Diethyl 2,2'-[1,3-phenylenebis(methylthio)]dibenzoate

RAIKKO KIVEKAS et al. 2049 Data collection Rigaku AFC-5S diffractometer w-20 scans Absorption correction: empirical, ~b-scan Train = 0.95, Tmax = 1.00 1185 measured reflections 1121 independent reflections 895 observed reflections [I > 2or(/)] Rim = 0.010 0max = 25 ° h = 0 --~ 13 k = 0 ---~ 13 l=-ll--> 11 3 standard reflections monitored every 150 reflections intensity variation: decline of - 1.20%, linear correction applied Refinement Refinement on F R = 0.044 wR = 0.055 S = 2.23 895 reflections 89 parameters w = 1/a2(F) (A/o')max = 0.033 mpmax = 0.2 e/~-3 Apmin = -0.3 e/~-3 Atomic scattering factors from Xtal3.0 (Hall & Stewart, 1990) Table 1. Fractional atomic coordinates and equivalent isotropic displacement parameters (/~2) Ueq = (1/3)E,~jUija i aj ai.aj. x y z Ueq S(1) 0.29308 (6) 0.52931 (6) 0.68847 (8) 0.0487 (3) O(l)t 0.4890 (5) 0.3466 (3) 0.7885 (4) 0.051 (2) C(I) 0.4610 (2) 0.7084 (2) 0.6846 (3) 0.0423 (9) C(2) 0.4254 (3) 0.8178 (3) 0.6224 (4) 0.064 (1) C(3) 0.4636 (3) 0.9239 (3) 0.6856 (5) 0.087 (2) C(4) 0.4161 (3) 0.5942 (3) 0.6139 (3) 0.045 (1) C(5) 0.2946 (3) 0.3770 (3) 0.6275 (4) 0.071 (1) C(6) 0.3968 (3) 0.3017 (3) 0.6893 (4) 0.071 (1) l Site occupation 0.5. Table 2. Selected geometric parameters (/~,, o) S(1)----C(4) 1.825 (3) C(1)---C(2) 1.393 (4) S(1)----C(5) 1.812 (4) C(1)---C(4) 1.497 (4) O(1)----C(6.) 1.366 (5) C(2)----C(3.) 1.371 (5) O(1)----C(6 I) 1.337 (6) C(3)----C(3 I) 1.368 (7) C(1)--C(1 i) 1.409 (4) C(5)---C(6) 1.447 (5) C(4)--S(1)----C(5). 100.6 (2) C(2)--C(3)----C(3 i) 119.9 (3) C(6)---O(1)---C(6 I) 121.8 (4) S(1)----C(4)----C(1) 110.9 (2) C(2)----C(1)---C(4.) 120.4 (3) S(1)----C(5)---C(6) 117.8 (2) C(2)--C(1)---C(1 I) 118.4 (3) O(1)--C(6)--C(5.) 120.0 (3) C(4)----C(1)--C(I i ) 121.2 (2) C(5)---C(6)---O(1 I) 119.0 (3) C(1)---C(2)---C(3) 121.7 (3) C(5)---S(1)--C(4)----C(1) - 161.8 (2) C(4)--S(1)---C(5)---C(6) 72.2 (3) C(6')---O(1)---C(6)---C(5)- 153.7 (4) C(4.)---C(1)---C(2)----C(3 ) 179.0 (4) C(11)----C(1)---C(2)---C(3) -0.5 (5) C(2)---C(1)----C(4)---S(1) - 103.0 (3) C(1 i)--C(1)--C(4)---S(1) 76.5 (3) C(1)--C(2)--C(3)--C(3 i) - 1.4 (7) S(1)--C(5)--C(6)---O(1.) - 1.0 (6) S(1)--C(5)---C(6)---O(11.) -43.1 (5) C(5 )---C(6)----O(1)---C(61) _ 153.7 (4) Symmetry code: (i) 1 - x, y, ~ - z. The structure was solved by direct methods (Gilmore, 1984) and successive Fourier syntheses. Refinement was performed by full-matrix least-squares methods, non-H atoms with anisotropic displacement parameters and H atoms either with isotropic displacement parameters [H(2), H(3), H(4A) and H(4B)] or included in the calculations at fixed positions (C-- H = 0.95/~,). The refinements were carded out with Xtal3.0 (Hall & Stewart, 1990). The figure was drawn using ORTEPII (Johnson, 1976). © 1994 International Union of Crystallography Printed in Great Britain - all rights reserved RK is grateful to Suomen Kultuurirahasto for the grant. Lists of structure factors, anisotropic displacement parameters, H- atom coordinates, complete geometry, including H-atom geometry, and torsion angles have been deposited with the IUCr (Reference: ABl168). Copies may be obtained through The Managing Editor, International Union of Crystallography, 5 Abbey Square, Chester CH1 2HU, England. References Blake, A. J. & Schrrder, M. (1990). Adv. Inorg. Chem. 35, 1-37. Casab6, J., Mestres, L., Escriche, L., Teixidor, F. & Perez-Jimenez, C. (1991). J. Chem. Soc. Dalton Trans. pp. 1969-1971. Escriche, L., Almajano, M. P., Casab6, J., Teixidor, F., Rius, J., Miravitlles, C., Kivekiis, R. & Sillanp~i, R. (1993). J. Chem. Soc. Dalton Trans. pp. 2969-2974. Gilmore, C. J. (1984). J. Appl. Cryst. 17, 42-46. Hall, S. R. & Stewart, J. M. (1990). Editors. Xtal3.0 Reference Manual. Univs. of Western Australia, Australia, and Maryland, USA. Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. KivekEs, R., Sillanpii~i, R., Escriche, L., Almajano, M. P., Teixidor, F. & Casabr, J. (1994). Acta Cryst. C50, 1249-1252. Lockhart, J. C., Mousley, D., Stuart Hill, M. N., Tomkinson, N. P., Teixidor, F., Almajano, M. P., Escriche, L., Casab6, J., Sillanpii~i, R. & Kivek~is, R. (1992). J. Chem. Soc. Dalton Trans. pp. 2889-2897. Murray-Rust, P., Biirgi, H.-B. & Dunitz, J. D. (1975). J. Am. Chem. Soc. 97, 921-922. Acta Cryst. (1994). C50, 2049-2051 Diethyl 2,2'-[1,3-Phenylenebis(methylthio)]- dibenzoate REtlO S ILLANP,7~ Department of Chemistry, University of Turku, FIN-20500 Turku, Finland RAIrXO KrvErAS Department of Chemistry, PO Box 6, FIN-O0014 University of Helsinki, Finland LLUIS ESCPaCHE, NATIVIDAD LUCENA, FRANCES(: TEIXIDOR AND JAUME CASAB6 Departament de Quimica (Unitat Inorggmica), Universitat Aut6noma de Barcelona and Institut de Cidncia dels Materials (CSIC), Campus de Bellaterra, 08193 Bellaterra, Barcelona, Spain (Received 9 February 1994; accepted 15 July 1994) Abstract The title molecule, C26H260452, assumes C2 symmetry with two C atoms and two H atoms of the cen- Acta Crystallographica Section C ISSN 0108-2701 ©1994 2050 C26H260452 tral phenyl ring located on the twofold axis. The S atoms are synplanar with the benzene moiety, so the observed geometry is suitable for CS2 coordination. The o-(ethoxycarbonyl)phenylthiomethyl moiety is approximately planar and its orientation is almost perpendicular with respect to the central phenyl group. Comment Our studies have demonstrated that dithioether macrocycles containing the 1,3-bis(R-thiomethyl)benzene (R = alkyl or aryl) unit are excellent neutral sensing molecules for silver(I)-selective membrane electrodes (Casab6, Mestres, Escriche, Teixidor & Perez-Jimenez, 1991). Molecular-dynamics calculations confirm that in the series of 2,5,8-trithia[9]benzenophanes only m-benzenophane, which contains the 1,3-bis(R-thio- methyl)benzene unit, has the necessary features to ensure chelating interactions with the silver(I) metal ion (Lockhart et al., 1992). No difference in the selective behaviour was observed as a function of the length and nature of the aliphatic macrocyclic chain. As part of these studies we are testing the relevance of the cyclic character of these molecules in silver(I) recognition. For this purpose we are synthesizing and characterizing acyclic molecules that include the 1,3- bis(R-thiomethyl)benzene unit as a preliminary step to incorporating them in membrane electrodes. Here we report the crystal structure of diethyl 2,2'-[1,3- phenylenebis(methylthio)]dibenzoate (I). r ° 7 (1) axial with respect to the central pyfidine ring (Sillanpiiii, Kivekiis, Escriche, Sfinchez-Castell6 & Teixidor, 1994). In the title compound, the bulky o-(ethoxycarbonyl)- phenylthiomethyl moiety is approximately planar. The C(2)---C(5)---S(1)---C(6) torsion angle is -73.9(3) ° and the orientation of the moiety is almost perpendicular with respect to the central phenyl group. Bond lengths agree with the values reported for (2,6-bis{[(2- methoxycarbonyl)phenyl] thiomethyl}pyridine)dichlorocopper(D) (Teixidor et al., 1991), but the C(13)---C(14) distance is slightly shorter than a normal single-bond length. ~23 H3 c3 HSB i HITCH. ~ ~ ~ H7 ~H~ )cs ~co H9 ' e.!o 02 f.~Ol - '*,,~,~. H 13 8 H14C~.~,,~1~ H148 t~ Cla HlZlA Fig. 1. ORTEPII (Johnson, 1976) plot of C26H2604S2 . Displacement ellipsoids are shown at 30% probability levels except for H atoms which are given arbitrary radii. Experimental The title molecule is an example of a ligand that can • coordinate tridentately to some metal ions [e.g. Pd n and Pt II] through two S atoms and one C atom. This reactivity may best be regarded as a result of electrophilic attack of the metal halide on the C(1) atom of the ligand with elimination of hydrogen halide (Constable, 1984). The intermediate carbanion is stabilized due to the inductive effect of the alkyl substituents in vicinal positions. The conformation of the title compound in the crystalline state is suitable for CS2 coordination because, with a value of -23.5(4) ° for the C(1)-- C(2)---C(5)---S(1) torsion angle, the orientation of the S(1) atom is synplanar with the C(1)---C(2) bond. The conformation differs from that of 2,6-bis(pnitrophenylthiomethyl)pyridine in which the molecular symmetry is C1 and the orientation of the other S atom is Dehydrated and deoxygenated ethanol was used in the synthesis. m-Dichloroxylene was commercially available (Aldrich) and used as received. Thiosalicyl ethyl ester (7.28 g, 40 mmol) was added to a stirred solution of sodium metal (0.93 g, 40 mmol) in ethanol (40 ml) and the mixture stirred for a further 10 min. The mixture was then added to a solution of mdichloroxylene (3.48 g, 20 mmol) in ethanol (40 ml). After the addition, a white precipitate appeared. The mixture was heated at 303-308 K under reflux and then cooled to room temperature. The precipitate was filtered off, washed with ethanol, vacuum dried and recrystaUized from 1,2-dimethoxyethane to afford the title compound as a white crystalline product suitable for X-ray diffraction analysis [yield 6.81 g (67%)]. Crystal data C26H2604S2 Mo Ka radiation Mr = 466.6 A = 0.71069 Monoclinic Cell parameters from 25 C2/c reflections REIJO SILLANPAA et al. 2051 a = 14.502 (2)/~, b = 10.904 (3)/~ c = 14.503 (2)/~, /3 = 90.34 (1) ° V = 2293.4 (7)/~3 Z=4 Dx = 1.351 Mg m -3 0 = 13.2-17.4 ° # = 0.251 mm -1 T = 296 K Cubic 0.35 x 0.35 x 0.25 mm White Data collection Rigaku AFC-5S diffractometer 0,,-20 scans Absorption correction: empirical, ~b-scan Tmtn= 0.96, Tmax = 1.00 2238 measured reflections 2144 independent reflections 1259 observed reflections [1 > 2tr(/)] Refinement Refinement on F R = 0.052 wR = 0.056 S = 1.78 1259 reflections 175 parameters w = 1/tr2(F) Rim = 0.016 0max = 25 ° h = -17 ---~ 0 k = -13 ~ 0 l = -17 ---, 17 3 standard reflections monitored every 150 reflections intensity variation: +0.5% (A/o-)max = 0.01 Apmax = 0.27 e A -3 Apmin = -0.23 e/~-3 Atomic scattering factors from International Tables for X-ray Crystallography (1974, Vol. IV) Table 1. Fractional atomic coordinates and equivalent isotropic displacement parameters (A 2) Beq = (4/3)EiEj/3ijai.aj. x y z Beq S(I) 0.66990 (7) 0.3953 (1) 0.68843 (6) 5.41 (5) O(1) 0.6261 (2) 0.7092 (3) 0.5028 (2) 6.2 (2) 0(2) 0.6503 (2) 0.6365 (3) 0.6430 (2) 7.2 (2) C(1) 1/2 0.2337 (5) 3/4 4.1 (3) C(2) 0.5816 (2) 0.1711 (4) 0.7348 (2) 4.3 (2) C(3) 0.5814 (3) 0.0439 (4) 0.7347 (3) 5.3 (2) C(4) 1/2 -0.0181 (6) 3/4 6.1 (4) C(5) 0.6728 (3) 0.2365 (4) 0.7247 (3) 5.4 (2) C(6) 0.6414 (2) 0.3873 (4) 0.5693 (2) 4.2 (2) C(7) 0.6333 (3) 0.2755 (4) 0.5242 (3) 4.9 (2) C(8) 0.6139 (3) 0.2714 (4) 0.4308 (3) 5.5 (2) C(9) 0.6016 (3) 0.3768 (4) 0.3803 (3) 5.1 (2) C(10) 0.6088 (3) 0.4875 (4) 0.4231 (3) 4.8 (2) C(ll) 0.6291 (2) 0.4957 (4) 0.5179 (2) 4.2 (2) C(12) 0.6364 (2) 0.6175 (4) 0.5627 (3) 5.0 (2) C(13) 0.6316 (4) 0.8302 (5) 0.5456 (4) 7.1 (3) C(14) 0.6155 (4) 0.9157 (5) 0.4754 (4) 9.4 (4) Table 2. Selected geometric parameters (/~, o) S(1)----C(5) 1.810 (5) C(6)----C(7) 1.388 (5) S(1 )---42(6) 1.776 (3) C(6)-----C(11 ) 1.408 (5) O(1)----C(12) 1.332 (5) C(7)---C(8) 1.384 (5) O(1)--C(I 3) 1.461 (5) C(8)--C(9) 1.374 (6) O(2)--42(12) 1.198 (4) C(9)----C(10) 1.362 (5) C(1)---C(2) 1.386 (4) C(10)--C(11) 1.407 (5) C(2)--C(3) 1.386 (5) C(11)---C(12) 1.483 (5) C(2)----C(5) 1.510 (5) C(13)---C(14) 1.399 (7) C(5)---S(1)--C(6) 103.9 (2) C(6)---C(7)----C(8) 120.4 (4) C(12)----O(1)---C(13) 113.3 (3) C(7)----C(8)----C(9) 121.4 (4) C(2)----C(1)----C(2') 120.9 (5) C(8)---C(9)---C(10) 119.3 (4) C(1)---C(2)----C(3) 119.4 (4) C(9)---C(10)---C(11) 121.1 (4) C(1)---C(2)---C(5) 122.1 (4) C(6)----C(1 I)--C(10) 119.3 (3) C(3)---C(2)--C(5) 118.3 (4) C(6)----C(1 I)----C(12) 120.8 (3) C(2)---C(3)----C(4.) 119.5 (5) C(10)----C(11)--C(12) 119.9 (4) C(3)----C(4)----C(3') 121.3 (6) O(1)----C(12)---O(2) 121.5 (4) S(1)----C(5)----C(2) 117.5 (3) O(1)----C(12)---C(11) 112.3 (4) S(1)--C(6)--C(7) 121.3 (3) O(2)---C(12)---C(11) 126.3 (4) S(1)----C(6)--C(11) 120.1 (3) O(1)---C(13)----C(14) 106.5 (4) C(7)---C(6)----C(1 I) 118.5 (3) Symmetry code: (i) 1 - x, y, ~ - z. The structure was solved by direct methods (Gilmore, 1984) and successive Fourier syntheses. Refinement was performed by full-matrix least-squares methods. Non-H atoms were refined with anisotropic displacement parameters and H atoms, except those of the methyl group, with fixed isotropic displacement parameters (1.2 x Beq of the carrying atom). H atoms of the methyl group were included in the calculations in fixed positions (C--H 0.948/~). The calculations were carded out using TEXSAN (Molecular Structure Corporation, 1989) on a VAXstation 3520 computer. The figure was drawn with ORTEPII (Johnson, 1976). Lists of structure factors, anisotropic displacement parameters, H- atom coordinates, complete geometry, including H-atom geometry, and torsion angles have been deposited with the IUCr (Reference: ABl169). Copies may be obtained through The Managing Editor, International Union of Crystallography, 5 Abbey Square, Chester CH 1 2HU, England. References Casab6, J., Mestres, L., Escriche, L., Teixidor, F. & Perez-Jimenez, C. (1991). J. Chem. Soc. Dalton Trans. pp. 1969-1971. Constable, E. D. (1984). Polyhedron, 3, 1037-1057. Gilmore, C. J. (1984). J. Appl. Cryst. 17, 42-46. Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Lockhart, J. C., Mousley, D., Stuart Hill, M. N., Tomkinson, N. P., Teixidor, F., Almajano, M. P., Escriche, L., Casab6, J., Sillanp~, R. & Kivek~is, R. (1992). J. Chem. Soc. Dalton Trans. pp. 2889-2897. Molecular Structure Corporation (1989). TEXSAN. Single Crystal Structure 4nalysis Software. Version 5.0. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA. Sillanp~, R., Kivekiis, R., Escriche, L., SAnchez-Castell6, G. & Teixidor, F. (1994). Acta Cryst. C50, 1284-1286. Teixidor, F., SAnchez-Castell6, G., Lucena, N., Escriche, L., Kivek~is, R., Sundberg, M. & Casab6, J. (1991). lnorg. Chem. 30, 4931--4935. Acta Cryst. (1994). C50, 2051-2054 2,6-Bis(phenyl amino) pyridine MARTTI KLINGA, MIKA POLAMO AND MARKKU LESKELZ, Department of Chemistry, Box 6, FIN-O0014 University of Helsinki, Finland (Received 5 January 1994; accepted 11 May 1994) Abstract The structure of the title compound, cl7nl5N3, consists of two independent molecules which are © 1994 International Union of Crystallography Printed in Great Britain - all rights reserved Acta Crystallographica Section C ISSN 0108-2701 ©1994