Dihalogen-bridged NHC-palladium(I) dimers: synthesis, characterisation and applications in cross-coupling reactions
Goossen, Lukas J.; Pirkl, Nico; Del Grosso , Alessandro; Mallick, Bert; Doppiu, Angelino; Chemical Communications  (2019) –; doi:10.1039/C9CC02239B

data_7123279
_publ_section_title
;
 Dihalogen-bridged NHC-palladium(I) dimers: synthesis, characterisation
 and applications in cross-coupling reactions
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC02239B
_journal_year                    2019
_chemical_formula_moiety         'C54 H73 Br N4 Pd, 2(C3 H6 O)'
_chemical_formula_sum            'C60 H85 Br N4 O2 Pd'
_chemical_formula_weight         1080.62
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-07
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.03.09 svn.r3491 for OlexSys, GUI svn.r5477)
;
_audit_update_record
;
2019-02-07 deposited with the CCDC.    2019-04-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.0258(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3520(2)
_cell_length_b                   21.7347(4)
_cell_length_c                   21.4568(4)
_cell_measurement_reflns_used    11817
_cell_measurement_temperature    102.7(9)
_cell_measurement_theta_max      76.1820
_cell_measurement_theta_min      4.0340
_cell_volume                     5759.52(18)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      102.7(9)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4409
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):
 
 # Type Start End Width t~exp~ \w \q \k \f Frames
 --------------------------------------------------------------------------
 1 \w -25.00 25.00 1.00 1.00 -- -42.53 37.00 60.00 50
 2 \w 17.00 91.00 1.00 1.00 -- 42.53-125.00 120.00 74
 3 \w 72.00 115.00 1.00 2.50 -- 112.00-115.00 -22.00 43
 4 \w 76.00 110.00 1.00 2.50 -- 112.00-111.00 30.00 34
 5 \w 64.00 113.00 1.00 2.50 -- 112.00-111.00 60.00 49
 6 \w 29.00 91.00 1.00 2.50 -- 112.00 -94.00 -30.00 62
 7 \w 29.00 92.00 1.00 2.50 -- 112.00 -94.00-120.00 63
 8 \w 125.00 151.00 1.00 2.50 -- 112.00 30.00 30.00 26
 9 \w 114.00 156.00 1.00 2.50 -- 112.00 45.00 -30.00 42
 10 \w 90.00 135.00 1.00 2.50 -- 112.00 30.00-150.00 45
 11 \w 88.00 137.00 1.00 2.50 -- 112.00 77.00 -30.00 49
 12 \w 88.00 153.00 1.00 2.50 -- 112.00 61.00 60.00 65
 13 \w 115.00 154.00 1.00 2.50 -- 112.00 45.00 120.00 39
 14 \w 84.00 158.00 1.00 2.50 -- 112.00 61.00 90.00 74
 15 \w 83.00 153.00 1.00 2.50 -- 112.00 61.00 30.00 70
 16 \w 29.00 108.00 1.00 2.50 -- 112.00 -94.00 120.00 79
 17 \w -114.00 -77.00 1.00 1.00 -- -42.53 -37.00-120.00 37
 18 \w -113.00 -15.00 1.00 1.00 -- -42.53 -57.00 -60.00 98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0497375000
_diffrn_orient_matrix_UB_12      -0.0649193000
_diffrn_orient_matrix_UB_13      -0.0044075000
_diffrn_orient_matrix_UB_21      0.0970327000
_diffrn_orient_matrix_UB_22      -0.0261341000
_diffrn_orient_matrix_UB_23      0.0374956000
_diffrn_orient_matrix_UB_31      -0.0604046000
_diffrn_orient_matrix_UB_32      0.0114102000
_diffrn_orient_matrix_UB_33      0.0611162000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0455
_diffrn_reflns_av_unetI/netI     0.0493
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            33081
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.995
_diffrn_reflns_theta_min         4.068
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.733
_exptl_absorpt_correction_T_max  0.370
_exptl_absorpt_correction_T_min  0.212
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015) 
Numerical absorption correction based on gaussian integration over 
a multifaceted crystal model Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.246
_exptl_crystal_description       prism
_exptl_crystal_F_000             2280
_exptl_crystal_size_max          0.113
_exptl_crystal_size_mid          0.089
_exptl_crystal_size_min          0.087
_refine_diff_density_max         0.835
_refine_diff_density_min         -0.438
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     649
_refine_ls_number_reflns         10492
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0427
_refine_ls_R_factor_gt           0.0334
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0347P)^2^+1.2933P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0769
_refine_ls_wR_factor_ref         0.0830
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8963
_reflns_number_total             10492
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc02239b2.cif
_cod_data_source_block           dea-564
_cod_original_cell_volume        5759.49(17)
_cod_database_code               7123279
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C14 H30 N5 Pd Br2'
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All Br(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Pd1-Br1 \\sim Pd1-Br2
 with sigma of 0.02
 Pd1-HB \\sim Pd1-HA
 with sigma of 0.02
 Br2-HB \\sim Br1-HA
 with sigma of 0.02
 Br2-HA \\sim Br1-HB
 with sigma of 0.02
3. Restrained planarity
 Pd1, Br1, Br2, HA, HB
 with sigma of 0.1
4. Others
 Sof(Br1)=Sof(HA)=1-FVAR(1)
 Sof(Br2)=Sof(HB)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C20(H20), C49(H49), C52(H52), C55(H55), C26(H26), C29(H29), C58(H58), C23(H23)
5.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C34(H34), C18(H18), C47(H47), C45(H45), C11(H11), C40(H40),
 C39(H39), C36(H36), C46(H46), C5(H5), C35(H35), C(H), C16(H16), C17(H17),
 C7(H7)
5.c Idealised Me refined as rotating group:
 C60(H60A,H60B,H60C), C51(H51A,H51B,H51C), C25(H25A,H25B,H25C), C31(H31A,H31B,
 H31C), C30(H30A,H30B,H30C), C50(H50A,H50B,H50C), C24(H24A,H24B,H24C), C59(H59A,
 H59B,H59C), C22(H22A,H22B,H22C), C28(H28A,H28B,H28C), C63(H63A,H63B,H63C),
 C21(H21A,H21B,H21C), C57(H57A,H57B,H57C), C54(H54A,H54B,H54C), C27(H27A,H27B,
 H1), C56(H56A,H56B,H56C), C65(H65A,H65B,H65C), C67(H67A,H67B,H67C), C64(H64A,
 H64B,H64C), C53(H53A,H53B,H53C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
 - Absorption correction using spherical harmonics
 - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.125
_oxdiff_exptl_absorpt_empirical_full_min 0.912