The title compound,
trans-[Pd(C
6H
4I)I(C
18H
15P)
2], has been crystallized from dichloromethane. The crystal structure of this complex reveals a slightly distorted square-planar coordination geometry of the Pd atom, which lies on a twofold rotation axis. The P atoms in the triphenylphosphine ligands lie slightly out of the planes of the phenyl rings. The crystal structure is stabilized by short intermolecular I
I contacts, weak C—H
π(arene) hydrogen bonds and π–π stacking interactions.
Supporting information
CCDC reference: 610727
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.003 Å
- R factor = 0.031
- wR factor = 0.064
- Data-to-parameter ratio = 41.0
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) I1 - Pd .. 10.40 su
| Author Response:
The crystal suffers from a stacking fault with approximately 2%
of the molecules displaced along the b axis. That effect is
responsible for creating slight disorder in the structure and
generating this alert. See _publ_section_exptl_refinement for
details.
|
Alert level C
DIFMX01_ALERT_2_C The maximum difference density is > 0.1*ZMAX*0.75
_refine_diff_density_max given = 4.320
Test value = 3.975
| Author Response:
See the note above and _publ_section_exptl_refinement.
|
DIFMX02_ALERT_1_C The maximum difference density is > 0.1*ZMAX*0.75
The relevant atom site should be identified.
| Author Response:
See the note above and _publ_section_exptl_refinement.
|
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 3.20
| Author Response:
See the note above and _publ_section_exptl_refinement.
|
PLAT097_ALERT_2_C Maximum (Positive) Residual Density ............ 4.32 e/A 3
| Author Response:
See the note above and _publ_section_exptl_refinement.
|
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
4 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: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
trans-iodo(
p-iodophenyl)bis(triphenylphosphine)palladium(II)
top
Crystal data top
[Pd(C6H4I)I(C18H15P)2] | F(000) = 1872 |
Mr = 960.85 | Dx = 1.783 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 7476 reflections |
a = 25.194 (7) Å | θ = 3.0–37.5° |
b = 13.375 (3) Å | µ = 2.36 mm−1 |
c = 11.419 (3) Å | T = 100 K |
β = 111.49 (3)° | Prism, light yellow |
V = 3580.4 (18) Å3 | 0.25 × 0.15 × 0.15 mm |
Z = 4 | |
Data collection top
Kuma KM-4 CCD diffractometer | 8814 independent reflections |
Radiation source: fine-focus sealed tube | 6153 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 37.5°, θmin = 3.0° |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2003) | h = −42→35 |
Tmin = 0.530, Tmax = 0.713 | k = −22→22 |
29727 measured reflections | l = −18→19 |
Refinement top
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 0.89 | w = 1/[σ2(Fo2) + (0.033P)2] where P = (Fo2 + 2Fc2)/3 |
8814 reflections | (Δ/σ)max = 0.001 |
215 parameters | Δρmax = 4.32 e Å−3 |
0 restraints | Δρmin = −1.35 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
I1 | 0.5000 | 0.95880 (2) | 0.2500 | 0.01936 (4) | |
I2 | 0.5000 | 0.23956 (2) | 0.2500 | 0.02018 (4) | |
Pd | 0.5000 | 0.75682 (2) | 0.2500 | 0.01027 (4) | |
P | 0.40012 (2) | 0.75168 (3) | 0.17949 (4) | 0.01080 (8) | |
C1 | 0.5000 | 0.60538 (17) | 0.2500 | 0.0113 (4) | |
C2 | 0.48188 (7) | 0.55267 (13) | 0.13715 (16) | 0.0124 (3) | |
H2 | 0.4695 | 0.5880 | 0.0596 | 0.015* | |
C3 | 0.48163 (7) | 0.44793 (13) | 0.13675 (17) | 0.0142 (3) | |
H3 | 0.4690 | 0.4124 | 0.0593 | 0.017* | |
C4 | 0.5000 | 0.39651 (18) | 0.2500 | 0.0148 (5) | |
C5 | 0.36724 (7) | 0.62811 (13) | 0.13341 (17) | 0.0133 (3) | |
C6 | 0.33987 (7) | 0.59999 (14) | 0.00802 (17) | 0.0155 (3) | |
H6 | 0.3332 | 0.6483 | −0.0568 | 0.019* | |
C7 | 0.32222 (8) | 0.50131 (14) | −0.02273 (19) | 0.0188 (3) | |
H7 | 0.3033 | 0.4829 | −0.1084 | 0.023* | |
C8 | 0.33210 (8) | 0.43003 (14) | 0.0708 (2) | 0.0208 (4) | |
H8 | 0.3211 | 0.3625 | 0.0492 | 0.025* | |
C9 | 0.35813 (7) | 0.45753 (14) | 0.19625 (19) | 0.0177 (3) | |
H9 | 0.3642 | 0.4091 | 0.2607 | 0.021* | |
C10 | 0.37534 (7) | 0.55630 (13) | 0.22762 (17) | 0.0149 (3) | |
H10 | 0.3927 | 0.5750 | 0.3136 | 0.018* | |
C11 | 0.36791 (7) | 0.79163 (13) | 0.29111 (16) | 0.0130 (3) | |
C12 | 0.31090 (7) | 0.76641 (13) | 0.26972 (18) | 0.0157 (3) | |
H12 | 0.2892 | 0.7300 | 0.1964 | 0.019* | |
C13 | 0.28607 (7) | 0.79461 (14) | 0.35571 (18) | 0.0177 (3) | |
H13 | 0.2475 | 0.7777 | 0.3408 | 0.021* | |
C14 | 0.31782 (8) | 0.84731 (14) | 0.46290 (19) | 0.0192 (4) | |
H14 | 0.3010 | 0.8662 | 0.5216 | 0.023* | |
C15 | 0.37415 (8) | 0.87276 (15) | 0.48516 (18) | 0.0189 (4) | |
H15 | 0.3956 | 0.9091 | 0.5588 | 0.023* | |
C16 | 0.39934 (7) | 0.84509 (13) | 0.39951 (17) | 0.0155 (3) | |
H16 | 0.4379 | 0.8626 | 0.4150 | 0.019* | |
C17 | 0.36791 (7) | 0.82459 (13) | 0.03620 (17) | 0.0137 (3) | |
C18 | 0.31405 (7) | 0.86981 (14) | 0.00174 (18) | 0.0151 (3) | |
H18 | 0.2937 | 0.8670 | 0.0572 | 0.018* | |
C19 | 0.29028 (7) | 0.91878 (14) | −0.11325 (18) | 0.0174 (3) | |
H19 | 0.2539 | 0.9494 | −0.1356 | 0.021* | |
C20 | 0.31938 (8) | 0.92319 (15) | −0.19556 (18) | 0.0196 (4) | |
H20 | 0.3029 | 0.9564 | −0.2742 | 0.023* | |
C21 | 0.37281 (8) | 0.87882 (16) | −0.16227 (19) | 0.0218 (4) | |
H21 | 0.3928 | 0.8816 | −0.2184 | 0.026* | |
C22 | 0.39710 (8) | 0.83023 (15) | −0.04686 (18) | 0.0190 (4) | |
H22 | 0.4338 | 0.8007 | −0.0244 | 0.023* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.01512 (7) | 0.01163 (7) | 0.02916 (10) | 0.000 | 0.00555 (6) | 0.000 |
I2 | 0.01860 (8) | 0.01238 (7) | 0.02921 (10) | 0.000 | 0.00835 (7) | 0.000 |
Pd | 0.00688 (7) | 0.01059 (7) | 0.01297 (8) | 0.000 | 0.00320 (6) | 0.000 |
P | 0.00718 (16) | 0.01322 (18) | 0.01158 (19) | 0.00002 (14) | 0.00294 (14) | −0.00124 (16) |
C1 | 0.0080 (9) | 0.0127 (10) | 0.0161 (11) | 0.000 | 0.0077 (8) | 0.000 |
C2 | 0.0100 (6) | 0.0163 (7) | 0.0115 (7) | 0.0014 (6) | 0.0048 (6) | 0.0001 (6) |
C3 | 0.0120 (7) | 0.0158 (7) | 0.0161 (8) | 0.0003 (6) | 0.0066 (6) | −0.0021 (7) |
C4 | 0.0107 (10) | 0.0153 (11) | 0.0199 (12) | 0.000 | 0.0073 (9) | 0.000 |
C5 | 0.0084 (6) | 0.0165 (7) | 0.0160 (8) | −0.0010 (6) | 0.0055 (6) | −0.0036 (7) |
C6 | 0.0108 (7) | 0.0198 (8) | 0.0154 (8) | −0.0027 (6) | 0.0044 (6) | −0.0032 (7) |
C7 | 0.0151 (7) | 0.0227 (8) | 0.0197 (8) | −0.0052 (7) | 0.0076 (6) | −0.0105 (8) |
C8 | 0.0171 (8) | 0.0182 (8) | 0.0318 (11) | −0.0051 (7) | 0.0143 (8) | −0.0089 (8) |
C9 | 0.0165 (8) | 0.0150 (7) | 0.0254 (9) | −0.0031 (6) | 0.0121 (7) | −0.0010 (8) |
C10 | 0.0121 (7) | 0.0165 (7) | 0.0185 (8) | −0.0023 (6) | 0.0083 (6) | −0.0044 (7) |
C11 | 0.0119 (7) | 0.0135 (7) | 0.0141 (8) | 0.0011 (6) | 0.0054 (6) | 0.0002 (7) |
C12 | 0.0132 (7) | 0.0166 (7) | 0.0184 (8) | −0.0008 (6) | 0.0072 (6) | −0.0023 (7) |
C13 | 0.0156 (8) | 0.0178 (8) | 0.0239 (9) | 0.0016 (7) | 0.0122 (7) | 0.0015 (8) |
C14 | 0.0245 (9) | 0.0175 (8) | 0.0198 (9) | 0.0043 (7) | 0.0131 (8) | 0.0017 (7) |
C15 | 0.0221 (9) | 0.0195 (8) | 0.0147 (8) | 0.0024 (7) | 0.0062 (7) | −0.0012 (7) |
C16 | 0.0134 (7) | 0.0167 (8) | 0.0143 (8) | 0.0011 (6) | 0.0027 (6) | −0.0001 (7) |
C17 | 0.0105 (7) | 0.0148 (7) | 0.0149 (8) | −0.0002 (6) | 0.0037 (6) | −0.0007 (7) |
C18 | 0.0102 (7) | 0.0169 (7) | 0.0178 (8) | 0.0006 (6) | 0.0047 (6) | −0.0007 (7) |
C19 | 0.0131 (7) | 0.0158 (7) | 0.0204 (9) | 0.0013 (6) | 0.0025 (6) | −0.0002 (7) |
C20 | 0.0175 (8) | 0.0221 (8) | 0.0161 (9) | 0.0005 (7) | 0.0026 (7) | 0.0002 (8) |
C21 | 0.0198 (9) | 0.0294 (10) | 0.0178 (9) | 0.0032 (7) | 0.0090 (7) | 0.0044 (8) |
C22 | 0.0132 (8) | 0.0256 (9) | 0.0185 (9) | 0.0034 (7) | 0.0062 (7) | 0.0019 (8) |
Geometric parameters (Å, º) top
Pd—I1 | 2.7015 (6) | C9—H9 | 0.950 |
Pd—P | 2.345 (1) | C10—H10 | 0.950 |
Pd—Pi | 2.345 (1) | C11—C16 | 1.397 (3) |
Pd—C1 | 2.025 (2) | C11—C12 | 1.407 (2) |
I2—C4 | 2.099 (3) | C12—C13 | 1.396 (2) |
P—C5 | 1.837 (2) | C12—H12 | 0.950 |
P—C11 | 1.824 (2) | C13—C14 | 1.385 (3) |
P—C17 | 1.820 (2) | C13—H13 | 0.950 |
C1—C2 | 1.391 (2) | C14—C15 | 1.389 (3) |
C1—C2i | 1.391 (2) | C14—H14 | 0.950 |
C2—C3 | 1.401 (2) | C15—C16 | 1.397 (3) |
C2—H2 | 0.950 | C15—H15 | 0.950 |
C3—C4 | 1.386 (2) | C16—H16 | 0.950 |
C3—H3 | 0.950 | C17—C22 | 1.399 (3) |
C4—C3i | 1.386 (2) | C17—C18 | 1.404 (2) |
C5—C6 | 1.394 (3) | C18—C19 | 1.391 (3) |
C5—C10 | 1.400 (3) | C18—H18 | 0.950 |
C6—C7 | 1.396 (3) | C19—C20 | 1.389 (3) |
C6—H6 | 0.950 | C19—H19 | 0.950 |
C7—C8 | 1.384 (3) | C20—C21 | 1.391 (3) |
C7—H7 | 0.950 | C20—H20 | 0.950 |
C8—C9 | 1.389 (3) | C21—C22 | 1.394 (3) |
C8—H8 | 0.950 | C21—H21 | 0.950 |
C9—C10 | 1.396 (3) | C22—H22 | 0.950 |
| | | |
P—Pd—C1 | 88.32 (2) | C9—C10—C5 | 120.5 (2) |
Pi—Pd—C1 | 88.32 (2) | C9—C10—H10 | 119.7 |
P—Pd—I1 | 91.68 (2) | C5—C10—H10 | 119.7 |
Pi—Pd—I1 | 91.68 (2) | C16—C11—C12 | 119.1 (2) |
P—Pd—Pi | 176.64 (2) | C16—C11—P | 121.1 (2) |
C1—Pd—I1 | 180.0 | C12—C11—P | 119.7 (2) |
C17—P—C11 | 107.77 (8) | C13—C12—C11 | 120.4 (2) |
C17—P—C5 | 102.63 (8) | C13—C12—H12 | 119.8 |
C11—P—C5 | 101.20 (8) | C11—C12—H12 | 119.8 |
C17—P—Pd | 111.21 (6) | C14—C13—C12 | 119.8 (2) |
C11—P—Pd | 116.59 (6) | C14—C13—H13 | 120.1 |
C5—P—Pd | 116.05 (6) | C12—C13—H13 | 120.1 |
C2—C1—C2i | 119.1 (2) | C13—C14—C15 | 120.5 (2) |
C2—C1—Pd | 120.4 (1) | C13—C14—H14 | 119.8 |
C2i—C1—Pd | 120.4 (1) | C15—C14—H14 | 119.8 |
C1—C2—C3 | 120.6 (2) | C14—C15—C16 | 120.2 (2) |
C1—C2—H2 | 119.7 | C14—C15—H15 | 119.9 |
C3—C2—H2 | 119.7 | C16—C15—H15 | 119.9 |
C4—C3—C2 | 119.6 (2) | C15—C16—C11 | 120.0 (2) |
C4—C3—H3 | 120.2 | C15—C16—H16 | 120.0 |
C2—C3—H3 | 120.2 | C11—C16—H16 | 120.0 |
C3i—C4—C3 | 120.5 (2) | C22—C17—C18 | 118.8 (2) |
C3i—C4—I2 | 119.8 (2) | C22—C17—P | 117.8 (2) |
C3—C4—I2 | 119.8 (2) | C18—C17—P | 123.3 (2) |
C6—C5—C10 | 118.8 (2) | C19—C18—C17 | 120.3 (2) |
C6—C5—P | 122.6 (2) | C19—C18—H18 | 119.8 |
C10—C5—P | 118.3 (2) | C17—C18—H18 | 119.8 |
C5—C6—C7 | 120.4 (2) | C20—C19—C18 | 120.5 (2) |
C5—C6—H6 | 119.8 | C20—C19—H19 | 119.8 |
C7—C6—H6 | 119.8 | C18—C19—H19 | 119.8 |
C8—C7—C6 | 120.4 (2) | C19—C20—C21 | 119.7 (2) |
C8—C7—H7 | 119.8 | C19—C20—H20 | 120.2 |
C6—C7—H7 | 119.8 | C21—C20—H20 | 120.2 |
C7—C8—C9 | 119.8 (2) | C20—C21—C22 | 120.2 (2) |
C7—C8—H8 | 120.1 | C20—C21—H21 | 119.9 |
C9—C8—H8 | 120.1 | C22—C21—H21 | 119.9 |
C8—C9—C10 | 120.0 (2) | C21—C22—C17 | 120.6 (2) |
C8—C9—H9 | 120.0 | C21—C22—H22 | 119.7 |
C10—C9—H9 | 120.0 | C17—C22—H22 | 119.7 |
| | | |
I1—Pd—P—C17 | 54.11 (6) | C17—P—C11—C16 | −110.5 (2) |
C1—Pd—P—C17 | −125.89 (6) | C5—P—C11—C16 | 142.2 (2) |
I1—Pd—P—C11 | −69.97 (6) | Pd—P—C11—C16 | 15.4 (2) |
C1—Pd—P—C11 | 110.03 (6) | C17—P—C11—C12 | 71.0 (2) |
I1—Pd—P—C5 | 170.91 (7) | C5—P—C11—C12 | −36.3 (2) |
C1—Pd—P—C5 | −9.09 (7) | Pd—P—C11—C12 | −163.2 (2) |
P—Pd—C1—C2 | 72.10 (8) | C16—C11—C12—C13 | 0.1 (3) |
Pi—Pd—C1—C2 | −107.90 (8) | P—C11—C12—C13 | 178.6 (2) |
P—Pd—C1—C2i | −107.90 (8) | C11—C12—C13—C14 | −0.3 (3) |
Pi—Pd—C1—C2i | 72.10 (8) | C12—C13—C14—C15 | 0.3 (3) |
C2i—C1—C2—C3 | 0.2 (1) | C13—C14—C15—C16 | −0.2 (3) |
Pd—C1—C2—C3 | −179.8 (1) | C14—C15—C16—C11 | 0.0 (3) |
C1—C2—C3—C4 | −0.4 (2) | C12—C11—C16—C15 | 0.1 (3) |
C2—C3—C4—C3i | 0.2 (2) | P—C11—C16—C15 | −178.4 (2) |
C2—C3—C4—I2 | −179.8 (1) | C11—P—C17—C22 | 160.6 (2) |
C17—P—C5—C6 | 17.0 (2) | C5—P—C17—C22 | −93.1 (2) |
C11—P—C5—C6 | 128.4 (2) | Pd—P—C17—C22 | 31.7 (2) |
Pd—P—C5—C6 | −104.5 (2) | C11—P—C17—C18 | −23.4 (2) |
C17—P—C5—C10 | −169.8 (2) | C5—P—C17—C18 | 82.9 (2) |
C11—P—C5—C10 | −58.5 (2) | Pd—P—C17—C18 | −152.4 (2) |
Pd—P—C5—C10 | 68.7 (2) | C22—C17—C18—C19 | 0.3 (3) |
C10—C5—C6—C7 | −1.6 (2) | P—C17—C18—C19 | −175.6 (2) |
P—C5—C6—C7 | 171.5 (2) | C17—C18—C19—C20 | 0.3 (3) |
C5—C6—C7—C8 | −0.5 (3) | C18—C19—C20—C21 | −0.4 (3) |
C6—C7—C8—C9 | 2.0 (3) | C19—C20—C21—C22 | −0.1 (3) |
C7—C8—C9—C10 | −1.3 (3) | C20—C21—C22—C17 | 0.6 (3) |
C8—C9—C10—C5 | −0.8 (3) | C18—C17—C22—C21 | −0.8 (3) |
C6—C5—C10—C9 | 2.3 (3) | P—C17—C22—C21 | 175.4 (2) |
P—C5—C10—C9 | −171.1 (2) | | |
Symmetry code: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···Cg1ii | 0.95 | 2.77 | 3.629 (3) | 150 |
Symmetry code: (ii) −x+1/2, −y+3/2, −z. |
Intermolecular π–π interactions (Å, °) topCg2 denotes the
centroid of ring C11–C16 and Cg3 of ring C17–C22; Cg···Cg is the distance
between ring centroids; the dihedral angle is that between the CgI and
CgJ planes; the interplanar distance is the perpendicular distance of CgI
from the plane of ring J; the offset is the lateral displacement of ring I
relative to ring J |
CgI | CgJ | Cg..Cg | Dihedral angle | Interplanar dist. | Offset |
2 | 3ii | 4.122 (3) | 10.1 (2) | 3.352 (3) | 2.399 (3) |
3 | 2iii | 4.122 (3) | 10.1 (2) | 3.316 (3) | 2.448 (3) |
Symmetry codes: (ii) x, 2-y, 1/2+z; (iii) x, 2-y, -1/2+z. |