The structure of dichlorobis[μ-(3-dimethylamino-1-propanethiolato)-μ-S,N]-dipalladium(II), (I) [Pd2(C5H12NS)2Cl2], and ac,bd,eg, fh-tetrakis[μ-(3-piperidinemethanethiolato)-μ-S,N]-tripalladium(II) dichloride dihydrate, (II) [Pd3(C6H12NS)4]Cl2.2H2O

1653 Acta Cryst. (1983). C39, 1653-1655 The Structure of Diehlorobis~-(3-dimethylaminol-propanethiolato)-~tS,N]-dipalladium(II), (I)[Pd2(C5H12NS)2CI2], and ae, bd, eg, fh-Tetrakis[/~-(3piperidinemethanethiolato)-l~-S,N]-tripalladium(II) Dichloride Dihydrate, (II) [Pd3(C6H12NS)4]CI2.2H20 BY X. SOLANS AND M. FONT-ALTABA Departamento Cristalograf{a y Mineralog{a, Universidad de Barcelona, Gran Via 585, Barcelona 7, Spain J. L. BRIANS6 Departamento Cristalograf(a y Mineralog(a, Universidad A ut6noma de Barcelona, Bellaterra, Barcelona, Spain AND J. SOLA, J. SUADES AND H. BARRERA Departamento Qu[miea Inorganiea, Universidad A ut6noma de Barcelona, Bellaterra, Barcelona, Spain (Received 4 February 1983; accepted 12 September 1983) Abstract. (I): Mr=520.15, monoclinic, P2Jn, a= 7.207 (2), b = 20.616 (4), c= 5.854 (1) A, fl= 96.05 (I) °, V= 864.9 (6) A 3, Z = 2, Ox= 2.00 Mg m -3, Mo K~t, 2 = 0.71069,4,, p = 2.553 mm -~, F(000) = 512, 298 K, R =0.060 for 1492 reflections. (II): Mr-947.07, triclinic, Pi, a = 12.666 (7), b--- 10.595 (6), c= 6.572 (5) A, a= 98.30 (2), fl--- 97.04 (2), y= 99.84 (2) °, V= 850(2)/~ 3, Z----1, Dx= 1.85 Mgm -3, MoK~ 2= 0.71069 A, /z = 1.958 mm -~, F(000) = 490, 298 K, R = 0.071 for 1879 reflections. (I) was solved by direct methods, using MULTAN and DIRDIF, (II) by the heavy-atom method. The four-membered Pd, S, Pd, S rings have a syn-exo conformation, with dihedral angles between the S, Pd, S planes of 154.4 (2) and 133.0 (3) ° for (I) and (II), respectively. Introduction. Synthesis of compounds with di-p-thiolato- (metal) 2 was carried out by the Department of Inorganic Chemistry of the Free University of Barcelona. In order to elucidate the geometry of the title compounds, X-ray analyses were carried out. Experimental. Yellow-orange elongated prisms, 0.3 × 0.1 x0.1mm(I), 0-7×0.2×0.2mm(II), Philips PW-1100 diffractometer, graphite monochromator, oa scan, cell parameters from 25 independent reflections, no significant variation of intensity in three standard reflections, measured each hour; (I) 1518 independent reflections with 0 < 30 °, range ofhkl: l0 to 10, 0 to 25 and 0 to 7, 1492 with__/>_ 2.5a(I); (II) 2008 with 0_< 25 ° , range of hkl: 14 to 14, 12 to 12 and 0 to 8, 1879 with I>2.5tr(I); Lp correction, absorption ignored; (I) direct methods [MULTAN80, Main, Fiske, Hull, Lessinger, Germain, Declercq & Woolfson (1980) and DIRDIF, Beurskens, Bosman, Doesburg, Gould, Van den Hark & Prick (1980)],(II) Patterson (SHELX76, Sheldrick, 1976); anisotropic full matrix, wllFol--IFcI ~ minimized (SHELX76), anomalousscattering factors for all atoms (International Tables for X-ray Crystallography, 1974); hydrogen atoms of (I) from AF synthesis; final R = 0.060(I) and 0.071 (II), R w = 0.063(I) and 0.076(II), d/tr = 2.8 in x of H(C1) (I) and 1.8 in U~ of O(W) (II), max. and min. Ap excursions in final AF synthesis 0.1 and -0.3 elk -3, respectively, in (I) and 0.2 and -0.2 elk -3 in (II), w=[aZ(Fo)+klFol2] -1 , k = 0.0127(I) and 0.0064(II); Digital VAX-750.t Discussion. Systematic extinctions and density measurements indicated P2~/n with Z-- 2 for (I). This would imply a Pd and S planar ring, which does not correspond to other results from the literature. As Fourier synthesis from DIRDIF revealed double peaks with equal height for both Pd and S atoms, their positions were considered to be disordered; significant differences between their temperature coefficients were not observed during the refinement (Table l). The distances between disordered atoms are 0.81 (1)A for Pd-..Pd*' and 1.935 (3)A for S...S*' atoms. The ordered atoms of (I) have higher values for anisotropic thermal coefficients (range of Beq 4.8-8.7 A2), which shows a slight disorder for these atoms; it was not possible to resolve two maxima from difference or t Lists of structure factors, anisotropic thermal parameters, some bond distances and angles and H-atom parameters for (I) have been deposited with the British Library Lending Division as Supplementary Publication No. SUP 38818 (19 pp.). Copies may be obtained through The Executive Secretary, International Union of Crystallography, 5 Abbey Square, Chester CH1 2HU, England. 0108-2701/83/121653-03501.50 © 1983 International Union of Crystallography 1654 [Pd2(CsH12NS)2CI 2] AND [Pd3(C6H12NS)4IC12.2H20 Fourier syntheses. The disorder consists of two localizations for the PdSPdS ring, according to the distances and angles between peaks (Table 2, Fig. 1). The Pd atom of each structure is linked to four atoms in a nearly planar fashion [largest deviation of atom from mean plane is 0.02 (1)A]. The Pd-S bond distances are slightly shorter [mean values: 2.279 (6) A for (I) and 2.305 (15)A for (II)] than values observed in the literature [mean value: 2.320(8)A, range: 2.301 (7)-2.432 (7) A] (Ahmed, Itoh, Matsuda, Ueda, Ishii & Ibers, 1977; Chert & Fackler, 1978; Fenn & Segrott, 1972; Fackler, 1976; Bonamico, Dessy & ~" :: :: // "* 7" CI :" '~ • • ,~,~'. , " 7 (o) Table 1. Positionalparameters (x 104)for (I) and (II) Beq= ( 8 ~ / 3 ) Z iZ jUoa*~.a*jai.a j. x y z Beq(A 2) (I)C IoH24CI2N2Pd2S2 Pd -542 (2) 812 (1) -234 (2) 3.2 (2) Pd* 732 (2) -703 (1) -1062 (2) 3.3 (2) CI -3218 (5) 1328 (1) -1088 (5) 6.5 (6) S 2180 (5) 253 (2) -117 (6) 3.4 (6) S* -1404 (6) 3 (2) -2819 (6) 3.6 (6) C(I) 3417 (16) 331 (6) 2387 (28) 8 (2) C(2) 3866 (26) 972 (7) 3420 (28) 8 (2) C(3) 2179 (25) 1357 (6) -5996 (29) 9 (2) N 698 (I I) 1545 (3) -7745 (12) 4 (I) C(4) --599 (21) 1896 (7) -6435 (26) 7 (2) C(5) 1359 (23) 1997 (8) 637 (22) 8 (6) (II)C24H4sN4Pd3S4.2C1.2H20 Pd(1) 0 0 0 3.1 (3) Pd(2) 2009 (I) 1345 (1) 8001 (2) 2.7 (2) CI 4549 (4) 7387 (6) 829 (14) 8.3 (9) S(1) -763 (3) 568 (4) 2944 (6) 2.9 (6) C(I 1) -1485 (14) 1905 (17) 2586 (28) 4 (3) C(12) -2542 (13) 1776 (17) 3647 (28) 4 (3) C(13) -3466 (13) 654 (20) 2446 (30) 4 (2) N(14) -3301 (12) -593 (14) 3045 (22) 4 (2) C(15) -3298 (15) -555 (20) 5370 (24) 4 (2) C(16) --2398 (20) 442 (21) 6577 (27) 6 (5) C(17) --2347 (18) 1812 (21) 6008 (31) 5 (3) S(2) -546 (3) -2043 (4) 838 (6) 3.0 (6) C(21) --1078 (14) -3206 (17) -1541 (27) 4 (2) C(22) -2048 (14) -4314 (16) -1351 (26) 3 (3) C(23) --3050 (16) -3862 (20) --1020 (26) 4 (2) N(24) -3055 (I 1) -3172 (14) 1109 (20) 4 (2) C(25) -2883 (14) --4102 (18) 2637 (27) 4 (2) C(26) -1832 (19) -4534 (17) 2521 (28) 5 (2) C(27) -1710 (13) -5147 (15) 227 (26) 4 (2) O 4737 (21) 6260 (21) 5246 (36) 10 (5) Table 2. Bond lengths (A) and angles (°) (II) (I) (II) for (I) and Pd-S 2.270 (3) Pd(1)-S(I) Pd-S* 2.294 (3) Pd(1)-S(2) Pd-CI 2.213 (3) Pd-N 2.220 (5) Pd*'-S' 2.271 (3) Pd(2)-S(1) Pd*'-S*' 2.282 (3) Pd(2)-S(2) Pd*'-CI 2.445 (3) Pd(2)-N(14) Pd*'-N 2.101 (5) Pd(2)-N(24) S...S* 2.929 (4) S(1)--.S(2) Pd...Pd* 3-305 (I) Pd(1)...Pd(2) S-Pd-S* 79.8 (1) S(1)-Pd(1)-S(2) S*-Pd-CI 91.8 (1) S(1)--Pd(1)-S(2') C1--Pd-N 95.9 (2) S-Pd-N 92.2 (2) Pd-S-Pd* 93.4 (1) Pd(I)-S(1)-Pd(2) Pd-S*-Pd* 92.5 (1) Pd(I)-S(2)-Pd(2) S'-Pd*'-S*' 80.1 (1) S(l)-Pd(2)-S(2) S'-Pd*'-CI' 92.2 (I) S(I)-Pd(2)-N(14) S*'-Pd*'-N' 95.3 (2) S(2)--Pd(2)-N(24) 2.315 (4) 2.322 (4) 2.299 (4) 2.283 (4) 2.086 (6) 2.110 (6) 2.982 (6) 3.217(1) 8o.o(1) 100.0 (1) 88.4(1) 88.6 (1) 81.2 (1) 95.6 (5) 94.8 (5) C(13)~ C(12) 2 i' ' ' c,~~--~2~ ~ - 7 C(27)// "-' '~-JS(2) ~,~2 6 ~,~ ~ .. (b) Fig. 1. ORTEP (Johnson, 1965) drawings of (a) molecule of (I) and (b) cation of (II). Fares, 1977; Piovesana, Sestili, Bellito, Flamini, Tomassini, Zanazzi & Zanzari, 1977; Girling & Amma, 1976; Pope & Boeyens, 1976; Fowler & Griffiths, 1978). The Pd-C1 and Pd-N bond distances are within the ranges observed in the papers of Fowler & Griffiths (1978). The differences observed in (I) are assigned to the disorder of these atoms. The four-membered rings have a syn-exo conformation, with dihedral angles between the S,Pd,S planes of 154.4 (2) ° in (I) and 133.0 (3) ° in (II). These dihedral angles are flatter than those observed in the literature (131.8 °, Fackler, 1976), which helps to explain the shortening of Pd-S distances. Moreover, this flattening reduces the S...S bite distances [2.929 (4) in (I), 2.982 (6) in (II) and 3.05 (8) A in the literature]. The piperidine and the Pd,S,C3,N rings have chair conformations, while the latter type of ring has boat and chair conformations in tetrakis(3-amino-1propanethiolato)trinickel(II) chloride (Brians6, Perucaud, Suades & Barrera, 1980). The crystal structures consist of discrete molecules or ions linked by van der Waals interactions and, in (II), by ionic forces. The shortest interionic distances are C1...N(14) 3.237 (7) and C1...N(24) 3.150 (7) A. This work was sponsored by the University of Barcelona. X. SOLANS, M. FONT-ALTABA, J. L. BRIANS6, J. SOLA. J. SUADES AND H. BARRERA 1655 References AHMED, J., ITOH, K., MATSUDA, I., UEDA, F., ISHII, Y. & IBERS, J. A. (1977). Inorg. Chem. 16, 620-624. BEURSKENS, P. T., BOSMAN, W. P., DOESBURG, n. M., GOULD, R. O., VAN DEN HARK, TH. E. M. & PRICK, P. A. J. (1980). DIRDIF. An automatic procedure for phase extension and refinement of difference structure factors. Tech. Rep. 1980/1. Univ. of Nijmegen, The Netherlands. 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