Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of sp(3) C-H Bonds.
Trammell, Rachel; See, Yi Yang; Herrmann, Aaron T.; Xie, Nan; Díaz, Daniel E; Siegler, Maxime A.; Baran, Phil S.; Garcia-Bosch, Isaac; The Journal of organic chemistry 82 (2017) 7887–7904; doi:10.1021/acs.joc.7b01069

data_4032631
_publ_section_title
;
 Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of
 sp(3) C-H Bonds.
;
_journal_issue                   15
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7887
_journal_page_last               7904
_journal_paper_doi               10.1021/acs.joc.7b01069
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C17 H26 Cu F3 N2 O5 S, C F3 O3 S'
_chemical_formula_sum            'C18 H26 Cu F6 N2 O8 S2'
_chemical_formula_weight         640.07
_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   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                100.056(3)
_cell_angle_beta                 95.648(4)
_cell_angle_gamma                100.226(4)
_cell_formula_units_Z            2
_cell_length_a                   7.7369(4)
_cell_length_b                   12.5096(6)
_cell_length_c                   13.5497(5)
_cell_measurement_reflns_used    5102
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      71.97
_cell_measurement_theta_min      3.59
_cell_volume                     1259.37(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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 0.995
_diffrn_measured_fraction_theta_max 0.993
_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  0.0413
_diffrn_reflns_av_unetI/netI     0.0857
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            14411
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.885
_diffrn_reflns_theta_min         3.342
_exptl_absorpt_coefficient_mu    3.623
_exptl_absorpt_correction_T_max  0.893
_exptl_absorpt_correction_T_min  0.781
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (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            blue
_exptl_crystal_density_diffrn    1.688
_exptl_crystal_description       'small block'
_exptl_crystal_F_000             654
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.492
_refine_diff_density_min         -0.583
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.990
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     435
_refine_ls_number_reflns         5155
_refine_ls_number_restraints     355
_refine_ls_restrained_S_all      1.273
_refine_ls_R_factor_all          0.0748
_refine_ls_R_factor_gt           0.0528
_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^)+(0.0584P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1231
_refine_ls_wR_factor_ref         0.1291
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3635
_reflns_number_total             5155
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01069_si_003.cif
_cod_data_source_block           '[(S1)CuII(H2O)2(CF3SO3)](CF3SO3)'
_cod_depositor_comments
'Adding full bibliography for 4032630--4032633.cif.'
_cod_database_code               4032631
_shelx_shelxl_version_number     2014/7
_twin_information
;
 * * * CRYSALIS TWIN DATA REDUCTION FINALIZING (38.43 (release 21-03-2016)) * * *
Laue class: 1bar - Friedel mate is equivalent
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 (   7.728   12.494   13.549   100.04    95.65   100.20)
Matrix 2 is taken from component 2 (   7.752   12.492   13.516   100.11    95.47   100.23)
Twin analysis: Component 1 with component 2
TL  =UB[1]-1*UB[2]:   0.9673  -0.0753  -0.0069     0.2147   1.0300   0.0966    -0.0772  -0.0991   0.9779   det 0.999465
TL-1=UB[2]*UB[1]-1:   1.0173   0.0744  -0.0001    -0.2175   0.9459  -0.0950     0.0583   0.1017   1.0130   det 1.000536
Rot= 8.9649 deg around the following vectors: 
Reciprocal space (hkl): -0.4153 0.1010 0.9041
Direct space (uvw)    : -0.7730 0.1182 0.6233
 
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:  -0.4117  -7.7823   0.7684  d=   0.0116
  2:  -0.2102   8.0341  -1.7896  d=   0.0259
  3:  -4.5303  -1.9918   2.5255  d=   0.0348
  4:  -2.2246  -4.0418  -4.4305  d=   0.0264
  5:   2.2989  -2.3240  -7.4537  d=   0.0374
  6:   4.4476   2.4177  -1.6238  d=   0.0395
  7:   2.4921   4.0097   4.0041  d=   0.0295
  8:  -3.4486   1.1181   6.7981  d=   0.0444
  9:  -1.1308   2.0055  -9.0210  d=   0.0332
 10:   1.5997   4.9994  -6.5172  d=   0.0338
 11:  -0.6463  -4.5914   8.3958  d=   0.0476
 12:  -1.5558   7.8317  -2.6714  d=   0.0239
 13:   3.4013  -6.1791   4.3737  d=   0.0306
 14:  -3.3745   5.8255   2.5706  d=   0.0347
DC PROFFITRRPTWIN ALL INFO: Component 2
DC PROFFITRRPTWIN INFO: Face list of component 2 
  1:  -0.9977  -7.3446  -0.0373  d=   0.0116
  2:   0.3839   7.8150  -1.0077  d=   0.0259
  3:  -4.7571  -1.1385   2.0917  d=   0.0348
  4:  -2.5631  -2.9182  -5.0288  d=   0.0264
  5:   2.1668  -1.9901  -7.6530  d=   0.0374
  6:   4.7045   1.4737  -1.1398  d=   0.0395
  7:   2.8329   2.8701   4.6092  d=   0.0295
  8:  -3.4259   1.1618   6.7992  d=   0.0444
  9:  -1.0000   3.0000  -9.0000  d=   0.0332
 10:   2.0000   5.0000  -6.0000  d=   0.0338
 11:  -1.0000  -5.0000   8.0000  d=   0.0476
 12:  -1.0000   8.0000  -2.0000  d=   0.0239
 13:   3.0000  -7.0000   4.0000  d=   0.0306
 14:  -3.0000   6.0000   3.0000  d=   0.0347
 
DC PROFFITRRPTWIN INFO: Step 4 - Analysing composite reflections of 2 components
 
Component 1: 14948 observations read
Component 2: 14991 observations read

29120 composite observations collected (28498 fully isolated, 622 overlapped), 107 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  |        419 |     1.4 <--- ALMOST SEPARATED
   0.20 - 0.40  |        135 |     0.5
   0.40 - 0.60  |         42 |     0.1
   0.60 - 0.80  |         16 |     0.1
   0.80 - 1.00  |         10 |     0.0 <--- FULLY OVERLAPPED
 -------------- | ---------- | ------------ 
      Total     |        622 |     2.1

 
DC PROFFITRRPTWIN INFO: Step 5 - Scaling data & analysing twin ratios of 2 components
 
Computed twin ratios:
Twin 1: 88.55% (3057 common observations, 959 merged)
Twin 2: 11.45% (2274 common observations, 959 merged)

Preparing data for SCALE3 ABSPACK...

SCALING COMPONENT 1

14804 of 14851 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-5637.6963 max=645686.0000
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=230.3396 max=4905.4507

SCALING COMPONENT 2

14808 of 14891 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-5637.6963 max=645686.0000
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=134.3394 max=4905.4507

Computed twin ratios:
Twin 1: 89.22% (3057 common observations, 959 merged)
Twin 2: 10.78% (2274 common observations, 959 merged)

DC PROFFITRRPTWIN INFO: Determining HKLF4 overlap threshold for completeness requirement (>=80.0%)
DC PROFFITRRPTWIN INFO: HKLF4 overlap threshold kept - 0.40

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: P-1
                       #        #        #      average    mean      mean        
          intensity measured   kept    unique  redundancy   F2     F2/sig(F2)   Rint   Rsigma
---------------------------------------------------------------------------------------------
    642272-    25989     1410     1410      491    2.9     61824.74    32.22    0.028    0.029
     25949-    13080     1504     1504      491    3.1     17987.37    17.10    0.045    0.048
     13053-     8004     1489     1489      491    3.0     10295.69    12.13    0.058    0.063
      7997-     5318     1452     1452      491    3.0      6548.15     9.03    0.071    0.075
      5317-     3427     1489     1489      491    3.0      4274.36     6.33    0.088    0.096
      3427-     2177     1547     1547      491    3.2      2784.26     4.51    0.119    0.127
      2176-     1283     1466     1466      491    3.0      1679.41     2.90    0.163    0.175
      1281-      659     1500     1500      491    3.1       934.64     1.68    0.267    0.286
       658-      279     1488     1488      491    3.0       468.05     0.88    0.419    0.468
       279-    -1325     1459     1459      498    2.9        90.71     0.21    0.829    1.374
-------------------------------------------------------------------------------------------
    642272-    -1325    14804    14804     4917    3.0     10431.55     8.59    0.050    0.052
 

Statistics vs resolution - point group symmetry: P-1
resolu-      #        #        #               average    mean      mean          
tion(A)   measured   kept    unique           redundancy   F2     F2/sig(F2)   Rint   Rsigma   RsigmaA
------------------------------------------------------------------------------------------------------
 inf-1.75     1269     1269      491             2.6     45534.16    23.06    0.028    0.030     0.033
1.75-1.39      943      943      491             1.9     15893.19     8.19    0.057    0.057     0.095
1.39-1.21     1752     1752      491             3.6     12706.73     9.47    0.064    0.070     0.094
1.21-1.10     1967     1967      491             4.0     10503.46     9.92    0.055    0.061     0.088
1.10-1.02     1737     1737      491             3.5      7129.10     7.84    0.054    0.060     0.108
1.02-0.96     1662     1662      491             3.4      5070.28     6.09    0.066    0.074     0.139
0.96-0.91     1564     1564      491             3.2      3954.59     5.48    0.079    0.084     0.160
0.91-0.87     1445     1445      491             2.9      3387.48     5.43    0.077    0.079     0.165
0.87-0.84     1330     1330      491             2.7      3124.73     5.78    0.076    0.079     0.154
0.84-0.81     1135     1135      498             2.3      2370.19     5.43    0.085    0.091     0.164
------------------------------------------------------------------------------------------------------
 inf-0.81    14804    14804     4917             3.0     10431.55     8.59    0.050    0.052     0.082
 

Statistics vs resolution (taking redundancy into account) - point group symmetry: P-1
resolu-      #        #        #       %       average    mean      mean          
tion(A)    kept     theory   unique complete  redundancy   F2     F2/sig(F2)   Rint  RsigmaB
--------------------------------------------------------------------------------------------
 inf-1.75     1269      493      491   99.6      2.6     45534.16    39.57    0.028    0.021
1.75-1.39      943      495      491   99.2      1.9     15893.19    11.81    0.057    0.064
1.39-1.21     1752      493      491   99.6      3.6     12706.73    16.99    0.064    0.054
1.21-1.10     1967      491      491  100.0      4.0     10503.46    18.93    0.055    0.045
1.10-1.02     1737      493      491   99.6      3.5      7129.10    15.10    0.054    0.060
1.02-0.96     1662      494      491   99.4      3.4      5070.28    11.43    0.066    0.079
0.96-0.91     1564      494      491   99.4      3.2      3954.59     9.95    0.079    0.090
0.91-0.87     1445      496      491   99.0      2.9      3387.48     9.55    0.077    0.096
0.87-0.84     1330      497      491   98.8      2.7      3124.73     9.71    0.076    0.093
0.84-0.81     1135      514      498   96.9      2.3      2370.19     8.72    0.085    0.106
--------------------------------------------------------------------------------------------
 inf-0.81    14804     4960     4917   99.1      3.0     10431.55    15.25    0.050    0.048
DC PROFFITRRPTWIN INFO: Step 7 - Generating output files
 
HKLF 4
Reflections read=14851, from those 14804 with overlapping factor < 0.400 written to file D:\Data\xs0933a\test_abs_twin1_hklf4.hkl, 47 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          14851     14411      5161     2.79      8.54     0.041     0.086

RINT ANALYSIS FOR OVERLAPPED REFLECTIONS
 Components measured    kept     unique redundancy F2/sig(F2) Rint      Rsigma
------------------------------------------------------------------------------
1,2            622       612       370     1.65      7.92     0.042     0.085

RINT ANALYSIS FOR ISOLATED REFLECTIONS
 Component measured     kept     unique redundancy F2/sig(F2) Rint      Rsigma
------------------------------------------------------------------------------
     1       14229     13799      4791     2.88      8.55     0.041     0.086
     2           0         0         0     0.00      0.00     0.000     0.000

5161 merged reflections saved into file: D:\Data\xs0933a\test_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 0.10781 
;
_shelx_res_checksum              82632
_shelx_hkl_checksum              5716