Dimethyl 2-(2,4,6-trimethoxy­benz­yl)malonate

Abstract

In the title compound, C₁₅H₂₀O₇, the benzene ring makes dihedral angles of 69.17 (5) and 80.81 (4)° with the two side chains of malonate. The two malonate side chains comprising C/C/O/C atoms are oriented at right angles [86.26 (6)°] with respect to each other. In the crystal structure, the crystal packing is stabilized by weak non-classical inter­molecular C—H⋯O hydrogen bonds, which link the mol­ecules into an infinite network.

Related literature

Substituted malonate, an important organic inter­mediate, is electrooxidized in methanol in the presence of halogen ions to afford the corresponding halomalonates, see: Okimoto & Takahashi (2002 ▶). For a related structure, see: Liu et al. (2010 ▶).

Experimental

Crystal data

• C₁₅H₂₀O₇

• M _r = 312.31

• Monoclinic,

• a = 11.6173 (15) Å

• b = 8.1192 (10) Å

• c = 17.236 (2) Å

• β = 103.968 (2)°

• V = 1577.7 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 296 K

• 0.28 × 0.24 × 0.20 mm

Data collection

• Rigaku Saturn CCD area-detector diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.904, T _max = 0.935

• 9686 measured reflections

• 3851 independent reflections

• 2969 reflections with I > 2σ(I)

• R _int = 0.019

Refinement

• R[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 0.112

• S = 1.05

• 3851 reflections

• 205 parameters

• H-atom parameters constrained

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.15 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5b⋯O2i	0.96	2.54	3.353 (2)	142
C5—H5a⋯O5ii	0.96	2.57	3.503 (2)	164
C3—H3⋯O6iii	0.98	2.54	3.499 (2)	168

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

Substituted malnoate is a very important organic intermediate. It is electrooxidized in methanol in the presence of halogen ions to afford the corresponding halomalonates (Okimoto & Takahashi, 2002). We have synthesized dimethyl 2-(quinolin-methyene)malonate, and reported its structure (Liu et al., 2010). We now report the synthesis and structure of the title compound, (I).

In the title compound ( Fig. 1), the benzene ring makes dihedral angles of 69.17 (5) and 80.81 (4)° with two side chains of malonate. In the crystal structure, the two malonate side chains comprising C/C/O/O atoms (C2/C3/O1/O2 and C113/C4/O3/C4) are oriented at right angles (86.26 (6)°) with respect to each other. In the crystal structure, the crystal packing is stabilized by weak non-classical intermolecular C—H···O hydrogen bonds which link the molecules into an infinite network; details have been provided in Table 1 and Fig. 2.

Experimental

An anhydrous methanol solution (130 ml) of 1-brommethyl-3,4,5-trimethoxy (26.0 g, 0.1 mol) was added to an anhydrous methanol solution (180 ml) of sodium methoxide (5.4 g, 0.1 mol) and dimethyl malonate (26.4 g, 0.2 mol). The mixture was refluxed for 6 hours. The product was isolated with silica gel column, then the solvent was removed and added petroleum ether (5 ml) to the white precipitate. The precipitate was then isolated, recrystallized from n-hexane, and dried in a vacuum to give the title compound in 75% yield. Colorless single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an n-hexane solution.

Refinement

The H atoms were included in calculated positions (C—H = 0.93–0.98 Å) and refined as riding with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C).

Figures

Fig. 1.

The title structure plotted with displacement ellipsoids at 50% probability level.

Fig. 2.

A unit cell showing intermolecular hydrogen bonds by dashed lines; the H-atoms not involved in H-bonds have been excluded for clarity.

Crystal data

C15H20O7	F(000) = 664
Mr = 312.31	Dx = 1.315 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3043 reflections
a = 11.6173 (15) Å	θ = 2.4–24.5°
b = 8.1192 (10) Å	µ = 0.11 mm−1
c = 17.236 (2) Å	T = 296 K
β = 103.968 (2)°	Prism, colourless
V = 1577.7 (3) Å3	0.28 × 0.24 × 0.20 mm
Z = 4

Data collection

Rigaku Saturn CCD area-detector diffractometer	3851 independent reflections
Radiation source: fine-focus sealed tube	2969 reflections with I > 2σ(I)
graphite	Rint = 0.019
Detector resolution: 7.31 pixels mm-1	θmax = 28.3°, θmin = 1.9°
ω and φ scans	h = −14→12
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −8→10
Tmin = 0.904, Tmax = 0.935	l = −19→22
9686 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.112	w = 1/[σ2(Fo2) + (0.0481P)2 + 0.3127P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
3851 reflections	Δρmax = 0.21 e Å−3
205 parameters	Δρmin = −0.15 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0172 (18)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.13204 (15)	0.9367 (2)	0.43372 (11)	0.0635 (4)
H1A	−0.2035	0.9372	0.3918	0.095*
H1B	−0.1042	1.0476	0.4447	0.095*
H1C	−0.1479	0.8893	0.4811	0.095*
C2	−0.07201 (11)	0.68523 (16)	0.39019 (7)	0.0404 (3)
C3	0.02668 (11)	0.59332 (15)	0.36509 (7)	0.0395 (3)
H3	0.0329	0.6362	0.3131	0.047*
C4	−0.01013 (11)	0.41471 (17)	0.35462 (8)	0.0421 (3)
C5	−0.10242 (17)	0.2143 (2)	0.26180 (11)	0.0722 (5)
H5A	−0.0371	0.1390	0.2762	0.108*
H5B	−0.1390	0.2036	0.2058	0.108*
H5C	−0.1595	0.1898	0.2922	0.108*
C6	0.14750 (11)	0.61262 (17)	0.42412 (8)	0.0424 (3)
H6A	0.1692	0.7282	0.4279	0.051*
H6B	0.1413	0.5765	0.4766	0.051*
C7	0.24446 (11)	0.51492 (15)	0.39988 (8)	0.0389 (3)
C8	0.26120 (11)	0.52716 (16)	0.32288 (8)	0.0403 (3)
H8	0.2142	0.5980	0.2861	0.048*
C9	0.34815 (11)	0.43345 (15)	0.30108 (8)	0.0390 (3)
C10	0.41922 (11)	0.32810 (16)	0.35617 (8)	0.0411 (3)
C11	0.40304 (11)	0.31759 (16)	0.43313 (8)	0.0429 (3)
C12	0.31541 (11)	0.41072 (16)	0.45482 (8)	0.0426 (3)
H12	0.3044	0.4030	0.5064	0.051*
C13	0.30064 (15)	0.5376 (2)	0.16826 (9)	0.0598 (4)
H13A	0.2188	0.5060	0.1589	0.090*
H13B	0.3260	0.5284	0.1194	0.090*
H13C	0.3097	0.6494	0.1868	0.090*
C14	0.61684 (16)	0.2734 (3)	0.35421 (15)	0.0899 (7)
H14A	0.6255	0.3796	0.3318	0.135*
H14B	0.6648	0.1946	0.3348	0.135*
H14C	0.6419	0.2792	0.4114	0.135*
C15	0.47068 (17)	0.2007 (2)	0.56275 (10)	0.0675 (5)
H15A	0.4958	0.3047	0.5876	0.101*
H15B	0.5227	0.1153	0.5893	0.101*
H15C	0.3911	0.1778	0.5665	0.101*
O1	−0.04280 (9)	0.84060 (12)	0.40905 (6)	0.0532 (3)
O2	−0.16628 (8)	0.62656 (13)	0.39094 (6)	0.0558 (3)
O3	−0.06001 (10)	0.38021 (14)	0.27852 (6)	0.0579 (3)
O4	0.00316 (11)	0.31615 (13)	0.40747 (6)	0.0613 (3)
O5	0.37059 (9)	0.43260 (12)	0.22680 (6)	0.0505 (3)
O6	0.49714 (9)	0.22459 (13)	0.33151 (6)	0.0539 (3)
O7	0.47421 (10)	0.20690 (14)	0.48168 (6)	0.0623 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0574 (9)	0.0518 (9)	0.0869 (12)	0.0155 (7)	0.0283 (8)	−0.0038 (8)
C2	0.0369 (6)	0.0443 (7)	0.0404 (6)	0.0060 (5)	0.0103 (5)	0.0068 (5)
C3	0.0389 (6)	0.0423 (7)	0.0400 (6)	0.0047 (5)	0.0150 (5)	0.0049 (5)
C4	0.0364 (6)	0.0462 (7)	0.0450 (7)	0.0040 (5)	0.0122 (5)	0.0005 (6)
C5	0.0692 (11)	0.0745 (12)	0.0693 (11)	−0.0141 (9)	0.0099 (9)	−0.0216 (9)
C6	0.0380 (6)	0.0429 (7)	0.0484 (7)	0.0028 (5)	0.0147 (5)	−0.0035 (6)
C7	0.0342 (6)	0.0365 (6)	0.0473 (7)	−0.0008 (5)	0.0125 (5)	−0.0037 (5)
C8	0.0371 (6)	0.0375 (6)	0.0481 (7)	0.0036 (5)	0.0136 (5)	0.0034 (5)
C9	0.0380 (6)	0.0365 (6)	0.0451 (7)	−0.0021 (5)	0.0150 (5)	−0.0022 (5)
C10	0.0377 (6)	0.0360 (6)	0.0505 (7)	0.0036 (5)	0.0124 (5)	−0.0061 (5)
C11	0.0420 (7)	0.0383 (7)	0.0467 (7)	0.0038 (5)	0.0078 (5)	−0.0010 (5)
C12	0.0432 (7)	0.0438 (7)	0.0422 (7)	0.0014 (5)	0.0129 (5)	−0.0018 (5)
C13	0.0678 (10)	0.0642 (10)	0.0507 (8)	0.0134 (8)	0.0206 (7)	0.0094 (7)
C14	0.0486 (10)	0.1037 (16)	0.1212 (18)	0.0205 (10)	0.0282 (10)	−0.0129 (13)
C15	0.0708 (11)	0.0756 (12)	0.0525 (9)	0.0189 (9)	0.0081 (8)	0.0119 (8)
O1	0.0482 (5)	0.0417 (5)	0.0760 (7)	0.0066 (4)	0.0271 (5)	0.0019 (5)
O2	0.0393 (5)	0.0585 (6)	0.0730 (7)	0.0012 (4)	0.0202 (5)	−0.0026 (5)
O3	0.0628 (6)	0.0628 (7)	0.0462 (6)	−0.0067 (5)	0.0098 (5)	−0.0055 (5)
O4	0.0764 (8)	0.0473 (6)	0.0553 (6)	−0.0060 (5)	0.0061 (5)	0.0080 (5)
O5	0.0555 (6)	0.0529 (6)	0.0487 (5)	0.0127 (4)	0.0238 (4)	0.0057 (4)
O6	0.0521 (6)	0.0520 (6)	0.0598 (6)	0.0174 (4)	0.0176 (5)	−0.0061 (5)
O7	0.0716 (7)	0.0625 (7)	0.0521 (6)	0.0302 (6)	0.0134 (5)	0.0090 (5)

Geometric parameters (Å, °)

C1—O1	1.4411 (17)	C8—C9	1.3869 (17)
C1—H1A	0.9600	C8—H8	0.9300
C1—H1B	0.9600	C9—O5	1.3668 (15)
C1—H1C	0.9600	C9—C10	1.3915 (18)
C2—O2	1.1973 (16)	C10—O6	1.3756 (15)
C2—O1	1.3262 (17)	C10—C11	1.3864 (19)
C2—C3	1.5159 (17)	C11—O7	1.3630 (16)
C3—C4	1.5104 (19)	C11—C12	1.3898 (18)
C3—C6	1.5298 (18)	C12—H12	0.9300
C3—H3	0.9800	C13—O5	1.4175 (18)
C4—O4	1.1941 (16)	C13—H13A	0.9600
C4—O3	1.3296 (16)	C13—H13B	0.9600
C5—O3	1.439 (2)	C13—H13C	0.9600
C5—H5A	0.9600	C14—O6	1.408 (2)
C5—H5B	0.9600	C14—H14A	0.9600
C5—H5C	0.9600	C14—H14B	0.9600
C6—C7	1.5165 (17)	C14—H14C	0.9600
C6—H6A	0.9700	C15—O7	1.4086 (19)
C6—H6B	0.9700	C15—H15A	0.9600
C7—C12	1.3839 (18)	C15—H15B	0.9600
C7—C8	1.3907 (18)	C15—H15C	0.9600
O1—C1—H1A	109.5	O5—C9—C8	124.92 (12)
O1—C1—H1B	109.5	O5—C9—C10	114.85 (11)
H1A—C1—H1B	109.5	C8—C9—C10	120.22 (12)
O1—C1—H1C	109.5	O6—C10—C11	120.62 (12)
H1A—C1—H1C	109.5	O6—C10—C9	119.40 (12)
H1B—C1—H1C	109.5	C11—C10—C9	119.70 (11)
O2—C2—O1	123.81 (12)	O7—C11—C10	115.20 (11)
O2—C2—C3	124.33 (12)	O7—C11—C12	124.66 (12)
O1—C2—C3	111.83 (11)	C10—C11—C12	120.08 (12)
C4—C3—C2	107.15 (10)	C7—C12—C11	120.16 (12)
C4—C3—C6	111.45 (10)	C7—C12—H12	119.9
C2—C3—C6	113.29 (10)	C11—C12—H12	119.9
C4—C3—H3	108.3	O5—C13—H13A	109.5
C2—C3—H3	108.3	O5—C13—H13B	109.5
C6—C3—H3	108.3	H13A—C13—H13B	109.5
O4—C4—O3	123.82 (13)	O5—C13—H13C	109.5
O4—C4—C3	124.86 (12)	H13A—C13—H13C	109.5
O3—C4—C3	111.32 (11)	H13B—C13—H13C	109.5
O3—C5—H5A	109.5	O6—C14—H14A	109.5
O3—C5—H5B	109.5	O6—C14—H14B	109.5
H5A—C5—H5B	109.5	H14A—C14—H14B	109.5
O3—C5—H5C	109.5	O6—C14—H14C	109.5
H5A—C5—H5C	109.5	H14A—C14—H14C	109.5
H5B—C5—H5C	109.5	H14B—C14—H14C	109.5
C7—C6—C3	112.73 (10)	O7—C15—H15A	109.5
C7—C6—H6A	109.0	O7—C15—H15B	109.5
C3—C6—H6A	109.0	H15A—C15—H15B	109.5
C7—C6—H6B	109.0	O7—C15—H15C	109.5
C3—C6—H6B	109.0	H15A—C15—H15C	109.5
H6A—C6—H6B	107.8	H15B—C15—H15C	109.5
C12—C7—C8	119.96 (11)	C2—O1—C1	115.31 (11)
C12—C7—C6	119.38 (11)	C4—O3—C5	116.19 (13)
C8—C7—C6	120.66 (11)	C9—O5—C13	117.23 (11)
C9—C8—C7	119.87 (12)	C10—O6—C14	114.95 (12)
C9—C8—H8	120.1	C11—O7—C15	118.30 (12)
C7—C8—H8	120.1

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5b···O2i	0.96	2.54	3.353 (2)	142
C5—H5a···O5ii	0.96	2.57	3.503 (2)	164
C3—H3···O6iii	0.98	2.54	3.499 (2)	168

Symmetry codes: (i) −x−1/2, y−1/2, −z+1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2.