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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1383.
Published online 2010 May 19. doi:  10.1107/S1600536810013930
PMCID: PMC2979390

Dimethyl 2-(2-quinolylmeth­yl)malonate

Abstract

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 [triangle]).

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Object name is e-66-o1383-scheme1.jpg

Experimental

Crystal data

  • C15H15NO4
  • M r = 273.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1383-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.095
  • S = 1.07
  • 2355 reflections
  • 184 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013930/pv2271Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

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

Figures

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

Crystal data

C15H15NO4F(000) = 576
Mr = 273.28Dx = 1.354 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4229 reflections
a = 10.626 (2) Åθ = 2.0–27.9°
b = 16.198 (3) ŵ = 0.10 mm1
c = 8.1859 (16) ÅT = 113 K
β = 107.92 (3)°Prism, colourless
V = 1340.6 (5) Å30.20 × 0.18 × 0.12 mm
Z = 4

Data collection

Rigaku Saturn CCD area-detector diffractometer2355 independent reflections
Radiation source: rotating anode2094 reflections with I > 2σ(I)
confocalRint = 0.033
Detector resolution: 7.31 pixels mm-1θmax = 25.0°, θmin = 2.4°
ω and [var phi] scansh = −12→7
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)k = −19→18
Tmin = 0.981, Tmax = 0.988l = −9→9
8841 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.095w = 1/[σ2(Fo2) + (0.0544P)2 + 0.2353P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.003
2355 reflectionsΔρmax = 0.23 e Å3
184 parametersΔρmin = −0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.133 (8)

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 (Å2)

xyzUiso*/Ueq
O10.42646 (9)0.11002 (5)0.37324 (10)0.0208 (2)
O20.28197 (9)0.17212 (5)0.48439 (11)0.0238 (3)
O30.57807 (9)0.20028 (5)0.71040 (11)0.0259 (3)
O40.58734 (10)0.12269 (6)0.94065 (12)0.0315 (3)
N10.24000 (10)−0.02029 (6)0.47394 (13)0.0193 (3)
C10.14301 (12)−0.06967 (7)0.37093 (16)0.0186 (3)
C20.13159 (14)−0.07574 (8)0.19515 (17)0.0249 (3)
H20.1898−0.04660.15190.030*
C30.03559 (14)−0.12414 (8)0.08742 (17)0.0275 (3)
H30.0287−0.1271−0.02850.033*
C4−0.05277 (13)−0.16937 (8)0.15063 (17)0.0240 (3)
H4−0.1164−0.20290.07710.029*
C5−0.04480 (13)−0.16388 (8)0.32021 (17)0.0217 (3)
H5−0.1036−0.19370.36120.026*
C60.05144 (13)−0.11361 (7)0.43356 (16)0.0186 (3)
C70.06142 (13)−0.10242 (8)0.60895 (16)0.0220 (3)
H70.0030−0.12930.65540.026*
C80.15648 (13)−0.05239 (8)0.70838 (16)0.0224 (3)
H80.1631−0.04440.82320.027*
C90.24603 (12)−0.01216 (7)0.63656 (15)0.0189 (3)
C100.35008 (13)0.04359 (8)0.74929 (15)0.0210 (3)
H10A0.40040.01270.84960.025*
H10B0.30650.08860.78860.025*
C110.44620 (12)0.07996 (7)0.66261 (15)0.0183 (3)
H110.49540.03440.63240.022*
C120.37365 (12)0.12590 (7)0.49881 (15)0.0182 (3)
C130.35706 (15)0.14582 (9)0.20836 (16)0.0306 (3)
H13A0.27090.12130.16510.046*
H13B0.40600.13570.12950.046*
H13C0.34810.20420.22110.046*
C140.54437 (12)0.13576 (8)0.78861 (16)0.0203 (3)
C150.67016 (15)0.25858 (9)0.81881 (19)0.0318 (4)
H15A0.63370.28010.90380.048*
H15B0.68550.30300.74980.048*
H15C0.75220.23120.87470.048*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0226 (5)0.0238 (5)0.0158 (5)0.0004 (4)0.0055 (4)0.0020 (3)
O20.0218 (5)0.0216 (5)0.0273 (5)0.0050 (4)0.0067 (4)0.0024 (4)
O30.0279 (5)0.0222 (5)0.0243 (5)−0.0075 (4)0.0032 (4)−0.0002 (4)
O40.0320 (6)0.0367 (6)0.0204 (5)−0.0099 (4)0.0004 (4)0.0007 (4)
N10.0180 (6)0.0198 (6)0.0194 (5)0.0002 (4)0.0048 (4)0.0000 (4)
C10.0166 (7)0.0180 (6)0.0205 (6)0.0025 (5)0.0046 (5)0.0006 (5)
C20.0233 (7)0.0314 (7)0.0216 (7)−0.0043 (6)0.0095 (6)−0.0014 (5)
C30.0283 (8)0.0353 (8)0.0188 (7)−0.0035 (6)0.0070 (6)−0.0043 (6)
C40.0198 (7)0.0245 (7)0.0247 (7)−0.0015 (5)0.0021 (6)−0.0039 (5)
C50.0190 (7)0.0194 (6)0.0262 (7)0.0003 (5)0.0062 (6)0.0026 (5)
C60.0179 (7)0.0156 (6)0.0218 (6)0.0039 (5)0.0054 (5)0.0032 (5)
C70.0240 (7)0.0212 (7)0.0224 (7)−0.0013 (5)0.0094 (6)0.0043 (5)
C80.0272 (7)0.0225 (6)0.0176 (6)0.0000 (5)0.0072 (6)0.0024 (5)
C90.0207 (7)0.0166 (6)0.0184 (6)0.0035 (5)0.0045 (5)0.0022 (5)
C100.0243 (7)0.0212 (6)0.0171 (6)−0.0012 (5)0.0059 (5)0.0012 (5)
C110.0193 (7)0.0174 (6)0.0173 (6)0.0010 (5)0.0044 (5)−0.0003 (5)
C120.0189 (7)0.0155 (6)0.0197 (6)−0.0034 (5)0.0052 (5)−0.0015 (5)
C130.0328 (8)0.0384 (8)0.0182 (7)−0.0002 (6)0.0044 (6)0.0070 (6)
C140.0180 (7)0.0215 (7)0.0212 (7)0.0028 (5)0.0059 (5)0.0002 (5)
C150.0280 (8)0.0252 (7)0.0368 (8)−0.0083 (6)0.0019 (7)−0.0041 (6)

Geometric parameters (Å, °)

O1—C121.3389 (15)C6—C71.4184 (18)
O1—C131.4454 (16)C7—C81.3542 (19)
O2—C121.2054 (15)C7—H70.9300
O3—C141.3309 (15)C8—C91.4212 (18)
O3—C151.4500 (16)C8—H80.9300
O4—C141.2052 (16)C9—C101.5039 (18)
N1—C91.3195 (16)C10—C111.5296 (17)
N1—C11.3705 (17)C10—H10A0.9700
C1—C21.4098 (18)C10—H10B0.9700
C1—C61.4222 (18)C11—C141.5189 (18)
C2—C31.3710 (19)C11—C121.5197 (17)
C2—H20.9300C11—H110.9800
C3—C41.4089 (19)C13—H13A0.9600
C3—H30.9300C13—H13B0.9600
C4—C51.3673 (18)C13—H13C0.9600
C4—H40.9300C15—H15A0.9600
C5—C61.4093 (19)C15—H15B0.9600
C5—H50.9300C15—H15C0.9600
C12—O1—C13115.21 (10)C9—C10—C11114.61 (10)
C14—O3—C15116.60 (10)C9—C10—H10A108.6
C9—N1—C1118.22 (11)C11—C10—H10A108.6
N1—C1—C2118.74 (11)C9—C10—H10B108.6
N1—C1—C6122.59 (11)C11—C10—H10B108.6
C2—C1—C6118.65 (12)H10A—C10—H10B107.6
C3—C2—C1120.65 (12)C14—C11—C12111.33 (10)
C3—C2—H2119.7C14—C11—C10109.35 (10)
C1—C2—H2119.7C12—C11—C10111.59 (10)
C2—C3—C4120.61 (12)C14—C11—H11108.1
C2—C3—H3119.7C12—C11—H11108.1
C4—C3—H3119.7C10—C11—H11108.1
C5—C4—C3119.93 (12)O2—C12—O1124.13 (11)
C5—C4—H4120.0O2—C12—C11124.46 (11)
C3—C4—H4120.0O1—C12—C11111.39 (10)
C4—C5—C6120.78 (12)O1—C13—H13A109.5
C4—C5—H5119.6O1—C13—H13B109.5
C6—C5—H5119.6H13A—C13—H13B109.5
C5—C6—C7123.60 (12)O1—C13—H13C109.5
C5—C6—C1119.35 (11)H13A—C13—H13C109.5
C7—C6—C1117.04 (12)H13B—C13—H13C109.5
C8—C7—C6119.63 (11)O4—C14—O3124.21 (12)
C8—C7—H7120.2O4—C14—C11124.03 (12)
C6—C7—H7120.2O3—C14—C11111.76 (10)
C7—C8—C9119.76 (11)O3—C15—H15A109.5
C7—C8—H8120.1O3—C15—H15B109.5
C9—C8—H8120.1H15A—C15—H15B109.5
N1—C9—C8122.73 (12)O3—C15—H15C109.5
N1—C9—C10118.51 (11)H15A—C15—H15C109.5
C8—C9—C10118.74 (11)H15B—C15—H15C109.5
C9—N1—C1—C2177.02 (11)C7—C8—C9—N11.02 (19)
C9—N1—C1—C6−1.52 (17)C7—C8—C9—C10179.55 (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—C11176.70 (11)
C1—C2—C3—C4−0.6 (2)C9—C10—C11—C14179.17 (10)
C2—C3—C4—C51.3 (2)C9—C10—C11—C1255.55 (14)
C3—C4—C5—C6−0.27 (19)C13—O1—C12—O2−6.25 (17)
C4—C5—C6—C7177.20 (12)C13—O1—C12—C11175.19 (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—O243.25 (16)
C2—C1—C6—C52.10 (17)C14—C11—C12—O199.32 (11)
N1—C1—C6—C71.92 (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—C11179.13 (10)
C1—C6—C7—C8−0.82 (18)C12—C11—C14—O4159.19 (13)
C6—C7—C8—C9−0.55 (19)C10—C11—C14—O435.42 (17)
C1—N1—C9—C80.03 (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, °)

D—H···AD—HH···AD···AD—H···A
C11—H11···O1i0.982.493.410 (2)157

Symmetry codes: (i) −x+1, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2271).

References

  • Okimoto, M. & Takahashi, Y. (2002). Synthesis, 15, 2215–2219
  • Rigaku/MSC (2005). CrystalClear Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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