Synthesis and Characterization of Symmetrically versus Unsymmetrically Proton-Bridged Hexa-Iron Clusters
De Silva, D. Nirosha T.; Dais, Tyson N.; Jameson, Geoffrey B.; Cutler, Daniel J.; Brechin, Euan K.; Davies, Casey G.; Jameson, Guy N. L.; Plieger, Paul G.; ACS Omega 6 (2021) 16661–16669; doi:10.1021/acsomega.1c02255

data_4518818
_publ_section_title
;
 Synthesis and Characterization of Symmetrically versus Unsymmetrically
 Proton-Bridged Hexa-Iron Clusters
;
_journal_issue                   25
_journal_name_full               'ACS Omega'
_journal_page_first              16661
_journal_page_last               16669
_journal_paper_doi               10.1021/acsomega.1c02255
_journal_volume                  6
_journal_year                    2021
_chemical_formula_moiety
'C78 H102 F6 Fe6 N12 O20, C78 H101 F6 Fe6 N12 O20, 2(B F4)'
_chemical_formula_sum            'C156 H203 B2 F20 Fe12 N24 O40'
_chemical_formula_weight         4126.23
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-03
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
????
;
_cell_angle_alpha                107.161(8)
_cell_angle_beta                 99.537(7)
_cell_angle_gamma                100.103(7)
_cell_formula_units_Z            1
_cell_length_a                   16.8193(10)
_cell_length_b                   17.3271(10)
_cell_length_c                   21.1897(15)
_cell_measurement_reflns_used    7152
_cell_measurement_temperature    160
_cell_measurement_theta_max      65.4
_cell_measurement_theta_min      6.6
_cell_volume                     5651.6(7)
_computing_cell_refinement
;
CrystalClear-SM Expert 2.0 rc14 (Rigaku, 2009)
;
_computing_data_collection
;
CrystalClear-SM Expert 2.0 rc14 (Rigaku, 2009)
;
_computing_data_reduction
;
CrystalClear-SM Expert 2.0 rc14 (Rigaku, 2009)
;
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      160
_diffrn_detector                 RX
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.946
_diffrn_measured_fraction_theta_max 0.946
_diffrn_measurement_details
;
scan:
	Number of images: 72
	           Slice: 20.0000 - 200.0000
	     Image width: 2.5000
	        Exp time: 240.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 0.0000
	             Phi: 90.0000
	             XTD: 127.4000
	          2theta: 0.0000
scan:
	Number of images: 72
	           Slice: 20.0000 - 200.0000
	     Image width: 2.5000
	        Exp time: 240.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 54.0000
	             Phi: 180.0000
	             XTD: 127.4000
	          2theta: 0.0000
scan:
	Number of images: 72
	           Slice: 20.0000 - 200.0000
	     Image width: 2.5000
	        Exp time: 240.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 54.0000
	             Phi: 0.0000
	             XTD: 127.4000
	          2theta: 0.0000
scan:
	Number of images: 70
	           Slice: 22.0000 - 197.0000
	     Image width: 2.5000
	        Exp time: 240.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 54.0000
	             Phi: 270.0000
	             XTD: 127.4000
	          2theta: 0.0000
scan:
	Number of images: 60
	           Slice: 20.0000 - 170.0000
	     Image width: 2.5000
	        Exp time: 240.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 0.0000
	             Phi: 270.0000
	             XTD: 127.4000
	          2theta: 0.0000
scan:
	Number of images: 54
	           Slice: 53.0000 - 188.0000
	     Image width: 2.5000
	        Exp time: 240.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 54.0000
	             Phi: 90.0000
	             XTD: 127.4000
	          2theta: 0.0000

;
_diffrn_measurement_device
;
Crystal Goniometer
;
_diffrn_measurement_device_type
;
Rigaku RAXIS conversion
;
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support Loop
_diffrn_orient_matrix_type       FS_PROCESS
_diffrn_orient_matrix_UB_11      -0.042882
_diffrn_orient_matrix_UB_12      0.006177
_diffrn_orient_matrix_UB_13      0.027473
_diffrn_orient_matrix_UB_21      -0.001687
_diffrn_orient_matrix_UB_22      -0.056931
_diffrn_orient_matrix_UB_23      0.002620
_diffrn_orient_matrix_UB_31      0.044848
_diffrn_orient_matrix_UB_32      0.024254
_diffrn_orient_matrix_UB_33      0.042610
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.126
_diffrn_reflns_av_unetI/netI     0.210
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            77177
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        65.4
_diffrn_reflns_theta_max         65.4
_diffrn_reflns_theta_min         6.6
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           40.0
_diffrn_source_power             2.0
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.662
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.346
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            Red
_exptl_crystal_density_diffrn    1.212
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Chunk
_exptl_crystal_F_000             2129
_exptl_crystal_size_max          0.752
_exptl_crystal_size_mid          0.382
_exptl_crystal_size_min          0.25
_refine_diff_density_max         1.617
_refine_diff_density_min         -0.839
_refine_diff_density_rms         0.087
_refine_ls_extinction_coef       0.00103(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1098
_refine_ls_number_reflns         18822
_refine_ls_number_restraints     217
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.1491
_refine_ls_R_factor_gt           0.1049
_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^)+(0.1782P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2810
_refine_ls_wR_factor_ref         0.3259
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9637
_reflns_number_total             18822
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao1c02255_si_001.cif
_cod_data_source_block           nds131a_f
_cod_depositor_comments
'Adding full bibliography for 4518818--4518819.cif.'
_cod_database_code               4518818
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H62A,H62B,H621} of C621, All C(H,H) groups, All C(H,H,H,
  H) groups, All N(H) groups
 At 1.5 times of:
  {H46A,H46B,H46C} of C461, {H42A,H42B,H42C} of C421, {H45A,H45B,H45C} of
  C451, {H41A,H41B,H41C} of C411, {H44A,H44B,H44C} of C441, {H2A,H2B,H2C} of C2
2. Restrained distances
 C621-N622 \\sim C621-N721
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O253 \\sim N252: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
N622 \\sim C623 \\sim C625 \\sim O627 \\sim C626 \\sim C624: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
N721 \\sim C722 \\sim C724 \\sim C723 \\sim C725 \\sim O726: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C12: within 1.7A with sigma of 0.05 and sigma for terminal atoms of 0.1 within
1.7A
O617 \\sim C615 \\sim C614 \\sim N612 \\sim C613 \\sim C616: within 1.7A with
sigma of 0.05 and sigma for terminal atoms of 0.1 within 1.7A
Uanis(C12) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(N662) \\sim Ueq, Uanis(N762) \\sim Ueq, Uanis(C663) \\sim Ueq,
Uanis(C764) \\sim Ueq, Uanis(C665) \\sim Ueq, Uanis(C766) \\sim Ueq,
Uanis(O667) \\sim Ueq, Uanis(O767) \\sim Ueq, Uanis(C666) \\sim Ueq,
Uanis(C765) \\sim Ueq, Uanis(C664) \\sim Ueq, Uanis(C763) \\sim Ueq: with sigma
of 0.04 and sigma for terminal atoms of 0.1
Uanis(F4) \\sim Ueq, Uanis(B2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F5) \\sim
Ueq, Uanis(F6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(N662) = Uanis(N762)
Uanis(C664) = Uanis(C763)
Uanis(C666) = Uanis(C765)
Uanis(O667) = Uanis(O767)
Uanis(C665) = Uanis(C766)
Uanis(C663) = Uanis(C764)
Uanis(N622) = Uanis(N721)
Uanis(C623) = Uanis(C723)
Uanis(C625) = Uanis(C725)
Uanis(O627) = Uanis(O726)
Uanis(C626) = Uanis(C724)
Uanis(C624) = Uanis(C722)
4. Others
 Sof(H66A)=Sof(H66B)=Sof(O767)=Sof(C766)=Sof(H76A)=Sof(H76B)=Sof(C764)=
 Sof(H76C)=Sof(H76D)=Sof(N762)=Sof(H762)=Sof(C763)=Sof(H76E)=Sof(H76F)=
 Sof(C765)=Sof(H76G)=Sof(H76H)=1-FVAR(1)
 Sof(H66C)=Sof(H66D)=Sof(C664)=Sof(H66E)=Sof(H66F)=Sof(N662)=Sof(H662)=
 Sof(C663)=Sof(H66G)=Sof(H66H)=Sof(C665)=Sof(H66I)=Sof(H66J)=Sof(O667)=
 Sof(C666)=Sof(H66K)=Sof(H66L)=FVAR(1)
 Fixed Sof: H62A(0.5) H62B(0.5) H621(0.5) C623(0.5) H62C(0.5) H62D(0.5)
 N622(0.5) H622(0.5) C624(0.5) H62E(0.5) H62F(0.5) C626(0.5) H62G(0.5)
 H62H(0.5) O627(0.5) C625(0.5) H62I(0.5) H62J(0.5) N721(0.5) H721(0.5)
 C722(0.5) H72A(0.5) H72B(0.5) C723(0.5) H72C(0.5) H72D(0.5) C725(0.5)
 H72E(0.5) H72F(0.5) O726(0.5) C724(0.5) H72G(0.5) H72H(0.5)
5.a Free rotating group:
 C623(N622,C624,C626,O627,C625,N721), B2(F3,F4,F5,F6), C614(C615,O617,C616,
 C613,N612), C722(C723,C725,O726,C724,C2), C664(N662,C663,C665,O667,C666,O767,
 C766,C764,N762,C763,C765)
5.b Ternary CH refined with riding coordinates:
 N652(H652), N632(H632), N642(H642), N622(H622), N721(H721), N612(H612),
 N662(H662), N762(H762)
5.c Secondary CH2 refined with riding coordinates:
 C641(H64A,H64B), C654(H65A,H65B), C653(H65C,H65D), C636(H63A,H63B), C661(H66C,
 H66D), C661(H66A,H66B), C631(H63C,H63D), C651(H65E,H65F), C644(H64C,H64D),
 C611(H61A,H61B), C635(H63E,H63F), C634(H63G,H63H), C646(H64E,H64F), C655(H65G,
 H65H), C656(H65I,H65J), C633(H63I,H63J), C645(H64G,H64H), C643(H64I,H64J),
 C621(H62A,H62B), C623(H62C,H62D), C624(H62E,H62F), C626(H62G,H62H), C625(H62I,
 H62J), C614(H61C,H61D), C615(H61E,H61F), C616(H61G,H61H), C613(H61I,H61J),
 C722(H72A,H72B), C723(H72C,H72D), C725(H72E,H72F), C724(H72G,H72H), C664(H66E,
 H66F), C663(H66G,H66H), C665(H66I,H66J), C666(H66K,H66L), C766(H76A,H76B),
 C764(H76C,H76D), C763(H76E,H76F), C765(H76G,H76H)
5.d Aromatic/amide H refined with riding coordinates:
 C55(H55), C35(H35), C52(H52), C33(H33), C36(H36), C54(H54), C32(H32),
 C56(H56), C221(H221), C34(H34), C53(H53), C51(H51), C7(H7), C231(H231),
 C241(H241), C261(H261), C211(H211), C251(H251), C621(H621)
5.e Fitted hexagon refined as free rotating group:
 C45(C55,C65,C15,C25,C35)
5.f Idealised Me refined as rotating group:
 C461(H46A,H46B,H46C), C421(H42A,H42B,H42C), C411(H41A,H41B,H41C), C451(H45A,
 H45B,H45C), C441(H44A,H44B,H44C), C2(H2A,H2B,H2C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              62085
_shelx_hkl_checksum              39468
_shelx_fab_checksum              97840
_olex2_submission_special_instructions 'No special instructions were received'