Heterolytic cleavage of H2by bifunctional manganese(i) complexes: impact of ligand dynamics, electrophilicity, and base positioning
Hulley, Elliott B.; Helm, Monte L.; Bullock, R. Morris; Chem. Sci. 5 (2014) 4729–; doi:10.1039/C4SC01801J

data_1517365
_publ_section_title
;
 Heterolytic cleavage of H2by bifunctional manganese(i) complexes: impact
 of ligand dynamics, electrophilicity, and base positioning
;
_journal_issue                   12
_journal_name_full               'Chem. Sci.'
_journal_page_first              4729
_journal_paper_doi               10.1039/C4SC01801J
_journal_volume                  5
_journal_year                    2014
_chemical_formula_moiety         'C62 H41 F24 Mn N O2 P4, C24 B F20, C6 H5 Br'
_chemical_formula_sum            'C92 H46 B Br F44 Mn N O2 P4'
_chemical_formula_weight         2302.84
_chemical_name_systematic        '[(Ph,Me-PNP)Mn(CO)2(bppm)][B(C6F5)4]'
_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
_audit_creation_date             2013-12-12
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.769(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.4905(12)
_cell_length_b                   14.9413(13)
_cell_length_c                   30.717(2)
_cell_measurement_reflns_used    9876
_cell_measurement_temperature    150
_cell_measurement_theta_max      23.930
_cell_measurement_theta_min      2.408
_cell_volume                     8955.5(11)
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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      150
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0696
_diffrn_reflns_av_unetI/netI     0.0800
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            103716
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.833
_diffrn_reflns_theta_min         1.530
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.809
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9506
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0593 before and 0.0485 after correction.
The Ratio of minimum to maximum transmission is 0.9506.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.708
_exptl_crystal_description       block
_exptl_crystal_F_000             4568
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.388
_refine_diff_density_min         -1.866
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1438
_refine_ls_number_reflns         21214
_refine_ls_number_restraints     251
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.1249
_refine_ls_R_factor_gt           0.0594
_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^)+(0.0604P)^2^+10.4826P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1270
_refine_ls_wR_factor_ref         0.1531
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12280
_reflns_number_total             21214
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc01801j2.cif
_cod_data_source_block           eh049_0m
_cod_depositor_comments
'Adding full bibliography for 1517360--1517366.cif.'
_cod_original_cell_volume        8955.4(12)
_cod_database_code               1517365
_shelxl_version_number           2013-2
_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
 Br1A-C87A \\sim Br1A-C91A
 with sigma of 0.02
 Br1-C86 \\sim C86A-Br1A
 with sigma of 0.02
 F21-C52 \\sim F19A-C52 \\sim F19-C52 \\sim F20A-C52 \\sim F20-C52 \\sim
F21A-C52
 with sigma of 0.02
 F10-C45 \\sim F10A-C45 \\sim F11-C45 \\sim F11A-C45 \\sim F12-C45 \\sim
F12A-C45
 with sigma of 0.02
 F13A-C60 \\sim F14A-C60 \\sim F15A-C60
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C91 \\sim C86 \\sim C87 \\sim C88 \\sim C89 \\sim C90: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
F21A \\sim F21 \\sim F19A \\sim F19 \\sim F20A \\sim F20: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C86A) = Uanis(C87A) = Uanis(C88A) = Uanis(C89A) = Uanis(C90A) =
Uanis(C91A)
4. Rigid body (RIGU) restrains
 C52, F19, F19A, F20, F20A, F21, F21A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C53, F22, F22A, F23, F23A, F24, F24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45, F10, F10A, F11, F11A, F12, F12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C60, F13, F13A, F14, F14A, F15, F15A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Br1A)=Sof(C89A)=Sof(H89A)=Sof(C90A)=Sof(H90A)=Sof(C91A)=Sof(H91A)=
 Sof(C86A)=Sof(C87A)=Sof(H87A)=Sof(C88A)=Sof(H88A)=1-FVAR(1)
 Sof(Br1)=Sof(C87)=Sof(H87)=Sof(C86)=Sof(C91)=Sof(H91)=Sof(C90)=Sof(H90)=
 Sof(C89)=Sof(H89)=Sof(C88)=Sof(H88)=FVAR(1)
 Sof(F23A)=Sof(F24A)=Sof(F22A)=1-FVAR(2)
 Sof(F22)=Sof(F24)=Sof(F23)=FVAR(2)
 Sof(F19A)=Sof(F21A)=Sof(F20A)=1-FVAR(3)
 Sof(F20)=Sof(F19)=Sof(F21)=FVAR(3)
 Sof(F11A)=Sof(F12A)=Sof(F10A)=1-FVAR(4)
 Sof(F12)=Sof(F10)=Sof(F11)=FVAR(4)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(5)
 Sof(F15)=Sof(F13)=Sof(F14)=FVAR(5)
6.a Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C26(H26A,H26B), C29(H29A,H29B)
6.b Aromatic/amide H refined with riding coordinates:
 C39(H39), C49(H49), C59(H59), C51(H51), C43(H43), C10(H10), C47(H47),
 C55(H55), C23(H23), C13(H13), C33(H33), C22(H22), C57(H57), C41(H41), C31(H31),
  C35(H35), C4(H4), C19(H19), C25(H25), C20(H20), C16(H16), C5(H5), C14(H14),
 C18(H18), C6(H6), C24(H24), C11(H11), C17(H17), C8(H8), C12(H12), C7(H7),
 C142(H142), C87(H87), C91(H91), C90(H90), C89(H89), C88(H88), C89A(H89A),
 C90A(H90A), C91A(H91A), C87A(H87A), C88A(H88A)
6.c Fitted hexagon refined as free rotating group:
 C87(C86,C91,C90,C89,C88), C89A(C90A,C91A,C86A,C87A,C88A)
6.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C)
;
_shelx_res_checksum              26297
_shelx_hkl_checksum              27428