Methyl (9aR*,10S*,11R*,13aS*,13bS*)-9-oxo-6,7,9,9a,10,11-hexa-hydro-5H,13bH-11,13a-ep-oxy-pyrrolo-[2',1':3,4][1,4]diazepino[2,1-a]isoindole-10-carboxyl-ate.

The title compound, C(17)H(18)N(2)O(4), is the methyl ester of the adduct of intra-molecular Diels-Alder reaction between maleic anhydride and 1-(2-fur-yl)-2,3,4,5-tetra-hydro-1H-pyrrolo-[1,2-a][1,4]diazepine. The mol-ecule comprises a fused penta-cyclic system containing four five-membered rings (viz. pyrrole, 2-pyrrolidinone, tetra-hydro-furan and dihydro-furan) and one seven-membered ring (1,4-diazepane). The pyrrole ring is approximately planar (r.m.s. deviation = 0.003 Å) while the 2-pyrrolidinone, tetra-hydro-furan and dihydro-furan five-membered rings have the usual envelope conformations. The central seven-membered diazepane ring adopts a boat conformation. In the crystal, mol-ecules are bound by weak inter-molecular C-H⋯O hydrogen-bonding inter-actions into zigzag chains propagating in [010]. In the crystal packing, the chains are stacked along the a axis.

Related literature

For reviews on the synthesis of isoindoles, see: Jones & Chapman (1996 ▶); Donohoe (2000 ▶). For reviews on intra­molecular cyclo­addition reactions of α,β-unsaturated acid anhydrides to furfuryl­amines (IMDAF reactions), see: Vogel et al. (1999 ▶); Zubkov et al. (2005 ▶). For related compounds, see: Zubkov et al. (2009 ▶, 2010 ▶, 2011 ▶).

Experimental

Crystal data

C17H18N2O4

M = 314.33

Monoclinic,

a = 11.5817 (12) Å

b = 9.0152 (10) Å

c = 14.8607 (16) Å

β = 112.749 (2)°

V = 1430.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.969, T max = 0.979

17904 measured reflections

4167 independent reflections

3685 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.099

S = 1.00

4167 reflections

209 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811040360/aa2027sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040360/aa2027Isup2.hkl

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

C17H18N2O4	F(000) = 664
Mr = 314.33	Dx = 1.459 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7472 reflections
a = 11.5817 (12) Å	θ = 2.7–32.6°
b = 9.0152 (10) Å	µ = 0.11 mm−1
c = 14.8607 (16) Å	T = 100 K
β = 112.749 (2)°	Prism, colourless
V = 1430.9 (3) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Bruker APEXII CCD diffractometer	4167 independent reflections
Radiation source: fine-focus sealed tube	3685 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 30.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −16→16
Tmin = 0.969, Tmax = 0.979	k = −12→12
17904 measured reflections	l = −20→20

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0545P)2 + 0.545P] where P = (Fo2 + 2Fc2)/3
4167 reflections	(Δ/σ)max < 0.001
209 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Experimental. IR (KBr), ν (cm-1): 3406, 1737, 1690; 1H NMR (CDCl3, 600 MHz, 300 K): δ = 1.83 (m, 1H, H6A), 2.16 (m, 1H, H6B), 2.78 (d, 1H, H9A, J9A,10 = 8.9), 2.84 (ddd, 1H, H6, J7B,6B = 6.9, J7B,6A = 10.6, J7,7 = 17.9), 2.91 (d, 1H, H10, J9A,10 = 8.9), 3.79 (s, 3H, CO2Me), 3.81 (ddd, 1H, H5B, J5B,6A = 5.8, J5B,6B = 8.3, J5,5 = 14.2), 4.02 (br. dd, 1H, H5A, J5A,6 = 8.3, J5,5 = 14.2), 4.55 (ddd, 1H, H7A, J7A,6A = 5.1, J7A,6B = 12.7, J7,7 = 17.9), 5.12 (d, 1H, H11, J11,12 = 1.7), 5.47 (s, 1H, H13B), 6.06 (dd, 1H, H2, J2,3 = 2.2, J1,2 = 3.4), 6.17 (dd, 1H, H1, J1,3 = 1.7, J1,2 = 3.4), 6.40 (dd, 1H, H12, J11,12 = 1.7, J12,13 = 5.8), 6.55 (dd, 1H, H3, J1,3 = 1.7, J2,3 = 2.2), 6.59 (d, 1H, H13, J12,13 = 5.8). EI—MS (70 eV) m/z (rel. intensity): 300 [M]+ (84), 282 (5), 271 (15), 254 (73), 237 (20), 225 (66), 211 (12), 202 (100), 187 (26), 172 (19), 158 (6), 144 (6), 135 (31), 106 (33), 98 (30), 91 (23), 79 (65), 54 (60), 43 (55). Anal. Calcd for C17H18N2O4: C, 64.96; H, 5.77; N, 8.91. Found: C, 64.88; H, 5.53; N, 8.66.

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; 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
O1	0.21252 (7)	0.13743 (9)	0.19684 (5)	0.01893 (16)
O2	0.12840 (7)	0.15880 (8)	−0.04077 (6)	0.01879 (15)
O3	0.00054 (7)	0.29911 (8)	0.00561 (6)	0.01676 (15)
C1	0.72407 (9)	0.21971 (11)	0.19832 (7)	0.01507 (18)
H1	0.7658	0.3084	0.2280	0.018*
C2	0.77184 (9)	0.10722 (12)	0.15513 (7)	0.01717 (19)
H2	0.8510	0.1073	0.1498	0.021*
C3	0.68230 (9)	−0.00134 (11)	0.12259 (7)	0.01630 (19)
H3	0.6892	−0.0906	0.0911	0.020*
N4	0.58103 (8)	0.04029 (9)	0.14314 (6)	0.01360 (16)
C5	0.46763 (9)	−0.04890 (11)	0.12104 (7)	0.01633 (18)
H5A	0.4717	−0.1360	0.0818	0.020*
H5B	0.3940	0.0110	0.0811	0.020*
C6	0.44989 (9)	−0.10258 (11)	0.21236 (7)	0.01676 (19)
H6A	0.5128	−0.1802	0.2446	0.020*
H6B	0.3658	−0.1479	0.1930	0.020*
C7	0.46293 (9)	0.02321 (11)	0.28511 (7)	0.01455 (18)
H7A	0.4117	−0.0004	0.3233	0.017*
H7B	0.5514	0.0302	0.3312	0.017*
N8	0.42359 (7)	0.16558 (9)	0.23701 (6)	0.01275 (15)
C9	0.30159 (9)	0.20771 (10)	0.19421 (7)	0.01331 (17)
C9A	0.29876 (8)	0.35968 (10)	0.14869 (7)	0.01202 (17)
H9A	0.2956	0.4404	0.1939	0.014*
C10	0.20435 (8)	0.39060 (10)	0.04251 (7)	0.01249 (17)
H10	0.1606	0.4872	0.0393	0.015*
C11	0.29855 (8)	0.40367 (10)	−0.00989 (7)	0.01305 (17)
H11	0.2602	0.3913	−0.0824	0.016*
C12	0.37240 (9)	0.54653 (11)	0.02527 (7)	0.01537 (18)
H12	0.3626	0.6368	−0.0099	0.018*
C13	0.45390 (9)	0.51866 (10)	0.11585 (7)	0.01456 (18)
H13	0.5158	0.5835	0.1582	0.017*
C13A	0.42597 (8)	0.36124 (10)	0.13604 (6)	0.01148 (17)
C13B	0.51312 (8)	0.26159 (10)	0.21615 (6)	0.01180 (17)
H13B	0.5593	0.3234	0.2750	0.014*
C13C	0.60588 (8)	0.17628 (10)	0.18918 (6)	0.01212 (17)
O14	0.38943 (6)	0.29270 (7)	0.04125 (5)	0.01203 (14)
C14	0.11017 (8)	0.26807 (10)	−0.00121 (7)	0.01313 (17)
C15	−0.09493 (10)	0.18619 (12)	−0.03298 (9)	0.0222 (2)
H15A	−0.1745	0.2235	−0.0332	0.033*
H15B	−0.0700	0.0972	0.0079	0.033*
H15C	−0.1049	0.1615	−0.0998	0.033*

	U11	U22	U33	U12	U13	U23
O1	0.0149 (3)	0.0210 (4)	0.0219 (3)	−0.0005 (3)	0.0083 (3)	0.0055 (3)
O2	0.0196 (3)	0.0164 (3)	0.0230 (4)	−0.0020 (3)	0.0111 (3)	−0.0050 (3)
O3	0.0122 (3)	0.0144 (3)	0.0241 (3)	0.0005 (2)	0.0075 (3)	0.0001 (3)
C1	0.0129 (4)	0.0176 (4)	0.0145 (4)	0.0001 (3)	0.0051 (3)	−0.0006 (3)
C2	0.0154 (4)	0.0220 (5)	0.0155 (4)	0.0049 (4)	0.0074 (3)	0.0020 (4)
C3	0.0209 (5)	0.0159 (4)	0.0138 (4)	0.0062 (4)	0.0086 (3)	0.0015 (3)
N4	0.0158 (4)	0.0116 (4)	0.0135 (3)	0.0007 (3)	0.0058 (3)	−0.0009 (3)
C5	0.0183 (4)	0.0132 (4)	0.0156 (4)	−0.0027 (3)	0.0045 (3)	−0.0025 (3)
C6	0.0168 (4)	0.0127 (4)	0.0199 (4)	−0.0014 (3)	0.0060 (4)	0.0012 (3)
C7	0.0144 (4)	0.0142 (4)	0.0139 (4)	0.0012 (3)	0.0043 (3)	0.0036 (3)
N8	0.0122 (3)	0.0126 (3)	0.0141 (3)	0.0007 (3)	0.0058 (3)	0.0022 (3)
C9	0.0144 (4)	0.0145 (4)	0.0117 (4)	0.0013 (3)	0.0058 (3)	0.0003 (3)
C9A	0.0122 (4)	0.0120 (4)	0.0124 (4)	0.0016 (3)	0.0054 (3)	0.0001 (3)
C10	0.0123 (4)	0.0113 (4)	0.0138 (4)	0.0015 (3)	0.0049 (3)	0.0002 (3)
C11	0.0133 (4)	0.0125 (4)	0.0136 (4)	0.0016 (3)	0.0054 (3)	0.0013 (3)
C12	0.0169 (4)	0.0118 (4)	0.0192 (4)	0.0003 (3)	0.0090 (3)	0.0021 (3)
C13	0.0160 (4)	0.0107 (4)	0.0187 (4)	−0.0010 (3)	0.0085 (3)	−0.0008 (3)
C13A	0.0125 (4)	0.0106 (4)	0.0119 (4)	0.0001 (3)	0.0053 (3)	−0.0015 (3)
C13B	0.0113 (4)	0.0119 (4)	0.0120 (4)	−0.0003 (3)	0.0044 (3)	−0.0010 (3)
C13C	0.0127 (4)	0.0119 (4)	0.0114 (4)	0.0009 (3)	0.0042 (3)	−0.0004 (3)
O14	0.0134 (3)	0.0115 (3)	0.0109 (3)	0.0019 (2)	0.0044 (2)	−0.0006 (2)
C14	0.0126 (4)	0.0140 (4)	0.0125 (4)	0.0017 (3)	0.0047 (3)	0.0024 (3)
C15	0.0159 (4)	0.0197 (5)	0.0320 (5)	−0.0038 (4)	0.0105 (4)	−0.0008 (4)

O1—C9	1.2241 (12)	N8—C13B	1.4728 (12)
O2—C14	1.2069 (12)	C9—C9A	1.5227 (13)
O3—C14	1.3417 (11)	C9A—C13A	1.5557 (13)
O3—C15	1.4482 (12)	C9A—C10	1.5584 (13)
C1—C13C	1.3790 (13)	C9A—H9A	1.0000
C1—C2	1.4217 (13)	C10—C14	1.5113 (13)
C1—H1	0.9500	C10—C11	1.5709 (13)
C2—C3	1.3709 (15)	C10—H10	1.0000
C2—H2	0.9500	C11—O14	1.4379 (11)
C3—N4	1.3735 (12)	C11—C12	1.5224 (13)
C3—H3	0.9500	C11—H11	1.0000
N4—C13C	1.3790 (12)	C12—C13	1.3355 (13)
N4—C5	1.4648 (12)	C12—H12	0.9500
C5—C6	1.5276 (14)	C13—C13A	1.5112 (13)
C5—H5A	0.9900	C13—H13	0.9500
C5—H5B	0.9900	C13A—O14	1.4437 (11)
C6—C7	1.5335 (14)	C13A—C13B	1.5211 (12)
C6—H6A	0.9900	C13B—C13C	1.4964 (12)
C6—H6B	0.9900	C13B—H13B	1.0000
C7—N8	1.4540 (12)	C15—H15A	0.9800
C7—H7A	0.9900	C15—H15B	0.9800
C7—H7B	0.9900	C15—H15C	0.9800
N8—C9	1.3602 (12)
C14—O3—C15	115.05 (8)	C14—C10—C9A	114.31 (7)
C13C—C1—C2	107.32 (9)	C14—C10—C11	111.46 (7)
C13C—C1—H1	126.3	C9A—C10—C11	99.53 (7)
C2—C1—H1	126.3	C14—C10—H10	110.4
C3—C2—C1	107.17 (9)	C9A—C10—H10	110.4
C3—C2—H2	126.4	C11—C10—H10	110.4
C1—C2—H2	126.4	O14—C11—C12	102.00 (7)
C2—C3—N4	108.73 (8)	O14—C11—C10	101.10 (7)
C2—C3—H3	125.6	C12—C11—C10	107.40 (7)
N4—C3—H3	125.6	O14—C11—H11	114.9
C3—N4—C13C	108.72 (8)	C12—C11—H11	114.9
C3—N4—C5	124.67 (8)	C10—C11—H11	114.9
C13C—N4—C5	126.59 (8)	C13—C12—C11	105.73 (8)
N4—C5—C6	113.07 (8)	C13—C12—H12	127.1
N4—C5—H5A	109.0	C11—C12—H12	127.1
C6—C5—H5A	109.0	C12—C13—C13A	104.76 (8)
N4—C5—H5B	109.0	C12—C13—H13	127.6
C6—C5—H5B	109.0	C13A—C13—H13	127.6
H5A—C5—H5B	107.8	O14—C13A—C13	102.28 (7)
C5—C6—C7	112.43 (8)	O14—C13A—C13B	111.49 (7)
C5—C6—H6A	109.1	C13—C13A—C13B	125.58 (8)
C7—C6—H6A	109.1	O14—C13A—C9A	100.37 (7)
C5—C6—H6B	109.1	C13—C13A—C9A	108.53 (7)
C7—C6—H6B	109.1	C13B—C13A—C9A	105.84 (7)
H6A—C6—H6B	107.8	N8—C13B—C13C	113.03 (8)
N8—C7—C6	112.31 (8)	N8—C13B—C13A	101.75 (7)
N8—C7—H7A	109.1	C13C—C13B—C13A	114.94 (7)
C6—C7—H7A	109.1	N8—C13B—H13B	108.9
N8—C7—H7B	109.1	C13C—C13B—H13B	108.9
C6—C7—H7B	109.1	C13A—C13B—H13B	108.9
H7A—C7—H7B	107.9	N4—C13C—C1	108.06 (8)
C9—N8—C7	123.21 (8)	N4—C13C—C13B	123.79 (8)
C9—N8—C13B	115.22 (8)	C1—C13C—C13B	128.00 (9)
C7—N8—C13B	120.66 (7)	C11—O14—C13A	95.53 (6)
O1—C9—N8	125.20 (9)	O2—C14—O3	123.77 (9)
O1—C9—C9A	127.32 (9)	O2—C14—C10	124.95 (9)
N8—C9—C9A	107.40 (8)	O3—C14—C10	111.22 (8)
C9—C9A—C13A	101.72 (7)	O3—C15—H15A	109.5
C9—C9A—C10	119.79 (8)	O3—C15—H15B	109.5
C13A—C9A—C10	101.68 (7)	H15A—C15—H15B	109.5
C9—C9A—H9A	110.9	O3—C15—H15C	109.5
C13A—C9A—H9A	110.9	H15A—C15—H15C	109.5
C10—C9A—H9A	110.9	H15B—C15—H15C	109.5
C13C—C1—C2—C3	−0.86 (11)	C10—C9A—C13A—C13	70.29 (8)
C1—C2—C3—N4	0.56 (11)	C9—C9A—C13A—C13B	−28.44 (9)
C2—C3—N4—C13C	−0.05 (10)	C10—C9A—C13A—C13B	−152.58 (7)
C2—C3—N4—C5	−178.73 (8)	C9—N8—C13B—C13C	−133.68 (8)
C3—N4—C5—C6	114.00 (10)	C7—N8—C13B—C13C	35.75 (11)
C13C—N4—C5—C6	−64.44 (12)	C9—N8—C13B—C13A	−9.87 (10)
N4—C5—C6—C7	49.81 (11)	C7—N8—C13B—C13A	159.56 (8)
C5—C6—C7—N8	30.48 (11)	O14—C13A—C13B—N8	−84.63 (8)
C6—C7—N8—C9	80.15 (11)	C13—C13A—C13B—N8	151.13 (8)
C6—C7—N8—C13B	−88.42 (10)	C9A—C13A—C13B—N8	23.60 (9)
C7—N8—C9—O1	5.44 (15)	O14—C13A—C13B—C13C	37.88 (10)
C13B—N8—C9—O1	174.58 (9)	C13—C13A—C13B—C13C	−86.36 (11)
C7—N8—C9—C9A	−177.68 (8)	C9A—C13A—C13B—C13C	146.11 (8)
C13B—N8—C9—C9A	−8.54 (10)	C3—N4—C13C—C1	−0.50 (10)
O1—C9—C9A—C13A	−160.63 (9)	C5—N4—C13C—C1	178.15 (9)
N8—C9—C9A—C13A	22.59 (9)	C3—N4—C13C—C13B	175.47 (8)
O1—C9—C9A—C10	−49.71 (13)	C5—N4—C13C—C13B	−5.89 (14)
N8—C9—C9A—C10	133.51 (8)	C2—C1—C13C—N4	0.83 (10)
C9—C9A—C10—C14	7.94 (11)	C2—C1—C13C—C13B	−174.91 (9)
C13A—C9A—C10—C14	118.89 (8)	N8—C13B—C13C—N4	29.70 (12)
C9—C9A—C10—C11	−110.93 (9)	C13A—C13B—C13C—N4	−86.51 (11)
C13A—C9A—C10—C11	0.01 (8)	N8—C13B—C13C—C1	−155.17 (9)
C14—C10—C11—O14	−84.18 (8)	C13A—C13B—C13C—C1	88.61 (11)
C9A—C10—C11—O14	36.79 (8)	C12—C11—O14—C13A	49.61 (8)
C14—C10—C11—C12	169.35 (7)	C10—C11—O14—C13A	−61.07 (7)
C9A—C10—C11—C12	−69.68 (8)	C13—C13A—O14—C11	−51.18 (8)
O14—C11—C12—C13	−30.93 (9)	C13B—C13A—O14—C11	172.30 (7)
C10—C11—C12—C13	74.90 (9)	C9A—C13A—O14—C11	60.57 (7)
C11—C12—C13—C13A	−1.82 (10)	C15—O3—C14—O2	3.79 (14)
C12—C13—C13A—O14	33.99 (9)	C15—O3—C14—C10	−178.93 (8)
C12—C13—C13A—C13B	162.06 (9)	C9A—C10—C14—O2	−84.24 (11)
C12—C13—C13A—C9A	−71.52 (9)	C11—C10—C14—O2	27.65 (13)
C9—C9A—C13A—O14	87.60 (7)	C9A—C10—C14—O3	98.52 (9)
C10—C9A—C13A—O14	−36.53 (8)	C11—C10—C14—O3	−149.60 (8)
C9—C9A—C13A—C13	−165.57 (7)

D—H···A	D—H	H···A	D···A	D—H···A
C9A—H9A···O1i	1.00	2.43	3.4334 (13)	180

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9A—H9A⋯O1i	1.00	2.43	3.4334 (13)	180

Symmetry code: (i) .