2,9,10-Trimeth­oxy­dibenzo[b,d]oxepin-7(6H)-one

Hou, Y.-J.; Song, S.-L.; Chu, W.-Y.; Sun, Z.-Z.

doi:10.1107/S1600536811053803

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o204

doi:10.1107/S1600536811053803

Open

access

2,9,10-Trimethoxydibenzo[b,d]oxepin-7(6H)-one

Yan-Jun Hou,^a Shu-Lin Song,^a Wen-Yi Chu ^a and Zhi-Zhong Sun ^a ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: hljusunzhizhong@163.com

(Received 2 December 2011; accepted 14 December 2011; online 21 December 2011)

The title compound, C₁₇H₁₆O₅, was prepared through a cyclization reaction of 2-(3′,4′,5-trimethoxybiphenyl-2-yloxy)acetyl chloride. The two benzene rings form a dihedral angle of 34.55 (5)°. The crystal structure does not feature any hydrogen bonds.

Related literature

For general background to the synthesis and properties of the title compound, see: Suau et al. (1996 ); Tandon et al. (2009 ). For the biological activity of methoxydibenzooxepin-one derivatives, see: Yoshioka et al. (1978 ).

Experimental

Crystal data

C₁₇H₁₆O₅
M_r = 300.30
Monoclinic, P 2₁ /c
a = 11.5474 (10) Å
b = 8.3776 (7) Å
c = 14.8801 (13) Å
β = 93.607 (1)°
V = 1436.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.32 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.968, T_max = 0.976
11231 measured reflections
3517 independent reflections
2517 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.127
S = 1.05
3517 reflections
202 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (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: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536811053803/rk2322sup1.cif

Supporting information file. DOI: 10.1107/S1600536811053803/rk2322Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053803/rk2322Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536811053803/rk2322Isup4.cml

checkCIF report

Comment top

The methoxydibenzooxepin–one derivatives have important antiviral activity and cause attention to new synthetic methods and investigation of similar compounds (Yoshioka et al., 1978). Many methoxydibenzooxepin–one derivatives directly prepared from methoxy 2–(biphenyl–2–yloxy) acetyl chloride (Suau et al., 1996; Tandon et al., 2009). The 2,9,10–trimethoxydibenzo[b,d]oxepin–7(6H)–one, (Fig. 1), was prepared from the previously synthesized 2–(3',4',5–trimethoxy biphenyl–2–yloxy) acetyl chloride.

The dihedral angle between the benzene ring (C1–C6) and benzene ring (C7–C12) is 34.55 (5)°. In the crystal structure neither classical nor non–classical hydrogen bonds are found.

Related literature top

For general background on the synthesis and properties of 2,9,10–trimethoxydibenzo[b,d]oxepin–7(6H)–one, see: Suau et al. (1996); Tandon et al. (2009). For the biological activity of methoxydibenzooxepin–one derivatives, see: Yoshioka et al.(1978).

Experimental top

To a solution of 2–(3',4',5–trimethoxybiphenyl–2–yloxy) acetyl chloride (5 mmol) in 20 ml trifluoroacetic anhydride was added anhydrous zinc chloride (1 mmol). After stirring the reaction mixture for 12 h at reflux temperature, the trifluoroacetic anhydride was recovered under reduced pressure and residue was added 20 ml water. The aqueous phases were extracted with 100 ml ethyl acetate. The organic extracts were washed with 200 ml saturated aqueous sodium chloride, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting crude material was purified via silica gel chromatography (5% ethyl acetate / hexane) to afford a translucent solid in a yield of 80%. Crystals suitable for single–crystal X–ray diffraction were obtained by recrystallization from methanol at room temperature in a total yield of 28%. Analysis found: C 67.9, H 5.3%; C₁₇H₁₆O₅ requires: C 67.9, H 5.4%. ¹H NMR (400 MHz, DMSO) 7.33 (s, 1H), 7.25 (d, J = 2.9 Hz, 1H), 7.16 (t, J = 4.4 Hz, 1H), 6.96 (dd, J = 8.7, 2.9 Hz, 1H), 4.75 (s, 2H), 3.97 (s, 1H), 3.86 (s, 1H), 3.82 (s, 2H), 2.50 (s, 2H).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.

2,9,10–trimethoxydibenzo[b,d]oxepin–7(6H)–one top

Crystal data top

C₁₇H₁₆O₅	F(000) = 632
M_r = 300.30	D_x = 1.388 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3123 reflections
a = 11.5474 (10) Å	θ = 2.7–25.0°
b = 8.3776 (7) Å	µ = 0.10 mm⁻¹
c = 14.8801 (13) Å	T = 295 K
β = 93.607 (1)°	Block, colorless
V = 1436.6 (2) Å³	0.32 × 0.26 × 0.24 mm
Z = 4

Data collection top

Bruker SMART APEX II CCD diffractometer	3517 independent reflections
Radiation source: fine–focus sealed tube	2517 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ– and ω–scans	θ_max = 28.3°, θ_min = 2.7°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −15→13
T_min = 0.968, T_max = 0.976	k = −11→11
11231 measured reflections	l = −19→18

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0578P)² + 0.2417P] where P = (F_o² + 2F_c²)/3
3517 reflections	(Δ/σ)_max < 0.001
202 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₇H₁₆O₅	V = 1436.6 (2) Å³
M_r = 300.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.5474 (10) Å	µ = 0.10 mm⁻¹
b = 8.3776 (7) Å	T = 295 K
c = 14.8801 (13) Å	0.32 × 0.26 × 0.24 mm
β = 93.607 (1)°

Data collection top

Bruker SMART APEX II CCD diffractometer	3517 independent reflections
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	2517 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.976	R_int = 0.022
11231 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.05	Δρ_max = 0.26 e Å⁻³
3517 reflections	Δρ_min = −0.18 e Å⁻³
202 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.64848 (13)	0.13216 (17)	0.18464 (10)	0.0430 (3)
C2	0.53334 (14)	0.09007 (19)	0.18643 (11)	0.0509 (4)
H2	0.4842	0.1508	0.2200	0.061*
C3	0.48957 (14)	−0.0412 (2)	0.13909 (11)	0.0515 (4)
H3	0.4115	−0.0682	0.1398	0.062*
C4	0.56459 (14)	−0.13171 (19)	0.09053 (11)	0.0477 (4)
C5	0.67990 (14)	−0.08725 (18)	0.08744 (11)	0.0466 (4)
H5	0.7286	−0.1475	0.0533	0.056*
C6	0.72465 (13)	0.04551 (17)	0.13424 (9)	0.0409 (3)
C7	0.84963 (13)	0.08803 (16)	0.13366 (9)	0.0396 (3)
C8	0.93022 (13)	−0.03654 (16)	0.12805 (10)	0.0426 (3)
H8	0.9037	−0.1414	0.1265	0.051*
C9	1.04778 (13)	−0.00803 (16)	0.12484 (10)	0.0422 (3)
C10	1.08923 (13)	0.15007 (17)	0.12771 (10)	0.0415 (3)
C11	1.01109 (13)	0.27300 (16)	0.13109 (10)	0.0428 (3)
H11	1.0380	0.3776	0.1309	0.051*
C12	0.89187 (13)	0.24533 (16)	0.13480 (10)	0.0403 (3)
C13	0.81824 (14)	0.39121 (18)	0.13527 (11)	0.0480 (4)
C14	0.71248 (14)	0.39826 (18)	0.18854 (11)	0.0520 (4)
H14A	0.7209	0.4871	0.2302	0.062*
H14B	0.6457	0.4201	0.1475	0.062*
C15	0.41610 (16)	−0.3191 (2)	0.04808 (13)	0.0642 (5)
H15A	0.4005	−0.3388	0.1097	0.096*
H15B	0.4046	−0.4156	0.0139	0.096*
H15C	0.3644	−0.2381	0.0237	0.096*
C16	1.09330 (15)	−0.28365 (17)	0.11482 (13)	0.0558 (4)
H16A	1.0540	−0.3101	0.1678	0.084*
H16B	1.1596	−0.3518	0.1108	0.084*
H16C	1.0414	−0.2983	0.0625	0.084*
C17	1.25317 (15)	0.32212 (19)	0.12655 (14)	0.0615 (5)
H17A	1.2195	0.3802	0.0758	0.092*
H17B	1.3358	0.3170	0.1230	0.092*
H17C	1.2354	0.3754	0.1811	0.092*
O1	0.68972 (10)	0.25851 (13)	0.23796 (7)	0.0506 (3)
O2	0.53211 (10)	−0.26715 (14)	0.04357 (9)	0.0641 (4)
O3	1.13016 (9)	−0.12153 (12)	0.11976 (9)	0.0558 (3)
O4	1.20699 (9)	0.16530 (12)	0.12625 (8)	0.0527 (3)
O5	0.84540 (10)	0.51664 (13)	0.09494 (9)	0.0650 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0423 (8)	0.0459 (8)	0.0414 (8)	0.0005 (6)	0.0062 (6)	−0.0007 (6)
C2	0.0459 (9)	0.0560 (9)	0.0521 (9)	0.0024 (7)	0.0131 (7)	−0.0034 (7)
C3	0.0379 (8)	0.0620 (10)	0.0553 (10)	−0.0048 (7)	0.0089 (7)	0.0018 (8)
C4	0.0464 (9)	0.0482 (8)	0.0488 (9)	−0.0073 (7)	0.0056 (7)	−0.0026 (7)
C5	0.0430 (9)	0.0461 (8)	0.0514 (9)	−0.0021 (7)	0.0097 (7)	−0.0063 (7)
C6	0.0408 (8)	0.0408 (7)	0.0416 (8)	−0.0006 (6)	0.0056 (6)	0.0007 (6)
C7	0.0395 (8)	0.0395 (7)	0.0400 (7)	−0.0004 (6)	0.0043 (6)	−0.0003 (6)
C8	0.0433 (8)	0.0332 (7)	0.0515 (9)	−0.0012 (6)	0.0044 (6)	−0.0002 (6)
C9	0.0411 (8)	0.0335 (7)	0.0519 (9)	0.0031 (6)	0.0025 (6)	0.0009 (6)
C10	0.0368 (8)	0.0371 (7)	0.0508 (8)	−0.0004 (6)	0.0038 (6)	0.0027 (6)
C11	0.0431 (9)	0.0325 (7)	0.0530 (9)	−0.0019 (6)	0.0036 (7)	0.0004 (6)
C12	0.0410 (8)	0.0360 (7)	0.0439 (8)	0.0033 (6)	0.0037 (6)	0.0000 (6)
C13	0.0451 (9)	0.0390 (8)	0.0593 (10)	0.0050 (6)	−0.0006 (7)	−0.0025 (7)
C14	0.0510 (10)	0.0454 (8)	0.0598 (10)	0.0061 (7)	0.0050 (8)	−0.0094 (7)
C15	0.0527 (11)	0.0744 (12)	0.0652 (11)	−0.0214 (9)	0.0006 (9)	−0.0076 (9)
C16	0.0530 (10)	0.0328 (8)	0.0812 (12)	0.0027 (7)	0.0023 (9)	−0.0053 (7)
C17	0.0462 (10)	0.0419 (9)	0.0967 (14)	−0.0078 (7)	0.0061 (9)	0.0024 (9)
O1	0.0527 (7)	0.0506 (6)	0.0492 (6)	−0.0018 (5)	0.0093 (5)	−0.0104 (5)
O2	0.0521 (7)	0.0640 (8)	0.0771 (8)	−0.0187 (6)	0.0115 (6)	−0.0191 (6)
O3	0.0422 (6)	0.0329 (5)	0.0922 (9)	0.0045 (4)	0.0037 (6)	−0.0005 (5)
O4	0.0371 (6)	0.0360 (5)	0.0852 (8)	−0.0015 (4)	0.0064 (5)	0.0038 (5)
O5	0.0541 (7)	0.0410 (6)	0.1010 (10)	0.0040 (5)	0.0143 (7)	0.0148 (6)

Geometric parameters (Å, º) top

C1—C2	1.377 (2)	C11—C12	1.401 (2)
C1—O1	1.3889 (18)	C11—H11	0.9300
C1—C6	1.395 (2)	C12—C13	1.4891 (19)
C2—C3	1.385 (2)	C13—O5	1.2595 (19)
C2—H2	0.9300	C13—C14	1.498 (2)
C3—C4	1.388 (2)	C14—O1	1.4159 (19)
C3—H3	0.9300	C14—H14A	0.9700
C4—O2	1.3724 (19)	C14—H14B	0.9700
C4—C5	1.386 (2)	C15—O2	1.414 (2)
C5—C6	1.394 (2)	C15—H15A	0.9600
C5—H5	0.9300	C15—H15B	0.9600
C6—C7	1.487 (2)	C15—H15C	0.9600
C7—C8	1.4042 (19)	C16—O3	1.4237 (17)
C7—C12	1.4049 (19)	C16—H16A	0.9600
C8—C9	1.382 (2)	C16—H16B	0.9600
C8—H8	0.9300	C16—H16C	0.9600
C9—O3	1.3504 (17)	C17—O4	1.4177 (18)
C9—C10	1.4081 (19)	C17—H17A	0.9600
C10—O4	1.3674 (18)	C17—H17B	0.9600
C10—C11	1.372 (2)	C17—H17C	0.9600

C2—C1—O1	118.73 (13)	C11—C12—C13	115.30 (12)
C2—C1—C6	121.28 (14)	C7—C12—C13	124.89 (14)
O1—C1—C6	119.90 (14)	O5—C13—C12	121.55 (14)
C1—C2—C3	121.03 (15)	O5—C13—C14	117.05 (13)
C1—C2—H2	119.5	C12—C13—C14	121.30 (14)
C3—C2—H2	119.5	O1—C14—C13	115.23 (13)
C2—C3—C4	118.62 (15)	O1—C14—H14A	108.5
C2—C3—H3	120.7	C13—C14—H14A	108.5
C4—C3—H3	120.7	O1—C14—H14B	108.5
O2—C4—C5	115.95 (14)	C13—C14—H14B	108.5
O2—C4—C3	123.86 (15)	H14A—C14—H14B	107.5
C5—C4—C3	120.19 (14)	O2—C15—H15A	109.5
C4—C5—C6	121.63 (14)	O2—C15—H15B	109.5
C4—C5—H5	119.2	H15A—C15—H15B	109.5
C6—C5—H5	119.2	O2—C15—H15C	109.5
C5—C6—C1	117.21 (14)	H15A—C15—H15C	109.5
C5—C6—C7	121.17 (13)	H15B—C15—H15C	109.5
C1—C6—C7	121.56 (13)	O3—C16—H16A	109.5
C8—C7—C12	117.84 (13)	O3—C16—H16B	109.5
C8—C7—C6	117.99 (13)	H16A—C16—H16B	109.5
C12—C7—C6	124.12 (13)	O3—C16—H16C	109.5
C9—C8—C7	121.98 (13)	H16A—C16—H16C	109.5
C9—C8—H8	119.0	H16B—C16—H16C	109.5
C7—C8—H8	119.0	O4—C17—H17A	109.5
O3—C9—C8	125.25 (13)	O4—C17—H17B	109.5
O3—C9—C10	115.14 (13)	H17A—C17—H17B	109.5
C8—C9—C10	119.62 (13)	O4—C17—H17C	109.5
O4—C10—C11	125.97 (13)	H17A—C17—H17C	109.5
O4—C10—C9	115.07 (12)	H17B—C17—H17C	109.5
C11—C10—C9	118.95 (13)	C1—O1—C14	113.68 (12)
C10—C11—C12	121.83 (13)	C4—O2—C15	117.35 (14)
C10—C11—H11	119.1	C9—O3—C16	117.73 (12)
C12—C11—H11	119.1	C10—O4—C17	117.43 (12)
C11—C12—C7	119.74 (13)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₆O₅
M_r	300.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	11.5474 (10), 8.3776 (7), 14.8801 (13)
β (°)	93.607 (1)
V (Å³)	1436.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.32 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART APEX II CCD diffractometer
Absorption correction	Multi-scan SADABS (Sheldrick, 1996)
T_min, T_max	0.968, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	11231, 3517, 2517
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.127, 1.05
No. of reflections	3517
No. of parameters	202
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.18

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Acknowledgements

We thank the National Natural Science Foundation of China (No. 20872030), the Foundation of Heilongjiang Education Committee (No. 12511383), the Key Laboratory of Chemical Engineering Process and Technology for High-Efficiency Conversion, College of Heilongjiang Province, and Heilongjiang University, China, for supporting this study.

References

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Suau, R., Lopez-Romero, J. M., Alonso, F. J. & Lobo, C. (1996). Tetrahedron, 52, 11307–11320. CrossRef CAS Web of Science Google Scholar
Tandon, V. K., Maurya, H. K., Kumar, B., Kumar, B. & Ram, V. J. (2009). Synlett, 18, 2992–2996. Web of Science CrossRef Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yoshioka, T., Kitagawa, M., Oki, M., Kubo, S., Tagawa, H. & Ueno, K. (1978). J. Med. Chem. 21, 633–639. CrossRef CAS PubMed Web of Science Google Scholar