Harkema, Sybolt

Veggel, Frank C.J.M. van

English

van Veggel, F.C.J.M.

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Structure of 2-[(4-cyanophenyl)methylene]-1,3-dithiole-4,5-dicarboxylic acid, dimethyl ester

University of Twente Research Information

393 Acta Cryst. (1992). C48, 393-395 Structure of 2-[(4-Cyanophenyl)methylenel-l,3-dithiole-4,5-dicarboxylic Acid, Dimethyl Ester BY FRANK C. J. M. VAN VEGGEL* Akzo Research Laboratories Arnhem, Department of  Organic and Polymer Chemistry, PO Box 9300, 6800 SB Arnhem, The Netherlands AND SYBOLT HARKEMA Laboratory of  Chemical Physics, University of  Twente, PO Box 217, 7500 AE Enschede, The Netherlands (Received 12 June 1991; accepted 23 July 1991) A b s t r a c t .  C15H11NO4S2, Mr = 333.39, triclinic, P1, a =20.611(7) ,  b = 9 . 4 5 2 ( 5 ) ,  c = 7 . 8 5 6 ( 4 )  A, a--- 98.52 (3), /3 = 96.05 (2), 9' = 93.0 (3) °, V = 1502 (2) ]k 3, Z = 4, Dx = 1.475 g cm-3, a(Mo Ka) = 0.7107 A, /z = 3.55 cm-1, F(000) = 688, T = 293 K, R = 0 . 0 5 1  (wR=0.059)  for 3388 reflections. The asymmetric unit contains two independent molecules which have a similar conformation. The dithiole ring is planar in both molecules and makes an angle with the phenyl ring of 2. I and 0.6 °, respectively. Thus the methylene-l,3-dithiole unit (electron donor) has a maximum zr overlap with the phenyl ring, that bears a p-cyano group (electron acceptor). In both mol- ecules the methyl esters are planar: one is almost parallel to the dithiole ring (angles of 9.8 and 8.5 °, respectively) and the other makes angles of 54.2 and 63.8 ° , respectively. E x p e r i m e n t a l .  The title molecule (see scheme) was prepared following the procedure reported by Mul- vaney & Chang (1980) for 2-(phenylmethylene)-l,3- dithiole-4,5-dicarboxylic acid, dimethyl ester, starting from p-cyanobenzaldehyde, dimethyl acetylenedicar- boxylate and carbon disulfide in the presence of (n-Bu)3P in diethyl ether at 250 K. Orange-red cubes were obtained by recrystallization from acetonitrile, dimensions 0.4 × 0.5 x 0.5 mm. COOMe ~ S ~ COOMe CN * To whom correspondence should be addressed. 0108-2701/92/020393-03503.00 Table 1. Positional parameters and their estimated standard deviations Beq = ( 8 zr~ / 3 ) Y-FjUoa~* aj*a,.aj. x y z n . ~ .  ~ , t~2)  SI 0.97420 (5) 0.2917 (1) 0.2758 (2) 4.31 (2) C2 0.9848 (2) 0.1072 (4) 0.2607 (5) 3.18 (8) $3 0.91830 (5) 0.0131 (1) 0.3257 (2) 3.90 (2) C4 0.8708 (2) 0.1585 (4) 0.3641 (5) 3.51 (9) C5 0.8958 (2) 0.2848 (4) 0.3362 (5) 3.82 (9) C6 1.0393 (2) 0.0545 (4) 0.2074 (5) 3.47 (9) C7 1.0587 (2) -0.0919 (4) 0.1891 (5) 3.17 (8) C8 1.0190 (2) -0.2093 (4) 0.2160 (6) 4.9 (I) C9 1.0410 (2) -0.3443 (4) 0.1973 (7) 5.4 (1) CI0 1.1018 (2) -0.3683 (4) 0.1480 (6) 4.1 (I) C11 1.1421 (2) - 0.2550 (4) 0.1176 (6) 4.2 (I) C12 1.1202 (2) -0.1194 (4) 0.1395 (5) 3.63 (9) C13 1.1220 (2) -0.5133 (5) 0.1236 (7) 5.5 (1) NI4  1.1364 (2) -0.6280 (4) 0.1038 (8) 8.3 (1) C15 0.8618 (2) 0.4196 (5) 0.3430 (6) 4.9 (1) O16 0.8083 (2) 0.4225 (4) 0.2631 (7) 11.0 (1) OI7 0.8913 (2) 0.5229 (3) 0.4351 (6) 8.2 (1) CI8 0.8613 (3) 0.6612 (5) 0.439 (1) 8.9 (2) C19 0.8073 (2) 0.1314 (5) 0.4319 (6) 4.4 (1) 020 0.7745 (2) 0.2241 (4) 0.4837 (5) 7.9 (1) O21 0.7947 (I) -0.0048 (3) 0.4358 (4) 5.63 (8) C22 0.7371 (3) -0.0462 (7) 0.5150 (7) 7.8 (2) $31 0.55995 (6) 0.2155 (I) 0.2519 (2) 4.86 (3) C32 0.5687 (2) 0.3954 (4) 0.2171 (5) 3.43 (9) $33 0.49813 (5) 0.4862 (1) 0.2501 ~1) 3.49 (2) C34 0.4519 (2) 0.3425 (4) 0.3053 (5) 3.08 (8) C35 0.4807 (2) 0.2197 (4) 0.3049 (5) 3.37 (8) C36 0.6250 (2) 0.4476 (4) 0.1714 (5) 3.72 (9) C37 0.6425 (2) 0.5919 (4) 0.1383 (5) 3.36 (9) C38 0.6024 (2) 0.7047 (4) 0.1500 (6) 4.3 (1) C39 0.6221 (2) 0.8373 (4) 0.1133 (6) 4.4 (1) C40 0.6831 (2) 0.8617 (4) 0.0663 (5) 3.79 (9) C41 0.7241 (2) 0.7518 (5) 0.0540 (6) 4.9 (1) C42 0.7045 (2) 0.6205 (5) 0.0911 (6) 4.3 (1) C43 0.7033 (2) 1.0000 (5) 0.0292 (6) 4.9 (1) N44 0.7193 (2) 1.1109 (5) 0.0011 (6) 7.1 (I) C45 0.4501 (2) 0.0845 (4) 0.3537 (5) 3.61 (9) 046 0.4359 (2) 0.0727 (3) 0.4927 (4) 4.85 (7) 047 0.4453 (2) -0.0199 (3) 0.2194 (4) 4.67 (7) C48 0.4192 (3) -0.1591 (5) 0.2490 (7) 5.7 (1) C49 0.3841 (2) 0.3644 (4) 0.3392 (5) 3.65 (9) 050 0.3451 (1) 0.2732 (3) 0.3564 (4) 5.46 (8) O51 0.3731 (1) 0.5018 (3) 0.3447 (4) 4.87 (7) C52 0.3077 (2) 0.5411 (6) 0.3740 (8) 6.8 (1) The cell parameters were obtained by least-squares fit using 25 centered reflections with 6 < 0 < 25 °. An Enraf-Nonius CAD-4 diffractometer was used for data collection, 5292 unique reflections, - 2 4  < h ___ 24, - 11 ___ k - 11, 0 -< l -< 9, [(sin0)/A]max = 0.5947 A -1. Intensities were measured in the w/20 © 1992 International Union of Crystallography 394 C15H11NO482  Table 2. Bond distances (A) and angles (°) Numbers in parentheses are estimated standard deviations in the least significant digits. SI---C2 1.757 SI---C5 1.733 C2--S3 1.757 C2---C6 1.334 S3---C4 1.737 C_A----C5 1.332 C4--C 19 1.490 C5--C15 1.482 C6----C7 1.452 C7---C8 1.399 C7---C12 1.390 C8---C9 1.369 C9----C10 1.371 C10--C11 1.385 C10---C13 1.445 CI 1---C 12 1.375 C13---N14 1.132 CI 5-----O16 1.214 CI 5-----O17 1.218 O17----C18 1.473 C19-"O20 1.186 C!9--O21 1.305 O21---C22 1.;458 C2--S 1----C5 Sl----C2--$3 S I----C2---C6 S3---C2--C6 C2--$3--C4 S3----C4---C5 $3-----C4---C 19 C5--C4---C19 S 1----C5---CA SI----CS----CI 5 C4---C5----C 15 C2----C6----C7 C6----C7---C8 C6----C7----C 12 C8---C7----C 12 C7----C8--C9 C8---C'9---C 10 C9---C10---C11 C9----C10---C13 CI 1----C 10----C13 CI0--C11---C12 C7--C12--C11 C10----C 13----N 14 C5----C 15---O 16 C5----C15--O 17 O16--C15--O17 C15----4) 17---C 18 C4----C 19--O20 C4-----C 19---O21 O20----C 19---4)21 C 19---O21---C22 (4) $31---C32 1.765 (4) (4) $31--C35 1.730 (4) (5) C32--$33 1.750 (5) (6) C32----C36 1.342 (6) (4) $33---C34 1.752 (4) (6) C34----C35 1.330 (5) (7) C34--C49 1.469 (6) (7) C35---C45 1.512 (6) (5) C36---C37 1.460 (6) (6) C37--C38 1.381 (6) (6) C37--CA2 1.392 (6) (6) C38---C39 1.377 (6) (6) C39----~40 1.365 (6) (6) C40----C41 1.373 (6) (7) C40---C43 1.431 (6) (6) C41---C42 1.366 (7) (6) C43--N44 1.142 (7) (6) C45--O46 1.180 (5) (5) C45--O47 1.326 (4) (6) 047--C48 1.456 (5) (6) C49--O50 1.181 (6) (6) C49--O51 1.326 (5) (7) O51--C52 1.449 (6) 96.7 (2) C32--$31--C35 96.6 (2) 112.1 (2) $31----C32--$33 112.3 (2) 120.2 (4) $31---C32--C36 120.1 (4) 127.6 (3) $33---C32-----C36 127.6 (4) 96.8 (2) C32--$33--C34 96.7 (2) 117.0 (3) $33---C34-----C35 116.6 (3) 116.9 (3) S33--C34--C49 117.9 (3) 126.1 (4) C35--C34--C49 125.4 (4) 117.3 (3) $31--C35--C34 117.7 (4) 116.2 (4) $31--C35--C45 117.3 (3) 126.4 (4) C34--C35--C45 124.9 (4) 129.5 (4) C32---C36---C37 129.0 (4) 124.1 (4) C36---C37---C38 125.3 (4) 118.8 (3) C36--C37--C42 t18.4 (4) 117.1 (4) C38--C37--C42 116.3 (4) 120.7 (4) C37--C38---C39 121.9 (4) 120.9 (5) C38---C39--C40 120.3 (4) 119.9 (4) C39----C40--C41 119.0 (4) 119.0 (4) C39--C40--C43 t20.0 (4) 121.1 (4) C41--C40---C43 120.9 (5) 118.9 (4) C40---C41--C42 120.4 (5) 122.4 (4) C37--C42---C41 IEl.§ (4) 178.5 (5) C40-----C43--N44 179.5 (6) 121.0 (4) C35---C45----O46 124.9 (3) 114.8 (4) C35---C45---O47 109.5 (3) 124.2 (5) O46---C45----O47 125.5 (4) 116.9 (4) C45----O47--C48 115.9 (3) 123.4 (4) C34--C49----O50 125.2 (4) 111.6 (4) C34---C49--4)51 109.7 (3) 125.1 (4) O50---C49--O51 125.1 (4) 117.8 (4) C49---4)51--C52 116.6 (3) scan mode [scan speed 4.1 ° s-1, scan width (0) 1 + 0.34tan0°]. Decay of three control reflections, meas- ured every hour, was < 1%. Correction was made for Lorentz and polarization factors. Number of observed reflections 3388 [Fo 2 > 3or(Fo2)]. No absorp- tion correction was used. Structure solved by direct methods (Germain, Main & Woolfson, 1971) and refined by full-matrix least squares. Weights for each reflection in the refinement (on F) were calculated from w = 4Fo2/ Or2(Fo2), o'2(Fo 2) = 0"2(/) -Jr- (pFo2)2; the value of the instability factor p was determined as 0.04. H atoms were placed in calculated positions and were refined. The number of parameters refined was 486: scale factor, isotropic extinction factor g [F¢orr--F J(1 + gIc); final value 2.1 x 10-7], positional and aniso- tropic thermal parameters for non-H atoms and positional and isotropic thermal parameters for H atoms. Refinement converged at R = 0.051, wR = 0.059, S = 1.88, (A/Or)max ~---0.2. Largest peak on the final difference Fourier map 0.40 e A -3. All calculations were performed using SDP (Frenz & Associates, Inc., 1983). Atomic scattering factors from International Tables for X-ray Crystallography (1974, Vol. IV). Atomic parameters of non-H atoms are given in Table 1.* Bond distances and bond angles are given in Table 2. Atom numbering of the title compound is shown in Fig. 1. Related literature. To the best of our knowledge no crystal structure of a para-substituted aromatic ring with a 4,5-functionalized methylene-l,3-dithiole moiety as electron donor and a cyano group as electron acceptor has been published. However, some related structures have been determined. The crystal structure of a dithiinofulvene deriv- ative with a methylene-l,3-dithiole-4,5-dicarboxylic * Lists of structure factors, anisotropic thermal parameters, H-atom parameters and complete lists of  bond lengths and angles have been deposited with the British Library Document Supply Centre as Supplementary Publication No. SUP 54552 (38 pp.). Copies may be obtained through The Technical Editor, Interna- tional Union of Crystallography, 5 Abbey Square, Chester CH1 2HU, England. [CIF reference: AL0486] czl C1~ :10 C13 FiNt4 016 Fig. 1. View of one independent molecule with the atom- numbering scheme. The atom numbers in molecule (2) are obtained by adding 30 to those of  molecule (1). FRANK C. J. M. VAN VEGGEL AND SYBOLT HARKEMA 395 acid, dimethyl ester unit has been reported by Lakshmikantham, Cava & Carroll (1984). A nio- bium complex with a methylene-l,3-dithiole-4,5-bis- (trifluoromethyl) unit has been published by Amaudrut, Sala-Pala, Guerchais & Mercier (1990). Beer, Frew, Johnson & Paul (1970) have reported an isothiathiophten containing a methylene-l,3-dithiole- 4-(4-bromophenyl) unit. The structure of (pivaloyl- methylene)-l,3-dithiole-4-pivaloyl has been reported by Galloy, Declercq & Van Meerssche (1978). A 4,5-unsubstituted methylene-l,3-dithiole derivative has been reported by Barnes, Paton & Nicholls (1982). The structures of the related compounds mentioned here are less accurate than that reported in this paper. References AMAUDRUT, J., SALA-PALA, J., GUERCHAIS, J. E. & MERCIER, R. (1990). J. Organomet. Chem. 391, 61-80. BARNES, J. C., PATON, J. D. & NICHOLLS, B. H. (1982). Acta Cryst. B38, 1525-1529. BEER, R. J. S., FREW, D., JOHNSON, P. L. & PAUL, I. C. (1970). J. Chem. Soc. Chem. Commun. pp. 154-155. FP~NZ, B. A. & ASSOOATES, INC. (1983). SDP Structure Deter- mination Package. College Station, Texas, USA. GALLOY, J., DECLERCQ, J.-P. & VAN MEERSSCrIE, M. (1978)..4cta Cryst. B34, 975-978. GERMAIN, G., MAIN, P. & WOOLFSON, M. M. (1971). Acta Cryst. A27, 368-376. LAKSHMIKANTHAM, M. V., CAVA, M. P. • CARROLL, P. J. (1984). J. Org. Chem. 49, 726-728. MULVANEY, J. E. & CHANG, D. M. (1980). Macromolecules, 13, 240-243. Acta Cryst. (1992). C48, 395--396 Structure of Methyl 2-(2,5-Dihydro-2-oxo-3-phenyl-5-furyl)lactate BY ROSEMARY C. HYNES Institute for Environmental Chemistry, National Research Council of Canada, Ottawa K1A 0R6, Canada (Received 2 May 1991; accepted 9 July 1991) Abstract. C!4Hi405,  M r = 262.26, monoclinic, P211n, a = 11.319 (3), b = 6.5115 (15), c =  18.105 (5) A,/3 = 105.660 (20) °, V = 1284.8 (6) A3, Z = 4, Dx = 1.356 g cm -3, A(Cu Kay) = 1.54056 A, /z = 8.26 cm- 1, F(000) = 553.89, T = 295 K, R = 0.036, wR = 0.033 for 1692 reflections with I > 2.50-(/). The structure determination established the identity of the product of a Co2(CO)8-catalyzed carbonylation reaction with an epoxy alcohol. Experimental. A colourless crystal of the title com- pound (1) was grown from THF solution. Cell parameters from 20 reflections in the 20 range 85-90 °. Data were collected on a Picker diffractom- eter using profile analysis (Grant & Gabe, 1978). Three standards measured every 100 reflections were used for scaling and had an overall drop in intensity of 6%. Averaging of symmetry-equivalent reflections gave a merging R value of 3.3%. Parameters related to crystal data and intensity collection are given in Table 1. The structure was solved by direct methods and refined by cycles of least-squares calculations. H atoms were located in a difference map and refined isotropically. Final atomic parameters are listed in Table 2. All non-H atoms were refined anisotrop- ically. All computing was performed with the NRCVAX system of structure-solving programs (Gabe, Le Page, Charland, Lee & White, 1989). Scattering factors from International Tables for X-ray Crystallography (1974, Vol. IV).* o o OH 0 o/CH3 CH3 (i) An ORTEPII plot of (1) is shown in Fig. 1. Bond lengths and angles, except those involving H atoms, are given in Table 3. A stereoplot showing packing of the unit cell has been included as Fig. 2. The structure consists of a planar lactone ring with maxi- mum deviation from planarity 0.0098 (18)A, rotated slightly from the plane of the phenyl ring, with a dihedral angle of 16.73 (6) °. The diastereomer adopts an anti configuration. The molecules are packed with the lactone rings approximately parallel to the b axis. The closest intermolecular approach is 2.14 (2)A * Lists of structure factors, anisotropic thermal parameters and least-squares-planes calculations have been deposited with the British Library Document Supply Centre as Supplementary Publi- cation No. SUP 54457 (15 pp.). Copies may be obtained through The Technical Editor, International Union of Crystallography, 5 Abbey Square, Chester CHI 2HU, England. ICIF reference: CR0352] 0108-2701/92/020395-02503.00 © 1992 International Union of Crystallography 

F. C. J. M. van Veggel

S. Harkema

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Acta Crystallographica Section C Crystal Structure Communications

A colourless crystal of the title compound (1) was grown from THF solution. Cell parameters from 20 reflections in the 20 range 85-90 °. Data were collected on a Picker diffractometer using profile analysis

C48, 395--396 Structure of Methyl 2-(2,5-Dihydro-2-oxo-3-phenyl-5-furyl)lactate BY ROSEMARY C. HYNES Institute for Environmental Chemistry, National Research Council of Canada, Ottawa K1A 0R6,

Cryst.

SDP Structure Determination Package. College Station,

http://purl.utwente.nl/publications/59241

Structure of 2-[(4-cyanophenyl)methylene]-1,3-dithiole-4,5-dicarboxylic acid, dimethyl ester

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