Tetra­amminepalladium(II) dichloride ammonia tetra­solvate

Grassl, T.; Korber, N.

doi:10.1107/S1600536814012355

inorganic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 7| July 2014| Page i32

https://doi.org/10.1107/S1600536814012355

Open

access

Tetraamminepalladium(II) dichloride ammonia tetrasolvate

Tobias Grassl ^a and Nikolaus Korber ^a ^*

^aInstitut für Anorganische Chemie, Universität Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany
^*Correspondence e-mail: nikolaus.korber@chemie.uni-regensburg.de

(Received 25 April 2014; accepted 27 May 2014; online 7 June 2014)

The title compound, [Pd(NH₃)₄]Cl₂·4NH₃, was crystallized in liquid ammonia from the salt Pd(en)Cl₂ (en is ethylenediamine) and is isotypic with [Pt(NH₃)₄]Cl₂·4NH₃ [Grassl & Korber (2014 ). Acta Cryst. E70, i31]. The Pd²⁺ cation is coordinated by four ammonia molecules, exhibiting a square-planar geometry. The chloride anions are surrounded by nine ammonia molecules. These are either bound in the palladium complex or solvent molecules. The packing of the ammonia solvent molecules enables the formation of an extended network of N—H⋯N and N—H⋯Cl interactions with nearly ideal hydrogen-bonding geometry.

CCDC reference: 1005539

Related literature

For weak intermolecular interactions such as hydrogen bonds and their application in crystal engeneering, see: Desiraju (2002 ); Desiraju (2007 ); Steiner (2002 ). For the structure of tetraamminepalladium(II) chloride monoydrate and complexation of palladium by carbohydrates, see: Bell et al. (1976 ); Ahlrichs et al. (1998 ). The structure of the platinum analogue is given by Grassl & Korber (2014)

Experimental

Crystal data

[Pd(NH₃)₄]Cl₂·4NH₃
M_r = 313.58
Monoclinic, P 2₁ /n
a = 7.6856 (5) Å
b = 10.1505 (7) Å
c = 8.7170 (6) Å
β = 100.384 (7)°
V = 668.90 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.76 mm⁻¹
T = 123 K
0.32 × 0.29 × 0.23 mm

Data collection

Agilent Xcalibur (Ruby, Gemini ultra) diffractometer
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012 ), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995 )] T_min = 0.649, T_max = 0.741
2418 measured reflections
1266 independent reflections
1076 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.058
S = 1.06
1266 reflections
100 parameters
All H-atom parameters refined
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1	0.86 (4)	2.49 (4)	3.351 (3)	175 (3)
N1—H1B⋯Cl1ⁱ	0.85 (3)	2.49 (4)	3.328 (3)	171 (3)
N2—H2A⋯N3ⁱⁱ	1.03 (4)	2.02 (4)	3.025 (5)	163 (3)
N1—H1C⋯N4	0.96 (4)	2.02 (5)	2.975 (5)	170 (3)
N2—H2B⋯Cl1ⁱ	0.73 (3)	2.66 (3)	3.384 (4)	172 (3)
N2—H2C⋯Cl1ⁱⁱⁱ	0.88 (5)	2.62 (5)	3.463 (3)	162 (4)
N3—H3A⋯Cl1	0.83 (3)	2.83 (3)	3.563 (4)	148 (3)
N4—H4A⋯Cl1^iv	0.91 (4)	2.65 (4)	3.563 (4)	173 (3)
N4—H4B⋯Cl1^v	1.00 (5)	2.61 (5)	3.606 (4)	174 (4)
N3—H3B⋯Cl1^vi	0.89 (5)	2.71 (5)	3.578 (4)	163 (3)
N3—H3C⋯Cl1^vii	1.09 (5)	2.48 (5)	3.535 (4)	162 (4)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z; (iii) -x, -y+1, -z; (iv) x+1, y, z; (v) -x+1, -y+1, -z+1; (vi) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (vii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: OLEX2.solve (Bourhis et al., 2014 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1005539

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536814012355/pk2523sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814012355/pk2523Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814012355/pk2523Isup3.mol

checkCIF report

Comment top

The crystal structure of the title compound was determined in the course of investigations into the reactivity of carbohydrates towards metal cations in liquid ammonia.

As in the platinum compound, the palladium cation forms a homoleptic ammine complex with a square-planar coordination geometry. Pd—N bond lengths are 2.032 (3) Å and 2.048 (3) Å, respectively, while the angles N—Pd—N are 88.59 (13)° and 91.41 (13)°. Ammonia ligands opposite to each other within the complex cation have staggered hydrogen atom positions (Fig. 1).

The chloride anion exhibits nine contacts to hydrogen atoms of ammonia molecules which are either bound in the complex or solvate molecules, forming a network of hydrogen bonds (Fig. 2 and Fig. 3). Bond angles (N—H···Cl) are between 148 (3)° and 175 (3)° whereas N—H···Cl bond lengths are observed with values between 2.48 (5) Å and 2.83 (3) Å. The two N—H···N bridges are close to 180°, with bond angles of 163 (3)° and 170 (3)° and bond lengths significantly less than the sum of the van der Waals radii of nitrogen and hydrogen (2.02 (4) Å and 2.02 (5) Å). These observations give strong evidence that a significant energy contribution from the hydrogen bond network drives the arrangement of the overall structure.

Related literature top

For weak intermolecular interactions such as hydrogen bonds and their application in crystal engeneering, see: Desiraju (2002); Desiraju (2007); Steiner (2002). For the structure of tetraamminepalladium(II) chloride monoydrate and complexation of palladium by carbohydrates, see: Bell et al. (1976); Ahlrichs et al. (1998). The structure of the platinum analogue is given by Graßl & Korber (2014).

Experimental top

0.25 g (1.05 mmol) Pd(en)Cl₂ and 0.188 g (1.05 mmol) D-(+)-glucono-1,5-lactone were placed under argon atmosphere in a reaction flask and 50 ml of dry liquid ammonia were condensed. This mixture was stored in a refrigerator at 237 K for one week to ensure that all substances were completely dissolved. The flask was then stored at 161 K for five months. After that period of time, clear colorless crystals of the title compound were found on the wall of the reaction vessel.

Structure description top

The crystal structure of the title compound was determined in the course of investigations into the reactivity of carbohydrates towards metal cations in liquid ammonia.

For weak intermolecular interactions such as hydrogen bonds and their application in crystal engeneering, see: Desiraju (2002); Desiraju (2007); Steiner (2002). For the structure of tetraamminepalladium(II) chloride monoydrate and complexation of palladium by carbohydrates, see: Bell et al. (1976); Ahlrichs et al. (1998). The structure of the platinum analogue is given by Graßl & Korber (2014).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: olex2.solve (Bourhis et al., 2014); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. : Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry code: (i) 1 - x, 1 - y, - z.
	Fig. 2. : The chloride anion is shown with its surrounding molecules. The predominant bond type is hydrogen bonding. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. : Extended network of hydrogen bonds in the crystal structure. The solvent ammonia molecules are oriented to optimize the hydrogen bond geometry. Displacement ellipsoids are drawn at the 50% probability level.

Tetraamminepalladium(II) dichloride ammonia tetrasolvate top

Crystal data top

[Pd(NH₃)₄]Cl₂·4NH₃	F(000) = 320
M_r = 313.58	D_x = 1.557 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.6856 (5) Å	Cell parameters from 1429 reflections
b = 10.1505 (7) Å	θ = 3.1–29.3°
c = 8.7170 (6) Å	µ = 1.76 mm⁻¹
β = 100.384 (7)°	T = 123 K
V = 668.90 (8) Å³	Block, clear colourless
Z = 2	0.32 × 0.29 × 0.23 mm

Data collection top

Agilent Xcalibur (Ruby, Gemini ultra) diffractometer	1266 independent reflections
Radiation source: fine-focus sealed tube	1076 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
phi and ω scans	θ_max = 25.7°, θ_min = 3.1°
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]	h = −7→9
T_min = 0.649, T_max = 0.741	k = −12→12
2418 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.058	All H-atom parameters refined
S = 1.06	w = 1/[σ²(F_o²) + (0.0075P)²] where P = (F_o² + 2F_c²)/3
1266 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[Pd(NH₃)₄]Cl₂·4NH₃	V = 668.90 (8) Å³
M_r = 313.58	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.6856 (5) Å	µ = 1.76 mm⁻¹
b = 10.1505 (7) Å	T = 123 K
c = 8.7170 (6) Å	0.32 × 0.29 × 0.23 mm
β = 100.384 (7)°

Data collection top

Agilent Xcalibur (Ruby, Gemini ultra) diffractometer	1266 independent reflections
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]	1076 reflections with I > 2σ(I)
T_min = 0.649, T_max = 0.741	R_int = 0.034
2418 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.058	All H-atom parameters refined
S = 1.06	Δρ_max = 0.45 e Å⁻³
1266 reflections	Δρ_min = −0.55 e Å⁻³
100 parameters

Special details top

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.35.21 Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark & Reid, 1995)

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

	x	y	z	U_iso*/U_eq
Pd1	0.5000	0.5000	0.0000	0.01592 (13)
Cl1	0.09460 (10)	0.66086 (7)	0.23005 (10)	0.0236 (2)
N1	0.4602 (4)	0.4827 (3)	0.2233 (3)	0.0200 (6)
N2	0.3507 (4)	0.3356 (3)	−0.0659 (4)	0.0219 (6)
N3	0.5125 (5)	0.8226 (3)	0.3132 (4)	0.0358 (8)
N4	0.7709 (4)	0.5695 (4)	0.4561 (4)	0.0353 (8)
H1A	0.364 (5)	0.525 (3)	0.229 (5)	0.038 (12)*
H1B	0.449 (4)	0.402 (3)	0.246 (4)	0.024 (10)*
H2A	0.382 (4)	0.294 (3)	−0.166 (5)	0.036 (10)*
H1C	0.556 (6)	0.521 (3)	0.296 (5)	0.046 (12)*
H2B	0.358 (4)	0.292 (3)	0.001 (4)	0.018 (11)*
H2C	0.238 (6)	0.355 (4)	−0.097 (5)	0.064 (14)*
H3A	0.403 (5)	0.818 (3)	0.287 (4)	0.017 (9)*
H4A	0.861 (5)	0.594 (3)	0.406 (4)	0.028 (10)*
H4B	0.817 (6)	0.507 (4)	0.541 (6)	0.066 (15)*
H3B	0.554 (6)	0.815 (4)	0.415 (6)	0.055 (14)*
H4C	0.751 (5)	0.646 (4)	0.517 (5)	0.062 (14)*
H3C	0.493 (6)	0.925 (5)	0.277 (6)	0.086 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.01442 (19)	0.0156 (2)	0.0177 (2)	−0.00015 (13)	0.00265 (14)	0.00067 (14)
Cl1	0.0235 (4)	0.0204 (4)	0.0260 (4)	0.0014 (4)	0.0024 (3)	−0.0023 (4)
N1	0.0242 (16)	0.0182 (16)	0.0186 (16)	−0.0026 (14)	0.0069 (13)	0.0011 (13)
N2	0.0226 (16)	0.0219 (16)	0.0210 (17)	−0.0041 (14)	0.0031 (14)	0.0023 (15)
N3	0.041 (2)	0.035 (2)	0.031 (2)	0.0050 (17)	0.0056 (17)	0.0004 (17)
N4	0.0296 (17)	0.042 (2)	0.0320 (19)	−0.0026 (17)	−0.0002 (15)	0.0059 (18)

Geometric parameters (Å, º) top

Pd1—N1ⁱ	2.032 (3)	N2—H2B	0.73 (3)
Pd1—N1	2.032 (3)	N2—H2C	0.88 (5)
Pd1—N2ⁱ	2.048 (3)	N3—H3A	0.83 (3)
Pd1—N2	2.048 (3)	N3—H3B	0.89 (5)
N1—H1A	0.86 (4)	N3—H3C	1.09 (5)
N1—H1B	0.85 (3)	N4—H4A	0.91 (4)
N1—H1C	0.96 (4)	N4—H4B	1.00 (5)
N2—H2A	1.03 (4)	N4—H4C	0.97 (4)

N1—Pd1—N1ⁱ	179.999 (1)	Pd1—N2—H2A	111.2 (18)
N1—Pd1—N2ⁱ	88.59 (13)	Pd1—N2—H2B	109 (3)
N1ⁱ—Pd1—N2ⁱ	91.41 (13)	Pd1—N2—H2C	112 (3)
N1ⁱ—Pd1—N2	88.59 (13)	H2A—N2—H2B	115 (3)
N1—Pd1—N2	91.41 (13)	H2A—N2—H2C	102 (3)
N2—Pd1—N2ⁱ	180.00 (10)	H2B—N2—H2C	108 (4)
Pd1—N1—H1A	107 (3)	H3A—N3—H3B	115 (4)
Pd1—N1—H1B	110 (2)	H3A—N3—H3C	84 (3)
Pd1—N1—H1C	112 (3)	H3B—N3—H3C	112 (4)
H1A—N1—H1B	110 (3)	H4A—N4—H4B	109 (3)
H1A—N1—H1C	108 (3)	H4A—N4—H4C	105 (3)
H1B—N1—H1C	109 (3)	H4B—N4—H4C	100 (4)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.86 (4)	2.49 (4)	3.351 (3)	175 (3)
N1—H1B···Cl1ⁱⁱ	0.85 (3)	2.49 (4)	3.328 (3)	171 (3)
N2—H2A···N3ⁱ	1.03 (4)	2.02 (4)	3.025 (5)	163 (3)
N1—H1C···N4	0.96 (4)	2.02 (5)	2.975 (5)	170 (3)
N2—H2B···Cl1ⁱⁱ	0.73 (3)	2.66 (3)	3.384 (4)	172 (3)
N2—H2C···Cl1ⁱⁱⁱ	0.88 (5)	2.62 (5)	3.463 (3)	162 (4)
N3—H3A···Cl1	0.83 (3)	2.83 (3)	3.563 (4)	148 (3)
N4—H4A···Cl1^iv	0.91 (4)	2.65 (4)	3.563 (4)	173 (3)
N4—H4B···Cl1^v	1.00 (5)	2.61 (5)	3.606 (4)	174 (4)
N3—H3B···Cl1^vi	0.89 (5)	2.71 (5)	3.578 (4)	163 (3)
N3—H3C···Cl1^vii	1.09 (5)	2.48 (5)	3.535 (4)	162 (4)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x, −y+1, −z; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1; (vi) x+1/2, −y+3/2, z+1/2; (vii) −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
N1—H1A···Cl1	0.86 (4)	2.49 (4)	3.351 (3)	175 (3)
N1—H1B···Cl1ⁱ	0.85 (3)	2.49 (4)	3.328 (3)	171 (3)
N2—H2A···N3ⁱⁱ	1.03 (4)	2.02 (4)	3.025 (5)	163 (3)
N1—H1C···N4	0.96 (4)	2.02 (5)	2.975 (5)	170 (3)
N2—H2B···Cl1ⁱ	0.73 (3)	2.66 (3)	3.384 (4)	172 (3)
N2—H2C···Cl1ⁱⁱⁱ	0.88 (5)	2.62 (5)	3.463 (3)	162 (4)
N3—H3A···Cl1	0.83 (3)	2.83 (3)	3.563 (4)	148 (3)
N4—H4A···Cl1^iv	0.91 (4)	2.65 (4)	3.563 (4)	173 (3)
N4—H4B···Cl1^v	1.00 (5)	2.61 (5)	3.606 (4)	174 (4)
N3—H3B···Cl1^vi	0.89 (5)	2.71 (5)	3.578 (4)	163 (3)
N3—H3C···Cl1^vii	1.09 (5)	2.48 (5)	3.535 (4)	162 (4)

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

References

Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Ahlrichs, R., Ballauff, M., Eichkorn, K., Hanemann, O., Kettenbach, G. & Klüfers, P. (1998). Chem. Eur. J. 4, 835–844. CrossRef CAS Google Scholar
Bell, J. D., Bowles, J. C., Cumming, H. J., Hall, D. & Holland, R. V. (1976). Acta Cryst. B32, 634–636. CrossRef CAS IUCr Journals Web of Science Google Scholar
Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2014). In preparation. Google Scholar
Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897. CrossRef CAS Web of Science IUCr Journals Google Scholar
Desiraju, G. R. (2002). Acc. Chem. Res. 35, 565–573. Web of Science CrossRef PubMed CAS Google Scholar
Desiraju, G. R. (2007). Angew. Chem. Int. Ed. 46, 8342–8356. Web of Science CrossRef CAS 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
Grassl, T. & Korber, N. (2014). Acta Cryst. E70, i31. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steiner, T. (2002). Angew. Chem., 114, 50–80. CrossRef Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 7| July 2014| Page i32

https://doi.org/10.1107/S1600536814012355

Open

access