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#$Date: 2016-03-21 07:50:34 +0200 (Mon, 21 Mar 2016) $
#$Revision: 178584 $
#$URL: svn://www.crystallography.net/cod/cif/4/06/95/4069586.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_4069586
loop_
_publ_author_name
'Vicente, José'
'Saura-Llamas, Isabel'
'Turpín, Juana'
'Bautista, Delia'
'de Arellano, Carmen Ramírez'
'Jones, Peter G.'
_publ_section_title
;
 Insertion of One, Two, and Three Molecules of Alkyne into the Pd−C
 Bond of Ortho-palladated Primary and Secondary Arylalkylamines
;
_journal_issue                   14
_journal_name_full               Organometallics
_journal_page_first              4175
_journal_paper_doi               10.1021/om9002895
_journal_volume                  28
_journal_year                    2009
_chemical_formula_sum            'C44 H66 Br2 F2 N2 O4 Pd2 S2'
_chemical_formula_weight         1161.73
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                106.439(2)
_cell_angle_beta                 103.292(2)
_cell_angle_gamma                104.686(2)
_cell_formula_units_Z            1
_cell_length_a                   10.1790(6)
_cell_length_b                   11.4544(7)
_cell_length_c                   11.6891(7)
_cell_measurement_reflns_used    3402
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.00
_cell_measurement_theta_min      2.18
_cell_volume                     1195.76(13)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_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      100(2)
_diffrn_detector_area_resol_mean 8.26
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.916
_diffrn_measurement_device_type  'Bruker SMART APEX CCD'
_diffrn_measurement_method       ω-scan
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0409
_diffrn_reflns_av_sigmaI/netI    0.0565
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            13910
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         28.17
_diffrn_reflns_theta_min         1.92
_exptl_absorpt_coefficient_mu    2.559
_exptl_absorpt_correction_T_max  0.9272
_exptl_absorpt_correction_T_min  0.8304
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            pale-yellow
_exptl_crystal_density_diffrn    1.613
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             588
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.802
_refine_diff_density_min         -1.571
_refine_diff_density_rms         0.129
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    'NH2 wtih DFIX, rigid methyls, others riding'
_refine_ls_matrix_type           full
_refine_ls_number_parameters     276
_refine_ls_number_reflns         5379
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0566
_refine_ls_R_factor_gt           0.0464
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0353P)²+0.8970P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0867
_refine_ls_wR_factor_ref         0.0904
_reflns_number_gt                4662
_reflns_number_total             5379
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om9002895_si_002.cif
_cod_data_source_block           ja621s
_cod_original_cell_volume        1195.76(12)
_cod_database_code               4069586
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
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 0.43633(3) 0.32973(3) 0.85327(3) 0.00969(9) Uani 1 1 d .
Br1 Br 0.33293(4) 0.53921(4) 0.95292(4) 0.01481(11) Uani 1 1 d .
N1 N 0.5146(4) 0.4618(3) 0.7617(3) 0.0136(7) Uani 1 1 d D
H01A H 0.550(4) 0.533(2) 0.825(3) 0.005(10) Uiso 1 1 d D
H01B H 0.581(4) 0.446(4) 0.732(4) 0.021(13) Uiso 1 1 d D
C1 C 0.2950(4) 0.2185(4) 0.5561(4) 0.0121(8) Uani 1 1 d .
C2 C 0.3368(4) 0.3421(4) 0.5496(4) 0.0147(8) Uani 1 1 d .
C3 C 0.3202(4) 0.3533(4) 0.4313(4) 0.0180(9) Uani 1 1 d .
H3 H 0.3488 0.4373 0.4275 0.022 Uiso 1 1 calc R
C4 C 0.2641(5) 0.2473(4) 0.3201(4) 0.0212(10) Uani 1 1 d .
H4 H 0.2544 0.2569 0.2408 0.025 Uiso 1 1 calc R
C5 C 0.2229(4) 0.1274(4) 0.3291(4) 0.0173(9) Uani 1 1 d .
F1 F 0.1622(3) 0.0202(2) 0.2218(2) 0.0254(6) Uani 1 1 d .
C6 C 0.2365(4) 0.1109(4) 0.4428(4) 0.0156(9) Uani 1 1 d .
H6 H 0.2061 0.0261 0.4447 0.019 Uiso 1 1 calc R
C7 C 0.2964(4) 0.1843(4) 0.6734(3) 0.0118(8) Uani 1 1 d .
C8 C 0.4121(4) 0.1447(4) 0.7251(4) 0.0127(8) Uani 1 1 d .
C9 C 0.3871(4) 0.0493(4) 0.7899(4) 0.0128(8) Uani 1 1 d .
C10 C 0.3621(4) 0.0860(4) 0.9001(4) 0.0125(8) Uani 1 1 d .
C11 C 0.3679(4) 0.2227(4) 0.9483(4) 0.0132(8) Uani 1 1 d .
O1 O 0.3364(3) 0.2678(3) 1.0406(3) 0.0191(6) Uani 1 1 d .
C12 C 0.3965(4) 0.4649(4) 0.6638(4) 0.0147(8) Uani 1 1 d .
H12A H 0.4320 0.5394 0.6386 0.018 Uiso 1 1 calc R
H12B H 0.3190 0.4772 0.6987 0.018 Uiso 1 1 calc R
C13 C 0.1445(4) 0.1295(4) 0.6749(4) 0.0136(8) Uani 1 1 d .
H13A H 0.1486 0.1022 0.7485 0.016 Uiso 1 1 calc R
H13B H 0.0898 0.0517 0.5978 0.016 Uiso 1 1 calc R
C14 C 0.0652(4) 0.2265(4) 0.6818(4) 0.0191(9) Uani 1 1 d .
H14A H 0.1167 0.3023 0.7598 0.029 Uiso 1 1 calc R
H14B H -0.0323 0.1859 0.6810 0.029 Uiso 1 1 calc R
H14C H 0.0603 0.2537 0.6091 0.029 Uiso 1 1 calc R
C15 C 0.5378(4) 0.1522(4) 0.6745(4) 0.0162(9) Uani 1 1 d .
H15A H 0.5469 0.2190 0.6357 0.019 Uiso 1 1 calc R
H15B H 0.5173 0.0681 0.6077 0.019 Uiso 1 1 calc R
C16 C 0.6802(4) 0.1847(4) 0.7754(4) 0.0183(9) Uani 1 1 d .
H16A H 0.7054 0.2711 0.8385 0.028 Uiso 1 1 calc R
H16B H 0.7555 0.1833 0.7363 0.028 Uiso 1 1 calc R
H16C H 0.6714 0.1207 0.8164 0.028 Uiso 1 1 calc R
C17 C 0.3848(5) -0.0851(4) 0.7232(4) 0.0181(9) Uani 1 1 d .
H17A H 0.3768 -0.1350 0.7795 0.022 Uiso 1 1 calc R
H17B H 0.4769 -0.0787 0.7065 0.022 Uiso 1 1 calc R
C18 C 0.2609(5) -0.1591(4) 0.5979(4) 0.0278(11) Uani 1 1 d .
H18A H 0.1690 -0.1708 0.6141 0.042 Uiso 1 1 calc R
H18B H 0.2675 -0.2440 0.5577 0.042 Uiso 1 1 calc R
H18C H 0.2670 -0.1097 0.5420 0.042 Uiso 1 1 calc R
C19 C 0.3133(4) 0.0016(4) 0.9716(4) 0.0173(9) Uani 1 1 d .
H19A H 0.3511 0.0537 1.0630 0.021 Uiso 1 1 calc R
H19B H 0.3529 -0.0697 0.9572 0.021 Uiso 1 1 calc R
C20 C 0.1504(5) -0.0549(4) 0.9305(4) 0.0230(10) Uani 1 1 d .
H20A H 0.1105 0.0153 0.9393 0.034 Uiso 1 1 calc R
H20B H 0.1224 -0.1029 0.9834 0.034 Uiso 1 1 calc R
H20C H 0.1133 -0.1137 0.8421 0.034 Uiso 1 1 calc R
O2 O 0.7681(3) 0.4378(3) 0.6821(3) 0.0235(7) Uani 1 1 d .
S1 S 0.91861(12) 0.47329(11) 0.76639(11) 0.0216(2) Uani 1 1 d .
C91 C 1.0317(5) 0.5625(5) 0.7001(5) 0.0292(11) Uani 1 1 d .
H91A H 1.0290 0.5040 0.6194 0.044 Uiso 1 1 calc R
H91B H 1.1306 0.6006 0.7583 0.044 Uiso 1 1 calc R
H91C H 0.9973 0.6315 0.6864 0.044 Uiso 1 1 calc R
C92 C 0.9463(5) 0.6048(4) 0.9056(4) 0.0260(10) Uani 1 1 d .
H92A H 0.9217 0.6741 0.8823 0.039 Uiso 1 1 calc R
H92B H 1.0473 0.6377 0.9585 0.039 Uiso 1 1 calc R
H92C H 0.8852 0.5748 0.9525 0.039 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 0.0033 0.0016 '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 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pd Pd -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 '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
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
C11 Pd1 C8 81.50(16) . .
C11 Pd1 C7 92.94(15) . .
C8 Pd1 C7 39.01(14) . .
C11 Pd1 N1 175.30(15) . .
C8 Pd1 N1 103.17(14) . .
C7 Pd1 N1 91.08(14) . .
C11 Pd1 Br1 88.74(11) . 2_667
C8 Pd1 Br1 121.10(11) . 2_667
C7 Pd1 Br1 159.08(11) . 2_667
N1 Pd1 Br1 88.38(9) . 2_667
C11 Pd1 Br1 97.11(12) . .
C8 Pd1 Br1 153.45(11) . .
C7 Pd1 Br1 115.17(10) . .
N1 Pd1 Br1 78.95(9) . .
Br1 Pd1 Br1 85.247(15) 2_667 .
Pd1 Br1 Pd1 94.753(15) 2_667 .
C12 N1 Pd1 111.7(2) . .
C2 C1 C6 118.2(4) . .
C2 C1 C7 127.7(3) . .
C6 C1 C7 114.0(3) . .
C1 C2 C3 119.0(4) . .
C1 C2 C12 123.3(4) . .
C3 C2 C12 117.7(4) . .
C4 C3 C2 122.7(4) . .
C5 C4 C3 117.1(4) . .
F1 C5 C4 119.2(4) . .
F1 C5 C6 118.2(4) . .
C4 C5 C6 122.6(4) . .
C5 C6 C1 120.4(4) . .
C8 C7 C13 123.2(3) . .
C8 C7 C1 117.5(3) . .
C13 C7 C1 111.0(3) . .
C8 C7 Pd1 69.6(2) . .
C13 C7 Pd1 111.9(2) . .
C1 C7 Pd1 117.4(3) . .
C7 C8 C9 119.7(3) . .
C7 C8 C15 121.0(3) . .
C9 C8 C15 115.0(3) . .
C7 C8 Pd1 71.4(2) . .
C9 C8 Pd1 107.9(3) . .
C15 C8 Pd1 111.1(3) . .
C10 C9 C8 118.7(4) . .
C10 C9 C17 123.9(4) . .
C8 C9 C17 117.4(3) . .
C9 C10 C11 114.9(3) . .
C9 C10 C19 127.6(4) . .
C11 C10 C19 117.1(3) . .
O1 C11 C10 123.2(4) . .
O1 C11 Pd1 121.4(3) . .
C10 C11 Pd1 115.4(3) . .
N1 C12 C2 111.5(3) . .
C7 C13 C14 112.8(3) . .
C8 C15 C16 113.4(3) . .
C9 C17 C18 113.4(3) . .
C10 C19 C20 111.6(3) . .
O2 S1 C92 107.2(2) . .
O2 S1 C91 105.4(2) . .
C92 S1 C91 97.7(2) . .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Pd1 C11 1.979(4) .
Pd1 C8 2.136(4) .
Pd1 C7 2.159(4) .
Pd1 N1 2.183(4) .
Pd1 Br1 2.5967(5) 2_667
Pd1 Br1 2.9128(5) .
Br1 Pd1 2.5967(5) 2_667
N1 C12 1.473(5) .
C1 C2 1.400(5) .
C1 C6 1.403(5) .
C1 C7 1.527(5) .
C2 C3 1.401(5) .
C2 C12 1.503(5) .
C3 C4 1.380(6) .
C4 C5 1.371(6) .
C5 F1 1.360(4) .
C5 C6 1.376(6) .
C7 C8 1.435(5) .
C7 C13 1.521(5) .
C8 C9 1.499(5) .
C8 C15 1.522(5) .
C9 C10 1.342(5) .
C9 C17 1.507(5) .
C10 C11 1.487(5) .
C10 C19 1.511(5) .
C11 O1 1.208(5) .
C13 C14 1.525(5) .
C15 C16 1.524(5) .
C17 C18 1.536(6) .
C19 C20 1.521(6) .
O2 S1 1.499(3) .
S1 C92 1.784(5) .
S1 C91 1.798(5) .
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C14 H14A Br1 0.98 2.92 3.867(4) 162.8 .
N1 H01B O2 0.865(19) 2.13(2) 2.986(5) 170(4) .
N1 H01A O1 0.852(18) 2.20(2) 3.032(4) 167(4) 2_667
C92 H92C Br1 0.98 2.89 3.855(5) 169.8 2_667
C3 H3 O2 0.95 2.51 3.261(5) 136.0 2_666
