exo,exo-4-(2-Hy­droxy­eth­yl)-10-oxa-4-aza­tricyclo­[5.2.1.02,6]dec-8-ene-3,5-dione

Tan, X.-J.; Li, C.-G.; Xing, D.-X.; Liu, Y.

doi:10.1107/S160053681200788X

organic compounds

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exo,exo-4-(2-Hydroxyethyl)-10-oxa-4-azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione

Xue-Jie Tan,^a ^* Chen-Guang Li,^a Dian-Xiang Xing ^a and Yun Liu ^a

^aSchool of Chemical and Pharmaceutical Engineering, Shandong Institute of Light Industry, Jinan 250353, People's Republic of China
^*Correspondence e-mail: tanxuejie@163.com

(Received 19 January 2012; accepted 22 February 2012; online 29 February 2012)

In the crystal of the title compound, C₁₀H₁₁NO₄, the hydroxy group forms an O—H⋯O_carbonyl hydrogen bond with an adjacent molecule, so forming chains which extend along (010). Further weak C—H⋯O hydrogen-bonding associations give an infinite three-dimensional network structure.

Related literature

For the first description of the title compound, see: Zhou & Chen (2000 ). For the synthesis of the title compound, see: Gramlich et al. (2010 ); William et al. (2008 ). For a molecular topology description, see: Braga & Grepioni (2007 ).

Experimental

Crystal data

C₁₀H₁₁NO₄
M_r = 209.20
Monoclinic, P c
a = 5.4619 (12) Å
b = 6.8337 (15) Å
c = 12.546 (3) Å
β = 92.047 (3)°
V = 467.97 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 K
0.32 × 0.27 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.964, T_max = 0.986
2628 measured reflections
1017 independent reflections
999 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.102
S = 1.05
1017 reflections
141 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H11⋯O3ⁱ	0.92 (6)	1.99 (6)	2.902 (3)	171 (5)
C2—H2⋯O3ⁱⁱ	0.98	2.40	3.338 (3)	160
C1—H1⋯O4ⁱⁱⁱ	0.98	2.44	3.216 (3)	136
Symmetry codes: (i) x, y+1, z; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[x+1, -y+2, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 2000) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681200788X/zs2178sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200788X/zs2178Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681200788X/zs2178Isup3.cml

checkCIF report

Comment top

The title compound C₁₀H₁₁NO₄ (I), common name N-2-hydroxyethyl unsaturated norcantharidin (HEUNC), is a derivative of unsaturated norcantharidin, showing weaker anti-cancer activity than norcantharidin, possibly associated with its structure. However its single-crystal structure has not been unambiguously determined since first prepared in 2000 (Zhou & Chen, 2000). In the present work, the crystal structure of (I) is reported, and its molecular packing mode is discussed on the basis of its structure. The absolute configuration of (I) has not been determined.

The asymmetric unit of the title compound contains only one molecule (Fig. 1) in which the conformation of the N-substituted ethanol side chain is stabilized by intramolecular C—H···O_carbonyl interactions (Table 1) [torsion angles C7—N1—C9—C10 and N1—C9—C10—O4, -73.826 (12) and 168.812 (9)°], respectively. If the ethanol side chain is not considered, the molecule has a Z-type configuration with planes C1, C4, C5, C6 (plane 1), C1, O1, C4 (plane 2) and C2, C3, C8, N1, C7, C9, O2, O3 (plane 3) all essentially planar [dihedral angles 50.161 (8)° between planes 1 and 2 and 53.439 (7)° between planes 2 and 3].

The hydroxy group forms intermolecular O—H···O_carbonyl hydrogen bonds (Table 1) giving chains which extend along (010) (Fig. 2). Each molecule (shown as O) gives further weak C—H···O hydrogen-bonding associations with six surrounding molecules (A–F) (Fig. 2), in which molecules B, D, E, F and O are nearly co-planar, with A and C lying on either side of the plane. An overall three-dimensional network structure is formed (Fig. 3).

At first glance, the hydrogen-bonded net found in (I) may be considered distorted primitive cubic with a long vertex symbol (4.4.4.4.4.4.4.4.4.4.4.4.*.*.*.) (Braga & Grepioni, 2007) but there is a difference in connectivity along the sloping plane [Miller Index (0.74 0 0.67)] with 4-membered or 6-membered primitive rings occurring from each of the 15 (6*5/2) angles, actually giving a long vertex symbol of (4.4.4.4.4.4.4.4.6.6.6.6.6.6.6.) (Figs. 4, 5).

Related literature top

For related literature [please be more specific], see: Zhou & Chen (2000). For the synthesis of the title compound, see: Gramlich et al. (2010); William et al. (2008). For a molecular topology description, see: Braga & Grepioni (2007).

Experimental top

For the synthesis of the title compound, see: Gramlich et al. (2010); William et al. (2008). Elemental analysis: Calcd: C 57.41; H 5.30; N 6.70%. Found: C 57.35; H 5.23; N 6.76%.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 2000) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I) with atom numbering scheme with thermal ellipsoids drawn at the 30% probability level.
	Fig. 2. Hydrogen bonding (shown as dashed lines) in the crystal structure of (I) viewed along the a axis.
	Fig. 3. Portion of the infinite three-dimensional packing diagram of (I) viewed down the b axis.
	Fig. 4. The (4.4.4.4.4.4.4.4.6.6.6.6.6.6.6.) topological diagram of (I) through abstracting every HEUNC molecule into one dummy atom viewed along the b axis.
	Fig. 5. A sub-unit of the topology diagram from Fig. 4, showing ring generation from each angle intersection.

exo,exo-4-(2-Hydroxyethyl)-10-oxa-4- azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione top

Crystal data top

C₁₀H₁₁NO₄	F(000) = 220
M_r = 209.20	D_x = 1.485 Mg m⁻³
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 380 reflections
a = 5.4619 (12) Å	θ = 2.5–28.1°
b = 6.8337 (15) Å	µ = 0.12 mm⁻¹
c = 12.546 (3) Å	T = 298 K
β = 92.047 (3)°	Block, colourless
V = 467.97 (18) Å³	0.32 × 0.27 × 0.12 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	1017 independent reflections
Radiation source: fine-focus sealed tube	999 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ϕ and ω scans	θ_max = 27.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −6→6
T_min = 0.964, T_max = 0.986	k = −8→6
2628 measured reflections	l = −15→16

Refinement top

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0815P)² + 0.0262P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1017 reflections	Δρ_max = 0.21 e Å⁻³
141 parameters	Δρ_min = −0.25 e Å⁻³
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.049 (13)

Crystal data top

C₁₀H₁₁NO₄	V = 467.97 (18) Å³
M_r = 209.20	Z = 2
Monoclinic, Pc	Mo Kα radiation
a = 5.4619 (12) Å	µ = 0.12 mm⁻¹
b = 6.8337 (15) Å	T = 298 K
c = 12.546 (3) Å	0.32 × 0.27 × 0.12 mm
β = 92.047 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1017 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	999 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.986	R_int = 0.015
2628 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	2 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.21 e Å⁻³
1017 reflections	Δρ_min = −0.25 e Å⁻³
141 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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) top

	x	y	z	U_iso*/U_eq
C1	0.5015 (4)	0.6269 (3)	0.0567 (2)	0.0398 (5)
H1	0.5792	0.7501	0.0365	0.048*
C2	0.2181 (4)	0.6363 (3)	0.06828 (17)	0.0315 (4)
H2	0.1262	0.6354	−0.0002	0.038*
C3	0.1740 (3)	0.4531 (3)	0.13644 (16)	0.0278 (4)
H3	0.0604	0.3600	0.1017	0.033*
C4	0.4403 (4)	0.3711 (3)	0.15055 (18)	0.0343 (5)
H4	0.4673	0.2790	0.2097	0.041*
C5	0.5103 (4)	0.2973 (3)	0.0421 (2)	0.0398 (5)
H5	0.5239	0.1676	0.0207	0.048*
C6	0.5483 (5)	0.4548 (3)	−0.0159 (2)	0.0437 (6)
H6	0.5941	0.4592	−0.0866	0.052*
C7	0.1541 (4)	0.8058 (3)	0.13860 (18)	0.0343 (4)
C8	0.0818 (4)	0.5321 (3)	0.24029 (17)	0.0293 (4)
C9	0.0159 (5)	0.8636 (3)	0.3226 (2)	0.0397 (5)
H7	0.1373	0.9666	0.3310	0.048*
H8	0.0135	0.7907	0.3889	0.048*
C10	−0.2353 (5)	0.9541 (3)	0.2993 (2)	0.0431 (6)
H9	−0.2430	1.0045	0.2270	0.052*
H10	−0.3604	0.8542	0.3048	0.052*
N1	0.0834 (3)	0.7331 (2)	0.23622 (15)	0.0321 (4)
O1	0.5762 (3)	0.5517 (2)	0.15900 (16)	0.0415 (4)
O2	0.1665 (5)	0.9769 (3)	0.1182 (2)	0.0589 (6)
O3	0.0215 (3)	0.4379 (3)	0.31657 (15)	0.0429 (4)
O4	−0.2821 (4)	1.1065 (3)	0.37087 (18)	0.0548 (5)
H11	−0.181 (10)	1.203 (8)	0.347 (5)	0.099 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0380 (12)	0.0327 (12)	0.0499 (13)	−0.0054 (8)	0.0163 (9)	−0.0014 (9)
C2	0.0376 (11)	0.0285 (10)	0.0285 (9)	0.0026 (7)	0.0043 (8)	0.0035 (8)
C3	0.0282 (9)	0.0255 (10)	0.0297 (10)	−0.0006 (7)	0.0026 (7)	−0.0006 (8)
C4	0.0352 (11)	0.0303 (10)	0.0376 (11)	0.0063 (8)	0.0026 (8)	0.0019 (8)
C5	0.0375 (11)	0.0338 (11)	0.0490 (13)	0.0053 (8)	0.0118 (9)	−0.0055 (10)
C6	0.0436 (12)	0.0421 (13)	0.0466 (13)	0.0023 (10)	0.0194 (10)	−0.0026 (11)
C7	0.0361 (9)	0.0291 (10)	0.0383 (11)	0.0017 (8)	0.0075 (8)	0.0023 (9)
C8	0.0276 (8)	0.0287 (9)	0.0315 (10)	0.0022 (7)	0.0011 (6)	−0.0008 (8)
C9	0.0433 (12)	0.0393 (12)	0.0368 (10)	0.0052 (9)	0.0034 (9)	−0.0079 (9)
C10	0.0461 (13)	0.0374 (11)	0.0463 (13)	0.0080 (10)	0.0069 (10)	−0.0047 (9)
N1	0.0342 (8)	0.0286 (8)	0.0338 (9)	0.0027 (7)	0.0056 (6)	−0.0010 (7)
O1	0.0295 (7)	0.0440 (9)	0.0509 (9)	−0.0032 (7)	−0.0010 (6)	−0.0090 (7)
O2	0.0812 (14)	0.0283 (9)	0.0692 (13)	0.0041 (9)	0.0316 (11)	0.0073 (9)
O3	0.0528 (10)	0.0418 (8)	0.0348 (8)	0.0032 (8)	0.0120 (6)	0.0078 (7)
O4	0.0668 (12)	0.0420 (10)	0.0569 (12)	0.0086 (9)	0.0218 (10)	−0.0096 (9)

Geometric parameters (Å, º) top

C1—O1	1.429 (3)	C5—H5	0.93
C1—C6	1.515 (3)	C6—H6	0.93
C1—C2	1.561 (3)	C7—O2	1.200 (3)
C1—H1	0.98	C7—N1	1.389 (3)
C2—C7	1.505 (3)	C8—O3	1.209 (3)
C2—C3	1.540 (3)	C8—N1	1.375 (3)
C2—H2	0.98	C9—N1	1.461 (3)
C3—C8	1.513 (3)	C9—C10	1.524 (4)
C3—C4	1.563 (3)	C9—H7	0.97
C3—H3	0.98	C9—H8	0.97
C4—O1	1.443 (3)	C10—O4	1.404 (3)
C4—C5	1.513 (3)	C10—H9	0.97
C4—H4	0.98	C10—H10	0.97
C5—C6	1.320 (4)	O4—H11	0.92 (6)

O1—C1—C6	102.24 (19)	C5—C6—C1	105.6 (2)
O1—C1—C2	100.56 (16)	C5—C6—H6	127.2
C6—C1—C2	106.08 (19)	C1—C6—H6	127.2
O1—C1—H1	115.4	O2—C7—N1	123.8 (2)
C6—C1—H1	115.4	O2—C7—C2	127.5 (2)
C2—C1—H1	115.4	N1—C7—C2	108.64 (18)
C7—C2—C3	104.83 (17)	O3—C8—N1	124.3 (2)
C7—C2—C1	109.78 (18)	O3—C8—C3	126.88 (18)
C3—C2—C1	101.17 (16)	N1—C8—C3	108.78 (17)
C7—C2—H2	113.4	N1—C9—C10	110.8 (2)
C3—C2—H2	113.4	N1—C9—H7	109.5
C1—C2—H2	113.4	C10—C9—H7	109.5
C8—C3—C2	104.57 (16)	N1—C9—H8	109.5
C8—C3—C4	111.56 (16)	C10—C9—H8	109.5
C2—C3—C4	101.02 (15)	H7—C9—H8	108.1
C8—C3—H3	112.9	O4—C10—C9	111.2 (2)
C2—C3—H3	112.9	O4—C10—H9	109.4
C4—C3—H3	112.9	C9—C10—H9	109.4
O1—C4—C5	101.84 (18)	O4—C10—H10	109.4
O1—C4—C3	100.13 (15)	C9—C10—H10	109.4
C5—C4—C3	106.37 (17)	H9—C10—H10	108.0
O1—C4—H4	115.5	C8—N1—C7	113.09 (18)
C5—C4—H4	115.5	C8—N1—C9	125.48 (19)
C3—C4—H4	115.5	C7—N1—C9	121.42 (18)
C6—C5—C4	105.9 (2)	C1—O1—C4	96.43 (16)
C6—C5—H5	127.0	C10—O4—H11	102 (3)
C4—C5—H5	127.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H11···O3ⁱ	0.92 (6)	1.99 (6)	2.902 (3)	171 (5)
C2—H2···O3ⁱⁱ	0.98	2.40	3.338 (3)	160
C1—H1···O4ⁱⁱⁱ	0.98	2.44	3.216 (3)	136
C9—H8···O3	0.97	2.58	2.911 (3)	100
C10—H9···O2	0.97	2.67	3.219 (3)	116

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁NO₄
M_r	209.20
Crystal system, space group	Monoclinic, Pc
Temperature (K)	298
a, b, c (Å)	5.4619 (12), 6.8337 (15), 12.546 (3)
β (°)	92.047 (3)
V (Å³)	467.97 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.32 × 0.27 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.964, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	2628, 1017, 999
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.102, 1.05
No. of reflections	1017
No. of parameters	141
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.25

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 2000) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H11···O3ⁱ	0.92 (6)	1.99 (6)	2.902 (3)	171 (5)
C2—H2···O3ⁱⁱ	0.98	2.40	3.338 (3)	159.7
C1—H1···O4ⁱⁱⁱ	0.98	2.44	3.216 (3)	135.6

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

Acknowledgements

This work is supported by the Science and Technology Development Project of Shandong Province in China (grant No. 2011GGB01164), The National Natural Science Foundation of China (NSFC, grant No. 21103100), and the Natural Science Foundation of Shandong Province in China (grant No. ZR2009BM040).

References

Braga, D. & Grepioni, F. (2007). Making Crystals by Design: Methods, Techniques and Applications, p. 65. Weinheim: Wiley-VCH. Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gramlich, W. M., Robertson, M. L. & Hillmyer, M. A. (2010). Macromolecules, 43, 2313–2321. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
William, H. H., Frank, P., Jacob, R. A., Brian, K. L., Jerred, C., Thomas, W. H., Shelley, Z., Matthew, J. T., Jeffery, L. W. & Willson, C. G. (2008). Macromolecules, 41, 719–726. Google Scholar
Zhou, Zh. H. & Chen, R. Y. (2000). Synth. Commun. 30, 3527–3533. Web of Science CrossRef CAS Google Scholar

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exo,exo-4-(2-Hy­dr­oxy­eth­yl)-10-oxa-4-aza­tri­cyclo­[5.2.1.02,6]dec-8-ene-3,5-dione

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

exo,exo-4-(2-Hydroxyethyl)-10-oxa-4-azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione