CRYSTAL ENGINEERING AND SOLID-STATE CHEMISTRY OF SOME BETA-NITROSTYRENES

被引:43
作者
PEDIREDDI, VR
SARMA, JARP
DESIRAJU, GR
机构
[1] UNIV HYDERABAD,SCH MED,PO CENT UNIV,HYDERABAD 500134,ANDHRA PRADESH,INDIA
[2] INDIAN INST CHEM TECHNOL,DIV INORGAN & PHYS CHEM,HYDERABAD 500007,INDIA
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 1992年 / 02期
关键词
D O I
10.1039/p29920000311
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The unusual solid state photodimerisation of (E)-beta-nitrostyrene to yield 'topochemical' and 'non-topochemical' cyclobutanes is accounted for by its disordered, photoreactive crystal structure which is monoclinic, P2(1)/c, Z = 4, a = 8.097(6) angstrom, b = 5.768(5) angstrom, c = 18.647(2) angstrom, beta = 117.71(5)-degrees. This structure permits a trans --> cis isomerisation which facilitates the formation of the anomalous product. However, 4-methyl-beta-nitrostyrene which has a very similar disordered structure is photostable in the solid state since the potentially 'reactive' double bonds are beyond the topochemical threshold. C-H ... O and C-H ... Cl interactions are important to the exclusion of Cl ... Cl interactions in the layered structure of the 4-chloro derivative, but this nitrostyrene forms mixed crystals with the 4-methyl compound in the disordered structure of the latter showing that the role of the Cl atom in the 4-chloro derivative is at best marginal. In contrast, the higher Cl stoichiometry in the 2,4-dichloro analogue results in a layered, photoreactive beta-structure characterised by Cl ... Cl and C-H ... O interactions. The structures of three layered alkoxy-beta-nitrostyrenes are very similar to each other and are held by strong, directional C-H ... O contacts. The 4-methoxy compound has a photostable crystal structure while the 3,4-methylenedioxy and 3,4-dimethoxy crystals appear to be capable of topochemical 2 + 2 cycloaddition. However, only the latter is photoreactive because of optimal double-bond-to-double-bond overlap in the crystal. The 4-bromo derivative is distinct from the 4-chloro compound and there are two molecules in the asymmetric unit because of conflicting packing requirements of the C-H ... O and Br ... O interactions. A survey of 84 intermolecular Br ... O contacts retrieved from 39 nitro-bromo crystal structures has revealed that at least some of these arise due to halogen polarisability. Atomic motion analysis in this crystal structure indicates the importance of lateral C-H ... O interactions.
引用
收藏
页码:311 / 320
页数:10
相关论文
共 30 条
[1]   PHOTOCHROMIC 1-ARYL-2-NITROALKENES [J].
BLUHM, AL ;
WEINSTEIN, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1965, 87 (23) :5511-&
[2]   CRYSTAL-CHEMISTRY OF SOME (ALKOXYPHENYL)PROPIOLIC ACIDS - THE ROLE OF OXYGEN AND HYDROGEN-ATOMS IN DETERMINING STACK STRUCTURES OF PLANAR AROMATIC-COMPOUNDS [J].
DESIRAJU, GR ;
KISHAN, KVR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (13) :4838-4843
[3]   PSEUDOINVERSION CENTERS IN SPACE GROUP P1 AND A REDETERMINATION OF THE CRYSTAL-STRUCTURE OF 3,4-DIMETHOXYCINNAMIC ACID - A STUDY OF NON-CRYSTALLOGRAPHIC SYMMETRY [J].
DESIRAJU, GR ;
CALABRESE, JC ;
HARLOW, RL .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 1991, 47 :77-86
[4]   FROM MOLECULAR TO CRYSTAL-STRUCTURE - POLYNUCLEAR AROMATIC-HYDROCARBONS [J].
DESIRAJU, GR ;
GAVEZZOTTI, A .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (10) :621-623
[5]   THE NATURE OF HALOGEN ... HALOGEN INTERACTIONS - ARE SHORT HALOGEN CONTACTS DUE TO SPECIFIC ATTRACTIVE FORCES OR DUE TO CLOSE PACKING OF NONSPHERICAL ATOMS [J].
DESIRAJU, GR ;
PARTHASARATHY, R .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (23) :8725-8726
[6]   SOLID-STATE DIMERIZATION OF BETA-NITROSTYRENE - A DISORDERED PHOTOREACTIVE CRYSTAL [J].
DESIRAJU, GR ;
PEDIREDDI, VR .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (16) :1112-1113
[7]  
DESIRAJU GR, 1986, P INDIAN AS-CHEM SCI, V96, P599
[8]  
DESIRAJU GR, 1989, CRYSTAL ENG DESIGN O, P85
[9]  
DESIRAJU GR, 1989, ACTA CRYSTALLOGR B, V45, P621
[10]  
DESIRAJU GR, 1987, ORGANIC SOLID STATE, P519