Structurally Diverse Diazafluorene-Ligated Palladium(II) Complexes and Their Implications for Aerobic Oxidation Reactions.
White, Paul B.; Jaworski, Jonathan N.; Fry, Charles G.; Dolinar, Brian S.; Guzei, Ilia A.; Stahl, Shannon S.; Journal of the American Chemical Society 138 (2016) 4869–4880; doi:10.1021/jacs.6b01188

data_4130196
_publ_section_title
;
 Structurally Diverse Diazafluorene-Ligated Palladium(II) Complexes and
 Their Implications for Aerobic Oxidation Reactions.
;
_journal_issue                   14
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4869
_journal_page_last               4880
_journal_paper_doi               10.1021/jacs.6b01188
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C42 H48 N4 O10 Pd2, 1.53(C H Cl3)'
_chemical_formula_sum            'C43.54 H49.54 Cl4.63 N4 O10 Pd2'
_chemical_formula_weight         1165.78
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-12-13
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                73.854(17)
_cell_angle_beta                 72.031(6)
_cell_angle_gamma                80.916(7)
_cell_formula_units_Z            2
_cell_length_a                   12.971(5)
_cell_length_b                   13.996(4)
_cell_length_c                   15.387(4)
_cell_measurement_reflns_used    9810
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      30.54
_cell_measurement_theta_min      2.16
_cell_volume                     2544.4(14)
_computing_cell_refinement       'SAINT+ Ver. 7.68A (Bruker-AXS, 2009)'
_computing_data_collection       'APEX2 Ver. 2012.14-3 (Bruker-AXS, 2012)'
_computing_data_reduction        'SAINT+ Ver. 7.68A'
_computing_molecular_graphics    SHELXTL
_computing_publication_material  SHELXTL
_computing_structure_refinement  SHELXTL
_computing_structure_solution    'ShelXS-2013 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '0.5\ \w and 0.5\ \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0233
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            72342
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.571
_diffrn_reflns_theta_min         1.435
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.006
_exptl_absorpt_correction_T_max  0.9514
_exptl_absorpt_correction_T_min  0.8464
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0881 before and 0.0369 after correction.
The Ratio of minimum to maximum transmission is 0.8896.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'reddish orange'
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.522
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1179
_exptl_crystal_size_max          0.258
_exptl_crystal_size_mid          0.192
_exptl_crystal_size_min          0.097
_refine_diff_density_max         2.252
_refine_diff_density_min         -2.357
_refine_diff_density_rms         0.147
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.287
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     949
_refine_ls_number_reflns         15379
_refine_ls_number_restraints     1524
_refine_ls_restrained_S_all      1.280
_refine_ls_R_factor_all          0.0679
_refine_ls_R_factor_gt           0.0653
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+18.9059P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1446
_refine_ls_wR_factor_ref         0.1458
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14529
_reflns_number_total             15379
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b01188_si_002.cif
_cod_data_source_block           Structure-L
_cod_original_cell_volume        2544.3(15)
_cod_database_code               4130196
_shelxl_version_number           2013-3
_shelx_estimated_absorpt_t_max   0.909
_shelx_estimated_absorpt_t_min   0.781
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{O5, O5A, O5B}
3. Restrained distances
 Pd2-O7A \\sim Pd2-O7
 with sigma of 0.01
 Pd1-O3A \\sim Pd1-O3
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C3A \\sim C4A \\sim C5A: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
O7 \\sim O8 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim O7A \\sim
O8A \\sim C16A \\sim C17A \\sim C18A \\sim C19A \\sim C20A: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
O3 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim O3A \\sim O4A \\sim C6A
\\sim C7A \\sim C8A \\sim C9A \\sim C10A \\sim O4: within 1.7A with sigma of
0.01 and sigma for terminal atoms of 0.02
Cl4 \\sim Cl5 \\sim Cl6 \\sim C44 \\sim Cl4A \\sim Cl5A \\sim Cl6A \\sim Cl4B
\\sim Cl5B \\sim Cl6B \\sim C44B \\sim C44A: within 1.8A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Cl8 \\sim C45 \\sim Cl9 \\sim Cl7: within 1.8A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O5 \\sim O6 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim O5A \\sim
O6A \\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A \\sim O5B \\sim O6B
\\sim C11B \\sim C12B \\sim C13B \\sim C14B \\sim C15B: within 1.7A with sigma
of 0.005 and sigma for terminal atoms of 0.01
Cl3 \\sim C43 \\sim Cl1 \\sim Cl2: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O5) = Uanis(O5A) = Uanis(O5B)
5. Same fragment restrains
{O1, O2, C1, C2, C3A, C4A, C5A}
{O3, O4, C6, C7, C8, C9, C10}
{O3A, O4A, C6A, C7A, C8A, C9A, C10A}
{O5, O6, C11, C12, C13, C14, C15}
{O5A, O6A, C11A, C12A, C13A, C14A, C15A}
{O5B, O6B, C11B, C12B, C13B, C14B, C15B}
{O7, O8, C16, C17, C18, C19, C20}
{O7A, O8A, C16A, C17A, C18A, C19A, C20A}
as
{O1, O2, C1, C2, C3, C4, C5}
6. Others
 1*[Sof(O5)+Sof(O6)+Sof(C11)+Sof(C12)+Sof(C13)+Sof(H13A)+Sof(H13B)+Sof(H13C)+
 Sof(C14)+Sof(H14A)+Sof(H14B)+Sof(H14C)+Sof(C15)+Sof(H15A)+Sof(H15B)+Sof(H15C)]+
 1*[Sof(O5A)+Sof(O6A)+Sof(C11A)+Sof(C12A)+Sof(C13A)+Sof(H13D)+Sof(H13E)+
 Sof(H13F)+Sof(C14A)+Sof(H14D)+Sof(H14E)+Sof(H14F)+Sof(C15A)+Sof(H15D)+
 Sof(H15E)+Sof(H15F)]+1*[Sof(O5B)+Sof(O6B)+Sof(C11B)+Sof(C12B)+Sof(C13B)+
 Sof(H13G)+Sof(H13H)+Sof(H13I)+Sof(C14B)+Sof(H14G)+Sof(H14H)+Sof(H14I)+
 Sof(C15B)+Sof(H15G)+Sof(H15H)+Sof(H15I)]=1 with esd of 0
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=1-FVAR(1)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(1)
 Sof(O3A)=Sof(O4A)=Sof(C6A)=Sof(C7A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=
 1-FVAR(2)
 Sof(O3)=Sof(O4)=Sof(C6)=Sof(C7)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=
 Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(2)
 Sof(O5)=Sof(O6)=Sof(C11)=Sof(C12)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=
 FVAR(3)
 Sof(O5A)=Sof(O6A)=Sof(C11A)=Sof(C12A)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=
 Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=
 Sof(H15F)=FVAR(4)
 Sof(O5B)=Sof(O6B)=Sof(C11B)=Sof(C12B)=Sof(C13B)=Sof(H13G)=Sof(H13H)=Sof(H13I)=
 Sof(C14B)=Sof(H14G)=Sof(H14H)=Sof(H14I)=Sof(C15B)=Sof(H15G)=Sof(H15H)=
 Sof(H15I)=FVAR(5)
 Sof(O7A)=Sof(O8A)=Sof(C16A)=Sof(C17A)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=
 Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C20A)=Sof(H20D)=Sof(H20E)=
 Sof(H20F)=1-FVAR(6)
 Sof(O7)=Sof(O8)=Sof(C16)=Sof(C17)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=
 FVAR(6)
 Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(C43)=Sof(H43)=FVAR(7)
 Sof(Cl4)=Sof(Cl5)=Sof(Cl6)=Sof(C44)=Sof(H44)=FVAR(8)
 Sof(Cl4A)=Sof(Cl5A)=Sof(Cl6A)=Sof(C44A)=Sof(H44A)=FVAR(9)
 Sof(Cl4B)=Sof(Cl5B)=Sof(Cl6B)=Sof(C44B)=Sof(H44B)=FVAR(10)
 Sof(Cl7)=Sof(Cl8)=Sof(Cl9)=Sof(C45)=Sof(H45)=FVAR(11)
 Uiso(Cl7)=Uiso(Cl8)=Uiso(Cl9)=Uiso(C45)=FVAR(12)
7.a Free rotating group:
 Cl1(Cl2,Cl3,C43), Cl4(Cl5,Cl6,C44), Cl4A(Cl5A,Cl6A,C44A), Cl4B(Cl5B,Cl6B,
 C44B), Cl7(Cl8,Cl9,C45)
7.b Ternary CH refined with riding coordinates:
 C43(H43), C44(H44), C44A(H44A), C44B(H44B), C45(H45)
7.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C22(H22), C23(H23), C29(H29), C30(H30), C31(H31), C32(H32),
 C33(H33), C34(H34), C40(H40), C41(H41), C42(H42)
7.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C3A(H3AA,H3AB,H3AC),
 C4A(H4AA,H4AB,H4AC), C5A(H5AA,H5AB,H5AC), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C),
 C10(H10A,H10B,H10C), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC), C10A(H10D,H10E,
 H10F), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C),
 C13A(H13D,H13E,H13F), C14A(H14D,H14E,H14F), C15A(H15D,H15E,H15F), C13B(H13G,
 H13H,H13I), C14B(H14G,H14H,H14I), C15B(H15G,H15H,H15I), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C18A(H18D,H18E,H18F), C19A(H19D,H19E,
 H19F), C20A(H20D,H20E,H20F)
;
_shelx_res_checksum              20215
_shelx_hkl_checksum              40215