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In the title complex, [Pd(C6H4O2)(C10H8N2)], the central Pd atom has a distorted cis planar four-coordination geometry defined by two O atoms of the benzene-1,2-diolate dianion and the two N atoms of a 2,2′-bipyridine ligand. The mol­ecule is essentially planar.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805027704/hg6238sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805027704/hg6238Isup2.hkl
Contains datablock I

CCDC reference: 287594

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.043
  • wR factor = 0.136
  • Data-to-parameter ratio = 16.2

checkCIF/PLATON results

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Alert level C PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 9
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The palladium complex [Pd(bpy)(cbdca)] (where bpy is 2,2'-bipyridine, and cbdca is 1,1-cyclobutanedicarboxylate ligand), with an aromatic ligand and a cis-square planar coordination geometry, has been shown to have better cytotoxic activity than cisplatin, cis-diamminedichloroplatinum(II), against P388 lymphocytic leukemia cells (Mansuri-Torshizi et al., 2001).

The planar aromatic ligands may interact easily with DNA, which is the principal target in the chemotherapy of tumors (Shehata, 2001; Cusumano & Giannetto,1997; Neidle et al., 1987).

We have synthesized and determined the crystal structures of several cis-coordinated palladium complexes with aromatic ligands, viz. [Pd(bpy)(cbdca)], [Pb(phen)(cbdca)] (where phen is 1,10-phenanthroline; Muranishi & Okabe, 2004), [Pd(bpy)(nad)], [Pd(biq)(nad)] (where nad is 2,3-naphthalenediol and biq is biquinoline; Okabe et al., 2004) and [Pd(phen)(ca)] (where ca is catechol is 1,2-benzenediol; Okabe et al., 2003). In this study, [Pd(bpy)(ca)], (I), has been synthesized and its structure determined.

In complex (I), the central Pd atom has a distorted cis-square planar coordination geometry with the two N atoms of the heterocycle and the two O atoms of the dianion of the ca ligand (Fig. 1). The overall structure resembles the structures of [Pd(byp)(nad)], (II), and [Pd(phen)(ca)], (III), which have similar bypyridyl and catecholate groups to (I).

The coordinate bond lengths and angles of (I) (Table 1) may be compared with those of (II) and (III), as well as those of other palladium complexes with non-aromatic ligands, suc as [Pd(en)M], (IV), and [Pd(en)C], (V) (where en is ethylenediamine, M is methymalonate and C is 1,1-cyclobutanedicarboxylate; Tercero et al., 2003). The Pd—O and Pd—N bond lengths of (I) resemble those of (II) and (III), in which the Pd—O bond lengths lie in the range 1.981 (2)–1.989 (2) Å and Pd—N in the range 2.001 (3)–2.019 (2) Å, but are slightly shorter than those of (IV) and (V), in which the Pd—O bond lengths lie in the range 1.995 (10)–2.027 (10) Å and Pd—N in the range 2.009 (11)–2.030 (2) Å. The O—Pd—O and N—Pd—N bond angles also resemble to those of (II) and (III), for which O—Pd—O lie in the range 84.84 (9)–85.09 (7)° and N—Pd—N in the range 80.78 (9)–81.69 (8)°, but are a little smaller than those of (IV) and (V), for which O—Pd—O lie in the range 89.51 (17)–92.69 (7)° and N—Pd—N in the range 84.09 (18)–84.15 (8)°. These differences may be explained by the difference in intramolecular mobility of the O and N atoms between the complexes with aromatic ligands and those with non-aromatic ligands, as explained by Okabe et al. (2003).

Experimental top

Bpy (7 mg, 0.0448 mmol) dissolved in dimethyl formamide (DMF, 1.0 ml) was reacted with palladium acetate, [Pd(CH3COOH)2] (10 mg), dissolved in DMF (2 ml), and then bpy (5 mg) dissolved in DMF (1 ml) was added. The mixture was allowed to stand at room temperature for a number of days to give red plate crystals of the complex.

Refinement top

All H atoms were located in difference Fourier maps, and then were placed at ideal positions and treated as riding, with a C—H distance of 0.93 Å and Uiso(H) = 1.2Ueq(carrier atom).

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 2000); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids for non-H atoms correspond to 50% probability.
(Benzene-1,2-diolato-κ2O,O')(2,2'-bipyridine-κ2N,N')palladium(II) top
Crystal data top
[Pd(C6H4O2)(C10H8N2)]F(000) = 736.0
Mr = 370.70Dx = 1.840 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 7.017 (2) Åθ = 14.8–15.0°
b = 23.873 (2) ŵ = 1.39 mm1
c = 8.118 (3) ÅT = 296 K
β = 100.30 (3)°Plate, red
V = 1338.0 (6) Å30.30 × 0.30 × 0.15 mm
Z = 4
Data collection top
Rigaku AFC-5R
diffractometer
Rint = 0.013
ω–2θ scansθmax = 27.5°
Absorption correction: ψ scan
(North et al., 1968)
h = 09
Tmin = 0.632, Tmax = 0.812k = 031
3414 measured reflectionsl = 1010
3079 independent reflections3 standard reflections every 150 reflections
2709 reflections with I > 2σ(I) intensity decay: 0.1%
Refinement top
Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.043 w = 1/[σ2(Fo2) + (0.0537P)2 + 6.095P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.136(Δ/σ)max < 0.001
S = 1.21Δρmax = 1.94 e Å3
3079 reflectionsΔρmin = 1.62 e Å3
190 parameters
Crystal data top
[Pd(C6H4O2)(C10H8N2)]V = 1338.0 (6) Å3
Mr = 370.70Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.017 (2) ŵ = 1.39 mm1
b = 23.873 (2) ÅT = 296 K
c = 8.118 (3) Å0.30 × 0.30 × 0.15 mm
β = 100.30 (3)°
Data collection top
Rigaku AFC-5R
diffractometer
2709 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.013
Tmin = 0.632, Tmax = 0.8123 standard reflections every 150 reflections
3414 measured reflections intensity decay: 0.1%
3079 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043190 parameters
wR(F2) = 0.136H-atom parameters constrained
S = 1.21Δρmax = 1.94 e Å3
3079 reflectionsΔρmin = 1.62 e Å3
Special details top

Refinement. Refinement using reflections with F2 > −10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pd10.76643 (5)0.00981 (2)0.00121 (4)0.0268 (1)
O10.8946 (6)0.0700 (2)0.1488 (4)0.0322 (8)
O20.7077 (5)0.0696 (2)0.1718 (4)0.0327 (8)
N10.8064 (6)0.0532 (2)0.1643 (5)0.0299 (9)
N20.6366 (6)0.0518 (2)0.1446 (5)0.0292 (9)
C20.7272 (7)0.1027 (2)0.1075 (6)0.030 (1)
C30.7401 (8)0.1490 (3)0.2116 (7)0.038 (1)
C40.8380 (9)0.1436 (3)0.3763 (7)0.042 (1)
C50.9177 (9)0.0929 (3)0.4326 (7)0.045 (1)
C60.9021 (9)0.0494 (3)0.3221 (7)0.039 (1)
C120.6294 (7)0.1019 (2)0.0683 (6)0.031 (1)
C130.5358 (8)0.1469 (3)0.1540 (7)0.037 (1)
C140.4500 (9)0.1404 (3)0.3204 (7)0.041 (1)
C150.4604 (9)0.0899 (3)0.3978 (7)0.043 (1)
C160.5546 (9)0.0459 (3)0.3072 (7)0.040 (1)
C170.8803 (7)0.1186 (2)0.0639 (6)0.029 (1)
C180.9567 (8)0.1683 (3)0.1350 (7)0.037 (1)
C190.9308 (9)0.2184 (3)0.0443 (8)0.043 (1)
C200.8272 (9)0.2185 (3)0.1180 (8)0.043 (1)
C210.7530 (8)0.1686 (3)0.1925 (7)0.037 (1)
C220.7783 (7)0.1188 (2)0.1039 (6)0.029 (1)
H30.68470.18290.17260.0455*
H40.84930.17430.44810.0508*
H50.98040.08850.54280.0544*
H60.96060.01550.35800.0465*
H130.53020.18110.10060.0444*
H140.38570.17030.37920.0490*
H150.40490.08530.50990.0514*
H160.56160.01150.35930.0481*
H181.02580.16840.24400.0442*
H190.98300.25150.09280.0521*
H200.80710.25200.17730.0521*
H210.68620.16870.30230.0447*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0307 (2)0.0266 (2)0.0221 (2)0.0011 (1)0.0019 (1)0.0011 (1)
O10.044 (2)0.030 (2)0.021 (2)0.002 (2)0.001 (1)0.000 (1)
O20.039 (2)0.030 (2)0.025 (2)0.002 (2)0.003 (1)0.000 (1)
N10.030 (2)0.035 (2)0.024 (2)0.001 (2)0.004 (2)0.001 (2)
N20.030 (2)0.036 (2)0.021 (2)0.001 (2)0.003 (2)0.002 (2)
C20.028 (2)0.039 (3)0.023 (2)0.001 (2)0.005 (2)0.000 (2)
C30.040 (3)0.041 (3)0.029 (3)0.004 (2)0.001 (2)0.004 (2)
C40.055 (4)0.043 (3)0.027 (3)0.001 (3)0.001 (2)0.009 (2)
C50.050 (3)0.056 (4)0.026 (3)0.001 (3)0.001 (2)0.002 (3)
C60.046 (3)0.039 (3)0.028 (3)0.004 (2)0.001 (2)0.004 (2)
C120.029 (2)0.036 (3)0.027 (2)0.002 (2)0.003 (2)0.001 (2)
C130.041 (3)0.040 (3)0.029 (3)0.002 (2)0.003 (2)0.002 (2)
C140.050 (3)0.042 (3)0.028 (3)0.007 (3)0.000 (2)0.008 (2)
C150.051 (3)0.046 (4)0.027 (3)0.004 (3)0.004 (2)0.004 (2)
C160.049 (3)0.041 (3)0.027 (3)0.002 (2)0.003 (2)0.001 (2)
C170.028 (2)0.033 (3)0.024 (2)0.002 (2)0.001 (2)0.002 (2)
C180.039 (3)0.043 (3)0.026 (2)0.004 (2)0.002 (2)0.006 (2)
C190.047 (3)0.037 (3)0.042 (3)0.007 (2)0.004 (3)0.007 (2)
C200.052 (3)0.034 (3)0.041 (3)0.000 (2)0.002 (3)0.008 (2)
C210.040 (3)0.041 (3)0.027 (3)0.001 (2)0.006 (2)0.007 (2)
C220.031 (2)0.033 (3)0.023 (2)0.003 (2)0.001 (2)0.002 (2)
Geometric parameters (Å, º) top
Pd1—O11.992 (4)C12—C131.380 (8)
Pd1—O21.980 (4)C13—C141.386 (8)
Pd1—N12.003 (4)C13—H130.930
Pd1—N21.993 (4)C14—C151.367 (9)
O1—C171.345 (7)C14—H140.930
O2—C221.354 (6)C15—C161.381 (9)
N1—C21.352 (7)C15—H150.930
N1—C61.339 (7)C16—H160.930
N2—C121.351 (7)C17—C181.385 (8)
N2—C161.350 (7)C17—C221.421 (7)
C2—C31.384 (8)C18—C191.398 (9)
C2—C121.469 (7)C18—H180.930
C3—C41.396 (8)C19—C201.386 (8)
C3—H30.930C19—H190.930
C4—C51.376 (9)C20—C211.395 (9)
C4—H40.930C20—H200.930
C5—C61.365 (9)C21—C221.384 (8)
C5—H50.930C21—H210.930
C6—H60.930
Pd1···Pd1i3.308 (1)C2···C17i3.322 (8)
Pd1···N2ii3.406 (5)C2···C22i3.496 (7)
Pd1···O1i3.427 (4)C2···C22ii3.563 (7)
O1···N2i3.325 (6)C2···C18i3.579 (8)
O1···C14ii3.437 (8)C3···C21ii3.468 (8)
O1···C5iii3.462 (7)C4···C21i3.514 (9)
O1···C15ii3.509 (8)C6···C22i3.512 (8)
O1···C13ii3.540 (7)C12···C22ii3.426 (8)
O1···N1i3.597 (6)C12···C18i3.436 (8)
O1···C12i3.598 (7)C12···C17i3.457 (7)
O2···C6i3.227 (8)C13···C17ii3.206 (8)
O2···C2ii3.284 (7)C13···C22ii3.368 (8)
O2···C12ii3.412 (7)C13···C18ii3.524 (8)
O2···N1i3.422 (6)C13···C18i3.574 (8)
O2···C15iv3.516 (7)C14···C17ii3.421 (8)
N1···C22i3.420 (7)C14···C18ii3.520 (9)
N1···C17i3.487 (7)
O1—Pd1—O285.6 (1)C2—C12—C13125.2 (5)
O1—Pd1—N197.9 (2)C12—C13—C14119.3 (6)
O1—Pd1—N2178.1 (2)C12—C13—H13120.4
O2—Pd1—N1175.7 (2)C14—C13—H13120.4
O2—Pd1—N296.2 (2)C13—C14—C15119.8 (6)
N1—Pd1—N280.3 (2)C13—C14—H14120.1
Pd1—O1—C17109.0 (3)C15—C14—H14120.1
Pd1—O2—C22109.0 (3)C14—C15—C16119.0 (5)
Pd1—N1—C2115.3 (3)C14—C15—H15120.5
Pd1—N1—C6125.2 (4)C16—C15—H15120.5
C2—N1—C6119.5 (5)N2—C16—C15121.4 (6)
Pd1—N2—C12115.9 (3)N2—C16—H16119.3
Pd1—N2—C16124.4 (4)C15—C16—H16119.3
C12—N2—C16119.7 (5)O1—C17—C18122.6 (4)
N1—C2—C3120.8 (4)O1—C17—C22118.2 (5)
N1—C2—C12114.3 (5)C18—C17—C22119.2 (5)
C3—C2—C12124.9 (5)C17—C18—C19120.6 (5)
C2—C3—C4118.6 (6)C17—C18—H18119.7
C2—C3—H3120.7C19—C18—H18119.7
C4—C3—H3120.7C18—C19—C20120.0 (6)
C3—C4—C5120.0 (6)C18—C19—H19120.0
C3—C4—H4120.0C20—C19—H19120.0
C5—C4—H4120.0C19—C20—C21120.1 (6)
C4—C5—C6118.2 (5)C19—C20—H20120.0
C4—C5—H5120.9C21—C20—H20120.0
C6—C5—H5120.9C20—C21—C22120.3 (5)
N1—C6—C5123.0 (6)C20—C21—H21119.8
N1—C6—H6118.5C22—C21—H21119.8
C5—C6—H6118.5O2—C22—C17118.2 (5)
N2—C12—C2114.1 (5)O2—C22—C21122.0 (4)
N2—C12—C13120.7 (5)C17—C22—C21119.8 (5)
Pd1—O1—C17—C18179.8 (4)N1—C6—C5—C42.8 (10)
Pd1—O1—C17—C221.9 (6)N2—PD1—O2—C22178.5 (3)
Pd1—O2—C22—C171.9 (6)N2—PD1—N1—C22.2 (4)
Pd1—O2—C22—C21177.8 (4)N2—PD1—N1—C6178.2 (5)
Pd1—N1—C2—C3178.1 (4)N2—C12—C2—C3179.8 (5)
Pd1—N1—C2—C121.5 (6)N2—C12—C13—C140.6 (9)
Pd1—N1—C6—C5176.9 (5)N2—C16—C15—C140.2 (10)
Pd1—N2—C12—C22.5 (6)C2—N1—C6—C52.7 (9)
Pd1—N2—C12—C13177.3 (4)C2—C3—C4—C50.6 (10)
Pd1—N2—C16—C15177.5 (5)C2—C12—N2—C16179.0 (5)
O1—PD1—O2—C220.7 (3)C2—C12—C13—C14179.7 (6)
O1—PD1—N1—C2177.0 (4)C3—C2—N1—C61.5 (8)
O1—PD1—N1—C62.6 (5)C3—C2—C12—C130.5 (9)
O1—C17—C18—C19177.1 (5)C3—C4—C5—C61.6 (10)
O1—C17—C22—O22.7 (7)C4—C3—C2—C12179.9 (6)
O1—C17—C22—C21177.0 (5)C6—N1—C2—C12178.8 (5)
O2—PD1—O1—C170.7 (3)C12—N2—C16—C150.9 (9)
O2—PD1—N2—C12174.9 (4)C12—C13—C14—C150.5 (9)
O2—PD1—N2—C163.6 (5)C13—C12—N2—C161.3 (8)
O2—C22—C17—C18178.9 (5)C13—C14—C15—C160.9 (10)
O2—C22—C21—C20179.7 (5)C17—C18—C19—C200.3 (10)
N1—PD1—O1—C17178.1 (3)C17—C22—C21—C200.0 (9)
N1—PD1—N2—C122.6 (4)C18—C17—C22—C211.4 (8)
N1—PD1—N2—C16178.9 (5)C18—C19—C20—C211 (1)
N1—C2—C3—C40.5 (9)C19—C18—C17—C221.3 (9)
N1—C2—C12—N20.6 (7)C19—C20—C21—C221.5 (10)
N1—C2—C12—C13179.1 (5)C19—C20—C21—C221.5 (10)
Symmetry codes: (i) x+2, y, z; (ii) x+1, y, z; (iii) x+2, y, z+1; (iv) x+1, y, z1.

Experimental details

Crystal data
Chemical formula[Pd(C6H4O2)(C10H8N2)]
Mr370.70
Crystal system, space groupMonoclinic, P21/n
Temperature (K)296
a, b, c (Å)7.017 (2), 23.873 (2), 8.118 (3)
β (°) 100.30 (3)
V3)1338.0 (6)
Z4
Radiation typeMo Kα
µ (mm1)1.39
Crystal size (mm)0.30 × 0.30 × 0.15
Data collection
DiffractometerRigaku AFC-5R
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.632, 0.812
No. of measured, independent and
observed [I > 2σ(I)] reflections
3414, 3079, 2709
Rint0.013
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.136, 1.21
No. of reflections3079
No. of parameters190
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.94, 1.62

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 2000), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), TEXSAN.

Selected geometric parameters (Å, º) top
Pd1—O11.992 (4)Pd1—N21.993 (4)
Pd1—O21.980 (4)O1—C171.345 (7)
Pd1—N12.003 (4)O2—C221.354 (6)
O1—Pd1—O285.6 (1)O2—Pd1—N1175.7 (2)
O1—Pd1—N197.9 (2)O2—Pd1—N296.2 (2)
O1—Pd1—N2178.1 (2)N1—Pd1—N280.3 (2)
 

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