Structure of 2-ethynyl-2-adamantanol

Lin, Shuw-Guann; Okaya, Y.; Chiou, D. M.; Noble, W. J. Le

doi:10.1107/s0567740882006803

Cited by 17 publications

(12 citation statements)

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“…Most notable is the cis arrangement of the amino and nitro groups about the molecular axis, and the intramolecular N(2)-H(2) O(2)-N( 1) hydrogen bond between them which lies nearly parallel to the triple bond. This hydrogen bond is of length 2.34(4) A [2.37(4) A] with an 3)"] at C( 7), and by 6.6(3)" [6.5( 3)"] at C (8) The interaction of the nitro oxygen atom is responsible for the trans bending of the alkyne; hydrogen bonding to an alkyne does not induce a significant change in bonding geometry. Similar results 24 have been reported for the 2,6,2'-trisubstituted tolan 14 which shows an intramolecular hydrogen bond between a phenolic H atom and a carbonyl 0 atom aligned parallel to the triple bond (2.01 A).$…”

Section: Crystallographic Datamentioning

confidence: 99%

Geometry distorting intramolecular interactions to an alkyne group in 1-(2-aminophenyl)-2-(2-nitrophenyl)ethyne: a joint experimental? theoretical study

Pilkington¹,

Wallis²,

Smith³

et al. 1996

J. Chem. Soc., Perkin Trans. 2

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X-Ray diffraction studies on the title compound show that in the crystalline state the amino and nitro groups lie to the same side of the triple bond and are hydrogen bonded to each other. There is a short contact to each alkyne carbon atom; one from a nitro oxygen atom, which leads to a trans bend in the alkyne, and one from an amino hydrogen atom. The analyses of the ab initio electron densities for this molecule and for its conformer with functional groups lying on opposite sides of the triple bond, using the theory of atoms in molecules, indicate that in both cases there is a bond path and associated (3, -1) critical point between the nitro oxygen atom and the nearer alkyne carbon atom, but not between the amino hydrogen atom and its alkyne carbon neighbour. Plots of the Laplacian for both conformers indicate local concentrations of 'lone-pair' density on the nitro oxygen atom, with local depletions in the valence shell charge concentration on the alkyne carbon atom, indicative of a nucleophile/electrophile type interaction. The geometry of the interaction of the alkyne with the amino hydrogen atom is far from optimal in the trans conformer.

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Section: Crystallographic Datamentioning

confidence: 99%

Geometry distorting intramolecular interactions to an alkyne group in 1-(2-aminophenyl)-2-(2-nitrophenyl)ethyne: a joint experimental? theoretical study

Pilkington¹,

Wallis²,

Smith³

et al. 1996

J. Chem. Soc., Perkin Trans. 2

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show abstract

“…This would appear, therefore, to be the ®rst example of this type of intermolecular interaction between two organometallic systems. OÐHÁ Á Á% interactions of this type were ®rst reported by Lin et al (1982) and were subsequently con®rmed by a neutron study (Allen et al, 1996). They are discussed in more detail by Desiraju & Steiner (1999).…”

Section: Commentmentioning

confidence: 71%

(η⁵-Cyclopentadienyl)(3-hydroxy-3-methylbut-1-ynyl-κC¹)(triphenylphosphine-κP)nickel(II): novel O—H...π bonding in an organometallic molecule

McAdam

Robinson

2007

Acta Crystallogr C

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In the title compound, [Ni(C(5)H(5))(C(5)H(7)O)(C(18)H(15)P)], the molecule adopts the expected half-sandwich structure with no unusual metal-ligand distances. No classical hydrogen bonds are found in the structure; instead, the OH group of the butynol unit is involved in an unusual O-H...pi interaction with the C[triple-bond]C group of an adjacent molecule. The crystal structure is further stabilized by C-H...O and C-H...pi interactions, leading to an extensive network of spiral columns.

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“…Thus, 216 structures have C-C C-H forming a normal atom-centred hydrogen bond to N, O, S or halogen atoms as well as accepting a donor-H to form a D-HÁ Á Á(C C) bond, as shown in 2-ethynyl-2adamantanol ( Fig. 2a, CSD refcode BETXAZ; Lin et al, 1982). A further 113 structures have the C-C C-H donor forming hydrogen bonds to (C C) or (phenyl) with the (C C) accepting a hydrogen from N-H, O-H or C(ar)-H. In 4-ethynylaniline (BUPQAE01; Dey et al, 2003) the C-C C-H donates to the phenyl ring, while the (C C) accepts both N-H and C(ar)-H, as shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

“…2 for a note on the depiction of the triple bonds. Formation of multiple interactions by ethynyl groups: (a) C-C C-HÁ Á ÁO and O-HÁ Á Á (C C) bonds in BETXAZ (Lin et al, 1982); (b) C-CÁ Á ÁC-HÁ Á Á(phenyl) and N-HÁ Á Á(C C) and C(phenyl)-HÁ Á Á(C C) in BUPQAE01 (Dey et al, 2003); (c) C-C C-HÁ Á ÁO and C-C C-HÁ Á Á(C C) bifurcation together with O-HÁ Á Á (C C) bonds in PICMAQ (Milroy et al, 2007). Note that Mercury (Macrae et al, 2006(Macrae et al, , 2008 draws triple bonds on the surface of a cylinder which are clearly visible when manipulated in three dimensions.…”

Section: Resultsmentioning

confidence: 99%

The versatile role of the ethynyl group in crystal packing: an interaction propensity study

Allen

Wood

Galek

2013

Acta Crystallogr Sect B

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It is well documented that the ethynyl group can act as a hydrogen-bond donor via its acidic C-H, and as a hydrogen-bond acceptor via the triple-bond π-density. Using the Cambridge Structural Database (CSD), it is shown that C-C≡C-H forms hydrogen bonds to N, O, S or halogens in 74% of structures in which these bonds can form. Additionally, the ethynyl group forms C-H···π interactions with itself or with phenyl groups in 23% of structures and accepts hydrogen bonds from O-H, N-H or C(aromatic)-H in 47% of structures where such bonds are possible. Overall, C-C≡C-H acts as a donor or acceptor in 87% of structures in which it occurs. These propensities for hydrogen-bond formation have been determined using quite tight geometrical constraints, and many more ethynyl groups form interactions with only slight relaxations of these constraints. We conclude that the ethynyl group makes crucial contributions to molecular aggregation in crystal structures, and this is exemplified by hydrogen-bond predictions for specific structures made using the statistical propensity tool now available in CSD system software.

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Structure of 2-ethynyl-2-adamantanol

Cited by 17 publications

References 0 publications

Geometry distorting intramolecular interactions to an alkyne group in 1-(2-aminophenyl)-2-(2-nitrophenyl)ethyne: a joint experimental? theoretical study

Geometry distorting intramolecular interactions to an alkyne group in 1-(2-aminophenyl)-2-(2-nitrophenyl)ethyne: a joint experimental? theoretical study

(η⁵-Cyclopentadienyl)(3-hydroxy-3-methylbut-1-ynyl-κC¹)(triphenylphosphine-κP)nickel(II): novel O—H...π bonding in an organometallic molecule

The versatile role of the ethynyl group in crystal packing: an interaction propensity study

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Structure of 2-ethynyl-2-adamantanol

Cited by 17 publications

References 0 publications

Geometry distorting intramolecular interactions to an alkyne group in 1-(2-aminophenyl)-2-(2-nitrophenyl)ethyne: a joint experimental? theoretical study

Geometry distorting intramolecular interactions to an alkyne group in 1-(2-aminophenyl)-2-(2-nitrophenyl)ethyne: a joint experimental? theoretical study

(η5-Cyclopentadienyl)(3-hydroxy-3-methylbut-1-ynyl-κC1)(triphenylphosphine-κP)nickel(II): novel O—H...π bonding in an organometallic molecule

The versatile role of the ethynyl group in crystal packing: an interaction propensity study

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(η⁵-Cyclopentadienyl)(3-hydroxy-3-methylbut-1-ynyl-κC¹)(triphenylphosphine-κP)nickel(II): novel O—H...π bonding in an organometallic molecule