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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2824.
Published online 2009 October 23. doi:  10.1107/S1600536809042639
PMCID: PMC2971291

2-(Methoxy­meth­yl)adamantan-2-yl 2-methyl­acrylate

Abstract

The title compound, C16H24O3, has a cage-type mol­ecular structure and is of inter­est with respect to its photochemical properties. The structure displays non-classical inter­molecular C—H(...)O hydrogen bonding, which links the mol­ecules into a three-dimensional network.

Related literature

For the synthesis of the title compound and its analogues, see: Hui et al. (2007 [triangle]); Isobe et al. (2007 [triangle]); Kikugawa (2009 [triangle]); Sasaki et al. (2007 [triangle]); Takahashi et al. (2006 [triangle]). For related photoresist preparations, see: Chen et al. (2009 [triangle]); Fedynyshyn (2009 [triangle]); Okago et al. (2009 [triangle]); Padmanaban et al. (2009 [triangle]); Yoo et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2824-scheme1.jpg

Experimental

Crystal data

  • C16H24O3
  • M r = 264.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2824-efi1.jpg
  • a = 14.1385 (12) Å
  • b = 7.5265 (7) Å
  • c = 13.9712 (12) Å
  • β = 102.461 (6)°
  • V = 1451.7 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 298 K
  • 0.40 × 0.35 × 0.30 mm

Data collection

  • Bruker SMART APEXII CCD diffractometer
  • Absorption correction: none
  • 9914 measured reflections
  • 3701 independent reflections
  • 2096 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.159
  • S = 1.03
  • 3701 reflections
  • 173 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.13 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; 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/S1600536809042639/rk2167sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809042639/rk2167Isup2.hkl

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

Acknowledgments

We thank Dr Yanhui Chen for his help with the refinement.

supplementary crystallographic information

Comment

The photoresist is the key material for the preparation of integrated circuit plates. With the development of integrated circuit, the quest for high performance of the photoresist is changing. From 1993 till now, 193 nm photoresist is always being a research hot spot. As the important monomers of polymer matrix for 193 nm photoresist, adamant-2-yl methacrylates are potential and the design of such compounds has received significant attention (Chen et al., 2009; Fedynyshyn, 2009; Hui et al., 2007; Isobe et al., 2007; Kikugawa, 2009; Okago et al., 2009; Padmanaban et al., 2009; Sasaki et al., 2007; Takahashi et al., 2006; Yoo et al. 2009).

As a part of studying the effect of side chain substitution on the structures of adamant-2-yl methacrylates, the crystal structure of 2-methyl-acrylic acid 2-methoxymethyl-adamantan-2-yl ester has been determined. The title compound is prepared via three steps including Grignard reaction, etherafication and esterification (Fig. 1). The conformation of the C═O and C═C bonds of the methacrylic group are syn to each other but not coplanar (Fig.2). The torsion angle O1–C9–C12═C16 is equal to 9.4 (3)°. The geometry of the molecule as well as 1.1996 (19)Å, 1.478 (2)Å and 1.340 (2)Å distances of O1–C9, C9–C12 and C12═C16 bonds, indicate no obvious delocalization of the electron pairs of C═O and C═C within the methacrylic group. The non-classical C16–H16A···O2i intermolecular hydrogen bonds link the molecules into a three-dimensional network (Table 1, Fig. 3). Symmetry code (i): x, -y+5/2, z-1/2.

Experimental

The synthesis of title compound was shown in Fig.1. The crude product was recrystalized by petroleum ether in the yield of 60%. 1H-NMR (CDCl3, 400 MHz): 1.58-2.53 (14H, m), 1.95 (3H, s), 3.35 (3H, s), 4.08 (2H, s), 5.52 (1H, s), 6.10 (1H, s); Elemental analysis (%) Calcd (Found): C: 72.25 (72.69), H: 9.16 (9.15), O: 18.40 (18.16).

Refinement

All H atoms attached to C atoms were treated as riding, with C–H = 0.9700Å for ethylene group, with C–H = 0.9700Å for methylene group, C–H = 0.9800Å for methyne group and C–H = 0.9600Å for methyl group with Uiso(H) = 1.2Ueq(C) of the carrier atoms to which they are attached and Uiso(H) = 1.5Ueq(C) for the methyl groups.

Figures

Fig. 1.
The synthesis path of title compound.
Fig. 2.
The molecular structure of title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.
Fig. 3.
Molecular packing in the crystal. Hydrogen bonds are shown as dashed lines.

Crystal data

C16H24O3F(000) = 576
Mr = 264.35Dx = 1.210 Mg m3
Monoclinic, P21/cMelting point: 318 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 14.1385 (12) ÅCell parameters from 2653 reflections
b = 7.5265 (7) Åθ = 3.0–25.0°
c = 13.9712 (12) ŵ = 0.08 mm1
β = 102.461 (6)°T = 298 K
V = 1451.7 (2) Å3Block, colourless
Z = 40.40 × 0.35 × 0.30 mm

Data collection

Bruker SMART APEXII CCD diffractometer2096 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
graphiteθmax = 28.7°, θmin = 1.5°
[var phi] and ω scansh = −19→18
9914 measured reflectionsk = −6→10
3701 independent reflectionsl = −18→18

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.159w = 1/[σ2(Fo2) + (0.0765P)2 + 0.0779P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3701 reflectionsΔρmax = 0.15 e Å3
173 parametersΔρmin = −0.13 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: 0.036 (4)

Special details

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

xyzUiso*/Ueq
O30.72029 (7)1.00159 (13)0.70066 (7)0.0492 (3)
C20.73378 (10)0.86448 (19)0.77704 (10)0.0475 (4)
C30.78456 (12)0.7003 (2)0.74679 (11)0.0523 (4)
H3A0.74190.64150.69120.063*
C40.87843 (11)0.7558 (2)0.71813 (11)0.0564 (4)
H4A0.90960.65230.69740.068*
H4B0.86410.83830.66360.068*
O20.59138 (8)0.97066 (16)0.82779 (9)0.0729 (4)
C60.80243 (11)0.9541 (2)0.86316 (11)0.0530 (4)
H6A0.77131.06040.88270.064*
C70.94636 (12)0.8433 (2)0.80430 (11)0.0614 (5)
H7A1.00640.87810.78510.074*
O10.63265 (9)0.83342 (17)0.58041 (9)0.0746 (4)
C90.67070 (11)0.9716 (2)0.60916 (12)0.0518 (4)
C100.63535 (12)0.8197 (2)0.79806 (13)0.0612 (5)
H10A0.59390.77080.73950.073*
H10B0.64320.73030.84910.073*
C110.89683 (12)1.0069 (2)0.83410 (12)0.0593 (5)
H11A0.88311.09020.77990.071*
H11B0.93951.06490.88890.071*
C120.66997 (12)1.1315 (2)0.54756 (11)0.0563 (4)
C130.87610 (14)0.6618 (3)0.91968 (12)0.0724 (6)
H13A0.89090.57920.97510.087*
C140.96933 (13)0.7145 (3)0.88993 (13)0.0743 (6)
H14A1.00090.60960.87120.089*
H14B1.01300.77010.94480.089*
C150.80964 (14)0.5713 (2)0.83353 (13)0.0682 (5)
H15A0.75070.53320.85250.082*
H15B0.84140.46700.81440.082*
C160.61220 (14)1.1289 (3)0.45791 (13)0.0762 (6)
H16A0.60881.22770.41730.091*
H16B0.57551.02850.43630.091*
C170.82633 (15)0.8258 (3)0.94946 (12)0.0694 (5)
H17A0.86860.88351.00460.083*
H17B0.76730.79130.96930.083*
C180.72945 (16)1.2843 (3)0.58613 (15)0.0865 (6)
H18A0.72061.37670.53760.130*
H18B0.79641.24980.60230.130*
H18C0.71051.32730.64390.130*
C190.50466 (14)0.9249 (3)0.85691 (17)0.0884 (7)
H19A0.47571.03010.87690.133*
H19B0.51890.84280.91070.133*
H19C0.46050.87090.80290.133*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O30.0590 (6)0.0445 (6)0.0440 (6)−0.0045 (5)0.0108 (5)0.0001 (5)
C20.0569 (9)0.0424 (9)0.0452 (8)−0.0030 (7)0.0152 (7)0.0032 (6)
C30.0641 (9)0.0441 (9)0.0484 (9)0.0007 (7)0.0116 (7)−0.0037 (7)
C40.0652 (10)0.0590 (10)0.0477 (9)0.0097 (8)0.0180 (8)−0.0025 (7)
O20.0659 (8)0.0589 (8)0.1038 (10)0.0058 (6)0.0402 (7)0.0083 (7)
C60.0657 (10)0.0538 (10)0.0410 (8)0.0004 (8)0.0148 (7)−0.0064 (7)
C70.0559 (10)0.0743 (12)0.0550 (10)0.0008 (8)0.0138 (8)−0.0043 (8)
O10.0801 (9)0.0617 (8)0.0703 (8)−0.0072 (6)−0.0098 (6)−0.0078 (6)
C90.0494 (9)0.0534 (10)0.0508 (9)0.0042 (8)0.0069 (7)−0.0043 (8)
C100.0634 (10)0.0510 (10)0.0750 (11)−0.0036 (8)0.0278 (9)0.0027 (8)
C110.0613 (10)0.0633 (11)0.0509 (9)−0.0100 (8)0.0070 (8)−0.0099 (8)
C120.0599 (10)0.0617 (11)0.0497 (9)0.0121 (8)0.0171 (8)0.0040 (8)
C130.0928 (14)0.0767 (13)0.0481 (10)0.0222 (11)0.0158 (10)0.0158 (9)
C140.0721 (12)0.0890 (14)0.0571 (10)0.0170 (10)0.0038 (9)−0.0038 (10)
C150.0838 (12)0.0502 (10)0.0742 (12)0.0096 (9)0.0252 (10)0.0105 (9)
C160.0827 (13)0.0820 (14)0.0611 (11)0.0171 (11)0.0097 (10)0.0073 (10)
C170.0880 (13)0.0784 (13)0.0442 (9)0.0110 (10)0.0197 (9)0.0033 (9)
C180.1140 (17)0.0687 (13)0.0771 (13)−0.0163 (12)0.0210 (12)0.0151 (11)
C190.0695 (12)0.0876 (15)0.1194 (17)0.0119 (11)0.0458 (12)0.0176 (13)

Geometric parameters (Å, °)

O3—C91.3379 (19)C11—H11A0.9700
O3—C21.4671 (17)C11—H11B0.9700
C2—C101.521 (2)C12—C161.340 (2)
C2—C61.530 (2)C12—C181.458 (2)
C2—C31.534 (2)C13—C141.518 (3)
C3—C41.525 (2)C13—C151.519 (3)
C3—C151.534 (2)C13—C171.523 (2)
C3—H3A0.9800C13—H13A0.9800
C4—C71.518 (2)C14—H14A0.9700
C4—H4A0.9700C14—H14B0.9700
C4—H4B0.9700C15—H15A0.9700
O2—C101.4004 (19)C15—H15B0.9700
O2—C191.4150 (19)C16—H16A0.9300
C6—C171.524 (2)C16—H16B0.9300
C6—C111.529 (2)C17—H17A0.9700
C6—H6A0.9800C17—H17B0.9700
C7—C111.519 (2)C18—H18A0.9600
C7—C141.520 (2)C18—H18B0.9600
C7—H7A0.9800C18—H18C0.9600
O1—C91.1996 (19)C19—H19A0.9600
C9—C121.478 (2)C19—H19B0.9600
C10—H10A0.9700C19—H19C0.9600
C10—H10B0.9700
C9—O3—C2122.37 (12)C6—C11—H11B109.7
O3—C2—C10108.39 (12)H11A—C11—H11B108.2
O3—C2—C6102.87 (11)C16—C12—C18122.91 (18)
C10—C2—C6113.42 (12)C16—C12—C9117.33 (17)
O3—C2—C3111.18 (11)C18—C12—C9119.75 (15)
C10—C2—C3112.16 (13)C14—C13—C15108.99 (13)
C6—C2—C3108.46 (12)C14—C13—C17110.06 (17)
C4—C3—C2109.71 (13)C15—C13—C17109.69 (15)
C4—C3—C15108.37 (13)C14—C13—H13A109.4
C2—C3—C15109.55 (12)C15—C13—H13A109.4
C4—C3—H3A109.7C17—C13—H13A109.4
C2—C3—H3A109.7C13—C14—C7109.36 (14)
C15—C3—H3A109.7C13—C14—H14A109.8
C7—C4—C3110.37 (12)C7—C14—H14A109.8
C7—C4—H4A109.6C13—C14—H14B109.8
C3—C4—H4A109.6C7—C14—H14B109.8
C7—C4—H4B109.6H14A—C14—H14B108.3
C3—C4—H4B109.6C13—C15—C3109.86 (15)
H4A—C4—H4B108.1C13—C15—H15A109.7
C10—O2—C19110.83 (14)C3—C15—H15A109.7
C17—C6—C11108.51 (14)C13—C15—H15B109.7
C17—C6—C2109.73 (14)C3—C15—H15B109.7
C11—C6—C2110.36 (11)H15A—C15—H15B108.2
C17—C6—H6A109.4C12—C16—H16A120.0
C11—C6—H6A109.4C12—C16—H16B120.0
C2—C6—H6A109.4H16A—C16—H16B120.0
C4—C7—C11108.58 (13)C13—C17—C6109.51 (12)
C4—C7—C14109.81 (15)C13—C17—H17A109.8
C11—C7—C14109.53 (13)C6—C17—H17A109.8
C4—C7—H7A109.6C13—C17—H17B109.8
C11—C7—H7A109.6C6—C17—H17B109.8
C14—C7—H7A109.6H17A—C17—H17B108.2
O1—C9—O3124.81 (15)C12—C18—H18A109.5
O1—C9—C12124.37 (16)C12—C18—H18B109.5
O3—C9—C12110.82 (14)H18A—C18—H18B109.5
O2—C10—C2111.15 (13)C12—C18—H18C109.5
O2—C10—H10A109.4H18A—C18—H18C109.5
C2—C10—H10A109.4H18B—C18—H18C109.5
O2—C10—H10B109.4O2—C19—H19A109.5
C2—C10—H10B109.4O2—C19—H19B109.5
H10A—C10—H10B108.0H19A—C19—H19B109.5
C7—C11—C6110.02 (14)O2—C19—H19C109.5
C7—C11—H11A109.7H19A—C19—H19C109.5
C6—C11—H11A109.7H19B—C19—H19C109.5
C7—C11—H11B109.7

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C16—H16A···O2i0.932.583.499 (2)171

Symmetry codes: (i) x, −y+5/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2167).

References

  • Bruker (2001). SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2005). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, K.-J., Huang, W.-S., Li, W.-K. & Varanasi, P. R. (2009). US Patent US2009130590.
  • Fedynyshyn, T. H. (2009). US Patent US2009068589.
  • Hui, C., Meng, Q.-W., Gong, B. & Qu, J.-P. (2007). Ganguang Kexue Yu Guang Huaxue, 25, 357–363.
  • Isobe, T., Kadota, M., Arai, Y. & Suzuki, M. (2007). Jpn Patent JP2007022918.
  • Kikugawa, T. (2009). Jpn Patent JP2008088152.
  • Okago, Y., Cho, Y.-H. & Kusaka, H. (2009). Jpn Patent JP2009114381.
  • Padmanaban, M., Chakrapani, S. & Lin, G.-Y. (2009). US Patent US2009042148.
  • Sasaki, M., Nishimura, Y. & &Akamatsu, J. (2007). Jpn Patent JP2007277118.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
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  • Yoo, G. U., Park, H. U. & Kim, S. T. (2009). KR Patent KR2009008039.

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