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_4130193
_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         'C17 H18 N2 O4 Pd, 1.47(C H Cl3)'
_chemical_formula_sum            'C18.47 H19.47 Cl4.42 N2 O4 Pd'
_chemical_formula_weight         596.65
_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   geom
_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                 101.520(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.376(3)
_cell_length_b                   12.988(2)
_cell_length_c                   17.735(3)
_cell_measurement_reflns_used    9802
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      70.02
_cell_measurement_theta_min      4.25
_cell_volume                     2341.9(9)
_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 0.991
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '0.60\ \w and 0.6\ \f scans'
_diffrn_radiation_collimation    '0.5 mm double-pinhole'
_diffrn_radiation_monochromator  'equatorially mounted graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0219
_diffrn_reflns_av_unetI/netI     0.0113
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            34816
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.000
_diffrn_reflns_theta_max         70.054
_diffrn_reflns_theta_min         4.250
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'Siemens, K FFCU 2K 90'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    11.278
_exptl_absorpt_correction_T_max  0.5111
_exptl_absorpt_correction_T_min  0.0805
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0507 before and 0.0339 after correction.
The Ratio of minimum to maximum transmission is 0.1575.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.692
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1190
_exptl_crystal_size_max          0.356
_exptl_crystal_size_mid          0.176
_exptl_crystal_size_min          0.106
_refine_diff_density_max         1.023
_refine_diff_density_min         -0.384
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.176
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     369
_refine_ls_number_reflns         4400
_refine_ls_number_restraints     138
_refine_ls_restrained_S_all      1.167
_refine_ls_R_factor_all          0.0253
_refine_ls_R_factor_gt           0.0247
_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^)+(0.0374P)^2^+2.6373P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0719
_refine_ls_wR_factor_ref         0.0723
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4294
_reflns_number_total             4400
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b01188_si_002.cif
_cod_data_source_block           Structure-H
_cod_original_cell_volume        2341.8(8)
_cod_database_code               4130193
_shelxl_version_number           2013-3
_shelx_estimated_absorpt_t_max   0.381
_shelx_estimated_absorpt_t_min   0.108
_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
 Cl5-C19 \\sim Cl4-C19 \\sim Cl6-C19 \\sim Cl2-C18 \\sim Cl1-C18 \\sim Cl3-C18
\\sim Cl2A-C18A \\sim Cl3A-
 C18A \\sim Cl1A-C18A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O3 \\sim C16 \\sim C17 \\sim O4 \\sim O4A \\sim C16A \\sim O3A \\sim C17A:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Same fragment restrains
{O3A, O4A, C16A, C17A}
as
{O3, O4, C16, C17}
5. Others
 Sof(O3A)=Sof(O4A)=Sof(C16A)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(1)
 Sof(O3)=Sof(O4)=Sof(C16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(1)
 Sof(Cl1A)=Sof(Cl2A)=Sof(Cl3A)=Sof(C18A)=Sof(H18A)=1-FVAR(2)
 Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(C18)=Sof(H18)=FVAR(2)
 Sof(Cl4)=Sof(Cl5)=Sof(Cl6)=Sof(C19)=Sof(H19)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C18(H18), C18A(H18A), C19(H19)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C11(H11), C12(H12), C13(H13)
6.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C17(H17A,H17B,H17C), C17A(H17D,H17E,H17F),
 C15(H15A,H15B,H15C)
;
_shelx_res_checksum              78141
_shelx_hkl_checksum              5327