Dimethyl 2-(4-methyl­benzyl­idene)malonate

Barakat, A.; Al-Majid, A.M.; Mabkhot, Y.N.; Choudhary, M.I.; Yousuf, S.

doi:10.1107/S1600536813012464

organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page o919

doi:10.1107/S1600536813012464

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Dimethyl 2-(4-methylbenzylidene)malonate

Assem Barakat,^a,^b ‡ Abdullah Mohammed Al-Majid,^a Yahia Nasser Mabkhot,^a M. Iqbal Choudhary ^c,^a and Sammer Yousuf ^c ^*

^aDepartment of Chemistry, College of Science, King Saud University, PO Box 2455, Riyadh 11451, Saudi Arabia, ^bDepartment of Chemistry, Faculty of Science, Alexandria University, PO Box 426, Ibrahimia 21321 Alexandria, Egypt, and ^cH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
^*Correspondence e-mail: dr.sammer.yousuf@gmail.com

(Received 28 April 2013; accepted 7 May 2013; online 18 May 2013)

In the molecule of the title compound, C₁₃H₁₄O₄, the benzene ring forms dihedral angles of 18.60 (7) and 81.36 (8)° with the two arms of the malonate moiety. The crystal structure features C—H⋯O interactions, which form chains running parallel to the b axis.

Related literature

For the biological activity and synthesis of alkylidene and arylidene malonates, see: Liu et al. (2012 ); Heydri & Tahamipour (2011 ); Xu & Wang (2011 ); Li et al. (2010 , 2011 ); Gallier et al. (2009 ); Besavaiah et al. (2004 ). For the structures of related compounds, see: Rappoport & Gazit (1986 )

Experimental

Crystal data

C₁₃H₁₄O₄
M_r = 234.24
Monoclinic, P 2₁ /c
a = 14.0516 (6) Å
b = 7.7446 (3) Å
c = 12.5113 (5) Å
β = 113.727 (1)°
V = 1246.44 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 273 K
0.55 × 0.36 × 0.16 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.951, T_max = 0.985
7125 measured reflections
2316 independent reflections
1850 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.136
S = 1.08
2316 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13C⋯O1ⁱ	0.96	2.49	3.442 (3)	170
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813012464/rz5063sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813012464/rz5063Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813012464/rz5063Isup3.cml

checkCIF report

Comment top

Alkylidene and arylidene malonates have attracted the attention of organic and medicinal chemists as building blocks of many organic compounds with diverse biological activities. Due to their distinct structural features, these compounds serve as precursors for Michael addition in multiple reactions, such as Aza-Michael addition, Mukaiyama-Michael reaction and Friedel-Crafts reactions (Liu et al., 2012; Heydri & Tahamipour, 2011; Xu & Wang, 2011; Li et al., 2010; Gallier et al., 2009). Particularly they are utilized for the synthesis of trisubstituted alkenes via Knoevenagel condensation (Li et al., 2011). These trisubstitued alkenes in turn can be useful for the preparation of various biologically active molecules (Besavaiah et al., 2004).

The structure of title compound, C₁₃H₁₄O₄, is composed of a dimethyl malonate (O1–O4/C8–C12) substituted benzylidene ring (C1–C7) (Fig. 1). The benzene ring forms dihedral angles of 18.60 (7) and 81.36 (8)° with the C9/C10/O1/O2 and C11/C12/O3/O4 side chains of malonate. In the crystal, the structure is stabilized via C13—H13C···O1 intermolecular interactions (Table 1) forming chains running parallel to the b axis (Fig. 2). All bond lengths and angles were found to be similar to those observed in other structurally related compounds (Rappoport & Gazit 1986).

Related literature top

For the biological activity and synthesis of alkylidene and arylidene malonates, see: Liu et al. (2012); Heydri & Tahamipour (2011); Xu & Wang (2011); Li et al. (2010, 2011); Gallier et al. (2009); Besavaiah et al. (2004). For the structures of related compounds, see: Rappoport & Gazit (1986)

Experimental top

To a 150 ml flame-dried round-bottom flask, equipped with a magnetic stir bar and fitted with a Dean-Stark apparatus, was added benzene (25 ml), toluene aldehyde (1.44 g, 12 mmol), piperidine (11 µL, 0.12 mmol), acetic acid (7 µL, 0.12 mmol), and dimethyl malonate (1.72 g, 13 mmol) under an argon atmosphere. The reaction mixture was allowed to reflux for 24 h. The reaction progress was monitored by ¹H-NMR spectroscopy. After completion of the reaction, the reaction mixture was diluted with ethyl acetate (50 ml) and extracted with water (2 × 25 ml) and brine (1 × 25 ml) and dried over Na₂SO₄ to obtain the crude alkylidene malonate. Flash column chromatography (petroleum ether/ethyl acetate, 95:5 v/v) afforded a solution of the title compound as a clear liquid. On standing for 2 days at room temperature, cube-like crystals (2.67 g, 11.4 mmol, 95° yield) were obtained. M. p. 331 K. All chemicals were purchased from Sigma- Aldrich.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of title compound with displacement ellipsoids drawn at 30% probability level.
	Fig. 2. Crystal packing of the title compound viewed down the c axis. Only hydrogen atoms involved in hydrogen bonding (dashed lines) are shown.

Dimethyl 2-(4-methylbenzylidene)malonate top

Crystal data top

C₁₃H₁₄O₄	F(000) = 496
M_r = 234.24	D_x = 1.248 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2372 reflections
a = 14.0516 (6) Å	θ = 3.1–26.3°
b = 7.7446 (3) Å	µ = 0.09 mm⁻¹
c = 12.5113 (5) Å	T = 273 K
β = 113.727 (1)°	Block, colourless
V = 1246.44 (9) Å³	0.55 × 0.36 × 0.16 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2316 independent reflections
Radiation source: fine-focus sealed tube	1850 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scan	θ_max = 25.5°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −17→11
T_min = 0.951, T_max = 0.985	k = −9→9
7125 measured reflections	l = −15→15

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0674P)² + 0.2125P] where P = (F_o² + 2F_c²)/3
2316 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₃H₁₄O₄	V = 1246.44 (9) Å³
M_r = 234.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.0516 (6) Å	µ = 0.09 mm⁻¹
b = 7.7446 (3) Å	T = 273 K
c = 12.5113 (5) Å	0.55 × 0.36 × 0.16 mm
β = 113.727 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2316 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1850 reflections with I > 2σ(I)
T_min = 0.951, T_max = 0.985	R_int = 0.021
7125 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.08	Δρ_max = 0.20 e Å⁻³
2316 reflections	Δρ_min = −0.17 e Å⁻³
154 parameters

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	0.15387 (12)	−0.05063 (19)	0.26275 (14)	0.0835 (5)
O2	0.03912 (10)	0.15029 (16)	0.16332 (11)	0.0631 (4)
O3	0.10137 (11)	0.30017 (18)	−0.02578 (11)	0.0775 (5)
O4	0.19102 (10)	0.45753 (15)	0.13086 (11)	0.0621 (4)
C1	0.36456 (14)	0.2423 (2)	0.04658 (15)	0.0594 (5)
H1A	0.2996	0.2897	0.0027	0.071*
C2	0.44558 (15)	0.2730 (2)	0.01473 (16)	0.0635 (5)
H2A	0.4340	0.3405	−0.0508	0.076*
C3	0.54418 (14)	0.2067 (2)	0.07690 (16)	0.0589 (5)
C4	0.55784 (15)	0.1057 (3)	0.17338 (17)	0.0649 (5)
H4A	0.6230	0.0592	0.2172	0.078*
C5	0.47681 (15)	0.0728 (2)	0.20574 (16)	0.0607 (5)
H5A	0.4883	0.0034	0.2704	0.073*
C6	0.37811 (13)	0.1409 (2)	0.14407 (14)	0.0521 (4)
C7	0.29555 (14)	0.0931 (2)	0.18075 (14)	0.0540 (4)
H7A	0.3116	0.0001	0.2321	0.065*
C8	0.20104 (13)	0.1592 (2)	0.15361 (14)	0.0517 (4)
C9	0.13063 (14)	0.0737 (2)	0.20022 (15)	0.0555 (4)
C10	−0.03757 (16)	0.0739 (3)	0.19883 (19)	0.0683 (5)
H10A	−0.1005	0.1405	0.1677	0.103*
H10B	−0.0114	0.0726	0.2825	0.103*
H10C	−0.0517	−0.0422	0.1698	0.103*
C11	0.15819 (13)	0.3100 (2)	0.07484 (14)	0.0512 (4)
C12	0.15580 (17)	0.6132 (2)	0.0614 (2)	0.0775 (6)
H12A	0.1839	0.7125	0.1098	0.116*
H12B	0.0813	0.6181	0.0295	0.116*
H12C	0.1790	0.6120	−0.0011	0.116*
C13	0.63181 (16)	0.2386 (3)	0.03988 (19)	0.0766 (6)
H13A	0.6081	0.3113	−0.0280	0.115*
H13B	0.6554	0.1305	0.0219	0.115*
H13C	0.6880	0.2943	0.1021	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0768 (10)	0.0778 (10)	0.1055 (11)	0.0191 (8)	0.0467 (8)	0.0389 (8)
O2	0.0565 (8)	0.0567 (7)	0.0771 (8)	0.0059 (6)	0.0280 (6)	0.0078 (6)
O3	0.0810 (10)	0.0704 (9)	0.0579 (8)	0.0043 (7)	0.0039 (7)	0.0042 (6)
O4	0.0622 (8)	0.0465 (7)	0.0703 (8)	0.0023 (6)	0.0191 (6)	0.0000 (5)
C1	0.0510 (10)	0.0607 (11)	0.0617 (10)	0.0083 (8)	0.0176 (8)	0.0066 (8)
C2	0.0654 (12)	0.0638 (12)	0.0616 (10)	0.0018 (9)	0.0260 (9)	0.0032 (9)
C3	0.0556 (10)	0.0563 (10)	0.0629 (10)	−0.0051 (8)	0.0218 (8)	−0.0171 (8)
C4	0.0476 (10)	0.0688 (12)	0.0669 (11)	0.0076 (9)	0.0111 (8)	−0.0072 (9)
C5	0.0561 (11)	0.0598 (11)	0.0582 (10)	0.0083 (9)	0.0148 (8)	0.0043 (8)
C6	0.0517 (10)	0.0460 (9)	0.0531 (9)	0.0034 (7)	0.0154 (7)	−0.0030 (7)
C7	0.0561 (11)	0.0482 (9)	0.0529 (9)	0.0039 (8)	0.0169 (8)	0.0051 (7)
C8	0.0525 (10)	0.0454 (9)	0.0524 (9)	0.0017 (7)	0.0161 (7)	−0.0002 (7)
C9	0.0584 (11)	0.0488 (10)	0.0579 (10)	0.0051 (8)	0.0220 (8)	0.0023 (8)
C10	0.0605 (11)	0.0678 (12)	0.0826 (13)	−0.0028 (10)	0.0349 (10)	−0.0023 (10)
C11	0.0438 (9)	0.0518 (10)	0.0551 (9)	0.0020 (7)	0.0170 (7)	0.0010 (7)
C12	0.0783 (14)	0.0483 (11)	0.1068 (16)	0.0099 (10)	0.0383 (13)	0.0147 (10)
C13	0.0645 (12)	0.0831 (14)	0.0874 (14)	−0.0078 (11)	0.0359 (11)	−0.0216 (11)

Geometric parameters (Å, º) top

O1—C9	1.200 (2)	C5—H5A	0.9300
O2—C9	1.319 (2)	C6—C7	1.457 (2)
O2—C10	1.447 (2)	C7—C8	1.334 (2)
O3—C11	1.1913 (19)	C7—H7A	0.9300
O4—C11	1.3226 (19)	C8—C11	1.490 (2)
O4—C12	1.452 (2)	C8—C9	1.491 (2)
C1—C2	1.370 (3)	C10—H10A	0.9600
C1—C6	1.398 (2)	C10—H10B	0.9600
C1—H1A	0.9300	C10—H10C	0.9600
C2—C3	1.386 (3)	C12—H12A	0.9600
C2—H2A	0.9300	C12—H12B	0.9600
C3—C4	1.385 (3)	C12—H12C	0.9600
C3—C13	1.500 (3)	C13—H13A	0.9600
C4—C5	1.377 (3)	C13—H13B	0.9600
C4—H4A	0.9300	C13—H13C	0.9600
C5—C6	1.391 (2)

C9—O2—C10	116.73 (15)	C11—C8—C9	116.87 (15)
C11—O4—C12	115.97 (14)	O1—C9—O2	124.07 (17)
C2—C1—C6	120.92 (16)	O1—C9—C8	124.21 (16)
C2—C1—H1A	119.5	O2—C9—C8	111.71 (15)
C6—C1—H1A	119.5	O2—C10—H10A	109.5
C1—C2—C3	122.19 (18)	O2—C10—H10B	109.5
C1—C2—H2A	118.9	H10A—C10—H10B	109.5
C3—C2—H2A	118.9	O2—C10—H10C	109.5
C4—C3—C2	117.06 (18)	H10A—C10—H10C	109.5
C4—C3—C13	121.26 (18)	H10B—C10—H10C	109.5
C2—C3—C13	121.67 (18)	O3—C11—O4	123.90 (16)
C5—C4—C3	121.31 (17)	O3—C11—C8	124.73 (16)
C5—C4—H4A	119.3	O4—C11—C8	111.37 (14)
C3—C4—H4A	119.3	O4—C12—H12A	109.5
C4—C5—C6	121.63 (18)	O4—C12—H12B	109.5
C4—C5—H5A	119.2	H12A—C12—H12B	109.5
C6—C5—H5A	119.2	O4—C12—H12C	109.5
C5—C6—C1	116.89 (17)	H12A—C12—H12C	109.5
C5—C6—C7	118.11 (16)	H12B—C12—H12C	109.5
C1—C6—C7	124.87 (15)	C3—C13—H13A	109.5
C8—C7—C6	131.27 (16)	C3—C13—H13B	109.5
C8—C7—H7A	114.4	H13A—C13—H13B	109.5
C6—C7—H7A	114.4	C3—C13—H13C	109.5
C7—C8—C11	124.44 (16)	H13A—C13—H13C	109.5
C7—C8—C9	118.63 (15)	H13B—C13—H13C	109.5

C6—C1—C2—C3	−0.3 (3)	C6—C7—C8—C9	176.17 (16)
C1—C2—C3—C4	0.5 (3)	C10—O2—C9—O1	−2.0 (3)
C1—C2—C3—C13	178.91 (17)	C10—O2—C9—C8	177.38 (14)
C2—C3—C4—C5	0.1 (3)	C7—C8—C9—O1	1.2 (3)
C13—C3—C4—C5	−178.38 (17)	C11—C8—C9—O1	178.61 (17)
C3—C4—C5—C6	−0.8 (3)	C7—C8—C9—O2	−178.12 (15)
C4—C5—C6—C1	0.9 (3)	C11—C8—C9—O2	−0.7 (2)
C4—C5—C6—C7	177.10 (16)	C12—O4—C11—O3	−1.6 (3)
C2—C1—C6—C5	−0.4 (3)	C12—O4—C11—C8	178.58 (14)
C2—C1—C6—C7	−176.28 (17)	C7—C8—C11—O3	98.3 (2)
C5—C6—C7—C8	166.38 (18)	C9—C8—C11—O3	−78.9 (2)
C1—C6—C7—C8	−17.8 (3)	C7—C8—C11—O4	−81.9 (2)
C6—C7—C8—C11	−1.0 (3)	C9—C8—C11—O4	100.88 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13C···O1ⁱ	0.96	2.49	3.442 (3)	170

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄O₄
M_r	234.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	14.0516 (6), 7.7446 (3), 12.5113 (5)
β (°)	113.727 (1)
V (Å³)	1246.44 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.55 × 0.36 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.951, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	7125, 2316, 1850
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.136, 1.08
No. of reflections	2316
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.17

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13C···O1ⁱ	0.9600	2.4900	3.442 (3)	170.00

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Footnotes

‡Additional correspondence author, e-mail: ambarakat@ksu.edu.sa.

Acknowledgements

This project was supported by the King Saud University, Deanship of Scientific Research, College of Science Research Center.

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