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

Mohamed, S.K.; Abdelhamid, A.A.; Gurbanov, A.V.; Maharramov, A.M.; Ng, S.W.

doi:10.1107/S1600536811000717

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o365

doi:10.1107/S1600536811000717

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

Shaaban K. Mohamed,^a Antar A. Abdelhamid,^b Atash V. Gurbanov,^b A. M. Maharramov ^b and Seik Weng Ng ^c ^*

^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 ); Shi (2008 ).

Experimental

Crystal data

C₁₃H₁₃ClO₃
M_r = 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 ) T_min = 0.942, T_max = 0.942
11255 measured reflections
2790 independent reflections
1968 reflections with I > 2σ(I)
R_int = 0.069

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.201
S = 1.02
2790 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811000717/hg2789sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000717/hg2789Isup2.hkl

checkCIF report

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).

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

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

C₁₃H₁₃ClO₃	F(000) = 528
M_r = 252.68	D_x = 1.351 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3560 reflections
a = 9.9956 (6) Å	θ = 2.2–27.8°
b = 7.7487 (5) Å	µ = 0.30 mm⁻¹
c = 16.2709 (10) Å	T = 295 K
β = 99.624 (1)°	Prism, colorless
V = 1242.49 (13) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	2790 independent reflections
Radiation source: fine-focus sealed tube	1968 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.942, T_max = 0.942	k = −10→9
11255 measured reflections	l = −21→21

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.201	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.1314P)²] where P = (F_o² + 2F_c²)/3
2790 reflections	(Δ/σ)_max = 0.001
156 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

C₁₃H₁₃ClO₃	V = 1242.49 (13) Å³
M_r = 252.68	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.9956 (6) Å	µ = 0.30 mm⁻¹
b = 7.7487 (5) Å	T = 295 K
c = 16.2709 (10) Å	0.20 × 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)
T_min = 0.942, T_max = 0.942	R_int = 0.069
11255 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.201	H-atom parameters constrained
S = 1.02	Δρ_max = 0.40 e Å⁻³
2790 reflections	Δρ_min = −0.52 e Å⁻³
156 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.17886 (7)	0.43778 (11)	0.15024 (4)	0.0663 (3)
O1	0.2270 (2)	0.3753 (3)	0.72305 (11)	0.0703 (6)
O2	0.42363 (15)	0.4336 (2)	0.59728 (11)	0.0555 (5)
O3	0.27248 (13)	0.6486 (2)	0.56982 (10)	0.0452 (4)
C1	0.13562 (19)	0.3488 (3)	0.41918 (13)	0.0399 (5)
C2	0.2540 (2)	0.4199 (3)	0.39776 (14)	0.0453 (6)
H2A	0.3252	0.4497	0.4397	0.054*
C3	0.2669 (2)	0.4463 (3)	0.31626 (14)	0.0467 (6)
H3	0.3460	0.4940	0.3031	0.056*
C4	0.1611 (2)	0.4015 (3)	0.25368 (14)	0.0437 (5)
C5	0.0440 (2)	0.3274 (3)	0.27150 (14)	0.0490 (6)
H5	−0.0258	0.2957	0.2290	0.059*
C6	0.03270 (19)	0.3015 (3)	0.35374 (14)	0.0453 (5)
H6	−0.0458	0.2509	0.3662	0.054*
C7	0.11396 (19)	0.3175 (3)	0.50496 (14)	0.0418 (5)
H7	0.0387	0.2501	0.5098	0.050*
C8	0.18613 (19)	0.3714 (3)	0.57758 (13)	0.0405 (5)
C9	0.1549 (2)	0.3219 (3)	0.66085 (15)	0.0501 (6)
C10	0.0339 (3)	0.2111 (4)	0.66738 (18)	0.0693 (8)
H10A	0.0333	0.1832	0.7248	0.104*
H10B	0.0385	0.1068	0.6362	0.104*
H10C	−0.0476	0.2727	0.6453	0.104*
C11	0.3088 (2)	0.4853 (3)	0.58325 (13)	0.0395 (5)
C12	0.3811 (2)	0.7742 (3)	0.57098 (17)	0.0535 (6)
H12A	0.4275	0.7563	0.5239	0.064*
H12B	0.4466	0.7634	0.6219	0.064*
C13	0.3162 (3)	0.9486 (3)	0.56615 (18)	0.0592 (7)
H13A	0.3836	1.0353	0.5626	0.089*
H13B	0.2764	0.9679	0.6151	0.089*
H13C	0.2470	0.9546	0.5176	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0540 (4)	0.0967 (7)	0.0483 (4)	0.0031 (3)	0.0085 (3)	0.0024 (3)
O1	0.0600 (11)	0.0996 (17)	0.0513 (11)	−0.0032 (11)	0.0095 (9)	0.0006 (10)
O2	0.0281 (8)	0.0621 (12)	0.0735 (12)	0.0041 (7)	−0.0001 (7)	0.0076 (8)
O3	0.0282 (7)	0.0479 (10)	0.0601 (9)	−0.0011 (6)	0.0091 (6)	−0.0004 (7)
C1	0.0237 (8)	0.0445 (12)	0.0514 (12)	−0.0006 (8)	0.0061 (8)	−0.0051 (9)
C2	0.0235 (9)	0.0614 (15)	0.0504 (12)	−0.0061 (9)	0.0049 (8)	−0.0091 (10)
C3	0.0280 (10)	0.0594 (15)	0.0533 (13)	−0.0052 (9)	0.0086 (9)	−0.0040 (10)
C4	0.0335 (10)	0.0524 (13)	0.0446 (11)	0.0046 (9)	0.0050 (8)	−0.0025 (10)
C5	0.0295 (10)	0.0605 (14)	0.0540 (13)	−0.0031 (10)	−0.0013 (9)	−0.0107 (11)
C6	0.0237 (9)	0.0528 (13)	0.0590 (13)	−0.0075 (9)	0.0060 (8)	−0.0092 (10)
C7	0.0246 (9)	0.0464 (12)	0.0555 (12)	−0.0016 (8)	0.0099 (8)	−0.0030 (10)
C8	0.0280 (9)	0.0422 (12)	0.0522 (12)	0.0038 (9)	0.0092 (8)	0.0033 (9)
C9	0.0405 (11)	0.0575 (15)	0.0545 (13)	0.0068 (10)	0.0147 (10)	0.0040 (11)
C10	0.0592 (16)	0.080 (2)	0.0759 (18)	−0.0097 (14)	0.0314 (14)	0.0065 (15)
C11	0.0284 (9)	0.0499 (13)	0.0400 (10)	0.0034 (9)	0.0046 (8)	0.0021 (9)
C12	0.0379 (11)	0.0576 (16)	0.0653 (14)	−0.0090 (10)	0.0092 (10)	0.0009 (12)
C13	0.0581 (16)	0.0522 (15)	0.0686 (17)	−0.0050 (12)	0.0140 (13)	−0.0020 (12)

Geometric parameters (Å, º) top

Cl1—C4	1.745 (2)	C6—H6	0.9300
O1—C9	1.213 (3)	C7—C8	1.344 (3)
O2—C11	1.201 (2)	C7—H7	0.9300
O3—C11	1.325 (3)	C8—C9	1.491 (3)
O3—C12	1.456 (3)	C8—C11	1.501 (3)
C1—C6	1.400 (3)	C9—C10	1.502 (4)
C1—C2	1.401 (3)	C10—H10A	0.9600
C1—C7	1.468 (3)	C10—H10B	0.9600
C2—C3	1.369 (3)	C10—H10C	0.9600
C2—H2A	0.9300	C12—C13	1.495 (4)
C3—C4	1.384 (3)	C12—H12A	0.9700
C3—H3	0.9300	C12—H12B	0.9700
C4—C5	1.377 (3)	C13—H13A	0.9600
C5—C6	1.376 (3)	C13—H13B	0.9600
C5—H5	0.9300	C13—H13C	0.9600

C11—O3—C12	116.98 (16)	O1—C9—C8	119.1 (2)
C6—C1—C2	117.2 (2)	O1—C9—C10	120.6 (2)
C6—C1—C7	118.26 (18)	C8—C9—C10	120.3 (2)
C2—C1—C7	124.50 (19)	C9—C10—H10A	109.5
C3—C2—C1	121.34 (19)	C9—C10—H10B	109.5
C3—C2—H2A	119.3	H10A—C10—H10B	109.5
C1—C2—H2A	119.3	C9—C10—H10C	109.5
C2—C3—C4	119.4 (2)	H10A—C10—H10C	109.5
C2—C3—H3	120.3	H10B—C10—H10C	109.5
C4—C3—H3	120.3	O2—C11—O3	125.2 (2)
C5—C4—C3	121.4 (2)	O2—C11—C8	124.1 (2)
C5—C4—Cl1	119.85 (17)	O3—C11—C8	110.72 (16)
C3—C4—Cl1	118.72 (18)	O3—C12—C13	106.71 (18)
C6—C5—C4	118.5 (2)	O3—C12—H12A	110.4
C6—C5—H5	120.8	C13—C12—H12A	110.4
C4—C5—H5	120.8	O3—C12—H12B	110.4
C5—C6—C1	122.12 (19)	C13—C12—H12B	110.4
C5—C6—H6	118.9	H12A—C12—H12B	108.6
C1—C6—H6	118.9	C12—C13—H13A	109.5
C8—C7—C1	130.0 (2)	C12—C13—H13B	109.5
C8—C7—H7	115.0	H13A—C13—H13B	109.5
C1—C7—H7	115.0	C12—C13—H13C	109.5
C7—C8—C9	123.8 (2)	H13A—C13—H13C	109.5
C7—C8—C11	123.3 (2)	H13B—C13—H13C	109.5
C9—C8—C11	112.85 (19)

C6—C1—C2—C3	1.7 (3)	C1—C7—C8—C11	1.8 (4)
C7—C1—C2—C3	−179.6 (2)	C7—C8—C9—O1	179.1 (2)
C1—C2—C3—C4	−0.2 (4)	C11—C8—C9—O1	0.2 (3)
C2—C3—C4—C5	−1.3 (4)	C7—C8—C9—C10	−2.4 (4)
C2—C3—C4—Cl1	179.48 (18)	C11—C8—C9—C10	178.7 (2)
C3—C4—C5—C6	1.2 (4)	C12—O3—C11—O2	1.0 (3)
Cl1—C4—C5—C6	−179.59 (18)	C12—O3—C11—C8	−178.29 (18)
C4—C5—C6—C1	0.4 (4)	C7—C8—C11—O2	−99.3 (3)
C2—C1—C6—C5	−1.8 (3)	C9—C8—C11—O2	79.6 (3)
C7—C1—C6—C5	179.4 (2)	C7—C8—C11—O3	80.1 (3)
C6—C1—C7—C8	−169.6 (2)	C9—C8—C11—O3	−101.1 (2)
C2—C1—C7—C8	11.7 (4)	C11—O3—C12—C13	−172.43 (19)
C1—C7—C8—C9	−177.0 (2)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃ClO₃
M_r	252.68
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	9.9956 (6), 7.7487 (5), 16.2709 (10)
β (°)	99.624 (1)
V (Å³)	1242.49 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.942, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	11255, 2790, 1968
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.201, 1.02
No. of reflections	2790
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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

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