Diaceto­nitrile­(2,2′-bi­pyridine-κ2N,N′)palladium(II) bis­(tri­fluoro­methane­sulfonate)

Adrian, R.A.; Gutierrez, M.C.; Arman, H.D.

doi:10.1107/S2414314622011518

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 12| December 2022| x221151

https://doi.org/10.1107/S2414314622011518

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Diacetonitrile(2,2′-bipyridine-κ²N,N′)palladium(II) bis(trifluoromethanesulfonate)

Rafael A. Adrian,^a ^* Marcela C. Gutierrez ^a and Hadi D. Arman ^b

^aDepartment of Chemistry and Biochemistry, University of the Incarnate Word, San Antonio, Texas 78209, USA, and ^bDepartment of Chemistry, The University of Texas at San Antonio, San Antonio, Texas 78249, USA
^*Correspondence e-mail: adrian@uiwtx.edu

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 29 November 2022; accepted 30 November 2022; online 6 December 2022)

In the title complex, [Pd(C₁₀H₈N₂)(CH₃CN)₂](CF₃SO₃)₂ or [Pd(bipy)(CH₃CN)₂](CF₃SO₃)₂, the palladium(II) ion is fourfold coordinated by two acetonitrile molecules and a bidentate 2,2′-bipyridine ligand in a distorted square-planar geometry.

Keywords: palladium; crystal structure; 2,2′-bipyridine; 2,2′-dipyridyl; bipy; coordinated acetonitrile; square planar; coordination complex.

CCDC reference: 2223394

Structure description

Palladium(II) complexes of 2,2′-bipyridine continue to be investigated due to their application in catalysis (Kitanosono et al., 2021 ) and remarkable antiproliferative activity against cancer cells (Fatahian-Nezhad et al., 2021 ; Tabrizi et al., 2020 ; Icsel et al., 2015 ). Our research group has been exploring the synthesis of palladium(II) and copper(II) complexes containing various ancillary ligands. With that in mind, herein, we report the synthesis and structure of the title complex, an excellent starting material for synthesizing novel palladium complexes.

The asymmetric unit contains only half of the title complex due to the presence of a vertical plane of symmetry along the a axis that bisects the bond between the pyridine rings, C1—C1ⁱ, and the Pd1, O1, F1, O3, and F4 atoms. The title complex exhibits a Pd^II ion in a distorted square-planar coordination environment defined by two N atoms of the bidentate 2,2′-bipyridine ligand and one nitrogen from each of the two coordinated acetonitrile molecules. Two trifluoromethanesulfonate ions sit outside the coordination sphere of the title complex balancing the charge of the metal (Fig. 1). The Pd—N1 and Pd—N2 bond lengths of 1.999 (2) Å and 2.012 (3) Å, respectively, are in good agreement with the only comparable palladium(II) 2,2′-bipyridine complex, a tetrafluoroborate salt, (1.993 and 2.004 Å) currently available in the CSD (Groom et al., 2016 ; version 5.43 with update of September 2022; refcode WEFCAL; Nesper et al., 1993 ). The N—Pd—N angles also correlate well with the previously referenced complex, with differences of less than one degree in all cases. All relevant bonds and angles are presented in Table 1.

Table 1
Selected geometric parameters (Å, °)

Pd1—N1	1.999 (2)	Pd1—N2	2.012 (3)

N1ⁱ—Pd1—N1	81.82 (14)	N1—Pd1—N2	176.99 (9)
N1—Pd1—N2ⁱ	95.18 (11)	N2—Pd1—N2ⁱ	87.83 (14)
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z]$ .

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level; H atoms are omitted for clarity. Symmetry code: (i) x, −y + $[{3\over 2}]$ , z.

In the molecular packing of the title complex, the palladium(II) complex ions align in layers along the b-axis orienting their coordinated acetonitrile toward the same direction, with the trifluoromethanesulfonate ions occupying the gaps between layers, as shown in Fig. 2. Meanwhile, adjacent layers alternate the orientation of the coordinated acetonitrile molecules. No directional supramolecular interactions are present in the crystal packing of the title compound.

Figure 2
Perspective view of the packing structure of the title complex; H atoms are omitted for clarity.

Synthesis and crystallization

Silver trifluoromethanesulfonate (0.154 g, 0.600 mmol) was added to a 40.0 ml acetonitrile suspension of (2,2′-bipyridine)dichloropalladium(II) (0.100 g, 0.300 mmol). The resulting solution was filtrated using a 0.45 mm PTFE syringe filter and heated at 323 K to reduce the volume to 10.0 ml. Crystals suitable for X-ray diffraction were obtained by vapor diffusion of diethyl ether over the saturated acetonitrile solution of the title complex at 277 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Pd(C₁₀H₈N₂)(C₂H₃N)₂](CF₃O₃S)₂
M_r	642.83
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	100
a, b, c (Å)	9.2732 (3), 12.5307 (2), 10.0983 (3)
β (°)	110.627 (3)
V (Å³)	1098.20 (6)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	9.49
Crystal size (mm)	0.15 × 0.13 × 0.09

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.746, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10720, 2318, 2234
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.093, 1.09
No. of reflections	2318
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.93
Computer programs: CrysAlis PRO (Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2223394

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622011518/vm4055sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622011518/vm4055Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314622011518/vm4055Isup3.mol

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2020); cell refinement: CrysAlis PRO (Rigaku OD, 2020); data reduction: CrysAlis PRO (Rigaku OD, 2020); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

Diacetonitrile(2,2'-bipyridine-κ²N,N')palladium(II) bis(trifluoromethanesulfonate) top

Crystal data top

[Pd(C₁₀H₈N₂)(C₂H₃N)₂](CF₃O₃S)₂	F(000) = 636
M_r = 642.83	D_x = 1.944 Mg m⁻³
Monoclinic, P12₁/m1	Cu Kα radiation, λ = 1.54184 Å
a = 9.2732 (3) Å	Cell parameters from 5466 reflections
b = 12.5307 (2) Å	θ = 4.7–75.7°
c = 10.0983 (3) Å	µ = 9.49 mm⁻¹
β = 110.627 (3)°	T = 100 K
V = 1098.20 (6) Å³	Block, clear colourless
Z = 2	0.15 × 0.13 × 0.09 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	2318 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2234 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.048
Detector resolution: 10.0000 pixels mm^-1	θ_max = 76.3°, θ_min = 4.7°
ω scans	h = −11→11
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2020)	k = −11→15
T_min = 0.746, T_max = 1.000	l = −12→12
10720 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.033	w = 1/[σ²(F_o²) + (0.0618P)² + 0.5328P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.093	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 0.75 e Å⁻³
2318 reflections	Δρ_min = −0.93 e Å⁻³
174 parameters	Extinction correction: SHELXL2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00084 (18)
Primary atom site location: dual

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.

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

	x	y	z	U_iso*/U_eq
Pd1	0.45413 (3)	0.750000	0.68769 (3)	0.01791 (13)
S1	0.95842 (11)	0.750000	0.87020 (10)	0.0194 (2)
S2	0.58391 (11)	0.750000	0.25835 (10)	0.0222 (2)
F1	1.2500 (3)	0.750000	0.8920 (3)	0.0318 (6)
F2	1.0991 (2)	0.66371 (16)	0.7117 (2)	0.0362 (5)
F4	0.8145 (3)	0.750000	0.1642 (3)	0.0343 (6)
F3	0.8599 (2)	0.83614 (19)	0.3585 (2)	0.0455 (5)
O2	0.9882 (2)	0.84692 (17)	0.9529 (2)	0.0240 (4)
O1	0.8188 (3)	0.750000	0.7478 (3)	0.0250 (6)
O3	0.5802 (4)	0.750000	0.3998 (3)	0.0276 (6)
O4	0.5311 (3)	0.65247 (18)	0.1802 (2)	0.0332 (5)
N1	0.3443 (3)	0.64555 (19)	0.5361 (2)	0.0201 (5)
N2	0.5598 (3)	0.8614 (2)	0.8330 (3)	0.0220 (5)
C1	0.2630 (3)	0.6910 (2)	0.4102 (3)	0.0192 (5)
C5	0.3494 (3)	0.5388 (2)	0.5486 (3)	0.0218 (6)
H5	0.405311	0.508152	0.635496	0.026*
C4	0.2733 (4)	0.4734 (2)	0.4351 (3)	0.0254 (6)
H4	0.277737	0.399608	0.445345	0.030*
C6	0.6305 (3)	0.9177 (2)	0.9187 (3)	0.0219 (6)
C2	0.1852 (3)	0.6298 (2)	0.2937 (3)	0.0241 (6)
H2	0.129953	0.662005	0.207740	0.029*
C3	0.1905 (3)	0.5194 (2)	0.3063 (3)	0.0248 (6)
H3	0.138764	0.476742	0.228681	0.030*
C7	0.7208 (4)	0.9927 (2)	1.0251 (3)	0.0255 (6)
H7A	0.688876	1.064212	0.994367	0.038*
H7B	0.827941	0.984372	1.038591	0.038*
H7C	0.705270	0.979190	1.112678	0.038*
C9	0.7904 (5)	0.750000	0.2872 (5)	0.0285 (9)
C8	1.1090 (5)	0.750000	0.7920 (5)	0.0265 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.02209 (19)	0.01259 (19)	0.01685 (19)	0.000	0.00414 (13)	0.000
S1	0.0234 (5)	0.0146 (5)	0.0189 (4)	0.000	0.0057 (4)	0.000
S2	0.0243 (5)	0.0181 (5)	0.0229 (5)	0.000	0.0067 (4)	0.000
F1	0.0236 (13)	0.0283 (14)	0.0400 (14)	0.000	0.0067 (11)	0.000
F2	0.0426 (11)	0.0326 (10)	0.0392 (11)	−0.0031 (9)	0.0217 (9)	−0.0121 (8)
F4	0.0387 (15)	0.0366 (15)	0.0341 (14)	0.000	0.0210 (12)	0.000
F3	0.0350 (11)	0.0549 (13)	0.0496 (13)	−0.0183 (10)	0.0187 (10)	−0.0220 (11)
O2	0.0303 (11)	0.0174 (10)	0.0225 (10)	0.0003 (8)	0.0069 (8)	−0.0030 (8)
O1	0.0236 (14)	0.0221 (15)	0.0248 (14)	0.000	0.0030 (11)	0.000
O3	0.0294 (16)	0.0280 (16)	0.0267 (15)	0.000	0.0113 (13)	0.000
O4	0.0362 (12)	0.0276 (12)	0.0357 (12)	−0.0069 (10)	0.0127 (10)	−0.0090 (9)
N1	0.0230 (11)	0.0161 (11)	0.0202 (11)	−0.0015 (9)	0.0065 (9)	0.0007 (9)
N2	0.0247 (12)	0.0168 (12)	0.0235 (12)	0.0027 (10)	0.0070 (10)	0.0021 (10)
C1	0.0212 (13)	0.0152 (14)	0.0207 (13)	−0.0006 (11)	0.0070 (11)	−0.0001 (10)
C5	0.0257 (14)	0.0171 (14)	0.0209 (13)	−0.0009 (11)	0.0061 (11)	0.0011 (11)
C4	0.0312 (15)	0.0154 (13)	0.0294 (14)	−0.0029 (12)	0.0104 (12)	−0.0021 (11)
C6	0.0251 (14)	0.0174 (14)	0.0205 (13)	0.0012 (11)	0.0045 (11)	0.0029 (11)
C2	0.0263 (14)	0.0219 (15)	0.0221 (13)	−0.0006 (12)	0.0060 (11)	0.0007 (11)
C3	0.0279 (14)	0.0214 (15)	0.0240 (13)	−0.0018 (12)	0.0078 (11)	−0.0048 (11)
C7	0.0281 (15)	0.0195 (14)	0.0249 (14)	−0.0041 (12)	0.0043 (12)	−0.0025 (12)
C9	0.028 (2)	0.029 (2)	0.027 (2)	0.000	0.0092 (18)	0.000
C8	0.028 (2)	0.022 (2)	0.029 (2)	0.000	0.0104 (18)	0.000

Geometric parameters (Å, º) top

Pd1—N1ⁱ	1.999 (2)	N1—C1	1.354 (4)
Pd1—N1	1.999 (2)	N1—C5	1.343 (4)
Pd1—N2	2.012 (3)	N2—C6	1.130 (4)
Pd1—N2ⁱ	2.012 (3)	C1—C1ⁱ	1.480 (5)
S1—O2ⁱ	1.444 (2)	C1—C2	1.376 (4)
S1—O2	1.444 (2)	C5—H5	0.9300
S1—O1	1.441 (3)	C5—C4	1.383 (4)
S1—C8	1.830 (4)	C4—H4	0.9300
S2—O3	1.441 (3)	C4—C3	1.382 (4)
S2—O4ⁱ	1.443 (2)	C6—C7	1.451 (4)
S2—O4	1.444 (2)	C2—H2	0.9300
S2—C9	1.833 (5)	C2—C3	1.389 (4)
F1—C8	1.341 (5)	C3—H3	0.9300
F2—C8	1.335 (3)	C7—H7A	0.9600
F4—C9	1.338 (5)	C7—H7B	0.9600
F3—C9	1.331 (3)	C7—H7C	0.9600

N1ⁱ—Pd1—N1	81.82 (14)	C5—C4—H4	120.5
N1ⁱ—Pd1—N2	95.18 (11)	C3—C4—C5	119.0 (3)
N1—Pd1—N2ⁱ	95.18 (11)	C3—C4—H4	120.5
N1—Pd1—N2	176.99 (9)	N2—C6—C7	178.1 (3)
N1ⁱ—Pd1—N2ⁱ	176.99 (9)	C1—C2—H2	120.5
N2—Pd1—N2ⁱ	87.83 (14)	C1—C2—C3	119.0 (3)
O2—S1—O2ⁱ	114.47 (17)	C3—C2—H2	120.5
O2ⁱ—S1—C8	103.28 (12)	C4—C3—C2	119.4 (3)
O2—S1—C8	103.28 (12)	C4—C3—H3	120.3
O1—S1—O2	115.28 (10)	C2—C3—H3	120.3
O1—S1—O2ⁱ	115.28 (11)	C6—C7—H7A	109.5
O1—S1—C8	102.79 (19)	C6—C7—H7B	109.5
O3—S2—O4ⁱ	114.85 (11)	C6—C7—H7C	109.5
O3—S2—O4	114.85 (11)	H7A—C7—H7B	109.5
O3—S2—C9	103.35 (19)	H7A—C7—H7C	109.5
O4ⁱ—S2—O4	115.7 (2)	H7B—C7—H7C	109.5
O4ⁱ—S2—C9	102.76 (12)	F4—C9—S2	111.1 (3)
O4—S2—C9	102.75 (12)	F3—C9—S2	111.4 (2)
C1—N1—Pd1	114.14 (18)	F3ⁱ—C9—S2	111.4 (2)
C5—N1—Pd1	126.1 (2)	F3—C9—F4	107.2 (2)
C5—N1—C1	119.8 (2)	F3ⁱ—C9—F4	107.2 (2)
C6—N2—Pd1	173.7 (2)	F3—C9—F3ⁱ	108.4 (4)
N1—C1—C1ⁱ	114.85 (15)	F1—C8—S1	111.4 (3)
N1—C1—C2	121.3 (2)	F2ⁱ—C8—S1	111.2 (2)
C2—C1—C1ⁱ	123.82 (17)	F2—C8—S1	111.2 (2)
N1—C5—H5	119.3	F2—C8—F1	107.3 (2)
N1—C5—C4	121.4 (3)	F2ⁱ—C8—F1	107.3 (2)
C4—C5—H5	119.3	F2ⁱ—C8—F2	108.2 (3)

Pd1—N1—C1—C1ⁱ	−3.37 (19)	O4—S2—C9—F4	60.23 (11)
Pd1—N1—C1—C2	177.7 (2)	O4ⁱ—S2—C9—F4	−60.23 (11)
Pd1—N1—C5—C4	−177.6 (2)	O4—S2—C9—F3ⁱ	−59.2 (3)
O2ⁱ—S1—C8—F1	−59.77 (10)	O4ⁱ—S2—C9—F3	59.2 (3)
O2—S1—C8—F1	59.77 (10)	O4ⁱ—S2—C9—F3ⁱ	−179.6 (2)
O2ⁱ—S1—C8—F2ⁱ	−179.4 (2)	O4—S2—C9—F3	179.6 (2)
O2—S1—C8—F2ⁱ	−59.9 (3)	N1—C1—C2—C3	0.1 (4)
O2—S1—C8—F2	179.4 (2)	N1—C5—C4—C3	0.1 (4)
O2ⁱ—S1—C8—F2	59.9 (3)	C1—N1—C5—C4	0.1 (4)
O1—S1—C8—F1	180.000 (1)	C1ⁱ—C1—C2—C3	−178.68 (19)
O1—S1—C8—F2	−60.3 (2)	C1—C2—C3—C4	0.1 (4)
O1—S1—C8—F2ⁱ	60.3 (2)	C5—N1—C1—C1ⁱ	178.68 (19)
O3—S2—C9—F4	180.000 (1)	C5—N1—C1—C2	−0.2 (4)
O3—S2—C9—F3	−60.6 (2)	C5—C4—C3—C2	−0.2 (4)
O3—S2—C9—F3ⁱ	60.6 (2)

Symmetry code: (i) x, −y+3/2, z.

Acknowledgements

We are thankful for the support of the Department of Chemistry and Biochemistry at the University of the Incarnate Word and the X-ray Diffraction Laboratory at the University of Texas at San Antonio.

Funding information

Funding for this research was provided by: National Science Foundation (award No. 1920059); Welch Foundation (award No. BN0032).

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