7-Meth­oxy­penta­cyclo­[5.4.0.02,6.03,10.05,9]undec­ane-8,11-dione

Kotha, S.; Ansari, S.; Cheekatla, S.R.

doi:10.1107/S2414314620013802

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 10| October 2020| x201380

https://doi.org/10.1107/S2414314620013802

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7-Methoxypentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecane-8,11-dione

Sambasivarao Kotha,^a ^* Saima Ansari ^a and Subba Rao Cheekatla ^a

^aDepartment of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai - 400076, India
^*Correspondence e-mail: srk@chem.iitb.ac.in

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 7 October 2020; accepted 15 October 2020; online 20 October 2020)

The structure of 7-methoxypentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecane-8,11-dione, C₁₂H₁₂O₃, at 150 K has monoclinic (P2₁/c) symmetry. The pentacycloundecane cage compound is composed of four five-membered rings, a planar four-membered ring and a six-membered ring in a boat conformation fused into a closed strained-cage framework. All of the five-membered rings adopt an envelope conformation.

Keywords: crystal structure; Diels–Alder reaction; intramolecular [2 + 2] photocycloaddition; pentacyclo [5.4.0.0^2,6.0^3,10.0^5,9]undecane.

CCDC reference: 1902538

Structure description

Polycyclic cage hydrocarbons act as valuable synthons in pharmaceutical and medicinal chemistry (Bisetty et al., 2006 ; Geldenhuys, et al., 2005 ). They are also useful candidates in energetic materials (Zhang et al., 2018 ). Most of the cage systems display functions in supramolecular chemistry and asymmetric catalysis (Gharpure et al., 2013 ). Oxygenated cage compounds show significant biological activity (Oliver et al., 1991 ; van Dijk et al., 2008 ). In addition, various rearrangement approaches in pentacycloundecane-containing cage frameworks provide an alternative route for the synthesis of biologically relevant frameworks such as D₃-trishomocubane derivatives that are not available by conventional multi-step synthetic routes (Liu et al., 2001 ; Sklyarova et al., 2013 ).

The bond angle C1—O1—C2 is 113.86°(16). Notably, the distance between the methoxy-substituted carbon atom, C2, and C3 is 1.521 (3) Å while the C8—C9 distance is 1.516 (3) Å. The methoxy substitution (presence of electron-donating group) has led to an elongation of the C2—C3 bond. Additionally, all bonds of the cyclobutane ring are not equal, the observed range being 1.552 (3)–1.579 (3) Å. Thus, a slight distortion is observed after substitution with a methoxy group (Fig. 1) compared to Cookson's dione skeleton (Linden et al., 2005 ).

Figure 1
Perspective view of the title compound. Displacement parameters are drawn at the 50% probability level.

Synthesis and crystallization

The title compound 1 was prepared (Fig. 2) from quinone 3, which was derived from the commercially available starting materials 4-hydroxy-3-methoxybenzaldehyde 2 (vanillin) and cyclopentadiene 4 using the reported method (Pratt et al., 1987 ) via a Diels–Alder reaction and [2 + 2] photocycloaddition as key steps (Mehta et al., 1984 ). The Diels–Alder adduct 5 (100 mg, 0.40 mmol, synthesized from quinone 3 via Diels–Alder reaction with freshly cracked cyclopentadiene 4) was dissolved in anhydrous ethyl acetate (300 ml) and irradiated in a Pyrex immersion well using a 125 W medium-pressure UV mercury-vapour lamp for 30 min under nitrogen at room temperature. After conclusion of the reaction as monitored by TLC, the solvent was evaporated under reduced pressure and the crude reaction mixture was purified by silica gel column chromatography using 40% ethyl acetate/petroleum ether as an eluent, which furnished 1 as a colourless solid. The resulting isolated compound was crystallized from petroleum ether and CHCl₃ (4:1) in a refrigerator by slow evaporation (83 mg, 83%). Colourless crystalline solid, m.p. 89–91°C; (lit. reported m.p. 85°C); ¹H NMR (500 MHz, CDCl₃): δ = 3.40 (s, 3H), 3.24–3.20 (m, 1H), 3.08–3.05 (m, 1H), 2.93 (s, 1H), 2.89 (s, 1H), 2.83 (d, J = 6.4 Hz, 1H), 2.68–2.58 (m, 2H), 2.00 (d, J = 11.4 Hz, 1H), 1.9 (d, J = 11.4 Hz, 1H) p.p.m. ¹³C NMR (125 MHz, CDCl₃): δ = 210.8, 209.9, 82.1, 54.7, 53.5, 50.8, 48.5, 43.9, 43.2, 41.9, 36.4 p.p.m. HRMS (ESI): m/z calculated for C₁₂H₁₂NaO₃ [M + K]⁺: 243.418; found: 243.415.

Figure 2
Reaction scheme for the synthesis of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₂H₁₂O₃
M_r	204.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	6.3136 (2), 11.6138 (5), 12.6330 (5)
β (°)	95.292 (3)
V (Å³)	922.37 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.34 × 0.28 × 0.23

Data collection
Diffractometer	Oxford Diffraction Xcalibur-S
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ )
T_min, T_max	0.965, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	4686, 1620, 1432
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.111, 1.10
No. of reflections	1620
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.19
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1902538

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620013802/bt4099sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620013802/bt4099Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620013802/bt4099Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: ShelXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

7-Methoxypentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecane-8,11-dione top

Crystal data top

C₁₂H₁₂O₃	F(000) = 432
M_r = 204.22	D_x = 1.471 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.3136 (2) Å	Cell parameters from 1649 reflections
b = 11.6138 (5) Å	θ = 3.3–32.8°
c = 12.6330 (5) Å	µ = 0.11 mm⁻¹
β = 95.292 (3)°	T = 150 K
V = 922.37 (6) Å³	Block, colourless
Z = 4	0.34 × 0.28 × 0.23 mm

Data collection top

Oxford Diffraction Xcalibur-S diffractometer	1432 reflections with I > 2σ(I)
Detector resolution: 15.9948 pixels mm^-1	R_int = 0.020
ω/q–scan	θ_max = 25.0°, θ_min = 3.7°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	h = −7→4
T_min = 0.965, T_max = 0.976	k = −13→13
4686 measured reflections	l = −13→15
1620 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0339P)² + 1.1811P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1620 reflections	Δρ_max = 0.31 e Å⁻³
137 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints

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. The H atoms were found in a difference map but refined using a riding model with C—H ranging from 0.98 Å to 1.00 Å and U(H) set to 1.2 U_eq(C) or 1.5 U_eq(C_methyl).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.5101 (2)	0.05611 (13)	0.88757 (12)	0.0213 (4)
O2	0.7295 (2)	0.00528 (14)	0.69852 (12)	0.0252 (4)
O3	0.1795 (2)	−0.10734 (14)	0.62216 (13)	0.0281 (4)
C1	0.7014 (4)	0.1112 (2)	0.93007 (18)	0.0231 (5)
H1A	0.8199	0.0856	0.8910	0.035*
H1B	0.7304	0.0910	1.0053	0.035*
H1C	0.6852	0.1949	0.9231	0.035*
C2	0.4378 (3)	0.09282 (18)	0.78544 (17)	0.0183 (5)
C3	0.5748 (3)	0.06703 (18)	0.69536 (17)	0.0186 (5)
C4	0.4765 (3)	0.13774 (19)	0.60217 (17)	0.0205 (5)
H4	0.5664	0.1421	0.5411	0.025*
C5	0.4380 (3)	0.25570 (19)	0.65426 (17)	0.0219 (5)
H5	0.5615	0.3100	0.6586	0.026*
C6	0.3617 (3)	0.21926 (19)	0.76243 (17)	0.0204 (5)
H6	0.3814	0.2757	0.8223	0.024*
C7	0.1322 (3)	0.17496 (19)	0.73067 (17)	0.0201 (5)
H7	0.0168	0.2055	0.7720	0.024*
C8	0.2040 (3)	0.04885 (19)	0.75312 (17)	0.0202 (5)
H8	0.1322	0.0060	0.8084	0.024*
C9	0.2003 (3)	−0.00636 (19)	0.64421 (18)	0.0211 (5)
C10	0.2401 (3)	0.0924 (2)	0.57020 (18)	0.0225 (5)
H10	0.2100	0.0735	0.4931	0.027*
C11	0.1045 (4)	0.1921 (2)	0.60828 (18)	0.0232 (5)
H11	−0.0461	0.1944	0.5759	0.028*
C12	0.2344 (4)	0.30022 (19)	0.59218 (18)	0.0239 (5)
H12A	0.1760	0.3693	0.6250	0.029*
H12B	0.2528	0.3151	0.5164	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0240 (8)	0.0213 (8)	0.0187 (8)	−0.0036 (7)	0.0019 (6)	0.0028 (6)
O2	0.0209 (8)	0.0287 (9)	0.0265 (9)	0.0030 (7)	0.0040 (6)	−0.0010 (7)
O3	0.0281 (9)	0.0185 (9)	0.0369 (10)	−0.0011 (7)	−0.0014 (7)	−0.0055 (7)
C1	0.0258 (12)	0.0230 (12)	0.0200 (11)	−0.0045 (10)	−0.0006 (9)	−0.0018 (9)
C2	0.0223 (11)	0.0147 (11)	0.0178 (11)	0.0000 (9)	0.0015 (9)	0.0009 (8)
C3	0.0167 (11)	0.0172 (11)	0.0223 (11)	−0.0036 (9)	0.0032 (8)	−0.0021 (9)
C4	0.0188 (10)	0.0250 (12)	0.0182 (11)	−0.0013 (9)	0.0045 (8)	−0.0004 (9)
C5	0.0237 (11)	0.0199 (12)	0.0222 (12)	−0.0044 (9)	0.0026 (9)	0.0015 (9)
C6	0.0260 (11)	0.0162 (11)	0.0194 (11)	−0.0004 (9)	0.0042 (9)	−0.0011 (9)
C7	0.0186 (11)	0.0176 (11)	0.0249 (12)	0.0029 (9)	0.0060 (9)	0.0000 (9)
C8	0.0181 (11)	0.0190 (11)	0.0243 (12)	−0.0009 (9)	0.0065 (8)	0.0031 (9)
C9	0.0130 (10)	0.0202 (12)	0.0292 (12)	0.0001 (9)	−0.0034 (8)	−0.0024 (9)
C10	0.0235 (12)	0.0234 (12)	0.0201 (12)	0.0013 (9)	−0.0009 (9)	−0.0034 (9)
C11	0.0209 (11)	0.0234 (12)	0.0249 (12)	0.0030 (9)	0.0001 (9)	0.0015 (10)
C12	0.0286 (12)	0.0187 (11)	0.0248 (12)	0.0024 (10)	0.0047 (9)	0.0048 (9)

Geometric parameters (Å, º) top

O1—C1	1.427 (3)	C5—C12	1.533 (3)
O1—C2	1.395 (3)	C6—H6	1.0000
O2—C3	1.209 (3)	C6—C7	1.555 (3)
O3—C9	1.210 (3)	C7—H7	1.0000
C1—H1A	0.9800	C7—C8	1.552 (3)
C1—H1B	0.9800	C7—C11	1.553 (3)
C1—H1C	0.9800	C8—H8	1.0000
C2—C3	1.521 (3)	C8—C9	1.516 (3)
C2—C6	1.564 (3)	C9—C10	1.516 (3)
C2—C8	1.579 (3)	C10—H10	1.0000
C3—C4	1.520 (3)	C10—C11	1.543 (3)
C4—H4	1.0000	C11—H11	1.0000
C4—C5	1.549 (3)	C11—C12	1.523 (3)
C4—C10	1.599 (3)	C12—H12A	0.9900
C5—H5	1.0000	C12—H12B	0.9900
C5—C6	1.549 (3)

C2—O1—C1	113.86 (16)	C6—C7—H7	117.0
O1—C1—H1A	109.5	C8—C7—C6	90.88 (16)
O1—C1—H1B	109.5	C8—C7—H7	117.0
O1—C1—H1C	109.5	C8—C7—C11	107.91 (17)
H1A—C1—H1B	109.5	C11—C7—C6	103.36 (17)
H1A—C1—H1C	109.5	C11—C7—H7	117.0
H1B—C1—H1C	109.5	C2—C8—H8	117.0
O1—C2—C3	118.11 (17)	C7—C8—C2	89.57 (16)
O1—C2—C6	121.84 (18)	C7—C8—H8	117.0
O1—C2—C8	111.03 (17)	C9—C8—C2	107.88 (17)
C3—C2—C6	103.41 (17)	C9—C8—C7	104.69 (18)
C3—C2—C8	108.99 (17)	C9—C8—H8	117.0
C6—C2—C8	89.53 (15)	O3—C9—C8	127.7 (2)
O2—C3—C2	127.2 (2)	O3—C9—C10	127.8 (2)
O2—C3—C4	128.1 (2)	C10—C9—C8	104.48 (18)
C4—C3—C2	104.68 (17)	C4—C10—H10	114.1
C3—C4—H4	113.9	C9—C10—C4	107.28 (17)
C3—C4—C5	102.57 (17)	C9—C10—H10	114.1
C3—C4—C10	108.83 (17)	C9—C10—C11	104.33 (18)
C5—C4—H4	113.9	C11—C10—C4	101.91 (17)
C5—C4—C10	102.63 (17)	C11—C10—H10	114.1
C10—C4—H4	113.9	C7—C11—H11	115.2
C4—C5—H5	115.4	C10—C11—C7	101.50 (17)
C4—C5—C6	101.95 (17)	C10—C11—H11	115.2
C6—C5—H5	115.4	C12—C11—C7	103.08 (18)
C12—C5—C4	103.79 (17)	C12—C11—C10	104.82 (18)
C12—C5—H5	115.4	C12—C11—H11	115.2
C12—C5—C6	103.25 (17)	C5—C12—H12A	112.7
C2—C6—H6	117.4	C5—C12—H12B	112.7
C5—C6—C2	107.77 (17)	C11—C12—C5	95.17 (17)
C5—C6—H6	117.4	C11—C12—H12A	112.7
C5—C6—C7	102.77 (17)	C11—C12—H12B	112.7
C7—C6—C2	90.01 (16)	H12A—C12—H12B	110.2
C7—C6—H6	117.4

O1—C2—C3—O2	10.0 (3)	C5—C4—C10—C11	0.4 (2)
O1—C2—C3—C4	−168.95 (17)	C5—C6—C7—C8	108.30 (17)
O1—C2—C6—C5	141.85 (19)	C5—C6—C7—C11	−0.3 (2)
O1—C2—C6—C7	−114.7 (2)	C6—C2—C3—O2	147.9 (2)
O1—C2—C8—C7	124.27 (18)	C6—C2—C3—C4	−31.0 (2)
O1—C2—C8—C9	−130.43 (18)	C6—C2—C8—C7	0.06 (16)
O2—C3—C4—C5	−134.1 (2)	C6—C2—C8—C9	105.37 (18)
O2—C3—C4—C10	117.7 (2)	C6—C5—C12—C11	−53.4 (2)
O3—C9—C10—C4	−111.3 (2)	C6—C7—C8—C2	−0.06 (16)
O3—C9—C10—C11	141.1 (2)	C6—C7—C8—C9	−108.45 (17)
C1—O1—C2—C3	65.0 (2)	C6—C7—C11—C10	74.92 (19)
C1—O1—C2—C6	−64.9 (2)	C6—C7—C11—C12	−33.4 (2)
C1—O1—C2—C8	−168.08 (17)	C7—C8—C9—O3	−155.1 (2)
C2—C3—C4—C5	44.8 (2)	C7—C8—C9—C10	27.8 (2)
C2—C3—C4—C10	−63.4 (2)	C7—C11—C12—C5	52.89 (19)
C2—C6—C7—C8	0.06 (16)	C8—C2—C3—O2	−117.9 (2)
C2—C6—C7—C11	−108.58 (17)	C8—C2—C3—C4	63.2 (2)
C2—C8—C9—O3	110.5 (2)	C8—C2—C6—C5	−103.48 (18)
C2—C8—C9—C10	−66.6 (2)	C8—C2—C6—C7	−0.06 (16)
C3—C2—C6—C5	5.9 (2)	C8—C7—C11—C10	−20.4 (2)
C3—C2—C6—C7	109.36 (17)	C8—C7—C11—C12	−128.80 (18)
C3—C2—C8—C7	−103.97 (18)	C8—C9—C10—C4	65.8 (2)
C3—C2—C8—C9	1.3 (2)	C8—C9—C10—C11	−41.8 (2)
C3—C4—C5—C6	−39.4 (2)	C9—C10—C11—C7	37.7 (2)
C3—C4—C5—C12	−146.43 (17)	C9—C10—C11—C12	144.74 (18)
C3—C4—C10—C9	−0.7 (2)	C10—C4—C5—C6	73.49 (19)
C3—C4—C10—C11	108.63 (19)	C10—C4—C5—C12	−33.6 (2)
C4—C5—C6—C2	20.5 (2)	C10—C11—C12—C5	−53.0 (2)
C4—C5—C6—C7	−73.64 (19)	C11—C7—C8—C2	104.29 (18)
C4—C5—C12—C11	52.71 (19)	C11—C7—C8—C9	−4.1 (2)
C4—C10—C11—C7	−73.82 (19)	C12—C5—C6—C2	128.00 (18)
C4—C10—C11—C12	33.2 (2)	C12—C5—C6—C7	33.8 (2)
C5—C4—C10—C9	−108.86 (19)

Acknowledgements

We thank Darshan S. Mhatre for his help with the data collection and structure refinement.

Funding information

Funding for this research was provided by: Department of Science and Technology, Ministry of Science and Technology, J C Bose Fellowship (award No. SR/S2/JCB-33/2010 to Prof. Sambasivarao Kotha); Defence Research and Development Organisation (grant No. ARDB/01/1041849/M/1 to Prof. Sambasivarao Kotha); University Grants Commission (scholarship to Saima Ansari, Subba Rao Cheekatla).

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