Anion control of tautomeric equilibria: Fe‒H vs. N‒H influenced by NH⋯F hydrogen bonding
Chambers, Geoffrey M.; Johnson, Samantha I.; Raugei, Simone; Bullock, R. Morris; Chemical Science  (2019) –; doi:10.1039/C8SC04239J

data_1550281
_publ_section_title
;
 Anion control of tautomeric equilibria: Fe--H vs. N--H influenced by
 NH&#x22EF;F hydrogen bonding
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC04239J
_journal_year                    2019
_chemical_formula_moiety         'C14 H27 Fe N O3 P2, C32 H12 B F24'
_chemical_formula_sum            'C46 H39 B F24 Fe N O3 P2'
_chemical_formula_weight         1238.38
_chemical_name_systematic
; 
 ? 
;
_chemical_properties_physical    Air-sensitive,Oxygen-sensitive
_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     iterative
_audit_creation_date             2016-11-27
_audit_creation_method
; 
Olex2 1.2 
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227) 
;
_audit_update_record
;
2017-12-12 deposited with the CCDC.
2018-11-23 downloaded from the CCDC.
;
_cell_angle_alpha                67.1494(13)
_cell_angle_beta                 86.3179(12)
_cell_angle_gamma                85.5446(12)
_cell_formula_units_Z            4
_cell_length_a                   12.4386(3)
_cell_length_b                   19.8125(5)
_cell_length_c                   23.4119(6)
_cell_measurement_reflns_used    9821
_cell_measurement_temperature    230
_cell_measurement_theta_max      26.383
_cell_measurement_theta_min      2.235
_cell_volume                     5297.1(2)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2013.10-0 (Bruker, 2013)'
_computing_data_reduction
; 
SAINT V8.34A, XPREP v2013/3, SADABS V2012/1, TWINABS V2012/1 
(Bruker, 2012 & 2013) 
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELX-2013-4 (Sheldrick, 2013)'
_computing_structure_solution    'SHELX-2013-4 (Sheldrick, 2013)'
_diffrn_ambient_temperature      230
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_wavelength_id  a09a_0m
_diffrn_reflns_av_R_equivalents  0.0416
_diffrn_reflns_av_unetI/netI     0.0370
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            83502
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.564
_diffrn_reflns_theta_min         1.117
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.470
_exptl_absorpt_correction_T_max  0.93446
_exptl_absorpt_correction_T_min  0.87835
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'SHELXTL/XPREP V2005/2 (Bruker, 2005)'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.553
_exptl_crystal_description       prism
_exptl_crystal_F_000             2492
_exptl_crystal_id                a09a_0m
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N, Exxon) to a 
0.3 mm cryo-loop (Hampton Research) with the 0 0 1 scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_size_max          0.583
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.238
_refine_diff_density_max         0.578
_refine_diff_density_min         -0.516
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1779
_refine_ls_number_reflns         22026
_refine_ls_number_restraints     1185
_refine_ls_restrained_S_all      1.177
_refine_ls_R_factor_all          0.0676
_refine_ls_R_factor_gt           0.0427
_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^)+(0.0687P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1149
_refine_ls_wR_factor_ref         0.1258
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14975
_reflns_number_total             22026
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc04239j2.cif
_cod_data_source_block           a09a_0m
_cod_database_code               1550281
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.896
_shelx_estimated_absorpt_t_min   0.771
_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 
 F46-F47 \\sim F46-F48 \\sim F47-F48 \\sim F46A-F47A \\sim F46A-F48A \\sim 
F47A-F48A 
 with sigma of 0.01 
 F34-F35 \\sim F34-F36 \\sim F35-F36 \\sim F34A-F35A \\sim F34A-F36A \\sim 
F35A-F36A 
 with sigma of 0.01 
 F31-F32 \\sim F31-F33 \\sim F32-F33 \\sim F31A-F32A \\sim F31A-F33A \\sim 
F32A-F33A 
 with sigma of 0.01 
 F25-F26 \\sim F25-F27 \\sim F26-F27 \\sim F25A-F26A \\sim F25A-F27A \\sim 
F26A-F27A 
 with sigma of 0.01 
 F43-F44 \\sim F43-F45 \\sim F44-F45 \\sim F43A-F44A \\sim F43A-F45A \\sim 
F44A-F45A 
 with sigma of 0.01 
 F37-F38 \\sim F37-F39 \\sim F38-F39 \\sim F37A-F38A \\sim F37A-F39A \\sim 
F38A-F39A 
 with sigma of 0.01 
 F40-F41 \\sim F40-F42 \\sim F41-F42 \\sim F40A-F41A \\sim F40A-F42A \\sim 
F41A-F42A 
 with sigma of 0.01 
 F16-F17 \\sim F16-F18 \\sim F17-F18 \\sim F16A-F17A \\sim F16A-F18A \\sim 
F17A-F18A 
 with sigma of 0.01 
 F7-F8 \\sim F7-F9 \\sim F8-F9 \\sim F7A-F8A \\sim F7A-F9A \\sim F8A-F9A 
 with sigma of 0.01 
 F1-F2 \\sim F1-F3 \\sim F2-F3 \\sim F1A-F2A \\sim F1A-F3A \\sim F2A-F3A 
 with sigma of 0.01 
 F10-F11 \\sim F10-F12 \\sim F11-F12 \\sim F10A-F11A \\sim F10A-F12A \\sim 
F11A-F12A 
 with sigma of 0.01 
 F4-F5 \\sim F4-F6 \\sim F5-F6 \\sim F4A-F5A \\sim F4A-F6A \\sim F5A-F6A 
 with sigma of 0.01 
 F19-F20 \\sim F19-F70 \\sim F20-F70 \\sim F19A-F20A \\sim F19A-F70A \\sim 
F20A-F70A 
 with sigma of 0.01 
3. Uiso/Uaniso restraints and constraints 
F1 \\sim F1A \\sim F2 \\sim F2A \\sim F3 \\sim F3A \\sim F4 \\sim F4A \\sim F5 
\\sim F5A \\sim F6 \\sim F6A \\sim F7 \\sim F7A \\sim F8 \\sim F8A \\sim F9 
\\sim F9A \\sim F10 \\sim F10A \\sim F11 \\sim F11A \\sim F12 \\sim F12A \\sim 
F13 \\sim F14 \\sim F15 \\sim F16 \\sim F16A \\sim F17 \\sim F17A \\sim F18 
\\sim F18A \\sim F19 \\sim F20 \\sim F21 \\sim F22 \\sim F23 \\sim F70 \\sim 
F25 \\sim F25A \\sim F26 \\sim F26A \\sim F27 \\sim F27A \\sim F28 \\sim F29 
\\sim F30 \\sim F31 \\sim F31A \\sim F32 \\sim F32A \\sim F33 \\sim F33A \\sim 
F34 \\sim F34A \\sim F35 \\sim F35A \\sim F36 \\sim F36A \\sim F37 \\sim F37A 
\\sim F38 \\sim F38A \\sim F39 \\sim F39A \\sim F40 \\sim F40A \\sim F41 \\sim 
F41A \\sim F42 \\sim F42A \\sim F43 \\sim F43A \\sim F44 \\sim F44A \\sim F45 
\\sim F45A \\sim F46 \\sim F46A \\sim F47 \\sim F47A \\sim F48 \\sim F48A \\sim 
F20A \\sim F70A \\sim F19A: within 2A with sigma of 0.01 and sigma for terminal 
atoms of 0.02 
Uanis(F1) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F2A) 
\\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F4) \\sim Ueq, 
Uanis(F4A) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F5A) \\sim Ueq, Uanis(F6) 
\\sim Ueq, Uanis(F6A) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F7A) \\sim Ueq, 
Uanis(F8) \\sim Ueq, Uanis(F8A) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F9A) 
\\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F10A) \\sim Ueq, Uanis(F11) \\sim Ueq, 
Uanis(F11A) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F12A) \\sim Ueq, Uanis(F13) 
\\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(F16) \\sim Ueq, 
Uanis(F16A) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F17A) \\sim Ueq, Uanis(F18) 
\\sim Ueq, Uanis(F18A) \\sim Ueq, Uanis(F19) \\sim Ueq, Uanis(F20) \\sim Ueq, 
Uanis(F21) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(F70) 
\\sim Ueq, Uanis(F25) \\sim Ueq, Uanis(F25A) \\sim Ueq, Uanis(F26) \\sim Ueq, 
Uanis(F26A) \\sim Ueq, Uanis(F27) \\sim Ueq, Uanis(F27A) \\sim Ueq, Uanis(F28) 
\\sim Ueq, Uanis(F29) \\sim Ueq, Uanis(F30) \\sim Ueq, Uanis(F31) \\sim Ueq, 
Uanis(F31A) \\sim Ueq, Uanis(F32) \\sim Ueq, Uanis(F32A) \\sim Ueq, Uanis(F33) 
\\sim Ueq, Uanis(F33A) \\sim Ueq, Uanis(F34) \\sim Ueq, Uanis(F34A) \\sim Ueq, 
Uanis(F35) \\sim Ueq, Uanis(F35A) \\sim Ueq, Uanis(F36) \\sim Ueq, Uanis(F36A) 
\\sim Ueq, Uanis(F37) \\sim Ueq, Uanis(F37A) \\sim Ueq, Uanis(F38) \\sim Ueq, 
Uanis(F38A) \\sim Ueq, Uanis(F39) \\sim Ueq, Uanis(F39A) \\sim Ueq, Uanis(F40) 
\\sim Ueq, Uanis(F40A) \\sim Ueq, Uanis(F41) \\sim Ueq, Uanis(F41A) \\sim Ueq, 
Uanis(F42) \\sim Ueq, Uanis(F42A) \\sim Ueq, Uanis(F43) \\sim Ueq, Uanis(F43A) 
\\sim Ueq, Uanis(F44) \\sim Ueq, Uanis(F44A) \\sim Ueq, Uanis(F45) \\sim Ueq, 
Uanis(F45A) \\sim Ueq, Uanis(F46) \\sim Ueq, Uanis(F46A) \\sim Ueq, Uanis(F47) 
\\sim Ueq, Uanis(F47A) \\sim Ueq, Uanis(F48) \\sim Ueq, Uanis(F48A) \\sim Ueq, 
Uanis(F20A) \\sim Ueq, Uanis(F70A) \\sim Ueq, Uanis(F19A) \\sim Ueq: with sigma 
of 0.01 and sigma for terminal atoms of 0.02 
4. Rigid body (RIGU) restrains 
 F1, F1A, F2, F2A, F3, F3A, F4, F4A, F5, F5A, F6, F6A, F7, F7A, F8, F8A, F9, 
 F9A, F10, F10A, F11, F11A, F12, F12A, F13, F14, F15, F16, F16A, F17, F17A, F18, 
  F18A, F19, F20, F21, F22, F23, F70, F25, F25A, F26, F26A, F27, F27A, F28, F29, 
  F30, F31, F31A, F32, F32A, F33, F33A, F34, F34A, F35, F35A, F36, F36A, F37, 
 F37A, F38, F38A, F39, F39A, F40, F40A, F41, F41A, F42, F42A, F43, F43A, F44, 
 F44A, F45, F45A, F46, F46A, F47, F47A, F48, F48A, F20A, F70A, F19A 
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004 
5. Others 
 Sof(F46A)=Sof(F47A)=Sof(F48A)=1-FVAR(1) 
 Sof(F46)=Sof(F47)=Sof(F48)=FVAR(1) 
 Sof(F34A)=Sof(F35A)=Sof(F36A)=1-FVAR(2) 
 Sof(F34)=Sof(F35)=Sof(F36)=FVAR(2) 
 Sof(F31A)=Sof(F32A)=Sof(F33A)=1-FVAR(3) 
 Sof(F31)=Sof(F32)=Sof(F33)=FVAR(3) 
 Sof(F25A)=Sof(F26A)=Sof(F27A)=1-FVAR(4) 
 Sof(F25)=Sof(F26)=Sof(F27)=FVAR(4) 
 Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(5) 
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(5) 
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(6) 
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(6) 
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(7) 
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(7) 
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(8) 
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(8) 
 Sof(F43A)=Sof(F44A)=Sof(F45A)=1-FVAR(9) 
 Sof(F43)=Sof(F44)=Sof(F45)=FVAR(9) 
 Sof(F37A)=Sof(F38A)=Sof(F39A)=1-FVAR(10) 
 Sof(F37)=Sof(F38)=Sof(F39)=FVAR(10) 
 Sof(F40A)=Sof(F41A)=Sof(F42A)=1-FVAR(11) 
 Sof(F40)=Sof(F41)=Sof(F42)=FVAR(11) 
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(12) 
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(12) 
 Sof(F20A)=Sof(F70A)=Sof(F19A)=1-FVAR(13) 
 Sof(F19)=Sof(F20)=Sof(F70)=FVAR(13) 
6.a Secondary CH2 refined with riding coordinates: 
 C4(H4A,H4B), C6(H6A,H6B), C8(H8A,H8B), C10(H10A,H10B), C12(H12A,H12B), 
 C13(H13A,H13B), C18(H18A,H18B), C20(H20A,H20B), C22(H22A,H22B), C24(H24A,H24B), 
  C26(H26A,H26B), C27(H27A,H27B) 
6.b Aromatic/amide H refined with riding coordinates: 
 C30(H30), C32(H32), C34(H34), C38(H38), C40(H40), C42(H42), C46(H46), 
 C48(H48), C50(H50), C54(H54), C56(H56), C58(H58), C62(H62), C64(H64), C66(H66), 
  C70(H70), C72(H72), C74(H74), C78(H78), C80(H80), C82(H82), C86(H86), 
 C88(H88), C90(H90) 
6.c Idealised Me refined as rotating group: 
 C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), 
 C14(H14A,H14B,H14C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C23(H23A,H23B, 
 H23C), C25(H25A,H25B,H25C), C28(H28A,H28B,H28C) 
;
_shelx_res_checksum              14921
_olex2_submission_special_instructions 'No special instructions were received'