Charge and Spin States in Schiff Base Metal Complexes with a Disiloxane Unit Exhibiting a Strong Noninnocent Ligand Character: Synthesis, Structure, Spectroelectrochemistry, and Theoretical Calculations.
Cazacu, Maria; Shova, Sergiu; Soroceanu, Alina; Machata, Peter; Bucinsky, Lukas; Breza, Martin; Rapta, Peter; Telser, Joshua; Krzystek, J.; Arion, Vladimir B.; Inorganic chemistry 54 (2015) 5691–5706; doi:10.1021/acs.inorgchem.5b00229

data_4343111
_publ_section_title
;
 Charge and Spin States in Schiff Base Metal Complexes with a Disiloxane
 Unit Exhibiting a Strong Noninnocent Ligand Character: Synthesis,
 Structure, Spectroelectrochemistry, and Theoretical Calculations.
;
_journal_issue                   12
_journal_name_full               'Inorganic chemistry'
_journal_page_first              5691
_journal_page_last               5706
_journal_paper_doi               10.1021/acs.inorgchem.5b00229
_journal_volume                  54
_journal_year                    2015
_chemical_formula_moiety         'C40 H66 N2 Ni O3 Si2, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C40.5 H67 Cl N2 Ni O3 Si2'
_chemical_formula_weight         780.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 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                 100.734(8)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.4256(6)
_cell_length_b                   30.342(19)
_cell_length_c                   16.672(3)
_cell_measurement_reflns_used    3880
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      29.3725
_cell_measurement_theta_min      2.4060
_cell_volume                     4685(3)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET) (compiled Aug 3 2011,13:03:54)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET) (compiled Aug 3 2011,13:03:54)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET) (compiled Aug 3 2011,13:03:54)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SIR2008 (Burla et al., 2007)'
_diffrn_ambient_temperature      200.00(10)
_diffrn_detector_area_resol_mean 16.1593
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega   -5.00   50.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.4284   57.0000 -180.0000 55

  2 omega  -18.00   21.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.4284  -99.0000 -150.0000 39

  3 omega  -22.00   25.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.4284  -99.0000   30.0000 47

  4 omega   55.00   88.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       17.2409  178.0000 -150.0000 33

  5 omega  -38.00   32.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       17.2409  -19.0000 -120.0000 70
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0596291000
_diffrn_orient_matrix_UB_12      -0.0097589000
_diffrn_orient_matrix_UB_13      -0.0136790000
_diffrn_orient_matrix_UB_21      -0.0004087000
_diffrn_orient_matrix_UB_22      -0.0176347000
_diffrn_orient_matrix_UB_23      0.0280027000
_diffrn_orient_matrix_UB_31      -0.0480478000
_diffrn_orient_matrix_UB_32      -0.0119734000
_diffrn_orient_matrix_UB_33      -0.0300891000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0437
_diffrn_reflns_av_unetI/netI     0.0737
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            23331
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         26.00
_diffrn_reflns_theta_min         2.41
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.556
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84357
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET) (compiled Aug 3 2011,13:03:54) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'clear dark green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.106
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1684
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.799
_refine_diff_density_min         -0.438
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     460
_refine_ls_number_reflns         9187
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.1079
_refine_ls_R_factor_gt           0.0689
_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^)+(0.0833P)^2^+2.7086P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1663
_refine_ls_wR_factor_ref         0.1837
_reflns_number_gt                6235
_reflns_number_total             9187
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic5b00229_si_002.cif
_cod_data_source_block           shi_670_la
_cod_depositor_comments
'Adding full bibliography for 4343111--4343113.cif.'
_cod_original_formula_sum        'C40.50 H67 Cl N2 Ni O3 Si2'
_cod_database_code               4343111
_chemical_oxdiff_formula         'C40 H50 Ni1 N4 O3 Si2'
_chemical_oxdiff_usercomment     LA_91
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
2. Others
 Fixed Sof: Cl1(0.5) Cl2(0.5) C41(0.5) H41A(0.5) H41B(0.5)
3.a Riding coordinates:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C),
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C), C33(H33A,H33B,H33C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C),
 C39(H39A,H39B,H39C)
3.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C23(H23A,H23B), C24(H24A,
 H24B), C25(H25A,H25B), C41(H41A,H41B)
3.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C13(H13), C15(H15), C26(H26), C28(H28), C34(H34)
;