{Bis[2-(3,5-dimethyl­pyrazol-1-yl-κN2)eth­yl]amine-κN}chloridopalladium(II) chloride 0.25-hydrate

Guzei, I.A.; Spencer, L.C.; Miti, N.; Darkwa, J.

doi:10.1107/S1600536810035427

{Bis[2-(3,5-dimethylpyrazol-1-yl-κN²)ethyl]amine-κN}chloridopalladium(II) chloride 0.25-hydrate

I. A. Guzei, L. C. Spencer, N. Miti and J. Darkwa

The title compound, [PdCl(C₁₄H₂₃N₅)]Cl·0.25H₂O, is a pseudopolymorph of the previously reported compound [PdCl(C₁₄H₂₃N₅)]Cl·2H₂O [de Mendoza et al. (2006). Acta Cryst. E62, m2934–m2936]. The cationic complex and chloride anion are disordered over two positions each in a 0.584 (4):0.416 (4) ratio. The geometry about the Pd atom is distorted square-planar. The pyrazole rings are almost perpendicular, forming a dihedral angle of 86.6 (6)° to each other, to mitigate steric conflict between their methyl groups.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810035427/su2207sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810035427/su2207Isup2.hkl Contains datablock I

CCDC reference: 797625

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean () = 0.000 Å
H-atom completeness 98%
Disorder in main residue
R factor = 0.023
wR factor = 0.057
Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....       <O1W
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         12
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ          ?
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.25 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         57

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C14 H23.5 Cl2 N5 O0.25 Pd1
            Atom count from _chemical_formula_moiety:C14 H24 Cl2 N5 O0.25 Pd1
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C14 H23.5 Cl2 N5 O0.25 Pd1
            Atom count from the _atom_site data:  C14 H23 Cl2 N5 O0.25 Pd1
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C14 H23.50 Cl2 N5 O0.25 Pd
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         56.00     56.00    0.00
           H         94.00     92.00    2.00
           Cl         8.00      8.00    0.00
           N         20.00     20.00    0.00
           O          1.00      1.00    0.00
           Pd         4.00      4.00    0.00
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................      50.00 Perc.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C1A    ..  C10A    ..       3.07 Ang.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......        691
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................      42.00 Perc.
PLAT793_ALERT_4_G The Model has Chirality at N3A     (Verify) ....          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   9 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Bis(pyrazolyl)alkylamines are frequently used as N^N^N ligands in metal complexes (Kunrath et al., 2003, Ajellal et al., 2006, Zhang et al., 2008), although bis(pyrazolyl)arylamines can act as bidentate N^N ligands (John et al., 2010).

Palladium dichloride reacts with bis(3,5-dimethylpyrazolyl)alkylamine to afford the title compound, in which the ligand acts as a tridentate N^N^N donor. It is a pseudopolymorph of the previously reported complex [PdCl(C₁₄H₂₃N₅]Cl.2H₂O, which contains two solvent water molecules per ionic complex (de Mendoza et al., 2006).

The title compound consists of discrete [PdCl(C₁₄H₂₃N₅)] cations and chloride anions (Fig. 1). The lattice also contains one quarter of a solvent water molecule per ionic complex. The geometry about the central palladium atom is slightly distorted square planar. This distortion is observed in the bond angles about the palladium atom and the deviation from planarity by the palladium and its four coordinating atoms (average r.m.s. of 0.07 (6) Å). The pyrazole rings are almost perpendicular to each other forming an average dihedral angle of 86.6 (6)° required to mitigate steric conflict between the methyl groups C1 and C14. The pyrazole rings are tilted av. 47.2 (11)° relative to the Pd coordination plane. The bond distances and angles are typical, as confirmed by a Mogul structural check (Bruno et al., 2004) and by comparing the values in the title compound to six similar compounds found in the Cambridge Structural Database (CSD, version 5.31, last update May 2010; Allen, 2002).

The cationic complex exhibits a "whole molecule disorder" over two positions, and the chloride anion is also disordered over two positions. The major components of the disordered moieties are present 58.4 (4)% of the time. There is one strong intermolecular hydrogen bond of the type N—H···Cl present in the ionic compound (Table 1). It is likely that when the solvent water molecule is present it participates in a hydrogen bond with atom Cl2A as indicated by the distance of 3.034 (5) Å between the two atoms. Since the hydrogen atoms on the solvent water molecule could not be located, no further information about a possible hydrogen bond can be obtained. The solvent water molecule cannot be present when atom Cl2, the major component of the disordered chloride anion, is present as it would place the O and Cl atoms in prohibitively close proximity.

Related literature top

For the previously reported pseudopolymorph, see: de Mendoza et al. (2006). For the use of bis(pyrazolyl)alkylamines as ligands in metal complexes, see: Kunrath et al. (2003); Ajellal et al. (2006); Zhang et al. (2008); John et al. (2010). For geometrical parameter checks, see: Bruno et al. (2004); Allen (2002).

Experimental top

A solution of [PdCl₂(NCMe)₂] (0.10 g, 0.39 mmol) and bis(3,5-dimethylpyrazolyl)ethylamine (0.10 g, 0.39 mmol) in dichloromethane (20 ml) was stirred at 233 K for 24 h. The resultant yellowish-orange solution was stored at 269 K for several days to form orange crystals. Yield: 0.06 g (35%). 1^H NMR (CDCl₃): 2.49 (s, 12H, CH₃, pz), 3.62 (t, ³J_H—H = 12.3 Hz, 4H, CH₂-pz), 4.00 (t, ³J_H—H = 12.3 Hz, 4H, CH₂—NH), 5.26 (s, 2H, CH, pz).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and FCF_filter (Guzei, 2007); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010) and modiCIFer (Guzei, 2007).

Figures top

Fig. 1. Molecular structure of the title compond. The thermal ellipsoids are shown at the 50% probability level. All hydrogen atoms connected to carbon atoms and the minor components of disordered atoms were omitted for clarity. The intermolecular hydrogen bond is shown as a dashed line. The solvent water molecule has an ocupancy of 25%.

{Bis[2-(3,5-dimethylpyrazol-1-yl-κN²)ethyl]amine- κN}chloridopalladium(II) chloride 0.25-hydrate top

Crystal data top

[PdCl(C₁₄H₂₃N₅)]Cl·0.25H₂O	F(000) = 898
M_r = 443.68	D_x = 1.636 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 11031 reflections
a = 10.5995 (8) Å	θ = 2.2–30.0°
b = 12.4740 (9) Å	µ = 1.33 mm⁻¹
c = 13.8168 (10) Å	T = 100 K
β = 99.865 (1)°	Block, yellow
V = 1799.8 (2) Å³	0.27 × 0.27 × 0.19 mm
Z = 4

Data collection top

Bruker CCD 1000 area-detector diffractometer	5182 independent reflections
Radiation source: fine-focus sealed tube	4450 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
0.30° ω and 0.4 ° ϕ scans	θ_max = 30.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→14
T_min = 0.715, T_max = 0.786	k = −17→17
26455 measured reflections	l = −18→19

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.057	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0271P)² + 0.7513P] where P = (F_o² + 2F_c²)/3
5182 reflections	(Δ/σ)_max = 0.001
415 parameters	Δρ_max = 0.44 e Å⁻³
691 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[PdCl(C₁₄H₂₃N₅)]Cl·0.25H₂O	V = 1799.8 (2) Å³
M_r = 443.68	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.5995 (8) Å	µ = 1.33 mm⁻¹
b = 12.4740 (9) Å	T = 100 K
c = 13.8168 (10) Å	0.27 × 0.27 × 0.19 mm
β = 99.865 (1)°

Data collection top

Bruker CCD 1000 area-detector diffractometer	5182 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	4450 reflections with I > 2σ(I)
T_min = 0.715, T_max = 0.786	R_int = 0.029
26455 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	691 restraints
wR(F²) = 0.057	H-atom parameters constrained
S = 1.01	Δρ_max = 0.44 e Å⁻³
5182 reflections	Δρ_min = −0.28 e Å⁻³
415 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pd1	0.80405 (12)	0.79001 (8)	1.01257 (6)	0.01812 (12)	0.584 (4)
Cl1	0.72843 (17)	0.72421 (12)	1.14792 (8)	0.0288 (3)	0.584 (4)
Cl2	0.67632 (16)	0.72034 (5)	0.71803 (7)	0.0260 (3)	0.584 (4)
N1	0.7742 (3)	0.9419 (3)	1.0504 (3)	0.0226 (6)	0.584 (4)
N2	0.7043 (4)	1.0067 (3)	0.9815 (3)	0.0227 (7)	0.584 (4)
N3	0.8628 (7)	0.8406 (9)	0.8864 (7)	0.0196 (12)	0.584 (4)
H3	0.8127	0.8008	0.8374	0.024*	0.584 (4)
N4	0.9397 (10)	0.6260 (7)	0.9251 (9)	0.0213 (12)	0.584 (4)
N5	0.8247 (14)	0.6423 (8)	0.9573 (12)	0.0211 (18)	0.584 (4)
C1	0.8615 (4)	0.9538 (4)	1.2288 (3)	0.0343 (8)	0.584 (4)
H1A	0.8131	0.8997	1.2586	0.051*	0.584 (4)
H1B	0.8834	1.0134	1.2748	0.051*	0.584 (4)
H1C	0.9402	0.9217	1.2137	0.051*	0.584 (4)
C2	0.7825 (4)	0.9942 (4)	1.1371 (3)	0.0245 (8)	0.584 (4)
C3	0.7174 (5)	1.0910 (5)	1.1218 (4)	0.0304 (9)	0.584 (4)
H3A	0.7074	1.1427	1.1704	0.036*	0.584 (4)
C4	0.6704 (5)	1.0979 (4)	1.0231 (4)	0.0266 (8)	0.584 (4)
C5	0.5964 (6)	1.1848 (5)	0.9651 (5)	0.0409 (11)	0.584 (4)
H5A	0.6469	1.2144	0.9182	0.061*	0.584 (4)
H5B	0.5777	1.2416	1.0095	0.061*	0.584 (4)
H5C	0.5160	1.1556	0.9292	0.061*	0.584 (4)
C6	0.7008 (4)	0.9829 (4)	0.8770 (4)	0.0238 (9)	0.584 (4)
H6A	0.6694	1.0465	0.8372	0.029*	0.584 (4)
H6B	0.6405	0.9231	0.8570	0.029*	0.584 (4)
C7	0.8313 (5)	0.9530 (5)	0.8579 (4)	0.0235 (9)	0.584 (4)
H7A	0.8344	0.9625	0.7872	0.028*	0.584 (4)
H7B	0.8959	1.0013	0.8956	0.028*	0.584 (4)
C8	0.9946 (5)	0.8097 (5)	0.8785 (4)	0.0286 (10)	0.584 (4)
H8A	1.0532	0.8700	0.9008	0.034*	0.584 (4)
H8B	0.9996	0.7950	0.8088	0.034*	0.584 (4)
C9	1.0378 (8)	0.7104 (5)	0.9401 (6)	0.0259 (12)	0.584 (4)
H9A	1.1180	0.6826	0.9218	0.031*	0.584 (4)
H9B	1.0558	0.7304	1.0104	0.031*	0.584 (4)
C10	1.0477 (4)	0.4927 (4)	0.8342 (2)	0.0369 (8)	0.584 (4)
H10A	1.0551	0.5399	0.7787	0.055*	0.584 (4)
H10B	1.0302	0.4193	0.8102	0.055*	0.584 (4)
H10C	1.1281	0.4940	0.8813	0.055*	0.584 (4)
C11	0.9421 (5)	0.5300 (4)	0.8827 (4)	0.0218 (9)	0.584 (4)
C12	0.8283 (4)	0.4817 (4)	0.8913 (3)	0.0233 (7)	0.584 (4)
H12	0.8009	0.4123	0.8685	0.028*	0.584 (4)
C13	0.7602 (7)	0.5541 (6)	0.9401 (5)	0.0233 (11)	0.584 (4)
C14	0.6270 (4)	0.5440 (4)	0.9603 (3)	0.0325 (8)	0.584 (4)
H14A	0.6253	0.5644	1.0286	0.049*	0.584 (4)
H14B	0.5982	0.4696	0.9498	0.049*	0.584 (4)
H14C	0.5701	0.5912	0.9160	0.049*	0.584 (4)
Pd1A	0.77404 (15)	0.77658 (11)	1.00983 (9)	0.01597 (15)	0.416 (4)
Cl1A	0.68638 (18)	0.69209 (17)	1.13068 (12)	0.0258 (3)	0.416 (4)
Cl2A	0.7350 (3)	0.72156 (8)	0.69987 (10)	0.0311 (5)	0.416 (4)
N1A	0.7336 (4)	0.9221 (4)	1.0594 (4)	0.0195 (8)	0.416 (4)
N2A	0.6665 (5)	0.9933 (5)	0.9944 (4)	0.0219 (9)	0.416 (4)
N3A	0.8351 (11)	0.8443 (12)	0.8917 (9)	0.0164 (12)	0.416 (4)
H3B	0.7974	0.8038	0.8379	0.020*	0.416 (4)
N4A	0.9562 (12)	0.6458 (9)	0.9264 (12)	0.0152 (14)	0.416 (4)
N5A	0.8447 (19)	0.6399 (11)	0.9623 (16)	0.0165 (17)	0.416 (4)
C1A	0.8271 (5)	0.9143 (4)	1.2373 (4)	0.0289 (10)	0.416 (4)
H1D	0.7743	0.8595	1.2619	0.043*	0.416 (4)
H1E	0.8529	0.9682	1.2885	0.043*	0.416 (4)
H1F	0.9036	0.8806	1.2197	0.043*	0.416 (4)
C2A	0.7510 (5)	0.9674 (5)	1.1478 (4)	0.0212 (10)	0.416 (4)
C3A	0.6937 (7)	1.0679 (6)	1.1386 (6)	0.0252 (11)	0.416 (4)
H3C	0.6909	1.1175	1.1904	0.030*	0.416 (4)
C4A	0.6421 (6)	1.0829 (5)	1.0422 (5)	0.0238 (11)	0.416 (4)
C5A	0.5703 (9)	1.1756 (7)	0.9907 (6)	0.0428 (16)	0.416 (4)
H5D	0.6213	1.2085	0.9457	0.064*	0.416 (4)
H5E	0.5539	1.2288	1.0392	0.064*	0.416 (4)
H5F	0.4887	1.1504	0.9533	0.064*	0.416 (4)
C6A	0.6608 (6)	0.9767 (6)	0.8892 (5)	0.0198 (11)	0.416 (4)
H6C	0.6234	1.0407	0.8527	0.024*	0.416 (4)
H6D	0.6053	0.9144	0.8672	0.024*	0.416 (4)
C7A	0.7925 (6)	0.9571 (6)	0.8680 (6)	0.0190 (12)	0.416 (4)
H7C	0.8533	1.0073	0.9072	0.023*	0.416 (4)
H7D	0.7936	0.9714	0.7976	0.023*	0.416 (4)
C8A	0.9775 (8)	0.8360 (6)	0.8929 (6)	0.0229 (12)	0.416 (4)
H8C	1.0202	0.9013	0.9233	0.027*	0.416 (4)
H8D	0.9939	0.8315	0.8246	0.027*	0.416 (4)
C9A	1.0336 (11)	0.7383 (7)	0.9498 (9)	0.0220 (15)	0.416 (4)
H9C	1.1202	0.7243	0.9348	0.026*	0.416 (4)
H9D	1.0424	0.7530	1.0211	0.026*	0.416 (4)
C10A	1.0903 (4)	0.5384 (4)	0.8307 (3)	0.0243 (8)	0.416 (4)
H10D	1.0891	0.5889	0.7762	0.036*	0.416 (4)
H10E	1.0908	0.4648	0.8059	0.036*	0.416 (4)
H10F	1.1673	0.5505	0.8799	0.036*	0.416 (4)
C11A	0.9752 (7)	0.5549 (6)	0.8762 (5)	0.0184 (11)	0.416 (4)
C12A	0.8706 (6)	0.4902 (5)	0.8755 (4)	0.0197 (10)	0.416 (4)
H12A	0.8595	0.4204	0.8478	0.024*	0.416 (4)
C13A	0.7836 (8)	0.5442 (8)	0.9224 (7)	0.0197 (14)	0.416 (4)
C14A	0.6521 (5)	0.5147 (5)	0.9364 (4)	0.0298 (11)	0.416 (4)
H14D	0.6495	0.5092	1.0068	0.045*	0.416 (4)
H14E	0.6285	0.4456	0.9047	0.045*	0.416 (4)
H14F	0.5917	0.5699	0.9070	0.045*	0.416 (4)
O1W	0.5114 (4)	0.7644 (3)	0.8052 (3)	0.0239 (8)	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0221 (3)	0.0185 (2)	0.01357 (11)	0.00310 (19)	0.0024 (2)	0.00027 (12)
Cl1	0.0386 (6)	0.0284 (5)	0.0217 (4)	0.0100 (4)	0.0115 (4)	0.0077 (3)
Cl2	0.0367 (6)	0.0176 (3)	0.0212 (3)	−0.0021 (3)	−0.0023 (3)	−0.0008 (2)
N1	0.0281 (18)	0.0243 (14)	0.0150 (11)	0.0044 (12)	0.0020 (12)	−0.0012 (9)
N2	0.025 (2)	0.0190 (14)	0.0216 (15)	0.0028 (13)	−0.0026 (12)	0.0003 (10)
N3	0.019 (3)	0.0227 (17)	0.0169 (13)	−0.001 (2)	0.0025 (16)	0.0033 (11)
N4	0.021 (2)	0.022 (3)	0.0189 (14)	−0.0030 (17)	−0.0023 (15)	−0.002 (2)
N5	0.018 (4)	0.0246 (19)	0.020 (2)	0.0068 (17)	0.002 (3)	0.0044 (14)
C1	0.0361 (19)	0.048 (3)	0.0175 (13)	−0.0009 (15)	0.0020 (12)	−0.0069 (15)
C2	0.0242 (19)	0.029 (2)	0.0202 (15)	−0.0046 (13)	0.0044 (12)	−0.0081 (13)
C3	0.031 (2)	0.023 (2)	0.039 (2)	−0.0032 (15)	0.0121 (15)	−0.0087 (16)
C4	0.022 (2)	0.0230 (18)	0.037 (2)	−0.0017 (13)	0.0088 (14)	0.0004 (14)
C5	0.040 (2)	0.0256 (18)	0.061 (3)	0.0132 (15)	0.0178 (19)	0.009 (2)
C6	0.028 (3)	0.0209 (14)	0.0195 (16)	−0.0031 (18)	−0.0034 (16)	0.0009 (11)
C7	0.032 (3)	0.0215 (15)	0.0156 (16)	−0.0040 (19)	−0.0001 (16)	0.0030 (11)
C8	0.0254 (19)	0.033 (3)	0.028 (2)	0.0020 (18)	0.0088 (13)	0.0016 (17)
C9	0.0310 (17)	0.027 (3)	0.0191 (19)	0.002 (2)	0.0020 (13)	0.002 (2)
C10	0.0388 (19)	0.053 (2)	0.0182 (12)	0.0216 (16)	0.0019 (12)	−0.0002 (14)
C11	0.025 (3)	0.022 (3)	0.0175 (14)	0.0099 (17)	0.0012 (16)	−0.0002 (16)
C12	0.031 (2)	0.0193 (15)	0.0172 (16)	0.0045 (16)	−0.0035 (13)	0.0013 (12)
C13	0.034 (3)	0.0192 (16)	0.017 (2)	0.0105 (16)	0.0048 (14)	0.0032 (14)
C14	0.0299 (18)	0.033 (2)	0.034 (2)	−0.0002 (14)	0.0056 (13)	0.0060 (14)
Pd1A	0.0168 (4)	0.0158 (3)	0.01479 (16)	0.0016 (2)	0.0015 (2)	0.00192 (15)
Cl1A	0.0246 (6)	0.0282 (7)	0.0266 (5)	0.0077 (5)	0.0097 (5)	0.0115 (5)
Cl2A	0.0471 (11)	0.0213 (5)	0.0215 (5)	0.0048 (5)	−0.0038 (5)	−0.0035 (3)
N1A	0.016 (2)	0.025 (2)	0.0169 (15)	0.0068 (14)	0.0022 (14)	0.0038 (13)
N2A	0.020 (2)	0.023 (2)	0.0231 (19)	0.0004 (17)	0.0029 (16)	0.0017 (14)
N3A	0.014 (4)	0.0178 (19)	0.016 (2)	0.000 (2)	−0.0004 (19)	−0.0007 (15)
N4A	0.016 (3)	0.015 (3)	0.0155 (19)	0.001 (2)	0.005 (2)	−0.004 (2)
N5A	0.012 (4)	0.015 (2)	0.021 (3)	0.0065 (18)	−0.003 (3)	0.0012 (17)
C1A	0.035 (3)	0.033 (3)	0.0186 (17)	0.0070 (18)	0.0032 (17)	−0.0008 (18)
C2A	0.021 (2)	0.023 (3)	0.0217 (18)	0.0015 (17)	0.0075 (16)	0.0012 (16)
C3A	0.028 (3)	0.022 (3)	0.028 (2)	−0.0028 (19)	0.0124 (18)	−0.0037 (18)
C4A	0.022 (3)	0.016 (2)	0.037 (3)	0.0018 (18)	0.0167 (18)	0.0000 (18)
C5A	0.056 (4)	0.031 (3)	0.048 (4)	0.021 (3)	0.028 (3)	0.013 (2)
C6A	0.018 (3)	0.019 (2)	0.021 (2)	0.0039 (19)	0.0006 (18)	0.0056 (14)
C7A	0.024 (4)	0.0173 (19)	0.015 (2)	−0.003 (2)	0.002 (2)	0.0025 (14)
C8A	0.032 (3)	0.017 (3)	0.020 (2)	0.0082 (19)	0.0079 (18)	0.0021 (18)
C9A	0.022 (2)	0.016 (3)	0.026 (3)	−0.002 (2)	−0.0006 (17)	−0.004 (2)
C10A	0.025 (2)	0.027 (2)	0.0230 (17)	0.0089 (15)	0.0092 (14)	0.0037 (15)
C11A	0.024 (3)	0.017 (3)	0.0131 (17)	−0.0023 (17)	−0.0006 (18)	0.0052 (16)
C12A	0.026 (3)	0.017 (2)	0.0171 (19)	0.003 (2)	0.0065 (19)	0.0016 (14)
C13A	0.019 (3)	0.024 (3)	0.016 (3)	−0.001 (2)	0.0010 (19)	0.001 (2)
C14A	0.025 (2)	0.036 (3)	0.028 (3)	−0.0013 (19)	0.0044 (17)	0.0051 (19)
O1W	0.0207 (18)	0.024 (2)	0.028 (2)	−0.0029 (14)	0.0055 (15)	−0.0101 (15)

Geometric parameters (Å, º) top

Pd1—N1	2.005 (4)	Pd1A—N1A	2.013 (5)
Pd1—N5	2.021 (8)	Pd1A—N5A	2.017 (10)
Pd1—N3	2.048 (6)	Pd1A—N3A	2.039 (8)
Pd1—Cl1	2.3079 (12)	Pd1A—Cl1A	2.3009 (16)
N1—C2	1.353 (5)	N1A—C2A	1.328 (8)
N1—N2	1.367 (6)	N1A—N2A	1.372 (8)
N2—C4	1.350 (7)	N2A—C4A	1.345 (10)
N2—C6	1.468 (6)	N2A—C6A	1.460 (9)
N3—C8	1.471 (7)	N3A—C7A	1.497 (14)
N3—C7	1.479 (11)	N3A—C8A	1.511 (11)
N3—H3	0.9300	N3A—H3B	0.9300
N4—C11	1.335 (9)	N4A—N5A	1.360 (19)
N4—N5	1.381 (14)	N4A—C11A	1.362 (13)
N4—C9	1.470 (9)	N4A—C9A	1.421 (12)
N5—C13	1.296 (14)	N5A—C13A	1.423 (17)
C1—C2	1.483 (6)	C1A—C2A	1.510 (8)
C1—H1A	0.9800	C1A—H1D	0.9800
C1—H1B	0.9800	C1A—H1E	0.9800
C1—H1C	0.9800	C1A—H1F	0.9800
C2—C3	1.388 (8)	C2A—C3A	1.390 (10)
C3—C4	1.372 (8)	C3A—C4A	1.364 (11)
C3—H3A	0.9500	C3A—H3C	0.9500
C4—C5	1.489 (8)	C4A—C5A	1.496 (11)
C5—H5A	0.9800	C5A—H5D	0.9800
C5—H5B	0.9800	C5A—H5E	0.9800
C5—H5C	0.9800	C5A—H5F	0.9800
C6—C7	1.500 (5)	C6A—C7A	1.495 (7)
C6—H6A	0.9900	C6A—H6C	0.9900
C6—H6B	0.9900	C6A—H6D	0.9900
C7—H7A	0.9900	C7A—H7C	0.9900
C7—H7B	0.9900	C7A—H7D	0.9900
C8—C9	1.528 (9)	C8A—C9A	1.515 (12)
C8—H8A	0.9900	C8A—H8C	0.9900
C8—H8B	0.9900	C8A—H8D	0.9900
C9—H9A	0.9900	C9A—H9C	0.9900
C9—H9B	0.9900	C9A—H9D	0.9900
C10—C11	1.476 (6)	C10A—C11A	1.479 (8)
C10—H10A	0.9800	C10A—H10D	0.9800
C10—H10B	0.9800	C10A—H10E	0.9800
C10—H10C	0.9800	C10A—H10F	0.9800
C11—C12	1.372 (5)	C11A—C12A	1.371 (6)
C12—C13	1.399 (5)	C12A—C13A	1.389 (7)
C12—H12	0.9500	C12A—H12A	0.9500
C13—C14	1.490 (7)	C13A—C14A	1.486 (9)
C14—H14A	0.9800	C14A—H14D	0.9800
C14—H14B	0.9800	C14A—H14E	0.9800
C14—H14C	0.9800	C14A—H14F	0.9800

N1—Pd1—N5	172.9 (5)	C7A—N3A—C8A	109.2 (9)
N1—Pd1—N3	90.9 (3)	C7A—N3A—Pd1A	116.1 (6)
N5—Pd1—N3	83.7 (5)	C8A—N3A—Pd1A	114.6 (7)
N1—Pd1—Cl1	91.86 (10)	C7A—N3A—H3B	105.2
N5—Pd1—Cl1	93.3 (4)	C8A—N3A—H3B	105.2
N3—Pd1—Cl1	175.9 (4)	Pd1A—N3A—H3B	105.2
C2—N1—N2	106.1 (4)	N5A—N4A—C11A	110.8 (8)
C2—N1—Pd1	134.2 (3)	N5A—N4A—C9A	117.7 (11)
N2—N1—Pd1	117.9 (3)	C11A—N4A—C9A	131.4 (9)
C4—N2—N1	110.7 (4)	N4A—N5A—C13A	105.7 (9)
C4—N2—C6	128.7 (4)	N4A—N5A—Pd1A	117.8 (11)
N1—N2—C6	119.0 (4)	C13A—N5A—Pd1A	131.7 (12)
C8—N3—C7	113.7 (6)	C2A—C1A—H1D	109.5
C8—N3—Pd1	114.5 (5)	C2A—C1A—H1E	109.5
C7—N3—Pd1	115.5 (5)	H1D—C1A—H1E	109.5
C8—N3—H3	103.7	C2A—C1A—H1F	109.5
C7—N3—H3	103.7	H1D—C1A—H1F	109.5
Pd1—N3—H3	103.7	H1E—C1A—H1F	109.5
C11—N4—N5	110.9 (7)	N1A—C2A—C3A	108.1 (6)
C11—N4—C9	129.6 (8)	N1A—C2A—C1A	122.5 (5)
N5—N4—C9	119.5 (8)	C3A—C2A—C1A	129.4 (6)
C13—N5—N4	106.5 (6)	C4A—C3A—C2A	107.9 (7)
C13—N5—Pd1	139.0 (8)	C4A—C3A—H3C	126.0
N4—N5—Pd1	114.5 (8)	C2A—C3A—H3C	126.0
N1—C2—C3	109.2 (4)	N2A—C4A—C3A	106.7 (7)
N1—C2—C1	122.3 (4)	N2A—C4A—C5A	122.3 (7)
C3—C2—C1	128.2 (4)	C3A—C4A—C5A	131.0 (7)
C4—C3—C2	107.0 (5)	C4A—C5A—H5D	109.5
C4—C3—H3A	126.5	C4A—C5A—H5E	109.5
C2—C3—H3A	126.5	H5D—C5A—H5E	109.5
N2—C4—C3	107.0 (5)	C4A—C5A—H5F	109.5
N2—C4—C5	122.5 (5)	H5D—C5A—H5F	109.5
C3—C4—C5	130.5 (5)	H5E—C5A—H5F	109.5
N2—C6—C7	110.8 (4)	N2A—C6A—C7A	109.7 (5)
N2—C6—H6A	109.5	N2A—C6A—H6C	109.7
C7—C6—H6A	109.5	C7A—C6A—H6C	109.7
N2—C6—H6B	109.5	N2A—C6A—H6D	109.7
C7—C6—H6B	109.5	C7A—C6A—H6D	109.7
H6A—C6—H6B	108.1	H6C—C6A—H6D	108.2
N3—C7—C6	111.2 (4)	C6A—C7A—N3A	111.5 (6)
N3—C7—H7A	109.4	C6A—C7A—H7C	109.3
C6—C7—H7A	109.4	N3A—C7A—H7C	109.3
N3—C7—H7B	109.4	C6A—C7A—H7D	109.3
C6—C7—H7B	109.4	N3A—C7A—H7D	109.3
H7A—C7—H7B	108.0	H7C—C7A—H7D	108.0
N3—C8—C9	111.6 (6)	N3A—C8A—C9A	111.3 (8)
N3—C8—H8A	109.3	N3A—C8A—H8C	109.4
C9—C8—H8A	109.3	C9A—C8A—H8C	109.4
N3—C8—H8B	109.3	N3A—C8A—H8D	109.4
C9—C8—H8B	109.3	C9A—C8A—H8D	109.4
H8A—C8—H8B	108.0	H8C—C8A—H8D	108.0
N4—C9—C8	111.4 (7)	N4A—C9A—C8A	112.0 (10)
N4—C9—H9A	109.3	N4A—C9A—H9C	109.2
C8—C9—H9A	109.3	C8A—C9A—H9C	109.2
N4—C9—H9B	109.3	N4A—C9A—H9D	109.2
C8—C9—H9B	109.3	C8A—C9A—H9D	109.2
H9A—C9—H9B	108.0	H9C—C9A—H9D	107.9
N4—C11—C12	105.8 (5)	C11A—C10A—H10D	109.5
N4—C11—C10	123.8 (5)	C11A—C10A—H10E	109.5
C12—C11—C10	130.4 (4)	H10D—C10A—H10E	109.5
C11—C12—C13	107.0 (5)	C11A—C10A—H10F	109.5
C11—C12—H12	126.5	H10D—C10A—H10F	109.5
C13—C12—H12	126.5	H10E—C10A—H10F	109.5
N5—C13—C12	109.7 (6)	N4A—C11A—C12A	107.7 (7)
N5—C13—C14	121.7 (6)	N4A—C11A—C10A	122.5 (6)
C12—C13—C14	128.2 (6)	C12A—C11A—C10A	129.8 (7)
N1A—Pd1A—N5A	170.5 (6)	C11A—C12A—C13A	108.2 (7)
N1A—Pd1A—N3A	90.8 (4)	C11A—C12A—H12A	125.9
N5A—Pd1A—N3A	84.5 (7)	C13A—C12A—H12A	125.9
N1A—Pd1A—Cl1A	91.72 (13)	C12A—C13A—N5A	107.1 (8)
N5A—Pd1A—Cl1A	93.9 (6)	C12A—C13A—C14A	130.8 (7)
N3A—Pd1A—Cl1A	173.5 (4)	N5A—C13A—C14A	122.1 (8)
C2A—N1A—N2A	107.5 (5)	C13A—C14A—H14D	109.5
C2A—N1A—Pd1A	133.8 (4)	C13A—C14A—H14E	109.5
N2A—N1A—Pd1A	118.5 (4)	H14D—C14A—H14E	109.5
C4A—N2A—N1A	109.8 (6)	C13A—C14A—H14F	109.5
C4A—N2A—C6A	128.9 (6)	H14D—C14A—H14F	109.5
N1A—N2A—C6A	119.3 (6)	H14E—C14A—H14F	109.5

N3—Pd1—N1—C2	−148.4 (4)	N3A—Pd1A—N1A—C2A	−138.0 (6)
Cl1—Pd1—N1—C2	34.7 (4)	Cl1A—Pd1A—N1A—C2A	48.0 (4)
N3—Pd1—N1—N2	49.4 (3)	N3A—Pd1A—N1A—N2A	47.0 (5)
Cl1—Pd1—N1—N2	−127.5 (2)	Cl1A—Pd1A—N1A—N2A	−127.0 (3)
C2—N1—N2—C4	0.6 (4)	C2A—N1A—N2A—C4A	0.0 (5)
Pd1—N1—N2—C4	167.4 (2)	Pd1A—N1A—N2A—C4A	176.2 (3)
C2—N1—N2—C6	167.5 (3)	C2A—N1A—N2A—C6A	165.0 (4)
Pd1—N1—N2—C6	−25.7 (4)	Pd1A—N1A—N2A—C6A	−18.7 (5)
N1—Pd1—N3—C8	120.0 (8)	N1A—Pd1A—N3A—C7A	−18.1 (9)
N5—Pd1—N3—C8	−64.6 (9)	N5A—Pd1A—N3A—C7A	170.2 (11)
N1—Pd1—N3—C7	−15.0 (7)	N1A—Pd1A—N3A—C8A	110.8 (9)
N5—Pd1—N3—C7	160.4 (8)	N5A—Pd1A—N3A—C8A	−60.9 (11)
C11—N4—N5—C13	3.8 (17)	C11A—N4A—N5A—C13A	−7 (2)
C9—N4—N5—C13	−176.5 (11)	C9A—N4A—N5A—C13A	176.1 (14)
C11—N4—N5—Pd1	−175.1 (8)	C11A—N4A—N5A—Pd1A	−165.3 (12)
C9—N4—N5—Pd1	4.6 (18)	C9A—N4A—N5A—Pd1A	18 (2)
N3—Pd1—N5—C13	−129.7 (19)	N3A—Pd1A—N5A—N4A	39.0 (17)
Cl1—Pd1—N5—C13	47.5 (18)	Cl1A—Pd1A—N5A—N4A	−147.3 (17)
N3—Pd1—N5—N4	48.7 (12)	N3A—Pd1A—N5A—C13A	−113 (2)
Cl1—Pd1—N5—N4	−134.1 (12)	Cl1A—Pd1A—N5A—C13A	61 (2)
N2—N1—C2—C3	0.2 (4)	N2A—N1A—C2A—C3A	0.4 (5)
Pd1—N1—C2—C3	−163.5 (3)	Pd1A—N1A—C2A—C3A	−175.0 (4)
N2—N1—C2—C1	−174.3 (3)	N2A—N1A—C2A—C1A	−177.0 (4)
Pd1—N1—C2—C1	22.0 (5)	Pd1A—N1A—C2A—C1A	7.6 (7)
N1—C2—C3—C4	−0.9 (4)	N1A—C2A—C3A—C4A	−0.6 (6)
C1—C2—C3—C4	173.2 (4)	C1A—C2A—C3A—C4A	176.5 (5)
N1—N2—C4—C3	−1.2 (4)	N1A—N2A—C4A—C3A	−0.4 (6)
C6—N2—C4—C3	−166.4 (4)	C6A—N2A—C4A—C3A	−163.6 (5)
N1—N2—C4—C5	178.4 (4)	N1A—N2A—C4A—C5A	179.9 (5)
C6—N2—C4—C5	13.1 (6)	C6A—N2A—C4A—C5A	16.7 (9)
C2—C3—C4—N2	1.2 (4)	C2A—C3A—C4A—N2A	0.6 (6)
C2—C3—C4—C5	−178.2 (4)	C2A—C3A—C4A—C5A	−179.7 (6)
C4—N2—C6—C7	121.7 (5)	C4A—N2A—C6A—C7A	112.8 (7)
N1—N2—C6—C7	−42.5 (5)	N1A—N2A—C6A—C7A	−49.0 (7)
C8—N3—C7—C6	−174.3 (6)	N2A—C6A—C7A—N3A	78.9 (9)
Pd1—N3—C7—C6	−39.0 (8)	C8A—N3A—C7A—C6A	−166.3 (7)
N2—C6—C7—N3	79.1 (7)	Pd1A—N3A—C7A—C6A	−34.8 (11)
C7—N3—C8—C9	160.3 (6)	C7A—N3A—C8A—C9A	160.0 (7)
Pd1—N3—C8—C9	24.4 (9)	Pd1A—N3A—C8A—C9A	27.7 (12)
C11—N4—C9—C8	112.6 (12)	N5A—N4A—C9A—C8A	−73.7 (19)
N5—N4—C9—C8	−67.0 (14)	C11A—N4A—C9A—C8A	109.9 (16)
N3—C8—C9—N4	46.6 (9)	N3A—C8A—C9A—N4A	44.1 (12)
N5—N4—C11—C12	−2.5 (13)	N5A—N4A—C11A—C12A	2.8 (18)
C9—N4—C11—C12	177.9 (11)	C9A—N4A—C11A—C12A	179.4 (15)
N5—N4—C11—C10	175.0 (9)	N5A—N4A—C11A—C10A	−178.8 (13)
C9—N4—C11—C10	−4.6 (16)	C9A—N4A—C11A—C10A	−2 (2)
N4—C11—C12—C13	0.3 (8)	N4A—C11A—C12A—C13A	2.6 (11)
C10—C11—C12—C13	−177.0 (5)	C10A—C11A—C12A—C13A	−175.7 (8)
N4—N5—C13—C12	−3.6 (15)	C11A—C12A—C13A—N5A	−6.7 (14)
Pd1—N5—C13—C12	174.9 (14)	C11A—C12A—C13A—C14A	175.5 (9)
N4—N5—C13—C14	−176.6 (9)	N4A—N5A—C13A—C12A	8 (2)
Pd1—N5—C13—C14	2 (2)	Pd1A—N5A—C13A—C12A	162.4 (15)
C11—C12—C13—N5	2.2 (11)	N4A—N5A—C13A—C14A	−173.8 (13)
C11—C12—C13—C14	174.6 (6)	Pd1A—N5A—C13A—C14A	−20 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Cl2	0.93	2.24	3.162 (12)	174
N3A—H3B···Cl2A	0.93	2.17	3.088 (15)	170

Experimental details

Crystal data
Chemical formula	[PdCl(C₁₄H₂₃N₅)]Cl·0.25H₂O
M_r	443.68
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	10.5995 (8), 12.4740 (9), 13.8168 (10)
β (°)	99.865 (1)
V (Å³)	1799.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.33
Crystal size (mm)	0.27 × 0.27 × 0.19

Data collection
Diffractometer	Bruker CCD 1000 area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.715, 0.786
No. of measured, independent and observed [I > 2σ(I)] reflections	26455, 5182, 4450
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.057, 1.01
No. of reflections	5182
No. of parameters	415
No. of restraints	691
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.28

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and FCF_filter (Guzei, 2007), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2009), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010) and modiCIFer (Guzei, 2007).