#------------------------------------------------------------------------------
#$Date: 2019-10-28 11:16:17 +0200 (Mon, 28 Oct 2019) $
#$Revision: 220006 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/51/48/4514845.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_4514845
loop_
_publ_author_name
'Romine, Andrew M.'
'Yang, Kin S.'
'Karunananda, Malkanthi K.'
'Chen, Jason S.'
'Engle, Keary M.'
_publ_section_title
;
 Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether
 Directing Group for Pd(II) Catalysis
;
_journal_issue                   9
_journal_name_full               'ACS Catalysis'
_journal_page_first              7626
_journal_paper_doi               10.1021/acscatal.9b01471
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C32 H22 F6 N2 O4 Pd S4, C2 H4 Cl2'
_chemical_formula_sum            'C34 H26 Cl2 F6 N2 O4 Pd S4'
_chemical_formula_weight         946.11
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-01
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                68.768(3)
_cell_angle_beta                 89.673(5)
_cell_angle_gamma                88.327(3)
_cell_formula_units_Z            1
_cell_length_a                   9.0381(9)
_cell_length_b                   10.3207(12)
_cell_length_c                   10.3832(11)
_cell_measurement_reflns_used    1838
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.30
_cell_measurement_theta_min      2.38
_cell_volume                     902.40(17)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2016)'
_computing_data_collection       'APEX3 v2016.1-0 (Bruker, 2016)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 8.258
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0384
_diffrn_reflns_av_unetI/netI     0.0405
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            10713
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.308
_diffrn_reflns_theta_min         2.104
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.967
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6793
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0657 before and 0.0481 after correction.
The Ratio of minimum to maximum transmission is 0.9110.
The λ/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.741
_exptl_crystal_description       block
_exptl_crystal_F_000             474
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.28
_refine_diff_density_max         1.071
_refine_diff_density_min         -0.431
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     269
_refine_ls_number_reflns         4397
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0369
_refine_ls_R_factor_gt           0.0317
_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/[σ²(Fo²)+(0.0248P)²+1.3308P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0773
_refine_ls_wR_factor_ref         0.0825
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3984
_reflns_number_total             4397
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            cs9b01471_si_014.cif
_cod_data_source_block           engle114_0m_a
_cod_database_code               4514845
_shelx_shelxl_version_number     2016/6
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_shelx_estimated_absorpt_t_max   0.773
_shelx_estimated_absorpt_t_min   0.760
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 F3'-C15 \\sim F1'-C15 \\sim F2'-C15
 with sigma of 0.01
 F3'-C15 \\sim F1-C15 \\sim F1'-C15 \\sim F2-C15 \\sim F2'-C15 \\sim F3-C15
 with sigma of 0.01
3. Others
 Sof(F3)=Sof(F1)=Sof(F2)=1-FVAR(1)
 Sof(F2')=Sof(F3')=Sof(F1')=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C7(H7A,H7B)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C2(H2), C9(H9), C13(H13), C11(H11), C10(H10), C3(H3), C12(H12), C4(H4)
;
_olex2_submission_special_instructions 'No special instructions were received'
loop_
_space_group_symop_operation_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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Pd1 Pd 0.500000 0.500000 0.500000 0.01518(7) Uani 1 2 d S T P . .
S1 S 0.49560(7) 0.25454(6) 0.21691(6) 0.02057(13) Uani 1 1 d . . . . .
S2 S 0.37482(7) 0.54516(6) 0.18647(6) 0.02416(14) Uani 1 1 d . . . . .
Cl1 Cl 0.71011(8) 0.09806(7) 0.97761(8) 0.03543(16) Uani 1 1 d . . . . .
O1 O 0.28874(18) 0.44361(17) 0.53686(17) 0.0220(3) Uani 1 1 d . . . . .
N1 N 0.5258(2) 0.36789(19) 0.39809(19) 0.0170(4) Uani 1 1 d . . . . .
F2' F 0.0846(3) 0.1627(3) 0.7388(4) 0.0476(10) Uani 0.838(10) 1 d D . . A 1
F3' F 0.0461(3) 0.2996(4) 0.5329(2) 0.0567(16) Uani 0.838(10) 1 d D . . A 1
F1' F 0.0242(3) 0.3700(3) 0.7025(4) 0.0466(10) Uani 0.838(10) 1 d D . . A 1
O2 O 0.3546(2) 0.2537(2) 0.7209(2) 0.0419(5) Uani 1 1 d . . . . .
C6 C 0.5991(2) 0.1635(2) 0.3639(2) 0.0184(4) Uani 1 1 d . . . . .
C1 C 0.6047(2) 0.2407(2) 0.4501(2) 0.0171(4) Uani 1 1 d . . . . .
C8 C 0.1700(3) 0.3918(2) 0.0983(2) 0.0220(5) Uani 1 1 d . . . . .
C15 C 0.1016(3) 0.2929(2) 0.6499(2) 0.0256(5) Uani 1 1 d D . . . .
C5 C 0.6675(3) 0.0323(2) 0.4006(3) 0.0226(5) Uani 1 1 d . . . . .
H5 H 0.661091 -0.021066 0.343168 0.027 Uiso 1 1 calc R . . . .
C19 C 0.4654(3) 0.3891(2) 0.2774(2) 0.0181(4) Uani 1 1 d . . . . .
C2 C 0.6822(3) 0.1893(2) 0.5747(2) 0.0213(5) Uani 1 1 d . . . . .
H2 H 0.686980 0.241401 0.633494 0.026 Uiso 1 1 calc R . . . .
C9 C 0.0777(3) 0.3742(3) 0.2105(3) 0.0262(5) Uani 1 1 d . . . . .
H9 H 0.085246 0.433599 0.261732 0.031 Uiso 1 1 calc R . . . .
C13 C 0.1573(3) 0.3041(3) 0.0247(3) 0.0258(5) Uani 1 1 d . . . . .
H13 H 0.219547 0.315691 -0.052506 0.031 Uiso 1 1 calc R . . . .
C14 C 0.2669(3) 0.3309(3) 0.6386(2) 0.0222(5) Uani 1 1 d . . . . .
C11 C -0.0367(3) 0.1831(3) 0.1748(3) 0.0295(5) Uani 1 1 d . . . . .
H11 H -0.106947 0.111498 0.201204 0.035 Uiso 1 1 calc R . . . .
C10 C -0.0256(3) 0.2701(3) 0.2478(3) 0.0284(5) Uani 1 1 d . . . . .
H10 H -0.088859 0.258860 0.324248 0.034 Uiso 1 1 calc R . . . .
C3 C 0.7519(3) 0.0604(3) 0.6102(3) 0.0260(5) Uani 1 1 d . . . . .
H3 H 0.805460 0.023312 0.694782 0.031 Uiso 1 1 calc R . . . .
C20 C 0.5597(3) 0.0023(3) 0.9501(3) 0.0354(6) Uani 1 1 d . . . . .
H20A H 0.521504 0.047440 0.854582 0.042 Uiso 1 1 calc R . . . .
H20B H 0.594217 -0.093370 0.962588 0.042 Uiso 1 1 calc R . . . .
C12 C 0.0547(3) 0.2000(3) 0.0625(3) 0.0298(5) Uani 1 1 d . . . . .
H12 H 0.046969 0.140288 0.011629 0.036 Uiso 1 1 calc R . . . .
C4 C 0.7452(3) -0.0169(3) 0.5244(3) 0.0264(5) Uani 1 1 d . . . . .
H4 H 0.795054 -0.105116 0.551435 0.032 Uiso 1 1 calc R . . . .
C7 C 0.2807(3) 0.5060(3) 0.0509(2) 0.0259(5) Uani 1 1 d . . . . .
H7A H 0.228935 0.591938 -0.010257 0.031 Uiso 1 1 calc R . . . .
H7B H 0.356605 0.480149 -0.005375 0.031 Uiso 1 1 calc R . . . .
F3 F 0.0806(15) 0.1765(15) 0.634(3) 0.072(10) Uani 0.162(10) 1 d D . . A 2
F1 F 0.0096(12) 0.3901(17) 0.567(3) 0.099(14) Uani 0.162(10) 1 d D . . A 2
F2 F 0.030(2) 0.276(4) 0.7624(18) 0.117(16) Uani 0.162(10) 1 d D . . A 2
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'
Cl Cl 0.1484 0.1585 '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'
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'
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'
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
O1 Pd1 O1 180.0 2_666 .
O1 Pd1 N1 90.86(7) 2_666 .
O1 Pd1 N1 89.14(7) . .
O1 Pd1 N1 89.14(7) 2_666 2_666
O1 Pd1 N1 90.86(7) . 2_666
N1 Pd1 N1 180.00(7) . 2_666
C19 S1 C6 90.03(11) . .
C19 S2 C7 102.35(11) . .
C14 O1 Pd1 116.19(15) . .
C1 N1 Pd1 124.09(15) . .
C19 N1 Pd1 123.57(16) . .
C19 N1 C1 112.29(19) . .
C1 C6 S1 109.85(17) . .
C5 C6 S1 128.55(19) . .
C5 C6 C1 121.6(2) . .
C6 C1 N1 113.42(19) . .
C2 C1 N1 126.0(2) . .
C2 C1 C6 120.6(2) . .
C9 C8 C7 122.2(2) . .
C13 C8 C9 119.1(2) . .
C13 C8 C7 118.7(2) . .
F2' C15 C14 110.6(2) . .
F3' C15 F2' 106.9(3) . .
F3' C15 F1' 111.0(3) . .
F3' C15 C14 112.5(2) . .
F1' C15 F2' 104.5(2) . .
F1' C15 C14 110.9(2) . .
F3 C15 C14 112.5(7) . .
F3 C15 F1 109.4(14) . .
F3 C15 F2 101.6(16) . .
F1 C15 C14 115.5(6) . .
F2 C15 C14 120.0(8) . .
F2 C15 F1 96.0(16) . .
C6 C5 H5 121.4 . .
C4 C5 C6 117.1(2) . .
C4 C5 H5 121.4 . .
S2 C19 S1 124.82(13) . .
N1 C19 S1 114.40(17) . .
N1 C19 S2 120.65(17) . .
C1 C2 H2 121.0 . .
C3 C2 C1 117.9(2) . .
C3 C2 H2 121.0 . .
C8 C9 H9 119.9 . .
C8 C9 C10 120.2(2) . .
C10 C9 H9 119.9 . .
C8 C13 H13 119.7 . .
C12 C13 C8 120.7(2) . .
C12 C13 H13 119.7 . .
O1 C14 C15 111.3(2) . .
O2 C14 O1 129.8(2) . .
O2 C14 C15 118.9(2) . .
C10 C11 H11 120.1 . .
C10 C11 C12 119.9(3) . .
C12 C11 H11 120.1 . .
C9 C10 H10 119.8 . .
C11 C10 C9 120.4(2) . .
C11 C10 H10 119.8 . .
C2 C3 H3 119.3 . .
C2 C3 C4 121.4(2) . .
C4 C3 H3 119.3 . .
Cl1 C20 H20A 109.8 . .
Cl1 C20 H20B 109.8 . .
C20 C20 Cl1 109.4(3) 2_657 .
C20 C20 H20A 109.8 2_657 .
C20 C20 H20B 109.8 2_657 .
H20A C20 H20B 108.2 . .
C13 C12 C11 119.9(2) . .
C13 C12 H12 120.1 . .
C11 C12 H12 120.1 . .
C5 C4 C3 121.4(2) . .
C5 C4 H4 119.3 . .
C3 C4 H4 119.3 . .
S2 C7 H7A 108.3 . .
S2 C7 H7B 108.3 . .
C8 C7 S2 116.12(17) . .
C8 C7 H7A 108.3 . .
C8 C7 H7B 108.3 . .
H7A C7 H7B 107.4 . .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Pd1 O1 2.0065(16) 2_666
Pd1 O1 2.0065(16) .
Pd1 N1 2.0142(18) 2_666
Pd1 N1 2.0142(18) .
S1 C6 1.736(2) .
S1 C19 1.734(2) .
S2 C19 1.728(2) .
S2 C7 1.820(2) .
Cl1 C20 1.787(3) .
O1 C14 1.276(3) .
N1 C1 1.400(3) .
N1 C19 1.311(3) .
F2' C15 1.340(3) .
F3' C15 1.295(3) .
F1' C15 1.304(3) .
O2 C14 1.213(3) .
C6 C1 1.399(3) .
C6 C5 1.392(3) .
C1 C2 1.392(3) .
C8 C9 1.389(4) .
C8 C13 1.387(3) .
C8 C7 1.509(4) .
C15 C14 1.549(3) .
C15 F3 1.288(7) .
C15 F1 1.330(7) .
C15 F2 1.288(7) .
C5 H5 0.9500 .
C5 C4 1.386(4) .
C2 H2 0.9500 .
C2 C3 1.379(3) .
C9 H9 0.9500 .
C9 C10 1.390(4) .
C13 H13 0.9500 .
C13 C12 1.385(4) .
C11 H11 0.9500 .
C11 C10 1.375(4) .
C11 C12 1.386(4) .
C10 H10 0.9500 .
C3 H3 0.9500 .
C3 C4 1.398(4) .
C20 C20 1.480(6) 2_657
C20 H20A 0.9900 .
C20 H20B 0.9900 .
C12 H12 0.9500 .
C4 H4 0.9500 .
C7 H7A 0.9900 .
C7 H7B 0.9900 .
