Structure of α-benzylidene-(±)-piperitone, an exception to topochemical behaviour

Kanagapushpam, D.; Ramamurthy, V.; Venkatesan, Κ.

doi:10.1107/s0108270187092783

Cited by 10 publications

(10 citation statements)

References 9 publications

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“…The numbering scheme is shown in Fig. 1 and the packing of the molecules viewed -4020(9) 1399 l(5) I0734( 5) 11670(8) 1 05 3 7( 7) 11741( 6) 14707( 7) 12476(8) 8 159( 8) 1 2 5 5 5( 9) 6 194( 8) 5788( 1 ) 6443( 1) 41 32( 2) 4896( 2) 5701( 2) 6723(2) 7 I 7 l(2) 4827( 2) 3523( 2) 4761( 3) 6712( 1) 6056( 1) 8 362( 2) 7596( 2) 6802( 2) 5778( 2) 5322( 2) 7672( 2) 8976( 2) 7742(3) 3527 4302( 1) 3716( 2) 4121( 2) 3988( 2) 3508( 3) 4007( 2) 4638( 2) 3356( 2) 5053 (2) 701 l( 1) 6231( 1) 6826( 2) 641 l( 2) 6549( 2) 7024( 3) 6528( 2) 5893(2) 7 172( 2) 5486( 2)…”

Section: Crystal Dataunclassified

“…The search for new organic materials with non-linear efficiency surpassing those existing has been pursued extensively in recent years.' As part of a research programme on developing good non-linear optical materials and to gain insight into the relation between the macroscopic non-linear susceptibility x (2) and the molecular packing in the unit ell,^-^ the crystal structure of the title compound has been determined. The necessary conditions to be satisfied for showing SHG are: (i) the space group must be non-centrosymmetric, (ii) the difference between the ground-state dipole moment and the excited dipole moment should be large and (iii) the molecule should have loosely bound electrons that can be displaced by an optical field.…”

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confidence: 99%

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Studies of non-linear optical organic materials: crystal and molecular structure of 2-dicyanomethylene-1,3-dioxolane

Dastidar¹,

Row²,

Venkatesan³

1991

J. Mater. Chem.

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Section: Crystal Dataunclassified

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confidence: 99%

Studies of non-linear optical organic materials: crystal and molecular structure of 2-dicyanomethylene-1,3-dioxolane

Dastidar¹,

Row²,

Venkatesan³

1991

J. Mater. Chem.

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“…Thus the chloro group is probably ineffective in inducing a /3-packing mode in these crystal structures. It is observed that all the benzylidene-DL-piperitones studied, namely the unsubstituted compound (Kanagapushpam et al, 1987), and the o-chloro, p-chloro (Venugopalan & Venkatesan, 1990), p-bromo (Venugopalan & Venkatesan, 1991) and p-fluoro derivatives (Kumar & Venkatesan, 1991) are a-packed. It is reasonable to conclude that the overall nonplanar nature of the molecule due to the presence of the cyclohexenone ring which is in a sofa conformation (Romers, Altona, Buys & Havinga, 1969) (see the relevant torsion angles in Table 4) and an isopropyl group does not lead to efficient crystal packing in the fl-mode.…”

Section: (3) Ci(i )---C(2)----c(1)mentioning

confidence: 99%

“…It should be mentioned that in the unsubstituted benzylidene-oL-piperitone, the attainment of ideal geometry by the reactive partners only increased the energy by 0.2 kJ mol-I although the crystal is photostable (Kanagapushpam et al, 1987).…”

Section: (3) Ci(i )---C(2)----c(1)mentioning

confidence: 99%

“…The various strategies adopted to attain the predictive design of organic solids include the use of steering groups such as chloro (Schmidt, 1971;Jones, Ramadas, Theocharis, Thomas & Thomas, 1981;Gnanaguru, Murthy, Venkatesan & Ramamurthy, 1984;Desiraju, 1987), acetoxy (Ramasubbu, Gnanaguru, Venkatesan & Ramamurthy, 1982;Murthy, Ramamurthy & Venkatesan, 1988), sulfur (Nalini & Desiraju, 1987), methylenedioxy (Desiraju, Kamala, Kumari & Sarma, 1984) etc. The steering ability of chlorine as a fl-packing promoter involving a short axis of translation of 4 A is well known (Gnanaguru et al, 1982;Desiraju, 1987) and this encouraged us to examine the photobehaviour of photoinert benzylidene-DL-piperitone (Kanagapushpam, Ramamurthy & Venkatesan, 1987) after chloro substitution.…”

Section: Introductionmentioning

confidence: 99%

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Solid-state photobehaviour and crystal packing of o-chlorobenzylidene-DL-piperitone: influence of molecular topology on photobehaviour

Venugopalan¹,

Venkatesan²

1992

Acta Crystallogr Sect B

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CIvHI9CIO, Mr = 274.7, triclinic, P]-, a = 11.154 (3), b = 12.685 (2), c = 12.713 (2) A, a = 100.68 (1), fl = x 113.58 (1),), = 104.50 (2) °, V = 1511.1 (6)/~3, Z = 4, Dm = 1.22, Dx = 1.215 Mg m -3, Cu Ka, A = 1.5418 A, /z = 2.16 mm 1, F(000) = 584, T = 293 K, v R = 0.057 for 3481 observed reflections. The title compound is photostable in the crystalline state and lattice-energy calculations have been employed to rationalize the photobehaviour. The well-known o fl-steering ability of the chloro group is not operative in this system as there are no CI-.-C1 interactions in the crystal lattice. All five benzylidene-DL-piperitone structures so far studied are a-packed and the molecular topology appears to be a deciding factor even in the presence of steering groups.

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The Factor beyond Schmidt's Criteria Impacting the Photo‐Induced [2+2] Cycloaddition Reactivity and Photoactuation of Molecular Crystals Based on Cyclic Chalcone Analogues

Yue

Dai

Jin

et al. 2023

Chemistry A European J

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Generally, the potential reactive "olefin pairs" in the molecular crystals satisfying Schmidt's criteria could undergo topological [2 + 2] cycloaddition. In this study, another factor that affects the photodimerization reactivity of chalcone analogues was found. The cyclic chalcone analogues of (2H)-one (BTO) have been synthesized. While the geometrical parameters for the molecular packing of the above four compounds did not exceed Schmidt's criteria, [2 + 2] cycloaddition did not occur in the crystals of BIO and BTO. The single crystal structures and Hirshfeld surface analyses revealed that interactions of C=O•••H (CH 2 ) existed between adjacent molecules in the crystal of BIO. Therefore, the carbonyl and methylene groups linked with one carbon atom in carbon-carbon double bond were tightly confined in the lattice, acting as a tweezer to inhibit free movement of the double bond and suppressing [2 + 2] cycloaddition. In the crystal of BTO, similar interactions of Cl•••S and C=O•••H (C 6 H 4 ) prevented free movement of the double bond. In contrast, the intermolecular interaction of C=O•••H only exists around the carbonyl group in the crystals of BFO and NIO, leaving the C=C double bonds to move freely and allowing the occurrence of [2 + 2] cycloaddition. Driven by photodimerization, the needle-like crystals of BFO and NIO displayed evident photo-induced bending behavior. This work demonstrates that the intermolecular interactions around carboncarbon double bond affect the [2 + 2] cycloaddition reactivity except for Schmidt's criteria. These findings provide valuable insights into the design of photomechanical molecular crystalline materials.

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Structure of α-benzylidene-(±)-piperitone, an exception to topochemical behaviour

Abstract: Abstract. C17H200, Mr=240-2, monoclinic,

Cited by 10 publications

References 9 publications

Studies of non-linear optical organic materials: crystal and molecular structure of 2-dicyanomethylene-1,3-dioxolane

Studies of non-linear optical organic materials: crystal and molecular structure of 2-dicyanomethylene-1,3-dioxolane

Solid-state photobehaviour and crystal packing of o-chlorobenzylidene-DL-piperitone: influence of molecular topology on photobehaviour

The Factor beyond Schmidt's Criteria Impacting the Photo‐Induced [2+2] Cycloaddition Reactivity and Photoactuation of Molecular Crystals Based on Cyclic Chalcone Analogues

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