Bis{μ-2-[(dimethyl­amino)­meth­yl]benzene­seleno­lato}bis­[chloridopalladium(II)] dichloromethane hemisolvate

Chakravorty, T.; Singh, H.B.; Butcher, R.J.

doi:10.1107/S1600536811055322

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages m113-m114

doi:10.1107/S1600536811055322

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Bis{μ-2-[(dimethylamino)methyl]benzeneselenolato}bis[chloridopalladium(II)] dichloromethane hemisolvate

Tapash Chakravorty,^a Harkesh B. Singh ^a and Ray J. Butcher ^b ^*

^aDepartment of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India, and ^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: rbutcher99@yahoo.com

(Received 22 December 2011; accepted 23 December 2011; online 7 January 2012)

The asymmetric unit of the title compound, [Pd₂(C₉H₁₂NSe)₂Cl₂]·0.5CH₂Cl₂, contains two half-molecules, each lying on a twofold axis; each molecule is chiral and of the same enantiomer. This is only possible as the molecule has a hinged cis arrangement about the Pd²⁺ coordination spheres. For this hinged dimeric structure, the angles between the two coordination planes in each molecule are 15.02 (5) and 14.91 (5)°. This hinged cis arragement also allows the two molecules to form pairs linked by secondary interactions between the Pd and Se atoms [3.4307 (9) and 3.4317 (9) Å] of adjoining molecules, leading to an overall tetrameric structure. During the refinement stages, it was noticed that there were dichloromethane solvent molecules present disordered about a twofold axis. After unsuccessful attempts were made to model this, they were removed using SQUEEZE.

Related literature

For applications of organoselenide and organotelluride ligands in materials science, see: Morley et al. (2006 ); Ford et al. (2004 ). For structures of dimeric Se-bridged Pd derivatives, see: Nakata et al. (2009 ); Chakraborty et al. (2011 ); Oilunkaniemi et al. (1999 , 2001 ); Brown & Corrigan (2004 ); Dey et al. (2006 ) and for structures of dimeric Te-bridged Pd derivatives, see: Oilunkaniemi et al. (2000 ); Kaur et al. (2009 ); Dey et al. (2006). For the use of the SQUEEZE routine in PLATON, see: Spek (2009 ).

Experimental

Crystal data

[Pd₂(C₉H₁₂NSe)₂Cl₂]·0.5CH₂Cl₂
M_r = 752.47
Orthorhombic, P 2₁ 2₁ 2
a = 14.2119 (1) Å
b = 14.7895 (1) Å
c = 12.0968 (1) Å
V = 2542.59 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.60 mm⁻¹
T = 293 K
0.35 × 0.24 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.655, T_max = 1.000
22757 measured reflections
5323 independent reflections
4971 reflections with I > 2σ(I)
R_int = 0.073

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.131
S = 1.06
5323 reflections
240 parameters
H-atom parameters constrained
Δρ_max = 1.29 e Å⁻³
Δρ_min = −1.45 e Å⁻³
Absolute structure: Flack (1983 ), 2261 Friedel pairs
Flack parameter: 0.015 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5A—H5AA⋯Cl1Aⁱ	0.93	2.91	3.782 (10)	156
C7A—H7AA⋯Cl1Aⁱ	0.97	2.94	3.853 (8)	158
C9A—H9AC⋯Cl1A	0.96	2.79	3.325 (10)	116
C5B—H5BA⋯Cl1Bⁱⁱ	0.93	2.94	3.808 (11)	156
C8B—H8BB⋯Cl1B	0.96	2.80	3.347 (11)	117
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+1]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811055322/hg5157sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055322/hg5157Isup2.hkl

checkCIF report

Comment top

The coordination chemistry of transition metal complexes with both organoselenide and organotelluride ligands is a rapidly growing area due to the ability of the resulting complexes to find applications in materials science (Morley et al., 2006; Ford et al., 2004), and investigations of oxidation additive to low valent transition metal centers. In addition to this, organotellurium compounds have been used in catalytic carbon-carbon formation. Bridged dimers of palladium mediated by Se (Nakata et al., 2009; Chakraborty et al., 2011; Oilunkaniemi et al., 1999; Oilunkaniemi et al., 2001; Brown & Corrigan, 2004; Dey et al., 2006) or Te (Oilunkaniemi et al., 2000; Kaur et al., 2009; Dey et al., 2006) have been previously reported. Such dimers involving two square planar coordination spheres can adopt either a coplanar or hinged arrangement. The arrangement of the donor ligands with respect to the bridging plane can be cis or trans. In the case of a hinged cis arrangemnt the possibility of chirality exisits. While the majority of previously determined Se/Te bridged Pd dimeric structures are both coplanar and trans, there have been a small number which exhibit either a hinged or cis arrangment of ligands about the bridging plane (Kaur et al., 2009; Oilunkaniemi et al., 2000). However, in no previous case has this resulted in a chiral structure.

The title compound, bis[chlorido-(µ(Se)-2-dimethylaminomethylbenzeneselenolate)palladium(II)], C₁₈H₂₄Cl₂N₂Pd₂Se₂, crystallizes in the chiral orthorhombic space group, P2₁2₁2. The asymmetric unit contains 2 half molecules, each lying on a 2-fold axis and each molecule is chiral and of the same enantiomer. This is only possible as the molecule has a hinged cis arrangement about the Pd coordination spheres (Fig. 1). For this hinged dimeric structure the angles between the two coordination planes in each molecule are 15.02 (5) and 14.91 (5)° respectively. This hinged cis arragement also allows the two molecules to form pairs linked by secondary interactions between the Pd and Se of an adjoining molecule (Fig. 2) leading to a tetrameric overall structure. Apart from this the Pd—Se, Pd—Cl and Pd—N bond lengths are in the normal ranges.

Related literature top

For applications of organoselenide and organotelluride ligands in materials science, see: Morley et al. (2006); Ford et al. (2004). For Se-bridged dimeric Pd structures, see: Nakata et al. (2009); Chakraborty et al. (2011); Oilunkaniemi et al. (1999, 2001); Brown & Corrigan (2004); Dey et al. (2006) and for Te-bridged dimeric Pd structures, see: Oilunkaniemi et al. (2000); Kaur et al. (2009); Dey et al. (2006). For the use of the SQUEEZE routine in PLATON, see: Spek (2009).

Experimental top

The ligand and complex were prepared using previously reported methods (Chakraborty et al., 2011). Crystallization of the selenolate was done at ambient temperature from dichloromethane/hexane (2:1).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of one of the two molecules of the asymmetric unit showing the hinged cis arrangement of the two Pd coordination planes. The two halves of the molecule are related by 1 - x, 1 - y, z.
	Fig. 2. The association of two dimeric units into a tetramer via matching and complementary secondary interactions between the Pd and Se of adjoining units. These interactions are shown by dashed lines.
	Fig. 3. Showing the packing of the tetrameric units. Secondary interactions between Pd and Se shown by dashed lines.

Bis{µ-2-[(dimethylamino)methyl]benzeneselenolato}bis[chloridopalladium(II)] dichloromethane hemisolvate top

Crystal data top

[Pd₂(C₉H₁₂NSe)₂Cl₂]·0.5CH₂Cl₂	F(000) = 1444
M_r = 752.47	D_x = 1.966 Mg m⁻³
Orthorhombic, P2₁2₁2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 16933 reflections
a = 14.2119 (1) Å	θ = 4.7–77.4°
b = 14.7895 (1) Å	µ = 4.60 mm⁻¹
c = 12.0968 (1) Å	T = 293 K
V = 2542.59 (3) Å³	Prism, orange
Z = 4	0.35 × 0.24 × 0.12 mm

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	5323 independent reflections
Radiation source: fine-focus sealed tube	4971 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
Detector resolution: 10.5081 pixels mm^-1	θ_max = 26.8°, θ_min = 2.6°
ω scans	h = −17→17
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	k = −18→18
T_min = 0.655, T_max = 1.000	l = −15→14
22757 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.051	w = 1/[σ²(F_o²) + (0.0803P)² + 6.8337P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.131	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 1.29 e Å⁻³
5323 reflections	Δρ_min = −1.45 e Å⁻³
240 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0067 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2261 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.015 (13)

Crystal data top

[Pd₂(C₉H₁₂NSe)₂Cl₂]·0.5CH₂Cl₂	V = 2542.59 (3) Å³
M_r = 752.47	Z = 4
Orthorhombic, P2₁2₁2	Mo Kα radiation
a = 14.2119 (1) Å	µ = 4.60 mm⁻¹
b = 14.7895 (1) Å	T = 293 K
c = 12.0968 (1) Å	0.35 × 0.24 × 0.12 mm

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	5323 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	4971 reflections with I > 2σ(I)
T_min = 0.655, T_max = 1.000	R_int = 0.073
22757 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.131	Δρ_max = 1.29 e Å⁻³
S = 1.06	Δρ_min = −1.45 e Å⁻³
5323 reflections	Absolute structure: Flack (1983), 2261 Friedel pairs
240 parameters	Absolute structure parameter: 0.015 (13)
0 restraints

Special details top

Experimental. The structure of the Te analog was also determined, but at low temperature. This compound is isostructural and isomorphous with the Se compound but in this case the solvent was ordered. An Acta E submission for this structure has been made and it is currently under review (jj2116).

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	0.53556 (3)	0.38325 (3)	1.09852 (5)	0.03277 (16)
Pd2	0.37837 (4)	0.46542 (3)	0.40196 (5)	0.03435 (17)
Se1A	0.60568 (5)	0.52886 (5)	1.11898 (6)	0.0382 (2)
Se1B	0.53041 (5)	0.39888 (5)	0.38141 (6)	0.0396 (2)
Cl1A	0.44999 (17)	0.24995 (14)	1.0741 (3)	0.0633 (7)
Cl1B	0.23941 (16)	0.54777 (17)	0.4277 (3)	0.0681 (7)
N1A	0.6735 (4)	0.3189 (4)	1.0840 (6)	0.0423 (15)
N1B	0.3119 (5)	0.3330 (4)	0.4160 (6)	0.0450 (15)
C1A	0.6601 (5)	0.5140 (5)	0.9762 (7)	0.0373 (15)
C2A	0.6352 (6)	0.5673 (6)	0.8858 (7)	0.0481 (18)
H2AA	0.5904	0.6126	0.8934	0.058*
C3A	0.6788 (7)	0.5518 (7)	0.7820 (8)	0.056 (2)
H3AA	0.6617	0.5858	0.7205	0.067*
C4A	0.7474 (8)	0.4854 (7)	0.7735 (8)	0.062 (3)
H4AA	0.7769	0.4760	0.7058	0.074*
C5A	0.7725 (7)	0.4333 (7)	0.8620 (9)	0.058 (2)
H5AA	0.8198	0.3903	0.8540	0.070*
C6A	0.7280 (6)	0.4437 (6)	0.9648 (7)	0.0446 (18)
C7A	0.7490 (5)	0.3843 (6)	1.0628 (7)	0.0443 (17)
H7AA	0.8073	0.3520	1.0496	0.053*
H7AB	0.7576	0.4219	1.1277	0.053*
C8A	0.6919 (8)	0.2716 (7)	1.1902 (9)	0.064 (3)
H8AA	0.7536	0.2452	1.1884	0.096*
H8AB	0.6458	0.2249	1.2007	0.096*
H8AC	0.6882	0.3141	1.2500	0.096*
C9A	0.6742 (7)	0.2505 (7)	0.9954 (9)	0.060 (2)
H9AA	0.7369	0.2278	0.9859	0.090*
H9AB	0.6531	0.2775	0.9276	0.090*
H9AC	0.6329	0.2016	1.0149	0.090*
C1B	0.5136 (6)	0.3459 (5)	0.5257 (7)	0.0397 (16)
C2B	0.5680 (6)	0.3721 (6)	0.6158 (7)	0.0479 (18)
H2BA	0.6138	0.4166	0.6083	0.057*
C3B	0.5523 (7)	0.3301 (7)	0.7180 (8)	0.058 (2)
H3BA	0.5878	0.3469	0.7792	0.070*
C4B	0.4861 (8)	0.2656 (7)	0.7282 (9)	0.065 (3)
H4BA	0.4768	0.2382	0.7965	0.078*
C5B	0.4311 (7)	0.2390 (6)	0.6379 (8)	0.055 (2)
H5BA	0.3868	0.1932	0.6462	0.066*
C6B	0.4427 (7)	0.2813 (5)	0.5347 (8)	0.0466 (19)
C7B	0.3803 (7)	0.2593 (5)	0.4390 (8)	0.0490 (19)
H7BA	0.4187	0.2492	0.3738	0.059*
H7BB	0.3463	0.2039	0.4545	0.059*
C8B	0.2391 (7)	0.3300 (8)	0.5030 (9)	0.061 (3)
H8BA	0.2149	0.2696	0.5090	0.092*
H8BB	0.1889	0.3706	0.4843	0.092*
H8BC	0.2662	0.3478	0.5724	0.092*
C9B	0.2642 (8)	0.3146 (8)	0.3089 (9)	0.075 (3)
H9BA	0.2160	0.2699	0.3197	0.112*
H9BB	0.3093	0.2925	0.2564	0.112*
H9BC	0.2364	0.3693	0.2815	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0294 (2)	0.0285 (2)	0.0404 (3)	0.00255 (18)	−0.0012 (2)	0.00392 (19)
Pd2	0.0316 (3)	0.0303 (3)	0.0412 (3)	−0.00305 (18)	−0.0025 (2)	−0.0019 (2)
Se1A	0.0338 (3)	0.0395 (4)	0.0412 (4)	0.0011 (3)	−0.0012 (3)	−0.0027 (3)
Se1B	0.0422 (4)	0.0342 (4)	0.0424 (4)	−0.0013 (3)	0.0037 (3)	−0.0015 (3)
Cl1A	0.0511 (11)	0.0351 (9)	0.104 (2)	−0.0069 (8)	0.0006 (12)	0.0004 (10)
Cl1B	0.0410 (10)	0.0524 (12)	0.111 (2)	0.0080 (9)	0.0036 (12)	0.0005 (13)
N1A	0.034 (3)	0.037 (3)	0.056 (4)	0.013 (2)	0.000 (3)	0.003 (3)
N1B	0.043 (3)	0.040 (3)	0.052 (4)	−0.015 (3)	−0.003 (3)	−0.003 (3)
C1A	0.033 (3)	0.037 (4)	0.042 (4)	−0.001 (3)	0.010 (3)	−0.002 (3)
C2A	0.056 (4)	0.046 (4)	0.043 (4)	0.001 (3)	0.008 (4)	0.007 (3)
C3A	0.069 (6)	0.051 (5)	0.047 (5)	−0.007 (4)	0.006 (4)	0.004 (4)
C4A	0.070 (6)	0.063 (6)	0.052 (5)	−0.013 (5)	0.017 (5)	−0.006 (4)
C5A	0.047 (4)	0.052 (5)	0.075 (6)	0.000 (4)	0.017 (4)	−0.002 (4)
C6A	0.034 (4)	0.046 (4)	0.055 (5)	0.002 (3)	0.000 (3)	−0.003 (3)
C7A	0.028 (3)	0.051 (4)	0.053 (4)	0.010 (3)	−0.003 (3)	0.001 (4)
C8A	0.065 (6)	0.063 (6)	0.064 (6)	0.030 (5)	−0.005 (5)	0.012 (5)
C9A	0.057 (6)	0.051 (5)	0.071 (7)	0.020 (4)	0.009 (5)	−0.008 (4)
C1B	0.043 (4)	0.031 (3)	0.046 (4)	0.002 (3)	0.004 (3)	0.006 (3)
C2B	0.042 (4)	0.055 (4)	0.047 (5)	0.000 (3)	−0.006 (3)	0.006 (4)
C3B	0.055 (5)	0.070 (6)	0.049 (5)	0.011 (5)	−0.008 (4)	0.005 (4)
C4B	0.073 (7)	0.057 (5)	0.065 (6)	0.012 (5)	0.011 (5)	0.019 (5)
C5B	0.058 (5)	0.049 (4)	0.059 (5)	0.006 (4)	0.003 (4)	0.017 (4)
C6B	0.051 (5)	0.030 (3)	0.058 (5)	−0.001 (3)	0.009 (4)	−0.001 (3)
C7B	0.061 (5)	0.029 (3)	0.057 (5)	−0.009 (3)	0.006 (4)	−0.003 (3)
C8B	0.055 (5)	0.065 (6)	0.063 (6)	−0.022 (5)	0.011 (5)	0.001 (5)
C9B	0.077 (7)	0.086 (8)	0.062 (6)	−0.051 (6)	−0.008 (5)	−0.013 (6)

Geometric parameters (Å, º) top

Pd1—N1A	2.186 (6)	C5A—H5AA	0.9300
Pd1—Cl1A	2.335 (2)	C6A—C7A	1.505 (12)
Pd1—Se1A	2.3858 (9)	C7A—H7AA	0.9700
Pd1—Se1Aⁱ	2.4043 (8)	C7A—H7AB	0.9700
Pd1—Se1Bⁱⁱ	3.4307 (9)	C8A—H8AA	0.9600
Pd2—N1B	2.180 (6)	C8A—H8AB	0.9600
Pd2—Cl1B	2.341 (2)	C8A—H8AC	0.9600
Pd2—Se1B	2.3872 (9)	C9A—H9AA	0.9600
Pd2—Se1Bⁱ	2.4021 (8)	C9A—H9AB	0.9600
Pd2—Se1Aⁱⁱⁱ	3.4317 (9)	C9A—H9AC	0.9600
Se1A—C1A	1.905 (8)	C1B—C2B	1.391 (12)
Se1A—Pd1ⁱ	2.4043 (8)	C1B—C6B	1.393 (12)
Se1B—C1B	1.928 (8)	C2B—C3B	1.402 (13)
Se1B—Pd2ⁱ	2.4021 (8)	C2B—H2BA	0.9300
N1A—C7A	1.468 (11)	C3B—C4B	1.345 (15)
N1A—C9A	1.474 (12)	C3B—H3BA	0.9300
N1A—C8A	1.486 (12)	C4B—C5B	1.400 (15)
N1B—C8B	1.477 (12)	C4B—H4BA	0.9300
N1B—C7B	1.487 (12)	C5B—C6B	1.406 (12)
N1B—C9B	1.488 (12)	C5B—H5BA	0.9300
C1A—C2A	1.393 (11)	C6B—C7B	1.493 (13)
C1A—C6A	1.425 (11)	C7B—H7BA	0.9700
C2A—C3A	1.419 (12)	C7B—H7BB	0.9700
C2A—H2AA	0.9300	C8B—H8BA	0.9600
C3A—C4A	1.388 (15)	C8B—H8BB	0.9600
C3A—H3AA	0.9300	C8B—H8BC	0.9600
C4A—C5A	1.367 (15)	C9B—H9BA	0.9600
C4A—H4AA	0.9300	C9B—H9BB	0.9600
C5A—C6A	1.404 (13)	C9B—H9BC	0.9600

N1A—Pd1—Cl1A	95.12 (19)	C1A—C6A—C7A	119.0 (7)
N1A—Pd1—Se1A	91.53 (18)	N1A—C7A—C6A	112.2 (6)
Cl1A—Pd1—Se1A	173.08 (7)	N1A—C7A—H7AA	109.2
N1A—Pd1—Se1Aⁱ	172.88 (18)	C6A—C7A—H7AA	109.2
Cl1A—Pd1—Se1Aⁱ	91.99 (6)	N1A—C7A—H7AB	109.2
Se1A—Pd1—Se1Aⁱ	81.38 (3)	C6A—C7A—H7AB	109.2
N1A—Pd1—Se1Bⁱⁱ	97.4 (2)	H7AA—C7A—H7AB	107.9
Cl1A—Pd1—Se1Bⁱⁱ	99.90 (8)	N1A—C8A—H8AA	109.5
Se1A—Pd1—Se1Bⁱⁱ	81.06 (3)	N1A—C8A—H8AB	109.5
Se1Aⁱ—Pd1—Se1Bⁱⁱ	80.97 (3)	H8AA—C8A—H8AB	109.5
N1B—Pd2—Cl1B	95.2 (2)	N1A—C8A—H8AC	109.5
N1B—Pd2—Se1B	91.72 (19)	H8AA—C8A—H8AC	109.5
Cl1B—Pd2—Se1B	172.69 (7)	H8AB—C8A—H8AC	109.5
N1B—Pd2—Se1Bⁱ	172.78 (19)	N1A—C9A—H9AA	109.5
Cl1B—Pd2—Se1Bⁱ	91.97 (7)	N1A—C9A—H9AB	109.5
Se1B—Pd2—Se1Bⁱ	81.09 (3)	H9AA—C9A—H9AB	109.5
N1B—Pd2—Se1Aⁱⁱⁱ	97.4 (2)	N1A—C9A—H9AC	109.5
Cl1B—Pd2—Se1Aⁱⁱⁱ	100.11 (9)	H9AA—C9A—H9AC	109.5
Se1B—Pd2—Se1Aⁱⁱⁱ	81.17 (3)	H9AB—C9A—H9AC	109.5
Se1Bⁱ—Pd2—Se1Aⁱⁱⁱ	80.83 (3)	C2B—C1B—C6B	122.1 (8)
C1A—Se1A—Pd1	88.4 (2)	C2B—C1B—Se1B	121.8 (6)
C1A—Se1A—Pd1ⁱ	107.9 (2)	C6B—C1B—Se1B	116.0 (6)
Pd1—Se1A—Pd1ⁱ	97.39 (3)	C1B—C2B—C3B	118.7 (8)
C1B—Se1B—Pd2	87.8 (2)	C1B—C2B—H2BA	120.7
C1B—Se1B—Pd2ⁱ	108.2 (2)	C3B—C2B—H2BA	120.7
Pd2—Se1B—Pd2ⁱ	97.66 (3)	C4B—C3B—C2B	120.4 (9)
C7A—N1A—C9A	108.7 (7)	C4B—C3B—H3BA	119.8
C7A—N1A—C8A	109.4 (7)	C2B—C3B—H3BA	119.8
C9A—N1A—C8A	107.7 (7)	C3B—C4B—C5B	121.2 (9)
C7A—N1A—Pd1	112.5 (4)	C3B—C4B—H4BA	119.4
C9A—N1A—Pd1	111.3 (5)	C5B—C4B—H4BA	119.4
C8A—N1A—Pd1	107.1 (5)	C4B—C5B—C6B	120.2 (9)
C8B—N1B—C7B	107.6 (7)	C4B—C5B—H5BA	119.9
C8B—N1B—C9B	107.2 (8)	C6B—C5B—H5BA	119.9
C7B—N1B—C9B	109.0 (8)	C1B—C6B—C5B	117.3 (8)
C8B—N1B—Pd2	112.8 (6)	C1B—C6B—C7B	121.2 (8)
C7B—N1B—Pd2	112.9 (5)	C5B—C6B—C7B	121.5 (8)
C9B—N1B—Pd2	107.1 (6)	N1B—C7B—C6B	111.9 (7)
C2A—C1A—C6A	120.6 (7)	N1B—C7B—H7BA	109.2
C2A—C1A—Se1A	122.9 (6)	C6B—C7B—H7BA	109.2
C6A—C1A—Se1A	116.5 (6)	N1B—C7B—H7BB	109.2
C1A—C2A—C3A	119.5 (8)	C6B—C7B—H7BB	109.2
C1A—C2A—H2AA	120.2	H7BA—C7B—H7BB	107.9
C3A—C2A—H2AA	120.2	N1B—C8B—H8BA	109.5
C4A—C3A—C2A	119.1 (9)	N1B—C8B—H8BB	109.5
C4A—C3A—H3AA	120.5	H8BA—C8B—H8BB	109.5
C2A—C3A—H3AA	120.5	N1B—C8B—H8BC	109.5
C5A—C4A—C3A	121.6 (9)	H8BA—C8B—H8BC	109.5
C5A—C4A—H4AA	119.2	H8BB—C8B—H8BC	109.5
C3A—C4A—H4AA	119.2	N1B—C9B—H9BA	109.5
C4A—C5A—C6A	121.0 (9)	N1B—C9B—H9BB	109.5
C4A—C5A—H5AA	119.5	H9BA—C9B—H9BB	109.5
C6A—C5A—H5AA	119.5	N1B—C9B—H9BC	109.5
C5A—C6A—C1A	118.1 (8)	H9BA—C9B—H9BC	109.5
C5A—C6A—C7A	123.0 (8)	H9BB—C9B—H9BC	109.5

N1A—Pd1—Se1A—C1A	60.9 (3)	Pd1—Se1A—C1A—C2A	113.8 (7)
Cl1A—Pd1—Se1A—C1A	−103.4 (7)	Pd1ⁱ—Se1A—C1A—C2A	16.6 (7)
Se1Aⁱ—Pd1—Se1A—C1A	−119.7 (2)	Pd1—Se1A—C1A—C6A	−65.4 (6)
Se1Bⁱⁱ—Pd1—Se1A—C1A	158.1 (2)	Pd1ⁱ—Se1A—C1A—C6A	−162.6 (5)
N1A—Pd1—Se1A—Pd1ⁱ	168.8 (2)	C6A—C1A—C2A—C3A	−0.7 (13)
Cl1A—Pd1—Se1A—Pd1ⁱ	4.5 (7)	Se1A—C1A—C2A—C3A	−179.9 (7)
Se1Aⁱ—Pd1—Se1A—Pd1ⁱ	−11.87 (5)	C1A—C2A—C3A—C4A	−1.7 (14)
Se1Bⁱⁱ—Pd1—Se1A—Pd1ⁱ	−94.00 (3)	C2A—C3A—C4A—C5A	1.3 (15)
N1B—Pd2—Se1B—C1B	−60.7 (3)	C3A—C4A—C5A—C6A	1.5 (16)
Cl1B—Pd2—Se1B—C1B	101.4 (7)	C4A—C5A—C6A—C1A	−3.9 (14)
Se1Bⁱ—Pd2—Se1B—C1B	120.0 (2)	C4A—C5A—C6A—C7A	176.2 (9)
Se1Aⁱⁱⁱ—Pd2—Se1B—C1B	−157.9 (2)	C2A—C1A—C6A—C5A	3.4 (12)
N1B—Pd2—Se1B—Pd2ⁱ	−168.8 (2)	Se1A—C1A—C6A—C5A	−177.4 (7)
Cl1B—Pd2—Se1B—Pd2ⁱ	−6.7 (7)	C2A—C1A—C6A—C7A	−176.6 (7)
Se1Bⁱ—Pd2—Se1B—Pd2ⁱ	11.94 (5)	Se1A—C1A—C6A—C7A	2.6 (10)
Se1Aⁱⁱⁱ—Pd2—Se1B—Pd2ⁱ	93.95 (3)	C9A—N1A—C7A—C6A	70.6 (9)
Cl1A—Pd1—N1A—C7A	163.2 (5)	C8A—N1A—C7A—C6A	−172.0 (7)
Se1A—Pd1—N1A—C7A	−14.9 (6)	Pd1—N1A—C7A—C6A	−53.1 (8)
Se1Aⁱ—Pd1—N1A—C7A	−20 (2)	C5A—C6A—C7A—N1A	−105.4 (9)
Se1Bⁱⁱ—Pd1—N1A—C7A	−96.1 (5)	C1A—C6A—C7A—N1A	74.7 (10)
Cl1A—Pd1—N1A—C9A	41.0 (6)	Pd2—Se1B—C1B—C2B	−112.6 (7)
Se1A—Pd1—N1A—C9A	−137.1 (6)	Pd2ⁱ—Se1B—C1B—C2B	−15.2 (7)
Se1Aⁱ—Pd1—N1A—C9A	−142.1 (15)	Pd2—Se1B—C1B—C6B	66.1 (6)
Se1Bⁱⁱ—Pd1—N1A—C9A	141.7 (6)	Pd2ⁱ—Se1B—C1B—C6B	163.5 (6)
Cl1A—Pd1—N1A—C8A	−76.5 (6)	C6B—C1B—C2B—C3B	1.8 (13)
Se1A—Pd1—N1A—C8A	105.4 (6)	Se1B—C1B—C2B—C3B	−179.5 (6)
Se1Aⁱ—Pd1—N1A—C8A	100.4 (16)	C1B—C2B—C3B—C4B	0.2 (14)
Se1Bⁱⁱ—Pd1—N1A—C8A	24.2 (6)	C2B—C3B—C4B—C5B	−0.3 (15)
Cl1B—Pd2—N1B—C8B	−39.8 (7)	C3B—C4B—C5B—C6B	−1.6 (15)
Se1B—Pd2—N1B—C8B	137.9 (6)	C2B—C1B—C6B—C5B	−3.6 (12)
Se1Bⁱ—Pd2—N1B—C8B	144.0 (14)	Se1B—C1B—C6B—C5B	177.7 (6)
Se1Aⁱⁱⁱ—Pd2—N1B—C8B	−140.7 (6)	C2B—C1B—C6B—C7B	175.2 (8)
Cl1B—Pd2—N1B—C7B	−162.1 (5)	Se1B—C1B—C6B—C7B	−3.5 (11)
Se1B—Pd2—N1B—C7B	15.6 (6)	C4B—C5B—C6B—C1B	3.4 (13)
Se1Bⁱ—Pd2—N1B—C7B	22 (2)	C4B—C5B—C6B—C7B	−175.4 (9)
Se1Aⁱⁱⁱ—Pd2—N1B—C7B	97.0 (6)	C8B—N1B—C7B—C6B	−74.1 (9)
Cl1B—Pd2—N1B—C9B	77.9 (7)	C9B—N1B—C7B—C6B	170.0 (7)
Se1B—Pd2—N1B—C9B	−104.4 (7)	Pd2—N1B—C7B—C6B	51.1 (8)
Se1Bⁱ—Pd2—N1B—C9B	−98.3 (17)	C1B—C6B—C7B—N1B	−72.6 (10)
Se1Aⁱⁱⁱ—Pd2—N1B—C9B	−23.1 (7)	C5B—C6B—C7B—N1B	106.2 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5A—H5AA···Cl1A^iv	0.93	2.91	3.782 (10)	156
C7A—H7AA···Cl1A^iv	0.97	2.94	3.853 (8)	158
C9A—H9AC···Cl1A	0.96	2.79	3.325 (10)	116
C5B—H5BA···Cl1B^v	0.93	2.94	3.808 (11)	156
C8B—H8BB···Cl1B	0.96	2.80	3.347 (11)	117

Symmetry codes: (iv) x+1/2, −y+1/2, −z+2; (v) −x+1/2, y−1/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Pd₂(C₉H₁₂NSe)₂Cl₂]·0.5CH₂Cl₂
M_r	752.47
Crystal system, space group	Orthorhombic, P2₁2₁2
Temperature (K)	293
a, b, c (Å)	14.2119 (1), 14.7895 (1), 12.0968 (1)
V (Å³)	2542.59 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.60
Crystal size (mm)	0.35 × 0.24 × 0.12

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)
T_min, T_max	0.655, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	22757, 5323, 4971
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.634

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.131, 1.06
No. of reflections	5323
No. of parameters	240
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.29, −1.45
Absolute structure	Flack (1983), 2261 Friedel pairs
Absolute structure parameter	0.015 (13)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5A—H5AA···Cl1Aⁱ	0.93	2.91	3.782 (10)	156.2
C7A—H7AA···Cl1Aⁱ	0.97	2.94	3.853 (8)	157.9
C9A—H9AC···Cl1A	0.96	2.79	3.325 (10)	116.1
C5B—H5BA···Cl1Bⁱⁱ	0.93	2.94	3.808 (11)	155.9
C8B—H8BB···Cl1B	0.96	2.80	3.347 (11)	116.9

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

Acknowledgements

HBS acknowledges the DST, New Delhi, for financial support. TC acknowledges the CSIR, New Delhi, for a fellowship. RJB acknowledges the NSF–MRI program (grant CHE-0619278) for funds to purchase the diffractometer.

References

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Volume 68| Part 2| February 2012| Pages m113-m114

doi:10.1107/S1600536811055322

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

Bis{μ-2-[(di­methyl­amino)­meth­yl]benzene­seleno­lato}bis­­[chloridopalladium(II)] di­chloro­methane hemisolvate

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Experimental

Crystal data

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Refinement

Supporting information

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metal-organic compounds

Bis{μ-2-[(dimethylamino)methyl]benzeneselenolato}bis[chloridopalladium(II)] dichloromethane hemisolvate