Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008626/fl6020sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008626/fl6020Isup2.hkl |
CCDC reference: 214580
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.009 Å
- Disorder in solvent or counterion
- R factor = 0.053
- wR factor = 0.144
- Data-to-parameter ratio = 17.6
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.48 From the CIF: _reflns_number_total 8029 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 8763 Completeness (_total/calc) 91.62% Alert C: < 95% complete PLAT_302 Alert C Anion/Solvent Disorder ....................... 21.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
A solution of Pd(PPh3)4 (57.5 mg, 0.05 mmol), mesitylboronic acid (935 mg, 5.7 mmol), 6,6''-dibromo-2,2':6',2''-terpyridine (740 mg, 1.9 mmol) and Na3PO4.12H2O (3 g, 7.9 mmol) in a mixture of DME (18 ml) and H2O (3 ml) were refluxed for 20 h under an argon atmosphere. The solution was cooled to room temperature and the solvent evaporated under reduced pressure. The residue was extracted with benzene, washed with brine and dried over MgSO4. Solvents were removed under reduced pressure to give white precipitate, which was collected with filtration and washed with hexane. The precipitate was dried in vacuo and recrystallized from toluene to give microcrystals. Yield 510 mg, 57%. (m.p. 553 K). Spectroscopic analysis: 1H NMR (CDCl3 at 298 K): 2.11 (s, 12H), 2.35 (s, 6H), 6.98 (s, 4H), 7.26 (d, 2H), 7.83 (t, 1H), 7.92 (t, 2H), 8.50 (d, 2H), 8.59 (dd, 2H); analysis calculated for C33H31N3: C 84.40, H 6.65, N 8.95%; found: C 84.04, H 6.55, N 8.92%. A solution of dmtpy (15.0 mg, 0.032 mmol) in CH2Cl2 (1.5 ml) was added to a solution of trans-Pd(MeCN)2Cl2 (8.3 mg, 0.032 mmol) in CH2Cl2(1.0 ml) and stirred at room temperature for 20 h to give a yellow precipitate. The yellow powder was washed with pentane and dried in vacuo. The product was recrystallized from dichloromethane/hexane to give crystals suitable for X-ray analysis. Spectroscpic analysis: 1H NMR (CDCl3 at 298 K) 2.18 (s, 12H), 2.23 (s, 6H), 6.78 (s, 4H), 7.39 (2H, d), 8.31 (2H, t), 8.95 (2H, d), 9.00 (1H, t), 9.21 (2H, d); analysis calculated for C69H68N6Pd3Cl12: C 48.01. H 3.97, N 4.87%; found: C 47.62, H 3.88, N 4.86%.
Data collection and cell refinement: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); data reduction: TEXSAN (Molecular Structure Corporation, 1999)
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
[PdCl(C33H31N3)]2[PdCl4]·4CH2Cl2 | Z = 1 |
Mr = 1810.82 | F(000) = 908 |
Triclinic, P1 | Dx = 1.574 Mg m−3 |
a = 10.6555 (7) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 21.3398 (5) Å | Cell parameters from 12443 reflections |
c = 8.5995 (1) Å | θ = 2.3–27.4° |
α = 91.21° | µ = 1.23 mm−1 |
β = 100.468 (7)° | T = 200 K |
γ = 83.566 (7)° | Platelet, orange |
V = 1910.75 (14) Å3 | 0.15 × 0.15 × 0.05 mm |
Rigaku R-AXIS-RAPID Imaging Plate diffractometer | 8029 independent reflections |
Radiation source: fine-focus sealed tube | 4933 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 2.1° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −27→27 |
Tmin = 0.777, Tmax = 0.940 | l = −11→11 |
9543 measured reflections |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.078P)2] where P = (Fo2 + 2Fc2)/3 |
8029 reflections | (Δ/σ)max < 0.001 |
455 parameters | Δρmax = 0.53 e Å−3 |
2 restraints | Δρmin = −1.36 e Å−3 |
[PdCl(C33H31N3)]2[PdCl4]·4CH2Cl2 | γ = 83.566 (7)° |
Mr = 1810.82 | V = 1910.75 (14) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.6555 (7) Å | Mo Kα radiation |
b = 21.3398 (5) Å | µ = 1.23 mm−1 |
c = 8.5995 (1) Å | T = 200 K |
α = 91.21° | 0.15 × 0.15 × 0.05 mm |
β = 100.468 (7)° |
Rigaku R-AXIS-RAPID Imaging Plate diffractometer | 8029 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 4933 reflections with I > 2σ(I) |
Tmin = 0.777, Tmax = 0.940 | Rint = 0.037 |
9543 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 2 restraints |
wR(F2) = 0.144 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.53 e Å−3 |
8029 reflections | Δρmin = −1.36 e Å−3 |
455 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pd1 | 0.36247 (4) | 0.190898 (18) | 0.51368 (5) | 0.04205 (13) | |
Pd2 | 1.0000 | 0.0000 | 1.0000 | 0.04568 (16) | |
Cl1 | 0.34252 (12) | 0.29833 (6) | 0.49358 (19) | 0.0549 (4) | |
Cl2 | 0.92476 (15) | −0.03122 (8) | 0.7432 (2) | 0.0689 (4) | |
Cl3 | 0.80997 (13) | 0.06468 (7) | 0.99641 (19) | 0.0596 (4) | |
Cl11 | 0.6628 (3) | 0.21062 (11) | 0.8485 (3) | 0.1074 (7) | |
Cl12 | 0.7226 (3) | 0.33957 (16) | 0.8612 (4) | 0.1533 (12) | |
Cl21 | 0.7376 (14) | 0.4774 (5) | 0.6671 (13) | 0.219 (6) | 0.632 (11) |
Cl22 | 0.6860 (13) | 0.5227 (3) | 0.3693 (8) | 0.200 (5) | 0.632 (11) |
Cl31 | 0.7697 (14) | 0.4826 (7) | 0.616 (3) | 0.243 (13) | 0.368 (11) |
Cl32 | 0.5549 (11) | 0.5472 (4) | 0.3748 (13) | 0.138 (5) | 0.368 (11) |
N11 | 0.5380 (4) | 0.1671 (2) | 0.4393 (5) | 0.0459 (10) | |
N21 | 0.4055 (4) | 0.1057 (2) | 0.6002 (6) | 0.0496 (11) | |
N31 | 0.1908 (4) | 0.1810 (2) | 0.5907 (5) | 0.0474 (11) | |
C1 | 0.6037 (7) | 0.2902 (4) | 0.8339 (10) | 0.083 (2) | |
H32 | 0.5497 | 0.2982 | 0.7283 | 0.100* | |
H33 | 0.5483 | 0.3001 | 0.9140 | 0.100* | |
C2 | 0.6980 (19) | 0.5429 (11) | 0.5590 (16) | 0.109 (8) | 0.632 (11) |
H34 | 0.6151 | 0.5644 | 0.5787 | 0.205* | 0.632 (11) |
H35 | 0.7645 | 0.5721 | 0.5878 | 0.205* | 0.632 (11) |
C3 | 0.672 (4) | 0.547 (2) | 0.538 (5) | 0.18 (3) | 0.368 (11) |
H36 | 0.6286 | 0.5649 | 0.6243 | 0.117* | 0.368 (11) |
H37 | 0.7290 | 0.5779 | 0.5171 | 0.205* | 0.368 (11) |
C12 | 0.6019 (5) | 0.1116 (2) | 0.5093 (7) | 0.0474 (13) | |
C13 | 0.7223 (5) | 0.0877 (3) | 0.4840 (7) | 0.0575 (15) | |
H1 | 0.7659 | 0.0511 | 0.5388 | 0.069* | |
C14 | 0.7791 (5) | 0.1177 (3) | 0.3773 (7) | 0.0591 (15) | |
H2 | 0.8617 | 0.1020 | 0.3574 | 0.070* | |
C15 | 0.7125 (5) | 0.1712 (3) | 0.3008 (7) | 0.0554 (14) | |
H3 | 0.7492 | 0.1917 | 0.2258 | 0.068* | |
C16 | 0.5927 (5) | 0.1954 (3) | 0.3319 (6) | 0.0475 (12) | |
C22 | 0.5287 (5) | 0.0793 (2) | 0.6075 (6) | 0.0464 (13) | |
C23 | 0.5722 (6) | 0.0257 (3) | 0.7002 (7) | 0.0583 (15) | |
H4 | 0.6577 | 0.0063 | 0.7071 | 0.069* | |
C24 | 0.4872 (7) | 0.0012 (3) | 0.7826 (7) | 0.0609 (16) | |
H5 | 0.5145 | −0.0364 | 0.8425 | 0.069* | |
C25 | 0.3629 (6) | 0.0308 (3) | 0.7789 (7) | 0.0634 (17) | |
H6 | 0.3060 | 0.0142 | 0.8364 | 0.076* | |
C26 | 0.3246 (5) | 0.0855 (3) | 0.6880 (7) | 0.0513 (14) | |
C32 | 0.2001 (5) | 0.1259 (3) | 0.6762 (7) | 0.0546 (14) | |
C33 | 0.1026 (6) | 0.1100 (3) | 0.7469 (7) | 0.0602 (16) | |
H7 | 0.1122 | 0.0716 | 0.8042 | 0.073* | |
C34 | −0.0102 (6) | 0.1503 (4) | 0.7342 (8) | 0.075 (2) | |
H8 | −0.0769 | 0.1415 | 0.7874 | 0.089* | |
C35 | −0.0229 (6) | 0.2033 (3) | 0.6428 (8) | 0.0659 (17) | |
H9 | −0.1013 | 0.2303 | 0.6283 | 0.080* | |
C36 | 0.0779 (5) | 0.2186 (3) | 0.5698 (7) | 0.0492 (13) | |
C41 | 0.5212 (5) | 0.2521 (3) | 0.2444 (7) | 0.0467 (12) | |
C42 | 0.5641 (5) | 0.3116 (3) | 0.2751 (7) | 0.0548 (14) | |
C43 | 0.4941 (7) | 0.3631 (3) | 0.1927 (8) | 0.0691 (18) | |
H10 | 0.5232 | 0.4035 | 0.2120 | 0.083* | |
C44 | 0.3830 (7) | 0.3576 (4) | 0.0830 (9) | 0.078 (2) | |
C45 | 0.3455 (7) | 0.2974 (3) | 0.0517 (8) | 0.0734 (19) | |
H11 | 0.2706 | 0.2927 | −0.0246 | 0.089* | |
C46 | 0.4126 (5) | 0.2447 (3) | 0.1268 (7) | 0.0546 (14) | |
C47 | 0.6824 (6) | 0.3210 (3) | 0.3985 (9) | 0.0724 (19) | |
H12 | 0.6764 | 0.3007 | 0.4976 | 0.088* | |
H13 | 0.6873 | 0.3663 | 0.4169 | 0.088* | |
H14 | 0.7595 | 0.3023 | 0.3606 | 0.088* | |
C48 | 0.3053 (11) | 0.4160 (4) | −0.0022 (12) | 0.130 (4) | |
H15 | 0.2208 | 0.4227 | 0.0290 | 0.150* | |
H16 | 0.2945 | 0.4095 | −0.1168 | 0.150* | |
H17 | 0.3512 | 0.4531 | 0.0269 | 0.150* | |
C49 | 0.3739 (7) | 0.1795 (3) | 0.0795 (8) | 0.0741 (19) | |
H18 | 0.3511 | 0.1594 | 0.1704 | 0.090* | |
H19 | 0.4458 | 0.1537 | 0.0449 | 0.090* | |
H20 | 0.2998 | 0.1834 | −0.0072 | 0.090* | |
C51 | 0.0520 (5) | 0.2740 (3) | 0.4578 (6) | 0.0486 (13) | |
C52 | 0.0319 (5) | 0.3350 (3) | 0.5200 (7) | 0.0535 (14) | |
C53 | −0.0018 (6) | 0.3860 (3) | 0.4141 (8) | 0.0628 (16) | |
H21 | −0.0159 | 0.4275 | 0.4539 | 0.073* | |
C54 | −0.0149 (6) | 0.3762 (3) | 0.2511 (9) | 0.0698 (18) | |
C55 | 0.0046 (6) | 0.3160 (3) | 0.1944 (8) | 0.0622 (16) | |
H22 | −0.0043 | 0.3093 | 0.0836 | 0.077* | |
C56 | 0.0374 (5) | 0.2646 (3) | 0.2964 (7) | 0.0535 (14) | |
C57 | 0.0494 (8) | 0.3475 (4) | 0.6958 (8) | 0.083 (2) | |
H23 | 0.1353 | 0.3294 | 0.7468 | 0.097* | |
H24 | −0.0155 | 0.3281 | 0.7399 | 0.097* | |
H25 | 0.0399 | 0.3931 | 0.7147 | 0.097* | |
C58 | −0.0559 (9) | 0.4319 (4) | 0.1361 (11) | 0.107 (3) | |
H26 | −0.1296 | 0.4580 | 0.1660 | 0.130* | |
H27 | −0.0800 | 0.4159 | 0.0284 | 0.130* | |
H28 | 0.0156 | 0.4574 | 0.1404 | 0.130* | |
C59 | 0.0539 (6) | 0.1991 (3) | 0.2235 (8) | 0.0697 (18) | |
H29 | −0.0049 | 0.1980 | 0.1218 | 0.085* | |
H30 | 0.0347 | 0.1678 | 0.2949 | 0.085* | |
H31 | 0.1426 | 0.1894 | 0.2068 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0328 (2) | 0.0427 (2) | 0.0498 (2) | −0.00475 (15) | 0.00403 (16) | 0.00628 (18) |
Pd2 | 0.0391 (3) | 0.0428 (3) | 0.0560 (4) | 0.0018 (2) | 0.0132 (3) | 0.0115 (3) |
Cl1 | 0.0418 (7) | 0.0444 (7) | 0.0806 (10) | −0.0025 (5) | 0.0168 (7) | 0.0079 (7) |
Cl2 | 0.0596 (9) | 0.0706 (10) | 0.0667 (10) | 0.0169 (7) | 0.0007 (7) | −0.0032 (8) |
Cl3 | 0.0456 (7) | 0.0628 (9) | 0.0684 (9) | 0.0104 (6) | 0.0143 (7) | 0.0052 (8) |
Cl11 | 0.1268 (19) | 0.0978 (15) | 0.0898 (15) | 0.0162 (13) | 0.0173 (13) | −0.0090 (12) |
Cl12 | 0.132 (2) | 0.152 (3) | 0.178 (3) | −0.066 (2) | 0.001 (2) | 0.004 (2) |
Cl21 | 0.410 (18) | 0.079 (4) | 0.161 (6) | −0.005 (7) | 0.048 (8) | 0.009 (4) |
Cl22 | 0.333 (15) | 0.156 (5) | 0.143 (5) | −0.057 (7) | 0.114 (7) | −0.010 (4) |
Cl31 | 0.119 (8) | 0.068 (6) | 0.54 (4) | 0.022 (5) | 0.074 (14) | 0.034 (12) |
Cl32 | 0.142 (9) | 0.112 (6) | 0.168 (8) | −0.044 (6) | 0.033 (6) | −0.001 (5) |
N11 | 0.039 (2) | 0.047 (2) | 0.049 (3) | −0.0032 (18) | 0.0013 (19) | −0.004 (2) |
N21 | 0.042 (2) | 0.048 (2) | 0.056 (3) | −0.0093 (19) | −0.002 (2) | 0.003 (2) |
N31 | 0.041 (2) | 0.046 (2) | 0.054 (3) | −0.0105 (19) | 0.001 (2) | 0.009 (2) |
C1 | 0.071 (5) | 0.090 (5) | 0.084 (5) | 0.003 (4) | 0.010 (4) | 0.009 (4) |
C2 | 0.086 (10) | 0.077 (13) | 0.18 (2) | −0.026 (9) | 0.043 (11) | 0.014 (13) |
C3 | 0.22 (5) | 0.11 (3) | 0.15 (4) | 0.11 (3) | −0.05 (3) | −0.03 (3) |
C12 | 0.037 (3) | 0.046 (3) | 0.054 (3) | −0.001 (2) | −0.003 (2) | −0.001 (3) |
C13 | 0.049 (3) | 0.053 (3) | 0.063 (4) | 0.008 (3) | −0.002 (3) | −0.008 (3) |
C14 | 0.040 (3) | 0.072 (4) | 0.062 (4) | 0.006 (3) | 0.009 (3) | −0.009 (3) |
C15 | 0.047 (3) | 0.067 (4) | 0.053 (3) | −0.004 (3) | 0.012 (3) | −0.002 (3) |
C16 | 0.034 (3) | 0.057 (3) | 0.049 (3) | −0.004 (2) | 0.005 (2) | 0.003 (3) |
C22 | 0.050 (3) | 0.040 (3) | 0.044 (3) | −0.001 (2) | −0.003 (2) | −0.010 (2) |
C23 | 0.072 (4) | 0.044 (3) | 0.050 (3) | 0.002 (3) | −0.006 (3) | −0.001 (3) |
C24 | 0.080 (4) | 0.044 (3) | 0.053 (4) | −0.007 (3) | −0.003 (3) | 0.002 (3) |
C25 | 0.074 (4) | 0.060 (4) | 0.055 (4) | −0.025 (3) | −0.003 (3) | 0.010 (3) |
C26 | 0.053 (3) | 0.046 (3) | 0.053 (3) | −0.016 (2) | 0.000 (3) | −0.004 (3) |
C32 | 0.049 (3) | 0.064 (4) | 0.050 (3) | −0.020 (3) | −0.004 (3) | 0.014 (3) |
C33 | 0.051 (4) | 0.070 (4) | 0.062 (4) | −0.020 (3) | 0.005 (3) | 0.017 (3) |
C34 | 0.050 (4) | 0.106 (5) | 0.074 (5) | −0.022 (4) | 0.011 (3) | 0.026 (4) |
C35 | 0.038 (3) | 0.085 (5) | 0.076 (4) | −0.011 (3) | 0.007 (3) | 0.016 (4) |
C36 | 0.032 (3) | 0.060 (3) | 0.056 (3) | −0.009 (2) | 0.007 (2) | 0.009 (3) |
C41 | 0.040 (3) | 0.050 (3) | 0.052 (3) | −0.005 (2) | 0.014 (2) | 0.003 (3) |
C42 | 0.041 (3) | 0.062 (4) | 0.063 (4) | −0.005 (3) | 0.015 (3) | 0.010 (3) |
C43 | 0.071 (4) | 0.055 (4) | 0.084 (5) | −0.010 (3) | 0.018 (4) | 0.010 (3) |
C44 | 0.077 (5) | 0.074 (5) | 0.076 (5) | 0.012 (4) | 0.007 (4) | 0.017 (4) |
C45 | 0.061 (4) | 0.084 (5) | 0.066 (4) | −0.001 (4) | −0.008 (3) | 0.008 (4) |
C46 | 0.044 (3) | 0.064 (4) | 0.055 (3) | −0.005 (3) | 0.006 (3) | 0.005 (3) |
C47 | 0.050 (4) | 0.074 (4) | 0.094 (5) | −0.018 (3) | 0.011 (3) | −0.010 (4) |
C48 | 0.149 (9) | 0.086 (6) | 0.128 (8) | 0.022 (6) | −0.031 (7) | 0.029 (6) |
C49 | 0.063 (4) | 0.093 (5) | 0.060 (4) | −0.016 (4) | −0.011 (3) | −0.008 (4) |
C51 | 0.031 (3) | 0.064 (3) | 0.049 (3) | −0.005 (2) | 0.003 (2) | 0.012 (3) |
C52 | 0.037 (3) | 0.063 (4) | 0.058 (3) | −0.001 (2) | 0.005 (2) | −0.003 (3) |
C53 | 0.057 (4) | 0.045 (3) | 0.083 (5) | −0.002 (3) | 0.006 (3) | −0.003 (3) |
C54 | 0.053 (4) | 0.081 (5) | 0.074 (5) | −0.003 (3) | 0.008 (3) | 0.029 (4) |
C55 | 0.062 (4) | 0.068 (4) | 0.055 (4) | 0.001 (3) | 0.012 (3) | 0.006 (3) |
C56 | 0.037 (3) | 0.062 (4) | 0.061 (4) | −0.003 (2) | 0.008 (3) | 0.007 (3) |
C57 | 0.081 (5) | 0.091 (5) | 0.072 (5) | −0.006 (4) | 0.007 (4) | −0.014 (4) |
C58 | 0.109 (7) | 0.092 (6) | 0.111 (7) | 0.002 (5) | 0.000 (5) | 0.046 (5) |
C59 | 0.061 (4) | 0.074 (4) | 0.069 (4) | 0.001 (3) | 0.004 (3) | 0.005 (4) |
Pd1—N21 | 1.953 (4) | C33—C34 | 1.386 (9) |
Pd1—N31 | 2.089 (4) | C33—H7 | 0.9500 |
Pd1—N11 | 2.091 (4) | C34—C35 | 1.371 (9) |
Pd1—Cl1 | 2.2859 (13) | C34—H8 | 0.9500 |
Pd2—Cl3 | 2.3149 (13) | C35—C36 | 1.409 (8) |
Pd2—Cl3i | 2.3149 (13) | C35—H9 | 0.9500 |
Pd2—Cl2i | 2.3190 (16) | C36—C51 | 1.511 (7) |
Pd2—Cl2 | 2.3190 (16) | C41—C42 | 1.401 (8) |
Cl11—C1 | 1.743 (8) | C41—C46 | 1.413 (8) |
Cl12—C1 | 1.718 (8) | C42—C43 | 1.387 (8) |
Cl21—Cl31 | 0.62 (3) | C42—C47 | 1.522 (8) |
Cl21—C2 | 1.665 (16) | C43—C44 | 1.388 (10) |
Cl22—Cl32 | 1.445 (11) | C43—H10 | 0.9500 |
Cl22—C2 | 1.665 (17) | C44—C45 | 1.394 (10) |
Cl22—Cl31 | 2.29 (3) | C44—C48 | 1.537 (10) |
Cl31—C3 | 1.70 (3) | C45—C46 | 1.368 (8) |
Cl32—C3 | 1.70 (3) | C45—H11 | 0.9500 |
N11—C16 | 1.362 (7) | C46—C49 | 1.523 (9) |
N11—C12 | 1.389 (6) | C47—H12 | 0.9800 |
N21—C26 | 1.355 (7) | C47—H13 | 0.9800 |
N21—C22 | 1.360 (7) | C47—H14 | 0.9800 |
N31—C36 | 1.354 (7) | C48—H15 | 0.9800 |
N31—C32 | 1.385 (7) | C48—H16 | 0.9800 |
C1—H32 | 0.9900 | C48—H17 | 0.9800 |
C1—H33 | 0.9900 | C49—H18 | 0.9800 |
C2—H34 | 0.9900 | C49—H19 | 0.9800 |
C2—H35 | 0.9900 | C49—H20 | 0.9800 |
C3—H36 | 0.9900 | C51—C56 | 1.381 (8) |
C3—H37 | 0.9900 | C51—C52 | 1.405 (8) |
C12—C13 | 1.380 (8) | C52—C53 | 1.405 (8) |
C12—C22 | 1.477 (8) | C52—C57 | 1.512 (9) |
C13—C14 | 1.390 (9) | C53—C54 | 1.397 (10) |
C13—H1 | 0.9500 | C53—H21 | 0.9500 |
C14—C15 | 1.386 (8) | C54—C55 | 1.372 (9) |
C14—H2 | 0.9500 | C54—C58 | 1.536 (9) |
C15—C16 | 1.392 (7) | C55—C56 | 1.393 (8) |
C15—H3 | 0.9500 | C55—H22 | 0.9500 |
C16—C41 | 1.494 (7) | C56—C59 | 1.525 (8) |
C22—C23 | 1.394 (7) | C57—H23 | 0.9800 |
C23—C24 | 1.397 (9) | C57—H24 | 0.9800 |
C23—H4 | 0.9500 | C57—H25 | 0.9800 |
C24—C25 | 1.397 (9) | C58—H26 | 0.9800 |
C24—H5 | 0.9500 | C58—H27 | 0.9800 |
C25—C26 | 1.399 (8) | C58—H28 | 0.9800 |
C25—H6 | 0.9500 | C59—H29 | 0.9800 |
C26—C32 | 1.487 (8) | C59—H30 | 0.9800 |
C32—C33 | 1.372 (8) | C59—H31 | 0.9800 |
N21—Pd1—N31 | 81.28 (18) | C34—C35—C36 | 121.4 (6) |
N21—Pd1—N11 | 80.39 (18) | C34—C35—H9 | 119.3 |
N31—Pd1—N11 | 160.31 (17) | C36—C35—H9 | 119.3 |
N21—Pd1—Cl1 | 161.42 (14) | N31—C36—C35 | 120.1 (5) |
N31—Pd1—Cl1 | 98.89 (12) | N31—C36—C51 | 121.5 (5) |
N11—Pd1—Cl1 | 100.78 (12) | C35—C36—C51 | 118.2 (5) |
Cl3—Pd2—Cl3i | 180.0 | C42—C41—C46 | 120.3 (5) |
Cl3—Pd2—Cl2i | 90.50 (5) | C42—C41—C16 | 120.2 (5) |
Cl3i—Pd2—Cl2i | 89.50 (5) | C46—C41—C16 | 119.4 (5) |
Cl3—Pd2—Cl2 | 89.51 (5) | C43—C42—C41 | 118.4 (6) |
Cl3i—Pd2—Cl2 | 90.50 (5) | C43—C42—C47 | 119.7 (6) |
Cl2i—Pd2—Cl2 | 180.0 | C41—C42—C47 | 121.8 (5) |
C16—N11—C12 | 117.9 (4) | C42—C43—C44 | 122.2 (6) |
C16—N11—Pd1 | 130.5 (3) | C42—C43—H10 | 118.9 |
C12—N11—Pd1 | 111.6 (4) | C44—C43—H10 | 118.9 |
C26—N21—C22 | 123.3 (5) | C43—C44—C45 | 117.7 (6) |
C26—N21—Pd1 | 116.8 (4) | C43—C44—C48 | 120.8 (7) |
C22—N21—Pd1 | 117.0 (4) | C45—C44—C48 | 121.4 (7) |
C36—N31—C32 | 118.0 (5) | C46—C45—C44 | 122.5 (6) |
C36—N31—Pd1 | 130.9 (4) | C46—C45—H11 | 118.8 |
C32—N31—Pd1 | 111.2 (4) | C44—C45—H11 | 118.8 |
Cl12—C1—Cl11 | 113.2 (4) | C45—C46—C41 | 118.6 (6) |
Cl12—C1—H32 | 108.9 | C45—C46—C49 | 120.5 (6) |
Cl11—C1—H32 | 108.9 | C41—C46—C49 | 120.8 (5) |
Cl12—C1—H33 | 108.9 | C42—C47—H12 | 109.5 |
Cl11—C1—H33 | 108.9 | C42—C47—H13 | 109.5 |
H32—C1—H33 | 107.8 | H12—C47—H13 | 109.5 |
Cl22—C2—Cl21 | 108.1 (15) | C42—C47—H14 | 109.5 |
Cl22—C2—H34 | 110.1 | H12—C47—H14 | 109.5 |
Cl21—C2—H34 | 110.1 | H13—C47—H14 | 109.5 |
Cl22—C2—H35 | 110.1 | C44—C48—H15 | 109.5 |
Cl21—C2—H35 | 110.1 | C44—C48—H16 | 109.5 |
H34—C2—H35 | 108.4 | H15—C48—H16 | 109.5 |
Cl32—C3—Cl31 | 126 (3) | C44—C48—H17 | 109.5 |
Cl32—C3—H36 | 105.9 | H15—C48—H17 | 109.5 |
Cl31—C3—H36 | 105.9 | H16—C48—H17 | 109.5 |
Cl32—C3—H37 | 105.9 | C46—C49—H18 | 109.5 |
Cl31—C3—H37 | 105.9 | C46—C49—H19 | 109.5 |
H36—C3—H37 | 106.2 | H18—C49—H19 | 109.5 |
C13—C12—N11 | 122.3 (5) | C46—C49—H20 | 109.5 |
C13—C12—C22 | 123.0 (5) | H18—C49—H20 | 109.5 |
N11—C12—C22 | 114.7 (4) | H19—C49—H20 | 109.5 |
C12—C13—C14 | 119.3 (5) | C56—C51—C52 | 120.6 (5) |
C12—C13—H1 | 120.4 | C56—C51—C36 | 120.5 (5) |
C14—C13—H1 | 120.4 | C52—C51—C36 | 118.6 (5) |
C15—C14—C13 | 118.4 (5) | C51—C52—C53 | 118.4 (5) |
C15—C14—H2 | 120.8 | C51—C52—C57 | 122.2 (6) |
C13—C14—H2 | 120.8 | C53—C52—C57 | 119.4 (6) |
C14—C15—C16 | 121.2 (6) | C54—C53—C52 | 120.8 (6) |
C14—C15—H3 | 119.4 | C54—C53—H21 | 119.6 |
C16—C15—H3 | 119.4 | C52—C53—H21 | 119.6 |
N11—C16—C15 | 120.7 (5) | C55—C54—C53 | 119.3 (6) |
N11—C16—C41 | 119.2 (4) | C55—C54—C58 | 120.2 (7) |
C15—C16—C41 | 120.0 (5) | C53—C54—C58 | 120.4 (7) |
N21—C22—C23 | 119.1 (6) | C54—C55—C56 | 121.2 (6) |
N21—C22—C12 | 113.9 (5) | C54—C55—H22 | 119.4 |
C23—C22—C12 | 127.0 (5) | C56—C55—H22 | 119.4 |
C22—C23—C24 | 118.5 (6) | C51—C56—C55 | 119.7 (6) |
C22—C23—H4 | 120.7 | C51—C56—C59 | 122.4 (5) |
C24—C23—H4 | 120.7 | C55—C56—C59 | 117.8 (6) |
C25—C24—C23 | 121.4 (6) | C52—C57—H23 | 109.5 |
C25—C24—H5 | 119.3 | C52—C57—H24 | 109.5 |
C23—C24—H5 | 119.3 | H23—C57—H24 | 109.5 |
C24—C25—C26 | 118.1 (6) | C52—C57—H25 | 109.5 |
C24—C25—H6 | 120.9 | H23—C57—H25 | 109.5 |
C26—C25—H6 | 120.9 | H24—C57—H25 | 109.5 |
N21—C26—C25 | 119.3 (6) | C54—C58—H26 | 109.5 |
N21—C26—C32 | 114.2 (5) | C54—C58—H27 | 109.5 |
C25—C26—C32 | 126.4 (6) | H26—C58—H27 | 109.5 |
C33—C32—N31 | 122.6 (6) | C54—C58—H28 | 109.5 |
C33—C32—C26 | 122.3 (5) | H26—C58—H28 | 109.5 |
N31—C32—C26 | 115.1 (5) | H27—C58—H28 | 109.5 |
C32—C33—C34 | 119.5 (6) | C56—C59—H29 | 109.5 |
C32—C33—H7 | 120.3 | C56—C59—H30 | 109.5 |
C34—C33—H7 | 120.3 | H29—C59—H30 | 109.5 |
C35—C34—C33 | 118.3 (6) | C56—C59—H31 | 109.5 |
C35—C34—H8 | 120.9 | H29—C59—H31 | 109.5 |
C33—C34—H8 | 120.9 | H30—C59—H31 | 109.5 |
C2—Cl21—Cl31—C3 | −7 (2) | Pd1—N21—C26—C32 | 12.7 (6) |
C2—Cl21—Cl31—Cl22 | −41.0 (16) | C24—C25—C26—N21 | 3.9 (8) |
Cl32—Cl22—Cl31—Cl21 | 14 (4) | C24—C25—C26—C32 | −176.0 (5) |
C2—Cl22—Cl31—Cl21 | 64 (3) | C36—N31—C32—C33 | −3.7 (8) |
Cl32—Cl22—Cl31—C3 | −40 (3) | Pd1—N31—C32—C33 | 176.5 (5) |
C2—Cl22—Cl31—C3 | 9 (3) | C36—N31—C32—C26 | 177.2 (5) |
C2—Cl22—Cl32—C3 | 1 (3) | Pd1—N31—C32—C26 | −2.6 (6) |
Cl31—Cl22—Cl32—C3 | 31 (2) | N21—C26—C32—C33 | 174.7 (5) |
N21—Pd1—N11—C16 | 166.3 (5) | C25—C26—C32—C33 | −5.4 (9) |
N31—Pd1—N11—C16 | 144.6 (5) | N21—C26—C32—N31 | −6.2 (7) |
Cl1—Pd1—N11—C16 | −32.5 (5) | C25—C26—C32—N31 | 173.7 (5) |
N21—Pd1—N11—C12 | −10.3 (3) | N31—C32—C33—C34 | −0.4 (10) |
N31—Pd1—N11—C12 | −32.0 (7) | C26—C32—C33—C34 | 178.7 (6) |
Cl1—Pd1—N11—C12 | 150.8 (3) | C32—C33—C34—C35 | 3.8 (10) |
N31—Pd1—N21—C26 | −11.1 (4) | C33—C34—C35—C36 | −3.3 (10) |
N11—Pd1—N21—C26 | 176.1 (4) | C32—N31—C36—C35 | 4.1 (8) |
Cl1—Pd1—N21—C26 | 80.8 (6) | Pd1—N31—C36—C35 | −176.1 (4) |
N31—Pd1—N21—C22 | −172.5 (4) | C32—N31—C36—C51 | −170.4 (5) |
N11—Pd1—N21—C22 | 14.7 (4) | Pd1—N31—C36—C51 | 9.4 (8) |
Cl1—Pd1—N21—C22 | −80.5 (6) | C34—C35—C36—N31 | −0.8 (10) |
N21—Pd1—N31—C36 | −172.6 (5) | C34—C35—C36—C51 | 173.9 (6) |
N11—Pd1—N31—C36 | −151.0 (5) | N11—C16—C41—C42 | 110.5 (6) |
Cl1—Pd1—N31—C36 | 26.2 (5) | C15—C16—C41—C42 | −71.0 (7) |
N21—Pd1—N31—C32 | 7.1 (4) | N11—C16—C41—C46 | −71.6 (7) |
N11—Pd1—N31—C32 | 28.7 (7) | C15—C16—C41—C46 | 106.9 (6) |
Cl1—Pd1—N31—C32 | −154.1 (3) | C46—C41—C42—C43 | 2.9 (9) |
Cl32—Cl22—C2—Cl21 | 115.1 (11) | C16—C41—C42—C43 | −179.2 (5) |
Cl31—Cl22—C2—Cl21 | −16.7 (11) | C46—C41—C42—C47 | −178.8 (5) |
Cl31—Cl21—C2—Cl22 | 51 (4) | C16—C41—C42—C47 | −0.8 (9) |
Cl22—Cl32—C3—Cl31 | −55 (3) | C41—C42—C43—C44 | 0.7 (10) |
Cl21—Cl31—C3—Cl32 | −97 (5) | C47—C42—C43—C44 | −177.6 (7) |
Cl22—Cl31—C3—Cl32 | 41 (2) | C42—C43—C44—C45 | −2.8 (11) |
C16—N11—C12—C13 | 5.7 (8) | C42—C43—C44—C48 | 178.0 (8) |
Pd1—N11—C12—C13 | −177.2 (4) | C43—C44—C45—C46 | 1.2 (11) |
C16—N11—C12—C22 | −172.1 (4) | C48—C44—C45—C46 | −179.6 (8) |
Pd1—N11—C12—C22 | 5.0 (5) | C44—C45—C46—C41 | 2.3 (10) |
N11—C12—C13—C14 | −4.1 (8) | C44—C45—C46—C49 | −175.2 (7) |
C22—C12—C13—C14 | 173.5 (5) | C42—C41—C46—C45 | −4.4 (9) |
C12—C13—C14—C15 | 0.4 (9) | C16—C41—C46—C45 | 177.7 (6) |
C13—C14—C15—C16 | 1.4 (9) | C42—C41—C46—C49 | 173.1 (6) |
C12—N11—C16—C15 | −3.7 (7) | C16—C41—C46—C49 | −4.8 (8) |
Pd1—N11—C16—C15 | 179.8 (4) | N31—C36—C51—C56 | 68.9 (7) |
C12—N11—C16—C41 | 174.8 (5) | C35—C36—C51—C56 | −105.7 (7) |
Pd1—N11—C16—C41 | −1.7 (7) | N31—C36—C51—C52 | −116.6 (6) |
C14—C15—C16—N11 | 0.3 (9) | C35—C36—C51—C52 | 68.8 (7) |
C14—C15—C16—C41 | −178.2 (5) | C56—C51—C52—C53 | −0.7 (8) |
C26—N21—C22—C23 | 5.1 (7) | C36—C51—C52—C53 | −175.2 (5) |
Pd1—N21—C22—C23 | 165.2 (4) | C56—C51—C52—C57 | −178.8 (6) |
C26—N21—C22—C12 | −176.1 (5) | C36—C51—C52—C57 | 6.7 (8) |
Pd1—N21—C22—C12 | −16.1 (6) | C51—C52—C53—C54 | −0.1 (9) |
C13—C12—C22—N21 | −171.3 (5) | C57—C52—C53—C54 | 178.1 (6) |
N11—C12—C22—N21 | 6.5 (6) | C52—C53—C54—C55 | 0.5 (10) |
C13—C12—C22—C23 | 7.3 (9) | C52—C53—C54—C58 | 178.1 (6) |
N11—C12—C22—C23 | −174.9 (5) | C53—C54—C55—C56 | −0.1 (10) |
N21—C22—C23—C24 | −0.1 (8) | C58—C54—C55—C56 | −177.7 (6) |
C12—C22—C23—C24 | −178.7 (5) | C52—C51—C56—C55 | 1.1 (8) |
C22—C23—C24—C25 | −2.7 (8) | C36—C51—C56—C55 | 175.5 (5) |
C23—C24—C25—C26 | 0.9 (9) | C52—C51—C56—C59 | −178.0 (5) |
C22—N21—C26—C25 | −7.1 (8) | C36—C51—C56—C59 | −3.6 (8) |
Pd1—N21—C26—C25 | −167.2 (4) | C54—C55—C56—C51 | −0.7 (9) |
C22—N21—C26—C32 | 172.9 (5) | C54—C55—C56—C59 | 178.4 (6) |
Symmetry code: (i) −x+2, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [PdCl(C33H31N3)]2[PdCl4]·4CH2Cl2 |
Mr | 1810.82 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 200 |
a, b, c (Å) | 10.6555 (7), 21.3398 (5), 8.5995 (1) |
α, β, γ (°) | 91.21, 100.468 (7), 83.566 (7) |
V (Å3) | 1910.75 (14) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.23 |
Crystal size (mm) | 0.15 × 0.15 × 0.05 |
Data collection | |
Diffractometer | Rigaku R-AXIS-RAPID Imaging Plate diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.777, 0.940 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9543, 8029, 4933 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.144, 1.00 |
No. of reflections | 8029 |
No. of parameters | 455 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.53, −1.36 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).
Pd1—N21 | 1.953 (4) | Pd1—N11 | 2.091 (4) |
Pd1—N31 | 2.089 (4) | Pd1—Cl1 | 2.2859 (13) |
N21—Pd1—N31 | 81.28 (18) | N21—Pd1—Cl1 | 161.42 (14) |
N21—Pd1—N11 | 80.39 (18) | N31—Pd1—Cl1 | 98.89 (12) |
N31—Pd1—N11 | 160.31 (17) | N11—Pd1—Cl1 | 100.78 (12) |
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Design of N-chelating ligands with various bulky substituents is an essential approach in developing N-chelating metal catalysis for polymerization. For example, Brookhart and co-workers have reported highly efficient Pd and Ni catalysts with α-diimino ligands for the polymerization of ethylene and α-olefin (Johnson et al., 1995). It was also reported that control of the bulkiness in pyridine bisimino ligands (3 N coordination) contributes to polymerization by their Fe and Co catalysis (Small et al., 1998; Britovsek et al., 1998). We have synthesized a palladium monochloride complex with a bulky terpyridine ligand, namely 6,6''-dimesityl-2,2':6',2''-terpyridine and determined the effect of the steric hindrance of the ligands, which perturbs the metal coordination geometry.
Fig. 1(a) shows the molecular structure. The asymmetric unit consists of one cation of PdII(dmtpy), half of a PdIICl4 anion and two dichloromethanes. Fig. 1(b) shows the cation part of the structure. Pd complex (I) has a distorted square-planar coordination formed by three N atoms and a chloride ion because of the extremely bulky terpyridyl ligands. The Pd1—N21 bond distance [1.953 (4) Å] with the central pyridine ring is shorter than those with the pyridine rings on either side [2.0913 (4) and 2.089 (4) Å]. The N21—Pd1—Cl1 angle is 161.42 (14)° and the Pd1 ion sits 0.156 Å from the N11—N12—N31 plane. It has been reported that similar 3 N with terpyridine and a chloride coordination gives an almost planer coordination geometry, with similar Pd—N bond distances and a linear N—Pd—Cl angle of 193.6° (Intille et al., 1973). The bulkiness of the dimesityl groups in the 6,6''-positions the of terpyridine ligands distrupts the square-planar coordination towards a tetrahedral geometry, that results in shortning of the Pd—Cl bond length from 2.331 (1) to 2.286 (1) Å. Our ligand design of bulky derivatization in terpyridine ligands successfully induces a distortion in Pd coordination geometry.