metal-organic compounds
trans-Chloromethyldipyridinepalladium(II)
aSchool of Chemistry, Cantocks Close, University of Bristol, Bristol BS8 1TS, England
*Correspondence e-mail: gareth.owen@bris.ac.uk
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 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 and the atom-labelling scheme. The 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 PdII—C,Cl,N (Allen et al., 1987). The molecules in the 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 M(pyridine)2Cl2] where M = Pd (Viossat et al., 1993) or Pt (Colamarino & Orioli, 1975).
is not isostructural with either [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
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Refinement
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H atoms were treated as riding, with C—H distances of 0.95 and 0.98Å and with Uiso(H) values of 1.2 and 1.5 times Ueq(C) for aromatic and methyl H atoms, respectively.
Data collection: SMART (Bruker, 1998); cell 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
https://doi.org/10.1107/S1600536805037268/bv6036sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805037268/bv6036Isup2.hkl
Data collection: SMART (Bruker, 1998); cell
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.[Pd(CH3)Cl(C5H5N)2] | F(000) = 1248 |
Mr = 315.08 | Dx = 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 |
Bruker SMART CCD area-detector diffractometer | 2785 independent reflections |
Radiation source: fine-focus sealed tube | 2555 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 8.2 pixels mm-1 | θmax = 27.5°, θmin = 2.4° |
φ and ω scans | h = −17→16 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −15→15 |
Tmin = 0.583, Tmax = 0.710 | l = −19→21 |
12619 measured reflections |
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(Fo2) + (0.0245P)2] where P = (Fo2 + 2Fc2)/3 |
2785 reflections | (Δ/σ)max = 0.001 |
137 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.74 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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
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