#------------------------------------------------------------------------------
#$Date: 2016-03-22 12:55:48 +0200 (Tue, 22 Mar 2016) $
#$Revision: 178967 $
#$URL: svn://www.crystallography.net/cod/cif/4/11/96/4119681.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4119681
loop_
_publ_author_name
'Ansis Maleckis'
'Jeff W. Kampf'
'Melanie S. Sanford'
_publ_section_title
;
 A Detailed Study of Acetate-Assisted C-H Activation at Palladium(IV)
 Centers
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6618
_journal_page_last               6625
_journal_paper_doi               10.1021/ja401557m
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety         'C28 H22 Br2 N3 Pd, Br2 I'
_chemical_formula_sum            'C28 H22 Br4 I N3 Pd'
_chemical_formula_weight         953.43
_chemical_name_systematic
;
 ?
;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 103.335(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   13.5583(3)
_cell_length_b                   12.5698(2)
_cell_length_c                   17.5426(12)
_cell_measurement_reflns_used    48097
_cell_measurement_temperature    85(2)
_cell_measurement_theta_max      68.30
_cell_measurement_theta_min      2.60
_cell_volume                     2909.1(2)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r12'
_computing_data_collection
'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r12'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      85(2)
_diffrn_detector_area_resol_mean 29.257
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Rigaku Saturn944+ CCD'
_diffrn_measurement_method       ω
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_source         'micro-focus rotating'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0581
_diffrn_reflns_av_sigmaI/netI    0.0235
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_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            80357
_diffrn_reflns_theta_full        68.22
_diffrn_reflns_theta_max         68.22
_diffrn_reflns_theta_min         4.37
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    20.096
_exptl_absorpt_correction_T_max  0.545
_exptl_absorpt_correction_T_min  0.287
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
    Higashi, T. (1995). Program for Absorption Correction.
    Rigaku Corporation, Tokyo, Japan.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    2.177
_exptl_crystal_description       plate
_exptl_crystal_F_000             1800
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.708
_refine_diff_density_min         -0.777
_refine_diff_density_rms         0.120
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.126
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     334
_refine_ls_number_reflns         5317
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.126
_refine_ls_R_factor_all          0.0253
_refine_ls_R_factor_gt           0.0251
_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/[σ²(Fo²)+(0.0153P)²+12.7199P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0588
_refine_ls_wR_factor_ref         0.0589
_reflns_number_gt                5271
_reflns_number_total             5317
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja401557m_si_001_2.cif
_cod_data_source_block           COMPLEX20
_cod_database_code               4119681
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
Pd1 Pd 0.396444(17) 0.13721(2) 0.828945(15) 0.00759(7) Uani 1 1 d .
I1 I 0.870750(16) 0.288972(18) 0.236268(14) 0.01192(7) Uani 1 1 d .
Br1 Br 0.49102(3) -0.02481(3) 0.87133(2) 0.01446(9) Uani 1 1 d .
Br2 Br 0.52681(3) 0.19249(3) 0.76299(2) 0.01582(9) Uani 1 1 d .
Br3 Br 0.84436(3) 0.30294(3) 0.38236(3) 0.01900(10) Uani 1 1 d .
Br4 Br 0.91361(3) 0.28788(3) 0.09157(2) 0.01438(9) Uani 1 1 d .
N1 N 0.3163(2) 0.0537(2) 0.72251(18) 0.0116(6) Uani 1 1 d .
N2 N 0.2812(2) 0.0815(2) 0.87777(18) 0.0088(6) Uani 1 1 d .
N3 N 0.3108(2) 0.2670(2) 0.78017(18) 0.0096(6) Uani 1 1 d .
C1 C 0.3624(3) -0.0073(3) 0.6785(2) 0.0182(8) Uani 1 1 d .
H1A H 0.4334 -0.0185 0.6949 0.022 Uiso 1 1 calc R
C2 C 0.3098(3) -0.0540(3) 0.6104(3) 0.0220(9) Uani 1 1 d .
H2A H 0.3442 -0.0963 0.5798 0.026 Uiso 1 1 calc R
C3 C 0.2061(3) -0.0385(3) 0.5870(2) 0.0209(9) Uani 1 1 d .
H3A H 0.1683 -0.0698 0.5399 0.025 Uiso 1 1 calc R
C4 C 0.1583(3) 0.0232(3) 0.6329(2) 0.0171(8) Uani 1 1 d .
H4A H 0.0871 0.0344 0.6181 0.021 Uiso 1 1 calc R
C5 C 0.2156(3) 0.0683(3) 0.7007(2) 0.0109(7) Uani 1 1 d .
C6 C 0.1693(2) 0.1389(3) 0.7535(2) 0.0099(7) Uani 1 1 d .
H6A H 0.0945 0.1418 0.7310 0.012 Uiso 1 1 calc R
C7 C 0.1859(3) 0.0906(3) 0.8340(2) 0.0112(7) Uani 1 1 d .
C8 C 0.1054(3) 0.0490(3) 0.8616(2) 0.0155(8) Uani 1 1 d .
H8A H 0.0378 0.0574 0.8318 0.019 Uiso 1 1 calc R
C9 C 0.1241(3) -0.0046(3) 0.9321(3) 0.0193(9) Uani 1 1 d .
H9A H 0.0699 -0.0341 0.9510 0.023 Uiso 1 1 calc R
C10 C 0.2230(3) -0.0146(3) 0.9748(2) 0.0170(8) Uani 1 1 d .
H10A H 0.2375 -0.0520 1.0231 0.020 Uiso 1 1 calc R
C11 C 0.3003(3) 0.0303(3) 0.9464(2) 0.0138(8) Uani 1 1 d .
H11A H 0.3682 0.0247 0.9761 0.017 Uiso 1 1 calc R
C12 C 0.2109(3) 0.2506(3) 0.7504(2) 0.0093(7) Uani 1 1 d .
C13 C 0.1505(3) 0.3308(3) 0.7107(2) 0.0122(7) Uani 1 1 d .
H13A H 0.0800 0.3191 0.6910 0.015 Uiso 1 1 calc R
C14 C 0.1928(3) 0.4281(3) 0.6997(2) 0.0154(8) Uani 1 1 d .
H14A H 0.1520 0.4832 0.6717 0.019 Uiso 1 1 calc R
C15 C 0.2954(3) 0.4438(3) 0.7302(2) 0.0151(8) Uani 1 1 d .
H15A H 0.3262 0.5098 0.7232 0.018 Uiso 1 1 calc R
C16 C 0.3522(3) 0.3620(3) 0.7710(2) 0.0125(7) Uani 1 1 d .
H16A H 0.4223 0.3731 0.7930 0.015 Uiso 1 1 calc R
C17 C 0.4666(3) 0.2182(3) 0.9313(2) 0.0112(7) Uani 1 1 d .
C18 C 0.5715(3) 0.2048(3) 0.9536(2) 0.0142(8) Uani 1 1 d .
H18A H 0.6049 0.1643 0.9214 0.017 Uiso 1 1 calc R
C19 C 0.6276(3) 0.2497(3) 1.0218(2) 0.0146(8) Uani 1 1 d .
H19A H 0.6990 0.2398 1.0362 0.017 Uiso 1 1 calc R
C20 C 0.5803(3) 0.3085(3) 1.0689(2) 0.0198(9) Uani 1 1 d .
H20A H 0.6185 0.3393 1.1159 0.024 Uiso 1 1 calc R
C21 C 0.4760(3) 0.3223(3) 1.0468(2) 0.0181(8) Uani 1 1 d .
H21A H 0.4438 0.3627 1.0799 0.022 Uiso 1 1 calc R
C22 C 0.4163(3) 0.2790(3) 0.9777(2) 0.0132(8) Uani 1 1 d .
C23 C 0.3048(3) 0.3027(3) 0.9649(2) 0.0136(8) Uani 1 1 d .
C24 C 0.2461(3) 0.2464(3) 1.0074(2) 0.0169(8) Uani 1 1 d .
H24A H 0.2769 0.1935 1.0438 0.020 Uiso 1 1 calc R
C25 C 0.1433(3) 0.2673(4) 0.9966(3) 0.0239(9) Uani 1 1 d .
H25A H 0.1037 0.2265 1.0241 0.029 Uiso 1 1 calc R
C26 C 0.0978(3) 0.3473(4) 0.9459(3) 0.0253(10) Uani 1 1 d .
H26A H 0.0271 0.3599 0.9374 0.030 Uiso 1 1 calc R
C27 C 0.1568(3) 0.4087(4) 0.9077(3) 0.0240(10) Uani 1 1 d .
H27A H 0.1269 0.4653 0.8744 0.029 Uiso 1 1 calc R
C28 C 0.2601(3) 0.3870(3) 0.9185(2) 0.0184(8) Uani 1 1 d .
H28A H 0.3006 0.4307 0.8937 0.022 Uiso 1 1 calc R
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pd Pd 0.1215 3.9337 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
I I -0.3257 6.8362 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
N3 Pd1 N2 91.87(12)
N3 Pd1 C17 94.12(13)
N2 Pd1 C17 92.68(13)
N3 Pd1 N1 84.55(12)
N2 Pd1 N1 85.25(12)
C17 Pd1 N1 177.49(13)
N3 Pd1 Br2 88.74(8)
N2 Pd1 Br2 175.35(8)
C17 Pd1 Br2 91.88(10)
N1 Pd1 Br2 90.22(8)
N3 Pd1 Br1 173.34(9)
N2 Pd1 Br1 89.17(8)
C17 Pd1 Br1 92.40(10)
N1 Pd1 Br1 88.98(8)
Br2 Pd1 Br1 89.707(15)
Br3 I1 Br4 174.354(15)
C1 N1 C5 119.5(3)
C1 N1 Pd1 123.9(3)
C5 N1 Pd1 116.6(2)
C11 N2 C7 121.0(3)
C11 N2 Pd1 121.8(2)
C7 N2 Pd1 116.9(2)
C16 N3 C12 119.8(3)
C16 N3 Pd1 122.7(2)
C12 N3 Pd1 117.2(2)
N1 C1 C2 121.9(4)
C1 C2 C3 119.0(4)
C4 C3 C2 119.1(4)
C3 C4 C5 119.0(4)
N1 C5 C4 121.4(4)
N1 C5 C6 116.2(3)
C4 C5 C6 122.4(3)
C7 C6 C12 115.5(3)
C7 C6 C5 110.1(3)
C12 C6 C5 108.0(3)
N2 C7 C8 119.7(3)
N2 C7 C6 119.0(3)
C8 C7 C6 121.1(3)
C9 C8 C7 119.8(3)
C8 C9 C10 119.0(4)
C11 C10 C9 119.3(4)
N2 C11 C10 121.0(3)
N3 C12 C13 120.6(3)
N3 C12 C6 118.3(3)
C13 C12 C6 120.7(3)
C12 C13 C14 119.9(3)
C13 C14 C15 119.0(3)
C16 C15 C14 119.0(3)
N3 C16 C15 121.6(3)
C18 C17 C22 120.2(3)
C18 C17 Pd1 114.5(3)
C22 C17 Pd1 125.3(3)
C19 C18 C17 121.1(4)
C20 C19 C18 120.0(3)
C19 C20 C21 119.2(4)
C20 C21 C22 122.6(4)
C17 C22 C21 116.9(3)
C17 C22 C23 128.8(3)
C21 C22 C23 114.2(3)
C28 C23 C24 118.2(3)
C28 C23 C22 121.7(4)
C24 C23 C22 119.7(3)
C25 C24 C23 120.5(4)
C24 C25 C26 120.5(4)
C25 C26 C27 119.4(4)
C26 C27 C28 119.8(4)
C23 C28 C27 121.2(4)
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
Pd1 N3 2.069(3)
Pd1 N2 2.070(3)
Pd1 C17 2.091(4)
Pd1 N1 2.199(3)
Pd1 Br2 2.4267(5)
Pd1 Br1 2.4300(4)
I1 Br3 2.6740(5)
I1 Br4 2.7316(5)
N1 C1 1.340(5)
N1 C5 1.343(5)
N2 C11 1.337(5)
N2 C7 1.347(5)
N3 C16 1.345(5)
N3 C12 1.351(4)
C1 C2 1.374(6)
C2 C3 1.385(6)
C3 C4 1.382(6)
C4 C5 1.383(5)
C5 C6 1.520(5)
C6 C7 1.506(5)
C6 C12 1.519(5)
C7 C8 1.393(5)
C8 C9 1.379(6)
C9 C10 1.382(6)
C10 C11 1.382(5)
C12 C13 1.381(5)
C13 C14 1.383(5)
C14 C15 1.385(5)
C15 C16 1.381(5)
C17 C18 1.396(5)
C17 C22 1.402(5)
C18 C19 1.382(6)
C19 C20 1.372(6)
C20 C21 1.388(6)
C21 C22 1.404(5)
C22 C23 1.507(5)
C23 C28 1.387(6)
C23 C24 1.401(6)
C24 C25 1.388(5)
C25 C26 1.389(7)
C26 C27 1.389(7)
C27 C28 1.397(6)
