Dimethyl 2-(2-quinolylmeth­yl)malonate

Liu, S.-X.; Zhang, Z.-H.; Yang, Y.-F.; Zhen, X.-L.; Han, J.-R.

doi:10.1107/S1600536810013930

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1383

https://doi.org/10.1107/S1600536810013930

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Dimethyl 2-(2-quinolylmethyl)malonate

Shou-Xin Liu,^a Zhao-Hui Zhang,^a Yu-Feng Yang,^a Xiao-Li Zhen ^b and Jian-Rong Han ^b ^*

^aCollege of Chemical & Pharmaceutical Engineering, Hebei University of Science & Technology, Shijiazhuang 050018, People's Republic of China, and ^bCollege of Sciences, Hebei University of Science & Technology, Shijiazhuang 050018, People's Republic of China
^*Correspondence e-mail: chlsx@263.net.

(Received 29 March 2010; accepted 15 April 2010; online 19 May 2010)

In the title compound, C₁₅H₁₅NO₄, the quinoline ring system and one of the malonate side chains are essentially coplanar (r.m.s. deviation = 0.0297 Å). The two malonate C—C(=O)—O—CH₃ side chains are oriented at right angles [89.68 (8)°] with respect to each other. The crystal packing is stabilized by weak non-classical intermolecular C—H⋯O hydrogen bonds, which link the molecules into dimers about inversion centers.

Related literature

For general background to the synthesis of halomalonates, see: Okimoto & Takahashi (2002 ).

Experimental

Crystal data

C₁₅H₁₅NO₄
M_r = 273.28
Monoclinic, P 2₁ /c
a = 10.626 (2) Å
b = 16.198 (3) Å
c = 8.1859 (16) Å
β = 107.92 (3)°
V = 1340.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.981, T_max = 0.988
8841 measured reflections
2355 independent reflections
2094 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.095
S = 1.07
2355 reflections
184 parameters
H-atom parameters constrained
Δρ_max = 0.23 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
C11—H11⋯O1ⁱ	0.98	2.49	3.410 (2)	157
Symmetry code: (i) -x+1, -y, -z+1.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810013930/pv2271sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810013930/pv2271Isup2.hkl

checkCIF report

Comment top

Substituted malonate 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 the title compound, (I), in our laboratory and report in this article its synthesis and crystal structure.

The molecular structure of (I) is presented in Fig. 1. In (I), the quinoline ring and the side chain atoms C10/C11/C14 are essentially planar [r.m.s. deviation, 0.0297 Å]. The two malonate side chains comprising C/C/O/C atoms (C11/C12/O1/C13 and C11/C14/O3/C15) are oriented at right angles (89.68 (8)°) with respect to each other. The crystal packing is stabilized by weak non-classical intermolecular C—H···O hydrogen bonds which link the molecules into dimers about inversion centers.

Related literature top

For general background to the synthesis of halomalonates, see: Okimoto & Takahashi (2002).

Experimental top

An anhydrous methanol solution (130 ml) of 2-brommethyl quinoline 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 4 h and the product was isolated with silica gel column. The solvent was removed and a little petroleum ether was added to the resultant to give pale-yellow precipitates which were isolated, recrystallized from n-hexane, and dried under vacuum to give the title compound (60% yield). Colorless single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an n-hexane solution.

Structure description top

For general background to the synthesis of halomalonates, see: Okimoto & Takahashi (2002).

Computing details top

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

Figures top

	Fig. 1. Ellipsoid plot.
	Fig. 2. Packing diagram.

Dimethyl 2-(2-quinolylmethyl)malonate top

Crystal data top

C₁₅H₁₅NO₄	F(000) = 576
M_r = 273.28	D_x = 1.354 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4229 reflections
a = 10.626 (2) Å	θ = 2.0–27.9°
b = 16.198 (3) Å	µ = 0.10 mm⁻¹
c = 8.1859 (16) Å	T = 113 K
β = 107.92 (3)°	Prism, colourless
V = 1340.6 (5) Å³	0.20 × 0.18 × 0.12 mm
Z = 4

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2355 independent reflections
Radiation source: rotating anode	2094 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.033
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 2.4°
ω and φ scans	h = −12→7
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −19→18
T_min = 0.981, T_max = 0.988	l = −9→9
8841 measured reflections

Refinement top

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)] = 0.035	H-atom parameters constrained
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0544P)² + 0.2353P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.003
2355 reflections	Δρ_max = 0.23 e Å⁻³
184 parameters	Δρ_min = −0.17 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: 0.133 (8)

Crystal data top

C₁₅H₁₅NO₄	V = 1340.6 (5) Å³
M_r = 273.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.626 (2) Å	µ = 0.10 mm⁻¹
b = 16.198 (3) Å	T = 113 K
c = 8.1859 (16) Å	0.20 × 0.18 × 0.12 mm
β = 107.92 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2355 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2094 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.988	R_int = 0.033
8841 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.07	Δρ_max = 0.23 e Å⁻³
2355 reflections	Δρ_min = −0.17 e Å⁻³
184 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.42646 (9)	0.11002 (5)	0.37324 (10)	0.0208 (2)
O2	0.28197 (9)	0.17212 (5)	0.48439 (11)	0.0238 (3)
O3	0.57807 (9)	0.20028 (5)	0.71040 (11)	0.0259 (3)
O4	0.58734 (10)	0.12269 (6)	0.94065 (12)	0.0315 (3)
N1	0.24000 (10)	−0.02029 (6)	0.47394 (13)	0.0193 (3)
C1	0.14301 (12)	−0.06967 (7)	0.37093 (16)	0.0186 (3)
C2	0.13159 (14)	−0.07574 (8)	0.19515 (17)	0.0249 (3)
H2	0.1898	−0.0466	0.1519	0.030*
C3	0.03559 (14)	−0.12414 (8)	0.08742 (17)	0.0275 (3)
H3	0.0287	−0.1271	−0.0285	0.033*
C4	−0.05277 (13)	−0.16937 (8)	0.15063 (17)	0.0240 (3)
H4	−0.1164	−0.2029	0.0771	0.029*
C5	−0.04480 (13)	−0.16388 (8)	0.32021 (17)	0.0217 (3)
H5	−0.1036	−0.1937	0.3612	0.026*
C6	0.05144 (13)	−0.11361 (7)	0.43356 (16)	0.0186 (3)
C7	0.06142 (13)	−0.10242 (8)	0.60895 (16)	0.0220 (3)
H7	0.0030	−0.1293	0.6554	0.026*
C8	0.15648 (13)	−0.05239 (8)	0.70838 (16)	0.0224 (3)
H8	0.1631	−0.0444	0.8232	0.027*
C9	0.24603 (12)	−0.01216 (7)	0.63656 (15)	0.0189 (3)
C10	0.35008 (13)	0.04359 (8)	0.74929 (15)	0.0210 (3)
H10A	0.4004	0.0127	0.8496	0.025*
H10B	0.3065	0.0886	0.7886	0.025*
C11	0.44620 (12)	0.07996 (7)	0.66261 (15)	0.0183 (3)
H11	0.4954	0.0344	0.6324	0.022*
C12	0.37365 (12)	0.12590 (7)	0.49881 (15)	0.0182 (3)
C13	0.35706 (15)	0.14582 (9)	0.20836 (16)	0.0306 (3)
H13A	0.2709	0.1213	0.1651	0.046*
H13B	0.4060	0.1357	0.1295	0.046*
H13C	0.3481	0.2042	0.2211	0.046*
C14	0.54437 (12)	0.13576 (8)	0.78861 (16)	0.0203 (3)
C15	0.67016 (15)	0.25858 (9)	0.81881 (19)	0.0318 (4)
H15A	0.6337	0.2801	0.9038	0.048*
H15B	0.6855	0.3030	0.7498	0.048*
H15C	0.7522	0.2312	0.8747	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0226 (5)	0.0238 (5)	0.0158 (5)	0.0004 (4)	0.0055 (4)	0.0020 (3)
O2	0.0218 (5)	0.0216 (5)	0.0273 (5)	0.0050 (4)	0.0067 (4)	0.0024 (4)
O3	0.0279 (5)	0.0222 (5)	0.0243 (5)	−0.0075 (4)	0.0032 (4)	−0.0002 (4)
O4	0.0320 (6)	0.0367 (6)	0.0204 (5)	−0.0099 (4)	0.0004 (4)	0.0007 (4)
N1	0.0180 (6)	0.0198 (6)	0.0194 (5)	0.0002 (4)	0.0048 (4)	0.0000 (4)
C1	0.0166 (7)	0.0180 (6)	0.0205 (6)	0.0025 (5)	0.0046 (5)	0.0006 (5)
C2	0.0233 (7)	0.0314 (7)	0.0216 (7)	−0.0043 (6)	0.0095 (6)	−0.0014 (5)
C3	0.0283 (8)	0.0353 (8)	0.0188 (7)	−0.0035 (6)	0.0070 (6)	−0.0043 (6)
C4	0.0198 (7)	0.0245 (7)	0.0247 (7)	−0.0015 (5)	0.0021 (6)	−0.0039 (5)
C5	0.0190 (7)	0.0194 (6)	0.0262 (7)	0.0003 (5)	0.0062 (6)	0.0026 (5)
C6	0.0179 (7)	0.0156 (6)	0.0218 (6)	0.0039 (5)	0.0054 (5)	0.0032 (5)
C7	0.0240 (7)	0.0212 (7)	0.0224 (7)	−0.0013 (5)	0.0094 (6)	0.0043 (5)
C8	0.0272 (7)	0.0225 (6)	0.0176 (6)	0.0000 (5)	0.0072 (6)	0.0024 (5)
C9	0.0207 (7)	0.0166 (6)	0.0184 (6)	0.0035 (5)	0.0045 (5)	0.0022 (5)
C10	0.0243 (7)	0.0212 (6)	0.0171 (6)	−0.0012 (5)	0.0059 (5)	0.0012 (5)
C11	0.0193 (7)	0.0174 (6)	0.0173 (6)	0.0010 (5)	0.0044 (5)	−0.0003 (5)
C12	0.0189 (7)	0.0155 (6)	0.0197 (6)	−0.0034 (5)	0.0052 (5)	−0.0015 (5)
C13	0.0328 (8)	0.0384 (8)	0.0182 (7)	−0.0002 (6)	0.0044 (6)	0.0070 (6)
C14	0.0180 (7)	0.0215 (7)	0.0212 (7)	0.0028 (5)	0.0059 (5)	0.0002 (5)
C15	0.0280 (8)	0.0252 (7)	0.0368 (8)	−0.0083 (6)	0.0019 (7)	−0.0041 (6)

Geometric parameters (Å, º) top

O1—C12	1.3389 (15)	C6—C7	1.4184 (18)
O1—C13	1.4454 (16)	C7—C8	1.3542 (19)
O2—C12	1.2054 (15)	C7—H7	0.9300
O3—C14	1.3309 (15)	C8—C9	1.4212 (18)
O3—C15	1.4500 (16)	C8—H8	0.9300
O4—C14	1.2052 (16)	C9—C10	1.5039 (18)
N1—C9	1.3195 (16)	C10—C11	1.5296 (17)
N1—C1	1.3705 (17)	C10—H10A	0.9700
C1—C2	1.4098 (18)	C10—H10B	0.9700
C1—C6	1.4222 (18)	C11—C14	1.5189 (18)
C2—C3	1.3710 (19)	C11—C12	1.5197 (17)
C2—H2	0.9300	C11—H11	0.9800
C3—C4	1.4089 (19)	C13—H13A	0.9600
C3—H3	0.9300	C13—H13B	0.9600
C4—C5	1.3673 (18)	C13—H13C	0.9600
C4—H4	0.9300	C15—H15A	0.9600
C5—C6	1.4093 (19)	C15—H15B	0.9600
C5—H5	0.9300	C15—H15C	0.9600

C12—O1—C13	115.21 (10)	C9—C10—C11	114.61 (10)
C14—O3—C15	116.60 (10)	C9—C10—H10A	108.6
C9—N1—C1	118.22 (11)	C11—C10—H10A	108.6
N1—C1—C2	118.74 (11)	C9—C10—H10B	108.6
N1—C1—C6	122.59 (11)	C11—C10—H10B	108.6
C2—C1—C6	118.65 (12)	H10A—C10—H10B	107.6
C3—C2—C1	120.65 (12)	C14—C11—C12	111.33 (10)
C3—C2—H2	119.7	C14—C11—C10	109.35 (10)
C1—C2—H2	119.7	C12—C11—C10	111.59 (10)
C2—C3—C4	120.61 (12)	C14—C11—H11	108.1
C2—C3—H3	119.7	C12—C11—H11	108.1
C4—C3—H3	119.7	C10—C11—H11	108.1
C5—C4—C3	119.93 (12)	O2—C12—O1	124.13 (11)
C5—C4—H4	120.0	O2—C12—C11	124.46 (11)
C3—C4—H4	120.0	O1—C12—C11	111.39 (10)
C4—C5—C6	120.78 (12)	O1—C13—H13A	109.5
C4—C5—H5	119.6	O1—C13—H13B	109.5
C6—C5—H5	119.6	H13A—C13—H13B	109.5
C5—C6—C7	123.60 (12)	O1—C13—H13C	109.5
C5—C6—C1	119.35 (11)	H13A—C13—H13C	109.5
C7—C6—C1	117.04 (12)	H13B—C13—H13C	109.5
C8—C7—C6	119.63 (11)	O4—C14—O3	124.21 (12)
C8—C7—H7	120.2	O4—C14—C11	124.03 (12)
C6—C7—H7	120.2	O3—C14—C11	111.76 (10)
C7—C8—C9	119.76 (11)	O3—C15—H15A	109.5
C7—C8—H8	120.1	O3—C15—H15B	109.5
C9—C8—H8	120.1	H15A—C15—H15B	109.5
N1—C9—C8	122.73 (12)	O3—C15—H15C	109.5
N1—C9—C10	118.51 (11)	H15A—C15—H15C	109.5
C8—C9—C10	118.74 (11)	H15B—C15—H15C	109.5

C9—N1—C1—C2	177.02 (11)	C7—C8—C9—N1	1.02 (19)
C9—N1—C1—C6	−1.52 (17)	C7—C8—C9—C10	179.55 (11)
N1—C1—C2—C3	−179.71 (12)	N1—C9—C10—C11	−4.71 (16)
C6—C1—C2—C3	−1.11 (19)	C8—C9—C10—C11	176.70 (11)
C1—C2—C3—C4	−0.6 (2)	C9—C10—C11—C14	179.17 (10)
C2—C3—C4—C5	1.3 (2)	C9—C10—C11—C12	55.55 (14)
C3—C4—C5—C6	−0.27 (19)	C13—O1—C12—O2	−6.25 (17)
C4—C5—C6—C7	177.20 (12)	C13—O1—C12—C11	175.19 (10)
C4—C5—C6—C1	−1.43 (18)	C14—C11—C12—O2	−79.24 (15)
N1—C1—C6—C5	−179.36 (11)	C10—C11—C12—O2	43.25 (16)
C2—C1—C6—C5	2.10 (17)	C14—C11—C12—O1	99.32 (11)
N1—C1—C6—C7	1.92 (17)	C10—C11—C12—O1	−138.19 (11)
C2—C1—C6—C7	−176.62 (11)	C15—O3—C14—O4	−1.50 (18)
C5—C6—C7—C8	−179.49 (12)	C15—O3—C14—C11	179.13 (10)
C1—C6—C7—C8	−0.82 (18)	C12—C11—C14—O4	159.19 (13)
C6—C7—C8—C9	−0.55 (19)	C10—C11—C14—O4	35.42 (17)
C1—N1—C9—C8	0.03 (17)	C12—C11—C14—O3	−21.44 (14)
C1—N1—C9—C10	−178.51 (10)	C10—C11—C14—O3	−145.21 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1ⁱ	0.98	2.49	3.410 (2)	157

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅NO₄
M_r	273.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	10.626 (2), 16.198 (3), 8.1859 (16)
β (°)	107.92 (3)
V (Å³)	1340.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.18 × 0.12

Data collection
Diffractometer	Rigaku Saturn CCD area-detector
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.981, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	8841, 2355, 2094
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.095, 1.07
No. of reflections	2355
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.17

Computer programs: CrystalClear (Rigaku/MSC, 2005), CrystalClear (Rigaku/MSC, 2005, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1ⁱ	0.98	2.49	3.410 (2)	157.0

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

This work was supported by the NSFC (grant No. 30873139).

References

Okimoto, M. & Takahashi, Y. (2002). Synthesis, 15, 2215–2219 Web of Science CrossRef Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar