10,11-Dihydr­oxy-4-aza­tricyclo[5.2.2.0^2,6]undec-8-ene-3,5-dione

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...O_carbon­yl, 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.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.043
• wR factor = 0.127
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7     ..  O5      ..       2.84 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H8     ..  O5      ..       2.96 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1     ..  O5      ..       2.73 Ang.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for O11    ..  O10     ..      99.00 Deg.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C8     ..  O5      ..      98.00 Deg.

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C1     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C2     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C6     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C7     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C10    = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C11    = ...          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   6 ALERT level G = General alerts; check

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

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 U_iso(H) = 1.2 U_eq(C/O/N).

Computing details

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

	Fig. 1. Perspective view of (I). Displacement ellipsoids are drawn at the 50% probability level.
	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.
	Fig. 3. View of the crystal packing down the c axis.
	Fig. 4. View of the crystal packing down the a axis.

10,11-Dihydroxy-4-azatricyclo[5.2.2.0^2,6]undec-8-ene-3,5-dione

Crystal data

C10H11NO4	F(000) = 440
Mr = 209.20	Dx = 1.575 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 76 reflections
a = 9.524 (2) Å	θ = 6–17.5°
b = 8.111 (2) Å	µ = 1.04 mm^−1
c = 11.586 (3) Å	T = 295 K
β = 99.71 (3)°	Prism, colourless
V = 882.2 (4) Å^3	0.53 × 0.23 × 0.23 mm
Z = 4

Data collection

Kuma KM-4 four-circle diffractometer	Rint = 0.029
Radiation source: fine-focus sealed tube	θmax = 80.2°, θmin = 5.6°
Graphite monochromator	h = −12→12
ω/2θ scans	k = 0→10
1973 measured reflections	l = 0→14
1891 independent reflections	3 standard reflections every 100 reflections
1410 reflections with I > 2σ(I)	intensity decay: 0.3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.127	w = 1/[σ^2(Fo^2) + (0.0746P)^2 + 0.224P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1891 reflections	Δρmax = 0.34 e Å^−3
137 parameters	Δρmin = −0.23 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.092 (5)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.32529 (18)	0.2170 (2)	0.60092 (15)	0.0296 (4)
H1	0.3621	0.2298	0.6847	0.035*
C2	0.19096 (16)	0.3221 (2)	0.56282 (13)	0.0255 (4)
H2	0.1184	0.2947	0.6105	0.031*
C3	0.22198 (17)	0.5054 (2)	0.56929 (15)	0.0282 (4)
O3	0.28269 (15)	0.58212 (16)	0.65367 (11)	0.0396 (4)
N4	0.16905 (15)	0.57479 (17)	0.46334 (13)	0.0307 (4)
H4	0.1667	0.6815	0.4481	0.037*
C5	0.11373 (17)	0.4610 (2)	0.37877 (15)	0.0277 (4)
O5	0.06147 (15)	0.49537 (16)	0.27993 (11)	0.0391 (4)
C6	0.13289 (17)	0.29072 (19)	0.43262 (14)	0.0260 (4)
H6	0.0414	0.2327	0.4235	0.031*
C7	0.24300 (18)	0.1890 (2)	0.37810 (15)	0.0291 (4)
H7	0.2162	0.1817	0.2928	0.035*
C8	0.38806 (18)	0.2644 (2)	0.41258 (17)	0.0348 (4)
H8	0.4420	0.3021	0.3581	0.042*
C9	0.43268 (18)	0.2726 (2)	0.52713 (17)	0.0348 (4)
H9	0.5232	0.3097	0.5595	0.042*
C10	0.28118 (17)	0.0364 (2)	0.57016 (15)	0.0300 (4)
H10C	0.3581	−0.0380	0.6045	0.036*
O10	0.15352 (13)	−0.00595 (16)	0.61250 (11)	0.0359 (3)
H10	0.1659	0.0053	0.6838	0.043*
C11	0.25367 (18)	0.0168 (2)	0.43507 (15)	0.0302 (4)
H11C	0.3384	−0.0361	0.4142	0.036*
O11	0.13623 (14)	−0.08778 (14)	0.39332 (11)	0.0356 (3)
H11	0.0642	−0.0513	0.4142	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0298 (8)	0.0270 (8)	0.0297 (8)	0.0006 (6)	−0.0012 (6)	0.0010 (6)
C2	0.0278 (8)	0.0239 (8)	0.0252 (7)	0.0015 (6)	0.0054 (6)	0.0018 (6)
C3	0.0308 (8)	0.0263 (8)	0.0283 (8)	0.0031 (6)	0.0071 (6)	−0.0010 (6)
O3	0.0525 (8)	0.0326 (7)	0.0314 (7)	−0.0035 (6)	0.0008 (6)	−0.0061 (5)
N4	0.0368 (8)	0.0212 (7)	0.0330 (8)	0.0008 (5)	0.0026 (6)	0.0020 (5)
C5	0.0278 (7)	0.0252 (8)	0.0300 (8)	0.0013 (6)	0.0044 (6)	0.0015 (6)
O5	0.0480 (7)	0.0334 (7)	0.0322 (7)	0.0010 (5)	−0.0037 (5)	0.0061 (5)
C6	0.0269 (7)	0.0217 (7)	0.0291 (8)	−0.0002 (6)	0.0042 (6)	0.0014 (6)
C7	0.0349 (8)	0.0248 (8)	0.0285 (8)	0.0041 (6)	0.0079 (6)	0.0001 (6)
C8	0.0330 (8)	0.0275 (8)	0.0475 (10)	0.0004 (7)	0.0172 (7)	0.0015 (7)
C9	0.0267 (8)	0.0287 (9)	0.0483 (10)	0.0023 (6)	0.0046 (7)	−0.0007 (7)
C10	0.0294 (8)	0.0251 (8)	0.0338 (9)	0.0009 (6)	0.0000 (6)	0.0040 (6)
O10	0.0398 (7)	0.0358 (7)	0.0311 (6)	−0.0068 (5)	0.0032 (5)	0.0039 (5)
C11	0.0340 (8)	0.0230 (8)	0.0336 (8)	0.0027 (6)	0.0053 (6)	−0.0015 (6)
O11	0.0424 (7)	0.0243 (6)	0.0387 (7)	−0.0019 (5)	0.0025 (5)	−0.0044 (5)

Geometric parameters (Å, º)

C1—C9	1.508 (3)	C6—H6	0.9800
C1—C2	1.539 (2)	C7—C8	1.502 (2)
C1—C10	1.548 (2)	C7—C11	1.541 (2)
C1—H1	0.9800	C7—H7	0.9800
C2—C3	1.516 (2)	C8—C9	1.325 (3)
C2—C6	1.538 (2)	C8—H8	0.9300
C2—H2	0.9800	C9—H9	0.9300
C3—O3	1.219 (2)	C10—O10	1.428 (2)
C3—N4	1.367 (2)	C10—C11	1.551 (2)
N4—C5	1.384 (2)	C10—H10C	0.9800
N4—H4	0.8829	O10—H10	0.8200
C5—O5	1.202 (2)	C11—O11	1.422 (2)
C5—C6	1.514 (2)	C11—H11C	0.9800
C6—C7	1.550 (2)	O11—H11	0.8200
C9—C1—C2	106.39 (13)	C8—C7—C11	105.30 (14)
C9—C1—C10	109.62 (14)	C8—C7—C6	109.28 (13)
C2—C1—C10	106.13 (13)	C11—C7—C6	107.95 (13)
C9—C1—H1	111.5	C8—C7—H7	111.4
C2—C1—H1	111.5	C11—C7—H7	111.4
C10—C1—H1	111.5	C6—C7—H7	111.4
C3—C2—C6	104.22 (12)	C9—C8—C7	114.33 (16)
C3—C2—C1	112.56 (13)	C9—C8—H8	122.8
C6—C2—C1	109.50 (13)	C7—C8—H8	122.8
C3—C2—H2	110.1	C8—C9—C1	114.78 (15)
C6—C2—H2	110.1	C8—C9—H9	122.6
C1—C2—H2	110.1	C1—C9—H9	122.6
O3—C3—N4	124.28 (16)	O10—C10—C1	111.24 (14)
O3—C3—C2	127.05 (15)	O10—C10—C11	108.25 (13)
N4—C3—C2	108.67 (14)	C1—C10—C11	108.82 (13)
C3—N4—C5	113.57 (14)	O10—C10—H10C	109.5
C3—N4—H4	125.2	C1—C10—H10C	109.5
C5—N4—H4	121.3	C11—C10—H10C	109.5
O5—C5—N4	124.53 (15)	C10—O10—H10	109.5
O5—C5—C6	127.31 (15)	O11—C11—C7	113.81 (14)
N4—C5—C6	108.16 (14)	O11—C11—C10	113.20 (14)
C5—C6—C2	104.59 (13)	C7—C11—C10	109.07 (13)
C5—C6—C7	111.13 (13)	O11—C11—H11C	106.8
C2—C6—C7	109.37 (13)	C7—C11—H11C	106.8
C5—C6—H6	110.5	C10—C11—H11C	106.8
C2—C6—H6	110.5	C11—O11—H11	109.5
C7—C6—H6	110.5
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—C6	61.26 (16)	C2—C6—C7—C11	66.40 (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—C9	58.76 (19)
C1—C2—C3—O3	−53.6 (2)	C7—C8—C9—C1	−4.5 (2)
C6—C2—C3—N4	8.35 (17)	C2—C1—C9—C8	−55.88 (19)
C1—C2—C3—N4	126.93 (15)	C10—C1—C9—C8	58.46 (19)
O3—C3—N4—C5	175.66 (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—O5	179.71 (16)	C9—C1—C10—C11	−44.65 (17)
C3—N4—C5—C6	−0.98 (19)	C2—C1—C10—C11	69.87 (16)
O5—C5—C6—C2	−174.55 (16)	C8—C7—C11—O11	−167.72 (14)
N4—C5—C6—C2	6.17 (17)	C6—C7—C11—O11	75.64 (17)
O5—C5—C6—C7	67.5 (2)	C8—C7—C11—C10	64.83 (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—C7	110.57 (14)	O10—C10—C11—C7	107.15 (15)
C1—C2—C6—C7	−10.07 (17)	C1—C10—C11—C7	−13.88 (18)
C5—C6—C7—C8	67.34 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O10	0.82	2.34	2.604 (2)	99
N4—H4···O11^i	0.88	1.98	2.857 (2)	171
O10—H10···O3^ii	0.82	1.96	2.768 (2)	166
O11—H11···O10^iii	0.82	2.10	2.852 (2)	153
C7—H7···O5^iv	0.98	2.84	3.231 (2)	105
C8—H8···O5^iv	0.93	2.96	3.214 (2)	98
C11—H11C···O5^iv	0.98	2.60	3.289 (2)	127
C1—H1···O5^v	0.98	2.73	3.279 (2)	116
C10—H10C···O5^v	0.98	2.58	3.303 (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.