Cyclometalated Pd(ii) and Ir(iii) 2-(4-bromophenyl)pyridine complexes with N-heterocyclic carbenes (NHCs) and acetylacetonate (acac): synthesis, structures, luminescent properties and application in one-pot oxidation/Suzuki coupling of aryl chlorides containing hydroxymethyl.
Xu, Chen; Li, Hong-Mei; Xiao, Zhi-Qiang; Wang, Zhi-Qiang; Tang, Si-Fu; Ji, Bao-Ming; Hao, Xin-Qi; Song, Mao-Ping; Dalton transactions (Cambridge, England : 2003) 43 (2014) 10235–10247; doi:10.1039/c4dt00833b

data_7030093
_publ_section_title
;
 Cyclometalated Pd(ii) and Ir(iii) 2-(4-bromophenyl)pyridine complexes
 with N-heterocyclic carbenes (NHCs) and acetylacetonate (acac):
 synthesis, structures, luminescent properties and application in one-pot
 oxidation/Suzuki coupling of aryl chlorides containing hydroxymethyl.
;
_journal_issue                   26
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10235
_journal_page_last               10247
_journal_paper_doi               10.1039/c4dt00833b
_journal_volume                  43
_journal_year                    2014
_chemical_formula_moiety         'C32 H31 Br Cl N3 Pd'
_chemical_formula_sum            'C32 H31 Br Cl N3 Pd'
_chemical_formula_weight         679.36
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-09-13
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 92.1390(12)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   18.7297(3)
_cell_length_b                   11.47367(16)
_cell_length_c                   27.2057(3)
_cell_measurement_reflns_used    5234
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      72.1820
_cell_measurement_theta_min      3.9390
_cell_volume                     5842.39(14)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      291.15
_diffrn_detector_area_resol_mean 16.2312
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega    2.00   27.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000 -180.0000 25

  2 omega  -93.00  -17.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   15.0000 -180.0000 76

  3 omega  -63.00  -32.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  178.0000  -60.0000 31

  4 omega  -78.00  -23.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -57.0000  -30.0000 55

  5 omega -119.00  -63.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  178.0000  -30.0000 56

  6 omega -109.00  -83.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  178.0000  -60.0000 26

  7 omega   37.00  115.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   77.0000  120.0000 78

  8 omega   44.00   96.00   1.0000    2.9300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  120.0000 52

  9 omega  122.00  174.00   1.0000    2.9300
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  150.0000 52

 10 omega   41.00   88.00   1.0000    2.9300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000   30.0000 47

 11 omega   42.00  102.00   1.0000    2.9300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000   60.0000 60

 12 omega   59.00   86.00   1.0000    2.9300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -180.0000 27

 13 omega   56.00   88.00   1.0000    2.9300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  150.0000 32

 14 omega   41.00   71.00   1.0000    2.9300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  -90.0000 30

 15 omega   60.00   90.00   1.0000    2.9300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000   60.0000 30

 16 omega   45.00   88.00   1.0000    2.9300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000  150.0000 43

 17 omega   46.00  103.00   1.0000    2.9300
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000    0.0000 57

 18 omega   88.00  173.00   1.0000    2.9300
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -180.0000 85

 19 omega  -77.00  -32.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000  120.0000 45

 20 omega  -47.00    6.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   30.0000  -60.0000 53
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0756759000
_diffrn_orient_matrix_UB_12      0.0475591000
_diffrn_orient_matrix_UB_13      -0.0077267000
_diffrn_orient_matrix_UB_21      -0.0252603000
_diffrn_orient_matrix_UB_22      0.1232925000
_diffrn_orient_matrix_UB_23      0.0135581000
_diffrn_orient_matrix_UB_31      0.0202155000
_diffrn_orient_matrix_UB_32      -0.0239950000
_diffrn_orient_matrix_UB_33      0.0544635000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0253
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            10895
_diffrn_reflns_theta_full        67.08
_diffrn_reflns_theta_max         67.08
_diffrn_reflns_theta_min         3.25
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.758
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59463
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.545
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2736
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.838
_refine_diff_density_min         -0.715
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     349
_refine_ls_number_reflns         5227
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0437
_refine_ls_R_factor_gt           0.0375
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0504P)^2^+7.0237P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0954
_refine_ls_wR_factor_ref         0.1007
_reflns_number_gt                4570
_reflns_number_total             5227
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c4dt00833b1.cif
_cod_data_source_block           201309144
_cod_depositor_comments
'Adding full bibliography for 7030091--7030097.cif.'
_cod_original_cell_volume        5842.37(14)
_cod_database_code               7030093
_chemical_oxdiff_formula         C20H20N4O4Pd1
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C8(H8), C10(H10), C11(H11), C14(H14),
 C16(H16), C22(H22), C23(H23), C26(H26), C28(H28)
2.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C)
;