[2,6-Bis(2-pyrimidinylthiomethyl)pyridine]dichlorocopper(II) methanol solvate

1062 [Sn(C6HsS)(C6H5)3] AND [Sn(C6H5S)2(C6H5)2] This work was partially supported by Conselho Nacional de Desenvolvimento Cientifico e Tecnol6gico (CNPq) and Fundagao de Amparo a Pesquisa do Estado de Minas Gerais (FAPEMIG). Lists of structure factors, anisotropic displacement parameters, H-atom coordinates and complete geometry have been deposited with the IUCr (Reference: SH1090). Copies may be obtained through The Managing Editor, International Union of Crystallography, 5 Abbey Square, Chester CH1 2HU, England. References Chieh, P. C. & Trotter, J. A. (1970). J. Chem. Soc. A, pp. 911-914. Clarke, P. L., Cmdwick, M. E. & WardeU, J. L. (1973). J. Organomet. Chem. 63, 279-285. Fair, J. (1991). XSCANS Users Manual. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Kwart, H., Schuit, G. C. A. & Gates, B. C. (1980).2. Catal. 61, 128-134. Miiller, E. G., Watkins, S. F. & Dahl L. F. (1976). J. Organomet. Chem. 111, 73-89. Shelddck, G. M. (1990). SHELXTLIPC Users Manual. Siemens Analytical X-ray Instnmaents Inc., Madison, grmconsin, USA. Acta Cryst. (1994). C50, 1062-1064 [2,6-Bis(2-pyrimidinylthiomethyl)pyridineldichlorocopper(II) Methanol Solvate R. SILLANP,~. Department of Chemistry, University of Turku, FIN-20500 Turku, Finland R. KIVEKLS by two C1- ions, one pyridine N atom and one pyrimidine N atom. The fifth coordination site is occupied by the S atom of a thiomethyl group. The methanol molecule occupies an otherwise empty space in the structure. Comment The coordination chemistry of 2,6-bis(R-thiomethyl)- pyridine changes considerably with the nature of the R group (Teixidor, Sfinchez-Castell6, Lucena, Escriche, Kivek/is, Sundberg & Casab6, 1991). The present ligand, 2,6-bis(2-pyrimidinylthiomethyl)pyridine, in the title compound, (I), has seven potential donor atoms, which afford a large number of different possible coordination modes. The title complex is a new example of this series and shows an asymmetric coordination mode of the multidentate ligand. .CH3OH (I) The structure consists of molecular complex units and methanol molecules. The complex is depicted in Fig. 1. The ligand is coordinated in a tridentate manner to the Cu 2÷ ion. The two Clions and two ligand N atoms form the equatorial plane around the Cu 2÷ ion. The fifth coordination site is occupied by the S atom of a thiomethyl group. The Cu----Cl distances are similar whereas Cu--N(1) and Department of Chemistry, University of Helsinki, PO Box 6, FIN-O0014, Finland L. EscRIcrm ANt) J. CASAB6 Departament de Quimica, Universitat Autdnoma de Barcelona, Campus de Bellaterra, 08193 Bellaterra, Barcelona, Spain G. SJ, NCHEZ-CASTELL6 Institut de Cidncia de Materials, CSIC, Campus de Bellaterra, 08193 Bellaterra, Barcelona, Spain (Received 17 June 1993; accepted 2 December 1993) Abstract In the title compound, [CuC12(C15H13N5S2)].CH3OH, the Cu 2÷ ion has square-pyramidal coordination geometry. The basal plane of the pyramid is formed © 1994 International Union of Crystallography Printed in Great Britain - all rights reserved HI2 C14 C13 NS C12 ~llml~mll~'~m~ H9 ~ C11 Hs II ' • CL2 /~C5 _~ H3 CL}. Ca 1-17 Fig. 1. ORTEPII (Johnson, 1975) plot of the title compound. Displacement ellipsoids are shown at 30% probability levels, except for those of the H atoms which are drawn with an isotropic displacement factor of 1.0. Acta Crystallographica Section C ISSN 0108-2701 ©1994 • ° °° R. SILLANPAA et al. 1063 Cu--N(2) differ (Table 2). The axial Cu--S(2) distance is elongated. No other angles around the Cu atom other than CI(1)---Cu--N(1) and CI(2)---Cu-- N(2) deviate much from the expected values for square-pyramidal geometry. Distortions are a result of the bulky ligand which forces the Cu u to adopt the observed geometry. The methanol molecule is disordered so that the O and C atoms could not be reliably distinguished. However, the structure was refined with C and O atoms of the solvent molecules in the positions as indicated in Table 1. Only H(C) atoms of methanol were included in final calculations. Experimental The title compound was synthesized when CuC12.2H20 (0.052 g, 0.30 nunol), dissolved in methanol (2 cm3), was added to a solution of 2,6-bis(2-pyrimidinylthiomethyl)pyddine (0.1 g, 0.30 retool) in methanol (2 cm3). A green crystalline solid suitable for X-ray diffraction analysis was obtained which was filtered off, washed with ethyl acetate (10 cm 3) and vacuum dried. Yield: 60% (0.089 g). Analysis: calculated for Cu CI6HI7CI2CuN5OS2, C 38.9, H 3.5, N 14.18, S 13.0, C1 14.4%; Cl(l) Cl(2) found, C 38.6, H 3.1, N 14.3, S 13.2, C1 14.8%. s(1) In the preparation of 2,6-bis(2-pyrimidinylthiomethyl)pyrids(2) ine, KOH 85% (2.09 g, 31.7 mmol) in ethanol (200 cm 3) o was stirred under reflux for 30 min with 2-mercaptopyrimidine N(1) N(2) (3.55 g, 31.7 mmol). Then, this solution was added to a solution N(3) of 2,6-bis(bromomethyl)pyridine (4.2 g, 15.8 mmol) in ethanol N(4) (100 cm 3) and was stirred under reflux for 1 h. The KBr formed N(5) was filtered out and discarded. The filtrate was evaporated under C(l) C(2) reduced pressure and the resulting yellow solid was recrystalc(3) lized in water to afford a white solid. Yield: 53 % (2.74 g). Analc(4) ysis: calculated for CIsH13NsS2, C 55.0, H 4.0, N 21.4, S 19.8%; c(5) found, C55.1,H4.1,N20.8, S 19.3%. ~HNMR(CDC13):64.49 c(6) (s, 4, py--CH2--S); 6 7.62 (m, 11, aromatic), c(7) C(8) Dehydrated and deoxygenated solvents were used in the sync(9) theses. 2,6-Bis(bromomethyl)pyridine was prepared according c(I0) to the procedure reported by Offermann & V6gtle (1977). 2- c(11) C(12) Mercaptopyrimidine is commercially available (Aldrich) and c(13) was used as received. Microanalyses were performed on a c(14) Perkin-Elmer 240-B instntment. Proton NMR spectra were c(15) recorded on a Bruker 400 MHz AC instrument, c(16) Crystal data [CuC12(CIsH13NsS2)].- Dx = 1.640 Mg m -3 CH3OH Mo Ka radiation Mr = 493.92 A = 0.71069 ,~, Monoclinic Cell parameters from 17 P21/ n reflections a = 8.561 (3) ,A, 0 = 4.5-13 ° b = 14.107 (4) ,~ # = 1.58 mm -I c = 16.582 (5) ,~, T = 296 K /3 = 92.72 (3) ° Prismatic V = 2000 (1) A 3 0.25 x 0.15 x 0.05 nun Z = 4 Green Data collection Rigaku AFC-5S diffractome- Rmt = 0.062 ter 0max = 25 ° w-20 scans Absorption correction: none 3945 measured reflections 3686 independent reflections 1716 observed reflections [I > 2tr(/)] Refinement Refinement on F R = 0.064 wR = 0.056 S = 1.31 1716 reflections 244 parameters H-atom parameters not refined h = 0 ---~ 10 kffi0 ---, 17 1 = -20 ~ 20 3 standard reflections monitored every 150 reflections intensity variation: -2.1% W-- l/cr2(F) (A/tr)m~ = 0.02 Apmax = 0.58 e/~-3 Apmin = -0.56 e A -3 Atomic scattering factors from International Tables for X-ray Crystallography (1974, Vol. IV) Table 1. Fractional atomic coordinates and equivalent isotropic displacement parameters (,~2) Beq = (4/3)~i~y/3uai.a j. x y z Beq 0.1600 (1) 0.35539 (9) 0.22743 (7) 2.68 (6) 0.3786 (3) 0.2876 (2) 0.1850 (2) 3.9 (1) 0.0917 (3) 0.4163 (2) 0.1050 (2) 4.1 (1) 0.2733 (4) 0.5141 (3) 0.4023 (2) 4.1 (2) -0.0403 (3) 0.2010 (2) 0.2093 (2) 3.2 (1) -0.080 (2) 0.279 (1) 0.4775 (8) 15 (1) -0.0324 (8) 0.4084 (5) 0.2737 (5) 2.3 (4) 0.252 (1) 0.3313 (6) 0.3458 (5) 2.8 (4) 0.390 (1) 0.3687 (7) 0.4702 (5) 4.1 (5) -0.228 (1) 0.1313 (6) 0.3195 (5) 3.8 (5) 0.029 (1) 0.0694 (6) 0.3136 (5) 3.2 (4) -0.012 (1) 0.4877 (7) 0.3184 (6) 2.5 (5) -0.132 (1) 0.5223 (7) 0.3627 (6) 3.5 (6) -0.274 (1) 0.4766 (8) 0.3618 (7) 3.9 (6) -0.296 (1) 0.3969 (8) 0.3117 (6) 3.4 (5) -0.174 (l) 0.3659 (7) 0.2672 (6) 2.4 (4) 0.143 (1) 0.5345 (7) 0.3159 (6) 3.4 (5) 0.304 (1) 0.3918 (7) 0.4042 (6) 3.2 (5) 0.285 (1) 0.2390 (8) 0.3612 (6) 3.5 (6) 0.365 (1) 0.2097 (8) 0.4287 (8) 3.9 (6) 0.423 (1) 0.279 (1) 0.4805 (7) 5.1 (7) -0.198 (1) 0.2861 (8) 0.2091 (6) 3.5 (5) -0.087 (I) 0.1262 (7) 0.2910 (6) 2.8 (5) -0.256 (1) 0.069 (1) 0.3793 (8) 5.2 (7) -0.145 (1) 0.0077 (9) 0.4083 (7) 4.4 (7) -0.001 (1) 0.0102 (8) 0.3736 (7) 4.3 (6) 0.038 (2) 0.246 (1) 0.5241 (9) 8 (1) Table 2. Selected geometric parameters (,A,, o) Cu--Cl(1) 2.244 (3) N(1)--C(1) 1.35 (1) Cu--CI(2) 2.257 (3) N(I)--C(5) 1.35 (1) Cu--N(I) 1.996 (7) N(2)--C(7) 1.35 (1) Cu--N(2) 2.108 (8) N(2)--C(8) 1.35 (1) Cu--S(2) 2.779 (3) N(3)--C(7) 1.33 (1) S(I)--C(6) 1.79 (1) N(3)--C(10) 1.31 (1) S(1)--C(7) 1.75 (1) N(4)--C(12) 1.31 (1) S(2)--C(11) 1.81 (1) N(4)--C(13) 1.36(1) S(2)--C(12) 1.78 (1) N(5)--C(12) 1.32 (1) O--C(16) 1.33 (2) N(5)--C(15) 1.33 (1) N(1)--Cu--N(2) 89.0 (3) C(I 1)--S(2)--C(12) 101.5 (5) N(1)--Cu--CI(1) 174.9 (2) Cu--N(1)--C(1) 115.8 (6) N(1)--Cu--CI(2) 91.2 (2) Cu--N(I)--C(5) 123.8 (7) N(1)--Cu--S(2) 79.6 (2) C(1)--N(1)--C(5) 120.2 (8) N(2)--Cu--CI(1) 86.7 (2) Cu--N(2)--C(7) 131.5 (7) N(2)--Cu--CI(2) 165.7 (2) Cu--N(2)--C(8) 113.3 (7) N(2)--Cu--S(2) 100.1 (2) C(7)--N(2)--C(8) 114.5 (9) CI(1)--Cu--CI(2) 93.7 (1) C(7)--N(3)--C(10) 117 (1) CI(1)--Cu--S(2) 98.7 (1) C(12)--N(4)--C(13) 115 (1) 1064 [CtlCl2 (C 15H13N5 S2)].CH3OH Cl(2)--Cu--S(2) 94.0 (1) C(12)--N(5)--C(15) 115 (1) C(6)--S(1)--C(7) 105.1 (5) S(1)--C(6)--C(1)--N(1) - 102.3 (9) C(1)--C(6)--S(1)--C(7) 61.5 (9) S(2)--C(ll)--C(5)--N(I) 44 (1) C(5)--C(11)--S(2)--C(12) 83.6 (8) The structure was solved by direct methods (Gilmore, 1984) and successive Fourier syntheses. Refinement was performed using full-matrix least-squares methods, with non-H atoms anisotropic and H atoms in calculated positions with fixed displacement parameters (1.2 x B~q of the carrying atom). Calculations were performed with TEXSAN (Molecular Structure Corporation, 1989) software using a VAXstation 3520 computer. The figures were drawn with ORTEPII (Johnson, 1976). RK thanks Suomen Kulttuurirahasto for a grant. Lists of structure factors, anisotropic displacement parameters, H-atom coordinates and bond distances involving H atoms have been deposited with the IUCr (Reference: ABI101). Copies may be obtained through The Managing Editor, International Union of Crystallography, 5 Abbey Square, Chester CH1 2HU, England. References Gilmore, C. J. (1984). J. Appl. Cryst. 17, 42-46. Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Molecular Structure Corporation (1989). TEXSAN. TEXRAY Single Crystal Structure Analysis Software. Version 5.0. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA. Teixidor, F., Sfinchez-Castell6, G., Lucena, N., Escriche, L., Kivek~s, R., Sundberg, M. & Casab6, J. (1991). Inorg. Chem. 311, 4931-4935. Offerman, W. & V6gtle, F. (1977). Synthesis, pp. 272-273. atoms of the aromatic six-membered ring are almost equidistant from the Ru atom, at distances close to the average value of 2.21 (3) ,A. The other metal-ligand distances are Ru--P 2.299 (2), Ru--Cll 2.411 (1) and Ru-- C12 2.408 (1) A. The distances and angles for the Ru environment show a pseudo-octahedral coordination in which the phenyl ring occupies three of the corners of the distorted octahedron. Comment This work is part of a project dealing with the reactivity of binuclear ruthenium complexes (Cabeza, MuUa & Riera, 1994), as the title compound, (I), is a derivative of [Ru2- C14(r/6-p-cymene)2]. The angles formed by the centroid I (I) (CZ) of the p-cymene phenyl ring and the other Ru ligands are CZ--Ru--P 131.1 (2), CZ--Ru--Cll 128.6 (2) and CZ--Ru--C12 128.5 (2) °. These values and the bond distances and angles of the tide compound are in good agreement with those found in similar compounds (Regragui, Dixneuf, Taylor & Carty, 1984; Cabeza, Mulla & Riera, 1994). Acta Cryst. (1994). C50, 1064-1065 [RuCI2 (PH2 Cy) (0 6-p-cymene) ] JUAN F. VAN DER I%4_AIqI.~N URL~ AND SANTIAGO GARCiA-GRANDA Departamento de Ouimica Fisica y Analitica, Universidad de Oviedo, Avda. Julian Claverla 8, 33006 Oviedo, Spain JAVIER A. C,~os.z~, AND IGNACIO DE[, RiO Departamento de Ouimica Orgrnica e lnorg~nica, Universidad de Oviedo, Avda. Julian Claveria 8, 33006 Oviedo, Spain (Received 27 October 1993; accepted 27 January 1994) Abstract The structure of dichloro(cyclohexylphosphine)(r/6-p - cymene)ruthenium, [RuC12(r/6-C10H14)(C6H13P)], is reported. The structure determination shows that the C © 1994 International Union of Crystallography Printed in Great Britain - all fights reserved © ~c3 cl ~ c8 © b Fig. 1. EUCLID (Spek, 1982) plot of the title compound showing the atomic numbering scheme. Displacement ellipsoids are shown at the 50% probability level. Experimental The compound was prepared in quantitative yield from [Ru2Ch- (rfl-p-cymene)2] and PH2Cy following the procedure described for the synthesis of the analogous complex [RuCl20aHPh2)(r/6- p-cymene)] (Regragui, Dixneuf, Taylor & Carty, 1984). Acta Crystallographica Section C ISSN 0108-2701 ©1994