Tetra­ethyl­ammonium (aceto­nitrile)­tri­chlorido­palladate(II)

Oberley, A.J.; Kadel, L.R.; Senaratne, N.K.; Eichhorn, D.M.

doi:10.1107/S2414314618007502

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 5| May 2018| x180750

https://doi.org/10.1107/S2414314618007502

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Tetraethylammonium (acetonitrile)trichloridopalladate(II)

Alan J. Oberley,^a,^b Lava R. Kadel,^a Nilmini K. Senaratne ^a and David M. Eichhorn ^a ^*

^aDepartment of Chemistry, Wichita State University, 1845 Fairmount, Wichita, KS 67260-0051, USA, and ^bDivision of Science and Mathematics, Newman University, 3100 McCormick, Wichita, KS 67213, USA
^*Correspondence e-mail: david.eichhorn@wichita.edu

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 17 May 2018; accepted 17 May 2018; online 31 May 2018)

A new square-planar palladium complex salt, (C₈H₂₀N)[PdCl₃(C₂H₃N)], has been formed with one of the Cl atoms in tetrachloridopalladate(II) replaced by an acetonitrile coordinated through the N atom. This compound could be a useful precursor for synthesis of palladium complexes. The complex salt crystallizes in the monoclinic P2₁/c space group.

Keywords: crystal structure; palladium.

CCDC reference: 1843858

Structure description

In the title compound (Fig. 1), the palladium is square planar, with three chlorine atoms, and one acetonitrile coordinated through the nitrogen. Charge balance for the monoanionic complex is provided by a tetraethylammonium ion. A search of the Cambridge Structural Database reveals one other complex with a (nitrile)PdCl₃ structure (Chitsaz et al., 2000 ) and ten complexes with the PdCl₃ moiety coordinated by a N donor (Urankar et al., 2010 ; Maronna et al., 2011 ; Gómez-Villarraga et al., 2017 ; Savel'eva et al., 2009 ; Lee et al., 2005 ; von Arnim et al., 1991 ; Kelly et al., 1991 ; Makotchenko & Buidina, 2009 ; Kelly et al., 1995 ; Aragay et al., 2008 ). Structures have also been reported of [(CH₃CN)₂PdCl₂] (Edwards et al., 1998 ; Ramirez de Arellano et al., 2006 ; Malecki, 2013 ; Malecki, 2017 ) and of [(CH₃CN)₃PdCl]⁺ (Demchuk et al., 2011 ). The title compound shows very similar Pd—N and Pd—Cl bond distances (Table 1) to all of the previously reported complexes.

Table 1
Selected geometric parameters (Å, °)

Pd1—Cl1	2.3040 (11)	Pd1—N1	2.024 (3)
Pd1—Cl2	2.2621 (10)	N1—C2	1.108 (5)
Pd1—Cl3	2.2953 (11)

Cl2—Pd1—Cl1	90.44 (3)	Cl3—Pd1—Cl1	177.84 (3)
Cl2—Pd1—Cl3	90.26 (3)	N1—Pd1—Cl2	177.08 (8)
N1—Pd1—Cl1	90.55 (9)	C2—N1—Pd1	171.1 (3)
N1—Pd1—Cl3	88.84 (9)

Figure 1
The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms drawn as spheres of arbitrary radii.

Synthesis and crystallization

The title compound was synthesized by dissolving 0.498 g of 3-ethyl-4-cyanopyrazole in 30 ml of acetonitrile, with some impurities left to settle. The solution was decanted, and added to a solution of 0.15 g of tetraethylammonium tetrachloridopalladate(II) in 50 ml of acetonitrile. The solvent was removed, and the precipitate was redissolved in acetonitrile. Diethyl ether was allowed to diffuse into the acetonitrile solution, and crystals appeared overnight.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	(C₈H₂₀N)[PdCl₃(C₂H₃N)]
M_r	384.05
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	7.286 (2), 17.379 (5), 12.950 (3)
β (°)	102.769 (13)
V (Å³)	1599.3 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.64
Crystal size (mm)	0.63 × 0.57 × 0.31

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Numerical (SADABS; Bruker, 2012 )
T_min, T_max	0.589, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	54175, 3516, 2804
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.092, 1.06
No. of reflections	3516
No. of parameters	150
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.91, −0.61
Computer programs: APEX2 and SAINT (Bruker, 2016 ), SIR2004 (Burla et al., 2007 ), SHELXL (Sheldrick, 2008 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1843858

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618007502/bt4069sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618007502/bt4069Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SIR2004 (Burla et al., 2007); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Tetraethylammonium (acetonitrile)trichloridopalladate(II) top

Crystal data top

(C₈H₂₀N)[PdCl₃(C₂H₃N)]	F(000) = 776
M_r = 384.05	D_x = 1.595 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.286 (2) Å	Cell parameters from 8735 reflections
b = 17.379 (5) Å	θ = 3.2–26.2°
c = 12.950 (3) Å	µ = 1.64 mm⁻¹
β = 102.769 (13)°	T = 150 K
V = 1599.3 (8) Å³	Irregular, reddish brown
Z = 4	0.63 × 0.57 × 0.31 mm

Data collection top

Bruker APEXII CCD diffractometer	3516 independent reflections
Radiation source: sealed X-ray tube	2804 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 5.6 pixels mm^-1	θ_max = 27.2°, θ_min = 3.7°
φ and ω scans	h = −9→9
Absorption correction: numerical (SADABS; Bruker, 2012)	k = −22→22
T_min = 0.589, T_max = 0.746	l = −16→16
54175 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0519P)² + 0.4406P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
3516 reflections	Δρ_max = 0.91 e Å⁻³
150 parameters	Δρ_min = −0.61 e Å⁻³
0 restraints

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	0.25580 (3)	0.43656 (2)	0.67953 (2)	0.03879 (10)
Cl1	0.32497 (12)	0.30742 (5)	0.70147 (6)	0.0518 (2)
Cl2	0.19617 (13)	0.44208 (4)	0.84354 (7)	0.0518 (2)
Cl3	0.19872 (15)	0.56612 (5)	0.65811 (9)	0.0645 (3)
N1	0.2950 (4)	0.43234 (17)	0.5297 (2)	0.0567 (8)
C1	0.2887 (7)	0.4325 (3)	0.3309 (3)	0.0967 (19)
H1A	0.1600	0.4424	0.2911	0.145*
H1B	0.3308	0.3824	0.3100	0.145*
H1C	0.3725	0.4729	0.3154	0.145*
C2	0.2927 (5)	0.4320 (2)	0.4438 (3)	0.0649 (10)
N2	0.2491 (3)	0.80441 (13)	0.48732 (17)	0.0363 (5)
C3	0.5222 (5)	0.8575 (2)	0.4139 (3)	0.0559 (8)
H3A	0.4597	0.8401	0.3428	0.084*
H3B	0.6589	0.8538	0.4223	0.084*
H3C	0.4874	0.9110	0.4235	0.084*
C4	0.4611 (4)	0.80727 (18)	0.4959 (2)	0.0450 (7)
H4A	0.5222	0.8264	0.5672	0.054*
H4B	0.5069	0.7543	0.4894	0.054*
C5	0.0118 (4)	0.74911 (19)	0.5853 (3)	0.0529 (8)
H5A	−0.0551	0.7241	0.5200	0.079*
H5B	−0.0451	0.7994	0.5920	0.079*
H5C	0.0030	0.7170	0.6462	0.079*
C6	0.2159 (4)	0.75965 (17)	0.5818 (2)	0.0441 (7)
H6A	0.2744	0.7082	0.5818	0.053*
H6B	0.2806	0.7865	0.6472	0.053*
C7	0.2554 (5)	0.93366 (18)	0.5807 (3)	0.0600 (9)
H7A	0.1960	0.9846	0.5739	0.090*
H7B	0.3905	0.9393	0.5844	0.090*
H7C	0.2362	0.9087	0.6454	0.090*
C8	0.1677 (4)	0.88483 (17)	0.4855 (3)	0.0499 (8)
H8A	0.0308	0.8807	0.4815	0.060*
H8B	0.1846	0.9114	0.4206	0.060*
C9	0.1992 (5)	0.6812 (2)	0.3746 (3)	0.0612 (9)
H9A	0.1275	0.6610	0.3070	0.092*
H9B	0.1670	0.6521	0.4330	0.092*
H9C	0.3341	0.6760	0.3774	0.092*
C10	0.1512 (5)	0.7654 (2)	0.3845 (2)	0.0532 (8)
H10A	0.0135	0.7698	0.3775	0.064*
H10B	0.1834	0.7938	0.3247	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.03429 (15)	0.03990 (17)	0.04187 (15)	−0.00227 (9)	0.00774 (10)	−0.00026 (9)
Cl1	0.0536 (4)	0.0426 (4)	0.0575 (4)	0.0055 (4)	0.0087 (3)	−0.0088 (3)
Cl2	0.0653 (5)	0.0451 (5)	0.0501 (4)	0.0020 (4)	0.0238 (4)	−0.0034 (3)
Cl3	0.0693 (6)	0.0423 (5)	0.0804 (6)	0.0015 (4)	0.0132 (5)	0.0140 (4)
N1	0.0544 (18)	0.070 (2)	0.0474 (16)	−0.0053 (14)	0.0142 (13)	−0.0013 (13)
C1	0.074 (3)	0.167 (6)	0.054 (2)	−0.021 (3)	0.024 (2)	0.003 (2)
C2	0.053 (2)	0.095 (3)	0.048 (2)	−0.0111 (18)	0.0134 (16)	0.0024 (17)
N2	0.0383 (12)	0.0328 (13)	0.0364 (11)	−0.0015 (10)	0.0056 (9)	0.0030 (9)
C3	0.055 (2)	0.056 (2)	0.0615 (19)	−0.0063 (16)	0.0226 (16)	−0.0014 (16)
C4	0.0394 (16)	0.0444 (18)	0.0496 (16)	−0.0019 (13)	0.0061 (13)	−0.0002 (13)
C5	0.058 (2)	0.048 (2)	0.0550 (17)	−0.0044 (15)	0.0195 (15)	0.0043 (14)
C6	0.0541 (18)	0.0394 (17)	0.0382 (14)	−0.0017 (14)	0.0085 (13)	0.0057 (12)
C7	0.069 (2)	0.0399 (19)	0.077 (2)	−0.0035 (16)	0.030 (2)	−0.0095 (16)
C8	0.0473 (17)	0.0362 (17)	0.0653 (19)	0.0015 (14)	0.0107 (14)	0.0114 (14)
C9	0.059 (2)	0.064 (2)	0.064 (2)	−0.0167 (18)	0.0215 (17)	−0.0266 (17)
C10	0.0543 (19)	0.063 (2)	0.0388 (15)	−0.0153 (17)	0.0036 (13)	−0.0013 (14)

Geometric parameters (Å, º) top

Pd1—Cl1	2.3040 (11)	C5—H5A	0.9800
Pd1—Cl2	2.2621 (10)	C5—H5B	0.9800
Pd1—Cl3	2.2953 (11)	C5—H5C	0.9800
Pd1—N1	2.024 (3)	C5—C6	1.509 (4)
N1—C2	1.108 (5)	C6—H6A	0.9900
C1—H1A	0.9800	C6—H6B	0.9900
C1—H1B	0.9800	C7—H7A	0.9800
C1—H1C	0.9800	C7—H7B	0.9800
C1—C2	1.457 (5)	C7—H7C	0.9800
N2—C4	1.524 (4)	C7—C8	1.517 (5)
N2—C6	1.514 (3)	C8—H8A	0.9900
N2—C8	1.516 (4)	C8—H8B	0.9900
N2—C10	1.524 (4)	C9—H9A	0.9800
C3—H3A	0.9800	C9—H9B	0.9800
C3—H3B	0.9800	C9—H9C	0.9800
C3—H3C	0.9800	C9—C10	1.517 (5)
C3—C4	1.515 (4)	C10—H10A	0.9900
C4—H4A	0.9900	C10—H10B	0.9900
C4—H4B	0.9900

Cl2—Pd1—Cl1	90.44 (3)	H5B—C5—H5C	109.5
Cl2—Pd1—Cl3	90.26 (3)	C6—C5—H5A	109.5
N1—Pd1—Cl1	90.55 (9)	C6—C5—H5B	109.5
N1—Pd1—Cl3	88.84 (9)	C6—C5—H5C	109.5
Cl3—Pd1—Cl1	177.84 (3)	N2—C6—H6A	108.5
N1—Pd1—Cl2	177.08 (8)	N2—C6—H6B	108.5
C2—N1—Pd1	171.1 (3)	C5—C6—N2	114.9 (2)
H1A—C1—H1B	109.5	C5—C6—H6A	108.5
H1A—C1—H1C	109.5	C5—C6—H6B	108.5
H1B—C1—H1C	109.5	H6A—C6—H6B	107.5
C2—C1—H1A	109.5	H7A—C7—H7B	109.5
C2—C1—H1B	109.5	H7A—C7—H7C	109.5
C2—C1—H1C	109.5	H7B—C7—H7C	109.5
N1—C2—C1	179.3 (5)	C8—C7—H7A	109.5
C6—N2—C4	107.4 (2)	C8—C7—H7B	109.5
C6—N2—C8	110.8 (2)	C8—C7—H7C	109.5
C6—N2—C10	110.5 (2)	N2—C8—C7	114.2 (3)
C8—N2—C4	111.0 (2)	N2—C8—H8A	108.7
C8—N2—C10	106.9 (2)	N2—C8—H8B	108.7
C10—N2—C4	110.5 (2)	C7—C8—H8A	108.7
H3A—C3—H3B	109.5	C7—C8—H8B	108.7
H3A—C3—H3C	109.5	H8A—C8—H8B	107.6
H3B—C3—H3C	109.5	H9A—C9—H9B	109.5
C4—C3—H3A	109.5	H9A—C9—H9C	109.5
C4—C3—H3B	109.5	H9B—C9—H9C	109.5
C4—C3—H3C	109.5	C10—C9—H9A	109.5
N2—C4—H4A	108.6	C10—C9—H9B	109.5
N2—C4—H4B	108.6	C10—C9—H9C	109.5
C3—C4—N2	114.7 (2)	N2—C10—H10A	108.4
C3—C4—H4A	108.6	N2—C10—H10B	108.4
C3—C4—H4B	108.6	C9—C10—N2	115.6 (3)
H4A—C4—H4B	107.6	C9—C10—H10A	108.4
H5A—C5—H5B	109.5	C9—C10—H10B	108.4
H5A—C5—H5C	109.5	H10A—C10—H10B	107.4

C4—N2—C6—C5	−178.5 (3)	C8—N2—C4—C3	−52.5 (3)
C4—N2—C8—C7	−57.2 (3)	C8—N2—C6—C5	60.2 (3)
C4—N2—C10—C9	64.6 (3)	C8—N2—C10—C9	−174.6 (3)
C6—N2—C4—C3	−173.7 (3)	C10—N2—C4—C3	65.8 (3)
C6—N2—C8—C7	61.9 (3)	C10—N2—C6—C5	−58.0 (3)
C6—N2—C10—C9	−54.0 (3)	C10—N2—C8—C7	−177.7 (3)

Acknowledgements

AO acknowledges Newman University for providing sabbatical support.

Funding information

Funding for this research was provided by: Newman University; Wichita State University.

References

Aragay, G., Pons, J., García-Antón, J., Solans, X., Font-Bardia, M. & Ros, J. (2008). J. Organomet. Chem. 693, 3396–3404. CrossRef Google Scholar
Arnim, H. von, Massa, W., Zinn, A. & Dehnicke, K. (1991). Z. Naturforsch. Teil B, 46, 992–998. Google Scholar
Bruker (2012). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2016). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G., Siliqi, D. & Spagna, R. (2007). J. Appl. Cryst. 40, 609–613. Web of Science CrossRef CAS IUCr Journals Google Scholar
Chitsaz, S., Neumüller, B. & Dehnicke, K. (2000). Z. Anorg. Allg. Chem. 626, 634–638. CrossRef Google Scholar
Demchuk, O. M., Kielar, K. & Pietrusiewicz, K. M. (2011). Pure Appl. Chem. 83, 633–644. CrossRef Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Edwards, P. G., Paisey, S. J. & Albers, T. (1998). Private communication (refcode: FEQCOT). CCDC, Cambridge, England. Google Scholar
Gómez-Villarraga, F., De Tovar, J., Guerrero, M., Nolis, P., Parella, T., Lecante, P., Romero, N., Escriche, L., Bofill, R., Ros, J., Sala, X., Philippot, K. & García-Antón, J. (2017). Dalton Trans. 46, 11768–11778. Google Scholar
Kelly, P. F. & Slawin, A. M. Z. (1995). Angew. Chem. Int. Ed. Engl. 34, 1758–1759. CSD CrossRef CAS Web of Science Google Scholar
Kelly, P. F., Slawin, A. M. Z., Williams, D. J. & Woollins, J. D. (1991). Polyhedron, 10, 2337–2340. CrossRef Google Scholar
Lee, H. M., Chiu, P. L., Hu, C.-H., Lai, C. L. & Chou, Y.-C. J. (2005). J. Organomet. Chem. 690, 403–414. CrossRef Google Scholar
Makotchenko, E. V. & Buidina, I. A. (2009). Russ. J. Coord. Chem. 35, 212–216. CrossRef Google Scholar
Malecki, J. G. (2013). Private communication (refcode: FEQCOT02). CCDC, Cambridge, England. Google Scholar
Malecki, J. G. (2017). Private communication (refcode: FEQCOT03). CCDC, Cambridge, England. Google Scholar
Maronna, A., Bindewald, E., Kaifer, E., Wadepohl, H. & Himmel, H. J. (2011). Eur. J. Inorg. Chem. pp. 1302–1314. CrossRef Google Scholar
Ramirez de Arellano, R., Asensio, G., Medio-Simon, M., Rodriguez, N. & Mancha, G. (2006). Private communication (refcode: FEQCOT01). CCDC, Cambridge, England. Google Scholar
Savel'eva, Z. A., Glinskaya, L. A., Popov, S. A., Klevtsova, R. F., Tkachev, A. V. & Larionov, S. V. (2009). Russ. J. Coord. Chem. 35, 668–673. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Urankar, D., Pevec, A., Turel, I. & Košmrlj, J. (2010). Cryst. Growth Des. 10, 4920–4927. CrossRef Google Scholar