[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)]

Yun, S.Y.; Lee, S.W.

doi:10.1107/S1600536808023167

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page m1084

doi:10.1107/S1600536808023167

Open

access

[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)]

Sung Yol Yun ^a and Soon W. Lee ^a ^*

^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 ); Gallicano & Paddock (1982 ).

Experimental

Crystal data

[Pd₃Cl₆(C₃₀H₄₂N₁₅P₃)]
M_r = 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 ) 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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.108
S = 1.07
3157 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −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 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

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

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

checkCIF report

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.

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

	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.

[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)] top

Crystal data top

[Pd₃Cl₆(C₃₀H₄₂N₁₅P₃)]	D_x = 1.097 Mg m⁻³
M_r = 1237.60	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₃/m	Cell parameters from 9849 reflections
Hall symbol: -P6c	θ = 2.4–27.2°
a = 17.2989 (3) Å	µ = 1.02 mm⁻¹
c = 14.4545 (6) Å	T = 296 K
V = 3746.02 (18) Å³	Block, yellow
Z = 2	0.24 × 0.20 × 0.16 mm
F(000) = 1224

Data collection top

Bruker SMART CCD area-detector diffractometer	3157 independent reflections
Radiation source: sealed tube	2098 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ϕ and ω scans	θ_max = 28.3°, θ_min = 3.6°
Absorption correction: multi-scan (North et al., 1968)	h = −23→22
T_min = 0.792, T_max = 0.854	k = −19→22
42917 measured reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0477P)² + 1.7582P] where P = (F_o² + 2F_c²)/3
3157 reflections	(Δ/σ)_max = 0.002
91 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Pd₃Cl₆(C₃₀H₄₂N₁₅P₃)]	Z = 2
M_r = 1237.60	Mo Kα radiation
Hexagonal, P6₃/m	µ = 1.02 mm⁻¹
a = 17.2989 (3) Å	T = 296 K
c = 14.4545 (6) Å	0.24 × 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)
T_min = 0.792, T_max = 0.854	R_int = 0.048
42917 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.07	Δρ_max = 0.52 e Å⁻³
3157 reflections	Δρ_min = −0.35 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Pd1	0.13572 (2)	0.37375 (2)	0.7500	0.05476 (14)
Cl1	0.02844 (7)	0.32969 (8)	0.64026 (8)	0.0961 (3)
P1	0.31769 (7)	0.56802 (7)	0.7500	0.0438 (2)
N1	0.2362 (2)	0.5861 (2)	0.7500	0.0472 (7)
N2	0.30675 (15)	0.50221 (15)	0.84168 (15)	0.0503 (5)
C1	0.3607 (2)	0.5175 (2)	0.9179 (2)	0.0697 (9)
C2	0.3213 (3)	0.4397 (3)	0.9672 (3)	0.0873 (12)
H2	0.3425	0.4290	1.0220	0.105*
N3	0.23411 (17)	0.41658 (16)	0.84595 (17)	0.0573 (6)
C3	0.2439 (2)	0.3792 (2)	0.9210 (3)	0.0743 (10)
C4	0.4433 (3)	0.6016 (3)	0.9398 (3)	0.1093 (17)
H4A	0.4555	0.6442	0.8914	0.164*
H4B	0.4921	0.5904	0.9449	0.164*
H4C	0.4359	0.6249	0.9974	0.164*
C5	0.1818 (3)	0.2838 (3)	0.9456 (4)	0.121 (2)
H5A	0.1345	0.2576	0.9008	0.181*
H5B	0.1570	0.2805	1.0058	0.181*
H5C	0.2139	0.2518	0.9458	0.181*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0519 (2)	0.0567 (2)	0.05085 (19)	0.02349 (16)	0.000	0.000
Cl1	0.0739 (6)	0.1049 (8)	0.0898 (7)	0.0300 (6)	−0.0295 (5)	−0.0085 (6)
P1	0.0508 (6)	0.0488 (6)	0.0333 (4)	0.0259 (5)	0.000	0.000
N1	0.0495 (18)	0.0505 (19)	0.0375 (15)	0.0218 (15)	0.000	0.000
N2	0.0538 (14)	0.0508 (13)	0.0433 (11)	0.0240 (12)	−0.0024 (10)	0.0062 (9)
C1	0.071 (2)	0.072 (2)	0.0544 (17)	0.0276 (18)	−0.0132 (15)	0.0103 (15)
C2	0.088 (3)	0.080 (2)	0.073 (2)	0.026 (2)	−0.019 (2)	0.0274 (19)
N3	0.0636 (16)	0.0503 (14)	0.0518 (13)	0.0238 (12)	−0.0023 (11)	0.0097 (10)
C3	0.074 (2)	0.064 (2)	0.068 (2)	0.0219 (18)	−0.0088 (17)	0.0191 (16)
C4	0.101 (3)	0.095 (3)	0.072 (2)	0.005 (2)	−0.041 (2)	0.024 (2)
C5	0.117 (4)	0.079 (3)	0.122 (4)	0.016 (3)	−0.028 (3)	0.047 (3)

Geometric parameters (Å, º) top

Pd1—N3	2.027 (2)	C1—C4	1.476 (5)
Pd1—N3ⁱ	2.027 (2)	C2—C3	1.389 (5)
Pd1—Cl1	2.2642 (10)	C2—H2	0.9300
Pd1—Cl1ⁱ	2.2641 (10)	N3—C3	1.317 (4)
P1—N1ⁱⁱ	1.557 (3)	C3—C5	1.494 (5)
P1—N1	1.589 (3)	C4—H4A	0.9600
P1—N2ⁱ	1.695 (2)	C4—H4B	0.9600
P1—N2	1.695 (2)	C4—H4C	0.9600
N1—P1ⁱⁱⁱ	1.557 (3)	C5—H5A	0.9600
N2—C1	1.381 (4)	C5—H5B	0.9600
N2—N3	1.384 (3)	C5—H5C	0.9600
C1—C2	1.367 (5)

N3—Pd1—N3ⁱ	86.36 (14)	C1—C2—H2	126.0
N3—Pd1—Cl1	178.26 (8)	C3—C2—H2	126.0
N3ⁱ—Pd1—Cl1	92.34 (8)	C3—N3—N2	107.0 (2)
N3—Pd1—Cl1ⁱ	92.34 (8)	C3—N3—Pd1	132.5 (2)
N3ⁱ—Pd1—Cl1ⁱ	178.26 (8)	N2—N3—Pd1	120.51 (16)
Cl1—Pd1—Cl1ⁱ	88.95 (6)	N3—C3—C2	109.7 (3)
N1ⁱⁱ—P1—N1	118.0 (2)	N3—C3—C5	122.7 (3)
N1ⁱⁱ—P1—N2ⁱ	108.78 (11)	C2—C3—C5	127.4 (3)
N1—P1—N2ⁱ	108.66 (11)	C1—C4—H4A	109.5
N1ⁱⁱ—P1—N2	108.78 (11)	C1—C4—H4B	109.5
N1—P1—N2	108.66 (11)	H4A—C4—H4B	109.5
N2ⁱ—P1—N2	102.86 (17)	C1—C4—H4C	109.5
P1ⁱⁱⁱ—N1—P1	122.0 (2)	H4A—C4—H4C	109.5
C1—N2—N3	109.5 (2)	H4B—C4—H4C	109.5
C1—N2—P1	131.1 (2)	C3—C5—H5A	109.5
N3—N2—P1	119.37 (17)	C3—C5—H5B	109.5
C2—C1—N2	105.7 (3)	H5A—C5—H5B	109.5
C2—C1—C4	128.3 (3)	C3—C5—H5C	109.5
N2—C1—C4	126.0 (3)	H5A—C5—H5C	109.5
C1—C2—C3	108.1 (3)	H5B—C5—H5C	109.5

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

Experimental details

Crystal data
Chemical formula	[Pd₃Cl₆(C₃₀H₄₂N₁₅P₃)]
M_r	1237.60
Crystal system, space group	Hexagonal, P6₃/m
Temperature (K)	296
a, c (Å)	17.2989 (3), 14.4545 (6)
V (Å³)	3746.02 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.24 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (North et al., 1968)
T_min, T_max	0.792, 0.854
No. of measured, independent and observed [I > 2σ(I)] reflections	42917, 3157, 2098
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.108, 1.07
No. of reflections	3157
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.35

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

Selected geometric parameters (Å, º) top

Pd1—N3	2.027 (2)	P1—N2	1.695 (2)
Pd1—Cl1	2.2642 (10)	N2—N3	1.384 (3)

N3—Pd1—N3ⁱ	86.36 (14)	Cl1—Pd1—Cl1ⁱ	88.95 (6)
N3—Pd1—Cl1	178.26 (8)	N1ⁱⁱ—P1—N1	118.0 (2)
N3ⁱ—Pd1—Cl1	92.34 (8)	N2ⁱ—P1—N2	102.86 (17)

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

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chandrasekhar, V. & Nagendran, S. (2001). Chem. Soc. Rev. 30, 193–203. Web of Science CrossRef CAS Google Scholar
Gallicano, K. D. & Paddock, N. L. (1982). Can. J. Chem. 60, 521–528. CrossRef CAS Web of Science Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, 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.