Dichlorido(4,5-diaza­fluoren-9-one-κ2N,N′)palladium(II)

Xu, Z.-G.; Liu, H.-Y.; Zhan, Q.-G.; Chen, J.; Xu, M.-J.

doi:10.1107/S1600536809035272

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page m1166

doi:10.1107/S1600536809035272

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Dichlorido(4,5-diazafluoren-9-one-κ²N,N′)palladium(II)

Zhi-Guang Xu,^a ^* Hai-Yang Liu,^b Qing-Guang Zhan,^a Jian Chen ^a and Min-Jian Xu ^a

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China, and ^bDepartment of Chemistry, South China University of Technology, Guangzhou 510641, People's Republic of China
^*Correspondence e-mail: chzgxu@scnu.edu.cn

(Received 27 August 2009; accepted 1 September 2009; online 5 September 2009)

The structure of the title compound, [PdCl₂(C₁₁H₆N₂O)], shows a nearly square-planar geometry for the Pd^II atom within a Cl₂N₂ donor set.

Related literature

For related palladium complexes, see: Klein et al. (1998 ).

Experimental

Crystal data

[PdCl₂(C₁₁H₆N₂O)]
M_r = 359.48
Monoclinic, P 2₁ /c
a = 5.131 (5) Å
b = 17.105 (5) Å
c = 12.763 (5) Å
β = 99.183 (5)°
V = 1105.8 (12) Å³
Z = 4
Mo Kα radiation
μ = 2.14 mm⁻¹
T = 293 K
0.35 × 0.33 × 0.25 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.477, T_max = 0.586
6785 measured reflections
2703 independent reflections
2198 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.058
S = 1.04
2703 reflections
178 parameters
All H-atom parameters refined
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035272/tk2532sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035272/tk2532Isup2.hkl

checkCIF report

Comment top

The title compound, (I), Fig. 1, shows the palladium atom to be coordinated by two chlorides and two nitrogen atoms, the latter derived from a chelating 4,5-diazafluoren-9-one (dafo) ligand. The coordination geometry is based on a square planar arrangement of the four donor atoms. Related palladium structures featuring dafo ligands are known (Klein et al., 1998).

Related literature top

For related palladium complexes see: Klein et al., (1998).

Experimental top

Compound (I) was synthesized hydrothermally from an aqueous mixture (10.0 ml) containing PdCl₂ (0.1758 g) and 4,5-diazafluoren-9-one (0.301 g) in a 30 ml Teflon-lined stainless steel vessel. In the vessel, the solution was heated to 413 K for 72 h then cooled to room temperature at a rate of 10 K per hour. Brown prisms were obtained after washed thoroughly with deionized water and air-drying.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level.

Dichlorido(4,5-diazafluoren-9-one-κ²N,N')palladium(II) top

Crystal data top

[PdCl₂(C₁₁H₆N₂O)]	F(000) = 696
M_r = 359.48	D_x = 2.159 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 13853 reflections
a = 5.131 (5) Å	θ = 1.8–28.2°
b = 17.105 (5) Å	µ = 2.14 mm⁻¹
c = 12.763 (5) Å	T = 293 K
β = 99.183 (5)°	Block, yellow
V = 1105.8 (12) Å³	0.35 × 0.33 × 0.25 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2703 independent reflections
Radiation source: fine-focus sealed tube	2198 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 10 pixels mm^-1	θ_max = 28.4°, θ_min = 2.0°
ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −22→13
T_min = 0.477, T_max = 0.586	l = −16→16
6785 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.058	All H-atom parameters refined
S = 1.04	w = 1/[σ²(F_o²) + (0.0199P)² + 0.6053P] where P = (F_o² + 2F_c²)/3
2703 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

[PdCl₂(C₁₁H₆N₂O)]	V = 1105.8 (12) Å³
M_r = 359.48	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.131 (5) Å	µ = 2.14 mm⁻¹
b = 17.105 (5) Å	T = 293 K
c = 12.763 (5) Å	0.35 × 0.33 × 0.25 mm
β = 99.183 (5)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2703 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2198 reflections with I > 2σ(I)
T_min = 0.477, T_max = 0.586	R_int = 0.028
6785 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.058	All H-atom parameters refined
S = 1.04	Δρ_max = 0.37 e Å⁻³
2703 reflections	Δρ_min = −0.54 e Å⁻³
178 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 Rfactors(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	0.08571 (4)	0.152850 (13)	0.283179 (18)	0.03075 (8)
N2	0.2819 (5)	0.16090 (14)	0.15176 (19)	0.0336 (6)
N1	0.2865 (4)	0.04745 (13)	0.30833 (19)	0.0303 (5)
C6	0.6231 (5)	0.08217 (18)	0.0892 (2)	0.0343 (7)
C4	0.6221 (6)	−0.01682 (17)	0.2253 (2)	0.0322 (6)
C5	0.7568 (6)	0.00609 (19)	0.1320 (2)	0.0378 (7)
O1	0.9357 (5)	−0.02803 (14)	0.10159 (19)	0.0532 (6)
C11	0.4449 (5)	0.04170 (17)	0.2364 (2)	0.0319 (6)
C10	0.4439 (5)	0.10020 (17)	0.1557 (2)	0.0317 (6)
C3	0.6398 (6)	−0.0784 (2)	0.2962 (3)	0.0402 (8)
C8	0.4677 (7)	0.1976 (2)	−0.0016 (3)	0.0434 (8)
C1	0.3028 (6)	−0.01242 (19)	0.3780 (3)	0.0367 (7)
C9	0.2942 (6)	0.2103 (2)	0.0695 (3)	0.0397 (7)
C7	0.6379 (7)	0.1337 (2)	0.0064 (3)	0.0414 (8)
C2	0.4742 (6)	−0.0747 (2)	0.3724 (3)	0.0413 (8)
Cl1	−0.10542 (16)	0.13410 (5)	0.42956 (7)	0.0445 (2)
Cl2	−0.11747 (16)	0.26981 (5)	0.24949 (7)	0.0479 (2)
H1	0.187 (6)	−0.0098 (17)	0.429 (2)	0.038 (9)*
H3	0.762 (7)	−0.123 (2)	0.295 (3)	0.052 (10)*
H4	0.753 (6)	0.1289 (19)	−0.038 (3)	0.048 (10)*
H2	0.477 (6)	−0.115 (2)	0.420 (3)	0.046 (9)*
H5	0.465 (6)	0.2338 (19)	−0.055 (3)	0.043 (9)*
H6	0.181 (6)	0.2543 (19)	0.064 (2)	0.046 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.02879 (12)	0.02863 (13)	0.03619 (14)	−0.00123 (9)	0.00940 (9)	−0.00117 (10)
N2	0.0321 (13)	0.0332 (14)	0.0364 (14)	−0.0019 (11)	0.0084 (10)	0.0016 (11)
N1	0.0293 (12)	0.0303 (13)	0.0328 (14)	−0.0010 (10)	0.0097 (10)	0.0015 (10)
C6	0.0300 (15)	0.0392 (18)	0.0341 (17)	−0.0042 (13)	0.0070 (12)	−0.0008 (13)
C4	0.0306 (15)	0.0341 (16)	0.0330 (17)	−0.0017 (12)	0.0086 (12)	−0.0034 (13)
C5	0.0351 (16)	0.0419 (18)	0.0373 (18)	−0.0013 (14)	0.0093 (14)	−0.0042 (14)
O1	0.0540 (14)	0.0596 (16)	0.0516 (15)	0.0154 (12)	0.0258 (12)	0.0029 (12)
C11	0.0281 (15)	0.0337 (16)	0.0340 (17)	−0.0032 (12)	0.0056 (12)	−0.0019 (12)
C10	0.0279 (14)	0.0343 (17)	0.0329 (16)	−0.0027 (12)	0.0049 (12)	0.0010 (13)
C3	0.0390 (18)	0.0366 (18)	0.046 (2)	0.0071 (14)	0.0092 (15)	0.0012 (15)
C8	0.051 (2)	0.045 (2)	0.0340 (19)	−0.0075 (16)	0.0075 (15)	0.0118 (15)
C1	0.0366 (17)	0.0387 (18)	0.0366 (18)	−0.0027 (14)	0.0112 (14)	0.0016 (14)
C9	0.0401 (18)	0.0362 (18)	0.043 (2)	0.0004 (15)	0.0070 (14)	0.0079 (14)
C7	0.0427 (19)	0.049 (2)	0.0345 (19)	−0.0075 (15)	0.0114 (15)	−0.0019 (15)
C2	0.0461 (19)	0.0348 (18)	0.044 (2)	0.0026 (15)	0.0122 (15)	0.0084 (15)
Cl1	0.0490 (5)	0.0435 (5)	0.0461 (5)	−0.0033 (4)	0.0235 (4)	−0.0035 (4)
Cl2	0.0470 (5)	0.0334 (4)	0.0651 (6)	0.0065 (4)	0.0147 (4)	0.0033 (4)

Geometric parameters (Å, º) top

Pd1—N1	2.076 (2)	C4—C5	1.521 (4)
Pd1—N2	2.094 (3)	C5—O1	1.203 (4)
Pd1—Cl2	2.2652 (11)	C11—C10	1.436 (4)
Pd1—Cl1	2.2672 (12)	C3—C2	1.391 (5)
N2—C10	1.326 (4)	C8—C9	1.387 (5)
N2—C9	1.356 (4)	C8—C7	1.392 (5)
N1—C11	1.323 (4)	C1—C2	1.390 (5)
N1—C1	1.350 (4)	H3—C3	0.99 (4)
C6—C10	1.382 (4)	H1—C1	0.95 (3)
C6—C7	1.387 (4)	H2—C2	0.92 (4)
C6—C5	1.531 (4)	H5—C8	0.92 (4)
C4—C11	1.375 (4)	H6—C9	0.95 (3)
C4—C3	1.382 (4)	H4—C7	0.89 (3)

N1—Pd1—N2	83.74 (10)	C4—C11—C10	111.1 (3)
N1—Pd1—Cl2	176.78 (7)	N2—C10—C6	128.8 (3)
N2—Pd1—Cl2	93.17 (8)	N2—C10—C11	120.2 (3)
N1—Pd1—Cl1	91.09 (7)	C6—C10—C11	111.0 (3)
N2—Pd1—Cl1	174.80 (7)	C4—C3—C2	116.1 (3)
Cl2—Pd1—Cl1	92.00 (4)	C9—C8—C7	122.3 (3)
C10—N2—C9	114.2 (3)	N1—C1—C2	121.3 (3)
C10—N2—Pd1	107.26 (19)	N2—C9—C8	121.6 (3)
C9—N2—Pd1	138.5 (2)	C6—C7—C8	116.4 (3)
C11—N1—C1	114.8 (3)	C1—C2—C3	122.2 (3)
C11—N1—Pd1	107.58 (19)	C7—C8—H5	121 (2)
C1—N1—Pd1	137.5 (2)	C9—C8—H5	116 (2)
C10—C6—C7	116.7 (3)	N1—C1—H1	115.8 (18)
C10—C6—C5	106.0 (3)	C2—C1—H1	122.8 (18)
C7—C6—C5	137.4 (3)	C1—C2—H2	119 (2)
C11—C4—C3	117.6 (3)	C3—C2—H2	119 (2)
C11—C4—C5	106.5 (3)	N2—C9—H6	116.7 (17)
C3—C4—C5	135.9 (3)	C8—C9—H6	121.8 (17)
O1—C5—C4	126.4 (3)	C4—C3—H3	124 (2)
O1—C5—C6	128.2 (3)	C2—C3—H3	120 (2)
C4—C5—C6	105.3 (2)	C6—C7—H4	124 (2)
N1—C11—C4	128.0 (3)	C8—C7—H4	120 (2)
N1—C11—C10	120.9 (3)

Experimental details

Crystal data
Chemical formula	[PdCl₂(C₁₁H₆N₂O)]
M_r	359.48
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.131 (5), 17.105 (5), 12.763 (5)
β (°)	99.183 (5)
V (Å³)	1105.8 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.14
Crystal size (mm)	0.35 × 0.33 × 0.25

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.477, 0.586
No. of measured, independent and observed [I > 2σ(I)] reflections	6785, 2703, 2198
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.058, 1.04
No. of reflections	2703
No. of parameters	178
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.54

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Natural Science Foundation of Guangdong Province (No. 8451063101000730). The authors thank Professor Zhong Min Su and Dr Kui Zhan Shao (Northeast Normal University) for their assistance with the X-ray crystallographic analysis.

References

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Klein, R. A., Witte, P., van Belzen, R., Fraanje, J., Goubitz, K., Numan, M., Schenk, H., Ernsting, J. M. & Elsevier, C. J. (1998). Eur. J. Inorg. Chem. pp. 319–330. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar