Tetra­kis(4-cyano­pyridine)­palladium(II) bis­(trifluoro­methane­sulfonate)

Adrian, R.A.; Gonzalez, D.M.; Tiekink, E.R.T.; Walmsley, J.A.

doi:10.1107/S1600536810027704

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages m957-m958

https://doi.org/10.1107/S1600536810027704

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Tetrakis(4-cyanopyridine)palladium(II) bis(trifluoromethanesulfonate)

Rafael A. Adrian,^a ‡ David M. Gonzalez,^a Edward R. T. Tiekink ^b ^* and Judith A. Walmsley ^c §

^aDepartment of Chemistry, University of the Incarnate Word, San Antonio, TX 78209, USA, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cDepartment of Chemistry, University of Texas at San Antonio, San Antonio, TX 78249, USA
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 9 July 2010; accepted 13 July 2010; online 17 July 2010)

The title salt, [Pd(C₆H₄N₂)₄](CF₃SO₃)₂, comprises Pd(4-cyanopyridine)₄ dications balanced by two trifluoromethanesulfonate anions. The Pd^II atom lies in a square-planar geometry defined by four N atoms which form equivalent Pd—N interactions. The 4-cyanopyridine ligands are twisted out of the N₄ plane, forming dihedral angles ranging from 66.5 (2) to 89.9 (2)°. In the crystal packing, columns of edge-to-edge dications define channels in which reside the anions. A range of C—H⋯N and C—H⋯O hydrogen-bonding interactions stabilizes the crystal packing.

Related literature

For related palladium(II) complexes with 4-cyanopyridine, see: Kopylovich et al. (2009 ); Lang et al. (2006 ); Taher et al. (2006 ).

Experimental

Crystal data

[Pd(C₆H₄N₂)₄](CF₃O₃S)₂
M_r = 820.99
Monoclinic, P 2₁ /c
a = 18.550 (4) Å
b = 9.2993 (19) Å
c = 20.688 (4) Å
β = 114.55 (3)°
V = 3246.1 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 153 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.829, T_max = 1.000
12799 measured reflections
5478 independent reflections
5000 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.128
S = 1.14
5478 reflections
442 parameters
H-atom parameters constrained
Δρ_max = 1.05 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Table 1
Selected bond lengths (Å)

Pd—N1	2.027 (4)
Pd—N3	2.031 (4)
Pd—N5	2.029 (4)
Pd—N7	2.027 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯N8ⁱ	0.95	2.56	3.489 (8)	166
C5—H5⋯O2	0.95	2.44	3.159 (6)	132
C7—H7⋯O5ⁱⁱ	0.95	2.52	3.202 (6)	129
C8—H8⋯N6ⁱⁱⁱ	0.95	2.53	3.441 (8)	160
C13—H13⋯O5ⁱⁱ	0.95	2.33	3.134 (7)	141
C16—H16⋯N6^iv	0.95	2.61	3.403 (8)	142
C22—H22⋯O3^v	0.95	2.52	3.170 (7)	126
C23—H23⋯O2	0.95	2.34	3.163 (7)	145
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y-1, z; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x, -y+1, -z+1; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810027704/ez2223sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810027704/ez2223Isup2.hkl

checkCIF report

Comment top

While studying the palladium-catalyzed hydration of nitriles, we sought to crystallize palladium(II) complexes with 4-cyanopyridine, similar to those created by Kopylovich et al. (2009), Lang et al. (2006) and Taher et al. (2006). The resulting yellow crystals that formed, (I), were found not to contain any ethylenediamine, but contained a palladium(II) center where the inner coordination sphere is occupied by 4-cyanopyridine ligands.

The molecular structure of (I) comprises a Pd(4-cyanopyridine)₄ dication, Fig. 1, and two trifluoromethanesulfonate anions. The palladium atom lies in a square planar geometry defined by four pyridine-N atoms which form experimentally equivalent Pd–N bond distances, Table 1. The palladium atom lies in the least-squares plane through the N₄ donor set with the r.m.s. deviation for the PdN₄ atoms being 0.021 Å. For steric reasons, each of the 4-cyanopyridine molecules is twisted with respect to the N₄ plane, forming dihedral angles with it of 72.21 (19), 66.5 (2), 80.1 (2), and 89.9 (2) ° for the N1-, N3-, N5-, and N7-pyridine rings, respectively.

In the crystal packing, molecules self-assemble into layers in the ab plane via C–H···N_cyano and C–H···O interactions, Table 2. The resulting 2-D array, Fig. 2, can be described as comprising rows of edge-to-edge complex dications that define channels in which reside the anions, Fig. 3.

Related literature top

For related palladium(II) complexes with 4-cyanopyridine, see: Kopylovich et al. (2009); Lang et al. (2006); Taher et al. (2006).

Experimental top

Pd(ethylenediamine)(trifluoromethanesulfonate)₂ was prepared by adding solid Ag(trifluoromethanesulfonate) to an aqueous solution of Pd(ethylenediamine)Cl₂ (0.050 g, 0.21 mmol). After stirring for 1 h, the mixture was filtered to remove AgCl. 4-Cyanopyridine (0.090 g, 0.85 mmol) was added to the Pd(ethylenediamine)(trifluoromethanesulfonate)₂ solution and heated at 323 K for 2 h. The solution was then allowed to evaporate at room temperature, yielding a yellow solid. X-ray diffraction quality crystals were obtained by vapor diffusion of diethyl ether over a CH₃CN solution of the title complex, (I). (0.026 g, 15% yield). IR (cm^-1, solid): ν(═CH) 3112 (w), 3083(w), 3022(w); ν(CN) 2244 (w); νs(CF₃) 1220 (s), νs(SO₃) 1028 (s). M.pt.: 498 K (dec.) with melting at 523 K.

Structure description top

For related palladium(II) complexes with 4-cyanopyridine, see: Kopylovich et al. (2009); Lang et al. (2006); Taher et al. (2006).

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the cation in (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. Supramolecular 2-D array (I) mediated by C–H···N and C–H···O contacts (blue and orange dashed lines, respectively). Colour code: Pd, orange; S, yellow; O, red; N, blue; C, grey; H, green.
	Fig. 3. Stacking of layers in (I), highlighting the formation of channels by the dications in which reside the anions. The C–H···N and C–H···O contacts are shown as blue and orange dashed lines, respectively. Colour code: Pd, orange; S, yellow; O, red; N, blue; C, grey; H, green.

Tetrakis(4-cyanopyridine)palladium(II) bis(trifluoromethanesulfonate) top

Crystal data top

[Pd(C₆H₄N₂)₄](CF₃O₃S)₂	F(000) = 1632
M_r = 820.99	D_x = 1.680 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4545 reflections
a = 18.550 (4) Å	θ = 2.4–26.7°
b = 9.2993 (19) Å	µ = 0.79 mm⁻¹
c = 20.688 (4) Å	T = 153 K
β = 114.55 (3)°	Block, pale-yellow
V = 3246.1 (14) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	5478 independent reflections
Radiation source: fine-focus sealed tube	5000 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −22→20
T_min = 0.829, T_max = 1.000	k = −9→11
12799 measured reflections	l = −24→22

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0534P)² + 6.3187P] where P = (F_o² + 2F_c²)/3
5478 reflections	(Δ/σ)_max = 0.001
442 parameters	Δρ_max = 1.05 e Å⁻³
0 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

[Pd(C₆H₄N₂)₄](CF₃O₃S)₂	V = 3246.1 (14) Å³
M_r = 820.99	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.550 (4) Å	µ = 0.79 mm⁻¹
b = 9.2993 (19) Å	T = 153 K
c = 20.688 (4) Å	0.20 × 0.20 × 0.20 mm
β = 114.55 (3)°

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	5478 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	5000 reflections with I > 2σ(I)
T_min = 0.829, T_max = 1.000	R_int = 0.035
12799 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.14	Δρ_max = 1.05 e Å⁻³
5478 reflections	Δρ_min = −0.74 e Å⁻³
442 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 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
Pd	0.254695 (18)	0.02757 (4)	0.766848 (17)	0.02851 (14)
S1	0.39867 (7)	0.39076 (14)	0.77597 (7)	0.0421 (3)
S2	0.11861 (7)	0.66442 (14)	0.77812 (7)	0.0384 (3)
F1	0.3763 (3)	0.3677 (5)	0.6440 (2)	0.0951 (14)
F2	0.4595 (3)	0.5294 (4)	0.7007 (3)	0.0944 (14)
F3	0.4938 (3)	0.3095 (5)	0.7191 (2)	0.0874 (13)
F4	−0.03138 (19)	0.7372 (4)	0.7237 (2)	0.0733 (10)
F5	−0.0103 (2)	0.5195 (4)	0.7061 (3)	0.0954 (15)
F6	0.0144 (2)	0.6830 (5)	0.64715 (19)	0.0856 (12)
O1	0.3355 (2)	0.4938 (4)	0.7542 (2)	0.0559 (10)
O2	0.3714 (2)	0.2450 (4)	0.7711 (2)	0.0571 (10)
O3	0.4674 (2)	0.4248 (5)	0.8390 (2)	0.0701 (13)
O4	0.1119 (2)	0.6364 (5)	0.8435 (2)	0.0661 (12)
O5	0.1394 (2)	0.8100 (4)	0.7697 (2)	0.0499 (9)
O6	0.1616 (2)	0.5589 (4)	0.7574 (2)	0.0545 (10)
N1	0.3470 (2)	−0.0809 (4)	0.84066 (18)	0.0300 (8)
N2	0.5954 (3)	−0.3914 (7)	1.0098 (3)	0.0771 (17)
N3	0.2329 (2)	0.1341 (4)	0.84253 (19)	0.0306 (8)
N4	0.1540 (3)	0.4235 (6)	1.0271 (3)	0.0672 (14)
N5	0.1614 (2)	0.1304 (4)	0.69095 (19)	0.0316 (8)
N6	−0.0892 (3)	0.4022 (6)	0.4987 (3)	0.0653 (14)
N7	0.2771 (2)	−0.0774 (4)	0.69126 (19)	0.0318 (8)
N8	0.3503 (3)	−0.3732 (6)	0.5062 (2)	0.0570 (12)
C1	0.3401 (3)	−0.2230 (5)	0.8488 (2)	0.0354 (10)
H1	0.2905	−0.2682	0.8230	0.042*
C2	0.4029 (3)	−0.3051 (5)	0.8936 (2)	0.0392 (11)
H2	0.3966	−0.4052	0.8988	0.047*
C3	0.4752 (3)	−0.2391 (6)	0.9307 (2)	0.0380 (11)
C4	0.4820 (3)	−0.0920 (6)	0.9233 (2)	0.0405 (11)
H4	0.5310	−0.0444	0.9490	0.049*
C5	0.4169 (3)	−0.0165 (5)	0.8782 (2)	0.0349 (10)
H5	0.4215	0.0843	0.8735	0.042*
C6	0.5424 (3)	−0.3230 (6)	0.9757 (3)	0.0501 (13)
C7	0.2062 (3)	0.0623 (6)	0.8847 (2)	0.0399 (11)
H7	0.2007	−0.0392	0.8804	0.048*
C8	0.1865 (3)	0.1317 (6)	0.9340 (3)	0.0437 (12)
H8	0.1679	0.0793	0.9634	0.052*
C9	0.1945 (3)	0.2796 (5)	0.9396 (2)	0.0360 (11)
C10	0.2225 (3)	0.3537 (5)	0.8974 (2)	0.0374 (11)
H10	0.2288	0.4552	0.9011	0.045*
C11	0.2414 (3)	0.2758 (5)	0.8491 (2)	0.0364 (11)
H11	0.2610	0.3258	0.8197	0.044*
C12	0.1719 (3)	0.3602 (6)	0.9892 (3)	0.0493 (13)
C13	0.0912 (3)	0.0632 (6)	0.6598 (3)	0.0390 (11)
H13	0.0869	−0.0332	0.6731	0.047*
C14	0.0258 (3)	0.1282 (6)	0.6098 (3)	0.0419 (12)
H14	−0.0230	0.0779	0.5882	0.050*
C15	0.0324 (3)	0.2699 (6)	0.5912 (2)	0.0424 (12)
C16	0.1042 (3)	0.3394 (6)	0.6227 (3)	0.0460 (12)
H16	0.1096	0.4360	0.6105	0.055*
C17	0.1682 (3)	0.2669 (5)	0.6723 (2)	0.0406 (11)
H17	0.2179	0.3142	0.6938	0.049*
C18	−0.0355 (3)	0.3426 (6)	0.5394 (3)	0.0514 (14)
C19	0.2442 (3)	−0.2063 (5)	0.6675 (2)	0.0383 (11)
H19	0.2079	−0.2450	0.6845	0.046*
C20	0.2615 (3)	−0.2836 (6)	0.6192 (3)	0.0425 (12)
H20	0.2377	−0.3746	0.6028	0.051*
C21	0.3145 (3)	−0.2260 (5)	0.5948 (2)	0.0370 (11)
C22	0.3479 (3)	−0.0935 (6)	0.6189 (3)	0.0453 (12)
H22	0.3839	−0.0519	0.6024	0.054*
C23	0.3278 (3)	−0.0227 (6)	0.6675 (3)	0.0426 (12)
H23	0.3509	0.0684	0.6847	0.051*
C24	0.3344 (3)	−0.3078 (6)	0.5450 (3)	0.0462 (13)
C25	0.4345 (4)	0.4002 (7)	0.7071 (4)	0.0596 (16)
C26	0.0176 (3)	0.6496 (6)	0.7111 (3)	0.0548 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd	0.0277 (2)	0.0264 (2)	0.0324 (2)	0.00416 (13)	0.01340 (16)	0.00318 (13)
S1	0.0410 (7)	0.0374 (7)	0.0541 (7)	−0.0029 (6)	0.0259 (6)	−0.0035 (6)
S2	0.0339 (6)	0.0349 (7)	0.0495 (7)	0.0020 (5)	0.0202 (5)	0.0073 (5)
F1	0.120 (4)	0.117 (4)	0.054 (2)	−0.012 (3)	0.042 (2)	−0.002 (2)
F2	0.125 (4)	0.060 (3)	0.141 (4)	−0.020 (2)	0.098 (3)	0.008 (2)
F3	0.105 (3)	0.089 (3)	0.106 (3)	0.034 (3)	0.081 (3)	0.019 (2)
F4	0.0419 (18)	0.072 (3)	0.097 (3)	0.0145 (18)	0.0206 (18)	−0.004 (2)
F5	0.059 (2)	0.055 (2)	0.155 (4)	−0.0209 (19)	0.027 (3)	−0.007 (2)
F6	0.069 (2)	0.119 (4)	0.053 (2)	−0.011 (2)	0.0098 (18)	−0.002 (2)
O1	0.051 (2)	0.045 (2)	0.075 (3)	0.0109 (18)	0.029 (2)	−0.0001 (19)
O2	0.072 (3)	0.038 (2)	0.078 (3)	−0.0120 (19)	0.048 (2)	0.0012 (19)
O3	0.045 (2)	0.097 (4)	0.063 (3)	−0.002 (2)	0.017 (2)	−0.026 (3)
O4	0.060 (2)	0.092 (3)	0.060 (2)	0.019 (2)	0.038 (2)	0.026 (2)
O5	0.041 (2)	0.038 (2)	0.066 (2)	−0.0062 (16)	0.0177 (18)	0.0011 (17)
O6	0.048 (2)	0.048 (2)	0.074 (3)	0.0121 (18)	0.032 (2)	0.002 (2)
N1	0.0284 (19)	0.031 (2)	0.0310 (19)	0.0028 (16)	0.0124 (16)	−0.0009 (16)
N2	0.047 (3)	0.080 (4)	0.086 (4)	0.017 (3)	0.009 (3)	0.031 (3)
N3	0.0274 (18)	0.029 (2)	0.0354 (19)	0.0015 (16)	0.0130 (16)	0.0055 (16)
N4	0.080 (4)	0.079 (4)	0.057 (3)	0.001 (3)	0.042 (3)	−0.014 (3)
N5	0.032 (2)	0.029 (2)	0.0340 (19)	0.0043 (16)	0.0146 (16)	0.0028 (16)
N6	0.058 (3)	0.064 (3)	0.058 (3)	0.018 (3)	0.007 (3)	0.010 (3)
N7	0.0269 (19)	0.033 (2)	0.0353 (19)	0.0051 (16)	0.0123 (16)	0.0062 (17)
N8	0.063 (3)	0.065 (3)	0.049 (3)	0.010 (3)	0.030 (2)	−0.005 (2)
C1	0.032 (2)	0.031 (3)	0.041 (2)	−0.001 (2)	0.013 (2)	−0.002 (2)
C2	0.043 (3)	0.031 (3)	0.039 (3)	0.007 (2)	0.013 (2)	0.002 (2)
C3	0.035 (3)	0.045 (3)	0.032 (2)	0.011 (2)	0.012 (2)	0.005 (2)
C4	0.030 (2)	0.051 (3)	0.038 (3)	−0.003 (2)	0.011 (2)	0.000 (2)
C5	0.039 (3)	0.032 (3)	0.036 (2)	−0.001 (2)	0.018 (2)	0.002 (2)
C6	0.037 (3)	0.055 (4)	0.051 (3)	0.008 (3)	0.011 (2)	0.009 (3)
C7	0.043 (3)	0.038 (3)	0.040 (3)	−0.001 (2)	0.019 (2)	0.004 (2)
C8	0.049 (3)	0.048 (3)	0.040 (3)	−0.005 (2)	0.025 (2)	0.000 (2)
C9	0.032 (2)	0.046 (3)	0.029 (2)	0.004 (2)	0.0117 (19)	0.000 (2)
C10	0.040 (3)	0.033 (3)	0.038 (2)	0.006 (2)	0.016 (2)	−0.001 (2)
C11	0.041 (3)	0.032 (3)	0.041 (3)	0.001 (2)	0.021 (2)	0.006 (2)
C12	0.052 (3)	0.057 (4)	0.043 (3)	0.001 (3)	0.024 (3)	−0.003 (3)
C13	0.039 (3)	0.038 (3)	0.043 (3)	0.005 (2)	0.019 (2)	0.008 (2)
C14	0.035 (3)	0.048 (3)	0.043 (3)	0.003 (2)	0.016 (2)	0.005 (2)
C15	0.044 (3)	0.047 (3)	0.036 (2)	0.017 (2)	0.017 (2)	0.003 (2)
C16	0.053 (3)	0.031 (3)	0.044 (3)	0.005 (2)	0.009 (2)	0.006 (2)
C17	0.042 (3)	0.034 (3)	0.039 (3)	0.003 (2)	0.009 (2)	0.001 (2)
C18	0.051 (3)	0.049 (3)	0.046 (3)	0.015 (3)	0.011 (3)	0.002 (3)
C19	0.043 (3)	0.038 (3)	0.042 (3)	−0.007 (2)	0.026 (2)	−0.007 (2)
C20	0.048 (3)	0.036 (3)	0.046 (3)	−0.009 (2)	0.022 (2)	−0.007 (2)
C21	0.036 (2)	0.040 (3)	0.034 (2)	0.010 (2)	0.014 (2)	0.003 (2)
C22	0.048 (3)	0.044 (3)	0.055 (3)	−0.005 (2)	0.032 (3)	−0.002 (2)
C23	0.046 (3)	0.036 (3)	0.055 (3)	−0.007 (2)	0.030 (3)	−0.005 (2)
C24	0.049 (3)	0.052 (3)	0.041 (3)	0.008 (3)	0.022 (2)	0.001 (2)
C25	0.076 (4)	0.044 (4)	0.077 (4)	−0.003 (3)	0.050 (4)	0.002 (3)
C26	0.047 (3)	0.044 (3)	0.073 (4)	−0.007 (3)	0.024 (3)	−0.002 (3)

Geometric parameters (Å, º) top

Pd—N1	2.027 (4)	C2—H2	0.9500
Pd—N3	2.031 (4)	C3—C4	1.388 (7)
Pd—N5	2.029 (4)	C3—C6	1.437 (7)
Pd—N7	2.027 (4)	C4—C5	1.373 (7)
S1—O3	1.430 (4)	C4—H4	0.9500
S1—O1	1.434 (4)	C5—H5	0.9500
S1—O2	1.435 (4)	C7—C8	1.377 (7)
S1—C25	1.808 (6)	C7—H7	0.9500
S2—O4	1.433 (4)	C8—C9	1.383 (7)
S2—O5	1.438 (4)	C8—H8	0.9500
S2—O6	1.439 (4)	C9—C10	1.372 (7)
S2—C26	1.815 (6)	C9—C12	1.465 (7)
F1—C25	1.338 (8)	C10—C11	1.392 (6)
F2—C25	1.313 (7)	C10—H10	0.9500
F3—C25	1.325 (7)	C11—H11	0.9500
F4—C26	1.325 (7)	C13—C14	1.366 (7)
F5—C26	1.304 (7)	C13—H13	0.9500
F6—C26	1.335 (7)	C14—C15	1.393 (7)
N1—C5	1.344 (6)	C14—H14	0.9500
N1—C1	1.345 (6)	C15—C16	1.377 (7)
N2—C6	1.137 (7)	C15—C18	1.439 (7)
N3—C11	1.327 (6)	C16—C17	1.379 (7)
N3—C7	1.346 (6)	C16—H16	0.9500
N4—C12	1.135 (7)	C17—H17	0.9500
N5—C13	1.343 (6)	C19—C20	1.373 (7)
N5—C17	1.347 (6)	C19—H19	0.9500
N6—C18	1.146 (7)	C20—C21	1.385 (7)
N7—C23	1.330 (6)	C20—H20	0.9500
N7—C19	1.342 (6)	C21—C22	1.376 (7)
N8—C24	1.140 (6)	C21—C24	1.447 (7)
C1—C2	1.379 (6)	C22—C23	1.377 (7)
C1—H1	0.9500	C22—H22	0.9500
C2—C3	1.380 (7)	C23—H23	0.9500

N1—Pd—N7	87.80 (14)	C10—C9—C12	118.8 (5)
N1—Pd—N5	178.15 (15)	C8—C9—C12	121.1 (4)
N7—Pd—N5	90.70 (14)	C9—C10—C11	118.0 (5)
N1—Pd—N3	92.21 (14)	C9—C10—H10	121.0
N7—Pd—N3	179.53 (15)	C11—C10—H10	121.0
N5—Pd—N3	89.29 (14)	N3—C11—C10	122.4 (4)
O3—S1—O1	116.1 (3)	N3—C11—H11	118.8
O3—S1—O2	115.4 (3)	C10—C11—H11	118.8
O1—S1—O2	113.0 (2)	N4—C12—C9	179.4 (7)
O3—S1—C25	103.2 (3)	N5—C13—C14	122.4 (5)
O1—S1—C25	103.9 (3)	N5—C13—H13	118.8
O2—S1—C25	102.9 (3)	C14—C13—H13	118.8
O4—S2—O5	114.7 (3)	C13—C14—C15	118.5 (5)
O4—S2—O6	115.7 (3)	C13—C14—H14	120.8
O5—S2—O6	113.4 (2)	C15—C14—H14	120.8
O4—S2—C26	103.9 (3)	C16—C15—C14	119.4 (5)
O5—S2—C26	102.8 (2)	C16—C15—C18	120.5 (5)
O6—S2—C26	104.2 (3)	C14—C15—C18	120.1 (5)
C5—N1—C1	119.0 (4)	C15—C16—C17	119.2 (5)
C5—N1—Pd	121.6 (3)	C15—C16—H16	120.4
C1—N1—Pd	119.3 (3)	C17—C16—H16	120.4
C11—N3—C7	119.1 (4)	N5—C17—C16	121.3 (5)
C11—N3—Pd	120.7 (3)	N5—C17—H17	119.4
C7—N3—Pd	120.2 (3)	C16—C17—H17	119.4
C13—N5—C17	119.2 (4)	N6—C18—C15	179.0 (6)
C13—N5—Pd	119.8 (3)	N7—C19—C20	121.7 (4)
C17—N5—Pd	121.0 (3)	N7—C19—H19	119.1
C23—N7—C19	119.3 (4)	C20—C19—H19	119.1
C23—N7—Pd	120.2 (3)	C19—C20—C21	118.6 (5)
C19—N7—Pd	120.4 (3)	C19—C20—H20	120.7
N1—C1—C2	122.0 (4)	C21—C20—H20	120.7
N1—C1—H1	119.0	C22—C21—C20	119.7 (4)
C2—C1—H1	119.0	C22—C21—C24	121.3 (5)
C1—C2—C3	118.8 (5)	C20—C21—C24	119.1 (5)
C1—C2—H2	120.6	C21—C22—C23	118.3 (5)
C3—C2—H2	120.6	C21—C22—H22	120.8
C2—C3—C4	119.2 (4)	C23—C22—H22	120.8
C2—C3—C6	120.0 (5)	N7—C23—C22	122.3 (5)
C4—C3—C6	120.8 (5)	N7—C23—H23	118.8
C5—C4—C3	119.0 (5)	C22—C23—H23	118.8
C5—C4—H4	120.5	N8—C24—C21	179.4 (6)
C3—C4—H4	120.5	F2—C25—F3	107.5 (5)
N1—C5—C4	122.0 (5)	F2—C25—F1	106.5 (6)
N1—C5—H5	119.0	F3—C25—F1	108.1 (5)
C4—C5—H5	119.0	F2—C25—S1	112.5 (4)
N2—C6—C3	178.1 (7)	F3—C25—S1	111.7 (4)
N3—C7—C8	121.9 (5)	F1—C25—S1	110.2 (4)
N3—C7—H7	119.0	F5—C26—F4	107.6 (5)
C8—C7—H7	119.0	F5—C26—F6	106.6 (5)
C7—C8—C9	118.5 (5)	F4—C26—F6	107.5 (5)
C7—C8—H8	120.8	F5—C26—S2	112.4 (4)
C9—C8—H8	120.8	F4—C26—S2	112.2 (4)
C10—C9—C8	120.1 (4)	F6—C26—S2	110.3 (4)

N7—Pd—N1—C5	105.2 (3)	Pd—N5—C13—C14	178.3 (4)
N3—Pd—N1—C5	−74.3 (3)	N5—C13—C14—C15	−0.7 (7)
N7—Pd—N1—C1	−70.1 (3)	C13—C14—C15—C16	0.9 (7)
N3—Pd—N1—C1	110.4 (3)	C13—C14—C15—C18	−179.2 (5)
N1—Pd—N3—C11	115.5 (4)	C14—C15—C16—C17	−0.2 (7)
N5—Pd—N3—C11	−65.6 (4)	C18—C15—C16—C17	179.9 (5)
N1—Pd—N3—C7	−67.5 (3)	C13—N5—C17—C16	0.9 (7)
N5—Pd—N3—C7	111.5 (3)	Pd—N5—C17—C16	−177.5 (4)
N7—Pd—N5—C13	81.3 (3)	C15—C16—C17—N5	−0.7 (8)
N3—Pd—N5—C13	−99.2 (3)	C23—N7—C19—C20	0.1 (7)
N7—Pd—N5—C17	−100.3 (4)	Pd—N7—C19—C20	−176.4 (4)
N3—Pd—N5—C17	79.2 (4)	N7—C19—C20—C21	0.0 (7)
N1—Pd—N7—C23	−88.8 (4)	C19—C20—C21—C22	−0.4 (7)
N5—Pd—N7—C23	92.3 (4)	C19—C20—C21—C24	178.8 (5)
N1—Pd—N7—C19	87.7 (4)	C20—C21—C22—C23	0.7 (7)
N5—Pd—N7—C19	−91.3 (4)	C24—C21—C22—C23	−178.5 (5)
C5—N1—C1—C2	−1.2 (7)	C19—N7—C23—C22	0.2 (7)
Pd—N1—C1—C2	174.3 (3)	Pd—N7—C23—C22	176.7 (4)
N1—C1—C2—C3	−0.5 (7)	C21—C22—C23—N7	−0.6 (8)
C1—C2—C3—C4	1.6 (7)	O3—S1—C25—F2	−62.4 (6)
C1—C2—C3—C6	−177.7 (5)	O1—S1—C25—F2	59.2 (6)
C2—C3—C4—C5	−1.1 (7)	O2—S1—C25—F2	177.3 (5)
C6—C3—C4—C5	178.2 (4)	O3—S1—C25—F3	58.7 (5)
C1—N1—C5—C4	1.7 (7)	O1—S1—C25—F3	−179.7 (4)
Pd—N1—C5—C4	−173.6 (3)	O2—S1—C25—F3	−61.6 (5)
C3—C4—C5—N1	−0.6 (7)	O3—S1—C25—F1	178.8 (4)
C11—N3—C7—C8	0.7 (7)	O1—S1—C25—F1	−59.5 (5)
Pd—N3—C7—C8	−176.3 (4)	O2—S1—C25—F1	58.5 (5)
N3—C7—C8—C9	0.2 (7)	O4—S2—C26—F5	−65.3 (5)
C7—C8—C9—C10	−0.9 (7)	O5—S2—C26—F5	174.8 (5)
C7—C8—C9—C12	177.8 (5)	O6—S2—C26—F5	56.3 (5)
C8—C9—C10—C11	0.6 (7)	O4—S2—C26—F4	56.1 (5)
C12—C9—C10—C11	−178.0 (4)	O5—S2—C26—F4	−63.8 (5)
C7—N3—C11—C10	−1.0 (7)	O6—S2—C26—F4	177.7 (4)
Pd—N3—C11—C10	176.1 (3)	O4—S2—C26—F6	175.9 (4)
C9—C10—C11—N3	0.3 (7)	O5—S2—C26—F6	56.0 (5)
C17—N5—C13—C14	−0.2 (7)	O6—S2—C26—F6	−62.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N8ⁱ	0.95	2.56	3.489 (8)	166
C5—H5···O2	0.95	2.44	3.159 (6)	132
C7—H7···O5ⁱⁱ	0.95	2.52	3.202 (6)	129
C8—H8···N6ⁱⁱⁱ	0.95	2.53	3.441 (8)	160
C13—H13···O5ⁱⁱ	0.95	2.33	3.134 (7)	141
C16—H16···N6^iv	0.95	2.61	3.403 (8)	142
C22—H22···O3^v	0.95	2.52	3.170 (7)	126
C23—H23···O2	0.95	2.34	3.163 (7)	145

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

Experimental details

Crystal data
Chemical formula	[Pd(C₆H₄N₂)₄](CF₃O₃S)₂
M_r	820.99
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	18.550 (4), 9.2993 (19), 20.688 (4)
β (°)	114.55 (3)
V (Å³)	3246.1 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.79
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku AFC12K/SATURN724
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.829, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12799, 5478, 5000
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.128, 1.14
No. of reflections	5478
No. of parameters	442
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.05, −0.74

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Pd—N1	2.027 (4)	Pd—N5	2.029 (4)
Pd—N3	2.031 (4)	Pd—N7	2.027 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N8ⁱ	0.95	2.56	3.489 (8)	166
C5—H5···O2	0.95	2.44	3.159 (6)	132
C7—H7···O5ⁱⁱ	0.95	2.52	3.202 (6)	129
C8—H8···N6ⁱⁱⁱ	0.95	2.53	3.441 (8)	160
C13—H13···O5ⁱⁱ	0.95	2.33	3.134 (7)	141
C16—H16···N6^iv	0.95	2.61	3.403 (8)	142
C22—H22···O3^v	0.95	2.52	3.170 (7)	126
C23—H23···O2	0.95	2.34	3.163 (7)	145

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

Footnotes

‡Additional correspondence author, e-mail: adrian@uiwtx.edu.

§Additional correspondence author, e-mail: judith.walmsley@utsa.edu.

Acknowledgements

This research was supported by National Institutes of Health grant No. SO6–08194. The authors also appreciate the support of the Chemistry Department at The University of the Incarnate Word.

References

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