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_4130192
_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         'C21 H24 N2 O8 Pd2, 1.87(C H Cl3)'
_chemical_formula_sum            'C22.87 H25.87 Cl5.6 N2 O8 Pd2'
_chemical_formula_weight         868.24
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2013-10-02
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.432(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.337(4)
_cell_length_b                   20.912(8)
_cell_length_c                   13.689(5)
_cell_measurement_reflns_used    9800
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.56
_cell_measurement_theta_min      2.40
_cell_volume                     3218(2)
_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
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0402
_diffrn_reflns_av_unetI/netI     0.0179
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            75418
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.566
_diffrn_reflns_theta_min         1.789
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.628
_exptl_absorpt_correction_T_max  0.9327
_exptl_absorpt_correction_T_min  0.8121
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1463 before and 0.0516 after correction.
The Ratio of minimum to maximum transmission is 0.8707.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.792
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1713
_exptl_crystal_size_max          0.166
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.067
_refine_diff_density_max         0.722
_refine_diff_density_min         -0.538
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     492
_refine_ls_number_reflns         7433
_refine_ls_number_restraints     132
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0226
_refine_ls_R_factor_gt           0.0197
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0167P)^2^+3.6391P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0477
_refine_ls_wR_factor_ref         0.0495
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6884
_reflns_number_total             7433
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b01188_si_002.cif
_cod_data_source_block           Structure-G
_cod_original_formula_sum        'C22.87 H25.87 Cl5.60 N2 O8 Pd2'
_cod_database_code               4130192
_shelxl_version_number           2013-3
_shelx_estimated_absorpt_t_max   0.899
_shelx_estimated_absorpt_t_min   0.774
_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. Restrained distances
 Cl1-C22 \\sim Cl1A-C22A \\sim Cl2A-C22A \\sim Cl2-C22 \\sim Cl3A-C22A \\sim
Cl3-C22
 with sigma of 0.01
 Cl6-C23 \\sim Cl6A-C23A \\sim Cl5A-C23A \\sim Cl5-C23 \\sim Cl4A-C23A \\sim
Cl4-C23
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Cl1A \\sim Cl1 \\sim C22A \\sim C22 \\sim Cl2A \\sim Cl2 \\sim Cl3 \\sim Cl3A:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Cl4 \\sim Cl5 \\sim Cl6 \\sim C23 \\sim Cl4A \\sim Cl5A \\sim Cl6A \\sim C23A:
within 1.7A with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C20A) = Uanis(O7A)
Uanis(C20) = Uanis(O7)
4. Rigid body (RIGU) restrains
 O7, C20, C21, O7A, O8A, C20A, C21A, O8
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(O7A)=Sof(O8A)=Sof(C20A)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(1)
 Sof(O7)=Sof(O8)=Sof(C20)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(1)
 Sof(Cl1A)=Sof(Cl2A)=Sof(Cl3A)=Sof(C22A)=Sof(H22A)=1-FVAR(2)
 Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(C22)=Sof(H22)=FVAR(2)
 Sof(Cl4)=Sof(Cl5)=Sof(Cl6)=Sof(C23)=Sof(H23)=FVAR(3)
 Sof(Cl4A)=Sof(Cl5A)=Sof(Cl6A)=Sof(C23A)=Sof(H23A)=FVAR(4)
 Sof(Cl4B)=Sof(Cl5B)=Sof(Cl6B)=Sof(C23B)=Sof(H23B)=FVAR(5)
 Sof(Cl4C)=Sof(Cl5C)=Sof(Cl6C)=Sof(C23C)=Sof(H23C)=FVAR(6)
 Uiso(Cl4B)=Uiso(Cl5B)=Uiso(Cl6B)=Uiso(C23B)=Uiso(Cl4C)=Uiso(Cl5C)=Uiso(Cl6C)=
 Uiso(C23C)=FVAR(7)
6.a Free rotating group:
 Cl4B(Cl5B,Cl6B,C23B,H23B), Cl4C(Cl5C,Cl6C,C23C,H23C)
6.b Ternary CH refined with riding coordinates:
 C22(H22), C22A(H22A), C23(H23), C23A(H23A)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C11(H11), C12(H12), C13(H13)
6.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C15(H15A,H15B,H15C), C17(H17A,H17B,
 H17C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C21A(H21D,H21E,H21F)
;
_shelx_res_checksum              10912
_shelx_hkl_checksum              86152