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_1517366
_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 H43 F24 Mn N O P4, C24 B F20, 2.5(C6 H5 Br)'
_chemical_formula_sum            'C100 H55.5 B Br2.5 F44 Mn N O P4'
_chemical_formula_weight         2512.36
_chemical_name_systematic
;
 ?
;
_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   mixed
_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                73.676(3)
_cell_angle_beta                 72.993(3)
_cell_angle_gamma                82.991(4)
_cell_formula_units_Z            2
_cell_length_a                   14.3935(9)
_cell_length_b                   15.8738(14)
_cell_length_c                   23.3799(17)
_cell_measurement_reflns_used    9984
_cell_measurement_temperature    140
_cell_measurement_theta_max      27.773
_cell_measurement_theta_min      2.598
_cell_volume                     4897.7(6)
_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      140
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_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  0.0326
_diffrn_reflns_av_unetI/netI     0.0386
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            83544
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.888
_diffrn_reflns_theta_min         2.011
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.354
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9401
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0461 before and 0.0325 after correction.
The Ratio of minimum to maximum transmission is 0.9401.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.704
_exptl_crystal_description       block
_exptl_crystal_F_000             2488
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.660
_refine_diff_density_min         -1.779
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1530
_refine_ls_number_reflns         23173
_refine_ls_number_restraints     271
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0917
_refine_ls_R_factor_gt           0.0641
_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^)+(0.0984P)^2^+8.0002P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1754
_refine_ls_wR_factor_ref         0.1934
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16619
_reflns_number_total             23173
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc01801j2.cif
_cod_data_source_block           eh051_0m
_cod_depositor_comments
'Adding full bibliography for 1517360--1517366.cif.'
_cod_original_formula_sum        'C100 H55.50 B Br2.50 F44 Mn N O P4'
_cod_database_code               1517366
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C86-Br1
 1.9 with sigma of 0.02
 Br3-C98
 1.9 with sigma of 0.02
 Br3A-C104
 1.9 with sigma of 0.02
 C1D-Br1B
 1.9 with sigma of 0.02
 Br7-C1F
 1.9 with sigma of 0.02
 C90G-Br4
 1.9 with sigma of 0.01
 C92-Br2
 1.9 with sigma of 0.02
 F10-F11 \\sim F11-F12 \\sim F12-F10
 with sigma of 0.02
 F10A-F11A \\sim F11A-F12A \\sim F12A-F10A
 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
 F19-F20 \\sim F20-F21 \\sim F21-F19
 with sigma of 0.02
 F19A-F20A \\sim F20A-F21A \\sim F21A-F19A
 with sigma of 0.02
 F1-C35 \\sim F3-C35 \\sim F2-C35
 with sigma of 0.02
 F13A-C52 \\sim F14-C52 \\sim F14A-C52 \\sim F15-C52 \\sim F15A-C52 \\sim
F13-C52
 with sigma of 0.02
 F10-C43 \\sim F12A-C43 \\sim F12-C43 \\sim F11A-C43 \\sim F11-C43 \\sim
F10A-C43
 with sigma of 0.02
 F18-C51 \\sim F17A-C51 \\sim F17-C51 \\sim F16A-C51 \\sim F16-C51 \\sim
F18A-C51
 with sigma of 0.02
 F19-C59 \\sim F19A-C59 \\sim F20-C59 \\sim F20A-C59 \\sim F21-C59 \\sim
F21A-C59
 with sigma of 0.001
 C1G-Br7 \\sim C1K-Br7
 with sigma of 0.02
 C95G-Br4 \\sim C91G-Br4
 with sigma of 0.02
3. Restrained planarity
 Br7, C1J, H1J, C1K, H1K, C1F, C1G, H1G, C1H, H1H, C1I, H1I
 with sigma of 0.1
 Br4, C91G, C92G, C93G, C94G, C95G, C90G
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
F2 \\sim F1A \\sim F1 \\sim F3A \\sim F3: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08
Br2 \\sim Br4: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C88 \\sim C87 \\sim C89 \\sim C86 \\sim C90 \\sim C91: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
Uanis(Br1B) = Uanis(Br3A)
Uanis(Br7) = Uanis(Br3)
Uanis(C104) = Uanis(C105) = Uanis(C106) = Uanis(C107) = Uanis(C108) =
Uanis(C109) = Uanis(C101) = Uanis(C102) = Uanis(C103) = Uanis(C98) = Uanis(C99)
= Uanis(C100)
Uiso(C1R) = Uiso(C11) = Uiso(C1A) = Uiso(C1B) = Uiso(C1C) = Uiso(C1D)
Uiso(C1F) = Uiso(C1K) = Uiso(C1J) = Uiso(C1I) = Uiso(C1H) = Uiso(C1G)
Uanis(C92) = Uanis(C93) = Uanis(C94) = Uanis(C95) = Uanis(C96) = Uanis(C97) =
Uanis(C91G) = Uanis(C92G) = Uanis(C93G) = Uanis(C94G) = Uanis(C95G) =
Uanis(C90G)
5. Rigid body (RIGU) restrains
 C43, F10, F11, F12, F10A, F11A, F12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F18, C51, F16, F16A, F17, F17A, F18A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F21, F19, F20, C59, F21A, F19A, F20A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F11A)=Sof(F12A)=Sof(F10A)=1-FVAR(1)
 Sof(F11)=Sof(F10)=Sof(F12)=FVAR(1)
 Fixed Sof: F21(0.36226) F19(0.36226) F20(0.36226) F18(0.70258) F16(0.70258)
 Br2(0.403) F15(0.54081) C92(0.403) C93(0.403) H93(0.403) C94(0.403) H94(0.403)
 C95(0.403) H95(0.403) C96(0.403) H96(0.403) C97(0.403) H97(0.403) F14(0.54081)
 F17(0.70258) F13(0.54081) F2(0.50957) F1(0.50957) F3(0.50957) F1A(0.49043)
 F3A(0.49043) F2A(0.49043) F15A(0.45919) F14A(0.45919) F13A(0.45919)
 F18A(0.29742) F16A(0.29742) F17A(0.29742) F21A(0.63774) F19A(0.63774)
 F20A(0.63774) Br3(0.397) C101(0.397) H101(0.397) C102(0.397) H102(0.397)
 C103(0.397) H103(0.397) C98(0.397) C99(0.397) H99(0.397) C100(0.397)
 H100(0.397) Br3A(0.375) C104(0.375) C105(0.375) H105(0.375) C106(0.375)
 H106(0.375) C107(0.375) H107(0.375) C108(0.375) H108(0.375) C109(0.375)
 H109(0.375) Br1B(0.126) C1R(0.126) H1R(0.126) C11(0.126) H11(0.126) C1A(0.126)
 H1A(0.126) C1B(0.126) H1B(0.126) C1C(0.126) H1C(0.126) C1D(0.126) Br4(0.097)
 C91G(0.097) H91G(0.097) C92G(0.097) H92G(0.097) C93G(0.097) H93G(0.097)
 C94G(0.097) H94G(0.097) C95G(0.097) H95G(0.097) C90G(0.097) Br7(0.102)
 C1J(0.102) H1J(0.102) C1K(0.102) H1K(0.102) C1F(0.102) C1G(0.102) H1G(0.102)
 C1H(0.102) H1H(0.102) C1I(0.102) H1I(0.102)
7.a Ternary CH refined with riding coordinates:
 N1(H1)
7.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C61(H61A,H61B)
7.c Aromatic/amide H refined with riding coordinates:
 C58(H58), C56(H56), C54(H54), C10(H10), C9(H9), C8(H8), C7(H7), C6(H6),
 C34(H34), C30(H30), C32(H32), C14(H14), C28(H28), C24(H24), C25(H25), C26(H26),
  C27(H27), C38(H38), C42(H42), C22(H22), C21(H21), C20(H20), C19(H19),
 C18(H18), C48(H48), C40(H40), C50(H50), C46(H46), C91(H91), C87(H87), C88(H88),
  C89(H89), C90(H90), C93(H93), C94(H94), C95(H95), C96(H96), C97(H97),
 C12(H12), C15(H15), C16(H16), C13(H13), C101(H101), C102(H102), C103(H103),
 C99(H99), C100(H100), C105(H105), C106(H106), C107(H107), C108(H108),
 C109(H109), C1R(H1R), C11(H11), C1A(H1A), C1B(H1B), C1C(H1C), C91G(H91G),
 C92G(H92G), C93G(H93G), C94G(H94G), C95G(H95G), C1J(H1J), C1K(H1K), C1G(H1G),
 C1H(H1H), C1I(H1I)
7.d Fitted hexagon refined as free rotating group:
 C92(C93,C94,C95,C96,C97), C101(C102,C103,C98,C99,C100), C104(C105,C106,C107,
 C108,C109), C1R(C11,C1A,C1B,C1C,C1D), C91G(C92G,C93G,C94G,C95G,C90G), C1J(C1K,
 C1F,C1G,C1H,C1I)
7.e Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C)
;
_shelx_res_checksum              10031
_shelx_hkl_checksum              63608