Electrocatalytic Reduction of CO2 with Palladium Bis-N-heterocyclic Carbene Pincer Complexes.
Therrien, Jeffrey A.; Wolf, Michael O.; Patrick, Brian O.; Inorganic chemistry  (2014) 141022083740000–; doi:10.1021/ic502056w

data_4341351
_publ_section_title
;
 Electrocatalytic Reduction of CO2 with Palladium Bis-N-heterocyclic
 Carbene Pincer Complexes.
;
_journal_name_full               'Inorganic chemistry'
_journal_page_first              141022083740000
_journal_paper_doi               10.1021/ic502056w
_journal_year                    2014
_chemical_formula_moiety
'C23 H32 N6 Pd, 0.5(C H2 Cl2), 2(B1 F4), 0.22(H2 O)'
_chemical_formula_sum            'C23.5 H33.75 B2 Cl F8 N6 O0.19 Pd'
_chemical_formula_weight         718.90
_chemical_name_systematic
;
 ?
;
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-09-22
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                76.396(8)
_cell_angle_beta                 85.371(9)
_cell_angle_gamma                69.781(8)
_cell_formula_units_Z            2
_cell_length_a                   8.3763(12)
_cell_length_b                   11.8244(17)
_cell_length_c                   16.462(3)
_cell_measurement_reflns_used    9920
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.11
_cell_measurement_theta_min      2.50
_cell_volume                     1487.1(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker-Nonius APEXII CCD area detector'
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_device
'Bruker-Nonius APEXII CCD area detector and D8 diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'TRIUMPH curved-crystal'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0402
_diffrn_reflns_av_unetI/netI     0.0610
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            26630
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.151
_diffrn_reflns_theta_min         1.882
_diffrn_source                   'sealed X-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.791
_exptl_absorpt_correction_T_max  0.895
_exptl_absorpt_correction_T_min  0.799
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/3 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0704 before and 0.0512 after correction.
The Ratio of minimum to maximum transmission is 0.8933.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.606
_exptl_crystal_description       irregular
_exptl_crystal_F_000             727
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.870
_refine_diff_density_min         -1.037
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     468
_refine_ls_number_reflns         7767
_refine_ls_number_restraints     533
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0667
_refine_ls_R_factor_gt           0.0468
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0504P)^2^+1.4389P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1012
_refine_ls_wR_factor_ref         0.1110
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6151
_reflns_number_total             7767
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic502056w_si_002.cif
_cod_data_source_block           mw221
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_radiation_probe' value 'X-ray' changed to 'x-ray' according
to
/home/saulius/struct/COD-crude-data--automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 2827 2014-09-09 07:05:25Z andrius 
;
_cod_original_formula_sum        'C23.50 H33.75 B2 Cl F8 N6 O0.19 Pd'
_cod_database_code               4341351
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.897
_shelx_estimated_absorpt_t_min   0.815
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 Cl1-Cl1_$1
 2.93 with sigma of 0.01
 C24-Cl1
 1.75 with sigma of 0.01
 C25-Cl3
 1.75 with sigma of 0.01
 C18-C19 \\sim C19-C20 \\sim C20-C21
 with sigma of 0.01
 C18A-C19A \\sim C19A-C20A \\sim C20A-C21A
 with sigma of 0.01
 C18-C20 \\sim C19-C21
 with sigma of 0.01
 C18A-C20A \\sim C19A-C21A
 with sigma of 0.091
 B1-F1 \\sim B1-F2 \\sim B1-F3 \\sim B1-F4
 with sigma of 0.01
 F1-F2 \\sim F1-F3 \\sim F1-F4 \\sim F2-F3 \\sim F2-F4 \\sim F3-F4
 with sigma of 0.01
 B1A-F1A \\sim B1A-F2A \\sim B1A-F3A \\sim B1A-F4A
 with sigma of 0.01
 F1A-F2A \\sim F1A-F3A \\sim F1A-F4A \\sim F2A-F3A \\sim F2A-F4A \\sim F3A-F4A
 with sigma of 0.01
 B2-F5 \\sim B2-F6 \\sim B2-F7 \\sim B2-F8
 with sigma of 0.01
 F5-F6 \\sim F5-F7 \\sim F5-F8 \\sim F6-F7 \\sim F6-F8 \\sim F7-F8
 with sigma of 0.01
 B2A-F5A \\sim B2A-F6A \\sim B2A-F7A \\sim B2A-F8A
 with sigma of 0.01
 F5A-F6A \\sim F5A-F7A \\sim F5A-F8A \\sim F6A-F7A \\sim F6A-F8A \\sim F7A-F8A
 with sigma of 0.01
 C24-Cl1 \\sim C24-Cl1_$1 \\sim C25-Cl2
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C22A) = Uanis(C22)
Uanis(N6A) = Uanis(N6)
Uanis(C21A) = Uanis(C21)
Uanis(C20A) = Uanis(C20)
Uanis(C19A) = Uanis(C19)
Uanis(C18A) = Uanis(C18)
Uanis(B1) = Uanis(B1A)
Uanis(F3A) = Uanis(F3)
Uanis(F1A) = Uanis(F1)
Uanis(F2) = Uanis(F2A)
Uanis(F4A) = Uanis(F4)
Uanis(F7) = Uanis(F7A)
Uanis(F5A) = Uanis(F5)
Uanis(F8) = Uanis(F8A)
Uanis(F6) = Uanis(F6A)
Uanis(B2) = Uanis(B2A)
Uanis(Cl2) = Uanis(Cl1)
Uanis(Cl3) = Uanis(Cl1) = Uanis(Cl2)
Uanis(C24) = Uanis(C25)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(N6A)=Sof(C22A)=Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(1)
 Sof(N6)=Sof(C22)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
 Sof(C18A)=Sof(H18C)=Sof(H18D)=Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C20A)=
 Sof(H20C)=Sof(H20D)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(2)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=
 Sof(H20B)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(2)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(B1A)=1-FVAR(3)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(B1)=FVAR(3)
 Sof(F5A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=Sof(B2A)=1-FVAR(4)
 Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(B2)=FVAR(4)
 Sof(Cl2)=Sof(Cl3)=Sof(C25)=Sof(H25A)=Sof(H25B)=0.5*(1-FVAR(6))
 Sof(C24)=Sof(H24A)=Sof(H24B)=0.5*FVAR(6)
 Sof(Cl1)=FVAR(5)
 Sof(O1)=Sof(H1D)=Sof(H1E)=FVAR(6)
6.a Free rotating group:
 O1(H1D,H1E)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C8(H8A,H8B), C14(H14A,H14B), C18(H18A,
 H18B), C19(H19A,H19B), C20(H20A,H20B), C18A(H18C,H18D), C19A(H19C,H19D),
 C20A(H20C,H20D), C25(H25A,H25B), C24(H24A,H24B)
6.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C10(H10), C11(H11), C12(H12), C16(H16), C17(H17)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C21A(H21D,H21E,
 H21F), C23A(H23D,H23E,H23F)
;
_shelx_res_checksum              46830
_shelx_hkl_checksum              8445
_olex2_submission_special_instructions 'No special instructions were received'