Dimethyl 2-(methyl­amino­methyl­ene)malonate

Martin Gróf; Jozef Kožíšek; Viktor Milata; Anton Gatial

doi:10.1107/S1600536808014773

. 2008 May 21;64(Pt 6):o1133–o1134. doi: 10.1107/S1600536808014773

Dimethyl 2-(methylaminomethylene)malonate

Martin Gróf ^a,^*, Jozef Kožíšek ^a, Viktor Milata ^b, Anton Gatial ^a

PMCID: PMC2961545 PMID: 21202643

Abstract

In the title compound, C₇H₁₁NO₄, which is an example of a push–pull alkene, a network of N—H⋯O and C—H⋯O interactions helps to establish the crystal structure. The investigated crystal turned out to be a non-merohedral twin with a ratio of twin components of 0.442 (3):0.558 (3). Two pairs of independent molecules (Z′ = 4) are linked by intermolecular N—H⋯O hydrogen bonds, forming independent chains; the chains are connected via intermolecular C—H⋯O contacts, building a three-dimensional network.

Related literature

For related literature, see: Bouzard (1990 ▶); Cook (1969 ▶); Dyke (1973 ▶); Freeman (1981 ▶); Gróf et al. (2008 ▶); Kálmán & Argay (1998 ▶); Bolte (2004 ▶).

Experimental

Crystal data

C₇H₁₁NO₄
M _r = 173.17
Triclinic,
a = 11.165 (2) Å
b = 12.073 (2) Å
c = 13.211 (3) Å
α = 113.70 (3)°
β = 93.71 (3)°
γ = 94.02 (3)°
V = 1618.1 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 K
0.43 × 0.15 × 0.08 mm

Data collection

Oxford Diffraction GEMINI R diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006 ▶) T _min = 0.968, T _max = 0.996
9295 measured reflections
9295 independent reflections
3920 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.091
wR(F ²) = 0.257
S = 0.90
9295 reflections
446 parameters
96 restraints
H-atom parameters constrained
Δρ_max = 1.13 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808014773/si2088sup1.cif

e-64-o1133-sup1.cif^{(28.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014773/si2088Isup2.hkl

e-64-o1133-Isup2.hkl^{(454.6KB, hkl)}

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
N1—H1⋯O1	0.86	2.08	2.689 (4)	127
N1—H1⋯O10	0.86	2.42	2.990 (4)	125
N2—H2⋯O5	0.86	2.08	2.687 (4)	127
N2—H2⋯O14ⁱ	0.86	2.30	2.893 (5)	127
N3—H3⋯O9	0.86	2.06	2.684 (4)	129
N3—H3⋯O2ⁱ	0.86	2.32	2.912 (5)	126
N4—H4⋯O13	0.86	2.08	2.698 (5)	128
N4—H4⋯O6	0.86	2.40	2.957 (5)	123
C4—H4A⋯O2	0.93	2.27	2.683 (7)	106
C6—H6A⋯O14	0.96	2.50	3.449 (7)	169
C11—H11A⋯O6	0.93	2.29	2.706 (6)	107
C11—H11A⋯O13	0.93	2.60	3.487 (6)	159
C14—H14A⋯O13	0.96	2.59	3.507 (6)	161
C18—H18A⋯O1	0.93	2.58	3.470 (6)	160
C18—H18A⋯O10	0.93	2.27	2.679 (6)	106
C25—H25A⋯O14	0.93	2.28	2.691 (6)	106
C27—H27A⋯O2ⁱ	0.96	2.59	3.340 (7)	135
C28—H28C⋯O6	0.96	2.60	3.024 (6)	107

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Grant Agency of the Slovak Republic, grant Nos. APVT-20–007304 and VEGA 1/0817/08.

supplementary crystallographic information

Comment

The title compound, C₇ H₁₁ N O₄, belongs to the so-called push-pull olefins. Push-pull alkenes are substituted ethylenes containing electron-donor groups (D) at one end and electron-acceptor groups (A) at the other end of the general formula D¹D²C=CA¹A². These compounds very often contain alkoxy, amino, alkylamino, dialkylamino or (hetero)aryl groups as electron-donor groups and cyano, acetyl, alkylester, methylsulfonyl or NO₂ groups as electron-acceptor groups. They are useful as starting reactants or intermediates for a lot of pharmaceutical, polymer and other syntheses (Cook, 1969; Dyke, 1973). Mainly enamines are frequently used as reactants or intermediates in chemical syntheses of drugs, polymers and dyes (Bouzard, 1990). But also alkoxymethylenes are often used in organic synthesis (Freeman, 1981).

Chemical and physical properties of the title related structures were recently discussed (Gróf et al., 2008 and literature cited therein).

The study of a similar compound, dimethyl 2-(aminomethylene)malonate, (Gróf et al., 2008) revealed that this structure exists in the solid phase as EZ conformer (E denotes away from C=C double bond orientation of the carbonyl oxygen in trans position; Z denotes towards to C=C double bond orientation of the carbonyl oxygen in cis position). The title compound exists in the solid phase as ZZa conformer (a denotes anti orientation of the methylamino group, e.g. away from the C=C double bond orientation).

The molecules I and II, and molecules III and IV of the title compound (Fig.1) show pseudo translation (Kálmán & Argay, (1998).

Experimental

To dimethyl 3-methoxymethylenemalonate (1.74 g, 10 mmol) in methanol (10 ml), an aqueous solution of methylamine (12 mmol) was added dropwise (amount according to concentration and density) over a period of 30 min with stirring. The slightly warmed mixture was stirred overnight at room temperature. The reaction mixture was then briefly heated to reflux (ca. 20 min). After ensuring that no starting derivative remained (thin-layer chromatography; Silufol 254, Kavalier Czechoslovakia; eluent chloroform-methanol 10:1 v/v, detection UV light 254 nm), the reaction mixture was evaporated on a vacuum evaporator and chromatographed on silica gel (eluent dichloromethane-methanol 10:1 v/v). Obtained product was recrystallized from minimal amount of chloroform and n-hexane mixture in refrigerator.

The solid phase mid-IR vibrational spectrum was recorded with a Nicolet model NEXUS 470 FTIR spectrometer at room temperature. The measurement was performed after mixing the powdered sample with KBr into a pellet.

The mid-IR vibrational frequencies of dimethyl 2-(methylaminomethylene)malonate are (in cm^-1): 3301 m; 3199 w, sh, b; 3092 vw; 3052 vw; 3039 vw; 3013 w; 2999 w; 2951 m; 2924 w, sh; 2905 vw, sh; 1701 vw, sh; 1680 v s; 1651 vw, sh; 1631 v s; 1612 w, sh; 1541 vw; 1478 w; 1450 m; 1430 m; 1405 m; 1360 s; 1330 vw, sh; 1322 m; 1281 s; 1225 s; 1187 m; 1151 s; 1082 m; 1042 w; 1018 m; 998 w; 942 vw; 837 vw, sh; 820 s; 808 s; 768 m; 759 vw, sh; 671 m; 579 w, b; 459 vw; 446 vw; 413 m.