Synthesis, crystal structure and Hirshfeld surface analysis of bis­[N-(4-chloro­benz­yl)-N-do­decyl­dithio­carbamato-κ2S,S′]palladium(II)

Pallavi, R.; Srinivasan, N.; Thirumaran, S.

doi:10.1107/S205698902600188X

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ISSN: 2056-9890

Volume 82| Part 4| April 2026| Pages 384-387

https://doi.org/10.1107/S205698902600188X

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Synthesis, crystal structure and Hirshfeld surface analysis of bis[N-(4-chlorobenzyl)-N-dodecyldithiocarbamato-κ²S,S′]palladium(II)

R. Pallavi,^a N. Srinivasan ^b and S. Thirumaran ^a ^*

^aDepartment of Chemistry, Annamalai University, Annamalainagar-608002, India, and ^bDepartment of Chemistry, Saveetha School of Engineering, Saveetha Institute of Medical And Technical Sciences (SIMATS), Saveetha Nagar, Thandalam, Chennai 602105, Tamil Nadu, India
^*Correspondence e-mail: [email protected]

Edited by J. Ellena, Universidade de Sâo Paulo, Brazil (Received 27 January 2026; accepted 19 February 2026; online 24 March 2026)

The title compound, [Pd(C₂₀H₃₁ClNS₂)₂], crystallizes about an inversion centre in the monoclinic space group C2/c. The Pd^II cation adopts a square-planar coordination geometry defined by four sulfur atoms from two N-(4-chlorobenzyl)-N-dodecyldithiocarbamate anions. The crystal packing features C—H⋯S hydrogen bonds, which form a belt motif. Hirshfeld surface analysis indicates that H⋯H (62.9%), S⋯H/H⋯S (14.0%) and Cl⋯H/H⋯Cl (11.1%) contacts dominate the intermolecular interactions.

Keywords: crystal structure; Hirshfeld surface analysis; dithiocarbamate; palladium.

CCDC reference: 2532016

1. Chemical context

Dithiocarbamates (R₂NCS₂⁻) form stable complexes with transition metals, lanthanides and actinides (Hogarth et al., 2005 ; Hitchcock et al., 2004 ; Mahato et al., 2015 ; Behrle et al., 2018 ). They can bind to metals in nine distinct coordination modes. The most common of these are monodentate and chelating bidentate coordination modes (Hogarth et al., 2005). The properties of complexes are influenced by the electronic configuration of the central metal cation and N-bonded organic (R) moiety of dithiocarbamate ligands (Hogarth et al., 2012 ; Godoy-Alcántar et al., 2025 ). Metal–dithiocarbamate complexes exhibit a wide range of applications in various fields, including catalysis, sensors, medicine, material science and rubber manufacturing (Ajiboye et al., 2022 ). In particular, Pd^II dithiocarbamate complexes show important biological activities, viz. antibacterial (Khan et al., 2016 ), antifungal (Ferreira et al., 2014 ), anticancer (Khan et al., 2016; Khan et al., 2011 ). Several studies on metal dithiocarbamate complexes indicated that the length of the alkyl chain (R) of the dithiocarbamate ligand enhances the solubility and activity of complexes (Hogarth et al., 2012).

As part of our work in this area, we report here the synthesis, crystal structure and Hirshfeld surface analysis of a Pd^II dithiocarbamate complex containing a long-chain alkyl group (dodecyl) (Fig. 1).

Figure 1
The molecular structure of the title complex, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms have been omitted for clarity. Symmetry-generated atoms were generated by the operation x + $[{\script{3\over 2}}]$ , −y + $[{\script{5\over 2}}]$ , −z + 1.

2. Structural commentary

The title complex crystallizes in the monoclinic space group C2/c. It is a four-coordinated structure in which the palladium atom is coordinated by four sulfur atoms from two N-(4-chlorobenzyl)-N-dodecyldithiocarbamate ligands (Fig. 1). This four-coordinate geometry results in square planar spatial configuration. The bond parameters for the metal–ligand interactions are Pd—S1 = 2.3166 (12) Å, Pd—S2 = 2.3271 (10) Å and the chelate angle S1—Pd—S2 is 75.32 (4) °. These values are typical for Pd^II dithiocarbamate complexes and indicate an even bonding of the palladium with the two ligand S atoms, without pronounced asymmetry in the bond lengths. For the metal coordination sphere, the calculated root-mean-square deviation = 0.00 Å, reflecting an almost perfect planarity of the S1, S2, S1ⁱ, S2ⁱ coordination [symmetry code: (i) x + $[{\script{3\over 2}}]$ , −y + $[{\script{5\over 2}}]$ , −z + 1] around the Pd^II atom. The τ₄ index (Yang et al., 2007 ) relative to the ideal square-planar geometry (D_4h) was calculated to quantitatively assess the degree of distortion of four-coordinate environment around Pd^II. For the title complex, the calculated τ₄ value is 0.0, which suggests that the title complex has an ideal square-planar geometry.

The C8—N1 bond is significantly shorter than C7—N1 and C9—N1 bonds, an observation nsistent with a significant contribution of the R₂NCS₂¹⁻ canonical form to the overall electronic structure of the dithiocarbamate ligand. The C8—S1 and C8—S2 bond lengths are almost equal [Δ(C—S) = 0.008 Å], showing the symmetric bidentate coordination of dithiocarbamate ligands.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, two C—H⋯S hydrogen bonds are observed between the sulfur atoms (S1 and S1ⁱ) of the dithiocarbamate functional group and neighbouring methyl group hydrogen atoms (H19B), which leads to the formation of a belt motif along the b-axis direction. Additional C—H⋯Cl interactions further contribute to the supramolecular arrangement (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19B⋯S1ⁱ	0.97	2.91	3.676 (6)	137
C12—H12A⋯Cl1ⁱⁱ	0.97	2.90	3.602 (2)	130
C10—H10B⋯Cg1ⁱⁱⁱ	0.97	3.24	3.982 (3)	134
Symmetry codes: (i) ; (ii) $[x, -y+2, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
Packing of the title complex viewed along the b axis.

A Hirshfeld surface analysis was performed using CrystalExplorer 21.0 (Spackman et al., 2021 ). The Hirshfeld surface and fingerprint plot calculations were performed on the entire molecule. The Hirshfeld surface mapped with d_norm is shown in Fig. 3, where white regions indicate contacts at van der Waals separations, red spots denote shorter contacts (e.g. hydrogen bonds) and blue regions indicate longer contacts. Thus, the red regions of the surface correspond to the S1⋯H19B interaction.

Figure 3
Hirshfeld surface mapped over d_norm, showing close intermolecular contacts, with red regions highlighting the S1⋯H19B interaction.

The overall two-dimensional fingerprint plot (Fig. 4) shows that the largest contribution to the surface interactions arises from H⋯H contacts, accounting for 62.9%. This is typical for complexes with a high degree of hydrogen saturation and indicates dense molecular packing (Tojiboyeva et al., 2025 ). The S⋯H/H⋯S (14.0%) and Cl⋯H/H⋯Cl (11.1%) contacts are consistent with the crystal packing data (Fig. 5), while Pd⋯H/H⋯Pd, Pd⋯Cl/H⋯Cl, C⋯C, S⋯Cl/Cl⋯S, C⋯Cl/Cl⋯C and N⋯C/C⋯N make only a small contribution. The crystal-packing data reveal the presence of significant hydrogen-bonding interactions. Minor contributions (1%) from Pd⋯H/H⋯Pd are important because complexes with M⋯H interactions are believed to act as catalysts in the synthesis of organic compounds (Wang et al., 2025 )

Figure 4
Two-dimensional fingerprint plots and the corresponding Hirshfeld surface mapped over d_norm for the title complex, showing the overall intermolecular interactions and their relative contributions, including H⋯H (62.9%), S⋯H/H⋯S (14.0%), Cl⋯H/H⋯Cl (11.1%) and C⋯H/H⋯C (8.6%) contacts.

Figure 5
Reaction scheme.

4. Synthesis and crystallization

N-(4-chlorobenzyl)-N-dodecylamine was synthesized (Fig. 5) by a procedure reported earlier (Gokul et al. 2025 ). 4-Chlorobenzaldehyde (5.3 mmol) and dodecylamine (4.6 mmol) were dissolved in methanol and the reaction mixture was stirred at room temperature for 4 h. After completion of the imine formation, sodium borohydride (13.6 mmol) was added portionwise to the reaction mixture under stirring. The reaction was allowed to proceed at room temperature until complete reduction was achieved. The solvent was removed and the amine was partitioned between dichloromethane and water. The organic layer was separated and evaporated to afford the corresponding amine. This was dissolved in 20 mL of ethanol. 4 mmol of NaOH in an aqueous solution were added to the amine solution followed by CS₂ (4 mmol) at 278 K and stirred for 30 min. An aqueous solution of PdCl₂ (2 mmol) was added to the reaction mixture. The obtained solid was purified by washing with ethanol and water and dried in a desiccator (yield: 61%). Single crystals appropriate for X-ray crystallographic analysis were successfully obtained by slow evaporation of a chloroform–acetonitrile solution. M.p. 392–394 K. IR (ATR), v (cm⁻¹): 1496 [C—N (thioureide)], 964 (C—S). ¹H NMR (400MHz, CDCl₃): δ 7.33 (d, J = 8.0 MHz, 4H), 7.24 (d, J = 8.4 MHz, 4H), 4.87 (s, 4H, 4-ClC₆H₄-CH₂), 3.56 [t, J = 8.0 MHz, 4H, CH₃-(CH₂)₉-CH₂-CH₂-N], 1.62 [b, 4H, (N-CH₂-CH₂-(CH₂)₉-CH₃], 1.25 [b, 36H, CH₃-(CH₂)₉-CH₂-CH₂-N], 0.88 {t, J = 7.2 MHz, 6H [CH₃-(CH₂)₉-CH₂-CH₂-N]}. ¹³C{¹H} NMR (100.6 MHz, CDCl₃): δ 129.1, 129.5, 132.9, 134.2 (aromatic carbons), 22.7, 26.7, 26.8, 29.1, 29.3, 29.4, 29.5, 29.6, 31.9 [CH₃-(CH₂)₁₀-CH₂-N], 14.1 [CH₃-(CH₂)₁₀-CH₂-N], 51.5 (4-ClC₆H₄-CH₂-N), 49.1 [CH₃-(CH₂)CH₂-N]. Analysis calculated for C₄₀H₆₂Cl₂N₂PdS₄: C; 54.81, H; 7.13, N; 3.20. Found: C; 54.61, H; 7.09, N; 3.18.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding with U_iso(H) = 1.2–1.5U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[Pd(C₂₀H₃₁ClNS₂)₂]
M_r	876.46
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	300
a, b, c (Å)	24.348 (2), 10.0966 (10), 18.3551 (17)
β (°)	91.168 (3)
V (Å³)	4511.3 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.74
Crystal size (mm)	0.14 × 0.12 × 0.05

Data collection
Diffractometer	Bruker D8 QUEST
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.904, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	52590, 5647, 2891
R_int	0.089

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.110, 1.14
No. of reflections	5647
No. of parameters	224
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.42
Computer programs: APEX2 and SAINT (Bruker, 2007 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ) and ShelXle (Hübschle et al., 2011 ).

Supporting information

CCDC reference: 2532016

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698902600188X/ex2098sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902600188X/ex2098Isup2.hkl

checkCIF report

Computing details top

Bis[N-(4-chlorobenzyl)-N-dodecyldithiocarbamato-κ²S,S']palladium(II) top

Crystal data top

[Pd(C₂₀H₃₁ClNS₂)₂]	F(000) = 1840
M_r = 876.46	D_x = 1.291 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.348 (2) Å	Cell parameters from 9549 reflections
b = 10.0966 (10) Å	θ = 2.2–24.0°
c = 18.3551 (17) Å	µ = 0.74 mm⁻¹
β = 91.168 (3)°	T = 300 K
V = 4511.3 (7) Å³	Block, gold
Z = 4	0.14 × 0.12 × 0.05 mm

Data collection top

Bruker D8 QUEST diffractometer	5647 independent reflections
Radiation source: microfocus sealed tube, INCOATEC IµS 3.0	2891 reflections with I > 2σ(I)
Multilayer mirror monochromator	R_int = 0.089
Detector resolution: 7.391 pixels mm^-1	θ_max = 28.4°, θ_min = 2.2°
ω and φ scans	h = −32→32
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −13→13
T_min = 0.904, T_max = 0.965	l = −24→24
52590 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.061	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0142P)² + 9.2012P]
S = 1.14	(Δ/σ)_max < 0.001
5647 reflections	Δρ_max = 0.44 e Å⁻³
224 parameters	Δρ_min = −0.42 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pd1	0.750000	1.250000	0.500000	0.06117 (16)
Cl1	0.64664 (9)	1.42872 (16)	0.00819 (8)	0.1468 (7)
S1	0.68053 (5)	1.11956 (12)	0.45024 (5)	0.0715 (3)
S2	0.77378 (5)	1.22145 (11)	0.37885 (5)	0.0687 (3)
N1	0.69935 (13)	1.0645 (3)	0.30989 (16)	0.0595 (9)
C1	0.70804 (16)	1.1576 (4)	0.1853 (2)	0.0574 (10)
C2	0.68411 (18)	1.2774 (4)	0.2019 (2)	0.0688 (12)
H2	0.680701	1.302004	0.250375	0.083*
C3	0.66525 (19)	1.3609 (4)	0.1480 (2)	0.0761 (13)
H3	0.649283	1.441608	0.159793	0.091*
C4	0.6702 (2)	1.3242 (5)	0.0765 (2)	0.0832 (14)
C5	0.6933 (2)	1.2056 (5)	0.0588 (2)	0.0880 (15)
H5	0.696394	1.181219	0.010160	0.106*
C6	0.71187 (19)	1.1229 (4)	0.1130 (2)	0.0736 (13)
H6	0.727339	1.041857	0.100787	0.088*
C7	0.73172 (16)	1.0684 (4)	0.2435 (2)	0.0641 (11)
H7A	0.734460	0.979389	0.224102	0.077*
H7B	0.768595	1.098199	0.256033	0.077*
C8	0.71556 (16)	1.1252 (4)	0.3701 (2)	0.0578 (10)
C9	0.64853 (17)	0.9868 (4)	0.3065 (2)	0.0677 (12)
H9A	0.629255	1.005795	0.260961	0.081*
H9B	0.625118	1.014413	0.345899	0.081*
C10	0.65798 (17)	0.8399 (4)	0.3121 (2)	0.0695 (12)
H10A	0.675688	0.809339	0.268330	0.083*
H10B	0.682612	0.822043	0.353150	0.083*
C11	0.60555 (18)	0.7636 (5)	0.3217 (2)	0.0798 (13)
H11A	0.590424	0.786847	0.368486	0.096*
H11B	0.579308	0.791221	0.284252	0.096*
C12	0.61147 (18)	0.6160 (5)	0.3182 (2)	0.0779 (13)
H12A	0.641449	0.589028	0.350463	0.093*
H12B	0.620959	0.590964	0.268979	0.093*
C13	0.55992 (19)	0.5430 (5)	0.3392 (3)	0.0909 (15)
H13A	0.549204	0.573552	0.386946	0.109*
H13B	0.530705	0.566729	0.304935	0.109*
C14	0.5644 (2)	0.3959 (5)	0.3413 (3)	0.0973 (16)
H14A	0.593812	0.371267	0.375025	0.117*
H14B	0.574098	0.364244	0.293312	0.117*
C15	0.5115 (2)	0.3280 (5)	0.3642 (3)	0.1018 (17)
H15A	0.502421	0.357928	0.412689	0.122*
H15B	0.481910	0.354883	0.331267	0.122*
C16	0.5149 (2)	0.1805 (6)	0.3644 (3)	0.1073 (18)
H16A	0.525073	0.151296	0.316190	0.129*
H16B	0.544204	0.154156	0.398044	0.129*
C17	0.4637 (2)	0.1101 (6)	0.3850 (3)	0.1143 (19)
H17A	0.434238	0.135662	0.351527	0.137*
H17B	0.453546	0.137875	0.433484	0.137*
C18	0.4695 (2)	−0.0404 (6)	0.3840 (4)	0.123 (2)
H18A	0.478499	−0.067410	0.334920	0.147*
H18B	0.500277	−0.064610	0.415632	0.147*
C19	0.4224 (2)	−0.1139 (6)	0.4060 (4)	0.128 (2)
H19A	0.392454	−0.096021	0.371693	0.153*
H19B	0.411336	−0.081435	0.453262	0.153*
C20	0.4301 (3)	−0.2613 (6)	0.4111 (4)	0.141 (2)
H20A	0.397226	−0.301396	0.428682	0.212*
H20B	0.460211	−0.280590	0.444016	0.212*
H20C	0.437974	−0.296058	0.363713	0.212*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0802 (3)	0.0613 (3)	0.0421 (2)	−0.0022 (3)	0.0038 (2)	0.0030 (2)
Cl1	0.253 (2)	0.1099 (12)	0.0762 (10)	0.0300 (13)	−0.0338 (11)	0.0153 (8)
S1	0.0860 (8)	0.0804 (8)	0.0484 (6)	−0.0111 (6)	0.0111 (6)	0.0011 (6)
S2	0.0813 (8)	0.0776 (8)	0.0474 (6)	−0.0123 (6)	0.0082 (5)	0.0001 (5)
N1	0.070 (2)	0.062 (2)	0.046 (2)	0.0002 (18)	0.0076 (17)	−0.0028 (16)
C1	0.069 (3)	0.058 (3)	0.045 (2)	−0.006 (2)	0.003 (2)	−0.003 (2)
C2	0.091 (3)	0.070 (3)	0.045 (2)	0.002 (2)	−0.001 (2)	−0.016 (2)
C3	0.102 (4)	0.064 (3)	0.062 (3)	0.008 (3)	−0.004 (3)	−0.008 (2)
C4	0.124 (4)	0.067 (3)	0.058 (3)	−0.003 (3)	−0.012 (3)	0.007 (2)
C5	0.139 (5)	0.079 (4)	0.046 (3)	−0.004 (3)	0.002 (3)	−0.005 (2)
C6	0.105 (4)	0.066 (3)	0.050 (3)	−0.004 (3)	0.009 (2)	−0.012 (2)
C7	0.071 (3)	0.067 (3)	0.055 (3)	0.001 (2)	0.009 (2)	−0.007 (2)
C8	0.074 (3)	0.053 (2)	0.047 (2)	0.007 (2)	0.005 (2)	0.0039 (19)
C9	0.068 (3)	0.076 (3)	0.059 (3)	−0.001 (2)	−0.001 (2)	−0.004 (2)
C10	0.072 (3)	0.069 (3)	0.068 (3)	−0.004 (2)	0.009 (2)	−0.007 (2)
C11	0.077 (3)	0.084 (4)	0.079 (3)	−0.011 (3)	0.008 (2)	−0.001 (3)
C12	0.082 (3)	0.079 (4)	0.073 (3)	−0.015 (3)	0.008 (2)	−0.003 (3)
C13	0.083 (4)	0.093 (4)	0.096 (4)	−0.013 (3)	−0.008 (3)	0.008 (3)
C14	0.087 (4)	0.097 (4)	0.107 (4)	−0.019 (3)	0.000 (3)	0.004 (3)
C15	0.085 (4)	0.093 (4)	0.127 (5)	−0.014 (3)	−0.001 (3)	0.014 (4)
C16	0.082 (4)	0.104 (5)	0.136 (5)	−0.010 (3)	−0.003 (3)	0.009 (4)
C17	0.090 (4)	0.102 (5)	0.151 (5)	−0.018 (4)	0.006 (4)	0.022 (4)
C18	0.100 (5)	0.116 (5)	0.153 (6)	−0.004 (4)	0.022 (4)	0.009 (4)
C19	0.113 (5)	0.120 (5)	0.151 (6)	−0.004 (4)	0.032 (4)	0.023 (4)
C20	0.127 (5)	0.109 (5)	0.189 (7)	0.003 (4)	0.025 (5)	0.020 (5)

Geometric parameters (Å, º) top

Pd1—S1ⁱ	2.3165 (12)	C11—H11A	0.9700
Pd1—S1	2.3166 (12)	C11—H11B	0.9700
Pd1—S2ⁱ	2.3271 (10)	C12—C13	1.513 (6)
Pd1—S2	2.3271 (10)	C12—H12A	0.9700
Cl1—C4	1.728 (5)	C12—H12B	0.9700
S1—C8	1.716 (4)	C13—C14	1.489 (6)
S2—C8	1.724 (4)	C13—H13A	0.9700
N1—C8	1.318 (4)	C13—H13B	0.9700
N1—C7	1.465 (4)	C14—C15	1.526 (6)
N1—C9	1.465 (5)	C14—H14A	0.9700
C1—C6	1.379 (5)	C14—H14B	0.9700
C1—C2	1.379 (5)	C15—C16	1.491 (6)
C1—C7	1.503 (5)	C15—H15A	0.9700
C2—C3	1.372 (5)	C15—H15B	0.9700
C2—H2	0.9300	C16—C17	1.491 (6)
C3—C4	1.371 (6)	C16—H16A	0.9700
C3—H3	0.9300	C16—H16B	0.9700
C4—C5	1.364 (6)	C17—C18	1.526 (7)
C5—C6	1.369 (6)	C17—H17A	0.9700
C5—H5	0.9300	C17—H17B	0.9700
C6—H6	0.9300	C18—C19	1.432 (7)
C7—H7A	0.9700	C18—H18A	0.9700
C7—H7B	0.9700	C18—H18B	0.9700
C9—C10	1.505 (5)	C19—C20	1.503 (7)
C9—H9A	0.9700	C19—H19A	0.9700
C9—H9B	0.9700	C19—H19B	0.9700
C10—C11	1.504 (5)	C20—H20A	0.9600
C10—H10A	0.9700	C20—H20B	0.9600
C10—H10B	0.9700	C20—H20C	0.9600
C11—C12	1.498 (6)

S1ⁱ—Pd1—S1	180.0	H11A—C11—H11B	107.5
S1ⁱ—Pd1—S2ⁱ	75.32 (4)	C11—C12—C13	113.1 (4)
S1—Pd1—S2ⁱ	104.68 (4)	C11—C12—H12A	109.0
S1ⁱ—Pd1—S2	104.67 (4)	C13—C12—H12A	109.0
S1—Pd1—S2	75.33 (4)	C11—C12—H12B	109.0
S2ⁱ—Pd1—S2	180.0	C13—C12—H12B	109.0
C8—S1—Pd1	86.98 (14)	H12A—C12—H12B	107.8
C8—S2—Pd1	86.47 (13)	C14—C13—C12	115.6 (4)
C8—N1—C7	121.9 (3)	C14—C13—H13A	108.4
C8—N1—C9	121.5 (3)	C12—C13—H13A	108.4
C7—N1—C9	116.6 (3)	C14—C13—H13B	108.4
C6—C1—C2	118.2 (4)	C12—C13—H13B	108.4
C6—C1—C7	120.0 (4)	H13A—C13—H13B	107.4
C2—C1—C7	121.8 (3)	C13—C14—C15	113.2 (5)
C3—C2—C1	121.2 (4)	C13—C14—H14A	108.9
C3—C2—H2	119.4	C15—C14—H14A	108.9
C1—C2—H2	119.4	C13—C14—H14B	108.9
C4—C3—C2	119.3 (4)	C15—C14—H14B	108.9
C4—C3—H3	120.4	H14A—C14—H14B	107.8
C2—C3—H3	120.4	C16—C15—C14	113.7 (5)
C5—C4—C3	120.7 (4)	C16—C15—H15A	108.8
C5—C4—Cl1	119.7 (4)	C14—C15—H15A	108.8
C3—C4—Cl1	119.6 (4)	C16—C15—H15B	108.8
C4—C5—C6	119.6 (4)	C14—C15—H15B	108.8
C4—C5—H5	120.2	H15A—C15—H15B	107.7
C6—C5—H5	120.2	C17—C16—C15	115.4 (5)
C5—C6—C1	121.2 (4)	C17—C16—H16A	108.4
C5—C6—H6	119.4	C15—C16—H16A	108.4
C1—C6—H6	119.4	C17—C16—H16B	108.4
N1—C7—C1	113.7 (3)	C15—C16—H16B	108.4
N1—C7—H7A	108.8	H16A—C16—H16B	107.5
C1—C7—H7A	108.8	C16—C17—C18	113.2 (5)
N1—C7—H7B	108.8	C16—C17—H17A	108.9
C1—C7—H7B	108.8	C18—C17—H17A	108.9
H7A—C7—H7B	107.7	C16—C17—H17B	108.9
N1—C8—S1	123.9 (3)	C18—C17—H17B	108.9
N1—C8—S2	124.9 (3)	H17A—C17—H17B	107.8
S1—C8—S2	111.2 (2)	C19—C18—C17	115.9 (5)
N1—C9—C10	113.4 (3)	C19—C18—H18A	108.3
N1—C9—H9A	108.9	C17—C18—H18A	108.3
C10—C9—H9A	108.9	C19—C18—H18B	108.3
N1—C9—H9B	108.9	C17—C18—H18B	108.3
C10—C9—H9B	108.9	H18A—C18—H18B	107.4
H9A—C9—H9B	107.7	C18—C19—C20	115.4 (5)
C11—C10—C9	112.6 (4)	C18—C19—H19A	108.4
C11—C10—H10A	109.1	C20—C19—H19A	108.4
C9—C10—H10A	109.1	C18—C19—H19B	108.4
C11—C10—H10B	109.1	C20—C19—H19B	108.4
C9—C10—H10B	109.1	H19A—C19—H19B	107.5
H10A—C10—H10B	107.8	C19—C20—H20A	109.5
C12—C11—C10	114.9 (4)	C19—C20—H20B	109.5
C12—C11—H11A	108.5	H20A—C20—H20B	109.5
C10—C11—H11A	108.5	C19—C20—H20C	109.5
C12—C11—H11B	108.5	H20A—C20—H20C	109.5
C10—C11—H11B	108.5	H20B—C20—H20C	109.5

C6—C1—C2—C3	−0.9 (6)	C9—N1—C8—S2	−178.5 (3)
C7—C1—C2—C3	176.6 (4)	Pd1—S1—C8—N1	178.9 (3)
C1—C2—C3—C4	0.2 (7)	Pd1—S1—C8—S2	−1.72 (18)
C2—C3—C4—C5	0.4 (8)	Pd1—S2—C8—N1	−179.0 (3)
C2—C3—C4—Cl1	−179.9 (4)	Pd1—S2—C8—S1	1.72 (18)
C3—C4—C5—C6	−0.2 (8)	C8—N1—C9—C10	−101.2 (4)
Cl1—C4—C5—C6	−179.9 (4)	C7—N1—C9—C10	77.4 (4)
C4—C5—C6—C1	−0.5 (7)	N1—C9—C10—C11	170.0 (3)
C2—C1—C6—C5	1.0 (7)	C9—C10—C11—C12	172.7 (4)
C7—C1—C6—C5	−176.5 (4)	C10—C11—C12—C13	171.4 (4)
C8—N1—C7—C1	−105.6 (4)	C11—C12—C13—C14	−176.3 (4)
C9—N1—C7—C1	75.8 (4)	C12—C13—C14—C15	178.9 (4)
C6—C1—C7—N1	−144.0 (4)	C13—C14—C15—C16	178.4 (5)
C2—C1—C7—N1	38.6 (5)	C14—C15—C16—C17	−178.7 (5)
C7—N1—C8—S1	−177.8 (3)	C15—C16—C17—C18	179.7 (5)
C9—N1—C8—S1	0.7 (5)	C16—C17—C18—C19	177.6 (6)
C7—N1—C8—S2	2.9 (5)	C17—C18—C19—C20	−174.9 (6)

Symmetry code: (i) −x+3/2, −y+5/2, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19B···S1ⁱⁱ	0.97	2.91	3.676 (6)	137
C12—H12A···Cl1ⁱⁱⁱ	0.97	2.90	3.602 (2)	130
C10—H10B···Cg1^iv	0.97	3.24	3.982 (3)	134

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, −y+2, z+1/2; (iv) −x+3/2, y+1/2, −z+1/2.

Acknowledgements

We acknowledge the technical assistance of the Single Crystal XRD facility supported jointly by DST and VIT under the DST-FIST scheme at VIT, Vellore.

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