9 Butyl 3,4,5,6,7,9 hexa­hydro 2H xanthene 1,8 dione

organic papers

Acta Cryst.(2005). E61, o1139–o1140 doi:10.1107/S1600536805006501 Zhu, Huang and Pan _C

17H22O3

o1139

Structure Reports Online

ISSN 1600-5368

9-Butyl-3,4,5,6,7,9-hexahydro-2

H

-xanthene-1,8-dione

Yu-Lin Zhu, Shen-Lin Huang and Yuan-Jiang Pan*

Department of Chemistry, Zhejiang University, Hangzhou 310027, People’s Republic of China

Correspondence e-mail: cheyjpan@zju.edu.cn

Key indicators

Single-crystal X-ray study

T= 298 K

Mean(C–C) = 0.005 A˚

Rfactor = 0.039

wRfactor = 0.089 Data-to-parameter ratio = 9.6

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

The title compound, C17H22O3, which was synthesized by the

condensation of cyclohexane-1,3-dione and n-valeraldehyde, includes a partially hydrogenated xanthene ring system. The molecule has crystallographic mirror symmetry. The central ring adopts a very shallow boat conformation while the symmetry-related outer six-membered rings have sofa confor-mations. Molecules form extended tapes in thec-axis direction though weak C—H O interactions.

Comment

The synthesis of 9-butyl-3,4,5,6,7,9-hexahydro-2H -xanthene-1,8-dione, (I), was initially reported in 1962 (Hellmann & Schroeder, 1962). In our experiment, the reaction of cyclo-hexane-1,3-dione and n-valeraldehyde in the presence of tri-methylsilyl chloride (TMSCl) affords (I) in 78% yield. Fig. 1 shows the molecular structure of (I).

The central ring is in a very shallow boat conformation, with atoms C1, C6, C1i and C6i [symmetry code: (i) 1x, y, z] exactly coplanar by symmetry and atoms O1 and C7 0.156 (4) and 0.263 (6) A˚ from this plane. Atoms O1 and C7–C11 lie on a crystallographic mirror plane at x = 12. The two outer

symmetry-related six-membered rings are each in a sofa conformation, with atoms C1, C2, C4, C5 and C6 forming a plane (r.m.s. deviation = 0.024 A˚ ) and atom C3 0.595 (4) A˚ from this plane. The bond lengths and angles in (I) are normal. The O2—C5—C6—C1 torsion angle of 176.2 (2) _{and the} C5—C6 bond length of 1.458 (4) A˚ indicate conjugation between the O2 C5 and C6 C1 bonds. The torsion angle of 61.8 (2) _{for C6—C7—C8—C9 defines the orientation of the} n-butyl group. Molecules are linked by weak C—H O interactions [H3A O2ii = 2.59 A˚ , C3 O2ii = 3.316 (4) A˚ and C3—H3A O2i = 132_{, symmetry code: (ii) x, 1y,}

1

2+z], forming tapes in thec-axis direction (see Fig. 2).

Experimental

Cyclohexane-1,3-dione (10 mmol), n-valeraldehyde (10 mmol) and dimethylformamide–acetonitrile (1:2v/v9 ml) were mixed in a 25 ml flask. TMSCl (10 mmol) was then added dropwise at room

temperature. The resulting reaction mixture was stirred at 353 K for 3 h, cooled to room temperature and precipitation was observed. The precipitate was isolated by filtering through a Buchner funnel, washed with ethanol and dried to give the crystalline powder. The powder was further purified by recrystallization from C2H5OH. The

crystalline product was dissolved in a DMF solution and single crystals suitable for X-ray structure analysis were obtained by slow evaporation of the solution at room temperature.

Crystal data

C17H22O3 Mr= 274.35

Orthorhombic,Cmc2₁ a= 15.121 (4) A˚ b= 8.872 (2) A˚ c= 11.025 (3) A˚ V= 1479.0 (7) A˚3 Z= 4

Dx= 1.232 Mg m 3

MoKradiation Cell parameters from 40

reflections = 4.6–15.0

= 0.08 mm1 T= 298 (2) K Block, colorless 0.500.260.26 mm

Data collection

SiemensP4 diffractometer !scans

Absorption correction: none 1011 measured reflections 955 independent reflections 638 reflections withI> 2(I) Rint= 0.010

max= 27.8

h= 0!19 k= 0!11 l=14!1 3 standard reflections

every 97 reflections intensity decay: 3.2%

Refinement

Refinement onF2 R[F2> 2(F2)] = 0.039 wR(F2_{) = 0.089} S= 0.88 955 reflections 100 parameters

H-atom parameters constrained w= 1/[2

(Fo2) + (0.0465P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.15 e A˚3

min=0.12 e A˚3

H atoms were placed in calculated positions, with C—H = 0.96– 0.98 A˚ , and refined in riding-model approximation with Uiso(H) values set equal to 1.2Ueq(carrier atom). In the absence of significant

anomalous dispersion effects, Friedel pairs were merged.

Data collection: XSCANS (Siemens, 1991); cell refinement:

XSCANS; data reduction: SHELXTL/PC (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:SHELXTL/PC; software used to prepare mate-rial for publication:SHELXTL/PC.

This research was funded by NSFC of China (No. 20375036).

References

Hellmann, H. & Schroeder, M. (1962).Gerany Ann.656, 85–89.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Siemens (1991).XSCANS.Version 2.10b. Siemens Analytical X-ray Instru-ments Inc., Madison, Wisconsin, USA.

Siemens (1994). SHELXTL/PC. Version 4.2. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13. Figure 1

View of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Unlabeled atoms are related by the symmetry code (1x, y, z).

Figure 2

supporting information

sup-1 Acta Cryst. (2005). E61, o1139–o1140

supporting information

Acta Cryst. (2005). E61, o1139–o1140 [https://doi.org/10.1107/S1600536805006501]

9-Butyl-3,4,5,6,7,9-hexahydro-2

H

-xanthene-1,8-dione

Yu-Lin Zhu, Shen-Lin Huang and Yuan-Jiang Pan

9-Butyl-3,4,5,6,7,9-hexahydro-2H-xanthene-1,8-dione

Crystal data

C17H22O3

Mr = 274.35

Orthorhombic, Cmc21

Hall symbol: C 2c -2

a = 15.121 (4) Å

b = 8.872 (2) Å

c = 11.025 (3) Å

V = 1479.0 (7) Å3

Z = 4

F(000) = 592

Dx = 1.232 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 40 reflections

θ = 4.6–15.0°

µ = 0.08 mm−1

T = 298 K Block, colorless 0.50 × 0.26 × 0.26 mm

Data collection

Siemens P4 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

1011 measured reflections 955 independent reflections 638 reflections with I > 2σ(I)

Rint = 0.010

θmax = 27.8°, θmin = 2.7°

h = 0→19

k = 0→11

l = −14→1

3 standard reflections every 97 reflections intensity decay: 3.2%

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.039}

wR(F2_{) = 0.089}

S = 0.88 955 reflections 100 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0465P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.15 e Å−3

Δρmin = −0.12 e Å−3

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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 Uiso*/Ueq Occ. (<1)

O1 0.5000 0.7222 (3) 0.3745 (2) 0.0439 (7) O2 0.33006 (12) 0.5093 (3) 0.0610 (2) 0.0674 (6) C1 0.42210 (15) 0.6886 (3) 0.3153 (2) 0.0367 (6) C2 0.34659 (17) 0.7700 (3) 0.3713 (3) 0.0479 (7) H2A 0.3484 0.8752 0.3473 0.058* H2B 0.3516 0.7654 0.4589 0.058* C3 0.25933 (19) 0.7014 (4) 0.3323 (3) 0.0598 (9) H3A 0.2500 0.6076 0.3757 0.072* H3B 0.2115 0.7695 0.3533 0.072* C4 0.2575 (2) 0.6716 (3) 0.1984 (3) 0.0581 (8) H4A 0.2551 0.7672 0.1559 0.070* H4B 0.2040 0.6164 0.1790 0.070* C5 0.33572 (18) 0.5839 (3) 0.1528 (3) 0.0447 (7) C6 0.41886 (15) 0.5978 (2) 0.2187 (2) 0.0355 (6) C7 0.5000 0.5174 (4) 0.1727 (3) 0.0390 (9) H7 0.5000 0.5256 0.0840 0.047* C8 0.5000 0.3482 (4) 0.2047 (4) 0.0439 (9)

H8A 0.4483 0.3022 0.1681 0.053* 0.50 H8B 0.5517 0.3022 0.1681 0.053* 0.50 C9 0.5000 0.3111 (4) 0.3377 (3) 0.0414 (9)

H9A 0.4482 0.3561 0.3749 0.050* 0.50 H9B 0.5518 0.3561 0.3749 0.050* 0.50 C10 0.5000 0.1437 (4) 0.3638 (4) 0.0526 (11)

H10A 0.4482 0.0990 0.3262 0.063* 0.50 H10B 0.5518 0.0990 0.3262 0.063* 0.50 C11 0.5000 0.1040 (5) 0.4965 (4) 0.0817 (16)

H11A 0.5000 −0.0037 0.5054 0.123*

H11B 0.4482 0.1451 0.5343 0.123* 0.50 H11C 0.5518 0.1451 0.5343 0.123* 0.50

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

sup-3 Acta Cryst. (2005). E61, o1139–o1140

C6 0.0367 (13) 0.0325 (12) 0.0372 (13) −0.0023 (10) −0.0017 (11) 0.0023 (12) C7 0.0452 (19) 0.0371 (19) 0.035 (2) 0.000 0.000 −0.0053 (17) C8 0.045 (2) 0.0375 (19) 0.049 (2) 0.000 0.000 −0.0094 (19) C9 0.043 (2) 0.0325 (18) 0.048 (2) 0.000 0.000 0.0001 (17) C10 0.058 (2) 0.0355 (19) 0.065 (3) 0.000 0.000 −0.001 (2) C11 0.130 (5) 0.047 (3) 0.067 (3) 0.000 0.000 0.013 (3)

Geometric parameters (Å, º)

O1—C1 1.379 (3) C7—C6i _{1.508 (3)}

O1—C1i _{1.379 (3) C7—C8 1.542 (5)}

O2—C5 1.213 (4) C7—H7 0.9800

C1—C6 1.336 (3) C8—C9 1.502 (5)

C1—C2 1.485 (3) C8—H8A 0.9700

C2—C3 1.515 (4) C8—H8B 0.9700

C2—H2A 0.9700 C9—C10 1.513 (5)

C2—H2B 0.9700 C9—H9A 0.9700

C3—C4 1.500 (5) C9—H9B 0.9700

C3—H3A 0.9700 C10—C11 1.504 (6)

C3—H3B 0.9700 C10—H10A 0.9700

C4—C5 1.502 (4) C10—H10B 0.9700

C4—H4A 0.9700 C11—H11A 0.9600

C4—H4B 0.9700 C11—H11B 0.9600

C5—C6 1.458 (4) C11—H11C 0.9600

C6—C7 1.508 (3)

C1—O1—C1i _{117.3 (3) C6}i_{—C7—C8 112.6 (2)}

C6—C1—O1 122.6 (2) C6—C7—C8 112.6 (2) C6—C1—C2 126.6 (2) C6i_{—C7—H7 107.5}

O1—C1—C2 110.8 (2) C6—C7—H7 107.5

C1—C2—C3 110.9 (2) C8—C7—H7 107.5

C1—C2—H2A 109.5 C9—C8—C7 115.9 (3)

C3—C2—H2A 109.5 C9—C8—H8A 108.3

C1—C2—H2B 109.5 C7—C8—H8A 108.3

C3—C2—H2B 109.5 C9—C8—H8B 108.3

H2A—C2—H2B 108.0 C7—C8—H8B 108.3

C4—C3—C2 111.4 (3) H8A—C8—H8B 107.4 C4—C3—H3A 109.3 C8—C9—C10 113.6 (3)

C2—C3—H3A 109.3 C8—C9—H9A 108.8

C4—C3—H3B 109.3 C10—C9—H9A 108.8

C2—C3—H3B 109.3 C8—C9—H9B 108.8

H3A—C3—H3B 108.0 C10—C9—H9B 108.8

C3—C4—C5 114.0 (3) H9A—C9—H9B 107.7 C3—C4—H4A 108.8 C11—C10—C9 114.5 (4) C5—C4—H4A 108.8 C11—C10—H10A 108.6

C3—C4—H4B 108.8 C9—C10—H10A 108.6

O2—C5—C6 121.6 (3) H10A—C10—H10B 107.6 O2—C5—C4 120.5 (3) C10—C11—H11A 109.5 C6—C5—C4 117.9 (3) C10—C11—H11B 109.5 C1—C6—C5 118.7 (2) H11A—C11—H11B 109.5 C1—C6—C7 121.6 (2) C10—C11—H11C 109.5 C5—C6—C7 119.6 (2) H11A—C11—H11C 109.5 C6i_{—C7—C6 108.9 (3) H11B—C11—H11C 109.5}

C1i_{—O1—C1—C6 15.0 (4) O2—C5—C6—C1 176.2 (2)}

C1i_{—O1—C1—C2 −163.21 (18) C4—C5—C6—C1 −0.8 (4)}

C6—C1—C2—C3 18.3 (4) O2—C5—C6—C7 −0.2 (4) O1—C1—C2—C3 −163.6 (2) C4—C5—C6—C7 −177.2 (2) C1—C2—C3—C4 −45.4 (3) C1—C6—C7—C6i _{−20.6 (4)}

C2—C3—C4—C5 51.3 (3) C5—C6—C7—C6i _{155.73 (19)}

C3—C4—C5—O2 154.9 (3) C1—C6—C7—C8 104.9 (3) C3—C4—C5—C6 −28.1 (4) C5—C6—C7—C8 −78.7 (3) O1—C1—C6—C5 −172.3 (2) C6i_{—C7—C8—C9 61.8 (2)}

C2—C1—C6—C5 5.6 (4) C6—C7—C8—C9 −61.8 (2) O1—C1—C6—C7 4.1 (4) C7—C8—C9—C10 180.0 C2—C1—C6—C7 −178.0 (3) C8—C9—C10—C11 180.0