Structure and Gas-Phase Thermochemistry of a Pd/Cu Complex: Studies on a Model for Transmetalation Transition States.
Oeschger, Raphael J.; Chen, Peter; Journal of the American Chemical Society 139 (2017) 1069–1072; doi:10.1021/jacs.6b12152

data_4125833
_publ_section_title
;
 Structure and Gas-Phase Thermochemistry of a Pd/Cu Complex: Studies on a
 Model for Transmetalation Transition States.
;
_journal_issue                   3
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1069
_journal_page_last               1072
_journal_paper_doi               10.1021/jacs.6b12152
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C53 H52 Cu N4 Pd, C F3 O3 S, 2(C H2 Cl2)'
_chemical_formula_sum            'C56 H56 Cl4 Cu F3 N4 O3 Pd S'
_chemical_formula_weight         1233.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-05-06
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.278(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.532(2)
_cell_length_b                   20.908(4)
_cell_length_c                   12.844(3)
_cell_measurement_reflns_used    9931
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      25.77
_cell_measurement_theta_min      2.54
_cell_volume                     2763.6(10)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker/Nonius Kappa Apex2'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'double mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0524
_diffrn_reflns_av_unetI/netI     0.0586
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            54931
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.095
_diffrn_reflns_theta_min         2.536
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms high brilliance'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.998
_exptl_absorpt_correction_T_max  0.7320
_exptl_absorpt_correction_T_min  0.6525
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0871 before and 0.0619 after correction.
The Ratio of minimum to maximum transmission is 0.8914.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.483
_exptl_crystal_description       plate
_exptl_crystal_F_000             1260
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.561
_refine_diff_density_min         -0.965
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Flack x determined using 5355 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.007(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     766
_refine_ls_number_reflns         14704
_refine_ls_number_restraints     272
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0508
_refine_ls_R_factor_gt           0.0383
_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^)+(0.0357P)^2^+0.3926P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0777
_refine_ls_wR_factor_ref         0.0830
_reflns_Friedel_coverage         0.942
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                12604
_reflns_number_total             14704
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b12152_si_002.cif
_cod_data_source_block           c040516_1_1_0m
_cod_original_cell_volume        2763.8(10)
_cod_database_code               4125833
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.825
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl4A-C55A \\sim Cl4-C55 \\sim Cl3A-C55A \\sim Cl3-C55
 with sigma of 0.02
 Cl4A-Cl3A \\sim Cl4-Cl3
 with sigma of 0.02
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F1A-F2A \\sim F2A-F3A \\sim F3A-F1A
 with sigma of 0.02
 F1-C56 \\sim F2A-C56A \\sim F2-C56 \\sim F3A-C56A \\sim F3-C56 \\sim F1A-C56A
 with sigma of 0.02
 S1-O3 \\sim S1-O1 \\sim S1-O2
 with sigma of 0.02
 O1-O2 \\sim O2-O3 \\sim O3-O1
 with sigma of 0.02
 S1-O2 \\sim S1A-O1A \\sim S1-O1 \\sim S1A-O3A \\sim S1-O3 \\sim S1A-O2A
 with sigma of 0.02
 O1-O2 \\sim O2-O3 \\sim O3-O1 \\sim O1A-O2A \\sim O2A-O3A \\sim O3A-O1A
 with sigma of 0.02
 O1-C56 \\sim O2-C56 \\sim O3-C56
 with sigma of 0.02
 S1A-C56A \\sim S1-C56
 with sigma of 0.02
3. Rigid bond restraints
 Cl3, Cl4, C55, Cl3A, Cl4A, C55A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S1, F1, F2, F3, O1, O2, O3, C56, S1A, F1A, F2A, F3A, O1A, O2A, O3A, C56A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C56A) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F2A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 Cl3, Cl4, C55, Cl3A, Cl4A, C55A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1, F1, F2, F3, O1, O2, O3, C56, S1A, F1A, F2A, F3A, O1A, O2A, O3A, C56A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(S1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(C56A)=
 Sof(Cl3A)=Sof(Cl4A)=Sof(C55A)=Sof(H55C)=Sof(H55D)=1-FVAR(1)
 Sof(S1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(C56)=Sof(Cl3)=
 Sof(Cl4)=Sof(C55)=Sof(H55A)=Sof(H55B)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C34(H34), C37(H37), C48(H48), C51(H51)
7.b Secondary CH2 refined with riding coordinates:
 C55(H55A,H55B), C55A(H55C,H55D), C54(H54A,H54B)
7.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C6(H6), C7(H7), C10(H10), C11(H11), C12(H12),
 C14(H14), C15(H15), C16(H16), C19(H19), C20(H20), C23(H23), C24(H24), C25(H25),
  C30(H30), C31(H31), C32(H32), C40(H40), C41(H41), C44(H44), C45(H45), C46(H46)
7.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,
 H39C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C), C53(H53A,
 H53B,H53C)
;
_shelx_res_checksum              15234
_shelx_hkl_checksum              55149
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-05-04
_olex2_date_sample_submission    2016-05-04
_olex2_submission_original_sample_id c040516_1_1
_olex2_submission_special_instructions 'No special instructions were received'