Methyl 2,2-diphenyl-2-(prop-2-yn-1-yl­oxy)acetate

Sumathi, H.P.; Flörke, U.; Yathirajan, H.S.; Dayananda, A.S.; Ramesha, A.R.

doi:10.1107/S1600536812007982

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o874

doi:10.1107/S1600536812007982

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Methyl 2,2-diphenyl-2-(prop-2-yn-1-yloxy)acetate

H. P. Sumathi,^a Ulrich Flörke,^b ^* H. S. Yathirajan,^a A. S. Dayananda ^a and A. R. Ramesha ^c

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, ^bDepartment Chemie, Fakultät für Naturwissenschaften, Universität Paderborn, Warburgerstrasse 100, D-33098 Paderborn, Germany, and ^cR. L. Fine Chemicals, Bangalore 560 064, India
^*Correspondence e-mail: ulrich.floerke@upb.de

(Received 3 February 2012; accepted 22 February 2012; online 29 February 2012)

The molecular structure of the title compound, C₁₈H₁₆O₃, exhibits a new R₂–C(COOMe)(OCH₂CCH) group. The C—O—C—C torsion angle is 153.3 (1)°. The dihedral angles are 79.89 (5)° between phenyl/phenyl planes, and 73.13 (5) and 79.05 (8)° for the two COOMe/phenyl plane pairs.

Related literature

For related literature on the background of this work, see: Ferguson et al. (1995 ); Ohkuma et al. (2000 ). For related structures, see: Narayanan et al. (2011 ); Shah et al. (2011 ); Siddaraju et al. (2010 ); Zhang et al. (2008 ); Zhang et al. (2011 ).

Experimental

Crystal data

C₁₈H₁₆O₃
M_r = 280.31
Monoclinic, P 2₁ /c
a = 12.6771 (17) Å
b = 9.2410 (13) Å
c = 12.7055 (18) Å
β = 93.090 (3)°
V = 1486.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 130 K
0.37 × 0.22 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.969, T_max = 0.992
13808 measured reflections
3545 independent reflections
2623 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.117
S = 1.02
3545 reflections
195 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812007982/nc2267sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007982/nc2267Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812007982/nc2267Isup3.cml

checkCIF report

Related literature top

For related literature on the background of this work, see: Ferguson et al. (1995); Ohkuma et al. (2000). For related structures, see: Narayanan et al. (2011); Shah et al. (2011); Siddaraju et al. (2010); Zhang et al. (2008); Zhang et al. (2011).

Experimental top

The title compound was obtained as a gift sample from R. L. Fine Chem., Bengaluru, India. X-ray quality crystals were obtained from toluene by slow evaporation (m.p. 318 K).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

Fig. 1. Molecular structure with labeling and displacement ellipsoids drawn at the 50% probability level.

Methyl 2,2-diphenyl-2-(prop-2-yn-1-yloxy)acetate top

Crystal data top

C₁₈H₁₆O₃	F(000) = 592
M_r = 280.31	D_x = 1.253 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1710 reflections
a = 12.6771 (17) Å	θ = 2.7–23.4°
b = 9.2410 (13) Å	µ = 0.09 mm⁻¹
c = 12.7055 (18) Å	T = 130 K
β = 93.090 (3)°	Prism, colourless
V = 1486.3 (4) Å³	0.37 × 0.22 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	3545 independent reflections
Radiation source: sealed tube	2623 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ϕ and ω scans	θ_max = 27.9°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −14→16
T_min = 0.969, T_max = 0.992	k = −12→12
13808 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: difference Fourier map
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0487P)² + 0.3727P] where P = (F_o² + 2F_c²)/3
3545 reflections	(Δ/σ)_max < 0.001
195 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₈H₁₆O₃	V = 1486.3 (4) Å³
M_r = 280.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.6771 (17) Å	µ = 0.09 mm⁻¹
b = 9.2410 (13) Å	T = 130 K
c = 12.7055 (18) Å	0.37 × 0.22 × 0.10 mm
β = 93.090 (3)°

Data collection top

Bruker SMART APEX diffractometer	3545 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2623 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.992	R_int = 0.045
13808 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.33 e Å⁻³
3545 reflections	Δρ_min = −0.19 e Å⁻³
195 parameters

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
O1	0.79582 (9)	0.45794 (12)	0.41949 (10)	0.0378 (3)
O2	0.66203 (9)	0.37609 (11)	0.51072 (9)	0.0296 (3)
O3	0.78724 (8)	0.22289 (11)	0.28970 (8)	0.0247 (3)
C1	0.72467 (12)	0.21809 (15)	0.38023 (11)	0.0203 (3)
C2	0.73393 (12)	0.36505 (15)	0.43855 (12)	0.0233 (3)
C3	0.66088 (16)	0.51182 (17)	0.56825 (15)	0.0393 (5)
H3A	0.7287	0.5250	0.6078	0.059*
H3B	0.6038	0.5100	0.6173	0.059*
H3C	0.6494	0.5920	0.5185	0.059*
C4	0.90005 (12)	0.22196 (19)	0.31004 (13)	0.0299 (4)
H4A	0.9188	0.1639	0.3738	0.036*
H4B	0.9261	0.3219	0.3222	0.036*
C5	0.94840 (13)	0.15941 (18)	0.21894 (14)	0.0302 (4)
C6	0.99076 (16)	0.1114 (2)	0.14631 (16)	0.0432 (5)
H6	1.0260 (19)	0.068 (3)	0.0870 (19)	0.073 (7)*
C11	0.60998 (11)	0.20274 (15)	0.33670 (11)	0.0199 (3)
C12	0.57858 (12)	0.25763 (17)	0.23856 (13)	0.0271 (4)
H12A	0.6288	0.3037	0.1969	0.032*
C13	0.47418 (13)	0.24566 (19)	0.20079 (13)	0.0326 (4)
H13A	0.4534	0.2830	0.1332	0.039*
C14	0.40033 (13)	0.17983 (17)	0.26091 (13)	0.0291 (4)
H14A	0.3292	0.1700	0.2343	0.035*
C15	0.43066 (12)	0.12818 (17)	0.36029 (13)	0.0279 (4)
H15A	0.3798	0.0853	0.4028	0.033*
C16	0.53494 (12)	0.13889 (16)	0.39776 (13)	0.0247 (3)
H16A	0.5554	0.1023	0.4657	0.030*
C21	0.76008 (11)	0.09067 (15)	0.45070 (11)	0.0198 (3)
C22	0.76063 (12)	−0.04599 (16)	0.40361 (13)	0.0255 (3)
H22A	0.7343	−0.0573	0.3327	0.031*
C23	0.79918 (13)	−0.16498 (17)	0.45948 (14)	0.0307 (4)
H23A	0.7992	−0.2575	0.4269	0.037*
C24	0.83784 (13)	−0.14904 (17)	0.56317 (14)	0.0312 (4)
H24A	0.8648	−0.2305	0.6015	0.037*
C25	0.83705 (13)	−0.01480 (18)	0.61038 (13)	0.0294 (4)
H25A	0.8628	−0.0040	0.6815	0.035*
C26	0.79855 (12)	0.10528 (16)	0.55403 (12)	0.0239 (3)
H26A	0.7988	0.1977	0.5868	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0357 (7)	0.0252 (6)	0.0539 (8)	−0.0100 (5)	0.0158 (6)	−0.0027 (5)
O2	0.0363 (7)	0.0233 (6)	0.0304 (6)	−0.0054 (5)	0.0122 (5)	−0.0064 (4)
O3	0.0162 (5)	0.0372 (6)	0.0210 (6)	0.0001 (4)	0.0048 (4)	0.0035 (4)
C1	0.0200 (8)	0.0221 (7)	0.0192 (7)	−0.0014 (6)	0.0044 (6)	0.0010 (6)
C2	0.0222 (8)	0.0225 (7)	0.0252 (8)	−0.0003 (6)	0.0006 (6)	0.0029 (6)
C3	0.0522 (12)	0.0246 (8)	0.0424 (11)	−0.0033 (8)	0.0146 (9)	−0.0111 (7)
C4	0.0174 (8)	0.0434 (10)	0.0292 (9)	−0.0015 (7)	0.0042 (7)	0.0028 (7)
C5	0.0207 (8)	0.0364 (9)	0.0338 (9)	0.0061 (7)	0.0034 (7)	0.0106 (7)
C6	0.0339 (11)	0.0559 (12)	0.0407 (11)	0.0179 (9)	0.0090 (9)	0.0058 (9)
C11	0.0183 (8)	0.0195 (7)	0.0222 (8)	0.0014 (5)	0.0029 (6)	−0.0005 (5)
C12	0.0207 (8)	0.0349 (8)	0.0259 (8)	−0.0001 (6)	0.0036 (7)	0.0052 (7)
C13	0.0283 (9)	0.0455 (10)	0.0237 (8)	0.0029 (7)	−0.0016 (7)	0.0074 (7)
C14	0.0191 (8)	0.0317 (8)	0.0361 (9)	0.0006 (6)	−0.0028 (7)	0.0011 (7)
C15	0.0195 (8)	0.0289 (8)	0.0355 (9)	−0.0009 (6)	0.0042 (7)	0.0077 (7)
C16	0.0211 (8)	0.0271 (8)	0.0261 (8)	0.0005 (6)	0.0026 (6)	0.0065 (6)
C21	0.0143 (7)	0.0222 (7)	0.0231 (8)	−0.0017 (5)	0.0022 (6)	0.0003 (6)
C22	0.0241 (8)	0.0262 (8)	0.0260 (8)	0.0000 (6)	−0.0011 (7)	−0.0031 (6)
C23	0.0254 (9)	0.0236 (8)	0.0430 (10)	0.0013 (6)	0.0001 (8)	−0.0024 (7)
C24	0.0214 (8)	0.0296 (8)	0.0418 (10)	0.0013 (6)	−0.0044 (7)	0.0100 (7)
C25	0.0231 (9)	0.0364 (9)	0.0277 (9)	−0.0020 (7)	−0.0068 (7)	0.0050 (7)
C26	0.0194 (8)	0.0263 (7)	0.0260 (8)	−0.0031 (6)	−0.0001 (6)	−0.0008 (6)

Geometric parameters (Å, º) top

O1—C2	1.1965 (18)	C12—H12A	0.9500
O2—C2	1.3312 (18)	C13—C14	1.381 (2)
O2—C3	1.4522 (18)	C13—H13A	0.9500
O3—C1	1.4327 (17)	C14—C15	1.385 (2)
O3—C4	1.4396 (18)	C14—H14A	0.9500
C1—C21	1.532 (2)	C15—C16	1.384 (2)
C1—C11	1.534 (2)	C15—H15A	0.9500
C1—C2	1.548 (2)	C16—H16A	0.9500
C3—H3A	0.9800	C21—C26	1.382 (2)
C3—H3B	0.9800	C21—C22	1.398 (2)
C3—H3C	0.9800	C22—C23	1.384 (2)
C4—C5	1.458 (2)	C22—H22A	0.9500
C4—H4A	0.9900	C23—C24	1.388 (2)
C4—H4B	0.9900	C23—H23A	0.9500
C5—C6	1.179 (3)	C24—C25	1.378 (2)
C6—H6	0.98 (2)	C24—H24A	0.9500
C11—C12	1.385 (2)	C25—C26	1.394 (2)
C11—C16	1.391 (2)	C25—H25A	0.9500
C12—C13	1.388 (2)	C26—H26A	0.9500

C2—O2—C3	116.02 (12)	C14—C13—C12	120.41 (15)
C1—O3—C4	116.32 (11)	C14—C13—H13A	119.8
O3—C1—C21	109.60 (11)	C12—C13—H13A	119.8
O3—C1—C11	105.57 (11)	C13—C14—C15	119.54 (15)
C21—C1—C11	112.45 (11)	C13—C14—H14A	120.2
O3—C1—C2	109.03 (11)	C15—C14—H14A	120.2
C21—C1—C2	112.47 (12)	C16—C15—C14	120.13 (15)
C11—C1—C2	107.43 (11)	C16—C15—H15A	119.9
O1—C2—O2	124.42 (14)	C14—C15—H15A	119.9
O1—C2—C1	124.47 (14)	C15—C16—C11	120.51 (14)
O2—C2—C1	111.08 (12)	C15—C16—H16A	119.7
O2—C3—H3A	109.5	C11—C16—H16A	119.7
O2—C3—H3B	109.5	C26—C21—C22	119.02 (13)
H3A—C3—H3B	109.5	C26—C21—C1	123.87 (13)
O2—C3—H3C	109.5	C22—C21—C1	116.90 (13)
H3A—C3—H3C	109.5	C23—C22—C21	120.55 (15)
H3B—C3—H3C	109.5	C23—C22—H22A	119.7
O3—C4—C5	108.41 (13)	C21—C22—H22A	119.7
O3—C4—H4A	110.0	C22—C23—C24	119.95 (15)
C5—C4—H4A	110.0	C22—C23—H23A	120.0
O3—C4—H4B	110.0	C24—C23—H23A	120.0
C5—C4—H4B	110.0	C25—C24—C23	119.87 (15)
H4A—C4—H4B	108.4	C25—C24—H24A	120.1
C6—C5—C4	177.6 (2)	C23—C24—H24A	120.1
C5—C6—H6	178.2 (14)	C24—C25—C26	120.22 (15)
C12—C11—C16	119.06 (14)	C24—C25—H25A	119.9
C12—C11—C1	120.77 (13)	C26—C25—H25A	119.9
C16—C11—C1	120.11 (13)	C21—C26—C25	120.38 (14)
C11—C12—C13	120.32 (15)	C21—C26—H26A	119.8
C11—C12—H12A	119.8	C25—C26—H26A	119.8
C13—C12—H12A	119.8

C4—O3—C1—C21	−52.38 (16)	C11—C12—C13—C14	0.4 (3)
C4—O3—C1—C11	−173.72 (12)	C12—C13—C14—C15	1.3 (3)
C4—O3—C1—C2	71.12 (15)	C13—C14—C15—C16	−1.8 (2)
C3—O2—C2—O1	0.2 (2)	C14—C15—C16—C11	0.7 (2)
C3—O2—C2—C1	−178.05 (13)	C12—C11—C16—C15	1.1 (2)
O3—C1—C2—O1	−10.3 (2)	C1—C11—C16—C15	178.21 (13)
C21—C1—C2—O1	111.46 (17)	O3—C1—C21—C26	119.93 (15)
C11—C1—C2—O1	−124.27 (16)	C11—C1—C21—C26	−122.97 (15)
O3—C1—C2—O2	167.95 (11)	C2—C1—C21—C26	−1.5 (2)
C21—C1—C2—O2	−70.27 (16)	O3—C1—C21—C22	−54.88 (16)
C11—C1—C2—O2	54.00 (15)	C11—C1—C21—C22	62.22 (17)
C1—O3—C4—C5	153.28 (13)	C2—C1—C21—C22	−176.34 (13)
O3—C1—C11—C12	−28.55 (17)	C26—C21—C22—C23	−0.1 (2)
C21—C1—C11—C12	−148.02 (14)	C1—C21—C22—C23	175.02 (14)
C2—C1—C11—C12	87.70 (16)	C21—C22—C23—C24	−0.1 (2)
O3—C1—C11—C16	154.35 (13)	C22—C23—C24—C25	0.4 (2)
C21—C1—C11—C16	34.87 (18)	C23—C24—C25—C26	−0.6 (2)
C2—C1—C11—C16	−89.40 (15)	C22—C21—C26—C25	−0.2 (2)
C16—C11—C12—C13	−1.6 (2)	C1—C21—C26—C25	−174.87 (14)
C1—C11—C12—C13	−178.74 (14)	C24—C25—C26—C21	0.5 (2)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆O₃
M_r	280.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	130
a, b, c (Å)	12.6771 (17), 9.2410 (13), 12.7055 (18)
β (°)	93.090 (3)
V (Å³)	1486.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.37 × 0.22 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.969, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	13808, 3545, 2623
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.117, 1.02
No. of reflections	3545
No. of parameters	195
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.19

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Sheldrick, 2008) and local programs.

Acknowledgements

HPS is grateful to the University of Mysore for research facilities. HSY thanks R. L. Fine Chemicals, Bangalore, India, for the gift of a sample of the title compound.

References

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