6,6′-Oxydichroman

Wang, M.; Ye, Y.-H.

doi:10.1107/S1600536807066779

organic compounds

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Volume 64| Part 1| January 2008| Page o308

https://doi.org/10.1107/S1600536807066779

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6,6′-Oxydichroman

Meng Wang ^a,^b and Yong-Hao Ye ^a,^b ^*

^aDepartment of Pharmacy, Second Affiliated Hospital of Soochow University, Suzhou 215004, People's Republic of China, and ^bCollege of Plant Protection, Nanjing Agricultural University, Nanjing 210095, People's Republic of China
^*Correspondence e-mail: adler_20008@yahoo.com.cn

(Received 15 November 2007; accepted 13 December 2007; online 18 December 2007)

The title compound, C₁₈H₁₈O₃, was synthesized from dichroman in concentrated sulfuric acid. The molecule has a twofold axis passing through the central O atom. The dihedral angle between the two symmetry-related benzene rings is 63.6 (3)°. Weak C—H⋯π interactions are present in the structure.

Related literature

For related literature, see: Allen et al. (1987 ); Li et al. (2006 , 2007 ); Xiao, Shi et al. (2007 ); Xiao, Xue et al. (2007 ); Huang et al. (2007 ); Zhang et al. (2007 ); Shi et al. (2007 ); Cao et al. (2007 ); Ruan et al. (2006 ).

Experimental

Crystal data

C₁₈H₁₈O₃
M_r = 282.32
Orthorhombic, F d d 2
a = 17.515 (4) Å
b = 29.660 (6) Å
c = 5.7680 (12) Å
V = 2996.4 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 (2) K
0.23 × 0.20 × 0.20 mm

Data collection

Bruker APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.981, T_max = 0.983
4727 measured reflections
855 independent reflections
810 reflections with I > 2σ(I)
R_int = 0.073

Refinement

R[F² > 2σ(F²)] = 0.073
wR(F²) = 0.216
S = 1.13
855 reflections
96 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the ring C1–C6.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯Cg1ⁱ	0.97	2.91	3.856 (6)	167
Symmetry code: (i) $[x+{\script{1\over 4}}, -y+{\script{3\over 4}}, z-{\script{1\over 4}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807066779/bq2049sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807066779/bq2049Isup2.hkl

checkCIF report

Comment top

Synthesized organic compounds with a pyran cycle are found being good biological activities (Li et al., 2007; Xiao, Shi et al., 2007; Xiao, Xue et al., 2007; Huang et al., 2007; Zhang et al., 2007; Shi et al., 2007; Cao et al., 2007; Ruan et al., 2006; Li et al., 2006). So we prepared a series of derivatives with pyran cycles. Here we report the crystal structure of the title compound.

The title compound consists of an oxygen atom bridged two chroman (Fig. 1). The molecule has a twofold axis symmetry position at the central O1 atom. The dihedal angle between the two symmetry-related benzene rings is 63.6 (3)°. In each chroman, all the atoms, except C8 atom, are nearly coplanar, with mean deviation from plane by 0.021 (4) Å. C8 atom is located 0.577 (4)Å above the plane defined by other non-hydrogen atoms. All the bond values are within normal ranges (Allen et al., 1987). There exists weak C8–H8B···Cg1 interaction (Cg1:C1—C6) (Table 1, Fig. 2).

Related literature top

For related literature, see: Allen et al. (1987); Li et al. (2006, 2007); Xiao, Shi et al. (2007); Xiao, Xue et al. (2007); Huang et al. (2007); Zhang et al. (2007); Shi et al. (2007); Cao et al. (2007); Ruan et al. (2006).

Experimental top

Dichroman was disolved in toluene solution and a few drops of concentrated sulfuric acid was added. The above solution was refluxed for two hours. After the solution was cooled to room temperature colorless microcrystals were precipitated. They were filtered, washed with toluene for three times. Yield: 32%.

Structure description top

For related literature, see: Allen et al. (1987); Li et al. (2006, 2007); Xiao, Shi et al. (2007); Xiao, Xue et al. (2007); Huang et al. (2007); Zhang et al. (2007); Shi et al. (2007); Cao et al. (2007); Ruan et al. (2006).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. Symmetry code (i): -x, 1 - y, z.
	Fig. 2. Molecular packing of (I) viewed down the c axis. The weak C–H···Cg interactions are shown as dashed lines.

6,6'-Oxydichroman top

Crystal data top

C₁₈H₁₈O₃	F(000) = 1200
M_r = 282.32	D_x = 1.252 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 872 reflections
a = 17.515 (4) Å	θ = 2.5–24.3°
b = 29.660 (6) Å	µ = 0.08 mm⁻¹
c = 5.7680 (12) Å	T = 298 K
V = 2996.4 (10) Å³	Prism, colorless
Z = 8	0.23 × 0.20 × 0.20 mm

Data collection top

Bruker APEX area-detector diffractometer	855 independent reflections
Radiation source: fine-focus sealed tube	810 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
φ and ω scans	θ_max = 26.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→21
T_min = 0.981, T_max = 0.983	k = −36→32
4727 measured reflections	l = −7→6

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)] = 0.073	H-atom parameters constrained
wR(F²) = 0.216	w = 1/[σ²(F_o²) + (0.1367P)² + 4.7011P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
855 reflections	Δρ_max = 0.32 e Å⁻³
96 parameters	Δρ_min = −0.55 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 631 Friedel pairs
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₈H₁₈O₃	V = 2996.4 (10) Å³
M_r = 282.32	Z = 8
Orthorhombic, Fdd2	Mo Kα radiation
a = 17.515 (4) Å	µ = 0.08 mm⁻¹
b = 29.660 (6) Å	T = 298 K
c = 5.7680 (12) Å	0.23 × 0.20 × 0.20 mm

Data collection top

Bruker APEX area-detector diffractometer	855 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	810 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.983	R_int = 0.073
4727 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	1 restraint
wR(F²) = 0.216	H-atom parameters constrained
S = 1.13	Δρ_max = 0.32 e Å⁻³
855 reflections	Δρ_min = −0.55 e Å⁻³
96 parameters	Absolute structure: Flack (1983), 631 Friedel pairs

Special details top

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 taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used 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) top

	x	y	z	U_iso*/U_eq
O1	0.5000	0.5000	0.0623 (13)	0.090 (2)
O2	0.7616 (2)	0.44456 (13)	0.5838 (9)	0.0779 (14)
C1	0.6782 (2)	0.43486 (12)	0.2525 (7)	0.0378 (9)
C2	0.6140 (2)	0.44952 (12)	0.1313 (7)	0.0387 (9)
H2	0.6008	0.4345	−0.0045	0.046*
C3	0.5687 (2)	0.48541 (13)	0.2029 (8)	0.0386 (9)
C4	0.5900 (2)	0.50701 (12)	0.4073 (8)	0.0412 (9)
H4	0.5609	0.5310	0.4615	0.049*
C5	0.6539 (2)	0.49345 (13)	0.5317 (8)	0.0413 (9)
H5	0.6670	0.5087	0.6669	0.050*
C6	0.69851 (19)	0.45734 (12)	0.4570 (7)	0.0360 (8)
C7	0.7245 (3)	0.39470 (15)	0.1747 (9)	0.0561 (12)
H7A	0.7590	0.4039	0.0521	0.067*
H7B	0.6904	0.3719	0.1122	0.067*
C8	0.7703 (3)	0.37452 (17)	0.3725 (12)	0.0640 (14)
H8A	0.7361	0.3583	0.4754	0.077*
H8B	0.8067	0.3531	0.3104	0.077*
C9	0.8113 (3)	0.40910 (16)	0.5053 (11)	0.0614 (15)
H9A	0.8355	0.3951	0.6384	0.074*
H9B	0.8511	0.4220	0.4091	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.081 (4)	0.128 (5)	0.060 (4)	0.032 (3)	0.000	0.000
O2	0.074 (2)	0.075 (2)	0.085 (3)	0.0149 (17)	−0.036 (2)	−0.021 (2)
C1	0.0383 (17)	0.0360 (17)	0.039 (2)	0.0011 (13)	−0.0009 (17)	−0.0039 (17)
C2	0.0395 (18)	0.0405 (17)	0.0360 (19)	0.0017 (14)	−0.0002 (17)	−0.0066 (16)
C3	0.0315 (16)	0.0445 (17)	0.040 (2)	0.0029 (13)	0.0022 (16)	0.0016 (17)
C4	0.0379 (18)	0.0384 (17)	0.047 (2)	0.0051 (14)	0.0054 (17)	−0.0053 (18)
C5	0.0408 (19)	0.0434 (19)	0.040 (2)	−0.0047 (15)	−0.0021 (17)	−0.0125 (17)
C6	0.0313 (15)	0.0370 (16)	0.040 (2)	−0.0023 (13)	−0.0014 (16)	0.0013 (16)
C7	0.065 (3)	0.053 (2)	0.051 (3)	0.019 (2)	−0.011 (2)	−0.010 (2)
C8	0.059 (3)	0.057 (2)	0.076 (4)	0.020 (2)	−0.010 (3)	−0.003 (3)
C9	0.048 (2)	0.064 (3)	0.072 (4)	0.0163 (19)	−0.018 (3)	−0.001 (3)

Geometric parameters (Å, º) top

O1—C3ⁱ	1.514 (5)	C4—H4	0.9300
O1—C3	1.514 (6)	C5—C6	1.394 (5)
O2—C6	1.379 (5)	C5—H5	0.9300
O2—C9	1.438 (6)	C7—C8	1.518 (7)
C1—C2	1.393 (5)	C7—H7A	0.9700
C1—C6	1.401 (6)	C7—H7B	0.9700
C1—C7	1.509 (5)	C8—C9	1.468 (7)
C2—C3	1.390 (5)	C8—H8A	0.9700
C2—H2	0.9300	C8—H8B	0.9700
C3—C4	1.393 (6)	C9—H9A	0.9700
C4—C5	1.388 (6)	C9—H9B	0.9700

C3ⁱ—O1—C3	115.2 (6)	C5—C6—C1	118.9 (3)
C6—O2—C9	121.3 (4)	C1—C7—C8	111.8 (4)
C2—C1—C6	118.6 (3)	C1—C7—H7A	109.3
C2—C1—C7	122.0 (4)	C8—C7—H7A	109.3
C6—C1—C7	119.3 (3)	C1—C7—H7B	109.3
C3—C2—C1	123.4 (4)	C8—C7—H7B	109.3
C3—C2—H2	118.3	H7A—C7—H7B	107.9
C1—C2—H2	118.3	C9—C8—C7	112.1 (4)
C2—C3—C4	116.8 (3)	C9—C8—H8A	109.2
C2—C3—O1	120.9 (4)	C7—C8—H8A	109.2
C4—C3—O1	122.4 (4)	C9—C8—H8B	109.2
C5—C4—C3	121.4 (3)	C7—C8—H8B	109.2
C5—C4—H4	119.3	H8A—C8—H8B	107.9
C3—C4—H4	119.3	O2—C9—C8	112.3 (4)
C4—C5—C6	121.0 (4)	O2—C9—H9A	109.1
C4—C5—H5	119.5	C8—C9—H9A	109.1
C6—C5—H5	119.5	O2—C9—H9B	109.1
O2—C6—C5	119.8 (4)	C8—C9—H9B	109.1
O2—C6—C1	121.3 (3)	H9A—C9—H9B	107.9

C6—C1—C2—C3	−0.1 (6)	C4—C5—C6—O2	−180.0 (4)
C7—C1—C2—C3	177.7 (4)	C4—C5—C6—C1	0.3 (6)
C1—C2—C3—C4	−0.2 (6)	C2—C1—C6—O2	−179.7 (4)
C1—C2—C3—O1	179.4 (3)	C7—C1—C6—O2	2.4 (6)
C3ⁱ—O1—C3—C2	142.1 (4)	C2—C1—C6—C5	0.1 (5)
C3ⁱ—O1—C3—C4	−38.3 (3)	C7—C1—C6—C5	−177.8 (4)
C2—C3—C4—C5	0.5 (6)	C2—C1—C7—C8	−158.0 (4)
O1—C3—C4—C5	−179.1 (4)	C6—C1—C7—C8	19.9 (6)
C3—C4—C5—C6	−0.6 (6)	C1—C7—C8—C9	−47.3 (6)
C9—O2—C6—C5	−176.6 (4)	C6—O2—C9—C8	−31.5 (7)
C9—O2—C6—C1	3.2 (7)	C7—C8—C9—O2	53.2 (7)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8b···Cg1ⁱⁱ	0.97	2.91	3.856 (6)	167

Symmetry code: (ii) x+1/4, −y+3/4, z−1/4.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₈O₃
M_r	282.32
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	298
a, b, c (Å)	17.515 (4), 29.660 (6), 5.7680 (12)
V (Å³)	2996.4 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.23 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEX area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.981, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	4727, 855, 810
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.216, 1.13
No. of reflections	855
No. of parameters	96
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.55
Absolute structure	Flack (1983), 631 Friedel pairs

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8b···Cg1ⁱ	0.97	2.906	3.856 (6)	166.49

Symmetry code: (i) x+1/4, −y+3/4, z−1/4.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Cao, P., Ding, H., Ge, H.-M. & Zhu, H.-L. (2007). Chem. Biodivers. 4, 881–886. Web of Science CrossRef PubMed CAS Google Scholar
Huang, X.-F., Ruan, B.-F., Wang, X.-T., Xu, C., Ge, H.-M., Zhu, H.-L. & Tan, R.-X. (2007). Eur. J. Med. Chem. 42, 263–267. Web of Science CrossRef PubMed CAS Google Scholar
Li, H.-Q., Ge, H.-M., Chen, Y.-X., Xu, C., Shi, L., Ding, H., Zhu, H.-L. & Tan, R.-X. (2006). Chem. Biodivers. 3, 463–472. Web of Science CrossRef PubMed Google Scholar
Li, H.-Q., Xu, C., Li, H.-S., Xiao, Z.-P., Shi, L. & Zhu, H.-L. (2007). ChemMedChem, 2, 1361–1369. Web of Science CrossRef PubMed CAS Google Scholar
Ruan, B.-F., Huang, X.-F., Ding, H., Xu, C., Ge, H.-M., Zhu, H.-L. & Tan, R.-X. (2006). Chem. Biodivers. 3, 975–981. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Shi, L., Ge, H.-M., Tan, S.-H., Li, H.-Q., Song, Y.-C., Zhu, H.-L. & Tan, R.-X. (2007). Eur. J. Med. Chem. 42, 558–564. Web of Science CrossRef PubMed CAS Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Xiao, Z.-P., Shi, D.-H., Li, H.-Q., Zhang, L.-N., Xu, C. & Zhu, H.-L. (2007). Bioorg. Med. Chem. 15, 3703–3710. Web of Science CrossRef PubMed CAS Google Scholar
Xiao, Z.-P., Xue, J.-Y., Tan, S.-H., Li, H.-Q. & Zhu, H.-L. (2007). Bioorg. Med. Chem. 15, 4212–4219. Web of Science CSD CrossRef PubMed CAS Google Scholar
Zhang, L.-N., Xiao, Z.-P., Ding, H., Ge, H.-M., Xu, C., Zhu, H.-L. & Tan, R.-X. (2007). Chem. Biodivers. 4, 248–255. Web of Science CrossRef PubMed CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o308

https://doi.org/10.1107/S1600536807066779

Open

access