Methyl 4-(trimethyl­silylethyn­yl)benzoate

Potts, S.; Das, D.; Bredenkamp, M.W.

doi:10.1107/S1600536808008192

organic compounds

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Volume 64| Part 6| June 2008| Page o966

doi:10.1107/S1600536808008192

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Methyl 4-(trimethylsilylethynyl)benzoate

Storm Potts,^a ^* Dinabandhu Das ^a and Martin W. Bredenkamp ^a

^aDepartment of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland, 7602, South Africa
^*Correspondence e-mail: storm@sun.ac.za

(Received 1 February 2008; accepted 26 March 2008; online 3 May 2008)

The title compound, C₁₃H₁₆O₂Si, was synthesized as a precursor for ethynylarene derivatives and crystallized from hexane. In the crystal structure, molecules are linked by weak C—H⋯O hydrogen bonds to form chains that pack in layers in a herringbone fashion.

Related literature

For related literature, see: Eddaoudi et al. (2001 ); Dybtsev et al. (2004 ); Kesanli et al. (2005 ); Zhao et al. (2004 ); Allen et al. (1987 ); Fasina et al. (2005 ).

Experimental

Crystal data

C₁₃H₁₆O₂Si
M_r = 232.35
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.1983 (11) Å
b = 7.1194 (12) Å
c = 29.530 (5) Å
V = 1303.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 100 (2) K
0.25 × 0.24 × 0.08 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.960, T_max = 0.987
8160 measured reflections
3050 independent reflections
2643 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.114
S = 1.10
3050 reflections
149 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ), 1136 Friedel pairs
Flack parameter: −0.01 (19)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯O1ⁱ	0.98	2.58	3.470 (4)	151
C12—H12A⋯O1ⁱⁱ	0.98	2.57	3.527 (3)	167
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2003 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ; Atwood & Barbour, 2003 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536808008192/ez2120sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808008192/ez2120Isup2.hkl

checkCIF report

Comment top

The title compound was isolated as a precursor in the synthesis of a series of ethynylarene-based ligands with terminal carboxylate groups. Interest in these kinds of ligands can be attributed to their ability to incorporate metal ions into M—O—C clusters, leading to novel metal-organic frameworks (MOFs), a category of compounds gaining increasing interest due to their potential applications for gas storage and separation and catalysis (Eddaoudi et al., 2001; Dybtsev et al., 2004; Kesanli et al., 2005; Zhao et al., 2004). The structure of the title compound (I) is shown in Fig. 1. Molecules of (I) pack in layers parallel to the (010) plane forming herring-bone motifs (Fig. 2). Analysis of the crystal packing shows that the molecules are arranged in alternating directions in the layer, due to the bulky trimethylsilyl groups facilitating the close packing of the molecules with the adjacent layer along the c axis. The methyl hydrogen atoms of the trimethysilyl group form C—H···O hydrogen bonds with the carbonyl oxygen atom on the adjacent molecule (Fig. 3).

The acetylenic bond distance [C9—C10 1.200 (3) Å] corresponds with the average value detailed in Allen et al. (1987) for C_sp≡ C_sp–C_sp2 (Ar).

Related literature top

For related literature, see: Eddaoudi et al. (2001); Dybtsev et al. (2004); Kesanli et al. (2005); Zhao et al. (2004); Allen et al. (1987); Fasina et al. (2005).

Experimental top

The title compound (I), was synthesized from trimethylsilylacetylene and 4-iodo(methylbenzoate) using a Sonogashira cross-coupling-type reaction as detailed in (Fasina et al., 2005). Recrystallization from hexane afforded crystals of the title compound.

¹H and ¹³C NMR spectra were recorded as an additional method of characterization, ¹H NMR (CDCl₃, 400 MHz): δ = 0.22 (9H, s, SiCH₃), 3.89 (3H, s, CO₂CH₃), 7.49–7.53 (2H, m, ArH), 7.95–7.99 (2H, m, ArH); ¹³C-NMR (CDCl₃, 75.5 MHz): δ = -0.44 (SiCH₃), 52.063 (OCH₃), 97.738 (CC), 104.16 (CC), 127.952 (ArH), 129.53 (ArH), 129.896 (ArH), 132.029 (ArH), 166.761 (CO)

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001; Atwood & Barbour, 2003); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. Herring-bone arrangement of the molecules, viewed down the c axis.
	Fig. 3. C—H···O hydrogen bonds formed between a methyl hydrogen of the trimethylsilyl group and a neighbouring carbonyl oxygen atom. Hydrogen bonds are shown as dashed lines.

Methyl 4-(trimethylsilylethynyl)benzoate top

Crystal data top

C₁₃H₁₆O₂Si	F(000) = 496
M_r = 232.35	D_x = 1.184 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P2ac2ab	Cell parameters from 1456 reflections
a = 6.1983 (11) Å	θ = 2.8–23.3°
b = 7.1194 (12) Å	µ = 0.16 mm⁻¹
c = 29.530 (5) Å	T = 100 K
V = 1303.1 (4) Å³	Plate, colourless
Z = 4	0.25 × 0.24 × 0.08 mm

Data collection top

Bruker APEX CCD area-detector diffractometer	3050 independent reflections
Radiation source: fine-focus sealed tube	2643 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
/w scans	θ_max = 28.3°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −7→8
T_min = 0.960, T_max = 0.987	k = −8→9
8160 measured reflections	l = −37→32

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)] = 0.058	H-atom parameters constrained
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0431P)² + 0.2577P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
3050 reflections	Δρ_max = 0.37 e Å⁻³
149 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1136 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (19)

Crystal data top

C₁₃H₁₆O₂Si	V = 1303.1 (4) Å³
M_r = 232.35	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.1983 (11) Å	µ = 0.16 mm⁻¹
b = 7.1194 (12) Å	T = 100 K
c = 29.530 (5) Å	0.25 × 0.24 × 0.08 mm

Data collection top

Bruker APEX CCD area-detector diffractometer	3050 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2643 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.987	R_int = 0.054
8160 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.114	Δρ_max = 0.37 e Å⁻³
S = 1.10	Δρ_min = −0.30 e Å⁻³
3050 reflections	Absolute structure: Flack (1983), 1136 Friedel pairs
149 parameters	Absolute structure parameter: −0.01 (19)
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
Si1	0.68188 (11)	0.55394 (11)	0.42983 (2)	0.01481 (17)
O1	0.1541 (3)	0.5852 (3)	0.12946 (6)	0.0236 (5)
O2	−0.1514 (3)	0.4974 (3)	0.16417 (6)	0.0182 (4)
C1	0.1563 (4)	0.5421 (4)	0.20957 (8)	0.0138 (5)
C2	0.3623 (4)	0.6175 (4)	0.21449 (9)	0.0138 (5)
H2	0.4368	0.6646	0.1888	0.017*
C3	0.4582 (4)	0.6241 (4)	0.25659 (9)	0.0146 (5)
H3	0.5981	0.6770	0.2598	0.017*
C4	0.3507 (4)	0.5533 (4)	0.29466 (8)	0.0133 (5)
C5	0.1428 (4)	0.4787 (4)	0.28942 (8)	0.0137 (5)
H5	0.0673	0.4322	0.3151	0.016*
C6	0.0467 (4)	0.4724 (3)	0.24702 (8)	0.0138 (5)
H6	−0.0936	0.4206	0.2436	0.017*
C7	0.0588 (4)	0.5439 (4)	0.16347 (8)	0.0145 (5)
C8	−0.2620 (4)	0.5084 (4)	0.12112 (9)	0.0220 (7)
H8A	−0.2696	0.6397	0.1113	0.033*
H8B	−0.4084	0.4581	0.1244	0.033*
H8C	−0.1831	0.4347	0.0985	0.033*
C9	0.4551 (4)	0.5535 (4)	0.33826 (8)	0.0149 (5)
C10	0.5448 (4)	0.5509 (4)	0.37428 (8)	0.0169 (5)
C11	0.9744 (4)	0.5113 (5)	0.42078 (10)	0.0299 (8)
H11A	0.9953	0.3856	0.4080	0.045*
H11B	1.0505	0.5202	0.4498	0.045*
H11C	1.0318	0.6055	0.3998	0.045*
C12	0.6371 (5)	0.7888 (4)	0.45560 (9)	0.0219 (6)
H12A	0.6989	0.8858	0.4360	0.033*
H12B	0.7068	0.7937	0.4854	0.033*
H12C	0.4819	0.8108	0.4591	0.033*
C13	0.5661 (5)	0.3652 (4)	0.46578 (10)	0.0272 (7)
H13A	0.4092	0.3806	0.4676	0.041*
H13B	0.6281	0.3728	0.4962	0.041*
H13C	0.5999	0.2426	0.4525	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0106 (3)	0.0178 (4)	0.0160 (3)	0.0025 (3)	−0.0022 (3)	−0.0019 (3)
O1	0.0155 (9)	0.0366 (12)	0.0188 (10)	−0.0016 (10)	0.0001 (8)	0.0049 (9)
O2	0.0108 (9)	0.0249 (11)	0.0189 (9)	−0.0047 (8)	−0.0051 (7)	0.0009 (7)
C1	0.0119 (11)	0.0130 (13)	0.0166 (12)	0.0010 (12)	−0.0024 (9)	−0.0018 (11)
C2	0.0115 (12)	0.0129 (13)	0.0171 (14)	0.0011 (10)	0.0019 (10)	0.0008 (10)
C3	0.0085 (12)	0.0145 (13)	0.0208 (14)	−0.0016 (10)	−0.0010 (10)	−0.0032 (11)
C4	0.0119 (11)	0.0115 (12)	0.0164 (12)	0.0039 (12)	−0.0024 (9)	−0.0016 (11)
C5	0.0127 (12)	0.0123 (13)	0.0162 (12)	−0.0025 (11)	0.0024 (9)	0.0015 (10)
C6	0.0115 (12)	0.0086 (13)	0.0213 (13)	0.0009 (10)	0.0001 (10)	−0.0019 (11)
C7	0.0124 (11)	0.0110 (12)	0.0199 (13)	0.0007 (11)	−0.0024 (10)	0.0001 (12)
C8	0.0181 (14)	0.0266 (17)	0.0212 (14)	−0.0029 (11)	−0.0079 (11)	−0.0028 (12)
C9	0.0134 (11)	0.0112 (12)	0.0202 (13)	−0.0005 (12)	−0.0010 (10)	−0.0013 (12)
C10	0.0122 (12)	0.0167 (14)	0.0218 (14)	−0.0009 (12)	0.0016 (10)	−0.0021 (12)
C11	0.0186 (14)	0.0392 (19)	0.0320 (18)	0.0086 (13)	−0.0050 (12)	−0.0188 (14)
C12	0.0231 (16)	0.0255 (16)	0.0171 (15)	0.0053 (12)	−0.0037 (12)	−0.0011 (12)
C13	0.0223 (16)	0.0280 (17)	0.0313 (18)	0.0039 (13)	−0.0063 (13)	0.0061 (14)

Geometric parameters (Å, º) top

Si1—C10	1.848 (3)	C5—H5	0.9500
Si1—C13	1.857 (3)	C6—H6	0.9500
Si1—C11	1.858 (3)	C8—H8A	0.9800
Si1—C12	1.858 (3)	C8—H8B	0.9800
O1—C7	1.202 (3)	C8—H8C	0.9800
O2—C7	1.344 (3)	C9—C10	1.200 (3)
O2—C8	1.447 (3)	C9—C4	1.441 (3)
C1—C6	1.390 (3)	C11—H11A	0.9800
C1—C2	1.392 (3)	C11—H11B	0.9800
C1—C7	1.490 (3)	C11—H11C	0.9800
C2—H2	0.9500	C12—H12A	0.9800
C3—C2	1.379 (4)	C12—H12B	0.9800
C3—H3	0.9500	C12—H12C	0.9800
C4—C3	1.401 (3)	C13—H13A	0.9800
C4—C5	1.403 (3)	C13—H13B	0.9800
C5—C6	1.387 (3)	C13—H13C	0.9800

C10—Si1—C13	108.75 (14)	O1—C7—O2	123.3 (2)
C10—Si1—C11	108.62 (12)	O1—C7—C1	124.5 (2)
C13—Si1—C11	109.95 (15)	O2—C7—C1	112.2 (2)
C10—Si1—C12	107.78 (13)	Si1—C11—H11A	109.5
C13—Si1—C12	111.06 (14)	Si1—C11—H11B	109.5
C11—Si1—C12	110.61 (14)	H11A—C11—H11B	109.5
C7—O2—C8	115.63 (19)	Si1—C11—H11C	109.5
C10—C9—C4	178.7 (3)	H11A—C11—H11C	109.5
C3—C4—C5	119.0 (2)	H11B—C11—H11C	109.5
C3—C4—C9	120.2 (2)	O2—C8—H8A	109.5
C5—C4—C9	120.8 (2)	O2—C8—H8B	109.5
C6—C1—C2	120.2 (2)	H8A—C8—H8B	109.5
C6—C1—C7	122.1 (2)	O2—C8—H8C	109.5
C2—C1—C7	117.7 (2)	H8A—C8—H8C	109.5
C2—C3—C4	120.4 (2)	H8B—C8—H8C	109.5
C2—C3—H3	119.8	Si1—C12—H12A	109.5
C4—C3—H3	119.8	Si1—C12—H12B	109.5
C3—C2—C1	120.2 (2)	H12A—C12—H12B	109.5
C3—C2—H2	119.9	Si1—C12—H12C	109.5
C1—C2—H2	119.9	H12A—C12—H12C	109.5
C9—C10—Si1	178.4 (3)	H12B—C12—H12C	109.5
C6—C5—C4	120.4 (2)	Si1—C13—H13A	109.5
C6—C5—H5	119.8	Si1—C13—H13B	109.5
C4—C5—H5	119.8	H13A—C13—H13B	109.5
C5—C6—C1	119.8 (2)	Si1—C13—H13C	109.5
C5—C6—H6	120.1	H13A—C13—H13C	109.5
C1—C6—H6	120.1	H13B—C13—H13C	109.5

C5—C4—C3—C2	−1.1 (4)	C2—C1—C6—C5	0.2 (4)
C9—C4—C3—C2	177.5 (2)	C7—C1—C6—C5	−178.3 (2)
C4—C3—C2—C1	0.7 (4)	C8—O2—C7—O1	−2.8 (4)
C6—C1—C2—C3	−0.2 (4)	C8—O2—C7—C1	175.9 (2)
C7—C1—C2—C3	178.3 (2)	C6—C1—C7—O1	−172.3 (3)
C3—C4—C5—C6	1.1 (4)	C2—C1—C7—O1	9.2 (4)
C9—C4—C5—C6	−177.5 (2)	C6—C1—C7—O2	9.0 (4)
C4—C5—C6—C1	−0.6 (4)	C2—C1—C7—O2	−169.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O1ⁱ	0.98	2.58	3.470 (4)	151
C12—H12A···O1ⁱⁱ	0.98	2.57	3.527 (3)	167

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₆O₂Si
M_r	232.35
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	6.1983 (11), 7.1194 (12), 29.530 (5)
V (Å³)	1303.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.25 × 0.24 × 0.08

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.960, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	8160, 3050, 2643
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.114, 1.10
No. of reflections	3050
No. of parameters	149
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.30
Absolute structure	Flack (1983), 1136 Friedel pairs
Absolute structure parameter	−0.01 (19)

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001; Atwood & Barbour, 2003), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O1ⁱ	0.98	2.58	3.470 (4)	151
C12—H12A···O1ⁱⁱ	0.98	2.57	3.527 (3)	167

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

Acknowledgements

The authors acknowledge SASOL for funding.

References

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