Interconversion and reactivity of manganese silyl, silylene, and silene complexes
Price, Jeffrey S.; Emslie, David J. H.; Chemical Science  (2019) –; doi:10.1039/C9SC04513A

data_1552514
_publ_section_title
;
 Interconversion and reactivity of manganese silyl, silylene, and silene
 complexes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC04513A
_journal_year                    2019
_chemical_formula_moiety         'C25 H52 Mn N P4 Si'
_chemical_formula_sum            'C25 H52 Mn N P4 Si'
_chemical_formula_weight         573.58
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-02-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-08-09 deposited with the CCDC.    2019-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.3395(10)
_cell_length_b                   18.5712(10)
_cell_length_c                   19.5632(12)
_cell_measurement_reflns_used    7762
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.00
_cell_measurement_theta_min      2.35
_cell_volume                     6299.7(6)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0564
_diffrn_reflns_av_unetI/netI     0.0614
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            41001
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.515
_diffrn_reflns_theta_min         1.915
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.674
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6292
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0564 before and 0.0511 after correction.
The Ratio of minimum to maximum transmission is 0.8433.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.210
_exptl_crystal_description       block
_exptl_crystal_F_000             2464
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.638
_refine_diff_density_min         -0.744
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.227
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     405
_refine_ls_number_reflns         9543
_refine_ls_number_restraints     735
_refine_ls_restrained_S_all      1.189
_refine_ls_R_factor_all          0.1117
_refine_ls_R_factor_gt           0.0846
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+34.4315P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1787
_refine_ls_wR_factor_ref         0.1859
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7105
_reflns_number_total             9543
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04513a3.cif
_cod_data_source_block           MnHSinBu_xylylNC
_cod_original_cell_volume        6299.6(6)
_cod_database_code               1552514
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.936
_shelx_estimated_absorpt_t_min   0.823
_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
 Mn1-P2B \\sim Mn1-P1A \\sim Mn1-P1
 with sigma of 0.005
 Mn1-P1B \\sim Mn1-P2A \\sim Mn1-P3
 with sigma of 0.005
 Mn1-P3A \\sim Mn1-P4
 with sigma of 0.005
 Mn1-P2 \\sim Mn1-P4A
 with sigma of 0.005
 N1-C1 \\sim C1-N1A
 with sigma of 0.005
 N1-C2 \\sim C2-N1A
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C14A) = Uanis(C14)
Uanis(C16) = Uanis(C15A)
Uanis(C16A) = Uanis(C15)
Uanis(C21) = Uanis(C18A)
Uanis(C20) = Uanis(C17A)
Uanis(C22) = Uanis(C19A)
Uanis(C23) = Uanis(C21A)
Uanis(C19) = Uanis(C25A)
Uanis(C18) = Uanis(C24A)
Uanis(P3A) = Uanis(P4)
Uanis(P4A) = Uanis(P2)
Uanis(P1A) = Uanis(P1)
Uanis(P3) = Uanis(P2A)
Uanis(C24) = Uanis(C22A)
Uanis(C20A) = Uanis(C25)
Uanis(C18A) = Uanis(C14B)
Uanis(C19A) = Uanis(C15B)
Uanis(P2A) = Uanis(P1B)
Uanis(C17A) = Uanis(C16B)
Uanis(C17B) = Uanis(C16A)
Uanis(P1A) = Uanis(P2B)
Uanis(C14A) = Uanis(C18B)
Uanis(C15A) = Uanis(C19B)
Uanis(N1) = Uanis(N1A)
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. Same fragment restrains
{P1, P2, C14, C15, C16, C17, C18, C19} sigma for 1-2: 0.002, 1-3: 0.004
as
{P3, P4, C20, C21, C22, C23, C24, C25}
{P1, P2, C14, C15, C16, C17, C18, C19} sigma for 1-2: 0.002, 1-3: 0.004
as
{P1A, P2A, C14A, C15A, C16A, C17A, C18A, C19A}
{P1, P2, C14, C15, C16, C17, C18, C19} sigma for 1-2: 0.002, 1-3: 0.004
as
{P3A, P4A, C20A, C21A, C22A, C23A, C24A, C25A}
{P1, P2, C14, C15, C16, C17, C18, C19} sigma for 1-2: 0.002, 1-3: 0.004
as
{P1B, P2B, C14B, C15B, C16B, C17B, C18B, C19B}
6. Others
 1*[Sof(P1)+Sof(P2)+Sof(C14)+Sof(H14A)+Sof(H14B)+Sof(H14C)+Sof(C15)+Sof(H15A)+
 Sof(H15B)+Sof(H15C)+Sof(C16)+Sof(H16A)+Sof(H16B)+Sof(C17)+Sof(H17A)+Sof(H17B)+
 Sof(C18)+Sof(H18A)+Sof(H18B)+Sof(H18C)+Sof(C19)+Sof(H19A)+Sof(H19B)+Sof(H19C)+
 Sof(P3)+Sof(P4)+Sof(C20)+Sof(H20A)+Sof(H20B)+Sof(H20C)+Sof(C21)+Sof(H21A)+
 Sof(H21B)+Sof(H21C)+Sof(C22)+Sof(H22A)+Sof(H22B)+Sof(C23)+Sof(H23A)+Sof(H23B)+
 Sof(C24)+Sof(H24A)+Sof(H24B)+Sof(H24C)+Sof(C25)+Sof(H25A)+Sof(H25B)+Sof(H25C)+
 Sof(P3A)+Sof(P4A)+Sof(C20A)+Sof(H20D)+Sof(H20E)+Sof(H20F)+Sof(C21A)+Sof(H21D)+
 Sof(H21E)+Sof(H21F)+Sof(C22A)+Sof(H22C)+Sof(H22D)+Sof(C23A)+Sof(H23C)+
 Sof(H23D)+Sof(C24A)+Sof(H24D)+Sof(H24E)+Sof(H24F)+Sof(C25A)+Sof(H25D)+
 Sof(H25E)+Sof(H25F)]+1*[Sof(P1A)+Sof(P2A)+Sof(C14A)+Sof(H14D)+Sof(H14E)+
 Sof(H14F)+Sof(C15A)+Sof(H15D)+Sof(H15E)+Sof(H15F)+Sof(C16A)+Sof(H16C)+
 Sof(H16D)+Sof(C17A)+Sof(H17C)+Sof(H17D)+Sof(C18A)+Sof(H18D)+Sof(H18E)+
 Sof(H18F)+Sof(C19A)+Sof(H19D)+Sof(H19E)+Sof(H19F)]+1*[Sof(P1B)+Sof(P2B)+
 Sof(C14B)+Sof(H14G)+Sof(H14H)+Sof(H14I)+Sof(C15B)+Sof(H15G)+Sof(H15H)+
 Sof(H15I)+Sof(C16B)+Sof(H16E)+Sof(H16F)+Sof(C17B)+Sof(H17E)+Sof(H17F)+
 Sof(C18B)+Sof(H18G)+Sof(H18H)+Sof(H18I)+Sof(C19B)+Sof(H19G)+Sof(H19H)+
 Sof(H19I)]=1 with esd of 0.001
 Sof(P3A)=Sof(P4A)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21A)=Sof(H21D)=
 Sof(H21E)=Sof(H21F)=Sof(C22A)=Sof(H22C)=Sof(H22D)=Sof(C23A)=Sof(H23C)=
 Sof(H23D)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25A)=Sof(H25D)=
 Sof(H25E)=Sof(H25F)=1-FVAR(1)
 Sof(P1)=Sof(P2)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=
 Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C17)=Sof(H17A)=Sof(H17B)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(P3)=Sof(P4)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=Sof(H21A)=
 Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C23)=Sof(H23A)=Sof(H23B)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=
 FVAR(1)
 Sof(P1A)=Sof(P2A)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15A)=Sof(H15D)=
 Sof(H15E)=Sof(H15F)=Sof(C16A)=Sof(H16C)=Sof(H16D)=Sof(C17A)=Sof(H17C)=
 Sof(H17D)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=
 Sof(H19E)=Sof(H19F)=FVAR(2)
 Sof(P1B)=Sof(P2B)=Sof(C14B)=Sof(H14G)=Sof(H14H)=Sof(H14I)=Sof(C15B)=Sof(H15G)=
 Sof(H15H)=Sof(H15I)=Sof(C16B)=Sof(H16E)=Sof(H16F)=Sof(C17B)=Sof(H17E)=
 Sof(H17F)=Sof(C18B)=Sof(H18G)=Sof(H18H)=Sof(H18I)=Sof(C19B)=Sof(H19G)=
 Sof(H19H)=Sof(H19I)=FVAR(3)
 Sof(N1A)=1-FVAR(4)
 Sof(N1)=FVAR(4)
7.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C16(H16A,H16B), C17(H17A,
 H17B), C22(H22A,H22B), C23(H23A,H23B), C16A(H16C,H16D), C17A(H17C,H17D),
 C22A(H22C,H22D), C23A(H23C,H23D), C16B(H16E,H16F), C17B(H17E,H17F)
7.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6)
7.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C),
 C14A(H14D,H14E,H14F), C15A(H15D,H15E,H15F), C18A(H18D,H18E,H18F), C19A(H19D,
 H19E,H19F), C20A(H20D,H20E,H20F), C21A(H21D,H21E,H21F), C24A(H24D,H24E,H24F),
 C25A(H25D,H25E,H25F), C14B(H14G,H14H,H14I), C15B(H15G,H15H,H15I), C18B(H18G,
 H18H,H18I), C19B(H19G,H19H,H19I)
;
_shelx_res_checksum              54271
_olex2_submission_special_instructions 'No special instructions were received'