(E)-1,1,4,4-Tetra­phenyl­but-2-yne-1,4-diol

Sundar, J.K.; Kumar, K.M.; Vijayakumar, V.; Suresh, J.; Natarajan, S.; Lakshman, P.L.N.

doi:10.1107/S160053681000629X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o679

doi:10.1107/S160053681000629X

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(E)-1,1,4,4-Tetraphenylbut-2-yne-1,4-diol

J. Kalyana Sundar,^a K. Mohan Kumar,^b V. Vijayakumar,^c J. Suresh,^d S. Natarajan ^a and P. L. Nilantha Lakshman ^e ^*

^aDepartment of Physics, Madurai Kamaraj University, Madurai 625 021, India, ^bEnvironmental and Analytical Division, School of Advanced Sciences, VIT University, Vellore 632 104, India, ^cOrganic Chemistry Division, School of Advanced Sciences, VIT University, Vellore 632 104, India, ^dDepartment of Physics, The Madura College, Madurai 625 011, India, and ^eDepartment of Food Science and Technology, University of Ruhuna, Mapalana, Kamburupitiya 81100, Sri Lanka
^*Correspondence e-mail: plakshmannilantha@ymail.com

(Received 15 February 2010; accepted 17 February 2010; online 20 February 2010)

The molecule of the title compound, C₂₈H₂₂O₂, is centrosymmetric with the inversion centre located at the mid-point of the C≡C bond [1.178 (5) Å]. The hydroxyl groups therefore lie on either side of the molecule. The crystal structure is stabilized by O—H⋯O hydrogen bonds, leading to the formation of a linear supramolecular chain along the b axis.

Related literature

For related structures, see: Braga et al. (1997 ); Steiner (1996 ).

Experimental

Crystal data

C₂₈H₂₂O₂
M_r = 390.46
Monoclinic, P 2₁ /n
a = 11.7760 (7) Å
b = 6.1154 (4) Å
c = 14.7620 (9) Å
β = 104.930 (8)°
V = 1027.20 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.23 × 0.21 × 0.19 mm

Data collection

Nonius Mach3 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.982, T_max = 0.985
2268 measured reflections
1793 independent reflections
1190 reflections with I > 2σ(I)
R_int = 0.019
2 standard reflections every 60 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.276
S = 1.09
1793 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1a⋯O1ⁱ	0.82	2.37	3.040 (3)	139
Symmetry code: (i) -x+1, -y, -z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681000629X/tk2631sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681000629X/tk2631Isup2.hkl

checkCIF report

Comment top

As part of our investigations on but-2-yne 1,4-diol molecules, the title molecule, (I), has been synthesized and structurally characterized. The molecule is centrosymmetric with the centre of inversion located at the mid-point of the C14≡C14ⁱ bond, Fig. 1; symmetry operation i: 1-x, 1-y, -z. From symmetry, the hydroxyl groups lie on opposite sides of the molecule. The C14≡C14ⁱ bond distance of 1.178 (5) Å is comparable with those in uncoordinated alkyne, i.e. 1.193 (3) A° (Braga et al., 1997), and 1.200 (4) Å in 2-butyne-1,4-diol (Steiner, 1996). The OH groups in (I) are engaged in intermolecular hydrogen bonding interactions (Table 1) that lead to the formation of a linear supramolecular chain along the b axis.

Related literature top

For related structures, see: Braga et al. (1997); Steiner (1996).

Experimental top

Sodium acetylide (2.5 ml, 18 wt%, 0.01 M) was placed in a round bottom flask, washed twice with dry THF to remove xylene and light mineral oil. A solution of benzophenone (1.82 g, 0.01 M) in dry THF (10 ml) was added drop-wise to the above mixture and stirred for 2 h. A slight excess of powdered ammonium chloride (5 g) was added gradually to decompose the sodium derivative. The mixture was allowed to stand overnight with stirring (to remove excess ammonia). The residue was extracted with dry THF, the organic layer was washed successively with water; dilute sulphuric acid and sodium hydrogen carbonate solutions, and then dried over magnesium sulphate. The obtained product was purified using column chromatography with hexane and ethylacetate (3:2). The obtained product was recrystallized from diethyl ether. M.pt.: 459–461 K, Yield: 52%.

Structure description top

For related structures, see: Braga et al. (1997); Steiner (1996).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. Symmetry operation i: 1-x, 1-y, -z.

(E)-1,1,4,4-Tetraphenylbut-2-yne-1,4-diol top

Crystal data top

C₂₈H₂₂O₂	F(000) = 412
M_r = 390.46	D_x = 1.262 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 11.7760 (7) Å	θ = 2–25°
b = 6.1154 (4) Å	µ = 0.08 mm⁻¹
c = 14.7620 (9) Å	T = 293 K
β = 104.930 (8)°	Block, colourless
V = 1027.20 (11) Å³	0.23 × 0.21 × 0.19 mm
Z = 2

Data collection top

Nonius Mach3 diffractometer	1190 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 25.0°, θ_min = 2.6°
ω–2θ scans	h = 0→13
Absorption correction: ψ scan (North et al., 1968)	k = −1→7
T_min = 0.982, T_max = 0.985	l = −17→16
2268 measured reflections	2 standard reflections every 60 min
1793 independent reflections	intensity decay: none

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.276	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.191P)² + 0.1322P] where P = (F_o² + 2F_c²)/3
1793 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₂₈H₂₂O₂	V = 1027.20 (11) Å³
M_r = 390.46	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.7760 (7) Å	µ = 0.08 mm⁻¹
b = 6.1154 (4) Å	T = 293 K
c = 14.7620 (9) Å	0.23 × 0.21 × 0.19 mm
β = 104.930 (8)°

Data collection top

Nonius Mach3 diffractometer	1190 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.019
T_min = 0.982, T_max = 0.985	2 standard reflections every 60 min
2268 measured reflections	intensity decay: none
1793 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.276	H-atom parameters constrained
S = 1.09	Δρ_max = 0.35 e Å⁻³
1793 reflections	Δρ_min = −0.29 e Å⁻³
136 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C14	0.4922 (3)	0.4489 (5)	0.03168 (19)	0.0503 (8)
O1	0.5081 (2)	0.0924 (4)	0.09705 (15)	0.0718 (9)
H1A	0.4679	0.0450	0.0471	0.108*
C12	0.5499 (2)	0.3958 (5)	0.20504 (18)	0.0443 (8)
C13	0.4735 (3)	0.3145 (5)	0.10995 (18)	0.0471 (8)
C11	0.5673 (3)	0.2553 (6)	0.2819 (2)	0.0619 (9)
H11	0.5343	0.1162	0.2752	0.074*
C6	0.3446 (3)	0.3186 (5)	0.11176 (17)	0.0496 (8)
C7	0.5985 (3)	0.5994 (5)	0.2167 (2)	0.0569 (9)
H7	0.5862	0.6945	0.1659	0.068*
C1	0.2929 (4)	0.1361 (7)	0.1416 (2)	0.0754 (12)
H1	0.3356	0.0079	0.1585	0.090*
C5	0.2780 (3)	0.5067 (6)	0.0880 (2)	0.0605 (9)
H5	0.3123	0.6296	0.0690	0.073*
C9	0.6848 (3)	0.5280 (7)	0.3798 (2)	0.0707 (11)
H9	0.7307	0.5718	0.4381	0.085*
C10	0.6348 (3)	0.3262 (7)	0.3685 (2)	0.0742 (11)
H10	0.6459	0.2334	0.4199	0.089*
C8	0.6667 (3)	0.6660 (7)	0.3044 (3)	0.0681 (10)
H8	0.6999	0.8049	0.3116	0.082*
C4	0.1615 (3)	0.5167 (8)	0.0917 (3)	0.0861 (14)
H4	0.1181	0.6442	0.0749	0.103*
C2	0.1750 (5)	0.1500 (11)	0.1458 (3)	0.0978 (17)
H2	0.1398	0.0299	0.1660	0.117*
C3	0.1116 (4)	0.3374 (12)	0.1204 (3)	0.1031 (19)
H3	0.0335	0.3425	0.1228	0.124*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C14	0.0636 (18)	0.0556 (19)	0.0336 (14)	0.0098 (14)	0.0161 (13)	0.0068 (12)
O1	0.129 (2)	0.0447 (14)	0.0443 (12)	0.0142 (13)	0.0267 (13)	−0.0013 (10)
C12	0.0537 (16)	0.0489 (17)	0.0340 (14)	0.0073 (13)	0.0182 (11)	0.0070 (12)
C13	0.0724 (19)	0.0384 (16)	0.0340 (15)	0.0061 (13)	0.0201 (13)	0.0056 (11)
C11	0.078 (2)	0.062 (2)	0.0448 (17)	−0.0043 (16)	0.0145 (15)	0.0139 (15)
C6	0.0677 (19)	0.0574 (19)	0.0246 (13)	−0.0177 (15)	0.0138 (12)	−0.0078 (12)
C7	0.067 (2)	0.0514 (19)	0.0527 (18)	0.0034 (15)	0.0167 (15)	0.0098 (14)
C1	0.105 (3)	0.076 (2)	0.0483 (19)	−0.031 (2)	0.0263 (18)	−0.0002 (17)
C5	0.063 (2)	0.066 (2)	0.0534 (19)	0.0021 (16)	0.0166 (15)	−0.0072 (16)
C9	0.059 (2)	0.099 (3)	0.0489 (19)	0.004 (2)	0.0057 (15)	−0.0053 (19)
C10	0.080 (2)	0.096 (3)	0.0424 (18)	0.004 (2)	0.0081 (16)	0.0191 (18)
C8	0.067 (2)	0.070 (2)	0.064 (2)	−0.0095 (18)	0.0111 (16)	−0.0126 (18)
C4	0.068 (2)	0.122 (4)	0.068 (2)	0.001 (2)	0.0177 (19)	−0.035 (2)
C2	0.108 (3)	0.132 (4)	0.063 (3)	−0.073 (3)	0.038 (2)	−0.032 (3)
C3	0.081 (3)	0.161 (5)	0.078 (3)	−0.046 (4)	0.039 (2)	−0.052 (3)

Geometric parameters (Å, º) top

C14—C14ⁱ	1.178 (5)	C1—C2	1.408 (7)
C14—C13	1.480 (4)	C1—H1	0.9300
O1—C13	1.445 (3)	C5—C4	1.389 (5)
O1—H1A	0.8200	C5—H5	0.9300
C12—C7	1.363 (4)	C9—C10	1.359 (5)
C12—C11	1.395 (4)	C9—C8	1.370 (5)
C12—C13	1.541 (4)	C9—H9	0.9300
C13—C6	1.526 (4)	C10—H10	0.9300
C11—C10	1.389 (5)	C8—H8	0.9300
C11—H11	0.9300	C4—C3	1.362 (7)
C6—C5	1.385 (5)	C4—H4	0.9300
C6—C1	1.395 (5)	C2—C3	1.366 (7)
C7—C8	1.396 (5)	C2—H2	0.9300
C7—H7	0.9300	C3—H3	0.9300

C14ⁱ—C14—C13	178.3 (4)	C2—C1—H1	120.6
C13—O1—H1A	109.5	C6—C5—C4	121.8 (4)
C7—C12—C11	119.4 (3)	C6—C5—H5	119.1
C7—C12—C13	122.5 (2)	C4—C5—H5	119.1
C11—C12—C13	118.1 (3)	C10—C9—C8	119.2 (3)
O1—C13—C14	108.4 (2)	C10—C9—H9	120.4
O1—C13—C6	109.5 (3)	C8—C9—H9	120.4
C14—C13—C6	110.7 (2)	C9—C10—C11	121.6 (3)
O1—C13—C12	107.7 (2)	C9—C10—H10	119.2
C14—C13—C12	111.3 (2)	C11—C10—H10	119.2
C6—C13—C12	109.2 (2)	C9—C8—C7	120.4 (3)
C10—C11—C12	119.0 (3)	C9—C8—H8	119.8
C10—C11—H11	120.5	C7—C8—H8	119.8
C12—C11—H11	120.5	C3—C4—C5	119.1 (5)
C5—C6—C1	118.7 (3)	C3—C4—H4	120.5
C5—C6—C13	120.7 (3)	C5—C4—H4	120.5
C1—C6—C13	120.6 (3)	C3—C2—C1	120.9 (4)
C12—C7—C8	120.4 (3)	C3—C2—H2	119.5
C12—C7—H7	119.8	C1—C2—H2	119.5
C8—C7—H7	119.8	C4—C3—C2	120.8 (4)
C6—C1—C2	118.7 (5)	C4—C3—H3	119.6
C6—C1—H1	120.6	C2—C3—H3	119.6

C14ⁱ—C14—C13—O1	7 (15)	C12—C13—C6—C1	−90.2 (3)
C14ⁱ—C14—C13—C6	−114 (15)	C11—C12—C7—C8	1.0 (5)
C14ⁱ—C14—C13—C12	125 (15)	C13—C12—C7—C8	179.7 (3)
C7—C12—C13—O1	137.1 (3)	C5—C6—C1—C2	0.4 (5)
C11—C12—C13—O1	−44.2 (3)	C13—C6—C1—C2	177.5 (3)
C7—C12—C13—C14	18.4 (4)	C1—C6—C5—C4	−1.0 (5)
C11—C12—C13—C14	−162.8 (3)	C13—C6—C5—C4	−178.1 (3)
C7—C12—C13—C6	−104.1 (3)	C8—C9—C10—C11	1.1 (6)
C11—C12—C13—C6	74.7 (3)	C12—C11—C10—C9	−0.6 (6)
C7—C12—C11—C10	−0.5 (5)	C10—C9—C8—C7	−0.6 (5)
C13—C12—C11—C10	−179.3 (3)	C12—C7—C8—C9	−0.4 (5)
O1—C13—C6—C5	−155.4 (2)	C6—C5—C4—C3	0.6 (5)
C14—C13—C6—C5	−36.0 (4)	C6—C1—C2—C3	0.5 (6)
C12—C13—C6—C5	86.8 (3)	C5—C4—C3—C2	0.4 (6)
O1—C13—C6—C1	27.6 (3)	C1—C2—C3—C4	−0.9 (7)
C14—C13—C6—C1	147.0 (3)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1a···O1ⁱⁱ	0.82	2.37	3.040 (3)	139

Symmetry code: (ii) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₂₈H₂₂O₂
M_r	390.46
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	11.7760 (7), 6.1154 (4), 14.7620 (9)
β (°)	104.930 (8)
V (Å³)	1027.20 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.23 × 0.21 × 0.19

Data collection
Diffractometer	Nonius Mach3
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.982, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	2268, 1793, 1190
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.276, 1.09
No. of reflections	1793
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.29

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1a···O1ⁱ	0.82	2.37	3.040 (3)	139

Symmetry code: (i) −x+1, −y, −z.

Acknowledgements

The authors thank the DST for support through the FIST programme. VV is grateful to DST-India for funding through the Young Scientist Scheme (Fast Track Proposal).

References

Braga, D., Grepioni, F., Walther, D., Heubach, K., Schmidt, A., Imhof, W., Görls, H. & Klettke, T. (1997). Organometallics, 16, 4910–4919. CSD CrossRef CAS Web of Science Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
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