metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 4| April 2012| Pages m483-m484

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

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 PdII 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[Beatty, A. M. (2001). CrystEngComm, 51, 1-13.]). 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[Tzeng, B.-C., Schier, A. & Schmidbaur, H. (1999). Inorg. Chem. 38, 3978-3984.]). For SSNH2 acting as a ligand and as auxiliary in the construction of hydrogen bonds in coordination compounds with PdII, see: Tzeng, Lee et al. (2004[Tzeng, B.-C., Lee, G.-H. & Peng, S.-M. (2004). Inorg. Chem. Commun. 7, 151-154.]), with PtII, see: Tannai et al. (2006[Tannai, H., Tsuge, K. & Sasaki, Y. (2006). Bull. Chem. Soc. Jpn, 79, 1223-1230.]), with CdII, see: Gao et al. (2009[Gao, Q., Zhang, C.-Y., Cui, Y. & Xie, Y.-B. (2009). Acta Cryst. E65, m838-m839.]) and with AuI, see: Tzeng et al. (1999[Tzeng, B.-C., Schier, A. & Schmidbaur, H. (1999). Inorg. Chem. 38, 3978-3984.]); Tzeng, Huang et al. (2004[Tzeng, B.-C., Huang, Y.-C., Wu, W.-W., Lee, S.-Y., Lee, G.-H. & Peng, S.-M. (2004). Cryst. Growth Des. 4, 63-70.]). For the thiol­ate form, see: Downie et al. (1972[Downie, T. C., Harrison, W., Raper, E. S. & Hepworth, M. A. (1972). Acta Cryst. B28, 1584-1590.]).

[Scheme 1]

Experimental

Crystal data
  • [Pd(C2H2N3S2)2(C18H15P)2]·2C2H6OS·0.5H2O

  • Mr = 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)

  • Rint = 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

  • Δρmax = 0.63 e Å−3

  • Δρmin = −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 DA 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[Bruker (2007). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


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 PdII, see: Tzeng, Lee et al. (2004), with PtII, see: Tannai et al. (2006), with CdII, see: Gao et al. (2009) and with AuI, 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.

Refinement top

H atoms on N were located on the Fourier map and refined isotropically (N—H = 0.90 Å). All H atoms were included in calculated positions (C—H = 0.93 Å), and refined using a riding model with U iso (H) = 1.2Ueq of the carrier atom. The DMSO solvent is disordered and was refined in two major positions using a free variable of Site Occupational Factor (SOF). The ratio of disordered atoms was 55/45 of SOF. O of H2O molecule is in crystallographic center of symmetry and its H atom (H2O) was not possible to locate on the fourier map.

Structure description 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.

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 PdII, see: Tzeng, Lee et al. (2004), with PtII, see: Tannai et al. (2006), with CdII, see: Gao et al. (2009) and with AuI, 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
[Figure 1] 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.
[Figure 2] 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·0.5H2OF(000) = 2176
Mr = 1060.58Dx = 1.414 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 6520 reflections
a = 14.6192 (18) Åθ = 2.2–25.0°
b = 13.2572 (16) ŵ = 0.73 mm1
c = 25.707 (3) ÅT = 298 K
V = 4982.3 (10) Å3Prism, orange
Z = 40.24 × 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 tubeRint = 0.107
Graphite monochromatorθmax = 25.5°, θmin = 2.1°
Detector resolution: 0.83 pixels mm-1h = 1717
ω scansk = 1615
38822 measured reflectionsl = 3130
4590 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H atoms treated by a mixture of independent and constrained refinement
S = 0.95 w = 1/[σ2(Fo2) + (0.0611P)2]
where P = (Fo2 + 2Fc2)/3
4590 reflections(Δ/σ)max = 0.001
322 parametersΔρmax = 0.63 e Å3
99 restraintsΔρmin = 0.37 e Å3
Crystal data top
[Pd(C2H2N3S2)2(C18H15P)2]·2C2H6OS·0.5H2OV = 4982.3 (10) Å3
Mr = 1060.58Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 14.6192 (18) ŵ = 0.73 mm1
b = 13.2572 (16) ÅT = 298 K
c = 25.707 (3) Å0.24 × 0.16 × 0.13 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2603 reflections with I > 2σ(I)
38822 measured reflectionsRint = 0.107
4590 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05799 restraints
wR(F2) = 0.137H atoms treated by a mixture of independent and constrained refinement
S = 0.95Δρmax = 0.63 e Å3
4590 reflectionsΔρmin = 0.37 e Å3
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
xyzUiso*/UeqOcc. (<1)
Pd0.50000.50000.50000.04092 (19)
S10.30706 (10)0.43464 (14)0.65323 (6)0.0614 (5)
S20.35991 (9)0.47537 (12)0.54222 (5)0.0494 (4)
C20.3886 (4)0.4746 (4)0.6078 (2)0.0428 (14)
N30.4650 (3)0.5019 (4)0.62829 (17)0.0527 (13)
N40.4655 (3)0.4920 (4)0.68230 (17)0.0526 (13)
C50.3896 (4)0.4590 (5)0.7008 (2)0.0561 (16)
N60.3726 (4)0.4426 (5)0.75160 (19)0.0872 (19)
H6A0.4270 (11)0.444 (4)0.7682 (6)0.105*
H6B0.331 (3)0.489 (3)0.7616 (8)0.105*
P10.56548 (10)0.35283 (12)0.53336 (5)0.0469 (4)
C70.6788 (4)0.3827 (5)0.5585 (2)0.0524 (16)
C80.7562 (5)0.3304 (6)0.5456 (3)0.084 (2)
H80.75210.27350.52460.101*
C90.8418 (5)0.3621 (8)0.5640 (3)0.107 (3)
H90.89430.32760.55410.128*
C100.8482 (6)0.4410 (8)0.5954 (3)0.105 (3)
H100.90500.46030.60830.126*
C110.7727 (5)0.4936 (7)0.6086 (3)0.098 (3)
H110.77840.54960.63010.117*
C120.6866 (5)0.4658 (6)0.5906 (3)0.073 (2)
H120.63510.50260.60000.088*
C130.5809 (4)0.2545 (5)0.4849 (2)0.0536 (16)
C140.5676 (4)0.2755 (5)0.4331 (2)0.0606 (17)
H140.55150.34010.42250.073*
C150.5787 (5)0.1981 (6)0.3965 (3)0.076 (2)
H150.57120.21220.36130.092*
C160.5999 (5)0.1033 (6)0.4115 (4)0.081 (2)
H160.60770.05310.38670.098*
C170.6099 (5)0.0812 (6)0.4624 (4)0.092 (3)
H170.62260.01530.47260.110*
C180.6013 (5)0.1553 (5)0.4991 (3)0.077 (2)
H180.60920.13950.53400.092*
C190.5104 (5)0.2807 (4)0.5842 (2)0.0555 (16)
C200.4262 (5)0.2343 (5)0.5738 (3)0.068 (2)
H200.39860.24510.54170.082*
C210.3831 (6)0.1739 (6)0.6093 (4)0.096 (3)
H210.32750.14360.60120.115*
C220.4222 (9)0.1586 (7)0.6560 (4)0.118 (4)
H220.39290.11770.68020.141*
C230.5037 (8)0.2019 (7)0.6685 (3)0.114 (3)
H230.52990.18990.70090.137*
C240.5477 (5)0.2642 (6)0.6326 (3)0.084 (2)
H240.60280.29480.64150.101*
S30.6482 (5)0.2367 (6)0.2460 (2)0.148 (2)0.555 (7)
O10.6973 (12)0.2972 (13)0.2789 (6)0.205 (6)0.555 (7)
C250.6929 (15)0.1269 (10)0.2344 (8)0.153 (5)0.555 (7)
H25A0.71490.09820.26630.230*0.555 (7)
H25B0.74280.13430.21040.230*0.555 (7)
H25C0.64740.08340.21950.230*0.555 (7)
C260.6108 (16)0.2920 (16)0.1935 (6)0.168 (6)0.555 (7)
H26A0.58590.35680.20230.252*0.555 (7)
H26B0.56410.25130.17770.252*0.555 (7)
H26C0.66050.30060.16940.252*0.555 (7)
S3A0.7135 (7)0.2550 (8)0.2128 (3)0.174 (3)0.445 (7)
O1A0.7568 (16)0.3180 (16)0.2464 (8)0.219 (6)0.445 (7)
C25A0.6772 (18)0.1491 (12)0.2385 (10)0.140 (5)0.445 (7)
H25D0.72540.11930.25880.210*0.445 (7)
H25E0.65950.10340.21130.210*0.445 (7)
H25F0.62560.16250.26050.210*0.445 (7)
C26A0.6357 (16)0.307 (2)0.1760 (10)0.176 (7)0.445 (7)
H26D0.65880.36900.16200.264*0.445 (7)
H26E0.58190.32030.19630.264*0.445 (7)
H26F0.62050.26200.14800.264*0.445 (7)
O20.50000.034 (2)0.25000.263 (14)*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd0.0372 (3)0.0535 (4)0.0320 (3)0.0035 (3)0.0035 (3)0.0020 (3)
S10.0524 (9)0.0909 (13)0.0409 (9)0.0164 (9)0.0029 (8)0.0012 (9)
S20.0407 (8)0.0700 (11)0.0374 (8)0.0005 (7)0.0034 (6)0.0048 (7)
C20.044 (3)0.047 (4)0.037 (3)0.004 (3)0.002 (3)0.005 (3)
N30.044 (3)0.072 (3)0.043 (3)0.004 (3)0.005 (2)0.004 (3)
N40.051 (3)0.070 (4)0.037 (3)0.010 (3)0.003 (2)0.005 (3)
C50.055 (4)0.073 (5)0.041 (4)0.006 (3)0.005 (3)0.000 (3)
N60.070 (4)0.154 (6)0.037 (3)0.015 (4)0.001 (3)0.005 (4)
P10.0462 (9)0.0563 (10)0.0381 (8)0.0086 (8)0.0024 (7)0.0037 (8)
C70.046 (4)0.071 (4)0.040 (3)0.012 (3)0.002 (3)0.011 (3)
C80.063 (5)0.128 (7)0.062 (4)0.024 (5)0.009 (4)0.018 (5)
C90.056 (5)0.178 (10)0.087 (6)0.037 (6)0.016 (4)0.026 (6)
C100.053 (5)0.178 (10)0.084 (6)0.010 (6)0.019 (4)0.009 (6)
C110.078 (6)0.128 (7)0.087 (6)0.015 (6)0.017 (5)0.023 (5)
C120.054 (4)0.094 (6)0.072 (5)0.006 (4)0.013 (4)0.010 (4)
C130.048 (4)0.071 (5)0.041 (4)0.005 (3)0.007 (3)0.005 (3)
C140.059 (4)0.058 (4)0.064 (5)0.005 (3)0.005 (4)0.003 (4)
C150.080 (5)0.093 (6)0.056 (4)0.010 (5)0.014 (4)0.015 (5)
C160.076 (5)0.069 (6)0.100 (7)0.002 (4)0.031 (5)0.030 (5)
C170.092 (6)0.070 (6)0.113 (7)0.031 (5)0.019 (5)0.006 (6)
C180.089 (5)0.068 (5)0.073 (5)0.034 (4)0.002 (4)0.005 (5)
C190.073 (5)0.048 (4)0.046 (4)0.016 (4)0.007 (4)0.001 (3)
C200.094 (6)0.052 (4)0.058 (4)0.002 (4)0.022 (4)0.002 (4)
C210.127 (8)0.068 (6)0.093 (6)0.024 (5)0.035 (6)0.006 (5)
C220.186 (12)0.069 (6)0.099 (8)0.011 (7)0.067 (8)0.012 (6)
C230.188 (11)0.100 (7)0.054 (5)0.009 (8)0.019 (7)0.027 (5)
C240.111 (6)0.087 (6)0.055 (5)0.012 (5)0.008 (4)0.013 (4)
S30.146 (5)0.196 (6)0.104 (4)0.051 (4)0.005 (4)0.006 (4)
O10.245 (14)0.220 (10)0.149 (11)0.009 (10)0.024 (9)0.004 (9)
C250.122 (11)0.218 (9)0.120 (11)0.086 (9)0.060 (9)0.007 (8)
C260.166 (11)0.186 (10)0.151 (10)0.042 (10)0.020 (9)0.042 (8)
S3A0.169 (7)0.230 (7)0.123 (6)0.024 (6)0.007 (5)0.011 (5)
O1A0.216 (14)0.267 (12)0.173 (13)0.040 (11)0.020 (10)0.008 (10)
C25A0.139 (11)0.166 (10)0.115 (10)0.080 (8)0.025 (9)0.014 (8)
C26A0.188 (14)0.198 (13)0.141 (13)0.019 (11)0.003 (10)0.046 (10)
Geometric parameters (Å, º) top
Pd—P1i2.3363 (15)C16—H160.9300
Pd—P12.3364 (15)C17—C181.368 (9)
Pd—S2i2.3407 (14)C17—H170.9300
Pd—S22.3407 (14)C18—H180.9300
S1—C51.748 (6)C19—C241.377 (8)
S1—C21.751 (5)C19—C201.402 (8)
S2—C21.736 (5)C20—C211.367 (9)
C2—N31.288 (7)C20—H200.9300
N3—N41.394 (6)C21—C221.344 (12)
N4—C51.284 (7)C21—H210.9300
C5—N61.348 (7)C22—C231.362 (12)
N6—H6A0.904 (10)C22—H220.9300
N6—H6B0.899 (10)C23—C241.396 (10)
P1—C191.807 (6)C23—H230.9300
P1—C131.817 (6)C24—H240.9300
P1—C71.821 (6)S3—O11.369 (12)
C7—C81.367 (8)S3—C251.623 (8)
C7—C121.382 (8)S3—C261.632 (7)
C8—C91.402 (10)C25—H25A0.9600
C8—H80.9300C25—H25B0.9600
C9—C101.324 (11)C25—H25C0.9600
C9—H90.9300C26—H26A0.9600
C10—C111.348 (10)C26—H26B0.9600
C10—H100.9300C26—H26C0.9600
C11—C121.391 (9)S3A—O1A1.358 (12)
C11—H110.9300S3A—C26A1.633 (8)
C12—H120.9300S3A—C25A1.640 (8)
C13—C141.374 (7)C25A—H25D0.9600
C13—C181.397 (8)C25A—H25E0.9600
C14—C151.401 (8)C25A—H25F0.9600
C14—H140.9300C26A—H26D0.9600
C15—C161.351 (10)C26A—H26E0.9600
C15—H150.9300C26A—H26F0.9600
C16—C171.348 (10)
P1i—Pd—P1180.0C16—C17—C18120.1 (7)
P1i—Pd—S2i94.12 (5)C16—C17—H17119.9
P1—Pd—S2i85.88 (5)C18—C17—H17119.9
P1i—Pd—S285.89 (5)C17—C18—C13121.1 (7)
P1—Pd—S294.12 (5)C17—C18—H18119.4
S2i—Pd—S2180.0C13—C18—H18119.4
C5—S1—C286.6 (3)C24—C19—C20116.7 (6)
C2—S2—Pd103.87 (19)C24—C19—P1124.2 (6)
N3—C2—S2127.2 (4)C20—C19—P1119.1 (5)
N3—C2—S1113.7 (4)C21—C20—C19122.4 (7)
S2—C2—S1119.0 (3)C21—C20—H20118.8
C2—N3—N4112.7 (5)C19—C20—H20118.8
C5—N4—N3113.3 (5)C22—C21—C20119.2 (9)
N4—C5—N6125.0 (5)C22—C21—H21120.4
N4—C5—S1113.6 (4)C20—C21—H21120.4
N6—C5—S1121.4 (5)C21—C22—C23121.4 (9)
C5—N6—H6A107.1 (13)C21—C22—H22119.3
C5—N6—H6B107.0 (13)C23—C22—H22119.3
H6A—N6—H6B116.7 (19)C22—C23—C24119.7 (9)
C19—P1—C1399.9 (3)C22—C23—H23120.2
C19—P1—C7105.3 (3)C24—C23—H23120.2
C13—P1—C7106.6 (3)C19—C24—C23120.7 (8)
C19—P1—Pd121.6 (2)C19—C24—H24119.7
C13—P1—Pd113.4 (2)C23—C24—H24119.7
C7—P1—Pd108.7 (2)O1—S3—C25115.4 (8)
C8—C7—C12118.7 (6)O1—S3—C26115.0 (9)
C8—C7—P1123.9 (6)C25—S3—C26112.7 (9)
C12—C7—P1117.4 (5)S3—C25—H25A109.5
C7—C8—C9120.3 (7)S3—C25—H25B109.5
C7—C8—H8119.8H25A—C25—H25B109.5
C9—C8—H8119.8S3—C25—H25C109.5
C10—C9—C8120.4 (8)H25A—C25—H25C109.5
C10—C9—H9119.8H25B—C25—H25C109.5
C8—C9—H9119.8S3—C26—H26A109.5
C9—C10—C11120.2 (8)S3—C26—H26B109.5
C9—C10—H10119.9H26A—C26—H26B109.5
C11—C10—H10119.9S3—C26—H26C109.5
C10—C11—C12121.4 (8)H26A—C26—H26C109.5
C10—C11—H11119.3H26B—C26—H26C109.5
C12—C11—H11119.3O1A—S3A—C26A115.7 (10)
C7—C12—C11119.0 (7)O1A—S3A—C25A114.9 (9)
C7—C12—H12120.5C26A—S3A—C25A111.7 (10)
C11—C12—H12120.5S3A—C25A—H25D109.5
C14—C13—C18118.2 (6)S3A—C25A—H25E109.5
C14—C13—P1120.2 (5)H25D—C25A—H25E109.5
C18—C13—P1121.5 (5)S3A—C25A—H25F109.5
C13—C14—C15119.1 (6)H25D—C25A—H25F109.5
C13—C14—H14120.4H25E—C25A—H25F109.5
C15—C14—H14120.4S3A—C26A—H26D109.5
C16—C15—C14121.1 (7)S3A—C26A—H26E109.5
C16—C15—H15119.5H26D—C26A—H26E109.5
C14—C15—H15119.5S3A—C26A—H26F109.5
C17—C16—C15120.3 (7)H26D—C26A—H26F109.5
C17—C16—H16119.8H26E—C26A—H26F109.5
C15—C16—H16119.8
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6A···N4ii0.90 (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
Mr1060.58
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)298
a, b, c (Å)14.6192 (18), 13.2572 (16), 25.707 (3)
V3)4982.3 (10)
Z4
Radiation typeMo Kα
µ (mm1)0.73
Crystal size (mm)0.24 × 0.16 × 0.13
Data collection
DiffractometerBruker SMART APEX CCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
38822, 4590, 2603
Rint0.107
(sin θ/λ)max1)0.605
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.137, 0.95
No. of reflections4590
No. of parameters322
No. of restraints99
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.63, 0.37

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

Selected bond lengths (Å) top
Pd—P12.3364 (15)P1—C191.807 (6)
Pd—S22.3407 (14)P1—C131.817 (6)
S2—C21.736 (5)P1—C71.821 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6A···N4i0.904 (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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Volume 68| Part 4| April 2012| Pages m483-m484
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