Home Physical Sciences Crystal structure of bis(N,N,N-ethyldimethylethanaminium) bis(heptaselenido-κ2Se1,Se7)palladate(II), C12H32N2PdSe14
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Crystal structure of bis(N,N,N-ethyldimethylethanaminium) bis(heptaselenido-κ2Se1,Se7)palladate(II), C12H32N2PdSe14

  • Kang-Woo Kim EMAIL logo and Di Wang
Published/Copyright: September 16, 2017

Abstract

C12H32N2PdSe14, monoclinic, P21/n (no. 14), a = 9.2236(9) Å, b = 15.1503(14) Å, c = 12.2198(12) Å, β = 109.683(2)°, V = 1607.8(3) Å3, Z = 2, Rgt(F) = 0.0397, wRref(F2) = 0.0958, T = 173 K.

CCDC no.:: 1567742

The crystal structure is shown in the figure. Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Crystal:Black block
Size:0.26 × 0.19 × 0.14 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:16.43 mm−1
Diffractometer, scan mode:Bruker APEX-II CCD, ϕ and ω
θmax:28.2°
N(hkl)measured, N(hkl)unique, Rint:15584, 3665, 0.054
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 2915
N(param)refined:133
Programs:SHELX [10], WinGX [11], Diamond [12], Bruker programs [13]
Table 2

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

AtomxyzUiso*/Ueq
Pd10.50000.00000.00000.01933(15)
Se10.48036(7)0.14493(4)0.07921(6)0.02584(15)
Se20.31769(7)0.14255(4)0.18877(5)0.02622(15)
Se30.44708(8)0.07441(4)0.36965(6)0.02924(16)
Se40.50652(8)0.19350(4)0.49904(6)0.03013(16)
Se50.27843(9)0.22367(5)0.53511(6)0.03686(19)
Se60.10631(8)0.28396(4)0.36411(6)0.03090(17)
Se70.12727(7)0.43654(4)0.37272(5)0.02603(16)
N10.5595(6)0.4203(3)0.2744(4)0.0230(11)
C10.6563(8)0.4905(4)0.2444(6)0.0320(15)
H1A0.75520.49330.30630.038*
H1B0.67510.47300.17400.038*
C20.5860(11)0.5808(5)0.2267(7)0.054(2)
H2A0.49070.57960.16280.081*
H2B0.65540.62170.21020.081*
H2C0.56700.59890.29590.081*
C30.3999(7)0.4121(4)0.1863(6)0.0333(16)
H3A0.34220.46500.18950.040*
H3B0.34840.36260.20750.040*
C40.3967(8)0.3992(5)0.0623(6)0.0379(17)
H4A0.45440.34740.05820.057*
H4B0.44150.44970.03860.057*
H4C0.29210.39240.01180.057*
C50.6426(8)0.3346(4)0.2855(6)0.0325(15)
H5A0.74680.34160.33670.049*
H5B0.64260.31600.21040.049*
H5C0.59190.29080.31660.049*
C60.5413(8)0.4404(5)0.3892(6)0.0393(17)
H6A0.61080.40430.44850.059*
H6B0.43730.42820.38480.059*
H6C0.56400.50150.40780.059*

Source of material

Na2PdCl4 (0.035 g, 0.12 mmol), Na2Se4 (0.129 g, 0.36 mmol) and Et2Me2NI (0.109 g, 0.48 mmol) were charged to a Pyrex tube with diameter of 9 mm under an argon atmosphere and about 0.5 mL MeOH was added as solvent. While the solvent was being frozen, the Pyrex tube was evacuated under vacuum and sealed with the use of a flame. The sealed tube was placed in an oven and heated at 80 °C for 3 days, then cooled to room temperature. Reddish black block crystals were isolated by filtration and washed with MeOH and diethyl ether several times. Crystals of [Et2Me2N]2[Pd(Se7)2] were obtained in 15% yield, based on Pd.

Experimenal details

H atoms were positioned geometrically and treated as riding, with C—H = 0.97 (CH2) and 0.96 (CH3) Å with Uiso(H) = 1.2 (1.5 for methyl) Ueq(C). H atoms of the CH3 were positioned to be staggered with respect to the shortest other bond to the atom to which the CH3 is attached.

Comment

The title compound, (Et2Me2N)2[Pd(Se7)2], which has been prepared by the solvothermal reaction of Na2PdCl4, Na2Se4 and Et2Me2NI with MeOH as a solvent, is composed of a 2D layered [Pd(Se7)2]2− anion and charge-balancing Et2Me2N+ cations. (Et2Me2N)2[Pd(Se7)2] features to possess the longest bridging polyselenide anion, the Se72− ligand. So far Se62− is the longest one as found in {(CH3)N(CH2CH2)3N}2[Pd(Se6)2], (EtNH3)2[Pd(Se6)2], K2PdSe10 and so on [1], [2], [3], [4]. In the case of polysulfide anions, the S72− ligand already exists as the longest bridging polysulfide ligand, as found in (Ph4P)4[In2S27] [5]. Instead of symmetric tetraalkylammonium cations such as Me4N+, Et4N+, and (n-Pr)4N+, an unsymmetric mixed alkyl ammonium cation, Et2Me2N+ was adopted to construct a new Pd polyselenide complex by virture of the counterion effect. The counterion effect had been documented, leading to a number of Pd polyselenides with novel structures [1], [2], [3], [4], [6].

For the structure of [Pd(Se7)2]2− in (Et2Me2N)2[Pd(Se7)2], the square planar geometry around Pd(II), coordinated by four bridging heptaselenide ligands, is quite ideal as Se-Pd-Se angles are in the range of 89.18(2)–90.82(2)° (cf. the upper figure). The Pd—Se and Se—Se distances are also typical, ranging from 2.4308(6) to 2.4396(6) Å, and from 2.3192(9) to 2.3661(9) Å, respectively, similar to those found in other [Pd(Sex)2]2− complexes [1], [2], [3], [7], [8], [9]. In the layers of [Pd(Se7)2]2−, heptaselenide Se72− ligand chains are connecting Pd metal centers, resulting in 32-membered rings composed of four Pd and twenty eight Se atoms (cf. the upper figure). The distances between two couples of Pd centers faced diagonally in the 32-membered ring are 15.1503(14) and 17.6160(13) Å. These distances are 10.807(4) and 15.050(5) Å for the 28-membered rings of {(CH3)N(CH2CH2)3N}2[Pd(Se6)2]. Compared to the (CH3)N(CH2CH2)3N+ cation, the smaller Et2Me2N+ cation interestingly stabilized the [Pd(Se7)2]2− anion with longer polyselenides and larger rings. As we can see from the side view of the [Pd(Se7)2]2− layers, the highly folded heptaselenide chains are considered to fill the possible empty space inside and between the layers, to leave smaller empty space enough for being filled with Et2Me2N+ cations (cf. the lower figure).

Acknowledgement

This work was supported by the Incheon National University Research Grant in 2015. The authors thank Dr. Ji-Eun Lee at Central Instrument Facility, Gyeongsang National University for the X-ray measurements.

References

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Received: 2017-4-7
Accepted: 2017-8-9
Published Online: 2017-9-16
Published in Print: 2017-11-27

©2017 Kang-Woo Kim et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

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