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In the title compound, trans-[PdCl2{P(C7H7)3}2], where P(C7H7)3 is tri-m-tolylphosphine, the Pd atom is on an inversion centre, resulting in a trans-square-planar geometry. Selected geometric parameters are Pd—P and Pd—Cl distances of 2.3289 (4) and 2.2897 (4) Å, respectively, and a P—Pd—Cl angle of 87.77 (2)°. The effective cone angle for the tri-m-tolylphosphine is calculated to be 165°.
Supporting information
CCDC reference: 613671
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.003 Å
- R factor = 0.027
- wR factor = 0.069
- Data-to-parameter ratio = 21.5
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.66
PLAT230_ALERT_2_C Hirshfeld Test Diff for C17 - C19 .. 6.09 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Pd - Cl .. 5.38 su
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).
trans-Dichlorobis(tri-
m-tolylphosphine)palladium(II)
top
Crystal data top
[PdCl2(C21H21P)2] | Z = 1 |
Mr = 786 | F(000) = 404 |
Triclinic, P1 | Dx = 1.391 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1864 (3) Å | Cell parameters from 7240 reflections |
b = 10.4434 (3) Å | θ = 2.3–28.3° |
c = 11.1137 (5) Å | µ = 0.75 mm−1 |
α = 108.102 (2)° | T = 100 K |
β = 114.206 (2)° | Cuboid, yellow |
γ = 102.811 (2)° | 0.21 × 0.15 × 0.13 mm |
V = 938.17 (7) Å3 | |
Data collection top
Bruker X8 APEX-II 4K KappaCCD area-detector diffractometer | 4673 independent reflections |
Graphite monochromator | 4360 reflections with I > 2σ(I) |
Detector resolution: 8.2 pixels mm-1 | Rint = 0.032 |
ω and φ scans | θmax = 28.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −13→13 |
Tmin = 0.858, Tmax = 0.909 | k = −13→13 |
44847 measured reflections | l = −14→14 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.027 | w = 1/[σ2(Fo2) + (0.0319P)2 + 1.0272P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.069 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 1.33 e Å−3 |
4673 reflections | Δρmin = −0.50 e Å−3 |
217 parameters | |
Special details top
Experimental. The intensity data were collected on a Bruker X8 APEXII 4 K KappaCCD
diffractometer using an exposure time of 10 s/frame. A total of 4504 frames
were collected with a frame width of 0.5° covering up to θ = 28.36° with
99.6% completeness accomplished. Spectroscopic analysis: 1H NMR (CDCl3, 600 MHz, δ, p.p.m.): 7.57 (s, 6H,
Ar), 7.44 (s, 6H, Ar), 7.21 (m, 6H, Ar), 7.12–7.03 (m, 6H, Ar), 2.33 (s, 18H,
CH3); 13C{H} NMR (CDCl3, 75.45 MHz, δ, p.p.m.): 137.9, 136.2, 132.6,
131.7, 130.1, 128.2, 22.0; 31P{H} NMR (CDCl3, 121.46 MHz, δ, p.p.m.):
24.64. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.8517 (2) | 0.49478 (19) | 0.71106 (19) | 0.0177 (3) | |
C2 | 0.9068 (2) | 0.59641 (19) | 0.66733 (19) | 0.0187 (3) | |
H2 | 0.8443 | 0.646 | 0.6311 | 0.022* | |
C3 | 1.0516 (2) | 0.6264 (2) | 0.6758 (2) | 0.0201 (3) | |
C4 | 1.1112 (2) | 0.7389 (2) | 0.6323 (2) | 0.0258 (4) | |
H4A | 1.0238 | 0.7591 | 0.5729 | 0.039* | |
H4B | 1.1568 | 0.7009 | 0.5741 | 0.039* | |
H4C | 1.1917 | 0.8299 | 0.7214 | 0.039* | |
C5 | 1.1400 (2) | 0.5501 (2) | 0.7274 (2) | 0.0240 (4) | |
H5 | 1.2385 | 0.5681 | 0.7332 | 0.029* | |
C6 | 1.0862 (2) | 0.4488 (2) | 0.7702 (2) | 0.0266 (4) | |
H6 | 1.1479 | 0.3979 | 0.8048 | 0.032* | |
C7 | 0.9419 (2) | 0.4208 (2) | 0.7628 (2) | 0.0235 (4) | |
H7 | 0.9057 | 0.3517 | 0.793 | 0.028* | |
C8 | 0.7177 (2) | 0.6107 (2) | 0.8804 (2) | 0.0195 (3) | |
C9 | 0.8601 (2) | 0.7336 (2) | 0.9697 (2) | 0.0221 (4) | |
H9 | 0.9372 | 0.7409 | 0.942 | 0.027* | |
C10 | 0.8923 (3) | 0.8465 (2) | 1.0992 (2) | 0.0270 (4) | |
C11 | 1.0461 (3) | 0.9804 (3) | 1.1916 (3) | 0.0387 (5) | |
H11A | 1.0427 | 1.0453 | 1.1439 | 0.058* | |
H11B | 1.1324 | 0.9495 | 1.2008 | 0.058* | |
H11C | 1.063 | 1.0333 | 1.2901 | 0.058* | |
C12 | 0.7780 (3) | 0.8328 (2) | 1.1379 (2) | 0.0297 (4) | |
H12 | 0.7976 | 0.9081 | 1.2256 | 0.036* | |
C13 | 0.6356 (3) | 0.7108 (2) | 1.0502 (2) | 0.0288 (4) | |
H13 | 0.559 | 0.7033 | 1.0785 | 0.035* | |
C14 | 0.6046 (2) | 0.6001 (2) | 0.9220 (2) | 0.0248 (4) | |
H14 | 0.5068 | 0.517 | 0.8622 | 0.03* | |
C15 | 0.5833 (2) | 0.2980 (2) | 0.6984 (2) | 0.0228 (4) | |
C16 | 0.6561 (2) | 0.2717 (2) | 0.8199 (2) | 0.0262 (4) | |
H16 | 0.7495 | 0.347 | 0.9073 | 0.031* | |
C17 | 0.5911 (3) | 0.1336 (2) | 0.8133 (3) | 0.0302 (4) | |
C18 | 0.6666 (3) | 0.1041 (3) | 0.9433 (3) | 0.0356 (5) | |
H18A | 0.6123 | 0.1171 | 0.9985 | 0.053* | |
H18B | 0.7773 | 0.1729 | 1.0079 | 0.053* | |
H18C | 0.6595 | 0.0029 | 0.9086 | 0.053* | |
C19 | 0.4539 (3) | 0.0271 (2) | 0.6861 (3) | 0.0324 (5) | |
H19 | 0.41 | −0.0661 | 0.6811 | 0.039* | |
C20 | 0.3795 (3) | 0.0519 (2) | 0.5673 (3) | 0.0343 (5) | |
H20 | 0.2842 | −0.0229 | 0.4815 | 0.041* | |
C21 | 0.4441 (2) | 0.1878 (2) | 0.5722 (3) | 0.0287 (4) | |
H21 | 0.3931 | 0.2051 | 0.4894 | 0.034* | |
P | 0.66511 (5) | 0.47356 (5) | 0.70156 (5) | 0.01677 (9) | |
Cl | 0.53757 (5) | 0.31954 (5) | 0.35465 (5) | 0.02334 (10) | |
Pd | 0.5 | 0.5 | 0.5 | 0.01543 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0170 (8) | 0.0211 (8) | 0.0210 (8) | 0.0101 (6) | 0.0128 (7) | 0.0106 (7) |
C2 | 0.0182 (8) | 0.0193 (8) | 0.0228 (8) | 0.0095 (6) | 0.0128 (7) | 0.0100 (7) |
C3 | 0.0196 (8) | 0.0191 (8) | 0.0217 (8) | 0.0066 (7) | 0.0131 (7) | 0.0069 (7) |
C4 | 0.0258 (9) | 0.0230 (9) | 0.0367 (10) | 0.0091 (7) | 0.0225 (8) | 0.0145 (8) |
C5 | 0.0180 (8) | 0.0303 (10) | 0.0275 (9) | 0.0116 (7) | 0.0144 (7) | 0.0123 (8) |
C6 | 0.0241 (9) | 0.0368 (11) | 0.0331 (10) | 0.0209 (8) | 0.0177 (8) | 0.0220 (9) |
C7 | 0.0242 (9) | 0.0308 (10) | 0.0302 (9) | 0.0171 (8) | 0.0182 (8) | 0.0206 (8) |
C8 | 0.0233 (8) | 0.0231 (8) | 0.0242 (8) | 0.0152 (7) | 0.0162 (7) | 0.0152 (7) |
C9 | 0.0255 (9) | 0.0255 (9) | 0.0253 (9) | 0.0142 (7) | 0.0173 (8) | 0.0144 (7) |
C10 | 0.0348 (10) | 0.0269 (10) | 0.0264 (9) | 0.0161 (8) | 0.0178 (8) | 0.0150 (8) |
C11 | 0.0443 (13) | 0.0316 (11) | 0.0307 (11) | 0.0089 (10) | 0.0199 (10) | 0.0070 (9) |
C12 | 0.0473 (12) | 0.0302 (10) | 0.0316 (10) | 0.0263 (9) | 0.0284 (10) | 0.0185 (9) |
C13 | 0.0397 (11) | 0.0364 (11) | 0.0399 (11) | 0.0278 (9) | 0.0323 (10) | 0.0259 (9) |
C14 | 0.0268 (9) | 0.0298 (10) | 0.0348 (10) | 0.0179 (8) | 0.0224 (8) | 0.0207 (8) |
C15 | 0.0278 (9) | 0.0222 (9) | 0.0387 (10) | 0.0165 (7) | 0.0260 (8) | 0.0204 (8) |
C16 | 0.0311 (10) | 0.0309 (10) | 0.0384 (11) | 0.0200 (8) | 0.0270 (9) | 0.0229 (9) |
C17 | 0.0425 (12) | 0.0387 (11) | 0.0485 (12) | 0.0308 (10) | 0.0391 (11) | 0.0326 (10) |
C18 | 0.0416 (12) | 0.0347 (11) | 0.0404 (12) | 0.0166 (10) | 0.0242 (10) | 0.0234 (10) |
C19 | 0.0386 (11) | 0.0239 (10) | 0.0547 (14) | 0.0167 (9) | 0.0358 (11) | 0.0215 (10) |
C20 | 0.0356 (11) | 0.0226 (10) | 0.0486 (13) | 0.0088 (8) | 0.0266 (10) | 0.0158 (9) |
C21 | 0.0306 (10) | 0.0224 (9) | 0.0430 (12) | 0.0116 (8) | 0.0247 (9) | 0.0175 (9) |
P | 0.0170 (2) | 0.0181 (2) | 0.0246 (2) | 0.01032 (17) | 0.01422 (18) | 0.01325 (18) |
Cl | 0.0271 (2) | 0.0222 (2) | 0.0279 (2) | 0.01682 (17) | 0.01626 (18) | 0.01186 (17) |
Pd | 0.01466 (9) | 0.01439 (9) | 0.02344 (10) | 0.00853 (7) | 0.01209 (7) | 0.01063 (7) |
Geometric parameters (Å, º) top
C1—C7 | 1.389 (2) | C12—C13 | 1.388 (3) |
C1—C2 | 1.399 (2) | C12—H12 | 0.95 |
C1—P | 1.8189 (17) | C13—C14 | 1.383 (3) |
C2—C3 | 1.394 (2) | C13—H13 | 0.95 |
C2—H2 | 0.95 | C14—H14 | 0.95 |
C3—C5 | 1.398 (3) | C15—C21 | 1.394 (3) |
C3—C4 | 1.503 (3) | C15—C16 | 1.395 (3) |
C4—H4A | 0.98 | C15—P | 1.8215 (18) |
C4—H4B | 0.98 | C16—C17 | 1.412 (3) |
C4—H4C | 0.98 | C16—H16 | 0.95 |
C5—C6 | 1.383 (3) | C17—C19 | 1.379 (3) |
C5—H5 | 0.95 | C17—C18 | 1.498 (3) |
C6—C7 | 1.396 (3) | C18—H18A | 0.98 |
C6—H6 | 0.95 | C18—H18B | 0.98 |
C7—H7 | 0.95 | C18—H18C | 0.98 |
C8—C9 | 1.392 (3) | C19—C20 | 1.366 (3) |
C8—C14 | 1.401 (2) | C19—H19 | 0.95 |
C8—P | 1.8188 (19) | C20—C21 | 1.400 (3) |
C9—C10 | 1.399 (3) | C20—H20 | 0.95 |
C9—H9 | 0.95 | C21—H21 | 0.95 |
C10—C12 | 1.392 (3) | P—Pd | 2.3289 (4) |
C10—C11 | 1.510 (3) | Cl—Pd | 2.2897 (4) |
C11—H11A | 0.98 | Pd—Cli | 2.2897 (4) |
C11—H11B | 0.98 | Pd—Pi | 2.3289 (4) |
C11—H11C | 0.98 | | |
| | | |
C7—C1—C2 | 119.62 (16) | C14—C13—C12 | 120.40 (18) |
C7—C1—P | 124.01 (13) | C14—C13—H13 | 119.8 |
C2—C1—P | 116.33 (13) | C12—C13—H13 | 119.8 |
C3—C2—C1 | 121.42 (16) | C13—C14—C8 | 119.90 (19) |
C3—C2—H2 | 119.3 | C13—C14—H14 | 120 |
C1—C2—H2 | 119.3 | C8—C14—H14 | 120 |
C2—C3—C5 | 118.01 (17) | C21—C15—C16 | 119.33 (18) |
C2—C3—C4 | 120.80 (17) | C21—C15—P | 119.20 (15) |
C5—C3—C4 | 121.18 (16) | C16—C15—P | 121.47 (16) |
C3—C4—H4A | 109.5 | C15—C16—C17 | 120.2 (2) |
C3—C4—H4B | 109.5 | C15—C16—H16 | 119.9 |
H4A—C4—H4B | 109.5 | C17—C16—H16 | 119.9 |
C3—C4—H4C | 109.5 | C19—C17—C16 | 118.8 (2) |
H4A—C4—H4C | 109.5 | C19—C17—C18 | 120.28 (19) |
H4B—C4—H4C | 109.5 | C16—C17—C18 | 120.9 (2) |
C6—C5—C3 | 121.02 (17) | C17—C18—H18A | 109.5 |
C6—C5—H5 | 119.5 | C17—C18—H18B | 109.5 |
C3—C5—H5 | 119.5 | H18A—C18—H18B | 109.5 |
C5—C6—C7 | 120.51 (17) | C17—C18—H18C | 109.5 |
C5—C6—H6 | 119.7 | H18A—C18—H18C | 109.5 |
C7—C6—H6 | 119.7 | H18B—C18—H18C | 109.5 |
C1—C7—C6 | 119.41 (17) | C20—C19—C17 | 121.80 (19) |
C1—C7—H7 | 120.3 | C20—C19—H19 | 119.1 |
C6—C7—H7 | 120.3 | C17—C19—H19 | 119.1 |
C9—C8—C14 | 119.07 (17) | C19—C20—C21 | 119.7 (2) |
C9—C8—P | 121.93 (13) | C19—C20—H20 | 120.1 |
C14—C8—P | 118.65 (15) | C21—C20—H20 | 120.1 |
C8—C9—C10 | 121.49 (17) | C15—C21—C20 | 120.1 (2) |
C8—C9—H9 | 119.3 | C15—C21—H21 | 119.9 |
C10—C9—H9 | 119.3 | C20—C21—H21 | 119.9 |
C12—C10—C9 | 118.17 (19) | C8—P—C1 | 104.74 (8) |
C12—C10—C11 | 121.51 (19) | C8—P—C15 | 104.42 (9) |
C9—C10—C11 | 120.30 (19) | C1—P—C15 | 108.57 (8) |
C10—C11—H11A | 109.5 | C8—P—Pd | 114.66 (6) |
C10—C11—H11B | 109.5 | C1—P—Pd | 109.91 (6) |
H11A—C11—H11B | 109.5 | C15—P—Pd | 113.96 (7) |
C10—C11—H11C | 109.5 | Cli—Pd—Cl | 180 |
H11A—C11—H11C | 109.5 | Cli—Pd—Pi | 87.772 (16) |
H11B—C11—H11C | 109.5 | Cl—Pd—Pi | 92.228 (16) |
C13—C12—C10 | 120.97 (19) | Cli—Pd—P | 92.228 (16) |
C13—C12—H12 | 119.5 | Cl—Pd—P | 87.772 (16) |
C10—C12—H12 | 119.5 | Pi—Pd—P | 180 |
| | | |
C7—C1—C2—C3 | −0.6 (3) | C16—C15—C21—C20 | −0.7 (3) |
P—C1—C2—C3 | 177.28 (14) | P—C15—C21—C20 | 179.78 (16) |
C1—C2—C3—C5 | 1.0 (3) | C19—C20—C21—C15 | −0.5 (3) |
C1—C2—C3—C4 | −178.33 (17) | C9—C8—P—C1 | 21.84 (17) |
C2—C3—C5—C6 | −0.6 (3) | C14—C8—P—C1 | −165.00 (14) |
C4—C3—C5—C6 | 178.70 (19) | C9—C8—P—C15 | 135.89 (15) |
C3—C5—C6—C7 | −0.1 (3) | C14—C8—P—C15 | −50.95 (16) |
C2—C1—C7—C6 | −0.1 (3) | C9—C8—P—Pd | −98.70 (15) |
P—C1—C7—C6 | −177.85 (15) | C14—C8—P—Pd | 74.46 (15) |
C5—C6—C7—C1 | 0.5 (3) | C7—C1—P—C8 | 89.03 (17) |
C14—C8—C9—C10 | −0.3 (3) | C2—C1—P—C8 | −88.75 (15) |
P—C8—C9—C10 | 172.86 (14) | C7—C1—P—C15 | −22.07 (19) |
C8—C9—C10—C12 | 0.4 (3) | C2—C1—P—C15 | 160.15 (14) |
C8—C9—C10—C11 | −178.33 (19) | C7—C1—P—Pd | −147.33 (15) |
C9—C10—C12—C13 | −0.2 (3) | C2—C1—P—Pd | 34.89 (15) |
C11—C10—C12—C13 | 178.5 (2) | C21—C15—P—C8 | 134.50 (15) |
C10—C12—C13—C14 | −0.1 (3) | C16—C15—P—C8 | −44.97 (17) |
C12—C13—C14—C8 | 0.3 (3) | C21—C15—P—C1 | −114.19 (16) |
C9—C8—C14—C13 | −0.1 (3) | C16—C15—P—C1 | 66.34 (17) |
P—C8—C14—C13 | −173.43 (15) | C21—C15—P—Pd | 8.65 (17) |
C21—C15—C16—C17 | 1.5 (3) | C16—C15—P—Pd | −170.82 (13) |
P—C15—C16—C17 | −178.99 (14) | C8—P—Pd—Cli | −7.92 (7) |
C15—C16—C17—C19 | −1.1 (3) | C1—P—Pd—Cli | −125.56 (6) |
C15—C16—C17—C18 | −179.27 (18) | C15—P—Pd—Cli | 112.34 (6) |
C16—C17—C19—C20 | −0.2 (3) | C8—P—Pd—Cl | 172.08 (7) |
C18—C17—C19—C20 | 178.0 (2) | C1—P—Pd—Cl | 54.44 (6) |
C17—C19—C20—C21 | 1.0 (3) | C15—P—Pd—Cl | −67.66 (6) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···Clii | 0.95 | 2.76 | 3.531 (2) | 139 |
C21—H21···Cl | 0.95 | 2.82 | 3.467 (2) | 126 |
Symmetry code: (ii) −x+1, −y, −z+1. |
Comparative geometric parameters (Å) for selected trans-[PdCl2(L)2]
complexes (L is a tertiary phosphine ligand) topL | Pd—P (Å) | Pd—Cl (Å) | Reference |
PPh3 | 2.337 (1) | 2.290 (1) | (a) |
PPh3 | 2.345 (1) | 2.296 (1) | (b) |
| 2.353 (1) | 2.281 (1) | |
P(m-tol)3 | 2.3289 (4) | 2.2897 (4) | (c) |
PCy3 | 2.3628 (9) | 2.3012 (9) | (d) |
PPh(tBu)2 | 2.398 (2) | 2.301 (2) | (e) |
PPh2Cy | 2.3257 (9) | 2.2995 (9) | (f) |
PPh2[p-(tBuNO)Ph] | 2.3298 (6) | 2.2865 (7) | (g) |
PPh2CHCO2H | 2.326 (1) | 2.305 (1) | (h) |
PPh2(NC5H10) | 2.324 (2) | 2.289 (2) | (i) |
Notes: Cy is cyclohexyl; (a) Ferguson et al. (1982);
(b) Kitano et al. (1983); (c) this work; (d) Grushin et
al. (1994); (e)
DiMeglio et al. (1990); (f) Meij et al. (2003); (g)
Leznoff et al. (1999); (h)
Edwards et al. (1998); (i) Burrow et al. (1994). |
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