Ketones as Directing Groups in Photocatalytic sp3 C-H Fluorination
Bume, Desta Doro; Pitts, Cody Ross; Ghorbani, Fereshte; Harry, Stefan Andrew; Capilato, Joseph N.; Siegler, Maxime A.; Lectka, Thomas; Chem. Sci.  (2017) –; doi:10.1039/C7SC02703F

data_1546779
_publ_section_title
;
 Ketones as Directing Groups in Photocatalytic sp3 C-H Fluorination
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC02703F
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H37 F O5'
_chemical_formula_sum            'C25 H37 F O5'
_chemical_formula_weight         436.54
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_audit_update_record
;
2017-06-15 deposited with the CCDC.
2017-08-11 downloaded from the CCDC.
;
_cell_angle_alpha                81.5019(14)
_cell_angle_beta                 84.6748(15)
_cell_angle_gamma                75.0869(16)
_cell_formula_units_Z            4
_cell_length_a                   6.62820(13)
_cell_length_b                   12.7871(2)
_cell_length_c                   29.3443(5)
_cell_measurement_reflns_used    36052
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      72.05
_cell_measurement_theta_min      3.61
_cell_volume                     2373.02(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'SHELXTL v6.10 (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL v6.10 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-2014/7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      110(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0218
_diffrn_reflns_av_unetI/netI     0.0320
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            52212
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.899
_diffrn_reflns_theta_min         3.050
_exptl_absorpt_coefficient_mu    0.723
_exptl_absorpt_correction_T_max  0.938
_exptl_absorpt_correction_T_min  0.833
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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            colorless
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       'thick plate'
_exptl_crystal_F_000             944
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.261
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 7634 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1234
_refine_ls_number_reflns         19284
_refine_ls_number_restraints     349
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0396
_refine_ls_R_factor_gt           0.0375
_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^)+(0.0821P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1066
_refine_ls_wR_factor_ref         0.1087
_reflns_Friedel_coverage         0.995
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                18138
_reflns_number_total             19284
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc02703f2.cif
_cod_data_source_block           12_minor
_cod_database_code               1546779
_shelx_shelxl_version_number     2014/7
_twin_information
;
 * * * CRYSALIS TWIN DATA REDUCTION FINALIZING (38.43f (release 19-07-2016)) * * *
Laue class: 1bar - 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 (   6.625   12.787   29.344    81.52    84.66    75.10)
Matrix 2 is taken from component 2 (   6.623   12.795   29.289    81.50    84.49    74.98)
Twin analysis: Component 1 with component 2
TL  =UB[1]-1*UB[2]:   1.0001   0.0008  -0.0004     0.9994  -0.9997   0.0003     0.8325  -0.0040  -1.0021   det 1.002347
TL-1=UB[2]*UB[1]-1:   0.9995   0.0008  -0.0004     0.9995  -0.9995  -0.0008     0.8263   0.0047  -0.9983   det 0.997659
Rot= -179.9050 deg around the following vectors: 
Reciprocal space (hkl): 0.8386 0.4189 0.3481
Direct space (uvw)    : 1.0000 0.0009 0.0001
 
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:   3.2394   6.5204  -1.6841  d=   0.1684
  2:  -0.1883   0.7290 -18.5190  d=   0.0576
  3:  -3.3864  -6.6036  -1.8121  d=   0.1934
  4:   0.3379  -0.4404  18.6505  d=   0.0394
  5:   0.9935   8.2938   3.3083  d=   0.1513
  6:   4.2281   3.3400   0.2953  d=   0.1489
  7:   4.1343   0.0524  -1.0974  d=   0.1505
  8:   0.0773  -7.9685  -3.4580  d=   0.1233
  9:  -4.1890  -0.5178   0.9115  d=   0.1556
 10:  -0.3962   7.7735   3.4603  d=   0.1442
 11:  -1.0049   6.9969   3.2078  d=   0.1372
 12:   0.0093  -7.0007   7.9888  d=   0.1057
 13:  -4.0054  -0.9966  -9.3305  d=   0.1362
 14:  -2.0079   0.0053 -15.6862  d=   0.0977
 15:  -1.0104   3.0049 -16.8500  d=   0.0749
 16:  -0.0099   4.0040 -15.0154  d=   0.0931
 17:  -0.0054  -2.9929 -18.0496  d=   0.0919
 18:  -3.0000  -6.9948  -9.5280  d=   0.1746
 19:   1.9935   1.0050 -15.3745  d=   0.1173
DC PROFFITRRPTWIN ALL INFO: Component 2
DC PROFFITRRPTWIN INFO: Face list of component 2 
  1:   3.2438  -3.2778   4.3884  d=   0.1684
  2:  -0.1795  -0.9024  18.3349  d=   0.0576
  3:  -3.3892   3.2168  -1.0201  d=   0.1934
  4:   0.3292   0.7633 -18.3412  d=   0.0394
  5:   0.9983  -7.2990  -2.4430  d=   0.1513
  6:   4.2285   0.8875   3.2146  d=   0.1489
  7:   4.1325   4.0806   4.5119  d=   0.1505
  8:   0.0722   8.0441   3.4788  d=   0.1233
  9:  -4.1875  -3.6700  -4.3738  d=   0.1556
 10:  -0.3911  -8.1681  -3.7455  d=   0.1442
 11:  -1.0000  -8.0000  -4.0000  d=   0.1372
 12:  -0.0000   7.0000  -8.0000  d=   0.1057
 13:  -4.0000  -3.0000   6.0000  d=   0.1362
 14:  -2.0000  -2.0000  14.0000  d=   0.0977
 15:  -1.0000  -4.0000  16.0000  d=   0.0749
 16:   0.0000  -4.0000  15.0000  d=   0.0931
 17:  -0.0000   3.0000  18.0000  d=   0.0919
 18:  -3.0000   4.0000   7.0000  d=   0.1746
 19:   2.0000   1.0000  17.0000  d=   0.1173
 
DC PROFFITRRPTWIN INFO: Step 4 - Analysing composite reflections of 2 components
 
Component 1: 59421 observations read
Component 2: 59332 observations read

65599 composite observations collected (12523 fully isolated, 53076 overlapped), 67 skipped due to one or more missing parts and 6 skipped due to I/sig<-3.0

OVERLAP STATISTICS

2 COMPONENTS

COMPONENTS 1, 2
 Overlap factor | # in range | % of all obs 
 -------------- | ---------- | ------------ 
   0.00 - 0.20  |      11356 |    17.3 <--- ALMOST SEPARATED
   0.20 - 0.40  |      10262 |    15.6
   0.40 - 0.60  |      10631 |    16.2
   0.60 - 0.80  |      11959 |    18.2
   0.80 - 1.00  |       8868 |    13.5 <--- FULLY OVERLAPPED
 -------------- | ---------- | ------------ 
      Total     |      53076 |    80.9

 
DC PROFFITRRPTWIN INFO: Step 5 - Scaling data & analysing twin ratios of 2 components
 
Computed twin ratios:
Twin 1: 69.31% (44454 common observations, 13375 merged)
Twin 2: 30.69% (38260 common observations, 13375 merged)

Preparing data for SCALE3 ABSPACK...

SCALING COMPONENT 1

28323 of 59366 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-4768245.0000 max=28872034.0000
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=563.4278 max=73453.1016
PROFFIT INFO: 14 observations on 'bad frames' rejected

SCALING COMPONENT 2

28676 of 59306 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-16779748.0000 max=28872034.0000
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=495.6320 max=98896.3516
PROFFIT INFO: 83 observations on 'bad frames' rejected

Computed twin ratios:
Twin 1: 69.33% (44442 common observations, 13371 merged)
Twin 2: 30.67% (38228 common observations, 13371 merged)

DC PROFFITRRPTWIN INFO: Determining HKLF4 overlap threshold for completeness requirement (>=80.0%)
DC PROFFITRRPTWIN INFO: New HKLF4 overlap threshold - 0.65

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: P1
                       #        #        #      average    mean      mean        
          intensity measured   kept    unique  redundancy   F2     F2/sig(F2)   Rint   Rsigma
  12855628-   311215     4535     4535     1497    3.0    767973.55    90.86    0.075    0.086
    311120-   163242     4927     4927     1497    3.3    223032.93    44.85    0.071    0.085
    163128-    97632     4860     4860     1497    3.2    125293.35    32.14    0.081    0.096
     97615-    63346     4545     4545     1497    3.0     79159.31    24.77    0.078    0.090
     63324-    42105     4296     4296     1497    2.9     52237.25    19.23    0.095    0.107
     42104-    28180     4241     4241     1497    2.8     34571.23    14.66    0.100    0.109
     28168-    18285     3989     3989     1497    2.7     23074.62    11.11    0.112    0.119
     18283-    10399     3791     3791     1497    2.5     14322.05     7.72    0.140    0.147
     10399-     4470     3684     3684     1497    2.5      7322.47     4.33    0.203    0.219
      4464-  -663386     3486     3486     1500    2.3      1600.84     1.26    0.543    0.773
  12855628-  -663386    42354    42354    14973    2.8    144030.60    26.93    0.079    0.091
 

Statistics vs resolution - point group symmetry: P1
resolu-      #        #        #               average    mean      mean          
tion(A)   measured   kept    unique           redundancy   F2     F2/sig(F2)   Rint   Rsigma   RsigmaA
 inf-1.75     4241     4241     1498             2.8    610150.07    76.63    0.083    0.092     0.010
1.75-1.41     4711     4711     1497             3.1    175696.53    32.65    0.072    0.085     0.026
1.41-1.24     5110     5110     1498             3.4    151473.97    28.81    0.087    0.108     0.029
1.24-1.13     5614     5614     1498             3.7    133954.17    27.56    0.072    0.091     0.030
1.13-1.04     5050     5050     1497             3.4     97280.25    22.35    0.071    0.083     0.036
1.04-0.97     4626     4626     1497             3.1     64097.53    17.58    0.073    0.081     0.047
0.97-0.92     4058     4058     1498             2.7     34887.94    12.69    0.086    0.093     0.066
0.92-0.88     3552     3552     1497             2.4     29069.14    12.29    0.086    0.092     0.069
0.88-0.84     3051     3051     1497             2.0     23738.98    12.20    0.080    0.083     0.071
0.84-0.81     2341     2341     1496             1.6     22995.09    14.14    0.073    0.075     0.061
 inf-0.81    42354    42354    14973             2.8    144030.60    26.93    0.079    0.091     0.024
 

Statistics vs resolution (taking redundancy into account) - point group symmetry: P1
resolu-      #        #        #       %       average    mean      mean          
tion(A)    kept     theory   unique complete  redundancy   F2     F2/sig(F2)   Rint  RsigmaB
 inf-1.75     4241     1848     1498   81.1      2.8    610150.07   135.47    0.083    0.006
1.75-1.41     4711     1670     1497   89.6      3.1    175696.53    63.19    0.072    0.015
1.41-1.24     5110     1656     1498   90.5      3.4    151473.97    56.77    0.087    0.016
1.24-1.13     5614     1716     1498   87.3      3.7    133954.17    56.43    0.072    0.016
1.13-1.04     5050     1976     1497   75.8      3.4     97280.25    44.19    0.071    0.020
1.04-0.97     4626     2032     1497   73.7      3.1     64097.53    33.18    0.073    0.027
0.97-0.92     4058     1906     1498   78.6      2.7     34887.94    22.83    0.086    0.040
0.92-0.88     3552     1922     1497   77.9      2.4     29069.14    20.44    0.086    0.043
0.88-0.84     3051     1942     1497   77.1      2.0     23738.98    18.79    0.080    0.045
0.84-0.81     2341     2042     1496   73.3      1.6     22995.09    18.83    0.073    0.042
 inf-0.81    42354    18710    14973   80.0      2.8    144030.60    50.11    0.079    0.014
 

Statistics vs resolution (taking redundancy into account) - Laue group (anomalous pairs merged): P1
resolu-      #        #        #       %       average    mean      mean          
tion(A)    kept     theory   unique complete  redundancy   F2     F2/sig(F2)   Rint  RsigmaB
 inf-1.73     4482      961      830   86.4      5.4    587664.82   170.78    0.087    0.004
1.73-1.39     4958      887      830   93.6      6.0    171377.92    76.02    0.080    0.012
1.39-1.22     5573      881      830   94.2      6.7    148520.28    75.53    0.102    0.013
1.22-1.11     5803      910      830   91.2      7.0    130894.50    74.33    0.087    0.013
1.11-1.02     4898     1009      830   82.3      5.9     88219.19    55.31    0.080    0.017
1.02-0.96     4532      986      830   84.2      5.5     58290.47    41.96    0.082    0.023
0.96-0.91     3816      940      830   88.3      4.6     32468.05    28.50    0.105    0.033
0.91-0.87     3385      926      830   89.6      4.1     28318.89    26.57    0.098    0.035
0.87-0.84     2807      918      830   90.4      3.4     23349.75    24.48    0.093    0.038
0.84-0.81     2100      936      833   89.0      2.5     22767.54    23.62    0.082    0.037
 inf-0.81    42354     9355     8303   88.8      5.1    144030.60    65.46    0.088    0.011
DC PROFFITRRPTWIN INFO: Step 7 - Generating output files
 
HKLF 4
Reflections read=59351, from those 42354 with overlapping factor < 0.652 written to file D:\Data\xs1380a\twin_abs_twin1_hklf4.hkl, 16997 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          59351     52212     19338     2.70     27.22     0.022     0.026

RINT ANALYSIS FOR OVERLAPPED REFLECTIONS
 Components measured    kept     unique redundancy F2/sig(F2) Rint      Rsigma
1,2          52979     46164     16497     2.80     27.79     0.022     0.026

RINT ANALYSIS FOR ISOLATED REFLECTIONS
 Component measured     kept     unique redundancy F2/sig(F2) Rint      Rsigma
     1        6372      6048      2841     2.13     22.95     0.020     0.029
     2           0         0         0     0.00      0.00     0.000     0.000

19338 merged reflections saved into file: D:\Data\xs1380a\twin_abs_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 0.30673 
;
_shelx_res_checksum              59115