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Bis(5-chloro-8-hy­droxy­quinolinium) tetra­chloridopalladate(II), (C9H7ClNO)2[PdCl4], (I), catena-poly[dimethyl­ammonium [[di­chloridopalladate(II)]-μ-chlorido]], {(C2H8N)[PdCl3]}n, (II), ethyl­enediammonium bis­(5-chloro­quinolin-8-olate), C2H10N22+·2C9H5ClNO, (III), and 5-chloro-8-hy­droxy­quinolinium chloride, C9H7ClNO+·Cl, (IV), were synthesized with the aim of preparing biologically active complexes of PdII and NiII with 5-chloro­quinolin-8-ol (ClQ). Compounds (I) and (II) contain PdII atoms which are coordinated in a square-planar manner by four chloride ligands. In the structure of (I), there is an isolated [PdCl4]2− anion, while in the structure of (II) the anion consists of PdII atoms, lying on centres of inversion, bonded to a combination of two terminal and two bridging Cl ligands, lying on twofold rotation axes, forming an infinite [–μ2-Cl–PdCl2–]n chain. The negative charges of these anions are balanced by two crystallographically independent protonated HClQ+ cations in (I) and by dimethyl­ammonium cations in (II), with the N atoms lying on twofold rotation axes. The structure of (III) consists of ClQ anions, with the hy­droxy groups deprotonated, and centrosymmetric ethyl­ene­di­ammonium cations. On the other hand, the structure of (IV) consists of a protonated HClQ+ cation with the positive charge balanced by a chloride anion. All four structures are stabilized by systems of hydrogen bonds which occur between the anions and cations. π–π inter­actions were observed between the HClQ+ cations in the structures of (I) and (IV).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112047452/fg3281sup1.cif
Contains datablocks I, II, III, IV, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112047452/fg3281Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112047452/fg3281IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112047452/fg3281IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112047452/fg3281IVsup5.hkl
Contains datablock IV

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112047452/fg3281IIIsup6.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112047452/fg3281IVsup7.cml
Supplementary material

CCDC references: 915099; 915100; 915101; 915102

Comment top

With the development of anticancer agents containing platinum, such as cisplatin or carboplatin, there is also an interest in the preparation of other transition metal complexes that can serve as anticancer drugs. Palladium, as a metal very analogous to platinum, forms complexes which are also promising agents for the development of new anticancer drugs.

In general, PdII complexes containing chelating ligands exhibit antiproliferative activity against the Sarcoma 180 tumor (Fricker, 1994). Due to the significant difference in reactivity of palladium and platinum complexes towards DNA, it has been suggested that PdII complexes might circumvent resistance to cisplatin-derived drugs in some tumor cell lines (Farrell, 1989; Shi et al., 2010). On the other hand, the activity of anticancer agent might be enhanced by the coordination of organic drugs with known biological activities to transition metals. A perfect example of this strategy was reported on trans-palladium(II) complexes with chloroquine, which has been used as an antimalarial (Miller, 1954) and anti-inflammatory drug (Ferrante et al., 1986). It has been shown that its coordination to the PdII atom resulted in an increased antitumor activity against four cancer cell lines comparing to chloroquine itself (Navarro et al., 2006).

Other examples of biologically active substances are 5-chloroquinolin-8-ol (ClQ) and halogenated derivatives of quinolin-8-ol (XQ), which were recently investigated for anticancer activity with positive results (Jiang et al., 2011). Promising anticancer activity of PdII complexes with different ligands mentioned above, as well as the activity of ClQ, motivated us to prepare square-planar complexes containing the [Pd(ClQ)Cl2]- anion. For the sake of comparison, we also tried to prepare analogous NiII complexes. Our initial efforts resulted in the preparation of two ionic complexes containing PdII atoms, viz. (HClQ)2[PdCl4], (I), and [NH2(CH3)2][PdCl3], (II), and two ionic compounds comprising only protonated and deprotonated ions of the ClQ ligand, viz. (NH3CH2CH2NH3)(ClQ)2, (III), and (HClQ)Cl, (IV). The structure of (II) is already known (Raper et al., 1997), therefore we report here the preparation of (I)–(IV) and the crystal structures of (I), (III) and (IV), while the structure of (II) is only compared with the structure of (I).

The structures of compounds (I) and (II) contain PdII atoms which are coordinated in a square-planar manner by four chloride ligands. However, in (I), there is an isolated [PdCl4]2- anion, while in (II) PdII atoms are bridged by a pair of trans-coordinated Cl- ligands, forming an infinite chain. Six types of [PdCl4]2- anion units were found in the Cambridge Structural Database (Allen, 2002). [PdCl4]2- occurs most frequently as an isolated anion (101 hits), as in (I). In other structures containing [PdCl4]2-, PdII atoms are bridged in different modes and different chain-like or polynuclear compounds are formed. The most popular bridging mode (34 hits) is by pair of cis-coordinated Cl- ligands bridging two PdII atoms which have two other terminal Cl- ligands and thus binuclear [Pd2Cl6]2- units are formed. There is also one compound of similar composition, however this contains two pairs of cis-coordinated Cl- ligands bridging three PdII atoms, giving a trinuclear [Pd3Cl8]2- complex (Schwarz et al., 2002). On the other hand, there are two structures with a pair of trans-coordinated bridging Cl- ligands, as in (II) (Raper et al., 1997; Yang et al., 2006). Another unusual bridging mode (2 hits) is reported by Hosokawa et al. (1994, 1998), where three chloride ligands act as bridging atoms. Finally, the last type of bridging mode contains four bridging chloride ligands and different types of chains or polynuclear complexes are formed (23 hits).

Thus, the structure of (I) belongs to the most frequently observed form of the [PdCl4]2- unit, i.e. as an isolated [PdCl4]2- anion, and its negative charge is balanced by two protonated molecules of ClQ (HClQ+) (Fig. 1).

Both HClQ+ cations are themselves planar [the largest deviation from the mean planes of the aromatic rings of the HClQ+ is 0.039 (3) Å for atom C12 and 0.019 (3) Å for atom N2]. The C—C and C—N(O) bond lengths within the pyridine and benzene rings have expected values compared with previously published compounds containing the ClQ molecule (Ng, 2009; García-Granda & Gómez-Beltrán, 1986), as well as complexes containing other halogen-substituted 8-HQ molecules (Di Vaira et al., 2004; García-Granda & Gómez-Beltrán, 1986; García-Granda et al., 1987; Kappaun et al., 2006; Potočňák & Vranec, 2012; Vranec & Potočňák, 2011; Vranec et al., 2012). The C—Cl bond lengths are close to the values for corresponding single bonds in aromatic rings (García-Granda & Gómez-Beltrán, 1986; García-Granda et al., 1987; Gniewek et al., 2006; Kappaun et al., 2006; Ng, 2009; Potočňák & Vranec, 2012; Vranec & Potočňák, 2011; Vranec et al., 2012). The Pd—Cl distances in the complex anion are also similar to previously reported compounds containing the [PdCl4]2- anion (Suyun et al., 2011; Carvalho et al., 2010). A distorted square-planar geometry around the PdII atom is confirmed by the Cl—Pd—Cl angles given in Table 1, where other selected bond lengths and angles are also summarized.

Except for ionic forces, the structure of (I) is also stabilized by a system of hydrogen bonds. Hydroxy and pyridinium H atoms from both HClQ+ cations are interconnected by Cl- atoms of the [PdCl4]2- anion and a wave-like plane parallel to (001) is formed (Fig. 2). Data characterizing all four hydrogen bonds are given in Table 2.

There are also ππ interactions in the structure of (I), which occur between the phenolic parts of both HClQ+ cations (Fig. 3). Data characterizing these interactions are consistent with the literature data on ππ interactions (Janiak, 2000). Dihedral angles between the planes of adjacent HClQ+ molecules are 3.65 and 3.88° for HClQ+(1) and HClQ+(2i), and HClQ+(1) and HClQ+(2ii) molecules, respectively, and the distances between the corresponding centroids of the phenolic parts are Cg1···Cg2i = 3.711 (1) and Cg1···Cg2ii = 3.576 (1) Å [symmetry codes: (i) x-1, -y+1/2, z-1/2; (ii) x, -y+1/2, z-1/2]. The angles between the benzene-ring normals and the Cg1···Cg2i and Cg1···Cg2ii centroid vectors are 22.97 and 20.22°, respectively.

In the structure of (II), the environment of the PdII atom is similar to that in (I) (Fig. 4). Nevertheless, as stated above, in this case, the [PdCl4]2- anion is part of a rarely occurring negatively charged [–µ2Cl–PdCl2–]n chain running along the c axis in which two PdII atoms are bridged by trans-coordinated Cl- ligands (Fig. 5). The negative charge of the repeating [PdCl3]- unit is balanced by the presence of a dimethylammonium cation.

Although the Cl- ligands have different bonding modes, the Pd–Cl bond lengths are still very similar (Table 3) and are close to those observed in (I); the same is also true for the Cl—Pd—Cl angles. The structure of the dimethylammonium cation exhibits normal features, both for bond lengths and for bond angles, confirming the sp3-hybridization of the C and N atoms (Raper et al., 1997; Melen et al., 2011).

The structure of (II) is also stabilized by a system of hydrogen bonds, which involve both amino H atoms and atom Cl2 of the [PdCl4]2- unit (Fig. 6). Due to these two hydrogen bonds, the cations and anions are linked to form a plane parallel to (010). Data characterizing hydrogen bonds for (II) are given in Table 4.

The structure of (III) consists of ethylenediammonium cations and ClQ- anions containing deprotonated hydroxy groups (Fig. 7). On the other hand, the structure of (IV) is formed by a protonated HClQ+ molecule, where the H atom is on the N atom of the ClQ molecule; the positive charge of the cation is compensated by the presence of a chloride anion (Fig. 8). To the best of our knowledge, compound (III) represents the first example of a structure with an isolated ClQ- anion, while (I) and (IV) are the second and third examples of structures with isolated HClQ+ cations (Allen, 2002).

The protonated and deprotonated ClQ molecules in (III) and (IV) are themselves planar [the largest deviation from the mean plane of the whole ClQ molecule is 0.005 (1) Å for atom N1 in (III) and 0.028 (2) Å for atom C5 in (IV)]. The C—C and C—N(O) bond lengths within the pyridine and benzene rings, as well as the C—Cl bond lengths, have values close to those for a previously published analogous (HClQ)NO3 compound (Ng, 2009), as well as for complexes containing other halogen-substituted 8-HQ molecules (Di Vaira et al., 2004; García-Granda & Gómez-Beltrán, 1986; García-Granda et al., 1987; Gniewek et al., 2006; Kappaun et al., 2006; Potočňák & Vranec, 2012; Vranec & Potočňák, 2011; Vranec et al., 2012). Selected bond lengths and angles for (III) and (IV) are given in Tables 5 and 6, respectively.

Except the ionic forces, the structures of both (III) and (IV) are stabilized by hydrogen bonds. All ammonium H atoms in (III) are involved in hydrogen bonding. One of them, H3N2, interacts with atoms O1ii and N1ii of the ClQ- anion, while other two H atoms, H1N2 and H2N2, interact with only one O atom, O1 and O1i, respectively [symmetry codes: (i) x, -y+3/2, z+1/2; (ii) -x+1, y+1/2, -z+3/2]. Due to these hydrogen bonds, a layered structure parallel to (100) is formed. Each layer comprises three planes, viz. a plane of ethylenediammonium cations surrounded by two planes of ClQ- anions with Cl1 atoms at the outer side of these two planes. These triple-plane layers are held together by weak London forces and Cl atoms in neighboring layers arrange themselves a zipper-like fashion with an interlayer Cl···Cliv distance of 3.888 (1) Å [symmetry codes: (iv) -x, y+1/2, -z+3/2; (v) -x, y-1/2, -z+3/2] (Fig 9). Data characterizing hydrogen bonds in (III) are summarized in Table 7.

Two hydrogen bonds were observed in the structure of (IV). One of them occurs between the chloride anion and the hydroxy H atom of the HClQ+ cation, while the second hydrogen bond occurs between the chloride anion and a pyridinium H atom of the HClQ+ cation and thus an R42(14) motif is formed (Bernstein et al., 1995). Data characterizing hydrogen bonds in (IV) are summarized in Table 8. There were also ππ interactions in the structure of (IV) between a pair of coplanar adjacent cations. The distance between parallel mean planes of the HClQ+ cations is 3.40 Å and the distance between the centroids of the pyridine and phenol parts of HClQ+ is 3.613 (1) Å. The angle between the benzene or pyridine ring normal and the centroids vector of 19.64°, as well as previously mentioned distances, are consistent with the literature data on ππ interactions (Janiak, 2000). Due to these interactions, the hydrogen-bonded motifs in (IV) are linked together and an infinite stair-like chain is formed (Fig. 10).

Related literature top

For related literature, see: Allen (2002); Bernstein et al. (1995); Carvalho et al. (2010); Di Vaira, Bazzicalupi, Orioli, Messori, Bruni & Zatta (2004); Farrell (1989); Ferrante et al. (1986); Fricker (1994); García-Granda & Gómez-Beltrán (1986); García-Granda, Beurskens, Behm & Gómez-Beltrán (1987); Gniewek et al. (2006); Hosokawa et al. (1994, 1998); Janiak (2000); Jiang et al. (2011); Kappaun et al. (2006); Melen et al. (2011); Miller (1954); Navarro et al. (2006); Ng (2009); Potočňák & Vranec (2012); Raper et al. (1997); Schwarz et al. (2002); Shi et al. (2010); Suyun et al. (2011); Vranec & Potočňák (2011); Vranec et al. (2012); Yang et al. (2006).

Experimental top

To prepare the compounds under study, we used NiCl2.6H2O (p.a.) and a 40% water solution of PdCl2 from Lachema. The solvents [ethanol (96%) and N,N'-dimethylformamide (DMF) (p.a.)] were also obtained from Lachema, while 5-chloroquinolin-8-ol (95%) was obtained from Sigma–Aldrich, ethylenediamine (99%) was obtained from Alfa Aesar and hydrochloride acid (35%) was obtained from ITES. All chemicals were used as received.

For the preparation of (HClQ)2[PdCl4], (I), an ethanolic solution (25 ml) of ClQ (48 mg, 0.270 mmol) was mixed with an ethanolic solution (5 ml) of PdCl2 (0.1 ml of 40% water solution of PdCl2; 24 mg of PdCl2, 0.135 mmol). Three drops of concentrated hydrochloride acid were then added to the solution, while mixing continuously. The prepared solution was then heated to boiling point (~353 K). Afterwards, the solution was allowed to cool to room temperature and after 7 d, orange prisms of (I) were filtered off and dried on air.

For the preparation of [NH2(CH3)2][PdCl3], (II), ClQ (48 mg, 0.270 mmol) was dissolved in ethanol (25 ml). An ethanolic solution (5 ml) of PdCl2 (0.1 ml of 40% water solution of PdCl2; 24 mg of PdCl2, 0.135 mmol) was then added. Three drops of concentrated hydrochloride acid were added to form an orange solution. After 15 d at room temperature an orange microcrystalline powder was filtered off and dried in air. Afterwards, the product was recrystallized in a mixture of of ethanol (25 ml) and DMF (2 ml). After several days, red–brown needle-like crystals of (II) were filtered off and dried in air.

For the preparation of (NH3CH2CH2NH3)(ClQ)2, (III), ClQ (38 mg, 0.22 mmol) was dissolved in ethanol (25 ml) and three drops of ethylenediamine were added. The light-yellow color of the solution changed to yellow–green. Subsequently, a water solution (2 ml) of NiCl2.6H2O (25 mg, 0.11 mmol) was added to the solution of ClQ, while mixing continuously. After 10 d at room temperature, yellow prisms of (III) were filtered off and dried in air.

For the preparation of (HClQ)Cl, (IV), ClQ (38 mg, 0.22 mmol) was dissolved in ethanol (20 ml) and this solution was mixed with a water solution (2 ml) of NiCl2.6H2O (25 mg, 0.11 mmol). Three drops of concentrated hydrochloride acid were then added to the solution, while mixing continuously. The dark-green solution set aside for crystallization at room temperature and after 15 d, light-yellow plates of (IV) were filtered off and dried in air.

Refinement top

The aromatic H atoms in all structures, as well as the methyl H atoms in (II), were placed in calculated positions and refined riding on their parent C atoms with C—H = 0.93 and 0.96 Å, respectively. Amine [for (II) and (III)], hydroxy and pyridinium [for (I) and (IV)] H atoms, as well as methylene H atoms in (III), were found in difference maps.

Computing details top

For all compounds, 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); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 50% probability for non-H atoms. H atoms are represented as small spheres of arbitrary radii. The dashed lines indicate the symmetry-independent hydrogen bonds.
[Figure 2] Fig. 2. Wave-like plane parallel to (001) formed by the system of hydrogen bonds (dashed lines) in (I). Only H atoms involved in the system of hydrogen bonds are shown because of clarity.
[Figure 3] Fig. 3. ππ interactions (dashed lines) between the aromatic rings of the cations in (I). [Symmetry codes: (i) x-1, -y+1/2, z-1/2; (ii) x, -y+1/2, z-1/2.]
[Figure 4] Fig. 4. The structure of (II), with displacement ellipsoids drawn at the 50% probability for non-H atoms. H atoms are represented as small spheres of arbitrary radii. The dashed line indicates the symmetry-independent hydrogen bond. [Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+2, y, -z+1/2.]
[Figure 5] Fig. 5. Part of negatively charged [–µ2-Cl–PdCl2–]n chain running along the c axis in (II). [Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, y, -z+3/2; (iv) -x+1, y, -z+1/2.]
[Figure 6] Fig. 6. The system of hydrogen bonds (dashed lines) in (II) forming a plane parallel to (010). [Symmetry code: (iii) x, -y+1, z-1/2.]
[Figure 7] Fig. 7. The structure of (III). Displacement ellipsoids are drawn at the 50% probability for non-H atoms. H atoms are represented as small spheres of arbitrary radii. The dashed line indicates the symmetry-independent hydrogen bond. [Symmetry code: (iii) -x+1, -y+1, -z+2.]
[Figure 8] Fig. 8. The structure of (IV). Displacement ellipsoids are drawn at the 50% probability for non-H atoms. H atoms are represented as small spheres of arbitrary radii. The dashed line indicates the symmetry-independent hydrogen bond.
[Figure 9] Fig. 9. Two triple-plane layers parallel with (100) formed by the system of hydrogen bonds (dashed lines) in (III). [Symmetry codes: (i) x, -y+3/2, z+1/2; (ii) -x+1, y+1/2, -z+3/2.]
[Figure 10] Fig. 10. Stair-like chain in (IV) formed by hydrogen bonds [R42(14) motifs are shown] and ππ interactions (dashed lines). [Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x+1, -y+1, -z+1.]
(I) Bis(5-chloro-8-hydroxyquinolinium) tetrachloridopalladate(II) top
Crystal data top
(C9H7ClNO)2[PdCl4]F(000) = 1200
Mr = 609.41Dx = 1.977 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4110 reflections
a = 7.2339 (2) Åθ = 3.0–29.1°
b = 21.7998 (8) ŵ = 1.71 mm1
c = 13.0306 (4) ÅT = 183 K
β = 94.903 (3)°Prism, orange
V = 2047.37 (11) Å30.29 × 0.14 × 0.05 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur (Sapphire2, large Be window)
diffractometer
4226 independent reflections
Radiation source: fine-focus sealed tube3467 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
Detector resolution: 8.3438 pixels mm-1θmax = 26.5°, θmin = 3.0°
ω scansh = 69
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
k = 2527
Tmin = 0.816, Tmax = 0.939l = 1614
8968 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0171P)2 + 0.0183P]
where P = (Fo2 + 2Fc2)/3
4226 reflections(Δ/σ)max = 0.001
278 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = 0.45 e Å3
Crystal data top
(C9H7ClNO)2[PdCl4]V = 2047.37 (11) Å3
Mr = 609.41Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.2339 (2) ŵ = 1.71 mm1
b = 21.7998 (8) ÅT = 183 K
c = 13.0306 (4) Å0.29 × 0.14 × 0.05 mm
β = 94.903 (3)°
Data collection top
Oxford Diffraction Xcalibur (Sapphire2, large Be window)
diffractometer
4226 independent reflections
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
3467 reflections with I > 2σ(I)
Tmin = 0.816, Tmax = 0.939Rint = 0.025
8968 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.054H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.44 e Å3
4226 reflectionsΔρmin = 0.45 e Å3
278 parameters
Special details top

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)

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
xyzUiso*/Ueq
Pd10.75083 (3)0.373726 (10)0.726874 (15)0.01454 (7)
Cl110.54189 (9)0.39239 (3)0.84992 (5)0.01980 (16)
Cl120.50724 (9)0.35196 (4)0.60614 (5)0.02160 (17)
Cl130.95767 (9)0.35740 (4)0.60553 (5)0.02442 (18)
Cl140.99715 (9)0.39547 (3)0.84913 (5)0.01880 (16)
Cl10.17959 (10)0.03163 (4)0.86297 (5)0.02952 (19)
Cl20.69473 (10)0.27089 (4)1.35240 (5)0.02894 (19)
C110.2368 (3)0.26863 (14)0.7750 (2)0.0223 (7)
H110.23760.31220.77560.027*
C120.1760 (4)0.23623 (15)0.8578 (2)0.0237 (7)
H120.13150.25770.91420.028*
C130.1804 (3)0.17353 (15)0.8578 (2)0.0210 (7)
H130.14420.15150.91570.025*
C140.2386 (3)0.14131 (13)0.77204 (19)0.0159 (6)
C150.2430 (3)0.07639 (14)0.76228 (19)0.0178 (6)
C160.2955 (3)0.04908 (14)0.6748 (2)0.0205 (6)
H160.29620.00560.66970.025*
C170.3485 (4)0.08484 (14)0.5928 (2)0.0208 (7)
H170.38360.06520.53230.025*
C180.3503 (4)0.14737 (14)0.59847 (19)0.0169 (6)
C190.2943 (3)0.17595 (13)0.68860 (19)0.0150 (6)
C210.7259 (3)0.51346 (15)1.3182 (2)0.0229 (7)
H210.72290.55651.32890.027*
C220.6796 (4)0.47335 (15)1.3948 (2)0.0239 (7)
H220.64310.48901.45800.029*
C230.6866 (3)0.41175 (15)1.3794 (2)0.0205 (7)
H230.65730.38471.43280.025*
C240.7367 (3)0.38742 (13)1.28509 (19)0.0150 (6)
C250.7454 (3)0.32436 (14)1.26052 (19)0.0177 (6)
C260.7947 (3)0.30549 (14)1.1662 (2)0.0196 (6)
H260.80140.26291.15130.023*
C270.8353 (4)0.34874 (13)1.0913 (2)0.0183 (6)
H270.86860.33501.02620.022*
C280.8278 (4)0.41018 (14)1.11068 (19)0.0164 (6)
C290.7794 (3)0.42975 (13)1.20898 (18)0.0138 (6)
O10.3999 (3)0.18659 (11)0.52533 (17)0.0248 (5)
O20.8623 (3)0.45605 (10)1.04542 (16)0.0239 (5)
N10.2934 (3)0.23839 (12)0.69567 (18)0.0189 (6)
N20.7743 (3)0.49082 (12)1.22992 (18)0.0175 (5)
H2O10.433 (4)0.1710 (16)0.489 (2)0.022 (11)*
H1O20.885 (4)0.4432 (15)0.999 (2)0.022 (10)*
H1N20.806 (4)0.5160 (16)1.189 (2)0.046 (11)*
H1N10.337 (4)0.2587 (16)0.650 (2)0.041 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.01750 (12)0.01365 (12)0.01301 (11)0.00059 (10)0.00440 (7)0.00018 (9)
Cl110.0220 (4)0.0212 (4)0.0173 (3)0.0000 (3)0.0082 (3)0.0005 (3)
Cl120.0219 (4)0.0267 (4)0.0163 (3)0.0038 (3)0.0022 (3)0.0003 (3)
Cl130.0223 (4)0.0350 (5)0.0170 (3)0.0011 (4)0.0073 (3)0.0025 (3)
Cl140.0198 (4)0.0209 (4)0.0160 (3)0.0019 (3)0.0036 (2)0.0031 (3)
Cl10.0275 (4)0.0322 (5)0.0286 (4)0.0044 (4)0.0008 (3)0.0132 (3)
Cl20.0282 (4)0.0255 (5)0.0328 (4)0.0051 (4)0.0010 (3)0.0128 (3)
C110.0168 (15)0.0178 (17)0.0314 (17)0.0033 (14)0.0029 (12)0.0114 (14)
C120.0139 (15)0.034 (2)0.0234 (16)0.0007 (15)0.0014 (11)0.0144 (14)
C130.0136 (15)0.032 (2)0.0174 (15)0.0033 (15)0.0001 (11)0.0052 (13)
C140.0107 (14)0.0203 (17)0.0161 (14)0.0007 (13)0.0024 (10)0.0003 (12)
C150.0121 (14)0.0201 (17)0.0206 (15)0.0026 (13)0.0021 (10)0.0045 (13)
C160.0168 (15)0.0156 (17)0.0282 (16)0.0023 (13)0.0038 (12)0.0001 (13)
C170.0196 (15)0.0222 (18)0.0204 (15)0.0023 (14)0.0008 (11)0.0030 (13)
C180.0160 (15)0.0184 (17)0.0159 (14)0.0024 (13)0.0006 (11)0.0010 (12)
C190.0105 (14)0.0156 (16)0.0181 (14)0.0006 (13)0.0031 (10)0.0010 (12)
C210.0187 (16)0.0221 (18)0.0271 (16)0.0041 (14)0.0026 (12)0.0097 (14)
C220.0168 (16)0.038 (2)0.0170 (15)0.0018 (15)0.0017 (11)0.0079 (14)
C230.0129 (15)0.032 (2)0.0161 (15)0.0032 (14)0.0005 (11)0.0018 (13)
C240.0108 (14)0.0182 (17)0.0157 (14)0.0013 (13)0.0013 (10)0.0003 (12)
C250.0146 (15)0.0172 (17)0.0209 (15)0.0055 (13)0.0018 (11)0.0088 (12)
C260.0172 (15)0.0149 (17)0.0259 (16)0.0013 (13)0.0020 (11)0.0027 (12)
C270.0196 (15)0.0185 (17)0.0166 (14)0.0011 (14)0.0008 (11)0.0030 (12)
C280.0159 (15)0.0194 (17)0.0139 (14)0.0014 (13)0.0012 (10)0.0007 (12)
C290.0123 (14)0.0142 (16)0.0144 (14)0.0005 (13)0.0023 (10)0.0006 (11)
O10.0361 (14)0.0216 (14)0.0175 (12)0.0045 (11)0.0072 (10)0.0009 (10)
O20.0389 (13)0.0203 (13)0.0135 (11)0.0006 (11)0.0084 (9)0.0003 (10)
N10.0178 (13)0.0165 (15)0.0222 (14)0.0026 (12)0.0010 (10)0.0006 (11)
N20.0192 (13)0.0136 (14)0.0197 (13)0.0009 (12)0.0013 (10)0.0001 (11)
Geometric parameters (Å, º) top
Pd1—Cl132.2956 (6)C19—N11.364 (4)
Pd1—Cl122.3089 (7)C21—N21.325 (3)
Pd1—Cl112.3313 (6)C21—C221.389 (4)
Pd1—Cl142.3350 (7)C21—H210.9500
Cl1—C151.728 (3)C22—C231.359 (4)
Cl2—C251.733 (3)C22—H220.9500
C11—N11.320 (3)C23—C241.414 (4)
C11—C121.392 (4)C23—H230.9500
C11—H110.9500C24—C291.408 (4)
C12—C131.367 (4)C24—C251.414 (4)
C12—H120.9500C25—C261.372 (4)
C13—C141.414 (4)C26—C271.406 (4)
C13—H130.9500C26—H260.9500
C14—C191.411 (4)C27—C281.365 (4)
C14—C151.421 (4)C27—H270.9500
C15—C161.368 (4)C28—O21.350 (3)
C16—C171.403 (4)C28—C291.422 (3)
C16—H160.9500C29—N21.360 (4)
C17—C181.365 (4)O1—H2O10.65 (3)
C17—H170.9500O2—H1O20.69 (3)
C18—O11.352 (3)N1—H1N10.82 (3)
C18—C191.419 (4)N2—H1N20.82 (3)
Cl13—Pd1—Cl1290.19 (2)N2—C21—H21120.4
Cl13—Pd1—Cl11178.86 (3)C22—C21—H21120.4
Cl12—Pd1—Cl1190.15 (2)C23—C22—C21120.1 (3)
Cl13—Pd1—Cl1489.83 (2)C23—C22—H22119.9
Cl12—Pd1—Cl14179.85 (3)C21—C22—H22119.9
Cl11—Pd1—Cl1489.84 (2)C22—C23—C24120.9 (3)
N1—C11—C12119.6 (3)C22—C23—H23119.5
N1—C11—H11120.2C24—C23—H23119.5
C12—C11—H11120.2C29—C24—C23117.0 (3)
C13—C12—C11119.9 (3)C29—C24—C25117.4 (2)
C13—C12—H12120.1C23—C24—C25125.5 (3)
C11—C12—H12120.1C26—C25—C24120.9 (3)
C12—C13—C14120.3 (3)C26—C25—Cl2120.3 (2)
C12—C13—H13119.8C24—C25—Cl2118.8 (2)
C14—C13—H13119.8C25—C26—C27120.4 (3)
C19—C14—C13117.9 (3)C25—C26—H26119.8
C19—C14—C15117.0 (2)C27—C26—H26119.8
C13—C14—C15125.1 (3)C28—C27—C26121.1 (3)
C16—C15—C14121.2 (3)C28—C27—H27119.5
C16—C15—Cl1119.8 (2)C26—C27—H27119.5
C14—C15—Cl1119.0 (2)O2—C28—C27126.7 (2)
C15—C16—C17120.4 (3)O2—C28—C29114.7 (3)
C15—C16—H16119.8C27—C28—C29118.5 (3)
C17—C16—H16119.8N2—C29—C24119.2 (2)
C18—C17—C16121.0 (3)N2—C29—C28119.2 (3)
C18—C17—H17119.5C24—C29—C28121.6 (3)
C16—C17—H17119.5C18—O1—H2O1109 (3)
O1—C18—C17126.5 (3)C28—O2—H1O2108 (3)
O1—C18—C19114.7 (3)C11—N1—C19123.7 (3)
C17—C18—C19118.8 (3)C11—N1—H1N1117 (2)
N1—C19—C14118.6 (3)C19—N1—H1N1119 (2)
N1—C19—C18119.8 (3)C21—N2—C29123.5 (3)
C14—C19—C18121.6 (3)C21—N2—H1N2116 (2)
N2—C21—C22119.1 (3)C29—N2—H1N2121 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H2O1···Cl11i0.65 (3)2.46 (3)3.106 (2)177 (4)
O2—H1O2···Cl140.69 (3)2.42 (3)3.109 (2)174 (3)
N2—H1N2···Cl14ii0.82 (3)2.47 (3)3.199 (3)149 (3)
N1—H1N1···Cl120.82 (3)2.47 (3)3.192 (3)147 (3)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+2, y+1, z+2.
(II) catena-Poly[dimethylammonium [[dichloridopalladate(II)]-µ-chlorido]] top
Crystal data top
(C2H8N)[PdCl3]F(000) = 496
Mr = 258.84Dx = 2.341 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 545 reflections
a = 7.7896 (7) Åθ = 3.1–28.9°
b = 13.2070 (11) ŵ = 3.51 mm1
c = 7.1410 (6) ÅT = 293 K
β = 91.359 (7)°Needle, red-brown
V = 734.44 (11) Å30.97 × 0.19 × 0.18 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur (Sapphire2, large Be window)
diffractometer
762 independent reflections
Radiation source: fine-focus sealed tube629 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
Detector resolution: 8.3438 pixels mm-1θmax = 26.5°, θmin = 3.1°
ω scansh = 59
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
k = 1615
Tmin = 0.214, Tmax = 0.603l = 88
1387 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.064 w = 1/[σ2(Fo2) + (0.0291P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
762 reflectionsΔρmax = 0.67 e Å3
40 parametersΔρmin = 0.68 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0188 (9)
Crystal data top
(C2H8N)[PdCl3]V = 734.44 (11) Å3
Mr = 258.84Z = 4
Monoclinic, C2/cMo Kα radiation
a = 7.7896 (7) ŵ = 3.51 mm1
b = 13.2070 (11) ÅT = 293 K
c = 7.1410 (6) Å0.97 × 0.19 × 0.18 mm
β = 91.359 (7)°
Data collection top
Oxford Diffraction Xcalibur (Sapphire2, large Be window)
diffractometer
762 independent reflections
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
629 reflections with I > 2σ(I)
Tmin = 0.214, Tmax = 0.603Rint = 0.020
1387 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.67 e Å3
762 reflectionsΔρmin = 0.68 e Å3
40 parameters
Special details top

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)

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
xyzUiso*/Ueq
Pd10.50000.50000.50000.0227 (2)
Cl10.50000.61090 (11)0.75000.0329 (4)
Cl20.74937 (14)0.42723 (9)0.61492 (15)0.0378 (3)
C10.9193 (6)0.3120 (4)0.1009 (6)0.0421 (11)
H1A0.86920.35570.00710.063*
H1B0.83140.27040.15300.063*
H1C1.00440.26980.04520.063*
N11.00000.3736 (4)0.25000.0349 (13)
H1N10.919 (8)0.406 (4)0.303 (9)0.09 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0241 (3)0.0254 (3)0.0185 (3)0.0004 (2)0.00107 (17)0.00164 (16)
Cl10.0471 (10)0.0294 (8)0.0224 (7)0.0000.0011 (6)0.000
Cl20.0324 (6)0.0441 (7)0.0365 (6)0.0103 (6)0.0051 (4)0.0005 (5)
C10.038 (3)0.044 (3)0.043 (3)0.006 (2)0.007 (2)0.006 (2)
N10.035 (3)0.032 (3)0.037 (3)0.0000.005 (3)0.000
Geometric parameters (Å, º) top
Pd1—Cl2i2.3010 (10)C1—H1A0.9600
Pd1—Cl22.3010 (10)C1—H1B0.9600
Pd1—Cl12.3092 (9)C1—H1C0.9600
Pd1—Cl1i2.3092 (9)N1—C1iii1.469 (5)
Cl1—Pd1ii2.3092 (9)N1—H1N10.86 (5)
C1—N11.469 (5)
Cl2i—Pd1—Cl2180.0N1—C1—H1B109.5
Cl2i—Pd1—Cl189.73 (3)H1A—C1—H1B109.5
Cl2—Pd1—Cl190.27 (3)N1—C1—H1C109.5
Cl2i—Pd1—Cl1i90.27 (3)H1A—C1—H1C109.5
Cl2—Pd1—Cl1i89.73 (3)H1B—C1—H1C109.5
Cl1—Pd1—Cl1i180.0C1—N1—C1iii112.8 (5)
Pd1—Cl1—Pd1ii101.27 (6)C1—N1—H1N1107 (5)
N1—C1—H1A109.5C1iii—N1—H1N1105 (5)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z+3/2; (iii) x+2, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···Cl20.86 (5)2.63 (6)3.3684 (16)145 (6)
N1—H1N1···Cl2iv0.86 (5)2.88 (6)3.402 (5)121 (5)
Symmetry code: (iv) x, y+1, z1/2.
(III) Ethylenediammonium bis(5-chloroquinolin-8-olate) top
Crystal data top
C2H10N22+·2C9H5ClNOF(000) = 436
Mr = 419.30Dx = 1.480 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3109 reflections
a = 15.8369 (5) Åθ = 3.2–29.5°
b = 6.8335 (3) ŵ = 0.37 mm1
c = 8.7459 (4) ÅT = 183 K
β = 96.087 (3)°Prism, yellow
V = 941.16 (7) Å30.32 × 0.30 × 0.18 mm
Z = 2
Data collection top
Oxford Diffraction Xcalibur (Sapphire2, large Be window)
diffractometer
1953 independent reflections
Radiation source: fine-focus sealed tube1610 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
Detector resolution: 8.3438 pixels mm-1θmax = 26.5°, θmin = 3.3°
ω scansh = 1919
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
k = 88
Tmin = 0.106, Tmax = 0.241l = 1010
6777 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0437P)2 + 0.3861P]
where P = (Fo2 + 2Fc2)/3
1953 reflections(Δ/σ)max < 0.001
147 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C2H10N22+·2C9H5ClNOV = 941.16 (7) Å3
Mr = 419.30Z = 2
Monoclinic, P21/cMo Kα radiation
a = 15.8369 (5) ŵ = 0.37 mm1
b = 6.8335 (3) ÅT = 183 K
c = 8.7459 (4) Å0.32 × 0.30 × 0.18 mm
β = 96.087 (3)°
Data collection top
Oxford Diffraction Xcalibur (Sapphire2, large Be window)
diffractometer
1953 independent reflections
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
1610 reflections with I > 2σ(I)
Tmin = 0.106, Tmax = 0.241Rint = 0.025
6777 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.39 e Å3
1953 reflectionsΔρmin = 0.19 e Å3
147 parameters
Special details top

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)

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
xyzUiso*/Ueq
Cl10.05358 (3)0.72953 (8)0.71628 (6)0.03992 (18)
C10.24967 (11)0.1971 (3)0.4904 (2)0.0265 (4)
H10.27050.08420.44340.032*
C20.16153 (11)0.2106 (3)0.4988 (2)0.0281 (4)
H20.12440.10980.45810.034*
C30.13066 (10)0.3702 (3)0.5661 (2)0.0271 (4)
H30.07140.38180.57330.032*
C40.18667 (10)0.5197 (2)0.62566 (18)0.0209 (4)
C50.16087 (10)0.6923 (3)0.6970 (2)0.0249 (4)
C60.21846 (11)0.8303 (3)0.75126 (19)0.0248 (4)
H60.19980.94510.79890.030*
C70.30545 (10)0.8038 (2)0.73709 (19)0.0224 (4)
H70.34440.90170.77650.027*
C80.33615 (10)0.6403 (2)0.66789 (17)0.0188 (3)
C90.27492 (9)0.4934 (2)0.61074 (18)0.0189 (3)
C110.53688 (10)0.5689 (2)0.9921 (2)0.0208 (4)
O10.41795 (6)0.61455 (16)0.65317 (12)0.0202 (3)
N10.30504 (8)0.3310 (2)0.54356 (16)0.0219 (3)
N20.50427 (9)0.7520 (2)0.91811 (17)0.0183 (3)
H11B0.5767 (11)0.512 (3)0.925 (2)0.024 (5)*
H2N20.4685 (12)0.801 (3)0.980 (2)0.020 (5)*
H11A0.5664 (11)0.601 (3)1.092 (2)0.023 (5)*
H1N20.4779 (14)0.722 (3)0.825 (3)0.036 (6)*
H3N20.5461 (14)0.839 (3)0.907 (2)0.037 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0186 (2)0.0518 (3)0.0505 (3)0.0073 (2)0.0087 (2)0.0129 (2)
C10.0265 (9)0.0261 (9)0.0266 (9)0.0013 (7)0.0019 (7)0.0035 (7)
C20.0240 (8)0.0300 (10)0.0295 (10)0.0046 (7)0.0000 (7)0.0025 (8)
C30.0183 (8)0.0350 (10)0.0278 (9)0.0022 (7)0.0021 (7)0.0024 (8)
C40.0201 (8)0.0257 (9)0.0169 (8)0.0015 (7)0.0021 (6)0.0031 (7)
C50.0178 (8)0.0347 (10)0.0226 (9)0.0059 (7)0.0049 (6)0.0011 (7)
C60.0272 (9)0.0268 (9)0.0210 (9)0.0075 (7)0.0054 (7)0.0023 (7)
C70.0231 (8)0.0235 (9)0.0206 (8)0.0000 (7)0.0015 (7)0.0023 (7)
C80.0193 (8)0.0225 (8)0.0148 (8)0.0012 (6)0.0024 (6)0.0033 (6)
C90.0186 (8)0.0227 (8)0.0156 (8)0.0028 (6)0.0025 (6)0.0023 (6)
C110.0175 (8)0.0217 (8)0.0234 (9)0.0008 (7)0.0031 (7)0.0003 (7)
O10.0164 (5)0.0256 (6)0.0189 (6)0.0006 (4)0.0037 (4)0.0004 (5)
N10.0210 (7)0.0225 (7)0.0222 (7)0.0019 (6)0.0020 (6)0.0012 (6)
N20.0180 (7)0.0201 (7)0.0173 (7)0.0021 (6)0.0044 (6)0.0009 (6)
Geometric parameters (Å, º) top
Cl1—C51.7437 (17)C7—C81.383 (2)
C1—N11.317 (2)C7—H70.9500
C1—C21.409 (2)C8—O11.3272 (18)
C1—H10.9500C8—C91.447 (2)
C2—C31.355 (3)C9—N11.365 (2)
C2—H20.9500C11—N21.477 (2)
C3—C41.416 (2)C11—C11i1.518 (3)
C3—H30.9500C11—H11B0.983 (19)
C4—C51.414 (2)C11—H11A0.974 (18)
C4—C91.429 (2)N2—H2N20.89 (2)
C5—C61.362 (3)N2—H1N20.90 (2)
C6—C71.408 (2)N2—H3N20.90 (2)
C6—H60.9500
N1—C1—C2124.21 (16)C6—C7—H7118.8
N1—C1—H1117.9O1—C8—C7122.80 (14)
C2—C1—H1117.9O1—C8—C9119.96 (14)
C3—C2—C1118.73 (16)C7—C8—C9117.23 (14)
C3—C2—H2120.6N1—C9—C4122.10 (14)
C1—C2—H2120.6N1—C9—C8117.43 (14)
C2—C3—C4119.99 (16)C4—C9—C8120.47 (15)
C2—C3—H3120.0N2—C11—C11i109.19 (16)
C4—C3—H3120.0N2—C11—H11B107.0 (11)
C5—C4—C3124.40 (15)C11i—C11—H11B110.9 (11)
C5—C4—C9118.45 (15)N2—C11—H11A108.4 (11)
C3—C4—C9117.15 (15)C11i—C11—H11A110.9 (11)
C6—C5—C4121.12 (15)H11B—C11—H11A110.3 (14)
C6—C5—Cl1119.26 (14)C1—N1—C9117.81 (14)
C4—C5—Cl1119.63 (13)C11—N2—H2N2105.8 (12)
C5—C6—C7120.38 (16)C11—N2—H1N2107.9 (13)
C5—C6—H6119.8H2N2—N2—H1N2111.8 (18)
C7—C6—H6119.8C11—N2—H3N2112.2 (13)
C8—C7—C6122.35 (15)H2N2—N2—H3N2110.0 (18)
C8—C7—H7118.8H1N2—N2—H3N2109.2 (18)
Symmetry code: (i) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N2···O1ii0.89 (2)1.88 (2)2.7427 (18)163.6 (16)
N2—H1N2···O10.90 (2)1.84 (2)2.7292 (18)168.7 (19)
N2—H3N2···O1iii0.90 (2)2.05 (2)2.8646 (18)149.0 (18)
N2—H3N2···N1iii0.90 (2)2.35 (2)3.051 (2)134.3 (17)
Symmetry codes: (ii) x, y+3/2, z+1/2; (iii) x+1, y+1/2, z+3/2.
(IV) 5-chloro-8-hydroxyquinolinium chloride top
Crystal data top
C9H7ClNO·ClZ = 2
Mr = 216.06F(000) = 220
Triclinic, P1Dx = 1.614 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.3980 (4) ÅCell parameters from 2895 reflections
b = 7.6612 (5) Åθ = 3.2–29.2°
c = 8.4536 (4) ŵ = 0.68 mm1
α = 72.400 (5)°T = 183 K
β = 76.797 (5)°Plate, light yellow
γ = 84.615 (5)°0.64 × 0.42 × 0.12 mm
V = 444.47 (4) Å3
Data collection top
Oxford Diffraction Xcalibur (Sapphire2, large Be window)
diffractometer
1836 independent reflections
Radiation source: fine-focus sealed tube1508 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 8.3438 pixels mm-1θmax = 26.5°, θmin = 3.2°
ω scansh = 99
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
k = 99
Tmin = 0.775, Tmax = 0.935l = 1010
5950 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H atoms treated by a mixture of independent and constrained refinement
S = 0.94 w = 1/[σ2(Fo2) + (0.0338P)2 + 0.2637P]
where P = (Fo2 + 2Fc2)/3
1836 reflections(Δ/σ)max < 0.001
126 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C9H7ClNO·Clγ = 84.615 (5)°
Mr = 216.06V = 444.47 (4) Å3
Triclinic, P1Z = 2
a = 7.3980 (4) ÅMo Kα radiation
b = 7.6612 (5) ŵ = 0.68 mm1
c = 8.4536 (4) ÅT = 183 K
α = 72.400 (5)°0.64 × 0.42 × 0.12 mm
β = 76.797 (5)°
Data collection top
Oxford Diffraction Xcalibur (Sapphire2, large Be window)
diffractometer
1836 independent reflections
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
1508 reflections with I > 2σ(I)
Tmin = 0.775, Tmax = 0.935Rint = 0.023
5950 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.073H atoms treated by a mixture of independent and constrained refinement
S = 0.94Δρmax = 0.28 e Å3
1836 reflectionsΔρmin = 0.20 e Å3
126 parameters
Special details top

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)

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
xyzUiso*/Ueq
Cl10.27168 (7)1.08850 (7)0.23024 (6)0.03076 (15)
Cl20.68520 (6)0.63769 (6)0.14647 (5)0.02654 (14)
C10.1109 (3)0.5638 (3)0.7615 (2)0.0243 (4)
H10.11340.47550.86870.029*
C20.2760 (3)0.6490 (3)0.7208 (2)0.0264 (4)
H20.39100.61730.79850.032*
C30.2706 (3)0.7787 (3)0.5677 (2)0.0235 (4)
H30.38270.83730.53960.028*
C40.1003 (2)0.8267 (2)0.4509 (2)0.0194 (4)
C50.0790 (3)0.9595 (2)0.2901 (2)0.0217 (4)
C60.0904 (3)0.9914 (3)0.1827 (2)0.0232 (4)
H60.10101.08130.07550.028*
C70.2500 (3)0.8925 (3)0.2289 (2)0.0233 (4)
H70.36650.91490.15150.028*
C80.2395 (2)0.7643 (2)0.3842 (2)0.0200 (4)
C90.0626 (2)0.7324 (2)0.4967 (2)0.0180 (4)
O10.38214 (19)0.66338 (19)0.44309 (17)0.0259 (3)
N10.0496 (2)0.6050 (2)0.65167 (18)0.0202 (3)
H1O10.466 (3)0.661 (3)0.366 (3)0.043 (7)*
H1N10.155 (3)0.538 (3)0.689 (3)0.048 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0274 (3)0.0355 (3)0.0313 (3)0.0103 (2)0.0104 (2)0.0127 (2)
Cl20.0241 (3)0.0285 (3)0.0207 (2)0.00215 (19)0.00148 (17)0.00325 (18)
C10.0267 (10)0.0240 (9)0.0211 (9)0.0051 (8)0.0013 (7)0.0084 (8)
C20.0206 (10)0.0325 (11)0.0263 (10)0.0063 (8)0.0031 (8)0.0129 (8)
C30.0178 (9)0.0297 (10)0.0268 (10)0.0016 (8)0.0025 (7)0.0151 (8)
C40.0186 (9)0.0228 (9)0.0209 (9)0.0001 (7)0.0035 (7)0.0131 (7)
C50.0213 (9)0.0237 (9)0.0242 (9)0.0030 (8)0.0071 (7)0.0121 (8)
C60.0274 (10)0.0235 (9)0.0193 (9)0.0022 (8)0.0049 (7)0.0068 (7)
C70.0194 (9)0.0287 (10)0.0213 (9)0.0048 (8)0.0015 (7)0.0093 (8)
C80.0170 (9)0.0243 (9)0.0207 (9)0.0004 (7)0.0025 (7)0.0110 (7)
C90.0196 (9)0.0180 (9)0.0187 (8)0.0015 (7)0.0023 (7)0.0094 (7)
O10.0164 (7)0.0364 (8)0.0222 (7)0.0041 (6)0.0006 (6)0.0084 (6)
N10.0204 (8)0.0209 (8)0.0199 (8)0.0007 (6)0.0026 (6)0.0085 (6)
Geometric parameters (Å, º) top
Cl1—C51.7398 (18)C5—C61.364 (3)
C1—N11.327 (2)C6—C71.409 (3)
C1—C21.394 (3)C6—H60.9500
C1—H10.9500C7—C81.372 (3)
C2—C31.367 (3)C7—H70.9500
C2—H20.9500C8—O11.347 (2)
C3—C41.413 (2)C8—C91.424 (2)
C3—H30.9500C9—N11.366 (2)
C4—C91.416 (2)O1—H1O10.79 (2)
C4—C51.415 (3)N1—H1N10.95 (3)
N1—C1—C2120.46 (17)C5—C6—H6119.6
N1—C1—H1119.8C7—C6—H6119.6
C2—C1—H1119.8C8—C7—C6120.90 (17)
C3—C2—C1119.33 (17)C8—C7—H7119.5
C3—C2—H2120.3C6—C7—H7119.5
C1—C2—H2120.3O1—C8—C7126.23 (16)
C2—C3—C4120.84 (18)O1—C8—C9115.51 (16)
C2—C3—H3119.6C7—C8—C9118.26 (16)
C4—C3—H3119.6N1—C9—C4119.21 (16)
C3—C4—C9117.52 (16)N1—C9—C8119.03 (16)
C3—C4—C5125.40 (17)C4—C9—C8121.75 (16)
C9—C4—C5117.06 (16)C8—O1—H1O1109.9 (18)
C6—C5—C4121.27 (17)C1—N1—C9122.60 (16)
C6—C5—Cl1119.26 (14)C1—N1—H1N1114.6 (15)
C4—C5—Cl1119.45 (14)C9—N1—H1N1122.8 (15)
C5—C6—C7120.72 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···Cl20.79 (2)2.21 (3)3.0001 (14)174 (2)

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formula(C9H7ClNO)2[PdCl4](C2H8N)[PdCl3]C2H10N22+·2C9H5ClNOC9H7ClNO·Cl
Mr609.41258.84419.30216.06
Crystal system, space groupMonoclinic, P21/cMonoclinic, C2/cMonoclinic, P21/cTriclinic, P1
Temperature (K)183293183183
a, b, c (Å)7.2339 (2), 21.7998 (8), 13.0306 (4)7.7896 (7), 13.2070 (11), 7.1410 (6)15.8369 (5), 6.8335 (3), 8.7459 (4)7.3980 (4), 7.6612 (5), 8.4536 (4)
α, β, γ (°)90, 94.903 (3), 9090, 91.359 (7), 9090, 96.087 (3), 9072.400 (5), 76.797 (5), 84.615 (5)
V3)2047.37 (11)734.44 (11)941.16 (7)444.47 (4)
Z4422
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)1.713.510.370.68
Crystal size (mm)0.29 × 0.14 × 0.050.97 × 0.19 × 0.180.32 × 0.30 × 0.180.64 × 0.42 × 0.12
Data collection
DiffractometerOxford Diffraction Xcalibur (Sapphire2, large Be window)
diffractometer
Oxford Diffraction Xcalibur (Sapphire2, large Be window)
diffractometer
Oxford Diffraction Xcalibur (Sapphire2, large Be window)
diffractometer
Oxford Diffraction Xcalibur (Sapphire2, large Be window)
diffractometer
Absorption correctionAnalytical
[CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
Analytical
[CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
Analytical
[CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
Analytical
[CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
Tmin, Tmax0.816, 0.9390.214, 0.6030.106, 0.2410.775, 0.935
No. of measured, independent and
observed [I > 2σ(I)] reflections
8968, 4226, 3467 1387, 762, 629 6777, 1953, 1610 5950, 1836, 1508
Rint0.0250.0200.0250.023
(sin θ/λ)max1)0.6280.6280.6280.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.054, 1.06 0.027, 0.064, 1.07 0.037, 0.093, 1.04 0.029, 0.073, 0.94
No. of reflections422676219531836
No. of parameters27840147126
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.44, 0.450.67, 0.680.39, 0.190.28, 0.20

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2001).

Selected geometric parameters (Å, º) for (I) top
Pd1—Cl132.2956 (6)C11—N11.320 (3)
Pd1—Cl122.3089 (7)C18—O11.352 (3)
Pd1—Cl112.3313 (6)C19—N11.364 (4)
Pd1—Cl142.3350 (7)C21—N21.325 (3)
Cl1—C151.728 (3)C28—O21.350 (3)
Cl2—C251.733 (3)C29—N21.360 (4)
Cl13—Pd1—Cl1290.19 (2)Cl13—Pd1—Cl1489.83 (2)
Cl13—Pd1—Cl11178.86 (3)Cl12—Pd1—Cl14179.85 (3)
Cl12—Pd1—Cl1190.15 (2)Cl11—Pd1—Cl1489.84 (2)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H2O1···Cl11i0.65 (3)2.46 (3)3.106 (2)177 (4)
O2—H1O2···Cl140.69 (3)2.42 (3)3.109 (2)174 (3)
N2—H1N2···Cl14ii0.82 (3)2.47 (3)3.199 (3)149 (3)
N1—H1N1···Cl120.82 (3)2.47 (3)3.192 (3)147 (3)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+2, y+1, z+2.
Selected geometric parameters (Å, º) for (II) top
Pd1—Cl2i2.3010 (10)Pd1—Cl1i2.3092 (9)
Pd1—Cl22.3010 (10)Cl1—Pd1ii2.3092 (9)
Pd1—Cl12.3092 (9)
Cl2i—Pd1—Cl2180.0Cl2—Pd1—Cl1i89.73 (3)
Cl2i—Pd1—Cl189.73 (3)Cl1—Pd1—Cl1i180.0
Cl2—Pd1—Cl190.27 (3)Pd1—Cl1—Pd1ii101.27 (6)
Cl2i—Pd1—Cl1i90.27 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z+3/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···Cl20.86 (5)2.63 (6)3.3684 (16)145 (6)
N1—H1N1···Cl2iii0.86 (5)2.88 (6)3.402 (5)121 (5)
Symmetry code: (iii) x, y+1, z1/2.
Selected bond lengths (Å) for (III) top
Cl1—C51.7437 (17)C8—O11.3272 (18)
C1—N11.317 (2)C9—N11.365 (2)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N2—H2N2···O1i0.89 (2)1.88 (2)2.7427 (18)163.6 (16)
N2—H1N2···O10.90 (2)1.84 (2)2.7292 (18)168.7 (19)
N2—H3N2···O1ii0.90 (2)2.05 (2)2.8646 (18)149.0 (18)
N2—H3N2···N1ii0.90 (2)2.35 (2)3.051 (2)134.3 (17)
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x+1, y+1/2, z+3/2.
Selected bond lengths (Å) for (IV) top
Cl1—C51.7398 (18)C8—O11.347 (2)
C1—N11.327 (2)C9—N11.366 (2)
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···Cl20.79 (2)2.21 (3)3.0001 (14)174 (2)
 

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