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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m1084.
Published online 2008 July 31. doi:  10.1107/S1600536808023167
PMCID: PMC2961992

3-2,2,4,4,6,6-Hexakis(3,5-dimethyl­pyrazol-1-yl)-2λ5,4λ5,6λ5-1,3,5,2,4,6-triaza­triphosphinine]tris­[cis-dichloridopalladium(II)]

Abstract

The title complex, [Pd3Cl6(C30H42N15P3)], possesses C 3 mol­ecular symmetry. The P and N atoms of the cyclo­triphosphazene and the Pd atom are located on the crystallographic mirror plane. Each of the three symmetry-related Pd atoms is coordinated by two chloride ligands and two exocyclic pyrazolyl N atoms, but not by the cyclo­triphosphazene N atoms.

Related literature

For related literature, see: Chandrasekhar & Nagendran (2001 [triangle]); Gallicano & Paddock (1982 [triangle]).

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Object name is e-64-m1084-scheme1.jpg

Experimental

Crystal data

  • [Pd3Cl6(C30H42N15P3)]
  • M r = 1237.60
  • Hexagonal, An external file that holds a picture, illustration, etc.
Object name is e-64-m1084-efi1.jpg
  • a = 17.2989 (3) Å
  • c = 14.4545 (6) Å
  • V = 3746.02 (18) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.02 mm−1
  • T = 296 (2) K
  • 0.24 × 0.20 × 0.16 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (North et al., 1968 [triangle]) T min = 0.792, T max = 0.854
  • 42917 measured reflections
  • 3157 independent reflections
  • 2098 reflections with I > 2σ(I)
  • R int = 0.048

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.108
  • S = 1.07
  • 3157 reflections
  • 91 parameters
  • H-atom parameters constrained
  • Δρmax = 0.52 e Å−3
  • Δρmin = −0.35 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808023167/kp2182sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808023167/kp2182Isup2.hkl

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

supplementary crystallographic information

Comment

Various cyclotriphosphazene-based ligands have been designed and utilized to prepare coordination and organometallic complexes (Chandrasekhar & Nagendran, 2001). In particular, the 6-membered cyclic ligand N3P3(3,5-Me2pz)6 (3,5-Me2pz = 3,5-dimethylpyrazolyl) has many potential donor sites due to the exocyclic pyrazolyl nitrogen atoms in addition to the ring nitrogen and phosphorus atoms. This ligand was previously reported to react with [PdCl2(PhCN)2] to give the title complex, which was not structurally characterized by X-ray difraction (Gallicano & Paddock, 1982). We chose the title complex to be used as a starting material with the C3-symmetry in preparing coordination polymers by treating it with organic linking ligands. In this context, we determined the three-dimensional structure of the title complex to confirm its molecular symmetry.

The central core has a perfectly planar hexagonal P3N3 unit, to which three surrounding square-planar palladium fragments (PdCl2N2) are perpendicular (Fig. 1, Table 1). The crystallographic mirror plane (z = 3/4) passes through the central cyclotriphosphazene ring (three P and three N atoms) and the three surrounding palladium atoms, and bisects the pendant germinal pyrazolyl ligands in each, symmetry related PdCl2(pyrazolyl)2 unit. A space filling model of the title complex (Fig. 2) shows its C3-symmetry and close packing. As previously predicted by NMR and IR spectroscopy (Gallicano & Paddock, 1982), each palladium metal is coordinated by two chloro ligands and exocyclic pyrazolyl N atoms, but not to the cyclotriphosphazene N atoms, and lies 0.022 (1) Å below the Cl2N2 plane. Each phosphorus atom is bound to four N atoms: two central cyclotriphosphazene N atoms and two exocyclic pyrazolyl N atoms. Consistently with our expectation, the P1—N1 (cyclotriphosphazene) bond is significantly longer than P1—N2 (pyrazolyl) bond. All the Pd···Pd separations are equal (7.7538 (6) Å) due to the crystallographic symmetry.

Experimental

The title complex was prepared by the literature method (Gallicano & Paddock, 1982). The product was recrystallized from a mixture of dichloromethane–hexane.

Refinement

All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were generated in ideal positions and refined in a riding model.

Figures

Fig. 1.
Molecular structure showing the 50% probability displacement ellipsoids. H atoms are omitted for clarity.
Fig. 2.
A space filling model of the title complex showing its C3 axis at the center of the cyclotriphosphazene ring: (a) red: Pd; green: Cl; orange: P; purple: N; grey: C; white, H.

Crystal data

[Pd3Cl6(C30H42N15P3)]Z = 2
Mr = 1237.60F000 = 1224
Hexagonal, P63/mDx = 1.097 Mg m3
Hall symbol: -P6cMo Kα radiation λ = 0.71073 Å
a = 17.2989 (3) ÅCell parameters from 9849 reflections
b = 17.2989 (3) Åθ = 2.4–27.2º
c = 14.4545 (6) ŵ = 1.02 mm1
α = 90ºT = 296 (2) K
β = 90ºBlock, yellow
γ = 120º0.24 × 0.20 × 0.16 mm
V = 3746.02 (18) Å3

Data collection

Bruker SMART CCD area-detector diffractometer3157 independent reflections
Radiation source: sealed tube2098 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.048
T = 296(2) Kθmax = 28.3º
[var phi] and ω scansθmin = 3.6º
Absorption correction: multi-scan(North et al., 1968)h = −23→22
Tmin = 0.792, Tmax = 0.854k = −19→22
42917 measured reflectionsl = −19→19

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.108  w = 1/[σ2(Fo2) + (0.0477P)2 + 1.7582P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.002
3157 reflectionsΔρmax = 0.52 e Å3
91 parametersΔρmin = −0.35 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 > 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)

xyzUiso*/Ueq
Pd10.13572 (2)0.37375 (2)0.75000.05476 (14)
Cl10.02844 (7)0.32969 (8)0.64026 (8)0.0961 (3)
P10.31769 (7)0.56802 (7)0.75000.0438 (2)
N10.2362 (2)0.5861 (2)0.75000.0472 (7)
N20.30675 (15)0.50221 (15)0.84168 (15)0.0503 (5)
C10.3607 (2)0.5175 (2)0.9179 (2)0.0697 (9)
C20.3213 (3)0.4397 (3)0.9672 (3)0.0873 (12)
H20.34250.42901.02200.105*
N30.23411 (17)0.41658 (16)0.84595 (17)0.0573 (6)
C30.2439 (2)0.3792 (2)0.9210 (3)0.0743 (10)
C40.4433 (3)0.6016 (3)0.9398 (3)0.1093 (17)
H4A0.45550.64420.89140.164*
H4B0.49210.59040.94490.164*
H4C0.43590.62490.99740.164*
C50.1818 (3)0.2838 (3)0.9456 (4)0.121 (2)
H5A0.13450.25760.90080.181*
H5B0.15700.28051.00580.181*
H5C0.21390.25180.94580.181*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pd10.0519 (2)0.0567 (2)0.05085 (19)0.02349 (16)0.0000.000
Cl10.0739 (6)0.1049 (8)0.0898 (7)0.0300 (6)−0.0295 (5)−0.0085 (6)
P10.0508 (6)0.0488 (6)0.0333 (4)0.0259 (5)0.0000.000
N10.0495 (18)0.0505 (19)0.0375 (15)0.0218 (15)0.0000.000
N20.0538 (14)0.0508 (13)0.0433 (11)0.0240 (12)−0.0024 (10)0.0062 (9)
C10.071 (2)0.072 (2)0.0544 (17)0.0276 (18)−0.0132 (15)0.0103 (15)
C20.088 (3)0.080 (2)0.073 (2)0.026 (2)−0.019 (2)0.0274 (19)
N30.0636 (16)0.0503 (14)0.0518 (13)0.0238 (12)−0.0023 (11)0.0097 (10)
C30.074 (2)0.064 (2)0.068 (2)0.0219 (18)−0.0088 (17)0.0191 (16)
C40.101 (3)0.095 (3)0.072 (2)0.005 (2)−0.041 (2)0.024 (2)
C50.117 (4)0.079 (3)0.122 (4)0.016 (3)−0.028 (3)0.047 (3)

Geometric parameters (Å, °)

Pd1—N32.027 (2)C1—C41.476 (5)
Pd1—N3i2.027 (2)C2—C31.389 (5)
Pd1—Cl12.2642 (10)C2—H20.9300
Pd1—Cl1i2.2641 (10)N3—C31.317 (4)
P1—N1ii1.557 (3)C3—C51.494 (5)
P1—N11.589 (3)C4—H4A0.9600
P1—N2i1.695 (2)C4—H4B0.9600
P1—N21.695 (2)C4—H4C0.9600
N1—P1iii1.557 (3)C5—H5A0.9600
N2—C11.381 (4)C5—H5B0.9600
N2—N31.384 (3)C5—H5C0.9600
C1—C21.367 (5)
N3—Pd1—N3i86.36 (14)C1—C2—H2126.0
N3—Pd1—Cl1178.26 (8)C3—C2—H2126.0
N3i—Pd1—Cl192.34 (8)C3—N3—N2107.0 (2)
N3—Pd1—Cl1i92.34 (8)C3—N3—Pd1132.5 (2)
N3i—Pd1—Cl1i178.26 (8)N2—N3—Pd1120.51 (16)
Cl1—Pd1—Cl1i88.95 (6)N3—C3—C2109.7 (3)
N1ii—P1—N1118.0 (2)N3—C3—C5122.7 (3)
N1ii—P1—N2i108.78 (11)C2—C3—C5127.4 (3)
N1—P1—N2i108.66 (11)C1—C4—H4A109.5
N1ii—P1—N2108.78 (11)C1—C4—H4B109.5
N1—P1—N2108.66 (11)H4A—C4—H4B109.5
N2i—P1—N2102.86 (17)C1—C4—H4C109.5
P1iii—N1—P1122.0 (2)H4A—C4—H4C109.5
C1—N2—N3109.5 (2)H4B—C4—H4C109.5
C1—N2—P1131.1 (2)C3—C5—H5A109.5
N3—N2—P1119.37 (17)C3—C5—H5B109.5
C2—C1—N2105.7 (3)H5A—C5—H5B109.5
C2—C1—C4128.3 (3)C3—C5—H5C109.5
N2—C1—C4126.0 (3)H5A—C5—H5C109.5
C1—C2—C3108.1 (3)H5B—C5—H5C109.5

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KP2182).

References

  • Bruker (1997). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chandrasekhar, V. & Nagendran, S. (2001). Chem. Soc. Rev.30, 193–203.
  • Gallicano, K. D. & Paddock, N. L. (1982). Can. J. Chem.60, 521–528.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography