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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m1057–m1058.
Published online 2008 July 23. doi:  10.1107/S1600536808022575
PMCID: PMC2961971

Di-μ-chlorido-bis­{[2-(morpholinometh­yl)phenyl-κ2 C 1,N]palladium(II)}

Abstract

The title compound, [Pd2(C11H14NO)2Cl2], has a dimeric structure with Cl atoms bridging the two Pd atoms, one half of the mol­ecule being generated by symmetry due to the crystallographic inversion centre located in the middle of the perfectly planar Pd2Cl2 ring. The five-membered ring adopts an envelope conformation, while the morpholino group has a chair conformation. The geometry around the metal centres is distorted square-planar, as a result of a strong intra­molecular N→Pd coordination trans to a Pd—Cl bond. In the crystal structure, the dimeric structure is strengthened by inter­molecular C—H(...)Cl hydrogen bonds. C—H(...)Cphen­yl inter­actions link the dimers into a columnar supra­molecular array along the a axis; the dimers are further connected by C—H(...)Ph inter­actions into a three-dimensional supra­molecular arrangement.

Related literature

For related literature, see: Copolovici et al. (2007 [triangle], 2008 [triangle]); Crispini et al. (1992 [triangle]); Fuchita et al. (1999 [triangle]); Mahalakshmi et al. (2003 [triangle]); Mentes et al. (1997 [triangle], 2004 [triangle], 2005 [triangle]); Phadnis et al. (2002 [triangle], 2003 [triangle]); Emsley (1994 [triangle]); IUPAC (1979 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1057-scheme1.jpg

Experimental

Crystal data

  • [Pd2(C11H14NO)2Cl2]
  • M r = 636.20
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1057-efi3.jpg
  • a = 8.1234 (6) Å
  • b = 16.4437 (13) Å
  • c = 8.8298 (7) Å
  • β = 101.9570 (10)°
  • V = 1153.88 (15) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.81 mm−1
  • T = 297 (2) K
  • 0.22 × 0.17 × 0.17 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.677, T max = 0.733
  • 9118 measured reflections
  • 2354 independent reflections
  • 2245 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.028
  • wR(F 2) = 0.059
  • S = 1.15
  • 2354 reflections
  • 137 parameters
  • H-atom parameters constrained
  • Δρmax = 0.49 e Å−3
  • Δρmin = −0.43 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808022575/hk2489sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022575/hk2489Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

Financial support from the Romanian Ministry of Education and Research within the programme ‘Excellency Research’ (contract No. 19/2006) is greatly appreciated. The authors also thank the National Center for X-ray Diffraction in Cluj-Napoca, Romania, for help with the solid-state structure determinations.

supplementary crystallographic information

Comment

There are scarce data reported upon the reactivity of triorganoantimony(III) compounds toward palladium(II) chloride or corresponding complexes. The compounds of the type [PdCl2(SbR3)2], R = iPr (Phadnis et al., 2002), ortho-tolyl (Mentes & Fawcett, 2005), were obtained by reaction of [PdCl2(COD)], COD = cycloocta-1,5-diene, with the corresponding stibines. The reaction of [PdCl2(PhCN)2] with SbR3 (R = 2-thienyl) resulted in a black insoluble powder (possible Pd metal) due to a decomposition process (Mahalakshmi et al., 2003), whilst the reaction of [PdCl2(PhCN)2] with tri(allyl)stibine and tris(2-methylallyl)stibine afforded the transmetalation products [Pd2(µ-Cl)2R2], R = allyl, 2-methylallyl, and the fate of the stibine residue is unknown (Phadnis et al., 2003). Reaction of SbPh3 with [PdCl2(COD)] or PdCl2 afforded trans-[PdCl(σ-Ph)(SbPh3)2] due to the easy cleveage of Sb—C bond in SbPh3, whilst reaction of Na2PdCl4 with SbPh3 gave cis-[PdCl2(SbPh3)2] contaminated with small amount of chloro σ-phenyl complex (Mentes et al., 1997). Related to our interest on the synthesis and chemical properties of organoantimony(III) compounds, we performed the reaction between Sb[C6H4CH2{N(CH2CH2)2O}-2]3 and [PdCl2(MeCN)2] in acetonitrile/chloroform mixture, at room temperature.

The title compound has a dimeric structure, with two palladacycles bridged through the chlorine atoms, resulting in a perfectly planar Pd2Cl2 core. One half of the molecule is generated by symmetry owing the crystallographic inversion centre located in the middle of the Pd2Cl2 ring. The cycle is distorted from the ideal square as reflected by the diferences in the Pd—Cl bond lengths and the Cl1—Pd1—Cl1i and Pd1—Cl1—Pd1i bond angles (Table 1) [symmetry code: (i) = 1 - x, 1 - y, -z].

The N atom from the pendant arm coordinates the metal centre resulting in a square planar (C,N)PdCl2 core, in which the distortion is mainly due to the PdC3N ring constraint. The two equivalent organic ligands from the dimer are in a trans arrangement with respect to the Pd···Pd axis (Fig. 1). The Pd1—C1 [1.971 (2) Å] bond is smaller than the sum of the corresponding covalent radii, its magnitude being similar to those found for related compounds for which partialy Pd—C multiple bond was assumed (Crispini et al., 1992, Fuchita et al., 1999, Mentes et al., 2004).

An almost ideal chair conformation was observed for the morpholinyl groups with torsion angles [C8—N1—C11—C10 = -52.6 (3)° and C10—O1—C9—C8 = 58.4 (3)°] similar with those found in 4-benzylmorpholin-4-ium chloride (Copolovici et al., 2007) and in tris[2-(morpholin-4-ylmethyl)phenyl -κ2C1,N]αntimony(III) (Copolovici et al., 2008).

As a result of the intramolecular coordination of the N1 atom from the organic ligand to Pd1 atom, a nonplanar five-membered ring is formed, with nitrogen atom lying out of the Pd1/C1/C2/C7 best plane [0.666 (2) Å]. The dihedral angle between the Pd1/N1/C7 and Pd1/C1/C2/C7 planes is 39.2 (1)°. This induces planar chirality (with the aromatic ring and the nitrogen atom as chiral plane and pilot atom, respectively, IUPAC, 1979). In the crystal of the title compound, the dimer contains both RN and SNi isomers.

In the crystal structure, the dimer is strengthened by hydrogen-bond type interactions (Table 2) involving the Cl from one molecular unit and the methylenic proton of the morpholinyl group from the other molecular unit from the same dimer [the sum of van der Waals radii of the corresponding atoms ΣrvdW (Cl,H) = 3.00 Å; Emsley, 1994] (Fig. 2).

Intermolecular CH···Cphenyl interactions (Table 2) between a methylene hydrogen from the pendant arm and a carbon atom from the aromatic ring of another dimer connect the molecular units in a columnar arrangement along the a axis. Furthermore, these arrays are interlinked by intermolecular C—H···Ph interactions (Table 2) in a three-dimensional supramolecular arrangement in the crystal structure (Fig.3).

Experimental

For the preparation of the title compound, PdCl2 (0.1 g, 0.56 mmol) in acetonitrile (40 ml) was refluxed for 3 h, and then allowed to cool to room temperature. A solution of Sb[C6H4CH2{N(CH2CH2)2O}-2]3 (0.369 g, 0.56 mmol) in CHCl3 (35 ml) was added and the mixture was stirred at room temperature for 30 h, under an N2 atmosphere. The reaction mixture was filtered off and the solvents were removed under vacuum. The yellow oil obtained was triturated with hexane (2 x 20 ml) and then washed with petroleum ether (2 x 10 ml) to give a yellow solid. Yellow crystals suitable for X-ray diffraction studies were obtained by slow diffusion of hexane into a solution of CH2Cl2 of the title compound (1:1 v/v ratio) (yield: 0.217 g, 47%). Anal. Found: C, 41.38; H, 4.63; N, 4.73. Calc. for C22H28Cl2N2O2Pd2 (636.22): C, 41.53; H, 4.44; N, 4.40%. FT—IR (KBr, cm-1): C—H stretch aromatic: 3038, 3035, 2958, 2891; 2857, 1436, 1114, 1069, 868, 745.

Refinement

H atoms were positioned geometrically, with C-H = 0.93 and 0.97 Å for aromatic and methylene H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C),

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry code: (i) 1 - x, 1 - y, -z].
Fig. 2.
: Intermolecular interactions in the title compound. Hydrogen bonds are shown as dashed lines [symmetry codes: (i) 1 - x, 1 - y, -z; (ii) -x, 1 - y, -z; (iii) x, 3/2 - y, 1/2 + z]. H atoms not involved in hydrogen bonding are omitted for clarity.
Fig. 3.
: A packing diagram of the title compound, showing the supramolecular arrangement.

Crystal data

[Pd2(C11H14NO)2Cl2]F000 = 632
Mr = 636.20Dx = 1.831 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4334 reflections
a = 8.1234 (6) Åθ = 2.5–27.3º
b = 16.4437 (13) ŵ = 1.81 mm1
c = 8.8298 (7) ÅT = 297 (2) K
β = 101.9570 (10)ºBlock, yellow
V = 1153.88 (15) Å30.22 × 0.17 × 0.17 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer2354 independent reflections
Radiation source: fine-focus sealed tube2245 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.026
T = 297(2) Kθmax = 26.4º
[var phi] and ω scansθmin = 2.5º
Absorption correction: multi-scan(SADABS; Bruker, 2000)h = −10→10
Tmin = 0.677, Tmax = 0.733k = −20→20
9118 measured reflectionsl = −11→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.059  w = 1/[σ2(Fo2) + (0.0166P)2 + 1.0911P] where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max = 0.002
2354 reflectionsΔρmax = 0.49 e Å3
137 parametersΔρmin = −0.43 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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 > 2sigma(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)

xyzUiso*/Ueq
Pd10.32057 (3)0.559622 (13)0.02382 (2)0.03252 (8)
Cl10.41182 (11)0.49501 (6)−0.17788 (9)0.0591 (3)
O10.4523 (3)0.69670 (15)0.4417 (3)0.0524 (6)
N10.2135 (3)0.61896 (14)0.1932 (3)0.0311 (5)
C10.1119 (3)0.59843 (17)−0.1126 (3)0.0332 (6)
C2−0.0122 (4)0.62200 (19)−0.0349 (4)0.0382 (7)
C3−0.1640 (4)0.6534 (2)−0.1153 (4)0.0564 (10)
H3−0.24600.6700−0.06240.068*
C4−0.1921 (4)0.6598 (2)−0.2752 (4)0.0578 (10)
H4−0.29320.6811−0.32960.069*
C5−0.0721 (4)0.6349 (2)−0.3534 (4)0.0494 (8)
H5−0.09300.6382−0.46080.059*
C60.0798 (4)0.60484 (19)−0.2732 (4)0.0401 (7)
H60.16140.5888−0.32700.048*
C70.0286 (4)0.6089 (2)0.1360 (4)0.0426 (7)
H7A−0.03180.64800.18640.051*
H7B−0.00550.55470.16010.051*
C80.2571 (4)0.5867 (2)0.3546 (3)0.0437 (8)
H8A0.25060.52780.35100.052*
H8B0.17430.60590.41120.052*
C90.4285 (4)0.6111 (2)0.4406 (4)0.0493 (8)
H9A0.44480.59170.54640.059*
H9B0.51250.58540.39290.059*
C100.4272 (4)0.7249 (2)0.2865 (4)0.0497 (8)
H10A0.50650.69830.23440.060*
H10B0.44790.78300.28620.060*
C110.2517 (4)0.70759 (18)0.2014 (3)0.0378 (7)
H11A0.17300.73510.25290.045*
H11B0.23650.72920.09720.045*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pd10.03461 (14)0.03664 (14)0.02611 (12)0.00850 (9)0.00582 (9)0.00045 (9)
Cl10.0574 (5)0.0891 (7)0.0284 (4)0.0394 (5)0.0034 (4)−0.0061 (4)
O10.0565 (14)0.0596 (15)0.0356 (12)0.0015 (12)−0.0028 (10)−0.0127 (11)
N10.0336 (12)0.0330 (12)0.0270 (12)−0.0006 (10)0.0071 (10)−0.0009 (10)
C10.0313 (14)0.0282 (14)0.0368 (16)0.0048 (12)−0.0006 (12)0.0000 (12)
C20.0324 (15)0.0417 (17)0.0391 (17)−0.0050 (13)0.0039 (13)−0.0066 (13)
C30.0319 (17)0.077 (3)0.057 (2)0.0086 (17)0.0022 (16)−0.0190 (19)
C40.0371 (18)0.069 (2)0.057 (2)0.0090 (17)−0.0122 (16)−0.0084 (19)
C50.0468 (19)0.056 (2)0.0398 (18)0.0014 (16)−0.0038 (15)0.0025 (16)
C60.0390 (16)0.0432 (17)0.0365 (16)0.0032 (14)0.0043 (13)0.0025 (14)
C70.0344 (16)0.0509 (19)0.0446 (18)−0.0057 (14)0.0131 (14)−0.0087 (15)
C80.060 (2)0.0444 (18)0.0291 (16)0.0036 (16)0.0144 (15)0.0038 (13)
C90.059 (2)0.059 (2)0.0274 (16)0.0164 (17)0.0032 (15)0.0011 (15)
C100.050 (2)0.050 (2)0.0455 (19)−0.0111 (16)0.0020 (15)−0.0035 (16)
C110.0464 (17)0.0309 (15)0.0343 (16)0.0022 (13)0.0042 (13)−0.0015 (12)

Geometric parameters (Å, °)

Pd1—Cl1i2.4815 (8)C7—H7A0.9700
Cl1—Pd12.3232 (8)C7—H7B0.9700
Cl1—Pd1i2.4815 (8)C8—N11.493 (4)
N1—Pd12.118 (2)C8—C91.496 (5)
C1—C21.387 (4)C8—H8A0.9700
C1—C61.392 (4)C8—H8B0.9700
C1—Pd11.971 (3)C9—O11.421 (4)
C2—C31.389 (4)C9—H9A0.9700
C2—C71.492 (4)C9—H9B0.9700
C3—C41.387 (5)C10—O11.421 (4)
C3—H30.9300C10—C111.495 (4)
C4—C51.369 (5)C10—H10A0.9700
C4—H40.9300C10—H10B0.9700
C5—C61.381 (4)C11—N11.489 (4)
C5—H50.9300C11—H11A0.9700
C6—H60.9300C11—H11B0.9700
C7—N11.492 (4)
Cl1—Pd1—Cl1i82.66 (3)C1—C6—H6119.7
N1—Pd1—Cl1174.34 (7)N1—C7—C2108.9 (2)
N1—Pd1—Cl1i102.76 (6)N1—C7—H7A109.9
C1—Pd1—Cl192.88 (9)C2—C7—H7A109.9
C1—Pd1—Cl1i175.53 (9)N1—C7—H7B109.9
C1—Pd1—N181.69 (11)C2—C7—H7B109.9
Pd1—Cl1—Pd1i97.34 (3)H7A—C7—H7B108.3
C10—O1—C9108.9 (2)N1—C8—C9113.6 (3)
C7—N1—C8107.9 (2)N1—C8—H8A108.8
C7—N1—Pd1104.01 (17)C9—C8—H8A108.8
C8—N1—Pd1117.35 (18)N1—C8—H8B108.8
C11—N1—Pd1111.92 (17)C9—C8—H8B108.8
C11—N1—C7108.0 (2)H8A—C8—H8B107.7
C11—N1—C8107.2 (2)O1—C9—C8112.4 (3)
C2—C1—C6118.8 (3)O1—C9—H9A109.1
C2—C1—Pd1114.2 (2)C8—C9—H9A109.1
C6—C1—Pd1127.1 (2)O1—C9—H9B109.1
C1—C2—C3120.7 (3)C8—C9—H9B109.1
C1—C2—C7115.4 (3)H9A—C9—H9B107.9
C3—C2—C7123.9 (3)O1—C10—C11110.8 (3)
C4—C3—C2119.4 (3)O1—C10—H10A109.5
C4—C3—H3120.3C11—C10—H10A109.5
C2—C3—H3120.3O1—C10—H10B109.5
C5—C4—C3120.4 (3)C11—C10—H10B109.5
C5—C4—H4119.8H10A—C10—H10B108.1
C3—C4—H4119.8N1—C11—C10112.2 (3)
C4—C5—C6120.2 (3)N1—C11—H11A109.2
C4—C5—H5119.9C10—C11—H11A109.2
C6—C5—H5119.9N1—C11—H11B109.2
C5—C6—C1120.5 (3)C10—C11—H11B109.2
C5—C6—H6119.7H11A—C11—H11B107.9
Pd1i—Cl1—Pd1—C1−179.66 (9)C1—C2—C7—N132.1 (4)
Pd1i—Cl1—Pd1—Cl1i0.0C3—C2—C7—N1−149.6 (3)
C11—N1—Pd1—C1−84.42 (19)N1—C8—C9—O154.4 (4)
C7—N1—Pd1—C131.98 (19)O1—C10—C11—N1−61.0 (4)
C8—N1—Pd1—C1151.0 (2)C10—C11—N1—C7168.6 (3)
C11—N1—Pd1—Cl1i96.05 (18)C10—C11—N1—C852.6 (3)
C7—N1—Pd1—Cl1i−147.55 (17)C10—C11—N1—Pd1−77.4 (3)
C8—N1—Pd1—Cl1i−28.5 (2)C2—C7—N1—C1177.7 (3)
C6—C1—C2—C3−1.6 (5)C2—C7—N1—C8−166.7 (3)
Pd1—C1—C2—C3177.7 (3)C2—C7—N1—Pd1−41.4 (3)
C6—C1—C2—C7176.8 (3)C9—C8—N1—C11−49.5 (3)
Pd1—C1—C2—C7−3.9 (3)C9—C8—N1—C7−165.6 (3)
C1—C2—C3—C41.1 (5)C9—C8—N1—Pd177.4 (3)
C7—C2—C3—C4−177.1 (3)C11—C10—O1—C961.6 (4)
C2—C3—C4—C50.4 (6)C8—C9—O1—C10−58.5 (4)
C3—C4—C5—C6−1.4 (6)C2—C1—Pd1—N1−16.4 (2)
C4—C5—C6—C10.9 (5)C6—C1—Pd1—N1162.9 (3)
C2—C1—C6—C50.6 (5)C2—C1—Pd1—Cl1162.0 (2)
Pd1—C1—C6—C5−178.6 (2)C6—C1—Pd1—Cl1−18.7 (3)

Symmetry codes: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9B···Cl1i0.972.493.370 (3)150
C7—H7B···C1ii0.972.673.588 (4)159
C11—H11A···Cgiii0.972.933.829 (3)154

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z; (iii) x, −y+3/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2489).

References

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