exo-4-[(1H-Benzimidazol-2-yl)meth-yl]-10-oxa-4-aza-tricyclo-[5.2.1.0]decane-3,5-dione.

In the title compound, C(16)H(15)N(3)O(3), the dihedral angle between the approximately planar benzimidazolyl group (r.m.s. deviation = 0.010 Å) and the pyrrolidine ring is 78.20 (6)°. The C-C-N bond angle of the bridging CH(2) group is 112.14 (16)°. In the crystal, mol-ecules are linked via N-H⋯N hydrogen bonds, forming infinite chains parallel to [101] and [10[Formula: see text]].

Related literature

For the bioactivity of norcantharidin (systematic name 4,10-dioxatricyclo­[5.2.1.02,6]decane-3,5-dione), see: Wang (1989 ▶). For the use of norcantharidin in synthesis, see: Hill et al. (2007 ▶). For a related structure, see: Zhu & Lin (2009 ▶).

Experimental

Crystal data

C16H15N3O3

M = 297.31

Orthorhombic,

a = 17.4294 (2) Å

b = 48.2746 (6) Å

c = 6.7947 (1) Å

V = 5717.04 (13) Å3

Z = 16

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

0.24 × 0.17 × 0.10 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.981, T max = 0.990

22741 measured reflections

2159 independent reflections

1690 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.087

S = 1.04

2159 reflections

199 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.10 e Å−3

Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811026602/qk2008sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811026602/qk2008Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811026602/qk2008Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H15N3O3	F(000) = 2496
Mr = 297.31	Dx = 1.382 Mg m−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 5637 reflections
a = 17.4294 (2) Å	θ = 2.5–29.8°
b = 48.2746 (6) Å	µ = 0.10 mm−1
c = 6.7947 (1) Å	T = 296 K
V = 5717.04 (13) Å3	Block, colourless
Z = 16	0.24 × 0.17 × 0.10 mm

Bruker SMART APEXII CCD diffractometer	2159 independent reflections
Radiation source: fine-focus sealed tube	1690 reflections with I > 2σ(I)
graphite	Rint = 0.038
ω scans	θmax = 29.8°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→24
Tmin = 0.981, Tmax = 0.990	k = −67→66
22741 measured reflections	l = −9→8

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)] = 0.035	H-atom parameters constrained
wR(F2) = 0.087	w = 1/[σ2(Fo2) + (0.0448P)2 + 1.1097P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2159 reflections	Δρmax = 0.10 e Å−3
199 parameters	Δρmin = −0.17 e Å−3
1 restraint	Absolute structure: 1753 Friedel pairs were merged
Primary atom site location: structure-invariant direct methods

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.

	x	y	z	Uiso*/Ueq
N2	−0.06276 (8)	0.10833 (3)	0.2792 (3)	0.0454 (4)
N1	0.04528 (8)	0.11596 (3)	0.4450 (3)	0.0428 (4)
H1A	0.0893	0.1229	0.4740	0.051*
N3	−0.02809 (8)	0.16452 (3)	0.1037 (3)	0.0431 (4)
O2	−0.07386 (9)	0.14915 (3)	−0.1930 (3)	0.0629 (4)
O1	−0.00312 (11)	0.18963 (4)	0.3811 (3)	0.0765 (5)
O3	−0.02560 (7)	0.22474 (3)	−0.0973 (2)	0.0556 (4)
C1	−0.07375 (10)	0.16595 (3)	−0.0624 (3)	0.0439 (4)
C2	−0.12089 (10)	0.19215 (3)	−0.0513 (3)	0.0431 (4)
H2B	−0.1761	0.1887	−0.0634	0.052*
C3	−0.09207 (12)	0.21403 (4)	−0.1970 (3)	0.0527 (5)
H3A	−0.0813	0.2068	−0.3288	0.063*
C4	−0.14630 (14)	0.23883 (4)	−0.1956 (5)	0.0713 (7)
H4A	−0.1995	0.2330	−0.2016	0.086*
H4B	−0.1357	0.2513	−0.3041	0.086*
C5	−0.12741 (14)	0.25219 (4)	0.0024 (4)	0.0700 (7)
H5A	−0.1088	0.2710	−0.0139	0.084*
H5B	−0.1716	0.2523	0.0892	0.084*
C6	−0.06469 (12)	0.23307 (4)	0.0784 (4)	0.0552 (5)
H6A	−0.0311	0.2417	0.1763	0.066*
C7	−0.09930 (11)	0.20533 (4)	0.1463 (3)	0.0464 (5)
H7A	−0.1434	0.2077	0.2341	0.056*
C8	−0.03878 (12)	0.18644 (4)	0.2306 (3)	0.0492 (5)
C16	0.02831 (10)	0.14281 (4)	0.1375 (4)	0.0519 (5)
H16A	0.0760	0.1511	0.1814	0.062*
H16B	0.0384	0.1333	0.0145	0.062*
C15	0.00198 (10)	0.12236 (3)	0.2871 (3)	0.0410 (4)
C9	−0.06167 (9)	0.09153 (3)	0.4452 (3)	0.0391 (4)
C10	−0.11496 (11)	0.07221 (4)	0.5106 (3)	0.0488 (5)
H10A	−0.1597	0.0687	0.4402	0.059*
C11	−0.09925 (12)	0.05847 (4)	0.6828 (4)	0.0571 (5)
H11A	−0.1339	0.0453	0.7288	0.068*
C12	−0.03280 (13)	0.06372 (5)	0.7903 (4)	0.0600 (6)
H12A	−0.0247	0.0543	0.9078	0.072*
C13	0.02144 (11)	0.08263 (4)	0.7270 (3)	0.0526 (5)
H13A	0.0660	0.0861	0.7984	0.063*
C14	0.00597 (10)	0.09617 (3)	0.5518 (3)	0.0395 (4)

	U11	U22	U33	U12	U13	U23
N2	0.0332 (7)	0.0520 (8)	0.0510 (10)	−0.0018 (6)	−0.0111 (7)	0.0068 (8)
N1	0.0308 (7)	0.0445 (7)	0.0532 (10)	−0.0010 (6)	−0.0124 (8)	−0.0003 (7)
N3	0.0394 (8)	0.0408 (7)	0.0490 (10)	0.0022 (6)	−0.0058 (7)	0.0065 (7)
O2	0.0768 (10)	0.0467 (7)	0.0652 (11)	0.0086 (7)	−0.0172 (9)	−0.0142 (8)
O1	0.0876 (11)	0.0950 (13)	0.0468 (11)	0.0081 (9)	−0.0214 (10)	−0.0072 (9)
O3	0.0472 (7)	0.0489 (7)	0.0708 (11)	−0.0026 (6)	0.0051 (8)	0.0100 (7)
C1	0.0451 (9)	0.0351 (8)	0.0514 (12)	−0.0021 (7)	−0.0074 (9)	0.0015 (8)
C2	0.0380 (9)	0.0387 (8)	0.0525 (11)	0.0014 (7)	−0.0062 (9)	−0.0002 (8)
C3	0.0624 (12)	0.0469 (10)	0.0489 (13)	0.0087 (9)	−0.0070 (11)	0.0047 (9)
C4	0.0740 (15)	0.0457 (10)	0.094 (2)	0.0098 (10)	−0.0194 (15)	0.0099 (13)
C5	0.0703 (13)	0.0407 (9)	0.099 (2)	0.0100 (10)	0.0017 (15)	−0.0043 (12)
C6	0.0576 (12)	0.0427 (9)	0.0654 (15)	−0.0041 (8)	−0.0085 (11)	−0.0086 (10)
C7	0.0447 (10)	0.0481 (9)	0.0466 (12)	0.0029 (8)	0.0035 (9)	−0.0034 (9)
C8	0.0493 (11)	0.0568 (11)	0.0414 (12)	−0.0011 (9)	−0.0015 (10)	0.0022 (9)
C16	0.0386 (9)	0.0511 (10)	0.0660 (15)	0.0073 (8)	−0.0002 (10)	0.0147 (10)
C15	0.0324 (8)	0.0416 (8)	0.0490 (12)	0.0040 (7)	−0.0080 (8)	0.0041 (8)
C9	0.0334 (8)	0.0393 (8)	0.0444 (11)	0.0033 (6)	−0.0079 (8)	−0.0022 (8)
C10	0.0394 (9)	0.0502 (10)	0.0570 (14)	−0.0041 (8)	−0.0060 (9)	−0.0017 (9)
C11	0.0535 (11)	0.0506 (10)	0.0671 (15)	−0.0001 (8)	0.0027 (12)	0.0114 (11)
C12	0.0610 (12)	0.0633 (12)	0.0558 (14)	0.0089 (10)	−0.0030 (11)	0.0175 (11)
C13	0.0470 (11)	0.0628 (11)	0.0480 (12)	0.0076 (9)	−0.0156 (10)	0.0025 (10)
C14	0.0333 (8)	0.0388 (8)	0.0463 (12)	0.0042 (7)	−0.0079 (8)	−0.0021 (8)

N2—C15	1.317 (2)	C5—C6	1.521 (3)
N2—C9	1.389 (2)	C5—H5A	0.9700
N1—C15	1.348 (3)	C5—H5B	0.9700
N1—C14	1.381 (2)	C6—C7	1.540 (3)
N1—H1A	0.8600	C6—H6A	0.9800
N3—C8	1.378 (3)	C7—C8	1.507 (3)
N3—C1	1.383 (3)	C7—H7A	0.9800
N3—C16	1.455 (2)	C16—C15	1.490 (3)
O2—C1	1.202 (2)	C16—H16A	0.9700
O1—C8	1.206 (3)	C16—H16B	0.9700
O3—C6	1.432 (3)	C9—C10	1.389 (3)
O3—C3	1.438 (3)	C9—C14	1.402 (2)
C1—C2	1.510 (2)	C10—C11	1.373 (3)
C2—C3	1.532 (3)	C10—H10A	0.9300
C2—C7	1.533 (3)	C11—C12	1.393 (3)
C2—H2B	0.9800	C11—H11A	0.9300
C3—C4	1.525 (3)	C12—C13	1.383 (3)
C3—H3A	0.9800	C12—H12A	0.9300
C4—C5	1.528 (4)	C13—C14	1.385 (3)
C4—H4A	0.9700	C13—H13A	0.9300
C4—H4B	0.9700
C15—N2—C9	104.80 (15)	C5—C6—H6A	113.7
C15—N1—C14	107.39 (14)	C7—C6—H6A	113.7
C15—N1—H1A	126.3	C8—C7—C2	104.70 (15)
C14—N1—H1A	126.3	C8—C7—C6	111.46 (16)
C8—N3—C1	113.23 (15)	C2—C7—C6	101.23 (17)
C8—N3—C16	123.08 (17)	C8—C7—H7A	112.9
C1—N3—C16	123.63 (17)	C2—C7—H7A	112.9
C6—O3—C3	96.35 (15)	C6—C7—H7A	112.9
O2—C1—N3	124.71 (16)	O1—C8—N3	124.0 (2)
O2—C1—C2	126.96 (19)	O1—C8—C7	127.3 (2)
N3—C1—C2	108.33 (16)	N3—C8—C7	108.75 (17)
C1—C2—C3	111.50 (17)	N3—C16—C15	112.14 (16)
C1—C2—C7	104.94 (16)	N3—C16—H16A	109.2
C3—C2—C7	101.50 (14)	C15—C16—H16A	109.2
C1—C2—H2B	112.7	N3—C16—H16B	109.2
C3—C2—H2B	112.7	C15—C16—H16B	109.2
C7—C2—H2B	112.7	H16A—C16—H16B	107.9
O3—C3—C4	102.38 (16)	N2—C15—N1	113.22 (17)
O3—C3—C2	101.96 (16)	N2—C15—C16	125.23 (18)
C4—C3—C2	109.49 (19)	N1—C15—C16	121.52 (16)
O3—C3—H3A	113.9	C10—C9—N2	129.97 (16)
C4—C3—H3A	113.9	C10—C9—C14	120.28 (17)
C2—C3—H3A	113.9	N2—C9—C14	109.74 (15)
C3—C4—C5	101.72 (19)	C11—C10—C9	117.63 (18)
C3—C4—H4A	111.4	C11—C10—H10A	121.2
C5—C4—H4A	111.4	C9—C10—H10A	121.2
C3—C4—H4B	111.4	C10—C11—C12	121.7 (2)
C5—C4—H4B	111.4	C10—C11—H11A	119.2
H4A—C4—H4B	109.3	C12—C11—H11A	119.2
C6—C5—C4	101.42 (18)	C13—C12—C11	121.7 (2)
C6—C5—H5A	111.5	C13—C12—H12A	119.1
C4—C5—H5A	111.5	C11—C12—H12A	119.1
C6—C5—H5B	111.5	C12—C13—C14	116.48 (19)
C4—C5—H5B	111.5	C12—C13—H13A	121.8
H5A—C5—H5B	109.3	C14—C13—H13A	121.8
O3—C6—C5	103.2 (2)	N1—C14—C13	132.96 (17)
O3—C6—C7	101.06 (15)	N1—C14—C9	104.84 (16)
C5—C6—C7	110.35 (16)	C13—C14—C9	122.19 (18)
O3—C6—H6A	113.7
C8—N3—C1—O2	179.8 (2)	C16—N3—C8—O1	−0.5 (3)
C16—N3—C1—O2	2.6 (3)	C1—N3—C8—C7	0.7 (2)
C8—N3—C1—C2	0.9 (2)	C16—N3—C8—C7	177.93 (16)
C16—N3—C1—C2	−176.28 (16)	C2—C7—C8—O1	176.4 (2)
O2—C1—C2—C3	−71.9 (2)	C6—C7—C8—O1	67.8 (3)
N3—C1—C2—C3	106.99 (19)	C2—C7—C8—N3	−2.0 (2)
O2—C1—C2—C7	179.06 (19)	C6—C7—C8—N3	−110.60 (19)
N3—C1—C2—C7	−2.10 (19)	C8—N3—C16—C15	77.7 (2)
C6—O3—C3—C4	55.9 (2)	C1—N3—C16—C15	−105.4 (2)
C6—O3—C3—C2	−57.41 (16)	C9—N2—C15—N1	0.1 (2)
C1—C2—C3—O3	−77.96 (19)	C9—N2—C15—C16	178.43 (18)
C7—C2—C3—O3	33.32 (17)	C14—N1—C15—N2	−0.4 (2)
C1—C2—C3—C4	174.13 (18)	C14—N1—C15—C16	−178.74 (17)
C7—C2—C3—C4	−74.6 (2)	N3—C16—C15—N2	55.2 (3)
O3—C3—C4—C5	−35.0 (2)	N3—C16—C15—N1	−126.70 (19)
C2—C3—C4—C5	72.7 (2)	C15—N2—C9—C10	−179.28 (19)
C3—C4—C5—C6	1.0 (2)	C15—N2—C9—C14	0.14 (19)
C3—O3—C6—C5	−55.61 (16)	N2—C9—C10—C11	−179.60 (19)
C3—O3—C6—C7	58.61 (15)	C14—C9—C10—C11	1.0 (3)
C4—C5—C6—O3	33.5 (2)	C9—C10—C11—C12	0.6 (3)
C4—C5—C6—C7	−73.8 (2)	C10—C11—C12—C13	−1.3 (4)
C1—C2—C7—C8	2.40 (19)	C11—C12—C13—C14	0.4 (3)
C3—C2—C7—C8	−113.79 (16)	C15—N1—C14—C13	−178.2 (2)
C1—C2—C7—C6	118.36 (16)	C15—N1—C14—C9	0.44 (19)
C3—C2—C7—C6	2.16 (17)	C12—C13—C14—N1	179.8 (2)
O3—C6—C7—C8	73.7 (2)	C12—C13—C14—C9	1.3 (3)
C5—C6—C7—C8	−177.5 (2)	C10—C9—C14—N1	179.13 (16)
O3—C6—C7—C2	−37.14 (17)	N2—C9—C14—N1	−0.36 (19)
C5—C6—C7—C2	71.6 (2)	C10—C9—C14—C13	−2.0 (3)
C1—N3—C8—O1	−177.7 (2)	N2—C9—C14—C13	178.48 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2i	0.86	1.97	2.827 (2)	175

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2i	0.86	1.97	2.827 (2)	175

Symmetry code: (i) .