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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

[μ3-2,2,4,4,6,6-Hexa­kis­(3,5-di­methyl­pyrazol-1-yl)-2λ5,4λ5,6λ5-1,3,5,2,4,6-tri­aza­triphosphinine]tris­­[cis-di­chloridopalladium(II)]

aDepartment of Chemistry (BK21), Sungkyunkwan University, Natural Science Campus, Suwon 440-746, Republic of Korea
*Correspondence e-mail: soonwlee@skku.edu

(Received 11 July 2008; accepted 23 July 2008; online 31 July 2008)

The title complex, [Pd3Cl6(C30H42N15P3)], possesses C3 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[Chandrasekhar, V. & Nagendran, S. (2001). Chem. Soc. Rev. 30, 193-203.]); Gallicano & Paddock (1982[Gallicano, K. D. & Paddock, N. L. (1982). Can. J. Chem. 60, 521-528.]).

[Scheme 1]

Experimental

Crystal data
  • [Pd3Cl6(C30H42N15P3)]

  • Mr = 1237.60

  • Hexagonal, P 63 /m

  • 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[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.792, Tmax = 0.854

  • 42917 measured reflections

  • 3157 independent reflections

  • 2098 reflections with I > 2σ(I)

  • Rint = 0.048

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 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

Table 1
Selected geometric parameters (Å, °)

Pd1—N3 2.027 (2)
Pd1—Cl1 2.2642 (10)
P1—N2 1.695 (2)
N2—N3 1.384 (3)
N3—Pd1—N3i 86.36 (14)
N3—Pd1—Cl1 178.26 (8)
N3i—Pd1—Cl1 92.34 (8)
Cl1—Pd1—Cl1i 88.95 (6)
N1ii—P1—N1 118.0 (2)
N2i—P1—N2 102.86 (17)
Symmetry codes: (i) [x, y, -z+{\script{3\over 2}}]; (ii) -y+1, x-y+1, z.

Data collection: SMART (Bruker, 1997[Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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.

Related literature top

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

Experimental top

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

Refinement top

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

Computing details top

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

Figures top
[Figure 1] Fig. 1. Molecular structure showing the 50% probability displacement ellipsoids. H atoms are omitted for clarity.
[Figure 2] 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.
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)] top
Crystal data top
[Pd3Cl6(C30H42N15P3)]Dx = 1.097 Mg m3
Mr = 1237.60Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63/mCell parameters from 9849 reflections
Hall symbol: -P6cθ = 2.4–27.2°
a = 17.2989 (3) ŵ = 1.02 mm1
c = 14.4545 (6) ÅT = 296 K
V = 3746.02 (18) Å3Block, yellow
Z = 20.24 × 0.20 × 0.16 mm
F(000) = 1224
Data collection top
Bruker SMART CCD area-detector
diffractometer
3157 independent reflections
Radiation source: sealed tube2098 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.048
ϕ and ω scansθmax = 28.3°, θmin = 3.6°
Absorption correction: multi-scan
(North et al., 1968)
h = 2322
Tmin = 0.792, Tmax = 0.854k = 1922
42917 measured reflectionsl = 1919
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0477P)2 + 1.7582P]
where P = (Fo2 + 2Fc2)/3
3157 reflections(Δ/σ)max = 0.002
91 parametersΔρmax = 0.52 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
[Pd3Cl6(C30H42N15P3)]Z = 2
Mr = 1237.60Mo Kα radiation
Hexagonal, P63/mµ = 1.02 mm1
a = 17.2989 (3) ÅT = 296 K
c = 14.4545 (6) Å0.24 × 0.20 × 0.16 mm
V = 3746.02 (18) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
3157 independent reflections
Absorption correction: multi-scan
(North et al., 1968)
2098 reflections with I > 2σ(I)
Tmin = 0.792, Tmax = 0.854Rint = 0.048
42917 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.108H-atom parameters constrained
S = 1.07Δρmax = 0.52 e Å3
3157 reflectionsΔρmin = 0.35 e Å3
91 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
Pd10.13572 (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) top
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, º) top
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.

Experimental details

Crystal data
Chemical formula[Pd3Cl6(C30H42N15P3)]
Mr1237.60
Crystal system, space groupHexagonal, P63/m
Temperature (K)296
a, c (Å)17.2989 (3), 14.4545 (6)
V3)3746.02 (18)
Z2
Radiation typeMo Kα
µ (mm1)1.02
Crystal size (mm)0.24 × 0.20 × 0.16
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(North et al., 1968)
Tmin, Tmax0.792, 0.854
No. of measured, independent and
observed [I > 2σ(I)] reflections
42917, 3157, 2098
Rint0.048
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.108, 1.07
No. of reflections3157
No. of parameters91
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.52, 0.35

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Pd1—N32.027 (2)P1—N21.695 (2)
Pd1—Cl12.2642 (10)N2—N31.384 (3)
N3—Pd1—N3i86.36 (14)Cl1—Pd1—Cl1i88.95 (6)
N3—Pd1—Cl1178.26 (8)N1ii—P1—N1118.0 (2)
N3i—Pd1—Cl192.34 (8)N2i—P1—N2102.86 (17)
Symmetry codes: (i) x, y, z+3/2; (ii) y+1, xy+1, z.
 

References

First citationBruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChandrasekhar, V. & Nagendran, S. (2001). Chem. Soc. Rev. 30, 193–203.  Web of Science CrossRef CAS Google Scholar
First citationGallicano, K. D. & Paddock, N. L. (1982). Can. J. Chem. 60, 521–528.  CrossRef CAS Web of Science Google Scholar
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds