Photochemical Resolution of a Thermally Inert Cyclometalated Ru(phbpy)(N-N)(Sulfoxide)<sup>+</sup> Complex.
Lameijer, Lucien N.; van de Griend, Corjan; Hopkins, Samantha L.; Volbeda, Anne-Geert; Askes, Sven H. C.; Siegler, Maxime A.; Bonnet, Sylvestre; Journal of the American Chemical Society 141 (2019) 352–362; doi:10.1021/jacs.8b10264

data_4133475
_publ_section_title
;
 Photochemical Resolution of a Thermally Inert Cyclometalated
 Ru(phbpy)(N-N)(Sulfoxide)<sup>+</sup> Complex.
;
_journal_issue                   1
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              352
_journal_page_last               362
_journal_paper_doi               10.1021/jacs.8b10264
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C32 H25 N6 O Ru S, F6 P'
_chemical_formula_sum            'C32 H25 F6 N6 O P Ru S'
_chemical_formula_weight         787.68
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                100.2336(18)
_cell_angle_beta                 90.1903(18)
_cell_angle_gamma                104.221(2)
_cell_formula_units_Z            8
_cell_length_a                   15.1228(4)
_cell_length_b                   16.8679(4)
_cell_length_c                   25.1053(4)
_cell_measurement_reflns_used    30094
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      72.04
_cell_measurement_theta_min      3.45
_cell_volume                     6101.7(2)
_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 0.999
_diffrn_measured_fraction_theta_max 0.998
_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  0.0397
_diffrn_reflns_av_unetI/netI     0.0666
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            73586
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.897
_diffrn_reflns_theta_min         2.749
_exptl_absorpt_coefficient_mu    5.975
_exptl_absorpt_correction_T_max  0.730
_exptl_absorpt_correction_T_min  0.309
_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            'dark red'
_exptl_crystal_density_diffrn    1.715
_exptl_crystal_description       needle
_exptl_crystal_F_000             3168
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.872
_refine_diff_density_min         -0.692
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.894
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1851
_refine_ls_number_reflns         25508
_refine_ls_number_restraints     483
_refine_ls_restrained_S_all      0.903
_refine_ls_R_factor_all          0.0510
_refine_ls_R_factor_gt           0.0364
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0459P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0854
_refine_ls_wR_factor_ref         0.0917
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19051
_reflns_number_total             25508
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            '[3]PF6.cif'
_cod_data_source_block           3_PF6
_cod_database_code               4133475
_shelx_shelxl_version_number     2014/7
_twin_info
;
 * * * 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 (  15.114   16.867   25.100   100.23    90.17   104.21)
Matrix 2 is taken from component 2 (  15.119   16.856   25.105   100.24    90.24   104.22)
Twin analysis: Component 1 with component 2
TL  =UB[1]-1*UB[2]:  -0.5351  -0.5241  -0.5050    -0.4652  -0.4760   0.5061    -0.9317   1.0462   0.0102   det 1.000242
TL-1=UB[2]*UB[1]-1:  -0.5342  -0.5229  -0.5054    -0.4667  -0.4758   0.5056    -0.9299   1.0479   0.0109   det 0.999758
Rot= 179.9408 deg around the following vectors: 
Reciprocal space (hkl): -0.4078 0.4089 0.8164
Direct space (uvw)    : -0.5389 0.6060 0.5852
 
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:   1.1890  -9.1540  -6.1873  d=   0.0745
  2:   8.7550   1.3312  -5.6291  d=   0.0374
  3:  -0.0217   9.2125   5.3676  d=   0.0603
  4:  -8.2410   3.5948   8.1148  d=   0.0368
  5:   5.0923  -4.5653 -11.9549  d=   0.0374
  6:  -5.4375   7.1239 -11.8312  d=   0.1990
  7:  -6.0260   5.7961   9.8403  d=   0.0362
  8:   6.3356  -7.9194   9.6180  d=   0.1677
  9:  -6.0006   5.0037  10.9984  d=   0.0434
 10:  -3.0114  -6.9792  -7.0233  d=   0.0323
 11:   3.0114   6.9792   7.0233  d=   0.0301
 12:  -5.0162  -2.9960  12.9853  d=   0.1259
 13:  -7.0130  -4.9735  -2.0277  d=   0.0426
 14:  -9.0036   3.0192   5.9857  d=   0.0484
DC PROFFITRRPTWIN ALL INFO: Component 2
DC PROFFITRRPTWIN INFO: Face list of component 2 
  1:   7.2787   0.6728 -10.7652  d=   0.0745
  2:  -2.5275  -7.5652  -6.8079  d=   0.0374
  3:  -7.5185  -1.6598   9.7320  d=   0.0603
  4:  -1.5792   6.2381  11.5188  d=   0.0368
  5:   5.7095  -6.2484  -9.6497  d=   0.0374
  6:   5.1595  -6.8341  12.3922  d=   0.1990
  7:  -4.7856   5.0293  11.7845  d=   0.0362
  8:  -4.1046   5.6745 -14.0850  d=   0.1677
  9:  -4.9702   5.9800  10.9432  d=   0.0434
 10:   8.8078   1.1754  -4.5895  d=   0.0323
 11:  -8.8078  -1.1754   4.5895  d=   0.0301
 12:  -2.3173  10.3318   1.6669  d=   0.1259
 13:   7.3715   4.6142   1.2879  d=   0.0426
 14:   0.2053   5.7914  11.6016  d=   0.0484
 
DC PROFFITRRPTWIN INFO: Step 4 - Analysing composite reflections of 2 components
 
Component 1: 78922 observations read
Component 2: 79004 observations read

134586 composite observations collected (111330 fully isolated, 23256 overlapped), 50 skipped due to one or more missing parts and 12 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  |       7436 |     5.5 <--- ALMOST SEPARATED
   0.20 - 0.40  |       4462 |     3.3
   0.40 - 0.60  |       4068 |     3.0
   0.60 - 0.80  |       4139 |     3.1
   0.80 - 1.00  |       3151 |     2.3 <--- FULLY OVERLAPPED
 -------------- | ---------- | ------------ 
      Total     |      23256 |    17.3

 
DC PROFFITRRPTWIN INFO: Step 5 - Scaling data & analysing twin ratios of 2 components
 
Computed twin ratios:
Twin 1: 49.21% (47810 common observations, 15622 merged)
Twin 2: 50.79% (48211 common observations, 15622 merged)

Preparing data for SCALE3 ABSPACK...

SCALING COMPONENT 1

67562 of 78874 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-435787.9688 max=2696093.7500
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=199.8493 max=11120.9072

SCALING COMPONENT 2

67915 of 78968 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-689698.0625 max=2819984.7500
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=199.8493 max=11507.5713

Computed twin ratios:
Twin 1: 49.44% (47810 common observations, 15622 merged)
Twin 2: 50.56% (48211 common observations, 15622 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
---------------------------------------------------------------------------------------------
   2581580-    57470     6609     6609     2124    3.1    130344.29    35.76    0.045    0.048
     57455-    30905     7031     7031     2124    3.3     42075.76    19.64    0.056    0.061
     30905-    19050     7002     7002     2124    3.3     24482.91    14.02    0.067    0.073
     19044-    11920     6805     6805     2124    3.2     15205.96    10.05    0.080    0.087
     11914-     7498     6819     6819     2124    3.2      9558.89     7.01    0.101    0.108
      7494-     4461     6718     6718     2124    3.2      5908.01     4.74    0.133    0.144
      4461-     2435     6596     6596     2124    3.1      3388.58     2.88    0.182    0.196
      2434-     1082     6664     6664     2124    3.1      1715.53     1.51    0.325    0.348
      1081-      295     6698     6698     2124    3.2       654.00     0.59    0.614    0.762
       294-   -39866     6620     6620     2130    3.1      -205.13    -0.10    0.981    1.843
-------------------------------------------------------------------------------------------
   2581580-   -39866    67562    67562    21246    3.2     23295.10     9.66    0.064    0.069
 

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-1.77     6393     6393     2124             3.0     73911.29    22.44    0.048    0.052     0.031
1.77-1.41     5021     5021     2124             2.4     42535.15    11.25    0.054    0.056     0.064
1.41-1.23     7446     7446     2124             3.5     26998.03     9.38    0.075    0.081     0.086
1.23-1.11     9270     9270     2124             4.4     21737.80     9.39    0.075    0.086     0.088
1.11-1.03     7734     7734     2124             3.6     17777.10     8.60    0.068    0.076     0.093
1.03-0.97     7454     7454     2124             3.5     15499.81     8.12    0.069    0.078     0.101
0.97-0.91     6969     6969     2124             3.3     12299.49     7.28    0.082    0.092     0.114
0.91-0.87     6460     6460     2124             3.0     10063.82     6.92    0.081    0.088     0.122
0.87-0.84     5856     5856     2124             2.8      7862.02     6.53    0.088    0.095     0.131
0.84-0.81     4959     4959     2130             2.3      7149.03     7.11    0.082    0.086     0.119
------------------------------------------------------------------------------------------------------
 inf-0.81    67562    67562    21246             3.2     23295.10     9.66    0.064    0.069     0.073
 

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-1.77     6393     2331     2124   91.1      3.0     73911.29    38.19    0.048    0.018
1.77-1.41     5021     2252     2124   94.3      2.4     42535.15    17.92    0.054    0.041
1.41-1.23     7446     2299     2124   92.4      3.5     26998.03    17.73    0.075    0.050
1.23-1.11     9270     2393     2124   88.8      4.4     21737.80    19.18    0.075    0.044
1.11-1.03     7734     2453     2124   86.6      3.6     17777.10    16.83    0.068    0.051
1.03-0.97     7454     2497     2124   85.1      3.5     15499.81    15.57    0.069    0.056
0.97-0.91     6969     2487     2124   85.4      3.3     12299.49    13.56    0.082    0.065
0.91-0.87     6460     2459     2124   86.4      3.0     10063.82    12.31    0.081    0.072
0.87-0.84     5856     2407     2124   88.2      2.8      7862.02    11.01    0.088    0.080
0.84-0.81     4959     2452     2130   86.9      2.3      7149.03    11.20    0.082    0.076
--------------------------------------------------------------------------------------------
 inf-0.81    67562    24032    21246   88.4      3.2     23295.10    17.53    0.064    0.042
DC PROFFITRRPTWIN INFO: Step 7 - Generating output files
 
HKLF 4
Reflections read=78874, from those 67562 with overlapping factor < 0.400 written to file D:\Data\xs1134a\twin_abs_twin1_hklf4.hkl, 11312 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          78874     73586     25568     2.88     10.92     0.040     0.068

RINT ANALYSIS FOR OVERLAPPED REFLECTIONS
 Components measured    kept     unique redundancy F2/sig(F2) Rint      Rsigma
------------------------------------------------------------------------------
1,2          23256     21010      7889     2.66     14.53     0.034     0.052

RINT ANALYSIS FOR ISOLATED REFLECTIONS
 Component measured     kept     unique redundancy F2/sig(F2) Rint      Rsigma
------------------------------------------------------------------------------
     1       55618     52576     17679     2.97      9.33     0.045     0.083
     2           0         0         0     0.00      0.00     0.000     0.000

25568 merged reflections saved into file: D:\Data\xs1134a\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 0.50558 
;
_shelx_res_checksum              31360
_shelx_hkl_checksum              53862