Startseite Crystal structure of (1,4,8,11-tetraazacyclotetradecane-κ4N,N′,N″,N‴)palladium(II) tetraiodidopalladate(II), C10H24I4N4Pd2
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Crystal structure of (1,4,8,11-tetraazacyclotetradecane-κ4N,N′,N″,N‴)palladium(II) tetraiodidopalladate(II), C10H24I4N4Pd2

  • Kwang Ha ORCID logo EMAIL logo
Veröffentlicht/Copyright: 7. Februar 2025

Abstract

C10H24I4N4Pd2, monoclinic, P21/n (no. 14), a = 8.955(7) Å, b = 15.587(13) Å, c = 14.752(12) Å, β = 95.63(2)°, V = 2049(3) Å3, Z = 4, R gt (F) = 0.0564, wR ref (F2) = 0.1562, T = 223 K.

CCDC no.: 2419895

The title crystal 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.

Table 1:

Data collection and handling.

Crystal: Brown Block
Size: 0.15 × 0.03 × 0.02 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 7.78 mm−1
Diffractometer, scan mode: Bruker APEX-II CCD, φ and ω scans
θmax, completeness: 26.2°, 100 %
N(hkl)measured, N(hkl)unique, Rint: 17507, 4064, 0.111
Criterion for Iobs, N(hkl)gt: Iobs > 2σ(Iobs), 2,273
N(param)refined: 181
Programs: Bruker, 1 SHELX, 2 ORTEPIII, 3 PLATON 4
Table 2:

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

x y z U iso */U eq
Pd1 0.12545 (13) 0.27536 (7) 0.11275 (8) 0.0307 (3)
N1 0.0496 (15) 0.1524 (7) 0.1099 (8) 0.039 (3)
H1 −0.0544 0.1536 0.0802 0.046*
N2 0.0835 (14) 0.2741 (7) 0.2455 (8) 0.038 (3)
H2 0.1796 0.2604 0.2815 0.046*
N3 0.2023 (13) 0.3975 (7) 0.1141 (8) 0.032 (3)
H3 0.3080 0.3966 0.1409 0.038*
N4 0.1660 (13) 0.2761 (7) −0.0216 (8) 0.035 (3)
H4 0.0684 0.2859 −0.0577 0.042*
C1 0.0406 (19) 0.1253 (9) 0.2057 (10) 0.046 (4)
H1A 0.1401 0.1087 0.2338 0.055*
H1B −0.0269 0.0760 0.2079 0.055*
C2 −0.0187 (17) 0.2005 (9) 0.2565 (10) 0.043 (4)
H2A −0.1210 0.2146 0.2312 0.051*
H2B −0.0203 0.1864 0.3211 0.051*
C3 0.027 (2) 0.3555 (10) 0.2837 (10) 0.052 (5)
H3A 0.0204 0.3479 0.3491 0.062*
H3B −0.0736 0.3674 0.2547 0.062*
C4 0.127 (2) 0.4311 (10) 0.2696 (10) 0.049 (5)
H4A 0.2312 0.4164 0.2911 0.059*
H4B 0.0971 0.4797 0.3058 0.059*
C5 0.1192 (18) 0.4576 (10) 0.1691 (10) 0.046 (4)
H5A 0.0139 0.4596 0.1438 0.055*
H5B 0.1613 0.5153 0.1647 0.055*
C6 0.201 (2) 0.4276 (9) 0.0183 (10) 0.044 (4)
H6A 0.2664 0.4776 0.0147 0.053*
H6B 0.0991 0.4432 −0.0065 0.053*
C7 0.2590 (16) 0.3518 (9) −0.0345 (10) 0.036 (4)
H7A 0.2547 0.3659 −0.0994 0.043*
H7B 0.3637 0.3397 −0.0124 0.043*
C8 0.2292 (19) 0.1968 (9) −0.0566 (11) 0.046 (4)
H8A 0.3306 0.1881 −0.0265 0.055*
H8B 0.2371 0.2031 −0.1220 0.055*
C9 0.136 (2) 0.1199 (9) −0.0409 (10) 0.049 (5)
H9A 0.1730 0.0714 −0.0746 0.059*
H9B 0.0325 0.1313 −0.0665 0.059*
C10 0.1334 (19) 0.0936 (9) 0.0578 (10) 0.042 (4)
H10A 0.0888 0.0363 0.0601 0.051*
H10B 0.2368 0.0900 0.0862 0.051*
Pd2 0.62080 (13) 0.25838 (7) 0.11234 (8) 0.0314 (3)
I1 0.64292 (13) 0.09931 (6) 0.05695 (8) 0.0451 (3)
I2 0.47652 (12) 0.20216 (7) 0.24688 (7) 0.0436 (3)
I3 0.60496 (13) 0.41773 (6) 0.17128 (8) 0.0451 (3)
I4 0.75794 (12) 0.31252 (6) −0.02647 (7) 0.0407 (3)

1 Source of materials

The black suspension of [Pd(cyclam)]I2 (cyclam = 1,4,8,11-tetraazacyclotetradecane; 0.0834 g, 0.149 mmol) and PdI2 (0.0543 g, 0.151 mmol) in dimethyl sulfoxide (DMSO; 5 ml) was heated at 120 °C for 3 h. After removal of the undissolved, the solvent was evaporated at 90 °C and the residue was washed with methanol, and dried at 60 °C, to give a dark brown powder (0.0989 g). Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation from a DMSO solution at 90 °C.

2 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 (1.63 e Å−3) and the deepest hole (−1.43 e Å−3) in the difference Fourier map are located 1.46 Å and 0.94 Å from the atom Pd2.

3 Comment

The crystal structures of the related cyclam–Pd(II) complexes [Pd(cyclam)][M(CN)4] (M = Pd, Pt, Ni) 5 , 6 , 7 and [Pd(cyclam)]I2·H2O 8 have been determined previously.

The title compound consists of a cationic Pd(II) complex [Pd(cyclam)]2+ and an anionic Pd(II) complex [PdI4]2−. Each Pd(II) ion is four-coordinated in a slightly distorted square-planar environment. 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 Pd(II) ion is coordinated by four I ligands. The Pd–N and Pd–I bond lengths are almost equal with d(Pd1–N) = 2.023(11)–2.049(12) Å and d(Pd2–I) = 2.623(2)–2.640(2) Å, respectively. In the crystal structure, the cationic and anionic complexes are linked by intermolecular N–H···I hydrogen bonds with distances of 3.635(12)–3.742(14) Å between the donor and acceptor atoms, to stabilize the three-dimensional packing. 4


Corresponding author: Kwang Ha, School of Chemical Engineering, Chonnam National University, Gwangju 61186, Republic of Korea, E-mail:

Acknowledgements

This study was financially supported by Chonnam National University (Grant number: 2024–1100-01). The author thanks the KBSI, Seoul Center, for the X-ray data collection.

References

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Received: 2025-01-16
Accepted: 2025-01-27
Published Online: 2025-02-07
Published in Print: 2025-04-28

© 2025 the author(s), published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  62. Crystal structure of (1,4,8,11-tetraazacyclotetradecane-κ4N,N′,N″,N‴)palladium(II) tetraiodidopalladate(II), C10H24I4N4Pd2
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