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Complexes of the composition trans-[Pd(L)2(OAc)2] have been postulated as intermediates during cyclo­palladation. The first structural characterization of such a precursor has now been achieved and its role in the reaction sequence has been established. Diacetato-κ2O-bis­[(S)-1-(4-fluorophenyl)­ethyl­amine-κN]­palladium(II), [Pd(O2CMe)2(4-FC6H3CHMeNH2)2] or [Pd(C2H3O2)2(C8H10FN)2], (I), was obtained from palladium(II) acetate and (S)-NH2CHMeC6H3F-4 in a 1:2 molar ratio. The intermediate was then reacted with additional palladium(II) acetate to give the acetate-bridged dinuclear complex di-μ-acetato-κ4O:O′-bis{[(S)-2-(1-amino­ethyl)-5-fluoro­phenyl-κ2C1,N]­palladium(II)} benzene hemisolvate, [Pd(4-FC6H3CHMeNH2)2(μ-O2CMe)]2·0.5C6H6 or [Pd2(C8H9FN)2(C2H3O2)2]·0.5C6H6, (II).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104010856/dn1048sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104010856/dn1048Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104010856/dn1048IIsup3.hkl
Contains datablock II

CCDC references: 245854; 245855

Comment top

The reaction of palladium(II) acetate and benzylamines under certain conditions results in the formation of a five-membered metallocycle, with the metal coordinated both to the amino N atom and the ortho C atom of the aromatic ring. Ryabov (1990) first postulated that this special case of orthometallation, often called cyclopalladation (Cope & Friedrich, 1968), proceeds via formation of an intermediate trans-bisacetato-bis(amino-ligand) complex. Our interest in building blocks for quasi-racemic crystals (Englert et al., 2000, 2002; Kalf et al., 2002; Reemers & Englert, 2002) induced us to study this reaction. In this context, we have recently performed a structural study of this pathway for primary amines (Calmuschi & Englert, 2002), a relatively new class of substrates for cyclopalladation (Calmuschi et al., 2003).

Vicente et al. (1997) infringed the historical second rule of Cope & Friedrich (Cope & Friedrich, 1968) by cyclopalladating primary amines which even contained electron-withdrawing substituents on the aryl ring. They confirmed Ryabov's theory about the intermediate bis(ligand) complex and reported NMR data for this class of compounds. We have now achieved the isolation and structural characterization of the first trans-[Pd(L)2(OAc)2] precursor complex: palladium(II)acetate and (S)-1-(4-fluorophenyl)ethylamine in a 1:2 molar ratio give [Pd(O2CMe)2(4-FC6H3CHMeNH2)2], (I). The reaction pathway is shown in the scheme. \sch

To the best of our knowledge, only one other PdII compound containing terminal acetate ligands and primary amines has been reported to date. That dinuclear complex represents a second intermediate in the cyclopalladation pathway and was separated and fully characterized by Vicente et al. (1997).

Complex (I) crystallizes in the monoclinic space group P21. The asymmetric unit contains two molecules of quite similar conformation, with the acetate groups and the H atoms of the amine N directed to the same face of the coordination plane (Fig. 1). The symmetrically independent molecules approach each other in a face-to-face fashion, hence interacting via two pairs of hydrogen bridges, each pair between an amine NH2 donor and uncoordinated acetate O atoms as acceptors. This conformation is probably stabilized by the intermolecular interactions and is therefore limited to the solid state. Table 2 gives geometric information about the hydrogen bonds in (I).

In terms of intramolecular geometry, complex (I) may best be compared with bis(acetato-O)bis(diethylamine-N)palladium(II). This mononuclear square-planar PdII complex, with two monodentate acetate and two secondary amine ligands coordinated to the metal in a trans geometry (Kravtsova et al., 1996), exhibits metal-ligand distances similar to those observed in (I). Due to the different hydrogen-bond donor-acceptor balance, this kind of interaction is limited to just one intramolecular hydrogen bond in the asymmetric unit of the centrosymmetric complex.

Further reaction of (I) with palladium(II) acetate results in the formation of [{Pd(µ-O2CMe)(4-FC6H3CHMeNH2)2], (II), thus proving the role of (I) as the primary intermediate in cyclopalladation. The orthometallated complex (II) crystallizes from benzene with 0.5 equivalents of solvent; the benzene molecules occupy the twofold axes in space group C2. The geometry of this acetate dimer corresponds to the inner isomer, with both methyl groups attached at the chiral atom pointing towards each other (Fig. 2). The Pd···Pd distance is 2.8733 (10) Å, slightly shorter than in the dinuclear complex of the unsubstituted amine ligand (Calmuschi & Englert, 2002). A two-dimensional network of hydrogen bonds in the ab plane is formed in (II) (Fig. 3). Table 4 gives details of the intermolecular hydrogen bonds. Both complexes (I) and (II) exhibit rather weak non-classical intermolecular hydrogen bonds.

Experimental top

Pd(OAc)2 and (S)—NH2CHMeC6H3F-4 were stirred in benzene in a molar ratio of 1:2 at room temperature for 2 h. The resulting mixture was filtered and the filtrate concentrated in vacuo. Addition of hexane afforded greenish-yellow crystals of the mononuclear intermediate complex, (I) (yield 89%). This product underwent further reaction with an additional equivalent of Pd(OAc)2 in benzene at 333 K for 1 d. The mixture was filtered and concentrated and the product, (II), was precipitated with hexane (yield 93%). Single crystals suitable for X-ray structure determination were obtained from solutions in a 1:1 benzene-hexane mixture. Alternatively, complex (II) may be obtained by reaction of equimolar amounts of Pd(OAc)2 and (S)—NH2CHMeC6H3F-4 in refluxing acetonitrile for 4 h.

Refinement top

Please give brief details of the constraints used in the H-atom treatment.

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: Please provide missing details.

Figures top
[Figure 1] Fig. 1. A view of the two independent molecules in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are indicated by dashed lines.
[Figure 2] Fig. 2. A view of the molecule of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Only those H atoms at the chiral centres are shown, as small spheres of arbitrary radii. The benzene hemisolvate has been omitted for clarity.
[Figure 3] Fig. 3. A view of the hydrogen-bonding interactions for (II).
(I) Diacetato-κ2O-bis[(S)-1-(1-aminoethyl)-4-fluorophenyl-κN]palladium(II) top
Crystal data top
[Pd(C2H3O2)2(C8H10FN)2]F(000) = 1024
Mr = 502.83Dx = 1.568 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 8096 reflections
a = 10.589 (2) Åθ = 1.8–28.4°
b = 17.537 (3) ŵ = 0.92 mm1
c = 11.686 (2) ÅT = 110 K
β = 100.954 (3)°Irregular, yellow
V = 2130.6 (7) Å30.80 × 0.70 × 0.60 mm
Z = 4
Data collection top
Make Model CCD area-detector
diffractometer
10628 independent reflections
Radiation source: fine-focus sealed tube10531 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
ϕ and ω scansθmax = 28.4°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 1414
Tmin = 0.500, Tmax = 0.577k = 2323
29128 measured reflectionsl = 1515
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.061 w = 1/[σ2(Fo2) + (0.0388P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
10628 reflectionsΔρmax = 0.65 e Å3
531 parametersΔρmin = 0.30 e Å3
1 restraintAbsolute structure: Flack (1983), with 5132 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.017 (11)
Crystal data top
[Pd(C2H3O2)2(C8H10FN)2]V = 2130.6 (7) Å3
Mr = 502.83Z = 4
Monoclinic, P21Mo Kα radiation
a = 10.589 (2) ŵ = 0.92 mm1
b = 17.537 (3) ÅT = 110 K
c = 11.686 (2) Å0.80 × 0.70 × 0.60 mm
β = 100.954 (3)°
Data collection top
Make Model CCD area-detector
diffractometer
10628 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
10531 reflections with I > 2σ(I)
Tmin = 0.500, Tmax = 0.577Rint = 0.017
29128 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.061Δρmax = 0.65 e Å3
S = 1.06Δρmin = 0.30 e Å3
10628 reflectionsAbsolute structure: Flack (1983), with 5132 Friedel pairs
531 parametersAbsolute structure parameter: 0.017 (11)
1 restraint
Special details top

Experimental. The values of Tmin and Tmax are 0.774044 and 1.000000 from SADABS.

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
xyzUiso*/Ueq
Pd10.096419 (12)0.385100 (7)0.230795 (11)0.01805 (4)
Pd20.446083 (12)0.454140 (6)0.300154 (11)0.01847 (4)
O130.04554 (14)0.47488 (8)0.32146 (12)0.0225 (3)
O230.39907 (15)0.54937 (8)0.37889 (12)0.0233 (3)
O210.49798 (14)0.36485 (8)0.21080 (12)0.0246 (3)
O110.13978 (15)0.28894 (8)0.15140 (12)0.0237 (3)
O120.20817 (15)0.35311 (8)0.00792 (13)0.0270 (3)
O240.32661 (15)0.48133 (8)0.51600 (13)0.0246 (3)
O220.45830 (16)0.27696 (9)0.33982 (14)0.0292 (3)
O140.09150 (17)0.56157 (9)0.19412 (16)0.0333 (3)
F120.52473 (15)0.22813 (8)0.86008 (12)0.0381 (3)
F220.93546 (14)0.26060 (9)0.87157 (13)0.0399 (3)
F210.02159 (17)0.59145 (9)0.33874 (13)0.0425 (3)
F110.41247 (15)0.55856 (10)0.35410 (13)0.0418 (3)
N110.01178 (16)0.42527 (10)0.07677 (14)0.0218 (3)
H11A0.00810.47940.07940.028*
H11B0.02970.40960.01540.028*
N120.21167 (16)0.34972 (9)0.38167 (14)0.0187 (3)
H12A0.26890.31220.36230.024*
H12B0.26240.39190.41420.024*
N210.32929 (15)0.48916 (9)0.14876 (14)0.0193 (3)
H21A0.31910.44750.09580.025*
H21B0.24690.50010.16570.025*
N220.55926 (16)0.41683 (10)0.45278 (14)0.0228 (3)
H22A0.54840.45120.51300.030*
H22B0.52750.36860.47140.030*
C2030.28024 (19)0.56805 (10)0.02839 (17)0.0211 (3)
C1160.2575 (2)0.32802 (11)0.68430 (18)0.0252 (4)
H1160.19810.36970.69210.033*
C1030.21799 (18)0.44650 (11)0.06276 (16)0.0234 (3)
C1110.2473 (2)0.29111 (11)0.57724 (17)0.0225 (4)
C2070.2037 (2)0.53067 (12)0.22982 (18)0.0311 (4)
H2070.21090.49900.29740.040*
C1140.4320 (2)0.24803 (12)0.76651 (18)0.0267 (4)
C2180.49619 (19)0.29564 (12)0.24995 (17)0.0239 (4)
C1130.4248 (2)0.20862 (12)0.6633 (2)0.0286 (4)
H1130.48370.16640.65690.037*
C1050.39921 (19)0.45376 (15)0.22561 (17)0.0297 (4)
H1050.47890.43250.27080.039*
C1150.3502 (2)0.30693 (11)0.78045 (17)0.0271 (4)
H1150.35700.33310.85540.035*
C2120.87573 (19)0.40098 (12)0.63917 (18)0.0260 (4)
H2120.91160.44920.61740.034*
C2060.1081 (2)0.58488 (13)0.23618 (19)0.0300 (4)
C1190.0051 (2)0.60398 (12)0.3519 (2)0.0303 (4)
H11C0.03360.65350.34010.039*
H11D0.01420.59080.43480.039*
H11E0.09850.60690.32530.039*
C1200.04962 (19)0.54350 (11)0.28273 (18)0.0236 (4)
C2050.0958 (2)0.63255 (13)0.14480 (19)0.0281 (4)
H2050.02810.67130.15310.037*
C2150.7758 (2)0.26266 (12)0.7017 (2)0.0298 (4)
H2150.74090.21440.72420.039*
C1120.3308 (2)0.23068 (12)0.56785 (18)0.0267 (4)
H1120.32340.20340.49370.035*
C2130.9337 (2)0.36368 (13)0.74238 (18)0.0283 (4)
H2131.00920.38550.79330.037*
C2200.35084 (18)0.54252 (11)0.47249 (16)0.0207 (3)
C1180.18528 (19)0.29346 (11)0.05590 (18)0.0234 (4)
C2170.5492 (3)0.23635 (14)0.1771 (2)0.0369 (5)
H21C0.64340.23610.19750.048*
H21D0.52230.24870.09420.048*
H21E0.51620.18590.19240.048*
C2080.2894 (2)0.52228 (12)0.12465 (18)0.0289 (4)
H2080.35730.48370.11780.038*
C2140.8819 (2)0.29580 (13)0.77002 (18)0.0292 (4)
C2100.70061 (18)0.40882 (11)0.45497 (17)0.0230 (4)
H2100.71080.37550.39000.030*
C1060.3505 (2)0.52204 (14)0.25641 (18)0.0311 (4)
C2110.76736 (18)0.36986 (11)0.56750 (17)0.0229 (4)
C1020.14873 (19)0.40337 (11)0.04398 (18)0.0245 (4)
H1020.15250.34890.02510.032*
C2040.1833 (2)0.62347 (12)0.04032 (18)0.0252 (4)
H2040.17690.65650.02600.033*
C2160.7195 (2)0.30024 (11)0.59878 (19)0.0268 (4)
H2160.64500.27730.54780.035*
C1100.14693 (19)0.31729 (12)0.47414 (17)0.0249 (4)
H1100.09680.35820.50120.032*
C1080.1748 (2)0.51666 (12)0.09654 (19)0.0305 (4)
H1080.09700.53940.05030.040*
C2020.37134 (18)0.55688 (10)0.08777 (16)0.0211 (3)
H2020.36440.60190.13590.027*
C1070.2398 (2)0.55505 (13)0.1944 (2)0.0328 (5)
H1070.20830.60390.21850.043*
C1040.33140 (19)0.41574 (13)0.12787 (18)0.0262 (4)
H1040.36360.36690.10450.034*
C2090.7559 (2)0.48621 (13)0.4330 (2)0.0304 (4)
H20A0.70390.50910.36300.040*
H20B0.84460.48000.42150.040*
H20C0.75480.51950.50010.040*
C2010.5118 (2)0.54898 (14)0.0762 (2)0.0321 (4)
H20D0.56690.55180.15360.042*
H20E0.53420.59030.02720.042*
H20F0.52450.49970.04040.042*
C1090.0542 (3)0.25476 (17)0.4234 (2)0.0487 (7)
H10A0.01070.27570.36010.063*
H10B0.01170.23430.48430.063*
H10C0.10150.21390.39290.063*
C2190.3263 (2)0.61772 (11)0.52821 (19)0.0288 (4)
H21F0.25420.64400.47870.037*
H21G0.40350.64960.53690.037*
H21H0.30520.60820.60510.037*
C1170.2085 (3)0.21667 (12)0.0039 (2)0.0344 (5)
H11F0.21650.22340.07770.045*
H11G0.13600.18260.00800.045*
H11H0.28790.19430.04780.045*
C1010.2151 (2)0.41534 (17)0.1475 (2)0.0378 (5)
H10D0.16740.38820.21560.049*
H10E0.30310.39550.12850.049*
H10F0.21730.46990.16500.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.01752 (6)0.01968 (6)0.01785 (6)0.00038 (5)0.00560 (5)0.00184 (5)
Pd20.01913 (7)0.02034 (6)0.01676 (6)0.00213 (5)0.00550 (5)0.00189 (4)
O130.0222 (6)0.0242 (6)0.0219 (6)0.0018 (5)0.0065 (5)0.0019 (5)
O230.0307 (7)0.0195 (6)0.0200 (6)0.0028 (5)0.0051 (5)0.0015 (5)
O210.0242 (7)0.0291 (7)0.0217 (7)0.0034 (5)0.0078 (5)0.0014 (5)
O110.0275 (7)0.0218 (6)0.0229 (7)0.0017 (5)0.0079 (5)0.0014 (5)
O120.0323 (8)0.0242 (6)0.0281 (7)0.0015 (6)0.0148 (6)0.0008 (5)
O240.0300 (7)0.0194 (6)0.0261 (7)0.0030 (5)0.0097 (6)0.0003 (5)
O220.0331 (8)0.0273 (7)0.0301 (8)0.0022 (6)0.0134 (6)0.0002 (6)
O140.0393 (9)0.0282 (8)0.0384 (9)0.0009 (7)0.0226 (7)0.0034 (7)
F120.0471 (8)0.0368 (7)0.0279 (6)0.0108 (6)0.0003 (6)0.0066 (5)
F220.0382 (7)0.0483 (8)0.0300 (7)0.0053 (6)0.0017 (5)0.0095 (6)
F210.0584 (10)0.0387 (8)0.0252 (7)0.0049 (7)0.0053 (6)0.0047 (5)
F110.0398 (8)0.0528 (9)0.0271 (7)0.0066 (7)0.0080 (6)0.0009 (6)
N110.0198 (7)0.0283 (8)0.0180 (7)0.0025 (6)0.0051 (6)0.0020 (6)
N120.0204 (7)0.0174 (7)0.0194 (7)0.0012 (6)0.0069 (6)0.0036 (5)
N210.0201 (7)0.0212 (7)0.0174 (7)0.0029 (6)0.0054 (6)0.0018 (6)
N220.0193 (7)0.0274 (8)0.0222 (8)0.0015 (6)0.0057 (6)0.0033 (6)
C2030.0249 (9)0.0188 (8)0.0215 (8)0.0002 (7)0.0090 (7)0.0037 (6)
C1160.0325 (10)0.0191 (8)0.0272 (9)0.0046 (7)0.0135 (8)0.0030 (7)
C1030.0211 (8)0.0258 (9)0.0229 (8)0.0045 (7)0.0032 (6)0.0043 (7)
C1110.0267 (9)0.0212 (8)0.0218 (8)0.0001 (7)0.0102 (7)0.0050 (7)
C2070.0509 (13)0.0214 (9)0.0216 (9)0.0038 (9)0.0085 (9)0.0009 (7)
C1140.0334 (10)0.0243 (9)0.0230 (10)0.0040 (8)0.0068 (8)0.0075 (7)
C2180.0191 (8)0.0271 (9)0.0244 (9)0.0031 (7)0.0018 (7)0.0004 (7)
C1130.0350 (11)0.0226 (9)0.0294 (10)0.0092 (8)0.0095 (8)0.0025 (7)
C1050.0211 (8)0.0441 (11)0.0234 (9)0.0009 (9)0.0028 (7)0.0086 (9)
C1150.0391 (11)0.0233 (9)0.0203 (8)0.0012 (8)0.0095 (8)0.0002 (7)
C2120.0230 (9)0.0307 (10)0.0261 (9)0.0022 (7)0.0090 (7)0.0039 (7)
C2060.0417 (12)0.0263 (10)0.0207 (9)0.0011 (9)0.0025 (8)0.0056 (8)
C1190.0338 (11)0.0230 (9)0.0377 (11)0.0026 (8)0.0158 (9)0.0033 (8)
C1200.0197 (8)0.0244 (9)0.0273 (9)0.0005 (7)0.0058 (7)0.0008 (7)
C2050.0297 (10)0.0292 (10)0.0265 (10)0.0058 (8)0.0081 (8)0.0045 (8)
C2150.0300 (10)0.0251 (9)0.0335 (11)0.0033 (8)0.0042 (8)0.0002 (8)
C1120.0372 (11)0.0250 (9)0.0198 (9)0.0019 (8)0.0101 (8)0.0001 (7)
C2130.0197 (8)0.0422 (11)0.0231 (9)0.0022 (8)0.0047 (7)0.0041 (8)
C2200.0207 (8)0.0206 (8)0.0198 (8)0.0007 (6)0.0017 (6)0.0007 (6)
C1180.0230 (9)0.0231 (8)0.0244 (9)0.0008 (7)0.0058 (7)0.0030 (7)
C2170.0446 (13)0.0336 (12)0.0349 (11)0.0088 (9)0.0140 (10)0.0039 (9)
C2080.0396 (11)0.0210 (8)0.0275 (10)0.0075 (8)0.0102 (8)0.0023 (7)
C2140.0286 (10)0.0331 (11)0.0253 (10)0.0089 (8)0.0039 (8)0.0015 (8)
C2100.0201 (8)0.0275 (9)0.0221 (8)0.0023 (7)0.0058 (7)0.0018 (7)
C1060.0286 (10)0.0398 (11)0.0222 (9)0.0082 (9)0.0018 (7)0.0057 (8)
C2110.0203 (8)0.0256 (9)0.0233 (8)0.0025 (7)0.0056 (7)0.0039 (7)
C1020.0219 (8)0.0226 (8)0.0286 (10)0.0016 (7)0.0039 (7)0.0008 (7)
C2040.0291 (10)0.0253 (8)0.0232 (9)0.0034 (7)0.0099 (7)0.0005 (7)
C2160.0274 (9)0.0230 (9)0.0290 (10)0.0015 (7)0.0026 (7)0.0042 (7)
C1100.0261 (9)0.0275 (9)0.0228 (8)0.0016 (7)0.0092 (7)0.0080 (7)
C1080.0304 (10)0.0248 (9)0.0315 (10)0.0002 (8)0.0064 (8)0.0037 (8)
C2020.0214 (8)0.0204 (8)0.0225 (8)0.0001 (6)0.0070 (6)0.0032 (7)
C1070.0376 (12)0.0254 (9)0.0315 (11)0.0012 (9)0.0035 (9)0.0007 (8)
C1040.0207 (9)0.0346 (10)0.0237 (9)0.0023 (7)0.0053 (7)0.0077 (8)
C2090.0270 (10)0.0327 (10)0.0321 (10)0.0064 (8)0.0068 (8)0.0056 (8)
C2010.0225 (9)0.0409 (11)0.0351 (11)0.0003 (8)0.0107 (8)0.0122 (9)
C1090.0442 (14)0.0514 (15)0.0450 (14)0.0276 (12)0.0054 (11)0.0224 (12)
C2190.0365 (11)0.0211 (9)0.0285 (10)0.0019 (8)0.0055 (8)0.0017 (7)
C1170.0489 (14)0.0213 (9)0.0370 (12)0.0042 (9)0.0182 (10)0.0019 (8)
C1010.0201 (9)0.0622 (15)0.0320 (11)0.0046 (9)0.0074 (8)0.0125 (10)
Geometric parameters (Å, º) top
Pd1—O112.0192 (15)C212—C2131.406 (3)
Pd1—O132.0271 (14)C212—H2120.9800
Pd1—N122.0409 (16)C206—C2051.382 (3)
Pd1—N112.0652 (16)C119—C1201.514 (3)
Pd2—O232.0144 (14)C119—H11C0.9801
Pd2—O212.0155 (14)C119—H11D0.9801
Pd2—N212.0507 (16)C119—H11E0.9801
Pd2—N222.0575 (17)C205—C2041.395 (3)
O13—C1201.289 (2)C205—H2050.9800
O23—C2201.298 (2)C215—C2141.377 (3)
O21—C2181.299 (2)C215—C2161.401 (3)
O11—C1181.299 (2)C215—H2150.9800
O12—C1181.233 (2)C112—H1120.9800
O24—C2201.235 (2)C213—C2141.375 (3)
O22—C2181.237 (3)C213—H2130.9800
O14—C1201.243 (3)C220—C2191.515 (3)
F12—C1141.369 (2)C118—C1171.516 (3)
F22—C2141.362 (2)C217—H21C0.9801
F21—C2061.368 (3)C217—H21D0.9801
F11—C1061.364 (2)C217—H21E0.9801
N11—C1021.479 (2)C208—H2080.9800
N11—H11A0.9500C210—C2091.519 (3)
N11—H11B0.9500C210—C2111.530 (3)
N12—C1101.498 (2)C210—H2100.9800
N12—H12A0.9500C106—C1071.382 (3)
N12—H12B0.9500C211—C2161.397 (3)
N21—C2021.496 (2)C102—C1011.524 (3)
N21—H21A0.9500C102—H1020.9800
N21—H21B0.9500C204—H2040.9800
N22—C2101.499 (2)C216—H2160.9800
N22—H22A0.9500C110—C1091.516 (3)
N22—H22B0.9500C110—H1100.9800
C203—C2081.400 (3)C108—C1071.391 (3)
C203—C2041.401 (3)C108—H1080.9800
C203—C2021.521 (3)C202—C2011.525 (3)
C116—C1151.395 (3)C202—H2020.9800
C116—C1111.395 (3)C107—H1070.9800
C116—H1160.9800C104—H1040.9800
C103—C1081.396 (3)C209—H20A0.9801
C103—C1041.402 (3)C209—H20B0.9801
C103—C1021.522 (3)C209—H20C0.9801
C111—C1121.397 (3)C201—H20D0.9801
C111—C1101.518 (3)C201—H20E0.9801
C207—C2061.380 (3)C201—H20F0.9801
C207—C2081.390 (3)C109—H10A0.9801
C207—H2070.9800C109—H10B0.9801
C114—C1151.378 (3)C109—H10C0.9801
C114—C1131.380 (3)C219—H21F0.9801
C218—C2171.518 (3)C219—H21G0.9801
C113—C1121.401 (3)C219—H21H0.9801
C113—H1130.9800C117—H11F0.9801
C105—C1061.378 (4)C117—H11G0.9801
C105—C1041.398 (3)C117—H11H0.9801
C105—H1050.9800C101—H10D0.9801
C115—H1150.9800C101—H10E0.9801
C212—C2111.397 (3)C101—H10F0.9801
O11—Pd1—O13174.33 (6)O24—C220—C219120.88 (17)
O11—Pd1—N1289.55 (6)O23—C220—C219114.15 (16)
O13—Pd1—N1287.67 (6)O12—C118—O11125.41 (18)
O11—Pd1—N1191.22 (6)O12—C118—C117120.71 (18)
O13—Pd1—N1191.83 (6)O11—C118—C117113.87 (18)
N12—Pd1—N11176.65 (7)C218—C217—H21C109.5
O23—Pd2—O21174.96 (6)C218—C217—H21D109.5
O23—Pd2—N2189.13 (6)H21C—C217—H21D109.5
O21—Pd2—N2187.98 (6)C218—C217—H21E109.5
O23—Pd2—N2291.23 (6)H21C—C217—H21E109.5
O21—Pd2—N2291.77 (7)H21D—C217—H21E109.5
N21—Pd2—N22178.36 (7)C207—C208—C203121.11 (19)
C120—O13—Pd1120.77 (12)C207—C208—H208119.4
C220—O23—Pd2118.64 (12)C203—C208—H208119.4
C218—O21—Pd2121.33 (12)F22—C214—C213118.6 (2)
C118—O11—Pd1119.84 (13)F22—C214—C215118.2 (2)
C102—N11—Pd1119.45 (12)C213—C214—C215123.2 (2)
C102—N11—H11A107.5N22—C210—C209109.22 (17)
Pd1—N11—H11A107.5N22—C210—C211110.68 (15)
C102—N11—H11B107.5C209—C210—C211114.48 (17)
Pd1—N11—H11B107.5N22—C210—H210107.4
H11A—N11—H11B107.0C209—C210—H210107.4
C110—N12—Pd1117.27 (12)C211—C210—H210107.4
C110—N12—H12A108.0F11—C106—C105118.84 (19)
Pd1—N12—H12A108.0F11—C106—C107117.9 (2)
C110—N12—H12B108.0C105—C106—C107123.3 (2)
Pd1—N12—H12B108.0C212—C211—C216118.83 (19)
H12A—N12—H12B107.2C212—C211—C210122.24 (18)
C202—N21—Pd2117.62 (12)C216—C211—C210118.92 (17)
C202—N21—H21A107.9N11—C102—C103112.30 (16)
Pd2—N21—H21A107.9N11—C102—C101109.61 (17)
C202—N21—H21B107.9C103—C102—C101111.03 (17)
Pd2—N21—H21B107.9N11—C102—H102107.9
H21A—N21—H21B107.2C103—C102—H102107.9
C210—N22—Pd2117.38 (12)C101—C102—H102107.9
C210—N22—H22A108.0C205—C204—C203121.24 (19)
Pd2—N22—H22A108.0C205—C204—H204119.4
C210—N22—H22B108.0C203—C204—H204119.4
Pd2—N22—H22B108.0C211—C216—C215121.26 (19)
H22A—N22—H22B107.2C211—C216—H216119.4
C208—C203—C204118.61 (19)C215—C216—H216119.4
C208—C203—C202120.95 (17)N12—C110—C109110.10 (18)
C204—C203—C202120.42 (17)N12—C110—C111109.87 (15)
C115—C116—C111121.47 (19)C109—C110—C111113.31 (17)
C115—C116—H116119.3N12—C110—H110107.8
C111—C116—H116119.3C109—C110—H110107.8
C108—C103—C104118.60 (19)C111—C110—H110107.8
C108—C103—C102122.48 (17)C107—C108—C103121.44 (19)
C104—C103—C102118.90 (18)C107—C108—H108119.3
C116—C111—C112118.72 (19)C103—C108—H108119.3
C116—C111—C110119.63 (18)N21—C202—C203109.37 (15)
C112—C111—C110121.65 (18)N21—C202—C201110.71 (16)
C206—C207—C208118.00 (19)C203—C202—C201113.36 (16)
C206—C207—H207121.0N21—C202—H202107.7
C208—C207—H207121.0C203—C202—H202107.7
F12—C114—C115117.93 (19)C201—C202—H202107.7
F12—C114—C113118.90 (19)C106—C107—C108117.8 (2)
C115—C114—C113123.2 (2)C106—C107—H107121.1
O22—C218—O21125.12 (18)C108—C107—H107121.1
O22—C218—C217120.60 (19)C105—C104—C103120.9 (2)
O21—C218—C217114.27 (18)C105—C104—H104119.5
C114—C113—C112118.08 (19)C103—C104—H104119.5
C114—C113—H113121.0C210—C209—H20A109.5
C112—C113—H113121.0C210—C209—H20B109.5
C106—C105—C104117.92 (18)H20A—C209—H20B109.5
C106—C105—H105121.0C210—C209—H20C109.5
C104—C105—H105121.0H20A—C209—H20C109.5
C114—C115—C116117.78 (19)H20B—C209—H20C109.5
C114—C115—H115121.1C202—C201—H20D109.5
C116—C115—H115121.1C202—C201—H20E109.5
C211—C212—C213120.51 (19)H20D—C201—H20E109.5
C211—C212—H212119.7C202—C201—H20F109.5
C213—C212—H212119.7H20D—C201—H20F109.5
F21—C206—C207117.9 (2)H20E—C201—H20F109.5
F21—C206—C205118.7 (2)C110—C109—H10A109.5
C207—C206—C205123.4 (2)C110—C109—H10B109.5
C120—C119—H11C109.5H10A—C109—H10B109.5
C120—C119—H11D109.5C110—C109—H10C109.5
H11C—C119—H11D109.5H10A—C109—H10C109.5
C120—C119—H11E109.5H10B—C109—H10C109.5
H11C—C119—H11E109.5C220—C219—H21F109.5
H11D—C119—H11E109.5C220—C219—H21G109.5
O14—C120—O13124.87 (18)H21F—C219—H21G109.5
O14—C120—C119119.96 (18)C220—C219—H21H109.5
O13—C120—C119115.15 (17)H21F—C219—H21H109.5
C206—C205—C204117.6 (2)H21G—C219—H21H109.5
C206—C205—H205121.2C118—C117—H11F109.5
C204—C205—H205121.2C118—C117—H11G109.5
C214—C215—C216117.8 (2)H11F—C117—H11G109.5
C214—C215—H215121.1C118—C117—H11H109.5
C216—C215—H215121.1H11F—C117—H11H109.5
C111—C112—C113120.75 (19)H11G—C117—H11H109.5
C111—C112—H112119.6C102—C101—H10D109.5
C113—C112—H112119.6C102—C101—H10E109.5
C214—C213—C212118.39 (19)H10D—C101—H10E109.5
C214—C213—H213120.8C102—C101—H10F109.5
C212—C213—H213120.8H10D—C101—H10F109.5
O24—C220—O23124.97 (17)H10E—C101—H10F109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11A···O140.952.112.867 (2)136
N11—H11B···O120.952.152.896 (2)134
N12—H12A···O220.952.163.029 (2)151
N12—H12B···O240.952.012.923 (2)161
N21—H21A···O120.952.173.040 (2)151
N21—H21B···O140.952.052.956 (2)160
N22—H22A···O240.952.412.930 (2)114
N22—H22B···O220.952.252.892 (2)124
(II) di-µ-acetato-κ4O:O'-bis{[(S)-1-(1-aminoethyl)-4-fluorophenyl- k2C2,N]palladium(II)} benzene hemisolvate top
Crystal data top
[Pd2(C2H3O2)2(C8H9FN)2]·0.5C6H6F(000) = 1284
Mr = 646.27Dx = 1.794 Mg m3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 8096 reflections
a = 22.504 (5) Åθ = 1.9–28.4°
b = 9.1632 (19) ŵ = 1.55 mm1
c = 12.279 (3) ÅT = 110 K
β = 109.131 (4)°Rod, yellow
V = 2392.2 (9) Å30.64 × 0.10 × 0.03 mm
Z = 4
Data collection top
Make Model CCD area-detector
diffractometer
5876 independent reflections
Radiation source: fine-focus sealed tube5354 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
ϕ and ω scansθmax = 28.3°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 3030
Tmin = 0.437, Tmax = 0.955k = 1112
12301 measured reflectionsl = 1614
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.070 w = 1/[σ2(Fo2) + (0.0282P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.002
5876 reflectionsΔρmax = 0.88 e Å3
303 parametersΔρmin = 0.80 e Å3
1 restraintAbsolute structure: Flack (1983), with 2732 Fridel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.09 (3)
Crystal data top
[Pd2(C2H3O2)2(C8H9FN)2]·0.5C6H6V = 2392.2 (9) Å3
Mr = 646.27Z = 4
Monoclinic, C2Mo Kα radiation
a = 22.504 (5) ŵ = 1.55 mm1
b = 9.1632 (19) ÅT = 110 K
c = 12.279 (3) Å0.64 × 0.10 × 0.03 mm
β = 109.131 (4)°
Data collection top
Make Model CCD area-detector
diffractometer
5876 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
5354 reflections with I > 2σ(I)
Tmin = 0.437, Tmax = 0.955Rint = 0.038
12301 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.070Δρmax = 0.88 e Å3
S = 1.01Δρmin = 0.80 e Å3
5876 reflectionsAbsolute structure: Flack (1983), with 2732 Fridel pairs
303 parametersAbsolute structure parameter: 0.09 (3)
1 restraint
Special details top

Experimental. The values of Tmin and Tmax are 0.702264 and 1.000000 from SADABS.

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
xyzUiso*/Ueq
Pd10.802745 (14)0.49553 (4)0.96888 (3)0.01569 (8)
Pd20.926332 (14)0.57378 (3)0.96899 (3)0.01476 (8)
O110.84187 (13)0.5838 (4)1.1387 (2)0.0199 (6)
O210.92259 (14)0.6997 (4)1.1068 (3)0.0194 (7)
O220.94070 (13)0.3776 (4)1.0736 (3)0.0181 (7)
O120.84135 (14)0.2947 (3)1.0289 (3)0.0190 (7)
F10.75675 (14)0.1274 (3)0.6132 (2)0.0345 (7)
F20.91083 (14)1.1354 (3)0.8504 (3)0.0333 (8)
N20.92915 (17)0.4592 (4)0.8281 (3)0.0177 (8)
H2A0.96550.39890.85040.023*
H2B0.89350.39700.80370.023*
N10.76473 (17)0.6888 (4)0.9021 (3)0.0200 (8)
H1A0.73990.72400.94600.026*
H1B0.79780.75670.91060.026*
C1080.7653 (2)0.4295 (6)0.8086 (4)0.0205 (10)
C2080.92068 (19)0.7396 (5)0.8673 (4)0.0159 (9)
C2060.91397 (19)0.9933 (6)0.8188 (4)0.0231 (10)
C1040.71066 (19)0.5051 (7)0.6127 (4)0.0262 (10)
H1040.68910.58080.55750.034*
C2020.93027 (19)0.5505 (5)0.7278 (4)0.0169 (9)
H2020.97140.53850.71750.022*
C2010.8796 (2)0.4982 (6)0.6186 (4)0.0280 (10)
H20A0.83850.50260.62960.036*
H20B0.88850.39730.60220.036*
H20C0.87940.56090.55380.036*
C2070.9157 (2)0.8863 (5)0.8967 (4)0.0208 (10)
H2070.91340.91140.97280.027*
C1100.9006 (2)0.2808 (5)1.0737 (4)0.0179 (9)
C1090.9257 (2)0.1395 (6)1.1328 (4)0.0235 (10)
H10A0.94640.15721.21530.031*
H10B0.95610.09831.09960.031*
H10C0.89090.07071.12210.031*
C2090.9022 (2)0.7483 (6)1.2806 (4)0.0269 (12)
H20D0.86740.81381.27810.035*
H20E0.94100.80511.29590.035*
H20F0.90760.67611.34200.035*
C2100.8877 (2)0.6706 (5)1.1659 (4)0.0188 (9)
C1070.7726 (2)0.2917 (5)0.7699 (4)0.0193 (10)
H1070.79420.21500.82400.025*
C1020.7245 (2)0.6845 (5)0.7774 (4)0.0226 (10)
H1020.68060.69040.77480.029*
C1030.73326 (19)0.5379 (5)0.7297 (4)0.0184 (10)
C2030.92310 (19)0.7083 (5)0.7565 (4)0.0188 (10)
C1010.7371 (3)0.8170 (6)0.7133 (5)0.0325 (13)
H10D0.78090.81530.71490.042*
H10E0.72950.90630.75070.042*
H10F0.70900.81470.63320.042*
C1050.7182 (2)0.3665 (6)0.5724 (5)0.0284 (12)
H1050.70230.34340.49000.037*
C2050.9163 (2)0.9668 (5)0.7092 (4)0.0262 (11)
H2050.91531.04670.65560.034*
C1060.7484 (2)0.2639 (6)0.6520 (5)0.0266 (11)
C2040.9202 (2)0.8215 (5)0.6784 (4)0.0229 (11)
H2040.92080.79830.60090.030*
C10.50000.8842 (11)0.50000.042 (2)
H10.50000.99120.50000.055*
C30.5522 (2)0.6557 (8)0.5667 (5)0.0424 (16)
H30.58960.60200.61310.055*
C20.5518 (3)0.8086 (8)0.5681 (5)0.0466 (17)
H20.58850.86200.61760.061*
C40.50000.5816 (11)0.50000.0386 (18)
H40.50000.47460.50000.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.01406 (14)0.01669 (17)0.01679 (17)0.00081 (14)0.00571 (12)0.00112 (15)
Pd20.01459 (14)0.01257 (16)0.01806 (17)0.00014 (14)0.00661 (12)0.00017 (15)
O110.0215 (14)0.0223 (17)0.0166 (15)0.0001 (15)0.0073 (12)0.0043 (15)
O210.0217 (16)0.0198 (18)0.0187 (17)0.0029 (14)0.0096 (14)0.0048 (14)
O220.0164 (15)0.0184 (18)0.0179 (17)0.0008 (13)0.0035 (13)0.0039 (14)
O120.0189 (15)0.0188 (17)0.0190 (17)0.0029 (13)0.0057 (13)0.0016 (14)
F10.0471 (18)0.0259 (16)0.0298 (16)0.0044 (14)0.0116 (14)0.0110 (14)
F20.0414 (17)0.0141 (15)0.0440 (19)0.0034 (13)0.0137 (15)0.0028 (15)
N20.0183 (18)0.015 (2)0.019 (2)0.0000 (14)0.0049 (16)0.0001 (15)
N10.0206 (18)0.019 (2)0.023 (2)0.0034 (16)0.0107 (17)0.0015 (17)
C1080.015 (2)0.021 (2)0.025 (3)0.0045 (19)0.0061 (19)0.000 (2)
C2080.0123 (19)0.014 (2)0.020 (2)0.0009 (17)0.0028 (17)0.0046 (19)
C2060.0178 (19)0.012 (2)0.037 (3)0.001 (2)0.0056 (19)0.001 (3)
C1040.019 (2)0.038 (3)0.022 (2)0.003 (2)0.0059 (18)0.006 (3)
C2020.0149 (18)0.018 (2)0.020 (2)0.0011 (16)0.0080 (16)0.0013 (18)
C2010.034 (2)0.026 (3)0.022 (2)0.004 (3)0.0070 (19)0.003 (3)
C2070.018 (2)0.021 (3)0.022 (3)0.0004 (19)0.006 (2)0.003 (2)
C1100.022 (2)0.017 (2)0.014 (2)0.0029 (19)0.0066 (18)0.003 (2)
C1090.026 (2)0.020 (2)0.023 (2)0.002 (2)0.006 (2)0.003 (2)
C2090.027 (3)0.032 (3)0.020 (3)0.005 (2)0.006 (2)0.010 (2)
C2100.017 (2)0.021 (2)0.016 (2)0.0029 (18)0.0030 (18)0.0014 (19)
C1070.016 (2)0.021 (3)0.021 (2)0.0017 (18)0.0056 (19)0.003 (2)
C1020.020 (2)0.024 (3)0.025 (3)0.002 (2)0.008 (2)0.004 (2)
C1030.0148 (19)0.021 (3)0.022 (2)0.0033 (16)0.0087 (18)0.0012 (18)
C2030.0105 (18)0.022 (2)0.022 (3)0.0019 (17)0.0024 (18)0.001 (2)
C1010.034 (3)0.031 (3)0.031 (3)0.001 (2)0.009 (3)0.005 (3)
C1050.023 (2)0.040 (3)0.023 (3)0.000 (2)0.008 (2)0.004 (2)
C2050.024 (2)0.023 (3)0.028 (3)0.0009 (19)0.003 (2)0.007 (2)
C1060.024 (2)0.026 (3)0.030 (3)0.006 (2)0.010 (2)0.010 (2)
C2040.020 (2)0.022 (3)0.023 (3)0.0003 (19)0.002 (2)0.005 (2)
C10.032 (4)0.063 (6)0.032 (5)0.0000.011 (4)0.000
C30.027 (3)0.075 (5)0.026 (3)0.011 (3)0.009 (2)0.010 (3)
C20.031 (3)0.070 (5)0.036 (3)0.008 (3)0.007 (3)0.001 (3)
C40.043 (4)0.049 (5)0.029 (4)0.0000.019 (3)0.000
Geometric parameters (Å, º) top
Pd1—C1081.965 (5)C201—H20B0.9801
Pd1—N12.020 (4)C201—H20C0.9801
Pd1—O122.065 (3)C207—H2070.9800
Pd1—O112.139 (3)C110—C1091.501 (7)
Pd1—Pd22.8717 (7)C109—H10A0.9801
Pd2—C2081.944 (4)C109—H10B0.9801
Pd2—N22.042 (4)C109—H10C0.9801
Pd2—O212.072 (3)C209—C2101.516 (6)
Pd2—O222.172 (3)C209—H20D0.9801
Pd2—Pd2i3.1494 (9)C209—H20E0.9801
O11—C2101.259 (5)C209—H20F0.9801
O21—C2101.259 (5)C107—C1061.392 (7)
O22—C1101.265 (5)C107—H1070.9800
O12—C1101.272 (5)C102—C1031.504 (6)
F1—C1061.373 (6)C102—C1011.523 (7)
F2—C2061.366 (6)C102—H1020.9800
N2—C2021.495 (6)C203—C2041.399 (7)
N2—H2A0.9500C101—H10D0.9801
N2—H2B0.9500C101—H10E0.9801
N1—C1021.503 (6)C101—H10F0.9801
N1—H1A0.9500C105—C1061.366 (8)
N1—H1B0.9500C105—H1050.9800
C108—C1071.378 (7)C205—C2041.394 (7)
C108—C1031.410 (6)C205—H2050.9800
C208—C2071.405 (7)C204—H2040.9800
C208—C2031.409 (7)C1—C2ii1.379 (8)
C206—C2071.362 (7)C1—C21.379 (8)
C206—C2051.385 (7)C1—H10.9800
C104—C1031.391 (6)C3—C41.372 (8)
C104—C1051.393 (8)C3—C21.401 (10)
C104—H1040.9800C3—H30.9800
C202—C2031.509 (6)C2—H20.9800
C202—C2011.525 (6)C4—C3ii1.372 (8)
C202—H2020.9800C4—H40.9800
C201—H20A0.9801
C108—Pd1—N183.00 (18)C206—C207—H207120.2
C108—Pd1—O1294.32 (17)C208—C207—H207120.2
N1—Pd1—O12177.14 (14)O22—C110—O12125.2 (4)
C108—Pd1—O11175.70 (19)O22—C110—C109116.8 (4)
N1—Pd1—O1192.76 (15)O12—C110—C109118.0 (4)
O12—Pd1—O1189.90 (13)C110—C109—H10A109.5
C108—Pd1—Pd2100.06 (12)C110—C109—H10B109.5
N1—Pd1—Pd293.59 (11)H10A—C109—H10B109.5
O12—Pd1—Pd285.89 (8)C110—C109—H10C109.5
O11—Pd1—Pd279.39 (8)H10A—C109—H10C109.5
C208—Pd2—N282.62 (18)H10B—C109—H10C109.5
C208—Pd2—O2194.42 (17)C210—C209—H20D109.5
N2—Pd2—O21177.03 (14)C210—C209—H20E109.5
C208—Pd2—O22173.12 (16)H20D—C209—H20E109.5
N2—Pd2—O2292.04 (13)C210—C209—H20F109.5
O21—Pd2—O2290.93 (13)H20D—C209—H20F109.5
C208—Pd2—Pd1109.59 (12)H20E—C209—H20F109.5
N2—Pd2—Pd199.79 (10)O11—C210—O21126.4 (4)
O21—Pd2—Pd180.85 (8)O11—C210—C209116.8 (4)
O22—Pd2—Pd175.52 (8)O21—C210—C209116.9 (4)
C208—Pd2—Pd2i89.85 (12)C108—C107—C106118.5 (5)
N2—Pd2—Pd2i83.24 (10)C108—C107—H107120.8
O21—Pd2—Pd2i97.12 (8)C106—C107—H107120.8
O22—Pd2—Pd2i85.19 (8)N1—C102—C103107.9 (4)
Pd1—Pd2—Pd2i160.532 (15)N1—C102—C101110.7 (4)
C210—O11—Pd1122.5 (3)C103—C102—C101116.1 (4)
C210—O21—Pd2123.5 (3)N1—C102—H102107.2
C110—O22—Pd2127.8 (3)C103—C102—H102107.2
C110—O12—Pd1120.2 (3)C101—C102—H102107.2
C202—N2—Pd2115.0 (3)C104—C103—C108119.3 (4)
C202—N2—H2A108.5C104—C103—C102123.0 (4)
Pd2—N2—H2A108.5C108—C103—C102117.7 (4)
C202—N2—H2B108.5C204—C203—C208120.2 (5)
Pd2—N2—H2B108.5C204—C203—C202122.4 (4)
H2A—N2—H2B107.5C208—C203—C202117.5 (4)
C102—N1—Pd1115.1 (3)C102—C101—H10D109.5
C102—N1—H1A108.5C102—C101—H10E109.5
Pd1—N1—H1A108.5H10D—C101—H10E109.5
C102—N1—H1B108.5C102—C101—H10F109.5
Pd1—N1—H1B108.5H10D—C101—H10F109.5
H1A—N1—H1B107.5H10E—C101—H10F109.5
C107—C108—C103120.0 (4)C106—C105—C104117.6 (5)
C107—C108—Pd1124.6 (4)C106—C105—H105121.2
C103—C108—Pd1115.2 (3)C104—C105—H105121.2
C207—C208—C203118.3 (4)C206—C205—C204117.2 (5)
C207—C208—Pd2125.2 (4)C206—C205—H205121.4
C203—C208—Pd2116.5 (3)C204—C205—H205121.4
C207—C206—F2118.6 (4)C105—C106—F1118.1 (4)
C207—C206—C205123.7 (5)C105—C106—C107123.4 (5)
F2—C206—C205117.7 (5)F1—C106—C107118.4 (5)
C103—C104—C105121.2 (5)C205—C204—C203121.0 (5)
C103—C104—H104119.4C205—C204—H204119.5
C105—C104—H104119.4C203—C204—H204119.5
N2—C202—C203108.2 (3)C2ii—C1—C2119.7 (9)
N2—C202—C201109.8 (4)C2ii—C1—H1120.2
C203—C202—C201113.6 (4)C2—C1—H1120.2
N2—C202—H202108.4C4—C3—C2119.6 (6)
C203—C202—H202108.4C4—C3—H3120.2
C201—C202—H202108.4C2—C3—H3120.2
C202—C201—H20A109.5C1—C2—C3120.2 (6)
C202—C201—H20B109.5C1—C2—H2119.9
H20A—C201—H20B109.5C3—C2—H2119.9
C202—C201—H20C109.5C3ii—C4—C3120.7 (9)
H20A—C201—H20C109.5C3ii—C4—H4119.7
H20B—C201—H20C109.5C3—C4—H4119.7
C206—C207—C208119.7 (5)
Symmetry codes: (i) x+2, y, z+2; (ii) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O12iii0.952.062.947 (5)155
N2—H2A···O22i0.952.022.877 (5)149
Symmetry codes: (i) x+2, y, z+2; (iii) x+3/2, y+1/2, z+2.

Experimental details

(I)(II)
Crystal data
Chemical formula[Pd(C2H3O2)2(C8H10FN)2][Pd2(C2H3O2)2(C8H9FN)2]·0.5C6H6
Mr502.83646.27
Crystal system, space groupMonoclinic, P21Monoclinic, C2
Temperature (K)110110
a, b, c (Å)10.589 (2), 17.537 (3), 11.686 (2)22.504 (5), 9.1632 (19), 12.279 (3)
β (°) 100.954 (3) 109.131 (4)
V3)2130.6 (7)2392.2 (9)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.921.55
Crystal size (mm)0.80 × 0.70 × 0.600.64 × 0.10 × 0.03
Data collection
DiffractometerMake Model CCD area-detector
diffractometer
Make Model CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.500, 0.5770.437, 0.955
No. of measured, independent and
observed [I > 2σ(I)] reflections
29128, 10628, 10531 12301, 5876, 5354
Rint0.0170.038
(sin θ/λ)max1)0.6680.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.061, 1.06 0.036, 0.070, 1.01
No. of reflections106285876
No. of parameters531303
No. of restraints11
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.65, 0.300.88, 0.80
Absolute structureFlack (1983), with 5132 Friedel pairsFlack (1983), with 2732 Fridel pairs
Absolute structure parameter0.017 (11)0.09 (3)

Computer programs: SMART (Bruker, 2001), SMART, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1990), Please provide missing details.

Selected geometric parameters (Å, º) for (I) top
Pd1—O112.0192 (15)O13—C1201.289 (2)
Pd1—O132.0271 (14)O23—C2201.298 (2)
Pd1—N122.0409 (16)O21—C2181.299 (2)
Pd1—N112.0652 (16)O11—C1181.299 (2)
Pd2—O232.0144 (14)O12—C1181.233 (2)
Pd2—O212.0155 (14)O24—C2201.235 (2)
Pd2—N212.0507 (16)O22—C2181.237 (3)
Pd2—N222.0575 (17)O14—C1201.243 (3)
O11—Pd1—O13174.33 (6)O23—Pd2—O21174.96 (6)
O11—Pd1—N1289.55 (6)O23—Pd2—N2189.13 (6)
O13—Pd1—N1287.67 (6)O21—Pd2—N2187.98 (6)
O11—Pd1—N1191.22 (6)O23—Pd2—N2291.23 (6)
O13—Pd1—N1191.83 (6)O21—Pd2—N2291.77 (7)
N12—Pd1—N11176.65 (7)N21—Pd2—N22178.36 (7)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N11—H11A···O140.952.112.867 (2)136
N11—H11B···O120.952.152.896 (2)134
N12—H12A···O220.952.163.029 (2)151
N12—H12B···O240.952.012.923 (2)161
N21—H21A···O120.952.173.040 (2)151
N21—H21B···O140.952.052.956 (2)160
N22—H22A···O240.952.412.930 (2)114
N22—H22B···O220.952.252.892 (2)124
Selected geometric parameters (Å, º) for (II) top
Pd1—C1081.965 (5)Pd2—O212.072 (3)
Pd1—N12.020 (4)Pd2—O222.172 (3)
Pd1—O122.065 (3)Pd2—Pd2i3.1494 (9)
Pd1—O112.139 (3)O11—C2101.259 (5)
Pd1—Pd22.8717 (7)O21—C2101.259 (5)
Pd2—C2081.944 (4)O22—C1101.265 (5)
Pd2—N22.042 (4)O12—C1101.272 (5)
C108—Pd1—N183.00 (18)C208—Pd2—N282.62 (18)
C108—Pd1—O1294.32 (17)C208—Pd2—O2194.42 (17)
N1—Pd1—O12177.14 (14)N2—Pd2—O21177.03 (14)
C108—Pd1—O11175.70 (19)C208—Pd2—O22173.12 (16)
N1—Pd1—O1192.76 (15)N2—Pd2—O2292.04 (13)
O12—Pd1—O1189.90 (13)O21—Pd2—O2290.93 (13)
Symmetry code: (i) x+2, y, z+2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O12ii0.952.062.947 (5)155
N2—H2A···O22i0.952.022.877 (5)149
Symmetry codes: (i) x+2, y, z+2; (ii) x+3/2, y+1/2, z+2.
 

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