(3Z)-Tri­cyclo­[6.3.3.01,8]tetra­dec-3-ene-10,13-dione

Schollmeyer, D.; Detert, H.

doi:10.1107/S2414314625011320

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 12| December 2025| x251132

https://doi.org/10.1107/S2414314625011320

Open

access

(3Z)-Tricyclo[6.3.3.0^1,8]tetradec-3-ene-10,13-dione

Dieter Schollmeyer ^a and Heiner Detert ^a ^*

^aUniversity Mainz, Duesbergweg 10-14, 55099 Mainz, Germany
^*Correspondence e-mail: [email protected]

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 25 November 2025; accepted 15 December 2025; online 24 December 2025)

The title compound, C₁₄H₁₈O₂, features a diquinane being annulated to a cyclooctene in twist-boat-chair conformation. In the crystal, C—H⋯O hydrogen bonds connect the molecules into centrosymmetric dimers, which are further connected into chains.

Keywords: crystal structure; propellane; diquinane.

CCDC reference: 2515991

Structure description

In a project on cyclooctatetraenophanes (Paquette & Kesselmayer, 1990 ; Paquette et al., 1992 ; Detert et al., 1995 ), the Weiss–Cook condensation (Mitschka et al., 1981 ) of cyclooct-1-ene-5,6-dione (Yates et al., 1972 ) gave, after acidic hydrolysis, the 4-ene isomer of the title compound with m.p. = 346 K. The title compound, C₁₄H₁₈O₂, m.p. = 366–369 K (Fig. 1), appeared as the main product in a single experiment, probably due to a prolonged acidic treatment. The propellane is composed of a diquinane unit (C1, C8–C14) with a six-membered carbon chain connecting the bridgehead carbon atoms. Both cyclopentanone groups adopt an envelope conformation, the diquinane subunit is C₂ symmetrical and the cyclooctene ring adopts a nearly twist-boat-chair conformation. Four molecules comprise the monoclinic unit cell.

Figure 1
View of the title compound with displacement ellipsoids drawn at the 50% probability level.

In the crystal, C12—H12A⋯O1 hydrogen bonds (Table 1, Fig. 2) connect the molecules into centrosymmetric dimers, while C12—H12B⋯O1 hydrogen bonds connect molecules with translation symmetry along the a-axis direction to form chains. These chains are connected via centers of inversion. A further hydrogen bond, C7—H7B⋯O2, connects these chains.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O2ⁱ	0.99	2.48	3.4277 (15)	159
C12—H12A⋯O1ⁱⁱ	0.99	2.49	3.4363 (15)	161
C12—H12B⋯O1ⁱⁱⁱ	0.99	2.56	3.5216 (14)	165
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) ; (iii) .

Figure 2
Partial packing diagram. View nearly along the a-axis direction. Hydrogen bonds are drawn with dashed lines.

Synthesis and crystallization

The title compound appeared in a single experiment and was purified by recrystallization from the mixed solvents of chloroform/propan-2-ol to yield colorless crystals with m.p. = 366–369 K. The annotation of NMR signals follows IUPAC nomenclature (cp: cyclopentane, co: cylooctene), assignment is based on two-dimensional NMR. ¹H-NMR (300 MHz, CDCl₃): δ = 5.83 (dt, 1 H, J_d = 190 Hz, J_t = 7.7 Hz), 5.70 (dt, 1 H, J_d = 190 Hz, J_t = 7.7 Hz), 2.62 (d, 2 H, J = 29 Hz, cp), 2.53 (m, 2 H, J = 29 Hz, cp), 2.42 (d, 2 H, J = 13 Hz, co), 2.37 (d, 2 H, J = 29 Hz, cp), 2.26 (d, 2 H, J = 29 Hz, cp), 2.23 (m, 2 H, co), 1.93 (m, 2 H,co), 1.77 (m, 2 H, co). ¹³C-NMR (75 MHz, CDCl₃): δ = 216.64 (C=O), 134.17, 127.81 (CH, alkene), 52.31 (bs), 52.11, 50.15 (2×CH_q, cp), 49.87 (2×2 CH₂, cp), 35.71, 35.24, 26.65, 26.23 (4×CH₂, co).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₈O₂
M_r	218.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	7.3752 (8), 14.2518 (12), 10.8516 (13)
β (°)	90.735 (10)
V (Å³)	1140.5 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.72 × 0.60 × 0.24

Data collection
Diffractometer	Stoe IPDS 2T
No. of measured, independent and observed [I > 2σ(I)] reflections	5539, 2712, 2530
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.117, 1.08
No. of reflections	2712
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.21
Computer programs: X-AREA WinXpose, Recipe and Integrate (Stoe & Cie, 2020 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 2515991

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314625011320/bt4191sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625011320/bt4191Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314625011320/bt4191Isup3.cml

checkCIF report

Computing details top

(3Z)-Tricyclo[6.3.3.0^1,8]tetradec-3-ene-10,13-dione top

Crystal data top

C₁₄H₁₈O₂	F(000) = 472
M_r = 218.28	D_x = 1.271 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.3752 (8) Å	Cell parameters from 10030 reflections
b = 14.2518 (12) Å	θ = 3.1–28.4°
c = 10.8516 (13) Å	µ = 0.08 mm⁻¹
β = 90.735 (10)°	T = 120 K
V = 1140.5 (2) Å³	Block, colorless
Z = 4	0.72 × 0.60 × 0.24 mm

Data collection top

Stoe IPDS 2T diffractometer	R_int = 0.022
Detector resolution: 6.67 pixels mm^-1	θ_max = 27.9°, θ_min = 3.1°
rotation method, ω scans	h = −9→9
5539 measured reflections	k = −18→17
2712 independent reflections	l = −14→12
2530 reflections with I > 2σ(I)

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0587P)² + 0.5072P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2712 reflections	Δρ_max = 0.46 e Å⁻³
145 parameters	Δρ_min = −0.21 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. Hydrogen atoms were placed at calculated positions and were refined in the riding-model approximation with C_methylene—H = 0.99 Å or with vinyl C—H = 0.95 Å, and with U_iso(H) = 1.2 U_eq(C).

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

	x	y	z	U_iso*/U_eq
O1	0.34531 (11)	0.41848 (6)	0.54746 (8)	0.0239 (2)
O2	1.05457 (12)	0.36839 (7)	0.21695 (8)	0.0257 (2)
C1	0.64732 (14)	0.28588 (8)	0.36384 (9)	0.0145 (2)
C2	0.53772 (15)	0.19405 (8)	0.38070 (10)	0.0186 (2)
H2A	0.512818	0.188121	0.469794	0.022*
H2B	0.419153	0.203398	0.338688	0.022*
C3	0.61074 (18)	0.09886 (9)	0.33785 (12)	0.0251 (3)
H3A	0.656113	0.106588	0.252984	0.030*
H3B	0.507690	0.054416	0.333558	0.030*
C4	0.7620 (2)	0.05340 (9)	0.41584 (13)	0.0310 (3)
H4A	0.728782	0.057295	0.503799	0.037*
H4B	0.769947	−0.013881	0.393859	0.037*
C5	0.94540 (19)	0.09744 (10)	0.40004 (12)	0.0287 (3)
H5	1.029040	0.066217	0.348308	0.034*
C6	0.99890 (16)	0.17679 (10)	0.45313 (11)	0.0243 (3)
H6	1.117424	0.199361	0.436903	0.029*
C7	0.88049 (15)	0.23258 (9)	0.53777 (10)	0.0208 (2)
H7A	0.957078	0.258313	0.605316	0.025*
H7B	0.791270	0.189606	0.575211	0.025*
C8	0.77751 (14)	0.31382 (8)	0.47614 (10)	0.0159 (2)
C9	0.65282 (15)	0.36043 (9)	0.57096 (10)	0.0190 (2)
H9A	0.624344	0.316026	0.638145	0.023*
H9B	0.711910	0.416559	0.607204	0.023*
C10	0.48199 (15)	0.38777 (8)	0.50110 (11)	0.0177 (2)
C11	0.50950 (15)	0.36783 (8)	0.36606 (10)	0.0178 (2)
H11A	0.558481	0.423645	0.323579	0.021*
H11B	0.393841	0.349429	0.325550	0.021*
C12	0.91158 (15)	0.38249 (8)	0.41639 (10)	0.0184 (2)
H12A	0.864300	0.447451	0.419465	0.022*
H12B	1.030510	0.380495	0.459657	0.022*
C13	0.92976 (14)	0.35030 (8)	0.28456 (10)	0.0171 (2)
C14	0.76690 (15)	0.29068 (8)	0.24869 (10)	0.0165 (2)
H14A	0.805928	0.227018	0.223961	0.020*
H14B	0.699427	0.319666	0.179023	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0172 (4)	0.0259 (5)	0.0288 (5)	0.0036 (3)	0.0058 (3)	−0.0024 (3)
O2	0.0205 (4)	0.0328 (5)	0.0239 (4)	−0.0049 (3)	0.0070 (3)	−0.0015 (4)
C1	0.0125 (5)	0.0175 (5)	0.0135 (5)	0.0006 (4)	−0.0002 (4)	−0.0001 (4)
C2	0.0170 (5)	0.0202 (5)	0.0185 (5)	−0.0025 (4)	0.0021 (4)	0.0001 (4)
C3	0.0297 (6)	0.0185 (6)	0.0271 (6)	−0.0030 (5)	0.0044 (5)	−0.0019 (4)
C4	0.0403 (8)	0.0193 (6)	0.0337 (7)	0.0060 (5)	0.0052 (6)	0.0029 (5)
C5	0.0306 (7)	0.0298 (7)	0.0259 (6)	0.0143 (5)	0.0041 (5)	0.0027 (5)
C6	0.0190 (5)	0.0333 (7)	0.0205 (5)	0.0105 (5)	0.0015 (4)	0.0040 (5)
C7	0.0178 (5)	0.0287 (6)	0.0160 (5)	0.0062 (4)	−0.0007 (4)	0.0016 (4)
C8	0.0129 (5)	0.0215 (5)	0.0134 (5)	0.0015 (4)	−0.0005 (4)	−0.0017 (4)
C9	0.0163 (5)	0.0258 (6)	0.0150 (5)	0.0030 (4)	0.0013 (4)	−0.0034 (4)
C10	0.0157 (5)	0.0168 (5)	0.0206 (5)	−0.0001 (4)	0.0024 (4)	−0.0008 (4)
C11	0.0155 (5)	0.0201 (5)	0.0176 (5)	0.0027 (4)	−0.0008 (4)	0.0001 (4)
C12	0.0148 (5)	0.0226 (5)	0.0178 (5)	−0.0018 (4)	0.0006 (4)	−0.0041 (4)
C13	0.0154 (5)	0.0181 (5)	0.0179 (5)	0.0008 (4)	0.0008 (4)	0.0002 (4)
C14	0.0165 (5)	0.0196 (5)	0.0135 (5)	−0.0013 (4)	0.0009 (4)	−0.0012 (4)

Geometric parameters (Å, º) top

O1—C10	1.2140 (14)	C6—H6	0.9500
O2—C13	1.2122 (14)	C7—C8	1.5334 (15)
C1—C14	1.5402 (14)	C7—H7A	0.9900
C1—C11	1.5487 (15)	C7—H7B	0.9900
C1—C2	1.5503 (15)	C8—C9	1.5395 (14)
C1—C8	1.5923 (14)	C8—C12	1.5403 (15)
C2—C3	1.5339 (17)	C9—C10	1.5130 (16)
C2—H2A	0.9900	C9—H9A	0.9900
C2—H2B	0.9900	C9—H9B	0.9900
C3—C4	1.5351 (19)	C10—C11	1.5089 (15)
C3—H3A	0.9900	C11—H11A	0.9900
C3—H3B	0.9900	C11—H11B	0.9900
C4—C5	1.503 (2)	C12—C13	1.5100 (15)
C4—H4A	0.9900	C12—H12A	0.9900
C4—H4B	0.9900	C12—H12B	0.9900
C5—C6	1.327 (2)	C13—C14	1.5179 (15)
C5—H5	0.9500	C14—H14A	0.9900
C6—C7	1.5030 (16)	C14—H14B	0.9900

C14—C1—C11	111.21 (9)	C7—C8—C9	109.34 (9)
C14—C1—C2	115.99 (9)	C7—C8—C12	110.26 (9)
C11—C1—C2	106.95 (8)	C9—C8—C12	113.54 (9)
C14—C1—C8	105.30 (8)	C7—C8—C1	115.81 (9)
C11—C1—C8	100.89 (8)	C9—C8—C1	105.06 (8)
C2—C1—C8	115.53 (9)	C12—C8—C1	102.75 (8)
C3—C2—C1	121.68 (9)	C10—C9—C8	106.08 (9)
C3—C2—H2A	106.9	C10—C9—H9A	110.5
C1—C2—H2A	106.9	C8—C9—H9A	110.5
C3—C2—H2B	106.9	C10—C9—H9B	110.5
C1—C2—H2B	106.9	C8—C9—H9B	110.5
H2A—C2—H2B	106.7	H9A—C9—H9B	108.7
C2—C3—C4	117.49 (11)	O1—C10—C11	126.38 (11)
C2—C3—H3A	107.9	O1—C10—C9	125.15 (11)
C4—C3—H3A	107.9	C11—C10—C9	108.46 (9)
C2—C3—H3B	107.9	C10—C11—C1	104.69 (9)
C4—C3—H3B	107.9	C10—C11—H11A	110.8
H3A—C3—H3B	107.2	C1—C11—H11A	110.8
C5—C4—C3	114.18 (11)	C10—C11—H11B	110.8
C5—C4—H4A	108.7	C1—C11—H11B	110.8
C3—C4—H4A	108.7	H11A—C11—H11B	108.9
C5—C4—H4B	108.7	C13—C12—C8	105.73 (9)
C3—C4—H4B	108.7	C13—C12—H12A	110.6
H4A—C4—H4B	107.6	C8—C12—H12A	110.6
C6—C5—C4	124.71 (12)	C13—C12—H12B	110.6
C6—C5—H5	117.6	C8—C12—H12B	110.6
C4—C5—H5	117.6	H12A—C12—H12B	108.7
C5—C6—C7	122.98 (12)	O2—C13—C12	125.88 (10)
C5—C6—H6	118.5	O2—C13—C14	124.64 (10)
C7—C6—H6	118.5	C12—C13—C14	109.48 (9)
C6—C7—C8	114.92 (9)	C13—C14—C1	106.04 (9)
C6—C7—H7A	108.5	C13—C14—H14A	110.5
C8—C7—H7A	108.5	C1—C14—H14A	110.5
C6—C7—H7B	108.5	C13—C14—H14B	110.5
C8—C7—H7B	108.5	C1—C14—H14B	110.5
H7A—C7—H7B	107.5	H14A—C14—H14B	108.7

C14—C1—C2—C3	32.71 (14)	C7—C8—C9—C10	−143.18 (10)
C11—C1—C2—C3	157.42 (10)	C12—C8—C9—C10	93.24 (11)
C8—C1—C2—C3	−91.21 (12)	C1—C8—C9—C10	−18.27 (12)
C1—C2—C3—C4	74.85 (14)	C8—C9—C10—O1	172.76 (11)
C2—C3—C4—C5	−75.41 (15)	C8—C9—C10—C11	−5.70 (12)
C3—C4—C5—C6	78.96 (17)	O1—C10—C11—C1	−150.31 (11)
C4—C5—C6—C7	0.5 (2)	C9—C10—C11—C1	28.13 (12)
C5—C6—C7—C8	−96.18 (15)	C14—C1—C11—C10	−149.04 (9)
C6—C7—C8—C9	176.29 (10)	C2—C1—C11—C10	83.40 (10)
C6—C7—C8—C12	−58.22 (13)	C8—C1—C11—C10	−37.76 (10)
C6—C7—C8—C1	57.88 (13)	C7—C8—C12—C13	92.57 (10)
C14—C1—C8—C7	−89.14 (11)	C9—C8—C12—C13	−144.36 (9)
C11—C1—C8—C7	155.10 (9)	C1—C8—C12—C13	−31.45 (10)
C2—C1—C8—C7	40.21 (12)	C8—C12—C13—O2	−158.91 (11)
C14—C1—C8—C9	150.13 (9)	C8—C12—C13—C14	20.82 (12)
C11—C1—C8—C9	34.36 (10)	O2—C13—C14—C1	179.06 (11)
C2—C1—C8—C9	−80.53 (11)	C12—C13—C14—C1	−0.68 (12)
C14—C1—C8—C12	31.12 (10)	C11—C1—C14—C13	89.44 (10)
C11—C1—C8—C12	−84.65 (9)	C2—C1—C14—C13	−148.08 (9)
C2—C1—C8—C12	160.46 (9)	C8—C1—C14—C13	−19.00 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O2ⁱ	0.99	2.48	3.4277 (15)	159
C12—H12A···O1ⁱⁱ	0.99	2.49	3.4363 (15)	161
C12—H12B···O1ⁱⁱⁱ	0.99	2.56	3.5216 (14)	165

Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z.

References

Detert, H., Lanter, J. C. & Paquette, L. A. (1995). J. Org. Chem. 60, 353–356. CrossRef CAS Google Scholar
Mitschka, R., Oehldrich, J., Takahashi, K., Cook, J. M., Weiss, U. & Silverton, J. V. (1981). Tetrahedron 37, 4521–4542. CrossRef CAS Google Scholar
Paquette, L. A. & Kesselmayer, M. A. (1990). J. Am. Chem. Soc. 112, 1258–1259. CrossRef CAS Google Scholar
Paquette, L. A., Kesselmayer, M. A., Underiner, G. E., House, S. D., Rogers, R. D., Meerholz, K. & Heinze, J. (1992). J. Am. Chem. Soc. 114, 2644–2652. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2020). X-RED32 and X-AREA. Stoe & Cie, Darmstadt, Germany, Google Scholar
Yates, P., Lewars, E. G. & McCabe, P. H. (1972). Can. J. Chem. 50, 1548–1556. CrossRef CAS Web of Science Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.