# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2022

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_rivy6
_database_code_depnum_ccdc_archive 'CCDC 1582351'
loop_
_audit_author_name
_audit_author_address
'Inigo Vitorica' 'University of Manchester'
_audit_update_record             
;
2017-10-26 deposited with the CCDC.	2022-01-03 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT308_rivy6               
;
PROBLEM: Single Bonded Metal Atom in Structure  (Unusual)        Fe1 Check
RESPONSE: Iron metal centres are appropriately connected having a distorted tetrahedral coordination enviroment 
;
# Added during the CSD deposition process: Thursday 26 October 2017 04:48 PM
# end Validation Reply Form

_audit_creation_date             2017-05-23
_audit_creation_method           
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_shelxl_version_number           2014/6
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '0.5(C28 H16 F4 Fe2 N8)'
_chemical_formula_sum            'C14 H8 F2 Fe N4'
_chemical_formula_weight         326.09
_chemical_melting_point          ?
_chemical_oxdiff_formula         FeN4F2C20H20
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 1 2/c 1'
_space_group_name_Hall           '-C 2yc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'

_cell_length_a                   8.2727(5)
_cell_length_b                   8.2567(4)
_cell_length_c                   19.3526(14)
_cell_angle_alpha                90
_cell_angle_beta                 97.498(6)
_cell_angle_gamma                90
_cell_volume                     1310.58(14)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    7235
_cell_measurement_temperature    100.00(14)
_cell_measurement_theta_max      26.5260
_cell_measurement_theta_min      3.4690
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    1.171
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69002
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.27b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.653
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0614
_diffrn_reflns_av_unetI/netI     0.0217
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            13800
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.370
_diffrn_reflns_theta_min         2.123
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -48.00  82.00   1.00   20.00    --   -7.30  76.00  90.00  130
  2  ω    -39.00  33.00   1.00   20.00    --   -7.30 -76.00 -60.00   72
  3  ω    -96.00  32.00   1.00   20.00    --   -7.30 -38.00  90.00  128
  4  ω    -48.00  31.00   1.00   20.00    --   -7.30  76.00-150.00   79
  5  ω     44.00  82.00   1.00   20.00    --   -7.30  76.00-150.00   38
  6  ω    -48.00  31.00   1.00   20.00    --   -7.30  76.00 150.00   79
  7  ω     48.00  82.00   1.00   20.00    --   -7.30  76.00 150.00   34
  8  ω    -48.00  33.00   1.00   20.00    --   -7.30  76.00 -90.00   81
  9  ω     44.00  82.00   1.00   20.00    --   -7.30  76.00 -90.00   38
 10  ω    -47.00  63.00   1.00   20.00    --   -7.30  38.00  60.00  110
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0827045000
_diffrn_orient_matrix_UB_12      -0.0250792000
_diffrn_orient_matrix_UB_13      0.0042425000
_diffrn_orient_matrix_UB_21      -0.0068520000
_diffrn_orient_matrix_UB_22      -0.0190862000
_diffrn_orient_matrix_UB_23      -0.0359978000
_diffrn_orient_matrix_UB_31      0.0242988000
_diffrn_orient_matrix_UB_32      0.0798780000
_diffrn_orient_matrix_UB_33      -0.0073666000
_diffrn_oxdiff_ac3_digest_frames 
;
01fdf04fde615f421bcda037efac789bc1007895ef1
;
_diffrn_oxdiff_ac3_digest_hkl    
;
01fd5a98b85f47d546654ac369435b9caf4138
;
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1307
_reflns_number_total             1350
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.534
_refine_diff_density_min         -0.813
_refine_diff_density_rms         0.111
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.222
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     170
_refine_ls_number_reflns         1350
_refine_ls_number_restraints     135
_refine_ls_R_factor_all          0.0594
_refine_ls_R_factor_gt           0.0585
_refine_ls_restrained_S_all      1.170
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0558P)²+11.5144P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1524
_refine_ls_wR_factor_ref         0.1529
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Uiso/Uaniso restraints and constraints
F1 \\sim F3 \\sim F4 \\sim F2: within 2A with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(F3) = Uanis(F4)
3. Rigid body (RIGU) restrains
 F1, F2, C7, C6, C5, C4, C9, C8, N1, C2, N3
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F3, F4, C14, C13, C12, C11, C16, C15, C10, N1, N3
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Others
 Sof(H13)=Sof(F4)=0.5*(1-FVAR(2))
 Sof(H14)=Sof(F3)=0.5*FVAR(2)
 Sof(H7)=Sof(F1)=0.5*(1-FVAR(3))
 Sof(H6)=Sof(F2)=0.5*FVAR(3)
 Fixed Sof: C13(0.5) C14(0.5) C11(0.5) C2(0.5) H2(0.5) C10(0.5) H10(0.5)
 C16(0.5) C5(0.5) H5(0.5) C4(0.5) C9(0.5) C8(0.5) H8(0.5) C7(0.5) C6(0.5)
 C15(0.5) H15(0.5) C12(0.5) H12(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C2(H2), C10(H10), C5(H5), C8(H8), C7(H7), C6(H6),
 C15(H15), C12(H12)
5.b Fitted hexagon refined as free rotating group:
 C5(C4,C9,C8,C7,C6)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Fe1 Fe 1.0000 0.67422(9) 0.7500 0.0189(3) Uani 1 2 d S T P . .
N3 N 0.6384(4) 0.3273(4) 0.70001(19) 0.0222(7) Uani 1 1 d . U . . .
N1 N 0.8323(4) 0.5206(4) 0.69921(19) 0.0218(7) Uani 1 1 d . U . . .
C13 C 0.4138(13) 0.5863(14) 0.5624(6) 0.036(2) Uani 0.5 1 d . U . A -1
H13 H 0.3171 0.5983 0.5324 0.043 Uiso 0.380(8) 1 calc R . . B -1
C14 C 0.5356(14) 0.7028(13) 0.5627(6) 0.036(2) Uani 0.5 1 d . U . A -1
H14 H 0.5158 0.7911 0.5329 0.044 Uiso 0.120(8) 1 calc R . . B -1
C11 C 0.5807(9) 0.4439(10) 0.6495(4) 0.0211(14) Uani 0.5 1 d . U . A -1
C2 C 0.7028(10) 0.4637(10) 0.7274(5) 0.0230(15) Uani 0.5 1 d . U . A -2
H2 H 0.6614 0.5165 0.7638 0.028 Uiso 0.5 1 calc R . . A -2
C10 C 0.7827(10) 0.3857(11) 0.7272(5) 0.0235(15) Uani 0.5 1 d . U . A -1
H10 H 0.8459 0.3343 0.7641 0.028 Uiso 0.5 1 calc R . . A -1
C16 C 0.7027(9) 0.5623(10) 0.6484(4) 0.0209(13) Uani 0.5 1 d . U . A -1
C5 C 0.7407(6) 0.1539(6) 0.6060(3) 0.0275(16) Uani 0.5 1 d . U . A -2
H5 H 0.6621 0.0735 0.6064 0.033 Uiso 0.5 1 calc R . . A -2
C4 C 0.7397(5) 0.2870(6) 0.6499(3) 0.0205(13) Uani 0.5 1 d G U . A -2
C9 C 0.8571(6) 0.4073(5) 0.6494(3) 0.0209(14) Uani 0.5 1 d G U . A -2
C8 C 0.9755(6) 0.3945(7) 0.6049(3) 0.0290(17) Uani 0.5 1 d G U . A -2
H8 H 1.0540 0.4749 0.6045 0.035 Uiso 0.5 1 calc R . . A -2
C7 C 0.9765(7) 0.2614(8) 0.5609(3) 0.0322(19) Uani 0.5 1 d G U . A -2
H7 H 1.0557 0.2528 0.5312 0.039 Uiso 0.133(12) 1 calc R . . C -2
C6 C 0.8591(8) 0.1411(7) 0.5615(3) 0.034(2) Uani 0.5 1 d G U . A -2
H6 H 0.8598 0.0521 0.5321 0.041 Uiso 0.367(12) 1 calc R . . C -2
C15 C 0.6818(11) 0.6953(10) 0.6040(5) 0.0274(16) Uani 0.5 1 d . U . A -1
H15 H 0.7622 0.7735 0.6026 0.033 Uiso 0.5 1 calc R . . A -1
C12 C 0.4340(10) 0.4551(11) 0.6052(5) 0.0288(17) Uani 0.5 1 d . U . A -1
H12 H 0.3535 0.3764 0.6050 0.035 Uiso 0.5 1 calc R . . A -1
F3 F 0.286(4) 0.597(4) 0.5161(16) 0.049(2) Uani 0.120(8) 1 d . U . A -5
F4 F 0.5053(14) 0.8320(11) 0.5181(5) 0.049(2) Uani 0.380(8) 1 d . U . A -6
F2 F 1.0873(11) 0.2486(14) 0.5183(5) 0.046(3) Uani 0.367(12) 1 d . U . A -3
F1 F 0.856(4) 0.025(4) 0.5180(15) 0.058(10) Uani 0.133(12) 1 d . U . A -4


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Fe1 N3 2.033(3) 3 ?
Fe1 N3 2.033(3) 4_656 ?
Fe1 N1 2.036(3) . ?
Fe1 N1 2.036(3) 2_756 ?
N3 Fe1 2.033(3) 3_445 ?
N3 C11 1.410(9) . ?
N3 C2 1.327(9) . ?
N3 C10 1.331(9) . ?
N3 C4 1.402(5) . ?
N1 C2 1.349(9) . ?
N1 C10 1.327(9) . ?
N1 C16 1.399(9) . ?
N1 C9 1.379(5) . ?
C13 H13 0.9300 . ?
C13 C14 1.392(15) . ?
C13 C12 1.361(14) . ?
C13 F3 1.30(3) . ?
C14 H14 0.9300 . ?
C14 C15 1.362(14) . ?
C14 F4 1.375(13) . ?
C11 C16 1.407(11) . ?
C11 C12 1.394(11) . ?
C2 H2 0.9300 . ?
C10 H10 0.9300 . ?
C16 C15 1.391(12) . ?
C5 H5 0.9300 . ?
C5 C4 1.3900 . ?
C5 C6 1.3900 . ?
C4 C9 1.3900 . ?
C9 C8 1.3900 . ?
C8 H8 0.9300 . ?
C8 C7 1.3900 . ?
C7 H7 0.9300 . ?
C7 C6 1.3900 . ?
C7 F2 1.316(8) . ?
C6 H6 0.9300 . ?
C6 F1 1.27(3) . ?
C15 H15 0.9300 . ?
C12 H12 0.9300 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N3 Fe1 N3 103.1(2) 3 4_656 ?
N3 Fe1 N1 103.08(14) 4_656 . ?
N3 Fe1 N1 123.24(14) 4_656 2_756 ?
N3 Fe1 N1 123.24(14) 3 . ?
N3 Fe1 N1 103.08(14) 3 2_756 ?
N1 Fe1 N1 102.9(2) . 2_756 ?
C11 N3 Fe1 126.4(4) . 3_445 ?
C2 N3 Fe1 124.0(4) . 3_445 ?
C2 N3 C4 103.5(5) . . ?
C10 N3 Fe1 124.7(4) . 3_445 ?
C10 N3 C11 103.4(5) . . ?
C4 N3 Fe1 127.3(3) . 3_445 ?
C2 N1 Fe1 123.3(4) . . ?
C2 N1 C9 104.2(5) . . ?
C10 N1 Fe1 123.6(4) . . ?
C10 N1 C16 104.1(5) . . ?
C16 N1 Fe1 126.7(4) . . ?
C9 N1 Fe1 127.3(3) . . ?
C14 C13 H13 119.5 . . ?
C12 C13 H13 119.5 . . ?
C12 C13 C14 121.0(10) . . ?
C13 C14 H14 118.0 . . ?
C15 C14 C13 123.9(10) . . ?
C15 C14 H14 118.0 . . ?
C16 C11 N3 107.8(6) . . ?
C12 C11 N3 131.3(7) . . ?
C12 C11 C16 120.9(8) . . ?
N3 C2 N1 115.6(7) . . ?
N3 C2 H2 122.2 . . ?
N1 C2 H2 122.2 . . ?
N3 C10 H10 121.6 . . ?
N1 C10 N3 116.8(7) . . ?
N1 C10 H10 121.6 . . ?
N1 C16 C11 107.7(7) . . ?
C15 C16 N1 130.5(7) . . ?
C15 C16 C11 121.7(8) . . ?
C4 C5 H5 120.0 . . ?
C4 C5 C6 120.0 . . ?
C6 C5 H5 120.0 . . ?
C5 C4 N3 131.5(3) . . ?
C5 C4 C9 120.0 . . ?
C9 C4 N3 108.5(3) . . ?
N1 C9 C4 108.2(3) . . ?
N1 C9 C8 131.8(3) . . ?
C8 C9 C4 120.0 . . ?
C9 C8 H8 120.0 . . ?
C9 C8 C7 120.0 . . ?
C7 C8 H8 120.0 . . ?
C8 C7 H7 120.0 . . ?
C8 C7 C6 120.0 . . ?
C6 C7 H7 120.0 . . ?
C5 C6 H6 120.0 . . ?
C7 C6 C5 120.0 . . ?
C7 C6 H6 120.0 . . ?
C14 C15 C16 115.3(8) . . ?
C14 C15 H15 122.3 . . ?
C16 C15 H15 122.3 . . ?
C13 C12 C11 117.1(9) . . ?
C13 C12 H12 121.5 . . ?
C11 C12 H12 121.5 . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.274
_oxdiff_exptl_absorpt_empirical_full_min 0.812
