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

Grassl, Tobias

Korber, Nikolaus

Acta Crystallographica Section E Structure Reports Online

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Tetraamminepalladium(II) dichlorideammonia tetrasolvateTobias Grassl and Nikolaus Korber*Institut fu¨r Anorganische Chemie, Universita¨t Regensburg, Universita¨tsstrasse 31,93053 Regensburg, GermanyCorrespondence e-mail: nikolaus.korber@chemie.uni-regensburg.deReceived 25 April 2014; accepted 27 May 2014Key indicators: single-crystal X-ray study; T = 123 K; mean (Pd–N) = 0.003 A˚;R factor = 0.027; wR factor = 0.058; data-to-parameter ratio = 12.7.The title compound, [Pd(NH3)4]Cl24NH3, was crystallized inliquid ammonia from the salt Pd(en)Cl2 (en is ethylenedia-mine) and is isotypic with [Pt(NH3)4]Cl24NH3 [Grassl &Korber (2014). Acta Cryst. E70, i31]. The Pd2+ cation iscoordinated by four ammonia molecules, exhibiting a square-planar geometry. The chloride anions are surrounded by nineammonia molecules. These are either bound in the palladiumcomplex or solvent molecules. The packing of the ammoniasolvent molecules enables the formation of an extendednetwork of N—H  N and N—H  Cl interactions with nearlyideal hydrogen-bonding geometry.Related literatureFor weak intermolecular interactions such as hydrogen bondsand their application in crystal engeneering, see: Desiraju(2002); Desiraju (2007); Steiner (2002). For the structure oftetraamminepalladium(II) chloride monoydrate andcomplexation of palladium by carbohydrates, see: Bell et al.(1976); Ahlrichs et al. (1998). The structure of the platinumanalogue is given by Grassl & Korber (2014)ExperimentalCrystal data[Pd(NH3)4]Cl24NH3Mr = 313.58Monoclinic, P21=na = 7.6856 (5) A˚b = 10.1505 (7) A˚c = 8.7170 (6) A˚ = 100.384 (7)V = 668.90 (8) A˚3Z = 2Mo K radiation = 1.76 mm1T = 123 K0.32  0.29  0.23 mmData collectionAgilent Xcalibur (Ruby, Geminiultra) diffractometerAbsorption correction: analytical[CrysAlis PRO (Agilent, 2012),using a multi-faceted crystalmodel based on expressionsderived by Clark & Reid (1995)]Tmin = 0.649, Tmax = 0.7412418 measured reflections1266 independent reflections1076 reflections with I > 2(I)Rint = 0.034RefinementR[F 2 > 2(F 2)] = 0.027wR(F 2) = 0.058S = 1.061266 reflections100 parametersAll H-atom parameters refinedmax = 0.45 e A˚3min = 0.55 e A˚3Table 1Hydrogen-bond geometry (A˚, ).D—H  A D—H H  A D  A D—H  AN1—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  Cl1iv 0.91 (4) 2.65 (4) 3.563 (4) 173 (3)N4—H4B  Cl1v 1.00 (5) 2.61 (5) 3.606 (4) 174 (4)N3—H3B  Cl1vi 0.89 (5) 2.71 (5) 3.578 (4) 163 (3)N3—H3C  Cl1vii 1.09 (5) 2.48 (5) 3.535 (4) 162 (4)Symmetry codes: (i) xþ 12; y 12;z þ 12; (ii) xþ 1;yþ 1;z; (iii) x;yþ 1;z;(iv) xþ 1; y; z; (v) xþ 1;yþ 1;zþ 1; (vi) xþ 12;yþ 32; zþ 12; (vii)x þ 12; yþ 12;zþ 12.Data collection: CrysAlis PRO (Agilent, 2012); cell refinement:CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used tosolve structure: OLEX2.solve (Bourhis et al., 2014); program(s) usedto refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics:DIAMOND (Brandenburg & Putz, 2012); software used to preparematerial for publication: OLEX2 (Dolomanov et al., 2009).Supporting information for this paper is available from the IUCrelectronic archives (Reference: PK2523).ReferencesAgilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.Ahlrichs, R., Ballauff, M., Eichkorn, K., Hanemann, O., Kettenbach, G. &Klu¨fers, P. (1998). Chem. Eur. J. 4, 835–844.Bell, J. D., Bowles, J. C., Cumming, H. J., Hall, D. & Holland, R. V. (1976). ActaCryst. B32, 634–636.Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann,H. (2014). In preparation.Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn,Germany.Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.Desiraju, G. R. (2002). Acc. Chem. Res. 35, 565–573.Desiraju, G. R. (2007). Angew. Chem. Int. Ed. 46, 8342–8356.Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann,H. (2009). J. Appl. Cryst. 42, 339–341.Grassl, T. & Korber, N. (2014). Acta Cryst. E70, i31.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Steiner, T. (2002). Angew. Chem., 114, 50–80.inorganic compoundsi32 Grassl and Korber doi:10.1107/S1600536814012355 Acta Cryst. (2014). E70, i32Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368supplementary materialssup-1Acta Cryst. (2014). E70, i32    supplementary materialsActa Cryst. (2014). E70, i32    [doi:10.1107/S1600536814012355]Tetraamminepalladium(II) dichloride ammonia tetrasolvateTobias Grassl and Nikolaus Korber1. Comment 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.2. Experimental 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.3. Refinement The crystal structure does not show any features where special refinement procedures had to be applied. All hydrogen atoms were located in difference maps and both bond angle/bond length and isotropic displacement parameters were refined.supplementary materialssup-2Acta Cryst. (2014). E70, i32    Figure 1Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry code: (i) 1 - x, 1 - y, - z. supplementary materialssup-3Acta Cryst. (2014). E70, i32    Figure 2The chloride anion is shown with its surrounding molecules. The predominant bond type is hydrogen bonding. Displacement ellipsoids are drawn at the 50% probability level. supplementary materialssup-4Acta Cryst. (2014). E70, i32    Figure 3Extended 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 Crystal data [Pd(NH3)4]Cl2·4NH3Mr = 313.58Monoclinic, P21/na = 7.6856 (5) Åb = 10.1505 (7) Åc = 8.7170 (6) Åβ = 100.384 (7)°V = 668.90 (8) Å3Z = 2F(000) = 320Dx = 1.557 Mg m−3Mo Kα radiation, λ = 0.71073 ÅCell parameters from 1429 reflectionsθ = 3.1–29.3°µ = 1.76 mm−1T = 123 KBlock, clear colourless0.32 × 0.29 × 0.23 mmData collection Agilent Xcalibur (Ruby, Gemini ultra) diffractometerRadiation source: fine-focus sealed tubeGraphite monochromatorphi and ω scansAbsorption correction: analytical [CrysAlis PRO (Agilent, 2012), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]Tmin = 0.649, Tmax = 0.7412418 measured reflections1266 independent reflections1076 reflections with I > 2σ(I)Rint = 0.034θmax = 25.7°, θmin = 3.1°h = −7→9k = −12→12l = −10→10supplementary materialssup-5Acta Cryst. (2014). E70, i32    Refinement Refinement on F2Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.027wR(F2) = 0.058S = 1.061266 reflections100 parameters0 restraintsPrimary atom site location: iterativeSecondary atom site location: difference Fourier mapHydrogen site location: inferred from neighbouring sitesAll H-atom parameters refinedw = 1/[σ2(Fo2) + (0.0075P)2] where P = (Fo2 + 2Fc2)/3(Δ/σ)max < 0.001Δρmax = 0.45 e Å−3Δρmin = −0.55 e Å−3Special details 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) x y z Uiso*/UeqPd1 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) U11 U22 U33 U12 U13 U23Pd1 0.01442 (19) 0.0156 (2) 0.0177 (2) −0.00015 (13) 0.00265 (14) 0.00067 (14)supplementary materialssup-6Acta Cryst. (2014). E70, i32    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) 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) D—H···A D—H H···A D···A D—H···AN1—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···Cl1iv 0.91 (4) 2.65 (4) 3.563 (4) 173 (3)N4—H4B···Cl1v 1.00 (5) 2.61 (5) 3.606 (4) 174 (4)N3—H3B···Cl1vi 0.89 (5) 2.71 (5) 3.578 (4) 163 (3)N3—H3C···Cl1vii 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.

Tetraamminepalladium(II) dichloride tetraammonia solvate

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