Dichlorido(4,7-diaza-1-azoniacyclo­nonane-κ2N4,N7)palladium(II) p-toluene­sulfonate

Anthony, T.A.; Arman, H.D.; Walmsley, J.A.

doi:10.1107/S1600536810016533

Volume 66
Part 6
Pages m638-m639
June 2010

Received 23 April 2010
Accepted 5 May 2010
Online 12 May 2010

Key indicators
Single-crystal X-ray study
T = 98 K
Mean (C-C) = 0.005 Å
R = 0.029
wR = 0.067
Data-to-parameter ratio = 18.2
Details

Dichlorido(4,7-diaza-1-azoniacyclononane-²N⁴,N⁷)palladium(II) p-toluenesulfonate

Timothy A. Anthony,^a Hadi D. Arman ^a ^* and Judith A. Walmsley ^a ^*

^aDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA
Correspondence e-mail: hadi.arman@utsa.edu, judith.walmsley@utsa.edu

The title compound, [PdCl₂(C₆H₁₆N₃)](C₇H₇SO₃), consists of a Pd^II atom bonded to two N atoms of the 1,4,7-triazacyclononane (TACN) ligand and two chloride ions, which define a distorted square-planar geometry. The third N atom of the TACN ligand is protonated and hydrogen bonds to the p-toluenesulfonate anion. The Cl-Pd-Cl angle is larger than the N-Pd-N angle. The packing is dominated by layers, which are formed by the criss-crossing of two different hydrogen-bonded chains. One chain is composed of hydrogen-bonded Pd(TACNH)Cl₂⁺ cations, while the second is formed through hydrogen bonding between the p-toluenesulfonate anion and the Pd(TACNH)Cl₂⁺ cation.

Related literature

For background to complexes of Pd^II and Pt^II with 1,4,7-triazacyclononane (TACN), see: McAuley & Whitcombe (1988); Blake et al. (1988, 1993); Margulis & Zompa (1992); Hunter et al. (1988); Davies et al. (2000). For the synthesis of TACN, see: Kang & Jo (2003). For Pd-N and Pd-Cl bond distances in Pd(en)Cl₂, see: Iball et al. (1975).

Experimental

Crystal data

[PdCl₂(C₆H₁₆N₃)](C₇H₇O₃S)
M_r = 478.70
Triclinic, $[P \overline 1]$
a = 6.6663 (11) Å
b = 7.0023 (11) Å
c = 19.646 (3) Å
= 92.149 (3)°
= 92.301 (3)°
= 103.084 (4)°
V = 891.5 (2) Å³
Z = 2
Mo K radiation
= 1.47 mm^-1
T = 98 K
0.39 × 0.25 × 0.14 mm

Data collection

Rigaku AFC12 Kappa goniometer diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) T_min = 0.839, T_max = 1.000
6224 measured reflections
3998 independent reflections
3941 reflections with I > 2(I)
R_int = 0.018

Refinement

R[F² > 2(F²)] = 0.029
wR(F²) = 0.067
S = 1.00
3998 reflections
220 parameters
H atoms treated by a mixture of independent and constrained refinement
_max = 0.62 e Å^-3
_min = -0.98 e Å^-3

Table 1
Selected geometric parameters (Å, °)

Pd1-N1	2.030 (2)
Pd1-N2	2.060 (2)
Pd1-Cl1	2.3053 (8)
Pd1-Cl2	2.3115 (7)

N1-Pd1-N2	82.71 (9)
Cl1-Pd1-Cl2	94.02 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
N1-H1aO1ⁱ	0.82 (6)	2.05 (6)	2.833 (3)	159 (6)
N2-H2aCl1ⁱⁱ	0.79 (5)	2.66 (6)	3.365 (2)	149 (5)
N3-H3aO2	0.75 (6)	2.04 (6)	2.743 (3)	156 (6)
N3-H3dCl2ⁱⁱⁱ	0.84 (5)	2.31 (6)	3.136 (3)	171 (5)
Symmetry codes: (i) x+1, y+1, z; (ii) x-1, y, z; (iii) x, y-1, z.

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: publCIF (Westrip, 2010).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2666 ).

Acknowledgements

Support from the Department of Chemistry at The University of Texas is gratefully acknowledged.

References

Blake, A. J., Gordon, L. M., Holder, A. J., Hyde, T. I., Reid, G. & Schröder, M. (1988). J. Chem. Soc. Chem. Commun. pp. 1452-1454..
Blake, A. J., Holder, A. J., Roberts, Y. V. & Schroder, M. (1993). J. Chem. Soc. Chem. Commun. pp. 260-262.
Davies, M. S., Fenton, R. R., Huq, F., Ling, E. C. H. & Hambley, T. W. (2000). Aust. J. Chem. 53, 451-456.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Hunter, G., McAuley, A. & Whitcombe, T. W. (1988). Inorg. Chem. 27, 2634-2639.
Iball, J., MacDougall, M. & Scrimgeour, S. (1975). Acta Cryst. B31, 1672-1674.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
Kang, J. & Jo, J. H. (2003). Bull. Korean Chem. Soc. 24, 1403-1406.
Margulis, T. N. & Zompa, L. J. (1992). Inorg. Chim. Acta, 201, 61-67.
McAuley, A. & Whitcombe, T. W. (1988). Inorg. Chem. 27, 3090-3099.
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Westrip, S. P. (2010). J. Appl. Cryst. 43. Submitted.

metal-organic compounds

Dichlorido(4,7-diaza-1-azoniacyclononane-2N4,N7)palladium(II) p-toluenesulfonate