data reports Bis[S-hexyl 3-(thiophen-2-ylmethylidene)dithiocarbazato-j 2 N 3,S]palladium(II) Structure description

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1 Bis[S-hexyl 3-(thiophen-2-ylmethylidene)dithiocarbazato-j 2 N 3,S]palladium(II) ISSN K. Begum, a * M. C. Sheikh, b R. Miyatake, c E. Zangrando d and M. S. Begum e Received 15 June 2016 Accepted 12 July 2016 a Department of Physics, Shahjalal University of Science and Technology, Sylhet 3114, Bangladesh, b Department of Applied Chemistry, Faculty of Engineering, University of Toyama, 3190 Gofuku, Toyama , Japan, c Center for Environmental Conservation and Research Safety, University of Toyama, 3190 Gofuku, Toyama , Japan, d Department of Chemical and Pharmaceutical Sciences, via Giorgieri 1, Trieste, Italy, and e Department of Chemistry, Shahjalal University of Science and Technology, Sylhet 3114, Bangladesh. *Correspondence china@sust.edu Edited by C. Rizzoli, Universita degli Studi di Parma, Italy Keywords: crystal structure; palladium(ii) complex; dithiocarbazate ligand. CCDC reference: In the title complex, [Pd(C 12 H 17 N 2 S 3 ) 2 ], the Pd II atom exhibits a square-planar coordination geometry with the N,S-chelating ligands arranged in a trans configuration. Intramolecular C HS hydrogen bonds are observed. In the crystal, molecules are linked by weak C HN hydrogen-bond interactions, forming chains parallel to the b axis. Structural data: full structural data are available from iucrdata.iucr.org Structure description The title compound is isomorphous and isotypic to the bischelated copper(ii) and nickel(ii) complexes (Begum et al., 2016). In the complex (Fig. 1), the two Schiff bases, in their deprotonated imino thiolate form, chelate the metal centre via the N1/N3 azomethine nitrogen and S2/S5 thiolate sulfur atoms in a trans-planar configuration exhibiting a pseudo-centrosymmetric arrangement. The molecular structure of similar non-coordinating ligands (Begum, Howlader et al., 2015; Begum, Zangrando et al., 2015) shows the -nitrogen and the thioketo sulfur atoms are trans located with respect to the C6 N2 bond. Thus, upon coordination the deprotonated ligand requires rotation by 180 about this C N bond in order to allow the N,S chelating behavior towards the metal. In the complex the ligand shows some geometrical variations with respect to the free species, the most significant being an elongation of the thioketo C6 S2 bond length with a concomitant decrease of the N1 C5 and increase of the N N bond lengths. The molecular conformation is enforced by intramolecular C HS hydrogen bonds (Table 1). The hexyl chains exhibit all carbon atoms in an anti conformation, this conformation being recognized as an energy minimum. In the crystal (Fig. 2), molecules are arranged 1of3

2 Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA C5 H4S (17) 129 C15 H20N4 i (19) 141 C17 H21S (16) 124 Symmetry code: (i) x þ 1; y 1 2 ; z þ 1 2. Table 2 Experimental details. Figure 1 The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. with the alkyl chains giving rise to a hydrophobic region and forming chains parallel to the b axis via weak C HN hydrogen bonds (Table 1). Synthesis and crystallization The title complex was prepared following a previously reported method (Begum et al., 2016). A solution of PdCl 2 (0.044 g, 0.25 mmol) in 25 ml methanol was added to a solution of S-hexyl-3-(2-thienylidene)dithiocarbazate (0.144 g, Crystal data Chemical formula [Pd(C 12 H 17 N 2 S 3 ) 2 ] M r Crystal system, space group Monoclinic, P2 1 /c Temperature (K) 173 a, b, c (Å) (3), (19), (4) ( ) (7) V (Å 3 ) (10) Z 4 Radiation type Mo K (mm 1 ) 1.10 Crystal size (mm) Data collection Diffractometer Rigaku R-AXIS RAPID Absorption correction Multi-scan (ABSCOR; Rigaku, 1995) T min, T max 0.653, No. of measured, independent and 27863, 6611, 5991 observed [F 2 >2.0(F 2 )] reflections R int (sin /) max (Å 1 ) Refinement R[F 2 >2(F 2 )], wr(f 2 ), S 0.021, 0.055, 1.08 No. of reflections 6611 No. of parameters 318 H-atom treatment H-atom parameters constrained max, min (e Å 3 ) 0.46, 0.41 Computer programs: RAPID-AUTO (Rigaku, 2010), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and publcif (Westrip, 2010). 0.5 mmol) in 10 ml methanol. The resulting mixture was refluxed with constant stirring for 4 h. The orange red precipitate formed was filtered off, washed with methanol and dried in vacuo over anhydrous CaCl 2. Orange red single crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation from a mixture of dichloromethane and acetonitrile (3:1 v/v). M.p. = 352 K. Refinement Crystal data, data collection and structure refinement details are summarized in Table 2. Figure 2 Crystal packing of the title complex viewed down the b axis. Acknowledgements MSB is grateful to the Department of Chemistry, Rajshahi University, for the provision of laboratory facilities. MCS acknowledges the Department of Applied Chemistry, Toyama 2of3 Begum et al. [Pd(C 12 H 17 N 2 S 3 ) 2 ]

3 University, for providing funds for single-crystal X-ray analyses. References Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. Begum, M. S., Howlader, M. B. H., Miyatake, R., Zangrando, E. & Sheikh, M. C. (2015). Acta Cryst. E71, o199. Begum, M. S., Zangrando, E., Howlader, M. B. H., Sheikh, M. C., Miyatake, R., Hossain, M. M., Alam, M. M. & Hasnat, M. A. (2016). Polyhedron, 105, Begum, M. S., Zangrando, E., Sheikh, M. C., Miyatake, R. & Hossain, M. M. (2015). Acta Cryst. E71, o265 o266. Farrugia, L. J. (2012). J. Appl. Cryst. 45, Rigaku (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Rigaku (2010). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Sheldrick, G. M. (2008). Acta Cryst. A64, Westrip, S. P. (2010). J. Appl. Cryst. 43, Begum et al. [Pd(C 12 H 17 N 2 S 3 ) 2 ] 3of3

4 full crystallographic data [ Bis[S-hexyl 3-(thiophen-2-ylmethylidene)dithiocarbazato-κ 2 N 3,S]palladium(II) K. Begum, M. C. Sheikh, R. Miyatake, E. Zangrando and M. S. Begum Bis[S-hexyl 3-(thiophen-2-ylmethylidene)dithiocarbazato-κ 2 N 3,S]palladium(II) Crystal data [Pd(C 12 H 17 N 2 S 3 ) 2 ] M r = Monoclinic, P2 1 /c Hall symbol: -P 2ybc a = (3) Å b = (19) Å c = (4) Å β = (7) V = (10) Å 3 Z = 4 Data collection Rigaku R-AXIS RAPID diffractometer Detector resolution: pixels mm -1 ω scans Absorption correction: multi-scan (ABSCOR; Rigaku, 1995) T min = 0.653, T max = measured reflections Refinement Refinement on F 2 R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 318 parameters 0 restraints Primary atom site location: structure-invariant direct methods F(000) = D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from reflections θ = µ = 1.10 mm 1 T = 173 K Prism, orange mm 6611 independent reflections 5991 reflections with F 2 > 2.0σ(F 2 ) R int = θ max = 27.5 h = k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.030P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.46 e Å 3 Δρ min = 0.41 e Å 3 Special details Refinement. Refinement was performed using all reflections. The weighted R-factor (wr) and goodness of fit (S) are based on F 2. R-factor (gt) are based on F. The threshold expression of F 2 > 2.0 sigma(f 2 ) is used only for calculating R- factor (gt). data-1

5 Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Pd (8) (11) (5) (4) S (3) (4) (2) (9) S (3) (4) (19) (9) S (3) (4) (2) (10) S (3) (4) (18) (8) S (3) (4) (18) (9) S (3) (4) (2) (9) N (9) (12) (6) (3) N (9) (13) (6) (3) N (9) (12) (6) (3) N (9) (12) (6) (3) C (13) (17) (8) (4) C (12) (17) (8) (4) C (11) (16) (8) (3) C (11) (15) (7) (3) C (11) (15) (7) (3) C (11) (15) (8) (3) C (12) (16) (8) (4) C (12) (17) (8) (4) C (12) (16) (8) (4) C (12) (17) (8) (4) C (12) (17) (8) (4) C (14) (19) (9) (4) C (12) (16) (8) (4) C (11) (16) (7) (4) C (11) (15) (7) (3) C (10) (14) (7) (3) C (10) (14) (7) (3) C (10) (14) (7) (3) C (12) (16) (8) (4) C (11) (16) (8) (3) C (12) (17) (8) (4) C (12) (16) (9) (4) C (13) (19) (9) (4) C (15) (2) (11) (5) H * H * H * H * H * H * H * H * H * H * data-2

6 H * H * H * H * H * H * H * H * H * H * H * H * H * H * H * H * H * H * H * H * H * H * H * H * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Pd (7) (7) (6) (4) (4) (4) S (2) (3) (19) (15) (15) (16) S (2) (2) (18) (16) (15) (16) S (3) (3) (2) (17) (17) (17) S (19) (18) (17) (14) (14) (14) S (2) (3) (17) (16) (15) (15) S (2) (3) (19) (16) (15) (16) N (7) (7) (6) (5) (5) (5) N (7) (7) (7) (5) (5) (5) N (7) (7) (6) (5) (5) (5) N (7) (7) (6) (5) (5) (5) C (9) (10) (8) (7) (7) (7) C (9) (9) (8) (7) (7) (7) C (8) (9) (8) (6) (6) (7) C (8) (8) (7) (6) (6) (6) C (8) (8) (7) (6) (6) (6) C (8) (8) (8) (6) (6) (6) C (9) (9) (8) (7) (7) (7) C (9) (10) (9) (7) (7) (7) C (9) (9) (9) (7) (7) (7) data-3

7 C (9) (9) (8) (7) (7) (7) C (9) (9) (9) (7) (7) (7) C (10) (12) (10) (8) (8) (8) C (9) (9) (7) (6) (6) (6) C (8) (9) (7) (6) (6) (7) C (8) (8) (8) (6) (6) (6) C (7) (8) (7) (6) (6) (6) C (8) (7) (7) (6) (6) (6) C (8) (8) (7) (6) (6) (6) C (9) (9) (8) (7) (6) (7) C (8) (8) (8) (6) (6) (7) C (9) (9) (8) (7) (7) (7) C (9) (9) (9) (7) (7) (7) C (10) (11) (10) (8) (8) (8) C (12) (12) (13) (9) (10) (10) Geometric parameters (Å, º) Pd1 S (4) C22 C (3) Pd1 S (4) C23 C (3) Pd1 N (14) C1 H Pd1 N (14) C2 H S1 C (18) C3 H S1 C (17) C5 H S2 C (19) C7 H S3 C (16) C7 H S3 C (19) C8 H S4 C (18) C8 H S4 C (16) C9 H S5 C (17) C9 H S6 C (15) C10 H S6 C (19) C10 H N1 N (18) C11 H N1 C (19) C11 H N2 C (2) C12 H N3 N (18) C12 H N3 C (19) C12 H N4 C (19) C13 H C1 C (3) C14 H C2 C (3) C15 H C3 C (3) C17 H C4 C (3) C19 H C7 C (3) C19 H C8 C (3) C20 H C9 C (3) C20 H C10 C (3) C21 H C11 C (3) C21 H C13 C (3) C22 H data-4

8 C14 C (3) C22 H C15 C (2) C23 H C16 C (3) C23 H C19 C (3) C24 H C20 C (3) C24 H C21 C (3) C24 H S1 N (15) C22 H13 iii S1 N (15) C22 H16 iii S1 C (16) C23 H1 xvi S2 C (16) C23 H13 iii S4 N (15) C23 H13 xvi S4 N (14) C23 H14 xvi S4 C (16) C24 H1 xvi S5 C (17) C24 H10 xvi N2 C (2) C24 H13 xvi N2 C (3) C24 H16 iii N4 C (19) C24 H26 xvii N4 C (3) H1 C12 xiv C5 C (2) H1 C23 x C17 C (2) H1 C24 x S5 C13 i (17) H1 H13 xiv N4 C15 ii (19) H1 H15 xiv C2 C15 iii (3) H1 H29 ix C3 C15 i (3) H1 H30 x C3 C16 i (2) H1 H32 x C4 C17 iii (2) H1 H33 x C12 C14 iv (3) H2 S2 i C13 S5 v (17) H2 N3 i C14 C12 vi (3) H2 C15 iii C14 C18 vii (2) H2 C17 i C15 N4 vii (19) H2 C21 ix C15 C2 iii (3) H2 H15 xiv C15 C3 v (3) H2 H20 iii C16 C3 v (2) H2 H21 i C17 C4 iii (2) H2 H23 ix C18 C14 ii (2) H2 H25 ix Pd1 H H2 H27 ix Pd1 H H3 S4 i S1 H H3 C13 i S1 H H3 C14 i S1 H H3 C15 i S1 H H3 C16 i S2 H H3 C17 i S3 H H3 C19 ix S3 H H3 H19 i S4 H H3 H20 iii S4 H H3 H20 i data-5

9 S4 H H3 H21 i S4 H H3 H23 ix S5 H H3 H25 ix S6 H H4 C13 i S6 H H4 C14 i N2 H H4 H17 viii N2 H H4 H18 i N2 H H4 H19 i N4 H H4 H21 iii N4 H H5 S6 iii N4 H H5 N4 iii C1 H H5 C18 iii C3 H H5 C19 iii C3 H H5 H22 iii C4 H H5 H24 iii C4 H H6 C8 viii C5 H H6 C9 viii C6 H H6 H6 viii C6 H H6 H7 viii C7 H H6 H9 viii C7 H H6 H11 viii C8 H H7 S1 viii C8 H H7 C22 xi C9 H H7 H6 viii C9 H H7 H9 viii C9 H H7 H24 xi C9 H H7 H25 xi C10 H H7 H28 xi C10 H H7 H29 xi C10 H H8 C20 iii C10 H H8 C22 xi C10 H H8 H12 xviii C11 H H8 H22 iii C11 H H8 H24 xi C12 H H8 H24 iii C12 H H8 H25 xi C13 H H8 H28 xi C15 H H8 H29 xi C15 H H9 S3 viii C16 H H9 C7 viii C16 H H9 H6 viii C17 H H9 H7 viii C18 H H9 H31 x C18 H H9 H32 x C19 H H10 C19 iii C19 H H10 C20 iii C20 H H10 C21 iii C20 H H10 C24 x data-6

10 C21 H H10 H22 iii C21 H H10 H24 iii C21 H H10 H26 iii C21 H H10 H31 x C22 H H10 H32 x C22 H H10 H34 x C22 H H11 S1 viii C22 H H11 N1 viii C22 H H11 N2 viii C23 H H11 C4 viii C23 H H11 C5 viii C24 H H11 C20 xi C24 H H11 H6 viii H1 H H11 H24 xi H2 H H11 H25 xi H3 H H12 C20 xi H5 H H12 C22 iii H5 H H12 H8 xviii H5 H H12 H24 xi H5 H H12 H24 iii H6 H H12 H25 xi H6 H H12 H26 iii H6 H H12 H28 iii H6 H H13 C21 iii H7 H H13 C22 iii H7 H H13 C23 iii H7 H H13 C23 x H7 H H13 C24 x H8 H H13 H1 xv H8 H H13 H26 iii H8 H H13 H28 iii H8 H H13 H30 iii H9 H H13 H31 x H9 H H13 H32 x H9 H H13 H33 iii H9 H H13 H34 x H10 H H14 S2 viii H10 H H14 N1 viii H10 H H14 N2 viii H10 H H14 C6 viii H11 H H14 C23 x H11 H H14 H31 x H11 H H15 C1 xv H11 H H15 C2 xv H12 H H15 C13 iv H12 H H15 C14 iv H12 H H15 H1 xv H12 H H15 H2 xv data-7

11 H13 H H15 H18 iv H13 H H15 H19 iv H13 H H15 H30 iii H14 H H15 H33 iii H14 H H16 S6 xi H14 H H16 C13 iv H18 H H16 C14 iv H19 H H16 C22 iii H20 H H16 C24 iii H22 H H16 H18 iv H22 H H16 H19 iv H22 H H16 H28 iii H22 H H16 H30 iii H23 H H16 H33 iii H23 H H17 Pd1 viii H23 H H17 S6 xi H23 H H17 N1 viii H24 H H17 C5 viii H24 H H17 C14 iv H24 H H17 H4 viii H24 H H17 H19 iv H25 H H18 S2 ii H25 H H18 S3 ii H25 H H18 S5 v H25 H H18 H4 v H26 H H18 H15 vi H26 H H18 H16 vi H26 H H18 H33 xii H26 H H19 S5 vii H27 H H19 S5 v H27 H H19 N4 vii H27 H H19 C12 vi H27 H H19 C18 vii H28 H H19 H3 v H28 H H19 H4 v H28 H H19 H15 vi H28 H H19 H16 vi H29 H H19 H17 vi H29 H H20 S4 vii H29 H H20 N3 vii H29 H H20 N4 vii H29 H H20 C2 iii H30 H H20 C3 iii H30 H H20 C18 vii H30 H H20 C19 vii H31 H H20 H2 iii H31 H H20 H3 iii H31 H H20 H3 v data-8

12 Pd1 H17 viii H20 H23 vii S1 H7 viii H21 S4 vii S1 H11 viii H21 C3 iii S1 H25 ix H21 C4 iii S1 H32 x H21 C5 iii S2 H2 v H21 H2 v S2 H14 viii H21 H3 v S2 H18 vii H21 H4 iii S2 H27 vii H21 H23 vii S3 H9 viii H22 C7 iii S3 H18 vii H22 C9 iii S3 H34 xi H22 H5 iii S4 H3 v H22 H8 iii S4 H20 ii H22 H10 iii S4 H21 ii H22 H32 xii S4 H32 xii H23 C2 ix S4 H33 xii H23 C3 ix S5 H18 i H23 C15 ii S5 H19 ii H23 H2 ix S5 H19 i H23 H3 ix S6 H5 iii H23 H20 ii S6 H16 xiii H23 H21 ii S6 H17 xiii H24 C8 iii N1 H11 viii H24 C9 iii N1 H14 viii H24 C10 xiii N1 H17 viii H24 C10 iii N2 H11 viii H24 H5 iii N2 H14 viii H24 H7 xiii N3 H2 v H24 H8 xiii N3 H20 ii H24 H8 iii N4 H5 iii H24 H10 iii N4 H19 ii H24 H11 xiii N4 H20 ii H24 H12 xiii C1 H15 xiv H24 H12 iii C1 H25 ix H25 S1 ix C1 H29 ix H25 C1 ix C1 H30 x H25 C2 ix C1 H32 x H25 C3 ix C1 H33 x H25 C4 ix C2 H15 xiv H25 C10 xiii C2 H20 iii H25 H2 ix C2 H23 ix H25 H3 ix C2 H25 ix H25 H7 xiii C2 H27 ix H25 H8 xiii C2 H29 ix H25 H11 xiii C3 H20 iii H25 H12 xiii C3 H21 iii H26 C9 iii C3 H23 ix H26 C24 xii data-9

13 C3 H25 ix H26 H10 iii C4 H11 viii H26 H12 iii C4 H21 iii H26 H13 iii C4 H25 ix H26 H32 xii C5 H11 viii H26 H34 xii C5 H17 viii H27 S2 ii C5 H21 iii H27 C2 ix C6 H14 viii H27 H2 ix C7 H9 viii H27 H34 xii C7 H22 iii H28 C8 xiii C8 H6 viii H28 C10 iii C8 H24 iii H28 C11 iii C8 H28 xi H28 C12 iii C8 H29 xi H28 H7 xiii C9 H6 viii H28 H8 xiii C9 H22 iii H28 H12 iii C9 H24 iii H28 H13 iii C9 H26 iii H28 H16 iii C9 H32 x H29 C1 ix C10 H24 xi H29 C2 ix C10 H24 iii H29 C8 xiii C10 H25 xi H29 H1 ix C10 H28 iii H29 H7 xiii C11 H28 iii H29 H8 xiii C11 H30 iii H29 H30 xvii C11 H31 x H30 C1 xvi C12 H1 xv H30 C11 iii C12 H19 iv H30 H1 xvi C12 H28 iii H30 H13 iii C12 H33 iii H30 H15 iii C13 H3 v H30 H16 iii C13 H4 v H30 H29 xii C13 H15 vi H30 H34 xii C13 H16 vi H31 C11 xvi C13 H33 xii H31 H9 xvi C14 H3 v H31 H10 xvi C14 H4 v H31 H13 xvi C14 H15 vi H31 H14 xvi C14 H16 vi H32 S1 xvi C14 H17 vi H32 S4 xvii C15 H2 iii H32 C1 xvi C15 H3 v H32 C9 xvi C15 H23 vii H32 H1 xvi C16 H3 v H32 H9 xvi C17 H2 v H32 H10 xvi C17 H3 v H32 H13 xvi C18 H5 iii H32 H22 xvii C18 H19 ii H32 H26 xvii data-10

14 C18 H20 ii H33 S4 xvii C19 H3 ix H33 C1 xvi C19 H5 iii H33 C12 iii C19 H10 iii H33 C13 xvii C19 H20 ii H33 H1 xvi C20 H8 iii H33 H13 iii C20 H10 iii H33 H15 iii C20 H11 xiii H33 H16 iii C20 H12 xiii H33 H18 xvii C21 H2 ix H34 S3 xiii C21 H10 iii H34 C21 xvii C21 H13 iii H34 H10 xvi C21 H34 xii H34 H13 xvi C22 H7 xiii H34 H26 xvii C22 H8 xiii H34 H27 xvii C22 H12 iii H34 H30 xvii S2 Pd1 S (15) C7 C8 H S2 Pd1 N (4) C9 C8 H S2 Pd1 N (4) C9 C8 H S5 Pd1 N (4) H7 C8 H S5 Pd1 N (4) C8 C9 H N1 Pd1 N (5) C8 C9 H C1 S1 C (9) C10 C9 H Pd1 S2 C (5) C10 C9 H C6 S3 C (8) H9 C9 H C13 S4 C (8) C9 C10 H Pd1 S5 C (5) C9 C10 H C18 S6 C (8) C11 C10 H Pd1 N1 N (10) C11 C10 H Pd1 N1 C (11) H11 C10 H N2 N1 C (14) C10 C11 H N1 N2 C (14) C10 C11 H Pd1 N3 N (10) C12 C11 H Pd1 N3 C (11) C12 C11 H N4 N3 C (13) H13 C11 H N3 N4 C (13) C11 C12 H S1 C1 C (15) C11 C12 H C1 C2 C (16) C11 C12 H C2 C3 C (15) H15 C12 H S1 C4 C (13) H15 C12 H S1 C4 C (12) H16 C12 H C3 C4 C (15) S4 C13 H N1 C5 C (15) C14 C13 H S2 C6 S (9) C13 C14 H S2 C6 N (13) C15 C14 H S3 C6 N (14) C14 C15 H S3 C7 C (11) C16 C15 H data-11

15 C7 C8 C (14) N3 C17 H C8 C9 C (14) C16 C17 H C9 C10 C (14) S6 C19 H C10 C11 C (14) S6 C19 H S4 C13 C (14) C20 C19 H C13 C14 C (14) C20 C19 H C14 C15 C (14) H22 C19 H S4 C16 C (12) C19 C20 H S4 C16 C (11) C19 C20 H C15 C16 C (14) C21 C20 H N3 C17 C (14) C21 C20 H S5 C18 S (8) H24 C20 H S5 C18 N (12) C20 C21 H S6 C18 N (13) C20 C21 H S6 C19 C (12) C22 C21 H C19 C20 C (13) C22 C21 H C20 C21 C (14) H26 C21 H C21 C22 C (14) C21 C22 H C22 C23 C (16) C21 C22 H S1 C1 H C23 C22 H C2 C1 H C23 C22 H C1 C2 H H28 C22 H C3 C2 H C22 C23 H C2 C3 H C22 C23 H C4 C3 H C24 C23 H N1 C5 H C24 C23 H C4 C5 H H30 C23 H S3 C7 H C23 C24 H S3 C7 H C23 C24 H C8 C7 H C23 C24 H C8 C7 H H32 C24 H H5 C7 H H32 C24 H C7 C8 H H33 C24 H S2 Pd1 N1 N (8) N2 N1 C5 C4 0.9 (2) S2 Pd1 N1 C (9) C5 N1 N2 C (11) N1 Pd1 S2 C (4) N1 N2 C6 S (19) S2 Pd1 N3 N (8) N1 N2 C6 S (10) S2 Pd1 N3 C (9) Pd1 N3 N4 C (14) N3 Pd1 S2 C (4) Pd1 N3 C17 C (9) S5 Pd1 N1 N (8) N4 N3 C17 C (19) S5 Pd1 N1 C (9) C17 N3 N4 C (11) N1 Pd1 S5 C (4) N3 N4 C18 S (18) S5 Pd1 N3 N (8) N3 N4 C18 S (9) S5 Pd1 N3 C (9) S1 C1 C2 C (18) N3 Pd1 S5 C (4) C1 C2 C3 C (19) C1 S1 C4 C (11) C2 C3 C4 S (17) C1 S1 C4 C (13) C2 C3 C4 C (12) data-12

16 C4 S1 C1 C (12) S1 C4 C5 N1 2.6 (3) Pd1 S2 C6 S (7) C3 C4 C5 N (14) Pd1 S2 C6 N (13) S3 C7 C8 C (9) C6 S3 C7 C (9) C7 C8 C9 C (12) C7 S3 C6 S (9) C8 C9 C10 C (12) C7 S3 C6 N (13) C9 C10 C11 C (12) C13 S4 C16 C (10) S4 C13 C14 C (17) C13 S4 C16 C (11) C13 C14 C15 C (18) C16 S4 C13 C (11) C14 C15 C16 S (16) Pd1 S5 C18 S (7) C14 C15 C16 C (12) Pd1 S5 C18 N (12) S4 C16 C17 N3 5.3 (2) C18 S6 C19 C (9) C15 C16 C17 N (13) C19 S6 C18 S (8) S6 C19 C20 C (9) C19 S6 C18 N (12) C19 C20 C21 C (12) Pd1 N1 N2 C (15) C20 C21 C22 C (12) Pd1 N1 C5 C (9) C21 C22 C23 C (12) Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1, y+1/2, z+1/2; (iii) x+1, y, z+1; (iv) x 1, y 1/2, z+1/2; (v) x, y+1/2, z 1/2; (vi) x+1, y 1/2, z 1/2; (vii) x+1, y 1/2, z+1/2; (viii) x, y, z+1; (ix) x+1, y+1, z+1; (x) x 1, y+1/2, z+1/2; (xi) x 1, y 1, z; (xii) x+2, y 1/2, z+1/2; (xiii) x+1, y+1, z; (xiv) x, y+1/2, z+3/2; (xv) x, y 1/2, z+3/2; (xvi) x+1, y+1/2, z 1/2; (xvii) x+2, y+1/2, z+1/2; (xviii) x, y 1, z+1. Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A C5 H4 S (17) 129 C15 H20 N4 vii (19) 141 C17 H21 S (16) 124 Symmetry code: (vii) x+1, y 1/2, z+1/2. data-13