Reduction of 2,2'-Bipyridine by Quasi-Linear 3d-Metal(I) Silylamides-A Structural and Spectroscopic Study
Muller, I.; Schneider, C.; Pietzonka, C.; Kraus, F.; Werncke, C.G.; Inorganics 7 (2019) 117–; doi:10.3390/inorganics7100117

data_1556441
_publ_section_title
;
 Reduction of 2,2'-Bipyridine by Quasi-Linear 3d-Metal(I) Silylamides-A
 Structural and Spectroscopic Study
;
_journal_name_full               Inorganics
_journal_page_first              117
_journal_paper_doi               10.3390/inorganics7100117
_journal_volume                  7
_journal_year                    2019
_chemical_formula_moiety
'0.25(C124 H248 K3 Mn4 N16 O18 Si16), 0.25(C12 H24 K O6)'
_chemical_formula_sum            'C34 H68 K Mn N4 O6 Si4'
_chemical_formula_weight         835.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_cell_angle_alpha                90
_cell_angle_beta                 96.555(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   34.8403(17)
_cell_length_b                   18.4715(11)
_cell_length_c                   14.5302(8)
_cell_measurement_reflns_used    45955
_cell_measurement_temperature    150
_cell_measurement_theta_max      29.435
_cell_measurement_theta_min      1.83
_cell_volume                     9289.8(9)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'STOE IPDS-2T'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0285
_diffrn_reflns_av_unetI/netI     0.0488
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       43
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            52126
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         1.834
_exptl_absorpt_coefficient_mu    0.518
_exptl_absorpt_correction_T_max  0.9764
_exptl_absorpt_correction_T_min  0.7891
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   'STOE X-Area'
_exptl_crystal_colour            'clear dark violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.194
_exptl_crystal_description       block
_exptl_crystal_F_000             3584
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.816
_refine_diff_density_min         -0.209
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.086(13)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.911
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1270
_refine_ls_number_reflns         21354
_refine_ls_number_restraints     1546
_refine_ls_restrained_S_all      0.890
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0368
_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^)+(0.0442P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0753
_refine_ls_wR_factor_ref         0.0786
_reflns_Friedel_coverage         0.940
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                16849
_reflns_number_total             21354
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            K_18c6_Mn2.cif
_cod_data_source_block           k(18c6)mn6
_cod_database_code               1556441
_shelx_estimated_absorpt_t_max   0.965
_shelx_estimated_absorpt_t_min   0.873
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.914(13)
 0.086(13)
2. 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
3. Restrained distances
 C1_1-C2_1 = C3_1-C4_1 = C5_1-C6_1 = C7_1-C8_1 = C9_1-C10_1 = C11_1-C12_1
 1.45 with sigma of 0.02
 O1_1-C1_1 \\sim O1_1-C12_1 \\sim O2_1-C2_1 \\sim O2_1-C3_1 \\sim O3_1-C4_1
\\sim O3_1-C5_1 \\sim O4_1-
 C6_1 \\sim O4_1-C7_1 \\sim O5_1-C8_1 \\sim O5_1-C9_1 \\sim O6_1-C10_1 \\sim
O6_1-C11_1
 O1_2-C1_2 \\sim O1_2-C12_2 \\sim O2_2-C2_2 \\sim O2_2-C3_2 \\sim O3_2-C4_2
\\sim O3_2-C5_2 \\sim O4_2-
 C6_2 \\sim O4_2-C7_2 \\sim O5_2-C8_2 \\sim O5_2-C9_2 \\sim O6_2-C10_2 \\sim
O6_2-C11_2
 O1_3-C1_3 \\sim O1_3-C12_3 \\sim O2_3-C2_3 \\sim O2_3-C3_3 \\sim O3_3-C4_3
\\sim O3_3-C5_3 \\sim O4_3-
 C6_3 \\sim O4_3-C7_3 \\sim O5_3-C8_3 \\sim O5_3-C9_3 \\sim O6_3-C10_3 \\sim
O6_3-C11_3
 with sigma of 0.02
 C1_1-C2_1 \\sim C3_1-C4_1 \\sim C5_1-C6_1 \\sim C7_1-C8_1 \\sim C9_1-C10_1
\\sim C11_1-C12_1
 C1_2-C2_2 \\sim C3_2-C4_2 \\sim C5_2-C6_2 \\sim C7_2-C8_2 \\sim C9_2-C10_2
\\sim C11_2-C12_2
 C1_3-C2_3 \\sim C3_3-C4_3 \\sim C5_3-C6_3 \\sim C7_3-C8_3 \\sim C9_3-C10_3
\\sim C11_3-C12_3
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O1_1 \\sim O2_1 \\sim O3_1 \\sim O4_1 \\sim O5_1 \\sim O6_1 \\sim C1_1 \\sim
C2_1 \\sim C3_1 \\sim C4_1 \\sim C5_1 \\sim C6_1 \\sim C7_1 \\sim C8_1 \\sim
C9_1 \\sim C10_1 \\sim C11_1 \\sim C12_1 \\sim O1_2 \\sim O2_2 \\sim O3_2 \\sim
O4_2 \\sim O5_2 \\sim O6_2 \\sim C1_2 \\sim C2_2 \\sim C3_2 \\sim C4_2 \\sim
C5_2 \\sim C6_2 \\sim C7_2 \\sim C8_2 \\sim C9_2 \\sim C10_2 \\sim C11_2 \\sim
C12_2 \\sim O1_3 \\sim O2_3 \\sim O3_3 \\sim O4_3 \\sim O5_3 \\sim O6_3 \\sim
C1_3 \\sim C2_3 \\sim C3_3 \\sim C4_3 \\sim C5_3 \\sim C6_3 \\sim C7_3 \\sim
C8_3 \\sim C9_3 \\sim C10_3 \\sim C11_3 \\sim C12_3: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
Uanis(O1_1) \\sim Ueq, Uanis(O2_1) \\sim Ueq, Uanis(O3_1) \\sim Ueq,
Uanis(O4_1) \\sim Ueq, Uanis(O5_1) \\sim Ueq, Uanis(O6_1) \\sim Ueq,
Uanis(C1_1) \\sim Ueq, Uanis(C2_1) \\sim Ueq, Uanis(C3_1) \\sim Ueq,
Uanis(C4_1) \\sim Ueq, Uanis(C5_1) \\sim Ueq, Uanis(C6_1) \\sim Ueq,
Uanis(C7_1) \\sim Ueq, Uanis(C8_1) \\sim Ueq, Uanis(C9_1) \\sim Ueq,
Uanis(C10_1) \\sim Ueq, Uanis(C11_1) \\sim Ueq, Uanis(C12_1) \\sim Ueq: with
sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C9_3) = Uanis(C10_3)
Uanis(C17B) = Uanis(C9)
5. Rigid body (RIGU) restrains
 O1_1, O2_1, O3_1, O4_1, O5_1, O6_1, C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1,
 C8_1, C9_1, C10_1, C11_1, C12_1
 O1_2, O2_2, O3_2, O4_2, O5_2, O6_2, C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2,
 C8_2, C9_2, C10_2, C11_2, C12_2
 O1_3, O2_3, O3_3, O4_3, O5_3, O6_3, C1_3, C2_3, C3_3, C4_3, C5_3, C6_3, C7_3,
 C8_3, C9_3, C10_3, C11_3, C12_3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O1)=Sof(O2)=Sof(O3)=Sof(O4)=Sof(O5)=Sof(O6)=Sof(C1)=Sof(H1A)=Sof(H1B)=
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(H10A)=
 Sof(H10B)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=0.5*(1-
 FVAR(2))
 Sof(O1)=Sof(O2)=Sof(O3)=Sof(O4)=Sof(O5)=Sof(O6)=Sof(C1)=Sof(H1A)=Sof(H1B)=
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(H10A)=
 Sof(H10B)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=0.5*FVAR(2)
 Fixed Sof: C21B(0.8) H21A(0.8) H21B(0.8) H21C(0.8) C22B(0.8) H22A(0.8)
 H22B(0.8) H22C(0.8) C23B(0.8) H23A(0.8) H23B(0.8) H23C(0.8) C2(0.2) H2A(0.2)
 H2C(0.2) H2D(0.2) C3(0.2) H3A(0.2) H3C(0.2) H3D(0.2) C9(0.2) H9A(0.2) H9C(0.2)
 H9D(0.2) O1(0.5) O2(0.5) O3(0.5) O4(0.5) O5(0.5) O6(0.5) C1(0.5) H1A(0.5)
 H1B(0.5) C2(0.5) H2A(0.5) H2B(0.5) C3(0.5) H3A(0.5) H3B(0.5) C4(0.5) H4A(0.5)
 H4B(0.5) C5(0.5) H5A(0.5) H5B(0.5) C6(0.5) H6A(0.5) H6B(0.5) C7(0.5) H7A(0.5)
 H7B(0.5) C8(0.5) H8A(0.5) H8B(0.5) C9(0.5) H9A(0.5) H9B(0.5) C10(0.5)
 H10A(0.5) H10B(0.5) C11(0.5) H11A(0.5) H11B(0.5) C12(0.5) H12A(0.5) H12B(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C01G(H01A,H01B), C01H(H01C,H01D), C01N(H01E,H01F), C01S(H01G,H01H), C01W(H01I,
 H01J), C01Z(H01K,H01L), C02E(H02A,H02B), C010(H01M,H01N), C011(H01O,H01P),
 C013(H01Q,H01R), C017(H01S,H01T), C022(H02C,H02D), C1(H1A,H1B), C2(H2A,H2B),
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B),
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C1(H1A,H1B),
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B),
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B),
 C12(H12A,H12B)
7.b Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C2A(H2AA), C3A(H3AA), C4A(H4A), C7A(H7A), C8A(H8A), C9A(H9AA),
 C10A(H10A), C1B(H1B), C2B(H2B), C3B(H3B), C4B(H4B), C7B(H7B), C8B(H8B),
 C9B(H9B), C11B(H11B)
7.c Idealised Me refined as rotating group:
 C00W(H00A,H00B,H00C), C11A(H11A,H11C,H11D), C12A(H12D,H12E,H12F), C13A(H13D,
 H13E,H13F), C14A(H14D,H14E,H14F), C15A(H15D,H15E,H15F), C16A(H16D,H16E,H16F),
 C17A(H17D,H17E,H17F), C18A(H18D,H18E,H18F), C19A(H19D,H19E,H19F), C20A(H20D,
 H20E,H20F), C21A(H21D,H21E,H21F), C12B(H12A,H12B,H12C), C13B(H13A,H13B,H13C),
 C14B(H14A,H14B,H14C), C15B(H15A,H15B,H15C), C16B(H16A,H16B,H16C), C17B(H17A,
 H17B,H17C), C18B(H18A,H18B,H18C), C19B(H19A,H19B,H19C), C20B(H20A,H20B,H20C),
 C21B(H21A,H21B,H21C), C22B(H22A,H22B,H22C), C23B(H23A,H23B,H23C), C2(H2A,H2C,
 H2D), C3(H3A,H3C,H3D), C9(H9A,H9C,H9D)
;
_shelx_res_checksum              196
_shelx_hkl_checksum              90438
_olex2_submission_special_instructions 'No special instructions were received'