1-Meth­oxy-1,1-di­phenyl­but-2-yne

Seidel, N.; Seichter, W.; Weber, E.

doi:10.1107/S2414314618004157

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 4| April 2018| x180415

https://doi.org/10.1107/S2414314618004157

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1-Methoxy-1,1-diphenylbut-2-yne

Nadine Seidel,^a Wilhelm Seichter ^a and Edwin Weber ^a ^*

^aInstitut für Organische Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, D-09596 Freiberg/Sachsen, Germany
^*Correspondence e-mail: edwin.weber@chemie-tu.freiberg.de

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 18 January 2018; accepted 12 March 2018; online 6 April 2018)

In the title compound, C₁₇H₁₆O, the phenyl rings are twisted relative to each other at an angle of 85.9 (1)°. The crystal structure features weak C—H⋯π interactions, which connect the molecules into a three-dimensional supramolecular network.

Keywords: crystal structure; 1,1,1-trisubstituted but-2-yne; C—H⋯π interaction.

CCDC reference: 1828942

Structure description

The title compound has been prepared as an intermediate for the synthesis of a potential `wheel-and-axle' molecule (Weber, 1996 ). Compounds of this latter type are significant crystalline inclusion hosts (Katzsch et al., 2015 , 2016 ) and important examples in the course of the development of the concept of crystal engineering (Hart et al., 1984 ; Bishop, 2012 ). Alternative approaches for the synthesis of the title compound have already been reported (Van Rijn et al., 1981 ; Kostikov et al., 1996 ; Maraval et al., 2008 ). One of these, which is closely related to the method we used for the synthesis of the compound, resulted in a yellow oil, while our preparative method yielded the compound as colourless crystals that were used for X-ray crystal structure analysis.

The asymmetric unit of the cell contains one molecule (Fig. 1), the aromatic rings of which are tilted to one another at an angle of 85.9 (1)°. The propyne unit of the molecule slightly deviates from linearity, showing an angle of 177.64 (12)° at C14. In the crystal structure (Fig. 2), the molecules are packed in neither a layered nor a stacked manner, but are connected via C—H⋯π interactions (Nishio et al., 2009 ). These involve the aromatic rings and the C≡C triple bond acting as acceptors (Table 1). The oxygen atom of the molecule does not participate in a comparable weak hydrogen bond (Desiraju & Steiner, 1999 ), probably due to steric hindrance.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C2–C7 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17A⋯Cg1ⁱ	0.98	2.81	3.423 (1)	121
C5—H5⋯Cg2ⁱⁱ	0.95	2.73	3.660 (1)	166
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
Perspective view of the title compound, showing 50% probability displacement ellipsoids for non-H atoms.

Figure 2
Packing diagram of the title compound viewed down the a axis.

Synthesis and crystallization

Under an atmosphere of argon, 1,1-diphenylprop-2-yne-1-ol (5.2 g, 25 mmol) was added to a stirred suspension of sodium hydride (6.0 g, 250 mmol, 10% in paraffin oil) in dry THF (250 ml). After stirring for 30 min, methyl iodide (21 ml, 330 mmol) was added and the mixture was heated to reflux for 16 h. After cooling, the mixture was quenched with water (50 ml) and extracted with diethyl ether. The combined organic layers were dried over sodium sulfate and the solvents evaporated to dryness, thus giving colourless crystals (5.8 g, 98%) with m.p. 329 K. ¹H NMR (500.1 MHz, CDCl₃): δ = 1.98 (s, 3H, C—CH₃), 3.31 (s, 3H, OCH₃), 7.26–7.27 (m, 8H, Ar—H), 7.52–7.54 (m, 2H, Ar—H) p.p.m. ¹³C NMR (125.8 MHz, CDCl₃): δ = 3.7 (C—CH₃), 52.1 (O—CH₃), 78.6 (Ar—C—C≡C), 80.8 (Ar—C–-O), 85.7 (C≡C—CH₃), 126.7 (Ar), 127.3 (Ar), 127.9 (Ar), 143.9 (Ar) p.p.m. IR (KBr): ν = 2230 cm⁻¹ (C≡C); GC—MS: m/z = 237 [M]⁺. Colourless plates were grown via slow evaporation of solvent from a 1:1 solvent mixture of ethanol and THF.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₆O
M_r	236.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.6483 (2), 10.6060 (3), 13.4332 (4)
β (°)	104.034 (1)
V (Å³)	1333.59 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.07
Crystal size (mm)	0.50 × 0.46 × 0.35

Data collection
Diffractometer	Bruker Kappa goniometer with an APEXII CCD area detector
No. of measured, independent and observed [I > 2σ(I)] reflections	13834, 2939, 2582
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.112, 1.06
No. of reflections	2939
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.31
Computer programs: APEX2 and SAINT-NT (Bruker, 2008 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Structural data

CCDC reference: 1828942

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618004157/bh4034sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618004157/bh4034Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618004157/bh4034Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-NT (Bruker, 2008); data reduction: SAINT-NT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

1-Methoxy-1,1-diphenylbut-2-yne top

Crystal data top

C₁₇H₁₆O	D_x = 1.177 Mg m⁻³
M_r = 236.30	Melting point: 329 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.6483 (2) Å	Cell parameters from 8020 reflections
b = 10.6060 (3) Å	θ = 2.4–33.1°
c = 13.4332 (4) Å	µ = 0.07 mm⁻¹
β = 104.034 (1)°	T = 100 K
V = 1333.59 (6) Å³	Irregular, colourless
Z = 4	0.50 × 0.46 × 0.35 mm
F(000) = 504

Data collection top

Bruker Kappa goniometer with an APEXII CCD area detector diffractometer	R_int = 0.025
Radiation source: Sealed X-ray tube	θ_max = 27.1°, θ_min = 2.2°
φ and ω scans	h = −12→11
13834 measured reflections	k = −13→9
2939 independent reflections	l = −17→17
2582 reflections with I > 2σ(I)

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0503P)² + 0.6393P] where P = (F_o² + 2F_c²)/3
2939 reflections	(Δ/σ)_max = 0.001
165 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³
0 constraints

Special details top

Refinement. The non-hydrogen atoms were refined anisotropically. The hydrogen atoms were positioned geometrically and refined isotropically using the riding model with C—H = 0.98 Å and U_iso(H) = 1.5 U_eq(C) for methyl groups, and C—H = 0.95 Å and U_iso(H) = 1.2 U_eq(C) for phenyl groups.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.44623 (8)	−0.10133 (8)	0.17564 (6)	0.0189 (2)
C1	0.36399 (11)	−0.01102 (11)	0.21645 (8)	0.0148 (2)
C2	0.24889 (11)	−0.08676 (11)	0.25168 (8)	0.0146 (2)
C3	0.25175 (12)	−0.21765 (11)	0.25575 (9)	0.0183 (2)
H3	0.3230	−0.2629	0.2326	0.022*
C4	0.14980 (13)	−0.28244 (12)	0.29387 (9)	0.0221 (3)
H4	0.1520	−0.3720	0.2964	0.027*
C5	0.04549 (12)	−0.21788 (12)	0.32810 (9)	0.0217 (3)
H5	−0.0230	−0.2626	0.3546	0.026*
C6	0.04201 (12)	−0.08689 (12)	0.32339 (9)	0.0205 (3)
H6	−0.0295	−0.0418	0.3464	0.025*
C7	0.14275 (12)	−0.02197 (11)	0.28520 (8)	0.0176 (2)
H7	0.1395	0.0675	0.2818	0.021*
C8	0.29562 (11)	0.08338 (11)	0.13200 (8)	0.0158 (2)
C9	0.19931 (12)	0.03667 (12)	0.04470 (9)	0.0200 (3)
H9	0.1779	−0.0509	0.0394	0.024*
C10	0.13505 (13)	0.11747 (14)	−0.03405 (9)	0.0245 (3)
H10	0.0689	0.0854	−0.0929	0.029*
C11	0.16720 (13)	0.24534 (14)	−0.02706 (10)	0.0269 (3)
H11	0.1226	0.3008	−0.0808	0.032*
C12	0.26422 (13)	0.29179 (13)	0.05828 (10)	0.0256 (3)
H12	0.2873	0.3790	0.0625	0.031*
C13	0.32831 (12)	0.21100 (11)	0.13811 (9)	0.0200 (3)
H13	0.3945	0.2434	0.1968	0.024*
C14	0.45375 (12)	0.05219 (11)	0.30794 (9)	0.0173 (2)
C15	0.52478 (12)	0.09973 (11)	0.38375 (9)	0.0194 (2)
C16	0.56975 (13)	−0.05142 (13)	0.14930 (10)	0.0246 (3)
H16A	0.5419	0.0189	0.1013	0.037*
H16B	0.6149	−0.1174	0.1170	0.037*
H16C	0.6374	−0.0214	0.2115	0.037*
C17	0.61243 (14)	0.15804 (13)	0.47669 (10)	0.0264 (3)
H17A	0.6757	0.0944	0.5170	0.040*
H17B	0.5503	0.1929	0.5177	0.040*
H17C	0.6700	0.2258	0.4576	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0169 (4)	0.0170 (4)	0.0252 (4)	0.0001 (3)	0.0099 (3)	−0.0019 (3)
C1	0.0141 (5)	0.0138 (5)	0.0163 (5)	−0.0004 (4)	0.0036 (4)	−0.0010 (4)
C2	0.0139 (5)	0.0168 (5)	0.0121 (5)	−0.0017 (4)	0.0013 (4)	−0.0006 (4)
C3	0.0171 (5)	0.0173 (6)	0.0211 (5)	−0.0008 (4)	0.0056 (4)	−0.0023 (4)
C4	0.0229 (6)	0.0172 (6)	0.0265 (6)	−0.0041 (5)	0.0066 (5)	−0.0011 (5)
C5	0.0189 (6)	0.0262 (6)	0.0207 (6)	−0.0057 (5)	0.0063 (4)	0.0007 (5)
C6	0.0176 (5)	0.0259 (6)	0.0190 (5)	0.0022 (4)	0.0063 (4)	−0.0008 (5)
C7	0.0193 (5)	0.0173 (6)	0.0160 (5)	0.0016 (4)	0.0038 (4)	0.0001 (4)
C8	0.0139 (5)	0.0190 (6)	0.0154 (5)	−0.0001 (4)	0.0052 (4)	0.0014 (4)
C9	0.0184 (5)	0.0241 (6)	0.0180 (5)	−0.0032 (4)	0.0050 (4)	−0.0013 (5)
C10	0.0184 (6)	0.0394 (8)	0.0152 (5)	−0.0024 (5)	0.0029 (4)	0.0026 (5)
C11	0.0215 (6)	0.0366 (7)	0.0235 (6)	0.0031 (5)	0.0068 (5)	0.0143 (5)
C12	0.0229 (6)	0.0218 (6)	0.0328 (7)	−0.0006 (5)	0.0078 (5)	0.0089 (5)
C13	0.0171 (5)	0.0201 (6)	0.0226 (6)	−0.0022 (4)	0.0040 (4)	0.0013 (5)
C14	0.0166 (5)	0.0163 (5)	0.0185 (5)	−0.0009 (4)	0.0035 (4)	0.0033 (4)
C15	0.0204 (5)	0.0179 (6)	0.0186 (5)	−0.0014 (4)	0.0026 (4)	0.0038 (4)
C16	0.0191 (6)	0.0259 (6)	0.0325 (7)	−0.0004 (5)	0.0134 (5)	0.0008 (5)
C17	0.0300 (7)	0.0262 (7)	0.0185 (6)	−0.0062 (5)	−0.0025 (5)	0.0020 (5)

Geometric parameters (Å, º) top

O1—C16	1.4248 (14)	C9—C10	1.3855 (17)
O1—C1	1.4347 (13)	C9—H9	0.9500
C1—C14	1.4811 (15)	C10—C11	1.389 (2)
C1—C2	1.5354 (15)	C10—H10	0.9500
C1—C8	1.5367 (15)	C11—C12	1.3830 (19)
C2—C3	1.3893 (16)	C11—H11	0.9500
C2—C7	1.3955 (15)	C12—C13	1.3947 (17)
C3—C4	1.3951 (16)	C12—H12	0.9500
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.3848 (17)	C14—C15	1.1928 (17)
C4—H4	0.9500	C15—C17	1.4643 (16)
C5—C6	1.3908 (18)	C16—H16A	0.9800
C5—H5	0.9500	C16—H16B	0.9800
C6—C7	1.3871 (16)	C16—H16C	0.9800
C6—H6	0.9500	C17—H17A	0.9800
C7—H7	0.9500	C17—H17B	0.9800
C8—C13	1.3877 (16)	C17—H17C	0.9800
C8—C9	1.3984 (15)

C16—O1—C1	114.85 (9)	C10—C9—H9	119.9
O1—C1—C14	110.67 (9)	C8—C9—H9	119.9
O1—C1—C2	106.07 (9)	C9—C10—C11	120.07 (11)
C14—C1—C2	107.59 (9)	C9—C10—H10	120.0
O1—C1—C8	109.33 (8)	C11—C10—H10	120.0
C14—C1—C8	112.19 (9)	C12—C11—C10	119.93 (11)
C2—C1—C8	110.81 (8)	C12—C11—H11	120.0
C3—C2—C7	119.23 (10)	C10—C11—H11	120.0
C3—C2—C1	121.74 (10)	C11—C12—C13	120.21 (12)
C7—C2—C1	118.95 (10)	C11—C12—H12	119.9
C2—C3—C4	119.85 (11)	C13—C12—H12	119.9
C2—C3—H3	120.1	C8—C13—C12	120.12 (11)
C4—C3—H3	120.1	C8—C13—H13	119.9
C5—C4—C3	120.81 (11)	C12—C13—H13	119.9
C5—C4—H4	119.6	C15—C14—C1	177.64 (12)
C3—C4—H4	119.6	C14—C15—C17	179.79 (14)
C4—C5—C6	119.36 (11)	O1—C16—H16A	109.5
C4—C5—H5	120.3	O1—C16—H16B	109.5
C6—C5—H5	120.3	H16A—C16—H16B	109.5
C7—C6—C5	120.09 (11)	O1—C16—H16C	109.5
C7—C6—H6	120.0	H16A—C16—H16C	109.5
C5—C6—H6	120.0	H16B—C16—H16C	109.5
C6—C7—C2	120.66 (11)	C15—C17—H17A	109.5
C6—C7—H7	119.7	C15—C17—H17B	109.5
C2—C7—H7	119.7	H17A—C17—H17B	109.5
C13—C8—C9	119.37 (11)	C15—C17—H17C	109.5
C13—C8—C1	122.75 (10)	H17A—C17—H17C	109.5
C9—C8—C1	117.86 (10)	H17B—C17—H17C	109.5
C10—C9—C8	120.29 (12)

C16—O1—C1—C14	−56.68 (12)	C1—C2—C7—C6	−176.11 (10)
C16—O1—C1—C2	−173.08 (9)	O1—C1—C8—C13	−116.64 (11)
C16—O1—C1—C8	67.39 (11)	C14—C1—C8—C13	6.52 (15)
O1—C1—C2—C3	9.86 (13)	C2—C1—C8—C13	126.80 (11)
C14—C1—C2—C3	−108.60 (11)	O1—C1—C8—C9	61.74 (12)
C8—C1—C2—C3	128.42 (11)	C14—C1—C8—C9	−175.10 (10)
O1—C1—C2—C7	−173.33 (9)	C2—C1—C8—C9	−54.83 (13)
C14—C1—C2—C7	68.21 (12)	C13—C8—C9—C10	−1.25 (17)
C8—C1—C2—C7	−54.77 (12)	C1—C8—C9—C10	−179.68 (10)
C7—C2—C3—C4	−0.53 (16)	C8—C9—C10—C11	0.66 (17)
C1—C2—C3—C4	176.27 (10)	C9—C10—C11—C12	0.46 (18)
C2—C3—C4—C5	−0.15 (17)	C10—C11—C12—C13	−0.98 (19)
C3—C4—C5—C6	0.59 (17)	C9—C8—C13—C12	0.73 (17)
C4—C5—C6—C7	−0.33 (17)	C1—C8—C13—C12	179.08 (10)
C5—C6—C7—C2	−0.35 (17)	C11—C12—C13—C8	0.38 (18)
C3—C2—C7—C6	0.78 (16)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C2–C7 and C8–C13 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17A···Cg1ⁱ	0.98	2.81	3.423 (1)	121
C5—H5···Cg2ⁱⁱ	0.95	2.73	3.660 (1)	166

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

Funding information

We acknowledge the financial support by the Deutsche Forschungsgemeinschaft (DFG Priority Program 1362 `Porous Metal-Organic Frameworks').

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