{2,6-Bis[(pyridin-2-yl)sulfanylmeth­yl]pyridine-κ2N,N′}(η3-prop-2-en­yl)palladium(II) hexa­fluoro­phosphate

Bruno, G.; Nicolò, F.; Tresoldi, G.; Drommi, D.; Mollica Nardo, V.

doi:10.1107/S1600536814003961

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 4| April 2014| Pages m134-m135

doi:10.1107/S1600536814003961

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{2,6-Bis[(pyridin-2-yl)sulfanylmethyl]pyridine-κ²N,N′}(η³-prop-2-enyl)palladium(II) hexafluorophosphate

Giuseppe Bruno,^a ^* Francesco Nicolò,^a Giuseppe Tresoldi,^a Dario Drommi ^a and Viviana Mollica Nardo ^a

^aDipartimento di Scienze Chimiche, Universita di Messina, Messina, Italy
^*Correspondence e-mail: gbruno@unime.it

(Received 7 December 2013; accepted 20 February 2014; online 15 March 2014)

The title compound, [Pd(C₃H₅)(C₁₇H₁₅N₃S₂)]PF₆, is built up by a [(η³-allyl)Pd]²⁺ fragment coordinated by a 2,6-bis[(pyridin-2-yl)sulfanylmethyl]pyridine ligand coordinated through the N atoms. One of the S atoms is at a close distance to the metal centeratom [3.2930 (8) Å]. The Pd^II atom is tetracoordinated in a strongly distorted square-planar environment mainly determined by the η³-allyl anion in which the central C atom is disordered over two equally occupied positions. The crystal packing is very compact and is characterized by a three-dimensional network of C—H⋯F interactions between the F atoms of each anion and several H atoms of the surrounding cationic complexes.

CCDC reference: 988035

Related literature

For the catalitic use of palladium η³-allyl complexes, see: De Vries (2012 ). For multidentate nitrogen/sulfur ligands, see: Betz et al. (2008 ). For the η³–η¹–η³ mechanism and syn--syn anti–anti isomerism, see: Solin & Szabo (2001 ); Takao et al. (2003 ); Barloy et al. (2000 ); Gogoll et al. (1997 ); Tresoldi et al. (2008 , 2010 ). For the synthesis and structural properties of palladium–allyl complexes, see: Scopelliti et al. (2001 ); Tresoldi et al. (2002 ); Baradello et al. (2004 ).

Experimental

Crystal data

[Pd(C₃H₅)(C₁₇H₁₅N₃S₂)]PF₆
M_r = 617.88
Monoclinic, P 2₁ /n
a = 13.663 (1) Å
b = 13.667 (1) Å
c = 13.727 (1) Å
β = 113.01 (1)°
V = 2359.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 293 K
0.4 × 0.32 × 0.29 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: integration (SADABS; Bruker, 2005 ) T_min = 0.634, T_max = 0.666
74899 measured reflections
5419 independent reflections
4912 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.114
S = 1.07
5419 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯F3ⁱ	0.93	2.42	3.270 (8)	151
C4—H4⋯F2ⁱⁱ	0.93	2.47	3.358 (6)	161
C8—H8⋯F4ⁱⁱⁱ	0.93	2.44	3.317 (8)	157
C12—H12A⋯F3^iv	0.97	2.45	3.126 (8)	126
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 988035

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814003961/bt6949sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814003961/bt6949Isup2.hkl

checkCIF report

Comment top

The chemistry of palladium-allyl complexes has been reported extensively. This interest has stemmed from the relevance to palladium-catalyzed allylic substitution reactions. Attack of the nucleophile on a cationic palladium η³-allyl complex is conventionally accepted as the crucial step in the catalytic cycle (De Vries 2012). Multidentate nitrogen ligands or multidentate sulfur nitrogen ligands have been used for the structure analysis of (η³-allyl)palladium complexes and the study of their influence upon the dynamic behaviour (Betz et al., 2008). One process encountered in (η³-allyl)palladium complexes is a syn anti isomerism which has been subject of research for many years. The η³-η¹-η³ mechanism is well established for many [Pd(η³-allyl)L1L2]⁺ cations (Solin et al., 2001). Other process usually observed is apparent allyl rotation or syn-syn anti-anti isomerism (Takao et al., 2003). Mechanisms proposed for this process include: i) an associative mechanism, involving a non-rigid five-coordinated intermediate (Barloy et al., 2000), ii) a dissociative mechanism with stabilization of tricoordinate intermediate, mostly, in some complexes with N-donor ligands (Gogoll et al., 1997). We have lately been interested in the use of potentially tridentate N, S, N ligands in coordination chemistry towards congested ruthenium(II)substrates. The contemporary presence of the congested substrate and sterically demanding ligand favoured the N,S-chelation of the thioether with formation of the four membered chelate ring (Scopelliti et al., 2001; Tresoldi et al., 2002) and the five membered chelate ring, (Baradello et al., 2004). However the exchange between these isomers was hampered by the very low abundance of the four membered species and the large value of the activation energy of the process (Tresoldi et al., 2008). The potentially polidentate N₃S₂ or N₅S₂ dithioethers, containing a 2,6-substitute linker with two thioether-heterocycle arms, were prepared and their reactions with some congested ruthenium substrates explored. Only the four membered species was obtained and the sulfur inversion observed. (Tresoldi et al., 2010) With the aim of favouring different modes of coordination of dithioethers and as extension of our stereodynamic studies, we have examined the reactions of the dithioethers with the solvate species [Pd(allyl)(acetone)₂]⁺, obtaining the species [Pd(allyl)(dithioether)]PF₆ stereo-chemically no-rigid. The Nouter, Ncentral-coordination of dithioether ligand with formation of seven membered chelate ring is favoured in the solid state while in solution the dynamic behaviour of the compounds involves the dithioether attempt to coordinate with all the donor atoms. In this paper the reaction of 2,6-bis(2-pyridylsulfanylmethyl)pyridine(psmp) with [Pd(C₃H₅)(acetone)]⁺, generate in situ from [Pd(C₃H₅)Cl]₂ and AgPF₆, led to the title compound,[Pd(C₃H₅)(psmp)]PF₆ (I).

Related literature top

For the catalitic use of palladium η³-allyl complexes, see: De Vries (2012). For multidentate nitrogen/sulfur ligands, see: Betz et al. (2008). For the η³–η¹–η³ mechanism and syn--syn anti–anti isomerism, see: Solin & Szabo (2001); Takao et al. (2003); Barloy et al. (2000); Gogoll et al. (1997); Tresoldi et al. (2008, 2010). For the synthesis and structural properties of palladium–allyl complexes, see: Scopelliti et al. (2001); Tresoldi et al. (2002); Baradello et al. (2004).

Experimental top

To a stirred solution, of [Pd(C₃H₅)Cl]₂ (91,5 mg, 0.25 mmol) in acetone (20 ml) was added AgPF₆ (126.4 mg, 0.5 mmol). After 30 m silver chloride was filtered. The solution of the solvento species was added to 15 ml of acetone containing 162.7 mg (0.5 mmol) of psmp and stirred for 2 h. The resulting solution was filterd on diethyl ether (120 ml) and a white precipitate was obtained, which was filtered, washed with diethyl ether (30 ml) and dried overnight. Yield 247 mg (80%). White crystals of I suitable for X-ray structure investigation were obtained from a solution in acetone-ether (1:3) on standing for ca 4 d at 253 K°. C₂₀H₂₀F₆N₃PPdS₂ (617.9) requires: C 38.88, H 3.26, N 6.80, S 10.38%; found: C 38.80, H 3.30, N 6.90, S 10.70%. Conductivity: ΛM(MeCN, 5x10–4 mol L-1, 20 °C) = 146 S cm2 mol-1. 1H NMR (500 MHz, [D6]acetone, 323 °C): δ8.65 (dd, J6,4 = 1.6 Hz, J_6,5 = 5.4 Hz, 2H, H6),8.02 (t, J = 7.8 Hz, 1H, H4'), 7.76 (d, 2H, H3', H5'), 7.67 (ddd, J4,5 = 7.8 Hz, J_4,3 = 8.2 Hz, 2H, H4), 7.38 (ddd, J_5,3 = 1.0 Hz, 2H, H3), 7.19 (ddd, 2H, H5), 6.13 (m, 1H, allyl CH), 5.14 (s, 4H, S—CH2), 3.97 (br, 4H, allyl syn-anti).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Perspective view of the title molecule with numbering of the atoms. Non H-atoms represented as displacement ellipsoids are plotted at the 30% probability level, while H atoms are shown as small spheres of arbitrary radius. The PF₆^- anion and one of the disordered C atoms have been omitted for clarity.

{2,6-Bis[(pyridin-2-yl)sulfanylmethyl]pyridine-κ²N,N'}(η³-prop-2-enyl)palladium(II) hexafluorophosphate top

Crystal data top

[Pd(C₃H₅)(C₁₇H₁₅N₃S₂)]PF₆	F(000) = 1232
M_r = 617.88	D_x = 1.739 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 136 reflections
a = 13.663 (1) Å	θ = 2.2–30.0°
b = 13.667 (1) Å	µ = 1.09 mm⁻¹
c = 13.727 (1) Å	T = 293 K
β = 113.01 (1)°	Prismatic, yellow
V = 2359.3 (3) Å³	0.4 × 0.32 × 0.29 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	5419 independent reflections
Radiation source: fine-focus sealed tube	4912 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: integration (SADABS; Bruker, 2005)	h = −17→17
T_min = 0.634, T_max = 0.666	k = −17→17
74899 measured reflections	l = −17→17

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0579P)² + 2.4402P] where P = (F_o² + 2F_c²)/3
5419 reflections	(Δ/σ)_max = 0.002
307 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.69 e Å⁻³

Crystal data top

[Pd(C₃H₅)(C₁₇H₁₅N₃S₂)]PF₆	V = 2359.3 (3) Å³
M_r = 617.88	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.663 (1) Å	µ = 1.09 mm⁻¹
b = 13.667 (1) Å	T = 293 K
c = 13.727 (1) Å	0.4 × 0.32 × 0.29 mm
β = 113.01 (1)°

Data collection top

Bruker APEXII CCD diffractometer	5419 independent reflections
Absorption correction: integration (SADABS; Bruker, 2005)	4912 reflections with I > 2σ(I)
T_min = 0.634, T_max = 0.666	R_int = 0.028
74899 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.07	Δρ_max = 0.57 e Å⁻³
5419 reflections	Δρ_min = −0.69 e Å⁻³
307 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2σ(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)
Pd1	0.88269 (2)	0.24170 (2)	0.51700 (2)	0.04910 (10)
S1	0.92247 (8)	0.38395 (7)	0.76617 (7)	0.0673 (2)
S2	0.63967 (7)	0.29098 (8)	0.34786 (9)	0.0729 (3)
P1	0.33006 (8)	0.11910 (9)	0.58509 (8)	0.0708 (3)
N2	0.8081 (2)	0.23926 (19)	0.6281 (3)	0.0568 (6)
N1	0.85839 (18)	0.39548 (17)	0.49428 (18)	0.0434 (5)
C6	0.9869 (2)	0.4005 (2)	0.6749 (2)	0.0540 (7)
H6A	1.0516	0.4381	0.7090	0.065*
H6B	1.0064	0.3372	0.6561	0.065*
C5	0.9163 (2)	0.4522 (2)	0.5770 (2)	0.0472 (6)
C1	0.7881 (2)	0.4391 (2)	0.4067 (2)	0.0520 (6)
C7	0.8199 (3)	0.2976 (3)	0.7103 (3)	0.0589 (8)
C2	0.7764 (3)	0.5391 (3)	0.4006 (3)	0.0678 (9)
H2	0.7273	0.5677	0.3396	0.081*
C3	0.8370 (3)	0.5967 (3)	0.4841 (4)	0.0737 (10)
H3	0.8303	0.6645	0.4801	0.088*
C12	0.7244 (3)	0.3743 (3)	0.3162 (3)	0.0686 (9)
H12A	0.7726	0.3371	0.2941	0.082*
H12B	0.6810	0.4148	0.2570	0.082*
C14	0.4859 (3)	0.3416 (4)	0.4160 (3)	0.0794 (11)
H14	0.5013	0.2825	0.4524	0.095*
C13	0.5421 (3)	0.3717 (3)	0.3584 (3)	0.0688 (9)
C4	0.9077 (3)	0.5525 (2)	0.5735 (3)	0.0626 (8)
H4	0.9495	0.5900	0.6313	0.075*
C15	0.4064 (4)	0.4005 (5)	0.4192 (5)	0.1015 (16)
H15	0.3664	0.3821	0.4576	0.122*
C11	0.7291 (3)	0.1721 (3)	0.6012 (4)	0.0767 (10)
H11	0.7209	0.1299	0.5454	0.092*
C9	0.6727 (4)	0.2240 (5)	0.7335 (5)	0.0987 (17)
H9	0.6269	0.2192	0.7687	0.118*
N3	0.5268 (3)	0.4554 (3)	0.3068 (3)	0.0924 (11)
C8	0.7514 (4)	0.2918 (4)	0.7639 (4)	0.0842 (12)
H8	0.7597	0.3341	0.8197	0.101*
C10	0.6609 (4)	0.1628 (4)	0.6513 (5)	0.0942 (15)
H10	0.6076	0.1157	0.6298	0.113*
C17	0.4487 (5)	0.5119 (5)	0.3121 (6)	0.118 (2)
H17	0.4362	0.5720	0.2776	0.141*
C16	0.3869 (4)	0.4866 (5)	0.3648 (6)	0.1136 (19)
H16	0.3321	0.5274	0.3640	0.136*
F1	0.2921 (4)	0.0312 (3)	0.6341 (3)	0.1496 (15)
F6	0.3721 (4)	0.2025 (4)	0.5351 (4)	0.175 (2)
F2	0.4174 (3)	0.1344 (4)	0.6926 (3)	0.1620 (18)
F3	0.2562 (5)	0.1880 (5)	0.6114 (5)	0.225 (3)
F5	0.3954 (5)	0.0555 (5)	0.5459 (5)	0.218 (3)
F4	0.2372 (4)	0.1053 (6)	0.4768 (4)	0.248 (4)
C18	0.9545 (4)	0.2038 (3)	0.4089 (4)	0.0780 (11)
H18A	1.0023	0.2399	0.4647	0.094*	0.5
H18B	0.9384	0.2234	0.3395	0.094*	0.5
H18C	0.8832	0.2196	0.3725	0.094*	0.5
H18D	1.0060	0.2322	0.3894	0.094*	0.5
C19	0.9081 (6)	0.1225 (5)	0.4289 (6)	0.0578 (16)	0.5
H19	0.8603	0.0866	0.3729	0.069*	0.5
C19A	0.9822 (11)	0.1423 (7)	0.4872 (13)	0.111 (4)	0.5
H19A	1.0552	0.1318	0.5180	0.133*	0.5
C20	0.9312 (4)	0.0929 (3)	0.5311 (4)	0.0826 (12)
H20A	0.9789	0.1286	0.5873	0.099*	0.5
H20B	0.8991	0.0372	0.5441	0.099*	0.5
H20C	0.8575	0.0980	0.5064	0.099*	0.5
H20D	0.9676	0.0519	0.5878	0.099*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.05044 (15)	0.03748 (13)	0.06055 (17)	−0.00211 (8)	0.02296 (11)	−0.00752 (8)
S1	0.0830 (6)	0.0675 (5)	0.0497 (4)	0.0056 (4)	0.0242 (4)	−0.0034 (4)
S2	0.0549 (5)	0.0693 (6)	0.0831 (6)	−0.0076 (4)	0.0145 (4)	−0.0209 (5)
P1	0.0635 (5)	0.0844 (7)	0.0655 (5)	−0.0011 (5)	0.0264 (4)	0.0102 (5)
N2	0.0555 (15)	0.0507 (14)	0.0676 (17)	0.0019 (11)	0.0279 (13)	0.0082 (12)
N1	0.0420 (11)	0.0404 (11)	0.0485 (11)	−0.0026 (9)	0.0184 (9)	−0.0029 (9)
C6	0.0487 (15)	0.0502 (16)	0.0546 (16)	−0.0003 (12)	0.0110 (12)	−0.0052 (13)
C5	0.0454 (13)	0.0422 (14)	0.0543 (15)	−0.0037 (11)	0.0198 (12)	−0.0038 (11)
C1	0.0463 (14)	0.0601 (17)	0.0497 (14)	−0.0007 (12)	0.0190 (12)	0.0035 (13)
C7	0.0612 (18)	0.0620 (19)	0.0571 (17)	0.0161 (15)	0.0271 (14)	0.0180 (15)
C2	0.0612 (19)	0.064 (2)	0.073 (2)	0.0070 (16)	0.0207 (17)	0.0240 (17)
C3	0.075 (2)	0.0418 (16)	0.101 (3)	0.0021 (16)	0.030 (2)	0.0125 (17)
C12	0.0597 (19)	0.089 (3)	0.0497 (17)	0.0001 (18)	0.0132 (14)	−0.0067 (17)
C14	0.071 (2)	0.080 (3)	0.082 (3)	−0.011 (2)	0.025 (2)	−0.018 (2)
C13	0.0490 (16)	0.074 (2)	0.068 (2)	−0.0065 (16)	0.0065 (15)	−0.0186 (18)
C4	0.0656 (19)	0.0416 (15)	0.078 (2)	−0.0077 (14)	0.0252 (17)	−0.0061 (15)
C15	0.080 (3)	0.113 (4)	0.121 (4)	−0.014 (3)	0.049 (3)	−0.031 (3)
C11	0.072 (2)	0.064 (2)	0.096 (3)	−0.0087 (18)	0.035 (2)	0.010 (2)
C9	0.082 (3)	0.123 (4)	0.114 (4)	0.019 (3)	0.063 (3)	0.048 (4)
N3	0.074 (2)	0.093 (3)	0.100 (3)	0.015 (2)	0.0233 (19)	0.010 (2)
C8	0.087 (3)	0.106 (3)	0.072 (2)	0.027 (3)	0.045 (2)	0.026 (2)
C10	0.072 (3)	0.094 (3)	0.126 (4)	−0.003 (2)	0.048 (3)	0.036 (3)
C17	0.089 (3)	0.102 (4)	0.153 (5)	0.028 (3)	0.039 (4)	0.022 (4)
C16	0.079 (3)	0.112 (5)	0.147 (5)	0.019 (3)	0.041 (3)	−0.012 (4)
F1	0.173 (4)	0.129 (3)	0.151 (3)	−0.037 (3)	0.068 (3)	0.034 (2)
F6	0.203 (5)	0.191 (5)	0.145 (3)	−0.071 (4)	0.083 (3)	0.039 (3)
F2	0.135 (3)	0.210 (5)	0.094 (2)	−0.044 (3)	−0.006 (2)	0.003 (3)
F3	0.278 (6)	0.211 (5)	0.264 (6)	0.164 (5)	0.192 (6)	0.149 (5)
F5	0.234 (6)	0.219 (6)	0.264 (6)	0.033 (5)	0.167 (5)	−0.062 (5)
F4	0.142 (4)	0.448 (11)	0.115 (3)	−0.104 (5)	0.009 (3)	0.073 (5)
C18	0.089 (3)	0.069 (2)	0.092 (3)	0.005 (2)	0.053 (2)	−0.017 (2)
C19	0.056 (4)	0.047 (3)	0.070 (4)	−0.001 (3)	0.024 (3)	−0.025 (3)
C19A	0.134 (10)	0.057 (5)	0.189 (13)	0.028 (6)	0.115 (10)	0.002 (7)
C20	0.106 (3)	0.0407 (17)	0.105 (3)	0.0147 (19)	0.046 (3)	−0.0080 (18)

Geometric parameters (Å, º) top

Pd1—C19A	2.073 (8)	C14—C13	1.364 (6)
Pd1—C20	2.124 (4)	C14—C15	1.365 (7)
Pd1—N1	2.132 (2)	C14—H14	0.9300
Pd1—C18	2.137 (4)	C13—N3	1.318 (6)
Pd1—C19	2.136 (6)	C4—H4	0.9300
Pd1—N2	2.141 (3)	C15—C16	1.364 (8)
S1—C7	1.761 (4)	C15—H15	0.9300
S1—C6	1.805 (3)	C11—C10	1.363 (6)
S2—C13	1.779 (4)	C11—H11	0.9300
S2—C12	1.795 (4)	C9—C8	1.357 (8)
P1—F5	1.489 (4)	C9—C10	1.363 (8)
P1—F2	1.506 (3)	C9—H9	0.9300
P1—F3	1.523 (5)	N3—C17	1.344 (7)
P1—F4	1.543 (4)	C8—H8	0.9300
P1—F6	1.553 (4)	C10—H10	0.9300
P1—F1	1.561 (4)	C17—C16	1.353 (8)
N2—C7	1.339 (5)	C17—H17	0.9300
N2—C11	1.353 (5)	C16—H16	0.9300
N1—C5	1.347 (4)	C18—C19A	1.299 (14)
N1—C1	1.350 (4)	C18—C19	1.360 (9)
C6—C5	1.490 (4)	C18—H18A	0.9300
C6—H6A	0.9700	C18—H18B	0.9300
C6—H6B	0.9700	C18—H18C	0.9300
C5—C4	1.375 (4)	C18—H18D	0.9300
C1—C2	1.374 (5)	C19—C20	1.373 (9)
C1—C12	1.497 (5)	C19—H19	0.9300
C7—C8	1.401 (5)	C19A—C20	1.278 (12)
C2—C3	1.370 (6)	C19A—H19A	0.9300
C2—H2	0.9300	C20—H20A	0.9300
C3—C4	1.370 (5)	C20—H20B	0.9300
C3—H3	0.9300	C20—H20C	0.9300
C12—H12A	0.9700	C20—H20D	0.9300
C12—H12B	0.9700

C19A—Pd1—C20	35.4 (3)	C15—C14—H14	120.8
C19A—Pd1—N1	134.0 (3)	N3—C13—C14	124.5 (4)
C20—Pd1—N1	169.28 (15)	N3—C13—S2	117.4 (3)
C19A—Pd1—C18	35.9 (4)	C14—C13—S2	118.1 (4)
C20—Pd1—C18	67.68 (19)	C3—C4—C5	119.5 (3)
N1—Pd1—C18	102.98 (14)	C3—C4—H4	120.3
C20—Pd1—C19	37.6 (2)	C5—C4—H4	120.3
N1—Pd1—C19	136.0 (2)	C16—C15—C14	118.6 (5)
C18—Pd1—C19	37.1 (2)	C16—C15—H15	120.7
C19A—Pd1—N2	131.5 (4)	C14—C15—H15	120.7
C20—Pd1—N2	97.96 (15)	N2—C11—C10	123.7 (5)
N1—Pd1—N2	91.68 (9)	N2—C11—H11	118.2
C18—Pd1—N2	165.10 (15)	C10—C11—H11	118.2
C19—Pd1—N2	128.3 (2)	C8—C9—C10	119.8 (4)
C7—S1—C6	107.62 (15)	C8—C9—H9	120.1
C13—S2—C12	101.6 (2)	C10—C9—H9	120.1
F5—P1—F2	94.4 (3)	C13—N3—C17	115.6 (5)
F5—P1—F3	173.1 (4)	C9—C8—C7	119.3 (5)
F2—P1—F3	91.5 (4)	C9—C8—H8	120.3
F5—P1—F4	88.0 (4)	C7—C8—H8	120.3
F2—P1—F4	177.5 (4)	C9—C10—C11	118.6 (5)
F3—P1—F4	86.1 (4)	C9—C10—H10	120.7
F5—P1—F6	83.8 (4)	C11—C10—H10	120.7
F2—P1—F6	92.4 (3)	N3—C17—C16	123.8 (6)
F3—P1—F6	92.6 (3)	N3—C17—H17	118.1
F4—P1—F6	88.3 (3)	C16—C17—H17	118.1
F5—P1—F1	93.0 (3)	C17—C16—C15	119.0 (5)
F2—P1—F1	87.4 (2)	C17—C16—H16	120.5
F3—P1—F1	90.7 (3)	C15—C16—H16	120.5
F4—P1—F1	92.0 (3)	C19A—C18—Pd1	69.3 (4)
F6—P1—F1	176.8 (3)	C19—C18—Pd1	71.4 (3)
C7—N2—C11	117.1 (3)	C19—C18—H18A	120.0
C7—N2—Pd1	131.0 (2)	Pd1—C18—H18A	70.5
C11—N2—Pd1	111.5 (3)	C19—C18—H18B	120.0
C5—N1—C1	118.4 (3)	Pd1—C18—H18B	130.8
C5—N1—Pd1	115.92 (19)	H18A—C18—H18B	120.0
C1—N1—Pd1	125.6 (2)	C19A—C18—H18C	120.0
C5—C6—S1	111.5 (2)	Pd1—C18—H18C	69.5
C5—C6—H6A	109.3	C19A—C18—H18D	120.0
S1—C6—H6A	109.3	Pd1—C18—H18D	134.7
C5—C6—H6B	109.3	H18C—C18—H18D	120.0
S1—C6—H6B	109.3	C18—C19—C20	120.5 (6)
H6A—C6—H6B	108.0	C18—C19—Pd1	71.5 (3)
N1—C5—C4	122.0 (3)	C20—C19—Pd1	70.7 (3)
N1—C5—C6	116.6 (3)	C18—C19—H19	119.7
C4—C5—C6	121.4 (3)	C20—C19—H19	119.7
N1—C1—C2	121.2 (3)	Pd1—C19—H19	130.8
N1—C1—C12	117.3 (3)	C20—C19A—C18	134.1 (12)
C2—C1—C12	121.5 (3)	C20—C19A—Pd1	74.5 (4)
N2—C7—C8	121.5 (4)	C18—C19A—Pd1	74.7 (5)
N2—C7—S1	125.4 (3)	C20—C19A—H19A	113.0
C8—C7—S1	113.0 (3)	C18—C19A—H19A	113.0
C3—C2—C1	120.2 (3)	Pd1—C19A—H19A	132.9
C3—C2—H2	119.9	C19A—C20—Pd1	70.1 (4)
C1—C2—H2	119.9	C19—C20—Pd1	71.7 (3)
C4—C3—C2	118.7 (3)	C19—C20—H20A	120.0
C4—C3—H3	120.7	Pd1—C20—H20A	70.5
C2—C3—H3	120.7	C19—C20—H20B	120.0
C1—C12—S2	113.3 (2)	Pd1—C20—H20B	130.4
C1—C12—H12A	108.9	H20A—C20—H20B	120.0
S2—C12—H12A	108.9	C19A—C20—H20C	120.0
C1—C12—H12B	108.9	Pd1—C20—H20C	69.0
S2—C12—H12B	108.9	C19A—C20—H20D	120.0
H12A—C12—H12B	107.7	Pd1—C20—H20D	134.3
C13—C14—C15	118.4 (5)	H20C—C20—H20D	120.0
C13—C14—H14	120.8

C7—S1—C6—C5	69.5 (2)	N1—C5—C4—C3	1.1 (5)
C1—N1—C5—C4	−1.7 (4)	C6—C5—C4—C3	−176.0 (3)
Pd1—N1—C5—C4	−179.3 (2)	C13—C14—C15—C16	−0.2 (7)
C1—N1—C5—C6	175.5 (3)	C7—N2—C11—C10	1.5 (6)
Pd1—N1—C5—C6	−2.1 (3)	Pd1—N2—C11—C10	−172.4 (4)
S1—C6—C5—N1	−94.4 (3)	C14—C13—N3—C17	−1.1 (7)
S1—C6—C5—C4	82.8 (3)	S2—C13—N3—C17	176.6 (4)
C5—N1—C1—C2	0.9 (4)	C10—C9—C8—C7	−0.3 (7)
Pd1—N1—C1—C2	178.4 (2)	N2—C7—C8—C9	1.6 (6)
C5—N1—C1—C12	−179.7 (3)	S1—C7—C8—C9	−175.9 (4)
Pd1—N1—C1—C12	−2.3 (4)	C8—C9—C10—C11	−0.3 (8)
C11—N2—C7—C8	−2.2 (5)	N2—C11—C10—C9	−0.3 (7)
Pd1—N2—C7—C8	170.3 (3)	C13—N3—C17—C16	−0.9 (9)
C11—N2—C7—S1	175.0 (3)	N3—C17—C16—C15	2.3 (10)
Pd1—N2—C7—S1	−12.5 (4)	C14—C15—C16—C17	−1.7 (9)
C6—S1—C7—N2	13.8 (3)	C19A—C18—C19—C20	25.8 (6)
C6—S1—C7—C8	−168.8 (3)	Pd1—C18—C19—C20	−53.0 (5)
N1—C1—C2—C3	0.4 (5)	C19A—C18—C19—Pd1	78.8 (6)
C12—C1—C2—C3	−179.0 (3)	C19—C18—C19A—C20	−34.2 (11)
C1—C2—C3—C4	−1.0 (6)	Pd1—C18—C19A—C20	49.4 (11)
N1—C1—C12—S2	62.6 (4)	C19—C18—C19A—Pd1	−83.6 (6)
C2—C1—C12—S2	−118.1 (3)	C18—C19A—C20—C19	33.8 (12)
C13—S2—C12—C1	70.3 (3)	Pd1—C19A—C20—C19	83.2 (6)
C15—C14—C13—N3	1.7 (6)	C18—C19A—C20—Pd1	−49.5 (11)
C15—C14—C13—S2	−176.0 (3)	C18—C19—C20—C19A	−26.3 (6)
C12—S2—C13—N3	24.4 (3)	Pd1—C19—C20—C19A	−79.6 (6)
C12—S2—C13—C14	−157.8 (3)	C18—C19—C20—Pd1	53.4 (5)
C2—C3—C4—C5	0.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F3ⁱ	0.93	2.42	3.270 (8)	151
C4—H4···F2ⁱⁱ	0.93	2.47	3.358 (6)	161
C8—H8···F4ⁱⁱⁱ	0.93	2.44	3.317 (8)	157
C12—H12A···F3^iv	0.97	2.45	3.126 (8)	126

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F3ⁱ	0.93	2.42	3.270 (8)	151
C4—H4···F2ⁱⁱ	0.93	2.47	3.358 (6)	161
C8—H8···F4ⁱⁱⁱ	0.93	2.44	3.317 (8)	157
C12—H12A···F3^iv	0.97	2.45	3.126 (8)	126

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

References

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Volume 70| Part 4| April 2014| Pages m134-m135

doi:10.1107/S1600536814003961

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