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organic papers

o1504

Huang, Zhu and Pan C15H17ClO DOI: 10.1107/S1600536804017994 Acta Cryst.(2004). E60, o1504±o1506 Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

(

E

)-2-(4-Chlorobenzylidene)cyclooctanone

Shen-Lin Huang,aYu-Lin Zhu,a Yuan-Jiang Pana* and Hai-Tong Wanb

aDepartment of Chemistry, Zhejiang University,

Hangzhou 310027, People's Republic of China, andbZhejiang College of Traditional Chinese Medicine, Hangzhou 310053, People's Republic of China

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

Key indicators

Single-crystal X-ray study T= 288 K

Mean(C±C) = 0.003 AÊ Rfactor = 0.036 wRfactor = 0.079

Data-to-parameter ratio = 20.1

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

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title compound, C15H17ClO, was synthesized directly from

the condensation of cyclooctanone with 4-chlorobenz-aldehyde, catalysed effectively by improved nanostructured Ni±B cluster in the presence of trimethylsilyl chloride (TMSCl). The eight-membered ring adopts a boat±chair conformation. The packing of the molecules in the crystal structure is determined mainly by CÐH O hydrogen bonds, together with CÐH interactions and weak±stacking interactions.

Comment

The aldol condensation reaction, which is performed in the presence of strong acids or bases, is one of the most useful reactions in organic chemistry. Ni±B/TMSCl is used as a catalytic system for the aldol condensation reaction, and the title compound, (I), was obtained in excellent yield. The structure of (E)-2-(2-¯uorobenzylidene)cyclooctanone, (II), has already been reported (Huanget al., 2004). We report here the structure of analog (I).

Fig. 1 shows the molecular structure of (I), which crystal-lizes in the space groupP21. The eight-membered ring adopts

a boat±chair conformation. In general, cyclooctanone can adopt two conformations,viz. crown or boat±chair (Allinger & Greenberg, 1959). The boat±chair conformation is favourable

Received 29 June 2004 Accepted 22 July 2004 Online 7 August 2004

Figure 1

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for the cyclooctanone ring of (I), in view of the chloro-benzylidene substituent.

There are no unusual bond lengths and angles in (I), and the geometry is in good agreement with that found in (II). The C1ÐC8ÐC9ÐC10 torsion angle of 179.84 (19) con®rms the

Econ®guration of the molecule with respect to the C8 C9 bond. The OÐC1ÐC8ÐC9 torsion angle of 29.4 (3),

together with normal C1 O and C8 C9 bond lengths (Table 1) indicate the absence of conjugation between these two double bonds. Also, the C8ÐC9ÐC10ÐC11 torsion angle of 42.4 (3), and the dihedral angle between the C8 C9ÐC10

plane and the benzene ring of 42.5 (1)show that the C8 C9

bond does not conjugate with the benzene ring.

In the ¯uoro analog, (II), benzene ring atoms C11 and C14 are hydrogen bonded to the O atom of symmetry-related molecules at (1ÿx, 1ÿy, zÿ1

2) and (x+12, 32ÿy, z),

respectively. In addition, atom C4 is involved in two separate CÐH interactions with the benzene ring of symmetry-related molecules at (1

2ÿx,32+y,12+z) and (x, 1 +y,z).

The supramolecular structure of (I), however, is completely different. A network of intermolecular CÐH O and CÐ H...interactions is present (Table 2). In addition, there is a comparatively weak±interaction between the benzene ring and a symmetry-related ring at (1ÿx,yÿ1

2, 2ÿz), with their

centroids separated by 5.530 (9) AÊ and a dihedral angle between the two planes of 85.0 (2)%.

Finally, it is worth mentioning that there is a large difference between the melting points of (I) and (II),viz. 362±364 and 465±466 K, respectively.

Experimental

A solution of cyclooctanone (1.0 mmol), 4-chlorobenzaldehyde (1.0 mmol) and TMSCl (1.1 mmol) in dimethylformamide (DMF, 1 ml) with 2 mol% of improved nanostructured Ni±B cluster was heated at 348 K for 5 h. A crystalline product precipitated directly when the whole reaction mixture was placed in a refrigerator over-night. This was isolated by ®ltration, washed with ethanol, and dried (yield 85%). The crystalline product was dissolved in a DMF/ methanol solution. Single crystals (m.p. 362±364 K) suitable for X-ray structure analysis were obtained by slow evaporation of the solution at room temperature.

Crystal data

C15H17ClO

Mr= 248.74 Monoclinic,P21

a= 7.474 (1) AÊ b= 10.545 (1) AÊ c= 8.568 (1) AÊ

= 100.223 (9)

V= 664.6 (1) AÊ3

Z= 2

Dx= 1.243 Mg mÿ3 MoKradiation Cell parameters from 34

re¯ections

= 2.8±15.2

= 0.27 mmÿ1

T= 288 (2) K Block, colorless 0.480.400.38 mm

Data collection

SiemensP4 diffractometer

!scans

Absorption correction: multi-scan (SHELXTL; Siemens, 1991) Tmin= 0.858,Tmax= 0.898

3675 measured re¯ections 3115 independent re¯ections 2310 re¯ections withI> 2(I)

Rint= 0.016 max= 27.7

h=ÿ9!9 k=ÿ13!13 l=ÿ11!11 3 standard re¯ections

every 97 re¯ections intensity decay: 3.5%

Re®nement

Re®nement onF2

R[F2> 2(F2)] = 0.036

wR(F2) = 0.079

S= 0.96 3115 re¯ections 155 parameters

H-atom parameters constrained w= 1/[2(F

o2) + (0.0378P)2] whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001 max= 0.14 e AÊÿ3 min=ÿ0.11 e AÊÿ3

Extinction correction:SHELXL Extinction coef®cient: 0.056 (4) Absolute structure: (Flack, 1983);

1473 Friedel pairs Flack parameter =ÿ0.01 (6)

Table 1

Selected geometric parameters (AÊ,).

ClÐC13 1.7489 (18) OÐC1 1.214 (2) C1ÐC8 1.494 (3)

C8ÐC9 1.339 (2) C9ÐC10 1.474 (2)

OÐC1ÐC8 121.19 (18) OÐC1ÐC2 118.48 (18)

C8ÐC1ÐC2ÐC3 ÿ100.7 (2) C1ÐC2ÐC3ÐC4 71.2 (3) C2ÐC3ÐC4ÐC5 ÿ62.5 (3) C3ÐC4ÐC5ÐC6 102.7 (3)

C4ÐC5ÐC6ÐC7 ÿ60.5 (3) C5ÐC6ÐC7ÐC8 ÿ49.9 (3) C2ÐC1ÐC8ÐC7 26.5 (3) C6ÐC7ÐC8ÐC1 73.9 (2)

Table 2

Hydrogen-bonding geometry (AÊ,).

DÐH A DÐH H A D A DÐH A

C14ÐH14 Oi 0.93 2.43 3.314 (3) 159

C4ÐH4B Cgii 0.97 2.87 3.806 (8) 164

C5ÐH5A Cgiii 0.97 3.27 4.065 (0) 141 Symmetry codes: (i) 2ÿx;1

2‡y;2ÿz; (ii)x;y;zÿ1; (iii) 1ÿx;yÿ12;1ÿz.Cgis the centroid of the benzene ring.

organic papers

Acta Cryst.(2004). E60, o1504±o1506 Huang, Zhu and Pan C15H17ClO

o1505

Figure 2

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H atoms were placed in calculated positions, with CÐH = 0.93 or 0.97 AÊ, and re®ned as riding atoms, with Uiso(H) = 1.2Ueq(carrier

atom).

Data collection: XSCANS (Siemens, 1994); cell re®nement:

XSCANS; data reduction: SHELXTL/PC (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:SHELXTL/PC; software used to prepare mate-rial for publication:SHELXTL/PC.

This work was supported by the NSFC of China (20375036) and Zhejiang Provincial Natural Science Foundation (Rc0042).

References

Allinger, N. L. & Greenberg, S. (1959).J. Am. Chem. Soc.81, 5733±5736. Flack, H. D. (1983).Acta Cryst.A39, 876±881.

Huang, S., Zhu, Y. & Pan, Y. (2004).Acta Cryst.E60, o1000±o1002. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

GoÈttingen, Germany.

Siemens (1991). SHELXTL/PC. Version 5.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Siemens (1994).XSCANS.Version 2.10b. Siemens Analytical X-ray Instru-ments Inc., Madison, Wisconsin, USA.

organic papers

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supporting information

sup-1 Acta Cryst. (2004). E60, o1504–o1506

supporting information

Acta Cryst. (2004). E60, o1504–o1506 [https://doi.org/10.1107/S1600536804017994]

(

E

)-2-(4-Chlorobenzylidene)cyclooctanone

Shen-Lin Huang, Yu-Lin Zhu, Yuan-Jiang Pan and Hai-Tong Wan

(E)-2-(4-Chlorobenzylidene)cyclooctanone

Crystal data

C15H17ClO

Mr = 248.74

Monoclinic, P21 Hall symbol: P 2yb

a = 7.474 (1) Å

b = 10.545 (1) Å

c = 8.568 (1) Å

β = 100.223 (9)°

V = 664.6 (1) Å3

Z = 2

F(000) = 264

Dx = 1.243 Mg m−3

Melting point = 362–364 K Mo radiation, λ = 0.71073 Å Cell parameters from 34 reflections

θ = 2.8–15.2°

µ = 0.27 mm−1

T = 288 K Block, colorless 0.48 × 0.40 × 0.38 mm

Data collection

Siemens P4 diffractometer

Radiation source: normal-focus sealed tube Graphite monochromator

ω scans

Absorption correction: multi-scan (SHELXTL; Siemens, 1991)

Tmin = 0.858, Tmax = 0.898 3675 measured reflections

3115 independent reflections 2310 reflections with I > 2σ(I)

Rint = 0.016

θmax = 27.7°, θmin = 2.4°

h = −9→9

k = −13→13

l = −11→11

3 standard reflections every 97 reflections intensity decay: 3.5%

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 > 2σ(F2)] = 0.036

wR(F2) = 0.079

S = 0.96 3115 reflections 155 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) + (0.0378P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001

Δρmax = 0.14 e Å−3 Δρmin = −0.11 e Å−3

Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 Extinction coefficient: 0.056 (4)

Absolute structure: 1473 Friedel pairs (Flack, 1983)

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supporting information

sup-2 Acta Cryst. (2004). E60, o1504–o1506

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 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)

x y z Uiso*/Ueq

Cl 0.31690 (7) 0.65545 (6) 1.17777 (6) 0.06703 (19)

O 1.14291 (19) 0.38191 (16) 0.66331 (17) 0.0743 (5)

C1 1.0234 (3) 0.4371 (2) 0.5745 (2) 0.0502 (5)

C2 1.0529 (3) 0.4676 (2) 0.4086 (2) 0.0567 (5)

H2A 0.9735 0.5370 0.3669 0.068*

H2B 1.1774 0.4956 0.4133 0.068*

C3 1.0170 (3) 0.3563 (3) 0.2968 (3) 0.0674 (6)

H3A 1.0842 0.2839 0.3466 0.081*

H3B 1.0654 0.3762 0.2018 0.081*

C4 0.8190 (3) 0.3175 (2) 0.2473 (3) 0.0703 (7)

H4A 0.8127 0.2499 0.1697 0.084*

H4B 0.7520 0.3891 0.1953 0.084*

C5 0.7242 (3) 0.2727 (2) 0.3813 (3) 0.0724 (7)

H5A 0.6553 0.1968 0.3462 0.087*

H5B 0.8167 0.2492 0.4709 0.087*

C6 0.5963 (3) 0.3678 (3) 0.4385 (2) 0.0655 (6)

H6A 0.5410 0.3274 0.5199 0.079*

H6B 0.4996 0.3874 0.3505 0.079*

C7 0.6829 (3) 0.4929 (2) 0.5055 (2) 0.0536 (5)

H7A 0.7123 0.5432 0.4187 0.064*

H7B 0.5943 0.5400 0.5525 0.064*

C8 0.8519 (2) 0.47659 (18) 0.6278 (2) 0.0426 (4)

C9 0.8657 (2) 0.50057 (19) 0.7830 (2) 0.0472 (5)

H9 0.9815 0.4899 0.8425 0.057*

C10 0.7261 (2) 0.54116 (17) 0.87409 (19) 0.0416 (4)

C11 0.5519 (2) 0.4895 (2) 0.8489 (2) 0.0465 (4)

H11 0.5190 0.4308 0.7679 0.056*

C12 0.4270 (3) 0.52420 (19) 0.9427 (2) 0.0486 (5)

H12 0.3115 0.4883 0.9262 0.058*

C13 0.4759 (3) 0.61224 (18) 1.0603 (2) 0.0455 (5)

C14 0.6459 (3) 0.6660 (2) 1.0892 (2) 0.0500 (4)

H14 0.6767 0.7259 1.1692 0.060*

C15 0.7705 (2) 0.62858 (18) 0.9957 (2) 0.0483 (5)

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sup-3 Acta Cryst. (2004). E60, o1504–o1506

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

Cl 0.0666 (3) 0.0807 (4) 0.0601 (3) 0.0020 (3) 0.0284 (2) −0.0054 (3)

O 0.0540 (8) 0.1060 (14) 0.0584 (9) 0.0241 (9) −0.0023 (7) −0.0089 (9)

C1 0.0475 (11) 0.0552 (12) 0.0460 (10) −0.0015 (10) 0.0030 (9) −0.0089 (9)

C2 0.0540 (11) 0.0627 (14) 0.0575 (12) −0.0080 (10) 0.0213 (9) −0.0051 (11)

C3 0.0759 (15) 0.0748 (15) 0.0552 (13) 0.0030 (13) 0.0217 (11) −0.0133 (12)

C4 0.0839 (16) 0.0735 (16) 0.0529 (12) −0.0070 (13) 0.0109 (11) −0.0173 (12) C5 0.0849 (17) 0.0661 (15) 0.0643 (13) −0.0249 (14) 0.0083 (12) −0.0109 (12)

C6 0.0503 (11) 0.0957 (18) 0.0480 (11) −0.0117 (12) 0.0016 (9) −0.0041 (12)

C7 0.0493 (11) 0.0683 (14) 0.0427 (10) 0.0102 (11) 0.0065 (9) 0.0089 (10)

C8 0.0413 (9) 0.0433 (11) 0.0427 (10) −0.0009 (9) 0.0055 (8) 0.0023 (8)

C9 0.0386 (9) 0.0555 (12) 0.0451 (10) 0.0001 (9) 0.0014 (8) −0.0006 (9)

C10 0.0423 (10) 0.0454 (11) 0.0355 (9) 0.0001 (9) 0.0027 (8) 0.0035 (8)

C11 0.0464 (10) 0.0513 (11) 0.0399 (9) −0.0032 (9) 0.0027 (8) −0.0057 (9)

C12 0.0437 (10) 0.0529 (12) 0.0479 (10) −0.0037 (9) 0.0051 (8) −0.0007 (10)

C13 0.0479 (10) 0.0505 (12) 0.0390 (9) 0.0063 (9) 0.0105 (8) 0.0064 (8)

C14 0.0591 (11) 0.0477 (11) 0.0420 (9) −0.0035 (11) 0.0061 (8) −0.0047 (10)

C15 0.0429 (10) 0.0563 (14) 0.0445 (9) −0.0101 (9) 0.0041 (8) 0.0007 (9)

Geometric parameters (Å, º)

Cl—C13 1.7489 (18) C6—H6B 0.9700

O—C1 1.214 (2) C7—C8 1.501 (2)

C1—C8 1.494 (3) C7—H7A 0.9700

C1—C2 1.512 (3) C7—H7B 0.9700

C2—C3 1.508 (3) C8—C9 1.339 (2)

C2—H2A 0.9700 C9—C10 1.474 (2)

C2—H2B 0.9700 C9—H9 0.9300

C3—C4 1.522 (3) C10—C15 1.387 (2)

C3—H3A 0.9700 C10—C11 1.392 (3)

C3—H3B 0.9700 C11—C12 1.385 (3)

C4—C5 1.527 (3) C11—H11 0.9300

C4—H4A 0.9700 C12—C13 1.371 (3)

C4—H4B 0.9700 C12—H12 0.9300

C5—C6 1.525 (3) C13—C14 1.373 (3)

C5—H5A 0.9700 C14—C15 1.389 (2)

C5—H5B 0.9700 C14—H14 0.9300

C6—C7 1.536 (3) C15—H15 0.9300

C6—H6A 0.9700

O—C1—C8 121.19 (18) H6A—C6—H6B 107.4

O—C1—C2 118.48 (18) C8—C7—C6 114.15 (18)

C8—C1—C2 120.32 (17) C8—C7—H7A 108.7

C3—C2—C1 113.11 (18) C6—C7—H7A 108.7

C3—C2—H2A 109.0 C8—C7—H7B 108.7

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sup-4 Acta Cryst. (2004). E60, o1504–o1506

C3—C2—H2B 109.0 H7A—C7—H7B 107.6

C1—C2—H2B 109.0 C9—C8—C1 115.92 (15)

H2A—C2—H2B 107.8 C9—C8—C7 125.33 (17)

C2—C3—C4 116.18 (18) C1—C8—C7 118.67 (16)

C2—C3—H3A 108.2 C8—C9—C10 130.09 (16)

C4—C3—H3A 108.2 C8—C9—H9 115.0

C2—C3—H3B 108.2 C10—C9—H9 115.0

C4—C3—H3B 108.2 C15—C10—C11 118.01 (16)

H3A—C3—H3B 107.4 C15—C10—C9 119.56 (16)

C3—C4—C5 115.57 (18) C11—C10—C9 122.33 (17)

C3—C4—H4A 108.4 C12—C11—C10 120.97 (18)

C5—C4—H4A 108.4 C12—C11—H11 119.5

C3—C4—H4B 108.4 C10—C11—H11 119.5

C5—C4—H4B 108.4 C13—C12—C11 119.06 (18)

H4A—C4—H4B 107.4 C13—C12—H12 120.5

C6—C5—C4 116.1 (2) C11—C12—H12 120.5

C6—C5—H5A 108.3 C12—C13—C14 122.02 (18)

C4—C5—H5A 108.3 C12—C13—Cl 118.64 (16)

C6—C5—H5B 108.3 C14—C13—Cl 119.34 (15)

C4—C5—H5B 108.3 C13—C14—C15 118.17 (18)

H5A—C5—H5B 107.4 C13—C14—H14 120.9

C5—C6—C7 116.01 (16) C15—C14—H14 120.9

C5—C6—H6A 108.3 C10—C15—C14 121.75 (17)

C7—C6—H6A 108.3 C10—C15—H15 119.1

C5—C6—H6B 108.3 C14—C15—H15 119.1

C7—C6—H6B 108.3

O—C1—C2—C3 80.4 (2) C7—C8—C9—C10 3.2 (3)

C8—C1—C2—C3 −100.7 (2) C8—C9—C10—C15 −141.3 (2)

C1—C2—C3—C4 71.2 (3) C8—C9—C10—C11 42.4 (3)

C2—C3—C4—C5 −62.5 (3) C15—C10—C11—C12 −0.1 (3)

C3—C4—C5—C6 102.7 (3) C9—C10—C11—C12 176.17 (17)

C4—C5—C6—C7 −60.5 (3) C10—C11—C12—C13 1.0 (3)

C5—C6—C7—C8 −49.9 (3) C11—C12—C13—C14 −0.8 (3)

O—C1—C8—C9 28.5 (3) C11—C12—C13—Cl 179.92 (15)

C2—C1—C8—C9 −150.33 (18) C12—C13—C14—C15 −0.2 (3)

O—C1—C8—C7 −154.6 (2) Cl—C13—C14—C15 179.03 (14)

C2—C1—C8—C7 26.5 (3) C11—C10—C15—C14 −1.0 (3)

C6—C7—C8—C9 −109.6 (2) C9—C10—C15—C14 −177.36 (18)

C6—C7—C8—C1 73.9 (2) C13—C14—C15—C10 1.1 (3)

C1—C8—C9—C10 179.84 (19)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

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sup-5 Acta Cryst. (2004). E60, o1504–o1506

C4—H4B···Cgii 0.97 2.87 3.806 (8) 164

C5—H5A···Cgiii 0.97 3.27 4.065 (1) 141

References

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