Rapid, Reversible Heterolytic Cleavage of Bound H2
Elliott B. Hulley; Kevin D. Welch; Aaron M. Appel; Daniel L. DuBois; R. Morris Bullock; Journal of the American Chemical Society 135 (2013) 11736–11739; doi:10.1021/ja405755j

data_4120275
_publ_section_title
;
 Rapid, Reversible Heterolytic Cleavage of Bound H2
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11736
_journal_page_last               11739
_journal_paper_doi               10.1021/ja405755j
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety
'C64 H46 Br F24 Mn N2 O P4, C3 H3 F0.5, C6 H5 F'
_chemical_formula_sum            'C73 H54 Br F25.5 Mn N2 O P4'
_chemical_formula_weight         1718.41
_chemical_name_systematic        (Ph,Bn-P2N2)Mn(Br)(CO)(bppm)
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-06-07
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.276(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.4201(7)
_cell_length_b                   14.1598(6)
_cell_length_c                   27.2989(11)
_cell_measurement_reflns_used    9786
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.174
_cell_measurement_theta_min      2.405
_cell_volume                     7100.4(5)
_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      100.15
_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  0.0458
_diffrn_reflns_av_unetI/netI     0.0345
_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       -23
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            147181
_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         30.199
_diffrn_reflns_theta_min         1.496
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.953
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.6610
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0493 before and 0.0428 after correction.
The Ratio of minimum to maximum transmission is 0.8861.
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    1.608
_exptl_crystal_description       block
_exptl_crystal_F_000             3454
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.882
_refine_diff_density_min         -0.517
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1063
_refine_ls_number_reflns         21020
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0372
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0381P)^2^+6.6564P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0835
_refine_ls_wR_factor_ref         0.0920
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16364
_reflns_number_total             21020
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja405755j_si_002.cif
_cod_data_source_block           eh006_0m
_cod_original_formula_sum        'C73 H54 Br F25.50 Mn N2 O P4'
_cod_database_code               4120275
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 F25-C1B \\sim F25A-C72
 with sigma of 0.02
 F16-C54 \\sim F18-C54 \\sim C54-F17 \\sim C54-C54
 with sigma of 0.02
 F16-F17 \\sim F17-F18 \\sim F18-F16
 with sigma of 0.02
 F16A-F17A \\sim F17A-F18A \\sim F18A-F16A
 with sigma of 0.02
 F18-C54 \\sim F18A-C54 \\sim F17A-C54 \\sim F17-C54 \\sim F16A-C54 
\\sim F16-C54
 with sigma of 0.001
3. others
 Fixed Sof: F26(0.5) F18(0.38744) F16(0.38744) F17(0.38744) F12A(0.57505)
 H72(0.44112) F10A(0.57505) F11A(0.57505) F15A(0.60913) F13A(0.60913)
 F14A(0.60913) H1B(0.55888) F13(0.39087) F25A(0.55888) F25(0.44112)
 F15(0.39087) F14(0.39087) F11(0.42495) F10(0.42495) F12(0.42495) F17A(0.61256)
 F18A(0.61256) F16A(0.61256)
4.a Secondary CH2 refined with riding coordinates:
 C100(H10A,H10B), C101(H10C,H10D), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,
 H13B), C25(H25A,H25B), C40(H40A,H40B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C15(H15),
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23),
  C24(H24), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C33(H33),
 C35(H35), C38(H38), C42(H42), C44(H44), C46(H46), C50(H50), C52(H52), C55(H55),
  C60(H60), C62(H62), C64(H64), C70(H70), C71(H71), C72(H72), C73(H73),
 C74(H74), C1B(H1B)
;
_shelx_estimated_absorpt_t_max   0.911
_shelx_estimated_absorpt_t_min   0.797
_shelx_res_checksum              22463
_shelxl_version_number           2013-2