Coordination of bis­(pyrazol-1-yl)amine to palladium(II): influence of the co-ligands and counter-ions on the mol­ecular and crystal structures

Mendoza, M. de los A.; Bernès, S.; Mendoza-Díaz, G.

doi:10.1107/S205698901402595X

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 1| January 2015| Pages 22-27

https://doi.org/10.1107/S205698901402595X

Open

access

Coordination of bis(pyrazol-1-yl)amine to palladium(II): influence of the co-ligands and counter-ions on the molecular and crystal structures¹

María de los Angeles Mendoza,^a Sylvain Bernès ^b ^*‡ and Guillermo Mendoza-Díaz ^a

^aDepartamento 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, and ^bDEP Facultad de Ciencias Químicas, UANL, Guerrero y Progreso S/N, Col. Treviño, 64570 Monterrey, N.L., Mexico
^*Correspondence e-mail: sylvain_bernes@Hotmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 10 October 2014; accepted 26 November 2014; online 1 January 2015)

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-dimethylpyrazol-1-yl)ethyl]amine, C₁₄H₂₃N₅. In all complexes, {bis[2-(3,5-dimethylpyrazol-1-yl-κN²)ethyl]amine-κN}chloridopalladium nitrate, [Pd(pza)Cl]NO₃, (1), {bis[2-(3,5-dimethylpyrazol-1-yl-κN²)ethyl]amine-κN}bromidopalladium nitrate, [Pd(pza)Br]NO₃, (2), {bis[2-(3,5-dimethylpyrazol-1-yl-κN²)ethyl]amine-κN}iodidopalladium iodide hemihydrate, [Pd(pza)I]I·0.5H₂O, (3), azido{bis[2-(3,5-dimethylpyrazol-1-yl-κN²)ethyl]amine-κN}palladium azide monohydrate, [Pd(pza)N₃]N₃·H₂O, (4), and bis[{bis[2-(3,5-dimethylpyrazol-1-yl-κN²)ethyl]amine-κN}(thiocyanato-κN)palladium] tetrakis(thiocyanato-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 molecule 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]²⁻ anion of this compound exhibits inversion symmetry and shows the Pd²⁺ 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 thiocyanate and isothiocyanate, i.e. is coordinating either through the N atom (in the cation) or the S atom (in the anion).

Keywords: crystal structure; coordination compounds; bis[2-(3,5-dimethylpyrazol-1-yl)ethyl]amine (pza) ligand; bis(pyrazol-1-yl)amine; palladium(II).

CCDC references: 1036262; 1036261; 1036260; 1036259; 1036258

1. Chemical context

The coordination chemistry of transition metals having a d⁸ shell is clearly dominated by the square-planar geometry, which gives strong crystal field stabilization, because filled orbitals d_z2 and degenerated orbitals (d_xz d_yz) do not interact directly with orbitals of the ligands. This holds true for group 10 metal complexes, for which the tetrahedral geometry is considered as an oddity (Alvarez et al., 2005 ).

We synthesized a series of such square-planar complexes, with general formula n[Pd(pza)X]Y·mH₂O, in which pza is the tridentate ligand bis-[2-(3,5-dimethylpyrazol-1-yl)ethyl]amine, and X, Y are halide, pseudohalide, nitrate, or a complex anion. This series was first considered within a larger project related to a systematic study of modifications of cis-platin, obtained through the substitution of NH₃ ligands by N-heterocyclic systems, like imidazole- and pyrazole-based ligands. The Pd^II synthetic chemistry may be easily transferred to Pt^II, with the advantage that Pd^II starting materials are somewhat cheaper than their Pt^II analogues. On the other hand, regarding the chemical crystallography, Pd^II complexes are almost always isostructural to their Pt^II analogues. Finally, any new Pd^II complex is also of potential interest for studies about the fundamental aspects of the catalysis of the Heck reaction type.

We thus focused our efforts on the crystallographic characterization of the Pd^II complexes obtained as single crystals, with the hope of rationalizing the effect of the co-ligand X and counter-ion Y on the molecular and crystal structures of the complex [Pd(pza)X]⁺ cations. An earlier report of the crystal structure of the starting material, [Pd(pza)Cl]Cl·2H₂O has been given (Mendoza et al., 2006 ), and we now report on the characterization of [Pd(pza)Cl]NO₃ (1), [Pd(pza)Br]NO₃ (2), [Pd(pza)I]I·0.5(H₂O) (3), [Pd(pza)N₃]N₃·H₂O (4), and 2[Pd(pza)NCS][Pd(SCN)₄] (5).

2. Structural commentary: molecular and crystal structures

Complex (1) is a result of the substitution of the counter-ion Y = Cl⁻ in the starting material, i.e. in the dihydrate [Pd(pza)Cl]Cl·2H₂O by a nitrate, but crystallizes as an anhydrous species, [Pd(pza)Cl]NO₃ (Fig. 1). As expected, the square-planar coordination of the metal cation is retained, and the conformation of the pza ligand is not affected by the counter-ion substitution. The cation conformation may be characterized by the dihedral angle between the pyrazole mean planes, 85.1 (3)° versus 87.62 (11)° in the chloride salt (Mendoza et al., 2006). A least-squares fit between the [Pd(pza)Cl]⁺ cations in the chloride and nitrate salts gives an r.m.s. deviation of 0.124 Å. However, the crystal structures are different because the water molecules in the chloride dihydrate are determinant for the supramolecular arrangement through hydrogen-bonding and intermolecular contacts. In (1), the nitrate ion interacts with the central amine group of the pza ligand, with a N10—H10⋯O1 separation of 1.98 Å. Other inter-ion contacts beyond the asymmetric unit are unexceptional, and the observed crystal structure is basically a consequence of Coulombic interactions rather than hydrogen bonds (Table 1).

Table 1
Hydrogen-bond geometry (Å, °) for (1)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯N20ⁱ	0.93	2.66	3.510 (10)	153
C7—H7C⋯Cl1	0.96	2.81	3.410 (10)	121
C8—H8A⋯O3ⁱⁱ	0.97	2.28	3.222 (10)	163
N10—H10⋯N20	0.90	2.57	3.453 (10)	167
N10—H10⋯O1	0.90	1.98	2.857 (9)	164
N10—H10⋯O2	0.90	2.45	3.186 (10)	140
C14—H14A⋯Cl1ⁱⁱⁱ	0.93	2.82	3.629 (9)	146
C16—H16A⋯O1^iv	0.96	2.64	3.572 (12)	164
C17—H17A⋯O3ⁱⁱ	0.96	2.53	3.491 (12)	175
C17—H17C⋯Cl1	0.96	2.79	3.367 (10)	119
C18—H18A⋯O2	0.97	2.51	3.364 (11)	146
C18—H18B⋯O1^iv	0.97	2.61	3.428 (11)	142
C19—H19A⋯O3^iv	0.97	2.47	3.112 (11)	124
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 1
View of the molecular structure of complex (1), corresponding to X = Cl⁻ and Y = NO₃⁻, with displacement ellipsoids for non-H atoms drawn at the 30% probability level. The inset is an overlay (Mercury; Macrae et al., 2008

) of the cations in (1) and (2), in which X = Br⁻.

Complex (2), with X = Br⁻ and Y = NO₃⁻ is isostructural with the X = Cl⁻ analogue (1). However, a slight relaxation of the folded pza ligand is observed, with a dihedral angle between pyrazole rings of 83.6 (2)°. An overlay between cations in (1) and (2) gives a small deviation of 0.049 Å (Fig. 1, inset). The nitrate anion interacts with the complex cation in (2) with a distance N10—H10⋯O1 = 1.98 Å (Table 2). Thus, the nature of the halogen co-ligand X in [Pd(pza)X]NO₃ seems to be unimportant for the resulting crystal structure.

Table 2
Hydrogen-bond geometry (Å, °) for (2)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯N20ⁱ	0.93	2.66	3.540 (7)	159
C7—H7C⋯Br1	0.96	3.06	3.500 (8)	110
C8—H8A⋯O3ⁱⁱ	0.97	2.30	3.219 (9)	157
N10—H10⋯N20	0.90	2.54	3.427 (6)	169
N10—H10⋯O1	0.90	1.98	2.857 (7)	166
N10—H10⋯O2	0.90	2.43	3.181 (8)	142
C14—H14A⋯Br1ⁱⁱⁱ	0.93	2.88	3.687 (6)	146
C16—H16A⋯O1^iv	0.96	2.65	3.511 (10)	150
C17—H17A⋯O3ⁱⁱ	0.96	2.55	3.485 (10)	164
C17—H17C⋯Br1	0.96	2.98	3.459 (8)	112
C18—H18A⋯O2	0.97	2.52	3.358 (9)	144
C18—H18B⋯O1^iv	0.97	2.65	3.468 (8)	142
C19—H19B⋯O3^iv	0.97	2.47	3.099 (9)	122
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Complex (3), built up with X = Y = iodide, crystallized as a hemihydrate, with two cation complexes and two free iodide ions in the asymmetric unit (Fig. 2). The square-planar geometry of Pd^II is retained, as well as the pza conformation. However, the relaxation of folding, observed with X = Br⁻ in compound (2), is amplified with X = I⁻: the angle between the pyrazole rings is now 79.0 (3) and 83.3 (3)°, for the Pd1 and Pd2 cations, respectively. There seems to be a regular trend for [Pd(pza)X]⁺ cations: the smaller the ionic radius of the co-ligand X, the closer the angle between the pyrazole rings is to 90°. A possible rationalization of this observation is that methyl groups substituting pyrazole rings at position 3 interact with the co-ligand X. This destabilizing steric interaction favors the twisting of pza, which in general adopts a non-crystallographic twofold rotation symmetry. However, the large iodide anion forces the separation between methyl groups, compared to the small chloride ion. In order to keep the coordination geometry around Pd^II as planar as possible, the heterocycles in pza then make a slight rotation motion, which is reflected in the deviation from orthogonality of these terminal rings. In other words, the combined twisting and folding motions of the pza ligand lead to as planar as possible a coordination environment for Pd^II. Counter-ions Y and lattice water molecules have only slight influences, if any, on the cation conformation. In the case of (3), the water molecule behaves both as a donor and acceptor group for hydrogen bonding. O—H⋯I bonds are formed with the non-coordinating iodide anions, and the central amine group of pza forms a N—H⋯O bond with the same water molecule (Table 3). However, as for previous complexes (1) and (2), no extended supramolecular structures are formed in the crystal.

Table 3
Hydrogen-bond geometry (Å, °) for (3)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯I3	0.85	2.68	3.497 (7)	161
O1—H2⋯I4	0.85	2.66	3.443 (10)	155
N10—H10A⋯I3ⁱ	0.90	2.94	3.653 (6)	137
N30—H30A⋯O1ⁱⁱ	0.90	2.22	3.011 (9)	146
N30—H30A⋯I4ⁱⁱ	0.90	3.30	3.853 (6)	122
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+1, -z.

Figure 2
View of the molecular structure of complex (3), corresponding to X = Y = I⁻, with displacement ellipsoids for non-H atoms drawn at the 30% probability level.

Using the pseudohalide X = Y = azide, compound (4) was crystallized as an hydrate, [Pd(pza)N₃]N₃·H₂O (Fig. 3). The nitrogen atoms in the coordinating N₃⁻ ligand are not sterically demanding as the iodide ion in (3) and, as a consequence, the pyrazole rings come back in a more orthogonal arrangement, identical to that observed in [Pd(pza)Cl]⁺. The dihedral angle between pyrazole rings is 87.3 (1)° in (4). The strongest hydrogen bond is found between the amine group of pza and the free azide ion, the N10—H10⋯N32 separation being 1.95 Å and the angle for the contact 171° (Table 4).

Table 4
Hydrogen-bond geometry (Å, °) for (4)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10—H10⋯N32	0.90	1.95	2.838 (11)	171
N10—H10⋯N31	0.90	2.66	3.460 (13)	148
O1—H11⋯N32ⁱ	0.84	2.67	3.295 (19)	132
O1—H12⋯N30	0.85	2.38	3.08 (2)	140
Symmetry code: (i) x+1, y, z.

Figure 3
View of the molecular structure of complex (4), corresponding to X = Y = N₃⁻, with displacement ellipsoids for non-H atoms drawn at the 30% probability level.

Finally, in the fifth compound (5), the counter-ion Y is a complex anion, namely [Pd(SCN)₄]²⁻. The formula for (5) is 2[Pd(pza)NCS][Pd(SCN)₄], and the anion is located about an inversion centre, while the cation is in a general position (Fig. 4). The pza ligand in [Pd(pza)NCS]⁺, in contrast to previous compounds, has the amine group N10 disordered over two positions, N10A and N10B, with occupancies 0.770 (18) and 0.230 (18), respectively. The same type of disorder was previously reported for an Au^III complex (Segapelo et al., 2011 ). In spite of this disorder, the general conformation of pza is identical to that observed in compounds (1)–(4), approximating the non-crystallographic twofold rotation symmetry. The co-ligand X = NCS⁻ coordinates through its N atom, and the local environment of the metal is very similar to that resulting from azide coordination in complex (4). The dihedral angle between pyrazole rings should thus be close to 90°. The actual value is 88.6 (1)°. The anion [Pd(SCN)₄]²⁻ is also square-planar, but with the ligands coordinating in a κS-fashion, while in the cation, the NCS ligand is bound in a κN-fashion to the metal cation. If complexes with bridging thiocyanate ligands are not considered, very few structures are known in which the ambidentate ligand NCS⁻ is bonded in two modes (κS- and κN-) to the same transition metal. In the case of Pd^II, classified as a soft acid in the Pearson's HSAB concept, the soft base SCN⁻ should have a preference for the κS-coordination. Apparently, only a few non-polymeric crystal structures have been reported including both coordination modes of SCN⁻ to this metal (e.g. Paviglianiti et al., 1989 ; Chang et al., 2005 ). In the crystal structure, weak hydrogen bonds between the disordered amino group and the NCS groups of neighbouring cations and anions are observed (Table 5).

Table 5
Hydrogen-bond geometry (Å, °) for (5)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10A—H10A⋯N24ⁱ	0.90	2.01	2.889 (9)	166
N10B—H10B⋯S1ⁱⁱ	0.90	2.71	3.52 (2)	151
Symmetry codes: (i) x, y, z-1; (ii) x-1, y, z.

Figure 4
View of the molecular structure of complex (5), corresponding to X = NCS⁻ and Y = [Pd(SCN)₄]²⁻, with displacement ellipsoids for non-H atoms at the 30% probability level. Only one position for the disordered amine group in the cation has been retained (N10A). In the anion, unlabelled atoms are generated by symmetry code (−x + 1, −y + 2, −z + 2).

3. Database survey

The ligand pza has been widely used in coordination chemistry. The current release of the CSD (Version 5.35 with all updates; Groom & Allen, 2014 ) affords 39 entries distributed over 18 articles. With Pd^II, two structures are reported to date, which are pseudopolymorphs with X = Y = Cl⁻ (Mendoza et al., 2006; Guzei et al., 2010 ). Other transition metals have been coordinated by pza and structures are available for Co^II (van Berkel et al., 1994 ; Massoud et al., 2012a , 2013 ), Ni^II (Ajellal et al., 2006 ; Massoud et al., 2012a, 2013), Cu^II (van Berkel et al., 1994; Martens et al., 1995 ; Kim et al., 2000 ; Monzani et al., 2000 ; Riklin et al., 2001 ; Massoud et al., 2012a,b , 2013), Zn^II (Burth & Vahrenkamp, 1998 ; Lian et al., 2007a ; Lee et al., 2007 ; Massoud et al., 2013), Cd^II (Griffith et al., 1987 ; Massoud et al., 2013), Re^I (Alves et al., 2002 ) and Au^III (Segapelo et al., 2011). The pza ligand generally behaves as a tridentate ligand, with exceptions for some Zn^II compounds, in which one pyrazole ring is not coordinating to the metal (Burth & Vahrenkamp, 1998; Lian et al., 2007a; Lee et al., 2007). Few complexes have also been prepared with s- and p-metals, viz. Li^I (Lian et al., 2007a), Mg^II (Lian et al., 2007b ), and Al^III (Lian et al., 2007a).

The conformation observed for pza is determined by the coordination number of the metal centre. For example, hexa-coordinated transition metals like Ni^II or Cd^II favor the facial coordination of pza, which is then found in a folded conformation, while coordination numbers 5 and 4 promote some defolding. The ligand pza with the dihedral angle between pyrazole rings very close to 0° has been observed in Co^II complexes (Massoud et al., 2012a, 2013). A conformation for pza close to that observed in (1)–(5) has been reported with Mg^II (Lian et al., 2007b) and Au^III (Segapelo et al., 2011).

4. Synthesis and crystallization

Complexes (1)–(5) were synthesized starting from [Pd(pza)Cl]Cl·2H₂O (Mendoza et al., 2006), by substitution of co-ligands and counter-ions, as depicted in Fig. 5.

Figure 5
General synthetic scheme for complexes (1)–(5).

Synthesis of (1). [Pd(pza)Cl]Cl·2H₂O (1 mmol) was dissolved in CH₃CN, and a solution of AgNO₃ (1 mmol in CH₃CN) was added slowly. The mixture was stirred for 1 h at room temperature. After elimination by filtration of the white precipitate of AgCl, the mixture was further stirred for 1 h. Evaporation of the solvent afforded complex (1) as a brown–yellow solid, in 82% yield, and crystals were obtained by recrystallization from CH₃CN.

Synthesis of (2). [Pd(pza)Cl]Cl·2H₂O (1 mmol) was dissolved in CH₃CN, and a solution of AgNO₃ (2 mmol in CH₃CN) was added slowly. The mixture was stirred for 2 h at room temperature, and the precipitated AgCl was removed by filtration. An aqueous solution of NaBr (1 mmol) was then added, and NaNO₃ precipitates, which was removed by filtration. The solution was further stirred for 5 h. Evaporation of the solvent afforded complex (2) as a yellow solid, in 76% yield, and crystals were obtained by recrystallization from CH₃CN.

Synthesis of (3). [Pd(pza)Cl]Cl·2H₂O (1 mmol) was dissolved in CH₃CN (5 ml) and a solution of 2 mmol of NaBF₄ in CH₃CN was added slowly. After elimination of NaCl by filtration, a solution of 2 mmol of NEt₄I in CH₃CN was added slowly, and the mixture, which turned red, was stirred for 6 h at room temperature. Evaporation of the solvent afforded complex (3) as a red solid, in 82% yield, and crystals were obtained by recrystallization from CH₃CN. Alternatively, complex (3) may be obtained in 89% yield by reacting an aqueous solution of [Pd(pza)Cl]Cl·2H₂O (1 mmol) and NaI (2 mmol) for 6 h at room temperature.

Synthesis of (4). [Pd(pza)Cl]Cl·2H₂O (1 mmol) was dissolved in CH₃CN. A solution of NaN₃ (2 mmol, CH₃CN/H₂O mixture 4:1, v/v) was added slowly. The formed precipitate of NaCl was eliminated by filtration, and the mixture was further stirred at room temperature for 10 h. Evaporation of the solvent afforded complex (4) as a yellow solid, in 61% yield, and crystals were obtained by recrystallization from CH₃CN.

Synthesis of (5). [Pd(pza)Cl]Cl·2H₂O (1 mmol) was dissolved in H₂O, and an aqueous solution of 2 mmol of KNCS was added slowly. The mixture was stirred for 10 h at room temperature. The formed pink solid, (5), was separated by filtration and dried in reduced pressure at 313 K. Yield: 48%. Crystals were obtained by recrystallization from a mixture of CH₃CN and CH₂Cl₂ (2:1, v/v).

5. Refinement

Crystal data, data collection and structure refinement details for (1)–(5) are summarized in Table 6. Data collection and refinement are routine works, except for a positional disorder found in (5) for sites N10A/N10B, for which the s.o.f. converged to 0.770 (18) and 0.230 (18), respectively. All H atoms bonded to C and N atoms were placed in calculated positions and refined as riding atoms, with fixed bond lengths of 0.93, 0.96, 0.97, and 0.90 Å for aromatic, methyl, methylene, and amine groups, respectively. In (3) and (4), H atoms for water molecules were found in difference maps, and first refined with free coordinates and restrained distances O—H = 0.85 (2) and H⋯H = 1.34 (4) Å. In the final cycles, water H atoms were fixed and refined as riding atoms. Isotropic displacement parameters for all H atoms were calculated as U_iso(H) = xU_eq(carrier atom), with x = 1.2 (methylene, aromatic, and amine groups) or x = 1.5 (methyl and water).

Table 6
Experimental details

	(1)	(2)	(3)	(4)	(5)
Crystal data
Chemical formula	[PdCl(C₁₄H₂₃N₅)]NO₃	[PdBr(C₁₄H₂₃N₅)]NO₃	[PdI(C₁₄H₂N₅)]I·0.5H₂O	[Pd(N₃)(C₁₄H₂₃N₅)]N₃·H₂O	[Pd(NCS)(C₁₄H₂₃N₅)]₂[Pd(NCS)₄]
M_r	465.23	509.69	630.58	469.85	1190.43
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/n	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/c	Triclinic, P $[\overline{1}]$
Temperature (K)	298	298	299	296	298
a, b, c (Å)	11.046 (2), 12.2941 (15), 14.0978 (16)	10.934 (6), 12.443 (4), 14.112 (6)	12.013 (4), 12.089 (4), 15.162 (5)	8.132 (3), 22.851 (5), 11.372 (3)	9.0286 (17), 10.532 (2), 13.066 (3)
α, β, γ (°)	90, 94.740 (16), 90	90, 94.76 (4), 90	106.17 (2), 97.34 (3), 106.79 (3)	90, 109.03 (2), 90	94.838 (14), 100.947 (12), 103.989 (13)
V (Å³)	1907.9 (5)	1913.4 (14)	1972.0 (11)	1997.8 (10)	1172.5 (4)
Z	4	4	4	4	1
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	1.14	3.08	4.08	0.96	1.45
Crystal size (mm)	0.40 × 0.12 × 0.10	0.60 × 0.40 × 0.18	0.20 × 0.15 × 0.04	0.50 × 0.40 × 0.40	0.40 × 0.40 × 0.12

Data collection
Diffractometer	Siemens P4	Siemens P4	Siemens P4	Siemens P4	Siemens P4
Absorption correction	ψ scan (XSCANS; Siemens, 1996 )	ψ scan (XSCANS; Siemens, 1996)	ψ scan (XSCANS; Siemens, 1996)	ψ scan (XSCANS; Siemens, 1996)	ψ scan (XSCANS; Siemens, 1996)
T_min, T_max	0.469, 0.517	0.206, 0.352	0.446, 0.523	0.266, 0.366	0.256, 0.378
No. of measured, independent and observed [I > 2σ(I)] reflections	4513, 3372, 2110	12224, 4962, 3329	8975, 6835, 4559	8431, 4032, 3528	8889, 5367, 4874
R_int	0.044	0.080	0.043	0.056	0.038
(sin θ/λ)_max (Å⁻¹)	0.596	0.677	0.595	0.623	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.158, 1.05	0.051, 0.148, 1.05	0.040, 0.101, 1.03	0.036, 0.097, 1.08	0.039, 0.107, 1.06
No. of reflections	3372	4962	6835	4032	5367
No. of parameters	230	231	414	248	282
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.45, −1.11	1.10, −1.01	0.85, −1.04	0.55, −1.04	0.83, −1.06
Computer programs: XSCANS (Siemens, 1996), SHELXS2014, SHELXL2014 and SHELXTL (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC references: 1036262; 1036261; 1036260; 1036259; 1036258

Crystal structure: contains datablocks 1, 2, 3, 4, 5, global. DOI: https://doi.org/10.1107/S205698901402595X/wm5076sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S205698901402595X/wm50761sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S205698901402595X/wm50762sup3.hkl

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S205698901402595X/wm50763sup4.hkl

Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S205698901402595X/wm50764sup5.hkl

Structure factors: contains datablock 5. DOI: https://doi.org/10.1107/S205698901402595X/wm50765sup6.hkl

checkCIF report

Computing details top

For all compounds, data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008). Molecular graphics: SHELXTL (Sheldrick, 2008) for (1), (3), (4), (5); SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008) for (2). For all compounds, software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(1) {Bis[2-(3,5-dimethylpyrazol-1-yl-κN²)ethyl]amine-κN}chloridopalladium nitrate top

Crystal data top

[PdCl(C₁₄H₂₃N₅)]NO₃	F(000) = 944
M_r = 465.23	D_x = 1.620 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.046 (2) Å	Cell parameters from 51 reflections
b = 12.2941 (15) Å	θ = 4.2–11.4°
c = 14.0978 (16) Å	µ = 1.14 mm⁻¹
β = 94.740 (16)°	T = 298 K
V = 1907.9 (5) Å³	Irregular, yellow
Z = 4	0.40 × 0.12 × 0.10 mm

Data collection top

Siemens P4 diffractometer	2110 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, FN4	R_int = 0.044
Graphite monochromator	θ_max = 25.1°, θ_min = 2.2°
ω scans	h = −13→2
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −14→1
T_min = 0.469, T_max = 0.517	l = −16→16
4513 measured reflections	2 standard reflections every 98 reflections
3372 independent reflections	intensity decay: 2.5%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0649P)² + 4.1623P] where P = (F_o² + 2F_c²)/3
3372 reflections	(Δ/σ)_max = 0.001
230 parameters	Δρ_max = 1.45 e Å⁻³
0 restraints	Δρ_min = −1.11 e Å⁻³
0 constraints

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

	x	y	z	U_iso*/U_eq
Pd1	0.72319 (6)	0.71729 (4)	0.48704 (4)	0.0531 (2)
Cl1	0.8178 (2)	0.79157 (19)	0.36252 (16)	0.0787 (7)
N1	0.6837 (6)	0.8628 (5)	0.5434 (4)	0.0526 (15)
N2	0.5729 (6)	0.8737 (5)	0.5775 (4)	0.0590 (17)
C3	0.5644 (8)	0.9712 (7)	0.6217 (6)	0.063 (2)
C4	0.6727 (8)	1.0222 (7)	0.6145 (6)	0.062 (2)
H4A	0.6935	1.0913	0.6372	0.074*
C5	0.7454 (8)	0.9534 (6)	0.5679 (6)	0.057 (2)
C6	0.4531 (9)	1.0055 (9)	0.6675 (8)	0.094 (3)
H6A	0.3833	0.9982	0.6227	0.141*
H6B	0.4614	1.0800	0.6874	0.141*
H6C	0.4433	0.9603	0.7219	0.141*
C7	0.8714 (9)	0.9703 (8)	0.5461 (8)	0.087 (3)
H7A	0.9208	0.9113	0.5717	0.131*
H7B	0.9010	1.0375	0.5740	0.131*
H7C	0.8752	0.9734	0.4784	0.131*
C8	0.4865 (8)	0.7861 (7)	0.5628 (6)	0.071 (2)
H8A	0.4758	0.7689	0.4955	0.086*
H8B	0.4086	0.8094	0.5827	0.086*
C9	0.5280 (9)	0.6844 (8)	0.6183 (7)	0.085 (3)
H9A	0.5163	0.6950	0.6851	0.102*
H9B	0.4782	0.6232	0.5956	0.102*
N10	0.6567 (6)	0.6590 (5)	0.6082 (4)	0.0592 (17)
H10	0.6972	0.6969	0.6553	0.071*
N11	0.7516 (6)	0.5655 (5)	0.4398 (4)	0.0592 (17)
N12	0.8073 (7)	0.4924 (5)	0.5011 (4)	0.0668 (19)
C13	0.8283 (8)	0.3993 (7)	0.4553 (6)	0.066 (2)
C14	0.7855 (8)	0.4148 (6)	0.3638 (6)	0.065 (2)
H14A	0.7896	0.3645	0.3148	0.078*
C15	0.7349 (7)	0.5173 (6)	0.3546 (5)	0.0550 (19)
C16	0.8887 (11)	0.3031 (8)	0.5040 (7)	0.096 (3)
H16A	0.8463	0.2837	0.5583	0.145*
H16B	0.9714	0.3210	0.5244	0.145*
H16C	0.8872	0.2429	0.4605	0.145*
C17	0.6704 (9)	0.5709 (8)	0.2707 (6)	0.081 (3)
H17A	0.5987	0.6063	0.2896	0.121*
H17B	0.6478	0.5173	0.2230	0.121*
H17C	0.7229	0.6238	0.2453	0.121*
C18	0.8104 (10)	0.5127 (7)	0.6030 (5)	0.078 (3)
H18A	0.8676	0.5707	0.6201	0.094*
H18B	0.8380	0.4477	0.6373	0.094*
C19	0.6873 (11)	0.5438 (7)	0.6310 (6)	0.080 (3)
H19A	0.6268	0.4969	0.5982	0.096*
H19B	0.6845	0.5323	0.6989	0.096*
N20	0.8548 (9)	0.7786 (5)	0.7798 (5)	0.069 (2)
O1	0.7422 (7)	0.7795 (6)	0.7736 (5)	0.0859 (19)
O2	0.9057 (8)	0.7441 (7)	0.7123 (6)	0.105 (2)
O3	0.9127 (7)	0.8085 (5)	0.8529 (5)	0.097 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0779 (5)	0.0434 (3)	0.0381 (3)	0.0043 (3)	0.0053 (3)	0.0013 (3)
Cl1	0.0987 (17)	0.0776 (15)	0.0621 (13)	0.0096 (13)	0.0200 (12)	0.0223 (11)
N1	0.056 (4)	0.045 (4)	0.057 (4)	0.001 (3)	0.009 (3)	−0.004 (3)
N2	0.065 (5)	0.060 (4)	0.052 (4)	−0.002 (4)	0.004 (3)	−0.003 (3)
C3	0.072 (6)	0.063 (5)	0.053 (5)	0.019 (5)	−0.003 (4)	−0.006 (4)
C4	0.068 (6)	0.047 (4)	0.070 (5)	0.006 (4)	0.005 (4)	−0.012 (4)
C5	0.065 (6)	0.046 (4)	0.061 (5)	−0.002 (4)	0.006 (4)	0.010 (4)
C6	0.082 (7)	0.102 (8)	0.100 (8)	0.024 (6)	0.010 (6)	−0.029 (6)
C7	0.095 (8)	0.063 (6)	0.105 (8)	−0.015 (5)	0.021 (6)	−0.005 (5)
C8	0.070 (6)	0.083 (6)	0.060 (5)	−0.007 (5)	−0.004 (4)	−0.010 (5)
C9	0.095 (8)	0.088 (7)	0.071 (6)	−0.030 (6)	0.011 (5)	−0.007 (5)
N10	0.083 (5)	0.053 (4)	0.042 (3)	−0.014 (4)	0.006 (3)	−0.003 (3)
N11	0.097 (5)	0.044 (3)	0.036 (3)	0.015 (4)	0.004 (3)	0.000 (3)
N12	0.098 (6)	0.050 (4)	0.050 (4)	0.013 (4)	−0.010 (4)	0.003 (3)
C13	0.081 (6)	0.050 (5)	0.069 (6)	0.010 (4)	0.015 (5)	0.003 (4)
C14	0.080 (6)	0.052 (5)	0.064 (5)	0.009 (5)	0.014 (5)	−0.007 (4)
C15	0.063 (5)	0.061 (5)	0.041 (4)	0.006 (4)	0.002 (4)	−0.008 (4)
C16	0.131 (9)	0.073 (7)	0.089 (7)	0.039 (6)	0.028 (7)	0.012 (5)
C17	0.100 (7)	0.096 (7)	0.045 (5)	0.023 (6)	−0.003 (5)	−0.010 (5)
C18	0.137 (9)	0.047 (5)	0.046 (5)	0.008 (6)	−0.017 (5)	0.004 (4)
C19	0.147 (9)	0.057 (5)	0.037 (4)	−0.013 (6)	0.007 (5)	0.005 (4)
N20	0.102 (7)	0.045 (4)	0.058 (5)	−0.003 (5)	−0.004 (5)	0.003 (4)
O1	0.086 (5)	0.094 (5)	0.077 (4)	−0.004 (4)	0.003 (4)	−0.018 (4)
O2	0.115 (6)	0.110 (6)	0.091 (5)	−0.002 (4)	0.005 (5)	−0.024 (4)
O3	0.136 (6)	0.073 (4)	0.075 (4)	−0.005 (4)	−0.039 (4)	−0.004 (3)

Geometric parameters (Å, º) top

Pd1—N11	2.015 (6)	N10—C19	1.485 (10)
Pd1—N1	2.019 (6)	N10—H10	0.9000
Pd1—N10	2.045 (6)	N11—C15	1.339 (9)
Pd1—Cl1	2.305 (2)	N11—N12	1.357 (8)
N1—C5	1.337 (9)	N12—C13	1.344 (10)
N1—N2	1.358 (9)	N12—C18	1.455 (10)
N2—C3	1.358 (10)	C13—C14	1.351 (11)
N2—C8	1.442 (10)	C13—C16	1.496 (12)
C3—C4	1.362 (11)	C14—C15	1.380 (11)
C3—C6	1.495 (12)	C14—H14A	0.9300
C4—C5	1.372 (11)	C15—C17	1.484 (11)
C4—H4A	0.9300	C16—H16A	0.9600
C5—C7	1.465 (12)	C16—H16B	0.9600
C6—H6A	0.9600	C16—H16C	0.9600
C6—H6B	0.9600	C17—H17A	0.9600
C6—H6C	0.9600	C17—H17B	0.9600
C7—H7A	0.9600	C17—H17C	0.9600
C7—H7B	0.9600	C18—C19	1.497 (13)
C7—H7C	0.9600	C18—H18A	0.9700
C8—C9	1.525 (13)	C18—H18B	0.9700
C8—H8A	0.9700	C19—H19A	0.9700
C8—H8B	0.9700	C19—H19B	0.9700
C9—N10	1.473 (11)	N20—O2	1.219 (10)
C9—H9A	0.9700	N20—O3	1.223 (9)
C9—H9B	0.9700	N20—O1	1.239 (9)

N11—Pd1—N1	174.3 (3)	C19—N10—Pd1	115.1 (5)
N11—Pd1—N10	91.6 (3)	C9—N10—H10	104.1
N1—Pd1—N10	83.0 (3)	C19—N10—H10	104.1
N11—Pd1—Cl1	91.30 (19)	Pd1—N10—H10	104.1
N1—Pd1—Cl1	94.30 (19)	C15—N11—N12	107.5 (6)
N10—Pd1—Cl1	172.9 (2)	C15—N11—Pd1	133.8 (5)
C5—N1—N2	106.4 (6)	N12—N11—Pd1	118.5 (4)
C5—N1—Pd1	135.9 (6)	C13—N12—N11	110.2 (6)
N2—N1—Pd1	117.2 (5)	C13—N12—C18	128.9 (7)
C3—N2—N1	110.4 (7)	N11—N12—C18	119.2 (6)
C3—N2—C8	130.9 (8)	N12—C13—C14	106.1 (7)
N1—N2—C8	118.7 (7)	N12—C13—C16	122.8 (8)
N2—C3—C4	106.1 (7)	C14—C13—C16	131.1 (8)
N2—C3—C6	122.5 (9)	C13—C14—C15	109.0 (7)
C4—C3—C6	131.3 (8)	C13—C14—H14A	125.5
C3—C4—C5	107.7 (7)	C15—C14—H14A	125.5
C3—C4—H4A	126.1	N11—C15—C14	107.2 (7)
C5—C4—H4A	126.1	N11—C15—C17	122.7 (7)
N1—C5—C4	109.3 (7)	C14—C15—C17	130.1 (7)
N1—C5—C7	122.6 (8)	C13—C16—H16A	109.5
C4—C5—C7	128.1 (8)	C13—C16—H16B	109.5
C3—C6—H6A	109.5	H16A—C16—H16B	109.5
C3—C6—H6B	109.5	C13—C16—H16C	109.5
H6A—C6—H6B	109.5	H16A—C16—H16C	109.5
C3—C6—H6C	109.5	H16B—C16—H16C	109.5
H6A—C6—H6C	109.5	C15—C17—H17A	109.5
H6B—C6—H6C	109.5	C15—C17—H17B	109.5
C5—C7—H7A	109.5	H17A—C17—H17B	109.5
C5—C7—H7B	109.5	C15—C17—H17C	109.5
H7A—C7—H7B	109.5	H17A—C17—H17C	109.5
C5—C7—H7C	109.5	H17B—C17—H17C	109.5
H7A—C7—H7C	109.5	N12—C18—C19	110.9 (7)
H7B—C7—H7C	109.5	N12—C18—H18A	109.5
N2—C8—C9	111.8 (7)	C19—C18—H18A	109.5
N2—C8—H8A	109.3	N12—C18—H18B	109.5
C9—C8—H8A	109.3	C19—C18—H18B	109.5
N2—C8—H8B	109.3	H18A—C18—H18B	108.1
C9—C8—H8B	109.3	N10—C19—C18	112.5 (7)
H8A—C8—H8B	107.9	N10—C19—H19A	109.1
N10—C9—C8	112.1 (7)	C18—C19—H19A	109.1
N10—C9—H9A	109.2	N10—C19—H19B	109.1
C8—C9—H9A	109.2	C18—C19—H19B	109.1
N10—C9—H9B	109.2	H19A—C19—H19B	107.8
C8—C9—H9B	109.2	O2—N20—O3	121.2 (10)
H9A—C9—H9B	107.9	O2—N20—O1	118.2 (8)
C9—N10—C19	112.7 (7)	O3—N20—O1	120.5 (9)
C9—N10—Pd1	115.0 (5)

C5—N1—N2—C3	1.1 (8)	C15—N11—N12—C13	1.2 (10)
Pd1—N1—N2—C3	173.7 (5)	Pd1—N11—N12—C13	−174.5 (6)
C5—N1—N2—C8	−179.0 (7)	C15—N11—N12—C18	−165.2 (8)
Pd1—N1—N2—C8	−6.4 (8)	Pd1—N11—N12—C18	19.0 (10)
N1—N2—C3—C4	0.1 (9)	N11—N12—C13—C14	0.4 (10)
C8—N2—C3—C4	−179.8 (8)	C18—N12—C13—C14	165.2 (9)
N1—N2—C3—C6	−179.2 (8)	N11—N12—C13—C16	180.0 (9)
C8—N2—C3—C6	0.9 (13)	C18—N12—C13—C16	−15.3 (15)
N2—C3—C4—C5	−1.2 (9)	N12—C13—C14—C15	−1.8 (10)
C6—C3—C4—C5	178.0 (9)	C16—C13—C14—C15	178.6 (10)
N2—N1—C5—C4	−1.8 (8)	N12—N11—C15—C14	−2.3 (9)
Pd1—N1—C5—C4	−172.4 (6)	Pd1—N11—C15—C14	172.5 (6)
N2—N1—C5—C7	177.9 (7)	N12—N11—C15—C17	176.7 (8)
Pd1—N1—C5—C7	7.3 (12)	Pd1—N11—C15—C17	−8.5 (13)
C3—C4—C5—N1	2.0 (9)	C13—C14—C15—N11	2.6 (10)
C3—C4—C5—C7	−177.8 (8)	C13—C14—C15—C17	−176.4 (9)
C3—N2—C8—C9	−113.1 (9)	C13—N12—C18—C19	−115.9 (10)
N1—N2—C8—C9	67.0 (9)	N11—N12—C18—C19	47.7 (10)
N2—C8—C9—N10	−45.8 (10)	C9—N10—C19—C18	168.9 (7)
C8—C9—N10—C19	−159.6 (7)	Pd1—N10—C19—C18	34.4 (8)
C8—C9—N10—Pd1	−25.0 (9)	N12—C18—C19—N10	−78.4 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···N20ⁱ	0.93	2.66	3.510 (10)	153
C7—H7C···Cl1	0.96	2.81	3.410 (10)	121
C8—H8A···O3ⁱⁱ	0.97	2.28	3.222 (10)	163
N10—H10···N20	0.90	2.57	3.453 (10)	167
N10—H10···O1	0.90	1.98	2.857 (9)	164
N10—H10···O2	0.90	2.45	3.186 (10)	140
C14—H14A···Cl1ⁱⁱⁱ	0.93	2.82	3.629 (9)	146
C16—H16A···O1^iv	0.96	2.64	3.572 (12)	164
C17—H17A···O3ⁱⁱ	0.96	2.53	3.491 (12)	175
C17—H17C···Cl1	0.96	2.79	3.367 (10)	119
C18—H18A···O2	0.97	2.51	3.364 (11)	146
C18—H18B···O1^iv	0.97	2.61	3.428 (11)	142
C19—H19A···O3^iv	0.97	2.47	3.112 (11)	124

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x−1/2, −y+3/2, z−1/2; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x+3/2, y−1/2, −z+3/2.

(2) {Bis[2-(3,5-dimethylpyrazol-1-yl-κN²)ethyl]amine-κN}bromidopalladium nitrate top

Crystal data top

[PdBr(C₁₄H₂₃N₅)]NO₃	F(000) = 1016
M_r = 509.69	D_x = 1.769 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.934 (6) Å	Cell parameters from 70 reflections
b = 12.443 (4) Å	θ = 5.0–12.5°
c = 14.112 (6) Å	µ = 3.08 mm⁻¹
β = 94.76 (4)°	T = 298 K
V = 1913.4 (14) Å³	Prism, yellow
Z = 4	0.60 × 0.40 × 0.18 mm

Data collection top

Siemens P4 diffractometer	3329 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.080
Graphite monochromator	θ_max = 28.8°, θ_min = 2.2°
ω scans	h = −14→14
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −16→16
T_min = 0.206, T_max = 0.352	l = −19→19
12224 measured reflections	3 standard reflections every 97 reflections
4962 independent reflections	intensity decay: 2.5%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.148	w = 1/[σ²(F_o²) + (0.0488P)² + 3.056P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
4962 reflections	Δρ_max = 1.10 e Å⁻³
231 parameters	Δρ_min = −1.01 e Å⁻³
0 restraints	Extinction correction: SHELXL2014, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.0042 (5)
Primary atom site location: structure-invariant direct methods

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

	x	y	z	U_iso*/U_eq
Pd1	0.72527 (4)	0.72194 (3)	0.49024 (3)	0.04869 (16)
Br1	0.82828 (6)	0.79805 (6)	0.36061 (5)	0.0713 (2)
N1	0.6855 (4)	0.8654 (4)	0.5458 (3)	0.0527 (10)
N2	0.5720 (4)	0.8754 (4)	0.5774 (3)	0.0559 (11)
C3	0.5614 (6)	0.9701 (5)	0.6223 (4)	0.0653 (15)
C4	0.6697 (6)	1.0215 (5)	0.6178 (5)	0.0683 (16)
H4A	0.6890	1.0898	0.6412	0.082*
C5	0.7463 (6)	0.9545 (4)	0.5723 (4)	0.0590 (14)
C6	0.4475 (7)	1.0010 (7)	0.6655 (6)	0.095 (3)
H6A	0.3795	0.9988	0.6179	0.143*
H6B	0.4561	1.0724	0.6908	0.143*
H6C	0.4330	0.9517	0.7157	0.143*
C7	0.8768 (6)	0.9714 (6)	0.5555 (6)	0.089 (2)
H7A	0.9217	0.9060	0.5686	0.134*
H7B	0.9105	1.0273	0.5966	0.134*
H7C	0.8827	0.9917	0.4904	0.134*
C8	0.4863 (6)	0.7883 (5)	0.5612 (5)	0.0694 (17)
H8A	0.4791	0.7704	0.4940	0.083*
H8B	0.4062	0.8114	0.5781	0.083*
C9	0.5245 (6)	0.6902 (6)	0.6176 (5)	0.0741 (18)
H9A	0.5108	0.7022	0.6838	0.089*
H9B	0.4740	0.6299	0.5949	0.089*
N10	0.6556 (4)	0.6634 (4)	0.6103 (3)	0.0566 (11)
H10	0.6956	0.7007	0.6579	0.068*
N11	0.7515 (5)	0.5725 (4)	0.4438 (3)	0.0590 (12)
N12	0.8088 (5)	0.5000 (4)	0.5054 (3)	0.0607 (12)
C13	0.8290 (6)	0.4082 (4)	0.4598 (4)	0.0596 (14)
C14	0.7837 (6)	0.4222 (5)	0.3675 (4)	0.0617 (14)
H14A	0.7853	0.3720	0.3188	0.074*
C15	0.7353 (5)	0.5240 (5)	0.3597 (4)	0.0577 (13)
C16	0.8890 (8)	0.3118 (6)	0.5076 (6)	0.091 (2)
H16A	0.8366	0.2833	0.5529	0.137*
H16B	0.9662	0.3325	0.5398	0.137*
H16C	0.9024	0.2581	0.4608	0.137*
C17	0.6657 (7)	0.5744 (6)	0.2765 (4)	0.081 (2)
H17A	0.6015	0.6186	0.2979	0.121*
H17B	0.6305	0.5194	0.2351	0.121*
H17C	0.7201	0.6179	0.2427	0.121*
C18	0.8102 (7)	0.5208 (5)	0.6062 (4)	0.0715 (18)
H18A	0.8671	0.5787	0.6233	0.086*
H18B	0.8384	0.4571	0.6412	0.086*
C19	0.6851 (7)	0.5506 (5)	0.6330 (4)	0.0704 (18)
H19A	0.6811	0.5390	0.7006	0.084*
H19B	0.6246	0.5045	0.5994	0.084*
N20	0.8449 (4)	0.7830 (3)	0.7852 (3)	0.0351 (8)
O1	0.7422 (7)	0.7835 (4)	0.7749 (4)	0.1053 (19)
O2	0.9013 (7)	0.7448 (6)	0.7245 (6)	0.125 (2)
O3	0.9009 (7)	0.8139 (5)	0.8568 (5)	0.113 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0552 (3)	0.0486 (2)	0.0429 (2)	0.00212 (18)	0.00814 (16)	0.00166 (16)
Br1	0.0761 (4)	0.0797 (4)	0.0608 (4)	0.0144 (3)	0.0225 (3)	0.0231 (3)
N1	0.048 (2)	0.057 (3)	0.054 (2)	0.002 (2)	0.012 (2)	−0.002 (2)
N2	0.048 (2)	0.069 (3)	0.051 (2)	0.006 (2)	0.008 (2)	−0.004 (2)
C3	0.070 (4)	0.067 (4)	0.058 (3)	0.018 (3)	0.002 (3)	−0.011 (3)
C4	0.082 (4)	0.057 (3)	0.065 (4)	0.005 (3)	0.005 (3)	−0.012 (3)
C5	0.068 (3)	0.048 (3)	0.061 (3)	−0.004 (3)	0.004 (3)	0.003 (3)
C6	0.078 (5)	0.120 (6)	0.089 (5)	0.034 (5)	0.013 (4)	−0.034 (5)
C7	0.071 (4)	0.079 (4)	0.120 (6)	−0.021 (4)	0.022 (4)	−0.013 (5)
C8	0.050 (3)	0.088 (5)	0.072 (4)	−0.002 (3)	0.014 (3)	−0.007 (3)
C9	0.069 (4)	0.081 (4)	0.075 (4)	−0.024 (4)	0.024 (3)	−0.009 (4)
N10	0.066 (3)	0.061 (3)	0.044 (2)	−0.011 (2)	0.010 (2)	−0.003 (2)
N11	0.077 (3)	0.055 (2)	0.045 (2)	0.011 (2)	0.005 (2)	0.002 (2)
N12	0.080 (3)	0.049 (2)	0.052 (3)	0.008 (2)	−0.003 (2)	0.001 (2)
C13	0.064 (3)	0.049 (3)	0.066 (3)	0.009 (3)	0.010 (3)	0.002 (3)
C14	0.069 (3)	0.058 (3)	0.059 (3)	0.010 (3)	0.008 (3)	−0.010 (3)
C15	0.057 (3)	0.062 (3)	0.054 (3)	0.009 (3)	0.004 (3)	−0.008 (3)
C16	0.110 (6)	0.067 (4)	0.096 (5)	0.032 (4)	0.010 (5)	0.008 (4)
C17	0.095 (5)	0.093 (5)	0.052 (3)	0.032 (4)	−0.009 (3)	−0.009 (3)
C18	0.107 (5)	0.050 (3)	0.055 (3)	0.006 (4)	−0.011 (3)	0.007 (3)
C19	0.109 (5)	0.057 (3)	0.046 (3)	−0.011 (4)	0.017 (3)	0.007 (3)
N20	0.051 (2)	0.0202 (15)	0.0322 (17)	−0.0047 (17)	−0.0085 (16)	−0.0046 (13)
O1	0.145 (6)	0.093 (4)	0.079 (4)	−0.003 (4)	0.014 (4)	−0.016 (3)
O2	0.115 (5)	0.117 (5)	0.139 (6)	−0.022 (4)	−0.021 (5)	−0.010 (5)
O3	0.140 (5)	0.090 (4)	0.103 (4)	−0.014 (4)	−0.027 (4)	0.006 (3)

Geometric parameters (Å, º) top

Pd1—N11	2.000 (5)	N10—C19	1.470 (8)
Pd1—N1	2.012 (4)	N10—H10	0.9000
Pd1—N10	2.048 (4)	N11—C15	1.330 (7)
Pd1—Br1	2.4194 (11)	N11—N12	1.368 (6)
N1—C5	1.330 (7)	N12—C13	1.339 (7)
N1—N2	1.359 (6)	N12—C18	1.444 (7)
N2—C3	1.347 (7)	C13—C14	1.366 (8)
N2—C8	1.438 (7)	C13—C16	1.500 (8)
C3—C4	1.352 (9)	C14—C15	1.373 (8)
C3—C6	1.482 (9)	C14—H14A	0.9300
C4—C5	1.378 (8)	C15—C17	1.484 (8)
C4—H4A	0.9300	C16—H16A	0.9600
C5—C7	1.480 (9)	C16—H16B	0.9600
C6—H6A	0.9600	C16—H16C	0.9600
C6—H6B	0.9600	C17—H17A	0.9600
C6—H6C	0.9600	C17—H17B	0.9600
C7—H7A	0.9600	C17—H17C	0.9600
C7—H7B	0.9600	C18—C19	1.496 (10)
C7—H7C	0.9600	C18—H18A	0.9700
C8—C9	1.498 (9)	C18—H18B	0.9700
C8—H8A	0.9700	C19—H19A	0.9700
C8—H8B	0.9700	C19—H19B	0.9700
C9—N10	1.484 (8)	N20—O2	1.195 (8)
C9—H9A	0.9700	N20—O3	1.200 (7)
C9—H9B	0.9700	N20—O1	1.121 (8)

N11—Pd1—N1	173.81 (19)	C19—N10—Pd1	115.5 (4)
N11—Pd1—N10	90.80 (19)	C9—N10—H10	104.1
N1—Pd1—N10	83.45 (19)	C19—N10—H10	104.1
N11—Pd1—Br1	91.58 (14)	Pd1—N10—H10	104.1
N1—Pd1—Br1	94.40 (13)	C15—N11—N12	106.7 (4)
N10—Pd1—Br1	173.21 (14)	C15—N11—Pd1	134.7 (4)
C5—N1—N2	106.3 (5)	N12—N11—Pd1	118.4 (3)
C5—N1—Pd1	136.9 (4)	C13—N12—N11	110.0 (4)
N2—N1—Pd1	116.2 (4)	C13—N12—C18	129.6 (5)
N1—N2—C3	110.5 (5)	N11—N12—C18	118.4 (5)
N1—N2—C8	118.7 (5)	C14—C13—N12	106.8 (5)
C3—N2—C8	130.8 (5)	C14—C13—C16	129.9 (6)
C4—C3—N2	106.4 (5)	N12—C13—C16	123.3 (6)
C4—C3—C6	131.8 (6)	C13—C14—C15	107.5 (5)
N2—C3—C6	121.9 (6)	C13—C14—H14A	126.2
C3—C4—C5	107.7 (5)	C15—C14—H14A	126.2
C3—C4—H4A	126.1	N11—C15—C14	109.0 (5)
C5—C4—H4A	126.1	N11—C15—C17	122.3 (5)
N1—C5—C4	109.0 (6)	C14—C15—C17	128.5 (5)
N1—C5—C7	122.6 (6)	C13—C16—H16A	109.5
C4—C5—C7	128.3 (6)	C13—C16—H16B	109.5
C3—C6—H6A	109.5	H16A—C16—H16B	109.5
C3—C6—H6B	109.5	C13—C16—H16C	109.5
H6A—C6—H6B	109.5	H16A—C16—H16C	109.5
C3—C6—H6C	109.5	H16B—C16—H16C	109.5
H6A—C6—H6C	109.5	C15—C17—H17A	109.5
H6B—C6—H6C	109.5	C15—C17—H17B	109.5
C5—C7—H7A	109.5	H17A—C17—H17B	109.5
C5—C7—H7B	109.5	C15—C17—H17C	109.5
H7A—C7—H7B	109.5	H17A—C17—H17C	109.5
C5—C7—H7C	109.5	H17B—C17—H17C	109.5
H7A—C7—H7C	109.5	N12—C18—C19	111.0 (5)
H7B—C7—H7C	109.5	N12—C18—H18A	109.4
N2—C8—C9	112.3 (5)	C19—C18—H18A	109.4
N2—C8—H8A	109.1	N12—C18—H18B	109.4
C9—C8—H8A	109.1	C19—C18—H18B	109.4
N2—C8—H8B	109.1	H18A—C18—H18B	108.0
C9—C8—H8B	109.1	C18—C19—N10	111.8 (5)
H8A—C8—H8B	107.9	C18—C19—H19A	109.3
N10—C9—C8	112.0 (5)	N10—C19—H19A	109.3
N10—C9—H9A	109.2	C18—C19—H19B	109.3
C8—C9—H9A	109.2	N10—C19—H19B	109.3
N10—C9—H9B	109.2	H19A—C19—H19B	107.9
C8—C9—H9B	109.2	O2—N20—O3	118.3 (6)
H9A—C9—H9B	107.9	O2—N20—O1	118.7 (5)
C9—N10—C19	113.3 (5)	O3—N20—O1	122.9 (6)
C9—N10—Pd1	113.9 (4)

C5—N1—N2—C3	0.7 (6)	C15—N11—N12—C13	0.7 (7)
Pd1—N1—N2—C3	173.2 (4)	Pd1—N11—N12—C13	−174.0 (4)
C5—N1—N2—C8	−178.2 (5)	C15—N11—N12—C18	−164.6 (6)
Pd1—N1—N2—C8	−5.6 (6)	Pd1—N11—N12—C18	20.7 (7)
N1—N2—C3—C4	0.8 (7)	N11—N12—C13—C14	−0.1 (7)
C8—N2—C3—C4	179.5 (6)	C18—N12—C13—C14	163.1 (7)
N1—N2—C3—C6	−178.8 (6)	N11—N12—C13—C16	−179.2 (6)
C8—N2—C3—C6	−0.2 (10)	C18—N12—C13—C16	−16.0 (11)
N2—C3—C4—C5	−1.9 (7)	N12—C13—C14—C15	−0.5 (7)
C6—C3—C4—C5	177.6 (7)	C16—C13—C14—C15	178.5 (7)
N2—N1—C5—C4	−1.9 (6)	N12—N11—C15—C14	−1.0 (7)
Pd1—N1—C5—C4	−172.0 (4)	Pd1—N11—C15—C14	172.4 (5)
N2—N1—C5—C7	176.5 (6)	N12—N11—C15—C17	174.4 (6)
Pd1—N1—C5—C7	6.3 (10)	Pd1—N11—C15—C17	−12.1 (10)
C3—C4—C5—N1	2.4 (7)	C13—C14—C15—N11	0.9 (7)
C3—C4—C5—C7	−175.8 (7)	C13—C14—C15—C17	−174.1 (7)
N1—N2—C8—C9	68.0 (7)	C13—N12—C18—C19	−114.3 (7)
C3—N2—C8—C9	−110.6 (7)	N11—N12—C18—C19	47.7 (7)
N2—C8—C9—N10	−47.3 (7)	N12—C18—C19—N10	−79.3 (6)
C8—C9—N10—C19	−158.6 (5)	C9—N10—C19—C18	168.4 (5)
C8—C9—N10—Pd1	−23.9 (7)	Pd1—N10—C19—C18	34.5 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···N20ⁱ	0.93	2.66	3.540 (7)	159
C7—H7C···Br1	0.96	3.06	3.500 (8)	110
C8—H8A···O3ⁱⁱ	0.97	2.30	3.219 (9)	157
N10—H10···N20	0.90	2.54	3.427 (6)	169
N10—H10···O1	0.90	1.98	2.857 (7)	166
N10—H10···O2	0.90	2.43	3.181 (8)	142
C14—H14A···Br1ⁱⁱⁱ	0.93	2.88	3.687 (6)	146
C16—H16A···O1^iv	0.96	2.65	3.511 (10)	150
C17—H17A···O3ⁱⁱ	0.96	2.55	3.485 (10)	164
C17—H17C···Br1	0.96	2.98	3.459 (8)	112
C18—H18A···O2	0.97	2.52	3.358 (9)	144
C18—H18B···O1^iv	0.97	2.65	3.468 (8)	142
C19—H19B···O3^iv	0.97	2.47	3.099 (9)	122

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x−1/2, −y+3/2, z−1/2; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x+3/2, y−1/2, −z+3/2.

(3) {Bis[2-(3,5-dimethylpyrazol-1-yl-κN²)ethyl]amine-κN}iodidopalladium iodide hemihydrate top

Crystal data top

[PdI(C₁₄H₂N₅)]I·0.5H₂O	Z = 4
M_r = 630.58	F(000) = 1196
Triclinic, P1	D_x = 2.124 Mg m⁻³
a = 12.013 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.089 (4) Å	Cell parameters from 68 reflections
c = 15.162 (5) Å	θ = 4.2–12.0°
α = 106.17 (2)°	µ = 4.08 mm⁻¹
β = 97.34 (3)°	T = 299 K
γ = 106.79 (3)°	Plate, orange
V = 1972.0 (11) Å³	0.20 × 0.15 × 0.04 mm

Data collection top

Siemens P4 diffractometer	4559 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.043
Graphite monochromator	θ_max = 25.0°, θ_min = 1.8°
ω scans	h = −14→3
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −13→13
T_min = 0.446, T_max = 0.523	l = −18→18
8975 measured reflections	3 standard reflections every 97 reflections
6835 independent reflections	intensity decay: 1.5%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: mixed
wR(F²) = 0.101	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0324P)² + 6.3989P] where P = (F_o² + 2F_c²)/3
6835 reflections	(Δ/σ)_max = 0.001
414 parameters	Δρ_max = 0.85 e Å⁻³
0 restraints	Δρ_min = −1.04 e Å⁻³
0 constraints

Special details top

Refinement. Geometry of the water molecule first regularized with soft restraints: DFIX 0.85 0.02 O1 H1 O1 H2 DANG 1.34 0.04 H1 H2 then fixed in last l.s. cycles.

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

	x	y	z	U_iso*/U_eq
Pd1	0.64608 (5)	0.84173 (5)	0.70510 (4)	0.03566 (15)
I1	0.75703 (5)	0.76282 (6)	0.57898 (4)	0.05531 (17)
N1	0.6227 (5)	0.7009 (6)	0.7556 (4)	0.0393 (15)
N2	0.6504 (5)	0.7285 (6)	0.8519 (4)	0.0405 (15)
C3	0.6317 (7)	0.6248 (8)	0.8731 (6)	0.045 (2)
C4	0.5940 (7)	0.5293 (8)	0.7912 (6)	0.047 (2)
H4A	0.5768	0.4468	0.7844	0.057*
C5	0.5864 (7)	0.5794 (7)	0.7195 (6)	0.045 (2)
C6	0.6539 (9)	0.6222 (10)	0.9712 (6)	0.067 (3)
H6A	0.7355	0.6698	1.0025	0.101*
H6B	0.6382	0.5391	0.9697	0.101*
H6C	0.6022	0.6560	1.0047	0.101*
C7	0.5422 (8)	0.5142 (8)	0.6166 (6)	0.062 (3)
H7A	0.5253	0.5693	0.5863	0.093*
H7B	0.4707	0.4460	0.6052	0.093*
H7C	0.6019	0.4852	0.5917	0.093*
C8	0.6637 (7)	0.8494 (7)	0.9118 (5)	0.046 (2)
H8A	0.7347	0.9082	0.9063	0.055*
H8B	0.6738	0.8519	0.9769	0.055*
C9	0.5567 (7)	0.8842 (8)	0.8854 (6)	0.049 (2)
H9A	0.4845	0.8156	0.8749	0.058*
H9B	0.5558	0.9523	0.9371	0.058*
N10	0.5581 (5)	0.9190 (6)	0.7995 (4)	0.0389 (15)
H10A	0.6005	0.9996	0.8206	0.047*
N11	0.6523 (5)	0.9860 (5)	0.6634 (4)	0.0355 (14)
N12	0.5449 (5)	1.0022 (6)	0.6428 (4)	0.0417 (15)
C13	0.5610 (7)	1.1056 (7)	0.6222 (5)	0.0433 (19)
C14	0.6808 (7)	1.1565 (8)	0.6286 (6)	0.051 (2)
H14A	0.7183	1.2276	0.6161	0.061*
C15	0.7350 (7)	1.0819 (7)	0.6569 (5)	0.0405 (18)
C16	0.4620 (8)	1.1495 (8)	0.5978 (7)	0.059 (2)
H16A	0.3928	1.0808	0.5603	0.089*
H16B	0.4854	1.2038	0.5626	0.089*
H16C	0.4438	1.1922	0.6545	0.089*
C17	0.8642 (7)	1.0992 (9)	0.6824 (6)	0.057 (2)
H17A	0.8845	1.0992	0.7457	0.085*
H17B	0.9107	1.1760	0.6780	0.085*
H17C	0.8806	1.0337	0.6398	0.085*
C18	0.4389 (6)	0.9129 (7)	0.6494 (6)	0.047 (2)
H18A	0.4311	0.8324	0.6081	0.056*
H18B	0.3694	0.9319	0.6276	0.056*
C19	0.4409 (7)	0.9094 (7)	0.7490 (6)	0.047 (2)
H19A	0.4181	0.9763	0.7843	0.057*
H19B	0.3821	0.8334	0.7461	0.057*
Pd2	0.89057 (5)	0.31577 (5)	0.31013 (4)	0.03801 (16)
I2	0.78206 (5)	0.41030 (5)	0.43265 (4)	0.06044 (19)
N21	0.8807 (5)	0.1716 (6)	0.3554 (4)	0.0408 (15)
N22	0.8361 (5)	0.0562 (6)	0.2895 (4)	0.0413 (15)
C23	0.8361 (7)	−0.0288 (8)	0.3313 (6)	0.0441 (19)
C24	0.8777 (7)	0.0336 (8)	0.4249 (6)	0.053 (2)
H24A	0.8851	−0.0005	0.4723	0.064*
C25	0.9072 (6)	0.1582 (8)	0.4373 (5)	0.0428 (19)
C26	0.7980 (8)	−0.1613 (8)	0.2781 (7)	0.061 (2)
H26A	0.7264	−0.1845	0.2309	0.091*
H26B	0.7830	−0.2070	0.3205	0.091*
H26C	0.8598	−0.1783	0.2482	0.091*
C27	0.9661 (8)	0.2630 (8)	0.5245 (6)	0.059 (2)
H27A	1.0039	0.3345	0.5090	0.089*
H27B	1.0251	0.2453	0.5618	0.089*
H27C	0.9078	0.2777	0.5597	0.089*
C28	0.8342 (7)	0.0419 (7)	0.1900 (5)	0.045 (2)
H28A	0.7730	0.0697	0.1648	0.055*
H28B	0.8152	−0.0439	0.1541	0.055*
C29	0.9540 (7)	0.1153 (7)	0.1807 (5)	0.0435 (19)
H29A	1.0163	0.1051	0.2217	0.052*
H29B	0.9618	0.0845	0.1163	0.052*
N30	0.9695 (5)	0.2441 (5)	0.2048 (4)	0.0380 (15)
H30A	0.9298	0.2498	0.1527	0.046*
N31	0.9132 (5)	0.4530 (6)	0.2548 (5)	0.0436 (16)
N32	1.0221 (5)	0.4929 (6)	0.2337 (5)	0.0437 (16)
C33	1.0186 (7)	0.5512 (8)	0.1718 (6)	0.051 (2)
C34	0.9048 (8)	0.5537 (8)	0.1536 (7)	0.061 (2)
H34A	0.8753	0.5902	0.1139	0.073*
C35	0.8427 (7)	0.4922 (8)	0.2053 (7)	0.054 (2)
C36	1.1245 (8)	0.5984 (9)	0.1333 (7)	0.070 (3)
H36A	1.1892	0.6565	0.1841	0.104*
H36B	1.1040	0.6375	0.0897	0.104*
H36C	1.1482	0.5314	0.1014	0.104*
C37	0.7122 (8)	0.4641 (10)	0.2050 (8)	0.079 (3)
H37A	0.6921	0.4198	0.2476	0.118*
H37B	0.6656	0.4153	0.1425	0.118*
H37C	0.6957	0.5392	0.2245	0.118*
C38	1.1151 (6)	0.4525 (7)	0.2691 (5)	0.044 (2)
H38A	1.1185	0.4627	0.3352	0.053*
H38B	1.1914	0.5033	0.2641	0.053*
C39	1.0946 (6)	0.3211 (7)	0.2160 (6)	0.0430 (19)
H39A	1.1120	0.3141	0.1544	0.052*
H39B	1.1481	0.2923	0.2497	0.052*
I3	0.44634 (6)	0.76946 (6)	0.10827 (4)	0.06206 (19)
I4	−0.00003 (8)	0.83190 (7)	0.05319 (5)	0.0843 (2)
O1	0.2414 (8)	0.8235 (8)	−0.0455 (6)	0.112 (3)
H1	0.3020	0.8127	−0.0184	0.168*
H2	0.1967	0.8227	−0.0063	0.168*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0346 (3)	0.0398 (3)	0.0366 (3)	0.0169 (3)	0.0098 (3)	0.0139 (3)
I1	0.0580 (4)	0.0757 (4)	0.0464 (3)	0.0390 (3)	0.0199 (3)	0.0212 (3)
N1	0.046 (4)	0.040 (4)	0.036 (4)	0.021 (3)	0.004 (3)	0.015 (3)
N2	0.041 (4)	0.041 (4)	0.039 (4)	0.014 (3)	0.008 (3)	0.013 (3)
C3	0.039 (4)	0.056 (5)	0.060 (5)	0.024 (4)	0.026 (4)	0.035 (5)
C4	0.051 (5)	0.041 (5)	0.059 (6)	0.023 (4)	0.018 (4)	0.022 (4)
C5	0.041 (4)	0.041 (5)	0.058 (5)	0.017 (4)	0.014 (4)	0.020 (4)
C6	0.078 (7)	0.090 (8)	0.058 (6)	0.040 (6)	0.027 (5)	0.045 (6)
C7	0.065 (6)	0.044 (5)	0.057 (6)	0.017 (5)	−0.004 (5)	−0.002 (4)
C8	0.054 (5)	0.050 (5)	0.030 (4)	0.015 (4)	0.009 (4)	0.013 (4)
C9	0.062 (6)	0.050 (5)	0.045 (5)	0.028 (4)	0.028 (4)	0.017 (4)
N10	0.035 (3)	0.033 (3)	0.048 (4)	0.011 (3)	0.013 (3)	0.012 (3)
N11	0.031 (3)	0.039 (4)	0.040 (4)	0.015 (3)	0.009 (3)	0.015 (3)
N12	0.035 (4)	0.044 (4)	0.051 (4)	0.018 (3)	0.009 (3)	0.017 (3)
C13	0.047 (5)	0.043 (5)	0.042 (5)	0.019 (4)	0.012 (4)	0.013 (4)
C14	0.048 (5)	0.049 (5)	0.053 (5)	0.007 (4)	0.009 (4)	0.025 (4)
C15	0.040 (4)	0.042 (5)	0.038 (4)	0.006 (4)	0.008 (3)	0.017 (4)
C16	0.065 (6)	0.059 (6)	0.071 (6)	0.038 (5)	0.013 (5)	0.030 (5)
C17	0.032 (4)	0.071 (6)	0.061 (6)	0.006 (4)	0.010 (4)	0.027 (5)
C18	0.029 (4)	0.042 (5)	0.065 (6)	0.011 (4)	0.003 (4)	0.018 (4)
C19	0.038 (4)	0.037 (5)	0.066 (6)	0.011 (4)	0.020 (4)	0.015 (4)
Pd2	0.0361 (3)	0.0380 (3)	0.0417 (3)	0.0144 (3)	0.0132 (3)	0.0122 (3)
I2	0.0549 (4)	0.0480 (3)	0.0688 (4)	0.0130 (3)	0.0295 (3)	0.0026 (3)
N21	0.042 (4)	0.040 (4)	0.038 (4)	0.014 (3)	0.009 (3)	0.009 (3)
N22	0.039 (4)	0.046 (4)	0.039 (4)	0.014 (3)	0.010 (3)	0.015 (3)
C23	0.034 (4)	0.054 (5)	0.051 (5)	0.018 (4)	0.013 (4)	0.023 (4)
C24	0.043 (5)	0.060 (6)	0.055 (6)	0.011 (4)	0.007 (4)	0.027 (5)
C25	0.030 (4)	0.060 (6)	0.036 (4)	0.006 (4)	0.009 (3)	0.022 (4)
C26	0.062 (6)	0.042 (5)	0.084 (7)	0.016 (4)	0.018 (5)	0.029 (5)
C27	0.063 (6)	0.063 (6)	0.043 (5)	0.006 (5)	0.013 (4)	0.019 (5)
C28	0.048 (5)	0.045 (5)	0.040 (5)	0.018 (4)	0.006 (4)	0.008 (4)
C29	0.052 (5)	0.050 (5)	0.038 (4)	0.028 (4)	0.012 (4)	0.017 (4)
N30	0.040 (4)	0.041 (4)	0.037 (3)	0.020 (3)	0.009 (3)	0.014 (3)
N31	0.036 (4)	0.038 (4)	0.062 (4)	0.015 (3)	0.018 (3)	0.019 (3)
N32	0.034 (4)	0.045 (4)	0.056 (4)	0.014 (3)	0.012 (3)	0.020 (3)
C33	0.052 (5)	0.047 (5)	0.067 (6)	0.020 (4)	0.019 (4)	0.032 (5)
C34	0.063 (6)	0.058 (6)	0.088 (7)	0.036 (5)	0.023 (5)	0.044 (5)
C35	0.041 (5)	0.042 (5)	0.085 (7)	0.018 (4)	0.010 (5)	0.026 (5)
C36	0.062 (6)	0.080 (7)	0.091 (7)	0.028 (5)	0.034 (6)	0.053 (6)
C37	0.048 (6)	0.082 (8)	0.124 (9)	0.031 (5)	0.019 (6)	0.052 (7)
C38	0.027 (4)	0.060 (6)	0.046 (5)	0.013 (4)	0.009 (3)	0.020 (4)
C39	0.034 (4)	0.054 (5)	0.052 (5)	0.023 (4)	0.013 (4)	0.025 (4)
I3	0.0659 (4)	0.0564 (4)	0.0662 (4)	0.0252 (3)	0.0144 (3)	0.0195 (3)
I4	0.1379 (7)	0.0760 (5)	0.0587 (4)	0.0551 (5)	0.0243 (4)	0.0319 (4)
O1	0.123 (7)	0.129 (7)	0.089 (6)	0.055 (6)	−0.014 (5)	0.047 (5)

Geometric parameters (Å, º) top

Pd1—N11	1.999 (6)	Pd2—N31	2.026 (6)
Pd1—N1	2.018 (6)	Pd2—N30	2.071 (6)
Pd1—N10	2.061 (6)	Pd2—I2	2.5987 (11)
Pd1—I1	2.5910 (11)	N21—C25	1.307 (9)
N1—C5	1.330 (10)	N21—N22	1.374 (8)
N1—N2	1.376 (8)	N22—C23	1.349 (10)
N2—C3	1.343 (10)	N22—C28	1.467 (9)
N2—C8	1.440 (10)	C23—C24	1.355 (11)
C3—C4	1.356 (11)	C23—C26	1.480 (12)
C3—C6	1.487 (11)	C24—C25	1.395 (12)
C4—C5	1.389 (11)	C24—H24A	0.9300
C4—H4A	0.9300	C25—C27	1.472 (11)
C5—C7	1.483 (11)	C26—H26A	0.9600
C6—H6A	0.9600	C26—H26B	0.9600
C6—H6B	0.9600	C26—H26C	0.9600
C6—H6C	0.9600	C27—H27A	0.9600
C7—H7A	0.9600	C27—H27B	0.9600
C7—H7B	0.9600	C27—H27C	0.9600
C7—H7C	0.9600	C28—C29	1.504 (11)
C8—C9	1.505 (11)	C28—H28A	0.9700
C8—H8A	0.9700	C28—H28B	0.9700
C8—H8B	0.9700	C29—N30	1.446 (9)
C9—N10	1.477 (10)	C29—H29A	0.9700
C9—H9A	0.9700	C29—H29B	0.9700
C9—H9B	0.9700	N30—C39	1.481 (9)
N10—C19	1.471 (10)	N30—H30A	0.9000
N10—H10A	0.9000	N31—C35	1.331 (10)
N11—C15	1.329 (9)	N31—N32	1.370 (8)
N11—N12	1.371 (8)	N32—C33	1.326 (10)
N12—C13	1.337 (10)	N32—C38	1.442 (9)
N12—C18	1.448 (10)	C33—C34	1.371 (12)
C13—C14	1.371 (11)	C33—C36	1.496 (12)
C13—C16	1.481 (11)	C34—C35	1.370 (12)
C14—C15	1.381 (11)	C34—H34A	0.9300
C14—H14A	0.9300	C35—C37	1.503 (12)
C15—C17	1.488 (11)	C36—H36A	0.9600
C16—H16A	0.9600	C36—H36B	0.9600
C16—H16B	0.9600	C36—H36C	0.9600
C16—H16C	0.9600	C37—H37A	0.9600
C17—H17A	0.9600	C37—H37B	0.9600
C17—H17B	0.9600	C37—H37C	0.9600
C17—H17C	0.9600	C38—C39	1.497 (11)
C18—C19	1.519 (11)	C38—H38A	0.9700
C18—H18A	0.9700	C38—H38B	0.9700
C18—H18B	0.9700	C39—H39A	0.9700
C19—H19A	0.9700	C39—H39B	0.9700
C19—H19B	0.9700	O1—H1	0.8507
Pd2—N21	2.023 (6)	O1—H2	0.8502

N11—Pd1—N1	172.4 (2)	N21—Pd2—N30	89.6 (2)
N11—Pd1—N10	82.6 (2)	N31—Pd2—N30	83.6 (2)
N1—Pd1—N10	90.1 (2)	N21—Pd2—I2	93.85 (17)
N11—Pd1—I1	91.33 (17)	N31—Pd2—I2	93.00 (18)
N1—Pd1—I1	95.91 (17)	N30—Pd2—I2	175.52 (17)
N10—Pd1—I1	173.96 (17)	C25—N21—N22	106.8 (6)
C5—N1—N2	105.8 (6)	C25—N21—Pd2	135.2 (6)
C5—N1—Pd1	136.5 (5)	N22—N21—Pd2	118.0 (5)
N2—N1—Pd1	117.6 (5)	C23—N22—N21	110.3 (6)
C3—N2—N1	109.8 (6)	C23—N22—C28	126.8 (7)
C3—N2—C8	129.0 (7)	N21—N22—C28	119.3 (6)
N1—N2—C8	119.1 (6)	N22—C23—C24	106.1 (7)
N2—C3—C4	108.0 (7)	N22—C23—C26	123.0 (7)
N2—C3—C6	123.6 (8)	C24—C23—C26	131.0 (8)
C4—C3—C6	128.3 (8)	C23—C24—C25	107.6 (8)
C3—C4—C5	106.1 (7)	C23—C24—H24A	126.2
C3—C4—H4A	126.9	C25—C24—H24A	126.2
C5—C4—H4A	126.9	N21—C25—C24	109.1 (7)
N1—C5—C4	110.1 (7)	N21—C25—C27	122.5 (8)
N1—C5—C7	121.7 (7)	C24—C25—C27	128.3 (8)
C4—C5—C7	128.2 (8)	C23—C26—H26A	109.5
C3—C6—H6A	109.5	C23—C26—H26B	109.5
C3—C6—H6B	109.5	H26A—C26—H26B	109.5
H6A—C6—H6B	109.5	C23—C26—H26C	109.5
C3—C6—H6C	109.5	H26A—C26—H26C	109.5
H6A—C6—H6C	109.5	H26B—C26—H26C	109.5
H6B—C6—H6C	109.5	C25—C27—H27A	109.5
C5—C7—H7A	109.5	C25—C27—H27B	109.5
C5—C7—H7B	109.5	H27A—C27—H27B	109.5
H7A—C7—H7B	109.5	C25—C27—H27C	109.5
C5—C7—H7C	109.5	H27A—C27—H27C	109.5
H7A—C7—H7C	109.5	H27B—C27—H27C	109.5
H7B—C7—H7C	109.5	N22—C28—C29	109.8 (6)
N2—C8—C9	111.2 (6)	N22—C28—H28A	109.7
N2—C8—H8A	109.4	C29—C28—H28A	109.7
C9—C8—H8A	109.4	N22—C28—H28B	109.7
N2—C8—H8B	109.4	C29—C28—H28B	109.7
C9—C8—H8B	109.4	H28A—C28—H28B	108.2
H8A—C8—H8B	108.0	N30—C29—C28	111.9 (6)
N10—C9—C8	111.5 (6)	N30—C29—H29A	109.2
N10—C9—H9A	109.3	C28—C29—H29A	109.2
C8—C9—H9A	109.3	N30—C29—H29B	109.2
N10—C9—H9B	109.3	C28—C29—H29B	109.2
C8—C9—H9B	109.3	H29A—C29—H29B	107.9
H9A—C9—H9B	108.0	C29—N30—C39	112.6 (6)
C19—N10—C9	114.8 (6)	C29—N30—Pd2	117.1 (5)
C19—N10—Pd1	109.8 (5)	C39—N30—Pd2	113.2 (5)
C9—N10—Pd1	116.8 (4)	C29—N30—H30A	104.0
C19—N10—H10A	104.6	C39—N30—H30A	104.0
C9—N10—H10A	104.6	Pd2—N30—H30A	104.0
Pd1—N10—H10A	104.6	C35—N31—N32	104.9 (6)
C15—N11—N12	106.5 (6)	C35—N31—Pd2	136.2 (6)
C15—N11—Pd1	137.8 (5)	N32—N31—Pd2	114.9 (5)
N12—N11—Pd1	115.4 (4)	C33—N32—N31	111.6 (6)
C13—N12—N11	110.1 (6)	C33—N32—C38	129.8 (7)
C13—N12—C18	131.7 (6)	N31—N32—C38	117.9 (6)
N11—N12—C18	118.1 (6)	N32—C33—C34	106.4 (7)
N12—C13—C14	107.1 (7)	N32—C33—C36	122.2 (8)
N12—C13—C16	123.2 (7)	C34—C33—C36	131.4 (8)
C14—C13—C16	129.7 (8)	C35—C34—C33	106.8 (8)
C13—C14—C15	106.8 (7)	C35—C34—H34A	126.6
C13—C14—H14A	126.6	C33—C34—H34A	126.6
C15—C14—H14A	126.6	N31—C35—C34	110.4 (7)
N11—C15—C14	109.4 (7)	N31—C35—C37	122.7 (8)
N11—C15—C17	121.0 (7)	C34—C35—C37	126.9 (8)
C14—C15—C17	129.5 (7)	C33—C36—H36A	109.5
C13—C16—H16A	109.5	C33—C36—H36B	109.5
C13—C16—H16B	109.5	H36A—C36—H36B	109.5
H16A—C16—H16B	109.5	C33—C36—H36C	109.5
C13—C16—H16C	109.5	H36A—C36—H36C	109.5
H16A—C16—H16C	109.5	H36B—C36—H36C	109.5
H16B—C16—H16C	109.5	C35—C37—H37A	109.5
C15—C17—H17A	109.5	C35—C37—H37B	109.5
C15—C17—H17B	109.5	H37A—C37—H37B	109.5
H17A—C17—H17B	109.5	C35—C37—H37C	109.5
C15—C17—H17C	109.5	H37A—C37—H37C	109.5
H17A—C17—H17C	109.5	H37B—C37—H37C	109.5
H17B—C17—H17C	109.5	N32—C38—C39	111.9 (6)
N12—C18—C19	112.9 (6)	N32—C38—H38A	109.2
N12—C18—H18A	109.0	C39—C38—H38A	109.2
C19—C18—H18A	109.0	N32—C38—H38B	109.2
N12—C18—H18B	109.0	C39—C38—H38B	109.2
C19—C18—H18B	109.0	H38A—C38—H38B	107.9
H18A—C18—H18B	107.8	N30—C39—C38	110.8 (6)
N10—C19—C18	113.5 (6)	N30—C39—H39A	109.5
N10—C19—H19A	108.9	C38—C39—H39A	109.5
C18—C19—H19A	108.9	N30—C39—H39B	109.5
N10—C19—H19B	108.9	C38—C39—H39B	109.5
C18—C19—H19B	108.9	H39A—C39—H39B	108.1
H19A—C19—H19B	107.7	H1—O1—H2	103.6
N21—Pd2—N31	173.1 (2)

C5—N1—N2—C3	0.4 (8)	C25—N21—N22—C23	−0.5 (8)
Pd1—N1—N2—C3	−178.9 (5)	Pd2—N21—N22—C23	179.8 (5)
C5—N1—N2—C8	−164.4 (6)	C25—N21—N22—C28	−160.6 (6)
Pd1—N1—N2—C8	16.2 (8)	Pd2—N21—N22—C28	19.8 (8)
N1—N2—C3—C4	1.1 (8)	N21—N22—C23—C24	1.9 (8)
C8—N2—C3—C4	164.1 (7)	C28—N22—C23—C24	160.1 (7)
N1—N2—C3—C6	179.5 (7)	N21—N22—C23—C26	−177.3 (7)
C8—N2—C3—C6	−17.5 (12)	C28—N22—C23—C26	−19.1 (12)
N2—C3—C4—C5	−2.2 (9)	N22—C23—C24—C25	−2.5 (9)
C6—C3—C4—C5	179.5 (8)	C26—C23—C24—C25	176.6 (8)
N2—N1—C5—C4	−1.8 (8)	N22—N21—C25—C24	−1.1 (8)
Pd1—N1—C5—C4	177.4 (6)	Pd2—N21—C25—C24	178.5 (6)
N2—N1—C5—C7	176.5 (7)	N22—N21—C25—C27	175.3 (7)
Pd1—N1—C5—C7	−4.2 (12)	Pd2—N21—C25—C27	−5.1 (12)
C3—C4—C5—N1	2.6 (9)	C23—C24—C25—N21	2.3 (9)
C3—C4—C5—C7	−175.7 (8)	C23—C24—C25—C27	−173.8 (8)
C3—N2—C8—C9	−109.2 (8)	C23—N22—C28—C29	−108.1 (8)
N1—N2—C8—C9	52.5 (9)	N21—N22—C28—C29	48.3 (9)
N2—C8—C9—N10	−76.7 (8)	N22—C28—C29—N30	−78.6 (8)
C8—C9—N10—C19	158.1 (7)	C28—C29—N30—C39	167.7 (6)
C8—C9—N10—Pd1	27.4 (8)	C28—C29—N30—Pd2	33.9 (8)
C15—N11—N12—C13	1.1 (8)	C35—N31—N32—C33	−1.7 (9)
Pd1—N11—N12—C13	175.7 (5)	Pd2—N31—N32—C33	159.5 (6)
C15—N11—N12—C18	−177.0 (6)	C35—N31—N32—C38	−173.3 (7)
Pd1—N11—N12—C18	−2.3 (8)	Pd2—N31—N32—C38	−12.0 (8)
N11—N12—C13—C14	0.7 (9)	N31—N32—C33—C34	2.0 (10)
C18—N12—C13—C14	178.4 (8)	C38—N32—C33—C34	172.3 (8)
N11—N12—C13—C16	−179.4 (7)	N31—N32—C33—C36	−176.9 (8)
C18—N12—C13—C16	−1.7 (13)	C38—N32—C33—C36	−6.6 (14)
N12—C13—C14—C15	−2.1 (9)	N32—C33—C34—C35	−1.5 (11)
C16—C13—C14—C15	177.9 (8)	C36—C33—C34—C35	177.3 (10)
N12—N11—C15—C14	−2.4 (8)	N32—N31—C35—C34	0.7 (10)
Pd1—N11—C15—C14	−175.2 (6)	Pd2—N31—C35—C34	−154.4 (7)
N12—N11—C15—C17	175.1 (7)	N32—N31—C35—C37	177.6 (9)
Pd1—N11—C15—C17	2.3 (12)	Pd2—N31—C35—C37	22.5 (14)
C13—C14—C15—N11	2.9 (9)	C33—C34—C35—N31	0.5 (11)
C13—C14—C15—C17	−174.4 (8)	C33—C34—C35—C37	−176.3 (10)
C13—N12—C18—C19	−113.8 (9)	C33—N32—C38—C39	−95.7 (10)
N11—N12—C18—C19	63.7 (9)	N31—N32—C38—C39	74.1 (8)
C9—N10—C19—C18	−164.8 (6)	C29—N30—C39—C38	−162.3 (6)
Pd1—N10—C19—C18	−30.8 (7)	Pd2—N30—C39—C38	−26.7 (7)
N12—C18—C19—N10	−41.1 (9)	N32—C38—C39—N30	−46.9 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···I3	0.85	2.68	3.497 (7)	161
O1—H2···I4	0.85	2.66	3.443 (10)	155
N10—H10A···I3ⁱ	0.90	2.94	3.653 (6)	137
N30—H30A···O1ⁱⁱ	0.90	2.22	3.011 (9)	146
N30—H30A···I4ⁱⁱ	0.90	3.30	3.853 (6)	122

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z.

(4) Azido{bis[2-(3,5-dimethylpyrazol-1-yl-κN²)ethyl]amine-κN}palladium azide monohydrate top

Crystal data top

[Pd(N₃)(C₁₄H₂₃N₅)]N₃·H₂O	F(000) = 960
M_r = 469.85	D_x = 1.562 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.132 (3) Å	Cell parameters from 65 reflections
b = 22.851 (5) Å	θ = 4.7–12.6°
c = 11.372 (3) Å	µ = 0.96 mm⁻¹
β = 109.03 (2)°	T = 296 K
V = 1997.8 (10) Å³	Prism, yellow
Z = 4	0.5 × 0.4 × 0.4 mm

Data collection top

Siemens P4 diffractometer	3528 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, FN4	R_int = 0.056
Graphite monochromator	θ_max = 26.3°, θ_min = 1.8°
2θ/ω scans	h = −10→10
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −28→1
T_min = 0.266, T_max = 0.366	l = −13→14
8431 measured reflections	3 standard reflections every 97 reflections
4032 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: mixed
wR(F²) = 0.097	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0346P)² + 1.7119P] where P = (F_o² + 2F_c²)/3
4032 reflections	(Δ/σ)_max = 0.001
248 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −1.04 e Å⁻³
0 constraints

Special details top

Refinement. Geometry of the water molecule first regularized with soft restraints: DFIX 0.85 0.02 O1 H1 O1 H2 DANG 1.34 0.04 H1 H2 then fixed in last l.s. cycles.

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

	x	y	z	U_iso*/U_eq
Pd1	0.35885 (3)	0.66267 (2)	0.24025 (2)	0.04508 (11)
N1	0.1428 (3)	0.62778 (11)	0.1211 (2)	0.0464 (6)
N2	−0.0024 (3)	0.62721 (12)	0.1552 (3)	0.0517 (6)
C3	−0.1283 (4)	0.59569 (14)	0.0740 (3)	0.0537 (8)
C4	−0.0629 (4)	0.57587 (15)	−0.0140 (3)	0.0565 (8)
H4A	−0.1212	0.5534	−0.0832	0.068*
C5	0.1059 (4)	0.59528 (13)	0.0184 (3)	0.0464 (7)
C6	−0.3035 (5)	0.5885 (2)	0.0869 (5)	0.0792 (12)
H6A	−0.2931	0.5670	0.1616	0.119*
H6B	−0.3777	0.5675	0.0164	0.119*
H6C	−0.3526	0.6263	0.0913	0.119*
C7	0.2369 (5)	0.58174 (18)	−0.0428 (4)	0.0643 (9)
H7A	0.1815	0.5620	−0.1201	0.096*
H7B	0.3256	0.5570	0.0105	0.096*
H7C	0.2885	0.6174	−0.0584	0.096*
C8	0.0001 (6)	0.65831 (19)	0.2670 (4)	0.0703 (11)
H8A	−0.1165	0.6594	0.2723	0.084*
H8B	0.0375	0.6983	0.2626	0.084*
C9	0.1213 (7)	0.6293 (3)	0.3823 (4)	0.0890 (15)
H9A	0.1389	0.6553	0.4528	0.107*
H9B	0.0675	0.5938	0.3988	0.107*
N10	0.2933 (5)	0.61468 (16)	0.3697 (3)	0.0689 (9)
H10	0.2793	0.5781	0.3385	0.083*
N11	0.5755 (4)	0.69476 (13)	0.3678 (2)	0.0563 (7)
N12	0.6733 (4)	0.65951 (14)	0.4606 (3)	0.0622 (8)
C13	0.8151 (5)	0.6887 (2)	0.5324 (3)	0.0683 (10)
C14	0.8074 (5)	0.7426 (2)	0.4839 (4)	0.0738 (12)
H14A	0.8889	0.7722	0.5131	0.089*
C15	0.6568 (5)	0.74619 (17)	0.3827 (3)	0.0597 (9)
C16	0.9454 (7)	0.6607 (3)	0.6430 (4)	0.0970 (17)
H16A	1.0466	0.6852	0.6721	0.146*
H16B	0.9778	0.6231	0.6199	0.146*
H16C	0.8952	0.6560	0.7080	0.146*
C17	0.5864 (7)	0.79739 (18)	0.3015 (5)	0.0816 (13)
H17A	0.6404	0.8325	0.3426	0.122*
H17B	0.4630	0.7997	0.2847	0.122*
H17C	0.6103	0.7931	0.2247	0.122*
C18	0.6068 (7)	0.6028 (2)	0.4785 (4)	0.0870 (15)
H18A	0.6858	0.5846	0.5524	0.104*
H18B	0.5994	0.5779	0.4078	0.104*
C19	0.4296 (7)	0.6086 (3)	0.4921 (4)	0.0988 (18)
H19A	0.4058	0.5744	0.5343	0.119*
H19B	0.4278	0.6427	0.5427	0.119*
N20	0.4246 (4)	0.70475 (14)	0.1065 (3)	0.0600 (7)
N21	0.3172 (4)	0.71867 (13)	0.0122 (3)	0.0589 (7)
N22	0.2246 (6)	0.7317 (2)	−0.0830 (4)	0.1040 (15)
N30	0.542 (2)	0.4721 (5)	0.2466 (9)	0.203 (6)
N31	0.416 (2)	0.4860 (4)	0.2612 (6)	0.157 (6)
N32	0.2861 (19)	0.4965 (4)	0.2913 (8)	0.183 (6)
O1	0.9351 (15)	0.4889 (3)	0.3750 (6)	0.244 (5)
H11	0.9691	0.4949	0.3136	0.366*
H12	0.8315	0.5015	0.3571	0.366*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.04258 (15)	0.05370 (16)	0.03330 (14)	−0.01038 (9)	0.00459 (10)	0.00120 (9)
N1	0.0367 (12)	0.0553 (15)	0.0446 (13)	−0.0056 (11)	0.0099 (11)	−0.0003 (11)
N2	0.0407 (14)	0.0581 (16)	0.0564 (16)	−0.0047 (11)	0.0159 (12)	−0.0024 (12)
C3	0.0363 (15)	0.0486 (17)	0.071 (2)	−0.0015 (13)	0.0100 (15)	0.0008 (15)
C4	0.0394 (16)	0.0531 (18)	0.065 (2)	−0.0003 (13)	0.0004 (15)	−0.0092 (15)
C5	0.0367 (14)	0.0488 (16)	0.0464 (16)	0.0012 (12)	0.0033 (12)	−0.0028 (13)
C6	0.0398 (19)	0.083 (3)	0.116 (4)	−0.0074 (18)	0.027 (2)	−0.006 (3)
C7	0.0514 (19)	0.073 (2)	0.065 (2)	−0.0005 (17)	0.0144 (17)	−0.0200 (18)
C8	0.063 (2)	0.088 (3)	0.071 (3)	−0.0140 (19)	0.036 (2)	−0.013 (2)
C9	0.084 (3)	0.127 (4)	0.062 (2)	−0.029 (3)	0.031 (2)	0.009 (3)
N10	0.072 (2)	0.082 (2)	0.0445 (15)	−0.0231 (17)	0.0080 (15)	0.0131 (15)
N11	0.0532 (16)	0.0667 (17)	0.0399 (14)	−0.0133 (13)	0.0028 (12)	−0.0016 (12)
N12	0.0562 (18)	0.078 (2)	0.0396 (15)	−0.0063 (14)	−0.0024 (13)	−0.0018 (13)
C13	0.050 (2)	0.100 (3)	0.0449 (18)	−0.001 (2)	0.0018 (15)	−0.022 (2)
C14	0.056 (2)	0.091 (3)	0.064 (2)	−0.021 (2)	0.0061 (18)	−0.028 (2)
C15	0.0526 (19)	0.068 (2)	0.0548 (19)	−0.0141 (16)	0.0129 (16)	−0.0172 (16)
C16	0.068 (3)	0.147 (5)	0.053 (2)	0.012 (3)	−0.012 (2)	−0.014 (3)
C17	0.090 (3)	0.060 (2)	0.084 (3)	−0.021 (2)	0.014 (3)	−0.003 (2)
C18	0.091 (3)	0.085 (3)	0.057 (2)	−0.012 (2)	−0.014 (2)	0.023 (2)
C19	0.098 (4)	0.135 (4)	0.047 (2)	−0.042 (3)	0.001 (2)	0.033 (2)
N20	0.0526 (16)	0.078 (2)	0.0443 (15)	−0.0160 (14)	0.0094 (14)	0.0058 (14)
N21	0.0582 (17)	0.0623 (17)	0.0562 (18)	0.0005 (14)	0.0188 (15)	0.0111 (14)
N22	0.093 (3)	0.124 (4)	0.077 (3)	0.006 (3)	0.004 (2)	0.048 (3)
N30	0.361 (17)	0.170 (8)	0.121 (6)	−0.016 (10)	0.140 (9)	0.001 (5)
N31	0.296 (17)	0.101 (5)	0.044 (3)	−0.072 (9)	0.014 (6)	−0.004 (3)
N32	0.293 (15)	0.094 (5)	0.087 (6)	−0.068 (7)	−0.041 (6)	0.019 (4)
O1	0.406 (14)	0.215 (7)	0.160 (6)	−0.041 (8)	0.159 (8)	−0.020 (5)

Geometric parameters (Å, º) top

Pd1—N1	2.002 (3)	N11—C15	1.332 (5)
Pd1—N20	2.014 (3)	N11—N12	1.360 (4)
Pd1—N11	2.020 (3)	N12—C13	1.351 (5)
Pd1—N10	2.041 (3)	N12—C18	1.443 (5)
N1—C5	1.334 (4)	C13—C14	1.342 (6)
N1—N2	1.358 (4)	C13—C16	1.498 (6)
N2—C3	1.343 (4)	C14—C15	1.383 (5)
N2—C8	1.451 (5)	C14—H14A	0.9300
C3—C4	1.355 (5)	C15—C17	1.485 (6)
C3—C6	1.488 (5)	C16—H16A	0.9600
C4—C5	1.373 (5)	C16—H16B	0.9600
C4—H4A	0.9300	C16—H16C	0.9600
C5—C7	1.483 (5)	C17—H17A	0.9600
C6—H6A	0.9600	C17—H17B	0.9600
C6—H6B	0.9600	C17—H17C	0.9600
C6—H6C	0.9600	C18—C19	1.504 (8)
C7—H7A	0.9600	C18—H18A	0.9700
C7—H7B	0.9600	C18—H18B	0.9700
C7—H7C	0.9600	C19—H19A	0.9700
C8—C9	1.512 (7)	C19—H19B	0.9700
C8—H8A	0.9700	N20—N21	1.184 (4)
C8—H8B	0.9700	N21—N22	1.139 (5)
C9—N10	1.490 (6)	N30—N31	1.129 (16)
C9—H9A	0.9700	N31—N32	1.239 (17)
C9—H9B	0.9700	O1—H11	0.8421
N10—C19	1.477 (5)	O1—H12	0.8503
N10—H10	0.9000

N1—Pd1—N20	93.98 (11)	C9—N10—Pd1	115.0 (3)
N1—Pd1—N11	176.78 (11)	C19—N10—H10	104.1
N20—Pd1—N11	89.15 (12)	C9—N10—H10	104.1
N1—Pd1—N10	84.03 (12)	Pd1—N10—H10	104.1
N20—Pd1—N10	175.99 (14)	C15—N11—N12	106.5 (3)
N11—Pd1—N10	92.80 (12)	C15—N11—Pd1	133.8 (3)
C5—N1—N2	106.1 (2)	N12—N11—Pd1	119.7 (2)
C5—N1—Pd1	135.4 (2)	C13—N12—N11	110.2 (3)
N2—N1—Pd1	117.6 (2)	C13—N12—C18	130.0 (4)
C3—N2—N1	110.3 (3)	N11—N12—C18	119.3 (3)
C3—N2—C8	131.0 (3)	C14—C13—N12	106.7 (4)
N1—N2—C8	118.7 (3)	C14—C13—C16	131.4 (4)
N2—C3—C4	107.0 (3)	N12—C13—C16	121.8 (5)
N2—C3—C6	122.1 (4)	C13—C14—C15	107.9 (4)
C4—C3—C6	130.9 (3)	C13—C14—H14A	126.1
C3—C4—C5	107.1 (3)	C15—C14—H14A	126.1
C3—C4—H4A	126.5	N11—C15—C14	108.7 (4)
C5—C4—H4A	126.5	N11—C15—C17	122.8 (3)
N1—C5—C4	109.5 (3)	C14—C15—C17	128.5 (4)
N1—C5—C7	122.4 (3)	C13—C16—H16A	109.5
C4—C5—C7	128.0 (3)	C13—C16—H16B	109.5
C3—C6—H6A	109.5	H16A—C16—H16B	109.5
C3—C6—H6B	109.5	C13—C16—H16C	109.5
H6A—C6—H6B	109.5	H16A—C16—H16C	109.5
C3—C6—H6C	109.5	H16B—C16—H16C	109.5
H6A—C6—H6C	109.5	C15—C17—H17A	109.5
H6B—C6—H6C	109.5	C15—C17—H17B	109.5
C5—C7—H7A	109.5	H17A—C17—H17B	109.5
C5—C7—H7B	109.5	C15—C17—H17C	109.5
H7A—C7—H7B	109.5	H17A—C17—H17C	109.5
C5—C7—H7C	109.5	H17B—C17—H17C	109.5
H7A—C7—H7C	109.5	N12—C18—C19	110.5 (4)
H7B—C7—H7C	109.5	N12—C18—H18A	109.5
N2—C8—C9	111.4 (4)	C19—C18—H18A	109.5
N2—C8—H8A	109.4	N12—C18—H18B	109.5
C9—C8—H8A	109.4	C19—C18—H18B	109.5
N2—C8—H8B	109.4	H18A—C18—H18B	108.1
C9—C8—H8B	109.4	N10—C19—C18	111.1 (4)
H8A—C8—H8B	108.0	N10—C19—H19A	109.4
N10—C9—C8	112.5 (3)	C18—C19—H19A	109.4
N10—C9—H9A	109.1	N10—C19—H19B	109.4
C8—C9—H9A	109.1	C18—C19—H19B	109.4
N10—C9—H9B	109.1	H19A—C19—H19B	108.0
C8—C9—H9B	109.1	N21—N20—Pd1	120.9 (2)
H9A—C9—H9B	107.8	N22—N21—N20	174.2 (4)
C19—N10—C9	111.7 (4)	N30—N31—N32	171.4 (11)
C19—N10—Pd1	116.0 (3)	H11—O1—H12	108.2

C5—N1—N2—C3	−1.0 (4)	C15—N11—N12—C13	−0.4 (4)
Pd1—N1—N2—C3	−171.8 (2)	Pd1—N11—N12—C13	177.6 (3)
C5—N1—N2—C8	178.7 (3)	C15—N11—N12—C18	172.2 (4)
Pd1—N1—N2—C8	7.9 (4)	Pd1—N11—N12—C18	−9.9 (5)
N1—N2—C3—C4	−0.2 (4)	N11—N12—C13—C14	−0.5 (5)
C8—N2—C3—C4	−179.8 (4)	C18—N12—C13—C14	−172.0 (5)
N1—N2—C3—C6	−178.9 (3)	N11—N12—C13—C16	179.2 (4)
C8—N2—C3—C6	1.5 (6)	C18—N12—C13—C16	7.7 (7)
N2—C3—C4—C5	1.3 (4)	N12—C13—C14—C15	1.2 (5)
C6—C3—C4—C5	179.8 (4)	C16—C13—C14—C15	−178.5 (5)
N2—N1—C5—C4	1.8 (4)	N12—N11—C15—C14	1.1 (4)
Pd1—N1—C5—C4	170.1 (2)	Pd1—N11—C15—C14	−176.5 (3)
N2—N1—C5—C7	−175.5 (3)	N12—N11—C15—C17	−177.7 (4)
Pd1—N1—C5—C7	−7.2 (5)	Pd1—N11—C15—C17	4.7 (6)
C3—C4—C5—N1	−1.9 (4)	C13—C14—C15—N11	−1.4 (5)
C3—C4—C5—C7	175.2 (3)	C13—C14—C15—C17	177.3 (4)
C3—N2—C8—C9	111.5 (5)	C13—N12—C18—C19	117.0 (5)
N1—N2—C8—C9	−68.1 (4)	N11—N12—C18—C19	−53.8 (5)
N2—C8—C9—N10	46.9 (5)	C9—N10—C19—C18	−171.5 (4)
C8—C9—N10—C19	157.6 (4)	Pd1—N10—C19—C18	−37.1 (6)
C8—C9—N10—Pd1	22.7 (5)	N12—C18—C19—N10	80.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10···N32	0.90	1.95	2.838 (11)	171
N10—H10···N31	0.90	2.66	3.460 (13)	148
O1—H11···N32ⁱ	0.84	2.67	3.295 (19)	132
O1—H12···N30	0.85	2.38	3.08 (2)	140

Symmetry code: (i) x+1, y, z.

(5) Bis[{bis[2-(3,5-dimethylpyrazol-1-yl-κN²)ethyl]amine-κN}(thiocyanato-κN)palladium] tetrakis(thiocyanato-κS)palladate top

Crystal data top

[Pd(NCS)(C₁₄H₂₃N₅)]₂[Pd(NCS)₄]	Z = 1
M_r = 1190.43	F(000) = 596
Triclinic, P1	D_x = 1.686 Mg m⁻³
a = 9.0286 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.532 (2) Å	Cell parameters from 75 reflections
c = 13.066 (3) Å	θ = 4.7–12.4°
α = 94.838 (14)°	µ = 1.45 mm⁻¹
β = 100.947 (12)°	T = 298 K
γ = 103.989 (13)°	Irregular_Plate, pink
V = 1172.5 (4) Å³	0.40 × 0.40 × 0.12 mm

Data collection top

Siemens P4 diffractometer	4874 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, FN4	R_int = 0.038
Graphite monochromator	θ_max = 27.5°, θ_min = 2.0°
2θ/ω scans	h = −11→6
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −13→13
T_min = 0.256, T_max = 0.378	l = −16→16
8889 measured reflections	3 standard reflections every 97 reflections
5367 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0569P)² + 1.1014P] where P = (F_o² + 2F_c²)/3
5367 reflections	(Δ/σ)_max < 0.001
282 parameters	Δρ_max = 0.83 e Å⁻³
0 restraints	Δρ_min = −1.06 e Å⁻³
0 constraints

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pd1	0.36057 (3)	0.61306 (2)	0.33358 (2)	0.03862 (9)
S1	0.88007 (13)	0.60961 (16)	0.47191 (8)	0.0735 (4)
N1	0.3690 (3)	0.4656 (3)	0.2291 (2)	0.0420 (6)
N2	0.2424 (3)	0.3584 (3)	0.2003 (2)	0.0453 (6)
C3	0.2603 (4)	0.2765 (4)	0.1225 (3)	0.0526 (8)
C4	0.4009 (5)	0.3330 (4)	0.0994 (3)	0.0545 (9)
H4A	0.4443	0.2987	0.0479	0.065*
C5	0.4667 (4)	0.4500 (4)	0.1663 (2)	0.0448 (7)
C6	0.1425 (6)	0.1487 (5)	0.0757 (4)	0.0814 (15)
H6A	0.0469	0.1661	0.0415	0.122*
H6B	0.1228	0.0957	0.1304	0.122*
H6C	0.1822	0.1024	0.0253	0.122*
C7	0.6181 (5)	0.5472 (5)	0.1716 (3)	0.0610 (9)
H7A	0.6078	0.6349	0.1879	0.091*
H7B	0.6475	0.5390	0.1050	0.091*
H7C	0.6969	0.5308	0.2254	0.091*
C8	0.1152 (4)	0.3501 (4)	0.2545 (3)	0.0531 (8)
H8A	0.1555	0.3552	0.3295	0.064*
H8B	0.0391	0.2653	0.2308	0.064*
C9	0.0363 (4)	0.4580 (4)	0.2354 (3)	0.0564 (9)
H9A	−0.0338	0.4356	0.1666	0.068*	0.770 (18)
H9B	−0.0264	0.4637	0.2874	0.068*	0.770 (18)
H9C	0.0179	0.4648	0.1608	0.068*	0.230 (18)
H9D	−0.0650	0.4328	0.2538	0.068*	0.230 (18)
N10A	0.1465 (5)	0.5881 (4)	0.2405 (5)	0.0423 (14)	0.770 (18)
H10A	0.1658	0.5870	0.1754	0.051*	0.770 (18)
N10B	0.1157 (15)	0.5806 (14)	0.2894 (18)	0.041 (4)	0.230 (18)
H10B	0.0858	0.5793	0.3513	0.049*	0.230 (18)
N11	0.3365 (3)	0.7611 (3)	0.4311 (2)	0.0450 (6)
N12	0.2638 (3)	0.8493 (3)	0.3896 (2)	0.0490 (6)
C13	0.2571 (5)	0.9392 (4)	0.4656 (4)	0.0641 (11)
C14	0.3268 (6)	0.9078 (5)	0.5585 (4)	0.0698 (12)
H14A	0.3399	0.9534	0.6251	0.084*
C15	0.3743 (5)	0.7964 (4)	0.5356 (3)	0.0571 (9)
C16	0.1801 (7)	1.0477 (6)	0.4450 (6)	0.0965 (19)
H16A	0.2306	1.1016	0.3993	0.145*
H16B	0.1883	1.1009	0.5102	0.145*
H16C	0.0717	1.0105	0.4120	0.145*
C17	0.4503 (7)	0.7208 (6)	0.6096 (3)	0.0769 (13)
H17A	0.5170	0.6803	0.5766	0.115*
H17B	0.3717	0.6535	0.6288	0.115*
H17C	0.5115	0.7793	0.6716	0.115*
C18	0.1923 (5)	0.8273 (4)	0.2784 (3)	0.0552 (9)
H18A	0.2722	0.8288	0.2380	0.066*
H18B	0.1442	0.8981	0.2613	0.066*
C19	0.0713 (4)	0.6981 (4)	0.2488 (3)	0.0517 (8)
H19A	0.0083	0.6857	0.3014	0.062*	0.770 (18)
H19B	0.0028	0.6979	0.1818	0.062*	0.770 (18)
H19C	0.0421	0.6799	0.1726	0.062*	0.230 (18)
H19D	−0.0209	0.7072	0.2734	0.062*	0.230 (18)
N20	0.5799 (4)	0.6337 (3)	0.4077 (3)	0.0558 (8)
C21	0.7053 (4)	0.6233 (4)	0.4336 (3)	0.0517 (8)
Pd2	0.5000	1.0000	1.0000	0.03984 (10)
S22	0.27722 (13)	0.83780 (12)	0.91759 (10)	0.0736 (3)
C23	0.2457 (4)	0.7188 (5)	0.9922 (3)	0.0567 (9)
N24	0.2159 (6)	0.6323 (5)	1.0375 (3)	0.0849 (13)
S25	0.45759 (12)	1.11365 (12)	0.85705 (8)	0.0604 (3)
C26	0.2664 (5)	1.0806 (5)	0.8121 (3)	0.0617 (10)
N27	0.1366 (6)	1.0626 (6)	0.7789 (4)	0.1036 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.03258 (13)	0.04589 (15)	0.03637 (13)	0.01607 (10)	0.00092 (9)	−0.00186 (9)
S1	0.0489 (5)	0.1354 (11)	0.0481 (5)	0.0505 (6)	0.0069 (4)	0.0103 (6)
N1	0.0391 (13)	0.0488 (15)	0.0379 (12)	0.0161 (11)	0.0053 (10)	−0.0014 (11)
N2	0.0382 (13)	0.0543 (16)	0.0404 (13)	0.0122 (12)	0.0071 (11)	−0.0062 (11)
C3	0.0485 (18)	0.060 (2)	0.0478 (17)	0.0214 (16)	0.0059 (14)	−0.0103 (15)
C4	0.051 (2)	0.069 (2)	0.0476 (18)	0.0254 (18)	0.0139 (15)	−0.0029 (16)
C5	0.0432 (16)	0.0583 (19)	0.0394 (15)	0.0249 (15)	0.0095 (12)	0.0067 (13)
C6	0.069 (3)	0.077 (3)	0.085 (3)	0.005 (2)	0.021 (2)	−0.031 (3)
C7	0.053 (2)	0.071 (3)	0.066 (2)	0.0196 (19)	0.0231 (18)	0.0106 (19)
C8	0.0507 (19)	0.058 (2)	0.0485 (18)	0.0084 (16)	0.0190 (15)	−0.0036 (15)
C9	0.0334 (16)	0.070 (2)	0.062 (2)	0.0129 (15)	0.0098 (15)	−0.0085 (18)
N10A	0.0321 (19)	0.059 (2)	0.038 (3)	0.0197 (16)	0.0053 (18)	0.0015 (17)
N10B	0.025 (5)	0.064 (8)	0.037 (9)	0.017 (5)	0.010 (5)	0.000 (6)
N11	0.0449 (14)	0.0451 (15)	0.0455 (14)	0.0178 (12)	0.0061 (11)	−0.0001 (11)
N12	0.0422 (14)	0.0464 (15)	0.0599 (17)	0.0171 (12)	0.0089 (12)	0.0043 (13)
C13	0.051 (2)	0.046 (2)	0.091 (3)	0.0135 (16)	0.012 (2)	−0.0113 (19)
C14	0.071 (3)	0.066 (3)	0.065 (2)	0.017 (2)	0.012 (2)	−0.021 (2)
C15	0.062 (2)	0.055 (2)	0.0474 (18)	0.0104 (17)	0.0080 (16)	−0.0063 (15)
C16	0.085 (4)	0.062 (3)	0.142 (5)	0.037 (3)	0.014 (4)	−0.015 (3)
C17	0.093 (4)	0.085 (3)	0.045 (2)	0.022 (3)	0.001 (2)	0.005 (2)
C18	0.0502 (19)	0.065 (2)	0.062 (2)	0.0296 (17)	0.0175 (16)	0.0199 (18)
C19	0.0364 (16)	0.075 (2)	0.0500 (18)	0.0282 (16)	0.0056 (13)	0.0091 (16)
N20	0.0388 (15)	0.0595 (19)	0.0648 (19)	0.0215 (13)	−0.0024 (13)	−0.0102 (15)
C21	0.0473 (19)	0.065 (2)	0.0425 (16)	0.0237 (16)	0.0014 (14)	−0.0029 (15)
Pd2	0.02961 (16)	0.0489 (2)	0.04031 (18)	0.01548 (13)	0.00172 (12)	0.00076 (14)
S22	0.0517 (6)	0.0667 (7)	0.0806 (7)	0.0003 (5)	−0.0215 (5)	0.0161 (5)
C23	0.0440 (18)	0.070 (2)	0.0495 (19)	0.0088 (17)	0.0082 (15)	−0.0040 (17)
N24	0.085 (3)	0.096 (3)	0.057 (2)	−0.007 (2)	0.015 (2)	0.016 (2)
S25	0.0460 (5)	0.0790 (7)	0.0549 (5)	0.0166 (4)	0.0031 (4)	0.0192 (5)
C26	0.056 (2)	0.081 (3)	0.051 (2)	0.032 (2)	0.0013 (17)	0.0122 (19)
N27	0.062 (3)	0.153 (5)	0.103 (4)	0.046 (3)	−0.001 (2)	0.044 (4)

Geometric parameters (Å, º) top

Pd1—N20	1.984 (3)	N10B—H10B	0.9000
Pd1—N1	2.005 (3)	N11—C15	1.340 (5)
Pd1—N11	2.009 (3)	N11—N12	1.353 (4)
Pd1—N10A	2.022 (4)	N12—C13	1.335 (5)
Pd1—N10B	2.111 (12)	N12—C18	1.447 (5)
S1—C21	1.607 (4)	C13—C14	1.362 (7)
N1—C5	1.342 (4)	C13—C16	1.493 (7)
N1—N2	1.365 (4)	C14—C15	1.372 (6)
N2—C3	1.336 (4)	C14—H14A	0.9300
N2—C8	1.449 (4)	C15—C17	1.478 (6)
C3—C4	1.366 (6)	C16—H16A	0.9600
C3—C6	1.496 (6)	C16—H16B	0.9600
C4—C5	1.379 (5)	C16—H16C	0.9600
C4—H4A	0.9300	C17—H17A	0.9600
C5—C7	1.482 (5)	C17—H17B	0.9600
C6—H6A	0.9600	C17—H17C	0.9600
C6—H6B	0.9600	C18—C19	1.493 (6)
C6—H6C	0.9600	C18—H18A	0.9700
C7—H7A	0.9600	C18—H18B	0.9700
C7—H7B	0.9600	C19—H19A	0.9700
C7—H7C	0.9600	C19—H19B	0.9700
C8—C9	1.494 (6)	C19—H19C	0.9700
C8—H8A	0.9700	C19—H19D	0.9700
C8—H8B	0.9700	N20—C21	1.153 (5)
C9—N10B	1.373 (14)	Pd2—S22	2.3085 (12)
C9—N10A	1.474 (6)	Pd2—S22ⁱ	2.3085 (12)
C9—H9A	0.9700	Pd2—S25	2.3227 (11)
C9—H9B	0.9700	Pd2—S25ⁱ	2.3227 (11)
C9—H9C	0.9700	S22—C23	1.656 (5)
C9—H9D	0.9700	C23—N24	1.133 (6)
N10A—C19	1.483 (5)	S25—C26	1.654 (4)
N10A—H10A	0.9000	C26—N27	1.133 (6)
N10B—C19	1.498 (15)

N20—Pd1—N1	91.68 (12)	C19—N10B—Pd1	111.8 (9)
N20—Pd1—N11	92.64 (12)	C9—N10B—H10B	103.3
N1—Pd1—N11	175.60 (11)	C19—N10B—H10B	103.3
N20—Pd1—N10A	172.5 (2)	Pd1—N10B—H10B	103.3
N1—Pd1—N10A	82.54 (18)	C15—N11—N12	106.7 (3)
N11—Pd1—N10A	93.08 (18)	C15—N11—Pd1	134.6 (3)
N20—Pd1—N10B	166.4 (7)	N12—N11—Pd1	118.6 (2)
N1—Pd1—N10B	94.8 (5)	C13—N12—N11	110.3 (3)
N11—Pd1—N10B	81.2 (5)	C13—N12—C18	129.9 (3)
C5—N1—N2	106.4 (3)	N11—N12—C18	119.4 (3)
C5—N1—Pd1	134.7 (3)	N12—C13—C14	107.0 (4)
N2—N1—Pd1	118.4 (2)	N12—C13—C16	123.0 (5)
C3—N2—N1	110.7 (3)	C14—C13—C16	129.9 (5)
C3—N2—C8	130.8 (3)	C13—C14—C15	107.3 (4)
N1—N2—C8	118.5 (3)	C13—C14—H14A	126.4
N2—C3—C4	106.7 (3)	C15—C14—H14A	126.4
N2—C3—C6	123.2 (4)	N11—C15—C14	108.7 (4)
C4—C3—C6	130.1 (3)	N11—C15—C17	123.2 (4)
C3—C4—C5	107.6 (3)	C14—C15—C17	128.1 (4)
C3—C4—H4A	126.2	C13—C16—H16A	109.5
C5—C4—H4A	126.2	C13—C16—H16B	109.5
N1—C5—C4	108.6 (3)	H16A—C16—H16B	109.5
N1—C5—C7	123.2 (3)	C13—C16—H16C	109.5
C4—C5—C7	128.2 (3)	H16A—C16—H16C	109.5
C3—C6—H6A	109.5	H16B—C16—H16C	109.5
C3—C6—H6B	109.5	C15—C17—H17A	109.5
H6A—C6—H6B	109.5	C15—C17—H17B	109.5
C3—C6—H6C	109.5	H17A—C17—H17B	109.5
H6A—C6—H6C	109.5	C15—C17—H17C	109.5
H6B—C6—H6C	109.5	H17A—C17—H17C	109.5
C5—C7—H7A	109.5	H17B—C17—H17C	109.5
C5—C7—H7B	109.5	N12—C18—C19	111.4 (3)
H7A—C7—H7B	109.5	N12—C18—H18A	109.4
C5—C7—H7C	109.5	C19—C18—H18A	109.4
H7A—C7—H7C	109.5	N12—C18—H18B	109.4
H7B—C7—H7C	109.5	C19—C18—H18B	109.4
N2—C8—C9	112.1 (3)	H18A—C18—H18B	108.0
N2—C8—H8A	109.2	N10A—C19—C18	110.4 (3)
C9—C8—H8A	109.2	C18—C19—N10B	116.8 (5)
N2—C8—H8B	109.2	N10A—C19—H19A	109.6
C9—C8—H8B	109.2	C18—C19—H19A	109.6
H8A—C8—H8B	107.9	N10A—C19—H19B	109.6
N10B—C9—C8	115.9 (6)	C18—C19—H19B	109.6
N10A—C9—C8	113.3 (3)	H19A—C19—H19B	108.1
N10A—C9—H9A	108.9	C18—C19—H19C	108.1
C8—C9—H9A	108.9	N10B—C19—H19C	108.1
N10A—C9—H9B	108.9	C18—C19—H19D	108.1
C8—C9—H9B	108.9	N10B—C19—H19D	108.1
H9A—C9—H9B	107.7	H19C—C19—H19D	107.3
N10B—C9—H9C	108.3	C21—N20—Pd1	164.8 (3)
C8—C9—H9C	108.3	N20—C21—S1	179.0 (4)
N10B—C9—H9D	108.3	S22—Pd2—S22ⁱ	180.0
C8—C9—H9D	108.3	S22—Pd2—S25	87.77 (4)
H9C—C9—H9D	107.4	S22ⁱ—Pd2—S25	92.23 (4)
C9—N10A—C19	112.4 (4)	S22—Pd2—S25ⁱ	92.23 (4)
C9—N10A—Pd1	115.1 (3)	S22ⁱ—Pd2—S25ⁱ	87.77 (4)
C19—N10A—Pd1	117.4 (3)	S25—Pd2—S25ⁱ	180.0
C9—N10A—H10A	103.2	C23—S22—Pd2	109.52 (14)
C19—N10A—H10A	103.2	N24—C23—S22	175.1 (4)
Pd1—N10A—H10A	103.2	C26—S25—Pd2	107.53 (16)
C9—N10B—C19	117.7 (11)	N27—C26—S25	176.9 (5)
C9—N10B—Pd1	115.0 (8)

C5—N1—N2—C3	0.8 (4)	C15—N11—N12—C13	0.6 (4)
Pd1—N1—N2—C3	173.4 (2)	Pd1—N11—N12—C13	179.3 (3)
C5—N1—N2—C8	−178.9 (3)	C15—N11—N12—C18	−172.6 (3)
Pd1—N1—N2—C8	−6.4 (4)	Pd1—N11—N12—C18	6.1 (4)
N1—N2—C3—C4	−0.9 (4)	N11—N12—C13—C14	−0.1 (5)
C8—N2—C3—C4	178.8 (4)	C18—N12—C13—C14	172.2 (4)
N1—N2—C3—C6	178.5 (4)	N11—N12—C13—C16	−178.4 (4)
C8—N2—C3—C6	−1.7 (7)	C18—N12—C13—C16	−6.1 (7)
N2—C3—C4—C5	0.6 (4)	N12—C13—C14—C15	−0.4 (5)
C6—C3—C4—C5	−178.8 (5)	C16—C13—C14—C15	177.7 (5)
N2—N1—C5—C4	−0.4 (4)	N12—N11—C15—C14	−0.8 (5)
Pd1—N1—C5—C4	−171.2 (3)	Pd1—N11—C15—C14	−179.3 (3)
N2—N1—C5—C7	179.1 (3)	N12—N11—C15—C17	177.5 (4)
Pd1—N1—C5—C7	8.3 (5)	Pd1—N11—C15—C17	−1.0 (7)
C3—C4—C5—N1	−0.1 (4)	C13—C14—C15—N11	0.8 (5)
C3—C4—C5—C7	−179.6 (4)	C13—C14—C15—C17	−177.4 (5)
C3—N2—C8—C9	−115.1 (4)	C13—N12—C18—C19	−113.4 (4)
N1—N2—C8—C9	64.6 (4)	N11—N12—C18—C19	58.3 (4)
N2—C8—C9—N10B	−75.9 (12)	C9—N10A—C19—C18	166.9 (4)
N2—C8—C9—N10A	−42.8 (5)	Pd1—N10A—C19—C18	30.0 (6)
N10B—C9—N10A—C19	−63.7 (12)	C9—N10A—C19—N10B	58.3 (11)
C8—C9—N10A—C19	−165.4 (4)	Pd1—N10A—C19—N10B	−78.6 (10)
N10B—C9—N10A—Pd1	74.3 (11)	N12—C18—C19—N10A	−77.7 (5)
C8—C9—N10A—Pd1	−27.4 (6)	N12—C18—C19—N10B	−46.7 (11)
N10A—C9—N10B—C19	68.0 (18)	C9—N10B—C19—N10A	−72.5 (18)
C8—C9—N10B—C19	160.4 (10)	Pd1—N10B—C19—N10A	64.0 (11)
N10A—C9—N10B—Pd1	−67.2 (12)	C9—N10B—C19—C18	−156.5 (11)
C8—C9—N10B—Pd1	25.2 (17)	Pd1—N10B—C19—C18	−20.0 (15)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10A—H10A···N24ⁱⁱ	0.90	2.01	2.889 (9)	166
N10B—H10B···S1ⁱⁱⁱ	0.90	2.71	3.52 (2)	151

Symmetry codes: (ii) x, y, z−1; (iii) x−1, y, z.

Footnotes

¹This work forms part of the PhD thesis of María de los Angeles Mendoza (Guanajuato, Mexico, 2010).

‡Currently unaffiliated to UANL.

Acknowledgements

The authors thank the Consejo Nacional de Ciencia y Tecnología (CONACyT) for the financial support of MAM during her postgraduate studies with grant No. 179804/194677.

References

Ajellal, N., Kuhn, M. C. A., Boff, A. D. G., Hörner, M., Thomas, C. M., Carpentier, J.-F. & Casagrande, O. L. Jr (2006). Organometallics, 25, 1213–1216. Web of Science CSD CrossRef CAS Google Scholar
Alvarez, S., Alemany, P., Casanova, D., Cirera, J., Llunell, M. & Avnir, D. (2005). Coord. Chem. Rev. 249, 1693–1708. Web of Science CrossRef CAS Google Scholar
Alves, S., Paulo, A., Correia, J. D. G., Domingos, Â. & Santos, I. (2002). J. Chem. Soc. Dalton Trans. pp. 4714–4719. Web of Science CSD CrossRef Google Scholar
Berkel, P. M. van, Driessen, W. L., Hämäläinen, R., Reedijk, J. & Turpeinen, U. (1994). Inorg. Chem. 33, 5920–5926. Google Scholar
Burth, R. & Vahrenkamp, H. (1998). Inorg. Chim. Acta, 282, 193–199. Web of Science CSD CrossRef CAS Google Scholar
Chang, X., Lee, K.-E., Jeon, S. I., Kim, Y.-J., Lee, H.-K. & Lee, S. W. (2005). Dalton Trans. pp. 3722–3731. Web of Science CSD CrossRef Google Scholar
Griffith, E. A. H., Charles, N. G., Lewinski, K., Amma, E. L. & Rodesiler, P. F. (1987). Inorg. Chem. 26, 3983–3989. CSD CrossRef CAS Web of Science Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CSD CrossRef CAS Google Scholar
Guzei, I. A., Spencer, L. C., Miti, N. & Darkwa, J. (2010). Acta Cryst. E66, m1243. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kim, J. H., Roh, S.-G. & Jeong, J. H. (2000). Acta Cryst. C56, e543–e544. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Lee, R. E., Park, Y. D. & Jeong, J. H. (2007). Acta Cryst. E63, m2679. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lian, B., Thomas, C. M., Casagrande, O. L. Jr, Lehmann, C. W., Roisnel, T. & Carpentier, J.-F. (2007a). Inorg. Chem. 46, 328–340. Web of Science CSD CrossRef PubMed CAS Google Scholar
Lian, B., Thomas, C. M., Casagrande, O. L. Jr, Roisnel, T. & Carpentier, J.-F. (2007b). Polyhedron, 26, 3817–3824. Web of Science CSD CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Martens, C. F., Schenning, A. P. H. J., Feiters, M. C., Berens, H. W., van der Linden, J. G. M., Admiraal, G., Beurskens, P. T., Kooijman, H., Spek, A. L. & Nolte, R. J. M. (1995). Inorg. Chem. 34, 4735–4744. CSD CrossRef CAS Web of Science Google Scholar
Massoud, S. S., Le Quan, L., Gatterer, K., Albering, J. H., Fischer, R. C. & Mautner, F. A. (2012a). Polyhedron, 31, 601–606. Web of Science CSD CrossRef CAS Google Scholar
Massoud, S. S., Louka, F. R., Obaid, Y. K., Vicente, R., Ribas, J., Fischer, R. C. & Mautner, F. A. (2013). Dalton Trans. 42, 3968–3978. Web of Science CSD CrossRef CAS PubMed Google Scholar
Massoud, S. S., Vicente, R., Fontenot, P. R., Gallo, A. A., Mikuriya, M., Albering, J. H. & Mautner, F. A. (2012b). Polyhedron, 46, 66–73. Web of Science CSD CrossRef CAS Google Scholar
Mendoza, M. de los A., Bernès, S. & Mendoza-Díaz, G. (2006). Acta Cryst. E62, m2934–m2936. Google Scholar
Monzani, E., Koolhaas, G. J. A. A., Spandre, A., Leggieri, E., Casella, L., Gullotti, M., Nardin, G., Randaccio, L., Fontani, M., Zanello, P. & Reedijk, J. (2000). J. Biol. Inorg. Chem. 5, 251–261. Web of Science CSD CrossRef PubMed CAS Google Scholar
Paviglianiti, A. J., Minn, D. J., Fultz, W. C. & Burmeister, J. L. (1989). Inorg. Chim. Acta, 159, 65–82. CSD CrossRef CAS Web of Science Google Scholar
Riklin, M., Tran, D., Bu, X., Laverman, L. E. & Ford, P. C. (2001). J. Chem. Soc. Dalton Trans. pp. 1813–1819. Web of Science CSD CrossRef Google Scholar
Segapelo, T. V., Guzei, I. A., Spencer, L. C. & Darkwa, J. (2011). Inorg. Chem. Commun. 14, 1706–1710. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 1| January 2015| Pages 22-27

https://doi.org/10.1107/S205698901402595X

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Coordination of bis­­(pyrazol-1-yl)amine to palladium(II): influence of the co-ligands and counter-ions on the mol­ecular and crystal structures1

1. Chemical context

2. Structural commentary: mol­ecular and crystal structures

3. Database survey

4. Synthesis and crystallization

5. Refinement

Supporting information

Footnotes

Acknowledgements

References

research communications

Coordination of bis(pyrazol-1-yl)amine to palladium(II): influence of the co-ligands and counter-ions on the molecular and crystal structures¹

2. Structural commentary: molecular and crystal structures