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The title compound, di­chloro-trans-bis­[tris(2-cyano­ethyl)­phosphine]­palladium(II), [PdCl2(C9H12N3P)2], was obtained by the addition of tris(2-cyano­ethyl)­phosphine to di­chloro-trans-bis­[aceto­nitrile]­palladium(II). The Pd atom lies on a centre of symmetry and the compound is isomorphous with the platinum analogue.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801009278/cv6031sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801009278/cv6031Isup2.hkl
Contains datablock I

CCDC reference: 170733

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.027
  • wR factor = 0.076
  • Data-to-parameter ratio = 17.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.636 Tmax scaled 0.636 Tmin scaled 0.614

Comment top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of the structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
(I) top
Crystal data top
[PdCl2(C9H12N3P)2]Dx = 1.540 Mg m3
Mr = 563.67Melting point = 186–188 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71069 Å
a = 9.1308 (11) ÅCell parameters from 22 reflections
b = 14.0077 (19) Åθ = 15.3–22.4°
c = 19.012 (3) ŵ = 1.13 mm1
V = 2431.7 (6) Å3T = 293 K
Z = 4Blocks, yellow
F(000) = 11360.52 × 0.43 × 0.40 mm
Data collection top
Nonius MACH3
diffractometer
1853 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.012
Graphite monochromatorθmax = 25.5°, θmin = 2.1°
ω–2θ scansh = 011
Absorption correction: ψ scan
(North et al, 1968)
k = 016
Tmin = 0.966, Tmax = 1.000l = 2222
2665 measured reflections3 standard reflections every 60 min
2256 independent reflections intensity decay: 0.8%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H-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 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
[PdCl2(C9H12N3P)2]V = 2431.7 (6) Å3
Mr = 563.67Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 9.1308 (11) ŵ = 1.13 mm1
b = 14.0077 (19) ÅT = 293 K
c = 19.012 (3) Å0.52 × 0.43 × 0.40 mm
Data collection top
Nonius MACH3
diffractometer
1853 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al, 1968)
Rint = 0.012
Tmin = 0.966, Tmax = 1.0003 standard reflections every 60 min
2665 measured reflections intensity decay: 0.8%
2256 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.076H-atom parameters constrained
S = 1.19Δρmax = 0.54 e Å3
2256 reflectionsΔρmin = 0.48 e Å3
133 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pd10.00000.50000.00000.02675 (11)
P10.01997 (8)0.43814 (6)0.11290 (4)0.02838 (18)
Cl10.16806 (10)0.61469 (7)0.03167 (5)0.0471 (2)
C10.2052 (3)0.4347 (2)0.15092 (17)0.0348 (7)
H1A0.20380.39390.19210.042*
H1B0.23130.49850.16630.042*
C20.3240 (4)0.3984 (3)0.1004 (2)0.0481 (9)
H2A0.34060.44550.06380.058*
H2B0.29110.33990.07810.058*
C30.4606 (4)0.3806 (3)0.1380 (2)0.0525 (10)
N40.5649 (4)0.3665 (3)0.1693 (2)0.0829 (13)
C50.0535 (4)0.3188 (2)0.12690 (18)0.0357 (7)
H5A0.15650.31860.11430.043*
H5B0.04640.30320.17650.043*
C60.0252 (4)0.2413 (2)0.0844 (2)0.0438 (8)
H6A0.12210.23110.10380.053*
H6B0.03660.26270.03610.053*
C70.0554 (5)0.1517 (3)0.0851 (3)0.0615 (12)
N80.1194 (6)0.0831 (3)0.0863 (3)0.1093 (19)
C90.0868 (4)0.5048 (2)0.17794 (18)0.0373 (8)
H9A0.05790.48370.22450.045*
H9B0.18940.48880.17190.045*
C100.0707 (4)0.6132 (2)0.1745 (2)0.0425 (8)
H10A0.10120.63580.12850.051*
H10B0.03120.63050.18110.051*
C110.1603 (4)0.6583 (2)0.2290 (2)0.0433 (8)
N120.2302 (4)0.6915 (3)0.27168 (19)0.0624 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.02414 (18)0.02724 (18)0.02888 (18)0.00261 (13)0.00360 (13)0.00037 (13)
P10.0256 (4)0.0289 (4)0.0307 (4)0.0012 (3)0.0017 (3)0.0010 (3)
Cl10.0466 (5)0.0453 (5)0.0493 (5)0.0203 (4)0.0152 (4)0.0047 (4)
C10.0290 (16)0.0391 (18)0.0363 (17)0.0017 (15)0.0065 (13)0.0012 (14)
C20.0296 (17)0.060 (2)0.055 (2)0.0056 (17)0.0022 (17)0.0055 (19)
C30.036 (2)0.052 (2)0.070 (3)0.0003 (18)0.0027 (19)0.005 (2)
N40.043 (2)0.102 (3)0.103 (3)0.009 (2)0.011 (2)0.025 (3)
C50.0352 (17)0.0324 (17)0.0396 (18)0.0003 (14)0.0051 (14)0.0054 (14)
C60.0424 (19)0.0326 (17)0.056 (2)0.0001 (16)0.0062 (17)0.0005 (16)
C70.072 (3)0.037 (2)0.075 (3)0.004 (2)0.021 (3)0.006 (2)
N80.125 (4)0.050 (2)0.152 (5)0.027 (3)0.056 (4)0.019 (3)
C90.0349 (18)0.0371 (18)0.0398 (18)0.0051 (15)0.0046 (15)0.0002 (15)
C100.0397 (19)0.0383 (18)0.049 (2)0.0013 (16)0.0080 (17)0.0071 (16)
C110.044 (2)0.0350 (18)0.051 (2)0.0005 (16)0.0031 (18)0.0065 (16)
N120.071 (2)0.052 (2)0.065 (2)0.0009 (18)0.018 (2)0.0110 (18)
Geometric parameters (Å, º) top
Pd1—Cl12.3018 (8)C5—C61.532 (5)
Pd1—Cl1i2.3018 (8)C5—H5A0.9700
Pd1—P12.3220 (9)C5—H5B0.9700
Pd1—P1i2.3221 (9)C6—C71.456 (5)
P1—C51.821 (3)C6—H6A0.9700
P1—C91.830 (3)C6—H6B0.9700
P1—C11.840 (3)C7—N81.125 (6)
C1—C21.536 (5)C9—C101.527 (5)
C1—H1A0.9700C9—H9A0.9700
C1—H1B0.9700C9—H9B0.9700
C2—C31.459 (5)C10—C111.464 (5)
C2—H2A0.9700C10—H10A0.9700
C2—H2B0.9700C10—H10B0.9700
C3—N41.140 (5)C11—N121.133 (5)
Cl1—Pd1—Cl1i180.00 (4)C6—C5—H5A108.9
Cl1—Pd1—P188.07 (3)P1—C5—H5A108.9
Cl1i—Pd1—P191.93 (3)C6—C5—H5B108.9
Cl1—Pd1—P1i91.93 (3)P1—C5—H5B108.9
Cl1i—Pd1—P1i88.07 (3)H5A—C5—H5B107.7
P1—Pd1—P1i180.0C7—C6—C5111.6 (3)
C5—P1—C999.98 (15)C7—C6—H6A109.3
C5—P1—C1104.92 (16)C5—C6—H6A109.3
C9—P1—C1103.74 (16)C7—C6—H6B109.3
C5—P1—Pd1116.66 (11)C5—C6—H6B109.3
C9—P1—Pd1113.10 (11)H6A—C6—H6B108.0
C1—P1—Pd1116.42 (11)N8—C7—C6178.9 (5)
C2—C1—P1114.3 (2)C10—C9—P1115.3 (2)
C2—C1—H1A108.7C10—C9—H9A108.5
P1—C1—H1A108.7P1—C9—H9A108.5
C2—C1—H1B108.7C10—C9—H9B108.5
P1—C1—H1B108.7P1—C9—H9B108.5
H1A—C1—H1B107.6H9A—C9—H9B107.5
C3—C2—C1110.7 (3)C11—C10—C9110.2 (3)
C3—C2—H2A109.5C11—C10—H10A109.6
C1—C2—H2A109.5C9—C10—H10A109.6
C3—C2—H2B109.5C11—C10—H10B109.6
C1—C2—H2B109.5C9—C10—H10B109.6
H2A—C2—H2B108.1H10A—C10—H10B108.1
N4—C3—C2177.9 (5)N12—C11—C10178.6 (4)
C6—C5—P1113.6 (2)
Cl1—Pd1—P1—C5165.15 (13)P1—C1—C2—C3169.1 (3)
Cl1i—Pd1—P1—C514.84 (13)C9—P1—C5—C6174.3 (3)
Cl1—Pd1—P1—C979.69 (13)C1—P1—C5—C667.0 (3)
Cl1i—Pd1—P1—C9100.31 (13)Pd1—P1—C5—C663.4 (3)
Cl1—Pd1—P1—C140.32 (13)P1—C5—C6—C7167.7 (3)
Cl1i—Pd1—P1—C1139.68 (13)C5—P1—C9—C10171.4 (3)
C5—P1—C1—C286.2 (3)C1—P1—C9—C1080.4 (3)
C9—P1—C1—C2169.3 (3)Pd1—P1—C9—C1046.7 (3)
Pd1—P1—C1—C244.4 (3)P1—C9—C10—C11179.8 (3)
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula[PdCl2(C9H12N3P)2]
Mr563.67
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)293
a, b, c (Å)9.1308 (11), 14.0077 (19), 19.012 (3)
V3)2431.7 (6)
Z4
Radiation typeMo Kα
µ (mm1)1.13
Crystal size (mm)0.52 × 0.43 × 0.40
Data collection
DiffractometerNonius MACH3
diffractometer
Absorption correctionψ scan
(North et al, 1968)
Tmin, Tmax0.966, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
2665, 2256, 1853
Rint0.012
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.076, 1.19
No. of reflections2256
No. of parameters133
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

 

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