Multiple, disparate redox pathways exhibited by a tris(pyrrolido)ethane iron complex.
Sazama, Graham T.; Betley, Theodore A.; Inorganic chemistry 53 (2014) 269–281; doi:10.1021/ic402210j

data_4337568
_publ_section_title
;
 Multiple, disparate redox pathways exhibited by a tris(pyrrolido)ethane
 iron complex.
;
_journal_issue                   1
_journal_name_full               'Inorganic chemistry'
_journal_page_first              269
_journal_page_last               281
_journal_paper_doi               10.1021/ic402210j
_journal_volume                  53
_journal_year                    2014
_chemical_formula_moiety
'6(C51 H56 Fe N4), 6(C16 H32 Li O4), 6(C6 H6)'
_chemical_formula_sum            'C438 H564 Fe6 Li6 N24 O24'
_chemical_formula_weight         6925.84
_chemical_name_common            '[(tpe)Fe(NHC6H4CCH3)][Li(THF)4]'
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   constr
_audit_creation_date             2013-07-03
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.879(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   29.056(6)
_cell_length_b                   12.987(3)
_cell_length_c                   52.124(12)
_cell_measurement_temperature    100(2)
_cell_volume                     19667(8)
_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-2013 (Sheldrick, 2013)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0885
_diffrn_reflns_av_unetI/netI     0.0905
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       67
_diffrn_reflns_limit_l_min       -67
_diffrn_reflns_number            352705
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.480
_diffrn_reflns_theta_min         1.042
_exptl_absorpt_coefficient_mu    0.281
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_density_diffrn    1.170
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             7452
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.069
_refine_diff_density_min         -0.660
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.488(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           fullcycle
_refine_ls_number_parameters     4543
_refine_ls_number_reflns         85867
_refine_ls_number_restraints     116
_refine_ls_restrained_S_all      1.428
_refine_ls_R_factor_all          0.1171
_refine_ls_R_factor_gt           0.0778
_refine_ls_shift/su_max          0.038
_refine_ls_shift/su_mean         0.003
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0630P)^2^+35.2259P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1695
_refine_ls_wR_factor_ref         0.1885
_reflns_Friedel_coverage         0.916
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                61671
_reflns_number_total             85867
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic402210j_si_001.cif
_cod_data_source_block           gts036
_cod_original_cell_volume        19667(7)
_cod_database_code               4337568
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N4A-H4A
 0.91 with sigma of 0.02
 N4B-H4B
 0.91 with sigma of 0.02
 N4D-H4D
 0.91 with sigma of 0.02
 N4E-H4EA
 0.91 with sigma of 0.02
 N4F-H4F
 0.91 with sigma of 0.02
3. Rigid bond restraints
 O1K, C1K, C2K, C3K, C4K
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O2K, C5K, C6K, C7K, C8K
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O1K \\sim C1K \\sim C2K \\sim C3K \\sim C4K: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
O2K \\sim C5K \\sim C6K \\sim C7K \\sim C8K: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C3E) = Uanis(C16E)
Uanis(C49F) = Uanis(C50F) = Uanis(C51F)
Uanis(C49E) = Uanis(C50E) = Uanis(C51E)
Uanis(C26F) = Uanis(C13F)
Uanis(O2L) = Uanis(O2LB)
Uanis(C5L) = Uanis(C5LB)
Uanis(C6L) = Uanis(C6LB)
Uanis(C7L) = Uanis(C7LB)
Uanis(C8L) = Uanis(C8LB)
Uanis(O3K) = Uanis(O3Z) = Uanis(O1K)
Uanis(C9K) = Uanis(C9Z) = Uanis(C1K)
Uanis(C10K) = Uanis(C10Z) = Uanis(C2K)
Uanis(C11K) = Uanis(C11Z) = Uanis(C3K)
Uanis(C12K) = Uanis(C12Z) = Uanis(C4K)
5. Same fragment restrains
{O1L, C1L, C2L, C3L, C4L}
as
{O2L, C5L, C6L, C7L, C8L}
{O1L, C1L, C2L, C3L, C4L}
as
{O2LB, C5LB, C6LB, C7LB, C8LB}
6. Others
 Sof(O2LB)=Sof(C5LB)=Sof(H5LD)=Sof(H5LC)=Sof(C6LB)=Sof(H6LC)=Sof(H6LD)=
 Sof(C7LB)=Sof(H7LC)=Sof(H7LD)=Sof(C8LB)=Sof(H8LC)=Sof(H8LD)=1-FVAR(1)
 Sof(O2L)=Sof(C5L)=Sof(H5LA)=Sof(H5LB)=Sof(C6L)=Sof(H6LA)=Sof(H6LB)=Sof(C7L)=
 Sof(H7LA)=Sof(H7LB)=Sof(C8L)=Sof(H8LA)=Sof(H8LB)=FVAR(1)
 Sof(O1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(C4)=Sof(H4G)=Sof(H4H)=1-FVAR(2)
 Sof(O3K)=Sof(C9K)=Sof(H9KA)=Sof(H9KB)=Sof(C10K)=Sof(H10A)=Sof(H10B)=Sof(C11K)=
 Sof(H11G)=Sof(H11H)=Sof(C12K)=Sof(H12A)=Sof(H12B)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C1G(H1GA,H1GB), C2G(H2GA,H2GB), C3G(H3GA,H3GB), C4G(H4GA,H4GB), C5G(H5GA,
 H5GB), C6G(H6GA,H6GB), C7G(H7GA,H7GB), C8G(H8GA,H8GB), C9G(H9GA,H9GB),
 C10G(H10E,H10F), C11G(H11K,H11L), C12G(H12E,H12F), C13G(H13W,H13X), C14G(H14W,
 H14X), C15G(H15W,H15X), C16G(H16E,H16F), C1H(H1HA,H1HB), C2H(H2HA,H2HB),
 C3H(H3HA,H3HB), C4H(H4HA,H4HB), C5H(H5HA,H5HB), C6H(H6HA,H6HB), C7H(H7HA,H7HB),
  C8H(H8HA,H8HB), C9H(H9HA,H9HB), C10H(H10G,H10H), C11H(H11M,H11N), C12H(H12G,
 H12H), C13H(H13Y,H13Z), C14H(H14Y,H14Z), C15H(H15Y,H15Z), C16H(H16G,H16H),
 C1Z(H1ZA,H1ZB), C2Z(H2ZA,H2ZB), C3Z(H3ZA,H3ZB), C4Z(H4ZA,H4ZB), C5Z(H5ZA,H5ZB),
  C6Z(H6ZA,H6ZB), C7Z(H7ZA,H7ZB), C8Z(H8ZA,H8ZB), C9Z(H9ZA,H9ZB), C10Z(H10I,
 H10J), C11Z(H11O,H11P), C12Z(H12I,H12J), C13Z(H13,H13|), C14Z(H14,H14|),
 C15Z(H15,H15|), C16Z(H16I,H16J), C1J(H1JA,H1JB), C2J(H2JA,H2JB), C3J(H3JA,
 H3JB), C4J(H4JA,H4JB), C5J(H5JA,H5JB), C6J(H6JA,H6JB), C7J(H7JA,H7JB),
 C8J(H8JA,H8JB), C9J(H9JA,H9JB), C10J(H10K,H10L), C11J(H11Q,H11R), C12J(H12K,
 H12L), C13J(H0AA,H2AA), C14J(H3AA,H5AA), C15J(H6AA,H7AA), C16J(H16K,H16L),
 C1K(H1KA,H1KB), C2K(H2KA,H2KB), C3K(H3KA,H3KB), C4K(H4KA,H4KB), C5K(H5KA,H5KB),
  C6K(H6KA,H6KB), C7K(H7KA,H7KB), C8K(H8KA,H8KB), C9K(H9KA,H9KB), C10K(H10A,
 H10B), C11K(H11G,H11H), C12K(H12A,H12B), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B),
  C4(H4G,H4H), C13K(H13S,H13T), C14K(H14S,H14T), C15K(H15S,H15T), C16K(H16A,
 H16B), C1L(H1LA,H1LB), C2L(H2LA,H2LB), C3L(H3LA,H3LB), C4L(H4LA,H4LB),
 C5L(H5LA,H5LB), C6L(H6LA,H6LB), C7L(H7LA,H7LB), C8L(H8LA,H8LB), C5LB(H5LD,
 H5LC), C6LB(H6LC,H6LD), C7LB(H7LC,H7LD), C8LB(H8LC,H8LD), C9L(H9LA,H9LB),
 C10L(H10C,H10D), C11L(H11I,H11J), C12L(H12C,H12D), C13L(H13U,H13V), C14L(H14U,
 H14V), C15L(H15U,H15V), C16L(H16C,H16D)
7.b Aromatic/amide H refined with riding coordinates:
 C4A(H4AA), C5A(H5A), C9A(H9A), C11A(H11A), C17A(H17A), C18A(H18A), C22A(H22A),
  C24A(H24A), C30A(H30A), C31A(H31A), C35A(H35A), C37A(H37A), C43A(H43A),
 C44A(H44A), C46A(H46A), C47A(H47A), C4B(H4BA), C5B(H5B), C9B(H9B), C11B(H11B),
 C17B(H17B), C18B(H18B), C22B(H22B), C24B(H24B), C30B(H30B), C31B(H31B),
 C35B(H35B), C37B(H37B), C43B(H43B), C44B(H44B), C46B(H46B), C47B(H47B),
 N4C(H4C), C4C(H4CA), C5C(H5C), C9C(H9C), C11C(H11C), C17C(H17C), C18C(H18C),
 C22C(H22C), C24C(H24C), C30C(H30C), C31C(H31C), C35C(H35C), C37C(H37C),
 C43C(H43C), C44C(H44C), C46C(H46C), C47C(H47C), C4D(H4DA), C5D(H5D), C9D(H9D),
 C11D(H11D), C17D(H17D), C18D(H18D), C22D(H22D), C24D(H24D), C30D(H30D),
 C31D(H31D), C35D(H35D), C37D(H37D), C43D(H43D), C44D(H44D), C46D(H46D),
 C47D(H47D), C4E(H4EA), C5E(H5E), C9E(H9E), C11E(H11E), C17E(H17E), C18E(H18E),
 C22E(H22E), C24E(H24E), C30E(H30E), C31E(H31E), C35E(H35E), C37E(H37E),
 C43E(H43E), C44E(H44E), C46E(H46E), C47E(H47E), C4F(H4FA), C5F(H5F), C9F(H9F),
 C11F(H11F), C17F(H17F), C18F(H18F), C22F(H22F), C24F(H24F), C30F(H30F),
 C31F(H31F), C35F(H35F), C37F(H37F), C43F(H43F), C44F(H44F), C46F(H46F),
 C47F(H47F), C1M(H1M), C2M(H2M), C3M(H3M), C4M(H4M), C5M(H5M), C6M(H6M),
 C1N(H1N), C2N(H2N), C3N(H3N), C4N(H4N), C5N(H5N), C6N(H6N), C1O(H1O), C2O(H2O),
  C3O(H3O), C4O(H4O), C5O(H5O), C6O(H6O), C1P(H1P), C2P(H2P), C3P(H3P),
 C4P(H4P), C5P(H5P), C6P(H6P), C1Q(H1Q), C2Q(H2Q), C3Q(H3Q), C4Q(H4Q), C5Q(H5Q),
  C6Q(H6Q), C1R(H1R), C2R(H2R), C3R(H3R), C4R(H4R), C5R(H5R), C6R(H6R)
7.c Idealised Me refined as rotating group:
 C1A(H1AA,H1AB,H1AC), C13A(H13A,H13B,H13C), C14A(H14A,H14B,H14C), C15A(H15A,
 H15B,H15C), C26A(H26A,H26B,H26C), C27A(H27A,H27B,H27C), C28A(H28A,H28B,H28C),
 C39A(H39A,H39B,H39C), C40A(H40A,H40B,H40C), C41A(H41A,H41B,H41C), C49A(H49A,
 H49B,H49C), C50A(H50A,H50B,H50C), C51A(H51A,H51B,H51C), C1B(H1BA,H1BB,H1BC),
 C13B(H13D,H13E,H13F), C14B(H14D,H14E,H14F), C15B(H15D,H15E,H15F), C26B(H26D,
 H26E,H26F), C27B(H27D,H27E,H27F), C28B(H28D,H28E,H28F), C39B(H39D,H39E,H39F),
 C40B(H40D,H40E,H40F), C41B(H41D,H41E,H41F), C49B(H49D,H49E,H49F), C50B(H50D,
 H50E,H50F), C51B(H51D,H51E,H51F), C1C(H1CA,H1CB,H1CC), C13C(H13G,H13H,H13I),
 C14C(H14G,H14H,H14I), C15C(H15G,H15H,H15I), C26C(H26G,H26H,H26I), C27C(H27G,
 H27H,H27I), C28C(H28G,H28H,H28I), C39C(H39G,H39H,H39I), C40C(H40G,H40H,H40I),
 C41C(H41G,H41H,H41I), C49C(H49G,H49H,H49I), C50C(H50G,H50H,H50I), C51C(H51G,
 H51H,H51I), C1D(H1DA,H1DB,H1DC), C13D(H13J,H13K,H13L), C14D(H14J,H14K,H14L),
 C15D(H15J,H15K,H15L), C26D(H26J,H26K,H26L), C27D(H27J,H27K,H27L), C28D(H28J,
 H28K,H28L), C39D(H39J,H39K,H39L), C40D(H40J,H40K,H40L), C41D(H41J,H41K,H41L),
 C49D(H49J,H49K,H49L), C50D(H50J,H50K,H50L), C51D(H51J,H51K,H51L), C1E(H1EA,
 H1EB,H1EC), C13E(H13M,H13N,H13O), C14E(H14M,H14N,H14O), C15E(H15M,H15N,H15O),
 C26E(H26M,H26N,H26O), C27E(H27M,H27N,H27O), C28E(H28M,H28N,H28O), C39E(H39M,
 H39N,H39O), C40E(H40M,H40N,H40O), C41E(H41M,H41N,H41O), C49E(H49M,H49N,H49O),
 C50E(H50M,H50N,H50O), C51E(H51M,H51N,H51O), C1F(H1FA,H1FB,H1FC), C13F(H13P,
 H13Q,H13R), C14F(H14P,H14Q,H14R), C15F(H15P,H15Q,H15R), C26F(H26P,H26Q,H26R),
 C27F(H27P,H27Q,H27R), C28F(H28P,H28Q,H28R), C39F(H39P,H39Q,H39R), C40F(H40P,
 H40Q,H40R), C41F(H41P,H41Q,H41R), C49F(H49P,H49Q,H49R), C50F(H50P,H50Q,H50R),
 C51F(H51P,H51Q,H51R)
;
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.911