Mendoza María de Los Angeles, Bernès Sylvain, Mendoza-Díaz Guillermo
Departamento de Ingenierías Química Electrónica y Biomédica, División de Ciencias e Ingenierías, Campus León, Universidad de Guanajuato, Loma del Bosque 103, Lomas del Campestre, León, Guanajuato 37150, Mexico.
DEP Facultad de Ciencias Químicas, UANL, Guerrero y Progreso S/N, Col. Treviño, 64570 Monterrey, N.L., Mexico.
Acta Crystallogr E Crystallogr Commun. 2015 Jan 1;71(Pt 1):22-7. doi: 10.1107/S205698901402595X.
The structures of a series of complexes with general formula n[Pd(pza)X]Y·mH2O (n = 1, 2; X = Cl, Br, I, N3, NCS; Y = NO3, I, N3, [Pd(SCN)4]; m = 0, 0.5, 1) have been determined, where pza is the tridentate ligand bis-[2-(3,5-di-methyl-pyrazol-1-yl)eth-yl]amine, C14H23N5. In all complexes, {bis-[2-(3,5-di-methyl-pyrazol-1-yl-κN (2))eth-yl]amine-κN}chlorido-palladium nitrate, [Pd(pza)Cl]NO3, (1), {bis-[2-(3,5-di-methyl-pyrazol-1-yl-κN (2))eth-yl]amine-κN}bromido-palladium nitrate, [Pd(pza)Br]NO3, (2), {bis-[2-(3,5-di-methyl-pyrazol-1-yl-κN (2))eth-yl]amine-κN}iodido-palladium iodide hemihydrate, [Pd(pza)I]I·0.5H2O, (3), azido{bis-[2-(3,5-di-methyl-pyrazol-1-yl-κN (2))eth-yl]amine-κN}palladium azide monohydrate, [Pd(pza)N3]N3·H2O, (4), and bis-[{bis-[2-(3,5-di-methyl-pyrazol-1-yl-κN (2))eth-yl]amine-κN}(thio-cyanato-κN)palladium] tetra-kis-(thio-cyanato-κS)palladate, [Pd(pza)NCS]2[Pd(SCN)4], (5), the Pd(pza)X complex cation displays a square-planar coordination geometry, and the pza ligand is twisted, approximating twofold rotation symmetry. Although the pza ligand is found with the same conformation along the series, the dihedral angle between pyrazole rings depends on the co-ligand X. This angle span the range 79.0 (3)-88.6 (1)° for the studied complexes. In (3), two complex cations, two I(-) anions and one water mol-ecule of crystallization are present in the asymmetric unit. In (5), the central amine group of pza is disordered over two positions [occupancy ratio 0.770 (18):0.230 (18)]. The complex Pd(SCN)4 anion of this compound exhibits inversion symmetry and shows the Pd(2+) transition metal cation likewise in a square-planar coordination environment. Compound (5) is also a rare occurrence of a non-polymeric compound in which the pseudohalide ligand NCS(-) behaves both as thio-cyanate and iso-thio-cyanate, i.e. is coordinating either through the N atom (in the cation) or the S atom (in the anion).
已确定了一系列通式为(n[Pd(pza)X]Y·mH_2O)（(n = 1, 2)；(X = Cl, Br, I, N_3, NCS)；(Y = NO_3, I, N_3, [Pd(SCN)4])；(m = 0, 0.5, 1)）的配合物结构，其中(pza)为三齿配体双-[2-(3,5-二甲基-吡唑-1-基)乙-基]胺，(C{14}H_{23}N_5)。在所有配合物中，{双-[2-(3,5-二甲基-吡唑-1-基-(κN(2)))乙-基]胺-(κN)}氯钯酸硝酸酯，([Pd(pza)Cl]NO_3)，（1），{双-[2-(3,5-二甲基-吡唑-1-基-(κN(2)))乙-基]胺-(κN)}溴钯酸硝酸酯，([Pd(pza)Br]NO_3)，（2），{双-[2-(3,5-二甲基-吡唑-1-基-(κN(2)))乙-基]胺-(κN)}碘钯酸碘化氢半水合物，([Pd(pza)I]I·0.5H_2O)，（3），叠氮基{双-[2-(3,5-二甲基-吡唑-1-基-(κN(2)))乙-基]胺-(κN)}钯叠氮一水合物，([Pd(pza)N_3]N_3·H_2O)，（4），以及双-[{双-[2-(3,5-二甲基-吡唑-1-基-(κN(2)))乙-基]胺-(κN)}(硫氰酸根-(κN))钯]四-(硫氰酸根-(κS))钯酸盐，([Pd(pza)NCS]_2[Pd(SCN)_4])，（5），(Pd(pza)X)配合物阳离子呈现平面正方形配位几何构型，且(pza)配体发生扭曲，近似具有二重旋转对称性。尽管沿该系列发现(pza)配体具有相同构象，但吡唑环之间的二面角取决于共配体(X)。对于所研究的配合物，该角度范围为(79.0 (3)-88.6 (1)°)。在（3）中，不对称单元中存在两个配合物阳离子、两个(I^-)阴离子和一个结晶水分子。在（5）中，(pza)的中心胺基在两个位置无序分布[占有率比为(0.770 (18):0.230 (18))]。该化合物的([Pd(SCN)_4]^{2 -})阴离子具有反演对称性，且(Pd^{2 +})过渡金属阳离子同样处于平面正方形配位环境中。化合物（5）也是一种罕见的非聚合化合物，其中拟卤化物配体(NCS^-)既表现为硫氰酸根又表现为异硫氰酸根，即通过(N)原子（在阳离子中）或(S)原子（在阴离子中）进行配位。
