Tetra­ammineplatinum(II) dichloride ammonia tetra­solvate

Grassl, T.; Korber, N.

doi:10.1107/S1600536814012343

inorganic compounds

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Volume 70| Part 7| July 2014| Page i31

https://doi.org/10.1107/S1600536814012343

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Tetraammineplatinum(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, [Pt(NH₃)₄]Cl₂·4NH₃, was crystallized in liquid ammonia from the salt PtCl₂. The platinum cation is coordinated by four ammonia molecules, forming a square-planar complex. The chloride anions are surrounded by nine ammonia molecules, either bound within the platinum complex or solvent molecules. The solvent ammonia molecules are packed in such a way that an extended network of N—H⋯N and N—H⋯Cl hydrogen bonds is formed. The structure is isotypic with [Pd(NH₃)₄]Cl₂·4NH₃ [Grassl & Korber (2014). Acta Cryst. E70, i32].

CCDC reference: 1005538

Related literature

For weak intermolecular interactions such as hydrogen bonds and their application in crystal engineering, see: Desiraju (2002 , 2007 ); Steiner (2002 ). For the structure of Magnus salt and tetraamminplatinous salts, see: Atoji et al. (1957 ); Cox (1932 ); Smolentsev et al. (2010 ). The Pd analogue is described by Grassl & Korber (2014 ).

Experimental

Crystal data

[Pt(NH₃)₄]Cl₂·4NH₃
M_r = 402.25
Monoclinic, P 2₁ /n
a = 7.6641 (2) Å
b = 10.1601 (3) Å
c = 8.7797 (2) Å
β = 100.975 (3)°
V = 671.15 (3) Å³
Z = 2
Mo Kα radiation
μ = 10.83 mm⁻¹
T = 123 K
0.2 × 0.1 × 0.1 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 = 0.162, T_max = 0.462
14167 measured reflections
1368 independent reflections
1276 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.009
wR(F²) = 0.021
S = 1.12
1368 reflections
100 parameters
All H-atom parameters refined
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Cl1	0.85 (2)	2.62 (2)	3.4437 (16)	162.8 (19)
N2—H2B⋯Cl1ⁱ	0.85 (2)	2.52 (2)	3.3594 (17)	169.0 (19)
N1—H1A⋯Cl1ⁱ	0.91 (2)	2.42 (2)	3.3155 (17)	170.2 (17)
N4—H4A⋯Cl1ⁱⁱ	0.89 (3)	2.81 (3)	3.6330 (19)	154 (2)
N1—H1B⋯Cl1ⁱⁱ	0.90 (3)	2.45 (3)	3.3440 (17)	173 (2)
N2—H2C⋯N4ⁱⁱⁱ	0.86 (2)	2.16 (2)	3.020 (2)	178 (2)
N3—H3A⋯Cl1	0.84 (3)	2.75 (3)	3.583 (2)	171 (2)
N4—H4B⋯Cl1	0.93 (4)	2.64 (4)	3.544 (2)	166 (3)
N4—H4C⋯Cl1^iv	0.82 (5)	2.82 (5)	3.608 (2)	163 (4)
N1—H1C⋯N3^v	0.89 (3)	2.08 (3)	2.970 (2)	178.1 (19)
N3—H3B⋯Cl1^vi	0.83 (3)	2.80 (3)	3.616 (2)	168 (3)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x+2, -y+1, -z+1; (vi) -x+1, -y+1, -z.

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: 1005538

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536814012343/pk2522sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814012343/pk2522Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814012343/pk2522Isup3.mol

checkCIF report

Comment top

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

In the crystal structure the platinum cation forms a homoleptic ammine complex with a square-planar coordination geometry. The Pt—N bond lengths are 2.0471 (16) Å and 2.0519 (15) Å, respectively. This is in good accordance with the bond lengths given by Smolentsev et al. (2010). The angles N—Pt—N are 89.24 (6)° and 90.76 (6)°, and within the complex, ammonia ligands opposite to each other have staggered hydrogen atom positions (Fig 1).

The chloride anion shows nine direct contacts to hydrogen atoms of ammonia molecules either bound in the complex or to solvate molecules, forming a network of hydrogen bonds (Fig. 2 and Fig. 3). The N—H···Cl bond angles range between 154 (2)° and 173 (2)° whereas N—H···Cl bond lengths have values between 2.42 (2) Å and 2.82 (5) Å. The two occurring N—H···N bridges are nearly linear, with bond angles of 178 (2)° and 178.1 (19)° and bond lengths considerably less than the sum of the van der Waals radii of nitrogen and hydrogen [2.16 (2) Å and 2.08 (3) Å]. This gives strong evidence that the arrangement of the overall structure is significantly driven by the energy contribution of N—H···N and N—H···Cl hydrogen bonds.

Related literature top

For weak intermolecular interactions such as hydrogen bonds and their application in crystal engeneering, see: Desiraju (2002, 2007); Steiner (2002). For the structure of Magnus salt and tetraamminplatinous salts, see: Atoji et al. (1957); Cox (1932); Smolentsev et al. (2010). The Pd analogue is described by Graßl & Korber (2014).

Experimental top

0.25 g (1.0 mmol) PtCl₂ and 0.21 g (1.00 mmol) N-acetylglucosamine were placed under argon atmosphere in a reaction vessel and 40 ml of dry liquid ammonia were condensed. The mixture was stored 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, clear colorless crystals of the title compound were found at the bottom of the flask.

Structure description top

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

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) 2 - x, 1 - y, 1 - 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.

Tetraammineplatinum(II) dichloride ammonia tetrasolvate top

Crystal data top

[Pt(NH₃)₄]Cl₂·4NH₃	F(000) = 384
M_r = 402.25	D_x = 1.991 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.6641 (2) Å	Cell parameters from 9522 reflections
b = 10.1601 (3) Å	θ = 3.1–30.6°
c = 8.7797 (2) Å	µ = 10.83 mm⁻¹
β = 100.975 (3)°	T = 123 K
V = 671.15 (3) Å³	Block, clear light colourless
Z = 2	0.2 × 0.1 × 0.1 mm

Data collection top

Agilent Xcalibur (Ruby, Gemini ultra) diffractometer	1368 independent reflections
Radiation source: fine-focus sealed tube	1276 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
phi and ω scans	θ_max = 26.4°, 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 = −9→9
T_min = 0.162, T_max = 0.462	k = −12→12
14167 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)] = 0.009	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.021	All H-atom parameters refined
S = 1.12	w = 1/[σ²(F_o²) + (0.0076P)² + 0.3355P] where P = (F_o² + 2F_c²)/3
1368 reflections	(Δ/σ)_max = 0.001
100 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Pt(NH₃)₄]Cl₂·4NH₃	V = 671.15 (3) Å³
M_r = 402.25	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.6641 (2) Å	µ = 10.83 mm⁻¹
b = 10.1601 (3) Å	T = 123 K
c = 8.7797 (2) Å	0.2 × 0.1 × 0.1 mm
β = 100.975 (3)°

Data collection top

Agilent Xcalibur (Ruby, Gemini ultra) diffractometer	1368 independent reflections
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]	1276 reflections with I > 2σ(I)
T_min = 0.162, T_max = 0.462	R_int = 0.022
14167 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.009	0 restraints
wR(F²) = 0.021	All H-atom parameters refined
S = 1.12	Δρ_max = 0.44 e Å⁻³
1368 reflections	Δρ_min = −0.29 e Å⁻³
100 parameters

Special details top

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, 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
Pt1	1.0000	0.5000	0.5000	0.01239 (4)
Cl1	0.40589 (5)	0.33782 (4)	0.26730 (5)	0.01904 (8)
N1	0.9576 (2)	0.48294 (16)	0.72243 (19)	0.0173 (3)
N2	0.8502 (2)	0.33479 (16)	0.43520 (18)	0.0178 (3)
N3	0.7320 (2)	0.4290 (2)	0.0434 (2)	0.0277 (4)
N4	0.5205 (3)	0.6754 (2)	0.3118 (2)	0.0328 (4)
H2A	0.740 (3)	0.352 (2)	0.405 (2)	0.030 (6)*
H2B	0.857 (3)	0.282 (2)	0.511 (3)	0.028 (6)*
H1A	0.941 (3)	0.398 (2)	0.747 (2)	0.024 (5)*
H4A	0.577 (4)	0.675 (3)	0.410 (4)	0.073 (10)*
H1B	0.858 (3)	0.526 (2)	0.732 (3)	0.034 (6)*
H2C	0.887 (3)	0.291 (2)	0.364 (3)	0.028 (6)*
H3A	0.648 (3)	0.406 (3)	0.086 (3)	0.043 (7)*
H4B	0.509 (4)	0.586 (4)	0.293 (4)	0.078 (10)*
H4C	0.428 (6)	0.714 (5)	0.315 (5)	0.140 (19)*
H1C	1.050 (4)	0.5111 (19)	0.792 (3)	0.029 (6)*
H3B	0.688 (4)	0.486 (2)	−0.021 (4)	0.049 (9)*
H3C	0.752 (3)	0.360 (3)	−0.014 (3)	0.058 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.01155 (5)	0.01255 (5)	0.01316 (6)	0.00056 (3)	0.00256 (3)	0.00081 (3)
Cl1	0.01979 (18)	0.01656 (19)	0.0203 (2)	0.00148 (17)	0.00270 (15)	−0.00201 (17)
N1	0.0185 (8)	0.0176 (8)	0.0165 (8)	0.0000 (6)	0.0049 (7)	0.0015 (6)
N2	0.0181 (8)	0.0173 (8)	0.0177 (8)	−0.0025 (6)	0.0026 (6)	0.0012 (7)
N3	0.0256 (9)	0.0332 (10)	0.0227 (9)	0.0001 (8)	0.0003 (7)	0.0057 (8)
N4	0.0483 (11)	0.0238 (10)	0.0252 (10)	−0.0071 (9)	0.0041 (8)	0.0005 (8)

Geometric parameters (Å, º) top

Pt1—N1	2.0471 (16)	N2—H2B	0.85 (2)
Pt1—N1ⁱ	2.0471 (16)	N2—H2C	0.86 (2)
Pt1—N2ⁱ	2.0519 (15)	N3—H3A	0.84 (3)
Pt1—N2	2.0519 (15)	N3—H3B	0.83 (3)
N1—H1A	0.91 (2)	N3—H3C	0.90 (3)
N1—H1B	0.90 (3)	N4—H4A	0.89 (3)
N1—H1C	0.89 (3)	N4—H4B	0.93 (4)
N2—H2A	0.85 (2)	N4—H4C	0.82 (5)

N1ⁱ—Pt1—N1	179.999 (15)	Pt1—N2—H2A	112.9 (14)
N1—Pt1—N2ⁱ	89.24 (6)	Pt1—N2—H2B	110.5 (14)
N1ⁱ—Pt1—N2ⁱ	90.76 (6)	Pt1—N2—H2C	112.5 (14)
N1ⁱ—Pt1—N2	89.24 (6)	H2A—N2—H2B	106.4 (19)
N1—Pt1—N2	90.76 (6)	H2A—N2—H2C	108.9 (19)
N2—Pt1—N2ⁱ	180.00 (7)	H2B—N2—H2C	105 (2)
Pt1—N1—H1A	111.1 (13)	H3A—N3—H3B	105 (3)
Pt1—N1—H1B	109.9 (16)	H3A—N3—H3C	105 (2)
Pt1—N1—H1C	111.9 (16)	H3B—N3—H3C	105 (2)
H1A—N1—H1B	106.9 (19)	H4A—N4—H4B	100 (3)
H1A—N1—H1C	105.9 (18)	H4A—N4—H4C	103 (3)
H1B—N1—H1C	111 (2)	H4B—N4—H4C	115 (4)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.85 (2)	2.62 (2)	3.4437 (16)	162.8 (19)
N2—H2B···Cl1ⁱⁱ	0.85 (2)	2.52 (2)	3.3594 (17)	169.0 (19)
N1—H1A···Cl1ⁱⁱ	0.91 (2)	2.42 (2)	3.3155 (17)	170.2 (17)
N4—H4A···Cl1ⁱⁱⁱ	0.89 (3)	2.81 (3)	3.6330 (19)	154 (2)
N1—H1B···Cl1ⁱⁱⁱ	0.90 (3)	2.45 (3)	3.3440 (17)	173 (2)
N2—H2C···N4^iv	0.86 (2)	2.16 (2)	3.020 (2)	178 (2)
N3—H3A···Cl1	0.84 (3)	2.75 (3)	3.583 (2)	171 (2)
N4—H4B···Cl1	0.93 (4)	2.64 (4)	3.544 (2)	166 (3)
N4—H4C···Cl1^v	0.82 (5)	2.82 (5)	3.608 (2)	163 (4)
N1—H1C···N3ⁱ	0.89 (3)	2.08 (3)	2.970 (2)	178.1 (19)
N3—H3B···Cl1^vi	0.83 (3)	2.80 (3)	3.616 (2)	168 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.85 (2)	2.62 (2)	3.4437 (16)	162.8 (19)
N2—H2B···Cl1ⁱ	0.85 (2)	2.52 (2)	3.3594 (17)	169.0 (19)
N1—H1A···Cl1ⁱ	0.91 (2)	2.42 (2)	3.3155 (17)	170.2 (17)
N4—H4A···Cl1ⁱⁱ	0.89 (3)	2.81 (3)	3.6330 (19)	154 (2)
N1—H1B···Cl1ⁱⁱ	0.90 (3)	2.45 (3)	3.3440 (17)	173 (2)
N2—H2C···N4ⁱⁱⁱ	0.86 (2)	2.16 (2)	3.020 (2)	178 (2)
N3—H3A···Cl1	0.84 (3)	2.75 (3)	3.583 (2)	171 (2)
N4—H4B···Cl1	0.93 (4)	2.64 (4)	3.544 (2)	166 (3)
N4—H4C···Cl1^iv	0.82 (5)	2.82 (5)	3.608 (2)	163 (4)
N1—H1C···N3^v	0.89 (3)	2.08 (3)	2.970 (2)	178.1 (19)
N3—H3B···Cl1^vi	0.83 (3)	2.80 (3)	3.616 (2)	168 (3)

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

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