Palladium(II) Weak-Link Approach Complexes Bearing Hemilabile N-Heterocyclic Carbene-Thioether Ligands.
Liu, Yuan; Kean, Zachary S.; d'Aquino, Andrea I; Manraj, Yashin D.; Mendez-Arroyo, Jose; Mirkin, Chad A.; Inorganic chemistry 56 (2017) 5902–5910; doi:10.1021/acs.inorgchem.7b00543

data_4345885
_publ_section_title
;
 Palladium(II) Weak-Link Approach Complexes Bearing Hemilabile
 N-Heterocyclic Carbene-Thioether Ligands.
;
_journal_issue                   10
_journal_name_full               'Inorganic chemistry'
_journal_page_first              5902
_journal_page_last               5910
_journal_paper_doi               10.1021/acs.inorgchem.7b00543
_journal_volume                  56
_journal_year                    2017
_chemical_formula_moiety         'C32 H44 N4 Pd S2, 2(B F4), H2 O'
_chemical_formula_sum            'C32 H46 B2 F8 N4 O Pd S2'
_chemical_formula_weight         846.87
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2017-03-31
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                113.418(2)
_cell_angle_beta                 105.753(2)
_cell_angle_gamma                90.132(2)
_cell_formula_units_Z            6
_cell_length_a                   12.4414(3)
_cell_length_b                   22.5034(6)
_cell_length_c                   22.5136(6)
_cell_measurement_reflns_used    8287
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.577
_cell_measurement_theta_min      4.536
_cell_volume                     5523.3(3)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.96
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.913
_diffrn_measured_fraction_theta_max 1.002
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0556
_diffrn_reflns_av_unetI/netI     0.0578
_diffrn_reflns_Laue_measured_fraction_full 0.913
_diffrn_reflns_Laue_measured_fraction_max 1.002
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            40595
_diffrn_reflns_point_group_measured_fraction_full 0.913
_diffrn_reflns_point_group_measured_fraction_max 1.002
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         63.681
_diffrn_reflns_theta_min         2.156
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    5.769
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6275
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0659 before and 0.0513 after correction.
The Ratio of minimum to maximum transmission is 0.8336.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.528
_exptl_crystal_description       block
_exptl_crystal_F_000             2604
_exptl_crystal_size_max          0.093
_exptl_crystal_size_mid          0.068
_exptl_crystal_size_min          0.039
_refine_diff_density_max         1.361
_refine_diff_density_min         -1.491
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1461
_refine_ls_number_reflns         17953
_refine_ls_number_restraints     123
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0658
_refine_ls_R_factor_gt           0.0541
_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^)+(0.0678P)^2^+16.5324P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1378
_refine_ls_wR_factor_ref         0.1482
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15138
_reflns_number_total             17953
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00543_si_005.cif
_cod_data_source_block           cx0819
_cod_database_code               4345885
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.806
_shelx_estimated_absorpt_t_min   0.616
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7757(10)
 0.2243(10)
2. 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, All O(H,H) groups
3. Restrained distances
 F19A-B5 \\sim F19-B5 \\sim F18-B5 \\sim F20A-B5 \\sim F20-B5 \\sim F17-B5
\\sim F22A-B6 \\sim F24-B6 ~
 F24A-B6 \\sim F21-B6 \\sim F23-B6 \\sim F22-B6
 with sigma of 0.01
 C31C-C29B \\sim C31B-C29B \\sim C32C-C29B \\sim C32B-C29B \\sim C30C-C29B
\\sim C30B-C29B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C30B \\sim C30C \\sim C31B \\sim C31C \\sim C32B \\sim C32C: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F24) \\sim Ueq, Uanis(F24A) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
5. Rigid body (RIGU) restrains
 F19, F19A, F20, F20A, F22, F22A, F24, F24A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C30B, C30C, C31B, C31C, C32B, C32C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O3, O3A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Sof(F19A)=Sof(F20A)=1-FVAR(1)
 Sof(F19)=Sof(F20)=FVAR(1)
 Sof(F22A)=Sof(F24A)=1-FVAR(2)
 Sof(F22)=Sof(F24)=FVAR(2)
 Sof(C30C)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31C)=Sof(H31D)=Sof(H31E)=
 Sof(H31F)=Sof(C32C)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(3)
 Sof(C30B)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31B)=Sof(H31A)=Sof(H31B)=
 Sof(H31C)=Sof(C32B)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(3)
 Sof(O3A)=Sof(H3AA)=Sof(H3AB)=1-FVAR(4)
 Sof(O3)=Sof(H3C)=Sof(H3D)=FVAR(4)
7.a Free rotating group:
 O1(H1A,H1B), O3(H3C,H3D), O2(H2C,H2D), O3A(H3AA,H3AB)
7.b Secondary CH2 refined with riding coordinates:
 C7B(H7BA,H7BB), C8B(H8BA,H8BB), C9B(H9BA,H9BB), C23B(H23A,H23B), C24B(H24A,
 H24B), C25B(H25A,H25B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C23(H23C,H23D),
 C24(H24C,H24D), C25(H25C,H25D), C7A(H7AA,H7AB), C8A(H8AA,H8AB), C9A(H9AA,H9AB),
  C23A(H23E,H23F), C24A(H24E,H24F), C25A(H25E,H25F)
7.c Aromatic/amide H refined with riding coordinates:
 C2B(H2B), C3B(H3B), C4B(H4B), C5B(H5B), C6B(H6B), C11B(H11B), C12B(H12B),
 C18B(H18B), C19B(H19B), C20B(H20B), C21B(H21B), C22B(H22B), C27B(H27B),
 C28B(H28B), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C11(H11), C12(H12),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C27(H27), C28(H28), C2A(H2A),
  C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C11A(H11A), C12A(H12A), C18A(H18A),
 C19A(H19A), C20A(H20A), C21A(H21A), C22A(H22A), C27A(H27A), C28A(H28A)
7.d Idealised Me refined as rotating group:
 C14B(H14A,H14B,H14C), C15B(H15A,H15B,H15C), C16B(H16A,H16B,H16C), C30B(H30A,
 H30B,H30C), C30C(H30D,H30E,H30F), C31B(H31A,H31B,H31C), C31C(H31D,H31E,H31F),
 C32B(H32A,H32B,H32C), C32C(H32D,H32E,H32F), C14(H14D,H14E,H14F), C15(H15D,H15E,
 H15F), C16(H16D,H16E,H16F), C30(H30G,H30H,H30I), C31(H31G,H31H,H31I), C32(H32G,
 H32H,H32I), C14A(H14G,H14H,H14I), C15A(H15G,H15H,H15I), C16A(H16G,H16H,H16I),
 C30A(H30J,H30K,H30L), C31A(H31J,H31K,H31L), C32A(H32J,H32K,H32L)
;
_shelx_res_checksum              20737
_shelx_hkl_checksum              1839
_olex2_date_sample_data_collection 2016-07-28
_olex2_date_sample_submission    2016-07-27
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id cx0819
_olex2_submission_special_instructions 'No special instructions were received'