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_1517361
_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         'C61 H41 Br F24 Mn N O P4, 2(C3.5 H4)'
_chemical_formula_sum            'C68 H49 Br F24 Mn N O P4'
_chemical_formula_weight         1610.81
_chemical_name_systematic        (Ph,Me-PNP)Mn(Br)(CO)(bppm)
_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
_audit_creation_date             2013-12-11
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                102.567(2)
_cell_angle_beta                 93.990(2)
_cell_angle_gamma                113.051(2)
_cell_formula_units_Z            2
_cell_length_a                   13.0764(5)
_cell_length_b                   16.0035(6)
_cell_length_c                   17.7414(6)
_cell_measurement_reflns_used    9822
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.603
_cell_measurement_theta_min      2.388
_cell_volume                     3284.5(2)
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.990
_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  0.0236
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            72383
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.641
_diffrn_reflns_theta_min         1.718
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.021
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6632
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0387 before and 0.0302 after correction.
The Ratio of minimum to maximum transmission is 0.8889.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.629
_exptl_crystal_description       block
_exptl_crystal_F_000             1616
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.502
_refine_diff_density_min         -0.440
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1012
_refine_ls_number_reflns         20091
_refine_ls_number_restraints     183
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0306
_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^)+(0.0361P)^2^+1.6249P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0735
_refine_ls_wR_factor_ref         0.0776
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16873
_reflns_number_total             20091
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc01801j2.cif
_cod_data_source_block           eh018_0m
_cod_depositor_comments
'Adding full bibliography for 1517360--1517366.cif.'
_cod_database_code               1517361
_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
 F18-C52 \\sim F18A-C52 \\sim F17-C52 \\sim F17A-C52 \\sim F16-C52 \\sim F16A-C52
 with sigma of 0.02
 F8-C43 \\sim F8A-C43 \\sim F9-C43 \\sim F7A-C43 \\sim F7-C43 \\sim F9A-C43
 with sigma of 0.02
 F11A-C44 \\sim F10-C44 \\sim F10A-C44 \\sim F12-C44 \\sim C41-C40 \\sim F11-C44
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F18 \\sim F17 \\sim F16 \\sim F16A \\sim F17A \\sim F18A \\sim C52: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
4. Others
 Sof(F12A)=Sof(F11A)=Sof(F10A)=1-FVAR(1)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(1)
 Sof(F8A)=Sof(F9A)=Sof(F7A)=1-FVAR(2)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(2)
 Sof(F18)=Sof(F17)=Sof(F16)=1-FVAR(3)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=FVAR(3)
 Fixed Sof: H62(0.5) C1F(0.5) H1F(0.5) C1B(0.5) C1H(0.5) H1H(0.5) C1D(0.5)
 H1D(0.5) C1C(0.5) H1C(0.5) C1E(0.5) H1E(0.5) C1G(0.5) H1GA(0.5) H1GB(0.5)
 H1GC(0.5) C1A(0.5) H1AA(0.5) H1AB(0.5) H1AC(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C61(H61A,H61B), C26(H26A,H26B)
5.b Aromatic/amide H refined with riding coordinates:
 C58(H58), C50(H50), C46(H46), C30(H30), C54(H54), C42(H42), C24(H24),
 C38(H38), C25(H25), C40(H40), C13(H13), C16(H16), C3(H3), C7(H7), C15(H15),
 C34(H34), C19(H19), C56(H56), C23(H23), C9(H9), C22(H22), C4(H4), C17(H17),
 C21(H21), C6(H6), C48(H48), C32(H32), C10(H10), C11(H11), C18(H18), C5(H5),
 C12(H12), C64(H64), C63(H63), C62(H62), C1F(H1F), C1H(H1H), C1D(H1D), C1C(H1C),
  C1E(H1E)
5.c Fitted hexagon refined as free rotating group:
 C1F(C1B,C1H,C1D,C1C,C1E)
5.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C1G(H1GA,H1GB,H1GC), C1A(H1AA,H1AB,H1AC)
;
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.822
_shelx_hkl_checksum              85012
_shelx_res_checksum              33236
_shelxl_version_number           2013-2