Aromatic C-F Hydroxylation by Nonheme Iron(IV)-Oxo Complexes: Structural, Spectroscopic, and Mechanistic Investigations.
Sahu, Sumit; Zhang, Bo; Pollock, Christopher J.; Dürr, Maximilian; Davies, Casey G.; Confer, Alex M.; Ivanović-Burmazović, Ivana; Siegler, Maxime A.; Jameson, Guy N. L.; Krebs, Carsten; Goldberg, David P.; Journal of the American Chemical Society 138 (2016) 12791–12802; doi:10.1021/jacs.6b03346

data_4130429
_publ_section_title
;
 Aromatic C-F Hydroxylation by Nonheme Iron(IV)-Oxo Complexes: Structural,
 Spectroscopic, and Mechanistic Investigations.
;
_journal_issue                   39
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12791
_journal_page_last               12802
_journal_paper_doi               10.1021/jacs.6b03346
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C35 H26 F4 Fe N5 O, Cl O4, H2 O'
_chemical_formula_sum            'C35 H28 Cl F4 Fe N5 O6'
_chemical_formula_weight         781.92
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 92.161(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4312(4)
_cell_length_b                   12.8954(3)
_cell_length_c                   18.3009(5)
_cell_measurement_reflns_used    10751
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      72.04
_cell_measurement_theta_min      6.12
_cell_volume                     3403.30(15)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.27t (release 29-11-2013 CrysAlis171 .NET)
(compiled Nov 29 2013,14:25:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.27t (release 29-11-2013 CrysAlis171 .NET)
(compiled Nov 29 2013,14:25:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.27t (release 29-11-2013 CrysAlis171 .NET)
(compiled Nov 29 2013,14:25:01)
;
_computing_molecular_graphics    'SHELXTL v6.10 (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL v6.10 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-2014/7 (Sheldrick, 2013)'
_diffrn_ambient_temperature      110(2)
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_source         'SuperNova (Cu) X-ray Source'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0165
_diffrn_reflns_av_unetI/netI     0.0153
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            22245
_diffrn_reflns_point_group_measured_fraction_full 0.909
_diffrn_reflns_point_group_measured_fraction_max 0.898
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.493
_diffrn_reflns_theta_min         3.831
_exptl_absorpt_coefficient_mu    4.946
_exptl_absorpt_correction_T_max  0.511
_exptl_absorpt_correction_T_min  0.255
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.27t (release 29-11-2013 CrysAlis171 .NET)
(compiled Nov 29 2013,14:25:01)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.526
_exptl_crystal_description       block
_exptl_crystal_F_000             1600
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.853
_refine_diff_density_min         -0.369
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.005(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1077
_refine_ls_number_reflns         12531
_refine_ls_number_restraints     584
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0340
_refine_ls_R_factor_gt           0.0332
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0723P)^2^+0.5324P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0904
_refine_ls_wR_factor_ref         0.0909
_reflns_Friedel_coverage         0.728
_reflns_Friedel_fraction_full    0.818
_reflns_Friedel_fraction_max     0.794
_reflns_number_gt                12165
_reflns_number_total             12531
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b03346_si_004.cif
_cod_data_source_block           4
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4130429
_shelx_shelxl_version_number     2014/7
_twin_information
;

 * * * CRYSALIS TWIN DATA REDUCTION FINALIZING (Version 1.171.37.27t (release 29-11-2013 CrysAlis171 .NET)) * * *
Laue class: 2/m (b-unique) - Friedel mate is different
Lattice type: P-lattice 
DC PROFFITRRPTWIN INFO: Step 1 - Loading orientation matrices (UB) of 2 components
 
DC PROFFITRRPTWIN INFO: Loading UB component 1
 
DC PROFFITRRPTWIN INFO: Loading UB component 2
 
DC PROFFITRRPTWIN INFO: Step 2 - Computing crossed twin laws
 
Twin law determination (relative to component 1)
Matrix 1 is taken from component 1 (  14.414   12.888   18.305    89.99    92.17    90.03)
Matrix 2 is taken from component 2 (  14.414   12.888   18.304    89.98    92.14    89.96)
Twin analysis: Component 1 with component 2
TL  =UB[1]-1*UB[2]:   1.0001  -0.0000   0.0009     0.0000  -1.0000   0.0000    -0.0943   0.0001  -1.0001   det 1.000070
TL-1=UB[2]*UB[1]-1:   1.0000  -0.0000   0.0009     0.0000  -1.0000  -0.0000    -0.0943  -0.0001  -1.0000   det 0.999930
Rot= 179.9985 deg around the following vectors: 
Reciprocal space (hkl): 0.9989 0.0000 -0.0471
Direct space (uvw)    : 1.0000 0.0007 0.0006
 
DC PROFFITRRPTWIN INFO: Step 3 - Loading reflections of 2 components
 
DC PROFFITRRPTWIN ALL INFO: Component 1
DC PROFFITRRPTWIN INFO: Face list of component 1 
  1:  -0.9898   0.9994 -11.9065  d=   0.0885
  2:   8.0056  -0.9997  -6.7555  d=   0.1543
  3:  -6.9937  -3.0010  -7.3395  d=   0.1577
  4:   5.0079  -3.0001  -9.4724  d=   0.1418
  5:  -8.0056   1.9997   6.7555  d=   0.1750
  6:  -3.0087   3.0003  10.2837  d=   0.1485
  7:   3.9918   4.0009   9.6228  d=   0.1548
  8:  -8.0057  -2.0004   6.7557  d=   0.1625
  9:  -3.0088  -3.9999  10.2842  d=   0.1096
 10:   0.9914  -3.9996   9.9066  d=   0.1066
 11:   3.9916  -3.9994   9.6234  d=   0.1209
 12:   7.9954  -1.9992   5.2454  d=   0.1488
 13:   8.0057   2.0004  -6.7557  d=   0.1507
 14:   2.0088   3.9999 -10.1898  d=   0.1193
 15:   7.0012  -4.9997  -1.6605  d=   0.1728
 16:   9.0015   0.0006  -1.8497  d=   0.1594
 17:   9.0007   2.0007  -0.8497  d=   0.1591
 18:   5.0005   7.0007  -0.4725  d=   0.1715
 19:  -5.0010   7.0000   1.4716  d=   0.1838
 20:   0.0086   3.9997 -10.0010  d=   0.1165
 21:  -9.0007  -2.0007   0.8497  d=   0.1897
 22:  -6.0006  -6.0007   0.5668  d=   0.1613
 23:  -1.0103  -0.9996  12.0953  d=   0.1011
 24:  -4.9945  -5.0009  -6.5281  d=   0.1491
 25:  -9.0014   0.9994   1.8496  d=   0.1859
 26:   5.0010  -7.0000  -1.4716  d=   0.1778
 27:  -4.0009   8.0001   1.3771  d=   0.1826
 28:   8.9973   2.0009   3.1505  d=   0.1510
 29:  -9.0041  -1.0005   4.8499  d=   0.1790
 30:   3.0069  -5.0003  -8.2834  d=   0.1622
 31:   5.9919  -0.9992   9.4344  d=   0.1201
 32:   1.0094  -3.0005 -11.0949  d=   0.1431
 33:   1.9899  -0.9994  11.8121  d=   0.0962
 34:   6.0081   1.0001  -9.5671  d=   0.1277
 35:   2.0046   7.0002  -5.1896  d=   0.1633
 36:  -4.9988  -7.0007  -1.5276  d=   0.1731
 37:  -2.9958   6.9998  -4.7176  d=   0.1638
 38:  -4.0089  -1.9999  10.3784  d=   0.1212
DC PROFFITRRPTWIN ALL INFO: Component 2
DC PROFFITRRPTWIN INFO: Face list of component 2 
  1:  -1.0002  -0.9993  12.0000  d=   0.0885
  2:   7.9998   1.0002   6.0013  d=   0.1543
  3:  -7.0001   3.0008   7.9992  d=   0.1577
  4:   4.9997   3.0005   9.0009  d=   0.1418
  5:  -7.9998  -2.0002  -6.0013  d=   0.1750
  6:  -2.9997  -3.0006 -10.0006  d=   0.1485
  7:   4.0002  -4.0008  -9.9997  d=   0.1548
  8:  -7.9998   1.9999  -6.0012  d=   0.1625
  9:  -2.9999   3.9996 -10.0004  d=   0.1096
 10:   1.0001   3.9995  -9.9998  d=   0.1066
 11:   4.0001   3.9994  -9.9994  d=   0.1209
 12:   8.0000   1.9994  -5.9989  d=   0.1488
 13:   7.9998  -1.9999   6.0012  d=   0.1507
 14:   1.9999  -3.9995  10.0003  d=   0.1193
 15:   6.9998   5.0000   1.0012  d=   0.1728
 16:   8.9999  -0.0002   1.0013  d=   0.1594
 17:   8.9999  -2.0003   0.0012  d=   0.1591
 18:   5.0001  -7.0003   0.0005  d=   0.1715
 19:  -4.9998  -7.0001  -1.0010  d=   0.1838
 20:  -0.0001  -3.9995  10.0000  d=   0.1165
 21:  -8.9999   2.0003  -0.0012  d=   0.1897
 22:  -6.0001   6.0003  -0.0007  d=   0.1613
 23:  -0.9998   0.9993 -12.0003  d=   0.1011
 24:  -5.0002   5.0007   6.9995  d=   0.1491
 25:  -8.9999  -0.9998  -1.0013  d=   0.1859
 26:   4.9998   7.0001   1.0010  d=   0.1778
 27:  -3.9998  -8.0002  -1.0009  d=   0.1826
 28:   9.0000  -2.0006  -3.9988  d=   0.1510
 29:  -8.9998   1.0000  -4.0013  d=   0.1790
 30:   2.9997   5.0005   8.0007  d=   0.1622
 31:   6.0001   0.9992  -9.9992  d=   0.1201
 32:   0.9997   3.0007  11.0004  d=   0.1431
 33:   2.0002   0.9992 -11.9998  d=   0.0962
 34:   5.9998  -0.9996   9.0009  d=   0.1277
 35:   2.0000  -6.9999   5.0001  d=   0.1633
 36:  -5.0001   7.0005   1.9995  d=   0.1731
 37:  -2.9999  -6.9998   4.9994  d=   0.1638
 38:  -3.9998   1.9996 -10.0006  d=   0.1212
 
DC PROFFITRRPTWIN INFO: Step 4 - Analysing composite reflections of 2 components
 
Component 1: 25026 observations read
Component 2: 24943 observations read

35254 composite observations collected (20590 fully isolated, 14664 overlapped), 38 skipped due to one or more missing parts

OVERLAP STATISTICS

2 COMPONENTS

COMPONENTS 1, 2
 Overlap factor | # in range | % of all obs 
 -------------- | ---------- | ------------ 
   0.00 - 0.20  |       4740 |    13.4 <--- ALMOST SEPARATED
   0.20 - 0.40  |       3089 |     8.8
   0.40 - 0.60  |       2864 |     8.1
   0.60 - 0.80  |       2319 |     6.6
   0.80 - 1.00  |       1652 |     4.7 <--- FULLY OVERLAPPED
 -------------- | ---------- | ------------ 
      Total     |      14664 |    41.6

 
DC PROFFITRRPTWIN INFO: Step 5 - Scaling data & analysing twin ratios of 2 components
 
Computed twin ratios:
Twin 1: 55.38% (18751 common observations, 8395 merged)
Twin 2: 44.62% (18407 common observations, 8395 merged)

Preparing data for SCALE3 ABSPACK...

SCALING COMPONENT 1

18282 of 25000 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-9741631.0000 max=40256348.0000
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=563.6312 max=348906.6875

SCALING COMPONENT 2

18281 of 24918 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-17459254.0000 max=40256348.0000
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=563.2318 max=354171.2188

Computed twin ratios:
Twin 1: 55.52% (18751 common observations, 8395 merged)
Twin 2: 44.48% (18407 common observations, 8395 merged)

DC PROFFITRRPTWIN INFO: Determining HKLF4 overlap threshold for completeness requirement (>=80.0%)
DC PROFFITRRPTWIN INFO: New HKLF4 overlap threshold - 0.72

DC PROFFITRRPTWIN INFO: Step 6 - Decomposed intensities statistics (HKLF4)
 
COMPONENT 1

 
Note: The Rint, Rsigma and RsigmaB values are computed for redundant data only!
	Mean F2 and F2/sig(F2) are given for all measured values!
Note: The RsigmaA values are computed for all measured values!

Help: For more information about computations of rint and rsigma please look into Crysalis help: 
 file:__#HELP_DTheoryAlgorithm_DataReductionOutput.html
 

Statistics vs intensity - point group symmetry: P2 (b-unique)
                      #        #        #      average    mean      mean        
         intensity measured   kept    unique  redundancy   F2     F2/sig(F2)   Rint   Rsigma
--------------------------------------------------------------------------------------------
 28806661- 1124954     3423     3423     1073    3.2   2912883.58   141.76    0.065    0.078
  1123736-  640482     2736     2736     1073    2.5    852375.00    65.55    0.059    0.064
   640267-  404459     2411     2411     1073    2.2    507253.08    43.15    0.077    0.081
   404455-  278307     2178     2178     1073    2.0    336877.53    31.51    0.079    0.081
   278231-  191465     2097     2097     1073    2.0    232263.07    23.93    0.087    0.092
   191416-  132371     2064     2064     1073    1.9    160187.77    17.36    0.112    0.115
   132292-   85833     1953     1953     1073    1.8    107088.58    12.66    0.120    0.126
    85817-   51852     1960     1960     1073    1.8     67403.19     8.82    0.124    0.123
    51813-   24956     1847     1847     1073    1.7     38042.87     5.19    0.155    0.161
    24955--1364372     1817     1817     1080    1.7      8327.75     1.64    0.445    0.548
------------------------------------------------------------------------------------------
 28806661--1364372    22486    22486    10737    2.1    689492.98    43.49    0.069    0.080
 

Statistics vs resolution - point group symmetry: P2 (b-unique)
resolu-      #        #        #               average    mean      mean          
tion(A)   measured   kept    unique           redundancy   F2     F2/sig(F2)   Rint   Rsigma   RsigmaA
------------------------------------------------------------------------------------------------------
 inf-1.85     4395     4395     1073             4.1   1980370.35   107.80    0.065    0.080     0.008
1.85-1.48     2571     2571     1073             2.4    844040.89    56.68    0.064    0.072     0.015
1.48-1.28     2223     2223     1073             2.1    538145.05    34.92    0.073    0.078     0.025
1.28-1.16     2088     2088     1073             1.9    411020.31    26.25    0.084    0.088     0.034
1.16-1.07     2870     2870     1073             2.7    361765.76    25.07    0.085    0.090     0.037
1.07-1.00     1996     1996     1073             1.9    314862.12    23.74    0.084    0.088     0.039
1.00-0.94     1600     1600     1073             1.5    217964.09    19.68    0.088    0.089     0.047
0.94-0.89     1629     1629     1073             1.5    156936.01    16.95    0.075    0.075     0.056
0.89-0.85     1619     1619     1073             1.5    110430.73    14.94    0.072    0.073     0.064
0.85-0.81     1495     1495     1080             1.4     84123.26    15.59    0.065    0.067     0.062
------------------------------------------------------------------------------------------------------
 inf-0.81    22486    22486    10737             2.1    689492.98    43.49    0.069    0.080     0.017
 

Statistics vs resolution (taking redundancy into account) - point group symmetry: P2 (b-unique)
resolu-      #        #        #       %       average    mean      mean          
tion(A)    kept     theory   unique complete  redundancy   F2     F2/sig(F2)   Rint  RsigmaB
--------------------------------------------------------------------------------------------
 inf-1.85     4395     1114     1073   96.3      4.1   1980370.35   219.38    0.065    0.004
1.85-1.48     2571     1096     1073   97.9      2.4    844040.89    92.70    0.064    0.009
1.48-1.28     2223     1194     1073   89.9      2.1    538145.05    52.74    0.073    0.016
1.28-1.16     2088     1195     1073   89.8      1.9    411020.31    39.17    0.084    0.023
1.16-1.07     2870     1165     1073   92.1      2.7    361765.76    44.15    0.085    0.023
1.07-1.00     1996     1311     1073   81.8      1.9    314862.12    35.98    0.084    0.024
1.00-0.94     1600     1456     1073   73.7      1.5    217964.09    26.09    0.088    0.030
0.94-0.89     1629     1536     1073   69.9      1.5    156936.01    22.30    0.075    0.038
0.89-0.85     1619     1631     1073   65.8      1.5    110430.73    19.51    0.072    0.045
0.85-0.81     1495     1719     1080   62.8      1.4     84123.26    19.28    0.065    0.042
--------------------------------------------------------------------------------------------
 inf-0.81    22486    13418    10737   80.0      2.1    689492.98    77.32    0.069    0.012
 

Statistics vs resolution (taking redundancy into account) - Laue group (anomalous pairs merged): P2/m (b-unique)
resolu-      #        #        #       %       average    mean      mean          
tion(A)    kept     theory   unique complete  redundancy   F2     F2/sig(F2)   Rint  RsigmaB
--------------------------------------------------------------------------------------------
 inf-1.80     4667      676      663   98.1      7.0   1937381.04   288.95    0.103    0.003
1.80-1.42     2869      669      663   99.1      4.3    757467.35   112.60    0.120    0.008
1.42-1.23     2402      722      663   91.8      3.6    483523.37    62.48    0.129    0.015
1.23-1.11     2773      683      663   97.1      4.2    398541.41    57.69    0.155    0.018
1.11-1.03     2799      679      663   97.6      4.2    335371.90    52.01    0.141    0.020
1.03-0.97     1482      706      663   93.9      2.2    252899.94    35.96    0.133    0.026
0.97-0.92     1477      702      663   94.4      2.2    181052.89    28.70    0.138    0.033
0.92-0.88     1399      715      663   92.7      2.1    137894.77    24.83    0.142    0.038
0.88-0.84     1366      739      663   89.7      2.1    105079.50    23.29    0.121    0.041
0.84-0.81     1252      733      671   91.5      1.9     83911.59    23.04    0.127    0.040
--------------------------------------------------------------------------------------------
 inf-0.81    22486     7025     6638   94.5      3.4    689492.98   103.10    0.115    0.012
DC PROFFITRRPTWIN INFO: Step 7 - Generating output files
 
HKLF 4
Reflections read=25000, from those 22486 with overlapping factor < 0.717 written to file C:\Users\msiegle2\Desktop\xs0190a\test4_twin1_hklf4.hkl, 2514 skipped
Use the HKLF 4 file(s) for structure solution.

HKLF 5 merged
RINT ANALYSIS FOR ALL HKLF5 REFLECTIONS
 Components measured    kept     unique redundancy F2/sig(F2) Rint      Rsigma
------------------------------------------------------------------------------
1,2          25000     22245     12627     1.76     48.13     0.016     0.019

RINT ANALYSIS FOR OVERLAPPED REFLECTIONS
 Components measured    kept     unique redundancy F2/sig(F2) Rint      Rsigma
------------------------------------------------------------------------------
1,2          14664     13187      7482     1.76     45.22     0.017     0.019

RINT ANALYSIS FOR ISOLATED REFLECTIONS
 Component measured     kept     unique redundancy F2/sig(F2) Rint      Rsigma
------------------------------------------------------------------------------
     1       10336      9058      5145     1.76     49.58     0.016     0.018
     2           0         0         0     0.00      0.00     0.000     0.000

12627 merged reflections saved into file: C:\Users\msiegle2\Desktop\xs0190a\test4_twin1_hklf5.hkl

Use this hkl file in SHELXL with BASF instruction, which has (components minus 1) entries, and HKLF 5 instruction.
E.g. Two component twin: 'BASF n2' in .ins file, BASF n1 can be computed as n1 = 1.0 - n2.
E.g. Three component twin: 'BASF n2 n3' in .ins file, BASF n1 can be computed as n1 = 1.0 - (n2 + n3).

BASF 0.44479 
;
_shelx_res_checksum              26881
_shelx_hkl_checksum              28306