Crystal structure of methyl (3RS,4SR,4aRS,11aRS,11bSR)-5-oxo-3,4,4a,5,7,8,9,10,11,11a-deca-hydro-3,11b-ep-oxy-azepino[2,1-a]iso-indole-4-carboxyl-ate.

The title compound, C15H19NO4, is the a product of the esterification of the corresponding carbonic acid with methanol. The mol-ecule comprises a fused tetra-cyclic system containing three five-membered rings (2-pyrrolidinone, tetra-hydro-furan and di-hydro-furan) and one seven-membered ring (azepane). The five-membered rings have the usual envelope conformations, with the quaternary C atom being the flap atom for the 2-pyrrolidinone ring, and the ether O atom being the common flap atom for the remaining rings. The seven-membered azepane ring adopts a chair conformation with the methine and middle methyl-ene C atoms lying above and below the mean plane defined by the remaining five atoms. The carboxyl-ate substituent is rotated by 77.56 (5)° with respect to the base plane of the tetra-hydro-furan ring. In the crystal, the mol-ecules are bound by weak C-H⋯O hydrogen-bonding inter-actions into puckered layers parallel to (001).

Related literature

For the synthesis of 2-(furan-2-yl)azepane, see: Asher et al. (1981 ▸); Shono et al. (1981 ▸); Nikolic & Beak (1997 ▸). For intra­molecular cyclo­addition reactions of α,β-unsaturated acid anhydrides to α-furyl­amines (IMDAF reactions), see: Vogel et al. (1999 ▸); Zubkov et al. (2005 ▸). For related compounds, see: Zylber et al. (1995 ▸); Evans et al. (1999 ▸); Kachkovskyi & Kolodiazhnyi (2007 ▸); Kharitonov et al. (2009 ▸); Aabid et al. (2010 ▸); Zubkov et al. (2010 ▸, 2011 ▸, 2014 ▸); Toze et al. (2011 ▸); Wang & Li (2012 ▸); Zaytsev, Mikhailova et al. (2012 ▸); Zaytsev, Zubkov et al. 2012 ▸); Zaytsev et al. (2013 ▸); Chen et al. (2013 ▸); Hizartzidis et al. (2014 ▸).

Experimental

Crystal data

C15H19NO4

M = 277.31

Triclinic,

a = 7.5460 (8) Å

b = 9.6984 (10) Å

c = 10.2894 (10) Å

α = 103.857 (2)°

β = 94.745 (2)°

γ = 106.620 (2)°

V = 691.24 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 290 K

0.30 × 0.25 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▸) T min = 0.959, T max = 0.969

9699 measured reflections

3268 independent reflections

2613 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.141

S = 1.03

3268 reflections

182 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2005 ▸); cell refinement: SAINT (Bruker, 2001 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015016679/tk5384sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015016679/tk5384Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015016679/tk5384Isup3.cml

Click here for additional data file.

a b a . DOI: 10.1107/S2056989015016679/tk5384fig1.tif

Esterification of 5-oxo-3,4,4a,5,7,8,9,10,11,11a-deca­hydro-3,11b-ep­oxy­azepino[2,1-a]iso­indole-4-carb­oxy­lic acid with methanol.

Click here for additional data file.

. DOI: 10.1107/S2056989015016679/tk5384fig2.tif

Mol­ecular structure of (I). Displacement ellipsoids are shown at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.

Click here for additional data file.

a . DOI: 10.1107/S2056989015016679/tk5384fig3.tif

Crystal packing of (I) along the a axis demonstrating the H-bonded puckered layers parallel to (001). Dashed lines indicate the weak inter­molecular C—H⋯O hydrogen-bonding inter­actions.

CCDC reference: 1422681

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H19NO4	Z = 2
Mr = 277.31	F(000) = 296
Triclinic, P1	Dx = 1.332 Mg m−3
a = 7.5460 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6984 (10) Å	Cell parameters from 4971 reflections
c = 10.2894 (10) Å	θ = 2.3–29.5°
α = 103.857 (2)°	µ = 0.10 mm−1
β = 94.745 (2)°	T = 290 K
γ = 106.620 (2)°	Prism, colourless
V = 691.24 (12) Å3	0.30 × 0.25 × 0.25 mm

Bruker APEXII CCD diffractometer	2613 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
φ and ω scans	θmax = 28.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→9
Tmin = 0.959, Tmax = 0.969	k = −12→12
9699 measured reflections	l = −13→13
3268 independent reflections

Refinement on F2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0765P)2 + 0.153P] where P = (Fo2 + 2Fc2)/3
3268 reflections	(Δ/σ)max < 0.001
182 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.55178 (19)	0.17386 (17)	0.75675 (18)	0.0471 (4)
H1	0.4515	0.2009	0.7244	0.056*
C2	0.5710 (2)	0.12672 (19)	0.86511 (18)	0.0491 (4)
H2	0.4866	0.1136	0.9255	0.059*
C3	0.7587 (2)	0.09790 (16)	0.87191 (15)	0.0403 (3)
H3	0.7723	0.0281	0.9240	0.048*
C4	0.91211 (19)	0.25575 (15)	0.91807 (14)	0.0356 (3)
H4	0.8735	0.3221	0.9899	0.043*
C4A	0.89714 (17)	0.30474 (14)	0.78642 (13)	0.0320 (3)
H4A	0.8720	0.4006	0.8028	0.038*
C5	1.04722 (18)	0.29945 (15)	0.69682 (14)	0.0352 (3)
O5	1.21692 (14)	0.35060 (14)	0.73347 (12)	0.0513 (3)
N6	0.96070 (17)	0.23177 (15)	0.56738 (12)	0.0414 (3)
C7	1.0663 (3)	0.2066 (3)	0.45696 (19)	0.0663 (5)
H7A	1.0931	0.1134	0.4506	0.080*
H7B	1.1852	0.2864	0.4788	0.080*
C8	0.9697 (5)	0.1996 (3)	0.3221 (2)	0.0920 (8)
H8A	0.8776	0.1011	0.2861	0.110*
H8B	1.0616	0.2089	0.2615	0.110*
C9	0.8730 (4)	0.3136 (3)	0.3181 (2)	0.0914 (8)
H9A	0.9526	0.4088	0.3778	0.110*
H9B	0.8637	0.3246	0.2268	0.110*
C10	0.6832 (4)	0.2847 (3)	0.3564 (2)	0.0873 (8)
H10A	0.6030	0.1913	0.2941	0.105*
H10B	0.6353	0.3632	0.3411	0.105*
C11	0.6606 (3)	0.2749 (2)	0.4981 (2)	0.0620 (5)
H11A	0.5277	0.2389	0.5017	0.074*
H11B	0.7103	0.3751	0.5592	0.074*
C11A	0.7550 (2)	0.17431 (17)	0.55118 (15)	0.0423 (3)
H11C	0.7081	0.0719	0.4914	0.051*
C11B	0.72833 (18)	0.17475 (15)	0.69564 (14)	0.0353 (3)
O12	0.76978 (13)	0.05080 (10)	0.73010 (10)	0.0362 (2)
C13	1.1022 (2)	0.24951 (16)	0.96810 (14)	0.0369 (3)
O13	1.15577 (16)	0.14282 (13)	0.93999 (12)	0.0503 (3)
O14	1.20359 (16)	0.38062 (13)	1.05547 (12)	0.0547 (3)
C14	1.3882 (3)	0.3891 (3)	1.1134 (2)	0.0785 (7)
H14A	1.4432	0.4823	1.1823	0.118*
H14B	1.4649	0.3831	1.0437	0.118*
H14C	1.3793	0.3076	1.1528	0.118*

	U11	U22	U33	U12	U13	U23
C1	0.0251 (7)	0.0436 (8)	0.0698 (11)	0.0131 (6)	0.0051 (7)	0.0090 (7)
C2	0.0352 (8)	0.0505 (9)	0.0634 (10)	0.0136 (6)	0.0208 (7)	0.0147 (7)
C3	0.0389 (7)	0.0414 (8)	0.0462 (8)	0.0148 (6)	0.0143 (6)	0.0171 (6)
C4	0.0346 (7)	0.0389 (7)	0.0350 (7)	0.0170 (6)	0.0074 (5)	0.0063 (5)
C4A	0.0276 (6)	0.0300 (6)	0.0393 (7)	0.0131 (5)	0.0028 (5)	0.0074 (5)
C5	0.0299 (6)	0.0378 (7)	0.0428 (7)	0.0134 (5)	0.0052 (5)	0.0169 (6)
O5	0.0271 (5)	0.0681 (8)	0.0603 (7)	0.0106 (5)	0.0047 (5)	0.0266 (6)
N6	0.0388 (7)	0.0508 (7)	0.0387 (6)	0.0172 (6)	0.0076 (5)	0.0158 (5)
C7	0.0728 (13)	0.0911 (15)	0.0516 (10)	0.0372 (11)	0.0287 (9)	0.0299 (10)
C8	0.153 (3)	0.0921 (17)	0.0439 (11)	0.0550 (17)	0.0284 (13)	0.0186 (11)
C9	0.135 (3)	0.0910 (17)	0.0566 (12)	0.0335 (16)	0.0119 (14)	0.0391 (12)
C10	0.105 (2)	0.0797 (15)	0.0733 (14)	0.0216 (14)	−0.0235 (14)	0.0358 (12)
C11	0.0454 (9)	0.0690 (12)	0.0734 (12)	0.0160 (8)	−0.0107 (8)	0.0323 (10)
C11A	0.0372 (7)	0.0424 (8)	0.0424 (8)	0.0088 (6)	−0.0039 (6)	0.0109 (6)
C11B	0.0273 (6)	0.0330 (7)	0.0450 (7)	0.0113 (5)	0.0011 (5)	0.0093 (5)
O12	0.0351 (5)	0.0309 (5)	0.0438 (5)	0.0132 (4)	0.0073 (4)	0.0085 (4)
C13	0.0395 (7)	0.0419 (7)	0.0327 (7)	0.0179 (6)	0.0056 (5)	0.0105 (5)
O13	0.0452 (6)	0.0456 (6)	0.0635 (7)	0.0234 (5)	0.0030 (5)	0.0123 (5)
O14	0.0458 (6)	0.0534 (7)	0.0541 (7)	0.0215 (5)	−0.0103 (5)	−0.0062 (5)
C14	0.0509 (11)	0.0831 (15)	0.0813 (14)	0.0250 (10)	−0.0251 (10)	−0.0073 (11)

C1—C2	1.315 (3)	C8—C9	1.495 (4)
C1—C11B	1.5182 (19)	C8—H8A	0.9700
C1—H1	0.9300	C8—H8B	0.9700
C2—C3	1.519 (2)	C9—C10	1.484 (4)
C2—H2	0.9300	C9—H9A	0.9700
C3—O12	1.4380 (18)	C9—H9B	0.9700
C3—C4	1.567 (2)	C10—C11	1.504 (3)
C3—H3	0.9800	C10—H10A	0.9700
C4—C13	1.5062 (19)	C10—H10B	0.9700
C4—C4A	1.5450 (19)	C11—C11A	1.531 (2)
C4—H4	0.9800	C11—H11A	0.9700
C4A—C5	1.5226 (18)	C11—H11B	0.9700
C4A—C11B	1.5508 (18)	C11A—C11B	1.515 (2)
C4A—H4A	0.9800	C11A—H11C	0.9800
C5—O5	1.2228 (17)	C11B—O12	1.4386 (16)
C5—N6	1.3502 (19)	C13—O13	1.1972 (17)
N6—C7	1.454 (2)	C13—O14	1.3389 (18)
N6—C11A	1.4718 (19)	O14—C14	1.440 (2)
C7—C8	1.490 (3)	C14—H14A	0.9600
C7—H7A	0.9700	C14—H14B	0.9600
C7—H7B	0.9700	C14—H14C	0.9600
C2—C1—C11B	105.23 (13)	C10—C9—C8	117.5 (2)
C2—C1—H1	127.4	C10—C9—H9A	107.9
C11B—C1—H1	127.4	C8—C9—H9A	107.9
C1—C2—C3	106.25 (13)	C10—C9—H9B	107.9
C1—C2—H2	126.9	C8—C9—H9B	107.9
C3—C2—H2	126.9	H9A—C9—H9B	107.2
O12—C3—C2	100.98 (12)	C9—C10—C11	118.87 (19)
O12—C3—C4	101.71 (10)	C9—C10—H10A	107.6
C2—C3—C4	106.12 (12)	C11—C10—H10A	107.6
O12—C3—H3	115.4	C9—C10—H10B	107.6
C2—C3—H3	115.4	C11—C10—H10B	107.6
C4—C3—H3	115.4	H10A—C10—H10B	107.0
C13—C4—C4A	115.38 (11)	C10—C11—C11A	116.12 (18)
C13—C4—C3	112.85 (12)	C10—C11—H11A	108.3
C4A—C4—C3	100.04 (11)	C11A—C11—H11A	108.3
C13—C4—H4	109.4	C10—C11—H11B	108.3
C4A—C4—H4	109.4	C11A—C11—H11B	108.3
C3—C4—H4	109.4	H11A—C11—H11B	107.4
C5—C4A—C4	119.20 (10)	N6—C11A—C11B	100.81 (11)
C5—C4A—C11B	100.41 (11)	N6—C11A—C11	112.40 (13)
C4—C4A—C11B	101.76 (10)	C11B—C11A—C11	112.17 (14)
C5—C4A—H4A	111.4	N6—C11A—H11C	110.4
C4—C4A—H4A	111.4	C11B—C11A—H11C	110.4
C11B—C4A—H4A	111.4	C11—C11A—H11C	110.4
O5—C5—N6	125.20 (13)	O12—C11B—C11A	111.09 (11)
O5—C5—C4A	126.66 (13)	O12—C11B—C1	101.52 (11)
N6—C5—C4A	108.11 (11)	C11A—C11B—C1	126.86 (12)
C5—N6—C7	121.55 (14)	O12—C11B—C4A	99.30 (10)
C5—N6—C11A	114.43 (12)	C11A—C11B—C4A	105.24 (11)
C7—N6—C11A	123.77 (14)	C1—C11B—C4A	109.56 (11)
N6—C7—C8	114.54 (19)	C3—O12—C11B	96.06 (10)
N6—C7—H7A	108.6	O13—C13—O14	123.64 (13)
C8—C7—H7A	108.6	O13—C13—C4	126.23 (13)
N6—C7—H7B	108.6	O14—C13—C4	110.07 (11)
C8—C7—H7B	108.6	C13—O14—C14	115.86 (13)
H7A—C7—H7B	107.6	O14—C14—H14A	109.5
C7—C8—C9	117.0 (2)	O14—C14—H14B	109.5
C7—C8—H8A	108.0	H14A—C14—H14B	109.5
C9—C8—H8A	108.0	O14—C14—H14C	109.5
C7—C8—H8B	108.0	H14A—C14—H14C	109.5
C9—C8—H8B	108.0	H14B—C14—H14C	109.5
H8A—C8—H8B	107.3
C11B—C1—C2—C3	−0.09 (17)	C10—C11—C11A—N6	65.8 (2)
C1—C2—C3—O12	−32.37 (16)	C10—C11—C11A—C11B	178.61 (16)
C1—C2—C3—C4	73.37 (16)	N6—C11A—C11B—O12	−76.52 (13)
O12—C3—C4—C13	−91.15 (13)	C11—C11A—C11B—O12	163.70 (12)
C2—C3—C4—C13	163.64 (12)	N6—C11A—C11B—C1	159.66 (13)
O12—C3—C4—C4A	32.02 (12)	C11—C11A—C11B—C1	39.9 (2)
C2—C3—C4—C4A	−73.20 (13)	N6—C11A—C11B—C4A	30.01 (13)
C13—C4—C4A—C5	17.25 (17)	C11—C11A—C11B—C4A	−89.77 (14)
C3—C4—C4A—C5	−104.12 (13)	C2—C1—C11B—O12	32.57 (15)
C13—C4—C4A—C11B	126.38 (12)	C2—C1—C11B—C11A	160.29 (14)
C3—C4—C4A—C11B	5.01 (12)	C2—C1—C11B—C4A	−71.75 (15)
C4—C4A—C5—O5	−49.29 (19)	C5—C4A—C11B—O12	82.53 (11)
C11B—C4A—C5—O5	−159.17 (14)	C4—C4A—C11B—O12	−40.49 (11)
C4—C4A—C5—N6	132.54 (12)	C5—C4A—C11B—C11A	−32.47 (12)
C11B—C4A—C5—N6	22.66 (13)	C4—C4A—C11B—C11A	−155.48 (11)
O5—C5—N6—C7	3.1 (2)	C5—C4A—C11B—C1	−171.63 (11)
C4A—C5—N6—C7	−178.69 (14)	C4—C4A—C11B—C1	65.35 (13)
O5—C5—N6—C11A	177.51 (13)	C2—C3—O12—C11B	50.39 (12)
C4A—C5—N6—C11A	−4.29 (16)	C4—C3—O12—C11B	−58.82 (11)
C5—N6—C7—C8	−152.76 (19)	C11A—C11B—O12—C3	171.91 (11)
C11A—N6—C7—C8	33.4 (3)	C1—C11B—O12—C3	−50.81 (12)
N6—C7—C8—C9	43.2 (3)	C4A—C11B—O12—C3	61.51 (11)
C7—C8—C9—C10	−81.4 (3)	C4A—C4—C13—O13	−91.08 (18)
C8—C9—C10—C11	62.4 (3)	C3—C4—C13—O13	23.1 (2)
C9—C10—C11—C11A	−48.4 (3)	C4A—C4—C13—O14	91.77 (14)
C5—N6—C11A—C11B	−16.60 (16)	C3—C4—C13—O14	−154.06 (12)
C7—N6—C11A—C11B	157.66 (15)	O13—C13—O14—C14	1.6 (2)
C5—N6—C11A—C11	103.02 (16)	C4—C13—O14—C14	178.86 (16)
C7—N6—C11A—C11	−82.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O5i	0.93	2.59	3.4576 (19)	156
C3—H3···O13ii	0.98	2.55	3.5259 (19)	174
C4A—H4A···O14iii	0.98	2.51	3.4190 (17)	154
C14—H14A···O5iv	0.96	2.56	3.279 (2)	132

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C1H1O5i	0.93	2.59	3.4576(19)	156
C3H3O13ii	0.98	2.55	3.5259(19)	174
C4AH4AO14iii	0.98	2.51	3.4190(17)	154
C14H14AO5iv	0.96	2.56	3.279(2)	132

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .