8-Phenyl-10-oxa-8-aza­tricyclo­[4.3.0.12,5]decane-7,9-dione

Zhu, W.-Z.; Lin, Q.-Y.

doi:10.1107/S1600536809000282

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o287

doi:10.1107/S1600536809000282

Open

access

8-Phenyl-10-oxa-8-azatricyclo[4.3.0.1^2,5]decane-7,9-dione

Wen-Zhong Zhu ^a and Qiu-Yue Lin ^a ^*

^aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China, and, College of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004, Zhejiang, People's Republic of China
^*Correspondence e-mail: sky51@zjnu.cn

(Received 25 December 2008; accepted 5 January 2009; online 10 January 2009)

The reaction of aniline with norcantharidin produced the imide title compound, C₁₄H₁₃NO₃, which shows no significant hydrogen bonds in the crystal structure. The dihedral angle between the phenyl and pyrrolidine rings is 48.48 (6)°.

Related literature

For the use of norcantharidin in synthesis see: Hill et al. (2007 ). For background, see: Wang (1989 ).

Experimental

Crystal data

C₁₄H₁₃NO₃
M_r = 243.25
Monoclinic, P 2₁ /c
a = 9.5914 (4) Å
b = 8.4345 (3) Å
c = 14.4101 (6) Å
β = 93.468 (3)°
V = 1163.62 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 (2) K
0.32 × 0.25 × 0.04 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.971, T_max = 0.996
18085 measured reflections
2699 independent reflections
1898 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.177
S = 0.61
2699 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯O2ⁱ	0.97	2.59	3.502 (3)	156
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809000282/at2701sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809000282/at2701Isup2.hkl

checkCIF report

Comment top

Norcantharidin are a variety of pharmacologically important compounds such as protein kinase inhibitors and antitumor properties (Wang, 1989). We have designed, synthesized and crystallized several norcantharidin derivatives to study their anticancer properties. In order to study on the relationship between the activity of norcantharidin and the importance of aromatic ring linked to the carboxyl, the norcantharidin derivative was synthesized and its crystal structure is reported here.

X-ray crystallography confirmed the molecular structure and the atom connectivity for the title compound, as illustrated in Fig. 1. In the compound, the dihedral angle between the mean planes of pyrrolidine (C7/C8/C13/C14/N1) rings and the phenyl (C1—C6) is 48.48 (6)°. It exhibits no unusual crystal packing features, and each molecule acts as a donor and acceptor for one C10—H10B···O2 weak intermolecular hydrogen bonds.

Related literature top

For the use of norcantharidin in synthesis see: Hill et al. (2007). For background, see: Wang (1989).

Experimental top

The title compound was synthesized by the condensation of norcantharidin (1 mmol) with aniline (1 mmol) in DMF (10 mL). After refluxing for 3 h, the reaction mixture was left to stand for two weeks, colourless crystals were isolated.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the molecule of (I) showing the atom-labelling scheme with displacement ellipsoids drawn at the 30% probability.

8-Phenyl-10-oxa-8-azatricyclo[4.3.0.1^2,5]decane-7,9-dione top

Crystal data top

C₁₄H₁₃NO₃	F(000) = 512
M_r = 243.25	D_x = 1.389 Mg m⁻³ D_m = 1.389 Mg m⁻³ D_m measured by not measured
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3324 reflections
a = 9.5914 (4) Å	θ = 2.1–27.7°
b = 8.4345 (3) Å	µ = 0.10 mm⁻¹
c = 14.4101 (6) Å	T = 296 K
β = 93.468 (3)°	Sheet, colourless
V = 1163.62 (8) Å³	0.32 × 0.25 × 0.04 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2699 independent reflections
Radiation source: fine-focus sealed tube	1898 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 27.7°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.971, T_max = 0.996	k = −11→10
18085 measured reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.177	H-atom parameters constrained
S = 0.61	w = 1/[σ²(F_o²) + (0.1908P)² + 0.6671P] where P = (F_o² + 2F_c²)/3
2699 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₄H₁₃NO₃	V = 1163.62 (8) Å³
M_r = 243.25	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.5914 (4) Å	µ = 0.10 mm⁻¹
b = 8.4345 (3) Å	T = 296 K
c = 14.4101 (6) Å	0.32 × 0.25 × 0.04 mm
β = 93.468 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2699 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1898 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.996	R_int = 0.041
18085 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.177	H-atom parameters constrained
S = 0.61	Δρ_max = 0.16 e Å⁻³
2699 reflections	Δρ_min = −0.17 e Å⁻³
163 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
N1	0.10268 (15)	0.22038 (16)	0.69370 (9)	0.0418 (4)
O1	−0.04620 (15)	0.1156 (2)	0.79702 (10)	0.0655 (4)
O2	0.19084 (14)	0.33610 (17)	0.56481 (9)	0.0579 (4)
O3	−0.13027 (14)	0.06451 (14)	0.54810 (10)	0.0526 (4)
C1	0.32246 (19)	0.0814 (2)	0.68510 (13)	0.0513 (4)
H1A	0.3026	0.0665	0.6217	0.062*
C2	0.4439 (2)	0.0209 (3)	0.72752 (17)	0.0620 (5)
H2A	0.5055	−0.0358	0.6927	0.074*
C3	0.4743 (2)	0.0442 (3)	0.82150 (17)	0.0646 (6)
H3A	0.5562	0.0034	0.8499	0.078*
C4	0.3832 (2)	0.1278 (2)	0.87295 (15)	0.0599 (5)
H4A	0.4042	0.1435	0.9361	0.072*
C5	0.2603 (2)	0.1891 (2)	0.83178 (13)	0.0493 (4)
H5A	0.1989	0.2457	0.8668	0.059*
C6	0.23040 (18)	0.16445 (19)	0.73715 (12)	0.0421 (4)
C7	0.09220 (19)	0.29901 (19)	0.60787 (11)	0.0432 (4)
C8	−0.05956 (18)	0.32348 (19)	0.57997 (11)	0.0432 (4)
H8A	−0.0820	0.4349	0.5668	0.052*
C9	−0.1114 (2)	0.2122 (2)	0.50018 (13)	0.0502 (4)
H9A	−0.0485	0.2054	0.4492	0.060*
C10	−0.2605 (2)	0.2614 (3)	0.46982 (14)	0.0592 (5)
H10A	−0.2906	0.2148	0.4104	0.071*
H10B	−0.2696	0.3758	0.4659	0.071*
C11	−0.3429 (2)	0.1933 (2)	0.54908 (16)	0.0585 (5)
H11A	−0.3931	0.2756	0.5802	0.070*
H11B	−0.4082	0.1120	0.5267	0.070*
C12	−0.22552 (19)	0.1238 (2)	0.61262 (14)	0.0488 (4)
H12A	−0.2570	0.0432	0.6556	0.059*
C13	−0.13944 (18)	0.25713 (19)	0.66061 (11)	0.0430 (4)
H13A	−0.1973	0.3369	0.6894	0.052*
C14	−0.02839 (18)	0.1892 (2)	0.72702 (12)	0.0449 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0422 (8)	0.0437 (7)	0.0400 (7)	0.0010 (6)	0.0060 (6)	0.0082 (6)
O1	0.0549 (8)	0.0882 (11)	0.0546 (8)	0.0025 (7)	0.0131 (6)	0.0281 (7)
O2	0.0542 (8)	0.0651 (8)	0.0555 (8)	−0.0097 (6)	0.0127 (6)	0.0158 (6)
O3	0.0538 (7)	0.0369 (6)	0.0678 (8)	0.0025 (5)	0.0099 (6)	−0.0059 (5)
C1	0.0465 (10)	0.0543 (10)	0.0534 (10)	−0.0008 (8)	0.0072 (8)	−0.0011 (8)
C2	0.0440 (10)	0.0628 (12)	0.0799 (14)	0.0028 (9)	0.0097 (9)	0.0026 (10)
C3	0.0417 (10)	0.0654 (13)	0.0851 (15)	−0.0065 (9)	−0.0098 (10)	0.0115 (11)
C4	0.0588 (12)	0.0611 (12)	0.0580 (11)	−0.0136 (9)	−0.0121 (9)	0.0061 (9)
C5	0.0533 (10)	0.0465 (9)	0.0481 (9)	−0.0053 (8)	0.0025 (8)	0.0012 (7)
C6	0.0414 (8)	0.0397 (8)	0.0456 (9)	−0.0038 (6)	0.0042 (7)	0.0050 (7)
C7	0.0486 (9)	0.0398 (8)	0.0415 (8)	−0.0053 (7)	0.0059 (7)	0.0044 (6)
C8	0.0490 (9)	0.0359 (8)	0.0444 (9)	−0.0014 (7)	0.0015 (7)	0.0053 (6)
C9	0.0568 (11)	0.0490 (9)	0.0450 (9)	−0.0032 (8)	0.0053 (8)	−0.0019 (7)
C10	0.0640 (13)	0.0534 (10)	0.0579 (11)	−0.0032 (9)	−0.0139 (9)	−0.0036 (9)
C11	0.0462 (10)	0.0540 (11)	0.0741 (13)	0.0006 (8)	−0.0060 (9)	−0.0081 (9)
C12	0.0434 (9)	0.0398 (8)	0.0639 (11)	−0.0005 (7)	0.0090 (8)	0.0043 (8)
C13	0.0441 (9)	0.0396 (8)	0.0459 (9)	0.0050 (7)	0.0082 (7)	0.0018 (7)
C14	0.0434 (9)	0.0472 (9)	0.0450 (9)	0.0024 (7)	0.0100 (7)	0.0044 (7)

Geometric parameters (Å, º) top

N1—C14	1.398 (2)	C5—H5A	0.9300
N1—C7	1.402 (2)	C7—C8	1.501 (2)
N1—C6	1.422 (2)	C8—C13	1.536 (2)
O1—C14	1.205 (2)	C8—C9	1.543 (2)
O2—C7	1.204 (2)	C8—H8A	0.9800
O3—C12	1.433 (2)	C9—C10	1.528 (3)
O3—C9	1.441 (2)	C9—H9A	0.9800
C1—C2	1.380 (3)	C10—C11	1.539 (3)
C1—C6	1.383 (2)	C10—H10A	0.9700
C1—H1A	0.9300	C10—H10B	0.9700
C2—C3	1.382 (3)	C11—C12	1.525 (3)
C2—H2A	0.9300	C11—H11A	0.9700
C3—C4	1.374 (3)	C11—H11B	0.9700
C3—H3A	0.9300	C12—C13	1.535 (2)
C4—C5	1.387 (3)	C12—H12A	0.9800
C4—H4A	0.9300	C13—C14	1.502 (2)
C5—C6	1.392 (3)	C13—H13A	0.9800

C14—N1—C7	111.99 (14)	O3—C9—C8	102.29 (14)
C14—N1—C6	123.71 (14)	C10—C9—C8	107.58 (15)
C7—N1—C6	124.01 (14)	O3—C9—H9A	114.2
C12—O3—C9	96.47 (12)	C10—C9—H9A	114.2
C2—C1—C6	119.77 (18)	C8—C9—H9A	114.2
C2—C1—H1A	120.1	C9—C10—C11	101.54 (15)
C6—C1—H1A	120.1	C9—C10—H10A	111.5
C1—C2—C3	120.2 (2)	C11—C10—H10A	111.5
C1—C2—H2A	119.9	C9—C10—H10B	111.5
C3—C2—H2A	119.9	C11—C10—H10B	111.5
C4—C3—C2	119.91 (19)	H10A—C10—H10B	109.3
C4—C3—H3A	120.0	C12—C11—C10	101.26 (16)
C2—C3—H3A	120.0	C12—C11—H11A	111.5
C3—C4—C5	120.8 (2)	C10—C11—H11A	111.5
C3—C4—H4A	119.6	C12—C11—H11B	111.5
C5—C4—H4A	119.6	C10—C11—H11B	111.5
C4—C5—C6	118.85 (18)	H11A—C11—H11B	109.3
C4—C5—H5A	120.6	O3—C12—C11	102.78 (16)
C6—C5—H5A	120.6	O3—C12—C13	101.63 (13)
C1—C6—C5	120.45 (17)	C11—C12—C13	110.30 (14)
C1—C6—N1	119.36 (16)	O3—C12—H12A	113.7
C5—C6—N1	120.16 (16)	C11—C12—H12A	113.7
O2—C7—N1	124.14 (17)	C13—C12—H12A	113.7
O2—C7—C8	127.30 (15)	C14—C13—C12	110.43 (14)
N1—C7—C8	108.55 (14)	C14—C13—C8	104.73 (14)
C7—C8—C13	105.51 (13)	C12—C13—C8	101.86 (13)
C7—C8—C9	112.30 (14)	C14—C13—H13A	113.0
C13—C8—C9	100.91 (14)	C12—C13—H13A	113.0
C7—C8—H8A	112.5	C8—C13—H13A	113.0
C13—C8—H8A	112.5	O1—C14—N1	124.09 (17)
C9—C8—H8A	112.5	O1—C14—C13	126.79 (16)
O3—C9—C10	103.26 (15)	N1—C14—C13	109.10 (14)

C6—C1—C2—C3	−0.6 (3)	C13—C8—C9—C10	74.97 (17)
C1—C2—C3—C4	0.1 (3)	O3—C9—C10—C11	31.94 (17)
C2—C3—C4—C5	0.2 (3)	C8—C9—C10—C11	−75.77 (17)
C3—C4—C5—C6	0.0 (3)	C9—C10—C11—C12	2.39 (18)
C2—C1—C6—C5	0.8 (3)	C9—O3—C12—C11	56.48 (16)
C2—C1—C6—N1	−177.25 (17)	C9—O3—C12—C13	−57.71 (15)
C4—C5—C6—C1	−0.6 (3)	C10—C11—C12—O3	−36.30 (17)
C4—C5—C6—N1	177.52 (16)	C10—C11—C12—C13	71.41 (18)
C14—N1—C6—C1	126.96 (18)	O3—C12—C13—C14	−74.48 (16)
C7—N1—C6—C1	−46.3 (2)	C11—C12—C13—C14	177.05 (15)
C14—N1—C6—C5	−51.1 (2)	O3—C12—C13—C8	36.33 (16)
C7—N1—C6—C5	135.62 (17)	C11—C12—C13—C8	−72.14 (17)
C14—N1—C7—O2	−178.77 (17)	C7—C8—C13—C14	−3.54 (17)
C6—N1—C7—O2	−4.8 (3)	C9—C8—C13—C14	113.50 (15)
C14—N1—C7—C8	−0.10 (19)	C7—C8—C13—C12	−118.62 (14)
C6—N1—C7—C8	173.85 (14)	C9—C8—C13—C12	−1.58 (16)
O2—C7—C8—C13	−179.03 (18)	C7—N1—C14—O1	176.01 (17)
N1—C7—C8—C13	2.35 (18)	C6—N1—C14—O1	2.0 (3)
O2—C7—C8—C9	71.9 (2)	C7—N1—C14—C13	−2.3 (2)
N1—C7—C8—C9	−106.67 (16)	C6—N1—C14—C13	−176.26 (14)
C12—O3—C9—C10	−54.79 (16)	C12—C13—C14—O1	−65.7 (2)
C12—O3—C9—C8	56.86 (16)	C8—C13—C14—O1	−174.64 (18)
C7—C8—C9—O3	78.51 (17)	C12—C13—C14—N1	112.55 (16)
C13—C8—C9—O3	−33.41 (16)	C8—C13—C14—N1	3.61 (18)
C7—C8—C9—C10	−173.12 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O2ⁱ	0.97	2.59	3.502 (3)	156

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃NO₃
M_r	243.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.5914 (4), 8.4345 (3), 14.4101 (6)
β (°)	93.468 (3)
V (Å³)	1163.62 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.32 × 0.25 × 0.04

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.971, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	18085, 2699, 1898
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.177, 0.61
No. of reflections	2699
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.17

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O2ⁱ	0.97	2.59	3.502 (3)	156

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

The authors acknowledge financial support from the Natural Science Foundation of Zhejiang Province, China (grant No. Y407301).

References

Bruker (2004). SAINT and APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hill, T. A., Stewart, S. G., Ackland, S. P., Gilbert, J., Sauer, B., Sakoff, J. A. & McCluskey, A. (2007). Bioorg. Med. Chem. 15, 6126–6134. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, G.-S. (1989). J. Ethnopharmacol. 26, 147–162. CrossRef CAS PubMed Web of Science Google Scholar