A potential anti­cancer agent: 5-chloro-7-iodo-8-hy­droxy­quinolinium dichlorido(5-chloro-7-iodo­quinolin-8-olato-κ2N,O)palladium(II) dihydrate

Vranec, P.; Potočňák, I.

doi:10.1107/S1600536811040803

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages m1508-m1509

doi:10.1107/S1600536811040803

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A potential anticancer agent: 5-chloro-7-iodo-8-hydroxyquinolinium dichlorido(5-chloro-7-iodoquinolin-8-olato-κ²N,O)palladium(II) dihydrate

Peter Vranec ^a ^* and Ivan Potočňák ^a

^aDepartment of Inorganic Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, SK-041 54 Košice, Slovakia
^*Correspondence e-mail: peter.vranec@student.upjs.sk

(Received 28 September 2011; accepted 4 October 2011; online 8 October 2011)

The title Pd^II coordination compound, (C₉H₆ClINO)[PdCl₂(C₉H₄ClINO)]·2H₂O, was prepared as a potential anticancer agent. Its structure is ionic and consists of a square-planar [PdCl₂(CQ)]⁻ complex anion (CQ is 5-chloro-7-iodoquinolin-8-olate), with the Pd^II atom surrounded by two chloride ligands in a cis configuration and one N,O-bidentate CQ molecule, a protonated anion of CQ as counter-cation and two non-coordinated water molecules. The water molecules are involved in O—H⋯O and N—H⋯O hydrogen bonds, which interconnect the HCQ⁺ cations into a chain parallel to [010]. Apart from these interactions, the structure is also stabilized by face-to-face π–π interactions [centroid–centroid = 3.546 (3) Å], which occur between the phenolic parts of the complex anions and cations.

Related literature

For background to square-planar complexes of platinum and palladium as potential chemotherapeutics, see: Bielawska et al. (2010 ); Bruijnincx & Sadler (2008 ); Ding et al. (2005 ); Garoufis et al. (2009 ). For structures of CQ complexes, see: Di Vaira et al. (2004 ) for [Cu(CQ)₂] and [Zn(CQ)₂(H₂O)]·H₂O·THF; Miyashita et al. (2005 ) for [ReCl₂(CQ)O(PPh₃)]. The structure of [Pd(8-HQ)₂] (8-HQ = 8-hydroxyquinoline) was previously described by Prout & Wheeler (1966 ). For other related structures, see: Cui et al. (2009 ); Guney et al. (2011 ); Screnci & McKeage (1999 ); Yue et al. (2008 ); Kapteijn et al. (1996 ); Fazeli et al. (2009 ); Gniewek et al. (2006 ). Structures of complexes containing other halogen-derivatives of 8-HQ may also be found in the Cambridge Structural Database, see: Allen (2002 ). For π–π interactions, see: Janiak (2000 ).

Experimental

Crystal data

(C₉H₆ClINO)[PdCl₂(C₉H₄ClINO)]·2H₂O
M_r = 824.31
Monoclinic, C 2/c
a = 34.3212 (10) Å
b = 7.7028 (2) Å
c = 18.4128 (5) Å
β = 104.455 (3)°
V = 4713.7 (2) Å³
Z = 8
Mo Kα radiation
μ = 3.89 mm⁻¹
T = 293 K
0.44 × 0.14 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.555, T_max = 1.000
24287 measured reflections
4641 independent reflections
3888 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.080
S = 1.14
4641 reflections
287 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.87 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Pd1—N1	2.009 (4)
Pd1—O1	2.035 (3)
Pd1—Cl1	2.2711 (14)
Pd1—Cl2	2.3107 (14)

N1—Pd1—O1	82.12 (15)
N1—Pd1—Cl1	94.01 (12)
O1—Pd1—Cl1	175.98 (10)
N1—Pd1—Cl2	175.90 (12)
O1—Pd1—Cl2	94.44 (10)
Cl1—Pd1—Cl2	89.47 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.82	2.18	2.782 (7)	131
N2—H2N⋯O4A	0.82 (6)	1.92 (6)	2.737 (10)	174 (6)
N2—H2N⋯O4B	0.82 (6)	1.96 (6)	2.683 (9)	146 (6)
O4A—H1O4⋯O2	0.85	2.00	2.787 (10)	155
C28—H28⋯O3ⁱ	0.93	2.48	3.347 (8)	155
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and CALC-OH (Nardelli, 1999 ); molecular graphics: DIAMOND (Brandenburg, 2001 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811040803/ff2030sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811040803/ff2030Isup2.hkl

checkCIF report

Comment top

Square-planar complexes of platinum and palladium, as potential chemotherapeutics, are studied worldwide (Bruijnincx & Sadler, 2008 and Bielawska et al., 2010). Unfortunately, many of these anticancer drugs exhibit significant side effects and their activity is relatively low (Screnci & McKeage, 1999). One of the approaches to overcome limitations connected with platinum- or palladium-based chemotherapy, new square-planar coordination compounds of these metals with biologically active ligands should be prepared. One of the examples of such ligand is 5-chloro-7-iodo-8-hydroxyquinoline (clioquinol, CQ), as it exhibits wide range of biological activity, including anticancer activity. CQ's favourable effect to human cancer cells is ascribed to its ability to chelate metal ions (Ding et al., 2005). In our efforts to prepare novel square-planar complexes of Pt and Pd with clioquinol of Cat[MCl₂(CQ)] (M = Pt or Pd; Cat = cation of +1 charge, such as Na⁺, K⁺ or Cs⁺) composition, we prepared crystals of HCQ[PdCl₂(CQ)].2H₂O (I) (HCQ = protonated molecule of CQ), which we believe has an increased anticancer activity. Here we present the structure of the title compound.

The molecular structure of the ionic HCQ[PdCl₂(CQ)].2H₂O (I) compound consists of discrete [PdCl₂(CQ)]^- anion in which the central Pd^II atom has a distorted square-planar configuration, protonated molecule of CQ (HCQ⁺) as cation, and two non-coordinated water molecules (Fig. 1). Complex anion is formed by Pd^II atom which is surrounded by two chlorido ligands in cis- configuration at 2.271 (1) (Pd1—Cl1) and 2.311 (1) Å (Pd1—Cl2) distances, which are close to Pd—Cl distances observed in other square planar Pd^II complexes (Cui et al., 2009), and one bidentately coordinated CQ molecule. This is bound to Pd^II atom by nitrogen atom of pyridine part and oxygen atom, which is ready to coordinate after deprotonation of the CQ's hydroxyl group in phenolic part; the Pd1—N1 (2.009 (4) Å) and Pd1—O1 (2.035 (3) Å) distances are normal (Yue et al., 2008). Both the coordinated and free protonated CQ molecules are nearly planar, with the largest deviation of atoms from the mean planes through the aromatic rings being 0.05 (1) Å. The geometric parameters within the individual rings resemble those found in similar compounds containing pyridine and phenolic rings (Guney et al., 2011 and Kapteijn et al., 1996). The C—X bonds (X = Cl and I; 1.742 (10) and 2.098 (2) Å in average, respectively) are usual for single C_sp2—X bonds (Fazeli et al., 2009 and Gniewek et al., 2006).

Besides the ionic forces, the structure is also stabilized by π-π interactions and hydrogen bonds. π-π interactions occur between the phenolic parts of the complex anion and the cation. The distance between centroids of these parts (Cg_An—Cg_Cat = 3.546 (3) Å) and angle between normal to the plane and vector connecting the two centroids (16.46°) are consistent with the values typical for the face-to-face π–π interactions (Janiak, 2000). Moreover, the distance between Pd1 atom and Cg_Catⁱ of another adjacent cation (i = x, 1 + y, z) of 3.497 Å and the angle between normal to the plane of HCQ⁺ cation and vector connecting Cg_Catⁱ and Pd1 of 171.96° indicate possible η⁶ semi coordination of the phenyl ring of the cation. Thus the coordination number of Pd atom can be considered as 4 + 1 with a tetragonal pyramidal coordination polyhedron. Due to these intermolecular contacts the cations and anions are linked to form a chain parallel with [010] (Fig. 2).

Two uncoordinated water molecules interconnect the HCQ⁺ cations via hydrogen bonds into a chain running along [010] (Fig. 3). Distances and angles characterizing these bonds are summarized in Table 2.

Related literature top

For background to square-planar complexes of platinum and palladium as potential chemotherapeutics, see: Bielawska et al. (2010); Bruijnincx & Sadler (2008); Ding et al. (2005); Garoufis et al. (2009). For structures of CQ complexes, see: Di Vaira et al. (2004) ([Cu(CQ)₂] and [Zn(CQ)₂(H₂O)].H₂O.THF); Miyashita et al. (2005) ([ReCl₂(CQ)O(PPh₃)]). The structure of [Pd(8-HQ)₂] (8-HQ = 8-hydroxyquinoline) was previously described by Prout & Wheeler (1966). For other related structures, see: Cui et al. (2009); Guney et al. (2011); Screnci & McKeage (1999); Yue et al. (2008); Kapteijn et al. (1996); Fazeli et al. (2009); Gniewek et al. (2006). Structures of complexes containing other halogen-derivatives of 8-HQ may also be found in the Cambridge Structural Database, see: Allen (2002). For π–π interactions, see: Janiak (2000).

Experimental top

Ethanolic solution of PdCl₂ prepared from 0.2 cm³ 40% water solution of PdCl₂ in 8 cm³ of ethanol (0.048 g PdCl₂; 0.27 mmol) was cooled down to -15 °C and mixed with a cold (-5 °C) THF solution of CQ (0.17 g CQ dissolved in 15 cm³ of THF; 0.54 mmol). Resulting solution was stirred at -15 °C for a while and then a cold (3 °C) aqueous solution of CsCl (0.046 g of CsCl dissolved in 2 cm³ of water; 0.27 mmol) was added. Yellow precipitation of I, which formed immediately after mixing, was filtered off, dried on air and analyzed by IR and elemental analysis. Mother liquor was left for crystallization in refrigerator at -5 °C and after few days we obtained a small amount of orange-red crystals of I. Crystals were filtered off, dried on air and analyzed by IR spectroscopy to prove their identity with the precipitation.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and CALC-OH (Nardelli, 1999); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of I. Displacement ellipsoids are drawn at the 50% probability for non-H atoms. H atoms are represented as small spheres of arbitrary radii. Only one position of the disordered O4 water molecule is shown.
	Fig. 2. Parallel stacking of the cation and the complex anion enabling π-π interactions in I (shown by dashed lines); i = x, 1 + y, z. Possible penta-coordination of Pd^II is suggested.
	Fig. 3. The system of hydrogen bonds (dashed lines) in I formed in the direction of b axis. Complex anions are not shown because of clarity.

5-chloro-7-iodo-8-hydroxyquinolinium dichlorido(5-chloro-7-iodoquinolin-8-olato-κ²N,O)palladium(II) dihydrate top

Crystal data top

(C₉H₆ClINO)[PdCl₂(C₉H₄ClINO)]·2H₂O	F(000) = 3104
M_r = 824.31	D_x = 2.323 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 14809 reflections
a = 34.3212 (10) Å	θ = 3.0–29.6°
b = 7.7028 (2) Å	µ = 3.89 mm⁻¹
c = 18.4128 (5) Å	T = 293 K
β = 104.455 (3)°	Needle, orange-red
V = 4713.7 (2) Å³	0.44 × 0.14 × 0.07 mm
Z = 8

Data collection top

Oxford Diffraction Xcalibur Sapphire2 diffractometer	4641 independent reflections
Radiation source: fine-focus sealed tube	3888 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
Detector resolution: 8.3438 pixels mm^-1	θ_max = 26.0°, θ_min = 3.0°
ω scans	h = −42→42
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2007)	k = −9→9
T_min = 0.555, T_max = 1.000	l = −22→22
24287 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ²(F_o²) + (0.0265P)² + 28.2625P] where P = (F_o² + 2F_c²)/3
4641 reflections	(Δ/σ)_max = 0.002
287 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.87 e Å⁻³

Crystal data top

(C₉H₆ClINO)[PdCl₂(C₉H₄ClINO)]·2H₂O	V = 4713.7 (2) Å³
M_r = 824.31	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 34.3212 (10) Å	µ = 3.89 mm⁻¹
b = 7.7028 (2) Å	T = 293 K
c = 18.4128 (5) Å	0.44 × 0.14 × 0.07 mm
β = 104.455 (3)°

Data collection top

Oxford Diffraction Xcalibur Sapphire2 diffractometer	4641 independent reflections
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2007)	3888 reflections with I > 2σ(I)
T_min = 0.555, T_max = 1.000	R_int = 0.049
24287 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ²(F_o²) + (0.0265P)² + 28.2625P] where P = (F_o² + 2F_c²)/3
4641 reflections	Δρ_max = 0.61 e Å⁻³
287 parameters	Δρ_min = −0.87 e Å⁻³

Special details top

Experimental. CrysAlis RED, Oxford Diffraction (2007), Analytical numeric absorption correction using a multifaceted crystal model.

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)
I1	0.699063 (11)	0.67835 (5)	0.58026 (2)	0.04530 (12)
Pd1	0.627824 (11)	0.95775 (5)	0.77655 (2)	0.02970 (11)
Cl1	0.59303 (5)	1.0787 (2)	0.85369 (8)	0.0471 (4)
Cl2	0.68728 (4)	1.0204 (2)	0.86375 (8)	0.0483 (4)
I2	0.611094 (11)	0.16194 (5)	0.507511 (19)	0.03868 (11)
Cl3	0.53299 (5)	0.6203 (2)	0.43378 (8)	0.0515 (4)
Cl4	0.54308 (4)	0.4700 (3)	0.72671 (9)	0.0574 (4)
O1	0.65529 (10)	0.8421 (5)	0.70322 (19)	0.0343 (8)
O2	0.69038 (11)	0.2391 (6)	0.6466 (2)	0.0469 (10)
H2	0.6854	0.1925	0.6052	0.070*
N1	0.57824 (12)	0.9057 (6)	0.6950 (2)	0.0329 (10)
C13	0.60872 (16)	0.6631 (7)	0.5168 (3)	0.0345 (12)
H3	0.6161	0.6098	0.4769	0.041*
N2	0.69550 (14)	0.4180 (6)	0.7764 (3)	0.0373 (11)
H2N	0.7156 (18)	0.398 (8)	0.761 (3)	0.045*
C12	0.63853 (15)	0.7155 (6)	0.5801 (3)	0.0288 (10)
C14	0.56918 (16)	0.6898 (7)	0.5132 (3)	0.0346 (12)
C11	0.62914 (14)	0.7916 (6)	0.6417 (3)	0.0274 (10)
C28	0.70063 (18)	0.4935 (8)	0.8424 (3)	0.0459 (15)
H28	0.7265	0.5133	0.8719	0.055*
C29	0.65883 (15)	0.3807 (7)	0.7305 (3)	0.0310 (11)
C19	0.58701 (14)	0.8219 (6)	0.6352 (3)	0.0279 (10)
C25	0.62410 (15)	0.4374 (7)	0.7528 (3)	0.0315 (11)
C23	0.58380 (15)	0.3332 (7)	0.6341 (3)	0.0331 (11)
H23	0.5587	0.3198	0.6008	0.040*
C18	0.54040 (16)	0.9481 (8)	0.6920 (3)	0.0441 (14)
H8	0.5346	1.0081	0.7319	0.053*
C22	0.61854 (15)	0.2761 (6)	0.6136 (3)	0.0302 (11)
C24	0.58658 (15)	0.4075 (7)	0.7019 (3)	0.0337 (11)
C21	0.65593 (15)	0.2950 (7)	0.6611 (3)	0.0304 (11)
C16	0.51643 (16)	0.8190 (8)	0.5717 (3)	0.0418 (13)
H6	0.4953	0.7889	0.5311	0.050*
C15	0.55647 (15)	0.7739 (7)	0.5712 (3)	0.0328 (11)
C27	0.66770 (19)	0.5433 (8)	0.8681 (3)	0.0451 (14)
H27	0.6713	0.5941	0.9151	0.054*
C26	0.62989 (17)	0.5169 (7)	0.8236 (3)	0.0388 (13)
H26	0.6077	0.5519	0.8403	0.047*
C17	0.50877 (17)	0.9044 (9)	0.6298 (3)	0.0538 (16)
H7	0.4825	0.9349	0.6292	0.065*
O4A	0.7649 (2)	0.3424 (13)	0.7353 (5)	0.0556 (18)	0.50
H1O4	0.7444	0.3321	0.6986	0.083*	0.50
H2O4	0.7819	0.2658	0.7303	0.083*	0.50
O4B	0.7706 (2)	0.4711 (14)	0.7626 (5)	0.0556 (18)	0.50
O3	0.72251 (16)	0.1567 (7)	0.5263 (3)	0.0780 (16)
H2O3	0.7047	0.0789	0.5129	0.117*
H1O3	0.7125	0.2474	0.5028	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0356 (2)	0.0526 (2)	0.0522 (2)	0.00153 (17)	0.01937 (17)	−0.00573 (18)
Pd1	0.0312 (2)	0.0324 (2)	0.02578 (18)	−0.00258 (17)	0.00749 (15)	0.00048 (16)
Cl1	0.0538 (9)	0.0550 (9)	0.0381 (7)	0.0005 (7)	0.0218 (7)	−0.0047 (6)
Cl2	0.0436 (8)	0.0610 (9)	0.0350 (7)	−0.0094 (7)	−0.0002 (6)	−0.0030 (7)
I2	0.0445 (2)	0.0382 (2)	0.03188 (18)	−0.00183 (16)	0.00673 (15)	0.00035 (15)
Cl3	0.0471 (9)	0.0655 (10)	0.0352 (7)	−0.0147 (7)	−0.0020 (6)	−0.0088 (7)
Cl4	0.0315 (7)	0.0886 (12)	0.0561 (9)	0.0108 (8)	0.0184 (7)	0.0014 (9)
O1	0.0263 (18)	0.045 (2)	0.0298 (18)	−0.0024 (16)	0.0042 (15)	−0.0069 (16)
O2	0.036 (2)	0.066 (3)	0.041 (2)	0.012 (2)	0.0132 (18)	0.006 (2)
N1	0.028 (2)	0.039 (2)	0.032 (2)	−0.0007 (19)	0.0082 (18)	0.0029 (19)
C13	0.045 (3)	0.033 (3)	0.026 (2)	−0.003 (2)	0.010 (2)	0.001 (2)
N2	0.028 (2)	0.044 (3)	0.036 (2)	−0.004 (2)	−0.0001 (19)	0.008 (2)
C12	0.028 (3)	0.027 (3)	0.034 (2)	0.002 (2)	0.011 (2)	0.001 (2)
C14	0.039 (3)	0.034 (3)	0.026 (2)	−0.006 (2)	0.000 (2)	0.001 (2)
C11	0.028 (3)	0.028 (3)	0.025 (2)	−0.001 (2)	0.003 (2)	0.006 (2)
C28	0.043 (3)	0.044 (3)	0.040 (3)	−0.012 (3)	−0.011 (3)	0.006 (3)
C29	0.027 (3)	0.033 (3)	0.031 (3)	−0.006 (2)	0.001 (2)	0.007 (2)
C19	0.028 (3)	0.028 (3)	0.028 (2)	−0.003 (2)	0.008 (2)	−0.001 (2)
C25	0.035 (3)	0.029 (3)	0.030 (2)	−0.002 (2)	0.008 (2)	0.007 (2)
C23	0.026 (3)	0.036 (3)	0.034 (3)	−0.003 (2)	0.003 (2)	0.002 (2)
C18	0.033 (3)	0.058 (4)	0.044 (3)	0.004 (3)	0.015 (3)	−0.006 (3)
C22	0.034 (3)	0.030 (3)	0.026 (2)	−0.002 (2)	0.005 (2)	0.002 (2)
C24	0.024 (2)	0.040 (3)	0.039 (3)	−0.002 (2)	0.013 (2)	0.007 (2)
C21	0.028 (3)	0.035 (3)	0.030 (2)	−0.001 (2)	0.010 (2)	0.005 (2)
C16	0.028 (3)	0.054 (4)	0.039 (3)	−0.003 (3)	0.000 (2)	0.001 (3)
C15	0.030 (3)	0.036 (3)	0.031 (3)	−0.003 (2)	0.005 (2)	0.007 (2)
C27	0.059 (4)	0.045 (3)	0.028 (3)	0.000 (3)	0.005 (3)	−0.004 (2)
C26	0.044 (3)	0.042 (3)	0.032 (3)	0.000 (3)	0.013 (2)	0.005 (2)
C17	0.027 (3)	0.079 (5)	0.054 (4)	0.001 (3)	0.008 (3)	−0.004 (3)
O4A	0.030 (3)	0.082 (6)	0.055 (4)	0.009 (4)	0.010 (3)	0.010 (4)
O4B	0.030 (3)	0.082 (6)	0.055 (4)	0.009 (4)	0.010 (3)	0.010 (4)
O3	0.083 (4)	0.075 (4)	0.063 (3)	−0.007 (3)	−0.007 (3)	−0.007 (3)

Geometric parameters (Å, º) top

I1—C12	2.096 (5)	C28—H28	0.9300
Pd1—N1	2.009 (4)	C29—C21	1.420 (7)
Pd1—O1	2.035 (3)	C29—C25	1.423 (7)
Pd1—Cl1	2.2711 (14)	C19—C15	1.416 (7)
Pd1—Cl2	2.3107 (14)	C25—C26	1.409 (7)
I2—C22	2.099 (5)	C25—C24	1.410 (7)
Cl3—C14	1.749 (5)	C23—C24	1.354 (7)
Cl4—C24	1.735 (5)	C23—C22	1.408 (7)
O1—C11	1.316 (6)	C23—H23	0.9300
O2—C21	1.347 (6)	C18—C17	1.407 (8)
O2—H2	0.8200	C18—H8	0.9300
N1—C18	1.327 (7)	C22—C21	1.369 (7)
N1—C19	1.373 (6)	C16—C17	1.338 (8)
C13—C14	1.358 (8)	C16—C15	1.419 (7)
C13—C12	1.405 (7)	C16—H6	0.9300
C13—H3	0.9300	C27—C26	1.366 (8)
N2—C28	1.319 (7)	C27—H27	0.9300
N2—C29	1.360 (6)	C26—H26	0.9300
N2—H2N	0.82 (6)	C17—H7	0.9300
C12—C11	1.385 (7)	O4A—H1O4	0.8502
C14—C15	1.409 (7)	O4A—H2O4	0.8499
C11—C19	1.440 (7)	O3—H2O3	0.8488
C28—C27	1.384 (9)	O3—H1O3	0.8483

N1—Pd1—O1	82.12 (15)	C26—C25—C24	125.5 (5)
N1—Pd1—Cl1	94.01 (12)	C26—C25—C29	117.7 (5)
O1—Pd1—Cl1	175.98 (10)	C24—C25—C29	116.7 (5)
N1—Pd1—Cl2	175.90 (12)	C24—C23—C22	120.6 (5)
O1—Pd1—Cl2	94.44 (10)	C24—C23—H23	119.7
Cl1—Pd1—Cl2	89.47 (6)	C22—C23—H23	119.7
C11—O1—Pd1	111.8 (3)	N1—C18—C17	121.5 (5)
C21—O2—H2	109.5	N1—C18—H8	119.2
C18—N1—C19	119.4 (4)	C17—C18—H8	119.2
C18—N1—Pd1	128.3 (4)	C21—C22—C23	121.1 (5)
C19—N1—Pd1	112.3 (3)	C21—C22—I2	121.1 (4)
C14—C13—C12	120.6 (5)	C23—C22—I2	117.8 (4)
C14—C13—H3	119.7	C23—C24—C25	121.6 (5)
C12—C13—H3	119.7	C23—C24—Cl4	119.5 (4)
C28—N2—C29	123.7 (5)	C25—C24—Cl4	118.8 (4)
C28—N2—H2N	118 (4)	O2—C21—C22	124.6 (5)
C29—N2—H2N	118 (4)	O2—C21—C29	117.4 (4)
C11—C12—C13	122.1 (5)	C22—C21—C29	118.0 (5)
C11—C12—I1	119.3 (4)	C17—C16—C15	120.6 (5)
C13—C12—I1	118.6 (4)	C17—C16—H6	119.7
C13—C14—C15	121.8 (5)	C15—C16—H6	119.7
C13—C14—Cl3	119.1 (4)	C14—C15—C19	116.5 (5)
C15—C14—Cl3	119.0 (4)	C14—C15—C16	126.9 (5)
O1—C11—C12	125.6 (4)	C19—C15—C16	116.6 (5)
O1—C11—C19	118.6 (4)	C26—C27—C28	119.3 (5)
C12—C11—C19	115.7 (4)	C26—C27—H27	120.4
N2—C28—C27	120.3 (5)	C28—C27—H27	120.4
N2—C28—H28	119.9	C27—C26—C25	120.9 (5)
C27—C28—H28	119.9	C27—C26—H26	119.6
N2—C29—C21	120.2 (5)	C25—C26—H26	119.6
N2—C29—C25	117.9 (5)	C16—C17—C18	120.2 (5)
C21—C29—C25	121.8 (4)	C16—C17—H7	119.9
N1—C19—C15	121.7 (4)	C18—C17—H7	119.9
N1—C19—C11	115.2 (4)	H1O4—O4A—H2O4	107.7
C15—C19—C11	123.1 (4)	H2O3—O3—H1O3	105.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.82	2.18	2.782 (7)	131
N2—H2N···O4A	0.82 (6)	1.92 (6)	2.737 (10)	174 (6)
N2—H2N···O4B	0.82 (6)	1.96 (6)	2.683 (9)	146 (6)
O4A—H1O4···O2	0.85	2.00	2.787 (10)	155
C28—H28···O3ⁱ	0.93	2.48	3.347 (8)	155

Symmetry code: (i) −x+3/2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	(C₉H₆ClINO)[PdCl₂(C₉H₄ClINO)]·2H₂O
M_r	824.31
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	34.3212 (10), 7.7028 (2), 18.4128 (5)
β (°)	104.455 (3)
V (Å³)	4713.7 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.89
Crystal size (mm)	0.44 × 0.14 × 0.07

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire2 diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.555, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	24287, 4641, 3888
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.080, 1.14
No. of reflections	4641
No. of parameters	287
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0265P)² + 28.2625P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.87

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and CALC-OH (Nardelli, 1999), DIAMOND (Brandenburg, 2001), SHELXL97 (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

I1—C12	2.096 (5)	Pd1—Cl2	2.3107 (14)
Pd1—N1	2.009 (4)	I2—C22	2.099 (5)
Pd1—O1	2.035 (3)	Cl3—C14	1.749 (5)
Pd1—Cl1	2.2711 (14)	Cl4—C24	1.735 (5)

N1—Pd1—O1	82.12 (15)	N1—Pd1—Cl2	175.90 (12)
N1—Pd1—Cl1	94.01 (12)	O1—Pd1—Cl2	94.44 (10)
O1—Pd1—Cl1	175.98 (10)	Cl1—Pd1—Cl2	89.47 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.82	2.18	2.782 (7)	130.7
N2—H2N···O4A	0.82 (6)	1.92 (6)	2.737 (10)	174 (6)
N2—H2N···O4B	0.82 (6)	1.96 (6)	2.683 (9)	146 (6)
O4A—H1O4···O2	0.85	2.00	2.787 (10)	154.6
C28—H28···O3ⁱ	0.93	2.48	3.347 (8)	154.7

Symmetry code: (i) −x+3/2, y+1/2, −z+3/2.

Acknowledgements

This work was supported by a grant from the Slovak Grant Agency (VEGA No. 1/0079/08) and by the VVGS (PF 27/2011/CH).

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