3,15-Dimeth­oxy-10-methyl­tricyclo­[9.4.0.02,7]penta­deca-1(11),2(7),3,5,9,12,14-heptaen-8-one

doi:10.1107/S160053681103100X

Acta Crystallogr Sect E Struct Rep Online. 2011 September 1; 67(Pt 9): o2282.

Published online 2011 August 11. doi: 10.1107/S160053681103100X

PMCID: PMC3200918

3,15-Dimethoxy-10-methyltricyclo[9.4.0.0^2,7]pentadeca-1(11),2(7),3,5,9,12,14-heptaen-8-one

Yaomin Zhu,^a Jianfei Yang,^b Xianfei Li,^b and Le Zhou^b^*

^aSchool of Materials Science and Engineering, Henan University of Science & Technology 471022, People’s Republic of China

^bCollege of Science, Northwest A&F University, Yangling 712100, People’s Republic of China

Correspondence e-mail: zhoulechem/at/yahoo.com.cn

Received July 6, 2011; Accepted August 2, 2011.

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

Abstract

The title molecule, C₁₈H₁₆O₃, contains three fused rings, of which the seven-membered cyclohept-2-enone ring has a screw-boat conformation. The two methoxyphenyl rings make a dihedral angle of 50.4 (2)°. In the crystal, molecules are linked by intermolecular C—H (...)

O hydrogen bonds, leading to a three-dimensional supramolecular architecture.

Related literature

The title compound was obtained through an aldol condensation reaction. For general background to aldol reactions, see: Machajewski & Wong (2000

); Nelson (1998

). For structures with C—H (...)

O hydrogen bonds, see: Broder et al. (2002

); Senthil Kumar et al. (2006

An external file that holds a picture, illustration, etc.
Object name is e-67-o2282-scheme1.jpg Object name is e-67-o2282-scheme1.jpg

Experimental

Crystal data

C₁₈H₁₆O₃
M _r = 280.31
Orthorhombic,
a = 7.6615 (10) Å
b = 12.2005 (16) Å
c = 15.545 (2) Å
V = 1453.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.43 × 0.31 × 0.17 mm

Data collection

Bruker SMART CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T _min = 0.964, T _max = 0.986
11119 measured reflections
2708 independent reflections
2083 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.090
S = 1.09
2708 reflections
193 parameters
H-atom parameters constrained
Δρ_max = 0.10 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: SMART (Bruker, 2004

); cell refinement: SAINT (Bruker, 2004

); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008

); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008

); molecular graphics: SHELXTL (Sheldrick, 2008

); software used to prepare material for publication: SHELXTL.

Table 1

Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681103100X/zj2016sup1.cif

Click here to view.^{(19K, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681103100X/zj2016Isup2.hkl

Click here to view.^{(133K, hkl)}

Supplementary material file. DOI: 10.1107/S160053681103100X/zj2016Isup3.cml

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

Acknowledgments

We are grateful to the National Natural Sciences Foundation of China (grant No. 20872057) and the Natural Science Foundation of Henan Province (No. 082300420040) for financial support.

supplementary crystallographic information

Comment

Direct aldol reactions provide an atom-economical approach to create the β-hydroxy carbonyl structural unit found in many natural products and drugs (Machajewski et al. 2000; Nelson, 1998.). In our study, we were interested to the intramolecular aldol condensation reaction. To our surprise, the resulting aldol adducts are further dehydrated to afford an enone compound. The title molecule is built up from three fused rings including two phenyl rings and one seven-membered ring (Fig. 1). The non aromatic seven-membered ring has a screw boat conformation. The two methoxyphenyl rings make dihedral angles of 50.4 (2) Å. In the crystal structure, the weak intermolecular C—H···O hydrogen bonds are observed. Thus, molecules are linked to each other by intermolecular C13—H13B···O3 hydrogen bonds (C13···O3 = 3.349 (3) Å), resulting in a one-dimensional chain. The chains are further connected through the formation of intermolecular C10—H10···O1 hydrogen bonds (C10···O1 = 3.283 (2) Å), leading to a three-dimensional supmolecular architecture, as shown in Fig. 2.

Experimental

2,2-dimethoxy-6,6-diacetyl-1,1-biphenyl (298 mm g, 1 mmol) was added to a solution of CH₃CH₂ONa (6.8 mg, 0.1 mmol) and enthanol (5 ml) at room temperature. The mixture was stirred, monitored by TLC. After 8 h, the mixture was extracted by ethyl acetate (3× 15 ml). The resulting solvent was removed in vacuo to yield the crude product. Purification by silica gel chromatography using 100 ~200 mesh ZCX II eluted by hexane-ethyl acetate (3:1, v/v) gave the yellow solid (196 mg, yield 70%). The crystalline compound was obtained through the slow volatilization of ethyl acetate containing the title compound.

Figures

Fig. 1.

View of the title molecular structure with atom numbering scheme and 50% probability displacement ellipsoids for non-hydrogen atoms.

Fig. 2.

View of three-dimensional structure (C—H···O hydrogen bonds are represented as dashed lines).

Crystal data

C₁₈H₁₆O₃	F(000) = 592
M_r = 280.31	D_x = 1.281 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2351 reflections
a = 7.6615 (10) Å	θ = 2.6–22.6°
b = 12.2005 (16) Å	µ = 0.09 mm⁻¹
c = 15.545 (2) Å	T = 295 K
V = 1453.1 (3) Å³	Block, yellow
Z = 4	0.43 × 0.31 × 0.17 mm

Data collection

Bruker SMART CCD area detector diffractometer	2708 independent reflections
Radiation source: fine-focus sealed tube	2083 reflections with I > 2σ(I)
graphite	R_int = 0.034
and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.964, T_max = 0.986	k = −14→14
11119 measured reflections	l = −18→18

Refinement

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0385P)² + 0.0759P] where P = (F_o² + 2F_c²)/3
2708 reflections	(Δ/σ)_max < 0.001
193 parameters	Δρ_max = 0.10 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)are estimated using the full covariance matrix. The cell e.s.d.'s are takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused when they are defined by crystal symmetry. An approximate (isotropic)treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.90746 (18)	0.51793 (11)	0.45436 (10)	0.0617 (4)
O2	0.6310 (2)	0.46929 (11)	0.35471 (8)	0.0590 (4)
O3	0.4247 (3)	0.68747 (15)	0.67899 (12)	0.0975 (6)
C1	0.8412 (3)	0.43948 (14)	0.50732 (12)	0.0435 (5)
C2	0.6641 (2)	0.45458 (13)	0.53147 (11)	0.0391 (4)
C3	0.5949 (3)	0.38457 (15)	0.59460 (11)	0.0423 (5)
C4	0.6961 (3)	0.29640 (16)	0.62432 (12)	0.0506 (5)
H4	0.6490	0.2483	0.6645	0.061*
C5	0.8624 (3)	0.27996 (16)	0.59543 (14)	0.0544 (5)
H5	0.9256	0.2196	0.6147	0.065*
C6	0.9376 (3)	0.35217 (15)	0.53789 (14)	0.0516 (5)
H6	1.0522	0.3421	0.5199	0.062*
C7	0.5694 (3)	0.55704 (15)	0.39995 (13)	0.0478 (5)
C8	0.5662 (2)	0.54490 (14)	0.48981 (12)	0.0415 (4)
C9	0.4791 (3)	0.62605 (15)	0.53714 (14)	0.0502 (5)
C10	0.4157 (3)	0.72015 (16)	0.49742 (18)	0.0658 (6)
H10	0.3607	0.7740	0.5300	0.079*
C11	0.4340 (3)	0.73350 (19)	0.41045 (19)	0.0756 (7)
H11	0.3966	0.7980	0.3844	0.091*
C12	0.5077 (3)	0.65175 (18)	0.36140 (17)	0.0657 (6)
H12	0.5160	0.6602	0.3021	0.079*
C13	0.3278 (3)	0.3040 (2)	0.66884 (15)	0.0734 (7)
H13A	0.2127	0.3251	0.6867	0.110*
H13B	0.3899	0.2736	0.7169	0.110*
H13C	0.3195	0.2501	0.6240	0.110*
C14	0.4239 (3)	0.40290 (18)	0.63578 (12)	0.0519 (5)
C15	0.3608 (3)	0.5025 (2)	0.65305 (13)	0.0634 (6)
H15	0.2579	0.5040	0.6848	0.076*
C16	0.4316 (3)	0.6103 (2)	0.62877 (14)	0.0624 (6)
C17	1.0812 (3)	0.5087 (2)	0.42411 (17)	0.0778 (7)
H17A	1.0926	0.4431	0.3904	0.117*
H17B	1.1596	0.5054	0.4722	0.117*
H17C	1.1091	0.5712	0.3893	0.117*
C18	0.6894 (4)	0.4865 (3)	0.26972 (15)	0.0946 (10)
H18A	0.7702	0.5466	0.2687	0.142*
H18B	0.5914	0.5032	0.2335	0.142*
H18C	0.7462	0.4215	0.2491	0.142*

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0433 (8)	0.0547 (8)	0.0872 (10)	−0.0025 (7)	0.0133 (8)	0.0130 (8)
O2	0.0767 (10)	0.0580 (8)	0.0422 (8)	0.0003 (8)	0.0094 (7)	0.0039 (7)
O3	0.1176 (15)	0.0921 (12)	0.0829 (12)	0.0259 (12)	−0.0124 (11)	−0.0455 (11)
C1	0.0437 (12)	0.0397 (9)	0.0472 (11)	−0.0009 (9)	0.0022 (9)	−0.0023 (8)
C2	0.0390 (10)	0.0380 (9)	0.0403 (10)	−0.0017 (8)	−0.0028 (8)	−0.0037 (8)
C3	0.0445 (11)	0.0457 (10)	0.0367 (9)	−0.0050 (9)	−0.0059 (9)	−0.0040 (8)
C4	0.0575 (14)	0.0501 (11)	0.0442 (12)	−0.0052 (10)	−0.0081 (10)	0.0055 (9)
C5	0.0585 (14)	0.0481 (11)	0.0566 (12)	0.0082 (10)	−0.0117 (11)	0.0036 (10)
C6	0.0429 (12)	0.0533 (11)	0.0586 (13)	0.0059 (10)	−0.0017 (11)	−0.0056 (10)
C7	0.0465 (12)	0.0436 (10)	0.0533 (12)	−0.0009 (10)	−0.0003 (10)	0.0048 (9)
C8	0.0371 (10)	0.0393 (9)	0.0481 (11)	−0.0021 (8)	−0.0021 (9)	−0.0003 (8)
C9	0.0426 (12)	0.0455 (10)	0.0626 (14)	0.0007 (9)	−0.0098 (10)	−0.0103 (10)
C10	0.0577 (14)	0.0449 (12)	0.0949 (19)	0.0099 (11)	−0.0053 (13)	−0.0067 (12)
C11	0.0739 (18)	0.0526 (13)	0.100 (2)	0.0139 (13)	−0.0096 (16)	0.0202 (14)
C12	0.0654 (15)	0.0643 (14)	0.0673 (16)	0.0037 (12)	−0.0007 (13)	0.0209 (13)
C13	0.0571 (15)	0.0989 (18)	0.0641 (15)	−0.0115 (14)	0.0047 (12)	0.0218 (14)
C14	0.0446 (12)	0.0717 (14)	0.0392 (11)	0.0011 (11)	−0.0005 (10)	−0.0001 (10)
C15	0.0490 (13)	0.0945 (18)	0.0467 (12)	0.0074 (13)	0.0045 (11)	−0.0071 (12)
C16	0.0564 (14)	0.0690 (14)	0.0616 (14)	0.0134 (12)	−0.0114 (12)	−0.0210 (12)
C17	0.0504 (14)	0.0781 (16)	0.105 (2)	−0.0057 (13)	0.0223 (14)	0.0109 (15)
C18	0.126 (3)	0.108 (2)	0.0490 (13)	0.030 (2)	0.0240 (15)	0.0192 (14)

Geometric parameters (Å, °)

O1—C1	1.361 (2)	C9—C16	1.483 (3)
O1—C17	1.416 (2)	C10—C11	1.369 (3)
O2—C7	1.365 (2)	C10—H10	0.9300
O2—C18	1.411 (3)	C11—C12	1.376 (3)
O3—C16	1.225 (2)	C11—H11	0.9300
C1—C6	1.381 (3)	C12—H12	0.9300
C1—C2	1.419 (3)	C13—C14	1.504 (3)
C2—C3	1.405 (2)	C13—H13A	0.9600
C2—C8	1.482 (2)	C13—H13B	0.9600
C3—C4	1.404 (3)	C13—H13C	0.9600
C3—C14	1.475 (3)	C14—C15	1.335 (3)
C4—C5	1.366 (3)	C15—C16	1.472 (3)
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.381 (3)	C17—H17A	0.9600
C5—H5	0.9300	C17—H17B	0.9600
C6—H6	0.9300	C17—H17C	0.9600
C7—C12	1.385 (3)	C18—H18A	0.9600
C7—C8	1.405 (3)	C18—H18B	0.9600
C8—C9	1.402 (3)	C18—H18C	0.9600
C9—C10	1.391 (3)

C1—O1—C17	119.71 (17)	C10—C11—H11	119.9
C7—O2—C18	118.37 (17)	C12—C11—H11	119.9
O1—C1—C6	123.45 (19)	C11—C12—C7	120.3 (2)
O1—C1—C2	115.18 (16)	C11—C12—H12	119.8
C6—C1—C2	121.35 (18)	C7—C12—H12	119.8
C3—C2—C1	117.83 (16)	C14—C13—H13A	109.5
C3—C2—C8	124.46 (17)	C14—C13—H13B	109.5
C1—C2—C8	117.70 (16)	H13A—C13—H13B	109.5
C4—C3—C2	119.13 (18)	C14—C13—H13C	109.5
C4—C3—C14	117.64 (18)	H13A—C13—H13C	109.5
C2—C3—C14	123.12 (17)	H13B—C13—H13C	109.5
C5—C4—C3	121.30 (19)	C15—C14—C3	123.2 (2)
C5—C4—H4	119.3	C15—C14—C13	118.9 (2)
C3—C4—H4	119.3	C3—C14—C13	117.48 (19)
C4—C5—C6	120.54 (19)	C14—C15—C16	128.9 (2)
C4—C5—H5	119.7	C14—C15—H15	115.6
C6—C5—H5	119.7	C16—C15—H15	115.6
C1—C6—C5	119.47 (19)	O3—C16—C15	120.5 (2)
C1—C6—H6	120.3	O3—C16—C9	121.5 (2)
C5—C6—H6	120.3	C15—C16—C9	116.94 (18)
O2—C7—C12	123.33 (19)	O1—C17—H17A	109.5
O2—C7—C8	115.82 (16)	O1—C17—H17B	109.5
C12—C7—C8	120.8 (2)	H17A—C17—H17B	109.5
C9—C8—C7	117.10 (17)	O1—C17—H17C	109.5
C9—C8—C2	122.44 (17)	H17A—C17—H17C	109.5
C7—C8—C2	120.26 (17)	H17B—C17—H17C	109.5
C10—C9—C8	121.1 (2)	O2—C18—H18A	109.5
C10—C9—C16	116.6 (2)	O2—C18—H18B	109.5
C8—C9—C16	121.94 (18)	H18A—C18—H18B	109.5
C11—C10—C9	120.0 (2)	O2—C18—H18C	109.5
C11—C10—H10	120.0	H18A—C18—H18C	109.5
C9—C10—H10	120.0	H18B—C18—H18C	109.5
C10—C11—C12	120.2 (2)

C17—O1—C1—C6	3.6 (3)	C3—C2—C8—C7	−132.37 (19)
C17—O1—C1—C2	−177.90 (18)	C1—C2—C8—C7	49.1 (2)
O1—C1—C2—C3	−171.97 (16)	C7—C8—C9—C10	−6.8 (3)
C6—C1—C2—C3	6.6 (3)	C2—C8—C9—C10	168.16 (18)
O1—C1—C2—C8	6.6 (2)	C7—C8—C9—C16	165.73 (19)
C6—C1—C2—C8	−174.83 (16)	C2—C8—C9—C16	−19.3 (3)
C1—C2—C3—C4	−6.6 (2)	C8—C9—C10—C11	1.6 (3)
C8—C2—C3—C4	174.93 (17)	C16—C9—C10—C11	−171.3 (2)
C1—C2—C3—C14	169.41 (17)	C9—C10—C11—C12	3.1 (4)
C8—C2—C3—C14	−9.1 (3)	C10—C11—C12—C7	−2.3 (4)
C2—C3—C4—C5	2.5 (3)	O2—C7—C12—C11	174.6 (2)
C14—C3—C4—C5	−173.75 (18)	C8—C7—C12—C11	−3.2 (3)
C3—C4—C5—C6	2.1 (3)	C4—C3—C14—C15	141.1 (2)
O1—C1—C6—C5	176.20 (18)	C2—C3—C14—C15	−34.9 (3)
C2—C1—C6—C5	−2.2 (3)	C4—C3—C14—C13	−31.5 (2)
C4—C5—C6—C1	−2.2 (3)	C2—C3—C14—C13	152.51 (19)
C18—O2—C7—C12	21.8 (3)	C3—C14—C15—C16	6.9 (3)
C18—O2—C7—C8	−160.3 (2)	C13—C14—C15—C16	179.3 (2)
O2—C7—C8—C9	−170.39 (17)	C14—C15—C16—O3	−141.6 (2)
C12—C7—C8—C9	7.6 (3)	C14—C15—C16—C9	49.7 (3)
O2—C7—C8—C2	14.6 (3)	C10—C9—C16—O3	−37.9 (3)
C12—C7—C8—C2	−167.46 (18)	C8—C9—C16—O3	149.3 (2)
C3—C2—C8—C9	52.8 (3)	C10—C9—C16—C15	130.6 (2)
C1—C2—C8—C9	−125.65 (19)	C8—C9—C16—C15	−42.2 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13B···O3ⁱ	0.96	2.40	3.349 (3)	171.
C10—H10···O1ⁱⁱ	0.93	2.58	3.283 (2)	133.

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x−1/2, −y+3/2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZJ2016).

References

Broder, C. K., Davidson, M. G., Trevor Forsyth, V., Howard, J. A. K., Lamb, S. & Mason, S. A. (2002). Cryst. Growth Des. 2, 163–169.
Bruker (2004). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
Machajewski, T. D. & Wong, C. H. (2000). Angew. Chem. Int. Ed. 39, 1352–1375. [PubMed]
Nelson, S. G. (1998). Tetrahedron Asymmetry, 9, 357–389.
Senthil Kumar, V. S., Christopher Pigge, F. & Rath, N. P. (2006). Cryst. Growth Des. 6, 193–196.
Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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