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_4343112
_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 Cu N2 O3 Si2'
_chemical_formula_sum            'C40 H66 Cu N2 O3 Si2'
_chemical_formula_weight         742.67
_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     heavy
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-04-23
_cell_angle_alpha                90.00
_cell_angle_beta                 110.435(12)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   14.2195(12)
_cell_length_b                   19.482(3)
_cell_length_c                   17.222(2)
_cell_measurement_reflns_used    3578
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.1566
_cell_measurement_theta_min      2.4351
_cell_volume                     4470.7(10)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.1593
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -78.00  -48.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.4284  178.0000  -60.0000 30

  2 omega  -20.00    9.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.4284  -99.0000 -120.0000 29

  3 omega  -16.00   22.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.4284  -99.0000   60.0000 38

  4 omega  -31.00   -4.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.4284   77.0000  -30.0000 27

  5 omega  -44.00   57.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.4284   19.0000  -90.0000 101
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0062605000
_diffrn_orient_matrix_UB_12      -0.0361046000
_diffrn_orient_matrix_UB_13      0.0024649000
_diffrn_orient_matrix_UB_21      0.0243259000
_diffrn_orient_matrix_UB_22      0.0014637000
_diffrn_orient_matrix_UB_23      -0.0295818000
_diffrn_orient_matrix_UB_31      0.0469249000
_diffrn_orient_matrix_UB_32      0.0040675000
_diffrn_orient_matrix_UB_33      0.0324547000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0374
_diffrn_reflns_av_unetI/netI     0.0670
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            20612
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         26.00
_diffrn_reflns_theta_min         2.44
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.576
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88991
_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    1.103
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1604
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.554
_refine_diff_density_min         -0.431
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     428
_refine_ls_number_reflns         8779
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.1184
_refine_ls_R_factor_gt           0.0666
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0825P)^2^+0.7697P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1564
_refine_ls_wR_factor_ref         0.1795
_reflns_number_gt                5373
_reflns_number_total             8779
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic5b00229_si_002.cif
_cod_data_source_block           shi_498_la
_cod_depositor_comments
'Adding full bibliography for 4343111--4343113.cif.'
_cod_original_cell_volume        4470.5(10)
_cod_database_code               4343112
_chemical_oxdiff_formula         'C40 H40 Cu1 N2 O5'
_chemical_oxdiff_usercomment     LA_74
_reflns_odcompleteness_completeness 99.89
_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. Restrained distances
 C35X-C33 \\sim C34-C33 \\sim C34X-C33 \\sim C36-C33 \\sim C36X-C33 \\sim
C35-C33 \\sim C25-C27 \\sim C25-
 C27X \\sim C25-C26 \\sim C25-C28X \\sim C25-C28 \\sim C25-C26X
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(C34) = Uiso(C34X) = Uiso(C36) = Uiso(C36X) = Uiso(C35) = Uiso(C35X) =
Uiso(C27X) = Uiso(C27) = Uiso(C28) = Uiso(C28X) = Uiso(C26X) = Uiso(C26)
4. Others
 Sof(C27X)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28X)=Sof(H28D)=Sof(H28E)=
 Sof(H28F)=Sof(C26X)=Sof(H26D)=Sof(H26E)=Sof(H26F)=1-FVAR(1)
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
 Sof(C36X)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C35X)=Sof(H35D)=Sof(H35E)=
 Sof(H35F)=Sof(C34X)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(2)
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C36)=Sof(H36D)=Sof(H36E)=Sof(H36F)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(2)
5.a Riding coordinates:
 C34(H34A,H34B,H34C), C36X(H36A,H36B,H36C), C28(H28A,H28B,H28C), C27(H27A,H27B,
 H27C), C26(H26A,H26B,H26C), C36(H36D,H36E,H36F), C35(H35A,H35B,H35C),
 C35X(H35D,H35E,H35F), C34X(H34D,H34E,H34F), C27X(H27D,H27E,H27F), C28X(H28D,
 H28E,H28F), C26X(H26D,H26E,H26F)
5.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C8(H8A,H8B), C17(H17A,H17B), C16(H16A,H16B), C10(H10A,H10B),
 C9(H9A,H9B)
5.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C20(H20), C22(H22), C3(H3), C7(H7), C5(H5)
5.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C40(H40A,H40B,H40C), C31(H31A,H31B,
 H31C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C11(H11A,H11B,H11C), C13(H13A,
 H13B,H13C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C)
;