metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

trans-Di­chloridobis(4-meth­oxy­aniline-κN)palladium(II)

aInstitute of General and Inorganic Chemistry, NAS Ukraine, Kyiv, prosp. Palladina 32/34, 03680 Ukraine
*Correspondence e-mail: bon@ionc.kiev.ua

(Received 29 April 2009; accepted 15 May 2009; online 23 May 2009)

In the title compound, [PdCl2(C7H9NO)2], the Pd atom is situated on a crystallographic centre of inversion. The coordination environment of the Pd atom shows a slightly distorted square-planar geometry. The crystal structure exhibits weak inter­molecular Pd⋯Cl inter­actions, with Pd⋯Cl distances of 3.6912 (6) Å. A chain-like arrangement of mol­ecules realized by inter­molecular N—H⋯Cl hydrogen bonds is observed along [010].

Related literature

For catalytic activity of Pd complex compounds, see: Ojwach et al. (2007[Ojwach, S. O., Westman, G. & Darkwa, J. (2007). Polyhedron, 26, 5544-5552.]). For anti­tumoral properties of Pd compounds, see: Casas et al. (2008[Casas, J. S., Castellano, E. E., Ellena, J., García-Tasende, M. S., Pérez-Parallé, M. L., Sánchez, A., Sánchez-González, A. & Touceda, A. (2008). J. Inorg. Biochem. 102, 33-45.]). For related structures, see: Bon et al. (2009[Bon, V., Dudko, A., Orysyk, S. & Pekhnyo, V. (2009). Acta Cryst. E65, m396.]); Pan et al. (2006[Pan, Y.-L., Zhao, F. & Yang, S. (2006). Acta Cryst. E62, m239-m240.]).

[Scheme 1]

Experimental

Crystal data
  • [PdCl2(C7H9NO)2]

  • Mr = 423.60

  • Monoclinic, P 21 /c

  • a = 4.7333 (1) Å

  • b = 6.0071 (1) Å

  • c = 27.6918 (5) Å

  • β = 94.806 (1)°

  • V = 784.60 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 1.53 mm−1

  • T = 173 K

  • 0.25 × 0.08 × 0.04 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: numerical (SADABS; Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.701, Tmax = 0.941

  • 4837 measured reflections

  • 1577 independent reflections

  • 1326 reflections with I > 2σ(I)

  • Rint = 0.024

Refinement
  • R[F2 > 2σ(F2)] = 0.023

  • wR(F2) = 0.049

  • S = 1.04

  • 1577 reflections

  • 106 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.31 e Å−3

  • Δρmin = −0.39 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1A⋯Cl1i 0.85 (3) 2.53 (3) 3.353 (2) 162 (2)
Symmetry code: (i) x, y+1, z.

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: publCIF (Westrip, 2009[Westrip, S. P. (2009). publCIF. In preparation.]).

Supporting information


Comment top

Coordination compounds of Pd with N-containing organic ligands attract considerable interest due to their antitumoral and catalytic activity (Casas et al., 2008; Ojwach et al., 2007). Similar structures with respect to the title compound differing in terms of the position of substituents at the aromatic ring were published earlier (Pan et al., 2006; Bon et al., 2009). The asymmetric unit of the title compound contains one-half of the molecule because Pd occupies a special position on the crystallographic centre of inversion. Pd shows a slightly distorted square-planar geometry of the coordination environment containing two chlorine atoms and two amino groups in trans position (Fig. 1). The crystal structure shows weak intermolecular Pd···Cl interactions with Pd—Cl distances of 3.6912 (6) Å. A chain-like arrangement of molecules realized by weak N—H···Cl hydrogen bonds is observed along 010 direction (Fig. 2; Table 1).

Related literature top

For catalytic activity of Pd complex compounds, see: Ojwach et al. (2007). For antitumoral properties of Pd compounds, see: Casas et al. (2008). For related structures, see: Bon et al. (2009); Pan et al. (2006).

Experimental top

The yellow plate shaped crystals of the title compound were grown by slow evaporation of 10 ml of an ethanolic solution containing a mixture of 0.01 M H2[PdCl4] and 4-methoxyaniline in a 1:2 molar ratio 1:2.

Refinement top

H atoms bonded to N were located in a difference map and refined freely. Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.98 Å for CH3 [Uiso(H) = 1.5Ueq(C)] and C—H = 0.95 Å for CH [Uiso(H) = 1.2Ueq(C)]

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. The title compound showing 50% probability displacement ellipsoids for the non-hydrogen atoms [Symmetry code: (i) -x, -y, -z].
[Figure 2] Fig. 2. Crystal packing of title compound, projection down the a axis. Dashed lines indicate hydrogen bonds [Symmetry code: (i) x, y + 1, z].
trans-Dichloridobis(4-methoxyaniline-κN)palladium(II) top
Crystal data top
[PdCl2(C7H9NO)2]F(000) = 424
Mr = 423.60Dx = 1.793 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2257 reflections
a = 4.7333 (1) Åθ = 3.0–26.4°
b = 6.0071 (1) ŵ = 1.53 mm1
c = 27.6918 (5) ÅT = 173 K
β = 94.806 (1)°Plate, yellow
V = 784.60 (3) Å30.25 × 0.08 × 0.04 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer
1577 independent reflections
Radiation source: fine-focus sealed tube1326 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
Detector resolution: 8.26 pixels mm-1θmax = 26.4°, θmin = 1.5°
ϕ and ω scansh = 25
Absorption correction: numerical
(SADABS; Bruker, 2005)
k = 77
Tmin = 0.701, Tmax = 0.941l = 3434
4837 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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.049H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0205P)2 + 0.3835P]
where P = (Fo2 + 2Fc2)/3
1577 reflections(Δ/σ)max < 0.001
106 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.39 e Å3
Crystal data top
[PdCl2(C7H9NO)2]V = 784.60 (3) Å3
Mr = 423.60Z = 2
Monoclinic, P21/cMo Kα radiation
a = 4.7333 (1) ŵ = 1.53 mm1
b = 6.0071 (1) ÅT = 173 K
c = 27.6918 (5) Å0.25 × 0.08 × 0.04 mm
β = 94.806 (1)°
Data collection top
Bruker APEXII CCD
diffractometer
1577 independent reflections
Absorption correction: numerical
(SADABS; Bruker, 2005)
1326 reflections with I > 2σ(I)
Tmin = 0.701, Tmax = 0.941Rint = 0.024
4837 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.049H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.31 e Å3
1577 reflectionsΔρmin = 0.39 e Å3
106 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
xyzUiso*/Ueq
Pd10.00000.00000.00000.01570 (9)
Cl10.30064 (12)0.26378 (11)0.02745 (2)0.02254 (15)
N10.1173 (4)0.2075 (4)0.05318 (8)0.0188 (5)
H1A0.162 (5)0.332 (5)0.0398 (9)0.019 (7)*
H1B0.282 (6)0.151 (5)0.0615 (10)0.029 (8)*
O10.6985 (4)0.2939 (4)0.21008 (7)0.0347 (5)
C10.0967 (5)0.2336 (4)0.09336 (9)0.0191 (5)
C20.2570 (5)0.4248 (4)0.09767 (9)0.0202 (6)
H20.22590.54020.07440.024*
C30.4636 (5)0.4498 (4)0.13583 (9)0.0231 (6)
H30.57420.58180.13870.028*
C40.5079 (5)0.2813 (5)0.16982 (9)0.0251 (6)
C50.3517 (6)0.0864 (5)0.16452 (10)0.0290 (6)
H50.38610.03100.18720.035*
C60.1466 (6)0.0617 (4)0.12644 (10)0.0256 (6)
H60.04010.07220.12290.031*
C70.8612 (6)0.4926 (6)0.21595 (11)0.0395 (7)
H7A0.97140.51300.18790.059*
H7B0.99030.48170.24540.059*
H7C0.73400.61990.21860.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.01623 (13)0.01298 (15)0.01751 (14)0.00122 (12)0.00092 (9)0.00012 (13)
Cl10.0220 (3)0.0164 (3)0.0292 (3)0.0035 (3)0.0023 (2)0.0032 (3)
N10.0196 (11)0.0148 (12)0.0217 (12)0.0004 (10)0.0008 (9)0.0007 (10)
O10.0334 (10)0.0448 (14)0.0237 (10)0.0059 (10)0.0100 (8)0.0007 (10)
C10.0191 (12)0.0210 (14)0.0173 (12)0.0030 (11)0.0029 (10)0.0047 (12)
C20.0245 (13)0.0187 (14)0.0177 (13)0.0003 (11)0.0040 (10)0.0011 (11)
C30.0221 (12)0.0239 (16)0.0230 (14)0.0030 (11)0.0009 (10)0.0037 (12)
C40.0222 (13)0.0359 (18)0.0171 (13)0.0067 (13)0.0000 (10)0.0053 (13)
C50.0380 (16)0.0260 (15)0.0226 (15)0.0066 (13)0.0005 (12)0.0049 (13)
C60.0329 (14)0.0191 (15)0.0245 (14)0.0004 (12)0.0013 (11)0.0004 (12)
C70.0320 (15)0.055 (2)0.0303 (15)0.0001 (17)0.0054 (12)0.0113 (17)
Geometric parameters (Å, º) top
Pd1—N12.042 (2)C2—C31.387 (3)
Pd1—N1i2.042 (2)C2—H20.9500
Pd1—Cl12.3010 (6)C3—C41.387 (4)
Pd1—Cl1i2.3010 (6)C3—H30.9500
N1—C11.449 (3)C4—C51.386 (4)
N1—H1A0.85 (3)C5—C61.380 (4)
N1—H1B0.90 (3)C5—H50.9500
O1—C41.376 (3)C6—H60.9500
O1—C71.422 (4)C7—H7A0.9800
C1—C21.376 (4)C7—H7B0.9800
C1—C61.387 (4)C7—H7C0.9800
N1—Pd1—N1i180.00 (8)C2—C3—C4119.7 (2)
N1—Pd1—Cl188.23 (7)C2—C3—H3120.2
N1i—Pd1—Cl191.77 (7)C4—C3—H3120.2
N1—Pd1—Cl1i91.77 (7)O1—C4—C5116.1 (3)
N1i—Pd1—Cl1i88.23 (7)O1—C4—C3124.1 (3)
Cl1—Pd1—Cl1i180.0C5—C4—C3119.7 (2)
C1—N1—Pd1113.89 (15)C6—C5—C4120.4 (3)
C1—N1—H1A111.6 (18)C6—C5—H5119.8
Pd1—N1—H1A107.2 (17)C4—C5—H5119.8
C1—N1—H1B114.1 (17)C5—C6—C1119.6 (3)
Pd1—N1—H1B104.4 (18)C5—C6—H6120.2
H1A—N1—H1B105 (2)C1—C6—H6120.2
C4—O1—C7116.8 (2)O1—C7—H7A109.5
C2—C1—C6120.1 (2)O1—C7—H7B109.5
C2—C1—N1120.1 (2)H7A—C7—H7B109.5
C6—C1—N1119.7 (2)O1—C7—H7C109.5
C1—C2—C3120.3 (2)H7A—C7—H7C109.5
C1—C2—H2119.8H7B—C7—H7C109.5
C3—C2—H2119.8
Cl1—Pd1—N1—C1105.56 (18)C7—O1—C4—C31.1 (4)
Cl1i—Pd1—N1—C174.44 (18)C2—C3—C4—O1177.0 (2)
Pd1—N1—C1—C2103.7 (2)C2—C3—C4—C52.0 (4)
Pd1—N1—C1—C673.9 (2)O1—C4—C5—C6177.2 (2)
C6—C1—C2—C31.9 (4)C3—C4—C5—C61.9 (4)
N1—C1—C2—C3179.5 (2)C4—C5—C6—C10.1 (4)
C1—C2—C3—C40.2 (4)C2—C1—C6—C52.0 (4)
C7—O1—C4—C5179.8 (2)N1—C1—C6—C5179.6 (2)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1ii0.85 (3)2.53 (3)3.353 (2)162 (2)
Symmetry code: (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula[PdCl2(C7H9NO)2]
Mr423.60
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)4.7333 (1), 6.0071 (1), 27.6918 (5)
β (°) 94.806 (1)
V3)784.60 (3)
Z2
Radiation typeMo Kα
µ (mm1)1.53
Crystal size (mm)0.25 × 0.08 × 0.04
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionNumerical
(SADABS; Bruker, 2005)
Tmin, Tmax0.701, 0.941
No. of measured, independent and
observed [I > 2σ(I)] reflections
4837, 1577, 1326
Rint0.024
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.049, 1.04
No. of reflections1577
No. of parameters106
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.31, 0.39

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.85 (3)2.53 (3)3.353 (2)162 (2)
Symmetry code: (i) x, y+1, z.
 

References

First citationBon, V., Dudko, A., Orysyk, S. & Pekhnyo, V. (2009). Acta Cryst. E65, m396.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationBruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCasas, J. S., Castellano, E. E., Ellena, J., García-Tasende, M. S., Pérez-Parallé, M. L., Sánchez, A., Sánchez-González, A. & Touceda, A. (2008). J. Inorg. Biochem. 102, 33–45.  Web of Science CrossRef PubMed CAS Google Scholar
First citationOjwach, S. O., Westman, G. & Darkwa, J. (2007). Polyhedron, 26, 5544–5552.  Web of Science CrossRef CAS Google Scholar
First citationPan, Y.-L., Zhao, F. & Yang, S. (2006). Acta Cryst. E62, m239–m240.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2009). publCIF. In preparation.  Google Scholar

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ISSN: 2056-9890
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