organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Ethyl (Z)-2-(4-chloro­benzyl­­idene)-3-oxo­butano­ate

aSchool of Biology, Chemistry and Material Science, Manchester Metropolitan University, Manchester, England, bDepartment of Organic Chemistry, Baku State University, Baku, Azerbaijan, and cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 6 January 2011; accepted 6 January 2011; online 12 January 2011)

The C=C double-bond in the title compound, C13H13ClO3, has a Z configuration. The aliphatic substituents at one end of the double bond, i.e. the CH3CO– and C2H5O2C– groups, are aligned at 82.1 (3)° with respect to each other.

Related literature

For related structures, see: Deng et al. (2007[Deng, P.-F., Chen, G.-B., Feng, Y.-Q. & Song, J. (2007). Acta Cryst. E63, o3532.]); Shi (2008[Shi, X. (2008). Acta Cryst. E64, o2462.]).

[Scheme 1]

Experimental

Crystal data
  • C13H13ClO3

  • Mr = 252.68

  • Monoclinic, P 21 /n

  • a = 9.9956 (6) Å

  • b = 7.7487 (5) Å

  • c = 16.2709 (10) Å

  • β = 99.624 (1)°

  • V = 1242.49 (13) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.30 mm−1

  • T = 295 K

  • 0.20 × 0.20 × 0.20 mm

Data collection
  • Bruker APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.942, Tmax = 0.942

  • 11255 measured reflections

  • 2790 independent reflections

  • 1968 reflections with I > 2σ(I)

  • Rint = 0.069

Refinement
  • R[F2 > 2σ(F2)] = 0.065

  • wR(F2) = 0.201

  • S = 1.02

  • 2790 reflections

  • 156 parameters

  • H-atom parameters constrained

  • Δρmax = 0.40 e Å−3

  • Δρmin = −0.52 e Å−3

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Trizma is a mildly-basic primary aminoalcohol that catalyzes Knoevenagel condensation reactions. The yield can be high under microwave irradiation; the title compound has been synthesized albeit by a conventional route. The carbon-carbon double-bond in C13H13ClO3 has a Z-configuration. The aliphatic substituents at one end of the double-bond, i.e., the CH3CO– and planar C2H5O2C– groups, are aligned at 82.1 (3) ° with respect to each other. Bond dimensions in the molecule compare favorably with those found in similar molecules (Deng et al., 2007; Shi, 2008).

Related literature top

For related structures, see: Deng et al. (2007); Shi (2008).

Experimental top

Trizma (0.01 mol), p-chlorobenzaldehyde (0.01 mol) and ethyl acetoacetate (0.02 mol) were heated in ethanol (50 ml) for 3 h. The reaction was monitored with TLC. The solid that separated was collected and recrystallized from ethanol to give a colorless crystals, m.p. 373 K (60% yield).

Refinement top

Carbon-bound H-atoms were placed in calculated positions [C–H 0.93 to 0.97 Å; U(H) 1.2 to 1.5U(C)] and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C13H13ClO3 at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
Ethyl (Z)-2-(4-chlorobenzylidene)-3-oxobutanoate top
Crystal data top
C13H13ClO3F(000) = 528
Mr = 252.68Dx = 1.351 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3560 reflections
a = 9.9956 (6) Åθ = 2.2–27.8°
b = 7.7487 (5) ŵ = 0.30 mm1
c = 16.2709 (10) ÅT = 295 K
β = 99.624 (1)°Prism, colorless
V = 1242.49 (13) Å30.20 × 0.20 × 0.20 mm
Z = 4
Data collection top
Bruker APEXII
diffractometer
2790 independent reflections
Radiation source: fine-focus sealed tube1968 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.069
ϕ and ω scansθmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1212
Tmin = 0.942, Tmax = 0.942k = 109
11255 measured reflectionsl = 2121
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.201H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.1314P)2]
where P = (Fo2 + 2Fc2)/3
2790 reflections(Δ/σ)max = 0.001
156 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.52 e Å3
Crystal data top
C13H13ClO3V = 1242.49 (13) Å3
Mr = 252.68Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.9956 (6) ŵ = 0.30 mm1
b = 7.7487 (5) ÅT = 295 K
c = 16.2709 (10) Å0.20 × 0.20 × 0.20 mm
β = 99.624 (1)°
Data collection top
Bruker APEXII
diffractometer
2790 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1968 reflections with I > 2σ(I)
Tmin = 0.942, Tmax = 0.942Rint = 0.069
11255 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0650 restraints
wR(F2) = 0.201H-atom parameters constrained
S = 1.02Δρmax = 0.40 e Å3
2790 reflectionsΔρmin = 0.52 e Å3
156 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.17886 (7)0.43778 (11)0.15024 (4)0.0663 (3)
O10.2270 (2)0.3753 (3)0.72305 (11)0.0703 (6)
O20.42363 (15)0.4336 (2)0.59728 (11)0.0555 (5)
O30.27248 (13)0.6486 (2)0.56982 (10)0.0452 (4)
C10.13562 (19)0.3488 (3)0.41918 (13)0.0399 (5)
C20.2540 (2)0.4199 (3)0.39776 (14)0.0453 (6)
H2A0.32520.44970.43970.054*
C30.2669 (2)0.4463 (3)0.31626 (14)0.0467 (6)
H30.34600.49400.30310.056*
C40.1611 (2)0.4015 (3)0.25368 (14)0.0437 (5)
C50.0440 (2)0.3274 (3)0.27150 (14)0.0490 (6)
H50.02580.29570.22900.059*
C60.03270 (19)0.3015 (3)0.35374 (14)0.0453 (5)
H60.04580.25090.36620.054*
C70.11396 (19)0.3175 (3)0.50496 (14)0.0418 (5)
H70.03870.25010.50980.050*
C80.18613 (19)0.3714 (3)0.57758 (13)0.0405 (5)
C90.1549 (2)0.3219 (3)0.66085 (15)0.0501 (6)
C100.0339 (3)0.2111 (4)0.66738 (18)0.0693 (8)
H10A0.03330.18320.72480.104*
H10B0.03850.10680.63620.104*
H10C0.04760.27270.64530.104*
C110.3088 (2)0.4853 (3)0.58325 (13)0.0395 (5)
C120.3811 (2)0.7742 (3)0.57098 (17)0.0535 (6)
H12A0.42750.75630.52390.064*
H12B0.44660.76340.62190.064*
C130.3162 (3)0.9486 (3)0.56615 (18)0.0592 (7)
H13A0.38361.03530.56260.089*
H13B0.27640.96790.61510.089*
H13C0.24700.95460.51760.089*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0540 (4)0.0967 (7)0.0483 (4)0.0031 (3)0.0085 (3)0.0024 (3)
O10.0600 (11)0.0996 (17)0.0513 (11)0.0032 (11)0.0095 (9)0.0006 (10)
O20.0281 (8)0.0621 (12)0.0735 (12)0.0041 (7)0.0001 (7)0.0076 (8)
O30.0282 (7)0.0479 (10)0.0601 (9)0.0011 (6)0.0091 (6)0.0004 (7)
C10.0237 (8)0.0445 (12)0.0514 (12)0.0006 (8)0.0061 (8)0.0051 (9)
C20.0235 (9)0.0614 (15)0.0504 (12)0.0061 (9)0.0049 (8)0.0091 (10)
C30.0280 (10)0.0594 (15)0.0533 (13)0.0052 (9)0.0086 (9)0.0040 (10)
C40.0335 (10)0.0524 (13)0.0446 (11)0.0046 (9)0.0050 (8)0.0025 (10)
C50.0295 (10)0.0605 (14)0.0540 (13)0.0031 (10)0.0013 (9)0.0107 (11)
C60.0237 (9)0.0528 (13)0.0590 (13)0.0075 (9)0.0060 (8)0.0092 (10)
C70.0246 (9)0.0464 (12)0.0555 (12)0.0016 (8)0.0099 (8)0.0030 (10)
C80.0280 (9)0.0422 (12)0.0522 (12)0.0038 (9)0.0092 (8)0.0033 (9)
C90.0405 (11)0.0575 (15)0.0545 (13)0.0068 (10)0.0147 (10)0.0040 (11)
C100.0592 (16)0.080 (2)0.0759 (18)0.0097 (14)0.0314 (14)0.0065 (15)
C110.0284 (9)0.0499 (13)0.0400 (10)0.0034 (9)0.0046 (8)0.0021 (9)
C120.0379 (11)0.0576 (16)0.0653 (14)0.0090 (10)0.0092 (10)0.0009 (12)
C130.0581 (16)0.0522 (15)0.0686 (17)0.0050 (12)0.0140 (13)0.0020 (12)
Geometric parameters (Å, º) top
Cl1—C41.745 (2)C6—H60.9300
O1—C91.213 (3)C7—C81.344 (3)
O2—C111.201 (2)C7—H70.9300
O3—C111.325 (3)C8—C91.491 (3)
O3—C121.456 (3)C8—C111.501 (3)
C1—C61.400 (3)C9—C101.502 (4)
C1—C21.401 (3)C10—H10A0.9600
C1—C71.468 (3)C10—H10B0.9600
C2—C31.369 (3)C10—H10C0.9600
C2—H2A0.9300C12—C131.495 (4)
C3—C41.384 (3)C12—H12A0.9700
C3—H30.9300C12—H12B0.9700
C4—C51.377 (3)C13—H13A0.9600
C5—C61.376 (3)C13—H13B0.9600
C5—H50.9300C13—H13C0.9600
C11—O3—C12116.98 (16)O1—C9—C8119.1 (2)
C6—C1—C2117.2 (2)O1—C9—C10120.6 (2)
C6—C1—C7118.26 (18)C8—C9—C10120.3 (2)
C2—C1—C7124.50 (19)C9—C10—H10A109.5
C3—C2—C1121.34 (19)C9—C10—H10B109.5
C3—C2—H2A119.3H10A—C10—H10B109.5
C1—C2—H2A119.3C9—C10—H10C109.5
C2—C3—C4119.4 (2)H10A—C10—H10C109.5
C2—C3—H3120.3H10B—C10—H10C109.5
C4—C3—H3120.3O2—C11—O3125.2 (2)
C5—C4—C3121.4 (2)O2—C11—C8124.1 (2)
C5—C4—Cl1119.85 (17)O3—C11—C8110.72 (16)
C3—C4—Cl1118.72 (18)O3—C12—C13106.71 (18)
C6—C5—C4118.5 (2)O3—C12—H12A110.4
C6—C5—H5120.8C13—C12—H12A110.4
C4—C5—H5120.8O3—C12—H12B110.4
C5—C6—C1122.12 (19)C13—C12—H12B110.4
C5—C6—H6118.9H12A—C12—H12B108.6
C1—C6—H6118.9C12—C13—H13A109.5
C8—C7—C1130.0 (2)C12—C13—H13B109.5
C8—C7—H7115.0H13A—C13—H13B109.5
C1—C7—H7115.0C12—C13—H13C109.5
C7—C8—C9123.8 (2)H13A—C13—H13C109.5
C7—C8—C11123.3 (2)H13B—C13—H13C109.5
C9—C8—C11112.85 (19)
C6—C1—C2—C31.7 (3)C1—C7—C8—C111.8 (4)
C7—C1—C2—C3179.6 (2)C7—C8—C9—O1179.1 (2)
C1—C2—C3—C40.2 (4)C11—C8—C9—O10.2 (3)
C2—C3—C4—C51.3 (4)C7—C8—C9—C102.4 (4)
C2—C3—C4—Cl1179.48 (18)C11—C8—C9—C10178.7 (2)
C3—C4—C5—C61.2 (4)C12—O3—C11—O21.0 (3)
Cl1—C4—C5—C6179.59 (18)C12—O3—C11—C8178.29 (18)
C4—C5—C6—C10.4 (4)C7—C8—C11—O299.3 (3)
C2—C1—C6—C51.8 (3)C9—C8—C11—O279.6 (3)
C7—C1—C6—C5179.4 (2)C7—C8—C11—O380.1 (3)
C6—C1—C7—C8169.6 (2)C9—C8—C11—O3101.1 (2)
C2—C1—C7—C811.7 (4)C11—O3—C12—C13172.43 (19)
C1—C7—C8—C9177.0 (2)

Experimental details

Crystal data
Chemical formulaC13H13ClO3
Mr252.68
Crystal system, space groupMonoclinic, P21/n
Temperature (K)295
a, b, c (Å)9.9956 (6), 7.7487 (5), 16.2709 (10)
β (°) 99.624 (1)
V3)1242.49 (13)
Z4
Radiation typeMo Kα
µ (mm1)0.30
Crystal size (mm)0.20 × 0.20 × 0.20
Data collection
DiffractometerBruker APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.942, 0.942
No. of measured, independent and
observed [I > 2σ(I)] reflections
11255, 2790, 1968
Rint0.069
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.201, 1.02
No. of reflections2790
No. of parameters156
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.40, 0.52

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

 

Acknowledgements

We thank Manchester Metropolitan University, Baku State University and the University of Malaya for supporting this study.

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDeng, P.-F., Chen, G.-B., Feng, Y.-Q. & Song, J. (2007). Acta Cryst. E63, o3532.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationShi, X. (2008). Acta Cryst. E64, o2462.  Web of Science CrossRef IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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