trans-Chloro­methyl­dipyridine­palladium(II)

Owen, G.R.; Haddow, M.F.

doi:10.1107/S1600536805037268

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 12| December 2005| Pages m2651-m2652

https://doi.org/10.1107/S1600536805037268

trans-Chloromethyldipyridinepalladium(II)

Gareth R. Owen ^a ^* and Mairi F. Haddow ^a

^aSchool of Chemistry, Cantocks Close, University of Bristol, Bristol BS8 1TS, England
^*Correspondence e-mail: gareth.owen@bris.ac.uk

(Received 20 September 2005; accepted 14 November 2005; online 19 November 2005)

The title compound, [Pd(CH₃)Cl(C₅H₅N)₂], has been synthesized by the reaction of [PdMeCl(COD)] (COD is 1,5-cyclooctadiene) with pyridine in dichloromethane; it is square-planar. The crystal structure features dipole–dipole and π stacking interactions.

Comment

trans-[Pd(pyridine)₂(Me)Cl], (I), was prepared by addition of an excess of pyridine to [PdMeCl(COD)] (COD is 1,5-cyclooctadiene). Fig. 1 shows the molecular geometry in the crystal structure and the atom-labelling scheme. The crystal structure comprises ordered individual square-planar molecules of trans-[Pd(pyridine)₂(Me)Cl] in a general position; the torsion angles C2—N1—Pd1—C1 and C7—N2—Pd1—C1 are 60.31 (13) and 54.71 (13)°, respectively. The angle between the planes of the pyridine rings is 67.33 (5)°.

Selected geometric parameters are given in Table 1. The bond lengths are in the usual range for Pd^II—C,Cl,N (Allen et al., 1987 ). The molecules in the crystal structure are packed in pairs with a Pd⋯Pd distance of 3.7731 (3) Å. In these pairs, the methyl ligand sits above the chloride ligand and vice versa in each case, which may reflect a dipole–dipole interaction between the two molecules (see Fig. 2). Some π stacking [interplanar distance of 3.403 (3) Å] occurs between the pyridine rings in adjacent pairs (see Fig. 3), with the rings offset by about one ring width.

The crystal structure is not isostructural with either [M(pyridine)₂Cl₂] where M = Pd (Viossat et al., 1993 ) or Pt (Colamarino & Orioli, 1975 ).

Figure 1
The molecular structure with the atom-labelling scheme. Displacement ellipsoids are shown at the 50% probability level, with H atoms represented as spheres of arbitrary size.

Figure 2
Pair of molecules within the crystal structure. H atoms have been omitted for clarity.

Figure 3
The π stacking in the crystal structure.

Experimental

A round-bottomed flask was charged with [PdMeCl(COD)] (0.100 g, 0.378 mmol) and CH₂Cl₂ (20 ml). Pyridine (0.15 ml, 1.833 mmol) was added to the solution and the mixture was stirred for 1 h. Hexane (50 ml) was added to the mixture and the volume was reduced to ca 20 ml. The resulting white solid was isolated by filtration, washed with two portions of diethyl ether (2 × 20 ml) and dried under vacuum to give a white solid (1.030 g, 0.327 mmol, 87%). A pale-yellow crystal of irregular shape was selected. IR (cm⁻¹, powder film): 1603 (s, pyridine). ¹H NMR (CDCl₃): δ 8.80 (m, 4H, o-pyridine), 7.69 (m, 2H, p-pyridine), 7.27 (m, 4H, m-pyridine), 0.73 (s, 3H, Pd—CH₃).

Crystal data

[Pd(CH₃)Cl(C₅H₅N)₂]
M_r = 315.08
Monoclinic, C 2/c
a = 13.2867 (9) Å
b = 11.9185 (8) Å
c = 16.2352 (10) Å
β = 109.5030 (10)°
V = 2423.5 (3) Å³
Z = 8
D_x = 1.727 Mg m⁻³
Mo Kα radiation
Cell parameters from 157 reflections
θ = 2.4–27.5°
μ = 1.72 mm⁻¹
T = 173 (2) K
Irregular block, pale yellow
0.40 × 0.30 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.583, T_max = 0.710
12619 measured reflections
2785 independent reflections
2555 reflections with I > 2σ(I)
R_int = 0.030
θ_max = 27.5°
h = −17 → 16
k = −15 → 15
l = −19 → 21

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.052
S = 1.29
2785 reflections
137 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0245P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Pd1—N1	2.0441 (13)
Pd1—C1	2.0457 (17)
Pd1—N2	2.0484 (13)
Pd1—Cl2	2.4612 (4)

N1—Pd1—C1	90.58 (6)
N1—Pd1—N2	177.92 (5)
C1—Pd1—N2	88.24 (6)
N1—Pd1—Cl2	90.15 (4)
C1—Pd1—Cl2	178.55 (5)
N2—Pd1—Cl2	90.99 (4)

Cl2—Pd1—N1—C6	56.97 (12)
C1—Pd1—N1—C2	60.31 (13)

H atoms were treated as riding, with C—H distances of 0.95 and 0.98Å and with U_iso(H) values of 1.2 and 1.5 times U_eq(C) for aromatic and methyl H atoms, respectively.

Data collection: SMART (Bruker, 1998 ); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805037268/bv6036sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805037268/bv6036Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

trans-Chloromethyldipyridinepalladium(II) top

Crystal data top

[Pd(CH₃)Cl(C₅H₅N)₂]	F(000) = 1248
M_r = 315.08	D_x = 1.727 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 157 reflections
a = 13.2867 (9) Å	θ = 2.4–27.5°
b = 11.9185 (8) Å	µ = 1.72 mm⁻¹
c = 16.2352 (10) Å	T = 173 K
β = 109.503 (1)°	Irregular block, pale yellow
V = 2423.5 (3) Å³	0.40 × 0.30 × 0.20 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	2785 independent reflections
Radiation source: fine-focus sealed tube	2555 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 8.2 pixels mm^-1	θ_max = 27.5°, θ_min = 2.4°
φ and ω scans	h = −17→16
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→15
T_min = 0.583, T_max = 0.710	l = −19→21
12619 measured reflections

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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.052	H-atom parameters constrained
S = 1.29	w = 1/[σ²(F_o²) + (0.0245P)²] where P = (F_o² + 2F_c²)/3
2785 reflections	(Δ/σ)_max = 0.001
137 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.74 e Å⁻³

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	0.062581 (9)	0.008712 (9)	0.372793 (8)	0.01997 (6)
Cl2	0.23773 (3)	−0.04033 (3)	0.36210 (3)	0.02563 (10)
N1	0.10037 (11)	0.17528 (11)	0.37603 (8)	0.0223 (3)
N2	0.02377 (11)	−0.15749 (10)	0.37380 (8)	0.0217 (3)
C1	−0.08206 (13)	0.04720 (14)	0.38455 (10)	0.0246 (3)
H1A	−0.1394	0.0220	0.3322	0.037*
H1B	−0.0872	0.1286	0.3910	0.037*
H1C	−0.0888	0.0095	0.4361	0.037*
C2	0.10611 (14)	0.24128 (14)	0.44480 (11)	0.0278 (4)
H2	0.0854	0.2113	0.4909	0.033*
C3	0.14110 (14)	0.35124 (14)	0.45058 (13)	0.0339 (4)
H3	0.1460	0.3953	0.5005	0.041*
C4	0.16875 (15)	0.39606 (14)	0.38265 (14)	0.0365 (4)
H4	0.1926	0.4715	0.3852	0.044*
C5	0.16141 (14)	0.33025 (14)	0.31124 (13)	0.0330 (4)
H5	0.1791	0.3598	0.2635	0.040*
C6	0.12756 (13)	0.21961 (13)	0.31028 (11)	0.0271 (4)
H6	0.1235	0.1738	0.2614	0.032*
C7	−0.06616 (13)	−0.20216 (13)	0.31811 (11)	0.0249 (3)
H7	−0.1147	−0.1547	0.2764	0.030*
C8	−0.09049 (14)	−0.31500 (13)	0.31948 (12)	0.0301 (4)
H8	−0.1546	−0.3443	0.2792	0.036*
C9	−0.01998 (15)	−0.38495 (14)	0.38043 (12)	0.0332 (4)
H9	−0.0351	−0.4626	0.3826	0.040*
C10	0.07253 (14)	−0.33933 (14)	0.43770 (12)	0.0311 (4)
H10	0.1219	−0.3852	0.4802	0.037*
C11	0.09239 (14)	−0.22639 (14)	0.43250 (11)	0.0260 (4)
H11	0.1566	−0.1958	0.4716	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.02057 (9)	0.01871 (8)	0.02094 (9)	−0.00136 (4)	0.00736 (6)	−0.00087 (4)
Cl2	0.0216 (2)	0.0274 (2)	0.0272 (2)	−0.00200 (15)	0.00724 (16)	−0.00500 (15)
N1	0.0211 (7)	0.0210 (6)	0.0253 (7)	−0.0023 (5)	0.0087 (6)	−0.0027 (5)
N2	0.0200 (7)	0.0218 (6)	0.0243 (7)	0.0001 (5)	0.0086 (5)	0.0008 (5)
C1	0.0240 (8)	0.0251 (8)	0.0260 (8)	0.0010 (6)	0.0100 (7)	0.0030 (6)
C2	0.0301 (9)	0.0269 (8)	0.0281 (9)	0.0009 (7)	0.0120 (7)	−0.0032 (7)
C3	0.0327 (10)	0.0262 (8)	0.0441 (11)	−0.0033 (7)	0.0143 (8)	−0.0117 (7)
C4	0.0312 (10)	0.0202 (8)	0.0626 (13)	−0.0029 (7)	0.0215 (9)	−0.0034 (8)
C5	0.0313 (10)	0.0287 (8)	0.0452 (11)	0.0007 (7)	0.0213 (8)	0.0063 (7)
C6	0.0271 (9)	0.0278 (8)	0.0280 (9)	−0.0005 (7)	0.0114 (7)	−0.0007 (7)
C7	0.0215 (8)	0.0251 (8)	0.0274 (8)	−0.0002 (6)	0.0075 (7)	0.0020 (6)
C8	0.0240 (9)	0.0272 (8)	0.0382 (10)	−0.0047 (7)	0.0093 (8)	−0.0035 (7)
C9	0.0336 (10)	0.0221 (8)	0.0481 (11)	−0.0015 (7)	0.0192 (8)	0.0015 (7)
C10	0.0310 (10)	0.0265 (8)	0.0368 (10)	0.0074 (7)	0.0125 (8)	0.0079 (7)
C11	0.0245 (9)	0.0280 (8)	0.0251 (8)	0.0011 (6)	0.0077 (7)	0.0006 (6)

Geometric parameters (Å, º) top

Pd1—N1	2.0441 (13)	C4—C5	1.376 (3)
Pd1—C1	2.0457 (17)	C4—H4	0.9500
Pd1—N2	2.0484 (13)	C5—C6	1.392 (2)
Pd1—Cl2	2.4612 (4)	C5—H5	0.9500
N1—C6	1.344 (2)	C6—H6	0.9500
N1—C2	1.347 (2)	C7—C8	1.385 (2)
N2—C7	1.344 (2)	C7—H7	0.9500
N2—C11	1.354 (2)	C8—C9	1.390 (2)
C1—H1A	0.9800	C8—H8	0.9500
C1—H1B	0.9800	C9—C10	1.381 (2)
C1—H1C	0.9800	C9—H9	0.9500
C2—C3	1.383 (2)	C10—C11	1.380 (2)
C2—H2	0.9500	C10—H10	0.9500
C3—C4	1.381 (3)	C11—H11	0.9500
C3—H3	0.9500

N1—Pd1—C1	90.58 (6)	C5—C4—C3	119.31 (16)
N1—Pd1—N2	177.92 (5)	C5—C4—H4	120.3
C1—Pd1—N2	88.24 (6)	C3—C4—H4	120.3
N1—Pd1—Cl2	90.15 (4)	C4—C5—C6	118.77 (17)
C1—Pd1—Cl2	178.55 (5)	C4—C5—H5	120.6
N2—Pd1—Cl2	90.99 (4)	C6—C5—H5	120.6
C6—N1—C2	118.22 (14)	N1—C6—C5	122.36 (16)
C6—N1—Pd1	119.36 (10)	N1—C6—H6	118.8
C2—N1—Pd1	122.27 (11)	C5—C6—H6	118.8
C7—N2—C11	118.14 (14)	N2—C7—C8	122.24 (15)
C7—N2—Pd1	123.18 (10)	N2—C7—H7	118.9
C11—N2—Pd1	118.68 (11)	C8—C7—H7	118.9
Pd1—C1—H1A	109.5	C7—C8—C9	119.23 (16)
Pd1—C1—H1B	109.5	C7—C8—H8	120.4
H1A—C1—H1B	109.5	C9—C8—H8	120.4
Pd1—C1—H1C	109.5	C10—C9—C8	118.67 (15)
H1A—C1—H1C	109.5	C10—C9—H9	120.7
H1B—C1—H1C	109.5	C8—C9—H9	120.7
N1—C2—C3	122.29 (17)	C11—C10—C9	119.22 (16)
N1—C2—H2	118.9	C11—C10—H10	120.4
C3—C2—H2	118.9	C9—C10—H10	120.4
C4—C3—C2	119.03 (17)	N2—C11—C10	122.49 (16)
C4—C3—H3	120.5	N2—C11—H11	118.8
C2—C3—H3	120.5	C10—C11—H11	118.8

C1—Pd1—N1—C6	−124.28 (13)	C3—C4—C5—C6	−0.9 (3)
Cl2—Pd1—N1—C6	56.97 (12)	C2—N1—C6—C5	0.2 (2)
C1—Pd1—N1—C2	60.31 (13)	Pd1—N1—C6—C5	−175.38 (13)
Cl2—Pd1—N1—C2	−118.44 (13)	C4—C5—C6—N1	1.0 (3)
C1—Pd1—N2—C7	54.71 (13)	C11—N2—C7—C8	0.4 (2)
Cl2—Pd1—N2—C7	−126.52 (12)	Pd1—N2—C7—C8	179.50 (13)
C1—Pd1—N2—C11	−126.19 (13)	N2—C7—C8—C9	0.1 (3)
Cl2—Pd1—N2—C11	52.58 (12)	C7—C8—C9—C10	−0.2 (3)
C6—N1—C2—C3	−1.5 (2)	C8—C9—C10—C11	−0.3 (3)
Pd1—N1—C2—C3	173.95 (13)	C7—N2—C11—C10	−0.9 (2)
N1—C2—C3—C4	1.6 (3)	Pd1—N2—C11—C10	179.97 (14)
C2—C3—C4—C5	−0.3 (3)	C9—C10—C11—N2	0.8 (3)

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bruker (1998). SMART (Version 5.054) and SAINT (Version 6.0). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Colamarino, P. & Orioli, P. L. (1975). J. Chem. Soc. Dalton Trans. pp. 1656–1659. CSD CrossRef Web of Science Google Scholar
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Viossat, B., Dung, N.-H. & Robert, F. (1993). Acta Cryst. C49, 84–85. CSD CrossRef CAS IUCr Journals Google Scholar

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