Frontier orbitals of photosubstitutionally active ruthenium complexes: an experimental study of the spectator ligands’ electronic properties influence on photoreactivity
Jang, Hyo Jin; Hopkins, Samantha L.; Siegler, Maxime A.; Bonnet, Sylvestre; Dalton Trans.  (2017) –; doi:10.1039/C7DT01540B

data_7043730
_publ_section_title
;
 Frontier orbitals of photosubstitutionally active ruthenium complexes: an
 experimental study of the spectator ligands&#x2019; electronic properties
 influence on photoreactivity
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT01540B
_journal_year                    2017
_chemical_formula_moiety         'C29 H20 F6 N6 Ru, 2(F6 P), C2 H3 N'
_chemical_formula_sum            'C31 H23 F18 N7 P2 Ru'
_chemical_formula_weight         998.57
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 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
;
2017-04-19 deposited with the CCDC.
2017-07-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.896(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6380(5)
_cell_length_b                   21.5817(10)
_cell_length_c                   19.0970(8)
_cell_measurement_reflns_used    12845
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      72.12
_cell_measurement_theta_min      3.02
_cell_volume                     3534.4(3)
_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  0.0460
_diffrn_reflns_av_unetI/netI     0.0641
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            37035
_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         71.887
_diffrn_reflns_theta_min         3.102
_exptl_absorpt_coefficient_mu    5.686
_exptl_absorpt_correction_T_max  0.862
_exptl_absorpt_correction_T_min  0.332
_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            red
_exptl_crystal_density_diffrn    1.877
_exptl_crystal_description       needle
_exptl_crystal_F_000             1976
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.349
_refine_diff_density_min         -1.866
_refine_diff_density_rms         0.152
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.990
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     599
_refine_ls_number_reflns         10903
_refine_ls_number_restraints     249
_refine_ls_restrained_S_all      0.993
_refine_ls_R_factor_all          0.0716
_refine_ls_R_factor_gt           0.0588
_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^)+(0.1066P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1541
_refine_ls_wR_factor_ref         0.1601
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8212
_reflns_number_total             10903
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt01540b2.cif
_cod_data_source_block           6_PF6
_cod_database_code               7043730
_shelx_shelxl_version_number     2014/7
_twin_information
;

 * * * CRYSALIS TWIN DATA REDUCTION FINALIZING (38.43 (release 21-03-2016)) * * *
Laue class: 2/m (b-unique) - 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 (   8.629   21.589   19.082    89.85    96.90    89.89)
Matrix 2 is taken from component 2 (   8.658   21.545   19.079    89.92    96.83    90.19)
Twin analysis: Component 1 with component 2
TL  =UB[1]-1*UB[2]:   0.9964  -0.0194   0.0043     0.1423   1.0002   0.0369    -0.0269  -0.0212   0.9984   det 0.998680
TL-1=UB[2]*UB[1]-1:   1.0007   0.0193  -0.0051    -0.1433   0.9962  -0.0362     0.0239   0.0216   1.0007   det 1.001322
Rot= 3.6017 deg around the following vectors: 
Reciprocal space (hkl): -0.2323 0.2184 0.9478
Direct space (uvw)    : -0.7007 0.1321 0.7011
 
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:  -0.9416  13.7916   0.9068  d=   0.0131
  2:  -0.7759   1.1876 -11.9242  d=   0.0575
  3:   0.8446 -13.6353  -2.3877  d=   0.0132
  4:   0.1809  -0.7435  12.2231  d=   0.0297
  5:   5.5133   2.3134  -0.6384  d=   0.2057
  6:  -0.0084   0.8177 -12.2716  d=   0.0348
  7:  -5.5191  -2.3353   0.9284  d=   0.2048
DC PROFFITRRPTWIN ALL INFO: Component 2
DC PROFFITRRPTWIN INFO: Face list of component 2 
  1:  -0.6810  13.8415   1.1833  d=   0.0131
  2:  -0.6931   1.7255 -11.9256  d=   0.0575
  3:   0.5945 -13.6184  -2.6641  d=   0.0132
  4:   0.1047  -1.2086  12.2202  d=   0.0297
  5:   5.5651   1.5378  -0.4569  d=   0.2057
  6:   0.0696   1.2596 -12.2629  d=   0.0348
  7:  -5.5729  -1.5692   0.7465  d=   0.2048
 
DC PROFFITRRPTWIN INFO: Step 4 - Analysing composite reflections of 2 components
 
Component 1: 45239 observations read
Component 2: 45113 observations read

69054 composite observations collected (48345 fully isolated, 20709 overlapped), 175 skipped due to one or more missing parts and 148 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  |       8853 |    12.8 <--- ALMOST SEPARATED
   0.20 - 0.40  |       6224 |     9.0
   0.40 - 0.60  |       3458 |     5.0
   0.60 - 0.80  |       1655 |     2.4
   0.80 - 1.00  |        519 |     0.8 <--- FULLY OVERLAPPED
 -------------- | ---------- | ------------ 
      Total     |      20709 |    30.0

 
DC PROFFITRRPTWIN INFO: Step 5 - Scaling data & analysing twin ratios of 2 components
 
Computed twin ratios:
Twin 1: 52.31% (27649 common observations, 4902 merged)
Twin 2: 47.69% (27105 common observations, 4902 merged)

Preparing data for SCALE3 ABSPACK...

SCALING COMPONENT 1

39626 of 44934 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-1047902.4375 max=14092588.0000
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=457.4903 max=88284.7422

SCALING COMPONENT 2

39881 of 44829 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-3040233.2500 max=14092588.0000
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=410.2565 max=108293.1172

Computed twin ratios:
Twin 1: 52.14% (27649 common observations, 4902 merged)
Twin 2: 47.86% (27105 common observations, 4902 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: P2/m (b-unique)
                       #        #        #      average    mean      mean        
          intensity measured   kept    unique  redundancy   F2     F2/sig(F2)   Rint   Rsigma
  11830985-   133689     3994     3994      705    5.7    335902.45    44.99    0.125    0.154
    133355-    69585     4172     4172      705    5.9     95615.30    21.18    0.135    0.166
     69558-    44529     4049     4049      705    5.7     55776.06    15.14    0.142    0.174
     44523-    27946     3958     3958      705    5.6     35800.75    10.92    0.160    0.193
     27938-    17264     4009     4009      705    5.7     22048.27     7.53    0.195    0.242
     17250-    10212     4044     4044      705    5.7     13668.87     5.03    0.211    0.253
     10212-     5504     3940     3940      705    5.6      7596.65     2.96    0.308    0.383
      5502-     2395     3916     3916      705    5.6      3730.02     1.51    0.435    0.533
      2393-      649     3859     3859      705    5.5      1445.84     0.61    0.734    1.139
       644-   -76719     3685     3685      705    5.2      -316.92    -0.05    0.985    2.729
  11830985-   -76719    39626    39626     7050    5.6     58059.25    11.18    0.144    0.176
 

Statistics vs resolution - point group symmetry: P2/m (b-unique)
resolu-      #        #        #               average    mean      mean          
tion(A)   measured   kept    unique           redundancy   F2     F2/sig(F2)   Rint   Rsigma   RsigmaA
 inf-1.76     4108     4108      705             5.8    196578.91    29.68    0.132    0.165     0.024
1.75-1.39     3481     3481      705             4.9    102563.86    14.55    0.119    0.144     0.054
1.39-1.21     5059     5059      705             7.2     61147.46    10.19    0.161    0.199     0.082
1.21-1.10     4953     4953      705             7.0     48359.99     9.96    0.156    0.197     0.089
1.10-1.02     4183     4183      705             5.9     36390.18     8.25    0.142    0.174     0.106
1.02-0.96     4156     4156      705             5.9     34745.35     8.40    0.149    0.186     0.106
0.96-0.91     3901     3901      705             5.5     27351.84     7.75    0.174    0.213     0.122
0.91-0.87     3711     3711      705             5.3     20818.20     6.77    0.171    0.207     0.139
0.87-0.84     3314     3314      705             4.7     19204.31     7.31    0.180    0.212     0.129
0.84-0.81     2760     2760      705             3.9     15576.77     7.36    0.188    0.219     0.129
 inf-0.81    39626    39626     7050             5.6     58059.25    11.18    0.144    0.176     0.067
 

Statistics vs resolution (taking redundancy into account) - point group symmetry: P2/m (b-unique)
resolu-      #        #        #       %       average    mean      mean          
tion(A)    kept     theory   unique complete  redundancy   F2     F2/sig(F2)   Rint  RsigmaB
 inf-1.76     4108      731      705   96.4      5.8    196578.91    70.45    0.132    0.011
1.75-1.39     3481      719      705   98.1      4.9    102563.86    33.46    0.119    0.027
1.39-1.21     5059      728      705   96.8      7.2     61147.46    26.02    0.161    0.034
1.21-1.10     4953      714      705   98.7      7.0     48359.99    24.35    0.156    0.036
1.10-1.02     4183      721      705   97.8      5.9     36390.18    18.46    0.142    0.046
1.02-0.96     4156      708      705   99.6      5.9     34745.35    18.55    0.149    0.047
0.96-0.91     3901      710      705   99.3      5.5     27351.84    16.59    0.174    0.056
0.91-0.87     3711      715      705   98.6      5.3     20818.20    14.05    0.171    0.065
0.87-0.84     3314      714      705   98.7      4.7     19204.31    14.51    0.180    0.064
0.84-0.81     2760      756      705   93.3      3.9     15576.77    13.57    0.188    0.070
 inf-0.81    39626     7216     7050   97.7      5.6     58059.25    25.61    0.144    0.030
DC PROFFITRRPTWIN INFO: Step 7 - Generating output files
 
HKLF 4
Reflections read=44934, from those 39626 with overlapping factor < 0.400 written to file D:\Data\xs0921a\xs0921a_max_abs_twin1_hklf4.hkl, 5308 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          44934     37035     11063     3.35     13.22     0.046     0.067

RINT ANALYSIS FOR OVERLAPPED REFLECTIONS
 Components measured    kept     unique redundancy F2/sig(F2) Rint      Rsigma
1,2          20709     16361      5519     2.96     17.93     0.038     0.052

RINT ANALYSIS FOR ISOLATED REFLECTIONS
 Component measured     kept     unique redundancy F2/sig(F2) Rint      Rsigma
     1       24225     20674      5544     3.73      9.32     0.068     0.106
     2           0         0         0     0.00      0.00     0.000     0.000

11063 merged reflections saved into file: D:\Data\xs0921a\xs0921a_max_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 0.47856 
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_shelx_res_checksum              14316