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The molecular structure of 5-norbornene - 2.3 endo-dicarboxylic anhydride
TetrahedronLetters No.57, pp. 5955-5958,1968. PergemonPress. Printed in Greet Britain.
THE MOLECULAR SlRUC'lUREOF 5-NORBORNENR- 2.3 ENDO-DICARBOXYLICANBYDRIDE R.
Destro, G.Filippini,C.hi.Gramaocioli and M.Simonetta Istituto
di Chimica Fisica, Universitii di Milano 20133 Milano. Italy
(Receivedin UK 15 October 1968; accepted for publication25 October 1968)
The conformationof the derivativesof norbornane and related hydrocarbons is a subject of considerableinterest, which is evident in an extensive series of experimentalphysico-chemioalstudies (1.2,3,4,5.6,7,8) and many semi-empiricalcalculations(9,10,11,12,13,14). This interest has prompted a determinationof the crystal struotare of S-norbornene2.3 endo-dicarboxylicanhydrideCgH803 by X-ray diffraction. The crystals of the substance are orthorhombic,space group P 21212I , with 2 - 13.5394 ( 2 0.0008) , 2 - 9.5648 (2 0.0016) , 2 - 5.9721 (+0.0003)t and four molecules per unit cell. These data were obtained by Cohen's back reflectionmethod, as described by Buerger (15) , using Cu Kd (A,-
1.54051 *
A2
-
radiation
1.54433i ) at a room temperatureof 21eC. The
effective radius of the camera (an ordinary Weissenberg)was determined by mounting the film according to Straumanis technique. The standard deviationswere taken from the sum of the residuals. according to Whittaker'andRobinson (16). The measured density is 1.417 g cm-3 and the correspondingcalculatedvalue is 1.409. The struaturewas solved by three-dimensionalPatterson synthesis and refined by least-squares. At the end of the refinement,the R index is 0.072 on 802 observed independentreflexions.
5955
No.57
Figure 1 - B&d
distances and angles in 5-norbornene-2,3 endo-
dicarboxylic anhydride. The molecule is seen along the direction corresponding to the maximum moment of inertia.
The most salient details of the moleoular geometry are reported
in
Fi
gure 1. The bridgehead angle C(l)-C(7)&(4) oan be comparedwith a value of 92.70 * 970 and 96“ , as found in the nuoleus of oyolopentadiene dimer (6) , trioyolo [3,2.1,02*4 I ootane (4) and norbornene (S),respeotively, by X-ray diffraction , or with 93.2O or 920, as obtained for norbornane and norbornadiene.respectively,by eleotron diffractionin gas phase (7). The length of the double bond C(S)-C(6) is normal : the single bonds C(l)-C(2) and C(3)&(4) are signifioantlylonger than C(l)-C(6) and C(4)-C(5).A similar effect ooours in the nuoleos of oyolopentadienedimer (6). In the norbornene nucleus, the atoms C(l),C(2).C(3)and C(4) are ooplanar within 0.02 %
; the atoms C(l),C(4),C(S)and C(6) are ooplanar
within 0.01 % . The dihedral angle between these two planes is 1130 ; the angles between them and the plane defined by C(l),C(4) and C(7) are 1170 and 1300 , respectively. The bond distances and angles in the anhydridegroup are similar to the ones of auocinio anhydride , as found by Ehrenberg (17) and Bisgini and Cannas (18) : all the carbon and oxygen atoms in this group are ooplanar within 0.04 !. Acknowledgement The financial support of Consiglio Nazionale delle Rioerche (C.N.R.) ia gratefully achnowledged.
No.57
REFERENCES (1) G.Fergueon~
C.
J.Fritahie,J.M.Bobertsonand G.A.Sim ,J.Chem.Soo. .1976 (1961)
(31 D.A.Brueobner,T.A.lfamor, (3) A.Ceaur and D.F.Grant ,
J.Chem.Soo.
Aota Cryat.
,799
(1962)
A!!' 55 (1965)
(4) .A.C.MnDonaldand J.Trotter , Aota Crvet. 11 , 243 (1965) (5) A.C.MaDonaldand J.Trotter , data Cruet. 2,9, 456 (1965) (6) R.Deatro,C.M.Gramaoafoli and M.Simonetta , Chem.Co~.,
568 (1968)
(7) Y.Morino,K.Kuohitsu,A.Yokoxechi , Bull.Chem.Soo.JaDan,i,O(6),1552 (1967) (8) J.K.Krieger, Suomen Kemiatilehti ,s_31 ,1348 (1958); ibidem B 32,109 (1959) ---(9) C.F.Wiloox,jr., J.Am.Chem.Soo.,zl.414 (1960) (10) G.J.Glei&er and P.von R.Schleyer, ,T.Am.Chem.Soc.. i,9.582 (1961) (11) N~L.kZlinger,J.A,Hira~h,~.A,Miller,I. J.Tpninski,F,A,vanCatledge, J.Am.Chem.Sotr., 2_0,1199(1968) (12) C.Y.Cben,L.J.W.LeFBvre and K&.S.Sundaram, J.Chem.Soo.,553 (1965) (131 C.F.Wilaox,jr.,S.Winatein and W.G.~~ill~, _J.Am.Chem.Soc., ii, 5450 (1960) (14) A.Wassermann
J.Chem.Soc.,
612 (11942)
(15) Y.J.Buerger X-Rev Crpstallonranhyp.431. John \Viley& Sona,New York (1943) (X6) B.Whittaker and G.Robineon The Calculus of Observation8p.246.Blaokie & Sons,London (1924) (17) M.Bhrenb@rg , Acta Crwt., (18) S.Bi~i~,~.C~n~
i,9,698 (1965)
Ricercs Soientifi~a.Rendi~.Sez.A ,I (6),1518 (1965)
THE MOLECULAR SlRUC'lUREOF 5-NORBORNENR- 2.3 ENDO-DICARBOXYLICANBYDRIDE R.
Destro, G.Filippini,C.hi.Gramaocioli and M.Simonetta Istituto
di Chimica Fisica, Universitii di Milano 20133 Milano. Italy
(Receivedin UK 15 October 1968; accepted for publication25 October 1968)
The conformationof the derivativesof norbornane and related hydrocarbons is a subject of considerableinterest, which is evident in an extensive series of experimentalphysico-chemioalstudies (1.2,3,4,5.6,7,8) and many semi-empiricalcalculations(9,10,11,12,13,14). This interest has prompted a determinationof the crystal struotare of S-norbornene2.3 endo-dicarboxylicanhydrideCgH803 by X-ray diffraction. The crystals of the substance are orthorhombic,space group P 21212I , with 2 - 13.5394 ( 2 0.0008) , 2 - 9.5648 (2 0.0016) , 2 - 5.9721 (+0.0003)t and four molecules per unit cell. These data were obtained by Cohen's back reflectionmethod, as described by Buerger (15) , using Cu Kd (A,-
1.54051 *
A2
-
radiation
1.54433i ) at a room temperatureof 21eC. The
effective radius of the camera (an ordinary Weissenberg)was determined by mounting the film according to Straumanis technique. The standard deviationswere taken from the sum of the residuals. according to Whittaker'andRobinson (16). The measured density is 1.417 g cm-3 and the correspondingcalculatedvalue is 1.409. The struaturewas solved by three-dimensionalPatterson synthesis and refined by least-squares. At the end of the refinement,the R index is 0.072 on 802 observed independentreflexions.
5955
No.57
Figure 1 - B&d
distances and angles in 5-norbornene-2,3 endo-
dicarboxylic anhydride. The molecule is seen along the direction corresponding to the maximum moment of inertia.
The most salient details of the moleoular geometry are reported
in
Fi
gure 1. The bridgehead angle C(l)-C(7)&(4) oan be comparedwith a value of 92.70 * 970 and 96“ , as found in the nuoleus of oyolopentadiene dimer (6) , trioyolo [3,2.1,02*4 I ootane (4) and norbornene (S),respeotively, by X-ray diffraction , or with 93.2O or 920, as obtained for norbornane and norbornadiene.respectively,by eleotron diffractionin gas phase (7). The length of the double bond C(S)-C(6) is normal : the single bonds C(l)-C(2) and C(3)&(4) are signifioantlylonger than C(l)-C(6) and C(4)-C(5).A similar effect ooours in the nuoleos of oyolopentadienedimer (6). In the norbornene nucleus, the atoms C(l),C(2).C(3)and C(4) are ooplanar within 0.02 %
; the atoms C(l),C(4),C(S)and C(6) are ooplanar
within 0.01 % . The dihedral angle between these two planes is 1130 ; the angles between them and the plane defined by C(l),C(4) and C(7) are 1170 and 1300 , respectively. The bond distances and angles in the anhydridegroup are similar to the ones of auocinio anhydride , as found by Ehrenberg (17) and Bisgini and Cannas (18) : all the carbon and oxygen atoms in this group are ooplanar within 0.04 !. Acknowledgement The financial support of Consiglio Nazionale delle Rioerche (C.N.R.) ia gratefully achnowledged.
No.57
REFERENCES (1) G.Fergueon~
C.
J.Fritahie,J.M.Bobertsonand G.A.Sim ,J.Chem.Soo. .1976 (1961)
(31 D.A.Brueobner,T.A.lfamor, (3) A.Ceaur and D.F.Grant ,
J.Chem.Soo.
Aota Cryat.
,799
(1962)
A!!' 55 (1965)
(4) .A.C.MnDonaldand J.Trotter , Aota Crvet. 11 , 243 (1965) (5) A.C.MaDonaldand J.Trotter , data Cruet. 2,9, 456 (1965) (6) R.Deatro,C.M.Gramaoafoli and M.Simonetta , Chem.Co~.,
568 (1968)
(7) Y.Morino,K.Kuohitsu,A.Yokoxechi , Bull.Chem.Soo.JaDan,i,O(6),1552 (1967) (8) J.K.Krieger, Suomen Kemiatilehti ,s_31 ,1348 (1958); ibidem B 32,109 (1959) ---(9) C.F.Wiloox,jr., J.Am.Chem.Soo.,zl.414 (1960) (10) G.J.Glei&er and P.von R.Schleyer, ,T.Am.Chem.Soc.. i,9.582 (1961) (11) N~L.kZlinger,J.A,Hira~h,~.A,Miller,I. J.Tpninski,F,A,vanCatledge, J.Am.Chem.Sotr., 2_0,1199(1968) (12) C.Y.Cben,L.J.W.LeFBvre and K&.S.Sundaram, J.Chem.Soo.,553 (1965) (131 C.F.Wilaox,jr.,S.Winatein and W.G.~~ill~, _J.Am.Chem.Soc., ii, 5450 (1960) (14) A.Wassermann
J.Chem.Soc.,
612 (11942)
(15) Y.J.Buerger X-Rev Crpstallonranhyp.431. John \Viley& Sona,New York (1943) (X6) B.Whittaker and G.Robineon The Calculus of Observation8p.246.Blaokie & Sons,London (1924) (17) M.Bhrenb@rg , Acta Crwt., (18) S.Bi~i~,~.C~n~
i,9,698 (1965)
Ricercs Soientifi~a.Rendi~.Sez.A ,I (6),1518 (1965)