Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801009278/cv6031sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801009278/cv6031Isup2.hkl |
CCDC reference: 170733
Compound (I) was synthesized by the reaction of P(CH2CH2CN)3 with [PdCl2(CH3CN)2] generated in situ by heating PdCl2 with CH3CN under reflux for 1.5 h. Two equivalents of P(CH2CH2CN)3 were added to the hot CH3CN solution of [PdCl2(CH3CN)2], causing an immediate colour change from orange to yellow. The reaction was heated under reflux for a further hour and filtered. The solvent was removed in vacuo from the filtrate and the sample crystallized from CH3CN to give an 84% yield of (I) as a yellow crystalline solid. Crystals suitable for X-ray diffraction were obtained by slow evaporation from a CH3CN solution.
All H atoms were clearly defined in difference maps and were then treated as riding atoms with a C—H distance 0.95 Å and Uiso(H) = 1.2Ueq(C). Examination of the structure with PLATON (Spek, 2000) showed that there were no solvent-accessible voids in the crystal lattice.
Data collection: CAD-4 Data Collection Software (Nonius, 1988); cell refinement: CAD-4 Data Collection Software; data reduction: maXus (Mackay et al., 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97 and PLATON.
Fig. 1. A view of the structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
[PdCl2(C9H12N3P)2] | Dx = 1.540 Mg m−3 |
Mr = 563.67 | Melting point = 186–188 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71069 Å |
a = 9.1308 (11) Å | Cell parameters from 22 reflections |
b = 14.0077 (19) Å | θ = 15.3–22.4° |
c = 19.012 (3) Å | µ = 1.13 mm−1 |
V = 2431.7 (6) Å3 | T = 293 K |
Z = 4 | Blocks, yellow |
F(000) = 1136 | 0.52 × 0.43 × 0.40 mm |
Nonius MACH3 diffractometer | 1853 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.012 |
Graphite monochromator | θmax = 25.5°, θmin = 2.1° |
ω–2θ scans | h = 0→11 |
Absorption correction: ψ scan (North et al, 1968) | k = 0→16 |
Tmin = 0.966, Tmax = 1.000 | l = −22→22 |
2665 measured reflections | 3 standard reflections every 60 min |
2256 independent reflections | intensity decay: 0.8% |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0248P)2 + 3.6835P] where P = (Fo2 + 2Fc2)/3 |
2256 reflections | (Δ/σ)max < 0.001 |
133 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
[PdCl2(C9H12N3P)2] | V = 2431.7 (6) Å3 |
Mr = 563.67 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.1308 (11) Å | µ = 1.13 mm−1 |
b = 14.0077 (19) Å | T = 293 K |
c = 19.012 (3) Å | 0.52 × 0.43 × 0.40 mm |
Nonius MACH3 diffractometer | 1853 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al, 1968) | Rint = 0.012 |
Tmin = 0.966, Tmax = 1.000 | 3 standard reflections every 60 min |
2665 measured reflections | intensity decay: 0.8% |
2256 independent reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.54 e Å−3 |
2256 reflections | Δρmin = −0.48 e Å−3 |
133 parameters |
Experimental. The reaction was carried out under N2, although the product was isolated in the air. Palladium(II) chloride was obtained from Aldrich Chemical Co. and tris(2-cyanoethyl)phosphine from Strem Chemicals; both were used as supplied. Analysis calculated for C18H24Cl2N6P2Pd: C 38.35, H 4.29, N 14.91, Cl 12.57%; found: C 38.16, H 4.23, N 14.72, Cl 12.35%; 31P NMR (CD3CN) δ P 15.41 p.p.m.; 1H NMR (CD3CN) δ 2.34 t 2H (P—CH2–),2.76 t 2H (–CH2CN); IR νmax (KBr) cm-1: 2243.1 (CN stretch). |
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. One of the nitrogen atoms has a large displacement parameter. However, attempts to model this as disorder over two positions were unsuccessful. 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 | 0.0000 | 0.5000 | 0.0000 | 0.02675 (11) | |
P1 | −0.01997 (8) | 0.43814 (6) | 0.11290 (4) | 0.02838 (18) | |
Cl1 | −0.16806 (10) | 0.61469 (7) | 0.03167 (5) | 0.0471 (2) | |
C1 | −0.2052 (3) | 0.4347 (2) | 0.15092 (17) | 0.0348 (7) | |
H1A | −0.2038 | 0.3939 | 0.1921 | 0.042* | |
H1B | −0.2313 | 0.4985 | 0.1663 | 0.042* | |
C2 | −0.3240 (4) | 0.3984 (3) | 0.1004 (2) | 0.0481 (9) | |
H2A | −0.3406 | 0.4455 | 0.0638 | 0.058* | |
H2B | −0.2911 | 0.3399 | 0.0781 | 0.058* | |
C3 | −0.4606 (4) | 0.3806 (3) | 0.1380 (2) | 0.0525 (10) | |
N4 | −0.5649 (4) | 0.3665 (3) | 0.1693 (2) | 0.0829 (13) | |
C5 | 0.0535 (4) | 0.3188 (2) | 0.12690 (18) | 0.0357 (7) | |
H5A | 0.1565 | 0.3186 | 0.1143 | 0.043* | |
H5B | 0.0464 | 0.3032 | 0.1765 | 0.043* | |
C6 | −0.0252 (4) | 0.2413 (2) | 0.0844 (2) | 0.0438 (8) | |
H6A | −0.1221 | 0.2311 | 0.1038 | 0.053* | |
H6B | −0.0366 | 0.2627 | 0.0361 | 0.053* | |
C7 | 0.0554 (5) | 0.1517 (3) | 0.0851 (3) | 0.0615 (12) | |
N8 | 0.1194 (6) | 0.0831 (3) | 0.0863 (3) | 0.1093 (19) | |
C9 | 0.0868 (4) | 0.5048 (2) | 0.17794 (18) | 0.0373 (8) | |
H9A | 0.0579 | 0.4837 | 0.2245 | 0.045* | |
H9B | 0.1894 | 0.4888 | 0.1719 | 0.045* | |
C10 | 0.0707 (4) | 0.6132 (2) | 0.1745 (2) | 0.0425 (8) | |
H10A | 0.1012 | 0.6358 | 0.1285 | 0.051* | |
H10B | −0.0312 | 0.6305 | 0.1811 | 0.051* | |
C11 | 0.1603 (4) | 0.6583 (2) | 0.2290 (2) | 0.0433 (8) | |
N12 | 0.2302 (4) | 0.6915 (3) | 0.27168 (19) | 0.0624 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.02414 (18) | 0.02724 (18) | 0.02888 (18) | 0.00261 (13) | 0.00360 (13) | 0.00037 (13) |
P1 | 0.0256 (4) | 0.0289 (4) | 0.0307 (4) | −0.0012 (3) | 0.0017 (3) | 0.0010 (3) |
Cl1 | 0.0466 (5) | 0.0453 (5) | 0.0493 (5) | 0.0203 (4) | 0.0152 (4) | 0.0047 (4) |
C1 | 0.0290 (16) | 0.0391 (18) | 0.0363 (17) | −0.0017 (15) | 0.0065 (13) | 0.0012 (14) |
C2 | 0.0296 (17) | 0.060 (2) | 0.055 (2) | −0.0056 (17) | 0.0022 (17) | −0.0055 (19) |
C3 | 0.036 (2) | 0.052 (2) | 0.070 (3) | −0.0003 (18) | −0.0027 (19) | 0.005 (2) |
N4 | 0.043 (2) | 0.102 (3) | 0.103 (3) | −0.009 (2) | 0.011 (2) | 0.025 (3) |
C5 | 0.0352 (17) | 0.0324 (17) | 0.0396 (18) | 0.0003 (14) | −0.0051 (14) | 0.0054 (14) |
C6 | 0.0424 (19) | 0.0326 (17) | 0.056 (2) | 0.0001 (16) | −0.0062 (17) | 0.0005 (16) |
C7 | 0.072 (3) | 0.037 (2) | 0.075 (3) | 0.004 (2) | −0.021 (3) | −0.006 (2) |
N8 | 0.125 (4) | 0.050 (2) | 0.152 (5) | 0.027 (3) | −0.056 (4) | −0.019 (3) |
C9 | 0.0349 (18) | 0.0371 (18) | 0.0398 (18) | −0.0051 (15) | −0.0046 (15) | −0.0002 (15) |
C10 | 0.0397 (19) | 0.0383 (18) | 0.049 (2) | −0.0013 (16) | −0.0080 (17) | −0.0071 (16) |
C11 | 0.044 (2) | 0.0350 (18) | 0.051 (2) | 0.0005 (16) | −0.0031 (18) | −0.0065 (16) |
N12 | 0.071 (2) | 0.052 (2) | 0.065 (2) | −0.0009 (18) | −0.018 (2) | −0.0110 (18) |
Pd1—Cl1 | 2.3018 (8) | C5—C6 | 1.532 (5) |
Pd1—Cl1i | 2.3018 (8) | C5—H5A | 0.9700 |
Pd1—P1 | 2.3220 (9) | C5—H5B | 0.9700 |
Pd1—P1i | 2.3221 (9) | C6—C7 | 1.456 (5) |
P1—C5 | 1.821 (3) | C6—H6A | 0.9700 |
P1—C9 | 1.830 (3) | C6—H6B | 0.9700 |
P1—C1 | 1.840 (3) | C7—N8 | 1.125 (6) |
C1—C2 | 1.536 (5) | C9—C10 | 1.527 (5) |
C1—H1A | 0.9700 | C9—H9A | 0.9700 |
C1—H1B | 0.9700 | C9—H9B | 0.9700 |
C2—C3 | 1.459 (5) | C10—C11 | 1.464 (5) |
C2—H2A | 0.9700 | C10—H10A | 0.9700 |
C2—H2B | 0.9700 | C10—H10B | 0.9700 |
C3—N4 | 1.140 (5) | C11—N12 | 1.133 (5) |
Cl1—Pd1—Cl1i | 180.00 (4) | C6—C5—H5A | 108.9 |
Cl1—Pd1—P1 | 88.07 (3) | P1—C5—H5A | 108.9 |
Cl1i—Pd1—P1 | 91.93 (3) | C6—C5—H5B | 108.9 |
Cl1—Pd1—P1i | 91.93 (3) | P1—C5—H5B | 108.9 |
Cl1i—Pd1—P1i | 88.07 (3) | H5A—C5—H5B | 107.7 |
P1—Pd1—P1i | 180.0 | C7—C6—C5 | 111.6 (3) |
C5—P1—C9 | 99.98 (15) | C7—C6—H6A | 109.3 |
C5—P1—C1 | 104.92 (16) | C5—C6—H6A | 109.3 |
C9—P1—C1 | 103.74 (16) | C7—C6—H6B | 109.3 |
C5—P1—Pd1 | 116.66 (11) | C5—C6—H6B | 109.3 |
C9—P1—Pd1 | 113.10 (11) | H6A—C6—H6B | 108.0 |
C1—P1—Pd1 | 116.42 (11) | N8—C7—C6 | 178.9 (5) |
C2—C1—P1 | 114.3 (2) | C10—C9—P1 | 115.3 (2) |
C2—C1—H1A | 108.7 | C10—C9—H9A | 108.5 |
P1—C1—H1A | 108.7 | P1—C9—H9A | 108.5 |
C2—C1—H1B | 108.7 | C10—C9—H9B | 108.5 |
P1—C1—H1B | 108.7 | P1—C9—H9B | 108.5 |
H1A—C1—H1B | 107.6 | H9A—C9—H9B | 107.5 |
C3—C2—C1 | 110.7 (3) | C11—C10—C9 | 110.2 (3) |
C3—C2—H2A | 109.5 | C11—C10—H10A | 109.6 |
C1—C2—H2A | 109.5 | C9—C10—H10A | 109.6 |
C3—C2—H2B | 109.5 | C11—C10—H10B | 109.6 |
C1—C2—H2B | 109.5 | C9—C10—H10B | 109.6 |
H2A—C2—H2B | 108.1 | H10A—C10—H10B | 108.1 |
N4—C3—C2 | 177.9 (5) | N12—C11—C10 | 178.6 (4) |
C6—C5—P1 | 113.6 (2) | ||
Cl1—Pd1—P1—C5 | 165.15 (13) | P1—C1—C2—C3 | 169.1 (3) |
Cl1i—Pd1—P1—C5 | −14.84 (13) | C9—P1—C5—C6 | 174.3 (3) |
Cl1—Pd1—P1—C9 | −79.69 (13) | C1—P1—C5—C6 | 67.0 (3) |
Cl1i—Pd1—P1—C9 | 100.31 (13) | Pd1—P1—C5—C6 | −63.4 (3) |
Cl1—Pd1—P1—C1 | 40.32 (13) | P1—C5—C6—C7 | 167.7 (3) |
Cl1i—Pd1—P1—C1 | −139.68 (13) | C5—P1—C9—C10 | 171.4 (3) |
C5—P1—C1—C2 | −86.2 (3) | C1—P1—C9—C10 | −80.4 (3) |
C9—P1—C1—C2 | 169.3 (3) | Pd1—P1—C9—C10 | 46.7 (3) |
Pd1—P1—C1—C2 | 44.4 (3) | P1—C9—C10—C11 | 179.8 (3) |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [PdCl2(C9H12N3P)2] |
Mr | 563.67 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 9.1308 (11), 14.0077 (19), 19.012 (3) |
V (Å3) | 2431.7 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.13 |
Crystal size (mm) | 0.52 × 0.43 × 0.40 |
Data collection | |
Diffractometer | Nonius MACH3 diffractometer |
Absorption correction | ψ scan (North et al, 1968) |
Tmin, Tmax | 0.966, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2665, 2256, 1853 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.076, 1.19 |
No. of reflections | 2256 |
No. of parameters | 133 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.48 |
Computer programs: CAD-4 Data Collection Software (Nonius, 1988), CAD-4 Data Collection Software, maXus (Mackay et al., 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2000), SHELXL97 and PLATON.
The use of tris(2-cyanoethyl)phosphine (CEP) as a ligand has attracted considerable interest since it has structural similiarity to n-alkylphosphines and yet possesses different electronic properties (Cotton et al., 1981). CEP has been utilized in the preparation of many metal complexes, including [HgCl2(CEP)]n (Bell et al., 1984) and Ni4(CO)6(CEP)4 (Bennett et al., 1967). The simple dichloro-trans-bis(CEP)platinum(II) complex is known (Khan et al., 1993), and as part of our continuing studies on transition metal CEP complexes, we decided to examine the palladium analogue dichloro-trans-bis[tris(2-cyanoethyl)phosphine]palladium(II), (I).
The title compound lies with the palladium on a centre of symmetry (Fig. 1) and is isomorphous with the platinum analogue. All molecular geometry parameters lie within the normal ranges (Allen et al., 1987; Orpen et al., 1989).