trans-Bis(5-amino-1,3,4-thia­diazol-2-thio­lato-κS2)bis­(triphenyl­phosphane-κP)palladium(II) dimethyl sulfoxide disolvate hemihydrate

Chontal-Vidal, F.; Arroyo-Gómez, M.; Hernández-Ortega, S.; Reyes-Martínez, R.; Morales-Morales, D.

doi:10.1107/S1600536812011555

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m483-m484

doi:10.1107/S1600536812011555

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trans-Bis(5-amino-1,3,4-thiadiazol-2-thiolato-κS²)bis(triphenylphosphane-κP)palladium(II) dimethyl sulfoxide disolvate hemihydrate

Felipe Chontal-Vidal,^a Maricela Arroyo-Gómez,^b Simón Hernández-Ortega,^a Reyna Reyes-Martínez ^a and David Morales-Morales ^a ^*

^aInstituto de Química, Universidad Nacional Autónoma de México, Circuito exterior, Ciudad Universitaria, México, DF 04510, Mexico, and ^bCiencias Básicas e Ingeniería, Recursos de la Tierra, Universidad Autónoma, Metropolitana. Av. Hidalgo Poniente, La Estación Lerma, Lerma de Villada, Estado de México, CP 52006, Mexico
^*Correspondence e-mail: rrm@uaem.mx

(Received 14 February 2012; accepted 16 March 2012; online 24 March 2012)

The title complex, [Pd(C₂H₂N₃S₂)₂(C₁₈H₁₅P)₂]·2C₂H₆OS·0.5H₂O, was obtained from the reaction of trans-[(Ph₃P)₂PdCl₂] with 5-amino-1,3,4-thiadiazole-2-thione (SSNH₂) in a 2:1 molar ratio. The Pd^II atom, located in a crystallographic center of symmetry, has a square-planar geometry with two triphenylphosphine P-coordinated molecules and two SSNH₂ ligands with the S atoms in a trans conformation. The latter ligand exhibits N—H⋯N hydrogen-bonding contacts formed by the amino group with the thiadiazole ring, generating a chain along the c axis. The asymmetric unit contains one half of the complex molecule along with disordered dimethyl sulfoxide and water molecules.

Related literature

For background to the design and synthesis of ligands that contain efficient metal coordination sites and hydrogen-bonding functionalities, see: Beatty (2001 ). The SSNH₂ (5-amino-1,3,4-thiadiazole-2-thiol) ligand exists in the thione and thiol forms and can converted into the thiolate form depending on the affinity of the metal, see: Tzeng et al. (1999 ). For SSNH₂ acting as a ligand and as auxiliary in the construction of hydrogen bonds in coordination compounds with Pd^II, see: Tzeng, Lee et al. (2004 ), with Pt^II, see: Tannai et al. (2006 ), with Cd^II, see: Gao et al. (2009 ) and with Au^I, see: Tzeng et al. (1999); Tzeng, Huang et al. (2004 ). For the thiolate form, see: Downie et al. (1972 ).

Experimental

Crystal data

[Pd(C₂H₂N₃S₂)₂(C₁₈H₁₅P)₂]·2C₂H₆OS·0.5H₂O
M_r = 1060.58
Orthorhombic, P b c n
a = 14.6192 (18) Å
b = 13.2572 (16) Å
c = 25.707 (3) Å
V = 4982.3 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 298 K
0.24 × 0.16 × 0.13 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
38822 measured reflections
4590 independent reflections
2603 reflections with I > 2σ(I)
R_int = 0.107

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.137
S = 0.95
4590 reflections
322 parameters
99 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Selected bond lengths (Å)

Pd—P1	2.3364 (15)
Pd—S2	2.3407 (14)
S2—C2	1.736 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6A⋯N4ⁱ	0.90 (1)	2.12 (2)	2.986 (7)	160 (5)
Symmetry code: (i) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812011555/br2190sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011555/br2190Isup2.hkl

checkCIF report

Comment top

Hydrogen bonds are commonly used to generate supramolecular assemblies of coordination complexes, in this field an important area of research is the design and synthesis of ligands that contain efficient metal coordination sites and hydrogen bonding functionalities (Beatty, 2001). In this context the ligand 5-amino-1,3,4-thiadiazole-2-thiol (SSNH₂) has been used as building block for the construction of hydrogen bonded frameworks. The ligand SSNH₂ can exists in the thione and thiol forms, however it can converted into the thiolate form depending on the affinity of the metal (Tzeng, et al., 1999). Several reports of SSNH₂ acting as a ligand and as auxiliary in the construction of hydrogen bonds in coordination compounds with Pd(II) (Tzeng, Lee et al., 2004), Pt(II) (Tannai, et al., 2006), Cd(II) (Gao, et al., 2009) and Au(I) (Tzeng, et al., 1999; Tzeng, Huang et al., 2004) have been informed in the literature. Thus, in this opportunity we would like to report the crystal structure of the Pd(II) complex, trans-[(Ph₃P)₂Pd(SSNH₂)₂] DMSO, H₂O.

The molecular structure of the title compound is shown in Figure 1. The selected bond distances and angles are listed in Table 1. Only half molecule of the complex is found in the asymmetric unit and an inversion operator is needed for the generation of a whole molecule. The Pd(II) atom in the complex exhibits a square-planar arrangement, however the geometry is forced by the steric hindrance and electronic repulsions due to the interactions between the phenyl and the heterocycle rings. The SSNH₂ ligands are bonded to the metal center by the sulfur atoms in a trans arrangement with the thiadiazole groups found out of the plane of the Pd(II) coordination environment. The distance C2-S2 confirms that the ligand exists in the thiolate form (Downie, et al., 1972). The free amine group of the ligand SSNH₂ forms a hydrogen bond N6—H6A···N4 with the nitrogen atom of the thiadiazole ring related by symmetry, generating a centrosymmetric eight-member cycle, that is extended along the c-axes to form a chain framework. These chains are kept together by weak C—H···π [C9–H9···Cg(C13–C18)] intermolecular interactions. The compound crystallized with one molecule of DMSO that exhibits disorder on its structure, and one molecule of water. Weak interactions of N6—H6B···O1 (DMSO) solvent and O2—H atom of the DMSO solvent are observed. Although the solvent molecules do not participate in the strong interactions, they are important in the stabilization of the compound in the crystal lattice.

Related literature top

For background to the design and synthesis of ligands that contain efficient metal coordination sites and hydrogen-bonding functionalities, see: Beatty (2001). The SSNH₂ (5-amino-1,3,4-thiadiazole-2-thiol) ligand exists in the thione and thiol forms and can converted into the thiolate form depending on the affinity of the metal, see: Tzeng et al. (1999). For SSNH₂ acting as a ligand and as auxiliary in the construction of hydrogen bonds in coordination compounds with Pd^II, see: Tzeng, Lee et al. (2004), with Pt^II, see: Tannai et al. (2006), with Cd^II, see: Gao et al. (2009) and with Au^I, see: Tzeng et al. (1999); Tzeng, Huang et al. (2004). For the thiolate form, see: Downie et al. (1972).

Experimental top

To a CH₂Cl₂ solution (20 ml) of trans-[(Ph₃P)₂PdCl₂] (50 mg, 0.07 mmol) a solution of 5-amino-1,3,4-thiadiazole-2-thiol (20 mg, 15 mmol) and triethylamine (2 ml) in CH₂Cl₂ (20 ml) was added dropwise, and immediate change from yellow to orange was noted and the resulting reaction mixture was allowed to proceed overnight at room temperature under stirring. After this time, a reddish-orangey precipitated was noted, and the solution was filtered under vacuum to afford compound trans-[(Ph₃P)₂Pd(SSNH₂)₂] (59 mg, 95% yield). Crystals suitable for single-crystal X-ray diffraction analysis were obtained from DMSO/ⁱPrOH.

Structure description top

For background to the design and synthesis of ligands that contain efficient metal coordination sites and hydrogen-bonding functionalities, see: Beatty (2001). The SSNH₂ (5-amino-1,3,4-thiadiazole-2-thiol) ligand exists in the thione and thiol forms and can converted into the thiolate form depending on the affinity of the metal, see: Tzeng et al. (1999). For SSNH₂ acting as a ligand and as auxiliary in the construction of hydrogen bonds in coordination compounds with Pd^II, see: Tzeng, Lee et al. (2004), with Pt^II, see: Tannai et al. (2006), with Cd^II, see: Gao et al. (2009) and with Au^I, see: Tzeng et al. (1999); Tzeng, Huang et al. (2004). For the thiolate form, see: Downie et al. (1972).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids at the 30% probability, the hydrogen atoms, DMSO and H₂O solvent are omitted for clarity.
	Fig. 2. The title compound is linked by N—H···N intermolecular interactions along the c axes, the hydrogen atoms for the interactions are drawn.

trans-Bis(5-amino-1,3,4-thiadiazol-2-thiolato- κS²)bis(triphenylphosphane-κP)palladium(II) dimethyl sulfoxide disolvate hemihydrate top

Crystal data top

[Pd(C₂H₂N₃S₂)₂(C₁₈H₁₅P)₂]·2C₂H₆OS·0.5H₂O	F(000) = 2176
M_r = 1060.58	D_x = 1.414 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 6520 reflections
a = 14.6192 (18) Å	θ = 2.2–25.0°
b = 13.2572 (16) Å	µ = 0.73 mm⁻¹
c = 25.707 (3) Å	T = 298 K
V = 4982.3 (10) Å³	Prism, orange
Z = 4	0.24 × 0.16 × 0.13 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2603 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.107
Graphite monochromator	θ_max = 25.5°, θ_min = 2.1°
Detector resolution: 0.83 pixels mm^-1	h = −17→17
ω scans	k = −16→15
38822 measured reflections	l = −31→30
4590 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ²(F_o²) + (0.0611P)²] where P = (F_o² + 2F_c²)/3
4590 reflections	(Δ/σ)_max = 0.001
322 parameters	Δρ_max = 0.63 e Å⁻³
99 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Pd(C₂H₂N₃S₂)₂(C₁₈H₁₅P)₂]·2C₂H₆OS·0.5H₂O	V = 4982.3 (10) Å³
M_r = 1060.58	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 14.6192 (18) Å	µ = 0.73 mm⁻¹
b = 13.2572 (16) Å	T = 298 K
c = 25.707 (3) Å	0.24 × 0.16 × 0.13 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2603 reflections with I > 2σ(I)
38822 measured reflections	R_int = 0.107
4590 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	99 restraints
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.63 e Å⁻³
4590 reflections	Δρ_min = −0.37 e Å⁻³
322 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pd	0.5000	0.5000	0.5000	0.04092 (19)
S1	0.30706 (10)	0.43464 (14)	0.65323 (6)	0.0614 (5)
S2	0.35991 (9)	0.47537 (12)	0.54222 (5)	0.0494 (4)
C2	0.3886 (4)	0.4746 (4)	0.6078 (2)	0.0428 (14)
N3	0.4650 (3)	0.5019 (4)	0.62829 (17)	0.0527 (13)
N4	0.4655 (3)	0.4920 (4)	0.68230 (17)	0.0526 (13)
C5	0.3896 (4)	0.4590 (5)	0.7008 (2)	0.0561 (16)
N6	0.3726 (4)	0.4426 (5)	0.75160 (19)	0.0872 (19)
H6A	0.4270 (11)	0.444 (4)	0.7682 (6)	0.105*
H6B	0.331 (3)	0.489 (3)	0.7616 (8)	0.105*
P1	0.56548 (10)	0.35283 (12)	0.53336 (5)	0.0469 (4)
C7	0.6788 (4)	0.3827 (5)	0.5585 (2)	0.0524 (16)
C8	0.7562 (5)	0.3304 (6)	0.5456 (3)	0.084 (2)
H8	0.7521	0.2735	0.5246	0.101*
C9	0.8418 (5)	0.3621 (8)	0.5640 (3)	0.107 (3)
H9	0.8943	0.3276	0.5541	0.128*
C10	0.8482 (6)	0.4410 (8)	0.5954 (3)	0.105 (3)
H10	0.9050	0.4603	0.6083	0.126*
C11	0.7727 (5)	0.4936 (7)	0.6086 (3)	0.098 (3)
H11	0.7784	0.5496	0.6301	0.117*
C12	0.6866 (5)	0.4658 (6)	0.5906 (3)	0.073 (2)
H12	0.6351	0.5026	0.6000	0.088*
C13	0.5809 (4)	0.2545 (5)	0.4849 (2)	0.0536 (16)
C14	0.5676 (4)	0.2755 (5)	0.4331 (2)	0.0606 (17)
H14	0.5515	0.3401	0.4225	0.073*
C15	0.5787 (5)	0.1981 (6)	0.3965 (3)	0.076 (2)
H15	0.5712	0.2122	0.3613	0.092*
C16	0.5999 (5)	0.1033 (6)	0.4115 (4)	0.081 (2)
H16	0.6077	0.0531	0.3867	0.098*
C17	0.6099 (5)	0.0812 (6)	0.4624 (4)	0.092 (3)
H17	0.6226	0.0153	0.4726	0.110*
C18	0.6013 (5)	0.1553 (5)	0.4991 (3)	0.077 (2)
H18	0.6092	0.1395	0.5340	0.092*
C19	0.5104 (5)	0.2807 (4)	0.5842 (2)	0.0555 (16)
C20	0.4262 (5)	0.2343 (5)	0.5738 (3)	0.068 (2)
H20	0.3986	0.2451	0.5417	0.082*
C21	0.3831 (6)	0.1739 (6)	0.6093 (4)	0.096 (3)
H21	0.3275	0.1436	0.6012	0.115*
C22	0.4222 (9)	0.1586 (7)	0.6560 (4)	0.118 (4)
H22	0.3929	0.1177	0.6802	0.141*
C23	0.5037 (8)	0.2019 (7)	0.6685 (3)	0.114 (3)
H23	0.5299	0.1899	0.7009	0.137*
C24	0.5477 (5)	0.2642 (6)	0.6326 (3)	0.084 (2)
H24	0.6028	0.2948	0.6415	0.101*
S3	0.6482 (5)	0.2367 (6)	0.2460 (2)	0.148 (2)	0.555 (7)
O1	0.6973 (12)	0.2972 (13)	0.2789 (6)	0.205 (6)	0.555 (7)
C25	0.6929 (15)	0.1269 (10)	0.2344 (8)	0.153 (5)	0.555 (7)
H25A	0.7149	0.0982	0.2663	0.230*	0.555 (7)
H25B	0.7428	0.1343	0.2104	0.230*	0.555 (7)
H25C	0.6474	0.0834	0.2195	0.230*	0.555 (7)
C26	0.6108 (16)	0.2920 (16)	0.1935 (6)	0.168 (6)	0.555 (7)
H26A	0.5859	0.3568	0.2023	0.252*	0.555 (7)
H26B	0.5641	0.2513	0.1777	0.252*	0.555 (7)
H26C	0.6605	0.3006	0.1694	0.252*	0.555 (7)
S3A	0.7135 (7)	0.2550 (8)	0.2128 (3)	0.174 (3)	0.445 (7)
O1A	0.7568 (16)	0.3180 (16)	0.2464 (8)	0.219 (6)	0.445 (7)
C25A	0.6772 (18)	0.1491 (12)	0.2385 (10)	0.140 (5)	0.445 (7)
H25D	0.7254	0.1193	0.2588	0.210*	0.445 (7)
H25E	0.6595	0.1034	0.2113	0.210*	0.445 (7)
H25F	0.6256	0.1625	0.2605	0.210*	0.445 (7)
C26A	0.6357 (16)	0.307 (2)	0.1760 (10)	0.176 (7)	0.445 (7)
H26D	0.6588	0.3690	0.1620	0.264*	0.445 (7)
H26E	0.5819	0.3203	0.1963	0.264*	0.445 (7)
H26F	0.6205	0.2620	0.1480	0.264*	0.445 (7)
O2	0.5000	0.034 (2)	0.2500	0.263 (14)*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd	0.0372 (3)	0.0535 (4)	0.0320 (3)	0.0035 (3)	−0.0035 (3)	0.0020 (3)
S1	0.0524 (9)	0.0909 (13)	0.0409 (9)	−0.0164 (9)	0.0029 (8)	0.0012 (9)
S2	0.0407 (8)	0.0700 (11)	0.0374 (8)	−0.0005 (7)	−0.0034 (6)	0.0048 (7)
C2	0.044 (3)	0.047 (4)	0.037 (3)	0.004 (3)	0.002 (3)	0.005 (3)
N3	0.044 (3)	0.072 (3)	0.043 (3)	−0.004 (3)	−0.005 (2)	0.004 (3)
N4	0.051 (3)	0.070 (4)	0.037 (3)	−0.010 (3)	−0.003 (2)	0.005 (3)
C5	0.055 (4)	0.073 (5)	0.041 (4)	−0.006 (3)	−0.005 (3)	0.000 (3)
N6	0.070 (4)	0.154 (6)	0.037 (3)	−0.015 (4)	0.001 (3)	0.005 (4)
P1	0.0462 (9)	0.0563 (10)	0.0381 (8)	0.0086 (8)	−0.0024 (7)	0.0037 (8)
C7	0.046 (4)	0.071 (4)	0.040 (3)	0.012 (3)	−0.002 (3)	0.011 (3)
C8	0.063 (5)	0.128 (7)	0.062 (4)	0.024 (5)	−0.009 (4)	−0.018 (5)
C9	0.056 (5)	0.178 (10)	0.087 (6)	0.037 (6)	−0.016 (4)	−0.026 (6)
C10	0.053 (5)	0.178 (10)	0.084 (6)	0.010 (6)	−0.019 (4)	−0.009 (6)
C11	0.078 (6)	0.128 (7)	0.087 (6)	−0.015 (6)	−0.017 (5)	−0.023 (5)
C12	0.054 (4)	0.094 (6)	0.072 (5)	0.006 (4)	−0.013 (4)	−0.010 (4)
C13	0.048 (4)	0.071 (5)	0.041 (4)	0.005 (3)	0.007 (3)	−0.005 (3)
C14	0.059 (4)	0.058 (4)	0.064 (5)	−0.005 (3)	0.005 (4)	−0.003 (4)
C15	0.080 (5)	0.093 (6)	0.056 (4)	−0.010 (5)	0.014 (4)	−0.015 (5)
C16	0.076 (5)	0.069 (6)	0.100 (7)	−0.002 (4)	0.031 (5)	−0.030 (5)
C17	0.092 (6)	0.070 (6)	0.113 (7)	0.031 (5)	0.019 (5)	−0.006 (6)
C18	0.089 (5)	0.068 (5)	0.073 (5)	0.034 (4)	0.002 (4)	0.005 (5)
C19	0.073 (5)	0.048 (4)	0.046 (4)	0.016 (4)	0.007 (4)	0.001 (3)
C20	0.094 (6)	0.052 (4)	0.058 (4)	−0.002 (4)	0.022 (4)	0.002 (4)
C21	0.127 (8)	0.068 (6)	0.093 (6)	−0.024 (5)	0.035 (6)	−0.006 (5)
C22	0.186 (12)	0.069 (6)	0.099 (8)	−0.011 (7)	0.067 (8)	0.012 (6)
C23	0.188 (11)	0.100 (7)	0.054 (5)	0.009 (8)	0.019 (7)	0.027 (5)
C24	0.111 (6)	0.087 (6)	0.055 (5)	0.012 (5)	0.008 (4)	0.013 (4)
S3	0.146 (5)	0.196 (6)	0.104 (4)	0.051 (4)	−0.005 (4)	0.006 (4)
O1	0.245 (14)	0.220 (10)	0.149 (11)	−0.009 (10)	−0.024 (9)	−0.004 (9)
C25	0.122 (11)	0.218 (9)	0.120 (11)	0.086 (9)	−0.060 (9)	−0.007 (8)
C26	0.166 (11)	0.186 (10)	0.151 (10)	0.042 (10)	−0.020 (9)	0.042 (8)
S3A	0.169 (7)	0.230 (7)	0.123 (6)	0.024 (6)	−0.007 (5)	0.011 (5)
O1A	0.216 (14)	0.267 (12)	0.173 (13)	−0.040 (11)	−0.020 (10)	0.008 (10)
C25A	0.139 (11)	0.166 (10)	0.115 (10)	0.080 (8)	−0.025 (9)	−0.014 (8)
C26A	0.188 (14)	0.198 (13)	0.141 (13)	0.019 (11)	−0.003 (10)	0.046 (10)

Geometric parameters (Å, º) top

Pd—P1ⁱ	2.3363 (15)	C16—H16	0.9300
Pd—P1	2.3364 (15)	C17—C18	1.368 (9)
Pd—S2ⁱ	2.3407 (14)	C17—H17	0.9300
Pd—S2	2.3407 (14)	C18—H18	0.9300
S1—C5	1.748 (6)	C19—C24	1.377 (8)
S1—C2	1.751 (5)	C19—C20	1.402 (8)
S2—C2	1.736 (5)	C20—C21	1.367 (9)
C2—N3	1.288 (7)	C20—H20	0.9300
N3—N4	1.394 (6)	C21—C22	1.344 (12)
N4—C5	1.284 (7)	C21—H21	0.9300
C5—N6	1.348 (7)	C22—C23	1.362 (12)
N6—H6A	0.904 (10)	C22—H22	0.9300
N6—H6B	0.899 (10)	C23—C24	1.396 (10)
P1—C19	1.807 (6)	C23—H23	0.9300
P1—C13	1.817 (6)	C24—H24	0.9300
P1—C7	1.821 (6)	S3—O1	1.369 (12)
C7—C8	1.367 (8)	S3—C25	1.623 (8)
C7—C12	1.382 (8)	S3—C26	1.632 (7)
C8—C9	1.402 (10)	C25—H25A	0.9600
C8—H8	0.9300	C25—H25B	0.9600
C9—C10	1.324 (11)	C25—H25C	0.9600
C9—H9	0.9300	C26—H26A	0.9600
C10—C11	1.348 (10)	C26—H26B	0.9600
C10—H10	0.9300	C26—H26C	0.9600
C11—C12	1.391 (9)	S3A—O1A	1.358 (12)
C11—H11	0.9300	S3A—C26A	1.633 (8)
C12—H12	0.9300	S3A—C25A	1.640 (8)
C13—C14	1.374 (7)	C25A—H25D	0.9600
C13—C18	1.397 (8)	C25A—H25E	0.9600
C14—C15	1.401 (8)	C25A—H25F	0.9600
C14—H14	0.9300	C26A—H26D	0.9600
C15—C16	1.351 (10)	C26A—H26E	0.9600
C15—H15	0.9300	C26A—H26F	0.9600
C16—C17	1.348 (10)

P1ⁱ—Pd—P1	180.0	C16—C17—C18	120.1 (7)
P1ⁱ—Pd—S2ⁱ	94.12 (5)	C16—C17—H17	119.9
P1—Pd—S2ⁱ	85.88 (5)	C18—C17—H17	119.9
P1ⁱ—Pd—S2	85.89 (5)	C17—C18—C13	121.1 (7)
P1—Pd—S2	94.12 (5)	C17—C18—H18	119.4
S2ⁱ—Pd—S2	180.0	C13—C18—H18	119.4
C5—S1—C2	86.6 (3)	C24—C19—C20	116.7 (6)
C2—S2—Pd	103.87 (19)	C24—C19—P1	124.2 (6)
N3—C2—S2	127.2 (4)	C20—C19—P1	119.1 (5)
N3—C2—S1	113.7 (4)	C21—C20—C19	122.4 (7)
S2—C2—S1	119.0 (3)	C21—C20—H20	118.8
C2—N3—N4	112.7 (5)	C19—C20—H20	118.8
C5—N4—N3	113.3 (5)	C22—C21—C20	119.2 (9)
N4—C5—N6	125.0 (5)	C22—C21—H21	120.4
N4—C5—S1	113.6 (4)	C20—C21—H21	120.4
N6—C5—S1	121.4 (5)	C21—C22—C23	121.4 (9)
C5—N6—H6A	107.1 (13)	C21—C22—H22	119.3
C5—N6—H6B	107.0 (13)	C23—C22—H22	119.3
H6A—N6—H6B	116.7 (19)	C22—C23—C24	119.7 (9)
C19—P1—C13	99.9 (3)	C22—C23—H23	120.2
C19—P1—C7	105.3 (3)	C24—C23—H23	120.2
C13—P1—C7	106.6 (3)	C19—C24—C23	120.7 (8)
C19—P1—Pd	121.6 (2)	C19—C24—H24	119.7
C13—P1—Pd	113.4 (2)	C23—C24—H24	119.7
C7—P1—Pd	108.7 (2)	O1—S3—C25	115.4 (8)
C8—C7—C12	118.7 (6)	O1—S3—C26	115.0 (9)
C8—C7—P1	123.9 (6)	C25—S3—C26	112.7 (9)
C12—C7—P1	117.4 (5)	S3—C25—H25A	109.5
C7—C8—C9	120.3 (7)	S3—C25—H25B	109.5
C7—C8—H8	119.8	H25A—C25—H25B	109.5
C9—C8—H8	119.8	S3—C25—H25C	109.5
C10—C9—C8	120.4 (8)	H25A—C25—H25C	109.5
C10—C9—H9	119.8	H25B—C25—H25C	109.5
C8—C9—H9	119.8	S3—C26—H26A	109.5
C9—C10—C11	120.2 (8)	S3—C26—H26B	109.5
C9—C10—H10	119.9	H26A—C26—H26B	109.5
C11—C10—H10	119.9	S3—C26—H26C	109.5
C10—C11—C12	121.4 (8)	H26A—C26—H26C	109.5
C10—C11—H11	119.3	H26B—C26—H26C	109.5
C12—C11—H11	119.3	O1A—S3A—C26A	115.7 (10)
C7—C12—C11	119.0 (7)	O1A—S3A—C25A	114.9 (9)
C7—C12—H12	120.5	C26A—S3A—C25A	111.7 (10)
C11—C12—H12	120.5	S3A—C25A—H25D	109.5
C14—C13—C18	118.2 (6)	S3A—C25A—H25E	109.5
C14—C13—P1	120.2 (5)	H25D—C25A—H25E	109.5
C18—C13—P1	121.5 (5)	S3A—C25A—H25F	109.5
C13—C14—C15	119.1 (6)	H25D—C25A—H25F	109.5
C13—C14—H14	120.4	H25E—C25A—H25F	109.5
C15—C14—H14	120.4	S3A—C26A—H26D	109.5
C16—C15—C14	121.1 (7)	S3A—C26A—H26E	109.5
C16—C15—H15	119.5	H26D—C26A—H26E	109.5
C14—C15—H15	119.5	S3A—C26A—H26F	109.5
C17—C16—C15	120.3 (7)	H26D—C26A—H26F	109.5
C17—C16—H16	119.8	H26E—C26A—H26F	109.5
C15—C16—H16	119.8

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···N4ⁱⁱ	0.90 (1)	2.12 (2)	2.986 (7)	160 (5)

Symmetry code: (ii) −x+1, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Pd(C₂H₂N₃S₂)₂(C₁₈H₁₅P)₂]·2C₂H₆OS·0.5H₂O
M_r	1060.58
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	298
a, b, c (Å)	14.6192 (18), 13.2572 (16), 25.707 (3)
V (Å³)	4982.3 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.24 × 0.16 × 0.13

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	38822, 4590, 2603
R_int	0.107
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.137, 0.95
No. of reflections	4590
No. of parameters	322
No. of restraints	99
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.37

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Pd—P1	2.3364 (15)	P1—C19	1.807 (6)
Pd—S2	2.3407 (14)	P1—C13	1.817 (6)
S2—C2	1.736 (5)	P1—C7	1.821 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···N4ⁱ	0.904 (10)	2.12 (2)	2.986 (7)	160 (5)

Symmetry code: (i) −x+1, y, −z+3/2.

Acknowledgements

RRM would like to thank CONACYT for a posdoctoral scholarship (agreement 290586-UNAM). Support of this research by CONACYT (154732) and PAPIIT (IN201711) is gratefully acknowledged.

References

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