Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023173/hb2403sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023173/hb2403Isup2.hkl |
CCDC reference: 650708
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (Wave) = 0.000 Å Some non-H atoms missing
- R factor = 0.074
- wR factor = 0.248
- Data-to-parameter ratio = 16.3
checkCIF/PLATON results
No syntax errors found
Alert level C CHEMW01_ALERT_1_C The difference between the given and expected weight for compound is greater 1 mass unit. Check that all hydrogen atoms have been taken into account.
Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C70 H44 Cl8 D2 N2 O4 P2 Pd1 Atom count from the _atom_site data: C70 H46 Cl8 N2 O4 P2 Pd1 ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.949 Tmax scaled 0.845 Tmin scaled 0.761 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G ALERT: Large difference may be due to a symmetry error - see SYMMG tests From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C70 H44 Cl8 D2 N2 O4 P2 Pd TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 280.00 280.00 0.00 H 176.00 184.00 -8.00 Cl 32.00 32.00 0.00 D 8.00 0.00 8.00 N 8.00 8.00 0.00 O 16.00 16.00 0.00 P 8.00 8.00 0.00 Pd 4.00 4.00 0.00 REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max 28.03 From the CIF: _reflns_number_total 14408 From the CIF: _diffrn_reflns_limit_ max hkl 21. 23. 22. From the CIF: _diffrn_reflns_limit_ min hkl -24. -23. -22. TEST1: Expected hkl limits for theta max Calculated maximum hkl 26. 26. 23. Calculated minimum hkl -26. -26. -23. REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 28.03 From the CIF: _reflns_number_total 14408 Count of symmetry unique reflns 8630 Completeness (_total/calc) 166.95% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 5778 Fraction of Friedel pairs measured 0.670 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Deblon et al. (2003); Defieber et al. (2007); Maire et al. (2004); Van den Berg et al. (2000).
Two equivalents of ligand (I) reacted cleanly with PdCl2(NCCH3)2 in toluene/acetonitrile solution to afford the title compound (II) in yields of over 90%. Single crystals of (II) were grown from a CDCl3 solution layered with Et2O. The crystals are unstable outside their mother-liquor, and a single-crystal was sealed in a Lindemann capillary for intensity collection, together with its mother-liquor.
All H atoms bound to carbon were included in calculated positions (C—H = 0.93–0.98 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).
The dibenzoazepine framgment containing the N2 atom was found disordered over two positions. The occupational parameters were determined to be 0.70 and 0.30. The non-hydrogen atoms of the six-menbered ring of this frament were refined with the atoms being forced into planarity. The deuterochloroform molecules were also found disordered. The disorder of the C2S molecule was modelled by two sets of chlorine positions with occupancies 0.60 and 0.40. The best model for the remaining solvent molecules was obtained by free refinement of its occupation factors, giving a partial occupation of approximatly 0.5 for both molecules. These occupations were fixed during the final refinements. All C—Cl distances were restrained to similar lenghts. The absolute structure was assigned from the known configuration of the starting binaphtol reagent used in the synthesis of ligand (I) and confirmed by refinement of the Flack (1983) absolute structure parameter.
P-olefin ligands constitute a rather new entry in the development of efficient bidentate ligand systems for organometallic reactivity and catalysis. Grützmacher et al. developed a new class of P-olefin ligands based on the dibenzo[b,f]cycloheptene and dibenzo[b,f]azepin motifs, several of them chiral (Maire et al., 2004). On the other hand, de Vries and Feringa (Van den Berg et al., 2000) showed that chiral phosphoramidites are highly versatile monodentate ligands and so we anticipated that the dibenzo[b,f]azepin molecule could be readily used to form new chiral phosphoramidite-olefin ligands such as (I). Ligand (I) has very recently been disclosed to be an excellent ligand for the enantioselective formation of allylic amines from allylic alcohols (Defieber et al., 2007).
Here, we report the crystal structure of a Pd(II) complex bearing the chiral ligand (I). The asymmetric unit of (II) consists of one metal complex molecule and three independent deuterocloroform molecules (two of which are half occupied). The Pd atom displays a distorted square planar environment, in which two ligands (I) are coordinated through their P atoms in a monodentade fashion and the remaining coordination sites are occupied by two chloride anions. The ligands are located in a cis configuration around the metal centre [P2—Pd1—P1 = 94.59 (7)°; Cl2—Pd—Cl1 = 89.24 (9)°]. The metal complex adopts pseudo-C2 symmetry about the Pd atom (Fig. 1). The naphtyl groups are twisted in both molecules as indicated by torsion angles of 50.39 (2)° for C1—C10—C11—C12 and 52.23 (2)° for C35—C44—C45—C46.
The crystal structure of (II) consists of a three-dimensional-hydrogen bonded network, which is self assembled via C—H··· π and C—H···Cl interaction [C27i···CL2: 3.741 (12) Å and C14i···Cl2: 3.613 (10) Å; i= x, 1 - y, 1/4 + z]. The coordinated chloride (Cl2) ion causes the self-assembly of the metal complex to generate a right-handed helical arrangement along the fourfold screw axis (41). Neighbouring helices are assembled by weak van der Waals interactions to afford a 3-D hydrogen-bonded assembly. This organization yields a framework with one-dimensional channels running along the c axis, where the deuterochloroform molecules are allocated, and which are sustained into the channels by C—H···Cl hydrogen bonding to the chloride ligands of the complex [Cl1···C2Sii: 3.358 Å; ii= x, 1 - y, -3/4 + z] (Fig 2).
For related literature, see: Deblon et al. (2003); Defieber et al. (2007); Maire et al. (2004); Van den Berg et al. (2000).
Data collection: CrystalClear (Rigaku/MSC Inc., 2000); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC Inc., 2004); program(s) used to solve structure: SHELXLTL-NT (Bruker, 1998); program(s) used to refine structure: SHELXLTL-NT; molecular graphics: SHELXLTL-NT and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXLTL-NT and PLATON (Spek, 2003).
[PdCl2(C34H22NO2P)2].2CDCl3 | Dx = 1.377 Mg m−3 |
Mr = 1431.03 | Mo Kα radiation, λ = 0.71070 Å |
Tetragonal, P41 | Cell parameters from 2378 reflections |
Hall symbol: P 4w | θ = 2.0–27.6° |
a = 19.866 (2) Å | µ = 0.67 mm−1 |
c = 17.497 (2) Å | T = 293 K |
V = 6905.2 (13) Å3 | Prism, yellow |
Z = 4 | 0.42 × 0.30 × 0.25 mm |
F(000) = 2896 |
Rigaku AFC7S Mercury diffractometer | 14408 independent reflections |
Radiation source: normal-focus sealed tube | 9124 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
Detector resolution: 14.6306 pixels mm-1 | θmax = 28.0°, θmin = 1.5° |
ω scans | h = −24→21 |
Absorption correction: multi-scan Jacobson (1998) | k = −23→23 |
Tmin = 0.802, Tmax = 0.891 | l = −22→22 |
79958 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.074 | H-atom parameters constrained |
wR(F2) = 0.248 | w = 1/[σ2(Fo2) + (0.1446P)2 + 3.0373P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
14408 reflections | Δρmax = 1.06 e Å−3 |
886 parameters | Δρmin = −0.72 e Å−3 |
593 restraints | Absolute structure: Flack (1983), with 5079 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (4) |
[PdCl2(C34H22NO2P)2].2CDCl3 | Z = 4 |
Mr = 1431.03 | Mo Kα radiation |
Tetragonal, P41 | µ = 0.67 mm−1 |
a = 19.866 (2) Å | T = 293 K |
c = 17.497 (2) Å | 0.42 × 0.30 × 0.25 mm |
V = 6905.2 (13) Å3 |
Rigaku AFC7S Mercury diffractometer | 14408 independent reflections |
Absorption correction: multi-scan Jacobson (1998) | 9124 reflections with I > 2σ(I) |
Tmin = 0.802, Tmax = 0.891 | Rint = 0.063 |
79958 measured reflections |
R[F2 > 2σ(F2)] = 0.074 | H-atom parameters constrained |
wR(F2) = 0.248 | Δρmax = 1.06 e Å−3 |
S = 1.07 | Δρmin = −0.72 e Å−3 |
14408 reflections | Absolute structure: Flack (1983), with 5079 Friedel pairs |
886 parameters | Absolute structure parameter: 0.02 (4) |
593 restraints |
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 | 0.46461 (3) | 0.15920 (3) | 0.07387 (5) | 0.05517 (19) | |
P2 | 0.51845 (11) | 0.13326 (10) | 0.18186 (12) | 0.0550 (5) | |
P1 | 0.54240 (10) | 0.23245 (9) | 0.03450 (12) | 0.0515 (4) | |
Cl2 | 0.39914 (12) | 0.18825 (12) | −0.03184 (14) | 0.0767 (6) | |
Cl1 | 0.38606 (14) | 0.07551 (13) | 0.10470 (16) | 0.0870 (8) | |
O1 | 0.5486 (3) | 0.2454 (3) | −0.0559 (3) | 0.0584 (13) | |
O2 | 0.6150 (2) | 0.2024 (2) | 0.0547 (3) | 0.0511 (12) | |
O4 | 0.5558 (3) | 0.1988 (3) | 0.2163 (3) | 0.0591 (13) | |
N1 | 0.5325 (3) | 0.3100 (3) | 0.0626 (4) | 0.0546 (15) | |
O3 | 0.4720 (3) | 0.1113 (3) | 0.2535 (3) | 0.0614 (13) | |
N2 | 0.5686 (4) | 0.0687 (3) | 0.1775 (4) | 0.0601 (16) | |
C1 | 0.5795 (5) | 0.2007 (4) | −0.1058 (4) | 0.060 (2) | |
C2 | 0.5371 (5) | 0.1683 (5) | −0.1609 (5) | 0.073 (2) | |
H2A | 0.4910 | 0.1760 | −0.1613 | 0.087* | |
C3 | 0.5653 (6) | 0.1268 (5) | −0.2116 (5) | 0.077 (3) | |
H3 | 0.5385 | 0.1092 | −0.2503 | 0.093* | |
C4 | 0.6333 (6) | 0.1087 (5) | −0.2095 (5) | 0.075 (2) | |
C5 | 0.6571 (8) | 0.0573 (6) | −0.2551 (7) | 0.094 (3) | |
H5 | 0.6287 | 0.0364 | −0.2899 | 0.112* | |
C6 | 0.7220 (10) | 0.0376 (8) | −0.2491 (8) | 0.118 (5) | |
H6 | 0.7376 | 0.0028 | −0.2800 | 0.141* | |
C7 | 0.7696 (7) | 0.0704 (6) | −0.1936 (7) | 0.101 (4) | |
H7 | 0.8145 | 0.0573 | −0.1908 | 0.121* | |
C8 | 0.7454 (6) | 0.1190 (5) | −0.1486 (6) | 0.081 (3) | |
H8 | 0.7739 | 0.1397 | −0.1136 | 0.098* | |
C9 | 0.6768 (5) | 0.1399 (4) | −0.1532 (5) | 0.063 (2) | |
C10 | 0.6474 (4) | 0.1920 (4) | −0.1040 (4) | 0.0544 (18) | |
C11 | 0.6907 (4) | 0.2292 (4) | −0.0508 (4) | 0.0519 (17) | |
C12 | 0.6748 (4) | 0.2308 (4) | 0.0278 (5) | 0.0525 (17) | |
C13 | 0.7195 (4) | 0.2582 (4) | 0.0825 (5) | 0.0581 (18) | |
H13 | 0.7101 | 0.2547 | 0.1344 | 0.070* | |
C14 | 0.7761 (4) | 0.2895 (4) | 0.0584 (6) | 0.068 (2) | |
H14 | 0.8055 | 0.3067 | 0.0949 | 0.082* | |
C15 | 0.7926 (4) | 0.2973 (4) | −0.0205 (5) | 0.0586 (19) | |
C16 | 0.8480 (5) | 0.3376 (6) | −0.0460 (7) | 0.088 (3) | |
H16 | 0.8754 | 0.3586 | −0.0101 | 0.105* | |
C17 | 0.8612 (5) | 0.3456 (6) | −0.1210 (7) | 0.089 (3) | |
H17 | 0.8984 | 0.3702 | −0.1372 | 0.106* | |
C18 | 0.8180 (6) | 0.3163 (6) | −0.1731 (7) | 0.093 (3) | |
H18 | 0.8261 | 0.3228 | −0.2249 | 0.112* | |
C19 | 0.7646 (5) | 0.2785 (5) | −0.1523 (5) | 0.077 (3) | |
H19 | 0.7380 | 0.2589 | −0.1898 | 0.092* | |
C20 | 0.7485 (4) | 0.2680 (4) | −0.0745 (5) | 0.0599 (19) | |
C21 | 0.5706 (4) | 0.3648 (4) | 0.0274 (6) | 0.062 (2) | |
C22 | 0.5534 (5) | 0.3884 (5) | −0.0429 (6) | 0.074 (2) | |
H22 | 0.5168 | 0.3706 | −0.0690 | 0.089* | |
C23 | 0.5926 (7) | 0.4409 (6) | −0.0759 (8) | 0.103 (4) | |
H23 | 0.5805 | 0.4615 | −0.1216 | 0.123* | |
C24 | 0.6528 (7) | 0.4604 (7) | −0.0339 (9) | 0.109 (4) | |
H24 | 0.6848 | 0.4874 | −0.0577 | 0.131* | |
C25 | 0.6625 (7) | 0.4415 (7) | 0.0337 (9) | 0.103 (4) | |
H25 | 0.6987 | 0.4599 | 0.0602 | 0.124* | |
C26 | 0.6224 (5) | 0.3950 (4) | 0.0710 (8) | 0.083 (3) | |
C27 | 0.6332 (6) | 0.3784 (5) | 0.1545 (8) | 0.093 (4) | |
H27 | 0.6774 | 0.3786 | 0.1717 | 0.111* | |
C28 | 0.5873 (7) | 0.3639 (5) | 0.2047 (7) | 0.083 (3) | |
H28 | 0.6020 | 0.3570 | 0.2545 | 0.100* | |
C29 | 0.5158 (5) | 0.3573 (4) | 0.1913 (6) | 0.071 (2) | |
C30 | 0.4712 (8) | 0.3774 (5) | 0.2496 (6) | 0.096 (4) | |
H30 | 0.4879 | 0.3960 | 0.2945 | 0.115* | |
C31 | 0.4029 (8) | 0.3694 (6) | 0.2403 (8) | 0.100 (4) | |
H31 | 0.3739 | 0.3837 | 0.2788 | 0.119* | |
C32 | 0.3770 (5) | 0.3413 (6) | 0.1763 (6) | 0.082 (3) | |
H32 | 0.3308 | 0.3351 | 0.1714 | 0.099* | |
C33 | 0.4200 (5) | 0.3218 (5) | 0.1183 (5) | 0.070 (2) | |
H33 | 0.4021 | 0.3032 | 0.0739 | 0.083* | |
C34 | 0.4880 (4) | 0.3293 (4) | 0.1245 (5) | 0.0581 (18) | |
C35 | 0.4326 (5) | 0.1589 (5) | 0.2915 (5) | 0.071 (2) | |
C36 | 0.3637 (6) | 0.1578 (6) | 0.2814 (7) | 0.086 (3) | |
H36 | 0.3439 | 0.1278 | 0.2473 | 0.104* | |
C37 | 0.3255 (6) | 0.2014 (6) | 0.3222 (9) | 0.099 (3) | |
H37 | 0.2788 | 0.1995 | 0.3188 | 0.119* | |
C38 | 0.3572 (9) | 0.2514 (7) | 0.3714 (7) | 0.110 (5) | |
C39 | 0.3148 (10) | 0.3015 (9) | 0.4059 (10) | 0.132 (5) | |
H39 | 0.2687 | 0.3015 | 0.3966 | 0.158* | |
C40 | 0.3424 (10) | 0.3484 (8) | 0.4520 (10) | 0.127 (5) | |
H40 | 0.3150 | 0.3792 | 0.4772 | 0.152* | |
C41 | 0.4097 (9) | 0.3507 (8) | 0.4613 (8) | 0.118 (4) | |
H41 | 0.4279 | 0.3842 | 0.4920 | 0.142* | |
C42 | 0.4522 (8) | 0.3057 (7) | 0.4274 (8) | 0.108 (4) | |
H42 | 0.4985 | 0.3100 | 0.4341 | 0.130* | |
C43 | 0.4255 (8) | 0.2510 (6) | 0.3809 (6) | 0.091 (3) | |
C44 | 0.4646 (6) | 0.2013 (4) | 0.3422 (5) | 0.077 (3) | |
C45 | 0.5384 (7) | 0.1966 (5) | 0.3536 (6) | 0.084 (3) | |
C46 | 0.5826 (5) | 0.1984 (4) | 0.2924 (5) | 0.070 (2) | |
C47 | 0.6528 (6) | 0.2003 (5) | 0.2969 (7) | 0.086 (3) | |
H47 | 0.6793 | 0.2051 | 0.2535 | 0.103* | |
C48 | 0.6815 (7) | 0.1945 (7) | 0.3696 (8) | 0.107 (4) | |
H48 | 0.7278 | 0.1981 | 0.3756 | 0.128* | |
C49 | 0.6400 (7) | 0.1831 (6) | 0.4341 (8) | 0.101 (3) | |
C50 | 0.6698 (11) | 0.1701 (9) | 0.5084 (11) | 0.142 (5) | |
H50 | 0.7160 | 0.1681 | 0.5172 | 0.171* | |
C51 | 0.6216 (11) | 0.1611 (10) | 0.5647 (12) | 0.149 (6) | |
H51 | 0.6392 | 0.1514 | 0.6127 | 0.178* | |
C52 | 0.5558 (10) | 0.1637 (8) | 0.5626 (11) | 0.136 (5) | |
H52 | 0.5295 | 0.1564 | 0.6058 | 0.163* | |
C53 | 0.5293 (9) | 0.1772 (7) | 0.4950 (6) | 0.115 (5) | |
H53 | 0.4828 | 0.1806 | 0.4904 | 0.138* | |
C54 | 0.5703 (8) | 0.1869 (5) | 0.4288 (6) | 0.096 (4) | |
C55 | 0.5962 (5) | 0.0410 (5) | 0.1050 (4) | 0.058 (2) | 0.695 (16) |
C56 | 0.5506 (5) | 0.0098 (5) | 0.0564 (5) | 0.065 (3) | 0.695 (16) |
H56 | 0.5062 | 0.0035 | 0.0718 | 0.078* | 0.695 (16) |
C57 | 0.5713 (6) | −0.0121 (5) | −0.0154 (5) | 0.077 (3) | 0.695 (16) |
H57 | 0.5407 | −0.0330 | −0.0479 | 0.092* | 0.695 (16) |
C58 | 0.6376 (7) | −0.0028 (6) | −0.0384 (4) | 0.085 (4) | 0.695 (16) |
H58 | 0.6514 | −0.0174 | −0.0864 | 0.102* | 0.695 (16) |
C59 | 0.6832 (6) | 0.0285 (6) | 0.0103 (5) | 0.077 (3) | 0.695 (16) |
H59 | 0.7276 | 0.0347 | −0.0051 | 0.092* | 0.695 (16) |
C60 | 0.6625 (5) | 0.0503 (5) | 0.0820 (5) | 0.066 (3) | 0.695 (16) |
C61 | 0.7128 (8) | 0.0813 (8) | 0.1411 (12) | 0.074 (3) | 0.695 (16) |
H61 | 0.7465 | 0.1079 | 0.1198 | 0.089* | 0.695 (16) |
C62 | 0.7154 (9) | 0.0763 (9) | 0.2117 (11) | 0.077 (3) | 0.695 (16) |
H62 | 0.7501 | 0.0984 | 0.2373 | 0.092* | 0.695 (16) |
C63 | 0.6679 (10) | 0.0385 (9) | 0.2562 (9) | 0.067 (3) | 0.695 (16) |
C64 | 0.6964 (7) | 0.0089 (8) | 0.3205 (10) | 0.080 (3) | 0.695 (16) |
H64 | 0.7424 | 0.0127 | 0.3293 | 0.096* | 0.695 (16) |
C65 | 0.6562 (7) | −0.0265 (7) | 0.3716 (8) | 0.083 (3) | 0.695 (16) |
H65 | 0.6753 | −0.0463 | 0.4146 | 0.099* | 0.695 (16) |
C66 | 0.5874 (7) | −0.0322 (7) | 0.3585 (9) | 0.074 (3) | 0.695 (16) |
H66 | 0.5605 | −0.0559 | 0.3927 | 0.088* | 0.695 (16) |
C67 | 0.5589 (7) | −0.0026 (8) | 0.2942 (11) | 0.066 (3) | 0.695 (16) |
H67 | 0.5129 | −0.0064 | 0.2854 | 0.079* | 0.695 (16) |
C68 | 0.5991 (10) | 0.0327 (10) | 0.2431 (9) | 0.061 (3) | 0.695 (16) |
C55A | 0.5723 (12) | 0.0395 (13) | 0.1022 (11) | 0.062 (4) | 0.305 (16) |
C56A | 0.5214 (11) | 0.0042 (13) | 0.0653 (13) | 0.059 (4) | 0.305 (16) |
H56A | 0.4794 | −0.0002 | 0.0881 | 0.071* | 0.305 (16) |
C57A | 0.5334 (14) | −0.0246 (12) | −0.0059 (14) | 0.077 (5) | 0.305 (16) |
H57A | 0.4994 | −0.0483 | −0.0306 | 0.092* | 0.305 (16) |
C58A | 0.5962 (16) | −0.0181 (14) | −0.0400 (12) | 0.084 (5) | 0.305 (16) |
H58A | 0.6042 | −0.0373 | −0.0876 | 0.100* | 0.305 (16) |
C59A | 0.6471 (13) | 0.0173 (14) | −0.0031 (14) | 0.078 (4) | 0.305 (16) |
H59A | 0.6891 | 0.0217 | −0.0260 | 0.094* | 0.305 (16) |
C60A | 0.6351 (11) | 0.0461 (13) | 0.0680 (14) | 0.067 (4) | 0.305 (16) |
C61A | 0.6951 (19) | 0.0703 (18) | 0.109 (2) | 0.069 (4) | 0.305 (16) |
H61A | 0.7288 | 0.0923 | 0.0816 | 0.083* | 0.305 (16) |
C62A | 0.7034 (19) | 0.060 (2) | 0.1941 (18) | 0.073 (4) | 0.305 (16) |
H62A | 0.7489 | 0.0623 | 0.2062 | 0.087* | 0.305 (16) |
C63A | 0.664 (2) | 0.048 (2) | 0.266 (2) | 0.069 (4) | 0.305 (16) |
C64A | 0.6841 (15) | 0.020 (2) | 0.335 (2) | 0.074 (4) | 0.305 (16) |
H64A | 0.7288 | 0.0238 | 0.3506 | 0.089* | 0.305 (16) |
C65A | 0.6376 (16) | −0.0119 (17) | 0.3818 (18) | 0.074 (5) | 0.305 (16) |
H65A | 0.6511 | −0.0301 | 0.4283 | 0.088* | 0.305 (16) |
C66A | 0.5707 (15) | −0.0169 (17) | 0.359 (2) | 0.067 (5) | 0.305 (16) |
H66A | 0.5396 | −0.0385 | 0.3900 | 0.080* | 0.305 (16) |
C67A | 0.5505 (19) | 0.010 (2) | 0.289 (3) | 0.064 (4) | 0.305 (16) |
H67A | 0.5058 | 0.0070 | 0.2741 | 0.077* | 0.305 (16) |
C68A | 0.597 (3) | 0.043 (2) | 0.2429 (19) | 0.060 (4) | 0.305 (16) |
C2S | 0.9015 (4) | 0.2278 (5) | −0.7074 (4) | 0.141 (6) | |
H2S | 0.9000 | 0.2771 | −0.7069 | 0.169* | |
Cl6 | 0.8807 (9) | 0.1984 (9) | −0.6167 (4) | 0.205 (8) | 0.60 |
Cl7 | 0.9823 (4) | 0.2023 (10) | −0.7313 (11) | 0.182 (7) | 0.60 |
Cl8 | 0.8439 (6) | 0.1985 (9) | −0.7743 (6) | 0.171 (6) | 0.60 |
Cl6A | 0.8781 (16) | 0.1686 (13) | −0.6377 (10) | 0.213 (10) | 0.40 |
Cl7A | 0.9894 (4) | 0.2278 (15) | −0.7147 (16) | 0.168 (9) | 0.40 |
Cl8A | 0.8676 (13) | 0.2024 (16) | −0.7954 (8) | 0.195 (10) | 0.40 |
C3S | 0.9472 (8) | 0.1616 (12) | −0.0093 (10) | 0.178 (16)* | 0.50 |
H3SA | 0.9545 | 0.2078 | 0.0085 | 0.214* | 0.50 |
Cl9 | 0.9319 (8) | 0.1577 (8) | −0.1072 (9) | 0.203 (5)* | 0.50 |
Cl10 | 1.0123 (7) | 0.1075 (7) | 0.0173 (9) | 0.191 (5)* | 0.50 |
Cl11 | 0.8718 (8) | 0.1281 (8) | 0.0235 (9) | 0.202 (5)* | 0.50 |
C1S | 0.8771 (9) | 0.1196 (7) | −0.3571 (9) | 0.174 (16)* | 0.50 |
H1S | 0.8296 | 0.1086 | −0.3486 | 0.209* | 0.50 |
Cl3 | 0.9285 (11) | 0.0522 (7) | −0.3290 (10) | 0.263 (8)* | 0.50 |
Cl4 | 0.8997 (9) | 0.1906 (7) | −0.3039 (8) | 0.226 (6)* | 0.50 |
Cl5 | 0.8915 (10) | 0.1362 (8) | −0.4541 (7) | 0.255 (8)* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0611 (4) | 0.0510 (3) | 0.0534 (3) | −0.0077 (2) | −0.0145 (3) | 0.0077 (3) |
P2 | 0.0676 (12) | 0.0490 (10) | 0.0485 (10) | −0.0017 (8) | −0.0124 (9) | 0.0068 (8) |
P1 | 0.0576 (11) | 0.0479 (10) | 0.0491 (10) | −0.0041 (8) | −0.0124 (8) | 0.0043 (8) |
Cl2 | 0.0803 (14) | 0.0791 (14) | 0.0707 (14) | −0.0126 (11) | −0.0330 (11) | 0.0156 (11) |
Cl1 | 0.0904 (16) | 0.0877 (16) | 0.0831 (16) | −0.0376 (13) | −0.0170 (13) | 0.0199 (13) |
O1 | 0.067 (3) | 0.057 (3) | 0.052 (3) | 0.002 (2) | −0.019 (3) | 0.002 (2) |
O2 | 0.058 (3) | 0.048 (3) | 0.047 (3) | 0.002 (2) | −0.007 (2) | 0.006 (2) |
O4 | 0.080 (4) | 0.050 (3) | 0.048 (3) | 0.002 (2) | −0.019 (3) | 0.003 (2) |
N1 | 0.052 (3) | 0.046 (3) | 0.065 (4) | −0.008 (2) | −0.007 (3) | 0.001 (3) |
O3 | 0.075 (4) | 0.056 (3) | 0.053 (3) | 0.007 (2) | −0.004 (3) | 0.014 (2) |
N2 | 0.075 (4) | 0.053 (4) | 0.053 (4) | 0.001 (3) | −0.007 (3) | 0.009 (3) |
C1 | 0.082 (6) | 0.059 (4) | 0.038 (4) | −0.005 (4) | −0.017 (4) | 0.003 (3) |
C2 | 0.094 (6) | 0.077 (6) | 0.047 (5) | −0.026 (5) | −0.014 (4) | 0.006 (4) |
C3 | 0.115 (8) | 0.070 (6) | 0.047 (5) | −0.027 (5) | −0.007 (5) | −0.016 (4) |
C4 | 0.105 (8) | 0.080 (6) | 0.039 (4) | −0.017 (5) | 0.001 (5) | −0.001 (4) |
C5 | 0.128 (10) | 0.092 (7) | 0.061 (6) | −0.018 (7) | 0.006 (6) | −0.019 (6) |
C6 | 0.171 (15) | 0.111 (10) | 0.071 (7) | −0.005 (9) | 0.006 (9) | −0.032 (7) |
C7 | 0.131 (9) | 0.097 (8) | 0.074 (7) | 0.021 (7) | 0.027 (7) | −0.020 (6) |
C8 | 0.103 (8) | 0.081 (6) | 0.060 (5) | 0.008 (5) | 0.005 (5) | −0.010 (5) |
C9 | 0.079 (5) | 0.061 (5) | 0.051 (5) | −0.003 (4) | −0.004 (4) | −0.007 (3) |
C10 | 0.072 (5) | 0.059 (4) | 0.032 (3) | −0.005 (4) | −0.007 (3) | 0.002 (3) |
C11 | 0.062 (4) | 0.050 (4) | 0.044 (4) | −0.009 (3) | −0.009 (3) | 0.001 (3) |
C12 | 0.048 (4) | 0.050 (4) | 0.059 (5) | 0.004 (3) | −0.012 (3) | 0.002 (3) |
C13 | 0.067 (5) | 0.055 (4) | 0.053 (4) | 0.006 (3) | −0.013 (4) | −0.014 (4) |
C14 | 0.064 (5) | 0.058 (4) | 0.083 (7) | −0.003 (4) | −0.016 (4) | −0.017 (4) |
C15 | 0.051 (4) | 0.057 (4) | 0.067 (5) | −0.005 (3) | −0.011 (4) | −0.007 (4) |
C16 | 0.060 (5) | 0.101 (8) | 0.102 (9) | −0.018 (5) | −0.016 (5) | −0.015 (6) |
C17 | 0.071 (6) | 0.117 (8) | 0.077 (7) | −0.032 (6) | −0.006 (5) | 0.014 (6) |
C18 | 0.101 (7) | 0.111 (8) | 0.068 (6) | −0.028 (6) | 0.007 (6) | 0.014 (6) |
C19 | 0.079 (6) | 0.095 (7) | 0.056 (5) | −0.018 (5) | 0.000 (4) | 0.006 (4) |
C20 | 0.061 (5) | 0.056 (4) | 0.063 (5) | −0.008 (3) | 0.000 (4) | 0.003 (4) |
C21 | 0.057 (5) | 0.043 (4) | 0.085 (6) | 0.001 (3) | 0.000 (4) | −0.006 (4) |
C22 | 0.080 (6) | 0.065 (5) | 0.078 (6) | 0.004 (4) | 0.014 (5) | 0.011 (5) |
C23 | 0.125 (7) | 0.093 (6) | 0.091 (6) | 0.008 (5) | 0.026 (5) | 0.012 (5) |
C24 | 0.110 (6) | 0.092 (6) | 0.125 (7) | −0.021 (5) | 0.038 (6) | −0.010 (6) |
C25 | 0.095 (6) | 0.097 (6) | 0.117 (7) | −0.023 (5) | 0.016 (5) | −0.020 (5) |
C26 | 0.063 (5) | 0.054 (4) | 0.131 (9) | −0.014 (4) | 0.020 (6) | −0.022 (6) |
C27 | 0.081 (7) | 0.077 (6) | 0.121 (10) | 0.008 (5) | −0.048 (7) | −0.042 (7) |
C28 | 0.105 (8) | 0.071 (6) | 0.074 (6) | −0.004 (5) | −0.007 (6) | −0.018 (5) |
C29 | 0.094 (7) | 0.049 (4) | 0.070 (6) | −0.001 (4) | −0.017 (5) | 0.000 (4) |
C30 | 0.165 (13) | 0.068 (6) | 0.054 (5) | 0.012 (7) | 0.011 (7) | −0.003 (4) |
C31 | 0.125 (11) | 0.091 (8) | 0.082 (8) | 0.011 (7) | 0.026 (8) | 0.016 (6) |
C32 | 0.069 (6) | 0.101 (7) | 0.076 (7) | 0.010 (5) | 0.005 (5) | 0.019 (6) |
C33 | 0.069 (5) | 0.082 (6) | 0.058 (5) | 0.009 (4) | −0.006 (4) | 0.011 (4) |
C34 | 0.060 (5) | 0.061 (5) | 0.053 (4) | 0.002 (3) | 0.000 (4) | 0.006 (4) |
C35 | 0.098 (7) | 0.067 (5) | 0.050 (5) | 0.008 (5) | 0.004 (5) | 0.014 (4) |
C36 | 0.089 (7) | 0.089 (7) | 0.081 (7) | 0.001 (5) | −0.007 (6) | 0.014 (6) |
C37 | 0.083 (7) | 0.107 (8) | 0.109 (9) | 0.011 (6) | 0.021 (7) | −0.002 (8) |
C38 | 0.161 (13) | 0.101 (9) | 0.067 (7) | 0.045 (9) | 0.031 (8) | 0.016 (6) |
C39 | 0.146 (8) | 0.123 (7) | 0.127 (8) | 0.021 (6) | 0.010 (6) | 0.016 (6) |
C40 | 0.150 (8) | 0.115 (7) | 0.114 (7) | 0.009 (6) | 0.025 (6) | −0.004 (6) |
C41 | 0.157 (8) | 0.106 (7) | 0.091 (6) | 0.000 (6) | 0.010 (6) | −0.011 (5) |
C42 | 0.149 (7) | 0.097 (6) | 0.079 (6) | 0.003 (6) | 0.006 (6) | 0.012 (5) |
C43 | 0.136 (11) | 0.078 (7) | 0.060 (6) | 0.007 (6) | −0.003 (6) | 0.014 (5) |
C44 | 0.113 (8) | 0.052 (5) | 0.065 (6) | 0.001 (4) | −0.001 (5) | 0.011 (4) |
C45 | 0.133 (9) | 0.054 (5) | 0.064 (6) | 0.012 (5) | −0.021 (6) | 0.010 (4) |
C46 | 0.100 (7) | 0.057 (5) | 0.054 (5) | 0.005 (4) | −0.015 (5) | −0.008 (4) |
C47 | 0.086 (7) | 0.077 (6) | 0.096 (8) | 0.005 (5) | −0.034 (6) | −0.010 (5) |
C48 | 0.104 (9) | 0.119 (10) | 0.097 (9) | −0.013 (7) | −0.053 (8) | 0.000 (7) |
C49 | 0.116 (6) | 0.101 (6) | 0.086 (6) | −0.015 (5) | −0.040 (6) | 0.017 (5) |
C50 | 0.146 (8) | 0.143 (8) | 0.139 (8) | −0.019 (7) | −0.031 (7) | −0.006 (7) |
C51 | 0.166 (9) | 0.154 (8) | 0.126 (8) | −0.013 (7) | −0.013 (7) | −0.002 (7) |
C52 | 0.156 (8) | 0.137 (8) | 0.116 (8) | −0.019 (6) | −0.015 (7) | 0.008 (6) |
C53 | 0.193 (14) | 0.110 (9) | 0.040 (5) | −0.018 (9) | −0.010 (7) | 0.017 (5) |
C54 | 0.167 (12) | 0.061 (5) | 0.059 (6) | −0.026 (6) | −0.029 (7) | 0.005 (4) |
C55 | 0.069 (5) | 0.045 (5) | 0.059 (5) | 0.015 (5) | −0.006 (4) | 0.011 (4) |
C56 | 0.077 (6) | 0.047 (5) | 0.072 (6) | 0.005 (5) | −0.004 (5) | 0.003 (4) |
C57 | 0.098 (7) | 0.060 (6) | 0.074 (6) | 0.026 (6) | −0.005 (6) | −0.008 (5) |
C58 | 0.107 (8) | 0.083 (7) | 0.064 (6) | 0.024 (7) | 0.005 (5) | −0.012 (5) |
C59 | 0.091 (7) | 0.073 (7) | 0.066 (5) | 0.010 (6) | 0.012 (5) | 0.015 (5) |
C60 | 0.075 (6) | 0.059 (5) | 0.064 (5) | 0.008 (5) | −0.003 (4) | 0.006 (5) |
C61 | 0.074 (6) | 0.056 (6) | 0.093 (5) | −0.003 (5) | −0.002 (6) | −0.004 (6) |
C62 | 0.081 (6) | 0.058 (7) | 0.092 (5) | −0.011 (5) | −0.021 (5) | −0.006 (5) |
C63 | 0.075 (5) | 0.048 (7) | 0.080 (6) | 0.006 (5) | −0.020 (4) | −0.001 (5) |
C64 | 0.086 (7) | 0.067 (8) | 0.087 (7) | 0.014 (6) | −0.033 (5) | −0.001 (6) |
C65 | 0.105 (8) | 0.072 (8) | 0.071 (7) | 0.039 (6) | −0.020 (6) | 0.008 (6) |
C66 | 0.096 (7) | 0.056 (8) | 0.069 (5) | 0.036 (6) | −0.004 (6) | 0.017 (5) |
C67 | 0.086 (6) | 0.040 (7) | 0.071 (6) | 0.021 (5) | −0.006 (5) | 0.019 (5) |
C68 | 0.075 (4) | 0.043 (8) | 0.065 (5) | 0.009 (5) | −0.019 (4) | 0.013 (5) |
C55A | 0.067 (5) | 0.059 (5) | 0.061 (5) | 0.005 (4) | −0.003 (3) | 0.002 (4) |
C56A | 0.074 (9) | 0.047 (9) | 0.056 (8) | 0.008 (8) | −0.016 (7) | 0.017 (7) |
C57A | 0.094 (9) | 0.060 (9) | 0.076 (9) | 0.011 (9) | −0.016 (9) | −0.007 (7) |
C58A | 0.101 (10) | 0.078 (10) | 0.072 (9) | 0.023 (9) | −0.007 (8) | −0.004 (8) |
C59A | 0.093 (8) | 0.068 (8) | 0.073 (7) | 0.012 (8) | 0.010 (6) | 0.003 (7) |
C60A | 0.076 (7) | 0.055 (7) | 0.070 (7) | 0.002 (7) | 0.005 (5) | 0.008 (6) |
C61A | 0.066 (7) | 0.056 (9) | 0.086 (6) | 0.010 (8) | 0.003 (7) | 0.008 (8) |
C62A | 0.076 (7) | 0.052 (10) | 0.089 (7) | 0.001 (8) | −0.012 (6) | 0.006 (8) |
C63A | 0.079 (6) | 0.051 (9) | 0.078 (6) | 0.007 (7) | −0.016 (5) | 0.002 (7) |
C64A | 0.085 (8) | 0.061 (10) | 0.077 (8) | 0.022 (8) | −0.018 (6) | −0.003 (8) |
C65A | 0.092 (10) | 0.057 (10) | 0.072 (8) | 0.037 (9) | −0.017 (7) | 0.012 (8) |
C66A | 0.085 (9) | 0.045 (11) | 0.070 (8) | 0.035 (9) | −0.009 (8) | 0.012 (8) |
C67A | 0.080 (7) | 0.046 (11) | 0.066 (8) | 0.020 (8) | −0.008 (6) | 0.013 (8) |
C68A | 0.077 (6) | 0.033 (9) | 0.069 (7) | 0.009 (8) | −0.012 (5) | 0.001 (7) |
C2S | 0.121 (11) | 0.148 (13) | 0.155 (15) | −0.028 (10) | −0.036 (10) | 0.019 (11) |
Cl6 | 0.224 (11) | 0.248 (18) | 0.143 (8) | −0.111 (13) | −0.047 (8) | 0.046 (10) |
Cl7 | 0.149 (8) | 0.182 (15) | 0.214 (17) | 0.004 (7) | −0.039 (8) | 0.025 (12) |
Cl8 | 0.209 (11) | 0.131 (8) | 0.173 (9) | −0.040 (8) | −0.092 (9) | 0.023 (8) |
Cl6A | 0.26 (2) | 0.179 (19) | 0.203 (18) | −0.047 (15) | −0.004 (17) | 0.037 (15) |
Cl7A | 0.153 (12) | 0.20 (2) | 0.155 (12) | 0.029 (11) | −0.047 (9) | −0.031 (13) |
Cl8A | 0.27 (2) | 0.138 (12) | 0.171 (14) | −0.101 (14) | −0.104 (15) | 0.046 (11) |
Pd1—P2 | 2.232 (2) | C40—C41 | 1.35 (2) |
Pd1—P1 | 2.232 (2) | C40—H40 | 0.9300 |
Pd1—Cl2 | 2.334 (2) | C41—C42 | 1.36 (2) |
Pd1—Cl1 | 2.343 (2) | C41—H41 | 0.9300 |
P2—O4 | 1.615 (6) | C42—C43 | 1.457 (19) |
P2—O3 | 1.617 (6) | C42—H42 | 0.9300 |
P2—N2 | 1.625 (7) | C43—C44 | 1.426 (16) |
P1—O2 | 1.601 (5) | C44—C45 | 1.483 (16) |
P1—O1 | 1.608 (6) | C45—C46 | 1.385 (15) |
P1—N1 | 1.630 (6) | C45—C54 | 1.473 (15) |
O1—C1 | 1.387 (11) | C46—C47 | 1.397 (15) |
O2—C12 | 1.397 (9) | C47—C48 | 1.398 (16) |
O4—C46 | 1.434 (10) | C47—H47 | 0.9300 |
N1—C34 | 1.448 (11) | C48—C49 | 1.42 (2) |
N1—C21 | 1.463 (10) | C48—H48 | 0.9300 |
O3—C35 | 1.396 (11) | C49—C54 | 1.391 (19) |
N2—C68A | 1.38 (3) | C49—C50 | 1.45 (2) |
N2—C55A | 1.441 (19) | C50—C51 | 1.38 (3) |
N2—C68 | 1.481 (13) | C50—H50 | 0.9300 |
N2—C55 | 1.487 (10) | C51—C52 | 1.31 (2) |
C1—C10 | 1.361 (12) | C51—H51 | 0.9300 |
C1—C2 | 1.432 (11) | C52—C53 | 1.32 (2) |
C2—C3 | 1.334 (14) | C52—H52 | 0.9300 |
C2—H2A | 0.9300 | C53—C54 | 1.428 (19) |
C3—C4 | 1.397 (15) | C53—H53 | 0.9300 |
C3—H3 | 0.9300 | C55—C56 | 1.3900 |
C4—C5 | 1.379 (16) | C55—C60 | 1.3900 |
C4—C9 | 1.450 (12) | C56—C57 | 1.3900 |
C5—C6 | 1.35 (2) | C56—H56 | 0.9300 |
C5—H5 | 0.9300 | C57—C58 | 1.3900 |
C6—C7 | 1.50 (2) | C57—H57 | 0.9300 |
C6—H6 | 0.9300 | C58—C59 | 1.3900 |
C7—C8 | 1.335 (14) | C58—H58 | 0.9300 |
C7—H7 | 0.9300 | C59—C60 | 1.3900 |
C8—C9 | 1.428 (15) | C59—H59 | 0.9300 |
C8—H8 | 0.9300 | C60—C61 | 1.564 (18) |
C9—C10 | 1.466 (12) | C61—C62 | 1.24 (3) |
C10—C11 | 1.467 (10) | C61—H61 | 0.9300 |
C11—C12 | 1.411 (11) | C62—C63 | 1.44 (2) |
C11—C20 | 1.444 (11) | C62—H62 | 0.9300 |
C12—C13 | 1.414 (10) | C63—C64 | 1.3900 |
C13—C14 | 1.352 (13) | C63—C68 | 1.3900 |
C13—H13 | 0.9300 | C64—C65 | 1.3900 |
C14—C15 | 1.428 (13) | C64—H64 | 0.9300 |
C14—H14 | 0.9300 | C65—C66 | 1.3900 |
C15—C20 | 1.415 (11) | C65—H65 | 0.9300 |
C15—C16 | 1.431 (13) | C66—C67 | 1.3900 |
C16—C17 | 1.348 (16) | C66—H66 | 0.9300 |
C16—H16 | 0.9300 | C67—C68 | 1.3900 |
C17—C18 | 1.380 (16) | C67—H67 | 0.9300 |
C17—H17 | 0.9300 | C55A—C56A | 1.3900 |
C18—C19 | 1.350 (14) | C55A—C60A | 1.3900 |
C18—H18 | 0.9300 | C56A—C57A | 1.3900 |
C19—C20 | 1.413 (13) | C56A—H56A | 0.9300 |
C19—H19 | 0.9300 | C57A—C58A | 1.3900 |
C21—C22 | 1.361 (13) | C57A—H57A | 0.9300 |
C21—C26 | 1.415 (14) | C58A—C59A | 1.3900 |
C22—C23 | 1.424 (16) | C58A—H58A | 0.9300 |
C22—H22 | 0.9300 | C59A—C60A | 1.3900 |
C23—C24 | 1.46 (2) | C59A—H59A | 0.9300 |
C23—H23 | 0.9300 | C60A—C61A | 1.47 (4) |
C24—C25 | 1.26 (2) | C61A—C62A | 1.51 (5) |
C24—H24 | 0.9300 | C61A—H61A | 0.9300 |
C25—C26 | 1.383 (16) | C62A—C63A | 1.501 (5) |
C25—H25 | 0.9300 | C62A—H62A | 0.9300 |
C26—C27 | 1.512 (19) | C63A—C64A | 1.3900 |
C27—C28 | 1.298 (17) | C63A—C68A | 1.3900 |
C27—H27 | 0.9300 | C64A—C65A | 1.3900 |
C28—C29 | 1.445 (16) | C64A—H64A | 0.9300 |
C28—H28 | 0.9300 | C65A—C66A | 1.3900 |
C29—C34 | 1.408 (13) | C65A—H65A | 0.9300 |
C29—C30 | 1.409 (16) | C66A—C67A | 1.3900 |
C30—C31 | 1.375 (19) | C66A—H66A | 0.9300 |
C30—H30 | 0.9300 | C67A—C68A | 1.3900 |
C31—C32 | 1.354 (18) | C67A—H67A | 0.9300 |
C31—H31 | 0.9300 | C2S—Cl7 | 1.734 (8) |
C32—C33 | 1.381 (14) | C2S—Cl8 | 1.737 (8) |
C32—H32 | 0.9300 | C2S—Cl6 | 1.740 (8) |
C33—C34 | 1.365 (12) | C2S—Cl7A | 1.751 (8) |
C33—H33 | 0.9300 | C2S—Cl8A | 1.755 (8) |
C35—C44 | 1.379 (14) | C2S—Cl6A | 1.756 (8) |
C35—C36 | 1.381 (15) | C2S—H2S | 0.9800 |
C36—C37 | 1.355 (17) | C3S—Cl11 | 1.736 (8) |
C36—H36 | 0.9300 | C3S—Cl9 | 1.741 (8) |
C37—C38 | 1.46 (2) | C3S—Cl10 | 1.746 (8) |
C37—H37 | 0.9300 | C3S—H3SA | 0.9800 |
C38—C43 | 1.37 (2) | C1S—Cl4 | 1.748 (8) |
C38—C39 | 1.44 (2) | C1S—Cl5 | 1.751 (8) |
C39—C40 | 1.35 (2) | C1S—Cl3 | 1.755 (8) |
C39—H39 | 0.9300 | C1S—H1S | 0.9800 |
P2—Pd1—P1 | 94.59 (7) | C39—C40—H40 | 120.1 |
P2—Pd1—Cl2 | 174.48 (10) | C40—C41—C42 | 122.7 (16) |
P1—Pd1—Cl2 | 88.86 (8) | C40—C41—H41 | 118.7 |
P2—Pd1—Cl1 | 87.73 (8) | C42—C41—H41 | 118.7 |
P1—Pd1—Cl1 | 174.22 (10) | C41—C42—C43 | 120.3 (16) |
Cl2—Pd1—Cl1 | 89.24 (9) | C41—C42—H42 | 119.8 |
O4—P2—O3 | 101.0 (3) | C43—C42—H42 | 119.8 |
O4—P2—N2 | 111.8 (3) | C38—C43—C44 | 119.0 (12) |
O3—P2—N2 | 100.0 (3) | C38—C43—C42 | 115.2 (13) |
O4—P2—Pd1 | 110.5 (2) | C44—C43—C42 | 125.7 (14) |
O3—P2—Pd1 | 116.4 (2) | C35—C44—C43 | 118.5 (11) |
N2—P2—Pd1 | 115.9 (3) | C35—C44—C45 | 120.2 (9) |
O2—P1—O1 | 102.0 (3) | C43—C44—C45 | 121.2 (10) |
O2—P1—N1 | 113.3 (3) | C46—C45—C54 | 114.9 (11) |
O1—P1—N1 | 99.0 (3) | C46—C45—C44 | 121.5 (9) |
O2—P1—Pd1 | 108.2 (2) | C54—C45—C44 | 123.6 (11) |
O1—P1—Pd1 | 117.5 (2) | C45—C46—C47 | 126.1 (9) |
N1—P1—Pd1 | 116.1 (2) | C45—C46—O4 | 118.8 (9) |
C1—O1—P1 | 123.4 (5) | C47—C46—O4 | 115.0 (9) |
C12—O2—P1 | 122.8 (4) | C48—C47—C46 | 117.1 (12) |
C46—O4—P2 | 120.9 (5) | C48—C47—H47 | 121.4 |
C34—N1—C21 | 115.7 (6) | C46—C47—H47 | 121.4 |
C34—N1—P1 | 123.3 (5) | C47—C48—C49 | 120.1 (12) |
C21—N1—P1 | 120.9 (6) | C47—C48—H48 | 119.9 |
C35—O3—P2 | 120.4 (5) | C49—C48—H48 | 119.9 |
C68A—N2—C55A | 126 (2) | C54—C49—C48 | 121.2 (11) |
C55A—N2—C68 | 119.5 (15) | C54—C49—C50 | 118.5 (15) |
C68A—N2—C55 | 115 (2) | C48—C49—C50 | 120.3 (14) |
C68—N2—C55 | 109.3 (10) | C51—C50—C49 | 112.2 (17) |
C68A—N2—P2 | 121 (2) | C51—C50—H50 | 123.9 |
C55A—N2—P2 | 113.0 (11) | C49—C50—H50 | 123.9 |
C68—N2—P2 | 126.5 (10) | C52—C51—C50 | 132 (2) |
C55—N2—P2 | 124.0 (6) | C52—C51—H51 | 114.1 |
C10—C1—O1 | 120.3 (7) | C50—C51—H51 | 114.1 |
C10—C1—C2 | 122.7 (8) | C51—C52—C53 | 115.5 (19) |
O1—C1—C2 | 116.8 (8) | C51—C52—H52 | 122.2 |
C3—C2—C1 | 118.6 (10) | C53—C52—H52 | 122.2 |
C3—C2—H2A | 120.7 | C52—C53—C54 | 121.7 (17) |
C1—C2—H2A | 120.7 | C52—C53—H53 | 119.2 |
C2—C3—C4 | 123.2 (9) | C54—C53—H53 | 119.2 |
C2—C3—H3 | 118.4 | C49—C54—C53 | 120.4 (11) |
C4—C3—H3 | 118.4 | C49—C54—C45 | 119.7 (12) |
C5—C4—C3 | 120.5 (10) | C53—C54—C45 | 119.8 (13) |
C5—C4—C9 | 120.3 (11) | C56—C55—C60 | 120.0 |
C3—C4—C9 | 118.9 (8) | C56—C55—N2 | 116.6 (6) |
C6—C5—C4 | 119.8 (11) | C60—C55—N2 | 123.2 (6) |
C6—C5—H5 | 120.1 | C55—C56—C57 | 120.0 |
C4—C5—H5 | 120.1 | C55—C56—H56 | 120.0 |
C5—C6—C7 | 121.6 (12) | C57—C56—H56 | 120.0 |
C5—C6—H6 | 119.2 | C58—C57—C56 | 120.0 |
C7—C6—H6 | 119.2 | C58—C57—H57 | 120.0 |
C8—C7—C6 | 117.8 (13) | C56—C57—H57 | 120.0 |
C8—C7—H7 | 121.1 | C57—C58—C59 | 120.0 |
C6—C7—H7 | 121.1 | C57—C58—H58 | 120.0 |
C7—C8—C9 | 121.5 (11) | C59—C58—H58 | 120.0 |
C7—C8—H8 | 119.3 | C58—C59—C60 | 120.0 |
C9—C8—H8 | 119.3 | C58—C59—H59 | 120.0 |
C8—C9—C4 | 118.8 (8) | C60—C59—H59 | 120.0 |
C8—C9—C10 | 123.6 (8) | C59—C60—C55 | 120.0 |
C4—C9—C10 | 117.6 (8) | C59—C60—C61 | 122.1 (8) |
C1—C10—C9 | 118.1 (7) | C55—C60—C61 | 117.8 (8) |
C1—C10—C11 | 122.1 (7) | C62—C61—C60 | 130.9 (15) |
C9—C10—C11 | 119.6 (7) | C62—C61—H61 | 114.6 |
C12—C11—C20 | 116.5 (7) | C60—C61—H61 | 114.6 |
C12—C11—C10 | 120.0 (7) | C61—C62—C63 | 123.6 (16) |
C20—C11—C10 | 123.5 (7) | C61—C62—H62 | 118.2 |
O2—C12—C11 | 120.6 (6) | C63—C62—H62 | 118.2 |
O2—C12—C13 | 117.5 (7) | C64—C63—C68 | 120.0 |
C11—C12—C13 | 121.8 (7) | C64—C63—C62 | 113.0 (14) |
C14—C13—C12 | 119.3 (8) | C68—C63—C62 | 126.9 (14) |
C14—C13—H13 | 120.4 | C63—C64—C65 | 120.0 |
C12—C13—H13 | 120.4 | C63—C64—H64 | 120.0 |
C13—C14—C15 | 122.8 (8) | C65—C64—H64 | 120.0 |
C13—C14—H14 | 118.6 | C64—C65—C66 | 120.0 |
C15—C14—H14 | 118.6 | C64—C65—H65 | 120.0 |
C20—C15—C14 | 117.3 (7) | C66—C65—H65 | 120.0 |
C20—C15—C16 | 119.9 (9) | C65—C66—C67 | 120.0 |
C14—C15—C16 | 122.6 (8) | C65—C66—H66 | 120.0 |
C17—C16—C15 | 121.2 (9) | C67—C66—H66 | 120.0 |
C17—C16—H16 | 119.4 | C68—C67—C66 | 120.0 |
C15—C16—H16 | 119.4 | C68—C67—H67 | 120.0 |
C16—C17—C18 | 118.2 (9) | C66—C67—H67 | 120.0 |
C16—C17—H17 | 120.9 | C67—C68—C63 | 120.0 |
C18—C17—H17 | 120.9 | C67—C68—N2 | 120.5 (12) |
C19—C18—C17 | 123.0 (11) | C63—C68—N2 | 119.4 (12) |
C19—C18—H18 | 118.5 | C56A—C55A—C60A | 120.0 |
C17—C18—H18 | 118.5 | C56A—C55A—N2 | 126.3 (14) |
C18—C19—C20 | 121.3 (10) | C60A—C55A—N2 | 113.6 (14) |
C18—C19—H19 | 119.3 | C57A—C56A—C55A | 120.0 |
C20—C19—H19 | 119.3 | C57A—C56A—H56A | 120.0 |
C19—C20—C15 | 116.2 (8) | C55A—C56A—H56A | 120.0 |
C19—C20—C11 | 122.4 (8) | C56A—C57A—C58A | 120.0 |
C15—C20—C11 | 121.4 (8) | C56A—C57A—H57A | 120.0 |
C22—C21—C26 | 121.6 (9) | C58A—C57A—H57A | 120.0 |
C22—C21—N1 | 120.5 (8) | C59A—C58A—C57A | 120.0 |
C26—C21—N1 | 117.8 (9) | C59A—C58A—H58A | 120.0 |
C21—C22—C23 | 118.8 (11) | C57A—C58A—H58A | 120.0 |
C21—C22—H22 | 120.6 | C60A—C59A—C58A | 120.0 |
C23—C22—H22 | 120.6 | C60A—C59A—H59A | 120.0 |
C22—C23—C24 | 116.0 (12) | C58A—C59A—H59A | 120.0 |
C22—C23—H23 | 122.0 | C59A—C60A—C55A | 120.0 |
C24—C23—H23 | 122.0 | C59A—C60A—C61A | 115 (2) |
C25—C24—C23 | 121.4 (12) | C55A—C60A—C61A | 123 (2) |
C25—C24—H24 | 119.3 | C60A—C61A—C62A | 121 (3) |
C23—C24—H24 | 119.3 | C60A—C61A—H61A | 119.3 |
C24—C25—C26 | 123.8 (14) | C62A—C61A—H61A | 119.3 |
C24—C25—H25 | 118.1 | C63A—C62A—H62A | 109.0 |
C26—C25—H25 | 118.1 | C61A—C62A—H62A | 109.0 |
C25—C26—C21 | 116.5 (13) | C64A—C63A—C68A | 120.0 |
C25—C26—C27 | 121.4 (11) | C64A—C63A—C62A | 130 (3) |
C21—C26—C27 | 122.1 (9) | C68A—C63A—C62A | 106 (3) |
C28—C27—C26 | 127.1 (10) | C65A—C64A—C63A | 120.0 |
C28—C27—H27 | 116.4 | C65A—C64A—H64A | 120.0 |
C26—C27—H27 | 116.5 | C63A—C64A—H64A | 120.0 |
C27—C28—C29 | 126.9 (11) | C64A—C65A—C66A | 120.0 |
C27—C28—H28 | 116.5 | C64A—C65A—H65A | 120.0 |
C29—C28—H28 | 116.5 | C66A—C65A—H65A | 120.0 |
C34—C29—C30 | 117.8 (10) | C67A—C66A—C65A | 120.0 |
C34—C29—C28 | 123.7 (9) | C67A—C66A—H66A | 120.0 |
C30—C29—C28 | 118.4 (10) | C65A—C66A—H66A | 120.0 |
C31—C30—C29 | 120.2 (11) | C68A—C67A—C66A | 120.0 |
C31—C30—H30 | 119.9 | C68A—C67A—H67A | 120.0 |
C29—C30—H30 | 119.9 | C66A—C67A—H67A | 120.0 |
C32—C31—C30 | 121.3 (12) | N2—C68A—C67A | 113 (3) |
C32—C31—H31 | 119.3 | N2—C68A—C63A | 127 (3) |
C30—C31—H31 | 119.3 | C67A—C68A—C63A | 120.0 |
C31—C32—C33 | 119.3 (11) | Cl7—C2S—Cl8 | 110.4 (6) |
C31—C32—H32 | 120.4 | Cl7—C2S—Cl6 | 110.0 (6) |
C33—C32—H32 | 120.4 | Cl8—C2S—Cl6 | 110.3 (5) |
C34—C33—C32 | 121.5 (9) | Cl6—C2S—Cl7A | 107.7 (16) |
C34—C33—H33 | 119.2 | Cl7A—C2S—Cl8A | 108.6 (6) |
C32—C33—H33 | 119.2 | Cl7—C2S—Cl6A | 102.5 (18) |
C33—C34—C29 | 119.8 (9) | Cl7A—C2S—Cl6A | 108.4 (6) |
C33—C34—N1 | 121.0 (8) | Cl8A—C2S—Cl6A | 108.4 (6) |
C29—C34—N1 | 119.1 (7) | Cl7—C2S—H2S | 108.7 |
C44—C35—C36 | 123.3 (10) | Cl8—C2S—H2S | 108.7 |
C44—C35—O3 | 117.6 (9) | Cl6—C2S—H2S | 108.7 |
C36—C35—O3 | 118.9 (9) | Cl7A—C2S—H2S | 91.7 |
C37—C36—C35 | 118.5 (11) | Cl8A—C2S—H2S | 106.4 |
C37—C36—H36 | 120.7 | Cl6A—C2S—H2S | 131.0 |
C35—C36—H36 | 120.7 | Cl11—C3S—Cl9 | 99.1 (12) |
C36—C37—C38 | 120.3 (12) | Cl11—C3S—Cl10 | 108.3 (13) |
C36—C37—H37 | 119.9 | Cl9—C3S—Cl10 | 111.3 (14) |
C38—C37—H37 | 119.9 | Cl11—C3S—H3SA | 112.4 |
C43—C38—C39 | 122.3 (16) | Cl9—C3S—H3SA | 112.4 |
C43—C38—C37 | 119.9 (11) | Cl10—C3S—H3SA | 112.4 |
C39—C38—C37 | 117.8 (16) | Cl4—C1S—Cl5 | 108.8 (6) |
C40—C39—C38 | 119.5 (18) | Cl4—C1S—Cl3 | 108.5 (6) |
C40—C39—H39 | 120.3 | Cl5—C1S—Cl3 | 108.7 (6) |
C38—C39—H39 | 120.3 | Cl4—C1S—H1S | 110.3 |
C41—C40—C39 | 119.9 (17) | Cl5—C1S—H1S | 110.3 |
C41—C40—H40 | 120.1 | Cl3—C1S—H1S | 110.3 |
D—H···A | D—H | H···A | D···A | D—H···A |
C2S—H2S···Cl1i | 0.97 | 2.47 | 3.358 (10) | 151 |
C27—H27···Cl2ii | 0.93 | 2.82 | 3.741 (12) | 172 |
C14—H14···Cl2ii | 0.93 | 2.84 | 3.613 (10) | 142 |
Symmetry codes: (i) −y+1, x, z−3/4; (ii) −y+1, x, z+1/4. |
Experimental details
Crystal data | |
Chemical formula | [PdCl2(C34H22NO2P)2].2CDCl3 |
Mr | 1431.03 |
Crystal system, space group | Tetragonal, P41 |
Temperature (K) | 293 |
a, c (Å) | 19.866 (2), 17.497 (2) |
V (Å3) | 6905.2 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.67 |
Crystal size (mm) | 0.42 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Rigaku AFC7S Mercury |
Absorption correction | Multi-scan Jacobson (1998) |
Tmin, Tmax | 0.802, 0.891 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 79958, 14408, 9124 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.248, 1.07 |
No. of reflections | 14408 |
No. of parameters | 886 |
No. of restraints | 593 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.06, −0.72 |
Absolute structure | Flack (1983), with 5079 Friedel pairs |
Absolute structure parameter | 0.02 (4) |
Computer programs: CrystalClear (Rigaku/MSC Inc., 2000), CrystalClear, CrystalStructure (Rigaku/MSC Inc., 2004), SHELXLTL-NT (Bruker, 1998), SHELXLTL-NT and DIAMOND (Brandenburg, 1998), SHELXLTL-NT and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C2S—H2S···Cl1i | 0.97 | 2.47 | 3.358 (10) | 151 |
C27—H27···Cl2ii | 0.93 | 2.82 | 3.741 (12) | 172 |
C14—H14···Cl2ii | 0.93 | 2.84 | 3.613 (10) | 142 |
Symmetry codes: (i) −y+1, x, z−3/4; (ii) −y+1, x, z+1/4. |
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P-olefin ligands constitute a rather new entry in the development of efficient bidentate ligand systems for organometallic reactivity and catalysis. Grützmacher et al. developed a new class of P-olefin ligands based on the dibenzo[b,f]cycloheptene and dibenzo[b,f]azepin motifs, several of them chiral (Maire et al., 2004). On the other hand, de Vries and Feringa (Van den Berg et al., 2000) showed that chiral phosphoramidites are highly versatile monodentate ligands and so we anticipated that the dibenzo[b,f]azepin molecule could be readily used to form new chiral phosphoramidite-olefin ligands such as (I). Ligand (I) has very recently been disclosed to be an excellent ligand for the enantioselective formation of allylic amines from allylic alcohols (Defieber et al., 2007).
Here, we report the crystal structure of a Pd(II) complex bearing the chiral ligand (I). The asymmetric unit of (II) consists of one metal complex molecule and three independent deuterocloroform molecules (two of which are half occupied). The Pd atom displays a distorted square planar environment, in which two ligands (I) are coordinated through their P atoms in a monodentade fashion and the remaining coordination sites are occupied by two chloride anions. The ligands are located in a cis configuration around the metal centre [P2—Pd1—P1 = 94.59 (7)°; Cl2—Pd—Cl1 = 89.24 (9)°]. The metal complex adopts pseudo-C2 symmetry about the Pd atom (Fig. 1). The naphtyl groups are twisted in both molecules as indicated by torsion angles of 50.39 (2)° for C1—C10—C11—C12 and 52.23 (2)° for C35—C44—C45—C46.
The crystal structure of (II) consists of a three-dimensional-hydrogen bonded network, which is self assembled via C—H··· π and C—H···Cl interaction [C27i···CL2: 3.741 (12) Å and C14i···Cl2: 3.613 (10) Å; i= x, 1 - y, 1/4 + z]. The coordinated chloride (Cl2) ion causes the self-assembly of the metal complex to generate a right-handed helical arrangement along the fourfold screw axis (41). Neighbouring helices are assembled by weak van der Waals interactions to afford a 3-D hydrogen-bonded assembly. This organization yields a framework with one-dimensional channels running along the c axis, where the deuterochloroform molecules are allocated, and which are sustained into the channels by C—H···Cl hydrogen bonding to the chloride ligands of the complex [Cl1···C2Sii: 3.358 Å; ii= x, 1 - y, -3/4 + z] (Fig 2).