Synthesis and crystal structure analysis of substituted bi­cyclo­[3.3.1]nona­nones

König, J.A.; Morgenstern, B.; Jauch, J.

doi:10.1107/S2056989025003299

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Volume 81| Part 5| May 2025|

https://doi.org/10.1107/S2056989025003299

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Synthesis and crystal structure analysis of substituted bicyclo[3.3.1]nonanones

Julien A. König,^a ^* Bernd Morgenstern ^b and Johann Jauch ^a

^aOrganic Chemistry II, Saarland University, 66123 Saarbrücken, Germany, and ^bService Center X-ray diffraction, Saarland University, 66123 Saarbrücken, Germany
^*Correspondence e-mail: julien.koenig@uni-saarland.de

Edited by S. P. Kelley, University of Missouri-Columbia, USA (Received 12 March 2025; accepted 11 April 2025; online 17 April 2025)

A set of novel bicyclo[3.3.1]nonanones, namely, 4-methoxybicyclo[3.3.1]non-3-ene-2,9-dione, C₁₀H₁₂O₃ (1), 4,9,9-trimethoxybicyclo[3.3.1]non-3-en-2-ol, C₁₂H₂₀O₄ (2), 4-methoxy-6-methyl-1-(3-methylbut-2-en-1-yl)-6-(4-methylpent-3-en-1-yl)bicyclo[3.3.1]non-3-ene-2,9-dione, C₂₂H₃₂O₃ (3) and 4-(tert-butyl)-4-hydroxy-2-methoxy-8-methyl-7-(3-methylbut-2-en-1-yl)-8-(4-methylpent-3-en-1-yl)bicyclo[3.3.1]non-2-en-9-one, C₂₆H₄₂O₃ (4), were synthesized and structurally elucidated by NMR, HRMS and X-ray crystallography.

Keywords: polycyclic; polyprenylated acylphloroglucinol; PPAPs; bridgehead substitution; carbocycles; crystal structure.

CCDC references: 2429999; 2430008; 2430001; 2430007

1. Chemical context

Polycyclic polyprenylated acylphloroglucinols (PPAPs) are a class of structurally complex natural products predominantly isolated from plants of the Hypericum and Garcinia genera. Characterized by a highly oxygenated polycyclic core densely decorated with various substituents, these compounds exhibit remarkable chemical diversity and biological activity (Yang et al., 2018 ). Notably, a single representative can already cover a wide range of different activities. The most important of these may include anti-inflammatory, antibacterial and antiviral activity, as well as cytotoxicity, antitumour properties and use as an antidepressant and neuroprotective agent. Hyperforin, the most prominent and best-studied PPAP to date, may serve as an example of the latter point in particular (Richard, 2014 ). The pronounced bicyclic framework, common to most PPAPs and many other natural compounds (Roy et al., 2023 ), makes them particularly compelling for research in natural product chemistry and medicinal applications.

Several approaches have been explored to synthesize polycyclic polyprenylated acylphloroglucines (PPAPs), yet achieving regioselective and diastereoselective control during modification of the core structure can be challenging due to the molecule's dense stereochemically rich framework. Consequently, precursors and intermediates often require rigorous confirmation of stereochemistry through advanced techniques, such as single-crystal X-ray diffraction, prior to further derivatization. Recent advancements in these stereochemical control strategies have opened new pathways not only to natural PPAPs but also to synthetic analogues with enhanced or modified bioactivity profiles.

In our approach to PPAP synthesis (König et al., 2024 , 2025 ), we focused on designing intermediate structures with a high degree of flexibility in substitution patterns, particularly at bridgehead positions. This flexibility is essential for achieving the precise stereochemical and functional complexity required for both natural and synthetic PPAPs, ultimately enhancing the efficiency and specificity of our synthetic route.

The title compounds 1–4 were synthesized as model structures to investigate the reductive and substitutional reactivity of the β-alkoxy enone system found in PPAP precursors.

2. Structural commentary

Crystals suitable for X-ray diffraction analysis were obtained for 1–4 and their molecular structures are illustrated in Fig. 1. Compound 1 crystallizes in the Sohnke space group P2₁ and was refined as an inversion twin. Compounds 2, 3 and 4 crystallize in centrosymmetric space groups (P $[\overline{1}]$ , P2₁/n and P2₁/c, respectively) and thus occur as enantiomeric pairs in the crystal. Notably, although compound 2 crystallizes in P $[\overline{1}]$ , the asymmetric unit contains two crystallographically distinct molecules (Z′ = 2), 2a and 2b, which are chemically mirror images of each other [Fig. 1(b)]. Both compounds are related to their respective crystallographically enantiomeric partners through the inversion centre in the unit cell. The five molecular compounds 1, 2a, 2b, 3 and 4 share a bicyclo[3.3.1]nonanone core structure but differ structurally at positions X⁴, X⁹, R⁵, R⁷, R^8eq and R^8ax (Fig. 2). In the crystal structures of compounds 2 and 4, the OH groups form a hydrogen-bonded network.

Figure 1
The molecular structures of compounds (a) 1, (b) 2a and 2b, (c) 3 and (d) 4, with the atom labelling and displacement ellipsoids drawn at the 50% probability level. The dashed line in part (b) indicates the intermolecular hydrogen bond between the enantiomeric compounds 2a and 2 b.

Figure 2
Numbering scheme for ring I (C1/C8/C7/C6/C5/C9) and ring II (C1–C5/C9) for the basic bicyclo[3.3.1]nonanone framework and its substituents X⁴, X⁹, R⁵, R⁷, R^8ax and R^8eq for the assignment of the molecular compounds 1, 2, 3 and 4.

To describe the structural characteristics of these molecules, puckering parameters (Cremer & Pople, 1975 ) were analyzed (Table 1). For consistent representation, all crystal structures were treated with a unified naming scheme for the bicyclo[3.3.1]nonane core (Fig. 2). The starting atom for rings I and II is C1, with the rotation direction chosen as C1 toward C8 for ring I and C1 toward C2 for ring II. Focus was placed on the folding of the two six-membered rings C1/C8/C7/C6/C5/C9 (I) and C1–C5/C9 (II). The influence of substituents of ring I on its expected chair conformation [⁶C₁; Fig. 3(a)] was determined using the puckering parameters. With regard to ring II, it is known that the introduction of three sp²-hybridized atoms into the bicyclo[3.3.1]nonane skeleton (X⁴ = O) leads to planarity of this part of the ring (Zefirov & Palyulin, 1991 ). Consequently one would expect a C_s-symmetric envelope conformation (E₉) for the six-membered ring in which there are five C atoms in the plane and C9 below [Fig. 3(b)]. However, replacing the sp²-hybridized C atom at position 4 of ring II with an sp³-hybridized C atom (X⁴ = OH/H) alters the folding of the respective ring, leading to a C₂-symmetric half-chair conformation (⁵H₉). In this conformation, four C atoms lie in the plane, with C5 positioned above and C9 below it [Fig. 3(c)].

Table 1
Puckering parameters Q (Å), Θ (°) and Φ (°) of the cyclohexane rings I and II of 1, 2a, 2b, 3 and 4

		Ring I			Ring II
	Q (Å)	Θ (°)	Φ (°)	Q (Å)	Θ (°)	Φ (°)
1	0.590 (2)	172.2 (2)	104.4 (1)	0.505 (2)	56.7 (2)	306.0 (2)
2a	0.591 (3)	169.6 (3)	140.4 (2)	0.534 (3)	48.3 (3)	284.1 (4)
2b^a	0.593 (3)	170.7 (3)	139.1 (2)	0.541 (3)	47.8 (3)	286.9 (4)
3	0.592 (2)	171.6 (2)	115.6 (1)	0.501 (2)	58.2 (2)	310.9 (2)
4	0.592 (1)	170.2 (1)	120.6 (7)	0.489 (1)	52.4 (1)	298.5 (2)
Note: (a) for 2b (the enantiomer of 2a), the tabulated values of Θ and Φ were calculated from the observed Θ′ and Φ′ using the equations Θ = 180° – Θ′ and Φ = 180° + Φ′.

Figure 3
Overview of the cyclohexane conformations (bold black bonds) and their symmetries as described in the text: (a) chair conformation (D_3d), with four atoms in the plane and atom C6 above and C1 below (⁶C₁); (b) envelope conformation (C_s) with atoms C1–C5 in the plane and C9 below (E₉); (c) half-chair conformation (C₂) with atoms C1–C4 in the plane and atom C5 above and C9 below (looking towards the twofold axis in the middle of bond C2—C3 and bond C5—C9).

The puckering parameters Q, Θ and Φ allow a complete description of the conformations of I and II in polar coordinates, with every possible conformation represented as a point on a sphere of radius Q, the polar angle Θ [angle with respect to the positive polar axis (the north pole) with 0 ≤ Θ ≤ 180°], and the azimuthal angle Φ (rotation around the equator with 0 ≤ Φ ≤ 360°) (Cremer & Pople, 1975; Giacovazzo et al., 2011 ). On this sphere, the ideal chair conformation (C) (D_3d) is located at the poles with Θ = 0° and Θ = 180° (Φ undefined). The two higher-energy states, half-chair (H) (C₂) and envelope (E) (C_s), are situated towards the equator at tan Θ = ± $[\sqrt 3/2]$ (Θ = 50.8°) and tan Θ = ± $[\sqrt 2]$ (Θ = 54.7°), and interconvert via pseudorotation [Φ = n × 60° + 30° for (H) and Φ = n × 60° for (E)]. Table 1 summarizes the puckering parameters for rings I and II. In the five investigated structures 1, 2a, 2b, 3 and 4 of the bicyclo[3.3.1]nonane core, all conformations of the six-membered rings I are very close to the ideal chair conformation (⁶C₁), with very tightly grouped Θ values (169.6 < Θ < 172.2°). In accordance with a previous report (Zefirov & Palyulin, 1991), the influence of substituents R⁵, R⁷, R^8eq and R^8ax, as well as the difference between the keto group at C9 in compounds 1, 3 and 4 compared to the dimethoxy group in 2, appears to have no significant impact on the ⁶C₁ conformation of ring I. Even bulky substituents in the axial position at C7, for example, OCH₂Ph [Inouye et al., 1987 ; Q = 0.561 (3) Å, Θ = 165.0 (3) and Φ = 118.1 (13)°] or CH₂CHC(CH₃)₂ [Biber et al., 2011 ; Q = 0.560 Å, Θ = 170.8 (5) and Φ = 128 (3)°] leave the six-membered ring I in a nearly ideal chair conformation with a small distortion towards ⁷E.

A closer examination of the puckering parameters for ring II reveals a slightly different picture. Compounds 1 and 3 with X⁴ = O adopt a nearly ideal envelope conformation (E₉) (1: Θ = 56.7° and Φ = 306.0°; 3: Θ = 58.2° and Φ = 310.9°), with C9 lying out of the plane of the ring and a mirror plane passing through atoms C3 and C9 [Fig. 3(b)]. When the C4 keto group is reduced to an alcohol (sp²→sp³), the ring exhibits greater flexibility. In this case, compound 2 adopts a conformation close to the half-chair form (⁵H₉) (2a: Θ = 48.3° and Φ = 284.1°; 2b: Θ = 47.8° and Φ = 286.9°), with a twofold axis passing through the bonds C2—C3 and C5—C9 [Fig. 3(c)]. In contrast, compound 4 is better described as a linear combination of E₉ and ⁵H₉ (Θ = 52.4° and Φ = 298.5°).

3. Supramolecular features

Compounds 2 and 4 feature an OH group at C4, with the H atom capable of acting as a donor in C—H⋯O hydrogen bonding (Tables 2 and 3). In the crystal structure of 2, there are two crystallographically independent molecules in the asymmetric unit, which are chemically enantiomers of each other. 2a and 2b are interconnected via hydrogen bonds [Fig. 4(a)]. 2a forms a hydrogen bond perpendicular to the a axis and directed along the b axis, with H2O as the donor and O8 in 2b as the acceptor [O2—H2O⋯O8 = 2.858 (3) Å and 176 (3)°]. Respectively, 2b forms another hydrogen bond nearly parallel to the first (angle between lines O2⋯O8 and O6⋯O4ⁱ; symmetry code: (i) x + 1, y, z: 13.67 (8)°], with H6O as the donor and O4 in 2a as the acceptor [O6—H6O⋯O4ⁱ; 2.863 (3)Å and 171 (3)°]. The distances between the strands are approximately equidistant [H6O⋯H2O = 3.82 (4) Å and H2Oⁱ⋯H6O = 3.92 (4) Å]. In both 2a and 2b, six atoms are involved in the bonding resulting in an infinite C(6) chain of hydrogen-bonded molecules along the a direction (Bernstein et al., 1995 ). The crystal structure of 4 possesses a crystallographic glide mirror plane, which transforms the hydrogen bonds between 4 with H2 as donor and its enantiomer with O3ⁱⁱ as acceptor [symmetry code: (ii) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ] into one another [Fig. 4(b)]. In this case, the hydrogen bonds are slightly tilted from the glide-plane in the c direction [angle between the line O3ⁱⁱ⋯O2 and the c-glide plane = 12.40 (4)°]. Here too an infinite C(6) chain forms. The symmetry class of this Frieze group is p11g (No. 5 in International Tables for Crystallography, 2010 ).

Table 2
Hydrogen-bond geometry (Å, °) for 2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6O⋯O4ⁱ	0.84 (1)	2.03 (1)	2.863 (3)	172 (3)
O2—H2O⋯O8	0.84 (1)	2.02 (1)	2.858 (3)	176 (3)
Symmetry code: (i) .

Table 3
Hydrogen-bond geometry (Å, °) for 4

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3ⁱ	0.85 (1)	2.06 (1)	2.8736 (11)	162 (2)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 4
Hydrogen-bonding network of 2 and 4. (a) Hydrogen bonds (blue dashed lines) perpendicular to the a direction between 2a and 2b via O2—H20 and O8, and O6—H6O and O4ⁱ [symmetry code: (i) x + 1, y, z]. The formed C(6) chain is aligned in a direction. (b) The hydrogen bonds (blue dashed lines) in the c direction via O2—H2 and O3ⁱⁱ [symmetry code: (ii) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ and via O2ⁱⁱⁱ—H2ⁱⁱⁱ and O3 [symmetry code: (iii) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ], are deflected by 12.40 (4)° against the c-glide plane (black dashed line). The formed C(6) chain has the symmetry of the Frieze group p11g.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.45, November 2024; Groom et al., 2016 ) indicated 441, 165 and 15 compounds incorporating a bicyclo[3.3.1]non-2-ene, bicyclo[3.3.1]non-2-en-9-one and 4-methoxybicyclo[3.3.1]non-3-ene-2,9-dione motif, respectively.

5. Synthesis and crystallization

5.1. 4-Methoxybicyclo[3.3.1]non-3-ene-2,9-dione (1)

The reaction was carried out in a round-bottomed flask under ambient conditions. To a solution of 4-hydroxybicyclo[3.3.1]non-3-ene-2,9-dione (97.9 mg, 0.59 mmol; Shishido et al., 1986 ; Schönwälder et al., 1984 ) in 6 ml of acetone was added K₂CO₃ (333 mg, 2.41 mmol) and dimethyl sulfate (70 µl, 0.74 mmol). The suspension was refluxed for 2 h. The reaction mixture was allowed to reach room temperature and treated with H₂O. The layers were separated and the aqueous layer was extracted thrice with Et₂O. The combined organic extracts were dried over anhydrous MgSO₄ and concentrated in vacuo. Purification of the residue by flash column chromatography (ⁿPen/Et₂O = 1:2) afforded 1 (yield: 84.2 mg, 0.47 mmol, 79%; m.p. 365.1–366.4 K) as a colourless solid.

¹H NMR (CDCl₃, 400 MHz): δ 5.79 (s, 1H), 3.79 (s, 3H), 3.21–3.19 (m, 2H), 2.22–2.16 (m, 1H), 2.14–2.07 (m, 1H), 2.00–1.86 (m, 2H), 1.79–1.60 (m, 2H); ¹³C NMR (CDCl₃, 100 MHz): δ 207.4, 195.6, 175.6, 105.9, 61.3, 56.9, 53.3, 32.6, 30.5, 17.5.

HRMS (ESI) m/z calculated for C₁₀H₁₂O₃⁺ [M + H]⁺: 181.08592, found: 181.08547.

5.2. 4,9,9-Trimethoxybicyclo[3.3.1]non-3-en-2-ol (2)

This compound was synthesized over two steps.

The reaction was carried out in a flame-dried round-bottomed flask under inert conditions. To a solution of 4-hydroxybicyclo[3.3.1]non-3-ene-2,9-dione (504 mg, 3.02 mmol; Shishido et al., 1986; Schönwälder et al., 1984) in 30 ml of dry methanol was added PTSA (117 mg, 0.62 mmol). The reaction mixture was refluxed overnight. The reaction mixture was allowed to reach room temperature and concentrated in vacuo. Purification of the residue by flash column chromatography (ⁿPen/Et₂O = 1:1) afforded 4,9,9-trimethoxybicyclo[3.3.1]non-3-en-2-one (yield: 593 mg, 2.62 mmol, 87%) as a colourless oil that solidifies in the cold.

¹H NMR (CDCl₃, 500 MHz): δ 5.47 (s, 1H), 3.64 (s, 3H), 3.12 (s, 3H), 3.05 (s, 3H), 2.74 (q, J = 3.2 Hz, 1H), 2.68–2.66 (m, 1H), 1.76 (tdd, J = 13.3, 5.1, 3.9 Hz, 1H), 1.66 (tdd, J = 13.6, 5.4, 4.4 Hz, 1H), 1.55 (dddt, J = 15.0, 4.7, 3.1, 1.6 Hz, 1H), 1.49 (dddt, J = 13.5, 5.0, 3.2, 1.6 Hz, 1H), 1.42–1.24 (m, 2H); ¹³C NMR (CDCl₃, 125 MHz): δ 199.7, 176.6, 103.7, 100.7, 56.1, 48.8, 47.7, 46.8, 42.1, 24.1, 22.7, 16.4.

HRMS (ESI) m/z calculated for C₁₂H₁₉O₄⁺ [M + H]⁺: 227.12779, found: 227.12863.

The reaction was carried out in a flame-dried round-bottomed flask under inert conditions. To a solution of 4,9,9-trimethoxybicyclo[3.3.1]non-3-en-2-one (704 mg, 3.11 mmol) in 60 ml of dry THF was added dropwise DIBAL-H (6.2 ml, 6.20 mmol, 1.0 M in hexane) at 195 K. After stirring for 2 h, the reaction mixture was warmed to 233 K and then to 273 K. The reaction mixture was treated with an aqueous solution of potassium sodium tartrate. The layers were separated, and the aqueous layer was extracted thrice with Et₂O. The combined organic extracts were dried over anhydrous MgSO₄ and concentrated in vacuo. Purification of the residue by flash column chromatography (ⁿPen/Et₂O = 1:1) afforded 2 (yield: 485 mg, 2.12 mmol, 69%; m.p. 336.8–337.4 K) as a colourless solid.

¹H NMR (CDCl₃, 400 MHz): δ 4.81 (d, J = 2.8 Hz, 1H), 4.57–4.52 (m, 1H), 3.54 (s, 3H), 3.19 (s, 3H), 3.16 (s, 3H), 2.52 (q, J = 3.0 Hz, 1H), 2.34–2.30 (m, 1H), 1.92–1.85 (m, 1H), 1.73 (ttd, J = 12.6, 4.4, 1.1 Hz, 1H), 1.61–1.31 (m, 5H); ¹³C NMR (CDCl₃, 100 MHz): δ 155.5, 101.7, 98.7, 68.6, 54.7, 47.6, 46.8, 40.5, 38.4, 24.7, 21.8, 15.75.

HRMS (ESI) m/z calculated for C₁₂H₁₉O₄⁻ [M – H]⁻: 227.12888,found: 227.12864.

5.3. 4-Methoxy-6-methyl-1-(3-methylbut-2-en-1-yl)-6-(4-methylpent-3-en-1-yl)bicyclo[3.3.1]non-3-ene-2,9-dione (3)

The reaction was carried out in a flame-dried round-bottomed flask under inert conditions. To a solution of 4-methoxy-6-methyl-6-(4-methylpent-3-en-1-yl)bicyclo[3.3.1]non-3-ene-2,9-dione (55.4 mg, 0.20 mmol; König et al., 2024) and prenyl bromide (1.1 ml, 9.52 mmol) in 2.2 ml dry THF was added over 3 min a freshly prepared solution of LDA (1.6 ml, 0.40 mmol) at 173 K. The now yellow solution was allowed to reach 195 K over 30 min and then treated with H₂O. The layers were separated, and the aqueous layer was extracted thrice with Et₂O. The combined organic extracts were dried over anhydrous MgSO₄ and concentrated in vacuo. Purification of the residue by flash column chromatography (ⁿPen/Et₂O = 3:1→1:1) afforded 3 (yield: 9.6 mg, 27.9 µmol, 14%; m.p. 341.9–342.2 K) as a colourless solid.

¹H NMR (CDCl₃, 400 MHz): δ 5.71 (s, 1H), 5.01 (tsept, J = 7.0, 1.2 Hz, 1H), 4.97 (tsept, J = 7.0, 1.2 Hz, 1H), 3.74 (s, 3H), 2.99 (s, 1H), 2.42 (d, J = 6.8 Hz, 2H), 2.08 (tt, J = 12.5, 6.1 Hz, 1H), 1.90 (tt, J = 12.7, 6.6 Hz, 1H), 1.82–1.78 (m, 2H), 1.76–1.69 (m, 1H), 1.68 (s, 3H), 1.66 (s, 3H), 1.63 (s, 3H), 1.60 (s, 3H), 1.38–1.32 (m, 1H), 1.22 (td, J = 11.3, 5.1 Hz, 2H), 1.00 (s, 3H); ¹³C NMR (CDCl₃, 100 MHz): δ 207.9, 197.8, 174.9, 133.8, 131.6, 124.0, 119.6, 106.0, 63.1, 62.6, 56.4, 42.4, 41.7, 34.5, 31.2, 29.3, 25.9, 25.7, 21.9, 21.3, 18.0, 17.5.

HRMS (ESI) m/z calculated for C₂₂H₃₃O₃⁺ [M + H]⁺: 345.24242, found: 345.24241.

5.4. 4-tert-Butyl-4-hydroxy-2-methoxy-8-methyl-7-(3-methylbut-2-en-1-yl)-8-(4-methylpent-3-en-1-yl)bicyclo[3.3.1]non-2-en-9-one (4)

The reaction was carried out in a flame-dried round-bottomed flask under inert conditions. To a solution of 4-methoxy-6-methyl-7-(3-methylbut-2-en-1-yl)-6-(4-methylpent-3-en-1-yl)bicyclo[3.3.1]-non-3-ene-2,9-dione (17.4 mg, 50.5 µmol; König et al., 2025) in 5 ml of dry THF was added dropwise t-BuLi (53 µl, 101 µmol) at 168 K. The reaction mixture was stirred for 90 min and then treated with a saturated aqueous solution of NH₄Cl. The layers were separated, and the aqueous layer was extracted thrice with Et₂O. The combined organic extracts were dried over anhydrous MgSO₄ and concentrated in vacuo. Purification of the residue by flash column chromatography (ⁿPen/Et₂O = 10:1) afforded 4 (yield: 19.0 mg, 47.3 µmol, 94%; m.p. 382.7.1–384.3 K) as a colourless solid.

¹H NMR (CDCl₃, 400 MHz): δ 5.07–5.01 (m, 3H), 3.56 (s, 3H), 2.83 (bs, 1H), 2.70 (s, 1H), 2.29 (ddd, J = 14.3, 3.9 Hz, 2.7 Hz, 1H), 2.23–2.16 (m, 1H), 2.10 (dd, J = 13.7, 4.9 Hz, 1H), 1.85–1.77 (m, 1H), 1.68 (s, 6H), 1.65–1.62 (m, 1H), 1.61 (s, 3H), 1.57 (s, 3H), 1.54–1.39 (m, 3H), 1.22–1.15 (m, 1H), 0.92 (s, 9H), 0.84 (s, 3H); ¹³C NMR (CDCl₃, 100 MHz): δ 212.0, 155.4, 132.7, 131.0, 124.9, 123.1, 101.6, 77.5, 58.6, 54.6, 52.2, 46.2, 41.2, 39.8, 38.5, 32.5, 28.2, 25.8, 25.7, 25.3, 21.7, 17.9, 17.5, 17.3.

HRMS (ESI) m/z calculated for C₂₆H₄₁O₃⁻ [M – H]⁻: 401.30612, found: 401.30503.

All compounds were crystallized after flash chromatography by dissolving 10 mg to 30 mg of the respective purified compound in a 10 ml round-bottomed flask with 1–2 ml DCM. The flasks were topped with a septum and a cannula to allow slow solvent evaporation. All solutions were left undisturbed at room temperature for two to four weeks to yield colourless to pale yellow crystals.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All H atoms were treated as recommended by Müller et al. (2006 ). A riding model was used for the C-bonded H atoms, with U_iso(H) = 1.5U_eq(methyl C) and 1.2U_eq(C) for other C-bound H atoms. The positional parameters of the O-bonded H atoms of 2a, 2b and 4 were refined using isotropic displacement parameters which were set at 1.5 times the U_eq value of the parent atom. In addition, restraints of 0.84 (1) Å were used for the O—H bond lengths. The crystal structure of compound 1 was refined as an inversion twin (BASF = 0.5).

Table 4
Experimental details

Experiments were carried out with Mo Kα radiation using a Bruker D8 VENTURE PHOTON II. Absorption was corrected for by multi-scan methods (SADABS; Krause et al., 2015 ).

	(1)	(2)	(3)	(4)
Crystal data
Chemical formula	C₁₀H₁₂O₃	C₁₂H₂₀O₄	C₂₂H₃₂O₃	C₂₆H₄₂O₃
M_r	180.20	228.28	344.47	402.59
Crystal system, space group	Monoclinic, P2₁	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/n	Monoclinic, P2₁/c
Temperature (K)	153	152	133	143
a, b, c (Å)	6.4819 (4), 7.4766 (5), 9.0627 (5)	7.7330 (15), 10.976 (2), 13.874 (3)	14.1871 (6), 6.3306 (2), 22.4159 (8)	15.1165 (5), 13.9068 (4), 12.8150 (4)
α, β, γ (°)	90, 99.546 (2), 90	101.984 (5), 92.032 (5), 90.293 (5)	90, 101.702 (1), 90	90, 113.218 (1), 90
V (Å³)	433.12 (5)	1151.2 (4)	1971.39 (13)	2475.81 (13)
Z	2	4	4	4
μ (mm⁻¹)	0.10	0.10	0.08	0.07
Crystal size (mm)	0.38 × 0.08 × 0.06	0.28 × 0.24 × 0.04	0.18 × 0.14 × 0.04	0.26 × 0.16 × 0.08

Data collection
T_min, T_max	0.699, 0.746	0.578, 0.746	0.687, 0.746	0.704, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	8258, 2031, 1948	8885, 4662, 2677	28995, 4348, 3271	87917, 5484, 4697
R_int	0.028	0.055	0.067	0.048
(sin θ/λ)_max (Å⁻¹)	0.658	0.625	0.642	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.074, 1.08	0.057, 0.139, 0.98	0.046, 0.116, 1.05	0.040, 0.108, 1.05
No. of reflections	2031	4662	4348	5484
No. of parameters	119	301	232	274
No. of restraints	1	2	0	1
H-atom treatment	H-atom parameters constrained	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.15	0.24, −0.24	0.28, −0.22	0.29, −0.20
Absolute structure	Refined as an inversion twin	–	–	–
Absolute structure parameter	0.5	–	–	–
Computer programs: APEX4 and SAINT (Bruker, 2021 ), SHELXT2018 (Sheldrick, 2015a ), SHELXL2019 (Sheldrick, 2015b ), ShelXle (Hübschle et al., 2011 ), DIAMOND (Brandenburg, 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2429999; 2430008; 2430001; 2430007

Crystal structure: contains datablocks 1, 2, 3, 4, global. DOI: https://doi.org/10.1107/S2056989025003299/ev2016sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989025003299/ev20161sup2.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989025003299/ev20162sup3.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989025003299/ev20163sup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989025003299/ev20164sup5.cml

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989025003299/ev20161sup6.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989025003299/ev20162sup7.hkl

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S2056989025003299/ev20163sup8.hkl

Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S2056989025003299/ev20164sup9.hkl

checkCIF report

Computing details top

4-Methoxybicyclo[3.3.1]non-3-ene-2,9-dione (1) top

Crystal data top

C₁₀H₁₂O₃	F(000) = 192
M_r = 180.20	D_x = 1.382 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 6.4819 (4) Å	Cell parameters from 6064 reflections
b = 7.4766 (5) Å	θ = 2.3–27.9°
c = 9.0627 (5) Å	µ = 0.10 mm⁻¹
β = 99.546 (2)°	T = 153 K
V = 433.12 (5) Å³	Rod, colourless
Z = 2	0.38 × 0.08 × 0.06 mm

Data collection top

Bruker D8 VENTURE PHOTON II diffractometer	1948 reflections with I > 2σ(I)
Radiation source: INCOATEC IÂµS microfocus sealed tube	R_int = 0.028
φ and ω scans	θ_max = 27.9°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −8→7
T_min = 0.699, T_max = 0.746	k = −9→9
8258 measured reflections	l = −11→11
2031 independent reflections

Refinement top

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)] = 0.030	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0364P)² + 0.0624P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2031 reflections	Δρ_max = 0.18 e Å⁻³
119 parameters	Δρ_min = −0.15 e Å⁻³
1 restraint	Absolute structure: Refined as an inversion twin
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.5

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. Refined as a 2-component inversion twin

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

	x	y	z	U_iso*/U_eq
O1	0.6356 (2)	0.20219 (18)	0.73144 (16)	0.0358 (3)
O2	0.80123 (19)	0.73388 (16)	0.49209 (12)	0.0255 (3)
O3	0.2740 (2)	0.7098 (2)	0.73484 (15)	0.0345 (3)
C1	0.6305 (3)	0.7548 (2)	0.70026 (17)	0.0214 (3)
H1	0.578127	0.868685	0.649526	0.026*
C2	0.7203 (2)	0.6369 (2)	0.59258 (16)	0.0207 (3)
C10	0.8884 (3)	0.6368 (3)	0.3793 (2)	0.0318 (4)
H10A	0.930016	0.721305	0.306964	0.048*
H10B	0.783321	0.554093	0.327603	0.048*
H10C	1.011125	0.569139	0.426813	0.048*
C3	0.7170 (3)	0.4564 (2)	0.59890 (18)	0.0241 (3)
H3	0.773987	0.388629	0.526623	0.029*
C4	0.6278 (3)	0.3647 (2)	0.71463 (18)	0.0242 (3)
C5	0.5211 (3)	0.4780 (2)	0.82067 (18)	0.0240 (3)
H5	0.397653	0.412087	0.846504	0.029*
C6	0.6779 (3)	0.5196 (2)	0.96573 (19)	0.0285 (4)
H6A	0.604837	0.586413	1.036072	0.034*
H6B	0.729428	0.405919	1.014438	0.034*
C7	0.8636 (3)	0.6296 (2)	0.93294 (18)	0.0277 (4)
H7A	0.951032	0.665124	1.028598	0.033*
H7B	0.950543	0.554829	0.877127	0.033*
C8	0.7938 (3)	0.7970 (2)	0.84179 (19)	0.0252 (4)
H8A	0.917481	0.854469	0.810933	0.030*
H8B	0.732289	0.882757	0.905492	0.030*
C9	0.4511 (3)	0.6540 (2)	0.74873 (17)	0.0224 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0417 (8)	0.0189 (6)	0.0482 (8)	0.0001 (6)	0.0112 (6)	0.0026 (5)
O2	0.0288 (7)	0.0263 (6)	0.0225 (5)	−0.0041 (5)	0.0078 (4)	−0.0002 (4)
O3	0.0259 (7)	0.0372 (7)	0.0423 (7)	0.0078 (6)	0.0109 (5)	0.0059 (6)
C1	0.0235 (8)	0.0187 (8)	0.0219 (7)	0.0019 (6)	0.0033 (6)	0.0010 (6)
C2	0.0190 (7)	0.0237 (7)	0.0189 (6)	−0.0012 (6)	0.0015 (6)	0.0008 (6)
C10	0.0338 (10)	0.0371 (9)	0.0274 (8)	−0.0049 (8)	0.0139 (7)	−0.0061 (8)
C3	0.0247 (8)	0.0227 (8)	0.0250 (8)	0.0005 (6)	0.0041 (6)	−0.0039 (6)
C4	0.0222 (9)	0.0205 (8)	0.0291 (8)	−0.0004 (6)	0.0020 (6)	0.0003 (6)
C5	0.0236 (9)	0.0231 (8)	0.0264 (8)	−0.0017 (6)	0.0070 (6)	0.0041 (6)
C6	0.0348 (10)	0.0282 (9)	0.0227 (7)	−0.0008 (7)	0.0050 (6)	0.0056 (6)
C7	0.0270 (9)	0.0315 (9)	0.0230 (7)	−0.0001 (7)	−0.0007 (6)	0.0008 (7)
C8	0.0283 (9)	0.0235 (8)	0.0237 (8)	−0.0037 (7)	0.0042 (6)	−0.0030 (6)
C9	0.0236 (8)	0.0225 (7)	0.0219 (7)	0.0021 (6)	0.0057 (6)	−0.0012 (6)

Geometric parameters (Å, º) top

O1—C4	1.225 (2)	C3—H3	0.9500
O2—C2	1.3377 (19)	C4—C5	1.529 (2)
O2—C10	1.443 (2)	C5—C9	1.505 (2)
O3—C9	1.208 (2)	C5—C6	1.554 (2)
C1—C2	1.502 (2)	C5—H5	1.0000
C1—C9	1.510 (2)	C6—C7	1.527 (3)
C1—C8	1.554 (2)	C6—H6A	0.9900
C1—H1	1.0000	C6—H6B	0.9900
C2—C3	1.351 (2)	C7—C8	1.526 (2)
C10—H10A	0.9800	C7—H7A	0.9900
C10—H10B	0.9800	C7—H7B	0.9900
C10—H10C	0.9800	C8—H8A	0.9900
C3—C4	1.451 (2)	C8—H8B	0.9900

C2—O2—C10	116.97 (14)	C9—C5—H5	109.7
C2—C1—C9	107.21 (13)	C4—C5—H5	109.7
C2—C1—C8	111.78 (13)	C6—C5—H5	109.7
C9—C1—C8	108.24 (12)	C7—C6—C5	111.67 (13)
C2—C1—H1	109.8	C7—C6—H6A	109.3
C9—C1—H1	109.8	C5—C6—H6A	109.3
C8—C1—H1	109.8	C7—C6—H6B	109.3
O2—C2—C3	125.52 (15)	C5—C6—H6B	109.3
O2—C2—C1	111.23 (14)	H6A—C6—H6B	107.9
C3—C2—C1	123.25 (14)	C8—C7—C6	111.97 (15)
O2—C10—H10A	109.5	C8—C7—H7A	109.2
O2—C10—H10B	109.5	C6—C7—H7A	109.2
H10A—C10—H10B	109.5	C8—C7—H7B	109.2
O2—C10—H10C	109.5	C6—C7—H7B	109.2
H10A—C10—H10C	109.5	H7A—C7—H7B	107.9
H10B—C10—H10C	109.5	C7—C8—C1	112.38 (14)
C2—C3—C4	120.89 (15)	C7—C8—H8A	109.1
C2—C3—H3	119.6	C1—C8—H8A	109.1
C4—C3—H3	119.6	C7—C8—H8B	109.1
O1—C4—C3	123.06 (16)	C1—C8—H8B	109.1
O1—C4—C5	119.00 (15)	H8A—C8—H8B	107.9
C3—C4—C5	117.94 (14)	O3—C9—C5	124.04 (16)
C9—C5—C4	110.31 (13)	O3—C9—C1	124.16 (15)
C9—C5—C6	107.41 (13)	C5—C9—C1	111.78 (14)
C4—C5—C6	110.00 (14)

C10—O2—C2—C3	1.4 (2)	C9—C5—C6—C7	−57.61 (19)
C10—O2—C2—C1	−178.52 (14)	C4—C5—C6—C7	62.47 (18)
C9—C1—C2—O2	149.74 (13)	C5—C6—C7—C8	52.43 (19)
C8—C1—C2—O2	−91.79 (15)	C6—C7—C8—C1	−50.79 (18)
C9—C1—C2—C3	−30.1 (2)	C2—C1—C8—C7	−63.52 (18)
C8—C1—C2—C3	88.33 (19)	C9—C1—C8—C7	54.34 (18)
O2—C2—C3—C4	179.00 (15)	C4—C5—C9—O3	125.58 (18)
C1—C2—C3—C4	−1.1 (3)	C6—C5—C9—O3	−114.54 (18)
C2—C3—C4—O1	−174.35 (17)	C4—C5—C9—C1	−56.12 (18)
C2—C3—C4—C5	5.1 (2)	C6—C5—C9—C1	63.76 (17)
O1—C4—C5—C9	−157.28 (16)	C2—C1—C9—O3	−123.17 (17)
C3—C4—C5—C9	23.2 (2)	C8—C1—C9—O3	116.10 (18)
O1—C4—C5—C6	84.41 (19)	C2—C1—C9—C5	58.54 (16)
C3—C4—C5—C6	−95.07 (17)	C8—C1—C9—C5	−62.20 (17)

4,9,9-Trimethoxybicyclo[3.3.1]non-3-en-2-ol (2) top

Crystal data top

C₁₂H₂₀O₄	Z = 4
M_r = 228.28	F(000) = 496
Triclinic, P1	D_x = 1.317 Mg m⁻³
a = 7.7330 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.976 (2) Å	Cell parameters from 1376 reflections
c = 13.874 (3) Å	θ = 3.0–25.0°
α = 101.984 (5)°	µ = 0.10 mm⁻¹
β = 92.032 (5)°	T = 152 K
γ = 90.293 (5)°	Plate, colourless
V = 1151.2 (4) Å³	0.28 × 0.24 × 0.04 mm

Data collection top

Bruker D8 VENTURE PHOTON II diffractometer	2677 reflections with I > 2σ(I)
Radiation source: INCOATEC IÂµS microfocus sealed tube	R_int = 0.055
φ and ω scans	θ_max = 26.4°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −9→9
T_min = 0.578, T_max = 0.746	k = −13→13
8885 measured reflections	l = −17→17
4662 independent reflections

Refinement top

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)] = 0.057	Hydrogen site location: mixed
wR(F²) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0513P)²] where P = (F_o² + 2F_c²)/3
4662 reflections	(Δ/σ)_max < 0.001
301 parameters	Δρ_max = 0.24 e Å⁻³
2 restraints	Δρ_min = −0.24 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
O3	0.2250 (2)	0.37070 (16)	0.13978 (14)	0.0244 (5)
O2	0.7476 (2)	0.61301 (17)	0.27191 (16)	0.0288 (5)
H2O	0.741 (4)	0.6909 (10)	0.278 (2)	0.043*
O1	0.5543 (2)	0.27872 (16)	0.40336 (14)	0.0248 (5)
O4	0.2372 (2)	0.50789 (16)	0.29210 (14)	0.0219 (4)
O5	1.0600 (2)	1.16441 (16)	0.39368 (14)	0.0252 (5)
O6	1.2486 (2)	0.75906 (17)	0.26446 (16)	0.0311 (5)
H6O	1.234 (4)	0.6854 (14)	0.271 (2)	0.047*
O7	0.7194 (2)	0.92784 (17)	0.13891 (14)	0.0252 (5)
O8	0.7424 (2)	0.87754 (16)	0.29317 (13)	0.0208 (4)
C1	0.4127 (3)	0.3167 (2)	0.2597 (2)	0.0207 (6)
H1	0.317759	0.267373	0.281279	0.025*
C2	0.5345 (3)	0.3652 (2)	0.3458 (2)	0.0206 (6)
C3	0.6152 (3)	0.4749 (2)	0.3592 (2)	0.0211 (6)
H3	0.695548	0.498054	0.413456	0.025*
C4	0.5835 (3)	0.5635 (2)	0.2916 (2)	0.0210 (6)
H4	0.514429	0.634247	0.327706	0.025*
C5	0.4824 (3)	0.5061 (2)	0.1964 (2)	0.0213 (6)
H5	0.430621	0.575362	0.168691	0.026*
C6	0.5910 (3)	0.4263 (3)	0.1161 (2)	0.0263 (7)
H6A	0.520091	0.406174	0.053892	0.032*
H6B	0.692026	0.476413	0.104437	0.032*
C7	0.6560 (3)	0.3048 (3)	0.1411 (2)	0.0276 (7)
H7A	0.749392	0.323841	0.192827	0.033*
H7B	0.705050	0.252400	0.081777	0.033*
C8	0.5107 (3)	0.2326 (2)	0.1773 (2)	0.0244 (7)
H8A	0.560293	0.161608	0.202263	0.029*
H8B	0.428924	0.198770	0.121522	0.029*
C9	0.3347 (3)	0.4262 (2)	0.2210 (2)	0.0200 (6)
C10	0.1260 (4)	0.4544 (3)	0.0941 (2)	0.0324 (7)
H10A	0.054707	0.406678	0.039144	0.049*
H10B	0.204374	0.510236	0.069224	0.049*
H10C	0.051003	0.503695	0.142526	0.049*
C11	0.0995 (3)	0.4525 (3)	0.3350 (2)	0.0306 (7)
H11A	0.019317	0.517320	0.364698	0.046*
H11B	0.147237	0.411031	0.385985	0.046*
H11C	0.037487	0.391278	0.283835	0.046*
C12	0.6804 (4)	0.3079 (3)	0.4830 (2)	0.0311 (7)
H12A	0.682747	0.240840	0.519879	0.047*
H12B	0.650051	0.386227	0.526962	0.047*
H12C	0.794670	0.316700	0.456675	0.047*
C13	0.9185 (3)	1.0473 (2)	0.2509 (2)	0.0212 (6)
H13	0.826248	1.109938	0.271311	0.025*
C14	1.0410 (3)	1.0473 (2)	0.3369 (2)	0.0203 (6)
C15	1.1210 (3)	0.9454 (2)	0.3512 (2)	0.0200 (6)
H15	1.203910	0.952686	0.404336	0.024*
C16	1.0862 (3)	0.8197 (2)	0.2871 (2)	0.0225 (6)
H16	1.019848	0.769528	0.326094	0.027*
C17	0.9785 (3)	0.8221 (2)	0.1917 (2)	0.0214 (6)
H17	0.923065	0.738204	0.168204	0.026*
C18	1.0814 (3)	0.8527 (2)	0.1075 (2)	0.0268 (7)
H18A	1.005550	0.839472	0.047137	0.032*
H18B	1.178675	0.793939	0.094485	0.032*
C19	1.1541 (3)	0.9861 (3)	0.1278 (2)	0.0281 (7)
H19A	1.249799	0.994633	0.178169	0.034*
H19B	1.201510	1.003598	0.066630	0.034*
C20	1.0141 (3)	1.0806 (3)	0.1641 (2)	0.0264 (7)
H20A	0.929714	1.083264	0.109210	0.032*
H20B	1.067692	1.164458	0.185194	0.032*
C21	0.8344 (3)	0.9177 (2)	0.2176 (2)	0.0198 (6)
C22	0.6196 (4)	0.8179 (3)	0.0962 (2)	0.0347 (8)
H22A	0.531624	0.838293	0.049607	0.052*
H22B	0.563015	0.786549	0.148393	0.052*
H22C	0.696186	0.754021	0.061296	0.052*
C23	0.6060 (3)	0.9566 (3)	0.3360 (2)	0.0288 (7)
H23A	0.535246	0.912043	0.375069	0.043*
H23B	0.533485	0.979948	0.283521	0.043*
H23C	0.656028	1.031866	0.378740	0.043*
C24	1.1744 (4)	1.1781 (3)	0.4781 (2)	0.0305 (7)
H24A	1.172238	1.264278	0.515319	0.046*
H24B	1.292245	1.157427	0.457040	0.046*
H24C	1.137482	1.121833	0.520074	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0254 (10)	0.0188 (10)	0.0306 (12)	0.0042 (7)	−0.0063 (9)	0.0099 (9)
O2	0.0218 (10)	0.0161 (10)	0.0522 (15)	−0.0008 (8)	0.0037 (9)	0.0149 (10)
O1	0.0323 (10)	0.0170 (10)	0.0288 (12)	0.0030 (8)	−0.0047 (9)	0.0141 (9)
O4	0.0210 (9)	0.0145 (10)	0.0318 (12)	0.0038 (7)	0.0054 (8)	0.0081 (8)
O5	0.0311 (10)	0.0146 (10)	0.0297 (12)	0.0001 (8)	−0.0046 (9)	0.0052 (9)
O6	0.0242 (10)	0.0181 (11)	0.0546 (15)	0.0102 (8)	0.0080 (10)	0.0145 (10)
O7	0.0263 (10)	0.0212 (11)	0.0296 (12)	−0.0021 (8)	−0.0062 (9)	0.0102 (9)
O8	0.0200 (9)	0.0168 (10)	0.0278 (12)	0.0046 (7)	0.0033 (8)	0.0091 (8)
C1	0.0223 (13)	0.0135 (14)	0.0289 (17)	0.0014 (10)	−0.0007 (12)	0.0106 (12)
C2	0.0225 (13)	0.0151 (14)	0.0271 (17)	0.0069 (10)	0.0043 (12)	0.0105 (12)
C3	0.0203 (13)	0.0194 (15)	0.0260 (17)	0.0031 (11)	−0.0013 (12)	0.0102 (12)
C4	0.0192 (13)	0.0148 (14)	0.0310 (17)	0.0022 (10)	0.0051 (12)	0.0086 (12)
C5	0.0210 (13)	0.0144 (14)	0.0320 (17)	0.0066 (10)	0.0036 (12)	0.0119 (12)
C6	0.0291 (15)	0.0262 (16)	0.0268 (17)	0.0032 (12)	0.0048 (13)	0.0120 (14)
C7	0.0271 (15)	0.0246 (16)	0.0310 (18)	0.0077 (12)	0.0030 (13)	0.0047 (14)
C8	0.0290 (15)	0.0155 (14)	0.0289 (18)	0.0075 (11)	−0.0036 (13)	0.0058 (13)
C9	0.0182 (13)	0.0169 (14)	0.0259 (16)	0.0028 (10)	0.0005 (12)	0.0071 (12)
C10	0.0336 (16)	0.0265 (17)	0.040 (2)	0.0082 (13)	−0.0095 (14)	0.0160 (15)
C11	0.0243 (14)	0.0288 (17)	0.043 (2)	0.0037 (12)	0.0103 (14)	0.0154 (15)
C12	0.0379 (17)	0.0286 (17)	0.0294 (18)	0.0076 (13)	−0.0025 (14)	0.0126 (14)
C13	0.0237 (13)	0.0108 (13)	0.0313 (17)	0.0035 (10)	−0.0031 (12)	0.0100 (12)
C14	0.0224 (13)	0.0147 (14)	0.0248 (16)	−0.0008 (10)	0.0024 (12)	0.0062 (12)
C15	0.0194 (13)	0.0186 (14)	0.0236 (16)	0.0027 (10)	−0.0010 (11)	0.0083 (12)
C16	0.0179 (13)	0.0152 (14)	0.0380 (18)	0.0080 (10)	0.0057 (12)	0.0127 (13)
C17	0.0213 (13)	0.0129 (13)	0.0310 (17)	0.0015 (10)	0.0012 (12)	0.0071 (12)
C18	0.0304 (15)	0.0226 (16)	0.0283 (18)	0.0014 (12)	0.0082 (13)	0.0063 (13)
C19	0.0311 (15)	0.0286 (17)	0.0273 (18)	−0.0036 (12)	0.0046 (13)	0.0118 (14)
C20	0.0258 (14)	0.0260 (16)	0.0309 (18)	−0.0042 (12)	−0.0027 (13)	0.0150 (14)
C21	0.0201 (13)	0.0166 (14)	0.0242 (16)	0.0006 (10)	−0.0015 (12)	0.0084 (12)
C22	0.0385 (17)	0.0254 (17)	0.039 (2)	−0.0050 (13)	−0.0139 (15)	0.0060 (15)
C23	0.0255 (15)	0.0244 (16)	0.040 (2)	0.0108 (11)	0.0106 (13)	0.0121 (14)
C24	0.0343 (16)	0.0291 (17)	0.0285 (18)	−0.0054 (13)	−0.0017 (14)	0.0079 (14)

Geometric parameters (Å, º) top

O3—C9	1.415 (3)	C10—H10B	0.9800
O3—C10	1.431 (3)	C10—H10C	0.9800
O2—C4	1.435 (3)	C11—H11A	0.9800
O2—H2O	0.843 (10)	C11—H11B	0.9800
O1—C2	1.367 (3)	C11—H11C	0.9800
O1—C12	1.431 (3)	C12—H12A	0.9800
O4—C9	1.427 (3)	C12—H12B	0.9800
O4—C11	1.431 (3)	C12—H12C	0.9800
O5—C14	1.365 (3)	C13—C14	1.497 (4)
O5—C24	1.425 (3)	C13—C21	1.536 (3)
O6—C16	1.438 (3)	C13—C20	1.541 (4)
O6—H6O	0.842 (10)	C13—H13	1.0000
O7—C21	1.406 (3)	C14—C15	1.328 (3)
O7—C22	1.436 (3)	C15—C16	1.496 (4)
O8—C21	1.429 (3)	C15—H15	0.9500
O8—C23	1.435 (3)	C16—C17	1.543 (4)
C1—C2	1.499 (4)	C16—H16	1.0000
C1—C9	1.533 (3)	C17—C18	1.529 (3)
C1—C8	1.538 (4)	C17—C21	1.534 (3)
C1—H1	1.0000	C17—H17	1.0000
C2—C3	1.329 (3)	C18—C19	1.533 (4)
C3—C4	1.500 (3)	C18—H18A	0.9900
C3—H3	0.9500	C18—H18B	0.9900
C4—C5	1.526 (4)	C19—C20	1.528 (4)
C4—H4	1.0000	C19—H19A	0.9900
C5—C9	1.528 (3)	C19—H19B	0.9900
C5—C6	1.543 (4)	C20—H20A	0.9900
C5—H5	1.0000	C20—H20B	0.9900
C6—C7	1.529 (4)	C22—H22A	0.9800
C6—H6A	0.9900	C22—H22B	0.9800
C6—H6B	0.9900	C22—H22C	0.9800
C7—C8	1.529 (4)	C23—H23A	0.9800
C7—H7A	0.9900	C23—H23B	0.9800
C7—H7B	0.9900	C23—H23C	0.9800
C8—H8A	0.9900	C24—H24A	0.9800
C8—H8B	0.9900	C24—H24B	0.9800
C10—H10A	0.9800	C24—H24C	0.9800

C9—O3—C10	116.1 (2)	H12A—C12—H12B	109.5
C4—O2—H2O	110 (2)	O1—C12—H12C	109.5
C2—O1—C12	116.2 (2)	H12A—C12—H12C	109.5
C9—O4—C11	116.6 (2)	H12B—C12—H12C	109.5
C14—O5—C24	116.6 (2)	C14—C13—C21	109.5 (2)
C16—O6—H6O	106 (2)	C14—C13—C20	110.8 (2)
C21—O7—C22	116.0 (2)	C21—C13—C20	109.1 (2)
C21—O8—C23	116.4 (2)	C14—C13—H13	109.1
C2—C1—C9	109.6 (2)	C21—C13—H13	109.1
C2—C1—C8	109.8 (2)	C20—C13—H13	109.1
C9—C1—C8	109.5 (2)	C15—C14—O5	126.7 (2)
C2—C1—H1	109.3	C15—C14—C13	122.6 (2)
C9—C1—H1	109.3	O5—C14—C13	110.7 (2)
C8—C1—H1	109.3	C14—C15—C16	122.8 (2)
C3—C2—O1	126.4 (2)	C14—C15—H15	118.6
C3—C2—C1	123.2 (2)	C16—C15—H15	118.6
O1—C2—C1	110.3 (2)	O6—C16—C15	108.7 (2)
C2—C3—C4	122.2 (2)	O6—C16—C17	110.7 (2)
C2—C3—H3	118.9	C15—C16—C17	114.2 (2)
C4—C3—H3	118.9	O6—C16—H16	107.7
O2—C4—C3	108.1 (2)	C15—C16—H16	107.7
O2—C4—C5	111.5 (2)	C17—C16—H16	107.7
C3—C4—C5	113.9 (2)	C18—C17—C21	109.5 (2)
O2—C4—H4	107.7	C18—C17—C16	114.9 (2)
C3—C4—H4	107.7	C21—C17—C16	108.0 (2)
C5—C4—H4	107.7	C18—C17—H17	108.1
C4—C5—C9	108.7 (2)	C21—C17—H17	108.1
C4—C5—C6	114.8 (2)	C16—C17—H17	108.1
C9—C5—C6	109.0 (2)	C17—C18—C19	114.0 (2)
C4—C5—H5	108.0	C17—C18—H18A	108.8
C9—C5—H5	108.0	C19—C18—H18A	108.8
C6—C5—H5	108.0	C17—C18—H18B	108.8
C7—C6—C5	114.4 (2)	C19—C18—H18B	108.8
C7—C6—H6A	108.7	H18A—C18—H18B	107.6
C5—C6—H6A	108.7	C20—C19—C18	111.1 (2)
C7—C6—H6B	108.7	C20—C19—H19A	109.4
C5—C6—H6B	108.7	C18—C19—H19A	109.4
H6A—C6—H6B	107.6	C20—C19—H19B	109.4
C6—C7—C8	111.6 (2)	C18—C19—H19B	109.4
C6—C7—H7A	109.3	H19A—C19—H19B	108.0
C8—C7—H7A	109.3	C19—C20—C13	111.6 (2)
C6—C7—H7B	109.3	C19—C20—H20A	109.3
C8—C7—H7B	109.3	C13—C20—H20A	109.3
H7A—C7—H7B	108.0	C19—C20—H20B	109.3
C7—C8—C1	111.1 (2)	C13—C20—H20B	109.3
C7—C8—H8A	109.4	H20A—C20—H20B	108.0
C1—C8—H8A	109.4	O7—C21—O8	109.84 (19)
C7—C8—H8B	109.4	O7—C21—C17	115.2 (2)
C1—C8—H8B	109.4	O8—C21—C17	104.9 (2)
H8A—C8—H8B	108.0	O7—C21—C13	105.2 (2)
O3—C9—O4	109.76 (19)	O8—C21—C13	113.6 (2)
O3—C9—C5	115.0 (2)	C17—C21—C13	108.3 (2)
O4—C9—C5	105.4 (2)	O7—C22—H22A	109.5
O3—C9—C1	105.0 (2)	O7—C22—H22B	109.5
O4—C9—C1	113.5 (2)	H22A—C22—H22B	109.5
C5—C9—C1	108.5 (2)	O7—C22—H22C	109.5
O3—C10—H10A	109.5	H22A—C22—H22C	109.5
O3—C10—H10B	109.5	H22B—C22—H22C	109.5
H10A—C10—H10B	109.5	O8—C23—H23A	109.5
O3—C10—H10C	109.5	O8—C23—H23B	109.5
H10A—C10—H10C	109.5	H23A—C23—H23B	109.5
H10B—C10—H10C	109.5	O8—C23—H23C	109.5
O4—C11—H11A	109.5	H23A—C23—H23C	109.5
O4—C11—H11B	109.5	H23B—C23—H23C	109.5
H11A—C11—H11B	109.5	O5—C24—H24A	109.5
O4—C11—H11C	109.5	O5—C24—H24B	109.5
H11A—C11—H11C	109.5	H24A—C24—H24B	109.5
H11B—C11—H11C	109.5	O5—C24—H24C	109.5
O1—C12—H12A	109.5	H24A—C24—H24C	109.5
O1—C12—H12B	109.5	H24B—C24—H24C	109.5

C12—O1—C2—C3	−3.0 (4)	C24—O5—C14—C15	−1.5 (4)
C12—O1—C2—C1	174.1 (2)	C24—O5—C14—C13	−179.6 (2)
C9—C1—C2—C3	−25.6 (4)	C21—C13—C14—C15	27.9 (4)
C8—C1—C2—C3	94.7 (3)	C20—C13—C14—C15	−92.4 (3)
C9—C1—C2—O1	157.2 (2)	C21—C13—C14—O5	−153.9 (2)
C8—C1—C2—O1	−82.5 (3)	C20—C13—C14—O5	85.8 (3)
O1—C2—C3—C4	−179.8 (2)	O5—C14—C15—C16	177.4 (2)
C1—C2—C3—C4	3.4 (4)	C13—C14—C15—C16	−4.7 (4)
C2—C3—C4—O2	−136.6 (3)	C14—C15—C16—O6	135.7 (3)
C2—C3—C4—C5	−12.2 (4)	C14—C15—C16—C17	11.7 (4)
O2—C4—C5—C9	165.22 (19)	O6—C16—C17—C18	−41.7 (3)
C3—C4—C5—C9	42.6 (3)	C15—C16—C17—C18	81.3 (3)
O2—C4—C5—C6	42.8 (3)	O6—C16—C17—C21	−164.30 (19)
C3—C4—C5—C6	−79.8 (3)	C15—C16—C17—C21	−41.3 (3)
C4—C5—C6—C7	68.5 (3)	C21—C17—C18—C19	54.7 (3)
C9—C5—C6—C7	−53.7 (3)	C16—C17—C18—C19	−67.0 (3)
C5—C6—C7—C8	48.6 (3)	C17—C18—C19—C20	−49.6 (3)
C6—C7—C8—C1	−50.6 (3)	C18—C19—C20—C13	51.3 (3)
C2—C1—C8—C7	−60.8 (3)	C14—C13—C20—C19	61.2 (3)
C9—C1—C8—C7	59.5 (3)	C21—C13—C20—C19	−59.4 (3)
C10—O3—C9—O4	53.5 (3)	C22—O7—C21—O8	−55.6 (3)
C10—O3—C9—C5	−65.1 (3)	C22—O7—C21—C17	62.5 (3)
C10—O3—C9—C1	175.8 (2)	C22—O7—C21—C13	−178.3 (2)
C11—O4—C9—O3	61.6 (3)	C23—O8—C21—O7	−59.8 (3)
C11—O4—C9—C5	−174.1 (2)	C23—O8—C21—C17	175.9 (2)
C11—O4—C9—C1	−55.6 (3)	C23—O8—C21—C13	57.7 (3)
C4—C5—C9—O3	177.56 (19)	C18—C17—C21—O7	56.6 (3)
C6—C5—C9—O3	−56.6 (3)	C16—C17—C21—O7	−177.58 (19)
C4—C5—C9—O4	56.6 (2)	C18—C17—C21—O8	177.5 (2)
C6—C5—C9—O4	−177.5 (2)	C16—C17—C21—O8	−56.7 (2)
C4—C5—C9—C1	−65.2 (3)	C18—C17—C21—C13	−60.9 (3)
C6—C5—C9—C1	60.6 (3)	C16—C17—C21—C13	64.9 (3)
C2—C1—C9—O3	179.1 (2)	C14—C13—C21—O7	178.6 (2)
C8—C1—C9—O3	58.6 (2)	C20—C13—C21—O7	−60.0 (3)
C2—C1—C9—O4	−61.0 (3)	C14—C13—C21—O8	58.4 (3)
C8—C1—C9—O4	178.5 (2)	C20—C13—C21—O8	179.81 (19)
C2—C1—C9—C5	55.7 (3)	C14—C13—C21—C17	−57.7 (3)
C8—C1—C9—C5	−64.8 (3)	C20—C13—C21—C17	63.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6O···O4ⁱ	0.84 (1)	2.03 (1)	2.863 (3)	172 (3)
O2—H2O···O8	0.84 (1)	2.02 (1)	2.858 (3)	176 (3)

Symmetry code: (i) x+1, y, z.

4-Methoxy-6-methyl-1-(3-methylbut-2-en-1-yl)-6-(4-methylpent-3-en-1-yl)bicyclo[3.3.1]non-3-ene-2,9-dione (3) top

Crystal data top

C₂₂H₃₂O₃	F(000) = 752
M_r = 344.47	D_x = 1.161 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.1871 (6) Å	Cell parameters from 5403 reflections
b = 6.3306 (2) Å	θ = 2.9–27.0°
c = 22.4159 (8) Å	µ = 0.08 mm⁻¹
β = 101.702 (1)°	T = 133 K
V = 1971.39 (13) Å³	Plate, colourless
Z = 4	0.18 × 0.14 × 0.04 mm

Data collection top

Bruker D8 VENTURE PHOTON II diffractometer	3271 reflections with I > 2σ(I)
Radiation source: INCOATEC IÂµS microfocus sealed tube	R_int = 0.067
φ and ω scans	θ_max = 27.1°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −18→18
T_min = 0.687, T_max = 0.746	k = −8→7
28995 measured reflections	l = −28→28
4348 independent reflections

Refinement top

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0448P)² + 0.8443P] where P = (F_o² + 2F_c²)/3
4348 reflections	(Δ/σ)_max = 0.001
232 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
O1	0.39938 (7)	0.15883 (17)	0.60348 (5)	0.0219 (2)
O2	0.65032 (8)	0.42454 (18)	0.51454 (5)	0.0248 (3)
O3	0.69009 (8)	0.20509 (19)	0.71052 (5)	0.0270 (3)
C1	0.53136 (10)	0.3264 (2)	0.66586 (7)	0.0180 (3)
H1	0.511136	0.232666	0.696903	0.022*
C2	0.48471 (10)	0.2511 (2)	0.60337 (7)	0.0177 (3)
C11	0.81757 (10)	0.2004 (3)	0.60868 (7)	0.0212 (3)
H11	0.807199	0.084368	0.633448	0.025*
C12	0.85993 (11)	0.1573 (3)	0.56230 (7)	0.0223 (3)
C13	0.89729 (12)	−0.0610 (3)	0.55400 (8)	0.0299 (4)
H13A	0.865158	−0.116923	0.514308	0.045*
H13B	0.884177	−0.153610	0.586396	0.045*
H13C	0.966851	−0.054570	0.555907	0.045*
C14	0.87732 (13)	0.3143 (3)	0.51526 (8)	0.0310 (4)
H14A	0.848722	0.261744	0.474485	0.047*
H14B	0.946743	0.333557	0.518615	0.047*
H14C	0.847832	0.449848	0.522063	0.047*
C15	0.55095 (12)	0.6122 (3)	0.74496 (7)	0.0265 (4)
H15A	0.532511	0.755107	0.754900	0.040*
H15B	0.621187	0.603420	0.750744	0.040*
H15C	0.528252	0.510118	0.771758	0.040*
C16	0.39580 (11)	0.5993 (3)	0.66583 (7)	0.0218 (3)
H16A	0.384466	0.751796	0.671266	0.026*
H16B	0.369708	0.565027	0.622540	0.026*
C17	0.33786 (11)	0.4754 (3)	0.70482 (7)	0.0257 (4)
H17A	0.339038	0.323133	0.694948	0.031*
H17B	0.367411	0.493600	0.748477	0.031*
C18	0.23549 (11)	0.5523 (3)	0.69309 (8)	0.0279 (4)
H18	0.225678	0.687173	0.709382	0.033*
C19	0.15695 (12)	0.4559 (3)	0.66287 (8)	0.0268 (4)
C20	0.15578 (14)	0.2407 (3)	0.63505 (9)	0.0399 (5)
H20A	0.104596	0.155924	0.646702	0.060*
H20B	0.218028	0.171697	0.649642	0.060*
H20C	0.143955	0.253524	0.590581	0.060*
C21	0.06030 (12)	0.5629 (3)	0.65247 (9)	0.0378 (5)
H21A	0.015217	0.476108	0.669694	0.057*
H21B	0.035856	0.580812	0.608633	0.057*
H21C	0.066863	0.701625	0.672309	0.057*
C22	0.34621 (11)	0.0763 (3)	0.54652 (8)	0.0271 (4)
H22A	0.288167	0.004550	0.553438	0.041*
H22B	0.386501	−0.024249	0.529772	0.041*
H22C	0.327832	0.192700	0.517674	0.041*
C3	0.52562 (10)	0.2750 (2)	0.55459 (7)	0.0202 (3)
H3	0.493355	0.222681	0.516124	0.024*
C4	0.61796 (11)	0.3789 (2)	0.55963 (7)	0.0190 (3)
C5	0.67586 (10)	0.4359 (2)	0.62303 (7)	0.0180 (3)
C6	0.65342 (11)	0.6707 (2)	0.63564 (7)	0.0218 (3)
H6A	0.692482	0.713146	0.675594	0.026*
H6B	0.672651	0.761032	0.604069	0.026*
C7	0.54739 (11)	0.7092 (2)	0.63586 (7)	0.0220 (3)
H7A	0.509788	0.691352	0.593857	0.026*
H7B	0.539427	0.857263	0.648144	0.026*
C8	0.50547 (10)	0.5620 (2)	0.67851 (7)	0.0191 (3)
C9	0.63940 (10)	0.3078 (2)	0.67122 (7)	0.0182 (3)
C10	0.78446 (11)	0.4122 (3)	0.62607 (7)	0.0222 (3)
H10A	0.804318	0.519739	0.599017	0.027*
H10B	0.818498	0.444174	0.668169	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0186 (5)	0.0217 (6)	0.0243 (6)	−0.0033 (4)	0.0018 (4)	−0.0049 (5)
O2	0.0266 (6)	0.0293 (6)	0.0191 (6)	0.0028 (5)	0.0061 (5)	0.0040 (5)
O3	0.0232 (6)	0.0330 (7)	0.0229 (6)	0.0051 (5)	0.0002 (5)	0.0084 (5)
C1	0.0191 (7)	0.0180 (7)	0.0164 (7)	0.0000 (6)	0.0026 (6)	0.0009 (6)
C2	0.0160 (7)	0.0134 (7)	0.0221 (7)	0.0018 (5)	0.0000 (6)	0.0001 (6)
C11	0.0162 (7)	0.0226 (8)	0.0235 (8)	−0.0006 (6)	0.0007 (6)	0.0025 (6)
C12	0.0171 (7)	0.0229 (8)	0.0253 (8)	0.0003 (6)	0.0007 (6)	−0.0007 (6)
C13	0.0256 (8)	0.0272 (9)	0.0359 (10)	0.0047 (7)	0.0039 (7)	−0.0028 (8)
C14	0.0327 (9)	0.0318 (10)	0.0308 (9)	0.0006 (7)	0.0119 (7)	0.0016 (8)
C15	0.0246 (8)	0.0327 (9)	0.0213 (8)	−0.0013 (7)	0.0022 (6)	−0.0069 (7)
C16	0.0208 (8)	0.0222 (8)	0.0219 (8)	0.0032 (6)	0.0031 (6)	−0.0022 (6)
C17	0.0224 (8)	0.0319 (9)	0.0231 (8)	0.0017 (7)	0.0050 (6)	−0.0011 (7)
C18	0.0246 (8)	0.0313 (9)	0.0291 (9)	0.0026 (7)	0.0087 (7)	−0.0041 (7)
C19	0.0254 (8)	0.0319 (10)	0.0235 (8)	0.0005 (7)	0.0060 (7)	0.0035 (7)
C20	0.0359 (10)	0.0408 (12)	0.0402 (11)	−0.0035 (9)	0.0009 (8)	−0.0066 (9)
C21	0.0230 (9)	0.0478 (12)	0.0417 (11)	0.0009 (8)	0.0048 (8)	0.0060 (9)
C22	0.0212 (8)	0.0291 (9)	0.0281 (9)	−0.0046 (7)	−0.0017 (7)	−0.0087 (7)
C3	0.0205 (7)	0.0212 (8)	0.0170 (7)	0.0018 (6)	−0.0008 (6)	−0.0037 (6)
C4	0.0203 (7)	0.0165 (7)	0.0194 (8)	0.0054 (6)	0.0022 (6)	0.0013 (6)
C5	0.0172 (7)	0.0185 (8)	0.0180 (7)	−0.0003 (6)	0.0025 (6)	−0.0006 (6)
C6	0.0241 (8)	0.0176 (8)	0.0245 (8)	−0.0014 (6)	0.0065 (6)	−0.0012 (6)
C7	0.0242 (8)	0.0159 (7)	0.0262 (8)	0.0026 (6)	0.0058 (6)	−0.0014 (6)
C8	0.0198 (7)	0.0201 (8)	0.0170 (7)	0.0013 (6)	0.0025 (6)	−0.0025 (6)
C9	0.0207 (7)	0.0163 (7)	0.0161 (7)	0.0005 (6)	0.0003 (6)	−0.0018 (6)
C10	0.0183 (7)	0.0236 (8)	0.0242 (8)	−0.0015 (6)	0.0035 (6)	−0.0002 (6)

Geometric parameters (Å, º) top

O1—C2	1.3445 (17)	C17—H17A	0.9900
O1—C22	1.4425 (19)	C17—H17B	0.9900
O2—C4	1.2263 (18)	C18—C19	1.329 (2)
O3—C9	1.2078 (18)	C18—H18	0.9500
C1—C2	1.501 (2)	C19—C20	1.497 (3)
C1—C9	1.518 (2)	C19—C21	1.505 (2)
C1—C8	1.575 (2)	C20—H20A	0.9800
C1—H1	1.0000	C20—H20B	0.9800
C2—C3	1.346 (2)	C20—H20C	0.9800
C11—C12	1.331 (2)	C21—H21A	0.9800
C11—C10	1.498 (2)	C21—H21B	0.9800
C11—H11	0.9500	C21—H21C	0.9800
C12—C13	1.505 (2)	C22—H22A	0.9800
C12—C14	1.505 (2)	C22—H22B	0.9800
C13—H13A	0.9800	C22—H22C	0.9800
C13—H13B	0.9800	C3—C4	1.450 (2)
C13—H13C	0.9800	C3—H3	0.9500
C14—H14A	0.9800	C4—C5	1.533 (2)
C14—H14B	0.9800	C5—C9	1.523 (2)
C14—H14C	0.9800	C5—C10	1.536 (2)
C15—C8	1.532 (2)	C5—C6	1.558 (2)
C15—H15A	0.9800	C6—C7	1.525 (2)
C15—H15B	0.9800	C6—H6A	0.9900
C15—H15C	0.9800	C6—H6B	0.9900
C16—C17	1.532 (2)	C7—C8	1.538 (2)
C16—C8	1.542 (2)	C7—H7A	0.9900
C16—H16A	0.9900	C7—H7B	0.9900
C16—H16B	0.9900	C10—H10A	0.9900
C17—C18	1.503 (2)	C10—H10B	0.9900

C2—O1—C22	117.71 (12)	C19—C20—H20C	109.5
C2—C1—C9	107.24 (12)	H20A—C20—H20C	109.5
C2—C1—C8	113.22 (12)	H20B—C20—H20C	109.5
C9—C1—C8	109.15 (12)	C19—C21—H21A	109.5
C2—C1—H1	109.1	C19—C21—H21B	109.5
C9—C1—H1	109.1	H21A—C21—H21B	109.5
C8—C1—H1	109.1	C19—C21—H21C	109.5
O1—C2—C3	125.94 (14)	H21A—C21—H21C	109.5
O1—C2—C1	111.29 (12)	H21B—C21—H21C	109.5
C3—C2—C1	122.77 (13)	O1—C22—H22A	109.5
C12—C11—C10	127.01 (15)	O1—C22—H22B	109.5
C12—C11—H11	116.5	H22A—C22—H22B	109.5
C10—C11—H11	116.5	O1—C22—H22C	109.5
C11—C12—C13	120.73 (15)	H22A—C22—H22C	109.5
C11—C12—C14	125.18 (15)	H22B—C22—H22C	109.5
C13—C12—C14	114.07 (14)	C2—C3—C4	121.28 (14)
C12—C13—H13A	109.5	C2—C3—H3	119.4
C12—C13—H13B	109.5	C4—C3—H3	119.4
H13A—C13—H13B	109.5	O2—C4—C3	121.74 (14)
C12—C13—H13C	109.5	O2—C4—C5	119.27 (14)
H13A—C13—H13C	109.5	C3—C4—C5	118.99 (13)
H13B—C13—H13C	109.5	C9—C5—C4	109.70 (12)
C12—C14—H14A	109.5	C9—C5—C10	113.49 (12)
C12—C14—H14B	109.5	C4—C5—C10	111.23 (12)
H14A—C14—H14B	109.5	C9—C5—C6	105.56 (12)
C12—C14—H14C	109.5	C4—C5—C6	107.55 (12)
H14A—C14—H14C	109.5	C10—C5—C6	108.98 (12)
H14B—C14—H14C	109.5	C7—C6—C5	113.00 (12)
C8—C15—H15A	109.5	C7—C6—H6A	109.0
C8—C15—H15B	109.5	C5—C6—H6A	109.0
H15A—C15—H15B	109.5	C7—C6—H6B	109.0
C8—C15—H15C	109.5	C5—C6—H6B	109.0
H15A—C15—H15C	109.5	H6A—C6—H6B	107.8
H15B—C15—H15C	109.5	C6—C7—C8	114.29 (13)
C17—C16—C8	117.03 (13)	C6—C7—H7A	108.7
C17—C16—H16A	108.0	C8—C7—H7A	108.7
C8—C16—H16A	108.0	C6—C7—H7B	108.7
C17—C16—H16B	108.0	C8—C7—H7B	108.7
C8—C16—H16B	108.0	H7A—C7—H7B	107.6
H16A—C16—H16B	107.3	C15—C8—C7	109.82 (13)
C18—C17—C16	110.21 (14)	C15—C8—C16	110.96 (12)
C18—C17—H17A	109.6	C7—C8—C16	107.18 (12)
C16—C17—H17A	109.6	C15—C8—C1	107.69 (13)
C18—C17—H17B	109.6	C7—C8—C1	109.14 (12)
C16—C17—H17B	109.6	C16—C8—C1	112.04 (12)
H17A—C17—H17B	108.1	O3—C9—C1	122.82 (14)
C19—C18—C17	128.37 (16)	O3—C9—C5	124.51 (14)
C19—C18—H18	115.8	C1—C9—C5	112.66 (12)
C17—C18—H18	115.8	C11—C10—C5	116.15 (13)
C18—C19—C20	124.57 (16)	C11—C10—H10A	108.2
C18—C19—C21	121.04 (17)	C5—C10—H10A	108.2
C20—C19—C21	114.36 (16)	C11—C10—H10B	108.2
C19—C20—H20A	109.5	C5—C10—H10B	108.2
C19—C20—H20B	109.5	H10A—C10—H10B	107.4
H20A—C20—H20B	109.5

C22—O1—C2—C3	0.3 (2)	C6—C7—C8—C15	67.77 (17)
C22—O1—C2—C1	−179.43 (13)	C6—C7—C8—C16	−171.61 (13)
C9—C1—C2—O1	147.89 (12)	C6—C7—C8—C1	−50.07 (17)
C8—C1—C2—O1	−91.66 (15)	C17—C16—C8—C15	−57.88 (18)
C9—C1—C2—C3	−31.9 (2)	C17—C16—C8—C7	−177.78 (13)
C8—C1—C2—C3	88.60 (17)	C17—C16—C8—C1	62.53 (17)
C10—C11—C12—C13	174.40 (15)	C2—C1—C8—C15	175.62 (12)
C10—C11—C12—C14	−4.1 (3)	C9—C1—C8—C15	−65.02 (15)
C8—C16—C17—C18	171.90 (13)	C2—C1—C8—C7	−65.22 (16)
C16—C17—C18—C19	107.5 (2)	C9—C1—C8—C7	54.14 (16)
C17—C18—C19—C20	1.7 (3)	C2—C1—C8—C16	53.33 (16)
C17—C18—C19—C21	−176.41 (16)	C9—C1—C8—C16	172.69 (12)
O1—C2—C3—C4	179.48 (14)	C2—C1—C9—O3	−122.71 (16)
C1—C2—C3—C4	−0.8 (2)	C8—C1—C9—O3	114.28 (16)
C2—C3—C4—O2	−170.94 (15)	C2—C1—C9—C5	58.69 (16)
C2—C3—C4—C5	8.2 (2)	C8—C1—C9—C5	−64.32 (15)
O2—C4—C5—C9	−162.44 (13)	C4—C5—C9—O3	128.82 (16)
C3—C4—C5—C9	18.39 (18)	C10—C5—C9—O3	3.7 (2)
O2—C4—C5—C10	−36.05 (19)	C6—C5—C9—O3	−115.57 (16)
C3—C4—C5—C10	144.78 (14)	C4—C5—C9—C1	−52.61 (16)
O2—C4—C5—C6	83.22 (16)	C10—C5—C9—C1	−177.70 (12)
C3—C4—C5—C6	−95.96 (15)	C6—C5—C9—C1	63.01 (15)
C9—C5—C6—C7	−55.72 (16)	C12—C11—C10—C5	117.26 (17)
C4—C5—C6—C7	61.36 (16)	C9—C5—C10—C11	68.76 (17)
C10—C5—C6—C7	−177.95 (13)	C4—C5—C10—C11	−55.51 (18)
C5—C6—C7—C8	52.82 (18)	C6—C5—C10—C11	−173.92 (13)

4-tert-Butyl-4-hydroxy-2-methoxy-8-methyl-7-(3-methylbut-2-en-1-yl)-8-(4-methylpent-3-en-1-yl)bicyclo[3.3.1]non-2-en-9-one (4) top

Crystal data top

C₂₆H₄₂O₃	F(000) = 888
M_r = 402.59	D_x = 1.080 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.1165 (5) Å	Cell parameters from 9769 reflections
b = 13.9068 (4) Å	θ = 2.9–27.1°
c = 12.8150 (4) Å	µ = 0.07 mm⁻¹
β = 113.218 (1)°	T = 143 K
V = 2475.81 (13) Å³	Prism, colourless
Z = 4	0.26 × 0.16 × 0.08 mm

Data collection top

Bruker D8 VENTURE PHOTON II diffractometer	4697 reflections with I > 2σ(I)
Radiation source: INCOATEC IÂµS microfocus sealed tube	R_int = 0.048
φ and ω scans	θ_max = 27.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −19→19
T_min = 0.704, T_max = 0.746	k = −16→17
87917 measured reflections	l = −16→16
5484 independent reflections

Refinement top

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)] = 0.040	Hydrogen site location: mixed
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.049P)² + 0.8245P] where P = (F_o² + 2F_c²)/3
5484 reflections	(Δ/σ)_max < 0.001
274 parameters	Δρ_max = 0.29 e Å⁻³
1 restraint	Δρ_min = −0.20 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
O1	0.58921 (6)	0.47108 (5)	0.43047 (6)	0.02376 (18)
O2	0.51178 (6)	0.14696 (6)	0.37950 (7)	0.02551 (18)
H2	0.5478 (10)	0.1689 (11)	0.3487 (12)	0.038*
O3	0.61221 (6)	0.30868 (6)	0.73617 (6)	0.02674 (19)
C1	0.65561 (7)	0.36534 (7)	0.58638 (9)	0.0191 (2)
H1	0.668130	0.427362	0.629287	0.023*
C2	0.58011 (7)	0.38158 (7)	0.46865 (9)	0.0187 (2)
C3	0.51410 (8)	0.31676 (8)	0.41130 (9)	0.0202 (2)
H3	0.470212	0.333360	0.336969	0.024*
C4	0.50402 (8)	0.21886 (7)	0.45585 (9)	0.0198 (2)
C5	0.58310 (8)	0.20205 (7)	0.57770 (9)	0.0202 (2)
H5	0.556494	0.158196	0.620023	0.024*
C6	0.67741 (8)	0.15818 (8)	0.57903 (10)	0.0229 (2)
H6A	0.718889	0.140699	0.658210	0.028*
H6B	0.661579	0.098106	0.533934	0.028*
C7	0.73503 (8)	0.22364 (8)	0.53245 (9)	0.0210 (2)
H7	0.695333	0.232637	0.449626	0.025*
C8	0.75364 (7)	0.32539 (8)	0.58735 (9)	0.0205 (2)
C9	0.61403 (7)	0.29414 (8)	0.64324 (9)	0.0197 (2)
C10	0.82710 (8)	0.16941 (9)	0.54227 (10)	0.0276 (2)
H10A	0.869428	0.213478	0.522244	0.033*
H10B	0.862400	0.148432	0.621810	0.033*
C11	0.80410 (8)	0.08302 (9)	0.46537 (10)	0.0274 (2)
H11	0.752582	0.090867	0.393411	0.033*
C12	0.84620 (9)	−0.00269 (9)	0.48468 (11)	0.0318 (3)
C13	0.92703 (13)	−0.03188 (12)	0.59291 (14)	0.0542 (4)
H13A	0.982739	−0.051060	0.576768	0.081*
H13B	0.906467	−0.086094	0.626814	0.081*
H13C	0.944762	0.022430	0.645939	0.081*
C14	0.81468 (12)	−0.07908 (11)	0.39421 (15)	0.0473 (4)
H14A	0.758079	−0.056563	0.329342	0.071*
H14B	0.798374	−0.137879	0.424891	0.071*
H14C	0.867064	−0.092552	0.369481	0.071*
C15	0.82707 (8)	0.32225 (9)	0.71095 (10)	0.0272 (2)
H15A	0.890430	0.304716	0.712693	0.041*
H15B	0.806850	0.274391	0.753214	0.041*
H15C	0.830812	0.385648	0.745833	0.041*
C16	0.78978 (8)	0.39199 (8)	0.51636 (10)	0.0255 (2)
H16A	0.848819	0.363159	0.513943	0.031*
H16B	0.740565	0.392664	0.437600	0.031*
C17	0.81238 (9)	0.49662 (9)	0.55609 (11)	0.0331 (3)
H17A	0.756181	0.525580	0.565571	0.040*
H17B	0.867730	0.498447	0.630446	0.040*
C18	0.83575 (9)	0.55326 (9)	0.47056 (12)	0.0347 (3)
H18	0.790871	0.547761	0.394072	0.042*
C19	0.91070 (9)	0.60995 (9)	0.48753 (12)	0.0336 (3)
C20	0.92557 (11)	0.65611 (12)	0.38952 (14)	0.0478 (4)
H20A	0.870648	0.641423	0.318709	0.072*
H20B	0.984685	0.631054	0.385359	0.072*
H20C	0.931060	0.725920	0.400634	0.072*
C21	0.98769 (13)	0.63083 (14)	0.60163 (15)	0.0597 (5)
H21A	1.048455	0.602150	0.606663	0.090*
H21B	0.969451	0.603470	0.660797	0.090*
H21C	0.995622	0.700564	0.612238	0.090*
C22	0.53199 (10)	0.49151 (9)	0.31424 (10)	0.0335 (3)
H22A	0.549538	0.554761	0.294582	0.050*
H22B	0.463789	0.491517	0.302071	0.050*
H22C	0.543299	0.442285	0.266167	0.050*
C23	0.40054 (8)	0.20444 (8)	0.45525 (10)	0.0244 (2)
C24	0.38671 (9)	0.26723 (9)	0.54585 (11)	0.0298 (3)
H24A	0.402128	0.334181	0.535978	0.045*
H24B	0.429455	0.244724	0.621440	0.045*
H24C	0.319688	0.262973	0.538096	0.045*
C25	0.32344 (9)	0.23243 (11)	0.33952 (11)	0.0378 (3)
H25A	0.335664	0.198822	0.279316	0.057*
H25B	0.325506	0.302032	0.328713	0.057*
H25C	0.259812	0.214354	0.336505	0.057*
C26	0.38494 (9)	0.09832 (9)	0.47587 (12)	0.0345 (3)
H26A	0.320208	0.089861	0.474739	0.052*
H26B	0.432888	0.078417	0.549936	0.052*
H26C	0.391761	0.058869	0.416106	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0315 (4)	0.0169 (4)	0.0221 (4)	−0.0007 (3)	0.0097 (3)	0.0035 (3)
O2	0.0346 (4)	0.0228 (4)	0.0247 (4)	−0.0073 (3)	0.0177 (3)	−0.0078 (3)
O3	0.0294 (4)	0.0363 (5)	0.0168 (4)	−0.0006 (3)	0.0115 (3)	−0.0018 (3)
C1	0.0230 (5)	0.0177 (5)	0.0171 (5)	−0.0021 (4)	0.0086 (4)	−0.0023 (4)
C2	0.0236 (5)	0.0171 (5)	0.0183 (5)	0.0011 (4)	0.0112 (4)	0.0010 (4)
C3	0.0239 (5)	0.0213 (5)	0.0155 (5)	−0.0003 (4)	0.0079 (4)	0.0008 (4)
C4	0.0247 (5)	0.0186 (5)	0.0181 (5)	−0.0039 (4)	0.0107 (4)	−0.0032 (4)
C5	0.0246 (5)	0.0191 (5)	0.0196 (5)	−0.0018 (4)	0.0117 (4)	0.0021 (4)
C6	0.0268 (5)	0.0188 (5)	0.0250 (5)	0.0012 (4)	0.0121 (4)	0.0027 (4)
C7	0.0218 (5)	0.0210 (5)	0.0213 (5)	0.0004 (4)	0.0096 (4)	−0.0002 (4)
C8	0.0204 (5)	0.0219 (5)	0.0196 (5)	−0.0016 (4)	0.0084 (4)	−0.0009 (4)
C9	0.0193 (5)	0.0237 (5)	0.0160 (5)	0.0018 (4)	0.0068 (4)	0.0013 (4)
C10	0.0239 (5)	0.0282 (6)	0.0318 (6)	0.0026 (4)	0.0120 (5)	−0.0021 (5)
C11	0.0279 (6)	0.0303 (6)	0.0269 (6)	0.0033 (5)	0.0140 (5)	−0.0008 (5)
C12	0.0348 (6)	0.0296 (6)	0.0382 (7)	0.0040 (5)	0.0222 (6)	0.0022 (5)
C13	0.0608 (10)	0.0476 (9)	0.0506 (9)	0.0248 (8)	0.0181 (8)	0.0114 (7)
C14	0.0577 (9)	0.0333 (7)	0.0629 (10)	0.0009 (6)	0.0364 (8)	−0.0108 (7)
C15	0.0239 (5)	0.0318 (6)	0.0230 (5)	−0.0012 (4)	0.0062 (4)	−0.0010 (5)
C16	0.0237 (5)	0.0267 (6)	0.0287 (6)	−0.0035 (4)	0.0131 (5)	0.0012 (4)
C17	0.0332 (6)	0.0293 (6)	0.0369 (7)	−0.0111 (5)	0.0140 (5)	−0.0011 (5)
C18	0.0268 (6)	0.0327 (6)	0.0399 (7)	−0.0055 (5)	0.0082 (5)	0.0079 (5)
C19	0.0278 (6)	0.0265 (6)	0.0461 (8)	−0.0023 (5)	0.0141 (5)	0.0053 (5)
C20	0.0330 (7)	0.0471 (8)	0.0615 (10)	−0.0042 (6)	0.0167 (7)	0.0222 (7)
C21	0.0559 (10)	0.0690 (12)	0.0518 (10)	−0.0365 (9)	0.0186 (8)	−0.0119 (8)
C22	0.0497 (8)	0.0228 (6)	0.0247 (6)	0.0035 (5)	0.0109 (5)	0.0072 (5)
C23	0.0237 (5)	0.0264 (6)	0.0250 (5)	−0.0062 (4)	0.0115 (4)	−0.0040 (4)
C24	0.0262 (6)	0.0340 (6)	0.0332 (6)	−0.0033 (5)	0.0160 (5)	−0.0062 (5)
C25	0.0253 (6)	0.0515 (8)	0.0318 (7)	−0.0085 (5)	0.0062 (5)	−0.0019 (6)
C26	0.0366 (7)	0.0293 (6)	0.0444 (7)	−0.0127 (5)	0.0232 (6)	−0.0050 (5)

Geometric parameters (Å, º) top

O1—C2	1.3640 (12)	C14—H14B	0.9800
O1—C22	1.4254 (14)	C14—H14C	0.9800
O2—C4	1.4357 (12)	C15—H15A	0.9800
O2—H2	0.846 (9)	C15—H15B	0.9800
O3—C9	1.2189 (13)	C15—H15C	0.9800
C1—C9	1.5058 (14)	C16—C17	1.5350 (17)
C1—C2	1.5073 (14)	C16—H16A	0.9900
C1—C8	1.5781 (14)	C16—H16B	0.9900
C1—H1	1.0000	C17—C18	1.5005 (18)
C2—C3	1.3305 (15)	C17—H17A	0.9900
C3—C4	1.5071 (14)	C17—H17B	0.9900
C3—H3	0.9500	C18—C19	1.3261 (17)
C4—C5	1.5652 (14)	C18—H18	0.9500
C4—C23	1.5741 (15)	C19—C21	1.495 (2)
C5—C9	1.5016 (15)	C19—C20	1.5042 (19)
C5—C6	1.5446 (15)	C20—H20A	0.9800
C5—H5	1.0000	C20—H20B	0.9800
C6—C7	1.5342 (15)	C20—H20C	0.9800
C6—H6A	0.9900	C21—H21A	0.9800
C6—H6B	0.9900	C21—H21B	0.9800
C7—C10	1.5439 (15)	C21—H21C	0.9800
C7—C8	1.5558 (15)	C22—H22A	0.9800
C7—H7	1.0000	C22—H22B	0.9800
C8—C15	1.5350 (15)	C22—H22C	0.9800
C8—C16	1.5414 (15)	C23—C24	1.5315 (16)
C10—C11	1.5051 (16)	C23—C25	1.5319 (17)
C10—H10A	0.9900	C23—C26	1.5338 (16)
C10—H10B	0.9900	C24—H24A	0.9800
C11—C12	1.3277 (17)	C24—H24B	0.9800
C11—H11	0.9500	C24—H24C	0.9800
C12—C13	1.498 (2)	C25—H25A	0.9800
C12—C14	1.5047 (19)	C25—H25B	0.9800
C13—H13A	0.9800	C25—H25C	0.9800
C13—H13B	0.9800	C26—H26A	0.9800
C13—H13C	0.9800	C26—H26B	0.9800
C14—H14A	0.9800	C26—H26C	0.9800

C2—O1—C22	116.82 (9)	H14A—C14—H14C	109.5
C4—O2—H2	107.9 (11)	H14B—C14—H14C	109.5
C9—C1—C2	106.68 (8)	C8—C15—H15A	109.5
C9—C1—C8	109.54 (8)	C8—C15—H15B	109.5
C2—C1—C8	113.50 (8)	H15A—C15—H15B	109.5
C9—C1—H1	109.0	C8—C15—H15C	109.5
C2—C1—H1	109.0	H15A—C15—H15C	109.5
C8—C1—H1	109.0	H15B—C15—H15C	109.5
C3—C2—O1	125.44 (10)	C17—C16—C8	117.27 (10)
C3—C2—C1	123.95 (9)	C17—C16—H16A	108.0
O1—C2—C1	110.61 (9)	C8—C16—H16A	108.0
C2—C3—C4	124.65 (9)	C17—C16—H16B	108.0
C2—C3—H3	117.7	C8—C16—H16B	108.0
C4—C3—H3	117.7	H16A—C16—H16B	107.2
O2—C4—C3	108.86 (8)	C18—C17—C16	109.94 (11)
O2—C4—C5	109.90 (8)	C18—C17—H17A	109.7
C3—C4—C5	111.18 (8)	C16—C17—H17A	109.7
O2—C4—C23	104.83 (8)	C18—C17—H17B	109.7
C3—C4—C23	111.22 (9)	C16—C17—H17B	109.7
C5—C4—C23	110.64 (8)	H17A—C17—H17B	108.2
C9—C5—C6	104.37 (8)	C19—C18—C17	128.62 (13)
C9—C5—C4	112.18 (8)	C19—C18—H18	115.7
C6—C5—C4	114.12 (9)	C17—C18—H18	115.7
C9—C5—H5	108.7	C18—C19—C21	124.14 (13)
C6—C5—H5	108.7	C18—C19—C20	121.07 (13)
C4—C5—H5	108.7	C21—C19—C20	114.76 (12)
C7—C6—C5	115.11 (9)	C19—C20—H20A	109.5
C7—C6—H6A	108.5	C19—C20—H20B	109.5
C5—C6—H6A	108.5	H20A—C20—H20B	109.5
C7—C6—H6B	108.5	C19—C20—H20C	109.5
C5—C6—H6B	108.5	H20A—C20—H20C	109.5
H6A—C6—H6B	107.5	H20B—C20—H20C	109.5
C6—C7—C10	108.08 (9)	C19—C21—H21A	109.5
C6—C7—C8	113.13 (9)	C19—C21—H21B	109.5
C10—C7—C8	114.26 (9)	H21A—C21—H21B	109.5
C6—C7—H7	107.0	C19—C21—H21C	109.5
C10—C7—H7	107.0	H21A—C21—H21C	109.5
C8—C7—H7	107.0	H21B—C21—H21C	109.5
C15—C8—C16	110.22 (9)	O1—C22—H22A	109.5
C15—C8—C7	111.66 (9)	O1—C22—H22B	109.5
C16—C8—C7	108.81 (9)	H22A—C22—H22B	109.5
C15—C8—C1	108.24 (8)	O1—C22—H22C	109.5
C16—C8—C1	109.51 (9)	H22A—C22—H22C	109.5
C7—C8—C1	108.35 (8)	H22B—C22—H22C	109.5
O3—C9—C5	124.47 (10)	C24—C23—C25	108.05 (10)
O3—C9—C1	122.56 (10)	C24—C23—C26	109.99 (10)
C5—C9—C1	112.80 (8)	C25—C23—C26	107.54 (10)
C11—C10—C7	111.61 (9)	C24—C23—C4	110.86 (9)
C11—C10—H10A	109.3	C25—C23—C4	110.35 (9)
C7—C10—H10A	109.3	C26—C23—C4	109.98 (9)
C11—C10—H10B	109.3	C23—C24—H24A	109.5
C7—C10—H10B	109.3	C23—C24—H24B	109.5
H10A—C10—H10B	108.0	H24A—C24—H24B	109.5
C12—C11—C10	128.65 (12)	C23—C24—H24C	109.5
C12—C11—H11	115.7	H24A—C24—H24C	109.5
C10—C11—H11	115.7	H24B—C24—H24C	109.5
C11—C12—C13	124.87 (13)	C23—C25—H25A	109.5
C11—C12—C14	120.48 (13)	C23—C25—H25B	109.5
C13—C12—C14	114.64 (12)	H25A—C25—H25B	109.5
C12—C13—H13A	109.5	C23—C25—H25C	109.5
C12—C13—H13B	109.5	H25A—C25—H25C	109.5
H13A—C13—H13B	109.5	H25B—C25—H25C	109.5
C12—C13—H13C	109.5	C23—C26—H26A	109.5
H13A—C13—H13C	109.5	C23—C26—H26B	109.5
H13B—C13—H13C	109.5	H26A—C26—H26B	109.5
C12—C14—H14A	109.5	C23—C26—H26C	109.5
C12—C14—H14B	109.5	H26A—C26—H26C	109.5
H14A—C14—H14B	109.5	H26B—C26—H26C	109.5
C12—C14—H14C	109.5

C22—O1—C2—C3	−9.12 (16)	C9—C1—C8—C7	54.45 (10)
C22—O1—C2—C1	171.02 (9)	C2—C1—C8—C7	−64.65 (11)
C9—C1—C2—C3	−27.68 (14)	C6—C5—C9—O3	−111.33 (11)
C8—C1—C2—C3	93.05 (12)	C4—C5—C9—O3	124.61 (11)
C9—C1—C2—O1	152.17 (8)	C6—C5—C9—C1	64.07 (11)
C8—C1—C2—O1	−87.10 (10)	C4—C5—C9—C1	−59.99 (11)
O1—C2—C3—C4	−178.78 (9)	C2—C1—C9—O3	−128.15 (10)
C1—C2—C3—C4	1.06 (17)	C8—C1—C9—O3	108.61 (11)
C2—C3—C4—O2	−122.62 (11)	C2—C1—C9—C5	56.35 (11)
C2—C3—C4—C5	−1.41 (14)	C8—C1—C9—C5	−66.88 (11)
C2—C3—C4—C23	122.37 (11)	C6—C7—C10—C11	66.44 (12)
O2—C4—C5—C9	150.21 (8)	C8—C7—C10—C11	−166.66 (9)
C3—C4—C5—C9	29.61 (12)	C7—C10—C11—C12	−142.25 (12)
C23—C4—C5—C9	−94.50 (10)	C10—C11—C12—C13	1.6 (2)
O2—C4—C5—C6	31.76 (11)	C10—C11—C12—C14	−177.64 (12)
C3—C4—C5—C6	−88.83 (10)	C15—C8—C16—C17	−57.38 (13)
C23—C4—C5—C6	147.06 (9)	C7—C8—C16—C17	179.86 (10)
C9—C5—C6—C7	−55.79 (11)	C1—C8—C16—C17	61.59 (12)
C4—C5—C6—C7	67.01 (12)	C8—C16—C17—C18	−173.70 (10)
C5—C6—C7—C10	178.96 (9)	C16—C17—C18—C19	−129.72 (15)
C5—C6—C7—C8	51.40 (12)	C17—C18—C19—C21	−2.1 (2)
C6—C7—C8—C15	71.38 (11)	C17—C18—C19—C20	175.86 (14)
C10—C7—C8—C15	−52.86 (12)	O2—C4—C23—C24	172.12 (9)
C6—C7—C8—C16	−166.73 (9)	C3—C4—C23—C24	−70.39 (12)
C10—C7—C8—C16	69.03 (11)	C5—C4—C23—C24	53.69 (12)
C6—C7—C8—C1	−47.73 (11)	O2—C4—C23—C25	−68.21 (11)
C10—C7—C8—C1	−171.97 (9)	C3—C4—C23—C25	49.28 (12)
C9—C1—C8—C15	−66.80 (11)	C5—C4—C23—C25	173.36 (9)
C2—C1—C8—C15	174.10 (9)	O2—C4—C23—C26	50.27 (11)
C9—C1—C8—C16	173.01 (8)	C3—C4—C23—C26	167.75 (9)
C2—C1—C8—C16	53.90 (11)	C5—C4—C23—C26	−68.16 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3ⁱ	0.85 (1)	2.06 (1)	2.8736 (11)	162 (2)

Symmetry code: (i) x, −y+1/2, z−1/2.

Puckering parameters Q (Å), Θ (°) and Φ (°) of the cyclohexane rings I and II of 1, 2a, 2b, 3 and 4 top

		Ring I			Ring II
	Q (Å)	Θ (°)	Φ (°)	Q (Å)	Θ (°)	Φ (°)
1	0.590 (2)	172.2 (2)	104.4 (1)	0.505 (2)	56.7 (2)	306.0 (2)
2a	0.591 (3)	169.6 (3)	140.4 (2)	0.534 (3)	48.3 (3)	284.1 (4)
2b^a	0.593 (3)	170.7 (3)	139.1 (2)	0.541 (3)	47.8 (3)	286.9 (4)
3	0.592 (2)	171.6 (2)	115.6 (1)	0.501 (2)	58.2 (2)	310.9 (2)
4	0.592 (1)	170.2 (1)	120.6 (7)	0.489 (1)	52.4 (1)	298.5 (2)

Note: (a) for 2b (the enantiomer of 2a), the tabulated values of Θ and Φ were calculated from the observed Θ' and Φ' using the equations Θ = 180° – Θ' and Φ = 180° + Φ'.

Acknowledgements

We thank Saarland University for continuous support. We acknowledge the Service Center X-ray Diffraction established with financial support from Saarland University and the Deutsche Forschungsgemeinschaft.

Funding information

Funding for this research was provided by: Deutsche Forschungsgemeinschaft (grant No. INST 256/506-1; grant No. INST 256/582-1).

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Synthesis and crystal structure analysis of substituted bi­cyclo­[3.3.1]nona­nones

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

5.1. 4-Methoxybi­cyclo­[3.3.1]non-3-ene-2,9-dione (1)

5.2. 4,9,9-Tri­methoxybi­cyclo­[3.3.1]non-3-en-2-ol (2)

5.3. 4-Meth­oxy-6-methyl-1-(3-methyl­but-2-en-1-yl)-6-(4-methyl­pent-3-en-1-yl)bi­cyclo­[3.3.1]non-3-ene-2,9-dione (3)

5.4. 4-tert-Butyl-4-hy­droxy-2-meth­oxy-8-methyl-7-(3-methyl­but-2-en-1-yl)-8-(4-methyl­pent-3-en-1-yl)bi­cyclo­[3.3.1]non-2-en-9-one (4)

6. Refinement

Supporting information

Acknowledgements

Funding information

References

research communications

Synthesis and crystal structure analysis of substituted bicyclo[3.3.1]nonanones

3. Supramolecular features

5.1. 4-Methoxybicyclo[3.3.1]non-3-ene-2,9-dione (1)

5.2. 4,9,9-Trimethoxybicyclo[3.3.1]non-3-en-2-ol (2)

5.3. 4-Methoxy-6-methyl-1-(3-methylbut-2-en-1-yl)-6-(4-methylpent-3-en-1-yl)bicyclo[3.3.1]non-3-ene-2,9-dione (3)

5.4. 4-tert-Butyl-4-hydroxy-2-methoxy-8-methyl-7-(3-methylbut-2-en-1-yl)-8-(4-methylpent-3-en-1-yl)bicyclo[3.3.1]non-2-en-9-one (4)