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_4343113
_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         'C42 H69 Mn N2 O5 Si2, 0.15(H2 O)'
_chemical_formula_sum            'C42 H69.3 Mn N2 O5.15 Si2'
_chemical_formula_weight         795.81
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-04-23
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                109.040(8)
_cell_angle_beta                 95.545(7)
_cell_angle_gamma                98.303(7)
_cell_formula_units_Z            6
_cell_length_a                   15.3998(13)
_cell_length_b                   21.477(2)
_cell_length_c                   22.0129(18)
_cell_measurement_reflns_used    5815
_cell_measurement_temperature    200.05(10)
_cell_measurement_theta_max      29.5270
_cell_measurement_theta_min      2.8554
_cell_volume                     6729.2(11)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_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      200.05(10)
_diffrn_detector_area_resol_mean 16.1593
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
  1 omega  -12.00   21.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.3503  -99.0000  -60.0000 33

  2 omega  -24.00    1.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.3503  -99.0000  150.0000 25

  3 omega   -1.00   85.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       17.1628   39.0000  -32.0000 86

  4 omega    1.00   28.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       17.1628   57.0000 -120.0000 27

  5 omega  -54.00   46.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       17.1628  -19.0000  -30.0000 100

  6 omega  -10.00   28.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       17.1628   77.0000  -90.0000 38

  7 omega    0.00   67.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       17.1628   57.0000 -180.0000 67

  8 omega   -4.00   44.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       17.1628  -77.0000   60.0000 48

  9 omega  -87.00  -35.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.3503 -178.0000   30.0000 52

 10 omega  -50.00   34.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       17.1628  -57.0000 -150.0000 84
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0221651000
_diffrn_orient_matrix_UB_12      -0.0246888000
_diffrn_orient_matrix_UB_13      0.0058938000
_diffrn_orient_matrix_UB_21      0.0380640000
_diffrn_orient_matrix_UB_22      0.0250069000
_diffrn_orient_matrix_UB_23      0.0162304000
_diffrn_orient_matrix_UB_31      -0.0166994000
_diffrn_orient_matrix_UB_32      0.0054711000
_diffrn_orient_matrix_UB_33      0.0298639000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1237
_diffrn_reflns_av_unetI/netI     0.1880
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            75413
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         25.50
_diffrn_reflns_theta_min         2.86
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.390
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64812
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.178
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             2577
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.021
_refine_diff_density_min         -0.574
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.979
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1388
_refine_ls_number_reflns         24946
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      0.983
_refine_ls_R_factor_all          0.2157
_refine_ls_R_factor_gt           0.0985
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1146P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2195
_refine_ls_wR_factor_ref         0.2760
_reflns_number_gt                10537
_reflns_number_total             24946
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic5b00229_si_002.cif
_cod_data_source_block           shi_818_al
_cod_depositor_comments
'Adding full bibliography for 4343111--4343113.cif.'
_cod_original_cell_volume        6729.3(10)
_cod_original_formula_sum        'C42 H69.30 Mn N2 O5.15 Si2'
_cod_database_code               4343113
_chemical_oxdiff_formula         'C40 H40 N2 O6 Si2 Mn1'
_chemical_oxdiff_usercomment     'AL_102, 0.5x0.2x0.1 verde inchis'
_reflns_odcompleteness_completeness 99.86
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C9B-C12Y \\sim C9B-C12B \\sim C9B-C11Y \\sim C9B-C11B \\sim C10B-C9B
 with sigma of 0.01
 Si2A-C19X \\sim Si2A-C19A
 with sigma of 0.01
 Si2A-C20X \\sim Si2A-C20A
 with sigma of 0.01
 Si2B-C22Y \\sim Si2B-C22B
 with sigma of 0.01
 C25B-C24B \\sim C25B-C24Y \\sim C23Y-C24Y \\sim C23B-C24B
 with sigma of 0.01
 Si2B-C23B \\sim Si2B-C23Y
 with sigma of 0.01
 Si1B-C20Y \\sim Si1B-C20B
 with sigma of 0.01
 C9C-C10C \\sim C9C-C3Z \\sim C9C-C12C \\sim C9C-C2Z \\sim C9C-C11C \\sim
C9C-C1Z
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C16B) \\sim Ueq, Uanis(C17B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uiso(C11B) = Uiso(C11Y)
Uiso(C12Y) = Uiso(C12B)
Uiso(C19X) = Uiso(C19A)
Uiso(C20A) = Uiso(C20X)
Uiso(C22B) = Uiso(C22Y)
Uiso(C23B) = Uiso(C23Y) = Uiso(C24B) = Uiso(C24Y)
Uiso(C20Y) = Uiso(C20B)
Uiso(C3Z) = Uiso(C12C) = Uiso(C2Z) = Uiso(C11C) = Uiso(C1Z) = Uiso(C10C)
4. Others
 Fixed Sof: H25A(0.6) H25B(0.6) H25C(0.4) H25D(0.4) C24B(0.6) H24A(0.6)
 H24B(0.6) C1Z(0.5) H1ZA(0.5) H1ZB(0.5) H1ZC(0.5) C12Y(0.5) H12A(0.5) H12B(0.5)
 H12C(0.5) C23B(0.6) H23A(0.6) H23B(0.6) C11B(0.5) H11A(0.5) H11B(0.5)
 H11C(0.5) C12C(0.5) H12G(0.5) H12H(0.5) H12I(0.5) C22Y(0.5) H22A(0.5)
 H22B(0.5) H22C(0.5) C20A(0.5) H20J(0.5) H20K(0.5) H20L(0.5) C11C(0.5)
 H11G(0.5) H11H(0.5) H11I(0.5) C20Y(0.5) H20A(0.5) H20B(0.5) H20C(0.5)
 C19A(0.5) H19G(0.5) H19H(0.5) H19I(0.5) C24Y(0.4) H24C(0.4) H24D(0.4)
 C23Y(0.4) H23C(0.4) H23D(0.4) C2Z(0.5) H2ZA(0.5) H2ZB(0.5) H2ZC(0.5) C11Y(0.5)
 H11D(0.5) H11E(0.5) H11F(0.5) C20B(0.5) H20D(0.5) H20E(0.5) H20F(0.5)
 C12B(0.5) H12D(0.5) H12E(0.5) H12F(0.5) C19X(0.5) H19J(0.5) H19K(0.5)
 H19L(0.5) C20X(0.5) H20M(0.5) H20N(0.5) H20O(0.5) C22B(0.5) H22D(0.5)
 H22E(0.5) H22F(0.5) O2W(0.25) H2WA(0.25) H2WB(0.25) O1W(0.2) H1WA(0.2)
 H1WB(0.2) C10C(0.5) H10D(0.5) H10E(0.5) H10F(0.5) C3Z(0.5) H3ZA(0.5) H3ZB(0.5)
 H3ZC(0.5)
5.a Riding coordinates:
 C38B(H38A,H38B,H38C), C5C(H5CA,H5CB,H5CC), C6C(H6CA,H6CB,H6CC), C32B(H32A,
 H32B,H32C), C32C(H32D,H32E,H32F), C33B(H33A,H33B,H33C), C11A(H11J,H11K,H11L),
 C10A(H10G,H10H,H10I), C31B(H31A,H31B,H31C), C33C(H33D,H33E,H33F), C4C(H4CA,
 H4CB,H4CC), C38C(H38D,H38E,H38F), C5A(H5AA,H5AB,H5AC), C5B(H5BA,H5BB,H5BC),
 C31C(H31D,H31E,H31F), C39B(H39A,H39B,H39C), C42C(H42D,H42E,H42F), C12A(H12J,
 H12K,H12L), C32A(H32G,H32H,H32I), C6B(H6BA,H6BB,H6BC), C33A(H33G,H33H,H33I),
 C39A(H39G,H39H,H39I), C42A(H42G,H42H,H42I), C10B(H10A,H10B,H10C), C22C(H22G,
 H22H,H22I), C37B(H37A,H37B,H37C), C4B(H4BA,H4BB,H4BC), C37A(H37G,H37H,H37I),
 C37C(H37D,H37E,H37F), C4A(H4AA,H4AB,H4AC), C21A(H21G,H21H,H21I), C6A(H6AA,H6AB,
 H6AC), C42B(H42A,H42B,H42C), C31A(H31G,H31H,H31I), C19B(H19A,H19B,H19C),
 C1Z(H1ZA,H1ZB,H1ZC), C39C(H39D,H39E,H39F), C22A(H22J,H22K,H22L), C38A(H38G,
 H38H,H38I), C19C(H19D,H19E,H19F), C20C(H20G,H20H,H20I), C21B(H21A,H21B,H21C),
 C12Y(H12A,H12B,H12C), C11B(H11A,H11B,H11C), C12C(H12G,H12H,H12I), C22Y(H22A,
 H22B,H22C), C21C(H21D,H21E,H21F), C20A(H20J,H20K,H20L), C11C(H11G,H11H,H11I),
 C20Y(H20A,H20B,H20C), C19A(H19G,H19H,H19I), C2Z(H2ZA,H2ZB,H2ZC), C11Y(H11D,
 H11E,H11F), C20B(H20D,H20E,H20F), C12B(H12D,H12E,H12F), C19X(H19J,H19K,H19L),
 C20X(H20M,H20N,H20O), C22B(H22D,H22E,H22F), O2W(H2WA,H2WB), O1W(H1WA,H1WB),
 C10C(H10D,H10E,H10F), C3Z(H3ZA,H3ZB,H3ZC)
5.b Secondary CH2 refined with riding coordinates:
 C25C(H25E,H25F), C16C(H16C,H16D), C16A(H16E,H16F), C25A(H25G,H25H), C23C(H23E,
 H23F), C25B(H25A,H25B), C25B(H25C,H25D), C24C(H24E,H24F), C24A(H24G,H24H),
 C17A(H17E,H17F), C16B(H16A,H16B), C17C(H17C,H17D), C18C(H18C,H18D), C23A(H23G,
 H23H), C18A(H18E,H18F), C17B(H17A,H17B), C18B(H18A,H18B), C24B(H24A,H24B),
 C23B(H23A,H23B), C24Y(H24C,H24D), C23Y(H23C,H23D)
5.c Aromatic/amide H refined with riding coordinates:
 C13B(H13B), C13A(H13A), C13C(H13C), C26C(H26C), C7B(H7B), C40A(H40A),
 C7A(H7A), C34C(H34C), C15A(H15A), C7C(H7C), C26A(H26A), C26B(H26B), C15C(H15C),
  C15B(H15B), C34A(H34A), C40C(H40C), C40B(H40B), C34B(H34B)
;