernstein et al., 1995) with the H···O distance of 2.34 Å and the O—H···O angle of 99°. The chemically equivalent C═O and C—N bonds of the succinimide system are not equal: C3═O3 1.219 (2) versus C5═O5 1.202 (2) Å and C3—N4 1.367 (2) versus C5—N4 1.384 (2) Å. Moreover, the five-membered succinimide ring is slightly puckered (torsion angles range from 1.0 (2)–8.4 (2)°).

Deviations from the expected bond lengths and the distorted conformation of rings are caused by the presence of different hydrogen bond patterns involving each of the carbonyl and hydroxyl groups (Table 1 and Fig. 2); for example: carbonyl O5 is involved in the C—H···O contacts only, while the C···O distances of the second carbonyl (i.e. O3) are longer than 3.35 Å. Strong inter-molecular O—H···O and N—H···O hydrogen bonds link hydroxyl, carbonyl and imide groups (Table 1), without typical imide···imide interactions. The hydroxyl O11 is involved in both intra- and inter-molecular hydrogen-bonding to O10 of the second hydroxyl group. A cyclic dimer is formed as a result of the inter-molecular hydroxyl···hydroxyl interaction around a center of symmetry (Fig. 2). The imide···hydroxyl N4—H···O11 hydrogen bond stabilizes the molecular tape running along the b axis (Fig. 3), while the hydroxyl···carbonyl O10—H···O3 bond links molecules lying in the neighbouring planes perpendicular to the c axis (Fig. 4). Numerous C—H···O contacts are also observed.

Related literature top

For related structures, see: Kossakowski & Krawiecka (2000). See also the Cambridge Structural Database (Version 5.28 and upgrades; Allen, 2002) for the structures of simple succinimide derivatives with mono- or bicyclic hydrocarbon fragments, refcodes IHEPUG, PHYPHM, ODEMAL, YITBUY, QICWOO, PEMWOU, PEMWUA, PESVOZ, WEWCAC and YEXTUQ. For related literature, see: Bernstein et al. (1995).

Experimental top

The Diels–Alder reaction was performed using a mixture of cis-3,5-cyclohexadiene-1,2-diole (30 cm3, 20% solution in ethyl acetate, 0.035 mol) and maleimide (5.14 g, 0.035 mol). After being refluxed for 2 h, the reaction mixture was cooled, the product was filtered off and recrystallized from ethyl acetate (m.p. 208–209°C).

Refinement top

The hydroxyl and imide H atoms were found from ΔF map, and next they were fixed at the O—H and N—H distances of 0.82 and 0.88 Å, respectively. Carbon-bonded H atoms were positioned geometrically and fixed with alkene and methine C—H distances of 0.93 and 0.98 Å, respectively. The displacement parameters of the H atoms were Uiso(H) = 1.2 Ueq(C/O/N).

Computing details top

Data collection: KM-4 Software (Kuma Diffraction, 1999); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Perspective view of (I). Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The N—H···O and O—H···O hydrogen bond pattern involving the central molecule (*). Hydrogen atoms have been omitted for clarity. For the symmetry codes see Table 1.
[Figure 3] Fig. 3. View of the crystal packing down the c axis.
[Figure 4] Fig. 4. View of the crystal packing down the a axis.
10,11-Dihydroxy-4-azatricyclo[5.2.2.02,6]undec-8-ene-3,5-dione top
Crystal data top
C10H11NO4F000 = 440
Mr = 209.20Dx = 1.575 Mg m−3
Monoclinic, P21/nCu Kα radiation
λ = 1.54178 Å
Hall symbol: -P 2ynCell parameters from 76 reflections
a = 9.524 (2) Åθ = 6–17.5º
b = 8.111 (2) ŵ = 1.04 mm−1
c = 11.586 (3) ÅT = 295 (2) K
β = 99.71 (3)ºPrism, colourless
V = 882.2 (4) Å30.53 × 0.23 × 0.23 mm
Z = 4
Data collection top
Kuma KM-4 four-circle
diffractometer		Rint = 0.029
Radiation source: fine-focus sealed tubeθmax = 80.2º
Monochromator: graphiteθmin = 5.6º
T = 295(2) Kh = −12→12
ω/2θ scansk = 0→10
Absorption correction: nonel = 0→14
1973 measured reflections3 standard reflections
1891 independent reflections every 100 reflections
1410 reflections with I > 2σ(I) intensity decay: 0.3%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.043  w = 1/[σ2(Fo2) + (0.0746P)2 + 0.224P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.127(Δ/σ)max < 0.001
S = 1.07Δρmax = 0.34 e Å−3
1891 reflectionsΔρmin = −0.23 e Å−3
137 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.092 (5)
Secondary atom site location: difference Fourier map
Crystal data top
C10H11NO4V = 882.2 (4) Å3
Mr = 209.20Z = 4
Monoclinic, P21/nCu Kα
a = 9.524 (2) ŵ = 1.04 mm−1
b = 8.111 (2) ÅT = 295 (2) K
c = 11.586 (3) Å0.53 × 0.23 × 0.23 mm
β = 99.71 (3)º
Data collection top
Kuma KM-4 four-circle
diffractometer		Rint = 0.029
Absorption correction: none3 standard reflections
1973 measured reflections every 100 reflections
1891 independent reflections intensity decay: 0.3%
1410 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.043137 parameters
wR(F2) = 0.127H-atom parameters constrained
S = 1.07Δρmax = 0.34 e Å−3
1891 reflectionsΔρmin = −0.23 e Å−3
Special details top

Experimental. 1H NMR (DMSO): δ 11.02 (s, 1H, N—H); 6.08–6.06 (t, 2H, C9—H, C10—H); 4.93 (s, 2H, C6—OH, C7—OH); 3.50 (s, 2H, C6—H, C7—H), 3.11 (s, 2H, C5—H, C8—H), 2.93 (s, 2H, C1—H, C4—H) Elemental analysis, calculated for C10H11NO4: C 57.42, H 5.26, N 6.72%; found: C 57.29, H 5.25, N 6.66%.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.32529 (18)0.2170 (2)0.60092 (15)0.0296 (4)
H10.36210.22980.68470.035*
C20.19096 (16)0.3221 (2)0.56282 (13)0.0255 (4)
H20.11840.29470.61050.031*
C30.22198 (17)0.5054 (2)0.56929 (15)0.0282 (4)
O30.28269 (15)0.58212 (16)0.65367 (11)0.0396 (4)
N40.16905 (15)0.57479 (17)0.46334 (13)0.0307 (4)
H40.16670.68150.44810.037*
C50.11373 (17)0.4610 (2)0.37877 (15)0.0277 (4)
O50.06147 (15)0.49537 (16)0.27993 (11)0.0391 (4)
C60.13289 (17)0.29072 (19)0.43262 (14)0.0260 (4)
H60.04140.23270.42350.031*
C70.24300 (18)0.1890 (2)0.37810 (15)0.0291 (4)
H70.21620.18170.29280.035*
C80.38806 (18)0.2644 (2)0.41258 (17)0.0348 (4)
H80.44200.30210.35810.042*
C90.43268 (18)0.2726 (2)0.52713 (17)0.0348 (4)
H90.52320.30970.55950.042*
C100.28118 (17)0.0364 (2)0.57016 (15)0.0300 (4)
H10C0.3581−0.03800.60450.036*
O100.15352 (13)−0.00595 (16)0.61250 (11)0.0359 (3)
H100.16590.00530.68380.043*
C110.25367 (18)0.0168 (2)0.43507 (15)0.0302 (4)
H11C0.3384−0.03610.41420.036*
O110.13623 (14)−0.08778 (14)0.39332 (11)0.0356 (3)
H110.0642−0.05130.41420.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0298 (8)0.0270 (8)0.0297 (8)0.0006 (6)−0.0012 (6)0.0010 (6)
C20.0278 (8)0.0239 (8)0.0252 (7)0.0015 (6)0.0054 (6)0.0018 (6)
C30.0308 (8)0.0263 (8)0.0283 (8)0.0031 (6)0.0071 (6)−0.0010 (6)
O30.0525 (8)0.0326 (7)0.0314 (7)−0.0035 (6)0.0008 (6)−0.0061 (5)
N40.0368 (8)0.0212 (7)0.0330 (8)0.0008 (5)0.0026 (6)0.0020 (5)
C50.0278 (7)0.0252 (8)0.0300 (8)0.0013 (6)0.0044 (6)0.0015 (6)
O50.0480 (7)0.0334 (7)0.0322 (7)0.0010 (5)−0.0037 (5)0.0061 (5)
C60.0269 (7)0.0217 (7)0.0291 (8)−0.0002 (6)0.0042 (6)0.0014 (6)
C70.0349 (8)0.0248 (8)0.0285 (8)0.0041 (6)0.0079 (6)0.0001 (6)
C80.0330 (8)0.0275 (8)0.0475 (10)0.0004 (7)0.0172 (7)0.0015 (7)
C90.0267 (8)0.0287 (9)0.0483 (10)0.0023 (6)0.0046 (7)−0.0007 (7)
C100.0294 (8)0.0251 (8)0.0338 (9)0.0009 (6)0.0000 (6)0.0040 (6)
O100.0398 (7)0.0358 (7)0.0311 (6)−0.0068 (5)0.0032 (5)0.0039 (5)
C110.0340 (8)0.0230 (8)0.0336 (8)0.0027 (6)0.0053 (6)−0.0015 (6)
O110.0424 (7)0.0243 (6)0.0387 (7)−0.0019 (5)0.0025 (5)−0.0044 (5)
Geometric parameters (Å, °) top
C1—C91.508 (3)C6—H60.9800
C1—C21.539 (2)C7—C81.502 (2)
C1—C101.548 (2)C7—C111.541 (2)
C1—H10.9800C7—H70.9800
C2—C31.516 (2)C8—C91.325 (3)
C2—C61.538 (2)C8—H80.9300
C2—H20.9800C9—H90.9300
C3—O31.219 (2)C10—O101.428 (2)
C3—N41.367 (2)C10—C111.551 (2)
N4—C51.384 (2)C10—H10C0.9800
N4—H40.8829O10—H100.8200
C5—O51.202 (2)C11—O111.422 (2)
C5—C61.514 (2)C11—H11C0.9800
C6—C71.550 (2)O11—H110.8200
C9—C1—C2106.39 (13)C8—C7—C11105.30 (14)
C9—C1—C10109.62 (14)C8—C7—C6109.28 (13)
C2—C1—C10106.13 (13)C11—C7—C6107.95 (13)
C9—C1—H1111.5C8—C7—H7111.4
C2—C1—H1111.5C11—C7—H7111.4
C10—C1—H1111.5C6—C7—H7111.4
C3—C2—C6104.22 (12)C9—C8—C7114.33 (16)
C3—C2—C1112.56 (13)C9—C8—H8122.8
C6—C2—C1109.50 (13)C7—C8—H8122.8
C3—C2—H2110.1C8—C9—C1114.78 (15)
C6—C2—H2110.1C8—C9—H9122.6
C1—C2—H2110.1C1—C9—H9122.6
O3—C3—N4124.28 (16)O10—C10—C1111.24 (14)
O3—C3—C2127.05 (15)O10—C10—C11108.25 (13)
N4—C3—C2108.67 (14)C1—C10—C11108.82 (13)
C3—N4—C5113.57 (14)O10—C10—H10C109.5
C3—N4—H4125.2C1—C10—H10C109.5
C5—N4—H4121.3C11—C10—H10C109.5
O5—C5—N4124.53 (15)C10—O10—H10109.5
O5—C5—C6127.31 (15)O11—C11—C7113.81 (14)
N4—C5—C6108.16 (14)O11—C11—C10113.20 (14)
C5—C6—C2104.59 (13)C7—C11—C10109.07 (13)
C5—C6—C7111.13 (13)O11—C11—H11C106.8
C2—C6—C7109.37 (13)C7—C11—H11C106.8
C5—C6—H6110.5C10—C11—H11C106.8
C2—C6—H6110.5C11—O11—H11109.5
C7—C6—H6110.5
C9—C1—C2—C3−54.17 (17)C2—C6—C7—C8−47.62 (17)
C10—C1—C2—C3−170.87 (14)C5—C6—C7—C11−178.63 (13)
C9—C1—C2—C661.26 (16)C2—C6—C7—C1166.40 (16)
C10—C1—C2—C6−55.44 (17)C11—C7—C8—C9−56.97 (19)
C6—C2—C3—O3−172.16 (16)C6—C7—C8—C958.76 (19)
C1—C2—C3—O3−53.6 (2)C7—C8—C9—C1−4.5 (2)
C6—C2—C3—N48.35 (17)C2—C1—C9—C8−55.88 (19)
C1—C2—C3—N4126.93 (15)C10—C1—C9—C858.46 (19)
O3—C3—N4—C5175.66 (16)C9—C1—C10—O10−163.83 (13)
C2—C3—N4—C5−4.84 (19)C2—C1—C10—O10−49.31 (17)
C3—N4—C5—O5179.71 (16)C9—C1—C10—C11−44.65 (17)
C3—N4—C5—C6−0.98 (19)C2—C1—C10—C1169.87 (16)
O5—C5—C6—C2−174.55 (16)C8—C7—C11—O11−167.72 (14)
N4—C5—C6—C26.17 (17)C6—C7—C11—O1175.64 (17)
O5—C5—C6—C767.5 (2)C8—C7—C11—C1064.83 (16)
N4—C5—C6—C7−111.73 (15)C6—C7—C11—C10−51.81 (17)
C3—C2—C6—C5−8.53 (15)O10—C10—C11—O11−20.65 (18)
C1—C2—C6—C5−129.17 (14)C1—C10—C11—O11−141.68 (13)
C3—C2—C6—C7110.57 (14)O10—C10—C11—C7107.15 (15)
C1—C2—C6—C7−10.07 (17)C1—C10—C11—C7−13.88 (18)
C5—C6—C7—C867.34 (18)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O11—H11···O100.822.342.604 (2)99
N4—H4···O11i0.881.982.857 (2)171
O10—H10···O3ii0.821.962.768 (2)166
O11—H11···O10iii0.822.102.852 (2)153
C7—H7···O5iv0.982.843.231 (2)105
C8—H8···O5iv0.932.963.214 (2)98
C11—H11C···O5iv0.982.603.289 (2)127
C1—H1···O5v0.982.733.279 (2)116
C10—H10C···O5v0.982.583.303 (2)130
Symmetry codes: (i) x, y+1, z; (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x, −y, −z+1; (iv) −x+1/2, y−1/2, −z+1/2; (v) x+1/2, −y+1/2, z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O11—H11···O100.822.342.604 (2)99
N4—H4···O11i0.881.982.857 (2)171
O10—H10···O3ii0.821.962.768 (2)166
O11—H11···O10iii0.822.102.852 (2)153
C11—H11C···O5iv0.982.603.289 (2)127
C10—H10C···O5v0.982.583.303 (2)130
Symmetry codes: (i) x, y+1, z; (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x, −y, −z+1; (iv) −x+1/2, y−1/2, −z+1/2; (v) x+1/2, −y+1/2, z+1/2.
references
References top

Allen, F. H. (2002). Acta Cryst. B58, 380–388.

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.

Kossakowski, J. & Krawiecka, M. (2000). Acta Pol. Pharm. 57, 53–56. [Please check year - 2000 here and in Related literature, but 2002 in original Comment]

Kuma Diffraction (1999). KM4 Software. Kuma Diffraction, Wrocław, Poland.

Sheldrick, G. M. (1990). SHELXTL/PC User's Manual. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.