trans-Bis(acridine-κN)dichloridopalladium(II)

Ha, K.

doi:10.1107/S1600536811053335

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page m54

doi:10.1107/S1600536811053335

Open

access

trans-Bis(acridine-κN)dichloridopalladium(II)

Kwang Ha ^a ^*

^aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
^*Correspondence e-mail: hakwang@chonnam.ac.kr

(Received 9 December 2011; accepted 11 December 2011; online 17 December 2011)

In the title complex, [PdCl₂(C₁₃H₉N)₂], the Pd^II ion is four-coordinated in an essentially square-planar environment by two N atoms from two acridine ligands and two Cl⁻ anions. The Pd atom is located on an inversion centre, and thus the asymmetric unit contains one half of the complex and the PdN₂Cl₂ unit is exactly planar. The dihedral angle between the PdN₂Cl₂ unit and the acridine ligand is 84.66 (6)°. In the crystal, the complex molecules are stacked in columns along the a axis connected by C—H⋯Cl hydrogen bonds, forming chains along [110]. In the columns, numerous intermolecular π–π interactions between the six-membered rings are present, the shortest ring centroid–centroid distance being 3.722 (4) Å.

Related literature

For the related crystal structures [PdX₂(acr)₂] (X = Br, I), see: Ha (2010a ,b ).

Experimental

Crystal data

[PdCl₂(C₁₃H₉N)₂]
M_r = 535.72
Triclinic, $[P \overline 1]$
a = 8.2114 (16) Å
b = 8.8910 (18) Å
c = 9.0105 (18) Å
α = 66.188 (4)°
β = 77.230 (4)°
γ = 66.885 (4)°
V = 551.99 (19) Å³
Z = 1
Mo Kα radiation
μ = 1.10 mm⁻¹
T = 200 K
0.20 × 0.12 × 0.09 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.679, T_max = 1.000
3488 measured reflections
2124 independent reflections
1626 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.107
S = 0.98
2124 reflections
142 parameters
H-atom parameters constrained
Δρ_max = 0.83 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Pd1—N1	2.055 (4)
Pd1—Cl1	2.2975 (15)

N1—Pd1—Cl1	89.75 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯Cl1ⁱ	0.95	2.74	3.589 (6)	149
Symmetry code: (i) -x, -y+2, -z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811053335/bq2326sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053335/bq2326Isup2.hkl

checkCIF report

Comment top

In the title complex, [PdCl₂(acr)₂] (acr = acridine, C₁₃H₉N), the Pd^II ion is four-coordinated in an essentially square-planar environment by two N atoms from two acridine (acr) ligands and two Cl^- anions (Fig. 1 and Table 1). The complex and the iodo analogue [PdI₂(acr)₂] crystallized in the triclinic space group P1, whereas the analogous bromo Pd(II) complex [PdBr₂(acr)₂] crystallized in the monoclinic space group C2/c (Ha, 2010a,b).

The Pd atom is located on an inversion centre, and thus the asymmetric unit contains one half of the complex and the PdN₂Cl₂ unit is exactly plane. The nearly planar acridine ligands, with a maximum deviation of 0.033 (4) Å from the least-squares plane, are parallel. The dihedral angle between the PdN₂Cl₂ unit and acridine ligand is 84.66 (6)°. The Cl atoms are in trans conformation with respect to each other and almost perpendicular to the acridine planes, with the bond angle N1—Pd1—Cl1 = 89.75 (12)°. In the crystal, the complex molecules are stacked in columns along the a axis and connected by C—H···Cl hydrogen bonds, forming chains along [110]. In the columns, numerous intermolecular π-π interactions between the six-membered rings are present, the shortest ring centroid-centroid distance being 3.722 (4) Å.

Related literature top

For the related crystal structures [PdX₂(acr)₂] (X = Br, I), see: Ha (2010a,b).

Experimental top

To a solution of Na₂PdCl₄ (0.2014 g, 0.685 mmol) in H₂O (20 ml) was added acridine (0.2561 g, 1.429 mmol), and the mixture was refluxed for 7 h. The precipitate was then separated by filtration, washed with acetone and pentane, and dried at 50 °C, to give a yellow powder (0.3369 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₃CN solution.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title complex, with displacement ellipsoids drawn at the 50% probability level for non-H atoms. Unlabelled atoms are related to the reference atoms by the (1 - x, 1 - y, -z) symmetry transformation.
	Fig. 2. View of the unit-cell contents of the title complex. Hydrogen-bond interactions are drawn with dashed lines.

trans-Bis(acridine-κN)dichloridopalladium(II) top

Crystal data top

[PdCl₂(C₁₃H₉N)₂]	Z = 1
M_r = 535.72	F(000) = 268
Triclinic, P1	D_x = 1.612 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2114 (16) Å	Cell parameters from 940 reflections
b = 8.8910 (18) Å	θ = 2.7–22.5°
c = 9.0105 (18) Å	µ = 1.10 mm⁻¹
α = 66.188 (4)°	T = 200 K
β = 77.230 (4)°	Block, yellow
γ = 66.885 (4)°	0.20 × 0.12 × 0.09 mm
V = 551.99 (19) Å³

Data collection top

Bruker SMART 1000 CCD diffractometer	2124 independent reflections
Radiation source: fine-focus sealed tube	1626 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.679, T_max = 1.000	k = −9→10
3488 measured reflections	l = −10→11

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0328P)²] where P = (F_o² + 2F_c²)/3
2124 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 0.83 e Å⁻³
0 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

[PdCl₂(C₁₃H₉N)₂]	γ = 66.885 (4)°
M_r = 535.72	V = 551.99 (19) Å³
Triclinic, P1	Z = 1
a = 8.2114 (16) Å	Mo Kα radiation
b = 8.8910 (18) Å	µ = 1.10 mm⁻¹
c = 9.0105 (18) Å	T = 200 K
α = 66.188 (4)°	0.20 × 0.12 × 0.09 mm
β = 77.230 (4)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2124 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1626 reflections with I > 2σ(I)
T_min = 0.679, T_max = 1.000	R_int = 0.056
3488 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 0.98	Δρ_max = 0.83 e Å⁻³
2124 reflections	Δρ_min = −0.66 e Å⁻³
142 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
Pd1	0.5000	0.5000	0.0000	0.0284 (2)
Cl1	0.27624 (19)	0.42136 (19)	0.1805 (2)	0.0413 (4)
N1	0.3976 (5)	0.7417 (5)	0.0224 (5)	0.0239 (10)
C1	0.2822 (7)	0.8767 (7)	−0.0814 (7)	0.0287 (13)
C2	0.2416 (7)	0.8596 (8)	−0.2178 (7)	0.0343 (15)
H2	0.2955	0.7513	−0.2350	0.041*
C3	0.1271 (7)	0.9955 (8)	−0.3232 (8)	0.0399 (16)
H3	0.1017	0.9806	−0.4132	0.048*
C4	0.0448 (7)	1.1580 (8)	−0.3032 (8)	0.0438 (17)
H4	−0.0363	1.2512	−0.3785	0.053*
C5	0.0810 (7)	1.1817 (8)	−0.1766 (8)	0.0407 (16)
H5	0.0246	1.2920	−0.1634	0.049*
C6	0.2011 (7)	1.0455 (7)	−0.0640 (7)	0.0302 (14)
C7	0.2430 (7)	1.0626 (7)	0.0674 (7)	0.0352 (15)
H7	0.1892	1.1714	0.0838	0.042*
C8	0.3604 (7)	0.9262 (7)	0.1749 (7)	0.0254 (13)
C9	0.4058 (8)	0.9384 (9)	0.3117 (8)	0.0411 (16)
H9	0.3519	1.0450	0.3321	0.049*
C10	0.5234 (9)	0.8029 (9)	0.4133 (8)	0.0439 (17)
H10	0.5517	0.8142	0.5040	0.053*
C11	0.6047 (8)	0.6432 (8)	0.3845 (7)	0.0407 (16)
H11	0.6886	0.5478	0.4557	0.049*
C12	0.5641 (8)	0.6259 (7)	0.2572 (7)	0.0350 (15)
H12	0.6208	0.5179	0.2397	0.042*
C13	0.4400 (7)	0.7629 (7)	0.1489 (7)	0.0269 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0283 (4)	0.0212 (4)	0.0363 (4)	−0.0025 (3)	−0.0064 (3)	−0.0144 (3)
Cl1	0.0379 (9)	0.0295 (9)	0.0540 (11)	−0.0098 (7)	0.0061 (8)	−0.0188 (8)
N1	0.024 (2)	0.020 (2)	0.028 (3)	−0.005 (2)	−0.001 (2)	−0.011 (2)
C1	0.023 (3)	0.030 (3)	0.029 (3)	−0.007 (3)	0.001 (3)	−0.009 (3)
C2	0.030 (3)	0.028 (3)	0.042 (4)	−0.001 (3)	−0.006 (3)	−0.017 (3)
C3	0.033 (3)	0.046 (4)	0.043 (4)	−0.011 (3)	−0.017 (3)	−0.013 (3)
C4	0.025 (3)	0.035 (4)	0.054 (5)	0.000 (3)	−0.012 (3)	−0.003 (3)
C5	0.029 (3)	0.030 (4)	0.059 (5)	−0.003 (3)	0.002 (3)	−0.021 (3)
C6	0.026 (3)	0.024 (3)	0.041 (4)	−0.006 (3)	0.000 (3)	−0.015 (3)
C7	0.031 (3)	0.023 (3)	0.051 (4)	−0.007 (3)	0.010 (3)	−0.020 (3)
C8	0.025 (3)	0.025 (3)	0.029 (3)	−0.011 (3)	0.008 (3)	−0.016 (3)
C9	0.045 (4)	0.047 (4)	0.043 (4)	−0.023 (4)	0.013 (3)	−0.028 (4)
C10	0.061 (4)	0.057 (5)	0.033 (4)	−0.039 (4)	0.000 (4)	−0.018 (3)
C11	0.057 (4)	0.037 (4)	0.032 (4)	−0.022 (3)	−0.010 (3)	−0.007 (3)
C12	0.050 (4)	0.022 (3)	0.035 (4)	−0.010 (3)	−0.008 (3)	−0.012 (3)
C13	0.029 (3)	0.027 (3)	0.029 (3)	−0.009 (3)	0.002 (3)	−0.016 (3)

Geometric parameters (Å, º) top

Pd1—N1ⁱ	2.055 (4)	C5—H5	0.9500
Pd1—N1	2.055 (4)	C6—C7	1.382 (8)
Pd1—Cl1ⁱ	2.2975 (15)	C7—C8	1.373 (7)
Pd1—Cl1	2.2975 (15)	C7—H7	0.9500
N1—C1	1.344 (6)	C8—C9	1.420 (7)
N1—C13	1.362 (6)	C8—C13	1.432 (7)
C1—C2	1.420 (7)	C9—C10	1.344 (8)
C1—C6	1.442 (7)	C9—H9	0.9500
C2—C3	1.350 (7)	C10—C11	1.416 (8)
C2—H2	0.9500	C10—H10	0.9500
C3—C4	1.402 (8)	C11—C12	1.344 (7)
C3—H3	0.9500	C11—H11	0.9500
C4—C5	1.353 (8)	C12—C13	1.406 (7)
C4—H4	0.9500	C12—H12	0.9500
C5—C6	1.408 (8)

N1ⁱ—Pd1—N1	180.0	C7—C6—C5	123.4 (5)
N1ⁱ—Pd1—Cl1ⁱ	89.75 (12)	C7—C6—C1	117.3 (5)
N1—Pd1—Cl1ⁱ	90.25 (12)	C5—C6—C1	119.4 (5)
N1ⁱ—Pd1—Cl1	90.25 (12)	C8—C7—C6	121.5 (5)
N1—Pd1—Cl1	89.75 (12)	C8—C7—H7	119.2
Cl1ⁱ—Pd1—Cl1	180.00 (8)	C6—C7—H7	119.2
C1—N1—C13	119.7 (4)	C7—C8—C9	123.2 (5)
C1—N1—Pd1	120.7 (3)	C7—C8—C13	118.6 (5)
C13—N1—Pd1	119.6 (3)	C9—C8—C13	118.2 (5)
N1—C1—C2	120.6 (5)	C10—C9—C8	121.6 (6)
N1—C1—C6	122.0 (5)	C10—C9—H9	119.2
C2—C1—C6	117.4 (5)	C8—C9—H9	119.2
C3—C2—C1	120.7 (5)	C9—C10—C11	119.8 (6)
C3—C2—H2	119.7	C9—C10—H10	120.1
C1—C2—H2	119.7	C11—C10—H10	120.1
C2—C3—C4	121.7 (6)	C12—C11—C10	120.4 (6)
C2—C3—H3	119.1	C12—C11—H11	119.8
C4—C3—H3	119.1	C10—C11—H11	119.8
C5—C4—C3	119.8 (6)	C11—C12—C13	122.0 (5)
C5—C4—H4	120.1	C11—C12—H12	119.0
C3—C4—H4	120.1	C13—C12—H12	119.0
C4—C5—C6	121.0 (5)	N1—C13—C12	121.2 (5)
C4—C5—H5	119.5	N1—C13—C8	120.9 (5)
C6—C5—H5	119.5	C12—C13—C8	118.0 (5)

Cl1ⁱ—Pd1—N1—C1	87.0 (4)	C5—C6—C7—C8	179.7 (5)
Cl1—Pd1—N1—C1	−93.0 (4)	C1—C6—C7—C8	1.6 (8)
Cl1ⁱ—Pd1—N1—C13	−96.5 (4)	C6—C7—C8—C9	−179.6 (5)
Cl1—Pd1—N1—C13	83.5 (4)	C6—C7—C8—C13	−0.2 (8)
C13—N1—C1—C2	177.5 (5)	C7—C8—C9—C10	−179.0 (6)
Pd1—N1—C1—C2	−6.0 (7)	C13—C8—C9—C10	1.5 (8)
C13—N1—C1—C6	0.2 (8)	C8—C9—C10—C11	0.0 (9)
Pd1—N1—C1—C6	176.8 (4)	C9—C10—C11—C12	−0.6 (9)
N1—C1—C2—C3	−179.3 (5)	C10—C11—C12—C13	−0.4 (9)
C6—C1—C2—C3	−2.0 (8)	C1—N1—C13—C12	−178.2 (5)
C1—C2—C3—C4	0.3 (9)	Pd1—N1—C13—C12	5.2 (7)
C2—C3—C4—C5	0.7 (10)	C1—N1—C13—C8	1.3 (8)
C3—C4—C5—C6	0.2 (9)	Pd1—N1—C13—C8	−175.2 (4)
C4—C5—C6—C7	180.0 (6)	C11—C12—C13—N1	−178.6 (6)
C4—C5—C6—C1	−2.0 (9)	C11—C12—C13—C8	1.9 (9)
N1—C1—C6—C7	−1.7 (8)	C7—C8—C13—N1	−1.4 (8)
C2—C1—C6—C7	−179.0 (5)	C9—C8—C13—N1	178.1 (5)
N1—C1—C6—C5	−179.9 (5)	C7—C8—C13—C12	178.1 (5)
C2—C1—C6—C5	2.8 (8)	C9—C8—C13—C12	−2.4 (8)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Cl1ⁱⁱ	0.95	2.74	3.589 (6)	149

Symmetry code: (ii) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[PdCl₂(C₁₃H₉N)₂]
M_r	535.72
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	8.2114 (16), 8.8910 (18), 9.0105 (18)
α, β, γ (°)	66.188 (4), 77.230 (4), 66.885 (4)
V (Å³)	551.99 (19)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.10
Crystal size (mm)	0.20 × 0.12 × 0.09

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.679, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3488, 2124, 1626
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.107, 0.98
No. of reflections	2124
No. of parameters	142
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.83, −0.66

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

Pd1—N1	2.055 (4)	Pd1—Cl1	2.2975 (15)

N1—Pd1—Cl1	89.75 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Cl1ⁱ	0.95	2.74	3.589 (6)	148.5

Symmetry code: (i) −x, −y+2, −z.

Acknowledgements

This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2010–0029626).

References

Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Ha, K. (2010a). Z. Kristallogr. New Cryst. Struct. 225, 663–664. CAS Google Scholar
Ha, K. (2010b). Z. Kristallogr. New Cryst. Struct. 225, 693–694. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar