Abstract
C14H24N8NiPd, monoclinic, P21/n (no. 14), a = 8.9786(9) Å, b = 8.3191(9) Å, c = 11.9489(12) Å, β = 94.772(3)°, V = 889.42(16) Å3, Z = 2, Rgt(F) = 0.0161, wRref(F2) = 0.0401, T = 223(2) K.
The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.
Crystal: | Yellow block |
Size: | 0.16 × 0.12 × 0.04 mm |
Wavelength: | Mo Kα radiation (0.71073 Å) |
μ: | 2.08 mm−1 |
Diffractometer, scan mode: | PHOTON 100 CMOS, φ and ω |
θmax, completeness: | 26.1°, 99% |
N(hkl)measured, N(hkl)unique, Rint: | 22001, 1744, 0.020 |
Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 1560 |
N(param)refined: | 112 |
Programs: | Bruker [1], SHELX [2], ORTEP-3 [3], PLATON [4] |
Atom | x | y | z | Uiso*/Ueq |
---|---|---|---|---|
Pd1 | 0.5000 | 0.5000 | 0.0000 | 0.02139(7) |
N1 | 0.41795(16) | 0.33776(18) | −0.11727(12) | 0.0284(3) |
H1 | 0.3156 | 0.3733 | −0.1432 | 0.034* |
N2 | 0.44102(16) | 0.33423(17) | 0.11395(11) | 0.0269(3) |
H2 | 0.5332 | 0.2763 | 0.1414 | 0.032* |
C1 | 0.4030(2) | 0.1818(2) | −0.05848(16) | 0.0359(4) |
H1A | 0.5006 | 0.1291 | −0.0464 | 0.043* |
H1B | 0.3353 | 0.1103 | −0.1038 | 0.043* |
C2 | 0.3413(2) | 0.2158(2) | 0.05258(16) | 0.0351(4) |
H2A | 0.2399 | 0.2593 | 0.0404 | 0.042* |
H2B | 0.3374 | 0.1165 | 0.0963 | 0.042* |
C3 | 0.3755(2) | 0.4014(2) | 0.21371(15) | 0.0348(4) |
H3A | 0.3525 | 0.3134 | 0.2640 | 0.042* |
H3B | 0.2817 | 0.4564 | 0.1898 | 0.042* |
C4 | 0.4807(2) | 0.5185(2) | 0.27674(16) | 0.0384(5) |
H4A | 0.5793 | 0.4679 | 0.2891 | 0.046* |
H4B | 0.4444 | 0.5386 | 0.3506 | 0.046* |
C5 | 0.5015(2) | 0.3217(2) | −0.21876(15) | 0.0382(4) |
H5A | 0.4484 | 0.2468 | −0.2714 | 0.046* |
H5B | 0.6005 | 0.2765 | −0.1972 | 0.046* |
Ni1 | 0.0000 | 0.5000 | 0.0000 | 0.02491(8) |
N3 | 0.2140(2) | 0.7799(3) | 0.00057(15) | 0.0485(5) |
N4 | −0.09581(18) | 0.6054(2) | 0.22392(13) | 0.0368(4) |
C6 | 0.1330(2) | 0.6736(2) | −0.00001(14) | 0.0325(4) |
C7 | −0.05582(19) | 0.5641(2) | 0.14010(15) | 0.0284(4) |
Source of material
To a solution of (1,4,8,11-tetraazacyclotetradecane)palladium(II) dichloride (0.1237 g, 0.328 mmol) in H2O (10 mL) was added K2Ni(CN)4⋅xH2O (0.1097 g; 0.455 mmol in anhydrous basis) and refluxed for 1 h. After cooling, the formed precipitate was separated by filtration, washed with H2O and acetone, and dried at 50 °C, to give a pale yellow powder (0.0765 g). Crystals suitable for X-ray diffraction were obtained by slow evaporation from an H2O/dimethyl sulfoxide (DMSO) solution at 90 °C.
Experimental details
Hydrogen atoms were positioned geometrically and allowed to ride on their parent atoms with d(C—H) = 0.98 Å, d(N—H) = 0.99 Å and Uiso(H) = 1.2Ueq(C,N) with the help of the SHELXL program (AFIX 23 or 13 options) [2]. The highest peak (0.31 e Å−3) and the deepest hole (−0.34 e Å−3) in the difference Fourier map are located 0.69 Å and 0.74 Å from atoms N1 and Pd1, respectively.
Comment
The crystal structures of the related heterometallic complexes [Ag(cyclam)M1(CN)4]n (cyclam = 1,4,8,11-tetraazacyclotetradecane; M1 = Pd, Pt) [5] and [Cu(cyclam)M2(CN)4]n (M2 = Ni, Pd, Pt) [6] have been determined previously. The structures are formed by one-dimensional cyanido-bridged chains.
The title compound consists of a cationic Pd(II) complex [Pd(cyclam)]2+ and an anionic Ni(II) complex [Ni(CN)4]2−. The title structure is isostructural with the previously reported cyanido-Pd complex [Pd(cyclam)][Pd(CN)4] [7]. Pd(II) and Ni(II) ions are four-coordinated in a slightly distorted square-planar environment and are located on an inversion center, respectively, and thus the asymmetric unit contains one half of the compound. In the cationic complex, the Pd(II) ion is coordinated by four N atoms from the tetradentate cyclam ligand, whereas in the anionic complex, the Ni(II) ion is coordinated by four C atoms from four CN− ligands. In the crystal structure, the cationic and anionic complexes are linked by intermolecular N—H⋯N4(cyanido) hydrogen bonds with d(N⋯N) = 2.977(2)–3.098(2) Å, forming a three-dimensional network [4]. In the reported heterometallic complexes, the metal ions (Ag, Cu) are coordinated by different bridging cyanido ligands in axial positions with d(Ag—N) = 2.567(9) Å in Pd complex and 2.529(9) Å in Pt complex [5], and d(Cu—N) = 2.5321(9) Å in Ni complex, 2.518(2) Å in Pd complex and 2.549(3) Å in Pt complex [6], respectively. In the title compound, on the contrary, such a cyanido-bridging is not observed: the distance between the Pd1 and N3(cyanido) atoms is relatively long with 3.467(2) Å [4].
Funding source: Basic Science Research Program through the National Research Foundation of Korea (NRF)
Award Identifier / Grant number: 2018R1D1A1B07050550
Funding statement: This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (grant number: 2018R1D1A1B07050550). The author thanks the KBSI, Seoul Center, for the X-ray data collection.
References
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©2019 Kwang Ha, published by De Gruyter, Berlin/Boston
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