In the title compound, [Pd(C6H5)Cl(C3H4N2){P(C6H5)3}], the phenyl and Cl ligands lie mutually trans. The compound is the first structurally characterized complex with four monodentate Cl, P, N and (non-carbenoid) C ligands in a square-planar four-coordinate palladium(II) environment. The pyrazole ligand is coplanar with the latter array. The pyrazole NH group forms a bifurcated hydrogen bond to Cl, with an intra- and intermolecular component.
Supporting information
CCDC reference: 248138
The H atoms were located in difference Fourier maps and placed in idealized positions, with C—H distances of 0.95 and N—H distances of 0.92 Å, and with Uiso(H) = 1.25Ueq(C,N).
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: Xtal (Hall et al., 1995); program(s) used to solve structure: Xtal; program(s) used to refine structure: CRYLSQ in Xtal; molecular graphics: Xtal; software used to prepare material for publication: BONDLA and CIFIO in Xtal.
Chloro(phenyl)(1
H-pyrazole-
κN2)(triphenylphosphine)palladium(II)
top
Crystal data top
[Pd(C6H5)Cl(C3H4N2)(C18H15P)] | Z = 2 |
Mr = 549.37 | F(000) = 556 |
Triclinic, P1 | Dx = 1.498 Mg m−3 |
Hall symbol: -p 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.817 (2) Å | Cell parameters from 12 reflections |
b = 10.797 (5) Å | θ = 14.5–15.6° |
c = 13.523 (7) Å | µ = 0.96 mm−1 |
α = 72.85 (4)° | T = 300 K |
β = 88.21 (3)° | Fragment, colourless |
γ = 63.55 (3)° | 0.70 × 0.52 × 0.25 mm |
V = 1217.8 (10) Å3 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 3887 reflections with I > 2σ(I) |
Radiation source: sealed tube | θmax = 25.0°, θmin = 1.6° |
Graphite monochromator | h = −11→11 |
2θ/ω scans | k = −12→11 |
Absorption correction: gaussian ABSORB in Xtal; Hall et al., 1995) | l = −16→0 |
Tmin = 0.63, Tmax = 0.73 | 60 standard reflections every 60 min |
4265 measured reflections | intensity decay: none |
4265 independent 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)] = 0.035 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.28 | |
3887 reflections | (Δ/σ)max = 0.003 |
289 parameters | Δρmax = 0.80 e Å−3 |
0 restraints | Δρmin = −0.77 e Å−3 |
0 constraints | |
Crystal data top
[Pd(C6H5)Cl(C3H4N2)(C18H15P)] | γ = 63.55 (3)° |
Mr = 549.37 | V = 1217.8 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.817 (2) Å | Mo Kα radiation |
b = 10.797 (5) Å | µ = 0.96 mm−1 |
c = 13.523 (7) Å | T = 300 K |
α = 72.85 (4)° | 0.70 × 0.52 × 0.25 mm |
β = 88.21 (3)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 4265 independent reflections |
Absorption correction: gaussian ABSORB in Xtal; Hall et al., 1995) | 3887 reflections with I > 2σ(I) |
Tmin = 0.63, Tmax = 0.73 | 60 standard reflections every 60 min |
4265 measured reflections | intensity decay: none |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.28 | Δρmax = 0.80 e Å−3 |
3887 reflections | Δρmin = −0.77 e Å−3 |
289 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pd | 0.27030 (4) | 0.24519 (3) | 0.36744 (2) | 0.0357 (3) | |
Cl | 0.17217 (15) | 0.46691 (13) | 0.41377 (11) | 0.0625 (14) | |
P | 0.38021 (12) | 0.33433 (12) | 0.23614 (8) | 0.0391 (10) | |
C11 | 0.4652 (5) | 0.2342 (5) | 0.1444 (3) | 0.043 (4) | |
C12 | 0.4097 (5) | 0.2891 (5) | 0.0395 (3) | 0.051 (5) | |
C13 | 0.4811 (7) | 0.2065 (7) | −0.0264 (4) | 0.065 (7) | |
C14 | 0.6047 (7) | 0.0742 (7) | 0.0112 (5) | 0.071 (7) | |
C15 | 0.6614 (6) | 0.0187 (6) | 0.1149 (5) | 0.068 (6) | |
C16 | 0.5930 (5) | 0.0987 (5) | 0.1820 (4) | 0.055 (5) | |
C21 | 0.5371 (5) | 0.3641 (4) | 0.2754 (3) | 0.043 (4) | |
C22 | 0.5565 (6) | 0.3697 (5) | 0.3744 (4) | 0.052 (5) | |
C23 | 0.6751 (7) | 0.3931 (6) | 0.4033 (5) | 0.069 (6) | |
C24 | 0.7742 (6) | 0.4111 (6) | 0.3342 (5) | 0.073 (7) | |
C25 | 0.7582 (6) | 0.4026 (6) | 0.2363 (5) | 0.069 (6) | |
C26 | 0.6401 (5) | 0.3808 (6) | 0.2061 (4) | 0.058 (5) | |
C31 | 0.2358 (5) | 0.5095 (5) | 0.1528 (3) | 0.041 (4) | |
C32 | 0.0900 (6) | 0.5267 (6) | 0.1368 (5) | 0.074 (6) | |
C33 | −0.0218 (6) | 0.6540 (7) | 0.0690 (6) | 0.091 (8) | |
C34 | 0.0111 (7) | 0.7652 (6) | 0.0181 (5) | 0.074 (6) | |
C35 | 0.1520 (7) | 0.7507 (6) | 0.0355 (5) | 0.082 (7) | |
C36 | 0.2652 (6) | 0.6237 (6) | 0.1024 (4) | 0.064 (6) | |
N1 | 0.1687 (4) | 0.1572 (4) | 0.4906 (3) | 0.044 (4) | |
N2 | 0.0836 (5) | 0.2382 (4) | 0.5494 (3) | 0.053 (4) | |
C3 | 0.0317 (6) | 0.1604 (6) | 0.6235 (4) | 0.064 (6) | |
C4 | 0.0848 (6) | 0.0269 (6) | 0.6131 (4) | 0.065 (6) | |
C5 | 0.1693 (6) | 0.0296 (5) | 0.5292 (4) | 0.054 (5) | |
C101 | 0.3327 (5) | 0.0649 (4) | 0.3279 (3) | 0.041 (4) | |
C102 | 0.4645 (6) | −0.0627 (5) | 0.3762 (4) | 0.055 (5) | |
C103 | 0.4952 (7) | −0.1914 (5) | 0.3581 (4) | 0.068 (6) | |
C104 | 0.3941 (8) | −0.1959 (6) | 0.2930 (4) | 0.072 (7) | |
C105 | 0.2629 (7) | −0.0698 (6) | 0.2433 (4) | 0.066 (7) | |
C106 | 0.2338 (6) | 0.0593 (5) | 0.2606 (3) | 0.051 (5) | |
H12 | 0.32390 | 0.38234 | 0.01226 | 0.08200* | |
H13 | 0.44271 | 0.24341 | −0.09818 | 0.09000* | |
H14 | 0.65218 | 0.01918 | −0.03431 | 0.09400* | |
H15 | 0.74798 | −0.07433 | 0.14081 | 0.08600* | |
H16 | 0.63287 | 0.06097 | 0.25357 | 0.07100* | |
H22 | 0.48794 | 0.35752 | 0.42298 | 0.07000* | |
H23 | 0.68750 | 0.39656 | 0.47191 | 0.08500* | |
H24 | 0.85379 | 0.42945 | 0.35377 | 0.08200* | |
H25 | 0.82903 | 0.41198 | 0.18854 | 0.08100* | |
H26 | 0.62876 | 0.37687 | 0.13757 | 0.08100* | |
H32 | 0.06574 | 0.45040 | 0.17274 | 0.08300* | |
H33 | −0.12218 | 0.66437 | 0.05827 | 0.09600* | |
H34 | −0.06509 | 0.85196 | −0.03000 | 0.08100* | |
H35 | 0.17417 | 0.82917 | 0.00141 | 0.07700* | |
H36 | 0.36445 | 0.61534 | 0.11316 | 0.07300* | |
H2 | 0.06363 | 0.33291 | 0.54049 | 0.06600* | |
H3 | −0.03116 | 0.19413 | 0.67405 | 0.06700* | |
H4 | 0.06794 | −0.05180 | 0.65460 | 0.07800* | |
H5 | 0.22122 | −0.05042 | 0.50356 | 0.06800* | |
H102 | 0.53404 | −0.06134 | 0.42272 | 0.06100* | |
H103 | 0.58703 | −0.27700 | 0.39019 | 0.08000* | |
H104 | 0.41398 | −0.28498 | 0.28206 | 0.08200* | |
H105 | 0.19268 | −0.07215 | 0.19817 | 0.09300* | |
H106 | 0.14443 | 0.14590 | 0.22513 | 0.06200* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pd | 0.03984 (17) | 0.03385 (16) | 0.03780 (17) | −0.01913 (13) | 0.01114 (12) | −0.01411 (12) |
Cl | 0.0750 (8) | 0.0500 (7) | 0.0758 (8) | −0.0326 (6) | 0.0342 (7) | −0.0337 (6) |
P | 0.0404 (6) | 0.0408 (6) | 0.0396 (6) | −0.0214 (5) | 0.0072 (5) | −0.0130 (5) |
C11 | 0.045 (2) | 0.047 (2) | 0.047 (2) | −0.027 (2) | 0.013 (2) | −0.018 (2) |
C12 | 0.055 (3) | 0.065 (3) | 0.047 (3) | −0.035 (2) | 0.010 (2) | −0.022 (2) |
C13 | 0.074 (4) | 0.089 (4) | 0.053 (3) | −0.048 (3) | 0.018 (3) | −0.034 (3) |
C14 | 0.082 (4) | 0.090 (4) | 0.072 (4) | −0.052 (4) | 0.036 (3) | −0.051 (3) |
C15 | 0.062 (3) | 0.061 (3) | 0.084 (4) | −0.026 (3) | 0.027 (3) | −0.032 (3) |
C16 | 0.053 (3) | 0.052 (3) | 0.057 (3) | −0.022 (2) | 0.015 (2) | −0.020 (2) |
C21 | 0.042 (2) | 0.037 (2) | 0.047 (2) | −0.0196 (19) | 0.0022 (18) | −0.0082 (18) |
C22 | 0.059 (3) | 0.053 (3) | 0.051 (3) | −0.027 (2) | 0.003 (2) | −0.021 (2) |
C23 | 0.075 (4) | 0.067 (3) | 0.070 (4) | −0.035 (3) | −0.012 (3) | −0.022 (3) |
C24 | 0.062 (3) | 0.064 (3) | 0.091 (4) | −0.034 (3) | −0.021 (3) | −0.011 (3) |
C25 | 0.051 (3) | 0.079 (4) | 0.079 (4) | −0.041 (3) | −0.001 (3) | −0.009 (3) |
C26 | 0.049 (3) | 0.069 (3) | 0.056 (3) | −0.033 (3) | 0.004 (2) | −0.012 (2) |
C31 | 0.038 (2) | 0.043 (2) | 0.043 (2) | −0.0183 (19) | 0.0046 (18) | −0.0142 (19) |
C32 | 0.048 (3) | 0.059 (3) | 0.103 (5) | −0.028 (3) | −0.009 (3) | −0.003 (3) |
C33 | 0.044 (3) | 0.081 (4) | 0.129 (6) | −0.022 (3) | −0.017 (3) | −0.015 (4) |
C34 | 0.061 (3) | 0.059 (3) | 0.073 (4) | −0.009 (3) | −0.011 (3) | −0.006 (3) |
C35 | 0.071 (4) | 0.053 (3) | 0.092 (4) | −0.027 (3) | −0.008 (3) | 0.015 (3) |
C36 | 0.052 (3) | 0.057 (3) | 0.074 (3) | −0.030 (2) | −0.004 (3) | 0.001 (3) |
N1 | 0.046 (2) | 0.043 (2) | 0.047 (2) | −0.0223 (17) | 0.0114 (16) | −0.0154 (17) |
N2 | 0.062 (2) | 0.045 (2) | 0.051 (2) | −0.0230 (19) | 0.0208 (19) | −0.0153 (18) |
C3 | 0.069 (3) | 0.064 (3) | 0.052 (3) | −0.030 (3) | 0.025 (3) | −0.010 (2) |
C4 | 0.073 (3) | 0.060 (3) | 0.061 (3) | −0.037 (3) | 0.019 (3) | −0.008 (3) |
C5 | 0.061 (3) | 0.047 (3) | 0.057 (3) | −0.030 (2) | 0.014 (2) | −0.014 (2) |
C101 | 0.047 (2) | 0.038 (2) | 0.039 (2) | −0.021 (2) | 0.0119 (18) | −0.0117 (18) |
C102 | 0.058 (3) | 0.050 (3) | 0.047 (3) | −0.018 (2) | 0.004 (2) | −0.014 (2) |
C103 | 0.088 (4) | 0.038 (3) | 0.058 (3) | −0.013 (3) | 0.016 (3) | −0.016 (2) |
C104 | 0.122 (5) | 0.045 (3) | 0.054 (3) | −0.039 (3) | 0.021 (3) | −0.021 (2) |
C105 | 0.103 (4) | 0.075 (4) | 0.046 (3) | −0.058 (3) | 0.015 (3) | −0.027 (3) |
C106 | 0.063 (3) | 0.050 (3) | 0.044 (2) | −0.029 (2) | 0.006 (2) | −0.015 (2) |
Geometric parameters (Å, º) top
Pd—Cl | 2.4174 (15) | C31—C36 | 1.370 (8) |
Pd—P | 2.2451 (12) | C32—C33 | 1.382 (7) |
Pd—N1 | 2.116 (4) | C32—H32 | 0.950 |
Pd—C101 | 1.995 (5) | C33—C34 | 1.365 (10) |
P—C11 | 1.824 (5) | C33—H33 | 0.952 |
P—C21 | 1.830 (6) | C34—C35 | 1.342 (10) |
P—C31 | 1.819 (3) | C34—H34 | 0.952 |
C11—C12 | 1.388 (6) | C35—C36 | 1.381 (6) |
C11—C16 | 1.393 (5) | C35—H35 | 0.951 |
C12—C13 | 1.397 (8) | C36—H36 | 0.950 |
C12—H12 | 0.951 | N1—N2 | 1.347 (6) |
C13—C14 | 1.355 (7) | N1—C5 | 1.319 (7) |
C13—H13 | 0.951 | N2—C3 | 1.349 (7) |
C14—C15 | 1.375 (8) | N2—H2 | 0.922 |
C14—H14 | 0.949 | C3—C4 | 1.347 (9) |
C15—C16 | 1.389 (9) | C3—H3 | 0.950 |
C15—H15 | 0.951 | C4—C5 | 1.385 (8) |
C16—H16 | 0.951 | C4—H4 | 0.950 |
C21—C22 | 1.381 (7) | C5—H5 | 0.949 |
C21—C26 | 1.392 (7) | C101—C102 | 1.390 (5) |
C22—C23 | 1.386 (10) | C101—C106 | 1.383 (8) |
C22—H22 | 0.949 | C102—C103 | 1.379 (9) |
C23—C24 | 1.365 (9) | C102—H102 | 0.951 |
C23—H23 | 0.953 | C103—C104 | 1.373 (10) |
C24—C25 | 1.372 (10) | C103—H103 | 0.949 |
C24—H24 | 0.950 | C104—C105 | 1.385 (7) |
C25—C26 | 1.378 (10) | C104—H104 | 0.948 |
C25—H25 | 0.952 | C105—C106 | 1.383 (9) |
C26—H26 | 0.951 | C105—H105 | 0.948 |
C31—C32 | 1.374 (8) | C106—H106 | 0.951 |
| | | |
Cl—Pd—P | 91.18 (5) | C32—C31—C36 | 118.1 (4) |
Cl—Pd—N1 | 89.96 (12) | C31—C32—C33 | 120.7 (6) |
Cl—Pd—C101 | 175.06 (14) | C31—C32—H32 | 119.7 |
P—Pd—N1 | 178.86 (12) | C33—C32—H32 | 119.6 |
P—Pd—C101 | 91.54 (13) | C32—C33—C34 | 120.2 (6) |
N1—Pd—C101 | 87.34 (17) | C32—C33—H33 | 119.9 |
Pd—P—C11 | 119.66 (18) | C34—C33—H33 | 120.0 |
Pd—P—C21 | 115.34 (14) | C33—C34—C35 | 119.5 (5) |
Pd—P—C31 | 108.89 (15) | C33—C34—H34 | 120.3 |
C11—P—C21 | 101.7 (2) | C35—C34—H34 | 120.2 |
C11—P—C31 | 103.1 (2) | C34—C35—C36 | 120.9 (6) |
C21—P—C31 | 106.9 (2) | C34—C35—H35 | 119.5 |
P—C11—C12 | 122.7 (3) | C36—C35—H35 | 119.6 |
P—C11—C16 | 117.9 (4) | C31—C36—C35 | 120.6 (6) |
C12—C11—C16 | 119.4 (5) | C31—C36—H36 | 119.8 |
C11—C12—C13 | 119.6 (4) | C35—C36—H36 | 119.6 |
C11—C12—H12 | 120.4 | Pd—N1—N2 | 120.1 (3) |
C13—C12—H12 | 120.0 | Pd—N1—C5 | 134.2 (3) |
C12—C13—C14 | 120.6 (5) | N2—N1—C5 | 105.7 (4) |
C12—C13—H13 | 119.7 | N1—N2—C3 | 110.1 (4) |
C14—C13—H13 | 119.7 | N1—N2—H2 | 125.0 |
C13—C14—C15 | 120.5 (6) | C3—N2—H2 | 124.9 |
C13—C14—H14 | 119.8 | N2—C3—C4 | 108.1 (5) |
C15—C14—H14 | 119.7 | N2—C3—H3 | 125.8 |
C14—C15—C16 | 120.1 (4) | C4—C3—H3 | 126.1 |
C14—C15—H15 | 120.2 | C3—C4—C5 | 105.0 (5) |
C16—C15—H15 | 119.7 | C3—C4—H4 | 127.3 |
C11—C16—C15 | 119.8 (4) | C5—C4—H4 | 127.8 |
C11—C16—H16 | 120.0 | N1—C5—C4 | 111.1 (5) |
C15—C16—H16 | 120.2 | N1—C5—H5 | 124.7 |
P—C21—C22 | 120.8 (4) | C4—C5—H5 | 124.1 |
P—C21—C26 | 120.6 (4) | Pd—C101—C102 | 121.8 (4) |
C22—C21—C26 | 118.6 (5) | Pd—C101—C106 | 119.6 (3) |
C21—C22—C23 | 120.5 (5) | C102—C101—C106 | 118.0 (5) |
C21—C22—H22 | 119.7 | C101—C102—C103 | 121.0 (5) |
C23—C22—H22 | 119.8 | C101—C102—H102 | 119.4 |
C22—C23—C24 | 120.4 (6) | C103—C102—H102 | 119.6 |
C22—C23—H23 | 119.8 | C102—C103—C104 | 120.3 (4) |
C24—C23—H23 | 119.8 | C102—C103—H103 | 119.9 |
C23—C24—C25 | 119.7 (7) | C104—C103—H103 | 119.8 |
C23—C24—H24 | 120.1 | C103—C104—C105 | 119.7 (6) |
C25—C24—H24 | 120.2 | C103—C104—H104 | 120.2 |
C24—C25—C26 | 120.6 (6) | C105—C104—H104 | 120.1 |
C24—C25—H25 | 120.0 | C104—C105—C106 | 119.7 (6) |
C26—C25—H25 | 119.4 | C104—C105—H105 | 120.1 |
C21—C26—C25 | 120.3 (5) | C106—C105—H105 | 120.2 |
C21—C26—H26 | 119.8 | C101—C106—C105 | 121.2 (4) |
C25—C26—H26 | 120.0 | C101—C106—H106 | 119.5 |
P—C31—C32 | 118.2 (4) | C105—C106—H106 | 119.2 |
P—C31—C36 | 123.7 (4) | | |
| | | |
Cl—Pd—P—C11 | −171.9 (2) | Pd—P—C11—C16 | −65.7 (5) |
Cl—Pd—P—C21 | 66.3 (2) | Pd—P—C21—C22 | −17.0 (4) |
Cl—Pd—P—C31 | −53.9 (2) | Pd—P—C31—C32 | −36.7 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···Cl | 0.92 | 2.44 | 3.060 (5) | 124 |
N2—H2···Cli | 0.92 | 2.58 | 3.229 (4) | 128 |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Pd(C6H5)Cl(C3H4N2)(C18H15P)] |
Mr | 549.37 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 300 |
a, b, c (Å) | 9.817 (2), 10.797 (5), 13.523 (7) |
α, β, γ (°) | 72.85 (4), 88.21 (3), 63.55 (3) |
V (Å3) | 1217.8 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.96 |
Crystal size (mm) | 0.70 × 0.52 × 0.25 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Gaussian ABSORB in Xtal; Hall et al., 1995) |
Tmin, Tmax | 0.63, 0.73 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4265, 4265, 3887 |
Rint | ? |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.076, 1.28 |
No. of reflections | 3887 |
No. of parameters | 289 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.80, −0.77 |
Selected geometric parameters (Å, º) topPd—Cl | 2.4174 (15) | Pd—N1 | 2.116 (4) |
Pd—P | 2.2451 (12) | Pd—C101 | 1.995 (5) |
| | | |
Cl—Pd—P | 91.18 (5) | P—Pd—C101 | 91.54 (13) |
Cl—Pd—N1 | 89.96 (12) | N1—Pd—C101 | 87.34 (17) |
Cl—Pd—C101 | 175.06 (14) | Pd—N1—N2 | 120.1 (3) |
P—Pd—N1 | 178.86 (12) | Pd—N1—C5 | 134.2 (3) |
| | | |
Cl—Pd—P—C11 | −171.9 (2) | Pd—P—C11—C16 | −65.7 (5) |
Cl—Pd—P—C21 | 66.3 (2) | Pd—P—C21—C22 | −17.0 (4) |
Cl—Pd—P—C31 | −53.9 (2) | Pd—P—C31—C32 | −36.7 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···Cl | 0.92 | 2.44 | 3.060 (5) | 124 |
N2—H2···Cli | 0.92 | 2.58 | 3.229 (4) | 128 |
Symmetry code: (i) −x, −y+1, −z+1. |
Ongoing interest in the catalytic behaviour of palladium(II) systems has resulted in an abundance of structurally characterized square-planar four-coordinate palladium(II) arrays with the four different donor atoms Cl, P, N, C, which form a significant component of the Cambridge Structural Database (CSD, Version?; Allen, 2000), with well over a hundred entries at present. Our current interest in the area has drawn our attention to the dearth of any simple `baseline' systems involving these atoms as simple monodentate donors; in the overwhelming majority of such systems, the pairs of N, C or N, P donors are incorporated, in consequence of various rationales, into chelates. Indeed, we have found only one such system in our CSD search and it is also `unusual' in that the C donor is a carbene (Haltni et al., 1990), a system also prominent in our present interests. Accordingly, the structure of the title complex, (I), a single-crystal obtained as an unexpected decomposition product during studies of poly(pyrazol-1-yl)methane complexes of palladium, is reported here, as it contains a new array of monodentate ligand types which serves as a reference point for the study of the above type. \sch
The results of the room-temperature single-crystal X-ray study of (I) are consistent with the stoichiometry and connectivity implied in the above formulation, the four monodentate ligands comprising a (`square'-)planar four-coordinate array about the divalent Pd atom [χ2 Pd/Cl/P/N1/C101 670; atom deviations 0.008 (1), −0.010 (2), 0.001 (2), 0.018 (4), and −0.120 (5) Å, respectively]. One neutral molecular formula unit, devoid of crystallographic symmetry, with the Cl and phenyl donors mutually trans, comprises the asymmetric unit of the structure of (I) (Fig.1). The angle sum about the Pd atom is 360.0°, the greatest deviation from orthogonality being 87.3 (2)°. Other significant geometries are presented in Table 1.
Perhaps the most interesting comparison which can be made is with the carbenoid system alluded to above. In that system, Pd—P (in PMe2Ph) is 2.255 (2) Å [cf. 2.245 (1) Å in (I)], Pd—N [in aziridine, HN(CH2)3, a cyclic array with C—N—C 88.7 (5)°] 2.109 (5) Å [cf. 2.116 (4) Å in (I)], Pd—Cl 2.363 (2) Å [cf. 2.417 (2) Å in (I)] and Pd—C {in C[N(CH2)3]NHC6H4OMe-p; N—C—N 118.6 (5)°} 1.990 (6) Å [cf. 1.995 (4) Å in (I)] [angle sum 360.0°; greatest deviation from orthogonality 91.1 (2)°]. The only notable difference is in the Pd—Cl distances, presumably to be ascribed to significant and unsurprizing differences in the trans-effects of the two types of trigonal-C donors. In both cases, the planes of the latter lie quasi-normal to the coordination plane. In (I), the interplanar dihedral angle is 89.0 (2)°, the Pd deviations δPd being 0.277 (8)°.
The pyrazole ring [χ2 0.4, δPd 0.025 (9) Å] is quasi-coplanar with the coordination plane [interplanar dihedral 3.9 (2)°], perhaps in consequence of the `protonic' H atom at N2 forming in-plane hydrogen-bonds to the adjacent Cl− ligand (Table 2), there being also a similar intermolecular contact.
The Pd—N1—N2/C5 angles are quite unsymmetrical [120.1 (3) and 134.2 (3)°, respectively]. The torsion angles (Table 1) show that the triphenylphosphine is rather distorted from exact threefold symmetry, while atom C11 is quasi-coplanar with the coordination plane, perhaps accounting for the enlargement of Pd—P—C11 and C21—P—C31.